-W
POLYCHLORT N ! ; i 3IPHENYLS
IH " ;r '' DSON RIVER
?o\ r.\LLS-FORT EDWA'!"', NBU v )RK STATE)
Pov.'il J. N."-li'.-^ ..
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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
(biomagnification).
o
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.
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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.
MATERIALS & METHODS
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.
437
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STATION 0
control)
BAKER FALLS
POWER GENERATING
STATION
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
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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
RESIDUES IN HUMAN AND ENVIRONMENTAL SAMPLES, 1961. Perrine
Research Laboratories, Environmental Protection Agency.
439
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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
(3.1)
Station 4 1.0 6.6
*Results of replicate analysis - a quality assurance
procedure.
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.
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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
Location
Station O
Station 1
(Above Outfall)
Station 3
Piscine Name
Notopia cornutui frontalis
(Agassiz)
(Northern Common Shiner)
Perca flavescens (Mitchell)
(Yellow Perch)
None
Amblopletea rupestris
ug/gm
wet-wt.
7.0
17.0
Name
Helisoma sp
Physa sp
Helisoma sp
Physa sp
ug/gm
wet-wt.
1.9
[0.45]
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
441
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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
discharge.
DISCUSSION
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
discharge.
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:
BIOTA
(Adsorption) (Grazing)
DISCHARGE=> AQUEOUS PHASE * PLANKTON »- SNAILS
I (Ingestion)
EPIFAUNAL COMMUNITIES
(Adsorption &
c ,. . . L--. (Ingestion)
Sedimentation)
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.
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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
443
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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.
AO(NOWLEDGMENTS
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).
GRANT, D. L., D. C. VTLLENEUVE, K. A. MC CULLY, and E. J.
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
(1973).
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 !_
(1972).
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