POLYCHLORT N  ! ; i  3IPHENYLS

                               IH " ;r  '•'• DSON  RIVER

                     ?o\ r.\LLS-FORT EDWA'••!"',  NBU v )RK STATE)

                     Pov.'il J.  N."-li'.-^  ..
        Polychlorinated Biphenyls in the Hudson River
         (Hudson Falls-Fort Edward, New York State)
                  Royal J. Nadeau and Robert A. Davis
               United States Environmental Protection Agency
                          Edison, N.J. 08817
    Polychlorinated biphenyls  (PCB's), as recently as 1966,
have been recognized as an environmental contaminant.  PCB's
are primarily used in industry and are even more persistent than
DDT.  These compounds are essentially nonalterable by microbial
or physical-chemical activities and are incorporable into living
protoplasm.  The bonding between the chlorine atom and the bi-
phenyl structure is resistant to shearing by natural degradation
processes, therefore PCB's are not easily metabolized by enzyme
systems presently found in nature (ALEXANDER 1975).

    The atomic structure of PCB's gives them specific chemical
characteristics very desirable for certain industrial uses, i.e.
dielectric fluids in capacitors and transformers,

    PCB's not only are incorporable into living biomass in
natural ecosystems, but are transferable within food webs; the
end result being a much higher concentration of these compounds
occurring in specific tissues of summit carnivores
    It has been estimated that 4 to 5 x 10  tons/year of PCB's
are lost into the Nation's fresh and coastal waters  (NISBET &
SARDFIM 1972).  An indication of the widespread contamination
of PCB's in today's society is illustrated in the Temporary
Tolerance Limits (Table 1) set by the FDA in certain food prod-
ucts (KTMSBRQUGH 1974).

                             TABLE 1

               Temporary Tolerance Limits of PCB's

                    Substrate                  Level  (ppm)
       Milk (fat basis)                              2.5
       Dairy Products  (fat basis)                    2.5
       Poultry  (fat basis)'                           5.0
       Eggs                                           -5
       Complete and finished animal  feeds             .2
       Animal feed components                        2,0
       Fish and shellfish  (edible portion)           5.0
      *Paper food-packaging material               10.0
      *Does not apply  to packaging material that is
       separated from  the food by a  barrier impermeable
       to PCB migration
Bulletin of Environmental Contamination & Toxicology,
Vol. 16, No. 4 © 1976 by Springer-Verlag New York Inc.

     This paper describes the presence and extent of contamination
 of water, sediments, and biota of the Hudson River by industrial
 use  and discharge of PCB's in the vicinity of Hudson Falls-Fort
 Edward, New York State.

 Description of Sampling Area - Hudson River (Figure 1)

     Station 0 is located near the town of Hudson Falls, New York
 in a hydroelectric impoundment area.  This station is upstream
 and  separated from the Ft. Edward discharge outfall by a hydro-
 electric dam  (height - 15m) .  At sampling time  (3:15 pm,
 August 12,  1974) the water was heavily laden with fibrous
 particulates being carried down from an upstream source.  Several
 paper  mills and fiber board manufacturers are located in Glens
 Falls, 3-5  miles upstream from Station 0.  In the main channel
 area,  the bottom is hard shale.  In the shallows where water
 velocity is less, large deposits of sediments intermixed with
 bark,  branches, lumber slabs, and cinders are found.  A sediment
 sample was  taken by coring into the sediments with a glass
 sampling jar and capping it underwater.  A subsurface water
 sample was  taken nearby.

     A  seine was used to collect fish near a patch of emergent
 vegetation  on an opposite bank from the sediment deposits (east
 bank). The gastropod (snail) populations associated with the
 emergent vegetation were sampled simultaneously.

     Station 1 is located at the junction of the Ft.  Edward out-
 fall and the Hudson River.  There are smaller known discharges
 between Station 1 and Station 0.  At Station 1 the Hudson River
 is a roaring, tumultuous river with a high velocity, high volume
 streamflow  (4466 cfs)l.   The river is heavily laden with heavy
 suspended loads of fibrous material.   Water and sediment samples
 were taken  at this point in the same manner as at Station 0
 (9:15  am, August 13, 1974).   The sediment sample was taken from
 a  small submerged cinder-gravel spit at the outfall junction.
 An upstream gastropod population was sampled several meters above
 the junction.   This station is only accessible by boat because
 the river banks are precipitous shale rock faces,  15m in height.

    Station 2  is located about 0.25 miles downstream from the
 ?V^«i  junction where water and sediment samples were collected
 (10:00  am, August 13,  1974).  River flow conditions  are  the same
 as at Station  1.  No macroinvertebrate or piscine populations
were observed  at this  station.   The water is  laden with  the same
 tibrous suspended materials  as  evidenced at Station  0   The river
bottom is mainly a shale  ledge.  A sediment sample was collected
 Calculated from N.Y.  State Water Resources Data Book,  1971.

                             STATION 0
           BAKER FALLS
                                           Village of
                                        HUDSON FALLS
                         STATION 2

                        STATION 3
                               Village of
                              FT. EDWARD
FIGURE  1 - Location of Sampling Sites in Hudson River in Hudson
          Falls-Fort Edward Area

from a remnant shale flake,  cinder deposit bank above the high
water mark.  All the collecting sites downstream from Baker Falls
were submerged until September 1973.   When an abandoned hydro-
electric dam at Fort Edward was removed,  the water level was
drastically  lowered 5-15 meters.

    Station  3  is located about 0.5 miles downstream from Station
1, water and sediment samples were collected (11:00 am, August
13, 1974).   In this area an extensive sludge bank exists as a
remnant  of past industrial activity.   The bank sediments consist
of gravel, cinders, lumber slabs,  and bark from logging activi-
ties that ceased 40 years  ago.  The sediment sample was collected
from a submerged deposit near the same area where several fish
were collected by seining.  In the shallow area, the fibrous
material, suspended at the upstream stations has flocculated onto
the river bottom, coating  the bottom with a "paper wrapping".

    Station  4  is located 0.75 miles downstream from Station 1.
Ihe river is slightly wider at this point with decreased velocity.
Fish populations are abundant in the shallow shoreline areas.
These populations were sampled by seining.  Water and sediment
samples  were collected in  the river,  three (3) meters upstream
from the junction of a small stream that flows in on the west
shore (1:15  pm, August 13, 1974).

Chemical Analysis

    A measured volume of water sample was extracted with hexane.
The extract  was dehydrated,  concentrated, and analyzed by comput-
erized gas chromatography/mass spectrometry (GC/MS).l

    The  sediment sample was partially dried and extracted by
column elution with a mixture of 1:1 acetone/hexane.  The extract
was washed with water to remove the acetone and then the poly-
chlorinated  biphenyls were extracted from the water with 15 per-
cent ClkCl^  in hexane.  This extract was then dehydrated, concen-
trated to a  suitable volume, and analyzed by computerized GC/MS.2

    The  biota  samples were blended with anhydrous sodium sulfate
(prewashed with redistilled acetone)  and the homogenate was ex-
tracted  with a mixture of  hexane and ethyl ether (3:1 v/v) .  The
extracts were  placed on a  20 gm florisil column, eluted with 25  ml
 A modification of methods published in METHODS FOR ORGANIC
 RESIDUES IN WATER AND WASTEWATER, 1971.  Environmental Protection
 Agency,  National Environmental Research Center, Cincinnati, Ohio.

2A modification of methods published in ANALYSIS OF PESTICIDE
 Research Laboratories, Environmental Protection Agency.

of hexane, and the volume of the eluate was adjusted so the final
concentration of PCB's was within the linear range of the gas
chromatograph.   The  sample of rock bass from the discharge re-
quired a 50  fold dilution before analysis.

    The presence of  PCB's in all samples was confirmed by ore-
chlorinating the samples with SbCl,- for four hours at 170  C to
form CT^IIQ-   '•'•ne ^12^10 was subsequently analyzed by gas
chronatography using a three-foot column of 3 percent Dexsil-300
at 200° C.

    Subsequently, a  GC/MS analysis of the rock bass extract was
performed along with analysis on Aroclor 1016 and 1242 standards.

Analysis  Results

    Detection of PCB' s in water and sediments was accomplished by
comparing computerized GC/MS Spectra of various Aroclor mixtures
including 1016 supplied by the discharger and EPA with environ-
mental sample extracts.

    PCB's identified as Aroclor 1016 were found in the water
samples at detectable concentrations at all sampling locations
except Station 0 (control) and Station 4 (furthest downstream)
(Table 2).
                             TABLE 2

     Analysis of Water and Sediment Samples for Aroclor 1016
   from the Hudson River in the Area of Fort Edward, New York

                                 Contamination Levels
                           Water ug/1        Sediment mg/kg
     Location                (ppb)           	(ppm)

     Station 0                 1.0                  6.9
     Station 1              2800.0               6700.0
     Station 2                 2.2                540.0
     Station 3                (3.0)*             2980.0
     Station 4                 1.0                  6.6

    *Results of replicate analysis - a quality assurance

    At all stations the sediments contained higher concentrations
of Aroclor 1016 than the water column because PCB's preferentially
adsorb onto suspended or already settled materials.

    The high contamination level at Station I indicates the ad-
sorptive capacity and constant exposure  of the sediments nearest
the outfall to the Aroclor 1016.  These  sediments were also
heavily laden with noticeable oil and grease which serves as a
solvent for PCB compounds.

    At Station 3, high concentrations (2980 mg/kg) occur in the
sediments, representing accumulated levels of PCB's,  HP fold
greater than the outfall concentration.   The high level is a
product of historical plus present adsorption and deposition of
PCB compounds.  The PCB level at Station 2 represents historical
deposition mainly.  Although PCB's in the water column are below
dectectable limits at Station 4, PCB's occur in significant
quantities in the sediments.

Biological Tissue

Station 0

    The samples collected above the discharge contained the later-
eluting PCB's with retention times of 84, 98, 104, 112, 125, 146,
and 174 relative to pp DDE.  These are characteristic of Aroclor
1254, another PCB that was used extensively prior to Aroclor 1016.
In addition, major PCB components were found at relative retention
times of 37, 40, 47, 54, 58, 70, and  78.  The relative concentra-
tion of the. PCB components found in the  control station samples
and the absence of PCB components eluting earlier than 28 suggest
that the PCB's in the biota can best  be  estimated as a mixture of
Aroclor 1254 and Aroclor 1248.  Using the later-eluting components
of Aroclor 1254 and the earlier-eluting  components of Aroclor
1248, the PCB concentrations in the biota samples were estimated
and are presented in TABLE 3.
                              TABLE 3

    PCB Concentrations in Biota Collected in the Hudson River

                                      Total PCB  Gastropod   Total PCB
Station O

Station 1
(Above Outfall)
Station 3
Piscine Name
Notopia cornutui frontalis
(Northern Common Shiner)
Perca flavescens (Mitchell)
(Yellow Perch)
Amblopletea rupestris

Helisoma sp
Physa sp

Helisoma sp
Physa sp



               rupestris (Rainesque)        350.0

                 (Northern Rock Ba»»)

 Station 4       Notropis cornutus frontalit           Helisoma sp

                     (Agassiz)            78.0    Physa sp      [27'°]
               (Northern Common Shiner)           Limnacea sp

    Distinctly different from the samples from the control  area
were the samples collected in the vicinity of  or below  the  dis-
charge.  It is evident from a chromatogram of  the sample  of bass
below the discharge that there are no major PCB components  eluting
after 78 relative to DDE.  Moreover, the 21, 28, and  32 components
are present in higher concentrations relative  to the  37 component.
This suggests that Aroclor 1242, Aroclor 1016, or a mixture of
these two formulations are present in the Hudson River  below  the


    The results illustrate that PCB's are ubiquitous  in distri-
bution within the Hudson River within a variety of substrates.
Nevertheless, higher-than-background concentration in the sedi-
ments and biota can be found in the inmediate  vicinity  of the PCB

    Although the pattern of accumulation and magnification  of
PCB's in the biota was similar to that reported in the  literature,
insufficient information exists on transfer rates of  PCB's  within
environmental substrates.  The PCB's being discharged are in  suf-
ficient quantities that contamination of all environmental  sub-
strates have occurred; water, sediment, and biota.

    Although an exact accumulation and transfer model could not be
determined for the sampling area, a hypothetical presentation is
given below:


                              (Adsorption)            (Grazing)
                                               I    (Ingestion)
                                   EPIFAUNAL COMMUNITIES
                             (Adsorption &
                             c  ,.      .  .      L--.	 (Ingestion)

                                    SHINERS, YOUNG PERCH

                                              1-^	 (Ingestion)

                                         ROCK BASS
    At all stations the biota had higher levels of PCB's than the
background water concentration.   At all stations,  except Station
3, the biota contain higher levels  of PCB's than the sediments.

    At all stations the snail populations are important accumula-
tors and concentrators of PCB's  (TABLE 4).   The species collected
are primarily herbivorous grazers,  living off the periphyton
growing on rocks, lumber  slabs,  and benthic surfaces.   The snails
ingest sedimented materials containing adsorbed PCB's along with
their natural food.

                             TABLE 4

       Concentration Factors of PCB's in the Hudson River

                                         Concentration Factor
   Location          Substrate      Tissue/Water   Tissue/Sediment

Station 0          Snails            >1.9 x 10?          3.63
                   Conmon Shiner     >7.0 x 10o           .98
                   Yellow Perch     >17.0 x 10            .41

Station 1
(Above Outfall)    Snails              45 x Kr          6.52

Station 3          Rock Bass          117 x 103           .12

Station 4          Snails             >27 x 10,         11.82
                   Conmon Shiner      >78 x 10           4.09

    The adsorbed PCB's remain biologically active within the food
web since snails are normal dietary constituents of larger game
fish.  This is a possible pathway for biomagnification.  Likewise,
the PCB's are remaining environmentally active and are not taken
out of circulation by the geologic sedimentation process.

    An indication of the seriousness of the problem in the Hudson
River is that the PCB level in the Perca flavescens (Yellow Perch)
at Station 0 is 68 times greater than that found in the same
species from Lake Erie (KELSO & FRANK 1974).   The fish analyzed in
the Lake Erie study were even older and larger than those col-
lected in the Hudson River.  The most probable route of contami-
nation for fish is through the dietary pathway and direct dif-
fusion across exposed gill, intestinal, and integument surfaces.
If the perch collected at Station 0 were older and larger, their
source of PCB's might be the snails, however, small perch are
mainly plankton and epifauna consumers (THARRATT 1969).

    It is significant that the shiners and snails both contained
PCB's, especially since these species are important grazers upon
periphyton communities and serve as food for large consumers,
namely the game fish; i.e., pike, pickerel, bass, and larger
yellow perch.

    The PCB level in the rock bass is greater than the maximum
level documented for fish taken from any industrial river of the
U.S. (NISBET & SAROFIM 1972).  This represents a new record for
PCB contamination of fresh water fish.

    Although the game fish species are not commercially utilized
in this stretch of the Hudson, sport fishing is a cannon wide-
spread recreational activity.  Ingestion of these fish by the
populace  would certainly lead to contamination of specific tis-
sues in their bodies.  Occurrence of PCB's in human tissues has

documented in the literature, especially in people who are con-
stantly exposed to PCB's through their occupation or life styles.
Even though these compounds have a comparatively low acute toxic-
ity for mammals, the long term effects may be much more insiduous
and devastating.  A number of investigators have shown that PCB's
induce production of liver mLcrosomal enzymes.  Others have shown
that PCB's can decrease Vitamin A content in the liver (CECIL, et
al. 1973).  Transplacental passage of PCB's has also been shown
"^GRANT, et al. 1971).  PCB's have been detected in human adipose
tissue in such widespread occurrence that 41-45 percent of the
U.S. population contains 1 ppm or more (PRICE & WELCH 1972).

    Little is known concerning the specific mode of entry of PCB's
into the organisms of the contaminated ecosystem.  Information on
transfer rates and modes is necessary before a plan of action can
be recommended for removing the contaminated substrates from the
Hudson Falls-Fort Edward area.


    We gratefully acknowledge and thank Dr. Bernard Dudenbostel
and Mr. David Speis for the determination of PCB' s in water and
sediment samples, and Dr. Gilman Veith of the National Water
Quality Laboratory at Duluth, Minn, for determining PCB levels
in biological specimens.

                        REFERENCE SECTION

ALEXANDER, M.:  Microbial Ecol. 2_, 17  (1975).

CECIL, H. L., S. J. HARRIS, J. BITMAN, and J. F. FRIES:  Bull,
  Env. Cont. ToxLcol. 9_, 179  (1973).

  PHILLIPS:  Env. Physiol. I, 61  (1971).

HANSEN, D. J., P. R. PARRISH, and J. FORESTER:  Gulf Breeze Env.
  Res. Laboratory Cont. 172  (1973).

KELSO, J. R., and R. FRANK:  Trans. Amer. Fish. Soc. 103, 577

KTMBROUGH, R. D.:  Critical Reviews in Toxicology 2^, 455  (1974).

NISBET, I. C. T., and A. F. SAROFIM:  Env. Health Perspectives,
  Experimental Issue l_  (1972).

PRICE, H. A. and R. L. WELCH:  Env. Health Perspectives,
  Experimental Issue iL  (1972).

THARRATT, R. C.:  Trans. Amer. Fish. Soc. 88  (1959).

TROUT, P. E.:  Env. Health Perspectives, Experimental Issue !_