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         - 180 -

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levels.  At least three candidate elutriate/slurry treatment processes  have
shown promise to date:  UV ozonalysis, biodegradation with  selected  fungi  and
molds, and amine assisted photolysis.   Retrievable synthetic sorbent and
polymer films both appear applicable as in situ approaches  at this  time.
     The information presented here is preliminary in nature.  Many  analytical
data are yet to be evaluated and numerous tests must still  be completed.  Only
after these have been concluded and viewed collectively can recommendations  be
made for implementation of mitigation activities on the James River.
                                      - 181 -

-------
                               REFERENCES

 1.   Ananymous.   "The  Stabilization Game," Environmental Science Technology.
     9.,  (7),  p.  622-623,  1975.

 2.   J.  L.  Maloch.   teachability and Physical Properties of Chemically
     Stabilized  Hazardous  Wastes.  EPA-600-1976-015, U.S. Environmental Pro-
     tection  Agency, Cincinnati, Ohio, p. 127-138, 1976.
                                        ^
 3.   C.  C.  Wiles and H. R.  Lubowitz.  A  Polymeric Cementing and Encapsulating
     Process  for Managing  Hazardous Wastes.  EPA-6QO/9-77-015, U.S. Environ-
     mental Protection Agency,  Cincinnati, Ohio, p. 139-150, 1976.

 4.   J.  W.  Keeley and  R.  M.  Engler.  Discussion of Regulatory Criteria for
     Ocean  Disposal  of Dredged  Materials:  Elutriate Test Rationale and Imple-
     mentation Guidelines.   Office Chief of Engineers, U.S. Army Report No.
     D-74-14, Dredged  Materials Research Program, March 1974.

 5.   G.  L.  Lee,  et al.  Research Study for the Development of Dredged Material
     Disposal Criteria.   Institute for Environmental Sciences, Contract
     Report No.  D-75-4, Dredged Materials Research Program, November 1975.

 6.   N.  A.  Esmen and R. B.  Fergus.  "Rain Acidity:  pH Spectrum of Industrial
     Drops,"  The Science  of the Total Environment.  6(1976) 223-226, El
     Sevier Publishing Company, Amsterdam.

 7.   H.  P.  Vind.  "The Role of  Microorganisms in the Transport of Chlorinated
     Insecticides,"  J. M.  Sharpley and A. M. Kaplan (editors).  Proceedings
     of the 3th  International Biodeterioration Symposium, 3_, 793, 797,
     Applied  Science Publishers, Ltd, London, 1975  (published 1976).

 8.   L.  R.  Brown, I. G. Alley and D. W.  Cook.  The Effect of Mirex and Caro-
     furan  on Estuarine Microorganisms.  National Environmental Research  Center,
     Office of  Research and Development, U.S. Environmental Protection Agency,
     Corvallis,  Oregon, 1975.

 9.   A.  S.  Jones and C. S.  Hodges,  "persistence of Mirex and its Effects on
     Soil Microorganisms," J. Agr. Food. Chem. 22,  (3) p. 435-439, 1974.

10.   P.  Androde, Jr.,  W.  B.  Wheeler and  D. A. Carlson.   "Identification of  a
     Mirex  Metabolite," Bull. Environ. Contam. Toxicol., 1_4,  (4) p. 473-479,
     1975.

11.   P.  Androde, Jr. and  W.  B.  Wheeler.   "Biodegradation of Mirex by Sewage
     Sludge Organisms," Bull. Environ. Contam. Toxicol., ]_]_,  (5) p. 415-146,
     1974.

12.   E.  E.  Gilbert, P. Lombardo,  E. J. Runowski and G. L. Walker.   "Prepar-
     ation  and  Insecticidal  Evaluation of Alcoholic Analogs of  Kepone," J_._
     Agr.  Food  Chem.,  1£, (2) p.  11-114, 1966.
                                       182 -

-------
13.   E.  G.  Alley, B.  R.  Layton and J.  P.  Minyard,  Jr.   "Identification  of
     the Photoproducts of the Insecticides  Mi rex and Kepone,"  Journal of
     Agricultural and Food Chemistry,  22.,  (3),  p.  442-445,  1975.

14.   J.  R.  Gibson, G. W.  Ivie and H.  W.  Dorough.   "Fate of  Mirex  and  Its
     Major  Photodecomposition Product in  Rats,"  Journal  of  Agricultural and
     Food Chemistry,  20,  (6), p.  1246-1248, 1972.

15.   D.  A.  Carlson, K. D. Konyha, W.  B.  Wheeler, G.  P.  Marshall and R.  G.
     Zaylskie.   "Mirex in the Environment:   Its  Degradation to Kepone and
     Related Compounds,"  Science. 194. (4268),  p.  939-941,  1976.

16.   G.  E.  Walsh, K.  Ainswenth and A.  J.  Wilson.   "Toxicity and Uptake  of
     Kepone in  Marine Unicellular Algae,"  - Short  Papers and Notes -  Chesa-
     peake  Science. Vol.  18,  No.  2, June  1977.

17.   M.  V.  Widman and M.  M.  Epstein.   Polymer  Film Overlay  System for Mercury
     Contaminated Sludge  - Phase  I.  U.S.  Environmental  Protection Agency,
     16080MTZ,  May 1972.

18.   Takenaka Komuten Co., Ltd.   Recent  Developments in Dredged Material
     Stabilization and Deep  Chemical  Mixing in  Japan,  Technical Report,
     June 23, 1976.

19.   M.  Suzuki, N. Aisawa, G. Okuno and  T.  Tokahashi.   "Translocation of
     Polychlorinatedbiphenyls in  Soil  into  Plants:   A  Study by a  Method of
     Culture of Soybean  Sprouts," Arch.  Environ. Contam. and ToxicoJ.,  5_,
     p.  343-352, 1977.
                                 - 183 -

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                        SESSION III
          "Related Sediment Contamination Problems"
CHAIRMAN
Dr. Leo J. Hetling
Director
Bureau of Water Research
New York State Department of Environmental Conservation

SPEAKERS

Edward G. Horn, Ph.D.
Research Scientist III
Bureau of Water Research
New York State Department of Environmental Conservation
"Hudson River - PCB Study Description and Detailed Work Plan"

T. J. Tofflemire, Dr. Engr.
Research Scientist III
Bureau of Water Research
New York State Department of Environmental Conservation
"Hudson River Sediment Distributions and Water Interactions Relative
      to PCB - Preliminary Indications"

Russell C. Mt.Pleasant
Director
Bureau of Monitoring and Surveillance
New York State Department of Environmental Conservation
           and
Carl  Simpson, Ph.D.
Research Scientist II
Environmental Health Center
New York State Department of Health
"The Use of Artifical Substances for Monitoring Toxic Organic
     Compounds:  Preliminary Evaluation Involving the PCB Problem
     in the Hudson River"

Paul M. Griffen
Manager
Separation Technology Project
Research and Development Center
General Electric Company
"Research Progress on Removal or Treatment of PCB in Hudson River
                    Sediment"
                                   - 184 -

-------
 HUDSON RIVER -  PCB
STUDY DESCRIPTION AND
 DETAILED WORK PLAN
   Edward G. Horn
         and
   Leo J. Hetling
         - 185 -

-------
                              INTRODUCTION








     On September 8, 1976 the New York State Department of Environmental




Conservation and the General Electric Company signed an agreement bringing




to a close the action brought against General Electric relating to the




discharge of polychlorinated biphenyls (PCBs) into the Hudson River.   This




paper presents a detailed description of the Department of Environmental




Conservation's program for implementing Section 3 of the settlement which




is tne portion related to monitoring and reclamation of the river.
                                   -  186  -

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                                 BACKGROUND









          Polychlorinated biphenyls (PCBs) were first manufactured in 1929




and their chemical properties were soon discovered to be ideal for a number




of industrial uses.  They are extremely stable chemically and biologically,




conduct electricity very poorly,and possess a very low solubility in water.




In the United States*they have been used for a wide variety of purposes, most




heavily as a heat transfer fluid and insulator in heavy electrical equipment.




But, these same chemical properties create a significant biological hazard.




          This hazard might have gone unnoticed had it not been for an indus-




trial accident in Japan that has come to be called the Yusho ("rice oil




disease") incident.  In 1968 this disease (manifest primarily as a serious




skin disorder) was traced to PCB contamination of rice oil during its manu-




facture.  Since that incident, more research has turned up rather frightening




facts.




          Yusho victims are still exhibiting symptoms of the poisoning and,




even though not exposed to additional PCBs, they still have high levels of




PCBs in their blood and other body tissues.  Several deaths among the victims




have been associated with malignant cancers, though it is not possible to




conclusively state that the PCBs caused the cancers.  Recent evidence shows




that the rice oil and tissues of Yusho patients also contained polychLorinated




dibenzofurans (PCDFs).  PCDFs are more toxic than PCBs.  It is therefore not




possible to conclusively associate the symptoms of this incident with PCB




poisoning. ^-L»^/




          Experiments with laboratory animals, including monkeys, however, con-




firm that many of the symptoms associated with Yusho are directly related to
                                       - 187 -

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consumption of PCBs and persist in the bodies of all experimental animals long




after they are removed from diets containing PCBs.  In addition to deaths being




noted at high doses, liver tumors have also been induced in mice and rats.  An




exhaustive summary of these effects can be found in the recent Criteria




Document for PCBs (1976) published by the Environmental Protection Agency(-*-)




and a report published by the United States Department of Health, Education




and Welfare' '.




          As a result of accumulating research on PCB toxicity, the United




States Food and Drug Administration (FDA) has set standards for allowable



                                (3)
levels of PCBs in various foods.









                             THE PCB SETTLEMENT









          Polychlorinated biphenyls were discovered to be a problem in the




Hudson River in 1975.  The United States Environmental Protection Agency and




Fish and Wildlife Service  analyzed samples of fish taken from the river  and




found that PCB concentrations were higher than the FDA limits by a substantial




margin. The fish could thus not legally be shipped for interstate sale.  Acting




on this and additional evidence that the Department of Environmental Conservation




(DEC) had itself collected, charges were brought against the General Electric




Company (GE) for polluting the river with the toxic substance PCB.  Adminis-




trative proceedings began on September 8, 1975.  On February 9, 1976, after




weeks of testimony and a substantial record of several thousand pages of trans-




cripts, prefiled testimony, reports, studies and other exhibits, the Hearing




Officer, Professor Abraham D. Sofaer,  found that DEC had presented overwhelming




evidence of GE's responsibility for high concentrations of PCBs in the upper




Hudson's waters, sediment, organisms and fish. In a 77-page interim opinion,










                                      - 188 -

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Professor Sofaer detailed the evidence and the violations^),  it is  interesting to




note that he found that the unlawful actions were the consequence of both corpor-




ate abuse and regulatory failure by the responsible Federal and State agencies.



          In order to determine the appropriate remedial measures, a second




phase of the hearing was held during the spring and summer of 1976.   As a




result of this hearing, a settlement agreeable to all parties was negotiated




and finalized exactly one year after the administrative proceedings  began,




September 8, 1976^.




          The settlement calls for  a comprehensive program of




at least $7 million to deal with PCBs in the Hudson River and related environ-




mental concerns.  General Electric was required to reduce its PCB discharges,




which had been averaging about 30 pounds per day until 1972, to one pound per




day beginning September 8,  1976, and to construct a wastewater treatment




facility at the Hudson Falls and Fort  Edward Capacitor Manufacturing Facilities.




Total PCB discharges from the plants were reduced to one gram  (0,022 pounds)




per day by May 1977.




          The agreement stipulated that GE was to cease using PCBs by July,




1977 and to perform $1 million of research on several items including the




environmental compatibility of any  substitute.  Finally, GE was required to




contribute $3 million to the Department as its share of additional work to




further monitor the presence and levels of PCBs; to investigate the need for




remedial action concerning PCBs present in the Hudson and to implement such




action, if necessary; and to aid in developing a program to regulate the




storage and discharge of substances hazardous to the environment.  New York




State was, by the agreement, obligated to provide an  additional  $3 million




for this work and the Commissioner of Environmental Conservation became
                                       - 189 -

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responsible for overseeing and expediting the required work.  An overview of




the provisions of the settlement related to studies of the Hudson River and




the Department's activity to date in implementing them is shown in Table 1.









                             ADVISORY COMMITTEE









          A key provision of the settlement is an Advisory Committee consisting




of independent experts and governmental and private interests which was estab-




lished to "review and make public recommendations to the Commissioner concerning




the scope, content, progress and results of the programs, studies and expendi-




tures".




          The PCS Settlement Advisory Committee  has been appointed and meets




monthly to carefully evaluate the work in progress and make recommendations




regarding results and further studies.




          The relationship of this Advisory Committee to the Department and




implementation of the settlement is given in Figure 1.









                          THE HUDSON RIVER PROBLEM









          In order to better understand the Hudson River PCB problem, it is




useful to know something about the river itself.




          For most purposes, the Hudson River Drainage Basin can be divided




into three sub-basins - the Upper Hudson River, the Mohawk River and the Lower




Hudson River as shown in Figure 2.




          Table 2 shows the relative area and water flows for these three basins.




From Ft.  Edward to Cohoes the Upper Hudson River is actually a series of low
                                         -  190  ~

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                                      Table  1

              Overview of Task Required by Section 3 of PCB Settlement
Settlement Provisions
Department Activity to Date
I.  Advisory Committee

    The Commissioner of Environmental
Conservation will establish an Advisory
Committee consisting of independent ex-
perts, governmental and private interests
which will, at regular meetings review and
make public recommendations to the Commis-
sioner concerning the scope,content,  progress
and results of the program, studies and
expenditures for which provision is  made
in the agreement.

II.  Other Funds

     In the event that the funds herein
provided for implementing remedial actions
concerning PCBs present in the Hudson River
shall be inadequate to assure protection of
public health and resources, then the
Department will use its best efforts to
obtain additional funds from sources other
than GE, that are necessary to assure such
protection.

II1^  Overall River Prograni

    1.   Monitor the presence and levels
of PCBs which have been discharged in
Hudson River waters in water, sediment
and biota.
An Advisory Committee has been formed and
it meets regularly.
No action can be taVen until a decision as
to the need for and cost of specific
remedial action is n^ide.
A monitoring program has been developed by
the Dept. and approved by the Advisory Com-
mittee.  This program includes contracts for
PCB mapping with Normandeau Assoc., PCB lab
analysis with O'Brien and Gere, and water and
sediment transport measurements with USGS.
An extensive program of fish, macroinvertebrate,
water and air monitoring by the Dept. is also
underway.

EPA special core study of estuary section
was carried out in December 1976.  Lamont-
Doherty Lab will carry out studies to follow-
up the results of this survey.

For more detail see Table 3.
                                      - 191  -

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Settlement Provisions
Department Activity to Date
    2.  Further investigate the need for
remedial action concerning PCBs present in
the Hudson River.
    3,  Implement remedial action if neces-
sary to protect public health and resources,
concerning PCBs present in the Hudson River.

    4.  Aid in developing a program to
regulate the storage and discharge of sub-
stances hazardous to the environment if
sufficient monies are available after im-
plementing remedial action concerning PCBs.

IV.  Workto be Carriedout by GE ($1 million)

     GE will condi ct research itself or by
contract on the ervironmental compatibility
of its substitute non-PCB dielectric capa-
citor fluids ($400,000).

     GE will conduct research to be approved
prior to being undertaken by the Commissioner
after his consul ation with the Advisory
Committee on the removal or treatment of
PCBs in supernatant liquids and sediments
from the Hudson River sludge($400,000).

     GE will conduct research as specified
by the Commissioner of the effects on the
environment of noi  more than three substances
which may be hazardous to the environment
and which are to be selected by the Com-
missioner after his consultation with the
Advisory Committee ($200,000).
Contracts for studies relating to taking no
remedial actions and to removal of PCB
contaminated sediments by dredging are under-
way (see Figure 5).

The Advisory Committee has approved main-
tenance dredging by DOT of a small section of
the east channel of the river near Ft. Edward.
An environmental assessment for this project
has been prepared*?'' )and  approved.  Dredging
is expected to take place during the summer
of 1977.  Experience from this project will
be useful in evaluating and design of future
projects.

No action can be taken until above studies
are received.
No action can be taken until a remedial
action program is decided upon and imple-
mented; however, an overall Hudson River
research program is being prepared by the
Advisory Committee.
A substantial amount of work on the substi-
tute nas been done by GE.  A preliminary
report'"^  on the substitutes has been pub-
lished and is under review.
                   (Q)
The work study plan   presented by GE has
been approved by the Commissioner on the
recoitoiendation of the Advisory Committee and
work is underway.
The Aivisory Committee has been asked to
reconcnend three substances for study.  They
have established a subcommittee for this
task.
                                  -  192 -

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                             Figure 1

        Organizational Chart for the PCS Settlement Between
General Electric and The Department of Environmental Conservation
                     COMMISSIONER'S OFFICE
                                        A.E
            PCB ADVISORY COMMITTEE
             Chairman/Co-Chairman
DEC Project
 Manager
Contractors
                                   DEC
                                  Staff
        General
        Electric
          A.  Give advice and respond to questions.

          B.  Managerial direction
              1.  Advise DEC about short-term and long-term
                  planning.

              2.  Receive and react to periodic reports from
                  DEC staff.

              3.  Assist DEC in evaluations.

              4.  Assist DEC in preparing reports and recommendations
                  to the Commissioner.

          C.  Technical resource.

          D.  Exchange of information.

          E.  Managerial direction.

          F.  Public access and information.
                          - 193 -

-------
                 75-
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                                                      VER.
          FIG. 2
  HUDSON RIVER BASIN
     10 5 0	10	to  10
                        - 194

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level dams and serves as part of the Champlain Canal  (Figures 3 and 4).  The




Mohawk River serves as the eastern portion of the New York State Barge Canal




and joins the Hudson River just above the Troy Dam.





          The lower Hudson Basin is tidal over its entire 150 miles (241 km),




Average tides are 4.4 feet (104 m) at the Battery, 3.0 feet  (1 m) at Beacon




and 4.8 feet (105 m) at Troy.  Tidal flows at Poughkeepsie have been




measured as 230,000 to 280,000 cfs (6,516-7,932 cms).    Dye studies have




shown that the flow actually oscillates with the tide, with  a very slow net




outflow.  Because of this tidal flow, salt-water intrusion extends quite a




distance upriver.  The 50 mg/1 (0005 o/oo) salinity fluctuates from 20 ml.




(32,2 km) above the Battery  (near Tappan Zee Bridge) to 70 mi. (112.7 km)




inland  (south of Poughkeepsie) depending on the freshwater flow.




          Testimony given    at the hearing clearly demonstrates that al-




though the levels of PCBs in fish and other animals are alarming, most of




the PCBs are held in the sediments on the river bottom and suspended in the




water.  Very little PCBs can be found in the water itself, but because of




bioaccumulation, it is enough to create a serious hazard.  "Clean" fish




placed in this water in cages ("live-cars") have accumulated dangerous PCB




levels in their flesh within one month   .




          Existing data indicates that the sediments in the  section im-




mediately below the GE discharges at Fort Edward are the  most contaminated.




General Electric discharged  large volumes of PCBs for at least 25 years.




Much of this probably accumulated in the sediments impounded behind the




dams south of the manufacturing plants,,  The first dam was located in




Fort Edward, but, for various reasons, it was removed in the late summer




of 1973   ;  Some of the contaminated sediment which subsequently moved
                                  - 196 -

-------
e^png
     U.S-8.S. «A«C
UPPER  HUDSON
 RIVER  BASIN
                         - 197 -
                                                 FIGURE 3

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downriver has been removed by Department of Transportation's  (DOT) dredging




to maintain the Champlain Canal.  Much, however, still remains, particularly




in the region between Fort Edward and the Thompson Island dam.




          The essence of the Hudson River problem is that these PCBs are




now slowly leaching back into the river and if no action is taken, may con-




tinue contaminating the river and its biological system far into the future.




It is also possible, however, that the contaminated sediments may be




covered or moved by nature to a section of the river where they may no




longer present a problem or that they may have so spread out over the




entire length of the river that no action is possible,,







                          THE PLAN OF STUDY







          Although research prior to and since the court proceedings demon-




strates a serious problem does exist with respect to PCBs in the Hudson




River, the complete scope of the problem and the appropriate remedial




action are not clear.  The State plan adopted is a complex program to




ascertain the seriousness and precise location of PCB contamination in the




Hudson River and to evaluate the cost, environmental as well as financial,




of any remedial action.  This program has been formulated by DEC,




approved by the Advisory Committee, and is now underway  (Figure 5).  A




summary of this plan follows









A.  Monitoring Study




          In order to define the concentrations and movements oE PCBs in




the river system, a comprehensive monitoring program has been developed.




The program(H) outlined in Table 3 includes monitoring  of fish, macro-
                                - 199 -
-------
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invertebrates, sediment, hydrology, wastewater treatment plant input,



water and air.  Some highlights of this program are described below.



          The Department's Division of Fish and Wildlife is responsible for



a basic biological monitoring program, and as part of this program, it: will



be  collecting fish at six sampling locations spread throughout the river



from Stillwater to the Tappan Zee Bridge.  Most of the sampling will take



place in the Lower Hudson River where commercial fishing interests are the



greatest.  Nine common species are expected to be sampled, mostly during



May and June, but American Shad were taken during their spawning run in



April.  In addition to these studies, macroinvertebrates are being sampled



throughout the spring and summer.



          These animals, as well as all other materials, will be analyzed



for PCBs by chemists at O'Brien and Gere Engineers of Syracuse, New York.



This firm follows a rigorous quality control program designed and monitored



by the Department of Health and can handle the large number of samples ex-



pected during the program,,  Before the study is complete, several thousand



samples will be analyzed for PCBs using a gas chromatograph-electron capture



detection.



          Normandeau Associates, Inc. of Bedford, New Hampshire, was



awarded a contract to map the river bottom measuring the sediment thickness



and PCB content from Fort Edward to the Troy dam, in the region where



sediment was shown to be most heavily contaminated.



          In December 1976, the EPA Region II office used a helicopter to



collect Hudson River sediments between Troy and the Tappan Zee Bridge



because sampling in this region had previously been scanty.  Results of


            (12")
this survey     suggested that the Lower Hudson River also has highly
                               - 201 -
-------
contaminated sediment in at least four of the twenty sites sampled.  To


further investigate this possible problem, a contract is in process with


Lament Doherty Geological Laboratory.  Lamont Laboratory has collected,


analyzed and archived cores in the Lower Hudson over the past several years.


With this unique collection and new ones from selected sites, it should be


possible to get a much better understanding of PCB levels throughout the


estuary portion of the Hudson River.


          The United States Geological Survey is cooperating in the study


by continuing their work on sediment transport, particularly during big


storms and the spring thaw. Because high water in the river often moves large


volumes of sediment, PCB measurements provide an indication of whether, and


how rapidly, contaminated sediments in the Upper Hudson move downriver.


          Not included as part of the program, but a study that will


contribute to it, is an aquatic ecology and water quality study being done

                                                                      (i QN
by Equitable Environmental Health, Inc. for Niagara Mohawk Power Corp.v  '


as input to their preparation of an environmental impact statement for


possible reconstruction of a hydraulic dam at Fort Edward.


B.  Need for Active Restoration


           All of this new information, and the previously collected data,


will be synthesized and analyzed by three different teams of scientists and


engineers.  Two of these teams have been commissioned to study the fate of


PCBs in the river if no action is taken to remove them.  The first, the


firm of Lawler, Matusky and Skelly of Tappan, New York, will concentrate


on PCB contaminants in the sediments and their movement in the river.  The


second, Hydroscience Associates, Inc. of Westwood, New Jersey, will concen-


trate its efforts on the biological systems and PCB uptake from the water


and sediments.
                              -  202 -
-------
       The third team is Malcolm Pirnie, Inc. from White Plains, New York,




who has been awarded a contract to determine the technical feasibility,




engineering methodology, cost and environmental impact of dredging con-




taminated sediments from the river.  Although many other methods have been




suggested for removing PCBs from the river, at the present moment, dredging




is the only proven technology which could be applied in the immediate future.




Other techniques would probably take at least five years before they could




be used on the necessary scale.  By then, the highly contaminated, and




presumably confined, sediments might well be elsewhere.




          Additional information on dredging of PCB contaminated sediments




will be gained as a result of dredging operations planned for the summer




of 1977(">').  Although the primary purpose of this operation is main-




tenance of the canal system in the Fort Edward area, the work will be closely




monitored in order to evaluate the practicality of dredging in PCB con-




taminated areas.



          Dovetailing with Malcolm Pirnie's work, Weston Environmental




Consultants of West Chester, Pennsylvania, are evaluating various landfills




and dredge material disposal sites.  If dredging is to be seriously con-




sidered, the dredged  materials must be treated and/or placed somewhere.




Leaching could return much of the PCBs back to the river unless adequate




precautions are taken.




          The results of these studies are due early in 1978.  Hopefully,




they will provide the basis for deciding whether remedial action is




desirable.  If dredging is the proper action to be taken, how, when and




where should it be done to provide the greatest removal with the least




environmental impact and least cost?  If it appears that dredging is unwise,
                                  -  203  -
-------
then what direction should DEC take in attempting to solve this problem?




The answers to these questions will not be simple but the work being




carried out as part of the PCB settlement will insure that in making them we




will have the best scientific input possible.




          A multitude of geologists, chemists, biologists and engineers




from State and Federal agencies,  private firms and educational institutions




are directly involved in this massive study.   A list of the principal




groups involved is given in Table 3.  Such a  cooperative endeavor, although




difficult, is becoming more commonplace as we realize the necessity of




integrating our scientific and technological  knowledge to solve problems




of our own making.  This study can be viewed  as a test to see if such an




effort can succeed.
                               - 204 -
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                                          Table  4
                  Estimate  of Direct  Expenses Related to GE/PCB Settlement
                                (September 1976  - March 1979)
Contract
Purpose
                                                                      Amount
                                                                        Total
            From GE
             PCB $
Normandeau

O'Brien and Gere

U.S. Geological
 Survey

Lawler, Matusky
 and Skelly

Hydroscience


Malcolm Pirnie
Malcolm Pirnie
Roy F. Weston

Lamont-Doherty
 Geol. Laboratory

Rensselaer Poly-
 technic Inst.

Dr. Edward Horn
Other Expenses

Advisory Committee

Monitoring equip-
 ment and supply

Project management


New York State
Surveying and mapping.                           $   98,686   $   98,686

PCB laboratory analysis.                            300,390      300,390

Increased monitoring of PCBs, flow and sediments.   120,000*      60,000
Study of no-action alternatives, with
emphasis on sediment-PCB movement.

Study of no-action alternatives, with  emphasis
on biological uptake of PCBs.

Environmental Impact Statement for East Channel
maintenance dredging; engineering analysis; pre-
paration of plan and specifications; permit
application.

Assessment of technology, cost and environmental
impact of dredging PCB-contaminated sediments.

Study of PCB landfill and spoil disposal sites.

Track down sources of PCBs in Hudson estuary.


PCB transport in Hudson River bedloaj sediments.
107,000      107,000
 58,442
 75,000**
58,442
270,000      270,000


225,000      225,000

 75,834       75,83-i


  5,000***         0
Coordinator of study and PCB Advisory Committee.      5,400        5,400

                        Subtotal                 $1,340,752   $1,200,75?
Operating expenses.                                  25,000

Office and field equipment needed to carry out       65,000
monitoring studies.

Special supplies and expenses related to project     19,248
management.
In-kind services related to monitoring, data
evaluation and study management.

                        Total
250,000
20,000

65,003


19,248


     00
                                                                     $1,700,000    $1,305,000
  * $60,000 matching funds  provided  by USGS.
 ** Funded  from Fort  Edward Dam  removal fund  (NYS  Legislative Appropriation,  Chap.  992 of
                                              the Laws of 1974).
*** NYS Science and Technology Foundation.
                                       - 206 -
-------
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                                                     -  207  -
-------
          If studies now underway indicate that no remedial action is ad-




visable, or if required action will cost less than $3.3 million, the




settlement specifies that the remaining funds will be utilized to aid in




developing a program to regulate the storage and discharge of substances




hazardous to the environment.
                                  -  208 -
-------
                                 REFERENCES
1.   Nisbet, Ian C.T. (1976), Criteria Document for PCBs, EPA 440/76-021.

2.   Subcommittee on the Health Effects of PCBs and PBBS (1976), Final
     Report, Department of Health, Education and Welfare, Washington, DC.

3.   Department of Health,Education and Welfare (April 1, 1977), Federal
     Register 42(63): 17487-17494.

4.   Sofaer, Abraham D. (1976), Interim Opinion and Order, File No. 2833.

5.   Sofaer, Abraham D. (1976), Recommendation of Settlement, File No. 2833.

6.   Malcolm Pirnie, Inc., (April 1977), Environmental Assessment of Main-
     tenance Dredging, Champlain Canal, Fort Edward Terminal Channel, Fort
     Edward, New York.

7.   Malcom Pirnie, Inc.  (May 1977), Supplement No. 1, Environmental Assess-
     ment of Maintenance Dredging, Champlain Canal, Fort Edward Terminal
     Channel, Fort Edward, New York.

8.   General Electric Company, (Feb. 28, 1977), Interim Report, Dielektrol
     Fluids, Environmental Impact Assessment Program, GE Co., Capacitor
     Products Dept.

9.   Griffen, P. M. and McFarland, C. M. (Feb. 22, 1977), Research on
     Removal or Treatment of PCB in Liquid or Sediments Dredged from the
     Hudson River, Proposed Study.

10.  Malcolm Pirnie, Inc., (1975), Investigation of Conditions Associated
     with the Removal of Fort Edward Dam.

11.  Mt.Pleasant, R., (Oct. 26, 1976), Hudson River PCB Monitoring Data
     Summary, Past, Present, Proposed, NYS Staff Report.

12.  EPA, (Feb. 23, 1977), PCBs in Lower Hudson River Sediments - A Pre-
     liminary Survey 12/11/76-12/15/76.

13.  Equitable Environmental Health, Inc., Study Plan for Upper Hudson River
     Related to the Ft. Edward and Hudson Falls Dam.
                                     -  209  -
-------
        Hudson River Sediment Distributions and Water Interactions

                   Relative to PCS - Preliminary Indications*
Introduction



     Substantial discharges of PCB to the Hudson River occurred for approximately



25 years near Ft. Edward and Hudson Falls, New York.   Due to the recent con-



struction of industrial treatment plants and in-plant changes to a substitute



compound for PCB, these discharges of PCB to the Upper Hudson have been



reduced to less than 1 gram per day.  It is believed that much of the PCB


                                                                            (1)
became adsorbed on the sediment, wood chips and organic debris in the river.



In 1973, the Ft. Edward Dam was removed and much of the PCB laden sediment



that had accumulated behind the dam washed downstream as bedload and suspended



load.  There were large dragline dredging projects in 1975 and again in


                                                     (2)
1977 near Ft. Edward to remove some of this material.  '  Several floods



over the years have greatly spread out the PCB laden sediment.  Routine



channel dredging for many miles downstream of Ft. Edward has removed some



additional PCB.  Barge traffic in the river may have contributed to spreading



out of the PCB laden sediment.  Extraction of PCB from the sediment to the



water and volatilization of PCB from the water may have reduced the PCB



concentrations in the first couple inches of bed sediment.  Biological



degradation and dilution  of the PCB laden sediment may have had a similar



effect.



Methods



     Roughly 700 grab samples and 250 cores of the bed sediment and 25 bedload



samples were taken in the Upper Hudson over a 40 mile river reach from



Ft. Edward to Troy, New York   .  Bedload samples were taken with the Bogardi T-3



and Helley Smith samplers.^ '  The cores averaged 14 inches (35 cm) in length



and were typically cut into 4 sections.  However, some cores were as long as



5 ft.(1.8 m) and were sectioned every inch.
*T.J. Tofflemire, N.Y.S. Dept. of Environmental Conservation, Albany,  N.Y.  and

 T.F. Zimmie, Civil Engineering Dept., Rensselaer Polytechnic Institute, Troy, N.Y.



                                     - 210 -
-------
Analyses on these sediments included grain size, volatile solids,  and PCB



on most of the samples.  PCB was always reported as 3 aroclors 1016, 1221,




and 1254 and the total.  Some of the sediments were subjected to 16 hour




soxlet extraction and some to 1 hour shaker extraction.  Many of these samples




were not yet analyzed for PCB at the time this paper was written.   Therefore,




the data indications are preliminary and subject to change as more data



                                                                           (5)
becomes available.  A lesser number of sediments indicated in Table 1 and 2




were analyzed in 1976 for dry bulk density, floatable solids, and total




extractables (oil and grease).  Some samples were examined under a binocular




microscope by a geologist and also subjected to energy dispersive x-ray


                                              (5)
analysis using a scanning electron microscope.




     Sediments were collected as indicated in Table 1 and placed in clean




1 quart glass jars with an aluminum foil seal, which were stored at  5°C



until use or analysis.  Some sediments were dried at 60°C and dry sieved



through clean brass sieves according to standard soil testing procedures.




Suspended solids, % solids and % volatile solids were done in accordance




with "Standard Methods  for the examination of water and wastewater",(APHA)



13th edition.  Turbidity was done with a Hach D.R.  Engineers Laboratory kit




(nephalometric type instrument).  Floatable solids  was done as follows:



The sediments were dried at 100°C, weighed, placed  in a known weight of




water and stirred for 1 minute.  The floatable matter was removed with a spatula.




The weight loss due to removing the floatable matter was determined and dividied




by the dry weight of sediment used to get % floatable.  By this procedure some




adsorbed water was removed in the floatable matter.




     Water samples for PCB analysis were collected  in hexane washed glass




bottles with ground glass stoppers.  Water and sediment samples were analyzed



for the three aarochlors of PCB by standard procedures used by the N.Y.S. Dept.




of Health, Albany, and adopted by O'Brien  and Gere Engineers, Syracuse.  If




not otherwise stated,  total PCB is used.


                                        - 211 -
-------
     For the sediment water mixing studies, 4 liter beakers and a standard




four position gang stirrer were used. Sediments of known moisture contents




were weighted wet and the proper dry sediment to Hudson River water weight




ratios obtained to simulate dredging conditions.  A total solution volume




of about 2.8 liters was used per beaker.  Parameters varied in the 13 jar tests




included mixing time, settling time, sediment to water ratio, and sediment PCB




concentration.  It was also decided to determine both soluble desorbed PCB




and total PCB including that in the suspended solids as desired.  To separate




the solids from the liquid, an International Model PR2 centrifuge was used at




3300 rpm and 2000 RCF.  The wet solids were transferred to an extraction thimble




and filtered therein.  The liquid was put back in the centrate.  The solids




in the thimbles were analyzed as sediment samples.  Centrifuging was not




sufficient to effect complete solids separations.  Therefore, 3 samples that




had been centrifuged were split and ^ filtered through a . 45 >u millipore




filter.  The filtered solids were also placed in the extraction thimble.




Then the liquid samples were submitted for PCB analysis according to standard




procedures.  For some of the water samples an emulsion formed, but it was




broken by adding and wasting methanal.  On the samples were an emulsion




occurred, 3 to 4 extractions with hexane, as opposed to the normal 2




extractions were performed, to remove essentially all the PCB.




     In addition, many 500 ml jar tests on 20 different polymers and chemicals




were conducted to determine the best coagulent for removing turbidity rapidly




from sediment water mixtures.




     Full scale dredging with cutterhead hydraulic dredge(figure 3) operated by




the N.Y.S. Department of Transportation was monitored at 3 sites. (A) Lock 1,




3 miles north of Waterford, N.Y.  (B) Bouy 212, 3 miles south of Ft. Edward,




N.Y. and (C)Lock 4 near Stillwater, N.Y.  The dredge pumped about 20-24 cfs(34-




41 cu W/ min.to individual spoils lagoon areas where most of the solids settled



                                         - 212 -
-------
and the water returned to the river through a wood overflow box structure.




The return flow was monitored daily and samples periodically taken for




turbidity, suspended solids, PCB and heavy metals.




     Polymers were fed on the dredge to improve the turbidity removal  in the




spoils lagoon.  They were fed by a Cole Palmer masterflex pump into a  line




receiving tap water dilution  and then into the suction side of the dredge




pump.  The polymers mixed with the dredged slurry in>the pipeline.  The




velocity in the pipeline was 20 ft/sec(7.1 m/s).  At Lock 1,three




different cationic polymers Drew Floe 410, Nalco 7134 and Calgon Cat floe B




were tried in 2-8 hour experiments on 3 different days.  At Bouy 212 Cat floe B




was fed continuously after 9:30 a.m. for almost every day of dredging.  At  Lock




4, Cat floe B was additionally fed at the second stage of a 3-stage lagoon




system through a gravity pipe diffuser.




     Salt tracer studies were performed to determine the retention times of the




spoils lagoons.  A 100 lb(45 kg) bag of calcium chloride was dumped at the




pipe entering the lagoon and the conductivity monitored at the overflow box




structure.  Styrofoam  chips were dumped and timed to also give approximate




flow through times.




Bed Sediment and Bedload Data




     The bed sediments typically contained wood chips, saw dust, shale chips,




cinders, and coal fragments in the coarse sizes, while the fine sizes contained




quartz and feldspar sand, fragments of the above,clay, muck and organic mate-




rial^).   The fine fractions (less than .42 mm) usually contained much less




wood.  The bedload samples had similarlies to  the bed sediment but generally




contained less silt clay and muck.  Figures 1 and 2 show sieved fractions of two




bed sediments.  Wood chips were noticed in the coarse fractions in Figure 2.




Previous studies have noted the river bed is often fissible black shale of  the





Trenton group  or Albany  clays.



                                         - 213 -
-------
     From the data in Table 2 and from microscopic examinations it was noted


that wood chips were often present in the >.4 mm size fractions of bed samples


but absent in the finer sizes.  This contributed to often causing the coarser


size fractions to have higher volatile solids and floatable solids and lower


bulk density.    For bed load samples, the wood was often present in the coarse



sieve fractions but absent in the finer fractions.  It is noted that saw dust is a


good adsorber for oil and that PCB is oil soluble.  The bedload from Waterford


had considerably more round shale pebbles, while the up river samples contained



more quartz and feldspar in the fine sands and more wood chips, angular shale

                                     (5)
chips and cinders in the coarse sizes


     For several typical samples that had wood chips, sand, and some muck,


the PCB was present throughout all grain sizes.  As indicated in Table 3,


PCB was as high in concentration in the very coarse materials (^2 nun) as in the


fine materials( 4- .075 mm).  For some samples, the medium size sands were often


lower in organics and PCB.  From the analysis of about 1000 bed samples it  was


generally found that the highest PCB occurred in muck deposits high in


volatile solids.  However, some bed samples of coarse sand and wood chips


were also moderately high in PCB.  The analysis of this data is not yet


complete however.


     For 45 sieved bedload samples taken from the Waterford Rt. 4 Bridge in


March 1977(201-49) there was a fairly good correlation of PCB and volatile


solids,  r ^ .86(4).  It was also noted that some bedload samples taken at


Ft. Edward and Schuylerville in March 1976 were high in volatile solids and


PCB.  However, the Waterford Rt. 4 Bridge bedload samples taken during high


flow in March 1976 contained no wood chips, low organics and low PCB while


some of the March 1977 samples at Waterford were higher in wood, organics


and PCB.  Table 4 summarizes the 1977 total calculated bedload movement


appeared relatively small considering suspended load PCB movements of 5,  000


                                        -  214  -
-------
-'•10,000 Ib/yr (2270-4540 kg/yr) over the Troy Dam. (8)   However,  some of the




PCB concentrations in the bedload were surprisingly  high,   80 ppm for example




on 4/1/77.  The bedload may have been higher in an open river without dams.




     Figure 4 provides a hydraulic profile of the Upper Hudson and indicates




the eight dams(7 river reaches) from Ft. Edward to Troy.  Although all




analyses on the 700 grabs and 250 cores are not all  complete, preliminary




indications are that the highest PCB concentrations  were in the first river




reach with values over 1000 ppm behind the Thompson  Island Dam.  Concentrations




of 25-100 ppm in this upper river reach were common  while the lowest river




reach(Lock 1 to Troy Dam) had concentrations of 5-25 ppm.   In the river, it  was




noted that the muck deposits typically occurred along the banks and the coarse




sands in the main channel.  Malcolm Pirnie Inc.(10)  found that the mean of the




700 grab sample D50 sizes was about .3 mm.  The D50  is the sieve size that passes




50% of the sample.  In addition,20% of the samples had a D50 of greater than 2 mm




while  another  10% of the samples had a D50 of less  than .06 mm(the silt size




division).




     The 250 cores from the Upper Hudson and their 1000 to 1200 subsections




were only partially analyzed at this writing.  However, there did appear to  be




a trend of the PCB being highest in the layer 3-8"(7.6 -20 cm) below the top




of the core.  Generally the PCB did not extend below  2 ft.  (.6 m)  in the core,




although there were exceptions to this.  Many of the cores were taken near the




river banks where muck deposits were most prevalent.




Sediment  Water  Interactions




     As described in more detail in another report(5), 13, 2.8 liter jar




tests were performed in which Hudson River sediment  was mixed with clean river




water in usually 1/10  sediment to water ratios.  After various settling times





after various solids separation procedures(centrifugation or filtration) PCB,







                                         - 215 -
-------
suspended solids, and turbidity were measured in the water and in the fine solids



separated from the water.  The sediment total PCB generally ranged from 10-300 ppm



and caused a total water PCB of 10 to 200 ppb and a soluble water PCB of 2-6 ppb.

                                                                                  3
This gave a sediment to soluble water PCB partition coefficient ranging between 10


and 10  and typically near 10  for mixed jar tests simulating dredging.  For a river


situation simulated by a fish tank experiment with water flowing over sediment

                                                          .(5)
in a tank, the partition coefficient appeared closer to 10 .    Diffusion


of the PCB off the bottom and into the entire water column may add a limiting



factor here since soluble PCB values for Upper Hudson River water are typically



less than .5 ppb.  Elutriate tests on Hudson River sediment authorized by N.Y.S.



Department of Transportation also confirmed soluble water PCB concentrations in



the 2-6 ppb range/    However, a few jar tests on sediments  high in PCB and



volatile solids indicated some unusually high soluble PCB values of about 50-

        (5)
100 ppb.     It is not yet known what the cause of this was.   However, it may



have been due to a fine suspended turbidity or to a high level of soluble oils



and TOC in the water or due to a scum accumulation on the water surface which was


included in the water sample tested for PCB.  Jar tests on Hudson River sediments



by Malcolm Pirnie(9) provided some other usefull insights. As the water to sediment


ratio increased from 10/1 to 10,000/1 there was a 30-40 fold  increase in the


total quantity of PCB suspended or extracted from a given weight of PCB in the


sediment.   This implies that higher river flows will extract more total pounds of


PCB from the river bed  and at the same time yield a higher partitioning coefficient.



     The data from the 13 jar tests were' plotted in Figure 5  and related PCB and



suspended solids in the water.  The PCB values and other data on the TOl sediment



were given in Tables 2 and 3.  The TOl sediment PCB was 26.45 ppm while the less



than .075 mm size fraction had a PCB of 35.55 ppm.
                                       -  216 -
-------
It is possible that the sediment fines suspended in the jar water after several




hours were much smaller than .075 mm and had a  PCB content  of 100 ppm.   If  this




is assumed, then the PCB in the water can be calculated directly  from the




suspended solids in the water as noted in Figure 6 for T01  sediment.




Correlating the PCB and suspended solids data in Figure 5,  gave an r-value




of .76.  In a jar test, it appeared that PCB in the sediment was  extracted




to the partition coefficient level in the water in less than one  hour.




     Many additional 500 ml jar tests were conducted on Hudson River  sediments




in which only turbidity and frequently suspended solids were measured (6).




Some of these are summarized in Table 5.  It was found that sediment  high in




volatile solids and in silt and clay caused high water turbidity  and  suspended




solids that did not settle quickly.  The addition of a 20 mg/1 cationic




polymer or 100 to 180 mg/1 of alum followed by 1.5 to 2.5 hrs. of settling




gave turbidities \ 50 JTU, and suspended solids
-------
Full Scale Dredging Data




     The N.Y.S. Department of Transportation hydraulic dredge shown in Figure




3 was monitored at 3 sites on the Upper Hudson-Lock 1, Bouy 212, and Lock 4.




The Lock 1 spoils lagoon was on a small island that had a fractured shale




bottom.  The lagoon walls or dikes were also made of shale chips and sand.




For the- first month of pumping at 20-24 cfs(34-4l cu m/min) into the lagoon,




there was almost no effluent over the spillway box leaving the lagoon.  The




dredging water filtered through the dike walls and bottom and returned to the




river.  This water was sampled on several occasions and found to have quite low




turbidity(< 20JTU).




     The rocks settled in the influent end of the lagoon as shown in Figure




6, and the fines near the effluent end of the lagoon.  The lagoon retention




time was about 15 minutes, and some short circuiting of the effluent out the




typical box shown in Figure 6 occurred.  As indicated in Table 6, the




combination of four factors-(A) 26% silt and clay in the sediment dredged,(B)




only 1% solids on the average pumped by the dredge,(C) short retention time of




15 minutes and (D) 15 ppm of total PCB in the sediment being pumped-resulted




in only 80% removal of suspended solids and 73% removal of PCB.  When 15-20




mg/1 of cationic polymer was temporarily fed on the dredge, these removals




increased to 96% for suspended solids and 95% for PCB.  However, with the short




retention time some of the flocculated sediment fines were flushed and scoured




out of the lagoon upon dredge start up.




     The Bouy 212 spoils lagoon site was on a silty loam soil and had deep,




well compacted dikes near the river bank.  There was much less percolation




here.   Figure 7 shows a portion of the dikes with sediment accumulated and the




lagoon drained.  Wood chips and sand were the dominant materials dredged.










                                         - 218 -
-------
A drag line shown in the background was used to pull accumulated sediment out




of the lagoon so that its limited volume was not filled up with  sediment.




As noted in Figure 8 an oil boom was used to retain the scum which  was found




extremely high in PCB (18,000 ppm dry wt).  The scum was partially  removed by




raking it up onto the dikes.  In the future a better scum removal  system is




recommended.  The sediment dredged had about 5%, the retention time was about




45 minutes and the sediment PCB was about 100 ppm.   Cat floe B was  fed on the




dredge most of the time.  Typical removals were 99% for suspended  solids and




PCB.  The polymer cut the effluent suspended solids and PCB about  in half as




noted in Table 6.  For both sites it was likely that there was only about a




5% increase in the downstream river concentration of PCB due to  the dredging




return flow.  Sampling of the river upstream and downstream of the  dredge




indicated that the loss of sediment due to dredge head disturbance  was minimal.




Additional discussions of these two sites (Lock 1 and Bouy 212)  are available




(6, 11, 12).




     The Lock 4 spoils lagoon was also on an island of fractured shale and there




was considerable seepage through the bottom and sides which was  observed to be




clear and have a turbidity of less than 20 JTU.  Figures 9 and 10  show the Lock  4




site which initially had 2 lagoons in series and later 3 lagoons in series. The




last lagoon was long and narrow.  It had brush and tall grass and  roughly a 30




minute retention at peak flow.  An oil boom was used to retain the  scum which




developed Cat floe B at 20 mg/1 was periodically fed on the dredge  or to the




effluent box before the last lagoon.  When the polymer was fed on  the dredge,




turbidity and suspended solids values were usually cut in half.   When polymer




was fed at the last box, turbidity values were dramatically reduced to less




than 10 JTU as opposed to no polymer values of over 500 JTU.











                                         - 219 -
-------
It is felt that excellent flocculation and mixing occurred as the effluent




passed through the long narrow channel with brush.  In addition,  the polymer




was not wasted by attachment to sand which settled in any event in the first




lagoon.  Some preliminary data on Lock 4 is given in Table 6.  The PCB results




were not yet available.




     It was also observed at this site that at a retention time of 15 minutes




or less there was a flushing of fines out of the first lagoon upon dredge




start up.  More details on the Lock 4 dredging and on intensive river




monitoring near the dredge head are available (13).
                                        - 220 -
-------
Summary Indications




                    Bed Sediment:




     The sediment from the Upper Hudson was typically a  mix of wood chips,




organic debris, cinders, coal fragments, shale chips and  sands,especially




in the main channel.  The muck and silt deposits were generally along the




banks and occasionally very high in PCB.  The PCB was not all  in the fine




material, but also in the coarse material.  Frequently the PCB concentrations




in the most contaminated cores were highest in the 3-8 inch(?.6-20 cm)  layer




below the top.




                    Bed Load:




     At Waterford, there was a good correlation between  PCB and volatile




solids in the bed load.  The bed load was a relatively small percentage of  the




total suspended load PCB transport.  There appears to be an increase in the




wood chips, volatile solids and PCB in the bed load at Waterford from April




1976 to March 1977.




                    Sediment-Water Interactions:




     From jar tests simulating dredging, the partition coefficient between




soluble PCB in the water and in the sediment was 103 to  K)5.  This coefficient




increased as the water to sediment ratio increased.  In  jar tests on various




Upper Hudson sediments, the reduction of turbidity and suspended solids in  the




water resulted in reduction of PCB and heavy metals in the water.  Cationic




polymers were effective in rapidly reducing the turbidity in the sediment




water mixtures.




                    Dredging Experience:




     In summary, it was observed that the removals of turbidity and suspended




solids in the dredging water mixture was a function of lagoon retention time,




polymer feed and the nature of the sediment dredged (% silt and clay, and




% volatile solids).  It was found that:



                                         - 221 -
-------
     1.  A retention time of one hour in the spoils lagoon is the first




step of best practical treatment to assure at least 90% removal of suspended




solids.  For coarse textured sediments with low % volatiles, the removals may




be greater.  Jar tests on the sediment water mixtures of the sediments to be




dredged are the simplest way of testing this in advance for a given site.  In




rivers such as the Hudson, which often have a velocity of 1 fps, the elutriate




test which measures only soluble pollutants, gives only part of the information




needed.




     2.  To achieve one hour flow through time as measured roughly by the




time from the addition of salt at the lagoon influent to the time of the peak




of the conductivity at the lagoon effluent, one of several steps must be taken.




          A.  The lagoon must be greatly oversized initially if no changes




              in the lagoon are to be made during operation, or




          B.  The lagoon must have sufficient depth so that the water level can




              be periodically raised as the sediment fills in the lagoon




              volume, or




          C.  Heavy equipment must be frequently used in the lagoon to remove




              accumulated sediment.




     3.  Longer retention times (1 hr. to 18rr hrs.) are encouraged and will




probably give suspended solids removals of 95-99%.  At long retention times,




it is doubtful that the cost of the polymer will be worth the results achieved.




     4.  20 mg/1 of cationic polymers, Nalco 7134, Cat floe B, and Drew floe 410




were found very effective in coagulating and flocculating turbidity in the




dredging lagoon.  They were most beneficial in reducing suspended solids when




the retention time was less than 30 minutes.   Retention times of 30-15 minutes




with polymer may achieve almost a good a removal of suspended as 1-2 hours with




no polymer.  Retention times of less than 15 minutes frequently five suspended



solids removals of no greater than 80% and should be basis of shutdown of dredging




                                        - 222 -
-------
t'ntil changes are made.  Upon dredge start-up at 15 mins.  Lagoon retention,  there is




often a large flushing of sediment fines out  of the lagoon.




     5.  The polymer is most effective  when fed in  the  second  stage  of  a




two-stage lagoon system.  Good mixing and flocculation  of  the  polymer  is




essential to improve its effectiveness.   Good mixing and flocculation  is




sometimes difficult to achieve when the polymer is  added between lagoons.




In such a case, it may be better to add the polymer on  the dredge and




benefit from the mixing in the pipeline.  Alum proved as effective as




cationic polymer in jar tests and is considerably cheaper.  However, the




large volumes to be fed and sludge production are problems with alum.




     6.  Chlorocarbons and PCB tend to  concentrate  in a scum or oil




layer which accumulates on the surface  of some dredging lagoons.  This  scum




layer should be periodically removed from the top of the lagoon and  buried or




disposed of properly.  An oil boom is the first step to retain the scum,  but




a method of removal such as a gravity scum drain-off must also be planned for




and built into the lagoon system.




     7.  Permeable sand or shale lagoon dikes provide very effective suspended




solids removal and will lengthen the retention time in  the lagoon.  However,




pollution of present or ptential well waters must be avoided.
                                         - 223 -
-------
                                 Reference Cited


(1)     Hudson River PCB Study Description and Detailed Work Plan,
        N.Y.S. Dept. of Environmental Conservation, Bureau of Water
        Research, July, 1977.

(2)     Environmental Assessment Statement Proposed Maintenance Dredging,
        Fort Edward, N.Y.  Malcolm Pirnie, Inc., White Plains, N.Y.,
        April, 1977.

(3)     Hudson River Survey 1976-1977, Final Report, Planimetric Maps and
        Cross-Section Maps, by Normandeau Associates, Inc., Bedford, New
        Hampshire, September, 1977.

(4)     Dyvik, R. and Gilchrist, C.,  "Comparison and Evaluation of Two
        Bedload Samples in the Hudson River", Master of Engineering Thesis,
        Rensselaer Polytechnic Institute, Troy, N.Y., May, 1977.

(5)     Tofflemire, T.J., "Preliminary Report on Sediment Characteristics and
        Water Column Interactions Relative to Dredging the Upper Hudson River
        for PCB Removal", N.Y.S. Department of Environmental Conservation,
        Albany, N.Y., April, 1976.

(6)     Tofflemire, T.J. , "Summary of Data Collected Relative to Hudson River
        Dredging", N.Y.S. Department  of Environmental Conservation, Room 519,
        50 Wolf Road, Albany, N.Y., December, 1976.

(7)     Engineering Report - Investigation of Conditions Associated with the
        Removal of Ft.  Edward Dam and Appendix F by Malcolm Pirnie, Inc., White
        Plains, N.Y., February, 1975.

(8)     Engineering Report - Preliminary Appraisal Sediment Transport Relations,
        Upper Hudson River by Malcolm Pirnie, Inc., April, 1976.

(9)     Aikins-Afful, E.P. unpublished jar tests data, Malcolm Pirnie Inc.,
        White Plains, N.Y., September, 1977.

(10)    "Evaluation of the Feasibility of Dredging PCB Contaminated Sediments,
        Upper Hudson River, N.Y.S. Base Data, Malcolm Pirnie, Inc., White Plains,
        N.Y., October,  1977.

(11)    Zimmie, T.F. and Tofflemire,  T.J., "Dredging PCB Contaminated Sediments
        in the Hudson River" Proc. of Geotechnical Engineering and Environmental
        Control Specialty Session, 9th ICSMFE, Tokyo, Japan, 1977.

(12)    Zimmie, T.F. and Tofflemire,  T.J., "Disposal of PCB Contaminated
        Sediments in the Hudson River" Proceedings of the Conf. on Geotechnical
        Practice for Disposal of Solid Waste Materials, June, 1977, ASCE, N.Y.,N.Y.

(13)    Tofflemire, T.J., "Unpublished data and memos on Lock 4 Dredging", N.Y.S.
        Dept. of Environmental Conservation, Room 519, 50 Wolf Road, Albany,
        N.Y.  12233, November, 1977.
                                      - 224 -
-------



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                                        TABLE 2.  SUMMARY SEDIMENT ANALYSES
New No.
11 PC3 T01
dried 100°C





11 PCS T01
Re sample

dried 60°C



11 PC3 T02





11 PC3 T03




11 PCS T06


11 PC3 T07





Bed Load
Z03


ZC8


Ass. No.
0068






1680
1681
1682
1633
1684
1685
1686
0072





02096





1690
1689
1688
1687

1749
1748
1747
1746
1745

02253
02252
02251
02260
02259
02258
Size Fract.
mm
Total
+2.0
+1.18
+ .595
+.420
+.210
-.210
+2.0
+1.18
+.59
+.42
+.21
+ .075
-.075
Total
+2.0
+1.18
+.595
+ .21
-.21
Total
+1.18
+.42
+.15
-.15
Total
+.42
+.15
+.075
-.07.5
Xatal
+1.18
+.42
+.15
+.075
-.075

+.84
+.25
-.25
,+.84
+.42
-.42
V»t *
on Sieve
100
10.1
12.1
37.6
17.2
15.4
7.0
12.0
12.1
32.1
15.5
19.0
7.1
2.2
100
70.0
17.0
7.1
3.2
2.6
100
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100
13.5
50.2
28.4
8.0
100
6.4
15.3
38.5
27.6
12.2

20.9
63.2
15.9
26.8
36.4
36.8
Volatile
Solids %
6.0
25.76
9.33
5.94
1.59
1.61
3.58








1.68
.94
2.63
4.66
2.76
24.0




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8.1
1.27
.12
16.5
1.82
.71
Floatable
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9.0
57.0
27.5
9.8
.7
2.4
2.5
23.8
34.4
12.7





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6.6
7.2
5.1
18.0




12.2
14.0
2.7
3.9
11.16
37
98
75
33
30*
30*







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Extracted
Comments com
62.5* solids 1029
Bulk density increased




**•
2227
2958
862
94
550
1700
1630
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Bulk density increased


V
60.5* solids_ TD<- '^3 '£'£
Bulk density increased 4731
greatly gl8
1 1090
^ - 3120
35* solids /~JC- ?-7"/>
Bulk density increased 15500
4 fold 11474
1 3449
1 2910
*' 5760

2230
901
7587
1536
811
359
PCB-ppm
Tot^l
20-40






36.9
36.1
41.1
4.85
5.75
25.85
35.55
4.5-13





3.3




19.0*
34.6
8.45
3.6
10.3
233**
671
257
127
87
155

135.8
13.35
3.35
65.7
8.4
2.4
 *S'jspected to  be  high  due to low test weight  used.
**1975 PC3 analyses
                                                               - 228 -
-------
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-------
                                        TABLE 4
                             HUDSON RIVER BEDLOAD MOVEMENT
Date
3/23/76

3/24/76
4/2/76



3/11/77
Sample
No.
Z01
Z02
Z03
Z04
Z05
Z06
Z07
Z08
Z09
Z10
Zll
Z12
Z13
Z01
thru
Z49
Bridge on Hudson, Station
Fort Edward, East 230
Fort Edward, East 150
Fort Edward, West 250
Fort Edward, West 380
Nor thumb e r land
Schuylerville , Lock 5
Schuylerville, East 170
Schuylerville, West 110
Fort Edward, West 280
Fort Edward, East 230
Schuylerville, West 110
Waterford Bridge, 110
Waterford Bridge, 270

Waterford Bridge, 260
Approx. Total
Flow- Bedload
cfs Ib/day
904
407
6,512
6,512
9000 869
36
1,309
9000 12,595
32,000 558,878
60,654
163,565
49,000 62,700
368,893

18,500 1,070
Total
PCB
ppm
14.3
36.5
28.5
11
23.7
26
34.2
27.5
116.4
16.0
9.5

39.
Total
PCB
Ib/day
.013
.015
.371
.399
.010
.001
.330
19.1
1.67
19.0
1.0
3.5

.0418
          and
3/14/77   Z71,
          Z72
3/15/77


3/16/77

4/1/77
Waterford Bridge, 100,
 470,260

Waterford Bridge, 260,
 470

Waterford Bridge 260

Waterford Bridge 260
54,100    86,318


62,100   183,538

45,700    14,976

21,500     8,269
                       6.1
         .53
30.     5.55

 4.81    .072

80.      .66
*  Estimated
                                                 - 231 -
-------
                                       Table 6

                       Summary  of Dredging Results  at 2 Sites
                                                  LOCK 1        BUOY 212
       LAGOON FLOW THRU TIME
       TYPICAL, BY SALT TRACER                    15 min.        45 min.

       LAGOON INFLUENT
           Average % solids                         1%             5%
           PCB in solids                          15 ug/g       100 ug/g

       LAGOON EFFLUENT
           Suspended solids, without polymer     2000 mg/1      500 mg/1
           Suspended solids, with polymer         400 rag/1      250 mg/1
           PCB, composite, without polymer         40 ug/1      100 ug/1
           PCB, composite, with polymer             8 ug/1       50 ug/1

       REMOVAL EFFICIENCIES
           Suspended solids, without polymer        80%           99%
           Suspended solids, with polymer           96%           99.5%
           PCB, without polymer                     73%           98%
           PCB, with polymer                        95%           99%

       SILT AND CLAY
           Percent passing //200 sieve (average)     26%            5%

        *Polymer fed between lagoons

                                        Table 5
                              LOCK 4

                               55 min.
                               460
                               230, 20*
                               99, 99.9*
                               20-30%
         Summary of Jar Test Results Using Typical Hudson River Sediments
Sediment Location
& Concentration     Float-    Vola-
                    ables %   tiles &
Schuylerville         962
Ft. Miller            241
Buoy 214-Ft.
  Edward              2.7       2         11
Behind T.I. Dam      17.5       7         45
Stillwater           13.4       3         10
Lock 1 in canal      18        24         26
Waterford Bridge      2.8       5.4       54
         For
    Settling Times
1.5-           18 -
2.5 hrs.        24 hrs.
                                                 Turb.   SS.   Turb.  SS.
   For
Chem. Coag-
ulation*
                         Turb.   SS.
1000   500  500   300      37   20
 200   150  100    50      -    -

 800   450  500   200      45
2500  1500  450   300      55
 300   168   -             32
1150   715  162    94      -
 675   462  170   150      37   30
       20
       45
        5
     hours settling
-------
                        £
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-------
                                FIGURE  5
     SUSPENDED  SOLIDS
            vs
     PCB for 2.8 liter JAR  TESTS
1000
 IOO
 6
 I
 CO
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£ 10
o
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           T02.6
                                                         TOI
Calculation for TOI

Based on 100 ppm PCB

m fines  (Susp, Solids)


Susp. Solids   PCB in water
                                                 1000

                                                 500

                                                 200

                                                 I 00

                                                 50

                                                 I 0
              100

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                           10                     100


                    WATER PCB CONCENTRATION- ppb
                          1000
                                     - 237 -
-------
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-------
                    Figure 7
         Bouy 212 Dredging Spoils Lagoon
Showing Wood Chips and Sediment after Dewaterino
                  October 1976
                   - 239 -
-------
              Figure 8
   Bouy 212 Dredging Spoils Lagoon
Showing Scum Retention During Operation
            October 1976
                - 240 -
-------
Figure 9 - Aerial Photograph of Lock 4
           Dredging Spoils Siie
           September, 1977
                - 241
-------
                                      Figure  10
                             MAP LOCK  4
                             SPOIL  SITE

                             Scale  l"= 200'

                             Key	Road
                                 	River Bank
HUDSON
 RIVER
                                                                Canal
                                                             xrf Box 2, Top VV. /
                                                               • Weir 87.3 IO|3[/77
                                                                         \
HOOSIC
 RIVER
                                                           p West Weir
                                                      Board 105.0,  lo|3|77


                                                      Used
                                                     of So. Weir 109.1

                                                 Stake 105.3
                                       - 242 -
-------
The use of artificial substrates for monitoring toxic organic compounds:

  A preliminary evaluation involving the PCB (polychlorinated biphenyl)

                  problem in the Hudson River,  New York
                                   by
                             Karl W. Simpson
                   Division of Laboratories and Research
                    New York State Department of Health
                          Russell C. Mt. Pleasant
                          Division of Pure Waters
          New York State Department of Environmental Conservation

                                   and

                               Brian Bush
                   Division of Laboratories and Research
                    New York State Department of Health
                                   - 243 -
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Introduction




     The following report concerns our ongoing efforts to use multiplate




sampling of macroinvertebrates for monitoring PCB (polychlorinated biphenyl)




contamination in the surface waters of New York State.  This method shows great




promise for providing information not available from more conventional data,




and it may be applicable to studies of other environmental contaminants.






Historical Development and Rationale




     The severity of PCB contamination in the Hudson River has been well es-




tablished through fish and sediment data (Spagnoli and Skinner, 1975; Nadeau




and Davis, 1976; New York State Department of Environmental Conservation, 1976;




U.S. Environmental Protection Agency, 1977).  While these data are of obvious




value in establishing the occurrence of PCB's in the river and its biota, they




leave some important questions unanswered.  The sediment data cannot predict




the amount of contamination entering the food web or show the period(s) over




which the PCB's accumulated.  Because fish are highly mobile and fairly long-lived,




it is difficult to know where and over what periods they assimilated these toxins.




     Use of macroinvertebrates as indicators does not entail such limitations.




Macroinvertebrates are part of the food web; and because they are relatively




immobile and have short life cycles, any PCB's they contain will have been




accumulated at a specific location and over a relatively short time.



     Functionally, macroinvertebrates serve as an intermediate step in the food




web, obtaining nutriment from detritus, various plants, and small animals and




passing it on to larger animals, such as fish and waterfowl.  In much the same




way, they accumulate and transfer contaminants (such as chlorinated hydrocarbons)




and are integral to the well-known process of biomagnification.
                                       - 244
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     Sanders and Chandler (1972) have shown that aquatic invertebrates rapidly




accumulate PCB's to levels several thousand times that of the surrounding




water.  When four species of aquatic insects were placed in water containing




1.1 to 2.8 parts per billion of Aroclor  1254, they accumulated between 5 and 30




parts per million in their body tissues after only 4 days, representing magnifi-




cation factors of from 1,400 to 22,000.  In a separate study, other immature




insects (mayflies) accumulated PCB's by a factor of 1,950 after the same exposure




period (Sodergren and Svenson, 1973).  This demonstrated ability to rapidly con-




centrate PCB's makes aquatic invertebrates valuable for monitoring surface




water contamination.  Since aquatic invertebrates are the mainstay in the diet




of many fish, this approach will also monitor the approximate levels of contamina-




tion in fish food.  This is particularly significant because food seems to be




the main source of organochlorines (including PCB's) to fish (Addison, 1976).




     Artificial substrate samplers have become popular in biological monitoring




because they are relatively easy to use in most aquatic habitats and because




they standardize several important sampling variables, including surface area




and substrate type (Beak et al., 1973; Weber, 1973).  They are of additional



value in monitoring toxic substances, since they can obtain samples from the




water column, for which data are often lacking.  Samples collected in this




manner not only can concentrate steady low levels, which are generally not




detectable in grab water samples; they also will  integrate  intermittently high




levels that would otherwise require continuous chemical monitoring.






Brief Description of Study Area




     The investigation reported here was carried out in the main stem of the




Hudson River from the village of Hudson Falls (mileage point 195) to Staatsburg




(m.p. 85).  In the short (4 miles) reach from Hudson Falls to Fort Edward
                                         - 245 -
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the river is largely unregulated, generally flowing through a series on nontur-




bulent pools and shallow riffle areas.  Moderate to heavy amounts of organic




pollution (mainly treated sewage and paper mill wastes) enter the river at




numerous intervals from Glens Falls to Fort Edward.  Until May 1977 two major




point sources of PCB's also entered the river in this reach.




     From Fort Edward (m.p. 191) to Troy (m.p. 153) the river is used as part




of the Champlain Canal and basically consists of a series of steplike navigation




pools.  Eight dams are used to regulate the height of the pools, and the main




channel is dredged periodically to maintain the minimum width and depth




requirements for navigation.




     From Troy south (the Lower Hudson) the river is unregulated and is a true




estuary:  the river bed is below sea level, and a tidal rise and fall of about




4 feet is observed at the Troy dam.  From Troy to Poughkeepsie (m.p. 70) the




water is mainly fresh (limnetic zone).  The oligohaline zone extends from




Poughkeepsie to Haverstraw Bay (m.p. 30), where salinity generally ranges between




50 and 200 mg/1 of Cl".  From that point to the mouth salinity varies from 200




to 2000 mg/1 of Cl", and the river is termed mesohaline (Howells, 1972).






Methods




     A pilot project was undertaken in 1976 to determine the feasibility of



using multiple (a type of artifical substrate) samplers to monitor PCB's in the




water column of the Hudson River.  The initial sampling network (Table I)




consisted of 13 stations at 3-20-mile intervals between Hudson Falls and




Staatsburg.  Stations 1 and 3 were controls, located upstream from the known




point discharges of PCB's in the Hudson River and Champlain Canal, respectively.




The remaining stations were all below the discharges.  Station 2 was in the




"natural" river; stations 4-8, in the canalized Upper Hudson; and stations 9-13,




in the limnetic zone of the Lower Hudson.
                                        - 246 -
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Because the results from 1976 were promising, the project was continued in
1977.  Stations 14-16 were added, extending the sampling network into Haverstraw
Bay, and station 3 (Champlain Canal) was dropped.
     Samples were obtained by exposing hardboard artificial substrates for
periods of 4-5 weeks.  In 1976, they were installed in mid-May (12-17) and
harvested approximately 4 weeks later (June 6-10).  Subsequent collections were
made at 5-week intervals (July 13-17; August 17-20; September 21-23).  During
1977, samplers were installed on June 6-9 and Harvested July 11-14, August
15-18, and September 19-22.  At the time of this writing, only the results from
the August survey were available.
     The actual sampling device was modified slightly from that originally
described by Hester and Dendy (1962).  Each sampler consisted of 10 plates of
tempered hardboard (smooth on both sides), 6-inches (15.2-cm) square and 1/8-
inch (0.3-cm) thick, mounted on a stainless steel turnbuckle.  Plates 1-5
(counting from the top) were separated by hardboard spacers 1-inch (2.5-cm)
square and 1/8-inch (0.3 cm) thick; plates 5-10, by spacers 1-inch square and
1/4-inch (0.6-cm) thick.
     Two samplers were installed at each station.  At stations 1-3 each sampler
was suspended 3 feet (0.9 m) below the water surface from a half-gallon
polyethylene float filled with Styrofoam packing material.  A 4" x 8" x 16"
cement block rested on the bottom and served as the anchor.  At the remaining
stations the samplers were suspended from navigation buoys at the same depth;
a brick attached to the bottom of each unit provided some stabilization against
the current.  All connections were made with 1/8-inch plastic-coated cable,
secured with cable clamps.  Brass swivel snaps were used between the cable
and sampler to facilitate removal and replacement of the samplers.
     Several precautions were taken to reduce the contamination of the samples
during harvesting.  In particular, contact of the samples with paints and
plastics was avoided, since these materials often contain PCB's (Bonner, 1976;
                                       - 247 -
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Peakall, 1975).  In the laboratory all processing materials, including 14-quart




galvanized steel buckets, wide-blade steel spatulas, and 1-quart glass jars,




were washed with acetone, then rinsed with distilled water.  A square of




aluminum foil was placed over each jar before capping in order to prevent




contamination from the paint and/or rubber gaskets on the jar lids.  In the




field, the exposed sampler was placed in a bucket, disassembled, and thoroughly




cleaned by scraping off each plate with a wide-blade spatula.  The slurry was




then poured in a sample jar, which was placed on ice and returned to the




laboratory for analysis.




     In the laboratory, a portion of each sample was retained for identification




of the organisms, and the remainder was submitted for chemical analysis.  Orig-




inally we had intended to pick the organisms from the residue and have them




analyzed separately.  However, the fauna of the Hudson (especially near Fort




Edward) is impaired by numerous industrial and municipal wastes and consists




mainly of chironomid midges and oligochaete worms (Simpson, 1976).  These




organisms are so small that 10,000 to 15,000 individuals would be required to




provide sufficient biomass for chemical analysis.  To expedite the evaluation




of this technique, the total residue from the samplers was analyzed.  Less




stressed rivers support a more diverse  fauna, including relatively large




organisms such as mayfly nymphs (Ephemeroptera) and caddisfly larvae (Trichoptera),




Under those conditions, obtaining sufficient biomass for analysis would be much




less of a problem.




     To prepare the samples for chemical analysis, they were first filtered




under suction on No. 41 Whatman filter paper.  The retained solids were trans-




ferred to a soxhlet extraction thimble and extracted with acetone/hexane, 2:1




for 2 hours,  then 1:1 overnight (16 hours).  The residual material was dried




at 70°C for 2 days and weighed to determine the dry weight of the sample.  The
                                         - 248 -
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two extracts were combined in a separatory funnel, and the lower aqueous phase




was drawn off and reextracted with hexane in another separator1/ funnel.  The




combined hexane layers were dried over sodium sulfate and divided into two equal




portions.  One portion was evaporated to dryness (70°C for 2 days) and weighed




to give the hexane-extractable fat content (this step was initiated in September




1976).  The remainder was concentrated to 2 ml in a Kuderna-Danish evaporator,




cleaned up by passage down a calibrated column of 2% deactivated Florisil




(10 g; 1-cm diameter), overlaid with anhydrous sodium sulfate.  A 40-ml fraction




eluted with hexane was collected, evaporated to 1.5 ml, and analyzed with a




Hewlett-Packard 5840A gas chromatograph with a ^3Ni detector.  The column




consisted of 1% Apiezon L (purified by eluting it from activated alumina with




hexane and collecting the colorless fraction) on 110-120-mesh Gaschrome Q.




     The quantity of PCB's in the sample was determined by measuring the areas




of the peaks observed and dividing them by the peak areas of standard mixtures




of Aroclor 1016 and 1242.  The means of these results were used to calculate




the quantity of PCB's per dry weight of material (Bush et al., 1975).






Results and Discussion




     One of the prime concerns at the outset of this study was possible con-




tamination of the samples from the sampling apparatus, particularly from the




hardboard plates.  Results from the two control stations ranged from 0.1 to 1.0




ppm (Table I) and indicated that contamination from the sampling method was




minimal.  Some PCB's were expected, since some contamination of the river




sediments has been found in the area above the point discharges (N.Y. State




Department of Environmental Conservation, 1976).  To eliminate any possibility




of contaminated hardboard, chemically inert porcelain plates could be used




in constructing the multiplate samplers,.
                                           - 249 -
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     The results generated to date are providing an insight into the spatial




and temporal distribution patterns of PCB's in the water column of the Hudson.




During all sampling periods for which data are available, consistently higher




concentrations have been found in the canalized portion of the Upper Hudson than




elsewhere in the river (Table II).  This is not surprising, since it is in




this reach that the highest levels have been found in fish and sediments.




Although PCB's are no longer being discharged by the General Electric facilities,




substantial amounts are probably finding their way into the water from highly




contaminated sediments.  Concentrations as high as 3,707 ppm have been found




in sediments accumulated behind the dams of the Upper Hudson (N.Y. State




Department of Environmental Conservation, 1976).




     Contamination of the Lower Hudson River, while less severe, was well above




background levels.  In June, July, and August 1976 all stations yielded PCB's in




excess of 6 times background levels (Table II).  The 100-year flood, which




occurred in the spring of 1976, may have significantly increased the passage of




PCB's from the upper to the lower river by resuspending and transporting




PCB-laden sediments downstream.  The Lower Hudson also receives contamination




from a variety of other sources, such as the Mohawk River, various municipal




and industrial outlets, and runoff (particularly leachates from landfills).



     To this point we have considered the results expressed in parts per




million per unit dry weight of the residue.  Clayton et al. (1977) have shown,




however, that lipid content is highly correlated with the PCB levels in marine




invertebrates, and they contend that lipid content is the most meaningful




normalization parameter for quantification of PCB results.  Beginning in




September 1976 we determined lipid content of the samples and thus have been




able to normalize the results (Table III, Fig. l)
                                          - 250 -
-------
     The normalized data lead to the same general conclusion as the nonnormalized




results, namely, that the greatest contamination is occurring in the canalized




portion of the Upper Hudson.  However, the two normalized profiles (Fig. l) show




a much more consistent pattern than the same data expressed per unit dry weight




(Fig. 2).  In both normalized curves, PCB concentrations progressively




increase from the control station to Schuylerville, decrease slightly at Still-




water, then peak at Waterford and gradually diminish downstream.  The disparity




of the nonnormalized data is apparent in the reach from Fort Edward to Stillwater.




In one profile there is a progressive decrease to Stillwater; in the other,




a steady increase.  The consistency of the normalized data confirm that this is




a more reliable method of expressing the results.




     The normalized data also show an interesting temporal change.  The August




1977 profile is smoother, with Upper Hudson levels lower and Lower Hudson levels




higher than in 1976.  This suggests that PCB's are becoming more widely and




evenly distributed throughout the river, although we do not know how much of




this is attributable to the intervening 100-year flood.  The hypothesis of a




steady trend in this redistribution will be tested and reevaluated with data




from additional surveys.




     The results presented above are providing valuable information supplemental




to fish and sediment data in the total assessment of PCB contamination in the




Hudson River.  Collection' of aquatic invertebrates with artificial substrates




will be continued to help evaluate the spatial and temporal distribution of




PCB's throughout the river.






Summary and Conclusions




     lo  Multiplate samples are proving to be an effective means of monitoring




PCB contamination in the water column of the Hudson River.




     2.  Results normalized to lipid content are more consistent than those
                                     - 251 -
-------
expressed per unit dry weight of residue.




     3.  Even with the abatement of the main point discharges in Fort Edward,




PCB contamination is a continuing problem in Hudson River water.  Concentrations




are highest in the canalized Upper Hudson but seem to be becoming more evenly




distributed throughout the river with the passage of time.
                                       - 252 -
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Literature Cited

Addison, R0F. 1976.  Organochlorine compounds in aquatic organisms:  their
     distribution, transport and physiological significance.  _In_ Lockwood, A.P.M.,
     ed. Effect of pollutants on aquatic organisms.  Cambridge Univ. Press.
     193 pp.

Beak, T.W0, T.C. Griffing, and A.G. Appleby.  1973.  Use of artificial substrate
     samplers to assess water pollution, pp. 227-241 I_n Cairns and Dickson,
     eds., Biological methods for the assessment of water quality.  American
     Society for Testing and Materials, Special Technical Publication No. 528.

Bonner, P., ed. 1976. PCB's - a review.  Great Lakes Focus 2(1):1 ff.

Bush, B., F. Baker, R. Dell'Acqua, C.L. Houck, and Fa-Chun Lo. 1975.  Analytical
     response of polychlorinated biphenyl homologues and isomers in thin-layer
     and gas chromatography.  J. Chromatogr. 109:287-295.

Clayton, J.R., Jr., S.P. Pavlou, and N.F. Breitner. 1977.  Polychlorinated
     biphenyls in coastal marine zooplankton; bioaccumulation by equilibrium
     partitioning.  Environ. Sci. Technol. 11:676-682.

Hester, F.E., and J.S. Dendy. 1962.  A multiple-plate sampler for aquatic
     macroinvertebrates.  Trans. Amer. Fish. Soc. 91:420-421.

Howells, G.P. 1972.  The estuary of the Hudson River, U.S.A. Proc. Royal Soc.
     Lond., Ser. B. 180:521-534.

Nadeau, R0Jo, and R.R. Davis.  1976.  Polychlorinated biphenyls in the Hudson
     River (Hudson Falls-Fort Edward, New York State).  Bull. Environ. Cont.
     Toxicol. 16:436-444.

New York State Department of Environmental Conservation. 1976.  PCB data in
     Hudson River fish, sediments, water, and wastewater.  SAN-P17 (500-3/76).
     24 pp.

Peakall, D.B. 1975.  PCB's and their environmental effects. CRC Critical Rev.
     Environo Cont. 5:469-508.

Sanders, H.O., and J0H0 Chandler. 1972.  Biological magnification of a poly-
     chlorinated biphenyl (Aroclor 1254) from water by aquatic invertebrates.
     Bull. Environ. Cont. Toxicol. 7_:257-263.

Simpson, K.W. 1976.  A water quality evaluation of the Hudson River based on the
     collection and analysis of macroinvertebrate communities.  In Fourth
     symposium on Hudson River ecology, Hudson River Environmental Society,
     Bronx,, N.Y.

Sodergren, A., and B0J. Svensson.  1973.  Uptake and accumulation of DDT and
     PCB by Ephemera danica (Ephemeroptera) in continuous-flow systems.  Bull.
     Environ. Cont. Toxicol. 9:345-350.
                                         - 253 -
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Spagnoli, J.J., and L.C. Skinner. 1975. PCB's in fish from selected waters in
     New York State.  New York State Department of Environmental Conservation,
     Bureau of Environmental Protection Technical Paper No. 75.

United States Environmental Protection Agency. 1977.  PCB's in the Lower Hudson
     River sediments: a preliminary survey.  Region II, Survey and Analysis
     Division, New York.

Weber, Cd., ed. 1973. Biological field and laboratory methods for measuring
     the quality of surface waters and effluents.  Environmental Protection
     Agency, Environmental Monitoring Series No. EPA-670/4-73-001.
                                        -  254 -
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Table I.  Total PCB content of Multipl,.te  Samples  from Hudson  River,  New York
         (expressed ad pom PCB/dry weight  of total residue).


Miles
Station Location from mouth June 1976 July 1976 Aug 1976
*i
2
*3
4
5
6
7
8
9
10
11
12
13
14
15
Hudson Falls,
near Chase Bag Co.
Ft." Edward, near
Rt. 197 bridge
Champlain Canal
Ft. Edward
Ft. Edward,
buoy 219
Ft. Miller,
buoy 189
Schuylerville,
buoy 147
Stil Iwater,
buoy 81
Waterford,
buoy 13
Troy, buoy 79
Castleton, buoy 53
Athens, buoy 88
Saugerties,
buoy 39
Esopus, buoy 9
New Hamburg ,
Diamond Reef buoy
Peekskill, buoy 19
197 0.4 0.6 • 0.5
195 6.2 7.4 3.3
195 - 0.3 0.2
194 25.4 57.0
189 25.5 18.3
182 12.5 12.4
169 - 23.8
158 5.6 12.0
153 3.3 - 2.8
136 4.9 10.5 200.0
116 2.6 5.0 9.0
102 3.2 11.0 4.5
87
67
43

Sept 1976 Aug 1977
1.0 0.1
2.2 2.6
0.2
9.2 2.8
18.8 4.1
11.8 8.9
9.0 10.8
13.9 5.2
6.4 2.4
11.0 2.8
0.0 3.4
1.0
0.7 1.6
1.4
0.8
  *  Controls,  upstream from the known  point  sources  of  PCB's.
                                          - 255 -
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Table II.  Ranges of PCB concentrations for Upper and Lower  Hudson Rivers  compared
           with background levels (expressed as  ppm PCB/dry  weight of  total residue),
Background
Date (stations 1 &/or 3)
June 1976
July 1976
August 1976
September 1976
*August 1977
0.4
0.3-0.6
0.2-0.5
0.2-1.0
0.1
Canalized Upper Hudson
(stations 4-8)
5.6-25.4
12.0-57.0
no data
9.0-18.8
2.8-10.8
Lower Hudson
(stations 9-13)
2.6- 4.9
5.0-11.0
2.8-200.0
0.0-11.0
0.8- 3.4
*Includes stations 14 and 15, added in 1977.
                                         - 256 -
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Table III. Multiplate PCB results normalized to lipid content (expressed as
          ppm PCB/mg lipids).
Miles
Station Location from mouth Sept. 1976 Aug. 1977
*1
2
*3
4
5
6
7
8
9
10
11
12
13
14
15
Hudson Falls, near
Chase Bag Co.
Ft. Edward, near
Rt. 197 bridge
Champlain Canal
Ft. Edward
Ft. Edward,
buoy 219
Ft. Miller,
buoy 189
Schuylerville,
buoy 147
Stillwater,
buoy 81
Waterford,
buoy 13
Troy, buoy 79
Castleton, buoy 53
Athens, buoy 88
Saugerties,
buoy 39
Esopus, buoy 9
New Hamburg, Diamond
Reef buoy
Peekskill, buoy 19
197
195
195
194
189
182
169
158
153
136
116
102
87
67
43
0.055 0.005
0.088 0.100
-
0.186 0.095
0.640 0.323
1.050 0.419
0.800 0.228
1.150 0.589
0.820 0.383
0.360 0.191
0.000 0.138
0.020
0.010 0.176
0.133
0.058
  * Controls, located upstream from the known point sources of PCB's,
                                       - 257 -
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               RESEARCH PROGRESS ON REMOVAL OR TREATMENT OF PCB
                           IN HUDSON RIVER SEDIMENT

                    BY:  PM Griffen, AR Sears, CM McFarland

INTRODUCTION
     An agreement signed with New York State in September 1976 stated that General
Electric would conduct research and pilot plant studies on the removal or treatment
of PCBs in sediments dredged from the Hudson River by the Department of Environmental
Conservation.  The agreement also stated that physical, chemical, and biological
techniques should be considered.
     Initial evaluations of the environmental situation revealed that PCBs have
diffusely infiltrated into river sediments and large organic debris at the bottom
of a high velocity region of the river.  Due to this physical situation, in situ
treatment approaches that require periodic additions, mechanical mixing, and subse-
quent reactant retrieval appear impractical.  Consequently, GE investigators have
concentrated on studies to minimize the quantity of material to be removed, maxi-
mize   the effectiveness of controlled landfills, and demonstrate the usefulness of
several separation, encapsulation, and destruction approaches.
     Preliminary results have been encouraging.  Rapid analytical procedures have
been developed to reduce sample turnaround time from 24 hours to less than 2 hours
thereby providing closer control over dredging operations.  Indications of rapid
PCB vaporization from spoil banks are being investigated, and the phenomena is being
quantified under controlled laboratory conditions in appartus specifically designed
for that purpose.  Preparations have been completed for prototype investigations of
distillation, excess air incineration, and limited air incineration on a 36 inch
multiple hearth furnace with a high temperature after burner.  Significant gains have
been made in locating and culturing microbes which degrade the lower chlorinated
biphenyls (less than 4 chlorines).  To date, 15 different strains have been positively
identified.  They are currently being studied for nutrient, pH, and symbiotic re-
quirements.
                                      - 260 -
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DISCUSSION
     Aroclors 1016 and 1242 make up more than 85% of the PCBs found in Hudson River
sediments below the General Electric Manufacturing facilities in Fort Edward down
to the Troy dam.  Concentrations of these Aroclors generally range from non-detect-
able to 100 parts per million(ppm) at depths of less than six inches.  Deposits
going as high as 1000 to 1500 ppm have been found but are contained in relatively
small regions of the river.  The cumulative effects of these sediment concentrations
on aquatic life have not been resolved, nor has the movement of the PCB infiltrated
sediments been scientifically predicted.  (Both problems are currently under study
by the NYS Department of Environmental Conservation).  Consequently, the minimum
allowable level  permitted to remain in the river sediments has not been determined,
the location of principal PCB deposits has not been established, and therefore, it
has not been possible to calculate the total sediment volume to be removed.  (Much
of these data should be available by the end of 1977).
     Pertinent characteristics of both the principal chlorinated biphenyls and the
Hudson River bottom material are qiven in Tables 1-a.ad-L!..    	
                                    TABLE I
                         Specifications of Aroclor 1016/1242
     Chlorine content
     Specific gravity
     Distillation range
     Evaporation loss  (neat)
     Decomposition temperature
     Solubility in water
     Solubility in organic solvents
Approximately 42% by weight
1.38 - 1.39 at 25°C
325 - 366°C
0 - 0.4% at 100°C for 6 hours
600°C or less
Less than 100 ppb
Soluble
                                       - 261 -
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                                   TABLE II
           Specifications of Hudson River Sediments at Fort Edward
     Organic content                          10 to 30% by dry weight
     Size distribution and composition        >6" organic rubble through fine clays
     Maximum incineration temperature
       (clinker formation)                    1200°C
     PCB affinity y_£ size                     Approximately equal  amounts of PCB
                                                are found on all size fractions
     Water content in settled solids          30 to 60%

     Some information has been obtained regarding the problems of  removing
chemically infiltrated sediments and controlling their disposal.  It was gained as a
result of extensive dredging necessitated by the redeposition of large quantities of
sediment from the region of the old Fort Edward dam (removed in 1973) to the Champlain
shipping channel and the East channel at Fort Edward.  About 800,000 cubic yards have
been dredged to date by the Department of Transportation and placed in landfills along
the river bank.  In parallel, the NYS DEC availed itself of the opportunity to develop
an approach for rapidly removing PCB from generated dredge waste water.  Their ap-
proach, using flocculation and subsequent settling of suspended solids, reduced the
total  PCB concentration in the dredgate to a level of less than 50 parts per billion
(ppb)  prior to its return to the river.  The concentration of PCB  in the settled,
dredged sediment appeared to average less than 30 ppm and has not  presented a major
leaching problem even from landfills with minimum control.
     With these data and observations for background, NYS DEC has  developed a pro-
gram which addresses the following:
     1.  Determination of toxicity, amount, and location of PCB in river.
     2.  Postulation of significant ecological effects due to existing
           PCBs in the river and those which could be generated due to
           their removal for land storage.
     3.  Development of dredging techniques for the selective removal
           of material.
     4.  Generation of a model regarding PCB dissipation pathways  from
           landfills so that storage facilities can be properly designed.
     5.  Selection and implementation of separation or destruction tech-
           niques if landfills cannot be properly constructed or maintained
           for safe and economical  disposal of PCB infiltrated sediments.
                                      T-. 262 -
-------
     General Electric's research program is aimed basically at Task 5 with areas of
study selected from the list shown in Table III.

                                    TABLE III
 Possible Methods of Functional  Treatment or Removal  of PCB from Sediments
        Approach
Controlled storage
Fixation or Encapsulation

Separation*
Destruction
Natural Dissipation
                   Techniques
-Lagoons, pits, tanks, etc.
-Portland cement or polymer  binder on dewatered
    sediments
-Selective transfer and subsequent absorption
    direct from sediments to an activated carbon
    scavenger
 Filtration, flocculation, and clarification of
    suspended solids from supernatant
 Distillation and solvent extraction from
    settled sediments
 Plant and animal uptake from settled sediments
-Incineration under either excess  or controlled
    air conditions
 Chemical decomposition
 Enhanced microbial biodegradation
 Photodegradation
-Vaporization
 Leaching
 Physical transport
 Natural biodegradation
*Each of these approaches must
     to accomplish an acceptabl
 be combined with storage or destructive techniques
 e disposal.
     A prime factor in the selection of a specific research approach was the necessity
to couple with current river sediment extraction techniques.  Since the technology of
dredging today is based upon a long-term evolution of equipment designs for removing
large quantities of sediments in the shortest possible time and lowest cost, selec-
tivity or precision of removal has not been an important factor.  Now, with attention
                                      - 263 -
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being directed towards retrieval of specific materials from water bodies followed by
the disposal of the extracted material, selectivity has acquired a much higher priority.
     Without the ability to remove specific material, large quantities of "clean"
sediment will be unnecessarily processed at an undue cost in time and money.   The
reasons for poor precision are many.  They include inadequate mapping, sediment in-
stability, and the inability of the dredge operator to detect the boundaries  of the
deposit.
     General Electric has been able to have an impact on this situation by developing
analytical techniques that will provide data on PCB concentrations in the sediments
while the dredging operation is in progress.
     Once the sediment has been determined to contain higher than acceptable  levels
of PCB, ft can be transported to previously prepared controlled storage areas.  With-
in these storage areas, the forces of nature will act to slowly degrade or dissipate
PCBs through natural  microbial action, soil chemistry, volatilization, leaching,
photodegradation, and physical transport by erosion or terrestrial animals.  Some of
these pathways can be controlled by dredge site design.  Those which are not  properly
understood are under investigation by DEC, subcontractors for DEC, and General
Electric.
     Decisions will be made in late 1977 or early 1978 as to what must be done to PCB
infiltrated sediments contained in controlled landfills.  If PCB removal or treatment
is deemed necessary,  by the State, the results of General Electric's investigations
will be utilized.

PRELIMINARY CONCLUSIONS
     PCBs have become diffusely distributed to the environment from point sources
all over tht world.  Retrieval of these chemicals is technically feasible although
extremely expensive.   If future studies of ecological effects show evidence that
outweighs the economic issue, then methodologies such as rapid detection, selective
removal, controlled storage, incineration, and biodegradation will become highly
developed and the every day tools of the environmental engineer.
                                       - 264 -
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                        SESSION IV

          "Current Research on the Pate and Effect of Kepone"
CHAIRMAN

Dr. Tudor Davles
Deputy Director
Environmental Research Laboratory at Gulf Breeze
Office of Research and Development
U. S. EPA

SPEAKERS

Mr. David J. Hansen
Research Aquatic Biologist
Environmental Research Laboratory at Gulf Breeze
U. S. EPA
"Effects of Kepone on Estuarine Organisms"

Mr. Steven C. Schimmel
Research Aquatic Biologist
Environmental Research Laboratory at Gulf Breeze
U. S. EPA
"Acute Toxicity of Kepone to Pour Estuarine Animals"

Mr. Lowell H.  Banner
Research Aquatic Biologist
Environmental Research Laboratory at Gulf Breeze
U. S. EPA
"Kepone Accumulation and Pood Chain Transfer"

Richard L. Garnas, Ph.D.
Research Scientist
Environmental Research Laboratory at Gulf Breeze
U. S. EPA
"Fate and Degradation of Kepone in Estuarine Microcosms"

Robert J. Hugget, Ph.D.
Project Manager
The Virginia Institute of Marine Science
"The Role of Sediments in the Storage, Movement and Biological
Uptake of Kepone in Estuarine Environments"

Donald J. O'Connor, Ph.D.
Environmental Engineering and Science Program
Manhattan College
"Preliminary Analysis of Kepone Distribution in the James River"
                                - 265 -
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                                 vR                       1 /
                 Effects of Kepone—'on Estuarine Organisms



         David J. Hansen, DelWayne R. Nimmo, Steven C. Schimmel,



                Gerald E. Walsh and Alfred J. Wilson, Jr.



                  U.S. Environmental Protection Agency



                    Environmental Research Laboratory



                       Gulf Breeze, Florida 32561







                                ABSTRACT







      Laboratory toxicity tests were conducted to determine the effect  of



 Kepone on and its accumulation by estuarine algae, mollusks, crustaceans,



 and fishes.  Nominal Kepone concentrations calculated to decrease  algal



 growth by 50 percent in static bioassays lasting seven days were:  350  ug/£,



 Chlorococcum sp.; 580 yg/£, Dunaliella tertiolecta; 600 pg/£, Nitzschia



 sp.;  and 600 yg/£, Thalassiosira pseudonana.  Measured Kepone concentra-



 tions calculated to cause 50 percent mortality in flowing-seawater



 toxicity tests lasting 96 hours were: 10 yg/Jl for the mysid shrimp



 (Mvsidopsis bahia); 120 yg/£ for the grass shrimp (Palaemonetes  pugio);



 >210 yg/Jt for the blue crab (Callinectes sapidus) ; 70 y g/jj, for the



 sheepshead minnow (Cyprinodon variegatus); and 6.6 p g/£ for the  spot



 (Leiostomus xanthurus).  Bioconcentration factors (concentration in
^Registered trademark, Allied Chemical Corporation, 40 Rector  Street,



  New York, New York 10006.  Kepone was purchased from Chem  Service,  West



  Chester, PA as 99% pure.  Our analyses indicated 88% purity.



 — Contribution No. 311, Environmental Research Laboratory,  Gulf  Breeze.
                                    - 266 -
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whole animals divided by  concentration  measured  in  water)  in these tests




were greatest for  fishes  (950  to  1,900)  and  less  for  grass  shrimp 420 to




930.




      Survival, growth, and  reproduction of  mysids  and  sheepshead minnows




were decreased  in  chronic bioassays  lasting  14 to 64  days.   Growth of mysids




and sheepshead  minnows was reduced by exposure to 0.07  yg/£ and  0.08  yg/£




respectively.   Bioconcentration factors  for  sheepshead  minnows  in the chronic




bioassay averaged  5,200  (range 3,100 to  7,000) for  adults  exposed for 28 days




and 7,200  (3,600 to 20,000)  for juveniles exposed for 36 days.   The chronic




toxicity and bioconcentration potential  of Kepone are more  important  factors




than its acute  toxicity in laboratory evaluations of  environmental hazard.




Therefore, these factors  should be considered when  attempting to assess




present impacts and attempting to limit  future impacts  of  this  insecticide




on the aquatic  environment.




                             INTRODUCTION




     Kepone  (decachlorooctahydro-1,3,4-metheno-2H-cylobuta  [cd]  pentalene




2-one) is an insecticide  that was manufactured and  formulated in the  United




States to control  ants, cockroaches  and  insect pests  of potatoes and  bananas.




Kepone is toxic to birds and mammals including man  (Jaeger,  1976)  and acutely




toxic to some estuarine organisms (Butler, 1963).   Recent  contamination  of




water, sediment, and biota in freshwater and estuarine  portions  of the James




River, Virginia has stimulated concern  about this chemical's hazard to




aquatic biota (Hansen et al., 1976).  This concern  was  based on  (1) the  con-




tinued occurrence  of. Kepone  in many  finfishes and shellfishes in amounts




that forced closure of fishing because  of  potential human health hazard  and




(2) laboratory studies which showed  that Kepone  is  highly bioaccumulative and




toxic to estuarine organisms, particularly in chronic exposures.   This paper




describes the results of these laboratory  toxicity  tests with estuarine  algae,




oysters,  crustaceans,  and fishes and chronic tests  with a crustacean  and a fish.




                                         - 267  -
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                         Experimental  Procedures




                            Acute  Toxicity




 Algae:   The  unicellular  algae  Chlorococcum  sp.,  Dunaliella tertiolecta,




 Nitzschia  sp.,  and  Thalassiosira pseudonana were exposed to Kepone for seven




 days  to  determine its effect on growth  (Walsh  et al.,  In press).   Algae  were




 cultured in  25  or 50 ml  of  growth  media and artificial seawater of 30  loo




 salinity and a  temperature  of  20°C (Hollister  et al.,  1975).   Kepone, in 0.1




 ml acetone,  was added to culture media  and  0.1 ml of  acetone  was  added to




 control  cultures.   Photoperiod consisted of 12 hours  dark and 12  hours of




 5000  lux illumination.   Effect on  growth was determined by electrophoto-




 metrically measuring optical density.   Also, algae grown for  6 days in media




 and then exposed to 100  yg/£ Kepone  for 24  hours were analyzed for Kepone




 content.








 Oysters:  The acute toxicity of Kepone  to embryos of  the eastern oyster




 (Crassostrea virginica)  was determined  by measuring its effect on develop-




 ment  of  fully-shelled, straight-hinged  veligers  in a  48 hour  static expo-




 sure^ .  Methods used were  those of  Woelke  (1972) and U.S. EPA (1975).  Test




 containers were l-£ glass jars that  contained  900 m£  of 20 C, 20  /oo




 salinity seawater and 25,000 ± 1,000  oyster embryos.   All test concentra-




 tions were triplicated.   The number  of  normal  and abnormal embryos were




 counted  microscopically  in  a Sedgewick-Rafter  cell at the end of  48 hours




 of exposure  to Kepone.








 Crustaceans  and Fishes:   The acute toxicity of Kepone to grass shrimp




 (Palaemonetes pugio), blue  crabs  (Callinectes  sapidus), sheepshead minnows




 (Cyprinodon  variegatus), and spot  (Leiostomus  xanthurus) was  determined in
— This research was performed  under  an EPA contract  by Mr.  Tom Heitmuller,




  Bionomics-EG&G,  Inc. Marine  Research Laboratory, Pensacola,  Florida 32507.






                                         - 268 -
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96-hour flow-through  toxicity  tests  (Schimmel  and Wilson,  In press).   Accli-




mation and testing procedures  were compatible  with  those of  Standard  Methods




(A.P.M.A., 1971).  Test animals were  caught  locally and 20 were  placed in




each 18£ aquarium.  Water  flow to each  aquarium was 68  2,/hour.   Stock solu-




tions of Kepone in acetone were metered  into experimental  aquaria  at  the




rate of 60 m£/hour.   Control aquaria  received  60 m£ of  acetone/hour.   At




the end of the experiment, surviving  animals were chemically analyzed for




Kepone content.




     The acute toxicity of Kepone to  mysids  (Mysidopsis bahia) was determined




by using intermittent  flows of water  from  a  diluter (Mount and Brungs, 1967)




or continuous flow of water from a siphon  and  Kepone from  an infusion pump




(Banner et al., 1975).  Thirty-two 48-hour-old juvenile mysids were placed  in




chambers (4 mysids per chamber), in each test  aquarium.  Chambers  con-




sisted of glass petri dishes to which a  15 cm.  tall cylinder of  210y  mesh




nylon screen was glued.   Water in the  chambers was renewed  by a self-




starting siphon which nearly emptied  and then  filled each  aquarium at




about 25 min. intervals.









                           Chronic Toxicity




Mysidopsis bahia:  The chronic toxicity  of Kepone to this  mysid  was deter-




mined in 19-day exposures that began with  48-hour-old juveniles.  (Nimmo




et al., In press).  This permitted time  for  production of  several  broods




for assessment of reproductive success  and survival of progeny.   Exposure




conditions, apparatus, and number of mysids  per concentration were identical




to those of the acute toxicity tests.  Three tests  were conducted; one to




assess effects on survival and reproduction  and two,  at lower concentra-




tions,  to determine effects on growth.   Data from the two  growth experiments




were pooled for statistical analysis.




                                         - 269 -
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Cyprinodon variegatus:  The chronic toxicity of Kepone to sheepshead minnows




was determined in a 64-day flow-through bioassay; 28-day adult exposure




followed by a 36-day exposure of their progeny  (Hansen, et al., In press).




We delivered Kepone, 0.0088 \ii of  the solvent  triethylene glycol, and 1.5£ of




filtered 30 C seawater (average salinity 15  /oo; (range, 8-26  /oo) to  each




70£ aquarium during each of 440 daily cycles of the dosing apparatus of  Schimmel




et al. (1974).  Seawater and solvent were delivered to the control aquarium.




Thirty-two adult females and 32 adult males were exposed to each concentration




of Kepone for 28 days.  Egg production was enhanced using injections of  50




international units of human chorionic gonadotrophic hormone on exposure




day 25 and 27 (Schimmel et al., 1974).  Eggs were fertilized on day 28 and




placed in chambers, glass petri dishes with 9-cm tall cylinders of 450y




nylon mesh.  Twenty embryos were used in each chamber.  Embryos from control




fish were placed in four chambers in the control aquaria and in four chambers




in each of the six aquaria receiving Kepone.    Embryos from  Eish in each of




the six aquaria receiving Kepone were placed in four chambers  in that aquarium




and in four chambers in the control aquarium.  Water in the  chambers was




exchanged by the action of a self-starting siphon in each aquarium that  caused




water levels to fluctuate 5 cm about 40 times per day.  In the 36-day exposure




to determine Kepone's effect on survival and growth of progeny, embryos  hatched,




and fry grew until they were juvenile fish.  Kepone content  of adult fish,  their




eggs, and juvenile fish was determined.




                         Statistical Analyses




     Probit analyses of growth and mortality data were used  to determine ECSO's




and LC50's.  Growth data for M. bahia were subjected to analysis of variance




(a = 0.05) and for C\ variegatus, analysis of covariance and Newman-Kuels




tests (a = 0.01) was used.
                                       - 270 -
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                           Chemical Analyses


     Water from acute and chronic tests with  crustaceans  and  fishes,  and


organisms surviving these tests, were  analyzed by  gas  chromatography.


Methods of extraction concentration, cleanup, and  quantification  were


described by Schimmel and Wilson  (In press).


                        Results and Discussion


                            Acute Toxicity






Algae:  Growth of marine unicellular algae was reduced by exposure to


Kepone in static tests  (Table 1).  Chlorococcum was  the most  sensitive


of the four algae tested with a 7-day  EC50 of 350  yg/£.   The  three less


sensitive species responded similarly  to Kepone with overlapping  confidence


limits for EC50's.  Algae exposed to 100 pg Kepone/£ of media accumulated


the chemical with Chlorococcum containing 0.80 pg/g; D_. tertiolecta,  0.23


pg/g; Nitzschia, 0.41 pg/g; and T_. pseudonana, 0.52  pg/g.   Butler (1963)


reported that when estuarine phytoplankton were exposed to 1,000  pg/£


carbon fixation was reduced by 95 percent.






Oysters:  The 48-hr EC50 for oyster larvae in static tests was less than


those of algae (Table 1).  The EC50, calculated using  nominal water concen-

                     21
trations, was 66 pg/£—.  Embryos from  56 pg/£ were fully  shelled  and  straight-


hinged but appeared smaller than those from controls.   The percentage of  nor-


mal embryos in 65 pg/£ was 32 percent  and in  87 pg/£ it was 0 percent.  The


concentration of Kepone calculated to  reduce  shell deposition of  juvenile


eastern oysters by 50 percent in a 96-hour flowing water  bioassay was 38  pg/£


in water of 14°C and 11 pg/£ in water  of 31°C (Butler,  1963).
                                        - 271 -
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Crustaceans and Fishes:  Kepone, at the concentrations tested, was acutely




toxic to mysids (Nimmo et al. , In press), grass shrimp, sheepshead minnows,




and spot but not to blue crabs (Schimmel and Wilson, In press) (Table 1).




Spot and mysids were the more sensitive species with 96-hour LC50 values




of 6.6 and 10 yg/fc.  Crabs exposed to as much as 210 yg Kepone/?, suffered




no significant mortality.  Symptoms of acute Kepone poisoning in fishes




included lethargy, loss of equilibrium and darkened coloration on the




posterior portion of the body; occasionally only in one quadrant.  Crus-




taceans became lethargic before death but exhibited no color change.




Butler (1963) reported forty-eight hour LC50 or EC50 values (based on nom-




inal concentrations) for other estuarine organisms were:  Brown shrimp




(Penaeus aztecus) 85 yg/£, longnose killifish (Fundulus similis) 84 yg/£,




and white mullet (Mugil curema) 55 yg/Sl.




     Kepone was bioconcentrated from water by all four species we exposed




for 96 hours.  Bioconcentration factors  (concentration in tissue divided




by measured Kepone in water) for fishes were similar (950 to 1,900).  Bio-




concentration factors for grass shrimp ranged from 420 to 930 and for blue




crabs 6 to 10.









                           Chronic Toxicity




Mysidopsis bahia:  Exposure of this mysid to Kepone for 19 days in the first




experiment decreased its survival and reduced the number of young produced




per female (Table 2) (Nimmo et al., In press).  At the highest concentration




(8.7 yg/fc) all mysids were dead within the first two days.  At lesser concen-




trations  (1.6 and 4.4 yg/£) mortality continued throughout the test.  Eighty-




four percent of the mysids survived exposure to 0.39 yg Kepone/£ water and
                                        - 272 -
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 91% survived  in control aquaria.   In  addition,  natural  reproduction was




 affected.  Average number of young mysids  produced  per  female  was 15 in




 control, 9 in 0.39 yg/£, and none  in  1.6  yg/£.   Mysids  that survived




 throughout the Kepone exposure appeared smaller than those in  control aquaria,




 therefore, two additional experiments were conducted to measure Kepone's




 effect on growth.




     In these experiments,  the average length  (tip  of carapace to end of




 uropod) of mysids exposed to Kepone was decreased  (Nimmo et al.,  In press).




 Females exposed to 0.072, 0.11, 0.23, or  0.41  pg/1  were significantly shorter




 than were control mysids; average  length  was 8.2 mm for exposed versus 8.6 mm




 for control female mysids.  Unexposed and  exposed males, however, were of




 similar average lengths, 7.7 to 8.0 mm.




 Cyprinodon variegatus;  Kepone was toxic  to adult sheepshead minnows exposed




 for 28 days (Table 3).  Symptoms of poisoning  included  : scoliosis, darken-




 ing of the body posterior to the dorsal fin, hemorrhaging near the brain,




 edema,  fin-rot, uncoordinated swimming and cessation of feeding.   Symptoms




were first observed on day  one in  24  pg/£,  two  in 7.8 yg/£, three in 1.9 ug/£,




and day eleven in 0.8 ug/£.  Mortalities began  5 to 8 days after  onset of




 symptoms.




     Kepone affected the progeny of 28 day exposed  adults.  In Kepone-free




water,  mortality of embryos from adults exposed to  0.05 to 0.8 yg/£ was




similar to that of embryos  from unexposed  adults (range 6 to 12 percent).




However,  in Kepone-free seawater,  25  percent of the embryos from  fish exposed




to 1.9 yg of Kepone/£ died; abnormal  development of 13  of these 20 embryos




preceded mortality;
                                           - 27^ -
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Table 1.  Acute toxicity of Kepone to estuarine organisms.  Algal and mollusk




toxicity tests were static and estimated nominal concentrations reducing  growth




of algae and embryonic development of oysters by 50 percent (EC50).  Toxicity




tests with crustaceans and fishes were flow-throughs that estimated the meas-




ured concentration in water lethal to 50 percent (LC50).  Ninety-five percent




confidence limits are in parentheses.
Organims
Temperature,
            Exposure




Salinity,     Duration,     EC50/LC50,
Mollusk




 Crassostrea virginica




Crustaceans
   20
                                               loo
  21
                                 Days
Algae
Chlorococcum sp.
Dunaliella tertiolecta
Nitzschia sp.
Thalassiosira pseudonana
20
20
20
20
30
30
30
30
7
7
7
7
350
580
600
600
(?70 Ann^i
(510-640)
(530-660)
(500-700)
66 (60-74)
Callinectes sapidus
Mysidopsis bahia
Palaemonetes pugio
Fishes
Cyprinodon variegatus
Leiostomus xanthurus

19
26
20
18
25
20
13
16
15
18
4
4
4
4
4
>210
10
120
70
6
(8.1-12)
(100-170)
(56-99)
.6 (5.3-8.8)
                                    -  274  -
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Table 2.  Effect of Kepone on the survival of Mysidopsis bahia and on average




number of young per female in a 19-day flow-through toxicity test.
Average Measured
Kepone Concentration
(yg/a)
Control
0.39
1.6
4.4
8.7
Percentage
Survival
91
84
50
3
0
Number of Young
per Female
15.3
8.9*
0
-
-
*Statistically significant at a=0.05 using 2 sample t-test
                                      - 275 -
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Table 3.   Effect of Kepone on and accumulation of Kepone by adult sheeps-




head minnows exposed for 28 days.
Average Measured
Exposure Concentration, yg/£
ND*
0.05
0.16
0.80
1.9
7.8
24.
Percentage
Mortality
5
5
0
22
80
100
100
Whole Body
Concentration, pg/g
ND
0.30
0.78
3.0
12.


*ND = Kepone not detected in control water (<0.02 ug/£) nor in control  fish




(<0.02 yg/g).
                                     - 276 -
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Table 4.  Mortality in progeny of adult  sheepshead minnows  that  were  exposed




to Kepone and in progeny of unexposed, control  fish.  Nominal  exposure  for




the 28-day exposure of adult  fish and  the  36-day exposure of progeny  were




the same.  Progeny exposure began with embryos  and ended with  juvenile  fish




from the embryos.  Residues are concentrations  of Kepone  (yg/g)  in  whole




juveniles, wet weight.
Measured Exposure
Concentration
yg/£

Control (ND)
0.08
0.18
0.72
2.0
6.6
33.

Progeny of
Mortality
%
10
22
12
28
40
40
100
Parental Fish
Unexposed Parents
Residue
yg/g
mi/
1.1
1.4
2.6
7.8
22.
-
History
Progeny of
Mortality
%
10
9
18
18
62
-
-

Exposed Parents
Residue
Hg/g
ND!'
1.6
1.0
1.9
8.4
-
-
_ ND = not detectable, <0.02 U3/£,  0.02  ug/g.
                                    - 277 -
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     Kepone in water affected progeny of exposed parents to a greater extent




than progeny of unexposed parents (Table 4).  Some embryos exposed to 2.0




developed abnormally and fry had more pronounced symptoms and they began to




die 10 days earlier when parental fish had been exposed to 1.9 yg/£ than




was observed in progeny from unexposed parents.




     Kepone also affected growth of sheepshead minnows in the 36-day exposure




of progeny (Figure 1).   The average standard length of juveniles exposed




to all Kepone concentrations was less than that of unexposed control juveniles.




Lengths decreased in direct proportion to increasing Kepone concentrations in




water and were generally not influenced by parental exposure.  A similar




decrease was also noted in weights, but because juveniles exposed to 0.72,




2.0, or 6.6 ug/£ were edematous, they weighed more than unexposed juveniles




of similar lengths.




     Kepone was bioconcentrated by sheepshead minnow adults and their progeny




exposed to the insecticide in water.  Kepone was bioconcentrated in adult




fish in direct proportion to concentration in exposure water (Table 3).  Con-




centration factors averaged 5,200 (range 3,100 to 7,000).  Kepone concentra-




tions in females and their eggs were similar and were 1.3 times greater than




amounts in males.   Concentrations of Kepone in juvenile fish, at the end of




the 36-day progeny exposure, increased with increased concentration of Kepone




in water (Table 4).  Prior exposure of parental fish apparently did not affect




final Kepone concentration in progeny.  Concentration factors for juvenile




fish .averaged 7,200 (range 3,600 to 20,000) and increased with decrease in




concentration of exposure.




     In our tests, Kepone was acutely toxic to, and accumulated by, estuarine




algae, mollusks, crustaceans, and fishes.  Chronic toxicity tests with




M. bahia and _C. variegatus revealed that Kepone affected survival, growth,









                                         -  278  -
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and reproduction.  Effects on growth were observed at one one-thousandth of




the 96-hour LC50.  Accumulation of Kepone was also greatest in chronic tests.




Therefore, chronic tests should be used to assess Kepone's environmental




hazard and to make decisions necessary to minimize its future impact on the




aquatic environment.
                                    - 279 -
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        EFFECT  OF  KEPONE  ON  LENGTH
     OF  JUVENILE  SHEEPSHEAD  MINNOWS
  14
UJ
_J

oho
UJ
(T
UJ
      0.05*

      0.16
      .CONTROL
PARENTS UNEXPOSED
PARENTS EXPOSED
     0               Ql              ID             10.0

     JUVENILE  EXPOSURE CONCENTRATION  (ug/l)

   Figure 1. Average standard length of juvenile sheepshead minnows
          exposed as embryos, fry, and juveniles for 36 days to 0,
          0.08, 0.18,' 0.72, 2.0, or 6.6 us of Kepone/£ of water.
          Parent fish in some instances also were exposed to similar
          concentrations of Kepone: 0, 0.05, 0.16, 0.80, or 1.9 pg/ Si.

   -'Concentration of Kepone in water, yg/?,, for parent fish exposed prior to
   placement of their embryos in Kepone-free water.
                            - £80 -
-------
                           Literature Cited



American Public Health Association.  1971.   Standard methods  for  the  exami-

     nation of water and wastewater.  American Public Health  Association.

     14th ed. Washington, D.C.  1193 p.

Bahner, L.H., C.D. Craft, and D.R. Nimmo.  1975.  A saltwater flow-through

     bioassay method with controlled temperature and salinity.  Progressive

     Fish Culturist.  37(3).  126-129.

Butler, P.A.  1963.  Pesticide-Wildlife  Studies.  U.S. Department  of  the

     Interior, Circular 167, Washington, D.C.  pp 11-25.

Hansen, David J., Larry R. Goodman, and  Alfred J. Wilson,  Jr..  Kepone  .

     Chronic effects on embryo, fry, juvenile, and adult  sheepshead minnows,

     (Cyprinodon variegatus Chesapeake Sci.  (In press).

Hansen, David J., Alfred J. Wilson, Jr., DelWayne R. Nimmo, Steven C. Schimmel,
                                                               >
     Lowell H. Bahner and Robert Huggett.  1976.  Kepone:  Hazard  to  Aquatic

     Organisms.  Science 193(4253): 528.

Hollister, T.A., G.E. Walsh, and J. Forester.  1975.  Mirex and marine  uni-

     cellular algae:  accumulation, population growth, and oxygen  evolution.

     Bull. Environ. Contain. Toxicol. 14: 753-759.

Jaeger, Rudolph J.  1976.  Kepone Chronology.  Science 193(4248):  94.

Mount,  D.I. and W.A. Brungs.  1967.  A simplified dosing  apparatus for  toxi-

     cological studies.   Water Res. 1:21-29.

Nimmo,  D.R., L.H. Bahner, R.A. Rigby, J.M. Sheppard, and  A.J.  Wilson, Jr.

     Mysidopsis bahia;  An estuarine species suitable for life-cycle  bioassays

     to determine sublethal effects of a pollutant.  Proceedings  Symposium on

     Aquatic Toxicology and Hazard Evaluation, American Society of Testing

     Materials.  Memphis, Tenn. 25-26 October 1976.  (In  press).
                                 - 281 -
-------
Srhlmmel, Steven C. and Alfred J.  Wi]son, Jr.  Acute toxicity of




     to four estuarine animals.  Chesapeake Sci. (In press).




Srhimmel, Steven C.,  David J. Hansen and Jerrold Forester.  1974.  Effects of




     Aroclor—1254 on laboratory-reared embryos and fry of sheepshead minnows




     (Cyprinodon variegatus).  Trans. Amer. Fish. Soc.  103(3): 582-586.




U.S. Environmental Protection Agency.  1975.  Methods for acute toxicity tests




     with fish, macroinvertebrates, and amphibians.  Ecological Research series.




     EPA-660/3-75-009: 61 p.




Walsh, Gerald E., Karen Ainsworth, and Alfred J. Wilson.  Toxicity and uptake




     of Kepone in marine unicellular algae.  Chesapeake Sci.  (In press).




Woelke, Charles E.  1972.  Development of a receiving water quality bioassay




     criterion based on the 48-hour Pacific oyster (Crassostrea gigas) embryo.




     Technical report 9: 93 p.
                                     - 282 -
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          ACUTE TOXICITY OF KEPONE  TO FOUR ESTUARINE ANIMALS








                                     SchLmmel, S. C. and Wilson, A. J.









                            ABSTRACT









     Recent contamination of the James River estuary Virginia, with




Kepone prompted acute flowthrough bioassays to determine the 96hour




toxicity of the insecticide to four estuarine species native to that




ecosystem.  The species and their 96-hour LC50 values were:  grass




shrimp (Palaemonetes pugio), 121 yg/£; blue crab  (Callinectes sapidus),




 210 pg/£; sheepshead minnow (Cyprinodon variegatus), 69.5 pg/£; and




spot (Leiostomus xanthurus), 6.6 pg/&.  Surviving animals were analyzed




for Kepone.   Average bioconcentration factors (the concentration of




Kepone in tissues divided by the concentration of Kepone measured in




seawater) were:  grass shrimp,  693; blue crab 8.1; sheepshead minnow,




1,548;  and spot, 1,221.
                                  - 283 -
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                          INTRODUCTION




     Few published data are available on Kepone toxicity to estuarine


animals.  Butler (1963) reported EC50 values (based on mortality or


loss of equilibrium in 48 hours for shrimp and on inhibition of shell


deposition in 96 hours for oysters) of 85 yg/£ for brown shrimp (Penaeus


aztecus) ; 57 yg/£ and 15 yg/£ for eastern oysters (Crassostrea virginica)


exposed at seawater temperatures of 14 C and 31 C, respectively.  Twenty
percent of the blue crabs (Callinectes sapidus) exposed to 1,000


Kepone died in 48 hours.  Butler's data were derived from flow-through


bioassays and based on nominal, not measured, concentrations of Kepone


in seawater.

                                                D
     Recent discharge of the insecticide, Kepone , into the James River


estuary, Virginia has resulted in contamination of that system's water,


sediment, and biota.  This contamination raised questions about the acute


and chronic effects of Kepone on the aquatic life in the estuary and  the


potential danger to humans by eating contaminated animals.


     In January 1976, .we initiated flow-through bioassays to determine


bioconcentration and acute toxic effects of Kepone on representative


species found in the James River estuary.  These were grass shrimp


(Palaemonetes pugio) , blue crab (Callinectes sapidus) , sheepshead


minnow  (Cyprinodon variegatus) , and spot (Leiostomus xanthurus) .
                                   - 284 -
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                      METHODS AND MATERIALS









     Acute toxicity was determined by exposing 20 animals per aquarium  to




different concentrations of Kepone for 96 hours in  flow-through bioassays




similar to those described by Lowe et al.  (1972).   All  test animals were




acclimated to laboratory conditions for at least ten days prior to testing.




The temperature and salinity of seawater in which they  were held were




allowed to vary with those of Santa Rosa Sound, Florida during acclimation




and testing.  Our acclimation and testing procedures were compatible with




those of Standard Methods  (A.P.M.A., 1971).  All test animals were captured




in the vicinity of the Gulf Breeze Laboratory and samples contained no




detectable Kepone (<0.02 yg/g).  During acclimation test animals were fed




frozen brine shrimp daily.  Animals were not fed during the tests, but




could obtain food (plankton and other particulate matter) from the unfil-




tered seawater.  Seawater was pumped from Santa Rosa Sound into a constant-




head trough in the laboratory and delivered to each 18  aquarium by a




calibrated siphon that delivered approximately 68£/hr.  One control and




five experimental aquaria were used in each test.   Stock solutions of




Kepone (88% pure), in reagent-grade acetone, were metered into experimental




aquaria at the rate of-60 mfc/hr.




     The 96-hour LC50 values were determined for both nominal and measured




concentrations of Kepone in seawater.  Nominal concentrations were those




calculated to be in seawater, based on the concentration of the stock




solution,  plus the stock solution and seawater flow rates.  The LC50 values




were based on measured Kepone concentrations determined by chemical analysis




of the exposure water.  Mortality data were subjected to probit analysis




to determine LC50 values and their 95% confidence limits (Finney, 1971).
                                  - 285 -
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    At the end of each 96-hour test, surviving animals from each con-




centration were sacrificed, rinsed with acetone, and pooled as a single




sample for residue analysis.




    Water samples were analyzed by extracting one liter of seawater




twice with 100 ml of methylene chloride.  The combined extracts were




concentrated to about 5 ml in a Kuderna-Danish Concentrator on a steam




table.  Fifteen milliliters of benzene were added and the extract recon-




centrated to remove the methylene chloride.  The extract was cleaned up




on a Florisil Column as described below.




    Tissues of shrimp, crabs, or fish were weighed in 150 mm x 25 mm




(O.D.) screw-top test tubes and extracted twice with 5 ml volumes of




acetonitrile for 30 seconds with a model PT 10-ST Willems Polytron




(Brinkman Instruments, Westbury, New York).  The mixture was centi-




fuged and the acetonitrile transferred to a 250-ml separatory funnel.




After the second extraction, the tissue was extracted with one 5-ml and




one 10-ml volume of acetone.  After each acetone extraction the tube




was centrifuged and the. acetone added to the 250-ml separatory funnel.




To the combined extracts, 100 ml of 2.0% aqueous sodium sulfate and 10 ml




of 1:1 diethyl ether-petroleum ether were added.  The separatory funnel




was shaken for one minute.  After the solvent phases had separated, the




lower aqueous phase was drained into a 250-ml beaker and the upper ether




layer was collected in a 25-ml Kuderna-Danish concentrator tube.  The




ether extraction was repeated three times with 5 ml of 1:1 diethyl ether-




petroleum ether.  The combined extracts were concentrated just to dryness




by placing the concentrator tube in a water bath at A5oC and blowing off







                                 - 286 -
-------
the solvent with a gentle stream of nitrogen.  The residue was transferred

to a 200 mm x 9 mm (I.D.) Chromaflex column  (Kontes Glass Co.) containing

2.3 gm of Florisil topped with 2.0 gm of anhydrous sodium sulfate.  The

column initially was washed with 10 ml of hexane and the residue  trans-

ferred with four 0.5 ml volumes of 5% diethyl ether in hexane.  The

column was eluted with 20 ml of 5% diethyl ether in hexane to remove PCB

and pesticides.  Kepone was eluted in a second elution of 40 ml of 1%

methanol in benzene.   Extracts were concentrated or diluted to appropriate

volumes for analyses by electron capture gas chromatography.

     Determinations were obtained by Varian Aerograph Model 2100  and
                            /
1400 Gas Chromatographs equipped with 182 cm x 2 mm (I.D.), glass columns

packed with 2% SP2100 and 9.75% SP2250: 9.97% SP2401 on 100/120 mesh

Supelcoport.  The operating parameters were:  oven temperature 185 C,

injector temperature 200 C, detector temperature 216 C, and nitrogen

carrier gas flow rate 25 ml/£ minute.

     The average recovery rate of Kepone from fortified tissue was 87%;

from water, 85%.  Residue concentrations were calculated on a wetweight
                                           i
basis without a correction factor for percentage recovery.  All samples

were fortified with an internal standard (dichlorobenzophenone) prior  to

analysis to evaluate the integrity of the results.
                                - 287  -
-------
                     RESULTS AND DISCUSSION



     Kepone, at concentrations tested, was acutely toxic to shrimp and

fishes but not to blue crabs.  The LC50 values varied widely among

species.  Spot were the most sensitive with a 96-hour LC50 of 6.6 yg/£;

the sheepshead minnow LC50 was over ten times higher (69.5 yg/&).  The

two crustaceans were less sensitive.  Grass shrimp LC50 was 120.9 yg/£,

and no significant mortality was observed in blue crabs measured concentra-

tions as high as 210 pg/£ (Tables 1 and 2).

     Although the sensitivity of fish to Kepone toxicity differed, the

symptoms of Kepone poisoning were similar.  An early symptom was lethar-

gic behavior followed by loss of equilibrium.  These symptoms occurred
                             /
in sheepshead minnows at 48 hours in 56 and 100 yg/fc concentrations and

96 hours in 18 and 32 yg/2, concentrations.  Spot exhibited the symptoms

in 48 hours when exposed to 7.5, 13.5 and 24 yg/£ Kepone.  An advanced

stage of poisoning was evident in dark coloration of portions of the

fish's body.  This color change was striking in that some fish had

normal coloration on one side of their bodies, while the other side was

nearly black with a sharp line of demarcation.  Some spot and sheepshead

minnows were darkened in only one quadrant of the body; for example, the

left side posterior to the pectoral fins.  These color changes were

always more marked and appeared earlier in the higher Kepone concentrations.

Hansen et al. (In press) also noted color changes in sheepshead minnows

exposed to a lower Kepone concentration (0.8 yg/Jl) over a longer duration

(11 days).  The same authors also noted that growth, reproduction and
                                  - 288 -
-------
survial of  sheepshead minnows  were affected in 36 days by Kepone concen-




trations as  low as  0.08  yg/liter,  which is 0.001 of our sheepshead




minnow  (LC50 (69.5  yg/liter).   If  we assume that the same ratio exists for




spot as Hansen et al. reported for sheepshead minnows, then the no-effect




level for spot would be  less  than  0.007 tig/liter based on our spot LC50




(6.6 yg/liter).




     No color changes were  observed in the two crustaceans although they




were lethargic in Kepone concentrations greater than 75 yg/liter.




     Kepone  was biocor. -.entrated by all trist animals in 96 hours, although




bioconcentration factors (concentration of Kepone in tissue divided by




measured Kepone in  water) varied from species to species (Table 1).  (The




bioconcentration factors for  fish  were similar, x = 1200-1500).  The two




fishes  bioconcentrated averages of 1.7 and 3.3 X the bioconcantration




factor  of the grass shrimp  and 150 and 190 X that of the blue crab.  This




difference has beeu noted in  similar bioassays with other organochlorine




insecticides.  ochimmel  et^  al.  (1976) reported that sheepshead minnows,




spot and pinf isli (Lagodon rhomboides) bicconcentrated 4 to 70 X more




heptachlor  tha^ ,->ras-i shrimp  or pink shrinp (Penaeus duorari'm).  A similar




relationship o.^urred when  some of the same rpecies wero1. expose-1 to toxa-




phene (Schimntf;! et  al..   In press) and die^drin (Parrish e_t^ a±_. , .i974)




in 96-hour bioassays.  The  reason  for an extremely low bioconcentration




factor  in thv blue  crab  compared to grass .ihrimp is not known.




     Further j;:udies over a longer period of time are required to better




understand  rhe more subtle  effects of Kepone on estuarine animals.  One




reason  Per this assefjsment  is  that most ueaths occurred after 48 hours




in our  tests.  These studies  should include:  (1) Icng-term bioconcen-




tration studies; (2) bioassays  which include the hatching and early develop-




ment of an estuarine animal; and (3) st'.dies to determine movement of




Kepone  through an estuarine food web.




                                    - 289 -
-------





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                         ACKNOWLEDGMENTS









     The authors wish to recognize the significant contributions of




Jerrold Forester and Johnnie Knight in the chemical analyses of water




and tissue samples and of James M. Patrick, Jr., for help in the




bioassays.
                                       - 292 -
-------
                        LITERATURE  CITED









AMERICAN PUBLIC HEALTH ASSOCIATION.   1971.   Standard  Methods  for the




     Examination of Water and Wastewater.   American Public  Health




     Association.  14th ed. Washington, D.  C.  1193  p.




BUTLER, P. A.  1963.  Pesticide-Wildlife  Studies—A review  of Fish and




     Wildlife Service Investigations  During 1961  and  1962.  U.S. Fish




     and Wildlife Circular.  167  pp.  11-25.




FINNEY, D. J.  1971.  Probit Analysis,  Cambridge  University Press.




     Great Britain, 333 p.




LOWE, J. I., P. R. PARRISH, J. M. PATRICK,  JR., and J.  FORESTER.  1972.




     Effects of the polycnlorinated biphenyl Aroclor   1254  on the




     American oyster, Crassostrea virginica.  Mar. Biol.  (Berlin)




     17: 209-214.




HANSEN, D. J., L. R. GOODMAN and  A. J.  WILSON,  JR.  Kepone:  Chronic




     Effects on Embryo, Fry, Juvenile and Adult Sheepshead  Minnows,




     Cyprinodon variegatus.  Chesapeake,  Sci.  (In press).




PARRISH, P. R., J. A. COUCH, J. FORESTER, J.  M. PATRICK,  JR., and




     G. H. COOK.  1974.  Dieldrin:  Effects on Several  Estuarine




     Organisms.  Proc. 27th Annu. Conf. Southeastern  Assoc. Game




     Fish. Comm. 427-434.




SCHIMMEL, S. C., J. M. PATRICK, JR.,  and  J.  FORESTER.   1976.   Heptachlor:




     Toxicity to and Uptake by Several Estuarine  Organisms. J.  Toxicol.




     Environ. Health.  1: 955-965.




	, J. M. PATRICK, JR., and  J;  FORESTER.   Uptake and toxicity of




     Toxaphene in several estuarine organisms.  Arch.  Environ.  Contam.




     Toxicol. (In press).




                                    - 293 -
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                       KEPONE ACCUMULATION AND FOOD CHAIN TRANSFER
L.H. Bahner, A.J.  Wilson, J.M. Sheppard, J.M. Patrick, L.R. Goodman, and




   G.E.  Walsh
                                  - 294 -
-------
ABSTRACT:   Accumulation,  transfer, and loss of Kepone in estuarine organisms




were studied in laboratory bioassays.  Kepone was bioconcentrated by oysters




(Crassostrea virginica),  mysids (Mysidopsis bahia), grass shrimp  (Palaemonetcs




pugio),  sheepshead minnows (Cyprinodon varicgatus), and spot  (Leiostomus




xanthurus),  from concentrations as low as 0.023 yg/£ seawater,  Biocon-




centration factors ranged from 10 to 340 in static exposures and  900 to




13,500 in flow-through bioassays and were dependent on species and exposure




duration.




     Depuration of Kepone from oysters in Kepone-free water was rapid  (35%




loss in 24 hours); however,  depuration of Kepone was slow in crustaceans and




fish, with tissue concentrations decreasing 30-50% in 24-28 days.




     Oysters,  fed Chlorococcum containing approximately 34 yg Kepone/g wet




weight,  attained 0.21 yg Kepone/g (wet tissue) in 14 days, but when fed




Kepone-free plankton, depurated Kepone to below detectable concentrations




(<.02 yg/g)  within 10 days.




     Spot obtained Kepone when fed live mysids that had grazed on Kepone-




laden brine shrimp.   Kepone residues (1.05 yg/g wet tissue) in these




fish approached the concentration of their food (1.23 yg/g wet tissue);




at the lower concentration tested, Kepone concentrations below detection




limits (<.2 yg/g) in prey accumulated in the predator to detectable concentra-




tions (0.02 yg/g) within 30 days.   Bioaccumulation factors (concentration of




Kepone in predator/concentration in prey) at 30 days were equal (0.85 spot/




mysid; 0.53 mysid/brine shrimp)in the high and low concentrations tested.
                                       - 295
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                                   Introduction




     Contamination of the James River water,  sediments,  and biota with

Kepone has prompted research to help define the routes of transfer of

the insecticide from water through selected estuarine trophic levels.  Biota

of the James River Estuary and Chesapeake Bay contain Kepone (Hansen et al.

1976), apparently due to transport of the chemical downstream from the freshwater

portion of the river.  Since no convenient method existed to assess the rate of

Kepone movement in the biota of the James River and Chesapeake Bay, laboratory

bioconcentration from water and bioaccumulation from food experiments were

designed to determine the rates and magnitudes of Kepone accumulated from water

and food by selected estuarine organisms.   It is important to determine the

accumulation of Kepone from water and food by various estuarine species, so
                               /
that the information can be used in the decision-making processes that may

affect the water quality for the biota in the Chesapeake Bay region or limit

transfer of Kepone to seafoods consumed by man.  The alga, oyster, mysid,

shrimp, and fish used in our experiments are representative of many ecologically

important species.  The top consumers in our food chains tested are endemic to

both the Chesapeake Bay area and northern Gulf of Mexico and are commercially

important human food items.  Leiostomus xanthurus, the top carnivorous

species of one laboratory food-chain, provides an estimated 21.5 million

pounds annual recreational catch for fishermen of the Middle Atlantic

states (U.S. Department of Commerce 1975).

     This study provides information about:  (1) the rates and magnitudes

of Kepone accumulation from water by estuarine biota; (2) rates of Kepone depura-

tion by animals in Kepone-free water; and  (3) rates of Kepone transfer through

laboratory food chains.
                                         - 296 -
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                                Methods



BIOCONCENTRAT10N OF KEPONE FROM WATER BY ESTUARINE ORGANISMS

Oysters

     Eastern oysters (Crassostrea vlrginica) were exposed to Kepone  (88% pure)

in a 56-day flow-through bioassay to determine the rates of uptake and

depuration of this insecticide.  Seawater (mean temperature 14.2 C; mean

salinity 15  /oo) was pumped from Santa Rosa Sound, Florida, into a con-

stant-head trough in the laboratory.  Approximately 440 A/hour was delivered

by siphons to each of three 166 £ aquaria.  Oysters (100/aquarium) were not

fed but could obtain plankton from the unfiltered seawater in which they

were held.  Stock solutions of Kepone in triethylene glycol (TEG) were metered
                               /
into the two experimental aquaria at the rate of 10 ml/day.  Measured concen-

trations of Kepone in the two experimental aquaria were 0.39 and 0.03 ug/£

seawater.  A control aquarium received 10 ml TEG/day.

     Oysters (56 mm to 92 mm, umbo to distal valve edge height; x" = 71.8 mm)

were collected, acclimated to laboratory conditions for ten days, exposed

to Kepone for 28 days, and then held for 28 days in Kepone-free seawater.

Five oysters were sampled-from each aquarium at 4 hours, 8 hours, 1 day,

8 days, and twice weekly thereafter to day 28.  During the 28-day depuration

portion of the test, oysters were sampled at similar intervals.  Analysis

methods for Kepone in water and tissues (whole-body, wet weight) were those

of Schimmel and Wilson (in press).

Crustaceans

     Mysids (Mysidopsis bahia), collected from laboratory cultures (Nimmo

et al.  in press), were exposed to average measured concentrations of 0.026
                                     - 297 -
-------
or 0.41 11 g Kepone/X, seawater for 21 days (moan temperature 27.2 C; mean




salinity 18  /oo) and in a second experiment, grass shrimp (Palaeinonetes




pugicp,  seined and acclimated to experimental conditions for 10 days, were




exposed to average measured concentrations of 0.023 or 0.40 yg Keponc/Jl sea-




water in a 28-day flow-through bLoassay (mean temperature 27 C; mean salinity




25  /oo).  Experimental methods used were those of Bahner et al.  (1975).




The grass shrimp were held for an additional 28-day period in clean seawater




to assess depuration of the insecticide.  Filtered seawater at a rate of approxi-




mately 60 £/hour flowed through each aquarium containing mysids or grass shrimp.




Mysids and shrimp were fed 48-hour-old Artemia nauplii daily.  Kepone content




of mysids and shrimp was determined weekly during exposure and depuration.




In a third experiment, grass shrimp were collected by seine from the Lafayette




River estuary near Norfolk, Virginia, and were held in flowing seawater  (mean




temperature 25.5 C; mean salinity 15  /oo) in the laboratory to determine the




extent of depuration of Kepone from field-exposed shrimp.   These shrimp were




analyzed for Kepone concentrations on days 7, 11, 17, and 21 after being trans-




ferred to flowing Kepone-free water in our laboratory.




Fishes




     Sheepshead minnow (Cyprinodon variegatus) adults, acclimated to lab-




oratory test conditions, were exposed to an average measured concentration




of 0.05 ug Kepone/£ of water (mean temperature 30 C; mean salinity 15  /oo)




for 28 days, using the methods of Hansen et al.  (in press) arid were held




in Kepone-free water for an additional week.  Ten fish, generally five females




and five males, were sampled on days 0,1,3,7,14,21, and 28 of exposure to Kepone




and on day 7 of depuration.
                                         - 298  -
-------
     Spot (J.eiostoinus^ xantburus) were seined,  acclimated for 10 dnys,




exposed to average measured concentrations of 0.029 or 0.4 yg Kcpone/£




of filtered flowing seawater (mean temperature 23 C; mean salinity ]8




 /oo) for 30 days and allowed to depurate the chemical for 24 days.  Com-




posite samples of three fish were sampled each week for residue analysis.




Spot, exposed to 0.4 yg Kepone/£ seawater and allowed to depurate for 24 days,




were dissected into Uver, brain, gills, muscle, and offal (rest of body tissues)




and analyzed for Kepone.




     Fillets (including scaleless skin) and the remaining portions of




sheepshead minnows and spot (wet weight) were analyzed for Kepone content.




The data were summed to calculate concentrations in whole fish.









BIOACCUMULATION OF KEPONE IN FOOD CHAINS CONSISTING OF ESTUARINE ORGANISMS




Algae-Oyster Food Chain




     The green alga, Chlorococcum sp., contaminated with Kepone was used as




food for oysters to determine if contaminated phytoplankton could be a significant




source of the pesticide to oysters.   Chlorococcum sp. was grown for 6 days




in one liter of culture medium in 2800-ml Fernbach flasks according to the




method of Hollister et al. (1975).  Random cultures were dosed with 0.1 mg Kepone




in acetone, while others served as controls after treatment.with acetone alone.




After 24 hours of exposure, algal cultures were harvested by centrifugation and




washed three times by resuspension in clean growth medium and centrifuga-




tion.  The cells were resuspended in 5& of seawater and fed to oysters by




using the methods of Bahner and Nimmo (1976).   Samples of the algae were




analyzed daily for Kepone.
                                   - 299 -
-------
     Rate of Kepone accumulation was determined by allowing oysters to feed


on control or Kepone contaminated green algae in flowing seawater.  Oysters


for this study were collected and acclimated for 10 days to laboratory con-


ditions in flowing seawater.   Twenty-four oysters were placed in each of two


aquaria (one control and one experimental) that received 60;?,  filtered sea-


water/hour (mean temperature 22 C, mean salinity 19  /oo) and were fed approxi-


mately 50 mjl of the appropriate (control or contaminated) algal suspension at


15-minute intervals for 14 days.   A 10-day depuration period followed the feed-


ing study during which the oysters received raw, unfiltered flowing seawater


and no additional Chlorococcum.  Oysters (n = 3 per sample) were analyzed for


Kepone content on days 0,7,10,14,17, and 24 of the experiment.
                               /

Plankton-Mysid-Fish Food Chain


     Transfer of Kepone from water to plankton to mysids to fish was investigated


by feeding living brine shrimp nauplii that were contaminated with 2.33 yg


Kepone/g tissue to mysids, that were then fed to spot, the top predator of this


laboratory food chain.  Juvenile spot were seined and acclimated according to


the methods previously described for sheepshead minnows and spot.  Mysids


(Mysidopsis bahia), the intermediate food organism, were collected from labora-

tory cultures.  Commercially available brine shrimp eggs were hatched during


48 hours in clean seawater or in seawater to which 0.005 or 0.1 mg Kepone/£ was


added (Bahner and Nimmo 1976).  The brine shrimp were harvested daily and served


as the "planktonic" food for the mysids.  Approximately 40 mysids were distrib-


uted among each of six compartments of two 30-Jl aquaria.  The compartments were
                                    - 300 -
-------
separated by coarse nylon screen that allowed for flow of water and Artemia




throughout each aquarium while confining the mysids to separate compartments.




Mysids that had fed on Artemia for 72 hours were harvested from one compart-




ment of each holding aquarium, rinsed with seawater, and fed to the spot.




Each compartment was refilled with mysids to provide for subsequent feeding




periods.   By this method, each of 12 juvenile spot, (average length 40 mm),




in each of three 30-£ glass aquaria, were fed 3 to 5 control or contami-




nated mysids daily.  Aquaria containing spot received 609. of seawater/hour to




prevent anoxia and to minimize bioconcentration of Kepone depurated from the




mysids.  Water averaged 19 C and 18  /oo salinity.  Brine shrimp, 30 to 45




mysids, 2 to 3 spot, and water from each aquarium were analyzed weekly for




Kepone.
                                        301 -
-------
                        Results and Discussion


B10CONCENTRATJON FROM SKAWATER

     Kepone was bioconcentrated from water by oysters, mysids, grass slirimp,

sheepshead minnows,  and spot in all concentrations tested (Figs. 1, 2, '3,

4, and 5; Table 1) and all species showed nearly equilibrated tissue concentra-

tions of Keponc within 8 to 17 days after exposure to Kupone began in wate.r.

Bioconcentration factors for Kepone in these species ranged from 2,100 to 13,rjOO

in long-term (>96 hrs) flow-through bioassays (Table 2). Kepone bioconcentrated

in oysters to approximately 10,000 tines the concentration in the exposure water

within 19 days.  Mysids bioconcentrated Kepone up to 13,000 times the amount

measured in the exposure water.  Each mysid (mean live-weight = 2.5 mg for 66

adults), exposed to 0.026 pg Kepone/£ for 14 days contained approximately 5.9 ng
                                 I
Kepone; therefore this amount of the chemical could enter food chains of

estuarine predators that consumed each mysid.  Stomachs of flounders from

Chesapeake Bay (standard length 25 to 174 mm) contained an average of twenty

mysids (Stickney et al. 1974); mysids comprised up to 14% of the diets of striped

bass from the York and Rappahannock Rivers.  Mysids xjere conspicuously absent

in gut analyses of James River striped bass, but decapod crustaceans  (i.e.

Palaemonetes sp.) accounted for 48% (by volume) of their diets  (Markel and
                                              >
Grant 1970).  Palaemonetes have one of the highest bioconcentration factors of

Kepone (Table 2), and like other decapod crustaceans, are one of the species

least sensitive to acute exposures of Kepone  (Schimmel and Wilson In press).

Grass shrimp bioconcentrated Kepone up to 11,000 times the concentration in the

exposure water.  After 28 days of exposure to 0.023 yg Keponc/I, each shrimp con-

tained approximately 8.6 ng Kepone, an amount that could be transferred to predators.
                                       - 302 -
-------
Bioconce.nl ration of  Kepone wan more efficient with increased concentrations




in water for all crustaceans tested (Table 2).




     Kepone was bioroncentratod from water by sheepshead minnows—important




omnivores that link energy transfer from detritus and benthic plants and




animals to carnivores in higher trophic levels.  Each fish  (mean weight 1.5  g)




contained approximately 0.54 yg Kepone after 28 days of exposure to 0.05 yg




Kepone/i; seawater.  Kepone concentrations were slightly higher in female sheeps-




head minnows (0.35 yg/g) than male fish (0.25 yg/g).




     Spot, a commercially valuable food fish, bioconcentrated Kepone from 0.029




yg/fc seawater;  each fish (mean weight 1.4 g) contained approximately 0.13 yg




Kepone.  The bioconcentration factors for Kepone in fish were similar to those




of other chlorinated hydrocarbon insecticides  (Schimmel et  al. 1975; Schimrnel




et al. 1976).  Kepone accumulated in edible fillets to near the whole-body con-




centrations in fish (Figs. 4, 5, & 6); therefore, one of the largest reserves




(22  /o) of Kepone in absolute weight is in the edibl'e portion of contaminated




fish.  Although the greatest body burdens of Kepone on a \jet-weight basis are




in the brain, liver, and gill tissues, the relatively large size of muscle and




offal tissues contributes large Kepone reserves to higher trophic levels (Fig. 6)




     Depuration of Kepone was not consistent among the species tested.




Clearance of the chemical from oysters was relatively rapid, with no Kepone




detected within 7 to 20 days after exposure ceased (Fig. 1)-.  Depuration of




Kepone from laboratory exposed grass shrimp  (Fig. 3) and fish (Fig. 4 & 5)




was slower; Kepone concentrations were reduced 30-50  /o in 24 to 28 days.




Grass shrimp from the Lafayette River depurated Kepone at rates similar




to thoso of laboratory exposed shrimp with approximately 20  /o of




the Kepone lost during 21 days in seawater containing no Kepone.  Spot that
                                         - 303 -
-------
were exposed to Keponc for 30 days 
-------
to almost reach equilibrium in 14 days;  but quantity of Kepone transferred




from these algae to oysters was limited,  probably due to rapid depuration




of the chemical from the oysters.  Kepone was not detectable (<0.02 yg/g)




10 days after the oysters received no contaminated food.  Most Kepone




was depurated from oysters within 96 hours; therefore,  if oysters in the natural




environment contain measurable Kepone residues,  a recent or continuous source of




Kepone from water and/or food has been available.




     The maximum overalx accumulation and transfer of Kepone or food-chain




factor from water to algae and finally to oysters was 2.1 (Table 4).




The food-chain factor was obtained by dividing the concentration of the




contaminant in the final consumer by the concentration of the contaminant




in the water of the primary producer.  The concentration measured in each




consumer can be compared with a lower trophic level to determine the bioaccu-




mulation factor of the contaminant for that predator-prey pair.  Bioaccumulation




factor is similar to bioconcentration factor, but the contaminant is in food




and is consumed by the predator.   The bioaccumulation factor for oysters




consuming algae under these test conditions was only 0.007 (Table 4).  These




data indicate that transfer of Kepone from algae by oysters was inefficient,




or that the uptake was'masked by the oyster's ability to depurate the chemical




quickly.




Plankton-Mysid-Fish Food Chain




     Spot accumulated Kepone by consuming live mysids that had grazed on




Kepone-laden brine shrimp (Fig. 8; Tables 3, 5).  Brine shrimp exposed




to 0.1 mg Kepone/H seawater contained whole-body residues of 2.33 ug/g after
                                         305 -
-------
48 hours.  Mysids that fed for 72 hours on these brine shrimp contained 1.23 yg




Kepone/g.  Kepone concentrations in spot that consumed the mysids for 30 days




were slightly less than those in the mysids (Fig.  9), but uptake of Kepone




exceeded depuration in fish as indicated by the positive slope of the uptake




curves.  The failure for residues to reach equilibrium during the test could




be attributed to the slow depuration of Kepone from fish tissues.




     Mysids, which consumed Artemia with residues of 0.05 or 2.33 ug Kcpone/g




(wet weight), attained 0.023 (estimated) or 1.23 yg Kepone/g whole-body residues




within 72 hours.  The estimated 0.023 yg Kepone/g whole-body mysids, obtained




by assuming the bioaccumulation factor of 0.85 (Table 5) for Kepone transfer




from mysids to fish as observed in the food chain beginning with 0.1 mg/J,,




also occurred in the food chain that began with 0.05 mg Kepone/£.  The residue




in mysids was then estimated to be 0.023 yg Kepone/g, which was consistent with




the estimated bioaccumulation factor of 0.5 for Kepone transfer from Artemia




to mysids for 72 hours.  The food-chain factors were different for this food




chain (3.9 compared to 10.5), since the bioconcentration factor for Kepone by




brine shrimp from the lower concentration in water (0.005 mg/Jl) was less than




that from the higher concentration (0.1 mg/S,).  The initial bioconcentration




of Kepone from water by planktonic food organisms was the dominant source of




Kepone to each member of this food chain, since bioaccumulation factors were




less than unity.




     In the field, lower concentrations of Kepone in seawater could result




in a duplication of Kepone residues found in the fish of this food chain




because the plankton could be expected to be chronically exposed to the con-




taminant.  Thus, the food-chain factor would be expected to increase  in the
                                        - 3Q6 -
-------
natural environment since bioconcentration factors for a chloriiiated hydro-


carbon pesticide (DDT) in feral plankton have been shown to exceed 4000X  (Cox


1971).  However, bioconcentration of Kepone could overshadow the amount of
                                                   •

the chemical received from food by the animals in this food chain.  Approxi-


mately 3,000 times as much Kepone in food as in water was needed to produce similar


concentrations in spot in 28 to 30 days.  Therefore, bioconcentration of  Kepone


was dominant in this food chain, but significant quantities (>85  /o) of


Kepone transferred from prey to predatory fish.  Rapid uptake from water  and



food, slow depuration, and appreciable solubility in water indicate that  Kepone


will transfer through food webs and pose threats to consumers.
                                   -  307 -
-------
                           LITERATURE CITED









Bahner, L.H., and D. R. Nimmo!  3976.  A precision live-feeder for  flow-




     through larval culture or food chain bioassays.  Prog. Fish-Cult.  38:  51-52.




	, C.D. Craft, and D.R. Nimmo.  1975.  A saltwater flow-through




     bioassay method with controlled temperature and salinity.  Prog.




     Fish-Cult. 37: 126-129.




Cox., J. L. 1971.  DDT residues in seawater and particulate matter  in  the




     California current system.  U.S. Natl. Mar. Fish. Serv. Fish.  Bull.




     69: 443-450.




Hansen, D. J., A. J. Wilson, D. R. Nimmo, S. C. Schimmel, L. H. Bahner, and




     R. Huggett.  1976.  Kepone:'  Hazard to aquatic organisms.  Science.  193:528.




 	, L. R. Goodman, and A. J. Wilson, Jr.  Kepone: Chronic effects




     on embryo, fry, juvenile and adult sheepshead minnows  (Cyprinodon




     variegatus).  Chesapeake Sci. In press.




Hollister, T. A., G. E. Walsh, and J. Forester.  1975.  Mirex and marine




     unicellular algae: accumulation, population growth and oxygen  evolution.




     Bull. Environ. Contain. Toxicol. 14: 753-759.




Markel, D. F., and G. C. Grant.  1970.  The summer food habits of young-of-




     the-year striped bass in three Virginia rivers.  Chesapeake Sci.




     11: 50-54.




Nimmo, D.R. , L. H. Bahner, R. A. Rigby, J. M.  Sheppard, and A. J. Wil-soh.




      1977.  "Mysidopsis bahia";  An estuarine species suitable for life-cycle




     bioassays in determining sublethal effects of a pollutant.  Presented




     at the Symposium on Aquatic Toxicology and Hazard Evaluation.   American




     Society of Testing Materials.  Memphis, Tennessee, October 25-26, 1976.








                                         - 308 -
-------
Parrish, P.R., J.A. Couch, J. Forester, J.M. Patrick,  Jr.,  and  G.H.  Cook.




     1974.  Dieldrin: Effects on Several Estuarine Organisms.   Proc.  27th.  Annu.




     Conf. Southeast Assoc. Game Fish Comm., 1973.  pp.  427-434.




Parrish, P.R., G.H. Cook, and J.M. Patrick, Jr.   1975.   Hexachlorobenzene:




     Effects on Several Estuarine Animals.  Proc. 28th Annu.  Conf.  Southeast




     Assoc. Game Fish Comm., 1974.  pp. 179-187.




Schimmel, S.C., and A.J. Wilson, Jr.  Acute toxicity  of Kepone  to  four estuarine




     animals.  Chesapeake Sci.  In press.




	, P. R. Parrish, D. J. Hansen, J. M. Patrick,  Jr., and  Jerrold




     Forester.  1975.  Endrin:  Effects on  several estuarine organisms.   Proc.




     28th Annu. Conf. Southeast Assoc. Game Fish  Comm.,  1974.   pp.  187-194.




	, J. M. Patrick, Jr., and Jerrold Forester.   1976.   Heptachlor;
     Toxicity to and uptake by several estuarine organisms.  _J.  Toxicol.




     Environ. Health  1:1-11.




Stickney, R. R., G. L. Taylor, and R. W. Heard  III.   1974.   Food habits




     of Georgia estuarine fishes I.  Four.species of  flounders  (Pleuroneti-




     formes: Bothidae).   U.S. Natl. Mar. Fish. Serv.  Fish.  Bull.  72:  515-525.




U.'S. Department of Commerce.  1975.  Fisheries  of the United States,  1974.




     National Oceanic and Atmospheric Administration,  National Marine Fisheries




     Service.  Current Fishery Statistics No. 6700. pp.  11-24.
                                          - 309 -
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                                      -  323  -
-------
TABLE 1.  Concentrations of Keponc  (yg/g wet  tissue) measured in oysters
          (£.  vi'n;inicn) exposed to 0.03 or 0.39  yg/S.  for 28 days, mysids
          (M.  bj2llijl) exposed to 0.026 or 0.43  yj;/£  for 21 dnys,  grass shrimp
          OP.  pu£j_q) exposed to 0.023 or 0.40  yg/£  for 28 dnys,  sheepshead
          minnows (C. varjcgatus) exposed  to  0.05 yg/£ for 28 days, and spot

(L. xanthurus)
exposed to G. 029 or 0.4
yg/£ for 30
days in flowing
water experiments. Animals were allowed to depurate Kepone for up

to
28 days in Kepone-free flowing seawater.
Duration
of
Exposure
(Days)

1/6
1/3
' 1
2
3
4
7
8
9
11
12
14
15
19
21
25
28
30
Duration
of
Depuration
1/6
1/3
1
2
4
7
11
14
21
24
28
*Final day
Oysters
0.03
H£/*
Whole
Body
0.01?.
0.031
0.036
-
-
o.ii
-
0.18
-
-
0.21
-
0.20
0.29
0.23
0.19
0.21*
•*.



0.30
0.30
0.14
-
0.074
<0.01
<0.01
<0.01
<0.01
-
<0.01
of exposure.
Oysters Mysids
0.39 0.026
yg/£ yg/fc
Whole Whole
Body Body
0.19
0.53
0.96
-
-
1.3 <0.04
0.16
2.2
-
0.15
2.4
0.19
2.5
3.5
3.6 0.12*
2.7
2.2*
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2.7
1.4
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0.18
0.18
0.055
0.039
0. 039
-
< 0. 01

Mysids
0.43
yg/£
Whole
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0.33

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6.3

4.7
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0.072


0.088
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0.12

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0.055
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0.035

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-

0.47

1.79


2.18
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3.15

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2.62

2.5

1.78
1.5
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0.84

                                       - 324 -
-------
TABLE 1.   (continued).
Duration Minnows Minnows
of 0.05 0.05
Exposure y_g/£ 1LE/L
(Days) Muscle Whole
Body
1/6
1/3
1 <0.01 <0.01
2
3 0.019 0.031
4
7 0.086 0.14
8
9
11
12
14 0.19 0.22
15 - -
19
21 0.21 0.24
25
28 0.29* 0.37*
30
Duration
of
Depuration
1/6
1/3
1
2
4
7 0.21 0.22
11
14
21
24
28
Spot Spot Spot Spot
0.029 0.029 0.40 0.40
n£/£ )'£/& IT,M VK/^
Muscle Whole Muscle Whole
Body Body






<0.02 0.037 0.50 0.73





0.055 0.072 0.86 0.76




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0.074 0.093 0.87 1.04

0.57 0.72

0.031 0.0469 0.38 0.52

*Final day of exposure.
                                        - 325 -
-------
TABLE 2.  Bioconcentration factors for selected species ey.posed to




          measured concentrations of Kapone in water.
Species
Chlorococcum sp.
Crassostrea virginica
"
Artemia salina
n
Mysidopsis bahia
"
Palaemonetes pugio
n
Cyprinodon variejjatus
Leiostomus xanthurus
"
"
"
n
n
"
Exposure Duration
Concentration of Exposure
(PB/A) (days)
100. (static) 1
0.03 19
0.39 2]
5. (static) 2
100. (static) "
0.026 21
0.41
0.023 28
0.4
0.05
0.029 30
0.4 "
1.5* 4
3.4*
4.4*
12.0*
16.0*
Mean
Bu'oconcentration
Factor
340
9,354
9,278
10
23
5,962
13,473
5,127
11,425
7,115
3,217
2,340
1,120
941
1,591
900
1,050
*Data from Schimmel and Wilson (in press).
                                        - 326 -
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-------
TABLE 4.  Kepone transfer in algae-oyster food chain.  Algae  (ChJorocLiccuwi sp.)
          grown in Kepone enriched media for 24 hrs was  fed to  oysters  (C.  virginica)
          for 14 days in flow-through feeding experiment.
(1)   Kepone (single dose)  in algal
      media (mg/£)

(2)   Kepone residues in
      algae after 24 hrs of
      exposure (mg/kg)

(3)   Bioconcentration
      factor from water
                                            Control
                                           food chain
                                            Control
                                            Control
                                              (ND)*
                          Exposed
                         food  chain
                             0.1
                       X =  34
                                                                       340
(4)  Kepone residues
      in oysters after 14 days
      of feeding

(5)  Bioaccurnulation factor
      from algae to oysters
(6)  Food chain factor
Control
 (ND)
                                                                         0.21
                              .007
                             2.1
*ND = non-detectable (<0.02 mg/kg).
                                          - 328 ~
-------
TABLE 5.  Kepone transfer in plankton-mysid-fish food chain.   Brine  shrimp
          (A. splina) were hatched duri.ng 48 hrs in Kepone  enriched  senwater
          and were fed to mysids (M. halrLa) for 7/ hrs.  Mysids were then
          fed to spot (L. xanthurus) for 30 days in flow-through  feeding
          experiment.
                                Control
                                food chain
      Low Exposure
      food chain
(1)   Kepone (single dose)
      in brine shrimp
      media (mg/£)

(2)   Kepone residues
      in brine shrimp
      after 48 hrs  of
      exposure (ing/kg)

(3)   Bioconcentration
      factor from
      water [(2) /(.I)]

(4)   Kepone residues
      in mysids after
      72 hrs of feeding
      (mg/kg)

(5)   Bioaccumulation factor
      from brine shrimp to
    •  mysids [(4) /(2)]

(6)   Kepone residues
      in spot  after 30 days
      of feeding (mg/kg)

(7)   Bioaccumulation factor
      from mysids to spot
                                Control
                                Control
                                  (ND)*
                                Control
                                  (ND)
                                Control
                                  (ND)
(8)   Food  chain factor
      0.005
      0.049
      0.043
      0.058
  x = 0.050
     10.
  3f = 0.023
 (estimated)
      0.5
(estimated)
      0.015
      0.024 __
  >c = 0.0195

     >0.85
(estimated)
     >3. 9
                                                                    High Exposure
                                                                    food chain
                        x =
                                                                      0.1
                                                                      1.3
                                                                      2.4
                                                                      3_.3_
                                                                      2.33~

                                                                     23.3
                                                                      0.89
                                                                      1.0
                                                                      1.8
                                                                    = 1.23

                                                                      0.53
                                                                      1.0
                                                                      1 . 1 ._
                                                                  jc = 1.05

                                                                     >0.85
                                                                    >10.5
*ND = non-detectable (<0.02 mg/kg).
                                     - 329 -
-------
THE FATE A11D DEGRADATION OF 14C-KEPONE IN ESTUARINE MICROCOSM'S
        R.L.  Garnas, A.W.  Bourquin, and P.II. Pritchard.

                Environmental Protection Agency
               Environmental Research Laboratory
                 Gulf Breeze, Florida   325611
                          Gulf Breeze 1
                    Contribution number 351
                               r 330 -
-------
ABSTRACT







     The fate of 14C-Kcpone was studied in static and continuous flov estuarine




microcosms.  Biotic and abiotic transformation and volatilization wore not




important processes in these studies.   Kepoirc dcsorbed readily fron salt r.arsh




sediments and Jamer River sediments.  While thin desorption \;ns independent of




environmental temperatures and saJinicy ranges, l\epone residues in sediment




influenced concentrations in the uater column.  Radioactivity was not extractable




from some Janes River sediir.ents, using recop.ni^cd analytJcal procedures.  In




larger continuous flow systems, benthic polycliaetus (Arericola cristr.re)




accumulated high residues of Kepone, died, and decomposed.  These residues \:ere




never available for desorption compared to sediment.  These data will allow




better prediction of the fate of Kepone in the aquatic environment.
                                     - 331 -
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INTRODUCTION
                                           i
     The Environmental Research Laboratory at Gulf Breeze provides EPA with data

related to water quality criteria, pesticide registration, and ocean dumping.
Following the contamination of the James River system with Kepone (Figure 1),
our facility responded with necessary data about the toxicity of Kepone to estuarine
organisms and its potential for bioaccuinulp.tion and bioir.agnification (Bourquin
£t^ c^L. , 1977a; Hansen et_ a!L. ,  1977; Schiminel and V7ilson, 1977; and Walsh _et_ _aJL ,
1977).   However, serious questions arose concerning the fate of Kepone in the
river.
     The fate of a pollutant is closely related to its toxicity; forces such  as
volatilization, sorption, metabolism, and abiotic transformation (photolysis,
hydro lye-is, chelation) affect the availability and toxicology of pollutants to
aquatic species.  A knowledge of the sites of Kepone concentration and rates  of
exchange associated with these sites is necessary for long term regulatory actions.
Sorption and transformation data are needed to determine whether the ecosysten
can remove the pollutant by degradation or eventual washout, or whether physical
assistance from dredging or damming is necessary.
     Presently, the research project at Manhatten College is directed towards
the mathematical analysis and modeling of Kepone in the James River.  The
projection of time required to reduce the levels of Kepone by various natural
processes such as adsorption-desorption and transformation are included as an
important phase of the project.  Unfortunately, insufficient data are available  for

Kepone.
     A variety'of laboratory microcosms have been developed to study the fate of
pollutants Ln the estuarine environment (Bourquin e_t_ jal_., 1977b) .  In the fol-
lowing paper, two of these systems vere used to examine the potential for movement
and transformation of 14-C Kepone.  These data complement other existing research
efforts and allow better prediction of the environmental fate of Kepone with  a

minimum of assumptions.              ~* 332 —
-------
 MATERIALS AND METHODS







 Sediment Collection and Characterization




    Range Point sediment was collected from a salt marsh located on Santa Rosa




 Sound near Gulf Brcc/.e, Florida.  The sediment was passed through a 2r.m stainless




 steel sieve and fractionated into water-suspendable particulate (?) end heavier




 sediments (S).-  The suspendable particulatc was primarily organic dc-trital




 material and combusted completely following ignition.  The heavier sediments vere




 mainly quartz sand with little organic content.




     Sediment grab samples were collected on two separate occasions from the James




 River system.  The first samples (A/26/77) were obtained from the estuary and




 stored at Gulf Breeze under flowing filtered seawater where they were used  for the




 majority of the studies to be reported.  The second set of samples (8/1/77) was




 collected from the river where the turbidity maximum had settled during the surfer.




 Sediments were characterized (Table I) for total organic carbon on ignition




 (500°C, A hours) and for particle size using the settling rate—soil hydrometer




 method (ASTM method 1)422-63, 1964).  While the first set of samples failed  to yield




 any significant Kepone residues, the second set of samples contained 0.18 ppm




 Kapone ("personal corjnunication, A.J. Wilson, EPA, Gulf Breeze, Florida).




     Since the majority of James sediment was clay-like material, K.-.olinite and




 Bentonite clays (Ward Scientific) were included in these studies as reference




 sediments (Bailey and White, 1970).





                                                                V




Environmental Fate Screening System







     A system (Figure 2) consisted of a 125 ml Erlenmeycr flask fitted with a No. 5




Neoprene stopper.   A capillary glass gas inlet allowed introduction of air or




nitrogen; the gas exit was fitted to a disposable Pastuer pipette filled with




XAD-4 resin (Rohm and Haas, Philadelphia, Pa.) ,to trap volatile compounds.  The




small size of the system allowed maximum replication and examination of different




                                       - 333 -
-------
cnvironiiif-ntal substrates and proco<;r;e:>.  SiiniJur systems ware sampled  sequentially



with tinK1 to indicate? rates of transport and L r.-in.s forn.it i on.



     lAC-Keponc was used to minimize involved analysis and  to facilitate,  simula-



tion of environmental levels.  Thi-; chc-niical was provided by Allied Cliuiuical



Corp. (Princeton, New Jersey) with a specific activity of 24.3 )iCi/iiM  and a purity



of 99%.  A stock solution was prepared in acetone .such, that 10 )il '.;a.s  equivalent



to 19.9 vig (1,941,000 dpm) .



     In the standard analytical procedure (Figure 3) , the system was fractionated



into water, suspendablo particulate, and un.su.sp^ndable sediment or sand by repeated



rinsing of the system with equivalent salinity water; Jai/.os sediments  were all



suspendable with this procedure and were not fractionated any farther.  Following



centrifugation (3000 RPM), an aliquot of the water was examined for radioactivity  by



scintill ition counting (Beckman LS-250 Liquid Scintillation System, Atlanta,  Georgia).



The sediment fractions were extracted repeatedly with acetonitrile, with  aliquots



taken for scintillation.  Following the addition of  2% sodium sulfate  water  to the



solvent extracts (4:1 water/solvent), the aqueous fractions were extracted with organic



solvent (1:1 petroleum ether/diethyl ether)  and analyzed by thin layer chromatography



(3:1 diethyl ether/n-hexane; Quanta Gram LQCDF, Quanta Industries, Fair field, New



Jersey) and autoradiography (Birchover Radiochromatogram Spark Chamber, Hitchin,



England-).  Periodically, the extracts were cleaned on florisil columns (2 gm, hcxane



washed; 20 ml rinse of 5% diethyl ether/hexnne;    final olution with  50  ml of 1%



methanol/benzene) and analyzed for Keponc, octachloro-Kcponc, and nonachloro-Kepone.



(standards provided by A. J. Wilson, EPA, Gulf Breeze, Florida) by electron capture



gas chromatography (Hewlett-Packard CC Model 5830A;  Ni63dctector; Model 18850A GC



terminal; 2 nra'id x 2 m glass, 2% OV-101 on Gas Chrom Q, 100/120).  Extracted



sediments were dried and combusted at 900°C (Harvey  Instrument OX-200  Combustion


                                                                               14
System, Hillsdalc, New Jersey) to liberate and trap  residual radioactivity as   C02.
                                      - 334 -
-------
     The XAD-4 resin traps were eluted with 4 ml portions of acetonitriJe directly


into two scintillation vials.  Since all routes of exit from the systems vere sampled


and all system components were subjected to a total analysis, a reliable budget for


radioactivity recovery was calculated for quality control of the data.


     Standard experimental conditions included 10 gm (wet weight) of sediment; 10Q ml


of Santa Rosa Sound water (18-24 ppth);  .constant temperature  of 25°C; 12/12 hr.


diurnal lighting (G.E. Vita Gro); water saturated air (Silent Giant); 19.9 pg 14-C--


Kepone (1,941,000 dpm) added in 10 yl acetone carrier to water column after 48 hr.


acclimation period; and duplicate systems sampled.  As an indicator of desorption,


water was periodically exchanged in systems halfway between sampling days by centri-


fugation of the system sediment and water (3000 RPM), decantation of water for analysis.


and resuspension of sediment in fresh salt water.


     For,Range Point studies, 50 gms (wet weight) of unsuspendable sediment and 2 gms


(wet weight)  of suspendable sediment were added to each system.


     Systems were sterilized by addition of 2 ml (2% v/v) Formalin.  Throughout the


study, sterility was confirmed by plating   0.1  ml   samples of water on Zoebell's


media (15 ppth) and observing the lack of colony formation.


     Anaerobic .systems were completely stoppered throughout the study and were


periodically purged with nitrogen gas.


     For salinity studies, low salinity water (0-3 ppth) was collected from the


Lower Escambia River and high salinity water (28-35 ppth) was collected from the


Gulf of Mexico.  James sediment remained suspended in low salinity systems;

                                                                 
-------
than normal (200 us/system) or diluting to prov.idc a tenfold lower concentration




(2 |!g/system).




     For Kaolinite and Bcntonite clay studies, 10 gm (dry weight) of clay and 100 ml




of Santa Rosa Sound water were used.  Higher contrifugation speeds (10,000 RPM)




were required to separate the sediment from the water.









Continuous Flow System




     These systems were designed to study the fate of pollutants resulting from the




biological activity of aquatic macro biota.  A system (Figure 4) consisted of a




standard 38 liter glass aquarium fitted with a plexiglass lid containing sampling




portals.  Air and water entered and exited the system through glass tubing coupled




to No. 8 Neoprene stoppers.  Raw filtered sea water (18-24 ppth) was continuously




fed through the system with a Harvard Model 1203 peristaltic pump.  The system was




aerated continuously, with exiting air sampled for volatiles by XAD-4 resin traps.




     For these studies tv.-o systems were structured with 9 cr.i of Range Point sedi-




ment and Santa Rosa Sound water to the 2S liter mark.   The systems v:ere allowed to




acclimate static with aeration for 48 hrs. (25°C; 12/12 diurnal  lighting).  Twelve




lugworas (Arenicola cristata) were added to one of the  tanks and a flow rate of 1




£/hr was started through both systems (washout rate = 0.1 hr  ); after four days,




the water flow was stopped and each system was spiked with 1 mg (100 x 10  dpia) of




14C-Kepone in 0.5 ml acetone.  After two days the water flow was.again started at




1 S./hr for both systems.  Aliquots of water (3 ml) were sampled directly for radio-




activity until background levels were obtained.




     Two beds of XAD-4 resin (75 ml wet volume in 250 ml separator}' funnel) were




alternated at the water exit of each system every 48 hr; following removal from a




system, the resin was transferred to a. glass thimble and extracted with methanol in




a Soxhlqt extractor overnight.  Following extraction the resin wa's returned to




the separatory funnel, rinsed with wnter, and used again.  Aliquots of the raethanol




were analyzed directly for radioactivity; like the analytical procedure with the




                                      - 336 -
-------
screening systems,  the methanol was diluted with 2% sodium sulfate water, extracted,


and analyzed by thin layer chroniatography/autoradiography and gas chromatography.


Cores were obtained by iiisertitig a 1.5 cm i.d. teflon tube into the sediment column,


sealing the top of  the tube with a Keoprene stopper, and extruding the intact core.


Cores were fractionated and analyzed like the screening systems.
                                       „      *

     Lugworns and algae were homogenized with acetonitrilc; the solvent was diluted


with aqueous sodium sulfate and extracted and analyzed like the screening systems.
                                       - 337 -
-------
RESULTS


Environmental Fate Screening System

     Initial studies examined Kepone fate with reference sediments.   Previous

experience with salt marsh sediment from Range Point (Bourquin _et_ a 1. ,  1977c) ,

made it a good candidate for these studies;  in addition, its high organic content

represented one extreme situation environmentally.   The results (Table  II)

with both unsterile and sterile (2% Formalin)  systems demonstrate rapid movement

of Kepone into the suspendable sediment  extract fraction (Pe), with  low levels

present in the heavier sediments (Se).   Volatility  (R)  and binding to sediuent

(Pc, Sc) were not major mechanisms of  Kepone transport in these sytems.  Fol-

lowing the initial spike at Day 0, an  equilibrium was established between the

sediment and water.  Constant levels of  Kepone were maintained in the water

column (W) even after system washing began on Day 13, resulting in a continuous

removal of compound from the system.  Sterility did riot affect the movement of

Kepone in these systems.  Analysis of  radioactivity failed to show any  trans-

formation of Kepone throughout the study.

     Ot'xer reference sediments included  Kaolinite (low surface area, low cation

exchange capacity) and Bentonite (high surface area, high cation exchange

capacity) clays.  The results in Table III demonstrate differences in Kepone

movement with these sediments.  Both systems maintained higher Kepone levels

in the water column compared to the Range Point systems, although the Bentonite

systems more closely mimicked the salt marsh systems.  Again binding and

volatility were not significant in Kepone transport; however, greater levels

were washed out of both clay systems with time compared to Range Point  systems.

Kaolinite studies displayed the greatest washout rate of any system studied

with 65% removed from the system after three washings.   Kepone did not decompose
        i
during these studies.


                                      -  338 -
-------
     As was previously mentioned,  grab samples were collected from the. James




River system on two separate occasions and displayed different particle size




distributions and residues of Kepone.   Experimental results with these sediments




are found in Tables IV and V, comparing the effects of sterility and ae.robiosis.




The data indicate that in most cases the systems behaved sir.ilar to the Range




Point studies.  Aerobiosis and sterility did not affect mov-^nent of 14-C Kepone;




again, degradation was lacking in  all  systems.  However, it is worth noting the




greater levels of bound radioactivity  (Pc) in Jamas sediments collected where




the turbidity maxir.um had settled.   This phenomenon was not observed with




sediments collected earlier in the estuary or with Range Point sediments.




     The remainder of these studies were conducted with James sediment collected




from the estuary (4/25/77).  Systems fortified with tenfold higher and tenfold




lower concentrations of Kepone (Table  VI)  displayed radioactivity distribution




similar to other studies mentioned. Again, Kepone did not degrade in these




systems.




     In studies with low salinity  water, sediment remained suspended throughout




the water column.  Finer particles containing about ten percent of the total




Kepone x>.'ere not fractionated from  these systems at standard centrifugatc speeds;




a higher, degree of centrifugation  resulted in Kepone water levels similar to




high salinity systems and the previous studies mentioned.  The suspension of




sediment and salinity differences  did  not  affect Kepone removal from the systems




with the washing procedure; Kepone did not degrade during this study.




     The data in Table VIII reflect  the effects of environmental sunlight




and temperature'on Kepone movement and transformation.  Comparison of these




data with other systems demonstrate little difference in radioactivity distri-




bution or washout.  Kepone did not degrade in these studies after 42 days of




outdoor exposure.






                                        - 339 -
-------
Continuous Flow System




     With the water flow condition?;  of  this  experiment  (1  ;,/hr,  48-72  hrs/resin




bed), the resin was efficient  in the removal  of  1'tC-Kepone from  raw soavater




(>99%);  the Soxhlet extraction procedure  removed all  radioactivity  from the




resin throughout these studies (>95% recovery).   Table  IX  contains  the levels




of radioactivity found in aliquots of water  fro- each system for the first




two weeks of the study.   Radioactivity  disappeared  faster  from water in the




system containing lugworms,  with only half as much  as the  system without




lugvorms by Day 2 when the flow was  started.   At that time some  of  the lugvrorr.s




moved to the surface of  the sediment, an  indication of  unfavorable  conditions;




by Day 5 all of the lugworms were dead, with fungal mats forming over the




tissues.  One lugworn was removed from  the system and found to contain high




levels of radioactivity  in its tissues  (3% of total spike  to system);  all of




the radioactivity was Kepone.   At these levels of accumulation,  the biological




component added to this  system could contain a large  fraction of the original




fortification (3% x 12 = 36%)  and would account  for the more rapid  removal




of radioactivity from the water in  that system.   The  other dead  lugworms were




left in the system, where they eventually decayed and completely decomposed.




     The radioactivity collected from the beds of resin at the water exit was




graphed over time as DPM/24JJ. to compensate  for irregularities in sampling periods.




The data in Figure 5 indicate  a similar washout  rate  of radioactivity from both




systems over the first 70 day  period.  By Day 48, eighty percent of the original




fortification had washed out of the  system without  lugworms and only 40% had




exited the lugworm system.  All of  this radioactivity was analyzed  as Kepone.




By that tine the lugvorms were completely decomposed  and fungal colonies had




disappeared from the sediment  surface;  however,  the radioactive Kepone present




in the tissues was not as available  for washout as  that present in the sediment.
                                     •* 340 -
-------
In fact lor the following 42 days (Figure 6), only 4X more Kepoue was washed




out from each systcn.   During that time the water flow rat'e affected the condition




of the systems and export of Kepone.  Ac a flow rate of 0.5 ?,/hr, large r.ats




of algae began to gro\, on the glass walls and sediment surface; and Keponc




levels in exiting water equilibrated at 60 pptr.  Samples of the algae never




contained appreciable levels of radioactivity.  At a flu-? rate of 0.75 fc/hr,




the algae disappeared from the glass walls and sedir.enl surface; and Kepone




residues in water readied a new equilibrium at 40 pptr.




     Cores taken throughout the study showed 14C-Kepone present in the suspencable




sediment fraction, with little indication of high levels of binding.  Cores




from the lugworm system taken later in the study (after Day 60), contained




30-40% higher levels of radioactivity compared to the system without lugworns.




Analysi- again revealed only Kepone present in the.radioactivity.
                                          - 341 -
-------
DISCUSSION







     These systems v.'trc used to indicate the najor environmental components




affecting the fate of Keponc.   Extrapolation of these data to the James River




system is hampered by severe scaling problems and  inadequacies in the experimental




protocol.  However;  these studies do val idate- current field monitoring practice:;




and offer direction for future field vork to supplement the existing data base




for mathematical modeling-




     Volatilization and transformation were not significant processes affecting




Kepone in these studies,  which implies that they ir:ay not be important: mechanisms




of Kepone removal fro™, the James River.   Concern with the possible environmental




formation of dechlorinated products of Kepone and  their accumulation in tissues




and ser^r.ent may be unwarranted; Kepone contaminating the Janes River is confined




to the aquatic component  and does not represent a  hazard to surrounding terrestrial




communities from air transport.  Current monitoring programs need not expand




analytically to include these  two areas of potential Kepone fate.




     The failure to extract radioactivity from sediment thas been characterized




as an indication of bound residues.  The significance of bound residues relative




to their environmental dissipation, monitoring, and toxicology has been addressed




by others (Kaufman e^ al^. ,  1976).  The availability of these residues for export




or accumulation is an area that requires further investigation.  In these




studies bound residues were only associated with sediments collected from the




turbidity maximum, which already contained high levels of Kepone and a greater




proportion of small particle sizes.  The immediate question relative to the James




River system is whether bJnding to sediments occurs to any great extent or is




merely an isolated event.  Further studies with these systems using other sediments




from the James River could answer this question.  Kepone levels in sediments from




field studies may be only conservative figures.,
                                      T« 342 ~
-------
     Studies with different concentrations of Kepone, water salinity, and system




temperature did not show any changes in the relative percent distribution or




washout of Kepone.  Kepone levels in the water were independent of temperature




and salinity, although lower salinity enhanced suspension of sediments contr.ir.ing




Kepone.  However, Kepone concentrations in the water colur.n were proportional




to the concentrations in the sediment. •System's at the high concentration (200 ug)




contained 100 tiir.es the \:ater and sedir.cnt radioactivity of the low concentration




systems at any tine; Kepone levels washed out of the high concentration systems




were 100 times those of the low concentration systems.  During washout, as




Kepone levels in sediments decreased, concentrations in the water colur.n




decreased.  While Kepone levels collected in the water resin beds of the continuous




flow systems equilibrated with time, the overall trend was decreasing Kepone




concer.tr-v.tions in the water that correlated with lower residues in the sedi~.er.ts.




Environmentally, higher concentrations  of Kepone detected in water may be indicative




of higher Kepone residues in sediments.




     Washout of radioactivity from all  systems correlated with decreasing levels




of Kepone in sediment extracts.  Except for Kaolinite clay studies, the type of




pediraei''. did not affect the desorption  of Kepone.  The Kepone equilibrium between




sediment and water was not biologically mediated.  The potential for Kepone




movement from sediment is important environmentally and represents a continuous




source of exposure to aquatic organisms.  In addition, this process is a nechanism




of Kepone removal from the James River  system.  Greater emphasis on water nonitoring




programs using high volume sampling methods will provide data related to Kepone




concentrations in sediments and Kepone  export from the system.  However, the




recalcitrant nature of Kepone, together with its dynamic movement potential,




forecast an environmental impact reaching beyond the James River system.
                                           343 -
-------
     Lugworms in continuous  flo\7  systems  accumulated  high  levels  of  Keponc;




Kepone did not desorh from these  tissues  foil owing  their decomposition,  although




it was solvent extractablc.   Kepone has a stronger  association with  biological




tissue compared to sediment;  this phenomenon  could  influence,  the  distribution




of Kepone in the James River  and  pay  account  for  the  correlatica  of  high sediment




organic content with corresponding hign residues  of Kepone from monitoring




efforts (personal communication,  Robert Huggctt,  Virginia  Institute  of Marine




Science).
                                        344
-------
                                 BIBLIOGRAPHY

Bailey, G.W. and J.L.  White.  3970.   Factors Influencing the Adsorption,
   Besorpf.ion, and Movement of Pesticides in Soil. Residue Review 32:
   29-92.

Bourquin, A.W.,  R.L. Garnas,  P.11. Pritchard, F.G. Wilkes, C.R. Gripe, and
   N.I. -Rubinstein. 1977b.  Interdependent Microcosms for the Assessment
   of Pollutants in the Marine Environment.-International Journal of
   Environmental Studies, In press.

Bourquin, A.W.,  M.A. Hood, and R.L. Garnas. 1977c.  An Artificial Microbial
   Ecosystem for Determining Effects and Fate of Toxicants in a Salt-
   Marsh Environment.  Development^ in Industrial Microbiology 18:185-191.

Bourquin, A.W.,  P.H. Pritchard, and W.R. Mahaffey. 1977a.  Effects of Kepone
   on Estuarine Microorganisms. Developments in Industrial Microbiology,
   19: In press.

Hansen, D.J., L.R. Goodi-.an, and A.J. Wilson. 1977.  Kepone:  Chronic Effects
   onTmbryo, Fry, Juvenile,  and Adult Shcepsbead Minnows (Cyprinodon varicsy.tus).
   Chesapeake Science 18:227-232.

Kaufmar. D.D., G.G. Still, G.D. Paulson, and S.K. Bandal. 1976.  Bound and
   Conjugated Pesticide Residues.  American Chemical Society Symposium, Series 29.

Schimmel, S.C. and A.J. Wilson. 1977.  Acute Toxicity of Kepone to Four Estuarine
   Animals.  Chesapeake Science 18:224-227.

Walsh, G.E., K.  Ainsvorth, and A.J. Wilson. 1977.  Toxicity and Uptake of Kepone
   in Marine Unicellular Algae.  Chesapeake Science 18:222-223.
                                          <- 345 -
-------
                                   TABLE I
                         SEDIMENT CHARACTERIZATION^
                                                        i

Total Organic on

Ignition
Sand (2.0 - 0.5 mm)
Old Silt (0.05 -
New Silt (0.05 -
Old Conventional
(<0.005 nrni)
New Conventional
(<0.00: rai)
0.005 mm)
0.002 mm)
Clay

Clay

4/26/77 6/15/77 8/1/77 Kaolinite
1.4% 1.5% 4.4% 4.1%
47.4% 44.3% 9.4% 8.8%
20.2% 25.5% 29.1% 25.1%
20.22 27.5% 34.5% 34.1%

32.4% 30.2% 61.5% 65.1%

32.4% 28.2% 56.1% 57.1%
Be-i-onita
0 . 01%
6.0%
5.2%
6.2%

88.8%

37.8%
 James Sedir.cnt I:  Collected 4/26/77; used up to 6/15/77 for all  studies;

2
 James Sediment II: Collected 8/1/77


3500°C; 4 hours.

4
 AST1I method D422-63, 1964.  Settling rate-soil hydrometer method..
                                         - 346 -
-------
                                    TABLE  II
                   RANGE POINT SYSTEMS  -  STERILE  AND UNSTERILE
DAY       V,        Sc       Sc         Pe        PC         R       WASH      TOTAL
Unsterile
0
3
6
10
13
17
24
31
Sterile
0
1
3
6
10
13
17
24
31
12.0
5.4
5.8
5.6
5.2
3.8
4.0
3.6

13.6
9.4
6.7
7.3
6.9
6.9
3.6
3.3
3.1
1.9
4.0
3.5
4.0
3.8
5.8
6.2
5.4

4.5
4.1
1.8
1.9
2.6
2.3
5.7
7.2
7.3
0.1
0.5
0.7
0.8
1.0
1.2
1.2
1.0

0.2
0.1
0.1
0.2
0.3
0.4
0.9
1.2
1.2 '
78.7
69.8
75.5
61.8
69.6
67.4
60.1
43.7

74.4
76.7
79.0
73.9
72.0
69.5
64 . 4
55.3
41.1
2.1
4.2
6.2
4.3
6.4
5.5
5.5
4.7

1.4
1.9
2.6
3.5
4.1
5.6
3.5
4.0
4.2
94.8
0.2 — 84.1
0.1 — 91.8
0.1 — 76.6
0.2 — 86.2
0.2 4.6 88.5
0.2 7.9 85.1
0.1 11.8 70.3

94.1
0.1 -- 92.3
0.1 — 90.3
1.3 — 88.1
0.5 — 86.4
0.5 — 85.2
1.4 7.1 86.6
0.7 10.4 82.1
1.0 14.4 72.3
                                         - 347 -
-------
DAY
W
                               TARL3: ITT




                  KAOIJ.KI.TE AND r.':"TON'ITE  SYSTEMS
PC
PC
R
WASH
TOTAL
Kaplinite
0
8
15
28
35
42
Bentonite
0
8
15
28
35
42
49

48.3
39.3
35.0
14.4
10.0
7.4

70.7
26.7
16.6
7.3
6.8
6.1
3.9

53.1
52.2
50.2
34.0
17.4
15.7

27.8
55.8
58.0
54.6
53.4
48.9
36.7
-
1.5
1.1
2.0
1.7
2.8
7.0

2.6
3.2
3.6
5.0
5.0
6.4
9.9
—
—
0.4
2.0
5.1 29.8
7.8 48.7
1.1 65.8

—
2.6
3.0
7.3 15.6
5.3 24.1
2.5 32.3
2.6 39.0

102.9
93.0
89.2
55.0
86.7
97.0

101.1
88.3
81.2
89.8
94.6
96.2
92.1
                                - 348 -
-------
JAMES RIVER
DAY
Unsterilc
0
11
18
25
Sterile -
0
II
18
25
Unsterile
'5
12
19
Sterile -
5
12
19
W
- Aerobic
18.5
13.0
6.1
4.5
Aerobic
16.2
12.3
6.4
3.7
SYSTEMS - AEROBICS IS AND
Pe PC R
-
76.9 2.1
74.0 5.8 0.3
58.4 2.2 0.4
41.8 3.8 0.1

74.5 2.1
74.6 5.0 0.4
61.2 1.7 0.2
41.6 3.1 1.7
- Anaerobic
16.2 72.6 4.4
12 :6
12.1
Anaerobic
18.8
13.4
11.2
75.9 4.7
77.1 5.2

72.5 2.7
74.7 1.8
76.6 6.7
STERILITY
WASH TOIA

97.
93.
9.7 76.
12.5 62.

92.
92.
11.4 80.
14.1 64.
93.
93.
94.

94.
89.
	 g/, t

L

5
3
8
7

8
3
9
2
2
2
4

0
9
5
- 349 -
-------
                              i'.n: v



     JAMES RIVER SYSTEMS II - CuLLLClT.D 8/1/77;  AEROBIOSIS






DAY     •   W        Te        PC       R       WASH      TOTAL
Aerobic
0
7
14
25
32
40
47
Anaerobic
0
7
14
25
32
40
47

15.9
8.1
7.2
3.9
3.3
3.2
3.0

12.1
6.3
8.2
5.6
4.1
•3.4
3.3

76.8
68.7
68.2
77.3
54.0
42.8
53.9

68.3
74.3
72.1
79.3
53.5 _
41.1
48.0

5" 4
26.2 0.1
23.7 _0.2
10.4 0.2
21.4 0.1
36.0 0.2
20.4 0.5

16.7
18.3
18.1
7.8
30.7
36.6
22.8

98 . 1
103.1
99.3
5.3 97.1
]0.5 89.3
13.7 95.9
17.7 95.5

97.1
98.9
98.4
6.5 99.2
12.6 100.9
15.6 96.7
20.5 94.6
                              - 350 -
-------
                           TADLE VI




              JAMES RIVER SYSTEMS - CONCENTRATIOM







DAY        W       " Pe        PC       R       WASP.      TOTAL
Lov? Concentration
0
7
14
24
30
35
42
High
0
7
14
24
30
35
42
20.
13.
11.
7.
6.
6.
6.
4
2
9
4
6
1
3
72.
75.
70.
70.
55.
64.
55.
0
4
7
1
2
0
8
6
7
6
6
7
7
6
.1
.3
.5
.6
.1
.4
.6
—
0.
0.
0.
1.
1.
1.
—
4
5
6 12.4
1 18.9
3 26.0
2 32.8
98
96
89
97
88
104
102
,5
.3
.6
.1
.9
.8
.7
Concentration
16.
17.
15.
10.
8.
7.
7.
1
S
5
0
5 •
5
1
79.
75.
67.
54.
55.
49.
40.
7
3
8
7 _
5
9
3
4
5
3
5
5
5
4
.8
.4
.7
.0
.5
.8
.7
—
0.
0.
0.
1.
1.
1.
—
2 -,- .
3
7 16.5
4 25.9
0 36.4
5 41.3 '
100
98
87
86
96
100
94
.6
.7
.3
.9
.8
.6
.9
                              - 351 -
-------
                                 TALLE VI1




                     JAiMES  RIVER SVSTi'.tlS - SALINITY







DAY     Wpre     Wpost       Pe       PC      R       WASH     TOTAL
Low Salinity
0
3
6
10
14
18
25
32
39
High
0
3
6
10
14
18
25
32
39
36.8
27.1
25.9
20.8
22.2
11.6
8.7
6.4
6.4
Salinity
19.1
. 14.0
12.3
9.7
9.9
6.4
5.7
4.9
4.6
—
18.9
16.8
14.7
13.4
7.8
5.9
5.2
4.6

—
12.7
11.0
•9.3
' S.4
5.2
4.9
4.2
3.6
55.6
65.0
59.7
71.9
67.1
64.9
59.8
55.7
52.5

73.2
75.6
71^-7
79.7
74.7
69.7
65.4
• 59.4
50.5
2.4
4.3
4.6
4.7
5.4
5.8
5.5
4.9
5.6

3.0
6.1
5.0
3.8
6.7 •
6.1
6.0
5.6
7.4
—
0.1
_ 0.2
0.4
0.8
0.3 12.8
0.4 19.4
0.5 24.1
0.3 30.5

—
0.4
0.4
0.4
1.9
1.7 9.71
2.1 15.9
3.8 20.5
1.0 28.0
94. S
96.5
90.4
97.8
95.5
95.4
93.8
91.6
95.3

95.3
96.1
89.4
93.6
93.2
93.6
95.1
94.2
91.5
                                   - 352 -
-------
                          TABU:  VITI
            JAMES RIVER SYSTEMS  - OUTDOOR STUDIES

DAY        W        Pe        PC      R       WASH      TOTAL
Light
0
3
7
10
13
23
-32
36
42
Dark
0
3
, 7
10
13
23
32
36
42

18.4
19.2
16.3
14.7 .
11.6
9.4
9.6
7.1
5.1

19.4
17.8
15.1
13.9
11.3
8.0
7.8
' 7.7
6.2

69.4
69.4
69.7
67.7
71.4
59.1
45.0
33.8
33.3

65.9
70.5
73.2 ~
73.5
77.0
65.9
61.3
43.4
43.6
-
3.1
4.8
5.4
7.6
7.5
9.3
6.5
4.7
5.0

3.4
4.7
5.3
6.6
6.4
9.0
6.4
5.9
5.4
-
—
0.4
"l.O
0.9
0.6
1.5 12.7
1.2 - 24.3
5.1 31.3
2.6 38.6

—
1.5
0.9
1.0
0.4
•1.6 10.9
3.1 19.0
8.0 29.4
1.7 33.3

90.9
93.8
92.4
90.9
91.1
92.0
86.6
82.0
84.6

88.7
94.5
94.5
95.0
95.1
95.4
97.6
94.4
90.2
                              - 353 -
-------
            TABLE IX




     RADIOACTIVITY IN WATER




Radioactivity DPM -(3 ml Aliquots)
DAY
0
1
2
2
3
4
5
7
8
14
WITHOUT
LUCWOKilS
16,720
10,790
8,650
begin flow - 1 t/hr
2,510
990
635
362
300
135
WITH
LUGVORMS
15,320
6,650
. 4,640

1,160
484
326
241
188
94
                - 354 -
-------
                                    FIGHTS
Figure 1.   Kcpone (decdchlorooctahydro-1,3 ,4-iiietheno-2li-cyclcbut;i(cd)
           pentalene-2--one).
Figure 2.  Environnental Fate Screening System.


Figure 3.  Analytical Fractionation Procedure.


Fipure 4.  Continuous Flow Microcosm.
Figure 5.  Continuous Flov? Systems:  Radioacti\rity  Collected in Water
           Resin Beds.
Figure 6.  Continuous Flow Systcns:  Effect of  Flow Rate Change on
           Radioactivity Export.
                                       - 355 -
-------
   i \: u-
- 356  -
-------
TRAP
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                               WATER
                                  -SEDIMENT
              - 357 *•
-------
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SUSPEflDAELE
PARTICULAR
            EXTRACTION
                         EXTRACT I Oil
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     (3c)        /(Pc)

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         SOLVENT
          (PE)
                    - 358 -
-------
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                                        - 361 -
-------
ACKNOWLEDGEMENTS
     We are indebted to Ronald Dirir.eier, Maurice  Inkel,  Thorns Maziarz, and




William Smith for their assistance in this endeavor.
                                          - 362 -
-------
  The Role of Sediments in the Storage,
Movement and Biological Uptake of Kepone
        in Estuarine Environments
              Annual Report

                   to:

   The Environmental Protection Agency



                  From:

    Robert J. Huggett, Project Manager
 The Virginia Institute of Marine Science
             For the period
          10/20/76 to 10/20/77
       Grant Identification Number
               R804993010
                    - 363 -
-------
                       Preface


     Included in this document are three sections which

describe the efforts of the Virginia Institute of Marine

Science's staff on the Role- of Sediments in the Storage,

Movement and Biological Uptake of Kepone in Estuarine
                              *
Environments.  The first section is entitled: "Kepone in

James River Sediment," by Maynard M. Nichols and Richard

C. Trotman.  The second, "Kepone Water-Sediment Elutriates,"

by Robert J. Huggett and the third, "Uptake of Kepone From

Suspended Sediments by Oysters,  Rangia and Macoma," is

by Dexter S. Haven and Reinaldo Morales-Alamo.

     Also attached is a progress report on the EPA funded

James River Hydrographical Survey Study which was conducted

in the late summer of 1977.
                          - 364 -
-------
               KEPONE IN JAMES RIVER SEDIMENTS
              An annual progress report to EPA
                             by   -.
         Maynard M. Nichols and Richard C. Trotman
                        October 1977

 1.  Purpose.
     This study aims to determine where kepone has accumulated in
the bottom sediments; that is, where are the sediment sinks for
kepone?  A second aim is to trace the routes and rates of trans-
port; that is, what happens to kepone-bound sediment when released
from its source?  Finally, how long will it take to reduce levels
of kepone in the sediment by natural processes?
     Results emerging from the study are of use to advise state
and federal authorities how to clean-up kepone pollution through
natural processes.  They provide basic data on sedimentary pro-
cesses for benthic ecosystem models; they are of use for evalu-
ating the effects of dredging kepone-rich sediments.  As a
tracer of sediment, kepone provides new information on sediment
dispersal and the circulation of fine-grained material in a
classic estuary.

 2.  Highlights of Activities.
     Efforts during the period were highlighted by the following:
         •Review of James River sediment data to predict fate of
          kepone for program formulation.
                              - 365 -
-------
•Presentation  of paper on  results historical  review,


 First  Kepone  Seminar, at  VIMS,  October  1976.


•Preliminary field  sampling  of surface sediments  along
                          *

 length of James in three  periods,  September,  December


 1976,  and March 1977; 37  to*52  stations  sampled  during


 each period;  18 cores obtained.


•Co-ordination conferences with EPA program manager,


 Dr.  Tudor Davies,  Gulf Breaze and  Virginia State Water


 Control Board,  October through December,  1976.


•Employment of project personnel, Mr. Richard Trotman,


 completed April 1977; sediraentologic effort  in  full


 swing.


•Liason with Battelle Northwest,  Dr. Onishi,  on  field


 programs and  math  model formulation.


•Liason with Manhatten College,  Dr. D. 0'Conner  and


 R. Thomann, concerning formulation of a math model


 for  sediment  and kepone transport.


•Development of structure  for mathematical model  of


 sediment-kepone transport with Dr. Kuo.


•Formulate plans for suspended sediment-kepone field



 study, May 1977.


•Follow-up sampling of bottom sediments  and selected


 cores of dredge disposal  sites, July  1977.  Continued


 lab  analyses of these samples and  previous samples.
                     - 366 -
-------
         'Preparation for field study;  filters,  field equipment,



          and field labs for processing suspended sediment,  June



          through July 1977.



         •Field observations, sampling and measurement of kepone



          on suspended sediment,  currents, and related parameters,



          August 1977.



         •Laboratory analyses of suspended sediment samples, total



          concentration, organic content, September through



          October 1977.



         •Participation in Second Kepone Seminar and kepone



          Symposium at the 4th International Conference on



          Estuaries.



         •Follow-up sampling of bed sediments in Hampton Roads



          and lower Chesapeake Bay in conjunction with closing



          of area to crabbing; 12 stations occupied.



         •Field sampling of bed sediments curtailed in October



          1977.  Data reduction largely complete.





 3.  Approach.



     Efforts during the period mainly consisted of field sampling,



laboratory analyses, and data reduction.  First, historical data



on kepone and James River sediments were reviewed to identify



probable kepone sediment sinks and relative rates of deposition.



Sampling stations were sited throughout the estuary in relation



to water depth, bathymetry, oyster grounds, depositipn patterns,



dredge and disposal sites, and in relation to the kepone source.





                              - 367 -
-------
Field procedures were worked out to sample freshly deposited sedi-
ment on the bed as well as in cores at selected sites.  Laboratory
procedure:? were set up to process samples for particle size and
organic content.  The horizontal and vertical distributions of
kepone were delineated graphically and evaluated with tirr.e over
one year in relation to basic information concerning sedimentary
processes and transport of fine-grained sediment.  An attempt was
made to determine from field samples the distribution of kepone
in relation to particle size and organic content.

 4.  Methods and Procedures.
     Bed sediments were obtained by a Petersen grab with a 0.05 m2
bite area or a 7.6 cm (3-inch) diameter corer.  The corer was
especially constructed for obtaining soft mud with minimal dis-
turbance.  Approximately 30 ml of sediment was obtained from the
top sediment surface and returned to the laboratory for analyses.
Stations were closely positioned by ranging or sextant bearings
on buoys and landmarks.  Samples were frozen prior to laboratory
analyses.
     In the laboratory bulk sediment samples were processed for:
(1) kepone content, (2) organic matter by loss on ignition, and
(3) particle size (percentage sand, silt and clay) by sieving
and pipette.  Additionally, the sieved fraction, less than 63u
of samples collected in September and December 1976, was analysed
for both kepone content and for particle size by a Coulter Counter,
Laboratory methods follow conventional procedures described in

                              - 368 -
-------
                     ORIGINAL
                      SAMPLE
                      FREEZER
                      STORAGE
                   PARTICLE SIZE
                  .   ANALYSES,
                 SIEVE AND PIPETTE
                           PARTICLE
                            SIZE
                           < 63U,
                          COULTER
                          COUNTER
              SAND
            FRACTION,
             STORED
SILT AND CLAY
  FRACTION,
 KEPONE ANAL.
    < 63U
Figure 1.  Scheme for laboratory processing of bed sediments.
                               - 369 -
-------
Moncure and Nichols (1968), Standard Methods (1973) and Folk

(1961).  Details are given in laboratory instructions on file at

VIMS sedimentological lab.  Figure"! summarizes steps in labora-

tory processing.


 5.  Results and Their Significance.

Spatial Variability.  A special study of variations in kepone

concentrations in bulk bed sediment over a small spatial range

was conducted at two selected stations:  (1) station 15 in lower

reaches near Wreck Shoal with 3 m water depth and (2) station

AOa in middle reaches at buoy 62 with 6 m water depth.  At sta-

tion 15,,four samples were taken at random from the top < 2 cm

of sediment and of the top < 15 cm of sediment, all from the

same grab.  Table 1 lists the results.  Spatial variations within

the 0.05 m2 area of the grab are relatively small with standard

deviations less than + 7 percent.


Table 1.  Variation in kepone concentrations in the top < 2 cm
          and the top <" 15 cm of sediment from a single grab;
          station 15, June 15, 1977.
Depth Interval     Kepone, ppm

    0-2 cm            0.026
                      0.025            Mean
                      0.029           Range
                      0.026        Std. Dev.

    0-6 cm            0.012            Mean
                      0.013           Range
                      0.013        Std. Dev.
                                              0.027
                                              0.025 - 0.029
                                              + .002 (+ 77.)

                                              0.013
                                              0.012 - 0.013
                                              + .001 (+ 87o)
     At station 40a one sample was taken of the top < 2 cm of sed-

iment from 10 successive grabs.  The grabs were obtained at random


                               - 370 -
-------
while the vessel drifted over distances of 225 m downstream and

135 m upstream from the station.  Results of the sampling and

analyses (Table 2) indicate a very-wide range of values within a
                                    •
distance less than 230 m.  Despite the low bottom relief and small

textural differences of the sediment at the site, kepone concen-

trations ranged as much as 0.41 ppm.  When surface samples were

taken at random from 12 successive grabs at the same station,

number 40a, (Table 2) (an anchor station with an area of about

200 m3) the kepone concentrations ranged 0.47 ppm with a standard

deviation of 44 percent.
Table 2.
Spatial variation in kepone concentrations from the
top < 2 cm of sediment of successive grabs at station
40a, July 5, 1977 (drift station) and July 20, 1977
(anchor station).
            Drift Station
Downstream
225 m
0.062
0.074
0.081
0.067
0.096
0.110
0.130
0.340
0.360
0.470



Mean 0.179
Range 0.062 -
Std. Dev. + 0.151
Upstream
135 m
0.021
0.025
0.029
0.023
0.017
0.013
0.027
0.033
0.029
0.023
Mean 0.024
Range 0.013 - 0.033
Std. Dev. 0.006 (257,)
Mean
0.470 Range
(+ 84%) Std. Dev.
                                                      Anchor
                                                      Station

                                                       0.27
                                                       0.17
                                                       0.44
                                                       0.21
                                                       0.14
                                                       0.27
                                                       0.33
                                                       0.39
                                                       0.34
                                                       0.61
                                                       0.61
                                                       0.28
                                                 0.338
                                                 0.14 - 0.61
                                                 + 0.153 (+ 447.)
                              - 371 -
-------
The marked variations are partly due to the sampling process
whereby some surface sediment is necessarily washed in the grab
or disturbed at depth.  However, most local variations are
inherent in the bed sediments which are affected by variations
in scour and fill, variations in texture and organic matter.
Such variations define rather broad limits which may be placed
on the kepone distribution as a function of location.  They
affect "seasonal" distributions inasmuch as the navigational
capability of relocating a station is no better than a circle
130 m in diameter.
Distribution of Kepone in Surface Sediments.  The sediments from
middle reaches are the most contaminated.  As shown in Figure 2,
average kepone concentrations in bulk bed sediments from the
channel (:> A m depth) are higher between mile 38 and 52 than
near the source (mile 63) or farther seaward in the estuary.
This is the zone of the turbidity maximum which lies landward
of the inner limit of salt intrusion.  Suspended sediment con-
centrations in this zone are higher than elsewhere most of the
year.
     When longitudinal distributions of kepone are compared for
surveys in December 1976, March 1977, and July 1977, there are
no significant trends with time.  Instead the concentrations
are relatively stable within a range of about 0.10 ppm.  How-
ever, the average levels of concentration from December 1976
through July 1977 in middle reaches (0.15 ppm) are generally

                               - 372 -
-------
0.3
£0.2
ci.

UJ

o
D_
LU O.I
            i  TURBIDITY     :
                MAXIMUM  ZONE
                                                      AVERAGE
                                                 VI :'-'iT>r   i^
            60
                                40                 20
                             DISTANCE  LANDWARD.miles
MOUTHED
  Figure 2.   Longitudinal distribution of average kepone concentrations
             in bed sediments  from the channel of the James Estuary;
             mean of December  1976, March and July 1977 values.
                                   - 373 -
-------
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lower than those measured earlier by VIMS in September 1976 and

by the Corps of Engineers in January 1976 when concentrations

were 0.27 to 0.48 ppm.

     The zone of high sediment contamination covers both channels

and contiguous shoals.  As shown in plan view, Figure 3, aver-

age concentrations are higher in the reach between Jamestown and

Weyanoke than elsewhere.  The highest average concentration is

in sediment from a shoal off Dancing Point.  Elsewhere, concen-

trations are locally high off mouths of tributary creeks such as

Bailey's Creek near the kepone source, Chippokes Creek, The

Thorofare, Jamestown and the Warwick River.  Substantial con-

centrations, ranging 0.66 to 1.20 ppm, are found in Burwell Bay.

However, concentrations are relatively low in narrowed reaches

around Hog Point.  Kepone content generally diminishes seaward

from Burwell Bay to Hampton Roads where concentrations are less

than 0.010 ppm.  Twelve sediment samples from lower Chesapeake

Bay in September 1977 all had concentrations less than 0.010 ppm.

Distribution of Kepone at Depth in Sediments.  Contamination of

bed sediments in zones of natural fill (undredged) extends to

about 40 cm below the bed surface (Figure 4).  Greatest contam-
                                    v
ination, often exceeding 0.50 ppm, occurs at depths of 10 to

20 cm below the surface.  However, in cores from shoals in the
                                                        s*
shipping channel where sedimentation is locally fast (i.e., 30a),

concentrations increase downward to a depth of 60 to 80 cm.  This

trend reflects the diminished supply of kepone-rich 'sediment with




                                - 375 -
-------
  KEPONE  IN  SEDIMENT
         CORES
                            DEPTH  KEPONE*
                               o_  o' 01 0-3 ppm
        ppm
    0 O.I 0.?. Q3
   20
   cm
   40


   GD
SPOIL
                                      NATURAL
                                        FILL
                                                 CHANNEL
                                                   FILL

                                                 UNDREDGED
                   60*
Figure 4.  Depth distribution of kepone in cores from selected sites
                               - 376 -
-------
time since the Summer of 1975.  Kepone content of old dredged



material decreases slightly with depth (i.e., cores 41a, 30b,



1.9-7.5).  The depth trend results from mixing of sediment dur-



ing dredging and disposal.  The contaminated sediment is most



likely mixed and "diluted" by uncontaminated sediment and thus



reduces the overall concentration.



     A few samples from the Jamestown-Daneing Point reach collected



in May 1967 showed dectable amounts of kepone (.038 and .018 ppm).



Although the content is law, the samples suggest that the life



span of kepone in the sediments is at least 10 years.



State of depone in Sediments.  The concentrations of kepone are



orders of magnitude greater in the bed sediments than dissolved in



estuary water.  An indication of the state of kepone storage in



the sediments is gained by examining its relation to percent clay



contentj mean particle size and organic content.



     Finer-grained sediments are generally the most contaminated.



A plot of mean grain size versus kepone concentrations throughout



the'estuary (Figure 5a) shows a great deal of scatter.  Likewise



a plot of percent clay content versus kepone concentrations varies



widely (Figure 5b).  Part of the scatter results from the great



variation in textural types throughout the estuary whereas kepone



content partly varies in relation to its source.  When kepone



content of samples from a single reach of the estuary is considered,



however,  there is a trend for higher kepone content in the fine-



grained sediment with high clay content.
                             - 377 -
-------
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     There is a distinct trend of increasing kepone content with



increasing organic content.  As shown in Figure 5c, organic-rich



sediments have higher kepone content than sediments with low



organic content.  As expected, samples landward from the kepone



source or from zones of scour, display wide scatter.  The trend



indicates kepone prefers organic matter, either adsorbed on



detrital particles or ingested when the organic matter was pro-




duced.  As organic matter slowly decomposes in the sediment,




there is an opportunity for kepone to escape into interstitial



or overlying water.






 6.  Discussion.



Sedimentary Sinks for Kepone.  The James Estuary is an environ-



ment where much river-borne sediment accumulates.  Zones of



active deposition may be expected to be areas of relatively high



sediment contamination.  On the other hand, zones where the bed



is scoured into older sediment or zones where river-borne sedi-



ments are by-passed, are zones of relatively low contamination.



Inasmuch as sedimentary processes are relatively slow, deposi-



tion sites are indicators of long-term processes.  They are an



end product of short-term variations induced by local wave and



current transport.



     Kepone contamination is generally greatest in sites of active



sedimentation:  (1) the Jamestown-Dancing Point reach which is



also the site of the turbidity maximum, (2) Burwell Bay, and



(3) tributary creek mouths.  Zones of sedimentation have been





                              - 379 -
-------
                                                                     o
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-  380  -
-------
delineated in a former study (Nichols, 1972) (Figure 6) from

differences in water depths over 35 and 70 years.  The rates of

sedimentation within the zones probably change with time but

the sites of deposition persist.

     Kepone concentrations are locally high off the mouth of

Bailey's Creek, the kepone source.  However, the rr.ain distribu-

tion does not display decreasing concentrations with distance

away from the source.  Instead, the main sink is in the middle

estuary, the zone of the turbidity maximum where suspended

sediments are trapped and deposited.  Sediments in this zone

are finer-grained than elsewhere, less than 8/1 mean size.  Clay

content in this zone is also higher than elsewhere in the

estuary.

Routes of Transport.  From the sedimentation patterns, kepone

distributions and existing hydraulic knowledge of the James, it

is possible to sketch the probable route of kepone-sediment

transport.  Both the source of kepone and the major source of

suspended sediment come from the same direction, landward or

upstream of the estuary.  Since the influx of sediment from

Bailey's Creek is very small in proportion to the influx of
                                    N.
sediment from the main river, it is probable the kepone was

mainly introduced in the dissolved form and bound to suspended

sediment from the main river.  Since the estuary is fresh above

Jamestown most of the year, net transport from Hopewell to

Jamestown is directed seaward.  When suspended sediment reaches



                            - 381 -
-------
the Jamestown area, transport is slowed down because net velocity


approaches zero in the null zone at the salt intrusion head.   The


null zone acts as a dynamic barrier, that restricts seaward trans-


port of river-borne suspended sediment carried near the bottom.


Only sediment carried near the surface is transported farther seaward


through the upper layer.  If this sediment settles downward,  it


is carried back upstream to the null zone by landward density


currents through the lower estuarine layer.   However,  sediment


carried over the shoals may escape the estuary through the upper


layer especially during floods like Agnes.  Nonetheless, the bulk


of the sediment load is trapped landward of the null zone.  As


a tracer of sediment, kepone supports this fact.  Most kepone


concentrations are located in or above the null zone and they


persist with time, both over the short-term, 8 months of sampling,


and over the long-term as demonstrated from the distributions at


depth in cores.  The data indicate that it will take a long time,


many years, to reduce levels of kepone in the sediment by natural


processes of decay and dispersal.  Part of the kepone will be


buried by "new" sediment but the most significant reduction will


come by "dilution" with uncontaminated sediment introduced during
                                        V

freshets and floods.  This trend has already started on the floor


of the shipping channel where sedimentation is  locally fast.
                             - 382 -
-------
              KKl'ONK WATKK-SKDIMKNT KI.UTIUATKS






     Many pollutants have an affinity to sediments which is



by tha surface charges on particles.  This is particularly true for



some of the trace metals - such as zinc - with the clay mineral



portion of the sediments.  The magnitudes of the surface charges are



affected by pH and salinity (Parks, 1967).  Therefore, it was necessary



to determine if Kepone behaved in a similar manner because, in the



James River, both the estuarine and the tidal fresh water portions



with their wide ranges of pH and salinity were contaminated by the



pesticide.  As well the distribution of Kepone in the bottom sediments



of the James show a marked increase in that portion usually in the



vicinity of the freshwater - saltwater interface.  At this boundary



the waters change from fresh, (salinity ^O.y') to saline, (salinities



0.5;'' to 20 - 25^).  Also in this region the pH of the water increases



from near 7 to 8 due to the buffering capacity of seawater.  With



these abrupt changes in pH and salinity coinciding with the change



in Kepone concentration, it appeared possible that fresh water



sediments, highly contaminated with the pesticide, were being "ex-



tracted" by estuarine waters as they traversed this boundary pro-



gressing seaward or that Kepone in solution was not adsorbed by



sediments in saline waters.  Therefore, experiments were conducted



in the laboratory to determine the extractibility of sediment-Kepone



by waters with varying ranges of salinity and pH.



     The experimental design included two phases.  The first phase



was to determine the accuracy and precision of the analysis of water



for dissolved Kepone and the second phase was to determine the amount



of Kepone removed from contaminated freshwater sediments by waters



with pH's ranging from 6 to 9 and salinities of <0.5^ and 2Q&.



                               - 383 -
-------
These range;; of pH's and salinities bracket those found in the
James River.
Phase I, Water-Kepone Analysis
     The method utilized for the Kepone-water extraction was one
developed by The Environmental Protection Agency, Research Triangle
Park (1975).  It involves liquid"extraction using benzene as the
organic solvent.  The extractions are carried out in seperatory
funnels with 3 successive treatments of the same water with benzene
at a ratio of 1:10 benzene to water.  The extracts are combined and
then dried by passing them through anhydrous sodium sulfate.  The
combined extracts are then analyzed by electron capture gas chroma-
tography.
     To check the efficiency and accuracy of the procedure, Kepone
free water, (obtained either from Kepone noncontaminated estuaries
such as the York or from laboratory deionized-double distilled
stocks), was spiked with known amounts of Kepone, extracted and
analyzed (Table I).
Phase II,  Water Extraction of Kepone From Sediments.
     The experimental design for this phase involved subjecting
Kepone contaminated sediments from the James River, obtained from
the fresh water portion, near Hopewell, to waters with varying pH's
and salinities.  The salinities were either fresh, (0.06/*), obtained
from the James River or saline, (19.5^), gotten from the mouth of
the York River at the Virginia Institute of Marine Science's facility.
The pH's of these waters were adjusted to the desired levels by
addition of either reagent grades of hydrochloric acid or sodium
hydroxide.
     After Che desired pH and salinity were achieved, a portion of
wet sediment (100 g   ) was placed in a flask and the water (250 ml) was
                                 - 384 -
-------
added and the mixture was agitated with a Wrist-Action Shaker for

1 hr.  Following this the sediments ware separated by centrifugation

and the supernatant water was extracted for dissolved Kepone by the

method previously described in the Phase I section of this report.

     In all, 36 separate extraction were analyzed and the resulting

water Kepons concentrations were comp.ared to that in the exposed
                                „      »
sediments.  The comparisons are reported as the percent removed by

a water of a given pH and salinity in Table II.

Discussion:

     The data from Phase I clearly show that the Benzene method of

extracting Kepone from water yields approximately 85^ or better of

the amount of the pesticide from solutions spiked at 1 ppb to 10 ppb.

However, at concentrations below 1 ppb the efficiency drops greatly •

for instance, 64^ yield at 0.5 ppb.  These yields can be used to

judge the accuracy obtained for Kepone analyses of water by this

method.  The precision estimates can be seen from the standard devia-

tions which show + 14,"'- or better for spiked solutions of 1 to 10 ppb,

The precision of the method for concentrations of 0.5 ppb are in the

same range which suggests that a portion of the "spike" may be

sorbed to the walls of the glassware or lost by some other means.

     Attempts were made to try solvents other than benzene, for

extraction, (ethyl acetate - toluene, methylene chloride) but with

the similar results - dissolved Kepone at concentrations less than

1 ppb may be 10Q'> in error.

     Since only at the 10 ppb Kepone concentration were the effect

varying salinities on the analysis compared, it is risky to judge

salinity effects on the method.  Evenso, there is no obvious effect

using natural waters of 0.06 and 19.5/a.
                                  - 385 -
-------
     The extraction experiments,  the results of which are given

in  Table II and Figure I, show that there is no apparent affect

of either salinity or pH, within the ranges used which approximate

those found in the James River, on the extractibility of Kepone

from sediments by water.  It must be..kept in mind, however, that
                                „     *
the amounts of Kepone extracted were in the tenths of ppb range.

Since the analytical methodology is less than ideal, at these con-

centrations some differences could go undetected.  Figure I shows

that all results are within 2 standard errors of each other which

implies no difference at the 95W  confidence interval.

     The data indicate that, if the analyses are correct, the

partitioning coefficient of Kepone from sediment to water is approx-

imately 6 x 10" , irrespective of natural ranges of pH and salinity.

It follows then, that the relatively high concentrations of Kepone

at the fresh water-salt water interface and upstream are likely due

to the turbidity maximum (mentioned in the sediment: section) rather

than chemical factors such as partitioning.
                                - 386 -
-------
                          References


Environmental Protection Agency, 1975, Preliminary Report on
     Kepone levels from Hopewell, Va area.  Briefing at Research
     Triangle Park, North Carolina

Parks, G. A., 1967. Aqueous Surface Chemistry of Oxides and Complex
     Oxide Minerals:  Equilibrium Concepts  in Natural Water Systems,
     p. 121-160.  In Gould, F. (Ed),-Advances in Chemistry, Series
     67.  American Chemical Society Publications.
                               - 387 -
-------
                TABLE I

Extraction Efficiencies of Kepone from
      Water by the Benzene Method
Salinity
0%, De ionized H00
' M 2
ii
ii
n
M
M
M
M
M
it
M '
it
n
ii
it
M
II
II
II
II
II
II
II
II
II
II
0.06% J
-------
TABLE I  (continued)
                            Adjusted          Spiked

         Salinity	pH	Kepone Concentration	% Recovery
   19.5% York R. H20         8.0             lOppb                    74/;

                                                                      85;
                                                                      73;;
II                  II                II


II                  II                II


II                  II               -. M
                                                                      99:
            II                  II                II                      I/."/

                                                                     lor;

                                                                      99%
                                       - 389 -
-------
        Salinity
        TABLE I

        Summary


Adjusted          Spiked            Average yield
   pH	Kepone Concentration   And Standard dcv
  Deionized + Distilled
 0.067o James River H20

19.57. York River H 0
  7.0
  7.0

  8.0
 lOppb

  5ppb

  Ippb

O.Sppb

 lOppb

 lOppb
98 +  2%

89 +  7%

85 + 14%

64 + 11%

85 +  8%

87 + 137.
                                    - 390 -
-------
                             Elutriate Results
SnHnlty

 0.06;",
  It

  II

  II

  II

  II

  II

  II

  II

  M
6.0
(Sediment + ppm  Kopone)
             ;' Kc:nov(.'(l
                            0.04".
                            0.06".
              0.11
              0.11
              0.09
              0.12
              '0.01
              0.07
              0.06
              0.06
              0.11
             7.0
              M

              II

              II

              11

              II

              It

              II
                                   ± -ill

                               STD. ERROR - 0.01
                               0.05 ± 0.01.'- of  total  Kepone in
                               sediment recovered  at  a  pit 6.0 -
                             .. 0.06
                               0.03 + 0.04' of  total  7enoru' v
                               scdi~cp.t recovered  at  a oil 7.0
                               + 0.06

                               STANDARD ERROR 0.01
  II

  It

  II
8.0
              it
                            0.06
                            0.09
                            0.09
                               0.08 +  .02" of total  Kepone in
                               sediment recovered  at pH 8.0 +
                               0.06'

                               STANDARD ERROR 0.01
  II

  II
9.0
 M
                            0.05
                            0.06
                               0.06 + 0.01'' of  total  Kepone in
                               sediment recovered  at  pH 9.0 +
                               0.06'

                               STANDARD ERROR 0.005
19.5;?*
  n
  it
5.0


6.0
                            0.03
              0.04
              0.06
              0.03
                               0.03 +? ,<-
                                            0.04 + 0.02"  of total Kepone in
                                            sediment  recovered at pH 6 +
                                            19.5'

                                            STANDARD  ERROR 0.009
  n
  n
             7.0
              0.02
              0.07
              0.04
                                            STANDARD  ERROR 0.015
                                            0.04 +  0.03..'  of total Kepone in
                                            sediment  recovered at pH 7 & 19.5
                                    - 391 -
-------
II
II
II
II

II
II
II
II
II
II
8.0
 M

 II

 II

 M

 II

 ir
 0.09
 0.06
 0.05
 0.06
-------
%  REMOVED
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    - 393 -
-------
        UlTAKK OK  KKl'ONK  FROM  SUSIT.NDK!)  SKI) IMKNTS
              BY OYSTERS,  KANf. 1A  AND  MACO.MA
                        Introduction


          Laboratory studies on the uptake of Kepone from

sediments in suspension by bottom-dwelling organisms were

undertaken by the Virginia Institute of Marine Science at

Gloucester Point, Virginia on December 1, 1976.  The first

two months were spe.it in acquisition and preparation of

laboratory equipment and space for the experiments.

          In the period of time since then, three series of

laboratory experiments were conducted with three species of

bivalves.  Eight experiments were completed with the oyster

Crassostrea virginica, five with the clam Rangia cuneata and

one with the clam Macoma balthica.  Most of these experiments

involved exposure of the animals to contaminated sediments

in suspension.  In -;wo of them, however, the animals were

placed in a bed of contaminated sediments with uncontaminated

river water flowing over them.

          This report presents the results of three series

of experiments followed by a discussion.

                                                       •
                    Materials and Methods


Apparatus

          A diagram of the basic arrangement of the apparatus

used to conduct the;>e experiments is shown on Figure 1.  The

units labelled A through D were used only during the first

series of experiments when ambient river water temperature

was below 10 C most of the time.  York River water was piped
                             - 394 -
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into a constantly-overflowing box (A) from which it was
pumped through heat exchangers (C) into a rectangular cas-
cading trough (D).   The latter served to allow bubbles
created by the escape of dissolved gases to dissipate before
reaching the animal trays.  This section of the system '.-.'as
not used in the lasi; two series of experiments when river
water temperatures were above 10 C.  Then, York River water
was piped directly :>nto a rectangular trough  (E) which was
suspended from the ceiling directly above the wet table
that held the experimental trays.  Water depth in the trough
was maintained at 20 cm by a drain standpipe of that height.
          Water to supply the experimental trays was siphoned
out of trough E with plastic tubing.  In the  first series
of experiments water flow rates were controlled by inserting
glass flowmeters (F,\ in the tubing siphons ahead of the
mixing chambers  (I),  In the last two series of experiments
the flowmeters were omitted.  Instead, flows were regulated
by the bore size of the plastic tubing used for siphons.
This eliminated constrictions in the tubing caused by adjust-
able clamps which enhanced flow interruptions due to clogging.
Siphons were cleaned daily and flow measurements made before
and after the siphons were cleaned.
          Water from the siphons entered a rectangular mixing
chamber made of acrylic plastic  (I), 25 cm in length, 16 cm
in width and 14 cm in height, through a smaller chamber  (2 cm
long, 3.5 cm wide and 14 cm high).  The smaller chamber was
connected to the larger one by a circular opening with a 2 cm
                              - 395 -
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diameter.  Contaminated sediment suspensions also entered
the mixing chamber through the same small chamber.  Stock
suspensions were kept well mixed in flasks  (H)  by magnetic
stirrers (J).   They were metered into the mixing chamber at

a constant rate by [peristaltic pumps (G) .
          River water and sediment suspensions were mixed
in the mixing chamber by magnetic stirrers.  Observation
showed that the mixing was complete before  the mixture flowed
cut of the mixing c.iamber.  Sedimentation in the chamber
was negligible.  The diluted sediment suspensions flowed into
the Experimental trays  (K) through a standpipe located at the
end opposite to the one through which water and sediments
entered the chamber.  The system set up was the same for
trays holding control animals except for elimination of
components G and H.
          In experiments with the clam  Rangia cuneata, York
River water salinit/ was reduced to between 5 and 6 /oo by
addition of fresh ground water pumped from  a shallow well.
A second rectangular trough  (P) was suspended below the one
receiving York River water  (E).  York River water was  siphoned
 (Q) from trough E into  trough P.  Fresh water was also piped
into a cascading trough similar to D to eliminate gas  bubbles
generated, by the change in pressure the ground water was
subjected to before it  flowed  into trough P.  Water of the
resulting lower salinity was then siphoned  into the -trays
holding  Rangia clams following the same system setup  labelled

F through K in Figure 1.
                             - 396 -
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          Figure 2 shows a partial view or the apparatus

used in the series of experiments.

          A system of sediment traps was usea to insure

that no contaminated sediments from our experiments escaped

into the floor drain which emptied into the York River.  The

first component was the wet table on which the experimental

trays were set (L in Figure 1).  A standpipe about 2.5 cm

high inserted in th<; drain hole of the wet table converted

the table into a sediment trap.  A plastic circular tank (50

cm high and 30 cm in diameter) received water from the wet

table through a pipe reaching close to the bottom.  The

tank overflowed near its top into a series of three rectangular

boxes (114 cm long and 25 cm wide), each with a 15 cm high

standpipe overflow.  The third box overflowed into the floor

drain.  The sediments and other excess solids obtained in

the experiments were collected in carboys for disposal.



Experimental Trays

          Two types of trays were used to hold experimental

animals.  In most experiments, a  tray made of acrylic plastic

49 cm long, 26 cm wide, and 8 cm  high, were used.  The over-

flow end was 6 cm high and that also was  the depth of the

water in the tray.  This tray was not compartmentalized and

the animals laid directly on the  bottom  (Figure 3).

          A larger  acrylic plastic tray,  81 cm long, 54 cm

wide and 8 cm deep was used in the third  series of experiments

to hold oysters whose biodeposits were collected.  A baffle
  i
                             ^ 397 -
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at the overflow end of the tray maintained water level at
a depth of 6.5 cm.  These trays were divided into 25 compart-
ments by plastic strips 2.5 cm high.  Each compartment held
cne oyster.  The compartments "facilitated separation and
collection of biodeposits.

Eiodeposits
          Biodeposibs produced by oysters receiving contaminated
sediments in suspension in the large trays were collected
every day with a bulb pipette.  The aggregates collected at
the end of each weekly period were then analyzed for Kepone.
Every tiir.e biodeposits were collected, sediments settling
out by gravity in the same tray were also collected and the
weekly accumulation also analyzed for Kepone contents.  Each
day, after biodeposits and sediments had been collected,
every compartment was cleaned of any remaining sediments.

Animals Buried In Mad
          A modification to the manner usually used to expose
ctnimals to contaminated sediments, i.e., by flowing sediment
suspensicns over thsm, was introduced in the third series
of experiments.  Oysters and  Rangia were buried partially
and fully, respectively, in beds of contaminated sediments
held in the smaller of the trays described above (Figure 4).
The sediment bed was  4 to 5 cm deep.  It was made up. of
unsieved sediments from the same batch used in simultaneous
experiments with flowing suspended sediments.
                              T- 398 -
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          Oysters were pressed into the sediments at about
a 30° ancle.   Up to one-third of their height was below the
sediment surface level.  The valve area over the gills pro-
truded above the sediment surface. 'Rangia were pressed into
the mud so that almost the whole animal was below the sedi-
ment surface level.  Within several hours they had buried
themselves fully into the sediment so that only their siphons
showed.  Water flowing over the animals and the sediment
bed had no sediments added to it and was approximately two
to three cm deep.


Source of Experimental Animals
          The animals used were obtained from areas  to be
free of Kepone .  R.ingia and Macoma were collected  from the
Eappahannock River and oysters came from the Piankatank
River.  All three species were acclimated to the experimental
temperatures and salinities under  flowing-water conditions
at least one week p;:ior to use.  Analysis before start of
each experiment showed them to be  free of contamination
with Kepone .


Preparation of Sediment Suspension
          Figure 5 presents a flow chart outline of  the steps
taken  in preparation of KeponeR contaminated sediment  suspensions,
All contaminated sediments were collected with a sediment
grab sampler at Jordan Point, in  the  James  River at  Hopewell
and represented the top 6 cm of the bottom.  They were trans-
                             -. 399 -
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ported to the laboratory in 2 or 3 large plastic bags each




containing about 2C kg of material.  The contents of each




bag was mixed and transferred to smaller bags in fractions




of approximately 5CO ml in volume. - The smaller bags were




stored in a freezer until needed.  Only sediments collected




on the same date were used in any one series of experiments.




          When needed, a bag of sediments was thawed, mixed




with well water and shaken mechanically in flasks for 12




hours or more.  The sediments were then wet-sieved through




a 63 u and the resulting suspension diluted up to 7000 ml




with well water.  This volume was labelled as stock suspension




and given an identification number.  It was maintained in




suspension by continuous agitation with a magnetic stirrer




a.nd bar.  Subsequently, to insure homogeneity in dosage,




it was divided into measured portions by alternately siphoning




a small volume into each of six containers and repeating the




cycle until each container had been filled to the desired




volume.




          The samples in two of the containers, with volumes




of approximately 403 and 200 ml, were used to determine  the




concentration of Kepone in the suspension and the dry weight




per unit volume of  the sediments in the suspension, respectively.




The suspension in  the other  four containers, usually with




volumes of 1200 and 1600 ml, was the material to be introduced




into the trays holding experimental animals.  The suspensions




in the  four containers were diluted in a ratio of 1:4 and




pumped  into the mix.ing chambers.




                              - 400 -
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Sampling of Animals in Trays

          Samples of the animals were analyzed for Kepone

at the start of each experiment and at approximately weekly

intervals thereafter for the four-weeks duration of the

experiment.  Each sample consisted usually of three or four

animals and at times of up to eight individuals in the case

of oysters and Rangia.  In the case of Macoma the number

ranged between seven and fifteen.  The shell of each animal

was carefully scrubbed after removal from the tray.



Kepone Analysis

          Analysis of all samples from concentration of

Kepone were done by personnel of the Department of Ecology

and Pollution in their laboratories.  The method used was

soxhlet extraction, fluorosil cleanup and electron-capture

gas croir.atography.



Determination of Kopone Concentration in Sediments

          The concentration of Kepone in the diluted sediment

suspension  flowing over the experimental animals was deter-

mined by computation of the product of four  factors:


                    Kc =  (sc}  (kc)  (dl)  (
-------
          d,  = factor by which stock suspension was diluted
               prior to being pumped into nixing chambers.

          d  = factor by which the suspension being pumped
               into mixing chambers was diluted; determined
               by the flow rate at' which it was being pumped
               and the flow rate of York River water flowing
               simultaneously into the mixing chamber.

          The factor &2 was controlled in each experiment by

selection of peristaltic pump settings that would deliver

a desired flow rate of the sediment suspension into the mixing

chamber.  The flow of river water into the mixing chamber

was also adjusted t.o the desired rate.  Flow of river water

was maintained relatively constant while the flow rate of

contaminated sediments was adjusted so that trays would

receive sediment suspensions at different rates.

          Some trays received what was labelled as low

concentrations of sediment  (and, therefore, also of Kepone)

while ot.ners received medium and high concentrations.

Throughout an experiment t!    itio between low, mejdium and

high concentrations remained fairly constant even though

Kepone concentrations in stock suspensions were variable.

As a result, the concentrations labelled as low were always

significantly lower than those labelled medium or high.   The

separation of low concentrations  from medium and high ones

is the main distinction made between concentrations in this

report.                                     ,



Preparation of Pat:i  for Analysis

           In the course of  one series of experiments  between

30 and 40  different stock  suspensions  (500 ml bags) were  used.
                            - 402 -
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Sodi-T.ent concentration and Kopcne concentration varied  irc.r.
one stock suspension to another.  Consequently, the experi-
mental animals in any one tray were not being exposed to a
constant concentration of Kepone daring the time they were
held in the trays.  However, throughout the duration of an
experiment, the racio between low, medium and high concentrations
remained fairly constant.  As an aid in interpretation  of
results, a weighted mean hourly concentration was computed
for each of the weekly periods as the sum of the products
of the concentration in each stock suspension and the length
of time (in hours) that particular suspension was used,
divided by the total number of hours in the weekly period.
Included in these computations, were short intervals during
which, for a variety of reasons, no sediments were being
added to the water flowing over the animals.  These intervals
were usually few and anywhere from 15 min to 2 hour in
duration.   Also involved was a final interval of eight  to
nine hours at the end of a weekly period when the animals
only received river water to allow them to eliminate material
held in their digestive tract.
          Despite the mining done before the sediment sample
was divided into 500 ml fractions, differences in sediment
and Kepone concentrations from one stock to another were
sometimes large.  "hus, differences of significant magnitude
were encountered sometimes between the mean hourly concentrations
for the different weekly periods in one experiment.  Since
there was a high correlation between the concentration  of
                            - 403 -
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Kepone 111 oyster cr.cats and its concentration in the sod irr.cnts,

and to eliminate the effect of the variations between stock

suspensions, the values for oyster meats were normalized

by re-computation based on the mean- hourly concentration of

Kepone in the sediments over the approximately four-weeks

duration of experiment.  The new values represent the con-

centration of Kepor.e expected in oyster meats if the con-

centration in sediments was constant.  The normalized values

were computed usinc a proportional equation.

                          Results

     Fourteen uptaxe  experiments were  completed  between

February  and Augu
-------
medium and high, mean hourly concentrations ranged between

0.040 and 0.153 ppm.

     Mean hourly concentrations for the total duration of

exposure (one, two, three or four weeks) in experiments where

levels were classified as low ranged between 0.027 and 0.058 ppb

(Tables 4 and 5).  In experiments where levels were classified
                     \
as mediam or high the range of mean hourly concentration was

betx-;een 0.057 and 0.153 ppb.

     Results are presented separately for each of the three

bivalve species.  No data are presented for the Kepone concen-

tration in animals: examined before the start of each experiment

or for control animals because in every case they were under the

level of detectabllity of the analytical procedure.



Crassos trea virginica

     Figures 6-8 show the concentration of Kepone in oysters

examined at weekly intervals after exposure to contaminated

sediments in suspension in three series of experiments.  The

values in parentheses give the mean hourly concentration of

Kepone in the sediments for the weekly period that immediately

preceded removal for analysis of that particular sample of oysters

     Results of the first series of experiments showed a uniform

progression in the: concentration of Kepone in oysters with time

(Figure 6).  There was indication that an asymototic level had

been reached after two weeks.  There also was a clear separation

between the three lines which represented high, medium and low

concentrations in sediments.  A uniform progression was also

evident in the second series of experiments although the


                          - 405 -
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absolute; concentrations attained in oyster  meats  were  lower
than in the first series and there was no indication that an
asymptotic level had been reached (Figure 7).   In  the third
series there was neither a uniform progression nor suggestion
of an asymptotic level.
     The three sets of lines in Figures 6-8 did not appear
to share a common pattern.  However, they did show that the
higher concentrations in oyscer meats were associated with the
higher concentrations in the sediments and vice versa.   When
the values for Kepone concentration in oyster meats in the three
series of experiments (Tables 1-3) were grouped into three classes
according to selected concentration ranges it was  found that
the values for Kepone in sediments also separated  into three
fairly distinguishable groups with different means.  Eleven
sediment: values associated with concentrations in  oyster meats
between 0 and 0.10 ppm had a mean of 0.038 ppb (range:  0.020 -
O.C98 ppb).  Twelve values for concentration in sediment associ-
ated with concentrations in oyster meats between 0.101 and 0.199
had a mean of 0.058 ppb (range: 0.023 - 0.088 ppb).  Five values
for sediments associated with concentrations in oyster meats of
0.20 ppn or greater had a mean of 0.095 ppb (range:  0.070 - 0.113
ppb).
     A plot of concentration of Kepone in oyster meats as a
function of concentration in suspended sediments appears in
Figure 9.  Regression analysis showed a correlation between the
two sets of data (correlation coefficient = 0.781).
     Having obtained rhis correlation, the values   for concentration
in oyster meats were normalized on the basis of a constant, hourly
                             - 406 -
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concentration of Kepone in the sediments.  The mean hourly
concentration of Kepone in sediments for the whole duration
of each experiment  (approximately four x-Joeks) was chosen as
the normalization constant.  The computed means appear in Table 4.
     Plots of the normalized-value's for oyster meat concentrations
appear in Figure 10 and 11.  The marked dips in meat concentra-
tions after two and three weeks of exposure during the third
series of experiments have been eliminated in the normalized
curves.  The normalized curves suggest that an asymptotic level
is reached after the first week of exposure in that series.
     The curves for the first and second series were slightly
altered by the conversion but the original trends shown were not
appreciably changed.  The curves for the first series still
indicate an asymptotic plateau.  Curves for the second series,
on the ether hand,  still show a trend of increasing concentration
in oyster meats with time.  The high value seen for the third week
in the borken line  for the first period results from a relatively
high value in the meats in the original data while the correspond-
ing value in the suspended sediments was relatively low (medium
concentration, Table 1).
     There were significant differences in the temperatures at
which the three series of experiments with oysters were conducted
(Table 6).  In the  first series, York  River water had to be
heated to raise it  to desirable levels.  The minimum and maximum
daily temperatures recorded near the source of our river water
supply for each of  the weekly periods included in the experiment
were:   1st week, 3.2-7.6°C; 2nd week, 6.4-10.4°C; 3rd week,
9.0-12.8°C;  and 4th week,  10.0-12.0°C.  Water temperatures in the
                           - 407 -
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c'xoer i mental trays ranged between 14.0 and 2L.O°C during the
four weeks Included, with tho average being between 17 and 18 °C
for each of the weekly periods.
     The second and third series...of experiments were conducted at
anbient temperatures.  These ranged b^rce^:.. 18.3 and 25.7°C
during the four weeks of the second series with an average for
each week in the range of 20.9 to 23.5°C (Table 6).  Daring
the third series the overall range was 25.0 to 34.0°C with the
weekly average ranging between 26.6 and 29.6°C.
     During the first series of experiments, daily salinities
ranged between 17.5 and 22.1"- for th-2 four weeks, and the -weekly
average ranged from 18.4 to 20.4"'. (Table 6).  Daring the second
series, the corresponding salinity ranges were 16.2 - 20.3^ and
17.1-19.4/.  Likewise, the ranges of the corresponding averages for
the third series v;ere 20.2-23.6' and 20.6-23.1,''.
     One of the experiments in the third series involved weekly
aniiysis of Kepone concentration in the meats of oysters that had
been held partially buried in an undisturbed bed of contaminated
sediments.  York River water flowing over the sediment bed was
uncontaninated by Kepone.  The concentration of Kepone in the
sediments forming the bed averaged 1.77 ppm in two samples
analyzed before the oysters were introduced (Table 7).  A mixed
sample from the sama tray analyzed after the oysters were removed
showed a  concentration of 2.89 ppm.  A sample collected, from
the top one centimi'ter layer of the tray after the oysters were
removed had a Kepone concentration of 2.24 ppm.
     After on.? week  in the sediment bed the Kepone concentration
in two samples of oysters averaged 0.037 ppoi (Table 7).  The
-------
concentration  i.n oyster meats decreased gradually during the



next three veaks below the detectability level of the analytical




techniques, j^-e^, 0.02 ppm.



     Mean sizes of oysters used in the three experiments appear



in Table 9.  They ranged between"?, and 8 cm in height during the



first and third series of experiments and between 5 and 6 era in



the second series.



Oyster Biodeposits



     Oysters concentrated Kepone in their biodeposits to levels



thousands of times higher than those found in the suspended



sediments (Table 8).  The concentration factors for feces ranged




from 11,000 to 55,000.  In pseudofeces, the range was between



3,000 to 20,000.  The concentration in feces was always higher



than that in pseudofeces but the magnitude of the difference varied



considerably between the paired sampled compared.



     Concentration of Kepone in sediments that settled by gravity



in the tray compartments was usually slightly higher than those



in pseudofeces.  However, it was also significantly lower than



that in feces.



Ra ng 1a c un o a ta



     Five experiments were conducted with the wedge clam Rangia



cuneata during the second and third series of experiments.  In



four, animals were exposed to contaminated sediments in suspension



and In one they were buried in a bed of contaminated sediments.



     The results obtained for R-ingia during the second series




of experiments are almost identical to those obtained for oysters



during the same series (Table 2, Figures 12 and 7).  Most of the



actual values found at any one weekly interval were close and the




line trends are similar.
-------
     The data for R,'!:]^'^. in the thrid series of experirr.ents



were sonex>?hat different from those for oysters (Table 3, Figures



13 and 8).  Distribution of the weekly values for R_ang ia meats



tended i:o remain at approximately the same level after tha first



week wit:h a slight dip in the thir-d week samples.  The oyster



data showed a greater vertical displacement of the weekly values.



The data for both animals showed a fairly distinct separation



between the lines for low and high Kepone concentrations in the



sediments.



     Rangia buried in undisturbed contaminated sediments



accumulated Kepone to low levels (Table 7, Figure 13).  After  the



fir~t week high of 0.05 ppm there was a gradual decrease with



time to 0.03 ppm after four weeks.  Rangia receiving low concen-



tration;; of Kepone in suspension accumulated slightly more Kepone



than those buried in the sediments even though the latter had  a



Kepone concentration several thousand times greater  (2 ppm in  the



bed sedrlmants vs. 0.02 to 0.06 ppb in the water column).



     Water temperatures in the trays holding Rangia  during the



second <;eries of experiments were slightly lower than during  the



third series (Table 6).  The range during the second series was -



between 18 and 20°C and during the th ird series it was between



20 and 22°C.  There was substantially no difference  in water



salinities during the two series.



     Mean sizes and Rangia used in these experiments appear in



Table 10.  They ranged between 4 and 5 cm in height.



Macoma balthica



     A 'single experiment was conducted with the clam Ma coma



balthica during tha second series.  Tne Macoma were held  in the



                             r. 410. -
-------
same tray with oysters receiving sediments in suspension at a


high concentration of Kepone.  However, they were placed in the


tray one week later than the oysters and consequently, they


remained in the tray one week after all the oysters had been


removed.


     The M.icfr.TVi laid directly on the bottom of the tray and,


being fairly small (average height was between 1.4 and 1.7 cm;


Table 11) were in close contact with the contaminated sediments


that settled on the tray bottom.  Sediments settling to the


bottom of the experimental trays were removed every two or three


days .


     The Macoma accumulated Kepone at the fastest rate of the


three species studied to date.  After three weeks the concentra-


tion was 0.33 ppm (Figure 14).  During the fourch week there


was a slight drop to 0.30 ppm.


     Mean water temperatures in the trays holding Mncoma ranged


between 21 and 24°C during the foar weekly periods (Table 6).


Meaa water salinities ranged between 17 aid 23/<.


     Mean sizes of Macoma used in these experiments appear in

Table 11.  Th?y ranged around 1.5 cm in height.


Condition ini?x.   Measurements of the meat quality of samples of


the experimental animals showed no significant differences between


those analyzed at the start of the experiments and those analysed


after approximately four weeks in the experimental trays.


                       Discussion


     The bivalves Crassostroa virginica, Rangla cuncata and


Macoma balthica concentrated Kepone from suspended sediments by


factors ranging between 1000 and 3000 over that in the water


column.
                           - 411 -
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There was little difference in the results obtained for Crass -



ostrea and R^ng_ia_.  Maccma, however,  accumulated Keponc in greater



concentrations than the other two species.



     Cras ^o^ tiro a and Ring la showed similar trends in uptake of



Kepone from suspension.   This showed that the two species have



similar feeding habits.   As suspension feeders, they are reacting




in a similar manner to the presence of the sediments in suspension.



Such a similarity was reinforced by the experiments in which



individuals of the two species were buried partly or fully in a



bed of contaminated sediments.  Neither one of the two species



accumulated much Kepone under those circumstances.  Water flo-/



over the sediment beds was relatively sloxs? and the water-sediment



in.erface was not disturbed.   Therefore, very little of the




sediment was re-suspended.  Concentrations in ^.-12iiil w-re slightly



higher than those for oysters and if there is any significance



to the difference It may be an inlicatio.-, that by being fully




buried with its siphon close to the sediment surface, Ring la



ha I access to sediments not available to oysters.



     The data for oysters  showed  i strong correlation between



the mean hourly concentration of Kepone  in suspended sediments,



computed for weekly intervals, and the mean concentration in



oyster samples exposed to  those sediments during the same weekly



period.  As illustrated in Figures 6-8, usually the Kepone in




oyster meats decreased or  increased from one week to the next



following a decrease or increase in Iv.'pone in  the sediments during



the intervening week.  The validity of such a correlation is  further



reinforced by the similarity between the patterns of the curve



for low and high  sediment  concentrations in each of the three




series of experiments.
-------
     A weaker correlation  (0.614) was also found in the data




 for Rg-i.gia. Furthar collection of data for Macorna will be



 necessary before it can ba determined if the relationship holds




 for that species.



     This correlation  indicates th-at, at tha temperatures included,



 oysters and possibly other bivalves such as Rangia and Macomi



 depurate themselves of Kepone continuously at the same time that



 they ingest and accumulate it.  Therefore, in order for the Kepone




 level to remain at a high  level, the Kepone concentration in



 suspension will also have  to remain at a correspondingly high




 level.



     Consequently, disturbance of river bottoms contaminated with




 Kepone by natural processes or other processes initiated by man,




 which would result in  an increase in the suspended sediment load,



 appear to be capable of causing a  sharp increase in the levels




 of Kepone in individuals of bivalve populations within reach of the



 increased load.  On the other hand, it would appear that such an



 increase in Kepone in  the affected animals would also decrease



 sharply once tha disturbance is terminated.



     It is difficult to evaluate with the data obtained to date



 the influence of temperature on the uptake and depuration of



 Kepone by oysters and  R-mgia.  More data are required to establish



 that.



     Further studies are planned to investigate this relationship



between Kepone in sediments and in bivalves.  The effect of con-



centrations in tb.2 sediments higher than those tested so far will



be considered.  The effect of higher water flows capable of






                            - 413 -
-------
causing suspension of surface sediments in a bed holding buried
animals vilI also be studied.  Experiments that include combina-
tions of contamination and depuration of bivalves will also be
condue ted.
     The levels of Kepone flowing Over animals in experimental
trays hr.ve been fairly low - never higher than 0.15 ppb in the
water column - in the experiments conducted so far.  This has
been dictated by restrictions in the capability of our system
and personnel to -maintain larger quantities of sediments in stock
suspensions and flowing over the animals around the clock for
four weeks.  Changes required to achieve higher sediment concentra-
tions will be implemented in the forthcoming series of experiments.
     The: data indicate that a leveling in the concentration of
Kepone in oysters and Rangia occurs  after the first week of
exposure.  This was seen best in the curves obtained by normali-
zation of the data using as a constant tha mean hourly concentra-
tion of Kepone in the sediments for the duration of each experiment.
Since no animal samples were analyzed for a period shorter than
one wee!-: it is quite possible that the leveling may occur  sooner
than one; week.  Either way, this is another Indication of the
efficiency of these bivalves to depurate themselves of Kepone
since it: is evidently a balance between uptake and depuration that
is responsible for the leveling off in the curves.
     Analysis of oyster biodeposits indicated that: Kepone is
concentrated in feces to levels many thousand times higher than
it is present in the water column.  These observations re-emphasize
the importance of the effect biodapositicn can have on the
physico-chemical characteristics of sediments.  At tha same time
                              -  414 -
-------
oysters rU'C'uniul ali' Keponc  In  their tissues  to  levels up  to

3000 tim-?s that in the water  column, they are  also  re-depositing

high concentrations of the chemical on  the  bottom.  This re-

deposition is being done in the form of material  less  likely

to be resuspended because of  its nature as  an  aggregate.

     Kepone concentration in  oyster pseudofeces was not much

different than that found in  sediments  that settled by gravity

onto the tray bottom.  Therefore, there appears to  be  no indica-

tion that pseudofeces contribute to the deposition  of  Kepone-rich

sediments any more than natural sedimentation  would.   However,

pseudofeces form an aggregate which like feces may  also  resist

re-: ,isr>e:ns ion to a greater extent than  naturally-settling

sediments.

     There is no way to establish to what extent  sediments

settling by gravity in experimental travs are  included in the
       •J  *•  O     ./      r               -•

samples of feces and pseudofeces collected.  However,  the concen-

trations recorded for feces are so much greater than in  the

natural sediments and the bulk of the feces was so  obviously

greater :han the fine blanket of sediments  on  the bottom of the

tray,  th.it it can be safely infered that their contribution to

:he values recorded for feces are minimal.



                    Literature Cited

Haven,  D.  S.  19jO.  Seasonal cycle of condition index of oysters
     in :he York and Rappahannock  Rivers.   Proc. Nat'1 Shellfish
     Assoc.  54: 42-65.
                                - 415 -
-------
oysters accumulate Keponc in their tissues Co levels up to

3000 tirr.es that in the water column, they are also re-depositir.g

high concentrations of the chemical on the bottom.  This re-

deposition is being done in the form of material less likely

to be resuspended because of its nature as an aggregate.

     Keponc concentration in oyster pseudofeces was not much

different than that found in sediments that settled by gravity

onto the tray bottom.  Therefore, there aopears to be no indica-

tion that pseudofeces contribute to the deposition of Kepone-rich

sediments any more than natural sedimentation would.  However,

pseudofeces form an aggregate which like feces may also resist

re-~ ispension to a greater extent than naturally-settling

sediments.

     There is no way to establish to what extent sediments

settling by gravity in experimental trays are included  in the

samples of feces and pseudofeces collected.  However, the concen-

trations recorded for feces are so much greater than in the

natural 'sediments and the bulk of the feces was so obviously

greater :!i.in the fine blanket of sediments on the bottom of the

tray, that it can be safely infered that their contribution to

the values recorded  for feces are minimal.



                    L i t o ra I u ri- C. i t p d

Haven, D. S. 1960. Seasonal cycle of condition index of oysters
     in ;he York and Ranpaliannock  Rivers.  Proc. Nat' 1 Shellfish
     Assoc. 54: 42-65.
                               - 416 -
-------
   Table 1.  Concentration of Kopone
             meats of oysters during
             iods in first series of
             24 February - 27 March,
                          in sediments and in the
                          successivc exposure per-
                          Kepone uptake experiments
                          1977
Exposure
 Period
 ;\To.
days
Sediments
Range
(Ppb)
Hourly
Mean
Meats
Fie an
(ppm)
Concentration
   Factor
Low Sediment Concentration
1
2
3
4
6.9
14.8
2L.S
29 . 2
0.014
0.014
0.003
0.015
- 0.039
- 0.06&
- 0.045
- 0.046
                                     0.027
                                     0.037
                                     0.023
                                     0.033
                                  0.086
                                  0.125
                                  0.135
                                  0.113
            3185
            3289
            5625
            3228
Medium Sediment Concentration
1
2
3
4
6.9
14 . 8
2L.8
29.2
0.027
0.027
0.006
0.029
- 0.083
- 0.142
- 0.091
- 0.092
                                     0.057
                                     0.073
                                     0.045
                                     0.067
                                  0.130
                                  0.160
                                  0.185
                                  0.133
            2281
            2078
            3854
            1900
High Sediment: Concentration
1
2
3
4
6.9
14.8
2L.8
29.2
0.040 -
0.054 -
0.008 -
0.044 -
0.197
0.197
0.133
0.137
                                     0.082
                                     0.104
                                     0.070
                                     0.098
                                  0.185
                                  0.250
                                  0.210
                                  0.257
            2256
            2294
            2838
            2495
            ^-Short period of time when no contaminated sediments
             were being added to the water flowing over the animals
             (i.e., sediment concentration = 0) are not included
             in range.  However, they were used in computing  the
             mean.  This includes the final 8-9 hours when animals
             were allowed to flush out sediments in their digestive
             tract prior to removal for analysis.
                                    - 417 -
-------
Table 2.  Concentration of Kepone in sediments nnd in animal
          meats during successive exposure n.-riods in second
          series of Kepone uptake experiments.  13 May - 19
          June, 1977.
Exposure
Period
Lo'rf Cone
Oysters :
1
2
3
4
Rangia:
1
2
3
4
Ko.
Days
entration

7.3
14.8
22.0
29.0

7.3
14.8
22.0
29.0

0.024
0.024
0.017
0.028

0.024
0.024
0.016
0.028
Sediments
Range

- 0.0781
- 0.058
- 0.040
- 0.055

- 0.077
- 0.057
- 0.039
- 0.054
(ppb)
Hourry
mean

0.042
0.035
0.026
0.038

0.039
0.034
0.025
0.037
                                                      Concentration
                                                        Factor
High Concentration

Oysters:
1
2
3
4
7.2
14.7
21.9
28.9
0.054
0.058
0.040
0.068
- 0.178
- 0.139
- 0.095
- 0.132
0.098
0.086
0.063
0.093
Rancia:
1
2
3
4
7.2
14.7
21.9
28.9
0.057
0.061
0.043
0.071
- 0.188
- 0.147
- 0.100
- 0.140
0.104
0.091
O.G&7
0.098
Macorna:
1
2
3
4
7.5
14.7
21.7
29.0
0.058
0.040
0.068
0.095
- 0.139
- 0.095
- 0.132
- 0.131
O.C86
0.063
0.093
0.098
                                               0.039
                                               0.058
                                               0.064
                                               0.096
                                               0.025
                                               0.050
                                               0.048
                                               0.083
                                               0.09
                                               0.16
                                               0.11
                                               0.23
                                               0.05
                                               0.14
                                               0.11
                                               0.22
                                               0.13
                                               0.19
                                               0.33
                                               0.30
 931
1667
2424
2526
 641
1453
1912
2237
 905
1860
1732
2484
 521
1545
1644
2254
1512
299°
3564
3067
             "Short periods of time when no contaminated sediments
             were being added to the water flowing over the animals
             (i.e., sediment concentration = 0 are not included in
             range.  However, they were used in computing the mean.
             This includes the final 8-9 hours when arrivals were
             allowed to flush out sediments in their digestive tracts
             prior to removal for analysis.
                                 - 418 -
-------
    Table 3. Concentration of Kepone in sediments and in the moats
             of oysters and R_OJ12ii during successive exposure periods
             in third series of Kepone uptake experiments.  8 July -
             9 August, 1977.
 Exposure   No.
  Period   Days
                	Sediments (ppb)
               T\ange
              Hourly
              ..mean
         Meats
         Mean
         (norn)
                         Concentration
                           Factor
 Low Sediment Concentration
Oysters:

  1
  2
  3
  4

Rangia:

  I
  2
  3
  4
           8.0
          15.4
          23.4
          31.0
           8.0
          15.4
          23.4
          31.0
             0.018
             0.012
             0.007
             0.008
        0.0871
        0.058
        0.041
        0.085
 High Sediment Concentration
 Oysters:

   1
   2
   3
   4

 Rangia:

   1
   2
   3
   4
 8.1
15.5
23.5
31.0
 8.1
15.5
23.5
31.0
0.046
0.031
0.019
0.019
0.058
0.039
0.021
0.023
0.223
0.096
0.078
0.195
0.284
0.121
O.OS6
0.230
        0.047
        0.020
        0.020
        0.035
0.020
0.014
0.008
0.008
- 0.097
- 0.066
- 0.044
- 0.082
0.058
0.026
0.024
0.041
0.113
0.043
0.040
0.088
0.153
0.065
0.053
0.126
          0.113
          0.067
          0.049
          0.067
                                       0.053
                                       O.G63
                                       0.041
                                       0.068
0.21
0.10
0.069
0.16
0.12
0.12
O.OS5
0.125
         2404
         3350
         2-50
         2030
                                   1COO
                                   2423
                                   1703
                                   1658
                                                         185S
                                                         2325
                                                         1725
                                                         1818
                                                         784
                                                        1846
                                                        1604
                                                         992
^Short  periods  of  time  when no contaminated sediments were being added to
 the  water flowing over the animals (i.e.,  sediment concentration = 0)
 are  not  included  in  raivge.  However,  they wore used in computing the mean
 This includes  the final  8-9 hours when animals were allowed to flush
 out  sediments  in  their digestive tract prior to removal for analysis.
                                   - 419 -
-------
Table 4. Normalised values for Kepone concentration in
         oysters exposed in laboratory trays to suspen-
         sions of sediments contaminated with Keponc.
         Presented as a function of the mean hourly
         concentration in sediments for the duration
         of each experiment.
Exposure Length Mean
Period of hourly
Exposure cone.
(days) Kepone
for each

First series
1
2
3
4
1
2
3
4
1
2
3
4
Second series
1
2
3
4
1
2
3
4

of experiments
6.9
14.8
21.8
29.2
6.9
14.8
21.8
29.2
6.9
14.8
21.8
29.2
of experiments
7.3
14.8
22.0
29.0
7.2
14.7
21.9
28.9
period
(ppb)
(24 Feb
0.027
0.037
0.023
0.033
0.057
0.073
0.045
0.067
0.032
0.104
0.070
0.098
(13 May
0.042
0.035
0.026
0.038
0.098
0.086
0.063
0.093
   Mean
  hourly
   cone .
  Kepone
   for
accumulated
time periods
    (ppb)
                            - 27 March 1977)

                                 0.027
                                 0.032
                                 0.029
                                 0.0303

                                 0.057
                                 0.066
                                 0.059
                                 0.0613

                                 0.082
                                 0.094
                                 0.085
                                 0.0903
                             - 11 June 1977)

                                 0.042
                                 0.038
                                 0.034.
                                 0.0353

                                 0.098
                                 0.092
                                 0.083
                                 0.0853
Actual
 cone.
Kepone
  in
oyster
meats
 (ppm)
                0.087
                0.125
                0.136
                0.113

                0.130
                0.1.60
                0.188
                0.1.33

                0.185
                0.250
                0.209
                0.257
                0.039
                0.058
                0.064
                0.096

                0.090
                0.160
                0.110
                0.230
                                                       Normalized
                                                          cor.c .
                                                         Kepone
                                                           in
                                                         oyster
                                                          (ppm)
             0.097
             0.101
             0.177
             0.103

             0.139
             0.134
             0.255
             0.121

             0.203
             0.215
             0.269
             0.236
             0.032
             0.058
             0.086
             0.088

             0.078
             0.158
             0.148
             0.210
                               - 420 -
-------
                               Table 4,  (con'Ul)
                                     Normalised values
             in ovstcr  meat'
Exposure
Period


Length
of
Exposure
(days)

Mean
hourly
cone .
Kepone
for each
period
(ppb)
                                           Mean
                                          hourly
                                           cone .
                                          Kepone
                                           for
                                        .accumul ated
                                        time oeriods
                                        	(ppb)
            Actual
             cone .
            Kepone
               in
             oyster
            meats-*-
             (oom)
                Norn-:a lizec
                   COP,c .
                  Kepone
                    in
                  03/8 C02,-
                  me a t s""
                   (ppm)
Third series of  experiments (3 July - 9 Aug. 1977)
          1
          9
          4
          1
          2
          3
          4
3.
15.
23.
31.
8.
15.
23.
31.
0
4
/
-4
0
i
5
5
0
0.
0.
0.
0.
0.
0.
0.
0.
047
020
020
035
113
043
040
088
0. 047
0.034
0.029..
0.0313
0.113
0.080
0.066
0.072
3
         0,
         0
         0,

         0,
         0,
         0
110
067
049
067

210
100
069
         0.160
0.
0.
0,
0.

0.
0.
0.
0.
072
104
076
059

133
167
124
131
           1  De-tr-rr.ir.ed  analytically
           2  Norr.all:-ed  value  computed proportionally
           3  Mean value  reference  used in computing normalized  values in
              oysuers
                                       - 421 -
-------
Table 5.  Mean hourly concentration of Kepone in
          sediment suspensions flowing over Rancia
          and Macoma during the total duration of
          each period of expos-ure in experimental
          trays.
              Total
             duration
           of exposure
              (days)
 Mean hourly
concentration
   Tor  each
weekly period
    (ppb)
 Mean hourly
concentration
   for  full
period  (ppb)
    Second series of experiments  (13 May - 11 June 1977)

    Low sediment concentration
               7. 3
              14.8
              22.0
              29.0
    0.039
    0 . 0 •* A
    0.025
    0.037
    0.039
    0.037
    0.033
    0.034
    High sediment concentration
               7.2
              14.7
              21.9
              28. 9
    0.104
    0.091
    O.C67
    0.093
    0.104
    0.097
    0.087
    0.090
    Third series of experiments  (8  July  -  9  August)
    Low sediment concentration

                8.0              0.05:
               15.4              0.026
               23.4              0.024
               31.0              0.041
                      0.058
                      0.043
                      0.036
                      0.037
    High  sediment  concentration

                8.1
               15.5
               23.5
               31.0
    0.153
    0.065
    0.053
    0.126
    0. 153
    0.111
    0.091
    0.100
                            - 422 -
-------
Table 5, Continued
                                 Moan hourly
                   Total         concentration      Moan hourly
                 duration          for each       concentration
                of  exposure      weekly period        for full
                   (davs)           ...  (oob)          Deriod foob)
Kacoma;    Second series of experiments  (8 July - 9 August  1977)

          High sediment concentration

                    7.5             0.086             0.036
                   14.7             0.06^             0.075
                   21.7             0.0 rO             0.031
                   29.0             0.098             0.085
                           - 423 -
-------
Tublo 6.  Hunqo and moan of  water temperature and
          salinity in trays holding animals during
          Kepone uptake experiments.
Weekly
Period
1st Series (Feb. 24
Oysters:
1st
2nd
3rd
4th
2nd Series (May 13
Oysters:
1st
2nd
.3rd
4th
Macoma :
1st
2nd
3rd
4th
Rangia:
1st
2nd
3rd
4th
3rd Series (July 8
Oysters:
1st
2nd
3rd
4th
Rangia: 1st
2nd
3rd
4th
Temperature
Range
- March 27, 1977)

14.0 - 20.8
15.0 - 21.0
16.1 - 20.8
14.8 - 19.6
- June 19, 1977)
18.3 - 25.0
21.3 - 25.0
22.3 - 25.7
20.5 - 25.0

21.3 - 25.0
22.3 - 25.7
20.5 - 25.0
20.7 - 25.9

16.6 - 21.2
13.7 - 20.8
19.0 - 22.3
18.0 - 21.3
- August 9, 1977)

26.9 - 34.0
26.8 - 32.0
25.0 - 30.0
26.5 - 30.9
20.5 - 24.3
20.4 - 24.9
19.0 - 22.0
20.0 - 23.2
(C)
Mean
*
17.2
17.7
18.5
17.0
20.9
22.4
23.5
21.5

22.4
23.5
21.5
23.7

18.6
19.5
20.4
19.2

29.6
29.3
26.6
28.5
22. 9
22^5
20.3
21.4
                                          Salinity  (o/oo)
                                          K-ange         Mean
                                         19.3
                                         19.1
                                         19.1
                                         1715
22.1
20.6
20.1
19.2
17.5 -
16.2 -
17.5 -
18.9 -
16.2 -
17.5 -
18.9 -
19.9 -
0.5 -
5.0 -
1.3 -
3.2 -
19.2
17.9
19.5
20.3
17.9
19.5
20.3
20.0
7.3
6.4
7.9
6.4
20.4
20.2
19.7
18.4
                                                         18.3
                                                         17.1
                                                         18.3
                                                         19.4
                                                         17.1
                                                         18.3
                                                         19.4
                                                         19.9
                                                          5.5
                                                          5.4
                                                          5,1
                                                          5.0
20.2
20.9
21.9
22.9
2.8
3.9
4.2
2.3
- 20.8
- 22.1
- 22.9
- 23.6
- 8.7
- 8.8
- 6.0
- 6.8
20.6
21.6
22.5
23.1
5.9
6.1
5.4
5.4
                           - 424 -
-------
    Tabl2 7.  Concentration of Kcpone  in  the  moats of
              oysters and Rangia  held  in  control  trays
              receiving no contaminated sediments and
              in test trays partially  or  fully buried
              in unsieved sediments' contaminated  with
              Kepone.  July 8 - August 9,  1977.   Means
              in parentheses.

                                  Kepone Cone.
                                   in  Anirr.als       Kepor.e  Ccr.c,
                 Cumulative         Buried in          in  Control
    Exposure         No.             Sediments           Anirr.als
     Period          Days          	(pnri)	     	LTJ2HL___

A.  Oystars (partially buried in  test  trays):

       1             8.5             0.034             ^0.007
                                     0.040
                                     (0.037)

       2             15.9             0.024             <0.009

       3             23.9  '           0.014             £0.005
                                     0.01,,
                                     (0.016)

       4             31.6             0.014             <0.004
                                    4.0.OOy
                                    «O.Co7)
    Rangia  (fully buried  in mud)

       1              8.5              0.067              0.011
                                      0.035
                                     (0.051)

       2             15.9              O.G53            <0.006
                                    "  0.039
                                     ( 0 . 0'" 6 )
    i

       3             23.9              0.029            <0.003
                                      0 . 03 o
                                     (0.033)

       4             31.6              0.034            flO.007
                                      0.031
                                     (0.032)
                           - 425 -
-------
Table 7 (Continued)


B.  Concentration of Kepone (in ppm) in unsieved sediments
    used in test trays in which animals were fully or partially
    buried.

       1.   Mixed sair.ples at start-of experiment:   0.71
           (Same sediments used in both travs)     2.83
                                                   (1.77)

       2.   Fractionated and mixed samples at end of experiment:

              a.  Mixed sample from oyster trays   2.89

              b.  Sample from top 1-crn layer in
                  oyster tray                      2.24

              c.  Mixed sample from Rangia tray    2.12

              d.  Sample from top 1-cm layer in
                  Rangia tray                      0.64
                                - 426 -
-------
- 427 -
-------
                  Table  9.  *!..!:)  height  (in en)  of (iv.tcrs in
                            diffrn-P.L  sa-.'pJes anal vr'.cd  for Kepone
                            durin; uptake i .-iperi r.eni s -   \'u":i;er  01
                            anir.als  in each sar.'.ple appears In
                            •Tare:! '.he ;es .
E xposurc
 Period
eo r,c .
i P.
sedira-r.s
First series of cx-c-ri
1 (4
2 (4
(3
3 (4
(3
4 (4
(3
(4
Second series of
1 (8
2 ^
(4
3 (3
(5
4 (4
(4
(5
Third Series of
1 (3
(-
2 (3
(3
~) o
\ -^
) 7
^ /
\ —7
) 7
) 7
) 7
) 7
ex
) 5
) 6
) 5
) 6
) 5
) 5
; 5
] 5
C'XP
] 8
> -i
-, 7
) 7
.3
-
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                                             - 428 -
-------
Exposure
Period
   Low
 Kcponc
  cone.
   in
sedinents
  Medium
  Kopone
   cone .
    in
sediments
  !iu;h
 Kepone
  cone.
   in
sedin-.encs
Aniir.als
 Buried
   in
  mud
Cuii L r
-------
      Table; 10. Mean  height  (in cm) of Raivia  In different
               sa:~ples  analyzed for Kepc:ie c'.irinc uptake
               experirr.er.es.   XuTiber of animals in each
               sample  appears in parentheses.
Exposure
 period
                               1.1
                            seci r r.ants
Si-c-r.d series  of  oxporir.or.cs (13 May

   1           (S)  4.?      (S) 4.6                     (3; 4.0

   2           (4)  4.9      (4) 4.8                     (4) 5.0
               (4)  4.9      (4) 4.3                     (4) 4.8

   3           (4)  4.7      (4) 4.7                     (4) 4.7
               (4)  4.7      (4) 4.8                     (4) 4.8

   4           (8)  4.6      (8) 4.7                     (8) 4.5
               (8)  4.7      (8) 4.7                     (7) 4.7
               (8)  4.8      (8) 4.6


Third  series  of experiments (8 July - 9 Au^.  1977)

   1
   2


   3


   4
(4)

(4)
(4)
(4)
(4)
(4)
(5)
5

4
4
5
5
5
4
.01

.99
.49
.00
.15
.03
.73
(2xi
(3)
(4)
(4)
(5)
(4)
(5^
(6)
5 .
4.
4.
4.
5.
4 .
4.
4.
31
90
88
92
02
89
S3
79
(3)
(3)
(4)
(3)
(4)
(4)
(5)
(5)
/
5
/
i
5
5
4
5
5
.85
.04
.92
.02
.12
.96
.00
.24
(5)

(6)

(6)

(5)
(5)
5.

4.

4.

4.
4.
20

74

98

88
75
                                 - 430 -
-------
Table 1:.   Moan height (in cm)  of Mace-a in different
           samples analysed for Kepone auring uptake
           experiments.   Number of animals in each sample
           appears in parentheses.
  Exposure                 High                 Control
   Period                  Kepone                Animals
                           cone .  ...
                            in
                         sod iments
  Second  series  of experiments  (13 May - 19 June 1977)

     1                     (15)  1.7              (10)  1.6

     2                     (12)  1.6              (10)  1.6

     3                     (12)  1.5              (11)  1.6

     4                     (10)  1.4              ( 7)  1.6
                             - 431 -
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                                                               - 432 -
-------
Kgy to ider.tification of components in Fi.uirc 1

     A.  Constantly-over flowing box providing York River water
         supply to system.

     B.  Subr.iers ible pump.

     C.  Heat exchanger system.

     D.  Cascading trough used to allow escape of gases coining out
         of suspension  as result of river water being heated up.

     E.  Constantly-overflowing overhead trough from which water
         for experimental trays was siphoned.

     F.  Flow ir.eter.

     G.  Peristaltic pump used to meter out sediment suspension.

     d.  Flask holding sediment suspension.

     I.  Mixing chamber receiving simultaneously York River water
         and sediment suspension.

     J.  Magnetic stirrer.

     K..  Experimental tray holding oysters.

     L.  Wot table holding experimental trays.

     M.  Drain pipe maintained a water level of about one-inch
         on vet table.  This served as first component of a series
         of sedir.-.ent trays.

     N.  Water from wet table overflowed into a series of three
         o;her si/dir.ent traps.

     0.  Siphon to mixing chamber of Kangia trays.

     P.  Constantly-flowing overhead trough from which water of low
         salintiy for experiinental trays was siphoned.

     Q.  Siphon used to add river water from Trough E to fresh water
         i.i Tray P.
                                   - 433 -
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         at  start  of third  series  of  experiments.
                               - 435  -
-------
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        selves fully.
                            - 436 -
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                      - 445 -
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                           - 446 -
-------
           s AiA'cr ."--«. jt,:,i/ Hvaro ' r.i'/n i ca 1 i.jur\,VY  S




              Pro—es,;  Report  (Nov.  1,  1977)
I,  Hydra^raphieal  Survey (Aur; . ,  1977)




           Four t r^n.u-e: ~  v ^ ro  occuni'oJ for  the




\c i. L ri  ^ r^ r c o s c 3 c i o n. 3  i. n c L u ^. o c z. n  G Ji c n u ^ ^.i ri s ^ o ^ .




(prirary)  scatiior.   r primary station,  r^oai.u/cJ
ar.d   ottom depth,  '.vhile the tvo  side car.r.^1




r:.(.>asurc:d ;op and bottom depths.   (fi^ur<.'3 or



positions are  .".eluded v;ithin).
                           s a comoilation of  information
concernin,,  ~acn  station.
                               - 447 -
-------
n
                                       rplcd from S/26/77
 ..t  15:3 co 3/23/77 ;,c l:-,CO.

•ation -46.31A - total der>th  17  feet
 Current rr.eter depth off  the  bottom:
               2 foor. and  7 . 5  feet
 Current r.ecer tir.e in:
               S/23/77 at  1C15
 Current rr.eter
               8/29/77 .:t  1-35
 Sar.ples taken at TV. id do:~)t>   included all oarar.eters
:ation ^6.51 3 - total  2coth  19.5 f»
 Current "eter dep;>. off  the  bottom:
               3  foot.   ul 10.5 feet
 Current rreter ti^.e  L
               8/23/7   :t: 1050
               8/2;-, -7  at  1'325
 Sarples taken at  * ^r>,  rid <-i:id bottom depths,  included
               all  parar e tors

ration -^.:1 C -  total  d.er>th 23 feet
 Current meter dooth  off  the hotter.:
               2  feet,  c.5 :Vet and 12.5  feet
 Current meter time  in:
               ; / ->•; / " 7  ~ t- P Q •' 0
               O - •	/ > / i  ci L L , -T U
 Current merer time  oat:
               0/29/77  at 1',-lJ
 Samples taken at  mid .'.<_pth, in^uded all  parameters,
               except kepone
                                   - 448 -
-------

                                                             \
                                                              "   " • \
                                                 4

                                                \ •
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    \ ,
' >  «'.   I
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               \  \

                                                             n':
                                                             i i
                                                        V.  -'
                                                                          *


                                                                        ~v» -1-
                                               -  449 -
-------
Vl
       l '
              -r \J
                                            \ -
                                             V
                                  \
                                 -  450 =
-------

- 451 -
-------
  C r<;\7' ••;
                  ')
                  i
     K
\
-,452 -
 '
-------
Sr.v i.-  73. :.•'-.  ;;.<::.pled frcr: OS(V 3/27/77  to S/29/77 11CO

  Sration  73.:'.  A  -  tola I dupch 15.5  feet

    Current r/.^rcr  depth off che bottom:
                   to  foot
    Current r.eter  t i/vo in:
                   8/23/77 at 1550 ...
    Current meter  t ~. ~c ouc :          .
                   S/29/77 at 1523
    Sarr.ples t.ikon  at. T.ij.! dopth. included all parameters
                   c-xceot ke-jone
  c •-
     i:ion  73.?. \  r> - local cooth  21.5  feet
    Current  ".-.-ter vlv.nth 01:  the  bottom:
                   2.J, 7.5 ar.J  13.0  feet

                   t/ 23/77 at  1512
    Current  r,.tcr ::-:o out:
                   S;2y/77 -it  1:45
    Sampler  taken from top,  rr.id, bottom, included
                   all parameters
  f t>:ti.-r.  ^ :•, . : -C. - tot.tl tie?th  12.5 ioet

    Current r.-^r J.i^tk. off  the  bottom:
                   5 /eet
    Current r^rer L:- e  in:
    Samples  taken at rr. i d depth,  included all parameters,
                                 - 453 -
-------
                   iro:n OvOO  d/24/77  to 1200  3/26/77
            7  A - ro~al ,:,'-t:h  33 foot
C,..-ru -t

Currer.t

Current
                 . .. ~ ,' /  /  . ; .
         ".e t c r  111 ~e o'.i t .
                c / 2 :' I 7 1  a: t
         .aken  at  '"id  d(.••'.
                             h,  incue
                -  rotal tL-ntrh :"3". 5
                'i- .  v . j ,  3 r.J ± u  i o c r.

                X  jI/77 at  1705
                  ' ' c, • "• ^  •- '-  i ' i n
                .,*..,/!  . I >-  i 't i. J
Sar.pl.c--  taken at  top,  r.U,  bootom, included
                all  oarar.eters
c •

C;i

Cu

Cu
                   "  total  depth  13.5  ice c

                    ''1. olf  tl'.c-  hotter.:
                 r, '.!.!/ /7  a-: 1 7 jjj
      r.c  rr.L-tcr  L !"".•_•  out:
                 _-  -, ~ , - -,   ^ 1 r -

      uS  tJ.ken  at  :  'vi  ^.^-::t:i ,  ^
                            - 454  -
-------
  ion  111  -  sa-oioj  froin 8/2-V77  at  0900 to 3/26/77 at 12.0
  .'r_i i-n  !!_!  A - L^:iL  i!..>pt h 13 feet

  Current  rvter di-^th  off the bottom.:
                 '. ',nd  11  feet

                 - •.;L'/77'at 1350
  U "LI "I* t~ Cj P. c.  ' -. O L ">.' r" * ".  O i "> Li v. '
                 .:. 29/77 at 1215
  Samples  Cakor.   :  :: i d dopfh,  included a'l parr.r.ct 2rs
                   ••:co'c r'.oor.c-
Sr.-.rior.  Ill " - tocai  depth 20  feet

  Current  :   er dcnth  off tro bottorri:
                 2 ,  7.5 a:id 13 feec
  Cur re lit  ":. :er t i::'c-  in:
                 ~/22 '77 at 1UO
  Current  rr.etcjr ti:"".(.'  cut:
                 c/29''77 at 1210
  Sarr.pl. .  taken ,:t  top, ::.id ,  and  bottom depth,  included
                 a I 1  narair.et er.s
         111  C -  -..-mi  d.-Dth 12  ieo
  C irrent  ™eter depth off the  bottom.


                         'at 1215
                    .
Samples  takm  ;t r:_i_d  depth, included all parar.et
                                                      c.-rs,
                             -  455 -
-------
    Tide.  :;au ;i'S '.cure installed in the-  foil,/,-:!:;:1; three




1 ocat ions .  They were  installed 0:1 u vvek  before the  field




ir.tenr ive  survey ar.d pulled CUL one v.'eek  after the




intensive  survov.  Currently,  ail tide  data are being  sen:.




to Fisher  and Porter for  reduction.




    Tide  £au£o stations:




    1)  T.sT3oden Pi  - at  Ft.  F.ustis




    2)  Pier  C h i c  . n o ~: n y i i o I i d a y I n r,  C.: r. p • r e u r. d




         (of  'It. 3, near  nouth of C'l".ick>::.u:v;ny)




    3)  U'escc  r, Va.  Pier (near Hcpewell)








II.  Data  ' d-actien




    All hy 'rcvraphical  and sediment  intensive data are




currently beir.•: keypunched.  Parameters  ir.v'Iuc:c  dissolved




o^^T•^TL^l, *_ u *". r^ u i ;d *!*.',  j. . i ^* i.* c. w * , v c v f  s1iiwJ.r,>v  t  ;•, .   * •. ^^-^




:clia.; and kcpene  concentration.   It  is  ..•:;:; r i L^a co




 "inish kcypun-":: n,?  and editing  by  the end  of  k"ev-_ --":. er,  15"




     Current rvcer  fil.r.s ^'ive  lie en  Jc-ve Ic p^/d and  are be in-7




;•: i. ,~/.red co be  r^-ad.   It is also  planned  '_o k^vc the  data




reduction uork  e.^    by the end  of  "kovctr.ber, 1977.
                                 - 456 -
-------
 PRELIMINARY ANALYSIS OF KEPONE DISTRIBUTION
             IN THE JAMES RIVER
             Donald J. O'Connor
              Kevin J. Farley
Environmental Engineering and Science Program
              Manhattan College
            Bronx, New York 10471
                      - 457 -
-------
Introduction




     The general purpose  of  this  research  project is to assess




the effect of synthetic materials,  such  as pesticides, on the




water quality and ecology  of  estuarine systems.   The present




phase of the project  is being  specifically directed to the ana-




lysis of the Kepone distribution  in the  James  River estuary in




the vicinity of and downstream from,  Hopewell,  Virginia.   The




ultimate goal is to provide  a  quantitative framework for  evalua-




tion of the time required  to  reduce the  Kepone  concentrations to




acceptable levels.




     Significant concentrations  of  Kepone  are  present in  various




phases of the estuarine system of  the James  River -- in solution,




in suspension, in the sediment and  in the  food  chain, particu-




larly in various species  of  fish.   The interrelationships, or




more specifically, the transport,  uptake and release of Kepone,




as shown in Figure II, are  thus  affected by  both physio-chemical




mechanisms, as well as bio-ecological phenomena.  The former of




these includes the hydrodynamic  transport  through the estuarine




system, adsorption to and  desorption  from  the  suspended and bed




solids, and the settling  and  resuspension  of these solids.  The




latter incorporates the assimilation  and excretion routes




through the various components of  the food chain.  Although




less significant for  Kepone-,  transfer to the atmosphere,  photo-




chemical oxidation and biological  degradation  are potentially




significant transport and  kinetic  processes.
                               - 458 -
-------
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                                                   -  459  -
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ACCUMULATION
IN FOOD CHAIN






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-  460  -
-------
T_he Distribution  of  Kepone  on Solids



     Natural  clays of  various types, and organic material, pos-



sess an adsorptive capacity.   The rates of adsorptive reactions



are being investigated experimentally under controlled labora-



tory conditions in order  to provide realistic kinetic coeffi-



cients for the Kepone  analysis.   The desorptive characteristics



of both the inorganic  and  organic fractions of the suspended



solids are also being  reviewed.   This phenomena of adsorption-



desorption is one of  the  important transfer routes in the ulti-



mate transfer of  Kepone from  the system.  Based on the Langmuir



Isotherms, equations  have  been developed to predict the spatial



and temporal  distributions  of Kepone in an advective-dispersive



estuarine system.  However,  due  to the preliminary nature of



this work, the less  complex,  advective, steady state model was



used for analysis.   Equations governing the water column and



estuarine bed for such a  system  are as follows:





1.  Water



               8m1

    Solids  U, -~—- = -K m,  +  "K  m0
              1 9x       si     u 2


                  8C

    Dissolved  U, 3—-  = -K  (r -r^m.C, + K.^m. - K, (C -C_)-K C,
                1 ox       oclll    dll    b!2   al
    Particulate  (U' '•*	.=  +-K- ('r  -r..)iii







2.   Bed



               om~     K

    Solids  U. -5—- = + —  m,  - K m0
             2 9-x      a    1     u 2








                               -  461 -
-------
                    9C

     Dissolved  U0  •—• =  -K  (r  -r „ ) m0C0+K , r 9m.+K, (C,-
                  /  ox      oc  2  <;2d22bl
     Partlculate  U
                    2  3
                                                   Ks

                                                   ~
where:



     the subscripts  1  and  2  denote the water column and estuarine



bed concentrations,  respectfully,
and where:



     U  - horizontal velocity



     C  - dissolved Kepone  concentration



     x  - longitudinal  distance



     K  - adsorption coefficient



     r  - solids adsorptive capacity
      C


     r  - Kepone concentration on the solids



     m  - solids concentration



     K. - desorption coefficient



     K.  - bed diffusion coefficient
      b


     K  - aeration  coefficient
      a


     P  - solids Kepone concentration



     K  - solids settling  coefficient
      s


     <*  - the ratio, of  bed  Volume to water column



          volume
     K  - solids  scour  coefficient
      u
[•m /sec]
[meters ]
[Mg/g]
[I/day]



[I/day]



tl/day]



[yg/g]


[I/day]






[dimensionless]



[I/day]
                                 - 462 -
-------
     As a  first  step,  this  preliminary analysis was simplified



by various  assumptions  -  subject to verification by the ongoing



field and  laboratory  studies.   The first of these assumptions -

                                  9m      3m

solids being  in  equilibrium i.e. TC	 and -~	 = 0, appears to be



a safe assumption  for  the  non-saline portion of the estuary.  In



addition,  the bed  solids  concentration,  m?, was said to be much



greater than  the suspended  solids concentration, m •  the aera-



tion term,  K  , was  taken  to be  negligible; and the solids
            Si


adsorptive  capacity,  r  ,  was assumed to  be much greater than



either of  the Kepone  concentrations on the solids, r  and r„.



The kinetic coefficients  -  K ,  K,, K , and K , were assigned
                             o    a   s       u


from the limited data  available.  Finally, for this "first-cut"



model, the  Kepone  concentrations on the  bed solids, r , were



assigned from data; these  concentrations were in turn utilized



in predicting the  Kepone  water  column concentrations.



     Based  on these assignments of coefficients, the longitudinal



distribution  of  total  and  dissolved Kepone in the water column



is presented  in  Figure  III  along with the State Water Control



Board 1976  Kepone  data.   The line of total Kepone concentration



fits the data quite well  and although the dissolved fraction of



Kepone is high,  this  concentration is merely a function of



Kepone kinetic coefficients, K   and K  - values which were



obtained from a  minimal ameunt  of sketchy data.  Further analysis



is presently  being  performed which will  predict both the water



column and  the bed  concentrations of Kepone.



     The above analysis will be further  complicated as the
                                 - 463 -
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                           - 464 -
-------
saline portion  of  the  estuary  is  approached.   As the lighter




clay particles  which  are  maintained  in suspension in the non-




saline area  encounter  the saline  region of  the estuary, floccu-




lation and agglomeration  may  occur,  increasing the size and




possibly the density  of  the  particles.   These factors result in




further deposition, which is  enhanced  by virtue of their occur-




rence in the null  zone  of the  estuary.   There are, therefore,




a variety of significant  factors  which may  account for the accu-




mulation of  solids and  Kepone  in  the estuarine bed at the fresh




water-saline interface.   These factors, along with the inability




to assume solids equilibrium  in  the  saline  region, have lead to




a detailed investigation  of  solid material  in the estuary.









Hydrodynamic Transport




     Since the  concentration  of  suspended  solids is  an important




factor as an accumulation site for Kepone,  the temporal ar, j




spatial distribution of the  solids within  the estuarine system




is a necessary  element  in the  analysis.   The  distribution is




determined by the hydraulic  transport  through the estuarine




system.   A two-dimensional (longitudinal-vertical) analysis has




been developed, based on  the fundamental principles  of momentum,




continuity and  state.
                                  - 465 -
-------
     In  this  analysis,  under steady state,  tidally  averaged



conditions,  the  longitudinal momentum equation  for  a later-



ally homogeneous  estuary is:
where p = density;  p  = pressure; N = vertical  eddy viscosity;



and u = horizontal  velocity.  The coordinates  for Eq.  1 are



shown in Fig.  IV  in which the longitudinal  x-axis is positive



toward the  ocean  and  the vertical z-axis  is  positive toward the



bed of the  estuary  channel.   Boundary  conditions  compatible



with Eq. 1  are,
          — =  0               at z = -n                     (2)
          d Z
           -N  ~ =  C /u, /u.     at z = h                      (3)
              d z    d  b  b
in which  -n  =  surface elevation and h =  average  depth;  C, =



dimensionless  friction coefficient; and  u   =  velocity at the



bed.  The  vertical  component of the momentum  equation is



simply  the hydrostatic pressure equation:
           1  <3p          .     •-                                , ,
           —  -~  = '-y                                           (4
           p  3 z    ^
                                   - 466 -
-------
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-------
     In order to solve  Eq.  1,  the  hydrostatic pressure., Eq. 4,




is expressed in terms of  the  horizontal  and vertical distribu-




tion of salinity.  The  equation  of  state which specifies the




density as a function of  salinity  is  given by:
          p = pf(l + aC)                                    (5)
in which p, = the density  at  zero  salt  content and a = 0.000757




(parts per thousand)   .  The  components of  the pressure force




are then evaluated  in  terms of  the observed vertical and longi-




tudinal salinity gradients  and  freshwater flow,  which are




assumed known from  measurement.




     The solution of the above  equations indicates that local




rather than boundary conditions  control the magnitude and




gradient of horizontal velocity  at a  particular  location.  Be-




cause of local control,  the velocity  at one location is rela-




tively independent  of  those at  other  locations.   This condition




occurs as a result  of  decoupling the  equations of motion and




salt transp or t.




     Results of this analysis are  presented for  Pritchard's June




1950 survey and Nichols' March  1965 survey  of the James River in




Figure V and VII respectfully.   In addition, the solution also




indicates the depth at which  the -net  horizontal  velocity is




zero.  Defining this depth  at a  number  of stations and interpo-




lating for others delineates  the plane  of no net motion for the




saline intrusion zone  of  the  estuary, Figures VI and VIII.  At




the tail of the salinity  intrusion, this plane meets the bed of










                              -  468 -
-------
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                                                 -  469  -
-------
              SALINITY CALCULATION FOR JAMES RIVER ESTUARY
                              (JUNE, 1950)
         . 10
          20
          30
    > 00 IN
    s£i
      V3 O
      >    0
          0.2
   i>
         -0.2



      *•   °
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SALIN

Ol
                                  I       I      1       !
                                 PLANE OF NO NET MOTION
                 0 = 6,000 cfs
                           18-23JUNE 1950
   9  ASSIGNED N
   B  CALCULATED c
  	f USED IN THE SALINITY MODEL
                   .•-•-•-•"•'
                       N^—
                             A^A-^

            «^rB    «
   • SURFACE LAYER

   A BOTTOM LAYER
                                               _L
40     35     30     25     20     15
         DISTANCE FROM MOUTH, miles
                                                     10
                            FIGURE  VI

SALINITY CALCULATION FOR JAMES  RIVER  ESTUARY (JUNE,  1950)
                              - 470 -
-------
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LEGEND
C ASSIGNED N ®
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	 t t/SfD /A/ 7>Y£ SALINITY
MODEL

	
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1 I -L,Jr**\ 1 I I
40      35      30      25     20
         DISTANCE FROM MOUTH, miles
                                                 15
10
                            FIGURE VIII
SALINITY  CALCULATION  FOR JAMES RIVER ESTUARY  (IIARCH,  1965)
                                  - 472 -
-------
the estuary.  Upstream of  this area, the horizontal velocity  in




the whole water  column is  in the seaward direction.




     The estuary  is  then segmented horizontally and the hori-




zontal flow  in  the  surface layer at each vertical  cross section




is first calculated.   Horizontal flow difference between two




adjacent vertical planes gives the vertical flow between the




surface and  bottom  layer,  from,which the vertical  velocity is




obtained by  dividing  by  the  average width of the segment.  This




procedure is  obviously a solution of the hydraulic continuity.




     The vertical flux of  salt due to dispersion between the




surface and  bottom  layers  is described by the dispersion coeffi-




cient, C, obtained  from  the  vertical eddy viscosity through




an empirical  relationship,
          E = N(l +  R. )                                       (6)
where Ri (Richardson  number)  is  defined as:
          Ri =    _                                        (7)
Equation 6 indicates  the  relationship between the two coeffi-




cients, whose general  validity  has  been shown by field data,




as presented by Officer.




     The tidal diffusion  and  velocity shear contributions, which




can be envisioned collectively  as  a longitudinal dispersion across




a vertical section  following  the  classical one-dimensional estu-




arine analysis, did not exhibit themselves in the portion of the









                             - 473 -
-------
estuary that our models were  concerned.




     The distribution of salinity was  used  to  test  the validity




of the hydrodynamic model - bottom  panels  of  Figures  VI and




VIII.  Based on these validations of  the hydrodynamic model, an




analysis of suspended solids  followed  by incorporating the set-




tling and scour rates with the  hydrodynamic  transport to deter-




mine the distribution of solids.  Settling  rates,  for the




present, were assumed constant  down the  length of  the estuary




and this rate was obtained from the average  particle  size, using




a modification of Stokes' Law.   Since  little  work  has yet been




performed on scouring rates in  estuaries,  these rates were




assigned merely to show that  a  good fit  can  be obtained.  Results




of this solids modeling, with and without  the  assigned scouring




rates, are presented in Figure  IX.




ASSIMILATION AND DEPURATION OF  KEPONE  IN THE  FOOD  CHAIN




     The transfer of Kepone from its  initial  discharge at Hope-




well to its accumulation in the fishery  stock  may  occur in a




number of ways.  It may be ingested directly  from  that which is




dissolved or suspended in the water;  it  may  be assimilated by the




phytoplankton-zooplankton; and  it may  be taken in  by  bottom




feeders from the material which has settled  in the  channel bed.




The predominant sites for settling  appear  to  be downstream from




Hopewell, in the region of -the  fresh  water-saline  interface, and




in.various dead zones in the  fresh  and saline  regions.  Experi-




ments involving assimilation  and depuration  of Kepone by various




species are being conducted.  The rates  of  accumulation and
                               - 474 -
-------
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                                              - 475 -
-------
excretion, equilibrium  conditions  and  concentrations,  lethal



and chronic - are being  analyzed  in  order  to incorporate these



kinetic factors in a food  chain analysis.



     Preliminary analysis  has  been made  in evaluating  the assi-



milation and depuration  kinetics  on  various species of fish.



Data from experimental  studies performed at EPA's Gulf Breeze



Laboratory are used to  evaluate the  relevant coefficients.  The



equation utilized in this  analysis - similar to the Langmuir



kinetic equation for the adsorption  to and desorption  from sus-



pended solids, is as follows:
           = K  (r -r)m(t)C  -  K,rm(t)
              O  c             d
where



     r  - Kepone concentration  in  the  biomass             h-g/g]



     m  - biomass concentration                          [g/£]



     t  - time                                            [days]



     K  - assimilation  coefficient                        [I/day]



     r  - biomass assimilation  capacity                   [yg/g]



     C  - dissolved Kepone  concentration                  [pg/£]



     K  - depuration coefficient                          [I/day]







The only assumption made  in-th'is analysis  was  that the biomass



assimilation capacity,  r  ,  was  taken  to be much greater than the



Kepone concentration in the biomass,  r.   Results of this analysis



for oysters  (Crassostrea, virginica)  are  presented in Figure X.
                                - 47S -
-------
 00
 LU
 D
 9

 00
 LU
 CC

 LU
 2
 O
 CL
 LU
10'
         0
            10      20     30     40      50

         ACCUMULATION — *--« - DEPURATION

                       TIME, days
             5        10

           ACCUMULATION
   15       20

-^^3—DEPURATION
                           TIME, days
                                                      60
25
                             FIGURE X

CALCULATION FOR THE ASSIMILATION AND DEPURATION OF KEPONE IN OYSTERS
                         - 477 -
-------
From these results, it can be  shown  that  the  bio-ecological




phenomena of assimilation and  depuration  can  be  modeled utili-




zing Langmuir kinetics if data  for  the  evaluation of  the relevant




coefficients is available.









CONCLUSION




     The equations presented in  this  report  appear to be suffi-




ciently realistic as a first approximation  in representing the




various phenomena under consideration.  At  the present time, the




analysis is being extended to  treat  the ecological system as a




continuum using trophic length  as  a  metric.   Given the inputs




from the sources in the vicinity  of  Bailey's  Bay, tiie transport




in the non-saline and saline regions  of the  James ebtuary and




the distribution of suspended  solids  and  Kepone,  the  food chain




model is being enlarged to include  the  uptake and excretion of




Kepone in the various trophic  levels  and  the  predation and




feeding associated with these  levels.   At  this time,  the saline




and non-saline regions of the  estuary  are  being  combined into




one continuous solution.  Steady  state  conditions, which repre-




sent average conditions during  various  seasons of the year, are




being assumed for these preliminary  steps  of  the  analysis.









ACKNOWLEDGEMENTS




     The research work described  in  this  report  is sponsored




by Gulf Breeze Research Laboratory,  Sabine  Island, Gulf Breeze




Florida, Grant Number R804563.   The  participation of  Gerald L.
                                - 478 -
-------
Schnoor is acknowledged.  Various phases of the computations




were performed by Cherng-Ju Kim and George A. Leahy, research




assistants in the Environmental Engineering and Science Program




at Manhattan College.
                               - 479 -
-------
                          SESSION V
           "Additional Presentations and Wrap-up"
CHAIRMAN
J. Gary Gardner
Regional Toxic Substances Coordinator
U.S. Environmental Protection Agency, Region III
SPEAKERS

Mr. Charles H. Whitlock
NASA Langley Research Center
"Remote Sensing Observations of Industrial Plumes at Hopewell, Virginia"

Dr. A. R. Paterson
Research Manager
Allied Chemical Corporation
"Allied Chemical Kepone Investigations"

Mr. Martin W. Brossman
Wrap-up, EPA Activities with Kepone
                                   - 480 -
-------
 REMOTE SENSING OBSERVATIONS

    OF INDUSTRIAL PLUMES

    AT HOPEWELL, VIRGINIA
     Charles H. Whit lock
             and
      Theodore A. Talay
NASA Langley Research Center
  Hampton, Virginia  23665
              - 481 -
-------
       REMOTE SENSING OBSERVATIONS OF INDUSTRIAL PLUMES
                     AT HOPEWELL, VIRGINIA
           Charles H. Whitlock and Theodore A. Talay
         National Aeronautics and Space Administration
                    Langley Research Center
                    Hampton, Virginia  23665
                         INTRODUCTION

     The National Aeronautics and Space Administration (NASA)
is investigating the potential of remote sensing for monitoring
various parameters in the marine environment in cooperation
with the Environmental Protection Agency (EPA) under Interagency
Agreement IAG-02^5-  One aspect of this effort is a research
program aimed at developing remote sensing strategies for the
monitoring of industrial outfalls.  Recent EPA field studies
have shown that 98 percent of all water discharge points are
detectable by changes in color or temperature which may be
monitored using remote sensing instrumentation.1

     Over the past several years, a series of aircraft remote
sensing experiments have been made over the James River at
Hope-well, Virginia.  The objective of these flights has been
to investigate the potential of various types of remote sensing
instruments for identification and quantification of several
water parameters.  Aerial mapping cameras were carried on each
of the aircraft experiments, and a thermal band was part of the
multispectral scanner data for all flights except one.  It is
the purpose of this document to synthesize the photographic and
thermal data which are presently available, such that appropriate
agencies may assess their value to solution of the Kepone
problem in a timely manner.  Industrial outfall plume patterns
over a wide range of tidal and river flow conditions are
presented.  A description of the aerial photography system
which gave the best images is also provided.
                    EXPERIMENTAL CONDITIONS

     The Langley Research Center has conducted a total of 30
aircraft remote sensing overpasses in the Hopewell area with
mapping-quality earners and multispectral scanner instruments.
Table 1 summarizes the environmental conditions and type of
data obtained for each experiment.
                               - 482 -
-------
                            TABLE 1.
                          SUMMARY OF
                  HOPEWELL,  VA. REMOTE  SENSING DATA
DATE
WIND SPEED
WIND DIRECTION
JAMES RIVER DISCHARGE
(AVERAGE - 7,432 cfs)
APPOMATTOX RIVER DISCHARGE
(AVERAGE - 1,590 cfs)
NUMBER OF OVERPASSES
PHOTO
SCANNER WITH THERMAL
TIDE AT OVERPASS
( CITY POINT)




Feb. 1,1974
5kls
E-NE
14, 028 cfs

1,780 cfs


1
0
MAX EBB
(3.7HRS
AFTER HIGH)



May 28, 1974
10 Ms
NW^
5, 306 cfs

786 cfs


5
1
0.9-2.0HRS
AFTER HIGH




May 17, 1977
<3 kts
SW(am) NE(pm)
2,808 cfs

580 cfs


24
24
INCOMING
TIDE
(1.7HRS
BEFORE LOW
T01.5HRS
AFTER HIGH )
The first experiment was conducted February 1, 197^? and consisted
of a single overpass.  A mapping camera was used along with an
experimental multispectral scanner; however, that particular
scanner did not have a band for thermal measurements.  Wind was
out of the east-northeast and river discharge was higher than
average.^  Flight overpass occurred with an outgoing tide near
the time of maximum ebb.

     The second experiment occurred on May 28, 197^-  The mission
included five overpasses with mapping quality photography and one
overpass with a multispectral scanner having a band for thermal
measurements.3  Wind was out of the northwest and river discharge
was below average.2  Again the overpasses occurred on an outgoing
tide.

     The third experiment occurred on May 17, 1977, and included
2k overpasses over a 9-hour period.  This experiment was a
cooperative effort between NASA, the Virginia State Water Control
Board, and the U.S. Army Corps of Engineers.  Winds were very
low and shifted in direction.  River discharge measurements
furnished by the Virginia State Water Control Board indicate low
river flow conditions.  Overpasses began 1.7 hours before low
tide, covered the incoming flow, and ended 1.5 hours after high
water.
                                 - 483 -
-------
     A detailed description of tidal conditions at time of
remote sensor overpass is shown in figure 1.  For ease of
presentation, overpass times are given in hours after high
tide at City Foinl .  From firure I, it is clear that remote
sensing data nave "leen obtained over most of the tidal cycle.
It must "be re-emphasised, however, that, river flow and wind
conditions were different on each of the days that experiments
were conducted so  caution is required in making a direct
comparison of flow patterns.  In the discussion which follows,
flow patterns are presented in the order shown in figure 1.
For reasons of brevity, data from all overpasses are not
shown.  For the May 28, 197^, data, photographic results are
presented for the overpass at 0.9 and 1.7 hours.  Thermal
images are shown  for the overpass at 2.0 hours.  Photographic
results are shown  for the February 1, 197^, overpass as well
as for the overpasses at 6.9, 8.U, 11.9, and 1.5 nours after
high tide from the Hay 17, 1977, experiment.  As indicated in
table 1, thermal measurements wore made for the May 17, 1977?
experiment but are not available at the present time.
                            RI.I3ULT3

     A photograph of the May 28, 197^, overpass at 0.9 hour
after high tide is shown in figure 2.  The original imagery
was taken on Kodak natural color aerial film from an altitude
of 5-3 kilometers.  Unfortunately, the photographic and report
reproduction process results in a considerable loss of contrast,
such that only gross features of the plume are evident.  Second-
generation transparencies (copied from the original negative)
do show a marked contrast between the Gravelly Run and Bailey
Creek plumes however.  Distinction ic possible because of the
different colors of the two discharges.^

     To enable a reproducible presentation of the Gravelly Run
and Bailey Creek plumes, the second-generation transparencies
for February 1, 197^ > May 28, 197^, arid May 17, 1977, were
copied on tracing paper for the region from the mouth of the
Appomattox River to beyond Tar Bay.  These sketches are meant to
convey the general limits of the plumes but are not intended to
relate to specific pollutant concenl rations or those subtle tonal
variations that are visible only on the originals.  Figure 3
shows the completed sketch for the cverpass at high tide plus
0.9 hour on May 28, 197^-  The gray ;.hading generally denotes
the black water masses of the .-amc- color as being discharged
from Bailey Creek.  The Gravelly Run plume is denoted by the
dotted areas.  Sketches of plume patterns were made only for
those situations where water depths were believed greater than
remote sensing penetration depths.  Secchi depth observations
                                 - 484 -
-------
(an indicator of the penetration depth) of Bailey Creek at low
tide from the Route 10 bridge were on the order of 8 cm (3-1  in).
Thus, the bottom was not visible in the aerial photographs for
all but the immediate shoreline areas.  The sketches, therefore,
represent plume patterns for the surface waters only.

     The sketch of the May 28, 19TU, image at high tide +0.9  hour
shows the flow to be predominately downstream (ebb flow).   The
Bailey Creek plume is seen to hug the shoreline of Bailey  Bay
and move downstream around Jordan Point and into a secondary
channel that passes through Tar Bay.  The Gravelly Run plume
covers a wide area immediately at the mouth of Bailey Creek.   A
hook-like feature near the mouth of Gravelly Run is notable.

     Figure U shows the sketch of plume patterns 0.80 hour later
(high tide +1.7 hours) on May 28, 197^-  This sketch shows a
change in plume patterns caused by the ebb flow condition  in  the
James River.  An extensive movement of the Bailey Creek plume
downstream, beyond Jordan Point, is evident and the Gravelly
Run plume is now located across the mouth of Bailey Creek, in a
more linear, shearing fashion.  The hook-like feature in the
previous sketch has shown evidence of downstream migration as
well.

     To lend support to the interpretation of the photographic
images, the May 28, 197^, thermal map for the Hopewell area is
presented in figure 5-  The image shown is based on raw,
unsmoothed multispectral scanner data which have been calibrated
in an approximate manner using historical data.  (Temperature
measurements were not taken in Gravelly Run or Bailey Bay  during
the May 28, 197^, experiment.)  Both previous studies^ and
Virginia State Water Control Board data indicate that the  Gravelly
Run discharge is approximately 10°C higher than the ambient
James River water upstream of Hopewell.  Figure 5 shows the
thermal pattern at high tide +2.0 hours or just 0.25 hour  after
that shown in figure k.  The shape of the Gravelly Run plume
deduced from the photographic image is very similar to that of
the thermal image 0.25 hour later.  The Gravelly Run plume may
be distinguished with remote sensing data because of both  its
color and temperature contrasts with the surrounding waters.

     Figure 6 is a blownup thermal image showing the Hopewell
waterfront area.  In this image, some smoothing was applied
to the raw multispectral scanner data before the map was
produced.  In spite of the smoothing process, several small
discharge points along the Hopewell waterfront can be observed
in addition to the effluents from Gravelly Run and Bailey  Creek.
                              - 485 -
-------
     Figure 1 is a sketch of the Hopewell area as imaged on
February 1, 197^, at high tide +3.7 hours aear maximum ebb flow
conditions.  Although the river flow conditions and winds are
changed from those on May 28, 197^, (table l), the features of
the flow are similar to those shown previously.  The Bailey Creek
plume is seen to be along the Bailey Bay shoreline, around
Jordan Point, and down the secondary channel into Tar Bay.  There
is some evidence of plume flow into the main navigation channel
of the James River.  The Gravelly Run plume has much the same
appearance as in figures k and 5-

     On May 17» 1977? a long-duration experiment was conducted
on the James River which included 2k overpasses of the Hopewell
area by an NASA aircraft carrying both a mapping camera and a
multispectral scanner.  The temporal extent of this experiment
is indicated on figure 1.  From these photographic images, four
were selected for sketches that exemplify the range of the tidal
cycle included in this experiment.  The river flow and wind
conditions were both low on this day as noted in table 1.
Figure 8 presents the conditions of high tide +6.9 hours and, in
fact, is the condition of slack water after ebb.  This should
demonstrate the maximum downstream extent of the Bailey Creek
plume just before the tide turns to flood.  Because of slack
water conditions, the Gravelly Run plume is seen to extend
outward from shore toward the main channel.  Also, the Bailey
Creek plume appears to be sheared off into the main navigation
channel off Jordan Point and mixed to the extent that it is not
visible in the photography after entering the main channel.  The
plume, however, remains highly visible in the secondary channel
into Tar Bay.

     Figure 9 shows the condition of high tide +Q.h hours when
the tide is on the flood.  James River water is seen to encroach
upon and move upstream around Jordan Point causing a disorganized
plume appearance.  The Gravelly Run plume is now seen to move
upstream toward City Point and in areas, to mix with Bailey
Creek plume waters.

     The conditions at high tide +11.9 hours for May 17, 1977,
are shown in figure 10.  This corresponds also to slack water
after flood and represents the probable maximum upstream extent
of the plumes on this day.  The Bailey Creek and Gravelly Run
plumes have been nearly swept clear of Jordan Point and nearshore
areas of Bailey Bay.  The Bailey Creek plume is seen to extend
beyond City Point and divide up between the two channels of the
Appomattox and James Rivers.  The Gravelly Run plume appears
extended in an upstream manner and disappears into the main
navigation channel of the James River.
                             - 486 -
-------
      The  final  sketch,  figure 11, is the condition following
high  tide at +1.5 hours, just after the tide is on the ebb.
Under these circumstances, James River waters are seen sweeping
into  the  Gravelly Run plume and dividing the Bailey Creek
plume into two  parts, one of which moves up in the main
navigational channel and the other around Bailey Bay and Jordan
Point into the  secondary channel.  These features may also be
seen  in figure  12 which is a reproduction of the near-infrared,
second-generation color transparency from which the sketch of
figure 11 was made.

      Of the aircraft remote sensing experiments conducted to
date, the use of color infrared film appears to give the most
descriptive images of the Hopewell area over a wide range of
solar elevation angles and haze conditions.  Details of the
photographic system which was successfully used on the May 17,
1977, experiment are described in table 2.
AERIAL
TABLE 2.
PHOTOGRAPHIC SYSTEM USED OVER HOPEWELL, VA. MAY 17, 1977
CAMERA AND SETTINGS
Camera - Zeiss aerial mapping
Lens - 15.2 cm 1 6 in )
Shutter speeds - 1/115 (morning mission)
1/200 (afternoon mission)
F-stop - Automatic exposure control
ASA number - 80
Field of view - 37 x 37 degrees
FILM AND FILTERS
Film - Kodak 2443
Film format - 22.9x 22.9 cm (9x9 in)
Emulsion number - Kodak 206 -2
Filter 1 - KLF 36
Filter 2 - Wratten 12 (minus blue-haze reduction)
AIRCRAFT ALTITUDE - 3270 m (10,730ft )
AIRCRAFT SPEED - 138 m/sec (268knots)
IMAGE OVERLAP - 60 percent

It is believed that this system might be useful to other agencies
for monitoring activities in the Hopewell area, particularly if
rapid response capabilities are required.
                             - 487 -
-------
                      CONCLUDING REMARKS

     The National Aeronautics and Space Administration is
investigating the potential of remote sensing for the monitor-
ing of various water quality parameters in cooperation with the
Environmental Protection Agency.  Over the past several years,
some 30 overflights of the Hopewell area have "been conducted.
Results indicate that surface-water plume patterns may be
observed with photographic and thermal remote sensing systems.
Long-duration experiments over a significant portion of the
tidal cycle provide information on hydraulic characteristics
which may aid scientific understanding and analytical modeling
of pollutant transport.  Multispectral scanner data of the
Hopewell area, not processed at the present time, may enable
definition of further details concerning river hydraulics  and
industrial discharge plume characteristics.
                              ~ 488 -
-------
                          REFERENCES

1.   Melfi, S. H.;  Koutsandreas,  J.  D.;  and Moran,  John:   Tracking
     Pollutants from a Distance.   Environmental Science and
     Technology, vol. II, no.  2,  February 1977, pp.  36-38.

2.   197^ Water Resources Data for Virginia.   USGS,  Richmond,
     Virginia, 19 71*.

3.   Johnson, R. W. ; Batten, C.  E.;  Bowker, D.  E.;  Bressette,  W.  E. ;
     and Grev, G. W.:  Preliminary Data from the May 28,  I9jk,
     Simultaneous Evaluation of Remote Sensors Experiment.   NASA
     TM X-72676, June 1975-

k.   Bloom, S. G.;  Birch, T. J.;  and Raines, G. E.:   The  Effect
     of the Thermal Discharge from the Hopewell Chemical  Plant on
     Bailey Bay.  Battelle Columbus  Laboratories, May 1972.
                               - 489 -
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               -  500 -
-------
FIGURE 12,- PHOTOGRAPH  FROM MAY  17, 1977 OVERPASS  AT
            HIGH TIDE + 1.5 HOURS.
                      - 501 -
-------
             ALLIED CHEMICAL KEPONE INVESTIGATIONS

      A. R. Paterson, R. J. Williams, D. E. Scheirer, J. Vitrone
     Two investigations have been in progress during the past year at
Allied Chemical in Morristown, NJ that seem to offer some promise in
relation to the Kepone problem.  One approach offers a possible means
of immobilization of the material in the James River.   The second pre-
sents a means of destruction for Kepone residues of varying concentra-
tions.

     The first investigation was initiated after we observed early in
the year that the majority of the Kepone in the river was associated
with the organic material in the bottom sediment.  We decided at that
point to attempt addition of small particles of coal as a means of
adsorbing Kepone and decreasing its availability.

     Early experiments indicated that Kepone is removed from solution
by coal and that the removal, though not rapid, continues for at least
28 days.  At that point we found that the Kepone concentration had been
decreased by 70%.

     The data are as follows:
Initial Kepone Particle
Concentration Size
96
96
1.
1.
1.
1.
1.


9
9
9
9
9
ppb
ppb
ppb
PPb
ppb
ppb
ppb
-8,
-8,
-8,
-8,
-8,
-8,
-8,
+14
+14
+14
+14
+14
+14
+14
mesh
mesh
mesh
mesh
mesh
mesh
mesh
Time °/<
4
12
15
3
1
7
15
days
days
minutes
hours
day
days
days
'•> Reduction Stirring
24%
35%
20%
40%
55%
65%
72%
3
3
15
3
hours
hours
minutes
hours
1-1/2 hours
1-1
1-1
12 hours
/2 hours
                               -  502 -
-------
     Further work with coal in the presence of Kepone containing
sediment indicated that the level  of dissolved Kepone decreased by
about 50%, when a thin layer of coal was placed on top of the soil.
The procedure and results are as follows:

Procedure

     Approximately 21-23 g (dry wt) of James River bottom soil
(Buoy #107) was added to a 60 OD X 142 mmL centrifuge bottle.  The
amount of soil was matched to within 0.3 g in a sample pair.   A 1-1/2
inch Teflon stir bar was added to each centrifuge bottle followed by
95 ml of distilled water.  A 5 ml  aliquot from a methanolic Kepone
solution (20.8 mg 14C labeled Kepone dissolved in 200 ml methanol was
then added to each centrifuge bottle.  The Kepone was mixed with the
soil by vigorous stirring for 30 minutes.  Each sample pair was then
centrifuged for about 30 minutes.   Each sample pair was then centri-
fuged for about 30 minutes to rapidly settle the soil particles.  The
samples were usually left at rest for 1-2 days before adding the coal.
About 1.5 g of -8,+14 mesh coal was added to one of the centrifuge
bottles in each sample pair.  The other sample (without coal) in the
pair served as a control.  The coal was added without any agitation of
the sample.  The amount of coal corresponded roughly to a monolayer of
coal over the soil.  After standing at rest for 1 to 12 days, each
sample pair was filtered using a 0.45   Millipore filter to remove any
suspended soil particles.  The filtrate was then transferred to a 250
ml separatory funnel and extracted for 5 minutes with 40 ml of toluene.
Four of five drops of concentrated sulfuric acid were added to the fil-
trate to aid in the extraction.  Following the extraction, the toluene
was transferred to a 50 ml volumetric flask.  The Kepone content was
determined by liquid scintillation using a cocktail consisting of 5 ml
of toluene from the 50 ml volumetric flask and 10 mL of Insta-Gel (Packard)
Results were expressed as the amount of Kepone in a 100 ml of water.

     Results of experiments carried out to date are as follows:
Sample 45 with coal

Sample 46 without coal


Sample 49 with coal

Sample 50 without coal


Sample 53 with coal

Sample 54 without coal
22 ppb remaining in solution
after 12 days
42 ppb remaining in solution
after 12 days

19 ppb remaining in solution
after 4 days
44 ppb remaining in solution
after 4 days

37 ppb remaining in solution
after 12 days
50 ppb remaining in solution
after 12 days
48% Reduction
57% Reduction
26% Reduction
                                   -  503  -
-------
Sample 57 with coal      40 ppb remaining in solution
                         after 1 day                       _?0, _  .   .
Sample 58 without coal   63 ppb remaining in solution       'ls> Keduct'lori
                         after 1 day

     We are hoping to run some tests in the near future with living
organism to evaluate the effect of added coal on Kepone uptake.

     The second investigation involves destruction of Kepone through
the use of caustic solutions at elevated temperature and pressure.

     Materials chosen for testing were Kepone, Mi rex and three samples
of clean-up wastes from the Baltimore plant.  In general, samples were
mixed with water to form solutions or slurries, concentrations up to
about 5%, in the presence of sufficient sodium hydroxide to provide a
one-half molar solution of sodium hydroxide at the completion of the
reaction, and held in the presence of oxygen from two to ten minutes
at temperatures of 300-350°C.  Sufficient pressure, 2000 psi - 2200 psi,
was applied to maintain water in the liquid state.  Alkali was used to
aid dehalogenation and prevent the formation of a substantial  carbon
dioxide gas phase.

     Experimental  variables have not been exhaustively explored, but
conditions were found at which Kepone concentrations in the reaction
product were reduced to less than the limit of detection using gas
chromatography with detection by electron capture.  The rate of Kepone
disappearance under these conditions appears to be at least three orders
of magnitude per minute.  The results for Mi rex were the same.

     An additional goal  was destruction of all organic matter in the
samples.   That this was achieved was evident from the chromatograms
obtained in the analyses.

     Our conclusions at this point are:

     1.  The high-temperature hydrolysis and oxidation is a technically
feasible means for disposal of Kepone and Kepone-bearing wastes.

     2.  The procedure should have wide applicability in disposing of
halogenated organics and organics in general.

     3.  The process would have an advantage over incineration in that.
in the event of mishap,  the material in process could be contained
readily and recycled if decomposition were incomplete.
                                  - 504
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                   SUMMARY OF KEPONE SEMINAR ISSUES


                                  by


                          Martin W.  Brossman

                    Environmental Protection Agency
                           Washington,  D.C.


     The past two days'  presentations and discussions have provided a
comprehensive survey of much of the  work related to the problem of
Kepone contamination in the James River.  I'll  now try to place this
material in perspective and describe the interrelationships.   A solution
to the Kepone contamination problem  in the James obviously involves a
full assessment of the nature and extent of the current contamination,
knowledge of the effect of the contamination on human health  and the
environment as well as its social and economic  impact, an analysis of
potential mitigative measures and an eventual assessment of various
action-no action alternatives.  Except for the  last item—assessment of
various action-no action alternatives—we have  heard presentations and
discussion directed to all of these  issues.   It would serve no useful
purpose now to categorize each individual presentation we have heard
into the issues I have listed.  However, much of the work described here
today is either being utilized in, or is an integral part of  the Kepone
Mitigation Feasibility Project we are conducting at EPA.  Our project
approach has been organized to address each of  the issues I have cited.
Therefore a discussion of the project itself may be the most  useful way
to place the types of efforts discussed here in perspective.   A few
background facts may be helpful.

     The Governors of Virginia and Maryland, in the Fall of 1976, jointly
requested that EPA evaluate the Kepone contamination of the James River
and its tributaries, and explore corrective or mitigative actions.  In
response to this request, a two-phased project plan was adopted.  Phase
I involves a detailed assessment of: (1) suspected continuing sources of
Kepone contamination; (2) the fate and transport of Kepone in the James
River system; (3) the current and long-range effects of Kepone contami-
nation on the biota; and  (4) an evaluation of mitigation and  removal
methods.  The results of Phase I are to provide a basis for action
recommendations.  Following a review of the Phase I recommendations by
EPA and the States of Virginia and Maryland, Phase II may involve a
decision to: seek funding for a major cleanup or mitigation program;
proceed with pilot testing of alternative corrective and mitigative
actions; or withhold action due to unfavorable cost/benefit assessments.
                                       505 -
-------
     An allocation of $1.4 million was made for the Phase I effort.  A
comprehensive work plan was developed and support studies were arranged
with the U.S. Army Corps of Engineers, the Energy Research and Develop-
ment Agency (ERDA), the EPA Gulf Breeze, Florida, Environmental Research
Laboratory, and the Virginia Institute of Marine Science.  Engineering
studies to contain, stabilize, or remove Kepone-contaminated sediments
have been conducted and eighteen alternatives to mitigate the Kepone
problem have been evaluated.  In addition, the Corps has contracted with
the U.S. Fish and Wildlife Service to investigate the wetland ecosystem
to compare plant and animal distribution patterns with unaffected areas.

     Under the interagency agreement with ERDA, the ERDA/Battelle Pacific
Northwest Laboratories are: (1) conducting sampling and analysis of the
suspected sources of Kepone contamination into the James River; (2)
obtaining in cooperation with the Virginia Institute of Marine Science,
water quality, sediment, hydrological and other data on the James River;
(3) modelling the transport and fate of sediments in the river; (4)
evaluating nonconventional Kepone mitigation techniques; and (5) assessing
the ecological impact of the current Kepone contamination and possible
mitigation approaches.  The EPA Gulf Breeze Laboratory provided scientific
data and analysis on the effect of Kepone on the estuarine biota, including
biological accumulation, plus distribution and fate of Kepone.  The
Virginia Institute of Marine Science is collecting field data on the
James River.  Results of these investigations are being integrated into
models of Kepone movement and sediment transport by Gulf Breeze and
ERDA/Battelle Laboratories, respectively.  The final report describing
the results of these investigative efforts will be completed in March
1978, and will be the basis for considering the Phase II efforts.
                                   - 506 -
-------