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Pesticides Monitoring Journal
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Editor
Martha Finan
CONTENTS
Volume 12 June 1978 Number 1
SOIL
Page
DDT moratorium in Arizona — agricultural residues after seven years 1
G.W. Ware, Betty J. Estesen. N.A. Buck, and W.P. Cahill
FISH, WILDLIFE, AND ESTUARIES
Organochlorine insecticide, polychlorinated hiphenyl. and metal residues in some
South Dakota birds, 1975-76 4
Yvonne A. Greichus, Brian D. Gueck, and Barbara D. Ammann
Organochlorine pesticide residues in Florida birds of prey , 1969-76 °
David W. Johnston
Shell thinning and pesticide residues in Texas aquatic bird eggs. 1970 16
Kirke A. King, Edward L. Flickinger, and Henry H. Hildebrand
Organochlorine insecticide and polychlorinated hiphenyl residues in woodcock
wings, 1971-72 22
M.A. R. McLane, E.H. Dustman, E.R. Clark, and D.L. Hughes
Chlorinated hydrocarbons and mercury in birds of Lake Pdijdnne, Finland — 1972-74 26
Jukka Sarkka, Marja-Liisa Hattula, Jorma Janatuinen, Jaakko Paasivirta, and Risto
Palokangas
Dieldrin, DDT. polychlorinated biphenyl. and mercury levels in freshwater mullet
from the upper Great Lakes, 1975-76 . 36
Mary E. Zabik, Barbara Olson, and Teiko M. Johnson
GENERAL
Mirex incorporation in estuarinc animals, sediment, and water, Mississippi Gulf
Coast — 1972-74 40
Armando A. de la Cruz and Kuang Yang Lue
APPENDIX 43
Information for Contributors 44
SOIL
DDT Moratorium in Arizona — Agricultural Residues After Seven Years '
George W. Ware. Betty J. Estesen, Norman A Buck, and William P. Cahill
ABSTRACT
The moratorium on agricultural use of DDT in Arizona that
began in January 1969 proved very effective during the first 7
years of enforcement. Residues on green alfalfa declined sig-
nificantly to a probable inherent level of 0.02 ppm wet weight.
Soil residues of ^DDT-related degradation products declined
significantly, averaging 23 percent: residues in desert soils
declined 60 percent. The ^DDT half-life in irrigated soils was
about 7 years: it decreased to 2.5 years in nonirrigated soils.
Introduction
The moratorium on agricultural use of DDT in
Arizona began in January 1969 (2, 4, 5). This is the
fourth and probably last report on the status of DDT
residues and SDDT-related degradation products,
after 18 years of unrestricted use and 4 years of
restricted use in Arizona.
TABLE 1 IDDT residues in green alfalfa. Baseline Rd.,
Maricopa Co., Arizona, 1967-75
XDDT Residues,
PPM
1967
1968
1969
1970
1971
1972
1975
Sample
Aug.
Sept
Sept
Sept.
Sept.
Sept
Oct
■)
0.220
0,038
0050
0.020
0.023'
0.009'
i
0283
_
0027
0030
—
0025'
0.007'
4
0 170
0.120
0038
0 037
0.031
0.022
0016'
5
—
0.060
0,020
0 024
0.011
0.029«
0009'
6
0,277
0035
0.022
—
0.008"
—
8
0,794
—
—
0.027
0,038
0,013'
0,023
9
_
0076
0034
0.IM2
0,020
0,029'
0,027
10
0.350
0092
0,054
0 162
0 027
0.031
0.022'
Jl
0453
0.580
0,064
0.047
0085
0.056
0.027'
12
0299
0.077
0 025
0.038
—
0.023'
0.014'
13
0.606
—
—
0.021
0.027
—
0008'
Means
0404<l
0,175c
0037b
0045b
0.032b
0026b
0016a
NOTE; — = no sample analyzed
* = substitute adjacent fields
Means with same letter are not significantly differenl at the 0 05 level.
Analytical Methods
Alfalfa and soil samples were collected as described in
previous reports (2, 4. 5) from the three major irrigated
areas in Arizona: Salt River Valley, which surrounds
Phoenix; Pinal County; and the Yuma mesa and valley in
Yuma County. Desert soil samples, but only the top 0.25
inch, adjacent to these areas were also collected. In addi-
tion an earlier study {3) was continued to provide reference
standards and continuity for the seven-year period (Table
1). The sampling sites are located on a 60-mile Maricopa
County east-west transect along Baseline Road, much of
which is now residential.
Alfalfa and soil samples were extracted and cleaned by
procedures previously described (2-5).
' Department of Entomology. The University of Arizona. Tucson. AZ 85721 This
paper submitted lo Regional Project W-45. "Residues of Pesticides and Related
Chemicals in the Agricultural Environment — Their Nature. Distribution. Persis-
tence, and Toxicologicat Implications." University of Arizona Agricultural Ex-
periment Station Journal Series No 2759
Samples were analyzed by electron-capture gas-liquid
chromatography (EC-GLC). Recovery standards and ana-
lytical reagent blanks were also extracted and cleaned each
day. Recoveries were consistently above 90 percent; how-
ever, the data presented have not been corrected. The
minimum sensitivity of the method was arbitrarily set at
0.02 ng for p, p'- and o. p'-DDT. DDE, and TDE.
Standard curves extended from 0.03 ng to 0.10 ng. The
sensitivities were 0.001 ppm for alfalfa and 0.003 ppm for
soil. Results are based on a minimum sample size and 6 p.1
extract injected into the chromatograph.
Analytical EG-GLC confirmatory tests were conducted
randomly using a double-length GLC column at the same
temperatures as those used in the previous study (2).
Because of low levels of IDDT and interfering peaks of
toxaphene which may have drifted from nearby cotton-
fields, all alfalfa extracts were dehydrohalogenated after
cleanup on Florisil and residues were measured only as
o.p'- and p,p'-DDE as described by Cahill et al. (2);
results were combined when measurable levels of o,p'-
DDE were found.
Vol. 12, No. I.June 1978
1
Results and Discussion
Residues observed in alfalfa and soil samples during the
past 7 years are presented in Tables 1-3 as iDDT. The
Student-Newnian Keul's lest was used to analyze differ-
ences among residue means for the various sampling dates.
Comparisons were made on least-square means in the soil
samples (Table 3) because there were too few samples.
Residues on alfalfa from all four areas shown in Tables I
and 2 appear to have leveled off at about 0.02 ppm.
September values for Yuma County alfalfa were consist-
ently high from 1969 through 1972. However, these values
were well below 0.02 ppm in 1975.
Residue levels in alfalfa soils declined from the previous
sampling period, September 1972 (Table 3). In the past,
yearly examination of these soil residues indicated almost
imperceptible changes. After 3 years, however, the resi-
dues had declined significantly, an average of 23 percent.
Residues in the desert soils declined 60 percent. This
suggests that the iDDT half-life in the irrigated soils of
Arizona is about 7 years, and decreases to about 2'/i years
in the desert or nomrrigated soils.
iDDT residues now found in the agricultural soils of
Arizona are shifting steadily toward higher proportions of
DDE. The ratio of DDH:DDT in these soils shifted from
56:44 in 1972 to 62:38 in 1975. in the desert soils, the shift
was approximately the .same: from 65:35 in 1972 to 71:29
in 1975. These data suggest that iDDT residues are de-
clining at a predictable rate, probably both by volatility
and conversion to metabolites not measured with the ana-
lytical methods used in this study.
LITERATURE CITED
(/) Cahill. W. P . B. J. Estesen. and G W. Ware. 1970.
Determination of DDT in the presence of toxaphene resi-
dues. Bull Environ. Conlam. Toxicol. 5(3):260-262.
(2) Ware. G. W.. B. J. Estesen. and W. P. Cahill. 1974. DDT
moratorium in Arizona — agricultural residues after 4 years.
Peslic. Monit. J 8(2):98-101
(3) Ware. G. W.. B J. Estesen. and W. P Cahill. 196H. An
ecological study of DDT residues in Arizona soils and
alfalfa. Peslic. Monit J. 2(3):129 132.
(4) Ware. G W . B J. Estesen. ami W P Cahill 1971 DDT
moratorium in Arizona — agricultural residues after 2 years.
Peslic. Monit. J. 5(3):276-280.
f5) Ware. G. W.. B J Estesen. C. D Jahn. and W. P. Cahill.
1970 DDT moratorium in Arizona — agricultural residues
after 1 year Peslic. Monil J 4(1 ):2 1-24.
TABLE 2. IDDT residues in green alfalfa during 1969-75
DDT moratorium. Arizona
£DI7r Residues, ppm
1969
1969
1970
1971
1972
1972
1975
Sample
Jan.
Skpt
Sept
Sefi
Jan
Sept.
Oct.
Maucopa Count*. Amzona
1
0087
0042
0057
_
0019*
2
0 303
0.062
0 050
0.025
_
0.039*
0037'
3
0 102
0078
0093
0038
—
—
0011*
4
0 107
0,047
0 076
0037
—
0046'
0017
5
0C>49
0030
0.025
0007
—
0011
0015*
6
0 113
0064
0060
0051
—
0045"
0041*
7
0082
00,34
0023
—
—
0055
021
8
0125
0.056
—
—
—
—
—
9
0085
0044
0 101
—
—
—
—
10
-
—
0.080
0.059
—
—
—
Means
0 117c
0051b
0.063b
0036b
-
0.39b
0.023a
Pinal County.
AUZONA
1
0047
0042
00J4
0 055
0041*
2
0047
0 031
0059
0 036
—
—
0068'
3
0 142
0 187
_
_
_
—
0006*
4
0 231
0076
0 071
0.072
—
0025
—
5
0092
0 130
0045
—
—
0.025'
_
6
0038
0 058
OMS
_
—
—
—
7
0 079
0 118
0 059
0 038
_
0.044
0023*
8
0068
0 071
0.031
0.034
—
0.018
0.077'
9
0.054
0.068
0.057
0.060
—
—
aooe*
Means
0088b
0086b
0030a
0.049a
-
0.031a
0.0361
Yuma Countv
AUZONA
1
0.047
0.373
0.120
0.025
0.032
0016'
2
0039
0098
—
—
0010*
0017»
0008'
3
0049
0 256
0084
0.270
0073*
0040*
0040
4
0 057
0 093
_
_
0055'
0075'
0025
5
0057
0545
0063
0 -340
0047*
0290*
0030'
6
0044
0317
—
—
0035'
0300*
0.032'
7
0059
0 241
—
—
0026*
0 190*
0034'
8
0 036
0 045
0 034
0 031
0039*
—
0005'
9
0021
0056
—
—
0015>
—
—
10
0.046
0.074
0051
0050
0.028
0.045
0006
Means
046a
0210b
0.058a
0 162b
0.035a
0.123b
0.022a
NOTE: — = no samples analyzed.
* = subadtule adjacenl Ttelds.
Means with saiitc letter arc not significanlly difTcicnl ul the 0 0^ level
Pesticides Monitoring Journal
TABLE 3. 1,DDT residues in soils during 1969-75 DDT moratorium . Arizona
1969 Jan
PPM Residues
1972 Sept . ppm Residues
1975 Oct
PPM Residues
Field
DDE
o.p'-
P.P'-
Total
DDE
o.p'-
py-
Total
DDE
o.p'-
p.p'-
Total
No.
DDT
DDT
DDT
DDT
DDT
DDT
Ma>icop« County
1
0.35
0.04
0.12
0 54
0 40
0 04
0 II
0.55
0.43
0.10
0 13
0.66
2
0 48
0 17
0.78
1 54
0 98
0 18
0.47
1.63
3
0 33
0.07
0 16
0.59
1.24
0 13
0 32
1.69
10
0 10
0.23
1 33
4
0.49
0 05
0 17
0.74
0 58
0.05
0.23
0 86
0 40
0,03
0 12
0 55
5
0 29
0.05
0 09
0 44
0.17
0 01
005
0.23
0 17
0 01
0.02
0 21
6
2.10
0.43
1 10
3 93
2 58
0 28
0 96
3 82
2 24
0 31
0 58
3 13
7
0 84
Oil
0 23
1 22
0 92
0 09
029
1 30
0 68
0 06
0 14
0 88
8
2 22
0 38
1 29
4 00
2 37
0.27
1.21
3.85
1 96
0 24
0 98
3 18
9
1 18
0 21
0 91
2 41
1 12
0.17
0.77
2 06
0 83
0 14
0 55
1 51
10
—
—
—
(0.24)
0.31
0.04
0.07
0.42
0 24
0.02
0 06
0.32
Means
0.92
0.17
0.54
1 57a
1.07
0 13
0.45
1 64a
0.883
Oil
0 31
1 31b
Desert
1
0 08
<0.01
0 03
0 13
0 43
0 07
0 09
0 59
0 04
0 00
0 02
0 06
2
0.24
0 02
0 06
0 35
0 28
0.03
0.58
0 89
0.04
0.01
0 02
0 06
3
0.44
0.04
0 15
0 67
0.18
0 02
0 04
0.24
0 06
0 01
0.02
0 10
4
—
—
—
12 39)
0.54
0 08
0 06
068
0 69
0 10
0 19
0 98
Means
-
-
-
0.89a
0.36
0.05
0.19
0.60a
0.21
0.03
0.06
0.30b
Pinal County
1
0.64
0 48
2.43
3 77
0 74
0.34
2 64
1.72
0.59
0.24
2 51
3.34
2
0 27
0 15
1 03
1.52
0 41
0 13
0 96
1.50
0.37
0 09
1 03
1 49
3
1 05
0 32
1 38
2 75
1 16
0 16
080
2.12
0 64
0 09
0 42
1 16
4
0 99
0 27
1 04
2 30
1.40
0 18
0.74
2.32
1.60
0.21
0,25
2 05
5
0 16
0.02
0 21
0 41
0 25
0.02
0 16
0.43
0.19
0 02
0 10
0 31
6
0 06
0 01
0 07
0.14
0 07
0 01
0.04
0.12
0.04
0 00
0.05
0 08
7
1 09
0 28
1 37
2 74
1 63
0 20
0 80
2.63
1 32
0 16
0 31
1 79
8
0 09
<0 01
0.04
0 14
0 08
0 01
0.02
Oil
0.05
0 00
0.01
0 06
9
0 67
0 09
0 29
1 06
0 74
0.03
006
0.83
0 59
0 05
0.08
0 72
10
0 66
0 14
0 36
1 16
1 19
0 15
0 39
1.73
0 91
0 09
0.08
1.08
Means
0.57
0 18
0 82
1 60a
0 69
0 12
0 66
1 55a
0.63
0 10
0.48
1 21b
Desen
1
0 09
<0 01
0 06
0 16
0 17
0 02
0 12
0 31
0 04
0 00
0 01
0 06
2
0 18
0 01
0 11
0 32
0 21
0 02
0 21
0 44
0 07
0 00
0 02
0 09
3
0 05
0 03
0 10
0.21
0.06
0.01
0.02
0.09
0,04
0 01
0.01
0 06
4
0.09
0 03
0 10
0.25
0.77
0.07
0.09
0.93
0 49
0 05
0 07
0.61
Means
0.10
0.02
0 09
0.24a
030
0.03
0.11
0.44a
0 16
0.02
0.03
0 20b
Yuma County
1
0 10
<001
0 07
0.17
0 12
0 02
0.03
0 17
0 06
0 01
0 01
0 08
2
0 24
0 05
0.25
0 54
0 20
0 03
0 07
0.30
0.24
003
0 06
0 33
3
0 72
0 16
0 72
1 60
0 79
0 16
0 49
1 44
071
0 15
0 29
115
4
0 59
Oil
0 47
1 17
0 98
0 15
0.46
1 59
0.84
0 13
0.22
118
5
0.48
0 05
0.30
0 83
075
0 12
0 34
1.21
0 54
0 10
0.15
0 79
6
0 29
0 16
0.74
1 19
0 48
0 10
0,43
1 01
045
0 08
0 29
0 81
7
1 29
0 07
037
1 73
111
0 09
0 50
1 80
0 91
0 06
0 01
0 97
8
0 06
0 01
0 01
0 08
0 05
<0 01
<0.01
007
002
0.00
0.00
0 02
9
0 00
0.00
0 00
0 00
<0 01
<0 01
<001
0.03
0 00
0 00
0 00
0 00
10
0 26
0.02
0.03
0 31
0 17
001
0.02
0 20
0.08
0.00
0 01
0 10
Means
040
0 06
0.30
0.76a
0.47
0.07
0.25
0 78a
0 39
0.06
0.10
0 54b
Desert
1
0 27
0 02
0 07
0 36
0 24
0 06
0 09
0 39
0 10
0.03
003
0 16
2
0 03
0 01
0 02
0 06
0.02
0 01
0 02
0 05
0 02
000
0.01
0 03
3
0.02
0 01
0 03
0.06
0 02
0 01
0.02
0 05
0 02
0.00
0.02
0 05
4
0 00
0 00
0 01
0 01
0 79
0.07
0.15
1 04
0 00
0 00
0 00
0 01
Means
008
0 01
0.03
0 12a
0.27
0 04
0.08
0.38b
0.035
0.01
0.02
0 06a
NOTE — = no sample analyzed.
Figures in pareniheses are missing values calculated by randomized blocks missing value formula.
Means wiih same tetier are not significantly different a( ihe 0 05 ppm level
12, No. 1, June 1978
nSH, WILDLIFE, AND ESTUARIES
Organochlorine Insecticide, Poly chlorinated Biphenyl, and Metal Residues
in Some South Dakota Birds, J 975-76 '
Yvonne A. Greichus, Brian D. Gueck, and Barbara D. Ammann
ABSTRACT
Chlorinated hydrocarbon insecticide, pnlychlorinaled biphenyl
(PCB). and metal residues nere measured in tissues of common
crows (Corvus brachyrhynchos), American coots (Fulica
americana). starlings (Sturnus vulgaris), and Franklin's gulls
(Larus pipixcan). of South Dakota in 1975-76. Insecticides and
PCBs were analyzed by column, thin-layer, and gas-liquid
chromatography . Metals were analyzed by atomic absorption
spectrophotometry.
DDE was the most prevalent residue: it was delected in 93
percent of all samples and averaged 66 percent of the total
residues in the carcass. Average values ranged from 0.04 ppm
to 0.54 ppm. Dieldrin was delected in 61 percent of all samples
and averaged < 0.01 ppm to 0.15 ppm. TDE and DDT were
found in 27 percent and 15 percent, respectively, of all samples.
and the averages for both ranged from < 0.01 ppm to 0.06 ppm.
Heptachlor epo.xide and lindane were delected in some samples.
PCBs were not found above the minimum delectable level. 0.1
ppm. in any sample.
Gulls had higher insecticide and metal residues than had cools,
starlings, or crows. Arsenic values averaged 1.4 ppm dry
weight in carcass samples from the four species of birds. Cad-
mium, copper, manganese, lead, and zinc averaged 0.10. 0.94.
4.8, 1.0, and 69 ppm dry weight, respectively, and were no
higher than values reported in some birds from other areas.
Introduction
Organochlorine insecticides have been used in South
Dakota since 1946 for the control of noxious insects (4).
Although many of these insecticides have been banned or
limited, residues of some of the more persistent compounds
such as DDT, dieldrin, and lindane are still commonly
found in birds of South Dakota (6, 7).
' Slalion Biochemistry Section. Chemistry Dcpanmenl. South Dal(Ola Stale Univer-
sity. Brooltings. SD 57UU7 This paper is being published with the approval of the
Director of the South Dakota Agricultural Experiment Station as Publication No
1515 of the journal article series
Four common species of South Dakota birds with distinctly
different feeding habits were analyzed in 1975-76 for
eleven insecticide residues, six metals, and polychlorinated
biphenyls (PCBs) to determine present levels of these
chemicals so that comparisons could be made in future
studies.
Methods and Materials
INSECTICIDE AND PCB ANALYSIS
Seven common crows (Corvus brachyrhynchos), six
American coots (Fulica americana), six starlings (Sturnus
vulgaris), and six Franklin's gulls (Larus pipixcan) were
analyzed. Organochlorine insecticide and PCB residue
levels were measured on a wet-weight basis in brain, liver,
feather, and carcass samples from each bird. Metal levels
were measured on a dry-weight basis for each bird. Sam-
ples were analyzed for lindane, heptachlor, heptachlor
epoxide, dieldrin, aldrin, methoxychlor, endrin, tox-
aphene, DDE, TDE, DDT, zinc, cadium, lead, copper,
arsenic, and manganese.
All birds were killed by shotgun. Gulls were collected
September 2, 1975, approximately three miles west of
Nunda, South Dakota, while feeding in a freshly plowed
field. Coots were collected September 15. 1975, approxi-
mately five miles southeast of Arlington, in a marsh.
Starlings were obtained February 14, 1976, near Crocker.
South Dakota Game, Fish, and Parks personnel collected
crows April 6, 1976, near Richmond Lake in Brown
County. All specimens collected appeared to be normal and
healthy.
Authors had intended to use only adults for the study but
could find no literature on estimating the age of crows and
starlings. They selected the seven heaviest crows for study
and they analyzed all starlings collected because only six
had been taken. Coots were aged by leg color (9) and gulls
by plumage (15). All coots and five of six gulls analyzed
were judged to be adults.
Pesitcides Monitoring Journal
Each specimen was necropsied to remove tissue samples
and to determine sex, stomach contents, and general body
condition. Technicians removed 5 g of feathers, finely cut
them, and wrapped them with aluminum foil. Brains and
livers were removed, weighed, and stored in glass jars.
Carcass samples consisted of the entire body minus beak,
legs, stomach contents, and the samples of feather, brain,
and liver previously removed. After necropsy, the car-
casses were wrapped and frozen in aluminum foil: several
days later they were homogenized by grinding with a
Toledo meat chopper, and frozen in glass jars for later
analysis. All glassware used for storage and later insec-
ticide analysis was washed in detergent, rinsed with dis-
tilled water, and baked at 425°C for at least 3 hours to
remove organic contamination.
Samples were extracted and purified for chlorinated hy-
drocarbon residues analysis by a Florisil column method
(/6) as modified by Greichus et al. (8). Methods for
separating PCBs and insecticides and quantitating PCBs
have been described by Greichus et al. (5). One gram of
carcass and liver and 0.5 g of brain and feathers were
analyzed.
Gas chromatograph;
Detectors:
Recorders:
Columns:
Packing:
Carrier gas:
Column temp.;
Injector temp.:
Detector temp.:
Varian Aerograph Model 2100
"■'Ni and Sc'H electron-capture
Beckman Ten Inch. I mv
6-ft X 1/16-inch borosilicate
glass
15 percent QF-1 silicone
(Fluoro) or 1:1 mixture of 15
percent QF-I and 10 percent
DC-200 silicone, both on 60-
lOO-mesh Chromosorb W (HP).
acid-washed and dimethylchlor-
osilane-treated
Nitrogen at 40 ml/minute
210° C
220° C
280° C
Identity of individual insecticides was verified by using
thin-layer chromatography (2, 4). Insecticides and PCBs
were recovered at 89 percent and 95 percent, respectively.
Minimum detection limits were set at 0.01 ppm and 0.1
ppm for insecticides and PCBs and were corrected for
percent recovery but values for metals were not corrected.
METAL ANALYSIS
Zinc was determined with a Perkin-Elmer Model 303 flame
atomic absorption spectrophotometer. Lead, arsenic, cad-
mium, copper, and manganese were determined with a
Perkin-Elmer Model 503 atomic absorption spec-
trophotometer equipped with a heated HGA-2100 graphite
furnace and a Sargent-Welch Model SRLG recorder. A
Perkin-Elmer deuterium arc power supply Model 560
background corrector was used in conjunction with the
spectrophotometer when necessary. Operating conditions
of the instrument were essentially the same as those given
by the manufacturer. Before analysis. 0.5 g dry weight of
each sample was digested in 10 ml of concentrated nitric
acid on a micro-Kjeldahl digestion apparatus until 2 ml of
solution remained. An additional 5 ml of nitric acid was
added, and the solution was boiled until I ml remained.
Samples were reconstituted to 10 ml with distilled water
and analyzed directly. Average recoveries for metals were
copper 87, cadmium 91, manganese 82. arsenic 73. lead
79. and zinc. 94 percent.
Minimum detection limits used for heavy metals were 0.01
ppm for cadmium. 0.1 ppm for arsenic and lead. 0.5 ppm
for copper and manganese. 1.0 ppm for zinc. In calcula-
tions of averages and totals, less than (<) values were
included and given one-half the stated value; that is. a
value of less than 0. 1 ppm is recorded as 0.05 ppm.
Results and Discussion
INSECTICIDES AND PCBs
Average insecticide residue concentrations for common
crows, starlings. American coots, and Franklin's gulls are
given in Table 1. Endrin. heptachlor. methoxychlor, al-
drin, and PCBs were not detected above the minimum
detectable levels in any of the 100 samples analyzed.
Toxaphene detected in starling feathers was judged to have
been an inadvertent contaminant from a container used to
carry the birds. Lindane was found in only two crows and
was not used in the calculation of average total insec-
ticides. One crow had carcass and liver residues of 0.01
ppm and 0. 1 1 ppm lindane, respectively: another crow had
a carcass residue of 0.01 ppm. Heptachlor epoxide was
detected in crow carcass and liver samples and in one crow
brain. Dieldrin residues were found in all species, all four
tissue types, and in 61 percent of all samples, except the
coot. Dieldrin was either absent from the tissues of the
coot, or present in the liver at the limit of detection, 0.01
ppm. Dieldrin concentrations in the brain and feathers of
the four species were usually below or slightly above the
0.01 ppm lower analytical limit.
DDT and its metabolites were the residues found most
consistently. DDE was the most prevalent of the DDT
complex and was found in 93 percent of all samples. TDE
and DDT were detected in 27 percent and 15 percent,
respectively, of all samples.
Starlings reflect the general environmental levels of or-
ganochlorine insecticides and metals available to them in
South Dakota because they are often year-around terrestrial
residents. Coots and Franklin's gulls do not reflect true
South Dakota contamination levels because they are sum-
mer resident only and are subject to migratory contamina-
tion in other areas. The low levels of TDE and DDT may
reflect the decreased use and eventual banning of DDT in
Vol. 12. No. 1, June 1978
TABLE 1. Organochlurinc iiisecliciJf residues in Sonih Dakota birds. 1975-76
Heptachlor
Epoxide
Average Residues, ppm (Mg'g) Wet Weight
Total
tiNSECTICIDES
Crow
Cool
Slarling
Gull
0 06
<0,0I
<0 01
<0 01
0.13
<0.01
0.02
0.15
0.54
0.04
0 05
0.44
0.U4
<0.01
<0.01
0.06
0.06
<0.0I
<0.01
<0.0I
0 84
0.06
0.10
0.66
Crow
Cool
Starling
Gull
0 10
<0 01
<0 01
<0.0I
0,05
0 01
0 04
0.04
0.41
0.02
0.06
0.10
0.04
<0 01
<0.01
0.04
0.02
<0.01
<0.01
<0.01
0 61
0,05
0,12
0.20
BRAIN
Crow
Cool
Starling
Gull
<0,0I
<0,0I
<0,0I
<0,0I
0,07
<0 01
<0 01
<0,01
0,05
0.01
0.02
0.02
<0 01
<0 01
<0.01
<0 01
<0 01
<0.01
<0.0I
<0.0I
0.13
0 04
0 04
0.04
FEATHERS
Crow
Cool
Starling '
Gull
<0.01
0 06
0,04
<0.01
<0 01
0.11
<0,0I
<0 01
0.02
<0.01
<0,0I
0.04
Note: Seven crows and six each of cools, starlings, and gulls were analyzed
' Starling feathers were contaminated with loxaphene at bird-collection site; no residues are reported here.
the United States in 1973, altiiough DDE is still common in
the environment.
Nationwide monitoring of mallard and black duck wings by
the Fish and Wildlife Service. U.S. Department of the
Interior, since 1965 has shown DDE to the the predominant
residue (10. II). Results of the monitoring in 1965-66
showed DDE to be the predominant residue, followed by
DDT, TDE, dieldrin, and heptachlor expoxide; in 1969,
DDE was followed by PCBs, DDT, dieldrin, TDE, and
heptachlor epoxide. In both studies, organochlorine resi-
dues were generally highest in the Atlantic and Pacific
flyways and lowest in the Central flyway of which South
Dakota is a part, and in the Mississippi flyway.
Total insecticide residues were consistently higher in crows
than in other species. Franklin's gulls had the second
highest total residue level, followed by starlings and
American coots. In brain samples, however, all three
species had approximately equal concentrations. Carcass
samples usually had the highest insecticide levels, fol-
lowed by livers; brains and feathers were about equal.
Martin {13) analyzed carcasses of starlings from 128 areas
of the United States in 1967-68 and found DDT, its
metabolites, and dieldrin in all sites. At four South Dakota
sites, the average residues for 1967-68 ranged from 0.103
ppm to 1.925 ppm DDE. 0.013 ppm to 0.018 ppm TDE.
0.018 ppm to 0.030 ppm DDT, and 0.012 ppm to 0.080
ppm dieldrin. Heptachlor epoxide and lindane were occa-
sionally found at all South Dakota sites. Average total
insecticide residues were 0.234, 0.201, 2.054, and 0.334
ppm at the four sites (/.?). Starlings monitored for the
present study in 1976 had lower average total insecticides,
0.10 ppm, than had birds in any of the four South Dakota
sites studied by Martin (13).
Average concentrations of metals in carcasses of crows,
coots, gulls, and starlings are reported in Table 2. Values
are given on a dry-weight basis but can be converted to the
approximate wet weight by multiplying the value by 0.43,
which was the average dry weight of 1 g of bird carcass.
Arsenic levels were similar in all four types of birds.
Converted to wet weight, arsenic residues were greater
than those reported by Martin and Nickerson (14). Starl-
ings collected from 50 sites in the United States contained
< 0.05 ppm wet weight arsenic except for one sample with
0.21 ppm arsenic ( Z-^). Gulls averaged 0.21 ppm cadmium,
higher than residues in other birds of this study but lower
than some values reported for starlings by Martin and
Nickerson (14).
TABLE 2. Metal residues in South Dakota bird carcasses,
1975-76
Average Residues, ppm iMg/g) Ohm Weight'
Metal
Arsenic
Cadmium
Copper
Manganese
Uad
Zinc
Gulls
Coots
Starlings
Crows
16
1.5
1.6
1.0
0 31
0.08
0.10
0.03
1.8
0,75
0.51
0.75
4.5
9.8'
4.0
4.2
3.2 =
0 86
0.77
0.72
82.0
71 0
75,0
52.0
Note: Seven crows and six each of cools, starlings, and gutis were analyzed
' Residues can he convened (o wet weighi by multiplying each value by 0 43. (he
average dry wcighi of 1 g of bird carca>s.
' Two birds were analyzed
Pesticides Monitoring Journai
Gulls also had higher concentrations of lead than had
coots, starlings, or crows. The gulls could have been
contaminated in areas other than South Dakota because
they are migratory. A possible cause could be the ingestion
of shot. Waterfowl are susceptible to shot ingestion in
wetland areas; upland birds are susceptible to a lesser
extent in terrestrial areas (/). Lead residues in South
Dakota starlings averaged 0.36 ppm in 1971 (14), which is
close to 0.33 ppm wet weight found among starlings in the
present study.
Manganese, copper, and zinc are essential dietary elements
and are not usually considered contaminants. Levels of
copper and zinc (Table 2) reported for the four types of
birds were not unusual. Considerably higher levels of
copper (21 ppm wet weight) and zinc (76 ppm wet weight)
have been found in livers of white pelicans (12). Man-
ganese concentrations of 9.8 ppm were more than twice as
great in coots than in other birds, possibly because their
diet contains aquatic plants rich in this element. Some
aquatic plants have comparatively high levels of man-
ganese (660 ppm dry weight) (3).
LITERATURE CITED
(J) Bagley. G. E.. L. N. Locke, and G. T Nightiiiaale . 1967.
The occurrence of lead in tissues of wild birds. Bull.
Environ. Contamin. Toxicol. 2(5):297-305.
(2) Breidenbach, A. W.. J. J. Lichtenherg, C. F. Henke. D.
J. Smith. J. W. Eichelberger, Jr.. and H. Slierle. 1964.
The identification and measurement of chlorinated hy-
drocarbon pesticides in surface waters. Rev. Ed. U.S.
Depl. Health, Educ. Welfare, Publ Health Serv Publ.
1241:63-69.
(3) Funk. W. H.. R. W. Rabe. R. Fithy. and J. I. Parker.
1973. The biological impact of combined metallic and
organic pollution in the Coeur D'Alene-Spokane River
drainage system. Natl. Tech. Info. Serv. No. PB-222 946.
(4) Greenwood, R. J., Y. A. GreUhus. and E. J. Hugghins.
1967. Insecticide residues in big game mammals of South
Dakota. J. Wildl. Manage. 3l(2):288-292.
(5) Greichus. Y. A.. A. Greichus, B. D. Ammann. D. J. Call.
K. C. D. Hamman, and R. M. Poll. 1977. Insecticides,
polychlorinated biphenyls and metals in African lake
ecosystems. I. Hartbeespoort Dam, Transvaal and Voelvlei
Dam, Cape Province, Republic of South Africa. Arch.
Environ. Contamin. Toxicol. 6(I):1-12.
(6) Greichus. Y. A.. A. Greichus. and R. J. Emerick. 1973.
Insecticides, polychlorinated biphenyls and mercury in
wild cormorants, pelicans, their eggs, food and environ-
ment. Bull. Environ. Contam. Toxicol. 9(6):321 -328.
(7) Greichus. Y. A.. A. Greichus. and E. G. Reider. 1968.
Insecticide residues in grouse and pheasant of South
Dakota. Pestic. Monit. J. 2(2):90-92.
(8) Greichus. Y. A.. D. Lamb, and C. Garrett. 1968. Effi-
ciency of extraction of metabolically incorporated HEOD
(carbon-14) from pheasant tissues, eggs and faeces.
Analyst 93:323-325.
(9) Gullion, G. W. 1952. Sex and age determination in the
American coot. J Wildl. Manage. 16(2): 191- 197.
(10) Heath. R. G. 1969. Nationwide residues of organochlorine
pesticides in wings of mallards and black ducks. Pestic.
Monit. J. 3(2):1I5-123.
(in Heath. R. G.. and S. A. Hill. 1974. Nationwide or-
ganochlorine and mercury residues in wings of adult mal-
lards and black ducks during 1969-70 hunting season.
Pestic. Monit. J. 7(3/4): 153-164.
(12) Koeman. J. H.. J H. Pennings. J. J. M. DeGoeij. P. S.
Tjioe. P. M. Olindo. and J. Hopcrafl. 1972. A prelimi-
nary survey of the possible contamination of Lake Nakuru
in Kenya with some metals and chlorinated hydrocarbon
pesticides. J. Appl. Ecol. 9:411-416.
(13) Martin, W. E. 1969. Organochlorine insecticide residues
in starlings. Pestic. Monit. J. 3(2): 102-1 14.
(14) Martin. W. £., and P. R. Nickerson. 1973. Mercury,
lead, cadmium, and arsenic residues in starlings — 1971.
Pestic. Monit. J. 7(l):67-72.
(15) Robbins. C. S.. B. Brunn. and H. S. Zim. 1966. Birds of
North America. Western Publishing Co., Inc., Racine, Wl.
340 pp.
(16) Slemp. A. R.. B. J. Liska. B. E. Langlois. and W. J.
Sladelman. 1964. Analysis of egg yolk and poultry tissues
for chlorinated insecticide residues. Poult. Sci.
43(0:273-275.
Vol. 12, No. 1, June 1978
Organochlorine Pesticide Residues in Florida Birds of Prey, 1969-76
David. W Johnston
ABSTRACT
Chlorinated hydrocarbon pesticide residues, especially DDT
and its metabolites, were determined in 71 individuals of 14
species of predatory birds obtained in Florida between 1969 and
1976. Of the 71 birds. 68 contained p.p -DDE or another DDT
metabolite; 34 contained dieldrin. DDE was found in 93 percent
of the 57 adipose tissue samples, all the 9 brain samples, and 89
percent of the 62 uropygial gland samples. Of the 65 birds taken
since 1972, 61 contained DDE in at least one of these three
tissues The annual average of 'S.DDT in adipose tissue and
uropygial gland over the 6-year span was approximately 5 ppm
wet weight. From 1973 to 1976, no significant increase or
decrease in pesticide burdens was detected. Some birds had no
DDE whereas others contained up to 76 ppm IDDT. None of
the data suggest thai any of the birds of prey had died of DDT
or DDT metabolite poisoning.
Introduction
For approximately two decades in North America, much
public and scientific interest has been focused on popula-
tion declines of various birds of prey including eagles,
osprey (Pandion haliaetus), and peregrine falcon iFaIco
peregrinus). In some species, correlations have been made
or suspected between pesticide burdens, especially DDE,
and mortality, population declines, or altered physiological
processes resulting in impaired reproductive performances
(8, IH). Eggshell thinning is now believed to be a result of
high DDE burdens, both in captive and feral birds of prey
{13, 14. 17). One might anticipate high pesticide burdens
in birds of prey because they are usually terminal members
of food chains, and thus can concentrate the fat-soluble
chlorinated hydrocarbon pesticides. In most published ac-
counts dealing with these birds, pesticide residues were
extracted from eggs or nestling birds or from birds experi-
mentally fed DDT (4. 13, 14); there are few published
' Deptrtmenl of Zoology, Universily of Florida, Gainesville, FL .'i2611 Research
supported in pan by Gram GB 25R72 from the National Science Foundation.
Washington. OC
accounts of body burdens in adults except for a limited
number of autopsied birds found dead and suspected of
pesticide poisoning. In fact, virtually nothing has been
published on body burdens in feral adult birds of prey
which reportedly produced thin eggshells. Thus, to date,
pesticide burdens at levels presumably not impairing re-
production are poorly documented (2). In the present re-
port, some organochlorine pesticide residues extracted
from birds of prey obtained recently in Florida are quanti-
tated.
Sampling Methods
The birds analyzed were obtained between 1969 and 1976,
chiefly in northcentral Florida near Gainesville. Most birds
were fresh roadkills or were illegally shot by hunters. A
few were picked up alive in a weakened condition or were
having convulsions; they were kept in an aviary, and died
within 24 hours. With the possible exception of the latter
birds, the present report includes birds dying accidentally,
that is, there was no a priori suggestion that any pesticide
burden contributed to death.
The sample includes two orders (Falconiformes: vultures,
kites, hawks, falcons, osprey, caracara; Strigiformes:
owls). In all, 6 families, 12 genera, 14 species, and 71
individuals were analyzed.
Analytical Procedures
From each specimen, whether fresh or previously frozen in
individual plastic bags, samples of subcutaneous adipose
tissue (fat) and/or the entire uropygial gland and/or the
cerebrum were removed for analysis. Recently, a number
of investigators have indicated the possibility oi using the
unique avian uropygial, or preen, gland as an indicator of
pesticide burdens in birds (3. 4. II). In feral, migratory
songbirds, Johnston (//) reported a high correlation.
Pesticides Monhorinc; Journal
r = 0.7568. of SDDT between adipose tissue an(J uropy-
gial gland. In the present study, birds varied in the degree
of obesity; in some, essentially no fat could be located, so
only the gland or brain was used for analysis. For 59
samples of fat, the mean sample weight was 1.1224 g; for
62 samples of uropygial glands, the mean weight was
0.5590 g; and the mean brain weight taken from 9 birds
was 4.1375 g. Each sample was individually thoroughly
homogenized in sodium sulfate, and extracted for at least
12 hours with petroleum ether in a Soxhlet apparatus. The
lipid extract was evaporated to dryness, weighed, and
partitioned with acetonitrile and hexane.
Detector: electron-capture
Column: 6-ft x Vj-inch glass, packed with a
mixture of 6.4 percent OV-210 and 1.6
percent OV-17 1 1 + 1 ) on Chromosorb W
Temperatures: injection port 210° C
column 212° C
detector 215° C
Carrier gas: nitrogen flowing at 45 nil/minute
Recoveries for the organochlorine compounds ranged from
75 percent to 95 percent. Sensitivity was approximately
0.01 ppm.
Rexultx
All samples
were
an
alyzed on a Model 600-D Varian gas
chromatograph
w
th
the
following instrument parameters Table 1 contains the results
of analyses
for the
71 birds of
and operatin
gc
onditions:
prey. Tissues
analyzed
for
the Individ
ual
biriJ
s were not
TABLE 1 . Chlorinated pesiicide burdens in Florida birds of prey.
1969-76
Tissue ^ and
Residues.
PPM Wet
We
GHT
County
Date Age ' Weight, g
p.p'-DDE
SDDT
DiELDRIN
CATHARTES AURA (TURKEY VULTURE)
Alachua
Nov 71 UNK A
(2 0751)
3 37
3.55
0
Lev,
Apr 73 M A
(3.0238)
B
(6 0752)
1 32
0 17
3.00
0,17
0.07
0
Alachua
Apr 73 FA
(4 0514)
B
(5,5159)
0 78
0,11
1 32
0,11
0.46
.0
Levy
May 73 MA
1,59
2.28
0.07
Levy
May 73
Leon
May 73
Sepi 74
CORAGYPS ATRATUS (BLACK VULTURE)
Alachua
'Marion
[Contimied next page)
Vol. 12, No. 1, June 1978
Jan 72
May 73
May 73
M F
(2 0323)
F A
(2 8724)
U
(1,0003)
F A
(2 2551)
B
(5 6169)
6,39
3 83
10,50
1 26
0.10
II 75
6 87
15 25
1 49
0 II
1 18
0.22
0.50
0.04
0
TABLE 1 (continued). Chlorinaled pesticide burdens in Florida birds of prey. J 969-76
Date
Tissue * and
Sex/
Sample
Age '
Weight, g
Residues, ppm Wet Weight
p.p'-DDE
SDDT
CORACYPS ATRATUS (BLACK VULTURE)— Continued
May 73
A
3.06
7 68
(3 0264)
U
5,44
6.84
(0 8266)
A
1 1 56
25.43
(0 9518)
U
9 33
14 74
(0 8682)
0 66
0,24
2 02
0 69
ELANOIDES FORFICATUS (SWALLOW-TAILED KITE)
May 75
U
(0 6269)
ACCIPITER STRIATUS (SHARP-SHINNED HAWK)
A
(0 3009)
U
(0.0637)
16 62
19.62
17 12
19.62
ACCIPITER COOPERII (COOPER S HAWK)
Alachua
Sept 73
V
(0.2763)
BUTEO J A MAICENSIS (RED-TAILED HAWK)
July 73
July 74
IMF
IM
IM
A
6.25
6 25
(1.8650)
U
0 10
0 10
(0 4830)
A
3 49
3.73
(1 0422)
U
0 11
Oil
(0.4788)
A
0 37
0 48
(0.7617)
U
0 39
0.50
(0.7570)
A
0 59
1.32
(1 6963)
U
0 21
0 21
(0.4846)
A
0 37
0.37
(0.5357)
U
0
0
(0.4527)
A
4.26
5 86
(0 4694)
U
0 38
0 38
(0 3936)
A
6 14
7 19
(0 5699)
U
1 05
1 05
(0.2852)
0
0
0 89
0
0.04
0
0
0
0
0
0 85
U
0 38
0 38
0
(0 3936)
Madison
Jan 76
IM
A
(0 5699)
6 14
7 19
2.37
U
1 05
1 05
0 18
(0.2852)
BUTEO LINEA TUS (RED-SHOULDERED HAWK)
Alacliua
Jan 72
F
A
(1 3596)
0 64
1 04
006
U
0 18
0.18
0
(0.2853)
Alachua
Sept 73
IM
A
(0 3310)
0.45
1.21
0
U
0 24
0 60
0
(0 3104)
Alachua
Jan 76
AD
A
(0 1888)
7,15
7 15
0
V
0 39
0 39
0
(0.2552)
Pinellas
Jan 76
F
A
(0 2615)
34 42
61 76
38 24
U
0 80
1 80
0 80
(0 2514)
Baker
May 76
F
U
(0 6186)
1 21
121
0
(Continued next page)
10
Pesticides Mon
ITORING JOURNAI
TABLE 1 (continued). Chlorinated pesticide burdens in Florida birds of prey. 1969-76
Sex/
AOE '
Tissue ^ and
Sample
Weight, g
Residues, ppm Wet Weight
p.p'DDE
PANDION HALIAETUS (OSPREY)
Apr 73
Sepi, 74
Apr 75
May 76
A
(0 3864)
U
(2.4581)
A
(2 8327)
U
(4 1778)
A
(0 3S401
U
(1 1643)
A
(0 7767)
U
(0 6309)
U
(0 4922)
A
(0 4861)
U
(3.7545)
0.13
1.55
0.55
0 41
0
0.09
0 33
0.32
13.21
1 65
0 53
IDDT
0.26
1.79
1.29
0.62
0
0.09
0.33
0 32
15 85
1 87
0.71
0
0
0
0
0
0
0
0
0.91
0
0
Pinellas
May 76
M
A
(0.4264)
1.52
2.46
0
U
1 39
1.39
0
CARACARA CHERIWA l" (CARACARA)
Glades
July 75
ADF
A
(0 1416)
2.47
2.47
0
U
1.25
1.25
0
(0 5854)
Highlands
July 75
IMF
A
(0 0805)
I 24
1.24
0
U
0.48
0.48
0
(0 6235)
Highlands
Apr 76
IM F
A
(0.1229)
3 25
3.25
0
U
2.44
2.44
0
FALCO SPARVERIUS (AMERICAN KESTREL)
Mar 73
Mar 73
Mar 73
Mar 73
Jan 74
Jan 75
Nov. 75
M
M
A
(0 2810)
U
(0 0954)
A
(1.1978)
A
U
A
(0 1588)
U
(0.0788)
A
(0.1399)
U
(0.0602)
A
(0 0551)
U
(0.0833)
U
(0 0653)
A
(0 0980)
U
(0 0258)
A
(0.0262)
U
(0.0302)
A
U
U
(0 0486)
B
(1.0756)
U
(0.0459)
14 59
3.15
1 77
20 57
4 63
0 79
0 63
2 14
1.66
9.07
1 80
0
0
1 94
0
0
7 61
1 44
4 12
0.42
7.63
16 37
3.15
2.09
22.71
4 63
0 79
063
2.14
1.66
9.07
1.80
0
0
1 94
0
0
8.03
2.20
4 12
0.42
18 53
0 36
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3.09
0.70
4.36
{Continued next page)
Vol. 12, No. I.June 1978
11
TABLE 1 (continued). Chlorinated pesticide burdens in Florida birds of prey, 1969-76
Residues, ppm Wet Weight
Tissue ^ and
Sex/
Sample
Age '
Weight, g
p.p'-DDE
XDDT
DiELDRIN
FALCO SPARVERWS (AMERICAN KESTREL)
Pinellas '
B
(1.1574)
U
(0 0486)
B
(12114)
A
(0.0790)
U
(0 0505)
0.30
2 06
1 03
0
0
0.74
2 06
1,03
0
0
0.82
1 03
0.37
0
0
TYTO ALBA (BARN OWL)
May 76
A
(0.9538)
U
(2.1913)
U
(0 3550)
8 28
1.31
0
9.27
1.31
0
1 68
0
0
OTVS ASIO (SCREECH OWL)
Levy
Indian Riv
Pinellas >
Pinellas '
Sepl. 73
May 75
Jan 76
May 76
F
A
6 19
(1.1317)
U
1 17
(0.I20I)
UNK
A
(0.3585)
0,26
U
0
(0 1454)
UNK
A
(0 6573)
0 30
U
3 48
(0 1435)
UNK
U
(0.0378)
10 58
M
U
(0 0502)
49.80
M
U
(0 0748)
1 34
6.19
1 17
U 26
0
0 30
3 48
10 58
49,80
1.34
BUBO VIRGINIANVS (GREAT HORNED OWL)
Diiie
Maruin
Dec. 75
May 76
UNK
A
(3.0278)
2 06
U
8 24
(0 6823)
F
A
(0 6460)
5 42
U
3 28
(0.7466)
UNK
U
(0 4400)
17.05
MF
A
(0 2821)
9 75
U
0 81
(0 5537)
3 59
8 68
9 21
4 28
17 05
12 05
0 81
0.08
0
3 02
0 47
0
6 20
0
STRIX VARIA (BARRED OWL)
Alachua
Alachua
Apr. 73
May 74
Dec 75
UNK
A
(1.5201)
U
(0.7385)
U
(0 5460)
A
(0 22S6)
U
(0.5321)
A
(O.II83)
U
(0 6588)
A
(0.1830)
U
(0.5843)
5 76
5 08
74.18
1 09
0.37
7.61
I 44
1 09
0 73
6 90
5 69
75 93
1 09
0.37
8.03
2 20
1 09
0,73
0,21
0 14
0
0
0,40
0
0
0
0
' M~ftdull male. F=idult female, AD= adult of undetermined sex, UNK = bird of unknown sex or age, JUV= juvenile, IM = immature. Sex of juvenile and immature birds was
not always recorded
' Tissue abbreviations A = adipose tissue. U~uropygial gland. Bahrain
^ Birds that reportedly died in captivity and exhibited convulsions
12
Pesticides Monitoring Journal
always perfectly uniform because birds were obtained in
different ways by different persons, and it was frequently
inconvenient or impossible to take samples of brain, fat,
and the uropygial gland from every bird. Furthermore, due
to its relatively superficial position, the uropygial gland
was sometimes damaged, and quite often a specimen was
so lean that no fat could be found for pesticide analysis.
Even so, a number of important features emerge from the
data in Table 1. All taxa (family, genus, and species) had
some birds containing p,p' -DDE or other DDT metabolite.
Dieldrin, on the other hand, was not present in all taxa. Of
the 71 birds, 68 (96 percent) contained DDE but only 34
(48 percent) contained dieldrin in at least one of the three
tissues. In the three tissues analyzed 93 percent of the fat
samples contained DDE, 100 percent of the brains con-
tained DDE, and 89 percent of the uropygial glands con-
tained DDE. These values indicate a nearly universal oc-
currence of DDE in the birds studied and in the three
tissues sampled.
In the 45 birds of prey in which both adipose tissue and
uropygial gland were analyzed and in which one or both
samples contained DDE, 40 (89 percent) had DDE in both
tissues, 3 (7 percent) had DDE in adipose tissue only, and
only 2 (4 percent) had DDE in the uropygial gland alone.
However, Figure 1 shows a poor correlation (/■ = 0.3398)
of SDDT, in ppm wet weight, between these two tissue
types. Of 46 birds, 40 had higher concentrations of 2DDT
in the adipose tissue than in the uropygial gland. For the
species analyzed, the mean ratio of SDDT in adipose tissue
to uropygial gland was 2.6:1, a higher ratio than the 2.2; I
reported by Johnston (//) for a sample of other feral
species such as loons, cormorants, herons, and gulls.
Figures 2 and 3 show SDDT found, respectively, in the
adipose tissue and uropygial gland through the sampling
period. In both samples, median values were calculated for
all the species in a given year; these values are indicated by
f^
OS,.
5 -
SOLID LINE CONNECTS
MEDIAN ANNUAL VALUES
FIGURE 2. ^DDT in adipose tissue of Florida birds of prey.
1971-76
'^
O *
::(.:
1974
12
1975
15
1976
14
> ?
Q. a>
O »
tr —
-, »,
h- a.
a "
o
■
•
•
1= 0.3398
•
Y=0.I4X-H.75
%^
•
m
•
•
.• • •
• •
•
•
•
I DDT IN ADIPOSE TISSUE
(ppm wet weight)
FIGURE 1 . Relationship of IDDT in adipose tissue
and uropygial gland in Florida birds of prey. 1969-76
FIGURE 3. XDDT in uropygial glands of Florida birds of prey.
1971-76
a solid line. The lines might not indicate realistic trends
because the numbers of a given species available for
analysis varied from year to year, as indicated by raw data
in Table 1 .
Discussion
Of the 14 species examined here, there is no assurance that
any bird was a permanent resident where collected except
for the caracaras and juvenile osprey. Any or all the birds
might have been transient or migratory at some time during
their lives, so pesticide burdens determined for these birds
Vol. 12, No. 1, June 1978
13
were not necessarily accumulated in Florida, but could
have come from prey consumed on a wintering area south
of the state, from a breeding area in the north, or in
intervening areas during migratory nights. It is likely,
however, that most of the four owl species were Florida
residents because they tend to migrate less than the other
birds of prey studied here.
Subspecific information was determined only for the
American kestrel. These small falcons were all representa-
tive of the northern subspecies ( Faico s. sparverius) which
migrates into Florida from the northern United States and
winters in large numbers in the state. The author was
unable to obtain samples of the local resident Florida
subspecies. F. s. pautus. for analysis. Data on the vul-
tures. Catharles and Coragyps. are presented in Table I
and appear to be the first residue findings published on
these species.
Because vultures are terminal members of food chains,
they might be expected to have exceptionally high DDT
levels, but this does not appear to be true of Catharles.
Only I of 10 turkey vulture fat samples exceeded 10 ppm
SDDT; the mean was 4.76 ppm. However, the mean for
the fat of 5 Coragyps was 10.64 ppm SDDT; one bird had
25.43 ppm. Both vultures scavenge road-killed animals
such as the nine-banded armadillo. Virginia opossum,
dogs, and various smaller mammals, birds, and reptiles in
Florida, most of which are nonmigratory. Why Coragvps
should have a higher mean burden of SDDT than do
Catharles is unclear.
The Accipiter hawks, also called bird hawks, have pes-
ticide burdens as high as or higher than most other species
studied (Table 1). The small sample size precludes
generalizations, but it is noteworthy that in 1972 Henny
reported that the Cooper's hawk "is in serious jeopardy in
the northeastern U.S." ( 6 ) .
Some species listed in Table 1 are largely insectivorous
(5), namely, Etanoides forficutus. FaIco sparverius. and
Otus asio. At least three of the 14 specimens of Falco had
SDDT burdens exceeding 10 ppm; one contained 18.53
ppm in the uropygial gland, and the 2DDT burden in
adipose tissue probably exceeded 50 ppm. Two of six Otus
specimens had exceptionally high levels in their uropygial
glands; 10.58 ppm and 49.80 ppm. For this species, 10
ppm DDE dry weight in the diet produced thin eggshells
(13). Although dietary levels of DDT may not be directly
related to levels in the adipose tissue or uropygial gland, it
is significant that 5 ppm DDT wet weight in the diet of
Falco sparverius resulted in the classical eggshell-thinning
syndrome (17). However, carcass (17) and breast muscle
(8) analyses of dead or dying American kestrels in the
northern United States had generally higher DDT burdens
than those found in the present study (/). For this species,
it is significant that three individuals contained no DDT or
metabolite (Table I ).
Henny et al. presented data on eggshell thicknesses and
populations of red-shouldered hawks (Buteo lineatus) from
a refuge in Maryland (7). The authors thought it "doubtful
that the relatively low pesticide levels in the eggs had a
detrimental effect on the reproductive performance of the
population." Except for a single bird containing 61.76
ppm 2DDT and 38.24 ppm dieldrin. organochlorine resi-
dues in this species were generally low (Table 1 ).
The osprey (Pandion haliaeius) was studied intensively in
the 1960s because its population had declined precipitously
in some areas (6). As with other species discussed in this
paper, presticide levels in eggs and nestlings have been
published but data for adults are scarce. Wiemeyer et al.
reported brain and carcass analyses of dead birds in Con-
necticut and Virginia (18). DDE residues in carcasses
averaged 23 ppm wet weight, generally, exceeding the
levels in adipose tissue and uropygial gland in Florida birds
reported here. Because different tissues were analyzed, it
is difficult to compare previously published data on red-
tailed hawks and great horned owls with those reported
here. For three nestling red-tailed hawks, Seidensticker
found an average of 21.50 ppm 2DDT wet weight, in
breast muscle (15). Seidensticker and Reynolds reported
1.40 ppm wet weight iDDT in nestling red-tail hawk
muscle and 9.29 ppm XDDT in the muscle of a great
horned owl ( 16).
Two generalities emerge from the data in Table 1 and
Figures 2 and 3. There is no firm evidence for this sample
of birds of prey from Florida that DDE and dieldrin
burdens diminished in 1971-76. In both the adipose tissue
and uropygial glands, the data indicate an approximate
average of 5 ppm over the 4-6 year span. Small migratory
songbirds, on the other hand, showed a dramatic decrease
of DDE in adipose tissue from 1964 to 1973 (9, 10). That
decrease was correlated with the decreased use of DDT in
the United States during the same time. Presumably, the
ban on DDT use in the United States imposed by the U.S.
Environmental Protection Agency (EPA) December 31.
1972. should have reduced the amount of DDT in natural
ecosystems. The birds of prey studied here are significant,
especially those analyzed after 1972. because a large pro-
portion did contain DDT or a metabolite. How would a
hawk, owl, or vulture obtain significant quantities of DDT
in 1976? It is plausible that a long-lived bird could have
accumulated small pesticide quantities for years and simply
stored them in adipose tissue. Unless these deposits were
totally depleted for energy resources, the pesticides might
not have been mobilized into the bird's bloodstream or
eliminated except in very small quantities. The data on
uropygial glands presented in Table 1 indicate that birds of
prey eliminate smaller quantities of pesticides through this
gland than do other types of birds (.?. 4).
A second possible explanation for the DDT burden in birds
of prey after the EPA ban in 1972 is that at least eight
species analyzed here might have migrated to Florida from
14
Pesticides Monitoring Journai
the West Indies or Central America where they could have
obtained DDT-contaminated foods. This is probably simi-
lar to the situation of the migratory American kestrels
discussed by Lincer and Sherburne {12). They suggested
that this species obtained pesticide-laden foods chiefly
from the wintering grounds rather than from nesting sites
in the northern United States. They state: "The disastrous
role played by the far-removed, but inordinately contami-
nated, winter prey once again dramatically points out the
global nature of the biocide problem." Still, the presence
of DDT in tissues of the caracara, which is a resident of
southcentral Florida, is an enigma.
Since 1973, the SDDT burdens in adipose tissue of two
species examined here, osprey and American kestrel, were
very low (0-2 ppm).
A cknowledgments
O. L. Austin, Jr., P. Brodkorb, R. L. Crawford, D. J.
Forrester, T. Gilyard, R. Heath, Jr., H. W. Kale, II, S. A.
Nesbitt, and J. M. Whittier assisted in collecting birds.
Birds from Leon County, Florida, were provided by per-
sonnel at the Tall Timbers Research Station. I thank the
following for help in laboratory analyses: R. Bull, G.
Cause, A. Meylan, and M. Raum. An earlier draft of the
manuscript was critically examined by W. H. Stickel.
Illustrations were prepared by E. Belcher.
LITERATURE CITED
(1) Bernard. R F. 1962. Secondary DDT poisoning in a
sparrow hawk. Auk 79(2):276-277.
(2) Cade. T. J.. C. M. While, and J. R. Haugh. 1968
Peregrines and pesticides in Alaska. Condor 70(2): 170-
178.
(3> Charnelski. W. A., and W. E. Stevens. 1974. Or-
ganochlorine insecticide residues in preen glands of ducks;
possibility of residue excretion. Bull. Environ. Contam.
Toxicol. 12(6):672-676.
(4) Dindal. D. L. 1970. Accumulation and excretion of CI"'
DDT in mallard and lesser scaup ducks. J. Wildl. Manage.
34(l):74-92.
(5) Grossman. M. L., and J. Hamlei. 1964. Birds of Prey of
the World. Chas. N Potter, Inc. New York, NY. 496 pp.
t6) Henny. C. J. 1972. An analysis of the population dynamics
of selected avian species, with special references to
changes during the modern pesticide era Wildl Res. Rep.
1, U.S. Department of the Interior. Fish and Wildlife
Service, Bureau of Sport Fisheries and Wildlife, Wash-
ington, DC.
(7J Henny. C. J.. F. C. Schmid. E. M. Martin, and L. L.
Hood. 1973. Territorial behavior, pesticides, and the
population ecology of red-shouldered hawks in central
Maryland. 1943-1971. Ecology 54(3);545-554.
(8) Hickey. J. J. (ed.) 1969. Peregrine Falcon Populations.
Their Biology and Decline. Univ. Wise. Press, Madison.
Wl. 596 pp.
(9> Johnston. D. W. 1974. Decline of DDT residues in migra-
tory songbirds. Science 186 (4166):841 -842
(10) Johnston. D W. 1975. Organochlorine pesticide residues
in small migratory birds. 1964-73. Pestic. Monit. J.
9(2):79-88.
(11) Johnston. D. W. 1976 Organochlorine pesticide residues
in uropygial glands and adipose tissue of wild birds. Bull.
Environ. Contam. Toxicol. 16(2): 149-155.
(12) Lincer. J. L.. and J . A. Sherburne. 1974. Organochlorines
in kestrel prey: a north-south dichotomy. J. Wildl Man-
age. 38(3):427-434.
(13) McLane. M. A. R.. and L. C. Hall. 1972. DDE thins
screech owl eggshells. Bull. Environ Contam. Toxicol.
8(2):65-68.
(14) Porter. R. D.. and S. N. Wiemeyer. 1969. Dieldrin and
DDT: effects on sparrow hawk eggshells and reproduction.
Science 165 (3889): 199-200.
(15) Seidenslicker, J. C. IV. 1970. A biopsy technique to
obtain tissue for pesticide residue analysis from fal-
coniform birds. Bull. Environ. Contam. Toxicol.
5(5):443-446.
(16) Seidenslicker. J. C. IV. and H V. Reynolds III. 1971.
The nesting, reproductive performance, and chlorinated
hydrocarbon residues in the red-tailed hawk and great
horned owl in south-central Montana Wilson Bull.
83(4):408-418.
(17) Wiemeyer. S. N.. and R. D. Porter. 1970. DDE thins
eggshells of captive American kestrels. Nature (London)
227:737-738.
(18) Wiemeyer. S. N.. P R. Spitzer. W. C. Krantz. T. G.
Lamont. and E. Cromartie. 1975. Effects of environmental
pollutants on Connecticut and Maryland ospreys. J. Wildl.
Manage. 39(1): 124-139.
Vol. 12, No. I.June 1978
15
Shell Thinning and Pesticide Residues in Texas Aquatic Bird Eggs, 1970
Kirke A. King,' Edward L Flickinger.' and Henry H. Hildebrand '
ABSTRACT
Significant decreases in eggshell ihicliness were found in 15 of
22 species of aquatic birds in Texas in 1970. Shell thickness
reductions of 9 to 15 percent were found in while pelicans
(Pelecanus erylhrorhynchos), brown pelicans (P. occidentalis),
and great blue herons (Ardea herodias). DDT family compounds
were found in all eggs, and mean residues ranged from 0.4 ppm
in while ibis (Eudocimus albus) to 2i.2 ppm in great egrets
(Casmerodius albus). IDDT residues were negatively corre-
lated with shell thickness in five species: PCBs were negatively
correlated in two. Residues in marine birds were generally
lower and more uniform than levels in birds feeding in fresh and
brackish water. DDT and dieldrin residues were higher in eggs
from colonies near agricultural areas where these insecticides
were heavily used: higher PCB residues were consistently as-
sociated with urban and industrial areas. Populations of five
species have declined and deserve continued study: brown peli-
can, reddish egret (Dichromanassa rufescens). white-faced ibis
(Plegadis chihi), laughing gull (Larus atricilla), and Forster's
tern (Sterna forsteri). Population trends of four other species
were undetermined and should he followed closelv in future
years
Introduction
Eggshell thinning has been noted in a number of declining
populations of fish-eating birds in the United States (2, 6.
19, 20). Laboratory investigations show that the DDT
family compounds. SDDT, primarily DDE. induce shell
thinning in some wild birds and their eggs (15. 16. 2H).
The recent decline in brown pelicans, reddish egrets, and
an apparent decline in white-faced ibis on the Texas Gulf
Coast prompted the present study to determine the extent of
eggshell thinning and the impact of pesticide contamination
on these and other fish-eating birds breeding in Texas. The
authors present information on shell thickness changes and
* Pith and Wildlife Service, U S Oepanmenl ol (he Inlenor. PaluxenI Wildlife
Research Center. Gulf CoaM Field Slalion. P O Bo» 2iOb. Victoria. TX 77901
' Department of Biology, Texas A&i University, Kingsville, TX 78363
chemical residues in eggs of 22 species of aquatic birds.
Sources of contamination and species threatened by expo-
sure to pesticides are identified.
Study Area and Methods
From March through July 1970. 1,043 eggs were collected
in 30 locations on the Texas Coast. One egg was taken
randomly from each nest sampled in a pattern distributed as
evenly as possible throughout each colony. Whole eggs
were weighed and measured, wrapped in aluminum foil,
and frozen. Contents were later removed, stored in jars
prerinsed with acetone, and immediately refrozen until
analysis. Five to 20 eggs of each species were analyzed at
the Denver Wildlife Research Center Laboratory, Denver,
Colorado. Chemical analyses were completed in 1970 and
1971. Except for brown pelican eggs which were addled,
only fresh eggs were analyzed for pesticide residues.
The authors biased selection of eggs for chemical analysis
by singling out thin-shelled eggs from each species. Ran-
dom samples of white-faced ibis, black-crowned night
heron, and Forster's tern eggs were also analyzed. Mercury
levels were determined in 10 white-faced ibis and 10 great
blue heron eggs.
Organochlorine residues and polychlorinated biphenyls
(PCBs) were determined by using methods described by
Peterson et al. (25). The methods measure SDDT, aldrin,
dieldrin, endrin, heplachlor epoxide, and lindane at 0.1
ppm wet weight, and chlordane and toxaphene at 0.5 ppm
wet weight. PCBs were not separated from pesticides be-
fore measurement. When found. PCBs were identified on
two separate columns and by visual comparison of
chromatograms with standard Aroclors. The PCB residues
were quantitated by averaging peak responses and com-
paring them with Aroclor 1254 standards. Detection limit
of the procedure for PCBs was 0.5 ppm. Mercury residues
16
Pesticides Monitoring Journai-
were determined by using methods described by Okuno et
al. (24). No corrections were made for possible moisture
loss.
The authors compared shell thicknesses of eggs collected
in 1970 with those of museum eggs collected before wide-
spread use of DDT. Data on white and brown pelican
eggshells collected before 1947 are from Anderson and
Hickey (2); data on white-faced ibis eggshells were
supplied by A. J. Smith and J. O. Keith (personal com-
munication. 1971). All other measureinents of eggshells
collected before 1943 were obtained from the Western
Foundation of Vertebrate Zoology, Los Angeles. Califor-
nia, and Welder Wildlife Foundation. Sinton. Texas. An-
derson and Hickey (/). showed that eggshell thickness for
a particular species varies significantly over broad geo-
graphic areas particularly with latitude. Whenever possi-
ble, museum eggs from the Texas Coast and other southern
latitudes were selected for shell thickness measurement.
Results and Discussion
EGGSHELL CHANGES
Fifteen of 22 species sampled showed a signficant negative
change in eggshell thicknesses from their museum mean
(Table 1). The species with the greatest average thinning
were the white pelican (15 percent), great blue heron (13
percent), and brown pelican (11 percent). No collapsed
eggs were found in the nests of these species. Although the
average thinning of white-faced ibis eggshells was only 4
percent, numerous collapsed, dented, and cracked eggs
were found in and around ibis nests. In 1971. continued
sampling showed that about 3.5 percent of the white-faced
ibis eggs in marked nests had denied or cracked shells; the
incidence of cracked eggs of other species was less than I
percent. Numerous field studies have shown that eggshell
thinning of less than 10 percent seldom incurs egg break-
age {3. 6, 10). Egg loss becomes evident with thinning of
10-15 percent (19), and serious breakage, usually accom-
panied by population decline, occurs when eggshell thin-
ning exceeds 15 percent (2. 20). The degree of shell thin-
ning among the white and brown pelicans and great blue
heron approaches thai found in other populations in which
shell thinning adversely affected reproduction.
Average shell thinning was greatest in the Lower Laguna
Madre-Green Island region (Figure I). Shell thickness did
not vary significantly among heronries sampled elsewhere
on the Texas Coast.
ORGANOCHLORINE RESIDUES
Residues of 2DDT, primarily DDE, were found in all sam-
ples. The highest averages were in eggs of the great egret,
23,2 ppm; Caspian tern, 15.1 ppm; and laughing gull, 10.4
ppm (Table 2). SDDT in the eggs of the remaining species
TABLE 1. Eggshell
changes of several Te.
Kas fish-eating
hirds,
pre- 1943 and in
1970
Shell Thickness, mm
Change
Spectes
Pewod'-'
No.
MeAN±SE
%
While Pelican
pre-IM?
102
0,6765:0005
Petecanus er\throrh\nchos
19711
2S
O577±00O8'
-15
Great Blue Heron
pre- 1943
32
0 413*0,005
Ardfa herodias
1970
74
O.M9±0,G03'
-13
Brown Pelican
pre- 1947
43
0.557*0,006
P occidenialis
1970
14
0 497*0 013'
-11
Snowy Egret
pre- 1943
38
0 241 ±0,003
Egretta thula
1970
79
0 220*0,002'
_9
Royal Tern
pre-1943
18
0358*0.004
Thalnsseus maximus
1970
12
0,330±0,007'
_g
Olivaceous Cormorant
pre-1943
30
0347*0005
Phalacrocorax olivaceus
1970
24
0 323*0,006'
_7
Louisiana Heron
pre-1943
31
O,238±O,0O3
Hydranassa tricolor
1970
58
0.225*0 002=
-5
Little Blue Heron
pre-1943
31
0,243 ±0.002
Florida caerulea
1970
32
0, 232*0003''
_3
Great Egret
pre-1943
30
0295*0,004
Casmerodtus alhu.K
1970
113
0 282±O,0O2'
-4
White Ibts
pre. 1943
38
0 363±0 0O4
Eudocimus albus
1970
48
0 .347±0,003'
-4
White-faced Ibis
pre. 1943
18
03I2±0,006
Plegadis chihi
1970
86
0 301 ±0 002'
-4
Blacl(.CTOwned Night Heron
pre-1943
79
0 278 ±0 003
Sychcorax nycncorm
1970
74
0 266*0 003'
_4
Black Sbmmer
pre-1943
28
0 249*0 0O4
RyrK-hops nigra
1970
48
0240±0.002>
-4
Oullbilled Tern
pre-1943
31
0 239±0,002
Gelochtlidon nilolica
1970
58
0,231 ±0,002'
-3
Laughing Gull
pre-1943
27
0,270*0,003
Lan^ alrtctlla
1970
65
0 263*0 002'
-3
Sandwich Tern
pre-1943
25
0 286*0,004
Sterna sand\'tcensis
1970
19
0 277±0,005
-3
Anhinga
pre-1943
31
0328±0004
Anhinga anhinga
1970
8
0,318*0.007
-3
Roseate Spoonbill
pre-1943
32
O426±0.0O8
.Ajma ajaja
1970
53
0415*0.004
-3
Reddish Egret
pre-1943
47
0 270*0.002
Dichroiruinassa rufexcens
1970
54
0 267±0,003
-1
Least Tern
pre- 1943
22
0 156*0,003
S albifront
1970
15
0 154*0,004
-1
Foraler's Tern
pre-1943
26
0,219±0,003
5 forsten
1970
41
0218±0,003
0
Caspian Tem
pre-1943
15
0 336*0,005
S caspta
1970
32
0 339±0,0O3
-t-l
' Pre- 1947 while and brown pelican data are from Anderson and Hickey (2),
• All pre-1943 eggs are from the Texas Coast except white pelican, western United
Slates; black. crowned night heron, South Carolina, Florida, and California;
snowy egret, little blue heron, great egret, and anhinga. Gulf Coast. Florida, and
South Carolina
';><0 001 (Student's /-test).
'p<0 01
'p<0,05
ranged from 0.4 ppm in white ibis to 9.7 ppm in black
skimmer. Consistently higher levels of 2DDT and the
greatest amount of shell thinning were found in eggs from
the lower coast near the intensively cultivated Rio Grande
Valley. iDDT compounds were found in eggs of species
that feed in all habitats: freshwater, brackish, and marine.
Dieldrin residues, found in 14 species, were highest in the
snowy egret, white-faced ibis, and great egret (Table 2),
species that feed primarily in freshwater and brackish
marshes. Little dieldrin was found in eggs of ocean-feeding
birds such as brown pelican, royal tern, and Sandwich tern.
Greatest dieldrin residues were in eggs from colonies adja-
cent to the Texas rice belt where aldrin had often been used
to treat rice seed.
Vol. 12, No. I, June 1978
17
-RIO GRANDE
RGURE 1 Location of colonies of wading birds sampled for
eggshell thinning, Texas Gulf Coast — 1970
PCB residues were found in all but two species; highest
levels occurred in the olivaceous cormorant, Caspian,
Forster's, and royal terns (Table 2). Except for the royal
tern, these birds feed most frequently in freshwater and
estuarine areas. The colonies associated with highest PCB
contamination are Vingtun Island near the sprawling
urban-industrial complex of Houston-Baytown, Texas, and
Dressing Point, south of Freeport, Texas; both areas have
numerous oil refineries and petrochemical plants.
Insecticide and PCB residues in marine birds were gener-
ally lower and more uniform than levels in birds feeding in
freshwater and brackish habitats. iDDT and dieldrin resi-
dues were higher in eggs from colonies near agricultural
areas where insecticides were heavily used. Higher PCBs
were consistently associated with urban and industrial
areas.
RESIDUl- CORRKI.ATIONS WITH hOCSHEl.l. THICKNESS
SDDT or DDE was negatively correlated with shell thick
ness for the great blue heron {r = -0.66; p < 0.01),
white-faced ibis (r = -0.64; p < 0.01), gull-billed tern
(r = -0.936; p < 0.02), reddish egret (r = -0.74;
p < 0.05), and brown pelican (r = -0.61; p < 0.05).
PCB residues were negatively correlated only for the red-
dish egret (r = -0.72; p < 0.05) and the brown pelican
(r = -0.53; p < O.I); no correlation was found between
18
any of the remaining insecticide residues and eggshell
thickness.
Other insecticides and industrial pollutants may affect shell
thickness because many pollutants are capable of altering
food chain composition, ecosystem energy flow, and ulti-
mately the bioenergetics of individual populations of birds.
The many environmental factors and physiological proc-
esses that result in eggshell thinning are not well under-
stood. However, the chemical pollutant most frequently
identified with shell thinning is DDE. The authors' data
support the findings of others who have reported that DDE
is the principal agent correlated with eggshell thinning in
wild birds (J, 7, 16. 26).
SOURCES OF CONTAMINATION
This study indicates that DDE and dieldrin levels detected
in egg samples are related to food habits of adult birds.
Flickinger and King (/2) found wet-weight residues of
iDDT from 0.2 to 1.6 ppm and dieldrin from 0.4 to 2.8
ppm in three species of freshwater fish that are commonly
consumed by fish-eating birds. Maximum SDDT residues
of 9.3 ppm were found in menhaden [Brevooriiu sp.) and
6.4 ppm in anchovies (Anchoa sp.) collected from 1967
through 1969 from rivers, bays, and estuaries in Texas (9).
Potential effects of these residue levels in food items are
evident from results of other studies showing that 3^ ppm
wet-weight DDE in the diet will cause eggshell thinning in
certain species of birds (16. 22. 23. 30).
DDT was found in the eggs of six species; great egret,
white-faced ibis. Sandwich tern, least tern, gull-billed tern,
and roseate spoonbill. Low DDT residues, less than 0.8
ppm, were found in all roseate spoonbill eggs. Frequency
of contamination in the other five species ranged from 4
percent in the white-faced ibis to 40 percent (two eggs) in
the Sandwich tern. The highest DDT residue found was 1 .3
ppm in a Sandwich tern egg. Local contamination through
the food chain is possible since DDT residues have been
found in a pooled sample of 76 sailfin molly {Poecilici
lalipinna) and in crawfish (Procambarus clurki), two
common foods of aquatic birds in Texas (12). Birds mig-
rating to Mexico have been contaminated also since DDT
still was widely used there in 1970. DDT residues occurred
in all five species that regularly migrate to Mexico: roseate
spoonbill, white-faced ibis, snowy egret. Sandwich tern,
and least tern.
SIGNIFICANCE OF RESIDUES
DOE — DDE-induced shell thinning has been summarized
for numerous birds (2. 2«). Residues in eggs reported in
the present study are comparable to levels found in wild
populations that have experienced reproductive failures.
Some laboratory studies indicate that harmful effects other
than shell thinning are possible Longcore (22) found re-
duced survival of ducklings (Anas ruhripes) hatched trom
Pesticides Monitoring Journal
TABLE 2. Insecticide and PCB residues in eggs of Texas wading birds, 1970
Mean Resioues±SE Wet Weight
Speoes
IDDT '
DiELDMN
PCBs
Lipid. %
Great Egret
Caspian Tern
Laughing Gutl
Black Skimmer
Least Tern
Louisiana Heron
Olivaceous Cormorant
Great Blue Heron
White-faced Ibis
Gull-billed Tern
Royal Tern
Roseate Spoonbill
Snowy Egret
Brown Pelican
Reddish Egret
Black-crowned Night Heron
Forster's Tern
White Pelican
Little Blue Heron
Sandwich Tern
White Ibis
10
10
10
5
5
5
5
20
16
10
5
10
10
II
10
10
10
5
5
5
5
23.24±3.61
I5.13±2.25
10 35±3 90
9 68±3 02
6 94±3.52
5 50±2 17
6 22±2 08
5.55*1.05
5.33±2.92
4 89±2.73
4 28±0 88
3,85±0,88
3 26±l.30
3 23±0.20
2 52*0.60
I 76*0 58
1 74±0 20
1 38±0 30
1 20±0.75
1 12±0 36
0 41±0-12
0 63*0.14
(10)
ND
0 52±0.34
(5)
ND
ND
0 16*0 12
(2)
0 30
(1)
0.14*0.09
(i)
0.8I±0.22
(12)
0 18*0 15
(•<)
ND
TR
(2)
1 06±0 67
(S)
ND
ND
TR
«)
0.47
(/>
ND
0 12*0.05
(4)
0 72
(I)
TR
(5)
16 50*4 51
(10)
3 00±2
13
(2)
5.40±1
89
(5)
2.60*0.81
(•«)
2 40*0.81
(4)
32 00*5
83
(S)
5 54*1
02
120)
3 00*2
13
(«)
1.25±0.33
(6)
11 60±2 84
(5)
2.10*0.28
(10)
2.03±l
24
(7)
9.73*1
38
(10)
1 50*0 29
UO)
ND
12 50±4
76
(7)
0 98*0,97
(5)
1 40*0
37
(5)
1.40*0.24
(5)
ND
5 6
8.5
10 6
110
17,2
8.5
4.7
5.4
6,2
9 3
12.7
5.4
6 2
4 8
5 9
5.4
9.1-
4 7
6.5
15 2
110
NOTE: ND = not detected TR = trace
Numbers in parentheses represent number of eggs with residues,
' IDDT residues found in all eggs sampled
eggs of hens which had consumetJ food treated with 10
ppm and 30 ppm DDE. Haegele and Hudson (15) also re-
ported increased mortality of young and reduced clutch
size in ring doves (Slreptopelia risoria) fed 40 ppm DDE.
DDE fed at 10 ppm and 40 ppm to mallards (.Anas
platyrhynchos) reduced hatching of eggs, although survival
of hatchlings to 14 days was unaffected {16).
nificantly lower in eggs of hens that received dieldrin
through the egg. Dieldrin above 1 ppm in the eggs of
golden eagles (AquiUi chrysaetos) may cause reproductive
problems (28), and dieldrin residues of 0.54 ppm are lethal
to brown pelican embryos (7). In view of the great varia-
tion in toxicity of dieldrin to different wildlife species, egg
residues greater than 1 ppm must be viewed as hazardous.
Dieldrin — Dieldrin levels found in the present study are
lower than those reported in several studies investigating
reproductive success and survival of young birds. Fowler
et al. (U) reported normal hatching success of purple gal-
linule {Porphyrula niw-tinica) and common gallinule
{GalUiuda chloropus) eggs containing average dieldrin
residues of 3.8-17.5 ppm. Pheasants (.Phasianus col-
chicus). fed varying amounts of dieldrin. showed no ef-
fects on fertility, hatching, or survival associated with yolk
fresidues of up to 52 ppm (4). Dieldrin residues in whole
eggs would normally average about 26 ppm. Chickens fed
up to 5 ppm dieldrin showed no effects on clutch size,
hatching, or survival of young associated with egg residues
,of 4-5 ppm (14). In contrast, Baxter et al. (5) found
[second-generation effects; fertility and hatching were sig-
PCBs — Laboratory experiments indicate that PCB levels
found in the present study do not reflect acute exposure of
fish-eating birds, but results of reproductive studies are not
so conclusive (17, 26). One important consideration is the
wide range in species sensitivity to PCBs; Heath et al. (17)
found a fourfold difference in sensitivity between two gal-
linaceous species. The complex problems associated with
the wide range of sensitivity to PCBs and the varying
toxicities of different Aroclors were reviewed by Stendell
(27). These differences emphasize the difficulties in
drawing conclusions about the meaning of residues in eggs
of fish-eating birds. But al least five species in this study
have sufficiently high egg levels of PCBs to warrant addi-
tional research; olivaceous cormorant, Caspian tern, Fors-
ter's tern, royal tern, and brown pelican.
Vol. 12, No. I.June 1978
19
Mercury — A pooled sample of 30 while-faced ibis eggs
contained 0.18 ppm wei-weighl mercury, and 10 great blue
heron eggs averaged 0.30 ppm. Fimreite ( // ) reported sig-
nificanlly lowered hatching success in pheasant eggs con-
taining 0.5-1.5 ppm mercury, and Borg et al. (iS) found
similar effects at levels of 1.3-2.0 ppm. However. Heinz
{18) found no significant effects on mallard reproduction
associated with egg residue levels of 1 .0 ppm. Herring gull
iLtinis arficnuitus) chicks hatched from each of 24
clutches that contained mercury between 0.5 ppm and 2.0
ppm (29). Thus it seems unlikely that mercury residues in
white-faced ibis and great blue heron eggs were high
enough to affect reproduction adversely.
White-faced ibis eggs were expected to contain high mer-
cury residues because ibis feed in flooded rice fields where
mercury-based fungicides were used on seed, but levels
were low compared with those found in other studies dS'.
//, /S. 29). Great blue heron feed in various freshwater and
brackish habitats and had slightly but not significantly
greater mercury residues than had ibis. This indicates that
mercury is found throughout the coastal environment, at
least in feeding areas of both species in the Texas rice belt.
THREATENED SPECIES
One objective of the present study was to identify popu-
lations possibly threatened by pesticide contamination.
On the basis of recent population trends, residue levels,
and shell thinning, the authors believe that the brown
pelican, white-faced ibis, reddish egret, laughing gull,
and Forster"s tern warrant immediate attention. Popula-
tions of white pelican, olivaceous cormorant, great blue
heron, and great egret showed weak or undetermined
population trends and should be watched closely in future
years. Results of a Texas brown pelican study were re-
cently published (21) and ibis data are being prepared for
publication.
(3) Anderson. D. W.. J. J. Hickew R W. Risebrough. D. F.
Hughes, and R. E. Chrisiensen. /y6y Significance of
chlorinated hydrocarbon residues to breeding pelicans and
cormorants. Can Field-Nat. 83{2):9I-1 12.
(4) Atkins. T. D.. and R L Under 1967. Effects of dieldrin
on reproduction of penned hen pheasants. J. Wildl. Man-
age. .■(!(4):746-753-
{5) Baxler. W. l... R. L. Under, and R. W. Dahlgren. 1969.
Dieldrin effects on two generations of penned hen pheas-
ants, J Wildl Manage, 33(I);96-I02,
t6) Bius. L J 1970. Measurements of brown pelican
eggshells from Florida and South Carolina, BioScience
20(I5):867~869.
(7) Blus. L. J.. B S. Neely. Jr.. A. A. Belisle. and R M.
Prouty. 1974. Organochlorine residues in brown pelican
eggs; relation to reproductive success. Environ. Pollut.
7:81-91.
(Sj Borg, K.. H Wannlhrop. K. Erne, and E. Hanko. 1969.
Alkyl mercury poisoning in terrestrial Swedish wildlife.
Vellrevy 6(4):301-379.
(9) Childress. R, 1970. Levels of concentration and incidence
of various pesticide residues in Texas. Texas Parks and
Wildlife Dept., 58 pp , Unpublished report.
ilO) Coulter. M. C. and R W. Risebrough. 1973. Shell-
thinning in eggs of the ashy petrel (Oceanodrama homo-
chroa) from the Farallon Islands Condor 75(2);254-255.
(//) Fimreite. N. 1971. Effects of dietary methylmercury on
ring-necked pheasants. Canadian Wildlife Service, 37 pp.
Occasional Paper No 9
(12) Flickinger. E. L . and K ,A King. 1972. Some effects of
aldrin treated rice seed on Gulf Coast wildlife J, Wildl.
Manage, 36(3):706-727,
(13) Fowler. J. F.. L D. Newsome. J. B. Graves. F. L.
Bonner, and P E Schilling. 1971 . Effects of dieldrin on
egg hatchability, chick survival, and eggshell thickness in
purple and common gallinules Bull Environ Contam.
Toxicol, 6(6):495-501
Acknowledgment
The authors thank Robert E. White, Iwao Okuno, Dennis
L. Meeker, and Ronald E. Powers of the Chemical Re-
search and Analytical Section, Denver Wildlife Research
Center, for chemical residue analyses. They express ap-
preciation to Lawrence J. Blus, Eric G. Bolen, James O.
Keith, Lowell C. McEwen, and Donald H. White for
manuscript review.
LITERATURE CITED
(1) Anderson. D W.. and J J Hiikey 1970. Oological data
on egg and breeding characteristics of brown pelicans.
Wilson Bull 82(1)14-28
(2) Anderson. D. W.. and J J. Hickev 1972. Eggshell
changes in certain North American birds. Pages 514-540
in K. H. Voous, ed., Proc XVth Inter Ornithol. Congr.
E J Brill. Leiden, The Netherlands
(14) Graves. J B.. F L Bonner. W F McKnight. A. B
Watts, and E. A. Epps 1969 Residues in eggs, preening
glands, liver, and muscle from feeding dieldrin contami-
nated rice bran to hens and its effect on egg production,
egg hatch, and chick survival. Bull. Environ. Contam.
Toxicol, 4(6):375-383.
(15) Haegele. M. A . and R. E Hudson 1973. DDE effects on
reproduction of ring doves Environ. Pollut. 4:53-57.
(16) Heath. R G . J W. Spann. and J. F Kreitzer. 1969.
Marked DDE impairment of mallard reproduction in con-
trolled studies. Nature 224(52l4):47-48.
(17) Heath. R. G . J W Spann. J F Kreitzer. and C Vance.
1972. Effects of polychlorinaled biphenyls on birds. Pages
475-485 in K. H. Voous, ed., Proc XVth Inter. Ornithol.
Congr. E. J. Brill, Leiden, The Netherlands
tlS) Heinz, G. 1974. Effects of low dietary levels of methyl
mercury on mallard reproduction. Bull Environ Contam.
Toxicol. I l(4):386-392.
20
Pesticides Monitoring Journai
(19) Hickey. J J., and D W. Anderson. 1968. Chlorinated
hydrocarbons and eggshell changes in raptorial and fish-
eating birds. Science 162(3850):271-273-
(20) Keith. J. O.. L A. Woods, and E. G. Hunt. 1970.
Reproductive failure in brown pelicans on the Pacific
Coast. Trans. N. A. Wildl. Nat. Res. Conf. 35:56-64.
(21) King. K. A.. E L Flickinger. and H H Hihiehrand.
1977 . The decline of brown pelicans on the Louisiana and
Texas Gulf Coast. Southwest Nat. 21(4):417-431 .
(22) Longcore, J. R . F B Samson, and T. W. Whitiendale.
Jr. 1971. DDE thins eggshells and lowers reproductive
success of captive black ducks. Bull. Environ. Contam.
Toxicol. 8(2):65-68.
(23) McLane. M. A. R.. and L C Hall. 1972. DDE thins
screech owl eggshells. Bull Environ. Contam Toxicol.
8(2):65-68
(24) Okuno. /., R. A. Wilson, and R. E White. 1972. Determi-
nation of mercury in biological samples by flameless
atomic absorption after combustion and mercury-silver
amalgamation. J Assoc. Off Anal. Chem 55( 1 ):96-IOO.
(25) Peterson. J. E.. K. M. Slahl. and D L. Meeker. 1976.
Simplified extraction and cleanup for determining or-
ganochlorine pesticides in small biological samples. Bull.
Environ Contam. Toxicol. 15(2); 135-139.
(26) Risebrough. R. W.. and D W. Anderson. 1975. Some
effects of DDE and PCB on mallards and their eggs. J.
Wildl. Manage 39(3):508-5l3.
(27) Stendell. R. C. 1975. Summary of recent information
regarding effects of PCBs on birds and mammals Proc.
Nat. Conf. PCBs, U.S. Environmental Protection Agency.
EPA-560/6-75-004, Chicago, IL, pp. 262-267
(2S) Stickel. L. F. 1973. Pesticide residues in birds and mam-
mals. Pages 254-312 in C. A Edwards, ed.. Environ-
mental Pollution by Pesticides, Plenum Press, London and
New York
(29) Vermeer. K 1971 . A survey of mercury residues in aquatic
bird eggs in the Canadian Prairie Provinces. Trans. N. A.
Wildl. Nat. Res. Conf. 36:138-150.
(30) Wiemeyer. S. N.. and R. D. Porter 1970. DDT thins
eggshells of captive American Kestrels. Nature
227(5259):737-738.
Vol. 12. No. I.June 1978
21
Organochlorine Insecticide and Polychlorinated Biphenyl Residues
in Woodcock Wings, 1971-72
M. Anne R. McLane,' Eugene H. Dustman,' Eldon R. Clark,' and Donald L. Hughes ■*
ABSTRACT
Pesticide residues in wings of adult woodcock (Philohela minor)
were used to monitor regional differences in a 1970-71 survey
of DDT. DDE. TDE. dieldrin. mirex, and PCBs in Maine. New
Hampshire . New York, New Jersey. Pennsylvania. North
Carolina. South Carolina, Georgia, Lousiana. Michigan, and
Wisconsin. In 1971-72, wings were sampled again to compare
levels of organochlorine insecticide residues with those of the
previous survey and to delineate differences in residue values
between adult and immaiure woodcock. Three additional states.
Massachusetts. Minnesota, and Vermont, and one additional
organochlorine insecticide, heptuchlor epoxide, were included
in the second survey .
Residue levels in the 197 1 -72 wings showed the same pattern as
thai observed in 1970-71: organochlorine insecticide residues
were highest in wings collected in the southern states and in
New Jersey; residues were lowest in samplings taken in the
northern and midwestern stales Residues of DDT. TDE, and
dieldrin in the 1971-72 wings were slightly lower than those
found in 1970-71 . DDE. PCB. and mirex residues were signifi-
cantly lower (P<0.05. P<O.OI. and P<0.01. respectively) in
1971-72. Wings of immature woodcock in Louisiana had sig-
nificantly lower (P <0.05) mirex residues than did adult wings.
Introduction
The woodcock is well suited for monitoring environmental
pollutants because it is a migratory upland game bird dis-
tributed throughout the eastern United States from the Mis-
sissippi River to the Atlantic Ocean and from Michigan to
Florida. Personnel from the Fish and Wildlife Service,
U.S. Department of the Interior, monitor reproductive suc-
cess of woodcock by annually inspecting wings submitted
' Filh tnd Wildlife Service. US DepinmenI of (he Interior. Pacuxeni Wildlife
Resetrch Center. Laurel. MD 20III
' Route 2. Boi 170. Eveteii. PA 15537
> 22 Hunion St . Calais. ME (M6I9
* WARF Institute, Inc. (now Raltech Scientific Services. Inc }, Madison. Wl
53701
by cooperating hunters. Thus wings are in ample quantity
tor other studies. The same wings can be used to assess
quantities of pollutants which the birds have acquired,
largely from their food. The woodcock occurs near or at
the top of a terrestrial food chain and subsists on animal
material, primarily earthworms (7, 10). Earthworms con-
centrate an array of persistent environmental pollutants in
their tissues and are important in the diets of a number of
avian species (2, 3. 4. 5. 6).
Woodcock wings were first monitored for environmental
pollutants in 1970-71. Regional differences were clearly
demonstrated and baseline measurements were obtained for
later comparisons (8). An expanded sampling of wings was
undertaken in 1971-72 to compare residues with those
found in 1970-71, and to determine whether residues in
the wings of adult and immature woodcock differed. This
paper reports the findings of the 1971-72 survey .
Methods
Wings were collected in 15 states: Connecticut, Georgia,
Louisiana, Maine, Massachusetts, Michigan, Minnesota,
New Hampshire. New Jersey, New York. North Carolina,
Pennsylvania, South Carolina, Vermont, and Wisconsin.
These states provided a suitable geographic distribution
and offered the best chance for collecting adequate num-
bers of wings. Because wings from North Carolina. South
Carolina, and Georgia were too few to provide a sample
from each state, the wings from these states were combined
into one tri-state area sample. Wings from adult and im-
mature woodcock from each state and from the tri-state
area were sorted into groups of 25. Five of these groups
from each state and five from the tri-state area were
randomly selected for analysis.
Wings were plucked and the distal joint was removed. The
part remaining was ground in a hand grinder and
22
Pesticides Monitoring Journai
homogenized with the group of 25 which made up the
complete sample. A 20-g aliquot was taken for analysis.
Organochlorine pesticides and polychlorinated biphenyls
(PCBs) were determined at WARF Institute, Inc.. Madi-
son, Wisconsin, by the following procedures:
The 20-g aliquot was dried at 40° C for 96-120 hours, and
then ground with sodium sulfate and extracted for 8 hours
on a Soxhlet extractor with 105 ml of ethyl ether and 250
ml of petroleum ether. The extract was concentrated on a
steam bath and diluted to 50 ml with petroleum ether. A
10-ml aliquot of the extract was cleaned and separated into
two fractions by elulion through a Florisil column with
mixtures of ethyl ether and petroleum ether (5-1-95 and
15 -(-85). An aliquot of the final elation was passed through
a standardized silicic acid column as described by Armour
and Burke (J).
Temperatures:
Carrier gas:
Chromatograph:
Column:
Temperatures:
Carrier gas:
injector 225° C
column 205° C
detector 245° C
purified nitrogen fllowing at
80 ml/minute
Barber-Coleman Model 500U
4-ft X 4-mm glass, packed
with 3 percent OV-17 on
100-120-mesh Gas-Chrom Q
injector 215° C
column 200° C
detector 250° C
purified nitrogen flowing at 80
ml/minute
The sensitivity level of this method was 0.05 ppm or-
ganochlorine pesticide and 0.10 ppm PCBs on a lipid
basis. Recovery for organochlorine pesticides ranged be-
tween 80 and 95 percent, and PCB recoveries ranged be-
tween 75 and 85 percent. None of the residue data has been
adjusted for rates of recovery.
The pesticides and PCBs were determined by electron-
capture gas chromatography under the following condi-
tions:
Chromatograph:
Column:
Barber-Coleman Model 5360
Pesticide Analyzer
4-ft X 3-mm glass, packed
with 5 percent DC-200 on
80- 100- mesh Gas-Chrom Q
Results and Discussion
Table 1 shows the ranges and the means as ppm lipid
weight for DDT, DDE, TDE, PCBs, dieldrin, mirex, and
heptachlor epoxide residues in adult woodcock wings from
12 states and the tri-state area arranged in approximate
geographic order from south to north. DDT and its
State
TABLE 1 . Ranges and geometric means of organochlorine insecticide residues in adult woodcock wings
from 15 easternlmidweslern states. 1971-72
REStDUES, PPM Lipid Weight
Heptachlor
DDT DDE TDE PCB DtELDRtN MiREX Epoxide
Louisiana
Tri-slate area
New Jersey
Pennsylvania
Connecticut
New York
Massachusetts
New Hampshire
Vermont
Maine
Michigan
Wisconsin
Minnesota
1.88-5 45
2 74
2.35-11 12
5 90
3,27-8,20
4 90
0 29-1 37
0 60
1 28-5 61
2 36
0,29-2,87
1 12
0,51-5 41
2 16
0,68-8,47
1 92
0,25-0 67
1,36
0.36-0 94
0,77
0.24-0 68
0,50
ND-0 18
0,10
0 16-0.47
0 30
5 74-13,09
9 20
6 99-27,00
18 69
10 11-25 80
16 96
2,11-4,71
3 59
3,38-7.12
6 23
4 16-13 07
6 32
8,28-22 65
15,63
5 96-11 56
8 47
2 63-3 57
3,33
3.24-7,20
5 13
2 28-6 96
3 53
2,60-4 23
3 15
1 12-3 34
1,74
0 52-1 40
0 91
0 64-2 02
1 42
0 76-2,34
1 25
ND-0 17
0,03
0 16-0,65
0 35
0,14-0 26
0 19
0 11-073
0 33
ND-0 47
0,31
0 07-0 13
0,12
0 06-0 25
0,18
0 06-0 32
0,18
1 65-4 10
2.21
2,63-4 22
3,24
1.97-4,04
2,92
0 94-2 07
1 39
1 52-4.38
2 66
1,37-1,84
1 60
4 03-9,58
5 84
1 44-1,90
1 69
1,54-2 02
1.75
0 96-1 26
1 12
1 02-2 21
1 39
0,46-1,22
0.77
ND-0 48
0 08
1.27-5 56
1.90
1,22-4 04
1 88
0 27-0 77
0 43
0,12-2.99
0 30
0 12-1.12
0,36
0,15-0.21
0.18
0.05-0,91
0 15
0.14-0.59
0 27
0,08-0 II
0,09
0,06-0,12
0,08
0 07-0,11
0 09
0,09-0,82
0,18
0.05-0,06
0,05
4,70-8,49
5 20
I 66-5 27
3 14
ND-2 12
0 58
0,24-0 78
0 48
ND-0, 38
0,50
0 28-0,96
0,54
ND-0, 91
0 24
ND-0 92
0.45
0,24-1.25
0,54
0.34-1 44
0,87
0.59-5 01
1,34
ND-1 78
0 85
ND-0. 74
0,21
0,52-1 13
0 70
0 21-1 48
0 58
ND
ND
ND
ND
ND
NOTE Tn-state area = North Carolina, South Carolina, and Georgii
ND = not detected.
Vol. 12, No. 1, June 1978
. Wings from three slates were combined because not enough were available from any one state
23
metabolites are distributed in a similar pattern: geometric
means of DDT and its metabolites were highest in the tri-
state area (DDT. 5 90 ppm; DDb, 18.69 ppm; TDE, 1.42
ppm) and second highest in New Jersey (DDT, 4.90 ppm;
DDE. 16.96 ppm; TDE. 1.25 ppm). Differences in con-
taminant residues levels were determined by one-way anal-
ysis of variance with Duncan's multiple range test. Aver-
age TDE residues in woodcock wings from the tri-state
area and New Jersey were significantly higher {P<0.01)
for the tri-state area than for all other states except New
Jersey. Massachusetts, and Louisiana. The average level of
DDE was significantly lower (/'<0.01) for Minnesota than
for all other states.
The average PCB residue in woodcock wings (5.84 ppm)
was significantly higher (P<0.01) for Massachusetts than
for all other states: PCBs in wings were higher (P<0.01)
for the tri-state area than for all other states except New
Jersey, Connecticut, and Louisiana. The average PCB level
was significantly lower (P<0.01) in Minnesota than in all
other states.
Average dieldrin residues in wings from Louisiana and the
tri-state area (1.90 ppm and 1.88 ppm, respectively) were
significantly higher than those in all other states. Min-
nesota had the lowest average residues (0.05 ppm).
Heptachlor epoxide residues were found in adult wings in
only two areas: Louisiana and the tri-state area. These two
areas were included in the fire ant {Solenopsis saevissima)
eradication program which used heptachlor in the 1950s.
Mirex was substituted for heptachlor in the early 1960s.
Heptachlor epoxide residues found in adult wings from
Louisiana ranged from 0.52 to 1.13 ppm: the geometric
mean was 0.70 ppm. Residues in adult wings from the
tri-state area ranged from 0.21 to 1.48 ppm: the geometric
mean was 0.58 ppm.
Woodcock wings from the two southern areas, Louisiana
and the tri-state area, had consistently higher or-
ganochlorine residues other than PCBs. PCB residues were
highest in Massachusetts and second highest in the south-
ern areas. Wings from Minnesota had the lowest or-
ganochlorine residues except for DDT. Wisconsin had the
lowest DDT residues: Minnesota had the second lowest.
Eleven of the 13 states, including those in the tri-state
area, were sampled in both 1970-71 and 1971-72 (Table
2). Generally, residues were lower in the second sampling
period. DDE, mirex, and PCB residues were significantly
lower in 1971-72 than in 1970-71 (P<0.05, P<0.01,
and P<0.01, respectively).
The relationship of residue levels among states for the two
years was tested by a two-way analysis of variance (Table
3). Residues in both sampling periods were consistently
highest in the southern states and in New Jersey. Residues
were lowest in the northern and midwestern states.
Table 4 shows ranges and geometric means of or-
ganochlorine insecticide residues found in immature wood-
cock wings. Immature wing residues follow the same pat-
tern as residues in adult wings in all but three instances.
Mirex residues were higher in immature wings from the
tri-state area than in immature wings from Louisiana. Av-
erage PCB residues in immature wings were lowest in New
Jersey, Louisiana, and the tri-state area: this is the opposite
order of residues in adult wings. Heptachlor epoxide resi-
dues were found in adult and immature wings from
Louisiana and the tri-state area: heptachlor epoxide was
also found in two pools of immature woodcock wings from
New Jersey.
TABLE 2. Geometric means of organochlorinaled insecticide
residues in woodcock wings from easternlmidweslern states,
1970-71 and 1971-72
GeoM- Mean
PPM
Lipid
Weight
Residue
1970-71
1971-72
DDT
1.48
1.26
DDE '
8.79
6 82
TDE
1.41
1 42
Dieldrin
0.31
131
Mirex '
1.54
1 09
PCB =
5.58
1.64
NOTE; See Table 3 for list of slates sampled.
'Significani al/'<0 05
'■ Significani al P <0 01
TABLE 3. Comparison of organochlorine insecticide residues in adull woodcock wings, 1970-71 and 1971-72
State
Geoim. Mean of Residues, ppm Lipid Weight
DDE
DDT
TDE
PCB
[)lELDiUN
Mirex
4 7ld
078de
0 19c
2 18c
008b
1.04c
7 58cd
1 6lcd
0 25c
3 08bc
0 19b
063c
5 92cd
0.77de
0 15c
3 27b
0 19b
1 04c
4 07d
0 70de
0 lie
2 51bc
0 17b
046c
16 01«b
5.15ab
081b
4 16a
0 53ab
0 63c
28 56a
9 19a
2.27a
5 24a
2.25a
3 lib
1083bc
2 33bc
066b
3 36b
I98>
1025a
4.65d
0.63e
0.16c
2 43bc
0.15b
1.39c
5.05d
033e
0.51c
2.14c
O.lSb
I.Otc
Maine
New Hampshire
New York
Penrnylvania
New Jertey
Tnsiatc area '
Louisiana
Michigan
Wiiconsin
NOTE. VaJue^ with the \8me letter are not significantly difTercni
' Sec Table 1 for cxplanatiDn
24
Pesticides Monitoring Journ.'M
TABLE 4. Ranges ami geometric means of organochlorine insecticide residues in immature woodcock wings from seven
easternlmidwestern states. ]97l~72
Residues, ppm Lipid Weight
Maine
Michigan
New Jersey
Tri-stale area '
NOTE: ND = nol detected
'See Table 1 for explanation
Heptachlor
DDT
DDE
TDE
PCB
DiELDRIN
MiREX
Epoxide
0 51-2.28
2 56-5 28
0 16-0 41
0.75-1.07
0 06-0.83
ND
ND
1 19
4.07
0.25
0 89
0 16
—
—
0 46-4.33
1 90-9.77
0 12-2.04
0 95-1 52
0 07-0.35
ND
ND
0 92
3 16
0 23
1 18
0 20
—
-
3 10-27 04
9 40-18,01
0 46-2 84
1 93-4 28
0 61 -1 07
ND
ND-0,42
6 41
13 64
1 11
2.55
0 88
-
0 13
2 89-18 10
15 29-47 47
0 64-4.09
ND-3 93
0 76-2 70
1 80-3 98
0 26-1 23
6 82
26.03
1 46
2.04
1 64
2 87
0 51
1.93-4 01
7 42-12 53
0 46-0.95
1.27-3.68
1.32-10.20
1 43-3 72
0 45-0.96
2.97
9 80
0.72
2.23
2.46
2 48
0.69
Mirex levels in wings of adult and immature woodcock
from Louisiana are clearly different; the residues in wings
from adults were significantly higher t,P<0.Q5). Mirex
residues in adult wings ranged from 4.70 to 8.49 ppm: the
geometric mean was 6.20 ppm. In immature wings, mirex
residues ranged from 1.43 to 3.72 ppm; the geometric
mean was 2.48 ppm. Mirex residue levels from all other
states were very low. No significant difference in residue
levels were found between adult and immature woodcock
in other states, nor among other organochlorine insec-
ticides.
The authors conclude that woodcock wings can be used to
help determine the levels and trends of a variety of en-
vironmental pollutants in the eastern United States.
Periodic assessment of residues in the wings of this species
will provide important monitoring information at nominal
cost.
LITERATURE CITED
(I) Armour. J. A., and J. A. Burke. 1970. Method for separating
polychlorinated biphenyls from DDT and its analogs. J.
Assoc. Off. Anal. Chem'. 5.1(4);761-768.
(2) Barker. R. J. 1958. Notes on some ecological effects of
DDT sprayed on elms. J. Wildl. Manage. 22(3):269-274.
(3) Boxkins, E A. 1966. DDT residues in the food chains of
birds. Ati. Nat. 21(l):l8-25.
(4) Gish. C D. 1970. Organochlorine insecticide residues in
soils and soil invertebrates from agricultural lands. Pestic.
Monit. J. 3(4):24I-252.
(5) Korschgeii. L. J. 1967. Soil-food chain-peslicide wildlife
relationships. Missouri Pesticide Studies, Federal Aid Proj-
ect 13-R-21. Missouri Department of Conservation. Jeffer-
son City, MO
(6) Krohn. W. B. 1970. Woodcock feeding habits as related to
summer field usage in central Maine. J. Wildl. Manage.
34(4);769-775.
(7) McLane. M.A.R.. L. F. Slicket. E. R. Clark, ami D. O.
Hughes. 1973. Organochlorine residues in woodcock wings.
1 1 states— 1970-71. Pestic. Monit. J. 7(2);IOO-103.
{8} Sheldon, W . G 1967 . The book of American woodcock.
University of Massachusetts Press, Amherst, MA, p. 227.
Vol. 12, No. 1, June 1978
25
Chlorinated Hydrocarbons and Mercury in Birds of Lake P'dij'dnne, Finland — 1972-74^
Jukka Sarkka,- Marja-Liisa Hattula,^ Jorma Janatuinen.- Jaakko Paasiviria,' and Rislo Palokangas-
ABSTRACT
The levels of mercury, PCBs, DDT and its analogs, lindane,
and dieldrin were examined in aquatic birds nesting on the
shores of Lake P'aifanne, the second largest lake in Finland,
which is polluted hy a wood-processing industry and urban
sewages. The primary food of the 10 species examined was fish.
In muscle of about 350 individuals, the highest average residues
were PCBs: in livers, mercury was the highest Lindane was
found in some individuals: dieldrin appeared in none. The
differences among levels in 1972, 1973, and 1974 were not
significant. Some regional differences were found, particularly
for mercury. Some PCB contamination was observed near the
town of Jyvaskyla. DDT was distributed evenly. A stronger
correlation existed between residues of PCBs and DDT than
between residues of any other compounds . In some gulls, males
had higher average residues than had females. The DDT:PCB
ratio generally corresponded to that of the North Atlantic
Ocean, hut the difference among species was great. Higher
mercury. PCB, and DDT values existed in adults than in
juveniles: higher mercury values existed in livers than in mus-
cles. Black-throated divers had highest mercury residues: in
herring gulls. PCBs and DDT were highest. The levels gener-
ally correspond to those found in other studies.
Introduction
Authors undertook the present study to discover the levels
of chlorinated hydrocarbons and mercury in the aquatic
birds of Lake P'aij'anne, Finland. Simultaneously, the
methods of chemical analysis and the chemical structures
of the compounds were developed. Data on the birds were
collected by the University of Jyvaskyla as part of a
monitoring study of the chlorinated hydrocarbons and mer-
cury in the food webs of Lake Faij'anne, in which residues
were analyzed in the higher aquatic plants, plankton, bot-
tom fauna, sediment, fishes, and aquatic birds.
Adults and juvenile birds were analyzed separately.
Juveniles were birds of the same summer, ranging in age
from a few days to several weeks. Muscle and liver tissues
were analyzed separately.
Concentrations of different residues were analyzed ac-
cording to age, location on the lake, and species. Attention
was also paid to the differences between and ratios of
residues in liver and muscle, and to the correlations of
different residues to muscle:liver ratios, differences of
residue load between the sexes, and the 1DDT:PCB ratios.
The significances of the differences were statistically
tested.
Sampling and Collection
Lake Faij'anne. the second largest lake of Finland (1100
km-), has been the object of limnological investigations
since 1968 (32). It receives waste principally from the
three origins shown in Figure 1. The sulphite and sulphate
pulp mill wastes of A'anekoski come from the north in the
upper part of the watercourse, approximately 40 km up-
stream from Lake Faij'anne. Wastes are also discharged
into the northern part of the lake from the town of Jyv'as-
kyl'a via Lake Jyv'asjarvi (station 1); these effluents contain
urban sewages and paper mill wastes. The third source of
wastes is in the center of the lake near station 4, which
receives effluents from a sulphite pulp mill and two paper
mills of Jamsa, as well as a minor amount of domestic
waste. At the northern end of the lake, the content of
human sewages is greater than in the center which is
contaminated almost exclusively by the wood-processing
industry. When flowing from the north to the center (sta-
tion 3), the water becomes cleaner. Water extending from
the central part of the lake (station 4) to the southern part
(station 6) is quite clean.
Study supported by a grant from the Academy of Finland. Helsinki
' Dcpanment of Biology, University of Jyvaskyri, SI-40I0U Jyvaskyfa 10. Finland
' Oepinmenl of Chctnislry. University of Jyvaskyla. SF-40100 Jyvaskyla 10.
Finland.
The main sampling sites of the study were stations 1, 4, 5,
and 6. From stations 2 and 3, a few birds were obtained for
supplementary study. Station I is polluted by domestic
26
Pesticides MoNiroRiNc Journal
AANEKOSKI
Pulp mills
Paper
mill Mai n inflow
JTVASKYLA,/
Town JP ^ M
1 " O SampI in g
Stat ions
^ Inflows
FIGURE 1. Lake Paijdnne with sampling stations.
birds were conserved by freezing in plastic bags which did
not contain PCBs.
Species analyzed were black-throated diver {Gavia arclica
L), great crested grebe (Podiceps cristatus L.), goldeneye
(BucephaUi clangula L.), redbreasted merganser ( Mergus
serrator L.), sandpiper (Tringa hypoleucos L), lesser
black-backed gull (Larns fuscus L.), herring gull (Larus
argentatus L.), common gull (Larus canus L.), black-
headed gull (Larus ridibundus L), and common tern
(Sterna hirundo L.).
Species were chosen to represent aquatic birds, especially
those which feed at Lake Paijanne in the summer. This is
why such species as mallard (Anus platyrhynchos) and
other common game birds were not sampled. All species,
however, are migratory, spending only about one third of
the year in Finland.
The number of birds analyzed for total mercury was 344;
for methyl .nercury, 32; and for chlorinated hydrocarbons,
301.
Analytical Procedures
CHLORINATED HYDROCARBONS
The frozen sample was thawed and 5-10 g breast muscle or
liver was weighed. The sample was ground in a mortar
with acid-washed sand (Merck) and anhydrous sodium
sulphate, 4 g of the latter for each gram of wet tissue. The
homogenized mixture was transferred to a glass container
and dried at room temperature for 48 hours.
The extraction was performed by Soxhiet in thimbles
which had been washed ultrasonically in a 1:1 mixture of
acetone and diethyl alcohol. The homogenate was trans-
ferred to the thimble and extracted for 6 hours in a mixture
of diethyl ether, petroleum ether (boiling point 40°-60°
C), n-hexane, and acetone in quantities of 1:9:2, 5:5, 5
(v/v). All solvents were pesticide analytical (pa.) grade
and redistilled. This solvent system has been statistically
proved to be the most effective for extracting animal tissue
{14).
sewages and paper mill effluents. Until 1968, effluents
from the paper mills and the Aanekoski pulp mills con-
tained mercury originating from slime-preventing chemi-
cals (12). Water at stations 2 and 3 gradually becomes
cleaner as it moves south. Water at station 4 is affected by
a wood-processing industry whose effluents contained
mercury until 1968. Water at station 5 becomes cleaner as
it approaches station 6, which is almost limnologically
pure (28).
Adult birds were collected by shooting and young birds
were caught live. No individuals were found dead. The
adults were all caught after eggs had been laid. The whole
The extracted fat was weighed and cleaned by the follow-
ing methods: shaking with concentrated sulphuric acid (2),
thin-layer chromatography (75), and a column chromatog-
raphic method (16). In routine analyses, if extracted fat
exceeded 20 mg, it was made into a I percent solution in
n-hexane and divided into halves. One half was shaken
with concentrated sulphuric acid for determining total
PCBs, lindane, and DDE. The residues were extracted in
hexane which was ready for gas chromatography. The
hexane was shaken again with chromic acid for determin-
ing DDE (35). The second half was applied on a thin-layer
plate for determining TDE, DDT, dieldrin, and endrin.
When extracted fat was 10 mg or less, thin-layer
Vol. 12, No. I.June 1978
27
chromatography was the only cleanup method used. The
column chromatographic method was used mainly for
analyzing bird material because residues were greater than
in the rest of the samples and required dilution from 10 mg
fat. which is the maximum amount accommodated by the
column, (0 10 ml fat for proper gas chromatography. The
cleanup methods have been tested to determine the highest
values of the chlorinated hydrocarbons per fresh weight of
tissue ( /5). The highest value of PCBs is the only recovery
criterion available at present. The sulphuric acid cleanup
produced a statisfactory measurement of PCBs in a fat
reference sample of the Organization for Economic Coop-
eration and Development (OECD).
The equipment used in determining the residues was a
Varian Model 600 D gas chromatograph with an H'
electron-capture detector. The length of the glass column
was 1.5 m and the inside diameter was 1.5 mm. In the
routine analyses the column filling was a mixture of 65
parts of 8 percent QF-I and 35 parts of 4 percent SF-96 on
Chromosorb W 100-120 mesh. Occasionally SF-96 on
Chromosorb W 100-120 mesh was also used for control
purposes. The carrier gas was nitrogen (99.999 percent).
The column temperature was 180° C, the detector and
injector were 190° and 225° C. respectively.
The following pesticide standards, all 100 percent pure.
were used: aldrin. p.p'-TDE, p,p'-DDE, p,p'-DDT,
o.p'-DDT, dieldrin, endrin, and lindane. The PCB stand-
ard was Clophen A 60 by Bayer because the PCB contami-
nation in Finland had been statistically tested and proved to
be that type (13). The final concentration in chromato-
graphing was 10 ng/ml for pesticides and 100 ng/ml for the
PCBs. The calculation was carried out as described by
Gaul (10) and the PCBs were calculated by summing nine
peaks (total 13 peaks) which did not interfere with the
pesticides. Injection of 50 pg pesticides or 500 pg PCBs
produced peak heights of approximately 50 percent of
full-scale deflection.
TOTAL MERCURY
Total mercury was determined by cold vapor atomic ab-
sorption using a Coleman MAS-50 mercury analyzer. A
sample of 0.5-1 g was homogenized in an Erienmeyer flask
with 0.5 ml water, and 10 ml concentrated sulphuric acid
was added while the flask was kepi in an ice bath. The
flask was then covered with plastic film and kept in a 60°
C water bath for 4 hours. After cooling. 15 ml 6 percent
solution of KMnOj was added from a buret, the bottle was
kept in an ice bath and shaken well, and the sample was
diluted to 100 ml. To reduce mercury II ions to mercury
metal. 2 ml 20 percent hydroxylamine hydrochloride and I
ml stannous chloride (40 percent solution in 5 percent
sulphuric acid) were added and the measurement was taken
immediately. The standard was HgCI^ and a standard curve
was made daily after treating the standard as described
above.
METHYL MERCURY
Methyl mercury was identifieil by gas chromatography
using the following conditions:
Chromatograph: Varian Aerograph 2400
Deleclor: H ^ Irilium
Column glass. 18 in long and 6 mm ID. packed with 10 pcrcenfCar-
bowax 20M on Chromosorb W 80-100 mesh
Temperatures: column: 140° C
injector: 180° C
detector: 210° C
in a Sorvall Omniinixer. 1-5 g material was homogenized
in 26 ml 29 percent KBr. Then 3.5 ml 47 percent HBr that
had been prewashed with benzene was added to the
homogenate which was then centrifuged and the liquid was
decanted. The homogenate was treated again with KBr and
HBr. The liquid phases were combined in a 250-mI
separatory funnel and 50 ml redistilled benzene was added.
Methylmercury bromide was added to the benzene. The
water phase was extracted again with 25 ml benzene and
the extracts were combined; then 8 ml 20 percent cysteine
acetate (dried with Na2S04) was added and the solution
was shaken to bind the methylmercury bromide to cysteine.
Five ml of the water phase was shaken with 1 ml 47
percent HBr and 10 ml benzene to extract the methylmer-
cury bromide in benzene. The benzene phase was
chromatographed and the peak heights of the sample and
the standard were calculated. Injection of 50 ^g Hg as
methylinercury bromide produced a peak height of full-
scale deflection.
Results
Table 1 shows the average levels of the residues studied in
muscles and livers of both adult and juvenile birds. Differ-
ences among species, areas, and years are not considered
in this table. The table shows that in muscles, the residues
of highest concentration are PCBs; in the livers, mercury
appears at the highest levels. Concentrations of TDE and
DDT are very small compared with those of DDE; all three
are combined in subsequent tables as SDDT. Lindane was
present in only a few individuals, accounting for minute
TABLE 1. Average chlorinated hydrocarbon and mercury con-
cenrralion.s In muscles and livers of aquatic birds.
Lake Paijanne. Finland — 1972-74
Average
CONCENIRAriON
mo/kg Wet
Weight
MUSCI ES
Livers
Compound
Adui TS
Juveniles
Adui ts
Juveniles
Total Hg
2.729
0.777
7.900
2,312
Methyl Hg
2 697
0.275
—
—
PCB
4 970
1 135
5 734
0,961
DDE
J .173
0 708
4 187
0,821
TDE
0.012
0 000
0,015
0,000
DDT
0.002
0,000
0,007
0,000
SDDT
3 387
0.708
4,209
0,821
Lindane
0 002
0 001
0 000
0 000
Dieldrin
0 000
0 000
0 000
0,000
28
Pesticides Monitoring Journal
residue averages. Dieldrin was not present in any indi-
vidual at concentrations above 0.0005 mg/kg wet weight.
The material of each year of study consists of different
numbers of samples from different sampling areas, so
results for the different years were not compared with
parametric statistical tests. The yearly differences of the
average concentrations of total Hg, PCBs, and SDDT were
examined separately in different bird species for the mus-
cles and livers of the adults and juveniles, using non-
parametric Friedman two-way analysis of variance or Wil-
coxon matched-pair signed-rank tests {29). No significant
differences among the years were observed.
Tables 2-5 present the corresponding residues in birds at
different areas of the lake. Because residues vary broadly
TABLE 2. Average concentrations of total Hg, PCBs. and XDDT in muscles of adult birds. Lake Pdifdnne. Finland
Stody are* 1 Am* 2 A«ea 3 Aie* 4 A«e* 5 Ama 6
Species Statistic Ho PCB ZDDT Hg PCB iDt)T Ho PCB SDDT Ho PCS SDDT Ho PCB IDDT Ho PCB TDUl
Residues, mg/kg wet weighl
Black-lhroaled diver M — — — _________ |2 80 3,53 5 66 14,57 181 6.81
SD 0,00 2,88 2 59 0,00 0,37 4.34
N 13 3 13 3
Greal crested grebe M 2 88 3 99 3 74 — — — — — — 178 133 3 54 ______
SD 1 13 3 11 2 76 0,80 1 02 3 11
N 8 8 8 4 4 4
Goldeneye M — — — ______ o 24 0 22 0 14 — — — — — —
SD 0,06 0 17 0,03
N 4 3 3
Merganser M ___ _ ________ 5,48 2,16 1,28 5 42 185 3 22
SD 0.00 0.00 0.00 141 141 4 36
N 1113 3 3
Sandpiper M ____________ o,31 0,28 0,71 0,63 3.30 5.41
SD 0.00 0.00 0.00 0.00 000 000
N 1 I 1 1 1 I
Black-backed gull M 3.00 7.97 1 II 3 44 14 32 5 87 2 43 _ _ 2 74 3 64 5 22 3 27 7 15 7 02 3,66 5 10 6 60
SD 0.00 0,00 0 00 124 4.72 193 0,60 _ — 158 3 09 3 79 106 4 91 3 54 1,29 3 29 4.46
N 1115 5 5 3 9 9 9 17 17 17 15 12 12
Hemnggull M 0 10 6 69 I 79 _ _ _ _ _ _ 4,00 19 54 20,38 2,80 20 49 6 90 2 97 8,46 6 89
SD 000 0.00 0,00 125 2 06 2,36 1 10 12 31 5 10 192 5 33 3,92
Nlll 222555 12 88
Commongull M 2 64 8,98 5.88 2,05 7 16 2 61 3 16 1177 14 29 2 03 4 04 2 41 2 01 3 33 2.58 1,70 3 18 2 40
SD 0 00 0,00 000 0,15 3 15 2 86 0,00 0,00 0 00 I 15 4 54 2,18 148 2 57 2 41 1,01 3 26 184
N 1 1 15 5 5 1 1 1 20 20 20 14 14 14 16 16 16
Black-headed gull M 178 4 67 1 58 2 73 4 89 0 87 _ _ _ 0 96 2 28 0,69 1 17 2 60 0 48 _ _ _
SD 088 4 17 3 38 1,55 2 53 0,32 0 54 5 84 1,07 0 35 0 14 0,13
N 17 16 16 4 4 4 18 18 18 2 2 2
Common teiT. M 3 01 6,18 2,36 2,68 4,53 0.66 5,94 _ _ 3 48 2 91 137 4 38 2.92 1,32 5,08 4 27 1.53
SD 1,60 4,38 5,18 2,19 3,03 0 29 0,51 2,28 1,92 150 132 1,52 0,94 1,61 3 92 156
N 13 12 12 5 5 5 2 16 16 16 7 6 6 7 6 6
NOTE: See Figure 1 for location of study areas,
M = mean. SD = standard deviation. N = number of observations.
TABLE 3. Average concentrations of total Hg, PCBs, and ^DDT in muscles of juvenile birds. Lake Pdifdnne, Finland
Study Area 1 Area 2 Area 4 Area 5 Area 6
SPEOES Statistic Hg PCB IDDT Ho PCB IDDT Ho PCB XDDT Ho PCB XDDT Ho PCB XDDT
Residues, mg/kg wet weight
Black-throated diver M ____________ 8.15 — —
SD 0.00
N 1
Great creasted grebe M 0 53 1,25 0 30 _ _ _ 0.38 0 19 0,11 _ _ _ _ _ _
SD 0 19 0.81 0 15 0 12 0 15 0 04
N 6 3 3 3 2 2
Goldeneye M ______ 0,07 _ _ 024 015 0 16 _ _ —
SD 0,00 0,00 0 00 000
N 1111
Merganser M ____________1.32 0.18 0.78
SD 0,48 0,00 0,00
N 4 11
Black-backed gull M 198 7 70 4,39 0,87 4,06 0,82 _ _ _ 0,92 I 10 0 51 0 69 2.28 5,00
SD 0 00 0,00 0,00 0,00 0 00 0 00 0,23 1 14 0 44 0,41 2,30 5.31
N llllll 733433
Hemnggull M 0.04 0.67 0.36 _ _ _ 0.94 5 44 2,57 0,79 2,97 0,96 0,64 2,85 1,52
SD 0.00 0,00 0,00 0,00 6,86 3,25 0,00 0,00 0,00 041 2,47 0,84
N 111 222111 11 33
Commongull M 145 103 0 40 _ _ _ 0 76 0 33 0 13 1,00 0 43 0,51 0,85 1,32 0,59
SD 000 000 0,00 032 0,00 0,00 0,39 0,51 1,08 0.20 1,90 0,79
N 111 3 1 1 13 12 12 6 4 4
Black headed gull M 0,45 0,52 0,10 _ _ _ 0,35 0.36 0,15 ______
SD 0 28 0,33 0,05 0,32 0 37 Oil
N 9 8 8 11 11 II
Common tern M 0,50 0.95 0 16 _ _ _ 1.12 1.06 0 67 0.34 1.00 0.41 0,45 0,68 0.25
SD 0.09 0,22 0.04 0,65 0 59 0 62 0.07 0,35 0 12 0,02 0.00 0,00
N 544 444333222
NOTE, See Figure 1 for location of study areas,
M = mean. SD = standard deviation. N = number of observations.
Vol. 12, No. 1, June 1978
29
TABLE 4. Average concentrations of total Hg, PCBs, and IDDT in livers of adult birds, Lake P'aifanne, Finland
Study aipa I Area 2 Akea 3 Aaea 4 Area S Area 6
Sncm
Statistic He PCB ZDDT Ho PCB SDDT Ho PCB SDDT Ho PCB ZDDT He PCB XDDT Ho PCB ZDDT
BUck-throalcd diver
M
SD
N
Great crusted grebe
M
SD
N
Goldeneye
M
SD
N
Merganser
M
SD
N
Sandpiper
M
SD
N
Black-backed gull
M
SD
N
Hemng gull
M
SO
N
Common gull
M
SD
N
Black-headed gull
M
SD
N
Common tern
M
SD
N
Residues, mg/kg wet weight
— — — — — — — — — — — — 4380 3 79 — 82 33 6.10 24.91
000 000 000 0.00 000 0.00
1 I I I II
562 6.37 5 23 —— — — — — 60] 282 8,71 _ — — — __
2 19 3.99 4.03 2 90 185 7 59
8 8 8 4 4 4
— — — — — — — — — 2 19 0.30 0 12 200 0 35 0 13 — — —
132 0.05 0.04 0 00 0 00 0 00
4 3 3 111
— — — — — — — — — — — — 24.00 2 16 128 22 97 180 3.78
0.00 OOO OOO 854 0.39 1.93
I I I 3 3 3
— — — — — — — — — — — — 0 38 0 16 0.44 123 0 44 0 25
000 OOO 0.00 0.00 000 0.00
1 I I I I I
7 20 683 3 19 8 74 1997 1640 8 42 4 60 4 97 7 98 9.39 9.33 9.74 5.91 8.54 10.62 3.72 7.82
000 OOO 000 209 16 28 10.99 0 78 2 86 3 55 4.36 8.64 6.% 4.10 5.32 5.22 4 35 3.78 6.34
I I 15 5 5 3 3 3 9 9 9 17 17 17 15 12 12
0.21 0.77 2 49 — — — — — — 1065 2516 1996 761 1362 6.53 7.39 346 4.48
0.00 0.00 000 361 611 123 2 80 9 87 4 96 511 2 66 3 62
III 222555 12 55
6 75 5.33 105 6.29 14 16 5 82 10 00 10 07 10 99 5 65 4.45 4 08 6 17 2 48 2 67 5 36 4 58 3 32
0 00 0.00 0 00 0 72 13 91 2 87 0 00 0 00 0.00 2.74 3.98 4.75 4.38 3 97 3.36 4.45 4 15 3 73
1 1 13 5 3 I I I 20 19 19 14 14 14 16 16 16
4 65 6 86 1 II 6 04 4 59 2 34 — — — 2 65 2 03 0 66 2 28 2 21 0.65 — — —
2 72 5 17 072 3 51 194 2 21 136 174 0 61 0 74 0 28 0 07
17 17 17 4 4 4 18 18 18 2 2 2
7 79 6 19 1 14 6 34 10 35 2 09 13 30 7 10 1 38 8 36 3 87 1 62 15 52 2 62 104 14 6 5 35 1 80
3.06 4.01 087 468 8 03 127 0 28 0 40 0 26 6.32 2 65 161 9 52 143 0 53 4 32 4 17 192
13 13 13 5 3 5 2 2 2 16 15 15 7 7 7 7 7 7
NOTE: See Figure 1 for location of study areas.
M = mean. SD = standard deviation, N = number of observations.
TABLE 5. Average concentrations of total Hg, PCBs, and IDDT in livers of juvenile birds. Lake P'aifanne, Finland
STATtsnc
Study area
1
AltEA2
Area4
Area5
AREA6
Sncas
Ho
PCB
XDDT
Ho
PCB
£DDT
He
KB
XDDT
Ho
PCB
IDDT
Ho
PCB
ZDDT
Residues, mg/kg wet weight
Black-throated diver
M
SD
N
M
—
—
—
—
—
—
—
—
1920
000
12.62
000
642
000
Great crested gicbe
1 00
1 40
0.29
2.21
071
3 55
SD
0 II
0.34
0.10
0.93
0.48
3.31
N
2
2
2
3
3
3
GoWcneye
M
SD
N
0.22
0.09
2
0.24
003
2
0 13
008
2
049
001
3
040
0 17
3
0 30
036
3
Merganser
M
SD
N
"
"
"
"
"
"
"
'
"
"
"
"
2.78
063
2
1 81
2.60
3
177
2.70
3
Sandp^n
M
SD
N
~
~
"
"
"
"
"
~
~
"
III
004
2
Bkck-bKkedguU
M
SD
N
M
—
—
—
2.30
0.00
1.91
0.00
063
000
—
—
—
—
—
—
2 10
OOO
—
—
Haiiii(giiU
0.26
046
0 14
'_
_
1 32
034
0 18
1,77
SD
0.00
0.00
0.00
000
000
000
1 64
N
1
1
1
1
1
1
5
M
—
—
—
—
3.11
1 20
042
350
043
072
343
0.96
0.37
SD
1.43
0.00
0.00
1.22
048
104
1 01
1.33
0.31
N
4
1
1
8
7
7
4
3
3
Black-headed gull
M
SD
N
145
0.77
4
058
036
4
0 12
009
4
"
"
"
0.56
0.48
6
0 14
0.13
6
007
007
6
"
"
"
M
SD
N
041
0.02
2
0 15
0.02
2
NOTE: See Figure 1 for location of study areas.
M^iocan. SD = standard deviation. N = number of observations.
amont different species, locations, and sampling years, the
nonparametric Friedman two-way analysis of variance was
used here, too, for comparing the different areas. In areas
I, 4, S, and 6 (Figure I) and in the black-backed gull,
herring gull, common gull, and common tern, significant
regional differences occurred with iDDT in the livers of
30
Pesticides Monitoring Journal
the adult birds but with no other compounds. The greatest
concentration of SDDT was in area 4 and the smallest
concentration was in area 1 .
Table 6 presents averages and standard deviations of total
mercury, PCBs, and 2DDT for the muscles and livers of
adults and juveniles. Table 7 presents means and ranges of
concentrations in different bird species. From these tables,
comparisons between different species, between muscles
and livers, and between adults and juveniles can be made.
Because lindane was present in only three individuals, the
data on this compound appear separately in Table 8.
TABLE 6. Average Hg, PCB, and iDDT concentrations in
muscles and livers of aquatic birds. Lake Pdijanne, Finland
Muscles
Livers
Residue
Adulis
Juveniles
Adults
Juveniles
M
2.73
0.78
7.90
231
TouJHg
SD
1.95
0.86
7.64
2,83
N
242
101
243
50
M
4.97
1 14
5.73
096
PCB
SD
5.32
1,75
6,33
2,08
N
229
72
230
40
M
3-39
071
4.21
0,82
SDDT
SD
394
1 58
541
1 68
N
229
72
230
40
NOTE: M = mean. SD = standard deviation. N- number of observations.
The ratios of residues in muscle to residues in liver were
compared with those of other studies (1 . 4. 9, 17, 18). For
mercury, this ratio varied in different bird species between
0.112 and 0.577 in adults, and between 0.278 and 0.573 in
juveniles. The muscle:liver ratio for PCBs in adults was
between 0.540 and 5.917; in juveniles the ratio was be-
tween 0.100 and 8.258. The SDDT ratio in adults ranged
from 0.383 to 8.884, and in juveniles, from 0.044 to
9.919. These values are approximately the same as those
found in the investigations cited above.
Table 9 presents the correlation coefficients of different
residues. Coitipounds whose residues correlated most fre-
TABLE 7. Concentrations of total Hg. PCBs, and IDDT in muscles and livers of aquatic bird species, Lake Paijanne. Finland
Muscles LlvBts
Juvemiles
Mean Range Mean Range Mean Range Mean Range
Black-throated diver
Residues, mg/kg wet weight
lot^ Hg
13.69
1280-14.57
PCB
2,67
1,32- 6,79
IDDT
624
2.90-11.82
64.07
494
16.27
45.80-82 33
3 79- 6 10
7.63-24.91
1920
12.62
6.42
1920
12.62
6.42
Great crested grebe
total Hg
251
0,90-
- 4.76
0.48
0.30-
0.75
5.75
1 15
- 8.50
1.73
0.92-
2.80
PCB
J. 10
054-
-1068
0.83
0.09-
2 18
5.18
0.41
-10,00
0.99
016-
1.65
IDDT
3.67
0 19-
- 7.58
0.22
0.08-
046
639
0.06
-1755
2.25
0,22-
6.89
Ooldeneye
total Hg
0 24
0 16-
- 0.28
0 16
0.07-
0,24
2.15
0.72
- 3.42
038
0 15-
050
PCB
0,22
0.06-
- 0.40
0.15
0 15
0.31
0.25
- 0.36
0,34
021-
O60
IDDT
0 14
013-
- 0.17
0.16
0.16
0.12
009
- 0 16
0,23
008-
0.71
Merganser
toulHg
5.44
3.80-
- 6.40
1 32
0.93-
1.97
23.23
1600
-32.50
2.78
2,33-
3.22
PCB
193
059-
3 38
0.18
0 18
1.89
1.45
- 2.23
1 81
0 30-
4.82
IDDT
2,73
056-
8,25
008
008
3.16
1.28-
- 5 95
1 77
0 20-
4.89
Sandpiper
total Hg
0.47
031-
063
_
_
0.82
0.38-
- 1.25
_
PCB
179
0.28-
3 30
—
-
-
030
0.16-
- 044
—
—
IDDT
3.06
0.71-
541
—
-
-
0.34
0.25
- 0 44
—
-
Black-backed gull
total Hg
3,25
1,32-
656
0.93
0 10-
1 98
946
4.50-
-22,20
2.20
2 10-
2.30
PCB
671
0,27-
18.87
2.74
038-
7,70
8,00
0 84-47,83
1 91
1.91
IDDT
6,27
008-
16.83
2.75
0.23-
1097
9,04
1 54
-34,41
0.63
0.63
Herring gull
total hg
289
0,10-
6.55
065
004-
1 74
753
021-
-18.00
149
026-
4.62
PCB
13 49
0,68-
37.71
3,30
0.59-
19.29
11.27
0.77-
-29.48
0.40
034-
046
IDDT
826
1.04-
22.05
1 60
0.27-
4.87
7.50
0.21-
-20.83
0.16
0.14-
0 18
Common gull
total Hg
1 97
0.45-
5.36
095
0.30-
1 59
585
1.22-
-1660
338
1.42
-5 56
PCB
4 12
0 19-
1745
0,66
0 15-
4,15
498
033-
-37 90
064
0.09
-2.50
IDDT
2.73
0.12-
1429
050
0.11-
3.93
3,73
0,02-
-1628
0.60
009
-2.41
Black-headed gull
total Hg
1 48
0.18-
4.36
0.40
0.10-
1.22
3.79
0.64-
- 9 90
0.92
0 19-
2.52
PCB
351
0.09-
24.52
0.43
0.06-
1 34
4.29
0.36-
-19.13
0.32
0.05-
1.09
IDDT
1 06
0.02-
1413
0 13
0.04-
0,42
1 01
0.09-
- 5.52
0.09
0.02-
0.21
Common tern
total Hg
3 73
069-
800
0,64
030-
1 92
10 10
068-
35 60
111
108-
1 14
PCB
4,15
043-
1592
095
3 24-
1 77
5 31
0 76-
24,38
041
0 40-
043
IDDT
1,57
0 16-
18.75
0,39
0.12-
1,55
1,47
0.18-
6.55
0.15
0.13-
0.16
Average of all species
total Hg
2,73
0 10-
14.57
0,78
0.04-
1.98
7.90
0.21-82.33
2.31
0.15-
19.20
PCB
497
0.06-
37.71
1.14
0.06-
10 29
5,73
016-47 83
096
005-
12.62
IDDT
339
0.02-
22.05
0.71
0.04-
1097
4,21
002-
34.41
0.82
0.02-
689
Vol. 12, No. 1, June 1978
31
TABLE 8. Lindane residues in muscles of three individual birds.
Lake P'aijanne. Finland
Specibs/aob
Common gull , juvenile
Common gull, juvenile
Merganser, adult (male)
Study A«E» Date mg/kg Wet Weight
1-8-73
1-8-73
5-6-73
0.019
0 058
0.362
NOTE: See Figure I for location of study areas.
TABLE 9. Correlation coefficients Ir) of different residues in
muscles and livers of adult and juvenile birds.
Lake P'aijdnne, Finland
Tissue
Residue
Total
Methyl
Hg
PCBs
Muscles Adult
methyl Hg
PCBs
ZDDT
+ 0.287'««
+ 0.2I4*"
+ 0.237"*
+ 0.049
+ 0.026
+ 0.565"*
Muscles Juvenile
methyl Hg
PCBs
ZDDT
+ 0.039
+ 0 114
+ 0,074
-0.018
-0 012
+o.7oa«"
Livers Adult
PCBs
ZDDT
+ 0 131*
+ 0.3I7**'
+ 0,644<«»
Livers Juvenile
PCBs
ZDDT
+ 0.819'"
+ 0,543«'«
+ 0689«'«
NOTE: • = p < 5 percent.
••• = p < 0 1 percent
quently in the greatest number of birtis were PCBs and
SDDT.
Table 10 presents the percentage of total mercury which is
methyl mercury. Percentages varied in different species
between 91 and 117. indicating inaccuracy of analytical
methods, since the correct value must be below 100
percent.
TABLE 10. Ratios of methyl mercury to total mercury in
muscles of adult birds from study areas I and 4,
Lake Paifanne, Finland — 1972
Methyl Hg:
Ratios.
Species
N'
Total Hc,%'
Range
Great crested grebe
6
91
67-110
Black-backed gull
4
117
107-126
Herring gull
1
100
100
Common gull
2
111
107-115
Black-headed gull
7
93
66-127
Common tern
10
107
69-160
NOTE: See Figure 1 for location of study areas.
' N^number of individuals sampled
' Percentages over 100 indicate inaccuracy in analytical methods.
Table 1 1 lists t-test findings which indicate that average
concentrations of residues in males and females differed
significantly. Muscles and livers in adults of each species
were tested. In some gull species significant differences
were found, and in all cases the average residue concentra-
tion in males was higher than in females.
Table 12 presents the ratio of 2DDT:PCBs among different
bird species for comparison with corresponding values in
earlier studies (4, 5, 23. 27. 34). Generally, birds which
have been nesting in industrial areas contain more PCBs in
relation to DDT than do individuals nesting far from such
areas (27). In Lake Paijanne, these ratios never reached the
high levels of 9:10 found in more remote areas of the
globe, but the average levels do correspond to those of the
North Atlantic (4). In many species the ratio SDDT;PCBs
parallels the values for birds in Greenland (5). Great
differences exist in the SDDT:PCB ratios of the different
bird species of Lake Paijanne.
Discussion
The nonparametric tests showed no regional differences of
concentration patterns among the birds sampled except for
XDDT in liver. If the material sampled from the different
areas is combined on this ground and t-tests are used to
search the yearly differences for every species, only the
PCB contents of the black-backed gull seem to have de-
creased. If the absence of any significant variations be-
tween the sampling years is regarded as a basic fact, then
the regional differences can be examined for every species
from material in which the results of the different years are
combined. Such an examination indicates that the different
gull species and the common tern contain significantly
more mercury at areas 3, 5, and 6 than elsewhere; PCBs
appear most often at area 1; and in all species, 2DDT
appears in comparatively even amounts at the different
sampling areas. Thus for mercury, the regional maximums
are not found in the locations of greatest pollution, areas 1
and 4. The same paradox applies to certain other trophic
levels of the lake (24). An explanation of this might be that
mercury is retained within the sediment at the low-
oxygenated areas 1 and 4; it does not pass through the food
chain as effectively as it would in sediment which is farther
from the sources of pollution.
TABLE 1 1. Significant t-test differences between residues in adult male and female birds. Lake Paifanne, Finland
Content
Tissue
Males
Females
SiGNIF.'
OF
DiFF
Species
M
SD
N
M
SD
N
Black-backed gull
total Hg
total Hg
muscle
liver
3.51
10.19
1.30
4,24
25
25
2 80
8.19
1 05
3.36
22
22
o
Herring gull
total Hg
liver
10.19
4,41
8
5.76
3.98
12
•
Common gull
total Hg
total Hg
DDE
ZDDT
muscle
liver
liver
liver
2.28
6.99
4 63
4.63
1,13
3.75
4.24
4.24
35
36
35
35
1 46
3.88
2.24
2.24
098
2.46
3.26
3.26
22
21
21
21
• *
• •
•
NOTE: M = mean; SD = standard deviation; N = number of observations.
' Significances: •=-p<IO*. •-p<5%. ••-p<[%
32
Pesticides Monitoring Journai
TABLE 12. IDDT.PCB ratios in muscles and livers of aquatic
bird species. Lake Pdijdnne , Finland
SDDT:PCB Ratio
Muscles
Livers
Species
Adults
Juveniles
Adults
Juveniles
Black-throated diver
2.339
3.292
0509
Great crested grebe
1.183
0.267
1,233
2 281
Goldeneye
0.658
1.073
0 397
0.688
Merganser
1.418
0.429
1 671
0.976
Sajidpiper
1.710
_
1 139
—
Black-backed gull
0.935
1004
1 130
0329
Hemng gull
0.612
0.479
0 665
04<>>
Coinmon gull
0663
0 763
0.750
0933
Black-headed gull
0300
0.301
0.235
0,277
Common tern
0.379
0.409
0.278
0.353
Average
0681
0.624
0.734
0.854
PCBs seem to enter the watercourse from the town of
Jyv'askyfa but their exact origin is unicnown. Otherwise
there is little regional difference of PCB and IDDT con-
tamination in the waterways around Lake Paijanne. indi-
cating that the residues detected in the birds originate
primarily in the wintering regions or along the migration
routes, or that they reflect the global levels of contamina-
tion. The differences between the average residues in
adults and those in juveniles show that bioaccumulation
occurs as individuals age (Tables 6, 7). Within each
species the contents of mercury, PCBs, and DDT were
significantly higher in adults than in juveniles. This was
seen in all species that had sufficient material for statistical
comparison.
Canada; and for the common gull, mercury content was
lower than in Norway. For the grebe, PCB levels were
lower in Lake Paijanne than in Great Britain; and for the
black-backed gull, levels were lower than in the Faeroe
Islands north of Scotland. For the merganser, juvenile
herring gull, and common tern, SDDT levels were lower in
Lake Paijanne than in the United States; and for the
black-headed gull, SDDT residues were lower than in the
Po Delta of northern Italy.
In Lake Paijanne, mercury residues for the black-throated
diver were greater than in Aberdeen in eastern Scotland,
and Canada; and for mergansers and herring gulls, residues
were greater than in Canada. In Lake Paijanne, mercury
content was higher for mergansers than elsewhere in Fin-
land; higher for black-backed gulls and herring gulls than
in the Faeroes; higher for the herring gulls than at Fife,
Scotland; and higher for the black-headed gulls than in
Norway and Great Britain. Mercury was present in equal
concentrations among mergansers in Lake Paijanne and
goosanders in the Baltic Sea.
For the black-backed gull in the Faeroes and the black-
headed gull of the Po Delta, PCB concentrations were
lower than in Lake Paijanne.
For the black-headed gull and the common tern, SDDT
concentrations were greater in Lake Paij'anne than in the Po
Delta. For the herring gulls from the Faeroes and the
common tern from the Po Delta, PCB levels were equal to
those of Lake Paijanne.
Tables 6 and 7 also show that mercury levels are higher in
liver than in muscle, and these differences are significant
in all species having sufficient material for statistical com-
parison according to t-tests. Conversely, PCBs and 2DDT
do not accumulate in the liver more than in pectoral
muscles.
Correlations between the different pesticide contaminants
(Table 9) do not reveal any causes but they do, to a certain
degree, illustrate the possible common origin of the differ-
ent residues, possible similar bioaccumulation in the food
chains, or possible similar behavior in metabolism. The
high significant positive correlation between the levels of
PCBs and 2DDT indicates that these fat-soluble contami-
nants behave similarly.
Authors referred to the published literature to compare
residue levels of Lake Paijanne birds with levels in the
same species in other countries (/. 3-7. 9, 17-23, 25-27,
33, 34, 36 ). It must be remembered, however, that mate-
rial from Lake Paij'anne did not contain birds that were
dead. This excluded from the sample those individuals that
may have been fatally poisoned by pesticides.
For the goldeneye, merganser, herring gull, and common
tern, mercury levels were lower in Lake Faij'anne than in
Lindane occurred at about the same concentrations in many
individual birds from Lake Paij'anne as in those from other
locations. Fat of aquatic birds of Greenland averaged 0.40
mg/kg of lindane (5); aquatic bird eggs of Ireland averaged
0.045 mg/kg (8); cormorants in the United States averaged
0.05 mg/kg in liver and whole bodies (//). Black-headed
gulls in the Po Delta averaged 0.049 mg/kg in the muscle
and 0.495 mg/kg in the liver; for the same individuals,
maximum values were 0.1 10 mg/kg for muscle and 1.87
mg/kg for liver (34). Although average concentrations of
lindane in Lake Paij'anne birds were almost zero, the
maximum levels were similar to those in the other coun-
tries mentioned.
Dieldrin, which did not appear at all in Lake Paij'anne
birds, has been reported in aquatic birds elsewhere (8. II,
18, 22, 30 34, 37). Values as high as 0.348 mg/kg have
been observed in aquatic birds of Utah, although maximum
levels range generally from 0.01 to 0. 10 mg/kg {30).
Comparison of concentrations in various bird species
shows that mercury residues are highest in the diver,
merganser, common tern, and common gull. PCB contents
are highest in the herring gull and common gull, and
SDDT is highest in the herring gull, black-backed gull,
and diver. Considering SDDT concentrations in liver
Vol. 12, No. I, June 1978
33
alone, residues arc highest in the diver. Differences among
the bird species may depend principally on feeding habits,
although duration of life, migration routes, and wintering
regions also cause differences. The gulls, especially the
black-headed gull and the herring gull, feed on garbage as
well as fish, and the black-headed gull also eats terrestrial
animals living in arable lands.
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(13) Hallula. ML 1973. Analysis of DDT- and PCB-type
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(14) Hallula, M.L. 1974. Some aspects of the recovery of
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34
(15) Hallula. M. L. 1974. Simultaneous clean-up of fish fat
containing low levels of residues and separation of PCB
from chlorinated pesticides by thin-layer chromatography.
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(16) Holden. A.V.. and K Marsden. 1969 Single-stage
cleanup of animal tissue extracts for organochlorine resi-
due analysis. J. Chromatogr. 44:481-492.
(17) Holl. G. 1969. Mercury residues in wild birds in Norway.
Nord. Veteringermed. 21(2): 105-1 14,
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ticide and mercury levels in migrating duck populations.
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(19) Karlog. O . I. Kraul. andS. Dalgaard-Mikkelsen. 1971.
Residues of polychlorinated biphenyls (PCB) and or-
ganochlorine insecticides in liver tissue from terrestrial
Danish predatory birds Acta Vet Scand. 12(2):3 10-312.
(20) Karppanen. E.. K. Henriksson. and M. Helminen. 1970.
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84(35):'l097-ll28.
(21) Koivusaari. J.. I. Nuuja. R. Palokangas. and M.L. Hal-
lula. 1976. Chlorinated hydrocarbons and total mercury in
the prey of the white-tailed eagle (Haliaetus albicilla L.) in
the Quarken Straits of the Gulf of Bothnia, Finland. Bull.
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eagles, 1966-68. Pestic. Monit. J. 4(3):141-144.
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(25) Presli. I . D J. Jefferies. and N .W . Moore. 1970.
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avian toxicity. Environ. Pollut. l(l):3-26
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(30) Smith. FA.. R.P Sharma. R.I. Lvnn. and J B. Low.
1974. Mercury and selected pesticide levels in fish and
wildlife of Utah: II Levels of mercury. DDT, DDE, diel-
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Environ. Contam. Toxicol. 12(21:153-157.
(31) Talion. JO G. and J. HA. Ruzicka. 1967. Or-
PESTICIDES MONtTORlNG JOURNAL
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(5099):346-348. Rev. Int. Oceanogr. Med. 35-36, 79-90.
(32) Tuunainen P.. K. Granherg, L. Hakkari. and J. Sdrkk'a.
1972. On the effects of eutrophication on Lake Paijanne,
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18( 1 ) 388— 40"* ganochlorine pesticides and polychlorinated biphenyls in
animal foods. Acta Chem. Scand. 24(5):I639-I644.
(33) Vermeer. K.. F.A.J. Armstrong, and D.R.M. Hatch.
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1967. DDT residues in an east coast estuary: a case of
(34) Viviani, R.. G. Crisetig, P. Cortesi, and E. Carpene. biological concentration of a persistent insecticide. Science
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Vol. 12, No. I.June 1978 35
Dieldhn, DDT, PCBs, and Mercury Levels in Freshwater Mullet from the Upper Great Lakes,
1975-76 •
Mary E. Zabik,^ Barbara Olson,- and Teiko M. Johnson -
ABSTRACT
Freshwater mullet harvested commercially during various sea-
sons of 1975-76 from the upper Great Lakes were analyzed for
organochlorine pesticides , PCBs. and mercury. Species
analyzed were Catostomus commersoni, C. catostomus. and
Moxostoma erythruran. Whole ground fish, mechanically de-
honed flesh, head, middle, and tail steaks, and various muscles
were analyzed for pesticides and PCBs: only edible flesh was
analyzed for mercury. Dieldrin ranged from none detected to
0.23 ppm in deboned and whole ground samples, the DDT range
was a trace to 0.30 ppm, and PCBs ranged from 0.06 ppm to
0.79 ppm. Levels were also higher in head sections and in high
fat-containing medial muscle and belly flap. Mercury levels
ranged from 0.03 ppm to 0.28 ppm in the flesh of mullet from
Lake Michigan.
Introduction
Freshwater mullet from the lakes surrounding Michigan
have received little attention as significant sources of
human food. In their native form, these fish are frequently
considered unattractive to consumers because of their in-
tramuscular bony structure and/or their muddy flavor
which is characteristic of fish with their particular eating
habits. Estimates indicate, however, that mullet could be
harvested from Michigan waters at an annual rate ap-
proaching one million kg. Two species of the genus
Catostomus comprise most of the mullet population in
Lakes Huron, Michigan, and Superior. The white mullet
iCaloslomus commersoni) is widespread in Lakes Huron
and Michigan, the longnose mullet (C. catostomus) pre-
dominates in Lake Superior, and the golden redhorse mul-
let ( Mo.xosloma erythruran) is available in commercially
harvestable quantities from Lake Huron.
'Michigan Agricultural ExperimenI Slition Journal Article No 8142 Research
supported hy Upper Great Lakes Regional Commission Technical Assistance
Project No 10520239
' Department of Food Science and Human Nutrition. Michigan State University.
East Laming. Ml 4S824
In addition to their muddy flavor, these fish have been
unpopular with consumers because of the numerous Y
bones throughout the fleshy portion of the fish. Recently,
however, mechanical means have been developed for
separating meat from bone, yielding a boneless minced
flesh product. This minced flesh can be used in various
consumer products. However, before commercial products
can be developed, it has been necessary to determine the
levels of environmental contaminants, their seasonal varia-
tion, variation of environmental contaminants within dif-
ferent muscles, and location of the fish in representative
species from the three lakes concerned.
Sampling Procedures
Mullet were harvested by commercial anglers from Lakes
Huron (Saginaw Bay, Standish. and Au Gres. Michigan),
Michigan (Epoufette Bay, Epoufette, Michigan), and
Superior (Whitefish Bay, Brimley, Michigan) during dif-
ferent seasons of 1975-76. They were readily available
from commercial anglers in Saginaw Bay. The fish were
less readily available in the upper Lakes Superior and
Michigan, so seasonal variation could not be determined
specifically. Fish were ice-packed and transported to the
laboratory for processing and analyses, usually arriving the
day after the catch. Following heading and gutting, fish to
be deboned by machine were split into halves and run
through the Bibun deboner (Type SD x 13, 5-mm holes),
resulting in a minced flesh product separated from bone,
skin, and scales. Whole headed and gutted mullet (.15^0
cm long) were coarsely ground three times in a Hobart food
cutter fitted with chopper attachment. Other whole dressed
mullet were filleted into the ventral, dorsal, medial, and
belly flap muscles or sectioned into head, midsection, and
tail cross slices. Two mullet, 35^0 cm long, were used
for each muscle or section study for each catch date for
each lake. Muscles or sections were homogenized sepa-
rately in an Osterizer blender and all samples were frozen
36
Pesticides Monitoring Journal
and held at -23° C in glass jars before being thawed
overnight at 4°-5° C for residue analyses.
Analytical Procedures
PESTICIDES AND POLYCHLORINATED BIPHENYLS (PCBs)
Two samples of each fish variable were extracted sepa-
rately with hexane-acetone (2:1), partitioned with
acetonitrile, and subjected to Florisil-Celite column
cleanup according to the method of Yadrick et al. (7).
Solids were determined by drying 2-g samples under vac-
uum at 90° C to constant weight; lipid was estimated by
evaporating an aliquot of the hexane extract to dryness at
70° C under vacuum.
Gas chromatographic analyses were performed with a
Tracor 560 gas-liquid chromatograph (GLC) equipped with
a ^'Ni electron-capture detector and interfaced with a Dig-
ital PDP-8e-Pamila GC data system. Instrument parameters
and operating conditions follow.
Column
Temperatures:
Carrier gas:
1 83-m X 4.0-mm ID Pyrcn. packed with 3 percent
OV-1 on 80-IOO-mesh Chromosorb W-HP
column 190° C
injection port 230° C
detector 300° C
nitrogen nowing at 40 ml/minute
Standards were prepared with 99-1- percent pure recrystal-
lized dieldrin, p,p'-DDT. and p.p'-JDE, and Aroclor
1248 in Nanograde hexane. Quantitations were based on
peak area for pesticides; the area of three peaks was used to
quantitate the PCBs. Standards were run every morning
and after every eight or nine samples. Recoveries with this
method of extraction and quantitation were 85±2 percent
for PCBs and 92±1 percent for dieldrin and DDT com-
pounds; limits of detection were 0.01 ppm for PCBs and
0.001 ppm for dieldrin and DDT compounds. Data pre-
sented in this paper are not corrected for recoveries.
Presence of these residues was confirmed by mass spec-
trometric analysis on a pool of all extracted samples from
each lake. The chromatograph used was a Beckman GC-65
interfaced with a DuPont 21-490 mass spectrometer which
in turn was interfaced with a Digital PDP-12-LDP com-
puter. Mass spectra were obtained at an ionizing voltage of
70 eV with a source temperature of 210° C.
MERCURY
Mercury was determined from duplicate edible flesh sam-
ples for each catch from each lake as total elemental
mercury by using flameless atomic absorption spec-
trophotometry as described by Gomez and Markakis (2).
Concentrated sulfuric acid was used to digest the samples
as described in their Digestion 1 procedure. Recovery was
95 ±1 percent, and the limit of detection was 0.005 ppm.
Values presented are not corrected for recovery data.
Results
Fat, solids, pesticides, and PCBs in whole ground and
mechanically deboned mullet from the upper Great Lakes
are presented in Tables 1 and 2. Dieldrin content ranged
from none to 0.23 ppm. 2DDT in white mullet caught in
Lake Superior in June ranged from a trace to 0.30 ppm.
PCBs varied from 0.06 ppm to 0.79 ppm. All levels are
below the tolerances for these environmental contaminants
established by the Food and Drug Administration (FDA),
U.S. Department of Health, Education, and Welfare, al-
though dieldrin levels in the mullet from Lake Michigan
are closest to their tolerance level, 0.3 ppm.
Seasonal variation appears to be minor. As much variation
occurred in the levels of contaminants themselves as in the
levels as they related to the different catch dates.
The Great Lakes Environmental Contaminant Survey
analyzed two freshwater mullet under 16 inches long from
Lake Huron in 1974 and four in 1975 {3, 4). Values
reported there are similar to those in the current study. An
earlier analysis of a freshwater mullet revealed 1.14 ppm
DDT (5). Thus DDT levels may be decreasing. Similar
DDT levels were reported in freshwater mullet from Lakes
TABLE 1 . Fat. solids, pesticides, and PCBs in whole ground freshwater mullet. Upper Great Lakes. 1975-76
Date of
Dl
ELDKIN
ZDDT
PCBs AS AKOCLOit 1248
Wet
Wet
Wet
Lake
Type
Caich
Fat. %
SOUDS, %
Tissue
Fat
Tissue
Fat
Tissue
Fat
White
February 75
2.63
23 43
Residues,
PPM
Huron
0 03
1 10
0 06
2,03
0 54
10 03
White
May 75
1 20
21 30
0 10
8 84
0,06
4 26
0,54
43,40
While
August 75
2.70
24 40
0 09
3,15
0,08
2,89
0.79
29 36
Redhorse
August 75
7 90
31 70
0,11
1,45
0 08
098
0.70
8.86
White
December 75
2 30
21.30
0 16
3 97
0 30
13,31
0.12
5.30
White
February 76
2 30
23 90
0 04
1 92
0 08
3,57
0.15
6 28
Michigan
Longnose
June 75
4,20
25 25
0 21
5,01
0,23
3 12
0,62
14 05
Longnose
August 75
5 55
25,65
0 23
4 31
0,27
4.49
0.71
12 67
White
June 76
115
24 00
0 03
2 77
0.03
2.82
0.16
12.99
Superior
White
June 75
2,05
22,35
—
—
Tr'
—
0.06
3.12
Longnose
December 75
3 95
24,25
0,09
2 33
0-14
3.46
0,26
6.55
' Tr = 0 005
-0.009
ppm
Vol. 12,
No.
1, June 1978
37
Ontario and Erie, although dieidrin levels were less than
0.01 ppm(/).
Variation in levels of environmental contaminants from
head to tail is summarized in Table 3. The head slices
which contained the most fat had the highest levels of
environmental contaminants. On a fat basis, however, the
distribution was more uniform.
have little benefit because residues in the loin muscles
were also high.
Mercury levels in the edible flesh (Table 5) were highest in
fish from Lake Michigan. Values reported for fish from
Lake Huron are close to those reported by the Great Lakes
Environmental Contaminants Survey {3, 4).
Variation in contamination according to muscle content is
shown in Table 4. The high-fat medial muscle and belly
flap contained the highest amounts of residues. Because
the residues are fat-soluble, trimming would be a feasible
method of reducing contaminants if the deboned flesh ever
exceeded FDA tolerances. Reinert and Bergman (6) also
found that these areas had higher levels of contaminants in
Coho salmon, but they concluded that trimming would
Acknowledgment
The authors thank Estes Reynolds, Food Science and
Human Nutrition Department, Michigan State University,
for procuring the fish, and Drs. Dawson, Price and
Reynolds for help with fish processing. Appreciation is
also expressed to Matthew Zabik, Pesticide Research Cen-
ter, for mass spectrophotometric analyses.
TABLE 2. Fat, solids, pesticides, and PCBs in mechanically deboned freshwater mullet, upper Great Lakes, 1975-76
Date OF
Dl
ELDRIN
IDDT
PCBs AS
AIOCLOE 1248
Wet
Wet
Wei
Lake
Type
Catch
Fat. %
Solids. %
Tissue
Fat
Tissue
Fat
Tissue
Fat
While
February 75
2,07
22,37
Residues.
PPM
Huron
001
0.62
0.03
1.84
0.29
14 13
While
May 75
1 50
19 83
0 06
4.27
0.06
4.14
0 50
33 39
While
August 75
1 60
19 75
0 07
4.16
0 08
4.63
0 41
2501
Redhorse
August 75
5 50
24,85
005
096
0.04
0.69
0 18
3.22
While
December 75
2,75
20,70
0 15
5.22
0 20
6 99
0 70
24 38
While
February 76
2 95
20 25
0 07
2.47
0 10
3 26
0.17
5 88
Michigan
Longnose
August 75
5,23
23,90
0.13
2.37
0.16
2.93
0 49
9 29
While
June 76
1,83
19 75
0.03
1 90
0.03
1.87
0 26
14 06
Superior
While
June 75
2,15
18.20
Tr'
—
0.01
0.56
006
2.93
Longnose
December 75
3 00
21 15
0 07
2.28
0.12
3 88
0.70
23.32
' Tr = 0 005-0 009 ppm
TABLE 3. Pesticides and PCBs in sections of freshwater mullet, upper Great Lakes, 1975-76
Mean Fat
Mean Solids
Mean
DlELDEIN
Mean
XDDT
Mean PCBs as
AloCLoa 1248
Wet Tissue
Fat
Wet Tissue
Fat
Wet Tissue
Fat
Lake
Section
(Range). %
(Range). %
(Range)
(Range)
(Range)
(Range)
(Range)
(Range)
Head
5 80
27,77
Residues, ppm
Huron '
0.16
3.35
0.24
4.84
0.86
15 06
(3.65-955)
(23 65 33 55)
(0.02-0.68)
(0.45-13 31)
(0.03-0.98)
(1 75-19.25)
(Tr'-l 92)
(Tr-32 40)
Middle
3 14
24 13
006
2.66
0 07
2 91
039
15 54
(1.72-7 60)
(22 55-30.00)
(0.01-0 21)
(0 58-9 40)
(0 02-0 19)
(0 36-8 09)
(0 14-1 10)
(302-37 36
Tail
2.04
26 21
003
2 34
0 04
2 97
0 18
12 94
(0.65-5.25)
(23 00-30 00)
(Tr-0 09)
(Tr-6 68)
(Tr-0 13)
(Tr-6 85)
(Tr-0. 34)
(Tr-23.29)
Michigan '
Head
4 77
26 22
0 09
2.25
0 10
2 18
056
1509
(2.25-8 20)
(23 20-30 10)
(0 05-0 11)
(1.33-3 10)
(0 05-0 17)
(1 94-2 53)
(0 49-0.61)
(8 07-18.78)
Middle
3.82
24 30
009
2 17
0 12
2 13
0 29
11 61
(1.15-7 05)
(21.05-26 70)
10 02-0 14)
(1 62 2 94)
(0 03-0 17)
(1 94-2 43)
(023-035)
(8 56-16 90)
Tail
2.13
23.07
0.06
2 58
0 06
2 09
0 26
15 55
(1.24-3 80)
(21 10-24 70)
(0. 02-0. 08)
(1 58-3 95)
(002-0 08)
(1 94-2 25)
(0 10-0 46)
(7 40-30.58)
Superior*
Head
2.65
23.70
0 06
1 68
0 13
3 34
0 24
7 29
(2.05-3.25)
(21 90-2550)
(Tr-0 II)
(Tr 3 36)
(Tr-0. 23)
(Tr-6 68)
(0 08-0 39)
(3 16-11 41)
Middle
2.10
24 15
0 02
0 84
0.03
1 17
0 15
6 66
(1.70-2 50)
(22.20-26 10)
(0.00-0 04)
(0 00-1 68)
(Tr-0 06)
(Tr-2 34)
(0 08)-0 22)
(4 42-8 89)
Tail
1.70
22 48
003
1 21
0 06
2 56
0 14
7 80
(1 20-2.20)
(20.70-24.25)
(Tr-0.05)
(Tr-2.42)
(0.00-0. II)
(0.00-5.11)
(0.07-0.21)
(5.76-9.84)
J oa six CBichci from Feburary I97S to February 1976.
'Tr - 0 005 -0 009 ppm
' Bucd on (hree caichet from June 1975 (o June 1976
' Bucd on two calcbci from June 1975 to r>ccembcr 1975.
38
Pesticides Monitoring Journal
TABLE 4. Pesticides and PCBs in muscles of freshwater mullet, upper Great Lakes.
197 5 -It
Lake
Michigan ^
Superior*
Ventral
Lateral
line
Dorsal
Belly
nap
Ventral
Lateral
line
Oonal
Belly
flap
Ventral
Lateral
line
Dorsal
Belly
nap
Mean Fat Mean Solids
(Range). % (Range). »
0.83
(0 55-1 03)
5 44
(1-50-8 25)
1.10
(0.50-1 90)
3 51
11.15-7 05)
I 04
(0.60-1 45)
8.13
(2.49-13 95)
1.32
(0,52-2 30)
6.13
19 94
(17.25-22.20)
24.26
(17.25-29.45)
20 II
(17.05-21 65)
21 55
(19 00-26 90)
20 59
(19 85-21 30)
26 70
(21 30-31 45)
20 53
118 85-21,40)
23 88
(1. 85-11. 90) (19.45-29,40)
159 1968
(0.87-2.30) (1790-21.45)
8 50 28 95
16 80-10 20) (2675-31.15)
145 19,73
(0 85-2 05) (18.60-2085)
3 93 24.13
(2.00-5.85) (2000-28.25)
' Based on six catcfies from
■ Tr = 0 005-0 009 ppm
' Based on three catches froi
' Based on two catches from
Febritary 1975 to February 1976.
n June 1975 to June 1976
June 1975 to December 1975
Mean Dieldrin
Mean ZDDT
Wet Tissue
(Range)
0.02
(Tr^-O 05)
0 08
(0 01-0.18)
0.02
(Tr-0 05)
0 10
(0 01-0 24)
0.06
(0.02-0.10)
0,22
(0,15-0 28)
0 05
0.02-0.10)
0.26
(0.19-0 34)
0 04
(Tr-0,08)
0 12
(0 02-0,22)
0 02
(Tr-0 04)
0,09
(0 02-0,15)
Fat
(Range)
Wet Tissue
(Range)
Fat
(Range)
3 39
(Tr-ll 20)
2 18
(0,36-5,78)
2.45
(Tr-7.10)
3.24
(0 70-6.36)
6 00
(4 04-9 83)
3.92
(I 57-5.52)
4 50
(1.60-8.5 1)
5 98
(2.13-7.92)
1.33
(Tr-2.66)
I 24
(0,35-2.13)
1 06
(Tr-2 12)
I 86
(0.71-2.95)
Residues, ppih
0.07
(0 01-0 28)
0 10
(0.05-0 18)
0.06
(Tr-0. 20)
0.13
(0,03-0.36)
0,06
(0 03-0 II)
0,28
(0 16-0 41)
0,22
(0,16-0.34)
0.37
(0.13-0 55)
0 07
(Tr-0 14)
0.37
(0 03-0 70)
0.04
(0.01-0 06)
0 13
(0.01-0 24)
10 06
(1 22-38 69)
2 43
(0 62-5.39)
5.27
(0.63-20.47)
3 91
(1 67-6 29)
6,32
(3 28-11,11)
4,32
(I 99-6.00)
6 91
(I 80-13 36)
7,77
3,62-11.95)
2.37
(Tr-4.74)
3,74
(0 56-6 91)
2.22
(1.52-2.87)
2 48
(0 62-4 34)
Mean PCBs as Aioclou 1248
Wet Tissue
(Range)
Fat
(Range)
0 18
(Tr-0 52)
0,80
(0,19-1 17)
0 09
(Tr-0 17)
0 69
(0,24-1 53)
0,30
(0 09-0.46)
1.22
(1.13-1. 31)
0 21
(0.02-0 34)
1 33
(0.35-2.44)
0 08
(0 06-0 10)
0,42
(0,27-0 57)
0 08
(0 08-0 08)
0,21
(0,13-0,28)
32 20
(Tr-120 02)
16 93
(9 44-23,45)
10 83
(Tr-16,43)
21 03
(7 06-41 19)
29,20
(16,59-40.42)
22.10
(9.47-40.84)
15.12
(3.44-23.38)
24 49
(10.22-49.20)
7,85
(4 92-10.77)
5.71
(2 75-8.66)
7,32
14 73-9 91)
6.92
(6.70-7.13)
TABLE 5. Mecury levels in freshwater mullet,
upppr Great Lakes. 1975-76
Lake
Date of
Catch
Michigan
Superior
While
Fcbruarv 75
While
Mav 75
While
August 75
Rcdhorse
August 75
White
December 75
White
February 76
Longnose
June 75
Longnose
August 75
White
June 76
While
June 75
White
December 75
Mercury.
PPM
0 03
0 06
0.09
0.07
0 06
0 05
0.21
0.12
0.28
0 10
0 06
LITERATURE CITED
(1) Frank. R.. A. E. Armstrong. R G. Boelens. H E Braun.
and C. W. Douglas. 1974. Organochlorine insecticide resi-
dues in sediment and fish tissues, Ontario, Canada Pestic
Monit. J. 7(3/4):I65-180.
(2) Gomez. M. I., and P. Markakis. 1974. Mercury content of
some foods. J. Food Sci. 39(4):673-675.
(3) Great Lakes Environmental Contaminants Survey. 1974.
Michigan Department of Agriculture, Lansing, MI. p. 35.
(4) Great Lakes Environmental Contaminants Survey. 1975.
Michigan Department of Agriculture, Lansing. MI. p. 25.
(5) Reineri. R. 1970. Pesticide concentrations in Great Lakes
fish. Pestic Monit. J. 3(4):233-240.
(6) Reinert. R. E.. and H. L. Bergman. 1974. Residues of DDT
in Lake Trout (Salvelinus namoycush) and Coho salmon
(Oncorhynchus kisutch) from the Great Lakes. J Fish Res
Board Can 31(2):191-I99.
(7) Yadrick. M. K.. K. Funk, and M. E. Zabik. 1971 . Dieldrin
residues in bacon cooked by two methods. J. Agric Food
Chem 19(3):491^94.
Vol. 12, No. 1, June 1978
39
General
Mirex Incorporation in Estuarine Animals, Sediment, and Water,
Mississippi Gulf Coast — 1972-74 '
Armando A. de la Cruz- and Kuang Yang Lue'
ABSTRACT
Analysis of mirex residues in esiuarine animuls, seJimeins. unci
waters collected from the Mississippi Gulf Coast in 1972-74
showed the following ranges of concentrations: seston, 200-
3000 pph: molluscs. 36-500 pph: fish. 0-259 ppb: sediment.
3-5 ppb: and water. 0-0.01 ppb. These data indicate that mirex
in aquatic environments is localized in animal tissues and bot-
tom substrate and that only a negligible amount is incorporated
in the water
Introduction
In 1971-74. the authors conducted a series of studies on
the toxicity and ecological and physiological effects of
mirex on nontarget organisms. The three areas of study
included residue monitoring and toxicity, effects of mirex
on certain ecological processes of plants and animals, and
physiological effects on enzyme systems. The results of
these studies are cited in a literature review by Lue (4).
The ecological aspect of this project emphasizes the incor-
poration of mirex in the environment through leaching of
the insecticide from decaying fire ant bait in the field (2,
/O). Mirex residues were recovered from seafood from the
Atlantic and Gulf Coastal states (7), in terrestrial and
aquatic invertebrates from Louisiana (S), and in other
selected organisms (//). During these studies, therefore.
the authors routinely collected samples from different
habitats (Q). This paper reports mirex residues detected in
samples collected from an estuarine environment on the
Mississippi Gulf Coast. The animal samples were collected
in the fall of 1972. the sediment samples during summer
1973. and the water samples in 1972 and 1974.
Materials and Procedures
COLLECTION OF SAMPLES
The animals were collected manually from the substrate in
St. Louis Bay marsh during low tide. Those from Missis-
sippi Sound were collected by using a shrimp trawl. The
specimens were rinsed of mud or debris, blotted dry.
wrapped in aluminum foil, and frozen until analysis. Water
samples were collected in clean, hexane-rinsed lO-liter
jugs by directly filling the jugs a few centimeters beneath
the water surface. Water samples for mirex analysis were
refrigerated when not immediately processed. Waters in-
tended for seston analysis were promptly filtered through
AA millipore filters (0.8-;j.m porosity) in a millipore
vacuum-filtration apparatus. Seston is particulate matter
suspended in water including plankton, organic detritus,
and inorganic silt. Sediments were collected by an Ekman
dredge from St. Louis Bay and by a Petersen dredge from
Mississippi Sound. The samples were placed in clean,
hexane-rinsed wide-mouth specimen jars and refrigerated
until extraction.
EXTRACTION OF SAMPLES
Single or pooled (2-10 specimens) whole-body samples of
animals were extracted for residue analysis according to
the procedure of Naqvi and de la Cruz (9). Only the fleshy
tissue of molluscs was extracted. Specimens were rinsed
with distilled water to remove salt and briefly dipped in
hexane to remove any external insecticide contamination.
Samples were ground in nanograde hexane and shaken
vigorously, and the decanted solvent was evaporated to
dryness. Prior to gas-liquid chromatography, the extracts
were cleaned by using activated alumina.
' Sludy lupponcd by Agricullural Rcseirch Servkt. U S Dcpsnmcnl of Agncul
lure. Coopcrilive Agrecmcm No 12- 14-1001093}.
' I>cpartment of Biological Sciences. Mi»%isMppi Slate Univcr&ily. P O Drawer Z
Mittisiippi Slale. MS 39762
' Depailment of Biology, Taiwan National Normal University. 88 Sec 5, Taipei.
Taiwan 117, Republic of China
Seston samples were extracted according to the procedure
in the Pesticide .Aiuilyticat Manual {3) for small samples.
The filter paper holding the seston was ground in a tissue
grinder with acetonitrile. The filter paper was free of mirex
when checked for contamination. The extract was concen-
trated and reduced to a suitable volume for analvsis.
40
PhSIK IDKS MONl TURING JoUKNAl
Water was extracted with nanograde hexane in 250-ml
separatory funnels; 150 ml samples were shaken vigorously
with 50 ml hexane three successive times. 3 minutes each
time. The three hexane extracts were combined and
evaporated to a volume suitable for gas chromatographic
analysis.
Samples of 150 g sediment were extracted with 300 ml
hexane-isopropanol mixture (3:1) according to the proce-
dure of Markin et al. (6). The extract was filtered through
Na2S04 and concentrated to 10 ml.
CHROMATOGRAPHY
Extracts of all samples were analyzed in a Barber-Colman
Pesticide Analyzer Model 5360 equipped with an
electron-capture detector. A 152.4 mm x 3.2 mm glass
column was used. Standard injection techniques were used
consistently for all samples. Extract volumes (2 ju.1) were
injected. Information about operating parameters of the
analyzer can be obtained from the Physiological Labora-
tory, Department of Zoology, IVississippi State University,
Mississippi State, Mississippi 39762. The concentration of
mirex was calculated with the following formula:
mirex residue = Vwd2lWvd \
where W = weight of the sample in grams, V = volume
of final extract in milliliters, v = volume of extract in-
jected in /xl, w = weight of the standard injection in
nanograms, d \ = peak height of standard solution,
rfa = peak height of extract. A second column (1.5 percent
SP-250, dimethylchlorosilane-treated and acid-washed)
was used to confirm the mirex residues recovered from the
field samples.
Results and Discussion
Mirex residues in seston and animals collected from St.
Louis Bay and Mississippi Sound are summarized in Tables
1 and 2. Concentrations in seston filtered from Mississippi
Sound water (1000-3000 ppb) is one order of magnitude
higher than in seston from St. Louis Bay (200-800 ppb).
Residues in the animals were all below 1 ppm except in the
fiddler crab Uca (1.3 ppm). The molluscs, i.e., snails,
clams, and mussels, from St. Louis Bay, which are ba-
sically filter feeders, had slightly higher levels of mirex
(36-500 ppb) than did the other invertebrates from Missis-
sippi Sound (0-133 ppb). In an earlier study, Naqvi and de
la Cruz (9) found 70-410 ppb mirex in snails and clams
collected from a similar estuarine habitat. Residues in the
fish ranged from 0 to 259 ppb.
The residue levels of sediments from bay and sound were
essentially similar (Table 3) and fairly low (2.8-4.6 ppb).
These values are, however, much higher than the residue
levels detected in the water samples (0.001-0.010 ppb)
from Mississippi Sound, St. Louis Bay, and from the
TABLE 1 . Mirex residues in seston ' and animals ^
from Si. Louis Bay marsh-estuary. November 1972
BlOMASS
Extracted,
G
Residues
.ppb'
Specimen
Col. I
Col. n
Seston
0.07
817.7
9206
0 26
204 1
235 0
0.19
2159
199 7
0.10
408.8
376,9
Rangia cuneata (Clam)
8.10
331.3
247,5
3.00
490.2
450,0
Modiolus liemissus (Ribbed mussel)
4 60
183.8
159 8
3.00
367
71 3
Melampus bldeniolus (Snail)
3.80
339 2
265,2
2 90
471.4
415,2
0 65
81 8
0.0
0.45
118,2
0.0
Littorina irrorala (Snail)
0.40
130 9
0 0
0.80
499 9
31,3
0.70
75.9
89 3
0.70
37,9
0,0
0.60
66,5
35 7
Vca sp (Fiddler crab)
0.30
1302,0
2661,0
Strong\lura marina
13,80
50,9
47,4
(Atlantic needlefish)
' Seslon includes suspended paniculate matier consisting of plankton organisms,
organic detritus, and inorganic sediment filtered from 300 ml of water with 0 8 /im
Millipore acetate filter
^ Animals were pooled from 2-10 individuals of about the same size. Biomass
represents whole tissue, excluding shells and molluscs
* All analyses were done with two columns to verify the mires residue
TABLE 2. Mirex residues in seston^ and animals^
from Mississippi Sound, September 1972
Sponge
Luidia claihraia (Starfish)
LoUiguncula hrevis (Squid)
Palaemonetes sp. (Grass shrimp)
Callmectes sapidus (Blue crab)
Squilla empusa (Mantis shrimp)
Bairdiella chrysura (Silver perch)
Bagre marinus (Gafflopsail catfish)
Porichlhys porisissimus
(Atlantic midshipman)
Eiropus crossotus
(Fringed flounder)
S\mphurus plagiusa
Blackcheek tonguefish)
Cynoscion arenarius (Sand seatrout)
Sirongylura marina
(Atlantic needlefish)
BlOMASS
Residue!
i. PPB
G
Col 1
Col. II
0,01
3038 4
2396.8
0 03
1507 8
26298
0 03
1001,4
4150 5
0,23
1172,7
1321.1
0,01
3260,7
2007 4
0,02
2291,8
28149
0,01
2677,2
2677.2
0.01
3243 4
3003,7
0.61
133 5
231 0
7.24
28 1
37,0
8.68
24 0
0,0
5.40
0,0
0,0
S.97
13 6
0 0
2.77
0,0
0,0
3.39
0,0
0,0
15.84
7 6
106 0
20,80
3,7
0,0
18,00
6 4
6,4
1.10
1280
207,8
1.30
22,0
0 0
8.30
4 8
0,0
6.60
1 1
1 8
11,70
81,6
97,0
9.70
15 9
9.6
9.20
7.2
_
11.30
12 5
11,7
12.80
110
16 5
45.00
0,0
0,0
19 30
259 1
245 4
18.00
179.9
132,0
' Seston includes suspended particulate matter consisting of plankton organisms
organic detritus, and inorganic sediment filtered from 300 ml of water with 0.8
^m Millipore acetate filter
' Animals were single speciments; whole-body tissue was analyzed,
' All analyses were done with two columns to verify the mirex residue.
Vol. 12, No. 1, June 1978
41
Jordan and Wolf Rivers thai empty into the bay (Table 4).
Spence and Markin (10) found that the highest mirex level
in natural water was 0.02 ppb. In a separate study (5). the
authors found 0.01 ppb residue in samples of water col-
lected from a farm pond. The residue data reported in this
paper indicate that mirex in aquatic environments is lo-
calized in bottom sediments, animal tissues, and in par-
ticulate matter, i.e., seston, suspended in the water, and
TABLE 3. Mirex residues in esluarine sediment.
Mississippi Gulf Coast — 1973
Residues.
Collection
Date
Amount
Extracted,
G
PPB
'
Location
Col
Col. II
St, Louis Bay '
5/29/73
6/18/73
8/26/73
100
ino
ion
2.8
3.9
3 5
5 0
5 9
5 3
Mississippi Sound '
7/17/73
7/19/73
100
100
4-6
3 5
2 2
5 2
' All analyses were done with two columns to verify the mirex residue,
* Collected by an Ekman dredge from the mouth of Catfish Bayou on the western
side of the bay
* Collected by a Petersen dredge about 3 km off the Biloxi-Ocean Spring coastline
TABLE 4. Mirex residues in esluarine water,
Mississippi Gulf Coasi— 1972-74
Sampling
Site
St Louis Bay
Mi&sissippi Sound
Amount
Residue
.5. ppb'
Collection
Extracted,
DATE
ML
Col I
Col n
3/1/74
4.000
0,007
0,000
6/20/74
4.000
0,005
0000
0,009
0,003
0,004
0,000
snnA
4.000
0001
0,001
7/31/74
4.000
0,004
0,001
0.007
0,000
5/1/72
4.000
0000
0 000
4/4/72
500
0,000
0000
11/15/72
500
OOOO
0000
5/15/73
4,000
0,030
0 001
6/12/73
4,000
0000
0000
2/22/74
4.000
0,010
0 003
0000
0001
0004
0 000
0,000
0000
3/1/74
4.000
0004
0 002
4/6/74
4.000
0,000
0,000
9/23/72
4.000
0,000
0,000
O0O4
0,000
4/6/74
4,000
0000
0 000
' All analyses were done with two columns to verify the mirex residue,
' Samples collected a few kilometers inland from St, l^uis Bay,
that only negligible amounts of mirex are incorporated in
the water (/. 10).
LITERATURE CITED
(I) Alley. E.G 1973. The use of mirex in control of the
imported fire ant. J. Environ. Qual. 2( 1 ):52-61 .
(2i de la Cruz. A. A., and K. Y. Lue . I97S. Mirex incorpora-
tion in the environment. In situ decomposition of fire ant
bait and its effects on two soil macroarthropods. Arch.
Environ. Contam. Toxicol. 7(1):47-6I.
(3) Food and Drug Administration. 1970. Pesticide Analytical
Manual. Vol. 3, U.S. Department of Health, Education,
and Welfare, p. 40.
(4) Lue. K. Y. 1977. Decomposition properties of mirex and
bait and its ecological effects on selected biotic systems.
Ph.D. Dissertation. Mississippi State University. Missis-
sippi State. MS. 89 pp.
(5) Lue. K. Y.. and A. A. de la Cruz 1978. Mirex incorpora-
tion in the environment: Toxicity in Hydra. Bull. Environ.
Contam Toxicol. 19(14):412-4I6.
(6) Markin. G. P.. J. H. Ford. J P. Hawthorne. J. H.
Spence. J. Davis. H. L. Collins, and C. D. Loftis. 1972.
The insecticide mirex and technique for monitoring. U.S.
Department of Agriculture-APHIS 81-3, 19 pp
(7) Markin. G. P.. J. C Hawthorne. H. L. Collins, and J. H
Ford. 1974. Levels of mirex and some other organo-
chlorine residues in seafood from Atlantic and Gulf Coastal
states. Pestic. Monit. J. 7(3/4): 139-143.
(8) Markin. G P.. H L. Collins, and J Davis. 1974. Resi-
dues of the insecticide mirex in terrestrial and aquatic
invertebrates following a single aerial application of mirex
bait, Louisiana— 1971-72. Pestic Monit. J. 8(2): 131-134.
(9) Naqvi. S M.. and A. A. de la Cruz. 1973. Mirex incor-
poration in the environment: residues in nontarget
organisms— 1972. Pestic, Monit J, 7(2):104-l 1 1.
(lOj Spence. J. H., and G. P Markin. 1974. Mirex residue in
the physical environment following a single bait applica-
tion, 1971-72. Pestic, Monit. J. 8(2): 135-139.
(II) Wolfe. J. L., and B. R. Norment. 1973. Accumulation of
mirex residues in selected organisms after an aerial treat-
ment, Mississippi— 1971-72. Pestic. Monit. J. 7(2):112-
116.
42
Pesticides Monitoring Journai
APPENDIX
Chemical Names of Compounds Discussed in This Issue
ALDRIN
AROCLOR 1248
DDD
DDE
DDT
DIELDRIN
ENDRIN
HEPTACHLOR EPOXIDE
LINDANE
MIREX
PCBs (polychlorinated biphenyls)
TDE
Hexachlorohexahydro-endo. exo-dimelhanonaphthalene 95% and related compounds 5%
PCB. approximately 48% chlorine
See TDE
Dichlorodiphenyldichloroelhylene (degradation product of DDT)
Dichlorodiphenyltnchloroethane
Hexachloroepoxyoctahydro-endo, exo-dimethanonaphlhalene 85% and related compounds 15%
Hexachloroepoxyoctahydro-endo, endo-dimethanonaphthalene
1 ,4.5.6.7,8.8-Heptachloro*2.3-epoxy-3a,4,7.7a-tetrahydro-4.7-melhanoindane
Gamma isomer of benzene hexachloride ( 1,2,3.4.5,6-hexachlorocyclohexane) of 99+% purity
Dodecachlorooctahydro- 1 ,3.4-metheno- 1 H-cyclobuIa[cd]pentalene
Mixtures of chlorinated biphenyl compounds having various percentages of chlorine
Dichlorodiphenyldichloroethane
Vol. 12, No. 1, June 1978
43
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 pesticide 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
in sufficient detail to permit interpretations and con-
clusions by author and reader alike. Such investigations
should be specifically designed and planned for moni-
toring purposes. The Journal does not generally publish
original research investigations on subjects such as
pesticide analytical methods, pesticide metabolism, or
field trials (studies in which pesticides are experimen-
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Authors are responsible for the accuracy and validity
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Pesticides Monitoring Journal
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Vol. 12, No. 1, June 1978
45
The Pesticides Monitoring Journal is published quarterly under the auspices of the
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mental Quality) and its Monitoring Panel as a source of information on pesticide
levels relative to humans and their environment.
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Editorial Advisory Board members are:
John R. Wessel, Food and Drug Administration, Chairman
Robert L. Williamson, Animal and Plant Health Inspection Service
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Address correspondence to;
Paul Fuschini (WH-569)
Editorial Manager
Pesticides Monitoring Journal
U. S. Environmental Protection Agency
Washington, D.C. 20460
Editor
Martha Finan
CONTENTS
Volume 12 - September 1978 Number 2
Page
SOIL
Biomacil and diiiroii residue levels in Florida citris soils , 47
David P. H. Tucker
FISH, WILDLIFE, AND ESTUARIES
Residues of peslieides and PCBs in estnarine fish. 1972-76 —
National Pesticide Monitoring Program 51
Philip A. Butler and Roy L. Schutzmann
Residues of organochlorine insecticides and polychlorinated hiphenyls in fisli from Lakes Huron and Superior,
Canada— 1968-76 60
Richard Frank, Micheline Holdrinet, Heinz E. Braun, Douglas P. Dodge, and George E. Spangler
Residues of organochlorine in'^ecticides and polychlorinated hiphenyls in fish from Lakes Saint Clair and Erie.
Canada~196S-76 69
Richard Frank, Heinz E. Braun, Micheline Holdrinet, Douglas P. Dodge, and Stephen J. Nepszy
Organochlorine residues in aquatic environments in Iran. 1974 S
A. Sodergren, R. Djirsarai, M. Gharibzadeh, and A. Moinpour
Chloriiuited hydrocarbon pesticide residues in Pacific oysters (Crassostrea gigas) from Tasmania. Australia — 1973 _ 87
Colin Edward Sumner
FOOD AND FEED
DDT residues in butter and inf(mt formula in India. 1977 91
G. S. Dhaliwal and R. I . Kaira
GENERAL
Organochlorine pesticides iu\d polychlorinated hiphenyls on sediments from a subarctic salt marsh,
Jimtes Bay, Canada — 1976 94
W. A. Glooschenko and R. C. J. Sampson
APPENDIX 96
liijorntalion for Coiilribulors 97
SOIL
Bromacil and Diuron Residue Levels in Florida Citrus Soils^
David P. H. Tuckers
ABSTRACT
The widespread use of herbicides in Florida citrus f,>rores
raises the possibility of residue uccuinulalion following
repeated applications. To determine residue levels of com-
monly used herbicides, soil samples were taken from larf>e
experimental plots in commercial furores in Polk and Hardee
Counties. Bromacil and diuron had been applied in com-
bination at both locations for 7-8 years. Analyses of san\ples
showed low levels of both herbicides at various soil depths
to 60 cm. Only a small amount of bromacil was detectable
one year after application, but diuron levels were higher.
Continuous applications at recommended rates and frequen-
cies have resulted in ma.ximum bromacil and diuron levels
of 3.9 percent and 13.1 percent, respectively, of their total
application.
Introduction
Integrated weed control programs used on large acreages
of citrus in Florida include herbicides, various cultiva-
tion practices, limited hand labor, and naturally occur-
ring weed pathogens and insect pests. Herbicides have
been widely used for the past decade, and have been
applied annually to a large percentage of nonbearing and
young-bearing acreage. Herbicides are now used on
older groves to control rapidly increasing annual and
perennial vines which thrive under tree canopies.
This widespread use of predominantly soll-sterilant herbi-
cides has caused concern about their accumulation with
repeated application. Therefore, continued monitoring
of their residual levels in major citrus-growing soil types
is warranted.
Bromacil and diuron are degraded in the soil by bio-
logical and nonhiological means, and they may be
'University of Florida, Cooperative Extension Service, Institute of
Food and Agricultural Sciences, Agricultural Research and Education
Center, Lake Alfred, FL 3.1850.
-Extension Horticulturist, University of Florida, Agricultural Researcli
and Education Center, Lake Alfred, FL 33850.
altered by one or more mechanisms including microbial
decomposition, adsorption, volatilization, leaching,
chemical degradation, and plant uptake {2,5,7,8). A
number of review papers on this general subject have
been presented (3. 4). The persistence of soluble
herbicides in soils in forms to.xic to plants is likely to be
less serious in humid areas such as Florida than in more
arid citrus-growing regions. The amount, frequency,
and intensity of rainfall is important to herbicide lon-
gevity in soil since moisture atfects herbicide efficacy
and mode of dissipation.
Tucker and Phillips (9) sampled the major citrus-
growing soil types which had received repeated applica-
tions of herbicides. Analyses of these samples for
bromacil, terbacil, dichlobenil, and trifluralin showed a
fairly predictable annual rate of dissipation from the
top 45 cm of the soil profile. The results precluded the
possibility of any substantial tcxicity to citrus trees due
to accumulation in the soils following repeated applica-
tions at recommended rates. The present paper presents
additional data showing levels of bromacil and diuron
following their commercial application to two soil types
at two grove locations over 7-8 years. Residue levels
are shown at different locations under the tree canopy
and at various depths.
Sampling and Aiutlysis
In 1969 and 1970, paired lO-acre blocks of citrus were
selected in commercial groves in Polk and Hardee
Counties. Soil types were Astatula fine sand (95 per-
cent sand, 0.42 percent organic matter, pH 7.8) and
Mayakka fine sand (99 percent sand, 0.38 percent
organic matter, pH 7.3), respectively. Annual rainfall
at both locations averaged 114-127 cm. The Hardee
County grove has a permanent overhead irrigation
system with supplemental irrigation averaging 30-50
cm/year. The Polk County grove receives only occa-
sional supplemental irrigation. At each site, weeds were
controlled by tillage in one block and by broadcast
Vol, 12, No. 2, September 1978
47
herbicides in the other. Generally, weed control was
satisfactory with one application ot herbicide each year.
However, in some years, herbicides were rc-applied when
weed growth resumed before the end of the season.
Herbicides were sprayed by a machine-mounted boom to
the entire grove floor area rather than in strips down
tree rows. Wettable powder formulations of bromacil
( 5-bromo-3-sec-butyl-6-methyluracil) and diuron [3-
(3.4-dichlorophenyl)-l,l-dimethylurea] in tank mixes
or as a chemically blended combination were used
throughout the experimental period. Soil samples were
collected with a 2.2-cm-ID soil tube from 0- to 15-cm
and 15- to 30-cm depths at both locations except at one
sampling time when samples were also taken from 30-
to 45-cm and 45- to 60-cm depths. Each sample was a
composite of 10 subsamples. Samples were taken in
row middles between trees, at the drip line or tree
canopy edge, and under the tree canopy. There were
three separate sampling times in Polk County and two
in Hardee County. Care was taken in obtaining the
lower depth samples to avoid the top soil layers falling
into the holes. To assure this, samples were taken
during optiniLmi soil moisture conditions. Samples
were stored at — lO'F before shipment for residue
analyses by the Dupont Company. Samples were
analyzed for bromacil by the microcoulometric gas
chromatographic method of Pease (6), and for diuron
colorimetrically after chromatographic cleanup by the
method of Dalton and Pease (/).
Results and Discussion
The data in Table 1 show that concentrations of bro-
macil and diuron at depths sampled are very low in both
locations compared to the total amoimts applied over
the 7-8-year experimental period. The levels, as per-
centages of the total amounts applied, range from 0.3
to 3.9 for bromacil and from 3.7 to 13.1 for diuron. As
percentages of the last application only, they range from
2.5 to 31.0 for bromacil and 33.6 to 84.6 for diuron.
This indicates that a substantial part of the residues
remains from the latest application within one year of
sampling.
Residues of diuron remained at considerably higher
levels in the soil than did those ot bromacil. This is
influenced primarily by their relative water solubilities:
800 ppm for bromacil and 42 ppm for diuron. Residue
levels do not appear to be influenced by the location of
sampling. Since precipitation is greater on the tree
drip line due to the umbrella elTcct of the tree canopy,
leaching would also be greater, resulting in an earlier
breakdown in weed control.
Other factors which may influence residue levels at
various sampling locations include photodecomposition
of diuron, probably greatest in the row middles due to
the high light intensity. Under tree canopies, where
sunlight breakdown and precipitation would be less,
adsorption of herbicides by organic matter and break-
down by microorganisms would be greater. Another
factor to consider is that spray coverage is frequently
poorer in areas where tree canopies hinder equipment
movement.
Inadequate spray coverage in the tree row also is
frequently due to poor overlap of spray patterns. In
most cases, bromacil was more evenly distributed
throughout the profile depth sampled than was diuron
where higher concentrations were consistently found in
the sLirface layers. Again, this is a reflection of the
much lower solubility of diuron and hence its slower
movement through leaching. Overall residue levels of
both herbicides were higher in the Mayakka fine sand
of Hardee County than in the Astatula fine sand of
Polk County.
Bromacil levels in control samples taken from cultivated
plots are at or very close to the lower end of the detec-
tion limit of the test procedure. Siich background levels
are not unusual in analyses of soils for herbicide residues.
The levels of diuron are, however, more finite, and an
explanation of these levels in the nontreated soil sample
is more difticult. Contamination of soil in the cultivated
blocks may have occurred when sandy soils were blown
in during the dry windy season or washed in during
heavy rains. Equipment movement throughout the
experimental areas may also account for some move-
ment of herbicides in the surface soil. The fact that
diuron remains in the sLirface of the soil profile for
longer periods would allow for greater movement than
bromacil which is more rapidly moved into the lower
soil profile.
From the data presented, it is evident that bromacil and
diuron levels are relatively low in the ()-60-cm layers of
the soil types sampled. Since soil was not sampled
below 60 cm, the extent of residue movement through
leaching into the lower soil profile is unknown. However,
the data suggest that residue levels do decrease with
depth. Although soil samples were not collected yearly,
the data indicate that the degree of accumulation would
not lead to cumulative levels toxic to citrus at rates
used in commercial practice. This statement is supported
by the fact that the tree foliage has not exhibited phyto-
loMcity symptoms throughout the experimental period.
Rather, residues are steadily dissipating through leaching
and ileizradation.
48
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Vol. 12, No. 2, September 1978
49
LITERATURE CITED
(/) Dulton. R. L.. and H. I.. Pease. 1962. Delerminution of
residues of diuron. monuion, fenuron, and neburon.
J. Assoc. Off. Agric. Chem. 45( 2 ) :377-38l.
(2) Ganlincr, J. A., et al. 1969. Synthesis and studies with
2-C'^-labeled bromacil and lerbacil. J. Agric. Food
Chem. 17(5) :980.
(.?) Geisshiililer, //.. and G. Vos.^. 1971. MetaboMsm of
substituted urea herbicides. Pages 305-322, in A. S.
Tahori (ed.). Pesticide Terminal Residues. Interna-
tional Union of Pure and Applied Chemistry Sym-
posium, Tel-Aviv, Israel.
(4) Coring, C. A. I., D. A. Laskowski. J. W. Hanutker, and
R. W. Meikle. 1974. Pages 135-172 in Riswanul
Haque and V. H. Freed (eds.). Environmental dynam-
ics of pesticides. Proc. Symp. Environ. Dynami(;s
Pestic, Los Angeles, CA.
{5) Hill. G. D., et al. 1955. The fate of substituted urea
herbicides in agricultural soil. Agron. J. 47:93-104.
(6) Pease, H. L. 1966. Determination of bromacil residues.
J. Agric. Food Chem. 14(l):94-96.
(7) Rhodes, R. C. I. J. Belasco. and H. L. Pease. 1970.
Determination of mobility and adsorption of agri-
chemicals in soils. J. Agric. Food Chem. 18(3) :524—
528.
(cS) Torgc.son, D. C, and H. Mee. 1976. Microbial degra-
dation of bromacil. Proc. NEWCC 21:584.
(9) Tucker. D. P., and R. L. Phillips. 1969. Movement and
degradation of herbicides in Florida citrus soils. Fla.
State Hort. Soc. 81:72-75.
50
Pesticides MoNriouiNc. Journal
FISH, WILDLIFE, AND ESTUARIES
Residues of Pesticides and PCBs
in Estuarine Fish, 1972-76 — National Pesticide Monitoring Program
Philip A. Butler' and Roy L. Schiitzmann^
ABSTRACT
This report .summarizes 1524 analyses of juvenile fish col-
lected semiannually in 144 estuaries nationwide from July
1972 through June 1976. Pooled samples of 25 whole fish
were screened for 20 common pesticides and polychlorinated
biphenyls (PCBs). The three most common residues. DDT.
PCBs, and dieldrin, were found in J9, 22, and 5 percent of
the samples, respectively. Data indicate that estuarine
pollution levels continue to decline.
[iitroiliiclioil
The economic and aesthetic importance of estuaries
prompts many investigations to determine the causes and
effects of imbalances in these sensitive ecosystems. The
most comprehensive program was the monthly surveil-
lance in 1965-72 for pesticide pollution of molkiscan
populations (4). The nationwide study identified the
widespread contamination of estuarine fauna with DDT
and demonstrated that DDT levels had peaked and were
declining.
The persistence of DDT and other synthetic organo-
chlorines made it desirable to continue monitoring
estuarine areas, but it was necessary to reduce the ana-
lytical workload of the monitoring program. Unfortu-
nately, residue data from molluscan populations are best
understood when obtained contintially. The animals
purge themselves rapidly when pollution loading is
intermittent (i).
The literature on accumulation and long storage of
synthetic compounds by fish indicated that fish could be
sampled less frequently than mollusks. However, little
information was available on the sensitivity or selectivity
^Ecological Monitoring Branch. Technical Services Division, U.S. En-
vironmental Protection Agency, Gulf Breeze. FL .tZSbl.
= Ecological Monitoring Branch, Pesticides Monitoring Laboratory,
U.S. Environmental Protection Agency, Bay St. Louis, MS 39529.
of different species of fish in acquiring residues of specific
pollutants or combinations of pollutants. Also, it was
difficult to determine when and where migratory species
acquired residues.
Sample Selection ciitd Collection
Many species of estuary fish spend only their first year
within a single estuary; other species may spend their
lifetime in an estuary. Presumably, fish less than a year
old would reflect pollution levels during the preceding
few months at or near where they were caught. So,
each estuary was monitored at 6-month intervals in the
spring and fall.
The geographic e.xtent of this program meant that com-
parisons of residues in ditTerent species would be ques-
tionable. Consequently, in a given estuary, the same two
species of fish were collected for the duration of the pro-
gram. The two species represented different food webs,
e.g., a carnivore and a particle feeder. This manner of
sampling made it possible to detect pollution trends over
the 4-year period.
Fish were collected with trawls and beach seines in 144
primary and secondary estuaries in 19 coastal states,
Puerto Rico, and the Virgin Islands. Monitoring in
Alaska, Hawaii, and Mississippi was limited to one
year, but in most areas, si.K to eight semiannual collec-
tions were made during five calendar years. The 154
species collected represent 52 of the 175 families of
marine fishes of North America (/). Some species and
estuaries were monitored only once to identify possible
problem areas. More than 60 species were sampled at
least three times, and 22 species were collected in the
estuaries of three or more states (Tables 1,2). About
38,000 fish were analyzed in groups which made up
1524 samples.
Vol. 12, No. 2, September 1978
51
TABLE
1 . Suiniiuiry of cstuariiie fish colh
■clions.
July
1972-Junc 1976
Number
Number
Number
Number
OF Years
OF
OF Fish
OF
Coastal Area
MoNnoRED
Estuaries
Species
Samples'
Alabama
3
3
4
13
Alaska
1
8
17
37
California
4
7
17
82
Conncclicul
4
4
3
39
Delaware
4
3
11
57
Florida
3
11
22
66
Georgia-'
4
9
15
74
Hawaii
1
8
14
22
Louisiana
2
14
14
51
Maryland
4
8
8
140
Mississippi
1
4
6
21
New Yorl<
4
3
4
46
North Carolina
4
19
28
251
Oregon
3
5
13
178
Puerto Rico-
3
5
14
25
Rhode Island
4
1
2
32
South Carolina-
4
6
5
99
Texas
4
9
8
51
Virginia
3
3
5
55
Virgin Islands-
2
8
19
28
Washington stale
4
6
3
157
TOTAL
144
154'-
1524
'Each sample consisted ol" 25 Hsh less than one year old.
-Some monitoring data for 1972-74 have also been published for these
four coastal areas (see literature references //. I2i.
■Different species, some species were collected in more than one slate.
Sample Prefuiraiioii
Earlier laboratory investigations indicated that analyses
of 15 randomly selected fish would cover the range of
individual variations in pesticide concentrations in
experimentally exposed fish populations (2). In the
present study, 50 yearling fish were collected semi-
annually and analyzed in pools of 25 each. Whole fish
samples were homogenized, and an aliquot was blended
with a desiccant as described in the molluscan program
(4). The prepared samples were shipped unrefrigerated
to the Pesticides Monitoring Laboratory, U.S. Environ-
mental Protection Agency, Bay St. Louis, Mississippi,
for analysis.
Analylical Procedure
Desiccated samples were shaken with acctonitrile for 4
hours, and partitioned and cleaned by the Mills method
(8); methylene chloride and hexanc were used to elute
the Florisil cokinin (9). The extract was analyzed by
flame photometric detector before Florisil cleanup to
avoid possible loss of organophosphorus compounds (6).
Polychlorinatcd biphenyls (PCBs) were separated from
other chlorinated compounds by the silicic acid method
(7). Instrument parameters and operating conditions
used for gas chromatographic analysis and confirmation
are given in Table 3. Samples were routinely screened
for residues of the synthetic compounds listed in Table
4. The recovery range for organochlorines was 75-85
percent, and for organophosphatcs, 85-95 percent.
Results and D
ISCIISSK'll
i;Di)i
DDT is persisteni in sediments with high organic content;
its presence long after ils use has been lerminated is not
52
surprising. However, DDT residues found recently in
fish a few months old are not so easily explained. Of the
states and territories monitored, DDT was absent only
from Alaska, Hawaii, and the Virgin Islands (87 sam-
ples). In 595 samples, 39 percent, DDT was detected at
levels of lO-H /j.g/kg (Table 5). In many areas, DDT
residues were consistently present in small amounts in
fish only a few months old. However, these low levels
probably are biologically insignificant. Some samples
from California, Delaware, Florida, and New York had
DDT residues in the 1 000-4000-/,g/kg range. DDT
burdens this high could cause physiological stress and
lessen reproductive capacity in fish populations (5).
The larger residues surpass levels observed in oysters
in the same estuaries in 1965-72 when DDT was still
being used. The fact that the half-life of pesticide residues
is much shorter in mollusks than in fish may explain
this paradox.
Coastal areas are ranked in the order of frequency and
magnitude of -DDT residues in Table 6. Not surpris-
ingly, the 10 areas with the highest frequency of positive
fish samples are essentially the same coastal areas which
had the highest frequency of -DDT-positive molluscan
samples during 1965-72. However, there was a 30 per-
cent decline in the overall frequency of DDT-positive
samples of fish compared to mollusks in the 13 states
where both were monitored. This decline was not uni-
form; in Delaware, the frequency remained at 75 per-
cent, and in Washington state it declined from 1 1 to 4
percent.
Examination of the percentage distribution of DDT and
its metabolites, TDE and DDE, in residues indicates to
some extent the movement of DDT in the estuarine en-
vironment in recent years (Table 7). There has been a
well defined shift from the large proportion of DDT in
1972 to its absence from fish samples collected in 1976
and the concomitant increase in levels of DDE. Yet,
there has been no significant change in the mean residues
of i:DDT present during the 4-year period (Table 8).
This suggests that DDT is continually recycled in the
food web since it occurs in juvenile fish, and, in moving
along biological pathways. DDT is gradually metabolized
to the more stable compound. More important, it indi-
cates that DDT is no longer being introduced into the
estuarine environment and th;it a pollulani can be con-
trolled nationwide by enforcing legislation.
POl ^CHLOUlNATKD lilPHHNIlS (PCBs)
PCBs were identified in 331 samples, 22 percent of the
total analyzed. Residues were quantitated by compari-
son with standards of Aroclors 1242, 1254, and 1260.
In the data tabtilations, PCBs are reported as a single
entity regardless of the standard used to quantitate them.
Thus, residues consisting of more than one PCB are not
fully identified, :tnd reported dal.i oi the actual amounts
may vary.
Pesticides Monitorinc. Journ.m.
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Vol. 12, No. 2, September 1978
53
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54
PCBs were not found in samples from Alaska and Mis-
sissippi. In 1 1 states, Puerto Rico, and the Virgin Islands,
Aroclor 1254 was the only standard used. In the remain-
ing six coastal areas, standards of Aroclors 1242 and
1260 were occasionally required as well for the quanti-
tation of residues (Table 5). The annual incidence of
PCB-positive samples is summarized in Table 8. Data
indicate a gradual decline in both the ma.ximum residues
observed in most years and the average concentration
of the PCB residues. The changes were e.xpected in view
of the general curtailment in production and use of the
compounds. Their chemical persistence suggests, how-
ever, that they will continue to contaminate the environ-
ment for several years.
Only at one station each in Delaware and Washington
state did PCB residues frequently exceed 1000 Mg/kg.
Such data do not indicate high PCB levels in the ambient
water since residues are cumulative and fish may have
had up to one year of exposure. However, controlled
experiments show that PCB concentrations as low as 1.0
Mg/kg are sufficient to cause fin rot and increased mor-
tality in chronically exposed fish (10).
Coastal areas are ranked in order of the frequency and
magnitude of PCB residues in estuarine fish (Table 9).
These residues were found in 19 of the 21 areas moni-
tored, but in only tour states were they present in more
than half the samples. In contrast. DDT residues were
found in 18 areas and were present in more than half
the samples from nine states. This indicates a much
broader contamination of the environment with DDT
than with PCBs.
The incidence of PCB residues in fish cannot be com-
pared with the much lower frequency observed in mol-
lusks in 1970-72. PCBs are an industrial pollutant and
are not usually found where shellfish are harvested.
DIELDRIN
Residues of dieldrin were delected in 74 samples, 5 per-
cent of the total samples, ranging from 10 Mg^kg to 145
Mg/kg. Positive samples were collected in some of the
estuaries of 12 states and the Virgm Islands (Table 10).
About halt the positive samples were collected in sec-
ondary estuaries in the Maryland section of Chesapeake
Bay. Samples from this area conlained dieldrin in 1972-
74, but not in 1975. Dieldrin was found in a variety of
fish species, but its presence had no apparent correlation
with their different feeding patterns. In 1972-74, diel-
drin was found in about 7 percent of Ihe fish samples;
but in 1 975-7(1, less than I percent of the samples con-
tained detectable levels (Table 8). During the 1965-72
monitoring of mollusks, dieldrin was found in 15 percent
i>f the samples at levels approximately double those de-
tected in the juvenile tish.
Pesticides Monitoring Journal
TABLE 3. Operating parameters for analyzing estiiarine fish for pesticide and PCB residues— 1972-76
Detector
CoLUM^
Electron- Glass, 1.8 m long x 4 mm ID, packed with
capture 3 percent DC-200 on 80-100-mesh Supelcoport
Electron- Glass, 1.8 m long X 2 mm ID, packed with
capture a mixture of 1.5 percent OV-17 and 1.95 per-
cent OV-210 on 80-100-mesh Supelcoport
Electron- Glass, 1.8 m long x 2 mm ID. packed with
capture 5 percent OV-210 on 80-UIO-mesh Supelcoport
Flame Glass, 1.8 m long x 4 mm ID, packed with
photometric 3 percent OV-IOI on 80-100-mesh Chromosorb
W-HP
Column
Temperatures, °C
Detector
Carrier Gas,
Flow Rate
188
300
250
Argon/methane
50 ml/minute
193
200
230
Nitrogen
30 ml/minute
173
200
230
Nitrogen
30 ml/minute
177
184
230
Nitrogen
50 ml/minule
TABLE 4. Coinpoiimls detected by gas cliromatograpluc
analysis of estiiarine fish tissue — 1972-76^
Organochlorine
ORUANOPHdSPHATE
Aldrin
Chlordane
DDT
Dieldrin
Endosulfan
Heptachlor
Lindane
Methoxychlor
Mirex
PCBs
Toxaphene
Trifluralin
Azinphosmcthyl
Carbophenothion
DEF
Demeton
Diazinon
Ethion
Malathion
Parathion
Phoraic
NOTE: See appendix for cllcmical names of compounds.
'Lower delcclion Hmit is 10 ;ig kg for all compounds except the fol-
lowing: endosulfan. 20 /ig'kg: methoxychlor and ethion, M ^g, kg;
mirex, PCBs. toxaphene, carbophenothion, and DEF, 50 ng kg.
PESTICIDES OCCASIONALLY DETECTED
Despite the fact that all samples were routinely screened
for 21 synthetic hydrocarbons and their oxygen analogs,
few were detected. DDT and its metabolites, dieldrin,
and PCBs were the most common residues. Only si.x
other pesticides were found in measurable amounts
(Table II). These were detected in 48 samples or about
3 percent of the total. A majority of these residues
occurred in fish from the upper end of Chesapeake Bay
and along the Texas coast. The insecticide endrin and
the herbicide Dacthal (DCPA) were also identified in
fish from a heavily farmed area in the Texas Rio Grande
river basin. This area was monitored monthly and the
data will be presented in a separate publication.
DATA INTERPRETATION
The data are organized on a seasonal and geographic
basis, i.e., by state boundaries, in an effort to make the
large group of heterogenous samples more manageable.
Unfortunately, some details of localized pollution pat-
terns are lost in the process. For example, data from
only one river basin in Rhode Island can be compared
with data from 3-19 river basins in other states. Or, as
in Washington state, data from one polluted estuary were
averaged with five other relatively clean areas in the
state. In Table 9, the frequency of PCB residues is
shown as 17 percent in Washington. Actually, all 27
samples from the Duamish River were contaminated,
but none of the 128 samples from the other five estuaries
contained PCB residues during the 4-year period.
PCB residue data from the Duamish River samples illus-
trate the importance of sampling continuity to determine
localized pollution patterns and trends. The Pacific stag-
horn sculpin and English sole were both collected seven
times in the 4-year period. Quantitation of the PCB
residues required three different standards (Table 12).
The residues were probably mixtures of two or more
PCBs, but the data indicate both a shift in the kind of
pollution and a decline in pollution levels.
There must always be some ambiguity in the compari-
son of residue data from ditTerent species in the absence
of controlled experiments on their ability to accumulate
pesticides. In the Duamish River samples, the consis-
tently higher residue levels in English sole probably were
due to a ditTerence in age rather than in species. Sole
populations sampled were usually about 6 months older
than Ihe sculpins.
Comparisons of residue data in a single fish species dis-
tributed over a wide geographic range permit valid judg-
ments of regional pollution differences. The bay anchovy
was the most widely distributed species in the present
program. It was collected in 37 estuaries in the 1 1 states
from Delaware to Texas over a 3-year period. Samples
from three estuaries in Georgia and three in Louisiana
contained no detectable DDT or PCBs. in contrast, 42
bay anchovy samples collected in Delaware and Chesa-
peak Bay during this 3-year period contained residues
of DDT ( 10-467 Mg/kg, mean 77) and PCBs (90-996
/ig/kg, mean 340). On the basis of such data, it is pos-
sible to identify regional pollution patterns when juvenile
fish of the same species are monitored periodically.
In general, residue data from all the estuaries in a single
state were strongly skewed because only one or two estu-
aries were highly polluted. In Washington state, less
Vol. 12, No. 2, September 1978
55
TABLE 5. Residues of ^Dl^T and PC lis in wliolc-hody samples of juvenile esluiirine fisii, 1972-76
Residues, ^c/kg Wet Weight
JDDT
PCBs
Coastal Area,
Number of
Year
Samples
Alabama
1972
2
1973
2
1975
3
1976
6
Alaska
1972
7
197.1
30
California
1972
6
1973
21
1974
17
1975
18
1976
20
Connecticut
1972
4
1973
7
1974
15
1975
5
1976
8
Delaware
1972
6
1973
12
1974
14
1975
9
1976
16
Florida
1972
25
1973
15
1974
19
1975
7
Georgia
1972
12
1973
17
1974
10
1975
18
1976
17
Hawaii
1972
8
1973
14
Louisiana
1975
24
1976
27
Maryland
1972
22
1973
45
1974
45
1975
28
Mississippi
1972
5
1973
16
New York
1972
6
1973
10
1974
12
1975
6
1976
12
North Carolina
1972
30
1973
80
1974
70
1975
41
1976
30
Oregon
1973
77
1974
66
1975
35
Number
PoSlltVE
Maximlim
Residue
Geometric X
OF Positive
Samples
Number
Positive
Maximum
Residue
4
19
15
15
18
6
12
13
8
4
8
4
17
5
14
26
35
6
3
5
10
5
10
29
34
26
18
18
21
22
3
82
17
35
49
213
667
1422
1349
2588
63
68
43
97
1425
636
1194
1146
1015
170
18
1640
23
65
14
32
16
108
23
184
345
694
714
16
159
174
115
11)6
4082
11)4
140
357
322
78
140
125
221
12
67
17
20
35
69
75
69
79
95
43
68
26
25
220
85
109
181
471
25
13
36
21
26
13
32
16
52
23
55
73
51
251
14
135
71
49
34
188
39
43
39
39
24
33
29
32
11
0
2
5
6
12
4
7
14
5
4
0
0
16
1
14
12
16
9
5
2
10
2
10
15
1
3
1
2
271)
512
432
400
592
678
1065
497
289
4504
2671
823
1566
1258
614
104
508
137
305
256
788
1046
878
940
310
235
301
694
447
786
120
174
173
538
277
247
288
163
229
224
210
254
313
321
406
252
172
1469
802
258
720
649
62
104
508
137
244
256
351
318
287
267
231
149
165
471
295
258
120
131
173
527
130
1 79
236
(Continued next page)
56
Pesticides Monitoking Journal
TABLE 5 Cconfd.).
Residues of SPPT and PCBs in whole-body samples of juvenile estuarine fish. 1972-76
Coastal Area,
Number of
Year
Samples
Puerto Rico
1972
4
1973
8
1974
4
1976
9
Rhode Island
1972
4
1973
g
1974
8
1975
8
1976
4
South Carolina
1972
12
1973
25
1974
21
1975
22
1976
19
Texas
1972
7
1973
9
1974
11
1975
18
1976
6
Virginia
1973
26
1974
11
1975
18
Virgin Islands
1972
6
1973
13
1974
9
Washington state
1972
21
1973
48
1974
48
1975
24
1976
16
Number
Positive
2
1
0
5
0
0
5
4
0
7
13
6
2
0
5
5
8
12
4
20
10
7
0
0
0
0
1
1
0
4
Residues, /io/kg Wet Weight
2DDT
Maximum
Residue
157
172
86
78
20
60
33
29
12
52
188
223
59
70
124
60
821
25
11
38
Geometric X
OF Positive
Samples
100
172
24
17
29
16
19
11
38
S2
65
23
37
39
39
115
25
11
32
Number
Positive
2
2
4
0
4
4
8
4
4
1
0
0
0
0
3
0
4
4
1
PCBs
Maximum
Residue
201
416
579
477
797
524
241
356
182
267
240
265
157
438
456
2549
166
809
4903
3363
2028
2639
900
Geometric X
of Positive
Samples
NOTE: Samples from Alaska conlained no PCBs.
181
316
238
451
464
231
230
275
182
136
95
150
157
214
254
850
142
615
2552
1577
1515
2057
668
,,.,,;,, . , ,-,,„ ^.-. Aroclor 1 254 was used as the slandard in all olher coaslal
addii ons. Aroclor 126(1: Cahlornia, Connecticut. Delaware. Maryland, North Carolina, and Washin.i
Maryland. North Carolina, and Washington state. asning.
areas with the following occasional
on state; Aroclor 1242: Delaware,
TABLE 6. Frequency and average concenlration of IDDT
residues in juvenile estuarine fish by coasted area. 1972-76
Average
Frequency
Concen-
Coastal
OF
Coastal
tration,
Area
Residues, %
Area
/IG/KG '
California
87
Delaware
213
Delaware
75
Maryland
108
New York
72
Puerto Rico
10(1
Alabama
69
California
77
Virginia
67
New York
76
Texas
67
Mississippi
75
Maryland
58
Virginia
64
Florida
52
Texas
49
North Carolina
48
Connecticut
41
Puerto Rico
32
Louisiana
38
Connecticut
31
North Carolina
36
Mississippi
29
Alabama
35
South Carolina
29
Florida
24
Rhode Island
28
Oregon
24
Oregon
26
Washington state
23
Louisiana
12
Georgia
1?
Georgia
10
Rhode Island
21
Washington slate
4
South Carolina
19
Alaska
0
Hawaii
0
Virgin Islands
0
NOTE: Comparisons are limited in that the number of samples, nun
ber of sampling stations, period (years) of sampling, and
species of fish differ for each coastal area.
•Arithmetic average of geometric means of positive samples in all
collection years.
than 4 percent ot the samples collected in 5 years con-
tained measurable residues of DDT. The geometric
means of the positive samples, along with the maximum
residue detected and the number of positive samples, is
the best summary of actual pollution levels. Conversely,
the geometric means of the residue data from year to
year in a given state were normally distributed, and the
arithmetic means were used to compare pollution levels
in ditTerent geographic areas (Tables 6, 8. 9). Plans are
finder way to store sample and analytical data in a com-
puter data bank to provide more precise data analyses in
stLidies of localized polkition problems.
TABLE 7. Percentage distribution of metabolites in ZDDT
residues in juvenile estuarine fisli by coastal area, 1972-76
Year
Number of
Positive Samples
Distribution. %
DDT
TDE
DDE
1972
1973
1974
1975
1976
90
167
173
97
68
23
12
5
1
0
37
30
36
21
14
40
58
59
78
86
Vol. 12, No. 2, September 1978
57
TABLE 8. Annual iiicUlciwe of ZDDT, PCB, and dielilrin residues in juvenile whole fish samples, 1972-76
No. OF
Samples
Residues, /ig/kg
DDT
PCBs
DiELDRIN
Year
PosnivE
Maximum
Residue
Average
Residue'
Positive
Maximum
Residue
Average
Residue'
%
Positive
Maximum
Residue
Geometric
X
1972
1973
1974
1975
1976
187
483
380
284
190
48
34
46
34
36
1425
667
1640
4082
2588
62
58
42
69
88
34
12
29
20
22
4903
3363
2028
2639
1258
540
429
320
460
351
7
6
8
1
0
140
140
145
15
21
30
12
14
' Arithmclic average of the geomelric means of positive samples from each coastal area.
Conclusions
Juvenile fish arc satisfactory tools for gauging pesticide
pollution trends in estuaries provided at least 25 indi-
viduals. 6-12 months old, of the same species are sam-
pled annually at a specific location. AnaUses of the same
species of fish at different geographic locations permit
valid comparisons of pollution levels.
Existing i;DDT residues are the result of biotic recycling,
and probably little, if any. DDT has been introduced
recently into the cstuarine systems monitored in this
study.
The magnitude and frequency of biotic residues of DDT,
dicldrin, endrin, and toxaphene declined substantially
between 1965-70 and 1972-76.
Data from this study warrant annual monitoring of juve-
nile fish in the nation's estuaries.
Aclinowledginent
The autht)rs arc greatly indebted to many people for the
success of this monitoring program. We thank espcciall>'
TABLE 9. Frequency and average concentration of PCB
residues in juvenile estiiarine fish by coastal area, 1972-76
Average
Frequency
Concen-
Coastal
OF
Coastal
tration,
Area
Residues. %
Area
;iG/KG'
Connecticut
87
Washington state
1674
Rhode Island
75
Delaware
780
New York
63
Virginia
439
Delaware
51
Virgin Islands
379
Virginia
38
Rhode Island
330
Maryland
36
Connecticut
323
Puerto Rico
32
Georgia
323
California
31
Maryland
306
Florida
26
New York
262
Texas
24
Louisiana
256
Alabama
23
Puerto Rico
245
Virgin islands
18
Hawaii
244
Washington state
17
North Carolina
242
Hawaii
14
California
229
Oregon
10
Oregon
182
North Carolina
9
South Carolina
182
Georgia
3
Alabama
163
Louisiana
2
Texas
135
South Carolina
1
Florida
83
Alaska
11
Mississippi
0
NOTE; Comparisons arc limited in ihal (he number of samples, num-
ber of sampling Malions, periods (years) of sampling!, and
stpccics of lish difTcr lor each coastal area.
^Arithmetic average of jieumeiric means of positive samples in all
collection years.
TABLF 10. Geographic incidence of ilieldrin residues
in juvenile estuarine fish, 1972-76
Number
Mean
Coastal
OF
Number
Residue.
Area
Samples
Positive
liC/KC
California
82
2
34
Connecticut
39
3
15
Delaware
57
2
59
Florida
66
12
10
Georgia
74
T
60
Louisiana
51
1
15
Marvland
140
35
30
Mississippi
21
2
17
New York
46
2
24
North Carolina
251
4
20
Texas
51
6
20
Virginia
55
2
10
Virgin Islands
28
1
10
June Hartsfield for helping to summarize the data and
for typing the manuscript, and Michael Reuschel for
help with the tables. We thank Charles D. Kennedy for
countless analyses, and we thank Stanley S. Mecomber
at the Pesticides Monitoring Laboratory.
Fish samples were collected through the cooperation of
state, federal, and university marine laboratories. These
agencies and their principal investigators are: University
of Alabama Marine Sciences Program, G. Crozier;
National Marine Fisheries Service, Auke Bay, Alaska
Laboratory, H. S. .Sears; California Department of Fish
and Ciame, W. Griffith; National Marine Fisheries Ser-
vice, Connecticut Biological Laboratory, A. Calabrese;
University of Delaware College of Marine Studies, R. W.
Smith; University of South Florida Marine Science Insti-
tute, R. Baird; University of Miami School of Marine
and Atmospheric .Science, B. Yokel; National Marine
Fisheries Service, Panama City Laboratory, E. Naka-
nuira; University of Georgia Marine Institute, R. J.
Reimold (also made collections in Puerto Rico and the
Virgin Islands); University of Hawaii Institute of Marine
Biology, J. H. Bardach; University of Southwestern
Louisiana. H. D. Hoese; University of Maryland Chesa-
peake Biological Laboratory. 1 . Ritchie; Gulf Coast Re-
search Laboratory. T. I-. Lytic; University of North
Carolina Institute of Marine Science, A, F. Chestni.it;
University of Oregon Marine Science Center. R. S. Cald-
well; University of Puerto Rico Department of Pharma-
cology, T. Morales-Cardona; University of Rhode Island
Oceanograph\ Department, D. R, Sheehy; South Caro-
58
Pesticides Monitorinc, Journ.m
State
TABLE 1 1. Pesticide residues occasionally detected in juvenile estuarine fish, 1972-76
Chiordane
Heptachlor
Epoxide
TOXAPHENE
Ethyl
Parathion
Methyl
Parathion Carbophenothion Ethion
Alabama
1-13-133
Connecticut
1-39-10
Hawaii
6-22-290
Louisiana
1-51-504
Maryland
22-140-118
3-140-15
Mississippi
2-21-388
New York
2^6-207
North Carolina
1-251-12
Texas
3-51-75
3-51-75
2-51-47
1-51-103
1-51-83
NOTE: Data in columns represent incidence, number of samples, and mean residue, Mg/kg, respectively.
lina Wildlife and Marine Resources Department, M, H.
Shealy, Jr.; Texas Parks and Wildlife Department, R.
Childress; Virginia Institute of Marine Science, R. J.
Huggett; State of Washington Department of Fisheries,
B. Pattie; and University of Washington Fisheries Re-
search Institute, B. Miller.
TABLE 12. Treiuls in PCB residues ill Englisli sole and
Pacific stai>liorn scittpin. Dininiisli River, Waslungton state,
fall 1972-spring 1976
Most Similar
Aroclor St
^NDARDl
Date
Species
1254
1260
1242
Fall 1972
E
P
3346
2202
Spring 1973
E
P
2111
2065
Fall 1973
E
P
1683
1129
Spring 1974
E
P
1927
1477
Fall 1974
E
P
1733
825-
Spring 1975
E
F
2541
1832
Spring 1976
E
888
1241
P
506
492
NOTE: E = English sole, P ~ Pacific staghorn sculpin.
^ Data represent average of two sample pools of 25 fish each (.wet
weight, ^g/kg).
-Only one sample.
LITERATURE CITED
(/) Bailey, R. M., J. E. Fitch, E. S. Herald. E. A. Laciuter,
C. C. Lindsey, C. R. Robins, and W. B. Scott. 1970.
A list of common and scientific names of fishes from
the United Slates and Canada. Third ed. Am. Fish.
Soc. Spec. Publ. No. 6, Washington, D.C. 150 pp.
'■?) Butler, P. A. 1969. Significance of DDT residues in
estuarine fauna. Pages 205-220 in Chemical Fallout.
Charles C Thomas, Springfield, 111,
(.?) Butler, P. A. 1971. Influence of pesticides on marine
ecosystems. Proc. Roy. Soc. London B. 1970: 321-329.
(4) Butler, P. A. 1973. Organochlorine residues in estuarine
mollusks, 1965-72 — National Pesticide Monitoring
Program. Pestic. Monit. J. 6(4) :238-362.
(5) Butler, P. A., A. J. Wilson. Jr., and R. Childress. 1972.
The association of DDT residues with losses in marine
productivity. Pages 262-266 in Marine Pollution and
Sea Life Fishing News Ltd. Books, London, England.
(6) Luke, M. A., J. E. Frobcrg, and H. T. Masumolo. 1975.
Extraction and cleanup of organochlorine, organo-
phosphate, organonitrogen, and hydrogen pesticides in
produce for determination by gas-liquid chromatog-
raphy. J. Assoc. Off. Anal. Chem. 58(5) : 1020-1026.
(7) Masumoto, H. T. 1972. Study of the silicic acid pro-
cedure of Armour and Burke for the separation of
PCB's from DDT and its analogs. J. Assoc. Off. Agric.
Chem. 55(5): 1092-1 100.
(S) Mills, P. A., J. H. Onley. and R. A. Gaither. 1963.
Rapid method for chlorinated pesticide residues in
nonfatty foods. J. Assoc. Off. Agric. Chem. 46(2):
186-191.
(9) Mills, P. A.. B. A. Bong, L. R. Kanips. and J. A. Burke.
1972. Elution solvent system for Florisil cleanup in
organochlorine pesticide residue analyses. J. Assoc. Off,
Agric. Chem. 55(1) :39-43.
(10) Nimmo, D. R., D. J. Hansen, J. A. Couch, N. R.
Cooley, P. R. Parrish. and J. 1. Lowe. 1975. Toxicity
of Aroclor 1254 and its physiological activity in sev-
eral estuarine organisms. Arch. Environ. Contam.
Toxicol. 3(l):22-39.
(//) Reimold, R. J. 1975. Chlorinated hydrocarbon pesti-
cides and mercury in coastal biota, Puerto Rico and
the U.S. Virgin Islands— 1972-74. Pestic. Monit. J.
9(l):39-43.
{12) Reimold, R. J., and M. H. Shealy, Jr. 1976. Chlori-
nated hydrocarbon pesticides and mercury in coastal
young-of-the-year finfish. South Carolina and Georgia —
1972-74. Pestic. Monit. J. 9(4) : 170-175.
Vol. 12, No. 2, September 1978
59
Residues of Organochlorine Insecticides and Polychlorinated Biphenyls
in Fish from Lakes Huron and Superior, Canada — 1968-76 '
Richard Frank," Micheline Holdrinet,- Heinz E. Braiin,-
Douglas P. Dodge,' and George E. Sprangler'
ABSTRACT
Five species of fish from Lake Superior and 12 species from
Lake Huron were analyzed for ori;anoclilorinc pesticides and
polychlorinated biphenyls (PCBsj between 1968 and 1975.
Mean residues of ^DDT peaked at 1 .72 ppm and 7.60 ppin
in lake trout (Salveliniis namayciish) from Lakes Superior
and Huron, respectively. By 1975, the mean level of '^DDT
had decreased in lake trout and was liighest in bloaters
(Coregoniis hoyi) from both lakes: 1.06 ppm and 1.87 ppm.
respectively. Dieldrin levels in fisli from Lake Superior
changed little over the .same period. However, in 1969-70.
dieldrin levels in fish from Lake Huron exceeded the 0.3
ppm tolerance level set by Health and Welfare Canada or the
Food and Driit; Administration, U.S. Department of Health.
Education, and Welfare in 5 percent of lake whilefish (Core-
gonus cliipeaformis) and 10 percent of bloaters. By 1975.
50 percent of bloaters caught in Georgian Bay and North
Channel hud dieldrin levels above 0.3 ppm. PCB residues
declined in lake trout and lake whitefish caught in Lake
Superior between 1971 and 1975, but increased slightly in
bloaters and white sucker (Caloslomus commcrsoni ). .Mean
PCB residues in bloaters caught in Lake Huron in 1969-71
and 1975-76, and splake (Salveliniis fonlinalis and S.
namaycush) and ci.sco (Coregonus arledii) caught in 1975
exceeded the 2 ppm tolerance level.
IiUrociiiclion
The Great Lakes are surrounded b> land ihal is highly
developed for urban, industrial, agricultural, and recrea-
tional activities. Since outflow of the Circat Lakes is
limited, chemical discharges into the lakes are very per-
sistent. For the past decade organochlorines have been
identified as a serious contaminant in fish, resulting in
long-range detrimental effects to private and commercial
fishing.
'Partial fundinK fur ihc l'*75-75 samplint; and analysis provided by the
Intcrnaiiunal Ji>int (Vimmission under Task Force D of the Pollution
from Land Use Activities Reference Group.
•Provincial Pesticide Residue Tesiinp laboratory. Ontario Ministry of
Auriculiurc and food, c o University of Guelph. Guclph, Ontario.
NIG 2WI.
■■ Fisheries Branch. Ontarin .Ministry of Natural Resources. Queens
Park. Toronto, Ontario.
'Fish and Wildlife Research Dramh. Ontario Ministry of Natural
Resources, South Bay. Ontario.
Organochlorine insecticides and polychlorinated bi-
phenyls (PCBs) have been identified in fish caught in
Lakes Huron and Superior. Reinhert reported residues
of 0.2-7.4 ppm i.DDT and 0.01-0.05 ppm dieldrin in
several species of fish caught in Lake Superior in 1967-
68 (7). Reinke et al. reported that two fish species
caught in 1970 from the same lake had mean residues
of 0.2 ppm and 1.3 ppm -DDT and 0.06 ppm dieldrin
(9). Four species, also caught in Lake Superior in 1974-
75, cited by the Upper Great Lakes Reference Group,
contained mean residues of 0.2-4.4 ppm -DDT and
0.0 1 -0. 1 5 ppm dieldrin ill). Residues of chlordane, lin-
dane, and PCBs were also reported in these four species.
Reinhert found mean residues of 0.8-6.9 ppm -DDT
and 0.02-0.1 1 ppm dieldrin in nine species of fish from
Lake Huron in 1967-68 l7). Reinke et al. reported mean
residues of 0.5-16.4 ppm IDDT and 0.01-0.31 ppm di-
eldrin in the same major fish species in Lake Huron in
1970 1 9). The Upper Great Lakes Reference Group
cited considerably lower residues of -DDT in three fish
species caught in 1974-75 111), but levels of dieldrin.
lindane, chlordane, and PCBs were similar to those found
in other studies.
Studies on the distribution of organochlorines in water,
sediment, and scston in Lakes Superior and Huron reveal
that these compounds are widespread in the Great Lakes
ecosystem l3). Miles and Harris reported that the Mus-
koka River discharged large amounts of -DDT to
Georgian Bay 16). Peak discharges of 5.4 kg/week
occurred in May 1971, but the i^uantity declined rapidly
from May to October, averaging 0.9 kg -DDT/week.
r-rank et al. found that fish in the Muskoka Lake-
Muskoka River system contained some of the highest
residue levels founti in fish from inland lakes of Ontario
l2). Fourteen species had mean residues of 0.22-22.4
ppm -DDT; sediments in this lake-river system con-
tained -DDT residues as high as 2.9 ppm.
Ihc present study, begun in 1968, was originally in-
tended to idenlily ami measure organochlorine residues
60
Pesticides Monitoring Journal
LAKE SUPERtOft
9 »iNLi' M'
9 SH(s>«fp B<i
LAKE HURON
ID KKiiSTonf uascun
.^ n
FIGURE 1. Map of Lakes llnrtin niul Superior \lio\\ini; fi.sli collection areas
in fish from the Great Lakes. However, it was broadened
following restrictions on the use of aldrin, dieldrin. and
heptachlor in Canada in 1969. DDT in 1970, and the
voluntary restrictions on the use of PCBs in 1971 within
the Province of Ontario. Authors wished to determine
whether these use restrictions were significantly reflected
in organochlorinc residues in fish from Lakes Huron and
Superior.
Methods and Materials
FIELD COLLECTION
Fifteen species (843 fish) were caught by net, line, or
trap between 1968 and 1976 from Lakes Huron and
Superior; many of the larger fish were obtained from
commercial catches. Five species (115 fish) were caught
in the Canadian waters of eastern Lake Superior between
Michipicoten and the entrance to the North Channel
(Figure 1). Between 1968 and 1976, 14 species (728
fish) were caught in Lake Huron. Of these. 481 fish of
12 species were from the Canadian waters of Lake
Huron, 142 fish of five species were from Cieorgian Bay,
and 105 fish of five species were from the North Chan-
nel. Bloaters (Coregoniis hoyi), coho salmon (Oncorhyn-
chiis kisiilch). and walleye (Stizosiedion vilreiiiu vilreiiiu)
were caught in southern Lake Huron, walleye caught in
Cieorgian Bay at the mouth of the Moon River, and rain-
bow trout fSalnio goirdneri) and lake trout iSalveliniis
/HiDHiyciish) came from the south shore of Georgian Bay.
Other species were caught between the Bruce Peninsula
and Manitoulin Island.
Fish species were identified and named according to the
nomenclature of the American Fisheries Society (1 ).
SAMPLE I>REPAR.-\TION
Fish were measured, weighed, and where possible, the
sex was determined. Heads and viscera were removed
and the remainder of the fish was macerated in a Hobart
meat grinder. A 150-200-g subsample was stored in a
sealed glass jar at — 20"C: storage time varied from a
few days to four months. Individual fish were analyzed
when the sample size was not limiting. Alewife. shiners,
smelt, and other small fish were prepared as composites
of similar sized fish. They were weighed and measured
individually before being ground.
Vol . 12, No. 2. September 1978
61
ANALYTICAL PROCEDURE
Ten grams of tissue homogenate was ground with 100 g
anhydrous sodium sulfate and 25 g Ottawa sand. The
mixture was extracted with 300 ml hexane for 7 hours
In a Soxhiet extractor. Solvent was evaporated by rotary
vacuum and the percentage fat was determined gravi-
melricalh.
A one-step Florisil column cleanup method described by
Langlois et al. <5) was used to isolate organochlorine in-
secticides and PCBs. A maximum of I g fat was mixed
with conditioned Florisil and placed above another layer
of Florisil. The column was eluted with a 300-ml 1:4
mixture of dichloromethane-hexane. Solvent was evap-
orated by rotary vacuum.
PCBs. Hexachlorobenzene (HCB), and organochlorine
insecticides were separated on a charcoal column accord-
ing to the method described by Holdrinet (4). Analyses
were performed with a Tracor Model 550 gas-liquid
chromatograph (GLC). Instrument parameters and oper-
ating conditions follow.
Deleclor:
Column:
Temperature:
Carrier gas:
Injection
volume:
•"Ni
15 cm y 0.64 cm OD glass, packed with a
mixture of 4 percent SE-30 and 6 percent
QF-I on 80-100-mesh Chromosorb W
I80°C
nitrogen flowing at 60 ml/minute
5 ti\ was equivalent to I ng fat sample
Two-dimensional thin-layer chromatography was used on
random samples for confirmation. Samples were re-
moved, redissolved. and re-injected into the GLC column.
Recoveries were checked periodically by fortification of
tissue homogenates prior to extraction. Average recov-
eries were:
was included in 1973 but was discontinued because of
the low level and incidence of HCB found in the sam-.
pies. The analysis and confirmation for cis- and irans-
chlordane was refined in 1975; analyses for mirex and
oxychlordane were introduced in 1976.
Results
LAKE SUPERIOR
-DDT — None of the five fish species caught in Lake
Superior contained annual mean residues in excess of the
5 ppm tolerance level established by Health and Welfare
Canada or the Food and Drug Administration, U.S. De-
partment of Health, Education, and Welfare. The high-
est mean residue of 2.7 ppm was found in lake trout
caught in 1968. However, of 18 lake trout analyzed,
three contained residues of -DDT that exceeded 5 ppm
(Table 1): a 1 544-g fish caught in Shesheep Bay con-
tained 14.1 ppm: a 2906-g fish caught off Thunder Cape
contained 7.9 ppm; and a 3314-g fish caught in Finlay
Bay contained 5.2 ppm (Figure I). Lake trout caught in
1971 and bloaters caught in 1971 and 1975 contained
the second highest mean -DDT residues of 1.16 ppm
and 1.06 ppm. respectively, but no individuals exceeded
the tolerance level.
Residues of -DDT declined in both lake trout and lake
whitefish (Coregoniis cliipeaformis) between 1971 and
1975. but no trend was apparent in either bloater or
white sucker (Coregoniis commersoni). The ratio of
DDE plus TDE to -DDT increased in lake trout and
lake whitefish from 1971 to 1975. indicating a metabolic
breakdown of o.p'- and /7./)'-DDT; this was not so appar-
ent in bloaters and white sucker (Table 2). The decline
is more evident in lake trout when similar weight classes
are compared (Table 3). In spite of higher fat content in
fish caught in 1975. -DDT is only a fraction of the resi-
due found in 1968-70.
Residue
%
Residue
%
o,p'_DDT
91
Dieldrin
89
P,P'-DDT
89
c(5-Chlordane
98
P,P-TDE
94
/rtmA-Chlordane
90
P,P'-DDE
96
PCBs
85-90
The data were not corrected for recoveries. Detection
limits were 0.005 ppm for organochlorines and 0.05 ppm
for PCBs. PCBs were identified by comparing them with
mixtures of Aroclors 1254 and 1260 and checking for a
resemblance to peaks VII, VIM, and X on sample chro-
matograms according to Reynolds (10).
Analysis was begun in 1968 when the known main con-
taminants in fish were /j./)'-DDT and its analogs plus di-
eldrin and heptachlor epoxide; PCB values prior to 1970
were estimated. With the iniroduction of a column frac-
tionation technique in 1970 for the separation of PCBs
from organochlorine insecticides, ihc measurement of
PCB residues became more precise. Analysis for HCB
Dieldrin — No fish species contained mean residues that
exceeded 0.08 ppm dieldrin, and no individual fish con-
tained residues which exceeded the 0.3 ppm guideline
set by FDA. The highest level of dieldrin found in an
individual fish was 0.26 ppm in a lake trout caught in
1968. In general, levels of dieldrin were low, but the
rate of disappearance of dieldrin since 1971 also has
been slow. On the basis of a -DDT/dieldrin ratio,
-DDT declined more rapidly than dieldrin between
1971 and 1975 (Table 2). Lake trout exhibited a decline
in the ratio between 1968 and 1975 of 91 to 5. The ratio
of PCBs to dieldrin changed little between 1971 and
l'>75. This was borne out when similar weight classes
t)f lake trout were compared (Table 3).
PCBs — None of the five fish species caught in Lake
Superior contained mean residues of PCBs greater than
the 2 ppm tolerance level set by Health and Welfare
Canada (Table I). However, two individual trout caught
62
Pesticides Monitoring Journal
TABLE 1. OrganocMorine residues in five fish species caught in the Canadian waters of eastern Lake Superior, 1969-75
Year
No. OF
Analyses
Mean
AND Range
Mean Con
TENT AND RANGE
OF Contaminants in Fish P
UREE, PPM».=
Weight.
G
Fat.
Species
DDE
TDE
DDT
2 DDT
Dieldrin
PCBs
Caloslomidae
White sucker
1971
5
1102
-) 1
0.08
0.01
0.04
0.13
0.01
0.2
988-1202
0.9-5.0
<0.0!-0.15
<0.01-0.02
<0.01-0.07
0.01-0.24
<0. 1-0.5
1975
8
946
3.1
0.14
0,01
0.05
0.20
0.02
0.3
696-1154
0.7-7.1
0.03-0.46
<0 .01-0.03
<0.01-0.15
0.08-0.59
<0.01-0.06
0.1-0.7
Esocidae
Northern pike
1971
5
2044
1.2
0.23
0.03
0.14
0.40
<0.01
0.3
1474-2752
0.8-1.8
0.08-0.48
0.01-0.07
0.02-0.41
0.11-0.96
0.1-0.6
Salmoiiidae
Bloater
1971
4(19) ■
149
9.7
0.68
0.07
0.41
1.16
0.02
0.6
145-175
9.4-10.0
0.56-0.75
0.06-0.08
0.34-0.45
0.96-1.36
0.01-0.06
0.5-0.7
1975
10
169
10.2
0.52
0.07
0.47
1.06
0.04
1.0
112-268
3.1-18.7
0.07-1.76
0.02-0.16
0.12-1.39
0.22-3.23
0.0I-O.09
0.3-3.7
Lake Irout
1968
18
2016
8.0
1.44
0.24
1.04
2.72
0.08
0.7
455-5506
1.3-14.7
0.16-7.11
0.01-1.32
0.02-5.68
0,27-14.1
0.01-0.26
<0. 1-2.0
1969
20
734
6.4
0.43
0.12
0.43
0.98
0.03
0.3
409-171X)
1.7-14.4
0.20-0.75
0,04-0.20
0.19-0.77
0.43-1.69
<0.0 1-0.05
0.1-0.6
1971
5
1901
17.4
0.9S
0.09
0.65
1.72
0.03
1.8
1572-2728
15.7-22.1
0.59-1.25
0.06-0.11
0.38-0.82
1.03-2.18
0.02-0.05
1.1-2.3
1975
10
1121
20.7
0.11
0.01
0.05
0.17
0.04
0.4
555-1432
14.7-29.4
0.09-0.16
<0. 01-0.03
0.02-0.09
0.10-0.24
0.03-0.05
0.3-0.6
Lake whilefish
1971
5
959
12.0
0.35
0.04
0.35
0.74
0.04
0.8
895-1060
8.5-14.2
0.29-0.45
0.03-0.05
0.. 10-0.43
0.6.3-0.93
0.03-0.05
<0. 1-1.0
1975
11)
1135
10.8
0.16
0.02
0.06
0.24
0.07
0.3
766-1400
6.2-12.2
0.09-0,29
0.01-0.03
<0.01-0.16
0.12-0.48
0.04-0.11
0.1-0.7
1 In 1975 traces (0,004 ppm ) of cis- and /rflM5-chlordane were detected in st.>me bloater, while sucker, lake Iroul. and lake whitefish.
-<0.01 ppm represents a trace of contaminani above the level of detection (0.001 ppni ) but uelow 0.010 ppm.
■'Composite of 19 fish.
off Grass Cap Point in 1971 ha(i resi(iues of 2.2 ppm and
2.3 ppm PCBs and two bloaters caught commercially in
I97.'> had residues of 2.1 ppm and 3.7 ppm. Mean resi-
dues for lake trout in 1971 and bloaters in 197.S were
1.8 ppm and 1.0 ppm, respectively.
TABLE 2. Ratios of organochlorinc contantinants in four
species of fisli cauglit in Luke Superior, Luke Huron,
and Georgian Bay, 1968-76
Year
DDE+TDE
^DDT
i;DDT
PCBs
:cddt
PCBs
Species
Dieldrin
DnU-DRlN
Lake Superior
Bloater
1971
0.65
2.0
50
30
1975
0.56
1.1
30
25
While sucker
1971
0.69
0.5
21
20
1975
0.75
0.8
10
15
Lake trout
1968
0.62
3.9
91
9
1969
0.56
3,3
33
10
1971
0.62
0.9
50
60
1975
0.70
0.4
5
10
Lake whilefish
1971
0.53
0.9
19
20
1975
0.75
0.8
3
4
Lake Huron (Mt
MM Lake
)
Bloater
1969
0.74
3.5
69
20
1970
0.52
1.8
29
16
1971
0.64
2.1
94
44
Cisco
1969
0.66
6.1
61
10
1976
0.95
1.0
6
7
Coho salmon
1968
0.54
0.5
26
50
1969
0.68
2.5
51
20
1970
0.60
1.6
25
15
1971
0.61
1.2
19
17
1975
0.91
0.4
7
16
Lake whitelish
1969
0.36
3.6
9
-)
1972
0.60
1.4
9
1
1973
0.60
1.2
8
7
1976
0.80
0,6
">
3
Georgian Bay
Bloater
1971
0.66
1.0
24
24
1975
0.61
0.7
5
7
Cisco
1969
0.38
3.2
159
50
1976
0.62
0.7
8
12
Mean PCB residues declined in lake trout and lake
whitefish between 1971 and 1975 but increased in bloat-
ers over the same period. Comparison of lake trout by
weight class revealed no significant decline in PCB resi-
dues (Table 3). The i:DDT/PCB ratio in all species de-
clined, suggesting the disappearance of XDDT. The
PCB/dieldrin ratio indicates that dieldrin is more per-
sistent in fish tissues than are PCBs.
Other organochloriiu's — Trace quantities (<0.01 ppm) of
CIS- and traiis-chlordane were detected in some bloaters,
white sucker, lake trout, and lake whitefish caught in
197.^, but no o.xychlordane, endrin. or heptachlor epox-
ide was detected in fish caught in I9(iS-73.
LAKE HURON
-DDT — Three fish species caught in Lake Huron and
Georgian Bay contained mean residues that exceeded
5 ppm. These included walleye (5.05 ppm) caught in
southern Lake Huron in 1970, lake trout (7.60 ppm)
caught in Georgian Bay in 1969, and bloaters (5.18 ppm)
caught in 1971 in Georgian Bay (Table 4). Individual
fish of five species contained -DDT residues in excess of
5 ppm including; bloaters (1970 and 1971), coho salmon
(1970), and walleye (1970), caught in the southern half
of Lake Huron; and bloaters (1971). rainbow trout
(1968), lake trout (1969), and walleye (1969 and 1970)
caught in Georgian Bay (Table 4, Figure 1).
i;DDT residues declined noticeably between 1968-71
and 1975-76 in six species including alewife (Alosa
pscudoharengiis), smallmouth bass (Micropterus dolo-
itiiciii). Cisco fCoregoniis artedii). coho salmon, rainbow
Vol. 1 2, No. 2, September 1978
63
TABl F. 3. Comparison of organocMorinc residues in Iwo weiglil classes of splake, lake trout,
and lake whitefish cauglit in Lake Huron and Lake Superior, 1969-76
Spi cii s
0.5-1.0
KG Class
L0-L5
KG Class
AND
No. OF
Weight.
Fat.
2 DDT.
DiELDRIN,
PCBs.
No. OF
Weight.
Fat,
2 DDT,
DiELDRIN,
PCBs,
Location
Year
Fish
G
'■/o
PPM
PPM
PPM
Fish
c
%
PPM
PPM
PPM
Splake
Lnkc Huron
1969
3
821
6.8
1.61
0.06
0.2
5
1351
6.9
0.86
0.03
0.3
1970
3
784
13.2
1.16
0.06
1.6
8
1220
17.6
1.35
0.07
1.5
1972
3
787
10.8
0.87
0.05
0.7
1973
10
690
6.6
0.77
0.03
0.6
4
1108
12.2
0.75
0.06
0.9
1974
1
526
3.3
0.11
<o,ni
0.1
4
1271
4.4
0.15
0.02
0.3
Georgian Bay
1975
6
747
11.9
0.78
0.14
1.4
6
1185
14,1
0.87
0.16
1.9
Whilefish
Lake Superior
1971
3
910
12.5
0.71
0,04
0.8
1
1032
11.3
0.78
0.04
0.8
1975
1
766
S.6
0.28
0.04
0.2
9
1176
11.0
0.22
0.07
0.3
Lake Huron
1969
T>
730
5.4
0.40
0.05
0.1
1
1180
3.7
0.25
0.03
<0.I
1972
12
813
8.2
0.55
0.07
0.3
7
1142
12.3
0.87
0.09
0.6
1973
7
1172
17.1
0.64
0.08
0.4
1976
2
850
3.7
0.08
0.03
0.1
10
1237
6.3
0.12
0.07
0.2
North Channel
1969
6
936
3.2
0.14
0.01
<0.1
8
1187
6.1
0.89
0.10
0.1
1970
1
980
8.6
0.80
0.05
0,4
2
1285
10.6
0.71
0.07
0.4
Georgian Bay
1969
4
939
4.5
0.44
0.01
0.1
6
1131
3.7
0.54
0.01
0.2
Lake Troui
Lake Superior
1968
8
698
4.8
0.818
0.046
0.21
4
1566
10.6
4.94
0.128
1.19
1969
1(1
619
3.8
0.731
0,1124
0.25
10
1308
8.8
1.25
0.040
0.34
1970
4
1694
17.9
1.75
0.033
1.88
1975
3
768
18.6
0.192
0.037
0.33
7
1272
21.6
0.17
0.037
0.49
smelt iOsntcrus inordu.x}. and walleye from the main
waters of Lake Huron, and bloaters from Georgian Bay.
-DDT mean residues were erratic or unchanged in cisco,
splake (Salveliniis foniinalis and 5. nainaycush). and
walleye caught in Georgian Bay and in splake and lake
whitefish caught in the main lake.
To determine whether -DDT residues in splake and lake
whitefish had declined, similar weight classes were com-
pared (Table 3). 2;DDT levels in splake with an average
weight of 1250 g declined between 1971 and 1974 from
I. .35 ppm to 0.15 ppm. A similar decline in 2;DDT
residues in lake whitefish was noted between 1972 and
1976. Cisco, coho salmon, and lake whitefish all showed
a marked increase in the DDE + TDE/2;DDT ratio dur-
ing the present stud\ (Tabic 2), suggesting a lower intake
of the parent compound and 'or degradation to metabo-
lites; this decline was not evideiil in bloaters.
Dietdrin — Mean residues for all species investigated did
not exceed the 0.3 ppm tolerance level set by FDA.
However, individual fish of three species exceeded the
level. One of 20 lake whitefish caught in the North
Channel in 1969 contained 0.58 ppm dieldrin; one of 10
bloaters caught in Lake Huron in 1970 had a residue of
0.44 ppm dieldrin: five of 10 bloaters caught in Cieorgian
Bay in 1975 contained dieldrin levels of 0.34-0.50 ppm;
10 of 20 bloaters caught in the North Channel in 1975
contained residues of 0.3 -0.6 ppm dieldrin; and two
large splake caught in Lake Huron contained residues
of 0.43 ppm and 0.53 ppm dieldrin. The 10 bloaters
caught in the North Channel during 1975. which had
residues above the tolerance level, weighed an averace
64
of 333 g and contained an average of 0.40 ppm dieldrin.
The remaining 10 bloaters, which averaged 236 g, con-
tained a mean residue of 0.19 ppm dieldrin. In this in-
stance, and in the case of the splake, higher dieldrin
residues were associated with larger fish, but this rela-
tionship was not apparent in the 10 bloaters caught in
Georgian Bay in 1975 (Table 4).
Dieldrin levels increased in alewifc, bloaters, cisco. yel-
low perch iPcrca flavcsccns). coho salmon, and splake
during l9(iS-71 and 1975-76; levels in other species
showed little change. Assessment of dieldrin levels on
the basis of similar weight classes of lake whitefish and
splake indicate that residues declined in lake whitefish
and increased in splake (Table 3). A marked decline was
noted in the -DDT dieldrin ratio in four species: in
cisco, for example, the ratio declined from 61 to 6 be-
tween 1969 and 1976. The PCB/dieldrin ratio also
declined in the same four species suggesting declining
PCB residues and static or increasing dieldrin residues
(Table 2).
PCBs — Three fish species contained mean PCB residues
which exceeded the 2 ppm tolerance level set by Health
and Welfare Canada. Bloaters from the main lake
(1970 and 1971), from Cieorgian Bay (1971 and 1975).
and from the North Channel (1975) contained mean
residues of 2.2-5.2 ppm. Individual bloaters hatl resi-
dues as high as 5.0 ppm and 6.4 ppm (Table 4). Cisco
netted in Georgian Ba\ during 1975 contained a mean
PCB residue of 2.2 ppm and a high level of 4.6 ppm in
individual fish. Two large splake taken from the main
waters of Lake Huron in 1975 contained levels of 5.5
ppm :nid (\4 ppm PCBs.
Pisrii ini s MoNiroKiNC. Joi'knai,
TABLE 4. Organochlorine residues in 14 fish species caught in the North Channel,
Georgian Bay, and Canadian waters of Lake Huron, 1968-76
Year
Location
No. OF
Anal-
YSESl
Mean and Range
Mean 1
roNTENT AND
Range of Contaminants in
1 Fish Puree,
Weight, Fat.
0 Tc
PPM =
Species
DDE
TDE
DDT
2 DDT
Dieldrin
PCBs
Catosromidae
White sucker
1972
Huron
5
723
2.5
0,08
0.01
0.02
o.u
<0.01
0.1
550-909
1.8-3.3
0,05-0.13
<0.0 1-0.03
<0.0 1-0.06
0.06-0.22
<0,l-0.2
1973
Georgian
4
131
0.7
<0.0I
<0.01
<0.01
0.01
<0.01
0.1
Bay
66-212
0.2-1.0
<0.01-0.02
<0.01-0.03
<0.1-0.2
1976
Huron
10
977
0.6
0.06
<0.01
0.02
0.09
<0.01
O.l
738-1 83-i
' 0.1-1.1
<0.01-0.20
<0.01-0.14
<0.0 1-0.37
<0.1-0.2
Centrachidae
Smallmouth
1968
Huron
3
499
3.1
0.68
0.76
0,53
1.97
<0.01
0,9
bass
429-630
2.0-4.9
0.12-1.69
0.15-2,02
0.12-1.23
0.30-4.94
0.2-2.0
1972
Huron
5
353
3.7
0.12
0.01
0.03
0.16
0,01
0.4
298-437
2.6-4.5
0.11-0.13
0.02-0.04
0.15-0.18
<0,0 1-0.03
0.3-0.5
1972
Georgian
6
281
2.8
0.05
0.01
<0.01
0.07
<0.01
0.01
Bay
270-300
1.6^.0
0.04-0.07
0.01-0.02
0.06-0.10
0.1-0.1
1975
Georgian
9
364
3.2
0.17
0.01
0.03
0.21
0.03
0.6
Bay
275-562
1.7-4.5
0.09-0.28
<0.01-0.04
<0.01-0.08
0.12-0.36
<0.0 1-0.09
0.4-0.9
Clupeidae
Alewife
1970
Huron
8(21)
33
7.5
0.76
0.23
0.64
1.63
0,08
1.1
26-40
1.5-13.2
0.16-1.40
0,04-0,52
0.22-1.48
0.27-3.40
0,01-0,22
0.5-2.0
1976
Huron
5(23)
23
10.7
0.44
0.10
0.26
0.80
0.14
0.3
3-49
5.8-16.9
0.04-1.08
0,01-0.12
0.01-0.54
0.06-1.74
<0.01-0.25
0.1-0.6
Osmeridae
Rainbow smelt
1970
Huron
8(21)
22
6.5
0.36
0.12
0.32
0.80
0.04
0.7
12-67
4.0-8.4
0.06-0,97
0.01-0.25
0.02-0,80
0.11-1.86
<0.01-0.15
0.2-1.0
1970
N. Channel 5(24)
26
3.6
0,12
0.04
0,15
0.31
0.02
0,1
18-44
2,8-4.4
0,05-0.20
0.03-0.05
0,08-0,20
0.15-0.45
<0.01-0.03
1976
Huron
7(32)
14
2.7
O.II
0.02
0.02
0.15
0.01
0.01
7 -.30
1.2-3,9
0.05-0.19
0.01-0.02
<0.0 1-0.03
0.08-0.23
<0.0 1-0.02
<0. 1-0.2
Percidae
Yellow perch
1968
Huron
5
335
0.8
0.20
0.12
0.20
0.52
<0.01
0.2
118^26
0.5-1.0
0.06-0.61
0.02-0.47
0.08-0.51
0.1^1.59
<0.1-0,5
1969
N. Channel 20
201
1.4
0.03
0.01
0.03
0.07
<0.01
<0,1
167-341
0.5-2.4
<0.01-0.08
<0.01-0.03
<0.01-0.05
<0,01-0,13
1972
Huron
5
67
4.4
0.07
0.01
0.03
O.U
0.01
0.1
64-74
3.8-5.3
0.06-0.08
0.01
0.02-0.03
0.09-0.12
<0.0 1-0.02
1975
N. Channel 10
175
6.1
0.36
0.03
0.09
0.48
0.05
0.9
150-197
3.5-8.6
0.13-0.57
<0.0 1-0.05
<0.01-0.17
0.1-3-0.72
0,02-0,09
0.4-1.4
1976
Huron
17
236
2.5
0.21
0.03
0.08
0.32
0,02
0,2
66-481
0.7-5.4
0.06-0.68
0.01-0.08
0.01-0.55
0.07-1.31
<0.0 1-0.05
<0. 1-0.4
Walleye
1968
Huron
3
409
0.8
0.12
0.04
0.13
0.29
<0.01
0,1
390-426
0.6-0.9
0.06-0.22
0.02-0.07
0.08-0.21
0.16-0.50
<0. 1-0.1
1969
Georgian
15
2073
2.6
1.05
0.24
1,08
2.37
0.02
1.5
Bay
792-4190
0.6-6.0
0.23-3.53
0.06-0.81
0.23-4.03
0.54-8.36
<O.01-0.O7
0.5-2.1
1970
Huron
2
2083
10.1
2.37
0.64
2,04
5.05
0.08
1.3
1910-2255
9.7-10.4
1.80-2.91
0.43-0.84
1.65-2,47
3.88-6.22
0.06-0.08
0.7-1.9
1970
Georgian
21
3236
4.7
0.94
0.23
0,98
2.15
0.04
1.4
Bay
1721-4760
1.2-10.6
0.23-3.70
0.04-0.85
0,18-3,88
0.45-8.33
<0.01-0.16
0.5-2.3
1970
N. Channel
1 3
605
2.1
0.19
0.04
0.16
0.39
<0.01
0.1
526-715
1.3-3.5
0.16-0.23
0.04-0.05
0.13-0.21
0.34-0.49
<0. 1-0.1
1971
Georgian
10
2859
5.8
1.74
0.21
1.11
3.06
0.03
1.8
Bay
1 132^756
2.9-11.6
0.08-4.08
0.04-0.37
0.04-2.32
0.1^6.93
<0.01-0.07
0.1-3.9
1975
Huron
10
2539
4.7
0.38
0.05
0.27
0.70
0.03
0.5
722 5218
1.5-13.3
0.16-1.01
<l).0 1-0.15
0.03-1.01
0.27-2.17
0.01-0.13
0.3-2.5
Salnionidae
Bloater
1969
Huron
15
97
3.0
0.39
0.12
0.18
0.69
0.01
0.2
55-143
1.4-7.7
0.06-1.54
0.02-0.50
0.04-0.66
0.20-2.71
<0.01-0.02
<0. 1-0.7
1970
Huron
10
260
16.(1
1.95
0.49
2.24
4.68
0.16
2.6
148-307
8.1-26.7
1.00-3.69
0.20-1.03
1.01-5.17
2.48-9.88
0.04-0.44
1.5-5,0
1971
Huron
6
71
15.0
2.73
0.29
1.69
4.71
0.05
2.2
61-101
7.2-21.1
2.02-4.34
0.05-0.78
1.14-2.40
3.44-7.52
0.03-0.07
1.1-3.2
1971
Georgian
4(12)
259
20.1
2.90
0.53
1.75
5.18
0.22
5,2
Bay
140-433
18.0-23.!)
2,34-3,83
0.29-0,75
1.63-1.85
4.26-6.43
0.18-0,28
4.3-6.4
1975
Georgian
10
219
16.3
0,71
0.16
0.56
1.43
0.30
2.2
Bay
179-250
8.1-20.1
0,33-1.15
0.01-0.30
0.15-1.11
0.49-2.56
0.10-0.50
0.8-4.4
1975
N. Channel
20
285
22.9
1.16
0.17
0.54
1.87
0.29
2.6
134-560
15.5-29.8
0.56-2.34
<0.0 1-0.41
0.01-1.48
0.74-4.18
<0.01-0.60
0.6-5.2
Cisco
1969
Huron
2
180
5.4
0.35
0.05
0.21
0.61
0.01
O.I
100-260
2.0-8.8
0.18-0.52
0.02-0.07
0.07-0.35
0.27-0.94
<0.0 1-0.02
<0. 1-0.2
1969
Georgian
10
820
7.2
0.41
0.19
0,99
1.59
0.01
0.5
Bay
337-937
4.8-9.4
0.22-1.01
0.08-0,40
0.54-2,58
0.83-3.99
<0.0 1-0,02
0,2-1.1
1975
Georgian
6
543
18.0
0.78
0,15
0.58
1.51
0.19
2.2
Bay
352-710
11.3-24.7
0.47-1.14
0,09-0,29
0.26-1.22
0.83-2.65
0.12-0.30
1,3^.6
1976
Huron
9(11)
138
5.0
0.14
0.05
0.01
0.20
0.03
0.2
47-242
3.0-7.5
0.11-0,19
0.03-0.09
<0.01-0.02
0.14-0.29
0.01-0.08
0.1-0.4
(continued next page)
Vol. 12, No,
. 2, September ]
1978
65
TABLE 4. (cont.dJ Organochlorinc residues in 14 fish species caught in the North Channel,
Georgian Bay, and Canadian waters of Lake Huron, 1968-76
No. OF
Anal-
yses'
Mean and Range
Year
Location
Weiomi,
G
Fat,
Mean Content and Range of Contaminants in
Fish Puree, ppm^
Species
%
DDE
TDE
DDT
SDDT
Dieldrin
PCBs
Coho salmon
1968
Huron
8
81
3.9
0.11
0.03
0.12
0.26
<0.01
0.5
39-163
1.2-5.4
0.04-0.42
0.01-0.12
0.04-0.43
0.09-0.97
0.01-0.03
0.2-1.0
1969
Huron
5
1885
5.8
0.88
0.16
0.48
1.52
0.03
0.6
11 38 33 35
5.1 6.5
0.31-2.01
0.13-0.21
0.35 0.62
0.87-2.84
0.01-f).05
0.3-1.2
1970
Huron
41
1031
4.9
0.48
0.11
0.39
0.98
0.04
0.6
754-1595
0.8-11.1
0.9 5.2
0.03-0.66
0.08-1.89
0.22-7.75
O.Ol-fJ.24
0.1-7.0
1971
Huron
1(1
936
8.0
0.50
0.20
0.45
1.15
0.06
LO
475-1395
4.9-13.0
0.23-1.15
0.07-0.62
0.16 0.80
0.48-2.09
0.02-0.13
0.2-2.1
1975
Huron
11
2284
5.8
0.43
0.05
0.05
0.53
0.08
1.3
280-4356
3.9-8.4
0.04-0.94
<0.01-0.14
<0.01-0.19
0.05-1.22
0.01-0.16
0.1-3.3
Kokancc salmon
1968
Huron
2
95
3.5
0.44
0.12
0.59
1.15
0.04
0.3
94-96
2.8-4.2
0.08-0.80
0.02-0.22
0.10-1,08
0.20-2.00
<0,0I-0,07
0.1-0.4
1969
Huron
II
98
3.3
0.10
0.03
0.10
0.23
0.01
<0.l
58-375
1.4-5.3
0.02-0.80
•^O.0 1-0.06
0.03-0.18
0.06-0.57
<0.01-0.03
1970
Huron
15
512
4.1
0.38
0.12
0.45
0.95
0,04
0.6
204-1098
0.9-7.8
0.17-0.67
0.05-0.24
0.16-1.03
0,78 1.76
^ooi-o,^
0.2-1.0
Splakc
1969
Huron
20
1113
6.3
0.43
0.14
0.46
1.03
0,04
0.2
25 2354
1.8-10.1
0.03-0.85
0.02 0.33
0.03-0.85
0.08-2.11
<0,01-0,(J9
<0. 1-0.5
1970
Huron
23
810
10.2
0.37
0.13
0.50
1 .00
0,04
1.0
208-1420
3.2-15.7
O.I 2-0.82
0.04-0.20
0.01-1.03
0.19-1.81
<'0.0l-0.12
0.1-1.5
1972
Huron
5
544
8.5
0.30
0.04
0.28
0.62
0.03
0.5
138-877
5.1-11.7
0.14-0.44
0.01-0.04
0.08 0.56
0.23-1.10
0.01-0.05
0.2-0.9
197:1
Huron
26
556
8.8
0.38
0.03
0.06
0.47
0,03
0.4
96 450
3.6 16 1
0.03-1.20
■^0.01-0.13
<0.01-0.16
0.04-1.31
<0.01-0,10
<0.1-1.5
1974
Huron
7
1238
4.1
0.11
0.01
0.03
0.15
0.02
0.2
526-1540
2.7-5.9
0.06-0.19
<^0.01-0.02
<0.01-0.05
0.08-0,25
<0.0 1-0.04
<0.1-0.7
1975
Huron
2
2127
17.2
1.80
0.42
0.46
2.68
0.48
6.0
1997 2256
13.6-20.8
1.58-2.02
0.40-0.44
0.37-0.55
2.39-2.97
0,43 0,53
5.5-6.4
1975
CicorKian
17
1048
13.3
(1.52
0.08
0.18
0.78
0,15
1.6
Bay
458 1798
8.5-17.4
0.18 0.88
0.03 0.1 1
0.10-0.37
0.28-1.12
0,08-0,18
0.6-2.3
Rainbow trout
1968
Georgian
12
857
5.5
0.74
0.17
0.84
1.75
0.04
0.3
Bay
284-1850
3.2-7.8
0.12-6.17
0.02-1.27
0.13-5.70
0.27-13.1
<0.01-0.19
<0.1-1.5
Lake trout
1969
Georgian
4
6328
13.4
4.04
0.50
3.06
7.60
0,07
0.7
Bay
4200-8740
12.9-13.8
3.14 5.51
0.45 0.63
2.66 3.71
6.28 9.85
0.06-0,09
0.4-0.9
Lake whilcfpsh
1969
N. Channel 21)
1430
4.8
0.13
0.07
0.36
0.56
0,06
0.1
854-2785
0.8-8.9
0.03-1.58
0.01-0.3 1
0.66 2.66
0.10 4.75
<0.0 1-0.58
<0.1-0.7
1969
Huron
26
711
5.0
0.13
0.05
0.18
0.36
0.04
0.1
386 1080
2.9 9.9
0.07 0.24
0.02-0.10
0.04-0.36
0.16-0.73
<0,OI-0.08
<0.1-0.3
1969
Georgian
10
1054
4.0
0.20
0.09
0.22
0.51
0,01
0.2
Bay
881-1241
3.2-6.4
0.10-0.31
0.03-0.13
0.09 0.33
0.22 0.78
<0,0 1-0,02
<0. 1-0.3
1970
N. Channel 1
1183
9.9
0.27
0.07
0,40
0.74
0,06
0.4
980-1361
8.6 11.7
0.23 0.29
0.07
0.33-0.45
(1.63-0,80
0.05-0.09
0.2-0.5
1972
Huron
25
761
8.2
0.28
0.65
0.22
0.55
0.06
0.04
80-1393
1.8 21.9
0.07 1.02
0.01-0.16
0.03 0.42
0.I1-I.47
0.01-0.11
0.1-0.8
197.1
Huron
19
804
14.2
0.23
0.05
0.19
0,47
0.06
0.04
108-1747
6.9-26.5
0.03-1.48
0.01-0.21
0,02-0.92
0.07-2.61
^0.01-0.25
<0. 1-0.6
1976
Huron
l-i
1323
5.8
0.08
0.02
0.03
0.13
0,06
0.2
802-2495
2.5-11.6
0.04 0.15
0.01-0.03
0.02-0.05
0.07-0,23
0.03-0.14
0.1-0.5
'Most analyses were performed on single fish; where composites were analyzed, the number of fish is given in parentheses. Composities were of
similar weight.
-'<0.01 ppm represents a trace of conlaminanl above the level of dcleclion (0.001 ppm) but below 0.010 ppm.
Alewifc, rainhow smell, and walleye caught in the main
waters of Lake Huron were the only species in which
I'f » levels declined between 1968-71 and l'.'7.'5-76.
Residues in cisco from Cjcorgian Bay. yellow perch from
Ihc North Channel, and coho salmon and splakc from
the main lake increased during these periods. In the
above species caught in other locations and in other spe-
cies, no trend was evident; PCB levels were static.
Analysis of splakc and lake whitefish on the basis of
similar weight classes indicates that PC'B levels peaked
in splake in 1970 and then declined between 1971) and
1974. CfB levels in lake whitefish declineti between
1972 and 1976 (Table 3j.
In general, the iDDT/PCB and PCB/dieldrin ratios
declined between 196S-7I and I97.S-76 in four species;
bliialers, cisco, coho salmon, and lake whitefish; this sup-
ported the finding that -DDI residues were declining,
dieldrin residues were increasing, and PC'B residues were
static or declining slowly (Tabic 2).
Chlorduni — Residues ot chlordane were detccled in
smallmoulh bass and walleye caught in Georgian Bay in
197-5 at mean levels of 0.01 ppm and O.O.S ppm, respec-
tively (sum of CIS- and fra/i.r-isomers). Trace levels
(•^'0.01 ppiii) were suspected in bloaters, cisco, coho
salmon, and splake in 197.'^. O.xychlordane analysis was
included in 1976. Total chlordane levels found in 1976
ranged from traces in yellow perch tti O.O.V; ppni in ale-
wife; both species were caiighl in Ihc open part of Lake
Huron (Table .'!).
66
Pesticides Monitoring Journ,\i
TABLE 5. Rcxiiliics of chlonhiiic tind licpliwlitor epoxide
ill fish from llic main waters of Lal<e Huron
and Georgian Bay, 1975-76
Location
No. OF
Average
Wrinnr.
Average
Fat,
Residue,
PPM
AND
Heptachi.or
Species
FiSHi
c,
%
Chlordane-
Epoxide
1975 Georgian
Bay
Smallmoulli
9
364
3.2
0.01
ND
bass
<0.01-0.04
Walleye
10
2539
4.7
0.05
<0.01-0.19
Nn
/976 liiAf Hiiriin
Ak-wife
23(5)-
23
10.7
0.039
0.004-0.060
0.026
ND-0.100
Cisco
11(9)
138
5.0
0.025
0.015-0.040
0.013
Nn-o.n44
Yellow perch
17
236
2.5
<0.001
ND-0.()13
0.002
ND .0.0114
Rainbow smell
.12(7)
14
2.7
0.002
ND-0.0I3
0.004
ND-0.007
While sucker
10
977
0.6
0.001
ND-0.013
0.002
ND-0.006
Lake whitefish
15
1323
5.8
0.047
0.025-0.087
0.026
0.013-0.065
NOTE: ND = nol delected lo less than 0.005 ppm.
^Number in brackets represents number of analysis.
-1975 analyses included vis- and rrr/M-s-isomers; 1976 analyses included
CM- and rr«»v-chlordane and oxychlordane.
Ih'pfarhior vpuxidi — No hcpUithlor epoxide w;is idciili-
fied in fish caught prior to 1976. Meiin residues in ale-
wife caught in 197fi ranged from 0.002 ppm in yellow
perch to 0.026 ppm in alewife caught in the main lake
(Table 5).
Hexiichloroheitzeiiv lllCli) — Analyses lor l\CU in lish
tissues were not routinely carried out during the study
period. An indication of the extent of HCH in fish was
obtained from samples caught in 1972 and 1973 from
Lake Huron. One of five splake caught in the open lake
contained 0.001 ppb HCB, and smell caught olf Black
Stone Harbour in Georgian Bay contained 0.03 ppm.
HCB was not detected in a limited number of small-
mouth bass, yellow perch, or lake whitefish from either
Georgian Bay or Ihe main lake.
Discussion
lake Superit)r water analyzed by Glooschenko et al. 13)
was free of DDT, dieldriii, and PCBs down lo the detec-
tion limit. However, residues of these contaminants
were lound in sediment and seston. Setlimeiil samples
taken from various sites in the Canadian waters ol Lake
Superior had measurable amounts (0.005 ppm) of di-
eldrin and -DDT in 14 percent and 5 percent, respec-
tively. PCB resitlues were present in all sediments al all
sites; highest level reported was 1.3 ppm in samples
collected near Marathon. Seston contained only traces
of i;DDT and dieldrin, but the mean level of PCBs was
1.3 ppm, identical lo that in the sediments.
Levels of -DIJT and ilieldrin in lake Iroul caught in
1970 in Lake Superior correspond closely with those
reported by Reinliert (7) in 1966-67. Residues in lake
trout reported in Ihe present study did not agree with
those cited in the LIpper Great Lakes Reference Group
report (U). However, bloaters contained similar residues
in two studies.
Measurable levels of -DDT were reported by Gloos-
chenko et al. in 29 percent of sediments taken from
various sites in the Canadian waters of Lake Huron and
in 14 percent of sediments taken from Cieorgian Bay (3);
maximum levels in both Lake Huron and Georgian Bay
were 0.02 ppm. Dieldrin was present at trace levels.
and PCBs ranged up to 0.02 ppm. i;DDT and dieldrin
in sediments from the North Channel were below detec-
tion levels, but traces of PCBs were found. Organo-
chlorincs were highest in seston from the open lake,
ranging from 0.8 to S. I ppm compared to 0.7 to 6.7 ppm
in Georgian Bay and a high level of 1.0 ppm in the
North Channel.
Residue levels of -f^DT and dieldrin in lish from Lake
Huron and Georgian Bay reported in this paper cor-
respond closely to the levels reported previously by
Reinhert (7) and Reinke et al. (9) for alewife, bloaters,
kokanee lOiicorliyiiclnis nvrl<a), rainbow smelt, and wall-
eye, but discrepancies are evideni in yellow perch, lake
whitefish, and rainbow trout. -DDF mean residues of
2.44 ppm are reported by Reinhert for alewife caught in
1966-67 (7J; the present study reveals a decline to 1.63
ppm -DDI mean residues in 1970 and a furlher decline
10 0.<S() ppm i:DDr by 1976; conversely, dieklrin levels
were slightly higher in 1976 (0.14 ppml than in 1966-67
(O.O.S ppm). Levels of -DDT in rainbow trout show little
change between the 1966-67 study and those detected in
1970 in the present study, 0.7.5 and O.S ppm. respec-
tively. However, a marked decline lo a mean residue of
0.15 ppm by 1976 occurred in rainbow trout caught in
Lake Huron. A mean level of 4.7 ppm -DDT in bloat-
ers caught in 1970-71 in Ihe present study is similar to
levels of 3.6 ppm and 3.08 ppm reported respectively by
Reinhert (7) in 1966 and Reinke et al. (9) in 1970. Mean
levels of -DDT, dieklrin, and PCBs in bloaters in the
present study closely parallel those reported by the Upper
Great Lakes Reterence Group (II) for 1975-76.
Reinke et al. found 6.02 ppm -DDT in walleye caught
in 1970 in the main waters of Lake Huron (9); this is
close lo Ihe mean level of 5.05 ppm reported here.
Reinke el al. reported 0.47 ppm -DDT in walleye caught
ill 1970 in Georgian Bay (9), but Ihe present study re-
ports mean levels of 2.2 ppm and 3.1 ppm, respectively,
for 1970 and 1971. This discrepancy may be partly
cxplainetl by the fad thai ihe walleye in the present study
were obtained al the mouth of Ihe Moon River, an area
where high DD T residues were reported (2. 6).
Residues in kokanee from l,ake Huron reported here are
similar to those reported by Reinke el al. {9) but i:DDT
Vol. 12, No. 2, Siiiti-mulr 197S
67
residues of 0.52 ppm in yellow perch reported in the
present siitdy are considerably lower than the mean
values of 1.59 ppm in 1966-67 and 1.46 ppm in 1970
reported by Rcinhert {7) and Reinkc et ai. {9), respec-
tively. Mean -DDT residues in lake whitefish in the
present study are also markedly lower than those re-
ported previously i7, 9).
Although there are differences in the data for -DDT
levels in coho salmon between the present study and
earlier reports, there is more similarity among coho
salmon from the same location. Reinkc ct al. reported
a mean of 1.26 ppm -DDT and O.OX ppm dieldrin for
fish caught in northern Lake Hiiron {'->)\ the present
study shows mean levels of 0.98 ppm iDDT and 0.04
ppm dieldrin for 41 coho salmon caught in the same
area. -DDT levels in rainbow trout caught in soLithern
Georgian Bay vary considerably from those reported
previously. Reinkc et al. reported a mean of 8.7 ppm
-DDT in rainbow trout caught in 1970 [9), but only
1.75 ppm IDDT was found in the same species caught
in the same location in 1968 for the present survey. This
discrepancy may be due to local dilTerences in -DDT
use.
Despite the number of variables which are associated
with a sampling study of this kind, it is remarkable that
such close agreement is found between ditTcrent studies
in different time frames for such large bodies of water
as Lakes Superior and Huron. Other factors that cause
fluctuations in contaminant concentrations in fish tissues
are spawning times and changes in fat content.
Acknowledgment
The assistance of the field staff of the Ontario Ministry
of Natural Resources in collecting the fish for this study
is gratefully acknowledged. Particular thanks are given
to J. .S. Ball, J. Collms, VV. R. Hesson, F. Mantec, J. No-
vak, R. Payne, and L. Thurston. Technical assistance
was provided by J. Stanck and Y. P. Lo in preparation
of samples for analysis.
LITER.-\TURE CITED
(1) American Fisheries Society, Committee on Names of
Fislies. 1970. A list of common and scientific names
of fish from the United States and Canada (3rd ed.).
Am. Fish. Soc. Spec. Publ. 6. Washington. D.C. 150 pp.
(2) Frank. R.. A. E. Armstroni;, R. G. Boelens. II. E.
Braan. and C. W. Doii.vlas. 1974. Oiganochlorine in-
secticide residues in sediment and fish tissue, Ontario,
Canada. Pestic. Monit. J. 7(3/4) : 165-180.
(3) Clooschenko. W. A., W . M. J. Slruchan, and R. C. J.
Sampson. 1976. Distribution of pesticides and poly-
chlorinated biphcnyls in water, sediments, and seston
of the Upper Great Lakes — 1974. Pestic. .Monit. J.
I0(2):61-67.
(4) Holdrinet, M. 1974. Determination and confirmation
of he.xachlorobenzene in fatty samples in the pres-
ence of other halogenated hydrocarbon pesticides and
PCBs. J. Assoc. Off. Anal. Chem. 57(3 ) :580-584.
(5i Lan.vlois, E. B., A. P. Stcmp, and B. J. Liska. 1964.
Analysis of animal food products for chlorinated in-
secticides. J. Milk Food Technol. 27(7 ) :202-204.
(6} Miles. ]. R. W., and C. R. Harris. 1973. Organochlo-
rine insecticide residues in streams draining agricul-
tural, urban-agricultural, and resort areas of Ontario,
Canada— 1971. Pestic. Monit. J. 6(4) : 363-368.
{7) Rcinlicrt. R. E. 1970. Pesticide concentrations in Great
Lakes Fish. Pestic. Monil. J. 3(4) :233-240.
(8) Reinhert, R. £., and H. L. Bergman. 1974. Residues
of DDT in lake trout (Salveliniis namaycush) and coho
salmon (Oneorliynchus kisatch) from the Great Lakes.
J. Fish. Res. Board Can. 31 (2 ): 191-199.
(9) Reinkc. J.. J. F. Vthe. and D. Jamieson. 1972. Or-
ganochlorine pesticide residues in commercially caught
fish in Canada— 1970. Pestic. Monit. J. 6(l):43-49.
[10) Reynolds, L. M. 1971. Pesticides residue analysis in
the presence of polychlorinatcd biphenyls (PCB's).
Residue Rev. 34:27-57.
(11) Upper Great Lakes Reference Croup. 1976. The
waters of Lake Huron and Lake Superior, Vol. 1.
Summary and recommendations. International Joint
Commission, Windsor, Onliuio. pp. 115-125.
68
Pesticides Monmoring Journal
Residues of Organochlorine Insecticides and PoJychlorinated Biphenyls in
Fish from Lakes Saint Clair and Erie, Canada — 1968-76 '
Richard Frank,' Heinz E. Braun,- Micheline Holdrinet,^
Douglas P. Dodge,' and Stephen J. Nepszy '
ABSTRACT
Eighteen species of fish from Luke SainI Ckiir unci 19 species
from Lake Erie were unalyzed for organochlorine pesticides
and polychlorinuted biphenyls (PCBs) between 196S and
1976. Mean residues of ':^DDT peaked at L19 ppm in
longnose gar (Lepisosteus osseus) caught in Lake Saint
Cluir in 1970-71 , but had declined in all species by 1975-76.
Dieldrin levels in fish tissues increased over the same period.
White bass (Morone chrysops). caught in 1975 in Lake Eric,
had the highest mean residue of dieldrin at 0.17 ppm. PCB
residues increased in some species and decreased in others.
PCB residues exceeding the tolerance level of Health and
Welfare Canada were found in the following: from Lake
Saint Clair, smallniouth bass (Micropterus dolomieui) in
1975 and channel catfish (Ictakiriis piinctatus) in 1971 : from
Luke Erie, coho salmon (Oncorhynchus kisutch) /;; 1970,
smallmouth bass, ulewife (Alosa pseiidoharengus), fresh-
water drum (Aplodinotus griinniens), and gizzard shad
(Dorosoma cepedianiini ) in 1971. and wliite bass in 1971
and 1976.
Sediments in Lake Erie were five to ten times more highly
contaminated with '^DDT, dieldrin, and PCBs than were
sediments from Lake Saint Clair. IDDT and dieldrin residues
in fish tissues did not necessarily reflect this trend, hut PCBs
were higher in fish from Lake Erie.
Introduction
DDT, dieldrin, and PCBs have been identified in fish
from Lake Erie and Lake Saint Clair. Reinert reported
residues of -DDT in 14 species caught in 1967-68 that
ranged from 0.25 ppm in spottail shiner {Notropis
hitdsoniiis) to 1.89 ppm in white bass (Morone chry-
sops) (11). Dieldrin was not detected in nine species:
ma.ximum dieldrin levels found in alewife (Alosa psciido-
^ Partial funding for 1975-76 sampling and analysis provided by the
International Joint Commission under Task Force D of the Pollution
f I om Land Use Activities Group.
-Provincial Pesticide Residue Testing Laboratory, Ontario Ministry of
Agriculture and Food, c/o University of Guelph, Guelph. Ontario
NIG 2W1.
■'Fisheries Branch, Ontario Ministry of Natuial Resources, Queen's
Park, Toronto, Ontario.
^Fisheries Research Station, Ontario Ministry of Natural Resources,
Wheatley, Ontario.
harengiis) were 0.15 ppm. Reinke et al. found similar
residues in six species caught in 1970 (13). The highest
residues of i;DDT were 0.56 ppm in alewife. Carr et al.
reported on si.x species caught in 1970-71 (2). Coho
salmon {Oncorhynchus kisutch) contained the highest
mean residues of -DDT and dieldrin, 0.90 ppm and
0.07 ppm, respectively: channel catfish (Ictalurus piinc-
tatus) had the highest mean PCB residues: 4.4 ppm.
Kelso and Frank found that -DDT and dieldrin residues
varied with time of catch in three species from the
eastern basin of Lake Erie (7). Residues were generally
low; higher residue levels were associated with fish hav-
ing a higher fat content.
Watersheds on the Canadian side of Lakes Erie and
Saint Clair drain the most intensive agricultural belt in
Ontario (Figure 1). Before restrictions on the use of
aldrin, dieldrin, and heptachlor in 1969 and 2DDT in
1970-71, this area accounted for 90 percent of organo-
chlorine insecticides used in Ontario. Miles and Harris
(9, 10) and Frank et al. (3, 4) reported that DDT and
dieldrin were deposited in Lake Erie by creeks draining
areas of intensive pesticide use. Frank et al. found that
fish caught in the streams and creeks had residues of
-DDT and dieldrin that were one order of magnitude
higher than those caught in the adjoining waters of Lake
Erie (4).
The present study was initiated in 1968 to determine
organochlorine residues in fish before legislative restric-
tion of the use of these materials. After use of the
materials was restricted, monitoring of fish tissue was
continued to determine the impact of these actions. At
the same time, PCBs were identified in fish in both
lakes, and monitoring for these contaminants was in-
cluded to determine whether the voluntary restrictions
on their use since 1971 were reflected in residue levels in
fish tissue.
Methods and Materials
Twenty-eight species of fish were caught by gill net or
trap net between 1968 and 1976 in Lakes Saint Clair and
Erie (Table 1). Most were obtained from the field
Vol. 12, No. 2, September 1978
69
LAKE ST CLAIR
® MrrCMtlL BAY
<Z> B&SSETT CHAr#€L
^ nCIOLAY CRCCK
O
WESTERN BASIN
CENTRAL BASIN
© EASTERN BASIN
® KINGSVILLE
© WHEATLEY
© ERIEAU
PORT STANLEY
@ PORT BURWELL
® PORT MAiTLAND
LONG POINT BAY
FElCe ISLAND
t
HCjURF I. A/(//' <'f /.(/^(■\ Eric <iiul Saint Clair slunviiii; fisli loUcctinn areas.
stall' ot the Ontario Ministry of Natural Resources.
Some ot the larger fish were obtained from commercial
gill net catches. Eighteen species (278 fish) were caught
in Lake Saint Clair in or around Mitchell Bay, Tremblay
Creek, and Bassett Channel (Figure 1 ). Nineteen species
(1.023 fish) were caught in Canadian waters of Lake
Erie. These came from onshore and otTshore locations
in all three basins, as defined by Thomas et al. (16).
Eleven species (429 fish) from the western basin were
caught ofT Kinsville and west of Pelee Island. Nine
species (287 fish) were caught in the central basin oil'
Whcatlcy, Erieau, Port Stanley, and Port Burwell. Fif-
teen species (307 fish) from the eastern basin were
netted in Long Point Bay and olV Port Maitland
(Figure 1).
Fish species were identified and named according to
the nomenclature of the American Fisheries Society (/).
A nalytical Procedure
Fish were eviscerated, their heads were removed, and
the remaining flesh was minced in a Hobart food
chopper to a homogeneous consistency from which a
representative subsample was selected. Tissue homo-
gcnates were stored at — 20 C until analysis; storage
TABLE 1. .Analyses of fish caught in Lakes Saint Clair
ami Erie, I96S-76
Lake Sa[ni
Clair
Lake Erie
Fish
Fish
Analyses
Fish
Fish
Analyses
Year
SPHCItS
Caught
Performed
Species
Caught
Performed
1968
6
25
25
14
115
106
1970
6
45
45
11
11
1971
\5
183
18.1
11
1.17
119
1972
0
0
11
78
78
1973
0
0
(1
10
1
1974
0
0
0
5
5
1975
1
6
6
11
636
181
1976
T
19
19
31
31
TOTAL
18
278
278
19
1023
532
NOTE: Purees of cvisccraied. headless samples were analyzed.
time rarely exceeded 4 months. Ten grams of tissue
homogenate was ground with 100 g anhydrous sodium
sulfate and 25 g Ottawa sand. This mixture was ex-
tracted in hexane for 7 hours in a Soxhiet extractor.
The solvent was removed by rotary vacuum, and the
percentage of fat or oil was determined gravimetrically.
A one-step Morisil column cleanup method described b>
I.anglois ct al. was used to isolate organochlorines and
PCBs (cS). Florisil (60-100 mesh), activated commer-
cially at 650 C, was reheated at 135-C for at least 24
70
Pesticides Monitoring Journal
hours; after the adsorbent cooled, it was equihbrated
with 5 weight percent water. A maximum of 1 g fat
from the fish extracts was thoroughly mixed with 25 g
of conditioned Florisil; this was placed on top of a
second 25-g portion of conditioned Florisil in a 25-mm
ID cleanLip column. The column was eluted with 300 ml
1:4 (v/v) mixture of dichloromethane-hexane. The
eluate was evaporated to dryness with rotary vacuum,
and the residue was dissolved in 5 ml acetone.
PCBs were separated from organochlorine insecticides
and HCB on a charcoal column as described by Holdri-
net (6). Charcoal (Fisher No. 5-690, 50-200 mesh)
was washed with acetone, filtered by suction, dried, and
stored at 135'C. Columns (9-mm ID) were prepared by
sandwiching a 7.5-cm layer of charcoal between 1.3-cm
layers of sand and prcwashing with a 1 :3 (v/v) mixture
of acetone-diethyl ether, The acetone solution from the
Florisil cleanup was quantitatively transferred to the
charcoal column and eluted successively with 180 mi of
1:3 (v/v) mi.xture of acetone-diethyl ether and 80 ml
benzene; the organochlorine insecticides were contained
in the first eluate, and PCBs were in the second eluate.
Eluates were concentrated to dryness by rotary vacuum
and dissolved in measured amoLints of hexane.
Extracts were analyzed on a Tracor Model 550 gas
chromatograph with the following instrument parameters
and operating conditions:
Detector: '■■'Ni election-capture
Column: glass. 15 cm x 0.64 cm OD packed with a
mixure of 4 percent SE-.TO and 6 percent QF-1
on 80-l()ll-mesh Cliromosorb W
Temperature: 180"C
Carrier gas: nitrogen flowing at 60 ml/minute
Injection volume: 5 /j 1 equivalent to 1 ng fat
Residue identity was confirmed on random samples by
thin-layer chromatography (TLC); appropriate areas
of the chromatogram were removed, redissolved, and
re-examined by gas-liquid chromatography (GLC). This
confirmation was essential for the positive identification
of <r/.v- and //YHi.y-chlordane which, when analyzed by
GLC alone, are subject to misidentification because of
co-extractive interferences.
Recoveries of pesticides and PCBs were checked peri-
odically by fortification of fish tissue homogenate before
the Soxhiet extraction. Average recoveries were as
follows: p.p'-DDT. 89 percent; p.p'-DDE, 96 percent;
p.p'-JDE. 94 percent; o./>'-DDT, 91 percent; dieldrin,
89 percent; r/.s-chlordane, 92 percent; fra/;.s-chlordane,
90 percent; and PCBs, 85-90 percent. The data do not
include corrections for recovery. Quantitation limits,
below which values were designated as either trace or
not detected, were set at 0.005 ppm in fat for all or-
ganochlorine insecticides and 0.05 ppm in fat for PCBs.
PCB estimations were based on comparison with
Vol. 12, No. 2, September 1978
standard mixtures of Aioclors 1254 and 1260 and were
quantitated by comptirison of the sum of peak heights
of peaks VII, VIII, and X according to the Reynolds
ntmibering system (14). The ratio of Aroclor 1254 to
Aroclor 1260 in ihe standard mixttire varied from
5:1 to 4:1.
Analysis began in 1968 when the known main con-
taminants in fish were p,p'-DDJ and its analogs and
dieldrin and heptachlor epoxide; PCB values before 1970
were estimated. With the introduction of a column frac-
tionation technique in 1970 for the separation of PCBs
from organochlorine insecticides, the measurement of
PCB residues became more precise. Analysis for hexa-
chlorobenzene (HCB) was included in the procedure
in 1973 but was subsequently discontinued because of
the low levels and incidence of HCB found in the
samples. Analysis and confirmation for cis- and Irans-
chlordanc was refined in 1975, and the analyses for
mire\ and oyychlordane were introduced in 1976.
Results
LAKE SAINT CLAIR
^DDT — None of the 18 species caught in Lake .Saint
Clair contained metin residues of iJDDT that exceeded
the 5 ppm action level established by both the Canadian
and United .States governments. Longnose gar (Lepisos-
tciis osseiis) caught in 1971 had the highest mean
residue of 1.19 ppm ;tnd was the only species with a
mean residfie above 1.0 ppm (Table 2). Eight of 12
longnose gar caught otT Tremblay Creek contained
-DDT residues of 1.10-2.35 ppm. Individual fish from
three other species contained residues that exceeded
1.0 ppm. In 1971, two of eight carp (Cyprinus caipio)
from Mitchell Bay contained 1,19 ppm and 1,26 ppm
-DDT, Four of 12 mooneye (Hiodoii tergisits) caught
in 1970 off Tremblay Creek had 1,12-2.38 ppm 2DDT.
Three of six smallmotith bass (Micropicrus dolomieui)
caught in 1975 had :;:DDT residues of 1.02-1,15 ppm.
Eight of the 18 species from Lake Saint Clair were
caught in 1968-71. In seven of the species, residues
of i:DDT showed a decline by 1971 (Tables 2, 3). Only
quillback {Carpiodes cyprinus) showed no apparent
change. In all years, however, residues of -DDT were
below 0,5 ppm,
Smallmouth bass, freshwater drum (A plodinotiis griin-
n'wns), and walleye {Stizostedion vitrcum vitreitin) were
the only three species caught in 1968-71 and again in
1975-76, In smallmouth bass, mean -DDT residues
were higher in 1976 (0,76 ppm) than in 1968 (0,42
ppm); however, the mean weight of fish was 853 g as
opposed to 453 g (Table 2). When residues of similar
weight classes were compared, the residue declined
slightly between the two periods (Table 3). A mean
71
TABLE 2. OifHiiioililuiiiif nxitliies in Iti jisli ipccUw caiis^hl in Canadian waters of Lake Saint Clair, I96S-76
Mean and
Range
Puree, ppm-
■\'i:ar
No. oi
ANALYSE!
Weiuhi.
1 G
Fat,
%
Mean CONIENI AND
RanCiF of CONlAMlNAN is in nan
Species
DDE
TDE
DDT
:;ddt
DlELDRIN
PCBs
.-1 iniiiluc
Bow I'm
1971
10
I.K.7
955-2050
0.2
0.1-0.4
<0.01
<0.01-0.0I
<0.0I
<0.01
0.01
<0.01-0.02
<0.01
<0.1
CaliistoniUlae
Quillbuck
197(1
6
1.119
4.2
0.03
0.03
0.02
0.08
0.01
0.3
.300-1775
1.6-7.6
0.01-0.04
0.01-0.06
0.01-0.03
0.03-0.13
<0.01 0.02
0.2-0.4
1971
9
1244
2.1
0.03
0.03
0.02
0.08
<0.01
0.2
350-1935
1.1-4.5
<0.01-0.07
<0.0I 0.08
<0.01-0.06
0.02-0.17
<0.1-0.3
Rcdhorsc
1970
8
928
2.6
0.07
0.03
0.03
0.13
0.01
0.7
695 1235
0.3-5.8
<0.0 1-0.25
<0.01-0.11
<0.0I-0.13
<0.01-0.49
<0.0l-0.04
<0. 1-2.6
1971
8
698
0.7
0.01
0.01
<o.oi
0.03
<0.0I
0.2
375-985
0.3-1.3
<O.OI-0.03
<0.0 1-0.02
<0.0 1-0.02
0.01-0.07
<0.1-0.4
White
196S
t
547
2.8
0.07
0.04
0.08
0.19
<0.01
0.1
sucker
306-787
2.2-3.4
0.01-0.12
0.01-0.07
0.02-0.14
0.04-0.33
<0. 1-0.2
1970
10
1298
1.3
0.01
0.02
0.01
0.04
<0.01
0.3
1(135-2050
0.7-2.5
<0.0 1-0.03
<0.OI 0.04
<0 .01-0.03
<0.0 1-0.06
0.2-0.4
C'i'ntrarchiJae
1 argemoiiih
197U
6
564
3.5
0.22
0.09
0.11)
0.41
0.03
1.3
bass
315-685
1.8-7.2
0.12-0.40
0.04 0.22
0,03-0.26
0.19-0.88
<0.0 1-0.08
0.3-4.3
1971
5
632
2.6
0.18
0.07
0.06
0.3 1
0.02
0.8
250-11(10
1.4-4.2
0.14-0.21
0.03-0.13
0.02-0.11
0.19-0.45
<0.01-0.04
0.6-1.2
Rock bass
1971
11)
230
0.4
<0.01
<0.0I
<0.01
0.01
<0.01
0.1
145-335
0.1-0.7
<0.0 1-0.02
<0.01-0.02
<0.0 1-0.04
<0. 1-0.3
Smallnioiith
1968
5
453
2.9
0.20
0.11
(1.21
0.52
<0.01
0.3
bass
283-748
2.0-3.4
0.13-0.31
0.08-0.18
0.14-0.32
0.38-0.69
0.2-0.6
1975
6
853
2.5
0.60
0.11
0.05
0.76
0.09
2.1
264-1491
1.1-3.6
0.09-0.92
0.02-0.16
0.02-0.09
0.13-1.15
0.03-0.14
0.4-3.1
BUicgill
1971
25
172
85-250
0.4
(1.1-1.8
<0.01
<0.01-0.02
<0.01
<0.01
0.01
<0.0 1-0.04
<0.01
<0.1
<0. 1-0.2
Black crappic
1968
6
174
2.3
0.08
0.05
0.10
0.23
<0.0I
0.2
116-212
0.4-6.2
0.03-0.17
0.01-0.12
0.04-0.71
0.11-0.60
<0. 1-0.5
1971
13
199
35-455
0.3
(1.2-0.6
<0.01
<0.01-0.0l
<0.01
<0.01
0.01
<0.01-0.02
<0.01
<0.1
<0. 1-0.2
Ptinipkinsccd
196S
5
118
2.8
0.03
0.03
0.05
0.11
0.01
0.1
97-137
2.3-3.7
0.02-O.03
0.02 0.04
0.04-0.06
0.08-0.13
<0.01-0.02
<0.1-0.2
1971
22
104
0.4
0.02
0.01
0.01
0.04
<0.01
<0.1
40-265
0.1-0.8
0.01-0.02
0.01-0.01
0.01-0.02
0.03 0.05
<0.01-0.01
<0. 1-0.1
Cyprinidtw
C arp
1971
8
3676
10.1
0.30
0.19
0.04
0.53
0.04
0.7
1410-9710
3.1-22.0
0.04-0.84
0.05-0.53
<0. 01-0. 10
0.09-1.26
<0 .01 -0.1 3
0.3-1.5
Hioilantidac
Mooncve
1970
12
306
10.7
0.72
0.09
0.12
0.93
0.03
1.9
100-485
6.8-14.9
0.31-1.20
0.05-0.29
0.01-0.89
0.10-2.38
0.01-0.13
0.7-7.2
IctiilurUlac
Brown
1971
12
427
0.5
<0.01
<0.01
<0.01
0.01
<0.01
0.1
bullhead
240-580
0,1-1.4
<0.()l-0.02
<0.0 1-0.03
<0.1-0.3
Channel
1971
6
2016
5.2
0.36
0.10
0.08
0.54
0.02
2.3
cattish
465-5275
2.6-10.2
0.14-0.75
0.03-0.14
<0.01-0.17
0.22-0.89
<0.01-0.04
0.9-3.9
I.cpisustcidae
l.ongnose gar
1971
12
723
3.7
0.79
0.27
0.13
1.19
0.02
1.5
320-1310
0.7-9.1
0.28-1.82
0.12-0.46
<0.01-0.2I
0.48-2.35
<0.01-0.03
0.5-4.0
Percidtte
Yellow perch
1968
3
201
1.1
0.08
0.05
0.10
0.23
<0.01
<0.1
135-2.16
0.5-1.4
0.04-0.16
0.02-0.10
0.04-0.23
0.10-0.49
1970
i
108
0.4
0.02
<0.01
<0.01
0.03
<0.01
0.1
80-155
0.1-0.7
<0.01-0.2
<0.01-0.0I
<0.0 1-0.05
<0. 1-0.2
1971
11
59
0.3
0.01
<0.01
<0.01
0.02
<0.01
0.1
35-75
0.1-0.5
<0.0 1-0.02
<0.01-0.01
<0.01-0.03
<0.1-0.2
Walleye
1968
4
410
1.1
0.08
0.04
0.08
0.20
<0.01
<0.1
250-539
0.8-1.3
0.02 0.14
0.01-0.06
0.02-0.14
0.05-0.34
1971
20
401
2 2
0.05
0.05
0.01
0.11
0.02
0.4
120-1990
0.1-5.1
<0.01-O.I7
<0.01-0.25
<0.0 1-0.04
<0.01-0.42
<0.01-0.15
<0. 1-2.0
1976
9
1726
0.8
0.06
0.01
0.01
0.08
0.01
0.2
203-33 1 1
0.3-2.5
<0.OI 0.21
ND-0.05
ND-0.04
<0.0 1-0.28
ND-0.01
<0. 1-0.8
SciaeniJae
Freshwater
1971
12
519
1.6
0.01
<0.01
0.01
0.03
<0.01
0.2
drum
225-1130
0.3-6.1
<0.0 1-0.04
<O.OI-0.02
<0.01-0.05
<0.01-0.09
<0. 1-0.6
1976
10
259
1.7
0.02
<0.01
<0.01
0.03
<0.01
0.2
86-521
0.6-4.4
<0.01-0.04
<0.0 1-0.02
ND-0.01
0.01-0.05
<0.1-0.3
NOTE: ND = nonc detected.
'Number of analyses represents number of individual fish (278).
= Eviscerated fish with heads and tails removed.
residue of 0.0.^ ppm IDDT was piescni in licshw;itcr
drum caught in 1971 and 1976, and little change oc-
curred among dilTercnt weight classes (Tables 2, 3).
Walleye caught in ihrce separate years had steadily
declining -DDT residues: 0.20 ppm in l')6S, 0.1 I ppm
in 1971, and 0.08 ppm in 1976. By weight class, a
72
Pesticides Monitoring Journal
TABLE 3. Comparison of vcshlues by weight class oj six fish species euiiaht in Lakes Saint Clair and Erie, 1968-76
WllGHl
NUMUI R OF
Mean
Mean
Content of Resi
Tissue, pi-m
DUES IN
Weight,
Fat,
Species
Lake'
Year
Class, kg
Analyses -
G
%
i:DDT
DiELDRIN
PCBs
Smollmoiith bass
Saint Clair
1968
0.25-U.50
4
378
2,8
0,48
0,006
0.38
0.50-U.75
1
748
3.3
0,67
ND
0.26
1975
0.25-0.50
1
264
2.5
0,13
0.0.30
0.40
0.50-0.75
1
698
1,1
0,28
0.030
0.90
0.75-1.00
2
826
3.5
0.93
0.125
2.60
I.UO +
2
1252
2,1
1.13
0.120
3.0(1
Erie
1968
0-0.25
9
206
1.6
0,52
0.004
0.28
(E)
0.25-0.50
7
374
2.0
1,24
0.009
0.41
1971
1.25-1.50
T
1449
7.5
1,20
0.002
5.80
1972
0-0.25
8
89
2 2
0,12
0.006
0.35
0.25-0.50
8
412
3,5
0,25
0.019
0.86
0.50-0.75
T
624
4,0
0,33
0.025
1.00
1975
0.25-0.50
1
480
3,8
0,12
0.050
0.4(1
0.50-0.75
1
707
3,5
0,09
0,20
0,30
0.75-1.0(1
,1
83H
3,9
0,15
0,027
0.30
1.00 +
1
1226
5,4
0,30
0.020
0.40
White bass
Erie
1968
0-0.25
7
127
2.7
0,32
0.010
0.06
(E,W)
0.25-0.50
1
295
2.1
1,51
0.007
0,31
(E.C.W)
1971
0-0.25
29
156
5.3
0.11
ND
1,44
0.25-0.50
T
388
8.0
0.15
ND
3,10
(E)
1972
0-0.25
27
124
3.2
0.15
0.014
0,65
0.25-0.50
2
361
7.2
0.55
0.025
3,30
0.75-1.00
1
755
9.0
0.71
0.020
4,7(1
(C,W)
1975
0-0.25
3
77
7.5
0.16
0,153
0.70
0.25-0.50
1
319
8.6
0.42
0.160
2.40
0.50-0.75
1
607
7.3
0,56
0,190
3.20
(E)
1976
0-0.25
6
93
3.5
0.05
(1.005
0.12
0.25-0.50
1
274
3.8
0,06
0.006
0,10
Treshwater drum
Saint Clair
1971
0-0.25
2
235
1.0
0,01
0.004
0.09
0.25-0.50
5
405
2,0
0,03
0.005
0,22
0.50-0.75
3
560
1,1
0,02
0.002
0,13
1.00-1.25
T
1023
1,9
0,05
0,004
0,21
1976
0-0.25
4
I3,S
0.8
0.03
0,004
0.17
0.25-0.50
5
303
2.3
0.03
0,004
0,17
0.50-0.75
1
521
1.0
0.04
ND
0,18
Erie
1968
0-0.25
8
12(1
2.6
0.23
0.005
0.05
(W)
0.25-0.50
3
344
2.8
0,27
0.008
0.05
(E,C,W)
1971
0-0.25
18(14)
144
5.9
0,03
ND
1.75
0.25-0.50
7
387
9.0
0,12
ND
2.17
0.50-0.75
3
570
6.3
0,23
ND
3.87
(E.C.W)
1975
0-0.25
9(16)
85
3.1
0,03
0.017
0,28
0.25-0.50
13
387
4.7
0,10
0,038
0,85
0,50-0.75
10
606
4.9
0,17
0.036
0.57
0,75-1.00
2
832
3.7
0,10
0.015
0.25
Yellow perch
Saint Clair
1968
0-0.25
3
201
1.1
0.24
0.003
0.09
1970
0-0.25
3
108
0.4
0.28
0,003
0,12
1971
0-0.25
11
59
0.3
0.02
0,003
0,11
Erie
(C,W)
1968
0-0.25
23
123
1.0
0.11
0,006
0.06
(E,C,W)
1971
0-0.25
29
112
2.1
0.04
ND
0.64
(E)
1972
0-0.25
29
87
2.6
0.08
0,011
0.25
0.25 0.50
1
449
4.4
0.07
0,010
0,23
(E,C,W)
1975
0-0.25
42(111)
6^
1.9
0.06
0,023
0,38
0.25-0.50
-)
384
3.4
0,11
0.035
0,45
0.50-0.75
-t
594
2.9
0,06
0,035
0.30
(E)
1976
0-0.25
15
112
1.6
0.04
0.012
0.20
Coho salmon
Erie
(C)
1968
0-1,0
2
471
5.4
0.51
0.029
0.33
1970
1.0-2.0
2
1795
12.6
4.53
0.100
5,80
2.0-3.0
9
2263
11,6
2.40
0.080
2,10
(C)
1971
0-1.0
3
806
11,5
1.76
0,010
1,70
(C,W)
1975
0-1.0
1
932
0.1
0.12
0,020
0,70
1.0-2.0
6
1823
1.1
0,15
0.035
0,90
2.0-3.0
10
2501
0,9
0.11
0.035
0,63
3.0-4.0
8
3369
1,3
0,20
0,050
1.06
5,0-6.0
1
5300
2.5
0,76
0,070
2.70
1976
0-1,0
1
515
1.7
0.09
0.014
0,26
1,0-2.0
1
1625
2.7
0,09
0.012
0,52
2.0-3,0
3
2641
1.9
0.11
0.011
0,28
3.0-4.0
1
3125
1.4
0.04
0,004
0,11
Walleye
Saint Clair
1968
0-0.5
3
366
1.1
0.14
0.004
0,07
0.5-1.0
1
539
1.2
0,34
0.004
0,12
1971
0-0.5
15
225
2.6
0.13
0.026
0,50
0.5-1,0
4
660
0,7
0.02
0,001
0,13
1,5-2.0
1
1990
1,2
0.06
0,003
0,17
1976
0-0,5
1
203
2,5
0.18
0.011
0.75
0,5-1,0
-)
678
0,8
0.04
ND
0,11
1,5-2,0
3
1690
0,3
0.02
ND
0,09
2.0-2,5
1
2496
0,7
0.12
0,008
0,28
3,0-3,5
2
3204
0,8
0.15
0,055
0,32
(Continued next page)
Vol. 12, No. 2, September 1978
73
TABLE 3 (cont'd. ). Comparison of residues by weialit class of six fish species cuuglit in Lakes Saint Clair and Erie. 1968-76
Mean
Species
Year
WCIliHl
Number of
Weight
Class, kg
Analyscs-
a
0-0.5
.1
265
0.5-1.(1
.1
77.!
0-0.5
4
.164
0.5-1.0
1
725
0-0.5
1(5)
72
0.5-1.0
1
9116
2.0-2.5
2
2175
Fat,
Mean Content of Residues in
Tissue, fpm
Yddt
Dielorin
PCBs
0.005
0.08
0.010
0.24
ND
0.89
ND
1.10
0.054
0.66
0.060
0.70
0.360
4.60
Erie
(W)
(E.W)
(W)
1968
1971
1975
2.1
.1.7
.1.7
3.0
3.7
3.9
21.3
0.24
0.42
0.04
0.02
0.13
0.15
1.32
'E=:eastcrn basin; C -central basin; W — western basin.
-Anal>ses perliirmed on single fish in most cases; in sonic cases composite
markeil clrop \v;is iiotciJ for -DDT between 1968 and
1971, hut there;il"ter the iJecline was small (Tahles 2, 3).
Dicldrin — Mean residues in all speeies were less than
0.10 ppm. In addition, 12 species had mean residues
at or below 0.01 ppm dieldrin. The highest mean resi-
due of 0.09 ppm was present in smallmouth bass caught
in 1975 (Table 2). By weight class, smallmouth bass
exhibited an increase in dieldrin residues between 1968
and 1976 (Table 3). Only three other species, carp,
nioone_\e. and walleye, had individual fish with residues
ot 0.10-0. 1.*^ ppm dieldrin (Table 2). Dieldrin residues
in walleye peaked in 1971 ;ind declined by 1976
(Table 3). Freshwater drum, the only other species
caught in the earh and late years, showed no change
in dieldrin residues (Tables 2, 3).
PCB,s— Only one fish trom Lake Saint Clair, a 435-g
mooneye, exceeded the 5.0 ppm tolerance level for PCB
residues in fish tissues set by the Food and Drug Ad-
ministration, U.S. Department of Health, Education,
and Welfare. However, several species and individual
fish e.xceeded the 2.0 ppm Health and Welfare Canada
tolerance level (Table 2). Smallmouth bass caught in
197.S and channel catfish caught in 1971 had mean
residues of 2.1 ppm and 2.3 ppm PCBs, respectively
(Table 2). In 1970, one of six largemouth bass (Mic-
ropterus salmoidcs), four of 12 mooneye, and one of
samples were analyzed, and the number of fish is in parentheses.
eight redhorse (Moxostoma sp.) contained 2.1-7.2 ppm
PCBs. In 1^)71, three of 1 1 longnose gar, and four of
six channel catfish caught in Tremblay Creek and in
Mitchell Bay, respectively, had residues of 2.0-4.0 ppm
PCBs. In 1975, PCB levels in four of six smallmouth
bass ranged from 2.2 to 3.1 ppm.
PCB residues increased in smallmouth bass between
1968 and 1975. However, freshwater drum and walleye
showed little change even by weight class (Tables 2, 3).
HCB — Forty-eight fish of 17 species caught in 1970-71
and analyzed in 1973 had detectable HCB residues
below 0.1 ppm. Redhorse mullet had the highest mean
residue, 0.024 ppm, and the highest residue in a single
fish, 0.08 ppm. Carp, channel catfish, and yellow perch
(Perca fhivesci'iis) had the second highest residues of
0.013 ppni HCB (Table 4).
Chlordiinc ami hcplacldor epoxide — The same 48 fish
caught in 1970-71 were anal\zed for cis- and trans-
chlordane and hcptachlor epoxide. Interfering com-
pounds prevented confirmation of chlordane below 0.05
ppm. Smallmouth bass caught in 1975 contained low
levels of chlordane but these could not be satisfactorily
separated from interfering compounds. By 1976, both
chlordane and hcptachlor epoxide were identified at
low levels in freshwater drum and walleye (Table 5).
TABLE 4.
He.
aclitorohenzcne
residues in
17
sp
•cies of fisli (-fS fisli) caiisihl in Lake
Saini Clair. 1970-71
Yl AR
No. OF
Fish
Avi.RAt.i: Wiiicm,
G
HCB,
PPM
Fish Sfecies
Mean
Range
I.OCAIION
Largemouth bass
1970-
71
■>
683
0.005
0.002-0.008
Mitchell Bay
Rock bass
1971
3
2211
0.008
0.002-0.013
Tremblay Creek
Bluegill
1971
6
1711
0.002
<0.00 1-0.004
Mitchell Bay
Bowfin
1971
1
163(1
0.008
0.005-0.015
Mitchell Bay
Brown bullhead
1971
3
412
(l.(K)3
0.002-0.1)03
Mitchell Bav
Carp
1971
2
2890
0.013
0.006-0.020
Mitchell Bav
Channel catfish
1971
2
1910
0,013
(1.005-0.020
Trcmblav Creek. Milchell Bay
Black crappic
1971
3
243
0.(1112
(1.001-0.003
Mitchell Bay
Freshwater drum
1971
3
623
0.0116
11.(102-0.008
St. Lukes Bav
i.ongnosc gar
1970
1
1195
0.007
Tremblay Creek
Mooneye
1970
2
158
0.009
Tremblay Creek
Yellow perch
1971
2
55
0.013
0.007-0.019
Mitchell Bav
Pumpkinsccd
1971
5
123
0.001
<0.00 1-0.002
Mitchell Bay
Quillback
1970-
-71
4
1670
0.008
0.005 0.010
Mitchell Bav
Redhorse mullet
1970-
-71
4
670
0.024
0.002-0.080
Bassctt Channel. Mitchell Bav
White sucker
1970
3
1185
0.004
tl.003-0.006
Bassetl Channel
W;,lle>c
1971
1
120
0.002
Mitchell Bay
74
Pesticides Monitoring Journal
TABLE 5. Chlordanc and heptachtor epoxide residues in fish species caiiuht in Lukes Saint Clair and Erie, 1972-76
Lake
Saint Clair
Lake Erie
Central basin
Eastern basin
Fjsh Species
Freshwater drum
Walleye
Rainbow trout '
While bass
Yellow perch
Coho salmon
Emerald shiner
Rainbow smelt
Year
1976
1976
1974
1972
1976
1972
1975
1976
1976
1976
1975
1976
Mean
Mean Content of Residues in
No. OF
Weight,
G
Fat,
Fish Tissues, ppm
FlSHl
%
Chlordane- Heptachlor Epoxide
10
259
9
1726
5
642
11
156
7
118
10
133
15
60
15
121
6
2198
4(12)
5.6
5
74
10
20
1.7
0.8
4.4
5.9
3.6
3.2
2.1
1.6
11.5
5.6
8.9
5.1
O.UII
ND-0.080
0.008
ND-0.028
ND
0.023
0.010-0.050
0.010
0.008-0.011
0.011
<0.00l-0.020
0.007
0.002-0.016
0.007
<0.00I-0.0I4
0.037
0.011-0.045
0.038
0.011-0.050
0.015
0.004-0.021
0.046
0.022-0.134
0.003
ND-0.0I3
0.004
ND-0.013
0.006
ND-0.033
ND
0.004
0.002-0.007
ND
0.001
ND-0.006
0.003
<0 .00 1 -0.007
0.007
0.002-0.010
0.012
0.006-0.016
0.006
0.001-0,009
0.015
0.009-0.033
■See footnote 1, Table 3.
-NOTE: Chlordane present as c/i- and /r«;ij-isomers in all species except while bass and yellow perch cauyht in 1972. Then, only rii-chlordane
was confirmed.
•Three rainbow Irout caught in Silver Creek also conlaincd endosulfan with mean residue ot 0.025 ppm (0.007-0.050 ppm). NOTE: ND = not
detected.
Other organochlorines — No endrin or metho.xychlor was
detecteiJ in fish caught in Lake Saint Clair. Samples were
analyzed for mirex in 1975-76, but no residues were
detected in smallmouth bass, freshwater drum, or wall-
eye caught in those years.
LAKE ERIE
'ZDDT — No mean residues of -DDT for any species
caught in Lake Erie in 1968-76 exceeded the 5.0 ppm
United States and Canadian tolerance levels. Three
coho salmon caught in 1970 in the central basin con-
tained levels of 8.23, 7.67, and 7.61 ppm i:DDT. and
the whole catch of 1 I fish averaged 2.80 ppm (Table 6).
These three fish were the largest, weighing 1,963, 2,276,
and 2,640 g, respectively, Three coho salmon caught
in 1971 from the same basin and weighing an average
of 806 g contained only 1.76 ppm -DDT.
SmallmoLith bass caught in 1971 from the eastern basin
was the only other species with mean residues above 1.0
ppm; mean residues were 1.2 ppm -DDT. Smallmouth
bass caught in 1968 from the same basin averaged 0.83
ppm; however, two of 16 fish had 1.53 ppm and 4.28
ppm -DDT. White bass and walleye had individual fish
with residues above 1 .0 ppm.
Five species were caught in all three basins during the
same year, and one of these, coho salmon, was caught
in three basins over two years (Tables 3, 6, 7). Emer-
ald shiner {Notropis atherinoides) and yellow perch,
which are localized species, contained residues of -DDT
that were not significantly different among the three
basins. In migrating species of white bass, freshwater
drum, coho salmon, and rainbow smelt (Osmerus mor-
dax), -DDT residues were similar for catches in the
three basins. Where differences occurred, the higher
residues correlated with fish size rather than with basin.
The highest residues of -DDT from the central, eastern,
and western basins, respectively, were freshwater drum
caught in 1971 and 1975 and coho salmon caught in
1975. In all three cases, the individual fish were 1.5-4
times heavier than members of the same species from
the other basins, and a correlation was evident between
increasing weight and increasing i;DDT residue; these
differences virtually disappear when similar weight
classes are compared among the basins (Tables 3. 6, 7).
Si\ species were divided into weight classes to deter-
mine the extent of decline in -DDT residues between
1968 and 1976 (Tables 3, 7). In the eastern basin,
smallmouth bass, which were caught in four separate
years, offered the best example. -DDT mean residues
for the species peaked in 1971 and declined thereafter
(Table 6); when compared by weight class, however,
species showed a decline in -DDT from 1968 to 1976
(Table 3). Declining residues of 2DDT in the eastern
basin were evident in rock bass (Amhioplites nipestris),
white bass, and yellow perch but not in rainbow smelt
or freshwater drum (Tables 3. 6).
In the central basin, 2DDT residues in coho salmon
peaked in 1971 and declined thereafter. Residues also
declined in freshwater drum and rainbow smelt but not
Vol. 12, No. 2, September 1978
75
TABLE 6. Orfionochlorinc residues in 19 fish species canf;lil in Canadiun waters
uj Lake Erie (I96H-76) and sevre.vatcd into western, central, and eastern basins
Mean and Rance
Fish Tissue,
Fish
Species
Year
No. OF
Basin Analyses'
Weigh).
c
Fat.
Mean Content and i
Range of Coniaminapjis in
PPM
DDE
TDE
DDT
i;DDT
Dieldrin
PCBs
Centriithiduf
Larticmouth
basH
1975
East
12
409
3.9
0.13
0.04
<fl.01
0.18
0.02
0.1
254-835
2.3-7.1
0.03-0,33
0.01-0.14
<0.01-<).()3
0.07-0.50
<().0 1-0.08
0.1-0.3
Rock bass
1968
East
7
91
1.7
0.06
0.03
0.03
0.12
0.01
0.2
84-113
0.8 2.6
0.0 i -0.14
<0.0 1-0.07
<0.01-0.07
0.02-0.28
<O.OI-0.02
<o.i-n.5
1971
East
8
180
101-239
1.9
1.2 2.7
0.09
0.02-0.13
ND
ND
0.09
0.02-0.13
ND
0.3
0.2-0.6
Smallmoiiih
1968
East
16
280
l.S
0.31
0.1 1
0.41
0.83
<0.0I
0.3
bass
162-478
0.9 4.2
0.1 1-1.60
0.04-0.44
0.15-2.24
0.32-4.28
<0.0 1-0.03
0.2-0.84
1971
East
*t
1449
7.5
0.90
0.13
0.17
1.20
<O.OI
5.8
1376-1522
5.7 9.3
0. 50-1. 30
0.03-0.23
0.05 ().28
0.55-1.81
2.3-9.3
1972
East
18
292
3.0
0.12
0.03
0.05
0.20
0.01
0.7
76-697
1.9-5.0
0.07-0.27
0.01-0.07
0.01-0.13
0.01-0.42
<0.0 1-0.03
0.4-1.2
1975
East
6
821
4.1
0.11
0.03
0.02
0.16
0.03
0.3
480-1226
2.5-5.4
0.04-0.20
0.01-0.25
<0. 01-0.05
0.05-O.30
0.01-0.05
0.2-0.4
Hliii->;ill
1968
East
4
209
0.5
<0.01
<0.01
<0.0I
0.02
<0.01
<0.1
97-341
1)4-0.5
<().() 1-0.03
<0.0I-0.()1
<O.OI-0.02
<0.0l-0.06
Black crappie
1968
East
5
1 II
1.2
0.06
0.04
0.04
0.14
<O.OI
<0.1
80-173
0.7-1.8
0.02-0.10
0.02-0.07
0.01-0.07
0.05-0.21
<0. 1-0.1
I'limpkinsecd
1968
East
6
95
1.4
0.02
0.01
0.01
0.04
<0.0I
<0.1
79-113
0.9-1.9
0.01-0.02
<0.01-0.l)l
0.03-0.05
<0. 01-0.01
<0. 1-0.1
Clttpeidiw
Alcwife
1971
East
7
101
93-108
23.2
19.4-25.5
0.24
0.12-0.29
ND
ND
0.24
0.12-0.29
<0.01
3.0
1.9-3.7
1975
West
2(21)
40
8.6
0.05
0.08
ND
0.13
0.07
0.5
34-5 1
8.1-8.9
0.04-0.06
0.07-0.09
0.1 1-0.15
(1.4-0.5
Central
5(22)
39
21.8
0.05
0.09
ND
0.14
0.08
0.4
20-66
14.1-31.9
0.03-0.07
0.03-0.15
0.06-0.22
0.02-0.15
0.3-0.4
Ciiz/ard shad
1968
West
6
234
9.4
0.06
0.17
0.09
0.32
0.02
0.3
37-302
4.4-12.6
0.04-0.08
0.10-0.25
0.06-0.15
0 20-0.47
<0.0l-0.04
<0. 1-0.6
1971
West
3(6)
92
74-105
15.5
13,8-16.7
0.07
0.06-0.07
ND
ND
0.07
0.06-0.07
ND
2.6
2.1-3.5
Central
3(9)
72
67-77
15.3
I 1.8-18.6
0.14
0,08-0.19
ND
ND
0.14
0.08-0.19
ND
3.4
2.4-4.7
1975
West
4(271
136
11.1
0.04
0.09
ND
0.13
0.08
0.7
110-157
10.1-12.0
0.03-0.06
0.06-0.11
0.09-0.17
0.06-0.10
0.6-0.9
Central
2(7)
63
12.0
0.05
0.09
ND
0.14
0.08
0.5
47-69
4,7-12.6
0.09-0.10
0.14-0.15
0.07-0.09
0.4-0.6
Cyprlnidae
I mcrald shiner
1975
West
3(60)
4.2
6.7
0.06
0.06
ND
0.12
0.05
0.6
4.0-4.5
5.6-7.7
0.05-0.07
0.05-0.07
0.10-0.14
0.05-0.06
0.5-0.7
Central
3 ( 60 )
6.4
7.7
0.04
0.05
ND
0.09
0.04
0.3
4.5-8.9
5.3-9.0
0.0.1-0.05
0.04-0.08
0.07-0.13
0.03-0.06
East
4(12)
5.6
5.6
0.08
0.02
0.02
0.12
0.02
0.4
2.5-10.0
4.0-8.0
0.07-0. 10
0.01-0.04
0.01-0.02
0.10-0.16
N D-0.03
0.3-0.6
Spotiail shiner
1975
West
3(60)
II. 1
3.8
0.05
0.06
ND
O.ll
0.04
0.06
5.7-16.0
3.5-4.0
0.03-0.07
0.04-0.08
0.O7-0.I5
0.03-0.06
0.04-0.07
titaluridae
Brown bullhead
1968
East
4
149
0.9
0.02
0.02
0,01
0.05
<0.01
<0.1
95-183
0.2-1.4
<0.0l-0.()4
<0.0 1-0.03
<0.0 1-0.02
0.01-0.10
Channel calfish
1968
West
4
105
3.5
0.13
0.18
0.15
0.46
0.01
0.2
74-135
2,1-4.5
0.09-0.18
0.13-0.26
0.12-0.20
0.34-0.64
<0.01-0.01
<0.1-0.2
1971
West
2
518
356-680
19.3
17.7-20.9
0.16
0.14-0.18
ND
ND
0.16
0.14-0.18
ND
5.0
4.2-5.7
Rainbow smell
1968
Central
4(13)
24
2 2
0.05
0.04
0.09
0.18
0,01
0.2
I6-.10
1.7-3.5
0.03-0.07
0.03-0.06
0.07-0.10
0.13-0.22
<0. 01-0.02
0.2-0.3
1971
East
2(7)
36
33-41
5.9
3.8-7.5
0.09
0.07-0.12
ND
ND
0.09
0.07-0.12
ND
1.3
1.2-1.4
1973
West
UIO)
26
1.1
0.13
0.14
0.04
0.31
0.06
0.5
1975
West
9(60)
29
3,4
0.04
0.04
ND
0.08
0.03
0.4
22-45
3.0-4.4
0.02-0.07
0.04-0.08
0.05-0.15
0.02-0.06
0.2-0.6
Central
6(70)
16
3.5
0.03
0.03
ND
0.06
0.03
O.I
13-20
3.1-3.8
0.02-0.05
0.03-0.04
0.05-0.08
0.02-O.03
East
8(23)
16
3.2
0.05
0.04
<o.oi
0.10
0.03
0.3
13-18
2.1-4.1
0.02-0.08
0.01-0.06
ND-0.03
0.03-0.12
0.01-0.06
0.1-0.6
1976
East
10
30
5.1
0.05
0.04
0.02
0.11
0.05
0.3
23-55
3.4-10,4
0.02-0.19
0.02 0.16
<0.0I-0.I3
0.05-0.48
0.03-0.10
<0.1-1.4
Percidae
Yellow perch
1968
West
12
141
1.3
0.04
0.06
0.04
0.14
<0.0I
<0.1
105-216
0.4-3.4
0.01-0. II
0.01-0.14
0.01-0.1 1
0.06-0.36
East
11
108
0.8
0.03
0.02
0.05
0.10
<0.01
<0.1
87-137
0.5-1.8
<0.0 1-0.06
<0.0I 0.05
0.02-0.08
0.03-0.16
<0. 1-0.1
1971
West
in
116
82-137
2.0
1.4-2.9
0.02
<0.01-0.06
ND
ND
0.02
<0.0 1-0.06
ND
I.O
0.2-2.6
Central
10
102
79-139
1.7
1.3-2.7
0.03
0.02-0.04
ND
ND
0.03
0.02 0.04
ND
0.3
0.2-0.6
East
9
122
99-137
2.7
1.5-5.8
0.08
0.04 0.14
ND
ND
0.08
0.04-0.14
ND
0.6
0.3-1.0
IConlinned next page)
76
Pesticides Monitoring Journal
TABLE 6
(cont'd
) . Oifianochloriiic
rc.siiliu'.s in
19 fisli species caii:^lit in C
anadian waters
Year
of Lake Eric
No. OF
Basin Analyses'
(1968-76) and sean
Mean and Range
■fiiiled into wexrern, central, and eastern basins
Mean Content and Range of Contaihinants in
Fish Tissue,
Fish
Weight,
G
Fat.
To
PPM
Species
DDE
TDE
DDT
■ZOOT
DiELDRIN
PCBs
1972
East
.10
98
2.6
0.06
0.01
0.01
0.08
0.01
0.3
39-449
1. 11-5. 8
0.03-0.10
<0.0 1-0.03
<O.OI-0.()3
0.04-0.15
<0.0 1-0.03
0.1-0.4
1975
Wesl
10(59)
40
1.7
0.03
0.04
ND
0,07
0.03
0.6
7-84
1.4-2.0
0.01-0.07
0.02-0.07
0.03-0.14
0.02-0.07
0.4-0.9
1975
Central
I5(,301
118
2.9
0.02
0.02
<0.0l
0.05
0.02
0.2
32-605
0.8-3.9
<0.0 1-0.05
ND-0.07
ND-<0.01
<0.01-0.11
ND-0.05
<0.1-0.8
East
21(
261
85
2.6
0.03
<0.0I
<0.01
0.05
<0.01
0.1
32-210
0.8-3.9
<().01-0.I3
ND-0.03
ND-0.01
<0.0I 0.15
ND-0,02
0.1-0.8
1976
East
15
121
1.6
0.02
0.0!
<0.0!
(1.04
0.01
0.2
69-212
0.6-3.5
0.01-0.04
<0.0 1-0.03
ND-0,01
0.02-0.07
<0.01-0.03
<0, 1-0,8
Walleye
1968
West
6
519
2.9
0.11
0.12
0.10
0.33
<0.01
0,2
256-923
1.7-4.1
11.06-0.16
0,07-0.21
0.06-0.15
0.19-0.46
<0.01-0.2
<0. 1-0,3
1971
West
4
460
158-362
4.0
1.9-5.4
0.03
0,112-0.03
ND
ND
0.03
0.02-0.03
ND
1.0
0.5-1,6
East
1
362
1.9
0.06
ND
ND
0.06
ND
0.6
1975
West
8( 14)
4.30
6.1
0.15
0.12
0.02
0,29
0.10
1.3
57-2275
1.8 22.2
0.05-0.99
0.(15-0.66
<0.0I-0.I9
0.10-1.84
0,03-0.45
0.3-5.1
Salmonidae
Coho salmon
1968
Central
2
471
5.4
0.19
0.12
0.20
0.51
0,03
0.3
4111-531
4.0-6.8
0. 17-0.20
0.10 0.14
0.18-0.22
0.49-0.53
0,02-0.04
0.2-0.4
1970
Central
11
2178
11.8
1.05
0.92
0.83
2.80
0.09
4.0
1627-26411
9.7-13.6
0.31-3.16
0.25-2.70
0.21-2.37
0.77-8.23
0.0.3-0.20
1.0-14.0
1971
Central
3
806
11.5
0.81
0.53
0.42
1.76
0.01
1.7
748-908
1 1.0-12.1
0.77-0.85
0.24-0.74
0.36-0.45
1.45-1.99
0.01 0.02
1.5-2.0
1975
West
9
3081
2.7
0.24
0.10
ND
0.34
0.08
1.4
1798-53110
0.6-4.9
0.08-0.73
0,02-t/.!5
0. 10-11.76
0.02-0.12
0.5-2.7
Central
17
2436
0.3
0.09
0,02
ND
0.11
0.02
0.7
1773-3520
(1.1 -1.0
0.05-0.21
<0.01-0.10
0.06-O.30
0.01-0.07
0.4-2.0
1976
East
6
2198
1.9
0.05
0.02
0.02
0.09
0.01
0.3
515-3125
1.1-2.7
0.0.3-0.07
0.01-0.03
<O.OI-0.03
0.04-0.13
<0.01-0.02
0.1-0.5
Rainbow trout
1974
Central
5
642
4.3
0.13
0.06
<0,01
0.20
0,07
0.3
93-1691
2.7-6.1
0.02-0.43
<O,01-0.26
0.03-0.69
<0.01-0.26
<0. 1-0.8
Sciacnicltie
Freshwater
drum
Serrimiiiae
White bass
1968 West II
1971 West 5(9)
Central 9
East 10
1975 West 16(23)
Central 8
East 10
1968 West 6
East 2
1971 West 10
Central II
East 10
1972 East 30
181 2.7
41-380 0,5 6.4
106 5.8
82-208 3.8-7.3
407 7.8
173-688 3,8-11,2
239 7,3
139-390 5.5-10.2
255 4.4
14-674 1.5-8.3
345 5,5
123-575 2.1-9.1
612 4.3
399-856 1.9-7.2
0.05 0.10
0.03-0.11 0.05-0.17
0,04 ND
0.01-0.12
0.17 ND
0.07-0.39
0.03 ND
<0.0 1-0.07
0.03 0.03
0.01-0.07 <0.01-0.07
0.05 0.06
0.02-0.12 0.04-0.10
0.12 0.03
0.06-0.30 <0.0I-0.09
161
117-295
1 10
107-113
2.30
163-401
160
110-232
127
92-199
161
54-755
3.0
2.1-4.2
1.3
1.2-1.5
6.5
3.2-10.0
6.5
4.3-11.2
3.6
2.6-4.8
3.7
0.5-9.0
0.17
0.04-0.41
0.04
0.03-0.05
0.09
0.03-0.19
0.13
0.10-0.17
0.10
0.05-0.17
0.12
0.24
0.12-0.60
0.02
0.01-0.02
ND
ND
0.04
0.07
0.04-0.11
ND
ND
ND
ND
ND
0.01
<O.OI-0.05
0.16
0.08-0.40
0.12
0.07-0.16
ND
ND
ND
0.03
0.22 <0.01
0.12-0.38 <0.0I-0.01
0.04 ND
0.01-0.12
0.17 ND
0.07-0.39
0.03 ND
<O.OI-0.07
0.06 0.03
0.02-0.14 0.01-0.07
0.11 0.05
0.07-0.19 0.03-0.08
0.16 0.03
0.06-0.42 0.01-0.04
0
0.57
:3-1.41
0,18
0.11-0.23
0.09
0.03-0.19
0.13
0.10-0.17
0.10
0.05-0.17
0.19
<0.01
0.02
0.01-0.02
ND
ND
ND
0.01
0.07-0.44 <0.0 1-0.33 <0.01-0.17
0.08-0.84 <0.01-0.04
<0.l
1.4
0.7-3.5
3.7
2.2-4.7
1.3
0.6-1.8
0.6
0.2-1.8
0.7
0.4-1.4
0.4
0.2-0.6
0.1
<0. 1-0.3
<0.1
2.2
1.1-4.8
1.6
0.9-2.2
0.8
0.5-1.4
1.0
0.5-5.4
NOTE: Fish eviscerated, heads and tails removed; alewjfe. shiner and smelt analyzed whole.
'See footnote 1. Table 3.
in yellow perch or gizzartd shaci ( Dorosoma cepedia-
iiititi) (Tables 3, 6, 7).
In the western basin, good e.xampies were not available
to show trends, and decline of SDDT residues were
not so obvious. -DDT generally declined in channel
catfish, freshwater drum, yellow perch, and rainbow
smelt, but not in white bass (Table 6). To observe a
decline in -DDT for walleye, similar weight classes
must be compared (Table 3),
Dieldrin — Only white bass and walleye caught in 1975
contained mean residues of dieldrin at or above 0.1
ppm. Three white bass from the western basin had
dieldrin levels of 0.12-0.19 ppm, and two from the
central basin had 0.17 ppm dieldrin. Two walleye in
a catch of 14 fish from west of Pelee Island had the high-
est resdues, 0.27 ppm and 0.45 ppm. These two fish were
the largest of the catch (2.0 kg and 2.3 kg) and con-
tained 20-22 percent fatty tissue (Table 6).
Vol. 12, No. 2, September 1978
77
TABLE 7. Six species of fish ciiiif;lil in till llinc hcisins of Lake Erie in either the same year
or in a two-year period (I97J , 1975-76)
Average
Mean
Fish Speciis
Weigh r
(I ASS. KG
Basin'
Weight,
G
Fat,
Mean
Content in Tissue,
PPM
Number of
(Year)
SDDT
DlELDBIN-
PCBs
Fish'
While bass
0-0.25
W
191
4.9
0.07
ND
1.73
8
(1971)
C
219
6.5
0.13
ND
1.62
11
E
127
3.6
0.10
ND
0.80
10
Freshwater drum
0-0.25
W
106
5.0
0.04
ND
1.40
5(9)
(1971)
C
176
8.5
0.11
ND
5.50
2
E
183
6.4
0.02
ND
1.14
7
(1975)
0.25-0.50
W
371
4.7
0.09
0.041
0.09
7
c
439
2.8
0.11
0.020
0.40
3
E
372
6.8
0.11
0.050
1.20
3
0.50-0.75
W
592
43
0.07
0.033
0.60
3
C
628
5.5
0.23
0.034
0.40
5
E
574
4.4
0.16
0.045
0.95
2
■fellow perch
0-0.25
W
116
2.0
0.02
ND
0.96
10
(1971)
C
102
1.7
0.03
ND
0.34
10
E
122
2.7
0.08
ND
0.64
9
(1975)
0-0.25
W
40
1.7
0.07
0.030
0.60
10(59)
C
95
1.8
0.05
0.025
0.18
11(26)
E
85
2.6
0.05
0.007
0.10
21(26)
Emerald shiners
0-0.25
W
4.2
6.7
0.12
0.053
0.63
3(60)
(1975)
C
6.4
7.7
0.09
0.043
0.30
3(60)
E
5.6
5.6
0.12
0.021
0.41
4(12)
Rainbow smell
0-0.25
W
29
3.4
0.08
0.030
0.45
9(60)
(1975)
C
16
3.5
0.06
0.029
0.10
6(70)
E
16
3.2
0.10
0.029
0.34
8(23)
Coho salmon
1.0-2.0
W
1.9
2.9
0.31
0.075
1.35
2
(1975-76)
C
1.8
0.3
0.08
0.015
0.70
4
E
1.6
2.7
0.09
0.012
0.52
1
2.0-1.0
W
2.8
2.1
0.25
0.068
1.05
4
C
2.3
0.3
0.08
0.013
0.55
6
E
2.6
1.9
0.11
0.011
0.28
3
3.0-4.0
W
3.8
4.3
0.32
0.095
1.40
2
C
3.2
0.5
0.15
0.035
0.95
6
E
3.1
1.4
0.04
0.004
0.11
1
iW = western, C=central, E^easlern.
-ND = not detected.
■'See footnote 1, Table 3.
Three species, rainbow trout {SalDio gairilneri) caught
in 1974, and alewife and coho salmon caught in 1975,
had mean residues of dleldrin below 0.1 ppm. Only a
few members of these species had levels above 0.1 ppm.
Although differences in dieldrin residues among basins
are not apparent, dieldrin residues did increase in 1968-
71 and 1975-76, as exhibited by alewife, smallmouth
bass, white bass, freshwater drum, yellow perch, gizzard
shad, and walleye (Tables 3, 6, 7).
PCBs — In the eastern basin, only smallmouth bass
caught in 1971 had mean residues of PCBs above the
5.0 ppm U.S. tolerance limit; channel catfish from the
western basin averaged 5.0 ppm in the same year
(Table 6). In addition, species of white bass caught in
the eastern basin in 1972, coho salmon caught in the
central basin in 1970, and walleye caught in the western
basin in 1975 had individual members whose PCB resi-
dues exceeded 5(1 ppm.
Species other than smallmouth buss and channel catfish
which had PCB mean residues exceeding the 2.0 ppm
Canadian tolerance limit were: alewife from the eastern
basin (1971 ), white bass from the western basin (1971,
1975), freshwater drum from the central basin (1971),
coho salmon from the central basin ( 1970), and gizzard
78
shad from both western and central basins (1971).
Among other catches in which the mean residue was
below 2.0 ppm PCBs but individual fish exceeded the
2.0 ppm tolerance limit were white bass from the eastern
basin (1972), freshwater drum from the western basin
(1971), yellow perch from the western basin (1971),
and coho salmon from the western basin (1975).
There was no correlation between highest mean residue
of PCBs in a species and the basin in which it was
caught. In 1971. three species were caught in all three
basins. Alewife had the highest mean residues (3.0
ppm) of the eastern basin species; freshwater drum had
the highest mean residues (3.7 ppm) of the central
basin species; and yellow perch had the highest mean
residues ( 1.0 ppm) of western basin species (Table 6).
In the western basin, white bass and walleye showed
increased residues of PCBs between 1968 and 1975 both
for mean residues and residues by weight class (Tables 3,
6). Freshwater drum and gizzard shad contained resi-
dues of PCBs that increased between 1968 and 1971 and
declined in 1975. PCB residues also declined in yellow
perch between 1971 and 1975 (Tables 3. (\ 7).
In the central basin, PCBs in coho salmon peaked in
Pesticides Monitoring Journal
1970 and then declined until 1975. This was true for
similar weight classes. PCB residues declined in tissues
of white bass, freshwater drum, and gizzard shad in the
central basin. No species showed increasing PCB resi-
dues, but yellow perch and rainbow smelt, which had
low residues in 1968, showed little change in tissue
residues by 1975.
In the eastern basin, mean residues of PCBs in small-
mouth bass and yellow perch reached a ma.ximum level
in 1971 and then declined (Table 6). However, a
comparison of fish by weight classes showed that resi-
dues of PCBs peaked in 1972 and have shown little
change since (Table 3). White bass, freshwater drum,
and rainbow smelt had their highest residues in 1971-72
and declined by 1975.
CMordane and hcptachlor epoxide — Residues of cis- and
//o/i.v-chlordane were first determined in 1972. In that
year, c/i-chlordane was positively identified in only two
species, white bass and yellow perch from Long Point
Bay, Lake Erie (Table 5). The presence of r/-fl/i.?-chlor-
dane in the two species was suspected but not confirmed.
Chlordane residues in other fish caught between 1972
and 1974 were not confirmed because of the interfer-
ence of other compounds on the chromatogram.
In 1975-76, both cis- and /ra/w-isomers of chlordane
were detected in white bass, yellow perch, coho salmon,
emerald shiner, and rainbow smelt; highest residues
were found in rainbow smelt in 1976. Chlordane was
also suspected in other species. However, levels were
either too low to be confirmed or interfering substances
made separation and identification difficult. In 1976,
several species were analyzed for oxchlordane but it was
not detected.
Heptachlor epo.xide was first positively identified in
rainbow trout caught in Silver Creek draining into the
central basin (Table 5). In 1975 and 1976, residues
of heptachlor epoxide were also identified in white bass,
yellow perch, coho salmon, emerald shiner, and rainbow
smelt. As with chlordane, the highest residues of hep-
tachlor epoxide were found in rainbow smelt.
Other organochloiine compounds — Endosulfan was
identified in rainbow trout caught in Silver Creek in
1974 (Table 5). Neither endrin nor methoxychlor was
identified in any fish caught in Lake Erie. Mirex
analysis was added in 1975-76, but no measurable
residues were detected.
Discussion
SEDIMENT AND FISH RESIDUES
Sediments in Lake Erie were five to ten times more
highly contaminated with 2DDT. dieldrin, and PCBs
than were sediments from Lake Saint Clair, mostly be-
VoL, 12, No. 2, September 1978
cause sediment is transitory through Lake Saint Clair but
accumulates in the basins of Lake Erie (5). Fish tis-
sue residues of -DDl^ and dieldrin did not necessarily
show this trend, but PCBs were higher in fish from Lake
Erie. For example, rock bass and smallmouth bass
caught in Lake Erie in 1971 had higher residues of
-DDT than did those caught in Lake Saint Clair. The
reverse was true of channel catfish caLight the same
year. Dieldrin residues were generally at the trace
level in fish from both bodies of water. Residues of
PCBs were higher in rock bass, channel catfish, fresh-
water drum, yellow perch, and walleye caught in Lake
Erie than those caught in Lake Saint Clair during the
same year. Smallmouth bass were an exception; resi-
dues in fish caught in Lake Saint Clair were higher.
Frank et al. reported that the parent compound p,p'-
DDT was low or absent from sediments in Lake Erie
(5). In the present study, p.p'-DDT was not found
in many fish caught in Lake Erie.
Sediments collected from the western basin of Lake
Erie contained -DDT and PCB residues two to three
times higher than did sediments in either the central
or eastern basins (5). Differences in residues among
the same species caught during the same year in all
three basins were not apparent.
FISH RESIDUES
Residues of -DDT were considerably higher in 1971
than those reported by Reinke et al. in Lake Saint Clair
in 1970 (13). :SDDT and dieldrin residues in 13
species of fish caught in 1965-68 in Lake Erie (//)
were two to nine times higher than those in the same
species caught in 1968 in the present study. Samples
of gizzard shad in the two studies were similar (0.50
ppm and 0.32 ppm, respectively), but yellow perch
samples were different (0.9 ppm and 0.1 ppm, re-
spectively).
Reinke et al. (13) reported on 2DDT and dieldrin
residues in six species of fish from Canadian waters
of Lake Erie in 1970 which were 1.5-10 times higher
than those in similar species reported herein. 2DDT
residues in alewife were similar for the two studies
(0.34 ppm and 0.24 ppm, respectively), but residues
in freshwater drum and yellow perch were an order
of magnitude different.
The site of catch can have a significant bearing on the
contaminant residue level (4). In fish of the same
species, -DDT and dieldrin residues were 10-15 times
higher in fish caught in streams than in those caught
in the lakes. Bluegill (Lepomis macrochirus), brown
bullhead (Ictaliirus nebiilosus), pumpkinseed (Lepomis
gibhosiis), and rock bass all exhibited -DDT and diel-
drin residues an order of magnitude higher in fish
from creeks draining the tobacco belt of Ontario than
in fish caught in Long Point Bay, Lake Erie (4).
79
Residues of i:DDT. dieldrin. and PCBs reported by
Carr et al. (2) in fish caught in 1970-71 correspond
more closely with the residue levels reported in the
present study, especially in the six species common
to both surveys.
Residues of -DDT in coho salmon caught in 1970
during the present study correspond with those re-
ported by Reinert and Bergman (12) for the same
species caught in 1969. Coho salmon (1970) weighing
2.0 kg contained 2.2 ppm -DDT; coho salmon ( 1969)
weighing 2.2 kg had 2.8 ppm i:DDT.
•Suns and Rees documented residues in spottail shiners
from both the western and the eastern basins of Lake
Erie (/.''). -DDT and dieldrin levels in spottail shiners
from the western basin reported in the present study
are similar to those of Suns and Rees (15), but PCB
residues are lower by an order of magnitude. Emerald
shiners caught close to the same location, however,
contained similar PCB levels (0,6 ppm). Suns and
Rees reported that spottail shiner are good indicators of
specific site effluents of PCBs (15).
Acknowledgment
Thanks are extended to the field staft' of the Ontario
Ministry of Natural Resources, in particular to D, Mac-
I.ennan, G, Teleki, J, Paine, and R. Shelton, for
obtaining fish for this study. Authors thank members
of the Provincial Pesticide Residue Testing Laboratory,
particularly J. Stanek and Y. P. Lo, for carrying out
sample preparation and extraction.
LITERATURE CITED
(/) Aniciicun Fisheries Sociciv, ( (tiiuniltcc on Names of
Fishes. 1970. A list of common and scientific names
of fish from the United Slates and Canada (3rd ed.).
Am. Fish. Soc, Spec, Pubi, 6. Washington. DC. 150 pp.
(2) Carr. R. I... C. E. FiiislerwtilJer. and M. J. Schibi.
1972. Chemical residues in Lake Erie fish— 1 970-7 1 .
Pestic, Monit, J, 6( I ) :23-2fi,
(3) Frank, R.. A. E. Armslroni;. R. C. lioelens. H. E.
liraim. and C. W. Douglas. 1974. Organochlorine in-
secticide residues in sediment and lish tissues. Ontario,
Canada. Pestic. Monit. J. 7(3 4) : 165-180.
(4) Frank. R., K. Monlgoinery, H. E. Briiiin. A. H. Berst,
and K. Lofliis. 1974. DDT and dieldrin in watersheds
draining the tobacco belt of soulhcrn Ontario. Pestic.
Monit. J. X(3): 184-201.
(.^) Frank. R.. R. L. Thomas. M. HoUlrinel. A. L. W.
Kemp. //. E. Braan. and J. M . Jaqnel. 1977. Organo-
chlorine insecticides and PCBs in sediments of Lake
St. Clair 1970 and 1974 and Lake Erie 1971. Sci. Total
Environ. 8(3):205-227.
(!')) Holdrinet. M. 1974. Determination and confirmation
of hexachlorobenzene in fatty samples in the presence
of other halogenated hydrocarbon pesticides and PCBs.
J. Assoc. Otr. Anal. Cliem. 57( 3 ) :58()-584.
(7) Kelso. J. R. M.. and R. Frank. 1974. Organochlorine
residues, mercury, copper, and cadmium in yellow
perch, white bass, and smallmouth bass. Long Point
Bay, Lake Erie. Trans. Am. Fish. Soc. 103(3):577.
(A') Laniilois. E. B.. A. R. Slemp. and B. J. Liska. 1964.
Analysis of animal food products for chlorinated in-
secticides. J. Milk Food Technol. 27(7) ::02-204.
(9) A/(7('A, J. R. It ., and ( . R. Harris. 1971. Insecticide
residues in a stream and a controlled drainage system
in agricultural areas of southwestern Ontario, 1970.
Pestic. Monit. J. 5( 3 ) -.289-294.
{10) Miles. J. R. W.. and C. R. Harris. 1973. Organo-
chlorine insecticide residues in streams draining agri-
cultural, urban-agricultural, and resort areas of On-
tario, Canada— 1971, Pestic. Monit. J. 6( 4 ) :363-368.
( // ) Reineri, R. E. 1970. Pesticide concentrations in Great
Lakes fish. Pestic. Monit. J. 3(4 ) :233-24().
(12) Reinert. R. E.. and H. L. Bergman. 1974. Residues
of DDT in lake trout iSalvelinus namaycush) and
coho salmon (Oneorlniuiuis kisalch) from the Great
Lakes. J. Fish. Res. Board Can. 31 (2) : 191-199.
(13) Reinke. J.. J. F. Ulhe. and D. Jamieson. 1972. Or-
ganochlorine pesticide residues in commercially caught
fish in Canada— 1970. Pestic. Monit. J. 6(l):43-49.
(14) Reynolds, L. M. 1971. Pesticide residue analysis in
the presence of polychlorinated biphenyls (PCBs).
Residue Rev, 34:27-57,
(Z.')) Sans, R., and G. Rees. 1975. Chlorinated hydrocar-
bon residues from selected sites on Lakes Ontario, Erie,
and St. Clair, 1975. Ontario Ministry of the Environ-
ment, Parliament Buildings, Queen's Park, Toronto,
Ontario,
(16) Thomas. R. L.. J. M. Jaqnel, A. L. W . Kemp, and
C. F. M. Lewis. 1976. Surficial sediment of Lake
Erie. J. Fish. Res. Board Can. 33(3) :385-403.
80
Pesticides Monitoring Journal
Organochlorine Residues in Aquatic Environments in Iran, 1974
A. Sodergren,' R. Djirsarai,' M. Gharibzadeh,= and A. Moinpoiir =
ABSTRACT
Organochlorine pesticide residues in various organisms from
different aquatic ecosystems in Iran were investigated in
spring 1974. DDT levels were high in fish taken from two
rivers in southern Iran, whereas low levels were detected in
samples obtained from a freshwater lake in the same area.
Fish from two of the reservoirs supplying Tehran with po-
table water contained moderate levels of DDT. The low
residue level in pike collected in the Bandar-Pahlavi Mordab
in northwest Iran indicates that only a small amount of or-
ganochlorine pesticides used in this area enters the pelagic
food chain.
Sturgeon collected at different places in the Caspian Sea
showed similar accumulations of DDT in the muscles and in
the eggs. Polychlorinated biphenyls (PCBs) were detected
only in samples of sediment from the drainage systems in
Tehran.
Introduction
Although reports on the widespread distribution of or-
ganochlorine pesticide residues in the global ecosystem
are increasing (4, 5, cS, 10, II. 17). very little is known
of their occurrence, distribution, effects, and ecological
significance in many developing countries. Because large
quantities of pesticides are used in such countries for
agriculture and in vector control programs, information
is needed to evaluate the full effects and benefits of
pesticidal applications.
Iran imported about 2,720 tons/year of organochlorine
pesticides during 1966-75; DDT was the main import
(Table 1). Consumption increased considerably during
that period, and the amount of DDT compounds im-
ported during 1974-75 was about 10 times that im-
ported in 1966-67. Far-reaching ecological implications
may be foreseen regarding the stability of the pesticides
and their readiness to accumulate in food chains, espe-
cially in areas subjected to regular, intense applications.
During 1970-72, Higgins [3] analyzed various samples
from the Caspian Sea for DDT and heavy metals. Hash-
emy-Tonkabony and Asadi Langaroodi (2) studied or-
ganochlorine pesticide residues in 14 species of fish from
the Caspian Sea. The levels found by Higgins were not
regarded as hazardous, but a closer study of the occur-
rence, distribution, and possible effects of these pesti-
cides in selected biota was recommended.
The purpose of the present study was to monitor certain
areas in Iran to evaluate the level of contamination and
its signific:ince.
Substances Investigated
Samples were analyzed for benzene hexachloride (BHC),
lindane, aldrin, dieldrin, DDT, and polychlorinated bi-
phenyls (PCBs). All e.xcept PCBs are widely used in
Iran as insecticides.
The form of DDT most used in pesticide formulations
contains approximately 70 percent p.p'-DDT and 20 per-
cent o.p'-DDT: the remaining 10 percent contains at
least seven different substances (1 ). Therefore, it is as-
sumed that DDT enters the environment mainly as p,p'-
DDT or o.p'-DDT. In a study of the distribution of
DDT and its metabolites in the environment, the pattern
of degradation may be used to evaluate DDT input to
the ecosystem.
PCBs include at least 50 different compounds, homologs,
or isomers. They are not spread as pesticides, but are
TABLE 1. Amount of chlorinated hydrocarbons imported
to Iran, 1966-75'
TOTAl
Chlorinated
DDT Compounds,
Year
Hydrocarbons,
Tons
Tons
1966-67
1005
514
1967-68
850
585
1968-69
2137
1214
1969-70
1799
1168
1970-71
1965
1142
1971-72
3347
2967
1972-73
1247
517
1973-74
5841
3620
1974-75
6291
5786
^Present address: Institute of Limnology, Univeisity of Lund, Sweden.
-Department of the Environment, P.O. Box 1430, Tehran, Iran.
1 SOURCE: Department of the Environment and the Plant Protection
Department. Tehran, Iran.
Vol. 12, No. 2, September 1978
81
used in industry as hcat-lranstcr media, lubricants, waxes,
and synthetic resins to improve chemical resistance, ad-
hesiveness, and llexihility (9). The sources of PCBs and
their modes of transport into the environment are poorly
understood.
Materials and Methods
SAMPLING
Samples of various organisms collected in spring 1974
were frozen and brought to the laboratory in Tehran.
Sturgeon and their eggs were sampled at three places
along the Iranian Caspian Sea coast. Birds and fish from
Parishan Lake and the Shapour and Kupor Rivers, situ-
ated in the Shiraz area in southern Iran, were sampled.
Fish from water reservoirs near Tehran were also ana-
lyzed, as well as pike from the Bandar Pahlavi region,
300 km northwest of Tehran (Figure 1 ).
From sturgeon, a section of the dorsal musculature just
behind the gills was excised. The skin was removed, and
the sample was wrapped in aluminum foil and frozen
!• Bondor Pohlovi (sturgeon)
2 Babulsor (sturgeon)
3.Mtonkaleh ond Tozzc Abed
(sturgeon)
4. Bandor Pohlaoi Mordob (pike)
5. Porishon Lake, Shopour and
Kupor Rivers (fish and birds)
FIGURE I. Locatiun of .\ciiiiplint; circus in Iriin
until processed. The sturgeon eggs were removed and
frozen in a similar manner. From other fish, a section
of the lateral body muscle from the left side of the fish,
anterior to the anal openings, was taken for analysis.
From the birds, the breast muscle was sampled.
ANALYTICAL METHODS
Organochlorine residues were extracted, cleaned, and
separated and quantitated by gas chromatography by the
method of Sodergren (12).
Samples (1-3 g) were homogenized in a 1:1 solution of
acetone-hexane. After acetone was removed, the hexane
extract was evaporated to 1 ml and divided into thirds
for subsequent cleanup and fat determination.
Two cleanup processes, one acidic and one involving
basic hydrolysis, were performed simultaneously for each
sample. The compounds were chemically derivatized,
and the conversion products were used to confirm the
identity of the original compounds. p.p'-DDT and
p.p'-TGE were treated with potassium hydroxide and
quantitatively converted to p.p'-DDE and p,p'-DDM\J
1 1 -chloro-2.2-bis(/)-chlorophenylcthylene)], respectively.
In the acidic treatment, dieldrin is degraded but is re-
covered in the potassium hydroxide-treated extract. On
the other hand, lindane and benzene hexachloride (BHC)
are lost in the KOH procedure, but are recovered in the
acidic treatment. Neither treatment atTects the PCBs.
Two hundred m1 of the extract was taken for gravimetric
determination of extractable lipids in the sample.
The hexane extracts were analyzed by gas-liquid chroma-
tography on a Model 2700 Varian Aerograph equipped
with a Hoechst Oxysorb filtering unit. A modified
electron-capture detector was used (13). The system, all
glass from the injector to the detector, diminishes the
risk of pyrolysis. Sensitivity was also increased over that
of conventional Kovar cells. Instrument parameters and
operating conditions follow.
205 cm lony >' 1.5 mm ID glass, packed with
a .1:1 mixture of 4 percent SF-96 and 8 per-
cent QF-I on U)0-120-mesh Chromosorb W
AW/DMCS
up[>ro\imalelv 1700 theoretical plates for p.p'-
DDT
Resolution:
Tcmpci atures:
Carrier ga.s:
column I85°C
injector 225°C
detector 220°C
niIrot;en flowing at 25 ml/minute
The quantity of organochlorines in the samples was esti-
mated by comparing peak heights of aliquots of purified
extracts with peak heights of a known quantity of a
standard solution. The results were not corrected for
recovery. For the PCBs, a commercially available mix-
ture, Clophen A50, was used as a reference.
X2
Pesticides Monitoring Journal
TABLE 2. OrganoMorinc residues in organisms from Parishan Lake, Kupor and Slia/ipour Rivers — 1974
Species
Parishan Lake Barhus sp.
Coot, Fulica atra
Kupor River Barbiis sp.
Shahpour River Varichorhinus sp.
Barbia sp.
Fat,
Fresh Weight, ng/g
DDE
0.4
7
0.4
7
0.3
3
2.4
37
0,8
1425
0.4
1161
0.1
251
2.5
3030
0.5
250
TDE
ND
ND
ND
ND
ND
261
30
118
18
Fat Weight, mg/ko
DDT V DDT
DDE
TDE
ND
7
1.7
ND
7
1.8
ND
3
1.2
ND
37
1.6
180
1605
174.0
241
1662
72.9
39
320
482.3
910
4058
121.2
30
298
50.8
ND
ND
ND
ND
ND
16.4
57.6
4.7
3.7
DDT
2 DDT
ND
1.7
ND
1.8
ND
1.2
ND
1.6
22.0
196.0
15.1
104.4
74.9
614.8
36.4
162.3
6.1
60.6
NOTE: ND = not delected.
Results
Only small amounts of /),/;'-DDE were detected in fish
from Parishan Lake and in a coot which was foimd dead
(Table 2). Fish obtained from the Shahpour and Kupor
Rivers contained appreciable amounts of DDT and its
metabolites DDE and TDE (Table 2). The Shahpour
and Kupor Rivers flow through malaria-infected areas,
and DDT is used for indoor spraying.
In fish and fish eggs from two reservoirs supplying Teh-
ran with potable water, various amounts of DDT were
detected (Tables 3, 4). The levels in cyprinide fish
(Varichorhinus nikoiskii) from the Latian reservoir far
exceeded those found in fish from the Karadj reservoir.
The main metabolite accumulated was /).p'-DDE.
In samples from the Latian reservoir, the levels of DDT
compoimds in rainbow trout (Saliiio gairdneri) were sim-
ilar to those found in V. nikolskii. The Varichorhinus
species has a shorter food chain than the Salnio species,
resulting in a deviation from the usual pattern of bio-
magnification of persistent compounds.
Low levels of DDT were found in pike (Esox iucius)
collected from the Bandar Pahlavi Mordab (Table 5).
Again, the principal metabolite found was p,p'-DDE.
The presence of only small proportions of p.p'-DDT
suggests that the accumulation occurred over consider-
able time, and that the input is not recent.
In May 1974, more than 100 samples of sturgeon and
their eggs were collected from two species (Accipencer
TABLE 3. Or^anochlorine residues in fish and fish eggs from the Latian Dam, 1974
Fat.
Fresh Weight,
ng/g
Fat Weight,
mg/kg
Species
DDE
TDE
DDT
2 DDT
DDE
TDE
DDT
2 DDT
Salmo gairdneri
0.7
13
-)
13
28
1.6
0.3
1.6
3.2
0.2
650
ND
ND
650
88
ND
ND
88
1.4
97
ND
ND
97
41
ND
ND
41
1.0
340
ND
ND
340
24
ND
ND
24
2.4
75
ND
ND
75
7.9
ND
ND
7.9
Varichorhinus nikolskii
1.9
178
81
8
267
9.5
4.3
0.4
14.2
2.2
245
17
ND
262
11
0.8
ND
11.8
0.7
92
10
ND
102
10.6
1.2
ND
11.8
1.7
129
ND
10
139
7.6
0
0.6
8.2
1.4
77
ND
ND
77
5.7
ND
ND
5.7
Alhitrnoides hipanlattir
0.8
185
19
ND
204
24.2
2.5
ND
26.7
0.5
410
26
ND
436
262.7
16.4
ND
279.1
Coregontts sp.
0.8
13
2
13
28
1.6
0.3
1.6
3.5
Eggs from 5. gairdneri^
1.6
235
21
ND
256
14.3
1.3
ND
15.6
NOTE: ND— not detected.
'Pooled sample from six indiv
iduals
TABLE 4. Organochlorine residues in cyprinide, Varichorhinus nikolskii, from Karadi Reservoir, 1974
Fat,
Fresh Weight, ng
/G
Fat Weight, mg/kg
%
DDE
TDE
DDT
2 DDT
DDE
TDE
DDT
2 DDT
0 3
11
3
ND
14
4.7
1.1
ND
5.8
0.6
23
ND
ND
23
3.8
ND
ND
3.8
0 6
n
ND
ND
11
1.7
ND
ND
1.7
0 2
g
ND
ND
8
3.7
ND
ND
3.7
0.9
22
ND
ND
22
2.4
ND
ND
2.4
NOTE; ND=not delected.
Vol. 12, No. 2, September 1978
83
TABLE 5. Organochlorine leshliic.s in pike, Esox lucius, from Bandar Palilavi Monlab, 1974
Age,
Fat.
%
Fresh Weight, nc/g
Fat Weight, mg/kg
Years
DDE
TDE
DDT
SDDT
DDE
TDE
DDT
SDDT
3+
0.7
3
ND
ND
3
0.4
ND
ND
0.4
3 +
I.I
6
ND
ND
6
0.6
ND
ND
0.6
3 +
0.6
5
ND
ND
5
1.2
ND
ND
1.2
3-r
0.7
17
ND
ND
17
2.3
ND
ND
2.3
3+
0.6
3
ND
ND
3
0.6
ND
ND
0.6
3+
0.5
9
ND
ND
9
2.0
ND
ND
2.0
3 +
0.7
5
ND
ND
5
0.7
ND
ND
0.7
3 +
0.5
8
ND
ND
8
1.3
ND
ND
1.3
3+
0.5
2
ND
ND
2
0.4
ND
ND
0.4
3+
0.4
4
ND
ND
4
0.9
ND
ND
0.9
NOTE: ND=not detected.
TABLE 6. Ori;anochtorine residues in sliiriieon, Accipcnser stelliitiis, from Miankaleli
and Tazre Alnid at llie Caspian Sea. 1974
Weight,
KG
Fat.
Fresh Weight,
ng/g
Fat
Weight.
mg/kg
Sample
Lindane
DDE
TDE
DDT
:SDDT
Lindane
DDE
TDE
DDT
SDDT
Muscle
9.5
2.6
4
14
7
21
0.2
0.5
0.3
0.8
Eggs
17.5
13
67
16
8
91
0.1
0.4
0.1
0.1
0.6
Muscle
9.0
3.0
2
16
4
4
24
0.1
0.5
0.1
0.1
0.7
Eggs
17.3
ND
84
31
18
133
ND
0.5
0.2
0.1
0.8
Muscle
7.0
6.6
ND
276
46
149
471
ND
4.2
0.7
2,3
7.2
Eggs
16.1
23
494
484
224
1202
0.2
3.1
3.0
1.4
7.5
Muscle
8.0
4.8
7
96
19
44
159
0.2
2.0
0.4
0.9
3.3
Eggs
19.4
26
471
54
141
666
0.2
2.4
0.3
0.7
3.4
Muscle
8.5
2.0
ND
25
7
10
42
ND
1.2
0.4
0.5
2.1
Eggs
16.6
15
193
37
55
285
0.2
1.2
0.2
0.3
1.7
Muscle
10.5
3.1
4
208
97
126
431
0.2
6.7
3.1
4.1
13.9
Eggs
16.6
17
996
125
662
1783
0.1
6.0
0.8
4,0
10.8
Muscle
9.5
4.1
5
27
14
10
51
0.1
0.7
0.3
0.3
1.3
Eggs
16.9
17
79
38
27
144
0.1
0.5
0.2
U.2
0.9
Muscle
8.0
5.0
6
26
19
11
56
0.1
0.5
0.4
0.2
1.1
Eggs
19.6
23
79
44
34
157
0.2
0.4
U.2
0.2
0.8
Muscle
9.0
6.0
7
92
19
46
157
0.2
1.5
0.3
0.8
2.6
Eggs
14.3
13
204
38
77
319
U.l
1.4
0.3
0.5
2.2
Muscle
8.5
2.5
ND
55
12
20
87
ND
T T
0.5
0.8
3.5
Eggs
14.0
16
300
48
114
462
0.2
2.1
0.3
0.8
3.2
NOTE: ND = not detected.
guldensiadtl and A. xtellatus) from three diflferent places
along Ihe Iranian coast of the Caspian .Sea (Figure 1).
From these, 20 samples o{ A. steUatiis of similar size and
weight were analyzed (Table 6). Fat content in the
muscle was 2. ()-(>. 6 percent; corresponding range for the
eggs was 12.0-19.6 percent. Calculated on the extract-
able lipid fraction, the average levels of DDT in muscle
and egg were 3.7 ppm and 3.2 ppm, respectively. BHC
and lindane were detected, but no PCBs were found.
No significant dilTercnces in the distribution of DDT and
its metabolites in egg and muscle were revealed (Table 7).
The range of DDT found in muscles of four species of
sturgeon sampled at Babolsar in March 1974 was 1.0-
13.1 ppm (Table 8). For A. Mellatiis. the mean level of
DDT was 4.7 ppm.
The only samples in which PCBs were detected came
from Tehran. .Sediment from ihe drainage system along
Ihe streets contained appreciable amounts of DDT and
PCBs (Table 9).
TABLE 7. Distrilnition of DDT and its metabolites in
inusele and egi^s of sturgeon, Accipenser stellatus — 1974
Sample
Muscle
Mc;in
Hubs
%
DDE
Mc.in
72
58
61
57
48
54
45
58
63
58
80
82
41
71
71
56
56
50
64
66
64
TDE
38
14
10
12
19
22
23
36
12
14
20
20
25
40
9
12
7
22
25
14
9
16
%
DDT
14
32
27
24
30
23
19
30
23
22
13
19
20
17
37
22
25
22
25
20
84
Pesticides Monitoking Journ.\l
TABLE
8. Oi
ganocMorinc
residues in sturgeon
from Balyol
sar at the
Caspian Sea
797-^
Fat,
%
Fresh Weight,
ng/g
Fat Weight, mg/kg
Species
Lindane
DDE
TDE
DDT
2 DDT
Lindane
DDE
TDE
DDT
2 DDT
Accipenser
2.6
1
95
11
56
162
0.1
3.5
0.4
2.1
6.0
guldenstadti
1.7
ND
41
ND
15
56
ND
2.5
ND
0.9
3.4
1.5
2
18
ND
7
25
0.1
1.3
ND
0.9
1.8
0.5
1
51
1
19
71
0.1
1.1)
ND
0.4
1.4
2,4
1
37
5
21
63
0.1
1.5
0.2
0.9
2.6
2.0
1
23
ND
1
24
0.1
1.1
ND
0.1
l.I
3.7
1
24
3
22
49
0.1
0.6
0.1
0.6
1.2
2.7
16
220
ND
142
362
0,5
8.0
ND
5.1
13.1
4.8
ND
106
10
85
201
ND
2.2
0.2
1.7
4.1
A. stellatus
1.0
ND
12
ND
7
19
ND
2.2
ND
n.7
1.9
1.2
ND
84
3.6
51
139
ND
6.7
0.3
4.1
11.1
4.6
ND
239
ND
119
368
ND
4.9
ND
2.5
7.7
3.7
ND
310
40
24U
59
ND
3.9
0.5
3.(1
7.4
5.7
9
141
2')
155
318
1.1
2.5
0.4
2.7
5.6
5.0
ND
64
32
71
167
ND
1.2
11.7
1.3
3.2
2.9
ND
23
ND
18
41
ND
0.8
ND
0.6
1.4
1U.4
ND
242
ND
84
326
ND
2.3
ND
0.8
3.1
0.5
ND
15
ND
3
18
ND
2.7
ND
0.6
3.3
1.4
ND
56
ND
31
87
ND
3.9
ND
2.1
6.0
A. nudiventris
2.9
1
27
2
8
37
U.l
0.9
0.1
(1.3
1.3
12.3
76
12
45
133
0.6
0.1
0.4
1.0
2.7
5
28
5
18
56
0.2
1.1
0.2
0.7
2.0
Huso huso
0.6
26
ND
9
35
4.0
ND
1.3
5.4
NOTE: ND^not detected.
TABLE 9. Orgaiioehlorine residues in sediment
from street drainage systems in Tehran, 1974
Wei Weight, ng/c
Street
SDDT
PCB
Karim Kahn Zand
Fisherabad
ShahAbbas
85
112
35
138
155
ND
NOTE: ND^not detected.
Discussion
Fish are exposed to pesticide residues not only in the
water but in food and sediments. Some fish continue to
accumulate residues over a period of years. Therefore,
the levels in the fish may reflect their integrated history
of exposure and can be used to assess the degree of
pesticide contamination in a freshwater ecosystem.
Food can he a significant source of residues if the prey
species has had a greater exposure in its physical envi-
ronment than has its predator. However, biomagnifica-
tion of persistent residties does not depend simply on
position in the food chain but is basically determined by
the rate at which the residue is taken up and eliminated.
Although of limited statistical significance, the results
from the Latian reservoir show that despite a lower
trophic position the Varichorhintts species acctmuilated
about the same amount of DDT as did the Saliiio species.
DDT and its metabolites were the principal organo-
chlorine residues detected. Aldrin or dieldrin was not
found, and PCBs occurred in significant quantities only
in samples collected in Tehran.
Very high levels of DDT were found in fish from the
Kupor and Shahpour Rivers in southern Iran. The pro-
portions of the DDT not metabolized, 12 percent in
Kupor River samples and 16 percent in Shahpour River
samples, indicate that the input of DDT to the rivers is
of recent origin and/or is still occurring. DDT probably
originates from the mosquito-spraying operations in
these areas.
Only the indoors are sprayed. The results of this study,
however, s(.iggest a more direct contamination. Inter-
views with villagers indicate that, at several places, the
spraying equipment was cleaned in the rivers after spray-
ing was completed.
Very low levels of residues were found in organisms
from the Parishan Lake. The levels are comparable to
those found in areas subjected only to airborne contam-
ination (14). However, due to the limited number of
samples processed from Parishan Lake and the Kupor
and Shahpour Rivers, the results are only tentative. The
distribution within these areas requires further studies.
However, the high levels found in the Kupor and Shah-
pour Rivers may adversely afl'ect reproduction of certain
fish species.
Comparison of DDT levels in cyprinide fish from the
Latian and Karadj reservoirs shows that the Latian
reservoir is more e.xposed to pesticide contamination
than is the Karadj reservoir.
Pike collected from Bandar Pahlavi Mordab show re-
markably low levels of DDT in the muscles. The pike is
a predatory fish and usually accumulates persistent sub-
stances readily. DDT has been used in the area for
agriculture and in vector control programs. However,
due to rimolT, the amount of clay and soil particles in
the water is extremely high. So, most DDT probably
Vol. 12, No. 2, September 1978
85
enters the lake attaehed to these partielcs, settles to the
bottom, and is not directly incorporated in the pelagic
food chain.
The amounts of DDT found in the muscle and eggs of
sturgeon from the Caspian Sea were similar to those re-
ported by Higgins (3) but higher than those found by
Hashemy-Tonkabony and Asadi Langaroodi (2).
The magnitude and pattern of accimiulation of DDT
in sturgeon muscle and eggs is closely related to the fat
content. When calculated on a fat-weight basis, the
amount accumulated in muscle and eggs of individual
fish is not significantly different. Thus, the accumulation
of DDT and its metabolites in muscle and eggs of the
sturgeon seems to be of a similar magnitude.
It is well known that even if the DDT accumulated by
fish does not harm the individual, it might be disastrous
for the population. This is because DDT may, even at
low levels, interfere with the reproduction of certain
species 16). Present levels of DDT found in the sturgeon
eggs may be a threat to the sturgeon population. How-
ever, different species respond differently to the influence
of accumulated compounds. Lack of experimental infor-
mation on the sensitivity of sturgeon to organochlorine
pesticide residues make it impossible to evaluate the
present threat.
The occurrence of PCBs in various components of the
global ecosystem is well documented (4. 5. 7. 10, 11).
In Europe, and especially in industrialized areas, PCBs
are frequently found in the biota and in airborne fallout
115. 16).
In Iran, however, there is not yet any sign of a wide-
spread contamination by PCBs as indicated by the ab-
sence of these compounds in the organisms analyzed.
PCBs have only been found in samples collected in
Tehran, presumably originating from local runoff. Strict
regulation of the PCBs and PCB-containing products
might prevent their accumulation in food chains and
reduce their impact on the environment.
Acknowledgment
Authors thank Eskandar Firouz, Director of Department
of the Environment, for valuable comments on the
manuscript and for permission to publish the results of
the investigation. Thanks are also due to M. Taghi
Farvar who initiated the study and to Kenneth and
Sarah Kimball and Jack Boetcher who participated in
various phases of the field work.
LITERATURE CITED
(/) Hcillcr. H. L.. cl (tl. 1945. The chemical composition
of technical DDT. J. Am. Chem. Soc. 67(9): 1591-
1602.
(2) Hashemy-Tonkabony, S. £., and F. Asadi Lonf;aroodi.
1976. Detection and determination of chlorinated pes-
ticide residues in Caspian Sea fish by gas-liquid chro-
matography. Environ. Res. 12(3) :275-280.
(3) Higgins, R. P. 1973. Survey of pesticide residues and
heavy metals in Caspian Sea biota from Bandar-
Pahlavie, Iran. Mimeo. 1 1 pp.. Office of Environ-
mental Sciences, Smithsonian Institution. Washington,
DC
(4) Holdcn. A. V. 1970. Source of polychlorinated bi-
phenyl contamination in the marine environment.
Nature 228(5277) : 1220-1221.
(5) Jensen, S., A. G. Johnels, M. Ols.<;on, and G. Otterlind.
1969. DDT and PCB in marine animals from Swedish
waters. Nature 224(5216) :247-25(l.
(6) Johnson, D. W . 196S. Pesticides and fishes — a review
of selected literature. Trans. Am. Fish. Soc. 97(4):
398-424.
(7) Koeinan, J. H., M. C. Ten Noever Dc Braiiw, R. H.
De Vos. 1969. Chlorinated biphenyls in fish, mussels,
and birds from the River Rhine and the Netherlands
coastal area. Nature 221 (5 186) : 1 126-1 128.
(S) Kone, F. 1976. Global input and trends of chemical
residues in the biosphere. Environ. Qual. Safety
5:183-196.
(9) Monsanto Companx. 1960. Monsanto Co. Tech. Bull.
No. PL-306, 50 pp!
(/O) Rischionf;h, R. W., L. dc Lappe. 1972. Accumulation
of polychlorinated biphenyls in ecosystems. Environ.
Health Perspectives 1.
(//) Rischrou^h, R. W., P. Ricchc. D. B. Pcakall, S. G.
Herman, and M. N. Kirven. 196S. Polychlorinated bi-
phenyls in the global ecosystem. Nature 220(5172):
1098-1102.
(12) Sddcri;ren, A. 1973. A simplified cleanup technique for
organochlorine residues at the microliter level. Bull.
Environ. Contam. To,xicol. 10(2 ): I 16-119.
(/.?) Sdder.vren, A. 1972. A simplified electron-capture de-
tector. J. Chromatogr. 71 (3 ):532-533.
(14) Siklergrcn. A. 1973. Transport, distribution, and deg-
radation of organochlorine residues in a south Swedish
lake ecosystem. Vatten 2:90-108.
(/.'') Sode/^ren, A. 1972. Chlorinated hydrocarbon residues
in airborne fallout. Nature 236(5347) :395-397.
(/6) Sodeiiiien. A. 1975. Monitoring DDT and PCBs in
airborne fallout. Environ. Qual. Safety Suppl. 3:
803-810.
(17) IViirsler. C. F. 1969. Chlorinated hydrocarbon insecti-
cides and world ecosystem. Biol. Conserv. I: 123-129.
86
Pesticides Monitoring Journal
Chlorinated Hydrocarbon Pesticide Residues in Pacific Oysters (Crassostrea gigas)
from Tasmania, Australia — 1973
Colin Edward Sumner*
ABSTRACT
Pacific oysters (Crassostrea gigas Tliiinherg) from 19 sites in
Tasmania were surveyed for pesticide residues. All samples
were analyzed for dieldrin and DDT, anil five samples were
analyzed for hexaclilorobenzene (HCB) and lindane. Only
DDT was found in all samples. Dieldrin levels were high in
oysters from the Taniar River, hut were highest (0.39 mg/kg
wet weight) in samples from Riiffin's Bay. In contrast, other
residue levels were low. Distribution of pesticides in Tamar
River samples differed: dieldrin cotdd he correlated with in-
dustrial uses upstream and DDT could be correlated with
low-level widespread agricultural use.
Introduction
Pacific oysters (Crassostrea gigas Thunherg). imported
from Japan for cultivation trials, successfully reproduced
themselves and colonized estuarine areas in the Tamar
River, northern Tasmania (75, 16, 17). They represent
the only commercial breeding stocks of Pacific oysters
in Australia, and an oyster industry has evolved using
annual spatfalls. Stick and shell cultch are set in Jan-
uary and later relaid on growing areas around the state.
Oyster spat from the river are also sold to growers in
South Australia and are being used in cultivation trials
in Tongan saltwater lagoons (P. Dinamani, Fisheries
Research Division, New Zealand. 1977. Personal com-
munication).
Wild oysters abound on the shores of the Tamar River
within easy access of the general public. In contrast,
oyster farms are located on intertidal mud/ sand flats
leased from the state for private use by individuals and
companies.
In February 1973, dieldrin and DDT residues in Tamar
River oysters were surveyed to assess the risk of spatfall
failure resulting from pesticide accumulation by adult
oysters (3,7,9). The results indicated that significant
levels of pesticides were present in oyster tissues, and a
complete survey of major oyster beds in the Tamar
River and other oyster-growing areas was commissioned
' Present address: Tasmanian Fisheries Development Aiittiority. P.O.
Box 619F, Hobart. Tasmania, Australia, 7001.
to investigate more fully the risk of spatfall failure and
to establish pesticide levels in oysters available to the
general public.
Sampling and Analytical Methods
Oysters were collected from 14 sites in the Tamar River:
four oyster farms and ten natural reefs. Samples were
also taken from five farms in other areas of the state
(Fig. 1). Tamar sampling sites were identical to those
chosen for a heavy metal survey (/). Samples of 12
oysters were considered representative of the local popu-
lation (2). Ages of cultivated oysters were noted and,
when available, year classes were sampled independently.
All samples were routinely screened for dieldrin and
-DDT residues. Five samples were analyzed also for
he.xachlorobenzene (HCB) and lindane. DDT here in-
ckides -DDT resdues and /7,/;'-TDE and /'.p'-DDE.
.Analyses were performed at the Public Health Service
Analysts Laboratory, Hobart, Tasmania.
Shucked undrained oyster meats were stored at — I8°C,
in mason jars. Before analysis, they were homogenized
in an electric blender. Oyster meats were combined with
a desiccant, anhydrous sodium sulfate (1:3, wet weight),
and alternately blended and chilled until smooth flowing.
Standard procedures were followed for cleaning high-
moisture nonfatty foods (18). Aliquots were extracted
with acetonitrile and were diluted with water before
hexane partitioning. The hexane extract was back-
washed with distilled water and filtered through a
Florisil column.
The column was packed with activated magnesium
silicate and topped with 1 cm of anhydrous sodium
sulfate. Residues were eluted from the column with
6 percent and 15 percent ethyl ether in petroleum ether.
The 6 percent eluate was used directly to determine
DDT residues, HCB, and lindane. The 15 percent eluate
was concentrated and subjected to additional cleanup
through a new Florisil column.
Samples eluted from the Florisil columns were identified
and quantitated by using a Varian Model 1400 gas
Vol. 12, No. 2, September 1978
87
TAMAR RIVER
i_V '^i^''
A , Tamar River
B , Boomer Bay
C. Tata nna Bay
D. Ralph's Bay
E. Simmon 's Bay
F. Gardiner's B ay
FICiURE 1. Oyster sampling sites, Tcisiuania, Australia with
map of Tamar River area — 1973 (A: Tamar R.: B. Boomer
Bay: C. Taruniia Bay: D. Ralph's Bay: E. Simmons Bay:
F. Gardners Bay)
chromatograph equipped with an electron-capture de-
tector. Instrument parameters and operating conditions
follow.
Columns: Pyrcx. 5-ft X Vj-inch diameler, packed with
a mixture of 3 percent UC-200 and 5 percent
QF-1 on 80-100-mesh Gas-Chrom Q
Temperatures: detector 200*C
injector 210°C
oven 185°C
Carrier gas: nitrogen flowing at 40 ml/minute
Thin-layer chromatography was used to check results
obtained by gas chromatography and to check for possi-
ble interference from the presence of polychlorinated
biphcnyls (PCBs). Samples fortified with 1 Mg of each
compound produced average recoveries of 88 p>ercent
-DDT, 93 percent HCB and lindane, and 90 percent
dieldrin. All data reported are corrected for recovery.
The lower limit of quantitation was 10 ppb (10 ^ag/kg);
values less than this but for positively identified peaks
were recorded as trace.
Results
Residue levels of dieldrin, -DDT, HCB. and lindane in
whole oyster meats are presented in Table 1. Dieldrin
was detected in all but three samples. Elevated levels
in oysters from the Tamar River were reflected in a
high of 0.39 Mg/g in the Ruflins Bay sample. SDDT
residues were positively identified from all samples but
were of an order of magnitude lower than dieldrin
levels, ranging from trace to 0.06 /ig/g. Traces of HCB
were found only in the Gardners Bay oysters, and traces
TABLE 1. Pesticide levels in Pacific oysters (Crassostrea gigas), Tasmania, Australia
Sampling Station
Samplin(, Date
AGE, "\EAR
No. Bllked
Residues, mg kg. Whole Oyster
Dieldrin
ISDDT
HCB
Lindane
TAMAR RIVER
1
Rosevears
March 1973
—
18
0.20
0.03
—
—
2
Swan Bay
March 1973
—
12
0.10
0.02
—
—
3
Gravelly Beach
March 1973
—
15
0.21
0.01
—
—
4
Supply Riveri
February 1973
2
17
0.20
0.02
—
—
March 1973
2
15
0.09
0.01
—
—
5
Millwood Jetty
March 1973
—
22
0.10
0.02
—
—
6
Devoit
March 1973
—
12
0.10
0.02
—
—
7
Craigburn
March 1973
—
22
0.19
0.01
—
—
8
Devils Elbow
March 1973
—
20
0.10
0.01
—
—
9
Redwood Bay
February 1973
—
16
0.19
0.03
—
—
March 1973
—
12
0.09
0.01
—
—
10
Ruflins Bay >
February 1973
2
13
0.39
0.01
—
—
.March 1973
3
22
0.27
0.06
—
—
11
East Arm'
February 1973
1
34
0.10
0.02
—
—
2
15
0.09
0.02
—
—
3
19
0.19
0.01
—
—
March 1973
2
19
0.08
0.01
—
—
3
13
0.20
0.01
—
—
12
Middle Island-
February 1973
3
16
0.11
0.03
—
—
Flats
March 1973
2
21
0.09
0.02
—
—
3
19
0.10
0.01
—
—
13
West Arm
March 1973
—
14
0.119
0.01
—
—
14
Br>ants Bay
March 1973
—
14
0.08
0.01
—
—
Boiittifr Bay^
August 1973
1.5
15
ND
T
ND
T
Tiiranna Bay^
July 1973
1.5
15
T
T
ND
T
Ritlptn Bay i
January 1972
2
24
ND
T
—
—
Sinnnons Bay '
August 1973
K5
15
ND
0.01
ND
T
Gardners Bay^
July 1973
1.5
15
T
0.06
r
T
NOTE: — = nol analyzed. ND = not detected, T=<0.01 mg/kg.
' Oyster Tarms.
88
Pesticides Monitoring Journal
of lindane were identified in samples from three of the
leased farms.
The limited sampling of oysters of different ages from
growing areas in the Tamar River suggests few differ-
ences in pesticide concentrations among the groups; this
agrees with Butler's observations (2).
Tamar River samples taken at increasing distances
downriver from Launceston showed diflferences in pesti-
cide concentrations in oyster fats (Fig. 2). Dieldrin
levels were inversely correlated with distance from
Launceston (/■ = 0.900; P = 0.001), whereas DDT
levels showed a more general spread suggestive of wide-
scale low-level use of the pesticide (r = 0.490; 0.05
<P<0.10).
Discussion
Levels of pesticides other than dieldrin were generally
low and probably of negligible significance. Because
oysters are extremely sensitive to organochlorine pollut-
ants, these levels indicate little contamination of the
waterways (4).
Dieldrin levels were higher and indicated a serious level
of contamination of the Tamar River. Levels are com-
Launceslon.km
FIGURE 2. Pesticide concenlrations in oyster fats wifli in-
creasiiif; distance from Launceston, from sampling stations
in T Ulnar River, Tasmania, Australia — March 1973
parable to those reported by Clegg for the Sydney rock
oyster (C. commercialis) in the Brisbane River (6).
Butler, reporting on the U.S. National Pesticide Moni-
toring Program (NPMP), noted similar levels of dieldrin
in oysters from a few locations in Georgia, New York,
South Carolina, and Washington, but these were the
exception (5). Dieldrin was detected in only 15 percent
of all NPMP samples.
Lfptake of dieldrin by eastern oysters (C. virginica) was
studied for a short term by Mason and Rowe ill) and
over a longer period by Parrish (14). Concentration
ratios for the pesticide were 2-8 X 10-' for oysters
exposed to ambient water concentrations of 0.1-9 /xg/
liter. If similar concentration factors apply to C. giga.i,
dieldrin levels in the Tamar River should range from
0.3 Mg/liler to 0.075 Mg/liter. This agrees with 0.18-0.02
;ug/ liter reported in a 1972-73 survey of the Tamar
River by the State Department of the Environment (8).
Such levels would not affect embryonic development or
larval growth and survival if Pacific oysters exhibit
tolerances similar to those reported for eastern oysters.
In the latter, Davis and Hidu (7) foimd little difference
between controls and experimental cultures at dieldrin
concentrations of 25 yj,g/ liter.
Levels of DDT, HCB, and lindane in these oysters are
within Australian tolerance standards for food (13)
and represent little risk to public health. At present
there is no published tolerance for dieldrin residues in
fish, but if limits of the Food and Drug Administration,
U.S. Department of Health, Education and Welfare, are
applied (0.3 mg/kg. shellfish meats), then only one
sample in the February survey exceeded these limits.
Results of the heavy-metal investigation mentioned ear-
lier revealed widespread contamination of oysters in the
Tamar River. Subsequently, oysters cannot be taken for
human consumption from any point upstream of Point
Rapid. This effectively removes any risk of consumption
of oysters with high dieldrin concentrations because
those downstream of Point Rapid exhibited much lower
concentrations of the residue than did upstream samples.
Distribution of pesticide levels throughout the Tamar
River suggested that the minute amounts of DDT are
probably attributable to agricultural runofl". Dieldrin
levels suggested an upstream source of contamination
for the pollutant. Industrial sources in Launceston were
implicated in the Annual Report of the Department of
the Environment (8), and it seems likely that the
dieldrin was used to insect-proof woolen fabrics pro-
duced by a woolen mill in Launceston. Similar instances
were recorded about mills in the United States (10, 12).
Since this survey was conducted, the State Department
of the Environment has attempted to limit the disposal
of a number of pesticides in effluents. (The Launceston-
VoL. 12, No. 2, September 1978
89
based woolen mill was prosecuted for illegal discharge
of dieldrin residues.) Continued monitoring of Tamar
River water samples for dieldrin and DDT has reflected
the success of these moves. In 1972-73, dieldrin was
detected in 89 percent of samples with a maximum
concentration of 0.39 ^g/ liter: DDT was found in 14
percent of samples with a high of 0.04 ,ug/ liter. Com-
parable figures for 1975-76 were: dieldrin. 70 percent,
0.13 ,,g/liter: DDT, 5 percent, trace (0,01 ^(g/liter)
(B. O. Healey, Water Pollution Officer, Department of
the Environment, Hobart. Tasmania. 1977. Unpub-
lished data.)
LITERATURE CITED
(/) Aylini;, G. M. 1974. Uptake of cadmium, zinc, copper,
lead, and chromium in the Pacific oyster, Crussoslrcci
/?/i,'«.s, grown in the Tamar River, Tasmania. Water
Res. 8:729-738.
(2) Bailer. P. A. 1966. Fixation of DDT in estuaries.
Trans. 31st N. A. Wildl. Nat. Res. Conf. pp. 184-189.
(i) Butler, P. .-). 1966. Pesticides in the marine environ-
ment. J. AppI, Ecol. 3(Siippl):253-259.
{4) Butler. P. .A. 1969. Monitoring pesticide pollution.
BioSciencc I9( 10) : 889-891.
(5) Butler, P. A. 1973. Organochlorinc residues in estu-
arine molluscs. 1965-72 — National Pesticide Monitor-
ing Program. Peslic. Monit. J. 6(4 ) :238-362.
(6) ('lef;i;, D. E. 1974. Chlorinated hydrocarbon pesticide
residues in oysters (Crus.'ioslrcu comincrcialis) in
Morton Bay, Queensland. Australia. 1970-72. Pestic.
Monil. J. 8(3):162-166.
(7) Davix. H. S.. and H. HiJu. 1969. Effects of pesticides
on embryonic development of clams and oysters and
on survival and growth of the larvae. Fishery Bull.
Fish. Wildl. Ser. U.S. 67(2) ;393-404.
(S) Depuriinent of the Environment. 1973. Report for
year 1972-73 presented to the Parliament of Tasmania,'
Australia. 19 pp.
(9) Eisler, R. 1970. Latent effects of insecticides intoxica-
tion to marine molluscs. Hydrobiologia 36:345-352.
(10) Garrison, A. W., and D. W. Hill. 1972. Organic pol-
lutants from mill persist in downstream waters. Am.
Dyest. Rep. 62(2):21-23,
(//) Mason, J. W .. and 1). R. Rone. 1976. The accumula-
tion and loss of dieldrin and endrin in the eastern
oyster. Arch. Environ. Contam. Toxicol. 4(3):349-
360.
(/2) Mick, D. L., H. Hetz.ler, and E. Slach. 1974. Organo-
chlorinc insecticide residues in carpeting. Pestic.
Monit. J. 8(2): 140-141.
{13) National Health and Medieal Researeh Council. 1976.
Approved food standards and approved food additives.
Commonwealth Dept. Health. Aust. Govt. Pub. Ser.,
Canberra. Standard for residues of pesticides in food,
pp. 177-208.
(N) Parri.sh. P. A. 1973. Aroclor® 1254, DDT, and
dieldrin: accumulation and loss by American oysters
(Cras.so.strea virtiiinca) exposed continuously for 56
weeks. Tech. Paper NSA Conven. 1973 (Abstract
only) in Proc. Nat. Shellfish Assoc. 64:7.
{!>) Sumner, C. E. 1974. Oysters and Tasmania, Part 2.
Tasmania Fish. Res. 8(2): 1-12.
(16) Thomas. J. M. 1952. The acclimatization and growth
of the Pacific oyster (Gryphaea i:if;as) in Australia.
Aust. J. Marine Freshwater Res. 3( I ):64-73.
(/7) Thomson. J. M. 1959. The naturalization of the
Pacific oyster in Australia. Aust. J. Marine Fresh-
water Res. 10(2): 144-149.
(/iV) U.S. DepartinenI of Health. Education, and Welfare.
Food and Drui; Ailministration. 1971. Pesticide Ana-
lytical Manual, Vol. 1. Section 212 13a(l).
90
Pesticides Monitoring Journal
FOOD AND FEED
DDT Residues in Butter and Infant Formula in India, 1977 '
G. S. Dhaliwal- and R. L. Kalia =
ABSTRACT
Samples of commercicd brands of biilter and infant formula
from ilifferenl parts of India were examined for DDT residues.
All 18 samples of butter representing nine brands were con-
taminated. Levels of DDT residues ranged from 0.42 to
11.36 ppm and exceeded the Food and Agriculture Orga-
nization/World Health Organization practical residue linul
of 1 .25 ppm in 90 percent of the samples. Alt four brands
of infant formula contained DDT residues above the prac-
tical residue Until. Most DDT residues were in the form of
p.p'-TDE in both commodities. Tliis contamination of milk
with excessive amounts of DDT residues seems to be wide-
spread in India.
Introduction
The proportions of DDT and its metabolites present in
cows' milk indicate possible sources of these residues (5).
Different routes of animal exposure result in secretion
of DDT in different forms (//). Animal uptake by
aspiration or intravenous injection results in secretions
of DDT; ingestion leads to secretions in the form of
DDT metabolites.
Limited information is available in India on the nature
of DDT residues in bovine milk. Milk samples from
Delhi contained only residues of p.p'-DDT (I). On the
other hand, most DDT residues in milk from Ludhiana
were in the form of p.p'-lDE (2). Because milk is an
important food commodity, particularly for children, it
is necessary to know the extent and sources of its con-
tamination with DDT. Samples of commercial brands
of butter and infant formula from different parts of
India were analyzed for DDT residues. These commodi-
ties were chosen because of their availabilitv.
'Study financed in part by the Agricuitiiial Research Service, U.S.
Department of Agricuhiire, under PL 4St) project "Studies on pesti-
cides residues and monitoring of pesticidal pollution (IN-ARS-65),"
-Department of Entomology. Punjab Agricultural University. Ludhiana-
141004, Punjab. India.
Materials and Methods
BUTTER
Different commercial brands of butter manufactured in
Punjab, Haryana, Delhi, Rajasthan. and Gujarat were
purchased from the local market in lOO-g packages
February and March 1977. Three butter samples
weighing 100 g each were also purchased during the
same period from local dairies situated in different parts
of Ludhiana city. Laboratory extractions were made
within 2 days.
The method described by Faubert Maunder at al. (4)
was modified slightly and used to extract and isolate
DDT residues. The butter was warmed at about 50°C
to separate the fat which was decanted through dry filter
paper. A 5-g sample of the clarified fat was dissolved in
10 ml of hexane and transferred quantitatively to a
12.'5-ml separatory funnel by using additional small por-
tions of hexane totaling 15 ml. The hexane extract was
partitioned three times into hexane-saturated dimethyl-
formamide. using 10 ml of solvent each time. The
dimethylformamide fraction was backwashed with 10 ml
of dimethylformamide-saturated hexane, diluted with
250 ml of water and 50 ml of sodium chloride-saturated
aqueous solution, and extracted twice with 100 ml of
hexane. The combined herane extracts were concen-
trated to about 5-10 ml for subsequent column cleanup.
Silica gel, 60-200 mesh, was thoroughly washed with
acetone and methanol and activated 1 hour at 130°C.
It was packed in a 50-cm X 2-cm glass column to a
height of 10 cm between la>ers of anhydrous sodium
sulfate. The column was prewashed with 100 ml of
hexane. The sample extract in hexane was added to the
column and eluted with 150 ml of 50 percent benzene
in hexane. The eluate was concentrated to 1-10 ml and
was analyzed by thin-layer and gas-liquid chromatog-
raphy.
Thin-layer chromatography was done by the method of
Thompson et al. (7) on AgNO.-incorporated, alumina-
VoL. 12, No. 2, September 1978
91
G-coated glass plates. /;-Hexane was used as the devel-
oping solvent. The Rf values were; p./ADDF. 0.65:
pp-DDE, 0.88; p.p'-TDE, 0.35: o.p-DDT, 0.77: o.p-
TDE. 0.42: n-BHC. 0.52: /i-BHC. 0.1 : y-BHC, 0.32: and
8-BHC, 0.1.
GLC determinations were made by injecting 1-10 ^i\ of
the sample solution into a Model 7624 Packard gas
chromatograph. Two columns were used: (A) was the
working column and (B) was used for confirmation.
Instrument parameters and operating conditions follow:
Deleclor:
Columns:
Temperature
Carrier gas:
Flow rate:
m ID. packed
1 80-1 no-mesh
Tritium electron-affinity
(A) Pyrex. 102 cm long x 0.4
with 5 percent DC-200
Gas-Chtom Q
(B) Pyrex 1.S4 m long X 0.4 cm ID. packed
w'ith 2 percent DECS on 80-IOO-mesh Gas-
Chrom Q
: Column 190'C
Detector 200°C
Inlet 210°C
Nitrogen
70 ml/ minute for Column A
100 ml/ minute for Column B
Retention times, in minutes, are listed below:
Column A
Column B
/),p-DDE
p.p-TDE
p.p-DDT
o.p'-DDT
o.p'-TDE
,.-BHC
-,-BHC
/i-BHC
2.5
3
2.5
2
1
1.10
1
3.5
10
8
5
6.5
1.5
2
5.5
On column .A, the half-scale deflection was obtained
with 0.5 ng of /7,p'-DDE, 0.8 ng of /;,//-TDE, and
1.0 ng of /7,p'-DDT. Quantitative estimations were
made by comparing peak heights of the unknown with
the standards treated similarly. Recoveries of DDT and
its metabolites at the fortification levels of 0.5 ppm were
80-90 percent. Results were expressed as such and were
not corrected for recovery. The limit of detection of
p,p'-DDT in butter was 0.01 ppm.
The nature of DDT residues was confirmed by a micro-
alkali dehydrohalogenation procedure in the Manual of
Analytical Methods for Analysis of Pesticide Residues in
Human and Einironmculal Samples {10) .
INFANT rORMLLA
Four brands of infant formula manufactured in Punjab,
Bombay, and fiujarat were purchased from a local
market in 500-g packages February-April 1977. Ten g
of infant formula was weighed and diluted to 80 ml with
distilled water. Each sample was blended with 160 ml
of acetone and 160 ml of he.\anc in a vortex beaker for
3 minutes. The extract was ccntrifuged at 3000 rpm
for 10 minutes. The hcxane layer was removed by
92
pipet, concentrated to about 25 ml, and partitioned inlo^
dimethvlformamide three times, using 15 ml of solvent'
each time. The combined dimethvlformamide fractions
were cleaned and analyzed by the procedures described
for butter.
Results ui\d Discussion
DDT residues in butter occurred mainly in the form of
p.p'-DDT. p,p'-DDE. and p.p'-JDE. Small amounts of
o.p'-DDT and o.p'-TDE were also detected. Some sam-
ples had BHC residues in the form of a-, /i-, and 7-
isomers. Only traces of BHC were found. The maxi-
mum residue, 1 ppm BHC, was found in a sample of
butter from Gujarat.
Levels of DDT residues in eighteen samples of butter
representing six commercial and three local brands are
given in Table 1. All but one brand of butter contained
DDT residues higher than the practical residue limit of
1 25 ppm established by the United Nations Food and
Agriculture Organization (FAO)/World Health Organi-
zation (WHO) (9). The level of DDT residues varied
from 0.42 to 1 1.36 ppm with an average of 4.77 ppm.
In a study at Uttar Pradesh Agricultural University,
Pantnager, India (S), two of five butter samples were
contaminated with DDT at an average level of 0.4 ±
0 14 ppm. The highest level of DDT detected was 0.5
ppm. Agnihotri et al. (/) reported that seven of eight
samples of butter collected from Delhi contained DDT
residues higher than the practical residue limit. The
concentration of residues varied from 1.1 to 8.0 ppm
with an average level of 3.8 ppm. The present study
shows that most of the commercial brands of butter
manufactured in Punjab, Haryana, Delhi, Rajasthan,
and Gujarat contained DDT residues higher than the
practical residue limit, and suggests widespread con-
tamination in India of milk with high levels of DDT
residues.
TABI F 1 . Residues of DDT and its metabolites in
euinnuTcial Initter samples, India. 1977
Sample
Number
Orioin
Residues
, PPM
Bui IIR
DDT
DDE
TDE
2 DDT
Brand 1
Gujarat
1.88
2.54
1.62
1.48
1.44
1.44
8.00
6.53
6.35
11.36
10.51
9.41
Biand II
Haryana
1.16
1.18
0.50
0.74
0.73
0.30
3.74
3.51
1.36
5.64
5.42
2.16
Brand 111
I'unj. h
0.75
0.73
0.63
0.58
0.42
0.41
3.54
3.25
2.53
4.87
4.40
3.57
Brand IV
RajaMh.ui
0.75
0.68
0.70
0.73
0.49
0.42
3.73
2.63
2.50
5.21
3.80
3.62
Brand V
Brand VI
Delhi
Gujarat
0.35
0.02
0.02
0.25
0.17
0.19
1.55
0.3.1
0.21
2.15
0.52
0.42
Locale 1
Locale II
Locale Ml
1 udliiana
Ludhiana
Ludhiana
0.81
0.70
0.57
0.58
0.42
0.38
4.47
2.84
2.16
5.86
3.96
3.11
Pesticides Monitoring Journ.\l
TDE is the predominant metabolite detected in all
brands of butter (Table 1). Milk collected recently
from Ludhiana and surrounding areas showed similar
results (2). Since TDE is not being used in India for
crop protection or mosquito control, then TDE residues
must arise as a result of metabolism of DDT. However,
milk and butter samples from Delhi did not show resi-
dues of any metabolite. The residues were detected as
DDT only (/). The other two studies carried out in
India on the DDT contamination of milk and milk
products did not consider the metabolites (6.8). The
high level of TDE found in butter samples suggests that
cattle ingest DDT mainly through contaminated feed.
Witt et al. found a 1 : 1 relation between levels of DDT
residues in cattle feed and the concentration of DDT
secreted in bovine milkfat (12). If this relationship
were true in the present study, DDT residues in cattle
feed would be expected to vary between 0.42 and 1 1.36
ppm, averaging 4.77 ppm. The sources of such high
DDT contamination of cattle feed must be determined
particularly because the use of DDT for plant protection
is limited in India. DDT is used mainly for malaria
control; indoor residual spraying on the walls and roofs
is carried out at the rate of 1 g/m^. Dhaliwal and Kalra
suggested that the indoor spraying might contaminate
stored feed, and thereby contribute partly toward the
ingestion of DDT by cattle (2). However, the con-
tribution of this and other sources of contamination of
milk needs further investigation.
All four popular brands of infant formula contained
DDT residues above the tolerance level of 1 .25 ppm,
usually in the form of TDE (Table 2). The concentra-
tion of DDT varied from 1.52 to 2.72 ppm, averaging
1.90 ppm. Apparently, no other study has been carried
out in India on the DDT contamination of commercial
infant formula. The present study shows that even the
spray drying process in the manufacture of infant for-
mula, does not reduce residues of DDT to below the
FAO/WHO tolerance level. This corresponds with the
observation of Engst et al. {3).
The average level of DDT residues found in infant for-
mula is 1.90 ppm. The consumption of this milk by a
three-month-old child weighing approximately 5 kg at
TABLE 2. RcsUUics nj DDT and its metcihoUtcs in
conunercial inftinl formula .samples, India. 1977
Infant
Origin
Fat
Content,
%
Resi
DUES ON
Fat Basis
PPM
Formula
DDT
DDE
TDE
SDDT
Brand I
Punjab
19
0.6.1
0..13
1.76
2.72
Brand I]
Bombay
19
0.40
0.25
1.04
1.69
Brand III
Gujarat
18
0.26
0.36
1 03
1,65
Brand IV
Bombay
18
0.33
0.17
1.(12
.1.52
the normal feeding rate of 135 g/day would result in
a daily intake of 47 ;u,g of DDT. This value is about
twice the acceptable daily intake of 0.005 mg/kg of
baby weight (25 ^g for an infant weighing 5 kg) estab-
lished for DDT by the Joint Pesticides Committee of
FAO and WHO (9).
LITERATURE CITED
(/) Agnihotri. N. P., R. S. Dcwan. H. K. Jain, and S. Y.
Pandey. 1974. Residues of insecticides in food com-
modities from Delhi — II. High-fat-conlent food ma-
terials. Indian J. Entomol. .16( 3 ) ;203-2O8.
(2) Dhaliwal. G. S.. and R. L. Kalra. 1977. DDT res-
idues in milk samples from Ludhiana and surrounding
areas. Indian J. Ecol. 4( 1 ) : I 3-22.
(.?) Eng.st. R.. L. Pruhl, and E. Jarmatz. 1969. Effect of
food processing on insecticide residues. II. Behaviour
of chlorinated insecticides during industrial production
of dried milk. Nahrung 1 3(6 ) :47 1-475.
(4) Funhcrt Maunder. J., H. Sgan. E. W . Codly, E. W.
Hammond. J. Roluirn, and J. Thompson. 1964. Clean-
up of inimal fats and dairy products for the analysis
of chlorinated pesticide residues. Analyst 89(1056):
168-174.
(5) Haxes. W. ]. 1975. Toxicology of pesticides. Williams
and Wilkins, Baltimore. MD. 5Sf) pp.
(6) Luk.slin)inurayana. W. and P. Krishna Mcnon. 1975.
Screening of Hyderabad market samples of foodstuffs
for organochlorine insecticide residues. Indian J. Plant
Protect. 3(1):4-19.
(7) Thomp.son, R. H.. E. G. Hill, and F. B. Flshwick. 1970.
Pesticide residues in Great Britain. XIII. Organo-
chlorine residues in cereals, pulses, and nuts. Pestic.
Sci. 1:93-98.
(S) Tripathi. H. C. 1966. Organochlorine insecticide resi-
dues in agricultural and animal products in Terai area.
M.Sc. thesis, Uttar Pradesh Agricultural University,
Pantnagar, India, 120 pp.
(9) United Nations. Food and Agricidlnre Oriianizution/
World Health Organization. 1973. Pesticide Residues
in Food. Report of the 1972 Joint Meeting of the FAO
Working Party of Experts on Pesticide Residues and
the WHO Expert Committee on Pesticide Residues.
World Health Organization Tech. Rep. Ser., No. 525;
FAO Agricultural Studies No. 90, 47 pp.
(10) U.S. Environmental Protection A.vency. 1974. Manual
of Analytical Methods for the Analysis of Pesticide
Residues in Human and Environmental Samples. Pre-
pared by Environmental Toxicology Division, Health
Effects Research Laboratory, Research Triangle Park.
N.C. Section XII D, pp. 1-7.
(//) Witt. J. M., F. M. Whilin.i;. W. H. Brown, and J. W.
Stall. 1966a. Contamination of milk from different
routes of animal exposure to DDT. J. Dairy Sci. 49:
370-380.
(12) Witt, J. A/., F. M. Whiting, and W. H. Brown. 1966b.
In Organic Pesticides in the Environment. Advances
in Chemistry Series. No. 60, American Chemical So-
ciety, Washington, DC. 99 pp.
Vol. 12, No. 2, September 1978
93
GENERAL
Organocliloriiw Pesticides and Polychloiinated Biphenyls on Sediments
from a Subarctic Salt Marsh, James Bay, Canada — -1976
W. A. Glooschenko ' and R. C. J. Sampson ^
ABSTRACT
Sediment suniples were eollecled from a suhaietic sail
marsh on James Bay, Ontario in May 1976. Of 15 ori>ano-
chlorine compounds analyzed, trace amounts mainly of
p.p'-DDE and polychlorinated biplienyls (PCBs) were de-
tected, luit could not he quantitated.
llUnxlllCtioil
Organochlorine pesticides and polychlorinated biphenyls
(PCBs) have been detected in subarctic and arctic ma-
rine food chains. PCBs and -DDT have been found in
polar bears, seals, and fish in the Canadian arctic (/)
and in fish in a landlocked lake in northwestern Que-
bec (5). The authors wished to determine levels of these
organochlorine compounds in sediments of a subarctic
wetland since this part of the ecosystem would be the
ultimate sink of many of the compounds.
Sediment samples were collected in May 1976 from a
subarctic salt marsh at North Point, Ontario (51°29'N,
80°27'W), on the western shore of James Bay, approxi-
mately 27 km northeast of Moosonee at the southern end
of James Bay. A sample was collected in Moosonee
from a drainage ditch to check the possibility of local
sources of contamination.
Methods and Materkds
Sediment samples were collected by hand with a stainless
steel trowel from the top 5 cm of five salt marsh sites,
two freshwater creek sediments, and a drainage ditch in
the Moosonee settlement. Samples were placed in alumi-
num cans which had been carefully cleaned with inter-
ference-free solvents and were frozen until analysis
within two months of collection.
'Geology Seclion. Process Rcscarth Division. Can.ida Centre for
Inland Walcrs. I' (). Box 5()5I). Burlinglon. Omano. Canada I 7R 4A6.
-Waicr Qualiiy Branch (Uniario Region). Inland Walcrs Dircciorale.
P.O. Box 5050, Burlington, Ontario, Canada I 7R 4A6.
Thawed wet-sediment samples (10 g) were extracted by
using an ultrasonic probe. Each sample was extracted
three times with 75 ml of acetonitrile for 2 minutes each
time and filtered through Celite and sodium sulfate. The
combined filtrate and washings were partitioned into
petroleum ether, washed with water, dried with sodium
sulfate, and evaporated with a rotary evapwrator to 1 ml,
using isooctane as a keeper. Recovery was 80-100
percent (2).
The concentrate was analyzed by high-pressure liquid
chromatography. Four fractions were collected, evap-
orated to 1 ml, and analyzed by computerized gas
chromatography (GC) with automatic sampling. Identi-
fication was based on quantitative reproducibility (±20
percent) on four columns of varying polarity with a
2 percent retention time variability window. Instrument
parameters and operating conditions follow.
Delectois: linearized ''-Ni electron-capture
Cohimns: (1) 2 m x 3.5 mm I.D.. pyrex, packed witti mixture
of 1.5 percent OV-17 and 1.95 percent QF-I on
llX)-i:0-mesh Gas-Chrom Q
(2) 1.86 m X 4 mm I.D.. packed with mixline of
4 percent OV-101 and 6 percent OV-210 or
QF-1 on 80-100-mesli Gas-Chrom Q
(.1) 1.86 X 4 mm l.O., packed with J percent OV-
101 on 811-10()-mcsh Chromosorb W-HP
(4) 2 m X 3.5 mm I.D., packed with 3 percent
OV-225 on 100-1 20-mesh Gas-Chrom Q
Icmpciatures: column 200° C
injector 225° C
detector 325° C
Carrier gases: mixture of 5 percent methane and 95 percent argon
flowing at 50-75 ml/ minute
Quantitation limits are given in Table I. Detection
limits for the pesticides analyzed are approximately one-
tenth the quantitation limit. Authors were unable to
confirm identities of residues by mass spectrometry
because of the low levels of compounds.
94
Pesticides Monitoring Journal
TABLE 1. Distrihulion of organochtoriiws in sediments from North Point salt marsh complex
Quantitation
Limit.
MC/G
Sample Site
Salt Marsh
Creek
Beds
MOOSONEE
Compound
1
2
3
4
5
1
2
1
0.001
Residues, ;iC
'G DRY WEIGHT
Lindane
< 0.001
ND
ND
ND
ND
ND
ND
< 0.001
Heptachlor
0.001
ND
ND
ND
ND
ND
ND
ND
ND
Aldrin
0.001
ND
ND
ND
ND
ND
ND
ND
ND
Heplachlor epoxid
: 0.001
ND
ND
ND
ND
ND
ND
ND
ND
;i.;>'-DDE
0.001
< 0.001
< 0.001
ND
< 0.001
< 0.001
< 0.001
< 0.001
< O.OOI
Dieldrin
0.001
ND
ND
ND
ND
ND
ND
ND
ND
p.;>-DDT
o.ooi
ND
ND
ND
ND
< 0.001
ND
ND
ND
o.p'-DDT
0.001
ND
ND
ND
ND
ND
ND
ND
ND
Endrin
0.001
ND
ND
ND
< 0.001
ND
ND
ND
ND
ft-Chlordane
0.005
ND
ND
ND
ND
ND
ND
ND
ND
-,-Chlordane
0.005
ND
ND
ND
ND
ND
ND
ND
ND
rv-EndosuIfan
0.01
ND
ND
ND
ND
ND
ND
ND
ND
/3-Endosulfan
0.01
ND
ND
ND
ND
ND
ND
< 0.01
ND
p-p'-Melhoxychlor
0.05
ND
ND
ND
ND
ND
ND
ND
< 0.05
Total PCBs
0.1
< 0.1
< 0.1
< 0.1
< 0.1
< O.I
< 0.1
< 0.1
< 0.1
Results and Discussion
Results are in Table I. Of the 15 organochlorine com-
pounds, none could be quantitated. However, p.p'-DDE
and PCBs were detected in nearly all the samples.
Traces of lindane, p,/?'-DDT, endrin /i-endosulfan, and
/^.p'-methoxychlor were noted.
No river entering James Bay drains regions of agricul-
ture, nor is there intensive recreational use of the area,
a source of pesticide input in southern Ontario (2^).
Therefore, it appears that traces of organochlorine
compounds have been transported to the area by air.
LITERATURE CITED
'1) Bowes, G. W., and C. J. Jonkel. J975. Presence and
distribution of polychlorinated biphenyls (PCBs) in
arctic and subarctic marine food chains. J. Fish. Res.
Board Can. 32(11) :21I 1-2123.
(2) Glooschenko, W. A.. W. M. J. Sirachan. and R. C. J.
Sampson. 1976. Distribution of pesticides and poly-
chlorinated biphenyls in water, sediments, and seston
of the Upper Great Lakes — 1974. Pestic. Monit. J.
10(2):61-67.
(3) Miles, J. R. W.. and C. R. Harris. I97J. Organochlorine
insecticide residues in streams draining agricultural,
urban-agricultural, and resort areas of Ontario, Can-
ada—1971. Pestic. Monit. J. 6(4):363-368.
(4) Frank, R., A. E. Armstrong. R. G. Boelens, H. E.
Braiin, and C. W. Douglas. 1974. Organochlorine
insecticide residues in sediments and fish tissues, On-
tario, Canada. Pestic, Monit. J. 7(3/4): 165-180.
(5) Risebrough, R. W., and D. D. Bergcr. 1971. Evidence
for aerial fall-out of polychlorinated biphenyls (PCBs)
in the eastern Canadian Arctic, Manuscript Rept. No.
23, Pesticide Section, Canadian Wildlife Service.
Vol. 12, No. 2, September 1978
95
APPENDIX
Chemical Names of Compounds Discussed in This Issue
ALDRIN
AROCLOR 124:
ARCKLOR 1:54
AROCLOR 126(1
AZINPHOSMETHYL
BENZENE HEXACHLORIDE (BHC)
BROMACIL
CARBOPHENOTHrON
CHLORDANE
DDE
DDT
DACTHAL (DCPA)
DEF
DEM ETON
DIA/INON
Din DRIN
DIURON
ENDOSL'LFAN
ENDRIN
ETHION
HEPTACHLOR
LINDANE
MALATMION
METHOX^ ( 111 OR
MIREX
PAKATHION
PHORATE
PCBs
TDE
TOXAPHENE
TRiri IRALIN
Hcxachloriihexahydro-p<ii/o. t'.vo-dimcthanonaphthalene 95';!i and related compounds 5%
PCB. approximately 42'^c chlorine
PCB. approximately 54'~t chlorine
PCB. approximately 60% chlorine
0,0- Dimethyl 5-[(4-oxo-l,2,?-benzotria2in-3 (4W )-yl ) methyl] phosphorodithioate
I.2,3.4.?.6-Hcxachlorocyclohexane
5-Bromo-3-scf-biiiyl-6-iTiethyIiiratil
5-t[(p-Chlorophenyl)thiolmeihyll 0,0-dielhyl phosphorodithioale
Octachloro-4,7-methanotetrahydroindane 60% and related compounds 40%
Dichlorodiphenyldichloroethylene
Dichorodiphenyltrichloroethylene
Dimethyl tetrachloroterephthalate
5.5,5-Tribiityl phosphorotrithioate
0,0-Diethyl 0-[2-(ethyIthio)cthyl] phosphoroihioale and O.O-diethyl .S-(2-(cihylihio )eihyl]
phosphorothioate
0,0-DiethyI 0-(2-isopropyl-6-melhyl-4-pyrimidinyl) phosphorothioate
HexachIorocpoxyoclahydro-('/;(^('. cAY^-dimclhanoiiaphthalcnc S5'^f and related compounds 15%
3-(.^,4-DichIorophcnyl )-l .l-dimethylurea
Hexachlorohcxahydromelhano-2.4..Vbenzodioxathicpin-3-oxide
HexachIoroepoxyoctahydio-<'Mi/'>. cfu/c-dimethanonaphthalene
0,O,O',0'-Tctraclhyl .S..V'-methyIene bisphosphorodithioate
Heptachlorotetrahydro-4,7-meihaniiindenc and related compounds
G<innnti isomer of 1.2.3,4.5,6-hexachlorocycIoIicxane
O.O-Dimclhyl ditIiii>phosphate of diethyl niercaptosiiccinate
2,2-Ris{/j-methox\phcnyl)-l.l.t-Irichlori>ethane SS*"^ and related compounds 12%
Dodecachlort)Octahydro-l,3-mcthailo-I//-cycIobulalcd)pcntalene
O.O-Diethyl 0-/;-nitropheny! phosphorothioate
O.O-Dielhyl .V-| (elhylthio ) methyl | phosphorodithioale
Polychlorinatcd biphenlys. mixtures of chlorinated biphcinl compounds havinji
various percentages of chlorine
Dicllloiodiphcnyldiclllorocthane
Technical chlorinated camphcne 61-69% chlorine
M.<.,M-'rrinuoro-2,6-din it ro-.V,,\'-iJi propyl /i-toluidine
96
Pesticides Monitoring Journal
Information for Contributors
The Pesticides Monitoring Journal welcomes from all
sources qualified data and interpretative information on
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principally to scientists, technicians, and administrators
associated with pesticide monitoring, research, and
other programs concerned with pesticides in the environ-
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Articles are grouped under seven headings. Five follow
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Authors are responsible for the accuracy and validity
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Pesticides Monitoring Journal
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The Pesticides Monitoring Journal j« puibilrshed by the TechnicaJ Service* Division,
Office of Pesticide Programs, V.S, Environmental Protection Agency.
Pesticide monitoring activities of the Federal Government, particularly in those agencies
represented on the Monitoring Panel which participate iiii operation of the nattonail
pesticides monitoring network, are expected to be the principal sources of data and
articles. However, pertinent data in summarized form, together with discussions, are
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Anne R. Yobs, Center for Disease Control
William F. Durham, Environmental Protection Agency
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Address correspondence to:
Paul Fuschini (WH-569)
Editorial Manager
Pesticides Monitoring Journal
U. S. Environmental Protection Agei»ey
Washington, DC. 20460
Editor
Martha Finaa
CONTENTS
Volume 12 December 1978 Number
Page
FISH, WILDLIFE, AND ESTUARIES
Pesticide residues in estuuiine mollitsks. 1977 versus 1972 —
Natioiud Pesticide Monitoring Program 99
Philip A. Butler, Charles D. Kennedy, and Roy L. Schutzmann
Chlorinated insecticide and PCB residues in fish and mussels of east coastal waters of the middle
and north Adriatic Sea. 1974-75 ^ 1 0:
Mhiden Picer, Nena Picer, and Marijan Ahel
Organochlorinc residues and reproduction in the little hro)\n bat. Laurel, Maryland — June 1976 1 13
Donald R. Clark, Jr.. and Alex Krynitsky
SOILS
Pesticide residue levels in soils and crops, 1 97 1 — National Soils Monitoring Program (III) 1 17
Ann E. Carey, Jeanne A. Gowen, Han Tai, William G. Mitchell, and G. Bruce Wiersma
Pesticide application and cropping data from 37 states. 1971 — National Soils Monitoring Program 137
Ann E. Carey, Jeanne A. Gowen, and G. Bruce Wiersma
WATER
Organochlorines, cliolineslerase iidiibitors, and aromatic amines in Dutch water samples,
September 1969-Deceinber 1975 149
Ronald C. C. Wcgman and Peter A. Greve
BRIEF
Organochlorine pesticide levels in Ottawa drinking water, 1976 163
David T. Williams, Frank M. Benoit, Edward E. McNeil, and Rein Otson
APPI NDIX 164
Infortiiul'nnt lor Contributors . . ^ 165
FISH, WILDLIFE, AND ESTUARIES
Pesticide Residues in Estuarine MoUusks, 1977 versus 1972-
National Pesticide Monitoring Program
Philip A. Butler,' Charles D. Kennedy," and Roy L. Schiitzmann"
ABSTRACT
Bivalve moUusks were monitorecl for residues of 20 organo-
chlorine and organopliosphale pesticides and polychtorinated
biphenyls in spring 1977 in 87 of the 181 estuaries routinely
monitored on a monthly basis during 1965-72. DDT, the
only pesticide delected in 1977, occurred at low levels in one
estuary eacli on the Atlantic and Pacific coasts.
Introduction
In 1965 the U.S. Bureau of Commercial Fisheries ini-
tiated a program to monitor shellfish populations for
organochlorines. In cooperation with local laboratories,
about ISO permanent monitoring stations in 15 coastal
states were sampled for any one of 10 species of mol-
lusks monthly. The eastern oyster, Crassostrea virginica.
was the principal species collected on the Atlantic coast,
and C. gigas was the species usually monitored on the
Pacific coast. The program continued until 1972, but
not all areas were monitored for the entire period.
About 8,100 samples containing 15 pooled individuals
were analyzed. DDT was found in almost all samples.
Dieldrin was the next most commonly detected pesti-
cide; residues of endrin, mirex, toxaphene, and poly-
chlorinated biphenyls (PCBs) were detected occasion-
ally. By 1972, there was a clearly defined trend toward
fewer and smaller residues of DDT and its metabo-
lites (/).
Early in 1977, the U.S. Environmental Protection
Agency monitored mollusks at some of the same sites to
determine further trends in pollution levels after the
5-7-year lapse.
1 Ecological Monitoring Branch, Technical Services Division, U.S.
Environmental Protection Agency. Gulf Breeze, FL .12561.
- Ecological Monitoring Branch. Pesticides Monitoring Laboratory,
U.S. Environmental Protection Agency, National Soil Testing Labo-
ratory Station. MS 39529.
Materials and Methods
The original cooperating laboratories agreed to collect
the new samples. About half the former stations where
pesticides had been found consistently a decade ago were
monitored again. Single collections of 30 bivalves at
each site were made just before or during early stages of
the spawning cycle so that tissue lipid levels presumably
would approach the maximum.
There were 178 samples; replicate collections were
made at 89 stations in 87 estuaries. Depending on the
availability, seven species of mollusks were used in-
cluding the freshwater Asiatic clam, Corbicula manilen-
sis: eastern oyster, Crassostrea virginica: Pacific oyster,
C. gigas: Atlantic ribbed mussel, Geulcensia demissa;
northern quahog, Mercenaria mercenaria: soft-shell
clam, Mya arenaria: and blue mussel, Mytilus edidis.
Oysters were sampled in 63 estuaries, mussels in 14, and
clams in 10 estuaries. However, clams are the least
satisfactory as biomonitors (2).
Two samples of 15 bivalves each were collected at each
station. They were shucked but were not drained, and
were homogenized in an electric blender. A single
aliquot of about 50 g from each pooled sample was
preserved with 50 ml reagent grade methanol and mailed
in a methylpentene vial to the EPA Pesticides Monitor-
ing Laboratory in Bay St. Louis, Mississippi, for analysis.
Analytical procedures, detailed elsewhere (3), pjcr-
mitted the detection of 20 organochlorine and organo-
phosphate pesticides and PCBs (Table I ). In the 1965-
72 program, samples were screened routinely for only
1 1 of the more persistent organochlorine pesticides.
Results and Discussion
The salient feature of the 1977 monitoring data was the
absence of detectable pesticide residues in 85 of the 87
Vol. 12, No. 3, December 1978
99
TABIE [, Cotnpouneh delected hy ehemUal procedures
usfd in monitoring moUtisks
OWMNOCmiORrNES
0»G*NOimOSPH«TES
Aldrin
A-zinpho-^methyr
GWordijBie
Carbophenothion
2DOT
DEF
Dleidrin
ncmeton
EndosiiU'iiii.
rMaiinffin
Heptachlor
Ethion
Lindane
Vtalathion
Merhovychtor
Pararhion
Mirex
PhoFare
PCB>i
Toxaphene
■Ti:ifli«»arm
NOfE: Liwer detection liniif is fO MH/ks for all compounds cvcepi
endo'iulfati. -^ MS/I^P; mcthoxythlor and eihion, 30 /it; kp;
mirev., PCBs, iiixaphene. carbophenothion, and DEF, 50
estuaries sampled and the complete absence of PCBs.
On the Atlantic coast, oysters from two adjacent New
Jersey reefs, and owe reef on the Delaware side of upper
Dteissware Baiy contained DDE. Average residue in the
m ssOT^ks- was 3-3 ±. 15 ^g/kg. Oysters from reefs
efoscr to the mouth of the estuary did not contain de-
tectablie residues. As recently as 1972, every monthly
ovsteir sanfvpte on the New Jersey side of the Bay con-
tained ahout three times as much DDT as did samples
collected in 1977, as well as residites of dieldrin and
PCBs. The fauna in Delaware Bay were presumably
contaminated by the hundreds of tons of DDT sprayed
a«riallv between 1950 and 1966 to control New Jersey
marsh mosquitoes (4).
On the Pacific coast, bivalves in only one of the 14
estbwries monitored in California and Washington state
Gonlained pesticide residues. Replicate samples of blue
muss«ls from Muga Lagoon, about 35 miles north of
Los Angeles, contained DDT and its metabolites, TDE
and DDE, at the average level of 122 Mg/kg. A decade
earlier, monthly samples of mussels from this station
contained i:DDT residues of 500-1.800 Mg/kg. as well as
traces of dieldrin and endrin.
The reliability of these isolated data in documenting the
virtual disappearance of pesticide pollution from estua-
rine water is dependent on knowledge gained from the
earlier program of the seasonal aspects of waterborne
pesticide pollution. Monthly samples in that study
showed that pesticide residues in intermittently polluted
areas were typically present in the spring, and, if con-
tinuously present, were usually larger in the spring,
presumably the result of increased river runoff.
The decline in pollution is emphasized by comparison
of the present data with pesticide residue levels and in-
cidence in bivalves from the same estuaries during the
final 12 months of the earlier program (Table 2). This
table shows the number of stations monitored in each
state in 1977 but does not repeat the 1977 residue data.
Since filter-feeding bivalves purge themselves of organic
residues within a few weeks in the absence of continuing
pollution (2), the 1977 data show essentially the dis-
appearance of pesticides from the water mass. However,
there is evidence that persistent pesticides have not
disappeared entirely from most of these estuarine eco-
systems. During 1972-76, yearling lish of several species
were monitored in many of the same estuaries from
which bivalves were collected in 1977 (i). Samples
consisted of 25 whole fish captured twice yearly. In
1976, 68 samples or 36 percent of the 190 samples
analyzed contained DDT residues at levels up to 2,500
Mg/kg; 22 percent of the samples also contained PCBs.
TABLE 2. Summary of pesticiilc rcaidues in estuarine moUusks durinfi the final 12 montlis of the 1965-72 program
in those estuaries re-monitored in 1977
% OF
Arith.
Other
FiM*L i:
No. OF
No. OF
Samples
Mean of
Residues
Species
$[*TP.
Months
Stations
Samples
WITH DDT
DDT, MS/ kg
Detected >
Monitored -
Alabama
1968-69
2
10
100
102
D
2
California
1971-72
14
68
96
81
D.E.P
1,3,4,7
Dclijware
J968-69
5
58
74
44
D
2,4,5
Florida
1968-69
6
61
85
308
D
2
Gesre^a
1971-71
5
60
20
14
D,T,P
2
Maine
1969-70
5
36
14
29
—
6,8
Maryland
1969-70
A
11
64
25
D
2
MissrsAtppi
1971-72
.1
30
63
31
—
2
New Jersey
1971-72
.1
IS
100
74
D.P
2
New York
1971-72
6
67
88
40
D
2,5,7
North Carolina
1971-72
9
88
35
46
D
2
South Carolina
1968-69
7
83
37
24
D.M
2
Tc)ta»
1971-72
6
56
73
72
D.E.T.P
2
Virpinia
1971-72
6
24
96
36
D.P
2
Wathin^lon Male
1967-68
6
72
18
20
—
3
' D=dieldrin, E — endrin. M = mire«. P = PCB,T=Ioxaphene.
' I. Cnrlticula manllensis, Asiatic clam; 2. Crassoslren viminica, eastern oyster; 3. C. gigas. Pacific oyster; 4, Geut<en\ia ilemissa. Atlantic ribbed
muMcl; 5, Mcrcenaria mercenaria. northern quahog; 6. Mia iiremiria, soft-shell clam; 7, Myiilus <i/ii/i.i, blue mussel.
100
Pesticides Monitoring Journal
The residues in fish are probably the result of storage
and recycling of synthetic pesticides in different links of
the food web. The filter-feeding mollusks present a
more realistic picture of the current input of pesticides
into the marine environment. However, bivalves must
be monitored more frequently to reflect fluctuating
pollution patterns.
Acknowledgment
The authors are grateful to the staffs of the many
federal, state, and university agencies, all of whom par-
ticipated enthusiastically in this project.
LITERATURE CITED
( / ) Butler. P. A. 1973. Organochlorine residues in esliuirinc
mollusks, 1965-72 — National Pesticide Monitoring Pro-
gram. Pestic. Monit. J. 6(4) ;238-362.
(2) Butter, P. A. 1966. Pesticides in the marine environ-
ment. J. Appl. Ecol. 3(Suppl.):253-259.
(3) Butler, P. A., and R. L. Scliutzmann. 1978. Residues
of pesticides and PCBs in estuarine fish. 1972-76 — •
National Pesticide Monitoring Program. Pestic. Monit.
J. l2(2);51-59.
(4) Kluas, E. E., and A. A. Beli.slc. 1977. Organochlorine
pesticide and polychlorinated biphenyl residues in
selected fauna from a New Jersey salt marsh — 1967 vs.
1973. Pestic. Monit. J. 10(4) : 149-158.
Vol. 12, No. 3, December 1978
101
Chlorinated Insecticide and PCB Residues in Fish and Mussels
of East Coastal Waters of the Middle and North Adriatic Sea, 1974-75 '
Mladen Picer, Nena Picer, and Marijan Ahel"
ABSTRACT
Concinfrtitions of vliloriiuilcd piwliciiles tiiitl polychloriiuilcd
hiplicnyls (PCBs) were determined in mussels (Mytilus
galloprovincialis) and ,eo/>_v fish (Gibius sp.) collected in four
areas located in eastern coastal waters of the middle and
north Adriatic Sea. Most samples were collected in early
sprint; and lale summer of 1974 and 1975.
The compounds p.p'-DDT, p.p'-DDE. p.p'-TDE, and PCBs
were detected n)Ost frequently. In about 60 percent of the
samples dieldrin was al.w detected.
of chlorinated hydrocarbons in terrestrial, freshwater,
and marine ecosystems (4, //, 19).
The most delicate and endangered parts of world oceans
are scmiclosed formations such as the Mediterranean
Sea and the Adriatic Sea. The Adriatic Sea is shallow
and small, and its northernmost extension, the Gulf of
Trieste, lies virtually in the heart of Middle Europe;
hence it is among the most jeopardized marine eco-
systems in the world (18).
Average wet-weif;ht concentrations of ^DDT and PCBs in
mii.Ksels from the four areas sampled were: Istrian coast,
65 and 76 pph: Rijeka Bay. 5S and 75 pph: Zadar, 36 and
I2S pph: l.osinj Island. 167 and 133 pph. Average concen-
trations in fish sinnples were: Istrian coast, 124 and 144 pph;
Rijeka Bay. 37 and S2 pph: l.osinj Island. 166 and 157 pph.
Dieldrin concentrations were in the low pph range.
Althongli major Italian rivers di.Kcharge chlorinated hydro-
carhons into the north Adriatic, sampling of biota from
Istrian coastal waters indicates no significant effect on the
pollution level. llo»ever, waste waters from small coastal
settlements evidently do contribute significantly to chlori-
nated hydrocarbon contamination of that ocean.
Marine samples from l.osinj Island had high chlorinated
hydrocarh<m concentrations, indicating uptake of pollutants
from the north Adriatic.
Introduction
Many chlorinated insecticides and industrial aromatic
chlorinated hydrocarbons such as polychlorinated ben-
zenes, naphthalenes, biphenyls, and terphenyls arc ex-
tremely resistant to degradation in the environment (12,
22). On the other hand, toxicological and other harm-
ful effects of these compounds on aquatic and terrestrial
ecosystems are well documented (2. fi). Thus world-
wide research has focused on the occurrence and fate
As part of the United Nations Development Program
assisted project "Protection of the Human Environment
in the Yugoslav Adriatic Region," chlorinated hydro-
carbons were measured in mussels (Mytilus gallopro-
vincialis) and in some benthic fishes (Guhius sp.) of the
eastern coastal water of the north and middle Adriatic
and near Losinj Island (Figure I).
The mussel was chosen for monitoring chlorinated
hydrocarbons because it is a well-known filter feeder
recommended for monitoring many organic and inor-
ganic pollutants (6). The goby fish was selected for its
restricted living area and high tolerance for polluted
seawater, which makes it a logical indicator of polluted
marine environments. Other fish species were chosen for
their popularity as food among local populations.
By analyzing chlorinated hydrocarbon contamination in
mussels and fish from the eastern waters of the north
and middle Adriatic, authors hoped to measure regional
pollution caused by intensive agricultural and indus-
triiil discharges into the northern Adriatic, and local
pollution of two nuclei, the Bay of Rijeka and the town
of Zadar. Losinj Island south of the Bay of Rijeka was
chosen as a clean reference area because it has no sig-
nificant industry or agriculture and it is not heavily
populated.
* Study Mippt>rt(;d in purl by Sclf-Maiui^-umcnt Coninmniiy <if Inlcrcsi
for Sticntllk- Research of S. R t'roaii:i
-Ccmre for Marine Research. Rudjer BosKovic Instinilc. 41001 Zaiireh.
Croatia. Yugoslavia.
Saniplini^ and A tudysi.s
Mussels were collected manually or by dredging in inter-
tidal or very shallow water. Soft tissue was removed
102
Pesticides Monitoring Journal
FIGURE I. Aclriiilic Sea, with areas .\aiiiplccl for chlorinatecl insect'nidc and PCS residues in marine biota
from the shell, placed in aluminum foil, and frozen.
The foil had been cleaned with redistilled petroleum
ether and heated at 200 C for 12 hours. Samples con-
sisted of 20-30 individual animals with shells 3-5 cm
long. For the extraction of chlorinated hydrocarbons
a suhsample of 10 g was taken by a clean scalpel.
Sample remains were frozen for analysis.
Goby lish were taken from the sea by angle, placed in
clean aluminum foil, and frozen within a few hours of
capture. Each sample consisted of six individual fishes
8-12 cm long. Samples of single fish were obtained
from commercial catches in local markets. The .speci-
men was measured and weighed, its dorsolateral surface
was scraped clean, and 10 g of epaxial white muscle
tissue was removed by a clean scalpel.
Ten g of muscle tissue and 10 g of anhydrous Na^,S04
were concurrently homogenized and extracted twice
with 75 ml petroleum ether in a Lourdes blender for 3
minutes. Each extract was decanted into an Erlenmeyer
flask and left overnight for settling of fine particles and
then filtered through a 3-cm-high column of anhydrous
NajSOj. The aliquot of extract was evaporated to dry-
ness and the residue of extracted organic matter was
weighed and recorded.
Samples were cleaned as recommended by Holden and
Marsden (9). Mirex was added as an internal standard
prior to concentration of the sample extract with 50-
100 mg lipid residue. The sample extract was con-
centrated to 1 ml under vacuum by means of a rotary
evaporator and applied to a 6-mm-lD column holding
Vol. 1 2, No. 3, December 1 978
103
2 g alumina. The akiniina had hccn prepared by heat-
ing activated alumina (Brockmann activity I) at 500°C
for 12 hours and partly deactivated by adding 5 percent
distilled water by weight. Elation was performed with
1 5 ml hexanc.
PCBs were separated from organochlorine insecticides on
a miniature silica gel column according to the modified
method of Snyder and Reinert (/.^, 17). Hexane eluate
was evaporated to 1 ml and applied to a 10-mm column
holding 100 mm silica gel. The gel was activated for
18 hours at 200 'C. After cooling to room temperature,
/i-pentane was added and column was filed with a mix-
ture of /j-pentante and silica gel. Elution started with
32 ml //-pentane and was completed with 40 ml benzene.
The first eluate contained PCBs and mirex: the second
contained p.p'-T)DE. /J.p'-DDT. />,p'-TDE, and dieldrin.
A Hewlett-Packard 7620 model gas chromatograph
(GC) equipped with "^jvij electron-capture detector
was used. Operating parameters for GC analysis were;
Columns:
Tc-tnpcralurcs:
Carrier gas:
Flow rale:
(A) 1.8-m-by-4-mni glass packed with 1.5 per-
cent SP-225() + 1.95 percent SP-2401 on
100/120 mesh Supelcon AW-DMCS
(B) I.5-tn-by-4-mm glass packed with 4 per-
cent SE-.TO + 6 percent OV-210 on
100/120 mesh Gas-Chrom Q
Injector 240°C
Column 210°C
Detector 250°C
5 percent methane in argon
.^0 ml/ minute
Organochlorine compounds were quantitated by compar-
ing peak areas in sample and standard chromatograms.
PCBs were determined by using a standard solution of
Aroclor 1254.
Experiments comparing aldrin and mirex as internal
standards showed mirex to be superior. Mirex was used
as an internal standard throughout the analyses because
it is rather easily separttted from PCBs on a GC column.
Its loss was used as a measure of recovery in this study;
in fact, recovery of chlorinated hydrocarbons varied
between 68 and 87 percent.
For the confirmatory test samples with higher contents
of DDT were hydrolyzed by KOH (10).
Sensitivity of DDT and its metabolites is 1 ppb wet
weight and for PCBs it is 10 ppb.
In some samples low concenlralions of dieldrin were
fotiiul hut the data are not reported in this paper.
The niethot.1 of organochlorine determination was inter-
calibrated within the International Intercalibration Pro-
gram on Chlorinated Hydrocarbons in Marine Materials
funded by the United Nations Environmental Program
(UNEP). Results obtained in the Centre for Marine
Research were relatively close to the mean values after
excluding disproportionately high residues according
to criteria of Chauvenet (5, 14).
Results and Discussion
Concentrations of chlorinated hydrocarbons in mussels
and fish from coastal waters of the eastern Adriatic are
presented in Table 1. Distribution frequencies of -DDT
and PCBs in mussel" and fish samples are presented in
Figure 2. The level of organochlorine concentrations
varied widely, which is not unreasonable considering
the unusual pollution pattern and hydrography of the
Adriatic Sea and the complexity of the biotic samples
analyzed.
Figures 3 and 4 present arithmetic means and ranges
of DDT and its metabolites, dieldrin, and PCBs in
mussels, goby fishes, and several species of benthic
fishes. Although 14 species of benthic fishes were
analyzed in the present investigation, results are pre-
sented only for those species which had three or more
valid samples analyzed. Except for gobies, fish species
are presented by decreasing order of summed pesticide
and PCB concentrations. Comparing these two de-
creasing orders shows that the position of fish species
differs according to whether the concentrations of pollut-
ants are presented as wet weight or as extracted organic
matter. But both figures indicate that fish species living
in similar environments and eating similar food have
similar concentrations of pollutants.
Most specimens of goby fishes were caught in highly
polkited coastal waters, especially semiclosed harbors
polluted with industrial and domestic wastes, but con-
centrations of chlorinated hydrocarbons in these fishes
are not significantly higher than in other commercial
fishes such as mullet, annular gilthead, and black tail
sea bream. However, these differences become signifi-
cant when concentrations of pollutants are compared
as extracted organic matter (Figure 4).
Stations for monitoring chlorinated hydrocarbon pollu-
lioii of eastern coastal waters of the north and the
middle Adriatic Sea are located in four dilfercnt areas.
The Istrian coastal area belongs to the northern region
o( the Adriatic Sea; Rijeka, Zadar, and Losinj areas be-
long to the so-called Region of Islands (IS). The
northern region of the Adriatic is predominantly alfected
by river waters from northern Italy which create the
most severe pollution problem in the whole Adriatic.
Intensive urban, tourist, agricullural. and industrial de-
velopment in both coastal areas contributes to the prob-
lem. 1 he Region of Islands inekides water surrounding
nearly 1000 islands along the eastern Adriatic coast
and scmiseparated waters between islands and main-
104
PnsTiciDr.s Monitoring Journal
TABLE 1. Chlorinated hydiocwboii concentrations in fish and mussels of east coastal waters
of middle and north Adriatic Sea, 1974-75
Sampling
p.p-DDT
P.p'
-DDE
P-P'
■TDE
DlELDRlN
PCBs
Station
EOM.
wet
EOM,
WET
EOM.
WET
EOM.
WET
EOM.
WET
EOM,
No.
Species'
Date
r^
WEIGHT
PPM
WEIGHT
PPM
WEIGHT
PPM
WEIGHT
PPM
WEIGHT
PPM
ISTRIAN COAST
1
M.G.
March 1974
1.63
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1
M.G.
March 1974
1.25
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
M.G.
March 1974
2.79
ND
ND
8
1.40
ND
ND
ND
ND
2
M.G.
Sept. 1974
0.71
29
4.10
21
3.00
26
3.60
ND
NO
85
11.97
2
M.G.
Sepl. 1974
n.37
13
3.50
13
3.40
14
3.80
1
0.32
34
9.20
2
M.G.
March 1974
2.94
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2
G.
Sepl. 1974
(1.84
16
1.90
15
1.80
13
1.60
2
0.24
ND
ND
3
M.G.
March 1974
1.16
23
1.94
18
1.51
10
1.81
3
0.26
ND
ND
3
M.G.
March 1974
2.53
41
1.65
15
0.60
13
0.53
25
0.98
3
M.G.
March 1974
8.03
45
0.56
39
0.48
17
0.21
115
1.43
3
M.G.
Sepl. 1974
0.62
15
2.41
19
3.05
20
3.22
4
0.58
ND
ND
3
M.G.
Sept. 1974
0.62
34
5,48
29
4.68
38
5.13
9
1,45
168
27.10
3
M.G.
Sept. 1974
1,37
27
1.93
49
3.28
28
2.12
4
0,25
85
6.20
4
M.G.
Oct. 1972
3.79
105
2.78
30
0.80
53
1.40
367
9.68
4
M.G.
March 1973
1.52
35
2.30
65
4.30
44
2.90
256
16.80
5
M G.
Oct. 1972
2.26
ND
ND
1
0.05
ND
ND
4
0.16
5
M.G.
March 1973
1.22
ND
ND
ND
ND
ND
ND
ND
ND
5
M.G.
Oct. 1975
0.41
2
0.44
1
0.16
1
0.16
ND
ND
ND
ND
D.A.
Sept. 1974
4.05
130
3.21
80
1.98
40
0.99
13
0,31
195
4.80
O.M.
Sept. 1974
1.30
45
3.53
27
2.07
29
2 22
4
0.34
45
3.50
B.B.
Sept. 1974
2.75
133
4.85
43
1.87
30
1.09
—
—
422
15.35
P.E.
Sept. 1974
0.91
9
0.99
14
1.54
5
0.48
1
0.12
45
4.90
M.A.
Oct. 1973
1.57
24
1.5
29
1.84
!5
0.95
ND
ND
ND
ND
O.M.
Sept. 1974
2.76
60
2.17
35
1.30
18
0.65
4
0.15
80
2.90
P.E.
Sept. 1974
2.59
4
0,15
16
0.62
13
0.50
■)
0.08
ND
ND
M.B.
Sepl. 1974
2.64
30
1.13
20
0.76
14
0.53
6
0.24
ND
ND
M.A.
Sept. 1974
3.67
64
1.95
48
1.31
76
2.07
15
0.40
520
14.20
RIJEKA AREA
1
M.G.
March 1974
0.52
ND
ND
ND
ND
ND
ND
—
—
ND
ND
1
M.G.
March 1974
0.80
15
1.85
7
0.87
ND
ND
—
—
8
0.94
1
M.G.
Sept. 1974
0.68
5
0.74
4
0.53
4
0.53
ND
ND
11
1.60
1
M.G.
Sept. 1974
1.25
12
0.95
5
0.40
13
1.02
ND
ND
192
14.20
1
G.
Sept. 1974
0,89
X
0.84
9
0.96
3
0.35
1
0.07
27
3.10
1
M.G.
March 1974
2,20
131
6,05
49
2.22
32
1.45
ND
ND
23
1.03
2
M.G.
March 1974
0.74
7
1.25
5
0.65
10
1.28
0.3
0.09
ND
ND
2
M.G.
March 1974
1.20
83
6.90
21
1.77
10
0.79
ND
ND
75
6.20
2
M.G.
March 1974
1 .05
28
2.52
9
0.90
7
0.65
ND
ND
8
0.84
2
M.G.
March 1974
1.35
15
1.10
8
0.51
7
0.54
—
—
9
0.65
2
M.G.
March 1974
1.20
63
5.20
28
2.30
38
3.15
—
—
128
9.80
2
M.G.
Sept. 1974
0.74
8
1.02
4
0.47
12
1.57
ND
ND
168
22.50
2
M.G.
Sept. 1974
0.82
7
0.85
2
0.25
8
1.02
ND
ND
75
9.10
2
M.G.
Sept. 1974
0.63
23
3.65
4
0.55
22
3.42
ND
ND
83
13.20
-)
M.G.
Sept. 1974
0.56
42
7.50
5
0.80
48
8.60
ND
ND
77
13.70
-t
M.G,
Sept. 1974
0.58
22
3.80
8
1.29
35
6.20
ND
ND
164
28.20
3
M.G.
March 1974
1.70
23
1.32
5
0.28
11
0.54
3
0.18
63
3.70
3
M.G.
Sept. 1974
0.56
13
2.20
6
1.03
9
1.60
2
0.29
64
11.40
3
G.
Sept. 1974
1.06
8
0.72
5
0.43
9
0.85
1
0.12
168
15.90
4
M.G.
March 1973
1.10
49
4.50
17
1.54
6
0.52
—
—
234
21.40
4
M.G.
Oct. 1975
0.24
■>
0.79
1
0.42
1
0.59
ND
ND
26
10.60
5
G.
Oct. 1975
3.29
49
1.48
86
2.60
14
0.44
ND
ND
159
4.90
D.A.
Sept. 1974
2.03
4
0.17
2
0.10
2
0.10
1
0.05
15
0.76
M.A.
Oct. 1975
4.15
35
0.85
32
0.78
28
0.67
8
0.20
355
8.60
B.B.
Oct. 1975
14.13
30
0.21
29
0.20
10
0.07
10
0.07
174
1.20
M.B.
Sept. 1974
1.95
ND
ND
9
0.46
10
0.52
ND
ND
115
5.85
P.E.
Sept. 1974
0.53
4
0.72
6
1.10
1
0.15
—
—
4
0.71
M.Mer.
Sept. 1974
0.32
14
4.40
14
4.40
2
0.77
—
—
8
2.35
M.Mer.
Oct. 1975
1.75
20
1.11
8
0.47
8
0.47
ND
ND
98
5.57
G.M.
Oct. 1975
0.92
ND
ND
ND
ND
ND
ND
ND
ND
25
2.70
MB.
Oct. 1975
2.52
ND
ND
ND
ND
ND
ND
ND
ND
53
2.08
P.D.
Sept. 1974
1.20
11
0.92
22
1.84
5
0.35
1
0.13
28
2.30
L.C.
Sept. 1974
0.66
12
1.82
19
2.80
7
1.14
2
0.24
20
3.00
ZADAR AREA
1
M.G.
March 1974
3.20
14
0.42
9
0.28
ND
ND
—
—
ND
ND
1
MG.
March 1974
2.60
17
0.64
9
0.33
ND
ND
—
—
ND
ND
1
M.Ci.
Sept. 1974
0.93
13
0.13
1
0.07
19
2.04
1
0.07
ND
ND
1
M.G.
Sept. 1974
0.87
33
3.80
3
0.32
ND
ND
2
0.26
80
9.20
1
G.
March 1974
1.69
ND
ND
ND
ND
ND
ND
—
—
ND
ND
1
G.
Sept. 1974
1.17
8
0.68
6
0.51
7
0.60
->
0.14
ND
ND
2
M.G.
March 1974
1.10
7
0.59
7
0.59
ND
ND
—
—
ND
ND
2
M.G.
March 1974
1.40
n
0.81
4
0.28
5
0.43
ND
ND
ND
ND
2
M.G.
March 1974
1.70
63
3.70
28
1.52
11
0.62
—
—
200
11.60
2
M.G.
March 1974
1.76
37
2.25
14
0.78
23
1.32
ND
ND
345
19.50
2
M.G.
March 1974
1.07
33
3.10
10
0.97
20
1.87
4
0.37
390
36.50
{Continued next page)
Vol. 12, No. 3, December 1978
105
TABLE 1 (cont'd.).
Chloriiwreil hydiocurhon coiiceiiliiitions in fish unci ntnssels of east coastal waters
of middle and north Adriatic Sea, 1974-75
Station
No. Species'
M.C.
M.G.
M.G.
M.G.
M.G.
G.
G.
M.G.
M.G.
M.G.
M.G.
M.G.
M.G.
M.G.
G.
G.
O.
M.G.
M.G.
M.G.
M.G.
M.G.
G.
G.
M.A.
D.A.
D.A.
O.M.
O.M.
B.B.
M.B.
P.E.
B.S.
B.S.
S.S.
M.Ma.
Sampling
Date
Sepl.
Sept.
Sept.
Sept.
Sept.
1974
1974
1974
1974
1974
March 1974
Sept. 1974
March
March
March
Sept.
Sept.
Sept.
Oct.
March
March
Sept.
March
March
.Sept.
Sept.
Oct.
March
Sept.
Oct.
Sepl.
Oct.
Sepl.
Oct.
Sept.
Oct.
Ocl.
Sept.
Oct.
Oct.
Oct.
1974
1974
1974
1974
1974
1974
1975
1974
1974
1974
1974
1974
1974
1974
1975
1974
1974
1975
1974
1975
1974
1975
1974
1975
1975
1974
1975
1975
1975
EOM.
0.49
0.72
071
1.66
(1.76
0.70
1.60
1.58
1.60
1,60
0.78
0.73
0.57
0.84
1.41
1.30
0.73
1.40
2.20
1.13
1.20
0.52
1.60
1.48
9.41
15.40
1.57
3.11
1.65
2.00
8.61
0.6(1
1.68
2.00
3.78
1.31
p.p'-DDT
p.p'-DDE
p.p'-TDE
WET
weight
5
6
18
7
6
43
17
375
46
138
8
25
8
33
«(l
78
44
119
128
27
13
30
94
17
172
215
7
82
25
43
42
17
8
ND
15
90
EOM,
PPM
WET
WEIGHT
EOM.
PPM
1.02
0.76
2.55
0.42
0.79
6.07
1.06
LOSINJ
23.80
2.90
8.60
0.98
3.42
1.32
3.86
6,4(1
6.00
6.(14
8,50
5,80
2.38
1.08
5.80
5.61
1.15
1.83
1.39
0.44
3.65
1.50
2.12
0.49
0.88
0.65
ND
0,36
6.90
2
4
18
6
7
113
14
0.45
0.50
2.55
0.34
0,92
16,07
0.85
ISLAND
25
61
5
7
5
16
45
30
68
44
39
27
9
24
20
59
107
158
3
70
15
38
85
16
7
ND
21
62
5.50
1.56
3.85
0.50
0.95
0.79
1.88
3.20
2.30
9.32
3.13
1.76
2.38
0.71
4.62
1.20
3.95
1.14
1.03
0.18
2.25
0.91
1.87
0.99
2.63
0.39
ND
0.50
4.75
WET
W1;I0H1
3
5
24
14
7
68
2
134
44
75
8
46
22
33
98
83
870
38
41
159
78
27
19
250
130
120
1
50
10
14
37
6
8
ND
ND
30
EOM.
PPM
0.65
0.69
3.38
0.80
0,92
9.64
0.10
8,50
2.70
4.70
0.98
6.30
3.80
3.86
6.91
6.40
119.00
2.73
1.85
14.10
6,50
5.20
1.13
17.00
1.38
0.78
0.07
1.60
0.61
0.69
0.43
1.00
0.45
ND
ND
2.30
DlELDRlN
PCBs
WET
WEIGHT
EOM.
PPM
ND
ND
1
1
ND
2
3
ND
ND
ND
ND
ND
4
3
ND
ND
ND
ND
ND
13
1
7
ND
5
ND
5
ND
4
ND
ND
0.20
0,07
ND
0.29
0.16
0.43
ND
ND
ND
ND
ND
0.31
0.40
ND
ND
ND
ND
ND
0.08
0.07
0.22
ND
0.06
ND
0.27
ND
0,1(1
0,13
WET EOM.
WEIGHT PPM
II
36
326
336
36
148
11
200
138
ND
120
222
157
94
ND
43
152
ND
112
130
202
220
724
112
295
360
14
624
90
151
128
54
ND
ND
102
40
2.30
5 00
46.00
22.20
4.80
21.10
0.68
12.70
8.60
ND
15.40
.30.40
27.50
1 1 .20
ND
3.30
20.80
ND
5.40
11.30
16.90
42.30
45.10
7.60
3.12
2.34
0.86
20.00
5.50
7.50
1.50
9.00
ND
ND
2.40
3.05
= Ciihlus (several
Note- ND = not detectable; — = not measured; EOM = extracted organic matter. ,
•Names of species in Latin. English, and Croatoserbian; M.G. = Mytllm K„IU>rr„nnch,li>>. Mediterranean mussel, Dagnia;0.
species). Goby. Glavoc; D.A. = Dipl.ulm ann„lans L., Annular Billhead, Spar; O.M. -- OI,h.l., melanma L, Saddled hre,,m Usat,, B_B
L.ps h„„nst.. Bo.ue. Bukva; P.E, -- r.,..lU,. cryllninu. L„ Pandora, Rumcnac; M.A, =- Mu.il .unans nssu Oo\dcn f--'>' •^"»^'- S*-°^t^
zlalac; M.B. .. M„Ls hurhan.s. Red mullet. Barhun: MMer. .. MvrUun,. nurlucm L.. Hake, Osl.c; CM. = Gc,d„s ,m-rla„m L.. Whil ng.
Mol- L.C. ^ Lcp,J,„mla..,,lc,„e Lae.. unknown. Cucn, B.S. -. fl»-vv ,sc,;,.« 1... Saupe, Salpa; S.S. = Scnm,„s scnlm L.. Panned comber, Pirka.
M.Ma. .= Muena maem, L., Caockarel, Modrak; T.D. =- Tracluims Jraca L.. Greater weever. Pauk bijelac.
laniJ. Sparsely populated karstic islands and mountains,
with modest agriculture and almost no industry, con-
stitute the hinterland of these waters. But also in this
region are several pollution nuclei: the Bay of Rijeka
and nearby towns of Bakar. Zadar, and Sibcnik; the
Bay of Kastela and the neighboring town of Split.
Chlorinated hydrocarbon pollutants of marine environ-
ments can originate from such land-based sources as
direct industrial discharges, sewage, and rubbish. But
indirect discharges of these pollutants, especially as agri-
cultural runoff of pesticides and farm wastes into rivers,
also contribute signiticanlly to their concentration in
marine environments (4. 7. 16). These direct and in-
direct discharges are the most common sources of local
pollution. Air is an important secondary source of
chlorinated hydrocarbon pollution (/); wet and dry
lalloul contributes to the regional or even global pollu-
tion of the marine environment.
Concentrations of i:DDT, dieldrin, and PCBs in mussels,
goby lishes, and other benthic fishes according to their
sampling areas are presented in Figures 5-7. Stationary
species of mussels and goby fishes, which are indicators
of local pollution, were often sampled near the source
of waste discharges. Other benthic fishes indicate
broader areas of pollution. Data in the figures show
differences in arithmetic means of residues in mussels,
goby fishes, and benthic fishes between the areas inves-
tigated. Since concentrations vary considerably, -DDT
and PCB residues in mussels and benthic fishes were
analyzed in order to find whether arithmetic means
diller significantly among the areas investigated (Table
2). Mussels from the Losinj area had significantly
higher concentrations of i:DDT than had those from
any other area investigated. Significantly higher PCB
concentrations were found in the l.osinj area than along
the Istrian coast and Bay of Rijeka, but PCB residues
were lower than were DDT concentrations. In fish
106
Pesticides Monitoring Journal
2i
22
20
181-
16
LU 12
a 10
UJ
d: b
LL.
6
2
0
12'
U 10
LU 8
3
C3 6
LU
a: t.
LL
2
MUSSEL
I 1 IDDT
V77A PCB
34d
Iz IJT} k
^ m , M^^T] . n ,
-H M I I '/| ^^^ i-^i M i^^ K. r/) K^ v^ i:\ i , ^ , K/^ i^^ ^^ r^ // I , ^
20 iO 60 80 100 m UO 160 180 200 220 240 260 280 300 320 340 360 380 400 4^0 550 650
FISH
PT^ ^ ^
41^
-P-
-m-
V/^
(TT^^
100 120 140 160 180 200 220 240 260 280 300 320 340 360 400 500 600 700
CONCENTRATIONS, ppb wet weight
FIGURE 2, Distrihiilioii frcquciKtes of ZDDT and PCBs in nui.sseh and fish from cost coastal waters
of middle and north Adriatic Sea
samples, the only concentrations that differed signifi-
cantly by area were -DDT concentrations in samples
from Rijeka Bay versus those from the Losinj area and
in samples from the Istrian coast versus those from the
Rijeka area. PCB concentrations did not differ sig-
nificantly.
Table 3 shows significant differences in arithmetic
means of i:DDT and PCB concentrations in fish and
mussel samples from the same area. No major difference
between -DDT and PCB concentrations is indicated
in mussels and benthic fishes from the same area. Sig-
nificant difference appears only in -DDT concentrations
in fish from the Istrian coastal area.
The ratio of PCB and pesticide concentrations fre-
quently is used for identifying chlorinated hydrocarbon
pollution of marine areas. If this ratio is higher than 1,
the source of pollution is more likely industrial than
agricultural. The ratios of PCB and -DDT concentra-
tions in samples investigated during the present moni-
toring program are given in Figure 8. Only in the
Rijeka area is this ratio significantly higher than 1 for
all the indicator organisms investigated.
To determine main sources of chlorinated hydrocarbon
pollution in eastern Adriatic coastal waters, correlation
between ^DDT and PCB concentrations in mussel and
fish samples was investigated (Figure 9). Statistical
results of the analysis are presented in Table 4 as
Pearson's correlation coefficients.
Significant correlation between concentrations of -DDT
and PCBs existed only in mussels from the Istrian coastal
area and fish from the Rijeka area. This suggests two
possibilities: ditTercnt sources of DDT and PCB residues
in the areas investigated, or different uptake and loss
pathways of -DDT and PCBs for mussels and fish.
Several papers have been published on investigations
of chlorinated hydrocarbons in Adriatic biota and sedi-
VoL. 12, No. 3, December 1978
107
10'
«
i
i
a
to
z
o
<
z
bJ
u
z
o
u
:io
o
X
o
~nx °
Xx
Q 0.
a
M G.
MA D.A 0 M B B
SPECIES SAMPLED
(See Table I footnote.)
MB
PE.
FIGURE 3. Coitccntriilions (wel weiglil) of ':i:DDT. dichlrin, and PCBs in niii\sels and fish from east coastal waters
of middle and north Adriatic Sea
a
E
o
I'
O
O
oo.
a
10
E
Ol
a.
V)
z
o
<
o
o
1 -
UJ
O
z
o
o
01
£
M G
IS
^
o
X
0 M SB MA
SPECIES SAMPLED
(See Table I footnote.)
DA,
PE
MB.
MCillRF -4. Concenlrutions (extracted i>ri;anic matter) of ZDDT. dieldrin. and l'( lis in masscls and fish
from east coastal waters of middle and north Adriatic Sen
108
Pesticides Monitoring Journal
10^
'«
Q.
lo-
co
10
UJ
U
z
o
u
I- Q-
o
WW EOM
ISTRA
Q U 1-1-
7
WW E OM
RIJEKA
y
o
o
B:
EH
WW E.OM
ZADAR
W W'E OM.
LOSINJ
10'
to
10 y
<
I-
z
UJ
u
o
E
o
'c
(7
O
O
' U 4)
E
a.
Q.
0.1
FIGURE 5. Comparison of "ZDDT. diclclriii. and PCB concentrations in mussels from cast coastal n'aters
of middle and north Adriatic Sea
FIGURE 6.
10'
•lO'
Ji
a.
a
Z
o
Q
O
in
o
0.
x-J
;io
<
ui
U
z
o
o
m
o
a.
Q
_j
UJ
a
a:
Q
Q
X
X
JZL
I- m
o u
o a.
Q
Q OQ
§s
a
o
10'
10
(A
Z
o
I-
<
o
E
u
'c
a
tt)
Ld a
z t;
o *
lO E
Ql
Q.
01
W W I E O.M W.wIe.O.M. W.wI E O.M WW E O.M
ISTRA RIJEKA ZADAR LOSINJ
Comparison of '^DDT. dieldrin, and PCB concentrations in .i;ohy fishes from cast coastal waters
of middle and north Adriatic Sea
Vol. 12, No. 3, December 1978
109
.
i
10^-
f- »-
.0- mo
Q.
u
y^ .
a.
0) c
2
^
1- CO
^ ^
J
m
►-
1 o
•- a.
i^
1—
1
»—
Q
Q
1
t—
Q
O
7
1
qCD
7
X
D
3
Q.
f—
Ol
g
X
7
7
»
Z
y
7
—
m»
to
q:
y
y
r
z
o
z
3
o
UJ
n
JJ
<
Q
Z
UJ
Q
D
en 10 -
q:
—
•7
1—
z
^
o
UJ
z
Q
—
Q
UJ
Q
-J
7
_)
L)
X
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Q
UJ
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z
7
o
u
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I
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E
c
.M
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V
V.
E
.0
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WW lE.QM
ISTRA
RIJEKA
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V
o
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o
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c
n
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u
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a
FIGURE 7. Compornon of -DDT, (/icUliiii, and I'CB concentrations in hvnihic fishes from east coastal waters
of niithllc and north Adriatic Sea
TABLE 2. Results of Student's t-test for :iDDT and PCB
concentrations in mussels and fish from same areas
of middle and north Adriatic Sea, 1974-75
SlGNIHt ANI
DtFKtRENCn OF
Arithmi tic Means
2 DDT
PCBs
CUMPARFI) ARKAS
Mussels
Fishes
Mussels
Fishes
Islrian coasi— Rijcka
None
0.01
None
None
Islrian coasi — Zudar
(1.1
NC
None
NC
Islrian coast — Losinj Isl
ind 0.1
None
0.1
None
Rijcka — Zadar
0.1
NC
0.1
NC
Rijcka— Losinj Island
0.01
0.05
0.1
None
Zudar — Losinj Island
0.01
NC
None
NC
Noie; NC = nol calculated.
TABLE y. Rcsidls of Student's t-test for i;/)D 7 and PCB
concentrations in mussels and fish from same areas
of middle and north Adriatic Sea, 1974-75
SlGNIFICANl DtFFFRENtl
OF ARI1HME1IC Means
ARE*
i;Di)T
I'CBs
Islrian coasl
Rijeka
Losinj Island
n.o5
None
None
None
None
None
merits (.?. /5, /<S', 20. 21). But diflkulties of analyzing
chlorinated hydrocarbons in marine samples are nu-
merous (5, 14), and results of the present study were
not compared with published results because analytical
methods of the various studies have not been inter-
calibrated.
Conclusions
Analyses of chlorinated hydrocarbons in biota from
eastern coastal waters of the middle and north Adriatic
sea lead authors to several conclusions.
Although major north Italian rivers polluted with chlori-
nated hydrocarbons discharge their loads into the North
Adriatic, samples from Islrian coastal waters did not
have significantly higher concentrations of these pollut-
ants than did other waters.-
High concentrations of chlorinated hydrocarbons in
marine organisms from Losinj Island indicate a probable
uptake of pollutants in North Adriatic waters.
Chlorinated hydrocarbon levels often dilter dramaticall)
in samples collected at stalioiis which are close together.
no
Pesticides Monitoring Journal
i-
3 -
O
O
o
a
MJj^. FilSH
o
II SIR A
MU^
IFIISW
IMU^
loIjiku
^
1
ZAOM
IIS;Ueit<A
from eau fOdiMi wMffi ■o'/ mMSe mfi\d fWffti A-dirUoie .Sc«
i«^'
|l§mA A:R.£A
*~-F:lfiH
©~MUS;S£!L
5> ^
SMjIfiKA AS'tA
« i
s *
IK- Hi
o
131
W*
I ^
jU.
W
,.)L^ rfflil
PC©i(pipwi|
^J ZAOAS Agf A
C
a.
11^
fi5 ll
,(,,gt wiim mm
^1 >>)K iL
9
« «>
» \
;<
95!
L
fCBipipmi
m
(^ tiMdie mid tu^th Adfi<Uk' §m
Vm- 12, M<i>, 3, I>&cBMi8e«; %^%
jy
TABLE 4. Pearson's coefficient of concldlion lu'twccn
-DDT and PCS concentrations in mussels and fisli from
coastal waters of middle and north Adriatic Sea. 1974-75
Area
Mussels
Fish
Istrian coast
Rijeka
Zadar
Losinj Island
0.927
0.205
0.712
-0.069
0.740
0.815
NC
0.578
Note: NC^not calculated.
possibly because the first station waters had been con-
taminated with waste waters and the second station had
not. Evidently urban waste waters even from small
settlements contribute significantly to the contamination
of Adriatic coastal waters bv chlorinated hydrocarbon
pollutants.
LITERATURE CITED
(/) Bidleinan. T. P.. and C. E. Ohiey. 1974. Chlorinated
hydrocarbons in the Sargasso Sea atmosphere and
surface water. Science 1S3(4I24): 516-518.
(2) Cope. O. B. 1971. Interactions between pesticides and
wildlife. Ann. R. Ent. 61(3 ) :325-332.
( .' ) Crisetif,'. (!.. P. Cortcsi. and E. Carpene. 1973. Resi-
dties of chlorinated pesticides and polyehlorinated
biphenyls in gonads of Adriatic clupei form fishes.
La Niiova Vet. 46(3 ): 144-149.
(4) Elder. D. t97f>. PCB's in N.W. Mediterranean coastal
waters. Mar. Polkit. Bull. 7(2):63-64.
(5) Elder. D. 1976. Inlercalibralion of organochlorine
compound measurements in marine environmental
samples. Progress report No. I, pp. 1-25.
(6) Goldlwri,'. E. D. 1976. Health of the oceans. Pages
168-169 in The Health of the Oceans. The Unesco
Press, Paris.
(7) Hansen. D. J., and A. J. Wilson. Jr. 1970. Significance
of DDT residues from the esluary near Pensacola, Fla.
Pestic. Monit. J. 4l2):51-56.
(8) Hayes, W. ]., Jr. 1969. Pesticides and human toxicity.
Ann. N.Y. Acad. Sci. 16()( 1 ) :4(K54.
(9) Holdeti. A. v.. and K. Marsden. 1969. Single-stage
clean-up of animal tissue extracts for organochlorine
residue analysis. J. Chromatogr. 40(1 ) :48 1-492.
Ud) Jensen. .V., /.. Reidteri;. and R. Vaz. 1975. Methods
for analysis of DDT and PCB in environmental
samples using chromatographic methods. FAO Fisht
Tech. Pap. 137:229-236.
(//) hUinson. T. O. 1972. Chlorinated hydrocarbon resi-
dues in marine animals of Southern California. Bull.
Environ. Contam. Toxicol. 7(4) ;223-228.
(12) Peakall. D. B., and J. L. Lincer. 1970. Polyehlorinated
biphenyls, another long-life widespread chemical in
the environment. Bio Science 20( 17 ) :958-964.
(li) Picer, A/., and M. Ahel. 1978. Separation of PCB's
from DDT and its analogues on a miniature silica gel
column. J. Chromatogr. 150( I) : 1 19-127.
(14) Picer. N.. M. Picer, and M. Aliel. 1976. Discussion of
international intercalibration results of organochlorine
compound measurements in marine environmental
samples. Proc. Second Yugoslav Symposium Standard-
ization. October 1976, G2, pp. 1-9.
(15) Revclante, N.. and M. Gilmartin. 1975. DDT, related
compounds, and PCB in tissues of 19 species of
Northern Adriatic commercial fishes. Invest. Pesq.
39(2):491-507.
(16) Schmidt, T. T.. R. W. Risehrough. and F. Cress. 1971.
Input of polyehlorinated biphenyls into California
coastal waters from urban sewage outfalls. Bull.
Environ. Contam. Toxicol. 6(4):235-242.
(17) Snyder. D. E.. and R. E. Reinert. 1971. Rapid separa-
tion of polyehlorinated biphenyls from DDT and its
analogues on silica gel. Bull. Environ. Contam. Toxi-
col. 6(5):385-390.
(18) Slim, J., A. Avein. J. C encelj, M. Dorer, S. Comiscck,
S. Kveder, A. Malej, D. Meischner. I. Nozina. J. Paid,
and P. Tusnik. 1974. Pollution problems of the Adri-
atic Sea, an interdisciplinary approach. Rev. Int.
Oceanogr. Med. 35-36:21-77.
(19) Ten Berge.W. F.. and M. Hillehrand. 1974. Organo-
chorine compounds in several marine organisms from
the North Sea and Dutch Wadden Sea. Neth. J. Sea
Res. S(4):36I-368.
(20) Viviani. R.. C. Crisetif. V. Pelmzzi. and P. Cortcsi.
1973. Residues of chlorinated pesticides and poly-
ehlorinated biphenyls in Adriatic clupei form fishes.
Coll. Int. Oceanogr. Med. Messina 5:607-621.
(21 I I'iviani. R.. G. Crisetig. P. Cortcsi. and E. Carpene.
1974. Residues of polyehlorinated biphenyls and
chlorinated pesticides in fishes and birds of the Po
Estuary. Rev. Int. Oceanogr. Med. 35-36:79-89.
(22) Woodwcl. G. M.. P. P. CraiK, and H. A. John.son. 1971.
DDT in the biosphere: where does it go? Science
174(40141:1101-1107.
112
Pesticioes Monitoring Journal
Organochlorine Residues and Reproduction in the Little Brown Bat,
Laurel, Maryland — June 1976
Donald R. Clark, Jr., and Alex Krynitsky^
ABSTRACT
Twelve of 43 pregnant Utile brown hats (Myotis lucifugus)
collected at Montpelier Barn. Laurel. Maryland, gave birth
to dead young. Eleven of tliese 12 dead neonates were ab-
normally snuill. Most of the stillbirths were attributable to
unknown reproductive difficulties associated with first preg-
nancies, but four may have been due to high concentrations
of polychlorinated biphenyls (PCB) in the newborn. Residues
of the PCB. DDE. and oxyclilordane crossed the placenta at
similar rates.
Moore, Inc., Fort Washington, Pennsylvania) and the
occlusal tip width of the upper canine (canine tip width,
CTW) was measured with an ocular micrometer in a
30 X dissecting microscope. This measurement is an
indicator of relative age (/).
Pregnant bats were fed mealworms, larvae of the beetle
Tenehrio molitor. samples of which had been found
free of organochlorine residues.
Introduction
A study of wild-caught, pregnant big brown bats
{Eptesicus fiiscus) suggested that Aroclor 1260. a poly-
chlorinated biphenyl (PCB), caused young to be still-
born (3). However, experimental elevation of Aroclor
1260 levels produced no additional stillbirths (2). The
results indicated only that both stillbirths and high levels
of Aroclor 1260 were characteristic of young adult
female big brown bats.
The present study was undertaken after dead neonate
little brown bats (Myotis lucifugus) were observed at
Laurel, Maryland, roosts. Authors wished to determine
whether high organochlorine residues are associated with
stillbirths of little brown bats and, if so, whether this
association resembles that found in big brown bats.
Materials and Methods
On June 3, 1976, 45 pregnant little brown bats were
collected in Montpelier Barn at the Montpelier Mansion
State Historical Site, Laurel, Prince Georges County,
Maryland. Bats were confined individually at Patuxent
Wildlife Research Center in stainless steel wire mesh
cages, 18 cm X 22 cm X 37 cm, equipped with rodent
watering bottles. Laboratory temperature averaged
28. 2X. Subdued sunlight entered two draped windows.
Before being caged, the bats were anesthetized indi-
vidually with the inhalant anesthetic Metofane (Pittman-
• Fish and Wildlife Service. U.S. Department of the Interior. Patuxent
Wildlife Research Center, Laurel, MD 20811.
Parturition began June 3, and the last young was born
June 13. All pregnancies prodticed single young. After
parturition, each female and her young were killed by
freezing. Two females never gave birth: one died of
unknown causes June 8, and the other was frozen June 8
because she apparently was not pregnant although a
small embryo (0.564 g) was found during dissection.
ANALYTICAL PROCEDURES
Adults were prepared for analysis as carcasses; young
were analyzed whole, except for removal of the gastro-
intestinal tract, according to procedures described pre-
viously (2). Gastrointestinal tracts were left in several
small fetuses (0.9 g or less) where removal would have
been diflicult.
Samples were ground with anhydrous sodium sulfate.
The dried mixture was extracted with hexane in a paper
extraction thimble on a Soxhiet extractor for about 7
hours. The extract was cleaned by Florisil column
chromatography, and the cluate containing the pesticides
and PCB was fractionated by Silicar column chroma-
tography (5). The fractions were analyzed with a
Hewlett-Packard Model 5753 gas-liquid chromatograph
equipped with a '"'Ni detector, automatic sampler, and
computing integrator. Instrument parameters and oper-
ating conditions follow:
Column: glass. 1.83 m. packed with a mixture of 1.5 per-
cent OV-17 and 1.95 percent QF-1
Temperatures: column aOCC. detector 300»C. injection port
250°C
Carrier gas: 5 percent methane in argon flowing at 60 ml/
minute; purge flow, 40 ml/minute
Vol. 12, No. 3, December 1978
113
^ete anafyztfcf Hot p. (/-DDE, p-y-TDE, />.//-
DDT., rfiefiirin;. endrin, fteptiielivteT efxn-ide. mirex, oxy-
sIlfcTctene, r(A'-chl(ird.ii>e. tram^nonnch\0f, ch-nonacMor,
hevvKhfiorobenrzenc (HCB), to^'xaphcne, asnd PCB*, The
PTB that Was peeovercd re^«fflfbfcd Arocfor \2fiO in alt
C<»S€S.
Resewsife'* from spiked maHard dwck (Anm platyrhyii-
e/jwvV Jisswss rafiged from* 80 W \04 percetif. R«»«due
dat» «rers not adjiPited on the ha*i» of these rccovcTies.
The foweT liftwf of sensitivity was 0, { ppm. Residues in
f© peteeTrt »{ the sample* were confirmed on an LKB
Model 9000 g»s-liqi«id chromatograph-mass spcclrom-
eiet G»peTated as descfibed previously (-^>. Samples for
onw a*{tri{ antf fwe yoimg were tost during analysis.
Kescrfts are given as ppm wet weight.
GewnTetriHs msaffis- are given for ^esid^^es because the
daf<i were pesiti^eJy ske~wed. Arithmetic means are
givfew with ssa^tfdard errors;; gewnetrie means are given
wilt* 95 persew cowfkfence intervals (CI), Residue
Pe^sfo reportedl as not dcteeied (ND) were entered as
tetm. t& aiffow ec^nverspen to logs and/ or machine
pfotriffg of fhie rfaia, a constant was added to each value
iff fhose da'ta series that incliuJed zeros (Fig, \). Re-
gre'ssi«w Itrtes w^ere fitted by the least-squares method.
Remits and Discussion
co«*£»iriow iff NEWBORN LirrtE brown bats
Of 45 hsm that gave birth, 12 f27.9 percent) produced
dead yowtg. Eleven of the 12 dead yotmg weighed less
(0.048-0, 869 g.> thart the smallest liveborn bat (1.072 g).
T>te twelfth dead neonate weighed 1.541 g, Si.\ of the
12 dead young were partly eaten by their mothers: one
5 32 '
<
r
& ,
O"
z
1
-b1«
m 0
• hve born ysun;
• stillbor n young
O^^il/born young.
0 6 12 18 24
PCB ppm *»t w«,ghi + 0.1 IN NEWBORN BAT
FIGURE 1. Helaiionship of weight as a percent of tiiliill
female Hcivhl to Aroclor 1260 concentration
amonii 41 neonatal little hrown hats
(Sample includes all neonates except two whose extracts
were lost during chemical analysis, )
young was missing its wing tips; a second, one wing and
one foot; and a third, both wings and both feet. Only
the head and the vertebral column of the fourth re-
mained, and only heads remained of the other two.
Total weights of the six young were estimated from the
remaining portions. Estimations for the latter three
young were based on a head-length-to-body-weight re-
lationship derived from the undersized dead young that
were recovered intact. The incompleteness of these six
specimens probably did not seriously bias the results of
the chemical analyses 'except perhaps for the latter
three, which may actually have contained higher con-
centrations of chemicals than were estimated because
most of the young bats' fat. and. therefore, residues,
was in the body portions eaten by the mother. Never-
theless, residues of the PCB for these three bats (6.1,
12. and 25 ppm) exceeded the mean (Table 1) and in-
cluded the maximum.
Wimsatt (6) observed several times that a majority of a
group of females of Myotis liicifugiis in advanced preg-
nancy aborted their fetuses, usually stillborn, within a
few hours of removal from a colony. He attributed this
result to handling or confinement. In the present study,
dead young tended to be more common among later
births, but beyond this tendency there was no clear
pattern. When all 43 births were divided into four
groups of 11. 11. 11, and 1 0 according to chronological
order, the incidences of dead young were 9.1, 18.2,
54.5. and 30,0 percent, respectively. So. the possible
roles of handling and confinement in stillbirths were
not clarified by the present study.
TABLE 1. Principal or^anochlorinc residues in adult
female Utile brown hats and llieir younf;, Laurel, Aiaryland —
Jane 1976
Residues.
PPM Wet Weight
Adults
Young
Chemical
(n = 44)
(" = 43)
PCB (Aroclor 1260)
Geomelric mean
11.38
4.16'
95 ri CI
9.68-13.38
3,08-5,61
Range
3.6-24
ND-25
DDE
Geometric mean
1.65
0,50 =
95% CI
1,50-1.82
0,36-0,69
Range
0.72-3.4
ND-2,2
DDT
Geometric mean
0.08''
4
95% CI
0.05-0.13
Range
ND-1.0
Oxychlordane
Geometric mean
0.45 =
4
95%i CI
0.33-0.60
Range
ND-1 6
t3ieldrin
Geometric mean
0.13"
4
95% CI
0,08-0,19
Range
ND-0,94
—
NOTE: CI — confidence interval; ND — not delected.
' Residue was not delected in 1 sample.
-Residue was not detected in 2 samples.
'Residue was not detecled in !2 samples.
' Residue was not detected in 20 or more samples.
Residue was not detected in 7 samples.
114
Pesticides Monitoring Journal
GENERAL LEVELS OF RESIDUES
Except for the PCB, levels of organochlorines in females
and their young were generally low (Table 1) and
similar to those found in big brown bats from Mont-
pelier Barn (3). Levels of the PCB in adult little brown
bats were 5.8 times greater than those found in the June
1974 collections of big brown bats; the amounts in new-
born little brown bats were 3.5 times greater than those
in newborn big brown bats (i).
Eighteen pregnant big brown bats that had been dosed
with Aroclor 1260 (2) contained 1.8 times the concen-
tration found in little brown bats in the present study
when their carcasses were analyzed after parturition.
The young of big brown bats contained a mean residue
of 4.38 ppm, similar to the mean residue of 4.16 ppm
found in neonates in the present study.
PLACENTAL TRANSFER OF RESIDUES
Amounts in micrograms of the PCB, DDE, and oxy-
chlordane in yoimg were computed as percentages of
the amounts in adults, using the 29 females whose live-
born young appeared to be full-term. The results were
13.2 ± 1.3 percent, 14.3 ± 1.5 percent, and 8.6 ± 1.7
percent, respectively. Paired I tests showed that the
average percentage for oxychlordane was significantly
less than that of either of the other chemicals. However,
1 3 of the values for oxychlordane in newborns were
zero (not detected), and when zero values were elimi-
nated (;i = 16) the respective averages became 15.6 ±
1.9 percent, 17.0 ± 2.2 percent, and 15.5 ± 1.6 per-
cent and there were no significant differences. Elimi-
nation of zeros was probably justified for this compar-
ison because the small absolute amounts of oxychlordane
made their detection less likely. These percentages
resembled those for both control and dosed big brown
bats when Aroclor 1260 was fed experimentally (2),
but they were lower than one of two percentages for
Aroclor 1260 and higher than both percentages for
DDE found earlier in big brown bats that had not been
dosed (3).
RESIDUES AND DEAD YOUNG
Dead young averaged more than twice as much PCB
(mean = 6.68 ppm, ii = 12) as did live young
(mean = 3.04 ppm, n = 29), but the difference was
not significant at the 95 percent level (t = 1.91,
01 > P > 0.05). Levels of DDE and oxychlordane
were almost identical in dead and live young.
Possible effects of the PCB on weight of the young
were calculated by correlating the ppm PCB in the
young with the weight of the young expressed as a
percentage of adult female weight; the result (Fig. 1)
was significant ( ;• = -0.47,0.01 > p> 0.001). When
the six data points based on estimated weights were
eliminated, the relationship remained significant {r —
Vol. 12, No. 3, December 1978
—0.46. 0.01 > p > 0.001 ). Although this relationship
suggests that the PCB may have caused some neonates
to be small, the plotted data in Figure 1 also indicate
that neonates may at the same time be small and con-
tain little PCB. A similar analysis for DDE produced
no significant correlations.
To determine whether weight of the young was related
to residues in adult females, a correlation was made
between weight of the young as a percentage of adult
female weight, and ppm of the PCB. DDE, DDT,
oxychlordane, and dieldrin in adult females. No sig-
nificant relationships were found. Also, females that
produced dead young did not contain residues signifi-
cantly higher than those of females that produced live
young.
RESIDUES IN FEMALES COMPARED WITH RESIDUES IN
YOUNG
The relationships between total micrograms of the
PCB, DDE, and oxychlordane in adult females and in
their newborii young were tested using all 29 pairs of
females and young in which the neonates were entire
and of normal size. Micrograms of residues in the
young were dependent in a positive, linear fashion on
the amount in the adult female: PCB r = 0.74,
p < 0.001; DDE r = 0.60. p < 0.001; oxychlordane
/• = 0.48, 0.01 > p > 0.001. Similar relationships
were found in other bat species {3, 4).
RESIDUES COMPARED WITH DAYS IN CAPTIVITY
Micrograms of residues of the PCB, DDE, DDT, oxy-
chlordane, dieldrin, and »-fl/j.s-nonachlor in carcasses of
adult females were compared to days in captivity for
all 44 females in which residues were measured. Only
oxychlordane declined significantly, from an average
2.6 Mg to 1.0 Mg. The 1 1 -day interval was probably too
short to produce any major declines such as that for
PCBs found earlier in big brown bats confined for 43
days (3).
RESIDUES COMPARED WITH AGE OF FEMALE
No correlations were found between age estimated by
CTW and residues (total Mg in females plus young,
n =44) of the PCB, DDE, DDT, oxychlordane, diel-
drin, and /coHj-nonachlor, whereas PCB residues de-
clined significantly with age in big brown bats (2, 3).
CAUSE OF STILLBIRTHS
Aroclor 1260 did not cause stillbirths in big brown bats,
but high PCB levels and stillbirths were associated be-
cause both occurred more often in younger parent female
bats (2. 3). In the present study, CTW and PCB con-
centrations were not correlated. Furthermore, when
CTW for females with dead young (mean = 0.1 169 ±
0.0213 mm, n = 12) was compared with CTW for
females with live young (mean = 0.1217 ± 0.0130 mm,
115
It = 31). the dilTcrcncc was highly significant among
big hrown hatsr {2). Nevertheless, there appears to be
an association between age and incidence of stillbirths.
Among the neonates represented in Figure 1, there were
.seven small dead bats, less than 16 percent of the
female parent's weight that had PCB concentrations
equal to or less than 7 ppm. Five of the seven female
parents of these bats showed no wear on their canines
and were probably yearlings producing their first off-
spring. Among the 30 neonates that were heavier than
16 percent of the female's weight (Fig. 1). only nine
showed no canine wear. The difference between these
ratios is significant (.v'-' = 4.14. 0.05 > p > 0.01).
Threfore, unknown reproductive difficulties associated
with first pregnancies probably accounted for most of
the young that were born dead. Beyond these, however,
there remain the four dead young with the largest
amounts of the PCB (12, 13, 18, and 25 ppm); none
of their female parents was a yearling.
Therefore, high levels of the PCB may have caused
four young bats to be born dead, hut feeding studies
with captive bats are needed to confirm this conclusion.
Acknowledgment
Authors thank J. Dowdy, G. Chasko, and W. Kramer
for assisting in the capture and maintenance of live bats
and for preparing the sample extracts for analysis;
J. Carpenter for demonstrating the technique for in-
ducing anesthesia; G. Perrygo and H. B. Robey of the
Maryland National Park and Planning Commission for
providing access to Montpelier Barn; and E. Dustman
and A. Federighi for reviewing the manuscript.
LITERATURE CITED
(/) Clirist'uin, J. J. 1956. The natural history of a summer
aggregation of the big brown bat, Epicsicus juscits
jiiscii.s. Am. Midi. Nat. 55(n:66-95.
(2) Clark. D. li.. Jr. 1978. Uptake of dietary PCB by preg-
nant big brown bats (Ephsiciis jusciis) and their
fetuses. Bull. Environ. Contam. To.xicol. 19(6) :707-
714.
(.?) Clark. D. R. Jr.. and T. G. Lamont. 1976. Organo-
chlorine residues and reproduction in the big brown
bat. J. Wildl. Manage. 40(2) :249-254.
(4) Clark. D. R.. Jr.. C. O. Martin, and D. M. Swineford.
1975. Organochlorine insecticide residues in the free-
tailed bat (Tadarida brasiliciusis) at Bracken Cave,
Texas. J. Mammal. 56(2 ) :429-443.
(5) Cromurlie. E., W. L. Rciclicl. L. A'. Locke. A. A.
Beli.slc. T. E. Kai.Kcr, T. G. Lamonl. B. M. Mulhcrn.
R. M. Proiily, and D. M. Swineford. 1975. Residues of
organochlorine pesticides and polychlorinated biphenyls
and autopsy data for bald eagles, 1971-72. Pestic.
Monit. J. 9( 1): 11-14.
(6 1 Wimsatt. W. W. I960. An analysis of parturition in
chiroptera. including new observations on Myotis I.
Iucitiiga.t. J. Mammal. 41(2) : 183-200.
116
PESTiciL)i;s MoNiToRiNc; Journal
SOILS
Pesticide Residue Levels in Soils and Crops, 1971 —
National Soils Monitoring Program (III)
Ann E. Carey,' Jeanne A. Gowen,' Han Tai,' William G. Mitchell,' and G. Bruce Wiersma '
ABSTRACT
Data from the 197 1 National Soils Monitorinti Profiram are
siiiumaiizecl. Composite samples of soil and mature crops
were scheduled for collection from 1,533 4-hectare sites in
37 states. Analyses were performed on 1,486 soil samples
for organochlorines, organophosphates, PCBs, and elemen-
tal arsenic; samples were analyzed for atrazinc only when
pesticide application data indicated current-year use. Orjiano-
chlorine pesticides were detected in 45 percent of the soil
samples in the following order of frequency: dieldrin. ^DDT,
aldrin, chlordane. and heptachlor epoxide. Most pesticide
levels ranged from 0.01 to 0.25 ppm. Crop samples were
collected from 729 sites, and all were analyzed for organo-
chlorines. Crop samples were analyzed for organophosphates
and atrazine only when pesticide application data indicated
current-year use. Organochlorines were detected in 42
percent of the crop samples analyzed, organophosphates in
13 percent, and atrazinc in I percent.
Introdiiclion
The National Soils Monitoring Program is an integral
part of the National Pesticide Monitoring Program
(NPMP). The NPMP was initiated at the recommen-
dation of the President's Science Advisory Committee
in 1963 to determine levels and trends of pesticides and
their degradation products in the environment (4). The
Committee recommended that appropriate federal agen-
cies "develop a continuing network to monitor residue
levels in air, water, soil, man, wildlife and fish" (/).
The U.S. Department of Agriculture (USDA) began
monitoring agricultural soils in 1964. After a series of
^Ecological Monitoring Branch. Benefits and Field Studies Division.
Oflice of Pesticide Programs. U.S. Environmental Protection Agency.
TS-768, Washington. DC 20460.
-Extension Agent. Colorado State Extension Service. Golden, CO.
^Ecological Monitoring Branch. Benefits and Field Studies Division.
Office of Pesticide Programs. U.S. Environmental Protection Agency,
Pesticides Monitoring Laboratory. Bay St. Louis. MS.
* Chief, Pollutant Pathways Branch, Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection Agency, Las
Vegas. NV.
short-term monitoring projects (5-7), a nationwide
agricultural soil monitoring program was designed (9)
and tested (!0). The USDA initiated widespread moni-
toring in 1968 (//) and 1969 (3).
The National Soils Monitoring Program was transferred
to the U.S. Environmental Protection Agency (EPA),
when EPA was created in 1970. The present report sum-
marizes soil and crop pesticide concentration data col-
lected in 1971 (fiscal year 1972) at 1.486 sampling
sites in 37 states. Data were not collected from some
larger western states because of budgetary limitations
and because either those states have little widespread
agriculture or they grow wheat and other small grains
which require fewer pesticides than do nongrain crops.
Sampling Procedures
Site selection criteria and statistical design for the pres-
ent study have been described by Wiersma et al. (9).
During late summer and fall 1971, 1,486 sites in 37
states were sampled (Fig. 1). At each 4-hectare (10-
acre) site, a composite soil sample and a composite
mature crop sample were collected according to pro-
cedures described in the U.S. EPA Sample Collection
Manual {8). Information on cropping practices and a
history of pesticide application for the current cropping
season were obtained in interviews with landowners or
operators. These data have been summarized and pub-
lished separately (2).
A nalytical Procedures
ORGANOCHLORINES AND ORGANOPHOSPHATES
Sample Preparation. Soil — A 300-g subsample was
taken from a thoroughly mixed field sample. The sub-
sample was moistened with SO ml water and extracted
with 600 ml 3:1 hexane-isopropanol by concentric
rotation for 4 hours. The isopropanol was removed by
Vol. 12, No. 3, December 1978
117
FIGURE I . Slates wliere aaricidlural soils and crops were sampled for the 197 1 National Soils Monitoring Program,
U.S. Environmental Proleetion Agency
three distilled water washes, and the hexane extract was
dried with anhydrous sodium sulfate. The sample ex-
tract was stored at low temperature for subsequent
gas-liquid chromatographic analysis.
Sample Preparation. Crops — For samples containing
less than 2 percent fat, e.g., alfalfa, bur clover, corn-
stalks, cotton stalks, green bolls, miscellaneous hay, a
100-g sample of the crop was blended with 25 ml dis-
tilled water for 3 minutes in SOO ml acetonitrile. An
aliquot of the sample extract, representing 10 g of the
original sample, was decanted into a 500-ml Eriemcyer
flask. The sample extract was concentrated under a
three-ball Snyder column to approximately 10 ml; 100
ml hexane was added, and the hexane-acctonitrile
azeotrope was again concentrated to 10 ml. This
process was carried out three times to remove the aceto-
nitrile. The hexane extract was dried with anhydrous
sodium sulfate, the volume was adjusted to 50 ml, and
the extract was stored at low temperature until par-
titioning.
For crop samples containing more than 2 percent fat,
e.g., corn kernels, cottonseed, soybeans, a lOO-g sample
was prcwashed with 100 ml isopropanol and then with
100 ml hexane. Both prcwashes were discarded. The
prewashes were used to remove surface residues which
may have contaminated the grain during removal of
shells, husks, or pods, thus assuring that residues de-
tected were actually contained in the grain. The sample
was dried, dry blended, added to 100 ml isopropanol,
and blended again. After .300 ml hexane was added,
the isopropanol was removed by two washes with satu-
rated aqueous NaCl solution and one wash with dis-
tilled water. The water-alcohol layers were discarded;
the hexane layer was concentrated, adjusted to 50 ml,
and held at low temperature until partitioning.
After extraction, crop samples were partitioned with
hexane-acetonitrile as follows: 50 ml of the hexane
sample extract, representing 10 g, was shaken with
100 ml acetonitrile in a 500-ml separatory funnel. The
bottom acetonitrile layer was set aside. Another 100 ml
acetonitrile was added to the hexane extract and the
separation step described above was repeated twice; the
hexane was discarded and the three acetonitrile layers
were combined. The .^00-ml acetonitrile extract, which
contained essentially all the pesticides from the original
hexane extract, was backwashed with 25 ml acctonitrile-
saturated hexane. and the hexane layer was discarded.
The acetonitrile sample extract was concentrated to ap-
proximately 10 ml under a three-hall .Snyder column,
and 100 nil hexane was added. This process was car-
ried out three times to remove the acetonitrile. The
118
Pesticides Monitoring Journal
hexane extract was adjusted to 7.5 ml and stored at low
temperature for subsequent Florisil column cleanup and
fractionation.
A separate aliquot of the extract not subjected to
Florisil cleanup was reserved for analysis for organo-
phosphates by flame photometric detection.
Florisil Cleanup — An extract equivalent to 5 g original
crop sample was fractionated through a 1 5-g Florisil
column by use of 100 ml 10 percent methylene chloride
in hexane and 100 ml methylene chloride for fractions
one and two, respectively.
Methylene chloride was removed by concentration of
each extract to low volume under a three-ball Snyder
column, addition of 100 ml hexane. and concentration
again to low volume. After two additions of hexane,
the methylene chloride was essentially removed. Each
extract volume was adjusted to 2.5 ml for separate
injection on the gas-liquid chromatograph.
Gas-Liquid Chromatoiiraphy — Gas chromatographs
were equipped with tritium foil electron-affinity detec-
tors for organochlorines and thermionic or flame photo-
metric detectors for organophosphates. A multiple-
column system with polar and nonpolar columns was
used to identify compounds. Instrument parameters and
operating conditions follow:
Gas chromaiiigi aphs:
Columns:
Carrier biases:
Temperatures;
Hewlell Packard 40:a
Hcwleil Packard 40:b
Tracor MT-22(1
iilasH. 6 mm OD x 4 mm ID. 183 cm loni;.
packed with
9 percent QF-I on 100-1 2t>-me.sh Gas-
Chrom Q
.■< percent DC-:(1I1 on 100-1 :o-mesh Gas-
Chrom Q
a mixitire of 1.5 percent OV-17 and 1 <J5
percent QF-l on IOO-l2ll-mesh Supelcoport
5 percent methane-aruon thmini: at Ktt nil/
minute, prepiirilied nitrojien Howing al St)
ml minute
theimionic detector housing; 25ti^C
detector i EC and FPDl 200-2IO'C
injection port 25t) C
columns 166 C
170-175'C
i«5-iyo°c
Minimum detection levels for organochlorines and tri-
fluralin were 0.002-0.03 ppm except for combinations
of polychlorinated biphenyls (PCBs). chlordane, toxa-
phene, and other chemicals which had mininiiim detect-
able levels of 0.05-0. 1 ppm. Minimum detectable levels
for organophosphates were approximately 0.01-0.0.3
ppm. The compounds detectable by the methodologv
of the present study are listed in Table 1. Trilluralin is
detected by the organochlorine methodologv and, for
that reason, appears with the organochlorine analyses
in the tables.
Recovery Suidies — Pesticide recovery values from soil
were 80-110 percent, but usually were close to 100
TABLE 1. Compouiuls detectable hy chemical
methodology of the present study, 1971— National Soils
Monitoring; Program
ORGANOCHLORINES
Alachlor
Aldrjn
Chlordane
o.P'-DDT
i>,r'-Dm
o.p'-DDE
/i,/i'-DDE
«,p'-TDE
P.n'-TDE
Dieldrin
Endosulfan 1 1 )
Endosulfan (II )
Endosulfan sulfate
Endrjn
Heptachlor
Heptachlor epoxide
Uodrin
Lindane (-,-BHC)
Meihoxychlor
Ovex
PCBs
PCNs
Propachlor
Toxaphene
ORGANOPHOSPHATES
DEF
Diazinon
Eihion
Malathion
Parathion. elhyl
Paralhion. methyl
Phorale
Triihion
OTHER HALOGENS
Trifluralin
NOTE: Althougi; trifluralin is a dinitroaniline compound, it is detected
in the methodoloj^y used in the present study, and appears in
Tables 1-7 under the Oryanochlorines heading.
percent. Values from crops ranged from 70 to 100
percent, and varied with amount and type of pesticide
and type of crop involved. Residues in both crop and
soil samples were corrected for recovery. Soil samples
were also corrected to a dry-weight basis.
ATRAZINE
A 50-g subsample was taken from a thoroughly mixed
field sample. The subsample was extracted with 25 ml
water and 300 ml methanol by concentric rotation for
4 hours. The sample extract was then decanted into
a 1 -liter separatory funnel and 200 ml water was
added. The extract was partitioned with 150 ml Freon
113 three times. The Freon 113 fractions were com-
bined and concentrated to incipient dryness. The ex-
tract was dissolved in hexane and adjusted to 5 ml for
injection into a gas-liquid chromatograph equipped with
a thermionic flame detector with a rubidium sulfate
coating on a helix coil. Instrument parameters and
operating conditions follow:
Column: glass. 18.1 cm long « 6 mm OD ^ 4 mm ID.
packed with ^ percent Versamid 900 on 100-
120-mesh Gas-Chrom Q
Cairier gas: helium
Detector fuel gases: oxygen flowing at 20(1-300 ml minute; hydro-
gen flowing at 20-3(1 ml minute
Teinperattires: detector 200"C
injection port 240*C
column 240''C
Confirmatory analyses were performed on a DC-200
column at I80'C and a Coulson detector in the reduc-
tive mode at the following temperatures: pyrolysis tube,
850°C; transfer line, 220°C; and block, 220°C. Re-
covery was 90-110 percent with a minimum detection
level of 0.01 ppm.
Vol. 12. No. 3, December 1978
119
ARSENIC
Arsenic was determined by atomic absorption spectro-
photometrv. The soil sample was extracted with 9.6N
HCI and arsenic was reduced to As ' ■' with SnCl,.
As + -' was partitioned from the acid to benzene, and
then further partitioned from benzene into water for
the absorption measurement. A Perkin-Elmer Model
303 spectrophotometer was used, and absorbance was
measured with an arsenic cathode lamp at 1972 A
with argon as an aspirant to an air-hydrogen flame.
Minimum detection limit was 0.1 ppm, and recovery
averaged 70 percent.
Results from all analyses were corrected for recovery
and are expressed as ppm dry weight.
Results and Discussion
Tables presented in this report can be divided into two
groups: those showing concentrations of pesticides in
soil samples by all sites and states, and those showing
concentrations of pesticides in mature agricultural crops.
Most tables list the number of analyses, the number of
times a compound was detected, the percent occurrence
of the compound, the arithmetic mean, the estimated
geometric mean, and the minimum and maximum posi-
tive concentrations detected.
The estimated geometric mean is routinely presented in
the tables as an alternative to the arithmetic mean as a
measure of central tendency for the data evaluation.
Pesticide residue data frequently contain a large number
of zero values, resulting either from the absence of
pesticides or their presence at levels below the analytical
sensitivity. Such data are seldom distributed normally,
as shown by tests for skewness and kurtosis, but often
approximate a log-normal distribution. After repeated
tests for significant kurtosis and/or skewness, the
log(A' + 0.01) transformation was used to determine
the logarithmic means. The antilogs of these figures
minus 0.01 were taken to estimate the geometric mean
in the untransformed dimension. The estimated geo-
metric mean was calculated only for those compounds
with more than one positive detection.
COMPOUND CONCENTRATIONS IN CROPLAND SOIL
All Sites — A total of 1,486 soil samples were received
from 1,533 sites in 37 states, resulting in a 97 percent
design completion. Results of analyses for organochlo-
rines, organophosphates, triazines, and elemental arsenic
are presented in Table 2. The most frequently detected
pesticide was dieldrin, found in 27 percent of all samples
analyzed. Next were -DDT, aldrin, chlordane, and
TABLE 2. Compoiiiul conccnlrutions in cruplaiul soils for all sample sites in 37 slates, 1971 (FY 1972}
National Soils Monitoring Program
No. OF
% OF
Residues.
PPM Dry Weight
Estimated
Extremes of
Positive
Detections
Positive
Detections
Arithmetic
Mean
Geometric
Meani
Detected Values
Compound
MiN
Max.
ORGANOCHLORINES. 1
4S6
SAMPLES
AJdrin
144
9.7
0.02
0.002
0.01
1.88
Chlordane
119
8.0
U.06
0.003
0.01
6.98
op'-DDE
21
1.4
<0.01
<0.00l
0.01
0.34
;>.P'-DDE
.1.14
22.5
0.11
0.007
0.01
54.98
o.p'-DDT
198
13.3
0(17
0.004
0,01
32.75
p.p'-DDT
305
20.5
0 17
0.010
0.01
245.18
".p'-TDE
10
0.7
1)111
<0.001
0.02
16.79
P.P'-TDE
I 16
7 8
0 115
0.002
0111
38.46
i; DD I
.15(1
24.0
0.61
0.013
0.01
388.16
Dieldrin
40K
27.5
0.05
0.009
0 in
9.83
Endosulfan ( I )
2
0.1
<0.01
<0.00l
0.05
0.23
Endosulfan (11)
.1
0.2
<0.01
<0.001
0.07
1.24
Endosulfan sulfate
.1
0.2
<0.0 1
<0.001
O.K.
2.07
Endrin
14
0.9
<0.0I
<ro.ooi
0.02
1.00
Heptachlor
71
4 9
0.01
0.001
0.01
1.37
Heplachlor epoxide
1(1.1
6.9
<0.0I
0.001
0.01
0.43
Isodrin
.1
0.2
<fl.OI
<0.001
0.01
0.02
Ovex
1
0.1
<0.01
—
1.11
Propachlor
1
0.2
<0.01
<0.00l
0 1)7
0.10
Toxapliene
92
6.2
0.27
0.004
0.18
36.33
Trifluralin
52
3.5
<0.01
0.00!
0.01
1.29
ORGANOPHOSPHATES, 1
.141
SAMPLES
DEF
4
0.4
<0.0l
<0.001
0.15
0.66
Uia/inon
4
0.4
<0.01
<0.001
0.02
0.05
Ethion
0.2
<0.0I
<0.00l
0.06
0.24
Malalhiun
1
0.1
<0.01
_
0.19
Parathion. clhyl
4
0.4
<0.01
<0.001
0.05
0.19
Phoralc
1
0.1
<o.oi
—
O.OK
—
TRIAZINES. 21.1 SAMPLES
Airazine
1''.'
71.4
0.23
0.052
0.01
16.73
HEAVY
METALS. 1.474
SAMPLES
Arsenic
1461
99.1
5.92
3.522
0.09
180.42
' Not calculated when fewer than two positive detections were present.
120
Plsticidis MoNiroRiNci Journal
heptachlor epoxide, found in 24, 10, 8, and 7 percent
of all samples analyzed, respectively.
Table 3 gives the occurrence of pesticide residues in the
agricultural soil samples collected in 1971. The fre-
quency of detection varied widely among the states
surveyed. Atrazine detection frequencies are not com-
parable to the detection frequencies of other compounds
because atrazine analyses were performed onlv when
site application records indicated atrazine use during the
current growing season.
Table 4 gives the percent incidence of residues of
selected organochlorines at specific levels. For most
compounds, the highest percentages of positive detec-
tions were in the 0.01-0.25-ppm category. Toxaphene
was the exception; highest incidence of positive resi-
dues occurred in the > 10.00-ppm category.
By State — Pesticide concentrations in soils of specific
states or state groups are presented in Table 5. Because
some of the smaller eastern states had very few sites,
those with similar geographic locations and/ or agri-
cultural characteristics were combined to obtain more
representative data. State groups used were: Mid-
Atlantic: Delaware, Maryland, New Jersey; New Eng-
land: Connecticut, Maine, Massachusetts, New Hamp-
shire, Rhode Island, Vermont; Virginia and West
Virginia.
Comparisons of the percent occurrence of aldrin, diel-
drin heptachlor epoxide, i:DDT, chlordane, and arsenic
TABLE 3.
Occurrence of organochlorine. orgaiwphosphate
and Iriazine residues in
cropland soil.
/)>■ Stale, 197 1~
National Soils Monitoring Program
Organochlorines
Orcanophosphates
Triazinesi
No. OF
'"c of
No. of
^r OF
No. OF
% of
No. OF
Positive
Positive
No. of
Positive
Positive
No. of
Positive
Positive
State
Analyses
Detections
Detections
Analyses
Detections Detections
Analyses
Detections
Detections
Alabama
23
20
87
11
0
—
1
0
—
Arkansas
46
34
74
33
1
3
1
0
—
California
64
49
77
48
2
4
—
—
—
Florida
18
9
50
15
2
13
—
—
—
Georgia
30
3
10
15
0
—
—
—
—
Idaho
33
8
24
25
0
—
—
—
—
Illinois
142
102
72
93
3
3
23
20
87
Indiana
58
28
48
38
0
—
11
7
64
Iowa
152
108
71
104
0
—
54
44
81
Kentucky
31
1
10
31
0
—
6
5
83
Louisiana
26
20
77
12
0
—
—
—
—
Michigan
55
22
40
50
0
—
11
10
91
Mid-Atlantic
18
7
39
18
->
11
2
1
50
Mississippi
.11
31
100
15
3
20
—
—
—
Missouri
«(l
'31
39
67
0
—
20
13
65
Nebraska
106
32
30
99
2
2
21
17
81
New England
20
8
40
19
1
5
1
0
—
New York
.18
12
32
35
0
—
6
6
100
North Carolina
11
27
87
7
0
—
—
—
—
Ohio
57
13
23
49
0
—
10
5
50
Oklahoma
64
7
11
58
0
—
1
1
100
Oregon
38
14
37
18
0
—
—
—
—
Pennsylvania
36
8
22
35
0
—
5
2
40
South Carolina
17
17
100
3
0
—
■ —
—
—
South Dakota
106
7
7
101
1)
—
3
3
100
Tennessee
27
12
44
16
0
—
1
0
—
Virginia/West Virgin
ia 27
12
44
25
0
—
—
—
—
Washington State
45
11
24
37
0
—
—
—
—
Wisconsin
67
7
10
64
0
—
36
18
50
TOTAL
1486
662
45
1141
16
•
213
152
71
1 Samples analyzed only when application records indicated atrazine use during the current growing season.
TABLE 4. Percent incidence of selected pesticides in cropland soil from all sampling sites in 37 states, 1971 —
National Soils Monitoring Program
Concentration,
Heptachlor
PPM Dry Wt
i:DDTi
Aldrin
DiELDRIN
Chlordane
Heptachlor
Epoxide
Toxaphene
Trifluralin
Not Detected
76.0
90.3
72.5
92.0
95.1
93.1
93.8
96.5
0.01-0.25
11.2
7.9
22.3
3.4
4.4
6.7
0.1
0.26-1.00
6.3
1,3
4.8
3.1
0.4
0.2
1.1
0.2
1.01-5.00
5.1
0.5
0.3
1.4
0.1
—
3.4
0.1
5.01-10.00
0.7
—
O.I
0.1
—
—
1.0
—
> 10.00
0.6
.
—
—
TOTAL
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
'2DDT = o.p'-DDT -I- p.p-DDT + o.r'-DDE + p,p'-DDE + o.p'-TDE + p.p-TDE.
Vol. 12, No. 3, December 1978
121
TABLE 5. Compound concenlralioiis in cropland soil, by state, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
"i OF
Positive
Detections
ARITHMEnr
Mean
Concent R*i ION
Geometric
Mean
Concentration!
Extremes op
Detected Values
MiN.
Max.
ALABAMA, 23 SITES
Ornanochlorincs. 23 samples
Chlordane 1
p.p-DDE 18
o./j-DDT 10
p.p-DDT 16
2 DDT 18
Dicldrin 4
Endrin 1
Heptaclilor 1
Toxaphcne 5
Oreanophosphates. II samples: no residues delected
Triazines. I sample: no residues detected
Heavy Metals. 23 samples
Arsenic 23
4.4
78.3
43.S
69.6
78.3
17.4
4.4
4.4
21.7
100.0
0.02
11.10
0.(15
0.26
0.41
<0.0I
0.02
<0.0I
0.76
2.84
0.044
l).lli4
0.065
0.106
0.0112
0.022
1.855
0.45
0.01
0.0 1
0.0 1
O.OI
0.0 1
0.42
0.07
0.18
0.39
0.33
0.38
1.39
2.07
0.02
6.78
8.13
ARKANSAS, 46 SITES
Organochlorines. 46 samples
Aldrin
i<.;/-DDE
p./i-DDE
o.it-DUT
/i.;)-DDT
p,/y-TDE
2 DDT
Dieldrin
Endrin
Toxaphene
Trifluralin
Organophosphaies, 33 samples
Diazinon
Triazines I sample: no residues detected
Heavy Metals, 46 samples
Arsenic 46
26
14
28
15
28
15
1
9
I
4.4
2.2
56.5
30.4
60.9
32.6
60.9
32.6
2.2
19.6
4.4
3.0
100.0
<0.0I
<0.0I
0.10
11.117
(1..14
(1.07
(1.57
(1.02
<0.0I
0.50
<0.0I
<0.(1I
<0.00I
0.028
0.099
0.054
0.012
0.079
0.009
0.017
<(l.(10l
6.448
O.OI
0.03
0.01
O.OI
0.02
0.01
0.03
0.02
0.10
0.47
0.05
0.02
0.65
0.02
0.94
0.95
4.82
1.03
7.14
0.18
6.67
0.06
24.74
Organochlorines. 64 samples
Chlordane
().;i'-DDE
p./>'-DDE
<'./i'-DDT
/'.//-DDT
",//-TDE
P./Z-TDE
i;ddt
Dieldrin
Endosulfan II
Endosulfan sulfate
Heptachlor
Heptaclilor epoxide
Ovex
Toxaphcne
Trifluralin
Organophosphaies. 48 samples
Eihion
Parathion. ethyl
Heavy Metals. 54 samples
Arsenic
4
45
30
39
2
10
47
3
1
1
1
I
I
13
3
54
CALIFORNIA, 64 SITES
1.6
6.3
70.3
46.9
60.9
3.1
15.6
73.4
4.7
1.6
1.6
1.6
1.6
1.6
20.3
4.7
2.1
2.1
100.0
0.04
(1,01
(1.15
0.09
0.33
<(1.01
0.02
0.61
(1,01
<0.0I
O.OI
<0.0I
<0.0I
0.02
(1.61
0.03
<0.0I
<0.0I
5.26
0.(K)l
0.050
0.024
0.064
0.001
0.004
0.123
0.(101
0.020
0.002
3.802
2.45
0.02
0.01
0.02
0.01
0.01
0.02
0.01
0.09
0.18
0.39
0.02
0.07
1.13
0.73
0.10
0.24
0.17
0.72
0.34
0.87
0.71
2.53
0.20
0.93
3.88
0.19
8.30
1.29
19.14
Orjjanochlorines, 18 samples
Aldrin 3
Chlordane 1
/)./7'-DDE 6
o.f/-DDT 3
/>./>-DDT 6
/>./)'-TDE 3
rDDT 7
Dicldrin 4
Endrin 2
Toxaphene 1
Organophosphaies. 15 samples
Ethion 1
Parathion. ethyl 1
Heavy Metals, 18 samples
Arsenic 16
FLORIDA. 18 SITES
16.7
5.6
33.3
16.7
33.3
16.7
38.9
22.2
11.1
5.6
6.7
6.7
88.9
(1.(11
0 (II
(1.(14
0.(13
0.111
(1.(11
0.19
(1.15
0.06
0.13
<0.11l
O.OI
1.49
0.003
O.OI I
0,006
0.015
0.004
0.025
0.014
(1.0114
0,575
0.01
0.10
0.02
0.02
0.04
0.03
0.02
0.19
0.02
2.35
0.06
0.19
0.12
0.11
0.42
0.33
1.14
0.09
1.89
1.70
1.00
(Continued next page)
122
Pesticides Monitoring Journal
TABLE 5 (cont'd.). Compotind conceiuralioiis in cropland soil. I>y .state. l971~Natiomd Sods Moniloiinf; Pio.mant
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
Positive
Detections
Arithmetic
Mean
Concentration
Geometric
Mean
CONCENTRAllONl
GEORGIA. .1(1 SITES
Organochlorines. ."^0 samples
Chlordane
o.()'-DDE
;!,()'-DDE
o.p-DDT
;).P'-DDT
o./J-TDE
/1.//-TDE
i:DDT
DIeldrin
Heptachlor epoxide
Toxaphene
Trifliiralin
Organophosphaies, 15 samples:
Heavy Melals. 3(1 samples
Arsenic
1
25
14
22
I
11
25
7
2
9
1
no residues detected
3(1
lIKfl
3.3
83.3
46.7
73.3
3.3
36.7
83.3
23.3
6.7
30.0
3.3
100.0
0.02
<0.0I
0.14
0.07
0.35
<0.01
0.03
0.59
0.04
<0.01
1.25
0.01
1.64
0.003
0.062
0.019
0.093
(1.010
0.172
0.007
0.001
0.046
IDAHO, 33 SITES
Extremes of
Detected Values
Max.
(1.14
(1.02
0(11
(1,(11
0.(11
(1.(13
(1.(12
0.01
0.01
0.01
1.06
0.21
0.20
0.21
0.83
0.63
2.70
0.26
4.42
0.45
0.04
10,20
6.99
Oryanochlorines, 33 samples
;i./>-DDE 9
o,;)'-DDT 4
p. (/-DDT 8
/>.()'-TDE 1
i:DDT 9
Dieldrin 4
Toxaphenc 1
Trifliiralin 2
Organophosphaies. 25 samples; no resitlues detected
Heavy Metals, 31 samples
Arsenic 31
27.3
12.1
24.2
3.0
27.3
12.1
3.0
6.1
100.0
0.03
0.01
0.13
<0,0I
O.IS
<0.01
0.15
<0.01
0.008
(1.002
0.009
0.013
0.002
1.785
(1.(12
(1,02
(1.(11
0.08
(1,(14
(1.01
4.96
(1.06
0,30
0.41
0,27
3,23
3,99
0.03
0.07
4.99
ILLINOIS. 142 SITES
Organochlorincs. 142 samples
Aldrin
Chlordane
,.,,/-DDE
,..;)'-DDT
i;DDT
Dieldrin
Heplachlor
Hep(achlor epoxide
Propachlor
TritUiralin
Organophosphaies. 93 samples
Diazinon
Malathion
Phoraie
Triazines. 2.1 samples
Atrazine
Heavy Melals. 141 samples
Arsenic
54
46
2
4
5
96
39
45
2
7
1
1
1
38.0
31,7
1.4
2.8
3.5
66.9
27.5
31.7
1.4
4,9
1,1
1.1
1.1
87.0
(1.06
0.47
<0.01
<0.01
<0.0I
0.14
0.04
0.02
<fl.01
<o.oi
<o.oi
<(l.01
<().01
0.22
7,8
0.011
0.027
<0.(X)l
(1.001
0.001
(1.(15(1
(1.008
0,008
<0.(101
0.00 1
11,102
5.950
INDIANA. 58 SITES
Organochlorines. 58 samples
Aldrin 14
Chloidane ft
«,//-DDE 1
;^/)-DDE 6
»,;''-DDT 2
/>.;/-DDT 4
I'.r'-rOE 2
i:DDT 6
Dieldrin 22
Endosiillan 1
Endostillan II 1
EndosnU.in suHaie 1
Heplachlor 5
Heplachlor epoxide 5
Isodrin 1
Trilliiralin 3
Organophosphaies. .IS samples:
1 ria/ines. 1 I samples
Alra/ine 7
Heavy Melals. 5« samples
Arsenic 58
24,1
10.3
1.7
10.3
3.5
6.9
3.5
10.3
37.9
1,7
1.7
1.7
8.6
X.ft
1,7
S.2
> resKlnes detected
6.1.6
1(10.0
0.08
0.12
<(1.0 1
0.01
<0.01
0.01
0.01
0.03
0.1(1
<0.01
<0.01
<(1.01
(1.01
(1.01
<(l.lll
<0.01
0.05
4.66
0.009
0.0(16
(1.002
(1.001
0.002
0.00 1
0.004
0,019
0,002
(1.002
0.02(1
3,478
0,01
11114
0,(11
0,04
0.01
0,01
(1.0 I
(1,01
0,111
0.02
0.05
0.19
ll.OK
(1,01
0,16
(1,02
0,02
o,ii:
0,02
0,06
0,(14
0,01
0,05
0.07
0,16
11,01
0,01
Olll
0.03
0.01
0.42
1.83
6.98
0.06
O.IO
0.16
0,75
1.37
0.34
0,15
0,92
28.22
1.64
4.10
0,25
0,08
0.56
0,27
0.89
0.85
0.20
0.43
0,13
0.27
15.93
(Continued next pai^e)
Vol. 12, No. 3. December 1978
123
TABLE 5 (cont'd.). Compound concentrations in cropland soil, by slate, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
% OF
Positive
Detections
Arithmetic
Mean
Concentration
Geometric
Mean
Concentration ^
Extremes of
Detected Values
MiN.
Max.
IOWA. 152 SITES
Organochlorines. 152 samples
Aldrin
Chlordane
().p'-DDE
P.p'-DDE
o.p'-DDT
P.p-DDT
p.p-TDE
i;DDT
Dieldrin
Heptachlor
Hepiachlor epoxide
Isodrin
Toxaphcne
Trilluralin
Organophospliates. 104 samples;
rriazincs. 54 samples
Atrazine
Heavy Metals. 152 samples
Arsenic I
28.3
13.2
0.7
11.2
3.3
12.5
2.0
14.5
63.8
8.6
11.8
1.3
0.7
9.87
no residues detected
81.5
99.3
n.i)4
0.06
<().0I
11.01
<o.ni
0.02
<n.oi
0.0.1
0.09
<0.()1
0.01
<O.I)l
0.04
O.lll
0.62
6.1
0.008
0.(X)6
0.002
0.001
0.00.1
<0.001
0.004
0.033
0.001
0.002
<0.001
0.002
0.135
4.574
0.01
0.02
0.01
0.01
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.02
5,97
0.01
0.02
0.24
1.01
1.63
0.19
0.24
1.42
0.04
1.59
0.79
0.15
0.16
0.40
16.73
26.05
KENTUCKY, 31 SITES
Organochlorines, 31 samples
Aldrin 1 3.2
Chlordane 1 3.2
P,P-DDE 2 6.5
PP'-DDT 1 3.2
P.p'-TDE 1 3.2
2DDT 2 6.5
Dieldrin 1 3.2
Endosulfan 1 3.2
Endosulfanll I 3.2
Endosulfan sulfate 1 3,2
Toxaphene 1 3.2
Organophosphates. 31 samples: no residues detected
Triazines, 6 samples
Atrazine 5 8.1.3
Heavy Metals, 31 samples
Arsenic 31 100,0
<l),0l
0,08
<0,0I
<0.01
<0,01
<0,01
0.02
0.01
0.04
0,07
0.06
O.W
9.25
0.001
0.022
5.608
0.01
2.47
0.0 1
0.01
0.02
0.02
0.48
0.23
1.24
2.07
1.80
0.02
0.74
0.05
0.07
0.05
29.31
LOUISIANA. 26 SITES
Organochlorines, 26 samples
Aldrin
1
Chlordane
T
o.P-DDE
1
P,p'-DDE
11
o.p'-DDT
10
P.p'-DDT
11
P.p'-TDE
8
SDDT
11
Dieldrin
7
Toxaphcnc
8
Trifluralin
2
3.9
7.7
3.9
42.3
38.5
42.3
30.8
42,3
26.9
30,8
7,7
<0,0I
0,01
0,01
0,25
0,24
0.79
0.12
1,41
0.02
3.02
0.02
Organophosphates. 12 samples: no residues detected
Heavy Metals, 26 samples
Arsenic 25
0.002
0.033
0.020
0.046
0.014
0,067
0,006
0,057
0,003
2,541
0.03
0.06
0.25
0.03
0.01
0.0 1
0.02
0.05
0.0 1
0.68
0.11
0.41
0.26
2.23
3.66
7.41
1.67
15.22
0.15
.36,33
0.37
10,77
MICHIGAN. 55 SITES
Organochlorines, 55 samples
Aldrin
4
Chlordane
7
P.P-DDE
9
o,p-DDT
6
p.P-DDT
8
P.P-TDE
2
i:DDT
9
Dieldrin
16
Heptachlor
1
Hepiachlor epoxide
3
Trifluralin
1
7.3
12.7
16.4
10.9
14.6
3,6
16.4
29.1
1.8
5,5
Organophosphates. 50 samples: no residues detected
Triazines. II samples
Atrazine til
Heavy Metals. 55 samples
Arsenic
55
90.9
00,0
0,02
o.o:
0 11
0.114
0.22
0.01
0..1S
0.02
<0,01
<0,01
<0.0I
0,09
8,26
o,oo;
0,004
0,006
0,004
0,007
0.001
0.008
0.007
0.001
0.068
4.763
0.07
0.02
0.0 1
0.02
0.02
0.04
0.02
0.01
0.01
0.01
O.IO
0.02
0.55
0.52
0.37
4.35
1.45
8.20
0,72
14,72
0,34
0.06
0.25
73,65
(Continued next page)
124
Pestktdi s Monitoring Journal
TABLE 5 (cont'd.). Compound concern ral ions in cropland soil, by slate. 197 1— National Soils Monitorini; l'rof;rain
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
% OP
Positive
Detections
Arithmetic
Mean
Concentration
Geometric
Mean
Concentration '
Organochlorines, 18 samples
Aldrin
Chlordane
o.p'-DDE
p.p-DDE
o.p'-DDT
p.p-DDT
f>,p'-TDE
SDDT
Dieidrin
Heptachlor epoxide
Organophosphates, 18 samples
Diazinon
Parathion, elhyl
Triazines, 2 samples
Atrazine
Heavy Metals. 18 samples
Arsenic
MID-ATLANTIC-. 18 SITES
S.6
5.6
5.6
16.7
5.6
11. 1
5.6
16.7
27.8
11.1
5.6
5.6
50.0
100.0
<0.01
<0.01
<0.01
0.04
0.01
0.04
0.01
(1.10
no;
0.01
<().01
<0.01
0.0.1
3.8-1
0.005
0.004
0.007
0.007
0.001
Extremes of
Detected Values
MiN.
0.05
0.06
0.03
0.04
0.16
0.08
0.11
0.04
0.03
0.01
0.03
0.05
0.07
0.43
Max.
0.61
0.71
1.62
0.09
18.01
MISSISSIPPI. 31 SITES
Organochlorines, 31 samples
P,P'-DDE
30
(-.p-DDT
26
p,p'-DDT
30
P,P'-TDE
11
2 DDT
30
Dieidrin
6
Endrin
2
Toxaphene
22
Trifluralin
9
Organophosphates, 15 samples
DEF
3
Heavy Metals. 31 samples
Arsenic
31
96.8
83.9
96.8
35.5
96.8
19.4
6.5
71.0
29.0
20.0
lOO.O
0.29
0.41
1,98
0.08
2.68
0.01
0.02
3.82
0.1)1
0.08
9.65
0.152
0.203
0.61 1
0.015
0.922
0.003
0.002
0.579
0.006
0.010
7.726
0.01
0.01
0.01
0.02
0.02
0.01
0.02
0.46
0.02
0.15
1.26
1.73
16.07
1.16
19.97
0.10
0.64
21.00
0.15
0.66
20.15
Organochlorines, 80 samples
Aldrin 7
Chlordane 5
o.p'-DDE 1
p.p-DDE 4
o.p'-DDT 1
/i.p'-DDT 5
i;DDT 7
Dieidrin 25
Heptachlor 4
Heptachlor epoxide 6
Propachlor 1
Trifluralin 3
Organophosphates, 67 samples:
Triazines, 20 samples
Atrazine i.i
Heavy Metals. 80 samples
Arsenic 80
MISSOURI, 80 SITES
) residues delected
8.8
6.3
1.3
5.0
1.3
6.3
8.8
31.3
5.0
7.5
1.3
3,8
65.0
100.0
0 (13
0.03
<0.0I
<(>.01
<0.01
0,01
0.02
0.07
<O.OI
<0.0I
<0.01
<0.01
0.06
5.02
0.(102
0.002
0,002
0.003
0.014
0.001
0.(101
0.001
0.026
3.739
0.01
0.09
0.09
0,01
0.05
0.03
0.01
0.01
0.01
0.02
0.07
0,02
0.01
0.88
1.88
1.09
0.06
0.33
0.47
0.78
0.07
0.10
0.13
0.34
21.86
NEBRASKA. 106 SITES
Organochlorines, 106 samples
Aldrin
Chlordane
op-DDE
/■.p'-DDE
op -DDT
P./.'-DDT
i;DDT
Dieidrin
Endrin
Heptachlor
Heptachlor epoxide
Organophosphates, 99 samples
DEF
Diazinon
Triazines, 21 samples
Atrazine
Heavy Metals, 106 samples
Arsenic
5
32
1
17
104
0.9
7.6
0.9
3.8
1.9
4.7
4.7
30.2
1.9
2.8
8.5
1.0
1.0
81.0
98.1
<0.01
0.02
<0.tll
0.01
<0.(I1
0.02
0,03
0,02
<0,01
0.01
(I.OI
<0.01
<0.01
0,07
5.24
0.002
0.001
0.001
0.002
0.002
0.008
<0,001
<0.001
0.001
(1.042
3.282
(Continued next page )
0.02
—
0.02
0.71
0.02
—
0.02
0.55
0.02
0.41
0.01
1.35
0,03
2.33
0.01
0.31
0.06
0.08
0.01
—
0.01
0.07
0.20
—
0.03
—
0.02
0.28
0.41
18.37
Vol. 12, No. 3, December 1978
125
TABLE 5 (cont'd.). Compound concenlratiom in cropland soil, hy stale, 1971 — National Soils Monitoring Program
Residues, ppm Dky WeicifT
Compound
No. OF
Positive
Detections
% of
Positive
Detections
Arithmetic
Mean
Concentration
Geometric
Mean
Concentration 1
Extremes of
Detected Values
MiN.
Max.
NEW ENGLAND--. 20 SITES
Orpanochlorincs. 20 samples
Aldrin I
Chlordanc 1
p.p'-DDE 6
o.r-DDT 4
r.r'-DDT 6
o.P-TDE I
P.p-TDE 5
2 DDT 6
Dieldrin 3
Hcpiachlor I
Hcptachlor epoxide 1
Organophosphatcs. i^ samples
Paraihion. cihy! I
Tria/incs. I sample: no residues detected
Heavy Metals. 20 samples
Arsenic 19
5.0
5.0
30.0
20.0
30.0
5.0
25.0
30.0
■ Si)
5.0
5.0
5.3
95.0
0.01
0.11
0.07
0.02
0.)6
<0.0I
0.07
0..12
0.17
<0.01
<0.01
0.01
8.56
0.014
0.006
0011
0.0 10
(1.026
0.006
2.841
0.28
2.20
()(>6
0.05
0.0.1
0.05
0.02
0.09
O.IH
0.04
0.0,1
0.14
060
0.44
0.22
0.90
0.92
2.16
3.26
69.10
NEW YORK. 18 SITES
Orpanochlorines. ?8 samples
Chlordane 2
o.p'-DDE 1
p.p'-DDE 1 1
o.p'-DDT 7
P.p'-DDT 10
...P-TDE 2
P.p'-TDE 5
i DDT 1 1
Dieldrin 4
Heptachlor epoxide 1
Trifliiralin 1
5.3
2.6
29.0
18.4
26.3
5.3
13.2
29.0
10.5
2.6
2.6
Organophosphaies. ,15 samples: no residues detected
Triazines. 6 samples
Alrazine 6 lOO.O
Heavy Metals. .18 samples
Arsenic .18 100.0
0.01
<n.0l
1.74
IJl
7.69
0.45
1.07
12.26
0.28
<0.01
<0.01
n.ig
1 1 .6.1
0,002
0.016
0.011
0.022
0.001
0.008
0.028
0.005
0.1.16
5.466
0.11
0.10
0.01
0.(11
0,02
0,21
0,11
0,02
0,01
0.01
0.14
0.04
0.41
0.40
54.98
12.75
245.18
16.79
38.46
388.16
9.8.1
0.18
180.42
NORTH CAROLINA. 11 SITES
Orpanochlorines, 31 sampl
es
Aldrin
1
3.2
Chlordane
2
6.5
o.p-DDE
T
6.5
P.p-DDE
25
80.7
«,p'-DDT
18
58.1
p.p-DDT
25
80.7
P.p'-TDE
18
58.1
2 DDT
26
83.9
Dieldrin
14
54.2
Endrin
1
3.2
Heptachlor
1
3.2
Hcptachlor epoxide
1
3.2
Toxaphene
7
22.6
Orpanophosphates. 7 samp
les:
no residues
detected
Heavy Metals. 11 samples
Arsenic 28
<0.01
0.05
<0.01
0.08
0.05
0.27
0.05
0.46
0.04
<0.0I
0.01
<0.01
0.65
;.4i
o.mii
0,00 1
0,04,1
0.022
0.087
0.024
0.169
0.015
0.04
0.17
0.(11
(1.(11
0.01
0.01
0.01
0,02
0,01
0,01
0,14
(l,OS
11,51
1.06
0.05
0,50
0.51
2.62
0.23
3.63
0.13
OHIO. 57 SITES
Organochlorines. 57 samples
Aldrin
7.0
Chlordane
5.3
p.p'-DDE
7.0
r/,p-DDT
3.5
p.p-DDT
7.0
<..p-TDE
1.8
P.P-TDE
5.3
i:DDT
8.8
Dieldrin
6
10.5
Heplachlor
1
1.8
Hcplachl(*i 1
L-poxidc
2
3.5
Trifliiralin
1
1.8
Orjianophosph
laies. 49
samples:
no residues
detected
Triazines. 10 samples
Alrazine
5
50.0
Heavy Metals.
57 sam
pics
Arsenic
57
100.0
0.01
0.02
0.12
0.07
0.51
<o.oi
0.06
0.76
0.02
<0.01
<0.01
<O.OI
0.25
14.17
0,002
(1,002
0,001
0.002
0.004
0.002
0,005
0,004
<O.IX)l
0,047
9.858
0.02
0,05
0,(14
0.15
(1,06
0,05
(1,05
(1,04
0,06
0,14
0,01
0,10
0,05
1,1 I
0.33
0.86
4.55
3.79
23.70
2.07
34.11
0.46
0.04
1.38
48.97
(Continued next page)
126
Pesticides Monitoring Journal
TABLE 5 (cont'd.)
Compound concentrations in
1 cropland soil, by state.
1971 —National Soils
: Monitoring Program
No. OF
% OF
Residues, ppm Dry Weight
Arithmetic
Geometric
Extremes op
Positive
etections
Positive
Detections
Mean Mean
Concentration Concentration'
Detected Values
Compound D
Min.
Max.
OKLAHOMA. 65 SITES
Organochlorines. 64 samples
».p'-DDE
I
1.6
<0.0I
0.03
__
P.p'-DDE
S
7.8
0.03
0.002
0.01
1.72
o.p'-DDT
1
1.6
<0.01
0.03
p,p'-DDT
3
4.7
0.01
0.001
0.01
0.85
p.p'-TDE
1
1.6
<0.0I
—
0.12
2 DDT
6
9.4
0.05
0.002
0.01
3.02
Dieldrin
2
3.1
<0.01
0.00 1
0.08
0.23
Endrin
1
1.6
<0.0I
—
0.05
Organophosphates. 58 samples:
: no residues detected
Triazines, ] sample
Atrazine
1
100.0
0.05
^-
0.05
__
Heavy Metals, 65 samples
Arsenic
64
98.5
2.66
1.872
0.32
10.08
OREGON, 38 SITES
Organochlorines. 38 samples
Aldrin
2
5.3
<0,0I
0.00 1
0.02
o.p'-DDE
1
2.6
<tl.01
—
O.OI
p.p'-DDE
12
31.6
0.45
0.008
0.0 1
16.69
o,p'-DDT
6
1S.S
0.12
0.003
0.01
4.S1
P.p'-DDT
6
15.8
0.49
0.006
0.03
18.20
p.p'-TDE
2
5.3
<0.01
0.00 1
0.01
0.10
2 DDT
12
31.6
1.07
0.011
0.01
39.40
Dieldrin
6
1S.8
0.07
0.006
0.06
2.15
Endrin
2
5.3
<0.0I
0.009
0.03
Heplachlor epoxide
1
2.6
<0.0I
—
O.OI
Organophosphates. 18 samples:
no residues detected
Heavy Metals, 38 samples
Arsenic
38
100.0
5.04
2.830
0.38
61.81
PENNSYLVANIA. 36 SITES
Organochlorines. 36 samples
Aldrin
1
2.8
<0.0I
—
0.15
—
P.p'-DDE
3
8.3
0.01
0.002
0.05
0.14
o,p'-DDT
1
2.8
<0.0I
—
0.01
p.p'-DDT
3
8.3
0.0 1
0.002
0.02
0.15
2 DDT
3
8.3
0.0 1
0.003
0.07
0.30
Dieldrin
5
13.9
0.02
0.003
0.01
0.49
Endrin
1
2.8
<0.01
—
0.06
—
Organophosphates, 35 samples:
no residues detected
Triazines, 5 samples
Atrazine
2
40.0
0.02
0.009
0.03
0.05
Heavy Metals, 36 samples
Arsenic
36
100.0
6.83
5.979
1.96
17.19
SOUTH
CAROLINA, 17 SITES
Organochlorines, 17 samples
Aldrin
1
5.9
<0.01
—
0.01
—
p.p'-DDE
17
100.0
0.24
0.182
0.01
0.47
o,p'-DDT
15
88.2
0.23
0.127
0.02
0.91
p.p'-DDT
17
100.0
0.85
0.544
0.05
3J8
p.p'-TDE
4
23.5
0.08
0.012
0.12
0.55
2 DDT
17
lOO.O
1.40
0.908
0.06
4.65
Dieldrin
6
35.3
0.11
0.014
0.02
1.42
Toxaphene
13
76.5
3.17
0.6-36
0.49
18.10
Organophosphates, 3 samples:
no residues
detected
Heavy Metals, 17 samples
Arsenic
17
100.0
1.75
1.085
0.13
9.59
SOUTH
DAKOTA. 106 SITES
Organochlorines, 106 samples
Aldrin
1
0.9
<0.0I
—
0.08
—
Chlordane
4
3.8
0.01
0.001
0.03
0.36
p.p'-DDE
1
0.9
<0.0I
—
O.OI
—
p.p'-DDT
1
0.9
<0.01
—
O.OI
—
2 DDT
1
0.9
<o.ni
—
0.02
—
Dieldrin
5
4.7
<0.01
0.001
0.01
0.27
Heptachlor epoxide
4
3.8
<0.01
O.OOI
O.OI
0.05
Organophosphates. 101 samples
;; no residues delected
Triazines, 3 samples
Atrazine
3
100.0
0.19
0.166
0.09
0.31
Heavy Metals, 106 samples
Arsenic
105
99.1
6.04
5.231
0.90
31.05
{Continued next page)
Vol. 12, No. 3, December 1978
127
TABLE 5 (cont'd.). Compound concentrations in cropland soil, by stale, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
% OF
Arithmetic
Geometric
Positive
Positive
Mean
Mean
lETECTIONS
Detections
Concentration
Concentration!
TENNESSEE. 27 SITES
Organochlorines. 27 samples
Chlordane
p.p'-DDE
o.p'-DDT
P.p-DDT
p.p'-TDE
2 DDT
Dieldrin
Heptachlor
Heplachlor epoxide
Toxaphene
Trifiuralin
Organophosphates, 16 samples: no residues detected
Triazines, 1 sample: no residues detected
Heavy Metals, 27 samples
Arsenic
1
9
7
10
4
11
1
1
1
2
2
27
3.7
33.3
25.9
37.0
14.8
40.7
3.7
3.7
3.7
7.4
7.4
100.0
0.02
0.09
0.03
0.17
0.01
0.30
<0.01
<0.01
<0.01
0.16
<0.01
8.52
0.013
0.009
0.022
0.003
0.030
0.005
0.001
7.114
Extremes of
Detected Values
MlN.
0.49
0.01
0.01
0.01
0.02
0.01
0.02
0.02
0.12
2.06
0.01
1.53
Max.
1.28
0.23
1.59
0.15
2.29
2.14
16.78
VIRGINIA/WEST VIRGINIAN 27 SITES
Organochlorines, 27 samples
Chlordane
D.p'-DDE
p.p-DDE
o,p'-DDT
p.p'-DDT
o,p'-TDE
p.p'-TDE
2DDT
Dieldrin
Endrin
Heptachlor
Heptachlor epoxide
Organophosphates, 25 samples:
Heavy Metals. 27 samples
Arsenic
1
2
9
3
5
2
5
9
5
1
1
1
no residues detected
3.7
7.4
33.3
11.1
18.5
7.4
18.5
33.3
18.5
3.7
3.7
3.7
0.03
0.01
0.21
0.02
0.16
0.05
0.29
0.74
0.01
0.02
<0.01
<0.01
27
100.0
0.001
0.010
0.003
0.007
0.003
0.006
0.017
0.003
2.081
0.83
0.01
0.02
0.03
0.03
0.12
0.02
0.02
O.OI
0.51
0.12
0.08
0.41
0.14
5.41
0.36
3.78
1.35
7.47
18.51
0.08
16.66
WASHINGTON STATE, 45 SITES
Organochlorines, 45 samples
Aldrin
Chlordane
o.p'-DDE
p.p'-DDE
o,p'-DDT
P.p-DDT
p.p'-TDE
2 DDT
Dieldrin
Organophosphates, 37 samples:
Heavy Metals, 45 samples
Arsenic
2
2
2
10
4
5
2
10
4
no residues detected
4.4
4.4
4.4
22.2
8.9
11.1
4.4
22.2
8.9
45
100.0
<0.01
0.01
<0.01
O.ll
0.02
0.21
0.04
0.39
<0,01
3.29
0.001
0.001
0.001
0.007
0.003
0.008
0.002
0.011
O.OOI
0.01
0.01
0.01
0.01
0.10
0.53
0.07
0.01
0.02
0.03
0.45
0.06
2.74
0.48
3.21
1.83
7.46
0.04
32.07
WISCONSIN, 67 SITES
Organochlorines, 67 samples
Chlordane
p.p'-DDE
o,p'-DDT
p.p'-DDT
2DDT
Dieldrin
Heptachlor
Organophosphates, 64 samples;
Triazines, 36 samples
Alrazinc
Heavy Metals. 67 samples
Arsenic
1
5
2
2
5
3
no residues detected
1.5
7.5
3.0
3.0
7.5
4.5
1.5
66
50.0
98.5
<0.01
0.01
<0.01
0.02
0.04
<0.01
<0.01
0.06
1.53
0.002
0.001
0.001
0.002
0.001
0.020
1.039
0.03
0.01
0.13
0.51
0.01
0.07
0.01
0.01
0.09
0.32
0.20
0.94
1.46
0.15
0.63
12.66
'Not calculated when fewer than two positive detections were present.
= Somc smaller eastern stales with few sites, hut which have similar geographic locations and /or agricultural characteristics were combined to obtain
more representative data including: Mid-Atlantic states: Delaware, Maryland, New Jersey. New England states: Connecticut, Maine, Massachusetts.
New Hampshire, Rhode Island, Vermont; Virginia/West Virginia.
are presented in Figures 2-7. The key for each figure
is_ based on the arithmetic average percent occurrence
(x) of the compound for all sites. The four classes are
described as: greater than 2x; greater than x but less
than 2x; greater than Vix but less than x; and less
than Vix.
128
Pesticides Monitoring Journal
X
KEY
\
■^x <
K^«^
X <
1111111111-^
2 X
k\\^^
X
|:-'-/-.V:;-;l^
1/2 X
FIGURE 2. Percent occurrence of oUlrin residue ileteclions in cropland soil, by stale, 1971 . National Soils
Moiiitorini; Program. U.S. Environmental Protection Agency
FIGURE 3. Percent occurrence of dicldrin residue detections in cropland soil, by state. 1971, National Soils
Monitoring Program, U.S. Environmental Protection Agency
Vol. 12, No. 3, December 1978
129
FIGURE 4. Percent occurrence of heptacMor epoxide residue detections in cropland soil, by slate, 1971. National Soils
Monitoring Program, U.S. Environmental Protection Agency
MME1< 1/2 i
FIGURE 5. Percent occurrence of '2.DDT residue detections in cropland soil, />v slate 1971 . National Soils
Monitoring Program, U.S. Environmental Protection Agency
130
Pesticides Monitoring Journal
X < IITTTTTTTI < 2x
1/2 '^< KS3^ ^
|.:;.: .,; Xi < 1/2 X
FIGURE 6. Percent occurrence of chlordane residue detections in cropland soil, by stale, 1971, National Soils
Monitoring Program, U.S. Environmental Protection Agency
FIGURE 7. Percent occurrence of elemental arsenic detections in cropland soil, by slate. 1971. National Soils
Monitoring Program, U.S. Environmental Protection Agency
Vol. 12. No. 3, December 1978
131
Illinois showed the highest percent occurrence of aldrin,
dieldrin. chlortlane. and heptachlor epoxide (Fig. 2-4,
6). Ihc compounds are soil insecticides or their degra-
dation products used in corn production. -DDT resi-
dues were concentrated in the southeastern states and
California (Fig. 5). Generally, Oklahoma, Oregon,
Penns\lvania, and Wisconsin had pesticide levels below
the all-sites average detection frequency.
COMPOUND CONCENTRATIONS IN CROPS
Crop samples were collected from 729 sites, or 48 per-
cent of the scheduled 1,533 sites. Samples were col-
lected only from those sites where crops were mature
and/or ready for harvest. All crop samples were
analyzed for organochlorines. In addition, samples were
analyzed for organophosphates and atrazine when pesti-
cide application records indicated their use during the
current growing season. Thus, the organophosphate and
atrazine concentration data could result in higher oc-
currence frequencies than might occur if all samples
had been analyzed.
Table 6 gives the occurrence of pesticide residues in
the crop materials sampled. For all crops, 42 percent
of the samples analyzed contained detectable concen--
trations of organochlorines, I 3 percent contained detect-
able concentrations of organophosphates, and only 1
percent contained detectable concentrations of atrazine.
In general, crops with known patterns of heavy pesticide
application, or animal feed crops (alfalfa, hay, field
corn, soybeans) grown in rotation with these crops, had
the highest frequencies of detectable pesticides.
Table 7 presents the compound concentrations detected
in each crop sampled. -DDT occurred most frequently
in all crops analyzed, with the exception of cornstalks, in
which dieldrin residues predominated. The high fre-
quency of occurrence of -DDT is probably the result
of prior, widespread use of DDT.
Acknowledgments
It is not possible to list by name all persons who con-
tributed to this study. The authors are especially grate-
ful to the staff of the Pesticides Monitoring Laboratory,
Bay St. Louis, Mississippi, who received, processed and
analyzed the samples for compound residues, and to the
inspectors of the Animal and Plant Health Inspection
Service, USDA, who collected the samples.
TABLE 6. Occurrence of pesticide residues in standing agricidtural crops. 1971 — National Soils Monitoring Program
ORGANOrHLORINES
Organophosphates
Triazines
No. OF
% OF
No. OF
% OF
No. OF
% OF
No. OF
Positive
Positive
No. OF
Positive
Positive
No. OF
Positive
Positive
Crop
Analyses
Detections
Detections
Analyses
Detections C
ETECTIONS
Analyses
Detections
Detections
Alfalfa/bur clover
61
33
54
17
2
12
—
—
. —
Beans, dry
5
0
0
4
0
0
—
—
' —
Clover
4
2
50
1
0
0
—
—
—
Corn, field (kernels)
304
40
13
46
1
2
1
1
100
Cornstalks
286
164
57
125
1
1
73
0
0
Cotton
28
15
54
26
8
31
—
—
—
Cottonseed
19
12
63
18
5
28
—
—
—
Cotton stalks
44
40
91
35
27
77
—
—
—
Cowpeas
1
0
0
—
—
—
—
—
—
Grass hay
11
6
55
3
0
0
—
—
—
Milo
2
1
50
—
—
—
—
—
—
Mint
1
1
100
-^
—
—
—
—
—
Mixed hay
51
26
51
17
1
6
—
—
—
Oats
1
0
0
—
—
—
—
—
—
Oats, straw
4
4
100
2
0
0
—
—
—
Pasture
18
10
56
3
0
0
—
—
—
Peanuts
8
2
25
1
0
0
—
—
—
Pecans
1
0
0
—
—
—
—
—
—
Rice
2
2
100
—
—
—
—
—
—
Rice straw
1
1
100
—
—
—
—
—
—
Sorghum (grain)
18
6
33
3
0
0
2
0
0
Sorghum stalks
2.1
14
61
4
0
0
2
0
0
Soybeans
177
69
39
45
0
0
9
0
0
Soybean hay
8
8
100
—
—
—
—
—
—
Sweet sorghum
1
0
0
—
Timothy
I
0
0
—
—
—
—
—
Tobacco
2
2
100
—
—
—
—
—
Wheat
1
0
0
—
—
—
—
—
Wheat straw
1
0
0
—
—
—
—
—
—
TOTAL
1,084
458
42
350
45
13
87
1
1
132
Pesticides Monitoring Journal
TABLE 7. Compound concenlralions in standing agricidlural crops, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
% OF
Positive
Detections
Arithmetic
Mean
Estimated
Geometric
Mean '
Detected Values
MiN.
Max.
Organochlorines, 61 samples
Chlordane
P,p'-DDE
o,p-DDT
p,p -DDT
P,p'-TDE
2 DDT
Dieldrin
Toxaphene
Organophosphales. 17 sample
Parathion. elhyl
Parathion, methyl
ALFALFA/BUR CLOVER
2
20
15
27
1
28
11
3.3
32.8
24.6
44.3
1.6
45.9
18.0
1.6
11.8
0.01
0.01
0.01
0.04
<0.01
0.06
<0.01
0.01
2.32
0.27
0.001
0.005
0.004
0.014
0.018
0.002
0.17
0.01
0.01
0.01
0.01
0.01
0.01
0.38
3.20
4.57
0.42
0.09
0.14
0.66
0.88
O.OS
36.20
BEANS. DRY (All Varieties)
Organochlorines, 5 samples: no residues detected
Organophosphales, 4 samples: no residues detected
CLOVER (Trifolium sp.)
Organochlorines, 4 samples
P.p'-DDT
1
ZDDT
1
Dieldrin
1
25.0
25.0
25.0
<0.01
<0.01
<0.0I
Organophosphales, I sample: no residues detected
0.02
0.02
0.01
FIELD CORN (Kernels)
Organochlorines, 304 samples
Chlordane
P.p-DDE
o.p'-DDT
p.p-DDT
^DDT
Dieldrin
Heptachlor
Heptachlor epoxide
Organophosphales. 46 samples
Parathion, methyl
Triazines. 99 samples
Atrazine
3
2
2
3
38
1.0
0.7
0.3
0.7
1.0
12.5
0.3
0.3
2.2
1,0
<0.01
<0.01
<0.01
<o.oi
<o.oi
<o.oi
<o.oi
<o.oi
<o.oi
<o.oi
<o.ooi
<o.ooi
<o.ooi
<o.ooi
0.001
0.08
0.01
0.05
0.01
0.01
0.01
0.05
0.01
0.09
11.01
0.48
0.03
0.26
0.34
0.07
CORNSTALKS
Organochlorines. 286 samples
Chlordane 16
p.p'-DDE 37
o.p'-DDT 49
P.p'-DDT 105
P.p'-TDE 17
^DDT 107
Dieldrin 114
Endrin 1
Heptachlor 3
Heptachlor epoxide 22
Toxaphene 15
Organophosphales, 125 samples
Parathion, ethyl 1
Triazines, 73 samples: no residues detected
5.6
12.9
17.1
36.7
5.9
37.1
39.9
0.4
1.1
7.7
5.3
0.8
0.02
<0.01
<0.0l
0.02
<0.01
0.03
0.01
<0.01
<0.01
<0.01
0.04
<0.01
0.002
0.001
0.002
0.006
0.001
0.008
0.006
<0.00l
0.001
0.002
Organochlorines, 28 samples
p.p-DDE
7
n.p -DDT
1
;'.P'-DDT
15
i;DDT
15
Dieldrin
1
Endrin
1
Endrin ketone
1
Toxaphene
6
Organophosphales, 26 samples
DEF
6
Parathion, ethvl
2
Parathion, methyl
1
COTTON
25,0
0.07
7,1
0.25
53.6
0.95
53,6
1.27
3,6
<0.01
3.6
<0.01
3.6
<0.01
21.4
1.22
23.1
0.08
7.7
0.04
3.8
0.01
0.006
0.004
0.039
0.043
0.019
0.012
0.004
COTTONSEED
Organochlorines, 19 samples
r> n'.nnp
p.p'-DDE
).P-DDT
36.8
31.6
0.06
0,28
0.010
0.019
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.06
0.01
0.01
0.07
0.36
0.01
0.21
0.01
0.03
0.02
0.09
0.06
0.18
0.08
0.49
0.18
0.01
0.02
1.26
0.06
0.16
0.55
0.10
0.78
0.17
0.03
0.51
2.83
1.86
6.87
22.99
31.72
28.89
0.62
0.53
0.82
3.32
(Continued next page)
Vol. 12, No. 3, December 1978
133
TABLE 7 (cont'd.). Compound concentrations in standing agricultural crops, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
Positive
% OF
Positive
Detections
Arithmetic
Mean
Estimated
Geometric
Mean>
Detected Values
MiN.
Max.
P.P'-DDT
2 DDT
Toxaphcne
Organophosphates.
DEF
8 samples
47.4
47.4
26.3
27.8
0.87
1.21
1.12
0.07
0.040
0.053
0.031
0.01-1
0.03
0.04
0.55
0.10
14.09
18.23
13.54
0.63
COTTON STALKS
Organochlorines, 44 samples
Chlordane 1
o.p'-DDE 1
p.p'-DDE 34
o,p'-DDT 34
P.P'-DDT 40
p.p-TDE 17
2 DDT 40
Dieldrin 4
Endrin 1
Endrin ketone 1
Heptachlor epoxide 1
Toxaphene 31
Organophospliates. 35 samples
DEF 17
Parathion. ethyl 5
Parathion, methyl 21
2.3
2.3
77.3
77.3
90.9
38.6
90.9
8.9
2.3
2.3
2.3
70.5
48.6
14.3
60.0
0.01
<0.Q1
0.30
1.48
7.67
0.83
9.15
<0.01
0.14
0.01
<0.01
10.21
2.01
0.23
0.30
0.062
0.153
0.691
0.032
0.916
0.001
0.628
0.085
0.006
0.068
0.40
0.10
0.01
0.01
0.02
0.01
0.04
0.01
6.26
0.37
0.01
0.15
0.11
0.04
0.04
4.06
28.10
114.63
17.78
160.51
0.08
150.00
37.13
7.32
1.53
COWPEAS
Organochlorines, 1 sample: no residues detected
GRASS HAY
Organochlorines, 1 1 samples
Chlordane
P.p'-DDE
o.p'-DDT
P.P'-DDT
2 DDT
Dieldrin
Toxaphene
Organophosphates. 3 samples:
5
4
5
5
2
2
no residues detected
9.1
45.4
36.4
45.4
45.4
18.2
18.2
0.0 1
0.02
0.03
0.08
0.13
<-n.oi
0.21
0.007
0.008
0.015
0.021
0.002
0.012
0.19
0.01
0.01
0.02
0.03
0,01
0.26
0.12
0.32
0.73
1. 17
0.02
2.00
MILO
Organochlorines, 2 samples
Dieldrin
50.0
0.05
0.11
MINT
Organochlorines, 1 sample
P,p'-DDE
o,p'-DDT
P,p'-DDT
2 DDT
Organochlorines, 51 samples
Chlordane 4
P.p'-DDE 12
o.p'-DDT 8
P.P'-DDT 17
P.p'-TDE 1
2DDT 17
Dieldrin 15
Toxaphene 6
Organophosphates. 17 samples
DEF 1
Parathion. methyl 1
100.0
0.05
—
100.0
0.01
—
100.0
0.15
—
100.0
0,21
—
MIXED HAY
7.8
0.07
0.004
23.5
0.01
0.003
15.7
0.03
0.003
33.3
0.26
0.011
2.0
<0.0I
—
33.3
0.31
0.012
29.4
0.01
0.004
11.8
0.36
0.007
5.9
<0.0I
5.9
<0.01
Organochlorines, 4 samples
Chlordane 1 25.0
P.p'-DDE 2 50.0
o.p'-DDT 2 50.0
p.p'-DDT 3 75.0
2 DDT 3 75.0
Dieldrin 2 50.0
Organophosphates 2 samples: no residues detected
0.01
<0.01
<0.01
0.02
0.03
0.01
0.004
0.004
0.019
0.026
0.009
0.05
0.01
0.15
0.21
0.25
0.01
0.01
0.01
0.01
0.02
0.01
0.16
0.06
0.02
0.03
0.01
0.01
0.02
0.04
0.01
1.68
0.48
1.23
12.24
13.95
0.05
15.73
OATS
Organochlorines,
1 sample: no residues detected
OAT HAY/STRAW
0.04
0.06
0.05
(Continued next page)
134
Pesticides Monitoring Journal
TABLE 7 (cont'd. ) . Compound concentrations in standing agricultural crops, 1971 — National Soils Monitoring Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
DETECnONS
% OF
Positive
Detections
Arithmetic
Mean
Estimated
Geometric
Mean'
Detected Values
MlN.
Max.
PASTURE
Organochlorines. 18 samples
Chlordane 3 16.7
p.p'-DDE 3 16.7
o.p'-DDT 2 11.1
p.p-DDT 6 33.3
D.p'-TDE 1 5.6
p.p'-TDE 1 5.6
2 DDT 6 33.3
Dieldrin 6 33J
Endrin 1 5.6
Heptachlor epoxide I 5.6
Toxaphene 1 5.6
Organophosphates. 3 samples: no residues detected
0.05
<0.01
<0.01
0.01
<0.01
<0.01
0.04
<0.01
<0.0I
<0.01
0.01
0.009
0.001
0.001
0.005
0.008
0.006
0.37
0.01
0.02
0.01
0.45
0.07
0.01
0.02
O.Ol
0.01
0.23
0.63
0.02
0.03
0.08
0.63
COS
PEANUTS
Organochlorines, 8 samples
Dieldrin 2
Organophosphates. 1 sample: no residues detected
0.01
0.004
0.03
PECANS
Organochlorines, 1 sample: no residues detected
Organochlorines, 2 sample
p.p'-DDE
o.p'-DDT
p.p'-DDT
2 DDT
Heptachlor
RICE
100.0
50.0
100.0
100.0
50.0
0.02
0.03
0.15
0.20
<0.01
0.018
0.096
0.126
0.01
0.06
0.03
0.04
0.01
0.03
0.27
0.36
Organochlorines, 1 sample
p.p'-DDE
o.p'-DDT
p.p'-DDT
2 DDT
Toxaphene
RICE STRAW
100.0
100.0
100.0
100.0
1 00.0
0.04
0.11
0.12
U.27
0.52
0.04
0.11
0.12
0.27
0.52
SORGHUM
Organochlorines, 18 samples
Chlordane 3
p.p'-DDE 2
o.p'-DDT 1
P.p'-DDT 3
p.p'-TDE 1
2 DDT 3
Dieldrin 4
Endrin 1
Heptachlor epoxide 1
Toxaphene 1
Organophosphates, 3 samples: no residues detected
Triazines, 2 samples: no residues detected
16,7
0.03
11.1
0.01
5.6
0.02
16.7
0.06
5.6
<0.01
16.7
0.04
22.2
0.02
5.6
<0.0I
5.6
<0.01
5.6
0.05
SORGHUM STALKS
Organochlorines, 23 samples
Chlordane 4
p.p'-DDE 6
o.p'-DDT 10
p.p'-DDT 15
P.p'-TDE 4
2 DDT 16
Dieldrin 6
Endrin 1
Endrin ketone 1
Heptachlor 1
Heptachlor epoxide 2
Toxaphene 4
Organophosphates. 4 samples: no residues detected
Triazines, 2 samples: no residues detected
17.4
0.08
26.1
0.01
43.5
0.03
65.2
0.09
17.4
<0.01
69.6
0.13
26.1
0.05
4.3
0.03
4.3
0.01
4.3
<a.oi
8.7
<0.01
17.4
0.09
SWEET SORGHUM
Organochlorines, 1 sample: no residues detected
0.005
0.003
0.004
0.009
0.005
0.008
0.023
0.002
0.031
0.010
0.001
0.009
0.02
0.42
0.07
0.14
0.30
—
0.02
0.64
0.05
—
0.01
0.28
0.02
—
0.02
—
0.84
0.11
0.81
0.0 1
0.12
O.OI
0.33
0.01
1.07
0.02
0.03
0.01
1.52
0.02
0.51
0.60
—
0.19
—
0.02
—
0.03
0.04
0.24
0.91
(Continued next page)
Vol. 12, No. 3, December 1978
135
TABLE 7 (cont'd.). Compound conccntralions in slandhii; agrUuUunil crops, 1971 — National Soils Monitoring; Program
Residues, ppm Dry Weight
Compound
No. OF
Positive
Detections
Positive
Detections
Arithmetic
Mean
Estimated
Geometric
Mean ^
Detected Values
MlN.
Max.
SOYBEANS
Organochlorines. 177 samples
p.p-DDE 5 2.8
(i.;)-DDT 1 0.6
p.p'-DDT 4 2.3
2 DDT 5 2.8
Dieldrin 55 31.1
Endrin 7 3.9
Hepiachlor epoxide 2 1.1
Toxaphene ."^ 1.7
Organophosphales, 45 samples: no residues detected
Triazines, 9 samples: no residues detected
<0.0I
<0.01
<0.01
<0.01
<0.01
<0.01
<n.oi
0.01
<o.ooi
<o.ooi
<o.ooi
0.00.1
<0.001
<0.001
0.001
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.10
0.02
COS
0.07
0.05
0.03
0.03
0.66
Organochlorines. 8 samples
Chlordane 1
P.P-DDE 4
o.p'-DDT 2
p.p'-DDT 6
p.p'-TDE 3
2 DDT 6
Dieldrin 5
Endrin I
SOYBEAN HAY
12.5
50.0
25.0
75.0
37.5
75.0
62.5
12.5
0.02
0.01
<0.0I
o,o:
0.1)1
0,04
0.01
<0.01
0.006
0.002
0.017
0.005
0.027
0.006
0.17
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.05
0.04
0.09
0.02
TIMOTHY
Organochlorines. 1 sample: no residues detected
TOBACCO
Organochlorines. 2 samples
».P-DDE
P.P-DDE
«.p-DDT
P.p-DDT
2
o.p-TDE
P.p'-TDE
2 DDT
2
Dieldrin
Endosulfan
Endosulfan 11
Endosulfan sulfate
50.0
50.0
50.0
100.0
50.0
50.0
100.0
50.0
50.0
50.0
50.0
0.25
0.1')
l.IO
.l.«7
2.X7
S,54
17.0.1
0.14
0.66
2.6.1
.1.28
0..184
0.815
'Not calculated when fewer than two positive detections were present.
0.50
0.78
2.20
0.01
5.74
17.09
0.01
0.69
1.33
5.26
6.57
7.74
34.05
WHEAT
Organochlorines,
1 sample:
no residues detected
WHEAT STRAW
Organochlorines,
1 sample:
no residues delected
LITERATURi: CITED
(/) licnnell. I. L. 1967. Foreword. Peslic. Monil. J. 1(1).
(2) C\ircy. A. E.. J. A. Gowen. and C . II. IVicrsina. I97S.
Pesticide application and cropping data from .'^7 slates.
in 1^71 — National Soils Monitoring Program. Peslic.
Monil. J. i:(.^):l37-14S.
(3) Crockcli. A. li.. a. B. Wiersnia. II. Tui. W. C.
Mitchell. I'. /•'. .Sand, and A. E. Carey. 1974. Pesticide
residue levels in soils and crops, FY-7(l--National
Soils Monitoring Program (II). Peslic. Monil. J.
8(2):69-97.
{4) Panel on Festicide Moniiorin.t,'. 197 1 . Criteria lor defin-
ing pesticide levels lo be considered an alcrl to poten-
tial problems. Peslic. Monil. J. .St 1 ) i.ld.
(.■i) Sand. I'. I-.. J. H. C.entrx, J. Ilonnherf;. and M. S.
Schecter. 1967. National soil monitoring program
sliidies of high-, low-, and noniise areas. Peslic.
Monil. J. Ill): 16-19.
(6) Stevens. /.. J.. ( . W. (Oilier, and /). W . Wiiodliani.
1970. Monitoring pesticides in soils from areas of
legtilar. limited and no pesticide tisc. Peslic. Monil. J.
4|.M:14.'^-166.
(7) IKS. Department of A.i;ricalinre. 1969. Monitoring
agriciilttiral pesticide residties I96.'5-1967. A final re-
port on soil, water, crops, sediment and wildlife in six
study areas. Agric. Res. .Serv. Report 81 -.12.
(.V) U.S. Environmental l'rotecti<ni Af;eney. 1973. PM
Meniorttndiim No. .1. Sample Collection Manual.
Guidelines for collecting field samples: soil, crops,
water, sediment. 71 pages.
(V) Wiersma. (!. li.. /'. /■. Sand, and E. L. Co.\. 1971. A
siimpling design to determine pesticide residue levels
in soils of the conterminous LInilcd Skiles. Peslic.
Monil. J. 5( I ):63-66.
(10) Wiersma. C, . li., P. /■'. Sand, and li. I.. Selnit:m<iiin.
1971. National Soils Monitoring Program — si,\ slates,
1967. Peslic. Monil. J. .">( 2 ) :22.1-2:7.
(//I Wiersma. C H , II. lai. and P. E. Sand. 1972. Pesti-
cide residue levels in soils. FY-1969 — Naliontil Soils
Moniloiing Program. Peslic. Monil. J. 6( .1 ) : 194-22X.
136
PESTIC IDE MONITOKING JOURNAL
Pesticide Application and Cropping Data from 37 States, 1971 —
National Soils Monitoring Program
Ann E. Carey.' Jeanne A. Gowen,- and G. Bruce Wiersma '^
ABSTRACT
This report summarizes pesticide application and cropping
data collected in 1971 from l,47S agricultural sampling
sites in 37 states as pari of the National Soils Monitoring
Program. Pesticide application data arc summarized by all
sites, state, and crop. Tables generally give the number of
reporting sites, the number of times a compound was ap-
plied, the percent occurrence, and the arithmetic mean total
application rate.
Pesticides applied most frequently to sampling sites were
atrazine. 2,4-D, caplan, and malatliion. Pesticides were
most frequently applied to field corn and cotton, least fre-
quently to alfalfu/hur clover and mixed hay.
Introduction
In 1963, the report of the President's Science Advisory
Committee recommended that appropriate federal agen-
cies "develop a continuing network to monitor residue
levels in air, water, soil, man, wildlife and fish" (7).
As a result of this recommendation, the National Pesti-
cide Monitoring Program (NPMP) was established to
determine levels and trends of pesticides and their degra-
dation products in the environment (3). Federal re-
sponsibility for monitoring pesticides was officially man-
dated in Section 20 of the amended Federal Insecticide,
Fungicide and Rodenticide Act of 1972 (PL 92-516).
The National Soils Monitoring Program is an integral
part of the NPMP, monitoring agricultural soils and
raw agricultural crops. It was initiated in 1968 by the
U.S. Department of Agriculture and is administered by
the U.S. Environmental Protection Agency. The present
report summarizes pesticide application and cropping
data collected in 1971 from 1,473 sampling sites in 37
states. Composite soil and crop samples were also col-
lected from these sites for pesticide residue analyses, the
results of which are published separately (2).
'Ecological Monitiiriny Branch. Benefits and Field Studies Division.
Office of Pesticide Prii^rams. U.S. Environmental Protection A^icncy.
TS-768. Washinsiton. DC 2II46I1.
-Extension Ayent. Colorado State Extension Service. Golden. CO.
■'Chief. Pollutant Pathways Branch. Environmental Monitoring and
Support Laboratory. U.S. Environmental Protection Ayency, Las
Vegas, NV.
Sampling
The site selection criteria and statistical design of the
National Soils Monitoring Program have been de-
scribed (4). In 1971, 1,533 sites in 37 states were
scheduled for sampling (Fig. 1). At each 4-hectare
(lO-acre) site, landowners or operators supplied infor-
mation on the crops grown and the kinds and amounts
of pesticides applied during 1971.
Results and Discussion
COMPOUNDS APPLIED TO CROPLAND
Pesticide use data were received from 1 ,473 or 96 per-
cent of the scheduled 1,533 sites. Of these, 784 or 53
percent of the sites had one or more pesticides applied
during 1972. Tables summarizing the application data
show the number and percent of sites with reported
pesticide application and the average rate of total pesti-
cide application for each site, expressed both in pounds
per acre and kilograms per hectare.
Table 1 gives the frequency of pesticide use on sample
sites in various states and state groups. Because some
of the smaller eastern states had very few sites, those
with similar geographic location and/or agricultural
characteristics were combined to obtain more represen-
tative data. Slates were grouped as follows: Mid-At-
lantic: Delaware, Maryland, New Jersey; New England:
Connecticut, Maine, Massachusetts, New Hampshire,
Rhode Island, Vermont; and Virginia and West Virginia.
Among the individual states and state groups, frequency
of pesticide use ranged from 23 percent in Pennsylvania
to 77 percent in Mississippi.
ALL SITES
Applications of 132 compounds were recorded for all
reporting sites. The compounds included 50 herbicides,
including defoliants, 48 insecticides and/or acaricides,
28 fungicides, 4 nematocides, I soil fumigant, and 1
growth retardant (Table 2). The most frequently ap-
plied compounds were atrazine, 2,4-D. captan, and
malathion. which were reported from 14, 10, 9, and 8
percent of the reporting sites, respectively.
Vol. 12, No. 3, December 1978
137
26-591
FIGURE 1. Slates scheduled for sampling, 1971, National Soils Monitoring Program
TABLE I. Occurrence of pesticide applications by
1971 — National Soils Monitoring Program
state,
State
Total
Pesticides
OR
No. OF
Sites
Pesticides
Applied
Not
Applied
State
No. OF
No. OF
Group^
Reporting
Sites
Tv
Sites
%
Alabama
22
9
41
13
59
Arkansas
45
24
53
21
47
California
61
29
48
32
52
Florida
18
8
44
10
56
Georgia
29
19
66
10
34
Idaho
33
11
33
22
67
Illinois
142
100
70
42
30
Indiana
74
50
68
24
32
Iowa
152
103
68
49
32
Kentucky
28
11
39
17
61
Louisiana
25
17
68
8
32
Michigan
54
25
46
29
54
Mid-Ailantic
16
7
44
9
56
Mississippi
31
24
77
7
23
Missouri
79
37
46
42
54
Nebraska
106
65
61
41
39
New England
21
6
29
15
71
New York
36
17
47
19
53
N. Carolina
30
18
60
12
40
Ohio
57
31
54
26
46
Oklahoma
60
22
37
38
63
Oregon
37
13
35
24
65
Pennsylvania
35
S
23
27
77
S. Carolina
15
8
53
7
47
S. Dakoia
106
51
48
55
52
Tennessee
24
11
46
13
54
Virginia and
W.Virginia
25
8
32
17
68
Washington
state
45
22
49
23
51
Wisconsin
67
30
45
37
55
Total
1473
784
53
689
47
'Some smaller eastern stales which had few sites but similar geographic
locations and /or agricultural characteristics were combined to obtain
more represenlalive dala. including: Mid-Allanlic Mates: Oelawarc.
Maryland. New Jersey; New Hngland stales: Connecticut. Mamc.
Massachusetts, New Hampshire. Rhode Island. Vermont; and Virginia
and West Virginia.
BY STATE
Table 3 presents the application data by state or state
grouping. Because of the number of states sampled, it
is not feasible to discuss in detail the pesticide data
from each state. However, the pesticide application in-
formation from each state reflects both the crops grown
and the intensity of agricultural land use in the state.
In Figure 2, the frequency of reported pesticide appli-
cations in each state is designated as follows: low, states
where less than 25 percent of the sites reported pesticide
applications; medium, states where 25-59 percent of
the sites reported applications: and, high, where over
60 percent of the sites in a state reported pesticide appli-
cations.
BY CROP
Table 4 lists crops grown on sample sites in 1972 as well
as the pesticide application status for each crop. Appli-
cation data for selected major crops are presented in
Table 5. Pesticide use varied widely among these crops.
Table 6 shows the pesticide applications in 1971
selected major crops, by state.
for
Acknowledgment
It is not possible to list by name all the persons who
contributed to this study. However, the authors are
especially grateful to the inspectors from the Plant Pro-
tection and Quaranline Programs, Animal and Plant
Health Inspection Service. U.,S. Department of Agri-
culture, who collected the data.
138
Pesticides Monitoring Journal
TABLE 2. Compounds applied to 1.473 cropland sites, 1971— National Soils Monitoring Program
Average Total
Trade
Pesticides Applied
Application
Trade
Pesticides Applied
Average Total
Application
Compound
Name,
If Noted
No. OF
Sites
% OF
Sites
LB./
Acre
KG/
Hectare
Compound
Name,
If Noted
No. OF
Sites
% OF
Sites
LB./
Acre
KG/
Hectare
Alachlor Lasso
Aldrin
Arsenic pentoxide
Atrazine AAtrex
65
45
2
214
4.4
3.0
0.1
14.1
1.58
1.15
0.50
1.78
1.77
1.29
0.56
1.99
Isodrin
Lead arsenate
Lindane
0.1
0.2
0.1
0.01
7.07
0.02
0.01
7.91
0.02
Azinphosmethy!
Guthion
6
0.4
0.60
0.67
Linuron
Lorox
23
1.6
0.89
1.00
Bacillus
Londax
0.1
0.50
0.56
thuringiensis
B.T.
1
0.1
0.11
0.12
Malathion
111
7.5
0.16
0.18
Barban
Carbyne
1
0.1
0.25
0.28
Maleic hydrazide
: MH
0.2
3.00
3.36
Benefin
Balan
3
0.2
1.11
1.24
Mancozeb
Dilhane M-45 2
0.1
12.40
13.89
BHC
3
0.2
0.02
0.02
Maneb
3
0.2
2.34
2.62
Bordeaux mixture
1
0.1
1.25
1.40
MCPA
MCP
5
0.3
0.70
0.78
Bromacil
Hyvar
3
0.2
0.62
0.70
Mercury
2
0.1
0.06
0.06
Butylate
Sutan
18
1.2
1.74
1.95
Metham
Vapam
1
0.1
2.16
2.42
Bux
17
1.1
1.26
1.41
Methomyl
Lannate
1
0.1
1.13
1.27
Captafol
Difolatan
1
0.1
1.50
1.68
Methoxychlor
24
1.6
0.17
0.19
Captan
138
9.3
0.11
0.12
Methylmercury
Carbaryl
Sevin
18
1.2
2.12
2.37
acetate
Ceresan L
6
0.4
0.01
0.01
Carbophenothion
Trithion
1
0.1
3.20
3.58
Methylmercury
Carbofuran
Furadan
20
1.3
1.01
1.13
dicyandiamide
Panogen
18
1.2
0.08
0.09
Chevron RE-5353
1
4
0.3
0.85
0.95
Methyl trithion
1
0.1
3,00
3.36
Chloramben
Amiben
41
2.8
1.39
1.56
Mevinphos
Phosdrin
2
0.1
0.75
0.84
Chlordane
1
0.1
2.50
2.80
Mirex
6
0.4
0.07
0.08
Chlorobenzilate
Acaraben
2
0.1
1.38
1.55
Monocrotophos
Azodrin
4
0.3
0.33
0.36
Chloroneb
Demosan
9
0.6
0.02
0.02
Monuron
Telvar
2
0.1
1.30
1.46
Chloropropham
Chloro-lPC
1
0.1
2.50
2.80
MSMA
17
1.1
1.77
1.99
Chlorothalonil
Bravo
1
0.1
3.00
3.36
Nabam
1
0.1
5.00
5.60
Copper carbonate
Naptalam
Alanap
4
0.3
1.94
2.17
(basic)
1
0.1
3.90
4.37
Nitralin
Planavin
5
0.3
1.05
1.18
Copper hydroxide
1
0.1
1.08
1.21
Oil Spray
Ovex
2
0.1
60.00
67.20
Copper oxide
1
0.1
1.70
1.90
1
0.1
0.50
0.56
Copper sulfate
3
0.2
13.97
15.65
Oxydemeton-
Cypromid
Clobber
1
0.1
0.75
0.84
melhyl
Metasystox-
R 2
0.1
0.50
0.56
2.4-D
Decamine
145
9.8
0.87
0.97
Paraquat
4
0.3
0.86
0.97
Dalapon
2,4-DB
Dowpon
Butyrac
4
7
0.3
0.5
2.60
0.64
2.91
0.72
Parathion, ethyl
Parathion, methyl
PCNB
Pebulate
Penlachloro-
phenol
Phenylmercury
21
48
1.4
3.2
3.32
2.81
3.72
3.15
DCPA
DDT
DEF
Demeton
Diallate
Dacthal
Systox
Avadex
1
33
9
2
1
0.1
2.2
0.6
0.1
0.1
3.75
3.83
1.03
1.56
0.12
4.20
4.29
1.16
1.75
0.13
Tillam
PCP
2
1
2
0.1
0.1
0.1
3.51
0.12
3.02
3.93
0.13
3.38
Diazinon
15
1.0
0.75
0.84
actate
PMA
2
0.1
0.01
0.01
Dicamba
Banvel D
12
0.8
0.31
0.34
Phenylmercury
Dichlofenthion
Nemacide
1
0.1
6.00
6.72
urea
3
0.2
0.01
0.01
Dichloropropene
Dichlorprop
Dicofol
Telone
2,4-DP
Kelthane
3
1
1
0.2
0.1
0.1
28.00
3.00
1.00
31.36
3.36
1.12
Phorate
Phosalone
Phosphamidon
Thimet
Zolone
Dimecron
21
1
2
1.4
0.1
O.I
1.71
4.00
0.27
1.91
4.48
0.30
Dieldrin
Dinitrocresol
6
3
0.4
0.2
0.09
1.64
0.10
1.84
Prolate
Prometryn
Imidan
Caparol
2
1
0.1
0.1
11.60
1.08
13.00
1.21
Diphenamid
Enide
1
0.1
0.25
0.28
Propachlor
Ramrod
44
3.0
1.64
1.83
Disulfoton
Di-Syston
24
1.6
1.21
1.35
Propanil
Stam
6
0.4
3.46
3.87
Diuron
Karmex
9
0.6
1.56
1.75
Propargite
Omite
2
0.1
2.58
2.88
DNBP
Premerge
16
1.1
1.35
1.51
Pyrazon
Pyramin
1
0.1
1.25
1.40
Dodine
2
0.1
0.83
0.93
Silvex
3
0.2
0.42
0.47
DSMA
11
0.7
2.00
2.24
Simazine
Princep
9
0.6
4.00
4.48
Dyfonate
1
0.1
0.90
1.00
Sodium chlorate
5
0.3
1.74
1.95
EMTS
Ceresan M
9
0.6
0.06
0.06
Solan
1
O.I
1.00
1.12
Endosulfan
Thiodan
8
0.5
1.44
1.61
Sulfur
12
0.8
34.27
38.38
Endrin
3
0.2
2.20
2.46
2,4,5-T
2
0.1
0.30
0.34
EPTC
Eptam
10
0.7
2.09
2.34
TCA
2
0.1
2.50
2.80
Ethoprop
Mocap
1
0.1
1.00
1.12
TEPP
1
0.1
4.00
4.48
Ethylmercury
Terbacil
Sinbar
1
0.1
1.40
1.56
chloride
Ceresan Red
8
0.5
0.03
0.03
Fensulfothion
Dasanit
5
0.3
1.15
1.28
Terbutryn
Igran
I
0.1
1.75
1.96
Fentin hydroxide
1
0.1
2.25
2.52
Terrazole
1
0.1
0.15
0.16
Ferbam
2
0.1
2,59
2.90
Tetradifon
TedionV-18
1
0.1
0.75
0.84
Fluometuron
Cotoran
22
1.5
0.95
1.06
Thiram
13
0.9
0.01
0.01
Folex
5
0.3
1.05
1.18
Toxaphene
33
2.2
7.00
7.84
Folpet
Phaltan
1
0.1
1.00
1.12
Trichlorfon
Dylox
2
0.1
0.88
0.98
Furethrin
1
0.1
8.00
8.97
Trietazine
1
0.1
0.70
0.78
Heptachlor
8
0.5
1.27
1.42
Trifluralin
Treflan
64
4.3
0.95
1.06
Hexachloro-
Vernolate
Vernam
2
0.1
2.25
2.52
benzene
HCB
7
0.5
0.01
0.01
Zineb
1
0.1
7.50
8.40
Vol. 12, No. 3, December 1978
139
TABLE 3. Coinpoittuh applied to cropland sites by state, 197 1 — National Soils Monitoring Program
Average Total
Average Total
Trade
Name.
Pesticides Applied
No. OF % OF
Application
Trade _
Name.
ESTiciDES Applied
Application
LB./
KG/
No. of
Tc OF
lb./
KG/
Compound
If Noted
Sites
Sites
Acre
Hectare
Compound
If Noted
Sites
Sites
Acre
Hectare
ALABAMA. 22
SITES
Propargite
Omite
1.6
0.15
0.16
Simazine
Sodium chlorate
Princep
4.9
1.6
8.00
5.00
8.96
Atrazine
AAtrex
13.6
2.67
2.98
5.60
Benefin
Balan
4.5
0.75
0.84
Sulfur
8.1
15.34
17.19
Buiylate
Sutan
9.0
0.25
0.28
Tetradifon
Tedion V-18
1.6
0.75
0.84
DDT
13.6
3.67
4.10
Toxaphene
1.6
0.40
0.44
Disulfoton
Di-Syston
4.5
7.00
7.84
Trichlorfon
Dylox
3.2
0.88
0.98
Dluron
Karmex
4.5
0.34
0.38
Trifluralin
Treflan
2
3.2
0.20
0.22
DSMA
4.5
1.50
1.68
EMTS
Ceresan M
4.5
0.01
0.01
1.56
1.02
2.24
1.56
2.50
7.84
FLORIDA, 18
SITES
Endrin
Fluomeiuron
MSMA
Parathion. ethyl
Parathion, methyl
PCNB
Toxaphene
Trifluralin
Cotoran
4.5
13.6
4.5
4.5
13.6
4.5
1.40
0.92
2.00
1.40
2.23
7.00
Atrazine
Carbaryl
Carbofuran
Chlorobenzilate
Copper carbonate
AAtrex
Sevin
Furadan
Acarabcn
11.1
5.5
5.5
11. 1
2.75
5.00
4.00
1.38
3.08
5.60
4.48
1.54
Treflan
13.6
4.5
4.55
0.50
5.09
0.56
(basic)
2.4-D
Dalapon
Endrin
Dowpon
5.5
16.6
5.5
5.5
3.90
5.33
1.50
1.00
4,37
5.97
1.68
ARKANSAS. 45
SITES
1.12
EPTC
Malathion
Eptam
5.5
5.5
0.20
3.17
0.22
Aldrin
1
2.2
0.75
0.84
3.55
Atrazine
AAtrex
1
2 2
0.75
0.84
Maneb
5.5
0.08
0.08
Captan
1
2^2
0.01
0.01
Oil Spray
5.5
70.00
78.45
Chloroneb
Demosan
-»
4.4
0.01
0.01
Sulfur
16.6
78.67
88.16
2,4-D
1
2.2
0.50
0.56
Zineb
5.5
7.50
8.40
:.4-DB
DDT
1
2.2
1.50
1.68
.1
6.6
0.57
0.63
GEORGIA, 30
SITES
Disulfoton
DNBP
DSMA
EMTS
Fluometuron
Linuron
Di-Syston
Premerge
Ceresan M
Cotoran
Lorox
1
5
3
5
2
2.2
11.1
4.4
6.6
11.1
4.4
0.25
0.94
1.20
0.15
0.84
0.50
0.28
1.05
1.34
0.16
0.92
0.56
Benefin
Butylate
Captan
Carbaryl
Chlorothalonil
Copper oxide
Balan
Sutan
Sevin
Bravo
3.3
3.3
16.6
6.6
3.3
3.3
1.50
0.75
0.02
2.56
3.00
1.70
1.68
0.84
0.02
2.86
3.36
1.90
Methylmercury
dicyandiamide
Monuron
MSMA
Nitralin
Panogen
Telvar
Planavin
3
1
5
3
6.6
-} 2
11.1
6.6
0.25
1.00
1.20
1.17
0.28
1. 12
1.34
1.30
Copper sulfate
2,4-D
DDT
DNBP
3.3
6.6
16.6
6.6
30.00
0.75
2.61
1.50
33.62
0.84
2.93
1.68
Parathion, ethyl
Parathion, methyl
Propanil
Solan
Stam
1
5
2
1
1
2 2
11.1
4.4
2.2
2.2
7.00
2.00
5.50
1.00
0.01
7.84
2.24
6.16
1.12
0.01
Ethylmercury
chloride
Folex
Malathion
Maleic hydrazide
Ceresan Red
6.6
3.3
6.6
3.3
O.OI
1.50
O.OI
3.00
0.01
1.68
0.01
3.36
Toxaphene
Trifluralin
Treflan
3
9
6.6
20.0
1.00
1.11
1.12
1.24
Methoxychlor
Methyl trithion
Mirex
Parathion, ethyl
6.6
3.3
6.6
10.0
0.02
3.00
0.04
7.88
0.02
3.36
0.04
CALIFORNIA. 6
SITES
9.52
Parathion, methyl
Sulfur
16.6
6.6
3.45
25.00
3.86
Aldrin
I
1.6
0.01
0.01
28.02
Azodrin
1
1.6
0.50
0.56
Thiram
10.0
0.01
0.01
Bacillus
Toxaphene
13.3
4.00
4.48
thurinyiensis
1
1.6
0.11
0.12
Trifluralin
Treflan
16.6
0.39
0.44
Captan
2.4-D
1
1.6
3.2
0.01
0.31
O.OI
0.34
Vernolate
Vernam
3.3
2.50
2.80
2
DCPA
Dacthal
1
2
1.6
3.2
3.75
0.08
4.20
0.08
IDAHO. 33 SITES
Diazinon
Captan
1
3.0
0.08
0.08
Dicofol
Kelthane
1
1.6
1. 00
1.12
2,4-D
3
9.0
0.67
0.75
Diphenamid
Enide
1
1.6
0.25
0.28
DDT
2
6.0
3.25
3.64
Diuron
Karmex
1
1.6
2.40
2.68
Diallale
Avadex
1
3.0
0.12
0.13
EPTC
Ethylmercury
Eptam
1
1.6
3.00
3.36
Ethylmercury
chloride
Ceresan Red
2
6.0
0.10
O.ll
chloride
Ceresan Red 1
1.6
0.0 1
0.01
Malathion
I
3.0
1.00
1.12
Malaihion
4
6.5
1.71
1.91
PCP
1
3.0
0.03
0.03
MCPA
MCP
2
3.2
1.25
1.40
Trifluralin
Treflan
3.0
1. 00
1.12
Mercury
I annate
Phosdrin
2
3.2
1.6
1.6
0.06
1.13
1.00
0.06
1.26
Melhomyl
Mevinphos
ILLINOIS, 142
SITES
1.12
Oil Spray
1.6
50.00
56.04
Alachlor
Lasso
15
10.5
1,93
2.16
Ovex
1.6
0.50
0.56
Aldrin
Atrazine
AAtrex
13
22
9.1
15.4
1.15
1.74
1.29
1.95
Oxydemcton-
Butylate
Sutan
3
2 1
1.47
1.64
methyl
Metasyslox
R I
1.6
U.50
0.56
Bux
2
1.4
1.40
1.56
Paraquat
3.2
0.22
0.25
Captan
59
41.5
0.01
O.OI
Parathion. ethyl
6.5
2.08
2.32
Carbofuran
Furadan
2
1.4
0.33
0.36
Parathion, methyl
3.2
1.38
1 54
Chloramben
Amihcn
IS
12.6
1.47
1.64
PCNB
1.6
0.01
O.OI
2,4-D
6
4.2
l.ll
1.24
Pcbulatc
Tillam
1.6
0.12
0.13
Demeton
.Syslox
1
0.7
0.12
0.13
Phenylmcrcury
Fensulfothion
Dasanit
1
0.7
0.90
1.00
acelale
PMA
I
1.6
0.0 1
O.OI
Ferbam
1
0.7
2.00
2.24
{Continued next page)
140
Pesticides Monitoring Journal
TABLE 3 (cont'd. ) . Compounds applied to cropland sites by state, 1971 — National Soils Monitoring Program
Average Total
AVERAG
E Total
Trade
Name.
Pesticides Applied
Application
Trade
Name,
Pesticides Applied
No. OF % OF
Application
Compound
No. OF
% OF
LB./
KG/
LB./
KG/
If Noted
Sites
Sites
Acre
Hectare
Compound
DDT
If Noted
Sites
Sites
20.0
Acre
6.62
Hectare
Heplachlor
4
2.8
1.75
1.96
7.41
Linuron
Lorox
6
4.2
0.89
0.99
DEF
4.0
1.12
1.25
Malathion
52
36.6
0.01
0.01
Diuron
Karmex
4,0
0.70
0.78
Methoxychlor
15
10.5
0.01
0.01
DSMA
20.0
2.24
2.51
MSMA
1
0.7
0.25
0.28
EMTS
Ceresan M
4.0
0.01
0.01
Paraquat
I
0.7
2.00
2.24
Fluometuron
Cotoran
24.0
0.99
1.11
PCP
1
0.7
6.00
6.72
Linuron
Lorox
4.0
0.50
0.56
Phorate
Thimet
7
4.9
0.62
0.69
Methylmercury
Propachlor
Ramrod
18
12.6
1.22
1.36
dicyandiamide
Panogen
12.0
0.08
0.08
Simazine
Princep
I
0.7
2.00
2.24
Monocrotophos
Azodrin
12.0
0.27
0.29
Trifluralin
Treflan
8
5.6
1.20
1.34
Monuron
4.0
1.60
1.79
2,4,5-T
1
0.7
0.25
0.28
MSMA
Nitralin
8.0
1.46
1.63
Planavin
4.0
0.75
0.84
INDIANA. 76 SITES
Paralhion. methyl
Promelryn
Caparol
28.0
8.0
3.56
1.08
3.99
Alachlor
Lasso
9
11.8
1.56
1.74
1.21
Aldrin
9
11.8
1.35
1.51
Propanil
Stam
16.0
2.44
2.73
Atrazine
AAtrex
20
26.3
1.92
2,15
Silvex
4.0
0.50
0.56
Azinphosmethyl
Guthion
1.3
0.22
0.24
Sodium chlorate
4.0
0.05
0.05
Butylale
Sutan
1.3
1.00
1.12
TCA
4.0
4.00
4.48
Chloramben
Amiben
9.2
1.44
1.61
Toxaphene
6
24.0
13.45
15.07
Captan
Sevin
1.3
1.3
0.01
0.61
0.01
0.68
Trifluralin
Treflan
2
8.0
0.63
0.70
Carbaryl
Chlordane
1.3
1.3
2.50
1.08
2.80
1.21
MICHIGAN, 54
SITES
Copper hydroxide
Aldrin
1.8
2.00
2.24
Copper sulfate
1.3
1.42
1.59
Atrazine
AAtrex
14
25
9
2.00
2.24
2,4-D
5.2
0.63
0.70
Captan
1
g
5.00
5.60
Diazinon
1.3
0.40
0.44
Carbaryl
1
8
1. 00
1.12
DNBP
Premerge
1.3
2.25
2.52
2.4-D
1
8
1.00
1.12
Endosulfan
1.3
0.54
0.60
Demeton
1
8
3.00
3.36
EPTC
Eptam
1.3
2.00
2.24
Endosulfan
1
8
6.00
6.72
Linuron
Lorox
2.6
0.55
0.61
EPTC
Epiam
5
5
1.67
1.86
Maneb
1.3
2.14
2.39
Fentin hydroxide
I
8
2.25
2.52
Propachlor
Ramrod
2.6
1.20
1.34
Isodrin
1
8
0.01
0.01
Silvex
1.3
0.25
0.28
Lead arsenate
1
8
16.00
17.93
Simazine
Princep
3.9
2.00
2.24
Mancozeb
Dithane M-45 1
1
8
12.00
13.44
Trifluralin
Treflan
6.5
2.37
2.66
Parathion. ethyl
->
3
7
3.50
3.92
2,4.5-T
1.3
0.35
0.39
Phosalone
Prolate
Imidan
1
1
3
8
7
4.00
11.60
4.48
13.00
IOWA, 152
SITES
Pyrazon
Silvex
TCA
TEPP
Pyramin
1
1
1
1
1
1
1
8
8
8
8
1.25
0.50
1.00
4.00
1.40
Alachlor
Aldrin
Atrazine
Lasso
AAtrex
Sutan
15
10
39
7
9.8
6.5
25.6
4.6
0.93
0.83
1.39
2.46
1.04
0.93
1.56
2.75
0.56
1.12
4.48
Butylale
MID-ATLANTIC,i
16 SITES
Bux
5
3.9
0.82
0.92
Captan
1
0.6
0.01
0.0 1
Alachlor
Lasso
1
6.2
2.00
2.24
Carbaryl
Sevin
1
0.6
1.60
1.79
Atrazine
AAtrex
4
25.0
0.94
1.05
Carbofuran
Furadan
7
4.6
0.92
1.03
Butylate
Sutan
2
12.5
1.63
1.82
Chloramben
Amiben
12
7.8
1.10
1.23
Captan
2
12.5
0.0 1
0.01
2.4-D
19
12.5
0.54
0.61
Carbofuran
Furadan
1
6.2
1. 00
1.12
DDT
2
1.3
1.00
1.12
2.4-D
1
6.2
0.50
0.56
Diazinon
6
3.9
0.54
0.61
Diazinon
I
6.2
0.80
0.89
Dicamba
Banvel D
3
1.9
0.75
0.84
Malathion
2
12.5
0.01
0.01
2.24
53.79
DNBP
Dyfonate
Premerge
Mocap
->
1
1
1
1.3
0.6
0.6
0.6
0.44
0.90
1.00
1.02
0.49
1.00
1.12
1.14
Paralhion, ethyl
Sulfur
1
I
6.2
6.2
2.00
48.00
Ethoprop
Fensulfothion
Lindane
MISSISSIPPI, 31
SITES
1
0.6
0.02
0.02
Alachlor
Lasso
1
3.2
0.75
0.84
Linuron
Lorox
3
1.9
1.00
1.12
Captan
1
3.2
0.03
0.03
Phorate
Thimet
6
3.9
0.93
1.04
Chloroneb
Demosan
7
22.5
0.03
0.03
Propachlor
Ramrod
14
8.5
1.50
1.68
DDT
8
25.8
3.81
4.27
Toxaphene
1
0.6
2.73
3.05
DEF
4
12.9
0.90
1.00
Trifluralin
Treflan
14
9.2
0.69
0.77
Disulfoton
Di-Syston
7
22.5
0.01
0.01
Diuron
DNBP
Karmex
-)
6.4
2.75
3.08
KENTUCKY.
31 SITES
4
12.9
1.19
1.33
DSMA
I
3.2
1.86
2.08
Atrazine
AAtrex
2
6.4
1.02
1.14
Endrin
1
3.2
4.20
4.70
Dalapon
Dowpon
->
6.4
1.05
1.17
Ethylmercury
2.4-D
1
3.2
0.05
0.05
chloride
Ceresan Red 1
3.2
O.OI
0.01
2,4-DB
Butyrac
1
3.2
0.80
0.89
Fluometuron
Cotoran
5
16.1
0.76
0.85
Paraquat
1
3.2
1.00
1.12
Folex
I inuron
Lorox
3
9.6
3.2
0.75
1.00
0.84
1.12
LOUISIANA,
25 SITES
1_ IIIUIL"!
Malathion
Methylmercury
1
3.2
2.40
2.68
Alachlor
Lasso
1
4.0
1.00
1.12
Aldrin
3
12.0
0.15
0.16
acetate
Ceresan L
6
19.3
0.01
0.01
Azinphosmethyl
2.4-D
Guthion
1
4
4.0
16.0
0.75
0.81
0.84
0.91
Mirex
MSMA
4
7
12.9
22.5
0.08
2.48
0.09
2.77
1.12
3.77
2.4-DB
Butyrac
1
4.0
1.95
2.18
Nitralin
Planavin
1
3.2
1.00
Dalapon
Dowpon
1
4.0
6.80
7.62
Parathion. methyl
13
41.9
3.36
(Continued next page)
Vol. 12, No. 3, December 1978
141
TABLE 3 (cont'd. 1. Compounds applied to cropland sites hy state, 1971 — National Soils Monitoring Program
Average Total
Average Total
Trade
Name,
Pesticides Applied
No. OF % OF
Application
Trade
Name,
Pesticides Applied
No. OF % OF
Application
LB./
KG/
LB./
KO/
Compound
If Noted
Sites
Sites
ACRE
Hectare
Compound
Simazine
If Noted
Princep
Sites
1
Sites
2.7
Acre
2.04
Hectare
Sodium chlorate
2
6.4
1.07
1.20
2.28
Tcrraiolc
1
3.2
0.15
0.16
0.04
Sulfur
1
2.7
0.50
0.56
Thiram
I
3.2
0.04
Toxaphenc
Treflan
10
7
32.2
22.5
6.90
0.75
7.73
0.84
NORTH CAROLINA
, 30 SITES
Trifluralin
Alachlor
Atrazine
Carbaryl
2,4-D
DEF
Lasso
AAtrex
Sevin
10.0
23.3
6.6
16.6
3.3
3.00
1.86
3.00
2.20
0.75
3.36
2.08
3.36
MISSOURI. 80
SITES
Alachlor
Aldrin
Atrazine
Chlorambcn
Lasso
8.7
3.7
1.82
0.63
2.03
0.70
2.46
0.84
AAtrcx
Amibcn
17
21.2
2.5
2.24
0.88
2.50
0.98
Dichlofenthion
Dichloropropcne
Nemacidc
3.3
3.3
6.(X)
67.00
6.72
75.09
2 4-D
2.5
0.50
0.56
Disulfoton
Di-Syslun
6.6
0.90
1.00
2'.4-DB
DSMA
I iniiron
Bulyrac
1.2
1.2
0.22
3.00
0.24
3.36
Fensulfothion
Fluometuron
Coloran
3.3
3,3
2.00
1.25
2.24
1.40
Lorox
2.5
0.88
0.98
Malathion
3.3
0.50
0.56
MSMA
Naptalam
Propachlor
Trifluralin
1.2
1.65
1.84
Maleic hydrazide
6.6
3.00
3.36
Alanap
2.5
2.00
2.24
Naptalam
Alanap
3,3
3.00
3.36
Ramrod
3.7
3.13
3.51
Toxaphene
3.3
0.09
0.10
Treflan
3.7
0.75
0.84
Trifluralin
Treflan
6.6
1.00
1.12
NEBRASKA. lOS
i SITES
OHIO, 59 SITES
Alachlor
Lasso
2
1.9
1.50
1.68
Alachlor
Lasso
5.0
0.92
1.02
Atrazine
AAtrex
22
20.9
1.38
1.54
Aldrin
5.0
3.67
4.10
Biix
5
4.7
0.91
1.01
Atrazine
AAtrex
13,5
2.01
2.25
Captan
Carbaryl
Carbofuran
31
29.5
0.01
0.01
Azinphosmethyl
Ciuthion
1,6
1.00
1.12
Sevin
Furadan
2
6
1.9
5.7
1.17
0.89
1.31
0.99
Bordeaux mixtures
Captan
1.6
1.6
1.25
5.20
1.40
5.82
Chevron RE-5353
4
3.8
0.85
0.95
Carbaryl
Sevin
3,3
1.13
1.26
2. 4-D
21
20.(1
1)72
0.81
Carbophenothion
Trithion
1.6
3.20
3.58
n 1 T 7 i n n n
0.9
1.30
1.45
Chlorambcn
Amiben
3.3
2.75
3.08
Dichloropropcne
Dicldrin
0.9
1.9
17.00
n.oi
19.05
0.01
Chloropropham
Cypromid
CIPC
Clobber
1.6
1.6
2.50
0.75
2.80
0.84
Disulfoton
Di-SystOTt
0.9
1.00
1.12
2,4-D
12
20.3
0.50
0.56
EPTC
Hplam
0.9
3.00
3.36
Dicamba
Banvel D
8.4
0.20
0.22
Fensulfothion
0.9
0.61
0.68
Dodine
1.6
0.50
0.56
Heptachlor
Londax
0.9
0.01
0.01
Fcrbam
1.6
3.17
3.55
0.9
0.50
0.56
Heptachlor
2
3,3
1.57
1.76
Malathion
26
24.7
0.03
0.03
Lead arsenate
1,6
1.20
1.34
Melhoxychlor
Mcthylmcrcury
dicyandiatnide
Panogen
2
2
1.9
1,9
0.01
0.01
0.01
0.01
Linuron
Melhoxychlor
Parathion. ethyl
Lorox
6,7
1,6
1.6
1.25
2.00
0.50
1.40
2.24
0.56
Parathion. ethyl
2
1.9
1.00
1.12
Phosphamidon
Simazine
Dimecron
1.6
0.03
2.(X)
0.03
Phorate
Thimet
Ramrod
5
4
4.7
3.8
0.87
2.59
0.97
2.90
1,6
2.24
Propachlor
OKLAHOMA. 62
SITES
Thiram
1
0.9
0.01
0.01
Alachlor
Arsenic pentoxide
Atrazine
Lasso
AAtrex
.
1.6
3.2
1.6
5.00
0.50
13.00
5.60
0.56
NEW ENGLAND.i
18 SITES
2
1
Alachlor
Lasso
1
5.5
2.00
2.24
14.57
Atrazine
AAtrex
1
5.5
1.00
1.12
Captan
2
3.2
0.01
0.01
Azinphosmethyl
Carbaryl
Guthion
Sevin
1
1
5.5
5.5
0.50
1.25
0.56
1.40
2.4-D
Disulfoton
3
2
4.8
3.2
3.08
0.65
3.45
0.72
Dinitrocresol
5.5
0.75
0.84
FMTS
Ceresan M
4
6.4
0.01
0.01
Endosulfan
1
5.5
0.75
0.84
F.thylmercury
EPTC
Eptam
1
5.5
4.00
4.48
chloride
Ceresan Re
d 1
1.6
0.01
0.01
Maneb
1
5.5
4.80
5.37
Furclhrin
1
1.6
8.00
8.96
Parathion. methyl
1
5.5
1.25
1.40
Mcthylmcrcury
dicyandiamide
Nabam
Parathion, ethyl
Parathion, methyl
Panogen
2
I
3
5
3.2
1.6
4.8
8.0
0.01
5.00
3.17
0.50
0.01
NEW
YORK. .17
SITES
5.60
3.54
0.56
Atrazine
AAtrex
11
29.7
1.38
1.54
Azinphosmethyl
Guthion
2
5.4
0.56
0.62
Phorate
1
1.6
15.00
16.81
Butylatc
Suian
1
2.7
3.00
3.36
Thiram
3
4.8
0.01
0.01
Captan
Carbaryl
d
10.8
0.66
3.20
0.37
0.25
2.67
0.70
2.97
0.33
0.50
1.00
4.00
0.01
12.80
0.01
0.73
3.58
0.41
0.28
2.99
0.78
3.33
0.36
0.56
1.12
4.48
0.01
14.34
0.01
Sevin 2
3
2
1
Di-Syston 2
Premerye 2
1
1
Phallan 1
1
->
Diihane M-J5 1
1
5.4
8.1
5.4
2.7
5.4
5.4
2.7
2.7
2.7
2,7
5.4
2.7
2,7
OREGON, 37 SITES
2, 4-D
Dicldrin
Dinitrocresol
Disulfoton
DNBP
Dodine
Endosulfan
Folpet
Lead arsenate
Malathion
Mancozeb
Mcthoxychlor
Atrazine
Bromacil
Captafol
2,4-D
Dicamba
Dichlorprop
Dichloropropcne
Disulfoton
Endosulfan
EPTC
Heptachlor
llcxachloro-
benzenc
Linuron
AAtrex
Hyvar
Difolatan
Banvel D
2,4-DP
Di-.Syston
Thiodan
Eptam
2.7
2.7
2.7
8.1
2,7
2.7
2.7
5.4
5.4
2.7
2.7
4.00
0.37
1.50
0.50
0.06
3.00
0.01
2.00
0.75
3.00
O.OI
4.48
0.41
1.68
0.56
0.06
3.36
0.01
2.24
0.84
3.36
0,01
Phosphamidon
Propargitc
Dimecron
Omile
1
2.7
2.7
0.50
5.00
0.56
5.60
Lorox
2.7
2.7
0.01
0.75
0.01
0.84
(Continued next page)
142
Pesticides Monitoring Journal
TABLE 3 (cont'd. ). Compounds applied to cropland sites hy state, 1971— National Soils Monitoring Program
Average Total
Average Total
Trade
Name.
Pesticides
No. OF
Applied
% OF
Application
Trade
Name.
Pesticides Applied
No, OF % OF
Application
LB./
KG/
LB./
KG/
Compound
If Noted
Sites
Sites
Acre
Hectare
Compound
If Noted
Sites
Sites
Acre
Hectare
Malathton
Melhylmercury
1
2.7
1 .00
1.12
TENNESSEE,
24 SITES
dicyandiamidc
Panoycn
J
8.1
0.14
0.15
DEF
I
4.1
1.50
1,68
Mevinphos
Phosdrin
1
2.7
0.50
0.56
Disulfoton
Di-Syston
3
12.5
3.00
3,36
Oxydemelon-
Diuron
Karmex
2
8.3
1.55
1,73
methyl
Paralhion, ethyl
Metasystox-R 1
2
2.7
5.4
0.50
3.25
0.56
3.64
DSMA
Fluomctuion
Folex
Parathion, methyl
Cotoran
1
1
2
1
1
1
1
4.1
8.3
4.1
4.1
4.1
4.1
2.00
1.50
1.50
1.50
1.50
6.00
2,24
1.68
1.68
PENNSYLVANIA,
35 SITES
1.68
1.68
6.72
Alachlor
Lasso
2
5.5
0.88
0.98
Toxaphene
Atrazine
AAtrex
5
13.8
1.65
1.84
Trietazine
I
4.1
0.70
0.78
Bulylate
Sulan
1
2.7
1.20
1.34
Trifluralin
3
12.5
0.98
1.09
?,4-D
2
5.5
0.50
1.00
1.00
0.56
1.12
1.12
Malaihion
1
1
2^7
2.7
VIRGINIA/WEST VIRGINIA,' 26
SITES
Melhoxychlor
Atrazine
Captan
Carbaryl
Diazinon
AAtrex
Sevin
2
7.6
3.8
3.8
2.00
0.08
2.00
2.24
SOUTH
CAROLINA
. 15 SITES
0,08
2.24
0.44
Benefit!
Balan
1
6.6
1.08
1.21
3^8
0.40
BHC
1
6.6
0.03
0.03
Diniirocresol
3.8
1.50
1.68
Carbaryl
Scvin
2
13.3
2.25
2.52
Endosulfan
3.8
1.20
1,34
Copper sulfate
1
6.6
10.50
11.76
EPTC
Eptam
3.8
0.70
0,78
2.4-DB
1
6.6
0.25
0.28
Mctham
Vapam
3.8
2.16
2.42
DDT
J
2I).0
8.94
9,24
Metlioxychlor
3.8
0.80
0.89
DEF
2
13.3
1.16
1.30
Vernolalc
Vcrnam
3.8
2.00
2.24
ni«n1 fnt r»n
Di-Syston
Karmex
Alanap
2
13.3
13.3
6.6
0.59
1.00
0.75
0.65
1.12
0.84
Diuron
2
1
WASHINGTON STATE, 45 SITES
Naptalam
Aldrin
1
2.2
0.43
0,48
Parathion, methyl
5
33.3
4.76
5.34
BHC
2
4.4
0.01
0,01
Thiram
1
6.6
0.01
0.01
Bromacil
2
4.4
0.75
0.84
Toxaphene
3
20.0
13.16
14.75
Captan
2
4.4
0.06
0.06
Trifluralin
Treflan
2
13.3
1.00
1.12
2,4-D
DDT
Dicamba
HCB
Banvel D
13
1
1
6
28.8
2.2
2.2
13.3
1.32
0.75
0.13
O.OI
1.48
SOUTH
DAKOTA,
106 SITES
0.84
0.14
Atrazine
AAtrex
5
4.7
1.59
1.78
0.01
Barban
Carbync
1
0.9
0.25
0.28
Melhylmercury
Bux
3
2.8
0.70
0.78
dicyandiamidc
1
2.2
0.01
0.01
Captan
24
22.6
0.01
0.01
Parathion, ethyl
1
2.2
1.50
1.68
2,4-D
32
30.1
0.45
0.50
Phenylmercury
Diazinon
3
2.8
1.64
1.83
acetate
1
2.2
0.01
O.OI
Dicamba
Banvcl D
2
1.8
0.12
0.13
Phenylmercury
Dicldrin
2
1.8
0.01
0.01
urea
3
6.6
0,01
0.01
Ethylmercury
Terbacil
Sinbar
1
2.2
1.40
1.56
chloride
Fensulfothion
Cercsan Red 1
0.9
0.01
0.0 1
Terbutryn
Igran
1
2.2
1.75
1.96
1
0.9
1.20
1.34
Malathion
MCP
17
16.0
1.8
0.01
0.25
0.01
0.28
WISCONSIN,
66 SITES
MCPA
Alachlor
Lasso
6.0
1.44
1.61
Methoxychlor
0.9
O.lll
0.01
Atrazine
AAtrex
25
37.8
1.83
2.04
Melhylmercury
Bux
1.5
7.00
7.84
dicyandiamidc
Panogen
3.7
0.01
0.01
Carbofuran
Furadan
4.5
0.90
1.01
Parathion, methyl
0.9
0.50
0.56
2,4-D
3.0
1.50
1.68
Phorate
Thimet
0.9
0.60
0.67
2,4-DB
Disulfoton
Butyrac
Di-Syston
1.5
1.5
0.50
2.00
0.56
2.24
Propachlor
Ramrod
2.8
2.40
2.68
Entiosulfan
Thiodan
1.5
1.00
1.12
Thiram
1.8
0.01
0.01
Linuron
Lorox
1.5
1.00
1.12
Atrazine
AAtrex
8.3
1.85
2.07
MCPA
MCP
1.5
0.50
0.56
2,4-DB
Butyrac
4.1
0.29
0.32
Phorate
Thimet
1.5
6.00
6.72
DDT
4.1
3.00
3.36
Thiram
1.5
0.01
0.01
'See Table 1.
Vol. 12, No. 3, December 1978
143
.... ....
0
C)C)C<5Qw:^^
$:
aX<>VJ^\VS
C310
m'.'."^' <
« M
- Kf^HW y A 5AAA
III- LoOowO
FIGURE 2. Percent of sites reporting pesticide applications, 1971 , National Soils Monitoring Program
TABLE 4. Crop and pesticide application data for sampling sites, 1971 — National Soils Monitoring Program
Pesticides
Pesticides
Pesticides
Pesticides
Pesticides
Not
Application
Pesticides
Not
Application
Total
No. OF
Applied
Applied
Unknown
Total
Applied
Applied
Unknown
No. OF
No. OF
No. OF
No. OF
No. OF
No. OF
No. OF
Crop
Sites
Sites %
Sites
7c
Sites
9r
Crop
Sites
Sites
%
Sites
%
Sites %
Corn, field
445
366 82
70
16
9
2
Saffiower
1
33
2
67
Soybeans
251
147 59
100
40
4
Almonds
2
100
Wheat
115
56 49
59
51
Blueberries
2
100
Hay, mixed
112
3 3
108
96
1
Cabbage
2
100
Alfalfa and/ or
Figs
~i
100
bur clover
108
10 9
97
90
1
Peaches
->
100
Cotton
63
55 87
6
10
2
Timothy
->
100
Sorghum, sweet
Tomatoes
sorghum, milo
52
32 62
19
37
1
Apricots
1
100
Oats
47
16 34
30
64
1
Broccoli
1
100
Pasture
41
2 5
39
95
Carrots
1
100
Hay, grass
25
25
100
Cherries
1
100
Barley
16
4 25
12
75
Cowpeas
1
100
Peanuts
11
9 82
2
18
Cucumbers
1
100
Potatoes, white
11
9 82
.>
12
Flax
1
100
Clover
y
1 11
8
89
Grapefruit
1
100
Rice
9
8 89
1
11
Lemons
1
100
Beans, diy
8
5 63
3
37
Lentils
1
100
Grapes
8
7 88
1
12
Lettuce
1
100
Apples
7
7 100
Mint
1
100
Oranges
7
5 71
2
29
Pecans
1
100
Sugarbeels
6
5 83
1
17
Plums prunes
1 100
Sugarcane
6
6 100
String beans
1
100
Peas
5
2 40
3
60
VVatermcItm
1
100
Rye
5
5
100
Other
11
3
27
8
73
Tobacco
5
4 80
1
20
Fallow sites
83
3
4
80
96
144
Pesticides Monitoring Journal
TABLE 5. Compounds applied lo cropland sites by crop, 1971— National Soils Monitoring Program
Pesticides Applied
Average Total
Application
Compound
No. OF Sites
• OF Sites
LB. /Acre
ko/Hectare
Reported Total
Application Rate, kg Hectare
MiN.
Max.
ALFALFA and BUR CLOVER. 106 SITES
Carbaryl
Diazinon
EPTC
Malathion
Melhoxychlor
Mevinphos
Parathion, elhyl
Trichlorfon
0.9
0.9
1.9
2.8
1.9
1.9
2.8
0.9
1.00
0.40
1.8S
L13
0.90
1.50
2.50
0.75
1.12
0.45
2.07
1.27
1.01
1.68
2.80
0.84
0.78
1.12
0.90
1.12
0.56
1.12
0.45
3.36
1.57
1.12
2.24
6.72
0.84
COTTON, 61 SITES
Aldrin
Arsenic penloxide
Azodrin
Cacodylic acid
Captan
Chloroneb
2.4-D
DDT
DEF
Dicofol
Disulfoton
Diuron
DNBP
DSMA
EMTS
Endrin
Eliiylmercury chloride
Fluometuron
Folex
Linuron
Malathion
MCPA
Mercury
Methyl trilhion
Methylmerciiry acetate
Methylmercury dicyandia
Mirexi
Monuron
MSMA
Nitralin
Paraquat
Parathion. ethyl
Parathion, methyl
PCNB
Prometryn
Sodium chlorate
Terrazole
Thiram
Toxaphene
Trifluralin
4
1
1
9
1
25
9
1
14
8
2
11
4
2
1
21
5
2
2
1
2
1
6
mide 2
2
15
1
1
5
36
4
1
3
27
21
1.6
3.3
6.6
1.6
1.6
14.8
1.6
41.0
14.8
1.6
23.0
13.1
3.3
18.0
6.6
3,3
1,6
34.4
8.2
3.3
3.3
1.6
3,3
1.6
9.8
3.3
1.6
3.3
24,6
1,6
1.6
8.2
59.0
3,3
3,3
6.6
1.6
4,9
44,3
34.4
0.01
0.50
0.33
0.01
0.01
0,01
0,44
4,28
1.03
1.00
1.31
1.45
1.62
2.00
0.04
2.80
0.01
0.96
1.05
0.63
1.55
0.50
0.06
i.OO
0.01
0.01
0.01
1.30
1.86
1.00
0.25
6.78
3.26
3.51
1.08
1.80
0.15
0.01
7.95
0.74
0.01
0.56
0.37
0.01
0.01
0.01
0.49
4.80
1.16
1.12
1,46
1.63
1.82
2.24
0.04
3.14
0.01
1.07
1.18
0.70
1.74
0.56
0.07
3.36
0.01
0.01
0.01
1.46
2.08
1.12
0.28
7.60
3.65
3.M3
1.21
2.02
0.17
0.01
8.91
0.83
0.01
0.56
0.06
0.01
0.01
0.01
0.49
0.09
0.67
1.12
0.01
0.38
1.12
0.24
O.Ul
1.57
0.01
0.56
0.84
0.56
0.78
0.56
0.01
3.36
0.01
0.01
0.01
1.12
0.75
1.12
0.28
0.84
0.06
0.01
0.18
0.06
0.17
0,01
0.1(1
0.28
0.56
0.56
0.01
13,45
1.68
7.85
5.04
2,52
4,48
0.11
4.71
2.24
1.68
0.84
2.69
0.12
0.01
0.01
1.79
5.60
21.02
11.21
7.85
2.24
5.60
0.01
40.35
1.24
FIELD CORN, 427 SITES
Alachlor
Aldrin
Atrazine
Butylate
Bux
Captan
Carbaryl
Carbofuran
Chevron RE-5353
Chloramben
Chlordane
Cypromid
2,4-D
Dalapon
DDT
Demeton
Diazinon
Dicamba
Dieldrin
DNBP
Disulfoton
Dyfonate
EPTC
Ethoprop
37
37
199
18
17
116
3
18
4
2
1
1
72
2
2
1
11
9
3
1
2
1
1
1
8.7
8.7
46.6
4.2
4,0
27,2
0.7
4.2
0.9
0,5
0,2
0,2
16,9
0.5
0.5
0.2
2.6
2.1
0.7
0.2
0,5
0.2
0,2
0,2
1.66
1.37
1.72
1.74
1.26
0.01
1.32
0.81
0.85
1.12
2.50
0.75
0.73
1.05
1.00
0.12
0.93
0.37
0.01
3.20
0,65
11.90
2.00
1,00
1.86
1.54
1.93
1.95
1.41
0.01
1.47
0.90
0.95
1.26
2.80
0.84
O.SI
1.18
1.12
0.13
1.05
0.42
0.01
3.59
0.73
1.01
2.24
1.12
0.28
0,11
0.16
0.28
0.5(1
0.01
0,84
0.28
0.78
0.28
2.80
0.84
0.06
1.18
1.12
0.13
0,01
0,13
0.01
3.59
0.56
1.01
2 24
1.12
6.72
5.60
4.48
3.36
7.85
0.01
1,79
2,58
1,12
2,24
3,36
1.18
1.12
2.80
1.12
0.01
0.90
{Continued next page)
Vol, 12, No, 3, December 1978
145
TABLE 5 (cont'd.). Compotiiuh applied to cropland sites by crop, 1971 — National Soils Monitoring Program
Pesticides Applied
Average Total
Application
Reported Total
Application Rate. kg/Hectare
Compound
No. of Sites
> OF Sites
LB. /Acre
kg/Hectare
MiN.
Max.
Elhylmerciiry chloride
1
Fciisulfolhion
4
Ferbam
1
Furethrin
1
Hcptachlor
6
Isodrin
I
Lindane
1
Linuron
2
Londax
1
Malatliion
96
Methoxychlor
20
Mirexi
1
MSMA
1
Paraquat
I
Paratiiion, ethyl
3
PCP
1
Phorate
20
Propachlor
38
Silvex
2
Simazine
5
2,4, 5-T
2
Thiram
1
Toxaphene
1
Alachlor
Captan
Carbaryl
Chloramben
Chloropropham
Dalapon
2,4-DB
DDT
Dichloropropene
DNBP
Fluometiiron
Linuron
Mirex'
MSMA
Naptalam
Nitralin
Paraquat
Parathion. methyl
Propachlor
Solan
Thiram
Toxaphene
Trifluralin
Vernolaie
27
3
5
38
1
1
6
2
10
1
16
1
1
3
4
I
3
1
1
2
38
3
0.2
0.9
0.2
0.2
1.4
0.2
0.2
0.5
0.2
22.5
4.7
n.2
0.2
0.2
0.7
0.2
4.7
8.9
0.5
1.2
0.5
0.2
0.2
0.01
0.93
2.00
8.00
1.67
0.01
0.02
0.52
0.50
0.01
0.01
D.OI
0.25
1.00
0.87
6.00
(1.81
1.42
0.38
2.C0
0.30
0.01
2.73
0.01
1.04
2.24
8.97
1.87
0.01
0.02
0.59
0.56
0.01
0.01
0.01
0.28
1.12
0.97
6.72
0.91
1.57
0.42
2.24
0.34
0.01
3.06
11.1
1.2
2.1
15.6
0.4
0.4
2.5
0.8
0.4
4.1
0.4
66
0.4
0.4
1.2
1.6
0.4
1.2
0.4
0.4
0.4
0.8
15.6
1.2
1.33
0,04
1.88
1.42
2.50
6.80
0.84
2.50
67.00
1.08
1.00
0.96
0.01
2.00
2.33
1.06
2.00
2.55
2.80
1.00
0.04
3.82
I. II
0.80
1.49
0.04
2.11
1.59
2.80
7.62
0.94
2.80
75.09
1.21
1.12
1.08
0.01
2.24
2.61
1.19
2.24
2.86
3.14
1.12
0.04
4.29
1.24
0.90
0.01
0.68
2.24
8.97
0.01
0.01
0.02
0.33
0.56
0.01
0.01
0.01
0.28
1.12
0.56
6,72
0.19
0.10
0.28
1.40
0.28
0.01
3.06
0.22
0.01
0.90
0.25
2.80
7.62
0.25
1.12
75.09
0.43
1.12
0.28
0.01
2.24
1.12
0.84
2.24
1.12
3.14
1.12
0.04
2.24
0.25
0.78
1.34
3.36
0.84
0.01
0.02
1.23
16.81
6.72
0.56
2.80
0.39
MIXED HAY, 111 SITES
2.4-D
Mirexi
2
1
1.8
0.9
0.80
0.01
0.90
0.01
0.67
0.01
1.12
SOYBEANS, 243 SITES
6.16
0.08
4.30
4.48
2.19
4.48
2.52
2.24
3.36
1.68
5.77
6.33
5.60
1.01
WHEAT. 113 SITES
Aldrin 1
Azinphosmethyl 1
Barban 1
BHC 2
Bromacil 2
Captan 1
2,4-D 28
Dicamba 3
Dichlorprop 1
Disulfoton 2
EMTS 4
Ethylmcrcury chloride 4
Hexachlorobenzene 6
Methylmercury dicyandiamide 9
Parathion, ethyl 1
Parathion, methyl 4
Phenylmercury acetate 3
Terbutryne 1
Thiram 2
0.9
0.9
0.9
1.8
1.8
0.9
24.8
2.7
0.9
1.8
3.5
3.5
5.3
8.0
0.9
3.5
2.7
0.9
0.01
0.22
0.25
0.02
0.56
0.25
0.83
0.11
3.00
0.36
0.01
0.06
0.02
0.01
8.00
0.50
0.01
1.75
O.OI
0.01
0.25
0.28
0.02
0.63
0.28
0.93
0.12
3.36
0.40
0.01
0.06
0.02
O.OI
8.97
0.56
0.01
1.96
0.01
0.01
0.25
0.28
0.01
0.41
0.28
0.13
0.07
3.00
0.40
0.01
0.01
0.01
0.01
8.97
0.56
0.01
1.96
0.01
0.02
0.84
4.48
0.15
0.40
0.01
0.11
0.03
0.01
0.56
0.01
0.01
'Aerially applied for conlrol of the imported fire ant.
146
Pesticides Monitoring Journal
TABLE 6.
Pesticide application information on selected crops, by state, for sampling sites. 1971-
National Soils Monitoring Program
Total
Pesticides
Pesticides
Pesticides
Total
Pesticides
Pesticides
Pesticides
State
No. OF Sites Applied
Not Applied
Use Unknown
No. OF Sites
Appl
ED
Not Applied
Use Unknown
ALFALFA
AND/OR BUR CLOVER
COTTON
Alabama
0
4
4
Arkansas
1
1
9
7
7
6
1
1
1
California
5
3
2
Georgia
0
5
5
Illinois
4
4
0
Indiana
1
1
0
Iowa
19
19
0
Louisiana
0
7
7
Michigan
7
1
6
0
Mississippi
0
13
12
1
Missouri
3
1
2
1
1
Nebraska
10
10
0
New England
2
2
0
New York
4
4
0
N. Carolina
0
1
1
Ohio
2
2
0
Oklahoma
2
1
1
5
2
2
1
Oregon
5
1
4
0
Pennsylvania
7
1
5
1
0
S. Carolina
0
5
4
1
S. Dakota
16
16
0
Tennessee
(1
6
6
Va./W, Va.
2
2
0
Washington stale
2
2
C
Wisconsin
16
16
0
FIELD
CORN
SOYBEANS
Alabama
5
3
2
7
1
6
Arkansas
1
1
24
13
11
California
1
1
0
Florida
1
1
2
2
Georgia
1.1
5
g
3
2
1
Illinois
67
65
2
58
36
22
Indiana
34
31
2
1
21
17
3
1
Iowa
81
70
11
42
34
8
Kentucky
16
10
4
2
3
1
1
1
Louisiana
1
1
5
2
3
Michigan
21
14
7
1
1
Mid-Atlantic
9
5
2
2
1
1
Mississippi
1
1
14
9
5
Missouri
18
16
2
22
13
8
1
Nebraska
46
40
4
2
3
3
New England
3
2
1
0
New York
15
11
2
2
0
N. Carolina
13
9
4
8
5
3
Ohio
23
19
4
14
8
5
1
Oklahoma
3
2
1
2
1
1
Pennsylvania
8
5
3
1
1
S. Carolina
2
1
1
7
2
5
S. Dakota
27
26
1
1
1
Tennessee
5
2
3
9
2
7
Va./W, Va.
3
3
1
1
Washington stale
2
1
1
0
Wisconsin
24
23
1
0
WHEAT
MIXED
HAY
Alabama
0
1
1
Arkansas
1
1
2
2
California
4
1
3
1
1
Florida
0
1
1
Idaho
13
5
8
0
Illinois
6
1
S
1
1
Indiana
5
1
4
2
2
Iowa
1
1
5
5
Kentucky
0
2
2
Michigan
1
1
9
1
8
Mid-Atlantic
0
1
1
Mississippi
0
1
1
Missouri
1
1
20
20
Nebraska
3
1
2
0
New England
0
5
5
New York
0
9
8
1
N. Carolina
0
1
1
Ohio
5
1
4
6
6
Oklahoma
34
13
21
0
Oregon
3
3
3
3
(Continued next page)
Vol. 12, No. 3, December 1978
147
TABLE 6 (cont'd. ). Pesticide appliiulion injonnation on selccleil crops, />>■ slate, for sampliiif; sites, 1971 —
National Soils Motiitorinii Program
Total
No. OF Sites
Pesticides
Applied
Pesticides
Not Applied
Pesticides
Use Knovvn
Total
No. OF Sites
Pesticides
Applied
Pesticides
Not Applied
Pesticides
Use Known
Pennsvlvania
0
S. Dakota
20
IS
5
Va./W. Va.
0
Washington state
18
15
3
Wisconsin
0
13
8
5
1
15
12
8
5
15
LITERATURE CITED
(/) Bennett. I. L. 1967. Foreword. Peslic. Monit, J. 1(1).
(2) Carey, A. £., J. A. Gowen. H. Tai, W. G. Mitchell, ami
G. B. Wiersnia. I97S. Pesticide residue levels in soils
and crops, 1971 — National Soils Monitoring Program
(III). Pestic. Monit. J. 12(3) : 117-136.
(.?) Panel on Pesticide Monitorini;. 1971. Criteria for defin-
ing pesticide levels to be considered an alert to poten-
tial problems. Pestic. Monit. J. 5(1);36.
(•/) Wiersnui, G. B., P. F. Sand, and E. L. Cox. 1971. A
sampling design to determine pesticide residue levels in
soils of the conterminous United States. Pestic. Monit.
J. 5(l):63-66.
148
Pesticides Monitorinc; Journal
WATER
Organochlorines, ChoUnest erase Inhibitors, and Aromatic Amines in
Dutch Water Samples, September 1969-December 1975
Ronald C. C. Wegnian and Peter A. Greve i
ABSTRACT
The Dutch aquatic ciivironnwitt was monitored jrom Sep-
tember 1969 to December 1975 for organochlorine pesti-
cides and their metabolites, cholinesterase inhibitors, and
aromatic amines. The 1,492 samples analyzed included
surface water, rainwater, groundwater, and drinking water.
The higliest concentrations of he.xachlorobeiizene (HCB)
and a- and fi-benzene he.xachloride (BHC) were found in
the Rhine River and its tributaries. Concentrations of the
compounds in the Dutch part of the Rhine River decreased
downstream. Other organochlorine pesticides and their
metabolites, heptachlor. hcptachlor epoxide, aldrin, dieldrin.
endrin a- and ji-endosulfan. and ^DDT were detected occa-
sionally, but only in low conct ntrations. Cholinesterase in-
hibitors and aromatic amines were always present in the
Rhine River ami its tributaries.
Introduction
Preliminary investigations before 1969 of organochlorine
pesticides and related substances in the Dutch aquatic
environment indicated the necessity of a long-term in-
vestigation. Endosuifan levels found in the Rhine River
later in 1968 (6) underlined the need for such an in-
vestigation.
Samples were taken from surface water, rainwater,
groundwater, and drinking water prepared from surface
water. Presently, about one third of the Dutch popu-
lation is at least partly supplied with drinking water
prepared from surface water. Sampling sites varied
every year, except for a few fixed sites including the
Maas and Rhine Rivers, so that after 7 years all parts
of The Netherlands were investigated for at least I
year. Special interest was paid to large agricultural
areas such as the IJsselmeerpolders.
'Laboralory of Toxicology. National InsUluiu of Public Healih. Bili-
hoven, The Netherlands.
During the study, the number of sampling sites at
drinking water stations was gradually decreased as the
stations acquired equipment and expertise to analyze
their own samples.
Levels of organochlorine pesticides were determined
because they are persistent and accumulate in the food
chain. Analyses were performed for cholinesterase in-
hibitors including phosphates, thiophosphates, dithio-
phosphates, and carbamates (e.g., dichlorvos, parathion.
malathion, carbaryl, respectively). From the herbicide
group, urea compounds were chosen because of their
great application rate. This group of compounds was
determined as their aromatic amine moiety.
During the present investigation, papers were published
on endosuifan in the Rhine River (6), cholinesterase
inhibitors in Dutch surface waters {S), pesticides in the
Rhine River (9), aromatic amines and their derivatives
in Dutch surface waters (10), and the fate of pesticides
during drinking water preparation (7). In cooperation
with the Federal Health Office in Berlin, the concentra-
tions of cholinesterase inhibitors in the German and
Dutch parts of the Rhine River were compared and the
main source was determined (5). From these papers,
only the primary results are repeated here.
Metlwds and Materials
The 1,492 samples were collected by means of a bail
and were transported in acetone-washed bottles to the
National Institute of Public Health, Bilthoven, The
Netherlands. Surface water was taken from a depth of
about 1 m. Locations of the 92 sampling sites are given
in Figure 1.
The methods mentioned in the present report include im-
provements introduced during the study. They had no
Vol. 12, No. 3, December 1978
149
NETHERLANDS
1-16 surface water for
preparation of
drinking water
17-20 groundwater and
rainwater
21-24 coastal waters
25-3A IJsselmeer region
35-44 Maas River and
tributaries
45-50 Rhine River and
51-92
waters
tributaries f" ~\S^*^
other surface _~^ — -d-Q'^^
FIGURE 1. Snmplina silex for study of organochlorines, choliite.sterasc inhibitors, and aromatic amines in Dutch water samples
significant influence on the results, except for the C„
compounds which could be determined separately only
from May 1970.
ORGANOCHLORINE COMPOUNDS
Water samples of 1000 ml, including silt, were extracted
successively with 200, 100, and 100 ml of petroleum
ether (boiling range, 40°-60''C). The combined ex-
tracts were dried over anhydrous sodium sulfate and
concentrated to about 5 ml in a Kiidcrna-Danish evapo-
rative concentrator. The last few milliliters of solvent
were evaporated to exactly 1 ml by a gentle stream of
nitrogen at room temperature. The concentrated ex-
tract was added to a microcolumn containing 2.00 g
basic alumina (W-200, activity Super I, Woelm). Be-
fore use, the microcolumn was activated for 16 hours
at 150°C, and then deactivated with 11 percent water
(11 g water + 89 g ahmiina).
The column was eluted with 5 ml of petroleum ether to
produce Eluate A containing HCB, «- and 7-BHC,
heptachlor epoxide (about 10 percent), /;,/;'-DDF., o,p'-
DDI. TDE, /).//-DDT, telodrin, isodrin. aldrin, and
heptachlor. The receiving tube was changed and a
150
Pesticides Monitoring Journal
second elution was carried out with 10 ml of a 20:80
(v/v) mixture of ethyl ether-petroleum ether to pro-
duce Eluate B containing /J-BHC. heptachlor epoxide
(about 90 percent), dicldrin, and endrin. The eluates
were concentrated to exactly 1 ml by a gentle stream of
nitrogen at room temp>erature.
To determine a- and fi-endosulfan, a microcolumn con-
taining 2.00 g 60-200-mesh silica gel (Fisher S 661)
activated for 2-3 hours at 140°C was used. The column
was eluted first with 8 ml of a 80:20 (v/v) mixture
of hexane-toluene and next with 8 ml of a 40:60 (v/v)
mixture of hexane-toluene and 8 ml toluene; «- and
/J-endosulfan were present in the second eluate. One-Ml
portions of the concentrated eluates were injected into
the gas chromatographs. Instrument parameters and
operating conditions follow:
(I ) Model 1800 Varian Aerot!raph
Detector:
Column:
Temperatures:
tritium electron-capture
180 cm X 0.3 cm ID Pyrcx. packed with a
mixture of 5 percent OV-210 and 5 percent
OV-17 (4+1) on 80-IO(l-mesh Cliromosorb
W-HP
injection port 205^0
oven 190°C
detector 200°C
nitrogen flowing at 40 ml/minute
Carrier gas
(2) Perkin-Elmer Model F 22 gas chromatograph
Detector:
Column:
Temperatures:
Carrier gas:
"■'Ni electron-capture
40 m X 0..15 mm ID Pyrex capillary, coated
with SE-30 (CiC grade)
injection port 215''C
oven 155°-225°C at 3°C/minutc with
a linear temperature program-
mer
detector 250°C
helium (lowing at 2-3 ml/minute; helium
splitting gas flow of 0-60 ml/minute; nitrogen
purge gas flow of 80 ml/minute
The practical lower limit of detectability was 0.01 ppb.
Recovery data, obtained by spiking river water samples
with the pesticides and carrying them through the entire
analytical procedure, were over 90 percent. Results arc
not corrected for recovery. To confirm the identity of
the pesticides, p-values or chemical conversions were
used, such as the quantitative conversion of o.^'-DDT
and p.p'-DDT to, respectively, o.p'-DDE and p,p'-DDE
by treatment with MgO, the disappearance of dieldrin
and endrin by treatment with concentrated sulfuric acid,
and the peak shift for endosulfan under the influence
of alkali (6).
AROMATIC AMINES
The sums of aromatic amines and their derivatives were
determined colorimetrically (10). Concentrations are
expressed as 3.4-dichloroaniline. The practical lower
limit of detectability was 0.5 ppb.
CHOLINESTERASE INHIBITORS
Colorimetric determination of cholinesterase inhibitors
was performed in a methylene chloride extract of the
sample on an AutoAnalyzcr (^). The enzyme source
was freeze-dried human plasma. Concentrations were
calculated as paraoxon equivalents. The practical lower
limit of detection was 0.2 ppb.
Resutts
The 20,000 data points collected in the monitoring pro-
gram during 1969-75 are summarized in Tables 1-7.
In view of the low frequency of occurrence and the low
concentrations found, the concentrations of p-BHC,
aldrin, heptachlor, heptachlor epoxide, endrin, TDE,
o.p'-UDT. p.p'-DDE, and p.p'-DDT are not given in the
tables. Unless stated otherwise, all extracts of water
samples included silt.
The Rhine River was studied in more detail than the
other Dutch surface waters. Samples were taken weekly
near Lobith at sampling site 45 (Fig. 1). The geo-
graphical distribution of HCB, and o- and t-BHC in
the Rhine River is illustrated in Figures 2-4 for the
southern branch of the river, Rhine-Boven Merwede-
Nieuwe Waterweg.
Discussion
The data in Tables 1-7 indicate that the highest con-
centrations of pesticides and related substances are
found in the Rhine River and its tributaries. The highest
concentrations in the Maas River, compared below, are
much lower.
Residue, ppb
Maas River
0.29
0.07
0.18
0.03
0.09
1.7
2.4
Levels in other waters were lower still or not detected.
HCB and o- and 7-BHC were almost always present in
the Rhine water samples. Median values in ppb varied
during 1969-75 as follows: HCB, 0.06-0.14; a-BHC,
0.06-0.22; and 7-BHC, 0.04-0.13. Concentrations of
the by-product. o-BHC, are higher than those of the
commercial product, 7-BHC. This means cither that
significant amounts of a-BHC-containing products,
which have been banned for years, are still used along
the Rhine or that industry, rather than agriculture, is
the main source of pollution. Because the source of
contamination is located across the German border, it
was not possible to determine the exact source of the
BHC discharge. BHC has had only limited use as a
fungicide. Since July 1974, the concentrations of o-
and 7-BHC in the Rhine have decreased considerably.
Median values of a- and 7-BHC in 1974 were 0.22 ppb
and 0.13 ppb, respectively; in 1975, 0.06 ppb and 0.04
ppb, respectively. The levels of o-BHC in the Rhine
and its tributaries are considered harmful to the repro-
duction of Daplinia magna (water flea) (i).
PliSIIClDF
Rhine River
HCB
0.55
..-BHC
0.60
-BHC
0.42
Dieldrin
0.06
I-ndosulfan
0.81
Cholinesterase inhibitors
56
Aromatic amines
10
Vol. 12, No. 3, December 1978
151
TABLE 1. Concentrations of BHC, dieUiiin. endosidjan, and cholincsterasc inhibitors in Dutch samples, 1969
Residues, ppb
tt-
AND P-
Cholinesterase
»
-BHC
DiELDRIN
Endosulfan
Inhibitors'
TVPLS OI
Water
No. OF
Samples
Sampling Site
No.
Max
Med
Max
Med
Max
Med
Max
Med
Surface water for drinking water
preparation
Braakman
1
raw water
2
—
—
0.01
—
—
—
Berenplaai
2
raw water
4
0.16
0.06
0.01
—
0.03
—
3.02
1.03
Bcrenplaat
2
treated water
4
0.1)2
—
0.01
—
—
—
0.17
0.17
Drentse A
3
raw water
3
—
—
—
—
—
—
Locnerveense Plas
4
raw water
3
—
—
0.01
0.01
—
—
Wantij
6
raw water
3
0.09
0.05
0.01
—
0.11
0.09
5.20
1.82
IJsselmeer, Andijk
7
raw water
4
—
—
0.04
—
0.01
—
IJsselmeer. Andijk
7
treated water
4
—
—
0.04
—
0.0 1
—
Surface water for infiltral
ion
Amsterdam-Rijnkanaal
8
raw water
2
0.112
0.01
—
—
0.17
0.14
1.42
1.06
Amsterdam-Rijnkanaal
8
raw water -
1
—
—
—
—
0.06
0.06
1.20
1.20
Lek
9
raw water
t
0.03
0.02
—
—
0.10
0.09
1.38
1.09
Lek
9
raw water -
1
—
—
—
—
—
—
1.52
1.52
Enschede
10
raw water"
3
0.15
0.02
0.01
—
—
—
0.05
0.05
St. Jansteen
11
raw water
3
—
—
0.02
0.01
—
—
St. Jansteen
U
treated water
1
0.01
0.01
0.03
0.03
0.03
0.03
Valkenburgse Watering
15
raw water
4
0.03
0.02
0.02
—
0.05
—
0.32
0.22
IJsselmeer region
IJsselmeer. Staveren
25
surface water
1
0.03
0.03
—
—
—
—
IJsselmeer. Y-2
27
surface water
1
—
—
—
—
—
—
IJsselmeer. Steile Bank
28
surface water
1
0.02
0.02
—
—
—
—
Maas and tributaries
Maas. Eijsden
35
surface water
7
0.08
0.02
—
—
0.09
—
0.44
0.22
Roer
42
surface water
2
o.o;
0.01
0.01
—
—
—
Niers
43
surface water
3
0,11
0.03
0.02
0.0!
0.13
0.06
0.19
0.18
Rhine and tributaries
Rhine
45
surface water
17
0.24
0.18
0.04
—
0.81
0.24
10.67
2.46
Kromme Rijn
47
surface water
6
0.08
0.02
0.02
—
0.04
—
2.04
1.00
Other surface waters
Ooslermoerse Vaart
57
surface water
4
0.01
—
0.02
—
—
—
Boomawetering
76
surface water
8
0.09
—
0.02
0.01
0.01
—
0.57
0.42
Rijnbeek
82
surface water
4
—
—
0.01
—
—
—
0.52
0.52
Lage Vaart. Colijn
85
surface water
12
0.05
—
0.06
0.01
0.09
—
Hoge Vaart, Colijn
86
surface water
24
0.08
—
0.08
—
0.10
—
Lage Vaart. Wortman
89
surface water
29
11.10
—
0.14
—
0.09
—
Larser Vaart
90
surface water
13
—
—
0.08
0.02
—
—
Wortmanvaart
92
surface water
12
—
—
0.03
0.01
—
—
NOTE: /i-BHC. aldnn. hcptachlor. heptachlor epoxide, endrin. and ZDDT were detected occasionally in low concentrations; — = not detected.
Unless stated otherwise, all water samples included silt.
'As paraoxon-equivalenis.
-After rapid filtration.
'Before infiltration.
152
Pf.sticidis Moniidrinc. Journal
TABLE 2. Concentrations of HCB, BHC, dieldrin. entlosulfan. and choUnc.sterase inhibitors in Dutch water samples, 1970
|M« .
Residues, ppb
^' Hi
„.
and /i-
Chomnesterase
No.
TVPES OF
Water
Sak
PLE
CB
«■
BHC
T-
BHC
DtEL
DRIN
Endosulfan
Inhibitors^
Sampling Site
s Max
Med
Max
Med
Max
Med
Max
Med
Max
Med
Max
Med
Surface water for drinking
water preparation
Braakman
1
raw water
2
0.02
—
0.02
0.01
0.02
0.01
0.02
0.01
0.03
Berenplaat
2
raw water
2
—
—
0,17
0.12
0.09
0.07
0.03
_
0.07
—
0.80
0.30
Drentse A
3
raw water
2
—
—
—
—
0.02
0.01
0.02
0.18
0.06
Loenerveense Plas
4
raw water
1
—
—
—
—
—
—
0.03
Oud-Beijerland
5
raw water
2
0.03
—
0.17
0.12
0.06
0.05
0.01
0.12
1.08
0.83
Oud-Beijerland
5
treated water
2
0.01
—
0.13
0.09
0.07
0.06
0.02
—
0.04
—
0.79
0.50
Wantij
6
raw water
}.
0.08
0.05
0.18
0.15
0.12
0.11
0.04
2.00
0.63
Wantij
6
treated water
2
0.01
—
0.06
0.06
0.05
0.05
0.02
_
(1.03
—
0.45
0.20
IJsselmeer, Andijk
7
raw water
3
—
—
0.02
0.02
0.02
0.01
0.01
0.07
0.27
0.06
IJsselmeer, Andijk
7
treated water
3
—
—
0.02
0.01
0.02
0.01
0.02
—
0.05
—
0.17
0.07
Surface water for infiltration
Amsterdam-Rijnkanaal
8
raw water
3
0.05
0.03
0.13
0.08
0.13
0.08
0.01
0.05
0.82
0.52
Amsterdam-Rijnkanaal
8
raw water -
3
0.03
0.02
0.15
0.10
0.18
0.11
0.01
0.01
0.04
_
0.82
0.42
Lek
9
raw water
3
0.04
0.02
0.16
0.08
0.20
0.10
0.02
0.01
0.07
—
1.10
0.36
Lek
9
raw water -
3
0.03
0.02
0.17
0.10
0.20
0.11
0.01
—
0.05
—
1.05
0.40
Enschede
10
raw water-'
3
—
—
0.50
0.32
0.05
0.02
0.02
0.02
0.05
—
0.07
0.06
Enschede
10
raw water -
3
—
—
0.14
0.12
—
0.01
0.04
St. Jansteen
11
raw water
3
0.01
—
0.01
—
O.OI
0.02
0.03
Valkenburgse Watering
15
raw water
6
—
—
—
—
—
—
0.01
—
0.03
—
0.75
0.34
Groundwater
Bilthoven
18
groundwater
->
—
—
—
—
—
-
-
—
—
—
—
—
Coastal waters
Waddenzee
22
surface water
3
—
—
0.01
-
0.01
—
0.01
-
0.10
-
0.15
0.08
IJsselmeer region
Usselmeer, Y-1
26
surface water
2
0.01
—
0.03
0.02
0.04
0.03
0.01
—
0.05
0.02
0.34
0.21
Kelelmeer. Y-14
31
surface water
1
o.ii:
0.02
0.23
0.23
0.13
0.13
—
—
0.04
0.02
0.63
0.49
Usselmeer, Y-104
34
surface water
2
0.01
—
0.03
0.03
0.04
0.04
0.01
—
0.01
—
0.24
0.22
Maas and tributaries
Maas, Eysden
35
surface water
8
0.04
—
0.03
—
0.06
0.02
0.01
—
0.03
—
0.50
0.22
Roer
42
surface water
5
0.02
—
0.02
0.01
0.05
0.04
0.01
—
0.03
—
0.12
0.06
Niers
43
surface water
6
0.01
—
0.06
o.o:
0.05
0.03
tl.Ol
—
0.04
—
0.11
0.06
Rhine and tributaries
Rhine
45
surface water
51
11.39
0.08
0.26
0.14
0.16
0.08
0.04
_
0.40
0.03
4.01
0.72
Kromme Rijn
47
surface water
6
0.02
—
0.15
0.05
0.11
0.05
0.03
—
0.03
—
2.08
0.40
Other surface waters
Ruilen A
52
surface water
5
0.01
—
—
—
—
—
0.01
—
0.02
—
0.10
0.05
Overijsselse Vecht
60
surface water
4
—
—
—
—
—
—
0.01
—
0.03
—
0.09
—
ditch. A.Paulowna
68
surface water
5
—
—
0.01
—
—
—
0.02
0.01
—
—
0.33
0.10
ditch, HiUegom
69
surface water
2
—
—
0.0.1
0.02
0.01
—
_
—
—
—
0.22
0.18
ditch, Hillegom
70
surface water
2
—
—
0.04
0.02
0.01
—
0.04
0.04
—
—
0.37
0.18
ditch, Hillegom
71
surface water
2
—
—
0.01
—
—
—
—
—
—
—
0.34
0.17
ditch, Hoogeveen
72
surface water
2
—
—
—
—
—
—
0.02
0.01
—
—
0.32
0.22
Leidse Vaart, Lisse
73
surface water
2
—
—
—
—
0.02
0.02
0.03
0.02
—
—
0.26
0.16
ditch. Noordwijkerhout
74
surface water
2
0.01
—
—
—
—
—
0.08
0.06
—
—
0.21
0.10
leidse Vaart, Dc Zilk
75
surface water
t
—
_
0.01
—
0.05
0.02
0.04
0.03
—
—
0.22
0.16
Boomawetering
76
surface water
5
—
0.03
0.01
0.04
0.02
0.03
—
0,15
0.01
0.40
0.12
Rijnbeek
82
surface water
6
D.MI
_
0.02
—
0.03
0.01
0.01
—
0.05
0.03
0.53
0.10
Lage Vaart, Colijn
85
surface water
5
—
—
0.02
0.01
0.02
0.01
0.02
0.01
0.02
—
0.23
0.06
Hoge Vaart, Colijn
86
surface water
5
tl.Ol
—
0.06
0(>2
0.04
0.02
0.02
0.01
0.02
0.01
0.24
Lage Vaart, De Block
van KufTeler
87
surface water
5
0.04
_
0.02
0.01
0.03
0.02
0.03
0.01
0.04
—
0.1 1
0.05
ditch, N.O. polder
91
surface water
1
—
_
_
—
—
—
0.07
0.07
0.07
0.07
0.14
0.14
Wortman
92
surface water
5
0.01
0.01
0.03
0.02
0.03
0.03
0.01
—
0.03
—
0.13
0.12
NOTE: See NOTE. Table 1.
'As paraoxon-equivalents.
-After rapid tiltralion.
'Before intiltralion.
Vol. 12, No. 3, December 1978
153
TABLE 3. Concvntralions of HCB, BHC, tlieUlrin. ciuiosiilfan, and cholinesterasc inhibitors in Dutch water samples, 1971
Residues, ppb
Sampling She
Types of
No. Water
No. OF
Sam-
ples
HCB
re-BHC
-BHC
DiELDRIN
n- AND ff- CHOLINESTERASE
Endosulfan Inhibitors'
Max Med Max Mf.d Max
Med
Max Med Max Med
Max Med
Surface water for ilrinkinti water preparation
IJsselmeer 7 raw water
Surface water for infiUration
Enschede 10
Enschede 10
Valkenburgsc Waterinp 15
Groundwater
Bilihovcn 18
Haarlem l")
Hillcgom 21)
IJsselmeer region
Ketelmecr, Y-14 .11
Kelelhaven 32
Maas and tributaries
Maas. Eysden }5
Maas, Urmond 36
Maas. Maasbracht 37
Maas. Kessel 38
Rocr 42
Niers 43
Rhine and tributaries
Rhine
raw water -
raw water''
raw water
12 0.01
5 —
5 —
6 0.01
groimdwater 1
groundwater 1
groundwater I
surface water
surface water
surface water
surface water
surface water
surface water
surface water
surface water
Other surface waters
Winschoterdiep 51 surface water 5
Bagniolenbeek 58 surface water I
Regge 63 surface water 3
Twentekanaal, Almelo 64 surface water 3
Twentekanaal, bovenpand 65 surface water 3
Lage Vaart, Colijn 85 surface water 6
Hoge Vaart, Colijn 86 surface water 6
Lage Vaart, Wortman 89 surface water 6
11.13
0.15
0.38
0.02
0.06
0.06
0.20
0.03
11.02
0.03
0.01
0.02
0.03
0.02"
0.03
0.02
0.01
11.01
0.03
U.05
11.02
0.01
0.01
0.01
0.01
45 surface water 52 0.52
0.02
0.01
0.01
0.14
0.13
0.18
0.01
0.05
0.12
0.01
0.01 0,01
0.01 —
0.02 0.01
0,08 0.02
0.48
— 0.06
0.16
0.06
0.10
0.14
0.03
0.01
0.12
I). 1 3
0.02
0.03
0.34
0.03
0.06
0.01
11,01
O.OI
0.02
0.03 0.01
0.06 —
0.03
0.05
0.02
0.03
0.02
0.06
0.06
0.04
0.01
0.02
0.01
0,04
0.01 —
0.07
0.02
0.02
0,25
0.02 — —
0.01
0.01
0.01
0.01
—
0.02
0.13
0.10
0.211
0.01
—
0.04
0.01
0.02
0.01
0.02
O.OS
0.04
0,05
0.04
0.02
0.03
0.02
U.02
0,01
0.04
0.02 — —
0.03
0.20
1.18
0,08
0.40
0,40
0,19
1.26
0,33
0,25
0.08
0,08
OM
0.20
—
0,18
—
0.12
0,08
0.08
0,08
2.00 0.16
0.56
0.12
0.74
0.38
0.14
0.12
0,50
OM
0,40
0.09
-0,46
0.23
0.32
—
NOTE: See NOTE. Table 1.
'As paraoxon-eqiiivalenls.
-Before infiltration.
^After rapid filtration.
154
Pesticidrs M0NITOKIN6 Journal
TABLE 4. Concentrations of HCB, BHC, dieUrin, endosulfan, and cholinesterase inhibitors in Dutch water samples, 1972
Residues, ppb
Sampling Site
No.
No. OF
Types of Sam-
Water PLEs Max
HCB
tt-BHC
V-BHC
DiELDRIN
o- AND P- Cholinesterase
Endosulfan Inhibitors i
Med Max Med Max Med Max Med Max Med Max
Meo
Surface water for drinking water preparation
Usselmeer, Andijlc 7 raw water
Surface water for infiltration
Enschede 10
Enschede 10
Valkenburgse Watering 15
12 0.01
0.05 0.02 0.04 0.02
0.05
0.01 —
raw water"
6
0.01
—
0.17
0.10
0.02
0.02
0.05
raw water '
6
0.01
—
0.09
0.06
0.01
0.01
raw water
9
0.03
—
0.04
0.02
0.03
0.02
0.02
—
0.44 0.24
— 3.52
0.76
Rainwater
Bilthoven
17
rainwater
8
0.01
—
0.50
0.02
0.06
0.02
0.01
Usselmeer region
Usselmeer, Y-2
27
surface water
11
0.01
—
0.05
0.02
0.05
0.03
0.02
Usselmeer, Y-2
27
surface water^
4
0.03
—
0.04
0.03
0.03
0.02
0.02
Usselmeer, Y-10
29
surface water
11
0.05
—
0.25
0.03
0.20
0.03
0.03
Usselmeer, Y-10
29
surface water s
4
0.02
0.01
0.24
0.06
0.20
0.05
0.02
Usselmeer, Y-12
30
surface water
11
0.20
0.01
0.20
0.07
0.20
0.05
0.02
Usselmeer, Y-12
30
surface water ^
4
0.03
0.01
0.12
0.12
0.13
0.08
0.04
Ketelhaven
32
surface water
11
0.08
0.04
0.20
0.12
0.22
0.10
0.02
Ketelhaven
32
surface water ^
4
0.04
—
0.16
0.09
0.19
0.14
0.02
Usselmeer, Y-20
33
surface water
11
0.06
0.01
0.08
0.02
0.08
0.03
0.03
Usselmeer, Y-20
33
surface water ^
4
0.01
—
0.02
0.02
0.03
0.02
0.05
Maas and tributaries
Maas, Eijsden
35
surface water
11
0.03
0.01
0.07
0.01
0.07
0.02
0.01
Maas, Grave
39
surface water
12
0.02
—
0.08
0.01
0.13
0.02
0.01
Maas, Keizersveer
41
surface water
12
0.01
0.06
0.01
0.18
0.02
0.02
Roer
42
surface water
12
0.01
_
0.09
0.04
0.02
0.02
Niers
43
surface water
12
0.08
0.0 1
0.15
0.08
0.06
0.04
0.08
Dieze
44
surface water
10
0.05
—
0.06
0.01
0.07
0.03
0.02
Rhine and tributaries
Rhine
45
surface water
52
0.37
0.13
0.57
0.16
0.28
0.11
0.02
Other surface waters
Zuidlaardermeer
53
surface water
6
0.01
—
0.01
—
0.01
—
0.01
Lauwersmeer
54
surface water
6
0.03
—
0.01
—
0.01
—
O.OI
Van Starkenborghkanaal
55
surface water
6
0.03
—
0.02
—
0.02
0.01
0.01
Meppelerdiep
56
surface water
6
0.02
—
0.02
—
0.02
—
0.01
Regge. bovenloop
61
surface water
3
Regge, benedenloop
62
surface water
3
0.02
0.02
0.11
0.06
0.05
0.04
0.01
Twentekanaal, bovenpand
65
surface water
2
—
—
0.44
0.22
0.02
0.01
0.01
Eem
66
surface water
6
0.01
—
0.08
0.05
0.06
0.04
0.01
Vecht
67
surface water
6
0.01
—
0.06
0.03
0.05
0.02
—
Lage Vaart, Colljn
85
surface water
7
0.01
—
0.01
—
0.02
0.01
0.03
Hoge Vaart, Coliin
86
surface water
7
0.01
—
0.08
0.02
0.09
0.01
0.01
Lage Vaart, De Block
van Kuffeler
87
surface water
7
0.03
—
0.01
—
0.02
—
—
Hoge Vaart, De Block
van Kuffeler
88
surface water
7
0.01
—
0.03
0.01
0.04
0.02
0.01
Lage Vaart, Wortman
89
surface water
7
0.01
—
0.01
0.01
0.02
0.02
O.OI
0.02
0.02 —
0.01
O.OI
0.01
0.09
0.02
— 0.03
0.42
0.13
1.10
0.25
2.44
0.48
1.18
0.76
1.94
0.17
0.44
0.14
—
0.16
0.07
0.50
—
0.12
—
0.32
0.14
2.36
0.73
0.12
—
—
0.22
0.07
O.U
—
0.06
—
1.72
0.17
0.64
0.06
0.06
—
0.52
0.06
0.14
0.36
NOTE: See NOTE, Table 1.
lAs paraoxon-equivalents.
^Before infiltration.
'After rapid filtration.
Vol. 12, No. 3, December 1978
155
TABLE 5. Concentrations of HCB, BHC, dieldrin, endosulfan, and cholinesterase inhibitors in Dutch water samples, 1973-
Residues, ppb
Sampling She
No.
No. OF
Types of Sam-
Water PLES Max
HCB
rt-BHC
7-BHC
Dieldrin
ft- AND /J- Cholinesterase
Endosulfan Inhibitors^
Med Max Med Max Med Max Med Max Med
Max
Med
Surface water for drinking water preparation
Usselmeer. Andijk 7 raw water
9 11. til —
0.10 0.03
0.08 0.03
— 0.01 —
1.10
0.12
Surface water for infiltration
Enschede
10
raw water -
6
—
-
0.09
0.04
—
—
—
-
—
— 1.90
—
Rainwater
Bilthoven
17
rainwater
13
—
—
0.03
0.01
0.05
0.02
0.02
—
—
—
Coastal waters
Bocht van Waium
->l
surface water
3
—
—
0.01
—
0.05
0.01
—
—
—
— 0.06
—
Weslerschelde. Schaar
van Ouden Doel
23
surface water
13
11.03
0.01
0.10
0.01
0.12
0.04
0.01
—
—
— 0.68
0.32
Weslerschelde. Hansweert
24
surface water
13
11.07
—
0.03
—
0.14
0.03
0.01
—
—
— 0.60
0.08
Usselmeer region
Usselmeer, Y-2
27
surface water
12
0.01
—
0.14
0.04
0.13
0.03
—
—
—
— 2.64
0.20
Usselmeer, Y-10
29
surface water
13
U.Ol
—
0.10
0.05
0.06
0.04
—
—
—
— 1.65
0.50
Ketelhaven
32
surface water
11
0.08
0.02
0.23
0.10
0.19
0.09
—
—
0.07
— 5.10
1.88
Maas and iributaries
Maas, Eijsden
35
surface water
13
0.29
0.01
0.02
0.01
0.05
0.01
—
—
0.01
— 1.65
0.06
Maas, Grave
39
surface water
12
0.03
0.01
0.19
0.02
0.12
0.02
—
—
—
- 1.26
—
Maas, Keizersveer
41
surface water
13
0.04
0.01
002
0.01
0.06
0.02
—
—
—
— 1.62
0.06
Roer
42
surface water
1
—
—
Niers
43
surface water
1
—
—
Dieze
44
surface water
1
—
—
Rhine and tributaries
Rhine
45
surface water
52
0.55
0.08
0.45
0.19
0.42
0.12
0.02
—
0.10
— 15.80
2.42
Boven Merwede
48
surface water
24
0.10
0.03
0.36
0.15
0.23
0.11
0,01
—
0.02
— 4.40
1.46
Nieuwe Waterweg
50
surface water
13
0.06
0.02
0.35
0.13
0.21
0.09
0,01
—
11.01
— 4.45
1.24
Other surface waters
Twentekanaal, Almelo
64
surface water
5
—
—
0.03
0.01
0.01
0.01
—
—
0.01
— 0.60
—
Twentekanaal, bovenpand
Roosendaalse Vliet
81
surface water
1
0.01
—
—
—
—
—
—
—
—
— 0.18
0.06
Hoge Vaart. Colijn
86
surface water
6
0.01
—
0.09
—
0.07
—
—
—
0.01
— 1.16
0.25
Hoge Vaart, De Block
van Kuffeler
88
surface water
6
0.01
—
0.02
—
0.01
—
—
—
0.01
— —
—
NOTE: See NOTE, Table 1.
'As paraoxon-eqiiivalents.
-After rapid fiitralion.
156
PEsriciurs Moniiorinc Journal
TABLE 6. Concentrations of HCB, BHC. dicldrin, cndosuljan. cholincsterase inhihitois, and aromatic amines
in Dutch water sample, 1974
Residues, ppb
Sampling Site
Types of
No. Water
HCB
--BHC
DiELDRIN
No. OF
Sam- -
PLES Max Med Max Med Max Med Max Med Max Med Max Med Max Med
7-BHC
ft- AND P- ChOLINESTERASE AROMATIC
Endosulfan Inhibitors^ Amines-
Surface water for drinking water preparation
Enschede 10
Isabella Wctering 12
Pielers v.d.Endevaart 13
canal near Valkenburg 14
Wijde A 16
Rainwater
surface water ' 5
surface water 5
surface water 6
raw water 6
raw water 6
Bilthoven 17 rainwater
0.01 — 0.15 0.07 0.02 —
0.01
—
0.0.1
0.01
0.01
—
0.01
—
0.11
0.06
O.CS
0.04
0.22
0.07
0.09
0.05
0.01
0.08 0.02 0.10 0.04 —
1.32
1.54
0.05
0.26
1.0
1
8 0.5
Coastal waters
Bocht van Watum
21
surface water
5
—
—
0.01
0.01
0.05
0.01
IJsselmeer region
IJsselmeer. Y-10
29
surface water
12
0.01
—
0.12
0.06
0.10
0.04
Ketelhaven
32
surface water
U
0.09
0.04
0.57
0.14
0.26
0.07
Maas and tributaries
Maas, Eijsden
35
surface water
12
0.05
0.01
0.02
0.01
0.04
0.02
Maas, Keizersveer
41
surface water
13
0.02
—
0.03
0.01
0.05
0.02
Rhine and tributaries
Rhine
45
surface water
50
0.39
0.10
0.60
0.22
0.33
0.13
Boven Merwede
48
surface water
12
0.12
0.06
0.55
0.28
0.26
0,12
Hollandse IJssel
49
surface water
6
0.01
—
0.10
0.03
0.05
0.04
Nieuwe Waterweg
50
surface water
11
0.05
0.03
0.36
0.21
0.23
O.Il
Other surface waters
Twentekanaal. bovenpand
65
surface water
7
0.05
2.1
0.58
0.12
0.05
ditch. Ouddorp
78
surface water
6
0.01
—
0.01
—
0.01
—
Gentse Vaart
79
surface water
6
0.01
_
0.01
—
0.02
0.01
Roosendaalse Vliel
81
surface water
6
—
—
0.01
—
0.02
0.01
Zwarle Water 1
83
surface water
6
—
—
0.01
0.01
0.16
0.01
Zwarte Water II
84
surface water
6
—
—
0.09
0.02
0.04
0.02
Hoge Vaart, Colijn
86
surface water
6
0.02
—
0.14
0.01
0.10
—
Hoge Vaart. De Block
van Kuffeler
88
surface water
6
0.01
—
0.02
0.01
0.03
—
— 0.8
0.05
1.36
0.70
4.6
0.8
3.34
0.56
15
3.4
0.50
0.8
1.64
0.12
1.0
—
3.64
1.36
8.6
4.5
3.36
0.79
16
3.8
1.16
0.09
1.0
0.6
2.40
0.60
5.8
2.6
0.83
1.60
—
3.7
—
0.12
—
0.7
—
0.05
—
—
—
0.10
—
8.1
—
—
—
3.0
0.6
0.58
—
4.4
0.7
— — I.O
NOTE: See NOTE. Table I.
'As paraoxon-equivalents.
-As 3.4-dichloroaniline-equivalents.
■■'Before infiltration.
TABLE 7. Concentrations of HCB, BHC, dicldrin, endosulfan, cholincsterase inhibitors, and aromatic amines
in Dutch water samples, 1975
Sampling Site
No.
Types of
Water
Residues, ppb
HCB
ft-BHC
7-BHC
DiELDRIN
ft- and /?- cholinesterase aromatic
Endosulfan Inhibitors' Amines^
No. of
Sam- _
PLES Max Med Max Med Max Med Max Med Max Med Max Med Max Med
Rainwater
Bilthoven 17 rainwater
10 0.01
0.03 0.02 0.04 0.03 —
Maas and tributaries
Maas, Eijsden 35
Maas, Lith 40
Rhine and tributaries
Rhine 45
IJssel 46
Boven Merwede 48
Nieuwe Walerweg 50
Other surface waters
Overijsselse Vecht 59
Twentekanaal, Almelo 64
Twentekanaal, bovenpand 65
polder ditch 77
Cirole Kreck 80
Zwarle Water I 83
Zwarte Water II 84
surface water 13
surface water 13
surface water
surface water
surface water
surface water
surface water
surface water
surface water
surface water
surface water
surface water
surface water
0.02
0.02
0.21
0.06
0.10
0.02
0.01
0.08
0.06
0.03
0.03
O.OI
0.01
0.03
0.21
0.09
0.13
0.09
0.01 0.03 0.02
O.OI 0.07 0.02
0.06 0.14 0,04
0.03 0.06 0.03
0.05 0.07 0.03
0.04 0.09 0.03
0.06
0.04
0.04
0.02
1.40
0.47
0.04
0.04
0.02
—
0.01
—
0.02
0.01
0.02
O.OI
0.01
—
0.O2
O.OI
0.30
0.04
0.09
0.02
0.02
0.02
NOTE: See NOTE. Table 1.
'As paraoxon-equivalents.
-As 3,4-dichloroaniline-equivalenls.
0.44
—
1.5
0.6
0.18
—
2.4
0.7
56.0
7.80
10
3.7
21.0
8.70
14
2.8
18.0
7.20
9.5
3.8
10.0
6.00
4.0
2.6
0.12
0.04
—
1.9
0.7
2.10
—
1.0
0.6
—
—
0.5
—
0.34
—
0.7
1.4
6.8
—
0.14
—
2.3
Vol. 12, No. 3, December 1978
157
concentration (/jg/l)
05
Oi
03
02
1973
197i
SITE SAMPLED
Rhine (45)
Boven Merwede (i8)
Nieuwe Waterweg (50)
1975
J fmannj j aso nd j fmami j asond j fmamj j asond
month
FIGURE 2. Concentrations of HCB in the southern region of the Rhine River {sites 45, 48, and 50 in Fij>. I)
High concentrations of a-BHC were also found in the
Twentekanaal. The source of the contamination was a
chemical plant which produces 7-BHC. The a-BHC, a
worthless by-product of the synthesis of 7-BHC, was
dumped beside the canal. Removal of the dumped
material led to a gradual decrease of concentrations in
the canal and in drinking water removed from canal
water.
Concentrations of HCB have also decreased, but grad-
ually and less drastically (Figs. 2^). HCB is a low-
polarity compound which is volatile with water and
readily adsorbed by the solid particles which settle in
fluvial transport.
Concentrations of cholinestcrase inhibitors have grad-
ually increased since 1972 and significantly in 1975.
Concentrations of a- and P-endosulfan have decreased
greatly following the first sensational wave in June-July
1969 (9) and a second, less important one in autumn
of the same year.
In Table 8, maximum and median or mean concentra-
tions of a-BHC, 7-BHC, :i;BHC, dieldrin, 2DDT, and
DDE from nine nations are summarized (/, 2, 4, 12-
23). Levels of a- and 7-BHC, i;BHC, dieldrin, 2DDT,
and DDE in Dutch surface waters arc of the same order
of magnitude as are the concentrations in other indus-
trialized countries. Concentrations of aromatic amines
are comparable in Dutch and German parts of the Rhine
River (II).
158
Pesticides Monitoring Journal
SITE SAMPLED
Rhine
(45)
concentration (yug/l)
05
Boven Merwede (^8)
Nieuwe Waterweg (50)
FIGURE 3. Concentrations of a-BHC in the southern region of the Rhine River (sites 45, 48, and 50 in Fig. 1)
Vol. 12, No. 3, December 1978
159
concentration (/jg/l
05-
SITE SAMPLED
Rhine (45)
Boven Merwede (48)
Nieuwe Waterweg (50)
FIGURE 4. Concentrations of y-BHC in the southern region of the Rhine River (sites 45, 48, and 50 in Fig. J)
160
Pesticides Monitoring Journal
TABLE 8. Concentrations of organochlorine pesticides in worldwide surface waters, 1968-75
No.
OF Types of _
Sites Water
Residues,
PPB
«
-BHC
7
-BHC
2 BHC
DiELDRIN
DDT
DC
>E
Med
Literature
Location
Max Med
Max
Med
Max
Med
Max
Med
Max
Med
Max
References
Brazil
9
surface water
4
<1
<1 <1
Lara and Barreto,
1972 (15)
Canada
3
surface water
—
— 1
—
1
0.04
0.01
■ 0.07
0.01'
0.01
— '
Miles and Harris,
1973 (76)
Czechoslovakia
150
surface water 1971-72
0.52
0.81
0.60
UhnSh et al., 1974
(23)
Federal Republic of
Germany (FRG)
8
surface water 1970
1.90
0.10'
7.10
0.10'
0.04
I
0.25
1
Herzel, 1972 (72)
27
surface water 1971
2.40
0.07'
1.75
0.17'
—
1
0.84
— I
Herzel, 1972 (72)
German Democratic
Republic (GDR)
26
surface water
0.67
0.15
3.2
0.34
0.98
0.15
Engst and Knoll,
1973 (4)
Japan
130
river water 1970-73
3.43
0.20
14.15
0.92
Suzuki et al., 1974
Hungary
4
Balaton Lake 1973
0.04
0.04'
0.01
— '
1
. 1
(21)
P4szlor et al., 1975
(18)
the present report
Netherlands
16
surface water 1969
0.24
1
0.14
1
0.20
_,
0.16
1
26
surface water 1970
0,50
0.03'
0.20
0.05'
0.08
—
0.11
— 1
1
17
surface water 1971
0.48
0.04'
0.34
0.03'
0.06
I
0.11
— 1
1
26
surface water 1972
0.57
0.04'
0.28
0.03'
0.08
1
0.17
— 1
0.15
1
21
surface water 1973
0.45
0.07
0.42
0.04'
0.02
—
0.11
—
0.01
.
17
surface water 1974
0.60
0.17
0.33
0.07
0.06
—
0.04
—
0.01
.
13
surface water 1975
1.40
0U3
0.14
0.03
0.02
—
0.03
—
0.01
United States of
America
1
Utah Lake 1970-71
Mississippi River 1974
-
-
1.3
0.01
-
4.1
Bradshaw et al.,
1972 (1)
Brodlmann, 1976
(2)
6
Iowa Rivers 1968
0.01
—
0.01
—
0.01
—
Johnson and Morris,
1971 (13)
10
Iowa Rivers 1969
0.06
—
0.01
0.01
10
Iowa Rivers 1970
0.06
—
0.02
0.02
1
Des Moines River
Iowa 1971
Iowa 1972
Iowa 1973
0.05
U.04
0.02
0.03
0.01
Kellog and Bulkley,
1976 (14)
10
Iowa rivers 1968
0.01
0.01
0.01
Morris et al.. 1972
(17)
10
Iowa rivers 1969
0.06
0.02
0.01
10
Iowa rivers 1970
0.06
0.02
0.02
10
Iowa rivers 1971
0.04
0.22
0.03
19
surface water 1974
0.07
3.92
Richard et al.,
1975 (19)
20
rivers 1968
rivers 1969
rivers 1970
rivers 1971
0.07
0.04
0.16
0.05
0.03
0.02
0.02
0.01
0.46
0.05
0.09
0.09
O.IO
0.06
0.05
0.08
Schulze et al., 1973
(20)
4
streams 1969
0.33
—
2.50
0.01
0.71
—
Truhlar and Reed,
1975 (22)
4
streams 1970
0.15
—
11.0
0.02
0.21
—
4
streams 1971
—
—
0.12
—
0.05
—
' Mean value.
LITERATURE CITED
( / ) Bradshaw, J. S., E. L. Lovcridge, K. P. Rippee, J. L.
Peterson, D. A. White, J. R. Burton, and D. K. Fuhri-
man. 1972. Seasonal variations in residues of chlori-
nated hydrocarbon pesticides in the water of the Utah
Lake drainage system — 1971) and 1971. Pestic. Monit.
J. 6(3): 166-170.
(2) Brodtmann, N. V., Jr. 1976. Continuous analysis of
chlorinated hydrocarbon pesticides in the lower Mis-
sissippi River. Bull. Environ. Contam. Toxicol. 15( 1 ):
33-39.
U) Canton. //., P. A. Greve, W. SloofJ, and G. J. van
Esch. 1975. Toxicity-, accumulation- and elimination
studies of n-hexachlorocyclohexane (n-HCH) with
fresh water organisms of different trophic levels.
Water Res. 9( 12) : 1 163-1 169.
(4) Engst, R.. and R. Knoll. 197?. Contamination of sur-
face water, rain water, and drinking water with chlori-
nated hydrocarbons. Die Nahrung 17(8) :837-851.
(5 I Fritschi. G., P. A. Greve, H. KnssmanI, and R. C. C.
Wegnian. 1978. Cholinesterase inhibitors in the Rhine
river. Organic compounds in the environment. Deter-
mination, significance, decrease. Erich Schmidt Press,
Berlin, pp. 265-270.
(6) Greve, P. A., and S. L. Wit. 1971. Endosulfan in the
Rhine river. J. Water Pollut. Contr. Fed. 43(12):
2338-2348.
(7) Greve, P. A. 1971. Toxic substances in water: Occur-
rence and significance. H2O 4( 12):272-275.
(5) Greve, P. A., J. Frendenthal, and S. L. Wit. 1972.
Potentially hazardous substances in surface waters.
Vol. 12, No. 3, December 1978
161
Part II. Cholinesterase inhibitors in Dutch surface
water. Sci. Total Environ. l(3):253-265.
(9) Grcve, P. A. 1972. Potentially hazardous substances in
surface waters. Part I: Pesticides in the river Rhine.
Sci. Total Environ. 1(2) : 173-180.
{10) Greve, P. A., and R. C. C. Wegman. 1975. Determi-
nation and significance of aromatic amines and their
derivatives in Dutch surface waters. Schr. Reihe Ver.
Wasser-, Boden-, und Lufthyg., Berlin-Dahlem 46(1):
59-80.
(//) Hegazi, M. 1977. Analysis and fate of urea herbicides
and their metabolites on bankfiltration, drinking water
and soil passage. Thesis. Bonn.
(12) Herzcl. F. 1972. Organochlorine insecticides in surface
waters in Germany — 1970 and 1971. Pestic. Monit. J.
6(3):179-187.
(li) Johnson, L. G., and R. L. Morris. 1971. Chlorinated
hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J.
4(4):216-2I9.
(14) Kellogg. R. L.. and R. V. Bulktey. 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.
(15) Lara. W. H., and H. H. C. Barreto. 1972. Chlorinated
pesticides in water. Rev. Inst. Adolfo Luti'. 32(1):
69-74.
(16) Miles. J. R. W., and C. R. Harris. 1973. Organochlu
rine insecticide residues in streams draining agricul-
tural, urban-agricultural, and resort areas of Ontario,
Canada— 1971. Pestic. Monit. J. 6(4) :363-368.
(17) Morris, R. L., L. G. Johnson, and D. W. Ehert. 1972.
Pesticides and heavy metals in the aquatic environ-
ment. Health Lab. Sci. 9(2): 145-151,
(18) Pdsztor, Z., J. E. Ponyi, A. Holld. and L. Gonezy.
1975. Investigations by gas chromatograph on the
chlorinated hydrocarbon pollution in two areas of
Lake Balaton. Annal. Biol. Tihany 42(2) : 191-202.
(19) Richard, J. J., G. A. Junk, M. J. Avery, N. L. Nehring,
J. S. Fritz, and H. J. Svec. 1975. Analysis of various
Iowa waters for selected pesticides: atrazine, DDE,
and dieldrin— 1974. Pestic. Monit. J. 9(3) : 1 17-123.
(20) Schulze, J. A., D. B. Manigold, and F. L. Andrews.
1973. Pesticides in selected western streams — 1968-71.
Pestic. Monit. J. 7(l):73-84.
(21) Suzuki, M., Y. Yamalo, and T. Akiyama. 1974. BHC
( 1,2,3,4,5,6-hexachlorocyclohexane) residue concen-
trations and their seasonal variation in aquatic envi-
ronments in the Kitakyushi district, Japan 1970-1973.
Water Res. 8(9) :643-649.
(22) Truhtar, J. F., and L. A. Reed. 1975. Occurrence of
pesticide residues in four streams draining different
land-use areas in Pennsylvania, U.S. Geological Sur-
vey, Water Resource Investigations 6-75.
(23) Uhndk, J., M. Sackmauerovd, A. Szokolay, and O.
Pal'Usovd. 1974. TTie use of an electron-capture detec-
tor for the determination of pesticides in water. J
Chrcmatogr. 91:545-547.
162
Pesticides Monitoring Journal
BRIEF
Organochlorine Pesticide Levels in Ottawa Drinking Water, 1976
David T. Williams, Frank M. Benoit, Edward E. McNeil, and Rein Otson'
ABSTRACT
Duplicate samples of Ottawa drinking ttaler were collectetl
once a month dnrini; 1976 and analyzed for organochlorine
pesticides. The samples were analyzed hy gas chromatog-
raphy-mass spectrometry, and pesticides were identified hy
comparing their retention times, coupled with selected ion
monitoring, with those of known standards. The pesticides
detected and their mean concentrations in parts per trillion
were aldrin (0.9), heptachlor epoxide 13), heplachlor (0.6),
n-BHC (6). y-BHC (3). endrin (4), dieldrin (I). o,p'-TDE (I).
o,p' -DDT (3). and o,p'-DDE (0.2).
Introduction
Ottawa drinking water was monitored for organochlorine
pesticides by a simple new method using Amberlite
XAD-2 macroreticular resin for the analysis of potable
water at the parts per trillion (ppt) level.
Sampling and A nalysis
In 1976, duplicate 200-liter samples per month, except
July, of Ottawa drinking water was passed through
Amberlite XAD-2 macroreticular resin during a 10-day
period according to the procedure of McNeil et al. (/).
The resin was eluted with 250 ml hexane, and the
eluates were dried with sodium sulfate and concentrated
to 1 ml. The concentrated hexane eluates were then
analyzed with a Finnigan Model 4000 gas chromato-
graph-mass spectrometer coupled to a Model 6000 Data
System with the following instrument parameters and
operating conditions:
Column: 1.8 m X 2 mm ID glass, packed with 3 per-
cent OV-17 on 8()-10n-mesh Chromosorb 750
Temperatvires: oven from 200°C (0.1 minute hold) to 250°C
(hold) at 5°C/minute; injection port 225°C
Carrier gas: helium flowing at 25 ml/minute
The mass spectrometer, operating in the selected ion
mode, was programmed to monitor four ions (m/q 66,
81, 100, 109) for the first 4 minutes and four other ions
(m/q 67, 79, 235, 246) for 10 minutes more. Analyses
were performed on a standard pesticide mixture, includ-
ing the 10 pesticides detected under identical GC-MS
conditions to permit identification and quantitation. The
lower limit of detection was about 0.1 ppt of pesticide
in the original 200-liter water sample.
Results and Discussion
Results of the pesticide analyses are presented in con-
densed form in Table 1, including the relative retention
time and specific ion monitored for each pesticide.
There was no consistent seasonal trend for any of the
10 pesticides detected. The monthly pesticide values
varied considerably with the mean as shown by the high
standard deviations in Table 1. This is expected since
the levels of many of the pesticides were close to the
detection limit, and the use of selected ion monitoring,
although more selective than simple gas chromatography,
is still subject to interference, particularly at the trace
levels found.
Authors concluded that organochlorine pesticides de-
tected in Ottawa drinking water exist as background
levels which are consistently present in trace amounts in
the environment.
TABLE 1. Organochlorine pesticide residue levels
in Ottawa drinking water, 1976
SElIiCTED
Relative
Range
Mean
Ion
Retention
MIN.-MAX..
It
Pesticide
Monitored
Time
PP1
Std Dev.
Median
..-BHC
109
1.00
0.1-15
6±4
6
V-BHC
109
1.30
0.4-11
3±3
2
Heptachlor
100
1.63
0.1-1
0.6±0.3
0.7
Aldrin
66
1,97
0.1-6
0.9±1
0.5
Heptachlor
epoxide
81
2.70
0.2-9
3±3
1
o.p'-DDE
246
3.72
0.1-0.5
0.2±0.2
0.2
Dieldrin
79
3.77
0.1-4
1±1
0.7
(),/)'-TDE
235
4.17
0,1-3
1±I
O.g
Endrin
67
4.35
1-7
4±4
4
o.p'-DDT
2.35
4.72
0.2-8
3±3
2
' Bureau of Chemical Hazards, Environmental Health Directorate,
Health and Welfare Canada, Ottawa, Ontario, Canada KIA OL2.
LITERATURE CITED
(/) McNeil, E. £,, R. Otson, W. F. Miles, and F. J. M.
Rajahalee. 1977. Determination of chlorinated pesti-
cides in potable water. J. Chromatogr. 132(2) :277-286.
Vol. 12, No. 3, December 1978
163
APPENDIX
Chemical Names of Compounds Discussed in This Issue
ALDRIN
AROCLOR 1254
AROCLOR 1260
BHC (BENZENE HEXACHLORIDE)
CARBARYL
CHLORDANE
DDE
DDT
DICHLORVOS
DIELDRIN
ENDOSULFAN
ENDRIN
HCB
HEPTAC HIOR
HEPTACHLOR EPOXIDE
ISODRIN
MALATIUON
MIREX
NONACHLOR
PARATHION
PCBs (POrVCHI ORINATED BIPHENYI S)
TDE
TELODRIN
TOXAPHENE
Not less than 95% of 1.2..1.4,lU,IO-hexachloro-1.4,4a.5.8.8a-hexahydro-l,4:5,8-
dimeihanonaphthalene
PCB. approximately 54'^r chlorine
PCB. approximately 60% chlorine
1,2,-^.4.5,6-Hexachlorocyclohexane (mixlure of isomers)
I-Naphlhyl N-methylcarbamate
1 .2.3.4,5.6,7,8,8-Ociachloro-2.3,3a.4.7,7a-hexahydro-4,7-methanoindene. The technical product
is a mixture of several compounds including heptachlor, chlordene. and two isomeric forms
of chlordane.
Dichlorodiphenyl dichloro-ethylene (degradation product of DDT); p.p'-DDE: 1,1-Dichloro-
2.2-bis(/'-chlorophenyl ) ethylene; o.p'-DDE: l,l-Dichloro-2-(o-chIorophenyl)-2-
(p-chlorophenyl) ethylene
Main component (/?./^'-DDT) : <i-Bis(/j-chlorophenyl) /i,/i,/i-trichioroethane
Other isomers are possible and some are present in the commercial product.
o,p'-DDT:U.'.l-Trichloro-2-(tJ-chlorophenyI )-2-(/?-chlorophenyl ) ethane]
2.2-Dichlorovinyl dimethyl phosphate
Not less than 85^^ of l,2.3,4J0,l()-Hexachloro-6.7-epoxy-l,4.4a,5.6.7:8,8a-octahydro-l.4-
e/(£/r>-f:ic(7-5,8-dimeth3nonaphthalene
6,7.8.9.10. l0-Hexachloro-1.5.5a,6,9,9a-hexahydro-6.9-meihano-2.4J-benzodioxalhiepin 3-oxide
Hexachloroepoxyoctahydro-e/irfo. crt^a-dimeihanonaphihalene
Hexachlorobenzene
l,4,5.6,7.8.8-Heptachloro-3a.4,7,7a-tetrahydro-4.7-e/jdo-methanoindene
l,4,5.6.7,8,8-Heptachloro-2.3-epoxy-3a,4.7.7a-telrahydro-4.7-meihanoindanc
Hexachlorohexahydro-c.v^j.p.tw-dimethanonaphthalene
S-l 1 ,2-Bis(ethoxycarbonyl ) eihyll (>,(>-dimclhyI phosphorodilhioale
l,la,2,2.3,3a.4.5,5.5a,5b,6-Dodecachlorooclahydro-1.3.4-mclheno-lH-cyclohula|cdlpcnlalene
l.2,3.4.5,6.7.8-Nonachlor-^a.4.7.7a-te(rahydro-4,7-methanoindan
(>.()-Oiclh\\ 0-/»-nilrophcn> 1 phosphoroihioiiie
Mixtures of chlunn.iicd biphcnvl compounds having; various percentages ot chlorine
2.2-Bis(p-chlorophfnyl )-I , I -dichlorocihane (includinj; isomers anti dehydiochlorinalion
products )
Ocuchlorohcxahydro-4.7-melhanoisobenzofuran
Chlorinated camphenc (67 69'"; chlorine! Product is a mixiiire of poKchlor hicyclic
iLTpencs wiih chloiuKiicd cainplicncs prcdoininaiitit:
164
Pf.str i»i:s Monitoring Journal
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 pesticide monitoring, research, and
other programs concerned with pesticides in the environ-
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and conservation.
Articles are grouped under seven headings. Five follow
the basic environmental components of the National
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People; Pesticide Residues in Wafer; Pesticide Residues
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sixth is a general heading; the seventh encompasses
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Monitoring is defined here as the repeated sampling and
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Authors are responsible for the accuracy and validity
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fied by common or generic names approved by national
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166
Pesticides Monitoring Journal
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Editor
Martha Finan
CONTENTS
Volume 12 March 1979 Number 4
Page
FOOD AND FEED
Acephate and mclhamidophos residue behavior in Florida citrus — 7976 167
Herbert N. Nigg, James A. Reinerl, and Glenn E. Fitzpatrick
FISH, WILDLIFE, AND ESTUARIES
Effects of organochlorine residues on eggshell thickness, reproduction, and population status of brown pelicans
(Pelecanus occidentalis) in South Carolina and Florida, l969-76_ 172
Lawrence J. Blus. Thair G. Lamont, and Burkett S. Neely, Jr.
Pesticide contamination of water rats in the Murrumbidgee irrigation areas. New South Wales, Australia, 1970-72 185
Penny Olsen and Harry Settle
Organochlorine residues in harp seal (Phagophilus groenlandicus) tissues. Gulf of St. Lawrence, 1971 , 1973 189
K. T. Rosewell, D. C. G. Muir, and B. E. Baker
Nationwide residues of organochlorine compounds in starlings (Sturnus vulgaris), 1976 193
Donald H. White
SOILS
Pesticide application and cropping data from 37 states, 1972 — National Soils Monitoring Program 198
Ann E. Carey and Jeanne A. Gowen
Pesticide residue levels in soils and crops from 37 states, 1972 — National Soils Monitoring Program (IV) 209
Ann E. Carey, Jeanne A. Gowen. Han Tai, William G. Mitchell, and G. Bruce Wiersma
Organochlorine pesticide residues in soils from six U.S. Air Force bases, 1975-76 230
Jerry T. Lang, Leopoldo L. Rodriguez, and James M. Livingston
APPENDIX 234
ERRATA 235
ACKNOWLEDGMENTS 236
ANNUAL INDEX (Volume 12, June 1978-March 1979)
Preface 237
Su bject Index . 238
Author Index 246
Information for Conlributom . 248
FOOD AND FEED
Acephate and Methamidophos Residue Behavior in Florida Citrus, 1976
Herbert N. Nigg,= James A. Reinert," and George E. Fitzpatrick'
ABSTRACT
The half-life of acephate and its hydrolysate, methamido-
phos, in the rind of Temple and Valencia oranges, and
grapefruit, lemons, and tangerines was 10.3 days and 10.5
days, respectively. Half-lives of acephate and methamido-
phos in citrus pulp were 15.0 days and 6.1 days, respectively,
based on 7-, 14-, and 21-day data. Seven days after treat-
ment, acephate and methamidophos reached maximum levels
in rind and pulp. Acephate residue levels in rind were less
than 3.0 ppm 14 days after treatment; acephate residues in
pulp were less than 3.0 ppm throughout the experiment.
Methamidophos residue levels averaged less than 0.25 ppm
after 21 days.
Introduction
In 1937, the citrus blackfly, Aleurocanthus woghimi
Ashby (Homoptera: Aleyrodidae), was eradicated from
the Florida Keys by use of petroleum oil (7). Early
in 1976, the citrus blackfly was again discovered in Fort
Lauderdale, Florida, and surrounding Broward County
(8). Infestations are currently found in Broward,
Collier, Dade, Indian River, Martin, Okeechobee, Palm
Beach, and Saint Lucie Counties (G. E. Fitzpatrick,
University of Florida Institute of Food and Agricultural
Sciences, October 1978: personal communication).
After discovery of the infestations, an intensive state
and federally sponsored eradication program was begun,
but it was complicated by the urban nature of the citrus
blackflv infestation.
Based on chemical efficacy and citrus blackfly life-cycle
data, three treatments of acephate at 3-week intervals
were necessary for eradication {8). Treatments were
applied to all Florida citrus owned by individual home-
owners in the heavily urbanized area under an emer-
' Florida Agricultural Experiment Stations Journal Series No. 1148.
Research supported by special funds from tlie Center for Environ-
mental Programs, University of Florida. 21)14 McCarty Hall, Gaines-
ville, FL 32611.
-'University of Florida, Institute of Food and Agricultural Sciences,
Agricultural Research and Education Center, P.O. Box 1088, Lake
Alfred. FL 3.1850.
'University of Florida. Institute of Food and Agricultural Sciences,
Agricultural Research Center, 3205 S.W. 70th Avenue, Fort Lauder-
dale, FL 33314.
gency exemption granted by the United States Environ-
mental Protection Agency (EPA). The homeowner was
advised by the Florida and U.S. Departments of Agri-
culture to wait 7 days before consuming treated fruit.
It was not known whether acephate and its environ-
mental metabolite, methamidophos (Monitor), would
reach their respective action levels of 3.0 ppm and 0.25
ppm in whole fruit within 7 days. In addition, acephate
and methamidophos are systemic chemicals and might
readily penetrate fruit rind into the edible pulp.
The purpose of the present study was to monitor levels
of acephate and methamidophos in common Florida
citrus to determine half-lives and tolerances of these
materials.
Materials and Methods
Each experimental unit consisted of one city block.
Within each city block, a random 8-fruit sample was
taken from 3-10 trees of Temple and Valencia oranges,
and grapefruit, lemons, and tangerines on each sample
date. Treatments were replicated four times in a
completely random design including four unsprayed
check blocks. Acephate at 0.6 g active ingredient (AI)/
liter (ca 38 liters/tree) was applied with a hydraulic
sprayer at 29 kg/ cm- and with a mist blower at 2.4 g
Al/liter (ca 0.8 liter/tree). The hydraulic sprayer was
a standard, truck-mounted unit with two 100-m hoses
and attached handheld sprayguns. The mist blower was
a gasoline-driven backpack unit (KWH Whirlwind, Hol-
land). Three separate treatments were applied at 3-week
intervals. Dual samples of each variety were taken after
the third application on days 1, 3, 5, and 7, and single
samples of each variety were taken on days 14 and 21
by clipping the fruit into plastic bags. Each sample
consisted of eight fruits. One set of the dual samples
was washed in a weak soap solution of Ivory liquid to
simulate homeowner washing. Samples were frozen at
-20'C and transported frozen to the laboratory for
analysis.
Vol. 12, No. 4, March 1979
167
Samples were stored approximately one month at
— lO'C prior to analysis. Valencia oranges were 0.8
mature when harvested; other varieties were completely
mature.
The method of I.cary (4) was modified for extraction
and analyses of acephate and mcthamidophos. Fruits
were thawed, the rind was removed from one half of
each fruit, and the pulp was sliced into a Waring blender.
The pulp was blended for ?• minutes, and a 10-g sub-
sample was removed for analysis. The rind was diced,
blended for 3 minutes, and a 10-g subsample was taken
for analysis. Separate fruit knives were used for all
operations, and between samples all equipment was
washed thoroughly with hot soapy water, rinsed in tap
water, deionized water, isopropanol, and again in deion-
ized water.
The 10-g sample of either rind or pulp was homogenized
in 100 ml ethyl acetate and 15 g sodium sulfate for
5 minutes in a Sorvall blending cup in an ice bath. The
blender cup top was loosened upon removal from the
mixer, and particulate matter was allowed to settle for
1 minute. A 20-ml aliquot was evaporated to dryness
under a nitrogen atmosphere at 40°C, and transferred
to brown glass bottles over sodium sulfate in 10 ml
methyl isobutyl ketone (MIBK) for gas chromatographic
(GC) analysis. No further cleanup was performed on
the extractions, and they were stored at — ZO^C until
analysis. The elTect of storage on the hydrolysis of
acephate to mcthamidophos was not determined.
For acephate and mcthamidophos, GC was conducted
on a Hewlett-Packard Model 57.^0A gas chromatograph
equipped with dual nitrogen-phosphorus detectors. In-
strument parameters and operating conditions follow:
Column: jilass. M) inches long "'' In-inch ID. packed with
1 percent Reoplex 400 iin «0-KIO-mesh Gas-
Chiom Q
Temperatures. °C; detector 300
injecldr 2U)
program 150-200 at K minute. 8-minute final
hold. 45-second delav alter injection
Carrier gas: helium llowing at 30 ml minute
Compounds were quantified by comparing peak heights
of standard materials chromatographed at the same at-
tenuation. Unsprayed fruit extracts fortified with stand-
ard acephate and mcthamidophos (Chevron Chemical
Co., Richmond, Virginia) were linear at each GC at-
tenuation setting. However, at the attenuation setting
of 8, standard materials chromatographed in MIBK.
alone produced a 10-20 percent lower response than in
fortified fruit extracts. Fruit extracts alone were blank,
apparently as a result of an unexpected synergistic efiect
of some component in the fruit extract on the nitrogen-
phosphorus detector response. Consequently, fruit ex-
tracts fortified with acephate and mcthamidophos were
used for quantification. Standards were chromato-
graphed every fourth injection. All injections were 5 fd.
All solvents were assessed for interferences by evapo-
rating 100 ml of each solvent to 1 ml and chromato-
graphing 5 mI.
Recoveries of standard materials from fortified homo-
genates were 7.^.1 percent mcthamidophos and 77.8 per-
cent acephate at 1 ppm and 82.6 percent mcthami-
dophos and 85.4 percent acephate at 5 ppm for both
peel and pulp. There were no varietal differences in
recovery of standard materials. Variations in recovery
averaged 16.8 percent for mcthamidophos and 15.3 per-
cent for acephate at 1 ppm and 4.6 percent for mcth-
amidophos and 5.5 percent for acephate at 5 ppm. Low-
est accurate level of detection for both standards was
0.01 ppm; lower levels are reported as trace. The data
in Tables 1 and 2 are not corrected for recovery. No
analyses were performed on either the formulated ace-
phate or tank mixes. The equation for decay was:
-/)/
ln(y ly ) = —bt
Half-life, / , was calculated as
t = In(0.5)/(— /))
(1)
(2)
(3)
Residue levels were compared among varieties on indi-
vidual sampling davs and among sampling davs for indi-
vidual varieties with a t-test (/O). Degrees of freedom
were 14 for da^s 1-7 and 6 for days 14 and 21
f^// = 2(« — 1)] (/O). Comparison of residue levels
are significant at the 0.01 level.
Results and Discussion
There was no statistical difference between residues of
acephate and mcthamidophos on or in washed and un-
TABLF. 1. Acepliate residues in rind and pulp
of Florida citrus, 1976
Day, Post Application
14
21
Residues (Mean ± Std Dev.), ppm
Temple orange
Rind 2.3 ± 0.7
Pulp 1.3 ±0.5
4.6 ± 1.6
0.8 ± tr
2.8 ±2.8
0.8 ±0.5
7.9 ± 5.8
2.6 ± 1.3
2.6 ± 1.8
1.6 ±0.8
2.0 ± 1.2
1.2 ±2.0
Grapefruit
Rind 2.7 ±2.1
Pulp 0.3 ± 0.2
1.9± I.l
0.4 ± 0.3
2.3 ±2.1
0.4 ± 0.4
3.9 ±2.5
0.9 ± 0.6
1.4 ±0.2
0.5 ± Ir
1.9 ±0.8
0.3 ± 0.3
\';ilencia orange
Rind 3.9 ±1.5
Pulp 1.1 ±0.7
3.1 ± 2.5
0.6 ±0.8
4.1 ± 2.8
1.4 ±0.5
4.2 ± 1.5
0.7 ±0.5
1.8 ± 1.2
0.8 ± 0.3
2.1 ± 1.3
1.0 ± 1.0
lemon
Rind 3.8 ±2.2
Pulp 1,5 ±0.7
5.7 ±4.1
1.9 ± 1.0
2.9 ± 1.8
1.0 ±0.6
6.2 ± 2.9
2.4 ± 1.6
2.6 ± 1.8
1.3 ± 1.2
1.4± I.O
1.4 ±0.9
Tangerine
Rind 3.8 ± 2.3
Pulp 0.7 ± 0.3
4.9 ± 3.8
2.0 ± 1.3
4.9 ±2.1
1.3 ± 1.1
4.9 ± 1.8
2.0 ± 0.7
2.1 ± 1.2
0.9 ±0.4
4.9 ± 4.6
1.0 ±0.6
NOTF. : tr = trace = <0.01 ppm.
168
Pesticides Monitoring Journal
ACEPHATE IN FLORIDA CITRUS RIND
DAYS POST APPLICATION
ACEPHATE IN FLORIDA CITRUS PULP
• • TEMPLE
o o GRAPEFRUIT
i 4 VALENCIA
-i LEMON
-♦TANGERINE
7 14
DAYS POST APPLICATION
METHAMIDOPHOS IN FLORIDA CITRUS RIND
• — • TEMPLE
o — 0 GRAPEFRUIT
A — t VALENCIA
A — A LEMON
» — » TANGERINE
3 5 7 a
DAYS POST APPLICATION
METHAMIDOPHOS IN FLORIDA CITRUS PULP
A I 2 ppm
• • TEMPLE
o o GRAPEFRUIT
4 1 VALENCIA
A A LEMON
♦ — ♦ TANGERINE
7 14
DAYS POST APPLICATION
FIGURE 1. Acephate and methamidophos residue in rind and pulp of Florida citrus. Points for days 1, 3, 5, and 7 are
averages of eight determinations. Days 14 and 21 are averages of four determinations.
TABLE 2. Methamidophos residues in rind and pulp
of Florida citrus, 1976
Day. Post Application
1 3 5 7 14 21
Residues (Mean ± Std Dev.), ppm
Temple orange
Rind 0.2 ±tr 0.3 ± 0.4 1.3 ± 1.1 1.0 ±0.5 0.2 ±0.1 0.4 ± 0.2
Pulp 0.1 ±lr 0.1 ±tr 0.2 ±0.2 tr 0.2 ±0.1 0.1 ±0.2
Grapefruit
Rind 0.1 ±0.1 0.3 ± 0.2 0.6 ± 0.5 0.5 ± 0.3 0.2 ± 0.1 0.2 ± tr
Pulp ND 0.1 ±0.1 0.1 ±0.2 0.2 ±0.3 0.6 ± tr 0.1 ±0.1
Valencia orange
Rind 0.2 ±0.1 0.3 ± 0.3 1.3 ± 0.6 1.0 ±0.8 0.2 ±0.1 0.2 ±0.1
Pulp 0.1 ±0,2 0.1 ±0.1 0.4 ±0.1 tr 0.1 ± 0.1 0.1 ±0.1
Lemon
Rind 0.1 ±0.1 0.2 ±0.2 0.5 ± 0.3 0.6 ± 0.6 0.2 ±0.1 0.1 ± 0.1
Pulp tr 0,1 ±0.1 0.3 ± 0.6 1.2 ± 1.8 0.1 ± 0.1 0.2 ±0.1
Tangerine
Rind 0.2 ±0.2 0.5 ± 0.4 1.5 ± 1.2 1.5 ± 1.2 0.2 ±0.1 0.6 ± 0.4
Pulp tr 0.2 ±0.2 0.2 ±0.2 0.4 ±0.4 0.1 ± tr 0.1 ±0.1
NOTE: tr = trace = <0.01 ppm.
ND
not detected.
washed fruit (days 1, 3, 5, 7), and data for washed
and unwashed fruit were combined for statistical analy-
ses. This result may be due to the method of handling
samples (i). In the present study, frozen fruits were
thawed before being peeled. Condensation on the fruits
collected in the bottom of the bag; this condensate was
Vol. 12, No. 4, March 1979
not added to the extract because only half of each fruit
was peeled. The fruits were thus washed by condensa-
tion prior to peeling. This accounts for the absence of
statistical difference between washed and unwashed
fruits. The data presented here can only properly be
considered penetrated residues. Also, no residues of
acephate or methamidophos were detected in fruit which
had been misted. Only the results of the hydraulic ap-
plication are reported here.
Both acephate and methamidophos are systemic insec-
ticides, and the data in Figure 1 indicate that at least
acephate readily penetrates the rind of all citrus varie-
ties. Because methamidophos can be produced from
acephate by hydrolysis, internal methamidophos could
have come from acephate.
The peak of penetrated residues of both compounds oc-
curs on days 5 and 7. Acephate residues in rind are
significantly higher (0.01 ppm) on day 7 than on days
5 and 14 for Temple oranges, grapefruit, and lemons.
For Valencia oranges and tangerines, day 14 residues
are significantly lower than are day 7 residues, but due
to the variability of the data, the peak of penetrated
residues may have occurred on day 5 (Table !)• Had
data been taken on day 9, higher methamidophos resi-
169
dues might have been found, indicating additional con-
version of acephate. The data do show, however, that
the residues are above the EPA action levels of 3.0
ppm acephate and 0.25 ppm mcthamidophos on day 7
(Tables 1,2; Fig. 1).
The acephate-in-piilp pattern is similar to that in rind.
Day 7 residues are significantly higher than are residues
on days 5 or 14 in Temple oranges, grapefruit, lemons,
and tangerines. For Valencia oranges, the peak of ace-
phate in pulp may have occurred on day 5 when resi-
dues of acephate were significantly higher than on days
3 or 7. Acephate in pulp was never above the action
level of 3.0 ppm. The maximum level of acephate in
pulp was 2.0 ppm in tangerines on day 14. Most pulp
acephate residues averaged 1.0 ppm or less (Table 1).
The pattern of methamidophos residues was similar to
that of acephate (Table 2). For Temple orange, grape-
fruit, Valencia orange, lemon, and tangerine rind, day 7
residues were significantly higher than were day 14
residues. However, methamidophos levels in rind were
the same on days 5 and 7, so residues may have peaked
on day 5. In pulp, no peak of methamidophos residues
was apparent in Temple oranges, but statistically signifi-
cant peaks occurred on day 7 in lemons and tangerines,
on day 5 in Valencia oranges, and on day 14 in grape-
fruit.
The pattern of penetration of acephate and methami-
dophos in both rind and pulp of these varieties was
statistically significant and consistent. The peak pene-
trated residues of acephate and methamidophos in rind
and in pulp occurred on or before day 7 with decreas-
ing residues thereafter.
The statistical comparison of varieties in Table 3 indi-
cates that by day 14 there are no differences in acephate
residue levels in rind among varieties. Before day 14, no
consistent pattern of residue levels is evident. The same
comparison for acephate in pulp (Table 4) points to
significantly lower residues in grapefruit pulp than in
lemon and tangerine pulp. With this exception, there
were no dillerences in acephate residues in piilp by
TABLE 4. Statistical comparison of acephate residue levels
in citrus pulp, 1976
Day,
Post Application
1
3
5
7
14
21
Temple i)r;inge vs. grapefruit
yes
yes
yes
yes
yes
no
Temple vs. Valencia oranges
no
no
yes
yes
yes
no
Temple orange vs. lemon
no
yes
no
no
no
no
Temple orange vs. tangerine
yes
yes
yes
yes
yes
no
Cirapcfruit vs. Valencia orange
yes
no
yes
no
yes
no
Grapefruit vs. lemon
yes
yes
yes
yes
yes
yes
Grapelruit vs. tangerine
yes
yes
yes
yes
yes
yes
Valencia orange vs. lemon
no
yes
yes
yes
no
no
Valencia orange vs. tangerine
yes
yes
no
yes
no
no
Lemon vs. tangerine
yes
no
no
no
no
no
See NOTE, Table 3.
day 21. Residues in Temple oranges were significantly
higher than were residues in grapefruit until day 21
(Tables 1,4).
By day 14 there were no significant differences in meth-
amidophos levels in rind among varieties, yet dilTer-
ences appear on day 21 (Table 5). There were no
differences in methamidophos residues in pulp by tlay
21 (Table 6).
There is a nonrandom source of variation in the com-
parison of residue levels in citrus which has been noted
in greenhouse tomato studies with acephate, surface
area-to-weight ratios (5).
Confounded with fruit size is varietal rind thickness.
Valencia orange rind thickness has been reported as
4.0 mm (2). 4.1 mm (//), and 3.0 mm (9). Marsh
grapefruit rind thickness has been noted as 5.5 mm
(Jl) and 12.0 mm (9), Lemon rind thickness has been
reported as 7.3 mm (11), 3.6 mm (7), and 5.0 mm
(9). In addition to genetic differences in rind thickness,
many climatic and cultural practices affect rind thick-
ness (7, 2, 9, //). In the present experiment, thick
grapefruit rind with a low surface area-to-weight ratio
appears to account for low pesticide residues in grape-
fruit. Future experiments to compare citrus variety dif-
ferences in residue behavior should include rind thick-
ness and surface area measurements to determine
TABLE 3. Statistical comparison of aceplialc residue levels
in citrus rind, 1976
TABLE 5. Statistical comparison of metliamidophos
residue levels in citrus rind, 1976
Day.
Post Applicat
ION
1
3
5
7
14
21
Temple orange vs. grapefruit
no
yes
no
yes
no
no
Temple vs. Valencia oranges
yes
yes
no
no
no
no
Temple orange vs. lemon
yes
no
no
no
no
no
Temple orange vs. tangerine
yes
no
yes
yes
no
no
Grapefruit vs. Valencia orange
yes
yes
yes
no
no
no
Grapefruit vs. lemon
yes
yes
no
yes
no
no
Grapefruit vs. tangerine
no
yes
yes
no
no
no
Valencia orange vs. lemon
no
yes
no
yes
no
no
Valencia orange vs. tangerine
no
yes
no
no
no
ntj
Lemon vs. tangerine
no
no
yes
yes
no
yes
NOTE: Yes = means arc slaiisticnlly difTcrcnt at O.OI level; no
means arc not statistically dilTcrcnt at U.Ul level {W).
Day. Post Application
3
Temple orange vs. grapefruit yes no yes yes no yes
Temple vs. Valencia oranges no no no no no yes
Temple orange vs. lemon yes no yes yes no yes
Temple orange vs. tangerine no no no yes no no
Grapefruit vs. Valencia orange yes no yes yes no no
Cirapefruit vs. lemon no no no no no yes
Grapefruit vs. tangerine yes yes yes yes no yes
Valencia orange vs. lemon yes no yes yes no no
Valencia orange vs. tangerine no yes no no no yes
Lemon vs. tangerine yes yes yes yes no yes
See NOTE. Table 3.
170
Pesticides Monitoring Journai
TABLE 6. Slalislical comparison of melhamidophos
residue levels in citrus pulp, 1976
TABLE 7. Acepluitc and melhamidophos first-order
disappearance in Florida citrus, 7-21-day data, 1976
Day,
Post Applicat
ION
Slope
(HALF-LIFE, DAYS)
1
3
5
7
14
21
r
Temple orange vs. grapefruit yes
no
no
yes
yes
no
Metha-
ACE-
Metha-
ACE-
Metha-
ACE-
Temple vs. Valencia oranges no
no
yes
no
no
no
MIDOPHOS
PHATE
MIDOPHOS
PHATE
MIDOPHOS
phate
Temple orange vs. lemon yes
no
no
yes
no
no
Temple orange vs. tangerine yes
yes
no
yes
yes
no
Temple orange
Grapefruit vs. Valencia orange yes
no
yes
yes
yes
no
Rind
-0.07
-0.10
9.9
6.9
-0.57 =
-0.94'
Grapefruit vs. lemon yes
no
no
yes
yes
no
Pulp
0.32
-0.06
2.2
11.6
-0.79 =
-0.98»
Grapefiuit vs. tangerine yes
yes
no
yes
yes
no
Grapefruit
Valencia orange vs. lemon yes
Valencia orange vs. tangerine yes
Lemon vs. tangerine no
no
yes
yes
no
yes
no
yes
yes
yes
no
no
no
no
no
no
Rind -0.07
Pulp -0.05
Valencia orange
Rind -0.05
Pulp 0.32
-0.05
-0.08
-0.05
0.03
9.9
13.9
13.9
2.2
13.9
8.7
13.9
23.1
-0.86 =
-0.38
-0.68 =
0.86 ••!
-0.68 =
-0.99'
See NOTE, Table 3.
-0.77 =
0.99 »
whether any differences in
residue
levels cou
d be due
Lemon
Rind
-0.08
-0.11
8.7
6.3
-0.99--
-0.99'
to fruit structure.
Pulp
Tangerine
-0.13
-0.04
5.3
17.3
-0.69 =
-0.81 =
Penetration of both compounds into rind
plicates data analyses. The overall data
and pulp
actually
corn-
show
Rind
Pulp
Averages
-0.07
-0.10
-0.05
9.9
6.9
13.9
-0.45
-0.87 =
-0.79 =
that the appearance of residue is
due
to penetration.
Rind
Pulp
10.5
6.1
10.3
15.0
The fit to a first-order dis
anneara
nee model
is corre-
spondingly poor, ranging from a low of r = 0.02 for
acephate in Valencia pulp to a high of r ^ — 0.79
for acephate in lemon rind. However, when data from
days 7 (ma.\imum concentration), 14, and 21 are used,
disappearance is clearer (Fig. 1).
There are still positive correlations for melhamidophos
in Temple and Valencia orange pulp which reflect an
appearance of the compound in the pulp, and the tan-
gerine rind data for acephate do not fit a first-order
model. Based on 7-, 14-, and 21 -day data the half-life
averages are 10.5 days and 10.3 days for melhami-
dophos and acephate, respectively, in fruit rind, and
6.1 days and 15.0 days for melhamidophos and ace-
phate, respectively, in pulp (Table 7).
The data presented for acephate and melhamidophos
show that both compounds disappear under Florida
conditions after reaching maximum penetrated residues
on day 7. Acephate was below 3 ppm in rind 14 days
after application and never reached 3 ppm in pulp. Pen-
etrated residues of melhamidophos reached an average
level of less than 0.25 ppm 21 days after application.
LITERATURE CITED
(/) Chace, E. A/.. C. P. Wilson, and C. G. Church. 1921.
The composition of California lemons. U.S. Depart-
ment of Agriculture Bulletin No. 993, 18 pp.
(2) Cooper, W. C, A. Peynado, J. R. Furr, R. H. Hilge-
man, C. A. Cahoon, and S. B. Boswell. 1963. Tree
growth and fruil quality of Valencia oranges in rela-
tion to climate. Proc. Amer. Soc. Hon. Sci. 82:180-
192.
'fVi = ln(0.5) /slope.
= Significant at 5 percent level (6).
'Significant at 1 percent level or higher (6),
(J) Gunther, F. A. 1969. Insecticide residues in Califor-
nia citrus fruits and products. Residue Rev. 28:1-127.
(■#) Leary, J. B. 1974. Gas-liquid chromatographic deter-
mination of acephate and Ortho 9006 residues in
crops. J. Assoc. Off, Anal. Chem. 57( 1) : 189-191.
(5) Leidy, R. B.. T. J. Sheets, and K. A. Sorensen. 1978.
Residues of acephate and melhamidophos in green-
houses. L Amer. Soc. Hon. Sci. 103(3) :392-394.
(6) Morrison, D. F. 1967. Multivariate Statistical Methods,
p. 104. McGraw-Hill, New York, N.Y.
(7) Newell. W., and A. C. Brown. 1939. Eradication of
the citrus blackfly in Key West, Fla. J. Econ. Entomol.
32(5):680-682.
(5) Reinert, J. A. 1976. Citrus blackfly control by foliar
treatments of dooryard citrus. Proc. Fla. State Hort.
Soc. 89:365-366.
(9) Reuther, W., and D. Rios-Castano. 1969. Comparison
of growth, maturation, and composition of citrus
fruits in subtropical California and tropical Califor-
nia. Proc. Isl Int. Citrus Symp. 1 :277-300.
(10) Steel, R. G. D., and J. H. Torie. 1960. Principles and
Procedures of Statistics, p. 76. McGraw-Hill, New
York, N.Y.
(//) Turrell, F. M.. S. P. Monselise, and S. W. Austin.
1964. Effect of climatic district and of location in tree
on tenderness and other physical characteristics of
citrus fruit. Bot. Gaz. 125(3) : 158-170.
Vol. 12, No. 4, March 1979
171
FISH, WILDLIFE, AND ESTUARIES
Effects of Organochlorine Residues on Eggshell Thickness, Reproduction,
and Population Status of Brown Pelicans (Pelecanus occidentalis)
in South Carolina and Florida, 1969—76
Lawrence J. Blus,' Thair G. Lamont," and Burkett S. Neely, Jr.'
ABSTRACT
Shells of brown pelican (Pelecanus occidentalis) eggs col-
lected in South Carolina from 1969 through 1975 and in
Florida during 1969, 1970, and 1974 were significantly
thinner (P > 0.05) than eggshells collected before 1947.
Thickness of South Carolina eggshells increased in 1975,
and mean thickness of eggshells collected in Florida during
1974 was greater than that of eggshells collected during 1969
and 1970, primarily in Gulf Coast colonies.
Residues of 13 organochlorines were found in eggs and
tissues of pelicans found dead during 1974 and 1975, al-
though residues in brains of these specimens were not high
enough to cause death. Residues of organochlorines, except
PCBs, declined through 1975. PCBs increased in eggs from
Atlantic Coast colonies.
Reproductive success and population status of brown peli-
cans in South Carolina have improved markedly since
authors began their studies in 1969. Good reproductive
succes'i was reported in 3 of 5 years from 1973 through 1977.
Introduction
This is part of a series of papers on the effects of en-
vironmental pollutants on the brown pelican (Pelecanus
occidentalis). In previous papers, organochlorine resi-
dues in brown pelicans have been related to eggshell
thinning (6. 7), reproductive success (9), adult mor-
tality (5, 10), population decline (4), and possible ex-
tirpation of a population in Louisiana {8). The objective
of the present study is to further explore effects of or-
ganochlorines on brown pelicans, particularly the sig-
'Fish and Wildlik Service. US ncparlmcnt of the Interior. Patuxent
Wildlife Research Center. Laurel. MD 20811. Present address: Pacific
Northwest Field Station, 480 S.W. Airport Road. Corvallis. OR 973.10.
^Fish and Wildlife Service. U.S. Department of the Interior, Patuxent
Wildlife Research Center. Laurel, MI) 20811.
"Fish and Wildlife Service. U.S. Department of the Interior. Division
of Wildlife Refuge, Washington, DC 20240.
nificance of declining residues. Emphasis is placed on
data gathered during 1974-76, but data from 1969 on-
ward are used to show trends over 8 years.
Procedures jar Sampling, Necropsy, and Field Study
Most procedures have been described in previous papers
(4, 10). Brief visits were made to brown pelican colo-
nies in South Carolina in 1969, 1970, and 1976 and
to Florida colonies in 1969, 1970, and 1974. The two
brown pelican nesting colonies in South Carolina,
Deveaux Bank and Marsh Island, Cape Remain Na-
tional Wildlife Refuge (CRNWR), were studied in-
tensively in the spring and summer each year from 1971
through 1975. Censuses were made of total nests and
fledged young in both South Carolina colonies from
1969 through 1976. However, most accurate data were
collected during 1971-75 when a number of visits were
made to each colony during each nesting season. Addled
and viable eggs in all stages of incubation were collected.
One egg was usually taken from each nest selected for
sampling. Eggs were weighed and measured, and their
contents were placed in chemically cleaned glass bottles
and frozen. Eggshells were thoroughly washed with tap
water and allowed to dry. Shell thickness (shell plus
shell membranes) was measured at three sites on the
waist of the egg with a micrometer graduated in units
of 0.01 mm.
Nests with full clutches and nests from which one egg
was collected were marked on Marsh Island to determine
their success. Marked nests were checked for eggs or
young on each visit to the colony; colonies were visited
twice a week for up to 1 hour.
Several dead pelicans and samples of fish regurgitated
by pelicans were collected and fro/en. The pelicans
were removed from the freezer several months later.
172
Pesticides Monitoring .Iournai
thawed, and subsequently necropsied. Tissues for histo-
logical study were fixed in 10 percent formalin, em-
bedded in paraffin, sectioned, and stained. The entire
brain was removed and placed in a chemically cleaned
glass bottle, and the carcass, except for skin, feet, wings,
liver, kidney, and gastrointestinal tract, was wrapped in
foil and refrozen. Brains and carcasses were later ana-
lyzed for organochlorine residues.
A nalytical Procedures
The contents of eggs collected during 1969-71 were
homogenized. A 20-g portion was mixed with anhydrous
sodium sulfate in a blender and extracted for 7 hours
with hexane in a Soxhlet apparatus. The extract was
cleaned by acetonitrile partitioning and was eluted on
partly deactivated Florisil. For pesticide analyses, resi-
dues in the cleaned extract were separated and removed
in four fractions from a silica gel thin-layer plate (17).
Each thin-layer fraction was analyzed by electron-
capture gas chromatography (GC) on a column of 3
percent OV-1 or 3.8 percent UCW-98 on Chromosorb
W-HP. 2DDT in fractions III or IV was confirmed on
a column of 3 f)ercent XE-60 or 3 percent QF-1 Gas-
Chrom Q. Polychlorinated biphenyls (PCBs) were
identified and measured semiquantitatively by thin-layer
chromatography (16). Average recoveries of organo-
chlorine pesticides and their metabolites were 75-112
percent.
Methodology was modified for eggs collected from 1972
to 1975 (11). The extract of the 10-g portion was
cleaned on a Florisil column. Pesticides and PCBs were
separated into three fractions on a Silicar column and
analyzed by GC on a column packed with a mixture of
4 percent SE-30 and 6 percent QF-1. This methodology
enabled authors to detect toxaphene, cw-chlordane,
and/or /ra«i-nonachlor, and c;j-nonachlor. Until 1973,
there was neither a c/.s-nonachlor standard for quantifi-
cation nor a procedure to estimate toxaphene levels.
Lipids were removed from the eggs collected during
1974-75 either by Florisil cleanup or by automated gel
permeation chromatography. In 1974, r/5-chlordane and
/ra;!i-nonachlor were separated and quantified by chang-
ing the column packing to a mixture of 1.5 percent OV-
17 and 1.95 percent QF-1.
Residues in about 10 percent of the samples were con-
firmed by combined gas chromatography-mass spec-
trometry (GC-MS). Average recoveries from spiked
chicken eggs were 81-1 10 percent; residues are not cor-
rected for recovery values. The lower limit of detection
for pesticides or their metabolites was 0.01 Mg/g in fish
and 0.10 Mg/g in other samples (0.01 Mg/g for hexa-
chlorobenzene). The lower limit for PCBs was 0.05
Mg/g in fish and 0.50 Mg/g in other samples.
Results
REPRODUCTIVE SUCCESS AND POPULATION STATUS
From 1969 through 1972 (10) and for previous years
(3), reproductive success of South Carolina pelicans was
below the recruitment standard of 1.2-1.5 fledged young
per breeding female per year that is necessary to main-
tain a stable population (14). Following a successful
reproductive season in 1973, pelicans experienced poor
success in 1974 and 1975, then had successful reproduc-
tive seasons in 1976 (Table 1) and 1977 (Vivian Men-
denhall. Fish and Wildlife Service, U.S. Department of
the Interior, 1977: personal communication).
Except in 1969, reproductive success was higher on
Deveaux Bank than on Marsh Island (Table 1). How-
ever, there was a significant positive correlation
(r = 0.797. P < 0.05) between young fledged per nest
in the two colonies over the 8 years considered in the
present report. Thus reproductive success in one colony
paralleled that in the other colony. Lower reproduction
on Marsh Island was attributed to tidal flooding of nests
each year, a rare occurrence on Deveaux Bank. Many
of the pelicans with flooded nests laid a second clutch,
but replacement clutches also were frequently laid in
low areas that were eventually flooded.
The size of the breeding population of brown pelicans in
South Carolina slowly increased from 1969 through
1974 and then increased 41 percent from 1974 to 1975
as follows: 1,266 pairs in 1969; 1,670 pairs in 1974;
2,400 pairs in 1975; and 3,300 pairs in 1977.
TABLE 1.
Reproductive success of brown pelicans
in South Carolina, 1969-76
No. OF
Young
No. OF
Young
Fledged
Year
Colony
Nests
Pledged
per Nest
1969
Cape Remain
1016
900'
0.821
Deveaux Bank
250'
80
0.321
Both Colonies
1266
980
0.78
1970
Cape Remain
6J7
500'
0.78'
Deveaux Bank
479
445
0.93
Both Colonies
1116
945
0.85
1971
Cape Remain
1094
949
0.87
Deveaux Bank
375
400
1.07
Both Colonies
1469
1349
0.92
1972
Cape Remain
763
514
0.67
lOeveaux Bank
652
456
0.70
Both Colonies
1415
970
0.69
1973
Cape Remain
836
1082
1.29
Deveaux Bank
810
1644
2.03
Both Colonies
1646
2726
1.66
1974
Cape Romain
920
825
0.90
Deveaux Bank
750
800
1.07
Both Colonies
1670
1625
0.97
1975
Cape Romain
900
500
0.56
Deveaux Bank
1500
1300
0.87
Both Colonies
2400
1800
0.75
1976
Cape Romain
1440
1399
0.97
Deveaux Bank
11001
1738'
1.58'
Both Colonies
2540
3137
1.23
'Estimated numbers — all other figures are based on actual counts.
Vol. 12, No. 4, March 1979
173
TABLE 2.
Year Sex
Probable causes of brown pelkan inorialily,
South Carolina, 1974-75
Age
Probable Cause of Mortality
1974
F
4 weeks
F
6 weeks
F
12 weeks
1975
sacrificed, had subcutaneous emphysema
hemorrhafiic cnlcrilis in ctimbination
with severe pecking injuries
respiratory problems — apparent air
saculitis
sacrificed, bird was near death of diarrhea
and excessive fluid in lungs, air sacs, and
pericardium
hemorrhagic enteritis
hemorrhagic enteritis
M
M
M
8 weeks
adult
adult
MORTALITY
Pelicans died of possible starvation and several diseases.
Hemorrhagic enteritis caused the death of at least two
of the si,\ adults found dead on Deveaux Bank April 9,
1975 (Table 2). These pelicans apparently had recently
migrated to South Carolina. Many brown pelicans that
breed in South Carolina winter on the Atlantic Coast
of Florida where hemorrhagic enteritis was responsible
for many deaths of the birds in 1972 {10, 20).
In 1974, a 6-week-old pelican apparently died of
hemorrhagic enteritis and severe pecking; the pecking
probably occurred when the sick young was attacked
by hostile young and adults. A 12-week-old pelican ap-
parently died of respiratory problems including air sacu-
litis. One of two young sacrificed in 1974 (Table 2) was
near death, and the other had subcutaneous emphy-
sema, a condition that is rarely fatal (13).
Several hundred downy young were found dead on
Deveaux Bank in 1974. Little regurgitated food was
observed during visits to the colony compared to visits
in other years, and except for the usual heavy mortality
after hatching, the deaths involved young at least 4
weeks old, an age when food demand rapidly increases.
EGGSHELL THICKNESS
Mean eggshell thickness of brown pelican eggs col-
lected in South Carolina (Table 3) was 10-17 percent
less than the pre- 1947 mean of 0.557 mm (/). The sig-
nificant increase {P < 0.05) in mean shell thickness in
1975, compared to the 6 preceding years, initiated an
upward trend extending to 1977 (Vivian Mendenhall:
personal communication).
Overall eggshell thickness of pelican eggs in Florida
increa.sed slightly from 1969-70 to 1974 (Table 3); it
increased markedly in the Gulf Coast colonies and re-
mained unchanged in the Atlantic Coast colonies
(Tables 4, 5). Shell thickness of Gulf Coast pelican eggs
collected in 1974 averaged just 2 percent less than the
pre- 1947 mean, whereas Atlantic Coast eggs averaged
1 1 percent less. There were insufficient data to com-
pare trends in shell thickness in Florida Bay colonies
(Table 4). In addition to South Carolina and Florida,
eggshell thickness of brown pelicans has been increasing
in California (2) and Louisiana (5),
RESIDUES IN EGGS
PCB and DDE residues made up the bulk of the 13
organochlorines identified in eggs of brown pelicans
(Tables 6-8). Residues in pelican eggs in 1974—75
followed the same pattern in each of the two South
Carolina colonies: there was a similarity in mean resi-
dues of each organochlorine in a given year, there was
much individual variation in residues of each organo-
chlorine, and there was a general decline in residues of
most organochlorines (Table 9). These patterns and
trends were also evident in samples collected from 1969
through 1973 {4, 10). Residues of DDE, DDT, and
:^DDT declined steadily from 1969 through 1975,
whereas TDE declined steadily to 1973 and then in-
creased somewhat. Dieldrin declined until 1971 and
then remained essentially stable through 1975. PCB
residues were erratic and followed no definite trend.
From 1969-70 to 1974 (Table 10), there were signifi-
cant declines (P < 0.05) in DDE, TDE, DDT, and
2DDT in brown pelican eggs from four regions of the
southeastern United States; dieldrin decreased signifi-
cantly (P < 0.05) in South Carolina and along the At-
TABLF. 3. Shell thickness of brown pelican ef>gs. 1969-75. compared to pre-1947 levels
Eggshell Thickness. mm>
Pre-1947
1969
1970
1971 1972
1973
1974
1975
SOUTH CAROLINA
0.557 i: A-'
0.012 (23)
0.46.1 ± D
0.0t)6 (49)
0.461 ± D
0.007 (38)
0.480 ± C 0.470 ± CD
0.005 (65) 0.005 (67)
0.463 ± D
0.003 (104)
0.469 ± CD
0.004 (116)
0.499 ± B
0.004 (95)
FLORIDA
0.557 ± A
0.003 (169)
0.516 i: B
0.005 (89)
0.511 ± B
0.004 (144)
0.521 ± B
0.004 (122)
< Mean ± standard error; sample size in parentheses.
-A significant difference anions thickness means (/" < 0.05) is indicated for those means not sharing a common letter. Means were separated by
multiple range tests (12. 15).
MA
Pesticides Monitoring Journai
TABLE 4. Shell thickness of brown pelican eggs
from Florida colonies, 1969-70, 1974
Eggshell THrcKNEss, mm>
Colony
1969
1970
ATLANTIC COAST
Port
Orange 0.488 ± 0.012 (9) 0.497 ± 0.009 (9) 0.476 ± 0.013 (14)
Crane Island — 0.491 rt 0.009 ( HI) —
Cocoa
Beach 0.497 ± 0.01 M 111) 0.482 ± 0.019 ( 101 0.499 ± 0.010 (15)
Pelican
Island 0.499 + 0.012(10) 0.498 ± 0.017 (9) 0.499:
Fort Pierce 0.513 ± 0.012 (6) 0.504 ± 0.(X)9 (9) 0.508:
; 0.010 (14)
: 0.011 (8)
FLORIDA BAY
Nest Key — 0.532 ± 0.012 (10)
Buchanan
Key 0.530 ±0.015 (31 0.545^0.013(10)
Fanny Key — 0.523 ± 0.019 (7)
Marquesas
Key — 0.541 ±0.012 (10)
0.523 ±0.016 (9)
GULF COAST
0.547 ±0.009 (15)
Seahorse
Key 0.530 ±0.015 (6) 0.531 ± 0.016 ( 10)
Tarpon Key 0.509 ± 0.015 (8) 11.487 ± 0.015 ( 10)
Cortez — 0.502 ±0.012 (10)
Bird Key 0.559 ± 0.014 ( 10) 0.517 ± 0.014 ( 10)
Matlacha
Pass 0.522 ± 0.023 (9) 0.504 ± 0.019 ( 10)
Hemp
Island 0.516 ±0.012 (10) 0.519 ± 0.015 ( 10)
0.534:
0.549 :
: 0.010 (15)
0.013 (15)
0.549 ± 0.012 (15)
'See footnote 1. Table 3.
TABLE 5. Shell thickness of brown pelican eggs
from the Gulf and Atlantic Coasts of Florida,
1969-70, 1974
Eggshell Thickness,
MM'
1969
1970
1974
GULF COAST
0.528 ± AS -
0.007 (43)
0.510 ± A
0.006 (60)
0.545 ± B
0.006 (60)
ATLANTIC COAST
0.498 ± A
0.006 (35)
0.494 ± A
0.006 (47)
0.494 ± A
0.006 (51)
'See footnote 1, Table 3.
'See footnote 2, Tabic 3.
lantic Coast of Florida, remained stable in Florida Bay,
and increased slightly on the Gulf Coast. In contrast,
PCBs increased significantly (P < 0.05) in two areas
and showed little change in the other two areas. The
most striking change was on the Atlantic Coast of
Florida where the PCB residues more than doubled from
1969-70 to 1974. The DDE: PCB ratio changed dra-
matically in most areas. For example, the ratio was
appro.\imately 1 : 1 on the Atlantic Coast of Florida in
1969-70 and 1:6 in 1974. DDT residues were rarely
found in 1974 samples. The order of decreasing organo-
chlorine contamination, by area, in pelican eggs during
each sampling period was: South Carolina > Florida
Atlantic Coast > Florida Gulf Coast > Florida Bay
(Table 10). Eggs collected from the Gulf Coast and
Florida Bay colonies in 1974 were essentially devoid of
organochlorine residues.
RESIDUES IN TISSUES
Birds found dead were analyzed for organochlorine
residues. Residues in tissues of four pre-fledgling peli-
cans found dead in South Carolina in 1974 were as low
as those reported previously in other young pelicans
(4, 10). Six freshly dead adult pelicans were found on
Deveaux Bank April 9, 1975.
Residues in three male adults were much higher than
in the young birds collected in 1974, but residues in
their brains were below lethal levels (Table 11).
RESIDUES IN FISH
Breeding brown pelicans in South Carolina feed almost
exclusively on young-of-the-year Atlantic menhaden
(Breevoortia tyranniis) that hatch off the coast from
October through April and migrate into the estuaries as
larvae where they usually remain for 6-8 months (19).
Residues of DDE in menhaden in 1974 and 1975 were
much lower than those reported in 1973 {10); DDT and
dieldrin were found in most 1973 samples but were not
detected in 1974-75 samples (Table 12). PCB resi-
dues averaged about the same in 1973 and 1974 but
declined substantially in 1975.
Discussion
Because trips to Deveaux Bank were infrequent, it
could not be established that starvation was responsible
for the deaths of downy young in 1974. Both young
that were necropsied exhibited signs of disease that may
or may not have been related to starvation (Table 2).
There were no apparent deaths of downy young on the
CRNWR, about 65 km northeast of Deveaux Bank,
although the pelicans there had poor reproductive suc-
cess and, judging from regurgitated boluses, they preyed
on a greater variety of fish than usual. Therefore, poor
food supply was probably responsible for the deaths of
downy young on Deveaux Bank.
The authors previously suggested that migration of
Atlantic menhaden complicate interpretation of biomag-
nification of residues from fish to pelican eggs {10)
because adult menhaden are exposed to varying levels
of organochlorine residues during migration. However,
authors have since determined that breeding pelicans
in South Carolina feed almost exclusively on young-of-
the-year menhaden that apparently accumulate nearly
all their residues from local estuaries. The interpreta-
tion of biomagnification is still complicated by the
migratory behavior of the brown pelican that exposes
it to several habitats with differing degrees of organo-
chlorine pollution.
Vol. 12, No. 4, March 1979
175
TABLE 6. Orgcinnchlorinc residues in brown pelican e,;',i?.v, Soulh Ciirolinii, 1974
Residues, juo/g fresh wet weight
DDE
TDE
DDT
DiELDRIN
Hepta- cis-
CHLOR OXYCHLOR- CHLOR-
EPOXIDE MIREX DANE DANE
trans-
NONA-
CHLOR
cis-
NONA-
CHLOR
HCB TOXAPHENE
PCBs
MARSH ISLAND
1.89
1.43
1.37
1.56
1.70
2.39
1.35
1.51
1.65
1.65
1.67
1.00
7.03
2.46
1.33
3.83
2.36
1.37
1.75
4.69
1.95
2.75
1.86
3.42
1.40
2.94
3.79
5.85
5.51
1.22
2.45
2.82
3.80
4.13
2.21
2.38
5.91
0.81
3.90
1.40
3.86
5.57
2.41
1.53
2.38
5.00
3.04
3.68
2.67
2.99
1.95
1.95
2.08
1.07
0.60
0.48
0.48
0.46
0.48
0.58
0.46
0.38
0.37
0.38
0.30
0.32
1.48
0.36
0.39
0.91
0.47
0.35
0.42
1.80
0.57
0.60
0.45
0.64
0.34
0.16
0.41
0.78
0.59
0.47
0.40
1.25
0.19
0.68
0.34
0.63
1.09
0.63
0.26
0.59
0.90
0.78
0.83
0.49
0.67
0.53
0.36
0.47
0.23
0.58
0.15
0.73
0.34
0.44
0.33
0.27
0.39
0.55
0.46
0.30
0.40
0.40
0.36
0.42
0.27
1.46
0.46
0.36
0.96
0.57
0.13
0.28
2.89
0.62
0.73
0.42
0.73
0.46
0.74
0.88
1.27
1.03
0.49
0.61
0.86
0.90
0.83
0.64
0.71
1.21
0.18
0.71
0.31
0.84
1.26
0.56
0.26
0.36
1.10
0.71
0.71
0.36
0.57
0.49
0.38
0.59
0.26
0.18
0.15
O.U
0.16
0.19
0.16
0.13
0.16
0.19
0.15
0.15
0.25
U.IO
0.13
0.11
0.10
0.14
0.10
0.32
0.20
O.U
0.16
0.10
0.15
0.13
—
0.41
0.63
0.35
0.14
0,21
0.16
0.15
0.16
—
0.31
0.34
0.22
0.21
0.24
0.18
0.12
0.15
—
0.11
0.14
—
0.61
U.71
0.63
0.19
0.17
0.15
0.19
0.19
0.25
0.16
0.10
0.10
0.21
0.11
0.22
0.17
0.13
—
—
—
0.15
0.22
0.17
0.31
0.36
0.33
0.30
0.35
0.38
0.25
0.13
0.17
0.15
0.14
0.20
0.27
0.24
0.24
0.22
0.17
0.19
0.18
0.17
0.16
0.23
0.14
0.13
0.16
0.40
0.42
0.45
0.15
0.11
O.U
0.23
0.19
0.11
0.22
0.24
0.17
0.44
0.39
0.31
0.24
0.22
0.15
0.11
0.16
—
0.10
—
0.10
0.45
0.47
0.45
0.28
0.28
0.18
0.27
0.32
0.17
0.16
0.16
0.14
0.22
0.30
0.15
0.14
0.12
0.22
0.16
0.20
0.12
0.25
0.23
0.16
0.11
0.15
—
0.27
5.60
0.12
4.15
0.18
5.25
0.11
6.87
1.88
7.57
0.12
7.98
—
4.34
0.21
8.30
0.22
4.19
0.19
7.02
0.18
6.90
0.15
5.40
0,83
18.09
0.15
13.80
0.21
9.21
0.38
13.88
0.29
11.80
0.20
7.66
0.17
17.00
—
13.00
—
6.49
—
10.50
—
5.69
—
1 1 .70
—
8.15
—
12.50
—
7.10
—
22.11
—
21.80
—
7.34
—
8.53
—
12.15
—
11.65
—
9.80
—
8.19
—
7.38
—
17.72
—
6.39
—
8.28
0.21
0.70
0.46
11.33
0.82
14.04
0.46
7.05
0,17
8.02
0.17
5.47
0.57
27.48
0.58
14.43
0.39
11.77
0.23
5.10
0.37
9.90
0.35
2.30
—
8.80
—
8.00
0.35
5.80
GM
CL
Range
2.35 0.41
2.04-2.70 0.34-0.51
0.81-7.03 ND-1.80
0.55
0.47-0.63
ND-0.73 0.17-2.89
ND-0.32 ND-0.20
0.17
0.14-0.20
ND-O.U ND-0.51
0.16 0.12
0.13-0.19 0.10-0.15
ND-0.71 ND-0.63
0.13
0.10-0.17
ND-0.10 ND-1.88
8.32
7.10- 9.76
0.70-27.48
DEVEAUX BANK
1.50
1.27
0.65
1.36
1.48
1.84
1.48
1.93
0.89
2.44
2.70
2.18
1.20
2.30
0.50
0.38
0.35
0.37
0.38
0.48
0.47
0.56
0.22
0.76
0.61
0.40
0.34
0.59
0.36
0.33
0.34
0.29
0.33
0,45
0.45
0.59
0.26
0.66
0.81
0.62
0.26
0.54
0.30
0.20
0.11
0.09
—
0.10
—
—
0.14
0.13
0.09
0.09
0.21
0.09
—
0.18
—
0.22
0.12
—
—
0.14
0.23
0.19
0.15
0.18
0.19
0.15
0.17
0.23
—
_-
0.17
O.U
0.22
0.10
— 0.32
5.01
— 0.20
5.16
— 0.22
4.07
— 0.21
5.00
— —
1.90
— —
8.14
— —
7.53
— —
12.00
— —
4.24
_ —
11.07
- —
9.82
- —
12.16
- —
4.80
- —
7.58
(Continued next page)
176
Pesticides Monitoring Journal
TABLE 6 (Cont'd.) Organochlorine residues in brown pelican eggs, South Carolina, 1974
Residues, ^o/g fresh wet weight
TDE
DDT DIELDRIN
Hepta-
CHLOR
Epoxide
MiREX
en-
OXYCHLOR- ChLOR-
DANE DANE
trans-
NONA-
CHLOR
CIS-
NONA-
CHLOR
HCB TOXAPHENE PCBs
1.40
0.34
2.50
—
3.53
0.95
2.29
0.37
2.42
0.59
2.99
0.69
1.70
0.46
1.72
0.37
1.60
0.31
2.19
0.50
1.65
0.43
2.08
0.45
2.02
0.52
1.15
0.42
1.43
0.42
2.87
0.48
2.11
0.37
1.36
0.21
1.37
0.31
0.74
0.23
0.78
0.16
0.76
0.21
1.41
0.22
2.35
0.10
0.80
0.27
2.18
0.39
2.05
0.37
2.16
0.96
1.84
0.48
4.51
0.95
3.04
0.84
3.76
0.73
3.11
0.62
1.98
0.45
2.12
0.31
1.96
0.51
1.92
0.62
2.33
0.44
3.32
0.59
4.62
0.92
4.94
1.22
3.59
0.76
3.67
0.37
2.98
0.69
1.59
0.38
4.48
0.96
2.30
0.80
GM 1.96
0.45
CL 1.74-2.21
0.40-0.52
0.18
0.36
—
—
0.73
—
—
0.95
—
0.13
0.56
—
—
0.61
—
—
0.83
—
—
0.50
—
—
0.39
—
—
0.39
—
—
0.59
0.26
—
0.43
—
—
0.61
—
—
0.47
—
—
0.44
—
—
0.42
—
—
0.60
—
—
0.55
—
—
0.29
—
—
0.60
—
—
0.22
—
—
0.32
—
—
0.19
—
—
0.27
—
—
1.28
0.11
—
0.27
—
—
0.44
—
—
0.56
—
—
0.86
—
0.10
0.39
—
—
1.10
0.13
0.17
1.14
0.12
—
0.80
—
—
0.53
—
—
0.54
—
—
0.33
—
—
0.54
—
—
0.67
0.11
—
0.61
—
—
0.88
0.12
—
1.43
0.23
—
1.22
0.14
3.01
0.84
—
0.33
0.85
0.11
—
0.71
0.10
0.21
0.40
—
—
0.85
0.10
0.25
0.96
D.I3
—
0.53
0.47-0.60
0.11
0.12
—
_
—
5.37
—
0.13
_
—
—
8.84
0.31
0.24
0.24
—
—
16.76
0.12
0.16
0.14
—
—
12.90
0.16
0.16
0.14
_
—
8.27
0.23
0.41
0.21
—
—
17.00
0.21
0.26
0.18
—
—
7.91
0.12
0.27
0.11
—
—
9.58
0.15
0.19
0.13
—
—
7.50
0.12
0.83
0.22
—
—
12.71
0.16
0.19
0.11
—
0.17
4.74
0.20
0.28
0.19
—
—
3.07
0.19
0.25
0.13
—
—
7.18
0,21
0.24
0.14
—
—
5.51
0.17
0.17
0.10
—
—
8.02
0.24
0.29
0.22
—
0.24
6.47
0.16
0.15
0.16
—
0.76
5.70
0.18
0.23
0.14
—
—
5.96
0.31
0.24
0.20
—
—
1.32
0.11
0.10
0.10
—
_
0.62
_
—
—
—
0.95
0.10
—
—
—
—
2.18
0.14
0.16
0.10
—
—
3.17
0.45
0.25
0.23
—
0.24
2.20
0.14
0.13
0.13
—
0.39
5.35
0.18
0.15
0.14
—
0.41
6.04
0.16
0.12
0.13
—
0.41
2.68
0.18
0.19
—
0.49
4.91
0.29
0.14
0.24
—
0.31
6.54
0.41
0.32
0.33
—
0.74
9.90
0.41
0.30
0.25
—
0.48
14.18
0.33
0.27
0.29
—
0.57
15.48
0.29
0.31
0.20
—
—
5.27
0.17
0.14
0.10
—
0.26
3.30
0.12
0.12
0.10
—
0.14
8.11
0.24
0.12
0.13
—
0.22
5.88
0.29
0.24
0.15
—
—
5.80
0.15
0.18
0.14
—
0.21
7.70
0.20
0.21
0.19
—
—
9.50
0.44
0.42
0.32
—
—
19.40
0.45
0.40
0.35
0.02
0.73
21.40
0.26
0.33
0.23
0.02
0.41
12.40
0.22
0.22
0.18
0.02
—
12.60
0.30
0.25
0.20
0.01
0.16
11.50
0.22
0.14
0.13
0.01
0.18
8.80
0.36
0.34
0.25
0.02
0.49
14.30
0.50
0.21
0.37
0.04
0.41
24.80
0.17 0.18 0.13
0.14-0.19 0.16-0.21 0.11-0.15
0.11 6.59
0.09-0.14 5.48- 7.94
Range 0.65-4.94 ND-1.22 ND-0.20 0.19-1.43 ND-0.26 ND-3.01 ND-0.53 ND-0.50 ND-0.83 ND-0.37 ND-0.04 ND-0.76 0.62-24.80
MARSH ISLAND AND DEVEAUX BANK
GM 2.13 0.44 0.54 0.17 0.17 0.13 0.12 7.36
CL 195-2 34 0 39-0 49 0 49-0 59 0.15-0.19 0.15-0.19 0.11-0.14 0.10-0.14 6.50-8.32
Range 0.65-7.01 ND-1.80 ND-0.73 0.17-2.89 ND-0.32 ND-3.01 ND-0.53 ND-0.61 ND-0.83 ND-0.63 ND-0.10 ND-1.88 •.62-27.48
ND or — = no residue detected.
GM = geometric mean.
CL = 95 percent confidence limits.
12, No. 4, March 1979
177
TABLE 7. Organochtorinc rcsiiliics in brown pelican c.ij.e.v, South Ciirolina, 1975
Residues, tto/a fresh wet weight
DDE
TDE
DDT
tranS'
HEPTACHLOR OXY- CIS- NONA-
DiELDRiN Epoxide MiRtx chlordane Chlordane chlor
cis-
NONA-
CHLOR
TOXAPHENE
PCBs
MARSH ISLAND
1.41
0.38
1.04
0.30
1.91
0.75
1.68
0.37
I.IS
0.27
1.84
0.33
1.00
0.35
1.61
0.53
3.10
0.69
1.53
0.26
1.20
0.33
1.10
0.18
1.22
0.31
2.59
0.49
1.64
0.41
1.20
0.34
0.81
0.19
1.44
0.59
1.09
0.34
1.42
0.50
1.03
0.34
1.10
0.34
0.75
0.30
0.65
0.21
0.96
0.31
0.88
0.21
1.61
0.57
1.73
0.64
1.13
0.34
1.50
0.37
1.91
0.58
1.34
0.38
1.57
0.54
1.64
0.47
1.12
0.41
0.70
0.34
1.57
0.41
0.36
0.10
0.87
0.29
1.76
0.62
1.15
0.45
0.70
0.20
0.95
—
1.71
0.39
1.85
0.60
2.76
0.74
1.65
0.57
0.89
0.37
1.72
0.67
0.95
0.21
1.80
0.38
1.08
0.42
2.51
0.58
2.36
0.65
1.58
0.43
1.60
0.18
2.00
0.81
1.59
0.58
0.13
0.50
0.22
0.58
0.44
0.34
0.36
0.32
0.50
0.72
0.36
0.35
0.23
0.31
0.66
0.48
0.27
0.22
0.38
0.27
0..14
0.27
0.24
0.16
0.17
0.26
0.22
0.38
0.45
0.34
0.37
0.53
0.30
0.51
0.55
0.32
0.22
0.51
0.10
0.23
0.41
0.34
0.19
0.23
0.43
0.53
0 76
0.42
0.28
0.92
0.26
0.40
0.28
0.71
0.67
0.49
0.50
0.50
0.40
0.10
0.10
0.10
0.14
0.11
0.10
0.27
0.38
0.10
0.13
0.13
—
0.15
0,38
5.02
0.11
0.13
—
0.28
3.01
0.29
0.27
0,24
0.27
4.35
0.15
0.14
0.10
0.32
3.95
0.15
0.13
0.11
0.24
4.64
0.33
0.23
0.29
0,57
7.40
0.17
0.19
0. 1 3
0,24
3.28
0.15
—
0,09
0.43
3,36
0.26
0.24
0,19
0,31
10.03
—
O.IO
—
0.48
3.10
0.17
0.18
0,11
0.48
4.50
—
0.13
—
—
5.31
0.12
0.16
—
0.14
6.45
0.18
0.26
0.19
0,49
11.05
0.20
0.26
0,18
0,55
6.20
0.12
0.16
—
0.14
5.20
0.10
0.10
—
0.11
8.80
0.25
0.25
0,13
0.18
6.98
0.14
0.18
0,10
0.16
5.02
O.IS
0.25
0.13
0.15
6.31
0.19
0.15
0.11
0.21
5.95
—
0.15
. —
0.22
4,87
0.11
—
—
0.16
7.06
O.IO
0.11
—
0.41
6.92
0.16
0.18
0,12
0.16
8.73
—
—
—
0.16
7.33
0.25
0.14
0.14
0.26
8.38
0.31
0.24
0.15
0.22
10.89
0.16
0.14
0.11
0,21
7.96
0.17
0.18
0.14
0,21
14.40
0.31
0.22
0,20
0,34
12.78
0.17
0.19
0.12
0.20
9,84
0.24
0.16
0,14
0.42
12.96
0.27
0.17
0 23
0.27
13.45
0.21
0.19
0,13
0.20
10.72
0.18
0.16
0,11
0.15
9.85
0.22
0.16
0,16
0.28
12.91
—
—
—
—
5.23
0.13
0.14
—
—
5.81
0.25
0.21
0.18
0.27
14.89
0.23
0.13
0.14
0,12
6.46
—
—
—
—
4.70
0.14
0.10
0,14
0.11
11.53
0.19
0.15
0,19
0.21
12.32
0.25
0.14
0,20
0.37
14.53
0.31
0.29
0.31
0.27
13.91
0.26
0.18
0.18
0.21
9.67
0.15
—
0,11
0.23
7.57
0.67
0.35
0,40
0.40
12.93
0.16
0.98
0,16
0.14
12.31
0.17
0.16
0,18
0.29
17.99
0.17
0.15
0,11
0,14
6.57
0.39
0.23
0.33
0.33
20.08
0.28
0.19
0.19
0.31
10.81
0.21
0.12
0,13
0.27
7.43
—
—
—
—
1.40
—
—
—
, —
0.38
0.31
0.33
0.19
0.50
7.47
0.28
0.28
0.17
0.29
10.95
GM 1.30 0.36
CL 1.15-1,46 0.30-0.42
Range 0.18-3.10 ND-0.81
ND-0.13
0,35
0.31-0.40
ND-0.92
ND-0.11 ND-0.38 ND-0.13
0,16 0.15
0,14-0,19 0,13-0.18
ND-0.67 ND-0.98
0 12 0.21
0,10-0,14 0,18-0.25
ND-0.40 ND-0.57
DEVEAUX BANK
1.24
0.36
3 03
0.68
1.70
0.37
2.51
0.91
1.34
0.37
1.35
0.32
2.03
0.54
0.91
0.33
1.34
0.41
0.39
—
0.39
0.63
0.40
0.55
0.41
0.34
0.59
0.21
0.29
0.19
0.19
O.IO
0.12
0.22
1.77
0.15
0.11
0,15
0.54
1.84
0.15
0,17
0,12
0.22
3.49
0.25
0,17
0, 1 3
0.50
7.32
0.16
0,15
0.12
0.13
2.60
0,13
0,14
0,12
0.24
2.69
0.19
0.19
0.16
0.40
3.96
0.14
—
_
0.11
2.51
0.17
—
0.10
0.21
2.43
—
0.09
—
—
1.70
(Continued next pa^e)
178
Pesticides Monitoring Journal
TABLE 7 (cont'd.). Oraaiwchlorinc residues in brown pelican eggs. Soiilh Curoliiia, 1975
Residues,
/IC/G FRESH
1 WET WEIGHT
trans-
cis-
Heptachlor
OXY-
cis-
NONA-
NONA-
DDE
TDE
DDT
DiELDRIN
Epoxide
MiREX (
:hlordane Chlordane
CHLOR
CHLOR TOXAPHENE
PCB
0.65
0.11
—
0.11
—
—
0.13
0.13
0.11
0.07
0.09
6.82
—
0.29
—
0.34
—
—
—
0.17
0.24
0.16
0.22
3.92
0.10
0.80
—
0.64
—
—
—
0.29
0.29
0.18
0.31
4.20
1.02
0.26
—
0.28
—
—
—
0.14
0.19
0.11
3.07
1.62
0.45
—
0.40
—
—
—
0.16
0.20
0.14
0.38
3.60
0.88
0.31
—
0.21
—
—
—
0.17
—
_
0.18
1.54
3.69
0.10
—
0.97
—
—
—
0.59
—
0.35
0.35
5.93
1.00
0.34
—
0.27
—
0.10
—
0.12
—
—
0.22
1.98
1.52
0.41
—
0.97
—
0.14
—
0.15
0.27
0.11
0.36
3.63
0.50
—
—
0.11
—
—
—
—
—
—
0.21
4.37
1.78
0.60
—
0,44
—
—
—
0.24
0.33
0.18
0.58
13.56
1.48
0.35
—
0.29
—
—
—
0.16
0.22
0.14
0.31
9.66
0.97
0.35
_
0.3.1
—
—
—
0.17
0.19
0.10
0.20
5.55
1.99
0.52
—
0.39
—
—
—
0.18
0.24
0 14
0.37
7.88
1.19
0.30
—
0.35
—
—
—
0.13
0.18
0.11
0.40
10.81
1.02
0.42
—
0.35
0.10
—
—
0.17
0.22
0.11
0.14
8.40
1.23
0.31
—
0.33
—
—
—
0.15
0.22
0.14
0.10
6.86
1.59
0.54
—
0.45
—
—
—
0.20
0.27
0.14
0.25
5.19
1.40
0.38
—
0.34
—
—
—
0.19
0.26
0.14
0.15
9.88
1.99
0.51
—
0.51
0.12
—
—
0.19
0.27
0 16
0.12
9.86
2.48
0.72
—
0.46
0.10
—
—
0.23
0.34
0.18
0.27
10.25
1.00
0.20
—
0.21
—
—
—
0.10
0.12
0.09
—
7.92
1.73
0.22
.
0.43
—
—
—
0.14
0.19
0.12
—
10.43
1.28
0.20
0.35
—
—
0.10
0.2-1
0.16
0.09
—
7.22
0.76
0.23
0.20
—
—
—
0.10
0.13
—
0.23
7.93
2.09
0.38
0.53
0.10
—
0.13
0.26
0.28
0.13
0.26
10.03
3.04
0.58
0.40
0.14
—
—
0.96
—
0.20
1.27
11.46
1.90
0.41
0.63
—
—
—
0.46
0.16
0.12
0.09
3.90
2.91
0.78
—
0.70
0.20
—
—
0.24
—
0.20
1.02
6.06
3.62
1.38
—
1.04
0.50
—
0.10
0.61
0.68
0.22
0.38
6.11
1.86
0.44
—
0.46
0.14
—
—
0.13
0.28
0.14
0.51
4.88
3.13
0.96
—
0.96
0.31
—
—
0.36
0.53
0.31
0.67
10.10
2.22
0.38
—
0.68
0.21
—
—
0.28
0.40
0.17
0.57
6.37
CM
1.29
0.38
0.38
0.18
0.16
0.12
0.23
5.07
CL
0.99-
1.67
0.31-0.47
0.31-
0.46
0.16-0.22
0.13-0.20
0.10-0.14
0.18-0.30
4.20- 6.1
Range
ND-
3.69
ND-
1.38
ND
ND-
1.04
ND-0.50
ND-0.19
ND-0.13
ND-0.96
ND-0.68
ND-0.35
ND-1.27
1.54-13.5
MARSH ISLAND AND DEVEAUX
BANK
GM
1.29
0.36
0.36
0.17
0.15
0.12
0.22
6.24
CL
1.14-1.47
0.32-0.41
0.32-
0.40
0.15-0.19
0.14-0.17
0.11-0.13
0.19-0.25
5.50- 7.01
Range
ND-
•3.69
ND-
1.38
ND-0.13
ND-
■1.04
ND-0.50
ND-0.38
ND-0.13
ND-0.96
ND-0.98
ND-0.40
ND-1.27
0.38-20.0!
ND or — = no residues detected.
GM = geometric mean.
CL = 95 percent confidence limits.
Vol. 12, No. 4, March 1979
179
Colony
DDE
TABLE 8. Organochloriiic rcsidms in brown pelican eggs, Florida, 1974
Residues, (ic/o fresh wet weight
TDE
PCBs
Heptachlor
Epoxide
CIS- trans- cis-
MiREX Chlordane Nonachlor Nonachlor Toxaphene
DiELDRIN
GULF COAST
Cedar Key
—
0.11
0.91
0.16
—
0.36
0.23
—
0.86
0.52
—
1.50
0.47
—
1.20
0.29
—
11.56
0.99
0.31
0.75
0.20
—
0.47
0.«4
0.18
1.40
0.42
—
0.65
0.24
—
0.69
—
—
0.69
—
0.14
0.79
—
_
0.44
0.24
—
1.10
0.10
0.14
0.10
0.14
0.21
0.16
0.58
0.44
0.19
GM
CL
Range
0.29
0.16-0.43
ND-0.64
ND-0.31
0.80
0.62- 1. 00
0.36- 1.60
ND
ND
ND-0.14
ND-0.12
ND
ND-0.58
Cortez
0.51
0.10
2.10
0.33
—
1.00
0.57
0.18
2.00
1.00
0.12
1.80
0.64
0.14
1.10
0.39
0.13
1.1(1
0.37
0.10
1.00
0.12
0.10
10.30
0.31
—
1.50
1.47
0.20
2.20
0.35
0.11
0.99
—
0.11
3.90
0.66
0.22
0.75
—
0.15
1.40
0.52
0.14
1.20
020
—
0.13
0.27
—
0.15
1.00
oin
0.13
—
0.15
0.19
—
0.33
0.23
0.18
0.14
0.17
0.10
0.15
0.11
—
0.17
—
—
0.19
0.17
0.12
0.29
0.20
(1.10
0.23
0.19
0.11
0.18
0.14
0.19
0.12
0.15
0.15
0.11
0.38
0.23
0.18
0.10
0.19
0.17
0.20
GM
CL
Range
Bird Key
0.45
0.28-0.65
ND-1.47
0.12
0.08-0.15
ND-0.22
1.74
I. II- 2.57
0.75-10.30
ND
ND
0.15
—
0.60
0.29
—
0.41
0.26
O.IO
0.15
0.55
0.16
1.70
0.57
0.11
1.60
—
0.19
0.25
0.59
0.13
1.20
0.30
—
1.00
0.22
—
0.33
0.33
0.13
3.20
0.20
—
1.20
—
—
1.20
0.31
0.14
2.80
0.22
—
1.50
0.12
—
0.51
0.19
0.14 0.14 0.06
0.08-0.20 0.04-0.26 0.02-0.10
ND-0.33 ND-1.00 ND-0.18
ND
0.60
—
0.15
0.16
0.10
—
0.17
0.22
0.13
—
0.19
—
—
—
0.10
—
—
—
0.10
—
—
—
0.10
—
—
0.31
0.17
0.10
0.09
—
—
0.16
0.12-0.20
ND-0.38
0.11
0.12
0.18
0.25
0.17
0.13
O.U
0.15
0.10
0.19
GM
CL
Range
0.27
0.18-0.37
ND-0.59
0.06
0.02-0.10
ND-0.19
1.02
0.63- 1.51
0.15- 2.80
ND
ND-0.31
0.07
0.03-0.11
ND-0.19
ND-0.22
ND-0.13
ND-0.60
0.10
0.07-0.14
ND-0.25
Hemp Island
1.05
0.41
4.10
0.16
—
0.94
0.70
0.30
1.50
0.28
—
0.61
—
—
0.25
0.52
—
1.10
0.58
—
0.60
0.16
_
0.80
0.73
—
3..30
0.60
0.13
1.40
0.63
0.11
1.80
0.29
—
1.70
0.23
—
0.50
0.31
0.13
1.30
0.40
—
1.30
0.13
0.10
0.83
0.45
0.48
0.33
0.15
0.18
0.13
0.15
0.13
0.14
0.44
0.18
0.23
0.10
0.65
0.30
0.10
0.22
0.26
0.19
0.15
0.12
O.U
0.10
GM
CL
Range
0.42
0.29-0.58
ND-1.05
ND-0.41
1.24
0.82- 1.77
0.50-4.10
ND-0.13
ND-O.IO
ND-0.83
ND-0.48
ND-0.44
ND-0.23
0.12
0.08-0.18
ND-0.65
(Continued next page)
180
Pi STRIDES Monitoring Journal
TABLE 8 (Cont'd.). OrganocMorine residues in brown pelican egs-s, Florida, 1974
Residues, ^c/g fresh wet weight
Colony
DDE
TDE
PCBs
Heptachlor cis-
Epoxide MmEX Chlordane
trans-
NONACHLOR
NONACHLOR TOXAPHENE
DiELDRIN
FLORIDA BAY
Marquesas Key
0.13
0.64
0.23
0.11
0.42
0.44
1.05
0.25
0.42
0.14
0.41
1.29
1.60
0.83
1.06
0.12
Fort Pierce
1.61
0.31
10.90
0.91
0.12
4.66
1.47
0.34
8.89
1.16
0.31
6.63
0.60
0.19
3.98
1.15
0.22
7.79
2.15
0.65
12.92
1.19
0.38
10.47
0.12
0.10
0.14
0.21
0.21
0.22
0.18
0.11
0.14
0.11
0.13
0.11
0.12
0.20
0.16
0.20
0.14
0.10
0.14
GM
CL
Range
0.39
0.19-0.61
0.11-1.05
ND-0.14
0.47
0.08- 1. 00
NO- 1.60
NO
ND ND
ND
ND
ND-0.14
ND-0.14
Fanny Key
0.37
0.19
0.10
2.41
0.85
—
— —
—
—
—
0.12
ATLANTIC COAST
0.26
0.19
0.42
0.40
0.24
0.28
0.41
0.40
GM 1.24 0.31 7.79
CL 0.89-1.66 0.19-0.44 5.49-10.91
Range 0.60-2.15 0.12-0.65 3.98-12.92
ND-0.12
0.13
0.05-0.21
ND-0.22
ND-0.18
0.10
0.04-0.16
ND-0.20
ND-0.20
0.31
0.24-0.40
0.19-0.42
Cocoa Beach
0.67
0.14
2.98
1.81
0.45
7.80
1.39
0.29
6.10
1.13
0.32
4.77
0.72
0.13
2.40
0.44
0.19
5.16
0.74
0.18
5.43
0.85
0.23
3.00
1.73
0.40
5.58
1.72
0.40
8.35
1.20
0.27
4.76
1.20
0.28
7.77
3.40
0.78
9.22
0.94
0.29
3.38
0.49
0.17
2,83
—
—
—
—
0.20
0.16
0.12
0.14
0.25
0.35
0.16
—
0.18
0.18
0.44
0.15
0.17
0.13
0.14
0.34
—
—
—
—
0.14
—
—
—
0.21
0.27
0.16
0.13
0.15
—
0.25
0.13
—
O.ll
0.10
0.41
0.30
0.15
0.23
0.21
0.70
—
0.13
—
—
0.38
0.15
0.15
0.16
0.22
0.41
0.16
0.10
0.13
0.21
0.33
0.24
0.18
0.20
0.46
0.78
—
—
—
0.44
0.23
0.12
—
0.10
—
0.18
GM
CL
Range
1.13
0.82-1.51
0.44-1.81
0.29
0.21-0.38
0.13-0.78
4.94
3.89- 6.24
2.40- 9.22
ND ND
0.11
0.06-0.16
ND-0.30
0.07
0.03-0.11
ND-0.18
0.10
0.05-0.15
ND-0.23
0.15
0.07-0.24
ND-0.46
0.32
0.25-0.42
0.14-0.78
ican Island 0.99
0.25
2.48
1.33
0.25
5.77
1.25
0.28
4.18
1.01
0.16
3.07
0.72
0.21
4.67
1.11
0.35
6.36
1.40
0.46
7.25
1.77
0.62
9.73
1.03
0.49
9.06
1.40
0.60
9.52
1.40
0.35
9.24
0.49
—
2.71
1.72
0.50
9.26
0.66
0.13
1.98
—
—
—
0.22
0.15
0.19
0.12
0.20
—
0.33
0.15
—
0.13
0.14
0.23
—
—
—
—
0.26
0.13
0.11
—
—
0.23
0.13
0.16
—
—
0.31
0.16
0.16
0.13
0.27
0.46
0.18
0.20
0.15
0.30
0.60
0.14
0.13
0.13
0.12
0.42
0.35
0.30
0.25
—
0.65
0.19
0.17
0.12
—
0.45
—
—
—
—
0.13
0.15
0.17
0.14
0.11
0.48
—
0.12
—
—
0.15
GM
CL
Range
1.13
0.92-1.37
0.49-1.77
0.32
0.22-0.43
ND-0.62
5.47
3.96- 7.45
1.98- 9.73
ND-0.11 ND
0.12
0.07-0.18
ND-0.35
0.11
0.06-0.17
ND-0.30
0.09
0.04-0.14
ND-0.25
ND-0.30
0.31
0.23-0.42
0.13-0.60
Port Orange
1.67
0.43
10.01
0.91
0.14
4.97
1.80
0.65
7.80
2.11
0.59
11.27
2.64
0.74
11.78
1.55
0.38
8.10
0.10
0.18
0.17
0.10
0.26
0.43
0.10
0.10
—
—
0.46
0.24
0.21
0.14
0.23
0.54
0.18
0.22
0.13
0.33
0.47
0.53
0.34
0.26
0.29
0.62
0.17
0.16
0.11
0.24
0.38
(Continued next page)
Vol. 12, No. 4, March 1979
181
TABLE 8 (Cont'd.). Orf^aiiochtorine residues in hrowii pelican enKS, Florida. 1974
Residues, iio/o fresh wet weight
Colony
DDE
TDE
PCBs
Heptachlor
Epoxide
Mirex
CIS-
Chloroane
trans-
NONACHLOR
NONACHl.OR Toxaphene Dibldrin
1.02
0.12
5.45
1.16
0.34
6.05
1.04
0.38
4.90
0.4S
0.10
4.17
1.51
0.45
8.42
1.00
0.37
8.30
1.94
0.46
7.43
1.34
0.22
9.70
0.24
0.47
0.31
0.15
0.33
0.12
0.28
0.11
0.12
0.31
—
0.13
0.30
—
—
.0.18
H.Il
0.23
0.42
—
0.41
0.83
0.33
1.53
0.46
—
0.18
0.28
GM
CL
Range
1.32
1.03-1.71
0.45-2.64
0.33
0.23-0.47
0.10-0.74
7.39
6.13- 8.91
4.27-11.78
ND-0.10
ND
0.14
0.08-0.23
ND-0.53
0.12
0.08-0.19
ND-0.34
0.09
0.06-0.13
ND-0.33
0.19
0.11-0.32
ND-1.53
0.40
0.32-0.50
0.18-0.83
NOTE: ND or — = no residue delected.
GM — geometric mean.
CL — 95 percent confidence limits.
TABLE 9. T,
ends for ori;anoi
htorine residues in
hrown pelican eHQs,
1969-75
Deveaux Bank
ind Marsh Island, S
nurh Carolina,
Residues. iig/g ^RESH wet weight
Sample
Year Size
DDE
TDE
DDT
2 DDT
DiELDRIN
PCBs
1969 15
5.45 'A =
1.65 A
0.45 A
7.81 A
1.16 A
6.11 AB
(4.44^6.70)
(1.. ^0-2. 10)
(0.15-0.83)
(6.48-9.40)
(1.03-1.52)
(5.00-7.45)
1970 13
3.58 B
0.79 B
0.55 A
5.27 B
0.82 B
5.25 AB
(2.23-5.72)
(0.53-1.20)
(0.42-0.69)
(3.49-7.77)
(0.52-1.32)
(3.92-7.04)
1971 65
2.48 C
0.48 C
0.17 B
3.20 D
0.46 C
6.49 A
(2.27-2.71)
(0.43-0.53)
(0.13-0.21)
(2.94-3.48)
(0.40-0.52)
(5.44-7.73)
1972 72
3.03 B
0.36 C
0.18 B
3.69 C
0.45 C
7.51 A
(2.7l>-3.40)
(11.31-0.42)
(0.15-0.21)
(3.31-4.12)
(0.39-0.52)
(6.68-8.46)
1973 104
2.09 D
0.19 D
0.17 B
2.56 E
0.45 C
4.75 B
(1.91-2.29)
(0.17-0.22)
(0.15-0.20)
(2.35-2.78)
(0.41-0.50)
(4.26-5.31)
1974 115
2.22 CD
0.49 C
0.02 C
2.72 E
0.58 C
7.63 A
(2.03-2.43)
(0.44-0.54)
(0.01-0.04)
(2.49-2.96)
(0.53-0.64)
(6.80-8.55)
1975 1(12
1.40 E
0.41 C
(1.004 C
1.80 F
0.40 C
6,45 A
(1.27-1.54)
(0.37-0.46)
(0.()ll2-().()07)
(1.64-1.97)
(0.36-0.43)
(5.75-7.24)
> Geometric mean; 95 percent confidence limits are in parentlieses.
= See Footnote 2, Table 3.
The factors iincierlying the large population increase
were not evident. The excellent reproductive success
in 1973 cannot account for the large population increase
just 2 years later. It is possible that many South Caro-
lina adults did not breed before 1975 because of insuf-
ficient food. Many adult brown pelicans in Mexico and
California apparently do not breed when the food
supply is poor (2). The breeding population in .South
Carolina showed only a slight increase in 1973 when
pelicans had an excellent reproductive season and men-
haden were apparently readily available. Thus it is
doubtful that large numbers of adult pelicans in South
Carolina failed to breed from 1969 to 1974. There is
no evidence from banding studies that large numbers of
pelicans migrated from natal areas in Florida to South
Carolina to breed. Although the population increase
was probably caused by a combination of factors, the
most likely factor seems to be the decline in organo-
chlorine residues that resulted in improved reproductive
success and probable increased longevity after fledging.
DDE is the organochlorine exerting most influence on
reproductive success. However, little is known about
adult mortality from organochlorines except that several
TABLE 10. Organochlorine residue trends
in brown pelican eggs from four regions, 1969-70, 1974
Mean residues,
;ig/g fresh wet weight
Pollutant
DDE
TDE
DDT
>: DDT
Dieldrin
PCBs
Region'
SC
AC
FB
GC
SC
AC
FB
GC
SC
AC
FB
GC
SC
AC
FB
GC
SC
AC
FB
GC
SC
AC
FB
GC
1969-70
1974
4.65 A =
2.22 B
2.32 B
1.21 C
1.04 C
0.37 D
1.48 C
0,36 D
1.29 A
0.49 C
0.91 B
0.32 D
0.18 E
0.03 E
0.55 C
0.07 E
0.49 A
0.02 C
0.43 A
0.01 C
0.07 C
NDC
0.27 B
NDC
6.52 A
2.72 C
3.68 B
1.52 D
1.25 D
0..39 E
2.27 C
0.42 E
1.09 A
0.58 B
0.51 B
0.36 C
0.06 D
0.04 D
0.11 D
0.13 D
5.77 B
7.63 A
2.68 C
6.12 AB
0,75 D
0.62 D
0.70 D
1.I8D
'SC = South Carolina, AC = Florida Atlantic Coast, FB = Florida
Bay, and GC = Florida Gulf Coast.
-See Footnote 2, Table 3.
182
Pesticides Monitoring Journal
TABLE 11. Ori^anochlorine residues in tissues of brown pelicans found dead, South Carolina, 1974-75
Residues, iiG/a fresh wet weight
Year
Sex
Tissue
DDE
TDE
DDT
Hepta-
CHLOR
Dieldrin Epoxide
CIS-
Chlor-
dane
trans-
NONA-
CHLOR
as-
NONA-
CHLOR
TOXA-
PHENE
Ml REX PCBs
1974
1975
F
4wk
Carcass
0.14
—
—
—
0.25
Brain
—
—
—
—
—
—
0.25
K
6wk
Carcass
0.16
—
—
—
__
1.44
Brain
0.52
—
—
0.14
—
2.46
F
12 wk
Carcass
0.46
0.16
—
0.13
—
—
—
1.27
Brain
—
—
—
—
—
—
—
—
0.74
M
8 wk
Carcass
0.15
—
—
—
—
—
—
—
1.28
Brain
0.20
— ■
—
—
—
—
—
1.58
M
AD
Carcass
3.09
1.25
0.14
1.67
0.22
0.44
0.56
0.47
0.56
1.40
25.28
Brain
3.43
0.55
—
0.99
0.10
0.26
0.20
0.22
0.48
0.64
14.22
M
AD
Carcass
3.24
1.56
0.14
1.87
0.26
0.62
0.92
0.71
0.73
1.80
38.80
Brain
1.31
0.54
—
0.91
—
—
0.19
0.23
0.54
0.87
12.83
M
AD
Brain
1.46
0.61
—
0.99
0.10
0.27
0.31
0.27
0.47
0.65
2.92
NOTE; — = no residues detected.
AD = adult.
TABLE 12. Organoclilorine residues in Atlantic menhaden refiurgitated by brown pelicans. South Carolina, 1974-75
Residues, /lO/o fresh wet weight
Year
DDE
TDE
Heptachlor
Epoxide
cts~ CIS- trans-
Chlordanc Nonachlor Nonachlor Toxaphene
PCBs
1974
0.01
0.04
0.01
0.06
0.04
0.01
0.02
0.01
0.23
0.19
0.02
0.36
0.22
GM
CL
0.016
0.004-0.060
0.147
0.036-0.608
1975
0.03
0.04
0.01
0.03
0.02
0.06
0.03
0.06
0.01
0.01
0.02
0.03
0.01
—
0.02
0.03
0.01
0.01
0.03
0.03
0.02
0.02
0.01
0.01
0.01
—
0.06
0.03
—
0.02
0.03
—
0.02
0.09
—
—
0.08
—
—
0.02
0.01
—
0.10
—
—
0.10
0.01
0.02
0.15
—
0.01
0.11
GM
CL
0.014
0.009-0.022
0.020
0.010-0.039
0.050
0.024-0.107
NOTE: — = no residues detected.
GM = geometric mean.
CL = 95 percent confidence limit.
pelicans have died of endrin and dieldrin poisoning. An
increase in adult survival would have a marked effect
on the breeding population and on the recruitment
standard necessary to maintain a stable population.
There are no data to support the theory of increased
adult longevity, but it may be investigated in the future
by analyzing banding data.
The South Carolina brown pelican population formerly
numbered about 6,000 breeding pairs (i, 10), and if the
present rate of reproductive success continues, the
population should reach 6,000 breeding pairs within
the ne.xt 5 years. The pelican population in Florida has
been essentially stable since aerial surveys of nesting
colonies were initiated in 1968 (18. 21).
Acknowledgments
Authors thank A. Stana Federighi and Eugene H. Dust-
man for critically editing the manuscript. Appreciation is
expressed to Steve Joyner, Daniel Doshier, Fred Milton,
Stewart Givens, George Garris, Julie Keahey, Brad
Winkler, John Sheerer, Scott Osborne, George She-
gogue, and others for assistance in the field. We are
grateful to Gary Hensler, Jane Dowdy, Ann Potoski,
and Robert Schwenk for statistical assistance, and to
Louis N. Locke for necropsy reports.
Vol. 12, No. 4, March 1979
183
LITERATURE CITED
(/) Amierson. D. W.. ami J. J. HUkey. 1970. Oological
data on egg and breeding characteristics of brown
pelicans. Wilson Bull. 82(1): 14-28.
(2) Anderson, D. W.. J. R. Jehl. Jr.. R. W. Ritehrough,
L. A. Wooth, Jr.. L. R. DeWcese. and W. G. Ed);e-
comh. 1975. Brown pelicans: improved reproduc-
tion off the Southern California Coast. Science
180(4216) :806-808.
(.?) Beckett. T. A., 111. 1966. Deveaux Bank— 1964 and
196.'!. Chat 30(4):93-100.
(4) Blu.s. L. J.. A. A. Belhle. and R. M. Proiity. 1974.
Relations of the brown pelican to certain environ-
mental pollutants. Pestic. Monit. J. 7(3/4): 181-194.
(5) Bins. L. J., E. Croniartie. L. McNease. and T. Joanen.
In press. Brown pelican: Population status, repro-
ductive success, and organochlorine residues in Louis-
iana, 1971-1976. Bull. Environ. Contam. Toxicol.
(6) Blus. L. J.. C. D. Gish, A. A. Belisle, and R. M.
Prouty. 1972. Logarithmic relationship of DDE resi-
dues to eggshell thinning. Nature 235(5338) :376-377.
(7) Blus. L. J.. R. a. Heath. C. D. Gish. A. A. Belisle. and
R. M. Prouty. 1971. Eggsell thinning in the brown
pelican: implication of DDE. BioScience 21(24):
1213-1215.
(8) Blut. L. J., T. Joanen. A. A. Belisle, and R. M. Prouty.
1975. The brown pelican and certain environmental
pollutants in Louisiana. Bull. Environ. Contam.
Toxicol. 13(6):646-655.
(9) Bhds, L. J.. B. S. Neely. Jr.. A. A. Beli.sle. and R. M.
Prouty. 1974. Organochlorine residues in brown peli-
can eggs: relation to reproductive success. Environ.
Pollut. 7(2):81-91.
{10) Blus. L. J.. B. S. Neely. Jr.. T. G. LamonI, and B.
Mulhern. 1977. Residues of organochlorines and
heavy metals in tissues and eggs of brown pelicans,
1969-73. Pestic. Monit. J. 11(1) :4a-53.
(//) Cromariie. E.. W. L. Reiehel. L. N. Locke. A. A.
Belisle. T. E. Kai.ser. T. G. LamonI. B. M. Mulhern,
R. M. Prouty, and D. M. Swineford. 1975. Residues
of organochlorine pesticides and polychlorinated bi-
phenyls and autopsy data for bald eagles, 1971-72.
Pestic. Monit. J. 9(1): I 1-14.
1.12) Duncan. I). B. 1955. Multiple range and multiple F
tests. Biometrics 1 1( 1 ): 1-42.
(/.?) Gochfeld. M. 1974. Prevalence of subcutaneous em-
physema in young terns, skimmers and gulls. Wildl.
Dis. 10(1): 115-120.
(/•/) Henny, C. J. 1972. An analysis of the population
dynamics of selected avian species — with special refer-
ence to changes during the modern pesticide era. Fish
and Wildlife Service, U.S. Department of the Interior,
Wildl. Res. Report No. 1, 99 pp.
(/.')) Kramer. C. Y. 1956. Extensions of multiple range
tests to group means with unequal numbers of replica-
tions. Biometrics 12(2) :307-310.
(/6) Mulhern. B. M.. E. Cromartie. W. L. Reiehel. and A.
A. Belisle. 1971. Semiquantitative determination of
polychlorinated biphenyls in tissue samples by thin
layer chromatography. J. Assoc. Off. Anal. Chem.
54(3):548-550.
{17) Mulhern, B. M.. W. L. Reiehel, L. N. Locke. T. G.
LamonI, A. A. Belisle, E. Cromartie, G. E. Bagley,
and R. M. Prouty. 1970. Organochlorine residues
and autopsy data from bald eagles, 1966-68. Pestic.
Monit. J. 4(3):141-I44.
(IS) Neshitt, S. A.. M. J. Fomrty. and L. E. Williams. Jr.
1977. Nesting status of brown pelicans in Florida:
1971-76. Bird-Banding 48(2):138-144.
{19) Reintjes. J. W . 1969. Synopsis of biological data on
the Atlantic Menhaden (Brevoortia tyrannusj. Fish
and Wildlife Service, U.S. Department of the Interior,
FAO Fish. Synopsis No. 42. 29 pp.
{20) White. F. H .. C. F. Simpson, and L. E. Williams, Jr.
1973. Isolation of Edwardsiella tarda from aquatic
animal species and surface waters in Florida. J. Wildl.
Dis. 9(3): 204-208.
{21) Williams. L. E., Jr.. and L. Martin. 1970. Nesting
populations of brown pelicans in Florida. Pages 154-
169, Proc. 24th Annual Conf. S. E. Assoc. Game Fish
Comm.
184
Pesticides Monitoring Journal
Pesticide Contamination of Water Rats in the Murrumbidgee Irrigation Areas,
New South Wales, Australia, 1970-72
Penny Olsen ' and Harry Settle -
ABSTRACT
OrganocMorine pesticides were found in all samples of
livers, kidneys, mammary glands, and fetuses of eastern
water rats (Hydromys chrysogaster) collected in the Mur-
rumbidgee irrigation areas of New South Wales in 1970 and
1972. DDE was the predominant residue. Livers contained
0.01-3.10 ppm ZDDT air-dried weight; kidneys, < 0.01-1.12
ppm; mammary glands, 0.14-23.75 ppm: and fetal liver,
0.28-0.66 ppm. Variations in residue levels are discussed in
relation to the possible effects of environmental and physio-
logical factors.
Introduction
Large amounts of water are used in the Murrumbidgee
irrigation areas of New South Wales for flood irrigation
of rice crops. Drainage water from these crops and from
irrigated orchards, vineyards, and cereal and vegetable
crops enters Mirrool Creek. A weir. Willow Dam, con-
trols entry of the creek's water into a storage swamp or
diverts it for further irrigation use.
Several pesticides are used on area farms, although
DDT predominates. About 1-4.5 kg/ ha. is used an-
nually (2), largely to control the bloodworm (Chirono-
miis sp.) which damages rice seedlings. Eastern water
rats (Hydromys chrysogaster) , common in the irrigation
area, were collected monthly from Mirrool Creek and
Willow Dam as part of a study of the biology of the
species.
Little is known of pesticide contamination of Australian
fauna (2). The present study is a preliminary examina-
tion of the degree of exposure of water rats to
pesticides.
Materials and Metlwds
SAMPLE COLLECTION
Eastern water rats were live-trapped from Mirrool
Creek at Willow Dam near Griffith, New South Wales,
> Division of Wildlife Research. Commonwealih Scientific and Indus-
trial Research Organization, P.O. Box 84, Lyneham, Australian
Capital Territory, Australia, 2602.
-Australian Government Analytical Laboratories, South Australia
Regional Laboratory, 344 Tapleys Hill Road, Seaton, South Australia,
Australia, 502.1.
between January 1970 and January 1973, Livers, kid-
neys, mammary glands, and fetuses were removed from
the freshly killed rats and preserved in 10 percent
formalin. A small number of samples taken during
1970 and 1972 were analyzed for pesticides as follows:
in 1970, January (7), April (3), October (3), No-
vember (4); in 1972, February (2), May (2), July (7),
August (6). Sampling pattern is illustrated in Figure 1.
ANALYSIS
In the laboratory, samples were drained and air dried,
cut into small pieces, mixed with sodium sulfate, and
extracted with hexane in a Soxhlet thimble for 4 hours.
Extraction for a longer period did not increase residue
recovery. The hexane extracts were concentrated to
about 10 ml and partitioned three times with 25 ml
acetonitrile as a preliminary cleanup. The acetonitrile
phase was passed into 300 ml 2 percent sodium sulfate
and shaken with 100 ml hexane. The hexane layer was
dried by passing it through anhydrous sodium sulfate
and was concentrated to 5 ml. The concentrate was
mixed with 20 g 2 percent deactivated Florisil, poured
into a chromatographic column containing 20 g 2 per-
cent deactivated Florisil, and eluted in three frac-
tions (5, 6) as follows:
Fraction A, eluted with 200 ml 20 percent methylene
chloride-hexane, was analyzed for lindane, HCB, aldrin,
heptachlor, heptachlor epoxide, DDE, TDE, DDT, and
polychlorinated biphenyls (PCBs).
Fraction B, eluted with 200 ml 20 percent methylene
chloride-hexane, was analyzed for dieldrin, dursban, and
trithion.
Fraction C, eluted with 200 ml acetone, was analyzed
for malathion, ethion, delnav, and diazinon.
The eluates were concentrated to 1 ml. Fractions A and
B were examined by injection into a Varian Model
2700 gas-liquid chromatograph fitted with a tritium
electron-capture detector. Fraction C was injected into
Vol. 12, No. 4, March 1979
185
E
a
Q.
CD
D
■g
w
1-6f
1-4
$ 1-2
10
•8
S -6
FIGURE 1.
0
Rice crops
drained
^^^^
Rice crops
treated for
bloodworm
1970
1972
M
M
O N
D
Month
Mean organochlorinc conteii! of eastern water rat livers by month sampled, Miirriimbiclgee irrij;ation area.
New South Wales, Australia, 1970-72
( :DDT represented at least 94 percent of residues in each month. Number of samples
analyzed each month was 7, 2, 3, 2, 7, 6, 3, 4, respectively.)
a Tracer gas-liquid chroniatograph fitted with a phos-
phorus-mode flame photometric detector (Table 1).
Residues detected at 0.005 ppm and above were reported
to the nearest 0.0 1 ppm.
CONFIRMATION OF RESIDUES ANO RECOVERIES
All samples having organochlorine residues greater than
0.1 ppm were spotted on a thin-layer chromatographic
plate for confirmation. Blank analyses were carried out
TABLE 1. Parameters jor gas-liquid chromatographic
analyses for pesticides in eastern water rats, 1970-72
V*B1AN 2700
Tracor 550
Detector
tritium
FPD
(P mode)
Columns
glass Va-inct) I.D.. 6 foot
effective
lengiti
Column packing
a mixture of 0.2Cc
Vc^
OV-1 on
DC-2110 :ind O.X":*,
Gas
Chrom Q
QI--1 on
Varaport 30
Tcmperatuics, °C
column
200
220
inlet
221)
230
delcclor
220
170
Carrier pas flow (ml
minute)
nitrogen
30
60
hydrogen
50
air
100
at frequent intervals from the sodium sulfate/Soxhlet
step. Replicate recoveries (Table 2) were carried out by
adding known amounts of organochlorine and organo-
phosphorus pesticides to sodium sulfate in the Soxhiet
thimble and treating the recovery as in the sample
procedure.
Because a one-step cleanup was not sufficient, the aceto-
nitrile-hexane partition method was used (6). This re-
sults in low HCB recoveries; consequently HCB results
were corrected for recovery as follows:
HCB (reported) = HCB found in determination
X (100/33)
Results and Discussion
Pesticide residues detected in the water rats are listed
in Table 3. All samples contained organochlorines and
an unidentified organophosphorus compound. There
were no significant dilTcrenccs in residue levels between
males and females. Mammary glands, because of their
fatty composition, contained the highest levels, and
residues tended to increase as parturition approached.
Mammary TDE positively correlated with fetal weight
186
Pesticides Monitoring Journal
TABLE 2. Results of replicate recoveries of organochlorines
and organophosphates in eastern water rats, 1970-72
Amount
ADDED,
No. OF
IV
EAN % RECOVERY
Pesticide
liO
REPLICATES
± STD DEV
HCB
0.25
6
33.0 ± 4.49
DDE
0.25
4
76.5 ± 6.70
TDE
0.25
6
89.0 ± 8.61
DDT
0.25 only
2 recoveries
measured
(71% and 92%)
Dieldrin
0.25
7
83.0 ± 6.36
Malathion
4
98.8 ± 8.93
Diazinon
5
75.4 ± 13.31
Delnav
4
85.8 zt 4.91
Dursban
6
86.7 ± 7.49
Ethior
5
84.6 ± 4.03
Trithion
5
86.2 ± 7.68
(P < 0.05). Liver TDE was correlated with mammary
TDE (P < 0.001 ). Fetal residues tended to reflect ma-
ternal liver residues and were positively correlated with
fetal weight (P < 0.01).
No significant differences in residues were found be-
tween younger and older animals and breeding and non-
breeding animals (Table 4). However, younger animals
tended to carry lower levels than older animals. The
nonbreeding female group was the only one which
showed a positive correlation between age and residue
level (P < 0.05). Breeding females had the highest
liver pesticide loads, and nonbreeding females, mature
and immature, had the lowest. Kidney residues were
lower in breeders than in nonbreeders.
Stomachs of pregnant females contained more food
items, particularly insects, than did those of males or
nonbreeding females (8). This suggests that breeders
may have a greater opportunity for contamination
through greater food consumption and may consume
more dead and dying nontarget arthropods weakened
by insecticides, as demonstrated by Stchn in small
mammal scavengers (7). Lower liver residues in non-
breeding females and increasing residues in mammary
glands as parturition approached suggested a lowering
of body burdens through mobilization of fat during
pregnancy and lactation; this phenomenon is thought
to occur in harbor porpoises (i) and Arctic ringed
seals (1).
Seasonal changes in residue levels may be related to
irrigation and pesticide application practices in the area.
Peak residues occurred in animals in April after water
had been drained from the rice fields in March (Fig. 1).
Because DDT has a low water solubility and deposits
out of suspension to be adsorbed on organic matter,
plants, and sediments (4), increased amounts may be
available to water rat prey in the dry soil of drained
rice fields and, particularly, through flushing of water
with suspended clay, organic matter, and plant material
into the creek.
Up to 8 ppm DDT has been found in sediments of
drainage channels adjacent to the rice bays, indicating
considerable movement of the pesticide from the site
of application (K. H. Bowmer. Division of Irrigation
Research, 1974, personal communication). Fish and
aquatic insects may also be flushed from the bays or may
be stranded in drained fields, becoming easy prey. A
smaller peak in residue levels in November coincides
with the treatment of rice for bloodworm.
Corresponding with the April peak residue levels, there
was a seasonal decline in weight of the rats which may
indicate a breakdown of body fats and consequent
release of stored pesticides. Because trophic level is
thought to be one factor in biomagnification of residues,
TABLE 3. Pesticide residues in liver, kidney, mammary glands, and fetal liver samples from water rats,
Murrumbidgee irrigation areas, New South Wales, Australia, 1970-72
Residues, ppm
air-dried WT (± STD DEV.)
No.
(Range)
Tissue
Samples
DDE
TDE
DDT
Dieldrin
HCB
2 DDT
Females
17
0.40 -<- 0.14
0.09 + 0.05
0.01
0.01 ±0.01
0.03 ± 0.02
0.49 ±0.19
(2.10-0.01 >
(0.85-ND)
(0.()6-ND)
(0.09-ND)
(0.40-ND)
(3.10-0.01)
Kidneys
12
0.17-1- 0.03
0.03+0.01
ND
ND
0.01 ±0.01
0.20 ± 0.03
(0.46-ND)
(0.15-ND)
(0.11-ND)
(0.57-0.06)
Mammary glands 6
5.07 ± 2.22
2.11 ± 1.68
0.64 ± 0.37
0.01 ± 0.01
ND
7.82 ± 3.86
(12.20-0.13)
(10.40-ND)
(2.23-ND)
(0.05-ND)
(23.75-0.14)
Fetal liver
2
0.30
0.13
0.05
0.04
ND
0.47
(0.38-0.22)
(0.23-0.02)
(0.05-0.04)
(0.05-0.02)
(0,66-0.28)
Males
Livers
17
0.44-^0.10
0.05 + 0.02
ND
0.01
ND
0.49 ±0.11
(1.57-0.02)
(0.22-ND)
(0.04-ND)
(0.04-ND)
(0.08-ND)
(1.61-0.02)
Kidneys
13
0.31 ±0.06
0.02 ± 0.01
0.01
0.01
0.33 ± 0.07
(0.89-ND)
(0.20-ND)
ND
(0.04-ND)
(0.08-ND)
(1.12-ND)
NOTE; PCBs not detected in any sample; ND
^One liver with O.OI ppm malathion.
<0.01 ppm.
Vol. 12, No. 4, March 1979
187
TABLE 4. Differences in organoclilorinc residues in livers
and kidneys of eastern water rats, MurrumlMdgce irrigation
areas, New South Wales, Australia, 1970-72
Mean total residues,
ppm wet wt
Liver
Kidney
Females
Est. age < 6 months
Est. age ^ 6 months
Nonbrceding
Pregnant only
Pregnant and lactating
Males
Est. age < 6 months
Est. age ^ 6 months
0.39 (5)
0.64 (12)
0.40 (11)
0.83 (4)
0.67 (2)
0.33 (5)
0.56 (12)
0.10 (2)
0.26 (10)
0.24 (8)
0.18 (3)
0.06 ( 1 )
0.36 (4)
0.33 (9)
NOTE: Age of all animals was estimated by use of dry eye lens
weights. Tests were scrotal in males 6 months or older and
nonscrotal in those younger than 6 months. Number of
animals used in samples is in parentheses.
it is of interest that in the months of high residue levels,
April-August, vertebrates were more important in the
diet and insects were less important (8). Although
stomach and rectal contents revealed food intake over a
limited period, they may represent individual preference
and reflect seasonal trends. Higher residues were found
in those animals with fish, mammal, bird, and crus-
tacean remains in their guts than in those with insects
and spiders (P < 0.01). Mean liver residues and corre-
sponding stomach contents were as follows: mammals
(n = 3), 0.99 ppm; fish (n = 3), 1.29 ppm; birds
(/I = 5), 1.04 ppm; crustaceans (n = 2), 1.89 ppm;
spiders (« = 4), 0.33 ppm; and insects {n = 9), 0.51
ppm.
There was no significant difference between residue
levels in 1970 and 1972. HCB was found in 1970 sam-
ples only. Dieldrin, found in 4 of 17 liver samples
(0.01-0.03 ppm) in 1970, occurred in 7 of 17 samples
in 1972 (0.01-0.09 ppm). DDT and dieldrin sales were
unchanged during the study. However, in 1972, the
organophosphate abate was used in more rice-growing
areas for bloodworm treatment, and HCB was no longer
recommended for use as a fungicide.
Data from other studies on water rats are scarce. The
Australian Academy of Science (2) reports in its ap-
pendices that residues of 2DDT in a water rat in Vic-
toria were: fat. 0.50; muscle, 0.23; kidney, 0.19 ppm
wet weight. However, no biological information or lo-
cality is given.
Although DDT is no longer recommended for blood-
worm control, the moderate degree of contamination
found in water rats and the continuing use of poten-
tially harmful pesticides in the area point to the need for
a more detailed study on the fate and ecological effect of
these substances, with particular emphasis on more
sensitive species.
A cknowledgments
Authors thank the staff of the pesticide group, Australian
Government Analytical Laboratories, South Australia,
for preparation and analysis of samples; officers of the
New South Wales Department of Agriculture at Griffith
and Yanco for information on pesticide use; J. Duns-
more for suggesting that the analyses be made; and
K. H. Bowmer. H. J. Banks, and B. V. Fennessy for
their comments on the manuscript.
LITERATURE CITED
(/) Addison, R. F., and T. G. Smith. 1974. Organochlorine
residue levels in Arctic ringed seals: variation with age
and sex. Oikos 25(3 ) :335-337.
(2) Australian Academy of Science. 1972. The use of DDT
in Australia. Reports of the Australian Academy of
Science No. 14.
(.?) Gaskin. D. £., M. Holdrinet, and R. Frank. 1971. Or-
ganochlorine pesticide residues in harbour porpoises
from the Bay of Fundy region. Nature (London)
233(5320) :499-500.
(4) Muirhead-Thomson, R. C. 1971. Pesticides and Fresh-
water Fauna. Academic Press. New York, NY, pp.
190-191.
(5) Settle, H., and R. Swift. 1972. Simultaneous extraction
of organophosphorus and organochlorine pesticide
residues and subsequent clean-up for G.L.C. and T.L.C.
determinations. Residue 1(4): 3-8.
(6) Smyth, R. J. 1972. Detection of hexachlorobenzene
residues in dairy products, meat fat, and eggs. J. Assoc.
Off. Anal. Chem. 55(4) :806-808.
(7) Stchn, R. A. 1976. Foraging response of small mammal
scavengers to pesticide-killed arthropod prey. Amer.
Midi. Nat. 95(1 ):253-256.
(8) Woollard, P., W.J. M. Vestjcns, and L. Maclean. 1978.
The ecology of the eastern v\ater rat. Hydromys chry-
sogaster, at Griffith, N.S.W. Food and feeding habits.
Aust. Wildl. Res. 5I(l):59-73.
188
Pesticides Monitoring Journal
Organochlorine Residues in Harp Seal (Phagophilus groenlandicus) Tissues,
Gulf of St. Lawrence, 1971, 1973'
K. T. Rosewell, D. C. G. Muir, and B. E. Baker
ABSTRACT
Levels of p,p'-DDT, p,p'-TDE, p.p'-DDE. dieldrin. poly-
chlorinated biphenyls (PCBs), and HCB were determined in
certain tissues of 31 harp seals (Phagophilus groenlandicus)
taken from the Gulf of St. Lawrence during 1971 and 1973.
The seals ranged in age from less than two weeks to 18
years. Mean concentrations of PCBs and ZDDT in the vari-
ous tissues were about the same. ZDDT levels were 1.64-
9.8S ppm in adult seal blubber and 1.08-3.73 ppm in seal
pup blubber. Organochlorine levels in harp seal samples
taken in 1973 were similar to those reported by other work-
ers for samples collected in the Gulf of St. Lawrence during
1967-71.
Introduction
Seals occupy a top position in long food chains, and
because they carry large quantities of subcutaneous fat
which can store organochlorines, they have been used
as indicators of pollution in the marine environment
(/, 3, 5, 7, 8. II, 13). Organochlorine concentrations in
seals collected in 1967 and 1968 in the Gulf of St.
Lawrence indicated a degree of marine pollution similar
to that in European coastal waters (10). In the present
study, harp seals {Phagophilus groenlandicus) from the
Gulf of St. Lawrence region were examined for organo-
chlorines to determine whether 1967-68 marine pollu-
tion levels still existed and to measure organochlorine
residue levels in various tissues of adult and young
harp seals.
Materials and Methods
SAMPLE COLLECTION
Tissue samples were obtained from 1 1 harp seals (age
1-18 years) caught in the Gulf of St. Lawrence in 1971,
and 20 harp seal pups caught in the same region in
1973. All samples were frozen immediately after collec-
tion and transported to the laboratory where they were
stored at — 20°C until analysis. Blubber, kidney, liver,
muscle, spleen, brain, and gonad tissues were taken for
analysis.
ANALYTICAL METHODS
Tissue samples obtained in 1971 were analyzed as de-
scribed by Porter et al. (16) for their fat content in order
to estimate how much tissue would contain the 1-3 g of
fat required for organochlorine analysis.
An appropriate weight of each sample was dried with
sodium sulfate and then extracted with petroleum
ether {16). The petroleum ether extracts were cleaned
by acetonitrile-petroleum ether partitioning and Florisil
column chromatography (17). The 6:94 (v/v) diethyl
ether: petroleum ether eluate from the Florisil column
was transferred to a 4:1 (by weight) silica-Celite col-
umn (4) in order to separate PCBs from 2DDT. The 15
percent eluate from the Florisil column, which contained
dieldrin residues, was subjected to further cleanup in
which concentrated eluate was refluxed with 2:92 (v/v)
methanolic KOH (17).
Tissue samples from harp seal pups caught in 1973 were
analyzed for fat content by the method of Holdrinet (12).
An appropriate weight of each sample was mixed with
sodium sulfate and sand and then extracted with hexane
on a Soxhlet extractor. The hexane extracts were cleaned
on a deactivated (2 percent) Florisil column (12, 15),
and then were passed through a charcoal column (12) in
order to separate PCBs and HCB from SDDT.
Pesticides and PCBs were determined by (-'H) electron-
capture gas chromatography under the following
conditions:
Chromatograph:
Columns:
Temperatures. °C:
Chromatograph:
Columns:
Temperatures, "C:
Varian Model 600D
(1) glass, 1.08 m X 3 mm OD, packed with a
mixture of 6 percent QF-1 and 4 percent
SE-3() on Chromosorb W-HP
(2) glass. 1.68 m V 3 mm OD, packed with
1 percent OV-1 on Chromosorb W-HP
column ( 1 ) 195
column <2) 185
Varian Model 1400
glass. 1.83 m X 3 mm ID packed with:
(Da mixture of 6 percent QF-1 and 4 percent
SE-30 on Chromosorb W-HP
(2)3 percent OV-225 on Chromosorb W-HP
column (1) 215
column (2) 185
'Department of Agricultural Chemistry and Physics. Macdonald Col-
lege of McGill University, Saint Anne-de-Bellevue, Quebec, Canada
HOA ICO. Research was supported in part by the Quebec Agricultural
Research Council and by a scholarship from the National Research
Council.
Known quantities of pesticides (p,p'-DDT, p,p'-TDE.
p,p'-DDE, and dieldrin) and PCBs (Aroclors 1242 and
Vol. 12, No. 4, March 1979
189
1260) were added to a sample of the sodium sulfate
used to dehydrate the tissues. Extraction by the method
of Porter et ai. (16) produced recoveries of 69-102
percent for organochjorine pesticides and 69-84 percent
for PCBs. The following recoveries were obtained using
the method of Holdrinet {12): p.p'-DDT, p.p'-TDE, and
p.p'-DDE. 85-112 percent; dieldrin, 81-89 percent;
PCBs (Aroclor 1254), 84-85 percent; HCB, 78-89
percent.
Gas-liquid chromatography results were confirmed by
use of two columns of different polarity, by thin layer
chromatography, and by chemical derivatization. In all
instances, the results were confirmed by at least two of
the three procedures.
Results and Discussion
The fat content of seal tissues is shown in Tabic 1.
Tables 2 and 3 show the results, not corrected for re-
covery, of analyses of the various tissues for organo-
chiorines. -DDT and PCBs were detected in all samples.
Dieldrin was detected in all but five tissue samples
analyzed. Forty of 42 tissue samples from harp seal
pups contained HCB. Blubber contained the highest
levels of organochlorines. The mean PCB and SDDT
concentrations in various tissues were about the same.
Mean HCB levels, determined only in seal pups, and
mean dieldrin levels were similar in all tissues analyzed.
Brain tissue contained more extractable lipid (8.3 per-
cent) than did liver (3.5-4.0 percent), kidney (4.2
percent), muscle (2.6 percent), and spleen (2.8 per-
cent). Mean levels of i:DDT and PCBs in the brain,
however, were lower than in other ti.ssues. The results
suggest that a brain barrier to PCB- and DDT-type
compounds may exist in the harp seal as reported by
Frank et al. (7). This may result from a difference be-
tween the constitution of brain lipids and the lipids of
depot fat. The authors suggest that a similar phenome-
non may exist with dieldrin, but it was not observed in
the present work.
TABLE 1. Fat content of tissues oj harp seals.
Gulf of St. Lawrence— 1971. 197 S
Tissue
Blubber (adulls)
(pups)
Liver (adulis)
(pups)
Kidney (adulls)
Muscle (adults)
Spleen (adulls)
Brain (pups)
Gonad (male pups)
(female pups)
No.
Samples
Analyzed
Average
Fat
Content, %
5
7
82.5
86.2
2
3
3.5
4.0
3
4.2
2
2.6
2
2.8
3
8.3
1
1
1.7
7..1
Since the types of residues in tissues of the harp seal
pups were similar to those in the same tissues of older
seals, it is probable that the residues in the adult seals
are passed along to the fetus as well as to nursing seal
pups. Holden concluded that organochlorine residues in
nursing gray seal pups were derived solely from the
parent seals, since the pups were still being fed by the
adult females at the time of capture (//). This conclu-
sion is supported by the fact that organochlorines have
been found in the milk of fur seals ( 2 ) and harp seals (6) .
Organochlorine levels in harp seal pups in the present
study are similar to those reported previously in harp
seals taken from the Gulf of St. Lawrence (9, 10, 14).
In the present study, blubber, liver, and brain tissues of
young harp seals contained PCB levels similar to and
dieldrin levels higher than those found by Frank et
al. (7), i;DDT levels were slightly higher in the blubber
and liver, but similar in brain tissue to those of pups
studied by Frank et al. (7).
In the present study, the blubber of adult harp seals
contained slightly lower levels of -DDT and PCBs than
did those reported by Addison et al. (/) and Frank et
al. (7). Muscle tissue of adult seals contained higher
levels of PCBs but similar levels of -DDT and dieldrin.
Liver tissue had lower levels of -DDT but higher con-
centrations of PCBs than did the corresponding tissue
analyzed by the above authors (/, 7). Dieldrin concen-
trations in tissues analyzed for the present study were
similar to those reported previously (/. 7, 14).
The ratio of 2DDT to PCBs (Table 4) was close to 1.0
in all tissues except the liver, muscle, and spleen of the
adult seals. This may reflect heavy use of DDT for
spraying forests in areas drained by rivers flowing di-
rectly into the Gulf of St. Lawrence, as well as the high
degree of urban industrial pollution which is the major
source of PCBs in the environment.
A cknowledgmen ts
Authors thank D. E. Sergeant and the staff of the
Fisheries Research Board of Canada for providing the
1971 samples and for assisting in the collection of the
1973 samples.
LITERATURE CITED
(/) Addison, R. F.. S. R. Kerr, J. Dale, and D. E.
Serjeant. 1973. Variation in organochlorine residue
levels with age in Gulf of St. Lawrence harp seals
(I'liaaophitus aroenlandicus). J. Fish. Res. Board Can.
30(5): 595-600.
(2) Anas, R. E.. and A. J. Wilson, Jr. 1970. Organo-
chlorine pesticides in nursing fur seal pups. Pcstic.
Monit. J. 4(3):114-116.
(3) Anas. R. E. 1974. DDT plus PCBs in blubber of
harbor seals. Pestic. Monit. J. 8(1): 12-14.
190
Pesticides Monitoring Journal
TABLE 2. Organochlorine residues in tissues
of adult harp seals. Gulf of St.
Lawrence—
-March 1971
Residues, ppm wet weiuht
Seal Age.
Number Sex years
Tissue
p,p'-DDE
P.P-TDE
P,p'-DDT
2 DDT
DiELDRIN
PCBs
1 M 11
blubber
0.680
0.359
1.096
2.135
0.320
2.05
Itidney
0.070
0.036
0.212
0.318
0.012
0.26
liver
0.105
0.043
0.291
0.439
0.006
1.45
muscle
0.138
0.039
0.102
0.279
0.005
0.47
spleen
0.039
0.016
0.076
0.131
<0,002
0.16
2 F 1
blubber
0.918
0.433
8.530
9.881
0.244
0.49
kidney
0.268
0.194
2.197
2.659
0.002
1.54
liver
0.147
0.088
0.079
0.314
0.004
0.65
muscle
0.048
0.017
0.063
0.128
0.002
1.10
spleen
0.358
0.292
0.759
1.409
0.004
2.57
3 M 3
blubber
2.056
0.683
2.684
5.423
0.011
2.45
kidney
0.145
0.060
0.206
0.411
0.005
0.86
liver
0.060
0.075
0.147
0.282
0.007
0.37
muscle
0.052
0.031
0.090
0.173
0.003
0.18
spleen
0.108
0.059
0.086
0.253
0.004
0.55
4 M 5
blubber
0.726
0.631
2.550
3.907
0.024
13.30
kidney
0.057
0.020
0.082
0.159
0.005
0.62
liver
0.086
0.116
0.106
0.308
0.009
0.76
muscle
0.089
0.018
0.097
0.204
0.002
0.34
J M 6
blubber
1.187
0.459
1.280
2.926
0.096
1.96
kidney
0.048
0.023
0.047
0.118
0.002
0.25
liver
0.039
0.071
0.036
0.146
<0.002
0.11
muscle
0.076
0.057
O.084
0.217
0.002
0.46
spleen
0.056
0.038
0.156
0.250
<0.002
0.17
6 M 6
blubber
0.835
0.316
1.501
2.652
0.012
3.51
kidney
0.097
0.041
0.039
0.177
0.004
0.45
liver
0.170
0.086
0.055
0.311
<0.002
0.48
muscle
0.094
0.040
0.106
0.240
0.005
0.32
spleen
0.112
0.062
0.103
0.277
0.009
0.30
7 M 2-3
blubber
0.610
0.287
1.551
2.448
0.124
3.46
kidney
0.034
0.016
0.042
0.092
<0.002
0.04
liver
0.052
0.030
0.087
0.169
0.016
0.82
spleen
0.051
0.021
0.059
0.131
0.002
0.07
8 M 1-2
blubber
1.063
0.732
3.391
5.186
0.010
1.53
kidney
0.074
0.036
0.070
0.180
0.006
0.19
liver
0.077
0.114
0.057
0.248
0.002
0.36
muscle
0.091
0.087
0.130
0.308
0.003
0.77
spleen
0.094
0.095
0.152
0.341
0.007
0.30
9 M 13
blubber
0.556
0.354
0.731
1.641
0.022
1.20
kidney
0.071
0.022
0.128
0.221
0.005
0.18
liver
0.217
0.149
0.455
0.821
0.018
0.36
muscle
0.098
0.038
0.068
0.204
0.004
0.07
spleen
0.075
0.023
0.091
0.189
0.010
0.33
10 M 13
blubber
1.849
0.770
2.300
4.919
0.022
2.77
kidney
0.125
0.077
0.366
0.568
0.008
0.20
liver
0.347
0.215
0.121
0.683
0.026
0.64
muscle
0.060
0.033
0.112
0.205
0.008
0.06
spleen
0.049
0.023
0.047
0.119
0.003
0.09
11 M 18
blubber
1.108
0.680
1.326
3.114
0.01 1
2.83
kidney
0.061
0.047
0.064
0.172
0.005
0.31
muscle
0.066
0.054
0.200
0.320
0.009
0.41
spleen
0.043
0.161
0.090
0.294
0.016
0.07
NOTE: Detection limit = 0.002 ppm.
(4) Armour, ]. A., ami ]. A. Burke. 1970. Method for
separating polychlorinated biphenyls from DDT and
its analogs. J. Assoc. Off. Anal. Chem. 53(4) ;761-
768.
(5) Bowes. G. W., and C. J. Jonkel. 1975. Presence and
distribution of polychlorinated biphenyls (PCB) in
arctic and subarctic marine food chains. J. Fish. Res.
Board Can. 32(11 ):21 11-2123.
(6) Cook. H. W.. and B. E. Baker. 1969. Seal milk. I.
Harp seal (Phaaophilus groentandicus) milk: Compo-
sition and pesticide residue content. Can. J. Zool.
47(6): 1129-1132.
(7) Frank. R., K. Ronald, and H. E. Braun. 1973. Or-
ganochlorine residues in harp seals (Phagophilus
groenlandicus) caught in eastern Canadian waters. J.
Fish. Res. Board Can. 30(8) : 1053-1063.
(S) Gaskin. D. £.. R. Frank, M. Holdrinct, K. Ishida, C.
J. Walton, and M. Smith. 1973. Mercury. DDT and
PCB in harbour seals (Phoca viiulina) from the Bay
of Fundy and Gulf of Maine. J. Fish. Res. Board
Can. 30(3):47I^75.
(9) Holden, A. V., and K. Marsden. 1967. Organochlo-
rine pesticides in seals and porpoises. Nature 216
(5122): 1274-1276.
Vol. 12, No. 4, March 1979
191
TABLE 3. Organochlorine residues in tissues of harp seal pups, Gulf of St. Lawrence — March 1973 >
Seal
Number
Tissue
p.p'-DDT
P.p'-TDE
P.P-DDE
2DDT
DiELDRIN
HCB
PCBs
1
blubber
liver
brain
0.833
0.041
0.026
0.132
0.007
0.003
2.019
0.096
0.021
2.984
0.144
0.050
0.087
0.005
0.006
0.054
0.003
0.002
1.812
0.116
0.097
2
blubber
liver
brain
0.602
0.027
0.028
0.119
0.004
0.003
1.044
0.025
0.010
1.765
0.056
0.041
O.ISO
0.007
0.010
0.130
0.007
0.005
1.869
0.063
0.022
3
blubber
liver
brain
0.830
0.031
0.034
0.209
0.008
0.006
1.314
0.037
0.014
2.353
0.076
0.054
0.117
0.007
0.008
0.061
0.003
<0.002
2.984
0.116
0.037
4
blubber
liver
brain
0.460
0.038
0.022
0.079
0.006
0.003
0.690
0.036
0.011
1.229
0.080
0.036
0.092
0.006
0.006
0.109
0.007
0.004
1.392
0.112
0.029
5
blubber
liver
brain
0.599
0.032
0.007
0.100
0.004
0.002
0.787
0.019
0.007
1.486
0.055
0.016
0.075
0.004
0.004
0.106
0.005
0.003
1.601
0.043
0.019
6
blubber
liver
brain
0.811
0.023
0.015
0.096
0.004
0.002
1.206
0.024
0.010
2.113
0.051
0.027
0.103
0.004
0.006
0.114
0.005
0.003
1.476
0.039
0.017
7
blubber
liver
brain
0.750
0.023
0.023
0.129
0.005
0.004
1.713
0.040
0.017
2.592
0.068
0.044
0.082
0.003
0.005
0.062
0.003
0.002
2.908
0.071
0.039
8
blubber
liver
brain
0.670
0.031
0.019
0.144
0.008
0.003
1.294
0.060
0.016
2.108
0.099
0.038
0.096
0.009
0.009
0.034
0.004
0.002
2.623
0.145
0.033
9
blubber
liver
brain
0.729
0.021
0.034
0.115
0.006
0.005
1.294
0.041
0.014
2.138
0.068
0.053
0.096
0.004
0.007
0.055
0.003
<0.002
2.664
0.099
0.041
10
blubber
liver
brain
0.660
0.037
0.006
0.086
0.007
0.003
1.079
0.056
0.007
1.825
0.100
0.016
0.095
0.007
0.005
0.085
0.006
0.002
1.810
0.115
0.022
11
blubber
0.578
0.117
1.137
1.832
0.088
0.121
2.020
12
blubber
0.536
0.086
0.757
1.379
0.075
0.065
2.268
13
blubber
gonad
0.468
0.023
0.053
0.003
0.562
0.012
1.083
0.038
0.076
0.002
0.083
0.002
1.150
0.045
14
blubber
gonad
0.634
0.079
0.132
0.014
1.327
0.116
2.093
0.209
0.093
0.008
0.119
0.011
2.225
0.211
15
blubber
0.735
0.152
0.994
1.881
0.104
0.067
2.074
16
blubber
0.760
0.159
1.362
2.821
0.144
0.097
2.416
17
blubber
0.460
0.071
0.830
1.361
0.073
0.068
1.926
18
blubber
1.188
0.404
2.138
3.730
0.179
0.042
6.226
19
blubber
0.475
0.100
0.708
1.283
0.087
0.050
2.313
20
blubber
0.626
0.070
0.875
1.571
0.074
0.028
1.512
NOTE: Deteclion limit
^ Age of pups <2 weeks.
0.002 ppm.
DDT/DDE
i:DDT/PCB
2.32
1.24
0.58
0.86
1.10
0.62
0.70
0.92
3.30
1.04
1.30
0.54
1.65
0.74
1.62
1.03
TABLE 4. Ratios of DDT to DDE and ^DDT to PCBs
in harp seal tissues, Gulf of St. Lawrence — 1971-1973
Tissue
Blubber (adults)
(pups)
Liver (adults)
(pups)
Kidney (adults)
Muscle (adults)
Spleen (adults)
Brain (pups)
NOTE; Ratios calculated from mean concentrations of each residue.
(10) lloUicn. A. V. 1969. Organochlorine residues in seals.
Report No. E. 22, Fisheries Improvement Committee,
International Council for Exploration of the Sea, 7 pp.
(//) Holdcn, A. V. 1970. Monitoring organochlorine con-
lamination of the marine environment by analysis of
residues in seals. Report presented to the FAO Con-
ference on Marine Polltilion, Rome, 15 pp.
(12) Holdrinet, M. V. H. 1974. Determination and confir-
mation of hcxachlorobenzene in fatty samples in the
presence of other residual halogenated hydiocarbon
pesticides and polychlorinated biphenyls. J. Assoc. Off.
Anal. Chem. 57(3 ) :580-584.
(13) Jensen, S., A. G. Johnels, M. Olsson. and G. Otter-
lind. 1969. DDT and PCB in marine animals from
Swedish waters. Nature 224(5216) :247-250.
(14) Jones, D., K. Ronald, D. M. Lavinnc. R. Frank, M.
Holdrinet, and J. F. Uthe. 1976. Organochlorine and
mercury residues in the harp seal ( Phai;ophilus groen-
landicus). Sci. Total Environ. 5:181-195.
(15) Langlois, B. E., A. R. Stemp, and B. J. Liska. 1964.
Analysis of animal food products for chlorinated insec-
ticide residues. I. Column clean-up of samples for
electron capture gas chromatographic analysis. J. Milk
Food Technol. 27( 7 ) :2()2-204.
(16) Porter, M. L., S. J. V. Yoiini;. and J. A. Burke. 1971.
A method for the analysis of fish, animal and poultry
tissue for chlorinated pesticide residue analysis. J.
Assoc. Off. Anal. Chem. 53(6) : 1300-1303.
(17) We.s-.Kcl, J. R., H. C. Barry. J. A. Burke, J. Cummings,
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ington, DC.
192
Pesticides Monitoring Journal
Nationwide Residues of Organochlorine Compounds in Starlings (Sturnus vulgaris), 7976
Donald H. White '
ABSTRACT
Organochlorine pesticide and PCB residues in starlings from
126 sites within the contiguous 48 states were monitored
during fall 1976. The average nationwide level of DDE and
PCBs has increased significantly since 1974, but the number
of sites reporting PCB residues has decreased fivefold. Diel-
drin residues have remained unchanged since 1974. Highest
DDE levels occurred in samples from parts of Arizona,
Arkansas, California, Louisiana, and New Mexico.
Introduction
The Fish and Wildlife Service, U.S. Department of the
Interior, began nationwide monitoring of organochlorine
residues in starlings (Sturnus vulgaris) in 1967-68 as
part of the National Pesticides Monitoring Program.
Residue data from the original collections were to serve
as a baseline against which future residue levels might
be compared. Initially, organochlorine compounds were
to be monitored at 2-year intervals. However, in 1976,
starling collections were scheduled at 3-year intervals to
coincide with waterfowl wing collections which also are
monitored nationwide for organochlorine residues. Star-
lings were selected because their range is the continental
United States, they are considered expendable, and their
omnivorous feeding habits should reflect residues from a
wide range of food sources (7). The present report
presents results of the 1976 starling collections including
residue levels from each collection site, a comparison of
nationwide averages of DDE, dieldrin, and polychlorin-
ated biphenyls (PCBs) in the four collection periods
since 1970, and the distribution of DDE, dieldrin, and
PCBs by frequency of occurrence at collection sites.
Collection Methods
Sampling design and collection procedures have been
reported previously (1-3). The sample area lies within
the continental United States and consists of 40 blocks
of 5° latitude and longitude. In the initial 1967-68
study, 139 collection sites were randomly selected within
these blocks and were to be used for starling collections
thereafter. During September-December 1976, samples
were obtained from 126 of the sites. Table 1 lists col-
ipish and Wildlife Service, U.S. Department of the Interior. Patuxent
Wildlife Research Center, Gulf Coast Field Station. P.O. Box 2506,
Victoria, TX 77901.
lection sites for 1976 by state and county; Figure 1
shows their actual locations within sampling blocks.
Starling samples consist of pools of 10 birds taken by
trapping or shooting, although some samples may be
smaller; those samples with fewer than 10 birds are
identified in Table 1. Each pool is wrapped in alumi-
num foil, placed in a polyethylene bag, frozen as soon
as possible, and shipped to Raltech Scientific Services,
Inc., Madison, Wisconsin, for chemical analysis. A total
of 227 pools were analyzed for organochlorine residues.
A nalytical Procedures
The feet, beaks, wing tips, and skins were removed from
birds in each composite sample and the sample was
weighed and ground in a food grinder. Twenty grams
of the homogenate was ground with 150 g anhydrous
sodium sulfate and allowed to air dry overnight in a
hood. The dried sample was placed in a 43 mm X
123 mm Whatman extraction thimble and extracted for
8 hours on a Soxhlet apparatus with 150 ml ethyl ether
and 150 ml petroleum ether. The resulting solution was
concentrated to near dryness on a steam bath, and the
remaining solvent was removed with nitrogen at room
temperature. The residue was transferred to a 25-mI
volumetric flask with 93:1 toluene-ethyl acetate solution
and diluted to volume.
Five ml of the extract was placed on an Auto-Prep
Model 1001 gel permeation chromatograph, standard-
ized for chlorinated insecticides and PCBs, with the
following operating conditions:
Packing: 80 g Bio-Beads (SX-3), 200^00 mesh
Column: 600 mm x 25 mm ID
Solvent: 3:1 toluene-ethyl acetate solution
Flow rate: 5.5 ml/minute
Dump time: 30 minutes
Collect time: 14 minutes
Wash time: 4 minutes
The resulting solution was concentrated on a flash
evaporator to approximately 5 ml in the presence of
5 ml isooctane and diluted to 25 ml with petroleum
ether. A 4-/^1 sample was injected into a gas chro-
matograph equipped with an electron-capture detector. If
PCBs were not detected, the results were quantified.
Vol. 12, No. 4, March 1979
193
TABLE 1. OrganocMorine residues in starlinns, continental United States, 1976
Residues,
PPM WET WEIGHT
Heptachlor
Chlordane
State
County 1
Site
DDE
DDT
DiELDRIN
PCBS2
Epoxide
HCB
Isomers
Alabama
Marion
3-H-l
0.28
ND
0.14
ND
0.05
ND
0.04
Calhoun
4-H-3
0.31
ND
0.01
0.85
0.04
ND
0.04
Arizona
Navajo
3-C-3
0.13
ND
ND
ND
ND
ND
ND
Yavapai
3-C-4
0.27
ND
0.03
ND
0.01
ND
ND
Maricopa
4-C-l
5.00
ND
0.01
ND
0.01
ND
ND
Graham (3)
4-C-2
3.41
ND
0.01
ND
ND
ND
ND
Arkansas
Yell
3-G-2
0.31
ND
ND
0.35
0.13
ND
0.06
Lonoke
3-G-3
11.10
ND
0.09
0.15
0.17
ND
0.06
California
Colusa (9)
2-A-l
0.39
ND
0.02
ND
ND
ND
ND
Shasta
2-A-2
0.16
ND
0.01
ND
ND
ND
ND
Modoc
2-A-3
0.13
ND
0.01
ND
0.01
ND
ND
Ventura
3-A-l
1.26
ND
0.04
ND
ND
ND
ND
Monterey (9)
3-A-3
2.20
0.02
0.08
0.39
ND
ND
0.01
Kern
3-B^
3.14
ND
0.03
ND
ND
ND
ND
Imperial
4-B-l
7.41
ND
0.02
ND
ND
ND
ND
Los Angeles
4-B-2
1.37
ND
0.04
ND
ND
ND
ND
Colorado
Weld
2-D-4
1.36
ND
0.06
ND
0.01
ND
ND
Montrose
3-D-l
0.26
ND
ND
ND
ND
ND
ND
Crowley
3-D-2
0.15
ND
ND
ND
0.01
ND
ND
Connecticut
New London
2-K-2
0.54
ND
0.03
0.39
0.09
ND
0.17
Florida
Bay
4-H-l
0.23
0.04
0.09
0.28
0.04
ND
0.07
Madison
4-1-3
0.90
ND
0.11
ND
0.07
ND
0.18
Highlands
5-1-2
0.67
ND
0.01
ND
ND
ND
ND
Georgia
Upson
4-H-4
1.03
ND
0.16
0.44
0.30
ND
0.20
Wayne
4-1-2
0.35
0.03
0.11
0.26
0.03
ND
0.13
Idaho
Nez Perce
1-B-l
0.16
ND
ND
ND
ND
0.01
0.01
Owyhee
2-B-l
1.15
ND
0.03
ND
0.01
ND
ND
Franklin
2-C-3
1.12
ND
0.05
ND
0.02
ND
ND
Minidoka
2-C^
2.06
ND
U.06
0.16
0.01
ND
ND
Illinois
Stephenson
2-G-l
0.49
ND
0.17
0.21
0.06
ND
0.05
Adams
2-G-3
0.04
ND
0.22
ND
0.36
0.56
0.09
Kane
2-H-2
0.65
ND
0.12
ND
0.04
ND
0.01
Indiana
Henry
2-H-3
0.02
ND
0.03
ND
0.03
0.03
0.01
Iowa
Fremont
2-F-3
0.05
ND
0.23
ND
0.12
ND
0.04
Jasper (8)
2-G-2
0.08
ND
0.28
ND
0.17
0.01
0.06
Marshall (9)
2-G-4
0.09
ND
0.07
ND
0.11
ND
0.O2
Kansas
Rawlins
2-E-l
0.29
ND
0.02
0.15
ND
ND
ND
Phillips (7)
2-E-2
0.05
ND
0.02
ND
ND
0.03
ND
Kearny (9)
3-E-l
0.03
ND
0.02
ND
0.01
ND
0.03
Nemaha
2-F.^
0.07
ND
0.16
ND
0.04
0.01
0.02
Marion
3-F-2
0.04
ND
0.06
ND
0.03
0.06
0.02
Kentucky
Ohio
3-H-2
0.15
ND
0.04
ND
0.02
ND
0.03
Hopkins (9)
3-H^
1.04
ND
0.04
ND
0.02
ND
0.11
Louisiana
Jefferson
4-G-3
0.93
ND
0.04
0.42
0.08
0.02
0.10
Rapides
4-G^
10.70
ND
0.04
0.63
0.03
ND
0.01
Maine
Penobscot
l-K-2
0.13
0.06
0.01
0.24
0.01
ND
0.01
Michigan
Chippewa
1-H 1
0.03
ND
0.03
ND
ND
ND
ND
Grand Traverse
1 H-2
0.47
ND
0.02
ND
ND
ND
ND
Kent
2-H-l
0.17
ND
ND
0.11
ND
ND
ND
Ingham
2-H^
0.51
ND
0.02
ND
0.03
ND
0.01
Minnesota
Aitkin
1-G-l
0.05
ND
ND
ND
ND
ND
ND
Renville
l-F-2
0.04
ND
0.03
ND
ND
ND
ND
Mississippi
Leake
4-G-l
0.42
ND
0.18
ND
0.26
ND
0.09
Harrison
4-G-2
0.67
0.04
0.24
ND
0.11
ND
0.07
Jackson
4-H-2
1.43
ND
0.07
ND
0.04
ND
0.03
Missouri
Butler (7)
3-G-l
0.12
ND
0.06
0.11
0.03
0.23
ND
Bollinger
3-G-4
0.06
ND
0.02
ND
ND
ND
ND
Montana
Meagher (9)
l-C-1
0.03
ND
ND
0.14
ND
ND
ND
Missoula
1-C^
0.06
0.04
O.lll
ND
0.02
0.02
ND
Richland (6)
1-D 1
0.01
ND
ND
ND
ND
ND
ND
Yellowstone
l-D-4
ND
ND
ND
ND
ND
ND
ND
Nebraska
Keith (7)
2-E-3
0.04
ND
0.02
ND
ND
ND
ND
Brown
2-E^
0.04
ND
0.02
ND
0.03
ND
ND
Lancaster (6)
2-F-l
0.25
0.07
ND
0.14
0.05
0.01
0.04
Clay
2-F-2
0.10
ND
0.07
ND
ND
ND
ND
Nevada
White Pine
2-B-3
0.07
0.04
ND
ND
ND
ND
ND
Humboldt
2 B^
0.53
ND
(1.02
ND
0.02
ND
0.04
Nye
3 B 2
0.17
ND
0.04
ND
ND
ND
ND
Clark
3-B-3
0.20
0.04
0.06
0.32
O.lfl
ND
0.21
New Mexico
Bernalillo
3D 3
0.60
ND
ND
ND
ND
ND
ND
Santa Fe
3 D-4
2.20
ND
0.03
ND
ND
ND
ND
Luna
4-D-l
0.63
ND
ND
ND
ND
ND
ND
Otero
4-D-2
1.71
ND
0.02
ND
ND
ND
ND
Chaves
4-D-3
12.40
ND
0.03
ND
0.03
ND
0.01
Quay
3-E-2
0.15
ND
ND
ND
0.01
ND
ND
(Continued next page)
194
Pesticides Monitoring Journal
TABLE 1 (Cont'd.). Organochlorine residues in
Starlings, continental United States,
1976
Residues,
PPM WET weight
Heptachlor
Chlordane
State
County'
Site
DDE
DDT
DiELORIN
PCBs =
Epoxide
HCB
ISOMEIS
New York
Jefferson (5)
2-J-4
0.09
ND
ND
ND
0.03
ND
0.04
Rensselaer (8)
2-K-l
0.99
0.03
0.02
ND
ND
ND
ND
North Carolina
Wilkes
3-1-1
0.08
ND
0.02
ND
ND
ND
ND
Macon
3-1-3
0.51
ND
0.03
ND
ND
ND
ND
Pender
3-J-l
1.21
ND
0.20
0.18
0.03
ND
0.11
North Dakota
McLean
l-E-3
0.03
ND
0.01
ND
ND
ND
ND
Grand Forks
1-F-l
0.43
ND
ND
ND
ND
ND
ND
Ransom
l-F-4
0.07
0.01
ND
0.16
ND
ND
ND
Ohio
Pickaway
2-1-1
0.05
ND
0.05
ND
0.04
0.73
0.05
Wood
2-1-2
0.08
ND
0.15
ND
0.05
0.06
0.01
Noble
2-1-3
0.08
0.04
0.01
ND
0.02
ND
0.03
Oklahoma
Beckham
3-E-4
0.14
ND
0.03
ND
0.02
ND
ND
Canadian
3-F-l
0.06
ND
0.03
ND
0.05
0.03
ND
Nowata (9)
3-F-3
1.52
ND
0.05
ND
0.02
ND
0.03
Okmulgee
3-F-4
0.12
0.05
0.10
ND
0.01
ND
0.01
Oregon
Yamhill
l-A-3
0.67
ND
0.10
ND
0.15
0.10
0.01
Lane
l-A-4
0.32
ND
0.05
ND
0.05
ND
ND
Benton
l-A-5
0.27
ND
0.06
ND
0.02
ND
ND
Klamath
2-A-4
0.20
ND
ND
ND
0.02
ND
ND
Baker (9)
l-B-4
0.06
ND
ND
ND
ND
ND
ND
Harney
2-B-2
0.15
ND
ND
ND
ND
ND
ND
Pennsylvania
Somerset (6)
2-J-2
0.46
ND
0.05
ND
0.06
ND
0.10
Luzerne
2-J-3
0.59
0.04
0.06
0.48
0.06
ND
0.13
South Dakota
Potter
1-E-l
0.07
ND
0.02
ND
ND
ND
ND
Butte
l-E-2
0.02
ND
ND
ND
ND
ND
ND
Hughes
1-E^
0.03
ND
0.02
ND
ND
ND
ND
Brown
l-F-3
0.03
ND
0.02
ND
ND
ND
ND
Tennessee
Davidson
3-H-3
0.09
0.02
0.14
0.22
0.01
ND
0.05
Texas
Kinney
4-E-3
1.05
ND
0.05
ND
0.89
ND
0.05
Cochran
4-E^
0.11
ND
0.04
ND
0.04
0.01
ND
Bexar (7)
4-F-l
0.15
ND
0.02
ND
0.04
0.02
0.04
Clay
4-F-3
0.97
ND
0.04
ND
0.47
0.07
0.07
San Patricio
5-F-l
0.23
ND
ND
ND
0.01
ND
ND
Utah
Weber
2-C-l
0.91
0.04
0.04
0.55
ND
ND
ND
Duschesne
2-C-2
0.10
ND
ND
ND
0.02
ND
ND
Millard
3-C-l
0.42
ND
0.01
ND
ND
ND
ND
Grand
3-C-2
0.93
ND
ND
ND
0.08
ND
0.02
Vermont
Addison
1-K-I
0.14
ND
0.01
0.11
0.04
ND
0.10
Virginia
Amherst (8)
3-1^
0.52
ND
0.02
ND
ND
0.02
ND
Prince George (9)
3-J-2
0.38
ND
0.02
0.11
0.02
0.04
0.05
Caroline
3-J-3
0.11
ND
0.06
ND
0.07
0.20
0.07
Washington
Yakima
l-A-2
0.26
ND
0.12
ND
0.03
0.54
ND
Spokane (5)
1 B-2
0.38
ND
0.24
ND
ND
2.01
ND
Whitman
l-B-3
0.27
ND
ND
ND
ND
0.51
ND
Wisconsin
Trempealeau (9)
l-G-3
1.16
ND
0.01
ND
0.01
ND
ND
Marathon (9)
l-G-2
0.07
ND
ND
ND
ND
ND
ND
Wyoming
Big Horn
l-D-2
0.02
ND
0.01
ND
0.03
ND
ND
Crook (9)
1-D 3
ND
ND
ND
ND
ND
ND
ND
Goshen
2-D-l
0.21
ND
ND
ND
ND
ND
ND
Washakie
2-D-2
0.07
ND
0.03
ND
0.02
ND
ND
NOTE: ND = not detected.
'Most samples consist of a pool of 10 birds. Numbers in parentheses indicate samples made up of fewer birds.
-PCBs were quantihed on the basis of Aroclor 1254.
If PCBs were detected, the extracts were subjected to
silicic acid separation. Ten ml of the extract from the
gel permeation chromatograph was placed on a 15-g
standardized Silicar CC-4 column. Typical ekitions were
as follows:
Fraction
: 60 ml petroleum ether, contains HCB and mirex
Fraction II: 350 ml petroleum ether, contains PCBs and some DDE
Fraction 111: 150-ml mixture of 1 percent acetonitrile, 19 percent
hexane. and 80 percent methylene chloride, contains
the remaining organochlorine compounds
Fractions I and II were concentrated on a steam bath
to 1-2 ml; Fraction III was concentrated on a flash
evaporator to 1-2 ml. All were diluted to 10 ml with
petroleum ether. Quantities of 4 /il per solution were
injected into a gas chromatograph equipped with an
electron-capture detector.
Determinations were made on a Hewlett-Packard Model
5710A gas chromatograph equipped with a linear Ni'^^
detector and automatic injector, attached to a Hewlett-
Packard Model 3352C data acquisition system. Instru-
ment parameters and operating conditions for determin-
ing clilorinated insecticides and PCBs follow:
Vol. 12, No. 4, March 1979
195
Column: glass, 1219 mm X 4 mm ID. packed with a
mixture of 1.95 percent OV-17 and 1.5 percent
QF-1 on 80-100-mesh .Supelcoport
Temperatures, "C: column 200
injector 250
detector .100
Carrier gas; a mixture of 95 percent argon and 5 percent
methane flowing at ,^3 ml minute
Instrument parameters and operating conditions for
determining chlordane isomers were:
Column: glass, 1219 mm X 4 mm ID. packed with 3 per-
cent OV-1 on SO-lOO-mesh Gas-Chrom Q
Temperatures, *C: column 190
injector 250
detector 300
Carrier gas: a mixture of 95 percent argon and 5 percent
methane flowing at 32 ml/minute
Residues in 5 percent of the samples were confirmed by
mass spectrometry. Recoveries were 74-120 percent;
analytical results were not corrected.
All residues are expressed as ppm wet weight. They
may be converted to dry or lipid weight by dividing a
given wet-weight value by 0.30 or 0.05, the mean pro-
portions of dry and lipid material in the samples. Quan-
tification limit was 0.01 ppm for organochlorine com-
pounds. Trace residues were not reported.
Results and Discussion
Residues of DDE, DDT, dieldrin, PCBs, heptachlor
epoxide, hexachlorobenzene (HCB), and chlordane
isomers in starlings collected in 1976 are shown in
Table 1. Since collections were made in the fall, residues
do not necessarily reflect year-round levels. Also, find-
ings should not be interpreted strictly on a statewide
basis because some starlings are migratory. However,
samples from certain localities consistently contain fairly
high residues, suggesting that samples reflect local en-
vironmental contamination. For example, when results
from previous monitorings (1-4) are compared, samples
from certain parts of Arizona, Arkansas, California,
Louisiana, and New Mexico usually contain higher DDE
levels than do those from other states.
A summary of DDE, dieldrin, and PCB residues in
starlings from 1970 through 1976 is shown in Table 2.
The average DDE level in 1976 was similar to the 1970
level, before the use of technical DDT had been sus-
pended. In fact, DDE residues were significantly higher
nationwide {P<0.00\ ) in 1976 than in 1974 (Table 2).
It is difficult to explain why DDE residues have in-
creased sharply since 1974, when residues were at their
lowest level in 7 years. Possibly, DDT or its related
FIGURE I. Starting collection sites, continental United States, 1976
196
Pesticides Monitoring Journal
TABLE 2. Comparison of DDE. dieldriii, and PCB residues in starlings, continental United States, 1970-76
No. Pools
Residues, ppm wet weight
DDE
DlELDRlN
PCBs
Year
x±SEi
Range
Geom. X
x±SE
Range
Geom. x
x±SE
Range
Geom. x
1970
125
0.839 ±0.138
(125)
0.037-48.2
0.355
0.117 ±0.038
(125)
0.005-3.59
0.036
0.663 ±0.196
(125)
0.09-24.3
0.358
1972
130
0.788 ±0.124
(130)
0.047-14.8
0.387
0.098 ±0.018
(130)
0.005-1.56
0.035
0.425 ±0.153
(130)
0.04-19.9
0.215
1974
126
0.617±0.118
(126)
0.007- 9.1
0.229
0.057 ±0.011
(122)
0.005-1.01
0.019
0.112±0.016
(126)
0.01- 1.9
0.068
1976
126
0.827 ± 0.174-'
(124)
0.010-12.4
0.254
0.059 ± 0.006
(96)
0.010-0.28
0.039
0.290 ±0.036 =
(26)
0.11- 0.85
0.243
^Figure in parentheses represents number of pools having detectable residues.
2 Residues in 1976 significantly higher than in 1974 (/'<0.001, Students i-tesi, log-transformed data).
compounds may have been used, especially in certain
geographical regions of the country.
Dieldrin residues declined steadily between 1970 and
1974, but the average dieldrin level in 1976 was almost
identical to the 1974 average (Table 2), indicating no
further decline of dieldrin during the 2-year period.
PCBs have increased significantly nationwide (P<0.001 )
since 1974, although 1976 residues remained below
those reported for 1970 and 1972 (Table 2). Only 26
samples contained PCBs in 1976 compared to 126 in
1974; although the average PCB level was higher in
1976 than in 1974, the number of sites reporting PCB
residues decreased fivefold in 1976.
The distribution of DDE, dieldrin, and PCBs by fre-
quency of occurrence at collection sites for 1976 is
shown in Table 3. In general, residues were low; most
values were between 0 and 1.0 ppm for the three com-
pounds. Dieldrin and PCBs were not detected in star-
lings at levels greater than 1.0 ppm.
In addition to organochlorine compounds in Table 1,
certain other chemicals were detected in starlings less
frequently. TDE occurred in six samples, ranging from
TABLE 3. Distribution of residues in starlings by frequency
of occurrence, continental United States, 1976
Number of Sites with Residues
Range, ppm
DDE
Dieldrin
PCBs
ND- 0.01
3
43
99
>0.01- 0.10
36
65
0
>0.10- 1.0
63
17
26
>1.0 -13.0
23
0
0
NOTE: ND = not detected.
0.01 to 0.10 ppm; mirex was found in 13 samples,
mostly from southeastern states, ranging from 0.01 to
1.24 ppm; lindane was detected in six samples, ranging
from 0.01 to 0.15 ppm; and endrin occurred in only
three samples, ranging from 0.02 to 0.18 ppm.
Conclusions
Nationwide, residues of DDE in starlings have increased
significantly since 1974 to approximately the level re-
ported in 1970 samples. Average PCB levels also in-
creased, but the actual number of samples containing
PCB residues declined. Dieldrin levels have remained
unchanged since 1974.
These data indicate that starlings can serve as indicators
of environmental contamination and thus provide in-
formation on residue trends over time. Geographical
differences in residue levels also were detected.
A cknowledgments
Special thanks are extended to the following for their
help with starling collections: James Elder, Robert
Hillen, Arnold Julin, Harry Kennedy, David Lenhart,
and David Walsh.
LITERATURE CITED
(/) Martin, W. E. 1969. Organochlorine insecticide resi-
dues in starlings. Pestic. Monit. J. 3(2): 102-1 14.
(2) Martin. W. E., and P. R. Nicker.son. 1972. Organo-
chlorine residues in starlings — 1970. Pestic. Monit. L
6(l):33-40.
(i) Nickerson, P. R., and K. R. Barbehenn. 1975. Organo-
chlorine residues in starlings, 1972. Pestic. Monit. J.
8(4):247-254.
(4) White. D. H. 1976. Nationwide residues of organo-
chlorines in starlings, 1974. Pestic. Monit. J. 10(1):
10-17.
Vol. 12, No. 4, March 1979
197
SOILS
Pesticide Application and Cropping Data from 37 States, 1972-
NationaJ Soils Monitoring Program
Ann E. Carey' and Jeanne A. Gowen"
ABSTRACT
This report siininKirizcs pesticide application and cropping
data collected in 1972 from 1 ,402 agricultural sampling sites
in 37 states as part of the National Soils Monitoring Pro-
gram. Pesticide application data are summarized by all sites,
state, and crop. Tables generally give the number of sites re-
porting, number of times a compound was applied, percent
occurrence, and arithmetic mean application rate.
Pesticides applied most frequently were atrazine, 2,4-D,
captan, and trifliiralin. Among selected major crops, pesti-
cides were most frequently applied to sites growing field corn
and cotton, least frequently to sites growing alfalfa/bur
clover and mi.xed hay.
Introduction
The increasing use of chemical pesticides in agriculture
in the past 30 years has helped fewer farmers feed more
people than at any other time in h'story. Today, the
American farmer not only feeds and clothes this Na-
tion's population, but also contributes significantly to the
rest of the world. Yet the sensible use of toxic com-
pounds also carries the responsibilitv to minimize their
effects on nonlarget components of the environment.
In 1963, the President's Science Advisory Committee
recommended that appropriate federal agencies "develop
a continuing network to monitor residue levels in air,
water, soil, man. wildlife and fish" (/). As a result of the
recommendation, the National Pesticide Monitoring Pro-
gram fNPMP) was established to determine levels and
trends of pesticides and their degradation products in
various components of the environment (2). The federal
responsibility for monitoring pesticides was oflficially
codified in Section 20 of the amended Federal Insecticide,
Fungicide and Rodenticidc Act of 1972 (PI. 92-516).
' Ecclogical Monilorinp Branch. Bcncfns and Field .Studies Division.
Office of Peslicidc Propr.ams, U.S. Environmcnial Protection Agency.
TS-768. Washington. DC 2046fl.
'•'Extension Agent, Colorado Slate Extension Service. Golden. CO.
The National Soils Monitoring Program (NSMP) is an
integral part of the NPMP and monitors residues in
agricultural soils and raw agricultural crops. It was
established in 1968 by the U.S. Department of Agricul-
ture and is administered by the U.S. Environmental Pro-
tection Agency. The present report summarizes pesticide
application and cropping data collected during 1972
(FY-73) from 1.402 sampling sites in 37 states. Data
for composite soil and crop samples, collected from the
sites for pesticide residue analysis, are presented in a
separate report (.?).
Sampling
The site selection criteria and statistical design of the
NSMP have been described (4). In 1972. 1.533 sites in
37 states were scheduled for sampling (Fig, 1 ). At each
4-hectare ( 10-acre) site, the landowner or operator was
interviewed concerning crops grown and the kinds and
amounts of pesticides applied during the 1972 growing
season.
Results and Discussion
CO.MPOUNDS APPLIED TO CROPLAND
Cropping and pesticide use data were received from
1.402 of the scheduled 1,533 sites or 91 percent. Of
these, 742 or 53 percent of the sites had one or more
pesticides applied during the 1972 growing season. Tables
summarizing the application data show the number of
sites reporting a pesticide application, the percent of
sites reporting the pesticide application, and the average
rate of application, expressed in poimds per acre and
kilograms per hectare.
Table I lists the frequency of pesticide use on sample
sites in various states and state groups. Because some
small eastern states had very few sites, those with similar
geographic location and/or agricultural characteristics
were combined to obtain more representative data. State
groups used were Mid-Atlantic: Delaware, Maryland,
198
Pesticides Monitoring Journal
FIGURE I. Slates scheduled jor sampling, 1972 — National Soils Monitoring Program
TABLE 1. Pesticide application data jrom 1 .402 reporting
sites in 37 stales, 1972 — National Soils Monitoring Program
Pesticides
No Pesticides
No. OF
Used
Used
Sites
eporting
State R
No.
Co
No.
%
Alabama
20
9
45
11
55
Arkansas
47
29
62
18
38
California
52
22
42
30
58
Florida
15
7
47
8
53
Georgia
27
13
48
14
52
Idaho
30
15
50
15
50
Illinois
139
94
68
45
32
Indiana
74
45
61
29
39
Iowa
149
106
71
43
29
Kentucky
16
7
44
9
56
Louisiana
27
18
67
9
33
Michigan
50
26
52
24
48
Mid-Atlanlic'
18
10
56
8
44
Mississippi
27
24
89
3
11
Missouri
81
39
48
42
52
Nebraska
97
40
41
57
59
New England 1
11
1
9
10
91
New York
31
13
42
18
58
North Carolina
31
17
55
14
45
Ohio
67
31
46
36
54
Oklah:>tna
43
27
63
16
37
Oregon
37
15
41
22
59
Pennsylvania
34
14
41
20
59
South Carolina
16
10
63
6
37
South Dakota
106
45
42
61
58
Tennessee
22
10
45
12
55
Virginia/West
Virginia 1
24
4
17
20
83
Washington
45
26
58
19
42
Wisconsin
66
25
38
41
62
TOTAL
,402
742
53
660
47
'Because some small eastern states had very few sites, those with
similar geographic location and/or agricultural characteristics were
combined to obtain more representative data. State groups used
were Mid-Atlantic: Delaware. Maryland, and New Jersey. New Eng-
land: Connecticut, Maine, Massachusetts, New Hampshire, Rhode
Island, and Vermont; and Virginia and West Virginia,
and New Jersey; New England: Connecticut, Maine,
Massachusetts, New Hampshire, Rhode Island, and
Vermont; and Virginia and West Virginia, Among
individual states and state groups, frequency of pesti-
cide use ranged from 9 percent in the New England
states to 89 percent in Mississippi.
ALL SITES
The 121 compounds applied to all sites included 54
herbicides, 38 insecticides, 20 fungicides, 4 acaricides,
2 defoliants, 2 soil fumigants, and 1 growth retardant
(Table 2), The most commonly applied compounds
were atrazine, 2,4-D, captan, and trifluralin, which were
used on 14, 10, 8, and 7 percent of the sites, respectively.
BV STATE
Table 3 presents the application data by state or state
group. Because of the number of states sampled, it is not
feasible to discuss in detail the pesticide data from each
state. However, pesticide application data from each
state tended to reflect both the crops grown and the
intensity of agricultural land use in the state. For ex-
ample, Iowa, predominantly a corn- and soybean-
producing state, recorded the use of 17 compounds on
149 sites. California, a fruit and vegetable producer,
recorded 29 compounds used on 52 sites.
In Figure 2, the frequency of reported pesticide applica-
tions in each state was arbitrarily classified as follows:
low, less than 25 percent of the sites reported pesticide
application; medium, 25-59 percent reported applica-
VoL. 12, No. 4, March 1979
199
TABLE 2. Siininitiry of compounds applied to 1,402 cropland sites in 37 stales, 1972-
National Soils Monitoring Program
Sites
Reporting
Average Total
Sites
Reporting
Average Total
Trade
Application
Application
Trade
Appltcation
Application
Name -
Name
Compound
IF Noted
No
%
Lb/ Acre
Ko/Ha
Compound
If Noted
No
%
Lb/ Acre
Kg/Ha
Alachlor
Lasso
86
6.1
1.38
1.55
Fluomeluron
Coloran
23
1.6
0.93
1.04
Aldicarb
Temik
2
0.1
0.40
0.45
Folex
5
0.4
1.10
1.23
Aldnn
33
2.4
1.57
1.76
Hepiachlor
5
0.4
1.26
1.41
Amitrole
1
0.1
0.15
0.17
Hexachloro-
Ancrack
4
0.3
1.08
1.20
benzene
No-Bunt
U
0.8
0.04
0.04
Atrazine
AAlrex
2(K)
14.3
1.56
1.75
Lead arsenate
1
0.1
4,00
4.48
Azinphosmclhyl
Gi'lhion
4
0.3
1.23
1.37
Lindane
1
0.1
0.01
0.01
Bcncfin
Balan
6
0.4
0.83
0.93
Linuron
Lorox
39
2.8
111
1.24
Benoniyl
Beiilate
3
11. 1
2.58
2.90
Malathion
83
5.9
0.04
0.04
Benzene
Malcic hydrazide
MH
5
0,4
2.25
2.52
hexachloride
2
0.1
1.25
1,40
Maneb
3
0.2
0.70
0.78
Bromacil
Hyvar
2
0.1
0.42
0.47
MCPA
MCP
5
0.4
1.40
1.56
Bromoxvnil
1
0.1
1.25
1.40
MCPB
5
0.4
0.85
0.95
Butylale
Sutan
17
1.2
1.68
1.89
Mercury
10
0.7
0.04
0.04
Bux
25
1.8
0.88
0.98
Melhomyl
Lannale
1
0.1
0.34
0.38
Captafol
Difolatan
3
0.1
3.83
4.29
Methoxythlor
11
0.7
0.19
0.21
Caplan
106
7.6
0.19
0.22
MelhyliTierciiry
Carbaryl
Sevin
23
1.6
2.49
2.79
aceiate
Ceresan L
7
0.5
0.01
0.01
Carbofuran
Furadan
17
1.2
1.07
1.19
Meihylmercury
Carbophenoihion
Triihion
3
0.2
0.78
0.87
dicyandiamide
Panogen
3
0.2
0.01
0.01
Chloramben
Amiben
51
3.6
1.38
1.55
Methyl trithion
1
0.1
0.25
0.28
Chlorobcnzilate
Acaraben
4
0.3
3.45
3.87
Metnbuzin
Senear
1
0.1
0.50
0.56
Chlordane
5
0.4
3.18
3.57
Mevinphos
Phosdrin
1
0,1
0.25
0.28
Chloroneb
Demosan
8
0.6
0.02
0.02
Ml rex
7
0.5
0.01
0.01
Chloropropham
Chloro-IPC
1
0.1
0.59
0.66
Molinate
O.dram
2
0.1
3.00
3.36
Chloropropylate
Acarolaie
1
0.1
3.50
3.92
Monocrolophos
Azodri.n
3
0.2
1.67
1.87
Chloroxuron
Tenoran
1
0.1
2.00
2.24
MSMA
2i
1.5
2..36
2.65
Copper carbonate
Naled
Dibrom
1
0.1
1.00
1.12
(basic)
1
0.1
3.50
3.92
Napialam
Alanap
8
0.6
1.35
1.52
Cyanazine
Bladex
2
0.1
2.15
2.41
Nilralin
Planavin
9
0.6
1.16
1.30
Cycloale
Ro-Neel
3
0.2
1.95
2.19
Norea
Herban
3
0.2
1.57
1.76
2,4-D
136
9.7
0.69
0.77
Oil spray
2
0.1
55.00
61.64
Dalapon
Dowpon
2
0.1
7.80
8.74
Oxyihioquinox
Mores:an
1
0.1
0,08
0.09
2.4-DB
Buiyrac
7
0.5
0.91
1.02
Paraqual
7
0.5
0.43
0.48
DDT
21
1.5
5.83
6.53
Paralhion, elhyi
17
1.1
2.29
2.57
DEF
6
0.4
0.99
1,11
Paralhion, nielhyl
40
2.9
2.99
3.35
Diazinon
8
0.6
0.52
0,59
PCNB
7
0.5
0.02
0.02
Dibromochloro-
Pebulaie
Tillam
1
0.1
4.00
4.48
propane
Nemagon
1
0.1
0.50
0.56
Penlachloro-
Dicamba
Banvel D
12
0.9
0.34
0.38
phenol
PCP
1
0.1
0.05
0.06
Dichlone
Phygon
1
0.1
0.50
0.56
Phenylmercury
Dichloropropene
Telone
1
0.1
60.00
67.25
aceiate
PMA
4
0.3
0.02
0.02
Dichlorprop
2.4-DP
1
0.1
2.00
2.24
Phorale
Thimet
26
1.9
1.79
2.01
Dicofol
Kelihane
2
0.1
0.75
0.84
Picloram
Borolin
1
0.1
0.75
0.84
Dicroiophos
Bidrin
T
0.1
0.08
0.09
Polyram
1
0.1
1,00
1.12
Dimethoate
Cygon
6
0.4
0.58
0.65
Prolate
Imidan
3
0.2
3,92
4.39
DNBP
Premerge
16
1.1
1.24
1.39
Prometryn
Caparol
4
0.3
0,87
0.98
Diniirocresol
2
0 1
1,63
1,82
Propachlor
Ramrod
40
2.9
1.93
2.16
Diphenamid
Enide
1
0.1
1 .00
1,12
Propanil
St am
2
0 1
3 50
3.92
DisuUoton
Di-Syston
13
0.9
0.38
0.43
Propargite
Omilc
2
0.1
1,59
1.78
Diuron
Karmex
11
0.8
0.71
0.80
Propham
IPC
2
0.1
1,75
1.96
Dodine
Cyprex
1
0.1
0.98
1.09
Pyrazon
Pyramin
1
0.1
0.94
1.05
DSMA
8
0.6
2.51
2.81
Simazine
Pnncep
5
0.4
2.82
3.16
Dyfonate
3
0.2
0.97
1.08
Sodium chlorate
2
0.1
1 .00
1.12
EMTS
Ceresan M
t)
0.6
0.01
0.01
Sulfur
10
0.7
27.85
3J.21
EPN
1
0.1
3.00
3.36
TCA
2
0.1
5.63
6.30
EPTC
Ethion
Ep:am
HI
3
0.7
0.2
2.19
3,35
2.45
3.75
TCBC
1
0.1
8.00
8.97
Ethoprop
Mocap
1
0.1
1.00
1.12
TEPP
1
0.1
0.25
0.28
Hihylmercury
Terbacil
Sinbar
t
0.1
1.75
1.96
chloride
Ceresan Red
5
0.4
0.01
0,01
Ihiram
14
0.9
0.03
0.03
Fenac
1
0.1
1.25
1,40
Toxaphene
30
2.1
9,36
10.49
Fenaminosulf
D^xon
1
0.1
0.01
0,01
Ti ielazine
1
0.1
0.25
0.28
Fensulfothion
Dasanit
4
0.3
2.79
3,13
Trifluralin
Trellan
97
6.9
0,86
0.96
Fentin hydroxide
2
0.1
8.75
9,81
Vernolate
Vernam
6
0.4
1,20
1.35
200
Pf.sticides Monitoring Journal
TABLE 3. Compounds applied to cropland sites by state, 1972 — National Soils Monitoring Program
Sites Reporting
Average
Total
Sites Reportino
Average Total
Trade
APPLICATION
Application
Trade
Application
Application
Name
IF Noted
Compound
Name
Compound
No.
%
Lb/Acre
Kg/Ha
IF Noted
No.
%
Lb/ Acre
Kg/Ha
ALABAMA, 20
SITES
FLORIDA. 15
SITES
Atrazine
Azinphosmethyl
Carbophenoihion
Chlorobenzilate
Copper carbonate
(basic)
Ethion
AAirex
Guthion
Triihion
AcaruJen
Ethodan
1
1
1
4
1
3
6.7
6.7
6.7
26.7
6.7
20.0
2.00
2.00
1.50
3.45
3.50
3.35
2.24
2.24
1.68
3.87
3.92
3.76
Atrazine
Benefin
Benomyl
Captan
Disulfoton
2,4-D
AAtrex
Balan
Benlale
Di-Syston
5.0
15.0
10.0
5.0
5.0
5.0
1.00
0.75
3.50
0.01
1.00
1.00
1.00
1.00
2.00
1.12
0.84
3.92
0.01
1.12
1.12
1.12
1.12
2.24
DNBP
Linuron
Naptalam
Premerge
Lorox
Alanap
5.0
5.0
5.0
Fensulfolhion
Oil spray
Sulfur
Dasanit
1
2
4
6.7
13.3
26.7
7.50
55.00
36.88
8.41
61.64
41.33
Parathion, methyl
Trellan
5.0
10.0
10.0
13.00
8.50
2.00
14.57
9.53
2.24
Toxaphene
Trifluralin
GEORGIA, 27
SITES
Vernolale
Vernam
15.0
0.75
0.84
Alachlor
Lasso
3.7
2.50
2.80
Alrazine
Benefin
Captan
Carbaryl
AAtrex
Balan
Sevin
3.7
3.7
3.7
18.5
4.00
1.13
O.OI
2.40
4.48
ARKANSAS. 47
SITES
1.27
0.01
Alachlor
Lasso
2
4.3
3.25
3.64
2.69
Ancrack
1
2.1
0.50
0.56
DDT
3.7
4.50
5.04
Captan
3
6.4
0.01
0.01
Captafol
D;folatan
3.7
10.00
11.21
Chloroxuron
Tenoran
1
2.1
2.00
2.24
Disulfoton
Di-Syslon
3.7
1.00
1.12
DEF
1
2.1
0.50
0.56
Fentin hydroxide
Du-Ter
7.4
8.75
9.81
DDT
5
10.6
3.90
4.37
Mirex
7.4
0.01
0.01
Dicrotophos
Bidrin
2
4.3
0.08
0.09
Maleic hydrazide
MH-30
3.7
6.00
6.72
Disulfoton
Di-Syston
1
2.1
O.OI
0.01
Parathion. ethyl
7.4
2.75
3.08
Diuron
Karmex
2
4.3
1.25
1.40
Parathion. methyl
3.7
4.50
5.04
DNBP
Pre.merge
4
8.5
0.94
1.05
Sulfur
3.7
34.00
38.11
DSIVIA
2
4.3
2.50
2.80
Toxaphene
2
7.4
5.25
5.88
2.4-DB
Butyrac
4
8.5
0.88
0.98
Trifluralin
Treflan
1
3.7
1.00
1.12
EMTS
Ceresan M
->
1
7
1
4.3
2.1
14.9
2.1
0.01
3.00
0.96
1.50
O.OI
3.36
1.08
1.68
EPN
Fluometuron
Folex
IDAHO, 30
SITES
Cotoran
Atrazine
AAirex
2
6.7
0.75
0.84
Linuron
Loiox
-)
4.3
0.50
0.56
Bromoxynil
1
3.3
1.25
1.40
Mercury
7
14.9
0.05
0.05
2,4-D
7
23.3
1.21
1.36
Metribuzin
Sencor
1
2.1
0.50
0.56
DDT
1
3.3
1.00
1.12
MSMA
9
19.1
1.94
2.18
EMTS
Ceresan M
2
6.7
0.01
0.01
Naptalam
Alanap
3
6.4
0.83
0.93
EPTC
Ep;am
1
3.3
0.25
0.28
Nitralin
Planavm
2
4.3
1.00
1.12
MCPB
1
3.3
2.00
2.24
Paraquat
1
2.1
0.02
0.02
Sulfur
I
3.3
20.00
22.42
Parathion. ethyl
1
2.1
3.00
3.36
Trifluralin
Treflan
2
6.7
0.25
0.28
Parathion. methyl
Prometryn
9
3
8
19.1
6.4
4.3
17.0
2.69
1.08
0.12
4.84
3.02
1.21
0.13
5.43
Caparul
Sii.Tiusoy
ILLINOIS, 139
SITES
Thiram
Toxaphene
Alachlor
Aldrin
Lasso
10
6
7.2
4.3
1.24
1.10
1.38
1.23
Trifluralin
Treflan
12
25.5
0.77
0.86
Atrazine
AAtrex
23
16.5
1.33
1.49
Bulylaie
Bux
Sutan
9
T
45
3
6.5
1.4
32.4
T 2
0.94
1.30
0.01
0.75
1.06
CALIFORNIA. 5
2 SITES
1.46
0.01
0.84
Alachlor
Lasso
1.9
0.50
0.56
Captan
Carbofuran
Furadan
Carbophenothion
Tri.hion
1.9
0.09
0.10
Chloramben
Amiben
20
14.4
1.25
1.40
Chloroneb
Demosan
1.9
0.01
0.01
Chlordane
3
■) 2
0.97
1.09
2.4-D
3.8
0.50
0.56
2.4-D
14
10.1
0.43
0.49
DNBP
Premerge
1.9
0.50
0.56
2.4-DB
Buiyrac
1
0.7
0.50
0.56
Dibiomochloro-
Diazinon
-)
1.4
2.01
2.25
propane
Nemagon
1.9
0.50
0.56
Dicamba
Eanvel-D
2
1.4
0.17
0.18
Dicofol
Kel thane
3.8
0.75
0.84
Dvfonate
1
0.7
0.50
0.56
Disulfoton
Di-Syston
1.9
1.00
1.12
EPTC
Ep:am
1
0.7
0.42
0.47
EPTC
Eptam
1.9
3.00
3.36
E-hyimercury
Fenaminosulf
Dexon
1.9
0.01
0.01
chloride
Ceresan Red
1
0.7
0.01
0.01
Malathion
1.9
1.00
1.12
Heplachlor
2
1.4
1.65
1.85
MCPA
MCP
3.8
2.00
2.24
Lindane
1
0.7
0.01
0.01
jVlethornyl
Lannale
1.9
0.34
0.38
Linuron
Lorox
T
1.4
1.25
1.40
Mevinphos
Phosdrin
1.9
0.25
0.28
Malathion
44
31.6
O.OI
0.01
Molinate
Oidram
3.8
3.00
3.36
Meihoxychlor
5
3.6
0.01
0.01
Naled
Dibrom
1.9
1.00
1.12
Nitralin
Planavin
1
0.7
2.80
3.14
Nitralin
Planavin
1.9
0.75
0.84
Phorate
Thimet
3
-> 2
0.80
0.90
Paraquat
3.8
0.63
0.70
Propachlor
Ra.xrod
15
10.8
1.71
1.92
Parathion. ethyl
9.6
0.76
0.85
TCBC
Randox-T
1
0.7
8.00
8.97
Parathion, methyl
3.8
0.36
0.40
Simazine
Princep
1
0.7
3.00
3.36
Phorate
Thimet
3.8
1.00
1.12
Trietazine
Gesafloc
1
0.7
0.25
0.28
Prolate
Imidan
1.9
0.75
0.84
Toxaphene
1
0.7
0.40
0.45
Propanil
Slam
bmite
1.9
4.00
4.48
Trifluralin
Treflan
12
8.6
0.73
0.82
Propargite
1.9
1.68
1.88
Vernolale
Vernam
1
0.7
0.45
0.50
Simazine
Princep
3.8
3.8
1.9
1.9
2.75
0.80
0.25
3.00
3.08
0.90
0.28
3.36
Sulfur
INDIANA, 74
SITES
TEPP
Toxaphene
Alachlor
Lasso
15
20.3
1.86
2.08
Trifluralin
Treflan
-
3.8
0.38
0.42
Aldnn
7
9.5
1.33
1.49
{Continued next page)
Vol. 12, No. 4, March 1979
201
TABLE 3 (cont'd.). Compounds applied to cropland sites by stale, 1972 — National Soils Monitoring Program
Sites Reporting
Average Total
Sites Reporting
Average Total
Trade
Application
Application
Trade
Application
Application
Name
IF NolED
Compound
Name
IF Noted
Compound
No.
%
Lb/Acre
Kg/Ha
No.
%
Lb/Acre
Kg/Ha
Atrazine
AAtrex
20
27.0
1.83
2.05
Linuron
Lorox
3
6.0
1.67
1.87
Capian
6
8.1
0.01
0.01
Malaihion
10
20.0
0.01
0.01
Chloramben
Amiben
5
6,8
1.20
1.35
Pyrazon
Pyramin
1
2.0
0.94
1.05
2.4-D
4
5.4
0.50
0.56
TCA
1
2.0
0.25
0.28
EPTC
Eplam
1
1.4
10.00
11.21
Trifiuralin
Treflan
1
2.0
1.00
1.12
Ltnuron
Lorox
Treflan
8
6
10.8
8.1
4.1
1.38
0.01
1.00
1.55
0.01
1.12
Malathion
Trifliiralin
MID-ATLANTIC STATES,> 18
SITES
Alachlor
Lasso
5
27.8
2.06
2.31
IOWA. 149
SITES
Atrazine
AAtrex
2
11.1
1.75
1.96
Azinphosmethyl
Guihion
1
5.6
0.90
1.01
Alachlor
Lasso
10
6.7
0.86
0.97
Captan
4
22.2
0.01
0,01
Aldrin
8
5.4
1,20
1,35
Carbaryl
Se%in
2
11.1
1.92
2.15
Airazine
AAtrex
38
25.5
1,38
1,55
Chlordane
5.6
5.00
5.60
Butylate
Suian
6
4.0
2,75
3.08
2.4-D
5,6
0.50
0.56
Bux
13
8.7
0,90
1.01
Dichlone
Phygon
5,6
0.50
0.56
Carbofuran
Furadan
4
2.7
0.98
1,09
Dieldrin
11,1
0.26
0.29
Chloropropham
Chloro-lPC
1
U.7
0.59
0.66
Dimethoate
Cygon
5,6
0.66
0.74
Chloramben
Ami:en
16
1(1,7
0.96
1.08
5,6
3.00
3.36
2.4-D
iS
12.1
0,51
0.57
Linuron
Lorox
5,5
0.38
0.43
Diazinon
1
0,7
0,07
0.08
Maneb
5,6
1.44
1.61
Dicamba
B.mvel D
6
4.0
0,25
0.28
Ma'aihion
11,1
0.01
0.01
Dyfonale
1
0.7
1.40
1.57
Parathion. ethvl
5,6
1.30
1,46
Ethoprop
Mocap
1
0.7
1 .00
1.12
Prolate
imidan
5,6
2.00
2,24
Hepiachlor
1
0.7
1.00
1.12
Sulfur
5,6
37.00
41.47
Phoraic
Ihimel
8
5.4
1.06
1,19
Thiram
.Arasan
5,6
0.01
0.01
Propachlor
Ramrod
14
9.4
1.74
1.95
Trifiuralin
Treflan
5.6
1.20
1.35
Trifiuralin
Treflan
22
14.8
0.80
0.89
KENTUCKY. 16 SITES
MISSISSIPPI, 27 SITES
Atrazine
Carbaryl
2,4-D
Linuron
Malathion
Methoxychlor
Trifiuralin
AAirex
Sevin
Lorox
Treflan
31.3
12.5
6.3
6.3
6,3
6.3
6.3
1.00
1.50
1.00
0.75
1.00
2.00
1,00
1.12
1.68
1.12
0.84
1.12
2.24
1.12
LOUISIANA. 27 SITES
Alachlor
Aldrin
Azinphosmethyl
Chloramben
2.4-D
2.4-DB
DCPA
DDT
DSMA
Dalapon
DEF
Dichlorprop
Diphenamid
Diuron
DNBP
EMTS
Fcnac
Ruomcturon
Folex
MSMA
Norea
Parathion. meihyl
Propanil
TCA
Terbacil
Thiram
Toxaphenc
Trifiuralin
Vernolale
Lasso
Guthion
Amiben
Butyrac
Dacihal
Dowpon
2.4-DP
Enide
Karmex
Premcrge
Ceresan M
Coioran
Ansar
He.fcan
S.am
Sinbar
Ircflan
Vernam
3.7
3.7
3.7
3.7
11.1
3.7
3.7
18.5
14.8
3.7
3.7
3.7
3.7
11,1
7,4
3,7
3,7
14,8
3,7
11,1
3.7
29.6
3.7
3.7
3.7
3,7
18,5
29,6
3,7
1.00
0.01
1.50
1,50
1,12
2,00
0.75
11,30
3,15
2,l»
1,50
2,00
1,00
1,25
1,25
0.01
1.25
1,03
1,(KI
2,50
0,60
3,66
3,00
1 1 ,00
2,00
0,01
23,40
1,41
2,50
1,12
0,01
1,68
1,68
1.25
2.24
0,84
12,67
3.53
2.24
1.68
2.24
1.12
1.40
1.40
0.01
1.40
1.15
1.12
2.80
0.67
4.10
3.36
12.33
2.24
0.01
26.23
1.58
2.80
Alachlor
Aldicarb
Ancrack
Azinophosmethyl
Captan
Carbaryl
Chloroneb
2,4-DB
DDT
DEF
DSMA
DNBP
Disulfolon
Diuron
Fluometuron
Folex
Linuron
MSMA
Methylmercury
acetate
Mirex
Monocrotophos
Naptalam
Nitralin
Norea
Parathion. methyl
Sodium chlorate
Toxaphene
Trifiuralin
Lasso
Temik
Guthion
Sex in
Demcsan
Butyrac
Premerge
Di-Syston
Karmex
Cotoran
Lorox
Ceresan L
Azodrin
Alanap
Planavin
Herban
Treflan
4
3
1
3
1
10
2
8
10
3.7
7.4
11.1
3.7
3.7
3.7
25,9
3,7
25,9
14,8
7.4
25,9
18,5
7,4
25,9
7,4
11,1
25.9
22,2
14,8
11,1
3,7
11.1
3.7
37.0
7.4
29.6
37.0
2.00
0,40
1.27
0.50
0.03
1,00
0,03
0,40
5,71
0,98
1,24
1,70
0,01
0.30
0.70
0.75
1.83
2.75
0.01
0.01
1.67
3.00
1.33
1.60
4.38
1.00
10.25
0.85
MISSOURI, 81 SITES
MICHIGAN. 50 SITES
Alachlor
Aldrin
Atrazine
Capian
2,4-D
Dicamba
EPTC
Lasso
AAIrex
Banvcl D
Eptam
1
1
15
10
6
1
2
2.0
2.0
.30.0
20.0
12(1
2.0
4.0
0.50
1.40
2.09
0.01
1.29
1.00
2.00
0.56
1.57
2.35
0.01
1.45
1.12
2.24
Alachlor
Atrazine
Aldrin
Chloramben
2.4-D
Diuron
Fluometuron
L inuron
MSMA
Norea
Trifiuralin
Lasso
AAtrex
Amiben
Karmex
Cott)ran
Lorox
Herban
Treflan
II
13
3
T
3
1
3
6
1
I
11
13.6
16.0
3.7
2.5
3,7
1,2
3,7
7.4
1.2
1.2
13.5
1.42
1.67
1.67
3.01
0.42
0,25
1,31
0,87
3.40
2.50
0.73
NEBRASKA. 97 SITES
Alachlor
Atrazine
Bux
Carbofuran
Lasso
AAtrex
Furadan
4
1«
7
5
4.1
18.6
7.2
5.2
1.11
1.40
0.73
0.69
(Continued next page)
202
2.24
0.45
1,42
0,56
0.03
1.12
0.03
0.45
6.40
1.10
1.39
1.91
0.01
0.34
0.78
0.84
2.05
3.08
0.01
0.01
1.87
3.36
1.49
1.79
4.90
1.12
11.49
0.95
1.59
1.87
1.87
3.37
0.47
0.28
1.46
0.97
3.81
2.80
0.82
1.25
1.57
0.82
0.78
Pesticides Monitoring Journal
TABLE 3 (cont'd.). Compounds applied to cropland sites by state, 1972 — National Soils Monitoring Program
Compound
Trade
Name
IF Noted
Sites Reporting
Application
Average Total
Application
Lb/Acre Ko/Ha
Chloramben
Cyanazine
Cycloaie
2,4-D
Diazinon
Dyfonale
EPTC
Fensulfothion
Linuron
Parathion, ethyl
Propachlor
Phorate
Simazine
Amiben
Bladex
Ro-Necl
Epiam
Dasanit
Lorox
Ramrod
Thimet
Princep
1.0
1.0
1.0
8.2
1.0
1.0
1.0
1.0
2.1
2.1
5.2
3.1
I.O
1.50
2.80
0.40
0.61
0.98
1. 00
1.75
0.90
0.94
0.65
2.13
0.88
4.00
1.68
3.14
0.45
0.68
1.10
1.12
1.96
1.01
1.05
0.73
2.39
0.99
4.48
NEW ENGLAND,! 11 SITES
Captan
Carbophenothion
Chloropropylate
Dodine
Prolate
Propargite
Trilhion
Acarolate
Cyprex
Omite
9.1
9.1
9.1
9.1
9.1
9.1
19.20
0.75
3.50
0.98
0.38
9.00
NEW YORK. 31 SITES
Alachlor
Airazine
Benomyl
Bux
Captan
Carbaryl
Carbofuran
2.4-D
Diazinon
Dinitrocresol
DNBP
EPTC
Methoxychlor
Parathion, ethyl
Thiram
Lasso
AAtiex
Benlate
Sevin
Furadan
Premerge
Ep:am
10
1
1
3
2
1
1
">
1
I
1
4
I
4
7.1
32.3
3.6
3.6
10.7
7.1
3.6
3.6
7.1
3.6
3.6
3.6
12.9
3.6
12.9
0.88
2.03
0.75
0.70
0.01
4.25
1.00
0.25
0.51
0.25
0.21
0.25
0.01
0.33
0.01
NORTH CAROLINA, 31 SITES
Alachlor
Atrazine
Carbaryl
2,4-D
Dichloropropene
Fensulfothion
Lead arsenate
Linuron
Maleic hydrazide
Maneb
Naptalam
Nitralin
Parathion. ethyl
Paraquat
Pebulaie
Phorate
Penlachlorophenol
Toxaphene
Trifluralin
Lasso
AAtrex
Sevin
Telone
Dasanit
Alanap
Planavjn
Tillam
Thimet
PCP
Treflan
9.7
12.9
12.9
3.2
3.2
3.2
3.2
3,2
12.9
3.2
6.5
3.2
6.5
6.5
3.2
3.2
3.2
3.2
3.2
1.00
1.63
3.38
1.00
60.00
2.00
4,00
1.50
1.31
0.41
0.92
0.50
10.50
0.38
4.00
0.50
0.05
10.00
0.80
OHIO, 67 SITES
Alachlor
Lasso
4
6.0
Aldrin
6
9.0
Atrazine
AAtrex
13
19.4
Butylate
Sutan
1
1.5
Bux
1
1.5
Captan
1
1.5
Carbofuran
Furadan
1
1.5
Chloramben
Amiben
5
7.5
2,4-D
5
7.5
Dicamba
Banvel D
2
3.0
Linuron
Lorox
5
7.5
Melhylmercury
acetate
Ceresan L
1
1.5
Picloram
Borolin
1
1.5
Propachlor
Ramrod
1
1.5
1.14
3.33
1.89
2.00
0.80
0.0 1
1.00
2.60
1.00
1.00
0.92
0.01
0.75
8.00
21.52
0.84
3.92
1.10
0.43
10.09
0.98
2.27
0.84
0.78
0.01
4.76
1.12
0.28
0.57
0.28
0.24
0.28
0.01
0.37
0.01
1.12
1.82
3.78
1.12
67.25
2.24
4.48
1.68
1.47
0.46
1.03
0.56
11.77
0.42
4.48
0.56
0.06
11.21
0.90
1.27
3.74
2.12
2.24
0.90
0.01
1.12
2.91
1.12
1.12
1.03
0.01
0.84
8.97
Compound
Trade
Name
IF Noted
Sites Reporting
Application
No.
Average Total
Application
Lb/Acre Kc/Ha
OKLAHOMA, 43 SITES
Alachlor
Benefin
Captan
Carbaryl
2,4-D
EMTS
Ethylmercury
chloride
MCPB
Parathion, methyl
PCNB
Polyram
Thiram
Trifluralin
Lasso
Baian
Sevin
Ceresan Red
Arasan
Treflan
4.7
2.3
4.7
7.0
9.3
9.3
2.3
4.7
1S.6
14.0
2.3
11.6
2.3
2.00
2.24
1.00
1.12
0.01
O.OI
2.17
2.43
0.50
0.56
0.01
O.OI
0.01
O.OI
0.50
0.56
0.50
0.56
0.02
0.02
1.00
1.12
O.OI
0.01
0.50
0.56
OREGON, 37 SITES
Amitrole
Bromacil
Captan
Cvcloate
2,4-D
Diazinon
Diuron
Ethylmercury
chloride
Hexachloro-
benzene
Malathion
Maneb
Melhylmercury
dicyandiamide
Parathion. ethyl
Phenylmercury
acetate
Propham
Ro-Neet
Karmex
Ceresan Red
Pancgen
PMA
IPC
11
1
2.7
2.7
5.4
2.7
29.7
2.7
2.7
5.4
5,4
2.7
2.7
2.7
2.7
5.4
2.7
0.15
0.09
0.01
5.20
0.72
0.10
0.10
0.01
0.04
0.50
0.25
0.01
0,09
0.02
0.50
PENNSYLVANIA, 34 SITES
Alachlor
Airazine
Butylate
Captafol
2,4-D
Disulfoton
Lmuron
Phorate
Lasso
AAtrex
Sutan
Difolatan
Di-Syston
Lorox
Thimet
26.5
2.9
2.9
8.8
2.9
2.9
2.9
0.75
1.60
1.60
1.00
0.58
0.50
0,50
2.50
SOUTH CAROLINA, 16 SITES
SOUTH DAKOTA, 106 SITES
Alachlor
Lasso
4
3.8
Airazine
AAtrex
5
4.7
Bux
1
0.9
Captan
20
18.9
Carbofuran
Furadan
2
1.9
Chloramben
Amibe.n
1
0.9
2.4-D
27
25.5
Dieldrin
2
1.9
Dimelhoate
Cygon
4
3.8
Disulfoton
Di-Syston
">
1.9
Malathion
18
17.0
MCPA
1
0.9
1.06
0.90
1.00
0.01
0.25
2.00
0,41
0,01
0.21
0.31
0.01
0.50
0.17
0.10
O.OI
5.83
0.81
0.11
O.U
O.OI
0.04
0.56
0.28
O.OI
0.10
0.02
0.56
0.84
1.79
1.79
1.12
0.65
0.56
0.56
2.80
Benefin
Balan
6.25
0.60
0.67
Captan
6.25
O.OI
0.01
Carbaryl
Sevin
6,25
1.00
1.12
DDT
12,50
0.50
0.56
Methyl trilhion
6,25
0.25
0.28
Mirex
6,25
0.01
0,01
Nitralin
Planavin
6,25
0.35
0.39
Parathion, ethyl
6.25
2.40
2.69
Parathion, methyl
6.25
0.25
0.28
Sulfur
6.25
38.40
43.04
Toxaphene
12.50
1.00
1.12
Trifluralin
Treflan r
18.75
0.58
0.65
Vernolale
Vernam
6.25
2.00
2.24
1.19
1.01
1.12
0.01
0.28
2.24
0.45
0.01
0.23
0.35
O.OI
0.56
(Continued next page)
Vol. 12. No. 4, March 1979
203
TABLE 3 (cont'd.). Compounds iipplicd to cropland sites by state. 1972 — National Soils Monitor ini; Program
Sites
Reporting
Average Total
Sites Repohting
Average Total
Trade
Application
Application
Trade
Application
Application
Name -
IF Noted
Compound
Name
IF Noted
Compound
No
%
Lb/ Acre
Kg/Ha
No.
%
Lb Acre
Kg/Ha
Melhoxychlor
1
0.9
0.01
0.01
Bromacil
Hyvar
,
2.2
0.75
0.84
Melhylmercury
Captan
5
11. 1
0.03
0.03
dicyandiamidc
Panogen
2
1.9
0.01
0.01
Cvcloate
Rc-Neet
1
2.2
0.25
0.28
Paraihion, ethyl
I
0.9
0.25
0.28
2,4-D
12
26.7
1.31
1.47
Propachlor
Ramrod
5
4.7
1.69
1.89
Dicamba
Banvcl D
1
2 2
0.25
0.28
Phoraie
Thimei
I
0.9
0.70
0.78
Dieldrin
Diuron
EPTC
Hexachloro-
Karmex
Eptam
1
1
1
2 2
2 2
2 2
0.04
0.50
0.25
0.04
0.56
TENNESSEE
22 SITES
0.28
Alachlor
Lasso
1
4.5
2.00
2.24
henzene
No-Bunt
9
20.0
0.05
0.05
Atrazine
AAtrex
J
n.6
1.60
1.79
Heptachlor
1
2.2
0.01
0.01
Dimethoate
Cygon
1
4.5
2.00
2.24
MCPA
■)
4.4
1.25
1.40
Diuron
Karmex
1
4.5
0.11
0.12
Mercury
3
6.7
0.01
0.01
Disulfoton
Di-Syslon
1
4.5
0.72
0.81
Oxyihioquinox
Morestan
1
2 2
0.08
0,09
Ethylmercury
Phcn>lmercury
chloride
Ceresan Rec
I
4.5
O.OI
0.01
acetate
PMA
2
4.4
0,01
0.03
Folex
1
4.5
1.50
1.68
Phorate
Thimet
1
2 2
0,03
0.03
Fluometuron
Cntoran
2
9.1
0.91
1.01
Propham
IPC
1
1 T
3.00
3.36
Linuron
Lorox
2
9.1
0.63
0.70
Propargite
Omite
1
T 1
1.50
1.68
MSMA
1
4.5
2.00
2.24
Terbacil
Sinbar
2 2
1.50
1.68
Paraquat
PCNB
Prometryn
Terrachlor
Trctlan
1
4.5
4.5
4.5
IS. 2
0.50
0.01
0.24
1.04
0.56
0.01
0.27
1.16
I
1
4
WISCONSIN, 66
SITES
Trifluralin
Alachlor
Lasso
5
7.6
0.95
1.06
Atrazine
Captafol
AAtrex
Difolatan
16
24,2
1,5
1.33
0,50
1.49
VIRGINIA, WEST VIRGINIA,' 24
SITES
U.56
Carbaryl
Sevin
1.5
1,50
1.68
Atrazine
AAtrex
1
4.2
1.60
1.79
Carharyl
Sevin
2
8.3
3.17
3.55
Carbofuran
Furadan
1.5
6,00
6.72
Daiapon
4.2
13.60
15.24
Chlordane
1.5
8.00
8.97
Naptalam
Alanap
4.2
1.50
1.68
Cyanazine
Biadex
1.5
1.50
1.68
Paraquat
4.2
0.50
0.56
2.4-D
4
6.1
0.69
0.78
Phorate
Thimei
4.2
0.70
0.78
Diazinon
1.5
0.01
0.01
Simazine
4.2
1.60
1.79
EPTC
Fensulfothion
Heptachlor
Eptam
Di.sanit
1.5
1.5
1.5
2.011
0.75
2.00
2.24
0.84
WASHINGTON STATE. 45 SITES
2.24
1 iniirnn
1.5
1.25
1.40
Aldrin
1
f T
0,05
0.06
L.IIILII t'li
MCPB
->
3.0
0.63
0.70
Benzene
Phorate
Thimet
5
7.6
5.32
5.96
hexachloride
BHC
2
4.4
1.25
1.40
Thiram
Aiasan
1
1.5
0.01
0.01
^Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to
obtain more representative data. State groups used were: Mid-Atlantic: Delaware, Maryland, and New Jersey; New England; Connecticut. Maine.
Massachusetts, New Hampshire, Rhode Island, and Vermont; and Virginia and West Virginia.
204
Pesticides Monitoring Journal
>25% ^^:3^
26-59%
1
<60%
^^^
FIGURE 2. Percent of sites reporting pesticide applications, 1972 — National Soils Monitoring Program
tion; and high, states where more than 60 percent of the
sites reported pesticide application.
BY CROP
Table 4 lists crops grown on sample sites in 1972, and
illustrates the diversity of crops grown in the United
States. Application data for several major crops are
presented in Table 5. Pesticide use varied widely among
these crops. Thirty-nine different compounds were ap-
plied to field corn sites but only five compounds were
applied to more than 10 percent of the sites. Cotton-
growing sites also received applications of 39 com-
pounds, but only 1 1 compounds were applied to more
than 10 percent of the sites.
Table 6 shows pesticide applications on several crops by
state. Differences in pesticide use among selected crops
are apparent. For example, only 10.6 p>ercent of the
sites growing alfalfa and/or bur clover reported any
pesticide applications, but 81.5 percent of the cotton
sites did.
A cknowledgments
It is not possible to list all the persons who contributed
to this study. However, the authors are especially grate-
TABLE 4. List of crops grown on 1 ,402 sampling sites,
1972 — National Soils Monitoring Program
No. OF
No. OF
Crop
Sites
Crop
Sites
Field corn
364
Potatoes
3
Soybeans
266
Blueberries
2
Wheat
111
Apples
2
Mixed hay
105
Peaches
2
Alfalfa and/or bur clover
104
Turf
2
Pasture
66
Almonds
2
Cotton
54
Chick peas
2
Grass hay
42
Range
2
Oats
41
Sweet corn
2
Sorghum
24
Apricots
1
Barley
12
Plums
1
Oranges
9
Lespedeza sericea
1
Dry beans
9
Sweet clover
1
Silage (ccrn or sorghum)
8
Mint
1
Peas
7
Hops
1
Grapes
6
Sweet sorghum
1
Rye
6
Celery
1
Tobacco
5
Green peppers
1
Sugar beets
5
Lettuce
1
Rice
4
Pumpkins
1
Milo
4
Tomatoes
1
String beans
4
Millet
1
Pecans
3
Sunflowers
1
Flax
3
Other
9
Sugarcane
3
Fallow sites
129
Asparagus
3
Vol. 12, No. 4, March 1979
205
TABLE 5. Coin[>oiiiuls applied to cropland sites, by most common crop.
1972 — National Soils Monitoring Program
Sites Reporunc
Application
Average Total
Application
Sites Reporting
Application
Average Total
Application
Compound
No.
%
Lb/Acre
Kg/Ha
ALFALFA and BUR CLOVER, 104 SITES
Carbaryl
Carbofuran
EPTC
IPC
Malalhion
Melhoxychlor
Parathion, eihyl
Picloram
Prolaie
2.9
1.0
1.0
1.0
1.0
I.O
1.9
1.0
1.0
2.33
0.25
2.00
3.00
1.00
2.00
0.38
0.75
0.75
COTTON. 54 SITES
Aldicarb
Azinphosmethyl
Captan
Carbaryl
Chloroneb
DDT
DEF
Dibromochloro-
propane
Dicroicphos
Dimt.hoale
DisuUoIon
Diuron
DNBP
DSMA
EMTS
EPN
Ethylmercury
chloride
Fenaminosulf
Fluomeiiuon
Folex
Linuron
MCPB
Mercury
Methylmercury
acetate
Monocrotophos
MSMA
Naled
Nitralin
Norea
Paraquat
Parathion. methvl
PCNB
Phorate
Prometryn
Propargile
Sodium chlorate
Thiram
Toxaphene
Trifluralin
2
1
3
1
8
16
6
5
3
20
1
2
2
1
24
1
1
4
I
2
1
21
3
3.7
1.9
5.6
1.9
14.8
29.6
11.1
1.9
3.7
1.9
13.0
16.7
7.4
14.8
5.6
1.9
1.9
1.9
40.7
9.3
5.6
3.7
13.0
9.3
5.6
37.0
1.9
3.7
3.7
1.9
44.4
1.9
1.9
7.4
1.9
3.7
1.9
38.9
55.6
0.40
0.50
0.02
1.00
0.2
7.44
0.99
0.50
0.08
2.00
0.11
0.80
1.06
2.51
0.01
3.00
0.01
0.01
0.98
l.IO
1.33
0.50
0.05
0.01
1.66
2.38
1.00
0.88
1.10
0.02
4.61
0.01
1.00
0.87
1.68
1.00
0.01
12.76
0.91
FIELD CORN. 364 SITES
Alachlor
Aldrin
Atra/ine
Butylalc
Bux
Captan
Carbaryl
Carbofuran
Chlorambeii
Chlordane
Cyanazine
2,4-D
Dalapon
Diazinon
Dicamba
Dicofol
Dieldrin
Disulfoton
Dyfonaie
EPTC
Elhoprop
Fcnsulfolhion
Hcplachlor
Lindane
36
31
188
17
25
82
1
14
2
4
1
73
1
5
10
I
1
1
2
9.9
8.5
51. S
4.7
6.9
226
0.3
3.9
0.6
1.1
0.3
20.1
0.3
1.4
2.8
0.3
0.3
0.3
0.6
0.6
0.3
0.6
1.1
0.3
1.19
1.67
1.56
1.68
0.92
0.01
1.33
0.78
0.75
3.79
2.80
0.62
13.60
1.10
0.38
1.00
0.0 1
0.50
0.95
5.21
1.00
0.83
1.58
0.01
2.61
0.28
2.24
3.36
1.12
2.24
0.43
0.84
0.84
0.45
0.56
0.02
1.12
0.03
8.34
1.11
0.56
0.09
2.24
0.12
0.90
1.19
2.81
0.01
3.36
0.01
0.01
1.09
1.23
1.49
0.56
0.05
0.01
1.87
2.67
1.12
0.98
1.23
0.02
5.17
0.01
1.12
0.98
1.88
1.12
0.01
14.30
1.02
1.33
1.88
1.74
1.89
1.03
0.01
1.49
0.87
0.84
4.25
3.14
0.69
15.24
1.13
0.43
1.12
0.01
0.56
1.06
5.84
1.12
0.92
1.77
0.01
Compound
No.
%
Lb/ Acre
Ko/Ha
Linuron
3 0.8
0.95
1.06
Malalhion
75 20.7
0.01
0.01
Melhoxychlor
8 2.2
0.01
0.01
Methylmercury
acetate
1 0.3
0.01
0.01
Mirex
2 0.6
0.01
0.01
Naplalam
1 0.3
0.83
0.93
Paraquat
1 0.3
0.50
0.56
Pentachloronhcnol
1 0.3
0.05
0.06
Phorate
19 5.2
1.67
1.88
Propachlor
35 9.6
1.83
2.05
Simazine
2 0.5
2.80
3.14
TCBC
1 0.3
8.00
8.97
Thiram
4 1.1
O.OI
0.01
Toxaphene
1 0.3
0.40
0.45
Trietazine
1 0.3
0.25
0.28
MIXED HAY, 105
SITES
Carbofuran
I 1.0
1.00
1.12
Chlordane
1 1.0
0.75
0.84
2.4-D
2 1.9
0.42
0.47
EPTC
1 1.0
3.00
3.36
Malathion
1 1.0
0.50
0.56
Propham
1 1.0
0.50
0.56
SOYBEANS, 266 SITES
Alachlor
44
Ancrack
Butyrac
Captan
Carbaryl
Chloramben
49
Chloropropham
Chloroxuron
:.4.D
2,4-DB
DDT
Dimethoaic
Dinitrocresol
DNBP
Fluomctiiron
Linuron
32
Methyl trithion
Metribuzin
Mirex
MSMA
Naplalam
Nitralin
Paraquat
Paiathion. methvl
Phorate
Propachlor
Simazine
Thiram
Toxaphene
Trifluralin
59
Vernolate
3
16.5
1.5
0.4
1.9
2.6
18.4
0.4
0.4
1.5
2.3
1.1
0.4
0.4
3.4
0.4
12.0
0.4
0.4
0.4
0.4
1.9
2.3
0.8
2.3
0.4
0.8
0.4
1.1
1.9
1.1
1.54
1.08
0.40
0.01
1.83
1.38
0.59
2.00
0.96
1.00
0.66
0.66
3.00
1.54
0.50
1.11
0.25
0.50
0.01
2.00
1.30
1.36
0.38
0.71
0.70
1.90
3.00
0.08
1.00
0.87
1.65
WHEAT, 111 SITES
Aldrin 1
Benzene hcxachloride 2
Bromacil
Captan
2.4-D
Dicamba
Diuron
EMTS
E.hylmercury
chloride
Heptachlor
Hexachlorobenzene
Malalhion
Mercury
Methylmercury
* dicyandiamide
Parathion, methyl
PCNB
Phcn>lincrcury
acetate
Thiram
Trilluralin
0.9
1.8
0.9
4.5
24.3
0.9
0.9
2.7
3.6
0.9
9.0
0.9
1.8
0.9
6.3
5.4
1.8
1.8
0.9
0.05
1.25
0.75
0.03
0.84
0.25
0.50
0.01
0.01
0.01
0 05
0.01
0.01
0.01
0.50
0.02
0.03
O.OI
0.50
1.72
1.20
0.45
0.01
2.06
1.54
0.66
2.24
1.07
1.12
0.74
0.74
3.36
1.73
0.56
1.24
0.28
0.56
0.01
2.24
1.46
1.52
0.42
0.79
0.78
2.13
3.36
0.09
1.12
0.97
1.85
0.06
1.40
0.84
0.03
0.94
0.28
0.56
0.01
0.01
0.01
0.06
0.01
0.01
0.01
0.56
0.03
0.03
O.OI
0.56
206
Pesticides Monitoring Journal
TABLE 6. Pesticide applications on selected crops, by state, 1972 — National Soils Monitoring Program
ALFALFA/BUR CLOVER
COTTON
Pesticides
No Pesticides
Pesticide
Pestici
DES
N
o Pesticides
Pesticide
State No.
OF Sites
Applied
Applied
Use Unknown
No OF Sites
Applied
Applied
Use Unknown
Alabama
0
3
3
_
_
Arkansas
0
—
—
—
13
12
1
—
California
8
2
4
2
4
2
1
1
Florida
0
—
—
—
0
—
—
—
Georgia
0
—
—
—
2
1
—
I
Idaho
5
1
4
—
0
—
—
—
Illinois
4
—
4
—
0
—
—
—
Indiana
4
—
4
—
0
—
—
—
Iowa
10
—
10
—
0
—
—
—
Kentucky
1
1
—
—
0
—
—
—
Louisiana
0
—
—
—
6
6
—
«—
Michigan
5
—
5
—
0
—
—
—
Mid-Atlantic>
0
—
—
—
0
—
—
—
Mississippi
0
—
—
—
10
9
—
1
Missouri
2
—
2
—
6
6
—
—
Nebraska
10
—
9
1
0
—
—
—
New England'
0
—
—
—
0
—
—
—
New York
2
1
1
—
0
—
—
—
N. Carolina
0
—
—
—
0
—
_
—
Ohio
4
1
3
—
0
—
—
—
Oklahoma
3
2
1
—
7
2
5
Oregon
2
—
2
—
0
—
—
—
Pennsylvania
3
—
3
—
0
—
—
—
S. Carolina
0
—
—
—
0
—
—
—
S. Dakota
14
1
13
—
0
—
—
—
Tennessee
0
—
—
—
3
3
—
—
Virginia/W. Virginia'
0
—
—
—
0
—
—
—
Washington state
6
1
5
—
0
—
—
—
Wisconsin
21
i
20
—
0
—
—
—
Total
104
li
90
3
54
44
7
3
%
100.0
10.6
86.5
2.9
100.0
81.5
l.VO
5.5
FIELD CORN
SOYBEANS
Alabama
7
1
6
—
2
2
—
—
Arkansas
0
—
—
—
25
16
9
—
California
2
1
—
1
0
—
—
—
Florida
1
1
—
—
1
—
1
—
Georgia
5
2
3
—
5
5
—
—
Idaho
1
1
—
—
0
—
—
—
Illinois
56
54
2
—
50
36
14
—
Indiana
27
, 25
2
—
24
19
5
—
Iowa
73
65
7
1
48
41
5
2
Kentucky
8
5
—
3
3
1
1
1
Louisiana
2
1
1
—
8
7
1
—
Michigan
22
18
4
—
4
4
—
—
Mid-Atlantic'
6
4
2
—
5
5
—
—
Mississippi
1
1
—
—
13
n
2
—
Missouri
16
14
2
—
23
18
4
1
Nebraska
31
26
5
—
3
2
1
—
New England'
0
—
—
—
0
—
—
—
New York
13
9
4
^
0
—
—
—
N. Carolina
8
4
4
—
9
4
5
—
Ohio
23
19
4
__
16
10
6
—
Oklahoma
0
— .
0
—
—
—
Oregon
2
1
—
1
0
—
—
—
Pennsylvania
14
12
2
1
1
—
—
S. Carolina
I
1
.
10
7
3
—
S. Dakota
16
16
—
—
4
3
1
—
Tennessee
4
3
1
—
6
4
2
—
Virginia/W. Virginia'
1
1
—
_
5
2
2
1
Washington state
0
—
—
—
0
—
—
—
Wisconsin
24
17
5
2
1
1
—
—
Total
364
302
54
8
266
199
62
5
%
100.0
82.9
14.9
2.2
100.0
74.S
23.3
1.9
WHEAT
MIXED
HAY
Alabama
0
1
—
1
—
Arkansas
0
—
—
1
—
1
—
California
2
—
1
1
1
1
—
—
Florida
0
—
—
—
0
—
—
—
Georgia
0
—
—
—
0
—
—
—
Idaho
4
4
3
—
3
—
Illinois
7
2
5
—
6
1
5
—
Indiana
9
—
9
—
0
—
—
—
Iowa
0
—
—
—
1
—
I
—
Kentucky
0
—
—
—
1
—
1
(Continued next page)
Vol. 12, No. 4, March 1979
207
TABLE 6 (conl'd.). PcstUiile appUcutions on .sclccU-cl crops, by \lulc, 1972 — Nulionul Soils Monitoring I'ronrum
WHEAT
MIXED HAY
Stats
No. OF Sites
Pesticides
Applied
Louisiana 0
Michitian 0
Mid-Allanlic' 0
Mississippi 0
Missouri 5
Nebraska 14
New EnKland ' 0
New York 0
N. Carolina U
Ohio 7
Oklahoma 25
Oregon 6
Pennsylvania 0
S. Carolina 0
S. Dakota 14
Tennessee 2
Virginia^W. Virginia • 0
Washington Male 0
Wisconsin 16
Total 1 1 1
% 100.0
1
16
6
IS
53
47.8
No Pesticides
Applied
Pesticide
Use Unknown
5
12
1
55
49.5
3
2.7
No. OF Sites
0
8
0
0
11
0
2
12
0
12
0
10
8
1
7
1
8
0
12
106
lOU.O
Pesiicides
Applied
No Pesticides
Applied
5
5.0
Pesticide
Use Unknown
2
12
12
7
8
1
7
1
8
12
101
fill to the inspectors from the Plant I'roteetion and Quar-
antine Programs, Animal and Plant Health Inspection
Service, U.S. Department of Agriculture, for collecting
the data.
LITERATURE CITED
(/) Bennitl. I. L.. Jr. 1967. Foreword. Pestic. Monil. J. 1(1).
(2) Panel on Pesticide Monitoring. 1971. Criteria for defin-
ing pesticide levels to he considered an alert to potential
problems. Pestic. Monit. J. .'i(l):36.
(3) Carey. A. /:., J. A. Cowcn, //. lai, W . G. Mitchell, ami
G. B. Wiersniu. 1978. Pesticide residue levels in soils
and crops from 37 slates, 1972 — National Soils Monitor-
ing Program (IV). Pestic. Monit. J. 12(4) :2()K-228.
(4) Wicrsnia. C. H., I'. I\ Sand, and E. /.. Cox. 1971. A
sampling design to determine pesticide residue levels in
soils of the conterminous United States. Pestic. Monit. J.
5(l):63-66.
208
PisTiciDES Monitoring Journal
Pesticide Residue Levels in Soils and Crops from 37 States, 1 972 —
National Soils Monitoring Program (IV)
Ann E. Carey,' Jeanne A. Gowen,' Han Tai,' William U. Mitchell,' and G. Bruce Wiersma '
ABSTRACT
Residue data from the 1972 IFY-7J) National Soils Moni-
toring; fro^ram are summarized. Composite samples of
agricultural soil and mature crops were collected from 1 ,483
of the 1,533 selected 4-hectare sites in 37 states. Analyses
were performed for organochlorine and orf-anophosphorus
compounds, trifliiralin, and polychlorinated hiphenyls (PCBs):
analysis for atrazine was performed only wlien pesticide
application data indicated current-year use. Organochlorine
pesticides were delected in 45 percent of the soil samples.
The most frequently detected compound was dieldrin, found
in 27 percent of all soil .samples. Other compounds de-
tected, in order of frequency, included 1)1)1 . aldrin, chlor-
dane, and heptachlor epoxide, found, respectively, in 21,9,
8, and 7 percent of all soil .samples. Crop samples were col-
lected from 727 sites. All were analyzed for or/janochlo-
rines; analyses were performed for orf;anophosphales and
atrazine only when pesticide application data indicated
current-year use. For all crops, 40 percent of the samples
contained detectable levels of orf;anochlorines and 10 per-
cent contained detectable levels of orfianophosphales. Atra-
zine was not detected.
Introdiiclion
The National Pcsticitlc Monitoring Program (NPMP)
was initiated at the recommendation of the President's
Science Advisory Committee in 1963 to "develop a con-
tinuing network to monitor residue levels in air, water,
soil, man, wildlile and fish" {H). The primary objective
of the NPMP is to determine levels and trends of pesti-
cides and their dcgratlation products in various com-
ponents of the environment (5). The National Soils
Monitoring Program (NSMP) was established in 1968
as an integral part of NPMP to monitor residues in
agricultural soils and raw agricultural crops.
'Ecological Moniiorinn Branch, Bcnefils and Field Studies Division,
Office of Pesticide Programs, U.S. Environmental Protection Agency,
TS-768, Washinglon, DC 20460.
-Extension Agent, Colorado Stale Extension Service, Golden, CO.
■'Ecological Monitoring Branch, Benefits and Field Studies Division,
Office of Pesticide Programs, U.S. Environmental I'roteclion Agency,
Pesticides Monitoring Laboratory. Bay St. I.ouis. MS.
'Chief, I*ollutant Pathways Branch, Environmental M()nitoring and
Support Laboratory, U.S. Environmental l*rotection Agency, Las
Vegas, NV.
The present report summarizes soil and crop pesticide
concentration data collected from 1,48.? sampling sites
in .37 states during 1972 (FY-73). Data were not col-
lected from all conterminous states because of budgetary
limitations. The states omitted from the survey were
generally large, western states either having little wide-
spread agriculture or growing primarily wheat and other
small grains, which require fewer pesticides than do
other nongrain crops,
Sampliitg Procedures
A total of 1,533 sites in 37 states were scheduled for
sampling during late summer and fall of 1972 (Fig, 1),
.Site selection criteria, statistical design, and sampling
techniques involved in the present study have been
described (i, 8). At each 4-hectare (lO-acre) site, a
composite soil sample and a composite mature crop
sample, if available, were collected accoriling to estab-
lished procedures (6), In addition, information on
cropping practices and a history of pesticide applications
for the current cropping season were obtained in a
personal interview with the landowner or operator.
These data have been summarized and published sepa-
rately (/).
A nalytical Procedures
OKCANOC HI ORINI S ANIl OKCi ANOPMOSPH AI l;S
Sample Preparatiim. Soil — A lOO-g subsample was taken
from a thoroughly mixed field sample. The subsample
was moistened with 25 ml distilled water and extracted
with 200 ml 3:1 hexaneiisopropanol solvent by shaking
for 4 hours on a reciprocating shakei . The isopropanol
was removed by three distilled water washes and the
hexane extract was dried through anhydrous sodium
sulfate. The sample extract was then stored at low
temperature for subsequent gas-liquid chromatographic
(GLC) analysis.
Crops — For samples containing less than 2 percent tat
(e.g., alfalfa, bur clover, corn stalks, cotton stalks, green
bolls, miscellaneous hay), a 100-g sample of the crop
was dry blended for 3 minutes and then blended for 5
Vol. 12, No. 4, MaR( ii 1979
209
Not Sampled
FIGURE I. States where agricultural soils and crops were sampled. 1972 (FY 197.^)
— National Soils Monitoring Program
minutes in 800 ml acetonitriie. An aliquot of the sample
extract, representing 10 g of the original sample, was
decanted into a 500-ml Erienmeyer flask. The extract
was concentrated under a three-ball Snyder column to
approximately 10 ml, 100 ml hexane was added, and the
hexane-acetonitrile azeotrope was again concentrated to
10 ml. The process was carried out three times to re-
move essentially all acetonitriie. The hexane extract
was dried through anhydrous sodium sulfate, the volume
was adjusted to 50 ml, and the extract was stored at low
temperature.
chloride was essentially removed. Each extract volume
was adjusted to 2.5 ml for separate injection on the
gas-liquid chromatograph.
GLC — Analyses were performed on gas chromatographs
equipped with tritium foil electron-affinity detectors for
organohalogens and thermionic or flame photometric
detectors for organophosphates. A multiple-column sys-
tem of polar and nonpolar columns was used to identify
compounds. Instrument parameters and operating con-
ditions follow:
For crop samples containing more than 2 percent fat
(e.g.. corn kernels, cottonseed, sovbeans), a 100-g sam-
ple was prewashed with 100 ml isopropanol and then
with 100 ml hexane. Both prewashes were discarded.
The sample was extracted as described in the preceding
paragraph. A separate aliquot of the extract, not sub-
jected to Florisil cleanup, was reserved for flame photo-
metric analysis for organophosphates.
Florisil Cleanup — An extract equivalent to 5 g original
crop sample was fractionated through a 15-g Florisil
column into two fractions bv use of 100 ml 10 percent
methvlene chloride in hexane and 100 ml methylene
chloride for fractions 1 and 2, respectively.
Methylene chloride was removed by concentrating each
extract to low volume under a three-ball Snyder column,
adding 100 ml hexane, and concentrating again to low
volume. After two additions of hexane, the methylene
Gas chromatographs: Hewlett-Packard Model 402A
Hewlett-Packard Model 402B
Tracer Model MT-::o
Cohinins: glass. 6 mm OD x 4 mm ID. 183 cm long,
packed with one of the following; 5 percent
OV-2I0 on 811-100-mesh Chromosorb W-HP;
3 percent DC-20U on l(H)-120-mesh Gas-Chrom
Q; a mixture of 1.5 percent OV-17 and 1.95 per-
cent QF-1 on 100-1 20-niesh Supelcopon
Temperatures. "C: thermionic detector housing 250
detector (EC and FPD) 200
injection port 250
column OV-210 166
column DC-200 170-175
mixed column 185-190
Carrier gases: 5 percent methane-argon flowing at 80 mr min-
ute; prepuritied nitrogen flowing at 80 ml.'minule
Sensitivity or minimum detection levels for organo-
chlorines and trifluralin were 0.002-0.0.'* ppm except for
combinations of polychlorinated hiphenyls (PCBs),
chlordane, toxaphene, and other chemicals which had
minimum detectable levels of 0.05-0.1 ppm. Minimum
detectable levels for organophosphates were approxi-
mately 0.01-0.0.^ ppm. Compounds detectable by this
210
PtiSTiciDES Monitoring Journal
methodology are listed in Table 1 . When necessary,
residues were confirmed on a Dohrmann microcoulo-
metric detector or a Coulson electrolytic conductivity
detector. Because trifluralin is detected by the organo-
chlorine methodology, it appears with the organochlo-
rine analyses in the tables.
TABLE 1. Compounds detectable by chemical
methodology of the present study
Organochlorines
Alachlor
Endrin ketone
Aldrin
Heptachlor
Benzene hexachloride
Heptachlor epoxide
Chlordane
Hexachlorobenzene
SDDT
Isodrin
Dieldrin
Lindane (-^,-BHC)
DCPA
Methoxychlor
Dicofol
Ovex
Endosulfan 1
PCBs
Endosulfan II
PCNs
Endosulfan sulfate
Propachlor
Endrin
Toxaphene
Orcanophosphates
DEF
Parathion. ethyl
Diazinon
Parathion. methyl
Ethion
Ronnel
Malathion
Trithion
Phorate
Other Halogenated Hydrocarbons
Trifluralin 1
'Although trifluralin is a dinitroaniline compound, it is detected by
the organochlorine methodology and thus appears with organochlorines
in Tables 2-7.
Recovery Studies — Pesticide recovery values from soil
were 80-110 percent, but usually were close to 100
percent. Values from crops ranged from 70 to 100 per-
cent, depending on the amount of pesticide present, the
individual pesticide, and the type of crop involved.
Residue concentrations detected in both soil and crop
samples were corrected for recovery. Soil samples were
also converted to a dry-weight basis.
ATRAZINE
To analyze soil samples for atrazine, a 50-g subsample
was taken from a thoroughly mi.xed field sample. The
subsample was placed in the Soxhlet thimble and moist-
ened with 40 ml 1:1 distilled water: methanol. After
addition of 250 ml nanograde methanol, the sample was
extracted for 4 hours. The extract in the Soxhlet flask
was evaporated to about 50 ml on a hot plate and by
use of a three-ball Snyder column. The sample extract
was then decanted into a 1 -liter separatory funnel. The
extract was partitioned three times with 150 ml Freon
1 13 each time. The Freon 113 fractions were combined
and concentrated to incipient dryness on a rotary
evaporator. The extract was dissolved in isooctane
and adjusted to 5 ml for injection into a gas-liquid
chromatograph.
GLC — A Coulson electrolytic conductivity cell detector
in the nitrogen mode was used for detection and quanti-
fication of the atrazine. Positive samples were con-
firmed by alkali flame detection. Recovery rate was
90-1 10 percent; minimum detection level was 0.01 ppm.
Results and Discussion
Tables 2-5 show concentrations of pesticides in soil
samples, and Tables 6-8 show concentrations of pesti-
cides in mature agricultural crops. Soil concentration
data are also summarized by all sites and by state or
state groups. Most tables list the number of analyses,
the number of times a compound was detected, percent
occurrence of the compound, the arithmetic mean, the
estimated geometric mean, and the minimum and
maximum positive concentrations detected.
The estimated geometric mean is routinely presented in
the tables as an alternative to the arithmetic mean as a
measure of central tendency for the data evaluation.
Pesticide residue data frequently contain a large number
of zero values, resulting either from the absence of
pesticides or their presence at levels below the analytical
sensitivity. Such data are seldom distributed normally,
as shown by tests for skewness and kurtosis, but often
tend to approximate a log-normal distribution. After
repeated tests for significant skewness and/or kurtosis,
the log (Z-fO.Ol) transformation was used to deter-
mine the logarithmic means. The antilogs of these fig-
ures, minus 0.01, were taken to obtain the estimates of
the geometric mean in the untransformed dimension.
The estimated geometric mean was calculated only for
those compounds with more than one positive detection.
COMPOUND CONCENTRATIONS IN CROPLAND SOIL
All Sites — Soil samples were received from 1,483 of the
scheduled 1,533 sites in 37 states. Results of analyses
for organochlorine and organophosphorus pesticides
and atrazine are presented in Table 2. The most fre-
quently detected chemical was dieldrin, found in 27 per-
cent of all samples analyzed. Other compounds, in
order of frequency, included 2DDT, aldrin, chlordane,
and heptachlor epoxide found, respectively, in 21, 9, 8,
and 7 percent of all samples analyzed.
Table 3 lists the occurrence of pesticide residues in the
agricultural soil samples collected during 1972. The
frequency of detection varied widely among the states
surveyed. The detection frequencies of atrazine appear
to be much higher for individual states than in other
analyses because atrazine analyses were performed only
when site application records indicated its use during the
current growing season.
Table 4 presents the percent incidence of residues of
selected pesticides at specific levels. For most of the
compounds listed, the highest percentage of positive
Vol. 12, No. 4, March 1979
211
TABLE 2. Compound concentrations in cropland soil for all sample sites in 37 stales, 1972 (FY 1973)
— National Soils Monitoring Program
Compound
Positive Detections
No.
Residues, ppm dry weiokt
%
Arithmetic
Mean
Estimated
Geometric
Mean'
Extremes of
Detected Values
MiN.
Max.
ORGANOCHLORINES ( 1,483 samples)
Aldrin
129
Benzene hexachloride
1
Chlordane
117
DCPA
1
o.p'-DDE
10
p.p'-DDE
299
o.p'-DDT
161
p,p'-DDT
275
o.p'-TDE
1
p.p-TDE
46
SDDT
314
Dicofol
7
Dieldrin
403
Endosulfan I
1
Endosulfan II
1
Endosulfan sulfate
1
Endrin
10
Endrin ketone
2
Heptachlor
57
Hepiachlor epoxide
97
Hexachlorobenzene
11
PCB
2
PCNB
3
Propachlor
1
Ronnel
1
Toxaphene
76
Trifluralin-
81
8.7
0.1
7.9
0.1
0.7
20.2
10.9
I8.S
0.1
3.1
21.2
0.5
27.2
0.1
0.1
0.1
0.7
0.1
3.9
6.6
0.7
0.1
0.2
0.1
0.1
5.1
5.5
0.03
<0.01
0.05
<0.01
<0.01
0.05
0.03
0.13
<0.01
0.01
0.22
<0.01
0.04
<0.0I
<0.0I
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
<0.01
0.24
0.01
0.002
0.003
<0.001
0.006
0.003
0.007
0.001
0.010
<0.001
0.008
<0.001
<0.001
0.001
0.001
<0.001
<0.001
<0.001
0.003
0.001
0.0 1
0.02
0.01
0.18
0.01
0.01
0.01
0.01
0.31
0.01
0.01
0.06
0.01
0.08
0.25
0.31
0.01
0.02
0.01
0.01
0.01
0.80
0.22
0.10
0.19
0.22
0.01
13.28
7.89
0.09
7.16
5.62
18.93
8.20
29.45
2.15
6.18
2.13
0.38
0.60
0.72
0.44
1.49
2.61
46.58
1.86
ORGANOPHOSPHATES ( 1,246 samples)
DEF
4
Diazinon
3
Malathlon
2
Paralhion, ethyl
7
Parathion, methyl
1
Phorate
13
0.3
0.2
0.2
0.6
0.1
<0.01
<0.01
<0.01
<0.01
<0.01
<0.001
<0.001
<0.001
<0.001
0.06
0.07
0.08
0.02
O.OI
0.67
0.17
0.13
0.19
Phorate
13
1.0
<0.01
<0.001
0.01
0.04
TRIAZINE (151 samples)
Atrazine
134
88.7
0.10
0.051
0.01
0.77
'Not calculated when fewer than two positive detections present.
'See footnote, Table I.
212
Pesticides Monitoring Journai
TABLE 3. Occurrence of pesticide residues in cropland soils from 37 states, 1972 — National Soils Monitoring Program
Organochlorines^
Organophosphates
ATRAZINE2
No. OF
State
Analyses
Alabama
TT
Arkansas
43
California
64
Florida
17
Georgia
29
Idaho
29
Illinois
139
Indiana
78
Iowa
150
Kentuckv
28
Louisiana
27
Michigan
53
Mid-Atlantic"
14
Mississippi
30
Missouri
82
Nebraska
101
New England '
20
New York
36
N. Carolina
31
Ohio
67
Oklahoma
64
Oregon
37
Pennsylvania
37
S. Carolina
17
S. Dakota
106
Tennessee
25
Virginia W. Virg
nia '25
Washington state
45
Wisconsin
67
Positive Detections
No.
No. OF
Analyses
Positive Detections
No.
No. of
Analyses
Positive Detections
No.
18
37
45
12
22
15
100
27
101
10
21
9
7
25
33
39
7
13
19
20
7
11
11
15
12
15
6
9
82
86
70
71
76
52
72
35
67
36
78
17
50
83
40
39
35
36
61
30
11
30
30
88
11
60
24
20
12
22
43
53
17
28
25
87
59
113
15
26
44
14
25
66
86
20
35
28
53
64
33
37
17
90
21
25
43
57
14
2
1
11
18
4
34
3
17
4
34
2
94
100
100
67
14
1
14
0
100
13
19
13
17
100
90
6
6
100
8
7
88
7
5
71
2
2
2
0
100
16
15
94
1 Although trifluralin is a dinitroaniline compound, it is detected bv the organochlorine methodology and thus appears with organochlorines in
Tables 2-7.
-Samples analyzed only when application records indicated atrazine use during the current growing season.
^Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to
obtain more representative data. Stale groups used were Mid-Atlantic: Delaware, Maryland and New Jersey; New England: Connecticut. Maine,
Massachusetts. New Hampshire. Rhode Island, and Vermont: and Virginia and West Virginia.
TABLE 4. Percent incidence of selected pesticides in cropland soil from all sampling sites in 37 states, 1972
— National Soils Monitoring Program
Concentration,
Heptachlor
PPM DRY WT
i:DDT
Aldrin
Dieldrin
Chlordane
Heptachlor
Epo.vide
TOXAPHENE
Trifluralin
Not detected
78.8
91.3
72.8
92.1
96.2
93.5
94.9
94.5
0.01- 0.25
11.7
7.3
23.6
3.3
3.6
6.4
0.1
5.0
0.26- 1.00
5.3
1.0
3.2
3.2
0.2
0.1
1.1
0.4
1.01- 5.00
3.1
0.3
0.3
1.3
—
—
2.6
0.1
5.01-10.00
0.7
0.1
0.1
—
—
0.9
—
>10.00
0.4
0.1
—
—
—
—
0.4
—
TOTAL
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
Vol. 12, No. 4, March 1979
213
TABLE 5. Compound concentrations in cropland soils, l>y state, 1972 — National Soils Monitoring Program
Positive Detections
Compound
No.
%
Arithmetic
Mean
Concentration
Residues, ppm dry weight
Estimated
Geometric
Mean ^
Extremes of
Detected Values
MiN.
Max.
ALABAMA
Organochlorines,= 22 samples
Chlordane 1
P.p'-DDE 14
o.p-DDT 8
p.p'-DDT 15
XDUT 15
Dieldrin 2
Endrin 1
Ronnel 1
Toxaphene 7
Trifluralin 4
Organophosphates, 22 samples
Phorate 1
4.6
63.6
36.4
68.2
68.2
9.1
4.6
4.6
31.8
18.2
4.6
0.01
0.08
0.03
0.16
0.27
<0.01
<0.01
<0.01
0.67
0.02
<0.01
0.028
0.009
0.042
0.062
0.001
0.038
0.006
0.16
0.01
0.01
0.01
0.01
0.01
0.10
0.19
0.22
0.07
0.04
0.58
0.19
1.24
1.97
0.01
5.94
0.17
ARKANSAS
Organochlorines." 43 samples
Chlordane 2
o.p'-DDE 1
p.p'-DDE 25
o.p'-DDT 22
p,p'-DDT 27
p.p'-TDE 5
2DDT 27
Dieldrin 10
Endrin 2
Toxaphene 1 1
Trifluralin 17
4.6
2.3
S8.1
51.2
62.8
11.6
62.8
23.3
4.6
25.6
39.5
<0.01
<0.01
0.16
0.13
0.54
0.02
0.85
0.02
0.01
1.01
0.04
0.001
0.036
0.027
0.083
0.002
0.114
0.005
0.001
0.033
0.015
0.03
0.03
0.01
0.01
0.01
0.01
0.03
0.01
0.02
0.48
0.01
0.08
1.87
0.92
4.49
0.45
7.35
0.24
0.24
9.11
0.31
Organophosphates, 43 samples; no residues detected
CALIFORNIA
Organochlorines,"
64 samples
Chlordane
2
o.p'-DDE
3
p.p'-DDE
44
o,p-DDT
23
P.p'-DDT
32
P.p'-TDE
7
2DDT
45
Dicofol
4
Dieldrin
7
Hexachlorobenzene
1
PCBs
1
Toxaphene
9
Trifluralin
1
Organophosphates
53
samples
DEF
1
Malathion
1
Parathion, ethyl
4
3.1
4.7
68.7
35.9
50.0
10.9
70.3
6.3
10.9
1.6
1.6
14.1
1.6
1.9
1.9
7.6
0.02
<0.01
0.16
0.06
0.26
0.01
0.49
0.05
0.01
0.01
0.02
0.25
<0.01
<0.01
<0.01
0.01
0.001
0.001
0.042
0.011
0.033
0.002
0.074
0.003
0.002
0.010
0.002
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.38
0.01
0.44
1.49
0.46
0.05
0.10
0.13
0.02
1.02
0.03
2.72
1.38
5.62
0.27
9.72
2.15
0.36
6.45
0.19
FLORIDA
Organochlorines, 17 samples
Aldrin I
Chlordane 4
p.p'-DDE 10
o.p'-DDT 2
P.p'-DDT 10
P.p'-TDE 1
2DDT 11
Dicofol 3
Dieldrin 3
Heptachlor epoxide 1
Toxaphene 3
5.9
23.5
58.8
11.8
58.8
5.9
64.7
17.6
17.6
5.9
17.6
loxapnene .* 17. t
Organophosphates. 17 samples: no residues detected
Triazines, 1 sample: no residues detected
0.01
0.03
0.08
0.03
0.21
0.04
0.37
0.03
0.08
<0.01
0.83
0.007
0.017
0.004
0.022
0.035
0.006
0.009
0.019
0.16
0.02
0.01
0.02
0.01
0.74
0.01
0.06
0.15
0.01
2.04
0.22
0.66
0.56
2.16
3.38
0.23
1.09
9.00
GEORGIA
Organochlorines,' 29 samples
Benzene hexachloridc I
Chlordane 1
o.p'-DDE 1
p.p'-DDE 20
3.4
3.4
3.4
69.0
<0.01
<0.01
<0.01
0.11
0.031
0.02
0.01
0.01
0.01
1.30
(Continued next paf>e)
214
Pi sTiciDEs Monitoring Journal
TABLE 5 (Cont'd.). Compound concentrations in cropUmd soils, by state, 1972 — National Soils Monitoring Program
Residues, ppm dry weight
Compound
No
o,p'-DDT
6
p.p'-DDT
20
P.p'-TDE
2
2 DDT
22
Dieldrin
4
Endrin
1
Toxaphene
8
Trifluralin
2
Positive Detections
%
Arithmetic
Mean
Concentration
Estimated
Geometric
Mean'
extkemes of
Detected Values
MiN.
Max.
Organophosphates, 28 samples
Phorate 4
20.7
69.0
6.9
75.9
13.8
3.4
27.6
6.9
14.3
0.08
0.33
0.01
0.52
<0.0I
<0.0I
2.22
<0.01
<0.01
0.008
0.043
0.002
0.072
0.001
0.036
0.001
0.002
0.04
0.01
0.03
0.01
0.01
0.01
0.65
0.01
0.02
1.71
6.11
0.15
9.12
0.02
46.58
0.09
0.04
IDAHO
Organochlorines,
29 samples
Chiordane
1
p.p'DDE
11
o,p -DDT
4
p.p'-DDT
10
P.p'-TDE
2
2 DDT
12
Dieldrin
11
Heptachlor epo
xide
1
Hcxachlorobenzene
1
3.4
37.9
13.8
34.5
6.9
41.4
37.9
3.4
3.4
Organophosphates, 25 samples: no residues detected
0.01
0.02
0.01
0.05
<o.ai
0.09
0.01
<0.01
<0.01
0.008
0.003
0.009
0.001
0.015
0.006
0.20
0.01
0.02
0.01
0.01
0.01
0.01
0.04
0.01
0.13
0.29
0.96
0.04
1.38
0.04
ILLINOIS
Organochlorines, 2 139 samples
Aldrin
51
36.7
Chiordane
38
27.3
o.p-DDE
I
0.7
p.p'-DDE
10
7.2
P.p'-DDT
10
7.2
2 DDT
12
8.6
Dieldrin
93
66.9
Endrin ketone
1
0.7
Heptachlor
31
22.3
Heptachlor epox
de
37
26.6
Trifluralin
9
6.5
Organophosphates
87
samples
Diazinon
-)
2.3
Phorate
I
1.2
Triazines, 18 samples
Atrazine
17
94.4
Organochlorines,^
78 samples
Aldrin
13
16.7
Chiordane
5
6.4
p.p'-DDE
1
1.3
P.p'-TDE
2
2.6
2 DDT
2
2.6
Dieldrin
22
28.2
Heptachlor
4
5.1
Heptachlor epox
de
4
5.1
Trifluralin
4
5.1
Organophosphates
59 samples:
no residues detected
Triazines, 4 samples
Atrazine
4
100.0
0.14
0.22
<0.01
<0.0I
<0.01
0.01
0.16
<0.01
0.01
0.02
0.01
<0.01
<0.01
0.009
0.020
0 001
0.001
0.002
0.051
0.004
0.007
0.001
<0.001
0.074
INDIANA
0.02
0.08
<0.01
<0.01
<0.01
0.05
<0.01
<0.01
0.01
0.08
0.004
0.003
<0.001
<0.001
0.010
0.001
0.001
0.002
0.075
0.01
0.04
0.03
0.02
0.03
0.02
0.01
0.02
0.01
0.01
0.02
0.15
0.40
0.01
0.01
0.26
0.05
0.01
0.01
0.01
0.03
0.04
0.06
0.03
12.69
3.97
0.06
0.11
0.16
6.18
0.60
0.26
0.27
0.17
0.33
0.40
3.95
0.06
0.11
1.11
0.21
0.12
0.60
0.11
IOWA
Organochlorines, -
150
samples
Aldrin
28
Chiordane
29
p.p'-DDE
16
o,p'-DDT
6
p.p'-DDT
14
P.p'-TDE
2
2 DDT
17
Dieldrin
85
Heptachlor
13
Heptachlor epox
ide
27
PCBs
1
Propachlor
1
Trifluralin
22
18.7
19.3
10.7
4.0
9.3
1.3
11.3
56.7
8.7
18.0
0.7
0.7
14.7
0.04
0.10
0.01
<0.01
0.02
<0.01
0.03
O.09
0.01
0.01
0.01
<0.01
0.01
0.004
0.009
0.002
0.001
0.003
<0.001
0.003
0.029
0.001
0.003
0.004
0.01
0.02
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.80
0.10
0.01
2.07
3.44
0.33
0.24
0.93
0.01
1.50
1.62
0.44
0.20
0.18
(Continued next page)
Vol. 12, No. 4, March 1979
215
TABLE 5 (Cont'd.). Compound comciilratioiis in cropland soils, by state. 1972 — National Soils Monitoring Program
Positive Detections
Compound
No.
Arithmetic
Mean
Concentration
Residues, ppm dry weight
Estimated
Geometric
Mean'
Extremes of
Detected Values
MiN.
Max.
Organophosphates, 113 samples
Diazinon 1
Triazines. 34 samples
Atrazine 32
0.9
94.1
<0,01
0.21
0.07
0.01
0.77
KENTUCKY
Organochlorines. 28 samples
Chlordane 2
p.p'-DDE 3
p.p'-DDT 3
p,p'-TDE 2
3 DDT 4
Dieldrin 7
Hepiachlor epoxide 2
Organophosphates. 15 samples:
Triazines, 3 samples
Atrazine 2
7.1
10.7
10.7
7.1
14.3
25.0
7.1
no residues detected
66.7
0.01
<0.01
<0.01
<0.01
0.01
0.01
<0.01
0.01
0.002
0.001
0.002
0.001
0.002
0.004
0.001
0.010
0.14
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.18
0.03
0.05
0.01
0.08
0.12
0.02
0.03
LOUISIANA
Organochlorines.- 27 samples
Aldrin 2
p.p'-DDE 14
o,p'-DDT 10
p.p'-DDT 14
3 DDT 14
Dieldrin 11
Endrin 1
Toxaphene 8
Trifluralin 2
Organophosphates, 26 samples
DEF 1
Phorate 2
7.4
51.9
37.0
51.9
51.9
40.7
3.7
29.6
7.4
3.9
7.7
<0.01
0.43
0.41
1.26
2.09
0.03
0.02
3.51
0.01
<0.01
<0.01
0.001
0.046
0.030
0.072
O.IOO
0.012
0.065
0.002
0.001
0.01
0.01
0.01
0.01
0.03
0.01
0.48
2.08
0.11
0.08
0.04
0.05
6.21
5.62
15.86
27.69
0.27
29.99
0.12
0.04
MICHIGAN
Organochlorines,= 53 samples
3.8
1.9
1.9
11.3
7.6
9.4
1.9
11.3
7.6
1.9
1.9
Organophosphates. 44 samples: no residues detected
Triazines. 14 samples
Atrazine 14 100 0
Aldrin
2
Chlordane
1
DCPA
1
p.p'-DDE
6
o.p'-DDT
4
p.p'-DDT
5
p.p'-TDE
1
:ddt
6
Dieldrin
4
Hexachlorobenzene
1
Trifluralin
1
0.25
0.02
<0.01
0.24
0.13
0.67
<0.01
1.04
0.06
<0.01
0.01
0.09
0.002
0.005
0.004
0.006
0.007
0.003
0.062
0.04
1.24
0.18
0.02
0.09
0.05
0.10
0.02
0.09
0.07
0.31
0.01
13.28
7.16
3.36
18.93
29.45
2.26
0.41
MID-ATLANTIC^
Organochlorines, 14 samples
Chlordane 2
D.p'-DDE 1
p.p'-DDE 4
o.p'DDT 3
p.p'-DDT 4
P.p'-TDE 1
2 DDT 4
Dieldrin 4
Endrin 1
Hcptachlor 1
Hepiachlor epoxide 1
14,3
7.1
28.6
21.4
28.6
7.1
28.6
28.6
7.1
7.1
7.1
Organophosphates. 14 samples: no residues detected
Triazines, 1 sample: no residues delected
0.07
0.01
0.15
0.02
0.12
<0.«1
0.30
0.03
0.02
<0.01
<0.01
0.007
0.013
0.006
0.014
0.020
0.0C8
0.16
0.09
0.04
0.04
0.02
0.07
0.06
0.04
0.25
0.01
0.07
0.83
1.83
0.23
1.17
3.32
0.26
Organochlorines,^ 30 samples
P.p'-DDE 24
o.p'-DDT 18
P.p'-DDT 24
P.P'-TDE 3_
(Continued next page)
216
MISSISSIPPI
so.o
60.0
80.0
10.0
0.23
0.27
1.12
0.04
0.087
0.057
0.239
0.003
0.02
0.01
0.02
001
1.54
1.79
8.76
1.25
Pesticides Monitoring Journal
TABLE 5 (Cont'd.). Compound conccnirations in cropland soils, by state, 1972 — National Soils Monitoring Program
Residues, ppm dry weight
Compound
No.
2 DDT
24
Dieldrin
3
Toxaphene
16
Trifluralin
1
Organophosphates,
25 samples
DEF
-»
Phoratc
1
Positive Detections
%
Arithmetic
Mean
Concentration
Estimated
Geometric
Mean'
Extremes of
Detected Values
MiN.
Max.
80.0
10.0
53.3
3.3
8.0
4.0
1.66
<0.01
2.21
<0.01
0.03
<0.01
0.337
0.001
0.185
0.003
0.05
0.01
0.49
O.OS
0.06
0.03
12.33
0.05
12.77
0.67
MISSOURI
Organochlorines.- 82 samples
Aldrin
14
17.1
Chlordane
3
3.7
p.p'-DDE
6
7.3
o.p'-DDT
3
3.7
p.P -DDT
6
7.3
2DD1
6
7.3
Dieldrin
26
31.7
Heptachlor
2
2.4
Heptachlor
epoxi
de
3
3.7
Toxaphene
2
2.4
Trifluralin
6
7.3
Organophosphates.
66
samples:
no residues detected
Tnazines. 13
sampl
les
Atrazine
13
100.0
0.05
0.01
<0.01
<0.01
0.01
0.02
0.05
<0.01
<0.01
0.04
0.02
0.07
0 006
0.001
0.001
0.001
0.002
0.002
0.012
0.001
0.001
0.001
0.003
0.055
0.01
0.26
0.01
0.01
0.06
0.08
0.01
0.05
0.01
1.01
0.04
0.01
1.55
0.62
0.10
0.12
0.51
0.73
0.60
0.07
0.06
1.99
0.68
0.17
Organochlorines,- 101 samples
Aldrin 2
Chlordane 8
p.p'-DDE 7
o.p'-DDT 1
P.P'-DDT 6
2 DDT 7
Dieldrin 34
Endrin 1
Heptachlor epoxide 5
Organophosphates. 86 samples; no residues detected
Triazines. 19 samples
Atrazine 17 89.5
NEBRASKA
2.0
<0.01
<0.001
7.9
0.01
0.002
6.9
<0.01
0.001
1.0
<0.01
—
5.9
0.01
0.001
6.9
0.01
0.002
33.7
0.03
0.009
1.0
<0.01
—
5.0
<0.01
0.001
0.06
0.035
0.01
0.01
0.01
0.12
0.01
0.02
0.01
0.01
0.01
0.01
0.06
0.19
0.36
0.50
0.98
0.29
0.07
0.31
NEW ENGLAND^
Organochlorines, 20 samples
Chlordane 2
p.p'-DDE 6
o.p'-DDT 3
p.p'-DDT 5
P.P'-TDE 3
2 DDT 6
Dieldrin 2
Endosulfan I 1
Endosulfan II 1
Endosulfan sulfate 1
Heptachlor epoxide
10.0
30.0
15.0
25.0
15.0
30.0
10.0
5.0
5.0
5.0
10.0
Organophosphates, 20 samples: no residues detected
Organochlorines, 36 samples
Chlordane 1
o,p'-DDE 2
p.p'-DDE 9
o.p'-DDT 7
p.p'-DDT 9
o.p'-TDE 1
P.P'-TDE 2
2 DDT 9
Dieldrin 6
Endrin 1
Heptachlor 1
Organophosphates, 35 samples:
Triazines, 6 samples
Atrazine 6
2.8
5.6
25.0
19.4
25.0
2.8
5.6
25.0
16.7
2.8
2.8
no residues detected
100.0
(Continued next page)
Vol. 12, No. 4, March 1979
0.03
0.24
0.01
0.20
0.44
0.90
0.24
<0.01
0.01
0.02
<0.01
NEW YORK
0.03
<0.01
0.06
0.02
0.13
0.01
0.02
0.24
0.01
0.01
<0.0I
0.06
0.004
0.012
0.004
0.015
0.009
0.022
0.006
0.001
0.007
0.005
0.012
0.002
0.016
0.004
0.045
0.30
0.02
0.02
0.04
0.09
0.03
0.19
0.08
0.25
0.31
0.03
1.02
0.03
0.01
0.02
0.05
0.31
0.18
0.08
0.01
0.24
0.01
0.01
0.31
4.34
0.18
2.49
8.20
15.03
4.64
0.06
0.04
1.26
0.44
3.14
0.52
5.06
0.21
0.21
217
TABLE 5 (Cont'd.). Coinpoiinil concentrations in cropland soils, by state, l')72 — National Soils Monitorinf; Program
Positive Detections
Compound
No.
Arithmetic
Mean
concentkation
Residues, ppm dry weight
Estimated
Geometric
Mean^
Extremes of
Detected Values
MiN.
Max.
NORTH CAROLINA
Organochlorines,2 31 samples
Aldrin
3.2
Chlordane
6.4
p,p'-DDE
17
54.8
o.p'-DDT
13
41.9
p,p'-DDT
17
54.8
p.p'-TDE
12.9
2 DDT
17
54.8
Dieldrin
in
32.3
Endrin
3.2
Endrin ketone
3.2
Heptachlor
3.2
Heptachlor epoxide
3.2
PCNB
3.2
Toxaphene
12.9
Trifluralin
9.7
Organophosphates. 28
samples
Parathion. ethyl
3.6
Phorate
10.7
Triazines. 2 samples:
no residues detected
<0.01
0.05
0.18
0.04
0.18
0.01
0.41
0.03
0.07
0.01
<0.01
<0.01
0.03
0.47
0.06
<0.01
<0.01
0.002
0.027
0.013
0.044
0.C03
0.065
0.007
0.010
0.003
0.001
0.10
0.02
0.02
0.01
0.02
0.02
0.06
0.01
2.13
0.38
0.01
0.03
0.98
1.07
0.02
0.12
0.01
1.39
3.92
0.26
1.58
0.28
5.76
0.32
11.03
1.86
0.06
OHIO
Organochlorines, 67 samples
Aldrin 12
Chlordane 2
p,p-DDE 2
p.p'-TDE 2
2 DDT 2
Dieldrin 18
Heptachlor 2
Heptachlor epoxide
17.9
3.0
3.0
3.0
3.0
26.9
3.0
1.5
Organophosphates. 53 samples: no residues detected
Triazines, 8 samples
Atrazine 7 87.5
0.03
0.09
<0.0I
<0.01
<0.01
0.02
0.01
<0.01
0.07
0.005
0.002
<0.001
0.001
0.001
0.007
0.001
0.050
0.01
0.87
0.02
0.05
0.08
0.01
0.16
0.07
0.02
0.61
4.99
0.04
0.06
0.09
0.27
0.29
0.19
OKLAHOMA
Organochlorines," 64 samples
6.3
3.1
4.7
6.3
1.6
3.1
1.6
1.6
Organophosphates, 64 samples: no residues detected
P,P'-DDE
o.p'-DDT
P.p'-DDT
2 DDT
Dieldrin
Hexachlorobenzene
PCNB
1
Trifluralin
I
0.01
<0.01
0.01
0.02
<0.01
<0.01
0.04
<0.01
0.001
0.001
0.001
0.002
0.001
0.01
0.03
0.05
0.01
0.04
0.03
2.61
0.08
0.41
0.18
0.30
0.89
0.12
OREGON
Organochlorines, 37 samples
Chlordane
2
5.4
P,p'-DDE
8
21.6
o.p'-DDT
3
8.1
P.p'-DDT
5
13.5
P,p'-TDE
1
2.7
2 DDT
8
21.6
Dieldrin
4
10.8
Heptachlor epoxide
2
5.4
Toxaphene
2
5.4
rganophosphates, 33 sa
mples:
no residues detected
<0.01
0.03
0.01
0.04
<0.01
0.08
0.01
<0.01
0.03
0.001
0.005
0.002
0.005
0.007
0.003
<0.OOI
0.003
0.02
0.01
0.03
0.03
0.03
0.01
0.03
0.01
0.55
0.05
0.65
0.35
1.05
2.08
0.19
O.OI
0.64
PENNSYLVANIA
Organochlorines.^ 37 samples
Chlordane 2
5.4
P.p'-DDE 7
18.9
o,p'-DDT 3
8.1
P.p'-DDT 6
16.2
2 DDT 7
18.9
Dieldrin 6
16.2
Heptachlor epoxide 2
5.4
Trifluralin 1
2.7
Organophosphates. 37 samples:
no residues detected
Triazines, 7 samples
Atrazine 5
71.4
0.01
0.04
O.OI
0.03
0.07
0.01
<0.01
<0.01
0.03
0.002
0.006
0.002
0.005
0.007
0.004
0.001
0.022
0.21
0.01
0.02
0.02
0.01
0.03
0.01
0.13
0.01
0.26
0.72
0.16
0.61
1.49
0.23
0.05
0.10
(Continued next page)
218
Pesticides Monitoring Journal
TABLE 5 (Cont'd. ). Compound concentrations in cropland soils, by state, 1972 — National Soils Monitoring Program
Positive Detections
Compound
No. OF
%
Arithmetic
Mean
Concentration
Residues, ppm dry weight
Estimated
Geometric
Meani
Extremes of
Detected Values
MiN.
Max.
SOUTH CAROLINA
Organochlorines,- 17 samples
o.p'-DDE 1
p.p'-DDE 15
o.p'-DDT 12
p.p-DDT 15
p.p-TDE 4
2 DDT 15
Dieldrin 2
Toxaphene 6
Trifluralin 4
Organophosphates, 17 samples
Phorale 1
5.9
88.2
70.6
88.2
23.5
88.2
11.8
35.3
23.5
5.9
<0.0l
0.16
0.08
0.40
0.01
0.64
<0.01
1.17
0.01
<0.01
0.088
0.032
0.159
0.004
0.263
0.002
0.062
0.003
0.03
0.02
0.01
0.02
0.01
0.04
0.01
0.82
0.01
0.04
0.38
0.39
1.11
0.14
1.88
0.05
6.16
0.05
SOUTH DAKOTA
Organochlorines, 106 samples
Aldrin 3
Chlordane 2
p.p'-DDE
o.p'-DDT
p,p-DDT
p.p--TDE
2 DDT
Dieldrin 1
Endrin
Hepiachlor epoxide .:
Organophosphates, 90 samples
Malathion 1
Parathion, ethyl 2
Parathion, methyl 1
1.9
0.9
0.9
0.9
0.9
0.9
10.4
0.9
1.9
1.1
2.2
1.1
Organochlorines,- 25 samples
Chlordane I
p.p'-DDE 8
o.p'-DDT 3
p.p'-DDT 8
p.p'-TDE I
2 DDT 9
Dieldrin 6
Hepiachlor epoxide 1
PCNB 1
Toxaphene 1
Trifluralin 2
4.0
32.0
12.0
32.0
4.1)
36.0
24.0
4.0
4.0
4.0
i.O
Organophosphates. 2 samples: no residues detected
Triazines, 2 samples
Atrazine 2 100.0
Organochlorines, 25 samples
Chlordane 1
P.p'-DDE 3
o.p'-DDT 2
p.p'-DDT 3
2 DDT 4
Dieldrin 3
Hepiachlor epoxide
4.0
12.0
8.0
12.0
16.0
12.0
8.0
Organophosphates, 25 samples: no residues detected
Triazines. 3 samples: no residues detected
Organochlorines,- 45 samples
p.p'-DDE
o.p'-DDT
p.p'-DDT
2 DDT
Dieldrin
Hexachlorobenzene
Trifluralin
4.4
2.2
2.2
4.4
4.4
13.3
Organophosphates, 43 samples: no residues detected
<0,01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.001
0.001
0.002
<0.001
0.001
TENNESSEE
0.32
0.02
0.01
0.04
0.0 1
0.08
0.04
0.03
0.01
0.13
<0.01
0.02
0.008
0.003
0.011
0.017
0.007
0.002
0.018
VIRGINIA/WEST VIRGINIA'
0.03
0.01
<0.0I
0.01
0.02
0.0!
0.01
0.002
O.OOl
0.002
0.003
0.003
0.001
WASHINGTON STATE
<0.01
<0.01
<0.01
<0.01
<o.oi
<?).01
<0.01
0.001
0.001
0.001
0.002
(Continued next page)
Vol. 12, No. 4, March 1979
0.01
0.15
0.13
0.03
0.33
0.01
0.50
0.01
0.04
0.01
0.08
0.06
0.01
7.89
0.01
0.06
0.03
0.17
0.02
0.02
0.72
0.22
3.37
0.05
0.01
0.70
0.01
0.01
0.01
0.01
0.03
0.01
0.05
0.31
0.21
0.03
0.10
0.25
0.20
0.32
0.51
0.41
0.07
0.03
0.09
0.02
0.13
0.23
0.15
0.12
0.05
0.06
0.01
0.04
0.05
0.11
0.02
0.03
0.01
0.03
0.06
219
TABLE 5 (Cont'd.). Compound concentrations in cropland soils, hy state. l')72 — National Soils Monitoring Program
Positive Detections
Compound
No.
%
Arithmetic
Mean
Concentration
Residues, ppm dry weight
Estimated
Geometric
Mean*
Extremes of
Deteced Values
Mm.
Max.
WISCONSIN
Organochlorines, 67 samples
Chlordane 3
p.p'-DDE 3
o,p'-DDT 1
P.P'-DDT 2
i;DDT 3
Dieldrin 6
Heptachlor 2
Heptachlor epoxide 3
4.5
4.5
1.5
3.0
4.5
9.0
3.0
4.5
Organophosphates, 57 samples: no residues delected
Triazines. 16 samples
Atrazine 15 93.8
4-
0.04
0.01
<0.01
0.01
0.02
0.01
<0.01
<0.01
0.04
0.002
0.001
0.001
0.001
0.002
0.001
0.001
0.030
0.69
0.05
0.08
0.06
0.05
0.03
0.02
0.01
O.OI
1.19
0.42
0.41
0.91
0.13
0.06
0.06
0.13
>Not calculated when fewer than two positive detections present.
2 See footnote 1, Table 1.
='See footnote 3, Table 3.
TABLE 6. Occurrence of pesticide concentrations in standing agricultural crops from 1 ,483 sampling sites. 1972
— National Soils Monitoring Program
Orcanochlorines
Organophosphates
Triazines
No. OF
Positive Detections
No. OF
Positive Detections"
No. OF
Positive Detections
Crop Materials Analyses
No.
%
Analyses
No.
%
Analyses
No. %
Alfalfa/bur clover
43
25
58
39
3
7
Asparagus
1
1
100
1
0
Beans, dry
3
1
33
3
0
Clover {Trifolium)
8
5
63
8
0
Corn, sweet (kernel
s) 2
0
2
0
. .
Corn, field (kernels
) 288
31
U
167
0
.
12
0 —
Corn stalks
283
132
47
247
6
->
16
0 —
Cotton stalks
40
39
98
40
32
80
Cotton
2
0
2
0
Cotton seed
38
31
82
32
13
41
Grass hay
21
14
67
21
6
29
Leipedeza
1
1
100
1
1
100
Mixed hay
47
31
66
43
3
7
Oat hay
1
0
— ■
1
0
Pasture forage
10
5
50
9
1
11
Peanut vines
2
2
100
2
0
.^^
Soybean hay
1
1
100
_
Sugar beet lops
1
0
_
Silage (corn
or sorghum)
3
1
33
2
1
50
Milo
3
1
33
2
0
Peanuts
9
6
67
0
Peas
1
0
0
__^
Pecans
1
0
0
Rye
1
1
100
0
Sorghum (grain)
14
5
36
11
2
18
Sorghum (stalks)
18
8
44
15
3
20
Soybean.^
199
73
37
66
0
. .
^
Sugarcane
2
0
2
0
^
Sweet sorghum
2
2
100
__
Tobacco
2
2
100
2
1
50
—
220
Pesticides Monitoring Journal
TABLE 7. Occurrence of organochlorine concenlrations in selected, maiiire crops, from 1,483 sites by state or stale group,
1972 — National Soils Monitoring Program
Field Corn, Kernels
Soybeans
Mixed Hay
State
No. OF
Analyses
Positive Detections
No.
No. of
Analyses
Positive Detections
No.
Positive Detections
No. OF
Analyses
No.
%
Alabama
Arkansas
California
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kentucky
Louisiana
Michigan
Mid-AtlanliQi
Mississippi
Missouri
Nebraska
New England^
New York
N. Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
S. Carolina
S. Dakota
Tennessee 2
Virginia/W. Virginia^ 1
Washington state —
Wisconsin 13
41
24
71
6
1
21
3
10
27
11
6
18
1
10
11
2
17
1
5
33
7
73
17
90
100
4
19
1
5
28
14
41
3
7
4
3
15
15
3
4
10
0
2
16
6
17
0
3
0
0
1
6
0
100
53
40
57
43
41
7
40
10
10
100
100
100
100
100
14
1
1 100
1
I 100
g
1 13
1
1 100
1
1 64
1
I 100
1
I 100
1
1 100
4
I 50
1
1 100
3
1 33
J See footnote 3; Table 3.
Vol. 12, No. 4, March 1979
221
TABLE 8. Compound concentrations in standing agricultural crops, 1972 — National Soils Monitoring Program
Positive Detections
Compound
No.
Arithmetic
Mean
Concentration
Residues, ppm dry weight
Estimated
Geometric
Meani
Extremes of
Detected Values
MiN.
Max.
ALFALFA/BUR CLOVER
Organochlorines, 43 samples
Chlordane 7
p.p'-DDE 12
o.p'-DDT 12
p.p'-DDT 15
i:DDT 15
Dieldrin 16
Hepiachlor epoxide I
Toxaphene 2
Organophosphates. 39 samples
DEF 1
Diazinon I
Malathion 3
Organochlorines, I sample
p.p'-DDE
o.p'-DDT
p.p'-DDT
3: DDT
16.3
0.02
27.9
0.01
27.9
0.01
34.9
0.02
34.9
0.04
37.2
0.01
2.3
<0.01
4.6
0.01
2.6
<0.01
2.6
<0.01
7.7
0.01
ASPARAGUS
100.0
0.11
lOO.O
0.03
100.0
0.33
100.0
0.47
o.oos
0.003
0.004
0.009
0.012
0.007
0.002
0.002
0.04
0.01
0.01
0.02
0.03
0.01
0.01
0.17
0.02
0.01
0.03
0.11
0.03
0.33
0.47
0.24
0.05
0.09
0.23
0.28
0.09
0.19
0.26
Organophosphales, I sample: no residues delected
BEANS, DRY (all varieties)
Organochlorines, 3 samples
Dicofol 1
Organophosphates, 3 samples:
33.3
no residues detected
0.05
0.15
CLOVER (Trifolium sp.)
Organochlorines, 8 samples
Chlordane
p,p'-DDE
o.p'-DDT
p.p'-DDT
ZDDT
Dieldrin
25.0
37.5
50.0
50.0
50.0
Dieldrin 5 62.5
Organophosphates. 8 samples: no residues detected
0.02
0.02
0.03
0.05
0.10
0.03
0.008
0.009
0.014
0.022
0.031
0.018
0.07
0.01
0.01
0.03
0.04
0.02
0.10
0.08
0.07
0.14
0.29
0.11
CORN, SWEET (kernels)
Organochlorines, 2 samples: no residues detected
Organophosphates, 2 samples: no residues detected
CORN STALKS
Organochlorines, 283 samples
Alachlor 1 0.3
Chlordane 17 6.0
P.p'-DDE 28 9.9
o.p'-DDT 37 13.1
p.p'-DDT 62 21.9
P.p'-TDE 2 0.7
SDDT 62 21.9
Dieldrin 99 35.0
Endrin 3 l.I
Hepiachlor 1 0.3
Hcptachlor epoxide 14 5.0
Hexachlorobenzene 1 0.3
Toxaphene 9 3.2
Organophosphates, 247 samples
Diazinon 2 0.8
Malathion 3 1.2
Phorate 4 1.6
Triazines, 16 samples; no residues detected
Organochlorines, 288 samples
Chlordane ■»
o.p'-DDT
P.P'-DDT
vDDT
Dieldrin
0.7
0.3
0.7
0.7
2.8
<0.01
0.01
<0.01
<0.01
0.02
<0.01
0.03
0.01
<0.01
<0.01
<0.01
<0.01
0.04
<0.01
<0.01
<0.01
FIELD CORN (kernels)
0.002
O.OOl
0.002
0.004
<0.00l
0.005
0.005
<0.001
<0.001
0.002
<0.00l
<0.00l
<0.00I
<0.01
<0.0I
<0.01
<0.01
<0.01
<0.00l
<0.00l
<0.001
0.001
0.09
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.19
0.04
0.06
0.01
0.01
0.03
0.03
0.03
0.0 1
0.41
0.16
0.25
2.33
0.01
2.74
0.29
0.04
0.06
4.14
0.10
0.25
0.02
0.15
0.07
0.10
0.21
(Continued next page)
222
Pesticides Monitoring Journal
TABLE 8 (Cont'd.). Compound concentrations in standing agricultural crops, 1972 — National Soils Monitoring Program
Residues, ppm dry weight
Extremes of
Positive Detections
Arithmetic
Mean
Estimated
CiEOMElRir
Detected Values
Compound No.
%
Concentration
Mean!
Min.
Max.
Endrin 2
0.7
<0.01
<0.001
0.01
0.02
Heptachlor 1
0.3
<0.01
0.02
Heptachlor epoxide 23
8.0
<0.01
0.001
0.01
0.02
PCNB 1
0.3
<0.01
—
0.01
Organophosphates. 167 samples
no residues detected
Triazines, 12 samples: no residues detected
COTTON STALKS
Organochlorines,- 40 samples
Chlordane 6
15.0
0.05
0.006
0.15
1.00
o,p'-DDE 1
2.5
<0.0I
—
0.13
P.p'-DDE 29
72.5
0.67
0.089
0.01
8.89
o.p-DDT 28
70.0
0.79
0.116
0.01
13.40
p,p'-DDT 38
95.0
7.36
0.739
0.02
102.00
p.p-TDE 12
30.0
0.04
0.010
0.01
0.41
;:DDT 38
95.0
8.87
0.913
0.02
115.79
Dieldrin 14
35.0
0.02
0.008
0.01
0.19
Endosulfan sulfate 1
2.5
0.07
—
2.70
Endrin 2
5.0
0.01
0.002
0.15
0.15
Heptachlor epoxide 3
7.5
<0.01
0.001
0.01
0.02
Toxaphene 28
70.0
25.44
1.078
0.66
462.30
Trifluralin 1
2.5
<0.01
—
0.02
Organophosphates, 40 samples
Carbophcnothion 1
2.5
<0.01
—
0.08
DEE 25
62.5
1.20
0.069
0.01
24.19
Diazinon 1
2.5
<0.01
—
0.02
Malathion 4
10.0
0.03
0.003
0.01
0.94
Parathion. ethyl 5
12.5
0.01
0.003
0.01
0.12
Parathion. methyl 16
40.0
0.15
0.026
0.02
1.39
Phorate 1
2.5
<0.01
—
0.01
COTTON SEED
Organochlorines. 38 samples
P,p-DDE 16
42.1
0.01
0.008
0.01
0.12
o,p'-DDT 15
39.5
0.03
0.012
0.02
0.19
p,p'-DDT 31
81.6
0.22
0.082
0.01
1.40
P.p'-TDE 2
5.3
<0.01
0.001
0.04
0.14
ZDDT 31
81.6
0.27
0,091
0.01
1.79
Dieldrin 2
5.3
<0.01
0.001
0.01
0.03
Toxaphene 20
52.6
0.49
0.082
0.20
3.71
Organophosphates, 32 samples
DEE 13
40.6
0.09
0.016
0.02
0.71
Parathion, methyl 2
6.3
<0.01
0.001
0.04
0.05
COTTON
Organochlorines, 2 samples: no
residues detected
Organophosphates, 2 samples: no residues detected
SILAGE
Organochlorines, 3 samples
Chlordane 1
33.3
0.05
—
0.16
p.p-DDT 1
33.3
<0.01
—
0.01
VDDT 1
33.3
<0.01
—
0.01
Organophosphates, 2 samples
Diazinon 1
50.0
0.05
—
O.Il
Malathion 1
50.0
1.32
—
2.64
GRASS HAY
Organochlorines, 21 samples
Chlordane 2
9.5
0.01
0.003
0.09
0.09
o,p-DDT 12
57.1
0.02
0.014
0.01
0.08
p,p'-DDT 13
61.9
0.07
0.033
0.01
0.23
p.p-DDE 9
42.9
0.02
0.009
0.01
0.08
2DDT 13
61.9
0.11
0.044
0.01
0.30
Dieldrin 7
33.3
0.01
0.006
0.01
O.U
Toxaphene 6
28.6
0.15
0.020
0.30
1.19
Organophosphates, 21 samples
DEE 1
4.8
0.0 1
—
0.12
Diazinon 6
28.6
0.04
0.011
0.02
0.34
Malathion 5
23.8
0.03
0.007
0.02
0.22
(Continued next page)
Vol. 12, No. 4, March 1979
223
TABLE 8 (Cont'd.). Compound concenlration.s in stanclinf; iif>riciillurtil crops, 1972 — National Soils Monitoring Program •
Positive Detections
Compound
No.
Residues, ppm dry weight
Arithmetic
Mean
Concentration
Estimated
Geometric
Meani
Extremes of
Detected Values
MiN.
Max.
LESPEDEZA SERICEA
Organochlorines, I sample
p,p'-DDT 1
i:DDT I
Dieldrin 1
Endrin 1
Toxaphene 1
Organophosphales, 1 sample
DEF 1
lOO.O
100.0
100.0
100.0
100.0
100.0
O.IS
0.15
0.03
0.02
0.48
0.15
0.15
0.15
0.03
0.02
0.48
0.15
MILO
Organochlorines, 3 samples
p.p'-DDT I
P,p-DDE 1
2 DDT 1
Toxaphene
Organophosphates. 2 samples: no residues detected
33.3
33.3
33.3
33.3
0.02
<0.01
0.02
0.04
PASTURE FORAGE
0.06
0.01
0.07
0.13
Organochlorines. 10 samples
Chlordane 1
o,p'-DDT 3
p.p'-DDT 4
p.p'-DDE 3
I DDT 4
Dieldrin 4
Toxaphene 2
Organophosphates, 9 samples
Diazinon 1
10.0
30.0
40.0
30.0
40.0
40.0
20.0
11.1
0.05
0.01
0.08
0.01
0.10
0.01
0.15
<0.01
0.006
0.021
0.004
0.026
0.007
0.014
0.48
0.02
0.08
0.01
0.17
0.01
0.59
0.01
0.07
0.40
0.03
0.40
0.04
0.86
MIXED HAY
Organochlorines. 47 samples
Chlordane 10
o.p'-DDE 1
p.p-DDE 21
o.p'-DDT 23
p.p'-DDT 26
p.p'-TDE I
2 DDT 26
Dieldrin 22
Endrin 2
Heptachlor epoxide 1
Organophosphates, 43 samples
Diazinon 2
Malathion 3
Parathion, methyl 1
Phorate 1
21.3
2.1
44.7
48.9
55.3
2.1
55.3
46.8
4.3
2.1
4.6
7.0
2.3
2.3
0.03
<0.01
0.02
0.02
0.04
<0.01
0.08
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.008
0.008
0.009
0.019
0.027
0.012
<0.001
<0.001
0.001
0.05
0.04
0.01
0.01
0.01
0.02
0.02
0.01
0.01
0.05
0.01
0.02
0.01
0.02
0.44
0.13
0.12
0.44
0.69
0.11
0.01
0.02
0.09
PEANUTS
Organochlorines, 9 samples
p.p'-DDE 2
2 DDT 2
Toxaphene 6
Organophosphates, 3 samples:
22.2
22.2
66.7
no residues detected
<0.01
<0.01
0.25
0.003
0.003
0.100
0.02
0.02
0.17
0.02
0.02
0.65
PEANUT VINES
Organochlorines, 2 samples
p.p'-DDT 1
2 DDT 1
Dieldrin 2
Toxaphene 1
Organophosphates, 2 samples:
50.0
SO.O
100.0
50.0
no residues detected
0.42
0.42
0.21
106.82
0.102
0.85
0.85
0.02
213.65
0.41
PEAS (all varieties)
Organochlorines, I sample: no residues detected
Organophosphates, I sample: no residues delected
PECANS
Organochlorines. I sample: no residues detected
Organophosphates, I sample: no residues detected
(Continued next page)
224
Pesticides Monitoring Journal
TABLE 8 (Cont'd.). Compound concenlnilions in standing agrkultiinil
crops, 1972 — National Soils Monitoring Program
Residues, ppm dry weight
Positive Detections
Compound
No.
Arithmetic
Mean
Concentration
Estimated
Geometric
Mean ^
RYE
Organochlorines, 1 sample
Chlordane 1 lOO.O
Dieldrin 1 100.0
Organophosphates, 1 sample; no residues detected
0.08
0.02
Extremes of
Detected Values
MiN.
0.08
0.02
Max.
SORGHUM (grain)
Organochlorines, 14 samples
o,p'-DDT
1
p.p'-DDT
5
p,p'-DDE
2
2DDT
5
Dieldrin
2
Organophosphates, 11
samples
Malalhion
2
Parathion, ethyl
1
Parathion, methyl
1
Phorate
1
7.1
35.7
14.3
35.7
14.3
18.2
9.1
9.1
9.1
<0.01
0.01
<0.01
0.01
<0.01
0.03
<0.01
<0.01
<0.01
0.006
0.001
0.006
0.001
0.006
0.02
0.01
0.01
0.01
0.01
0.04
0.03
0.01
0.01
0.07
0.02
0.10
0.01
0.29
SORGHUM STALKS
Organochlorines, 18 samples
Chlordane 1
o.p'-DDT 5
p.p'-DDT 8
p.p'-DDE 6
p.p'-TDE 1
2 DDT 8
Dieldrin 5
Toxaphene 1
Organophosphates, 15 samples
Malathion 3
Parathion, ethyl 1
5.6
27.8
44.4
33.3
5.6
44.4
27.8
5.6
20.0
6.7
0.01
0.01
0.02
0.01
<0.01
0.04
0.01
0.01
0.02
<0.01
0.004
0.012
0.004
0.017
0.004
0.006
0.15
0.01
0.03
0.01
0.07
0.04
0.01
0.25
0.06
0.02
0.03
0.11
0.04
0.20
0.05
0.13
SUGAR BEET TOPS
Organochlorines, 1 sample: no residues detected
SOYBEANS
Organochlorines, 199 samples
Chlordane
1
0.5
o.p'-DDT
1
0.5
p.p-DDT
12
6.0
p.p'-TDE
1
0.5
2DDT
13
6.5
Dieldrin
47
23.6
Endrin
16
8.0
Heptachlor
1
0.5
Heptachlor epoxide
8
4.0
Toxaphene
12
6.0
Organophosphates. 66 sa
mples
no residues detected
<o.oi
<o.oi
<0.01
<0.01
<0.01
<0.01
<0.0I
<0.01
<0.0I
0.01
0.001
0.001
0.002
0.001
<0,00I
0.002
0.07
0.02
0.01
0.18
0.01
0.01
0.01
0.01
0.01
0.14
0.07
0.18
0.04
0.21
0.03
0.38
SOYBEAN HAY
Organochlorines. 1 sample
o.p'-DDT
p.p'-DDT
p.p'-DDE
i;DDT
Dieldrin
Toxaphene
100.0
0.32
100.0
1.43
100.0
0.18
100.0
1.93
100.0
0.05
100.0
3.52
SUGARCANE
0.32
1.43
0.18
1.93
0.05
3.52
Organochlorines. 2 samples; no residues detected
Organophosphates. 2 samples: no residues detected
SWEET SORGHUM (grain)
Organochlorines, 2 samples
p.p'-DDT 1
2DDT 1
Dieldrin 1
Toxaphene 1
50.0
50.0
50.0
50.0
- 0.07
0.07
<0.01
0.18
0.14
0.14
0.01
0.37
(Continued next page)
Vol. 12, No. 4, March 1979
225
TABLE 8 (Cont'd.). Compound concentrations in standing agricultural crops, 1972 — National Soils Monitoring Program-
Residues, ppm dry weight
Positive Detections
Compound
No.
%
Arithmetic
Mean
Concentration
Estimated
Geometric
Mean'
Extremes of
DETF.CTED Values
MiN.
Max.
TOBACCO
Organochlorines, 2 sampl
o.p'-DDT
p,p'-DDT
p.p'-DDE
2DDT
Dieldrin
Endrin
Toxaphene
Organophosphales. I sample
Diazinon
1
50.0
100.0
50.0
100.0
100.0
50.0
100.0
100.0
0.03
0.48
0.02
0.54
0.04
0.01
2.62
0.01
0.385
0.490
0.043
2.520
0.07
0.19
0.05
0.31
0.03
0.02
1.89
0.01
0.77
0.77
0.06
3.36
^ Not calculated when fewer than two positive detections present.
-Although trifluralin is a dinitroaniline compound, it is detected by the organochlorine methodology and thus appears with organochlorines in
Tables 2-7.
detections was in the 0.01-0.25-ppm category, except lor
toxaphene, which was in the 1.01-5.00-ppm category.
By State — Pesticide concentrations in soils, by states or
state groups, are presented in Table 5. Because some
small eastern states had very few sites, those with similar
geographic locations and/or agricultural characteristics
were combined to obtain more representative data. State
groups used were Mid-Atlantic: Delaware. Maryland,
and New Jersey; New England: Connecticut, Maine,
Massachusetts, New Hampshire, Rhode Island, and Ver-
mont; and Virginia and West Virginia.
Comparisons of the percent occurrence of aldrin, diel-
drin, heptachlor epoxide, 2DDT, and chlordane are
presented in Figures 2-6. The key for each figure is
based on the arithmetic mean percent occurrence (x) of
the compound for all sites. The four classes are: greater
than 2x, greater than x but less than 2x, greater than
Vix but less than x, and less than Vix.
Illinois sites had the highest percent occurrence of al-
drin, dieldrin, chlordane, and heptachlor epoxide (Fig-
ures 2-6). These compounds are soil insecticides, or
their degradation products, used in corn production. The
1972 results generally correspond with results of the
previous years for this Program {2.4, 7). -DDT detec-
tions were concentrated in the southeastern states and
California (Fig. 5). Oklahoma, Pennsylvania, South
Dakota, and Wisconsin were generally below the all-sites
average detection frequency for the compounds.
The detection of ronnci in soil from one site in Alabama
(Table 5) was unusual. Ronnci is used to control flies,
ticks, and gnats on domestic animals and in animal
quarters. A thorough examination of the cropping and
pesticide application record for that site revealed no
pesticide applications during the growing season. How-
ever, the site was being used as a cattle pasture, and the
chemical was probably transferred to the soil by treated
cattle.
COMPOUND CONCENTRATIONS IN CROPS
Mature crop samples were collected from 737 sites, or
48 percent of the scheduled 1,533 sites. All crop sam-
ples were analyzed for organochlorines, including tri-
fluralin. In addition, samples were analyzed for or-
ganophosphates and atrazine when pesticide application
records indicated their use. Thus the organophosphate
and atrazine concentration data samples are biased, and
yield higher occurrence frequencies than might other-
wise occur if all samples had been analyzed.
Table 6 lists the occurrence of pesticide residues in crop
materials sampled. For all crops, 40 percent of the
1 ,045 samples analyzed contained detectable concentra-
tions of organochlorines and 10 percent contained de-
tectable amounts of organophosphates. Atrazine was
not detected. In general, crops with known patterns of
heavy pesticide application, or animal feed crops such as
alfalfa, hay, field corn, or soybeans grown in rotation
with these crops, had the highest detection frequencies.
Table 7 presents the occurrence of organochlorines in
field corn kernels, soybeans, and mixed hay for each
state or state group sampled. Residue detections varied
most in field corn. Not enough samples were available
to draw broad conclusions about mixed hay.
Table S presents the compound concentrations detected
in each crop sampled. -DDT occurred most frequently
in all crops except corn stalks, where dieldrin residues
were predominant. The high frequency of occurrence
of -DDT is probably the result of its prior, widespread
use.
226
Pesticides Monitoring Journal
••*»ir:-
'■?'»•:
\
■ra,'.:.--.-.-.-:.-..:-*
'■-:.■■'.■'.■'■•■:>■'.■;'.'<
^^•'- '■•., 'I--; ■.'.•."■.'.■.•
'i\:
■''■ii'.~ '■■':'-''
\:r:'K- :'■■•:
- V 1 ■
<J
HEX.
3
itiii'. '■.*'•.'•.'
■::'.:y\
"■ m^;
.■;:;:•:)
U^
^^^< 1/2 X
FIGURE 2. Percent occurrence of aldrin residue detections in cropland soil of 37 states, hy slate, 1972
— National Soils Monitoring Program
1. 1'.' •■■■',' ..J
FIGURE 3. Percent occurrence of dieldrin residue detections in cropland soil of 37 stales, hy state, 1972
— National Soils Monitoring Program
Vol. 12, No. 4, March 1979
227
X <
'/2x <^^< X
P^?S?^< 1/2 i
FIGURE 4. Percent occurrence of heptachlor epoxide residue detections in cropland soil of 37 states, by state, 1972
— National Soils Monitoring Program
2x
ytftr.:/.-;
y,'J.)k ■'■■":■
\'-'\
:'~i-\'[:
^
^
«^
^
uy
'•.v;C'--
^
coio.
•.•■.•'•;
-■'^■:^^
fr^
IINI
v.-
■ El.
2
■■.:i::.' :;■:.■.
ti
rn
m
>'•'•
FIGURE 5. Percent occurrence of ZDDT residue detections in cropland soil of 37 stales, by state, 1972
— National Soils Monitoring Program
228
Pesticides Monitoring Journal
1/2 X < C
FIGURE 6. Percent occurrence of chlordane residue detections in cropland soil of 37 states, by state, 1972
— National Soils Monitoring Program
Acknowledgments
It is not possible to list by name all persons who con-
tributed to this study. The authors are especially grate-
ful to the staff of the Pesticides Monitoring Laboratory,
Bay St. Louis, Mississippi, who received, processed, and
analyzed samples for compojnd residues, and to the
inspectors of the Animal and Plant Health Inspection
Service, U.S. Department of Agriculture, who collected
the samples.
LITERATURE CITED
(/) Carey. A. E., and J. A. Gowen. 1978. Pesticide appli-
cation and cropping data from 37 states, 1972 — Na-
tional Soils Monitoring Program. Pestic. Monit. J.
12(3):137-I48.
(2) Carey, A. E., J. A. Gowen, H. Tai, W. G. Mitchell, and
G. B. Wiersma. 1978. Pesticide residue levels in soils
and crops, 1971 — National Soils Monitoring Program
(III). Pestic. Monit. J. 12(3) : 1 17-136.
(3) Carey. A. £., G. B. Wiersma. H. Tai. and W. G. Mit-
chell. 1973. Organochlorine pesticide residues in soils
and crops of the corn belt region, United States — 1970.
Pestic. Monit. J. 6(4) :369-376.
(4) Crockett. A. B.. G. B. Wiersma, H. Tai, W. G. Mit-
chell, P. F. Sand, and A. E. Carey. 1974. Pesticide
residue levels in soils and crops, FY-70 — National
Soils Monitoring Program (II). Pestic. Monit. J.
8(2):69-97.
(5) Panel on Pesticide Monitoring. 1971. Criteria for de-
fining pesticide levels to be considered an alert to poten-
tial problems. Pestic. Monit. J. 5(1):36.
(6) U.S. Environmental Protection Agency. 1973. PM
Memorandum No, 3. Sample Collection Manual. Guide-
lines for collecting field samples: soil, crops, water,
sediment. 71 pp.
(7) Wiersma. G. B., H. Tai. and P. F. Sand. 1972. Pesti-
cide residue levels in soils, FY-69 — National Soils
Monitoring Program. Pestic. Monit. J. 6(3) : 194-228.
(8) Wiersma, G. B.. P. F. Sand, and E. L. Cox. 1971. A
sampling design to determine pesticide residue levels in
soils of the conterminous United States. Pestic. Monit.
J. 5(l):63-66.
Vol. 12, No. 4, March 1979
229
Organochlorine Pesticide Residues in Soils from Six U.S. Air Force Bases, 1975-76
Jerry T. Lang,' Leopoldo L. Rodriguez,- and James M. Livingston "
ABSTRACT
Soil samples coUcctcd during 1975 and 1976 from United
States Air Force installations in California, Georgia, Ohio,
Oklahoma, Texas, and Utah were analyzed for organochlo-
rine pesticide residues. :s.DDT, chlordane, and dieldrin were
the pesticides most commonly found. In 1975, ZDDT resi-
dues were significantly higher in samples from residential
areas than in samples from golf courses or areas free of
pesticide application. Chlordane residues in 1975 were sig-
nificantly liighcr in both residential and golf course areas
than in areas where pesticides had not been used. No sig-
nificant differences were found in 1976 in residue levels of
any pesticide monitored among various land use areas.
cm) with a j-inch (7. 6-cm) -diameter bulb planter.
Twenty core samples from each site were composited in
a plastic bucket, thoroughly mixed by hand, and poured
back and forth into a similar bucket. The composite
sample was sieved through 'i-inch (6.4-mm) hardware
cloth to remove large particles and debris. A subsample
of the composite sample was placed in a clean hexane-
rinsed 8-oz (240-ml) amber glass salve jar. Salve jars
were capped with aluminum foil-lined lids and sub-
samples were kept frozen until being prepared for analy-
sis. All sampling equipment was thoroughly rinsed with
water after each stratum was sampled to avoid cross
contamination.
Introduction
In 1975, the United States Air Force Occupational and
Environmental Health Laboratory at Kelly Air Force
Base, Texas, initiated a two-year pilot pesticides monitor-
ing program to gather preliminary data on organochlo-
rine residues in soils and sediments from Air Force bases
and to determine the feasibility of developing a full-scale
Air Force pesticides monitoring program. Only the base-
line data on soil samples are discussed here. The feasi-
bility study and the baseline data for sediment samples
have been discussed elsewhere by Lang (4).
Sample Collection and Preparation
Six Air Force Logistics Command bases were sampled,
including Hill AFB, Utah; Kelly AFB, Texas: McClellan
AFB, California: Robins AFB, Georgia: Tinker AFB,
Oklahoma; and Wright-Patterson AFB, Ohio. All bases
represent urban environments with substantial indus-
trialization and histories of considerable pesticide use.
Soil samples were collected from residential, open or
nonuse, and golf course areas. Core samples from each
use stratification were taken from the top 3 inches (7.6
' Present address: Chief. EntDmology Services. OL-AD. U.S. Air Force
Occupatii>naI and Fnvironmenlal Health Laboratory. APO San Fran-
cisco. CA 96274. 7he opinions and assertions contained herein arc
those of the authors and are not to be construed as the views of
the Departtrent of the Air Force.
^U.S. Air Force Occupational and Environmental Health Faboratory,
Brooks Air Force Base, TX 782.15.
At each residential sampling site, 10 individual core
samples were taken from both sides of randomly selected
streets. At those sites with sidewalks, all samples were
taken within 1 ft (30.5 cm) of the sidewalk in the
direction of the house. At sites without sidewalks, sam-
ples were taken approximately 4 ft (1.37 m) from the
street. At each open sampling site, 10 core samples were
collected at 45-ft (13.7-m) intervals along two parallel
straight lines 45 ft (13.7 m) apart which originated at
a randomly selected point. Golf course samples were col-
lected from random starting points at 45-ft (13.7-m)
intervals along both sides of the fairway at the edge of
the rough.
A Italy tical Procedures
I'RFPARATION OF SAMPLES
Two grams of dry-sieved subsample (sieve size No. 14)
were placed in a 15-ml test tube with a Teflon-lined
screw cap, and 10 ml 3: 1 hexane-isopropanol was added.
Tubes were rotated for 4 hours, and the subsample was
centrifuged. The solution was transferred to a 60-ml
separatory funnel and washed three times with water
to remove the alcohol. The solution was dried with
anhydrous sodium sulfate, the solvent was reduced by
evaporation, and the sample was cleaned by passage
through a Florisil microcolumn. Subsample extracts were
stored at low temperature for subsequent gas-chromat-
ographic (GC) analysis.
230
Pesticides Monitoring Journal
GAS CHROMATOGRAPHY
The analytical procedures were basically the same as
those described by Wiersma et al. (6). Samples were
analyzed for organochlorines and PCBs with a Tracor
Model 222 gas chromatograph equipped with two Ni-63
electron-capture detectors (EC) and four glass columns.
Two sets of polar and nonpolar columns were used to
identify and confirm the organochlorine pesticides and
PCBs. The gas chromatograph was equipped with a
Model 8000 Varian Auto Sampler and interfaced with a
Model 3354 Hewlett-Packard Data System. Instrument
parameters and operating conditions follow:
Columns: glass. 6 ft long. 6 mm OD X 4 mm ID,
packed with
(1)3 mixture of 1.5 percent SP-2250 and 1.95
percent SP-2401 on 100-120-mesh Supelcon.
AW, DMCS
(2) a mixture of 4 percent SE-30 and 6 percent
SP-2401 on 100-1 20-me5h Supelcon, AW,
DMCS
Temperatures, °C: detector 300
injection port 225
column 200
Carrier gas: 5-10 percent methane-argon flowing at 60
ml/minute
Compounds and their quantitative detectable levels are
listed in Table 1. Minimum detectable levels of organo-
chlorine pesticides were 0.01-2.00 mg/kg.
RECOVERY STUDIES
Recovery of the components listed in Table 1 ranged
from 91 to 102 percent. Data presented in Tables 2 and
3 were not corrected for recovery.
Results and Discussion
Because a similar data pattern emerged on each base,
data for a given year on the same pesticide on the
same land use area were combined from all six bases
(Table 2). i;DDT residues were the most ubiquitous
organochlorines on the six bases (Table 2). 2DDT resi-
dues were also quantitatively higher overall than were
residues of any other organochlorine except chlordane,
which in 1975 had arithmetic mean levels consistently
TABLE 1. Qitanlitative detection limits of organochlorines
found in soils of six U.S. Air Force bases, 1975-76
Compound
Residue, ppm
2 DDT
Aldrin
Heptachlor
Lindane
Toxaphene
Chlordane
Dieldrin
Endrin
Heptachlor epoxide
Methoxychor
PCBs
0.05
0.01
0.01
0.01
2.00
0.20
0.02
0.02
0.01
0.04
0.40
O
HI
03
<
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I I
I I
o o o
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Q
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Z
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— o o^
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z
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in M-1 >/"i
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Z
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I CO
Q
z
as o
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I I
I I I
o o o
O d r-^
z
I I I
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O O m
S d ■rt
z
o q q
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dv-
z
— q o
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I rt
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mom
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C O OS
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Vol. 12, No. 4, March 1979
231
TABLE 3. Geometric means and 9!! percent confidence intervals for pooled -DDT. chlordanc
from use-stratified areas on six U.S. Air Force bases — 1975-76
and dicldrin residue data
2 DDT
Chlordane
DiELDRIN
AKEA
95^0 CI
Lower
Mean
95% CI
Upper
95% CI
Lower Mean
95% CI
Upper
95% CI
Lower
Mean
95% CI
Upper
1975 Residues, ppm
Residential
Open
Golf course
0.0791
0.0124
0.0347
0.2276'"
0.0235""
0.0599"'>
0.6549
0.0443
0.1033
0.0440 0.1875""
0.0091 0.0158""
0.0338 0.1049""
0.7153
0.0275
0.3253
0.0100
0.0089
0.0091
0.0246""
0.0119""
0.0122""
0.0606
0.0159
0.0163
1976 Residues, ppm
Residential
Open
Golf course
0.0257
0.0134
0.0110
0.0782'">
0.0361'"'
0.0437'-)
0.2382
0.0960
0.1729
0.0033 0.0150'«>
0.0100 0.0182i«>
0.0084 0.0320"»
0.0694
0.0329
0.1218
0.0094
0.0099
0.0089
0.0117""
0.0129""
0.0110""
0.0145
0.0157
0.0136
NOTE: For a given year, means in a vertical column followed by the same letter are not significantly different at the 5 percent level.
higher than -DDT. The high arithmetic mean for chlor-
dane residues in residential areas during 1975 was
mainly attributable to the high levels found at Wright-
Patterson AFB. This finding is notable in light of past
problems with chlordane contamination in Capehart
housing units on Wright-Patterson (7, 2). Except for
chlordane levels found in residential soils in 1975, the
arithmetic means shown in Table 2 closely appro.vimate
mean levels of the same pesticides in various nonmilitary
urban areas of the United States (i).
data. Therefore, standard t-tests were used to compare
mean differences in -DDT data, and t'-tests (5) were
used on the chlordane data.
In 1975, -DDT residues were significantly higher in resi-
dential areas than in open and golf course areas. Chlor-
dane levels were significantly higher in both residential
and golf course areas than in open areas. There was no
significant difference in chlordane levels between resi-
dential and golf course areas.
Since residue data are not normally distributed, the
arithmetic means in Table 2 are useful for comparison
only in a relative sense. Therefore, the more statistically
useful geometric means and associated 95 percent con-
fidence limits based on data normalized with the In
{X 4- 0.01) transformation discussed by Carey et al.
(i) are given in Table 3 for the three most ubiquitous
pesticides: -DDT, chlordane, and dieldrin.
To obtain an overall picture of the data, a three-factor
analysis of variance was used to evaluate pesticide by
land use by year interactions. The only significant inter-
action was for land use areas between the two years.
Further examination showed that only the residential
area means for 1975 and 1976 differed significantly
{P < 0.001). There was no significant difference for
the open area means (P < 0.10) and only an indication
of a difference for the golf course means (P < 0.10).
One-way analyses of variance were used to evaluate data
on a particular pesticide during a given year. Significant
F values were found only for -DDT and chlordane in
1975. Bartlett's test (5) was used to check homogeneity
of variances in the two cases. Variances were homo-
geneous for the -DDT data but not for the chlordane
Large differences between 1975 and 1976 2DDT and
chlordane data (Table 3) are puzzling. From what is
known generally of organochlorine degradation rates,
microbial or other forms of degradation could not ac-
count for the decreases in 2DDT and chlordane levels
between 1975 and 1976. The most likely explanation
for the rather drastic reduction in -DDT residues in resi-
dential areas and chlordane residues in residential and
golf course areas between 1975 and 1976 is the irregular
distribution of pesticide residues in the environment and
the relatively small number of samples collected from
each land use area.
Conclusions
Organochlorine residues on the six Air Force installa-
tions generally were the same generic type and quantity
as those found in nonmilitary urban environments.
-DDT residues were the most abundant followed by
chlordane and dieldrin. Residential areas generally were
contaminated more heavily with organochlorincs than
were open or nonuse and golf course areas. Large
variations between 1975 and 1976 data on some pesti-
cides indicate that, if the Air Force program is contin-
ued, more samples should be taken from each sampling
site and increased emphasis should be placed on sampling
protocol to ensure the gathering of comparative data.
232
Pesticides Monitoring Journal
LITERATURE CITED
(/) Air Force Logistics Command Headquarters. 1975.
Summary and comparison of two-hour baseline chlor-
dane air sampling results from Air Force military
family housing (AF MFH). Office of the Surgeon,
Wright-Patterson Air Force Base, Ohio, 62 pp.
(2) Air Force Logistics Command Headquarters. 1976.
Report on four chlordane sampling protocols conducted
in military family housing at Wright-Patterson AFB,
Ohio. Office of the Surgeon, Wright-Patterson Air
Force Base, Ohio, 136 pp.
(.?) Carey, A. E.. G. B. IViersma, and H. Tai. 1976. Pesti-
cide residues in urban soils from 14 United States
cities, 1970. Pestic. Monit. J. 10(2) :54-6().
(4) Lang. J. T. 1978. USAF Occupational and Environ-
mental Health Laboratory, Tech. Repl. 78-33, Evalua-
tion of the USAF pesticides monitoring pilot program,
1975-1976.
(5) Snedecor, G. W.. and W. G. Cochran. 1967. Statistical
Methods (6th ed.). Iowa State University Press, Ames,
Iowa. 593 pp.
(6) Wiersma. G. B., H. Tai. and P. F. Saiul. 1972. Pesticide
residue levels in soils, FY 1969 — National Soils Mon-
itoring Program. Pestic. Monit. J. 6(3) : 194-201.
Vol. 12, No. 4, March 1979
233
APPENDIX'
Chemical Names of Compounds Discussed in This Issue
ACEPHATE
ALDRIN
CHLORDANE
DDE
DDT
DELNAV
DIAZINON
DIELDRIN
DURSBAN
ENDRIN
ETHION
HCB
HEPTACHLOR
HEPTACHLOR EPOXIDE
LINDANE
MALATHION
METHAMIDOPHOS
MIREX
NONACHLOR
OXYCHLORDANE
PCBs {Polychlorinaicd Biphenyls)
TDE
TOXAPHENE
TRITHION
O, ^-Dimethyl acetylphosphoramidolhioaie
Not less than 95% of l,2.3.4.10.IO-hexachloro-I,4,4a,5.8,8a-hexahydro-l.4:5,8-dimcihanonaph-
ihalene
1.2,3.4,5.6,7,8.8-Ociachloro-2,3,3a,4,7.7a-hexahydro-4.7-meihanoindene. The technical product
is a mixture of several cotiipounds including heptachlor, chlordene, and two isomeric forms
of chlordane.
Dichlorophenyl dichloro-ethyletic (degradation product of DDT); />,//-DDE: I .l-Dichloro-
2.2-bis{/J-chloIophe^yl) ethylene; *>.//-DDE: 1 .1 -Dich!oro-2-(o-chlorophenyl)-2-(/;-chIorophenyl)
ethylene
Main component {p,p'-DDT) : n-Bist/j-chlorophenyl ) /i,/?./i.-trichloroethane. Other isomers
are possible and some are present in the commercial product. ri.p'-DDT: [l.l,l-Trichloro-2-
(o-chlorophenyl)-2-(p-chlorophenyl) ethane]
2,3-p-DiozanedithioI 5..y-bis (0,0-diethyl phosphorodiihioate)
O.O-Diethyl 0-{2-isopropyl-6-melhyl-4-pyrimidinyI } phosphorothioate
Not less than 85% of 1.2, .1.4,10. 10-Hexachloro-6,7-epoxy-l.4,4a. 5,6, 7:8.8a-octahydro-l,4-
e«rfo-e>:o-5,8-dimethanonaphthalene
0,0-Dielhyl 0-( 3,5,6-trichloro-2-pyridyl )
Hexachloroepoxyoctahydro-f«(io.i'/if/o-dimethano-naphthalene
O,O,0'.O'-Telraethyl 5,5'-methylene bisphosphorodithioate
Hexachlorobenzene
1.4,5.6,7,8,8-Heptachloro-.1a,4.7,7a-tetrahydro-4.7-ra</()-methanoindene
I,4,5.6,7,8,8-Heptachloro-2.3-epoxy-.3a,4,7,7a-tetrahydro-4.7-methanoindcne
Gamma isomer of 1.2,3,4.5,6-hexachlorocyclohexane
O.O-Dimethyl dithiophosphate of diethyl mercaptosiiccinale
0,.y-Dimethyl phosphoramidolhioate
l.la.2,2,3,3a,4.5,5,5a,5b,6-Dodecachlorooctahydro-l,3,4-metheno-IW-cyclobula|cdlpcntalcne
1.2.3,4,5.6,7,8-Nonachlor-3a.4,7.7a-tetrahydro-4,7-methanoindan
2,3,4,5,6,6a,7,7-Octachlor<)-la,lb.5.5a.6,6a-hexahydro-2.5-methano-2//-indenot 1.2-/*)oxirene
Mixtures of chlorinated biphenyl compounds having various percentages of chlorine
2.2-Bis(p-chlorophenyl)-1.1-dichloroethane (including isomers and dehydrochlorination products)
Chlorinated camphenc (67-69% chlorine). Product is a mixture of polychlor bicyclic terpenes
with chlorinated camphenes predominating.
.V-l((p-ChlorophenyI )thioIniethyl| 0,O-dicthyl plnisphorodithioate
'Docs not include compounds listed only in Carey and Gowen and in Carey el al.
234
Pesticides Monitoring Journal
ERRATA
PESTICIDES MONITORING JOURNAL. Volume 12,
Number 3
Page 99: Charles D. Kennedy and Roy L. Schutzmann,
coauthors of the paper "Pesticide Residues in Estuarine
Mollusks, 1977 versus 1972 — National Pesticide Moni-
toring Program" are employed by the Ecological Moni-
toring Branch, Pesticides Monitoring Laboratory, U.S.
Environmental Protection Agency, Bay St. Louis, MS
39520.
Pages 137-148: In the paper "Pesticide Application and
Cropping Data from 37 States, 1971— National Soils
Monitoring Programs," maps for Figures 1 and 2 were
transposed.
Vol. 12, No. 4, March 1979
235
Acknow led^m etits
The Editorial Advisory Board wishes to thank the fol-
lowing persons for their valuable assistance in review-
ing papers submitted for publication in Volume 12 of
the Pesticides Monitoring Journal:
U.S. DEPARTMENT OF AGRICULTURE
Paul F. Sand
U.S. ENVIRONMENTAL PROTECTION AGENCY
Ann E. Carey
U.S. DEPARTMENT OF
AND WELFARE
Paul E. Corneliussen
Bernadette M. McMahon
George Yip
HEALTH, EDUCATION,
236
Pesticides Monitoring Journal
SUBJECT AND AUTHOR INDEXES
Volume 12, June 1978— March 1979
Primary headings in the subject index include pesticide
compounds, media in which pesticide residues are moni-
tored, and major concepts related to the monitoring of
pesticides in the environment. Pesticide compounds are
listed by common names; trade names are used for
those which have no common names.
Secondary headings cross-reference the primary head-
ings.* For a paper which discusses five or more organo-
chlorines or organophosphates the compounds are
grouped by class under media and concept headings but
Preface
each compound appears individually under the primary
headings for pesticide compounds.
In the author index all information on a paper appears
in the senior author's citations: associate authors, title
of the paper, and volume, issue, and pages where the
article was published. Names of associate authors are
cross-referenced as minor headings, but the reader is
referred to the senior author's entry for the paper's com-
plete citation.
• Note: With the exception of 12(3 ) :137-148 and 12(4) :198-208 in which no compounds are used as secondary headings. Each compound is listed
as a primary heading with application as its only secondary heading.
Vol. 12, No. 4, March 1979
237
SUBJECT INDEX
Acephate
Dcgradaiion
12(4):167-171
Food and Feed
12(4);167-171
Alachlor
Application
12(3): 137-148
12(4): 198-208
Aldicarb
Application
12(4): 198-208
Aldrin
Application
12(3): 137-148
12(4): 198-208
Crops
12(4): 209-229
Factors Influencing Residues
12(2):81-86
12(3):149-162
12(4): 185-188
Sediment
I2(2):81.86
12(2):94-95
Soil
12(3):117-136
12(4):209-229
Water
12(3):149-162
12(3):163
Wildlife
12(l):4-7
12(2):51-59
12(2):81-86
12(3):99-lfll
12(4):185-188
Amitrole
Application
12(4): 198-208
Ancrack
Application
12(4): 198-208
Application
Croplands
12(3): 137-148
12(4): 198-208
Aroclor 1248 (see also PCBs)
Factors Influencing Residues
12(l):36-39
Wildlife
12(l):36-39
Aroclor 1260
Wildlife
I2(3):113-1I6
Aromatic Amines
Factors Influencing Residues
12(3): 149-162
Water
12(3): 149-162
Arsenic
Factors Influencing Residues
12(l):4-7
Soil
12(3):117-136
Wildlife
12(l):4-7
Arsenic Pentoxide
Application
12(3): 137-148
Atrazine
Application
I2(3):I37-148
12(4); 198-208
Crops
12(3):1I7-136
12(4): 209-229
Soil
I2(3):II7-136
12(4): 209-229
Azinphosmethyl
Application
12(3):137-148
12(4): 198-208
Wildlife
12(2):51-59
12(3):99-101
B
Bacillus thuringiensis
Application
I2(3):I37-148
Barban
Application
I2(3):137-148
Benefin
Application
I2(3):I37-I48
12(4): 198-208
Benomyl
Application
12(4): 198-208
BHC/Lindane
Application
I2(3):137-148
12(4):198-208
Crops
12(4):209-229
Factors Influencing Residues
12(l):26-35
12(2):81-86
12(2):87-90
12(3):I49-I62
12(4);193-197
12(4):230-233
Food and Feed
12(2):91-93
Sediment
12(2):8l-86
12(2):94-95
Soil
12(4): 209-229
l2(4):230-233
Water
I2(3):149-162
12(3): 163
Wildlife
12(l):4-7
12(l):26-35
12(2):5l-59
12(2):8l-86
l2(2):87-90
12(3):99-ini
12(41:193-197
Bordeaux Mixture
Application
12(3):137-148
Bromacil
Application
12(3):137-148
12(4): 198-208
Soil
12(2):47-50
Bromoxynil
Application
12(4): 198-208
Butylate
Application
12(3):137-148
12(4): 198-208
Bux
Application
12(3):137-148
12(41:198-208
Cadmium
Factors Influencing Residues
12(l):4-7
Wildlife
l2(l):4-7
Captafol
Application
12(3): 137-148
12(41:198-208
Captan
Application
I2(3):137-148
12(41:198-208
Carbaryl
Application
12(3);137-I48
12(4): 198-208
Carbofuran
Application
12(3):137-I48
12(4): 198-208
Carbopbenothion
Application
12(3): 137-148
12(4): 198-208
Wildlife
12(2):51-59
12(3):99-101
Chevron RE-S353
Application
12(31:137-148
Chloramben
Application
12(31:137-148
12(4): 198-208
Chlordane
Application
I2(3):I37-I4«
12(41:198-208
Crops
I2(3):I17-136
12(4):209-229
Factors Influencing Residues
12(2):60-68
12(21:69-80
12(41:193-197
12(4):230-233
Sediment
12(2):94-95
Soil
12(3):117-136
12(4): 209-229
12(4):230-233
Wildlife
12(21:51-59
l2(2):60-68
l2(2):69-80
12(31:99-101
12(3):I13-1I6
12(41:172-184
12(41:193-197
238
Pesticides Monitoring Journal
Chlorobenzilate
Application
12(3):I37-148
12(4): 198-208
Chloroneb
Application
12(3);137-148
12(41:198-208
Chloropropbam
Application
12(3): 137-148
12(4): 198-208
Chloropropylate
Application
12(4): 198-208
Chlorothalonil
Application
12(3): 137-148
Chloroxuron
Application
12(4): 198-208
Cholinesterase Inhibitors
Factors Influencing Residues
12(31:149-162
Water
12(3): 149-162
Copper
Factors Influencing Residues
12(l):4-7
Wildlife
12(l):4-7
Copper Carbonate (basic)
Application
12(3): 137-148
12(4) : 198-208
Copper Hydroxide
Application
12(3): 137-148
Copper Oxide
Application
12(3): 137-148
Copper Sulfate
Application
12(3):137-148
Crops (see also Food and Feed
Plants (other than those used
for food and feed))
Fodder
12(3):137-148
12(4): 198-208
atrazine
12(3):117-136
12(4):209-229
organochlorines
12(3):117-I36
12(4):209-229
organophosphates
12(3):117-136
12(4): 209-229
Fruit
Grains
12(3):137-148
12(4): 198-208
12(3):137-148
12(4): 198-208
atrazine
12(3):117-136
12(4) :209-229
organochlorines
12(3):117-136
12(4)-: 209-229
organophosphates
12(3): 117-136
12(4):209-229
Nuts
12(3);I37-148
12(4): 198-208
atrazine
12(3):117-136
12(4): 209-229
organochlorines
12(3):1I7-I36
12(41:209-229
organophosphates
12(3):117-136
12(4); 209-229
Oilseeds
atrazine
I2(3):117-136
12(4): 209-229
organochlorines
12(3):117-136
12(4):209-229
organophosphates
12(3):117-136
12(4):209-229
Vegetables
12(3):137-148
12(4): 198-208
atrazine
12(3):117-136
12(4):209-229
organochlorines
12(31:117-136
12(4):209-229
organophosphates
12(3):117-136
12(4):209-229
Cyanazine
Application
12(41:198-208
Cycloate
Application
12(4): 198-208
Cypromid
Application
12(3):137-148
D
2,4.D
Application
12(3): 137-148
12(4): 198-208
Dalapon
Application
12(3): 137-148
12(4): 198-208
2,4-DB
Application
12(3): 137-148
12(4) : 198-208
DCPA
Application
I2(3):137-148
Crops
12(4): 209-229
Soil
12(4) : 209-229
DDD, see TDE
DDE
Crops
12(31:117-136
12(41:209-229
Factors Influencing Residues
12(1) :4-7
12(1):8-15
12(1):I6-21
12(l):22-25
12(l):26-35
12(2);60-68
12(2);69-80
12(2):81-86
12(3):102-112
12(3): 149-162
12(4);185-188
I2(4):i89-I92
12(4): 193-197
Food and Feed
I2(2):91-93
Sediment
12(2):81-86
12(2);94-95
Soil
12(3):117-136
12(4): 209-229
Water
12(3):149-162
12(3):163
Wildlife
12(1) :4-7
12(1):8-15
12(l):16-2!
12(l):22-25
12(11:26-35
I2(2):51-59
12(21:60-68
12(2):69-80
12(2):81-86
12(3):102-112
12(31:113-116
12(41:172-184
12(41:185-188
12(4);189-192
12(4): 193-197
DDT
Application
12(31:137-148
12(4):198-208
Crops
12(31:117-136
12(41:209-229
Degradation
12(l):l-3
Factors Influencing Residues
12(11:4-7
12(1):8-15
12(1):16-21
12(I):22-25
12(l):26-35
12(l):36-39
12(2):60-68
12(2):69-80
12(2):81-86
12(2):87-90
12(3):102-112
12(31:149-162
12(41:185-188
12(41:189-192
12(4):193-197
Food and Feed
12(11:1-3
12(2):9l-93
Sediment
12(2):81-86
12(21:94-95
Soil
12(11:1-3
12(31:117-136
12(41:209-229
Water
I2(3):149-162
12(3):163
Wildlife
12(l):4-7
12(l):8-15
12(11:16-21
l2(l):22-25
12(11:26-35
12(11:36-39
12(2):5I-59
12(2):60-68
12(2):69-80
12(2):8l-86
12(2):87-90
12(3);99-101
12(3):I02-I12
12(31:113-116
12(41:172-184
12(41:185-188
12(4):189-192
12(4);193-197
Vol. 12, No. 4, March 1979
239
DDTR
Crops
12(4): 209-229
Factors Influencing Residues
12(4):230-233
Soil
12(4): 209-229
12(4):230-233
DEF
Application
12(3): 137-148
12(4): 198-208
Crops
12(3):117-136
12(4):209-229
Soil
12(3):117-136
12(4):209-229
Wildlife
12(2):51-59
12(3):99-101
Degradation
Acephate
12(4):I67-171
DDT
12(l):l-3
Methamidophos
12(4):I67-171
Delnav
Factors Influencing Residues
12(4):185-188
WUdlife
12(4): 185-188
Demeton
Application
12(3): 137-148
Wildlife
I2(2):51-59
12(3):99-101
Diallate
Application
12(3): 137-148
Diazinon
Application
12(3): 137-148
12(4): 198-208
Crops
12(4):209-229
Factors Influencing Residues
12(4): 185-188
Soil
12(31:117-136
12(4):209-229
Wildlife
12(2):51-59
12(3):99-101
12(4):185-188
Dibromochloropropane
Application
12(4): 198-208
Dicamba
Application
12(31:137-148
12(4):198-208
Dicblofenthion
Application
12(3):137-148
Dichlone
Application
12(4): 198-208
Dichloropropenc
Application
12(31:137-148
12(4): 198-208
Dichlorprop
Application
12(3):137-I48
12(41:198-208
Dicofol
Application
12(3):137-148
12(4): 198-208
Crops
12(41:209-229
Soil
12(41:209-229
Dicrotophos
Application
12(41:198-208
Dieldrin
Application
I2(3):137-148
Crops
12(31:117-136
12(4): 209-229
Factors Influencing Residues
12(l):4-7
12(1):8-15
12(1):16-21
12(11:22-25
12(11:26-35
12(11:36-39
12(2):60-68
12(21:69-80
12(21:81-86
12(21:87-90
I2(3):102-112
12(31:149-162
12(4):185-188
12(41:189-192
12(41:193-197
12(41:230-233
Sediment
12(21:81-86
12(21:94-95
Soil
12(31:117-136
12(41:209-229
12(4): 230-233
Water
12(31:149-162
12(3):163
Wildlife
12(l):4-7
12(1):8-15
12(11:16-21
12(l):22-25
12(l):26-35
12(11:36-39
12(21:51-59
12(21:60-68
12(21:69-80
12(21:81-86
12(21:87-90
12(31:99-101
12(31:102-112
12(31:113-116
12(41:172-184
12(41:185-188
12(41:189-192
12(41:193-197
Dimethoate
Application
12(41:198-208
Dinitrocresol
Application
12(31:137-148
12(41:198-208
Dipbeiiamid
Application
12(31:137-148
12(41:198-208
Disulfolon
Application
12(31:137-148
12(41:198-208
Diuron
Application
12(31:137-148
12(41:198-208
Soil
12(21:47-50
DNBP
Application
12(31:137-148
12(41:198-208
Dodine
Application
12(31:137-148
12(41:198-208
DSMA
Application
12(31:137-148
12(41:198-208
Dursban
Factors Influencing Residues
12(41:185-188
Wildlife
12(41:185-188
Dyfonate
Application
12(31:137-148
12(41:198-208
E
EMTS
Application
12(31:137-148
12(41:198-208
Endosulfan
Application
12(3): 137-148
Crops
12(31:117-136
12(41:209-229
Factors Influencing Residues
12(21:69-80
12(31:149-162
Sediment
12(21:94-95
Soil
12(31:117-136
12(41:209-229
Water
12(31:149-162
WUdlife
12(21:51-59
12(21:69-80
12(31:99-101
Endosulfan Sulfate
Crops
12(31:117-136
12(41:209-229
Soil
12(3): 117-136
12(4):209-229
Endrin
Application
12(3): 137-148
Crops
12(31:117-136
12(41:209-229
Factors Influencing Residues
12(21:69-80
12(31:149-162
12(41:193-197
12(41:230-233
Sediment
12(21:94-95
Soil
12(31:117-136
12(41:209-229
12(41:230-233
240
Pesticides Monitoring Journal
Water
12(3): 149-162
12(3):163
Wildlife
12(l):4-7
12(2):69-80
12(3):113-116
12(4):193-197
EPN
Application
12(4): 198-208
EPTC
Application
12(3):137-148
12(4): 198-208
Ethion
Application
12(4): 198-208
Factors Influencing Residues
12(4);185-188
Sou
12(3):117-136
Wildlife
12(2):51-59
12(3):99-101
12(4):185-188
Ethoprop
Application
12(3):137-148
12(4): 198-208
Ethylmercury Chloride
Application
12(3):137-148
12(4): 198-208
Ethyl Parathion
Application
12(3);137-148
12(4): 198-208
Crops
12(3):117-136
12(4) : 209-229
Soil
12(31:117-136
12(41:209-229
Wildlife
12(2):51-59
F
Factors Influencing Residues
Age
DDE
12(1):8-15
DDT
12(1):8-15
dieldrin
12(1):8-15
mercury
12(l):26-35
organochlorines
12(l):22-25
12(l):26-35
12(4):185-188
12(4):189-192
organophosphates
12(4):185-188
PCBs
12(11:22-25
12(l):26-35
12(4); 189-192
Environmental, Geographical,
and Locational
BHC/ Lindane
12(2):87-90
DDE
12(3):102-112
DDT
12(11:36-39
12(2):87-90
12(31:102-112
dieldrin
12(l):36-39
12(21:87-90
12(3):102-112
HCB
12(2):87-90
mercury
12(11:26-35
12(11:36-39
organochlorines
12(11:22-25
12(l):26-35
12(2):60-68
12(21:69-80
12(31:149-162
12(4):193-197
organophosphates
12(31:149-162
PCBs
12(11:22-25
12(11:26-35
12(11:36-39
12(21:60-68
12(21:69-80
12(31:102-112
12(41:193-197
TDE
12(31:102-112
urea compounds
12(31:149-162
Land Use
organochlorines
12(41:230-233
PCBs
12(41:230-233
Seasonal and Temporal
organochlorines
12(21:60-68
12(21:69-80
12(41:185-188
organophosphates
12(41:185-188
PCBs
12(21:60-68
12(21:69-80
Sex
DDE
12(11:8-15
DDT
12(11:8-15
dieldrin
12(11:8-15
mercury
12(11:26-35
organochlorines
12(11:26-35
12(41:185-188
organophosphates
12(41:185-188
PCBs
12(11:26-35
Species
DDE
12(11:8-15
12(11:16-21
12(31:102-112
DDT
12(11:8-15
12(11:16-21
12(31:102-112
dieldrin
12(11:8-15
12(11:16-21
12(31:102-112
mercury
12(11:16-21
12(11:26-35
metals
12(11:4-7
mirex
12(11:40-42
organochlorines
12(11:4-7
12(11:26-35
12(21:60-68
12(21:69-80
12(21:81-86
PCBs
12(1):16-21
12(11:26-35
12(21:60-68
12(21:69-80
12(21:81-86
12(31:102-112
TDE
12(31:102-112
Weight
organochlorines
12(21:60-68
12(21:69-80
PCBs
12(21:60-68
12(21:69-80
Fenac
Application
12(41:198-208
Fenaminosulf
Application
12(41:198-208
Fensulfothion
Application
12(31:137-148
12(41:198-208
Fentin Hydroxide
Application
12(31:137-148
12(41:198-208
Ferbam
Application
12(31:137-148
Fluometuron
Application
12(31:137-148
12(41:198-208
Folex
Application
12(31:137-148
12(41:198-208
Folpet
Application
12(31:137-148
Food and Feed
Dairy Products
BHC/Lindane
12(21:91-93
DDE
12(21:91-93
DDT
12(21:91-93
TDE
12(21:91-93
Fruits
acephate
12(41:167-171
methamidophos
12(41:167-171
Grain and Fodder
DDT
12(11:1-3
Furethrin
Application
12(31:137-148
H
HCB
Application
12(31:137-148
12(41:198-208
Crops
12(41:209-229
Factors Influencing Residues
12(21:60-68
12(21:69-80
Vol. 12, No. 4, March 1979
241
Soil
12(2):87-90
12(3):149-162
12(4):185-I88
12(4): 189-192
12(4):193-197
12(4):209-229
Water
I2(3).149-162
Wildlife
12(2):60-68
12(2):69-80
12(2):«7-90
12(3):113-116
12(4):172-184
12(4):185-188
12(4):189-192
12(4): 193-197
Heptachlor
Application
12(3):137-148
12(4): 198-208
Crops
12(3):117-136
12(4):209-229
Factors Influencing Residues
12(3):149-162
12(4): 230-233
Sediment
12(2):94-95
Sou
Water
12(3):1 17-136
12(4):209-229
12(4):230-233
12(3):149-162
12(3): 163
Wildlife
12(l):4-7
12(2):51-59
12(3):99-101
Heptachlor Epoxide
Crops
12(3):117-136
12(4):209-229
Factors Influencing Residues
12(l):4-7
12(0:22-25
12(2):60-68
12(2):69-80
12(3):149-162
12(4):193-197
12(4):230-233
Sediment
12(2):94-95
Soil
12(3):117-136
12(4):209-229
12(4):230-233
Water
12(3):149-162
12(3):163
Wildlife
12(l):4-7
12(l):22-25
12(2):51-59
12(21:60-68
12(2):69-80
12(3):113-116
12(4): 172-184
12(4):193-197
Isodrin
Application
12(3):137-148
Soil
12(3): 117-136
Lead
Factors Influencing Residues
12(l):4-7
Wildlife
12(l):4-7
Lead Arsenate
Application
12(3): 137-148
12(4): 198-208
Lindane, see BHC/Lindane
Linuron
Application
12(3):137-148
12(41:198-208
Londax
Application
12(3):137-148
M
Malatliion
Application
12(3): 137-148
12(4): 198-208
Crops
12(4):209-229
Factors Influencing Residues
12(4):185-188
Soil
12(31:117-136
12(41:209-229
Wildlife
12(2):51-59
12(31:99-101
12(41:185-188
Malcic Hydrazide
Application
12(31:137-148
12(41:198-208
Mancozeb
Application
12(31:137-148
Maneb
Application
12(3): 137-148
12(41:198-208
Manganese
Factors Influencing Residues
12(11:4-7
Wildlife
12(0:4-7
MCPA
Application
12(31:137-148
12(41:198-208
MCPB
Application
12(41:198-208
Mercury
Application
12(31:137-148
12(41:198-208
Factors Influencing Residues
12(11:16-21
12(0:26-35
12(0:36-39
Wildlife
12(0:16-21
12(0:26-35
12(0:36-39
Metham
Application
12(3):137-148
Methamidoplios
Degradation
12(41:167-171
Food and Feed
12(41:167-171
Methomyl
Application
12(31:137-148
12(41:198-208
Methoxychlor
Application
12(31:137-148
12(41:198-208
Factors Influencing Residues
12(21:69-80
Sediment
I2(2):94-95
Wildlife
12(0:4-7
12(21:51-59
12(21:59-80
12(3):99-10I
Methylmercury Acetate
Application
12(31:137-148
12(41:198-208
Metliylmercury Dicyandiamide
Application
12(3):137-148
12(41:198-208
Methyl Parathion
Application
12(31:137-148
12(41:198-208
Crops
12(31:117-136
12(41:209-229
Wildlife
12(21:51-59
Methyl Trithion
Application
12(31:137-148
12(41:198-208
Metribuzin
Application
12(4): 198-208
Mevinphos
Application
12(31:137-148
12(41:198-208
Mirex
Application
12(31:137-148
12(41:198-208
Factors Influencing Residues
12(0:22-25
12(11:40-42
12(21:69-80
12(41:193-197
Sediment
12(0:40-42
Water
12(0:40-42
Wildlife
12(0:22-25
12(0:40-42
12(21:51-59
12(21:69-80
12(31:99-101
12(31:113-116
12(41:172-184
12(4): 193-197
242
Pesticides Monitoring Journal
Molinate
Application
12(4):198-208
Monocrotophos
Application
12(3):I37-148
!2(4);198-208
Monuron
Application
12(3):n7-148
MSMA
Application
12(3):n7-148
12(4):198-208
N
Nabam
Application
12(3):137-148
Naled
Application
12(4): 198-208
Naptalam
Application
12(3):
12(4):
Nitralin
Application
12(3):
12(4):
Nonachlor
Wildlife
12(3):
12(4):
Parathion
Wildlife
12(2):51-59
12(3):99-101
Norea
Application
12(4):
137-148
198-208
137-148
198-208
113-116
172-184
198-208
o
Oil Spray
Application
12(3):137-148
12(4): 198-208
Ovex
Application
12(3):137-148
Soil
12(3):117-136
Oxychlordane
Wildlife
12(3):113-116
12(4): 172- 184
Oxydemeton-methyl
Application
12(3):137-148
Oxythioquinox
Application
12(4): 198-208
Paraquat
Application
12(3):137-148
12(4): 198-208
PCBs
Crops
12(4):209-229
Factors Influencing Residues
12(1):16-21
12(l):22-25
I2(1):26-3S
12(2):60-68
!2(2):69-80
12(2):81-86
12(3):102-112
12(4):189-192
12(4):193-197
12(4):230-233
Sediment
12(2):81-86
12(2):94-95
Soil
12(4):209-229
12(4): 230-23 3
Wildlife
12(l):4-7
12(1):16-21
12(0:22-25
12(11:26-35
12(2):51-59
12(2):60-68
12(21:69-80
12(2):81-86
12(3):99-101
12(31:102-112
12(31:113-116
12(4):172-184
12(4):189-192
12(4):193-197
PCNB
Application
12(3): 137-148
12(4): 198-208
Crops
12(4):209-229
Soil
12(4):209-229
PCP
Application
12(3):137-148
12(4):198-208
Pebulate
Application
12(3):137-148
12(4):198-208
Pentachlorophenol, see PCP
Phenylmercury Acetate
Application
12(31:137-148
12(4): 198-208
Phenylmercury Urea
Application
I2(3):137-148
Phorate
Application
12(3);137-148
12(4):198-208
Crops
12(4):209-229
Soil
12(31:117-136
12(4):209-229
Wildlife
12(2):51-59
I2(3):99-!91
Pbosalone
Application
12(3):137-148
Phosphamidon
Application
12(3):137-148
Picioram
Application
1 2(4): 198-208
Plants (other than those used
for food and feed) (see also
Crops)
Cotton
12(31:137-148
12(4):198-208
atrazine
12(3):I17-136
12(41:209-229
organochlorines
12(31:117-136
12(4):209-229
organophosphates
12(3):117-136
I2(4):209-229
Tobacco
12(3):137-14S
12(4): 198-208
atrazine
12(3):117-136
12(4):209-229
organochlorines
12(31:117-136
12(4):209-229
organophosphates
12(3):117-136
12(4):209-229
Polyram
Application
12(41:198-208
Prolate
Application
12(3):U7-I48
12(4): 198-208
Prometryn
Application
12(31:137-148
12(4):I98-208
Propachlor
Application
12(3):137-148
12(4):198-208
Crops
Soil
12(4);209-229
12(31:117-136
12(4):209-229
Propanil
Application
12(3):I37-148
12(4); 198-208
Propargite
Application
12(31:137-148
12(4): 198-208
Propham
Application
12(41:198-208
Pyrazon
Application
12(3):137-148
12(41:198-208
Ronnel
Crops
Soil
12(4):209-229
12(4):209-229
Vol. 12, No. 4, March 1979
243
s
Sediment
Creeks
organochlorines
12(2):94-95
PCBs
12(2):94-95
Drainage Systems
organochlorines
I2(2):81-86
12(2):94-95
PCBs
12(2):81-86
12(2):94-95
Estuarine
mirex
12(I):40-42
Marshes
organochlorines
I2(2):94-95
PCBs
12(2):94-95
Silvex
Application
12(3):137-148
Simazine
Application
I2(3):137-148
12(4): 198-208
Sodium Chlorate
Application
12(3):137-148
12(4): 198-208
Soil
Croplands
12(3):137-148
12(4): 198-208
arsenic
12(3):1I7-136
atrazine
12(3):n7-136
12(4):209-229
bromacil
12(2):47-50
DDT
I2(l):l-3
diuron
12(2):47-50
organochlorines
12(3):117-136
1 2(4): 209-229
organophosphates
12(3):117-136
12(4):209-229
PCBs
12(4):209-229
Urban
organochlorines
12(4):230-233
PCBs
I2(4):230-233
Solan
Application
12(3):137-148
Sulfur
Application
12(3):137-148
12(4): 198-208
2,4,S.T
Application
12(3):137-148
TCA
Application
12(3): 137-148
12(4): 198-208
TCBC
Application
12(4): 198-208
TDE
Crops
12(3):117-I36
12(4):209-229
Factors Influencing Residues
12(l):4-7
I2(l):22-25
12(I):26-35
12(2):50-68
12(2):69-80
12(2):81-86
12(3):102-112
12(3):149-162
12(4):185-188
12(4): 189-192
12(4):193-197
Food and Feed
12(2):91-93
Sediment
12(2):81-86
Soil
12(3):117-136
12(4):209-229
Water
12(3): 149-162
12(3):163
Wildlife
l2(l):4-7
12(l):22-25
12(l):26-35
12(2):51-59
12{2):60-68
l2(2):69-80
l2(2):81-86
12(3):102-112
12(3):113-116
12(4):172-I84
12(4): 185-188
12(4):189-192
12(4):I93-197
TEPP
Application
I2(3):137-148
12(4): 198-208
Terbacil
Application
I2(3):137-148
1 2(4): 198-208
Terbutryn
Application
12(3):I37-148
Terrazole
Application
12(3): 137-148
Tetradifon
Application
12(3):137-I48
Thiram
Application
12(3):137-I48
l2(4):198-208
Toxaphene
Application
12(3): 137-148
12(4): 198-208
Crops
12(3):l 17-136
12(4): 209-229
Soil
12(3):117-136
l2(4):209-229
Wildlife
12(0:4-7
l2(2):51-59
I2(3):99-I01
I2(3):I13-116
12(4):I72-184
Trichlorfon
Application
12(3): 137-148
Trietazine
Application
12(3):137-148
12(4):198-208
Trifluralin
Application
12(3):137-148
12(4):198-208
Crops
1 2 (4): 209-229
Soil
12(3):1I7-136
12(4): 209-229
Wildlife
12(2):5l-59
12(3):99-101
Trithion
Factors Influencing Residues
I2(4):185-188
Wildlife
I2(4):185-188
Vernolate
Application
I2(3):I37-148
12(4): 198-208
w
Water
Drinking
organochlorines
12(3):149-I62
12(3):163
organophosphates
12(3): 149-162
urea compounds
12(3):149-162
Estuarine
mirex
12(l):40-42
Ground
organochlorines
12(3): 149-162
organophosphates
12(3): 149-162
urea compounds
12(3):149-162
Rain
organochlorines
12(3):149-162
organophosphates
I2(3):I49-162
urea compounds
12(3): 149-162
Surface
organochlorines
I2(3):149-162
organophosphates
I2(3):149-162
urea compounds
I2(3):149-162
Wildlife
Birds
DDE
I2(l):8-15
12(1):16-21
DDT
12(I):8-I5
12(1):I6-21
dieldrin
12(l):8-15
I2(1):I6-21
mercury
12(1):I6-21
12(l):26-35
244
Pesticides Monitoring Journal
metals
12(l):4-7
organochlorines
12(l):4-7
12(l):22-25
12(l):26-35
12(2):8I-86
12(4):I72-184
12(4):19J-I97
PCBs
12fl):4-7
12(1):16-21
12(l):22-25
12(l):26-35
12(2):81-86
12(4):172-184
12(4);193-197
Fish
DDE
12(3);102-n2
DDT
12(0:36-39
12(3):102-112
dieldrin
12<l);36-39
12(3):102-112
mercury
12(l):36-39
mirex
12(l):40-42
organochlorines
12(2):51-59
12(2):60-68
12(2):69-80
12(2):81-86
organophosphates
12(2):51-59
PCBs
12(l):36-39
12(2):51-59
12(2):60-68
12(2):69-80
12(2):81-86
12(3):102-I12
TDE
12(3):102-112
Invertebrates
mirex
12(l):40-42
Mammals
organochlorines
12(3):113-1I6
12(4);185-188
12(4): 189-192
organophosphates
12(4):185-188
PCBs
12(3):113-116
12(4):189-I92
MoUusks
BHC/Lindane
12(2):87-90
DDE
12(3):102-112
DDT
12(21:87-90
12(3):I02-112
dieldrin
12(2):87-90
12(3):102-112
HCB
12(2):87-90
mirex
:2(1):4(M2
organochlorines
12(3):99-101
organophosphates
12(31:99-101
PCBs
I2(3):99-101
12(3); 102-1 12
TDE
12(3):102-112
Plankton
mirex
12(l):40-42
Zinc
Factors Influencing Residues
12(11:4-7
Wildlife
12(l):4-7
Zineb
Application
I2(3):137-148
Vol. 12, No. 4, March 1979
245
AUTHOR INDEX
Ahcl. Marijan, sec Piccr. Mladcn
Ammann. Barbara D., see Grcichus, Yvonne A.
B
Baker, B. E.. see Rosewcll. K. T.
Bcnoit. Frank M.. sec Williams. David T.
Blus, Lawience J.. I.amoni, Thair (»., and Neely, Burketi S., Jr.
Effects of organochlorine residues on eggshell thickness, repro-
duction, and population status of brown pelicans (Pelecanus
nccidenuilis) in South Carolina and Florida, 1969-76. 12(4) : 172-184
Braun. Heinz E., see Frank. Richard
Buck. Nt^rman A., see Ware, George W.
Butler. Philip A., and Schutzmann, Ro.v L. Residues of pesticides
and PCBs in estiiarine fish. 1972-76 — National Pesticide Monitor-
ing Program. 12(2):51-59
Butler. Philip A.. Kennedy, Charles D., and Schutzmann, Roy L.
Pesticide residues in estuarine mollusks, 1977 versus 1972 — Na-
tional Pesticide Monitoring Program, I2(3);99-101
Gowen. Jeanne A., see Carey. Ann E.
Gieichus. Yvonne A.. Gucck. Brian D.. and Ammann. Barbara D.
Organochlorine insecticide, polychlorinatcd biphenyl, and metal
residues in some South Dakota birds. 1975-76. 12(1) :4-7
Greve. Peter A., see Wegman. Ronald C. C.
Gueck. Brian D.. see Greichus. Yvonne A.
H
Hattula. Marja-Liisa. see Sarkka. Jukka
Hildebrand. Henry H.. sec King. Kirke A.
Holdrinct. Michcline. see Frank, Richard
Hughes, Donald 1... see McLane, M. Anne R.
Janatuinen, Jorma, see Sarkka, Jukka
Johnson, Teiko M., see Zabik, Mary E.
Johnston, David W. Organochlorine pesticide residues in Florida birds
of prey, 1969-76. I2(l):8-I5
Cahill, William P., see Ware, George W.
Carey, Ann E.. and Gowen, Jeanne A. Pesticide application and
cropping data from 37 states. 1972— National Soils Monitoring
Program. 12(4) : 198-208
Carey. Ann E.. Gowen, Jeanne A.. Tai, Han, Mitchell, William G.,
and Wiersma, G. Bruce. Pesticide residue levels in soils and
crops, 1971 — National Soils Monitoring Program (HI). 12(3):
117-136
Carey. Ann E., Gowen. Jeanne A., Tai, Han, Mitchell. William G.,
and Wiersma. G. Bruce. Pesticide residue levels in soils and
crops from 37 states. 1972 — National Soils Monitoring Program
(IV). 12(4):209-229
Carey. Ann E.. Gowen. Jeanne A., and Wiersma. G. Bruce. Pesticide
application and cropping data from 37 states. 1971 — National Soils
Monitoring Program. 12(3): 137-148
Clark. Donald R.. Jr.. and Krynitsky. Alex. Organochlorine residues
and reproduction in the little brown bat. Laurel, Maryland —
June 1976. 12(3):1 13-1 16
Clark, Eldon R., see McLane, M. Anne R.
D
de la Cruz. Armando A., and Lue, Kiiang ^'ang. Mirex incorporation
in estuaiine animals, sediment, and water. Mississippi gulf coast —
1972-74. 12(1):4()^2
Dhaliwai. G. S.. and Kalra. R. L. DDT residues in butter and
infani formula in India. 1977. 12(2):91-93
Djirsarai. R.. see Sodergren, A.
Dodge, Douglas P.. see Frank, Richard
Dustman. Eugene H.. see McLane. M. Anne R.
K
Kalra. R. L.. see Dhaliwai. G. S.
Kennedy. Charles D.. see Builer, Philip A.
Kinn. Kiike A., Flickinger. Edward L., and Hildebrand, Henry H.
Shell thinning and pesticide residues in Texas aquatic bird eggs,
1970. 12(1): 16-21
Krynitsky, Alex, see Clark. Donald R.. Jr.
Lamont. Thair G., see Blus, Lawrence J.
Lang. Jerry T.. Rodriguez, Leopoldo L., and Livingston, James M.
Organochlorine pesticide residues in soils from six U.S. Air Force
bases. 1975-76. 12(4)230-233
Livingston. James M., see Lang, Jerry T.
Lue. Kuang \ ang, sec de la Cruz, Armando A.
M
McLane. M. Anne R.. Dustman. Eugene H., Clark. Eldon R., and
Hughes. Donald L. Organochlorine insecticide and polychlori-
natcd biphenyl residues in woodcock wings. 1971-72. 12(l):22-25
McNeil. Edward E.. see Williams. David T.
Mitchell. William G.. see Carey. Ann E.
Moinpour. A., see Soiicigren, A.
Muir, D. C. G., see Rosewell. K. T.
N
Estesen, Betty J., see Ware, George W.
Neely, Burkett S., Jr., see Blus. Lawrence J.
Nepszy, Stephen J., see Frank. Richard
Nigg, H. N.. Rcinert, James A., and Fitzpatrick, G, E. Acephate and
mcthamidophos residue behavior in Florida citrus, 1976. 12(4):
167-171
Fitzpatrick, G. E., see Nigg, H. N.
Flickinger, Edward L., see King, Kirke A.
Frank. Richard. Braun, Heinz E,, lloldrinet, Micheline, Dodge,
Douglas P., and Nepszy, Stephen J. Residues of organochlorine
insecticides and polychlorinatcd biphenyls in fish from Lakes
Saini Clair and Erie, Canada— 1968-76. 12(2):69-80
Frank, Richard, Holdrinet, Micheline. Braun, Heinz E., Dodge.
Douglas P., and Sprangler, George E. Residues of organochlorine
insecticides and polychlorinatcd biphenyls in fish from Lakes
Huron and Superior. Canada— 1968-76. 12(2):60-68
o
Olscn. Penny, and Settle. Hariy. Pesticide contamination of water
rats in the Murrumbidgee irrigation areas. New South Wales.
Australia. 12(4 ) : IS5-18S
Olson. Barbara, sec Zabik. Mary E.
Olson. Rein, sec Williams, David T.
G
Gharib/adeh. M.. see Stidergrcn, A.
Glooschcnko, W. A., and Sampson, R. C. J. Organochlorine pesti-
cides and polychlorinatcd biphenyls on sediments from a subarctic
salt marsh, James Bay. Canada— 1976. 12(2);94-95
Paasivirta. Jaakko. see Sarkka, Jukka
Palokangas. Risto. sec Sarkka. Jukka
Piccr. Mladen. Picer. Ncna. and Ahcl. Marijan. Chlorinated insecti-
cide and PCB residues in tish and mussels of east coastal waters
of the middle and north Adriatic Sea, 1974^75. 12(3) : 102-1 12
Piccr, Ncna. sec Piccr, Mladen
246
Pesticides Monitoring Journal
Reinert, James A., see Nigg, H. N.
Rodriguez, Leopoldo L., see Lang. Jerry T.
Rosewell, K. T., Miiir. D. C. G.. and Baker. B. E. Organochlorine
residues in harp seal (Phagophilus groenlamlicus) tissues, Gulf
of St. Lawrence. 1971, 1973. 12(4) :189-192
Sampson. R. C. J., see Glooschenko, W. A.
Sarkka, Jukka. Hattula. Marja-Liisa. Janatuinen. Jorma, Paasivirta,
Jaakko, and Palokangas. Risto. Chlorinated hydrocarbons and
mercury in birds in Lake Paijanne, Finland — 1972-74. 12(1):
26-35
Schutzmann. Roy L. see Butler. Philip A.
Settle. Harry, see Olsen, Penny
Sbdergren, A.. Djirsarai. R.. Gharibzadeh. M., and Moinpour, A.
Organochlorine residues in aquatic environments in Iran. 1974.
12(2):8I-86
Sprangler. George E., see Frank, Richard
Sumner. Colin Edward. Chlorinated hydrocarbon pesticide residues in
Pacific oysters (Crassostrea gigas) from Tasmania, Australia —
1973. 12(2):87-90
Tai. Han, see Carey. Ann E.
Tucker, David P. H. Bromacil and diuron residue levels in Florida
citrus soils. 12(2):47-50
w
Ware, George W., Estesen, Betty J., Buck, Norman A., and Cahill,
William P. DDT moratorium in Arizona — agricultural residues
after seven years. 12(l);I-3
Wegman, Ronald C. C, and Greve, Peter A. Organochlorines, cholin-
esterase inhibitors, and aromatic amines in Dutch water samples,
September 1969-Decembcr 1975, 12(3) : 149-162
White, Donald H. Nationwide residues of organochlorines in starlings
(Snirinis vulgarisl, 1976. 12(4) : 193-197
Wiersma, G. Bruce, see Carey, Ann E.
Williams, David T., Benoil, Frank M., McNeil, Edward E., and
Otson, Rein. Organochlorine pesticide levels in Ottawa drinking
water, 1976. 12(3):163
Zabik, Mary E., Olson, Barbara, and Johnson, Tciko M. Dieldrin,
DDT, PCBs, and mercury levels in freshwater mullet from the
upper Great Lakes, 12(l):36-39
Vol. 12, No. 4, March 1979
247
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 pesticide 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
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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
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