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BOSTON PUBLIC LIBRARY 
GOVSBAiMENT QOCU^tKTS UEPARTMtWT 



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" O O J 



PESTICIDES 
MONITORING 

JOURNAL 




JUNE 1981 



VOLUME 15 NUMBEI 



PEMJAA (15) 1-75 (I^A^^/i^J?^/?)^ 






rnEy, /^.Q . j^A 



The Pesticides Monitoring Journal is published quarterly under the auspices of the 
Federal Working Group on Pest Management (responsible to the Council on Environ- 
mental Quality) and its Monitoring Panel as a source of information on pesticide 
levels relative to humans and their environment. 

The Working Group is comprised of representatives of the U.S. Departments of Agri- 
culture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; 
Transportation; and Labor; and the Environmental Protection Agency. 

The Monitoring Panel consists of representatives of the Agricultural Research Service, 
Animal and Plant Health Inspection Service, Extension Service, Forest Service, 
Department of Defense. Fish and Wildlife Service, Geological Survey, Food and Drug 
Administration, Environmental Protection Agency, National Marine Fisheries Service, 
National Science Foundation, and Tennessee Valley Authority. 

The Pesticides Monitoring Journal is published by the Management Support Division in 
the Office of Toxic Substances, U.S. Environmental Protection Agency. 

Pesticide monitoring activities of the Federal Government, particularly in those agencies 
represented on the Monitoring Panel which participate in operation of the national 
pesticides monitoring network, are expected to be the principal sources of data and 
articles. However, pertinent data in summarized form, together with discussions, are 
invited from both Federal and non-Federal sources, including those associated with 
State and community monitoring programs, universities, hospitals, and nongovernmental 
research institutions, both domestic and foreign. Results of studies in which monitoring 
data play a major or minor role or serve as support for research investigation also 
are welcome; however, the Journal is not intended as a primary medium for the 
publication of basic research. Publication of scientific data, general information, trade 
names, and commercial sources in the Pesticides Monitoring Journal does not represent 
endorsement by any Federal agency. 

Manuscripts received for publication are reviewed by an Editorial Advisory Board 
established by the Monitoring Panel. Authors are given the benefit of review comments 
prior to publication. For further information on Journal scope and manuscript prepara- 
tion, see Information for Contributors at the back of this issue. 

Editorial Advisory Board members are: 

John R. Wessel, Food and Drug Administration, Chairman 

Robert L. Williamson, Animal and Plant Health Inspection Service 

Anne R. Yobs, Center for Disease Control 

William F. Durham, Environmental Protection Agency 

Gerald E. Walsh, Environmental Protection Agency 

G. Bruce Wiersma, Environmental Protection Agency 

William H. Stickel, Fish and Wildlife Service 

Allan R. Isensee, Science and Education Administration — Agricultural Research 

Herman R. Feltz, Geological Survey 

Address correspondence to: 

PaulFuschini (TS-793) 

Editorial Manager 

Pesticides Monitoring Journal 

U. S. Environmental Protection Agency 

Washington, D.C. 20460 

Editor 

Roberta B. Maltese 



CONTENTS 



Volume 15 June 1981 Number 1 



Page 
FISH, WILDLIFE, AND ESTUARIES 

Polychlorinated Biphenyls and Other Organic Chemical Residues in Fish from Major 

United Slates Watersheds Near the Great Lakes, 1978 1 

Oilman D. Veith, Douglas W, Kuehl, Edward N. Leonard, Kenneth Welch, and 
Glenn Pratt 

Organochlorine Pesticide Residues in Some Indian Wild Birds 9 

Bhupendra S. Kaphalia, Mirza M. Husain, Tejeshwar D. Seth, Ashwini Kumar, 
and Coimbatore R. Krishna Murti 

Cadmium, Lead, Mercury, Arsenic, and Selenium Concentrations in Freshwater 

Fish, 1976-77 — National Pesticide Monitoring Program 14 

Thomas W. May and Gerald L. McKinney 

FOOD AND FEED 

Pesticide, Heavy Metal, and Other Chemical Residues in Infant and Toddler Total 

Diet Samples— (ID— August 1975-July 1976 39 

Roger D. Johnson, Dennis D. Manske, Dallas H. New, and David S. Podrebarac 

Organochlorine Pesticides and PCBs in Cod-Liver Oil of Baltic Origin, 1971-80 51 

Jerzy Falandysz 

Pesticide, Metal, and Other Chemical Residues in Adult Total Diet Samples — {XII) 

—August 1975-July 1976 54 

Roger D. Johnson, Dennis D. Manske, and David S. Podrebarac 

APPENDIX ^ 70 

ERRATUM 72 

MEETING NOTICE 73 

Information for Contributors 74 



FISH, WILDLIFE, AND ESTUARIES 

Polychlorinated Biphenyls and Other Organic Chemical Residues in Fish from 
Major United States Watersheds Near the Great Lakes, 1978 

Oilman D. Veith/ Douglas W. Kuehl," Edward N. Leonard,' Kenneth Welch," and Glenn Pratt* 



ABSTRACT 

wenty-six composite samples of fish were collected during 
978 from United States watersheds near the Great Lakes 
nd analyzed for polychlorinated biphenyls (PCBs) and 
dated organic chemicals. PCB mixtures resembling Aroclor 
254 were found in all samples, and mixtures resembling 
'roclor 1242 (or 1016) were found in 77 percent of the 
vnples. Total PCB concentrations in the whole-fish com- 
osite samples ranged from 0.13 to 14.6 ppm; 65 percent of 
le samples contained > 2 ppm PCBs. DDT and its metab- 
Hles were also found in all samples. ZDDT concentration 
'as 1.66 ppm, and 81 percent of the samples contained 
: 1.0 ppm ZDDT. Chlordane ranged from < 0.007 to 2.57 
pm in 38 percent of the samples. Hexachlorobenzene was 
jund in 65 percent of the samples, ranging from <^0.005 
) 0.447 ppm. Other chemicals identified by gas chroma- 
Jgraphy/mass spectrometry included petroleum hydro- 
^rbons and chlorobenzenes, chlorostyrenes, chlorophenols, 
nd chlorinated aliphatic compounds. Fish from the Ashta- 
ula River (Ohio), Rocky River (Ohio), and Wabash River 
ndiana) contained extremely complex residues of chlori- 
ated and other organic chemicals. 

Introduction 

a 1976, authors extended their gas-liquid chromatogra- 
hy/mass spectrometry (GLC/MS) exploratory studies 
f organic chemical residues in Great Lakes fish to in- 
lude residues in fish from major United States rivers 
M the purpose of tabulating polychlorinated biphenyls 
PCBs) and other xenobiotic chemicals accumulating in 
^e aquatic environment. A previous work (6) showed 
lat the types and concentrations of chemical residues 
1 fish varied immensely among rivers in the same area 
f the country. Fish in some rivers in eastern Michigan 
nd Ohio contain PCB residues almost exclusively. 



U.S. Environmental Protection Agency. Environmental Research Lab- 
ratory, 5201 Congdon Boulevard, Duluth, MN 55804 
U.S. Environmental Protection Agency, National Pollutant Discharge 
Umination System (NPDES) Permits Branch-Region V, 230 S. Dear- 
3'n, Chicago. IL 60605 



whereas fish from the Ashtabula River nearby in Ohio 
contain at least 19 major chlorinated chemicals in addi- 
tion to PCBs. Fish from rivers a few miles apart differ 
in hexachlorobenzene (HCB) residues by a factor of al- 
most 3,000. 

The wide variation in both the types and amounts of 
chemicals in different waters suggests that it is not cost- 
effective to apply trend-monitoring programs to the 
problem of determining the extent of contamination by 
toxic chemicals. Trend monitoring requires a predeter- 
mined list of chemicals to monitor, precise methods for 
measuring small differences in concentration, and, to 
minimize biological variability, a fairly rigid sampling 
protocol with respect to species and size. In contrast, the 
initial problem regarding toxic industrial chemicals is 
the identification of every major chemical component of 
residues from hundreds of industrial areas. Such areas 
may not have diverse fish populations because of the 
contamination. Finally, order-of-magnitude estimates of 
residue concentrations by GLC/MS may be used to di- 
rect enforcement-related field studies to "hot-spots" for 
more intensive studies. 

A previous work (6) indicated that taking composite 
samples of any fish near the mouth of a river provides 
a convenient, enriched sample of bioaccumulable chemi- 
cals being discharged into the entire watershed and ex- 
cludes the bulk of the less persistent, nonaccumulable 
chemicals attributable to natural products and sanitary 
wastes. Because the accumulation of chemicals in fish 
species varies considerably less than the concentration 
of chemicals in rivers and areas of rivers, composite 
samples also provide adequate estimates of relative con- 
centrations in the sampling areas. This paper presents 
the results of exploratory studies of chemicals in fish 
from rivers in Minnesota, Wisconsin, Indiana, Michigan, 
Ohio, and New York (Figure 1). 



OL. 15, No. 1, June 1981 



1 




■> 1976 SAMPLES 
• 1978 SAMPLES 



FIGURE 1. Map of U.S. EPA Region V showing siles where fish samples were collected for GLC/MS analyst 

bioacciimiilating hazardous organic chemical residues 



Materials and Methods 

COLLECTION OF FISH 

The areas that were sampled for detailed GLC/MS 
analyses in 1976 and the 26 sampling areas for the pres- 
ent study (1978) are shown in Figure 1. Table 1 gives a 
brief description of the 1978 sampling locations. 

State and federal field personnel used nets and other 
conventional apparatus to collect fish. Sampling areas 
included known problem areas disclosed by previous 
studies as well as rivers for which little data were avail- 
able. Where possible, samples were collected near mouths 
of rivers or confluence of major tributaries. Sample 
areas are designated as general areas of rivers rather 
than exact locations because of the migratory nature of 
many fish and the tendency of bioaccumulable chemicals 
to contaminate large areas near the discharge. Samples 
were wrapped in solvent-rinsed aluminum foil, frozen, 
and shipped with dry ice to the Environmental Research 
Laboratory in Duluth, Minnesota. 

PREPARATION OF SAMPLES 

The procedures for preparation and analysis of samples 
have been described previously (6). Composite whole- 



fish samples were homogenized with a Hobart t 
grinder. Subsamples weighing 20 g were extracted 
Soxhlet extractor with a 1:1 mixture of hexane 
methylene chloride. Following Florisil column clea 
samples were analyzed by electron-capture (EC) 
flame-ionization (FI) GLC and multiple-ion-dete( 
(MID) GLC/MS. 

GLC analysis provided measurement of PCBs, F 
DDE, and 2DDT, as well as information on the ( 
plexity of the residue with respect to other nonf 
organic chemicals. MID GLC/MS was used to qu 
tate cis- and /ran.r-chlordane, cis- and trans-nona-d 
heptachlor epoxide, and oxychlordane. A procec 
blank was performed with every fifth sample. Dupli 
analyses of several samples gave results within 4 pei 
for both EC GLC and MID GLC/MS. Recovery I 
laboratory-raised fathead minnows spiked with 1 
PCB and 50 ppb pesticides was >92 percent for ' 
compound. 

A second subsample (100 g) of each fish was Sox 
extracted in a 1:1 mixture of hexane and meth) 
chloride, cleaned by gel-permeation chromatogn 
(2), and qualitatively analyzed by full mass r 



Pesticides Monitoring Join 



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15, No. 1, JraE 1981 



(m/z 50-550) scanning GLC/MS. Again, procedural 
blanks were performed with every fifth sample, and 
spiking experiments showed >90 percent recovery. 



ANALYSES 

The GLC/MS analyses were performed on a Finnigan 
4000 mass spectrometer interfaced to an INCOS data 
system. Instrument parameters and operating conditions 
follow : 

Column; glass, capillary, 30-m long by 0.25-mm (ID), 

coated with SE-30 
Temperature. °C: column programmed from 100 to 225° at 4°/ 

minute (with a 20-minute hold) 

ion source 280 
Carrier gas: helium flowing at 30 cm/second 

Mass scan: 50-550/2 seconds 

Electron energy: 70 eV 
Emission: 350 mA 

MID GLC/MS analyses were also performed on the 
above equipment, with the same temperature program- 
ming, followed by a 20-minute hold. The mass spec- 
trometer was computer-controlled to monitor six ions 
for equal time during a 2-second period. The six ions 
were m/z 373 for chlordane, m/z 409 for nonachlor, 
m/z 272 for heptachlor, m/z 355 for heptachlor epox- 
ide, m/z 387 for oxychlordane, and m/z 442 for de- 
fluorotriphenylphosphene (DFTPP). 

DFTPP was used as an internal standard for MID quan- 
tification. Each extract was spiked with DFTPP to give 
a concentration of 10 ng/jiJ. Two standards of the chlor- 
dane components of 5 ng/ju,l and 20 ng//J each were 
used as samples after each set of five fish samples. Quan- 
tification was based on a lO-ng/^al solution with standard 
INCOS software. The quantified standards gave values 
within 4 percent of expected values. The limit of de- 
tectability was 0.50 ppb wet weight. 

Ion source was operated as above with an emission of 
350 mA. 

Results and Discussion 

PCBs were found in all 26 samples at concentrations 
ranging from <0.1 ppm in fish from the upper reaches 
of Cattaragaus Creek, New York, to 14.6 ppm in fish 
from the Raisin River, Michigan. Aroclor 1254 consti- 
tuted over 50 percent of the total PCB residues in the 
majority of the samples. Aroclor 1016/1242 was found 
in 20 of the 26 samples at concentrations ranging from 
<0.1 to 9.83 ppm in Raisin River fish. These results are 
consistent with the authors' previous study of 58 sam- 
ples, in which Aroclor 1016/1242 was present in 77 
percent of the samples (6). 

Fish from the Fox River (Wisconsin), Raisin River 
(Michigan), and Ashtabula and Greater Miami Rivers 
(Ohio) remain heavily contaminated with PCBs. Twelve 
other samples contained PCB residues >2 ppm. Al- 



though PCB concentration in the edible portion o: 
fish is expected to be lower than that in the whole 
the present data suggest that 65 percent of the fish 
pies would pose significant hazards to animals, su( 
mink, feeding on the fish (i) . 

DDT, once the major organochlorine contaminai 
fish in many U.S. waterways, is a minor contamina 
the river systems investigated in the present study 
though DDE was found in all samples, 2DDT coi 
tration in 81 percent of the samples was below 1.0 
the maximum concentration was 1.66 ppm, in 
Ontario fish. 

HCB was the next most prevalent organochlorine f 
in the present study; 65 percent of the samples 
tained measurable quantities. Although most sar 
contained <0.05 ppm HCB, Ashtabula River fish 
tained 0.447 ppm. The authors' previous work (6 
vealed concentrations of 3.14 ppm HCB in fish fron 
Ashtabula River in 1976. The apparent decline m£ 
the result of sampling variability or of pollution-a 
ment measures taken since the 1976 discovery. The 
that fish analyzed in the present study were coll 
upstream from the alleged discharge (3) into the 
tabula River may also be significant. An ongoing 
investigation is a direct result and a primary bene 
this type of biomonitoring, because areas of highest 
lamination are identified for more intensive stuu 
minimum cost. 

Chlordane and components of technical chlordane I 
found in 38 percent of the samples. Although fish I 
most of the rivers contained <0.05 ppm chlordane! 
from the Grand River, Michigan, and Rocky I 
Ohio, contained 2.57 ppm and 2.68 ppm, respect 
The total nonachlor concentrations in these fish 
3.07 ppm and 1.82 ppm, respectively. Heptachloi 
heptachlor epoxide were found only in fish fron 
Wabash, Ashtabula, and Huron Rivers and Lake 
tario. Oxychlordane was present in Rocky River, I 
Ontario, and Lake Erie fish at a maximum conce) 
tion of 167 ppb. The coho salmon caught at the n\ 
of the Cattaragaus Creek, New York, are undouti 



Lake Erie fish, which would account for the oxyc 
dane residues. 



In addition to chemicals quantified by GLC or 
GLC/MS, the results of exhaustive GLC/MS stud> 
the fish extracts are summarized in Table 2. The fill 
organic chemicals identified in Table 2 are aliphati^ 
aromatic hydrocarbons. Heptadecane, pentadecanei 
related hydrocarbons are natural products of bsl: 
algae, as well as the results of petroleum contamini 
from mixtures such as fuel oil. Present methodology 
mits only qualitative statements about the sourd^i 
these compounds, based on FI GLC chromatogii 



Pesticides Monitoring Joif 



dinecarboxamide appeared to be as common as 
adecane in fish from these rivers. 

iachloroanisole was identified in 15 of the 26 sam- 
of fish. The authors have observed halogenated 
3les in effluents of sewage treatment plants receiv- 
the respective halogenated phenols (4). Present in- 
lation suggests that the anisoles arise from methyla- 
of the corresponding phenols by bacteria. Studies at 
Environmental Research Laboratory in Duluth (un- 
ished data) have shown that fish exposed to halo- 
ited phenols do not produce the anisoles metaboli- 
'. The presence of pentachloroanisole may therefore 
; from the widespread use of pentachlorophenol as a 
d preservative. Because the bioconcentration factor 
the methyl derivative of phenols is several orders of 
nitude greater than that of the phenol, pentachloro- 
ole as an environmental contaminant is probably the 
It of selective bioaccumulation of a more persistent 
ibolite of pentachlorophenol. 

tachloronorbornene and hexachloronorbornadiene 
! found only in the Wabash River fish collected 
w Terre Haute, Indiana. These two compounds are 
•mediate chemicals in the production of cyclodiene 
icides, and their occurrence is linked to manufac- 
ig sites for these pesticides. These chemicals were 
ided in Table 2 because they are unique in the 
lash River, not because of widespread occurrence, 
ie data confirm the authors' studies of fish from the 
:r Wabash (6) and suggest a source of contamina- 
in the vicinity of Terre Haute, Indiana. The only 
r identification of heptachloronorbornene and hexa- 
ronorbornadiene in the aquatic environment was 
irted by the Food and Drug Administration, U.S. 
artment of Health and Human Services, in fish from 
Mississippi River below Memphis, Tennessee (5). 

:x was identified only in Lake Ontario fish. The com- 
jd was first observed in 1973 and was extensively in- 
gated by state and federal agencies. 

Is were identified in all samples and, although the 
1-, penta-, and hexachlorobiphenyl homologs were 
lominant, PCBs containing two or three chlorine 
IS were found in 19 of the 26 samples. 

above-mentioned quantitative and qualitative data 
ent a reasonably comprehensive description of the 
nical residues that contaminate fish in some major 
rs. However, these data fail to illustrate adequately 
leed for improved biomonitoring or analytical meth- 
development. Fish from many of the rivers contain 
lue mixtures that are similar to the GLC chromato- 
1 of the Maumee River fish presented in Figure 2. 

chromatogram was obtained by using a 30-m, wall- 
sd capillary column and an electron-capture detec- 
Although there are many chemicals in this extract, 
is, HCB, and natural products account for all peaks 



in the chromatogram. Therefore, the residues in this 
area are comparatively simple to work with, and routine 
GLC methods should be adequate for any surveillance 
work. 

In contrast, the Ashtabula, Wabash, and Tittabawassee 
Rivers contain extremely complex mixtures of bioaccu- 
mulable chemicals. An electron-capture capillary chro- 
matogram of extract of fish from the Ashtabula River 
is shown in Figure 3. Chemicals identified include tetra-, 
penta-, and hexachlorobutadiene; chlorinated benzenes 
up to hexachlorobenzene; penta- and hexachlorobutyla- 
mines; and numerous hexa-, hepta-, and octachlorosty- 
renes. Despite the identification of almost 100 chemicals 
in this sample, those identified to date are largely only 
those in the highest concentrations. A comprehensive 
study of residues in fish from the Ashtabula and Wabash 
Rivers is presented elsewhere (3). 

Even though progress has been made in developing 
methods for rapid characterization of chemical residues, 
the long lists of chemicals being published from studies 
of environmental samples should not lead to the conclu- 
sion that present methods are thorough or adequate. In 
many of the rivers the authors have studied during the 
past four years, chemicals are present that cannot be 
identified without improved cleanup methods and in- 
strumental techniques. More important, the number of 
sample sites studied would have to be increased by an 
order of magnitude in order to screen even a single sam- 
ple from industrial areas over the next five years. Major 
improvements in the current state-of-the-art methods for 
GLC/ MS screening will have to be made before an ade- 
quate number of samples can be thoroughly studied. 

LITERATURE CITED 

(/) Aulerich, R. J., R. K. Ringer, H. L. Seagran, and W. G. 
Youatt. 1971. Effects of feeding echo salmon and other 
Great Lakes fish on mink reproduction. Can. J. Zool. 
49(5) :61 1-616. 

(2) Kiiehl, D. W.. and E. N. Leonard. 1977. Isolation of 
xenobiotic chemicals from tissue samples by gel permea- 
tion chromatography. Anal. Chem. 50( 1) : 182-185. 

(3) Kuehl. D. W.. E. N. Leonard. K. ]. Welch, and G. D. 
Veith. 1980. Identification of hazardous organic chemi- 
cals in fish from the Ashtabula River, Ohio, and 
Wabash River, Indiana. J. Assoc. Off. Anal. Chem. 
63(6): 1238-1244. 

(4) Kuehl. D. W., G. D. Veith, and E. N. Leonard. 1978. 
Brominated compounds found in waste-treatment efflu- 
ents and their capacity to bioaccumulate. In Water 
Chlorination, Vol. 2, Ann Arbor Science Publishers, 
Inc., Ann Arbor, Mich. pp. 175-192. 

(5) Spehar, R. L., G. D. Veith, D. L. DeFoe, and B. A. 
Bergstedt. 1977. A rapid assessment of the toxicity of 
three chlorinated cyclodiene insecticide intermediates to 
fathead minnows. National Technical Information 
Service, Washington, DC, EPA-600/3-77-099. 22 pp. 

(6) Veith, G. D., D. W. Kuehl, E. N. Leonard, F. A. 
Puglisi, and A. E. Lemke. 1979. Polychlorinated bi- 
phenyls and other organic chemical residues in fish 
from major watersheds of the United States, 1976. 
Pestic. Monit. J. 13(1) :l-n. 



15, No. 1, JtTNE 1981 



TABLE 2. Chemical contaminants identified by GLC/MS in fish from United States rivers near the Great Lakesf 



Chemical 

Contaminant 



Wisconsin Fox 
River River 



Lake 
Pepin 



Wabash 


Wabash 










River 


River 










(above 


( below 




St. 




Tittaba- 


Terre 


Terre 


White 


Joseph 


Grand 


wassee 


Haute) 


Haute ) 


River 


River 


River 


River 



Raisin 
River 



Scioto Ashtai' 
River Rivi i 



Tridecane 

Tetradecane 

Pentadecane 

Hexadecene 

Hexadecane 

Heptadecene 

Heptadecane 

Octadecane 

Nonadecane 

Eicosane 



Naphthalene 

Methylnaphthalene 

Dimethylnaphthalene 

Biphenyl 

Melhylbiphenyl 

C2-Biphenyl 

Phenanthrene 

Fluoranthene 

Pyrene 

Fluorene 



Dibenzofuran 

Acenaphthalene 

Methylbenzanthracene 

Dibenzothiophene 

Pyridinecarboxamide 

Terphenyl 

Phenylnaphthalene 

Pentachlorobenzene 

Hexachlorobenzene 

Peniachloroanisole 



1 




1 


1 


I 1 

1 


1 


1 
1 


1 
1 


1 1 
1 1 


I 






1 1 


1 







Penlachlorophenol 

Pentachlorobenzyl alcohol 

DDE 

TDE 

DDMU 

DDT 

Heptachloronorbornene 

Heptachloronorbornadiene 

Mirex 

Photomirex 



Endrin 

Monochlorobiphenyl 

Dichlorobiphenyl 

Trichlorobipheny! 

Tetrachlorobiphenyl 

Pentachlorobiphenyl 

Hexachlorobiphenyl 

Heptachlorobiphenyl 

Octachlorobiphenyl 

Hexachlorostyrene 



Heptachlorostyrene 

Octachlorostyrene 

Chlordane 

Nonachlor 

Heptachlor 

Heptachlor epoxide 

Oxychlordane 



NOTE: 1 = Confirmed by GLC and MS retention time data; 2 = confirmed by MS data; 3 = suggested by MS data. 



Pesticides Monitoring JctN 



BLE 2 (cont'd.). 





















Great 


Great 






















Maumee 




Miami 


Miami 






Catta- 














San- 


River 


Maumee 


River 


River 




Catta- 


RAGAUS 


ON 


Chagrin 


Rocky 


CONNEAUT 


Black 


Portage 


dusky 


(Water- 


River 


(MlAMIS- 


(Eliza- 


Lake 


RAGAUS 


Creek 


ER 


River 


River 


River 


River 


River 


River 


VILLE) 


(COLLEN) 


burg) 


BETHiowN) Ontario 


Creek 


(Mouth) 






2 






2 






















2 






2 












2 








2 


1 


1 














1 


1 


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1 




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15, No. 1, June 1981 




^.j^-— v-^ 





30 

MINUTES 



FIGURE 2. Capillary electron-capture chromatogram of fish extract from Maumee River, Ohio. 




FIGURE 3. Capillary electron-capture chromatogram of fish extract from Ashtabula River, Ohio. 



Pesticides Monitoring Jot. 9 



Organochlorine Pesticide Residues in Some Indian Wild Birds ' 

Bhupendra S. Kaphalia, Mirza M. Husain, Tejeshwar D. Seth, Ashwini Kumar, and Coimbatore R. Krishna Murti 



ABSTRACT 

sidiies of BHC and DDT were estimated by gas-liquid 
'omatographic analysis of tlie internal body organs, depot 
, and blood plasma of a few species of Indian wild birds 
itured in and around the urban area of Lucknow. Total 
IC and y-BHC (lindane) levels were high in breast muscle. 
?r, heart, and lung tissues of pigeon, crow, and vulture, 
npared witli the respective tissues of chicken, cattle egret, 
i kite. More lindane and total BHC was found in tissues 
vulture compared with other species. The major part 
BHC isomers in the brain of birds examined was ac- 
mted for by a-BHC. Total BHC detected in depot fat of 
\ws was 29.7 ppm; lesser amounts were found in vulture, 
e, and cattle egret, respectively. Total DDT levels were 
■nparable in the blood plasma of chicken, pigeon, crow, and 
tie egret, although residues generally showed the follow- 
order in the tissues examined: chicken < pigeon < cat- 
egret < crow < kite < vulture. High levels of DDT 
re delected in depot fat of crow, kite, and vulture (50.8, 
0, and 95.3 ppm, respectively). Avian species thus reflect 
•logical tnagnification of BHC and DDT residues, presum- 
y due to their food habits. 



Introduction 

ganochlorine pesticides and related compounds have 
:n detected in significant amounts in the environment 
i in human body tissues (8). Pesticides are dispersed 
h during their manufacture and by their extensive 
! for controlling vector-borne diseases and crop pests. 

vironmental contamination from persistent organo- 
orines has been recognized as a threat to wildlife for 
ire than two decades. Many residues have been found 
tissues and eggs of birds in Europe and North Amer- 
(7, 20, 23. 24). Some reports {10) of high mortal- 
of birds have been attributed to poisoning by organo- 
orines. The bioconcentration of DDT and other or- 
lochlorine residues is apparently associated with the 
'itat and dietary habits of different species of birds 
4, 9, 17, 23). For example, earthworms are the prin- 
al source of DDT for robins (/). These pesticides 
er the bodies of earthworms through soil, which is 
largest reservoir of pesticide residues. 



iustrial Toxicology Research Centre, Post Box 80, Mahatnia 
dhi Marg, Lucknow-226001. India 



Certain species of birds, because of their worldwide dis- 
tribution, are considered good indicators of environmen- 
tal pollution by pesticides {16). For example, crows 
have been used by many workers {11, 15, 18, 21. 22). 
The present report deals with DDT and BHC residues 
in wild pigeon {Columha livia), house crow {Corvus 
splendens), common pariah kite {Milvus migrans), Ben- 
gal vulture (Gyps bengalensis), and cattle egret (Bubul- 
cus ibis). Farm-bred chickens were taken for compari- 
son. 

Materials and Methods 

Wild pigeon, crow, kite, vulture, and cattle egret (three 
birds in each species) were obtained through commer- 
cial bird trappers during February and March 1980, 
from the urban area of Lucknow, a major city located 
26°52' north and 80°56' east in the Indo-Gangetic 
plain. It is one of the most populated regions in the 
world, with a tropical climate. Chickens (average body 
weight 500 g) were purchased from the State Live Stock 
Farm, Lucknow. Within 24 hours of capture, birds were 
sacrificed, blood was collected in heparinized containers, 
and plasma was separated. Depot fat and internal body 
organs were excised. The average bird weights were 200, 
305, 750, 4200, and 260 g for pigeon, crow, kite, vul- 
ture, and cattle egret, respectively. 

ANALYSIS FOR ORGANOCHLORINE PESTICIDE RESIDUES 

Blood Plasma — One milliliter blood plasma was mixed 
with 3 ml concentrated formic acid (98 percent pure) 
and extracted with «-hexane by shaking 1 hour. The n- 
hexane extract was washed with glass-distilled water and 
cleaned by concentrated H^SO^ treatment according to 
Dale et al. (6), as modified in the Arrhenius Labora- 
tory, Analytical Chemistry, University of Stockholm, 
Sweden. 

Body Tissues — Minced tissue (2 g) from body organs 
was thoroughly homogenized with 7 ml formic acid and 
transferred to a 50-ml conical flask. The homogenizing 
tube and pestle were washed twice with 5-ml portions of 
n-hexane, and the washings were collected in the flask. 
The homogenate was shaken in a 40 °C water bath for 
1 hour and then the solvent layer was withdrawn. 



15, No. 1, June 1981 



Minced depot fat (0.5 g) was homogenized with 3 ml 
formic acid and 5 ml n-hexane, transferred to a 50-ml 
conical flask, and treated as above. 

The extracts of brain and body fat samples above were 
partitioned with acetonitrile (saturated with ?i-hexane) 
to remove fat. Pesticide residues were re-extracted in 
n-hexane. The solvent extract was passed through a col- 
umn filled with anhydrous Na^SOj and collected in a 
round-bottomed flask. The column was washed with 10 
ml ;i-hexane and the washings were added to the original 
filtrate. The solvent extract was evaporated to dryness 
under reduced pressure and then re-dissolved in 5 ml 
n-hexane. Fractions (2 ml) were treated with 2 ml fum- 
ing HoSO^ and centrifuged, and the solvent layer was 
withdrawn. 

Pesticide residues were determined by gas-liquid chro- 
matography (Varian Aerograph Series 2400), using 
electron-capture detection ( 'H), at the following operat- 
ing conditions: 



Carrier gas: 



Gas pressure: 

Gas flow: 

Detector temperature: 

Injector temperature: 

Column temperature: 

Column: 



pure nitrogen passed through silica gel and 

molecular sieve to remove moisture and 

oxygen, respectively 

65 psi 

40 ml/minute 

200 °C 

190°C 

ISO'C 

glass spiral column, 6 ft < 

coated with 1.5 percent OV-17 



Vb in. ID, 
-I- 1.95 per- 



cent OV-210 



Residue peaks were identified by thin-layer chromatog- 
raphy (TLC) on silica gel G-coated glass plates {14) 
and comparison with reference standards obtained from 
PolyScience Corp., Niles, Illinois. Further confirmation 



of the residues was done by chemical methodology 
and column chromatography (79). 

Recoveries of BHC isomers, DDT, and DDT metabi 
(p,/7'-DDE and p,p'-TDE) in the fortified sampli 
liver, brain, muscles, and body fat were between 7C 
94 percent. Sensitivity of the method was about ( 
ppm for BHC isomers, aldrin, and p,p'-DDE and £ 
0.002 ppm for p,p'-DDT. 

All reagents and chemicals used were high purity 
were checked for interferences under the experim 
conditions. 

Results and Discussion 

The concentrations of BHC and DDT residues in 1 
plasma, brain tissue, and depot fat are summarize 
Tables 1 and 2. Levels of total BHC, y-BHC (lindi 
and total DDT in breast muscle, liver, heart, lung, 
ney, and spleen of birds are shown in Figure 1 
values are expressed in terms of whole-tissue wet we 
results were not corrected for recovery. 

DDT and BHC and their residues are widely distril 
in the ecological system. Although BHC residues* 
excreted rapidly (13), slow accumulation does occ 
the body tissues and body fat on chronic exposure. '. 
and derivatives are quite stable and are resistai 
enzymic action; thus, residues accumulate in biolc 
tissues. The levels of DDT residues present in the 
are occasionally taken as an index of contaminatici 
DDT and DDT metabolites of the local environri 
The general tendency appears to be that the smalle 



TABLE 1. Range and geometric mean values of total BHC and y-BHC {lindane) residues in blood plasma, brain 

depot fat of some wild birds and chickens i 









Residues, ppm Whole 


-Tissue Wet Weight 




T 




Blood Plas 


MA 


Brain 


Tissue 


Depot Fat 


Bird 


Total BHC 


LlNDANi: 


Total BHC 


Lindane 


Total BHC 


Lin < 


Chicken 


0.007 1 


0.002 


0.014 


0.001 


0.208 


0.1 f 




0.006-0.010 = 


0.002-0.003 


0.008-0.025 


0.001-0.002 


0.121-0.310 


0.075 f 




(0.008)3 


(0.002) 


(0.016) 


(0.002) 


(0.253) 


(0.18 


Pigeon 


0.048 


0.016 


0.316 


0.020 


— 






0.045-0.053 


0.015-0.019 


0.215-0.607 


0.014-0.034 


— 






(0.048) 


(0.016) 


(0.355) 


(0.021) 


— 




Crow 


0.030 


O.OIl 


0.246 


0.014 


21.815 


6. 5 




0.015-0.062 


0.006-0.024 


0.213-0.266 


0.01O-O.016 


15.532-29.726 


3.99t 1' 




(0.035) 


(0.013) 


(0.248) 


(0.014) 


(22.487) 


(6.'b 


Kite 


0.060 


0.028 


0.093 


0.012 


5.468 


2. 1; 

1.182 If 




0.043-0.094 


0.020-0.051 


0.030-0.168 


0.009-0.019 


3.328-12.414 




(0.064) 


(0.031) 


(0.119) 


(0.013) 


(6.567) 


(3.1 ; 


Vulture 


0.106 


0.066 


1.132 


0.26 


12.628 


10. ) 




0.066-0.143 


0.044-0.080 


0.759-2.047 


0.142-0.683 


6.510-19.823 


4.951- f 




(0.112) 


(0.068) 


(1.247) 


(0.335) 


(13.980) 


(11.' » 


Cattle egret 


0.004 


0.048 


0.126 


0.053 


6.309 


4.: ' 




0.056-0.075 


0.040-O.057 


0.032-0.175 


0.042-0.080 


5.623-7.239 


3.567 |( 
(5.(i 

h 




(0.064) 


(0.048) 


(0.132) 


(0.055) 


(6.344) 



1 Geometric mean. 

« Range. 

■ Arithmetic mean. 



10 



Pesticides Monitoring Jou f 



LE 2. 



Range and geometric mean values of DDT and DDT metabolites in blood plasma, brain, and depot fat of 

some wild birds and chickens 









Residues, ppm Whole 


-Tissue Wet Weight 






'OUND 


Blood Plasma 


Brain 


Depot Fat 


Blood Plasma 


Brain 


Depot Fat 






CHICKEN 






PIGEON 




DDE 


0.002 


0.002 


0.222 


0.004 


0.012 







0,002-0.003 


0.001-0.002 


0.190-0.250 


0.003-0.006 


0.005-0.021 







(0.002) 


(0.002) 


(0.226) 


(0.004) 


(0.014) 


— 


FDE 


0.002 


0.001 


0.055 


0.001 


0.001 


— 




0.002-0.002 


0.001-0.001 


0.045-0.083 


ND-0.002 


ND-0.003 


— 




(0.002) 


(0.001) 


(0.059) 


(0.001) 


(0.001) 


— 


DDT 


0.003 


0.008 


0.272 


0.003 


— 







ND-0.007 


0.007-0.009 


0.236-0.298 


0.002-0.007 


ND 







(0.004) 


(0.008) 


(0.274) 


(0.004) 


— 


— 


DDT 


0.009 


0.011 


0.587 


0.009 


0.013 


— 




0.005-0.012 


0.00 9-0.012 


0.55O-O.670 


0.005-0.014 


0.005-0.023 







(0.009) 


(0.010) 


(0,590) 


(0.010) 


(0.017) 


— 






CROW 






KITE 




DDE 


0.035 


0.035 


18.595 


0.100 


0.038 


23.108 




0.024-O.044 


0.025-0.064 


15.081-21.069 


0.043-0.192 


0.026-0.053 


4.652-60.00 




(0.036) 


(0.039) 


(18.798) 


(0.119) 


(0.040) 


(36.287) 


rDE 


0.007 


0.003 


2.107 


0.317 


0.019 


11.275 




0.006-0.010 


ND-0.024 


1.151-3.530 


0.229-O.420 


0.014-O.027 


2.850-43.886 




(0.007) 


(0.011) 


(2.327) 


(0.327) 


(0.020) 


(19.391) 


)DT 


ND 


ND 


2.107 


— 


— 


— 




— 


— 


ND-5.024 


ND 


ND 


ND 




ND 


ND 


(2.289) 


— 


— 


— 


DDT 


0.018 


0.004 


12.563 


0.044 


0.003 


4.496 




0.014-0.024 


ND-0.030 


4.488-63.421 


0.027-O.074 


ND-0.027 


2.454-8.148 




(0.019) 


(0.018) 


(24.958) 


(0.048) 


(0.009) 


(5.049) 


DDT 


0.066 


0.063 


44.486 


0.522 


0.076 


44.986 




0.052-0.080 


0.031-0.128 


31.197-89.713 


0.346-0.655 


0.075-0.077 


10.310-120.115 




(0.067) 


(0.074) 


(50.788) 


(0.543) 


(0.076) 


(67.014) 






VULTURE 






CATTLE EGRET 




DDE 


0.183 


0.587 


35.070 


0.029 


0.027 


3.014 




0.106-0.245 


0.298-1.052 


20.297-53.948 


0.026-0.033 


0.018-0.035 


2.131-3.049 




(0.196) 


(0.655) 


(37.878) 


(0.030) 


(0.028) 


(3.110) 


rDE 


0.209 


0.386 


39.543 


0.004 


0.004 


6.991 




0.133-0.317 


0.228-1.022 


25.197-61.909 


0.003-0.006 


NID-0.014 


2.289-23.478 




(0.222) 


(0.499) 


(40.736) 


(0.005) 


(0.006) 


(10.710) 


DDT 


0.039 


0.095 


6.162 


0.003 


— 


3.979 




0.023-0.060 


0.038-0.229 


2.477-15.113 


ND-0.006 


ND 


1.418-7.854 




(0.028) 


(0.122) 


(7.946) 


(O.OOJ) 


— 


(4.976) 


DDT 


0.479 


1.204 


87.945 


0.041 


0.038 


17.048 




0.292-0.685 


0.644-2.535 


53.051-143.92 


0.037-0.045 


0.035-0.045 


8.360-36.267 




(0.509) 


(1.416) 


(95.353) 


(0.042) 


(0.039) 


(20.323) 



lal the higher the ratio of food consumption per 
weight, regardless of food habits. Thus, within the 
; food habit group, smaller individuals are likely to 
5t larger amounts of pesticide residues. Age and 
' size of the species are also important in influencing 
accumulation of pesticide residues. However, food 
ts and the food-chain concentration mechanism are 
; important in determining the total body burden of 
cide residues. 

e 1 shows that levels of BHC and lindane present in 
d plasma, brain tissue, and depot fat of kite and 
3 egret are comparable. Relatively high levels of 
BHC were detected in crow and pigeon brain, as 
oared with blood plasma levels. Vulture (a carrion- 
:r) contained 1.25 ppm total BHC and 0.34 ppm 
ne in the brain, which are many times higher than 
oncentrations present in other species of birds stud- 
As high as 29.73 ppm total BHC was recorded 
: 'age, 22.49 ppm) in crow depot fat. 



BHC levels in liver, heart, lung, and kidney were gen- 
erally high in pigeons and crows (Figure 1). Breast 
muscles and spleen of vulture exhibited relatively high 
accumulation of BHC. Kite and cattle egret showed gen- 
erally low concentrations of these compounds in tissue. 
Compared with other isomers of BHC, lindane accumu- 
lation was high in the tissues of vulture and cattle egret. 
However, the a-isomer accounted for the major burden 
of this compound in brain tissue of all birds studied. A 
single specimen of pigeon ovary examined in the present 
study contained 1.21 ppm total BHC and 0.31 ppm lin- 
dane. Residue levels found in the tissues and blood 
plasma of chicken were relatively low. 

Until 1962 (S), carcasses of random samples of birds 
had been analyzed for aldrin, dieldrin, or DDT. DDE is 
the primary breakdown product of DDT and is univer- 
sally distributed; exposure to this compound is essentially 
a continuous one. Residues of parent compound, DDT, 
and the metabolite TDE are less frequent. Results of 



15, No. 1, June 1981 



11 




0-600- 






5 














-2 S 


too - 


- 




O 


200 - 


O 
O 






O 

o 




o 



=,-^. 



O400- 



b 


(M 










b "> 


fs. 






ro U3 






o 
b 


•" O 

O. 




d- Lung 



^jrn^^D Ami 



Totot H C H 




e Kidney 



3mS^L 





■551 1'' 




i^ji; 


" -» s 


n 




i 




Total HCH 



lotal DDT 



f. Spte«n 



FIGURE 1. Total BHC, lindane, and lotal DDT in internal 
body organs of different species of birds. 



the present study show a positive correlation of E 
concentration in blood and brain, as well as in bl^ 
and depot fat, as suggested by several workers (2, 
Levels of DDT and DDT metabolites in blood plas 
brain, and depot fat are presented in Table 2, and t 
DDT levels in the rest of the tissues are given in FiguL, 

1 
Few samples of lungs, spleen, and depot fat of c 
showed measurable levels of o,p'-DDT. p,p'-DDT 
not detected in lung, kidney, and brain tissue of pig 
and cattle egret. p.p'-TDE was not found in the lung 
these birds. Relatively high levels of p.p'-DDE were 
served in different body organs of cattle egret, comp< 
with those present in other birds examined. More t 
70 percent of total DDT was present as p.p'-DDl 
most body organs of pigeon. An equivalent concer 
tion of p.p'-DDT and comparatively low levels of i 
TDE in body organs of crow, and to some ex 
chicken, indicate that the exposure is rather contini 
from different environmental sources. Vulture and 
contained high concentrations of p,p'-DDE and ; 
TDE, compared with the levels of parent compc 
(p,p'-DDT). 

Total DDT levels were 0.59, 20.32, 50.79, 67.10, i 
95.35 ppm in depot fat of chicken, cattle egret, ci 
kite, and vulture, respectively. In other tissues, total J 
dues of DDT generally occurred in the following oni 
chicken < pigeon < cattle egret < crow < 
< vulture. Total DDT detected was 0.01, 0.01, C 
0.07, 0.054, and 0.51 ppm in blood plasma and C 
0.02, 0.04, 0.07, 0.08, and 1.42 ppm in brain tissu ^ 
chicken, pigeon, cattle egret, crow, kite, and vulture 
spectively. The sample of pigeon ovary analyzed > 
tained 1.01 ppm total DDT. 

DDT and its metabolites show a consistent biomagni] 
tion in wild birds, presumably through the food-c' 
concentration mechanism. Flesh-eating birds had sh 
higher body burdens of DDT than non-flesh-eating c 
Thus, birds of the upper trophic zone in the food c 
show higher bioaccumulation of DDT residues. I 
levels present in birds are perhaps a reflection of the 
vironmental status of the habitat and food choice 
particular avian species. 

A cknowledgment 

Authors thank Narayan Singh for technical assista ■ 
S. H. Mehdi for illustrations, and M. M. Lai for sta i 
cal analysis. 

LITERATURE CITED 

(/) Barker, R. J. 1958. Notes on some ecological elt 
of DDT sprayed in elms. J. Wildl. Manage. 22(3):p 

(2) Brown, J. R., and L. Y. Chow. 1975. Comparil 
study of DDT and its derivatives in human t ( 



12 



Pesticides Monitoring Jom^ 



samples in Norfolk County and Holland Marsh, On- 
tario. Bull. Environ. Contam. Toxicol. 13:483—488. 
Cramp, S., P. J. Conder, and J. S. Ash. 1964. The 
risk of bird life from chlorinated hydrocarbon pesti- 
cides. Royal Soc. Prot. Birds Kept. 1962-July 1963, 
p. 24. 

Cramp, S., and P. J. S. OIney. 1966. The sixth report 
of the joint committee of the British Trust for Orni- 
thology and the Royal Society for the Protection of 
Birds on toxic chemicals in collaboration with the 
Game Research Association. July 1964-December 
1966, p. 26. 

Dale, W. E., T. B. Gaines, and W. J. Hayes, Jr. 1962. 
Storage and excretion of DDT in starved rats. Toxicol. 
Appl. Pharmacol. 4(1):89. 

Dale. W. E., J. W. Miles, and T. B. Gaines. 1970. 
Quantitative method for determination of DDT and 
DDT metabolites in blood serum. J. Assoc. Off. Anal. 
Chem. 53(6): 1287-1292. 

Eades, J. F. 1966. Pesticide residues in the Irish en- 
vironments. Nature 210(5036) :650. 
Edwards, C. A. 1976. Persistent Pesticides in the En- 
vironment. 2nd ed. CRC Press, Cleveland, Ohio. 170 
pp. 

Henny, C. J. 1977. Birds of prey, DDT and tussock 
moths in Pacific Northwest. Trans. North Am. Wildl. 
Nat. Resour. Conf. 42:397^11. 

Hunt, E. G., and A. I. Bischoif. 1960. Inimical effects 
on wild life of periodic DDD applications to Clear 
Lake. Calif. Fish Game 46(1) :91. 
Ishida, ]., Y. Ogino, and M. Imanaka. 1977. Birds in 
Relation to Environmental Pollution. Part 4, Organo- 
chlorine pesticides and PCB in organs. Okayame-ken 
Kenkyo, Hoken Senta Nempo-1, Japan, pp. 195-197. 
Jensen, S., L. Renberg, and R. Vaz. 1975. Methods for 
analysis of DDT and PCB in environmental samples 
using chromatographic methods. FAO Fish. Tech. Pap. 
137:229-236. 

Koransky, W., J. Portig, H. W. Voliland. and I. Klem- 
pau. 1964. Elimination of a- and 7-hexachlorohexane 



and effects of liver microsomal enzymes. Arch. Exptl. 
Pathol. Pharmakol. 247( l):49-60. 

(14) Kovacs, M. F., Jr. 1963. Thin layer chromatography 
for chlorinated pesticide residue analysis. J. Assoc. 
Off. Agric. Chem. 46(5) :884-893. 

(15) Malasuyama, E. 1977. Results of environmental pol- 
lution monitoring using crow as an indicator. Pestic. 
Abstr. 10(77): 1602. 

(16) Moore, N. W. 1966. Pesticides in the environment and 
their effects on wild life. Blackwell, Oxford, UK. p. 
311. 

(17) Moore, N. W., and C. H. Walker. 1964. Organic 
chlorine insecticide residues in wild birds. Nature 
(London) 201 (4924) : 1072-1073. 

(18) Osawa, T., K. Takahashi, Y. Mishima, and M. Mawa- 
riya. 1978. Residues of organochlorine pesticides and 
PCB in wild birds, especially in crows. Pestic. Abstr. 
1I(78):508. 

(19) Picer, M.. N. Picer, and M. Ahel. 1978. Chlorinated 
insecticide and PCB residues in fish and mussels of 
east coastal waters of the middle and north Adriatic 
Sea, 1974-75. Pestic. Monit. J. 12(3) : 102-1 12. 

(20) Robinson, J., and M. Roberts. 1968. Accumulation, 
distribution and elimination of organochlorine insecti- 
cides by vertebrates. Soc. Chem. Ind. Monogr. 29: 
106-119. 

(21) Tagaki, F., R. Kaise, and S. Watanabe. 1978. Survey 
on environmental pollution using crows as an index. 
Pestic. Abstr. 11 (78): 1029. 

(22) Takeshiia, T. 1977. Heavy metal content of crow's 
feathers and organochlorine compound content of 
their internal organs. Pestic. Abstr. 10(77=) : 1646. 

(2.?) Turner. J. C, S. R. B. Solly, J. C. M. Mot-krinjnen, 
and V. Shanks. 1978. Organochlorine, fluorine and 
heavy metal levels in some birds from New Zealand 
Estuaries. N.Z. J. Sci. 21(1):99-102. 

(24) U.S.D.I. Fish and Wildlife Studies. 1963. A review of 
Fish and Wildlife Service investigations during the cal- 
endar year. U.S.D.I. Fish Wildl. Serv. Circ. 199 
(1964): 129. 



15, No. 1, June 1981 



13 



Cadmium, Lead, Mercury, Arsenic, and Selenium Concentrations in 
Freshwater Fish, 1976-77 — National Pesticide Monitoring Program 

Thomas W. May ' and Gerald L. McKinney ' 



ABSTRACT 

As pari of the National Pesticide Monitoring Program, the 
Fish and Wildlife Service, U.S. Department of the Interior, 
collected freshwater fish during 1976-77 from 98 monitor- 
ing stations and analyzed them for residues of cadmium, 
lead, mercury, arsenic, and selenium. Range and geometric 
mean values in mg/kg wet weight follow: Cd, 0.01-1.04, 
0.07; Pb. 0.10-4.92, 0.32; Hg, 0.01-0.84, 0.11; As, 0.05- 
2.92, 0.27; Se, 0.05-2.87, 0.56. An arbitrary 85th percentile 
was calculated for concentrations of each element in fish to 
identify monitoring stations having fish with higher-than- 
normal concentrations: Cd. 0.11 mg/kg; Pb, 0.44; Hg, 0.19; 
As, 0.38; Se, 0.82. Log-transformed mean concentrations in 
fish from 1976-77 monitoring stations are compared with 
means from the same stations in 1972 (Cd, Hg, Pb, As, Se) 
and 1973 (Se) to depict temporal trends in whole-body con- 
centrations: Cd, significant decline; Pb, no significant differ- 
ence; Hg, significant decline: As, significant increase: Se, no 
significant difference. Because of changes in laboratories and 
analytical procedures, these conclusions should be used cau- 
tiously as trend information. Production, consumption, and 
disposal of cadmium, lead, mercury, arsenic, and selenium 
are discussed as potential environmental sources of the ele- 
ments to the aquatic environment. Specific environmental 
sources are suggested for monitoring stations having trace 
element levels exceeding calculated 85th percentiles. 

Introduction 

The National Pesticide Monitoring Program (NPMP) 
is a Federal program established to monitor nationwide 
environmental contaminants in air, soil, water, humans, 
plants, and animals. United States government agencies 
participating in NPMP are the U.S. Environmental 
Protection Agency (EPA); Geological Survey, U.S. 
Department of the Interior; Food and Drug Adminis- 
tration, U.S. Department of Health and Human Serv- 
ices; U.S. Department of Agriculture; and Fish and 
Wildlife Service, U.S. Department of the Interior. 

The Fish and Wildlife Service (FWS) is responsible 
for monitoring selected environmental contaminants in 



1 Fish and Wildlife Service, U.S. Department of the Interior. Columbia 

National Fisheries Research Laboratory. Route 1. Columbia, MO 

65201 

' U.S. Environmental Protection Agency, Surveillance and Analysis 

Division. Region VII. 25 Funston Rd., Kansas City, MO 66115 



freshwater fish. Although primary emphasis has b 
placed on organic contaminants, selected trace elemi 
have been determined intermittently. In 1969, 3 o 
posite samples, each of a different species and consis 
of 3 to 5 whole adult fish, were collected from 
sampling stations and analyzed for mercury (i 
Cadmium, lead, and arsenic were added to the progn 
in 1971, and selenium was added in 1972. San 
collections included a replicate for each species in IS 
but for only one of three species from each statioi 
1972. In 1973, all samples were analyzed for seleni. 
but only selected samples were analyzed for mercii 
arsenic, lead, and cadmium. The 1971-73 analyses v 
conducted by the Denver Wildlife Research Cer 
FWS (87). Samples were collected from 97 station 
1974, but no trace elements were analyzed. San 
collections were suspended during the 1975 samp 
year to enable a technical and administrative review 
fish-monitoring activities. The freshwater fish-monito 
program was reviewed internally and restructured, 
responsibility for NPMP in FWS was shifted to 
Columbia National Fisheries Research Laboraii 
(CNFRL). 

In 1976, collection stations were increased from 10( 
117 to include a more extensive coverage of the Gi 
Lakes. Collections were then modified to include di| 
cate composite samples of a bottom-dwelling species i 
one composite of a representative predatory specie 
each station. A list of acceptable bottom-dwellers 
predator species, listed in order of priority in Tabl 
was developed. The collections included 146 sam 
from 52 stations in 1976 and 163 samples from 
stations in 1977 (Figure 1). The purpose of this re 
is to present and interpret heavy metals data gatht 
for the NPMP during 1976-77. 

Environmental Sources of Heavy Metals 

Production, consumption, and disposal processes o I 
result in the transport of trace elements to the aqu i 
environment. The U.S. EPA has established priors 
for trace element contamination problems and thif 
to resources by including 1 3 trace elements on i 



14 



Pesticides Monitoring Jour' 



BLE 1. Sequenlial priority for selection of bottom- 
ding and predator species of fish, as established by the 
National Pesticide Monitoring Program ' 



[TOM FEEDERS (commercially or recreationally significant, if 
ible) 

Carp (Cyprintis carpio) 

Common sucker ICaloslomiis commersoni) or other members of 

the sucker family 

Channel catfish {Ictalurus punctatiis) or other members of the 

catfish family 

Other, with justification 

iDATORS (should be an important sport fish) 
Cold water stations: rainbow trout (Salmo gairdneri) , brown 
trout (Salmo trutta), brook trout (Salvelinits tontinalis) , lake 
trout {Salvelinus namayciish) 

Warm-water stations: largemouth bass iMicroptertis salmoides), 
or other member of the sunfish family, such as crappie {Poxomis 
sp.), bluegill iLepomis macrochirus) , etc. 

Cool-water stations: walleye (Srizostedion vitreitm) or other 
members of the perch family 

Other, with justification, but must be representative of the drain- 
age system 

Dm National Pesticide Monitoring Program, Freshwater Fish Col- 
on Instructions, internal memorandum issued annually to FWS 
ional Pesticide SpeciaUsts. 



priority pollutants chemicals list. In this section, authors 
attempt to link production-consumption practices asso- 
ciated with cadmium, lead, mercury, arsenic, and 
selenium to environmental sources to clarify the ra- 
tionale for monitoring concentrations of these trace 
elements in freshwater fish. 

CADMIUM 

Cadmium has a close geochemical association with zinc, 
and natural geochemical sources of cadmium are linked 
with zinc deposits occurring as massive-sulfide and 
sulfides in strataform carbonates. Nearly all domestic 
cadmium is produced as a by-product of zinc concen- 
trates and imported zinc smelter flue dusts (66). The 
primary domestic producers of cadmium in 1978 were 
AMAX Zinc Co.. Inc., Sauget, lOinois; ASARCO Inc., 
Corpus Christi, Texas, and Denver, Colorado; Bunker 
Hill Co., Kellogg, Idaho; National Zinc Co., Bartlesville, 
Oklahoma; New Jersey Zinc Co., Palmerton, Pennsyl- 
vania; and St. Joe Zinc Co., Monaco, Pennsylvania. 




A 1976 TREND MONITORING STATION 

O '977 TREND MONITORING STATION 

D INACTIVE STATION 

# = TO OR > THAN 85TH PERCENTILE (SEE TEXT FOR EXPLANATION) 



o 



URE 1. Stations sampled for determination of some metals in freshwater fish as part of National Pesticide Moni- 
toring Program, 1976-77. 



.. 15. No. 1, June 1981 



15 



Of the domestic consumption of cadmium, 95 percent 
is divided into five principal uses: plating, pigments, 
alloys, batteries, and plastic stabilizers. Electrically or 
mechanically plated hardware used in vehicles and other 
equipment accounted for 40-45 percent of domestic 
cadmium consumption in 1978. The production of red, 
orange, yellow, and maroon pigments consumed 15 
percent of the supply, and most of the rest was used in 
nickel-cadmium batteries, special-purpose alloys, and 
compounds providing heat and light stability to plastics, 
particularly polyvinyl chloride (65). 

In addition to smelter production of cadium metal, pri- 
mary producers have emphasized production of various 
cadmium compounds in recent years (63). Cadmium 
is used in the manufacture of pesticides for control of 
moles and plant diseases affecting residential lawns and 
golf courses (63). 

Cadmium is released to the environment primarily from 
four sources: the electroplating industry; the smelting 
and refining of zinc, lead, and copper; the application 
of phosphate fertilizer; and surface mine drainage (15. 
80). The tendency of cadmium to concentrate in sedi- 
ments (15) may result in a persistent source of the 
contaminant to various trophic levels in the aquatic 
environment. Studies indicate that fish accumulate 
cadmium from the water and through the food chain; 
both modes of uptake can be toxic (80). 

The electroplating industry uses cadmium plating for 
corrosion protection. Wastewater is generated from 
countercurrent rinses, rinses following chromating, 
dumping of the chromating solution, and purging of 
the plating-recovery loop (82). Plant outlet pipes often 
lead to municipal sewage treatment plants, where about 
50 percent of the cadmium remains with sewage sludge, 
and the rest is discharged (81). Incineration of sewage 
sludge volatilizes cadmium, whereas deposition in land- 
fill areas subjects streams and groundwater to contamina- 
tion. Snowmelt from the roofs and grounds of plating 
firms can contain more than 1 ppm cadmium, originat- 
ing as particulate droplets of plating solutions exhausted 
from the interiors of the firms by fans and accumulating 
on the roofs or walls or the ground below the discharge 
point (55). Perimutter and Lieber (70). who traced 
the spread of cadmium from a plating plant, found 
groundwater containing up to 10 ppm cadmium. 

When zinc ores are roasted, cadmium is volatilized and 
partly collected as fumes or flue dust. The rest is re- 
leased to the atmosphere and deposited in the area 
surrounding the smelter (15). The soil around a 
smelter facility that had been operating for 80 years 
was contaminated with cadmium within a radius of at 
least 10 miles (76). Flue dust returned to the smelter is 



often stored in waste cinder banks, which are a sou 
of pollution due to leaching and erosion from r; 
water (78). Suspended sediments containing up to 
percent cadmium have been reported in streams fi 
high runoff areas near copper and zinc smelters (7 
Inland smelters and mills generally have extensive ; 
heaps and tailing ponds along streams for waste dispo 
Estuarine and river refineries generally dispose of wa 
directly into the water through outfalls. 

Phosphate ores used in fertilizer manufacture may c 
tain from 9 to 130 ppm cadmium (77). Runoff fil 
agricultural areas where phosphate fertilizers are x 
could result in substantial cadmium loading to 
aquatic environment. 

The primary sources of cadmium contamination dui 
mining are the emission of particulates and the lead 
of cadmium from the overburden. Ores are enric 
by flotation techniques to yield a 40-60 percent i 
mium metal product. Because the cadmium concen 
tion in a mine is only a few percent, most of 
original ore mass becomes tailing waste. As much 
18-36 percent of the cadmium may be retained in 
tailings (15). Mine waters from sulfide ores can con 
more than 40 ppm cadmium, but levels of 0.1 to 2 j 
are more common (15). Draining from coal mil 
areas also poses a threat: Eight bituminous coals f: 
Kentucky and Pennsylvania had 1-2 ppm cadmium (i. 

Low concentrations (<0.1 ppm) of cadmium in (j 
are deceptive, because cadmium is extremely toxic ■( 
cumulative. Benoit et al. (6), who measured cadm 
levels in various tissues of brook trout exposed to ( 
mium in water for up to 38 weeks, reported that 
kidney accumulated the highest concentration, folio 
by the liver and gills. Exposed fish placed in f 
water lost cadmium rapidly from gill tissue but did 
lose it from either the kidney or liver. In a similar 
week exposure of rainbow trout to cadmium, madfi 
Kumada et al. (29), almost no cadmium was lost f 
the kidney of exposed fish returned to fresh water. 

LEAD 

Lead is a major constituent of certain geological for 
tions, including stratabound deposits, volcanic-sedir 
tary deposits, replacement deposits, veins, and cor I 
metamorphic deposits. Lead ore deposits commi 
contain the sulfide mineral galena (PbS), which is o 
associated with sphalerite (ZnS), pyrite (FeSj), cha 
pyrite (CuFeS,), and other sulfur salts (64). 

Most domestic primary lead production (88 percii 
originates from the limestone or dolomite stratabct 
deposits of southeastern Missouri (66). The silver- 1 
vein system of Idaho's Coeur d'Alene District pro\ ' 
8 percent of domestic primary lead, and the res 



16 



Pesticides Monitoring Jooh 



vided by replacement deposits in Colorado (3 per- 
t) and Utah (1 percent). In 1978, primary lead was 
Ited and refined at seven U.S. plants (65): four 
\RCO plants in El Paso, Texas; East Helene, Mon- 
i; Omaha, Nebraska; and Glover, Missouri; and 
[AX in Buick, Missouri; St. Joe Minerals in Hercu- 
;um, Missouri; and Bunker Hill in Kellogg, Idaho, 
ause of the relative ease of reclaiming the metal, old 
ip lead (secondary lead) accounted for 51 percent 
domestic consumption in 1978. More lead is now 
duced from secondary sources than from domestic 
■,(66). 

transportation industry is the major end user of 
1: 51 percent is consumed in storage batteries and 
percent in lead alkyl compounds that are used as 
jline antiknock additives. The electrical industry (8 
:ent consumption) has long depended on lead for 
le coverings where corrosion or moisture problems 
f exist. Because of its toxicity, lead is no longer 
i in interior paints and has been largely replaced 
;xterior paints by zinc and titanium pigments. Lead 
nents are still the preferred base material for corro- 
I protection in structural and highway components 
percent of total consumption). In the ammunition 
jstry, lead remains the major metal in shot and 
ill-caliber bullets (4 percent consumption). The con- 
iction industry (3 percent consumption) is using 
■easing amounts of lead as a sound barrier in parti- 
is and ceilings, as well as in roofing, piping, flashing, 
. caulking. Various other industries use lead for many 
erent purposes and together account for 1 3 percent 
:onsumption (66). 

id enters the environment from several sources. The 
or source of lead emissions (88 percent) is the 
ibustion of leaded gasoline. Although environmental 
rictions, initiated in 1972 to control air pollution, 
e reversed the growth in use of lead antiknock 
itives, unleaded gasoline accounted for only 33 per- 
t of the gasoline sold in 1978 (83). The average 

I content in pooled (leaded and unleaded) gasoline 
1972 was 1.2 g/gal. Under cruise conditions, lead 
■mitted from automobile exhausts in the form of 

II particles, most of which are < 1 fi.m in mass 
Man equivalent diameter (32). Such a small par- 
: size increases the residence time of lead emitted 

the atmosphere and, consequently, dispersion from 
point of emission. The small size of the particles 
tted is generally characteristic of urban lead aero- 
, and concentration of lead in ambient air is strongly 
elated with automobile traffic density (39). Thus, 
ospheric fallout and surface runoff of lead into 
: ims and rivers should be most intense where water- 
I s flow through metropolitan areas. 



Smelting and mining of lead, zinc, and copper have 
caused marked environmental contamination problems, 
even though lead emissions from these sources are small 
relative to vehicle exhausts. Sediments containing up to 
17 percent lead by weight have been found below zinc 
and copper extractive industries, in streams used for 
irrigation and drinking water (78). The pollution hazard 
is greatest where there is erosion of waste cinder banks, 
tailings, and slag heaps. Although most large smelters 
are equipped with efficient dust and fume collection 
systems that claim 98 percent recovery (64), the re- 
covered flue dusts are sometimes stored in unprotected 
waste cinder banks, where leaching and erosion by rain- 
water result (78). Despite efficient stack collection 
systems, aerial fallout of lead has resulted in severe 
local contamination. Leaves of post oak (Quercus 
stcllaia) and shortleaf pine (Pinus echinata) within 0.5 
mile of a lead smelter in Missouri contained levels of lead 
as high as 8,125 and 11,750 ppm (7). Samples of 
various plant species containing normal lead concen- 
trations could be obtained only beyond a 20-mile radius 
from the smelter-mining-milling complex. The deaths 
of 20 horses prompted the analyses of samples of forage 
grass in the vicinity of another Missouri smelter, in 
which concentrations as high as 14,700 ppm lead were 
reported (7). 

Lead mines associated with limestone or dolomite 
stratabound deposits (Missouri's Old and New Lead 
Belts) must pump out 5,000-7,000 gal/min of ground- 
water in order to operate. The relatively clear water is 
typically cycled through the mill and ffotation concen- 
trators and ends up containing mud, organic flotation 
agents, and other wastes. This effluent is discharged into 
valleys formed by dams of coarser mill tailings, and 
the final effluent is the tailing pond outfall. In the New 
and Old Lead Belt mining-milling areas, tailing pond 
outfalls have resulted in the deposition of a dark lead- 
bearing dolomite mud on stream bottoms; the mud in 
turn is covered by a gray algal-bacterial slime. Benthic 
fauna were found to be intolerant of the dolomite mud 
covering (78) . 

Other environmental sources of lead are landfills or 
dumps, fly ash from coal-burning power stations, coal 
combustion, sewage sludge, and application of pesticides 
containing lead (47). Small emissions occur from lead 
oxide manufacturing and fuel oil combustion (39). 
Coal mining could contribute significant quantities of 
lead to the environment during flood erosion (78). 

Upon entering natural waters, most lead is precipitated 
to the sediment bed as carbonates or hydroxides (80). 
Laboratory studies have shown that lead compounds can 
be transformed to tetraalkyllead, but the exact mecha- 
nism is still unclear. Wood et al. (90) proposed a Type I 
microbial methylation reaction for lead, where the high 



I. 15, No. 1, June 1981 



17 



redox potential of the Pb IV/Pb II redox couple causes 
Pb IV to act as an attacking electrophile. Subsequent 
heterolytic cleavage of the Co-C methylcobalamin bond 
results in the transfer of a carbanion methyl group to 
the more oxidized form of the element. Jarvie et al. 
(25), however, were unable to achieve methylation of 
trimethyllead salts and lead nitrate by this microbial 
pathway and, instead, proposed a chemical mechanism 
for conversion of the compounds to tetramethyllead in 
active anaerobic sediments. Other workers (57) have 
demonstrated the methylation of lead(II) compounds 
to tetramethyllead by microorganisms, which suggests 
other routes of methylation besides the mentioned micro- 
bial and chemical routes. It is not now known whether 
lead, like mercury, can accumulate through the food 
chain as an alkylated entity. Because divalent lead is 
the principal form accumulated by aquatic animals, 
the possibility of methylation of ionic lead in vivo can- 
not be disregarded (80, 53). Tetraalkyllead compounds 
have been found in various marine tissues (53). 

MERCURY 

Mercury has an impressive list of uses encompassing 
many different types of industry and has almost 3.000 
distinct applications (72). The largest end user in the 
United States is the electrical apparatus industry, which 
accounts for 42 percent of total consumption and in- 
cludes the manufacture of mercury batteries and alkaline 
energy cells, vapor discharge lamps, rectifiers, and 
switches. The second greatest use (16 percent) is in 
the electrolytic preparation of caustic soda and chlorine 
(chloralkali industry), where the continuous-flow mer- 
cury cathode cell still accounts for about 20 percent of 
total chloralkali-producing capacity (4). Mercury con- 
sumption in the United States for chloralkali purposes 
has been reduced sharply since the 1960's for at least 
three reasons: a decrease in the number of new mercury 
cell chloralkali plants, modification of existing plants 
to reduce mercury losses, and conversion of some plants 
to the diaphragm process. The paint industry consumes 
13 percent of the mercury used in the United States. 
mostly for mildew proofing (58). Industries manufac- 
turing industrial control instruments consumed about 8 
percent of U.S. mercury supplies in the manufacture of 
switches, relays, gauges, pump seals, and valves. Other 
uses, which account for about 15 percent of total 
mercury consumption, include those in agriculture, den- 
tistry, general laboratory applications, and pharmaceu- 
ticals (4). Mercury consumption for pesticide use in 
agriculture is down sharply from the late 1960's, but a 
relatively small number of mercury pesticide formula- 
tions are currently available (5, 58). The U.S. paper 
and pulp industry no longer uses mercury as a slimacide, 
but still may be consuming mercury at the combined 
chloralkali-pulping operations (12). 



There are two primary ways mercury reaches the aqi< 
ic environment: pre- 1975 chloralkali operations < 
pre- 1972 paper-pulping operations. Although the int 
duction of mercury to the environment from these 
dustries is now relatively small, stream and lake s{i 
ments contaminated from discharges 10-15 years i 
are a persistent mercury source, and methylation 
anaerobic microbes initiates bioconcentration and f( 
chain bioaccumulation (12). Seepage from some we 
disposal areas of closed chloralkali plants continues 
contaminate streams and reservoirs (56). Higher-th 
background mercury sediment concentrations have b" 
found more than 100 miles downstream from a s 
thetic fiber operation that stopped using mercury 
years ago (3). 

Although U.S. mercury consumption and indust 
mercury loss have been reduced from early 1970 lev 
mercury contamination associated with increased c 
and crude oil production may pose future proble 
Fossil fuels contain from 10 ppb to several ppm n 
cury, depending on the coal type (12). Inasmuch 
the United States is preparing for a dramatic intensif 
tion of coal mining, combustion, and conversion 
appears likely that an environmental mercury prob 
will be present for some time to come. 

Bacteria present in most natural waterways can coni 
mercury to methylmercury. Ridley et al. proposes 
Type I microbial methylation reaction for mercury 1 
is very similar to that already mentioned for lead ( 
90). Most of the mercury in fish exists as methyln 
cury derived largely from food. Some authors h 
suggested that water, as well as food, is a major soi 
of methylmercury in fish (80). 

ARSENIC 

Arsenic occurs in association with complex base-mi 
ores, chiefly those of copper, lead, gold, and to a lei 
extent, cobalt and tin (60, 66). The element is a mil 
constituent of those ores and is regarded as a troul 
some impurity in smelting and refining of base me 
The recovery of arsenic in residues from fumes, si I 
mings. and flue dusts involves sophisticated technoll 
and is costly and relatively inefficient. As a result, 
refinery incentive for arsenic recovery is closely cc 
lated with concurrent economics and market conditi i 
In 1978, all domestic production of arsenic was i 
fined to the copper smelting-refining complex of 
American Smelting and Refining Company (ASARC 
in Tacoma, Washington. Anaconda, another large No 
western copper smelting company located in Bi' 
Montana, has arsenic-refining facilities that have 
mained unused for the past several years. Bee: \ 
domestic arsenic production is so limited and availab J 
is so closely tied to prevailing copper prices, the Ur ' 



18 



Pesticides Monitoring Joub^ 



;es historically has met most of its requirements for 
inical compounds by importation (60). For example, 
nestic production supplied only 10.5 percent of total 
;. arsenic demand in 1973 and about 50 percent in 
'8 (60, 66). 

riost all arsenic (97 percent) enters end-product 
lufacturing in the form of white arsenic or As20:,. 
; other 3 percent is in the metallic form and is used 
an additive in specialized lead and copper alloys, 
hty-two percent of white arsenic is consumed in the 
nufacture of agricultural pesticides, such as lead 
;nate, calcium arsenate, sodium arsenite, and organic 
;nicals that are used as insecticides, herbicides, 
gicides, algicides, desiccants, and defoliants (60). 
janoarsenical compounds include cacodylic acid, di- 
ium methanearsonate (DSMA), monosodium meth- 
arsonate (MSMA), and sodium cacodylate (5, 60). 
; only extensive use of arsenic that is not based on 
toxicity is in the glass industry, where it is used as a 
olorizer and as a constituent of opalescent glass and 
imels. Other small uses (60) are in the paint industry 
gments), pyrotechnics (constituent of fireworks), 
irmaceuticals (treatment for skin disorders and 
:ping sickness), electronics (diodes, transistors, and 
!rs), and the metals industry (as an additive to 
rous alloys to increase cast iron strength). 

ienic enters the aquatic environment by four primary 
ites: (1) Dissemination by air pollution. Because of 

complexity, inefficiency, and expense of removing 
enic from smelter stack gases, the element has be- 
ne a major air pollution problem in states having 
elting-refining operations (60). Coal combustion is 
)ther important source of arsenic to the air. (2) 
alter solid waste disposal. Because no domestic 
tallurgical plants, except ASARCO, process commer- 
1 arsenic, the disposal of fumes, skimmings, and flue 
its could constitute a solid waste pollution problem 
:cting both soil and water. (3) Arsenical pesticides, 
ntinued use is expected for many years to meet the 
nand for effective pest control in the face of expand- 

agricultural production (60, 66). (4) Geologic. 
;ause arsenic is found in association with specific 
ilogic formations of volcanic origin, ground and sur- 
e waters in some areas of the western United States 
'e high arsenic levels (31 ) . 

ienic occurs in natural waters primarily in the 
;nate-arsenite forms (27, 79). Inorganic forms of 
;nic can be methylated by various microorganisms, 
uding fungi, methanogenic bacteria, yeasts, and 
cellular algae (43). Evidence suggests that arsenic 
s in the lower oxidation states perform a free-radical 
ick (homolytic cleavage) on the Co-C bond of 
hylcobalamin or nucleophilic attack on 5-adenosyl- 



methionine, as well as on methylcobalamin (49, 90). 
Fish apparently can biosynthesize organoarsenic com- 
pounds within the gastrointestinal tract (34, 43). How- 
ever, the main source of arsenic for fish is primarily 
organoarsenic compounds that are synthesized at lower 
stages in the food chain (34). Generally, arsenic is not 
biomagnified in aquatic food chains. Penrose et al. (44) 
suggested that organisms at each trophic level convert 
inorganic arsenic to a detoxified organic form, orga- 
nisms at the next higher trophic level then rapidly 
excrete the ingested organic arsenic, precluding food 
chain bioaccumulation. 

SELENIUM 

In 1978, all primary selenium was produced as a by- 
product from the processing of copper refinery slimes 
to recover gold, silver, and tellurium. Three copper 
refineries (AM AX Copper, Inc., Carteret, New Jersey; 
ASARCO Inc., Amarillo, Texas; and Kennecott Copper 
Corp., Magna, Utah) accounted for all domestic pro- 
duction of selenium (62, 66). Secondary production, or 
recycling, was limited; only about 1 percent of the 
1978 consumption was recovered from xerographic and 
rectifier scrap and chemical waste products. Domestic 
consumption of selenium decreased steadily from 1974 
to 1977 and increased slightly in 1978 (66). Major end 
uses of selenium in 1978 (66) were in electronic and 
photocopier components (35 percent), glass manufac- 
turing (30 percent), and chemicals and pigments (25 
percent). The electronics industry used selenium in dry- 
plate rectifiers for many years, but silicon, germanium, 
and cadmium have largely replaced it in these applica- 
tions. The use of metal drums coated with photocon- 
ducting amorphous selenium in the dry photographic 
process of xerography has become a major end use of 
the metal. Selenium has the property of converting light 
energy directly into electrical energy — a property that 
has enabled the development of numerous photocell 
devices, such as photographic exposure meters and solar 
batteries (41). 

The glass and ceramics industry adds selenium to glass 
melt to control final product color. Selenium is used 
to neutralize green tinting caused by iron impurities, 
resulting in the manufacture of clear glass. Addition of 
more selenium to the melt produces a pink-to-ruby red 
glass. Its use in dark-colored glass in buildings and 
vehicles to reduce glare and heat transfer is increasing. 

A large number of selenium compounds have commer- 
cial uses, ranging from semiconductor research to anti- 
dandruff agents in shampoos. Much of the selenium 
consumed by the chemical industry is used to prepare 
pigments containing selenium. A major class of pigments 
is the cadmium sulfoselenide compounds, which have 
superb resistance to sunlight, heat, and chemical attack 
(41). 



-. 15, No. 1, June 1981 



19 



The primary sources of selenium in the environment 
are geologic and industrial. Selenium closely resembles 
sulfur chemically, and sulfur or sulfide deposits of 
bismuth, copper, iron, lead, mercury, silver, and zinc 
sometimes contain as much as 20 percent selenium (68). 
Other sulfate minerals, such as barite and jarosite, con- 
tain selenium, and native sulfur can contain more than 
0.1 percent selenium. Other geologic formations con- 
taining selenium include sandstones, limestones, and 
shales. Sandstones containing > 100 ppm selenium have 
been found in Wyoming {17, 91). The Niobrara for- 
mation, a limestone region of South Dakota, contains 
> 40 ppm selenium in chalky shales and marls. Phos- 
phate rocks associated with limestone may contain 
from 1 to 300 ppm selenium, suggesting the occurrence 
of selenium in phosphate fertilizers. Of the sedimentary 
rocks, shales have been mainly responsible for cases of 
selenium poisoning in animals in the United States. For 
example, vegetation in some areas of the Pierre Forma- 
tion near the Missouri River in southern South Dakota 
has potentially toxic selenium concentrations. These 
shales are considered highly seleniferous and have 
selenium levels ranging from 1 to > 30 ppm (41). 

Industry releases selenium to the environment through 
combustion of coal and fuel oil, nonferrous smelting 
and refining processes, metal refining, and glass manu- 
facturing. Domestic coal averages 3.2 ppm selenium 
(46). Average selenium concentrations are 1.3 ppm in 
lignite coal and 2.08 ppm in central and western U.S. 
coals (42). In one study, about 53 percent of the 
selenium in coal was emitted to the atmosphere during 
combustion, either as volatilized selenium or in asso- 
ciation with fly ash particles too small to be trapped 
by precipitators (41). Coal combustion accounted for 
62 percent of the total industrial emission of selenium 
in 1970 (41). EPA found that crude oil contained an 
average of 0.4 ppm selenium (41), and Hashimoto et al. 
(19) reported averages of 0.92 ppm in raw petroleum 
and about 1.0 ppm in heavy petroleum. Smelting and 
refining of nonferrous metals produces slag heaps and 
tailing dumps containing high concentrations of seleni- 
um. Thus, solid wastes from metal mining and milling 
may be a more serious source of selenium pollution 
than is atmospheric fallout from base metal smelting 
and refining (41). Selenium emissions are high in glass 
manufacturing, because the high temperature of the 
glass melt volatilizes selenium (41). 

Attempts to correlate atmospheric concentrations of 
selenium with the location of industrial selenium emis- 
sions have generally met with only limited success. For 
example, Traversy et al. (24) found the highest selenium 
concentrations in precipitation samples at or near highly 
industrialized locations in the Great Lakes region, and 
Copeland (10) showed that selenium concentrations in 
Lake Michigan zooplankton increased near Chicago. In 



these two situations, the effects of selenium from ind 
trial emissions appeared to be localized, and nati 
sources of selenium may generally be more import 
than anthropogenic ones (41). 

Ingestion may be the most important mode of selenii 
uptake by aquatic biota, but more research is neen 
to confirm this possibility (56). Phillips and Rii 
(80) concluded that the poor survival of stocked 
in a highly seleniferous Colorado lake was due to 
accumulation of excess selenium through the fi 
chain. Several species of molds and microorganisms i 
methylate selenium (41). Little is known, howe^ 
about selenium methylation pathways in the aqux 
environment. 

Methods and Materials 

SAMPLE COLLECTION 

Fish were collected by FWS biologists, state fish 
game personnel, and local commercial fishermen, \ 
used a variety of nonchemical collecting techniq 
(e.g., trapping, electrofishing, seining). After the ti 
length and weight of each fish had been determir 
the sample composites were separately wrapped 
aluminum foil, frozen, and shipped to CNFRL. 

Fish from frozen composites were reduced to ice-ci 
sized blocks with a Hobart Model 5212 food sen 
band saw. Blocks were passed twice through a l£| 
(Hobart 1 hp Model 4822) or small (Hobart Vi 
Model 4612) meat grinder, depending on total c( 
posite size and weight. Between sample homogen 
tions, the band saw and disassembled grinder com 
nents were washed with hot water or steam and rin: 
with deionized water. About 400-g portions of groij 
fish were placed in an acid-cleaned glass jar witl 
Teflon-lined cap and stored in a freezer. In 1976, fro 
10-g portions of 83 samples representing 44 stati 
were sent to the EPA Region VII Laboratory in Kai 
City for digestion and analysis. All samples colleci 
in 1977 were prepared and analyzed at CNFRL. 

DIGESTION AND ANALYSIS OF SAMPLES COLLECTED IN 

Arsenic, Cadmium, and Lead — Five grams of tha' 
fish homogenate were placed in 10-in. Technicon dige 
tubes. Ten milliliters of concentrated HNO, was ad I 
to each tube, and the sample-acid mixture was heic 
room temperature for 1 hr to reduce foaming w i 
heat was applied. Samples were heated on a Techni 
Model BD-40 block digestor at 150°C for 60 mini 
and at 250°C for 90 minutes. The gradual incn; 
from room temperature to 150'^C allowed the sam i 
to dissolve with little foaming; heating to 250°C ■ 
required to overcome reflux action at the constric 
of the digestor tube. Samples were heated to dryit 



20 



Pesticides Monitoring JoukI 



lecompose lipid material. If the sample was black 
n dryness was reached, it was removed from the 
stor. cooled, treated with an additional 10 ml con- 
rated HNO,, and returned to a cold digestion block 
for 90 minutes at 250°C. Subsequent addition of 
nl portions of acid was continued until the appear- 
i of a white residue indicated complete digestion, 
white residue was dissolved with 10 ml 10 percent 
0:, at 90°C. Dilution to 50 ml with deionized water 
Med a final acid matrix of 2 percent HNO,. This 
:edure allowed simultaneous preparation of up to 
tissue samples, with only HNO;, as the oxidizing 
. Unfortunately, the recovery of selenium by this 
hod was incomplete, precluding the use of selenium 
I originating from the 1976 samples. 

I tissue digestates (2 percent HNO,) were analyzed 
a Jarrell-Ash Model 975 Atomcomp inductively 
pled argon plasma (ICAP) optical emission spectro- 
tometer. Samples were introduced in a cross-flow 
iilizer at 1.4 ml/min by a Gilson eight-channel 
ip. An autosampler maintained sample flow at 30 
ples/hr. Other pertinent ICAP parameters follow: 



Incident RF power; 
Reflected RF power: 
Observation heiglit: 
Sample argon flow rate: 
Coolant argon flow rate: 



l.I kW 
20 W 

15 mm above load coil 
0.5 1/min 
18 1/min 



ection limits for arsenic, cadmium, and lead were 
i, 0.05, and 0.10 mg/kg, respectively. 

■cury — One gram of sample was placed on the 
cm of a dry BOD bottle; 1 ml each of concentrated 
■O^ and HNO, was added, and the bottle was placed 
water bath at 58°C until the tissue was completely 
olved (30-60 minutes). The bottle was cooled to 
^ in an ice bath, and 1 g KMn04 crystals was added 
maintain oxidizing conditions. The digestate was 
ed, loosely capped, and held overnight at room 
perature (75). 

cold-vapor atomic absorption method for mercury 
lysis (75) can be summarized as follows: Each 
:state was diluted with distilled water to a final 
ime of 125 ml, and 6 ml sodium chloride-hydrox- 
nine sulfate solution was added to reduce excess 
nanganate. After 30 seconds, 5 ml stannous sulfate 
tion was added and the bottle was immediately 
;hed to the aeration apparatus. Mercury vapors were 
pt into a Plexiglass absorption cell and measured 
I Coleman MAS-50 mercury analyzer system (26). 
action limit was 0.02 mg/kg. 

5STI0N AND ANALYSIS OF SAMPLES COLLECTED IN 1977 

cury, Cadmium, and Lead — Mercury, cadmium, 
lead residues in fish were oxidized by acid digestion 

. 15, No. 1, June 1981 



in heated, enclosed glass bombs (45-ml acylation tubes, 
Regis Chemical Co.), which allow oxidation and re- 
covery of all three meals with a single digestion. Diges- 
tion tubes were cleaned by successive rinsing with 
concentrated HNO,, HCI, and ultrapure water (15-18 
megohm-cm specific resistivity). Cleaned tubes were 
oven-dried, cooled, and covered with sheet polyethylene 
before the sample was introduced. Teflon caps for the 
tubes were soaked successively for several hours in 
boiling concentrated HNO3 and HCI, followed by a 
final rinsing with ultrapure water. 

Approximately 2 g (±0.01 g) thawed fish homogenate 
was weighed into tared digestion tubes. Sub-boiling- 
point, distilled concentrated HNO, (2 ml) and double- 
distilled HCIO^ (1 ml) were added and the mixture was 
vortex mixed, capped loosely, and allowed to predigest 
overnight at room temperature (/). The mixture was 
vortex mixed again, and the bomb was sealed and 
placed in a heated aluminum block (65 °C) for 48 
hours. The sample was quantitatively transferred and 
diluted to a final weight of 50 ± 0.01 g with 1 percent 
HCI. Diluted digestates were stored in cleaned poly- 
propylene bottles (38) for cadmium and lead analyses 
or borosilicate test tubes for mercury analysis (14). 

Mercury was determined by flameless atomic absorp- 
tion spectrophotometry (AAS) (28). The analytical 
system was automated with a Technicon Autosampler 
IV and Proportioning Pump III, with appropriate 
pump tubes, pulse suppressors, mixing coils, and locally 
fabricated phase separator (Figure 2). Atomic absorp- 
tion measurements were made on a Perkin-Elmer Model 
305B spectrophotometer, using the 253.7-nm resonance 
line from an electrodeless discharge lamp. Scale expan- 
sion up to 10 X was used when appropriate. The detec- 
tion limit was about 0.01 mg/kg. The absorption cell 
was constructed from a Pyrex tube about 100 mm long 
and 6 mm I.D. with quartz end windows. Side arms of 
4-mm-O.D. Pyrex were attached near each end of the 
cell for vapor passage. The cell was heated to 35-40°C 
with a high-intensity radiant heat projector (Cole- 
Parmer Dyna Lume Model 3151-6) to prevent con- 
densation on the end windows. 

Lead and cadmium were measured with a Perkin-Elmer 
Model 305B spectrophotometer equipped with an 
HGA-2100 graphite furnace and an AS-1 autosam- 
pling system. Table 2 specifies the instrument conditions 
for measuring each element. A four-point additions 
procedure to correct for chemical and matrix interfer- 
ences was performed on each diluted digestate: 

( 1 ) Digestate -\- 0.00 ppm Pb; + 0.00 ppm Cd 

(2) Digestate -f 0.02 ppm Pb; + 0.002 ppm Cd 

(3) Digestate -f 0.04 ppm Pb; + 0.004 ppm Cd 

(4) Digestate + 0.06 ppm Pb; -f 0.006 ppm Cd 

21 



Pulse Suppressors 




-ff 




Hydroxylamine Hydrochloride 1.5% 



Stannous Chloride 10% 



J 



D(5 1 



SaTiplef 
Wash H20 



FIGURE 2. Flow scheme for automated digestion and determination of mercury. 



TABLE 2. Instrumental conditions for atomic absorption 

measurement of cadmium, lead, arsenic, and selenium in 

freshwater fish from the United States, 1977 



Condition 


Cadmium 


Lead 


Arsenic Selenium 


Wavelength, nm 


228.8 


283.3 


193.7 


196.0 


Spectral band width, nm 


0.7 


0.7 


0.7 


2.0 


Temperature ramping 


no 


no 


no 


no 


Drying time, °C 


90(30) 


90(30) 


— 


, — 


(time, seconds) 










Charring time. °C 


400(20) 


400(20) 


— 


— 


(time, seconds) 










Atomization temp.. °C 


2200(7) 


2300(7) 


— 


— 


(time, seconds) 










Purge gas and flow 


Ar(20) 


Ar(20) 


Ar 


Ar 


(ml/minute) 










Gas mode 


normal 


normal 


EDL 


— 


Source 


EDL 


EDL 


no 


EDL 


Background correction 


Dij^rc 


DiArc 


5 mv 


no 


Scale expansion 


3X 


lOx 


PR I 


3X 


Recorder full scale 


10 mv 


10 mv 


— 


10 mv 


AS-1 injection volume 


10 Hi 


10 Hi 


none 


— 


Tube type 


uncoated 


uncoated 


— 


— 


Quaru cell temp., "C 


— 


— 


— 


800 


Reductant 


— 


— 


1000 


NaBH. 


Reaction flask volume, ml 


— 


— 


NaBH< 


10 


Analysis cycle time 


— 


— 


10 


PR II 


Detection limit, mg/kg 


0.01 


0.1 


0.05 


0.05 



The average of two injections was used as one additions 
point. Correlation coefficients (r) below 0.999 for the 
line of best fit were rejected, and corresponding diges- 
tates were rerun. 



point, distilled concentrated HNO^ (5 ml) was ad 
the flask was loosely covered with sheet polyethyl, 
and the mixture was predigested overnight at r| 
temperature. Subboiled HNO, (25 ml) and del 
distilled HCIO4 (3 ml) were added, and the flask 1 
heated on a micro-Kjeldahl rack to drive off Hf 
After digestion had proceeded through the HCIO4 f 
ing and reaction stages, additional heat was applie^ 
drive off the acid. When about 0.5 ml HCIO4 remai- 
the flasks were removed from the heat, cooled, 
contents were diluted with 3 percent HCl to 
volumes of 100 ml. Diluted digestates were store« 
linear polyethylene bottles before analysis. 

Predigestion sample preparation for selenium was 
same as that for arsenic. Following predigestion, 2.' 
subboiled HNO^ and 1 ml double-distilled HCIO4 1 
added and the flask was heated to drive off Hf 
Digestion was allowed to proceed through HCIO4 1 
ing and reaction stages. The HCIO^ reaction stage 
characterized by an initial foaming with subseq 
clearing (decoloration) of the digestate. Care was ti 
to terminate the digestion before HCIO4 was driver ' 
(88). Cooled digestates were diluted to 100 ml wi I 
percent HCl and transferred to linear polyethy* 
bottles. 



Arsenic and Selenium — For arsenic digestions, approxi- 
mately 2 g (±0.01 g) thawed fish homogenate was 
weighed into a tared, 100-ml Kjeldahl flask. Sub-boiling- 



Arsenic and selenium were analyzed with a PeK 
Elmer MHS-1 mercury-hydride system in conjunc 1 
with a Perkin-Elmer Model 305B spectrophotomiiil 



22 



Pesticides Monitoring JouBf 



-ument conditions for measuring the elements are 
d in Table 2. On the MHS-1 system, a reaction 
: containing 10 ml diluted digestate was installed 
1 polypropylene manifold. Argon was recycled in 
3sed circuit through the reaction flask and a heated 
tz cell. An NaBH4 pellet (Alfa Ventron) was dis- 
,ed into the flask and reacted with the digestate 

to form hydrogen, which reduced the metals to 
tile arsine and hydrogen selenide. The gas stream 
led the hydrides into the heated quartz cell where 

were decomposed and measured. Complete analy- 
from addition of the digestate to readout on the 
trophotometer, proceeded automatically for each 

a. 

■ISTICAL TREATMENT 

vo-way analysis of variance (ANOVA) with sta- 
i and years as main effects was used to test two 
hypotheses: (1 ) There was no significant difference 
letal residue concentrations due to location, and (2) 
5 was no effect due to time (1972-73 vs. 1976-77). 
eneral, stations were confounded by species differ- 
s across years. The following adjustments were 
e in the data sets before statistical testing: 

i) Absolute values were used for all less than ( < ) 

ita. 

)) Selenium values for 1972 and 1973 were avail- 

ile for only 44 of the stations sampled in 1977. 

tierefore, the two-way ANOVA data set for selen- 

m consisted of 44 stations and 3 years (1972, 1973, 

id 1977). 

;) The detection limit for cadmium in 1977 sam- 

es (O.OI ppm) was one-fifth the limit in 1972 and 

*76 samples (0.05 ppm). Therefore, we adjusted 

1 1977 cadmium values <0.05 mg/kg to 0.05, to 

iminate bias due to differences in detection limits. 

he two-way ANOVA data set consisted of 82 

atching stations and two time periods (1972 vs. 

)76-77). 

i) The two-way ANOVA data set for lead and mer- 

iry also consisted of 82 stations and two time periods 

1972 vs. 1976-77). 

;) Detection limits for arsenic were 0.05 ppm for 

le 1972 and 1977 samples and 0.25 ppm for 1976 

mples. Because most of the 1977 arsenic concentra- 

Dns were <0.25 mg/kg, the results of arsenic residue 

lalyses for the 1976 stations were not included in 

e two-way ANOVA set; consequently, only 44 

atching stations and 2 years (1972 vs. 1977) 

mained. 

error sum of squares to estimate variation within 

/idual samples was obtained from a preliminary 

way ANOVA with an unbalanced cell size (52). 

method of weighted squares of means (52) was 

used to make inferences about main effects. All 



analyses were performed on log-transformed data [logio 
(1 -f- cone.)] 

Results 

The precision and accuracy of the 1976-77 trend- 
monitoring analyses were determined by duplicate 
sample sets and samples containing inorganic spikes. 
A duplicate sample set is defined as two aliquots of 
tissue from the same sample composite carried through 
the entire digestion-analytical procedure. The average 
difference of duplicate sets was within 25 percent for 
all elements, except for mercury in 1976 samples (37 
percent) and lead in 1977 samples (70 percent). Aver- 
age recoveries from spiked samples were within 10 
percent of the added quantity, except for mercury in 
1976, for which average recovery was 64 percent (Table 
3a). Analyses of reference materials yielded average 
values within the specified certification ranges for all 
elements (Table 3b). 

TABLE 3. Quality control results of the 1976-77 trend- 
monitoring analyses 

a. Recoveries of elements from spiked samples 



1976 









Mean 








Mean 








CONCN., 


RECOV- 






CONCN., 


RECOV- 




Element 


« 


tiO/ML 


ERY, % 


S.D. 


n 


tIG/ML 


ERY, % 


S.D. 


Cadmium 


14 


0.1 


92 


10 


7 


0.004 


106 


7 


Lead 


13 


0.1 


91 


10 


8 


0.040 


102 


12 


Mercury 


6 


0.001 


64 


15 


8 


0.010 


98 


12 


Arsenic 


14 


0.1 


98 


17 


17 


0.004 


94 


10 


Selenium 


— 


— 


— 


— 


15 


0.0O4 


101 


17 



b. Reference materials — 1977 



Certified 
Reference concn. range, 

material ^ element ^ig/o 



Mean 

CONCN., 
MG/G S.D. 



NBS 


cadmium 


0.27 ± 0.04 


11 


0.31 


0.02 


Bovine liver 












NBS 


lead 


0.34 ± 0.08 


9 


0.38 


0.05 


Bovine liver 












NBS 


mercury 


0.016 ±0.002 


12 


0.016 


0.005 


Bovine liver 












FDA 


arsenic 


11 ±2 


13 


10.5 


1.37 


Cod 












NBS 


arsenic 


3.3 ±0.4 


18 


3.27 


0.35 


Albacore tuna 












FDA 


selenium 


1.4 ±0.4 


13 


1.36 


0.21 


Cod 












NBS 


selenium 


3.6 ± 0.4 


18 


3.68 


0.40 


Albacore tuna 













NOTE: n ~ number of samples; S.D. = standard deviation; FDA = 
Food and Drug Administration; NBS = National Bureau of Standards. 

Locations, species sampled, average size, and trace ele- 
ment concentrations for 1976-77 trend-monitoring 
samples are listed in Table 4. Eighty-three samples 
collected in 1976 were analyzed by the EPA Region 
VII Laboratory. The 1977 samples (157 samples of 
163 collected) were analyzed by CNFRL. The data 
ranges in mg/kg wet weight were Pb, 0.10-4.92; Hg, 
0.01-0.84; Cd, 0.01-1.04; As, 0.05-2.92; and Se, 0.05- 



15, No. 1, June 1981 



23 



2.87. To examine potential temporal trends of trace 
element concentrations, 1976-77 data for lead, mercury, 
cadmium, and arsenic were compared with those re- 
ported by Walsh et al. (87) for the same stations in 



1972. Because selenium concentrations were not 
ported for the 1976 collections, 1977 selenium coni 
trations were compared with those from the s; 
stations in 1972 and 1973. 



TABLE 4. Conccnirntions of cadmium, lead, mercury, arsenic, and selenium in whole-fish samples collected for the Nati 

Pesticide Monitoring Program, 1976-77 



( 


Station Number 
AND Location 

(FIGURE 1 ) 


Species ' 


No. 

OF 

Fish 


Average Size 




Residues, 


mg/kg Wet Weight 






Length, 

INCHES 


Weight, 

LB 






Cadmium 


Lead 


Mercury Arsenic 


Sele 






ATLANTIC 


COASTAL STREAMS 












1. 


Pennobscot River, 
Old Town, Me. 


white perch 
white sucker - 


5 
5 
5 


9.8 
14.3 
14.1 


0.5 

1.18 

1.16 


<0 05 
<0.05 


0.12 
0.13 


0.23 
0.20 


<0.25 
<0.25 




51. 


Kennebec River, 
Hinckley. Me. 


yellow perch 
white sucker 


5 
5 

5 


9.6 
14.2 
14.5 


0.36 
1.22 
1 22 


<0.05 
0.06 


0.13 
0.13 


0.34 
0.16 


<0.25 
<0.25 




52. 


Lake Champlain, 
Burlington, Vt. 


northern pike 
brown bullhead 


5 
5 
5 


17.8 
11.1 
10.7 


1.48 

0.8 

0.64 


<0.05 
<0.05 


<0.10 
0.34 


0.21 
0.04 


<0.25 
<0.25 




53. 


Merrimac River, 
Lowell, Mass. 


largemouth bass 
white sucker 


4 
5 
5 


9.7 
11.8 
12.6 


0.48 
0.64 
0.76 


<0.05 
0.06 


0.21 
1.23 


<0.02 


<0.25 
<0.25 




2. 


Connecticut River, 
Windsor Locks, Conn. 


white perch 
white catfish 


5 
5 
5 


9.2 
11.6 

12.1 


0.46 
0.74 
0.88 


0.11 
0.25 
0.16 


0.40 
1.19 
0.79 


0.27 
0.08 
0.12 


<0.25 
<0.25 
<0.25 




3. 


Hudson River, 
Poughkeepsie, N.Y. 


largemouth bass 
goldfish 


5 
5 
5 


12.1 
11,3 
11.1 


0.92 
1.18 
1.08 


<0.05 
0.20 
0.32 


0.10 
3.07 
3.83 


0.09 
0.05 
0.06 


<0.25 

<0.25 

0.68 




54. 


Raritan River, 
Highland Park, N.J. 


carp 


5 


17.3 


3.14 


<0.05 


0.23 


0.05 


<0.25 




4. 


Delaware River, 
Camden, N.J. 


white perch 
white sucker 


5 
5 
5 


7.0 
15.4 
15.2 


0.2 
1.7 
1.6 


0.22 
0.20 
0.16 


1.57 
0.98 
1.17 


0.14 
0.12 
0.14 


0.21 
0.10 
0.10 


M 
0.: 

0,: 


5. 


Susquehanna River, 
Conowingo Dam, Md. 


white perch 
channel catfish 
carp 


5 
6 

5 

5 


6.3 
10.7 
16.6 
16.7 


0.1 
0.4 
1.9 
1.9 


0.05 
0.04 
0.02 
0.05 


0.44 
0.19 
0.34 
0.26 


0.10 
0.05 
0.08 
0.11 


0.28 
<0.05 

o.n 

0.11 




6. 


Potomac River, 
Little Falls, Md. 


largemouth bass 
carp 


5 
5 
5 


12.2 
19.0 
17.5 


1.2 
3.9 
2.9 


<0.01 
0.04 
0.04 


0.15 
0.78 
0.33 


0.20 
0.12 
0.09 


<0.05 
0.13 
0.16 


0.- 
0.. 
0.. 


55. 


James River, 
Richmond, Va. 


smallmouth bass 
redhorse 


5 
4 
4 


9.2 
16.0 
17.5 


0.4 
1.8 

2.2 


0.03 
0.81 
0.36 


0.14 
0.32 
0.15 


0.12 
0.25 
0.18 


0.06 
0.10 
0.07 


0, 

c: 

0. 


7. 


Roanoke River, 
Roanoke Rapids, N.C. 


white catfish 


5 
5 


11.1 
12.2 


0.54 
0.86 


<0.05 


0.16 


0.05 


<0.25 




8. 


Cape Fear River, 
Elizabcthtown. N.C. 


gizzard shad 


5 
5 


13.7 
13.3 


1.06 
0.96 


0.08 


0.40 


0.04 


0.26 




56. 


Pee Dee River, 
Dongola, S.C. 


white catfish 


4 

5 


15.1 
14.7 


1.35 
1.26 


<0.05 


0.20 


0.45 


<0.25 




9. 


Cooper River, 
Summerton, S.C. 


striped bass 
channel catfish 


2 
5 
5 


26.0 
13.3 
13.9 


7.3 

0.86 

0.8 


<0.05 


0.28 


<0.02 


<0.25 




10. 


Savannah River, 
Savannah, Ga. 


largemouth bass 
channel catfish 
white catfish 
carp 


4 
3 
3 
4 


10.9 
15.1 
13.8 
14.6 


0.83 
1.33 
1.63 
1.83 


<0.05 
0.08 
0.17 


<0.10 
<0.10 
<0.10 


0.12 
0.06 
0.14 


<0.25 
0.63 
1.46 




57. 
11. 


Altamaha River, 
Doctortown, Ga. 

St. Johns River, 
Welaka, Fla. 


brown bullhead 
channel catfish 
largemouth bass 

inactive « 


5 
3 

5 


14.6 
17.4 
15.4 


1.56 

1.9 

2.1 


<0.05 
<0.05 


0.30 
0.18 


0.14 
0.34 


<0.25 
<0.25 




12. 


St. Lucie Canal, 
Indiantown, Fla. 


largemouth bass 
white catfish 
channel catfish 


5 
5 
3 


15.3 
13.4 
19.8 


2.26 
1.24 
3.03 


<0.05 
<0.05 


<0.10 
0.14 


<0.02 
0.06 


<0.25 
<0.50 





24 



Pesticides Monitoring Joui^ 



BLE 4. (cont'd.). 



Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for 
the National Pesticide Monitoring Program, 1976-77 



TATioN Number 
AND Location 

(FlGUKEl) 


Species ' 


No. 

OF 

Fish 


Average Size 




Residues, 


MG/KG Wet Weight 




Length, 

inches 


Weight, 

LB 




Cadmium 


Lead 


Mercury Arsenic 


Selenium 


Androscogin River, 
Lewislon, Me. 


yellow perch 
white sucker 


5 
5 
5 


9.3 
12.2 
12.4 


0.38 
0.68 
0.38 


<0.05 
<0.05 


0.16 
0.24 


0.20 
0.11 


<0,25 
<0.25 


— 






GULF COAST 


STREAMS 












Suwanee River, 
Old Town, Fla. 


inactive 


















Apalachicola River, 
Jim Woodruff Dam, Ala. 


largemouth bass 
spotted sucker 


5 
5 
5 


14.1 
17.5 
18.4 


1.56 

2.38 
2.82 


0.02 
0.02 
0.03 


0.18 

<0.10 

0.16 


0.11 
O.U 
0.17 


O.U 

<0.05 

0.07 


0.23 
0.52 
0.52 


Alabama River, 
Chrysler, Ala. 


mixed species^ 
largemouth bass 
freshwater drum 


3 
5 
8 


13.5 
15.9 
10.2 


1.77 

2.3 

0.66 


0.02 
0.03 
0.03 


0.19 

<0.10 

0.15 


0,16 
0,55 
0,07 


0.13 
0.20 
0.21 


0.34 
0.31 
0.65 


Tombigbee River, 
Mcintosh, Ala. 


mixed species ' 
freshwater drum 


4 

5 


13.9 
11.7 


2.3 
0.78 


0.03 
0.04 


0.20 
0.13 


0,18 
0.50 


0.18 
0,09 


0,44 
0,77 


Mississippi River, 
Luling, La. 


freshwater drum 


5 

5 
5 


13.0 
14.1 
14.3 


1.1 

1.58 

1.58 


0.03 
0.03 
0.02 


0.17 
0.12 
0.17 


0.03 
0.10 
0.12 


0.26 
0.13 
0.18 


0.44 
0.45 
0.67 


Brazos River, 
Richmond, Tex. 


alligator gar 

striped mullet 
striped mullet = 
gizzard shad 


3 
5 

5 
5 


18.5 
14.1 
13.3 
9.9 


1.0 
1.3 
1.1 
0.4 


0.02 
0.03 
0.02 
0.01 


<0.10 
0.48 
0.46 
0.65 


0.31 
0,01 
0.02 
0,04 


0.08 
1.48 
1.40 
0.60 


0.24 
0.40 
0.24 
0.26 


Colorado River. 
Wharton, Tex. 


largemouth bass 
channel catfish 

gizzard shad 


3 
5 
5 
5 


9.4 
12.4 
13.3 
12.2 


0.4 
0.6 
0.8 
0.8 


0.01 
0.06 
0.04 
0.01 


0.10 

0.14 

<0.10 

0.20 


0.12 
0,03 
0,05 
0,01 


0.05 

<0.05 

0.07 

0.85 


0.44 
0.30 
0.29 
0.32 


Nueces River, 
Mathis, Tex. 


largemouth bass 
gizzard shad 


5 

5 

5 


13.3 
11.3 
11.3 


1.5 
0.6 
0.7 


<0.01 
0.03 
0.03 


<0.10 
0.61 
0.56 


0,18 
0,02 
0.02 


0.21 
0.53 
0.37 


0.29 
0.29 
0.47 


Rio Grande, 
Brownsville, Tex. 


channel catfish 
gizzard shad 


3 

5 
5 


12.6 
11.6 
11.8 


0.63 
0.56 
0.52 


— 


— 


— 


— 


— 


Rio Grande, 
Elephant Butte, N.M. 


not collected ' 


















Rio Grande, 
Alamosa, Colo. 


brown trout 
white sucker 


5 
5 
5 


11.18 

10.7 

10.8 


0.62 
0.52 
0.52 


<0.05 
<0.05 


0.39 
0,10 


0.03 
0.04 


<0.25 
<0.25 


— 


Pecos River, 

Red Bluff Lake, Tex. 


not collected 


















San Antonio River, 
McFaddin, Tex. 


channel catfish 
alligator gar 
smallmouth bass 


3 
3 
3 


19.2 
22.9 
18.3 


4.8 
2.2 
6.6 


0,02 
0.17 
0.02 


0.25 
O.U 
0.71 


0.13 
0.28 
0.06 


<0.05 
0.13 
0.09 


0.41 
0.17 
0.66 






GREAT LAKES 


DRAINAGE 













Genessee River, 
Scottsville, N.Y. 



St. Lawrence River, 
Massena, N.Y. 



Lake Ontario, 
Port Ontario, N.Y. 



Lake Erie, 
Erie, Pa. 



Lake Huron, 
Bay Port, Mich. 



pumpkinseed 
carp 


5 
5 
5 


5,1 
15.9 
15.5 


0.2 

2.3 
2.2 


0.03 
0.02 
0.03 


0.62 
0.35 
0.23 


0.09 
0.04 
0.04 


0.06 
0.09 
0.14 


0.28 
0.19 
0.37 


smallmouth bass 
white sucker 


5 
5 


12.6 
14.1 


1.2 
1.3 


0.01 
0.03 


0.14 
0.41 


0.26 
0.19 


0.67 
0.16 


0.45 
0.31 


rock bass 
channel catfish 


5 
5 
5 


8.6 
14.1 
14.2 


0.5 
0.9 
0.9 


0.03 
0.02 
0.04 


0.20 
0.22 
0.20 


0.36 
0.07 
0.07 


0.31 
0.10 
0.16 


0.36 
0.30 
0.29 


yellow perch 
white sucker 


5 
5 
5 


8.6 
11.3 
11.4 


0.4 
0.6 
0.7 


0.03 
0.05 
0.05 


<0.10 
0.19 
0.16 


0.08 
0.05 
0.05 


O.U 
0.17 
0.17 


0.67 
0.69 
0.50 


carp 
carp* 
yellow perch 


5 

5 
5 
5 


18.7 
17.1 
7.6 
7.5 


3.72 
2.9 
0.2 
0.2 


0.04 
0.02 
0.02 
0.01 


0.49 
0,22 
0.23 
0.23 


0.23 
0.05 
0.04 
0.03 


0.10 

0.13 

<0.05 

<0.05 


0.35 
0.64 
0.44 
0.34 



15, No. 1, June 1981 



25 



TABLE 4. (cont'd.). 



Concentrations of cadiniiiin. lead, mercury, arsenic, and selenium in whole fish samples collected 
the National Pesticide Monitoring Program. 1976-77 



< 


TATioN Number 
AND Location 
(FIGURE 1) 


Species i 


No. 

OF 

Fish 


Average Size 




Residues, 


MG/KO Wet Weight 






Length, 
inches 


Weight, 

LB 






Cadmium 


Lead 


Mercury Arsenic 


Seii 


21. 


Lake Michigan. 
Sheboygan, Wis. 


bloater 
lake trout 


5 
5 
5 
4 


10.1 
10.0 

27.5 
23.8 


0.52 
0.56 
6.6 

4.5 


0.01 

0.02 

<0.01 

0.02 


0.15 

0.15 

<0.10 

<0.10 


0.03 
0.04 
0.19 
0.19 


2.92 
2.91 
1.20 
1.33 


0, 
0. 
0. 



22. 


Lake Superior, 
Bayfield, Wis. 


lake trout 
lake whitefish 


6 

3 


24.7 
20.3 


5.0 
2.86 


0.02 
0.05 


<0.10 
<0.10 


0.43 
0.03 


0.56 
0.47 






102. 


Lake Superior, 
Keeweenaw Point, Mich. 


bloater 
lake trout 


5 
5 

A 


10.4 
10.3 
22.0 


0.60 
0.60 
4.40 


0.03 
0.30 
0.02 


0.12 
<0.10 
<0.10 


0.11 
0.10 
0.10 


1.33 
1.19 
0.39 







103. 


Lake Superior, 
Whitefish Point, Mich. 


lake trout 
lake whitefish 


4 
5 
5 


23.9 
19.2 
19.8 


5.1 
3.0 
2.8 


0.02 
0.04 
0.04 


0.14 
0.29 
0.11 


0.26 
0.05 
0.07 


0.43 
0.41 
0.97 







104. 


Lake Michigan, 
Beaver Island, Mich. 


bloater 
lake trout 


4 
5 


11.3 
25.7 


0.6 
5.9 


0.02 
<0.01 


0.12 
<0.10 


0.04 
0.27 


2.41 
0.92 






105. 


Lake Michigan, 
Saugatuck, Mich. 


bloater 
lake trout 


5 
5 
5 


11.4 
11.3 

24.7 


0.6 
0.6 

4.7 


0.03 
0.01 


0.31 
<0.10 


0.05 
0.25 


2.30 
0.94 






MISSISSIPPI RIVER SYSTEM 


67. 


Allegheny River, 
Natrona, Pa. 


walleye 

silver redhorse 
golden redhorse 


3 
5 
5 


12.4 
10.6 
13.2 


0.63 
0.48 
0.94 


0.07 


0.19 


0.07 


0.26 




23. 


Kanawha River, 
Winfield, W.Va. 


black crappie 

carp 

brown bullhead 


5 
5 
5 


6.3 
14.8 
9.6 


0.14 
1.44 
0.46 


<0.05 


<0.10 


<0.02 


<0.25 




68. 


Wabash River, 
New Harmony, Ind. 


largemouth bass 
carp 


5 
5 
5 


10.7 
16.8 
16.1 


0.72 

2.7 

2.38 


0.06 
0.18 


0.17 
0.22 


0.10 


<0.25 
<0.25 




24. 


Ohio River, 
Marietta, Ohio 


sauger 
carp 


5 

4 


13.9 
17.2 


1.18 
2.92 


<0.05 
0.22 


0.26 
2.49 


0.10 
0.05 


<0.25 
<0.25 




69. 


Ohio River, 
Cincinnati, Ohio 


sauger 
channel catfish 

smallmouth buffalo 


5 
5 
4 
5 
3 


13.7 
11.1 
15.5 
12.2 
13.7 


1.04 

0.5 

1.3 

1.08 

1.8 


<0.05 
<0.05 


0.10 
0.42 


0.10 
0.04 


<0.25 
<0.25 




70. 


Ohio River, 
Metropolis, 111, 


largemouth bass 
carp 


5 
5 
5 


14.2 
16.5 
16.2 


1.72 
2.52 
2.12 


<0.05 
0.18 


<0.10 
0.25 


0.30 
0.15 


<0.25 
<0.25 




25. 


Cumberland River, 
Clarksville, Tenn. 


largemouth bass 

carp 

spotted sucker 


4 
5 
4 


9.8 
13.4 
12.2 


0.52 
1.16 
0.76 


— 


— 


— 


— 




71. 


Tennessee River, 
Savannah. Tenn. 


not collected 


















106. 


Lake Huron, 
Alpena, Mich. 


lake trout 
white sucker 


5 
5 
6 
5 


23.4 
19.0 
16.3 
12.7 


4.3 
2.8 
1.9 
0.9 


<0.01 
0.04 
0.02 
0.02 


<0.10 
0.39 
0.28 
0.13 


0.23 
0.07 
0.03 
0.02 


0.51 
0.11 
0.10 
0.16 


0. 





107. 


Lake St. Clair. 
Mt. Clemens. Mich. 


walleye 
carp 


5 
5 
5 


20.3 
20.4 
20.1 


2.7 
4.5 
4.5 


0.06 
0.15 
0.16 


0.13 
1.83 
0.78 


0.84 
0.60 
0.32 


0.24 
0.13 
0.09 


0. 




108. 


Lake Erie, 

Port Clinton, Ohio 


walleye 
carp 


5 
5 
5 


15.9 
15.9 
16.7 


1.6 

2.5 
2.4 


<0.01 
0.03 
0.03 


<0.10 
0.19 
0.21 


0.09 
0.03 
0.04 


0.36 
0.15 
0.21 


0, 
0. 



109. 


Lake Ontario, 
Roosevelt Beach. N.Y. 


inactive 


















110. 


Lake Ontario, 
Cape Vincent, N.Y. 


inactive 


















72. 


Wisconsin River, 
Woodsman, Wis. 


smallmouth bass 
carp 


5 
5 

5 


12.9 
17.2 
17.7 


1.12 

2.3 

2.46 


0.07 


0.23 


0.14 


<0.2S 





26 



Pesticides Monitoring Joui ' 



LE 4. (cont'd.). 



Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for 
the National Pesticide Monitoring Program, 1976-77 



ATiON Number 
ND Location 

(FIGURE 1) 



Species > 



Des Moines Rivet, 
Keosauqua, Iowa 



Illinois River, 
Beardstown, 111. 

Mississippi River, 
Little Falls, Minn. 

Mississippi River, 
Guttenberg, Iowa 

Mississippi River, 
Cape Girardeau, Mo. 

Mississippi River, 
Memphis, Tenn. 

Arkansas River, 
Pine Bluff. Ark. 

Arkansas River, 
Keystone Reservoir, Okla. 

Arkansas River, 

John Martin Reservoir, Colo. 

Verdigris River, 
Oologah, Okla. 

Canadian River, 
Eufaula, Okla. 

White River, 
DeValls Bluff. Ark. 

Yazoo River, 
Redwood, Miss. 

Red River, 
Alexandria, La. 

Red River, 

Lake Texoma, Okla. 

Missouri River, 
Hermann, Mo. 

Missouri River, 
Nebraska City, Neb. 

Missouri River, 
Garrison Dam, N.D. 

Missouri River, 
Great Falls, Mont. 

Big Horn River, 
Hardin, Mont. 

Yellowstone River, 
Sidney. Mont. 

James River, 
Olivet. S.D. 

North Platte River, 
Lake McConaughy, Neb. 

South Platte River, 
Brule, Neb. 



carp 

walleye 

black crappie 
carp 



walleye 
black bullhead 



largemouth bass 
carp 

white crappie 
carp 

smallmouth buffalo 

bluegill 
carp 

largemouth bass 
carp 

inactive 

while bass 
carp 

white bass 
river carpsucker 

white crappie 
bigmoulh buffalo 

black crappie 
bigmouth buffalo 

smallmouth buffalo 



largemouth bass 
gizzard shad 

freshwater drum 

goldeye 
carp 



walleye 

white sucker 



goldeye 

longnose sucker 
redhorse sucker 

goldeye 
white sucker 



sauger 
carp 

goldeye 
carp 

walleye 
carp 

green sunfish 
carp 



No 


AVERAO: 


E Size 




Residues, 


MG/KG Wet Weight 




OF 

Fish 


Length, 

INCHES 


Weight, 

LB 




Cadmium 


Lead 


Mercury Arsenic J 


Selenium 


5 
5 
3 


15.6 

15.4 
16.5 


1.94 
1.94 
1.53 


0.06 

1.04 

<0.05 


0.27 

0.41 

<0,10 


0.07 
0.06 


<0.25 
<0.25 
<0.25 


— 


5 
5 

5 


8.2 
14.1 
14.2 


0.32 
1.22 
1.40 


<0.05 
<0.05 


0,23 
0.32 


0,09 
0.05 


<0.25 
<0.25 


— 


5 

5 
5 


11.1 
8.2 
7.9 


0.5 

0.32 

0.28 


0.06 


0.10 


0.32 


<0.25 


— 


5 
5 
5 


14.1 
19.9 
21.3 


1.72 
3.56 
4.48 


<0.05 
<0.05 


0.55 
0.30 


0.05 
0.05 


<0.25 
<0.25 


— 


5 
5 
5 


8,7 
14.4 
15.4 


0,24 
1.26 
1.68 


<0.05 
0.45 


0.13 
0.49 


0.17 
<0.02 


<0.25 
0.30 


— 


3 
3 


17.3 
16.4 


2.63 
2.97 


0.02 
0.03 


<0,10 
0,13 


0.04 
0.05 


0.14 
0.11 


0.25 
0.33 


5 
5 


6.3 
19.8 


0.1 

3.78 


0.02 
0.05 


0.27 
0.18 


0.05 
0.07 


0.12 
0.12 


0.23 
0.33 


5 
5 

5 


13.7 
17.9 
17,8 


1.8 
2.1 
2.4 


<0.01 
0.12 
0.09 


<0.10 
0.39 
0.44 


0,17 
0.15 
0,21 


0.20 

<0.05 

0.07 


0.67 
0.54 
0,65 



5 
5 
5 


12.4 
17.8 
16.1 


0.9 

2.5 
2.1 


0.02 
0.54 
0.78 


0.11 
0.75 
0.82 


0.07 
0.09 
0.09 


0.55 
0.08 
0.09 


0.60 
0.50 
0.44 


5 
5 
5 


13.9 
13.0 

12.2 


1.4 
1.1 
0.7 


<0.01 
0.02 
0.02 


<0.10 
0.38 
0.38 


0.34 
0.13 
0.06 


0.65 
0.08 
0.16 


0.35 
0.28 
0.38 


5 
3 
3 


8.5 
15.1 
15.5 


0.2 

1.87 

1.87 


0.02 
0.04 
0.04 


0.15 
0.17 
0.24 


0.18 
0.13 
0.14 


0.12 
0.06 
0.12 


0.24 
0.54 
0.41 


5 
5 

5 


9.3 
15.0 
15.5 


0.9 
2.0 
2.2 


<0.01 
0.02 
0.04 


0.10 
0.10 
0.11 


0.14 
0.04 
0.06 


0.16 
0.10 
0.09 


0.43 
0.41 
0.38 


5 
5 

5 


17.1 
17.3 
17.0 


2.8 

3.14 

2.94 


0.01 
0.02 
0.01 


0.19 
0.12 
0.15 


0.10 
0.13 
0.10 


<0.05 

0.05 

<0.05 


0.22 
0.32 
0.35 


5 

5 
5 


10.4 

10.4 

9.9 


0.6 
0.4 
0.3 


0.03 
0.05 
0.05 


0.31 
1.14 
1.44 


0.12 
0.02 
0.02 


0.11 
0.55 
0.61 


0.72 
0.89 
0.86 


5 


16.3 


2.2 


0.03 


<0.10 


0.24 


0.06 


0.66 


5 

5 
5 


12.5 
14,8 
15.3 


0.7 
1.7 
1.8 


0.03 
0.06 
0.06 


2.43 
0.75 
0.86 


0.09 
0.03 
0.05 


<0.05 
0.10 
13 


0.73 
1.28 
1.52 


5 
5 
5 


17.3 
14.2 
14.3 


1.64 
1.18 
1.18 


<0.01 
0.03 
0.03 


0.10 
0.47 
0.30 


0.22 
0.08 
0.07 


0.18 
0.32 
0.23 


0.70 
0.73 
0.73 


9 

3 

5 


12.7 
16.6 
17.1 


0.7 

1.97 

2.36 


0.06 
0.18 
0.44 


0.13 

0.32 
0.14 


0.12 
0.06 
0.15 


0.08 
0.42 
0.10 


1.36 
0.33 
0.29 


10 
10 
10 


12.4 
14.2 
12.5 


0.5 
1.2 
0.8 


0.03 

0.01 

<0.01 


0.11 

0.10 

<0.10 


0.19 
0.09 
0.05 


0.06 
0.09 
0.06 


2.87 
1.71 
1.07 


5 

5 
5 


12.7 
14.8 
20.7 


0.58 
1.62 
3.82 


0.02 
C.04 
0.24 


<0.10 

<0.10 

0.17 


0.22 
0.12 
0.15 


0.06 
0.16 
0.08 


1.75 
0.88 
0.82 


5 

5 
5 


14.1 
16.1 
16.2 


0.9 
2.0 
2.0 


0.03 
0.05 
0.10 


0.92 
1.95 
1.08 


0.23 
0.07 
0.09 


<0.05 
0.06 
0.07 


0.82 
0.53 
0.57 


5 
5 
5 


17.2 
19.1 
20.1 


1.6 

3.0 
3.8 


<0.01 
0.09 
0.08 


0.42 
0.54 
0.94 


0.04 
0.17 
0.10 


0.81 
0.13 
0.20 


0.73 
0.81 
0.63 


5 
5 
5 


5.4 
10.1 
9.6 


0.1 
0.5 
0.4 


0.01 
0.02 
0.02 


1.25 
0.49 
0.53 


0.06 
0.01 
0.02 


0.09 
0.14 
0.05 


2.08 
2.05 
2.53 



15, No. 1, June 1981 



27 



TABLE 4. (cont'd.). 



Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected 
the National Pesticide Monitoring Program, 1976-77 



£ 


TATiON Number 
AND Location 

(FIGURE 1) 


Species ^ 


No. 

OF 

Fish 


Average Size 




Residues, 


MO /kg Wet Weight 






Length, 
inches 


Weight, 

LB 






Cadmium 


Lead 


Mercury Arsenic 


Sele> 


89. 


Platte River, 
Louisville, Neb. 


goldeye 

river carpsucker 


5 
5 
5 


12.8 
13.4 
14.6 


0.7 
1.0 
1.4 


0.03 
0.06 
0.10 


0.97 
1.33 
1.74 


0.10 
O.ll 
0.12 


0.07 
0.13 
0.07 


1.0 
1.0 
1.1 


90. 


Kansas River, 
Bonner Springs, Kans. 


freshwater drum 
carp 


5 

5 
5 


9.3 
19.1 
19.3 


0.34 

3.5 

3.58 


0.02 

0.07 

<0.01 


<0.10 
0.16 
0.21 


0.10 
0.13 
0.12 


0.08 

<0.05 

0.09 


0.8 
0.8 
1.0 


111. 


Mississippi River, 
Lake City. Minn. 


walleye 
white sucker 


5 
5 


21.1 
17.8 


3.76 
2.56 


0.06 
0.05 


0.25 
0.25 


0.11 
<0.02 


<0.25 
<0.25 


- 


112. 


Mississippi River, 
Dubuque, Iowa 


largemouth bass 
carp 


5 
5 
5 


9.6 
18.5 
17.9 


0.48 
2.98 
2.84 


<0.05 
<0.05 


<0.I0 
0.14 


0.05 
0.04 


<0.25 
<0.25 


- 


116. 


Souris River, 
International Border, N.D. 


northern pike 


5 


19.5 


1.66 


<0.05 


0.37 


— 


<0.25 


- 








HUDSON BAY 


DRAINAGE 












34. 


Red River, 

Noyes, Minn. 


Sanger 
white sucker 


5 
5 
5 


13.1 

12.4 
13.9 


0.62 
0.52 
1.14 


<0.05 
0.16 


<0.10 
<0.10 


0.45 
0.13 


<0.25 
<0.25 


- 








COLORADO RIVER SYSTEM 










-i 



35. Green River, 
Vernal, Utah 



36. Colorado River, 

Imperial Reservoir, Ariz 



91. Colorado River, 
Lake Havasu, Ariz. 

92. Colorado River, 
Lake Mead, Nebr. 



93. 



Colorado River, 
Lake Powell, Ariz. 



channel catiish 
carp 



channel catfish 
carp 



channel catfish 
carp 



largemouth bass 
carp 



12.5 
13.6 
12.5 



5 16.8 

Not collected 
5 14.8 



19.0 
15.9 



0.54 

1.3 

1.24 

1.34 

1.84 

2.28 
1.88 



<0.05 <0.10 <0.02 <0.25 
<0.05 0.18 <0.02 0.30 



5 


13.8 


1.46 


<0.05 


0.27 


0.14 


<0.25 


5 


13.5 


1.1 


0.21 


0.35 


0.15 


0.26 


5 


13.5 


1.2 


0.22 


0.16 


0.07 


<0.25 



94. Gila River, 

San Carlos Reservoir, Ariz. 

114. Bear Creek, 

Brigham City, Utah 



115. Colorado River, 
Yuma, Colo. 



not collected 

channel catfish 
carp 

mullet 

carp 

largemouth bass 





13.3 
11.5 
14.7 


0.9 

0.96 

1.68 


0.09 


<0.10 


— 


<0.25 




13.5 
11.7 
12.0 


0.99 
0.81 
1.02 


<0.05 
<0.05 


0.23 
0.20 


<0,02 
0.03 


<0.25 
<0.25 



INTERIOR BASINS 



37. Truckee River, 
Fernley, Nebr. 

38. Utah Lake, 
Provo, Utah 

93. Bear River, 
Preston, Idaho 



carp 

Tahoe sucker 



walleye 
carp 



5 


16.1 


3.02 


0.03 


0.26 


0.37 


0.07 


5 


8.8 


0.34 


0.02 


0.14 


0.39 


0.15 


5 


8.7 


0.32 


0.02 


0.28 


0.32 


0.19 


5 


19.8 


3.62 


, 








— 


5 


18.9 


3.32 


— 


_ 


— 


— 


5 


18.8 


3.24 


— 


— 


— 


— 



inactive 



CALIFORNIA STREAMS 



39. Sacramento River, 
Sacramento. Calif. 

40. San Joaquin River, 
Los Banos, Calif. 



28 



largemouth bass 
goldfish 




12.5 
12.4 
10.2 


1.2 
1.3 
0.7 


0.02 
0.11 
0.06 


<0.10 
0.19 
0.21 


0.14 
0.19 
0.09 


0.19 
0.23 
0.22 


0.: 
0.; 
o.< 


striped bass 
Sacramento blackiish 




13.0 
12.3 
11.0 


0.9 
0.8 
0.6 


<0.01 
<0.01 
<0.01 


<0.10 

<0.10 

0.12 


0.08 
0.07 
0.16 


0.33 
0.12 
0.09 


l.( 

1.: 












Pesticides 


Monitoring 


Jour 



BLE 4. (cont'd.). Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for 

the National Pesticide Monitoring Program, 1976-77 



Station Number 

AND Location 

(FIGURE 1) 



Species ' 



No. 

OF 

Fish 



Average Size 



Residues, mg/kg Wet Weight 



Length, Weight, 

INCHES LB Cadmium Lead Mercury Arsenic Selenium 



COLUMBIA RIVER SYSTEM 



Snake River, 
Hagerman, Idaho 


northern squawtish 
largescale sucker 

rainbow trout 


5 
5 

5 
5 


15.3 
13.7 
13.5 
13.8 


1.18 
0.92 
0.94 
1.0 


— 


— 


— 


— 


Snake River, 
Lewiston, Idaho 


northern squawfish 
largescale sucker 


5 
5 
5 


15.2 
15.4 
15.9 


1.14 
1.28 
1.36 


<0.05 
0.10 
0.07 


0.10 
0.12 
0.10 


0.31 
0.07 
0.11 


<0.25 
0.50 
1.11 


Salmon River, 
Riggins, Idalio 


largescale sucker 


5 
4 


18.2 
17.9 


1.7 
2.1 


0.12 


0.23 


0.19 


0.50 


Snake River, 

Ice Harbor, Wash. 


channel catfish 
largescale sucker 


5 
5 

5 


13.0 
14.7 
14.8 


0.54 
1.14 
1.12 


0.10 
0.09 
0.07 


0.21 
0.17 
0.11 


0.10 
0.04 
0.05 


0.61 

<0.25 
<0.25 


Yakima River, 
Granger, Wash. 


black crappie 
largescale sucker 


4 
5 
5 


6.0 
11.6 
12.1 


0.1 

0.56 

0.66 


0.14 
<0.05 


0.19 
0.10 


0.05 
0.09 


0.50 
0.61 


Willamette River, 
Oregon City, Oreg. 


smallmouth bass 
chiselmouth 


3 
5 
5 


9.2 
10.2 
10.8 


0.5 
0.4 
0.5 


<0.05 
0.20 


0.12 
0.85 


0.13 
<0.02 


<0.25 
1.15 


Columbia River, 
Booneville Dam, Oreg. 


northern squawfish 
largescale sucker 


5 
5 
5 


13.5 
14.3 
12.4 


0.9 

1.08 

0.82 


<0.05 
0,15 


<0.10 
<0.10 


0.23 
0.05 


<0.25 
0.87 


Columbia River, 
Pasco, Wash. 


carp 


5 

5 


11.4 
11.6 


0.66 
0.7 


<0.05 
<0.05 


0.34 
0.13 


<0.02 
<0.02 


<0.25 
0.35 


Flathead River, 
Creston. Mont. 


northern squawfish 
longnose sucker 


5 
4 
3 


13.6 
15.2 
12.8 


0.74 

1.1 

1.0 


- 


— 


— 


— 


Columbia River, 
Grand Coulee, Wash. 


yellow perch 
largescale sucker 


5 

5 
5 


7.9 
16.4 
17.3 


0.26 
1.58 
1.74 


<0.05 
0.33 


0.16 

2.57 


0.03 
<0.02 


<0.25 
0.30 



PACIFIC COAST STREAMS 



Klamath River, 


yellow perch 


5 


9.2 


0.4 


<0.01 


<0.10 


0.09 


<0.05 


0.16 


Hornbrook, Calif. 


Klamath sucker 


5 


12.4 


0.7 


<0.01 


<0.10 


0.06 


0.11 


<0 05 






5 


12.5 


0.7 


0.01 


0.10 


0.03 


0.12 


0.08 


Rogue River, 


black crappie 


5 


9.1 


0.76 


<0.01 


<0.10 


0.16 


<0.05 


0.11 


Gold Ray Dam, Oreg. 


Klamath sucker 


5 


8.7 


0.28 


0.01 


<0.10 


02 


0.11 


0.06 






5 


9.1 


0.32 


0.01 


<0.10 


0.03 


0.13 


0.12 



ALASKAN STREAMS 



Chena River. 
Fairbanks, Alaska 

Kenai River, 
Soldatna, Alaska 



Artie grayling 
longnose sucker 

not collected 



5 


10.5 


0.38 


0.02 


0.27 


0.07 


0.05 


0.80 


5 


14.6 


1.26 


0.03 


0.13 


0.08 


0.17 


0.32 



HAWAIIAN STREAMS 



Waikele Stream, 
Waipahu, Hawaii 

Manoa Stream, 
Honolulu, Hawaii 



Cuban limia 


28 


1.9 


<0.10 


0.05 


0.38 


0.04 


0.08 


0.77 




28 


2.4 


<0.10 


0.05 


0.51 


0.05 


0.10 


0.80 


Chinese catfish 


3 


6.9 


0.2 


0.11 


0.80 


0.12 


0.10 


0.43 


tilapia 


33 


6.9 


0.23 


0.03 


2.28 


0.02 


0.27 


0.38 




3 


6.3 


0.2 


— 


— . 


— 


— 


— 


Cuban limia 


36 


2.7 


<0.10 


— 


— 





_ 


— 




37 


2.7 


<0.10 


0.03 


4.93 


0.05 


0.49 


0.12 



mmon names for species from the continental United States follow thr^sc designated in "A list of common and scientific names of fishes 

m the United States and Canada", American Fisheries Society Special Publication No. 6, 3rd Edition^ 1970. 

lere two or more rows of data follow a species name, the data represent replicate samples. 

shes ( — ) =: not analyzed (sample not submitted, or inadequate digestion procedure, e.g.. 1976 Se data). 

ictive — stations so designated have been temporarily deleted fromverse conditions, etc.). 

xed species = white catfish, carp, and spotted sucker. 

xed species — freshwater drum, spotted sucker, and smallmouth buffalo. 

t collected = personnel were unable to obtain fish samples (e.g., ad the NPMP collection station network. 



.. 15, No. 1, June 1981 



29 



As expected, location effects were highly significant 
(P < 0.001 ) for all five elements (Table 5). Effects due 
to time were significant for mercury, arsenic, selenium 
(P < 0.001), and cadmium (P < 0.05), but not for 
lead (P ^ 0.213). Interactions between main effects 
were not significant. 

TABLE 5. Results of two-way analysis of variance (weight- 
ed squares of means) on concentrations of lead, mercury, 
cadmium, arsensic, and selenium in freshwater fish, United 
States, 1976-77 



TABLE 6. Mean concentrations of lead, mercury, ci 
mium, arsenic, and selenium in whole fish ' 



Source 



Deorpes 

OF Sum of 

Freedom Squares 



Mean 
Square 



Significance 
Level 



Lead 












Stations 


81 


4.536 


0.056 


5.905 


0.001 


Years 


1 


0.014 


0.014 


1.553 


0.213 


Interaction 


81 


0.661 


0.008 


0.860 


0.791 


Error 


368 


3.490 


0.009 






Mercury 












Stations 


81 


0.367 


0.004 


3.305 


0.001 


Years 


1 


0.023 


0.023 


16.874 


0.001 


Interaction 


81 


0.059 


0.0007 


0.531 


0.999 


Error 


364 


0.499 


0.001 






Cadmium 












Stations 


81 


0.432 


0.005 


2.196 


0.001 


Years 


1 


0.015 


0.015 


6.434 


0.011 


Interaction 


81 


0.126 


0.001 


0.645 


0.991 


Error 


368 


0.894 


0.002 






Arsenic 












Stations 


43 


0.804 


0.018 


7.875 


0.001 


Years 


I 


0.051 


0.051 


21.774 


0.001 


Interaction 


43 


0.090 


0.002 


0.887 


0.671 


Error 


217 


0.515 


0.002 






Selenium 












Stations 


43 


2.579 


0.60 


13.173 


0.001 


Years 


2 


0.160 


0.080 


17.663 


0.001 


Interaction 


86 


0.273 


0.003 


0.698 


0.976 


Error 


352 


1.603 


0.004 







Significant differences in mercury (P < 0.001) and 
cadmium concentrations (P < 0.05) were observed 
from 1972 to 1976-77 (Table 6); lead concentrations 
did not decline significantly, but arsenic concentrations 
increased significantly (P < 0.001). The two-way 
ANOVA indicated an effect for selenium due to time 
(P < 0.001. Table 6). Mean selenium concentrations 
for 1973 were significantly lower than those for 1972 
selenium values (a priori test, 0.001 < P < 0.005). 
A posteriori comparison (54) of mean selenium levels 
indicated no significant differences between 1972 and 
1977 samples. Because of changes in laboratories, ana- 
lytical procedures, station, fish species, size and age of 
fish, etc., these results should be used cautiously as 
temporal trend information. 

Discussion 

The average percent difference between duplicates for 
cadmium, mercury, arsenic, and selenium was consid- 
ered acceptable, particularly because some duplicates 
had elemental concentrations near the detection limit. 
Recoveries from spiked samples, and reference mate- 



Mean Concentrations, mg/kg wet weight = 



Element 



1972 



Sicnifica: 
(P) 



Lead 


0.354 
(0.322-0.387) 


0.338 
(0.297-0.380) 


>0.05 (^ 


Mercury 


0.153 
(0.142-0.164) 


0.112 
(0.099-0.126) 


<0.001 


Cadmium 


0.112 
(0.098-O.126) 


0.085 
(0.068-0.102) 


<0.05 


Arsenic 


0.127 
(0.108-0.146) 


0.207 
(0.184-0.231) 


<0.001 


Selenium ^ 


0.604 
(0.567-0.641) 


0.576 
(0.534-0.619) 


<0.001 



1 Matching stations in years. 

" Figures in parentheses are 95 percent confidence intervals. 

=1 The mean concentration (and 95% CI) for selenium in 1973 

0.455 (C. 422-0. 488) mg/kg. This was the only element having matcl 

station data in 1973. The P value (<0.001) results from the two-' 

ANOVA on all 3 years. 

rials, indicated satisfactorily accurate recovery of f 
elements in all years, except for mercury in the spil 
samples for 1976. The low recovery (64 percent) 
mercury (Table 3) suggests problems during sami 
digestion and analysis. 

Imprecision in lead-quality control data indicates tji 
measured lead values may not accurately reflect av 
age levels in fish tissues. The accuracy and precis 
of lead spike recoveries (91 ± 10 percent and 102 j 
12 percent) and National Bureau of Standards refereij 
material analyses (Table 3) indicate that digestion £i 
analytical techniques were satisfactory. Nonunifol 
distribution of lead in fish tissue and authors' inabij 
to achieve complete homogenization were more lik| 
the causes of imprecision. For example, in tuna, 
lead content of epidermis tissue is several thousand tir 
that in muscle tissue from the same fish (9, 59). Mi 
of the lead in the epidermis is associated with mui 
(9). Similarly, rainbow trout (Salmo gairdneri) ac 
mulate lead in mucus and scales (85, 86). As a res 
lead digestate concentrations are difficult to correl i 
with muscle tissue dry weights because of mucosal sli i 
contamination (89). 

To approximate normal background ranges for wh( 
fish trace element concentrations, station means of I 
transformed individual data values (Table 4) w 
calculated for each element and arranged in orden 
increasing concentration. The stations with transfomii 
mean values exceeding the 85th percentile were t 
identified (Table 7). The antilog of this 85th percent 
was arbitrarily used to distinguish stations with h|i 
metal concentrations. Though the 85th percentile nf 
not be meaningful biologically, it was considered abn 
background and potentially worth further study. Autb ) 



30 



Pesticides Monitoring JourI'^ 



\BLE 7. Stations from which fish had trace element con- 
ntration equal to or exceeding the 85th percentile for the 
1976-77 trend-monitoring collection 





85th Percentile, 


Stations (in order of increasing 


EMENT 


mo/kg 


CONCENTRATION ) 


dmium 


O.U 


70, 68, 43, 107, 45, 24, 93, 2, 98, 
3, 4, 33, 75, 73, 55, 78 


ad 


0.44 


99. 78. 87, 53, 88, 2, 107, 82, 98, 
24, 4. 31. 86, 89, 3, 100 


:rcury 


0.19 


43, 22, 1, 70, 66, 57, 83, 59, 51, 
34, 74, 14, 37, 56, 107 


senic 


0.38 


3, 66, 82, 43, 22. 46, 44, 42, 103, 
45, 10, 60, 102, 105, 104, 21 


enium 


0.82 


82, 4, 90, 89, 85, 31, 40, 84, 88 



tempted to suggest sources that could account for the 
gher values encountered at these stations. It should 
recognized that relating specific sources of metals to 
;vated concentrations of the elements in freshwater 
h is speculative. The intent is to provide a metal 
urce perspective for the drainage basins to help 
mfy elevated metal concentrations in fish from these 
eas. 

.DMlUM 

idmium concentrations in freshwater fish had a range 
0.01-1.04 ppm, a mean of 0.067 ppm, and an 85th 
rcentile of 0.11 ppm. The decrease in cadmium 
ncentrations in fish since 1972 (Table 6) parallels 
dmium metal production and consumption, which 
clined over the same period (63). NPMP stations 
which fish had cadmium concentrations equal to or 
ceeding the 85th percentile (Table 7) are discussed 
low in relation to possible contaminant sources, 

lantic Coastal Streams — Fish from four rivers, the 
mnecticut (station 2), the Hudson (station 3), the 
;laware (station 4), and the James (station 55), all 
ntained mean cadmium concentrations exceeding 0.17 
m. Each of these river systems lies in a heavily 
lustrialized area. A zinc smelting company, which is 
primary cadmium producer, is on the Lehigh River, a 
butary of the Delaware. Metal fumes from the 
lelter's low stacks have killed trees in the Lehigh 
illey, and river sediments contained 5.4 ppm cadmium 
8). The James River receives eflfluents from numerous 
emical, fertilizer, and other industries (16). 



from zinc-smelting activity from a primary cadmium 
producer located on the Ohio River at Monaco, Penn- 
sylvania. Similarly, a lead-smelting and refining com- 
plex at East Helena, Montana may be the primary source 
of cadmium in fish collected at station 33 (Great Falls, 
Montana. Miesch and Huff'man (76) found cadmium 
contamination in soil 10 miles from a smelter in Helena 
Valley. It was estimated that 290 tons of cadmium had 
been added to the soil within a radius of 1-19 km from 
the smelter stacks. Superphosphate fertilizers are a 
suspect source at station 73 (Des Moines River), where 
high cadmium levels may reflect substantial agricultural 
runoff. High cadmium fluxes have been reported for the 
Mississippi River as it flows through mineralized areas 
in Tennessee, Missouri, and Kentucky (15). Cadmium 
levels in carp at Cape Girardeau, Missouri (station 75, 
Mississippi River), are probably the result of numerous 
sources, A zinc company at Sauget, Illinois (East St. 
Louis), has discharged waste on the Mississippi flood- 
plain, forming a black sludge containing 0.1 percent 
cadmium (78). A large lead-smelting facility at Hercu- 
laneum, Missouri, has discharged eflluent directly into 
the river. The smelter's slag piles along the banks of 
the Mississippi contained from 19 to 250 ppm cadmium, 
and much slag has been bulldozed into the river (78). 
In addition, industrial and municipal sewage effluents 
from St. Louis and phosphate fertilizer runoff" may 
contribute to the cadmium load at this station. 

The highest cadmium mean value was in carp from 
station 78 on the Verdigris River at Oologah, Oklahoma. 
A zinc company in Bartlesville, Oklahoma, may supply 
cadmium to the upper Verdigris River area as a result 
of particulate fallout from smelter stack emissions (55). 
The 85th percentile value of 0.11 ppm was character- 
istic of fish from station 70 on the Ohio River and 
probably reflects the relatively heavy industrialization 
of the lower river area. 

Colorado River System — Southwestern Colorado and 
north-central Utah contain major deposits of lead and 
zinc ores, and numerous active mines are located there 
(61). A geologic source of cadmium, as well as mine 
waste drainage into tributaries of the Colorado River, 
could account for elevated cadmium levels in fish 
from Lake Powell, Arizona (station 93). 



eat Lakes Drainage — Like the Atlantic coastal 
earns. Lake St. Clair (station 107) is surrounded by 
iieavily industrialized area. Cadmium residues in fish 
)m the area ranged from 0.06 to 0.16 ppm, apparently 
iginating from a number of industrial sources in and 
ar Detroit, 

ississippi River System — The 0.22-ppm cadmium level 
carp from station 24 at Marietta, Ohio, may result 



Columbia River System — Bottom sediments of the Wil- 
lamette River and its numerous tributaries have cad- 
mium concentrations ranging from 0.5 to 1 ppm (73). 
Concentrations of 2.5 ppm cadmium were found in 
sediment samples near the river mouth downstream from 
Portland, Oregon. Uniformity in sediment cadmium con- 
centrations throughout the Williamette River basin sug- 
gests a geologic source of the metal. Active lead-zinc- 
silver mining in the Salmon River basin (station 43) may 



iL. 15, No. 1, June 1981 



31 



account for the elevated concentrations in large-scale 
suckers (23, 21). High cadmium concentrations in fish 
from Grand Coulee, Washington (station 98), may re- 
flect industrial waste from Spokane and activities of the 
Bunker Hill smelting complex at Kellogg, Idaho. Water 
from the South Fork of the Coeur d'Alene River has 
contained up to 0.45 ppm cadmium, corresponding to a 
cadmium transport of 240 lb cadmium/ day (22, 37). 
The South Fork drains an area where thousands of tons 
of mine ground tailings of lead-zinc-silver ores were 
dumped decades ago (15). The Bunker Hill and asso- 
ciated smelters have tailing ponds extending for over 4 
miles in the flood plain of the South Fork of the Coeur 
d'Alene River (7S). 



Lead concentrations in freshwater fish (Table 4) ranged 
from 0.10 to 4.93 ppm and averaged 0.32 ppm. The 
trend in lead concentrations (Table 6) indicated no sig- 
nificant change from 1972 to 1976-77. The NPMP sta- 
tions having concentration means at or above the 85th 
percentile of 0.44 ppm are discussed below. 

Atlantic Coastal Streams — Segments of the Atlantic 
coastal streams where stations 2, 3, 4, and 53 are located 
contain many different types of industry. Industrial 
sources of lead could include those from metal finishing, 
brass manufacturing, lead alkyl manufacturing, primary 
and secondary lead smelting, coal combustion, and lead 
oxide manufacturing. River mud in the vicinity of a New 
Jersey zinc company, located on a tributary of the Dela- 
ware River, contained 0.13 percent lead {78). The St. 
Lawrence, New York, area contains a geologic source of 
lead; the Balmat mine, located there, ranks 18th in 
domestic output (67). The headwaters of the Hudson 
River may receive a lead flux from these ore deposits. 

Great Lakes Drainage — Lake St. Clair (station 107), 
like the Atlantic coastal streams, is bordered by substan- 
tial industry and has a well-documented history of pol- 
lution (13). Lake St. Clair may receive urban lead 
aerosol fallout from the Detroit area, as well as effluents 
from numerous Detroit industries. 

Mississippi River System — The Missouri-Oklahoma- 
Kansas vicinity is the location of stratabound deposits 
characteristically containing lead ores (64). Thus, in 
addition to point industrial sources of lead, the Verdigris 
River (station 78) and Red River (station 82) may re- 
ceive lead from geologic origins. Fish residues at station 
24 (Ohio River) may be affected by effluents (aerial 
fallout, tailing erosion, etc.) from a zinc company at 
Monaca, Pennsylvania. High concentrations at stations 
88 and 89 (South Platte River), presumably reflect in- 
dustrial discharges from Denver. The Pierre Shale of the 
Great Plains region contains low concentrations of lead 



and may provide a natural source of lead for statio 
31,86, 87, and 88 (69). 

Columbia River System — Lead residues from fish 
Grand Coulee, Washington (station 98), may be 
fluenced by several lead sources affecting Franklin 
Roosevelt Lake. These are industrial effluents from Sf 
kane, lead-zinc mining in Pend Oreille, Washingtc 
natural stratabound deposits in Metaline Falls, Washit 
ton; and the mining-smelting complex at the South Fc 
of the Coeur d'Alene River. The Spokane water sup] 
has had concentrations of copper and zinc above th( 
allowed by Public Health Drinking Water Standar 
The source is erosion and leaching of heavy metals fn 
slag and tailing piles along the South Fork of the Cot 
d'Alene River (78). 

Hawaiian Streams — Waikele Stream (station 99) and 
tributaries total 117 miles in length and drain a 45 
square-mile watershed. Diversions for domestic and aj 
cultural uses and highly permeable soils contribute 
extreme variations in flows, which ranged from 0.02 
13,600 ftVsecond over 24 years. Heavy urban runofl 
characteristic of the flood flows in the lower reaches 
the stream. Agricultural and residential use of If 
arsenate has occurred in the drainage area, and vehi 
sources of lead are prevalent. The Manoa-Palola stre 
system (station 100) drains an area of about 9.35 mi 
characterized by high vehicle density. Air quality d 
have reflected high levels of lead aerosols and ot 
vehicle pollutants in the area. Lead arsenate has 8 
been applied in the past for agricultural use and tern; 
control (Lenhart, D. J. 1979. Regional Pesticide Speed 
ist. Fish and Wildlife Service, U.S. Department of fl 
Interior, Portland, Oregon, personal communication)! 

MERCURY 

Mercury concentrations in fish in 1976-77 (Table ( 
ranged from 0.01 to 0.84 ppm, and averaged 0.11 pr 
The decline of mercury levels in freshwater fish si I 
1972 (Table 6) is probably due to an overall reduct) 
of industrial mercury emissions, coupled with a relaii 
decrease in total domestic mercury consumption o| 
the same period (65). NPMP monitoring stations ha\' 
fish with mercury concentrations exceeding the 85th ji 
centile (0.19 ppm; Table 7) are discussed below. 

Atlantic Coastal Streams — The Penobscot and Kenneii 
River stations 1 and 51 have a long history of chlorali; 
and paper-pulping operations (Haines, T. A. 1979. Ft 
Research Station Leader, Fish and Wildlife Serv ( 
Orono, Maine, personal communication). Unfiltcf 
water samples from various sites in both rivers had tt( 
mercury levels in 1971 that equaled or exceeded the P 
(lig/ liter recommended by the National Academy of !i 
ences Water Quality Criteria (35, 40). U.S Geologjc 
Survey water quality data (retrieved through STORIH 



32 



Pesticides Monitoring Jour ' 



JO substantiated concentrations > 0.2 /^g/ liter; some 
lues as high as 0.5 ju,g/ liter were reported from the 
inobscot River in 1978 (74). An old paper industry 
Hartsville on a tributary to the Pee Dee River (station 
i), most likely discharged mercury that became en- 
ipped in sediments years ago. Georgia's Altamaha 
ver (station 57) was studied intensively in 1970, and 
srcury residues of 1.0 ppm in largemouth bass were 
ported by the Georgia Water Control Board (18). A 
rge pulp processing company is just above this sam- 
ing site (station 57), at Doctortown, Georgia. 

ulf Coast Streams — Alabama's Tombigbee River (sta- 
)n 14) and Alabama River (station 59) both exceeded 
e 85th percentile of 0.19 ppm. with fish from station 
having a mean concentration of 0.33 ppm. There 
;re two chloralkali plants contaminating the Tombig- 
e in the early 1970's (12) — one at Mcintosh and the 
her at river mile 26 (Smith, B. W. 1970. Assistant 
nief of Fisheries Section. Alabama Game and Fish 
Dmmission, personal communication). Mercury con- 
ntrations have been relatively high in fish from the 
labama River throughout the NPMP samplings (20, 
'), but the source of mercury has not been identified. 

reat Lakes Drainage — The Lake St. Clair (station 
)7) mercury problem originated from chloralkali op- 
ations at Sarnia, Ontario, and is well documented (12, 
f). In 1970, mercury concentrations in fillets from four 
lecies of Lake St. Clair fish exceeded 1 ppm (67). An- 
her Great Lakes station at which fish had mercury 
incentrations greater than 0.19 ppm was station 22 on 
ike Superior. The Ontario Department of Lands and 
Drests reported mercury concentrations > 0.5 ppm in 
e muscle of fish from different parts of Lake Superior 
1970 (12). The source was presumably chloralkali 
ants at Marathon and Thunder Bay. The St. Lawrence 
iver (station 66) was listed by FDA as seriously con- 
minated in 1970. Mercury cell chloralkali plants are 
ill operating along the river at Cornwall, New York, 
id Beauharnois and Shawinigan, Quebec (13). 

'ississippi River System — In the Red River (station 
I), which drains into Lake Winnipeg in Manitoba 
evince, the 0.28-ppm mercury concentration in fish 
ceeds the 85th percentile. The source of mercury has 
)t been identified. Station 70 at Metropolis, Illinois, is 
rectly downstream from the confluence of the Ken- 
cky and Ohio Rivers. Two mercury cell chloralkali 
ants are located at Calvert City, Kentucky, near the 
outh of the Kentucky River (13). 

terior Basins — Pre- 1900 gold and silver milling opera- 
)ns of the Nevada Comstock Lode introduced substan- 
I amounts of mercury into the Truckee and Carson 
ver drainage systems; in bottom sediments, total mer- 
ry concentrations were as high as 20 ppm in 1971 



(48). Concentrations in fish (0.50-2.72 ppm) were 
highest in white bass, a piscivorous species from Lahon- 
tan Reservoir. Bottom sediments in the Truckee River 
basin (station 37) contained greater than background 
mercury concentrations, as a result of ore milling activ- 
ity in the Washoe Valley (72). 

Columbia River System — The Columbia River system, 
including the tributary Yakima, Willamette, Snake, and 
Salmon Rivers is on the East Pacific Rise, the location 
of major mercury deposits (cinnabar) in the Western 
Hemisphere. There are secondary mercury mining op- 
erations in Washington and Idaho, as well as gold min- 
ing, where mercury was used to recover gold from its 
ores by amalgamation (12). In 77 percent of northern 
squawfish samples from the Salmon River, the axial 
musculature contained mercury concentrations higher 
than 0.5 ppm (8). 

ARSENIC 

Arsenic concentrations in fish (Table 4) ranged from 
0.05 to 2.92 ppm and averaged 0.27 ppm. The increase 
in arsenic in freshwater fish since 1972 (Table 6) may 
be the result of dissemination by air pollution, smelter 
solid waste disposal, and continued use of arsenical 
pesticides. Contamination sources for arsenic are sug- 
gested here for the ^ 85th percentile (^ 0.38 ppm) 
NPMP stations. 

Atlantic Coastal Streams — No specific industrial source 
for arsenic in the Hudson River (station 3) is known. 
Extensive industrialization of the river, however, pre- 
sumably accounts for high arsenic concentrations in fish. 
In Georgia and South Carolina, substantial numbers of 
cotton farms (71) border the Savannah River and its 
tributaries (station 10). Arsenicals were used exten- 
sively on cotton from the early 1940's through the mid- 
dle 1960's in Georgia (Winstead, E. E. 1979. Assistant 
Commissioner, Georgia Department of Agriculture, 
Atlanta, personal communication). Agricultural runoff 
of applied arsenicals would provide a persistent source 
of arsenic to sediment beds. 

Gulf Coast Streams — In 1976, the Southern Plains states 
had more than 5 million acres planted in cotton, com- 
pared with slightly over 3 million for the Delta states 
(57). The highest concentration of cotton farms in the 
Southern Plains occurs along the Rio Grande Valley and 
western Texas Panhandle. Stations 82 and 60 are located 
on the Red and Brazos River systems, respectively, that 
drain these cotton-growing areas. Arsenic acid was the 
most heavily applied arsenical in 1976 in the Southern 
Plains, followed by sodium cacodylate and DSMA (57). 

Great Lakes Drainage — Relatively high arsenic levels 
have been reported in many areas of Lake Michigan. In 
the southern portion (stations 21 and 105), sediment 



)L. 15, No. 1, June 1981 



33 



concentrations have reached values as high as 30 ppm 
(50). In the northern portion (station 104), arsenic has 
accumulated in ferromanganese nodules that exist in the 
Green Bay area (50). One of the more striking cases of 
arsenic pollution involves the Ansul Co. of Marinette, 
Wisconsin (located close to the Menominee River, which 
empties into Green Bay). That company was a major 
manufacturer of methanearsonic acid (MAA) and 
cacodylic acid (CA), both arsenical herbicides (2). The 
company stored arsenic-contaminated sodium chloride 
and sodjum sulfate manufacturing by-products in un- 
protected salt piles on the bank of the river. Precipita- 
tion runoff from the piles produced levels of > 200 ppm 
arsenic in river sediments. Groundwater below the piles 
had total arsenic concentrations in excess of 6,000 ppm. 
Sediment levels adjacent to the salt piles were 2 percent 
arsenic by weight. As a result, the Menominee River is 
responsible for contributing 30-50 tons of arsenic per 
year to Lake Michigan (2). Marsh (36) concluded that 
there was a definite accumulation of lead and arsenic in 
and around Grand Traverse Bay in northeast Lake 
Michigan. Lead arsenate pesticides, used as orchard 
spray, accounted for all of the arsenic and about half 
of the lead buildup. 

In contrast to Lake Michigan, specific sources of arsenic 
in Lake Superior (stations 22, 102, and 103) and the 
St. Lawrence River (station 66) were not readily appar- 
ent. A nonpoint source affecting all of the Great Lakes 
was mentioned by Traversy et al. (24), who reported 
that arsenic levels in precipitation were higher than those 
in water from the Great Lakes and surrounding rivers. 
The elevated arsenic precipitation levels were especially 
prevalent at or near highly industrialized locations such 
as Toronto, Sarnia, and Hamilton. 



1970 to 1977. The arsenic levels in the present repo^ 
are similar to those found by the Upper Lakes Referenn 
Group (84). At stations where arsenic seems to 1 
higher than background levels — i.e., greater than tl 
85th percentile (0.38 ppm) — concentrations in bloate 
(Coregonus spp.) tended to be about double those 
lake trout (stations 21, 102, 104, and 105). The ten 
ency of bloaters to concentrate arsenic is apparent fro 
other work (II, 84) and may be related to a prima 
diet of zooplankton, which has been shown to bioco 
centrate arsenic (80). 

I 

Columbia River System — Stations 42-46 had mean i 
senic residues above the calculated 85th percent] 
(Table 7). Such a preponderance of "high" stations) 
a relatively small geographical area gives credence 
the following four possible sources of arsenic pollution 

1. Volcanic eruptions in the central Cascade area dun 
the Eocene epoch resulted in a large accumulation I 
volcanic deposits referred to as the Fisher formation, 
some instances, arsenic and perhaps boron were a p. 
of the pyroclastic debris that formed the so-called Fish 
rocks. Arsenic released from Fisher rocks by percolati 
subsurface water has resulted in arsenic groundwa 
contamination in some areas of the southern Willame 
Valley (31). This geologic source of arsenic may 
present in other areas of the Columbia River system. 

2. A copper-smelting facility at Tacoma, Washingt( 
and the lead-smelting refineries located at Kellogg, Ida 
(Bunker Hill), and East Helena, Montana, may prov 
airborne sources of arsenic to the Columbia River si 
tern. Soil and water pollution are possible through smi 
er solid waste disposal (78). 



A mine and copper smelting facility at White Pine, 
Michigan, is on the Mineral River, which drains into 
southern Lake Superior. Wash water and smelter runoff 
flow into Mineral River, as well as uncontrolled erosion 
from slag piles and tailing pond outfalls (78). Any of 
these effluents could contain substantial amounts of 



Arsenic concentrations in whole fish from the Great 
Lakes have been reported by Lucas et al. (33) and 
Traversy et al. (24) for the period from 1968 to 1971. 
Lucas et al., who analyzed 19 fish of 3 species, found a 
mean of 0.16 ppm arsenic, whereas Traversy et al., who 
analyzed 43 whole fish samples of 15 species, reported a 
mean of 0.063 ppm. The present authors report a mean 
arsenic concentration level of 0.72 ppm for fish from 
Great Lakes stations, including data from 33 sample 
composites of 10 different species. Although species, 
location, and methodology differences cannot be ruled 
out, the mean differences suggest a significant increase 
in arsenic concentrations in Great Lakes fish from 



34 



3. Active mining of copper, lead, and gold may prest 
mine water and mine tailing disposal problems, becai 
arsenic is found in association with these base-ma 
ores. 

4. In the headwater regions of the Yakima, monosodi 
methanearsonate (MSMA) and cacodylic acid are c; 
rently used for thinning in forestry (Gregory, S. I 
1979. Field Station Leader, Columbia National Fisheij 
Research Laboratory, Fish and Wildlife Service, C 
vallis, Oregon, personal communication). 

SELENIUM 

Concentrations of selenium in fish ranged from 0.05" 
2.87 ppm and averaged 0.56 ppm. Stations having m 
concentration levels exceeding the 85th percentile (C 
ppm) are discussed below. 

Atlantic Coastal Streams — Fish from station 4 on I 
Delaware River at Camden, New Jersey, had cond 
trations exceeding the 85th percentile, not only i 

Pesticides Monitoring JovRt 



enium (0.82 ppm), but also for cadmium and lead. 
le elevated trace element concentrations in these fish 
jbably reflect the highly industrialized character of 
; Delaware River. 

'ssissippi River System — The Big Horn (station 84) 
d Yellowstone (station 85) River tributaries of the 
ssouri River are closely associated with Montana's 
rt Union coal formation and outcroppings of phos- 
ate beds in Montana and Wyoming (45, 71). Sele- 
im concentrations in fish from these rivers may result 
im a geologic source of the element. Selenium sources 
the aquatic environment at the South Platte River 
ir Denver (station 88) may be industrial effluents or 
posits of coal, barite, and sulfur ore (77). Phosphate 
i outcroppings are located along the Kansas-Missouri 
rder close to station 90 on the Kansas River (77). 
enium concentrations in fish from stations 80 and 31 
ly also reflect a geologic source of the element, pri- 
irily sedimentary rocks associated with the Pierre 
mation. 

Ufornia Streams — The source of selenium in fish at 
tion 40 on the San Joaquin River is unknown. Selo- 
e, a selenium-containing pesticide, was registered for 
; on citrus in California in the I960's {41). This 
terial may have been applied in the San Joaquin 
itx valley and, if so, could still be a source of sele- 
im to the aquatic environment. 

Summary 

mary sources of the trace elements to the aquatic 
/ironment follow: 

dmium: electroplating industry, zinc-lead-copper 
elting and refining, phosphate fertilizers, sulfide ore- 
oing activities. 

ad: combustion of gasoline, lead-zinc-copper smelt- 
: operations, sulfide ore-mining activities, coal com- 
ition. 

:rcury: pre-1975 chloralkali industry, pre-1972 paper- 
iping operations, synthetic fiber industries, coal com- 
ition. 

senic: copper-lead-gold smelting and refining, coal 
nbustion, smelter solid waste disposal, arsenical pestl- 
es, geologic. 

enium: geologic, industrial. 

ce in the environment, there is evidence that all five 
:e elements may undergo biologically mediated trans- 
mation reactions that yield organometallic compounds 
t are routed through the food chain. 



Trace element concentrations (mg/kg wet weight) in 
whole fish in 1976-77 follow: 







Geometric 




85th 


Metal 


Range 


Mean 


Median 


Percentile 


Cadmium 


0.01-1,04 


0.07 


0.05 


0,11 


Lead 


0.10-4.92 


0,32 


0,19 


0,44 


Mercury 


0.01-0.84 


0.11 


0.09 


0.19 


Arsenic 


0.05-2.92 


0.27 


0.25 


0.38 


Selenium 


0.05-2.87 


0.56 


0.50 


0,82 



Temporal trends in whole-fish trace element concentra- 
tions (mg/kg wet weight) from 1972 to 1976-77 were 
as follows: cadmium, significant decline; lead, no sig- 
nificant difference; mercury, significant decline; arsenic, 
significant increase; and selenium, no significant differ- 
ence (1972 vs. 1977). 

Ackn owledgm en ts 

We thank each of the following persons for providing 
information: Marc Anderson, Water Chemistry Pro- 
gram, University of Wisconsin, Madison. Wis.; Jim 
Andreasen, CNFRL Field Research Station Leader, 
FWS, Victoria, Tex.; Frank M. D'ltri, Institute of Water 
Research and Department of Fisheries and Wildlife, 
Michigan State University, E. Lansing, Mich.; Stan 
Gregory, CNFRL, Field Research Station Leader, FWS, 
Corvallis, Oreg.; Terry Haines, CNFRL, Field Research 
Station Leader, Orono. Me.; David Lenhart, ECE Co- 
ordinator, Region 1, FWS, Portland, Oreg.; Dan Martin, 
CNFRL, Field Research Station Leader, FWS, Yankton, 
S.D.; Lawrence W. Nicholson, Great Lakes Fishery 
Laboratory, FWS, Ann Arbor, Mich,; Mike Saiki, 
CNFRL, Field Research Station Leader, FWS, Davis, 
Calif.; Barry W. Smith, Assistant Chief of Fisheries, 
Alabama Game and Fish Commission, Montgomery, 
Ala.; Max W. Walker, Environmental Specialist, Georgia 
Department of Natural Resources, Atlanta, Ga.; Parley 
Winger, CNFRL, Field Research Station Leader, FWS, 
Athens, Ga.; E. E. Winstead, Assistant Commissioner, 
Georgia Department of Agriculture, Atlanta, Ga. 

We especially thank the FWS biologists, state fish and 
game personnel, and local commercial fishermen who 
assisted in the collection of the 1976-77 NPMP fish 
samples. 

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36 



PESTicroES Monitoring JourncJ 



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15, No. 1, June 1981 



37 



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Wyoming, Laramie, Wyo. 64 pp. 



38 



Pesticides Monitoring Jouw" 



FOOD AND FEED 

Pesticide, Heavy Metal, and Other Chemical Residues in Infant and Toddler 
Total Diet Samples — (11)— August 1975-July 1976 ' 

Roger D. Johnson, Dennis D. Manske, Dallas H. New, and David S. Podrebarac 



ABSTRACT 

Food and Drug Administration, U.S. Department of 
'th and Human Services, initiated the Total Diet Study 
964 to monitor residues of pesticides and other chemi- 
ingested in the average diet of the United States' hearli- 
■aler, the young adult male. In August 1974, one-third 
le adult market baskets were replaced with infant and 
ler market baskets. Averages and ranges of residues for 
second in a series of infant and toddler baskets, for 
'1st 1975-July 1976, are reported. Included are results of 
■minations for zinc, cadmium, lead, selenium, arsenic, 
mercury. Results of recovery studies conducted with 
lounds of each residue type are also presented. 

Introduction 

Food and Drug Administration (FDA), U.S. De- 
ment of Health and Human Services (formerly U.S. 
artment of Health, Education, and Welfare), has 
[ monitoring the United States' total diet since 1964 
), 11-17). The program began with surveillance of 
s for fission products from atmospheric tests of 
■nonuclear weapons. Later, the emphasis was di- 
;d toward pesticide residues in foods. For several 
s the program focused on the total diet of the 16- 
9-year-oId male, statistically the United States' 
tiest eater. In August 1974, 10 of the 30 market 
ets were replaced with the total diet of 6-month-old 
Its and 2-year-old toddlers. The 10 market baskets 
collected in 10 cities that ranged in population 
1 fewer than 50,000 to one million or more. 

Is in each of 11 broad classes, as listed in Table 1, 
prepared separately, composited into a slurry, and 
>'zed for organochlorine and organophosphorus pes- 
es, carbaryl, herbicides, metals, and a few industrial 
licals. Methodologies included atomic absorption 
troscopy, fluorometry, gas chromatography, thin- 



TABLE 1. Commodity classes of infant and toddler foods 

analyzed for pesticides, metals, and other chemical residues, 

August 1975-July 1976 



Key 


Food Class 


I 


Drinking water ' 


II 


Whole milk, fresh i 


III 


Other dairy and substitutions, infant 




Other dairy and substitutions, toddler 


IV 


Meat, fish, and poultry, infant 




Meat, fish, and poultry, toddler 


V 


Grain and cereal products, infant 




Grain and cereal products, toddler 


VI 


Potatoes ■■ = 


VII 


Vegetables, infant 




Vegetables, toddler 


VIII 


Fruit and fruit juice, infant 




Fruit and fruit juice, toddler 


IX 


Oils and fats i. ^ 


X 


Sugar and adjuncts, infant 




Sugar and adjuncts, toddler 


XI 


Beverages ^- * 



I and Drug Administration, Kansas City District Office Labora- 
L009 Cherry St., Kansas City, MO 64106 



NOTE: Use key with Table 3. 

^ Because of similarity between infant and toddler diets, single deter- 
minations for certain classes of food are made and reported for both. 
- No infant composite for western region. 

■^ No infant composite from the north-central, western, and southern 
regions. 
* No infant composite from north-central region. 

layer chromatography, mass spectroscopy, and estab- 
lished extraction and cleanup techniques (7, 8, 10, 18, 
19). Except for the water composite (9), quantitation 
limits and instrumental conditions were the same as 
those described for the adult market baskets. 

Results 

The infant composites of the present series contained 
301 residues of 31 compounds, with 51 residues at the 
trace level. In comparison, the first infant composites 
reported last year contained 306 residues of 28 com- 
pounds; 121 were reported at the trace level. 

Toddler composites of the present series showed 473 
residues of 38 compounds; 76 were present in trace 
amounts. The first toddler series last year reported 468 
residues of 30 compounds with 179 at the trace level. 



15, No. 1, June 1981 



39 



The chemical compounds found, the number of findings, 
and the range for each are listed in Table 2. TTie fre- 
quency of occurrence of each compound by food class 
is presented in Table 3. Table 4 shows the level of every 
residue found within each food class. The averages given 
in Table 4 are based on the total number of composites 
examined for that food class. Trace values were treated 
as zero in calculating these averages. Table 5 shows the 
intake of pesticide and industrial chemical residues in 
terms of /xg/kg body weight/day, and Table 6 shows the 
intake of six metals in terms of /xg/day (mg/day for 
zinc). For comparison, the findings for the 1975 fiscal 
year are also shown. The most common residues and 
their average levels are discussed below for each of the 
1 1 food classes. No findings have been corrected for 
recoveries. 

DRINKING WATER 

Infant and Toddler — -Tap water samples analyzed were 
taken from the same location as the market basket. The 
result of a single analysis is that reported for both infant 
and toddler composites. The water was used to prepare 
other market basket items requiring dilution or addition 
of water. Only two metal residues were found: four 
samples contained zinc averaging 0.170 ppm for the 
series, and one sample contained cadmium, averaging 
0.002 ppm. 

WHOLE MILK, FRESH 

Infant and Toddler — This composite was common to 
both diets. Averages for chlorinated pesticide residues 
included 0.001 ppm p,p'-DDE; trace a-BHC (hexa- 
chlorocyclohexane); trace dieldrin; and a trace of 
heptachlor epoxide. Averages for the three metals 
found were 6.80 ppm zinc; 0.007 ppm cadmium; and 
0.002 ppm selenium. A trace of PCP was detected in 
one composite. 

OTHER DAIRY AND SUBSTITUTIONS 

Infant — The variation in infants' and toddlers' diets be- 
comes apparent with these composites. Dieldrin was 
found in four composites averaging trace for the series. 
Averages of other organochlorines were traces of o-BHC, 
heptachlor epoxide, methoxychlor, and /?,p'-DDE. A 
trace of PCP was found in one composite. Averages 
for metal residues were 5.38 ppm zinc, 0.004 ppm 
cadmium, and 0.013 ppm lead. 

Toddler — All 10 composites contained dieldrin, averag- 
ing 0.003 ppm, and «-BHC, averaging 0.002 ppm. 
Averages of other pesticide residues included 0.004 
ppm p,p'-DDE, 0.001 ppm heptachlor epoxide, and 
traces of octachlor epoxide, methoxychlor, HCB, and 
lindane. A trace of PCP was found in one composite. 
Averages of metal residues included 5.94 ppm zinc, 
0.016 ppm selenium, 0.013 ppm cadmium, 0.006 ppm 
lead, and a trace of mercury. 



40 



TABLE 2. Chemical and metal residues found in in] 
and toddler food composites from 10 United States citie 
August 197 5 -July 1976 



Chemical Found 



No. OF 

Composites 

With Residues 



No. OF Positive 

Composites With 

Residues 

Reported as 

Trace ' Range, i 



INFANT 



Zinc 

Cadmium 

Lead 

Selenium 

P.p'-DDE 2 

Dieldrin 

Malathion 

a-BHC 

Heptachlor epoxide 

Mercury 

PCP 

CIPC 

Arsenic 

Dichloran 

Endosulfan ^ 

HCB 

Endrin 

Lindane 

Toxaphene 

Octachlor epoxide 

TCNB 

P,P-DDT ' 

Chlordane 

Diazinon 

Methoxychlor 

Parathion 

Ethion 

Fonofos 

Carbaryl 

TCTA 

Perthane 



85 

59 

35 

21 

17 

15 

12 

9 

6 

4 

4 

3 

3 

3 

3 

3 

2 

2 

2 

2 

1 

1 

1 

1 

1 

1 

1 

1 

1 



TODDLER 



Zinc 


100 





0.100-3i 


Cadmium 


77 





0.005-0. 


Lead 


35 





0.050-0. 


Dieldrin 


31 


6 


O.OOI-O. 


a-BHC 


29 


12 


0.0006-0. 


Selenium 


27 





0.020-0, 


P.P'-DDE = 


26 


4 


0.001-0. 


Heptachlor epoxide 


20 


13 


0.001-0. 


Malathion 


16 





0.005-0. 


Lindane 


15 


3 


0.001-0. 


HCB 


14 


8 


0.0007-0. 


Arsenic 


11 





0.030-0. 


Octachlor epoxide 


10 


9 


0. 


Mercury 


7 





0.002-0. 


PCP 


6 


5 


0. 


CIPC 


5 





0.023-0. 


PCA 


4 





0.002-0. 


Pentachlorobenzene 


4 


1 


0.001-0. 


Toxaphene 


4 


3 


Oj 


Dichloran 


3 





0.012-0. 


PCNB 


3 





0.001-0. 


Diazinon 


3 


1 


0.001-0; 1 


Chlordane 


3 


2 


0. 


Parathion 


3 


3 


T 


p,p -DDT 2 


2 


1 


0. 


P,p'-TDE 2 


2 


1 


0. 


Fonofos 


2 





O.OOI-O. 


Ronnel 







0. 


Endrin 







0. 


2,4-D 







0. 


TCNB 







0. 


rra/ij-Nonachlor 







0. 


PCTA 







0. 


TCTA 




1 


T 


Ethion 




1 


T 


o-PhenylphenoI 




1 


T 


Methoxychlor 




1 


T 


PCP methvl ether 







0. 


^ Chemicals detected by 


the specific analytical methodology below 


limit of quantitation were confirmed qualitatively 


and reportet i 


trace (T). The limits 


of quantitation 


vary with 


residues and .-> 


classes. 








• Other isomers also included in reporting 






» Reportings include isomers I and II and sulfate. 






Pesticides 


Monitoring Jour» 



LE 3. Frequency of occurrence of chemical and metal 
ues, by food class, in infant and toddler food composites 
rom 10 United States cities — August 1975-July 1976 

Food Class ' 

icAL I II III IV V VI VII vin IX X XI 

NUMBER OF OCCURRENCES IN INFANT FOODS 





4 


10 


10 


10 


10 


8 


10 


9 


2 


7 


5 


ium 


1 


4 


4 


7 


10 


8 


10 


6 


2 


6 


1 










1 


8 


6 


6 


8 


5 








1 


Lim 





1 





10 


10 




















IDE 





3 


4 


5 





3 


2 














in 





2 


4 


6 





2 








1 








Won 














10 











2 













3 


5 


1 























chlor epoxide 





I 


3 

















2 








ry 











2 








1 








1 










1 


1 





1 








1 




























3 

















,c 














3 




















Iran 

















1 





2 











ulfan 

















1 


1 


1 






















2 





1 

















1 


























2 








le 














2 




















hene 


























2 








ilor epoxide 











2 








































1 

















DT 




















1 














lane 


























1 








on 














1 




















xy chlor 








1 


























ion 




















1 














1 























1 











:is 


























1 








71 























1 




























1 

















ne 























1 












NUMBER OF OCCURRENCES IN TODDLER FOODS 



im 

DE 

:hlor epoxide 

lion 

le 



ilor epoxide 

ry 



hlorobenzene 

tiene 

ran 

on 

ane 

ion 

DT 

)E 

>s 



Jonachlor 



ylpiienol 
lychlor 
ethyl ether 



10 10 



10 10 

10 8 

4 9 

8 10 

8 9 



10 10 
10 10 



10 



able 1 for key to food classes. 

15, No. 1, June 1981 



MEAT, FISH, AND POULTRY 

Infant — These infant composites contained among the 
highest number of residues. Metals dominated 37 of the 
53 residues, with averages of 16.8 ppm zinc, 0.094 ppm 
selenium, 0.087 ppm lead, 0.023 ppm cadmium, and 
0.002 ppm mercury. Of the 16 nonmetals. dieldrin was 
found in six composites averaging a trace for the 
series; /7,p'-DDE, averaging 0.003 ppm for the series, 
was found in five composites; HCB, octachlor epoxide, 
and a-BHC averaged a trace. 

Toddler — Ninety-nine residues were found. All 10 com- 
posites contained residues of p,p'-DDE, ranging from 
0.002 to 0.016 ppm. and dieldrin, ranging from 0.001 
to 0.003 ppm. Heptachlor epoxide, p,p'-TDE, p,p'- 
DDT, hexachlorobenzene (HCB), a-BHC, lindane, 
octachlor epoxide, ronnel, and /ra«j-nonachlor averaged 
a trace for the series. Average metal residues included 
27.5 ppm zinc and 0.180 ppm selenium. Lesser amounts 
of arsenic, lead, cadmium, and mercury, averaging 
0.092, 0.030, 0.010, and 0.006 ppm, respectively, were 
also found. 

GRAIN AND CEREAL PRODUCTS 

Infant — All 10 composites contained malathion, rang- 
ing from 0.003 to 0.049 ppm and averaging 0.020 ppm. 
There was one report of diazinon at the 0.010 ppm 
level, and only traces of lindane and PCP were found. 
Averages for the metals were 14.6 ppm zinc, 0.189 
ppm selenium, 0.046 ppm lead, 0.027 ppm cadmium, 
and 0.018 ppm arsenic. 

Toddler — Like the infant composites, these toddler 
composites all contained malathion residues, ranging 
from 0.006 to 0.025 ppm and averaging 0.012 ppm. 
Diazinon, averaging trace amounts, was found in three 
composites. Averages for the metals found were 10.3 
ppm zinc, 0.179 ppm selenium, 0.065 ppm lead, 0.026 
ppm cadmium, and 0.008 ppm arsenic. 

POTATOES 

Infant — The chlorinated herbicide CIPC was found in 
three composites, ranging from 0.023 to 0.469 ppm 
and averaging 0.073 ppm for the series. TCNB 
averaged 0.003 ppm for the series. Other organo- 
chlorine pesticides averaging trace amounts included 
p.p'-UUE, dieldrin, dichloran, endosulfan, TCTA, and 
HCB. Of the metals found, zinc averaged 2.72 ppm, 
lead averaged 0.061 ppm, and cadmium averaged 
0.048 ppm. 

Toddler — The chlorinated herbicide CIPC was found 
in five composites, ranging from 0.023 to 0.469 ppm 
and averaging 0.156 ppm for the series. TCNB was 
found in one composite at 0.026 ppm, and dieldrin, 
lindane, p,p' -DDE, TCTA, and HCB averaged a 
trace. The metals zinc and cadmium averaged 3.92 



41 



TABLE 4. Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 Un 

States cities — August 1975-July 1976 





Residvie, 


PPM 


Chemical 


Residue, 


PPM 


Chemical 


Infant 


Toddler 


Infant 


TODDLEK 


I. WATER 




DIELDRIN 












Average 

Positive composites 


T 


0.003 


ZINC 










Average 


0.170 


0.170 


Total number 


4 


10 


Positive composites 






Number reported as trace 


2 





Total number 


4 


4 


Range 


0.001 


0.001-O.C 


Number reported as trace 








METHOXYCHLOR 






Range 


0.200-0.600 


0.200-0.600 


Average 


T 


T 


CADMIUM 






Positive composites 






Average 


0.002 


0.002 


Total number 


1 


I 


Positive composites 






Number reported as trace 


1 


1 


Total number 


1 


1 


Range 


T 


T 


Number reported as trace 








CADMIUM 






Range 


0.02 


0.020 


Average 


0.004 


0.013 








Positive composites 
Total number 
Number reported as trace 
Range 


4 

0.005-0.020 


7 



II. WHOLE 


MILK, FRESH 










0.006-O.t 


ZINC 

Average 


6.80 


6.80 


u-BHC 

Average 


T 


0.002 


Positive composites 






Positive composites 






Total number 


10 


10 


Total number 


S 


10 


Number reported as trace 
Range 




3.30-28.8 



3.30-28.8 


Number reported as trace 
Range 


4 
0.001 




0.001-0.( 


a-BHC 

Average 


T 


T 


p,p'-DDE 

Average 


T 


0.004 


Positive composites 
Total number 


3 


3 


Positive composites 
Total number 


4 


8 


Number reported as trace 
Range 


2 
0.0006 


2 
0.0006 


Number reported as trace 
Range 


4 
T 


1 
0.001-0.( 


P,P'-DDE 

Average 


0.001 


0.001 


LEAD 

Average 


0.013 


0.006 


Positive composites 
Total number 


3 


3 


Positive composites 
Total number 


1 


1 


Number reported as trace 
Range 
DIELDRIN 


1 
0.002-0.005 


1 

0.002-0.005 


Number reported as trace 
Range 
PCP 
Average 



0.130 




0.060 


Average 


T 


T 


T 


T 


Positive composites 
Total number 


2 


2 


Positive composites 
Total number 


1 


1 


Number reported as trace 

Range 
CADMIUM 
Average 
Positive composites 

Total number 



0.001 

0.007 

4 



0.001 

0.007 

4 


Number reported as trace 

Range 
SELENIUM 
Average 
Positive composites 

Total 

Number reported as trace 

Range 


1 

T 


1 

T 

0.016 

4 

0.030-O.t 


Number reported as trace 

Range 
PCP 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
HEPTACHLOR EPOXIDE 
Average 
Positive composites 

Total number 

Number reported as trace 



0.005-0.040 



0.005-0.040 




T 

I 

1 
T 

T 

I 

1 


T 

1 

1 
T 

T 

1 

1 


OCTACHLOR EPOXIDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 
MERCURY 
Average 
Positive composites 

Total number 




T 

6 
6 

T 

T 
1 


Range 
SELENIUM 


T 


T 


Number reported as trace 

Range 
HCB 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 






0.002 


Average 

Positive composites 

Total number 

Number reported as trace 

Range 


0.002 

1 

0.02 


0.002 

1 


0.020 




T 

5 
4 
0.0007 








LINDANE 

Average 




T 


in. OTHER DAIRY 


AND SUBSTITUTIONS 








Positive composites 
Total number 






ZINC 








1 


Average 


5.38 


5.94 


Number reported as trace 







Positive composites 






Range 




0.002 


Total number 


10 



10 









Number reported as trace 


IV. MEAT, FISH, 


AND POULTRY 




Range 
HEPTACHLOR EPOXIDE 


2.90-8.50 


1.60-14.6 










ZINC 






Average 


T 


0.001 


Average 


16.84 


27.52 


Positive composites 






Positive composites 






Total number 


3 


8 


Total number 


10 


10 


Number reported as Uace 


3 


3 


Number reported as trace 








Range 


T 


0.001-0.003 


Range 


8.90-36.3 


11.3-34. 



42 



Pesticides Monitoring Joui* 



.E 4 (cont'd.). 



Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 
United States cities — August 1975-July 1976 



Residue, ppm 



Residue, ppm 



Chemical 



Infant 



Toddler 



Chemical 



4IUM 

age 

ive composites 

■tal number 

imber reported as trace 

inge 

age 

ive composites 

■tal number 

imber reported as trace 

inge 

[lUM 

age 

ive composites 

tal number 

imber reported as trace 

Jige 

URY 

age 

ive composites 

tal number 

imber reported as trace 

nge 

•RIN 

age 

ive composites 

tal number 

mber reported as trace 

nge 

age 

ive composites 

tal number 

mber reported as trace 

nge 

ige 

ive composites 

;al number 

mber reported as trace 

nge 

)E 

ige 

ve composites 

al number 

mber reported as trace 

ige 

;hlor epoxide 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 

IC 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 

CHLOR EPOXIDE 

ge 

ve composites 

al number 

mber reported as trace 

Ige 

E 

ge 

ve composites 

al number 

Tiber reported as trace 

Ige 

T 

ge 

ve composites 

al number 

Tiber reported as trace 

Ige 



0.094 



0.180 



10 



0.040-0.220 


9 

0.110-0.300 


0.087 


0.030 


8 

0.050-0.180 


3 


0.050-0.190 


0.023 


0.010 


7 

0.010-0.100 


9 


0.008-0.020 


0.002 


0.006 


2 

0.004-0,016 


6 

0.005-0.020 


T 


0.002 


6 

4 
0.002-0.003 


10 

1 
0.001-0.003 


T 


T 


2 
2 
T 


4 
2 
0.0007-0 .0009 


T 


T 


1 
1 
T 


8 

7 
0.0007 


0.003 


0.005 


5 

2 

0.002-0.019 


10 



0.002-0.016 


T 


T 


2 
2 
T 


4 
3 
0.004 



0.092 

7 

0.060-0.290 

T 

9 

8 
0.002 



2 
1 
0.002 



Infant 



TODDLEK 



LINDANE 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
RONNEL 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

rranj-NONACHLOR 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



4 
3 
0.003 



1 


0.002 



1 

0.006 



V. GRAIN AND CEREAL PRODUCTS 



2 
1 

0.005 



ZINC 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
SELENIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ARSENIC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

MALATHION 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

PCP 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LINDANE 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

DIAZINON 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



14.6 

10 



6.8-20.3 

0.189 



0.027 



0.018 

3 

0.040-0.090 

0.020 

10 



0.003-0.049 

0.046 



2 

0.004 

0.001 

1 


0.010 



10.29 

10 



6.30-18.9 

0.179 



10 


10 








0.140-0.250 


0.080-0.290 



0,026 



10 


10 








0.020-0.050 


0.018-O.040 



0.008 

2 

0.030-0.050 

0.012 

10 



0.006-0.025 

0.065 



6 


0.050-O.100 


5 

0.060-0.210 


T 


T 


1 
1 
T 


1 
1 
T 



3 
1 

0.00 1-0.00 J 



15, No. 1, June 1981 



43 



TABLE 4 (cont'd.). 



Levels of chemical and metal residues, by food class, in infant and toddler food composites froi 
United States cities — August 1975-July 1976 







Residue, ppm 


Chemical 




Residue, ppm 


Chemical 


Infant Toddler 


Infant Toddle 




VI. 


POTATOES 




VII. 


VEGETABLES 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 
Total number 
Number reported as trace 
Range 

LINDANE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

P,p'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DICHLORAN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ENDOSULFAN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CI PC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

TCNB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

TCTA 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

HCB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



2.72 



0.30-4.30 



0.061 



3 
1 

0.001-0.002 

T 




0.006 



I 
1 
T 

0.073 

3 


0.023-0.469 



0.003 

1 

0.026 



1 
1 
T 



3.92 

10 



0.300-8.20 

0.078 



6 

0.050-0.120 


6 


0.050-0.350 


0.048 


0.045 


8 

0.020-0.130 


10 



0.010-0.120 


T 


T 


2 
1 
0.002 


2 
1 

0.002 



1 


0.007 



3 
1 
0.002 



0.156 



0.023-0.469 



0.003 



1 

0.026 



1 
1 
T 



1 
1 
T 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

MERCURY 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

PARATHION 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

p,p'-DDE 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

P,P'-DDT 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ENDOSULFAN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

PCP 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LINDANE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

a-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



3.66 

10 



1,80-6.40 

0.078 



0.060-0.240 

0,043 

10 


0.010-0.120 



1 

0.002 



1 
1 
T 



2 


0.002-0.004 



1 
1 
T 

0,004 

1 


0,037 



3,49 



1 
1 
T 



1 


0,002 



1 
1 
T 



2 

0.002 



44 



Pesticides Monitoring Jou i 



LE 4 (cont'd.). 



Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 
United States cities — August 1975-July 1976 







Residue. 


PPM 


Chemical 




Residue, 


PPM 


Chemical 


Infant 


Toddler 


Infant 


Toddler 


VIII. 


FRUITS AND FRUIT JUICES 




MALATHION 
















Average 




0.025 


0.041 


















Positive composites 








rage 




0.610 


0.870 


Total number 




2 


6 


tive composites 








Number reported 


as trace 








>tal number 




9 


9 


Range 




0.015-0.035 


0.005-0.187 


umber reported 


as trace 








TOXAPHENE 








ange 




0.300-1.00 


0.200-2,40 


Average 

Positive composites 




T 


0.007 


•age 




0,066 


0.062 


Total number 




2 


4 


live composites 








Number reported 


as trace 


2 


3 


)tal number 




5 


5 


Range 




T 


0.075 


umber reported 


as trace 








DIELDRIN 








inge 




0.070-0.290 


0,080-0,240 


Average 




0.001 


0.001 


ISULFAN 








Positive composites 








■age 




T 




Total number 




1 


5 


tive composites 








Number reported 


as trace 





3 


)tal number 




1 




Range 




0.002 


0.002-0.007 


umber reported 


as trace 


1 




ENDRIN 








mge 




T 




Average 




0.006 


0.001 


HANE 








Positive composites 








■age 




T 




Total number 




2 


1 


tive composites 








Number reported 


as trace 


1 





)tal number 




1 




Range 




0.011 


0.009 


jmber reported 


as trace 


1 




HEPTACHLOR EPOXIDE 






inge 




T 




Average 




T 


0.001 


LORAN 








Positive composites 








age 




0.001 


0.005 


Total number 




2 


2 


tive composites 








Number reported 


as trace 


2 


1 


)tal number 




2 


3 


Range 




T 


0.007 


imber reported 


as trace 








FONOFOS 








inge 




0.006-0.007 


0.012-0,026 


Average 




T 


T 


HUM 








Positive composites 














Total number 




1 


2 


age 




0.007 


0.005 


Number reported 


as trace 


1 





Eive composites 
ttal number 




6 


4 


Range 




T 


0.001-0.002 


Jmber reported 


as trace 








CHLORDANE 








inge 




0.010-0.017 


0.010-0.020 


Average 

Positive composites 




T 


0.014 


ARYL 








Total number 




1 


3 


age 




T 




Number reported 


as trace 


1 


2 


tive composites 








Range 




T 


0.137 


ital number 




1 












Jmber reported 


as trace 


1 




p,p'-DDE 








inge 




T 




Average 

Positive composites 
Total number 






T 

1 


■age 




T 


T 


Number reported 


as trace 




1 


tive composites 








Range 






T 


)tal number 




1 


1 










Jmber reported 


as trace 




1 


LEAD 








mge 




T 


T 


Average 

Positive composites 






0.050 


)N 








Total number 






6 


age 




T 


T 


Number reported 


as trace 







tive composites 








Range 






0,060-0.120 


ital number 




1 


1 


HCB 

Average 

Positive composites 








Jmber reported 
inge 


as trace 


1 
T 


1 
T 






0.002 


NYLPHENOL 








Total number 






4 


age 






T 


Number reported 


as trace 




1 


tive composites 








Range 






0.001-0.016 


)tal number 
Jmber reported 


as trace 




1 
1 


PCNB 








mge 






T 


Average 






0.001 






Positive composites 
















Total number 
Number reported 


as trace 




3 




IX. OILS AND FATS 















Range 
PCA 






0.001-O.0O5 














age 




20.3 


14.43 


Average 






0.005 


ive composites 








Positive composites 








tal number 




2 


10 


Total number 






4 


imber reported 


as trace 








Number reported 


as trace 







nge 




20.2-20.4 


10.6-19.2 


Range 






0.002-0.044 


lUM 








PENTACHLOROBENZENE 






age 




0.074 


0.062 


Average 






0.001 


ive composites 








Positive composites 








tal number 




2 


10 


Total number 






4 


imber reported 


as trace 








Number reported 


as trace 




1 


nge 




0.067-0.080 


0.040-0.110 


Range 






0.001-0.009 



15, No. 1, June 1981 



45 



TABLE 4 (cont'd.). 



Levels of chemical and metal residues, by food class, in infant and toddler food composites froi 
United States cities — August 1975-July 1976 



Residue, ppm 



Chemical 



Infant 



SELENIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
PARATHION 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
ARSENIC 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
PCTA 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
PCP METHYL ETHER 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 



X. SUGAR AND ADJUNCTS 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 
CADMIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
MERCURY 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
SELENIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
PCP 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
LINDANE 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
a-BHC 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
LEAD 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 



2.73 

7 

0.20-20.7 

0.005 

6 

0.007-0.010 

0.0006 




0.006 



Toddler 



0.011 

2 


0.050-0.060 

T 

2 
2 
T 

0.003 

1 


0.030 



I 


0.003 



1 


0.002 



5.51 

10 


1.50-12.5 

0.015 

10 



0.010-0.020 



0.004 

1 

0.040 

0.007 

1 

0.070 

0.001 

6 



0.001-0.003 

T 

6 

3 
0.001-O.0O2 

0.028 

2 

0.090-0.190 



Residue, ppm 



Chemical 



Infant 



Toddle 



ARSENIC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 
2.4-D 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 



0.004 

1 

0.040 

0.002 

1 

0.025 



XL BEVERAGES 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 
CADMIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 
LEAD 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 



0.314 



0.180 



5 

0.100-1.00 


7 

0.100-0 


0.007 


0.002 


1 

0.012 


2 

0.010 


0.011 


0.007 


1 

0.080 


1 

0.070 



NOTE: Average residues are based upon the total number of cc 
ites examined; trace values were treated as zero. It is quite p 
that average values reported as T can be well below the detection 
of the method for that composite. 



ppm and 0.045 ppm, respectively, and were four^ 
all 10 composites; lead was found in six compo] 
averaging 0.078 ppm for the series. 



VEGETABLES 

Infant — The highest level for a chlorinated pesh 
was 0.037 ppm endosulfan found in one compi 
There were two reports of p.p'-DDE, 0.002 ppmi 
0.004 ppm, and trace findings of parathion and j 
DDT. Average residues of metals included 3.66 
zinc, 0.078 ppm lead, 0.043 ppm cadmium, and a 
of mercury. 

Toddler — Trace averages were reported for parat 
dieldrin, lindane, PCP, p.p'-DDE and a-BHC. 
lead, and cadmium accounted for 26 of the toti 
residues and averaged 3.49, 0.081, and 0.026 i 
respectively. 



FRUITS AND FRUIT JUICES 

Infant — The chlorinated pesticide Perthane® ana 
carbamate pesticide carbaryl were found only ir 
food group, in one composite at the trace level. < 



46 



Pesticides Monitoring Jot)( 



LE 5. Intake of pesticide and industrial chemical 
ndues by infants and toddlers, market basket surveys 
FY 1975 \s FY 1976 

Residue, ^g/kg Body Wt/Day 



TABLE 6. Dietary intakes of metals by infants and 
toddlers, FY 1975 vs FY 1976 



Infant 



Toddler 



FY 75 



FY 76 



FY 75 



FY 76 



chlor epoxide 

hlor 

L 

ulfan I 

ulfan II 

ulfan sulfate 
L 



ryl 
lane 



ran 

il 



)S 

)hos 

le 

lion 

xychlor 

1 parathion 

lylphenol 

ordane 

ion 

hloroanisole 
iilorobenzene 



ND 
0.0153 
0.0153 

0.1276 
T 
T 

0.1276 

0.0097 

ND 

0.0097 

ND 

ND 
ND 
ND 

0.0228 
ND 
T 
ND 

0.0020 

ND 

ND 

T 

0.0383 
ND 
ND 
ND 
ND 

0.0044 
ND 

0.0133 

0.2028 
T 

ND 
ND 
T 
T 

0.0053 
ND 

0.0005 

0.0073 

0.0154 



tachlorothioanisole) ND 
ne ND 

3ne 



lene 
fonachlor 



henothion 



ND 

T 

ND 

0.2573 
ND 
ND 
ND 



ND 

0.0249 
0.0249 

0.0682 
T 

ND 
0.0682 

0.0001 

ND 

0.0001 

0.001 1 
0.0045 
0.0368 
0.0424 

0.0055 

ND 

T 

T 

0.0321 

ND 

ND 

0.0053 

0.0230 

ND 

T 

ND 

T 

0.0009 

ND 

0.0049 

0.0865 

T 

ND 
ND 
0.0008 
T 
ND 
ND 
ND 
ND 
T 

ND 

T 
ND 

T 

ND 
T 

ND 

0.0019 

ND 



ND 
0.0502 
0.0502 

0.1598 
0.0064 
0.0037 
0.1699 

0.0057 

ND 

0.0057 

ND 

ND 

0.0078 

0.0078 

0.0211 

ND 

0.0047 

ND 

0.0458 

ND 

ND 

0.0067 

0.0506 

ND 

ND 

ND 

ND 

0.0064 

0.0033 

0.0341 

0.1374 

ND 

ND 

ND 

T 

ND 
0.0058 

ND 
0.0007 
0.0024 
0.0214 

ND 
ND 
ND 

T 

T 

0.0467 

ND 

T 
ND 



ND 

0.0412 
0.0412 

0.0985 
0.0046 
0.0018 
0.1049 

0.0057 

ND 

0.0057 

ND 

ND 
ND 

ND 

0.0132 
ND 
ND 
0.0100 
0.3942 
0.0058 

ND 
0.0030 
0.0342 
ND 
ND 
0.0007 
0.0002 
0.0042 

ND 

0.0096 

0.1488 

T 

ND 
T 
T 
0.0013 
0.0064 
0.0003 
0.0013 
0.0007 
0.0162 

0.0004 
ND 
ND 
ND 

0.0022 
0.0127 
0.0050 
0.0074 
ND 



: ND r= not detected; T =^ Trace (below the limits of quantita- 
etected and verified, but not quantifiable). 



ides reported at the trace level included endo- 
1, PCP, and ethion. Dichloran was found in two 
osites and averaged 0.001 ppm for the series. Low- 
metal residues included zinc, lead, and cadmium, 
ging 0.610, 0.066, and 0.007 ppm, respectively. 

ler — Dichloran, found in three composites, ranged 

0.012 to 0.026 ppm for a series average of 0.005 

Traces of PCP, ethion, and the fungicide o- 



Residue, jig/day 



Infant 



Toddler 



Metal 



FY 75 



FY 76 



FY 75 



FY 76 



Lead 

Cadmium 
Zinc 1 
Arsenic - 
Selenium 
Mercury 



20.79 
5.16 
5.33 
2.76 

21.63 
0.03 



26.94 
12.33 
8.15 
0.42 
10.81 
0.56 



25.61 
10.72 

8.26 
11.10 
58.38 

0.94 



30.12 
14.19 

9.46 
12.28 
44.99 

0.81 



1 Values are mg/day. 

- Values calculated as arsenic Irioxide (As^O^) . 



phenylphenol were also reported. Zinc, lead, and cad- 
mium all averaged below 1.0 ppm. 

OILS AND FATS 

Infant — Only two of the 10 market baskets included a 
separate composite of oils and fats for the infant. Mala- 
thion, endrin, and dieldrin averaged 0.025, 0.006, and 
and 0.001 ppm, respectively. Trace averages were re- 
ported for toxaphene, heptachlor epoxide, and chlor- 
dane. 

Fonofos, an organophosphorus pesticide, was found 
only in this food group, at the trace level. Both com- 
posites had residues of zinc, 20.2 ppm and 20.4 ppm, 
and cadmium, 0.067 ppm and 0.080 ppm. 

Toddler — A total of 71 residues was reported for these 
10 composites. The metals accounted for 29 residues 
and included zinc (average 14.43 ppm), cadmium 
(average 0.062 ppm), lead, selenium, and arsenic. 
Three organophosphorus pesticides were reported: 
malathion in six composites, ranging from 0.005 to 
0.187 ppm and averaging 0.041 ppm for the series; 
parathion traces in two composites; and fonofos in 
two composites, ranging from 0.001 to 0.002 ppm and 
averaging trace for the series. Malathion residues 
averaged highest of the nonmetals and appeared in the 
most composites. Among the organochlorine com- 
pounds, toxaphene averaged 0.007 ppm and was 
reported in four composites. Other organochlorine 
residues included PCA, dieldrin, pentachlorobenzene, 
chlordane (average 0.014 ppm), HCB, heptachlor 
epoxide, PCNB, p.p'-DDE, PCTA, and PCP methyl 
ether. 



SUGAR AND ADJUNCTS 

Infant — Only three metal residues were reported for 
these infant composites. Zinc was found in seven com- 
posites, ranging from 0.20 to 20.7 ppm, for a series 
average of 2.73 ppm. Cadmium was found in six com- 



15, No. 1, June 1981 



47 



posites, ranging from 0.007 to 0.010 ppm and averag- 
ing 0.005 ppm for the series. One residue of mercury 
was reported at 0.006 ppm for a series average of 
0.0006 ppm. 

Toddler — In contrast, the toddler composites had 38 
residues of nine different compounds: five metals, two 
chlorinated herbicides, and two organochlorine pesti- 
cides. Averages of the metals included 5.51 ppm zinc, 
0.015 ppm cadmium, 0.028 ppm lead, and 0.004 ppm 
each for arsenic and selenium. Two composites con- 
tained herbicides: PCP at 0.07 ppm and 2,4-D at 
0.025 ppm. Six residues were reported for each of the 
chlorinated pesticides, lindane and a-BHC, with ranges 
0.001 to 0.003 ppm and 0.001 to 0.002 ppm, respec- 
tively. 

BEVERAGES 

Infant — Only three metal residues were reported for 
these composites. Zinc was found in five composites, 
ranging 0.100 to 1.00 ppm, and averaging 0.314 ppm 
for the series; 0.012 ppm cadmium and 0.080 ppm 
lead were reported for one composite. 

Toddler — The metal residues found in these toddler 
composites were the same as those found in the infant 
composites. Zinc was found in seven composites, rang- 
ing from 0.100 to 0.500 ppm, and averaging 0.180 
ppm for the series. Cadmium was reported twice at 
the 0.01 ppm level, and lead was reported once at 
0.070 ppm. 

Discussion 

INFANT 

The infant composites contained a total of 301 resi- 
dues: 207, or 68.7 percent, were metals; 86, or 28.6 
percent, were pesticides; and the remaining 2.7 per- 
cent included seven herbicide residues and one fungi- 
cide residue. In comparison, a total of 306 residues was 
reported for the first infant composite series: 199 (65 
percent) metals, 99 (32.3 percent) pesticides, five 
fungicides, one herbicide, and two industrial chemicals. 

Of the metal residues, zinc, occurring most frequently, 
was found in 85 composites with the highest level, 36.3 
ppm, occurring in the meat-fish-poultry composite. 
Although 59 cadmium residues were reported, the 35 
lead residues, ranging from 0.050 to 0.290 ppm, might 
be of greater significance. The highest level of lead 
residues was found in the fruit and fruit juice compos- 
ites. All but one of the 21 selenium residues were found 
in the meat-fish-poultry composites. Arsenic was re- 
ported at low levels in three grain-cereal composites. Six- 
teen chlorinated pesticide compounds were reported in 
69 residues; 43 were found at the trace level. Of these, 
the most frequently occurring residues were dieldrin and 
p,/?'-DDE, found mostly in the dairy composites and 



the meat composites. Endosulfan, found in one ■ 
table composite at 0.037 ppm, was the chlorii 
pesticide occurring at the highest level. 

Malathion, an organophosphorus pesticide, was f 
in each of the 10 grain and cereal composites, w 
high value of 0.049 ppm. In addition to 0.010 
diazinon found in one composite, single trace ami 
of three other organophosphorus pesticides wen 
ported: parathion, ethion, and fonofos. A single 
of carbaryl, the only carbamate pesticide screened 
found once in the fruit-fruit juice composite. 

Only two herbicides were found in the composites, 
chlorinated herbicide CIPC, which is usually foui 
potatoes, was reported for three potato compc 
ranging from 0.023 to 0.469 ppm, and trace amoui 
PCP were found in four composites. The funj 
TCNB was reported in one potato composite at i 
ppm. 

TODDLER 

A total of 473 residues was found in the toddler 
composites. Of these, the six metals accounted foi 
residues, or 54.3 percent of the total, the 17 chlori 
pesticides accounted for 164, or 34.6 percent, ani 
six organophosphorus pesticides were reportec 
times for 5.4 percent of the total. The remainin; 
percent included four chlorinated herbicides four 
times, three chlorinated fungicides found eight t 
one industrial chemical found four times, an, 
phenylphenol found once. 

Zinc, ranging from 0.100 to 34.0 ppm, was foun 
almost every composite. Cadmium was the second 
frequently occurring residue, but the range, 0.0( 
0.120 ppm, was much lower. Most of the lead 
dues, with a range of 0.050 to 0.350 ppm, were 1 
in the grain, potato, vegetable, and fruit compel 
All 10 grain composites and nine meat compj 
contained selenium residues. The meat-fish-pc( 
composites contained seven of the 11 arsenic res) 
and six of the seven mercury residues, which have^ 
traced to the seafood portion of the composite. | 

Seventeen chlorinated pesticides accounted for 
or 34.6 percent, of all the residues; these were If 
predominantly in the dairy and meat-fish-poultry f 
posites. The most frequently detected chlorinated 
cide was dieldrin, found in every dairy and mealji 
poultry composite. a-BHC and DDE were also i) 
several times in those two composites. 

The most prevalent organophosphorus pesticidei 
malathion, found in all 10 grain-cereal composite^ 
in six oil-fat composites. Other reportable organol 
phorus pesticides were diazinon, parathion, foil 
and ronnel, each residue found in either the \\ 
cereal or the oil-fat composites. The herbicides 



48 



Pesticides Monitorxno Joofc 



icides represented a small number of residues. 

■ four chlorinated herbicides were reported: CIPC 
ues, found in five potato composites, ranged from 
3 to 0.469 ppm; PCP, 2,4-D, and PC? methyl 

■ were scattered throughout the other food groups. 
t of the eight residues of the three chlorinated 
icides detected were found in the fat-oil composite. 

ichlorobenzene, an industrial chemical, was present 
e toddler diet but was not found in the infant diet; 
is detected in four oil-fat composites and ranged 
0.001 to 0.009 ppm. The fruit-fruit juice com- 
es contained one residue of the fungicide o- 
ylphenol at the trace level. 

; 7 shows the number of occurrences of each 
ue type as found in each food class. 

very studies were done for many of the more 
non residues. In each case, simultaneous determi- 
ns were made on an unfortified composite and on 
mposite fortified with a known level of residue. 
5 8 lists the contributions from the unfortified com- 
3, and the total amount of residue recovered 
igh the method. A single determination was made 
ach reported recovery. In some cases only a few 
losites were fortified with a particular compound; 

are presented for information only. In other cases, 
tempt was made to investigate the recovery of the 

frequently found residues from a variety of prod- 
natrices and to provide a basis for a meaningful 
ation of the methods. The data are presented in 
:8. 

A ckttowledgments 

ors acknowledge the contributions of all staff 

bers assigned to the Total Diet Section, Food and 

Administration, Kansas City District Laboratory. 

,E 7. Types and number of residues, by food class, 
>und in infant and toddler total diet samples from 10 
United States cities — August 1975-July 1976 

Food Class ^ 

F 

E I II III IV V VI VII VIII IX X XI 

INFANT 



les 

ides 

ial chemicals 

ides 



23355343233 
— 45536457 — — 



1 — 



1 



1 



TODDLER 



les 

ides 

ial cliemicals 

ides 



23565333553 

— 48 11 2552 11 2 — 

— — — — — 2— 1 2 — — 



TABLE 8. Recovery data on residues found in infant and 

toddler total diet samples from 10 United Slates cities — 

August 1975-July 1976 



1 1 



1 — 



1 



1 



2 — 



By in Table 1. 









Range OF 


Range of 










Unforti- 


Total 


Number 




Type of 


Spike 


fied 


Residue 


of 




Food 


Level, 


Composite, 


Found, Recovery 


Residue 


Composite 


PPM 


PPM > 


PPM >■- 


Studies 


NONMETALS 


Oxychlordant 


; Fatty 


0.003 




0.0027-0.0039 


2 




Nonfatty 


0.003 




0.0026 


1 


Heptachlor 


Fatty 


0.003 




0.0027-0.0031 


2 


epoxide 


Nonfatty 


0.003 




0.0027 


1 


Ethion 


Fatty 


0.010 




-trace 


2 




Nonfatty 


0.010 




0.010 


1 


DCPA 


Fatly 


0.005 


0-0.001 


0.0045-0.007 


4 




Nonfatty 


0.005 




0.00043-0.0064 
(0.0043) 


8 


Methyl 


Fatty 


0.005 




0.0011-0.003 


2 


parathion 


Nonfatty 


0.005 




0.0014-0.0053 


4 


Perthane 


Fatty 


0.010 




0.005-0.0094 


3 




Nonfatty 


0.010 




0.0009-O.0131 
(0.0087) 


8 


Tetradifon 


Fatty 


0.100 




0.065-0.090 


2 




Fatty 


0.020 




0.019 


1 




Nonfatty 


0.100 




0.048-0.109 


4 




Nonfatty 


0.020 




0.016-0.024 


2 


Endosulfan 


Fatty 


0.010 




0.006-0.008 


2 


sulfate 


Nonfatty 


0.010 




0.004-0.013 


4 


Malathion 


Fatty 


0.005 




0.0025-0.0049 


2 




Nonfatty 


0.005 




0.0043-0.0056 


3 


Phosalone 


Fatly 


0.02 




0.018 


1 




Nonfatty 


0.02 




0.009-0.015 


2 


Leptofos 


Fatty 


0.05 




0.039-0.049 


2 




Nonfatty 


0.05 




0.004-0.046 


4 


PCP 


Fatty 


0.02 


0-0.010 


0.0007-0.018 


4 




Falty 


0.04 




0.020-0.024 


3 




Nonfatty 


0.02 


0-0.003 
(0.0012) 


0.003-0.016 
(0.0096) 


6 




Nonfatty 


0.04 


0-0.004 


0.02S-O.032 


3 


Picloram 


Falty 


0.10 




0-0.075 


2 




Nonfatty 


0.10 




0.033 


1 


2,4-D 


Fatty 


0.04 




0-0.042 


3 




Nonfatty 


0.04 




0.026-0.039 


5 


Silvex 


Fatty 


0.04 




0.008-0.022 


2 




Nonfatty 


0.04 




0.023-0.039 


2 


MCP 


Fatty 


0.020 




0.009-0.011 


2 


2-methyI- 


Nonfatty 


0.020 




0.009-0.013 


3 


4-chloro- 


Nonfatty 


0.040 




0.029-0.036 


2 


phenoxy- 












acetic acid 












2,4-DB 


Fatty 


0.02 




0.014 


1 




Nonfatty 


0.02 




0.012-0.017 


2 




Nonfatty 


0.04 




0-O.026 


2 


2,4,5-T 


Falty 


0.02 


0-0.002 


0.004-0.022 


2 




Falty 


0.04 




0.016 


1 




Nonfatty 


0.02 




0.007-0.0196 


4 




Nonfatty 


0.04 




0.025-0.029 


2 


Carbaryl 


Nonfatty 


0.20 




0.02-0.20 
(0.18) 


17 


o-Phenyl- 


Nonfatty 


0.40 




0.08-0.40 


16 


phenol 








(0.30) 




Fonofos 


Fatty 


0.01 




0.002-0.004 


2 




Nonfatty 


0.01 




0.006-0.008 
(0.007) 


5 


Toxaphene 


Falty 


0.20 




0.201-0.240 


2 




Nonfatty 


0.20 




O.125-O.204 
(0.170) 


4 


METALS 


Arsenic 


Fatly 


0.30 




0.25-0.30 


3 




Fatty 


0.40 


0-0.10 


0.34-0.535 
(0.462) 


5 




Nonfatty 


0.30 




0.17-0.32 


3 




Nonfatty 


0.40 


0-0.03 


0.24-0.385 
(0.313) 


12 


Cadmium 


Falty 


0.10 


0.002-O.086 
(0.030) 


0.095-0.162 
(0.116) 


11 




Nonfatty 


0.10 


0-0.371 
(0.0195) 


0.090-0.162 
(0.116) 


19 


Lead 


Fatty 


0.20 


0-0.119 
(0.039) 


0.099-0.260 
(0.187) 


11 




Nonfatty 


0.20 


0-0.072 
(0.031) 


0.084-0.345 
(0.196) 


19 



15, No. 1, June 1981 



49 



TABLE 8 (cont'd.). Recovery data on residues found in 

infant and toddler total diet samples from 10 Unted States 

cities — August 1975-July 1976 









Range of 


Range of 










Unforti- 


Total 


Number 




Type of 


Spike 


fied 


Residue 


of 




Food 


Level, 


Composite, 


Found, 


Recovery 


Residue 


Composite 


PPM 


PPM 1 


PPM ■■ = 


Studies 


Mercury 


Fatty 


0.06 


0-0.019 
(0.005) 


0.047-0.089 
(0.069) 


7 




Nontatty 


0.04 


0-0.003 
(0.001) 


0.045-0.056 
(0.052) 


4 




Nonfatty 


0.06 


0-0.002 
(0.0002) 


0.065-0.136 
(0.079) 


13 


Selenium 


Fatty 


0.20 


0-0.20 
(0.07) 


0.19-0.45 
(0.30) 


6 




Fatty 


0.40 


0-0.20 
(0.03) 


0.26-O.50 
(0.39) 


5 




Nonfatty 


0.20 


0-0.29 
(0.04) 


0. 18-0. 56 
(0.25) 


11 




Nonfatty 


0.40 


0-0.15 
(0.034) 


0.25-0.54 
(0.36) 


6 


Zinc 


Fatty 


5.0 


1.62-19.2 
(7.33) 


5.95-24.0 
(12.2) 


6 




Fatty 


25.0 


5.0-30.2 
(17.9) 


28.5-52.6 
(41.7) 


5 




Nonfatty 


10.0 


6.3-7.4 
(7.0) 


14.8-18.2 
(16.8) 


3 




Nonfatty 


5.0 


0-7.55 
(2.67) 


4.55-12.6 
(7.37) 


14 



1 Numbers in parentheses represent average residue levels. 

2 Values are uncorrected for badtground. 



LITERATURE CITED 

(/) Corneliussen, P. E. 1969. Pesticide residues in total 
diet samples (IV). Pestic. Monit. I. 2(4) :140-152. 

(2) Corneliussen, P. E. 1970. Pesticide residues in total 
diet samples (V). Pestic. Monit. J. 4(3):89-105. 

(3) Corneliussen, P. E. 1972. Pesticide residues in total 
diet samples (VI). Pestic. Monit. I. 5(4) :313-330. 

(4) Duggan, R. £., H. C. Barry, and L. Y. Johnson. 1966. 
Pesticide residues in total diet samples. Science 151 
(3706):101-104. 

(5) Duggan. R. E.. H. C. Barry, and L. Y. Johnson. 1967. 
Pesticide residues in total diet samples (II). Pestic. 
Monit. J. 1(2):2-12. 

(6) Duggan, R. E., and F. J. McFarland. 1967. Assess- 



ments include raw food and feed commodities, m 
basket items prepared for consumption, meat sa: 
taken at slaughter. Pestic. Monit. I. 1(1): 1-5. 

(7) Finocchiaro, J. M., and W. R. Benson. 1965. 
layer chromatographic determination of cai 
(Sevin) in some foods. J. Assoc. Off. Agric. ( 
48(4):736-738. 

(8) Food and Drug Administration. 1971. Pesticide 
lytical Manual, Vols. I and 11. U.S. Departme 
Health and Human Services, Washington, D.C. 

(9) Food and Drug Administration. 1976. Comp! 
Program Guidance Manual. 7305.002, Part IV, 
a, 2(a). 

(10) Himdley, H. K., and J. C. Underwood. 1970. Del 
nation of total arsenic in total diet samples. J. i 
Off. Anal. Chem. 53(6) : 1 176-1 178. 

(//) Johnson, R. D.. and D. D. Manske. 1975. Pes 
residues in total diet samples (IX). Pestic. Moi 
9(4): 157-169. 

(12) Johnson, R. D., and D. D. Manske. 1977. Pes 
and other chemical residues in total diet samples 
Pestic. Monit. J. 1 1(3) :1 16-131. 

(13) Johnson, R. D., D. D. Manske, D. H. New, and 
Podrebarac. 1979. Pesticide and other chemical re 
in infant and toddler total diet samples — (I) — A 
1974-July 1975. Pestic. Monit. J. 13(3):87-98. 

{14) Manske, D. D., and P. E. Corneliussen. 1974. Pes 
residues in total diet samples (VII). Pestic. Mo 
8(2):110-124. 

(15) Manske, D. D., and R. D. Johnson. 1975. Pes 
residues in total diet samples (VIII). Pestic. Mo 
9(2):94-105. 

(16) Manske, D. D.. and R. D. Johnson. 1977. Pesticic 
other chemical residues in total diet samples 
Pestic. Monit. J. 10(4) : 134-148. 

(17) Martin, R. J., and R. E. Duggan. 1968. Pesticid( 
dues in total diet samples (III). Pestic. Moi 
l(4):ll-20. 

(18) Official Methods of Analysis. 1975. AOAC, Arli: 
VA, 1 2th ed., sections 25.026-25.030, 25.065-2 
25.103-25.105, 25.117-25.120, 25.143-25.147. 

(19) Porter, M. L.. R. J. Gajan, and J. A. Burke. 
Acetonitrile extraction and determination of ca| 
in fruits and vegetables. J. Assoc. Off. Anal. < 
52(1):177-181. 



50 



Pesticides Monitoring Joup 



Organochlorine Pesticides and PCBs in Cod-Liver Oil 
of Baltic Origin, 1971-80 

Jerzy Falandysz ' 



ABSTRACT 

mocMorine pesticides and polychlorinated biphenyls 
Bs) in cod-liver oil of Bailie origin were monitored diir- 
1971-80. Residues of DDT and its metabolites. PCBs. 
he.xachlorobenzene were present in all samples. Gen- 
y, ZDDT residues declined, but the reason for the 
ne is unknown. 

Introduction 
of technical DDT as an insecticide in countries sur- 
iding the Baltic has been prohibited since 1971. The 
nochlorine pesticides presently used for agricultural 
OSes in Poland are toxaphene, methoxychlor. endo- 
in, and lindane. DDT was widely used in agriculture 
has been detected at high levels in tissues of Baltic 
ne mammals, fish, and birds (7). The prohibition 
[le agricultural use of DDT in Poland was reflected 
le nearly tenfold reduction of 2DDT residue levels 
dipose fat of slaughtered animals during the last 
de (A. Niewiadowska. Veterinary Institute, Pulawy, 
), personal communication). However, so far there 

been no reports showing a decline of 2DDT residue 
s in animals of the Baltic Sea. Another class of or- 
chlorine compounds, polychlorinated biphenyls 
Bs), occurs throughout the Baltic environment. 
, polychlorinated terphenyls (PCTs) have been 
d recently in Baltic marine organisms (2, 13, 15). 
rmation on production and industrial use of PCBs 
PCTS in countries surrounding the Baltic remains 
ure. Some quantities of PCBs are produced and 
able in Poland under the trade name Chlorofen 

12). PCBs have also been produced in West 
nany as Clophen, in the Soviet Union as Sovol, 
in Czechoslovakia as Delor. This paper presents the 
ts of analyses of cod-liver oil of Baltic origin for 
ues of hexachlorobenzene (HCB), 2DDT, and 



Analytical Methods 

3les of cod-liver oil were obtained from a factory 
dynia. The procedures for isolation and determina- 

rinary Hygiene Research Station, ul. Kaprow 10, PL 80-316 
:k, Poland 



tion of the organochlorines have been presented else- 
where (4). Two cleanup processes were used. The oil 
sample was dissolved in «-hexane; 1 ml n-hexane was 
used for every 20 mg fat extracted. Twenty mg fat 
was cleaned with 1 ml of a 1 : 1 mixture of fuming 20-25 
percent sulfur dioxide and concentrated sulfuric acid in 
a screw-capped, Teflon-lined test tube (2, 4, 8). The 
colorless hexane layer was injected directly into the 
gas chromatograph. In addition, a 4-ml aliquot of 
cleaned sample was subjected to alcoholic potassium 
hydroxide hydrolysis in a screw-capped. Teflon-lined 
test tube. The test tube was immersed for 15 minutes in 
the water bath at 50 °C. After cooling, the mixture was 
shaken with 4 ml distilled water. Following separation, 
the upper hexane layer was injected into the gas chro- 
matograph. The residues were quantitated by electron- 
capture gas chromatography. Instrument parameters and 
operating conditions follow: 

Chromatograph: PYE 104 

Detector: o^Ni 

Column: glass, 150 cm long by 4 mm ID packed with a 

2:1 mixture of 8 percent QF-1 and 4 percent 
SF-96 on 100-120 mesh Gas-Chrom Q 

Temperatures. °C: detector 210 

column oven 195 

Carrier gas: argon flowing at ml/min 

PCBs were quantified by comparing sample peaks with 
that of PCB standard Clophen A 50, which appeared 
on the gas chromatogram after p,p'-DDE. DDE content 
was calculated from the total height of the peak with 
retention time equal to that of standard p,p'-DDE. p,p'- 
DDT and p,p'-TDE were calculated from the difference 
in height of peaks with retention times equal to those 
of p,p'-DDT and p.p'-TDE before and after hydrolysis 
with alcoholic potassium hydroxide. In recovery experi- 
ments, the calculated values and standard deviations, in 
ppm, were as follows: HCB, 0.27 ± 0.015; DDE, 5.8 
± 0.25; TDE, 5.1 ± 0.39; DDT, 1.3 ± 0.14; and 
PCBs, 11 ± 0.84 (4). 

Results and Discussion 

The levels of organochlorine residues in cod-liver oil are 
presented in Table 1. DDT and its metabolites were 
present in all samples. DDE levels ranged from 1.1 to 



15, No. 1, June 1981 



51 



TABLE 1. Mean and range ippm) oj chlorinaled hydrocarbons in cod-liver oil of Baltic origin, 1 97 1 -SO 





n 


HCB 


P.P' 


-DDE 


P.P 


-TDE 


P,P' 


-DDT 


SDDT 


PCBs 


Year 


Mean 


Range 


Mean 


Range 


Mean 


Range 


Mean 


Range 


Mean 


Range 


Mean 


Range 


1971 




0.24 




4.6 




2.3 




6.6 




13 




4.8 




1972 




0.36 




4.2 




4.6 




8.4 




17 




9.5 




1973 




0.28 


0.20-0.32 


7.2 


4.1-9.3 


3.7 


2.2-4.5 


10 


8.4-12 


22 


15-26 


5.7 


4.3-7.0 


1974 




0.23 


0.10-0.37 


5.5 


1.3-9.8 


2.9 


0.69^.8 


5.7 


2.1-9.4 


14 


4.0-22 


5.9 


2.2-9.0 


1975 




0.23 


0.12-0.34 


8.3 


2.9-17 


3.5 


1.4-5.4 


5.0 


2.2-8.5 


17 


8.9-28 


8.6 


4.6-13 


1976 


11 


0.30 


0.16-0.44 


8.3 


1.1-24 


3.5 


1.0-6.5 


4.6 


1.1-8.9 


16 


3.3-38 


8.6 


3.1-16 


1977 




0.35 


0.26-0.54 


5.3 


3.1-9.3 


3.9 


3.0-5.0 


3.9 


3.2-5.9 


13 


9.8-20 


9.6 


4.9-16 


1978 




0.32 


0.28-0.41 


4.1 


4.1-4.2 


2.9 


2.7-3.1 


2 2 


1.3-3.0 


9.2 


8.2-9.8 


7.1 


5.5-8.5 


1979 




0.24 




4.2 




5.2 




2.1 




11 




4.3 




1980 




0.29 


0.28-0.30 


3,4 


3.0-3.8 


1.9 


1.3-2.5 


1.2 


0.59-1.8 


6.5 


4.9-8.1 


5.1 


4.7-5.6 



NOTE: Mean is arithmetic mean. 



24 ppm, TDE from 0.69 to 6.5 ppm, and DDT from 
0.59 to 12 ppm; 2DDT levels ranged from 3.3 to 38 
ppm. PCBs. resembling Clophen A 50, and HCB were 
also detected in all samples, at levels ranging from 
2.2 to 16 ppm and from 0.10 to 0.54 ppm, respectively. 
All samples contained at least trace amounts of a- and 
y-BHC. Because the residues of these isomers were 
negligible by comparison, they were excluded from the 
table. 



It should be pointed out that much higher leveli 
organochlorines than those noted in Table 1 have 
found in the livers of some specimens of cod frorr 
Baltic. For example, the livers of cod taken from 
Kattegat in 1973 contained PCBs ranging from 4 t 
ppm and averaging 13 ppm wet weight; livers of 
taken from the Rivo Fiord in 1975 contained I 
ranging from 29 to 57 ppm and averaging 38 ppm 
weight {13. 14). 



Many papers have been published on organochlorine 
residues in the liver of cod from the Baltic (/, 5. 6, 8, 
10, 11, 13, 14, 16-18), but only several for cod-liver 
oil (7, 3, 10). The cod-liver oil of Baltic origin is unfit 
for medical purposes because of its high contamination 
with DDT and PCBs. The main Polish catches of cod are 
taken in the southern Baltic (Figure 1, regions 25 and 
26) (9). The cod-liver oil produced in the factory in 
Gdynia, Poland, is manufactured from fresh cod livers. 
The crude cod-liver oil produced on board the fishing 
vessels operating in the southern Baltic is also delivered 
to the factory in Gdynia. After clarification, the crude 
cod-liver oil is usually mixed with that produced from 
the previous catch and is stored in a large-capacity 
tank. For the present study, all samples were taken 
from oil dispatched from the factory. Those particular 
lots of oil were taken from the day-by-day production 
or from the storage tank, mainly mixed oil. The annual 
production of cod-liver oil in 1975. 1976. and 1977 was 
280, 316, and 220 tons, respectively. Table 1 shows that 
2DDT may have declined, but that decline cannot be 
verified because the mean values for organochlorines 
must be at least corrected by the quantity of oil in the 
particular lot analyzed — information that was not avail- 
able to authors. Also, it has been shown (11, 16, 17) 
that the organochlorine residues in livers of cod from 
the western Baltic can be correlated to the length of the 
fish. The lengths of the cod from which livers were 
obtained for processing in the present study were not 
uniform. Cod caught in the southern Baltic generally 
range from 25 to 120 cm long. In 1970, the cod were 
predominantly 39 to 44 cm long, and in 1971, 45 to 50 
cm long (9). 



The following extreme ranges for 2DDT have I 
been noted: Levels in cod taken from the souti 
Baltic in 1970-71 ranged from 14 to 57 ppra« 
averaged 26 ppm wet weight and 66 ppm lipid W( 
(6); levels in cod taken from the Sund during 
ranged from 1.4 to 53 ppm and averaged 8.7 ppm 
weight and 29 ppm lipid weight (13). 




FIGURE 1. Baltic Sea, with division of the sampling f 
according to International Council for the Exploration < t 
Sea 



52 



Pesticides Monitoring Jout 



LITERATURE CITED 

Falaiidysz, J. 1977. Residues of organochlorine pesti- 
ticides, polychlorinated biphenyls and he.xachloro- 
benzene in some cod-liver oils available at Polish 
market in years 1971-1976 (In Polish). Farm. Pol. 
33(6): 35 1-356. 

Falandysz. J. 1980. Chlorinated hydrocarbons in gulls 
from the Baltic south coast. Mar. Pollut. Bull. 11(3); 
75-80. 

Falandysz. J., and E. Kcdehka. 1979. Residues of hexa- 
chlorobenzene, chlorinated diphenylethylenes, and 
polychlorinated biphenyls in cod-liver oils in the years 
1976-1978 (In Polish). Farm. Pol. 35(6) :337-341. 
Falandysz, J., and I. Stangret. 1979. Use of concen- 
trated sulphuric acid and alcoholic potassium hydroxide 
for analysis of residues of organochlorine pesticides, 
polychlorinated bi- and terphenyls in fish oils and 
cod-liver oils (In Polish). Farm. Pol. 35( 8) :465-472. 
Falandysz, J., B. Michalska, J. Trojanowska, and S. 
Wodecka. 1980. Residues of chlorinated hydrocarbons 
in Baltic cod liver and in canned cod-liver products 
(In Polish). Rocz. Panstw. Zakl. Hig. 31 (2) : 163-168. 
Huscbenheth, E. 197 S. The contamination of fish with 
chlorinated hydrocarbons (In German). Arch. Fisch 
Wiss. 24(1-3): 105-1 16. 

Jensen, S., A. G. Johnels. M. Olssoii. and G. Otter- 
lind. 1969. DDT and PCB in marine animals from 
Swedish waters. Nature (London) 224(5216) :247- 
250. 

Jensen. S., A. G. Johnels, M. Olsson, and G. Otterlind. 
1972. DDT and PCB in herring and cod from the 
Baltic, the Kattegat and the Skagerrak. Ambio. Spec. 
Rep. 72(l):71-85. 

Kosior, M. 1976. Cod of the Southern Baltic in the 
years 1969-1972 (In Polish). Pr. Mor. Inst. Ryb. 18 
(Ser. A): 183-214. 



{10) Lipka, E., M. Zarecz, E. Grochowska, and B. Dobo- 
szynska. 1978. Studies on DDT appearance in Baltic 
Sea fish. Part II. Determination of DDT and its 
metabolites in cod liver and cod liver products (In 
Polish). Bromatol. Chem. Toksykol. 1 1(2) : 171-175. 

(//) Luckas. B.. M. Berner, and P. Herbert. 1978. The 
contamination of cod livers from Baltic Sea cod catches 
with chlorinated hydrocarbons in 1976/77 (In Ger- 
man). Fischereiforschung 16(2):77-81. 

(12) Liizak, J., M. Rybak, and D. Zycinski. 1976. Effect of 
Chlorofen on aqueous organisms and chemical char- 
acteristics of changes in aqueous medium caused by 
this substance (In Polish). Rocz. Panstw. Zakl. Hig. 
27(5):555-561. 

(/J) Noren, K., and K. Rosen. 1976. Levels of organo- 
chlorine pesticides and PCB in fish from Swedish 
waters (In Swedish). Var Foeda 28(Suppl. l):2-55. 

(14) Ohiin, B., and R. Vaz. 1978. Methylmercury and PCB 
levels in fish and mussels caught off the west coast of 
Sweden in connection with dredging operations (In 
Swedish). Var Foeda 30(Suppl. l):3-23. 

(15) Renberg, L., G. Sundstrom, and L. Rcutergardh. 1978. 
Polychlorinated terphenyls (PCT) in Swedish white- 
tailed eagles and in grey seals: a preliminary study. 
Chemosphere 7(6) :477-482. 

(16) Schneider, R.. and C. Osterroht. 1976. On the chlori- 
nated hydrocarbon levels in cod livers from the Kiel 
Bight (Western Baltic). International Council for the 
Exploration of the Sea. CM. E:31. 

(17) Schneider, R., and C. Osterroht. 1976/77. Residues of 
chlorinated hydrocarbons in cod livers from the Kiel 
Bight in relation to some biological parameters. 
Meeresforschung 25 ( 3-4) : 105-1 14. 

(18) Westoo, G., and K. Noren. 1970. Levels of organo- 
chlorine pesticides and polychlorinated biphenyls in 
fish caught in Swedish waters or kept for sale in 
Sweden, 1967-1970 (In Swedish). Var Foeda. 22(9- 
10):93-146. 



15, No. 1, June 1981 



53 



Pesticide, Metal, and Other Chemical Residues in Adult Total Diet 
Samples~(XII)— August 1975-July 1976 ' 

Roger D, Johnson, Dennis D. Manske, and David S. Podrebarac 



ABSTRACT 

This report is the twelfth in the series on the presence of 
pesticide and other chemical residues in the average diet of 
the United States' heartiest eater, the young adult male. 
Twenty market baskets were collected in 20 U.S. cities that 
ranged in population from < 50,000 to 1 million or more. 
Composites of 12 food classes were analyzed. Averages and 
ranges of residues found are reported for August 1975 
through July 1976. by food class. In addition to the pesticide 
and chemical residues, data for lead, cadmium, selenium, 
mercury, arsenic, and zinc are included. The individual items 
making up the dairy and meat composites in four market 
baskets were analyzed separately for pesticide residues, and 
the results are included. Results of recovery studies of pesti- 
cides and chemicals within various food classes are also 
presented. 

Introduction 

In 1964, the Food and Drug Administration (FDA), 
U.S. Department of Health and Human Services (for- 
merly U.S. Department of Health. Education, and 
Welfare), initiated a Total Diet Program (7), sometimes 
called the Market Basket study. Its purpose was to 
monitor the atmosphere for fission products from at- 
mospheric tests of thermonuclear weapons in May 1961. 
Later, the program was e.xpanded to include pesticide 
residues and certain nutrients. 

At its inception, the program was primarily concerned 
with the adult diet, which was defined as a market 
basket of food representing the basic two-week diet of a 
16-to- 19-year-old male, statistically the United States' 
heartiest eater. Beginning in August 1974. 10 of the 30 
market baskets collected per year were changed to repre- 
sent the basic two-week diet of infants (6-month-old) 
and toddlers (2-year-old) {13). 

The market baskets were collected in four different geo- 
graphic areas, wi'h the specific diet of the particular 
region determining the composition of the market bas- 
ket. Foods were prepared for normal home consump- 
tion, and every food item was then placed into one of 



the 12 composite classes listed in Table 1. For e 
food class. 20 composites, one from each market baf 
were prepared. Each composite, containing foods 
similar characteristics, was analyzed for certain me 
residues of organochlorine, organophosphorus, 
carbamate pesticides, herbicides, and industrial ch 
cals. Methodologies included atomic absorption spec 
copy, fluorometry. polarography, gas chromatogra 
thin-layer chromatography, mass spectroscopy, andei 
lished extraction and cleanup techniques (8-10, 18, 
Amounts and types of residues found from June 1 
through July 1975 have been tabulated in earliei 
ports (/-5, 11-17). This report covers the results 
tained from August 1975 through July 1976 for i 
market baskets collected in 20 different cities. Re 
for the 10 infant and toddler market baskets colle 
during the same period are presented in a sep; 
report. 

Results 

During this reporting period, 1,039 residues of 471 
ferent compounds were found in the 240 compc 
examined. In the previous reporting period, 959 resij 
of 42 diff'erent compounds were found in the same ii 
ber of composites. The 47 compounds are listed ii| 



^ Food and Drug Administration, Kansas City District Office Labora- 
tory. 1009 Cherry St.. Kansas City, MO 64106 



54 



creasi 


ng order of 


frequency in Table 2. Table 3 si 


the frequency of 


occurrence of each compound by 


class. 


and 


Table 


4 shows the levels of every rei 


found 


with 


in each food class. The average value in 1 


TABLE 1. 


Classes of adult food composites analyzet 


pestici 


des. 


metals. 


and other chemical residues, A I 
1975-July 1976 


Key 






Food Class 


I 






Dairy products 


n 






Meat, fish, and poultry 


III 






Grain and cereal products 


IV 






Potatoes 


V 






Leafy vegetables 


VI 






Legume vegetables 


VII 






Root vegetables 


VIII 






Garden fruits 


IX 






Fruits 


X 






Oils. fats, and shortening 


XI 






Sugar and adjuncts 


XII 






Beverages (including drinking water) 








Pesticides Monitoring Jow[i 



iLE 2. Chemical and metal residues found in adult 
! composites from 20 United States cities — August 1975- 
July J 976 



TABLE 3. Frequency of occurrence, by food class, of 

pesticides, metals, and other chemical residues in adult food 

composites from 20 United States cities — August 1975- 





No. OF 


No. of Positive 
Composites with 














"^ ' 


-r 1 \j 
















IICIL 














Po'^" f, . r 












JND C 


Composites 
rH Residues 


Residues Reported 
AS Trace • 


Range, 

PPM 


Chemical 












rn 




\_l,rt33 - 










Wl 


I 


II 


III 


IV 


V 


VI 


VII VIII IX 


X 


XI 


XII 




239 
170 





0.100 -76.0 






N 


umber of Occurrences 








lium 





0.010 - 0.100 
































85 





0.040 - 0.820 


Zinc 




20 


20 


20 


20 


20 


20 


20 


20 


20 


20 


20 


19 


rin 


60 


16 


0.001 - 0.086 


Cadmium 




3 


17 


20 


20 


19 


14 


19 


18 


5 


18 


14 


3 


ium 


57 





0.010 - 0.340 


Lead 







5 


12 


5 


2 


17 


8 


14 


11 


6 


3 


2 


3DE2 


52 


16 


0.001 - 0.048 


Dieldrin 




15 


19 


1 


4 


2 





1 


13 


2 










C 


46 


31 


0.0003- 0.007 


Selenium 




4 


20 


20 


3 


1 


5 


2 
















lie 


31 





0.030 - 0.460 


P.p'-DDE 




14 


20 





3 


8 


1 


3 


2 













ichlor epoxide 


30 


19 


0.001 - 0.003 


a-BHC 




17 


19 

















3 


1 




5 





Ihion 


29 


3 


0.004 - 0.096 


Arsenic 




1 


17 


8 








1 


1 


1 










1 


Liry 


24 





0.006 - 0.080 


Heptachlor 


epoxide 


13 


15 





2 

























ine 


24 


11 


0.0006- 0.004 


Malathion 










19 






















3 







19 


12 


0.0002- 0.0060 


Mercury 







18 


1 

















1 




1 


2 


tilor epoxide 


17 


15 


0.0020 


Lindane 




2 


7 


1 





1 








5 







7 





)DT 


16 


9 


0.0030- 0.010 


HCB 




5 


11 























3 








iulfan sulfate 


13 


5 


0.003 - 0.030 


Octachlor e 


poxide 


5 


12 
































sulfan 1 


12 


1 


0.0010- 0.0110 


P.p'-DDT 







15 








1 























sulfan 11 


11 


5 


0.002 - 0.0120 


Endosulfan 


sulfate 











2 


6 








3 


2 











oran 


10 


1 


0.002 - 0.163 


Endosulfan 


I 














5 








6 


1 











non 


10 


2 


0.001 - 0.004 


Endosulfan 


II 














5 








4 


2 











3 


8 





0.002 - 0.114 


Dichloran 
















4 


1 








4 





1 





DE 


7 


6 


0.004 


Diazinon 










5 





2 








2 


1 











n 


6 


2 


0.005 - 0.050 


TCNB 










1 


6 











1 














hion 


5 





0.002 - 0.006 


P.p'-TDE 







7 


































5 





0.010 - 0.229 


Ethion 







1 














1 


1 


3 











lal® 


5 


1 


0.002 - 0.014 


Parathion 
















1 


2 


1 


1 














i 


5 


2 


0.002 - 0.003 


CI PC 













5 


























iryl 


5 


4 


0.050 


DCPA 
















3 





2 

















ol 


4 





0.007 - 0.028 


PCNB 































5 








choloroaniline 


4 


1 


0.007 - 0.018 


Carbaryl 

























2 


3 











ane 


3 





0.014 - 0.044 


Dicofol 




























4 











jxychlor 


3 


2 


0.013 


Pentachloroaniline 





























4 










3 


3 


T 


Perthane 
















2 











1 











n 


2 





0.026 - 0.040 


Methoxychlor 


3 





































2 





0.026 - 0.060 


PCS 




1 


2 
































chlorobenzene 


2 





0.004 - 0.005 


Captan 




























2 













2 





0.002 - 0.005 


PCP 


































1 


1 


:1 


2 





0.002 - 0.006 


Pentachloro 


benzene 





























2 








phos 


2 


1 


0.009 


PCTA 































2 








dane 


2 


2 


T 


Ronnel 







1 


1 





























2 







0.008 


Leptophos 

























2 














4ethyl ether 







0.002 


Chlordane 










1 


1 


























Nonachlor 







0.002 


P-BHC 
















1 























iphenothion 







0.195 


PCP Methyl ether 





























1 








lone 







0.008 


rra/is-Nonachlor 





1 
































nylphenol 




1 


T 


Carbopheno 


thion 























1 














ihene 




1 


T 


Phosalone 




























1 



















o-Phenylphenol 
































1 













Toxaphene 
















1 























nicals capable 


of being detected by the specific 


analytical meth- 































gy may be confirmed qualitatively but are not quantifiable when 
are present at concentrations below the limit of quantitation, 
of quantitation varies with residue and food class. 



' See Table 1 for key to food classes. 



based on the 20 composites examined; trace resi- 
, if present, were treated as zero in calculating the 
ages. For this reason, an average value reported as 
can be well below the detection limits of the 
lods for that compound. 

;an et al. reported the human dietary intake of 
:ides and industrial chemicals detected in mg/kg 
weight/ day, for the period July 1969 through 
1976 (6). Comparative values for fiscal years 
-75 are also given (6). Because Duggan et al. do 
eport dietary intakes for metals determined in the 
I Diet studies, they are shown here in Table 5 for 
'6. The daily intakes in /xg/day (mg/day for zinc) 



are listed in Table 5 by food group, together with the 
percentage of the total daily intake contributed by each. 

The most common residues and their maximum levels 
for each of the 12 food classes are discussed below. No 
findings have been corrected for recovery. 

DAIRY PRODUCTS 

Metal residues were found most frequently and at the 
highest levels in dairy products. Averages were 4.92 ppm 
zinc, 0.004 ppm selenium, 0.004 ppm arsenic, and 0.002 
ppm cadmium. Of the organochlorine residues, p,p'- 
DDE levels, ranging from 0.001 to 0.010 ppm and aver- 
aging 0.002 ppm for the series, were the highest. Other 



15, No. 1, June 1981 



55 



TABLE 4. Levels of chemical and metal residues, by food class, in adult food composites from 20 United States ci 

August 1975~July 1976 



Chemical 



Residues, ppm Chemical 



I. DAIRY PRODUCTS 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

P,P'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

HEPTACHLOR EPOXIDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

SELENIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

OCTACHLOR EPOXIDE 

Average 

Positive composites 



4.92 

20 



3.50-5.90 



0.002 

14 
6 

0.0010-0.0100 



15 

7 

0.001-0.003 



13 
10 
0.001 



0.004 

4 



0.02-0.03 



a-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

METHOXYCHLOR 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

HCB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LINDANE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ARSENIC 

Average 

Positive composites 



Total number 




5 




Total number J 


Number reported as trace 




S 




Number reported as trace ( 


Range 




T 




Range ( 


PCB 










Average 




T 






Positive composites 










Total number 




1 






Number reported as trace 




1 






Range 




T 








II. 


MEAT. 


FISH, 


AND POULTRY 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

MERCURY 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported a^ trace 

Range 

P,P'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 





SELENIUM 






32.2 


Average 

Positive composites 






20 


Total number 









Number reported 


as 


trace 


25.3-76.0 


Range 
LEAD 






0.02 


Average 

Positive composites 






18 


Total number 









Number reported 


as 


trace 


0.007-0.08 


Range 
ARSENIC 






0.01 


Average 

Positive composites 






17 


Total number 









Number reported 


as 


trace 


0.01-0.03 


Range 
p,p'-TDE 






0.010 


Average 

Positive composites 






20 


Total number 






1 


Number reported 


as 


trace 


0.002-0.048 


Range 







56 



Pesticides Monitoring Joi* 



,E 4. (cont'd.). 



Levels of chemical and metal residues, by food class, in adult food composites from 20 United Slates 
cities — August 1975-July 1976 



Residues, ppm 



Chemical 



Residues, ppm 



DT 

age 

ive composites 

tal number 

imber reported as trace 

inge 



age 

ive composites 

tal number 

imber reported as trace 

nge 

CHLOR EPOXIDE 

age 

ive composites 

tal number 

imber reported as trace 

nge 





DIELDRTN 


0.002 


Average 




Positive composites 


15 


Total number 


9 


Number reported as trace 


0.003-0.01 


Range 




HCB 


T 


Average 




Positive composites 


19 


Total number 


17 


Number reported as trace 


0.001 


Range 




HEPTACHLOR EPOXIDE 


T 


Average 




Positive composites 


12 


Total number 


10 


Number reported as trace 


0.002 


Range 



0.007 

19 

1 
0.001-0.086 



11 
8 

0.0002-0.002 



15 
9 

0.001-O.0O2 



EL 

age 

ive composites 

tal number 

imber reported as trace 

nge 



PCB 

T Average 

Positive composites 
1 Total number 

Number reported as trace 

0.006 Range 



2 
2 
T 



^NE 

age 

ive composites 

tal number 

mber reported as trace 

nge 



7 

3 

0.0006-0.003 



(rans-NONACHLOR 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



1 

0.002 



iN 

age 

ive composites 

tal number 

mber reported as trace 

nge 



1 
1 
T 



III. GRAIN AND CEREAL PRODUCTS 



ige 

ive composites 

lal number 

mber reported as trace 

nge 



SELENIUM 
9.0 Average 

Positive composites 
20 Total number 

Number reported as trace 

5,5-15.5 Range 



0.19 

20 


0.04-0.34 



Ige 

ive composites 

:al number 

mber reported as trace 

nge 



CADMIUM 
0.05 Average 

Positive composites 
12 Total number 

Number reported as trace 

0.04-0.14 Range 



0.03 

20 



0.02-0.05 



FHION 

Ige 

ive composites 

al number 

mber reported as trace 

Ige 



DIELDRIN 
0.02 Average 

Positive composites 
19 Total number 

Number reported as trace 

0.004-0.096 Range 



1 


0.003 



;dane 

ge 

ve composites 

al number 

Tiber reported as trace 

Ige 



1 
1 
T 



ARSENIC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



0.02 



0.0303-0.10 



JRY 

■ge 

ve composites 

al number 

nber reported as trace 

Ige 

15, No. 1, June 1981 



DIAZINON 
T Average 

Positive composites 
1 Total number 

Number reported as trace 

0.01 Range 



5 



0.001-0.004 

57 



TABLE 4. (cont'd.). 



Levels of chemical and metal residues, by food class, in adult food composites from 20 United S 
cities — August 1975-July 1976 



Chemical 



Residues, ppm 



Chemical 



Residues 



TCNB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

RONNEL 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 





LINDANE 


T 


Average 




Positive composites 


1 


Total number 





Number reported as trace 


0.002 


Range 



1 



0.002 



IV. POTATOES 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

TCNB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

HEPTACHLOR EPOXIDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ENDOSULFAN SULFATE 

Average 

Positive composites 



5.18 

20 

2.6-14.5 



0.007 



6 



0.002-0.114 



2 


0.001-O.002 



CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

SELENIUM 

Average 

Positive composites 





20 



0.02- 



C 

5 



0.06- 

1 

4 
0.001- 



Total number 


2 


Total number 






Number reported as trace 





Number reported 


as trace 


( 


Range 


0.003-0.012 


Range 




O.ISU 


CIPC 




CHLORDANE 






Average 


0.04 


Average 




1 


Positive composites 




Positive composites 






Total number 


5 


Total number 






Number reported as trace 





Number reported 


as trace 




Range 


0.01-O.23 


Range 




1 


p,p-DDE 










Average 


T 








Positive composites 










Total number 


3 








Number reported as trace 


2 








Range 


0.003 










V. LEAFY VEGETABLES 






ZINC 




CADMIUM 






Average 


2.67 


Average 






Positive composites 




Positive composites 






Total number 


20 


Total number 




1 


Number reported as trace 





Number reported 


as trace 




Range 


1.7-7.0 


Range 




0.02 


ENDOSULFAN I 




ENDOSULFAN II 




1 


Average 


O.OOI 


Average 






Positive composites 




Positive composites 






Total number 


5 


Total number 






Number reported as trace 





Number reported 


as trace 




Range 


0.001-0.011 


Range 




o.oow 


ENDOSULFAN SULFATE 




LINDANE 






Average 


0.004 


Average 






Positive composites 




Positive composites 






Total number 


6 


Total number 






Positive composites 


2 


Number reported 


as trace 




Range 


0.008-0.030 


Range 




r 



58 



Pesticides Monitoring Joi|i 



E 4. (cont'd.)- 



Levels of chemical and metal residues, by food class, in adiill food composites from 20 United States 
cities — August 1975-July 1976 



Residues, ppm 



Chemical 



Residues, ppm 



HION 

ige 

ve Composites 

al number 

mber reporled as trace 

ige 

'HENE 

ige 

ve composites 

:al number 

mber reported as trace 

Ige 



Ige 

ve composites 

al number 

mber reported as trace 

Ige 

ORAN 

Ige 

ve composites 

al number 

nber reported as trace 

Ige 

ANE 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 



Ige 

ve composites 

al number 

;nber reported as trace 

Ige 



1 



0.004 



1 
1 
T 



0.007 



2 



0.06-0.09 



0.002 



4 

1 

0.002-0.025 



0.003 



0.024-0.044 



0.001 



3 



0.002-0.014 



DIAZINON 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

P,P'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

P.P'-DDT 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

SELENIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

P-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



2 
1 
0.003 



0.003 



8 

3 

0.001-0.023 



1 

0.005 



2 
1 
0.002 



1 

0.010 



1 


0.008 



VI. LEGUME VEGETABLES 



Ige 

ve composites 

al nun'iber 

mber reported as trace 

Ige 

[UM 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 

lUM 

Ige 

ve composites 

al number 

Tiber reported as trace 

Ige 

IE 

ge 

ve composites 

al number 

nber reported as trace 

ge 



7.62 

20 



5.30-12.0 



0.01 

14 



0.01-0.07 



0.008 



5 



0.02-0.05 



1 



0.001 



LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ARSENIC 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 

PARATHION 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DICHLORAN 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 



0.26 

17 



0.08-0.82 



0.004 



1 

0.07 



0.002-0.003 



0.001 



1 


0.027 



VII. ROOT VEGETABLES 



ge 

•"e composites 

al number 

nber reported as 

ge 





LEAD 


2.32 


Average 




Positive composites 


20 


Total number 





Number reported as trace 


1.30-^.60 


Range 



0.036 

8 



0.06-0.14 



15, No. 1, June 1981 



59 



TABLE 4. (cont'd.). 



Levels of chemical and metal residues, by food class, in adult food composites from 20 United S 
cities — August 1975-July 1976 



Chemical 



Residues, ppm 



Chemical 



CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

SELENIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DCPA 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 





ARSENIC 






0.027 


Average 

Positive composites 






19 


Total number 









Number reported 


as 


trace 


0.01-0.08 


Range 
PARATHION 






0.002 


Average 

Positive composites 






2 


Total number 









Number reported 


as 


trace 


0.020 


Range 
P.P'-DDE 






T 


Average 

Positive composites 






1 


Total number 






1 


Number reported 


as 


trace 


T 


Range 
ETHION 






T 


Average 

Positive composites 






2 


Total number 






1 


Number reported 


as 


trace 


0.004 


Range 







VIII. GARDEN FRUITS 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ENDOSULFAN I 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ENDOSULFAN SULFATE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

DIAZINON 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

p,p'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

a-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 





LEAD 




2.08 


Average 

Positive composites 




20 


Total number 







Number reported 


as trace 


1.20-3.50 


Range 
ARSENIC 




0.02 


Average 

Positive composites 




18 


Total number 







Number reported 


as trace 


0.01-0.04 


Range 
LEPTOPHOS 




0.002 


Average 

Positive composites 




13 


Total number 




2 


Number reported 


as trace 


0.002-0.009 


Range 
ENDOSULFAN II 




T 


Average 

Positive composites 




6 


Total number 




1 


Number reported 


as trace 


0.002-0.004 


Range 
CARBARYL 




T 


Average 

Positive composites 




3 


Total number 




2 


Number reported 


as trace 


0.005 


Range 
LINDANE 




T 


Average 

Positive composites 




2 


Total number 




1 


Number reported 


as trace 


0.002 


Range 
PARATHION 




T 


Average 

Positive composites 




2 


Total number 




2 


Number reported 


as trace 


T 


Range 
ETHION 




T 


Average 

Positive composites 




3 


Total number 







Number reported 


as trace 


0.004-0.007 


Range 





60 



Pesticides Monitoring Joib 



,E 4. (cont'd.). 



Levels of chemical and metal residues, hy food class, in adult food composites from 20 United States 
cities — August 1975-July 1976 



Residues, ppm 



Chemical 



Residues, ppm 



3FENOTHION 

age 

ive composites 

tal number 

mber reported as trace 

nge 





TCNB 


0.010 


Average 




Positive composites 


1 


Total number 





Number reported as trace 


0.195 


Range 



1 


0.002 



IX. FRUITS 



age 

ive composites 

lal number 

mber reported as trace 

nge 

,ORAN 

age 

ive composites 

tal number 

mber reported as trace 

age 

[ANE 

age 

ive composites 

;al number 

mber reported as trace 

age 

iULFAN I 

ige 

ve composites 

:al number 

mber reported as trace 

ige 

iULFAN SULFATE 

Ige 

ve composites 

al number 

muber reported as trace 

age 

XONE 

ige 

ve composites 

;al number 

mber reported as trace 

iige 

RIN 

Ige 

ve composites 

al number 

mber reported as trace 

age 



Ige 

ve composites 

al number 

mber reported as trace 

age 

JRY 

Ige 

ve composites 

al number 

aaber reported as trace 

Ige 



2.44 

20 



0.10-19.0 


LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


0.009 

4 



0.006-0.163 


CARBARYL 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

1 


0.014 


DICOFOL 

Average 

Positive composites 

Number reported as trace 

Range 


T 

1 

0.007 


ENDOSULFAN II 
Average 

Positive composites 
Total number 
Number reported as trace 
Range 


T 

2 

1 
0.005 


CADMIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 


T 

1 

0,008 


ETHION 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

2 

0.001 


DIAZINON 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

1 

0.001 


CAPTAN 
Average 

Positive composites 
Total number 
Number reported as trace 
Range 



0.041 

11 


0.05-0.11 



3 
3 
T 



0.003 

4 



0.007-0.028 



2 
1 
0.012 



0.003 



5 


0.01-0.02 



3 



0.005-0.006 



1 


0.004 



0.003 



2 

0.026-0.040 



1 

0.015 



X. OILS, FATS, AND SHORTENING 



ge 

ve composites 

al number 

Tiber reported as trace 

>ge 





CADMIUM 


4.14 


Average 




Positive composites 


20 


Total number 





Number reported as trace 


0.20-6.20 


Range 



0.016 

18 



0.01-0.03 



15, No. 1, June 1981 



61 



TABLE 4. (cont'd.). 



Levels of chemical and metal residues, by food class, in adult food composites from 20 United I 
cities — August 1975-July 1976 



Chemical 



Residues, ppm 


Chemical 


0.003 

7 

2 

0.005-0.03 


P,P'-DDE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

3 

2 

0.002 


MERCURY 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


0.002 

1 

0.04 


HCB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

5 

2 

0.002-0.003 


PENTACHLOROANILINE 
Average 

Positive composites 
Total number 
Number reported as trace 
Range 


T 

1 
1 
T 


LINDANE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


0.028 

6 


0.05-0.14 


SELENIUM 
Average 
Positive composites 

Total number 

Number reported as trace 

Range 


T 

2 


0.004-0.005 


PCTA 

Average 

Positive composites 

Total numuber 

Number reported as trace 

Range 



MALATHION 
Average 

Positive composites 
Total number 
Number reported as trace 
Range 

DIELDRIN 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

ARSENIC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

PCNB 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

a-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

LEAD 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

PENTACHLOROBENZENE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



PCP METHYL ETHER 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



1 



0.002 



XL SUGAR AND ADJUNCTS 



ZINC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 

CADMIUM 

Average 

Positive composites 

Total number 

Number reported a . trace 

Range 

LINDANE 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



2.95 

20 



0.10-16.0 


PCP 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


0.011 

14 



0.01-0.03 


o-PHENYLPHENOL 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 


T 

7 

3 

0.001-0.003 


a-BHC 

Average 

Positive composites 

Total number 

Number reported as trace 

Range 



62 



Pesticides Monitoring Jo J 



E 4. (cont'd.). 



Levels of chemical and metal residues, by food class, in adult food composites from 20 United States 
cities — August 1975-July 1976 



Residues, ppm 



Chemical 



Residues, ppm 



PHION 

ige 

ve composites 

al number 

mber reported as trace 

ige 

ORAN 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 





LEAD 


T 


Average 




Positive composites 


3 


Total number 


1 


Number reported as trace 


0.005-0.008 


Range 




MERCURY 


T 


Average 




Positive composites 


1 


Total number 





Number reported as trace 


0.005 


Range 



0.015 

3 


0.06-O.14 



1 

0.012 



XII. BEVERAGES 



Ige 

ve composites 

al number 

mber reported as trace 

Ige 

IC 

ge 

ve composites 

al number 

mber reported as trace 

Ige 

Ige 

ve composites 

al number 

mber reported as trace 

Ige 





LEAD 


0.46 


Average 




Positive composites 


19 


Total number 





Number reported as trace 


0.20-1.90 


Range 




CADMIUM 


0.008 


Average 




Positive composites 


1 


Total number 





Number reported as trace 


0.15 


Range 




MERCURY 


0.001 


Average 




Positive composites 


1 


Total number 





Number reported as trace 


0.026 


Range 



0.004 

2 



0.04-0.05 

0.002 

3 

0.01 

0.001 

2 



0.006-0.018 



Average values are based on 20 composites examined; trace residues, if present, were treated as zero in calculating averages. Thus, an 
value of "T" can be well below detection limits of the methods for that compound. 



TABLE 5. 


FY 76 daily intakes, by food group 


, of metals in the diet 


of United States adults 








Lead 


Cadi 


muM 


Zinc 


Arsenic i 


Selenium 


Mercury 






% Total 




% Total 




% Total 




% Total 




% Total 




% Total 


Food Group 


HG/day 


Intake 


tJG/DAY 


Intake 


mo/day 


Intake 


|aG/DAY 


Intake 


HG/day 


Intake 


^ig/day 


Intake 


)airy products 


0.00 


0.0 


1.63 


5.0 


3.72 


19.4 


3.17 


4.8 


3.26 


2.4 


0.00 


0.0 


'leat. fish, and poultry 


3.67 


5.2 


2.63 


8.0 


8.44 


44.1 


49.46 


74.4 


52.52 


38.7 


5.29 


81.3 


Jrains and cereal products 


19.90 


28.0 


11.97 


36.4 


3.81 


19.9 


7.56 


11.4 


78.41 


57.8 


0.21 


3.2 


'otatoes 


5.15 


7.2 


7.46 


22.7 


0.82 


4.3 


0.00 


0.0 


0.59 


0.4 


0.00 


0.0 


.eafy vegetables 


0.38 


0.5 


2.43 


7.4 


0.15 


0.8 


0.00 


0.0 


0.03 


0.02 


0.00 


0.0 


-egume vegetables 


18.98 


26.7 


0.82 


2.5 


0.56 


2.9 


0.28 


0.4 


0.61 


0.4 


0.00 


0.0 


loot vegetables 


1.27 


1.8 


0.87 


2.6 


0.08 


0.4 


0.10 


0.1 


0.06 


0.04 


0.00 


0.0 


jarden fruits 


6.07 


8.5 


1.42 


4.3 


0.15 


0.8 


0.36 


0.5 


0.00 


0.0 


0.00 


0.0 


•ruits 


9.07 


12.8 


0.66 


2.0 


0.54 


2.8 


0.00 


0.0 


0.00 


0.0 


0.10 


1.5 


)ils, fats, and shortening 


2.04 


2.9 


1.11 


3.4 


0.30 


1.6 


0.00 


0.0 


0.16 


0.1 


0.02 


0.3 


ugar and adjuncts 


1.24 


1.7 


0.87 


2.6 


0.24 


1.3 


0.00 


0.0 


0.00 


0.0 


0.04 


0.6 


leverages (including 


3.31 


4.7 


1.02 


3.1 


0.32 


1.7 


5.57 


8.4 


0.00 


0.0 


0.85 


13.1 


drinking water) 


























Total intake 


71.08 


100.0 


32.89 


100.0 


19.13 


100.0 


66.50 


100.0 


135.64 


99.9-' 


6.51 


100.0 



calculated as arsenic trioxide (AsuOs). 
ot total 100 because of rounding error. 



ichlorine compounds present at low levels included 
' (hexachlorocyclohexane), dieldrin, heptachlor 
e, octachlor epoxide, methoxychlor, HCB (hexa- 
benzene), and lindane. A trace of an industrial 
:al, a PCB (polychlorinated biphenyl), was found 
of the composites. No organophosphorus com- 
i were found. 



MEAT, FISH. AND POULTRY 

Metal residues dominated this food class, with the fol- 
lowing series averages: 32.2 ppm zinc (range 25.3-76.0 
ppm), 0.20 ppm selenium, 0.19 ppm arsenic, 0.02 ppm 
mercury, 0.014 ppm lead, and 0.01 ppm cadmium. Of 
the organochlorine residues, p,p'-DDE, ranging from 
0.002 to 0.048 ppm and averaging 0.010 ppm for the 



15, No. 1, June 1981 



63 



series, was found in all 20 composites; dieldrin, averag- 
ing 0.007 ppm. was reported in 19 composites; and p,p'- 
DDT averaged 0.002 ppm with positive findings in 15 
composites. Trace averages were reported for p.p'-TDE, 
a-BHC, HCB, octachlor epoxide, heptachlor epoxide, 
ronnel, lindane, and rran^-nonachlor. Traces of ethion, 
an organophosphorus pesticide, and a PCB also were 
found in one and two composites, respectively. 

GRAIN AND CEREAL PRODUCTS 

All 20 composites contained zinc, selenium, and cad- 
mium residues, averaging 9.0, 0.19, and 0.03 ppm, re- 
spectively. Twelve composites had lead residues, averag- 
ing 0.05 ppm for the series, and eight composites had 
arsenic residues, for a series average of 0.02 ppm. Mala- 
thion, one of two organophosphorus pesticides, was 
reported in 19 composites and averaged 0.02 ppm for 
the series; the other, ronnel, occurred as a trace amount 
in one composite. Also reported were traces of dieldrin. 
chlordane, TCNB, lindane, diazinon. and mercury. 

POTATOES 

Zinc, ranging from 2.6 to 14.5 ppm, and cadmium, 
ranging from 0.02 to 0.09 ppm, were reported for all 20 
composites, with averages of 5.18 and 0.05 ppm, respec- 
tively. Lead, averaging 0.03 ppm for the series, was 
found in five composites, and selenium, ranging from 
0.02 to 0.05 ppm in three composites, averaged 0.006 
ppm for the 20-composite series. CIPC, ranging from 
0.01 to 0.23 ppm in five composites, averaged 0.04 ppm 
for the series. TCNB averaged 0.007 ppm for the series 
with a range of 0.002-0.114 ppm in six composites. 
Traces of heptachlor epoxide, dieldrin, endosulfan sul- 
fate, p.p'-DDE, and chlordane were also found. 

LEAFY VEGETABLES 

Only zinc, ranging from 1.7 to 7.0 ppm and averaging 
2.67 ppm, was reported for all 20 composites. Cadmium 
ranged from 0.02 to 0.10 ppm in 19 composites and 
averaged 0.04 ppm for the series. The most frequently 
reported pesticide was p.p'-DDE, averaging 0.003 ppm 
for the series, with eight reported findings. Endosulfan I, 
ranging from 0.001 to 0.011 ppm, and endosulfan II, 
ranging from 0.002 to 0.004 ppm, were each reported 
for five composites; endosulfan sulfate, ranging from 
0.008 to 0.030 ppm, was reported for six composites. 
Other reportable residues and their averages included 
dichloran, 0.002 ppm; DCPA, 0.001 ppm; Perthane®. 
0.003 ppm; and lead, 0.007 ppm. Traces of lindane, 
diazinon, parathion. toxaphene. dieldrin, p,p'-DDT, 
selenium, and /J-BHC were also found. 

LEGUME VEGETABLES 

Legume vegetables exhibited high metal residues. Zinc, 
reported in all 20 composites, ranged from 5.30 to 12.0 
ppm and averaged 7.62 ppm. Lead ranged from 0.08 to 
0.82 ppm and averaged 0.26 ppm for the series. Cad- 



mium, ranging from O.OI to 0.07 ppm, averaged 
ppm for the series. Arsenic and selenium occurre( 
frequently. The pesticides parathion. p,p'-DDE, 
dichloran were found at low levels. 

ROOT VEGETABLES 

Zinc ranged from 1.30 to 4.60 ppm and averaged 
ppm for the 20 composites. Cadmium, ranging 
0.01 to 0.08 ppm in 19 composites, averaged 0.027 
overall. Lesser amounts of lead, arsenic, and selei 
averaging 0.036, 0.004, and 0.002 ppm, respect 
were also reported. Only traces of parathion, die 
p,p'-DDE, DCPA, and ethion were found. 

GARDEN FRUITS 

Four metals were reported in this food class: 
ranging from 1.20 to 3.50 ppm in 20 composite; 
averaging 2.08 ppm; cadmium, ranging from 0.( 
0.04 ppm in 18 composites and averaging 0.02 ppi 
the 20-composite series; lead, ranging from 0.06 to 
ppm in 14 composites and averaging 0.081 ppm ft 
series; and arsenic, reported in one composite at 
ppm. The most significant pesticide residue, die 
ranged from 0.002 to 0.009 ppm in 13 composite 
averaged 0.002 ppm for the series. Carbophenothio 
found in one composite at 0.195 ppm. with a 
average of 0.01 ppm. The following trace average:! 
were reported: leptophos; endosulfan I, II, and si 
carbaryl; diazinon; lindane; p,p'-DDE; para 
a-BHC; ethion; and TCNB. 

FRUITS 

The two most prevalent residues in this food classi 
zinc, reported for all 20 composites, ranging from 
to 19.0 ppm and averaging 2.44 ppm, and lead, ra 
from 0.05 to 0.11 ppm in 11 composites and avei! 
0.041 ppm for the series. Cadmium, ranging frorr 
to 0.02 ppm in five composites, averaged 0.003 pp i 
the series. Both dichloran and dicofol were fou i 
four composites and averaged 0.009 ppm and 1 
ppm. respectively, for the series. Ethion ranged 1 
0.005 to 0.006 ppm for three composites but ave' 
trace for the series. Less frequently occurring re i 
were carbaryl, averaging a trace for the series; c: [ 
endosulfan I, II, and sulfate; Perthane; phosalone; J 
non; dieldrin; and o-BHC. Mercury, 0.015 ppmi 
reported for one composite. 

OILS, FATS. AND SHORTENING 

High zinc levels, ranging from 0.20 to 6.20 ppi 
averaging 4.14 ppm, were reported for 20 com 
Cadmium, ranging from 0.01 to 0.03 ppm in 18(c 
posites, averaged 0.016 ppm for the series. Sevemji 
posites contained malathion residues, ranging from 
to 0.03 ppm; series average was 0.003. Lead, ave- 
0.028 ppm for the series, ranged from 0.05 to 0.1 



64 



Pesticides Monitoring JohIi 



.E 6. Pesticide residues in individual commodities of dairy composite oj four market basket samples — August 1975- 

July 1976 



IE Found 



Commodity' 



Whole 
Milk (4) 



Evaporated Ice Cottage Processed Natural 

Milk (4) Cream (4) Cheese (4) Cheese (4) Cheese (4) Butter (4) 



Skim 
Milk (4) 



Ice 
Milk (2) 



:s found 
ge, ppm 


1 
T 


4 
T-0.002 


4 
T-0.002 


3 
T 


4 
0.002-0.005 


4 
0.001-O.008 


4 
0.008-O.011 


2 
T-O.OOl 


DE 

;s found 
;e, ppm 


2 
0.002-0.003 


4 
T-0.020 


3 
0.002-O.010 


2 
0.003-0.009 


4 
0.002-0.016 


3 
T-0.004 


4 
0.004-0.132 


2 
0.002-0.006 


;s found 
le, ppm 


1 
T 


2 
T 


3 
T 


1 

0.001 


3 
T-O.OOl 


3 
T-0.002 


4 1 
T-0.004 T 


1 
T 


•h\oT epoxide 
;s found 
•e, ppm 




2 

T 


2 
T 


1 

T 


3 
0.002-0.005 


4 
T-0.004 


4 
0.004-0O19 




,n 

;s found 

se, ppm 




4 
T-0.002 


4 
T-0.002 


2 
T 


4 
0.005-0.010 


4 
0.003-0.010 


4 
0.017-0.053 




sychlor 
;s found 
se, ppm 




1 

0.016 


1 
T 


1 
T 




1 
T 


1 
0.141 




,e 

:s found 

se, ppm 






2 
T 




1 
0.001 




2 
T-0.002 




lor epoxide 
s found 
!e, ppm 






1 
T 




3 
T-0.002 


3 
T 


3 
0.004-0.008 




5T 

s found 

le, ppm 










2 
T 


1 

T 






)E 

s found 

;e, ppm 












1 
T 







T = trace, 
■milk and nonfat dry milk not included because no residues were found 
«rs in parentheses indicate number of times that commodity was analyzed. 



composites. Pentachloroaniline, averaging 0.002 
for the series, was found in four composites. The 
ning residues included HCB, selenium, PCNB, 
i, pentachlorobenzene, dieldrin, a-BHC, arsenic, 
)DE, and lindane. One composite contained 0.008 
nercury. 

I AND ADJUNCTS 

tietal residues were among the highest in this food 
Zinc, ranging from 0.10 to 16.0 ppm, was reported 
20 composites and averaged 2.95 ppm. Cadmium, 
in 14 composites, averaged 0.011 ppm for the 
Lead, ranging from 0.06 to 0.14 ppm in three 
asites, averaged 0.015 ppm for the series. Mercury 
12 ppm was reported for one composite. Other resi- 
tvere a-BHC, PCP, lindane, malathion, o-phenyl- 
1, and dichloran. 

tAGES 

found in 19 composites at levels ranging from 0.20 
ppm, averaged 0.46 ppm for the series. The 
ning residues, each found in three or fewer com- 
s, had the following series averages: cadmium. 



0.002 ppm; lead, 0.004 ppm; mercury, 0.001 ppm; ar- 
senic. 0.008 ppm; and PCP, 0.001 ppm. 

Discussion 

Of the 240 composites analyzed, 125, or 52 percent, 
contained organochlorine pesticide residues, compared 
with 49, 48, 52, and 54 percent reported for fiscal years 
1975, 1974, 1973, and 1972, respectively. Organophos- 
phorus residues in the current reporting period were 
found in 45, or 18.7 percent, of the composites. Corre- 
sponding findings for fiscal years 1975, 1974, 1973, and 
1972 were 25, 28, 31, and 28 percent, respectively. The 
present report and that for FY 75 were based on 20 
market baskets, whereas all earlier reports were based 
on 30 market baskets. 

Sixty percent of the 346 organochlorine residues in the 
current reporting period were found in two food classes: 
dairy products and meat-fish-poultry. The remaining 
organochlorine residues were distributed among the 
other food classes with the garden fruits and leafy vege- 
tables containing half of them. No organochlorine resi- 



15, No. 1, June 1981 



65 



TABLE 7. Pesticide residues in individual commodities of meal and fish composites of four market baskets, 

July 1976 



Residue Found 



Roast 
Beef (4) 



COMMODirV 1 



Ground 
Beef (4) 



Pork 
Chops (4) 



Bacon 

(4) 



Chicken 

(4) 



Fish 

Fillet (4) 



Dieldrin 
Times found 
Range, ppm 



4 
T-0.003 



0.006-0.007 



0.002-0.006 



2 
T-2.25 



0.002-0.007 



1 
T 



p,p'-TDE 

Times found 
Range, ppm 



1 
0.008 



1 
0.016 



0.007 



2 
T-0.081 



HCB 

Times found 
Range, ppm 



3 

T-0.002 



2 

0.002 



0.002 



0.030 



0.002-0.008 



2 
T-0.003 



1 
T 



a-BHC 

Times found 
Range, ppm 



2 
T-O.OOl 



2 
0.001 



1 

T 



2 
0.002 



1 
T 



p.p '-DDE 
Times found 
Range, ppm 



3 

T-0.048 



1 
0.031 



0.002-0.152 



0.002-0.028 



0.010-0.875 



Heptachlor epoxide 
Times found 
Range, ppm 



2 2 

0.001-0.009 0.002 



2 
T-0.005 



2 
T 



Ethion 
Times found 
Range, ppm 

Octachlor epoxide 
Times found 
Range, ppm 



1 
0.002 



1 
0.05 



1 

0.002 



3 

T-O.OU 



1 

0.003 



rran^-Nonachlor 
Times found 
Range, ppm 




1 
0.034 


1 
0.003 






p,p'-DDT 
Times found 
Range, ppm 




1 

0.034 


2 
T-0.141 




3 

0.023-0.130 


Endrin 
Times found 
Range, ppm 








1 
0.001 




PCB (Aroclor 1254) 
Times found 
Range, ppm 


1 
T 






1 

T 


T 

1 


Chlordane 
Times found 
Range, ppm 








1 
T 


1 
T 


Lindane 
Times found 
Range, ppm 












TCNB 

Times found 
Range, ppm 

























NOTE: T = trace. 

1 Numbers in parentheses indicate the number of times the item was analyzed. 



66 



Pesticides Monitoring Joii" 



Frank- 
furters (4) 



Beef 

Liver (4) 



Eggs (4) 



Commodity! 



Ham (4) 



Round 
Steak (4) 



Veal (1) 



Lamb (2) 



Shrimp (2) 



4 1 

0.004-0.054 0.014 



T-0.018 



2 
T-0,002 



2 1 

O.002-O.O04 T 



1 
T 



0,001-0.002 T 



2 
T 



2 
T 



2 
0.002 



1-0.003 T-0.004 



T-0.004 



3 
T 



2 
T-0.003 



4 2 

4-0.030 T-0.029 T-0.003 



3 1 

0.002-0.026 0.002 



0.006-0.026 



0.011-0.037 



3 1 

1-0.002 T-0.002 0.005 



0.002 



2 1 

T-0.002 T 



1 
0.002 



1 
0.003 



1 
T 



15, No. 1, June 1981 



67 





TABLE 8 


. Recovery data on residues found in 


adult total diet samples, August 1975-July 1976 








Range of 












Range of 






Type OF 




Unforti- 


Range of 


No. of 




Type of 




Unforti- 


Range op Nc 




Food 


Spike fied Com- 


Total Resi- 


Recov- 




Food 


Spike 


fied Com- 


Total Resi- Ri 




Com- 


Level, 


POSITE, 


due Found, 


ery At- 




Com- 


Level 


posite, 


DUE Found, eri 


Residue 


posite 


PPM 


PPM 


PPM 1-2 


tempts 


RESIDtm 


posite 


PPM 


PPM 


PPM 1.= IE 


Heptachlor 


fatty 


0.003 


0-0.001 


0.0023-0.0035 


4 


Picloran 


fatty 


0.10 


0.00 


0.00-0.043 


epoxide 








(0.0031) 












(-) 




nonfalty 


0.003 


0-0.001 


0.0027-O.0039 
(0.0032) 


6 




nonfatty 


0.10 


0.00 


0.033-O.075 
(0.046) 


Oxychlordane 


fatty 


0.003 


0-0.0007 


0.0022-0.0031 
(0.0027) 


4 


Silvex 


fatty 


0.04 


0.00 


0.00-O.032 
(0.015) 




nonfatty 


0.003 


0-0.0006 


0.0024-O.0035 
(0.0027) 


6 




nonfatty 


0.04 


0.00 


0.020-O.053 
(0.033) 


Ethion 


fatty 


0.01 


0.00 


0-0.0056 

(-) 

0.0066-0.012 


4 


2,4-DB 


fatty 


0.02 


0.00 


T-O.005 

(-) 

0.0O-O.033 




nonfatty 


0.01 


0.00 


6 






0.04 


0.00 










(0.0086) 












(0.014) 


DCPA 


tatty 


0.005 


0.00 


0.0027-0.0047 
(0.0037) 


6 




nonfatty 


0.02 


0.00 


O.002-O.015 
(0.008) 




nonfatty 


0.005 


0-0.0084 


0.0029-0.0059 
(0.0050) 


12 






0.04 


0.00 


0.00-O.038 
(0.025) 


Perthane 


fatty 


0.01 


0.00 


T-0.0104 
(0.0069) 


6 


2,4,5-T 


fatty 


0.02 


0.00-0.001 


0.0058-0.021 
(-) 




nonfatty 


0.01 


0.00 


0.0035-0.014 
(0.0091) 


12 






0.08 


0.00 


0.026-0.059 
(-) 


Methyl 


tatty 


0.005 


0.00 


0.0022-0.0030 


3 




nonfatty 


0.02 


0.00 


0.003-0.0198 
(0.014) 
0.032-0.069 
(0.048) 


parathion 


nonfatty 


0.005 


0.00 


(0.0026) 

0.0031-0.0045 

(0.0037) 


5 






0.08 


0.00 


Endosulfan 


tatty 


O.OI 


0.00 


0.002-0.0076 


2 


MCP 


fatty 


0.02 


0.00 


0.009-0.013 


sulfate 








(0.0048) 




2-methyl-4- 








(0.011) 




nonfatty 


0.01 


0.00-O.004 


0.0035-0.0143 
(0.0095) 


6 


chlorophenoxy- 
acetic acid 


nonfatty 


0.02 


0.00 


0.0055-0.026 
(0.014) 


Tetradifon 


fatty 


0.02 


0.00 


T-0.027 
(0.015) 


4 


Carbaryl 


nonfatty 


0.20 


0.00 


0.00-0.20 
(0.157) 






0.10 


0.00 


0.088-0.089 
(-) 


2 


o-Phenylphenol 


nonfatty 


0.40 


0.00 


0.00-0.40 
(0.24) 




nonfatty 


0.02 


0.00 


0.0104-0.022 


8 




















(0.0160) 




Arsenic 


fatty 


0.30 


0.00-0.35 


0.26-0.81 






0.10 


0.00 


0.054-0.188 
(0.109) 


6 






0.40 


0.00-0.28 


(0.376) 
0.37-0.86 


Malathion 


fatty 


0.005 


0.00 


0.0037-0.0038 


2 




nonfatty 


0.30 


0.00-0.03 


(0.44) 
0.19-0.46 




nonfatty 


0.005 


0.00 


( — ) 

0.0022-0.0064 

(0.0041) 


6 






0.40 


0.00-0.03 


(0.30) 

0.13-0.57 

(0.44) 


Phnsalone 


fatty 


0.02 


0.00 


0.0-0.017 


3 












X iii^aaivi^' 








(-) 




Cadmium 


fatty 


0.10 


0.00-0.027 


0.094-0.199 




nonfatty 


0.02 


0.00-0.002 


0.007-O.026 
(0.0166) 


6 




nonfatty 


0.10 


0.00-0.058 


(0.113) 
0.058-O.156 


Leptophos 


fatty 


0.05 


0.00 


0.016-0.040 


3 










(0.116) 










(0.027) 




Lead 


fatty 


0.20 


0.0O-0.14 


0.020-0.340 




nonfatty 


0.05 


0.00 


0.030-0.053 
(0.043) 


6 




nonfatty 


0.20 


0.00-0.310 


(0.133) 
0.058-0.480 


Fonofos 


fatty 


0.01 


0.00 


0.002 


1 










(0.211) 




nonfatty 


0.01 


0.00 


0.0067-O.0095 
(0.0083) 


6 


Mercury 


fatty 


0.06 


0.00-0.049 


0.018-0.110 

(0.073) 

0.062-0.088 


Toxaphene 


fatty 


0.20 


0.00 


0.148 


1 




nonfatty 


0.06 


O.OO-O.Oll 




nonfatty 


0.20 


0.00 


0.147-0.226 


6 










(0.075) 










(0.187) 




Selenium 


fatty 


0.20 


0.00-0.23 


0.00-0.39 


2,4-D 


fatty 


0.04 


0.00-0.009 


0.00-0.050 
(0.021) 


7 


..JklWIIlUlll 


nonfatty 


0.20 


0.00-O.24 


(0.227) 
0.11-0.48 




nonfatty 


0.04 


0.00 


0.008-0.046 
(0.028) 


14 










(0.216) 


PC? 


fatty 


0.02 
0.04 


0.00-0.003 
0.00-0.001 


0.0012-0.009 

(0.007) 

0.00-0.030 


4 
7 


Zinc 


fatty 


5.0 
25.0 


1.23-6.20 
4.00-76.00 


5.74-11.00 

(9.54) 

29.00-99.00 




nonfatty 


0.02 


0.0-0.0004 


(0.015) 

0.003-0.018 

(0.0084) 


1 




nonfatty 


5.0 


0.10-12.00 


(54.2) 

4.68-15.0 

(8.09) 






0.04 


0.00-0.0062 


0.003-0.039 
(0.022) 


1 






25.0 


0.38-15.50 


24.38-38.0 
(29.8) 



NOTE: T = trace. 

1 Numbers in parentheses represent average residue levels. 

' These values are uncorrected for background. 



68 



Pesticides Monitoring Joi R 



> were found in beverage composites and only two 
; found in the legume vegetable composite. 

56 organophosphorus residues constitute about 14 
:ent of the total pesticide residues reported, with 
ithion representing 29 of them. Nineteen were found 
rain and cereal products, seven in fats and oils, and 
e in the sugar composites. No organophosphorus 
lues were four»d in the dairy products, potatoes, or 
:rage composites. 

carbamate pesticide carbaryl occurred in five com- 
tes, once at the 0.05 ppm level and four times at the 
i level. The method for determination of carbaryl 
also detect the fungicide o-phenylphenol, which was 
Tted in one sugar composite at the trace level. 

I industrial chemicals were detected. Trace amounts 
PCB, Aroclor 1254, were found in one dairy com- 
te and in two meat-fish-poultry composites. Low 
s of pentachlorobenzene were found in two fat 
posites. 

ill the residues reported, 606, or 58 percent, were 
lis. Zinc was reported in almost every composite, 
the highest levels being found in the meat com- 
es. Cadmium was found in 170 composites and lead 
5 composites; both were found throughout the vari- 
;lasses of foods with fewest findings in the dairy and 
leverage composites. The 57 selenium residues, 31 
lie residues, and 24 mercury residues were found 
ominantly in the meat-fish-poultry composites and 
i-cereal composites. 

idition to the analysis of the various food class com- 
es, four market baskets, one from each region, were 
ted for individual item analysis of two food groups, 
item-by-item analysis often provides a more ex- 
; picture as to the source of residues within a 
Josite. The dairy and meat classes were chosen 
use those composites have consistently contained 
tiighest levels of organochlorine and organophos- 
us residues. Tables 6 and 7 present these findings. 

ivery studies were conducted with each market bas- 
Composites were fortified with known compounds 
^senting each type of residue (metal, pesticide, etc.), 
:orrections were made for the unfortified composite 
ibution. The total amount recovered through the 
od was determined. These results are presented in 



A cknowledgments 

authors acknowledge the contributions of all staff 

bers assigned to the Total Diet Section, Food and 

Administration, Kansas City District Laboratory. 



LITERATURE CITED 

(/) Corneliussen, P. E. 1969. Pesticide residues in total 
diet samples (IV). Pestic. Monit. J. 2(4) : 140-152. 

(.2) Corneliussen, P. E. 1970. Pesticide residues in total 
diet samples (V). Pestic. Monit. J. 4(3):89-I05. 

(3) Corneliussen, P. E. 1972. Pesticide residues in total 
diet samples (VI). Pestic. Monit. J. 5(4) :313-330. 

(4) Duggan, R. £., H. C. Barry, and L. Y. Johnson. 1966. 
Pesticide residues in total diet samples. Science 151 
(3706): 101-104. 

(5) Duggan, R. E., H. C. Barry, and L. Y. Johnson. 1967. 
Pesticide residues in total diet samples (II). Pestic. 
Monit. J. 1(2):2-12. 

(6) Duggan, R. E., P. E. Corneliussen, M. B. Duggan, 
B. M. McMahon, and R. J. Martin. 1981. Pesticide 
residue levels in foods in the United States from July 
1, 1969, to June 30, 1976. Pestic. Monit. J. (sub- 
mitted). 

(7) Duggan. R. E., and F. J. McFarland. 1967. Residues 
in food and feed. Assessments include raw food and 
feed commodities, market basket items prepared for 
consumption, meat samples taken at slaughter. Pestic. 
Monit. J. 1(1): 1-5. 

(S) Finocchiaro, J. M., and W. R. Benson. 1965. Thin- 
layer chromatographic determination of carbaryl 
(Sevin) in some foods. J. Assoc. Off. Anal. Chem 
48(4):736-738. 
(9) Food and Drug Administration. 1971. Pesticide Ana- 
lytical Manual. Vols. 1 and II. U.S. Department of 
Health and Human Services, Washington, D.C. 

(10) Hundley, H. K., and J. C. Underwood. 1970. Determi- 
nation of total arsenic in total diet samples. J. Assoc. 
Off. Anal. Chem. 53(6) :1 176-1178. 

(//) Johnson, R. D., and D. D. Manske. 1975. Pesticide 
residues in total diet samples (IX). Pestic. Monit J 
9(4):157-169. 

(/2) Johnson, R. D.. and D. D. Manske. 1977. Pesticide 
and other chemical residues in total diet samples (XI) 
Pestic. Monit. J. 11 ( 3 ) : 1 1 6-1 3 1 . 

(13) Johnson, R. D., D. D. Manske, D. H. New, and D. S. 
Podrebarac. 1979. Pesticide and other chemical resi- 
dues in infant and toddler total diet samples — (I) 

August 1974-July 1975. Pestic. Monit. J. 13(3):87-98. 

(14) Manske. D. D., and P. E. Corneliussen. 1974. Pesti- 
cide residues in total diet samples (VII). Pestic Monit 
J. 8(2):110-124. 

{15) Manske, D. D., and R. D. Johnson. 1975. Pesticide 
residues in total diet samples (VIII). Pestic. Monit J 
9(2):94-105. 

(16) Manske, D. D., and R. D. Johnson. 1977. Pesticide and 
other chemical residues in total diet samples (X) 
Pestic. Monit. J. 10(4) : 1 34-148. 

(17) Martin. R. J., and R. E. Duggan. 1968. Pesticide resi- 
dues in total diet samples (III). Pestic Monit J 
1(4): 11-20. 

(18) Official Methods of Analysis. 1975. AOAC, Arling- 
ton, VA, 12th ed., sections 25.026-25.030,' 25.065- 
25.070, 25.103-25.105, 25.117-25.120, 25.143-25.147. 

(19) Porter, M. L., R. J. Gajan, and J. A. Burke. 1969. 
Acetonitrile extraction and determination of carbaryl 
in fruits and vegetables. J. Assoc. Off. Anal. Chem 
52(1):177-181. 



15, No. 1, June 1981 



69 



APPENDIX 



Chemical Names of Compounds Discussed in This Issue 



ALDRIN 

AROCLOR 1016 or 1242 

AROCLOR 1242 

AROCLOR 1254 

BHC (Benzene Hexachloride) 

CAPTAN 

CARBARYL 

CARBOPHENOTHION 

CHLORDANE 

CIPC 

2,4-D 

DACTHAL 

2,4-DB 

DDE 

DDMU 

DDT 

DIAZINON 

DICHLORAN 

DICOFOL 

DIELDRIN 

ENDOSULFAN 

ENDOSULFAN SULFATE 

ENDRIN 

ETHION 

FONOFOS 

HCB 

HEPTACHLOR 

HEPTACHLOR EPOXIDE 

LEPTOPHOS 

LINDANE 

MALATHION 

MCP 



Hexachlorohexahydro-enrfo^exo-dimelhanonaphthalene 95% and related compounds 5% 

PCB, approximately 42% chlorine 

PCB, approximately 42% chlorine 

PCB, approximately 54% chlorine 

1,2,3,4,5,6-Hexachlorocyclohexane (mixture of isomers) 

N-Trichloromethylthio-4-cyclohexene-l,2-dicarboximide 

1-Naphthyl methylcarbamate 

■y-[[(p-ChlorophenyI)thio]methyl] 0,0-diethyl phosphorodithioate 

Technical: 60% octachloro-4,7-methanotetrahydroindane and 40% related compounds 

Isopropyl N-(3-chlorophenyl) carbamate 

2,4-Dichlorophenoxyacetic acid 

Dimethyl tetrachloroterephthalate 

4- (2,4-Dichlorophenoxy) butyric acid 

Dichlorodiphenyldichloroethylene (degradation product of DDT) 

l-Chloro-2,2-bis (p-chlorophenyl ) ethylene 

Dichloro diphenyl trichloroethane. Principal isomer present (p,p'-DDT; not less than 70%: 1,1.1-trichlo^ 
bis (p-chlorophenyl ) ethane 

0,0-Diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate 

2,6-Dichloro-4-nitroaniline 

l,l-Bis(chlorophenyl)-2.2,2-trichloroethanol 

Hexachloroepoxyoctahydro-endo,ej:o-dimethanonaphthalene 85% and related compounds 15% 

Hexachlorohexahydromethano-2,4,3-benzodioxathiepin 3-oxide 

l,4,5,6.7,7-Hexachloro-5-norbornene-2,3-dimethano! cyclic sulfate 

Hexachloroepoxyoctahydro-endo.e/irfo-dimethanonaphthalene 

0,0, 0'.O'-Tetraethyl 5,S'-methylene bisphosphorodithioate 

O-Ethyl S-phenyl ethylphosphonodithioate 

Hexachlorobenzene 

Heptachlorotetrahydro-4,7-methanoindene 

l,4,5,6.7.8,8-Heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 

0-(4-Bromo-2,5-dichlorophenyl) 0-methyl phenylphosphonothioate 

Gamma isomer of benzene hexachloride (BHC) 

0,0-Dimethyl dithiophosphate of diethyl mercaptosuccinate 

See MCPA 



(Continued next page) 
70 



Pesticides Monitoring Joi'lt 



APPENDIX (continued) 



rHOXYCHLOR 

[■HYL PARATHION 

EX 

4ACHLOR 

ACHLOR EPOXIDE 

'CHLORDANE 

ATHION 

s (Polychlorinated Biphenyls) 
B 



s (Polychlorinated Terphenyls) 

THANE 

ISALONE 

iTOMIREX 

-ORAM 

INEL 

■T 

B 

A 

RADIFON 
APHENE 
TP 



2-Methyl-4-chlorophenoxyacetic acid 

2,2-Bis(p-methoxyphenyl),l,l,l-trichloroethane 88% and related compounds 12% 

0,0-Dimethyl O-p-nitrophenyl phosphorothioate 

Dodecachlorooctahydro-l,3,4-metheno-l//-cyclobuta[cd]pentalene 

l,2,3,4,5,6,7,8,8-Nonachloro-3a,4,7,7a-tetrahydro-4.7-methanoindan 

l-e.xo-2-fn(/o-4,5,6,7,8,8a-Oclachloro-2,3-e-xo-epoxy-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene 

l-*>.vo-2-6'ntio-4.5,6,7,8,8a-Octachloro-2,3-f-xo-epoxy-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene 

0,0-Diethyl O-p-nitrophenyl phosphorothioate 

Pentachloroaniline 

Mixtures of chlorinated biphenyl compounds having various percentages of chlorine 

Pentachloronitrobenzene 

Penlachlorophenol 

Pentachlorothioanisole 

Mixtures of chlorinated terphenyl compounds having various percentages of chlorine 

1, 1-Bis (ethylphenyl) -2,2-dichloroethane 

S-[6-Chloro-3-(mercaptomethyl)-2-benzoxazolinone) 0,0-diethyl phosphorodithioate 

l,2,3,4,5,5,6,7,9,10,10-Undecachloropentacyclo[5.3.0.0=».03.''.0«.«]decane 

4-Amino-3,5,6-trichloropicoUnic acid 

0,0-Dimethyl 0-(2,4,5-trichlorophenyl) phosphorothioate 

2,4,5-Trichlorophenoxyacetic acid 

l,2,4,5-Tetrachloro-3-nitrobenzene 

Tetrachlorothioanisole 

Dichloro diphenyl dichloroethane (l,l-dichloro-2,2-bis(p-chlorophenyl)ethane, principal component) 

4-Chlorophenyl 2,4,5-trichlorophenyI sulfone 

Technical chlorinated camphene (67-69% chlorine) 

2- (2,4,5-Trichlorophenoxy) propionic acid 



15, No. 1, June 1981 



71 



ERRATUM 

Pesticides Monitoring Journal, Volume 14, 
Number 4, page 136. The abstract of the article 
"Organochlorine Residues in Fish: National Pesti- 
cide Monitoring Program, 1970-74" should be 
corrected to read as follows: 

Highest PCB residues were found in the industrial- 
ized areas of the Northeast and Midwest. . . . 



72 



Pesticides Monitoring Joi|i 



PLANT GROWTH REGULATOR WORKING GROUP 
EIGHTH ANNUAL MEETING 

August 3-6, 1981 

The Plant Growth Regulator Working Group (PGRWG) is announcing its 
eighth annual meeting, to be held at the Don Cesar Hotel, St. Petersburg, Florida, 
August 3-6, 1981. 

The meeting will feature two symposia: 

• Natural Products as Plant Growth Regulators 

• Plant Growth Regulators in Biological Systems 

Fifty-two technical papers will be presented by industry and university scientists, 
covering a range of chemicals being tested or having potential for future food 
production and crop management. 

The best basic and the best applied paper presented by a student will receive a 
$100 award. 



For further information contact 

Dr. L. H. Aung 

Virginia Polytechnic Institute and State University 

Blacksburg, VA 24061 

(703-961-6511) 



5, No. 1, June 1981 73 



Information for Contributors 



The Pesticides Monitoring Journal welcomes from all 
sources qualified data and interpretative information on 
pesticide monitoring. The publication is distributed 
principally to scientists, technicians, and administrators 
associated with jjesticide monitoring, research, and 
other programs concerned with pesticides in the environ- 
ment. Other subscribers work in agriculture, chemical 
manufacturing, food processing, medicine, public health, 
and conservation. 

Articles are grouped under seven headings. Five follow 
the basic environmental components of the National 
Pesticide Monitoring Program: Pesticide Residues in 
People; Pesticide Residues in Water; Pesticide Residues 
in Soil; Pesticide Residues in Food and Feed; and 
Pesticide Residues in Fish, Wildlife, and Estuaries. The 
sixth is a general heading; the seventh encompasses 
briefs. 

Monitoring is defined here as the repeated sampling and 
analysis of environmental components to obtain reliable 
estimates of levels of pesticide residues and related 
compounds in these components and the changes in 
these levels with time. It can include the recording of 
residues at a given time and place, or the comparison of 
residues in different geographic areas. The Journal will 
publish results of such investigations and data on levels 
of pesticide residues in all portions of the environment 
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Authors are responsible for the accuracy and validity 
of their data and interpretations, including tables, charts, 
and references. Pesticides ordinarily should be identi- 
fied by common or generic names approved by national 
or international scientific societies. Trade names are 
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employed should be described in detail. If reference is 
made to procedures in another paper, crucial points or 
modifications should be noted. Sensitivity of the method 
and limits of detection should be given, particularly 



74 



when very low levels of pesticide residues are b 
reported. Specific note should be made regarding 
rection of data for percent recoveries. Numerical c 
plot dimensions, and instrument measurements shi 
be reported in metric units. 

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PESTICIDES 
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JOURNAL 



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VOLUME 15 NUMBER 2 
PEMJAA(15) 77-110 (1981) 




^rEx /^9:/5y^ 



p 



CONTENTS 



Volume 15 September 1981 Number 2 



Page 



HUMANS 



Chlorinated Hydrocarbon Pesticides in Blood of Newborn Babies in India 77 

Mohammed K.J. Siddiqui. Mukesh C. Saxena, Ajeet K. Bhargava, Coimbatore R. 
Krishna Murti, and D. Kutty 

FISH, WILDLIFE, AND ESTUARIES 

Organochlorine Insecticide Residues in Soil and Earthworms in the Delhi Area, India. 

August-October, 1974 80 

Dharam Vir Yadav, Pradeep K. Mittal, Hari C. Agarwal, and M.K. Krishna Pillai 

Organochlorine Insecticide Concentrations in Fish of the Des Moines River. Iowa, 

1977-78 ^ 86 

Ross V. Bulkley. Siu-Yin Theresa Leung, and John J. Richard 

Organochlorine and Metal Residues in Eggs of Waterfowl Nesting on Islands in Lake 

Michigan off Door County, Wisconsin. 1977-78 90 

Susan D. Haseltine, Gary H. Heinz. William L. Reichel, and John F. Moore 

Persistence of Dieldrin in Water and Channel Catfish from the Des Moines River, Iowa, 

1971-73 and 1978 98 

Siu-Yin Theresa Leung, Ross V. Bulkley, and John J. Richard 

DDT and BHC Residues in Some Body Tissues of Goals, Buffalo, and Chickens, 

Lucknow, India 103 

Bhupendra S. Kaphalia and Tejeshwar D. Seth 

APPENDIX 107 

ANNOUNCEMENTS 108 

Information for Contributors 109 



HUMANS 



Chlorinated Hydrocarbon Pesticides in Blood of Newborn Babies in India 



Mohammed K.J. Siddiqui,' Mukesh C. Saxena,' Ajeet K. Bhargava,- Coimbatore R. Krishna MurtI,- and D. Kutty- 



ABSTRACT 

Jmbilical cord blood collected during labor of 100 Indian 
vomen was analyzed for organochlorine pesticides by 
',as-liquid chromatography with electron-capture detection, 
iignificant levels of p,p' -DDT and its metabolites. p.p'-TDE 
md p.p' -DDE. as well as a-. (J-, and y-isomers of BHC were 
'stimated. Residues in the neonatal blood were related to age, 
iietelic habits, and area of residence of the mothers. The 
lud\ highlights the extent of placental transfer of the body 
nirden of toxic chemicals from the mother to the fetus. 



Introduction 

In recent years, man has become more conscious of the 
A/ay in which the environment is polluted by chemicals 
hat harm plants, animals, and humans. Organochlorine 
pesticides have been a major cause of concern to 
:cologists, not only because they persist so long in the 
environment (77. 14) but also because of the readiness 
with which they accumulate in the human body. Their 
;endency to accumulate in fatty tissues (i), because of 
their lipophilic nature and resistance to biodegradation 
(2), has caused significant residue burdens in adipose 
tissues (8), blood (7, 4), and even human milk (7, 10, 
13. 18). 

These toxic agrichemicals have access to the growing 
fetus through placental tissue (5, 12, 15). Stillborn 
infants have been determined to be contaminated with 
such compounds (6). Earlier studies have also drawn 
attention to the presence of organochlorine pesticides in 
the cord blood of the fetus (16, 17). 

Persistent organochlorine pesticides like DDT, which 
have been banned in other countries, are still commonly 
used in India in agriculture and malaria eradication 



Industrial Toxicology Research Centre. Post Box 80. Lucknow-226001 , India 
Obstetrics and Gynaecology Department. King George's Medical College. 
Lucknow-226001. India 



programs. Therefore, it was considered worthwhile to 
assess organochlorine residues in neonatal blood in 
India. The present report also relates the extent of 
placental transfer of these compounds from mother to 
child according to age, dietetic habits (vegetarian/ 
nonvegetarian), and area of residence (rural/urban). 



Materials and Methods 

A total of 100 pregnant women were studied. The 
women were admitted to Queen Mary's Hospital, 
associated with the Department of Obstetrics and 
Gynaecology, King George's Medical College, Luck- 
now, capital of the most populous state in India. None 
of the women, on inquiry, reported any accidental or 
occupational exposure to any of the pesticides studied. 
None of the women suffered from any serious diseases 
except mild hypertension. Umbilical cord blood of 
these subjects was collected in heparinized vials during 
labor and stored at 10°C until the analysis was carried 
out, generally within 48 hours. 

A 1-ml aliquot of blood was mixed with 5 ml formic 
acid and 2 ml «-hexane in a 25-ml conical flask. 
Contents were shaken 1 hour at 37°C in a mechanical 
shaker, and centrifuged 10 minutes at 2,000 rpm in a 
refrigerated centrifuge. Losses due to evaporation were 
made up by weighing the container before and after 
shaking. The upper layer (hexane) was recovered by 
disposable suction pipet. The extracted samples were 
further cleaned up according to the method of Dale et 
al. (9) as follows: 

The hexane extract plus 1 ml distilled water in a clean 
test tube were kept in a liquid air-methanol bath to 
remove traces of formic acid. The unfrozen hexane 
phase was further treated with 1 ml fuming H2SO4 
(three times) to remove the fat. Recoveries through this 
cleanup procedure were greater than 84% for all 
pesticides in the fortified samples, except lindane. 



Vol. 15, No. 2, September 1981 



77 



which was recovered at about 79%. The cleaned 
samples in hexane were analyzed for organochlorine 
pesticides on a Varian Aerograph Series 2400 gas-liquid 
chromatograph, equipped with an electron-capture 
detector CH). The operating conditions of the instru- 
ment were as follows: 



Camer gas: purified nitrogen (99.9%) passed through sUica gel 

and molecular sieve to remove inoisture and oxygen, 
respectively 



Gas pressure: 
Row rate: 


65 psi 
45 ml/min 


Temperatures, °C 


injector 190 
colmun 180 




detector 200 


Attenuation: 


4x10-' 


Current: 
Column: 


10-' (lamp 

glass spiral column, 6 ftxi/s-in- ID. packed with 

l.S^c OV-17 + 1.95% OV-210 on 80-100-mesh Gas- 




Chrom Q 


Sample size: 


4-8 [i.\ 



Pesticide standards were obtained from PolyScience 
Corp., Niles, Illinois. Compounds were quantitated by 
comparing the peak area of detected pesticides in the 
samples with those of known pesticide standards. The 
presence of detected residues was further confirmed by 
thin-layer chromatography. 



Results and Discussion 

Levels of organochlorine pesticides estimated 
neonatal blood are summarized in Tables 1-3. 



the 



The results of random sampling grouped on the basis of 
age (Table 1), dietetic habits (Table 2), and area of 
residence (Table 3) of the mother have been computed. 
Residues of total BHC (45.79 ppb) were highest in the 
neonatal blood from mothers 26-34 years old compared 
with 32.97 ppb observed in 18-25-year old mothers, 
i.e., residues were about 39% higher for the upper age 
group. Likewise, significant difference was observed in 
the levels of lindane between the two age groups 
(P<0.05). There was no variation in the concentration 
of total DDT (SDDT) residues in the two age groups. 
However, concentrations of p.p'-DDT, the parent 
compound, were about three times greater in the 
26-34-year old group compared with those in the 
18-25-year old mothers (/'<0.005). Relatively higher 
concentrations of DDT metabolites (DDE, 23.1 ppb; 
TDE, 8.01 ppb) were detected in the neonates 
associated with the older women compared with the 
younger age group (DDE, 12.33 ppb; TDE, 5.84 ppb). 

Differences in the levels of total BHC and its isomers in 
neonatal blood on the basis of vegetarian vs. nonvegeta- 
rian diets of the mother were not significant: Cord blood 
associated with vegetarian mothers contained 38.3 ppb 
BHC compared with 35.64 ppb BHC for nonvegetarian 



78 



mothers. Cord blood associated with vegetarian mother 
contained 62.22 ppb total DDT compared with 50.0' 
ppb total DDT in cord blood associated with nonvegeta 
rian mothers. BHC (47.38 ppb) was detected in th 
blood of newborns of mothers residing in urban area 
compared with 27.06 ppb in that of neonates of rura 
mothers (P<0.05). A statistically significant differenc 
(P<0.05) was also observed in the levels of lindan 
(-y-BHC) between the two residential groups. There wa 
no significant difference in total DDT residues by arej 
of residence, but a slightly higher concentration of DDlj 
was estimated in urban subjects, i.e., 22.81 ppb vs 
15.48 ppb in rural subjects. The relatively higher level 

TABLE I . Organochlorine pesticides delected (ppb) in cor* 

blood collected at term from 100 pregnant women, by age 

group 



Women 18-25 Years Old 
(58 Cases) 



Women 26-34 Years Old 
(42 Cases) 



Pesticides 


Arithmetic 






Arithmetic 


Detectted 


Range Mean 


SE 


Range 


Mean S 


Total BHC 


6,9-278.3 32,97 


16,89 


4,20-104,92 


45,79 5, 


Lindane* 


1,60-78,69 10,27 


2,18 


3,10-27,98 


14,99 1, 


p.p'DDE 


2.16-144,37 12.33 


1,98 


2,05-78,14 


23,10 4, 


p.p'-TDE 


NI>48.21 5.84 


1,25 


ND-48,21 


8,01 2, 


p.p'-DDT* 


1,43^9,21 7,30 


2,32 


ND-57,52 


22,13 2, 


SDDT' 


7 79-1029 85 49,55 


23,23 


4,59-149,62 


51 18 8, 



• Statistically significant {P<0.05 and 0,005. respectively). 
' XDDT = total DDT equivalent. 

TABLE 2. Organochlorine pesticides detected (ppb) in coi 
blood collected at term from 100 pregnant women, by 
dietetic habit 



Vegetarian Diet (36 Cases) Nonvegetarian Diet (64 Cas 



Pesticides 
Detected 



Range 



Arithmetic 
Mean 



SE 



Range 



Arithmetic 

Mean 



Total BHC 

Lindane 

p.p'DDE 

p.p'-TDE 

pp-DDT 

SDDT 



6,9-278,43 
2,1-78,68 
1,8-850 00 
NI>48 21 
ND-55,56 
403-1029,85 



38,3 
12,47 
35,33 
6,55 
14,89 
62.22 



7 29 
0.34 
23.26 
1 85 
3,05 
8,50 



4,18-104,92 

1,8-29,81 

1,9 + 150,00 

0,89-32,09 

1,78-140.00 

2.73-240,41 



35.64 
11.41 
20,53 
8,49 
17,08 
50,07 



TABLE 3. Organochlorine pesticides detected ippb) in co: 

blood collected at term from 100 pregnant women, by are 

of residence 



Urban Population (48 Cases) Rlral Popllation (52 Cas 



Pesticides 
Detected 



Range 



Arithmetic 
Mean 



SE 



Range 



Arithmetic 

Mean 



Total BHC* 2,0-507,84 



Lindane* 
p.p -DDE 
PP' 
PP' 



-TDE 
-DDT 
ZDDT 



1 28-175,73 
1 02-257,50 
ND-48,21 
5-50 23 
2,73-338,43 



47,38 
16,94 
22,81 
7,33 
13,71 
41,60 



13 87 
0,72 
7,05 
3,88 
2,19 

10,88 



3,0-76,97 

1.8-33,43 

2.2-144.37 

ND-32,09 

ND-140,00 

7,14-222,11 



27 06 
8,88 

15,48 
6,25 

17,08 

40,65 



' Statistically significant (/'<0,05 and 0,05. respectively). 



Pesticides Monitoring Journ 



f DDE compared with DDT suggest that mothers were 
xposed either to DDE or to long-term low levels of 
)DT, presumably the latter. 

lecause histories revealed no accidental or occupational 
xposure to any of the detected pesticides, subjects 
/ere exposed through the food chain and the environ- 
lent. Placental transfer is undoubtedly responsible for 
le presence of these toxicants in newborn babies. A 
ossible route of entry has been traced in Figure 1 . 

SPRAY 

(vector control and 
agricultural use) 

air pollution ''' 





INHALATION 
LUNG 



ABSORPTION 

i 
MATERNAL CIRCULATION 

PLACENTA 
CORD BLOOD 



FOOD CHAIN 
CONTAMINATION 



FIGURE 1 . Possible route of entry for pesticides into 
developing embryo. 

Relatively higher concentrations of BHC in neonatal 
lood associated with mothers in the older age group 
lay be the result of comparatively longer periods of 
xposure to this food and environmental contaminant. It 
/ould be advisable for pregnant women to avoid areas 
/here pesticides are sprayed and to decrease consump- 
lOn of fatty foodstuffs. 

Acknowledgment 

authors express their gratitude to H.O. Mishra for 
istrumental facilities and to Swaran Lata and B.K. 

iingh for technical assistance. 



LITERATURE CITED 

/) Agar^\^al, H. C. et al. 1976. Residues of DDT, its 
metabolites in human blood samples in Delhi. Bull. 
W.H.O. 54(3):394. 

2) Anonymous. 1979. Chemicals and the environment. 
Pestic. Abstr. 12(5);253. 

3) Bindra. O. S., and R. L. Kalra. 1973. A review of work 
done in India on pesticide residues. In Progress and 



Problems in Pesticide Residues Analysis. O. S. Bindra 
and R. L. Kalra, eds. Joint Publ. of PAU, Ludhiana, and 
ICAR, New Delhi, p. 9. 

(4) Brown, J. R., and L. Y. Chow. 1975. Comparative study 
of DDT and its derivatives in human blood samples in 
Norfolk County and Holland Marsh, Ontario. Bull. 
Environ. Contam. Toxicol. 13(4):483^88. 

(5) Casarett, L. J., G. C. Fryer, W. L. Yauger, and H. W. 
Klemmer. 1968. Organochlorine pesticide residues in 
human tissues — Hawaii. Arch. Environ. Health 
17(3):306-311. 

(6) Curley, A., M. F. Copeland, and R. D. Kimbrough. 
1969. Chlorinated hydrocarbon insecticides in organs of 
still-bom and blood of new-bora babies. Arch. Environ. 
Health 19(5);628-632. 

(7) Curley, A., and R. Kimbrough, 1969. Chlorinated 
hydrocarbon insecticides in plasma and milk of pregnant 
and lactating women. Arch. Environ. Health 1 8(2): 156- 
164. 

(8) Dale, W. E.. M. F. Copeland. and W. J. Hayes. 1965. 
Chlorinated insecticides in the body fat of people in 
India. Bull. W.H.O. 33:471^77. 

(9) Dale, W. £., J. W. Miles, and T. B. Gaines. 1970. 
Quantitative method for DDT and DDT metabolites in 
blood serum. J, Assoc. Off. Anal. Chem. 53(6); 1287- 
1292. 

(10) Gladden, B., and W. Rogan. 1977. Environmental 
contamination of foods for infants. Environ. Health 
Perspect. 20:248. 

(11) Gowda, T. K. S.. andN. Sethunathan. 1976. Persistence 
of endrin in Indian rice soils under flooded conditions. J. 
Agric. Food Chem. 24(4):750-752. 

(12) Grasso, C. 1975. Transplacental passage of organoch- 
lorine insecticides. In Proc. Int. Symp, on Recent 
Advances in Assessment of Health. Effects of Environ- 
mental Pollution. Commission of the European Com- 
munities, Luxembourg, pp. 861-875. 

(13) Hashemy-Tonkabony, S. E., and F. Fateminassab. 
1977. Chlorinated pesticide residues in milk of Iranian 
nursing mothers. J. Dairy Sci. 60(1 2); 1858-1 860. 

(14) Mathews. H. B.. P. R. Chen, H. M. Mahendale, and M. 
W. Anderson. 1974. The metabolism, storage and 
excretion of highly chlorinated compounds by mammals. 
In Mechanism of Pesticide Action, G. K. Kohn, ed., p. 
55. 

(15) O'Leary, J. A., J . E. Davies, W. F. Edmudson, and G. 
A. Reich. 1970. Transplacental passage of insecticides. 
Am. J. Obstet. Gynecol. 107(1 ):65-68. 

(16) Polishuk. Z. W., M. Wassermann, D. Wassermann, Y. 
Groner, S. Lazarovici, and L. Tomatis. 1970. Effects of 
pregnancy on the storage of organochlorine insecticides. 
Arch. Environ. Health 20(2):215-217. 

(17) Rappolt. R. T.. and W. E. Hall. 1968. p,p'-DDE and 
p.p'-DDT residues in human placentas, cords and 
adipose tissues. Clin. Toxicol. l(l):57-62. 

(18) Thacher, P. S. 1979. Toxic human milk may become a 
serious global problem. World Environ. Rept. 
5(I8):Aug. 16. 



'OL. 15, No. 2, September 1981 



79 



FISH, WILDLIFE, AND ESTUARIES 

Organochlorine Insecticide Residues in Soil and Earthworms in the Delhi Area, India, 

August-October, 1974 



Dharam Vir Yadav.' Pradeep K Miltal. Han C. Agarwal." and M K Krishna Pillai 



ABSTRACT 

DDT residues in soil ami earlhworms from 50 sites in Delhi 
were monitored. DDT was detected in all but nvo samples 
each of soil and earthworms. Among DDT residues. 
p,p'-DDE was most common and was found in 48 samples 
each of soil and earthworms; p.p'-DDT was detected in only 
43 soil samples and 46 earthworm samples. p.p'-TDE and 
o.p'-DDT were also present in smaller concentrations in 29 
and 15 soil samples and in 43 and 25 earthworm scmiples. 
respectively. Maximum total DDT concentration of 2 .6 ppm 
was detected in the sod from Durga Nagar in the vicinity of a 
DDT factory. The highest concentration of 37.7 ppm total 
DDT in earthworms was also obtained from the same .site. 
The maximum concentration factor found in the earthworms 
was 551. The total DDT concentration in the earthworms and 
soil showed significant correlation. 



Introduction 

Large-scale use of organochlorine insecticides, espe- 
cially DDT. by agricultural and health agencies has 
resulted in global contamination of the ecosystem (10. 
24). Because of its lipophilic tendency, coupled with its 
stability and persistence, DDT in the environment 
accumulates in nontarget organisms (10). DDT residues 
in soil are known to be concentrated by earthworms. 
Levels of DDT residues in soil and earthworms in a 
given area indicate the extent of environmental con- 
tamination over a period of time. 

DDT has been used extensively in the Delhi area for 
agricultural and mosquito control, and so this study was 
undertaken to assess the extent of DDT pollution. In 
addition, a DDT factory in Delhi might be contributing 



' R.M College. Depanmem of Zoology. Delhi-1 10007. India 

- Universilv of Delhi. Depanmem of Zoology. Delhi-1 10007. India 



to the. environmental contamination of the surroundini 
areas. 

Materials and Methods 

Soil samples and earthworms were collected from 5 
different sites in Delhi (Figure 1) from August t 
October 1974. The earthworms were of the one specie 
available in the area, Pheretima posthiima (L. Vaill 
Samples were dug from the upper 15 cm of soil, place 
in polyethylene bags, and transported to the laboraton 
within 6 hours. In the laboratory, the living earthworn( 
were removed from the soil, washed with water, an 
stored in a freezer. The soil was air-dried and mixe 
thoroughly, and at least three samples of 10 g each wei 
stored in a freezer. Physical and chemical properties ( 
the soil were not studied. 

Earthworms from each site were pooled to obtain 
sample weight of about 10 g. Pooled samples we< 
accurately weighed, and insecticide residues wej 
extracted by homogenizing the pooled samples wi| 
four times their weight of anhydrous sodium sulfate j 
acetone-hexane (1 -I- 1). The mixture was stirred forj 
hour and filtered. The residue was extracted three timij 
more with acetone-hexane (1 -I- 1). The total volunj 
of solvents used was 100 ml. The soil samples we| 
moistened, mixed with equal weights of anhydro 
sodium sulfate, and ground with a mortar and pestl 
Samples were mixed with acetone-hexane (59 -I- 4f 
shaken for 1'/: hours, and filtered. The residue w 
extracted three times more. The total volume 
solvents used was 100 ml. The extract (earthworms 
soil) was washed with 100 ml of 2% sodium sulfaij 
and the hexane layer was filtered through anhydro | 
sodium sulfate. The extract was then concentrated j 
flash evaporation and cleaned on an alumina column i| 
described by Holden and Marsden (14). The clean | 
sample was analyzed by gas-liquid chromatograp i 



80 



Pesticides Monitoring Journ 




KALKAJI TCHnf 



® 



FIGURE 1. Areas sampled for DDT residues in soil and 
earthworms in Delhi. 



LC). Instrument parameters and operating conditions 
;re as follows: 

jas-liquid chromatograph: Hewlett Packard Model 7300 series 



Jetector: 


electron-capture 


rolumn: 


coiled glass, 2 m x 4 mm ID packed with 1.5% 




SP 2250/1.95% SP 2401 on 100-120-mesh Supel- 




con AW-DMCS 


remperatures, °C: 


detector 200 




injector 200 




column 190 


_amer gas; 


nitrogen flowing at 70 ml/min 



:aks were identified by comparing relative retention 
nes with those of standards. Identifications were 
■nfirmed by GLC on another column packed with 6% 
icone DC- 11 on 80-100-mesh Chromosorb W-AW 
d 5% DEGS on 100-120-mesh Gas-Chrom Q. 
p'-DDT, p,p'-TDE, and o,p'-DUY were confirmed 



by dehydrochlorination (9). Peaks for p,/?'-DDE and 
DDMU were confirmed if they coincided with the 
dehydrochlorinated products from p,p'-DDT and p.p'- 
TDE. Further confirmation was performed by thin-layer 
chromatography of the pooled extract. Solvent systems 
used were heptane-acetone (98 -I- 2) and hexane- 
chloroform (90 -I- 10). The spots corresponding to the 
position of standards were scraped, extracted, and 
analyzed by GLC. 

Recovery of DDE, TDE, p.p'-DDT, and o.p'-DDl 
from spiked soil samples was 89.7%, 88.5%, 96.1%, 
and 91.8%; recovery was 93.6%, 93.9%, 97.8%, and 
83.7% from spiked earthworms. However, data pre- 
sented have not been corrected for recoveries. The 
detection limit of the method under the conditions used 



u. 15, No. 2, September 1981 



was about 0.1 ng for DDE, TDE, p.p'-DDT. and 
o.p'-DDT. 

Results and Discussion 

The areas from which samples were collected and the 
range of DDT and its metabolites found are given in 
Figure 1 . The levels of organochlorine residues in soil 
and earthworms, and the locations where they were 
found, are presented in Tables 1 and 2. Organochlorine 
insecticide residues detected in soil and earthworms 
were predominantly DDT and its metabolites. Tipathi 
{19} reported DDT in 120 of 138 samples analyzed 
from Tarai area in Uttar Pradesh, India. In the present 
study, residues in soil ranged from about 0.01 to 2.61 
ppm; the highest concentration was found at Durga 
Nagar (Area 17). where the DDT factory is located. 

Other areas, such as Inderlok (Area 31), I. A. R.I. (Area 
48b), and R.K. Puram (Area 36). also had appreciably 
higher concentrations of total DDT residues. Concentra- 
tions of DDT residues were below detection limits at two 
sites, Wazirabad pumping station (Area 47) and Vivek 
Vihar (Area 24). Total DDT concentration as high as 
29.45 ppm in agricultural soils (7) and 388.16 ppm in 
urban soils (5) has been reported in the United States. 
Lang et al. (75) found a maximum of 13.93 ppm total 
DDT from a survey of six U.S. Air Force Bases. The 
occurrence of DDT residues in Delhi soils might be 
predominantly attributed to volatilization and subse- 
quent dispersal of DDT in the vicinity of the factory; 
DDT has been shown to volatilize into the atmosphere 
(21), from which it ultimately reaches the surface soils. 
In addition to the dispersal from the DDT factory, 
large-scale use of DDT in the control of malaria might 
have resulted in widespread contamination of Delhi 
soils. DDT residues in soils are highly stable and persist 
for a long time (22). However, Agnihotri et al. (2) 
reported up to 959c loss of DDT in 6 months from 
agricultural soils under tropical conditions. Therefore, 
the comparatively lesser concentration of DDT in Delhi 
soils might be due to their loss under the tropical 
environment. 

In earthworms, the concentration of total DDT residues 
varied from 0.1 ppm to 37.74 ppm, with a maximum 
concentration factor of 551 (Tables 1 and 2). The 
highest concentration of DDT was detected in samples 
from Durga Nagar, where DDT concentration in the soil 
was also highest. However, the concentration factor, 
which was obtained by dividing the concentration of 
DDT in the earthworms by the concentration in the soil, 
was only 14.5 at Durga Nagar. compared with 551 at 
one site l.A.R.I. (Area 48a). Barker (3) reported total 
DDT as high as 680 ppm in Lumbricus rubellus and 492 
ppm in Helodriliis zeteki. compared with 37.7 ppm 
DDT in P . posthuma in the present investigation. There 



TABLE 1. Concentration (range in ppm) of DDT and its 

metabolites in soil and earthworms collected from different 

areas in Delhi during 1974 



SAMPL.bTYPt ;).p'-DDE o.p'-DDT p.p'-lDE /j.p'-DDT Total DD 

Soil 001-0.81 0.01-0.27 0,01-0,60 001-1,20 01-2,6 

(48) (15) (29) (43) (48) 

Eanhwi.rms 0,02-9 78 02-3,89 0,01-8,69 0,03-20 60 0,10-37,7 

(48) (25) (43) (46) (48) 

NOTE: Fitly samples each ol soil and earthworms were analyzed. Numbers 
parentheses indicate number of samples with positive detection. 



are several other reports showing the concentration ( 
DDT residues in earthworms (12, 13, 23). Total DD 
concentration in earthworms and soil from the san 
area showed significant correlation (r = 0.792; 
P<0.01). Similarly, Gish (13) observed a line: 
relationship between pesticide residues in earthworn 
and soil. Edwards and Thompson (12) obtaine 
significant correlation between residues in earthworn 
and soil from data collected by different worker 
However, Wheatley and Hardman (23) found that DD 
residues in earthworms and soil were not relate 
linearly. 

DDT in soil and earthworms was comprised mainly i 
p.p'-DDT and its metabolites /J.p'-DDE and p,/?'-TDl 
In certain samples, o,/j'-DDT was also detected, 
addition to p,p' -DDJ and its metabolites (Tables 1 ar 
2). These are commonly reported DDT components 
soils (4, 17, 18). Carey et al. (6-8) reported o.p'-DC 
and o.p'-TDE residues in addition to these common 
occurring metabolites. DDT in soils undergoes tran 
formation in the presence of various physical, chemici 
and biological factors and degrades to DDE, tl 
terminal residue of DDT (76). TDE is also formed 
the soil, mainly a result of microbial degradation (20 

The occurrence of DDT metabolites in earthworms m. 
be due either to their direct uptake from soil or 
metabolism of DDT by the earthworms (7, 77, 25). T 
proportions of DDT metabolites (DDE and TDE) 
relation to unchanged DDT showed large variations 
different soil and earthworm samples. However, 
majority of these samples contained higher concenti 
tions of p,p'-DDT than its metabolites, suggesting tl 
p.p'-DDT was being transferred quite frequently 
these soils. The higher proportions of DDE and TDE 
certain samples may be due to the faster degradation 
p,p'-DDT in soil in those particular areas; DI 
degradation depends on various environmental facto i 
Ware et al. (27) showed a shift in DDE: DDT ratio frci 
56:44 to 62:38 after 3 years in Arizona soils. T 
variable proportions of DDT metabolites in relation I 
unchanged DDT in the earthworms might have bzi 
due to variations in the duration of exposure to r 
insecticide and its concentration in the soils. 



82 



Pesticides Monitoring JouR^i' 



TABLE 2. Concentration (in ppm) of DDT and its metabolites in soil(S) and earthworms(E) from different areas in Delhi 

during 1974 



AREAS 




p.p'DDE 


o.p -DDT 


p.p'JDE 


p.p'-DDl 


Total DDT 


CoNCN Factor 


1. Old Jamuna Bridge 


s 


008 


0.01 





0,21 


0.30 




Kashmere Gale 


E 


0,32 


— 


0.01 


1.02 


1.35 


4.5 


2. Raj Ghat 


s 


0,07 


— 





0.01 


0.08 






E 


0,18 


— 


0.15 


0.81 


1.14 


14.3 


3. Lajpat Nagar 


S 


0.01 


— 





0.08 


0.09 






E 


0,23 


— 


0.24 


0.76 


1.23 


13.7 


4. Wazirpur 


S 


005 


— 


— 


0.02 


0.07 






E 


069 


0.09 


0.98 


2.41 


4.17 


59.6 


5. Azadpur 


S 


008 


— , 


— 


0.02 


0.10 






E 


003 


— 


— 


0.07 


0.10 


1.0 


5. South Extn Pt -II 


S 


0.10 


— 


0.04 


0.05 


0.19 






E 


0.03 


— 


0.10 


0.14 


0.27 


1.4 


7. Kalindi Colony 


S 


0.05 








0.01 


0.06 






E 


0.03 


— 


0.01 


0.14 


0.18 


3.0 


S. Safdaijang Enclave 


S 


006 


— 


— 


0.04 


O.IO 






E 


0.92 


005 


0.04 


0.65 


1.66 


16.6 


?. Timarpur 


S 


0.19 


— 





0.04 


0.23 






E 


005 


— 


— 


0.06 


0.11 


0.48 


). Naraina 


S 


0.05 


— 


0.50 





0.55 






E 


0.05 


0.02 


0.83 


— 


0.90 


1.6 


1. Delhi Airport 


S 


0.14 


— 


0.04 


0.20 


0.38 






E 


0.89 


0.19 


0.24 


1.13 


2.45 


6.4 


I. Kataria Nursury 


S 


0.11 


— 


— 


0.04 


0.15 




Nizamuddin 


E 


1 65 


0.37 


0.02 


1.80 


3.84 


25.6 


i. Palam Road 


S 


0.06 


— 





0.02 


0.08 






E 


0.75 


— 


— 


1.54 


2.29 


28.6 


t. Roshanara Garden 


S 


0,10 


0.02 


0.06 


0.08 


0.26 






E 


18 


— 


0.02 


0.27 


0.47 


1.8 


j. Delhi Zoo 


S 


0,03 


— 


0.02 


0.01 


0.06 






E 


0,14 


— 


0.03 


0.20 


0.37 


6.2 


5. Punjabi Bagh 


S 


0,06 


— 


0.01 


0.02 


0.09 






E 


0.40 


— 


0.68 


0.77 


1.85 


20.6 


^ Durga Nagar 


S 


0.76 


0.08 


0.57 


1.20 


2.61 






E 


5.24 


3.21 


8.69 


20.60 


37.74 


14.5 


!. Kalkaji 


S 


0.02 


— 


— 





0.02 






E 


19 


— 


— 


0.16 


0.35 


17.5 


*. Greater Kailash 


S 


0.02 


— 








0.02 






E 


0.58 


0,10 


0.08 


0.43 


1.19 


59.5 


). Govind-Puri 


S 


005 


— 


0.04 


0.04 


0.13 






E 


0.02 


— 


0.97 


0.97 


1.96 


15,1 


1. Jamia Nagar 


S 


0.15 


— 


0.03 


0.04 


0.22 






E 


0.59 


— 


0.01 


0.03 


0.63 


2.9 


!. Okhla 


S 


0.02 


— 


001 


0.02 


0.05 






E 


0.12 


— 


0.07 


0.14 


0.33 


6.6 


1. Navin Shahdara 


S 


0.10 


0.02 


0.05 


0.27 


0.44 






E 


0.26 


— 


0.03 


0.30 


0.59 


1.3 


1. V.vek Vihar 


S 
E 


— 


— 


— 


— 


— 




). Central 


S 


0.04 




0.05 


0.05 


0.14 




Secretariat 


E 


0.13 


— 


0.49 


0.27 


0.89 


6,4 


i. Geeta Colony 


S 


0.06 


0.01 


0.02 


0.05 


0.14 






E 


0.92 


— 


0.62 


1.56 


3.10 


22.1 


'. Jheel 


S 


0.03 


— 


0.01 


0.02 


0.06 






E 


1.72 


— 


— 


— 


1.72 


28.7 


i. Tilak Nagar 


S 


0.09 


— 


0.01 


— 


0.1 






E 


0.54 


— 


0.44 


0.2 


1.18 


11.8 


h Moti Nagar 


S 


0.03 


— 


— 


0.03 


0.06 






E 


6.10 


1,50 


1 90 


8.60 


18.10 


302 


). Shanti Nagar 


S 


0.01 


— 








0.01 






E 


1.20 


— 


0,05 


0.03 


1.28 


128 
















continued 


OL. 15, No. 2, 


September 1981 












83 



TABLE 2. (cont'd). 



31 Inderlok 


S 
E 


0,19 
9.78 


0,27 
2,30 


0.60 
5.63 


0.91 
9.30 


1.97 
27.01 


13.7 


32, Budha Memorial Park 


S 
E 


0.02 
0.83 


0,01 
0.02 


0.01 
0.22 


0.02 
0.62 


0.06 
1.69 


28.2 


33, Pusa Chowk Karol Bagh 


S 
E 


0.04 
0.38 


0.02 


0.03 
0.17 


0.20 
1.29 


0.27 
1.86 


6.9 


34 Pahar Ganj 


S 
E 


0,04 
0,05 


0.04 


0.01 
0.05 


0.27 
0.78 


0.32 
0.92 


2.9 


35, Ajmal Khan Park 


S 
E 


0,01 
0,02 


— 


0.10 
0.10 


0.01 
0.07 


0.12 
0.19 


1.6 


35 R K, Puram 


S 
E 


0.19 
0.87 


0.03 
0.04 


0.01 
0.08 


0.57 
2.55 


0.80 
3.54 


4.4 


37. Dhaula Kuan 


S 
E 


0.04 
0.22 


0.04 


0.03 


O.U 
1.03 


0.15 
1.32 


8.8 


38- Wazirabad 


S 
E 


0.19 
0.26 


0.01 


O.OI 
0.11 


0.38 
0.48 


0.59 
0.85 


1.4 


39, Nirankarl Colony 


S 
E 


0.02 
0.31 


0.01 
0.03 


0.01 
0.14 


0.09 
0.63 


0.13 
1.11 


8.5 


40. Radio Colony 


S 

E 


0.81 
3.16 


0.02 


0.04 
0.33 


0.16 
0.42 


1.01 
3.93 


3.9 


41, Subhadra Colony 


S 
E 


0.34 
1,55 


0.05 


0.06 
0.50 


0.89 
1.54 


0.69 
3.64 


5.3 


42. Karam Pura 


S 
E 


0.11 
0.26 


0.01 
0.09 


0.09 
0.20 


0.29 
2.13 


0.50 
2.68 


5.4 


43. Bharat Nagar 


S 
E 


0.03 
0.03 


0.02 
0.02 


0.02 
0.43 


0.17 
0.23 


0.24 
0.71 


3.0 


44. Raja Garden 


S 
E 


0.09 
0.14 


0.02 
0.02 


0.32 
0.22 


0.24 
0.34 


0.67 
0.72 


1.1 


45. Daya Basti 


S 
E 


0.12 
0.18 


0.03 
0.05 


0.06 
0.17 


0.32 
0.72 


0.53 
1.12 


2.11 


46. Delhi University 


S 
E 


0.02 
0.31 


0.26 


0.22 


0.03 
0.73 


0.05 
1.52 


30.4 


47. Wazirabad Pumping 
Station 


S 
E 


— 


— 


— 


— 


— 





48. Indian Agnc. Research 
Inst. 


S 
E 


0.02 
0.57 


3.89 


2.32 


0.01 
9.74 


0.03 
16.52 


551 


48(a) Indian Agric Research 
Inst. 


S 
E 


0.05 
0.12 


0.20 


0.08 


0.08 
0.51 


0.13 
091 


7 


48(b) Indian Agric. Research 
Inst. 


S 
E 


0.75 
0.36 


0.10 

1.77 


1.12 


0.27 

6.00 


1.12 
9.25 


8.3 



Acknowledgments 

This work was partly supported by a grant from the 
Department of Science and Technology under the Man 
and Biosphere Programme. One of the authors, D.V. 
Yadav, was a recipient of an All India University 
Grants Commission Junior Research Fellowship. 



LITERATURE CITED 

(/) Agarwal, H.C.. D.V. Yadav. and M.K.K. Pillai. 1978. 
Metabolism of '"C-DDT in Pheretima posthuma and 
effect of pretreatment with DDT, lindane, and dieldrin. 
Bull. Environ. Contam. Toxicol. 19:295-299. 

(2) Agnihotri. N.P.. S.Y. Pandey. H.K. Jain, and DP. 
Srivastava. 1977. Persistence of aldrin, dieldrin, lin- 
dane, heptachlor, and p.p'-DDT in soil. J. Enlomol. 
Res. 1:89-91. 

(i) Barker. R.J. 1958. Notes on some ecological effects of 
DDT sprayed on elms. J. Wildl. Manage. 22:269-274. 



(4) Brown. JR.. L.Y. Chow, and F.C. Chai. 1975. 
Distribution of organochlorine pesticides in an agricultu- 
ral environment, Holland Marsh, Ontario — 1970-72. 
Pestic. Monit J. 9(l):30-33. 

(5) Carey. A.E.. 1979. Monitoring pesticides in agricultural 
and urban soils of the United States. Pestic. Monit. J. 
13(0:23-27. 

(6) Carey. A.E.. P. Douglas. H. Tai. W.G. Mitchell, and 
G.B. Wiersma. 1979. Pesticide residue concentrations in 
soils of five United States cities, 1971 — Urban Soils 
Monitoring Program. Pestic. Monit. J. 13(l):17-22. 

(7) Carey. A.E.. J.A. Gowen. H. Tai. W.G. Mitchell, and 
G.B. Wiersma. 1979. Pesticide residue levels in soils 
and crops from 37 states, 1972 — National Soils Monitor- 
ing Program (IV). Pestic. Monit. J. 12(4):209-229. 

(8) Carey. A.E.. G.B. Wiersma. and H. Tai. 1976. 
Pesticide residues in urban soils from 14 United States 
cities, 1970. Pestic. Monit. J. 10(2):54-60. 

(9) Chau. A.S.Y. 1972. Analysis of chlorinated hydrocarbon 
pesticides in water and waste waters. Inland Waters 
Branch, Environment Canada, Ottawa, Ontario, Canada, 
pp. 1-56. 



84 



Pesticides Monitoring Journa 



70) Edwards. C.A. 1970. Pesticides in the Environment. 

Chemical Rubber Co., Cleveland, Ohio. 
;/) Edwards. C.A.. and K.A. Jeffs. 1974. Rate of uptake of 

DDT from soil by earthworm. Nature (London) 47:157- 

158. 

12) Edwards. C.A., and A.R. Thompson. 1973. Pesticides 
and the soil fauna. Residue Rev. 45:1-81. 

13) Gish, CD. 1970. Organochlorine insecticide residues in 
soils and soil invertebrates from agricultural lands. 
Pestic. Monit. J. 3(4):241. 

14) Holden. A.V.. and K. Marsden. 1969. Single stage clean 
up of animal tissue extracts for organochlorine residue 
analysis. J. Chromatogr. 44:481^92. 

75) Lang. J.T.. L.L. Rodriguez, and J.M. Livingston. 1979. 
Organochlorine pesticide residues in soils from six U.S. 
Air Force Bases, 1975-76. Pestic. Monit. J. 12(4):230- 
233. 

16) Maisumura. F. 1973. Degradation of pesticide residues 
in the environment. In Environmental Pollution by 
Pesticides, Vol. 3, C.A. Edwards (ed.). Plenum Press, 
London, U.K. pp. 494-513. 

17) Miles. J.R.W.. C.R. Harris, and P. Moy. 1978. 
Insecticide residues in organic soil of the Holland Marsh, 
Ontario, Canada, 1972-75. J. Econ. Entomol. 71:91- 
10!. 

18) Suzuki. M.. Y. Yamato. and T. Walanobe. 1977. 



Organochlorine insecticide residues in field soils of the 
Kitakyushu District — Japan, 1970-74. Pestic. Monit. J. 
ll(2):88-93. 

(79) Tripathi. H.C. 1966. Organochlorine insecticide re- 
sidues in agricultural and animal products in Tarai area. 
M.Sc. thesis, U.P. Agric. Univ., Pant Nagar, India. 

(20) Tu, CM., and J.R.W. Miles. 1976. Interaction between 
insecticides and soil microbes. Residue Rev. 64:17-65. 

(27) Ware. G.W.. W.P. Cahill. and B.J. Esteson. 1975. 
Volatilization of DDT and related materials from dry and 
irrigated soils. Bull. Environ. Contam. Toxicol. 14:88- 
97. 

(.22) Ware. G.W., B.J. Estesen. N.A. Buck, and W.P. Cahill. 
1978. DDT moratorium in Arizona — agricultural re- 
sidues after seven years. Pestic. Monit. J. 12(1): 1-3. 

(23) Whealley. G.A.. andJ.A. Hardman. 1968. Organochlor- 
ine insecticide residues in earthworms from arable soils. 
J. Sci. Food Agric. 19:219-225. 

(24) Woodwell. G.M.. P.P. Craig, and H.A. Johnson. 1971. 
DDT in the biosphere: Where does it go? Science 
1974:1101-1107. 

(25) Yadav, D.V.. M.K.K. Pillai. and H C. Agarwal. 1976. 
Uptake and metabolism of DDT and lindane by 
earthworm Pheretima posthuma. Bull. Environ. Con- 
tam. Toxicol. 16:541-545. 



OL. 15, No. 2, September 1981 



85 



Organochlorine Insecticide Concentrations in Fish of the Des Moines River, Iowa, 1977-78' 



Ross V. Bulkley,- Siu-Yin Theresa Leung." and John J- Richard ' 



ABSTRACT 

Organochlorine insecticides were measured in fish of the Des 
Moines River. Iowa, in 1977 and 1978 to determine whether 
concentrations exceeded allowable levels and to compare 
differences among species. Significant differences in mean 
concentrations of dieldrin. "LDDT. and hcplachlor epo.\ide in 
whole-body samples of seven species of fish, Dorosoma 
cepedianum, Carpiodes carpio, Cyprinus carpio, Ictalurus 
punctatus, Pomoxis annularis, Micropterus salmoides, Sti- 
zostedion vitreum. could not be adequately explained by body 
size, position of species in the food chain, or percent body fat. 



of southwestern Minnesota and flows southeasterly 
across Iowa to the Mississippi. It is the largest river ir 
Iowa. About 79% of the watershed upstream from De; 
Moines is cropland (primarily com and soybeans), 6^ 
is permanent pasture, 57c is forest, and 7% is urban (7) 
Normal annual precipitation over the drainage are: 
ranges from 62.5 to 77.5 cm from north to south am 
averages 70.7 cm (19). The major source of pollution ii 
the river is nonpoint agricultural runoff (8). 

Sampling and Analysis 



Introduction 

The use of organochlorine insecticides on midwestern 
farmland to control agricultural insects has caused 
widespread contamination of fish in streams and rivers. 
Dieldrin residues in catfish (Ictalurus) and buffalo fish 
(Ictiobus) caused closure of certain commercial fisheries 
in Iowa during the 1970's and generated considerable 
public concern (2, 3. 4, 9, 10, 14). Several years after 
DDT, aldrin, dieldrin, and other insecticides were 
removed from the market, these chemicals or their 
breakdown products were still present in water, 
sediment, and fish of the Des Moines River and at least 
dieldrin was evidently still being washed into the river 
from farmland (11). Leung (//) examined pesticide 
concentrations in water, sediment, and seven species of 
fish collected from 1977 to 1978 in conjunction with the 
impoundment of water behind the newly constructed 
Saylorville Dam in central Iowa. She detected no 
noteworthy seasonal or spatial differences in concentra- 
tion of dieldrin, SDDT, or heptachlor expoxide in 
whole-body analyses of Des Moines River fish. The 
portion of the study reported here concerns variation in 
insecticide residues in different species of fish. 

The Des Moines River rises in the glacial moraine area 



' This study was conducted as part of Project 2225 of the Iowa Agriculture and 
Home Economics Experiment Station, Ames, Iowa, in cooperation with the 
Iowa Cooperative Fishery Research Unit, which is sponsored by the Iowa 
State Conservation Commission, Iowa State University, and the Fish and 
Wildlife Service, US, Department of the Interior. 

^ Utah Cooperative Fishery Research Unit, Logan, UT 84322 

' Minnesota Pollution Control Agency, Roseville, MN 551 13 

■' Iowa State University, Ames, lA 5001 1 



SAMPLE COLLECTION AND PREPARATION 

Three collection sites were established on the De 
Moines River in central Iowa. The drainage area total 
about 14,530 km- above Station I at Boone, 15.081 km 
above Station 2, and 15,128 km- above Station 3 a 
Saylorville. Stream distance from Station I to Station '. 
is about 76 km. 

Fish samples were collected quarterly from Octobe 
1977 to October 1978 with gill nets, hoop nets, am 
electrofishing gear. Species analyzed for pesticid 
residues were three forage fish, including gizzard shai 
(Dorosoma cepedianum), river carpsucker (Carpiode 
carpio), and carp (Cyprinus carpio); and four piscivor 
ous fish, including channel catfish (Ictalurus pitnc 
tatus), white crappie (Pomoxis annularis), largemout 
bass (Micropterus salmoides), and walleye (Stizostedio, 
vitreum). Each species was not always collected z 
every station during each quarter, but all species wer 
collected at one or more stations each quarter 
Specimens were grouped by collection data, location 
species, and length. Authors attempted to collect sma 
juveniles within a limited length range and to avoi 
large, old fish of each species. Individuals in the sam 
group were ground together in a hand grinder and the 
mixed manually in an effort to obtain a homogenou 
mixture. Subsamples were then taken, wrapped i 
aluminum foil, and frozen until analysis. 

ANALYSIS 

The method of tissue analysis described in the Pesticid 
Analytical Manual of the U.S. Department of Healt 



86 



Pesticides Monitoring Journa 



and Human Services (18) was used, with slight 
modification. After samples were thawed, a 25-30 g 
subsample was extracted with 200 ml of 65% acetonit- 
rile-water for 5 minutes in a 1 -liter stainless steel 
blender. The samples were filtered and transferred to a 
1-liter separatory funnel; 100, ml petroleum ether, 600 
ml water, and 10 ml saturated aqueous sodium chloride 
were added. The pesticides were partitioned into the 
organic layer by vigorously shaking for 30-60 seconds. 
The aqueous layer was discarded. The petroleum ether 
layer was washed with two 100-ml portions of water to 
remove the remaining acetonitrile, and then transferred 
to a 100-ml graduated cylinder, and the recovered 
volume was recorded. The wet weights of tissue 
samples were corrected for the losses of acetonitrile- 
water mixture and petroleum ether. The extracts were 
subjected to Florisil column cleanup. The eluate was 
concentrated to 10 ml for quantification. Results were 
expressed in nanograms of pesticide per gram of fish 
tissue (ppb wet weight). 

Dieldrin, p,p'-DDE, p.p'-TDE, p,p'-DDT, and hep- 
tachlor epoxide were quantified by gas chromatography. 
Instrument parameters and operating conditions were as 
follows: 



TABLE I . Number and length of fish collected from Des 
Moines River, Iowa. J977-78 



Gas chromatograph: 

Detector: 

Columns: 

Temperatures, "C 

Carrier gas: 



Tracer 550 

^^Ni electron-capture 

packed with 10% DC-200 

packed with 4% SE-30/6% OV-210 

detector 340 
columns 210 

flowing at 90-100 ml/min 



Values were not corrected for the ca 80% recovery 
obtained in extraction. Preliminary tests revealed little 
interference from polychlorinated biphenyls (PCBs) and 
chlordane. The majority of the PCBs were present as 
Aroclor 1242 or 1246 which did not interfere in the 
other pesticide analyses. No chlordane was observed in 
water or fish samples. Pesticide detection limits were 
about 10 ppb. One of the authors, John J. Richard, 
supervised all analyses. Authors transformed data on 
pesticide concentrations to log 10 values before 
conducting analysis of variance or r-tests or computing 
correlation coefficients. 

Results 

Carp were most abundant and walleyes were least 
abundant in the collections (Table 1). Because large 
older fish were not included in the composited samples, 
mean length of samples for the seven species was 
ivithin a 120-mm range. Average length of forage fish 
ivas 56 mm less than that of piscivorous fish. 

Dieldrin and SDDT were detected in all 173 samples 
inalyzed. Heptachlor epoxide was present in quanti- 



No 



Total Length, mm 



Species 



Gizzard shad 

River carpsucker 

Carp 

Channel catfish 

White crappie 

Walleye 

Largemouth bass 



Fish 


Mean 


Range 


377 


137 


56-212 


302 


178 


76-400 


536 


151 


83-402 


86 


253 


98-487 


217 


134 


75-332 


40 


232 


144_430 


132 


225 


95-387 



fiable amounts in most samples but was not detected in 
at least 15% of the samples from a given species; it was 
not found in 33% of river carpsucker samples, 27% of 
carp samples, and 15%-23% of the samples of other 
species. Most of the samples with undetectable heptach- 
lor epoxide were collected at Station 2 in October 1977. 
Average concentrations of dieldrin and SDDT were 
somewhat similar; concentrations of heptachlor epox- 
ide, when present, were considerably lower. 

Comparison of concentrations of the three insecticides 
indicated significant differences among fish species for 
all three chemicals (Table 2). Differences were greatest 
in dieldrin concentrations (P <0.01). Levels of dieldrin 
were highest in gizzard shad and channel catfish (114 
ppb), and lowest in walleyes (28 ppb). Patterns of 
heptachlor epoxide concentrations were similar to those 
for dieldrin (P <0.01). Concentrations of SDDT were 
more similar among species, but still significantly 
different (P <0.05). 



TABLE 2. Mean insecticide concentrations in whole-body 
samples of fish from Des Moines River. Iowa, 1977-78 





No 


Concentration. 


PPB 


Species 


Dieldrin 


ZDDT 


Heptachlor 




Samples 






Epoxide 


Gizzard shad 


20 


114(14-191) 


57 (8-188) 


14 (0-68) 


River carpsucker 


39 


63 (7-197) 


64(10-329) 


7 (0-42) 


Carp 


39 


35 (13-62) 


42 (12-125) 


5 (0-23) 


Channel catfish 


17 


114(31-240) 


67 (16-136) 


16(0-42) 


White crappie 


23 


60(15-301) 


44 (6-72) 


6(0-19) 


Walleye 


11 


28 (7-62) 


76(7-138) 


2(0-6) 


Largemouth bass 


24 


58(15-182) 


65 (7-109) 


7 (0-23) 



NOTE: Range is given in parentheses. 



Levels of insecticides in the three forage species were 
compared with those found in the four piscivorous 
species to determine if bioaccumulation through the 
food chain was evident. Differences between concentra- 
tions found in the forage fish and the fish-eating species 
were not statistically significant for any of the three 



^OL. 15, No. 2, September 1981 



87 



chemicals. Average whole-body concentrations (ppb) 
were as follows; 



TABLE 4. Correlation coefficient (r) between percent body 

fat and insecticide concentrations for combined composite 

samples offish collected during July and October 1978 



Forage fish 
Piscivorous fish 



Dieldrin 
71 
65 



IDDT 

54 
65 



Heptachlor epoxide 
9 



Inasmuch as whole-body concentrations of the three 
insecticides failed to correlate significantly with posi- 
tion of species in the food chain, authors compared 
pesticide concentration to percent body fat. Only fish 
sampled during the last two quarters, July and October 
1978, were available for fat analysis (Table 3). Average 
percent body fat was highest in gizzard shad (17) and 
lowest (2) in walleyes. Fat concentrations were similar 
in July and October samples of each species except 
gizzard shad. Concentrations of fat in shad samples 
were 7% in July and 29% in October. 



TABLE 3. Average percent fat content and mean 

whole-body insecticide levels in seven species of fish 

collected in Julv and October 1978 





No 


Fat, 


Concentration, 


PPMi 








Heptachlor 


Fish Species 


Fish 


% 


Dieldrin 


SDDT 


EPO.XIDE 


Gizzard shad 


104 


17.0 


81 (0.48) 


55 (0 32) 


14 (0,08) 


River carpsucker 


72 


5,4 


45 (0,83) 


39(0,72) 


3 (0,06) 


Carp 


91 


4,5 


35 (0,78) 


45 (1,00) 


6(0 13) 


Channel catfish 


3 


8,5 


101 (1,19) 


101 (1 19) 


10(0,12) 


White crappie 


79 


2,7 


56 (2,07) 


46 (1,70) 


8 (0,30) 


Walleye 


26 


2,0 


26(1,30) 


106 (5,30) 


2 (0,10) 


Largemouth bass 


52 


4,0 


61 (1,52) 


75(1,87) 


8 (0,20) 



'Based on ppm fat shown in parentheses. 



The correlation between percentage fat and insecticide 
concentrations within each species was first examined. 
In July samples, correlation was significant at the 0.01 
level between percent fat and dieldrin and heptachlor 
epoxide levels for white crappies and between percent 
fat and SDDT for gizzard shad. In October samples, 
correlation was significant at the 0.05 level between 
percent fat and dieldrin and heptachlor epoxide in 
largemouth bass. Percent fat was not significantly 
correlated with insecticide concentrations in the other 
species. 

In combined July and October samples (Table 3), the 
relation between percent fat and dieldrin was significant 
at the 0.05 level or higher in river carpsucker, carp, 
white crappies, and largemouth bass (Table 4). Correla- 
tion coefficients for gizzard shad and walleyes, 
although not statistically significant, suggested a similar 
relation. Body fat was significantly correlated with 
SDDT only in gizzard shad, whereas correlation 
between fat and heptachlor epoxide was significant in 
both white crappies and largemouth bass. 





No 






Heptachlor 


Species 


Samples 


Dieldrin 


SDDT 


Epoxide 


Gizzard shad 


5 


0.70 


0,93* 


0.45 


River carpsucker 


9 


0,73* 


0,25 


0.69 


Carp 


8 


0,83** 


0,32 


0.26 


Channel catfish 


1 


— 


— 


— 


White crappie 


10 


0,90" 


0,41 


0.82** 


Walleye 


6 


070 


0,47 


0.46 


Largemouth bass 


13 


0,84»» 


0,36 


0.85»* 



*Significant at 0.05 probability level. 
•♦Significant at 0.01 probability level. 



But even though fish species varied widely in mean 
percent body fat, differences in concentrations of each 
of the three insecticides were evidently not caused by 
differences in body fat. When the seven species were 
compared, correlation coefficients were 0.65 for fat vs. 
whole-body dieldrin concentrations, —0.12 for fat vs. 
whole-body SDDT concentrations, and 0.80 for fat vs. 
whole-body heptachlor epoxide concentrations. These 
coefficients were not statistically significant. 

Expression of insecticide concentrations on the basis of 
fat content also failed to reduce species differences 
(Table 3). White crappies contained over 2 ppm dieldrin 
on a fat basis and gizzard shad only 0.48 ppm. 
Walleyes contained the highest SDDT concentrations 
on the basis of fat (5.30 ppm) and gizzard shad the 
lowest (0.32 ppm), whereas concentrations of heptach- 
lor epoxide in terms of fat were very low in all species. 

These relatively high levels of pesticide per unit of body 
fat in white crappies, walleyes, and other species (Table 
3) suggested one additional comparison — concentration 
of pesticide in forage fish vs. piscivorous fish on a fat 
basis, for evidence of biological magnification. Mean 
concentrations of insecticide on a fat basis in gizzard 
shad, river carpsucker, and carp (forage fish) were 
lower than those in catfish, crappies, walleyes, and bass 
(piscivorous fish) as follows: dieldrin, 0.70 ppm vs. 
1.52 ppm; SDDT, 0.68 ppm vs. 2.51 ppm; andi 
heptachlor epoxide, 0.09 ppm vs. 0.18 ppm. Thesei 
differences suggested that biological magnification ir 
the food chain was occurring. However, even though 
concentrations were seemingly higher on the basis of fai 
in all piscivorous fish than in forage fish (except foi 
heptachlor epoxide in carp), only those for dieldrin 
were significantly higher (P = 0.05, t = 3.50). 

Discussion 

Body concentrations of an insecticide frequently diffe'i 
from one species of fish to another from the same bod; 
of water. Many factors, including length and weight 



Pesticides Monitoring Journai 



age, food, fat content, enzyme systems, and trophic 
levels, have been considered by researchers to explain 
species variation in insecticide concentrations (5, 8). 
Lyman et al. (/2) and Matsumura (13) observed that 
fish species also vary greatly in their ability to 
metabolize and eliminate insecticides. Additional varia- 
tion may arise from uneven exposure due to differences 
in location of capture or time of year. In our study, five 
samples were collected over a I -year period at three 
locations on the river. Seasonal and spatial differences 
in pesticide concentrations were not statistically signi- 
ficant within species, with minor exceptions (//). 
However, fish may be captured at the same location and 
still have been exposed to different levels of pesticide. 
Bottom-dwelling species are in contact with greater 
concentrations of pesticide adsorbed on bottom and 
suspended sediment than are species occupying strata 
near the water surface where suspended sediment levels 
are lower. Whether fish can absorb pesticides directly 
from sediment in significant amounts is still uncertain. 

Percent body fat tended to explain levels of insecticides 
within certain species, as has been noted by many 
researchers (7, 6, 16, 17). but did not explain 
differences in concentrations among the seven species 
in the present study. Gizzard shad and channel catfish 
had higher percent fat in their bodies than did other 
species tested and also accumulated greater concentra- 
tions of dieldrin and heptachlor epoxide on a wet- 
weight basis. Even expression of concentrations in the 
seven species of fish on the basis of fat or oil content 
did not reduce differences in insecticide level among 
species. Reinert (16) found less difference in DDT and 
dieldrin concentrations in fish species when concentra- 
tions were expressed in terms of oil content of the fish. 

Position of a species in the food chain was related to 
insecticide concentration — especially dieldrin — in the 
present study when concentrations were expressed on 
the basis of fat content. Most striking was a 5.30-ppm 
SDDT level in the highly piscivorous walleye vs. 0.32, 
0.72, and 1.00 ppm in the three forage species. This 
relation between position in the food chain and 
insecticide level was not evident when the comparisons 
were based on whole-body concentrations instead of on 
fat content alone. Authors' data illustrate once again the 
many factors influencing insecticide dynamics in fresh- 
water fish and the difficulty in attributing differences to 
a single factor. 



LITERATURE CITED 

(/) Anderson. R. B.. and W. H. Everhart. 1966. Concentra- 
tions of DDT in landlocked salmon (Salmo salar) at 



Sebago Lake, Maine. Trans. Am. Fish. Soc. 95:160- 
164. 

(2) Anonvmous. 1970. Crisis in Iowa water. Iowa Waltonian 
12(4)': 1-3. 

(3) Bulkley, R. V. (ed.) 1977. Pesticides in Iowa surface 
waters: summary of a workshop held March 1977. Iowa 
State Water Resources Research Institute, ISWRRI-83. 
Iowa State University, Ames, Iowa. 117 pp. 

(4) Bulkley. R. V.. L. R. Shannon. andR. L. Kellogg. 1974. 
Contamination of channel catfish from agricultural 
runoff. Iowa State Water Resources Research Institute 
Completion Rept. 62. Project No. A-042-IA. 144 pp. 

(5) Bulkley. R. V., R. L. Kellogg, and L. R. Shannon. 1976. 
Size-related factors associated with dieldrin concentra- 
tions in muscle tissue of channel catfish Ictalurus 
punctatus. Trans. Am. Fish. Soc. 105:301-307. 

(6) Earnest. R. D.. and P. E. Benville. Jr. 1971. 
Correlation of DDT and lipid levels for certain San 
Francisco Bay fish. Pestic. Monit. J. 5(3):235-241 . 

(7) Iowa Department of Environmental Quality. 1976. 
Water quality management plan, Des Moines River 
basin, Des Moines, Iowa. 

(8) Johnson, D. W. 1973. Pesticide residues in fish. In C. 
A. Edwards (ed.). Environmental Pollution by Pesti- 
cides. Plenum Press, London, U.K., pp. 181-212. 

(9) Johnson. L. G.. and R. L. Morris. 1971. Chlorinated 
hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J. 
4(4):216-219. 

(10) Kellogg. R. L., and R. V. Bulkley. 1976. Seasonal 
concentrations of dieldrin in water, channel catfish, and 
catfish-food organisms, Des Moines River, Iowa — 
1971-73. Pestic. Monit. J. 9(4): 186-194. 

Ul) Leung, S. T. 1979. The effect of impounding a river on 
the pesticide concentration in warmwater fish. Ph.D. 
thesis, Iowa State University Library, Ames, Iowa. 155 
pp. Univ. Microfilm No. 8010239. 

(/2) Lyman. L. D.. W. A. Tompkins, and J. A. McCann. 
1968. Massachusetts pesticide monitoring study. Pestic. 
Monit. J. 2(3):109-122. 

(13) Matsumura. F. 1977. Absorption, accumulation and 
elimination of pesticides by aquatic organisms. In M. A. 
Q. Khan (ed.). Pesticides in Aquatic Environment. 
Plenum Press, New York, N.Y., pp. 77-105. 

(14) Morris. R. L., and L. G. Johnson. 1971. Dieldrin levels 
in fish from Iowa streams. Pestic. Monit. J. 5(1):12-16. 

(15) Ostle, B. 1954. Statistics in Research. Iowa State 
College Press, Ames, Iowa. 487 pp. 

(16) Reinert, R. E. 1970. Pesticide concentrations in Great 
Lakes fish. Pestic. Monit. J. 3(4):233-240. 

(17) Reinert, R. E.. and H. L. Bergman. 1974. Residues of 
DDT in lake trout (Salvelinus namavcush) and coho 
salmon (Oncorhynchus kisutch) from the Great Lakes. J. 
Fish. Res. Board Can. 31:191-199. 

(18) U.S. Dept. of Health and Human Services. Food and 
Drug Administration. 1970. Pesticide Analytical Manu- 
al, Vol. 1, sec. 212.1. U.S. Government Printing Office, 
Washington, D.C. 

(19) U.S. Dept. of Interior. Geological Survey. 1970. Floods 
in the Upper Des Moines River basin, Iowa. H. H. 
Schwob, Iowa City, Iowa. 49 pp. 



Vol. 15, No. 2, September 1981 



89 



Organochlorine and Metal Residues in Eggs of Waterfowl Nesting on Islands in Lake Michigan 

off Door County, Wisconsin, 1977-78 



Susan D. Haseltine, Gary H. Heinz, William L. Reichel, and John F. Moore' 



ABSTRACT 

One egg from each of 114 red-breasted merganser fMergus 
serratorj nests in 1977 and 92 nests in 1978 was collected and 
later analyzed for organochlorines, polybrominated biphenyls 
(PBBs), polychlorinated styrenes (PCSsj, and metals. One 
egg was also collected from each of the dabbling duck nests 
located. Twenty-nine of these eggs were analyzed for 
organochlorines and metals in 1977: 10 eggs were analyzed 
in 1978. All merganser eggs contained DDE, polychlorinated 
biphenyls (PCBs), and dieldrin: all but one egg collected in 
1978 contained DDT. DDE and PCS levels had declined 
since 1975 to a geometric mean of 7.4 ppm DDE and 20 ppm 
PCBs in 1977 and 7.6 ppm DDE and 19 ppm PCBs in 1978. 
Dieldrin residues in eggs had not declined from 1975 levels: 
the geometric mean was 0.78 ppm in 1977 and 0.76 ppm in 
1978. Other organochlorines were present at low levels. 
Mercury residues averaged >0.50 ppm in merganser eggs 
and had not declined since 1975 . Other metals were present 
at low levels. Dabbling ducks generally had much lower 
organochlorine and Hg residues than mergansers: DDE and 
PCBs were the only organochlorines present in the majority of 
eggs. Geometric means of PCBs and DDT in dabbling duck 
eggs did not exceed 2.0 ppm and 1 .0 ppm. respectively. PBBs 
and PCSs were detected only in a few merganser eggs, at low 
levels. Eggshell thickness for red-breasted merganser eggs 
averaged 0.359 mm in 1977 and 0.355 mm in 1978, which is 
only 2%-3% below pre-1946 thicknesses. Mallard fAnas 
platyrhynchos) eggshell thicknesses averaged 0.331 mm in 
1977 and 0.337 mm in 1978. 



Introduction 

Organochlorine residues, especially polychlorinated 
biphenyls (PCBs) (18), have been a contaminant 
problem in Lake Michigan biota for years, and fish have 
accumulated high concentrations of these lipid-soluble 
compounds (26). The build-up is especially persistent in 
the Green Bay watershed (2). Fish-eating birds nesting 
in this watershed accumulate high organochlorine 
residues (10) and exhibit significant eggshell thinning 
(6). 



In 1975, red-breasted merganser (Mergus serrator) and 
common merganser (Mergus merganser) eggs collected 
on islands off Door County, Wisconsin, contained up to 
29 ppm DDE and 113 ppm PCBs; shells were 17.7% 
thinner than eggshells collected before the use of DDT 
(27). In 1977 and 1978, authors studied the reproduc- 
tive success of mergansers on several islands in the 
same area (Figure 1). The present paper reports the 
levels of organochlorines and metals in eggs randomly 
collected from the nests of mergansers and other 
waterfowl on the islands. 

Sample Collection and Preparation 

All but two of the eggs in the present study were 
obtained from Spider, Hog, and Pilot islands (Figure !). 



OO IllAND 




LONGITUDE 



' Fish and Wildlife Service, U.S. Department of the Interior, Patuxent Wildhfe 
Research Center. Laurel, MD 20811 



FIGURE 1. Location of islands where waterfowl eggs were 

collected for residue analyses. Lake michigan. 1977 and 

1978. 



90 



Pesticides Monitoring Journal 



One red-breasted merganser nest each was found on 
Gravel and Plum islands. The main three islands were 
divided into 5-6-m transects and each transect was 
searched by at least two people. Eggs were randomly 
selected, one egg per clutch, from all merganser and 
many dabbling duck nests that contained three or more 
eggs. Nests containing fewer than three eggs were 
revisited several times and, if more eggs were added, 
then they too were sampled. 

Waterfowl nesting on the three islands during the 2-year 
study included red-breasted mergansers, common mer- 
gansers, mallards {Anas plan rhynchos). gadwalls (Anas 
strepera), and black ducks (Anas ntbripes). Red- 
breasted mergansers were by far the most prevalent 
species; eggs were taken from 1 14 nests in 1977 and 92 
nests in 1978. Common merganser nests (two) were 
found only in 1978. In 1977, 22 mallard, 4 gadwall, 
and 3 black duck nests were sampled. In 1978, eggs 
from five mallard and five gadwall nests were collected 
and analyzed for organochlorines and a few metals. 

Eggs were labeled and carried in egg cartons to the 
laboratory. Eggs were cleaned and the length, breadth, 
and weight of each was measured. Volume was 
measured by water displacement if whole and if cracked 
was considered comparable to another egg of the same 
species with the same length and breadth measure- 
ments. Because dehydration and/or loss of lipid may 
occur in embryonated eggs, a specific gravity of 1.0 
was assumed for all eggs; residue values (ppm) were 
based on egg volume (25). 

All eggs were opened at the equator and the contents 
were stored frozen in a glass jar until chemical analysis. 
Stage of embryonic development based on the mallard 
was noted. Eggshells were rinsed with membranes 
intact and air-dried for at least 2 weeks before being 
measured and weighed. Thickness was measured three 
times at the equator of each egg with a Starrett lOlOM 
micrometer having 0.01-mm graduations. A mean of 
these three values was considered the shell thickness for 
each egg. 



Statistical Analysis 

Comparisons of organochlorine and metal levels in eggs 
randomly collected during 1977 and 1978 were made by 
using a Mann-Whitney U-test. Geometric means and 
ranges and nonparametric correlations are presented 
because some organochlorines did not show a normal 
distribution. Pre- 1946 eggshell thicknesses in red- 
breasted and common mergansers, as reported by White 
and Cromartie (27), were compared with 1977 and 1978 
values by means of Student's r-test. Intercorrelations of 



residues were tested with Spearman correlation coef- 
ficients. 

Analytical Procedures 



ORGANOCHLORINES, POLYCHLORINATED STYRENES. AND 
POLYBROMINATED BIPHENYLS 

Eggs were analyzed for p,p'-DDE, p.p'-lDE, p,p'- 
DDT, dieldrin, heptachlor epoxide, oxychlordane, 
c/i-chlordane, /ra«.y-nonachlor, tw-nonachlor, endrin, 
hexachlorobenzene (HCB), mirex, toxaphene, PCB, 
PBB, and PCS residues. Samples were ground with 
anhydrous sodium sulfate and extracted in a Soxhlet 
apparatus. Extracts were cleaned on a Florisil column, 
and pesticides and PCBs were separated into three 
fractions on a SilicAR® column, as described by 
Cromartie et al. (4). The SilicAR procedure was 
modified for the 1978 samples: The cleaned extracts 
were separated into four fractions, which produces a 
discrete fraction for endrin and dieldrin (16). 

Instrument parameters and operating conditions for 
quantitation of PCB, PCS, PBB, and pesticide residues 
were as follows: 



Gas-liquid chromatograph; 



Detector: 



Columns: 



Hewlett-Packard Model 5713 or 5840A equip- 
ped with automatic sampler and digital pro- 
cessor 

"Ni 

PCBs, PCSs, pesticides: glass. 183x0.4 cm 
ID, packed with 15% OV-17/1 95% QF-I on 
100-120-mesh Supelcoport at I96-I98°C and 
with 5% methane in argon flowing at 60 
ml/min 

PBBs: glass. 183x0 4 cm ID. packed with 
3% OV-I on 80-IOO-mesh Supelcoport at 
245°C and with 5% methane in argon flowing 
at 100 ml/min 



Pesticides were measured by digital integration of peak 
areas; PCBs were estimated by comparing total area 
with that of Aroclor 1260; PCS values were estimated 
on the octachlorostyrene peak (24), and PBB values 
were based on hexabromobiphenyl. Toxaphene esti- 
mates were based on the area of two peaks eluting after 
DDT (23). 

Average percentage recoveries from spiked chicken 
eggs were DDE, 91; TDE, 97; DDT, 93; dieldrin, 99; 
heptachlor epoxide, 78; oxychlordane, 97; cis- 
chlordane, 102; fra«.y-nonachlor, 99; endrin, 90; HCB, 
75; mirex, 92; and Aroclor 1260, 101. Residue levels 
were not corrected for recovery. The lower limits of 
reportable residues were 0.10 ppm for pesticides, 0.50 
ppm for PCBs, 0.02 ppm for PBBs, and 0.05 ppm for 
PCSs. Endrin was quantified as low as 0.05 ppm in the 
1977 samples and as low as 0.02 ppm in the 1978 
samples. Residues in 63 specimens were confirmed on 
an LKB 9000 or a Finnigan 4000 Series gas chromato- 
graph-mass spectrometer (76). 



Vol. 15, No. 2, September 1981 



91 



METALS 

Analyses for chromium (Cr), lead (Pb), copper (Cu), 
zinc (Zn), cadmium (Cd), arsenic (As), and selenium 
(Se) in 1978 were performed at Patuxent Wildlife 
Research Center, Laurel. Maryland. Eggs were homo- 
genized in a Virtis blender. A 5-g portion was placed in 
a Vycor crucible for Pb, Cu, Zn, Cd, and Cr analyses, 
and a 2-g portion was placed in a 125-ml Erienmeyer 
flask for As and Se analyses. 

Pb. Cu. Zn. Cd. Cr— After drying for 2 hours at 1 10°C, 
the Vycor crucible was covered and placed in a muffle 
furnace at 200°C for 2 hours. The temperature was then 
increased to 550°C at a rate of 100°C/hr and the sample 
was left to ash overnight. The ash was cooled, 
dissolved in approximately 4 ml nitric and hydrochloric 
acids over a hot plate, transferred to a 12-ml 
polypropylene tube, and diluted to 10 ml with distilled. 
deionized water. Residues were determined by compari- 
son with aqueous standards on a Perkin-Elmer Model 
703 atomic absorption spectrophotometer. Except for 
the Pb line of 217.0 nm, the standard conditions as 
published by the manufacturer were used. 

As. Se — The 2-g sample was dissolved in 40 ml 
concentrated nitric acid over a hot plate and heated 
slowly to boil away all but 1 ml of acid, which was then 
transferred to a 50-ml polypropylene tube and diluted to 
50 ml with distilled, deionized water. Arsenic and 
selenium were determined by the method of additions 
on a Perkin-Elmer Model 403 atomic absorption 
spectrophotometer equipped with a Perkin-Elmer MHS- 
1 hydride generator. Authors performed the As analyses 
at 193.7 nm with a 59c NaBH4 reducing solution at 
1,000°C, and the Se analyses at 196.0 nm with a 10% 
NaBHa reducing solution at 900°C. 

Recoveries from spiked chicken livers ranged from 83% 
to 110%; residues were not corrected on the basis of 
these data. The lower limits of reportable residues, on a 
wet-weight basis, were 0.10 ppm for Pb, Cu, Zn, Cd, 
and Se, and 0.05 ppm for Cr and As. 

All mercury (Hg) analyses and As and Se analyses in 
1977 were made by Environmental Trace Substances 
Research Center, Columbia, Missouri. Mercury sam- 
ples were first wet-digested in nitric acid. Stannous 
chloride was added to reduce ionic Hg to elemental Hg, 
which was measured photometrically in the vapor phase 
by atomic absorption. The lower limit of quantification 
was 0.001 ppm Hg, wet weight. 

Arsenic samples of 0.25 g were added to 15 ml 
concentrated nitric acid and 1 ml perchloric acid and 
heated to fumes. The samples were cooled and diluted 
to 25 ml with distilled, deionized water. A lO-ml 
aliquot of each sample was run in duplicate on a 



Perkin-Elmer MHS-1 hydride system with a NaBH4 
pellet at 1,000°C. The lower limit of quantification was 
0.005 ppm As, dry weight. 

Selenium was determined with the Se 77' method 
outlined by McKown and Morris {21). The lower limit 
of quantification was 0.01 ppm Se, dry weight. 

Results and Discussion 

MERGANSERS 

Organochlorines — In 1977. all 114 red-breasted mer- 
ganser eggs contained PCBs, DDE, dieldrin, and DDT. 
Geometric means for these four organochlorines were 
20, 7.4, 0.78, and 0.36 ppm, wet weight, respectively. 
In 1978, all 92 of the red-breasted merganser eggs 
contained PCBs, DDE, and dieldrin; 91 of the 92 eggs 
contained DDT. Geometric means for the four residues 
were 19, 7.6, 0.76, and 0.31 ppm, respectively (Table 
1). The means of these four organochlorines did not 
change significantly (P>0.05) between 1977 and 1978, 
but the range of PCBs (up to 229 ppm in 1977, but only 
36 ppm in 1978) and of DDE (up to 28 ppm in 1977, 
but only 16 ppm in 1978) decreased. The range of 
dieldrin and DDT did not change dramatically between 
1977 and 1978. 

Although PCB values from the present study are not 
easily compared quantitatively with previous findings, 
there is a general downward trend. In 1969, Faber and 
Hickey (6) reported an arithmetic mean of 84 ppm 
PCBs, wet weight, in red-breasted merganser eggs from 
the Green Bay area. In 1975, the mean had decreased to 
45 ppm PCBs (27). Our arithmetic means were 25 ppm 
and 20 ppm, respectively. The same trend was apparent 
in DDE residues for these 4 years: 44 ppm in 1969 (6), 
16 ppm in 1975 {27). 8.3 ppm in 1977, and 8.1 ppm in 
1978. Dieldrin residues showed no such decrease; 
arithmetic means for the 4 years were 0.77 ppm in 
1969, 1.0 ppm in 1975, 0.86 ppm in 1977. and 0.81 
ppm in 1978. DDT was not reported singly in 1969. but 
in 1975 the mean (0.62 ppm) was slightly higher than in 
1977 and 1978. This is also true for TDE values. The 
mean value of 0.40 ppm reported in 1975, with 17 of 
18 eggs containing TDE, was higher than the 0.16 ppm 
and 0.07 ppm means found in 1977 and 1978, 
respectively. The incidence of TDE had also dropped 
dramatically in 1978 (Table I). A slight decrease was 
also apparent in the 1978 common merganser eggs with 
regard to DDE, PCBs, DDT, and TDE when compared 
to 1975 values {27). The 1978 dieldrin values j.v= 1.7 
ppm) were higher than those found in 1975 (.v = 0.64 
ppm). 

Other organochlorine residues were found at low levels 
in merganser eggs collected during 1977 and 1978. 
Mirex and endrin residues decreased from 1975 values 



92 



Pesticides Monitoring Journal 



TABLE 1. Organochlohne. PBB, and PCS residues in the eggs of waterfowl nesting on three Lake Michigan islands off the 

tip, of Door County, Wisconsin, J 977-78 



Hepta- 

chlor toxa. 

PCB' DDE DDT TDE DiELDRiN Epoxide phene HCB 



MlREX Endrin 



OXY 


CIS NON- 


TRANS- 


CIS- 


CHLOR- 


ACHLUR 


NONA- 


Chlor- 


DANE 




CHLOR 


DANE 



PCS 



PBB 













RED-BREASTED MERGANSER, 


1977 (114)- 












20,0' 

4,9-229' 

114' 


7.4 

2.4-28 

114 


0.36 

0.09-1.7 

114 


0.14 

ND-0.71 

97 


0.78 

0.25-2.3 

114 


0.20 0.14 0.06 0.05 0.05 

ND-0.88 ND-0.89 ND-0-3 NE>-0.25 ND-0.05 

109 57 24 12 3 


0,30 

ND-0.84 

III 


0.11 

ND-0.41 

79 


0.22 

ND-0.73 

103 


0.08 

ND-0.28 

46 


NA 


0.06 

ND-0.13 

109 














RED-BREASTED MERGANSER. 


1978 {<, 


12) 












19.0 

6.6-36 

92 


7.6 

2.3-16 

92 


0.31 

ND-0.61 

91 


0.06' 

ND-0,33 

19 


0.76 

0.20-1.9 

92 


0.22 0.27' 0.05 0.05 0.03 

ND-0.55 ND-0.64 ND-0.2 ND-0.4 ND-0.08 

91 88 11 7 28 


0.41" 

ND-0.9 

91 


0.14 

ND-0.31 

86 


0.33» 0.15' 0.04 

ND-0.67 ND-0.28 ND-0.80 

90 87 29 


NA 


COMMON MERGANSER. 1978 (2) 


40.0 
33^8 

2 


190 
19-20 

2 


0.18 
0,1-0,34 


0.07 
ND-0.11 

1 


1.7 
1.5-1.9 

2 


0.44 

2 


0.24 0.14 ND 
0.20-0,28 ND-0.37 
2 1 


ND 


0.76 
0.73-0 80 

2 


0.44 

1 


1 2 

0.96-1.5 

2 


0.22 
2 


0.08 

ND-0.25 

1 


NA 


MALLARD. 1977 (22) 


2.0 

ND-10 

18 


0.89 

ND-3.6 

21 


0.06 

ND-0.27 

4 


ND 


0.06 

ND-0.18 

2 


ND 


0,05 ND ND 
ND-0,12 

2 


ND 


0.05 
ND-0.09 

1 


ND 


0.05 

ND-0.13 

3 


ND 


NA 


ND 


MALLARD. 1978 (5) 


1.1 
0.25^.9 

5 


1.0 

0.28-4.2 
5 


ND 


ND 


0.13 

ND-0 53 

3 


ND 


ND ND ND 


ND 


ND 


ND 


0.06 

ND-0.13 

1 


ND 


ND 


NA 


GADWALL. 1977 |4> 


1.1 0.35 

0,78-2.2 0.13-0.55 

4 5 


ND 


ND 


ND 


ND 


ND ND ND 


ND 


ND 


ND 


ND 


ND 


NA 


ND 


GADWALL. 1978 |5) 


1.3 

0,73-2.5 

5 


0.80 

0.45-1.4 

5 


ND 


ND 


0.24 
ND-0.56 

4 


ND 


0.06 ND ND 
ND-0.10 

1 


ND 


ND 


ND 


0.06 

ND-0.09 

1 


ND 


ND 


NA 


BLACK DUCK. 1977 (3) 


2.2 

0.71-6.7 

3 


0.77 

0.21-2.5 

3 


ND 


ND 


ND 


ND 


ND ND ND 


ND 


ND 


ND 


ND 


ND 


NA 


ND 



NOTE; NA = no analyses performed for that substance; ND = No residue of quantifiable leveL Levels over which quantification was possible were 1 ppm for all 

chemicals e.xceptendnn.O 05 ppm( 1977). 02 ppm ( 1978). PCB = 0,50 ppm; PCS = 05 ppm. PBB = 0,02 ppm Samples with no detectable residues were calculated in 

the means as one-half the quantification level, 

' PCB as Aroclor 1260. 

^ Number in parentheses = total number of eggs analyzed. 

' Geometric mean, ppm wet weight. 

■* Range. 

' Number of total samples analyzed which contained residues of reportable level. 

' Significantly different from residues in the eggs of the same species. 1977. Mann-Whitney U-test, P < 0.01. 

' Significantly different from residues in the eggs of the same species. 1977, Mann-Whitney U-test, P < 0.025. 

" Significantly different from residues in the eggs of the same species, 1977, Mann-Whitney U-test, P < 0.005. 



(27, Table 1). In fact, mirex was detected in only 12 
and 7 eggs collected from red-breasted merganser nests 
in 1977 and 1978, respectively, and endrin in only 3 
and 28 eggs, respectively. Levels of toxaphene, 
oxychlordane, trans-nonacMor , and c/i-chlordane in- 
creased slightly, but significantly, from 1977 to 1978. 
PBBs were detected in 109 of the 114 red-breasted 
merganser eggs analyzed in 1977. and PCSs were 
detected in 29 of the 92 red-breasted merganser eggs 
analyzed in 1978 and in one of the two common 



merganser eggs. 
(Table 1). 



The residues were extremely low 



Metals — Mercury was detected in all merganser eggs in 
1977 and 1978 (Table 2). The arithmetic mean in both 
years for red-breasted merganser eggs was 0.55 ppm 
Hg, which is similar to the 0.56-ppm Hg levels found 
during 1975. The mean value of Hg in common 
merganser eggs did not differ significantly in 1975 
(0.56 ppm Hg) and 1978 (0.58 ppm). Arsenic and 



Vol. 15, No. 2, September 1981 



93 



TABLE 2. Metol residues in the eggs of waterfowl nesting on three Lake Michigan islands off Door County, Wisconsin, 

1977-78 



Species 
AND Year 












RESIDIj'ES. PPM 


Wet Weight 








Hg 


As 


Se 


Cr 


Pb 


Cu 


Zn 


CD 


Red-breasted merganser 


1977 


052' 
0.24-1 3- 
(113113)' 


0.060 

0040-0.083 

(5/5) 


0.74 
060-0.82 

(5/5) 


NA 


NA 


NA 


NA 


NA 


Red-breasted merganser 


1978 


0.51 

0.26-1.3 

(92/92) 


0.060 
ND-O.U 

(1/7) 


0.61 
0.47-1.0 

(7/7) 


0.12 

ND-0.24 

(6/7) 


0,93 
0.53-1.4 

(7/7) 


0.75 
0.54-1.0 

(7/7) 


15 
12-20 
(7/7) 


ND 


Common merganser 


1978 


0.58 

0.46-0.73 

(2/2) 


NA 


NA 


NA 


NA 


NA 


NA 


NA 


Mallard 1977 






0.08 
0.07-0.39 

(22/22) 


0.013 
ND-0.022 

(3/5) 


0.54 
28-0.81 

(5/5) 


NA 


NA 


NA 


NA 


NA 


Mallard 1978 






0.08 

0.05-0.17 

(5/5) 


NA 


NA 


NA 


NA 


NA 


NA 


NA 


Gadwall 1977 






0.07 
0.04-0.13 

(4/4) 


NA 


NA 


NA 


NA 


NA 


NA 


NA 


Gadwall 1978 






0.04 

0.03-0.12 

(5/5) 


NA 


NA 


NA 


NA 


NA 


NA 


NA 


Black duck 1977 






0.12 
06-0.19 

(3/3) 


NA 


NA 


NA 


NA 


NA 


NA 


NA 



NOTE: NA = not analyzed; ND = None detected above the level of quantification. Any egg containing less than this level of residue was averaged into the mean 

using one-half the lower limit of detection. 

' Geometric mean 

■ Range 

' (Number of samples that contained quantifiable levels of residue/number of eggs analyzed). 



selenium residues in merganser eggs were generally low 
(Table 2) and did not change from 1977 to 1978. 
Chromium, lead, copper, and zinc were detected in 
1978 in the seven eggs analyzed; geometric means were 
0.12, 0.93, 0.75, and 15 ppm, respectively. Cadmium 
was not detected at quantifiable levels. 

Banded Hens — Six red-breasted merganser hens, cap- 
tured and banded on their nests in 1977, were 
recaptured on their nests in 1978. The residues of six of 
the major contaminants in the eggs collected from these 
nests are listed in Table 3. As was the case with other 
nests checked, the only significant change between 
1977 and 1978 was the TDE residues; both the amount 
and incidence of TDE had decreased. Levels of Hg 
were slightly, but not significantly, higher in the eggs 
from the nests of banded hens; otherwise, residues were 
comparable. 

DABBLING DUCKS 

Organochlorines — Generally, organochlorine residues 
were much lower in dabbling duck than in merganser 
eggs (Table 1). DDE and PCBs were the only 
organochlorines found in the majority of dabbling duck 
eggs. Geometric means of DDE for the 2 years ranged 
from 0.35 ppm in 1977 gadwall eggs to 1.0 ppm in 



1978 mallard eggs. Geometric means for PCBs in 
dabbling duck eggs ranged from 1.1 ppm in 1977 
gadwall and 1978 mallard eggs to 2.2 ppm PCBs in 
1977 black duck eggs. Other organochlorines — DDT, 
dieldrin, toxaphene, oxychlordane, rrawi-nonachlor — 
were detected at very low levels in a few eggs. PCSs 
and PBBs were not present in any of the eggs analyzed. 

Metals — Mercury residues were also lower in dabbling 
duck eggs than in merganser eggs (Table 2). Geometric 
means ranged from 0.04 ppm Hg in 1978 gadwall eggs 
to 0.12 ppm Hg in 1977 black duck eggs. Arsenic and. 
selenium were measured in 1977 mallard eggs, and thei 
geometric means were 0.013 ppm As and 0.54 ppm Se, 
wet weight. Three of five eggs contained As; all five 
eggs contained Se. 

EGGSHELL THICKNESS 

Mean eggshell thickness for 92 randomly collected! 
red-breasted merganser eggs of less than 9 days 
incubation was 0.359 mm in 1977. In 1978, the mean 
thickness for 87 eggshells was 0.355 mm. This is a 
2.2% and 3.3% decrease from pre- 1946 values, 
respectively (Table 4). but a 14%-15% increase in thei 
shell thickness over those measured in 1969 (6) and 
1975 {27). The same pattern is reflected in common 



94 



Pesticides Monitoring Journal., 



TABLE 3. Organochlorine and mercury residues in randomly sampled eggs from clutches of ihe same six red-breasted 

mergansers in Door County. Wisconsin. 1977-78' 









Residues 


ppMWtT Weight 






Year 


DDE 


PCB 


TDE 


DDT 


DlELDRlN 


Hg 


1977 
1978 


7 5 ± 1.92' 
6' 

7.9 + 1.14 
6 


19 ± 4.3 
6 

20 ± 1.0 
6 


10 ± 012 
5 

0.06 ± 0.008 

1 


0,28 ± 0.048 
6 

0.32 i 0.066 
6 


0.67 ± 113 
6 

0.85 ± 0.145 
6 


0.62 ± 0.080 
6 

0.70 ± 0.130 
6 



' The same six nests were sampled both years. 

■ Mean ± standard error. 

' Number of samples that contained quantifiable levels of a residue. Those under that level were assigned a value of one-half the detection limit. 



merganser eggshells. The 0.414-mm mean found in 
1978 eggs was only 3.2% lower than the pre-DDT 
reports, whereas the 1975 values were 23.5% thinner. 
Mallard eggshell thickness from the study averaged 
0.331 mm in 1977 and 0.337 mm in 1978. Although 
authors could locate no measurements of mallard 
eggshell thickness from the pre-DDT era for compari- 
son with these values, they are comparable to those of 
black duck eggs from the Atlantic Flyway collected 
before the use of DDT and in 1978 (12). 

The decrease in DDE over the sampling years, rather 
than any change in residue levels of other organochlor- 
ines or metals, is most likely responsible for the 
improvement in eggshell thickness in both species of 
mergansers. DDE has been implicated in both field (3, 
6. 10) and laboratory studies (11, 20) as the primary 
cause of avian eggshell thinning. And again in this 
study, DDE was correlated with eggshell thickness in 
the red-breasted mergansers (Figure 2, r = 0.029). The 
slope of the relation was significantly different from 
zero (P<0.02). The correlation was weak, but signi- 
ficant, as was the correlation of several other organoch- 
lorines (oxychlordane, trans-nonacMor. hexachloroben- 
zene) to eggshell thickness. Because of the additional 
significant correlations, authors cannot show statistical- 
ly that decreasing residues of DDE were alone 
responsible for improved eggshell thickness in 1977 and 
1978. We do, however, feel that the evidence points to 
DDE, and that other organochlorines are correlated with 
eggshell thickness because all the major chlorinated 
hydrocarbons react similarly in biological systems and 
their residues are therefore correlated with each other 
(Table 5). The only major residue which is not 
correlated to the others is Hg. DDE residues were 
correlated to this metal in the 1978 sample. Other 
organochlorines show no such correlation. 

POTENTIAL BIOLOGICAL EFFECTS 

The relationship of contaminants and reproductive 
success of red-breasted mergansers will be thoroughly 
discussed in a manuscript now in preparation, but some 
general observations on the effects of contaminants on 
waterfowl are discussed below. PCBs were the most 



abundant contaminant found in red-breasted merganser 
eggs. The levels detected were below levels found to 
have no effect on hatchability and survival of young in 
pen studies with mallards. This is true of studies where 
both natural (5) and artificial (13) incubation were used. 
Comparable levels in the egg were associated with 
embryo mortality in ring doves (Streptopelia risoria) 
(22) and decreased growth in young chickens (Callus 
domesticus) (15). 



40 
_ 39 
I 38 
S 37 
i 36 
^ 35 
^ 34 
^0 33 

1.0 

O 32 

O 

uj 31 

30 



\ • . • J •:• • •• 






1.09(101 D°E (PP"!) 

FIGURE 2. Correlation of DDE residues (log. ppm wet 

weight) with eggshell thickness of red-breasted merganser 

eggs collected in 1977 and 1978 on islands in northern Lake 

Michigan. 

TABLE 4. Shell thickness in eggs of waterfowl nesting on 
islands in northern Lake Michigan' 

Shell Thickness, mm 



Year Red-breasted Merganser Common Merganser 



Mallard 



Pre-1946 0.367 ± 0.001=' 
(8/105)" 

1975 0.302 ± 0.004='' 

(18/178) 

1977 0.359 ± 0.002' 

(92/92) 

1978 0.355 ± 0.002' 

(87/87) 



0.426 ± 0.011=' — ' 

(3/33) 

0.314 ± 0.006* — 

(2/16) 

— 0.331 ± 0.008 
(6/6) 

0.414 ± 0.003' 337 ± 0.025 
(2/2) (4/4) 



Mean ± standard error of the mean of all eggs measured; means with 
different letters are statistically different, Student's Mest. P < 0.01. 

•' Data are from White and Cromanie (1977). 

^ No data are available. 

' (Number of clutches represented/number of eggs measured). 



Vol. 15, No. 2, September 1981 



95 



TABLE 5. Correlation of five organochlorines and mercury 

in the eggs of red-breasted mergansers. Door Coi<nt\\ 

Wisconsin. 1977-78' 







HtPTACHLOK 




Residue DDE 


DDT DitLDRIN 


Epoxide 


Hg 


1977 


PCBs II (199** 


315** 0-244** 


0.392** 


154 


DDE 


0.503** 0475** 


0,594** 


149 


DDT 


706* • 


0,661** 


035 


Dieldnn 




836** 


036 


Heplachlor epoxide 






1)40 


1978 


PCBs 0S7S** 


344** 0,459** 


0,620** 


1) 183 


DDE 


0,379** 0,498** 


692** 


207* 


DDT 


0,718** 


490** 


028 


Dieldnn 




734** 


II 1148 


Heptaehlor epoxide 






II IIM2 



Spearman Lorrelalion coefficient, 
** /•<001, 



DDE residues in the mergansers were below those 
associated with significant eggshell thinning and low- 
ered reproductive success in captive black ducks (20) 
and mallards (77), but above levels found in popula- 
tions of brown pelicans {Pelecatuis occidentalis) which 
displayed eggshell thinning and reproductive problems, 
along with a variety of organochlorine-associated 
problems (3). Dieldrin residues in the merganser eggs 
were lower than residues in the eggs of barn owls (Tyto 
alba) on a 0.5-ppm dieldrin diet over 2 years 
(Mendenhall, V., E. Klaas, and A. McLane, manu- 
script in preparation) and in the eggs of ring-necked 
pheasant (Pbasianus colchicus) on a 20-ppm dieldrin 
diet (7). Field populations of purple gallinules (Por- 
phyrula niariinlca) reproduced successfully with egg 
dieldrin residues of 9-17 ppm (9), but brown pelican 
reproduction was affected when eggs carried a dieldrin 
burden in the same range as the merganser eggs {3). 

Mercury contamination in red-breasted merganser eggs 
was above the 0.5-ppm level suggested to be associated 
with decreased hatchability in pheasant eggs (7), but 
below that found in mallard eggs from hens on a 
0.5-ppm Hg diet (7*7) and below Hg levels in two 
red-breasted merganser eggs collected near a site of Hg 
contamination in New Brunswick (S). Other metal 
residues found in merganser eggs were in the same 
range as metal residues found in eggs of other wild 
species of bird (i, 72, 77. 19). 

In spite of contaminant levels in the eggs, which have 
been associated with reproductive problems in other 
fish-eating or waterfowl species in the laboratory or 
field, red-breasted mergansers were fairly successful in 
hatching broods on the islands in Lake Michigan. 
Hatching success averaged 8\.1% in 1977 and 82.6% in 
1978. Dabbling ducks showed far lower contaminant 



levels in their eggs and averaged a little better in 
hatching success— 90.2% in 1977, 92.1% in 1978. 

Summary 

DDE and PCB residues in red-breasted merganser eggs 
collected in Door County, Wisconsin, during 1977 and 
1978 had decreased from levels found in 1975. Dieldrin 
and Hg residues in the eggs had not decreased since 
1975. Low levels of other organochlorines were found 
in the eggs. Eggshell thickness was only 2% -3% below 
that of pre-1946 eggshells, but the difference was 
statistically significant. This was a substantial increase 
from thickness measurements in 1975, which authors 
believe was primarily due to the decrease in DDE 
residues in the population. Although the contaminant 
levels in eggs are considered deleterious in other species 
and environments, and a general, low-level contamina- 
tion by many organochlorines was found, hatching 
success appeared unaffected or only marginally affected 
in the red-breasted merganser. Dabbling ducks — mal- 
lards, gadwalls, black ducks — nesting on the same 
islands laid eggs containing low levels of PCBs and 
DDE; a few eggs contained extremely low levels of 
chlordane isomers, toxaphene, and dieldrin. Hatching 
success was slightly better in dabbling duck nests than 
in merganser nests. 

Acknowledgments 

Donald White, Charles Kjos, Thomas Erdman, James 
Hale, Ronald Nicotera, James Elder, and Ruth Hine 
were of much assistance in designing, setting up, and 
discussing the study with us. Charles Kjos. Thomas 
Erdman, Richard Hoppe, Barbara Braun, Nancy Miller, 
Boyd Jones, and Patricia Heinz assisted us in collection 
of field data. The assistance of Douglas Louk, Thomas 
Heazel, Nancy Miller, and Timothy Grunwald in 
collating and analyzing data is appreciated. Eugene 
Dustman and Lowell McEwen reviewed the manu- 
script. 

LITERATURE CITED 

(7) Baxter. W. L.. R. L. Under. andR. B. Dahtgren. 1969. 
Dieldrin effects in two generations of penned hen 
pheasants. J. Wildl. Manage. 33(1):96-102. 

(2) Bertrand. G.. J. Lang, and J. Ross. 1976. The Green 
Bay watershed — past/present/future. Tech. Rep. No. 
229. Univ. Wise. Sea Grant Coll. Prog., pp. 85-96. 

(i) Blus. L. J.. B. S. Neely. Jr.. T. G. Lamont. and B. 
Mulhern. 1977 . Residues of organochlorines and heavy 
metals in tissues and eggs of brown pelicans, 1969-73. 
Pestic. Monit. J. ll(l):40-33. 

(4) Cromartie. £., W. L. Reichel, L. N. Locke. A. A. 
Betisle, T. E. Kaiser, T. G. Lamont, B. M. Mulhern, R. 
M. Proury. and D. M. Swineford. 1975. Residues of 
organochlorine pesticides and polychlorinated biphenyls 
and autopsy data for bald eagles, 1971-72. Pestic. 
Monit. J. 9(l):ll-14. 



96 



Pesticides Monitoring Journal 



(5) Custer. T. W.. and G. H. Heinz. 1980. Reproductive 
success and nest attentiveness of mallard ducks fed 
Aroclor 1254. Environ. Pollut. 21A(4):313-318. 

(6) Faber, R. A., and J. J. Hickey. 1973. Eggshell thinning, 
chlorinated hydrocarbons, and mercury in inland aquatic 
bird eggs, 1969 and 1970. Pestic. Monit. J, 7(l):27-36. 

(7) Fimreite, N. 1971 . Effects of dietary methylmercury on 
ring-necked pheasants. Can. Wildl. Serv. Occas. Paper. 
No. 9, 39 pp. 

(8) Fimreite, N.. W. Holsworth. J. A. Keith. P. Pearce. and 
I. Gruchy. 1971. Mercury in fish and fish-eating birds 
near sites of industrial contamination in Canada. Can. 
Field Nat. 85(3):211-220. 

(9) Fowler, J. F.. L. D. Nevvsom. J. B. Graves. F. L. 
Bonner, and P. E. Schilling. 1971. Effect of dieldrin on 
egg hatchability, chick survival and eggshell thickness in 
purple and common gallinules. Bull. Environ. Contam. 
Toxicol. 6(6):495-501. 

UO) Gilman, A. P.. G. A. Fox, D. B. Peakall. S. M. Teeple. 
T. R. Carroll, and G. T. Haymes. 1977. Reproductive 
parameters and egg contaminant levels of Great Lakes 
herring gulls. J. Wildl. Manage. 41(3):458-468. 

(//) Haegele. M. A., and R. H. Hudson. 1974. Eggshell 
thinning and residues in mallards one year after DDE 
exposure. Arch. Environ. Contam. Toxicol. 2(4):356- 
363. 

(12) Haseltine. S. D.. B. M. Mulhern. and C. Stafford. 1980. 
Organochlorine and heavy metal residues in black duck 
eggs from the Atlantic Flyway, 1978. Pestic. Monit. J. 
14(2):53-57. 

(13) Haseltine. S. D.. and R. M. Prouty. 1980. Aroclor 1242 
and reproductive success of adult mallards (Anas 
platyrhynchos). Environ. Res. 23(l):29-34. 

(14) Heinz. G. H. 1979. Methylmercury: Reproductive and 
behavioral effects on three generations of mallard ducks. 
J. Wildl. Manage. 43(2):394-401. 

(15) Holleman. K. A.. B. D. Barnett, and G. W. Wicker. 
1976. Response of chicks and turkey poults to Aroclor 
1242. Poult. Sci. 55(6):2354-2356. 

(16) Kaiser. T. E.. W. L. Reichel. L. N. Locke. E. 
Cromartie. A. J. Krynitsky, T. G. Lamont, B. M. 
Mulhern. R. M. Prouty. C. J. Stafford, and D. M. 
Swineford. 1980. Organochlorine pesticide, PCB, and 



PBB residues and necropsy data for bald eagles from 29 
states — 1975-77. Pestic. Monit. J. 13(4):145-149. 

(17) King, K. A.. D. L. Meecker. and D. M. Swineford. 
1980. White-faced ibis populations and pollutants in 
Texas, 1969-1976. Southwest. Nat. 2(25):225-240. 

(18) Kleinerl. S. 1976. The PCB problem in Wisconsin. Rep. 
to Environ. Qual. Comm., Wise. Assembly, Madison, 
Wisconsin. 23 pp. 

(19) Lincer. J. L.. and B. McDuffte. 1974. Heavy metal 
residues in the eggs of wild American kestrels (Faico 
sparverius Linn.). Bull. Environ. Contam. Toxicol. 
12(2);227-232. 

(20) Longcore, J. R., F. B. Samson, and T. W. Whittendale. 
Jr. 1971. DDE thins eggshells and lowers reproductive 
success of captive black ducks. Bull. Environ. Contam. 
Toxicol. 6(6):485-490. 

(21) McKown. D. M., and J. S. Morris. 1978. Rapid 
measurement of selenium in biological samples using 
instrumental neutron activation analysis. J. Radioanal. 
Chem. 43(1):41 1-420. 

(22) Peakall. D. B., and M. L. Peakall. 1973. Effect of a 
polychlorinated biphenyl on the reproduction of arti- 
ficially and naturally incubated dove eggs. J. Appl. Ecol. 
10(3):863-868. 

(23) Prouty. R. M.. W. L. Reichel. L. N. Locke. A. A. 
Belisle, E. Cromartie, T. E. Kaiser, T. G. Lamont, B. 
M . Mulhern. and D. M. Swineford. 1977. Residues of 
organochlorine pesticides and polychlorinated biphenyls 
and autopsy data for bald eagles. 1973-74. Pestic. 
Monit. J. 11(3):134-137. 

(24) Reichel. W. L., R. M. Prouty. and M. L. Gay. 1977. 
Identification of polychlorinated styrene compounds in 
heron tissues by gas-liquid chromatography-mass spec- 
trometry. J. Assoc. Off. Anal. Chem. 60(l):60-62. 

(25) Stickel. L. F., S. N. Wiemeyer, and L. J. Blus. 1973. 
Pesticide residues in eggs of wild birds: Adjustment for 
loss of moisture and lipid. Bull. Environ. Contam. 
Toxicol. 9(4):193-196. 

(26) Veith. G. D. 1975. Baseline concentrations of polychlor- 
inated biphenyls and DDT in Lake Michigan fish, 1971. 
Pestic. Monit. J. 9(l):21-29. 

(27) White. D. H.. and E. Cromartie. 1977. Residues of 
environmental pollutants and shell thinning in merganser 
eggs. Wilson Bull. 89(4):532-542. 



Vol. 15, No. 2, September 1981 



97 



Persistence of Dieldrin in Water and Channel Catfish from the Des Moines River, Iowa, 1971-73 

and 1978' 



Siu-Yin Theresa Leung,- Ross V. Bulkley,' and John J. Richard^ 



ABSTRACT 

This study was conducted to determine if dieldrin concentra- 
tions in water and fish of the Des Moines River. Iowa, 
decreased after registration of the compound was withdrawn 
by the Environmental Protection Agency in 1975 . Mean June 
concentrations of dieldrin in river water decreased from 50 
ppt in 1971 to 11 ppt in 1978. Average daily transport of 
dieldrin was 156 g in 1971 and 70 g in 1978. Juh levels in 
channel catfish muscle were 75 ppb in 1973 and 46 ppb in 
1978. Dieldrin was still present in significant concentrations 
in the aquatic system 3 years after registration withdrawal. 

Introduction 

Des Moines River, the largest river in Iowa, rises in the 
glacial moraine area of southwestern Minnesota and 
flows southeasterly across Iowa to the Mississippi River 
(Figure 1). About 79% of the watershed upstream from 
Des Moines in central Iowa is cropland, primarily com 
and soybeans; 6% is permanent pasture, 5% is forest, 
and 7% is urban (2). Normal annual precipitation over 
the drainage area ranges from 62.5 to 77.5 cm from 
north to south and averages 70.7 cm (9). Monthly 
precipitation is usually greatest in June. Heavy rainfall 
and cloudbursts occasionally cause high river flows in 
summer and early fall. The major source of pollution in 
the river is nonpoint agricultural runoff (2). 

From 1961 to 1965, aldrin was applied to Iowa soil at 
the rate of 5-6.5 million pounds per year for control of 
western com rootworm. Use decreased to 2 million 
pounds annually by 1973 as root worms became 
increasingly resistant to aldrin (5). Although use of 
aldrin was finally banned by the U.S. Environmental 
Protection Agency in 1975, this compound and its 



' This siudy was conducted by the Iowa Cooperative Fishery Research Unit as 
part of Project 2225 of the Iowa Agiicuhure and Home Economic Experiment 
Station, Ames. Iowa, in cooperation with the Iowa State Conservation 
Commission, Iowa Stale University, and the Fish and Wildlife Service. U.S. 
Department of the Interior. 

■ Minnesota Pollution Control Agency, Roseville, MN 55113 

' Utah Cooperative Fishery Research Unit. Logan. UT 84322 

'' Iowa State University, Ames, lA 50011 



degradation products are still being detected in the 
aquatic environment. 

From 1971 to 1973, Kellogg and Bulkley {4. 5) studied 
seasonal dieldrin concentrations in river water, channel 
catfish (Ictalurus putictatiis) , and catfish-food organ- 
isms. During 1977 and 1978, Leung conducted another 
study of the Des Moines River (6), including the 
collection site used by Kellogg and Bulkley. In the 
present study, authors compare dieldrin levels in water 
and fish of the Des Moines River, Iowa, before and 
after banning of the parent compound, aldrin. 




Saylorville 



Des Moines I 



• Collection sution 



10 10 20 30 40 50 
I I \ I I I I 

Scale m mdes 



FIGURE 1 . Des Moines River watershed including common 
sampling site of Kellogg and Bulkley (5) and present study. 



98 



Pesticides Monitoring Journal 



The common collection site of Kellogg and Bulkley (4. 
5) and the present authors is located near Boone, about 
426 km (265 miles) upstream from the mouth of the 
river. Drainage area of the stream above this point is 
about 14.530 km- (5,610 square miles). Some calcula- 
tions on river flow and sediment load were based on 
data collected by the U.S. Geological Survey (11-14) at 
Saylorville, Iowa, 76 km downstream from Boone. 

Materials and Methods 

WATER 

From April through November, single 1 -liter water 
samples were collected monthly during 1971, two 
1 -liter samples were collected weekly or at 2- week 
intervals during 1972, three 2-liter samples were 
collected twice weekly or weekly during 1973 (5), and 
single 4-liter samples were collected weekly or at 
2-week intervals during 1978. In 1971, 1972, and 1973, 
samples were collected by submerging a clean glass 
container approximately 30 cm below the water surface 
and sealing it with a Teflon- or aluminum-foil-lined 
screw cap. The 1978 samples were similarly collected 
in a stainless steel sampling bucket and stored in amber 
reagent bottles sealed with Teflon-lined screw caps. 

Unfiltered samples were extracted twice with 60 ml of 
15% ethyl ether-hexane in 1971 and with 60 ml hexane 
in 1972 (75). Extracts were combined and concentrated 
to 1 ml in a Kudema-Danish evaporator for quantita- 
tion. The 1973 and 1978 samples were filtered through 
pre-extracted Whatman No. 40 filter paper to separate 
the dissolved from the suspended fractions. The filter 
paper containing the suspended pesticides was Soxhlet- 
extracted with 300 ml acetonitrile for 18 hours. The 
pesticides were then partitioned into petroleum ether by 
adding 1,200-1,400 ml redistilled water and extracting 
with 180 ml petroleum ether. Florisil cleanup was 
applied on 1972 samples but not on 1978 samples. The 
samples were concentrated to 1 ml for quantitation, as 
described above. 

The dissolved fraction (filtrate) of the samples was 
analyzed for pesticide residues differently in 1973 than 
in 1978. In 1973, the filtrate was extracted twice with 
120 ml of 15% ethyl ether-hexane, followed by a third 
extraction with 150 ml hexane. The extracts were 
combined and concentrated to 1 ml for quantitation. 
Florisil cleanup was applied when necessary. In 1978, 
macroreticular resin, XAD-2, was used to extract 
dissolved pesticides (3). The filtrate was decanted into a 
5-liter glass reservoir and passed through a resin column 
by gravity at a flow rate of 20-30 ml/min. The 
pesticides were eluted from the column with 30 ml 
diethyl ether into a 60-ml separatory funnel. The first 
20-ml portion was collected and passed through the 
column again. Then a fresh 10-ml portion of ether was 



passed through and combined with the original 20 ml. 
The water layer was drained from the separatory funnel 
and the final traces of water were removed from the 
eluate by adding 10-15 ml petroleum ether and 2-3 g 
anhydrous sodium sulfate. The mixture was shaken 
about 30 seconds and the extract was transferred to a 
concentration flask. The sample was then concentrated 
to 1 ml for quantitation without further treatment. 

nsH 

Channel catfish were collected with gill nets and hoop 
nets and by electrofishing. The samples were grouped 
by collection data and total length. Samples of dorsal 
muscle tissue from individuals in the same group were 
ground, pooled, homogenized, wrapped in aluminum 
foil, and frozen until analysis. Tissues were analyzed by 
the method described in the Pesticide Analytical 
Manual of the U.S. Department of Health and Human 
Services (10), with slight modification. After the 
samples were thawed, 20-65 g subsamples were 
extracted with 200-350 ml of 65% acetonitrile-water 
for 5-10 minutes in a 1-liter blender. The samples were 
filtered and transferred to a 1 -liter separatory funnel, to 
which 100 ml petroleum ether, 600 ml water, and 10 ml 
saturated aqueous sodium chloride were added. The 
pesticides were partitioned into the organic layer by 
vigorously shaking 30-60 seconds. The aqueous layer 
was discarded and the petroleum ether layer was 
washed twice with 100 ml water. Interferences were 
removed by Florisil cleanup; additional charcoal 
cleanup was used in 1973. The elution was concentrated 
to 1-10 ml for quantitation. The wet weights of tissue 
samples were corrected for losses of the acetonitrile- 
water mixture and petroleum ether. Concentrations 
were expressed in nanograms of pesticide per gram of 
fish tissue (ppb) on a wet-weight basis. 

QUANTinCATION 

Instrument parameters and operating conditions for 
quantification and confirmation were as follows: 



1971. 1972. and 1973 
Gas chromatograph; 
Detector: 
Columns; 



Carrier gas: 

I97S 

Gas chromatograph: 

Detector: 

Columns: 



Carrier gas: 



Beckman GC-5 

discharge electron-capture 

packed with 5<7<: OV.210, at 180°C 

packed with a mixture of 1 .59f OV- 17 and I 95% 

QF. at 200°C 

helium flowing at 100 ml/min 

Tracor. Model 550 

''^Ni electron-capture, maintained at 340°C 

packed with 10% DC-200, at 210°C 

packed with a mixture of n OV-210 and b% 

SE-LTOat 210°C 

nitrogen, flowing at 90-100 ml'min 



Values obtained were not corrected for percent recov- 
ery. Detection limits were approximately 10 ppt for 
water and 10 ppb for fish tissue. All analyses were 
conducted under the supervision of one of the authors, 



Vol. 15, No. 2, September 1981 



99 



John J. Richard, at the Ames Laboratory, U.S. 
Department of Energy, Iowa State University, Ames, 
Iowa. 

Results 

Dieldrin is transported in rivers in two forms: dissolved 
in the water and adsorbed on suspended sediment and 
organic material. During the study period, combined 
(total) concentrations of dissolved and suspended 
dieldrin in the Des Moines River tended to be highest in 
June and July, although monthly differences were much 
less in 1973 and 1978 than earlier (Table 1). Kellogg 
and Bulkley (5) attributed this seasonal trend to 
application of aldrin to farmland during the April-May 
planting season and to spring rainfall. For the period 
May-October 1971-1973, mean combined dieldrin 
concentrations decreased 70% (from 30 to 9 ppt), 
whereas the difference between 1973 and 1978 concen- 
trations (9 vs. 7 ppt) was not statistically significant. 



TABLE 2. Monthly mean dissolved and suspended dieldrin 

concentrations in Des Moines River water near Boone, 

Iowa, 1973 and 1978 







1973' 






1978 






No OF 


CONCN. 


NO/LITER 


No of 


CONCN. 


NO/LITER 














Measure- 


Dissolved Suspend- 


Measure- 


Dissolved Suspend- 


Month 


ments 




ED 


ments 




ED 


April 
May 
June 


2 
7 
8 


12 
6 
6 


3 
3 

4 


4 

5 
4 


2 
3 
5 




July 
August 
Seplember 
October 


7 
6 
4 
3 


8 
4 
3 
3 


4 
2 
2 

1 


3 

4 
4 

3 


5 

2 
2 
1 




November 


1 


1 


1 


2 


1 




Overall mean 


5 


3 




3 


4 



' Kellogg (4). 

TABLE 3. Mean daily stream flow and sediment 
load, Des Moines River, Iowa — Ma\ to October, 1971-73, 
1978' 



TABLE 1 . Monthly mean dieldrin concentrations in Des 
Moines River water near Boone, Iowa 



Mean Daily Stream Flow. 

M'/SEC 



Mean Sediment Load, mg/liter 

















Month 


1971 


1972 


1973 


1978 


1971 


1972 


1973 


1978 




Mean 


concentration, ngliter' 


% Total in 
Dissolved State 






May 

June 

July 

August 

September 

October 

Mean 


66.1 

110.9 

979 

14.7 

5.7 

4.3 

49,9 


137,9 
116,4 
83,6 
114,9 
42.3 
59,7 

92,5 


244,6 
175,1 
92,5 
26,4 
44,2 
186,4 

128,2 


105,6 
132,3 
161,1 
82.1 
94.0 
70.8 

107.6 


205 

390 

300 

61 

35 

7 

166 


459 
287 
275 
420 
212 
233 

314 


448 
384 
377 
205 

245 
357 

336 


93 
196 


Month 


1971 


1972 


1973 


1978 


1973 


1978 


256 
173 


May 
June 
July 
August 


10(1) 
50(1) 
40(1) 
30( 1 ) 
30( 1 ) 
20(1) 

30 


10(4) 

24(5) 
23(2) 
10(2) 
10(1) 
10(1) 

11 


8(7) 
10(8) 
12(7) 
6(6) 
4(4) 
3(3) 

9 


5(5) 
11(4) 
8(3) 
5(4) 
8(4) 
6(3) 

7 


74 
63 
64 
67 
62 
60 

65 


61 
46 
64 
43 
28 
18 

43 


334 
55 

184 


September 
October 

Mean 


' 1971-73 data from 


Kellogg (-4) and 


Kellogg 


and Bu 


Ikley (5). 







NOTE: Number of measurements in parentheses. 
' 1971-73 data from Kellogg (-4). 



One apparent difference was that the percentage of 
dieldrin in the dissolved state decreased on the average 
from 65% in 1973 to 43% in 1978 (Table 1). The 
percentage was similar only in July of the 2 years 
(64%). Inasmuch as dieldrin is more readily available to 
aquatic organisms in the dissolved state, concentrations 
in dissolved and suspended states were examined for the 
2 years for which data were available (Table 2). 
Dissolved dieldrin levels were slightly lower each 
month (except November) in 1978 than in 1973, but 
differences were not statistically significant. 

Changes in pesticide residues in the aquatic habitat may 
also be compared on the basis of estimated amounts of 
the chemical being transported downriver. Estimates are 
based on concentrations in the dissolved and suspended 
states, stream flow, and sediment load. Mean stream 
flow on sampling days was lowest in 1971, the year 
when concentrations of total dieldrin were highest 
(Table 3). Flows in 1973 were the highest on the 



TABLE 4. Estimated transport of dieldrin in Des Moines 
River. Iowa. 1971-73. 1978 

Dieldrin. g/day 



Month 


1971 


1972 


1973 


1978 


May 


57 


119 


169 


46 


June 


479 


242 


151 


126 


July 


338 


166 


96 


111 


August 


38 


99 


14 


35 


September 


15 


36 


15 


65 


October 


7 


52 


58 


37 


Mean 


156 


119 


84 


70 



average for the 4 years of sampling. Stream flow for thei 
6-month sampling period averaged 20.6 mVsec higher, 
and mean sediment concentration averaged 152 mg/ 
liter greater, in 1973 than in 1978. Data summarized in 
Tables 1 and 2 were used to estimate dieldrin transport. 
Variation in daily amounts was greatest in 1971, when 
479 g/day was transported in June and only 7 g/day in 
October (Table 4). Variation was least in 1978, 35-126 
g/day. Mean daily transport decreased continuously 
from 1971 to 1978, from 156 to 70 g/day. Total amount 



100 



Pesticides Monitoring Journal 



of dieldrin transported down river during the period 
May-October decreased rapidly from 1971 to 1973 and 
then leveled off (Figure 2). Rate of annual decrease was 
5 kg/year between 1971 and 1972, 6.5 kg/year between 
1972 and 1973, and only 0.5 kg/year from 1973 to 
1978. 



1971 1972 1973 1974 1975 1976 1977 1978 

FIGURE 2. Estimated amounts of dieldrin transported in the 

Des Moines River past Boone, Iowa. May to October 

1971-78. 



Concentrations in muscle tissue of channel catfish were 
examined next to determine if dieldrin residues in fish 
had decreased. Comparisons of dieldrin in Des Moines 
River catfish were made on fish of similar length 
captured during the same season of the year (/). Under 
these restrictions, only data on catfish 201-300 mm in 
total length, collected from June to September, were 
compared (Table 5). Concentrations were higher in 
1973 than in 1971 in all months except June. Mean 
levels for the 4-month period were 43 ppb in 1971 and 
86 ppb in 1973. Comparison of data for July suggested 
a 39% reduction in concentration from 1973 to 1978. 



TABLE 5. Dieldrin concentrations in the muscle tissue of 

channel catfish 201-300 mm long from the Des Moines River 

near Boone. Iowa. 1971. 1973, and 1978 





1971 






1973' 






1978 




No OF 


Dieldrin. 


No Of Dieldrin. 


No OF 


Dieldrin. 


Month 


Fish 




PPB 


Fish 




PPB 


Fish 


PPB 


June 


9 




33 


12 




22 





_ 


July 


6 




61 


12 




75 


8 


46 


August 


4 




35 


12 




133 








September 


3 




44 


12 




113 


— 


— 



' Data from Kellogg 14) and Kellogg and Bulkley 15). 



Discussion 

It is not uncommon for pesticide residues in water to 
increase with rainfall and stream flow. Dieldrin 
concentrations might vary directly or inversely with 
flow in the Des Moines River (5). The amount of 
pesticide transported by any one storm depends on 
variables such as duration of storm runoff, antecedent 
soil/moisture conditions, rainfall intensity, and the 
source of runoff in the watershed. During the study 
years, most Iowa farmland was plowed in late fall so 
that the land was clear of vegetation in early spring 
when final preparations, including aldrin application, 
were made for planting. Heavy rains during the spring 
sometimes transport huge quantities of soil from the 
bare fields into the streams. Dieldrin concentrations 
may follow sediment and flow levels on these occa- 
sions. Over half the sediment in Iowa streams comes 
from sheet erosion of the land. Later in the growing 
season, when vegetation covers much of the soil and 
tends to trap sediments, a higher proportion of the 
suspended sediment resulting from rainfall may be due 
to sloughing of the river banks. Thus, dieldrin 
concentrations under these conditions may be unrelated 
to flow or suspended sediment levels. Timing of rainfall 
and runoff in relation to time of aldrin application also 
complicates the relationship between flow and dieldrin 
concentrations in river water. In our study we made 
monthly comparisons to depress day-to-day differences 
in dieldrin concentrations in water that resulted from 
these variables. 

Dieldrin concentrations in the Des Moines River 
decreased greatly from 1971 to 1973 but not significant- 
ly from 1973 to 1978. During July, concentrations in 
catfish muscle were lower in 1978 than in 1973, but the 
difference was less than that between monthly samples 
in 1973, and between several 1971 and 1973 samples. 
Inasmuch as dieldrin was banned in 1975, these data 
demonstrate the persistence of this compound in the 
environment. Our data suggest that dieldrin is still being 
washed into the river from croplands. Even after surface 
transport ceases, the long half-life of this chemical 
under certain environmental conditions indicates that it 
will be present in the river for some years. Nash and 
Woolson (7) repojted that dieldrin in soils had a 
half-life of 8-10 years. In certain watersheds, dieldrin 
half-life was 4-9 years (5). Differences in analytical 
techniques used in the authors' two studies could have 
resulted in an underestimate of the rate of decrease from 
1971 to 1978 because the later techniques used were 
presumably more accurate; however, considerable diel- 
drin was obviously still present in the river and in 
channel catfish in 1978. 

LITERATURE CITED 

(/) Bidkley. R. V.. R. L. Kellogg, and L. R. Shannon. 1976. 
Size-related factors associated with dieldrin concentra- 



VoL. 15, No. 2, September 1981 



101 



tions in muscle tissue of channel catfish. Icla/nrns 
punclatiis. Trans. Am. Fish. Soc. 105(2):301-307. 
(2) Iowa Depanmeni of Environmenlal QualiTy. 1976. 
Water quality management plan, Des Momcs River 
basin, Des Moines, Iowa. 

(i) Junk. G.A..J.J. Richard. M. D. Gneser. D. Witiak. J. 
K. Witiak. M. D. Aiguello. R. Vick. H. J. Svec, J. S. 
Fritz, and C. V. Colder. 1974. The use of macroreticu- 
lar resins in the analysis of water for trace organic 
contaminants. J. Chromatogr. 99:745-762. 

(4) Kellogg. R. L. 1974. Dieldrin contamination of channel 
catfish, invertebrates and minnows from the Des Moines 
River. M.S. thesis, Iowa State University, Ames, Iowa. 
115 pp. 

(5) Kellogg. R. L.. and R. V. Bulkley. 1976. Seasonal 
concentrations of dieldrin in water, channel catfish, and 
catfish-food organisms, Des Moines River — Iowa, 1971- 
1973. Pestic. Monit. J. 9(4):186-194. 

(6) Leung. S. T. 1979. The effect of impounding a river on 
the pesticide concentration in warm water fish. Ph.D. 
thesis, Iowa State University. Ames, Iowa. 155 pp. 
Univ. Microfilm No. 8010239. 

(7) Nash. R. G.. and E. A. Woolson. 1967. Persistence of 
chlorinated hydrocarbon insecticides in soils. Science 
157:924-927. 



(S) Schnoor, J . 1979. Pesticide trends in Iowa rivers. 3rd 

Ann. Conf. Water Qual. Corps Eng. Reservoirs, March 

21, 1979, Iowa City, Iowa. 3 pp. 
(9) Schwob. H. H. 1970. Floods in the upper Des Moines 

River basin, Iowa. U. S. Geological Survey, Iowa City, 

Iowa. 49 pp. 
{10) U.S. Department of Health and Human Services. Food 

and Drug Administration. 1970. Pesticide Analytical 

Manual, Vol. 1, Sec. 212.1. U.S. Government Printing 

Office, Washington, DC. 
(//) U.S. Department of the Interior. Geological Survev. 

1972. 1971 Water resources data for Iowa. Iowa City, 
Iowa, 349 pp. 

(12) U.S. Department of the Interior. Geological Survey. 

1973. 1972 Water resources data for Iowa. Iowa City, 
Iowa. 303 pp. 

(13) U.S. Department of the Interior. Geological Survey. 

1974. 1973 Water resources data for Iowa. Iowa City, 
Iowa. 335 pp. 

(14) U.S. Department of the Interior. Geological Survey. 
1978. 1977 Water resources data for Iowa. Iowa City, 
Iowa. 259 pp. 

(15) U.S. Environmental Protection Agency. 1971 . Methods 
for organic pesticides in water and wastewater. National 
Environmental Research Center, Cincinnati, Ohio. 38 
pp. 



102 



Pesticides Monitoring Journal 



DDT and BHC Residues in Some Body Tissues of Goats, Buffalo, and Chickens, Lucknow, India 



Bliupendra S Kaphalia and Tejeshwar D. Seth' 



ABSTRACT 



Materials and Methods 



Muscle, liver, brain, and abdominal body fat samples of 
goals, buffalo, and chickens, all common meal sources in 
India, were analyzed by gas-liquid chromalography (GLC)for 
residues of DDT and benzene hexachloride (BHC). A few 
samples of goat and buffalo bone marrow were also included. 
Relatively high residue levels were found in body fat and bone 
marrow compared with other tissues. DDT and BHC residue 
levels were highest in chicken body fat, averaging 4.157 ppm 
^DDT and 3.879 ppm BHC. DDT content was much higher in 
goat and buffalo bone marrow than in the corresponding body 
fat. DDT levels in brain samples were highest (0.138 ppm) in 
buffalo. p.p'-TDE levels were higher than p.p'-DDE levels in 
buffalo: overall DDT levels were lowest in goats. BHC 
residues were generally low in buffalo: a-BHC accounted for 
most BHC residues in brain tissues. Greater accumulations of 
DDT and BHC were found in leg muscles than in breast 
muscles of chickens. 

Introduction 

Pesticide residues in animals and poultry killed to meet 
human food needs are an important source of human 
pesticide burdens. Pesticide residues in human foods, 
especially meat products, have been sufficiently 
documented in many countries (2, 4. 6, 8, 10). About 
half the observed pesticide residues in human diets are 
of animal origin (5, 13). High levels of pesticide 
residues have been detected in the meat or in food 
cooked in animal fat (15) and about 35'7f-40% of the 
SDDT intake by humans has been through meat. fish. 
and poultry (7). Body fat of people abstaining from 
eating meat contained about half as much 51DDT as fat 
from people in the general population (9). 

In a study conducted in India, four of 1 1 meat samples 
contained pesticide residues (7). However, information 
available on residues in India is scanty, although DDT 
and BHC are still used in large quantities. Thus, data on 
DDT and BHC residues in the tissues of goats, buffalo, 
and chickens, the common meat sources in India, are 
presented in this communication. 



Industrial Toxicology Research Centre. Post Box 80, Mahatma Gandhi Marg, 
Lucknow 226001. India 



High-purity analytical reagent grade chemicals and 
solvents were used. Glassware was rinsed with acetone 
before use. 

COLLECTION OF SAMPLES 

Generally, breast muscle, liver, whole brain, and 
abdominal fat samples of goats, buffalo, and chickens 
were collected from slaughterhouses situated in and 
around the city of Lucknow. That city is the capital of 
the largest state, Uttar Pradesh, where 14% of the total 
livestock population of India is raised. A few samples 
of goat and buffalo bone marrow were also collected. 
Collected samples were placed in aluminum foil and 
frozen until analysis. Whole brain was mixed thorough- 
ly before being weighed for extraction. Analyses were 
performed within one week after collection of samples. 

EXTRACTION AND CLEANUP 

Homogenization of biological tissues in the presence of 
concentrated formic acid disrupts cell structure for 
efficient extraction of organochlorine pesticide residues 
in a suitable organic solvent (3). This technique is 
particularly convenient when a large number of 
biological samples must be analyzed. 

Finely minced 2-g samples of muscle, brain, and liver 
tissues were homogenized thoroughly with 7 ml formic 
acid and transferred to 50-ml conical flasks. The 
homogenizing tube and pestle were washed twice with 5 
ml portions of «-hexane which were then added to the 
conical flask. For body fat and bone marrow samples, I 
g of each was homogenized with 5 ml formic acid and 5 
ml «-hexane and transferred to a conical flask. Again, 
the homogenizing tube and pestle were washed twice 
with 5 ml portions of the solvent which were added to 
the conical flask. The contents were shaken in a 40°C 
shaker water bath for 1 hr. The solvent phase was 
withdrawn after centrifugation. The residue material 
was extracted again with 5 ml solvent, and the solvent 
extracts were combined. Fat in the extracts of body fat. 
bone marrow, and brain samples was removed by 
acetonitrile partitioning (77). and pesticide residues 



Vol. 15, No. 2. September 1981 



103 



were re-extracted in «-hexane solvent. The solvent 
phase was isolated and washed twice with glass- 
distilled water. Finally, the solvent phase was dried by 
passing it through an anhydrous sodium sulfate column 
into a round-bottom flask. The column was washed with 
10 ml solvent, the eluate was collected in the 
round-bottom flask, and the solvent phase was evapo- 
rated to dryness. The residue was then dissolved in 5 ml 
«-hexane and the solvent layer (2 ml) was mixed with 2 
ml concentrated sulfuric acid. The solvent phase was 
recovered after centrifugation at 3000 rpm for 3 minutes 
and was transferred to clean glass-stoppered vials. 
Aliquots were passed through a silica gel column to 
check for PCB contamination (72). Samples were 
analyzed by gas-liquid chromatography (GLC) with the 
following instrument parameters and operating condi- 
tions: 

Chromatograph; Varian Aerograph. Series 2400 

Detector; 'H electron-capture 

Column: glass spiral, 6 ft long b> ' x-m ID. packed v.ilh 

80-100-mesh Gas-Chroni Q coated with a nii.xture 

ol 1 .S% OV-17 and 1,95<7, OV-210 by weight 
Temperatures. ^C: injector 200 

detector 200 

column 180 
Carrier gas: lOLAR-I grade nitrogen purified by bemg passed 

through silica gel and a molecular sieve to remove 

moisture and oxygen, respectively: pressure, 65 

psi; flowing at 40 ml/min 

Residue peaks were confirmed by thin-layer chroma- 
tography (TLC), using reference standards obtained 
from PolyScience Corp., Niles, Illinois. Recoveries of 
isomers and metabolites of DDT and BHC ranged from 
70% to 89% from the fortified samples of liver, brain, 
muscles, and body fat. Sensitivity of the method was 
0.001 ppm for isomers of BHC, aldrin. and p.p'-DDE. 
and 0.002 ppm for p.p'-TDE and p.p'-DDT. 

Results and Discussion 

Widespread application of pesticides and spillage 



during their transportation or storage are the main 
sources of environmental contamination. Domestic 
animals and poultry have little chance for contact with 
industrial chemicals. However, their feed has been 
found to be a major source of DDT and BHC (14). and 
domestic food animals and poultry are a major source of 
pesticide contamination of the human body. 

DDT and BHC residues found in goats, buffalo, and 
chickens are presented in Tables 1, 2, and 3, 
respectively. Table 4 shows the relative accumulation 
of pesticide residues in chicken leg and breast muscles. 
2BHC. lindane (7-BHC), p.p'-DDE. p.p'-TDE. o.p'- 
DDT, and p.p'-DDT were determined in the present 
study. Results are expressed on a whole-tissue, wet- 
weight basis and are not corrected for recovery. 

GOATS 

All goat tissues contained DDT residues except 
o.p'-DDJ which was not detected in bone marrow, 
body fat. or liver tissues. Average levels of XDDT in 
specific tissues were 0.577 ppm in bone marrow, 0. 193 
ppm in body fat, 0.053 ppm in liver, 0.019 ppm in 
brain, and 0.020 ppm in muscle. Generally, among 
DDT residues, p.p'-DDE was found in the greatest 
quantity. Average BHC and lindane levels were 0.536 
ppm and 0.134 ppm in body fat and 0.203 ppm and 
0.063 ppm in bone marrow samples, respectively. BHC 
residue levels were lowest in muscle tissue, but higher 
in brain than in liver tissues. 

BUFFALO 

DDT residues were detected generally in all buffalo 
tissues. o.p'-DDJ was detected only in muscle tissues. 
Of the DDT residues. p.p'-TDE residues were highest 
and were detected in all body tissues. 

The average levels of SDDT in specific tissues were: 
3.009 ppm in bone marrow. 1.043 ppm in body fat. 



TABLE 1 . Residue levels of BHC and DDT in some body tissues of goals. Lucknow. India 



TlSSLE 



Residues, ppm Wet Weight 



Lindane 


BHC 


fP-DDE 


F p -TDE 


f DDT 


pp-DDT 


iDDT 


0,003-0 007 


010-0 034 


001-0 003 


002-0 005 


ND-0 011 


0,002-fl 039 


OOS-0 (H5 


0,005 1 001 


01810 002 


0002±0001 


002 ±0 001 


0006±000l 


008±0 00l 


0020±0003 


(24) 


(24) 


(24) 


124) 


(22) 


124) 


(241 


0,008-0,018 


0,033-0 115 


002-0 008 


00,1-0 013 


ND-0,a03 


ND-0015 


0,013-0,027 


0,010±0,001 


068 ±0 007 


004±0 001 


005 ±0 001 


001 ±0,001 


007 ±0,001 


0019±0,001 


(14) 


114) 


(141 


(14) 


(3) 


(13) 


114) 


0,006-0,014 


020-0 067 


0,002-0 115 


0,004-0,039 


003 


ND-0 015 


0,009-0 190 


0.009±OOOI 


032 ± 002 


028±0 0Ol 


01,1 ±0,002 


_ 


007±0 00l 


053 ±0011 


(18) 


118) 


(181 


tl8l 


(11 


(17) 


(18) 


0,054-0 347 


146-1 522 


017-0 467 


006-0 420 


ND 


006-0 097 


0039-1 014 


0,1 34 ±0,024 


0,536±0 100 


093 ±0,029 


056 ±0 026 


ND 


027 ±0 006 


193±006l 


(16) 


(16) 


(16) 


1I6) 




(16) 


(161 


0.036-0.123 


0,114-0 470 


0,093-1,806 


0,025-0 294 


ND 


023-0,476 


169-2 816 


0.063*0.013 


203 ±0 044 


358 ±0 207 


065 ±0 032 




106 ±0 055 


577 ±0 320 


(81 


18) 


(8) 


(8) 




181 


18) 



Muscle (24) Range 

Meani SE 
Tissue^ with residues 

Brain ( 14) Range 

Mean±SE 
Tissues wilh residues 

Liver ( 18) Range 

Mean ± SE 
Tissues with residues 

Body fat (16) Range 

Mean ± SE 
Tissues with residues 

Bone marrow (81 Range 

Mean :t SE 
Tissues with residues 



NOTE Number in tirsi column indicates number of samples analyzed. SE = standard error. ND = noi detected 



104 



Pesticides Monitoring Journal 



TABLE 2. Residue levels of BHC and DDT in some body tissues of buffalo. Lucknow, India 



Residues, ppm Wet Weight 



Tissue 



Lindane 


BHC 


f p-DDE 


CP-TDE 


OP DDT 


pp. DDT 


SDDT 


0.00 m), 015 

0,004±0.001 
(22) 


0.006-0,029 
0.012±0.002 

(22) 


001-0.011 

0.005*0.001 

(22) 


0,002-0 (MS 

011 ±0 001 

(22j 


0,002-0.008 
003 ±0001 

(22) 


0.002-0.023 

0.006 ±0.002 

(22) 


0.011-0.081 

0.028 ±0.006 

(22) 


00O7-O0I6 

0,012»0,001 

(16) 


0.024-0.117 

0.076 ±0.006 

(161 


0.009-0.071 

047 ±0.004 

(16) 


0,009-0,054 

0.038 ±0,003 

(16) 


NO 


0.007-0.078 

0.044 ±0.004 

(16) 


0.027-0.211 

0.1 38 ±0.01 2 

(161 


005-0 022 

o.oi2±aooi 

(17) 


0020-0 090 

0.038 ±0.004 

(17) 


011-0 478 

0.074 ±0.027 

(17) 


0,024-0 285 

0094±0,019 

(171 


ND 


0.002-0.107 

0.018±O.0O7 

(17) 


0.043-0 635 

0.205 ±0.045 

(17) 


0.011-0.209 

0.058±0.011 

(17) 


0.039-0,485 

0.165 ±0.027 

(17) 


0.036-0.587 

0.284±0.O41 

(17) 


0,049-1,414 

0,490 ±0.086 

(17) 


ND 


0.021-0.920 

0.1 83 ±0.055 

(17) 


0.116-3.143 

1.043+0.181 

(17) 


041-0,198 
121 ±0033 

(51 


0.123-0.366 

0.252±0.52 

(5) 


0.135-1.544 

0.773 ±0.246 

(5) 


0,165-2,605 
1,289±0,446 

(5) 


ND 


0.019-1.718 
0.720±0.351 

(5) 


0.337-5.038 
3.009 ±0.985 

(5) 



Muscle (22) Range 

Mean ± SE 
Tissues with residues 

Brain (16) Range 

MeaniSE 
Tissues with residues 

Liver (17) Range 

Mean ± SE 
Tissues with residues 

Body fat (17) Range 

Mean ± SE 
Tissues with residues 

Bone marrow (5) Range 

Mean ± SE 
Tissues with residues 



NOTE: See note. Table I 



TABLE 3. Residue levels of BHC and DDT in some body tissues of chickens, Lucknow . India 



Residues, ppm Wet Weight 



Tissue 



Lindane 


BHC 


p,p-DDE 


P.P-TDE 


o.pDDT 


p.p-DDT 


IDDT 


0.002-0 037 


0.014-0.243 


0007-0,251 


0.002-0 021 




0.002-0. 107 


0.010-0 .166 


0.017 ±0.003 


0.109 ±0.024 


090 ±0,024 


007 ±0 002 


ND 


0.030 ±0.0 10 


138 ±0.030 


(10) 


(10) 


(10) 


(10) 




(10) 


(101 


0.012-0.051 


0,108-0,230 


009-0,052 


0,002-0.505 


ND-0.024 


ND-0.022 


0.022-0.121 


0.027 ±0 002 


162 ±0,007 


022 ±0,003 


038 ±0.002 


0.005 ±0 001 


0.011 ±0 002 


0.082 ±0.006 


(19) 


(19) 


(19) 


(19) 


(10) 


(16) 


(19) 


0004-0.091 


0,040-0,445 


0039-0,537 


0.047-0.447 


ND-0.130 


ND-0 130 


0,134-1 447 


0.049 ±0 004 


195±0018 


0,253 ±0,025 


170 ±0.023 


0.040±0.013 


0.025±0006 


0,535 ±0 068 


(20) 


(20) 


(20) 


(201 


(18) 


(18) 


(20) 


0.284-^ 150 


0,819-14,104 


0095-10,939 


0.043-6 372 


ND 


ND-3.200 


0,480-20,832 


1.217±0 188 


3 879 ±0 580 


2 377±0,586 


0.778±0306 




0.644±0301 


4,157±1 027 


(221 


(22) 


(22) 


(22) 




(20) 


(22) 



Muscle (lOi Range 

Mean i SE 
Tissues with residues 
Brain (19) Range 

Mean ± SE 
Tissues with residues 

Liver (20) Range 

Mean ± SE 
Tissues with residues 

Body fat (22) Range 

Mean±SE 
Tissues with residues 



NOTE: See note. Table I 



TABLE 4. Relative accumulation of BHC and DDT residues in chicken leg and breast muscle, Lucknow, India 



Residues, ppm Wet Weight 



Lindane 


BHC 


p p -DDE 


p.p TDE 


ppDDT 


I DDT 


0.036 


0.243 


0.251 


0.016 


0068 


0,366 


0.018 


0.132 


117 


005 


0.019 


0,154 


0.037 


0.216 


0.170 


0.021 


0,107 


0.326 


0.019 


177 


062 


0004 


0,011 


0.084 


0.007 


0.034 


0.063 


0.008 


0031 


110 


0002 


014 


0018 


0003 


0,008 


0031 



Chicken A Leg 

Breast 

Chicken B Leg 

Breast 

Chicken C Leg 

Breast 



0.205 ppm in liver, 0. 138 ppm in brain, and 0.028 ppm 
in muscle. BHC levels were 0.252, 0.165. 0.038, 
0.076, and 0.012 ppm in the respective tissues. 
Relatively high levels of lindane which accounted for 
about half of the total BHC residues were detected in 
bone marrow samples. Mean values of lindane were 
comparable in liver and brain samples. 

CHICKENS 

DDT residues as high as 20.832 ppm DDT, 10.939 
ppm p.p'-UDE, 6.372 ppm p.p'-TDE, and 3.2 ppm 



/7,p'-DDT were detected in chicken body fat. SDDT 
averages in specific tissues were 4. 157 ppm in body fat, 
0.535 ppm in liver, 0.138 ppm in muscle, and 0.082 
ppm in brain. All chicken body tissues contained 
p.p'-DDE and p.p'-TD¥. residues, p.p' -DDE accounted 
for most of the DDT residues except in brain samples, 
where p,p'-TDE was highest. cp'-DDJ was not 
detected in muscle and body fat samples. 

BHC residues were also detected in all chicken tissues. 
Average levels were comparable to S^DDT levels in the 



Vol. 15, No. 2, September 1981 



105 



body fat, brain, and muscles. In chicken body fat 
samples, total BHC varied from 0.819 to 14.104 ppm 
and lindane varied from 0.284 to 4.15 ppm. The 
accumulation of organochlorine pesticide residues 
(Table 4) was always higher in leg muscle than in breast 
muscle. 

Conclusion 

Accumulation of persistent organochlorine pesticide 
residues in the body and their //; vitro biotransformation 
varies from species to species. Various environmental 
factors and dietary habits of individual species are also 
involved in bioaccumulation and biodegradation of the 
residues. Buffalo brain contained highest DDT residues 
in brain, although overall DDT contamination was 
highest in chickens. DDT concentration was always 
higher in goat and buffalo bone marrow than in body 
fat. In general, p.p'-DDE was the major metabolite 
found in biological tissues, hut p.p'-TDE was the major 
metabolite in buffalo body tissues and accounted for 
nearly 40%^50% of SDDT. The levels of p.p'-TDE 
were also higher than p.p'-DDE levels in chicken brain 
tissue. The accumulation of residues was always higher 
in leg muscle than in the breast muscle of chickens. 
DDT levels were found in the following order of 
increasing concentration: goat<buffalo<chicken. Total 
BHC levels were also higher in chicken than in the 
other food animals, and a-BHC accounted for the major 
amount of total BHC in their brain tissues. 

Acknowledgment 

Authors thank C. R. Krishna Murti, Director, Industrial 
Toxicology Research Centre, Lucknow. for his keen 
interest in this work and are grateful to Shri G. S. 
Tandon and Shri B. K. Singh and the Instrument 
Section in general for conducting GLC analyses. 

LITERATURE CITED 

{!) Bmdru. OS., and R. L. Kalra. 1 97 J. Progress and 
problems in pesticide residue analysis. Punjab Agricultu- 
ral University and Indian Council of Agricultural 
Research. Ludhiyana, Punjab. India. 

(2) Bressau. C. 1976. Evaluation of pesticide residues ni 
meat and meat products. Chem. Abstr. 85:138001. 



(3) Dale. W. £.. J. W. Miles, and T. B. Gaines. 1970. 
Quantitative method for determination of DDT and DDT 
metabolites in blood serum. J. Assoc. Off. Anal. Chem. 
53(6):1287-1292. 

(4) Dejonckheere . W.. W. Steurbaul. and R. H. Kips. 1975. 
Pesticide residues in meat and meat products. Rev. 
Agric. (Brussels) 28(6):1541-I553. 

(5) Duggan. R. E.. and G. Q. Lipscomb. 1969. Dietary 
intake of pesticide chemicals in the United States (II) 
June 1966-April 1968. Pestic. Monit. J. 2(4): 153-162. 

(6) Duggan. R. E.. G. Q. Lipscomb. E. L. Co.x. R. E. 
Heatwole. and R. C. Kling. 1971. Pesticide residue 
levels in foods in the United States from July 1, 1963 to 
June 30. 1969. Pestic. Monit. J. 5(2):73-2l2. 

(7) Duggan. R. £.. and J. R. Wealherwa.x. 1967. Dietary 
intake of pesticide chemicals. Science 157(3792):I006- 
1010. 

(8) Ewald. P.. E. Forschner, and H. O. Wolf. 1976. 
Pesticide contents of meat: studies oriented towards 
slaughtered animals and various wild kinds, Dtsch. 
Tieraerztl. Wochenschr. 83:337-340. 

(9) Ha\es. W. J.. G. E. Quinbx. K. C. Walker. J. W. Elliot, 
and W. M. Upholl. 1958. Storage of DDT and DDE in 
people with different degrees of exposure to DDT. Arch. 
Ind. Health 18:398-406. 

{10) Khristos. D.. 1. Isvetana. and Z. Calina. 1973. Residual 

amounts of organochloride pesticides in animal fat. Vet. 

Med. Nauki 1:9-13. 
(//) Mills. P. A. 1961. Collaborative study of certain 

chlorinated pesticides in dairy products. J. Assoc. Off. 

Anal. Chem. 44(2):171-175. 

(12) Picer. M.. N. Picer. and M. Ahel. 1978. Chiormated 
insecticide and PCB residues in fish and mussels of east 
coastal waters of middle and north Adriatic Sea, 
1974-75. Pestic. Monit. J. 12(3):102-l 12. 

(13) Riclwn-Bac. L.. and M. Hascoet. 1974. Pesticide 
residues and organochlorine pollutants in foods of animal 
origin. Comm. EUR Communities (Rep) EUR, 1974, i 
EUR 5196, Probl. Raised Contam. Man Environ, i 
Persistent Pestic. Organo-Halogenated Compounds, pp. 
163-174. 

(14) Tripalhi. H. C. 1966. Organochlorine pesticide residues 
in agricultural and animal products in Terai area. M.Sc. 
Thesis. U.P. Agricultural University. Pantnagr. 

(15) Walker. K. C. M. B. Coette. and G. S. Balchelor. 
1954. Pesticide residues in foods: Dichlorodiphenyl 
trichloroethane and dichlorodiphenyl dichlorocthylene 
contents of prepared meals. J. Agric. Food Chem. 
2:1034-1037. 



106 



Pesticides Monitoring Journ.al 



APPENDIX 



Chemical Names of Compounds Discussed in This Issue 



^LDRIN 

/VROCLOR 1242 

^ROCLOR 1246 

/SlROCLOR 1260 

BHC (Benzene Hexachlonde) 

CHLORDANE 

DDE 

DDMU 

DDT 

DICOFOL 
DIELDRIN 
ENDRIN 
HCB 

HEPTACHLOR EPOXIDE 

LINDANE 

MIREX 

NONACHLOR 

OXYCHLORDANE 

PBBs (PnKbrominaled Biphenyls) 

PCBs (Polychlonnaied Biphenyls) 

PCSs (Polychlonnaied Styrenes) 

IDE 

TOXAPHENE 



Hexachlorohexahydro-eH^c e.tp-dimethanonaphihalene 9f>'7f and related compounds 5% 

PCB, approximately 42^ chlorine 

PCS. approximately 46% chlorine 

PCB. approximately 60% chlorine 

1 ,2.3.4,5,6-HexachlorocycIohexane (mixture o\ isomers) 

Technical: 60% octachloro-4.7-methanotetrahydroindane and 40% related compounds 

Dichiorodiphenyldichloroethylene (degradation product ot DDT) 

l-ChIoro-2.2-bis(/7-chlorophenyl) ethylene 

Dichloro diphenyl tnchloroethane. Pnncipal isomer present ip.p'-DDT. not less than 70%^); 1 .1.I-trichloro-2.2-bis(;J- 
ch!o^ophenyl )ethane 

I.l-Bis(chlorophenyl)-2.2.2-trichloroethanol 

Hexachloroepoxyoctahydro-eHf/p.t'AY'-dimeihanonaphihalene 85% and related compounds 15% 

Hexachloroepoxyoctahydro-ffft/^'.cnt/o-dimethantinaphthalene 

Hexachlorobenzene 

1 .4.5,6.7.8,8-Heptachloro-2.3-epoxy-3a.4.7.7a-tetrahydro-4.7-methanoindan 

Gamma isomer of benzene hexachloride (BHC) 

Dodecachlorooctahydro-1 ,3,4-metheno-IW-cyclobuta[cd|pentatene 

l.2.3.4.5.6,7.8.8-Nonachloro-3a.4.7.7a-telrahydro-4.7-methanomdan 

l-e.vo-2-eWo-4.5.6.7.8.8a-Octachloro2.3-('A('-epoxy-2.3.3a.4.7,7a-hexahydro-4.7-methanomdene 

Mixtures of brominaled bipheny! compounds having various percentages of bromine 

Mixtures ot chlormated biphenyi compounds having various percentages of chlorme 

Mixtures of chlormated styrenes havmg various percentages ot chlorme 

Dichloro diphenyl dichloroethane ( 1 .l-dichloro-2.2-bis(/j-chlorophenyl)ethane. principal component) 

Technical chlorinated camphene (67-69% chlorine) 



Vol. 15, No. 2, September 1981 



107 



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CONTENTS 



Volume 15 December 1981 Number 3 



FISH, WILDLIFE, AND ESTUARIES 



Page 



Factors Influencing Dieldrin and DDT Residues in Carp from the Des Moines River, 

Iowa, 1977-80 ^ 111 

Wayne H. Hubert and Edward D. Ricci 

Influence of a New Impoundment on Pesticide Concentrations in Warmwater Fish, 

Saylorville Reservoir, Des Moines River, Iowa, 1977-78 117 

Siu-Yin Theresa Leung, Ross V. Bulkley, and John J. Richard 

Polychlorinated Bipheiiyls in Clams and Oysters from New Bedford Harbor, Massa- 
chusetts. March 1978 123 

Walter I. Hatch, Donald W. Allen, Phillips D. Brady, Alan C. Davis, and 
John W. Farrington 

Nationwide Residues of Organochtorine Compounds in Wings of Adult Mallards aiui 

Black Ducks. 1979-80 128 

Brian W. Cain 



HUMANS 

Organochlorine Pesticide Residues in Human Milk Samples from Comarca Lagunera, 

Mexico, 1976 135 

L. Albert, P. Vega, and A. Portales 



WATER 

I.2-Dihromo-3-chloropropane Residues in Water in South Carolina, 1979-80 139 

George E. Carter, Jr., and Melissa B. Riley 



APPENDIX 143 

ERRATUM 144 

Information for Contributors 145 



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represented on the Monitoring Panel which participate in operation of the national 
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Address correspondence to; 

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Pesticides Monitoring Journal 

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Editor 

Roberta B. Maltese 



FISH, WILDLIFE, AND ESTUARIES 



Factors Influencing Dieldiin and DDT Residues in Carp 
from the Des Moines River, Iowa, 1977-80^ 

Wayne H. Hubert and Edward D. Ricci" 



ABSTRACT 

Concentrations of dieldrin and DDT in muscle tissue and 
fat of carp, Cyprinus carpio, from the Des Moines River, 
Iowa, differed significantly with month of collection, fish 
age, and sampling location. Pesticide levels expressed on the 
basis of wet weight of flesh often differed from those ex- 
pressed on a fat basis. Fish from reservoirs tended to have 
higher levels of dieldrin, but not of DDT, than did fish from 
riverine locations. 

Introduction 

Interpretation of data from organochlorine pesticide 
residue monitoring programs for freshwater fish is diffi- 
cult because numerous factors influence sample vari- 
ability. Identification of the factors that contribute to 
sample variability would improve the reliability of mon- 
itoring programs. Authors assessed the influence of 
selected variables in concentrations of aldrin and DDT 
in carp (Cyprinus carpio) from a midwest river, the Des 
Moines. 

Aldrin and DDT were extensively used to control in- 
sects on midwestern cropland for many years. About 3 
million kg of aldrin was applied to Iowa cropland in the 
mid-1960"s to control corn rootworm and cutworm 
(16), The U.S. Environmental Protection Agency can- 
celed registration of aldrin in 1975, and its use was 
discontinued in 1978. The pesticide DDT was used pri- 
marily to control European cornborer, Dutch elm dis- 



• Journal Paper No. J-10204 of the Iowa Agriculture and Home Eco- 
nomics Experiment Station, Ames, lA. Project No. 2465. Financed by 
a grant from the U.S. Department of Defense, Army Corps of Engi- 
neers, and made available through the Engineering Research Institute, 
Iowa State University, to the Iowa Cooperative Fishery Research 
Unit. 

2 Iowa Cooperative Fishery Research Unit, Iowa State University, 
Ames, lA 50011. The Unit is jointly supported by Iowa State Univer- 
sity, the Iowa State Conservation Commission, and the Fish and 
Wildlife Service, U.S. Department of the Interior. 



ease, and mosquitoes during the I950's and 1960's; it 
use was banned in 1970. 

Both aldrin and DDT convert to persistent forms in 
nature, dieldrin and DDE or TDE, respectively. These 
compounds have long half-lives under field conditions — 
8-10 years for dieldrin and 10-20 years for DDE 
(13, 15) — and tend to be strongly adsorbed to soil 
particles (7, 14). Because of these factors and the 
widespread use of these compounds on cropland, mid- 
western waters continue to be contaminated through 
soil erosion. Chlorinated hydrocarbons, being hydro- 
phobic, lipophilic chemicals, are absorbed from water 
into the fat of fish. 

The Des Moines River is the largest stream within 
Iowa. More than 80% of its drainage is cultivated, and 
the major source of contamination of the river is non- 
point agricultural runoff (9). Two reservoirs have been 
constructed on the river for flood control, water quality 
control, and recreational purposes. Red Rock Dam, 
completed in 1969, impounds 4,200 ha of water at nor- 
mal pool level. Saylorville Dam, completed in 1977, 
impounds 2,200 ha at normal pool level. A pesticide 
monitoring program was established on the Des Moines 
River in 1977, and several fish species were assessed 
for organochlorine pesticide residues from 1977 to 1979 
(2, 3, 12). The cost of monitoring several species led to 
consideration of limiting analysis to a single sentinel 
species. Carp were selected because they are abundant 
and easy to collect in both the river and reservoirs. The 
objectives of the present paper are to compare wet 
weight of flesh- and fat-based units of measure for 
dieldrin and 2DDT residues in carp; to assess the 
influence of sampling month, fish age, and sampling 
location in the river on residue concentrations; and to 
evaluate trends in dieldrin and 5DDT residue concen- 
trations in Des Moines River carp from 1977 to 1980. 



Vol. 15, No. 3, December 1981 



111 



Methods 

Sampling stations were established at two impounded 
and two riverine locations on the Des Moines River 
(Figure I): Red Rock Reservoir; the river 80 km up- 

Vlcinity Map 




Sampling locations marked with X 



FIGURE 1, Sampling stations for carp on the Dcs Moines 
Rivi'r, Iowa. 

stream from Red Rock Reservoir at Des Moines; 
Saylorville Reservoir; and the river 80 km upstream 
from Saylorville Dam at Boone. Carp were collected 
from each location by electrofishing and hoop netting. 
Five samples were made up from each sampling loca- 
tion in June and in September. Each sample consisted 
of equal weights of lateral muscle from 10 fish of the 
same age. Fish ages were determined by standard scale- 
reading techniques (11 ); only 2- to 4-year-old fish were 
used. Fat content of individual samples was deter- 
mined by the modified Babcock method (7). 

Lateral muscle tissue samples were analyzed for di- 
eldrin, p.p'-DDT. /J.p'-TDE, and p,p'-DDE by the meth- 
ods described in the Pesticide Analytical Manual [8). 
Tissue samples were ground in a 35% water-acetoni- 
trile solution with a high-speed blender for 10 minutes. 
The sample was filtered, the filtrate was transferred to a 
1-liter separatory funnel, 100 ml petroleum ether was 
added, and the mixture was shaken briefly. Then, 600 
ml distilled water and 10 ml saturated saline solution 
were added and mixed by tumbling for 1 minute. After 
the layers had separated, the aqueous fraction was dis- 
carded. The solvent layer was washed with distilled 
water and filtered through a 50-cm anhydrous sodium 
sulfate column. The sample volume was recorded, and 
the extract was subjected to the standard Florisil clean- 
up procedure (8). 



A Tracor 550 gas chromatograph equipped with a "^Ni 
electron-capture detector was used for gas chromato- 
graphic analysis. A 4% SE-30/6% SP-2401 column 
was used for separating and quantifying the pesticides. 
Detected values were corrected for 80% extraction 
efficiency. 

Statistical procedures included the Student's /-test and 
the Pearson Product Movement Correlation Coefficient. 
All decisions to reject null hypotheses were at P < 0.10, 
because sources of variability were being sought. 



Results 



FAT IN CARP MUSCLE 



Fat content of carp muscle ranged from 0.8% to 3.3% 
(Table 1). Between June and September, fat content of 

TABLE 1. Fat content of carp muscle used for pesticide 
analysis from the Des Moines River, Iowa, 1980 





Carp 

ACE. 

Years 




Percent Fat 




Month of 
Collection 


Red Rock 
Reservoir 


River at 
Des 

Moines 


Saylor- 
ville 
Reservoir 


River at 
Boone 


June 


3 


1.5 
1.8 
2.3 


1.8 
1.9 
2.2 


1.4 
1.6 
1.6 


1.8 
1.9 

2.3 




4 


1.7 
1.9 


2.2 
3.3 


1.4 


1.8 

2.4 


(Mean) 




(1.8) 


(2.3) 


(1.6) 


(2.0) 


Sept. 


2 


1.4 
1.1 


1.6 
2.0 


1.8 
2.4 


0.8 
l.I 




3 


1.9 
2.6 


1.3 
1.4 


1.7 
2.5 


1.2 
1.6 




4 


1.7 


1.8 


2.2 


1.6 


( Mean) 




(1.7) 


(1.6) 


(2.1) 


(1.3) 



fish decreased significantly at the two riverine sites, Des 
Moines (0.10 > P > 0.05) and Boone (0.01 > P > 
0.001), increased significantly in Saylorville Reservoir 
fish (0.3 > P > 0.01 ), and did not change significantly 
in Red Rock Reservoir fish. Fat content differed signifi- 
cantly between fish samples from Saylorville Reservoir 
and those from the river at Boone in both June and 
September. Fat levels were higher in river fish in June 
(0.02 > P > O.OI ) and in reservoir fish in September 
(0.01 > P > 0.001). These demonstrated variations in 
fat content indicated the need to consider this variable 
in the pesticide residue analyses. 

dieldrin 

In 1980. concentrations of dieldrin ranged from 10 to 
128 ug/kg of flesh and from 630 to 5,790 |.tg/kg of 
fat (Table 2). Mean levels of dieldrin in flesh and in fat i 
declined between June and September at the four sam-j 
pling locations. The differences in mean levels were ' 
statistically significant at Red Rock Reservoir (0.10 > 
P > 0.05), the river at Des Moines (0.10 > P > 0.05), 



Pesticides Monitoring Journal 



TABLE 2. Dieldrin residues in muscle of carp from the Des Moines River, Iowa, 1980 





Carp 

AOE, - 

Years 








Residues 


iug/kg 










Red Rock Reservoir 


River at 


Des Moines 


Saylorville 


Reservoir 


River 


AT Boone 


Collection 


Flesh ' 


Fat 


Flesh i 


Fat 


Flesh i 


Fat 


Flesh i 


Fat 


June 


3 


83 
73 
63 


4,580 
3,150 
4,170 


30 
55 
33 


1,360 
3,060 
1,710 


33 
51 
54 
56 


2,850 
2,030 
3,840 
3,520 


41 
41 
50 


2,170 
1,790 

2,780 




4 


75 
110 


4,410 
5,790 


55 
128 


3,860 
2,500 


34 


2,410 


48 
66 


2,760 
2,640 


(Mean) 




(81) 


(4,420) 


(60) 


(2,500) 


(46) 


(2,930) 


(49) 


(2,430) 


Sept. 


2 


34 
53 


3,070 
3,750 


11 
15 


630 
750 


29 

43 


1,600 
1,770 


16 

21 


2,030 
1,930 




3 


58 
59 


3,090 
2,210 


10 

41 


770 
2,950 


36 

45 


1,450 
2,650 


15 

24 


1,250 
1,480 




4 


84 


4,930 


23 


1,250 


30 


1,360 


36 


2,270 


(Mean) 




(58) 


(3,410) 


(20) 


(1,270) 


(37) 


(1.770) 


(22) 


(1,790) 


1 Wet-weight basis. 





















and the river at Boone (0.01 > P > 0.001) when ex- 
pressed on a wet-weight flesh basis. On a fat basis, the 
differences were statistically significant in the river at 
Des Moines (0.10 > P > 0.05), the Saylorville Reser- 
voir (0.05 > P > 0.02), and the river at Boone 
(0.05 >P> 0.02). 

Statistically significant variation in mean dieldrin level 
related to fish age was noted in June (0.10 > P > 
0.05) but not in September, when wet-weight flesh was 
used as the analytical basis. No statistically significant 
variation due to age was observed in either June or 
September on a fat basis. 



Trends in mean concentrations of dieldrin in carp 
muscle at the four sampling locations from 1977 to 
1980 are illustrated in Figure 2. The 1977-79 samples 
were collected and analyzed in the same manner as 
described for 1980 samples. Size ranges of the fish indi- 
cate that the 1977-79 samples were predominantly com- 
posed of 2- and 3-year-old fish. Fish from the im- 
pounded sites tended to have higher levels of dieldrin 
than did those from the riverine sites (Figure 2). Sub- 
stantial variation in dieldrin levels between sampling 
periods occurred at all locations, but the magnitude of 
the fluctuations was greatest in the reservoirs. 



Differences in mean levels of dieldrin in carp samples 
occurred between some sampling locations. In June, no 
significant differences occurred between the reservoirs 
and their associated riverine stations when concentra- 
tions were expressed on a flesh basis, but a significantly 
higher level was observed in Red Rock Reservoir fish 
compared with fish from the river at Des Moines 
(0.02 > P > 0.01) on a fat basis. In September, di- 
eldrin concentrations in fish were significantly higher 
at both Red Rock and Saylorville reservoirs than at 
the upstream locations (0,01 > P > 0.001 and 0.05 > 
P > 0.02, respectively) on a flesh basis, but a signifi- 
cant difference was observed only between Red Rock 
Reservoir and the river at Des Moines on a fat basis. 

Levels of dieldrin were significantly higher in samples 
from Red Rock Reservoir than in those from Saylor- 
ville Reservoir in June (0.01 > P > 0.001 for flesh, 
0.05 > P >> 0.02 for fat) and in September (0.05 > 
P > 0.02 for flesh, 0.02 > P > 0.01 for fat). No sig- 
nificant differences were observed between riverine 
locations. 



• — 


— • 


River a\ Boone 


owa 






•-- 


— • 


Saylorwille Reset 


voir 






a — 


— o 


River at Des Mo 


nes 


low 


a 


0-- 


--C 


Red RocV Reser\ 


oir 








/ J. 




I 






/ 






1 \ 






/ 


. 


' 




/ 




/ \ 


/ 




\ 


s / 




' \ 






\ 


If 




1 \\ 


/ 




■ 


/ \ 




1 \\ 


/ 







^ 200 

Q. 
Q. 

13 175 

t/l 

™ 150 

-- 125 

c 

i 100 

I 75 

o 
c 
o 

5 25 

C 

5 

Oct Apr July Oct Apr July Oct June Sept 
1977 1978 1978 1978 1979 1979 1979 1980 1980 

FIGURE 2. Variation in dieldrin residues in flesh of carp 

from four sampling locations on the Des Moines River, 

Iowa, 1977-SO. Data for 1977-79 taken from Baumann 

et at. (2, 3). 




Vol. 15, No. 3, December 1981 



113 



TOTAL DDT 

The concentration of :iDDT (DDT, TDE, and DDE) 
in carp muscle ranged from 18 to 191 [^ig/kg of flesh 
and from 1,090 to 9,910 iig/kg of fat in 1980 samples 
(Table 3). In June, iDDT was composed of 54.8% 
DDE, 24.6% TDE, and 20.6% DDT in the average 
sample. Proportions were similar in September — 53.3% 
DDE, 27.9% TDE, and 18.8%- DDT. 

2DDT levels in fish samples declined from June to 
September. The difference was statistically significant on 
a flesh basis at all sampling locations: Red Rock Reser- 
voir (0.02 > P > 0.01), the river at Des Moines 
(0.05 > P > 0.02), Saylorville Reservoir (0.10 > P 
> 0.05) and the river at Boone (0.01 > P > 0.001). 
The concentration of ^-DDT in the fat was significantly 
lower in September only in fish from the reservoirs: Red 
Rock (0.02 > F > 0.01) and Saylorville (0.05 > 
P > 0.02), 

The mean level of 5DDT was significantly higher in 
4-year-old fish than in 3-year-old fish on both flesh 
(0.02 > P > 0.01) and fat (0.10 > P > 0.05) bases 
in June. No differences among samples of 2-, 3-, and 
4-year-old fish were observed in September. 

Mean ^-DDT in carp varied significantly between some 
sampling locations. Concentrations were significantly 
higher in samples from Saylorville Reservoir than in 
samples from the upstream site near Boone in both 
June (0.10 > P > 0.05) and September (P > 0.001) 
on a flesh basis, but only in June on a fat basis 
(0.02 > P > 0.01 ). In September, mean level of 5DDT 
was significantly higher in fish from the river at Des 
Moines than in fish from Saylorville Reservoir on 
both flesh (0.10 > P > 0.05) and fat (0.01 > P > 
0.001 ) bases. This was the only comparison made in 
which the mean level of pesticide residues was higher 
in samples from a riverine location than in samples 
from the associated downstream impoundment. 



Comparison of samples from the two reservoirs showed 
no significant differences in mean iDDT. However, 
statistically significant differences in mean iDDT oc- 
curred between fish from the two riverine sites in both 
June and September. Mean levels of 5DDT were sig- 
nificantly higher in both flesh (0.02 > P > 0.01 in 
June, 0.01 > P > 0.001 in September) and fat (0.01 > 
P > 0.001 in June, 0.01 > P > 0.001 in September) 
of fish sampled near Des Moines than in those collected 
at Boone. 

Mean 2DDT concentration in carp samples declined 
substantially between October 1977 and July 1978 at 
the two riverine locations (Figure 3). 5DDT levels in 



250 

a 225 

a. 

i^ 200 

s 

2 175 

m 

c 150 

I 125 

c 

S 100 



75 



50 



25 




Oct Apr July Oct Apr July Oct June Sept 
1977 1978 1978 1978 1979 1979 1979 1980 1980 

FIGURE 3. Vaiialion in total DDT residues in flesh of 

carp from four sampling locations on the Des Moines Ri^er, 

Iowa, 1977-SO. Data for 1977-79 taken from Baumann 

et al. (2, 3). 



TABLE 3. Total 


DDT 


(DDT, TDE, 


and DDE) 


residues 


in muscles of 


carp from 


the Des Moines River, 


Iowa, 1980 




Carp 
Ace, 
Years 








Residues, 


^g/kg 








Month of 
Collection 


Red Rock Reservoir 


River at 


Des Moines 


Saylorville Reservoir 


River at Boone 


Flesh 


Fat 


Flesh 


Fat 


Flesh 


Fat 


Flesh 


Fat 


June 


3 


55 

125 

76 


4,240 
5,490 
2,670 


83 
88 
88 


3,980 
4,860 
4,340 


96 

74 
46 
85 


4,720 
2,820 
5,270 
6,020 


35 
50 
55 


2,890 
2,170 
1,560 




4 


149 
130 


7,650 
7,830 


191 
159 


4,810 
8,690 


185 


9,910 


28 
55 


1,830 
1,290 


(Mean) 




(107) 


(5,780) 


(122) 


(5,340) 


(97) 


(5,760) 


(45) 


(1,950) 


Sept. 


2 


31 
20 


2,230 
1,820 


51 
79 


3,200 
3,940 


40 

53 


2,920 
1,670 


28 

21 


2.500 
2,660 




3 


41 
44 


2,170 
1,680 


43 
50 


3,270 
3,570 


53 
54 


2,150 
3,090 


23 
18 


1,880 
1,090 




4 


56 


3,310 


91 


5,070 


43 


1,930 


29 


1,800 


(Mean) 




(38) 


(2,240) 


(63) 


(3,810) 


(49) 


(2,350) 


(24) 


(1,990) 



114 



Pesticides Monitoring Journal 



carp have fluctuated substantially at all locations since 
1978, with no indication of significant differences in 
trends between impounded and riverine locations. 

Discussion 

The lipophilic nature of organochlorine pesticide resi- 
dues results in significant associations between fat con- 
tent and pesticide levels in fish (4. 5, 12). It has been 
suggested that the variance in organochlorine pesticide 
residue samples may be reduced by normalizing on a 
fat basis. Statistically significant variation in fat content 
of Des Moines River carp was observed between sam- 
pling months, ages of fish, and sampling location, indi- 
cating a need to consider the fat content in data analy- 
ses. However, normalization on a fat basis in Des 
Moines River carp samples did not reduce the vari- 
ability of the data. Comparisons of dieldrin and 2DDT 
concentrations between sampling months, fish ages, and 
sampling locations produced results that were different 
on fat and flesh bases in several instances. 

The mean levels of both dieldrin and SDDT in Des 
Moines River carp varied between sampling periods. A 
decline was observed between June and September 
1980. Concentrations of dieldrin and 5DDT in carp 
from the Des Moines River fluctuated dramatically be- 
tween sampling periods from 1977 to 1979, but a 
spring-to-autumn decline did not consistently occur. 
During 1971-73, before the use of dieldrin was dis- 
continued, seasonal trends in dieldrin concentrations in 
Des Moines River channel catfish (Ictahinis punc'tatiis) 
were related to corn planting and aldrin application 
{10). Present patterns are more complicated and prob- 
ably relate to several factors, including water tempera- 
ture (and, consequently, metabolic rates of fish) before 
sampling (6), fat content of the fish (4, 5), extent of 
pesticide contamination in bottom sediments and on 
agricultural land within the watershed (17), tillage 
practices by farmers, and precipitation before sampling. 
The results indicate that evaluation of variations in 
organochlorine pesticide residues relative to sampling 
locations or time should be made on fish of the same 
age. The need to consider fish age was shown in June 
when levels of dieldrin and SDDT were significantly 
higher in 4-year-old than in 3 -year-old fish. Similar 
variation relative to age has been described in channel 
catfish from the Des Moines River {4, 5). 

The present study showed that impoundments within a 
river system may affect the data developed in a moni- 
toring project. Dieldrin in carp muscle tended to be 
higher in fish from reservoirs than from upstream 
riverine sites, but the same trend did not hold con- 
sistently for SDDT. Whole-body analyses of carp in 
1977 and 1978 showed no difference in either dieldrin 
or 5DDT levels between Saylorville Reservoir and 



either upstream or downstream locations {12). Differ- 
ences in dieldrin and SDDT occurrence relative to the 
impoundments indicated that the dynamics of the two 
types of pesticide residues are different within reser- 
voirs. Differences also were noted between riverine and 
impounded locations. 

Concentrations of dieldrin and SDDT in 1980 carp 
samples from the Des Moines River were below Food 
and Drug Administration, U.S. Department of Health 
and Human Services, standards of 300 ppb dieldrin and 
5 ppm DDT for food fish. Dieldrin in some samples of 
channel catfish fiesh from Des Moines River impound- 
ments in 1977 (6) and 1979 {3) exceeded those stan- 
dards, thereby indicating the need for monitoring as 
well as the need to define the relation between organo- 
chlorine pesticide residues in sentinel species, such as 
carp, and other fish species. 

Analysis of 1977-79 data (2, 3) from the Des Moines 
River showed a significant correlation {r = 0.51, 
0.02 > P > 0.01) between mean levels of dieldrin in 
carp and channel catfish samples taken at the same time 
and location, but not between concentrations in carp 
and those in walleye (Stizostedion vitreum vitreum), 
or largemouth bass (Micropienis salmoides). From 
1977 to 1979, the mean dieldrin level in channel catfish 
exceeded that of carp by 2.2 times in samples from Red 
Rock Reservoir and by 3.1 times in samples from 
Saylorville Reservoir; however, the factor varied sub- 
stantially between sampling dates. Leung (72) found 
a positive correlation (r = 0.56) between percentage 
fat of various species found in the Des Moines River 
and dieldrin levels in the flesh. She noted that channel 
catfish tended to have double the fat content and triple 
the dieldrin concentrations of carp, but observed no 
similar relations in SDDT concentrations. The extent 
of the relation between species and fat content pro- 
vides some basis for extrapolating dieldrin levels ob- 
served in carp to those in channel catfish, but not for 
SDDT or for other species. The relation between di- 
eldrin levels in carp and catfish would probably be 
strengthened if variables such as fish age, fat content, 
and capture location were controlled. 

A cknowledgments 

Authors thank John Richard, U.S. Department of En- 
ergy, for conducting the chemical analyses and review- 
ing the manuscript, and John Nickum, Jim Mayhew, 
and Gary Atchison for reviewing the manuscript. 

LITERATURE CITED 

(/) Association of Official Agricultural Chemists. 1965. 
Official Methods of Analysis, 10th Ed., Arlington, 
Va. p. 957. 



Vol. 15, No. 3, December 1981 



115 



(2) Baumann, E. R., C. A. Beckert, M. K. Butler, and 
D. M. Soballe. 1979. Water quality studies— EWQOS 
sampling Red Rock and Saylorville Reservoirs, Des 
Moines, Iowa. Engineering Research Institute, Iowa 
State University, Ames, Iowa. 364 pp. 

(i) Baumann, E. R., C. A. Beckert, M. K. Butler, and 
D. M. Soballe. 1980. Water quality studies— EWQOS 
sampling Red Rock and Saylorville Reservoirs, Des 
Moines River, Iowa. Engineering Research Institute, 
Iowa State University, Ames, Iowa. 484 pp. 

(4) Bulkley, R. V. 1978. Variations in DDT concentra- 
tion in muscle tissue of channel catfish, Ictalurus 
punctatus, from the Des Moines River, 1971. Pestic. 
Monit. J. Il(4):165-169. 

(5) Bulkley. R. V., R. L. Kellogg, and L. R. Shannon. 
1976. Size-related factors associated with dieldrin con- 
centrations in muscle tissue of channel catfish, Ictalu- 
rus punctatus. Trans. Am. Fish. Soc. 105(2) ;301-307. 

(6) Bulkley, R. V., T. S. Leung, and J. Richard. 1978. 
Des Moines River pesticide monitoring. Proc. Seminar 
on the Water Quality in the Corps of Engineers' 
Reservoirs in Iowa. March 9, 1978. U.S. Army Corps 
of Engineers, Rock Island District, Rock Island, 111. 
8 pp. 

(7) Eye, J. D. 1968. Aqueous transport of dieldrin resi- 
dues in soils. J. Water Pollut. Control Fed. 40 (8, 
Part 2) :3 16-332. 

(5) Food and Drug Administration. 1970. Pesticide Ana- 
lytical Manual, Vol. 1, Sec. 212.1. U.S. Department 
of Health and Human Services, Washington, D.C. 

(9) lon-a Department of Environmental Quality. 1976. 
Water quality management plan. Des Moines River 
basin. Des Moines, Iowa. 



(10) Kellogg, R. L., and R. V. Bulkley. 1976. Seasonal con- 
centrations of dieldrin in water, channel catfish, and 
catfish-food organisms, Des Moines River, Iowa — 
1971-73. Pestic. Monit. J. 9(4) : 186-194. 

(//) Lagler, K. F. 1956. Freshwater Fishery Biology. Wm. 
C. Brown Co., Dubuque, Iowa. 421 pp. 

(12) Leung, S. T. 1979. The effect of impounding a river 
on the pesticide concentration in warmwater fish. 
Ph.D. dissertation, Iowa State University, Ames. 
155 pp. 

(13) Mach, R. G., and E. A. Woolson. 1967. Persistence 
of chlorinated hydrocarbon insecticides in soils. Sci- 
ence 157(3791 ):924-927. 

(14) Pfisler, R. M., P. R. Dugan, and J. 1. Frea. 1969. 
Microparticulates: isolation from water and identifi- 
cation of associated chlorinated pesticides. Science 
166(3907) :878-879. 

(15) Schnoor, J. L. 1979. Pesticide trends in Iowa rivers. 
Proc. Seminar on the Water Quality in the Corps of 
Engineers' Reservoirs in Iowa. March 21. 1979. U.S. 
Army Corps of Engineers, Rock Island District, Rock 
Island, 111. 

(16) Schnoor, J. L. 1980. Fate and transport of dieldrin in 
Iowa rivers: residues in fish and water following a 
pesticide ban. Proc. Seminar on the Water Quality in 
the Corps of Engineers' Reservoirs in Iowa. March 27, 
1980. U.S. Army Corps of Engineers, Rock Island 
District, Rock Island, 111. 

(17) Weber, J. B. 1972. Interaction of organic pesticides 
with particu'ate matter in aquatic and soil systems. 
Pages 55-120 in R.F. Gould, Ed. Fate of Organic 
Pesticides in the Aquatic Environment. American 
Chemical Society, Washington, D.C. 



116 



Pesticides Monitoring Journai 



Influence of a New Impoundment on Pesticide Concentrations in Warmwater Fish, 
Saylorville Reservoir, Des Moines River, Iowa, 1977-78^ 

Siu-Yin Theresa Leung," Ross V. Bulkley,' and John J. Richard ' 



ABSTRACT 

Samples of seven species of warmwater fish were collected 
above, within, and below newly impounded Saylorville Res- 
ervoir, Des Moines River, Iowa, from October 1977 to 
October 1978. Whole-body analyses by gas chromatography 
were significantly higher in river carpsiicker (Carpiodes 
cyanazine and for the organochlorine insecticides dieldrin, 
p,p'-DDE, p,p'-TDE, p,p'-DDT, and heptachlor epoxide. 
Only the organochlorine insecticides were detected in fish 
tissue. Concentrations of dieldrin and heptachlor epoxide 
were significantly higher in river carpsucker (Carpiodes 
carpio) from the reservoir than in those from the river. 
Other species of fish showed no differences in pesticide 
concentration related to locality of collection. 

Introduction 

The construction of a reservoir on a river increases the 
complexity of pesticide dynamics in the aquatic system. 
Impoundments for flood control, water supplies, energy 
development, recreation, and other purposes are be- 
coming increasingly numerous in the United States. 
During 1977-78, a study was conducted on Saylorville 
Reservoir, a new impoundment on the Des Moines 
River up stream from Des Moines, Iowa, to determine 
the rate of pesticide deposition in the reservoir and the 
effect of impoundment on pesticide accumulation in 
different species of fish. The discussion here addresses 
pesticide accumulation in the fish. Elsewhere, Leung (6) 
reported on seasonal pesticide fluctuations and pesticide 
deposition in the reservoir. 

The Des Moines River rises in the glacial moraine area 
of southwestern Minnesota and flows southeasterly 
across Iowa to join the Mississippi (Figure 1). It is the 
largest river in Iowa. About 79% of the watershed up- 
stream from Des Moines is cropland, primarily corn 



' This study was conducted as part of Project 2225 of the Iowa Agri- 
culture and Home Economics Experiment Station. Ames, Iowa, in 
::ooperation with the Iowa Cooperative Fishery Research Unit, which 
is jointly sponsored by the Iowa State Conservation Commission, Iowa 
State LIniversity, and the Fish and Wildlife Service, U.S. Department 
jf the nterior. 

•Minnesota Pollution Control Agency, Roseville, MN 55113 
' Utah Cooperative Fishery Research Unit, Logan, UT 84322 
Iowa Slate University, Ames, lA 50011 




FIGURE 1. Upper Des Moines River watershed, showing 
sampling sites. 

and soybeans; 6% is permanent pasture, 5% is forest, 
and 7% is urban (4). Normal annual precipitation over 
the drainage area ranges from 62.5 to 77.5 cm from 
north to south and averages 70.7 cm (S). Precipitation 
is usually heaviest in June, but heavy rainfall and cloud- 
bursts occasionally cause high river flows in summer 
and early fall. The major source of contamination of 
the river is agricultural runoff. 

Three collection stations were set up for this study: 
Station 1 at Boone, Iowa, is about 73 km upstream 
from Saylorville Dam; Station 2 is located in Saylor- 
ville Reservoir; and Station 3 is located at the town of 
Saylorville, about 3 km downstream from Saylorville 
Dam. Drainage areas at the three points, upstream to 
downstream, are 14,530, 15,081, and 15,128 km-, re- 
spectively. 

Gates on the Saylorville Reservoir were closed in April 
1977. During the study period, the reservoir remained 



Vol. 15, No. 3, December 1981 



117 



within 1.2 m of conservation pool level, and average 
water retention time was about 40 days (1). Volume 
at conservation pool level was about 90 million m-'. 

Materials and Methods 

Fish samples were collected quarterly at Stations 1, 
2, and 3 from October 1977 to October 1978, with gill 
nets, hoop nets, and electroshockers. Species analyzed 
for pesticide residues were gizzard shad (Dorosoma 
cepedianum), river carpsucker (Carpiodes carpio), com- 
mon carp {Cyprimis carpio), channel catfish (Ictaluriis 
punctatus), white crappie (Pomoxis annularis), large- 
mouth bass (Micropterus salmoides), and walleye (Sti- 
zostedion vitreum). Specimens were grouped by collec- 
tion date, location, species, and body length. An at- 
tempt was made to collect small specimens and to avoid 
large, old fish of each species. Small fish were selected 
on the assumption that most of their life occurred after 
impoundment, and that they would be less likely than 
old fish to have migrated between sampling stations. 
With few exceptions, all fish selected for sampling were 
subadult, and many were young-of-the-year. Mean total 
lengths ranged from 137 mm for gizzard shad to 
232 mm for walleyes (Table 1). 

Fish in the same group were ground together in a 
hand grinder and then mixed manually in an effort to 



obtain a homogeneous mixture. Subsamples were then 
wrapped in aluminum foil and frozen until analysis. 
Because preliminary analyses indicated that atrazine, 
alachlor, cyanazine. dieldrin, p.p'-DDE, p.p'-TDE, 
p.p'-DDT, and heptachlor epoxide were present in water 
or fish, these substances were selected for study. Con- 
centrations of pesticides in water are listed in Table 2. 

TABLE 2. Mean weekly dissolved pesticide concentrations 

(ng/liter) at eacli Des Moines River station where fish were 

collected, September 1977 to November 1978 ' 



Station 



Chemical 



1 



Mean 



Atrazine 225 (<10-1356) 221 (0-1167) 

Alachlor 115 (0-1450) 80 (0-1125) 

Cyanazine 71 (0-500) 90 (0-6601 

Dieldrin 3 (0-14) 3 (<l-6) 

p.p'-DDE= <1 <1 



222 (< 10-1000) 223 

72 (0-725) 89 

111 10-640) 91 

3 (<l-6) 3 

<1 <1 



NOTE; Numbers in parentheses are ranges. 

' Values are from Ref. 6. 

- Mean concentration of p,p'-DDE on suspended sediment was 7 ng/kg 

(0-66) at Station 1. 4 ng/kg (0-25) at Station 2, and 6 ng/liter 

10-132) at Station 3. 

Authors used standard methods of tissue analysis (7) 
with slight modification. After thawing, 25-30-g sam- 
ples were extracted with 200 ml of 65% acetonitrile- 
water for 5 minutes in a 1 -liter stainless steel blender. 
The sample was then filtered into a 250-ml graduated 



TABLE 1. Number of fish and range in length of fish 



collected from the Des Moines River for 
1977-78 



pesticide residue analysis. 





Date 








Length, mm- 








Station ' 


Gizzard 
Shad 


River 
Carpsucker 


Common 
Carp 


Channel 
Catfish 


White 
Crappie 


Walleye 


Largemouth 
Bass 


1 


Oct. 1977 


45 
(136-199) 


33 

(76-278) 


64 

(83^02) 








4 
(144-180) 


1 
(195) 




Apr. 1978 





46 

(85-328) 


91 

(85-130) 
















Jul. 1978 





58 
(103-368) 


42 
(131-269) 


34 
(98-247) 


13 
(108-141) 


19 

(175^30) 


8 

(230-315) 




Oct. 1978 


40 

(146-205) 


23 
(152^00) 


52 
(140-272) 


5 
(154-413) 


16 
(132-170) 


4 
(180-279) 


18 

(120-348) 


2 


Oct. 1977 


56 

(104-163) 


6 

(131-307) 


35 
(103-191) 


10 

(310^87) 


31 

(75-295) 


5 
(160-300) 


46 

(95-260) 




Apr. 1978 


6 

(128-195) 


6 

(198-367) 


69 

(105-216) 


17 
(232-430) 


4 
(87-98) 


3 
(245-282) 


6 

(96-262) 




Jul. 1978 


34 
(67-212) 


25 
1177-381) 


18 
(155-241) 


9 

(285-457) 


10 
(137-305) 


2 
(350-351) 


26 

(123-387) 




Oct. 1978 


63 
(100-199) 


27 
(176-400) 


39 
(165-312) 


8 
(240-3981 


7 
(160-178) 





23 
(166-310) 


3 


Apr. 1978 





22 
(140-335) 


40 

(100-189) 





46 

(81-324) 










Jul. 1978 


40 
(56-101) 


7 
(140-290) 


47 

(135-238) 


3 
(220-290) 


56 

(112-332) 


3 
(202-286) 


4 
(246-310) 




Oct. 1978 


93 
(112-189) 


49 
(141-342) 


39 
(131-226) 





34 
(82-189) 










Total fish 


377 


302 


536 


86 


217 


40 


132 



' See Figure 1 for locations of stations. 
- Range is in parentheses. 



118 



Pesticides Monitoring Journal 



cylinder and transferred to a 1 -liter separatory funnel; 
100 ml petroleum ether, 600 ml water, and 10 ml 
saturated aqueous sodium chloride were added to the 
filtrate. The pesticides were partitioned into the organic 
layer by vigorous shaking for 30-60 seconds. The 
aqueous layer was discarded. The petroleum ether layer 
was washed with two 100-ml portions of water to 
remove the remaining acetonitrile and was transferred 
to a 100-ml graduated cylinder, and the recovered 
volume was recorded. The wet weight of a tissue sample 
was corrected for the losses of acetonitrile-water 
mixture and petroleum ether. The extracts were then 
subjected to Florisil column cleanup. The eluate was 
concentrated to 10 ml for quantification. Results were 
expressed in nanograms of pesticide per gram of fish 
tissue (parts per billion, wet-weight basis). 

Instrument parameters and operating conditions for the 
quantification of (a) alachlor, cyanazine, dieldrin. 
p.p'-DDE, p,p'-TDE, p,p'-DDT, and heptachlor epox- 
ide, and (b) atrazine follow: 



Gas chromatograph: 
Detectors: 



Columns; 



Temperatures: 



Carrier gas: 



Tracer 550 

(a) "^Ni electron capture 

(b) N-P 
glass, 4 mm id 

packed with 10% DC-200 on 80-IOO-mesh 

Gas-Chrom Q 
glass, 4 mm id 
paclfed with a mixture of 4% SC-30 and 

6% OV-210 on 80-100-me5h Gas-Chrom 

Q 
detectors (a) 340° C 
(b) 240° C 
column 210° C 
nitrogen flowing at 90-100 ml/min 



Values were not corrected for the ca 80% recovery 
rate obtained in the extraction. Previous studies (5) 
and preliminary tests revealed little interference from 
polychlorinated biphenyls (PCBs) and chlordane. The 
majority of the PCBs were present as Aroclor 1242 or 
1246, which did not interfere with the other pesticide 
analyses. No chlordane was observed in water or fish 
samples. Pesticide detection limits were about 10 ^ig/kg. 
Where necessary, authors transformed data on pesticide 
concentrations to log 10 values before conducting anal- 
ysis-of-variance or /-tests or computing correlation 
coefficients. 

Results 

The herbicides atrazine, alachlor, and cyanazine were 
not detected in the fish samples. The insecticides diel- 
drin and p.p'-DDE were found in all samples, and 
heptachlor expoxide, p.p'-DDT, and p.p'-TDE were 
found in most. Dieldrin usually occurred in greater 
concentrations than did other insecticides. DDT oc- 
curred in lower concentrations than did its metabolite. 
Probably because the length of fish within samples was 
limited, no consistent relation was evident between 
pesticide concentration and body length in any species 
except largemouth bass (r = 0.66, P = 0.01). There- 
fore, data were pooled for each species except bass to 
compare location and time of year (Table 3). 

Because gizzard shad, channel catfish, white crappies, 
and walleyes were not captured at each station on each 



TABLE 3. Monthly mean whole-body insecticide levels in seven species of Des Moines River fish, 1977-78 



Residues, ^g/kg Wet Weight 



Dieldrin 



:SDDT 



Heptachlor Epoxide 



Species 


Station 


Date 


Number of 
Analyses i 


Mean 


Range 


Mean 


Range 


Mean 


Range 


Gizzard shad 


1 


Oct. 1977 


3 


171 


142-191 


24 


8-49 


10 


8-13 






Apr. 1978 





— 


— 














Jul. 1978 





— . 



















Oct. 1978 


2 


112 


87-137 


71 


71-72 


16 


12-21 






Mean 




147 




43 




13 






2 


Oct. 1977 


3 


65 


64-77 


20 


13-27 











Apr. 1978 


1 


119 





188 




10 








Jul. 1978 


3 


73 


53-111 


61 


42-71 


14 


7-26 






Oct. 1978 


3 


143 


132-157 


54 


52-59 


17 


15-19 






Mean 




96 




59 




10 






3 


Oct. 1977 





_ 

















Apr. 1978 





— 



















Jul. 1978 


1 


14 


— 


31 


__ 


2 








Oct. 1978 


4 


137 


107-182 


69 


56-104 


29 


12-68 






Mean 




113 




61 




21 




River carpsucker 


1 


Oct. 1977 


4 


44 


24-58 


72 


49-99 











Apr, 1978 


6 


34 


7-33 


52 


19-86 


3 


0^ 






Jul. 1978 


4 


58 


11-114 


40 


10-64 


7 


0-13 






Oct. 1978 


4 


69 


20-197 


35 


18-64 


3 


0-11 






Mean 




49 




50 




3 






2 


Oct. 1977 


2 


39 


31-48" 


56 


19-94 











Apr. 1978 


1 


182 


— 


66 




28 








Jul. 1978 


4 


146 


122-175 


61 


44-89 


31 


23-42 






Oct. 1978 


4 


100 


46-148 


59 


49-67 


12 


3-20 



Mean 



Vol. 15, No. 3, December 1981 



113 



18 



119 



TABLE 3. (cont'd.). Monthly mean whole-body insecticide levels in seven species of Des Moines River fish, 1977- 





Station 


Date 


Number of 
Analyses ' 




Residues, /xg/kg Wet Weight 






DlELDRIN 


2 DDT 


Heptachlor Epoxide 


Species 


Mean Range 


Mean Range 


Mean Range 



Carp 



Channel catfish 



White crappie 



Walleye 



Largemouth bass 



Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 



Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 



47 
25 
26 

32 

47 
48 
47 
26 

40 

19 
34 
46 
29 

31 



24 
47 
32 

35 



36 



33 
50 

43 
81 

65 



13-71 
7^M 
8-50 



43-51 
31-62 
42-51 
14-40 



13-27 
23-52 
34-59 
19-51 



13-31 
39-59 
23-39 



59 


31-98 


79 


73-85 


67 




71 


69-74 


158 


115-240 


192 


180-215 


120 


73-168 


136 




101 


— 


53 


50-56 


29 


— 


45 




39 


15-63 


21 





58 


38-79 


88 


— 


50 




94 


31-301 


55 


24-100 


63 


63-64 


76 




11 


— 


31 


12^4 


15 


14-17 


22 




20 


7-34 


42 


— 


62 


— 



220 


89-329 


36 


27-46 


39 


29-63 


93 




64 


39-101 


38 


18-62 


32 


15-70 


29 


12-56 


43 




18 


14-25 


46 


22-78 


35 


21^9 


61 


35-125 


43 




31 


20-43 


50 


45-57 


60 


42-85 



47 



29 


22-37 


132 


129-136 


70 




25 


16^0 


79 


53-109 


90 


73-118 


51 


42-61 


62 




101 


— 


49 


47-51 


59 


— 


52 




17 


6-35 


37 


— 


47 


38-53 


71 


— 


36 




49 


28-60 


44 


40-54 


63 


54-72 


50 




too 


— 


101 


70-138 


119 


119-120 


107 




8 


7-10 


30 


— 


55 


— 



31-66 

22-182 



25 



92 

92 

84 

64 
82 

76 



1 
4 
13 
2 



36-90 
60-109 



2-6 

2-11 

0-3 



0-2 
3-A 
8-23 
0-4 



5-13 
7-11 
0-3 



3-14 
7-14 
2-4 



12 


6-22 


8 


7-9 


10 










19 


9-25 


40 


37^2 


14 


9-19 


18 




10 


— 


7 


6-8 


1 


— 


5 










5 


— 


7 


3-11 


6 


— 


4 




8 


4-19 


10 


4-18 


5 


4-6 


8 







— 


3 


1-5 





— 


1 










5 


— 


6 


— 



6-12 
0-23 



120 



Pesticides Monitoring Journaij 



TABLE 3. (cont'd.). Monthly mean whole-body insecticide levels in seven species of Des Moines River fish, 1977-78 

Residues, /xg/kg Wet Weight 



Species 



Station 



Date 



Number of 
Analyses i 



DiELDRIN 



Mean 



Range 



2 DDT 



Mean 



Heptachlor Epoxide 



Mean 



Range 



Oct. 1977 

Apr. 1978 

Jul. 1978 

Oct. 1978 

Mean 

Oct. 1977 

Apr. 1978 

Jul, 1978 

Oct. 1978 

Mean 



37 
73 
50 
65 

55 



49 
49 



15-50 
22-124 
22-90 
21-125 



14 


7-20 


55 


32-80 


69 


50-93 


70 


31-90 



55 



72 



72 









12 


6-18 


8 


4-10 


7 


1-11 



^ Number of fish pooled for each analysis can be estimated by dividing total fish caught for that species on the collecting date and station given 
in Table 1 by number of analyses rtm. 



collection date, spatial and temporal trends of pesticide 
levels in these species were difficult to determine and 
were examined selectively. Data from Station 2 that 
were suitable for checking seasonal trends in pesticide 
concentration revealed no consistent seasonal trend in 
dieldrin concentrations among these four species. Con- 
centrations of dieldrin were highest in gizzard shad and 
white crappies in October 1978 and in channel catfish 
and walleyes in July. Available data revealed no statis- 
tically significant difference in dieldrin levels in the four 
species above, in, or below the reservoir. 

More detailed data were available for river carpsuckers 
and carp. Dieldrin levels in individual samples of river 
carpsuckers ranged from 7 to 197 ppb; the mean was 
63 ppb (Table 3). Again, no consistent seasonal trend 
was observed among fish from the three stations, and 
differences with respect to time of year were not statis- 
tically significant. Although dissolved dieldrin concen- 
trations in water samples were similar at all three 
stations, carpsuckers collected in the reservoir during 
1978 contained significantly higher dieldrin concentra- 
tions than did those collected above or below the 
reservoir during the corresponding sampling period 
(F = 11.3, P = 0.001). 

Dieldrin concentrations in carp ranged from 13 to 
62 ppb; mean was 36 ppb (Table 3). Seasonal differ- 
ences in dieldrin concentration in carp were significant 
(F = 5.79, P = 0.01). Dieldrin concentrations were 
nearly constant in carp collected at Station 1 in October 
1977 and April and July 1978 and had decreased in 
October 1978; the concentrations in carp collected at 
Stations 2 and 3 were highest in July. No consistent 
spatial trend was found among sampling dates. Mean 
dieldrin concentrations in carp collected at Stations 1, 2, 
and 3 were not significantly different throughout the 
sampling period. 



Because dieldrin concentration in largemouth bass was 
related significantly to fish length, authors did not con- 
sider length when examining spatial and seasonal trends. 
Residues obtained by determining the difference between 
measured dieldrin concentration and calculated con- 
centration, based on the regression formula of body 
length versus dieldrin (dieldrin [ppb] = 44.01 + 0.43 
total body length [mm]), were used to compare sta- 
tions. Largemouth bass of similar length, captured 
above and within the reservoirs, had similar concentra- 
tions of dieldrin. The single sample from below the 
reservoir was insufficient for comparison. Data on fish 
from Station 2 suggested that dieldrin concentrations in 
bass of similar length were highest in April, but the 
differences among sampling dates were not statistically 
significant. 

No consistent seasonal trend for combined DDT-DDE- 
TDE (iiDDT) levels was evident for any species of fish 
examined (Table 3). Greatest mean values occurred in 
October 1978 for five species and in April 1978 for the 
other two. At Station 2 (in the reservoir), where data 
were most nearly complete, concentrations were greatest 
in April in gizzard shad and river carpsuckers; in Octo- 
ber 1978 in carp, crappies, and bass; and in July in 
channel catfish and walleye. Differences among stations 
were also not statistically significant. Mean concentra- 
tions in all species were greater in fish captured below 
the reservoir than in fish captured in the reservoir. In 
five species, mean concentrations in reservoir fish were 
either lower or equal to those found in fish collected 
above the reservoir. 

Heptachlor epoxide occurred at lower levels than did 
dieldrin and ^-DDT in all species (Table 3). Concen- 
trations were usually greatest in fish collected during 
July 1978. No distinct and consistent spatial trend was 
observed among species, except in river carpsuckers. 



Vol. 15, No. 3, December 1981 



121 



Heptachlor epoxide levels in 1978 were significantly 
higher in river carpsuckers collected in the reservoir 
than in those collected either above or below it 
(F = 20.39, P = 0.0001). 

Discussion 

The lack of measurable amounts of atrazine, alachlor, 
or cyanazine in fish tissue, even though significant con- 
centrations of these compounds were usually present 
in the surrounding water, agreed with reports of rapid 
elimination of herbicides by exposed fish, with little or 
no accumulation of the compounds in body tissue (2, 
3, 9. 10). 

Not only did reservoir-captured fish other than river 
carpsucker fail to contain greater concentrations of 
insecticide than did fish captured above or below the 
reservoir, but fish collected where total insecticide con- 
centrations in water were greatest also did not contain 
greater levels than fish collected elsewhere. Total con- 
centrations of dieldrin in the river water above the 
reservoir were significantly higher than those within and 
below the reservoir (6), but concentrations in the fish 
collected from those locations did not reflect this spatial 
difference. A possible reason is that they absorbed only 
dieldrin in the dissolved state. Average concentrations of 
dieldrin detected in the aqueous phase of the river water 
were similar at all three locations over the study period 
(Table 2). Higher concentrations of dieldrin detected 
above the reservoir were due to the portion that was 
adsorbed onto the suspended sediment of the water. 
This adsorbed portion would probably be less available 
to fish. Another possibility is that the insecticide con- 
centrations in the river water were so low at all three 
stations that fish were capable of metabolizing and 
eliminating the compounds as fast as they were ab- 
sorbed and thus showed no difference in trace amounts 
left in the body. 

Another possible explanation for lack of difference in 
pesticide concentrations in fish above, in, and below the 
reservoir may have been the newness of the reservoir 
and the short retention time for water. The reservoir 
was impounded in April 1977; consequently, the study 
period covered most of the first year of impoundment. 
Leung (6) estimated that 16 kg of dieldrin and 20 kg 
of p.p'-DDE were deposited in the reservoir between 
September 1977 and October 1978. Perhaps these 
amounts were too small to be recycled in sufficient 
quantity from sediment and accumulated by the fish 
through the food chain, if in fact bioaccumulation 
occurs in the reservoir. The potential for recycling 
pesticides from bottom sediment exists because dieldrin 
was present in all samples of Saylorville Reservoir 
bottom sediment analyzed during the study and ranged 
from 0.6 to 12.0 |.ig/kg (6). 'S.DDT was present in some 



form in most samples and ranged from 0.0 to 17.1 
(^(g/kg. Heptachlor epoxide was detected in four of 42 
bottom samples collected and never exceeded 2.0 |.ig/kg. 
Also, water passed through the reservoir in fewer than 
40 days during most of the study period because the 
reservoir was not full. The short retention time might 
also have affected movement of the deposited pesticide 
through the food chain by inhibiting buildup of phyto- 
plankton and zooplankton populations. The effect of 
retention time in the reservoir on pesticide dynamics is 
not well known and would require further study. Also, 
inasmuch as this investigation covered only the first 
year of impoundment and deposition of pesticide-laden 
sediment, the occurrence and distribution of pesticides 
should be re-examined after several years of reservoir 
aging. 

A cknowledgments 

Analyses were conducted under the supervision of John 
J. Richard, at the Ames Laboratory, U.S. Department 
of Energy, Iowa State University, Ames, Iowa. 

LITERATURE CITED 

(/) Baumann, E. R., C. A. Beckert, M. K. Butler, and 
D. M. Sobalh'. 1979. Water qua'ity studies— EWQOS 
sampling. Red Rock and Saylorville Reservoirs, Des 
Moines River, Iowa. Engineering Research Institute 
Annual Report, Iowa State University, Ames, Iowa. 
354 pp. 

(2) Cope, O. B., E. M. Wood, and G. H. Wallen. 1970. 
Some chronic effects of 2,4-D on the bluegill {Lepo- 
mis macrochiius) . Trans. Am. Fish. Soc. 99(1):1-12. 

(.?) Frank, P. A. 1972. Herbicidal residues in aquatic en- 
vironments. Pages 135-148 In R. F. Gould, ed. Fate 
of organic pesticides in the aquatic environment. Adv. 
Chem. Ser. III. American Chemical Society, Washing- 
ton. D.C. 

(4) Iowa Department of Environmental Quality. 1976. 
Water quality management plan. Des Moines River 
basin. Des Moines, Iowa. 

(5) Kellogg. R. L.. and R. V. Bulkley. 1976. Seasonal 
concentrations of dieldrin in water, channel catfish, 
and catfish-food organisms, Des Moines River, Iowa — 
1971-73. Pestic. Monit. J. 9(4) :186-194. 

(6) Leung, S. T. 1979. The effect of impounding a river 
on the pesticide concentration in warmwater fish. 
PhD. thesis. Iowa State University, Ames, Iowa. 155 
pp. Univ. microfilm No. 8010239. 

(7) U.S. Department of Health and Human Services, Food 
and Drug Administration. 1970. Pesticide Analytical 
Manual 1(212.1). U.S. Government Printing Office, 
Washington, D.C. 

{8) U.S. Department of Interior, Geological Survey. 1970. 
Floods in the upper Des Moines River basin, Iowa. 
H. H. Schwob. Iowa City, Iowa. 49 pp. 

(9) Walker, C. R. 1963. Endothal d:rivatives as aquatic 
herbicides in fishery habitats. Weeds 11:226-232. 
(10) Wojtalik, T. A., T. F. Hall, and L. O. Hill. 1971. 
Monitoring ecological conditions associated with wide- 
scale app'ications of DMA 2,4-D to aquatic environ- 
ments. Pestic. Monit. J. 4(4) : 184-203. 



122 



Pesticides Monitoring Journal 



Polychlorinated Biphenyls in Clams and Oysters from New Bedford Harbor, 

Massachusetts, March 1978^ 

Walter I. Hatch,'-' Donald W. Allen, =•* Phillips D. Brady,''-' 
Alan C. Davis," and John W. Harrington " 



ABSTRACT 

Polychlorinalcd biphenyl (PCS) concentrations in clams 
(Mercenaria mercenaria) and oysters (Crassostrea virgin- 
ica) from 17 stations of the western and New Bedford 
Harbor areas of Buzzards Bay, Massachusetts, clearly show 
that the New Bedford Harbor area is severely polluted. Up 
to 5 ppm PCBs {dry weight) were found in shellfish tissue. 
The most likely sources of the PCBs are chronic releases 
from two electrical component manufacturers in New Bed- 
ford. Close proximity of the shellfish to the source of input 
is indicated by a high relative abundance of the di-, tri-, and 
tetrachlorobiphenyls. The data suggest that the New Bed- 
ford Harbor area should be considered, along with the Hud- 
son River and Chesapeake Bay, one of the major sources 
of PCB inputs to the northeastern United Slates coastal area. 

Introduction 

Following Jensen's report identifying polychlorinated 
biphenyls (PCBs) in organisms inhabiting Swedish 
waters (10), there emerged with each succeeding year 
further evidence of worldwide contamination (15). Al- 
though the U.S. Toxic Substances Control Act (1976) 
restricts further contamination, the toxicity of these 
compounds in conjunction with their resistance to en- 
vironmental degradation (7) requires examination of 
their proximate and long-term effects on marine life. 
Their distribution and movement through the environ- 
ment must be continuously monitored. Of particular 
concern are coastal areas where commercial and recre- 
ational shellfishing and fishing in benthic environments 
known to possess hazardous levels of PCBs may result 
in human consumption of contaminated organisms. 



' Woods Hole Oceanographic Institution Contribution Number 4428. 

rhis study was supported in part by U.S. Environmental Protection 

Agency. Grant R 8042-15, the "Mussel Watch" Program, and the 

National Oceanographic and Atmospheric Administration, Office of 

Sea Grant. Grant O. NA79AA-D-00102. 

' Department of Biology. Southeastern Massachusetts University, North 

Dartmouth. MA 

' St. Mary's College of Maryland, P.O. Box 52, St. Mary's City, MD 

!0686. To whom correspondence should be sent. 

P.O. Box 79. Westport, MA 02791 

Commonwealth of Massachusetts, Division of Marine Fisheries, 
Sandwich, MA 

Department of Chemistry, Woods Hole Oceanographic Institution, 
■Voods Hole, MA 02543 



The presence of two large electrical component manu- 
facturers, which use and discharge PCBs, combined 
with the existence of a local fishery suggested the im- 
portance of studying the distribution and accumulation 
of PCBs in the New Bedford, Massachusetts, area. This 
study used edible clams (Mercenaria mercenaria L.) and 
oysters (Crassostrea virginica) as indicators for several 
reasons: They are sessile and thus indicative of regional 
PCB distribution; they inhabit the benthic sediments in 
which large quantities of PCBs have been identified; 
they are microphagous and selectively process particles 
of the size range that adsorb PCBs (3: private com- 
munication: B. Dangle. 1978. U.S. Environmental Pro- 
tection Agency, Toxic Substances Pesticides Branch, 
Air and Hazardous Material Division, Boston, Mass.); 
and they are significant in local sport and commercial 
fisheries. 

Materials and Methods 

COLLECTION OF SPECIES 

Clams ranging in size from 37 to 106 mm were ob- 
tained with an epibenthic sled at depths varying from 
3 to 12 meters. The majority of sampling sites were 
located in Buzzards Bay within a 5.8-nauticaI-mile 
radius of the entrance to New Bedford Harbor (Fig- 
ure I). For comparison, additional specimens were col- 
lected from the Westport River, 1.0 nautical miles from 
its mouth and 14.0 nautical miles from New Bedford 
Harbor. These organisms served as low-level control 
samples. The precise locations of sampling sites within 
the study area were determined largely by the distribu- 
tion of the organisms. The Slocum River estuary was 
also sampled. Because M. mercenaria was not avail- 
able, authors collected Crassostrea virginica (Gmelin) 
as the representative bivalve for this area. 

All sampling was conducted during the week of 
March 11, 1978. Thus, the reported effects of water 
temperature on PCB concentrations (4) were obviated. 
Bottom characteristics of collection sites ranged from 
soft mud to unsorted sand densely infiltrated with shell 
debris. 



^OL. 15, No. 3, DECEMBER 1981 



123 



\^- 







K H O D F I S I. A H l> SOUND 




^,ibVj'/ilJt 



^ 



W 7i'jo' 7rio' 71* 7crW 

FIGURE 1. Sites along Buzzards Bay for the sampling of shellfish contaminated with PCBs. 



ANALYTICAL METHODS 

PCBs were quantitatively determined in pooled tissue 
homogenates. All chromatographic reagents, glassware, 
and equipment contacting the samples were copiously 
rinsed with reagent grade, redistilled solvents (Fisher 
Scientific Co.), in the following sequence: methanol, 
acetone, toluene, and hexane. 

The shucked clams including mantle cavity water were 
homogenized (Polytron R. Kinematica GmbH), lyo- 
philized, and extracted three times with hexane — one 
50-ml portion and two 25-ml portions. The extracts 
were filtered through a column of powdered sodium 
sulfate (NaoSOj) to remove residual water and particu- 
lates and then concentrated to 1 ml for column 
chromatographic cleanup. The cleanup columns were 
packed with 10 g of 200-mesh alumina and 8 g of 
60-200-mesh silica gel, both deactivated 5% with water. 



The columns were first eluted with 15 ml hexane. PCBs 
were then collected in a 50-ml hexane-toluene 
(80 + 20) elution and quantitatively concentrated for 
gas-liquid chromatographic (GLC) analysis. GLC in- 
strument parameters and operating conditions were as 
follows: 



Chromatograph: 

Detector: 

Column: 



Temperatures: 



Pulse interval: 
Carrier gas: 

Detector purge: 
Chart speed: 



Hewlett-Packard, 7620A 
•'■^Ni electron-capture 

glass, 6-ft long by 2-mm ID, packed with a 
mixture of 1.5% OV-17 and !.95% QF-1 on 
100-200-mesh Chromosorb W(AW) 
injection port 225°C 
oven, isothermal 190°C 
detector 300°C 

50 mseconds 

a mixture of 95% argon and 5% methane flow- 
ing at 20 ml/min 
40 ml/min 
0.5 inches/min | 



PCBs were quantitated by comparing the summation 
of eight individual peak areas with a separately injected 
Aroclor 1254 or 1242 standard. The limit of detection, 



124 



Pesticides Monitoring Journal 



based on (he studies of shellfish by Goldberg et al. (6), 
was 0.001 ppm dry weight. Recovery of PCBs from 
samples spiked with Aroclor 1254 before extraction 
was 80% -90% or better. PCBs were confirmed by 
glass capillary gas chromatographic/ mass spectrometric 
(GCMS) analyses at the Woods Hole Oceanographic 
Institution Laboratory using a Finnigan Model 1015 
SL system modified for glass capillary GC. 

Results 

PCBs reported as Aroclor 1254 were detected in all 
samples, ranging from 4.19 ppm dry weight in sam- 
ples collected adjacent to the harbor down to 0.232 
ppm in samples collected approximately 3 nautical miles 
from the harbor (Table 1 ) . Samples from Westport 

TABLE L Aroclor 1254 concentrations in Mercenaria 
mercenaria and Crassostrea virginica, 1978 









Av. CONCN 








Corrected for 








80% Extn 




AV. CONCN 


Av. CONCN 


Efficiency, 




X 10-e g/g 


X 10-« E/g 


X 10-« g/g 


Sampling Site 


Dry Wt ■ 


Wet Wt 


Dry Wt 




Mercenaria i 


mercenaria 




1 


4.19 


0.524 


5.24 


2 


1.36 


0.170 


1.70 


3 


1.75 


0.218 


2.19 


4 


0.443 


0.055 


0.553 


5 


1.54 


0.192 


1.92 


6 


1.42 


0.177 


1.77 


7 


0.290 


0.036 


0.362 


8 


0.625 


0.078 


0.781 


9 


0.537 


0.067 


0.671 


10 


0.232 


0.029 


0.290 


11 


1.04 


0.130 


1.30 


12 


0.879 


O.IIO 


1.10 


13 


0.008 


0.001 


0.010 




Crassostrea 


virginica 




14 


0.560 


0.070 


0.700 


15 


2.57 


0.321 


3.21 


16 


2.28 


0.284 


2.84 


17 


1.47 


0.184 


1.84 



1 Samples were analyzed at Southeastern Massachusetts University 
Laboratories. 

Harbor, Massachusetts (Site 13), containing 0.008 ppm 
PCB were considered indicative of background con- 
centrations. 

Examination of the data suggests a gradient of decreas- 
ing concentration from point-source contamination sim- 
ilar in pattern to that reported from the upper Hudson 
River (/). The lower concentrations found in protected 
coves and estuaries indicate minimal PCB input from 
urban runoff. 

The Commonwealth of Massachusetts has prohibited 
commercial fishing north of a line drawn from Ricket- 
son's Point, Dartmouth (41°34'38"N; 70°56'19"W), to 



Black Rock, Fairhaven (41°34'41"N; 70°51'45"W). 
Sampling sites south of this closed fishing area, how- 
ever, showed PCB concentrations comparable to those 
within the restricted area. High PCB concentrations at 
Sites 6 and 8 may be due to transport paralleling the 
mass flow of water in Buzzards Bay (14). The ele- 
vated PCB concentration of Site 1 1 may be due to tidal 
flushing along the major shipping channel away from 
the harbor. 

A few samples were analyzed in more detail in the 
Woods Hole Oceanographic Institution Laboratory. 
These analyses showed that the PCBs were composed 
of a mixture of components similar to Aroclor 1242 
or 1016 and 1254. In addition, authors analyzed a 
sample of scallops {Aeqiiipecten irradians Lamarck) 
from Cleveland Ledge Light (Figure 1 ) supplied by the 
Falmouth, Massachusetts, shellfish warden. The data 
from these analyses are presented in Table 2. 

TABLE 2. Mixture of Aroclors 1242 and 1254 in selected 

samples from New Bedford Harbor and Buzzards Bay, 

Massachusetts, 1978 



Residues x 10-« g/g 
Dry Wt i 



Site 



Organism 



1242 



1254 



1.46 
0.20 
0.185 



3 Mercenaria mercenaria 1.59 

10 Mercenaria mercenaria 0.22 

Cleveland Ledge Aeqiiipecien irradians 0.093 

' Samples were analyzed at Woods Hole Oceanographic Institute. 

Discussion 

In compliance with the U.S. Toxic Substance Control 
Act, the manufacturing facilities abutting New Bed- 
ford Harbor have severely curtailed the discharge of 
PCBs into harbor waters. AH PCB use was, in fact, 
suspended as of September 1978 (Private Communica- 
tions: Anonymous. 1978. Aerovox Inc. spokesperson; 
Robinson, W. 1978. Cornell Dubilier, Inc., spokes- 
person, both of New Bedford, Mass.). 

However, the discharge of large amounts of PCBs over 
the last 38 years, coupled with the affinity of PCBs for 
sediments (8), has resulted in severely contaminated 
sediments in this area. The literature reveals little data 
for PCBs in sediments from this area. Harvey and 
Steinhauer (9) reported 8.4 x 10"« g PCB/g dry weight 
in outer New Bedford Harbor sediment samples in 
1973. Gilbert et al. (,5), reported values of 0.175- 
0.543 X 10-6 g/g dry weight for concentrations of 
PCBs in surface sediments from eight stations in Buz- 
zards Bay outside New Bedford Harbor. 

deLappe and Risebrough (i) analyzed mussels (Mytilus 
ediilis L.) from inner New Bedford Harbor and re- 



VoL. 15, No. 3, December 1981 



125 



ported a phenomenally high concentration of 110 x 10"^ 
g PCB/g dry weight. They also analyzed water from 
the area and found concentrations up to 580 x 10"'-' g 
PCB/ liter of dissolved and particulates combined. 



Critical questions of the size of the reservoir of PCBs 
in the sediments of the harbor and the extent to which 
they are a source for contamination of other areas of 
Buzzards Bay remain and are being pursued. 



Samples of shellfish, bottom fish, and sediments from 
the New Bedford Harbor area were analyzed in 1976 
and 1977 for PCBs. Concentration ranged as follows; 
0.5-620 X 10 " g PCBs/dry weight sediments; up to 
11.7 X 10'' g PCBs/g wet weight of lobster {Hoinarus 
americanus Milne-Edwards) edible tissue; and up to 
20.0 X 10"6 g PCBs/g wet weight black back flounder 
(Pseudopleuronectes americanus, Walbaum) edible tis- 
sue (unpublished data: Commonwealth of Massachu- 
setts, Department of Environmental Quality Engineer- 
ing, 1976-77). These data led to the closure of the 
New Bedford Harbor area as previously noted. 

Summerhayes et al. (14) and Stoffers et al. (72) in- 
vestigated trace metal contamination of New Bedford 
Harbor sediments. They found up to 1% Cu in sur- 
face sediments in the inner harbor and concluded that 
the harbor area was slowly leaking trace metal-contam- 
inated sediments to nearby Buzzards Bay. Processes 
active in movement of trace metal-contaminated sedi- 
ments are likely to be active in the movement of PCBs 
in the same sediments. 

Thus, even though PCB discharges by industry have 
been curtailed, harbor sediments contain high concen- 
trations of PCBs and can act as a source of PCB con- 
tamination of the harbor for some time to come. Young 
et al. {16) clearly demonstrated that PCB-contaminated 
sediments can be a source of PCB contamination for 
shellfish. Rhoads (11) showed that tidal influences in 
Buzzards Bay result in resuspension of surface sedi- 
ments in some areas with the resulting probability of 
transport to other areas of the bay. Disturbance of the 
sediments in New Bedford Harbor by natural events 
such as tidal movement or storms or by man-induced 
activities such as dredging will probably result in con- 
tamination of other Buzzards Bay areas. 

This may be the reason PCBs were detected in the bay 
sediments by Gilbert et al. (5) and in scallops at 
Cleveland Ledge Light in the present study. However, 
PCBs are so ubiquitous in coastal regions near indus- 
trialized areas that authors cannot be certain at present 
of the origin of the low concentrations of PCBs at 
Cleveland Ledge Light and Buzzards Bay surface sedi- 
ments. 

Data on PCBs in New Bedford Harbor are sufficient 
to identify this area as one of high PCB concentration 
in both sediments and biota. However, the exact mag- 
nitude of the problem has not yet been investigated. 



The few higher-resolution measurements available to 
us at this time indicate that there is a substantial con- 
centration of the di, tri- and tetrachlorobiphenyls in 
the area compared with the amounts of penta- and 
hexachlorobiphenyls usually found in environmental 
samples. This indicates a proximity of the samples 
analyzed to source of input via efl^luents. The di- and 
trichlorobiphenyls are more reactive than the penta- 
and hexachlorobiphenyls and, as distance and time 
between input and measurement increase, there is a 
greater probability that the less-chlorinated biphenyls 
will undergo reaction (15). The electrical component 
manufacturers in New Bedford used primarily Aroclor 
1242 and 1016 mixtures. Thus, the input of the less- 
chlorinated analogs is expected. The New Bedford 
Harbor and Buzzards Bay ecosystems provide a sys- 
tem to study the biogeochemistry of the various PCB 
isomers and authors are currently pursuing this investi- 
gation. 

Our data on the PCBs in oysters from the Slocum 
River estuary (Table 1 ) may suggest a second problem 
with PCBs in the greater New Bedford area. PCB con- 
centrations in C. virginica from the Slocum River es- 
tuary are in excess of those in M. mercenaria collected 
off the river mouth. It is possible that lateral transport 
of contaminated sediments from the New Bedford 
Harbor area to a point upstream in the adjacent Slocum 
River would exceed transport to a point off the mouth 
of the river. This is unlikely but cannot be ascertained 
because of lack of knowledge about sediment transport 
in the area. A second possibility is the release of PCBs 
from a landfill site to the aquifer feeding the Slocum 
River. It has been established that there are over 
200,000 kg of PCBs buried in the New Bedford munici- 
pal landfill located on the aquifer feeding the Slocum 
River valley. A few preliminary measurements have 
shown that some PCBs are present in waters draining 
from the landfill (13). Extensive contamination of 
groundwaters was not found, based on a few measure- 
ments. However, time series measurements and mass 
flow calculations have not been made (13). This prob- 
lem merits more extensive study because the aquifer 
represents the primary source of drinking water for 
the town of Dartmouth, Massachusetts. 

Recent measurements of PCBs in the common blue 
mussel (Mytihts ediilis) and in oysters (Crassostrea 
virginica) collected around the coast of the United 
States have shown that the northeastern U.S. coastal 
area is more contaminated with PCBs on a regional 



126 



Pesticides Monitoring Journal 



basis than most other areas of the coast (6). The data 
and discussions presented here suggest that the New 
Bedford Harbor area should be considered along with 
the Hudson River and Chesapeake Bay as one of the 
sources of these regionally elevated concentrations. 

Acknowledgments 

Authors thank the officials and scientists of the Com- 
monwealth of Massachusetts, Office for Environmental 
Affairs, and its various departments for making avail- 
able unpublished file data and discussions. 

LITERATURE CITED 

(!) Berle, P. A. A. 1978. The Hudson River: A reclama- 
tion plan. 15 pp. New York State Department of En- 
vironmental Conservation, Albany, N.Y. 

(2) Courtney, W. A. M., and G. R. W. Denton. 1976. 
Persistence of polychlorinated biphenyls in the hard 
clam (Mercenaria mercenaria) and the effect upon the 
distribution of these pollutants in the estuarine en- 
vironment. Environ. Pollut. 10(l):55-64. 

(i) deLappe, B. W., and R. W. Risebrough. 1980. The 
sampling and measurement of hydrocarbons in natu- 
ral waters. Pages 29-68 in Hydrocarbons and Halo- 
genated Hydrocarbons in the Aquatic Environment. 
B. K. Afghan and D. Mackay (Eds.). Plenum Press, 
New York, N.Y. 

(4) Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr. 1970. 
A polychlorinated biphenyl (1254) in the water, sedi- 
ment and biota of Escambia Bay, Florida, Bull. En- 
viron. Contam. Toxicol. 5( 1) : 171-180. 

(5) Gilbert, T., A. Clay, and A. Barker. 1973-74. A site 
selection and study of ecological effects of disposal of 
dredged materials in Buzzards Bay, Massachusetts. 
New England Aquarium Report to U.S. Army Corps 
of Engineers, New England Division, 70 pp. 

(6) Goldberg, E. D., V. T. Bowen, J. W. Farrington, 



G. Harvey, J. M. Martin, P. L. Parker, R. W. Rise- 
brough, W. Robertson, E. Schneider, and E. Gamble. 
1978. The mussel watch. Environ, Conserv, 5(2): 
101-105, 

(7) Hammond, P. B., I. C. T. Nisbet, and A. S. Sarofin. 
1972. Polychlorinated biphenyls — environmental im- 
pact. Environ. Res. 5(1) :249-262. 

(5) Haque, R., D. Schmedding, and V. H. Freed. 1974. 
Aqueous solubility, adsorption and vapor behavior of 
polychlorinated biphenyl Aroclor 1254. Environ, Sci, 
Technol. 8(2) ; 139-142. 

(9) Harvey, G. R., and W. G. Steinhauer. 1976. Environ- 
mental Biogeochemistry, Vol. I, Chapter 15, Ann 
Arbor Science Publishers, Inc, Ann Arbor, Mich, 
(10) Jensen, S. 1966. Report of a new chemical hazard. 

New Sci. 32(512) :612-615. 
(//) Rhoads, D. C. 1974. Organism-sediment relations on 
the muddy sea floor. Oceanogr. Marine Biol. Rev. 
12:263-300. 

(12) Staffers, P., C. Suminerhayes, U. Forslner, and S. R. 
Patchineclam. 1977. Copper and other heavy metal 
contamination in sediments from New Bedford Har- 
bor, Massachusetts: A preliminary note. Environ. Sci. 
Technol. 1 1 (9) :819-821. 

(13) Stralton, C. L., K. L. Tullle, and J. M. Allan. 1978. 
Final Task Report, Research Request No, 4, Contract 
No, 68-01-3248, U, S, Environmental Protection 
Agency, Washington, D.C, 

{14) Summerhayes, C. P., J. P. Ellis, P. Sloffer, S. Briggs, 
and M. G. Fitzgerald. 1977. Fine-grained sediment 
and industrial waste distribution and dispersal in New 
Bedford Harbor and western Buzzards Bay, Massa- 
chusetts, Tech, Rept, No, 76-115, Woods Hole Ocean- 
ographic Institution, Woods Hole, Mass. 

(15) U . S. Environmental Protection Agency. 1976. Criteria 
document for PCBs, Massachusetts Audubon Society, 
prepared by U.S. Department of Commerce, National 
Technical Information Service, PB-255-397, 

(16) Young, D. R., T. C. Heesen, and D. J. McDermolt. 
1976. An offshore biomonitoring system for chlori- 
nated hydrocarbons. Marine Pollut. Bull. 7(8):156- 
159. 



Vol. 15, No. 3, December 1981 



127 



Nationwide Residues of Organochlorine Compounds in 
Wings of Adult Mallards and Black Ducks, 1979-80 



Brian W.Cain' 



ABSTRACT 

Organochlorine residues in wings of adult mallards (Anas 
platyrhynchos) and black ducks (Anas rubripes) were mon- 
itored nationwide from birds harvested during the 1979-80 
hunting season. DDE residues were found in all samples. 
DDT residues had declined from levels reported in 1976 on 
a flyway basis but the decline was significant fP < 0.05} 
only in the Pacific Flyway. Levels of DDT, DDE, TDE, 
and dieldrin were low on a flyway basis, and all but DDE 
declined significantly fP < 0.05) in the percent occurrence. 
Polychlorinated hiphenyls (PCB) levels were lower in mal- 
lard wings from all flyways compared with 1976 data, but 
percent occurrence had significantly IP < 0.05) increased. 
Pools from Alabama and New Mexico continued to show 
higher DDE residues than pools from other areas. 



relation between DDT residues in the wing and those 
in breast skin, breast muscle, brain, kidney, liver, and 
other tissues from captive mallards and scaup 
ducks (1). 

This paper presents results from the mallard and black 
duck wings collected during the 1979-80 hunting sea- 
son and includes the mean residue levels for each state. 
The percentage of the pools from each flyway that con- 
tain a particular contaminant residue is presented and 
compared with the 1976-77 hunting season. The mean 
value of organochlorine residues in wings by major fly- 
ways is presented and compared with the 1976 col- 
lection. 



Introduction 

During the 1965-66 hunting season, the Fish and Wild- 
life Service, U.S. Department of the Interior, as part 
of the National Pesticide Monitoring Program (2), 
began to monitor organochlorine pesticides in duck 
wings collected by hunters. Justification for this method 
of collection was given by Johnson et al. (5). The black 
duck ranges over a large part of the Atlantic Flyway 
and the mallard is found throughout the rest of the 
contiguous 48 states. Thousands of wings collected 
each year by cooperating hunters are sent to collection 
sites in each of the four flyways. Waterfowl migrate 
twice a year within four major flyways that consist of 
states or parts of states in which the birds feed or rest 
for short periods of time. Millions of waterfowl spend 
the winter months in the southern portions of these fly- 
ways, and may be exposed to environmental contami- 
nants different from those found in northern nesting 
areas. 

Heath and Prouty (4) successfully tested the monitor- 
ing methodology in 1965 using mallard and black duck 
wings collected from New York and Pennsylvania. A 
later report showed there was a highly significant cor- 



Methods 



WING COLLECTIONS 



' Fish and Wildlife Service, U.S. Department of the Interior, Patuxent 
Wildlife Research Center, Laurel, MD 20811 



During the 1979-80 hunting season, cooperating water- 
fowl hunters mailed approximately 11,660 wings from 
adult mallards or black ducks to a regional collection 
point within each of the four flyways. Each wing was 
sent in a separate envelope that listed the date, county, 
and state where the bird was harvested. The wings were 
held in frozen storage until March or early April 1980 
when biologists determined the sex and maturity of 
each bird. Only adult wings were used for the pesticide 
monitoring program to maintain the sampling consis- 
tency established by Heath and Hill (i). Wings from 
each state were sorted randomly into pools of 25 wings, 
and random samples of these pools were made by using 
a random numbers table. The number of pools taken 
was such that about 50% of the wings submitted from 
a state were selected for organochlorine analyses. Each 
pool of 25 wings was wrapped in aluminum foil, tagged 
with a coded number, frozen, and shipped to Raltech 
Scientific Services, Inc. (formerly WARF Institute, Inc.) 
in Madison, Wisconsin. There were 24 pools of black 
duck wings and 29 pools of mallard wings from the 
Atlantic Flyway, 64 pools of mallard wings from the 
Mississippi Flyway, 54 pools of mallard wings from the 
Central Flyway, and 44 pools of mallard wings from 
the Pacific Flyway. 



128 



Pesticides Monitoring Journal 



ANALYTICAL PROCEDURES 

Wings in eacli pool were trimmed by removing most of 
the feathers and the distal joint with a pair of scissors. 
Remaining portions were homogenized in a Hobart 
grinder, and approximately 10 g was removed, weighed, 
and placed in a preweighed 150-ml beaker. The beaker 
and sample were oven-dried 2 weeks at 40°C and 
reweighed, and the sample dry weight was recorded. 
Approximately 40 g homogenized sample was weighed 
into a 250-ml beaker and mixed with 100 g anhydrous 
sodium sulfate, placed overnight in a hood, and then 
transferred to a 43-mm by 123-mm prewashed What- 
man extraction thimble plugged with glass wool. The 
thimble was placed in a desiccator overnight and then 
extracted for 8 hours in a Soxhlet apparatus with a 
mixture of 150 ml each of ethyl ether and petroleum 
ether. This solution was then concentrated on a steam 
bath, and the residue was transferred to a 50-ml volu- 
metric flask and diluted to volume with a mixture of 
dichloromethane-cyclohexane (15 + 85). 

A 5-ml aliquot of the extract was placed in an Auto- 
Prep 1001 gel permeation chromatograph that had been 
standardized for chlorinated insecticides and PCB com- 
pounds. The column was glass, 600 mm by 25 mm, and 
packed with 60 g of 200-400-mesh Bio-Beads (SX-3). 
The solvent was dichloromethane-cyclohexane (15 + 
85) at the flow rate of 5.5 ml/min. The resulting solu- 
tion was concentrated on a flash evaporator to approxi- 
mately 1 ml in the presence of 5 ml iso-octane and 
diluted to 25 ml with petroleum ether. A 10-ml aliquot 
of this gel permeation extract was placed in a 25-g 
silica-gel 60 column and three elutions were prepared. 
The first was eluted with 90 ml petroleum ether and 
contained hexachlorobenzene (HCB) and mirex; the 
second was eluted with 200 ml petroleum ether and 
contained PCB compounds and DDE; and the third was 
eluted with 150 ml of a mixture of acetonitrile-hexane- 
dichloromethane (1 + 19 -f 80) and contained the 
remaining chlorinated insecticides. Fraction three was 
concentrated on a flash evaporator to I ml and diluted 
to 10 ml with petroleum ether. Four microliters from 
each fraction was injected into a gas chromatograph 
equipped with an electron-capture detector. 

Instrument parameters and operating conditions ap- 
plied to all samples except where difTerences are noted: 

Column: 2 m by 4 mm 

Packings: (1) organochlorine pesticides and PCBs: a mix- 

ture of 1.95% OV-n and 1.5% QF-I on 
100-200-mesh Supelcoport 

(2) chlordane isomers: 3% OV-1 on 80-100- 

mesh Gas-Chrom Q 
Temperatures, °C column 200 

injector 250 

detector 300 
Carrier gases: a mixture of 95% argon and 5% methane 

Flow rates (1) 33 ml/min 

(2) 32 ml/min 



Lipids were determined by using a 5-ml aliquot of the 
Soxhlet extract in a preweighed 2-dram vial. The vial 
was placed in a 40°C oven for 3 days to remove the 
solvent and then reweighed, and the amount of the 
lipids was calculated. 

All residues are expressed as ppm wet weight and may 
be converted to an approximate dry or lipid weight 
by dividing by 0.60 or 0.14, the mean proportions of 
dry or lipid material in the samples, respectively. Mean 
residue values were calculated by using 0.00 as the 
value for samples in which no residue was reported at 
the 0.01 -ppm sensitivity level. The recovery percentages 
from spiked samples were DDE, 85; TDE, 125; di- 
eldrin, 98; heptachlor epoxide, 90; and Aroclor 1254, 
118. Analytical results have not been corrected for re- 
covery. Residues in 5% of the pools were confirmed 
by mass spectrometry. 

The percentage occurrence of the organochlorines in 
wings from each flyway were compared with the 1976 
collection data by using a test for two population pro- 
portions. Mean residue levels of DDE. DDT, TDE, 
dieldrin, and PCBs were compared on a flyway basis 
with the published 1976 data of White (8) by using 
only those samples with a detectable residue level. A 
/-test comparison was made on each data pair that had 
detectable residues in at least 50% of the pools col- 
lected. A P < 0.05 was necessary for significance for 
all statistical comparisons. 



Results and Discussion 

Residues of DDE, DDT, TDE, dieldrin, and PCBs in 
the duck wings from the 1979-80 hunting season are 
presented in Table I. These data, collected from 5,268 
wings (215 pools), are presented as mean values for 
each state in a flyway and are arranged in a North to 
South direction. Data in Table 1 should not be inter- 
preted on a statewide basis alone because waterfowl 
migrate and may cover a wide area and range of habi- 
tats in many states. Samples from some localities (i.e., 
Alabama and New Mexico) continue to show higher 
residues of DDT and DDE than do samples from the 
other localities. This situation in Alabama was reported 
earlier (3, 7, 8), and a possible source of the contami- 
nation was described by O'Shea et al. (6). 

The highest DDE level, 3.28 ppm, was detected in a 
pool composed of wings from Arizona and New Mex- 
ico, and the lowest level of DDE residue, 0.02 ppm, 
occurred in pools from Florida and Kentucky. DDE 
residues occurred in all wing pools; however, DDT, 
TDE, and dieldrin were found in fewer pools in the 
1979-80 wing collection than in the 1976-77 collection 



Vol. 15, No. 3, December 1981 



129 



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131 



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132 



Pesticides Monitoring Journal 



(Table 2). The highest level of dieldrin was 1.18 ppm in 
a pool from Alabama (Table I ) . PCBs were detected 
in all pools from the Atlantic Flyway and were found 
in at least 90% of the pools from the other three fly- 
ways (Table 2). This is a significant increase (P < 0.05) 
in the percentage occurrence of PCBs over that re- 
ported for the 1976-77 hunting season (Table 2). The 
highest residues of PCBs were 1.80 ppm in a pool of 
black duck wings from New York and 1.62 ppm in a 
pool of mallard wings from North Carolina. Three 
pools from the Pacific Flyway, two from the Central 
Flyway, and one from the Mississippi Flyway did not 
have PCB residues at the 0.01 -ppm limit of detection 
(Table 1). 



In addition to the organochlorine compounds listed in 
Table 1, heptachlor epoxide, chlordane isomers, and 
hexachlorobenzene (HCB) were found in duck wings, 
but less frequently. Residues of these three compounds 
seldom exceeded 0.1 ppm, so these data were not in- 
cluded in Table 1. The percentage occurrence of these 
three compounds and the percentage occurrence of 
mirex and endrin are presented in Table 2 and com- 
pared with the 1976-77 wing data. Hexachlorocyclo- 
hexane, lindane, and toxaphene residues were found in 
only three pools at the 0.01 -ppm level. 

Means of DDE, DDT, TDE, dieldrin, and PCBs in the 
1976 and 1979 collections are presented by flyways in 
Table 3. To compare these residues with the data pre- 



TABLE 2. Comparison of ihe percent occurrence of organochlorine residues in duck wings by flywav for the two 

collection periods of 1976-77 and 1979-80 





Year of 
Collection 


No. OF 
Pools 






Organochlorine Residues, ppm 


Wet Weight 








Species 


DDE 


DDT 


TDE Dieldrin 


PCBs 


Hepta- 
chlor 
Epoxide 


Mirex 


Endrin 


HCB 


Chlor- 
dane 
Isomers 


ATLANTIC FLYWAY 


Black duck 
Black duck 
Mallard 
Mallard 


1976-1977= 
1979-1980 
1976-1977 
1979-1980 


32 
24 
20 
29 


100, s 
100. 
100, 
100, 


69, 
38, 
60. 
52b 


66. 84, 
29, 58„ 
50. 85. 
17„ 62„ 


100. 
100, 
100. 
100. 


34, 

4, 

50. 

14,, 


19, 
13. 

50. 
3b 


3. 
0, 
5. 
3, 


16, 

21 „ 

10. 

3h 


59. 
58, 
55. 
48b 



MISSISSIPPI FLYWAY 


Mallard 
Mallard 


1976-1977 
1979-1980 


69 

64 


100, 
100, 


87. 
28b 


38. 78, 61, 
13b 64b 98b 


45, 
28b 


29, 

2b 


4. 
8b 


7, 
2b 


22. 
16, 


CENTRAL FLYWAY 


Mallard 
Mallard 


1976-1977 
1979-1980 


56 

54 


100, 
100, 


79. 

22b 


45, 64. 13, 
2b 22b 90b 


48, 
30b 


14, 
Ob 


2. 
0. 


9, 
4b 


14, 
7b 


PACIFIC FLYWAY 


Mallard 
Mallard 


1976-1977 
1979-1980 


50 
44 


100. 
100, 


92. 
57b 


58. 62, 14, 
7b 39b 93b 


32, 
23b 


4, 
0, 


0, 
0. 


24, 
23. 


14. 
5b 



1 Detection limit ^0.01 ppm. 
^ Data taken from White (8). 
3 1979-80 percent occurrence is significantly different (P<0.05) than 1976-77 percent occurrence where subscript letters (a or b) differ. 



TABLE 3. 


Means and standard errors of organochlorine residues in waterfowl wing pools by major flyway 


1976 and 1979 




Residues, ppm Wet Weight 




Species 


Flyway Year Pools DDE DDT TDE Dieldrin 


PCBs 



Black duck Atlantic 1976^ 32 

1979 24 

Mallard Atlantic 1976 20 

1979 29 

Mallard Mississippi 1976 69 

1979 64 

Mallard Central 1976 56 

1979 54 

Vlallard Pacific 1976 50 

1979 44 



0.39 -I- 0.07 

(32) 
0.32 ± 0.04 

(24) 
0.32 ± 0.07 

(20) 
0.27 ± 0.03 

(291 
0.25 ± 0.04 

(69) 
0.17 ± 0.03 

(64) 
0.28 + 0.17 

(56) 
0.10 ±0.02 

(54) 
0.22 ± 0.04 

(50) 
0.35 ± 0.08 

(44) 



0.06 -1- 0.01 


0.03 H- 0.00 


(22) 


(21) 


0.02 -*- 0.00 


0.04 + 0.03 


(9) 


(7) 


0.07 -1- 0.01 


0.02 + 0.01 


(12) 


(10) 


0.02 -t- 0.0 1 


0.01 + 0.00 


(15) 


(5) 


0.07 -1- 0.01 


0,05 + 0.03 


(60) 


(26) 


0.05 + 0.01 


0.05 -1- 0.02 


(18) 


(8) 


0.05 -t- 0.01 


0.04 -1- 0.01 


(44) 


(25) 


0.03 -*- 0.01 


0.02 ■+■ 0.00 


(12) 


(1) 


0.06 -t- 0.01 = 


0.03 + 0.00 


(46) 


(29) 


0.02 + 0.01 


0,02+0.01 


(25) 


(3) 



0.04 -^ 0.01 

(27) 
0.03 ± 0,01 

(14) 
0.06 + 0.03 

(17) 
0.05 ± 0.03 

(18) 
0.05 ± 0.01 

(54) 
0.05 ± 0.03 

(41) 
0.03 ± 0.01 

(36) 
0.02 ± 0.00 

(12) 
0.02 ± 0.00 

(31) 
0.02 ± 0.00 

(17) 



0.52 ± 0.08 

(32) 
0.63 -I- 0.09 

(24) 
0.52 ±0.18 

(20) 
0.45 ± 0.07 

(29) 
0.23 ± 0.03 

(42) 
0.11 ±0.02 

(63) 
0.15 ±0,01 

(7) 
0,06 ± 0.01 

(49) 
0.16 ±0.04 

(7) 
0.07 ± 0.02 

(41) 



VOTE: Values in parentheses are actual number of pools containing residues; means were calculated using these values. 
Data taken from White (8). 
■Significant difference (P < 0.05). 



v'OL. 15, No. 3, December 1981 



133 



sented from the 1976 collection (8), the author calcu- 
lated the mean values by using only the wing pools that 
contained the residues. A trend toward lower mean 
values for most of these residues in both the mallard 
and black duck wings was not significant (F > 0.05). 

The only significant decline (P < 0.05) was DDT 
residues in mallard wings from the Pacific Flyway 
(Table 3). Residues of DDT, TDE, and dieldrin were 
all low in the four flyways, and the percentage occur- 
rence of these contaminants has declined significantly 
(P < 0.05) since 1976. PCB residues were low in mal- 
lard wings from the Mississippi, Central, and Pacific 
Flyways, but their percentage occurrence increased sig- 
nificantly (P < 0.05) above the 1976 level (Table 2). 

Conclusions 

Mean values of DDE residues in mallard and black 
duck were not significantly (P > 0.05) lower than 
those reported for 1976 in all flyways. DDT, TDE, 
and dieldrin residues in duck wings have declined sig- 
nificantly (P < 0.05) in the percentage occurrence in 
all flyways. The decline of PCB residues in mallard 
wings from all flyways was not significant (P > 0.05). 
PCBs. however, occurred in a significantly (P < 0.05) 
larger percent of the 1979-80 pools than in the 1976 
pools. 

A cknowledgnienls 

The author thanks the following people in the U.S. 
Fish and Wildlife Service for their help in the wing col- 
lections: Samuel M. Carney, Michael F. Sorensen, and 
Elwood M. Martin from the Office of Migratory Bird 



Management; Environmental Contaminant Evaluation 
Stall Specialist James B. Elder in Region 3: Eugene W. 
Hansmann in Region 6; and David J. Lenhart in Re- 
gion 1 . Biological aides Ellen PafTord and Lynn Palmer 
helped prepare the wings for shipment. Christine Bunck 
provided the statistical advice and computations, and 
Patty McDonald compiled the tables. E. H. Dustman 
and D. H. White reviewed the manuscript. 

LITERATURE CITED 

(/) Dimial. D. L., and T. J. Peterle. 1968. Wing and body 
tissue relationships of DDT and metabolite residues in 
mallard and lesser scaup ducks. Bull. Environ. Contam. 
Toxicol. 3(1 ):37-48. 

(2) Hcatli. R. G. 1969. Nationwide residues of organo- 
chlorine pesticides in wings of mallards and black 
ducks. Pestic. Monit. J. 3(2): 115^123. 

(.?) Healh. R. G ., ciiiJ S. A. Hill. 1974. Nationwide organo- 
chlorine and mercury residues in wings of adult mal- 
lards and black ducks during the 1969-70 hunling 
season. Pestic. Monit. J. 7(.^/4) : 153-164. 

{4) Heath. R. G., and R. M. Proiity. 1967. Trial monitor- 
ing of pesticides in wings of mallards and black ducks, 
Bull. Environ. Contam. Toxicol. 2(2): 101-110. 

(.5) Johnson. R. E.. T. C. Carver, and E. H. Dustman. 
1967. Indicator species near top of food chain chosen 
for assessment of pesticide base levels in fish and wild- 
life — clams, oysters, and sediment in estuarine environ- 
ment. Pestic, Monit. I. 1(1) :7-13. 

(6) O'Shea. T. J.. IV. J. Flemin.i; III. and E. Cromartie. 
I9S(). DDT contamination at Wheeler National Wild- 
life Refuge. Science 209:509-510. 

(7) White. D. H.. and R. G. Heath. 1976. Nationwide 
residues of organochlorines in wings of adult mallards 
and black ducks. 1972-73. Pestic. Monit. J. 9(4):176- 
185. 

(<S) While. D. H. 1979. Nationwide residues of organo- 
chlorine compounds in wings of adult mallards and 
black ducks, 1976-77. Pestic. Monit. J. 13(1):12-16. 



134 



Pesticides Monitoring Journal 



HUMANS 



Organochlorine Pesticide Residues in Human Milk Samples from Comarca 

Lagunera, Mexico, 1976 

L. Albert,' P. Vega,= and A. Porlales' 



ABSTRACT 

Milk samples were obtained from 15 nursing mothers in the 
agricultural region of Comarca Lagunera, Mexico, and were 
analyzed for organochlorine pesticide residues. Nine difjerent 
types of residues were found. Of these, p,p'-DDE, p,p'-DDT, 
and 13-BHC occurred most frequently. All samples had con- 
centrations of DDT-derived compounds higher than the 
practical limit recommended by the U.N. Food and Agri- 
culture Organization/World Health Organization for DDT 
in cows' milk. Residues of other chlorinated hydrocarbons 
were present at levels similar to those found in human milk 
in other developing countries. 

Introduction 

In the developing countries, organochlorine pesticides 
are used in large quantities to control agricultural pests 
and the vectors of endemic diseases. Although there 
have been few studies to determine organochlorine resi- 
dues in human milk samples, some studies have been 
carried out in Guatemala {20, 28), Portugal (12), and 
Argentina (10). 

In spite of high production, import, and use of these 
compounds in Mexico, there had been no studies of 
their presence in human milk. The present study is 
a preliminary evaluation of those residues in human 
milk from Comarca Lagunera. This is an important 
agricultural region of Mexico, on the border of the 
states of Durango and Coahuila, where the principal 
crop is cotton. 

Comarca Lagunera was selected because previous anal- 
yses have shown consistently high levels of organo- 



1 INIREB, Ap. Postal 63, Xalapa, Veracruz, Mexico. To whom all 

correspondence should be addressed. 

' Laboratory of Environmental Chemistry, Department of Chemistry, 

CIEA-IPN, Mexico, D. F., Mexico 

' School of Medicine, University of Coahuila, Torreon, Coahuila, 

Mexico 



chlorine pesticide residues in foodstuffs and animal 
feeds (3. 4) and in human adipose tissue (2). 

Methods and Materials 

All solvents were distilled twice in all-glass systems and 
checked by a 100-fold concentration test. Florisil was 
standardized for oil retention ability and activity. Be- 
fore use, all reagents were checked for electron-captur- 
ing impurities. 

Fifteen human milk samples were collected during 
March 1976 from voluntary donors at the University 
Hospital in Torreon, the main city of Comarca. All 
donors had lived in the area for 4 or more years. Four 
donors were from medium-income homes and 1 1 were 
from low socioeconomic levels. Seven lived in urban 
areas and eight lived in rural areas of Comarca. 
Donors' ages ranged from 16 to 30 years, with infants 
ranging in age from 1 to 29 days. All samples were 
manually expressed directly into wide-mouth jars that 
had been thoroughly cleaned. Jars were closed with 
Teflon-lined caps and stored in a refrigerator until 
samples were analyzed. 

Lipids were extracted at the School of Medicine in 
Torreon immediately after sampling was completed. 
The volume of each sample was measured and the lipids 
were extracted with a BD-1 solution (75) at 3:2 (v/v) 
sample rsolution ratio. Extracted lipids were carefully 
transferred to clean vials and weighed. Extractable 
lipids averaged 1.91% ± 0.97%. Lipids were frozen 
and taken to the CIEA-IPN laboratories in Mexico 
City, where they were kept at — 20°C until analysis. 

Three sets of analyses were carried out; each was com- 
prised of five samples. Along with each set, a blank 
and a sample of milk lipids fortified with 1 ppm (i-BHC 



Vol. 15, No. 3, December 1981 



135 



and 3.5 ppm p,p'-DDE (lipid basis) were also analyzed. 
Recoveries ranged from 96% to 103%. 

The lipids were dissolved in /i-hexane and transferred 
to a chromatographic column prepared with 10 g 
Florisil deactivated with 2% water. The column was 
eluted with 100 ml of a 70:30 (v/v) mixture of petro- 
leum ether-CHXL (7). The eluate was concentrated 
carefully and the residue was dissolved in n-hexane for 
gas-liquid chromatographic (GLC) analysis. No further 
cleanup was necessary. 

[dentification and quantitation were carried out by GLC 
under the following conditions: 



Chromatographs: 

Detectors; 

CoUimn^i: 



Varian Aerograph, Models 1440 and 2440 
electron-capture tritium and scandium tritiide 
glass, 6-ft long by 2-mm ID, packed with either 
(a) 3% OV-101 or (b) 3% OV-210, both on 
100-120-mesh Gas-Chrom Q 

Temperatures: column (a) 170°C 

column (b) I50°C 

Carrier gas: high-purity nitrogen flowing through (a) at 40 

ml'min and through (b) at 35 ml/min 

Qualitative identification was accomplished by compari- 
son of retention times with those of known standards 
provided by the U.S. Environmental Protection Agency. 
Quantitation was based on relative peak heights of in- 
dividual standard solutions of each compound. The 
minimum detectable level was 0.005 |.(g/g (extractable- 
lipid basis) for all compounds. 

Identity was confirmed routinely by the multicolumn 
technique (//). using a column packed with a mixture 
of 2% QF-1 and 2% SE-30 on 100-120-mesh Gas- 
Chrom Q. Column temperature was 150°C and carrier 
gas was nitrogen flowing at 35 ml/min. All samples 
containing more than 0.5 ^ig/g (extractable-lipid basis) 
of p.p'-DDE and p.p'-DDT were confirmed by chemical 
derivation (8) and by thin-layer chromatography (TLC) 
(7). Samples containing above 0.2 ug [^-BHC/g were 
confirmed only by TLC. 

Results and Discussion 

The number of chlorinated hydrocarbon residues per 
sample ranged from five to nine, with five to six com- 
pounds per sample occurring most often. 

The following compounds were identified: hexachloro- 
benzene, (t-BHC, |5-BHC, p.p'-DDE, p.p'-TDE, p.p'- 
DDT, dieldrin, endrin, and heptachlor epoxide. Those 
found more frequently in concentrations higher than 
0.01 |.ig/g were p-BHC. p.p'-DDE. and p,p'-DDT. 
However. p,p'-DDT was found in only 1 1 samples, 
whereas p,p'-DDE was present in all samples. Hexa- 
chlorobenzene and p,p'-TDE occurred at concentrations 
above 0.01 ug/g in only four and five samples, respec- 
tively; dieldrin, heptachlor expoxide, a-BHC, and en- 
drin were found only in trace concentrations — below 



0.01 |.ig/g. Among these, the most frequent was di- 
eldrin, which was identified in 13 samples, and hepta- 
chlor epoxide, which was present in 7. These data are 
summarized in Table 1. 

The means, ranges, and standard deviations for these 
compounds are presented in Table 2. These data are 
calculated both on an extractable-lipid basis (ug/g) 
and in whole milk (i^ig/ml). Only the results from sam- 
ples with more than 0.01 |.ig/g of a given compound 
were considered for these calculations. Total equivalent 
DDT was obtained by multiplying the values for p,p'- 
DDE and p,p'-TDE by the appropriate factors before 
addition. 

Among the compounds with high percent occurrences. 
p.p'-DDE was found at the highest mean concentration. 



TABLE 1. Occurrence of organochlorine pesticide residues 

in liuniiin h?i7A samples from Comarca Lagunera, Mexico, 

J 976 









Samples with 




Total 


Positive 


Residue Levels 




Samples 


Above 0.01 


ixi/i 


Compound 


n/N 


% 


n/N 


"o 


Hexachlorobenzene 


915 


60 


4/15 


11 


a-BHC 


4/15 


27 


— 


— 


/3-BHC 


15/15 


100 


15/15 


100 


Dieldrin 


13/15 


87 


— 


— 


Endrin 


2/15 


13 


— 


— 


Heptachlor epoxide 


7/15 


47 


— 


— 


p.p -DDE 


15/15 


100 


15/15 


100 


P.p'-DDT 


15/15 


100 


11/15 


73 


p.p'-TDE 


15/15 


100 


5/15 


33 



NOTE: n =: number 
samples. 



of positive samples; N ^= total number of 



TABLE 2. Concentrations of organochlorine pesticide res- 
idues in human milk samples from Comarca Lagunera, 
Mexico. 1976' 



Concentrations of Residues ^g/g 




EXTRACTABLE LIPID 


Whole Milk 




x + so 


x + sn 


Compound 


(Range) 


(Range) 


Hexachlorobenzene 


0.21 -1-0.23 


0.002 + 0.002 




(ND-0.481 


lND-0 0041 


/3-BHC 


1.63 -1-0.94 


0.030 + 0.026 




(0,46-3.58) 


(0.007-0.1001 


P.P'-DDE 


10.35 -1- 11.02 


0.202 -1- 0.266 




( 1 .36-36.01 1 


(0013-0 984) 


p,p'-DDT 


1.98 + \l<i 


0.049 + 0.073 




(T-6.041 


(T-0,243l 


P,P'-TDE 


0.56 + 0.37 


0.015 ±0.016 




(T-1.061 


(T-0,043l 


Total Equiv. DDT = 


13.18-1- 13.39 


0.266-^0.348 




(1.51^3.861 


(0.020-1.198) 



NOTE: I = mean concentration; SD ^ standard deviation; NO 

= <0.0fl5 |Ug/g extraciable lipids; T = Trace (0.01 ^g/g >T>0,005 

^'g/g exiractable lipids). 

' Calculations based on samples with residues >0.01 fxi/i extractable 

lipids. 

= DDT - 1.115 DDE + 1.11 TDE. 



136 



Pesticides Monitoring Journal 



followed by p,p'-DDT and p-BHC. Total equivalent 
DDT ranged from 1.21 to 35.09 times the practical 
limit (1.25 ^ig/g, lipid basis) recommended by FAO/ 
WHO for DDT alone or combined with TDE and 
DDE in cows' milk (26); the mean concentration 
of p,p'-DDT was 1.98 ^ig/g, 1.58 times the FAO/ 
WHO limit. The concentrations of p,p'-DDE ranged 
from 1.08 to 28.81 times the limit. Therefore, concen- 
trations of DDT-derived compounds in all samples were 
higher than the FAO/ WHO practical limit. The mean 
concentration of (3-BHC (1.63 \ig/g) was equivalent 
to 8.15 times the limit of 0.2 |.(g/g recommended by 
FAO/WHO for the ^-isomer (lindane) in cows" milk 
(26). p-BHC was above this limit in all samples. 



The results of the present study and similar surveys in 
other countries are presented in Table 3. It is evident 
that the higher values for p.p'-DDE. p-BHC, and total 
equivalent DDT in human milk correspond to levels 
found in other developing countries such as Guatemala, 
Portugal, Argentina, and Chile. 

Several other studies (9, 19} have indicated that high 
concentrations of organochlorine residues in human milk 
may adversely affect neonates. Other investigators have 
shown the effects of the chronic ingestion of low levels 

of some pesticides are more severe in young and mal- 
nourished animals (6, 16). 



The finding of residues of the cyclodienic compounds 
dieldrin, heptachlor epoxide, and endrin in the human 
milks analyzed, although at low levels, is a matter of 
concern. These pesticides are being increasingly used 
in Mexico, even though their persistence and toxico- 
logical effects have caused their use to be severely re- 
stricted in other countries. 



Mother's milk is an important source of nutrition for 
infants in the region studied, especially in the low socio- 
economic groups in which malnourishment of mother 
and child is also frequent. In view of the high values 
obtained for organochlorine pesticide residues in human 
milk in the present study, further related research in 
this region and throughout Mexico is essential. 



Also noteworthy is the presence of hexachlorobenzene 
residue, which heretofore has only been reported in de- 
veloped countries (1. 17, 22, 23). 

The mean value (lipid basis) of p,p'-DDE calculated 
as DDT (11.81 ^ig/g) represented 89.60% of the aver- 
age total equivalent DDT. This could indicate that most 
of the DDT-derived material in the human milks 
analyzed originated in the food chain due to excessive 
past use of DDT in the region (5). 

In general, the organochlorine residue levels found in 
the present study of human milk would be unacceptable 
in cows' milk in other countries. 



A cknowledgments 

This work was carried out at the laboratory of Environ- 
mental Chemistry of the Department of Chemistry, 
CIEA-IPN, with instruments donated by the Organiza- 
tion of the American States. We thank V. W. Kadis 
from the Food Laboratory, Edmonton, Canada, and 
J. R. W. Miles from the London Research Station, 
Agriculture Canada, Ontario, Canada, for technical ad- 
vice; J. F. Thompson from U.S. EPA, Research Tri- 
angle Park, N.C., for providing the pesticide standards; 
M. E. Cabrian, of the School of Medicine, Torreon, for 
his interest and general help; and G. Massieu and J. E. 
Herz from CIEA-IPN for their continued support and 
encouragement. 



TABLE 3. Average concentrations of some organochlorine pesticide residues in human milk from various countries, 

1965-79 





Year 




Concentrations in 


Whole Milk, ^g/m! 




COUNTRY' 


/3-BHC 


p,P -DDE 


P.p'-DDT 


Total Equiv. DDT 


United States (27) 


1965 








0.08 


0,12 


Holland >.25) 


1971 


0.004 


0.03 


0.016 


— 


Australia {23) 


1975 


— 


0.080 


0.015 





Sweden {27) 


1972 


— 


0.059 


0.020 





United States )14) 


1977 


0.003 


0.035 


0.008 


— 


Canada (New Brunswick) (78) 


1974 


— 


0.035 


0.013 


— 


Canada (77) 


1979 


0.002 


0.035 


0.006 


__ 


New Guinea (Sepik) (7J| 


1972 


— 


0.096 


0.181 





New Guinea (Saidorl (7.i) 


1972 


— 


0.002 


0.001 





Portugal (Lisbon! {12) 


1974 


— 


0.223 


0.100 


0.323 


Portugal (Bragan<;al (72) 


1974 


— 


0.040 


0.023 


0.063 


Guatemala (La Bomba) {20) 


1973 


— 


1.02 


1.00 


2.15 


Guatemala (La Bomba! {20) 


1976 


— 


— 


— 


0.587 


Guatemala (Guatemala City) (?.') 


1976 


— 


— 


— 


0.233 


Argentina (70) 


1974 


0.042 


0.092 


0.046 


0.140 


Chile (24) 


1978 


— 


0.15 


0.092 


0.25 


Mexico (This Study) 


— 


0.030 


0.202 


0.049 


0.266 



Vol. 15, No. 3, December 1981 



137 



LITERATURE CITED 

(/) Acker, L.. and E. Schulte. 1970. Uber das Vorkom- 

men von Chlorierten Biphenylen und Hexachlorbenzol (/^j 

neben Chlorierten Inzecticiden in Humanniilch und 
Menschlichem Fettgewebe. Naturwissenschaften 57 
(10);497-498. {16) 

(2) Albeit. L„ F. Mendez, M. Cebridn. and A. Portales. 
1980. Organochlorine pesticide residues in human adi- 
pose tissue in Mexico: Results of a preliminary study (//) 
in three Mexican cities. Arch. Environ. Health 35(5): 
262-269. 

(J) Albert. L.. and R. Reyes. 1978. Plaguicidas Organo- 
chlorados II. Contaminacion de Algunos Que'os 
Mexicanos por Plaguicidas Organochlorados. Rev. Soc. ( IS) 

Quim. Mex. 22(2):65-72. 

(4) Albert. L.. R. Reyes, and S. Saval. 1975. Pesticide 
residue problems in Mexico. Rev. Soc. Quim. Mex. 
19(5):216. 

(5) Bordas. E. 1973. El Empleo de los Insecticidas Agri- (/9) 
colas y la Contaminacion en el Ambiente Rural Mexi- 

cano. Memoria de la 1 Reunion Nacional sobre 
Problemas de Contaminacion Ambiental. 11:1111- {20) 

1117. 

(6) Boyd, E. M. 1972. Protein deficiency and pesticide 
toxicity. Charles C. Thomas, Springfield, 111. 

(7) Canada National Health and Welfare. Health Pro- [21) 
tection Branch. 1973. Analytical methods for pesticide 
residues in food. 

(S) Chan. A. S. Y. 1972. Analytical methods for waters {22) 

and wastewaters. Environment Canada, Ottawa, On- 
tario, Canada. 
(9) Fahim M. S., R. Bennett, and D. G. Hall. 1970. {23) 

Effect of DDT on the nursing neonate. Nature 
228:1222-1223. 

{10) Garcia Fernandez. J. C. 1974. Estudios y Comentarios {24) 

sobre Impregnacion Humana por Plaguicidas Organo- 
clorados en la Repiiblica Argentina. Medicina 34{4): 
393-4)0. 

(//) Goulden. R.. E. S. Goodwin, and L. Davies. 1963. {25) 

Improvement of identification in the gas-liquid chro- 
matographic analysis of agricultural samples for 
residues of some chlorinated pesticides. Analyst 88: {26) 

941-958. 

(72) Graca, /., A. M. S. Silva Fernandez, and H. C. Mou- 
rao. 1974, Organochlorine insecticide residues in 
human milk in Portugal. Pestic. Monit. J. 8(3):148- (27) 

156. 

(13) Hornabrook, R. W.. P. G. Dyment. E. D. Gomes, and 

J. S. Wiseman. 1972. DDT residues in human milk (28) 

from New Guinea natives. Med. J. Austr. 1:1927- 

1300. 

(14) yo/mo/i, I'., G. J. K. Lin, J. Armbrnster, L. L. Kettel- 



hut, and B. Drucker. 1977. Chlorohydrocarhon pesti- 
cide residues in human milk in Greater St. Louis, 
Missouri— 1977. Am. J. Clin. Nutr. 30: 1 106-1 109. 
Lam perl, L. M. 1964. Rapid separation of fat for 
pesticide residue analysis of mi.k products. J. Dairy 
Sci. 1013-1014. 

Lu. F. C. D. C. Jessiip, and A. Lavallee. 1965. Tox- 
icity of pesticides in young versus adult rats. Food 
Cosmet. Toxicol. 3:591-596. 

Mes, J., and D. J. Davies. 1979. Presence of poly- 
chlorinated biphenyl and organochlorine peslicide 
residues and the absence of polychlorinated terphenyls 
in Canadian human milk samples. Bull. Environ. 
Contam. Toxicol. 21:381-387. 

Miisial, C. J., O. Hutzinticr, V. Zitko, and J. Croker. 
1974. Presence of PCS. DDE and DDT in human 
milk in the provinces of New Brunswick and Nova 
Scotia, Canada. Bull. Environ. Contam. Toxicol. 
12:258-267. 

O'Leary, J. A., J. E. Davies, W. F. Edmun.wn. and 
G. A. Reich. 1970. Transplacental passage of pesti- 
cides. Am. J. Obstet. Gynecol. 107( 1 ) :65-68. 
Olszyna-Marzys, A. £., M. de Campos, M. Taghi- 
Farvar, and M. Thomas. 1973. Residues de Plagui- 
cidas Clorados en la Leche Humana en Guatemala. 
Bol. Of. Sanit. Panam. 74:93-107. 

Qninbv, G. E.. J. F. Armslroni;, and W. F. Dnrliam. 
1965.'dDT in human milk. Nature 207(4998) :726- 
728. 

Siyali, D. .S. 1973. Polychlorinated biphenyls, hexa- 
chlorobenzene and other organochlorine pesticides in 
human milk. Med. J. Austr. 2( 17):815-81S. 
Stacey. C. I., and B. W. Thomas. 1975. Organo- 
chlorine pesticide residues in human milk. Western 
Australia— 1970-71. Pestic. Monit. J. 9(2):64-66. 
Tapia. R., R. Bocic. and N. Dimitroff. 1978. Niveles 
de DDT y DDE en Tejido Adipose y Leche Humana 
por Chromatografia de Gases. Thesis, University of 
Chile, Santiago de Chile. 

Tninslra. L. G. M. Tli. 1971. Organochlorine insecti- 
cide residues in human milk in the Leiden Region. 
Neth. Milk Dairy J. 25(l):24-32. 

t/iV Food and Ai-riciilliire Ori^'unizalion/World Health 
Organization. 1974. Recommended international toler- 
ances for pesticide residues. CAC/RS 65-1974. Rome, 
Italy. 

Westoo. G., and K. Noren. 1972. Levels of organo- 
chlorine pesticide and polychlorinated biphenyls in 
Swedish human milk. Var Foda. 24(4) :41-54. 
Winter, A/., M. Thomas. S. Wernick, S. Levin, and 
M. Taghi-Farvar. 1976. Analysis of pesticide residues 
in 290 samples of Guatemalan mother's milk. Bull. 
Environ. Contam. Toxicol. 16:652-657. 



138 



Pesticides Monitoring Journal 



WATER 



],2-Dibromo-3-chloropropane Residues in Water in South Carolina, 1979-80 

George E. Carter. Jr., and Melissa B. Riley = 



ABSTRACT 

During 1979-80. a total of 236 water samples were col- 
lected from 205 sites in South Carolina. Well water, surface 
water (lakes, ponds, and rivers), and municipal water were 
sampled and analyzed for the soil fumigant 1 .2-dibromo-3- 
chloropropane (DBCP). DBCP levels ranged from non- 
detectable to 0.05 fig/liter (ppb) in an area of noniise 
(background). No municipal water .samples in the state 
exceeded the background level. In the area of high use of 
DBCP, 37% of the surface water samples exceeded the 
background level, but none exceeded 0.4 fig/liter. Twenty- 
seven percent of the well water samples from the high-use 
area exceeding the background level, and 10.2% of the 
samples exceeded 1 fig/ liter. All samples exceeding I 
ng/liter came from a small area within one county. The 
possible mode of contamination was not determined. 

Introduction 

Soil fumigation for nematode control is a key factor in 
a program against peach tree short life, a condition that 
has decimated southeastern peach orchards (I, 5). 
Both pre- and postplant treatments are required for 
growing healthy peach trees (Prunus persica (L.) 
Batsch) (3). l,2-Dibromo-3-chloropropane (DBCP) is 
the postplant nematicide used to control ring (Macro- 
Dosthonia xenoplax Raski) and root-knot (Meloidogyne 
^pp.) nematodes. Peach trees have no resistance to 
either nematode, DBCP is the only pesticide cleared for 
aostplant treatment of orchards, and no other pesticide 
las been effective for controlling the nematodes well 
inough to prevent premature death of peach trees. Low 
;oncentrations of DBCP have been reported in Cali- 
wnia groundwater samples {4), which led to questions 
5f groundwater contamination in South Carolina. The 
Jurpose of the present study was to determine the 



This research was partially funded by grants from the Southern 
legion Pesticide Impact Assessment Program and the U.S. Environ- 
nental Protection Agency. Contribution No. 1944 of the South Caro- 
ina Agricultural Experiment Station. 

Department of Plant Pathology and Physiology, Clemson University 
:iemson. SC 29631 



levels of DBCP present in water samples collected in 
South Carolina. 

Materials and Methods 

WATER SAMPLE COLLECTION 

Three areas of South Carolina were selected for their 
DBCP usage: (I) Piedmont area, non-use; (2) Coastal 
area, scattered agricultural use; and (3) Sandridge area, 
extensive agricultural use. During 1979-80, three types 
of water samples were collected from each area as 
follows: well water from privately owned wells; sur- 
face water from ponds, rivers, and lakes; and water 
from homes supplied by municipal sources. Samples 
were collected in new canning jars which were discarded 
after one collection. Jars were rinsed with glass-distilled, 
pesticide grade ethyl acetate, covered with ethyl acetate- 
rinsed aluminum foil, and closed with jar caps and 
rings. Jars were filled to the top from home taps (well 
and municipal) or by submerging into ponds, rivers, 
and lakes, leaving no head space, and were placed in 
ice immediately after collection. The location of the 
sample and any information on the agricultural prac- 
tices of the area were recorded at the time of collection. 
Sites yielding samples containing over 1 ppb DBCP 
were resampled to verify results. 

EXTRACTION 

This procedure was obtained from the California De- 
partment of Food and Agriculture (2) and was modi- 
fied by the addition of a centrifugation step. Five glass 
beads, rinsed with ethyl acetate, were combined with a 
I60-ml water sample and 10-ml gla.ss-distilled, pesticide- 
grade ethyl acetate in a round-bottom boiling flask 
that was attached to a modified Stark and Dean trap 
and condenser. The flask was placed in a heating 
mantle; full voltage was applied until the mixture began 
to bofi and then was reduced to one-third maximum. 
The mixture was allowed to reflux 15 minutes or until 
the ethyl acetate was distilled over to the trap. The 



/OL. 15. No. 3, December 1981 



139 



heating mantle was turned off and the condenser was 
washed with distilled water. After 5 minutes, the dis- 
tillate was removed and centrifuged 10 minutes at 
17, 500g in a Sorvall RC2-B refrigerated centrifuge. 
The ethyl acetate layer was transferred to an ethyl 
acetate-washed, screw-cap tube to which a small amount 
of anhydrous sodium sulfate was added. An aluminum 
foil liner rinsed with ethyl acetate was placed between 
the test tube and the screw cap. Samples were kept in 
the freezer after extraction and before gas chromato- 
graphic analysis. 

Glassware blanks were run by placing 30 ml ethyl 
acetate in the boiling flask of the extraction apparatus 
and refluxing it 15 minutes. A 10-ml quantity was 
then collected to be used as a glassware blank. Glass- 
ware was cleaned by placing it overnight in sodium 
dichromate-sulfuric acid cleaning solution, and then 
rinsing it three times with distilled water and ethyl ace- 
tate. 

GAS CHROMATOGRAPHY 

The concentration of DBCP in water samples was de- 
termined by use of a Varian 3700 gas chromatograph 
connected to a CDSlll chromatography data system 
and recorder. Instrument parameters and operating con- 
ditions were as follows: 



Detector ; 
Column 



Temperatures 



Carrier gas; 
Retention time: 
Detection limit ; 



'■'Ni electron-capture 

2 m by 2 mm glass, packed with 10% OV-101 

on 80-inO-mesh Chromosorb W-HP 

column: 1I10°C for 3 min, tlien increased 

column: 4°/min for 7 min, tlien increased 

column: 18°/min for 5.66 min, and then held 

column: at 230°C for 4.33 min 

injector 220'C 

detector 280°C 

nitrogen llowing at 30 mlmin 

5.7."; minutes for DBCP 

0,008 ppb 



Recovery percentage was determined from the mean 
value of four fortified samples (50 ng DBCP added to 
160 ml distilled, deionized water). This value, 88%, 
was used to calculate DBCP present in the samples. 
Levels of DBCP were calculated by the data system, 
using an external standard method of calibration. 

DBCP standards were prepared in ethyl acetate, using 
a 99.6% pure analytical standard (AMVAC Chemical 
Corp.); standards and sample extracts were kept in 
different freezers. The gas chromatograph was cali- 
brated using a 5 pg DBCP/ul standard as the first 
sample every day. Ethyl acetate blanks were run after 
every sample containing DBCP. 

Either of the following apparatus and operating con- 
ditions was used to confirm the presence of DBCP: 

Column: 2 m by 2 mm glass, packed with 3% 

OV-216 on 80-100-mesh Chromosorb 
W-HP 



140 



1 emperatures, °C 



DBCP retention time: 

OR 
Column; 



Temperatures, °C 



DBCP retention time: 
Carrier gas (both columns): 
Detection limit (both) 



column 75 

injector 270 

detector 250 
2,1 min 

2 m by 2 mm glass, packed with 2% 

DEGS on 80-100-mesh Chromosorb 

W, A/W 

column 100 

injector 250 

detector 250 

1.2 min 

nitrogen flowing at 40 ml min 

0,008 ppb 



MASS SPECTROMETRIC ANALYSIS FOR DBCP 

Selected samples were taken to Research Triangle In- 
stitute in Research Triangle Park, North Carolina, for 
analysis. Methane-enhanced negative ion chemical ioni- 
zation mass spectrometric analysis was conducted on 
one of two gas chromatograph-mass spectrometers un- 
der the following conditions: 



CiC MS: 
Column: 
Temperatures. "C: 



Electron energy: 

Box current ; 

Accelerating voltage; 

OR 

GC MS: 

Column: 

Temperatures, ' C : 



LKB 2091 

25-m WCOT SE-30 capillary 

column: 1(I0°C for 4 min. then 

240°C 
injector 210 
ion source 210 
50 eV 
250 ^A 
3.5 kV 



Electron energy: 



Finnigan Model 4000'PPNICI 

25-m SP2I00 capillary 

column 70° for 1 min. then 8° /min to 

250°C 
injector 250 
ion source 250 
70 eV 

The appearance of the characteristic ions (m/z 79, 81, 
158, 160, and 162) in the correct retention window was 
used to confirm the presence of DBCP in the samples. 
Tentative confirmation was based on the observation 
of the m/z 79 and 81 ions in the correct retention 
window. Selected samples were concentrated before 
analysis by placing the sample in ice with a stream of 
nitrogen flowing over it. 

Results and Discussion 

Distribution of the 236 water samples is shown in 
Table 1. Samples from the Piedmont area (non-use of 
DBCP) appeared to contain a background level of 
DBCP or a compound indistinguishable from DBCP 
at levels from 0.008 ppb (limit of detection) to 0.05 



TABLE 


I. Distribiiiion of waler samples analyzed for 




DBCP in Soiilh Carolina 


1979-80 










No, OF 


AREA 


Type of Water No, 


OF Sites 


Samples 


Piedmont 


well 


8 


8 


(Non-use) 


surface 


15 


18 




municipal 


3 


3 


Sandridge 


well 


49 


63 


(High use) 


surface 


46 


60 




municipal 


8 


8 


Coastal 


well 


24 


24 


( Scattered 


usel surface 


33 


33 




municipal 


19 


19 



Pesticides Monitoring Journali 



MUNICIPAL 

VA/ATEn 
3 SITES 




WELL 
WA TE R 
8 SITES 




SURFACE 
WATER 
IS SI TE S 



FIGURE 1. Percentage of sites showing DBCP contami- 
nation (pph) in Piedmont area of South Carolina. Detection 
limit = 0.008 pph. ND represents no detectable residue 
of DBCP. 



ID 



u 
led 



MUNICIPAL 

WATE R 

IB SITES 




V/VELL 

WATER 

Sa SITES 



SURFACE 
WATER 
33 SITES 




10 



UJ 



U TO 

I 



IV1UNICIPAL VA/ATEP 
a SITES 



I I L_ 



SURFACE \A/ATER 

ae SITES 




\A/ELL WATER 
as SITES 




D 
Ul 

PP B 



FIGURE 3. Percentage of sites showing DBCP contami- 
nation (pph) in Sandridge area of South Carolina. Detection 
limit = 0.008 pph. ND represents no detectable residue 
of DBCP. 



Original 
Sample 


Neighbors of 
Original Sample 



Neighbors of 
Second Samples 



226 
22) 



222 
223 



22t 
229 
220 



Verification Samples 



Verified by 216. 217. 
Confirmed by GC/MS 



Verified by 221. 
Confirmed by GC/MS 



Verified by 213. 220 
Confirmed by GC/MS 



Verified by 219. 
Confirmed by GC/MS 



207 

2oe 

209 



210 
212 



verified by 211, 
Not conf 1 nned by 
GC/HS 



FIGURE 2. Percentage of sites showing DBCP contami- 
nation (pph) in Coastal area of South Carolina. Detection 
limit = 0.008 pph. ND represents no detectable residue 
of DBCP. 



[*) Samples containing above 1 opb 



FIGURE 4. Treatment of original water samples contain- 
ing above 1 ppb DBCP (numbers indicate sample numbers). 



Vol, 15, No. 3, December 1981 



141 



ppb (Figure 1 ). Although the compound was tested un- 
der two sets of gas chromatographic conditions and at 
significantly different polarities, and on the mass spec- 
trometer, the low level prevented positive identification. 
Levels of DBCP up to 0.05 ppb were therefore con- 
sidered to be background levels. 

In the coastal area of South Carolina (scattered use 
of DBCP). no well water or municipal water sample and 
only one surface water sample exceeded the background 
level (Figure 2). Samples were obtained in the Sand- 
ridge area of South Carolina (high use of DBCP) 
showed a greater variability in DBCP concentrations 
(Figure 3 ) . No municipal water sample exceeded the 
background level, but surface and well water samples 
varied from none to more than 1 ppb. Seventeen sur- 
face water samples in the Sandridge area contained 
DBCP, but none were above 0.04 ppb, and 10 were 
below 0.1 ppb. 

Five well water samples contained greater than 1 ppb 
DBCP. All of these samples were verified by resampling 
at a later date. Two of the sites were located in a ran- 
dom survey, and the remaining three were found when 
the nearest neighbors to the original samples were sam- 
pled, as shown in Figure 4. When the samples contain- 
ing more than 1 ppb DBCP were tested by mass spec- 
trometry, four of the five were confirmed to contain 
DBCP. 

This study indicates that low levels of a material that 
is indistinguishable from DBCP may exist in ground- 
water where no agricultural use has occurred. This pos- 
sibility must be considered when data concerning trace 
amounts of DBCP are analyzed. One must consider 
whether the material is authentic DBCP and, if so, 
whether it resulted from agricultural use. 



Most samples from the high-use area did not exceed 
the background levels found in samples from the non- 
use area, but several well water samples from the high- 
use locality did exceed the background levels. Hydrol- 
ogy of the area, the nature of well construction, and 
use patterns of DBCP in the vicinity of the wells were 
not studied. Therefore, it is impossible to conclude that 
contamination in this area was due to agricultural ap- 
plication of products containing DBCP. Further study 
is necessary to identify the source of contamination in 
these five wells. 

A cknowledgments 

Authors appreciate the assistance of Edo Pellizzari and 
Ken Tomer of the Research Triangle Institute in con- 
ducting the mass spectrometer analyses. 



LITERATURE CITED 

(/) Chandler . W. A.. J. //. Owen, and R. L. Livingston. 
1962. Sudden decline of peach trees in Georgia. Plant 
Dis. Rep. 46(12):831-834. 

(2) Jackson. T., and S. Frederickson. 1978. Determination 
of DBCP in crops, soil, water, bark, and leaves. 
Memorandum, California Department of Food and 
Agriculture, October 24. 

(i) Managing Peach Tree Shori Life in the Southeast. 
I97S. J. A. Brittain and R. W. Miller, Jr., Eds. Clem- 
son University Extension Service Circular 585, De- 
cember. 

1.4) Peoples, S. A.. K. T. Maddy, W. Ciisick, T. Jackson, 
C. Copper, and A. S. Frederickson. 19S0. A study of 
samples of well water collected from selected areas in 
California to determine the presence of DBCP and 
certain other pesticide residues. Bull. Environ. Contani. 
Toxicol. 24(4):611-618. 

(5) Zehr. E. /., R. W. Miller, and F. H. Smith. 1976. Soil 
fumigation and peach rootstocks for protection against 
peach tree short-life. Phytopathology 66(5) :689-694. 



142 



Pesticides Monitoring Journal 



APPENDIX 



Chemical Names of Compounds Discussed in This Issue 



^ACHLOR 

.DRIN 

<OCLOR 1016 or 1242 

WCLOR 1242 

lOCLOR 1246 

ROCLOR 1254 

PRAZ'NE 

€C (Benzene Hexachloride) 

iLORDANE 

fANAZINE 

DE 

DT 

lELDRlN 

MDRIN 

CB 

EPTACHLOR EPOXIDE 

(NDANE 

IREX 

:Bs (Polychlorinated Biphenyls) 

DE 

3XAPHENE 



2-Chloro-2',6'-dietliyl-N-(methoxymethynacetaniIide 

Hexachlorohexahydro-efirfo. exo-dimethanonaphthalene 95% and related compounds 5% 

PCS, approximately 42% chlorine 

PCB, approximately 42% chlorine 

PCB, approximately 46% chlorine 

PCB, approximately 54% chlorine 

2-Chloro-4-(ethylamino)-6-(isopropylamino)-5-triazine 

1,2,3.4,5,6-Hexachlorocyclohexane (mixture of isomers) 

Technical: 60% octachloro-4,7-melhanotetrahydroindane and 40% related compounds 

2-[[4-Chloro-6-(ethylamino)-5-triazin-2-yl]amino]-2-methyIpropionitrile 

Dichlorodiphenyldichloroethylene (degradation product of DDT) 

Dichloro diphenyl trichloroethane. Principal isomer present (p,p'-DDT; not less than 70%): 1,1,1-trichloro- 
2,2,-bis( p-chlorophenyl ) ethane 

Hexachloroepoxyoctahydro-enrfo.e:co-dimethanonaphthalene 85% and related compounds 15% 

Hexachloroepoxyoclahydro-eni/o,endo-dimethanonaphthalene 

Hexachlorobenzene 

l,4,5,6,7,8,8-Heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 

Gamma isomer of benzene hexachloride (BHC) 

Dodecachlorooctahydro-l,3,4-metheno-lH-cyclobuta[cd]pentalene 

Mixtures of chlorinated biphenyl compounds having various percentages of chlorine 

Dichloro diphenyl dichloroethane ( 1 ,l-dichloro-2.2-bis (p-chlorophenyl)ethane, principal component) 

Technical chlorinated camphene (67-69% chlorine) 



OL. 15, No. 3, December 1981 



143 



ERRATUM 

Pesticides Monitoring Journal, Volume 15, Number 2, 
page 78, of the article "Chlorinated Hydrocarbon Pesti- 
cides in Blood of Newborn Babies in India" by 
M. K. J. Siddiqui et al. Line 9 in the right column and 



Tables 1-3 should be corrected to read as follows: 

There was a significant difference (P < 0.005) in total 
DDT residues by area of residence, but a slightly higher 
concentration of DDE was estimated in urban sub- 
jects, . . . 



TABLE 1. Ori>anochlorine pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by 

age group 



PEsncints 


Women 


18-25 Years Old (58 Cases) 




Women 


26-34 Years Old (42 Cases) 




















Detected 


Range 


Arithmetic 


Mean 


SE 


Range 


Arit 


HMETIC MI;AN 


SE 


Total BHC 


6.9-278.3 


32.97 




16.89 


2.0-507.84 




45.79 


5.90 


Lindane* 


1.28-78.69 


10.27 




2.18 


3.10-175.73 




14.99 


1.23 


r.p'-DDE 


1.02-850.0 


12.33 




1.98 


2.05-78.14 




23.10 


4.75 


p.p'-DDU 


ND^8.21 


5.84 




1.25 


ND-48.21 




8.01 


2.85 


P.p'-DDT' 


ND-140.0 


7.30 




2.32 


ND-57.52 




22.13 


2.37 


SDDT' 


2.73-1029.85 


59.65 




25.51 


4.59-149.62 




51.18 


8.51 



*, ** Statistically significant (P<0.05 and 0.005, respectively). 
2DDT = total DDT equivalent. 



TABLE 2. 



Organochlorine pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by 

dietetic habit 



Pesticides 


Vegetarian Diet (36 Cases) 




Nonvegetarian 


Diet (64 Cases) 
















Detected 


Range Arithmetic Mean 


SE 


Range 


Arithmetic Mean 


SE 


Total BHC 


6.9-278.43 38.3 


7.29 


2.0-507.84 




35.64 


3.13 


Lindane 


1.28-78.68 12.47 


0.34 


1.8-175.73 




11.41 


1.10 


P.p'-DDE 


1.02-850.0 15.33 


3.26 


1.9-150.0 




20.53 


4.39 


p.p'-DDD 


ND^8.21 6.55 


1.85 


0.89-32.09 




8.49 


1.80 


p.p'-ddt 


ND-55.56 14.89 


3.05 


1.78-140.0 




17.08 


3.55 


i;DDT 


4.03-1029.85 62.22 


8.50 


2.73-240.41 




50.07 


7.78 



TABLE 3. Organochlorinc pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by 

area of residence 



. 


LIrban 


Population (48 Cases) 




Rural 


Population (52 Cases) 




Detected 


































Pesticides 


Range 


Arithmetic 


Mean 


SE 


Range 


Arithmetic 


Mean 


SE 


Total BHC 


2.0-507.84 


47.38 




13.87 


3.0-76,97 


27.06 




2.31 


Lindane** 


1.28-175.73 


16.94 




0.72 


1.8-33.43 


8.88 




1.63 


p.p-DDE 


1.02-257.50 


22.81 




7.05 


2.2-850.0 


15.48 




4.38 


P.p'-DDD 


ND^8.21 


7.33 




3.88 


ND-32.09 


6.25 




1.43 


p.p -DDT 


0.5-50.23 


13.71 




2.19 


ND-140.0 


17.08 




4.43 


vDDT*** 


2.73-338.43 


41.60 




10.88 


7.14-1029.85 


68.23 




13.84 



•* Siaiistically significant (P<0.05, 0.05, and 0.005, respectively). 



144 



Pesticides Monitoring Journah 



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