An:hivell
of
E novni nt aornnrinne~nl ~l li~o n o
Arch. Environ. Contam. Toxicol. 13,373-381 (1984)
9 1984Springer-VedagNew YorkInc.
Levels of Polychlorinated Biphenyls, DDE, and Mirex in Waterfowl Collected in New York State, 1979-1980 Kihyun S. Kim .1, Michael J. Pastel*, Jai S. Kim .2, and Ward B. Stone** * Department of Atmospheric Science, State University of New York at Albany, 1400 Washington Avenue, Albany, New York 12222 and ** Wildlife Pathology, Wildlife Resources Center, New York State Department of Environmental Conservation, Delmar, New York 12054
Abstract. Levels of polychlorobiphenyls (PCBs),
DDE, and mirex were measured in the subcutaneous fat, breast muscle, liver, and brain of sixty-three waterfowl collected in New York State during 1979 and 1980. Mean PCB levels were 7.5 gg/g in fat and 1.3 #g/g in breast muscle on a wet weight basis. The FDA tolerance level is 3.0 gg/g in fat on a wet weight basis. Mean DDE and mirex levels were 0.34 #g/g and 0.10 #g/g in fat and 0.16 ~g/g and 0.07 /zg/g in breast muscle on a wet weight basis, respectively. Comparisons and correlations were made of contaminant levels in the various tissues by different concentration bases, and PCB concentrations were compared to the Aroclor | (PCB) type. Potential health hazards are discussed. Comparisons to earlier studies show declined levels. Mergansers are the most contaminated species.
Waterfowl are susceptible to adverse effects of environmental contamination by industrial chemicals and pesticides. Reviews are available concerning the use and distribution of many of these contaminants, including polychlorinated biphenyls (PCBs) (Hutzinger et al. 1974), 1-1'-(dichloroethylidene) bis 4-chlorobenzene [CAS 72-55-9] (DDE) (O'Shea et al. 1980), and 1,1a,2,2,3,3a,4,5,5,5a,5b,6-dodecachloro- 1,3,4-metheno- 1H-cyclobuta [cd]pentalene [CAS 2385-85-5] (mirex) (Kaiser 1978). PCBs are toxic to avian systems by themselves (Bush et al. 1Permanent address: Massachusetts Institute of Technology, Cambridge, MA 2 To whom correspondence should be addressed
1974) and in conjunction with DDE (Sodergren and Ulfstrand 1972). PCBs and DDE are widespread throughout New York State. Mirex is centered mainly in the Niagara River-Lake Ontario region (Pickett and Dossett 1979). Migratory waterfowl provide a good indication of general pollution of North American waterways. Many birds travel through a large region and are exposed to a wide range of environmental contaminants. Since the birds have relatively large amounts of fat, lipophilic contaminants, such as PCBs and many pesticides, are of special concern. During migration, the birds rely heavily on their fat reserves (King and Farner 1965). High levels of organochlorine contaminants may pose a problem to the aquatic birds and the hunters who shoot them for food. Since PCBs pose a potential health hazard to humans, the Federal Food and Drug Administration (FDA) has set tolerance levels limiting the amount of PCBs in milk and dairy products, eggs, poultry, and fish and shellfish that can be sold in interstate commerce (FDA 1979). Poultry tolerance levels are enforced by the U.S. Department of Agriculture (USDA) (FDA 1979). Neither agency has jurisdiction over wildfowl. The FDA and U S D A methods of analysis differ slightly since they monitor different products. FDA uses the edible portion (e.g., in fish) and performs a solvent extraction of lipids with a coextraction of the lipophilic contaminants (FDA 1977). For poultry, U S D A methods specify using the fat tissue, which is heated and the melted lipids drawn off for analysis (Horwitz 1980). The most common concentration basis reported in the literature is the wet
K.S. Kim et al.
374
weight basis, although some reports (Cromartie et al. 1975) use the lipid basis. The objectives of the current study were to determine the levels of PCBs, DDE, and mirex in various tissues of w~.terfowl collected in New York State, to compare these levels to the tolerance levels established for poultry, to provide an indication of possible health hazards to hunters who consume the birds, to estimate the PCB Aroclor | type, and to investigate comparisons and correlations based on tissue, sex, age, collection site, species, and feeding habits according to different concentration bases (i.e., wet-, dry-, or hexane-extractable lipid (HEL)weight).
hexane-extractable lipid (HEL) determination. After evaporation of the solvent, the vial was reweighed. The remaining 9.0 mL portion of the extract was concentrated to 2 mL under dry nitrogen. Some sample extracts, including fat and merganser breast muscles, developed a precipitate upon concentration. These were brought to a volume of 10.0 mL, of which only 2.0 mL was used, to avoid saturating the chromatographic column. The appropriate dilution factor was included in subsequent calculations. The extract was transferred to a column containing 10 g of 2% deactivated Florisil| (60/100 mesh) topped with 2 g anhydrous Na2SO4. Florisil was activated at 450~ cooled, and deactivated with distilled water. The column was eluted with hexane, and the first 40 mL collected. This fraction contains PCBs, DDE, and mirex. More polar compounds, such as triglycerides, dieldrin, and DDT, remained on the column. The collected fraction was treated with mercury to remove any possible sulfur contamination, then concentrated to 1.0 mL for analysis.
Materials and Methods
Analysis Sample Collection Sixty-three waterfowl were collected from New York State and sent to the Pathology Unit of the New York State Department of Environmental Conservation (DEC), where they were assigned a log number and subjected to a pathological examination. The birds included two Canada geese (Branta canadensis), two American brant (B. bernicla), sixteen mallards (Anas platyrhynchos), two domestic White Pekin ducks (A. p. domesticus), eight black ducks (A. rubripes), one mallard-black duck hybrid, three bluewinged teal (A. discors), three green-winged teal (A. carolinensis), one gadwall (A. strepera), five greater scaup (Aythya marila), one goldeneye (Bucephala clangula), three bufflehead (B. albeola), two white-winged scorer (Melanitta deglandi), one surf scoter ( M. perspicillata ), one hooded merganser ( Lophodytes cacullatus ), six American mergansers (Mergus merganser), three red-breasted mergansers (M. serrator), one eared grebe (Podiceps caspicus), and two American coot (Fulica americana). Fifteen birds were collected from the Niagara River, in western New York, and thirty-two from the Hudson River, in eastern New York. The sex, age (juvenile or adult), gross weight, collection site, and date and cause of death were recorded for each bird.
Sample Preparation During necropsy, portions of the subcutaneous fat, breast muscle, and the entire liver and brain were removed from the bird and plaeed in a clean glass jar with an aluminum foil-lined lid. The samples were stored at - 1 5 ~ until prepared for analysis. Prior to analysis, the sample was thawed and minced. If the sample weighed more than 10.0 g (wet weight), a 10.0 g subsample was used; otherwise, the entire sample was used, and the wet weight recorded. The sample was frozen in tared glass centrifuge tubes and lyophilized for 15 hr, and the dry weight recorded. The sample was transferred to a Soxhlet apparatus and extracted with 100 mL hexane for 5 hr. The extract was quantitatively transferred to a Kuderna-Danish apparatus equipped with a graduated receiving tube, and concentrated to about 5 mL. The volume was brought to 10.0 mL with hexane. A 1.0 mL aliquot was removed and placed in a tared glass vial which was set aside for
Analysis was performed with a Hewlett-Packard Model 5840A digital gas chromatograph equipped with a 63Ni electron capture detector and an automatic liquid sampler, all under microprocessor control. The column used was a 2 m • 2 mm ID glass packed with 2% Apiezon L on Chromosorb W-HP (100/120 mesh). The column was maintained at 180~ for 5 min, then increased by 3~ to 225~ Total time was 95 rain. The injection volume was 4.5 ~tL, and the temperature 225~ The detector was maintained at 300~ The carrier gas was argon-methane (95:5) with a flow rate of 25 mL/min). The instrument was calibrated as described in a previous study (Pastel et al. 1980) using a mixture of 2 # g / m L each Aroclors| 1016, 1221, 1254, and 1260, plus 50 ng/mL, 3,4,3',4'-tetrachlorobiphenyl and 100 ng/ml each p,p'-DDE and mirex. Thirty-eight peaks were resolved in the standard. The major PCB components of each peak were assigned as described in the previous study, with additional information from more recent capillary column work (Bush et al. 1982). The pesticide peaks and their response factors were determined by the analysis of individual standard solutions (100 ng/mL). The E C / G C results were filed in a Univac 1100/80 computer, and a Basic program run which calculated PCB, DDE, and mirex concentrations on wet weight, dry weight, and HEL weight bases. Total PCB was measured by summing all of the calibrated peaks. Individual Aroclors were estimated by a single peak unique to that Aroclor. The peak due to trichlorobiphenyls was used for Aroclor | 1016 [A-1016], one due to a hexachlorobiphenyl for A-1254, and one due to a heptachlorobiphenyl for A-1260. Since the present work was completed, high-resolution capillary gas chromatographic analysis has shown that for environmental sampies, the pattern of peaks in the trichlorobiphenyl region more closely resembles that for A-1242 than for A-1016 (B. Bush, NYS Health Dept., 1981: unpublished data). Since A-1016 was used in the calibration mixture, the results are reported in terms of A-1016. Recoveries for the method were reported previously based on peak components in each Aroclor mixture (Pastel et al. 1980). The recoveries for most components ranged from 60% to 80% and the results are uncorrected for recovery. The detection limit for PCBs was 0.010 #g/g for a 10.0 g (wet weight) sample. The detection limit for DDE was 0.001 /~g/mL with no PCB interference and 0.01/~g/mL with PCB interference.
375
PCBs and Chlorinated Pesticides in Waterfowl, New York Table 1. Description of samples a Collection Age
Site
County
F F
Ad Ad
2.75 NR
Peekskill
Rock West
6/77 3/79
diazinon trauma
9-2 8-1
F M
Ad Ad
1.25 0.93
Bay Park L Ontario
Nas Jeff
1/8o 10/79
trauma trauma
75-33 75-34 1-16 1-25 4-16 1-17 1-18 4-11 4-12 4-13 4-14 4-15 4-18 4-19 4-24 4-25
F F F F F M M M M M M M M M M M
Ad Ad Ad Ad Ad Ad Ad Ad Juv Juv Ad Ad Juv Ad Ad Ad
NR NR 1.20 1.21 1.32 1.31 1.25 1.39 1.23 1.37 1.29 1.45 1.18 1.32 1.17* 1.13"
Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson Hudson
Col Col Col Col Col Col Col Col Col Col Col Col Col Col Col Col
1C ~79 1C r79 10 r79 1C 179 10 ~79 10 r 10 r 10 t79 1s r79 10179 10 t79 10 t79 10t79 10 t79 10/79 10 t79
shot shot shot shot shot shot shot shot shot shot shot shot shot shot shot shot
1-7 3-29
M M
Ad Ad
2.11 3.81
Nassau L
West Rens
10/79 11/79
sacrificed sacrificed
4-10 4-20 4-21 9-7 4-9 4-22 4-23 9-1
F F F F M M M M
Ad Ad Ad Ad Ad Ad Juv Ad
1.15 1.07 0.90* 1.12 1.29 1.09" 0.96* 1.29
Hudson R Hudson R Hudson R Reynolds Ch Hudson R Hudson R Hudson R Shelter I
Col Col Co/ Nas Col Col Col Surf
10/79 10/79 10/79 11/79 10/79 10/79 10/79
1/80
shot shot shot shot shot shot shot shot
Mallard/black hybrid
8-33
M
Ad
1.29
Atlantic O
Surf
12/79
shot
Blue-winged teal
I-9 1-13 1-14
F F F
Juv Juv Juv
0.44 0.40 0.43
Hudson R Hudson R Hudson R
Col Col Col
10/79 10/79 10/79
shot shot shot
Green-winged teal
4-26 4-27 4-28
F F F
Juv Juv Ad
0.35 0.31 0.31
Hudson R Hudson R Hudson R
Col Col Col
10/79 10/79 I0/79
shot shot shot
Gadwall
4-17
F
Juv
0.70
Hudson R
Col
10/79
shot
Greater scaup
8-10 8-31 8-32
F F F
Ad Ad Ad
0.84 0.90 0.85
Niagara F Atlantic O Atlantic O
Nia Surf Surf
12/79 1/80 12/79
trauma shot shot
Canada Goose American Brant Mallard
White Pekin Black Duck
Sex
20-2 61-32
Death
Gross weight (kg)
Species
Log number
The detection limits for mirex were 0.04 t~g/mL and 0.001 ttg/mL, respectively, with and without PCB interference. The presence of PCBs, DDE, and mirex were confirmed with a Finnigan Series 9500/1015D/6000 G C / M S / D a t a System, following the procedures reported previously (Pastel et al. 1980). The detection limits for GC-MS were 20 ng A-1254, 3 ng DDE, and 3 ng mirex. Quality control (QC) procedures, based on the recommendations of the American Chemical Society (MaeDougall 1980), included the analysis of system blanks and QC standards (every eighth analysis). All solvents were ultra-high purity. All reagents were
R R R R R R R R R R R R R R R R
Date
Cause
solvent washed. Glassware was washed with strong detergent, distilled water rinsed, baked out (200~ 6 hr), and solvent rinsed. No spurious contamination peaks were detected in the system blanks.
Results Table 1 indicates the species, assigned log numbers, sex, a g e , g r o s s w e i g h t , c o l l e c t i o n s i t e a n d c o u n t y ,
376
K. S. Kimet al.
Table 1. (cont'd)
Log number
Sex
Age
Gross weight (kg)
8-34 7-32
F M
Ad Juv
Goldeneye
7-25
F
Bufflehead
8-11 1-15 7-26
White-winged scoter
Species
Collection
Death
Site
County
Date
Cause
0.97 1.20
Atlantic O Niagara R
Surf Nia
12/79 12/79
shot accident
Juv
1.04
Niagara R
Nia
12/79
accident
F M M
Juv Ad Juv
0.37 0.45 0.47
Niagara R Hudson R Niagara R
Nia Col Nia
12/79 10/79 12/79
accident shot accident
1-22
F
Ad
1.09
1-19
M
Ad
1.54
Hudson R Hudson R
Col Col
10/79 10/79
shot shot
Surf scoter
1-11
F
Juv
0.64
Hudson R
Col
10/79
shot
Hooded merganser
7-33
F
Ad
1.11
Niagara R
Nia
12/79
accident
American merganser
7-22 7-17 7-18 7-19 7-20 7-21
F M M M M M
Ad Ad Ad Ad Ad Ad
1.50 2.05 2.12 2.04 2.04 2.14
Niagara Niagara Niagara Niagara Niagara Niagara
R R R R R R
Nia Nia Nia Nia Nia Nia
12/79 12/79 12/79 12/79 12/79 12/79
accident accident accident accident accident accident
Red-breasted merganser
7-28 7-23 7-24
F M M
Ad Ad Ad
1.06 1.66 1.78
Niagara R Niagara R Niagara R
Nia Nia Nia
12/79 12/79 12/79
accident accident accident
Eared grebe
7-29
F
Juv
0.59
Niagara R
Nia
12/79
accident
American coot
1-10
F F
Juv Juv
0.52 0.40
Hudson R Hudson R
Nia Nia
10/79 10/79
shot shot
1-12
a Abbreviations & Explanations: Sex: Age: Gross weight: County:
F--female, M--male Ad--adult, Juv--juvenile *--indicates entrails removed, NR--not recorded Rock--Rockland West--Westchester Nas--Nassau Jeff--Jefferson Col--Columbia Rens--Rensselaer Surf Suffolk Nia--Niagara Cause of death: diazinon--pesticide poisoning trauma--flew into building or struck by car shot--shot by hunter sacrificed--killed by owner accident--swept over Niagara Falls
a n d t h e d a t e a n d c a u s e o f d e a t h for e a c h b i r d . C a n a d a goose N o . 20-2 d i e d o f d i a z i n o n p o i s o n i n g , Buff l e h e a d N o . 8-11 w a s slightly e m a c i a t e d , a n d W h i t e P e k i n N o . 1-7 w a s s a c r i f i c e d b e c a u s e it h a d b u m b l e f o o t , a n o n - t e r m i n a l f o o t i n f e c t i o n . O t h e r w i s e , all o f t h e b i r d s w e r e in g o o d h e a l t h , as i n d i c a t e d b y t h e gross w e i g h t s a n d p a t h o l o g i c a l e x a m i n a t i o n s . E x c e p t f o r t h e t w o d o m e s t i c d u c k s , all o f t h e w a t e r f o w l
a r e m i g r a t o r y . C o l l e c t i o n sites a r e m a r k e d b y c o u n t y on t h e m a p in F i g u r e 1. T h e r e s u l t s o f t h e a n a l y s e s a r e p r e s e n t e d in T a b l e s 2 a n d 3. T a b l e 2 lists t h e P C B , D D E , a n d m i r e x c o n c e n t r a t i o n s on a w e t w e i g h t b a s i s for t h e f o u r tissues a n a l y z e d for all s a m p l e s . T h e b i r d s a r e l i s t e d b y species a n d log n u m b e r . T a b l e 3 s u m m a r i z e s t h e o v e r a l l m e a n s a n d s t a n d a r d d e v i a t i o n s for t h e c o n -
PCBs and Chlorinated Pesticides in Waterfowl, New York N
LAKE ONTARIO
,-~)
NIAGARA .- ..... _~_...... " ~-
ER,E~ LAKE
(
~
('
HUDSON /.,VER LONGISLAND SOUND
~ffLANTIC
OCEAN
Fig. I. Map of collection sites by counties: 1) Niagara, 2) Jefferson, 3) Rensselaer, 4) Columbia, 5) Rockland, 6) Westchester, 7) Nassau, and 8) Suffolk
taminants for the four tissues on wet weight, dry weight, H E L weight bases. The term H E L is used, because not all lipids are hexane-extractable, and not all extractions in other studies are performed using hexane as the solvent. A value below the detection limit was treated as zero.
Discussion
Statistical comparisons and correlations were made between the various sets of data using the F-test for variance, t-test for means, and r-test of correlations (Natrella 1963). Unless otherwise indicated, all tests were performed with confidence a = 0.01. The results show that the mean PCB concentration for fat on a wet weight basis (7.5 #g/g) was well above the FDA 3.0 #g/g tolerance level for domestic poultry (FDA 1979). However, PCB in breast muscle on a wet weight basis (1.3 #g/g) was less than 3.0 #g/ g. Mean DDE and mirex levels were within the FDA tolerance levels for all tissues. There was no significant difference for PCB, DDE, or mirex levels in fat (wet weight) between males and females, juveniles and adults, or birds collected from the Hudson River and those from the Niagara River. A comparison of mallards and black ducks v s mergansers shows no significant difference for contaminants in fat (wet weight). However, in the breast muscle (wet weight) there is a difference in PCB (a = 0.05), and in the liver (wet weight) there are differences in DDE and mirex (both a = 0.05). In all three cases, the mergansers are higher. The higher levels of PCBs in the mergansers may be explained by higher lipid concentrations in their breast muscle. H E L weight expressed as a percentage of wet weight
377
shows average lipid concentrations of 5.4% for mergansers and 2.1% for the other birds. Lipid levels in the liver ~ire about the same (3.1% and 3.7%, respectively). Mergansers are fish-eaters, but a comparison based on feeding habits (predominantly fish and macroinvertebrate feeders v s all others) shows no significant difference in the contaminant levels in any tissue Investigations on different bases were made of the relationships of PCB levels in the various tissues. These show no significant difference between fat, on wet or dry weight bases and fat on an H E L basis. Comparisons between levels in fat and muscle show significant differences (a = 0.01) on any basis. DDE and mirex concentrations were significantly greater in fat tissue, and PCB concentrations were more than five times greater in the fat on a wet-weight basis. However, a significant difference was not discernible between fat on a wet-weight basis and muscle on a lipid-weight basis, even at a = 0.1. There is no correlation between wet weight fat and muscle (r = 0.01), dry weight fat and muscle (r = +0.13), or wet weight fat and liver (r = +0.01). However, there is a correlation of r = +0.59 (significant at a = 0.01) between fat (wet weight) and muscle ( H E L weight) PCB levels. There is no similar correlation between fat and liver PCB levels (r = +0.30). Although there was no significant difference in concentrations of PCBs by collection site, different types of Aroclors are evident, as shown in Table 4 and in Figure 2. Table 4 lists the estimated Aroclor levels and ratios of A-1016 and A-1260 to A-1254 according to the two main collection sites--the Niagara River and the Hudson River; mean levels of DDE and mirex are also included. These are illustrated in bar chart form for muscle and fat (wet weight) in Figure 2. The levels of A-1254 and A-1260 in fat are similar for both sites, and the ratio, A-1260/A-1254, is also similar. For all tissues, the A- 1016/A- 1254 ratio was substantially higher for birds from the Niagara River than for those from the Hudson River. This matches the contamination patterns for these two areas, since PCB contamination of the Hudson is predominantly from an A-1016 type and of the Niagara from an A-1254 type (Pastel e t a L 1980; Bush e t al. 1982). However, the birds do not acquire all of their contaminant burdens from their respective collection sites, as indicated by the levels of A- 1260 in the Hudson birds and A- 1016 in the Niagara birds. Neither collection site yielded birds contaminated exclusively by one type of Aroclor. Pesticide levels are higher in the birds from the Niagara River. Although the birds were collected in New York State, they acquire contaminants from throughout their migratory regions.
9-2 8-1
75-33 75-34 1-16 1-25 4-16 1-17 1-18 4-11 4-12 4-13 4-14 4-15 4-18 4-19 4-24 4-25
1-7 3-29
4-10 4-20 4-21 9-7 4-9 4-22 4-23 9-1
Can ad a goose
American brant
Ma llar d
White Pekin
Black duck
1-13 1-14
4-26 4-27 4-28
Greenwinged teal
1-9
Bluewinged teal
8-33
20-2 61 - 32
Species
Mallard/ Black Hybrid
Log number
6.1
*
0.69 0.51
12
16
*
2.7 3.2 5.0 3.4 5.1 19. 14 1.8
*
0.14
0.63 0.99 4.8 26. 7.9 2.8 11 2.5 22 3.4 2.1 0.01 5.1
5.0 6.1
0.96
*
*
* *
P CB
0.01 0.01 *
ND
ND ND
*
ND 0.18 0.15 ND 0.10 1.0 0.22 ND
0.05 *
ND ND * 0.06 0.01 0.17 ND 0.31 0.12 0.28 ND 0.32 0.15 ND ND ND
* 0.02
* *
DDE
Subcutaneous fat
ND ND *
ND ND ND
*
ND ND ND ND ND ND 0.39 ND
ND *
ND ND * ND ND ND ND ND ND ND ND ND ND ND ND ND
* ND
* *
Mirex
~
9
ND ND
*
ND ND ND
0.32 1.2 0.81
0.22 0.29
ND
ND ND ND ND ND ND 0.02 0.02
0.06 0.27 0.14 0.34 0.10 0.17 0.13 0.20
0.16
0.11 *
ND ND ND ND ND ND ND ND 0.t6 ND ND 0.02 0.01 ND
0.39
0.64 0.79 0.23 0.55 0.37 0.45 0.12 0.40 0.30 0.73 0.05 0.47 0.56 0.05
0.14
0.24 *
* ND
ND ND
DDE
0.01
9
9
9
0.40 0.50
PCB
Breast muscle
* * *
* ND ND
0.28 1.3 0.75
*
0.45 * * * 1.0 * * 0.45
0.46 0.22
1.5 0.31 0.29 0.11 0.32 0.48 0.33 0.49 0.66 1.6 0.05 0.10 * *
*
*
0.24 0.90
0.28 0.43
PCB
Liver
ND ND ND
ND
ND ND ND ND ND ND 0.01 ND
ND *
ND ND ND ND ND ND ND ND ND ND ND ND ND ND
*
ND
* ND
ND ND
Mi re x
C o n t a m i n a n t s ( # g / g - - w e t weight)
Table 2. PCB, DDE, and mirex concentrations ( # g / g - - w e t weight) in four tissues a
* *
*
ND ND ND
*
ND * * * ND * * 0.09
ND 0.04
ND 0.03 ND ND ND ND ND ND 0.25 ND ND 0.01 * *
*
*
ND 0.10
ND ND
DDE
* *
*
ND ND ND
*
ND * * * ND * * 0.01
ND 0.01
ND ND ND ND ND ND ND ND ND 0.25 ND ND * *
*
*
ND ND
ND ND
Mirex
0.05 *
0.98
* * *
0.14
0.30 0.15 0.94 0.16 0.16 0.21 0.04 0.02
0.28 1.2
0.15 0.43 0.02 0.16 0.14 0.24 0.07 0.20 1.1 0.46 0.24 0.07 3.0 0.09
*
*
0.22 *
* *
P CB
Brain
ND *
ND
* * *
ND
ND ND 0.01 ND ND ND ND ND
0.02 ND
ND ND ND ND ND ND ** ND ND ND ND ND ND ND
*
*
ND *
* *
DDE
ND *
ND
* * *
ND
ND ND 0.01 0.01 0.01 ND ND ND
0.02 ND
ND ND ND ** ND ND ** ND ** 0.10 ** ND ND ND
*
ND *
* *
M ir ex
OO
7-33
Surf scorer
Hooded merganser
a Explanations: * - - N o t measured ** - - < 0 . 0 0 4 Izg/g N D - - N o t detected PCB < 0.010 DDE < 0.001 < 0.01 Mirex < 0.00l < 0.04
Coot
American
vg/g #g/g ~tg/g gg/g ~g/g
1-10 t-12
2.3
8.6
10 14
0,05
26 * 1.2
*
*
1,7 9,8
3.9
14
5,4 11
53 0,24 2.8
1.2
2.1 7,9 15 * 3,4
3.6
PCB
ND ND
0.002
2.6 * 0.17
0.59 2.0 * 0.78 * 0.18
1.1
ND
0.17 ND
ND ND ND
ND
ND 1.6 1.5 * 0.54
ND
DDE
Subcutaneous fat
(no PCB interference) (PCB interference) (no PCB interference) (PCB interference)
1-11
White-winged scoter
7-29
1-22 1-19
Bufflehead
Eared grebe
8-11 1-15 7-26
Goldeneye
7-28 7-23 7-24
7-25
Greater scaup
Redbreasted merganser
8-10 8-31 8-32 8-34 7-32
Gadwall
7-22 7-17 7-18 7-19 7-20 7-21
4-17
Species
American merganser
Log number
Table 2. (cont'd)
ND ND
ND
2.5 * 0.05
0.26 ND * ND * 0.19
0.39
ND
ND ND
ND ND ND
ND
0.13 ND ND * 0,38
ND
Mirex
* ND ND
0.10 ND ND
0.45 0.51 0.93
0.71 0.74
9
0.40
ND
0.09 0.14
0.13 ND 0.01
ND 1.3 0,08 0.70 1.5 2.0
1.6
0,71
0.22 0.94
0,58 0.05 0.12
*
* 0.05 0.03 0.01 0.14
ND
DDE
0.93 6,5 0.61 20 5.7 13
9
0.24 0.38 0.11 2.2
9
0.20
PCB
Breast muscle
ND ND
ND
* ND 0.01
ND ND ND 0,79 ND 1.8
0.21
ND
0.04 ND
ND ND ND
*
* ND ND ND 0,14
ND
Mirex
Contaminants ( u g / g - - w e t weight)
0.55 0.87
1.3
0.74 1.7 0,76
* 2.9 1,5 0.77 1.7 1.8
1.3
0.69
0.47 0.83
ND ND
ND
0.13 0,05 ND
* 0,77 0,16 0.06 0.69 0.40
0.23
ND
0.10 ND
* ND 0.01
ND
0.41 * 0.07 0.08
0.05 * * 0.01 0.07
*
DDE
2.1 * * 0.22 1.3
*
PCB
Liver
ND ND
ND
0.17 ND ND
* 0,57 0.17 ND 0.25 0.27
0.12
ND
0.05 ND
* ND ND
0.11
ND * * ND 0.09
*
Mirex
* *
2.2
0.11 0.43 *
0.91 1.7 0,30 0.58 1.7 2.3
*
0.26
* *
0.38
ND ND *
ND ND ND ND 0.04 0.20
*
ND
ND
ND ND
0.02 1.3 0.33
ND 0.01
1.9
ND
DDE
0.29
0.12
PCB
Brain
* *
ND
0.03 ND *
0.03 0.36 0.04 0.08 0.08 0.32
*
ND
ND
ND 0.04
ND ND
ND
Mirex
=e
e~
"0
e~
ca.
"O
(3
K.S. Kim et al.
380 Table 3. Overall means ___s (/~g/g) of PCB, DDE, and mirex concentration on different basesa
PCB
DDE
wet wt
dry wt
HEL b wt wet wt
Mirex dry wt
HEL b wt
wet wt
dry wt
HEL b wt
Subcutaneous fat 7.5 _+ 9.1
8.1 + 11.0 14 _+ 24
0.34 _+ 0.68
0.39 _+ 0.68
1.1 _+ 2.7
0.10 +_ 0.40
0.12 + 0.46 0.45 + 2.50
Breast muscle 1.3 + 3.2
4.2 _+ 9.7 32 + 42
0.16 + 0.41
0.46 + 1.13
3.1 +_ 6.9
0.07 + 0.29
0.18 +_ 0.76 0.87 + 3.35
Liver
0.82 + 0.67 2.7 + 2.1 27 _+ 21
0.09 + 0.18
0.27 + 0.52
2.5 _+ 5.0
0.06 _+ 0.12
0.19 __. 0.36 1.9 + 3.7
Brain
0.61 + 0.73 2.4 + 2.9 11 +_ 18
0.017 _+ 0.064 0.052 + 0.183 0.17 _+ 0.58 0.027 _+ 0.074 0.10 + 0.23 0.37 + 0.93
a ND treated as 0.00 b HEL--hexane-extractable lipid
Table 4. Comparison of mean concentrations for three Aroclors| DDE, and mirex and ratios of types of Aroclors by collection sitea
Mean concentrations (ug/g--wet weight)
Ratios
A-1016
A-1254
A-1260
DDE
Mirex
A-1016/A-1254
A-1260/A-1254
0.20 0.16 0.05 0.03
3.0 0.62 0.27 0.13
1.9 0.26 0.27 0.08
0.61 0.49 0.19 0.05
0.30 0.23 0.12 0.08
0.07 0.26 0.19 0.27
0.63 0.42 1.00 0.66
0.46 0.09 0.13 0.05
2.8 0.11 0.26 0.05
2.2 0.05 0.13 0.04
0.10 0.02 0.02 0
0.01 0 0.01 0
0.16 0.88 0.50 1.05
0.78 0.53 0.50 0.23
Niagara River
Fat Muscle Liver Brain Hudson River
Fat Muscle Liver Brain
a ND treated as 0 in the calculations T h e p a t t e r n s o f c o n t a m i n a n t s in t h e b i r d s m a y p r o v i d e a c l u e to t h e i r m o v e m e n t s . T h e s e h i g h levels o f c o n t a m i n a n t s pose a d i r e c t t h r e a t to t h e b i r d s . S o d e r g r e n a n d U l f s t r a n d (1972) s t u d i e d t h e e f f e c t s o f P C B a n d D D T on r o b i n s w h i c h w e r e f o r c e d to use t h e i r f a t reserves. T h e y f o u n d t h a t D D T a n d its m e t a b o l i t e s a f f e c t e d t h e b o d y transfers of PCBs, and that both were detrimental to t h e h e a l t h o f t h e b i r d s , e s p e c i a l l y u n d e r stress conditions. B u s h et al. ( 1 9 7 4 ) f o u n d a c o r r e l a t i o n o f P C B levels w i t h e m b r y o m o r t a l i t y a n d c h i c k d e f o r m a t i o n in c h i c k e n s d o s e d w i t h P C B . S c o t t et al. ( 1 9 7 5 ) r e p o r t e d h i g h levels o f D D E in c o m m o n m u r r e s (Uria aalge) w h i c h h a d a n a b n o r m a l l y h i g h m o r t a l i t y r a t e one s e a s o n ( s u m m e r 1969). Because of the association between organochlorine contamination and avian reproductive failure (Fox et al. 1978), G i l m a n et al. ( 1 9 7 8 ) i n v e s t i g a t e d t h e effects o f i n j e c t i n g p r i s t i n e H e r r i n g g u l l (Larus argentatus) e g g s w i t h o r g a n o c h l o r i n e c o n t a m i n a n t s e x t r a c t e d f r o m gull eggs c o l l e c t e d n e a r L a k e O n t a r i o . T h e y o b s e r v e d no i n c r e a s e in e m b r y o o r c h i c k m o r -
t a l i t y , w h i c h l e d to t h e c o n c l u s i o n t h a t e i t h e r t h e c o n t a m i n a n t s affect t h e a d u l t b i r d o r a n u n i d e n t i f i e d c o n t a m i n a n t is t h e a g e n t o f r e p r o d u c t i v e f a i l u r e . Hunters should be aware of the potential health p r o b l e m s to w h i c h t h e y a r e e x p o s e d . A c c o r d i n g to f e d e r a l s t a n d a r d s for p o u l t r y , a t o l e r a n c e level o f 3.0 p p m on a f a t b a s i s ( F D A 1979), t h e m e a n P C B levels w o u l d m a k e t h e s e b i r d s u n f i t f o r h u m a n c o n sumption. The New York State Department of EnVironmental C o n s e r v a t i o n c o n d u c t e d a h u n t e r s u r v e y for t h e w a t e r f o w l s e a s o n s b e t w e e n 1976 a n d 1979 ( M o s e r 1980). T h e a v e r a g e n u m b e r o f d u c k s p e r h u n t e r for t h e 1978 season w a s 3.3, b u t s o m e h u n t e r s h a r v e s t e d m a n y m o r e ; 8.3% o f t h e h u n t e r s t o o k 20 or m o r e , a n d 2.8% t o o k 40 o r m o r e . T h e t o t a l n u m b e r of h u n t e r s w a s n e a r l y 78,000. A l s o , a c c o r d i n g to t h e survey, m o s t ( 7 8 % ) o f t h e w a t e r f o w l c o l l e c t e d in N e w Y o r k S t a t e a r e d a b b l i n g d u c k s (e.g., m a l l a r d , b l a c k d u c k , w o o d d u c k , a n d t e a l ) . T h e r e s t a r e m a i n l y ( 2 0 % ) d i v e r s (e.g., s c a u p , scoters, b u f f l e h e a d , a n d g o l d e n e y e ) . F o r t u n a t e l y , h o o d e d a n d o t h e r m e r g a n s e r s , t h e m o s t h i g h l y cont a m i n a t e d g r o u p a c c o r d i n g to t h e p r e s e n t s t u d y ,
PCBs and Chlorinated Pesticides in Waterfowl, New York MEAN
CONCENTRATIONS
RATIOS
FAT
i.O " 0.78
4.00
ii
0,-
2.2
2.0( IOC 0.46
References
0.61
0.2- 0.16 Ot~lI
r~o Q~O.oml oi. MIREX
rq NIAGARA RIVER 9 HUDSON RIVER
0.86
0.8 0.6
l.OC
- -
A-IOI6/ A-1260/ /A-1254 .IA-1254
1.0
MUSCLE
i
0.4 0.62
0.5C 0
F
0.4-
A-IOI6 A-1254 A-1260 DDE
r
to hunters concerning the consumption of waterfowl. Periodic analysis should be made in order to monitor the levels of contamination in waterfowl.
0.7" 0.63
==
381
" 97
o26
0.49
0,2
rl
' z0 10L02 90
A-1016 A-1254 A-1260 DDE
MIREX
o A-1016i/ A-1260/'/ I'A-1254 /A-1254
Fig. 2. A comparison by collection site of the mean concentrations of PCBs and pesticides in subcutaneous fat and breast muscle tissue from migratory aquatic birds, and of the ratios of the levels of different Aroclor mixtures in the birds. The light bars correspond to birds from the Niagara River, and the dark bars to those from the Hudson River
comprised less than 2% of the harvest. Most of the birds have substantially lower levels of contamination in the muscle tissue than in the fat. Mallard, for example, have PCB concentrations of 6.7 and 0.40 /zg/g (wet-weight) in the fat and muscle, respectively. These birds may be fit for consumption if the fat is removed during preparation or cooking. Mergansers, also, have high levels of PCBs in the muscle tissue. Even though the levels of contamination are high, they are declining. A study of waterfowl collected in New York State in 1972 (Baker et al. 1976) showed mean PCB levels (/~g/g-wet weight) in greater scaup (n = 18) of 3.1 in muscle, 5.2 in liver, and 2.1 in brain. Mean PCB levels in mallard (n = 6) were 1.4 in muscle, 1.4 in liver, and 1.5 in brain. No measurements were made on fat tissues in this study. The level found in the present study was 0.40 in muscle. The levels of PCBs, DDE, and mirex in waterfowl reported here indicate continued wide-spread contamination of the birds' migration region. This contamination cannot be assumed to be isolated to New York State. Based largely on these PCB levels, the states of New York and New Jersey issued warnings
Baker F, Tumasonis C, Stone W, Bush B (1976) Levels of PCB and trace metals in waterfowl in New York State. NY Fish Game J 23:82-91 Bush B, Conner S, Snow J (1982) Sensitive and accurate PCB analysis by glass capillary gas chromatography. J Assoc Off Anal Chem 65:555-566 Bush B, Tumasonis C, Baker F (1974) Toxicity and persistence of PCB homologs and isomers in the avian system. Arch Environ Contam Toxicol 2:195-211 Cromartie E, Reichel W, Locke L, Belisle A, Kaiser TE, Lamont T, Mulhern B, Prouty R, Swineford D (1975) Residues of organochlorine pesticides and polychlorinated biphenyls and autopsy data for bald eagles, 1971 - 1972. Pestic Monit J 9:1114 Food and Drug Administration (1977) Pesticide Analytical Manual, Vol I, U.S. Department of Health and Human Services, US Govt Prin~ing Office, Washington, DC, Section 211 9 13 --(1979) Polychlorinated biphenyls (PCBs); reduction of tolerances. Fed Reg June 1979 44:38330-38340 Fox GA, Gilman AP, Peakall DB, Anderka FW (1978) Behavioral abnormalities of nesting Lake Ontario gulls. J. Wildl Manage 42:477-483 Gilman AP, Hallett D J, Fox GA, Allan L J, Learning W J, PeakaU DB (1978) Effects of injected organochlorines on naturally incubated herring gull eggs. J Wildl Manage 42:484-493 Horwitz W (ed) (1980) Official Methods of Analysis of the Association of Official Analytical Chemists, 13th ed, AOAC Washington, DC, Ch 29, pp 466-471 Hutzinger O, Safe S, Zitko V (1974) The Chemistry of PCBs. CRC Press, Cleveland, OH. pp 1-39, 133-148 Kaiser K (1978) The rise and fall of mirex. Environ Sci Technol 12:520-528 King JR, Farner DS (1965) Studies of fat deposition in migratory birds. Ann NY Acad Sci 131:422-440 MacDougall D (1980) Guidelines for data acquisition and data quality evaluation in environmental chemistry. Anal Chem 52:2242-2249 Moser J (1980) A report of New York's zoned waterfowl seasons 1976-1979. NYS Department of Environmental Conservation, Albany, NY, pp 7-9 Natrella M (1963) Experimental Statistics. National Bureau of Standards Handbook 91. US Department of Commerce, US Govt Printing Office, Washington, DC O'Shea T, Fleming WJ III, Cromartie E (1980) DDT contamination at Wheeler National Wildlife Refuge. Science 209:509510 Pastel M, Bush B, Kim JS (1980) Accumulation of polychlorinated biphenyls in American shad during their migration in the Hudson River, Spring 1977. Pestic Monit J 14:11-22 Pickett RL, Dossett DA (1979) Mirex and the circulation of Lake Ontario. J Phys Oceanog 9:441-445 Scott JM, Wiens JA, Claeys RR (1975) Organochlorine levels associated with a common murre die-off in Oregon. J Wildl Manage 39:310-320 Sodergren A, Ulfstrand S (1972) DDT and PCBs relocate when caged robins use fat reserves. Ambio 1:36-40 Manuscript received August 2, 1983 and in revised form November 17, 1983.
