Ecological Research Series
Chlorinated Hydrocarbons in the Lake
Ontario Ecosystem (IFYGL)
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis, Oregon 97330
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH STUDIES
series. This series describes research on the effects of pollution
on humans, plant and animal species, and materials. Problems are
assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine the
fate of pollutants and their effects. This work provides the technical
basis for setting standards to minimize undesirable changes in living
organisms in the aquatic, terrestrial and atmospheric environments.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and
Development, EPA, and approved for publication. Approval does
not signify that the contents necessarily reflect the views and
policies of the Environmental Protection Agency, nor does mention
of trade names or commercial products constitute endorsement or
recommendation for use.
-------
EPA-660/3-75-022
JUNE 1975
CHLORINATED HYDROCARBONS IN THE
LAKE ONTARIO ECOSYSTEM (IFYGL)
by
Clarence L. Haile
Gilman D. Veith
G. Fred Lee
William C. Boyle
Grant #800608
Program Element 1BA026
ROAP/Task No. 21AKP/14
Project Officer
Michael D. Mull in
Grosse He Laboratory
National Environmental Research Center
Grosse lie, Michigan 48138
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OREGON 97330
For sale by the Superintendent of Documents, U.S. Government
Printing Office, Washington, D.C. 20402
-------
ABSTRACT
Lake Ontario fish, water, sediment, net plankton, Cladophora, and
benthos were examined for DDT group pesticides, dieldrin, and PCBs.
Endrin, BHC group pesticides, and heptachlor were also identified
in some fish samples. Average concentrations ranged from 28 ng/1
(t-DDT, e.e., sum of DDT, DDE, and ODD), 4.8 ng/1 (dieldrin), and
55 ng/1 (PCBs as Aroclor 1254 equivalent) for water to 1.40 yg/g
(t-DDT), 0.07 yg/g (dieldrin), and 5.15 yg/g (PCBs) for whole fish.
DDE levels were generally similar to t-DDT levels, except for sediments
where ODD and DDT contributed significantly to t-DDT values. PCB/t-DDT
ratios averaged 2.6 for all samples except for sediment (7.0) and
benthos (5.3).
This report was submitted in fulfillment of Project Number R-800608,
by the University of Wisconsin, under the (partial) sponsorship of
the Environmental Protection Agency. Work was completed as of August
1974.
-n-
-------
CONTENTS
Page
Abstract ii
Acknowledgements v
Sections
I Conclusions 1
II Recommendations 3
III Introduction 4
IV Methods 5
V Results and Discussion 13
VI References ' 27
-m-
-------
TABLES
No. Page
1 Gas Chromatographic Columns and Conditions. 10
2 Chlorinated Hydrocarbons and Fat in Lake Ontario Fish. 14
3 DDT and PCBs in Lake Ontario Fish Fat. 16
4 Chlorinated Hydrocarbons in Lake Ontario Water. 19
5 Chlorinated Hydrocarbons in Lake Ontario Sediment. 21
6 Chlorinated Hydrocarbons in Lake Ontario Net Plankton. 23
7 Chlorinated Hydrocarbons in Lake Ontario Cladophora. 25
8 Chlorinated Hydrocarbons in Lake Ontario Benthic Fauna. 25
-------
ACKNOWLEDGEMENTS
We wish to thank John Carr, Nelson Thomas, Sam Mozley, Don McNaught,
and the officers and crews of the Researcher, Advance II, and Kaho
for their assistance in sample collection. Technical assistance was
provided by Richard Pyter, Walter Gunthier, Katherine Benkert,
Judy Capelli and Paul Choitz. We are especially grateful to David
Armstrong for his review and comments on the manuscript.
-v-
-------
SECTION I
CONCLUSIONS
Lake Ontario fish, water, sediment, net plankton, Cladophora, and
benthic fauna contained significant concentrations of DDT group
pesticides, dieldrin, and PCBs. Endrin, heptachlor, and BHC group
pesticides (especially lindane, y BHC) were also identified in some
fish.
Lake-wide concentrations of t-DDT, dieldrin, and PCBs (Arochlor 1254
equivalent) for fish (alewives, smelt, and slimy sculpin) ranged from
0.95 to 1.40 yg/g, 0.04 to 0.07 yg/g, and 2.35 to 5.13 yg/g, respectively
Lake Ontario water was found to contain "total" concentrations
(dissolved + particulate) of 28 ng/1 , 4.8 ng/1, and 55 ng/1 for t-DDT,
dieldrin, and PCBs. Water collected off Oswego contained comparatively
high levels of DDT group pesticides, dieldrin, and PCBs, while waters
off Hamilton contained higher t-DDT levels, and waters off the mouth
of the Niagara River showed higher PCB concentrations.
Average sediment t-DDT, dieldrin, and PCB concentrations were 22, 1.2,
and 120 ng/g, respectively. Sediment off the mouth of the Welland
Canal showed higher levels of all three contaminants while sediments
off the mouth of the Niagara River contained higher levels of PCBs
and dieldrin. Sediments off Oswego and at an eastern mid-lake site
showed higher levels of PCBs and dieldrin, respectively.
Average concentrations in net plankton were 3.5 yg/g (t-DDT), 0.12 yg/g
(dieldrin), and 7.2 yg/g (PCBs). Corresponding concentrations in
Cladophora were 229, 13, and 515 ng/g for t-DDT, dieldrin, and PCBs,
respectively. Lake Ontario benthic fauna were found to contain 99,
6.9, and 471 ng/g t-DDT, dieldrin, and PCBs, respectively, with
benthos taken off Hamilton exhibiting levels approximately four times
benthos off Rochester and Oswego.
-1-
-------
High concentrations of PCBs in waters and sediments off the mouth of the
Niagara River and Oswego indicate the importance of the Niagara and Oswego
Rivers as inputs of PCBs associated with settlable particulates. In
most cases, t-DDT concentrations were similar to concentrations of the
DDT metabolite, DDE, except in sediments where DDT and ODD contributed
much larger fractions.
PCB/t-DDT ratios for all samples fell in the range of 1.9 to 3.1
except for sediment (7.0) and benthos (5.3).
Relative chlorinated hydrocarbon concentrations for various segments of
the Lake Ontario ecosystem were about 1; 2,500; 10,000; 150,000; and
300,000 for water, sediment, benthos, net plankton, and fish, relatively.
Although these concentration differences indicated large accumulation
factors for chlorinated hydrocarbons in fish, considerable additional
information is required to elucidate mechanisms of chlorinated hydrocarbon
transport and accumulation that will allow an assessment of the probable
impact on the aquatic ecosystem when contaminant inputs to the lake are
altered.
-2-
-------
SECTION II
RECOMMENDATIONS
Although Lake Ontario fish contained accumulated chlorinated hydro-
carbons at levels several orders of magnitude higher than amounts in
their food organisms and the lake water, processes of uptake and
elimination of these contaminants by fish are uncertain. The mechanisms
controlling these processes should be determined and their relative
importance evaluated to aid in understanding the relationships between
contaminant concentrations in water and in the associated biota. The
elucidation of these relationships will allow an assessment of the
probable impact on the aquatic ecosystem when contaminant inputs to the
lake are altered.
Since chlorinated hydrocarbons associated with the dissolved and particul-
ate (organic and inorganic) fractions of lake waters may interact
differently within the lake ecosystem, analytical methods should be
developed to separate and quantitate the contaminant concentrations in
these fractions.
Lake Ontario waters and sediments near the mouths of the Niagara and
Oswego Rivers were found to contain significantly higher concentrations of
PCBs than the other waters and sediments sampled. This indicated the
necessity to determine the levels and forms (dissolved or associated with
particulates) of PCBs in these rivers to allow an assessment of their
importance as sources of PCBs to the Lake Ontario ecosystem.
Since fish are capable of accumulating chlorinated hydrocarbon concentra-
tions several orders of magnitude higher than the surrounding water, Lake
Ontario fish should be extensively examined for halogenated hydrocarbons
not previously identified or confirmed in fish. Some compounds, although
present in lake waters at undetected levels, may be of considerable
importance due to their toxicities even at very low levels.
-3-
-------
SECTION III
INTRODUCTION
Measurements of pesticide residues in the Great Lakes have shown
excessive levels of several chlorinated hydrocarbons. Polychlorinated
biphenyls (PCBs) and DDT group pesticides (i.e., DDT, DDE, ODD, and
related isomers) have been confirmed in Lake Michigan fish at levels
exceeding U.S. Food and Drug Administration action limits, and dieldrin
has been found at levels approaching the action limit (Veith, 1970;
Reinert,1970). The pesticide contamination problem in Lake Ontario
has received less attention than in Lake Michigan where residue
concentrations in several segments of the ecosystem may be higher
(Reinert, 1970; Veith, 1973). Although studies of chlorinated hydrocarbon
contamination in Lake Ontario fish have been conducted (Reinert, 1970;
Kaiser, 1974), information concerning other segments of the ecosystem
is incomplete.
This study was conducted as a part of the International Field Year
for the Great Lakes to provide baseline information on the levels of
DDT group pesticides, dieldrin, and PCBs in Lake Ontario fish, water,
sediment, net plankton, Cladophora, and benthic fauna. This information
will allow a more complete assessment of the chlorinated hydrocarbon
problem in Lake Ontario and contribute to an understanding of
chlorinated hydrocarbon transport in aquatic ecosystems.
-4-
-------
SECTION IV
METHODS
SAMPLING
Alewives (Alosa pseudoharengusj, smelt (Osmerus mordax), slimy sculpin
(Cottus cognatus), water, sediment, net plankton, Cladophora, and
benthos samples were obtained from several near-shore and mid-lake
sites on Lake Ontario during the summer of 1972. Sampling was more
intensive near Rochester, Oswego, and Hamilton. Samples were also
collected off Cobourg and Olcott, at the eastern end of the lake,
and at four mid-lake sites. Figure 1 shows the locations of the
sampling stations. Water samples were taken (Van Dorn type sampler)
just below the surface, at 10 m below the surface, and at 10 m above
the sediment at each station. Fish were trawl-netted at 18 to 73 m
and mixed plankton netted (64 urn mesh opening) at 5 to 10 m. Cladophora
was gathered at 1 to 2 m depths. Sediments were sampled with a Ponar
grab, and benthos were captured using a epibenthic sled. All samples
were transported and stored frozen or near 4°C in glass or metal
containers to minimize chemical changes and contamination.
EXTRACTION AND CLEANUP
Fish
Extraction and cleanup of whole fish were conducted according to the
procedures described by Veith (1970). Frozen fish (a combined
sample of at least eight individuals for each species captured at
each site) were ground twice to homogenize the flesh before weighing
out six 10 g sub-samples. Each sub-sample was blended with 70 g
anhydrous Na^SO, and extracted for at least 4 hr with 170 ml of 1:1
ethyl ether-hexane (v/v) in an all-glass Soxhlet extractor. The
extracts were concentrated to 20 ml in an air stream and 2 ml aliquots
were removed for analysis of non-volitile fats and oils (residue after
evaporation at 150°C for 20 min). The remaining extracts were subjected
to liquid chromatographic cleanup and fractionation. The extracts were
placed on 20 g columns of florisil (Fisher F-100, 60-100 mesh washed
-5-
-------
wsp
wC
TORONTO
HAMILTON
fb
wfsbpC
wp
Figure 1. Lake Ontario sampling sites for chlorinated hydrocarbon analysis. Notations are:
f-Fish, w-Water, s-Sediment, p-Net Plankton, C-Cladophora, b-Benthos.
Station numbers are IFYGL station identifiers.
-------
with hexane and activated by heating to 650°C for 2 hr) and topped with
anhydrous NazSC^ to prevent deactivation of the fTori si 1 by water.
The columns were sequentially eluted with 200 ml each of 6, 12, and 50%
ether in hexane (v/v). Since preliminary gas chromatographic analysis
of the 12 and 50% eluates failed to provide identification of compounds
of interest, notably dieldrin and endrin, which were identified in the
6% eluates, only the 6% eluates were considered for subsequent examination.
The presence of dieldrin and endrin in the less polar fractions likely
resulted from some deactivation of the florisil by water vapor prior to
use. The 6% eluates were concentrated (air stream) to 50 ml before
removing 5 ml aliquots for preliminary gas chromatographic determination
of DDE (generally the largest peak on the chromatogram). The remaining
portions'were concentrated to less than 10 ml before placing on 20 g
columns of silicic acid (washed with hexane, dried at 130°C overnight,
and partially deactivated with 2.1% water). Elution with 250 ml hexane
produced the PCB fractions. Further elution with 200 ml 3:1 dichloro-
methane-hexane (v/v) allowed elution of the chlorinated pesticide
fractions. These fractions were evaporated in an air stream, hexane
was added, and the fractions were re-evaporated. This process was
repeated several times to insure complete removal of the dichloromethane.
Water
Each water sample (10 1) was extracted at the collection site by passage
through a column of six polyurethane foam plugs at a flow rate of 250 ml/min
using the procedure described by Uthe et_ aj_. (1972). Preparation of the
plugs involved Soxhlet extractions (at least 4 hr) with 1:1 ethyl ether-
hexane (v/v) to remove contaminants followed by coating the plugs with
a 1% solution of DC-200 silicone oil in hexane and air-drying. Following
extraction of water samples, the plugs were removed from the column and
again extracted (4 hr) with 1:1 ether-hexane (v/v). The columns were
rinsed several times with acetone. The combined extracts from the plugs
and column rinsings were reduced to about 5 ml in an air stream before
cleanup by liquid chromatographic procedures similar to those for cleanup
of fish extracts.
-7-
-------
Sediment
Samples were allowed to air dry at room temperature before weighing
out six 25 g sub-samples for analysis. The sub-samples were thoroughly
ground by mortar and pestle, mixed with anhydrous NapSO., and extracted
with 170 ml 1:1 ether-hexane (v/v) in all-glass Soxhlet extractors for
4 hr. The extracts were concentrated to about 10 ml before liquid
chromatographic cleanup in a manner similar to that used for fish
extracts.
Net Plankton and Cladophora
Net plankton and Cladophora samples were transferred to tared centrifuge
tubes and sub-divided into sub-samples of about 1 g where appropriate.
After centrifuging at 2000 rpm for 25 min, the supernatant was decanted
rapidly into separatory funnels, 2 ml acetone was added to each tube,
and the samples were allowed to air-dry. The tubes were weighed and
sample dry weights were determined by difference. Water decanted from
each tube was extracted twice with 25 ml of hexane to recover materials
released from the cells. A 35 ml portion of the extract was added to
the corresponding sample tube and the tube was shaken periodically over
a 36 hr period. The extract was decanted and the residue extracted a
second time with a 35 ml portion of fresh hexane. The combined
extracts were concentrated to 5 ml for cleanup by procedures similar
to those for fish extracts.
Benthos
Mixed benthic fauna (largely Pontiporeia affinis) were dried at
room temperature and separated into at least three 10 g aliquots before
extraction and cleanup by procedures identical to those used for sediment
samples.
PESTICIDE DETERMINATION
Qualitative Determination
Pesticide fractions of all fish and several water, sediment, plankton,
Cladophora,and benthos extracts from silicic acid cleanup were
-------
chromatographed (Varian Aerograph 1500 or 1700) on four gas
chromatographic (GC) columns eluting into electron capture detectors
(^H or 63^-]-) to allow multiple column peak-matching identification of
fraction components. The GC columns and column conditions utilized are
listed in Table 1. To facilitate peak matching, peak retention times
were converted to relative retention times (relative to the retention
time of p,p'-DDE) for each set of column and conditions. A file of
relative retention times of many chlorinated pesticides and metabolites
was compiled from chromatograms of single- and multi-component pesticide
standard solutions and from retention time data reported by Thompson
et^ aj_. (1969). Positions of significant peaks on chromatograms of
pesticide fractions on the four columns were converted to relative retention
times for comparison with the relative retention times of standards in
the file. Peak identity assignments were made based on four matched
relative retention times for peaks of similar height.
Several pesticide and PCB fractions from silicic acid liquid
chromatographic cleanup of fish extracts were examined by gas chromatography/
mass spectrometric (GC/MS) limited mass range scan techniques for DDE,
dieldrin, and DDT. The fractions were chromatographed (Varian Aerograph
1400) on a 1.8 m x 4 mm ID glass column of 3% DC-200 on 60-80 mesh
Gas-Chrom Q, with column and injector temperatures of 175°C and 200°C,
respectively, eluting (by a helium flow of 10 ml/min) directly into the
ion source of a quadrupole mass spectrometer (Finnigan 1015C) focused
on narrow m/e ranges characteristic of the degradation patterns of DDE,
dieldrin, or DDT. DDE ana DDT were monitored by focusing on m/e ranges
of 246-250 and 235-239, respectively, adapting procedures described by
Bonelli (1972). Dieldrin was detected by monitoring the m/e range of
261-267. Identities were based on the response of this selective
detector consistent with appropriate retention times.
Quantitative Determination
For determination of DDE in fish, the 5 ml aliquots taken from extracts
after florisil cleanup were diluted to 10 ml and chromatographed on a
1.5 m x 2 mm ID glass column of 3% DC-200 on 80-100 mesh Chromasorb W, and
-9-
-------
Table 1. GAS CHROMATOGRAPHIC COLUMNS AND CONDITIONS.
Stationary Phase3
Column Length (m)
Column Temperature (°C)
Detector Temperature (°C)
Injector Temperature (°C)
Carrier Gas (Np) Flow
(ml/min)
1.5% 0V- 17/1. 95% QF-1
2.1
185
210
210
15
2% OV-101/3% QF-1
1.5
150
190
210
12
1% QF-1
3
185
210
210
36
3% OV-17
2.1
185
210
210
24
aSolid support was 100-120 mesh Gas-Chrom Q.
All columns are 2 mm ID coiled glass tubes.
-------
eluted with N2 carrier flow of 40 ml/min into an electron capture
detector (3H). The column, detector, and injector temperatures were
200, 210, and 225°C, respectively. The relatively large p,p'-DDE peak
of the chromatograms allowed its determination through peak height
comparison with standards.
Pesticide fractions from silicic acid cleanup of fish, water, sediment,
net plankton, Cladophora,and benthos extracts were chromatographed on
a 3 m x 2 mm ID glass column of 1% QF-1 on 100-120 mesh Gas-Chrom Q to
determine the DDT group pesticides and dieldrin. Column, detector,
and injector temperatures were 180, 200, and 215°C, respectively,
and the N2 flow was 30 ml/min. An electron capture detector (3H or Ni)
was used. All fractions were diluted to 2 ml (with hexane) before
determination except for fish extracts which were diluted to 25 ml.
Areas of peaks identified as DDT group pesticides and dieldrin were
measured by a disc integrator and compared with standards. Since DDE
is not fractionated cleanly into the pesticide fraction during silicic
acid chromatography of extracts of water ,net plankton, Cladophora.and
benthos, the PCB fractions were also chromatographed as above to
determine their DDE content. Sediment PCB fractions could not be
similarily examined because of severe interferences.
The DDE content of several fish PCB fractions from silicic acid
cleanup was determined by GC/MS limited mass range scan techniques.
Chromatographic conditions were similar to those described for the
qualitative determination of DDE. Peak heights were compared with
those of standards.
PCB DETERMINATION
Perchlorination
PCB fractions from silicic acid cleanup of fish, water, sediment,
net plankton, benthos, and Cladophora extracts were perchlorinated by
procedures described by Veith (1973). Fractions were evaporated to
dryness in glass vials, SbCls (0.2 ml) was added to each vial, and the
vials were sealed with teflon-lined screw caps before heating to 180°C
11-
-------
for 6 hr. After cooling to near 0°C in an ice bath, 1 ml of 6N_ HC1
was added to each vial to destroy the residual SbClg. The reaction
solutions were extracted with five 1 ml portions of hexane. The hexane
extracts were combined and passed through a disposable pipet containing
anhydrous Na^SO, to remove traces of water. Some highly colored
extracts from sediment PCB fractions were washed with 1 ml of 10% KOH
in anhydrous methanol to remove interfering inorganics. All
perchlorinated extracts were reduced to 2 ml for GC determination of
decachlorobiphenyl (DCB) except fish extracts which were analyzed at
25 ml.
Determination of Decachlorobiphenyl
Perchlorinated PCB fractions were chromatographed on a 1.5 m x 2 mm
ID glass column of 1.5% OV-17/1.95% QF-1 on 100-120 mesh Gas-Chrom Q
with N9 flow rate of 50 ml/min into an electron capture detector
o L-C o
( H or Ni). Column, detector, and injector temperatures were 200,
210, and 230°C, respectively. Peak heights of DCB in the extracts were
compared with those of standards and the DCB content was converted
numerically to equivalent concentrations of Aroclor 1254.
The results of these analytical methods are reported without correction
with respect to recovery during sample extraction and extract cleanup.
The number of significant digits of the data reported reflects only
analytical precision. Sampling precision was also considered in judge-
ment of the significance of differences between sampling rates.
-12-
-------
SECTION V
RESULTS AND DISCUSSION
FISH
All pesticide fractions from silicic acid cleanup of fish extracts
contained DDT group pesticides and dieldrin, based on identification
by multiple column GC and peak-matching techniques. In addition,
several other common chlorinated hydrocarbon pesticides were identified
in the extracts of fish from some sampling sites using this technique.
Notably, endrin was identified in all fish taken off Prince Edward Point
and from Mexico Bay, but was apparently absent in fish from a transect
between Galloo Island and Stoney Island, the other eastern lake sampling
site. Endrin was not identified in fish collected from western lake
sites off Hamilton, Olcott, and Rochester. The BHC family pesticides
were identified in fish taken off Olcott, Rochester, Prince Edward
Point, and in Mexico Bay, with lindane (y BHC) generally the major
constituent. Heptachlor was identified in slimy sculpin taken off
Rochester. Although identity assignments from a limited file of
compounds were based on peak-matching which is subject to some of the
ambiquity inherent in complex chromatograms, the use of a four-column
system tended to decrease the incidence of these ambiguities.
The GC/MS limited mass range identity assignments of extract components
provided positive identification of chlorinated hydrocarbons in fish.
Using this technique, all fish pesticide fractions examined were shown
to contain DDE, ODD, DDT, and dieldrin. In addition, the PCB fractions
of extracts from most fish contained significant levels of DDE, while
ODD, DDT, and dieldrin were undetectable (less than 2 ng/g on a whole
fish basis).
Concentrations of t-DDT (sum of DDT, DDE, and ODD), dieldrin, and PCBs
(expressed as Aroclor 1254 equivalent) found in whole fish (i.e. wet
weight basis) and the extractable fat contents of the fish are shown
in Table 2. The DDE values shown resulted from preliminary DDE
-13-
-------
Table 2. CHLORINATED HYDROCARBONS AND FAT IN LAKE ONTARIO FISHC
Species
Alewi fe
Alewife
Alewife
Alewife
Alewife
Alewife
Smelt
Smelt
Smelt
Smelt
Smelt
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Location
Hami 1 ton
Olcott
Rochester
Mexico Bay
Prince Edward Pt.
Galloo-Stoney
Hamilton
Olcott
Rochester
Prince Edward Pt.
Galloo-Stoney
Hami Iton
Olcott
Rochester
Mexico Bay
Prince Edward Pt.
Galloo-Stoney
Fat
Of
10
3.6
5.2
3.4
3.1
1.2
2.4
4.9
3.0
4.1
6.7
6.0
9.8
5.1
4.3
5.7
7.6
8.6
DDE
0.46
0.77
0.71
0.79
0.81
0.96
1.36
0.85
1.37
0.86
0.91
0.94
1.10
1.11
1.28
0.83
0.60
ODD
0.07
0.07
0.10
0.07
N.D.
0.08
0.06
0.05
0.13
0.10
0.10
N.D.
0.15
0.10
N.D.
0.15
0.12
DDT
0.14
0.16
0.18
0.13
N.D.
0.18
0.23
0.20
0.29
0.23
0.24
N.D.
0.29
0.26
0.26
0.25
0.17
Total DDT
1 1 n / n u/h(~i~lo "fick
y y/ y wnu i c i i b r
0.67
1.00
0.99
0.99
0.81
1.22
K65
1.10
1.79
1.19
1.25
0.94
1.54
1.41
1.54
1.23
0.89
Dieldrin
0.04
0.03
0.04
0.03
0.03
0.04
0.04
0.02
0.03
0.06
0.07
N.D.
0.06
0.05
0.10
0.11
0.04
PCB
3.12
1.73
4.36
0.94
0.14
3.81
2.47
2.62
3.25
3.49
1.40
2.89
9.17
4.32
6.49
1.58
3.33
N.D. indicates that no determination was made.
-------
determinations on the extracts following florisil liquid chromatographic
cleanup, while the ODD and DDT levels were obtained from determinations
on pesticide fractions following silicic acid cleanup. DDE was also
determined on the silicic acid pesticide fractions by electron capture
GC and on the silicic acid PCB fractions by limited mass range GC/MS
techniques. The sum of DDE in the silicic acid pesticide and PCB
fractions was considerably less than the amount in the preceding
florisil eluate, in some cases as much as 50% less. However since DDE
was the largest peak for chromatograms of extracts after florisil cleanup,
PCB contribution to the DDE peak was probably small. In most cases, the
major contribution to t-DDT values was from DDE. Quantitatively, DDT
and ODD were minor constituents, making up less than 26% and 14% of
the total, respectively. Although dieldrin concentrations shown (Table 2)
are of interest, the low levels observed do not allow evaluation of
possible station-to-station or species-to-species relationships. The
higher levels of t-DDT observed provide a better basis for comparisons.
Individual variation in the chlorinated hydrocarbon contents of the
fish were decreased by sampling an aggregate of ground whole fish of
several age-weight classes for each species collected at each site.
Because chlorinated hydrocarbon levels have been related to the fat
content of the fish (Veith, 1973), these variations likely are further
decreased by examining chlorinated hydrocarbon concentrations in
relation to the extractable fats contents of the whole fish. Table 3
shows t-DDT and PCB levels in fish based on fat content. This data
indicates that the more migratory alewives and smelt accumulate higher
t-DDT levels on a fat basis (averages of 36.2 yg/g and 30.5 yg/g) than
the less migratory slimy sculpin (16.9 yg/g) (Scott and Grossman, 1973).
Relative standard deviations for t-DDT levels (fat basis) for the
species are 53, 36, and 66% for alewives, smelt, and slimy sculpin,
respectively. Comparison of these variations with the average relative
deviation for analytical replicates for extracts of an aggregated
sample (14%) suggests that these variations are partly related to
differences in chlorinated hydrocarbon levels among the sampling sites.
-15-
-------
Table 3. DDT AND PCBs IN LAKE ONTARIO FISH FAT
(yg/g)
Species
Alewife
Alewife
Alewife
Alewife
Alewife
Alewife
Smelt
Smelt
Smelt
Smelt
Smelt
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Slimy Sculpin
Location
Hami 1 ton
Olcott
Rochester
Mexico Bay
Prince Edward Pt.
Galloo-Stoney
Hamilton
Olcott
Rochester
Prince Edward Pt.
Galloo-Stoney
Hami 1 ton
Olcott
Rochester
Mexico Bay
Prince Edward Pt.
Gal loo-Stoney
Total DDT
18.6
19.2
29.1
31.9
67.5
50.8
33.7
36.7
43.7
17.8
20.8
9.6
30.2
32.8
27.0
16.2
10.4
PCB PCB/Total DDT
86.7
33.3
128.2
30.3
11.7
158.8
50.4
87.3
79.3
52.1
23.3
29.5
179.8
100.5
113.9
60.3
38.7
4.7
1.7
4.4
0.9
0.2
3.1
1.5
2.4
1.8
2.9
1.1
3.1
6.0
3.1
4.2
3.7
3.7
-16-
-------
This is supported by the highest relative standard deviation for the
slimy sculpin. Considering the slimy sculpin data shown in Table 3,
the waters off Olcott, Rochester, and of Mexico Bay may contribute
to greater accumulaion of DDT group pesticides by slimy sculpin than
water off Hamilton, Prince Edward Point, and between Galloo and Stoney
Islands. The lake bottom characteristics of these areas may also be
important factors in the chlorinated hydrocarbon accumulation in the
bottom-feeding sculpin.
The lake-wide average for t-DDT (whole fish) in smelt (1.40 yg/g) for
1972 compares favorably with that reported by Reinert (1970) for Lake
Ontario fish captured from 1965 to 1968 (1.58 yg/g) although the
alewife value (0.95 yg/g) is less than half that reported in 1970
(1.99 yg/g). Reinert (1970) did not report on Lake Ontario slimy
sculpin. Dieldrin levels reported by Reinert (1970) for alewives and
smelt caputred from 1967 to 1968 (0.11 yg/g and 0.06 yg/g, respectively)
are comparable to levels in fish for 1972 (0.04 yg/g for alewife and
smelt).
PCB concentrations (2.65 yg/g) found in smelt (Table 2) were similar
to those reported by Veith (1973) for Lake Michigan smelt (2.7 yg/g).
However, concentrations found in alewives (2.35 yg/g) were considerably
lower than values reported for Lake Michigan alewives (4.6 yg/g). For
both lakes, PCB levels were expressed as Arochlor 1254 equivalent.
Slimy sculpin were not included in the Lake Michigan report.
Lake Ontario slimy sculpin exhibited highly variable PCB and t-DDT
concentrations on a fat basis. The relative standard deviation for PCB
levels in slimy sculpin (fat basis) was 65% about a mean of 97.1 yg/g.
Corresponding relative standard deviation values for alewives and smelt
were about 80% (mean = 74.8 yg/g) and 44% (mean = 58.5 yg/g), respectively.
This indicates greater station-to-station variation for PCB accumulation
in slimy sculpin and alewives than in smelt. Furthermore, the waters
near Olcott, Rochester and in Mexico Bay contributed to greater
accumulation of PCB concentrations by sculpin than waters off Hamilton,
-17-
-------
Prince Edward Point, and between Gal loo and Stoney Islands, which
is in agreement with the trend for DDT accumulation.
A large variation was observed in PCB/t-DDT ratios for fish (Table 3).
Average values, however, (2.5 for alewives, 1.9 for smelt, and 4.0 for
slimy sculpin), were comparable to those reported by Veith (1973)
(1.4 for alewives and 2.6 for smelt) for Lake Michigan fish. PCB/t-DDT
ratios were often cited due to chemical similarities between PCBs and
persistent DDT metabolites, although their importance has not been
well established.
WATER
The t-DDT, dieldrin, and PCB concentrations for water are shown in
Table 4. Since there were no apparent relationships between concentra-
tions and depth, with the one exception as discussed below, determinations
from different depths were treated as replicates for each site and
averaged. Lake-wide averages for t-DDT and dieldrin were 28 ng/1 and
4.8 ng/1, respectively. Relative standard deviations for t-DDT and
dieldrin were 54% and 85%, respectively, indicating considerable
site-to-site variation. Waters off Hamilton, Cobourg, and Oswego showed
high levels of t-DDT. Dieldrin levels were highest off Cobourg and
Oswego. The anomalously high dieldrin level for waters of Oswego
resulted from a very high surface water value (34.9 ng/1) which was
averaged with a much lower levels found in samples of deeper waters
(1.7 ng/1 and 1.1 ng/1). In all waters, except off Oswego, DDE was
the major component of the DDT group pesticides. ODD contributed 0 to
19%, while DDT represented 6 to 13% in most cases. The t-DDT in waters
off Oswego contained higher proportions of ODD and DDT, 28% and 26%,
respectively. Waters from the Deep Hole area of the Rochester Basin
showed a t-DDT level of 16 ng/1 with DDT contributing over 40%.
-18-
-------
Table 4. CHLORINATED HYDROCARBONS IN LAKE ONTARIO WATER
(ng/1)
Location
Hami 1 ton
Toronto
Niagara River
Olcott
Cobourg
Rochester
Deep Hole
Oswego
IFYGL
Station
Identifier
1
8
13
30
36
60
75
90
Station
Depth
m
33
76
13
24
24
25
229
21
DDE
37.4
20.5
13.9
26.6
45.2
29.9
9.4
22.4
ODD
2.5
1.6
0.9
7.1
4.5
< 0.5
< 0.5
13.8
DDT
4.5
1.4
2.4
4.6
7.2
2.3
6.5
12.8
Total DDT
44
24
17
38
57
32
16
49
Dieldrin
3.1
3.5
2.1
3.9
9.9
2.2
1.3
12.6
PCB
49
35
97
44
45
40
56
77
-------
PCB concentrations for Lake Ontario waters were between 35 and 56 ng/1,
except for waters off Oswego (77 ng/1) and the mouth of the Niagara
River (97 ng/1). The lake-wide average concentration was 55 ng/1.
Neglecting the two highest concentrations, the lake-wide average
becomes 45 ng/1 with a relative standard deviation of 16%. Other than
these south-shore areas, the PCB content of Lake Ontario waters appears
relatively uniform. The PCB/t-DDT ratios for Lake Ontario waters
averaged 2.1, a value comparable to that for Lake Ontario fish.
Since the water sampling and extraction procedures did not discriminate
between dissolved and particulate fractions, the t-DDT, dieldrin, and
PCB concentrations shown in Table 4 represent "total" concentrations.
The contribution of contaminants associated with net plankton (i.e.,
particles larger than 64 urn) to the "total" levels found in Lake Ontario
waters is estimated to be less than 1%. This estimate was calculated
from the contaminant concentrations found in net plankton (Table 6)
from three areas of Lake Ontario, phytoplankton cell counts determined
for these areas during the month these areas were sampled for
chlorinated hydrocarbons (Stoermer, 1973), and dry weight per cell
values reported for a laboratory algal culture (Lee et_aj_., 1971).
Thus DDT group pesticides, dieldrin, and PCBs in the Lake Ontario waters
sampled are likely dissolved or associated with particles that will
pass through a 64 urn net (e.g., nanoplankton and small inorganic
particles).
SEDIMENT
Sediment concentrations of t-DDT, dieldrin, and PCBs are shown in
Table 5. Lake-wide averages for sediment t-DDT and dieldrin are 22 ng/g
and 1.2 ng/g, respectively, with relative standard deviations of 72%
and 61%, respectively. These variations are indicative of significant
site-to-site differences. Sediments taken off the mouth of the Well and
Canal and at the eastern mid-lake site showed higher levels of dieldrin
and t-DDT. Sediment from three of the eight sites showed DDE contributions
to t-DDT levels of less than 50%. ODD was the major contributor to t-DDT
-20-
-------
Table 5. CHLORINATED HYDROCARBONS IN LAKE ONTARIO SEDIMENT
(ng/g dry sediment)3
Location
Wei land Canal
Niagara River
Olcott
Cobourg
Mid- lake
Rochester
Oswego
Mid-lake East
IFYGL
Station
Identifier
12
13
30
36
46
60
91
93
DDE
12
11
4.8
8.0
11
8.0
9.0
16
ODD
15
3.5
5.6
0.9
5.4
1.5
5.1
31
DDT
12
0.7
1.2
0.9
2.8
0.2
3.8
7.4
Total DDT
39
15
12
10
19
10
18
54
Dieldrin
2.6
1.4
0.9
0.6
0.5
0.9
0.8
2.1
PCB
245
155
80
43
79
84
158
N.D.
J.D. indicates no determination was made.
-------
in sediments from the eastern mid-lake site and off the Well and Canal.
The DDE levels shown in Table 5 must be considered underestimates,
however, since it was not possible to measure the DDE contents of
sediment PCB fractions due to interferences. Lake-wide t-DDT and
dieldrin averages were comparable generally to those found by Leland
et al_. (1973) for southern Lake Michigan top interval sediments (18.5
ng/g and 2.0 ng/g, respectively). However, the Lake Michigan sediments
showed major DDT contributions (ca. 50%) to the t-DDT, while Lake Ontario
data showed DDT contributions no greater than 31%. Sediment PCB
concentrations averaged 120 ng/g. PCB concentrations in sediments off
the mouths of the Welland Canal and Niagara River and off Oswego,
(mean = 184 ng/g) averaged more than twic the concentrations found at
the four other sites (mean = 72 ng/g). Considering the high PCB contents
found for lake water off the mouth of the Niagara River and off Oswego,
the Niagara and Oswego Rivers may be important sources to Lake Ontario
of PCBs associated with settlable particulates.
The PCB/t-DDT ratios exhibited a low relative standard deviation of 33%
about a mean of 7.0. This mean may be too high due to underestimation
of DDE levels. It is unlikely, however, that the DDE content of the
sediment extracts could be great enough to decrease PCB/t-DDT ratios
to levels similar to those for the fish and water.
NET PLANKTON
DDT group pesticides, dieldrin, and PCB levels (dry weight basis) found
in mixed net plankton are shown in Table 6. Although the samples were
predominantly viable phytoplankton, the sampling method also collects
smaller zooplankton, detritus, and suspended inorganic matter.
Contributions of these minor components could not be assessed. Lake-wide
averages for t-DDT and dieldrin were 3.5 yg/g and 0.12 yg/g on a dry
weight basis, respectively, with corresponding relative standard
deviations of 42% and 91%. In nearly every case, DDE comprised over
75% of the t-DDT concentrations.
-22-
-------
Table 6. CHLORINATED HYDROCARBONS IN LAKE ONTARIO NET PLANKTON
\a
(yg/g dry weight)'
GO
i
Location
Hamilton
Mid-lake West
Cobourg
Mid-lake
Rochester
Deep Hole
Mid-lake East
IFYGL
Station
Identifier
1
10
36
45
60
75
96
DDE
4.00
3.52
3.26
1.49
1.19
5.89
2.45
ODD
0.09
0.37
< 0.05
0.07
< 0.05
0.04
0.09
DDT
0.04
0.12
< 0.05
0.78
< 0.05
< 0.05
0.86
Total DDT
4.1
4.0
3.3
2.3
1.2
5.9
3.4
Dieldrin
0.24
0.25
< 0.05
0.16
0.02
0.02
0.18
P'CB
3.4
10.6
7.6
3.6
N.D.
11.8
6.0
N.D. indicates that no determination was made.
-------
Net plankton PCB levels averaged 7.2 yg/g. Plankton from the Deep Hole
of the Rochester Basin and the mid-lake west site, show high PCB levels
contributing to a relative standard deviation of 49% for the lake-wide
average PCB concentration. The average PCB/t-DDT ratio (3.1) was
somewhat higher than for water or fish.
Chlorinated hydrocarbon levels for plankton appeared high compared to
concentrations in fish. However, plankton concentrations were expressed
on a dry weight basis while fish concentrations were on a whole fish
(wet weight) basis. Assuming whole fish are about 20% dry weight
(F.D.A., 1969), typical fish t-DDT, dieldrin, and PCB concentrations were
7.0 yg/g, 0.3 yg/g, and 13.2 yg/g dry weight (smelt), respectively.
On this basis, net plankton concentrations of these chlorinated
hydrocarbons were about 50% less than concentrations in fish.
CLADOPHQRA
The results of determinations of DDT group pesticides, dieldrin, and
PCB levels in extracts of Cladophora are shown in Table 7. Most samples,
except those off Toronto and in the Black River Bay, were from the
south shore of Lake Ontario. The exact sampling site locations of four
of the samples is uncertain. The average t-DDT, dieldrin, and PCB
levels (dry weight basis) were 229, 13, and 515 ng/g, respectively, with
relative standard deviations of 40, 64, and 39%, respectively. These
concentrations are 10 to 100 times less than for net plankton. The
average PCB/t-DDT ratio of 2.3 was near the corresponding averages for
fish and water.
BENTHOS
DDT group pesticide, dieldrin, and PCB levels determined for extracts
of benthic fauna, largely Pontiporeia, are shown in Table 8. Of the
three samples taken, one off Hamilton showed t-DDT, dieldrin, and PCB
levels approximately four times those determined for benthos off Oswego
and Rochester. Also, ODD made a significantly larger contribution to the
t-DDT in benthos off Rochester than other samples. Average t-DDT and
PCB levels, 99 ng/g and 471 ng/g on a dry weight basis, respectively,
-24-
-------
Table 7. CHLORINATED HYDROCARBONS IN LAKE ONTARIO CLADOPHORA
(ng/g dry weight)
Location
Black River Bay
Black River Bay
South Shore3
South Shore9
South Shore9
South Shore9
Rochester
Toronto
aSpecific sampling
DDE
344
129
97
194
347
192
165
196
site
Table 8. CHLORINATED
Location
Hamilton
Rochester
Oswego
DDE
124
34
26
ODD
4.8
0.45
19
26
17
30
5.2
13
unknown.
DDT
7.4
1.9
2.5
4.7
1.1
16
6.0
8.0
HYDROCARBONS IN
(ng/g dry
ODD
26
1.8
3.4
weight)
DDT
59
6.1
2.4
Total DDT
357
131
119
225
365
238
176
217
LAKE ONTARIO
Total DDT
209
42
32
Dieldrin
1.9
6.5
14
14
4.0
25
16
21
BENTHIC FAUNA
Dieldrin
14.8
2.9
3.0
PCB
860
333
232
607
436
576
411
666
PCB
976
341
97
-25-
-------
were quite comparable to levels reported by Flotard (1974) for
Pontiporela of the western shore of Lake Michigan, 130 ng/g and 310 ng/g,
respectively. The PCB/t-DDT ratios averaged 5.3. This value is somewhat
higher than that calculated from the concentrations reported by Flotard
(1974) or ratios calculated for all other samples reported except sediment.
Although some sediment contamination may be indicated, the benthos PCB/t-DDT
ratio is comparable to that for slimy sculpin (4.0), whose diet is
primarily benthic fauna (Scott and Grossman, 1973).
-26-
-------
SECTION VI
REFERENCES
BoneTli, E.J. 1972. Gas Chromatograph/Mass Spectrometer Techniques
for Determination of Interferences in Pesticide Analysis. Anal.
Chem. 44:603-606.
Flotard, R.D. 1974. PCBs in Lake Sediments. Ph.D. Thesis (Water
Chemistry), University of Wisconsin, Madison (in progress).
Kaiser, K.L.E. 1974. Mirex: An Unrecognized Contaminant of Fishes
from Lake Ontario. Science 185:523-525.
Lee, C.C., R.F. Harris, J.K. Syers, and D.E. Armstrong. 1971.
Adenosine Triphosphate Content of Selenastrum capricornutum.
Appl. Microbiol. 21:957-958.
Leland, H.V., W.N. Bruce, and N.F. Shimp. 1973. Chlorinated Hydrocarbon
Insecticides in Sediments of Southern Lake Michigan. Environ. Sci.
Technol. 7:833-838.
Reinert, R.E. 1970. Pesticide Concentrations in Great Lakes Fish.
Pestic. Monit. J. 3:233-240.
Scott, W.B. and E.J. Crossman. 1973. Freshwater Fishes of Canada.
Fish. Res. Bd. Can. Bulletin 184, Ottawa. 966 p.
Stoermer, E.F. 1973. Analysis of Phytoplankton Composition and Abundance
During IFYGL. In: First Annual Reports of EPA Grants Funded for IFYGL.
Ecol. Res. Series #EPA-660/3-73-021. U.S. Environmental Protection
Agency, Grosse He Laboratory, Grosse He, Michigan, pp. 90-109.
Thompson, J.F., A.C. Walker, and R.F. Moseman. 1969. Evaluation of
Eight Gas Chromatographic Columns for Chlorinated Pesticides.
J.A.O.A.C. 52:1263-1277.
U.S. Food and Drug Administration. 1969. Pesticide Analytical Manual,
Volume 1. U.S. Department of Health, Education and Welfare, Washington,
D.C.
-27-
-------
Uthe, J.F., J. Reinke, and H. Gesser. 1972. Extraction of Organochlorine
Pesticides from Water by Porous Polyurethane Coated with Selective
Absorbent. Environ. Letters 3:117-135.
Veith, G.D. 1970. Environmental Chemistry of PCBs in the Milwaukee
River. Ph.D. Thesis (Water Chemistry), University of Wisconsin,
Madison. 180 p.
Veith, G.D. 1973. Chlorinated Hydrocarbons in Fish from Lake Michigan.
A final report on Project #16020PBE to the U.S. Environmental Protection
Agency, National Water Quality Laboratory, Duluth, Minnesota. University
of Wisconsin-Madison, Water Chemistry Department, Madison, Wisconsin.
129 p.
-28-
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-660/3-75-022
3. RECIPIENT'S ACCESSI Of* NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
Chlorinated Hydrocarbons in the Lake Ontario
Ecosystem.
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
C.L. Haile, G.D. Veith*, G.F. Lee*, W.C. Boyle
*NWQL, Duluth, Minn.; **Univ. of Texas - Dallas
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Water Chemistry Program
University of Wisconsin
Madison, Wisconsin
11. CONTRACT/GRANT NO.
R-800608
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Lake Ontario fish, water, sediment, net plankton, Cladophora, and benthos were
examined for DDT group pesticides, dieldrin, and PCBs. Endrin, BHC group
pesticides, and heptachlor were also identified in some fish samples. Average
concentrations ranged from 28 ng/1 (t-DDT), 4.8 ng/1 (dieldrin), and 55 ng/1
(PCBs as Aroclor 1254 equivalent) for water to 1.40 yg/g (t-DDT), 0.07 yg/g
(dieldrin), and 5.15 yg/g (PCBs) for whole fish. DDE levels were generally
similar to t-DDT levels, except for sediments where ODD and DDT contributed
significantly to t-DDT values. PCB/t-DDT ratios averaged 2.6 for all samples
except for sediment (7.0) and benthos (5.3).
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
PCBs
DDT
Dieldrin
Biota
Water
Sediment
Lake Ontario
3. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
21. NO. OF PAGES
20. SECURITY CLASS (This page)
22. PRICE
EPA Form 2220-1 (9-73)
* U.S. GOVERNMENT PRINTING OFFICE: I975-698-638 /I62 REGION 10
------- |