ENVIRONMENTAL
CHEMICALS
HUMAN & ANIMAL HEALTH
PROCEEDINGS
4th Annual Conference
1975
-------
ENVIRONMENTAL CHEMICALS
HUMAN AND ANIMAL HEALTH
Proceedings of 4th Annual Conference
Sponsored by
Colorado State University
College of Veterinary Medicine
and Biomedical Sciences
Institute of Rural Environmental Health
and
Division of Pesticides Programs
Environmental Protection Agency
Edited by Eldon P. Savage
Held at
Colorado State University
Fort Collins, Colorado
July 7-11, 1975
-------
CONTENTS
Page
Contents i
Preface iv
Conference Participants vi
Methyl Bromide Poisoning
E. Edsel Moore 1
Tetrachlorodibenzodioxin (TCDD) Plus Waste Motor Oil Equals
Disaster
A. A. Case, D.V.M 5
Vinyl Chloride Monomer: A Literature Condensation
Helen S. Warren and James Edward Huff 11
Differential Pulse Polarographic Determination of Some
Carcinogenic Nitrosamines
Kiyoshi Hasebe and Janet Osteryoung 33
The Pesticide Reporting System
Dan W. Bench 55
Field Studies for Characterization of Acute Pesticide Poisonings
Eldon P. Savage 57
Survey of Chemical Spills in Highway and Rail Transport
Edward M. Svetich 69
Arsenic: Potential Hazards of Environmental Exposure
Anna S. Hammons, Eric B. Lewis, Helen M. Braunstein and
James Edward Huff 75
Chronic Toxicity of Hexachlorobenzene in Rats: A Preliminary
Study
R. L. Younger, James H. Johnson, Donald E. Clark and
Hilton H. Mollenhauer 95
Environmental Exposure to Pesticides in Utah
Stephen L. Warnick and J. Wanless Southwick 101
Analysis of Acute Pesticide Poisonings for 1970-74
C. W. Miller 109
Recycling Pesticide Containers
Paul E. Huber 117
-------
Page
Regulation of Pesticide Storage and Disposal
Raymond F. Krueger 121
Air Sampling for Pesticides
David L. Spencer 125
Persistence of Termiticides in Soil
Virgil K. Smith 127
Polychlorinated Biphenyls - Residues in Sewage Treatment Plants
and Their Incidence in a River Ecosystem
Richard E. Johnson 131
EPA's Ambient Pesticide Monitoring Programs - An Overview
Ann E. Carey 133
Monitoring of Agriculture Insecticides into the Cooperative Cotton
Pest Management Program in Arizona, 1971
H. Richardson 139
Monitoring of Agriculture Pesticides in a Cooperative Pest
Management Project in North Carolina, 1971, First Year of Study
D. W. Woodham, M. C. Ganyard, C. A. Bond and R. G. Reeves . . 167
Environmental Effects Monitoring of Insecticides Used in Forest
Insect Suppression Programs
Roger E. Sandquist 185
Pesticide Use in Forest Pest Management Programs - Suppression
Alternatives
Frederick W. Honing 191
Photochemical Confirmation of Pesticides
Robert C. Hanisch and R. G. Lewis 193
An Industrial Hygiene Look at the Plastics Industry
Bobby J. Gunter 201
Pulse Polarographic Analysis for Some Auxin Herbicides
Jeffrey Whittaker and Jdnet Oateryoung 203
Fate of Pesticides in the Environment
Dallas C. Miller 217
Acute Pesticide Poisonings
John D. Tessari 221
Pesticide Usage Study
John W. Kliewer 223
Applicator Certification
David J. Combs 225
ii
-------
Page
The Certification of Pesticide Applicators and Opportunity for
Training
Gerald T. Weekman .
Monitoring of Selected Ecological Components of the Environment in
Four Alabama Counties (1972-1974) ..........
John Elliott ......................... 233
Design for Plenum Housing Study
Thomas M. Conway ....................... 281
Statistical Design for a National Study to Determine Levels of
Chlorinated Hydrocarbon Insecticides in Human Milk
E. G. Johnson and T. J. Keefe ................ 287
iii
-------
iv
-------
Preface
The Fourth Annual Conference on Environmental Chemicals: Human
and Animal Health was held on the campus of Colorado State University
during the week of July 7-11, 1975.
The purpose of/ this Conference is to explore the environmental,
ecological, human and animal health effects of environmental chemicals.
Over 100 people representing 29 states and Canada attended the 1973
Conference.
I wish to express our sincere appreciation to fellow staff members
of Colorado State University and the Environmental Protection Agency for
assistance in the program.
E. P. Savage
Editor
-------
vi
-------
CONFERENCE PARTICIPANTS
Andreassen, David C., Pesticide Accident Officer, Environmental Protection
Agency, Pesticides Branch, Room 907, 26 Federal Plaza, New York,
New York 10007
Beaulieu, Andrew J., Bureau of Veterinary Medicine, Food and Drug Administra-
tion, 5600 Fishers Lane, HFV-430, Rockville, Maryland 20852
Bench, Dan W., Pesticide Disposal Coordinator, Air and Hazardous Materials
Division, Environmental Protection Agency, Region VIII, 1860 Lincoln
Street, Denver, Colorado 80203
Bixby, Bill, Environmental Protection Agency, Consumer Safety Officer,
517 Gold Avenue, Room 1005, Albuquerque, New Mexico 87101
Bond, C. A., U.S.D.A. National Monitoring Lab, Route 1, Box 214,
Gulfport, Mississippi 39501
Carey, Ann E., Project Officer, National Soils Monitoring Program (WH-569),
Environmental Protection Agency, Washington, D.C. 20460
Case, Arthur A., M.S., D.V.M., Professor of Veterinary Medicine and Surgery,
University of Missouri, Columbia, Missouri 65201
Collette, James R., Environmental Health Representative, Northeast Colorado
Health Department, Court House, Akron, Colorado 80720
Combs, David J., State Program Manager, State Assistance Section, Air and
Hazardous Materials Division, Environmental Protection Agency, Region
VIII, 1860 Lincoln Street, Denver, Colorado 80203
Coon, M. J., Professor and Chairman, Department of Biological Chemistry,
University of Michigan Medical School, Ann Arbor, Michigan 48104
Corey, Dr. Beverly Fay, Veterinary Medical Officer, Bureau of Veterinary
Medicine, Food and Drug Administration, HFV-330, 5600 Fisher Lane,
Rockville, Maryland 20852
Covert, Kendall N., Consumer Safety Officer, Environmental Protection Agency,
654 Federal Building, 511 Northwest Broadway, Portland, Oregon 97209
Elder, Dr. James, U.S. Fish and Wildlife, Federal Building, Twin Cities,
Minnesota 55111
Elliott, John, Specialist in Pesticide Education, Cooperative Extension
Service, Auburn University, United States Department of Agriculture,
Auburn, Alabama 36830
Frandsen, Lyn, Consumer Safety Officer, Environmental Protection Agency,
1200 Sixth Avenue, Seattle, Washington 98101
vii
-------
Frier, Victor, Jr., Accident Prevention Coordinator, Federal Aviation
Administration, Rocky Mountain Region, 10455 East 25th Avenue,
Aurora, Colorado 80010
Gibson, J. W., Supervisor of Environmental Programs, Oklahoma Department
of Agriculture, 122 Capitol Building, Oklahoma City, Oklahoma 73105'"
Gill, Jeanne A., Agronomist, Ecological Monitoring Branch, WH-569, Environ-
mental Protection Agency, Washington, D.C. 20460
Gore, W. R., Sanitarian, State of California, 806 South Main, Yreka,
California 96097
Greiner, Gregory Paul, Maintenance Supervisor, Marine World/Africa USA,
Marine World Parkway, Redwood City, California 94065
Gunter, Bobby J., Ph.D., Regional Industrial Hygienist, National Institute
for Occupational Safety and Health, Department of Health, Education
and Welfare, 11023 Federal Building, Denver, Colorado 80202
Hammons, Anna S., Biomedical Sciences Section, Information Center Complex,
Information Division, Oak Ridge National Laboratory, Union Carbide
Corporation, P.O. Box X, Oak Ridge, Tennessee 37830
Hanisch, Robert C., National Environmental Research Center, Environmental
Protection Agency, Research Triangle Park, North Carolina 27711
Hawes, Ralph, Research Engineer, Rockwell International, Rocky Flats
Division, P.O. Box 464, Golden, Colorado 80401
Herring, Kenneth, SMSgt., NCOIC, Occupational Health, Environmental Health
Branch, United States Air Force School of Aerospace Medicine, Brooks
Air Force Base, Texas 78235
Honing, Frederick W., Assistant Director of Forest Insect and Disease Manage-
ment, Forest Service, United States Department of Agriculture,
Washington, D. C. 20250
Huff, James E., Ph.D., Associate Director, Toxicology, Information Systems
Office, Oak Ridge National Laboratory, Oak Ridge, Tennessee.
Huber, Paul E., Balcom Chemicals, Inc., P.O. Box 667, Greeley, Colorado 80631
Hughes, Daniel M., Agricultural Extension, Route 1, Box H-4, DeRidder,
Louisiana 70634
Iwagoshi, Stanley, Environmental Health Representative, Northeast Colorado
Health Department, 610 Colorado Avenue, #9, Brush, Colorado 80723
Jagger, Herbert F., Director of Environmental Health, Northeast Colorado
Health Department, 700 Columbine, Sterling, Colorado 80751
Johnsen, Richard E., Ph.D., Associate Professor, Pesticide Research Laboratory,
Department of Zoology and Entomology, Colorado State University, Fort
Collins, Colorado 80523
viii
-------
Keefe, Thomas, Ph.D., Assistant Professor, Department of Statistics, Colorado
State University, Fort Collins, Colorado 80523
Kiesler, Hans, Inspector, Environmental Protection Agency, 100 California
Street, San Francisco, California 94111
Kliewer, John W., Ph.D., Field Studies Coordinator, Epidemiologic Pesticide
Studies Center, Medical University of South Carolina, Charleston,
South Carolina 29401
Krueger, Ray, Office of Pesticides Programs, Operations Division (WH-576),
Environmental Protection Agency, Washington, D.C. 20460
Lund, John L., Sr., CMS, School of Aerospace Medicine, Brooks Air Force Base,
San Antonio, Texas 78235
McClain, Carroll, Chief Sanitarian, Galveston County Health District,
P.O. Box 939, La Marque, Texas 77568
McDonald, Victor, Federal Aviation Administration, Rocky Mountain Region,
10455 East 25th Avenue, Aurora, Colorado 80010
Miller, Charles W., EPA Project Officer, Environmental Protection Agency,
Region VIII, Epidemiologic Pesticide Studies Center, Colorado State
University, Spruce Hall, Fort Collins, CO 80523
Miller, Dallas E., State Program Manager, State Assistance Section, Air and
Hazardous Materials Division, United States Environmental Protection
Agency, Region VIII, 1860 Lincoln Street, Denver, Colorado 80203
Minyard, William B., Registered Sanitarian, State of Arkansas, Department of
Health, 434 South Cokley, Lake Village, Arkansas 71653
Moore, E. Edsel, Director, Pesticides Program, Division of Environmental
Services, Kentucky Department for Human Resources, Frankfort, Kentucky
40601
Mullins, Elmer H., Chemist, Arizona Department of Health Services, State
Laboratory, 1716 West Adams, Phoenix, Arizona 85007
Nordstrom, Ken, Sanitarian, Weld County Health Department, 1516 Hospital
Road, Greeley, Colorado 80631
Osteryoung, Janet G., Ph.D., Associate Professor, Institute of Rural
Environmental Health, Departments of Microbiology and Civil Engineering,
Colorado State University, Fort Collins, Colorado 80523
Richardson, H., Plant Protection and Quarantine Programs, United States
Department of Agriculture, Brownsville, Texas 78520
Ricotta, Sylvia A., Chemist, Food and Drug Administration, 500 New Custom
House, Denver, Colorado 80202
Sandquis.t, Roger E., Entomologist, Forest Service, United States Department
of Agriculture, Washington, D.C. 20250
ix
-------
Smith, Virgil K., Principal Entomologist, Southern Forest Experiment Station,
Forest Service, United States Department of Agriculture, P.O. Box 2008,
Evergreen Station, Gulfport, Mississippi 39501
Southwick, J.W., Ph.D., Project Director, Utah Community Study on Pesticides,
State of Utah, Department of Social Services, Division of Health, 44
Medical Drive, Salt Lake City, Utah 84113
Stow, Ron, Sanitarian, Weld County Health Department, 1516 Hospital Road.,
Greeley, Colorado 80631
Stevenson, Bill, Ph.D., Assistant Branch Chief, Human Effects Monitoring
Branch, Office of Pesticides Programs, Environmental Protection Agency,
Washington, D.C. 20460
Svetich, Edward M., Environmental Specialist, Scott County Health Department,
Davenport, Iowa 52801
Talcott, Raymond J., Atomics International, Rocky Flats Division, P.O. Box 888,
Golden, Colorado 80401
Thomas, William, Pesticides Staff Specialist, United States Fish and Wildlife,
17 Executive Park Drive Northeast, Atlanta, Georgia 30329
Triolo, Andrew D., Agronomist, Air and Hazardous Materials Division,
Pesticides Branch, Environmental Protection Agency, Region I, J.F.K.
Federal Building, Boston, Massachusetts 02203
Underwood, Joseph C., Food and Drug Administration, Tenth and Cherry, Kansas
City, Missouri 64106
Warnick, Stephen L.,Ph.D., Chief of Toxicology, Intermountain Laboratories,
Inc., 166 East 5900 South, Salt Lake City, Utah 84107
Warren, Helen S., Biomedical Sciences Section, Information Center Complex,
Information Division, Oak Ridge National Laboratory, Oak Ridge,
Tennessee 37830
Weber, Phyllis, Environmental Investigator (Pesticides), Surveillance and
Analysis Division, Pesticides Section, Environmental Protection Agency,
100 California Street, San Francisco, California 94122
Weekman, Gerald T., Extension Specialist In Charge, Department of Entomology,
North Carolina State University, Raleigh, North Carolina 27607
Younger, R.L., D.V.M., Veterinary Medical Officer, Veterinary Toxicology and
Entomology Research Laboratory, Southern Region, Agricultural Research
Service, United States Department of Agriculture, P.O. Drawer GE,
College Station, Texas 77840
Yoder, Franklin, Director, Weld County Health Department, 1516 Hospital Road,
Greeley, Colorado 80631
-------
Colorado Epidemiologic Pesticide Studies Center, Institute of Rural
Environmental Health, Spruce Hall, Colorado State University,
Fort Collins, Colorado 80523
Dr. Eldon P. Savage
Dr. Charles W. Miller
Sebina Hobson - Secretary
Betsy Alt T ^ „ .,
„ , , n , Loretta Munsell
Fred Applehans ., „ ,
Trj j • ™ Gary Norwood
Virginia Boyes B ' < ,
TW „„„ „, „£„„ Bil1 Pemberton
Dr. Roy Bucnan T „ ,
_ „ _, , Jerry Rench
Dr. Gus Cholas ., . J „ , .
T , _ - Craig Sandstrom
John Conley _. .T _
_ _ ' David Spencer
Tom Conway T^
Linda Davis John Tessari
Sandra Ford . . , _, . ,
Anthony Toth
^ Lorene Webber
Jane Gordon ^^ Westbrook
Gary Mihlan mi
Ted Mohr Dr>
Lawrence Mounce
xi
-------
xii
-------
METHYL BROMIDE POISONING
E. Edsel Moore
Kentucky Department for Human Resources
On February 16, 1975, three members of a rural Southeastern Kentucky
family awakened with symptoms of nausea, vomiting, weakness, and extreme
dizziness. Later in the day a 6 year old male was admitted to the Uni-
versity of Kentucky Medical Center in a comatose condition responding only
to deep pain.
On February 17, 1975, the forty-two year old grandparents of the
above child were admitted to the University of Kentucky Medical Center,
The grandmother was actively convulsing at the time of admission, and the
grandfather was lethargic with an unsteady broad-based gait and dysarthria.
On February 19, 1975, an epidemiological investigation was conducted.
It was determined that on the preceding Friday that the 6 year old child
was taken to the family physician and received an injection of Penicillin
for a sore throat condition. On February 15 the 6 year old was again
taken to the family physician for sore throat and received another in-
jection of pesnicillin. On February 16th the child appeared to be much worse
experiencing severe nausea and vomiting. In the A.M. hours the child was
again seen by the family physician and received a third penicillin injection
and although not feeling very well, the physician did not suspect there
was anything seriously wrong and the child returned home. In the after-
noon the child became listless and had spastic movements on the right side
of his body but was not experiencing a full blown seizure. The child was
again taken to the family physician and was referred to the University of
Kentucky Medical Center with a tentative diagnosis of meningitis. The
child was transported to the emergency room by the grandparents. Since
the child was comatose and responding only to deep pain, he was immediately
admitted to the Pediatric Ward. The grandfather submitted himself to the
emergency room complaining of nausea, and vomiting. The grandmother
complained of the same but did not submit herself to the emergency room.
Subsequently, the grandfather was sent home without further observation or
treatment.
The following day the child continued to alternate from deep stupor
to delirium. Upon arising on the morning of the 17th, the grandparents
experienced severe dizziness with continued nausea and vomiting. The
grandfather could not locate the phone number of the life squad and since
his wife was very ill he decided to take her to the family physician. As
they proceeded to the family vehicle they fell in the yard before reaching
it. (It is thought that at this time his wife began her seizures). The
grandfather had great difficulty in driving the vehicle because of
dizziness and he fell on the floor upon entering the physician's office.
The grandmother was also experiencing seizures at the time the private
physician saw her. The grandparents were advised to return home and
prepare to go to the University of Kentucky Medical Center for medical
attention. Since their condition continued to deteriorate on the return
trip home, an ambulance was summoned to transport the grandparents to
the medical center. The grandmother was admitted with status epilepticus
and the grandfather was admitted with listlessness, wide-staggering gait,
and slurred speech.
-------
Diagnostic tests were being made by the University of Kentucky
Medical Center Laboratory to determine the cause of the child's delirium
and deep stupor. During this period, it was determined that he had a
liver enlargement and a diagnosis of Reye's Syndrome was entertained.
The drugs being administered to the grandmother were only effective
in controlling the seizures for a few moments at most. Her tentative
clinical diagnosis was an attack of viral encephalitis. The full blown
seizures continued with an alarming frequency, meanwhile the grandfather
became more alert and orientated although he continued to have slurring
of speech and ataxia. All three were placed under the care of a
neurologist. The neurologist in charge of the case contacted the Depart-
ment for Human Resources for assistance as he had not observed a similar
syndrome as exhibited by the three patients. The condition of all three
family members remained clinically unchanged during the 19th. A depart-
ment epidemiologist conducted an interview with the grandfather on the
proceeding evening in an effort to determine any events or unusual ex-
periences that might allude to the symptoms experienced by the victims
as those observed fit no distinct pattern that was recognizable to the
attending physician. During the course of the interview, all facts and
information related by the grandfather appeared to be normal and routine
with the exception of the purchase and storage of methyl bromide as, a
serious neurotoxin that is extensively used as a soil sterilant in the
preparation of tobacco plant beds.
During the afternoon of February 19, two human resources staff members
trekked to the farm family homestead to determine what circumstances with
the "methyl bromide may have precipitated the family's illness. A
thorough search of the home did not reveal anything dramatic or extra-
ordinary. Members of the local health department accompanied the in-
vestigators and learned from other family members that the affected
family had on Friday afternoon purchased 2 cases of methyl bromide gas
consisting of 24 one pound cans and had stored them in the back part
of the home near the bedrooms just prior to the grandfather departing
on a hunting trip that was scheduled to last most of the night. Relatives
of the affected family suspected that the methyl bromide may have caused
the victims' illness and had removed the methyl bromide from the house
to an outside shed previous to the investigation. The domicle had been
aired completely after the victims were transported to the medical
facilities in Lexington. Examination of the two cases of methyl bromide
revealed that 11 of the 48 cans were lightweight. A field demonstration
of submerging two of the lightweight cans in a container of hot tap water
revealed that gas was escaping from the cans. Methyl bromide boils at
40 degrees Fahrenheit and at room temperature the leaking gas was escaping
from around the seals on top of the can. The outside temperature at the
time of the demonstration was 30 degrees Fahrenheit.
The cans also contained 2% chloropicrin (tear gas) to warn users of
escaping gas as methyl bromide is colorless and odorless and in a closed
environment would normally cause tearing of the eyes and difficulty in
breathing.
-------
This finding resulted in a visit of the establishment from which
the leaking containers were purchased. A similar demonstration resulted
in the detection of leaking containers that were stored in the retail
sales area of the establishment. Subsequently, the proprietor of the
establishment contacted all recent purchasers of methyl bromide and
advised them of leaking containers and to store them in an outside well
ventilated area.
As a result of the field investigation, the Environmental Protection
Agency was alerted and a national search for leaking containers was
initiated in other states. The news media in Kentucky was alerted to the
problem and responded by advising the farm community of proper storage
practices. Subsequent actions by the Environmental Protection Agency
resulted in stop order sales and interstate movement of PSethyl bromide
that was produced by the manufacturer in question. Officials of the
Environmental Protection Agency reported that in an 8 state tobacco-
growing area that from 5 to 10 percent of the cans remaining in inventory
at the distributor and retail level were found to be lightweight or
completely empty. On February 20 the grandfather experienced a psychotic
break, and was placed in the psychiatric ward and a therapy of Thorazine
was begun where slow response ensued. The grandfather was discharged
from the hospital on March 4, 1975. He was to return to the psychiatric
clinic in one week, but failed to do so. The six year old grandchild's
clinical condition gradually improved but at times responded inappropri"-
ately. He was discharged on March 9, 1975 although reportedly not fully
recovered. Attending physicians felt that a more rapid recovery would
ensue in more familiar surroundings and environment.
The grandmother's progress was very slow and she experienced full
blown seizures for 6 days. On February 25, 1975 she developed bilateral
pneumonia. A tracheotomy was installed and she was placed in an oxygen
tent in critical condition. She began to respond gradually and was
discharged on March 20, 1975.
On May 2, 1975 she was seen in the neurology clinic where she stated
she felt better and able to think more clearly and able to walk inde-
pendently, although moderately ataxic. She continued to experience
myoclonic jerking of limbs but much less pronounced than previously.
Tests for the presence of methyl alcohol and bromide performed by
the Human Resources chemistry laboratory on the patient's blood were in-
conclusive. This may be because the supply of initial blood drawn at
the time of admission was exhausted in attempting to determine the
causitive agent in the poisoning episode. It is not clear when the
samples were drawn that were analyzed for the presence of the aforementioned
compounds, however, the time factor ranges between 24 and 72 hours. This
time period may have allowed the systems to metabolize post exposure r
residues in the victims' bodies.
-------
-------
TETRACHLORODIBENZODIOXIN (TCDD) PLUS WASTE MOTOR
OIL EQUALS DISASTER
A. A. Case, D. V. M.
University of Missouri
The title for our present discussion was not lifted from a news-
paper or television announcement but concerns the complex and deadly
sequence of events which followed the use of discarded motor oil to
settle the dust and kill insects inside two large horse riding arenas,
an open riding track, and some other areas which were not directly
connected with the horse industry (1).
Several reports over the period from the original warning by
Case (1) in 1971 to the latest in Science by Center for Disease Control
(CDC) workers (2,3,4,5) have summarized the potential hazards of care-
less and irresponsible disposal of such supertoxic substances as tetra-
chlorodibenzodioxin (TCDD) into channels where, by ignorance or otherwise,
the environment of man and animals may be contaminated. This very type
of incident was discussed in considerable detail by Huff and Wassom of
Oak Ridge in their paper delivered at the second conference here in July,
1973 (6). Both the Oak Ridge and CDC workers have described in consider-
able detail the history, chemistry, toxicological aspects, and environ-
mental considerations of a number of the highly chlorinated dioxins and
furans. The interested reader is referred to these (2,3,4,5,6). Kimbrough
as well as others have published a series of papers on chlorinated com-
pounds and problems with toxic substances which may contaminate such (2,4,
5,6,7). Case and Coffman (8) and Case (9) have described the clinical
toxic syndromes in horses and other animals involved in this incident
series; our observations support in general those published by others.
It seems easy to "second guess" persons involved in such "accidents"
as the one described here, but the toxic potential and extent of contami-
nation was not realized by the owners of the horses and others until it
was too late to prevent exposure of persons and animals to the supertoxic
substances which were present.
It was the attending veterinarian who was called to treat one of
the first horses to be affected in the first enclosed arena that was
aware of a toxic agent being present; because of the noxious and very
irritating, pungent fumes, he told the owners to clear the horses from
the arena and adjacent boarding stable and to stay out until the fumes
cleared. His warning went largely unheeded by those who were to suffer
most from exposure to the TCDD, which was later proved to be present in
a concentration of about 32 parts per million (PPM) (2,5). The many
persons that visited the other places treated with the waste oil contam-
inated with the TCDD industrial waste, including the author, can comment
on the very irritating nature of the fumes and the pungent odor which
was easily detected at considerable distances from the arenas (1,2,5^9,11).
The pungent odor and apparent high volatile characteristics at ordinary
summer temperatures also complicated the process of sampling the arena
"tanbark", and the later decontamination procedures used at the three
-5
-------
heavily contaminated arenas. Several laboratories also experienced
difficulty in working with this problem at various times, largely,
because the exact nature of the toxic substance was not known until
1974; all indications called for "extreme caution" in protecting
personnel working with any aspect of the problem. Our later findings
did prove the wisdom of being very careful with the sampling and
analysis procedures (2,3,5).
A member of our staff when the original poisoning reports came in,
who is now with the Missouri Health Department, was largely responsible
for the location of the main point source of the TCDD in a storage area
of a manufacturing plant that had gone out of existence several years
earlier. The company which now controls the location of the toxin has
taken precautions to prevent any additional "accidents", but the problem
now, is: "What can be done with the toxic residue which contains about
350 parts per million of TCDD?" (11).
Wide spread coverage in the news media has called attention to the
fact that, at present, there is no safe, effective, and approved (legal)
way to properly dispose of such supertoxic substances as TCDD, and re-
lated compounds (Anon-a,b,c,d,e—11). Just a summary quote (of quotes)
from the mass media indicates the major problem that Missouri as well
as the other authorities have to solve: "Minnesota doesn't want it";
EPA won't allow it to be moved; "We have the problem of disposal and
no way to solve it"; "No one told me it was toxic—I even tasted it.'";
"Cattle from Missouri will be tested for TCDD...": and many, many more
such quotes from the persons cited anonymously (11) indicate that more
and more persons are becoming aware of the problem associated with toxic
waste disposal. They are calling, loud and clear, for help I They also
want action, and the sooner, the better.
As was so well stated at this conference in July, 1973, TCDD and
TCDF are very dangerously toxic substances for those working with them,
as well as being real environmental hazards that should be eliminated(6).
The question remains: HOW? Abelson (10) had raised this point in his
editorial in 1970, well before the episodes discussed here took place,
but he proved an excellent prophet.
The complete toll in animal life from the known foci of contamina-
tion by TCDD may never be known, but the cost of the "mistake and acci-
dent series" described here has been very high, especially to those
immediately concerned (1,5,8,9,lie). It may very well go much higher
(6,llc,e,f). Figure 1 shows only the known foci contaminated by TCDD
which are described here as associated with treatment of riding areas
used by owners and others working mostly with pleasure horses.
The implications for the beef cattle industry and those who are in
the dairy industry are serious; it remains to be seen if forebodings
expressed by the mass media prove to be well founded (lle,f).
Morrison reviewed very well the present status of the whole situa-
tion as it pertains to disposal of waste oil materials. For the most
part, there are really no standard orders for such procedure. His
-------
o
o
o
3
en
o
i-h
03
-J I-!
(0
(U
CO
H
O
O
o
o
3
rt
5-
O
0
S
H-
CO
CO
o
MISSOURI
IT-MOSCOW Hills-Shenandoah
2-New Bloomfield-Timberline
3-Fenton-Bubbling Springs
4-St.James-Spill because of
overload
5-Verona-Storage site-Point
Source of TCDD
LOUIS CITY
-------
article is highly recommended reading for anyone who is interested in
the whole or partial implications of environmental protection while
conserving and recycling waste materials, including waste oil and "spent"
industrial wastes of all kinds (12).
References
1. Case, Arthur A. Disaster. Sheep Breeder and Sheepman. Vol.LXXXXI
(ll):24-26, 1971.
2. Kimbrough, Renate. Toxicity of Chlorinated Hydrocarbons and Related
Compounds. Arch. Environ. Health, Vol. 25:125-131, August, 1972.
3. . The toxicity of Polychlorinated Polycyclic Com-
pounds and Related Chemicals. CRC Critical Reviews in Toxicology,
445-448, January, 1974.
4. , and Ralph E. Linder. The Toxicity of Technical
Hexachlorobenzene in the Sherman Strain Rati A Preliminary Study.
Research Communications in Chemical Pathology and Pharmacology,
Vol. 8(4):653-663, August, 1974.
5. Carter, C.D., Renate Kimbrough, J.A. Liddle, R.E. Cline, M.M. Zack,Jr.,
W.F. Barthel, R.E. Koehler, and P.E. Phillips. Tetrachlorodibenzo-
dioxin: An Accidental Poisoning Episode in Horse Arenas. Science,
Vol. 188(May 16, 1975):738-740.
6. Huff, James E., and John S. Wassom. Hazardous Contaminants: Chlori-
nated Dibenzodioxins and Chlorinated Dibenzofurans. Proceed. 2nd
Annual Conference Environmental Chemicals in Human and Animal Health,
Colorado State University, Fort Collins, Colorado, 1973, pp.175-197.
7. Piper, W.N., J.Q. Rose, P.J. Gehring. Also, Piper, W.M., and J.Q.
Rose. Excretion and Tissue Distribution of 2,3,7,8-Tetrachlorodibenzo-
p-dioxin in the Rat, cited by Huff and Wassom.
8. Case, Arthur A., and James R. Coffman. Waste Oil: Toxic for Horses.
Veterinary Clinics of North America, Vol. 3(2) -.273-277, 1973.
9. Case, Arthur A. Toxicosis of Public Health Interest. Clin. Toxicol.,
Vol. 5(2): 267-270, 1972.
10. Abelson, Phillip H. Pollution by Organic Chemicals. Science, 170(3957) ;
editorial page.
11. Anon.-Series: News Releases:
a. Chemical That Killed Horses No Longer Used - St. Louis Globe
Democrat, Wed., August 28, 1974: 9A.
b. Chemical Kills -Animals, Harms St. Louis Girls - Columbia Missourian,
under AP release from Jefferson City, Mo., August, 1974.
c. Tank of Super-poison Stored on Missouri Soilr- Columbia Missourian,
Friday, February 7, 1975. Feature by Staff Writer Bert Lindler.
-------
d. Toxic Chemical May Go to Minnesota - M* release from Shakopee,
Minnesota in Columbia Missourian, April, 1974.
e. More Care Planned for Dioxin Tank - AP Release from Jefferson
City, Missouri from. Columbia Missourian, Friday, May 23, 1975:15.
f. Southern Missouri Cattle Being Tested for Dioxin - Feature in
Columbia Missourian by Bert Lindler (staff writer), May, 1975.
12. Morrison, Ed. Waste Oil Down the Drain. Environmental Action,
May 10, 1975:8-10.
-------
10
-------
VINYL CHLORIDE MONOMER:
A LITERATURE CONDENSATION*
Helen S. Warren and James Edward Huff
Toxicology Information Response Center/Biomedical Sciences Section
Information Center Complex/Information Division
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37830
ABSTRACT
Vinyl chloride monomer (VCM) is a colorless, flammable, and toxic
gas with a faintly sweet and pleasant odor and is used principally in
making polyvinyl chloride. Usually handled as a liquid under pressure,
VCM ranks twenty-third (based on production volume) in the 1974 chemical
products list at a production rate of 2,540,000,000 kg (5.6 billion pounds).
First synthesized and investigated in Germany by Regnault in 1835 VCM did
not enter the industrial category until World War II, when its polymeri-
zation capabilities were recognized and rapidly exploited.
Not known to occur in nature, VCM is nonetheless present in the
environment in large quantities — United States plants discharge annually
200,000,000 pounds into the atmosphere. Occupational exposure presents
the most hazardous avenue for human contact. The VCM work force in the
United States is estimated at 1500 in monomer synthesis, with an additional
5,000 working in the polymerization processes.
In January 1974, the report of four industry workers dying from rare
angiosarcoma of the liver triggered one of the most intensive epidemiologi-
cal and toxicological searches in the history of industrial medicine.
Our overview of VCM chronicles historical developments, summarizes
the reference literature, reviews physical and chemical properties, lists
production and use data, sketches biologic aspects, and examines proposed
standards.
By acceptance of this article, the publisher or recipient acknowledges
the U.S. Government's right to retain a nonexclusive, royalty-free license
in and to any copyright covering the article.
*Work sponsored by the Toxicology Information Program, National Library
of Medicine, under contract with the Oak Ridge National Laboratory operated
by Union Carbide Corporation Nuclear Division for the Energy Research and
Development Administration.
11
-------
INTRODUCTION
In 1974 the Toxicology Information Response Center (TIRC) began com-
piling a literature collection on the health effects of vinyl chloride
monomer (Warren and Huff, 1975). Interest was stimulated when the B. F.
Goodrich plant located in Louisville, Kentucky, notified the National
Institute of Occupational Safety and Health that an exceedingly rare liver
cancer, angiosarcoma, had been identified in autopsies of deceased workers
who had been engaged in the processing of vinyl chloride monomer, and that
vinyl chloride could bear a causal relationship to these cases (Creech
and Johnson, 1974).
HISTORY
In the early nineteenth century in the School of Mines' Laboratory,
Paris, Regnault (1835) synthesized vinyl chloride while working with
ethylene dichloride. About 100 years age, in the 1870s, VCM polymerization
capability was discovered, but not until the 1930s and particularly during
the Second World War was this polymerizing capability exploited, and the
production of poly(vinyl chloride) became a major industry. By 1973 VCM
production in the United States was at the 5.3 billion pound level
(Anderson, E. A., 1975). Monomer production, now largely by the chlorina-
tion of ethylene, is a continuous large-scale, highly automated process
conducted in 15 plants throughout the United States with about 1500
employees. An abbreviated chronicle of VCM is listed in Table 1.
Production of poly(vinyl chloride) and its copolymers had reached
the 4.6 billion pound level in 1973 following an annual growth rate of 14
percent over the past five years. Approximately 5,000 workers were em-
ployed in 43 polymerization facilities in the United States. It is in
the polymerization processes of manufacturing that the greatest exposure
to the monomer has occurred.
The long interval between the industrialization of the vinyl chloride
polymerization process and the first recognition of VCM as a carcinogen
remains one of the sinister facets of this reactive monomer, for this
time delay represents the latent period of the carcinogen within the
human organism, and may mean that the VCM-associated cancer cases detected
to date represent the start of a growing and unfortunate clinical statistic.
LITERATURE
In most crisis-related chemical-human episodes, the media — radio
and television, newspapers and newsmagazines, newsletters, and popular
magazines — report rapidly the occupational or/and the consumer insults
and injuries. Government regulatory agencies and research institutions
plan and initiate telling research projects or expand existing programs
to determine the facts. Symposia are convened, bringing together experts
to decipher the available information and organize a future plan of
attack. Shortly thereafter and with increasing rapidity investigative
reports appear.
12
-------
TABLE 1
DEVELOPMENT OF VINYL CHLORIDE
1835 First noted by Regnault.
1878 Polymerization capability recognized.
1928 Commercial production noted by the U.S. Tariff Commission.
1937 Patent granted for the preparation of poly(vinyl chloride).
1973 Production of vinyl chloride: 5 billion Ibs/year from 15
manufacturing plants. Production of poly(vinyl chloride):
4.5 billion Ibs/year from 43 manufacturing plants. Over
7500 fabrication plants employed 350,000 to 700,000 workers.
Growth rate around 14%.
1974 Recognized as a carcinogenic agent.
13
-------
The literature on VCM has proliferated rapidly as the concern and,
resources of science, medicine, labor, industry, and government have been
mobilized to elucidate the mechanisms of VCM toxicity as well as the r-eal
and^ potential exposure hazards. The scientific community is, striving; to
formulate, in the context of vinyl chloride, an index to the risks inherent
in an ever-widening circle of chemicals, industries, processes, and exposed
populations.
Two major conferences were held in 1974: the New York Academy of
Sciences' "Toxicity of Vinyl Chloride-Polyvinyl Chloride" convened on
May 10 and 11, 1974 (Selikoff and Hammond, 1975) and the National Institute
of Environmental Health Sciences' "Public Health Implications of Components
of Plastics Manufacture" met on July 29-31, 1974 (Environ. Health Perspect.
11, 1975).
Our compilation (Warren and Huff, 1975) of 264 annotated literature
references is directed toward the health aspects of vinyl chloride with a
few key historical and analytical references included. Annotations were
prepared from the published reports except for a few instances in which
time did not allow their acquisition or translation; in these cases, the
abstract source used is noted with the citation.
Until 1960 literature detailing the toxic effects of vinyl chloride
was sparse; more recently, however, the number of published reports has
risen sharply. This trend is noted in the selected reports of this
compilation:
' 1835-1959 (125 years), 17 reports;
1960-1969 (10 years), 43 reports;
1970-1974 (5 years), 102 reports.
The reference collection has been made a part of the data base hold-
ings of the Oak Ridge National Laboratory's Information Center Complex and
will be updated as the literature accumulates. The updated publication
will include not only the vinyl chloride collection (now containing 325
references) but the compilation on vinylidene chloride monomer (now con-
taining 46 references). This combined report will be available some time
in the second quarter of 1976 through the National Technical Information
Service in Springfield, Virginia 22161.
14
-------
PHYSICAL AND CHEMICAL PROPERTIES
Vinyl chloride monomer (VCM; CH2=CH-C1) is a small molecule possessing
a reactive double bond which facilitates polymerization and alkylation.
It is a faintly sweet and pleasant smelling, colorless gas with a molecular
weight of 62.5, and a chlorine content of 54.73 percent. It liquefies
in a freezing mixture, melts at -160 and boils at -14 C (Merck Index, 8th
Ed., 1968). It is only slightly soluble in water, but is soluble in
alcohol, and very soluble in ether. The monomer has a low flash point,
forming explosive mixtures when present in concentrations between 4 per-
cent and 22 percent. Because of this feature, VCM is handled and shipped
as a liquid under pressure. Until 1974 this explosive characteristic was
thought to be its most dangerous aspect. For VCM synthesis, halogenation
of ethylene has displaced the addition of hydrogen chloride to acetylene
as the most important route of production.
The monomer polymerizes readily in light or with a catalyst but does
not undergo other reactions in the absence of other reactive chemicals.
In the presence of nitrogen oxides it reacts at a rate of 8 to 10 percent
per hour to form products which include ozone, nitrogen dioxide, carbon
monoxide, formaldehyde, formic acid and formyl chloride. This low reaction
rate indicates that VCM can be considered as a stable pollutant of the
atmosphere under certain conditions (Appendix 6, EPA Vinyl Chloride Task
Force Report, 1974). Table 2 is a VCM information fact sheet.
Vinylidene chloride monomer (VDC) contains one additional chlorine
atom, is often found as a contaminant to vinyl chloride, and readily
polymerizes to form Saran wrap and other products. VCM, VDC, and other
closely related chlorinated hydrocarbons are depicted in Table 3.
PRODUCTION AND USES
A forecast implies that VCM may be in short supply by 1977 (Greek,
1975). Production capacity is nearly 7 billion pounds per year. Usually
handled as a liquid under pressure, VCM ranked twenty-third (based on pro-
duction volume) in the 1974 top 50 chemical products list —
2,540,000,000 kg (5.6 billion pounds) (Anderson, 1975).
The polymer is produced by batch process; in 1973 production
amounted to over 4.5 billion pounds with an average annual growth rate
of 14 percent (EPA Task Force, 1974). Facilities which polymerize the
gaseous monomer into poly(vinyl chloride) resin number 43. During the
polymerization process, involving an estimated 5,000 employees, employee
exposure is most likely to occur. The number of fabrication plants in
which the poly (vinyl chloride) resin is fashioned into consumer prod-
ucts is unknown: estimates range above 7,500 with an employee roster
ranging from 350,000 to 700,000 workers. The ten major companies manu-
facturing the bulk of VCM are listed in Table 4. Locations show a
preponderance for the South, particularly the southwestern states. The
five top-ranked account for 56 percent (3,860 lbs/6,840 Ibs) of the
production capacity.
15 ,
-------
TABLE 2
VINYL CHLORIDE FACT SHEET
Synthetic, colorless, flammable, toxic gas with a faintly sweet and
pleasant odor under normal temperature and pressure.
Synonyms and Trade Names
Registry No, 75~01-4
Chlorethene
Chlorethylene
Chloroethene
Chloroethylene
Ethylene Monochloride
Monochloroethene
Mono chloro ethylene
VC
VCM
Vinyl Chloride Monomer
Vinyl C Monomer
Chemical Formula
HHC=CHC1 or C2H3C
Molecular Weight
62.50
Explosive Limits
Lower 4%
Upper 22%
Flash Point
~78°C
Boiling Point
-13.9 PC
SOLUBILITY
Slightly soluble in water C<0.11% w/ at 25°C)
Soluble in Ethanol, Ether, Carbon Tetrachloride, and Benzene
16
-------
TABLE 3
VINYL CHLORIDE MONOMER AND
CLOSELY RELATED COMPOUNDS
H-J><>
C1
H Cl
Cl Cl
Vinyl
Chloride
Vinylidene
Chloride
Trichloroethylene
Cl Cl
? s1/
rC=C~C=
C
Tetrachloroethylene
Chloroprene
17
-------
TABLE 4
VINYL CHLORIDE MONOMER PRODUCTION CAPACITY
Capacity
'(Millions of
Company
Allied Chemical
Continental Oil
Dow Chemical
Ethyl Corporation
B. F. Goodrich
Monochem
CBorden/
Uniroyal)
PPG Industries
Shell Oil
Stauffer Chemical
Tenneco
TOTAL
Location
Baton Rouge
Lake Charles, La.
Freeport, Texas
Oyster Creek, Tex,
Plaquemine, La,
Baton Rouge
Houston
Calvert City, Ky,
Geismar, La.
Guayanilla, P.R.
Lake Charles, La.
Deer Park, Tex,
Norco, La,
Long Beach, Calif,
Houston
Ibs. per year)
350
600
150
720
430
300
150
1000
300
500
400
840
700
170
230
6840
Rank
9
5
13
3
7
10
13
. 1
10
. 6
8
2
4
12
11
Source; Greek, 1975
18
-------
End uses of the poly(vinyl chloride), (-H2C-CH(C1)-)X, are shown
in Table 5. Eight market categories adequately represent the major
PVC products. The building and construction industry (Market Category
II) uses the bulk of the manufactured PVC—a total of 926,000 metric
tons or 43 percent of the market. Home products (Market Category IV)
commit 13 percent; the other six categories range from 5 to 9 percent
of the PVC market (EPA Vinyl Chloride Task Force,, Appendix 1, 1974).
POTENTIAL AVENUES OF EXPOSURE
The chief source of environmental and occupational exposure to VCM
lies in the manufacturing processes, particularly during polymerization.
Estimates place the annual VCM loss to the atmosphere at between 4.5 to
7.5 percent of product manufactured or an excess of 200 million pounds,
and probably over 50 million pounds of PVC escape to the air (Executive
Summary, EPA Vinyl Chloride Task Force Report, 1974), Periodically,
the polymerization reactors are opened after the batch processing is
completed; at this point much of the VCM loss to the atmosphere takes
place and the highest occupational exposure occurs.
The EPA has proposed a 10 ppm VCM air emission standard affecting
58 existing plants in the United States^*-17 ethylene dichloride/vinyl
chloride plants and 41 polyvinyl chloride plants, as well as any con-
structed in the future (Pest. Chem, News, 1975). Fabricating plants
are not covered because monitoring of five fabricating plants found
little or no VCM in surrounding air. Ambient air samples near manu-
facturing plants (within 1/2 mile) have seldom shown more than 1 ppm
VCM, but higher peaks have been found due to either accidental dis-
charges or periodic variations in the processes within the plants
(Executive Summary, EPA Vinyl Chloride Task Force Report, 1974).
Vinyl chloride has a low reaction rate and is a relatively stable
contaminant in the atmosphere. In direct sunlight and with other
reactive chemicals, laboratory tests indicate that perhaps 8 to 10
percent is reacted per hour, On cloudy days, at night, during fall and
winter, or in temperature inversion conditions, the buildiup of VCM
in the atmosphere could be of toxicological significance.
Consumer contact with vinyl chloride occurs chiefly through use of
fabricated PVC products. However, the monomer itself has been used as
a propellant in certain aerosols. A 30-second release of VCM aerosol
has been calculated to result in a concentration as high as 400 ppm in
the air of a closed room, some of which may persist for several hours
(EPA Vinyl Chloride Task Force Report, 1974). Table 6 lists some
calculated levels of exposure to VCM aerosols for members of an average
family (Gay, 1975). With the recall of VCM aerosols, and the ban on
their sale which took place in April, 1974, this source of contamination
should be largely eliminated (Fed. Reg. 39(82):14753-4 (1974).
19
-------
TABLE 5
MAJOR PVC PRODUCTS
1973
Market Category Products 1000 metric tons Percent
I. Apparel Baby pants 12
Footwear 66
Outerwear 31
109 5.05
II. Building and Extruded foam molding 26
Construction Flooring 211
Lighting 5
Panels and siding 39
Pipe and conduit 525
Pipe fitting 44
Rainwater systems,
soffits, fascias 16
Swimming pool liners 18
Weatherstripping 16
Windows 26
926 42,91
III. Electrical Wire and Cable 194
194 8,99
IV. Home Appliances 20
Furniture 145
Garden hose 18
Housewares 51
Wall coverings and
wood surfacing films 54
288 13.34
V. Packaging Blow molded bottles 36
Closure liners and
gaskets 9
Coating 9
Film 59
Sheet 35
148 6.86
VI. Recreation Phonograph records 66
Sporting goods 25
Toys 88
179 8.29
20
-------
TABLE 5 (Cont'd)
MAJOR PVC PRODUCTS
Market Category
VII. Transportation
VIII. Miscellaneous
Products
Auto Mats
Auto tops
Upholstery and seat
covers
Agriculture (incl,
pipe)
Credit cards
Laminates
Medical tubing
Novelties
Stationery supplies
Tools and hardware
Other
TOTAL
1973
1000 metric tons
18
15
83
116
Percent
5.38
66
8
23
23
7
18
8
45
198
215?
9.18
100.00
Source: EPA Preliminary Assessment of Environmental Problems Associated
with Vinyl Chloride and Polyvinyl Chloride, Appendix 1, 1974,
•21
-------
TABLE 6
ESTIMATED WEEKLY EXPOSURES TO VINYL CHLORIDE AEROSOLS
AMONG FAMILY MEMBERS
Family
Member
Mother
Father
Direct
Exposure
Product Use (ppm h
week)
Hairspray
Deodorant
Insecticide
Room deodorant or disin-
fectant
Furniture polish or window
cleaner
TOTAL
Hairspray
Deodorant
Insecticide
Room deodorant or disin-
175
42
25
50
292
^"42"
25
Indirect
Exposure
(ppm h
week)
70
21
10
50
100
2BT
70
21
10
50
Total
(ppm h
week)
245
63
10
75
150
54~3
70
63
35
50
fectant
Furniture polish or window
cleaner
TOTAL
67
100
100
318
Children
Hairspray
Deodorant _^^
Insecticide
Room deodorant or disinf*
fectant
Furniture polish or window
cleaner
TOTAL
70
21
10
50
100
251
70
21
10
50
100
251
Source: Gay, B. W., Ann, N,Y. Acad, Sci., 246:286^295 0-975),
22
-------
Leakage of unreacted monomer from finished products becomes impor-
tant in such uses as food packaging, water conduit and pipe linings,
floor covering, and wearing apparel. Just how much monomer remains in
the polymer resin to be potentially released during use of fabrication
is uncertain, but depends largely on manufacturing processes. Probably
not more than 5 to 20 ppm remains in most finished products, but in
unusual cases as high as 8,000 ppm of unreacted monomer have been re-
ported in the PVC resin (EPA Vinyl Chloride Task Force Report, 1974),
Some monomer is undoubtedly dissipated with the manipulations of
fabrication and with aging.
VCM migration from PVC pipe or pipe linings has not been proven.
If established, however, it would be particularly important in potable
water supply systems, Preliminary data indicate that the levels of VCM
detected in water flowing through PVC pipe in actual use are below the
levels which have been associated with adverse effects in experimental
animals. EPA's Water Supply Research Division in Cincinnati has
developed methods of analysis for VCM in water in the detection range
of 0.02 ug (.Bellar, T. A. 1975). The trend has been toward increased
use of plastic bottles and especially of PVC bottles. Migration of VCM
from PVC bottles into alcoholic beverages has been established
(Environment (15(5), 1973). Whiskey is an effective extractor and as
much, as 10 to 20 ppm VCM have been found in whiskey bottled in PVC.
The amount of migration depends upon the amount of residual monomer
left in the resin at the time of manufacture, and upon the time of
storage or contact with the PVC packaging. Some manufacturers have
suggested a food grade of resin for bottling alcoholic beverages, and
the modern resins now in use are predicted not to exhibit VCM migration
to foods.
The sanitary disposal of plastic products containing PVC is a
growing problem as the population and the uses of plastics grow. The
possibility of contamination by the monomer from incineration or leach-
ing from landfills is a necessary subject for investigation.
BIOLOGICAL ASPECTS
Adverse biological effect of vinyl chloride on the human organism
have been known for several years. As early as 1949, Russian investiga-
tors (Tribukh, et al., 1949) noted that hepatitis-like liver symptoms
had Been found in 25 percent of the workers in a vinyl chloride factory.
In 1957 another Russian scientist (Filatova, 1957) wrote a paper on
anginoneuroses, the effects of VCM on the nervous system impinging on
the cardiovascular system, observed in vinyl chloride workers. In 1961
Torkelson, Oyen, and Rowe (1961) suggested that U.S. industry should
operate under a time-weighted average of 50 ppm vinyl chloride monomer,
on the basis of liver changes noted in rabbits and rats; Dow Chemical
lowered the allowable level in its own plants.
23
-------
Exposure to the monomer has been greatest at the polymerization
stage of the manufacturing processes. After polymer emptying, the
polymerized scale which clings to the walls of the reactors must be
cleaned away. Formerly this required the entrance of an employee, the:
poly-cleaner, into the reactor where he manually scraped the deposit
from the walls. Pockets of the gas were often enclosed in the crusts
which had to be broken and scraped away, and the exposure to vinyl
chloride within the vessel could be very high. A very common complaint
of the poly-cleaner was Raynaud's phenomenon—a condition in which the
fingers became very sensitive to cold, and would become white and
painful very suddenly on any slight change in temperature. The signs
and symptoms were ascribed to a combination of chemical insult—the
vinyl chloride, a physical insult—the vibrations from the physical
scraping, and some personal idiosyncracy in the heritable make-up which
made the individual susceptible. Modern manufacturing processes now
use pressurized methods of cleaning which do not require entry to the
reactors or manual scraping. In virtually all cases of industrial vinyl
chloride exposure investigated, including the cancer cases, the patients
have been poly-cleaners at some time in their industrial career.
Throughout the 1960s observations, investigations, and reports were
made on the poly-cleaner's disease. Named "Occupational Acroostyeolysis"
because of the manifest effect on the bony structure, chiefly of the
fingers, acroosteolysis is nearly always accompanied by Raynaud*s
phenomenon. Telltale signs and symptoms include shortening and clubbing
of the fingertips, with a dissolution of the bony structure in a typical
band-like pattern. When workers are removed from exposure to vinyl
chloride, symptoms generally disappear, changes tend to be reversible,
and recovery is sometimes apparently complete. An exhaustive epidemio-
logical survey, planned to study the relationship between vinyl chloride
and acroosteolysis in over 5,000 VCM and PVC workers, revealed that the
disease was systemic rather than a localized affliction (Dinman, Cook,
Dodson, 1971). All reports concerned workers who had received large
amounts of exposure and who had worked as reactorrcleaners. Lange
(.1974) suggested that the term "acroosteolysis" was too limited in
scope. Considering the observed systemic effects, a more suitable name
would be "vinyl chloride disease."
Viola (1970) reported that vinyl chloride had produced cancer in
rats at exposures of 30,000 ppm, 4 hours/day, 5 days/week for ten months.
These large exposures are similar to those which a poly-cleaner might
be subjected. Reactor-cleaning in most plants has been an entry point
to employment. Many persons began work at that station, and were,
therefore, exposed to such high amounts.
Further detailed investigation was obviously indicated. Maltoni
mounted extensive experiments in specially constructed facilities (a) to
test Viola's results at high-dose rates, b) to determine the lowest
inhalation level that might be carcinogenic, c) to study the latent
effects of low-dose rates through life-time observations, d) to determine
if ingestion of vinyl chloride produced malignancy, and e) to determine
if the offspring of animals exposed to the inhalation might develop tumors
through a transplacental effect. Three species were used—mice, hamsters,
and two strains of rats.
24
-------
By 1972 Maltoni's experiments pointed to the development of tumors
in rats receiving 500 ppm vinyl chloride by inhalation, This exposure
level had been accepted by the American Conference of Governmental In-
dustrial Hygienists several years previously, and had been accepted by
the Occupational Health and Safety Administration (OSHA) when OSHA was
established in 1970.
In December 1973, when Creech diagnosed angiosarcoma of the liver
in an autopsy, recalled that another employee died from the same type of
rare tumor, and examined company records and discovered a third case of
angiosarcoma, he then realized the possibility of an occupationally re-
lated cause and notified the National Institute of Occupational Safety
and Health. A tremendous investigative effort was launched into every
phase of VCM—manufacturing, uses, and environmental contamination, with
particular attention to the biological effects and epidemiology.
OSHA set an Emergency Temporary Standard of 50 ppm VCM (Stender,
1974a) effective April 1, 1974. Keplinger et al. (1975) found that mice
developed angiosarcoma on exposure to 50 ppm VCM. OSHA immediately
proposed a "no-detectable" level, but decided to wait until hearings
could be held to assess the effect on the health of workers and on the
economics of the industry.
In October 1974, OSHA published the proposed Standard effective
January 1, 1975, ruling that the limit of exposure in a tiroes-weighted
average over an eight hour day must be no more than 1 ppm (Stender,
1974b). A ceiling of 5 ppm was set for any 15-minute period. The
implementation of the Standard was delayed by appeal but into effect
on April 1, 1975. Some details of the Standard are shown in Table 7.
In the meantime, in his experiment BT1, Maltoni (1974) used two
sets of controls—one received no treatment and one received vinyl
acetate parallel to the vinyl chloride experiment at the 2,500 ppm
level (Table 8). Neither control produced tumors. But a wide range of
dose-dependent tumors resulted from varying levels of exposure to vinyl
chloride at 131 weeks into the experiment. At 10,000 ppm VCM tumor
incidence was 39 percent. At 500 ppm tumor incidence equaled 16 percent.
No tumors were evident in those rats inhaling 50 ppm VCM for 4 hours/
day, 5 days/week. However, when this experiment was ended one month
later, at 135 weeks, and the remaining animals were sacrificed, one
nephroblastoma, one angiosarcoma of the liver, one diffused angiosarcoma
of the abdomen, plus several other tumors (total of nine) were found
at the 50. ppm level.
In another experiment, Maltoni (1975) used breeder rats which
inhaled VCM four hours daily from the 12th to 18th day of pregnancy.
Subcutaneous angiosarcoma appeared in 2 out of 46 offspring, with a
Zymbal gland carcinoma in a third.
25
-------
TABLE 7
STANDARD FOR EXPOSURE TO VINYL CHLORIDE
Effective April 1, 1975
APPLIES: Monomer, Polymer, Fabrication, Transportation,
LEVEL: 1 ppm averaged over 8 hours; 5 ppm averaged over 15 minutes.
ACTION LEVEL: 0,5 ppm averaged over 8 hours (Exemptions),
MONITORING} 1 ppm Above *•** Monthly
Below *"- Quarterly
Daily Roster above 1 ppm kept for 30 years.
APPROVED RESPIRATORS: Through 1975, optional above 25 ppm.
After April 1976, mandatory above 1 ppm.
WARNING SIGNS AND LABELS
MEDICAL SURVEILLANCE: Specified tests,
Every 6 months after more than 10 years
of employment.
Annually for all others; after any emergency,
Physician's written statement of suitability
for employment placement.
Records retained for 20 years beyond employment
or 30 years.
26
-------
Table 8. Experiment BT1: Results After 131 Weeks
Groups and
treatment
I
VA 2,500 ppm
II
VC 10,000 ppm
III
VC 6,000 ppm
IV
VC 2,500 ppm
V
VC 500 ppm
VI
VC 250 ppm
VII
VC 50 ppm
VIII
No treatment
Total
Animals
(Sprague-
Dawley rats
Survi-
Total vors
96
69
72
74
67
67 1
64 3
68 1
577 5
Zymbal
glands
carcinomas3
No.
13
5
2
3
-
—
_
23
Nephroblas-
tomas°
No..
3
3
6
3
5
-
_
20
Animals with tumors
Angiosarcomas
Liver c Other sites
No. No.
-
6
j
11 la
9 3e
7 2f
2 28
- -
»» -^
35 8
Other type
and/ or
site
No.
^,
•u
5h
1
I1
I1
lk
21
-
^
10
Total
No.m
_.
27
21
21
16
11
-
.^
96
fMetastases to lung.
Metastases to liver and/or to lung and spleen.
,Metastases to lung.
eAngiosarcoma in subcutaneous fibrosing angioma.
Two intra-abdominal angiosarcomas (1 contiguous
to spleen and 1 to ovary); 1 ossifying angiosarcoma
of neck.
One pulmonary angiosarcoma; 1 angiosarcoma of uterus.
''One intra-abdominal angiosarcoma (near to spleen); 1
, intrathoracic ossifying angiosarcoma.
Two Zymbal gland adenomas; 1 neurilemmoma of the ear;
1 mammary carcinoma; 1 cystoadenocarcinoma of ovary.
iSebaceous gland carcinoma of skin.
1 Zymbal gland adenoma; Minimal deviation hepatoma; One Zymbal gland adenoma} 1 salivary gland carcinoma.
Total No, of tumors,
Source; Maltoni, C..; Lefeonine, G,, Environ. Res, 7C3); 387^405 (1974)
-------
In March 1975, Maltoni reported to the Royal Academy of Science
in Sweden that rats receiving VCM by gastric intubation (ingestion), in
doses of 3.3, 16.6, and 50 rag/Kg in olive oil, developed angiosarcoma at
the 16.6 and 50 mg/Kg levels (C&EN, 1975). Undoubtedly this has impli-
cations for the PVC food packaging industry if shown that VCM does
migrate into food from wrapping materials in any appreciable degree.
Despite one manufacturer's protest that 16.6 mg/Kg level was equivalent
to a Frenchman drinking 16,000 bottles of wine in one day, Canada has
already announced intentions to prohibit the sale of any food in a
package from which any amount of VCM may be detected (Food Chem, News,
1975).
COMMENT
Environmental and human exposure to real and potentially hazardous
agents is on the increase. This is inevitable as more and more chemicals
are introduced into the end product armamentarium. The number of unique
chemical substances recorded in the fij.es of the CAS Chemical Registry
System passed 3 million early in 1975 (CAS Report, 1975), a total which
includes all unique substances indexed for CHEMICAL ABSTRACTS since
January 1965, Substances new to the file are being registered at a rate
of more than 30,000 per year. Of these, industry introduces into the
market from 300 to 500 new chemical compounds each year (Douglas, 1972),
Unfortunately many chemicals are introduced without adequate toxicological
testing.
Research teams from many disciplines are attacking the problems of
VCM with the knowledge that it may serve as a test case for many other
chemicals.
Epidemiologists are trying to determine the full extent of the
lem, through mortality studies, company records, and clinical examinations
of thousands of employees. Chromosomal aberrations as well as teratogenic
effects have been reported (Infante, 1975).
Research seeks to understand the mechanisms of the disease, and to
identify the agent (s), possibly a metabolite, which is responsible. A
dependable testing procedure is being sought which will detect biologi-
cal damage before it reaches a harmful or irreversible stage. Acrooste-
olysis has seldom appeared in an angiosarcoma victim, and angiosarcoma,
at present, cannot be detected until the terminal stages. Various
batteries of procedures are being used in diagnostic and epidemiological
studies, but no simple method of detection has yet been discovered.
Unfortunately, the possibility exists that there may be no immediate
signals of harm. With a 20-year latency period and large numbers of
workers exposed, the number of angiosarcoma cases may well continue to
rise for the next two decades, even if all exposure is reduced to the
1 ppm level requested by OSHA.
28
-------
The fact that the cancer does not usually appear until many years
after acute or/and continuous exposure imposes difficulties when at-
tempting to assign carcinogenicity unequivocally to any one particular
compound. The interactions of chemicals complicate the picture to a
frustrating degree. In the case of vinyl chloride, its near relative,
vinylidene chloride, is also suspect, often occurs with vinyl chloride,
and the interaction between the two is at present a subject of research.
Some results indicate that vinyl chloride may protect the organism
against a more severe damage by vinylidene chloride.
With increased incidence of and exposure to potential carcinogens,
other types of cancer may begin to appear. The carcinogenicity of vinyl
chloride would have been much less readily recognized if the resulting
tumors had been a more common type, The cancers caused by vinyl chloride
may well be only an early warning of problems yet to come.
The resources and cooperation of science, medicine, labor, govern-
ment and the ever-widening circle of exposed populations are obligatory
in the identification and control of the unknown risks inherent in our
modern industrial civilization.
The key to understanding the injury caused by VCM and homologs
depends on determination of the basic chemical processes involved
(Reynolds et al., 1975). Pogo recognized this when he said, "We have
met the enemy, and he is us."
ACKNOWLEDGMENTS
We are grateful to Dr. G. U, Ulrikson, Director of the Information
Center Complex, to Helga B. Gerstner, Director of the Toxicology
Information Response Center, and to Dr. Eldon P, Savage, Colorado State
University for their patience, understanding and guidance. Their support
and the capable assistance of their staff is most warmly appreciated,
29
-------
REFERENCES
1. Anderson, E. A., Special Report: C&EN's Top Fifty, Chemical
and Engineering News, _53 (18): 29-33 (1975).
2. Anonymous, Spectrum: News of the Month, Environment 15(5):
22 (1975).
3. Bellar, T. A., Lichtenberg, J, J.; Eichelberger, J, W, The
Determination of Vinyl Chloride at the ug/1 Level in Water by
Gas Chromatography. National Environmental Research Center,
U.S. Environmental Protection Agency, Cinn,, Ohio 45268,
Unpublished (1975).
4. CAS Report, No. 4, Chemical Abstracts Service, Columbus, Ohio
43210 (August, 1975).
5. Chemical and Engineering News, 53{U):7 (1975).
6. Cook, W. A.; Giever, P. M.; Dinman, B, D,; Magnuson, H, J,,
Occupational Acroosteolysis. II. An Industrial Hygiene Study,
Arch. Environ. Health 22i 74~82 (1971).
7. Creech, J. L.; Johnson, M. N., Angiosarcoma of Liver in the
Manufacture of Polyvinyl Chloride, J. Occup. Med, 16_(3): 150-151
(1974).
8. Dinman, B, D.; Cook, W. A,; Whitehouse, W. M,; Magnuson, H. J,;
Ditcheck, T,, Occupational Acroosteolysis. I, An Epidemiological
Study, Arch. Environ, Health 22.: 61-73 (1971),
9. Dodson, V. N,; Dinman, B. S.; Whitehouse, W, M,; Nasr, A, N, M.;
Magnuson, H. J., Occupational Acroosteolysis. Hit Clinical
Study, Arch. Environmental Health 22;.83-91 (1971),
10. Douglas, W. 0., The Three Hundred Year War, 215 pp, Random House,
1972.
11. Environmental Protection Agency Task Force, Preliminary Assessment
of the Environmental Problems Associated with Vinyl Chloride and
Polyvinyl Chloride. Report on the Activities and Findings of the
Vinyl Chloride Task Force (.1974).
12. Environmental Protection Agency Task Force. Appendices 1~9,
Preliminary Assessment of the Environmental Problems Associated
with Vinyl Chloride and Polyvinyl Chloride, Report on the
Activities and Findings of the Vinyl Chloride Task Force (1974),
13. Filatova, V. S,, Sanitary-Hygienic Conditions of Work in the
Production of Polyvinyl Resins and Measures of Improvement.
Gig. Sanit, ^2Cl):38-42 (1957).
14.. Food Chemical News, 17(.9):3-4 (1975),
30
-------
15. Gay, B. W., Estimated Weekly Exposures to Vinyl Chloride Aerosols
Among Family Members. Ann. N. Y. Acad. Sci, 246_:286 (1975).
16. Greek, B. F., Vinyl Chloride May Face Shortage by 1977. C&EN 53
(32):8-10 (1975).
17. Infante, P. F., Oncogenic and Mutagenic Risks in Communities with
Polyvinyl Chloride Production Facilities; Conference On Occupational
Carcinogenesis, Abstract, N. Y. Acad, Sci., (to be published).
18. Keplinger, M. L.; Goode, J. W.; Gordon, D. E.; Calandra, J. C.,
Interim Results of Exposure of Rats, Hamsters, and Mice to Vinyl
Chloride, Ann. N. Y. Acad. Sci, 246:219-224 (1975),
19. Lange, C. E.; Juehe, S.; Stein, G.; Veltman, G,, Die Sogenannte
Vinylchlorid-Krankheit—eine Berufsbedingte System~-Sklerose?
(The so-called Vinyl Chloride Sickness - an Occupations-Related
Systemic Sclerosis?), Int. Arch. Arbeitsmed, 32_;l-32 (1974),
20. Maltoni, C.; Lefemine, G., Carcinogenicity Bioassays of Vinyl
Chloride. I, Research Plan and Early Results, Environ, Res,
_7(3): 387-405 (1974),
21. Maltoni, C,; Lefemine, G,, Carcinogenicity Bioassays of Vinyl
Chloride: Current Results, Ann. N. Y. Acad. Sci. 246_: 195-218
(1975).
22. Merck Index, 8th ed., Merck & Co., Rahway, N. J, (1968),
23, Pesticide Chemical News 4.C3);26 C1975),
24. Regnault, V., Ueber die Zusammensetzung des Chlorokohlenwasserstoffs,
(The Synthesis of Chlorinated Hydrocarbons), Ann, Chem, 14:22^28
(1835).
25, Reynolds, E. S.; Moslen, M. T,; Szabo, S,; Jaeger, R, J.; Murphy,
S. D., Hepatotoxicity of Vinyl Chloride and 1,1-Dichloroethylene,
Amer. J. Path. 81(1):219-236 (1975).
26. Selikoff, I, J,; Hammond, E. C., Toxicity of Vinyl Chloride-
Polyvinyl Chloride, Ann, N. Y, Acad, Sci, 246^:1-337 (1975).
27. Stender, J,, Emergency Temporary Standard for Exposure to Vinyl
Chloride, Fed. Register 39_(67): 12342-12344 (1974a),
28, Stender, J., Standard for Exposure to Vinyl Chloride, Fed,
Register 39(194):35890-35898 Cl974b),
29. Torkelson, T, R, ; Oyen, F,; Row.e, V, K, , The Toxicity of Vinyl
Chloride as Determined by Repeated Exposure of Laboratory
Animals, Amer. Ind. Hyg, Assoc, J, 22(5);354-361 (1961),
31
-------
30. Tribukh, S. L.; Tikhomirova, N. P.; Levina, S, V.; Kozlov, L. A.,
(Working Conditions and Measures for Their Improvement in Production
and Use of Vinyl Chloride Plastics), Gig, Sanit, No. 10:38-44
C1949). (CA 44:1744a).
31. U. S. Environmental Protection Agency, Vinyl Chloride. Emergency
Suspension Order Concerning Registrations for Certain Products and
Intent to Cancel Registrations. Fed. Reg. _39(82): 14753-4 (1974).
32. Viola, P. L., Cancerogenic Effect of Vinyl Chloride, Abstracts.
Tenth Int. Cancer Conf., Houston, Texas Session 56:742 Abstract
No. 29 (1970).
33. Warren, H.; Huff, J. E., Health Effects of Vinyl Chloride Monomer:
An Annotated Literature Collection, Environ, Health Perspect. 11:
251-319 (.1975).
32
-------
DIFFERENTIAL PULSE POLAROGRAPHIC DETERMINATION OF SOME
CARCINOGENIC NITROSAMINES
Kiyoshi Hasebe and Janet Osteryoung
Departments of Civil Engineering and Microbiology
Colorado State University
Fort Collins, Colorado 80523
INTRODUCTION
Secondary amines react with nitrite under acid conditions to form
W-nitrosamines, many of which are carcinogenic, mutagenic, or tetratogenic
(1-4). Secondary amines are common constituents of foodstuffs and can
react with naturally occurring or added nitrite under food processing
or storage conditions or in the stomach to form W-nitrosamines. The most
important potential human exposure to these compounds is in cured meat
products. Studies of the prevalence, toxicity, and significance to
public health of these compounds requires analyses at the 5-10 yg/kg
level which corresponds roughly to solutions at the 10 M level. Many
analytical methods such as spectrophotometry (5), gas-liquid chromato-
graphy (7,8), and gas chromatography—mass spectroscopy (6) have already
been applied to the determination of W-nitrosamines. Of these techniques,
only the GC-MS approach now provides both qualitative and quantitative
information sufficiently reliable for routine analytical operation, but
the GC-MS analysis is time consuming and expensive and can be applied
only to volatile compounds.
In this paper we describe the pulse polarographic behavior of some
nitrosamines and report suitable conditions for analysis. The nitro-
samines studied are W-nitrosopyrrolidine (NOPyr) and two of its derivatives,
W-nitrosoproline (NOPro) and W-nitroso-4-hydroxyproline (NOHOPro). NOPro
is relatively nonvolatile and unstable with respect to temperature. It
melts with decomposition at 100°C and on mild heating of a slightly alka-
line aqueous solution decarboxylates to form NOPyr. NOPro is not
carcinogenic, but is found in most fatty cured meats (e.g. bacon), and
its decarboxylation product, NOPyr, is one of the most potent carcinogens
so far identified. The decarboxylation reaction apparently takes place
to some extent under meat processing conditions (9, 10). The 4-hydroxy
derivative is also of interest because the precursor amino acid occurs
free in foods.
There is little information about polarographic analysis for W-nitro-
samines in the literature (11, 12). In trace analysis, DC polarography
has insufficient sensitivity and AC polarography is usually limited by
the irreversibility of the electrode process. Pulse polarography is a
well-established electrochemical technique which minimizes capacitative
current and, especially in the differential mode, is proving to be a
versatile technique for trace determination of metals and non-metals
(13, 14). Pulse polarography has the advantage of providing sensitive,
rapid analysis with simple, inexpensive equipment, and in principle has
less demanding sample cleanup requirements than the GC-MS technique.
33
-------
The differential pulse (DP) mode peak current provides lower detection
limits than does the normal pulse (NP) mode limiting current, but the
former is more sensitive to solution conditions, for its magnitude
depends on the kinetics of the electrochemical process.
The polarographic reduction of some W-nitrosamines has already been
studied (15-20). In general at mercury electrodes they exhibit an
irreversible four electron reduction in acid solution to the corresponding
unsymmetric hydrazine and an irreversible two electron reduction in
basic solution to nitrous oxide and the precursor amine (17).
For the purposes of analytical method development we have determined
the following: the conditions under which the NP limiting current is
diffusion controlled and therefore insensitive to small changes in
conditions, the effects of pH on NP and DP currents, the effects of
some solvents, supporting electrolytes, and surface active substances
on reactant adsorption and hence on the reduction kinetics and the DP
or NP currents, and the effects of instrumental parameters such as
pulse height in the DP mode. At the same time, we have examined the
effects of solution parameters on capacitative background currents
because, especially in the DP mode, these currents are large and play
an important role in determining the detection limit (21, 22). Finally,
we have determined sensitivities and detection limits for these compounds
under representative sets of good conditions.
EXPERIMENTAL
Polarographic data were obtained with a Model 174 Polarographic
Analyzer (Princeton Applied Research Corporation, Princeton, New Jersey)
and a Model 172 Drop Timer, The polarograms were recorded on an Omni-
graphic Model 2000 X-Y recorder (Houston Instrument Company, Austin,
Texas). The dropping mercury electrode used had the following
characteristics: mercury flow rate m = 1.92 mg s"1 in deionized water
at open circuit and natural drop time t
-------
N*-nitrosoproline was synthesized as follows. To 11.5 mg of L-(-)-
proline in about 80 ml of 0.1M hydrochloric acid, 0.69 g of sodium nitrite
was added slowly with cooling in a cold water bath. After reacting 1 day,
the mixture was accurately diluted to 100 ml with 0.1 M hydrochloric acid.
W-nitroso-4-hydroxyproline was synthesized similarly. NOPro crystals were
prepared according to a modification of the method of Lijinsky Vt at. (24),
i.e. 6 g of L-proline was dissolved in HC1 (4 ml) and water (20 ml) with
cooling in a water-ice bath, and 5 g of NaN02 was added slowly. After
1 hr, the water was evaporated from the reaction mixture using a rotary
evaporator, and NOPro was extracted with pure acetone. To this extract
5 g of silica gel (60-200 mesh) and 2 g of activated charcoal (60-200 mesh)
were added, and then filtered off. Acetone was removed by evaporation in a
cold bath with a stream of N£. The first crop of crystals was recrystallized
from chloroform. The white crystalline product was identified and purity
established by NMR spectra, IR spectra, UV spectra and melting point
measurements.
N-nitrosamine stock solutions were prepared in 0.1 M HC1. These
solutions were found to be stable as determined by polarography for
periods exceeding 4 months.
The pH of the polarographic solutions was adjusted with Britton-
Robinson buffer in the pH range from 1.8 to 11.9. Below about pH 1 the
measurements were made in I^SOit or HC1.
Stock solutions of the synthesized nitrosamines prepared directly
from the precursor amine contain electroactive impurities which do not
interfere with the electrochemical nitrosamine reductions. Based on
spectrophotometric measurements, the nitrite concentration in these solu-
tions is about 100 times the nitrosamine concentration.
RESULT AND DISCUSSION
Effects of pH. The effects of pH on the reductions are shown in
Figures 1, 2, and 3 and in Table 1. The data are in general accord with
results on other N-nitrosamines and support the mechanism of reduction
of the protonated form in acid solution. Free NOPyr is directly reduced
in basic solution. However, in the same pH range NOPro and NOHOPro are
present only as anions and therefore are not directly reduced. This
makes it possible to analyze mixtures of, say, NOPyr and NOPro by
determining the total concentration in acid solution and the NOPyr
concentration alone in basic solution.
The decrease in current at low pH for NOPyr in the DP mode is un-
doubtedly real and due to a decrease in the reduction rate under these
conditions. Experiments at lower pH values continue this trend. It is
most important analytically that the DP current is very sensitive to
changes in rate and mechanism, and therefore may change in unusual and
unpredictable ways even when the NP or DC currents are well behaved.
35
-------
Diffusion Control. Dependence of limiting current on mercury head
.has been studied in the DC, NP and DP polarographic modes. For diffusion-
.controlled waves, the height of the DC or NP wave'is approximately propor-
tional to h^orr when the natural drop time is used, and to h^ with a
mechanically controlled drop time. (2->) We have analyzed the data by
.plotting values of log i versus log h to obtain the power of h. The
•results generally indicate that the limiting currents are diffusion-
.contr oiled.
Therefore, the diffusion coefficients of these N-nitrosamines were
estimated by using the DC polarographic data and the Ilkovic equation,
•taking into account the varition of drop time. The results are shown in
Table II. The diffusion coefficient of Tl+ ion was measured under the
same conditions to provide a check on the results, and gives excellent
agreement with the published value of 2.00 x 10~5 cm2s~T (26).
The value of D for NOPyr is somewhat larger than that of the others,
but there is no reason to suspect experimental error in this value.
Two values are given for D for NOPro, one based a standard solution
of proline converted to NOPro and one "based on a standard solution of
NOPro prepared from synthesized NOPro. It is felt that the concentration
of the second solution is more accurately known. However, both values
are given because all other data for NOPro are based on the first
solution. Probably all absolute currents reported for NOPro should be
multiplied by the ratio of the square roots of these D values, 1.067.
Temperature Dependence. The temperature dependence of the polaro-
graphic reduction of the W-nitrosamines has been studied. E% or Ep of
NOPro observed in mixtures containing 44 v/v% ethanol (apparent pH =
2.45) and Eig or Ep of the same compound in mixtures containing 20 v/v%
ethanol (apparent pH = 1.90) were nearly independent of the temperature
within experimental error. Also Eig or Ep of NOPyr in aqueous solutions
was almost temperature independent.
Some of the relative temperature coefficients of the current for
N-nitrosamine reduction in the temperature range from 1 to 44°C are
shown in Table III. These results correspond to activation energies of
diffusion and therefore are typical of diffusion-controlled reactions.
Effect of Organic_Solvents. If miscible organic solvents are
present in the polarographic solution and there are no resulting specific
chemical effects, the limiting current should decrease due to changes
in the drop time and the diffusion coefficient with changing ionic
strength and the viscosity of the medium. Figure 4 shows the effect
of ethanol on the limiting current and half-wave or peak potential for
the reduction of NOPro. A similar phenomenon has also been observed in
the cases of the other N-nitrosamines in alcohol-water mixtures. For
example, the wave height or peak current of NOPyr in polarographic solu-
tions containing 20 v/v% ethanol is about 45% of that in the aqueous
solution only. It is important to note that the presence of the organic
solvent in the polarographic solution decreases the sensitivity. However,
the reduction of NOPro or NOHOPro is also diffusion-controlled in ethanol
or methanol-water mixtures as it is in water by criteria of the relative
temperature coefficient and the mercury head dependence of the limitng
current.
36
-------
The NP and DC currents in ethanol-water mixtures are those to be
expected from the change in viscosity of the solvent. The currents
relative to current in water at 20°C are all about 0.04 larger than
those predicted from viscosity data for 0.1 F LiBr in ethanol-water
mixtures at 25°C (27). On the other hand, the currents in methanol-
water mixtures are much larger than those predicted from similar
viscosity data. Over the range 0-30% methanol the decrease in current
is only about 5% while the square root of the viscosity for 0.1 F LiBr
in water-methanol mixtures at 25°C changes by about 20%. This lack of
agreement with Stokes-Einstein behavior for methanol casts some doubt
on the agreement in ethanol, for the latter may be due to fortuitous
cancellation of other effects. However, the point remains that these
solvent mixtures are not regular solutions, that the viscosity-
composition diagrams have pronounced maxima, and that because of this
apparently trivial changes in solvent composition can cause substantial
changes in current.
The Presence of Surfactants. Because adsorption is important to the
reduction rate, we have studied the effect of various surfactants on the
DP current. We have investigated the effects of peptone (an enzyme digest
of proteins), gelatine, methyl red, and Triton X-100. These compounds
represent reasonable but simplified models of a complex matrix of surface
active compounds. None of these substances affected the DP peak current
at concentrations <_ 10~3%, although all decreased the current at higher
concentrations.
Effect of Modulation Amplitude. In general, the larger the pulse
amplitude, the greater the peak current and the greater the sensitivity.
Small pulse amplitudes, however, give better resolution and less instru-
mental error (14).
For reversible reactions, the peak height-pulse amplitude relation-
ship predicts that at small pulse amplitudes the peak current is linear
in pulse amplitude but approaches as a limiting value the NP diffusion
current. Therefore there is no advantage in going to a very large
pulse amplitudes (> 50-100 mV, depending on n) because there is not an
appreciable gain in sensitivity. However for an irreversible reaction
the linear region of peak height dependence on pulse amplitude extends
to much larger pulse amplitudes. This is illustrated in Figure 5. This
makes it much more advantageous to work at larger pulse amplitudes to
obtain better sensitivity when one is dealing with irreversible reactions.
Figure 5 also shows that, as in the reversible case, the peak
potential is linear in pulse amplitude. However, the slope, - 0.4, is
less than the reversible slope of 0.5.
Supporting Electrolyte and Detection Limit. For reduction of organic
molecules with involvement of prior chemical reaction and adsorption the
choice and concentration of supporting electrolyte can substantially change
the reversibility and hence the magnitude of the DP peak current for the
reaction. We have examined several supporting electrolytes at about pH 1
where there is no variation in current with pH (cf Fig. 1-3). The results
are summarized in Table IV. Especially in 0.1 M ^SO^ containing 10~3
37
-------
tetrabutyl ammonium bromide, the DP background current is very small
because of the adsorption of tetrabutyl ammonium ion. However, the
reduction of N-nitrosamines is inhibited by the adsorption of these ions,
and no peak appears.
The effects of ionic strength were investigated from I = 0.01 — 0.51
M using solutions 0.01 or 0.1 M in HC1 with added KC1. In the DP mode
peak currents are constant for ionic strength I ^0.04 M. At lower ionic
strengths the current increases with decreasing ionic strength as one
might anticipate from double layer effects.
Figures 7 and 8 show typical differential pulse polarograms at the
10~ 7 M level of NOPro in 0.1 M HCl or 0.1 M K250k + 10~3 M tetramethyl
ammonium chloride. If the current offset in the instrument and modulation
amplitude of -100 mV are used, detection limits are about 8 x 10~8 M.
For example, calculation of the detection limit for NOPro under the
conditions of Figure 9 according to the procedure of Skogerboe and Grant
(28) gives d.l. =TT= 7.11 x 10~8 M, where t is the t statistic,
at the 99% confidence level, s the pooled standard deviation of the
calibration curve (2.93 nA) and m its slope (0.1386 yA/yM). The data
from which this value was calculated are displayed in the calibration
curve of Figure 9. The detection limit for NOHOPro is somewhat higher
than for the other two compounds. For NOPro, a detection limit of
8 x 10~8 corresponds to about 10 yg/1 which is adequate for laboratory
studies and for many investigations of the prevalence of nitrosamines
in the environment (29).
CREDIT
This work was supported in part by NIH Grant CA 15028-01 and by
NSF Grant GP 31491X.
38
-------
TABLE I
pH Dependence of M-nitrosamine Reduction
Ei vs. pH, mv/pH
Mode
DC
NP
DP
NOPro
137
160
160
NOHOPro
130
130
110
NOPyr
79
84
84
39
-------
TABLE II
Diffusion Coefficients
Depolarizer pH Da (cm2s~lx 10s)
Tl+ 1.98 2.00 ± 0.12
NOPro 1.96 0.752 ± 0.035
NOHOPro 1.96 0.669 ± 0.031
NOPyr 9.09 1.19 ± 0.17
NOPro 1.90C 0.349 ± 0.009
NOProd 2.10 0.856+0.064
a. The true value of these coefficients may be expected to
lie within the range above mentioned with a 99% probability;
b. Supporting electrolyte: 0.1 M LiCl + B-R buffer.
c. 20 v/v % EtOH
d. Based on solution prepared with synthesized NOPro crystals.
40
-------
TABLE III
Relative Temperature Coefficient for N-Nitrosamine reduction
/V Al\ 100\
iu; i/*
20UC
— 1
Mode
DC
NP
DP
DCa
NOPro
1.64
-
-
1.93
NOHOPro
1.39
1.49
1.60
-
NOPyr
1.52
1.57
1.06
-
20 v/v% E + OH
pH 1.49-2.00
41
-------
TABLE IV
Various Supporting Electrolytes for Determination of N-nitrosamines
a
Supporting electrolyte
V vs SCE
AE Concn. Range
mV M (x 107)
0.1 M LiCl + B-R
(pH 1.8 - 1.9)
0.1 M HC1
(pH 0.80)
0.1 M HjjSCh, + 0.1 M Na2SOif
(pH 1.15)
0.1 M H2SO., + 0.1 M MgSO.,
(pH 1.12)
0.1 M toSOi, + 0.1 M CaSO.,
(pH 0.95)
-0.765
-0.675
-0.705
100
7 - 50
-0.685
50 and 100 0.8 - 80
50 1-20
50 background
current unstable
50 1-10
0.1 M H2SO<» + 0.1 M (NHOaSOu -0.70
(pH 1.05)
0.1 M H2SOi» + (10-2 - 10~3) M BufNBr
0.1 M H2SOi» + (10-2 - 10-3) M MeifNCl -0.680
(pH 1.1)
0.1 M H2SOi» + 0.1 M Me^NCl
0.1 M H2SOi» + ID"3 M Pn»NBr
(PH 1.1)
0.1 M H2SOi» + 10"2 M Pn«NBr
(pH 1.1)
0.1 M H2SO* + 5 x 10-2 M EtuNClO*
(pH 1.2)
-0.69
-0.840
-0.710
50
50 and 100
no peak appears;
background current
small
50 and 100 0.9 - 20
50
50
50
50 and 100
background current
unstable
background current
unstable
1-8
1-8
a. Data for W-nitrosoproline. The other compounds give similar results.
42
-------
Captions for Figures
Figure 1. Effect of pH on the wave heights and half-wave or peak
potentials for W-nitrosoproline in 0.1 M LiCl containing
50 v/v% B-R buffer. 1.00 x 10"1* M NOPro; scan rate v:
2 mVs"1; modulation amplitude (AE): -50 mV.
Figure 2. Effect of pH on the wave heights and half-wave or peak
potentials for W-nitroso-4-hydroxyproline. 1.00 x 10"1* M
NOHOPro; other conditions same as Figure 1.
Figure 3. Effect of pH on the wave heights and half-wave or peak
potentials for W-nitrosopyrrolidine. 1.08 x lO"4 M NOPyr.
Other conditions same as Figure 1.
Figure 4. Effect of the volume fraction of ethanol on the wave or peak
height and half-wave or peak potentials for W-nitrosoproline.
1.00 x 10-4 M NOPro; v: 2 mVs'1; AE: -50 mV.
Figure 5. Effect of modulation amplitude on the peak height and peak
potential for W-nitrosopyrrolidine in 0.1 M LiCl containing
50 v/v% B-R buffer at pH 1.94. 1.08 x I0~k M NOPyr; v:
2 mVs"1.
Figure 6. Differential pulse polarograms of W-nitrosoproline in 0.1
M HC1 (pH 1.0). (.1.00 - 20.0) x 10~7 M NOPro; v: 2 mVs-1;
AE: -50 mV.
Figure 7. Differential pulse polarograms of W-nitrosoproline in 0.1
M H2SOif containing 10~3 M TMAC (pH 1.1). (2.00 - 12.0) x
10-7 M NOPro; v: 2 raVs"1; AE: -50 mV.
Figure 8. Calibration curve W-nitrosoproline by DP. Supporting
electrolyte: 0.1 M H2SOit + 0.1 M Na2SOjt (pH 1.15); v:
2 mVs"1; AE: -50 mV; o: without peptone; o: 10~3% peptone.
43
-------
1.00 x 10"
1-30R
Q50
NOPro in 01M LiO
-f B-R buffer
15 i
10,5
Ip 'np
dc
Figure 1
44
-------
-4
1-00 «10 M NOHOPro
in 0.1 M LiCI + B - R buffer
2.00
LU
o
CO
> 1.50
a
LU
I
too
0.50
• dc
O dpp
D npp
IP,
•
Inp
15, 3
10, 2
5, 1
0 2 4 6 8 u 10
pH
0
Figure 2
45
-------
160 r
0.8O
1.08 xlO M 1-Nitroso pyrrolidine
in 0-1 M LiCI + B-R buffer
7 8 9 1O 11 12
-1O, 5
O
-------
'dc ;
3,15
2,10
1, 5
0, 0
0
- 1.3
- 1.1
m
O
CO
- 0.9
LLJ
- 0.7
10 2O 30 40 50
v/v % Ethanol
0.5
Figure 4
47
-------
40
30
20
10
O 10 25 50
AE, mV
0788
0.86
Ul
U
«/>
•
(A
084 >
Ul
I
0.82
100
0.80
Figure 5
48
-------
-p-
VO
Differential Pulse Polarograms
0.2
0.4
0.6
1.00 x 10 7M -1-80x10 6M NOPro.
in 0.1 M HCI
Ep=-0.675V
0-8
Figure 6
1.0 1-2
-E vs. SCE
1-4
-------
Wi
o
2.00 x 10 - 1.20 x 10 6M NOPro
in 0 1 M H2SO4+ 10~3M TMAC
pH 1.1
E =- 0-680 V
supporting electrolytes
0.2
0.4
0.6 0.8
Figure 7
1.0 1.2
-E vs. SCE
1-4
-------
0.20
0-15
"lo-io
0.05
0
0
2 4 6 8 10
[NOProJ, M(xlQ7)
Figure 8
12
51
-------
REFERENCES
1. P. N. Magee and J. M. Barnes, Advanc. Cancer Res., 10, 163 (1967).
2. H. Druckrey, R. Preussmann, S. Ivankovic and D. Schmahl,
Z. Kresforch, 6>9, 103 (1967).
3. A. Wolff and A. E. Wasserman, Science, 177, 15 (1972).
4. T. Aune, Nord. Vet. - Med., J24, 356 (1972).
5. B. Gowenlock and W. Luttke, Quart. Rev., 12, 321 (1958).
6. T. A. Gough and K. S. Webb, J. Chromatogr.. 79^, 57 (1973).
7. R. H. White, D. C. Havery, E. L. Roseboro and T. Fazio, J. Assoc.
Of fie. Anal. Chem.. _57, 1380 (1974).
8. E. T. Huxel, R. A. Scanlan and L. M. Libbey, J. Agr. Food Chem.,
22, 698 (1974).
9. D. D. Bills, K. I. Hildum, R. A. Scanlan, and L. M. Libbey, J. Agr.
Food Chem.. 21, 876 (1973).
10. E. T. Huxel, R. A. Scanlan, and L. M. Libbey, J. Agr. Food Chem.. 22,
698 (1974).
11. C. L. Walters, E. M. Johnson and N. Ray, Analyst. 95, 485 (1970).
12.' F. L. English, Anal. Chem.. 23, 344 (1951).
13. J. G. Osteryoung and R. A. Osteryoung, Amer. Laboratory, ^, 8 (1972).
14. J. H. Christie, J. G. Osteryoung and R. A. Osteryoung, Anal. Chem..
45, 210 (1973).
15. I. M. Kolthoff and A. Liberti, J. Amer. Chem. Soc.. 2P_ 1884 (1948).
16. B. Martin and M. Tashdjian, J. Phys. Chem.. 60, 1028 (1956).
17. H. Lund. Acta, Chem. Scand., 11, 990 (1957).
18. L. Holleck and R. Schindler, Z. Elektrochem.. 62. 942 (1958).
19. F. Pulidori, G. Borghesani, C. Bighi, and R. Pedriali, J. Electroanal.
Chem., _27_, 385 (1970).
20. G. Borghesani, F. Pulidori, R. Pedriali and C. Bighi, J. Electroanal.
Chem., _32, 303 (1971) .
21. D. J. Myers and Janet Osteryoung, Anal. Chem.. 46, 356 (1974).
52
-------
22. J. H. Christie and R. A. Osteryoung, J. Electroanal. Chem., 49, 301
(1974).
23. A. E. Wasserman, Research Leader, Meat Composition and Quality
Research, USDA Eastern Regional Research Laboratory, Private
Communication.
24. W. Lijinsky, L. Reefer, and J. Loo, Tetrahedron, 2£, 5137 (1970).
25. I. M. Kolthoff and J. J. Lingane, "Polarography," Vol. 1, 2nd Ed.,
Interscience, New York, New York, (1952) page 86.
26. Idem, page 52.
27. H. C. Jones, "Conductivity and Viscosity in Mixed Solvents," Carnegie
Institution of Washington. Publ. No. 80, (1907).
28. R. K. Skogerboe and C. L. Grant, Spectros. Letters, _3, 215 (1970).
29. R. Preussmann, "On the Significance of N-nitroso Compounds as
Carcinogens and on problems related to their chemical analysis,"
pp. 6-9, in W-Nitrosb Compounds Analysis and Formation, LARC
Sci. Publ. No. 3, Lyon. (1972).
.53
-------
54
-------
THE PESTICIDE REPORTING SYSTEM
Dan W. Bench
Accident Investigation Officer, Region VIII
U. S. Environmental Protection Agency
The Pesticide Branch in EPA Region VIII Headquarters received a
telephone call last fall from the state laboratory in Bismarck, North
Dakota regarding a pesticide problem. Two turkey flocks totaling about
12,500 birds had been contaminated with dieldrin. The state agencies
had no legislative authority to control this problem and the federal
government could not act unless interstate commerce was involved. There
was concern that meat from these birds might be marketed to unsuspecting
North Dakota residents,
The meat from 7,500 turkeys was salvaged after the skin, fat, and
bones had been discarded. The remaining 7,500 turkeys had such high
dieldrin levels that there was no alternative but to request their disposal,
At the last minute the scheduled disposal was called off and the birds
were placed in the hands of a local Hutterite religious colony. An attempted
"feed out" of the dieldrin during the next several months was unsuccessful.
Officials had reason to believe that the colony was preparing to
market the birds through normal distribution channels, This has not yet
materialized. The birds at this time are used for human consumption by the
colony and it is reported that individual turkeys can be informally pur-
chased by visitors.
During the investigation of this incident, I came across reports of
dieldrin contaminated geese from a Hutterite colony in Montana, reports
that dieldrin contaminated grain had been ground into flour in North
Dakota, and reports that pesticide contaminated pork had been marketed
in Minnesota. None of these incidents had been reported to EPA and no
resources are committed to follow-up and documentation.
It is not known how many similar pesticide episodes remain undiscovered.
This episode, like most, could easily have been overlooked because outside
of the EPA Pesticide Episode Reporting System, there is no responsibility
for documentation and reporting to a centralized information collection point.
A focal point for the recording and study of documented pesticide
episodes has long been needed if similar incidents are to be avoided in
the future. To supply this focal point, the Pesticide Episode Reporting
System (PERS) has been established by the EPA in accordance with its
responsibilities under the Federal Insecticide, Fungicide, and Rodenticide
Act. The PERS supplies information to a nationwide computer data bank
designed specifically for pesticide episodes. The success of this system
will depend on the resources allotted to it and on the cooperation of
government agencies and individuals having knowledge of pesticide episodes.
The EPA is responsible for the regulation of pesticides through
registration, suspension and/or cancellation of registration, and the
content of label instructions. An effective PERS can make a significant
contribution.to data upon which regulatory decisions must be based.
55
-------
Those who maintain that there are no significant pesticide problems
can remain complacent in this belief because data upon which to form a
representative picture has not yet been collected. Sufficient resources
have not been devoted to the documentation and reporting of pesticide
episodes. The information that has been gathered remains isolated in
the files of state and federal agencies throughout the contry. Aside from
the already mentioned lack of resources, some of the reasons for poor
reporting are fear of further restriction on certain pesticide uses, fear
of liability on the part of the applicator, and desire to maintain undis-
rupted working relationships between applicators and government agencies.
In implementing the PERS we have contacted pesticide related state
and federal agencies. We have attempted to establish a focal point within
each state through which reports would be passed to the Regional Office
In Region VIII we enter into the PERS only reports that have been investi-
gated by the Regional Office or by one of the pesticide study projects or
that we have received from cooperating agencies. Since most of the reporting
agencies have a direct relation with the agricultural community we do not
receive spurious or uninvestigated reports. Reports originally received
at the Regional Office are referred to the pesticide study projects or to
the appropriate state agencies fo.r investigation and subsequent reporting.
We are working to develop additional reporting sources. Among these,
the Poison Control Centers may make significant contributions when resources
become available for them to investigate suspected pesticide poisonings.
Substantial reporting from the medical profession has not yet developed.
Reports we have obtained indicate that pesticide effects can easily be
confused with "something that's going around right now,11
Inquires into pesticide effects customarily dismiss subjective symptoms
such as headache, fatigue, or nausea because they cannot be validated by
known physiological indicators. The cost of pesticide induced effects that
result in lost efficiency and in a diminution of the quality of life is
unknown.
We are aware of a large greenhouse operation where light nausea is
regarded as. "jus.t part of the job" and is ignored because there are no
obvious short term side effects. In another instance, a farmer requested
that I. refer him to a physician specializing in pesticide problems. He
explained that his living depended on his farm but that whenever he was
exposed to 2,4--D he had Intense headaches. Physicians are only beginning
to take notice of pesticide effects and it is doubtful that there are any
medical solutions to his problem. Since 2,4-D is registered as a broad
leaf herbicide and not for controlling farmers we could supply him with
little information concerning his problem. These two examples indicate
that more resources should be devoted to an examination of the side effects
of pesticide uses. It is likely that situations like these are common
throughout the country but until they are reported to a centralized agency '"'
for analysis, nothing can be done to correct them.
In conclusion, there is a need for more complete reporting of pesticide
episodes to enable EPA to better protect the public and the environment.
The protection can be accomplished through increased regulation when neces^
sary and through the avoidance of unnecessary regulation that might result
from a few highly visible incidents.
56
-------
FIELD STUDIES FOR
CHARACTERIZATION OF ACUTE
PESTICIDE POISONINGS
Eldon P. Savage, M.P.H., Ph.D.
Chief, Chemical Epidemiology Section
Institute of Rural Environmental Health
Colorado State University
Acute poisonings by pesticides are a continuing problem in the
United States because of our reliance on synthetic chemicals to assist
in greater crop yields and to control disease-carrying insects and
rodents. All pesticides are considered to be toxic compounds and
many are potentially capable of causing illness or even death when
improperly handled. Morbidity and mortality from pesticides depend on
several factors including the toxicity of the particular pesticide,
route of exposure, and formulation. Epidemiological characteristics
such as age, sex, race, physical and mental health status, as well as
time and place interrelationships are also important in pesticide
poisonings (1).
Past studies have shown mortality from pesticides to be
approximately one per million population. Although the mortality may
vary from year to year, it remains at approximately the same rate (2).
Since information on morbidity is not as available or as reliable as
data for mortality, we do not have accurate data on morbidity on a
national basis. In special studies on morbidity, the ratio of fatal
to non-fatal cases has ranged from 1 to 13 to 1 to 750 cases. Some
researchers have suggested that if we count significant illnesses only,
that the ratio is estimated to be about 1 to 100. (2)
The state of California maintains good annual records on pesticide
poisonings in their report on occupational diseases. Accidental
57
-------
deaths due to pesticides and other agricultural chemicals in California
during 1951 to 1970 were highest in children, 93 out of 167, and lowest
in occupationally exposed workers, 36 out of 167; the rest of the
fatalities, 38, occurred in adults in a non-work situation. Arsenic
and organophosphorous compounds accounted for most of the deaths (3).
In 1970, organophosphates (OP) (332), halogenated hydrocarbons (HC)
(96), carbamates (C) (13), and herbicides (H) (214) accounted for 655
or 44% of the reports of occupational disease in California (3).
Reich et al. noted that certain areas in the United States have
reported many cases of pesticide poisoning (4). For example, in the
lower Rio Grande Valley of Texas where large amounts of organophosphate '
pesticides are used, about 275 acute pesticide poisoning cases occurred
from 1960 through 1966. In 1964 there was a striking increase in the
number of cases observed. This rise coincides with the introduction of
certain organophosphate insecticides used to control crop pests,
especially insects attacking cotton. The number of cases of poisoning
observed in 1965 and 1966 was about the same, near 70 each year.
Hospital and poison control center records of pesticide poisonings
which occurred in the area were reviewed to define their epidemiological
and clinical characteristics. These records revealed the occurrence of
129 well-documented cases of acute pesticide intoxication between 1961
and 1967. The majority of these cases occurred during the summer months
and principally involved teen-age boys occupationally exposed by the
dermal route.
The occupationally exposed, such as farmers, orchardists, field-
workers, applicators, swampers, flaggers, mixers and femulators have
traditionally accounted for many pesticide poisoning cases. These
58
-------
workers are often exposed to relatively high levels of pesticides when
actively engaged in working directly with the compounds (5).
In recent years use of the more persistent organochlorine
pesticides has declined, primarily due to their restricted use. Trends
are currently toward the usage of the less persistent compounds. Some
of these are of low toxicity and others are highly toxic. Unless these
more toxic compounds are used with great caution, there is a possibility
that the reduction in the older, more persistent chlorinated hydrocarbons
may lead to an increased incidence of poisoning (6). A preliminary
study of hospital records in Colorado indicates that during the last
five years organophosphate pesticides were responsible for nearly twice
as many intoxications as the organochlorine pesticides. Home and garden
usage of pesticides may also account for an increased number of pesticide
poisonings because of the increased interest in home vegetable gardening.
The objective of this study is to develop nationwide incidence
rates on the number of hospitalized acute pesticide poisoning cases among
the U.S. population. The incidence rate being the number of cases of
hospitalized acute pesticide poisonings for a given year. For example,
to be listed as an acute hospitalized pesticide poisoning case, the
first step requires that the patient see a doctor. The second step
requires that the physician be adequately familiar with pesticide
poisonings to diagnose the case. The third step requires the patient's
illness to be of such severity to require hospitalization.
Hospitalized acute pesticide poisonings in the United States are
treated at some organized hospital. Probably the most complete list of
hospitals is the list included in the American Hospital Association's
publication entitled, "The 1973 AHA Guide to the Health Care Field."
59
-------
This list includes both hospitals registered by the American Hospital
Association and osteopathic hospitals listed by the American Osteopathic
Hospital Association, U.S. Government hospitals, and long-term care
facilities. Any institution that meets requirements adopted by the
House of Delegates may be included in the list.
Hospitals accepted for registration in the American Hospital
Association must meet several requirements. One requirement states
/
that "a current and complete medical record shall be maintained by the
institution for each patient and shall be available for reference". The
requirements further state "the completed records in general shall
contain at least the following: the patient's identifying data and
consent forms, medical history, record of physical examination,
physician's progress notes, operative notes, nurse's notes, routine
x-ray and laboratory reports, doctor's orders, and final diagnosis". (7)
Although all member hospitals must maintain the necessary records, there
may be a wide range in completeness of hospital records on individual
cases.
Historically, a nationwide study to determine the number of
hospitalized acute pesticide poisoning cases has never been completed.
Because of the lack of these data we do not currently have nationwide
morbidity figures. This study of acute pesticide poisonings will yield
valuable information on the kinds of pesticides involved, epidemiolog-
ical patterns, place and person characteristics of exposure, and patterns
of treatment.
From a list of the general hospitals in the United States, a
sample will be selected according to the sampling scheme described
below. Each hospital represents a cluster of cases, and once a
60
-------
hospital ±s selected the entire cluster is observed to count the
number of pesticide cases occurring within that cluster.
Each hospital selected will be visited and patient records
examined by field epidemiologists specifically trained to abstract the
desired information. The degree of completeness of the hospital
records surveyed in this study may have a great deal to do with the out-
come of the study. Ideally we would like complete data on time-person-
place relationships, pesticide involved, diagnosis, treatment, prognosis,
and related circumstances of the pesticide incident.
The sampling frame consists of approximately 7,000 general
hospitals — as defined by the American Hospital Association — in the
United States. In order to increase the precision of the estimates of
interest, the population of general hospitals have been stratified
according to the pesticide usage in their respective areas into one of
two strata: low pesticide usage, and high pesticide usage.
Thus, each general hospital — that is, a potential sampling
unit — can be classified according to pesticide usage levels (geographic
area), state, and pesticide study center (Colorado, Iowa, and South
Carolina). This hierarchial classification scheme then constitutes
what is known as the frame; it is from this sampling frame that the
study sample will be selected.
The general hospitals were stratified by the recorded number of
admissions for the 1973 calendar year, as reported by the American
Hospital Association. The stratification plan is also by Center and
State.
The stratum boundaries, i.e., A.. , A?, ..., A , and the allocation
J_ ff * ID
of the number of hospitals sampled within each area were determined on
61
-------
the basis of the actual distribution of admission rates for the
hospitals included in the sampling frame. The allocation of the sample
to each stratum was constructed so that each stratum had at least some
limiting lower sampling rate.
The estimate for the state of Colorado can be computed as
follows:
Let y. = total hospitalized acute pesticide poisoning cases per
year in the i stratum of the low usage area in Colorado
XL
i = total admissions/year for all general hospitals in the
i stratum of the low usage area of Colorado.
x. = total admissions/year for the sampled hospitals in the
i stratum of the Low usage area of Colorado.
One estimate of the total number of hospitalized acute poisoning
cases for the i stratum in the low usage area of Colorado is then
X^ L
i
The estimate for the low usage area is
YL - m AI
Y " E YT
i=l 1
The estimate for the high usage area follows the same format as above.
The estimate for Colorado would then be given by
A AT AYJ
Y = TT + YH
The estimate for other regions then follow from these subregions.
The population is composed of hospitals varying widely in size.
62
-------
The principal variable to be measured is closely related to the size
of the hospitals. A good measure of size, namely the number of admissions,
is available for setting up the strata.
Nonresponse refers to the failure to measure some of the units in
the sample. With continuous data, any sizable proportion of nonresponse
usually makes it impossible to assign useful confidence limits to the
sample results. Nonresponse in this study is expected to fall into one
of the following types:
1. Inability to answer due to change in hospital codes.
2. Inavailability of hospital administrator or record librarian.
3. Hard core administrators who refuse admission to hospital
records due to confidentiality.
A problem that may occur infrequently is non-response due to
inadequate coding of hospital records. Although the majority of
hospitals use the PAS, ICDA, or H-ICDA codes, occasionally a hospital
uses a "home designed" code for records that make the records irretriev-
able.
Quality Control
In order to check on the quality of the survey work performed by
the field epidemiologists, a 5% resample will be completed on the total
number of hospitals surveyed. This will check the thoroughness of
the field epidemiologists in abstracting the patient records. The need
for quality control will also be lessened through more involved training
of the field epidemiologists.
Consequently, the training consisted of three phases: (1) a
workship training course; (2) an initial field trial; and (3) a second
training course. The second training course will serve to identify
63
-------
.and moderate some of the problems in the execution of the field trial.
Further, as a means of controlling the quality of the data,
selected staff will be trained to edit, as well as to code, the completed
data sheet.
Degree of Precision Desired
Using notation presented above, the estimate of the total number
.of acute pesticide poisonings can be written in the form
50 V "
Y = T F Y
11
i-1 J-l J
where Y. . is the estimated total number of hospitalized acute pesti-
cide poisonings in 'the jth usage level in the ith state and n. equals
1 or 2 depending on the state; that is,
viih
Y.. = E -=J£ X...
ijh
where y..,, x. ., , and X.., have been defined in the above example.
ijh ijh ijh
If n. ., and N ., denote the sample and population, respectively,
number of hospitals in the hth stratum of the jth usage level in the
/>
ith state, then the variance of the estimate Y is approximately
50 n. N. ., (N ., - n ,)
Var(Y) = E E E -^-^ — ^ - i12- S2 where S2 is the approximate
i=l j=l nijh dijh dijh
variance of Y..: S2 = S2 + R2 S2 - 2R...p..,S S
lj dijh ^ijh ^h xijh «h ijh ^ijh xijh
With respect to the above formula, R denotes the true population ratio
TT
•$, p denotes the correlation coefficient between X and Y, and S2
x y
and S2 denote the population variances of Y and X, respectively.
A
64
-------
Some basic premises of the study on acute pesticide poisonings are
that acute pesticide poisonings do not occur randomly but that they
occur in patterns which reflect the interrelationships of the underlying
causes. In conjunction with this basic premise, we know that knowledge
•
of the patterns of acute pesticide poisonings has value in prediction of
future acute poisoning cases and also provides an important basis for
devising methods of control and prevention of acute pesticide poisonings.
The occurrence of acute pesticide poisonings by age may be an impor-
tant factor in prevention of future cases. The relationship of differ-
ence in age distribution is necessary before other differences can be
taken into account. The age data of acute pesticide poisonings in
this study will be broken down into age groups on a five to ten year
basis such as 0-4, 5-9, 10-19, 20-29, etc. These data will then be
used as a basis for other data analysis.
The occurrence of acute pesticide poisonings by sex is an easily
ascertained characteristic. The simplest method of describing this
relationship is to depict the ratio of acute pesticide poisoning cases
in males to cases in females. These can also be age adjusted.
Racial and ethnic origin may also be used to adequately describe
the variations in the number of cases hospitalized for acute pesticide
poisonings.
Several acquired attributes of the person hospitalized for acute
pesticide poisonings will be collected in the study.
Occupation of the person hospitalized with pesticide poisoning is
very important. Studies in Texas suggest that loaders are much more
apt to be poisoned than spray pilots. This is the type of information
that will be gathered on a national basis.
Place relationships to acute pesticide poisonings are necessary to
65
-------
describe the spatial distribution of population and poisonings in terms
of state, EPA regions and national levels. Analyses of acute pesticide
poisonings by place will raise important general questions—are the
number of acute pesticide poisonings due to heavier usage, characteristics
of the physical environment, or due to the characteristics of those who
work with pesticides in the areas.
Urban-rural differences: Since the hospitals have been selected
to represent both those hospitals with large and low admission rates as
well as those from high and low use areas, there will be data to deter-
mine urban-rural differences, and variations between high and low use
areas. In the United States census, the population is classified by
residence as urban, rural-farm, and rural non-farm according to land use
and population density. The hospitals in this study also serve rural
and urban areas. Therefore, it is anticipated that a pattern of acute
pesticide poisonings can be developed to depict their occurrence in
urban and rural settings in both high and low usage areas.
Patterns of acute pesticide poisonings in time will also be con-
sidered. Time can be divided into units varying from minutes to hours
to seasons to years, decades, etc. In acute pesticide poisonings,
minutes and hours are important in determining length of exposure prior
to onset of symptoms and hospitalization of the case.
The frequency of the acute pesticide episode will also vary with
season and results from the study will be depicted to emphasize the
link between the activity of pesticide usage and the occurrence of
pesticide poisonings. We do not expect to be able to determine changes
in the incidence of acute pesticide poisonings for secular or long term
trends in acute pesticide poisoning incidence.
66
-------
Those properties which describe the pesticide involved in the acute
pesticide poisoning will be collected in detail. This will include
toxicity of the compound, type of formulation, carrier, how the compound
was used and related data. On the basis of such evidence pesticides can
be ranked according to their frequency of involvement in acute pesticide
poisoning episodes. In this gradient of involvement, parathion might be
used to illustrate near maximal involvement, and malathion to illustrate
low involvement. These compounds can then be compared with their toxicity
and usage pattern to determine their importance in the pattern of acute
pesticide poisoning epidemiology.
Results of all of the above data can then be used by EPA for future
development in the registration and enforcement processes.
Summary of the data will contain, for example, a cross-tabulation of
the number of acute hospitalized pesticide poisonings against such epidemio-
logical variables as age, sex, occupation, race, place, time of day,
season, pesticide formulation, diagnosis, treatment, prognosis and outcome.
Associated statistical tests, such as multi-dimensional chi square contingen-
cy tests, will also be presented.
The results of this study will give us a true picture of the number
of cases hospitalized by pesticide poisonings. These data will be useful
in developing educational programs to minimize poisonings, to aid in pes-
ticide regulatory decisions and to delineate areas that need further study.
67
-------
References
1. Anderson, M. L., L. A. Fiedler and W. Williams. Proceedings of the
Training Course: Pesticides and Public Health (Advanced). U.S.
Environmental Protection Agency, Pesticide Office, Division of
Pesticide Community Studies. Chamblee, Georgia. 1971.
2. Hayes, Wayland J. Epidemiology of Pesticides Proceedings of Short
Course in Occupational Health Aspects of Pesticides. University
of Oklahoma. Norman, Oklahoma. 1964.
3. Occupational Disease in California Attributed to Pesticides and
Other Agricultural Chemicals. State of California, Department of
Public Health, Bureau of Occupational Health and Environmental
Epidemiology. 1970.
4. Hayes, Wayland, Jr. Pesticides and Human Toxicity. In Annals of
the New York Academy of Sciences (H.F. Kraybill, Ed.). Vol. 160,
art. 1, pp. 40-54, 1969.
5. Reich, G. A., G. L. Gallaher, and J. S. Wiseman. Characteristics of
Pesticide Poisoning in South Texas. Texas Medicine. Vol. 64, No. 9,
pp. 56-58. 1968.
6. Smith, D. A. and J. S. Wiseman. Pesticide Poisoning. Texas
Medicine. Vol. 67, No. 2, pp. 56-59. 1971.
7. A. H. A. Guide to Health Care Facilities. American Hospital
Association. Chicago, Illinois. 1973.
68
-------
SURVEY OF CHEMICAL SPILLS IN HIGHWAY AND RAIL TRANSPORT
Edward M. Svetich
Scott County Health Department
Davenport, Iowa
Abstract
In the United States during the 3 year period from January 1971
through December 1973, over 12,000 incident reports of unintentional
release of hazardous materials were made to the United States Depart-
ment of Transportation. This system of reporting hazardous materials
incidents was established to comply with the Hazardous Materials Trans-
portation Control Act of 1970.
The statistics compiled during this period indicate that many of
the incidents reported occur while such materials are being transported
by highway or rail carriers. It is assumed that only a small percentage
of chemical releases are reported and as a result, there is no sound
evidence as to just how large the problem is.
Utilizing United States Department of Transportation statistics,
this paper will survey the incidents reported.
Hazardous materials transportation incidents have caused deaths,
injuries and property damage. Much of this could have been avoided or
minimized had the causes of previous incidents been identified and appro-
priate preventative measures taken. With this thought in mind, a nation-
wide intermodal system for the reporting of hazardous materials incidents
was established to provide the United States Department of Transportation
with the factual data necessary to comply with the Hazardous Materials
Transportation Control Act of 1970.
This system of requiring reporting of hazardous materials incidents
is two-fold in that an immediate telephone notice is required under cer-
tain conditions, arid a detailed written report is required whenever there
is any unintentional release of a hazardous material during transporta-
tion ojr temporary storage related to transportation.
The success of this program depends greatly on the quality of the
information submitted on the report. Generally, most of the required
information is available at the time of the incident, but since leaking
and damaged containers are destroyed, and spills are cleaned up, some
investigation is often necessary in order to obtain all of the facts.
The Chemical Transportation Emergency Center, or CHEMTREC for short,
is a public service provided by the Manufacturing Chemists Association
at its offices in Washington, D.C. CHEMTREC provides immediate advice
for those at the scene of emergencies, then promptly contacts the shipper
69
-------
of the chemicals involved for more detailed assistance and appropriate
follow-up.
CHEMTREC operates around the clock, seven days a week to receive
direct-dial toll-free calls from any point in the continental United
States through a wide area telephone service (WATS) number, 800-424-
9300. As circumstances warrant, the National Transportation Safety
Board or appropriate offices of other agencies may be notified.
HAZARDOUS MATERIAL INCIDENTS 1971-1973
During a three year period from January 1971 through December 1973,
725 carriers submitted 12,600 incident reports citing unintentional
release of hazardous materials. Reporting carriers are categorized as
highway, rail, water and air.
Highway carriers accounted for 644 reports or 89% of the total 725
reporting carriers. These carriers submitted 11,400 reports or 90% of
the total reported.
Rail carriers accounted for 45 reports or 6% of the total number of
carriers reporting. Rail carriers submitted 1,100 reports or 9% of the
total reports submitted.
Water and air carriers submitted 35 (1/4 of 1% of the total submit-
ted) and 85 reports (1/2 of 1% of the total submitted) respectively
during this same time period.
HIGHWAY CARRIERS
Looking a little closer at the 11,000 plus reports submitted by
highway carriers, we find that 8,500 of the reports involved the unin-
tentional release of hazardous materials from a package (other than a
tank). Breaking this figure down further we see that - 4,000 involved
paint and paint related commodities - 2,000 involved batteries and electro-
lyte acid and - 1,000 involved corrosive cleaning compounds.
2,500 of the reports submitted by highway carriers involved unintent-
ional release of hazardous materials from tank trucks or tank trailers.
The breakdown is as follows: - 2,000 involved gasoline and related pro-
ducts - 250 involved various acids and - 200 involved low pressure gases.
RAIL CARRIERS
Rail carriers submitted 1,000 plus reports, of which 700 involved
unintentional release of hazardous materials from tank cars. The most
often named materials in these reports were low pressure gases, sulfuric
acid, anhydrous ammonia and liquid caustic soda. Over 400 of the reports
involved the unintentional release of hazardous materials from packages.
Ammonium nitrate fertilizers and mixtures were named most often in these
incidents.
70
-------
PACKAGES - CONTAINERS AND FAILURE CAUSES
Of the 3,200 incident reports in which tank trucks and tank cars
were the container, 1,600 cited "external puncture" as the packaging
failure cause. This was generally due to collisions or derailments.
A large percentage of spills from tank trucks were due to overfills,
with a lesser portion happening when hoses were disconnected or when
hoses burst during loading or unloading. As to tank cars, many spills
happen merely because the dome cover wasn't properly closed.
Container integrity, including valves and other component parts,
was involved in a comparatively small percentage of these tank car and
tank truck incidents.
A total of 9,300 incidents involving packages from which hazardous
materials escaped were reported. One third (3,000) of these reports
indicated that metal drums or pails were the packages. Data on drums
and pails was somewhat varied, and 1,500 gave "specs", and 1,500 merely
said drum or pail. There were 1,400 reports that indicated fiberboard
boxes with 250 reports giving the "spec" such as 12b, and 1,150 merely
said fiberbox. Over 50% of these 9,300 reports indicated the cause of
the failure of the container to be either "external puncture", "dropped
in handling" or "damaged by other freight". The latter category usually
indicates improper blocking and bracing.
"Container integrity" types of failures, such as weld and chime
failures, loose caps on inner bottles and faulty closures on fiber boxes
accounted for 30% of the 9,300 reports. Loose caps on inner bottles are
becoming more of a problem as plastic bottles become more popular.
LOSS
The 12,600 incidents on unintentional release of hazardous materials
reported in the three year period from January 1971 through December 1973
were directly related to 59 fatalities and 982 injuries.
A total of 63% of these reports included a property damage figure.
A total of 1,100 reports out of 2,200 reports (50%) in 1971 included a
property damage figure; 2,640 reports out of 4,400 (60%) in 1972 included
such a figure; and 4,200 reports out of the 6,000 reports in 1973 (70%)
included a property damage report.
INCIDENT REPORTS FROM STATE OF IOWA
All 133 incidents of unintentional release of hazardous materials
reported from the State of Iowa during the period of January 1971 through
December 1973 originated with highway and rail carriers. No incidents
were reported from air or water carriers. This fact probably isn't too
notable, however, because of Iowa's lack of what might be considered busy
airports or barge or water terminals which would handle large quantities
of hazardous materials.
71
-------
Being primarily agricultural in nature, most of Iowa is served
by rail and highway transport in order to get agricultural chemicals,
petroleum products, etc. to those rural areas being supplied. At the
same time, Iowa is the mid point in transportation both east and west
across the country and as such is subject to a large volume of traffic
both on its highways and rail lines.
Although percentages were not available to me from other states
reporting incidents of release of hazardous chemicals, I think that by
looking at Iowa's statistics, we can get.a general idea of the situation
that exists with most incidents reported.
Corrosives and flammable liquids account for the majority of reported
incidents in this three year period. This can possibly be explained
because these materials are shipped in larger quantities for longer
distances and hence are subject to more "on the road" hazards and because
the danger involved in an incident is readily apparent when a release is
discovered. Other agencies or emergency services would be necessary to
prevent injuries because of the known hazard with such materials, with
the result that there is a greater chance that such unintentional releases
would be reported.
One thing is obvious, however. There are certainly many, many more
carriers transporting hazardous materials who are not reporting incidents
of unintentional release of these materials. There are probably several
thousand carriers transporting hazardous materials, and yet between
January 1971 and December 1973 only 725 carriers reported 12,600 incidents.
Simple mathematics means that these 725 carriers averaged 17.4 incidents
each. Hopefully, this isn't the case for each carrier, but if not,
then some of the reporting carriers must be responsible for a totally
unacceptable number of reported incidents. One such incident is unaccept-
able—17.4 incidents is disastrous as well as catastrophic.
If the figures are correct and estimating 3,000 carriers who handle
hazardous materials, then one out of every four carriers is going to have
a release of hazardous material before the cargo is unloaded.
There is no easy solution. The reasoning behind the decision not
to report an incident of this type escapes me. Whether it is fear of
federal controls or lack of common sense, the result is the same; too
many people are being subjected to the unnecessary exposure to hazardous
materials with tragic results both now and in the future.
72
-------
Chemical Transportation Incidents Reported in Iowa
1971-1973
TOTAL REPORTS
Corrosives
Flammable Liquids
Non-Flammable Gas
Class B Poison
Oxidizing Material
Total '71- '73
133
43%
42%
7%
3%
2%
1971
22
59%
27%
9%
—
—
1972
33
33%
52%
3%
6%
3%
1973
78
42%
44%
6%
3%
3%
1974
85
38%
46%
7%
5%
1%
73
-------
References
1. Manufacturing Chemists Association, 1975. CHEMTREC Chemical
Transportation Emergency Center. Manufacturing Chemists
Association booklet, Washington, D.C.
2. U. S. Department of Transportation. 1975. Computer Readout
Memo on Hazardous Materials Incidents. U.S. Department of
Transportation 1975. 5 pp.
3. U. S. Department of Transportation, 1975. Indicators of
Hazardous Materials Shipment Violations. U. S. Department
of Transportation, leaflet, 2 pp.
4. U. S. Department of Transportation, 1975. Preliminary Statistics:
Hazardous Materials Incident Reports. U. S. Department of
Transportation, leaflet, March, 1975. 2 pp.
5. U. S. Department of Transportation, 1975. Statistical Fact Sheet:
Hazardous Materials Incident Reports. U.S. Department of
Transportation, leaflet, March, 1975. 2 pp.
6. Zercher, John C. 1971. Chemical Transportation Emergency
Information. Manufacturing Chemists Association publication
September, 1971. Washington, D.C. 5 pp.
74
-------
ARSENIC: POTENTIAL HAZARDS OF ENVIRONMENTAL EXPOSURE*
Anna S. Hammons, Eric B. Lewis
Helen M. Braunstein, and James Edward Huff
Biomedical Studies Group
Biomedical Sciences Section
Information Center Complex/Information Division
Oak Ridge National Laboratory
Oak Ridge, TN 37830
Summary
Arsenic occurs naturally in the environment in low concentrations
and is distributed widely via water leaching, plant uptake, and
volcanic activity. Industrially produced trivalent arsenic—the
most toxic form—also contributes to environmental distribution of
arsenic.
Arsenic compounds are used in glass, pigment, and bronze-plating
industries; as pesticides, animal hide and wood preservatives, growth
stimulants in poultry and swine; and in certain therapeutic agents.
Most arsenic produced is recovered as a by-product of lead, copper, and
gold extraction.
Arsenic is released directly into the environment through production
and use of arsenic compounds. Inorganic arsenic levels in water in some
parts of the world (for example, Formosa and Argentina) have been found
to be higher than elsewhere. Arsenic can be present in food as a con-
taminant or as pesticide residues.
Because arsenic does not appear to progressively concentrate in
the food chain the greater potential environmental hazard is from
contaminated drinking water supplies. Other hazards include accidental
ingestion of readily available household arsenic preparations by
children and ingestion by domestic animals of forage contaminated by
arsenical defoliants.
Elemental arsenic is generally considered harmless when ingested
because absorption is low and therefore most is eliminated unchanged.
Most compounds of arsenic, however, are extremely toxic. White arsenic
or arsenic trioxide—commercially the most important form of arsenic—
is historically the most implicated of the poisons used for criminal
*Work supported jointly by the Solid and Hazardous Waste Research
Laboratory, U.S. Environmental Protection Agency; the Toxicology
Information Program, National Library of Medicine; and Division of
Biological and Environmental Research, U.S. Energy Research and
Development Administration; under contract with the Oak Ridge National
Laboratory operated by Union Carbide Corporation Nuclear Division for
the U.S. Energy Research and Development Administration under
Contract No. W-7405-eng-26.
75
-------
purposes. The pentavalent organic arsenicals are considerably less
poisonous than the inorganic trivalent forms. The gas—arsine—is
one of the most toxic forms of arsenic; however, environmental exposure
is unlikely. The primary mechanism of trivalent arsenic toxicity is
enzyme inactivation via combination with sulfhydryl groups. Arsine
combines with hemoglobin to form a powerful hemolytic poison. Heavy
chronic arsenic exposure is associated with skin cancer, but the role
of arsenic as a carcinogen is controversial. Although all tissue
contain low levels of arsenic, this metal has no known nutritional value.
Introduction
Arsenic is historically notorious as a poison used for criminal
purposes. Even though arsenic is ubiquitous in nature and has been used
for centuries, the mechanism of action and effects of chronic low-level
arsenic exposure in living organisms are not completely understood.
However, as with any material potentially hazardous to human health,
unnecessary dissemination should be avoided and care should be exercised
in the use and disposal of such compounds.
Occurrence and Sources
Arsenic occurs naturally in the environment with deposits of
complex base-metal ores primarily valuable for copper, gold, and silver.
Estimated background arsenic concentrations in the earth's crust range
from 0.1 to 40 ppm; sea water averages approximately 0.003 ppm arsenic;
uncontaminated rivers contain an average of 0.0004 ppm; and soils contain
6 ppm (Bowen, 1966). Rainwater has been reported to contain as much as
14,000 ppm arsenic (Smith, 1972). McCabe et al. (1970) determined that
only 2 of 969 United States public water supply systems exceeded the
mandatory U.S. Public Health Service limit of 0.01 mg/1 (Federal
Register, 1975). Arsenic accumulates in soils and sediments; for
example, sediments in a New York lake contained 60 to 70 ppm whereas
the surrounding water contained only 0.004 to 0.043 ppm (Lis and
Hopke, 1973). A survey by Louria et al. (1972) determined arsenic in
air ranges from undetectable in rural areas up to 0.09 yg/m and to
0.75 yg/m-*—the nation's maximum at the time of the survey in El Paso,
Texas.
Production and use of arsenic compounds result in additional release
of arsenic into the environment. Phosphate rock used to make fertilizers
and detergents contains some arsenic and therefore may eventually con-
taminate both rural and urban waterways (Environment, 1971). Up to 36
ppm arsenic has been found in laundry products. Certain fungi, yeasts,
and bacteria mobilize arsenic in soils and sediments by methylation to
gaseous derivatives of arsine (Ferguson and Gavis, 1972) which volatize
and enter the atmosphere. Arsenic also enters the environment in
smelter stack gas, in emissions from the burning of fossil fuels, and
from leaching of exposed wastes from mining and ore processing activities
(Ferguson and Gavis, 1972).
Because treatment facilities are insufficient, common disposal of
arsenical wastes is by burial which could represent potential hazards.
Over 45,000 metric tons of arsenic wastes are stockpiled in various areas
76
-------
of the United States awaiting proper treatment (Ottinger et al., 1973).
Several incidences of poisoning as a result of arsenic burial are
documented by the United States Environmental Protection Agency (1974).
For example, several persons required hospitalization after drinking water
from a Minnesota well drilled near an arsenic burial 30 years before.
A commercial laboratory in Pennsylvania contaminated groundwater by
disposing of arsenic wastes by surface storage within the plant area.
Uses
Surprisingly, the oldest uses of arsenic were medicinal; arsenicals
were used in the treatment of nutritional disturbances, arthritis, asthma,
and skin diseases (Junkins, 1963). Arsenic was used in medicines in the
Orient as long ago as several thousand years. However, medicinal uses
of arsenicals have decreased substantially with the exception of use
against amebic dysentery and the late neurological stages of African
trypanosomiasis (Doak and Freedman, 1970). Arsenic was used most fre-
quently as a drug in a tonic known as Fowler's solution (potassium
arsenite). Before the advent of antibiotics, syphilis was treated with
arsenicals, the earliest of which were arsphenamine and neoarsphenamine.
These compounds are oxidatively cleaved in the body to oxophenarsine,
which later displaced arsphenamine and neoarsphenamine for the treatment
of syphilis (Osol and Pratt, 1973).
Years ago mountaineers in Styria and in the Alps of Switzerland
and the Tyrol could be observed eating relatively large quantities of
native arsenic, presumably elemental arsenic, believing that it in-
creased endurance, appetite, and strength, and cleared the complexion
(Schroeder and Balassa, 1966). The apparent tolerance to arsenic
developed by these mountaineers may be explained on the basis of low
solubility and poor absorbability of the form ingested (Osol and Pratt,
1973). Conversely, no tolerance has been observed following parenteral
administration of arsenic compounds.
Currently, arsenic compounds are used mainly in manufacturing
insecticides, weed killers, fungicides, antifouling paints, and as a
wood preservative. The first pesticide was copper acetoarsenite
or Paris green which was used to control the Colorado potato beetle
(Frost, 1967). Lesser amounts of arsenic are used in the manufacture
of special glasses and enamels and as an alloying constituent (Hamilton
and Hardy, 1974). Arsenicals are also used as a food additive to stimu-
late growth in poultry, sheep, and swine (Junkins, 1963). Specific
arsenic compounds and past and present uses are listed in Tables 1, 2,
and 3.
Toxicity
Arsenic can be absorbed via inhalation, ingestion, or contact with
the skin (Sullivan, 1969). Absorbed arsenic is excreted in urine, feces,
skin, hair, nails, and possibly a trace from the lungs. Arsenite has
a strong affinity for kidney, liver, hair, nails and skin (Schroeder and
Balassa, 1966). Urinary excretion appears to be the most important route
of elimination of pentavalent arsenic compounds, while intestinal ex-
cretion is more important for trivalent arsenicals.
77
-------
Table 1. MEDICINAL USES OF ARSENIC COMPOUNDS
Compound
Uses
Arsenic triodide
OO
Arsenic trioxide
Arsenious acid solution
Cacodylic acid
Chloroarsenol
Methanearsenic acid
Oxyophenarsine HC1
Arsphenamine
Neoarsphenamine
Potassium arsenite solution
(Fowlers solution)
Formerly internally for chronic dermatitides
(including syphilitic), various chronic
arthroses, and certain cases of lymphadenitis,
and topically as stimulant in dermatitis.
Formerly for dermatitides, chronic
bronchitis, asthma, anemia, topically for
skin neoplasms.
Has been used for blood dyscrasias.
Formerly for various skin diseases.
Formerly as tonic.
Has been used in anemia, leukemia, and psoriasis.
Formerly for syphilis.
Has been used in chronic myelogenous leukemia,
chronic dermatitides.
Source:
Modified from Sullivan (1969)*
-------
Table 2. VETERINARY USES OF ARSENIC COMPOUNDS
Compound
Uses
Arsenious acid solution
Arsenic trioxide
Arsonacetic acid
Lead arsenate
Potassium arsenite solution
(Fowlers solution)
Sodium arsenite
In certain blood diseases, anemias, and skin
disorders.
For pulmonary emphysema, chronic coughs,
anemia, general debility, chronic non-
parasitic skin disease.
Disodium salt used to treat anaplasmosis
(babesiasis); as general stimulant in nervous
disease; for eclampsia of bitches, and with
adjuncts in chronic eczema and follicular
mange.
Has been reported useful for tapeworms of
cattle, goats, and sheep.
For pulmonary emphysema, chronic coughs, anemia,
general debility, chronic nonparasitic skin
diseases.
Used topically against ticks of ruminants.
Source:
Modified from Sullivan (1969),
-------
Table 3. USES OF ARSENIC COMPOUNDS OTHER THAN
MEDICINAL OR VETERINARY USES
Compound
Uses
Arsenic add
Arsenic disulflde
Arsenic henriselenlde
Arsenic pentoxide
Arsenic trichloride
Arsenic trfoxlde
(white arsenic)
Arsenic trlsulflde
Arslne
Cacodyllc add
Calcium arsenate
Cuprlc acetoarsenlte
(Paris green)
In the manufacture of arsenates.
As pigment 1n painting, 1n fireworks as blue
fire and to give an Intense white flame; to
manufacture shot; for calico printing and
dyeing, tanning and depilating hides.
In manufacture of glass.
In manufacture of colored glass, 1n adheslves
for metals; 1n wood preservatives; 1n weed
control; as fungicide.
In the ceramic Industry; 1n the synthesis of
chlorine-containing arsenicals (I.e., chloro
derivatives of arsenic).
Arsenic trloxlde 1s the primary material for
all arsenic compounds. Used 1n the manufac-
ture of glass, Paris green, enamels, weed
killers, textile mordants, metallic arsenic;
for preserving hides, killing rodents. Insects;
1n sheep dips and weed killers.
In manufacture of glass, particularly Infrared
transmitting glass; 1n manufacture of oil
cloth, linoleum; In electrical semiconductors,
photoconductors; as pigment; for depilating
hides, 1n pyrotechnics.
For chemical analyses.
As herbicide.
As Insecticide, particularly against Insects
destructive to plant; as mollusdclde.
As Insecticide, wood preservative; as pigment,
particularly for ships and submarines.
80
-------
Table 3. USES OF ARSENIC COMPOUNDS OTHER THAN
MEDICINAL OR VETERINARY USES (Cont'd)
Compound
Uses
Cuprlc arsenlte
(Scheele's green)
Disodium methyl arsenate
Lead arsenate
Potassium arsenate
Potassium arsenite
Methanearsenic acid
Sodium arsenate dibasic
Sodium arsenlte
Zinc arsenate
As pigment, wood preservative, Insecticide.
fungicide, rodentldde.
As weedkiller (crabgrass); for some control
over silver or goose grass, knotweed, and
chickweed.
As constituent of various Insecticides for
larvae of gypsy moth, boll weevil, etc.
In textile, tanning, and paper Industries.
In insectlcidal formulations (especially
fly paper).
In manufacture of mirrors to reduce the silver
salt to metallic silver.
Disodium salt, as herbicide.
The technical grade, about 98 percent pure,
is used in dyeing with Turkey-red oil and
in printing fabrics.
The technical grade, 90 to 95 percent pure,
is used in manufacture of arsenical soap for
use on skin, for treating vines against
certain scale disease, as Insecticide
(especially for termites).
As insecticide.
Source:
Modified from Sullivan (1969).
81
-------
Arsenic, a metalloid, forms alloys with metals but also reacts
with carbon, hydrogen, and oxygen (Frost, 1967). Kinetically
stable bonds are formed between arsenic and sulfur and carbon in
organic compounds (Ferguson and Gavis, 1972). The primary mode of
arsenic toxicity is generally explained as enzyme inactivation
through a reaction with sulfhydryl groups of cysteine in proteins
(Dreisbach, 1974; Ferguson and Gavis, 1972).
One of the most toxic compounds of arsenic is the gas arsine—
the most powerful hemolytic poison found in industry (Hamilton
and Hardy, 1974). Arsine poisoning usually results in renal failure
(Teitelbaum and Kier, 1969). A single exposure to 100 ppm arsine
may be sufficient to cause death or serious illness; however, occupational
exposure to arsine can be controlled and it is unlikely that one would
be environmentally exposed to toxic levels (Smith, 1972).
Trivalent arsenic, more toxic than pentavalent arsenic, produces a
more dramatic immediate physiological response. As little as 0.2 to 0.3
gm of arsenic trioxide or "white arsenic" can be fatal to an adult
(Gleason et al., 1969). Trivalent arsenicals are reno- and hepatotoxic
(Schroeder and Balassa, 1966). The mortality in acute poisoning is 50
to 75 percent, death usually occurring in 48 hours. Lethal doses of
several arsenic compounds are listed in Table 4. Symptoms of acute
and chronic arsenic poisoning are listed in Table 5. Acute symptoms are
mainly gastrointestinal, while chronic exposure also involves the
nervous system, the liver and kidneys, and the skin.
A causal relationship has been shown between skin cancer and
heavy exposure to inorganic arsenic in drugs., in drinking water with a
high arsenic content, and in the occupational environment (World Health
Organization, 1973). Controversy surrounds the apparent increased risk
of other types of cancer in certain smelter workers chronically exposed
to high levels of inhaled arsenic trioxide. Industrial reports to the
Occupational Safety and Health Administration showed lung and lymphatic
cancer rates several times higher in persons employed in two pesticide
plants than would normally be expected in the general population (Chemical
and Engineering News, 1974). Cancer has not been induced in laboratory
animals from arsenic exposure and until this is accomplished doubt will
remain as to whether these obviously higher risks can be attributed to
arsenic exposure. Negative results from several animal experiments
are shown in Table 6. (United States Environmental Protection Agency,
1971). Two of the experiments actually show a decrease in tumor
incidence with oral exposure to arsenic.
The most common effects in persons occupationally exposed to arsenic
are dermatitis, possibly even ulceration of the skin, and perforation
of the nasal septum (Hamilton and Hardy, 1974; Smith, 1972).
Although the history of arsenic as a poison is exaggerated, several
incidences of accidental mass arsenic poisonings have been reported.
The last reasonably well documented account of an epidemic of arsenic
poisoning occurred in England and Wales in the latter part of 1900
(Satterlee, 1960). Poisoning was traced to arsenic contaminated beer.
82
-------
table 4. TOXICITY OF SEVERAL ARSENIC COMPOUNDS
OD
u>
Compound
Arsenic acid
Arsenic pentoxide
Arsenic trioxide
(white arsenic)
AS2°3
Arsine
Cacodylic acid
(CH3) As(0) OH
Calcium arsenate
Ca_ (AsO. )
Species
Rabbits
Rat
Rabbits
Human
Human
Dog
Rat
Human
Dog
Various
Rat
Dose
8 mg/kg
Oral-48 to 100 mg/kg
i.v.-8 mg/kg
Oral-70 to 180 mg
0.0 to 0.5 g
Oral-30 to 70 mg/kg
Oral-138 mg/kg
250 ppm
s.c. 1.0 g/k
35 to 100 mg/kg
Oral-298 mg/kg
Effect
50
LD50
Lethal
"V
Lethal
LD50
Lethal in
30 minutes
Lethal
LD50
Reference
Sullivan (1969).
Farm Chemicals Handbood (1975).
Sullivan (1969).
U.S. EPA (1971).
Sullivan (1969).
U.S. EPA (1971).
U.S. EPA (1971).
U.S. EPA (1971).
Sullivan (1969).
Sullivan (1969).
U.S. EPA (1971).
-------
Table 4. TOXICITY OF SEVERAL ARSENIC COMPOUNDS (Cont'd)
oo
Compound
Copper acetonarsenite
(Paris Green)
(CH3COO) 2Cu. 3Cu(As02) 2
Disodium methyl arsenate
CH3As03Na2 - 6 H20
Lead arsenate
PbHAs04
Potassium arsenite
KAs00.HA 00
z s /
Sodium arsenite
NaAs02
Species
Rat
Mammals
Rat
Rat
Human
Rat
Guinea Pig
Dose
Oral-22 mg/kg
Oral-50 mg/Kilo
Oral-80 mg/kg
Oral-14 mg/kg
Oral -325 mg
Oral -<50 mg/kg
Oral -14 to 30 mg/kg
Effect
LD50
Test animals
tolerate well
above 50 mg/Kilo
body weight
LD50
L?50
Lethal
LD50
Lethal
Reference
Farm Chemicals Handbook
(1975)
Sullivan (1969)
Sullivan (1969)
Sullivan (1969)
U.S. EPA (1971)
U.S. EPA (1971)
Sullivan (1969)
-------
Table 5. SYMPTOMS OF ARSENIC POISONING
Acute
Chronic
oo
Feeling of throat constriction
Difficulty in swallowing
Epigastric discomfort
Violent abdominal pain
Vomiting
Watery diarrhea
Oligurlgu
Occasionally restlessness, vertigo,
muscle spasm, delirium, and
coma occur
Shock and death occur in
severe cases
Malaise and fatigue
Intermittent nausea
Vomiting
Diarrhea
Hyperp1gmentat1on
Scaling of the skin
Epithetiomas may develop years
later
Nervous manifestation marked by
paralysis, confusion, and anemia
Development of characteristic
streaks across fingernails
Polyneur1t1s
Altered hematopoiesis
Degeneration of liver and kidneys
-------
Table 6. CARCINOGENICITY IN MAMMALS EXPOSED TO ARSENIC COMPOUNDS
Agent
Species
Animals with tumors
Dose
Reference
oo
ON
Arsenic Mouse
trloxlde
Sodium Mouse
arsenlte
Rat
Rat
Potassium Human
arsenate
(Fowler's solution)
0/75
Possible decrease 1n
methylcholanthrene-
Induced skin tumors 1n
one strain of mouse
Significant decrease 1n
tumor Incidence
Significant decrease 1n
tumor Incidence
No tumors above control
Positive
0.0155 1n
drinking water
0.01X 1n drinking
water for 8 mos.
8.67 mg/1 for
life span
8.67 rng/1 for
life span
8.67 mg/1 In drinking
water for life span
0.80 nig/kg of diet
Baronl et al. (1963).
Mllner (1969).
Schroeder (1970).
Kanlsawat & Schroeder
(1967).
Source:
Modified from U.S. Environmental Protection Agency (1971).
-------
Table 7.
ARSENIC IN FOODS
(wet weight)
Food
Pg/g
Food
yg/g
Fish and Seafood
Shrimp, fresh frozen 1.50
Scallops, fresh 1.67
Haddock 2.17
Clams, fresh frozen 2.52
Oysters, frozen 2.70
Oysters, fresh 2.90
Conch, fresh 3.10
Conch, dried, whole 5.63
Kingfish 8.86
Range 2.17 to 8.86
Mean 3.45
Meats
Chicken breast
Egg lecithin
Pork kidney
Pork loin
Gelatin
Lamb chop
Pork liver, No. 1
Beef, stewing
Pork liver, No. 2
0.0
0.0
0.0a
0.06
0.19
0.35
1.07
1.30
1.40
Vegetables and Grains
Beets 0.0
Corn oil 0.0
Corn oil lecithin 0.0
Cottonseed oil 0.0
Soy lecithin 0.0
Turnip 0.0
Red pepper 0.06
Yellowpear tomatoes 0.10
Corn 0.11
Rice, U.S.A. 0.13
Rye, seed 0.16
Wheat, whole 0.17
Beet greens 0.24
Garlic, fresh 0.24
Cherry tomatoes 0.37
Rhubarb 0.48
Rice, Madagascar 0.48
Swiss Chard 0.56
Kellogg's Special K 0.66
Corn meal 0.78
Puffed rice 1.60
Mushrooms 2.90
Range 0.0 to 2.90
Mean 0.41
Range 0.0 to 1.40
Mean 0.49
87
-------
Table 7. ARSENIC IN .FOODS
(wet weight) (Cont |jd)
Food
pg/g
Food
yg/g
Fruits
Apple
Orange
Pear
Grapes, wild
0.0
0.0
0.0
0.17
Range 0.0 to 0.17
Mean 0.04
Miscellaneous
Coffee
Milk, dry skimmed
Sugar, granulated
Sugar, lump
Milk, evaporated
Butter, unsalted
Water, spring,
double deionized
Water, spring, tap
Cocoa, Hershey's
Tea
Salt, table
Salt, sea
Range 0.0 to 2.83
Mean
0.72
Note;
where 0.0 is reported, the specimen contained less than 0.02 wg/g wet
weight. The analytical method used was sensitive to 0.5 yg/specimen
of ash.
Source:
Modified from Schroeder and Balassa (1966).
88
-------
This conclusion has since been disputed and the presence of selenium is
suspected to at least have contributed to, if not caused, the poisonings
(Frost, 1967). Contaminated rice fed to children in two orphanages in
Indonesia caused mass acute poisoning in 1969; fortunately, all recovered
(Tjaij and Azia, 1971). Arsenic contaminated drinking water and foodstuffs
in Chile reportedly were the causes of endemic chronic poisoning of 457
patients during the period 1968 to 1971 (Zaldivar, 1974). Most of these
cases were children from 10 to 15 years old. Because of its availability
in household preparations arsenicals pose a potential hazard to children
via accidental ingestion. For example, two cases of fatal poisonings
from arsenic-containing weed killer and rat poison are described by
Petry and Rennert (1970).
Arsenicals have also been involved in poisoning domestic animals
grazing on forage previously sprayed with herbicides or insecticides
containing arsenic. For example, several feeder lambs in Arizona died
and many others became ill after grazing in an alfalfa pasture (Nelson
et al., 1971). Autopsy showed rather extensive damage to the gastroin-
testinal tract. As established later: 10 days before the animals were
released into the field, a spray plane, due to a broken hose, had acci-
dentally released a cotton defoliant containing arsenic acid over part
of the field.
The greatest potential hazard of environmental arsenic to the
general population is from ingestion of drinking water containing high
concentrations of arsenic (Ferguson and Gavis, 1972). Fortunately,
arsenic is apparently not concentrated along a food chain (Ball and
Hooper, 1966). Data on arsenic concentration by plants and animals is
contradictory. However, the more toxic trivalent compounds, which are
primarily excreted in the feces rather than the urine apparently
accumulate with prolonged exposure (Lourla, 1972). Arsenic can be present
in food as a natural contaminant or a residue of lead or calcium arsenate
used as insecticides, particularly on potatoes and fruit (World Health
Organization, 1973).
The most toxic arsenicals are well tolerated at levels which
supply 10 to 20 ppm arsenic in the diet; the least toxic arsenicals
are tolerated at levels up to at least 1,000 ppm in the diet (Frost,
1967). The average diet provides an arsenic intake of about 1,000
yg/day (Schroeder, 1970). Arsenic has no known nutritional role (Frost,
1967). All tissues contain some arsenic—marine invertebrates have
especially large amounts (Leatherland et al., 1973). Arsenic concentra-
tions in a variety of foods are listed in Table 7. Kingfish at 8.86
yg/g had the highest concentration of arsenic; while the lowest measured
levels were in fruits—less than 0.02 yg/g wet weight.
Conclusions
The literature on arsenic is controversial. The possibility of
interconversions between pentavalent and trivalent forms in the human
body as well as in the environment and the improbability of dealing
with "pure" forms of arsenic contribute to the difficulties in studying
the effects of arsenicals. When discussing the effects of arsenic care
89
-------
should be taken to distinguish between the pentavalent and the trivalent
forms. Pentavalent arsenic, the form usually found in food, is excreted
rapidly, and does not appear to accumulate in human tissues; whereas
trivalent arsenic, the principal form industrially produced, is highly
toxic and most investigators seem to agree that this form does accumulate
in mammalian tissues with prolonged exposure.
Current background arsenic levels in the environment apparently do
not have a detrimental effect on the general population or the ecosystem.
However, as evidenced by reports of accidental poisonings of humans and
of domestic animals, commercial arsenicals improperly handled can create
serious hazards. Unfortunately, as is the case with many environmental
trace contaminants, the full implication of chronic low level exposure
to arsenic is not understood. The possibility exists that sub-clinical
effects sometimes taken for granted or attributed to other causes are
actually the results of exposure to trace contaminants. The lack of
knowledge about the fate of arsenicals in soils and natural waters adds to
the difficulty in determining the impact of arsenic contamination on the
ecosystem.
on
-------
REFERENCES
74
1. Ball, R.C. and F. H. Hooper. 1966. Use of As-Tagged Sodium In a
Study of Effects of an Herbicide on Pond Ecology. In: Isotopes in
Weed Research. International Atomic Energy Agency, Vienna.
pp. 149-163.
2. Bowen, H.J.M. 1966. Trace Elements in Biochemistry. Academic
Press, New York. pp. 174-175.
3. Doak, G. 0. and L. D. Freedman. 1970. Arsenicals, Antimonials,
and Bismuthials. In: Medicinal Chemistry. 3rd ed., Burger, A.
(ed.). Wiley-Interscience, New York. pp. 610-625.
4. Dreisbach, R. H. 1974. Handbook of Poisoning: Diagnosis,
Treatment. 7th ed. Lange Medical Publications, Los Altos,
CA. pp. 194-197.
5. Environment. July 19, 1971. Trace Metals: Unknown, Unseen
Pollution Threat.
6. Farm Chemicals Handbook. 1972. Meister Publishing Co.,
Willoughby, OH.
7. Federal Register. 1975. .40(51): 11994-11995.
8. Ferguson, J. F. and J. Gavis. 1972. A review of the Arsenic
Cycle in Natural Waters, Water Res. j>: 1259-1274.
9. Frost, D. V. 1967. Arsenicals in Biology—Retrospect and
Prospect. Fed. Proc. 26:194-208.
10. Gleason, M. N., R. E. Gosselin, H. C. Hodge, and R. P. Smith (eds.).
1969. Clinical Toxicology of Commercial Products. Acute Poisoning.
3rd ed. The Williams and Wilkins Co., Baltimore, MD. pp. 32-34.
11. Hamilton, A. and H, Hardy (eds.). 1974. Industrial Toxicology.
3rd ed. Publishing Sciences Group, Inc., Acton, Mass. pp. 31-39.
12. Junkins, R. L. 1963. Arsenic and Its Radioisotopes in the
Environs. In: Radioecology—Proceedings of the First National
Symposium on Radioecology. Schultz, V., and A. W. Klement, Jr.
(eds.). Reinhold Publishing Corp., New York, and The American
Institute of Biological Sciences, Washington, DC.
13. Leatherland, T. M. and J. D. Burton. 1974. The Occurrence of
Some Trace Metals in Coastal,Organisms with Particular Reference
to the Solent Region. J. Marine Biol. Assoc., U.K. 54:457-468.
14. Lis, S. A. and P. K. Hopke. 1973. Anaomalous Arsenic Concentrations
in Chautauqua Lake. Environ. Letters 5:45-51.
91
-------
15. Louria, D. B., M. M. Joselow, and A. A. Browder. 1972. The
Human Toxicity of Certain Trace Elements. Ann. Intern. Med.
7(5(2): 307-319.
16. McCabe, L. J., J. M. Symons, R. D. Lee, and G. G. Robeck. 1970.
Survey of Community Water Supply Systems. J. Am. Water Works
Assoc. 6^:670-687.
17. Nelson, H. A., M. ,R, Crane, and K. Tomson. 1971. Inorganic
Arsenic Poisoning in Pastured Feeder Lambs. J. Am. Vet. Med.
Assoc. 158(11):1943-1945.
18. Osol, A. and Pratt, R. 1973. The United States Dispensatory.
27th Edition. J. B. Lippincott Co., Philadelphia, pp. 154-156, 820.
19. Ottinger, R. S., J. L. Blumenthal, D. F. Dal Porto, G. I. Gruber,
M. J. Santy, and C. C. Shin, 1973. Recommended Methods of Reduc-
tion, Neutralization, Recovery, or Disposal of Hazardous Waste,
Vol. 1. Report No. EPA-670/2-73-053-a, 203 pp.
20. Petry, J. St., 0. M. Rennert, H. Choi, and S. Wolfson. 1970.
Arsenic Poisoning in'Childhood. Clin. Toxicol. _3(4):519-526.
21. Satterlee, H. S. 1960. The Arsenic-Poisoning Epidemic of 1900:
Its Relation to Lung Cancer in 1960—an Exercise in Retrospective
Epidemiology. New Eiig. J. Med. 263 (14):676-684.
22. Schroeder, H. A. 1970. A Sensible Look at Air Pollution by Metals.
Arch. Environ. Health 21:798-806.
23. Schroeder, H. A. and J. J. Balassa. 1966. Abnormal Trace Metals
in Man: Arsenic. J. Chron. Pis. 19:85-106.
24. Smith, R. G. 1972. Arsenic in Metallic Contaminants and Human
Health. Lee, D.H.K. (ed.). Academic Press, New York, pp. 158-162.
25. Sullivan, R. J. 1969. Preliminary Air Pollution Survey of Arsenic
and Its Compounds. National Air Pollution Control Administration
Publication No. APTD 69-26, Raleigh, NC, 60 pp.
26. Teitelbaum, D. T. and L. C. Kier. 1969. Arsenic Poisoning. Report
of Five Cases in the Petroleum Industry and a Discussion of the
Indications for Exchange Transfusion and Hemodialysis. Arch.
Environ. Health 19;133-143.
27. Tjaij, J. K., and D. Azia. 1971. A Mass Acute Poisoning from
Rice Contaminated with Arsenic in Two Orphanages. Paediatr.
Indones. 11:91-94.
28. United States Environmental Protection Agency. 1971. Inorganic
Chemical Pollution of Freshwater. Water Quality Criteria Data
Book, Vol. 2, Pub. No. 18010, DPV 07/71, Litton Inc., U.S.
Government Printing Office, Washington, D.C. 280 pp.
92
-------
29. United States Environmental Protection Agency. 1974. Disposal of
Hazardous Waste. Report No. SW-115, U.S. Government Printing Office,
Washington, B.C. 110 pp.
30. World Health Organization. 1973. Arsenic and Inorganic Arsenic
Compounds. In: IARC Monographs on the Evaluation of Carcinogenic
Risk of Chemicals to Man. Some Inorganic and Organometallic
Compounds, Vol. 2. International Agency for Research on Cancer.
pp. 48-69.
31. Zaldivar, R. 1974. Arsenic Contamination of Drinking Water and
Foodstuffs Causing Endemic Chronic Poisoning. Beitr. Path. Bd.
151:384-400.
93
-------
94
-------
CHRONIC TOXICITY OF HEXACHLOROBENZENE IN RATS: A PRELIMINARY STUDY
by
R. L. Younger, James H. Johnson, Donald E. Clark, and Hilton H. Mollenhauer
Veterinary Toxicology and Entomology Research Laboratory, Agricultural Re-
search Service, USDA, P. 0. Drawer GE, College Station, Texas 77840
Several thousand cases of acquired porphyria cutanea tarda were re-
corded in Turkish Nationals from 1955 to 1959 in the southeastern region of
Turkey. Affected individuals had consumed, as food, wheat that had been
treated with the fungicide hexachlorobenzene (HCB, C6Clg). The disease oc-
curred mainly in the 4- to 14-year age group, and acute skin manifestations
appeared after relatively long periods of exposure. Systemic effects of the
disease were permanent in some children.2
In the United States in 1973, violative levels (>0.5 ppm) of HCB were
detected in body fat of livestock and poultry. In Louisiana, the sources of
HCB residues in cattle were traced to chemical waste disposal practices of
manufacturing plants which produce chlorinated hydrocarbons. EPA approved
HCB as a fungicidal agent in 1971 to control diseases of seed grains, but in-
dustrial contamination of the environment appears to be more important as a
source of exposure for livestock and poultry.
Administration of HCB to experimental animals induces hepatic porphyria
and morphologic alterations in hepatic tissue.3,6,7,9,13 Histologic changes
primarily consist of enlargement, vacuolar degeneration, necrosis, and pro-
liferation of smooth endoplasmic reticulum of hepatocytes. Almost all of
these HCB studies in experimental animals were relatively short-term studies
and were primarily designed to investigate experimental hepatic porphyria.
The present study was designed to evaluate the chronic effects of low dietary
levels of HCB after long periods of exposure in the rat.
MATERIALS AND METHODS
a
As part of a current two-year feeding study, HCB (99+% purity) was
incorporated into feed,^ and was continuously fed to Sprague—Dawley
ratsc (150 to 300 grams initial body weight) at dietary levels of 0, 1,
5, 10, and 25 ppm for up to 18 months. For each dose level, 50 rats of
each sex were used.
After 3, 6, 12, and 18 months of treatment, five rats were randomly
selected from each of the treatment groups and blood and urine samples
collected. These animals were then killed, final body and organ
weights recorded, and tissue samples removed for microscopy and residue
analyses.
Q
HCB supplied by Chem Services, Inc., West Chester, PA.
Laboratory Rat Chow, Ralston-Purina, St. Louis, MO.
°Texas Inbred Mice Co., Houston, TX.
95
-------
Routine hematology (total red and white cell counts, packed cell
volumes, hemoglobin concentrations, and differential leukocyte counts),
serum alkaline phosphatase levels, and urinary 6-aminolevulinic acid
levels were determined by standard laboratory procedures.
13
Since HCB is a hepatotoxic compound, microscopy was limited to the
liver. Hepatic tissue was fixed in 10% neutral buffered formalin, section-
ed, and stained with hematoxylin and eosin for light microscopic examina-
tion. For electron microscopy, small tissue samples from liver were fixed
in glutaraldehyde-paTaformaldehyde and osmium tetroxide and then stained
with uranyl acetate and lead citrate for study with the electron microscope
as described elsewhere.
A gas chromatograph equipped with a nickel-63 electron capture
detector was used to determine HCB residues in brain, heart, liver,
kidneys, spleen, and abdominal fat. Tissue samples of equal weight from
each dose level were pooled by sex. Non-fatty tissues were dried for
3 hours at 110 C before sample preparation. The tissues were extracted
three times each by blending in a tissue homogenizer with pesticide
quality hexane and extracts combined. Then, aliquots of the combined
extracts were injected into the gas chromatograph after appropriate dilu-
tion. Results of residue analyses were expressed as ppm HCB based on
weight of extracted fat for adipose tissue or weight of dry tissue for
non-fatty tissues.
RESULTS
Clinical Aspects—The general health of all rats remained unaffected.
No physical signs of toxicity were observed in HCB-treated rats. A slight
increase in the mortality rate for the 25 ppm rats was observed. Mortality
levels in 1, 5, and 10 ppm rats were comparable to controls. Routine hema-
tology, serum alkaline phosphatase levels, and urinary 6-aminolevulinic
acid levels for HCB-treated rats remained within normal limits throughout
the exposure period. Actual liver weights for the 25 ppm rats were greater
than controls after 3, 6, and 12 months, but no differences were noted after
18 months of treatment. Liver -weights of the 1, 5, and 10 ppm rats were
comparable to controls. At necropsy, no gross lesions were observed in liver
of HCB-treated rats or controls.
Microscopic Features—Light microscopic changes were most pronounced
in liver sections from the 10 and 25 ppm HCB-treated rats at 1 year, but
changes were evident 6 months after treatment. Microscopic changes included
marked enlargement of hepatocytes, vacuolar degeneration of hepatocytes,
hepatocellular disarray, foci of fatty metamorphosis, necrosis of isolated
hepatocytes, and megalohepatocytes with hyperchromatic nuclei and
hypertrophied nucleoli. Distribution of these changes was irregular within
the liver lobule. For the 5 ppm HCB-treated rats, histologic changes in
hepatocytes were less pronounced after 1 year of exposure when compared to
the 10 or 25 ppm rats. Hepatic changes were not evident after 6 months of
exposure for the 5 ppm rats.
Tracer MT-220, Tracer Instruments, Austin, TX.
96
-------
Ultrastructural changes were observed in hepatocytes as early as
3 months after onset of exposure in HCB-treated rats that received doses
as low as 5 ppm, but changes were most pronounced at the 25 ppm level and
1 year of exposure. In some hepatocytes, smooth endoplasmic reticulum
(SER) proliferated and became the predominant feature of the cell. In
others, SER appeared to be replaced by a storage product, presumably
glycogen. Mitochondrial distortions were noted; elongated forms and swollen
forms. SER proliferation and elongated mitochondrial forms were usually
associated with the lower dietary levels of HCB, whereas the replacement of
SER by glycogen deposits and swollen mitochondrial forms was usually associ-
ated with the higher dietary levels of HCB. Lipid vesicles were prominent
in many hepatocytes in liver of rats exposed to 25 ppm HCB for 1 year.
Preliminary evidence after 18 months of exposure suggests that
histologic changes in hepatocytes from HCB-treated rats were no greater, and
possibly less severe, than changes observed 1 year after onset of exposure.
No histologic changes were found in liver sections from rats exposed
to 1 ppm HCB for 18 months.
Residues of HCB—Tissue residues of HCB were related to dose level and
duration of exposure. No significant sex difference was found in tissue
levels of HCB. Adipose tissue, 1, 5, 10, and 25 ppm rats, accumulated an
average of 22, 82, 149, and 473 ppm HCB, respectively, after 3 months
exposure and increased to an average of 37, 133, 283, and 799 ppm HCB,
respectively, after 18 months exposure. For non-fatty tissues, highest
HCB residues usually occurred in kidneys, followed by liver, spleen, brain,
and heart. Their levels in non-fatty tissues were about 10 to 20% of the
fat level in the same group of rats.
DISCUSSION
Chronic ingestion of 1, 5, 10, and 25 ppm HCB by rats for 18 months
did not produce adverse clinical effects. The general health of all rats
remained unaffected for 18 months. Ingestion of HCB at these levels did
not influence hematologic values, serum alkaline phosphatase levels, or
urinary 6-aminolevulinic acid levels. Although a slight increase in
mortality rate was observed for 25 ppm rats, no differences occurred
between 1, 5, or 10 ppm HCB-treated rats and controls.
Microscopic changes that we observed are compatible with previously
reported changes in hepatocytes and liver sections from laboratory animals
after ingestion of HCB.3,6,7,9,13 ye consider the light microscopic and
ultramicroscopic changes that we observed in hepatocytes as nonspecific
changes because similar type alterations can result after exposure to
many foreign compounds, including chlorinated hydrocarbons.5,10,11 Pro-
liferation of the SER is a nonspecific hepatic response associated with
induction of the hepatic enzyme systems which accomplishes biotransforma-
tions of most exogenous compounds.5»10»H We observed alterations in
mitochondrial shape within hepatocytes of liver section from HCB-treated
rats. Presently, mitochondrial distortions are considered as nonspecific
changes of cell injury since they occur also from exposure to other toxic
substances. Only in a few cases such as the mitochondrial myopathies^
or inherited disorders^ can mitochondrial change be considered the primary
97
-------
effect of a toxin. Based solely on morphologic changes within rat
hepatocytes, a no-effect dosage for 18 months exposure appears to be 1 ppm
RGB in dry feed.
Hexachlorobenzene is a lipid-soluble non-polar chlorinated hydrocarbon
compound. Thus, it is preferentially stored in adipose tissue. In our
study, HCB residues accumulated in all rat tissues examined in a dose
dependent manner. Levels of HCB were highest in adipose tissue followed by
kidney, liver, spleen, brain, and heart. Rats concentrated HCB residues
in their adipose tissue several times the dietary level in feed.
SUMMARY
Male and female rats were continuously fed a diet containing 0, 1,
5, 10, or 25 ppm hexachlorobenzene (HCB) for 18 months. At 3, 6, 12, and
18 months after onset of exposure, five rats of each sex and each dose level
were bled and urine samples collected to determine hematologic values, serum
alkaline phosphatase levels, and urinary 6-aminolevulinic acid levels. These
animals were then killed and their tissues removed for HCB residue analysis.
In addition, hepatic tissue was fixed and stained for examination with light
and electron microscopes.
No overt signs of toxicity were observed during the 18 months of
exposure. Hematologic values, serum alkaline phosphatase levels, and
urinary 6.-aminolevulinic acid levels remained within normal limits through-
out this period.
Light and electron microscopic studies revealed nonspecific changes
in liver sections from 5, 10, and 25 ppm rats. Histologic changes were
most pronounced after 12 months of exposure for the 10 and 25 ppm rats.
The changes, included enlargement and vacuolar degeneration of hepatocytes,
hepatocellular disarray, foci of fatty metamorphosis, necrosis of isolated
hepatocytes, megalohepatocytes with hyperchromatic nuclei and hypertrophied
nucleoli, proliferation of smooth endoplasmic reticulum, and elongated and/
or swollen mitochondria. Hepatocytic changes were not observed in liver /
from 1 ppm rats.
HCB residues accumulated in all rat tissues examined. Tissue residue
profiles indicated that adipose tissue had the highest HCB content followed
by kidneys, liver, spleen, brain, and heart.
98
-------
SELECTED REFERENCES
1. Booth, N. H., and McDowell, J. R.: Toxicity of Hexachlorobenzene and
Associated Residues In Edible Animal Tissues. J. Amer. Vet. Med. Ass.,
166, (Mar. 15, 1975):591-595.
2. Cam, C., and Nigogosyan, G.: Acquired Toxic Porphyria Cutanea Tarda
Due to Hexachlorobenzene. J. Amer. Med. Assoc., 183, (1963):88-91.
3. Campbell, J. A. H.: Pathological Aspects of Hexachlorobenzene Feeding
in Rats. S. Afr. J. Lab. Clin. Med., 9, (Dec. 1963);203-206.
4. Goldfischer, S., Moore, C. L., Johnson, A. B., Spiro, A. J., Valsamis,
M. P. Wisniewski, H. K., Ritch, R. H., Norton, W. T., Rapin, I., and
Gartner, L. M.: Peroxisomal and Mitochondrial Defects in the Cerebro-
Hepato-Renal Syndrome. Science 182, (Oct. 5, 1973):62-64.
5. Kappas, A., and Alvares, A. P.: How the Liver Metabolizes Foreign
Substances. Sci. Amer., 232, (June 1975):22-31.
6. Kimbrough, R. D., and Linder, R. E.: The Toxicity of Technical Hexa-
chlorobenzene in the Sherman Strain Rat. A Preliminary Study. Res
Commun Chem Pathol Pharmacol, 8, (Aug. 1974):653-664.
7. Medline, A., Bain, E., Menon, A. I., and Haberman, H. F.: Hexachloro—
benzene and Rat Liver. Arch Pathol., 96, (Jul. 1973):61-65.
8. Mollenhauer, H. H., Johnson, J. H., Younger, R. L., and Clark, D. E.:
Ultrastructural Changes in Liver of the Rat Fed Hexachlorobenzene.
Amer. J. Vet. Res., (1975): In Press.
9. Ockner, R. K., and Schmid, R.: Acquired Porphyria in Man and Rat Due
to Hexachlorobenzene Intoxication. Nature, 189, (1961);499.
10. Parke, D. V.: The Biochemistry of Foreign Compounds. Pergamon Press,
London, (1968).
11. Remmer, H., and Merker, H. J.: Effect of Drugs on the Formation of
Smooth Endoplasmic Reticulum and Drug-Metabolizing Enzymes. Annals
NY Acad Sci, 123, (1965):79-97.
12. Tandler, B., and Hoppel, C. L.: Mitochondria. Academic Press,
New York and London, (1972).
13. Vos, J. G., van der Maas, H. L., Musch, A., and Ram, E.: Toxicity of
Hexachlorobenzene in Japanese Quail with Special Reference to Porphyria,
Liver Damage, Reproduction, and Tissue Residues. Toxicol Appl
Pharmacol, 18, (Apr. 1971):944-957.
99
-------
100
-------
ENVIRONMENTAL EXPOSURE TO PESTICIDES IN UTAH
Stephen L. Warnick* and J. Wanless Southwick**
ABSTRACT
Pesticide residues were identified and measured in Utah's air, water,
soil, food, housedust, and human tissues. Pesticide levels in air and
water (in parts per trillion) were found to be very low in comparison
with housedust and human adipose tissue (in parts per million).
No overt health effects from exposure to pesticide residues were
found in people with regular occupational contact with pesticides. The
need for additional study of environmental exposure to pesticides in Utah
was recognized.
INTRODUCTION
When we talk about the problem of environmental pollution, we need
numbers. Scientific monitoring, with reliable numbers, is the first
step to effective environmental management. Baseline measurements and
repeated observations are the only way to detect desirable or undesirable
changes in the environment. The objective of the work described in this
paper is to monitor pesticides in Utah's environment, thus providing some
of the numbers needed to evaluate the impact of pesticides in Utah.
The problem of pesticides in the environment has aroused considerable
public concern. Over one billion pounds of pesticides are used annually
in the U.S. (1) and about one million pounds in Utah (Table 1). This
compares to about 10 million pounds used in Arizona and 140 million
pounds used in California (3).
Pesticides play a vital role in food production and disease control.
As a result of this heavy usage and because some of these chemicals are
very persistent, they can be found in the food we eat, the air we breathe,
the homes we live in, and each of us carries our own body burden of
pesticides. The value of pesticides to man and pesticide impact on the
environment both need to be considered when environmental quality control
plans are developed.
Utah is one of twelve states under contract with the Environmental
Protection Agency (EPA) to carry out a Community Study on Pesticides.
* Stephen L. Warnick, Ph.D., formerly Project Director and Principal
Investigator Utah Community Study on Pesticides, State of Utah, Department
of Social Services, Division of Health, 44 Medical Drive, Salt Lake City,
Utah 84113. Presently, Chief of Toxicology, Intermountain Laboratories,
Inc., 166 East 5900 South, Salt Lake City, Utah 84107
** J. Wanless Southwick, Ph.D., Project Director Utah Community Study
on Pesticides, State of Utah, Department of Social Services, Division of
Health, 44 Medical Drive, Salt Lake City, Utah 84113
The work upon which this publication is based was performed pursuant
to Contract No. 68-02-0571 with the Environmental Protection Agency.
101
-------
The study, conducted by the Utah State Division of Health, is now in the
sixth year. The objective is investigation of the effect pesticides may
have on human health. An important part of this research is to evaluate
man's environmental exposure to pesticides. Analyses of environmental
samples have been done by Intermountain Laboratories, Inc., under a
subcontract with the Utah State Division of Health. Human tissue
samples were analyzed at the Utah State Division of Health Laboratory.
METHODS
A large number of samples representing varied elements of Utah's
environment were collected and analyzed for pesticide residues.
Air samples were collected using ethylene glycol impingers, following
methods outlined by the Environmental Protection Agency. Water samples
were collected from the Division of Health's routine water quality
sampling program. Only a few soil samples have been collected thus far.
Food and housedust samples were collected from homes of participants
in a long-term study of workers with occupational exposure to pesticides.
Part of the homes sampled were homes of people without direct occupational
exposure to pesticides who served as controls in the study.
Food samples represented a sample of the total diet as taken from a
regularly prepared meal at each participant's home. Housedust was taken
from vacuum cleaners in the homes of each participant.
Blood samples from participants in the long-term study were analyzed
for pesticide residues as were bloods from Utah's general population.
Adipose tissue samples from autopsy cases were analyzed for pesticide
residues during 1969-1970.
Sample extraction, clean-up, and analyses were performed according to
the methods presented in the Community Pesticide Studies Laboratories
"Manual of Analytical Methods" (4), prepared by the Perrine Primate
Research Laboratories. The Perrine Laboratory also provided the pesticide
standards used in this study and carried out a quality control program in
which both Intermountain Laboratories and the Division of Health
Laboratory participated. fi_
A MicroTek 220 Gas Chromatograph, equipped with a Ni electron
capture detector, was used for the pesticide analyses of both laboratories.
Recovery studies have shown that for the pesticides reported, at least 90%
are recovered routinely. A two-column system was used for confirmation.
RESULTS
Pesticide usage in Utah was estimated by contacting commercial outlets
of pesticides within the State. During 1971 about 79,000 pounds of
chlorinated hydrocarbon insecticides were sold in Utah. Chlordane was
the primary chlorinated hydrocarbon insecticide sold, accounting for more
than half of the total tonnage.
During the same period, about 191,000 pounds of organophosphates were
sold, with parathion and malathion being the primary insecticides. Arsen-
icals, carbamates, and other miscellaneous insecticides accounted for
about 94,000 pounds more.
Herbicide sales dwarfed insecticide sales. Approximately 806,000
pounds were sold in Utah during 1971, with ethylene dibromide and 2,4-D
being the two primary pesticides. Table 1 summarizes pesticide sales in
Utah for 1971.
102
-------
Table 1. Summary of 1971 Pesticide Sales in Utah
in Pounds of Active Ingredients
1971
PESTICIDE GROUP. ESTIMATE
Chlorinated Hydrocarbons 79,000
Organophosphates 191,000
Carbamate Insecticides 13,000
Inorganic Insecticides 70,000
Herbicides 806,000
Miscellaneous • 11,000
TOTAL 1,170,000
With this much pesticide being used in Utah, the logical question is
how much can be found in the environment and in the human population?
Air monitoring in Utah for the past three years has shown that
pesticide levels in Utah's ambient air are minimal. Table 2 shows the
chlorinated hydrocarbon pesticides commonly found in air samples.
Occasionally organophosphates (diazinon, parathion, and dursban) were
detected in some air samples.
TABLE 2. AVERAGE PESTICIDE RESIDUE LEVELS FOUND IN AIR SAMPLES
COLLECTED AT FOUR SALT LAKE CITY LOCATIONS DURING 1971 AND 1972 (ng/MJ)
PESTICIDE
3 BHC
Heptachlor
Epoxide
Chlordane
p, p1 -DDE
Dieldrin
o, p'-DDT
p, p'-DDD
p, p1 -DDT
Total DDT
UNIVERSITY
OF UTAH
0.9
0.3
0.8
0.6
0.7
0.8
1.1
1.8
4.3
RUDY GUN
CLUB
0.6
0.1
0.3
0.6
0.3
0.1
0.3
0.5
1.5
MURRAY
0.6
0.1
0.4
0.4
0.2
0.1
0.2
0.4
1.1
MILLCREEK
GARDENS
0.4
0.2
0.5
0.5
0.3
0.1
0.1
0.5
1.2
103
-------
Water monitoring indicated only minimal levels of pesticides in
Utah's water. Even raw sewage water had lower levels of pesticide
residues than allowed in the newly proposed drinking water standards (5).
Chlorinated hydrocarbons were commonly detected in•the low parts-per-
trillion range. Occasionally we found small organophosphate residues
including parathion, diazinon, and malathion.
Table 3 shows culinary water contained the lowest levels of total DDT,
while domestic wastewater had the highest. Culinary water did not differ
significantly from surface water in levels of total DDT.
Of the few (19) soil samples analyzed, total DDT averaged 0.41 ppm
compared to 0.03 ppm for dieldrin and 0.08 ppm for chlordane. A system-
atic soil sampling effort is currently underway to more accurately
estimate pesticide residues in Utah's soils.
TABLE 3. RESIDUES OF TOTAL DDT IN WATER SAMPLES FROM UTAH
(IN PARTS PER TRILLION)
WATER TYPE
Culinary Water,
Surface Water
Domestic Waste
Industrial Waste
NUMBER OF
SAMPLES
114
108
82
37
MEAN
(PPT)
18.5
26.4
72.1
43.7
STANDARD
DEVIATION
29.6
48.8
73.9
60.8
Food and housedust samples received from participants in the long-term
study showed no convincing evidence that food from homes of occupationally
exposed participants had any more pesticide residues than did food from
control participants. There was, however, some evidence that housedust in
homes of occupationally exposed participants had more pesticide residues
than did housedust from control participant homes.
Pesticide levels tend to be about 350 times greater in housedust than
in food. Table 4 gives a summary of pesticide residues found in 47 food
and 37 housedust samples.
104
-------
TABLE 4. SUMMARY OF AVERAGE FOOD AND HOUSEDUST PESTICIDE RESIDUES
FROM UTAH (IN PARTS PER BILLION)
FOODHOUSEDUST
PESTICIDE EXPOSED CONTROL EXPOSED CONTROL
Lindane
$ BHC
Heptachlor Epoxide
Chlordane
p, p'-DDE
Dieldrin
o, p'-DDT
p, p'-DDD
p, p'-DDT
Total DDT
2
6
2
2
11
4
2
3
4
20
1
5
2
1
8
3
2
2
3
15
185
362
214
715
476
1,916
2,145
1,374
8,187
12,183
189
340
161
462
236
1,679
805
366
2,682
4,089
Pesticide residues in man's environment contribute to his body burden
of pesticide residues. Table 5 shows average pesticide residue levels in
400 bloods from Utah's general population. These data indicate that body
burdens of chlorinated hydrocarbons increase with increasing age. Total
DDT levels in sera of people over 21 years of age averaged about 25 ppb
compared to 47 ppb for those over 65 years of age.
Higher pesticide residues were found in people with occupational
exposure to pesticides, but the residues found depended on the work situa-
tion of the person exposed. For example, pest control operators (who
used significant quantities of dieldrin and chlordane) had higher serum
residues of dieldrin and chlordane than did mosquito abatement workers
who had little contact with these two pesticides.
DISCUSSION AND CONCLUSIONS
Pesticide usage in Utah is small compared to other parts of the
country. Pesticide residues in Utah's air tend to be minimal and compare
closely with levels found in other areas of the country. This may be
due to widespread distribution of pesticides at low levels in the atmo-
sphere.
Pesticide residue levels in water and soil seem to be lower than
residue levels reported from other areas of the country.7-8 in no case
did pesticide residues measured in water samples exceed the proposed
standards for drinking water.•*
Pesticide residues in food samples were only about one-twentieth of
what has been described as acceptable.^ Careful regulation of pesticide
residues in food and forage is probably responsible for a 22 percent
decline in chlorinated hydrocarbons in food from total diet samples
since 1969.10
105
-------
TABLE 5. PESTICIDE RESIDUE AVERAGES IN SERA OF UTAH'S GENERAL POPULATION FOR 1972 (in ppb)
o
Ox
Overall
Men
Women
Under 21 years
21+ years
21-64 years
65+ years
SAMPLE
SIZE
400
174
226
55
345
296
49
DIELDRIN
.98
1.05
.93
.86
1.00
.96
1.27
HEPTACHLOR
EPOXIDE
.84
.93
.78
.56
.89
.85
1.11
3BHC
1.76
1.85
1.69
1.43
1.81
1.77
2.02
p,p'-DDE
24.60
27.15
22.64
15.83
26.00
24.76
33.51
p.p'-DDT
6.26
6.74
5.89
5.71
6.35
6.05
8.12
TOTAL
DDT
35.09
38.49
32.48
24.96
36.71
35.00
47.00
-------
Housedust seems to be surprisingly high in pesticide residues
compared with other elements of the environment. Table 6 shows typical
levels of pesticide residues in the various samples we tested. The fact
that housedust is substantially higher in pesticide residues may indi-
cate that people get a significant portion of their exposure to pesticides
from dust in the air at home.
The fact that housedust from homes of people with occupational exposure
was significantly higher in pesticide residues than housedust from control
homes could imply that families of the occupationally exposed may get
significantly more exposure to pesticides. The contribution of dust in
the air at home to the human body burden of pesticides needs to be further
explored.
The body burden of pesticides in people of Utah compares closely with
other areas of the country.H Serum residue levels are consistently lower
than adipose tissue levels. There is some evidence that DDT residues in
human adipose tissue may be declining.12
We have been able to identify and measure pesticide residues in human
tissues and in environmental samples. We have not been able to identify
any adverse health effects from environmental exposure to pesticide resi-
dues, even in the case of the more heavily exposed people who have regular
occupational contact with pesticides.
The evaluation of environmental exposure to pesticides in Utah is not
complete, but based on our present perspective, it seems that the value of
pesticides in agriculture and public health is complemented by an absence
of overt health effects from exposure to pesticide residues.
Table 6. Comparison of Typical Levels of Pesticide Residues in
Elements of Utah's Environment.
ENVIRONMENT
Air
Water
Soil
Food
Housedust
Human Serum
Human Adipose
TOTAL DDT
0.002
0.036
410.000
15.000
4,089.000
35.000
7,300.000
UNIT OF MEASURE
yg/m
Wg/1
. yg/Kg
yg/Kg
yg/Kg
yg/Kg
yg/Kg
107
-------
REFERENCES
1. Frear, D.E.H., 1972, "Pesticides Handbook—Entoma," College Science
.Publishers, State College, Pennsylvania. 279 pp.
2. Roan, C. C. et^ al_., 1969. "Pesticide Use in Arizona as Shown by
Sales," Progressive Agriculture in Arizona, Vol. XXI, No. 3,
pp. 14-15, College o£ Agriculture, University of Arizona, Tucson,
Arizona.
3. Fielder, Jerry W., 1970. "Pesticide Use Report," California Dept. of
Agriculture.
4. Thompson, J. F., H. F. Enos, M. F. Cramner, F. J, Biros, and L. A.
Richardson, "Analysis of Pesticide Residues in Human and Environ-
mental Samples." A manual prepared for use by Community Studies
Projects and Pesticide Monitoring Laboratories by the Primate
Research Laboratories, Environmental Protection Agency, Perrine,
Florida,
5. Hartung, H. 0., 1973. Revisions to the 1962 Drinking Water Standards.
Willing Water 17(8): 12-14.
6. Yobs, Ann, 1972. "Incidence of Pesticide Residues in Ambient Air."
Report given at the Community Studies Project Director's Meeting,
January, 1972, in Chamblee, Georgia.
7. Lichtenberg, J. J., J. W. Eichelberger, R. C. Dressman, J. E. Longbottom,
"Pesticides in Surface Waters of the United States—A Five-Year
Summary, 1964-1968." Pesticides Monitoring Journal, Vol. 4, No. 2,
September, 1970.
8. Stevens, L. J., C. W. Collier, and D. W. Woodham, "Monitoring Pesticides
in Soils." Pesticides Monitoring Journal, Vol. 4, No. 3, December, 1970.
9. Duggan, R. E. and J. R. Weatherwas, 1967. "Dietary Intake of Pesticide
Chemicals." Science. 157 (3792): 1006-1010.
10. Corneliussen, P. E., 1972. "Pesticide Residues in Total Diet Samples."
Pesticides Monitoring Journal, (4).
11. Yobs, Ann, 1972. "Mean Levels of Selected Chlorinated Hydrocarbon
Pesticide Residues in Adipose of the General Population." Report
given at the Community Studies Project Director's Meeting, June,
1972, at Chamblee, Georgia.
12. Warnick, S. L., 1972. "Organochlorine Pesticide Levels in Human Serum
and Adipose Tissue, Utah—Fiscal Years 1967-1971," Pesticides
Monitoring Journal 6(1): 9-13.
108
-------
ANALYSES OF ACUTE PESTICIDE POISONINGS FOR 1970-74
C. W. Miller1
With the nationwide introduction and increased use of pesticides
in agriculture, structural pest control, and home and garden care, an
increase in the degree of exposure by the general population can be
expected. The Environmental Protection Agency (EPA) is charged with the
responsibility for determining the possible adverse health effects which
might occur as a result of such exposure. The Community Pesticides
Studies (now the Epidemiologic Studies Program), Technical Services
Division, Office of Pesticide Programs, was assigned the responsibility
of investigating and assessing this pesticide health problem. To carry
out its mission, the Community Pesticides Studies Program established'
projects by contractual arrangement in 14 diverse geographic locations
throughout the United States.
When pesticide involvement was suspected, either in accidental-or
intentional situations, attempts were made to determine the source and
dose of the toxicant, route of exposure, signs and symptoms of intoxi-
cation peculiar to the compound, rapidity of symptom onset, and
effectiveness of the treatment given. Consultation and analytical ^M
laboratory services were made available to attending physicians on
request for confirmation of the etiology, monitoring of the individual
during treatment or identification of the suspect pesticide involved.
Medical surveillance of survivors was maintained, when possible, to '
assess any post-exposure residual effects.
Accident data from the 14 Community Pesticides Study Projects should
not be considered all of the pesticide-related incidents that may have
occurred within the State in which the Projects are located. The
investigative aspects of the Projects were restricted to a selected :
site, generally a three or four county area of high-pesticide usage.
For example, the Arizona project investigated only five acute poisoning
incidents in 1972 (Table 1). However, a telephone survey of aerial
applicators operating within the State was made during the same year
and an additional 59 cases of poisonings attributable to pesticides
were discovered. Of these, 53 cases required immediate medical treat-
ment and three entailed hospitalization for an average period of 56 -
hours. Thus, the data reported in this article reflect only a summation
of those cases investigated by the project laboratories. These cases
are indicative of the situation within limited areas and are nonrepre-
sentative of the Nation as a whole.
Table 1 provides an enumeration of the cases investigated by each
State Project. Although some poisoning episodes involved more than one
individual, the "cases" listed represent "persons poisoned" so that case-
fat 11 ity rates can be ascertained. Case-fatality rates have only been
calculated for the total number of cases per year and for the major
Field Studies Coordinator, Epidemiologic Studies Program, Technical
Services Division, Office of Pesticide Programs, Environmental Protection
Agency.
109
-------
Table 1; Cases' of Suspected Acute' Pesticide P6is6nings!"and Deaths
Investigated by the Community Pesticides Studies Programs During
' 1970-1974.
Project
rr
. , I/
Arizona—
t.:v • •
California
Colorado
Fiorida-^
',! C
Hawaii
Idaho
). j 3
Michigan
Mississippi
New, Jersey
S. Carolina
ds
Texas
Utah
c
Washington
Totajl
Case/Fatality
rates
1970
:•*/&
44/0
8/0
30/6
18/0
11/0
8/0
5/0
5/0
14/2
3/2
26/0
3/0
8/1
186/12
6.4
1971
'" 6/1
5/0
6/0
30/12
2/0
2/0
19/0
1/0
5/1 .
13/1
7/1
43/0
, 3/0
14/1
156/17
10.9
1972
5/1
38/3
7/0
26/3
4/0
12/1
10/0
0/0
2/0
11/0
5/0
29/1
3/1
5/0
157/10
6.4
'1973
_
62/0
9/0
. -.
. 3/0.
9/0
5/0
6/0
11/2
3.8/0
2/0
16/0
8/1
20/0
189/3
1.6
1974
• •• . •. _. •
8/2
15/0
.. - -
13/1
12/0
6/1
3/0
0/0
8/1
16/2
12/0
11/0
17/0
121/7
5.8
total
14/3
157/5 • ,'',;:'•
45/0 ;
-------
categories, as described further on in this article, in which specific
associations can be made. The data show a decrease in the number of
cases between 1970 and 1971, with what appears to be a leveling-off
period for 1971 and 1972 with approximately the same number of cases
occurring in both these years. In 1973, the number of cases exceeds
all previous years, surprisingly at a time when two of the projects
ceased operations. It is believed that this increase reflects the ban
on DDT and subsequent increased usage of the organophosphates. It
could also be speculated that a greater number of cases would have been
reported had these other two projects been functioning. The number of
cases in 1974 was the lowest of the 5 year period, possibly reflecting
increased awareness of the hazard organophosphates present.
Considering the case-fatality rates for these years, 1971 was the
highest with 10.9 percent of all cases resulting in death. During this
year, 4 deaths were reported as a result of a freakish traffic accident.
If these deaths were to be excluded from the 1971 data, the case-fatality
rates would be closely compatible for 1970-71-72. Interestingly, the
year with the highest number of cases (1973) had the lowest case-fatality
ratio (1.6), whereas in 1974, the lowest number of cases reported had
a case-fatality rate approximating the earlier years.
In further analyzing the data, these pesticide poisonings are
categorized in general terms in Table 2. As the Projects were primarily
involved in working with individuals or groups whose occupation in some
manner placed them in close association with pesticides, it is not
surprising that the data shows the largest number of incidents occurred
in this occupationally exposed group. There was little variation in the
number of cases during 1970-73; however in 1974, the total number of
cases in this category was approximately half that reported for previous
years. It can also be noted that, although this category has the
greatest number of cases, it also has the lowest case-fatality rate.
The major route of exposure for this group was by dermal sorption,
inhalation, or a combination of both.
Incidents in the home rank second in this general categorization.
Approximately 70 per cent were caused by accidental ingestion of the
pesticide. Generally this was the result of storage of the pesticide
in areas accessible to children and inability of children to comprehend
the hazardous warnings on the label or storage of the pesticide in an
improper container (i.e., coke bottle). The case-fatality rate for this
category is 12.9 percent and is evidence of the greater degree of
toxicity resulting from oral ingestion as compared to inhalation or
dermal contact.
The categories of suicides and homicides is self explanatory. The
classification "Other" encompasses situations difficult to categorize.
For example:
1. A person is admitted to the Emergency Room of a hospital in
a comatose condition, as a result of accidental or intentional
ingestion of a pesticide. The person may expire during treat-
ment and no relative, friend, or associate can explain the
circumstances surrounding the situation.
Ill
-------
Table 2. General Categories in Which Suspected Acute Pesticide Poisonings
and Deaths Resulting from Pesticide Exposure Were Reported.
Occupational
Home
Suicide
Homicide
Other
Total
1970
133/2
(1.5)
26/6
(23.0)
17/4
(23.5)
0/0
10/0
186/12'
1971
113/5
(4.4)
14/3
(21.5)
6/3
(50.0)
2/1
21/5
156/17
1972
127/2
(1.6)
14/4
(28.5)
7/2
(28.6)
0/0
9/2
157/10
1973
141/0
(0.0)
45/2
(4.4)
2/1
(50.0)
0/0
1/0
189/3
1974
66/0
(0.0)
33/2
(6.0)
5/2
(40.0)
9/1
8/2
121/7
Total
580/9
(1.6)
132/17
(12.9)
37/12
(32.4)
11/2
49/7
809/47
Figures in parenthesis are case/fatality rates.
112
-------
2. An aerial applicator crashes and the resultant fire limits
the value of analytical procedures which might establish
pesticide involvement.
3. Four deaths recorded in 1971 were the result of a traffic
accident (as previously mentioned) in which pesticides were
implicated. A passenger car and a truck carrying cylinders
of methyl bromide were involved. The cylinders were punctured
in the accident.
Thus, unusual situations, such as those described above, have been
assigned to the category "Other" and are included in this report as
examples of the difficulties which can be encountered in attempting to
assign pesticide-related incidents into simple categories.
Table 3 presents a breakdown of the major groups involved in
poisonings from the general category of "Occupational". As previously
mentioned, this category consistantly had the greatest number of cases.
Considering the 14 projects were concerned with investigating possible
adverse effects of pesticides, a natural group to study would be people
exposed to these chemicals. In developing a working rapport with such
individuals, the projects would be more atuned to occupational poisonings
by reason of close working contact and analytical laboratory services
of value in ascertaining exposure or poisoning. Thus the data presented
herein should not be misconstrued as meaning more poisonings occur among
the occupationally exposed but rather should be viewed in the proper
perspective of the close working relationship between the projects and
said individuals.
In order of rank, farm workers were reported as having experienced
the greatest number of poisonings followed by loaders/mixers, formulators,
ground applicators, farmers, aerial applicators, pest control operators
and miscellaneous occupations. In the miscellaneous category are
included suspected poisoned individuals whose occupation occasionally
resulted in exposure and subsequent suspected poisoning. Generally,
such incidents were infrequent and did not occur each year.1 For example,
in 1970, 1972, and 1973 there were 2, 18, and 35 firemen respectively
who were exposed to pesticide fumes during the course of fighting fires
and required treatment. Similarly, isolated instances of suspected
poisonings in mosquito abatement workers, greenhouse workers, and
construction workers were also reported.
As previously mentioned, accidents in the home were the second
leading cause of suspected pesticide poisonings reported to and investi-
gated by the projects. Of the total 132 cases, 82 (62 percent) involved
children under the age of fourteen. Table 4 gives data for each year
with respect to the number of cases involving children as compared to
the total cases reported, and the number of child fatalities as compared
to the total number of deaths encountered. There was a decrease in
cases involving children from 1970-72, however in 1973 and 74 a marked
increase in such cases occurred. As cited earlier, the major cause
of these poisonings was the result of improper storage of pesticides
either in an improper container or in areas easily accessible to
113
-------
Table 3. Major Occupations in Which Acute Pesticide Poisonings and
Deaths Were Reported.
Formulator
Farmer
Farm Worker
Ground Appl.
Aerial Appl.
Loader/Mixer
BCQ
Mis.c.
Total
1970
17/0^
5/0
63/1
8/0
11/1
14/0
1/0
14/0
133/2
1971
10/1
10/0
56/1
6/0
7/2
12/0
2/0
10/1
113/5
1972
13/0
4/0
41/1
20/1
8/0
18/0
2/0
21/0
127/2
1973
32/0
13/0
11/0
7/0
8/0
25/0
1/0
44/0
141/0
1974
0/0
10/0
11/0
12/0
4/0
17/0
2/0
10/0
66/0
Total
72/1
42/0
182/3
53/1
38/3
86/0
8/0
99/1'
580/9
I/ 17/0 represents 17 cases with zero deaths.
114
-------
Table 4. Acute Pesticide Poisonings and Deaths Among
Children Fourteen Years of Age and Under.
1970 1971 1972 1973 1974
Children
Ages 18/3 11/5 7/1 23/1 23/2
0-14
Percent of 18/186 11/156 7/157 23/189 23/121
Total Cases 9.6% 7.1% 4.4% .12.1% 19.0%
Percent of 3/12 5/15 1/10 1/3 2/7
Total Deaths 25% 33.0% 10% 33% 28.5%
115
-------
children. It is uncertain as to the reason for the increase during the
later years. A possible explanation could be increased usage by the
homeowner himself, where previously a professional applicator may have
applied the pesticide.
116
-------
RECYCLING PESTICIDE CONTAINERS
Paul E. Huber
Balcom Chemicals, Inc., Greeley, Colorado
The disposal of any waste material presents certain problems, de-
pending upon the type of waste material and the amount to be disposed
of. The disposal of used pesticide containers is no exception. Perhaps
the main problem associated with disposal of used pesticide containers
arises from the fact that virtually no pesticide container can be emptied
completely. There are always some residues, however small, in otherwise
empty containers, and these residues can present certain hazards to
humans, animals, and/or plants if not handled properly.
Pesticides are economic poisons; that is, they are chemicals speci-
fically designed to adversely affect or modify certain unwanted or unde-
sirable target organisms, whether they are insects, mites, fungi, weeds
or other undesirable plant growth, nematodes, rodents, or other pest
species. These chemicals, being economic poisons, must be able to affect
the target organisms as efficiently as possible, that is, with the least
cost possible, or at least at a cost which can be justified on the basis
of the desirable effects obtained.
In order for a pesticide to be efficient it must accomplish its de-
sired effect on the pest species at a relatively low dosage rate. How-
ever, pesticides, like other chemicals, can also have an adverse effect
on other, "non-target" organisms at relatively low dosage rates. Herein
lies the problem in disposal of used pesticide containers and the pesti-
cide residues contained in them.
An old concept recognized for many years in the medical profession,
"The Dose Makes the Poison", reveals that two things must be considered
in evaluating the "poisonous effect" of a material: (1) the material
itself and the specific effect it exerts on the organism in question,
and (2) the amount of material the subject is exposed to. In other
words, the subject organism, whatever it is, will be affected in some
certain, specific way by exposure to the specific material in question,
whatever that is, but the degree or severity of the effect will depend
on the amount of material to which the organism is exposed. The type
and amount, then, determine the dose, and the dose determines the
poisonous effect.
Now, the probability that a subject or organism will, under certain
conditions, be exposed to some material in a dose large enough to cause
an adverse effect on it can be termed "hazard". The specific degree,
or amount, of hazard associated with exposure to a material, then, is a
measure of the likelihood of injury occurring under those specific
conditions. This is the general concept of the term, hazard, as it will
be used herein.
As indicated earlier, the disposal of used pesticide containers can
present certain hazards to humans, animals, and/or plant life. The type
of container used and the type of material it contained are the first
consideration to be given. For example, small amounts of paper bags
117
-------
can usually be disposed of by burial in non-crop lands away from water
supplies, or burned if local and state laws permit, and the product label
states this as an acceptable disposal method. If the amount of such con-
tainers is large, and particularly if they held relatively volatile,
poisonous materials, it would probably be wiser to bury such containers
in a sanitary landfill.
It appears that, at least at the present time, glass and plastic
containers are best disposed of by destroying them and burying them in a
sanitary landfill. It does not appear practical to recycle these con-
tainers at the present time. The same is true for small metal containers.
One should not dispose of such containers in any manner in which the con-
tainers might be salvaged for other uses, especially by persons who might
not be aware of the hazards associated with the reuse of such containers.
Our main concern here is with the disposal, recycling or reuse of
metal pesticide drums. Obviously, not to recycle or reuse such drums
would be a waste of valuable resources. However, recycling and reuse of
these drums can be hazardous, particularly if such drums and their con-
tents are handled by persons who do not recognize and understand the
hazards, or are unwilling or unable to cope with them.
A quick view of some hazards associated with the disposal, recycling
or reuse of pesticide drums may help in understanding and solving the
problem. First, because pesticides are economic poisons, small amounts
of them may have adverse effects on certain specific organisms. Thus,
they are relatively hazardous to those organisms. Small amounts of 2,4-D
or other weed killers, for example, may have adverse effects on certain
types of plants or trees which may be exposed to water containing wash
solutions from drums which held these materials. Likewise, small amounts
of certain insecticides can be hazardous to humans and animals, so persons
handling such drums must not only be aware of the hazards, but be equipped
to handle these drums safely. This means they must use proper safety
equipment (e.g., rubber gloves, respirators, rubber footwear, etc.) and
use drum washing equipment designed to contain and handle toxic residues
lof this type. Also, care must be taken so no residue is released to the
environment where it might have an effect on other humans or animals,
including fish, downstream from the drum washing facility.
There are several different types of pesticides: insecticides, miti-
cides, herbicides, fumigants,.etc. There are also several classes of pest-
icides within each type; for example: organic phosphate insecticides,
chlorinated hydrocarbon insecticides, carbamate insecticides, etc.
Further, there are Technical liquids, .arid various formulated products,
such as: emulsifiable concentrates, flowables, oil solutions, etc., many
of which are formulated into materials containing different concentrations
of pesticides. Each type and class of pesticide and each formulation may
require somewhat different wash solutions to effectively remove and de-
grade the residual chemical from used drums. Ideally, the drum recondi-
tioner should be able to remove all traces of pesticide from the used
drum, decompose the pesticide into relatively innocuous materials, and
end up with a reconditioned drum which can be used without hazard to man
or the environment in which he lives.
118.
-------
Our current system Is designed to clean 55-gallon drums which have
been used for technical grade organic phosphate insecticides, but we
believe it can be used as well for drums which have contained formulated
organic phosphate insecticides. With possible changes in the wash solu-
tions used, we believe the same system can also be used for drums which
have contained other types of formulated products, such as chlorinated
hydrocarbons, 2,4-D type weed killers, and possibly others. However,
some details remain to be worked out before we would feel confident in
handling these drums properly.
First, the outside of the drum is washed with a high-pressure
washer. This recirculates a detergent solution from a large tank
through the wash nozzle, over the drum and back into the tank. Hard-
to-remove deposits can be removed by hand scrubbing or wire-brushing.
Next, the bungs are removed and the drum inserted over the flush
tank. Drums are positioned so that the 2" bung opening is placed over
a modified drum washing nozzle. A 15-HP electric motor drives a centri-
fugal pump which recirculates the decontamination solution, an alkaline-
hypochlorite-detergent solution, throughout the inverted drum. Since
this system is still under development, we cannot be more specific about
the decontamination solutions yet. Modifications may be required before
we are satisfied with these solutions.
At the present time we believe 1 to 2 minutes flushing time will be
sufficient for our purposes. Then the drum is moved over a similar drum
washing nozzle located above a similar but double-sized tank called our
first wash. A high-speed 10-HP-driven centrifugal pump recirculates the
decontamination/wash solution throughout the drum after which it flows
back into the tank. This tank and the two succeeding wash tanks are
large enough to accomodate two 55-gallon drums each at the same time.
The pumps, motors and piping are all large enough to handle at least
two drum washing nozzles at a time without significant loss of either
pressure or volume.
From the first wash tank, the drums are then moved to the second
wash tank where the washing is repeated, using a similar decontamination/
wash solution. From the second wash tank the drums are moved to the
third wash tank, and the washing is repeated again, this time with either
a decontamination/wash soution, or a clear water wash. After draining,
the drums are moved off of the third tank and rinsed off with clear water.
They can be rinsed inside with clear water again, if necessary.
The next step is inspection of the drum for faults in the liner or
the drum Itself. 'A light positioned inside the drum is used for visual
inspection of the lining. If the lining is not intact, that is, if any
flaws can be detected, the drum is marked for service other than as a
lined drum, or for destruction. If serious defects appear in the drum,
the drum is marked for destruction. These drums are crushed, using a
drum crusher we built, and taken to a steel mill for recycling of the
steel.
119
-------
Serviceable drums are then pressure tested, using a 3-arm Tight
Head Leak Tester, according to DOT specs. This unit pressurizes the-
drums with air to 7 pounds per square inch and forces the pressurized
drum under water to test for leaks. All leaking drums are marked for
destruction, as above.
After thorough drying, the drums are fitted with good bungs and
all new gaskets, and the drums are painted. At the present time we
are using a fast drying synthetic enamel, but we may find other paints
that work better. Finally, the drums can be coded, where necessary,
for the type of service into which they can be put.
The solution in the flush tank is checked periodically to make
sure it is still serviceable. At the time it no longer appears satis-
factory to use, it is pumped out into drums for disposal. We are still
working to develop an improved monitoring system. For the time being
we simply check the pH of the solution to maintain a pH of 8 to 14,
preferably 8 to 12, and a chlorine content of no less than 3% by titira-
tion with thiosulfate.
When the flush tank is emptied of spent decontamination solution,
it is refilled from the solution in our first wash tanks; this tank is
then refilled with solution from the second wash tank, and that, in turn
is refilled with solution from the third wash tank. Fresh water is used
to refill the third wash tank. All solutions are checked and adjusted
to contain the proper amount of decontamination chemicals, etc. In this
way all solutions are periodically replenished and kept fresh with a
minimum of spent solutions to be disposed of. A few reconditioners are
using a system somewhat like this. At least one of them recirculates
the spent solution through a sludge tank and filter system. This
approaches a zero discharge plant system. '
i
At the present time, since we are still in the early stages of
development, we don't know how frequently the flush solution will have
to be'replaced or how many drums can be flushed out before the solution
would need replacing. However, we believe the approach is sound and
reasonable and, with additional work, will become a practical operation
in the immediate future.
120
-------
REGULATION OF PESTICIDE STORAGE AN©' DISPOSAL
Raymond F. Krueger
U. S. Environmental Protection Agency
The disposal of excess pesticides and empty pesticide containers
is a widely recognized problem. But why is it a problem? We know that
some environmental damage does occur and there are recorded cases of
human and animal injury that can be cited. The magnitude of numbers of
empty containers also brings attention to this problem. There are
estimates of 11,000,000 total containers used in the United States
each year; upwards to 250,000 30 to 50 gallon drums; 15,000,000 5 gallon
cans; 25,000,000 1 gallon cans.
To add to the problem, there are serious gaps in technology. More
information is needed on the fate of pesticides when they are placed in
the ground. There are deficiencies in our knowledge of the incineration
of pesticide compounds. And to add to this, there is a lack of adequate
disposal facilities.
The 92nd Congress was made aware of these problems and responded by
adding Section 19 to the FIFRA amendments that were passed in 1972.
Section 19 covers disposal and transportation of pesticides. It requires
the Administrator to publish regulations and procedures on the proper
disposal of pesticides and empty containers. There are other provisions
which I will not go into here.
Progress on publishing regulations up to this point has included
the publication of acceptance regulations which specify the terms under
which the Administrator will accept suspended and cancelled pesticides
for disposal. In the same publication, that appeared in the Federal
Register May 1, 1974, was a set of recommended procedures on the storage
and disposal of pesticides. These provide the EPA recommendations on
the storage of pesticides, the disposal of excess pesticides and the
disposal of empty containers.
The most recent efforts of EPA, in the development of regulations
on disposal and storage were proposed regulations which were published
in the Federal Register, October 15, 1974. These regulations prohibit
the worst acts of disposal in contrast with the recommended procedures
which are not regulations and do not have force and effect of law.
The prohibitions that have been proposed apply to the disposal of
pesticides, pesticide containers, residues and pesticide-derived wastes.
There are 5 prohibited acts in this new regulation. The first covers
open dumping which is defined as, "any land surface disposal in a manner
which is exposed to the elements, to vectors and scavengers, which is
inconsistent with environmentally sound land disposal guidelines and
dumping for which no provisions were made to avoid contamination of
ground water."
121
-------
The hazard of open dumping which we are trying to control with this
regulation is best demonstrated by some of the cases which we have
received through our Pesticide Episode Review System. In one case report
received in 1974, three children suffered eye irritations after they
had been playing with a paper bag that had contained pesticide dust.
In another case, a 7-year-old child was brought to an emergency room
suffering from organophosphate poisoning. It was found that she had
been making mud pies with water from a carelessly discarded pesticide
can. In yet another case, a farmer placed a third of a bag of left-
over pesticide along with some other empty bags on a brush pile to be
burned. The brush pile happened to be in a cow pasture where cows
gained access to it, two cows died.
In yet another instance, 10 pigs suffered fatal exposure to pesti-
cides when they were turned into a field where the farmer had cleaned
his spray equipment. ;
The second prohibited act in the regulations covers Open Burning
which means: "combustion of pesticides or pesticide' containers by any
means other than in a pesticide incinerator." There are some exceptions
to this in that small quantities of emptied combustible containers, up
to fifty pounds or the amount accumulated in a single day's work may be
burned, providing due regard is given to wind direction and water con-
tamination and such burning must be consistent with Federal, State and
local regulations.
The basic reason for this regulation is to control the potential
release of toxic and otherwise harmful vapors that occur when pesticides
are burned in open fires. An example of the kind of injury that can
occur from this is shown in a case where a fire in a small storeroom that
contained pesticides, resulted in injuries to 22 firemen, 3 grounds
keepers, 1 newsman and a student.
The third prohibited act covers water dumping which means: "no
disposal into lakes, ponds, sewers or other water systems." Exceptions to
this include pesticides registered for use in water, use in compliance
with ocean dumping permits or suitable effluent guidelines. Hazards of
water dumping are well known. The effects of pesticides on aquatic life
can be quite serious. An example was a case where a considerable amount
of endrin was disposed of in a storm drain at a pesticide warehouse.
The storm drain led into a drainage ditch which emptied into a creek
which emptied into a river, etc. The result was 12,565 fish killed at
a cost to the company of $8,228.60, plus $7,512.29 for the investi-
gation.
The fourth prohibited act covers contamination of food or feed.
This means: "that no pesticide, pesticide product, pesticide container
or pesticide derived waste shall be stored or disposed of in a manner
contrary to label directions, or in their absences, in a manner which
may result in their confusion with or contamination of food, feed and
food or feed packaging materials." Exceptions to this are products for
home use and garden use may be stored in food or feed establishments,
and of course, products for use in animal feed are also exempt.
122
-------
To illustrate this hazard, a case was reported where a part of a
can of pesticides placed in a pickup truck with the grain spilled con-
taminating the grain which was later fed to horses. Four of 12 died.
In another case, a field worker, during a mid-morning break, went to
the farm truck where drinking water was usually stored. He drank from
a bottle found there which contained a toxic pesticide. He expired 12
hours later.
The last prohibited act is well injection, which means: "the
disposal under pressure or vacuum of pesticide wastes through a hole,
shaft or other opening to sub-surface stratum." This regulation does
not totally prohibit the use of well injection as a disposal system,
however, it requires approval by an appropriate State agency and EPA
Regional Administrator before pesticide disposal by this means can
be undertaken. Since well injection is not a widely used mode of dis-
posal of excess pesticides, cases of mismanagement have not been re-
ported, however, the reason for this regulation is the potential
hazard involved, that is large areas can be contaminated if well
injection goes wrong and cleanup is extremely difficult.
As previously stated, these regulations are intended to prohibit
the worst acts of disposal. They do not provide prescriptive guidance
to disposers. Guidance of this kind will be provided through other
means.
Future EPA strategy on disposal does not include the development of
further regulations, rather the intent is to concentrate on other options
to control the problem.
The basic means of providing information on disposal to the user
will be the label statement. Under section 3 of the FIFRA, Registration
and Classification, the registrant will be required to provide with each
reregistration, renewal or new product registration, a label statement
on container disposal. The statement must appear on the label in a
specified size type and location. The registrant will also be required
to provide information in support of that statement.
The applicator certification program instituted under Section 4 of
the FIFRA will be utilized as a media to provide disposal information to
applicators during the certification process. Improved disposal practices
should result.
Technology development will continue at about the present level with
investigations into incineration and landfill technology of pesticides and
other hazardous materials.
EPA recently awarded a grant under which model guidelines for
cleanup and disposal programs will be prepared covering the cleanup and
disposal program within a state and for the development of an Environmental
Impact Statement for such projects.
123
-------
We will also continue to study the available information to gain
better problem definition including review of the reports we receive on
injuries resulting from disposal management. Future strategies will
be guided by the results.
References
1. Federal Register, Vol. 39, No. 200, October 15, 1974, pp. 36847-36950.
2. Federal Register, Vol. 39, No. 85, May 1, 1974, pp. 15236-15241.
3. Federal Register, Vol. 40, No. 129, July 3, 1975, pp. 28242-28286.
4. Federal Register, Vol. 39, No. 197, October 9, 1974, pp. 36446-36452.
5. Gehlbach, S. H. and Williams, W. A. Pesticide Containers: Their
Contribution to Poisoning, Arch Environ Health 30:49-50 1975.
6. U.S. Environmental Protection Agency, Pesticide Episode Review System,
Personal Communications 1971-1975.
124
-------
AIR SAMPLING FOR PESTICIDES
David L. Spencer
Colorado State University
ABSTRACT
During the past few years there has been an extensive effort to
monitor the environment for pesticide residues.
The various sources of the pesticide residues detected in air have
been summarized by several investigators; however, comparatively little
data are currently available on types of pesticide residues and levels of
pesticides in air.
Several ambient air sampling devices are available and each has its
advantages and disadvantages. Some of the more commonly used samplers
include:
1. Greenburg-Smith impingers
2. Midwest Research Institute Sampler (MRI)
3. High Volume Air Sampler
4. Nylon Cloth Screen
5. Syracuse University Research Corporation (SURC)
A discussion of results from a comparative study of pesticide air
samplers will be presented.
125
-------
126
-------
PERSISTENCE OF TESMITICIDES IN SOIL
Virgil K. Smith
Forest Service—USDA, Gulfport, Mississippi
Damage from subterranean termites costs American homeowners millions
of dollars each year. These pests occur in every state except Alaska.
They are most destructive in the temperate and subtropical states but are
also becoming a serious problem in northern states because central heating
apparently enables them to live and work year-round in cold climates.
One of the best ways to control termites is by chemical treatment of
soil under and around the building; such treatment can kill or repel termites
for many years (Johnston,et al. 1971). One of our primary responsibilities
at the Wood Products Insect Laboratory in Gulfport, Mississippi, is to test
soil treatments for efficacy, persistence, and environmental impact.
A good soil treatment must be economical and persistent so that it gives
many years of protection. Therefore, these chemicals must be hydrophobic to
resist leaching by rainfall or rising water tables; they must have a low vapoi
pressure and they must be stable compounds to remain toxic or repellent to
subterranean termites of all species.
Four chemicals, which are recognized as good termiticides and have been
used nationwide, are aldrin, chlordane, dieldrin, and heptachlor. These
materials have been evaluated in southern Mississippi for over 20 years in
a sandy loam soil, unprotected except for a pine-hardwood forest cover.
The rainfall in this area averages over 6 feet per year. All four of these
chemicals are still giving 100 percent control, and the tests are continuing
(Smith,et al. 1972).
These same chemicals are being examined in several locations through-
out the Nation to evaluate exposure to various soils, climates, and species
of termites. In most locations the chemicals are showing similar efficacy
and behavior to that obtained in the southern Mississippi study area.
However, in Arizona, heptachlor has changed to 1-hydroxychlordene and
subsequently to its epoxide, l-hydroxy-2,3-epoxychlordene (Carter,et al.
1971). Both of these are more polar and, therefore, more water soluble
than heptachlor or its usual degradation product, heptachlor epoxide. Thus,
it is likely that heptachlor will not have the same long-term effectiveness
in Arizona soils as it has had in Mississippi.
Not only must termiticides persist in the soil, they must remain where
placed if they are to pose no environmental threat (Smith 1969). Gas
chromatographic analyses and bioassay have shown that there is a minimum
of movement of aldrin, chlordane, dieldrin, and heptachlor. For example, in
the Mississippi field study, when 1 percent chlordane was applied at 1 pint
of water emulsion per square foot, only traces of the insecticide were found
8 to 9 inches below the treated surface and 3 to 4 inches away horizontally.
Other organochlorine chemicals show similar lack of vertical or horizontal
movement (Smith 1968).
127
-------
The soil within and around the treated sites, and the area downgrade
from the study areas will be extensively sampled again in the fall of 1975.
The analyses of these samples should indicate if there has been any movement
or degradation of these four chemicals since the last extensive sampling
5 years ago.
We feel that our studies of efficacy, movement, and degradation of
termiticides have shown that the chemicals now recommended for termite
control, when properly applied, will remain as placed and environmentally
safe for many years. However, we are also investigating other possibilities.
For example, we are looking for a termiticide that will be persistent in the
soil under a building but rapidly degradable should it become exposed to
sunlight or other biodegradation forces. Chemicals are selected on the
basis of their chemical and physical properties, toxicity or repellency to
termites, toxicity to mammals, history of other uses, and their stability in
soils. Laboratory screening tests eliminate all but the most promising
termiticides, which are then evaluated in the field. Ultimately, research
like this should give us additional methods of dealing with the termite
threat.
128
-------
REFERENCES CITED
Carter, F. L., C. A. Stringer, and D. Heinzelman, 1971. l-hydroxy-2,3-
epoxychlordene in Oregon soil previously treated with technical
heptachlor. Bull. Environ. Contam. Toxic. 6(3): 249-254.
Johnston, H. R., V. K. Smith, and R. H. Seal, 1971. Chemicals for sub-
terranean termite control: Results of long-term tests. J. Econ.
Entomol. 64(3): 745-748.
Smith, V. K., 1968. Pesticides in soil. Long-term movement of DDT
applied to soil for termite control. Pestic, Monit. J. 2(1):55-57.
, 1969. Termite control and the natural environment. Br. Wood
Preserv. Assoc. Termite Symp. 1969: 101-104.
, R. H. Beal, and H. R. Johnston, 1972. Twenty-seven years of
termite control tests. Pest Control, 40(6):28, 42, 44.
129
-------
1,30
-------
POLYCHLORINATED BIPHENYLS - RESIDUES IN SEWAGE TREATMENT PLANTS
AND THEIR INCIDENCE IN A RIVER ECOSYSTEM
Richard E. Johnsen
Colorado State University
ABSTRACT
Polychlorinated biphenyl (PCB) residues have been monitored in Fort
Collins sewage sludge, initially in 1969, and continuously since the fall
of 1972. Samples of sewage treatment plant effluent water, river sediment,
fish and a few miscellaneous samples have been analyzed periodically since
early 1973. Since water and sediment upstream from the sewage outfalls
have undetectable or very low levels of PCBs, the sewage plants are impli-
cated as the primary source of PCBs into the river ecosystem. PCBs in
sludge have declined to a plateau level over the past two years but fish
do not show such a decline. For small fish, the whole sample was used while
in larger fish, samples of liver, muscle and gonad were analyzed. Dis-
cussion will center on residues in fish as a function of age, the impli-
cations of the residues found, and the analytical problems inherent in
cleanup and quantitation of a multi-component pollutant.
131
-------
132
-------
EPA'S AMBIENT PESTICIDE MONITORING PROGRAMS—AN OVERVIEW
Ann E. Carey
U.S. Environmental Protection Agency
Under the Federal Insecticide, Fungicide, and Rodenticide Act, as
amended, the Environmental Protection Agency is responsible for designing
and implementing a National Pesticide Monitoring Plan. A Plan is currently
in the review stage, but an existing National Pesticide Monitoring network
has been operated for several years and is coordinated by an inter-agency
body called the Monitoring Panel, of the Federal Working Group on Pest
Management. In addition to EPA, the agencies represented on this panel
are the Food and Drug Administration, which is responsible for monitoring
food and feed, the Department of Agriculture, which is responsible for
monitoring red meat and poultry, the Fish and Wildlife Service of USDI,
which monitors freshwater fish and various birds, and the Department of
Defense which has its own limited monitoring program on military reserva-
tions. The other environmental components are being monitored by the
Environmental Protection Agency. They include air, freshwater, estuaries,
the oceans, soil, crops associated with the soil,and human tissue. These
programs are the direct responsibility of the Ecological Monitoring
Branch in the Technical Services Division of the Office of Pesticide
Programs.
During this time, I'd like to talk a little bit about ambient pesti-
cide monitoring and then describe each of the monitoring programs we
operate and show you some of the results we've obtained.
Since some of you may already be involved with pesticide enforcement
actions, I'd like to distinguish ambient monitoring for pesticides, from
enforcement monitoring. Enforcement monitoring is the collection of
samples and the analysis of those samples to insure compliance with
laws and standards, while ambient monitoring is designed to determine
general environmental levels and trends, or changes in these levels over
time. The important distinction to note here is that enforcement
monitoring is often geared to detecting extremes for conformance to
standards, while ambient monitoring must be representative of the com-
ponent (air, soil, water, etc.) sampled because inferences about the
component, as a whole, will be drawn. However, many of the problems
associated with ambient monitoring can also be related to enforcement
monitoring.
All monitoring systems operate through three basic phases:
1. There is the field collection of the samples,
2. The laboratory chemical analyses of these samples, and
3. The analysis and interpretation of the resulting data.
I'm going to use the National Soils Monitoring Program to describe
each of these three phases and then only describe the field collection
phase for the remaining systems, since that is really the only different
phase among the programs.
133
-------
THE NATIONAL SOILS MONITORING PROGRAM
The National Soils Monitoring Program began in the U.S. Department
of Agriculture and was designed to collect statistically valid samples
from the nation's cropland, noncropland and urban areas. A total of
13,300 sites in the cropland and noncropland areas were identified with
1/4 of this number to be sampled each year. The design proved too
ambitious for the available resources and noncropland is no longer
sampled. The number of cropland sites sampled since the program was
instituted has ranged from 1500-1700 per year compared to a design
level of about 2200.
Since the program has not been able to consistently cover the whole
nation, a modified design has been developed for FY 1976. To date,
baseline data on pesticide residue levels have been collected for
cropland soil in 48 states; 28 states have data for noncropland soil;
and 42 urban areas have been sampled in our urban monitoring program.
For the cropland and noncropland sampling, a lO^acre sample site
is used. At each site, 50 2 x 3 inch cores are collected on an evenly-
spaced, 5 x 10 grid. Where a crop is available, it is also sampled.
In urban areas, we use a 50 x 50 ft. plot, with 16 soil cores being
taken over a 4 x 4 grid.
The collected cores are then sieved and thoroughly mixed three
times through a 1/4" mesh and a two-^-quart subsample is taken. Equipment
is carefully washed to insure that there is no possibility of cross-
contamination between sampling sites. For each site a map is made to
enable us to go back to that site after the appropriate time interval
to take trend data.
The following information is also obtained from the farmer:
The crops grown on the site
Irrigation used
Pesticides used
Crop each pesticide applied to
Formulation
Pounds of active ingredient applied
Method of application
After the sample has been collected in the field, it is sent to
our Pesticide Monitoring Laboratory at the Mississippi Test Facility,
Here the samples are analyzed using primarily gas-liquid chromatography.
We also have atomic absorption spectrometers and a polarograph for our
heavy metals work, liquid-liquid chromatography and a mass spectrometer
for confirmatory work.
At this laboratory there are an additional 24 persons who provide
the analytical support for the soil, water, estuarine and ocean systems,
as well as various special projects. This amounts to an incoming sample
load of about 6,000 samples per year and well over 12,000 analyses.
Most samples are routinely analyzed for chlorinated hydrocarbons and
134
-------
organophosphates. Additionally, for cropland soil, arsenic and
triazine analyses are also conducted. Heavy metal analyses for lead,
cadmium, arsenic and mercury are run on estuarine samples and urban
soil samples.
When the chemical analyses have been completed, the resulting data
are returned to Branch headquarters in Washington where they are
statistically analyzed using either small, desktop computers such as the
Hewlett Packard, 9100-B, or handled by our larger computer support
programs. Presently all of our monitoring programs are computerized.
THE NATIONAL ESTUARINE MONITORING PROGRAM
The objective of the National Estuarine Monitoring Program is to
determine pesticide levels in fish in estuaries. Approximately 113
estuaries are sampled for herbivorous and carnivorous fish. Collections
have been made twice a year; in FY 76 the schedule will go to once a
year. Sampling teams attempt to collect only young of the year, since
this age group indicates the current contamination load in the estuary.
The samples are shipped to the Pesticide Monitoring Laboratory at
Bay St. Louis, Mississippi, for analysis.
Originally, this program sampled crustaceans and shellfish which
are good indicators of recent contamination. They are, however, able
to purge themselves of residues within a fairly short period of time.
Since insufficient resources were available to continue the program of
monthly collections of shellfish, the program was redesigned in FY 1972.
Fin fish were selected since they retain pesticide residues longer,
are mobile, and therefore, a better overall indicator and integrator of
pesticide pollution in an estuary.
THE NATIONAL HUMAN TISSUE MONITORING PROGRAM
The purpose of the Human Monitoring Program is to determine, on a
national scale, the incidence and level of exposure to pesticides
experienced by the general population and to identify changes and trends
in these parameters when they occur. Pesticide residues and their
metabolites that are detected reflect a human's total exposure to these
chemicals and his/her physiologic ability to handle them. This program
was initiated in 1967 by the Pesticides Programs, Communicable Disease
Center of the Public Health Service, and was transferred to the
Environmental Protection Agency upon its creation in 1970.
The major activity of this program is the collection and chemical
analysis of samples of human adipose tissue which are obtained through
cooperating pathologists in 75 collection sites selected according to
an experimental design in the conterminous 48 states.
All analyses for this program are conducted by contract laboratories
using only methodologies specified by the program. These laboratories
are equipped with gas-liquid chromatographs with electron capture and
other detectors. They are required to maintain acceptable performance
levels in the interlaboratory quality assurance program moderated by
the Pesticides and Toxic Substances Effects Laboratory. This laboratory
135
-------
also serves as technical consultants for the analytical portions of the
program. All samples are analyzed for selected chlorinated hydrocarbon
insecticides and polychlorinated biphenyls using a multi-residue approach.
This multi-residue procedure is capable of detecting some qrganochlorine
pesticide residues and metabolites as well as polychlorinated biphenyls.
A proportionate stratified sampling design is followed,for selecting
cities from which samples .are collected. The number of cities needed in
each census division is determined based on population distribution.
This type of design provides samples which are representative of the
pesticide residue levels in the general population. For each collection
site, an annual sample quota reflective of the demographic (age, sex, and
race) distribution of that particular census Division is established.
Adipose tissue collected by cooperating pathologists is from postmortem
examinations and from specimens previously removed during therapeutic
surgery. Information recorded for each tissue sample analyzed includes
age, sex, race, height, weight, pathological diagnosis, and occupation.
Geographic residence is assumed to be in -the general location of the
collection site. Since the objective of the program is to reflect the
pesticide burden in the general population, samples are not collected
from victims of known or suspected pesticide poisonings, from chronically
ill patients, or from patients institutionalized for extended periods.
Other human substances, such as urine, blood and milk, are being
collected for analysis to detect some of the newer classes of pesticides.
Currently a special project measuring organophosphate insecticide
metabolities in urine is underway.
THE NATIONAL WATER MONITORING PROGRAM
The National Water Monitoring Program is a cooperative effort
between EPA and the U. S, Geological Survey. The current design calls
for water samples to be taken quarterly and sediment samples to be taken
biannually at 153 sampling sites in 17 major drainage basins across the
country. Problems encountered with both the analytical methodologies
and sample collection equipment have delayed the implementation of this
program. However, all scheduled collections will be made in FY 1976.
Once the data are available, an intensive evaluation will be made to
determine whether or not to modify the present sampling design.
THE NATIONAL AIR MONITORING PROGRAM
The National Monitoring Program for Pesticides in air was in
existence from 1970 through 1972, and detected low levels of a large
number of residues. That program was discontinued primarily because of
instrumentation problems. When we first took over this program in 1972,
we felt that the program should not be reinitiated until a sampler was
developed that could detect a wide range of pesticidal residues. Since
that time, however, we've come to the realization that there may be no
one, all-purpose sampler for pesticides in air.
Dave Spencer has already explained the types of air samplers currently
available and the advantages and disadvantages to each one, so I won't
136
-------
go into that aspect. Presently our Branch is operating a pilot monitoring
program for pesticides in air in three cities. In FY 1976 we hope to
expand the program to six cities.
THE OCEAN MONITORING PROGRAM
The oceans are generally considered an important sink for many
persistent pollutants and to date there has been no systematic monitoring
of the oceans for pesticide residues on a continuing basis. The National
Marine Fisheries Service approached us, suggesting that a cooperative
program might be established between themselves and the Environmental
Protection Agency. Basically, they agreed to supply ship time, collect
fish samples at sea, and our Agency would then do the chemical analyses
and supply other monitoring support. Knowing that the Agency could not
afford to pay the cost of ship time, we took advantage of this situation.
In FY 1975, fish samples were collected at 114 sites on six ocean cruises
off both coasts of the United States. The original design has been
modified for FY 1976 to include only those areas where residues were de-
tected in the FY 1975 sampling.
FEED MONITORING
As mentioned earlier, the Food and Drug Administration is responsible
for monitoring feed. However, after the episode with dieldrin contamina-
tion of chickens over a year ago, there was astrong feeling within the
agency that a more comprehensive pesticide monitoring program be
established for animal feed and feed components. When FDA was contacted
by Ecological Monitoring Branch representatives, they proposed an
expanded, cooperative feed monitoring program between FDA and EPA.
This has been agreed to by both agencies. The first 100 samples have
been received and are being analyzed at our MTF Pesticide Monitoring
Laboratory.
137
-------
138
-------
MONITORING OF AGRICULTURAL INSECTICIDES INTO THE
COOPERATIVE COTTON PEST MANAGEMENT PROGRAM IN ARIZONA, 1971
H. Richardson
A County-wide cotton pest management program was initiated in
Pinel County, Arizona in 1971 as a cooperative endeavor of the United
States Department of Agriculture and the University of Arizona Depart-
ment of Entomology. The main objective of this pilot study was to
establish a more ecologically, economically and socially acceptable
system for protecting cotton from insect pests.
During the first year of the study various aspects of this pest
management program were organized and executed, including an environmental
impact analysis program. This report concerns results obtained from the
latter program.
Both biotic (birds, snakes, lizards, frogs, fish, etc.) and
abiotic (soil, sediment, water) type samples were collected in this
program.
SAMPLING PROCEDURES
The sample collection and analysis programs were designed in a
fashion to obtain comparisons of residues within and outside the project
areas, before treatment and at harvest. The effects, if any, of
pesticide treatments on pond water and aquatic life were also determined
by collecting samples of water, sediment and aquatic organisms from
ponds located near the cotton sites.
Biotic samples collected in the 1971 program included: (1) birds,
(2) toads and frogs, (3) snakes, (4) lizards, (5) insects (aquatic and
terrestrial) and (.6) fish (minnows). Abiotic samples collected were
(1) pond water, (2) pond sediment and (3) soil from cotton fields.
Cotton fields in the Pest Management Program were selected to
provide at least one site in each cotton growing area of Pinel County,
further restricted to areas adjacent to or nearby permanent or semi-
permanent water. The sites outside the program were chosen for their
location near an in-program cotton site. Pesticide treatment informa-
tion was obtained for each of the sampling sites, when available;
this information is given in Table 1.
Random soil samples were collected within and outside program areas
utilizing a core-type sampling device as described in a previous publi-
cation by Woodham, et al. (6). All soil was composited, screened,
weighed, stored and shipped according to these procedures.
Sediment samples were randomly collected with an Eckman^ Dredge,
composited, subsampled, stored and shipped according to the previously
mentioned publication. Approximately 10 drags of the dredge were
required for each sample. Sediment was collected as near as possible
to where the corresponding water sample was collected.
139
-------
Random water samples were collected as near as possible to the
sediment sampling site. This was accomplished utilizing the dredge
previously mentioned. By varying the depth of the dredge, without bottom
samples, a representative one-gallon sample of pond water, was obtained.
Birds, mammals, lizards, frogs, toads and snakes were collected by
shooting with either a .22 calibre rifle with birdshot or a 12 gauge
shotgun within the various sampling sites. Minnows and other fish were
collected utilizing a small-mesh minnow seine, water beetles were collected
with sediment samples. Grasshoppers were collected in the fields
utilizing nets. Crickets and some of the ants were collected by hand;
the remaining ants were collected with an aspirator-type sampling device.
Soil, sediment and water samples were stored in a refrigerator
(cs. 40°F.) pending shipment to the Brownsville Laboratory. Samples were
shipped via the fastest possible means and stored at 40 F pending
analyses. All biological samples were immediately frozen (0°F) pending
shipment. Shipments were made in styrof.oam biomailers with dry ice by
air mail; once samples were received in the laboratory, they were
immediately unpacked and stored again in a 0°F freezer pending subsequent
residue analysis.
PREPARATION OF SAMPLES
Extraction
Soil Samples
Representative 300 gram soil samples- were extracted with 600 ml
of a 3:1 (v/v) hexane-isopropyl alcohol solvent mixture in half-gallon
Mason jars on a concentric rotator for 4 hours as described in a
previous procedure by Woodham, et al. (6). After rotation, 300 ml of
the extract was filtered into 1000 ml separatory funnels where the
alcohol was removed by washing 3 times with equal volumes of distilled
water. The hexane extract was dried by filtering through a layer of
anhydrous granular sodium sulfate into amber sample bottles. The bottles
were sealed and kept under refrigeration pending subsequent GLC analysis.
Soil extracts did not normally require any cleanup prior to residue
analyses.
Sediment Samples
Sediment samples were prepared and stored as previously described
for the soil samples, except 250 grams of anhydrous, granular sodium
sulfate was added to absorb the excess water in the samples. Normally,
sediment samples contained excessive amounts of sulfur which interfered
with the normal analysis for both organophosphates and chlorinated hydro-
carbon pesticide residues. These samples were treated utilizing the
sulfur removal procedure of Schutzmann, et al. (3).
140
-------
Water Samples
Water samples were extracted according to the procedure described
by Woodham, et al. (.6). Briefly, the procedure involved extraction of
representative 500 gm subsamples in 1000 ml separatory funnels 3 times
with 100 ml portions of Nanograde (Mallinckdrodt, Inc.) dichloromethane.
The organic layers were filtered through a layer of granular anhydrous
sodium sulfate to remove any entrained water into 500 ml Erlenmeyer
flasks. One millileter of a 0.01% Nujol in hexane solution and glass
beads were added and the solvent evaporated through Snyder columns to
ca. 5 ml on a warm (40-50°C) water bath. One hundred millileters of
Nanograde hexane was added through the Snyder columns and the solvent
again evaporated to ca. 5 ml. The concentrated extracts were transferred
to 15 ml stoppered, graduated centrifuge tubes where the volume was
adjusted to 12.5 ml with Nanograde hexane. Samples were stored in a
refrigerator pending subsequent glc analysis. Water samples did not
normally require cleanup before residue analysis.
Biological Samples
Larger biological samples (rabbits, birds, lizards, snakes, fish,
etc.) were prepared according to the procedure utilized by Woodham,
et al. (6) by first thoroughly grinding in a Hobart (Hobart Mfg. Co.)
food grinder, then weighing representative 25 gram subsamples into
1000 ml Waring blender jars with 150 ml of a 3:1 mixture of Nanograde
hexane: is.opropyl alcohol and blended at low speed for two minutes. The
macerated materials were then transferred into half-gallon Mason jars
with 250 ml of the hexane:isopropyl alcohol mixture, the jars sealed and
rotated concentrically for four hours. The extracts were then filtered
through glass wool into 1000 ml separatory funnels where the alcohol was
removed with three successive washings of equal volumes of distilled
water, discarding the aqueous layers. The hexane extracts were filtered
through layers of anhydrous granular sodium sulfate into graduated
cylinders where measured aliquots were collected. These aliquots were
transferred into amber sample bottles, sealed and stored in a refrigerator
pending subsequent cleanup.
Smaller biological samples, mainly insects, weighing 10 grams or
less were weighed and transferred into micro-blender cups with 50 ml of
Nanograde isopropyl alcohol and blended for 2 minutes at high speed.
The mucerates were transferred into one quart Mason jars with 150 ml of
Nanograde hexane, the jars sealed and rotated concentrically for four
hours at 30 rpm. Extracts were then filtered into 500 ml separatory
funnels where all alcohol and water were removed by 3 successive
washings with equal portions of distilled water. The extracts were
dried and stored under refrigeration as described previously.
Cleanup
Biological samples were cleaned up first by a liquid:liquid partition-
ing between two immiscible organic solvents (hexane:acetonitrile) to
remove fats and oils as described by Woodham, et al. (6). Briefly, the
procedure involved transfer of 10 gram aliquots of the extracts into
250 ml separatory funnels, diluting to exactly 50 ml with Nanograde
141
-------
hexane and partitioned 3 times with 100 ml portions of Nanograde
acetonitrile saturated with hexane. The hexane layers were discarded;
the combined acetonitrile layers were collected in 500 ml separatory
funnels and washed once with 20 ml of Nanograde hexane saturated with
acetonitrile to remove any remaining traces of fats or oils.
The acetonitrile fraction was divided into two equal portions for
further processing as follows: (1) Organophosphates - one half of the
acetonitrile fraction was transferred into 250 ml Erlenmeyer flasks,
1 ml of a 0.01% solution of Nujol in hexane and glass beads added and
the solvent evaporated to ca. 5 ml on hotplates through Snyder columns.
The concentrated extracts were transferred to 15 ml graduated, stoppered
centrifuge tubes where the volume was adjusted to exactly 12.5 ml with
Nanograde acetonitrile. The stoppered tubes were stored in the refriger-
ator pending subsequent GLC analysis, (2) Chlorinated hydrocarbons -
the remaining half of the aliquots were transferred into 250 ml Erlenmeyer
flasks, glass beads and 1 ml of a 0.01% Nujol in hexane solution added
and the solvent evaporated to ca. 10 ml on hotplates through Snyder
columns. The flasks were cooled and 100 ml of hexane was added through
the Snyder columns and the evaporation procedure described previously was
repeated on a hot water bath. This step was repeated two additional times,
the flasks sealed and stored in a refrigerator pending subsequent
Florisil (Floridin Co.) column cleanup.
Florisil Cleanup
Preparation and description of the Florisil chromatographic cleanup
columns were described in the previous publication by Woodham, et al. (6).
Only 2 fractions were collected from the columns, since organophosphate
residue analysis was performed from the hexane:acetonitrile partitioned
samples.
Aliquots from the extraction procedure were transferred into the
hexane prewashed columns and eluted first with 100 ml of Nanograde hexane,
then with 100 ml of a 15% diethyl ether in hexane solution, collecting
each eluate in separate 250 ml Erlenmeyer flasks. Eluates were evapora-
ted and stored as described in the previous publication. The less polar
pesticide residues such as lindane, heptachlor, aldrin, DDE, TDE, DDT,
toxaphene and others were contained in the first fraction, while the
second fraction contained the more polar residues, dieldrin, endrin,
heptachlor, epoxide, and others.
GAS CHROMATOGRAPHIC ANALYSIS
Gas-liquid chromatography (glc) determinations were made utilizing
MY-220 gas-liquid chromatographs (Tracor, Inc.) equipped with Ni-63
high-temperature electron capture detectors and a Melpar Flame Photo-
ifletric Detector (FPD). The FPD detector was designed to operate in both
the sulfur (394 mp) and the phosphorous (526 mp) modes simultaneously.
,142
-------
The instruments were operated utilizing the following operating
parameters:
Columns (61 x 1/4", glass):
(1) 3% DC-200 on 100-200 mesh Gas Chrom-Q (Applied Science
Laboratories, State College, Pa.).
(.2) 3% OV-1 on 80-100 mesh Chromosorb-W (Johns-Manville, Inc.).
(.3) 5% QV-1 on 100-120 mesh Gas Chrom-Q (Applied Science).
(4) An 11% mixture of 1.95% QF-1:1.5% OV-17 on 80-100 mesh
Gas Chrom-Q (Applied Science).
A 3% DC-200 column as described in (1) was also utilized
for the FPD analyses of organophosphate residues.
Temperatures (Isothermal):
Columns - 200°C
Injectors - 250°C
Detectors - EC - 300°C
FPD - 200°C
Gas Flow Rates:
Nitrogen (carrier) - 80 ml per minute
Air - 40 ml per minute
Hydrogen - 75 ml per minute
Oxygen - 20 ml per minute
Recorder chart speed was 30 inches per hour; sensitivity was ad-
justed to obtain approximately half full-scale deflection of the recorder
pen with a 0.05 ng injection of aldrin on the electron capture detectors
and 1.50 ng of ethyl parathion on the FPD detector. Calculations were
based on peak heights obtained from analytical standards compared with
identical peaks in the samples. Lower limits of sensitivity were deter-
mined to be 0.01 ppm (.0.01 ppb for water) for the organophosphates and
chlorinated hydrocarbon pesticides.
Toxaphene was analyzed utilizing the GC method of Hawthorne and
Dawsey (2). Extraction, cleanup and other processing steps were identi-
cal with that utilized for the organochlorine and organophosphate resi-
dues. Briefly, the quantitation procedure involves comparison of peak
heights of the four major peaks in a toxaphene standard with peak heights
of these peaks in the environmental samples. Gas chromatographic operating
parameters were identical with those described previously for organo-
chlorine and organophosphate pesticides on the 3% DC-200 column. When
interfering peaks were present which would interfere with any of the four
major peaks of toxaphene, as few as two of these peaks were utilized for
quantitation. Lower limits of sensitivity were determined to be 0.05 ppm
(0.05 ppb for water).
143
-------
Doubtful pesticide peaks were confirmed by several methods; thin-
layer chromatography (TLC), Schutzmann, et al. (4): partitioning
coefficients (p-values), Howman and Beroza (1), chemical means, Woodham,
et al. (5) and multiple column methods. Pesticide peaks which were not
at least twice the "noise" level were rejected.
RECOVERY
A series of control samples extracted, cleaned up and analyzed in
identical manner as the unknowns, was included with each group of samples.
These controls included a solvent check, non-fortified sample and a sample
fortified with known amounts of the pesticides suspected. These controls
were necessary in order to monitor any possible contamination of solvents,
determine any pesticides in the "blank" sample material and to determine
extraction and analytical efficiency of the entire procedure. No inter-
fering peaks were detected in the solvents; pesticides detected in the
blank samples were subtracted from those in the fortified samples to
obtain recovery percentages. Average recovery values are listed in
Table No. 2.
RESULTS AND DISCUSSION
Residue data for the 1971 Arizona Pest Management Project is given
in Tables 3-9. No detectable residues of organophosphate or organochlorine
pesticides were found in the pond water or sediment sampled inside or
outside program areas. Table 3 presents residue data for the soil samples
collected within and outside the program areas, before pesticide treat-
ments began and at harvest. The organophosphate, ethyl parathion, was
detected in trace amounts (0.13 and 0.03 ppm) in soil from sites 2A and
3A, respectively, both within the program area, at harvest. No detect-
able organophosphate residues were found in soil collected preceding
initiation of pesticide treatments or in soil from outside the program
area. Detectable residues of ethyl parathion were found in soil from
sites IB, 2B, 3B, 5B, 7B and 8B at harvest outside program areas, ap-
parently a result of drift from serial treatments in adjacent cotton
fields.
Residues of several organochlorine pesticides were detected in all
soil preceding pesticide treatments and at harvest, within and outside
program areas. Residues ranging from 0.29 ppm to 1.43 ppm p,p'-DDE,
0.11 ppm to 1.49 ppm p,p'-DDT and <0.05 ppm to 3.94 ppm toxaphene were
detected in soil from sites within the program area before the pesticide
application season. At harvest, residues ranged from 0.21 ppm to 0.76
ppm p,p'-DDE, 0.11 ppm to 1.33 ppm p,p'-DDT and 1.18 ppm to 5.18 ppm
toxaphene in the program area. Outside the program area, the same
organochlorine pesticide residues were detected, ranging from 0.50 ppm
to 1.82 ppm p,p'-DDE, 0.25 ppm to 1.53 ppm p,p'-DDT and <0.05 ppm to
2.68 ppm toxaphene in pretreatment soil. At harvest, organochlorine
pesticide residues ranging from 0.33 ppm to 1.24 ppm p,p'-DDE, 0.31 ppm
to 0.86 ppm p,p'-DDT and 2.41 ppm to 4.04 ppm toxaphene were detected
in soil collected outside the program area.
144
-------
Residue data for pesticides in biologicals are given in Tables
4-9. Ethyl parathion residues were detected in four biological samples;
0.03 ppm in a frog sample collected before treatment within the program
area, 1.24 ppm in a sample of minnows collected before treatment within
the program area, 0.08 ppm in another sample of minnows also collected
before treatment inside the program area, and 0.03 ppm in a rabbit sample
collected before treatment outside the program area. No other organo-
phosphate pesticide residues exceeding the detectable limits of 0.01 ppm
were found in biological samples.
Organochlorine pesticide residues were detected in all of the biologi-
cal samples, predominantly p,p'-DDE, p,p'-DDT and other isomers of
DDE, DDT, and TDE (DDD). Residues of other organochlorine pesticides
were also detected, but not as consistent and in lower concentrations.
Residue patterns were similar between samples collected from program
areas and outside program areas except the concentrations were generally
lower in samples from outside the program areas.
Pretreatment samples collected inside the program areas showed sig-
nificant residues of: heptachlor epoxide in 14% of the frogs and 33% of
the fish samples; o,p'-DDE in 43% of the frogs, 100% of the fish, 9% of
the birds, 17% of the lizards and snakes and 50% of the insect samples;
p,p'-DDE in all of the frogs, fish, birds and lizards and 75% of the
insect samples collected; o,p'-TDE in 43% of the frog samples; p,p'-TDE
in 71% of the frogs, 100% of the fish and 33% of the snake and lizard
samples; o,p'-DDT in 71%, 67% and 25% of the frogs, fish and insect
samples, respectively; p,p'-DDT in 86% of the frog samples, 100% of the
fish samples, 27% of the birds, 33% of the lizards and 25% of the insect
samples.
Harvest samples collected inside the program areas indicated sig-
nificant residues of p,p'-DDE in all of the frogs, fish and lizards
collected, in 94% of the birds and 55% of the insects collected. Sig-
nificant residues of p,p'-DDT were detected in only the frogs (92% of
samples) and lizards (42% of samples). All other organochlorine pesticide
residues were below 0.05 ppm.
Pretreatment samples collected outside program areas produced
significant residues of heptachlor epoxide in 7% of the insect samples;
o,p'-DDE residues in 25%, 100%, 15% and 31% of the frogs, lizards,
and insects, respectively; p,p'-DDE residues in significant quantities
in the frogs (100% of samples), fish (100% of samples), birds (100% of
samples), lizards (77% of samples), insects (33% of samples) and rabbits
(50% of samples); dieldrin residues in frogs (37% of samples), fish
(.67% of samples) and insects (14% of samples); significant o,p'-TDE
residues were detected in only the frogs (12% of samples) and insects
(14% of samples); p,p'-TDE residues were detected in frogs, fish, lizards,
and insects for 87%, 100%, 46%, and 7%, respectively; p,p'-DDT residues
were detected in significant concentrations in 87% of the frogs, 100%
of the fish, 17% of the birds, 31% of the lizards, and 7% of the
insect samples.
145
-------
Harvest samples collected outside program areas indicated only
significant residues of p,p'-DDE and p,p'-DDT. Residues of p,p'-DDE
exceeding 0.05 ppm were detected in 100% of the frogs, lizards and
fish, 94% of the birds, and 62% of the insect samples. Harvest residues
of p,p'-DDT exceeding 0.05 ppm were found in 100% of the frogs and 50%
of the lizard samples collected.
Significant accumulations of pesticides utilized during the 1971
growing season in the Arizona Cotton Pest Management Program were not
indicated, except for toxaphene in soil samples. A significant increase
of toxaphene residues (between pretreatment and harvest) was noted in
soil from program areas and also outside these areas. This was probably
due to a number of factors, drift, leaching, runoff, mechanical movement
and many others. No toxaphene residues exceeding detectable limits
were found in sediment, water or biological samples inside or outside
program areas, which indicates that no problem exists for transfer of
this chlorinated camphene to the biological food chain in harmful levels.
Conversely, detectable residues of dieldrin, (3-BHC and heptachlor
epoxide which did not appear in soil, -sediment or water in detectable
quantities, were found in essentially all of the biological materials
sampled, with the exception of rats and rabbits. These residues were
apparently a result of pesticide treatments from previous years.
Residues of DDT, DDE and IDE which appeared in soil samples, but
not in sediment and water, wer.e also present in all of the biologicals
sampled, including aquatic organisms. These residues were also apparently
a result of past pesticide treatments.
In order to establish a trend of accumulation or decline of pesticide
residues, a longer study must be conducted. The present study will be
continued for a minimum of 3 and most likely 5 years before any baseline
may be established. This is necessary to produce evidence of the success
of this integrated system of pest control and how it may be applied to
future programs of this type.
146
-------
Table No. 1:
Pesticide Treatment Information, Final County, Arizona, 1971
Site
No.
1A
2A
3A
4A
5A
6A
Application
Date
8/25/71
7/14/71
7/24/71
7/30/71
8/5/71
8/12/71
8/20/71
_„
,-„._._,-„-
7/23/71
8/6/71
8/15/71
8/22/71
7/23/71
7/30/71
8/4/71
8/11/71
Pesticide
Strobane/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
No Information
Available
No Information
Available
Dimethoate
Malathion
Ethyl Parathion
Methyl Parathion/
Toxaphene
Sevin-Molasses
Sevin-Mo lasses
Sevin-Molasses
Sevin-Molasses
Amount Applied (Actual)
Per Acre
1/3 gal.
1/3 gal.
1 pt.
1-1/2 pt.
1-1/2 pt.
1 pt.
1-1/2 pt.
,
-,
Not Available
Not Available
Not Available
Not Available
2 Lb.
2 Lb.
2 Lb.
2 Lb.
147
-------
Table No. 1 cont'd
Site
No.
6A
(cont'd)
7A,
8A
Application
Date
8721/71
8/27/71
7/16/71
7/25/71
8/2/71
8/9/71
8/12/71
8/16/71
8/27/71
9/11/71
9/14/71
9/23/71
7/17/71
7/28/71
Pesticide
Methyl Parathion/
Toxaphene
Methyl' Parathion
Toxaphene
Methyl Parathion/
Toxaphene
Methyl Para'thion/
Toxaphene
Methyl Parathion/
Toxaphene
Methyl. Parathion/
Toxaphene
Ethyl Methyl
Parathion
Endrin
Methyl Parathion/
Toxaphene
Methyl Parathion/
Toxaphene
Ethyl Methyl
Parathion
Ethyl Parathion/
Toxaphene
Ethyl Methyl
Parathion
Endrin
Ethyl Methyl
Parathion
Ethyl Parathion
Toxaphene
Ethyl Methyl
Parathion
Amount Applied (Actual)i
Per Acre
1 qt.
3-1/4 qt.
1-1/2 qt.
1-1/2 qt.
1-1/2 qt.
1/3 gal.
1/3 gal.
1 pt.
1/3 gal.
1/3 gal.
1 pt.
1/3 gal.
1/6 gal.
1 qt.
1/6 gal.
1 qt.
1 qt.
1 pt.
148
-------
Table No. 1 cont'd
Site
No.
8A
(cont'd)
9A
Application
Date
8/22/71
9/1/71
7/26/71
7/30/71
8/7/71
8/10/71
8/15/71
8/25/71
8/29/71
10A
Pesticide
Ethyl Methyl
Parathion/
Toxaphene
Ethyl Parathion/
Toxaphene
Ethyl Parathion/
Methyl Parathion
Ethyl Parathion/
Methyl Parathion
Methyl Parathion/
Toxaphene
Methyl Parathion/
Toxaphene
Methyl Parathion/
Toxaphene
Methyl Parathion/
Toxaphene
Methyl Parathion/
Toxaphene
No Information
Available
Amount Applied (Actual)
Per Acre
1/3 gal.
1/3 gal.
1/3 gal.
1/3 gal.
1/3 gal.
1/3 gal.
1/3 gal.
1 qt.
1 qt.
149
-------
Table No. 2:
Average Pesticide Recoveries from Fortified Environmental Sample Materials
Recovery, %
Sample
Material
Soil
Sediment
Water
!_, Lizards and
Ui . Snakes
° Frogs, Toads
and Polliwogs
Birds, Nestlings
and Eggs
Fish and Fresh
Water Clams
Insects
Ethyl
Parathion
102.2
93.0
89.8
88.4
95.8
93.5
86.4
95.7
Methyl
Parathion
96.4
80.0
91.3
85.4
88.4
94.8
96.0
103.3
Mala-
thion
101.5
86.0
89.2
82.6
83.4
97.0
84.6
106.3
Methyl
Trithion
100.6
90.0
78.9
82.6
97.8
93.6
60.8
101.8
6- Y-
Ethion BHC BHC
107.3 91.0 89.0
89.0 85.5 94.2
99.6 93.6 92.4
74.1 100.0 97.0
96.3 100.0 97.0
95.2 100.0 75.6
72.6 100.0 78.9
99.8 100.0 100.5
Hepta-
chlor
84.1
86.1
93.0
100.9
. _ .
101.2
86.4
72.7
88.6
Aldrin
89.4
80.8
89.9
103.5
95.1
69.0
58.4
76.2
Heptachlor
Epoxide
94.8
91.9
94.6
82.9
101.2
85.8
81.4
100.5
o,p-
DDE
79.7
85.5
95.6
71.5
76.0
93.2
100.2
93.6
p,p' Diel-
DDE drin
91.0 91.0
85.5 85.5
93.5 93.1
82.9 82.9
76.0 96.8
89.0 85.8
100.2 78.9
88.9 96.5
End-
rin
91.0
79.4
95.9
96.8
96.8
91.9
76.3
102.7
o,p' p.p'
TDE IDE
91.0 91.0
77.0 85.5
95.0 93.4
86.0 80.5
76.0 76.0
82.3 92.3
104.8 109.1
104.0 98.7
0,p'
DDT
91.0
87.7
92.9
83.3
76.0
83.7
91.5
101.0
P.P'
DDT
93 .0
88. 6
93.5
80.8
76.0
92.9
95.5
97.0
Toxa-
phene
-91.0
85.5
93.6
82.9
98.0
85.8
100.2
95.7
-------
Table No. 3:
Pesticide Residues in Soil From Pest Management Areas, Final County, Arizona, 1971
Site
No.
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
IB
Sampling
Date
7/13/71
11/24/71
6/25/71
11/24/71
7/13/71
11/29/71
7/6/71
11/23/71
7/6/71
11/23/71
7/13/71
11/30/71
7/9/71
11/22/71
7/12/71
12/2/71
7/13/71
12/1/71
7/2/71
7/17/71
11/29/71
Ethyl 4/
Parathion—
<0.01
<0.01
<0.01
0.13
<0.01
0.03
<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
<0.01
0.10
e-
BHC
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Heptachlor
Epoxide
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Residue, ppm—
°»P* P»p'
DDE DDE
IN PROGRAM
<0.01 1.42
<0.01 0.53
<0.01 1.33
<0.01 0.67
<0.01 0.65
<0.01 0.68
<0.01 1.43
<0.01 0.72
<0.01 0.61
<0.01 0.38
<0.01 0.29
<0.01 0.21
<0.01 1.00
<0.01 0.76
<0.01 0.58
<0.01 0.39
<0.01 0.59
<0.01 0.33
<0.01 0.70
OUT OF PROGRAM
<0.01 1.29
<0,01 1.24
/ 2J
Diel-
drin
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
3/
o,p'
TDE
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
p,p'
TDE
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
<0.01
-
o,p'
DDT
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
p»p"
DDT
1.00
0.60
1.33
0.67
1.06
0.68
1.49
0.92
0.61
0.38
0.11
0.11
1.08
1.07
1.39
0.99
0.45
0.35
0.77
0.36
0.33
Toxa-
phene
2.31
3.61
1.90
2.06
1.97
2.52
3.94
4.71
2.51
2.57
0.85
1.18
3.20
5.18
<0.05
1.39
0.86
2.21
2.48
1.83
2.41
-------
Table No. 3 cont'd
NJ
_ ., I/ 2/ 3/
Residue, ppnt— , — , —
Site
No.
2B
3B
4B
5B
6B
7B
8B
9B
10B
Sampling
Date
7/16/71
11/24/71
7/23/71
11/29/71
7/16/71
7/15/71
11/23/71
7/16/71
11/30/71
7/22/71
11/2/71
7/21/71
11/23/71
7/14/71
12/1/71
7/21/71
12/2/71
Ethyl .
Parathion-
<0.01
0.02
<0.01
0.05
<0.01
<0.01
0.06
<0.01
<0.01
<0.01
0.01
<0.01
0.02
<0.01
<0.01
<0.01
<;0.01
R— •
BHC
<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
<0.01
<0.01
<0.01
<;0.01
Heptachlor
Epoxide
<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
<0.01
<0.01
<0.01
<0.01
o,pf
DDE
<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
<0.01
<0.01
<0.01
<0.01
p,pf
DDE
1,64
0.79
0.85
0.58
0.50
0.66
0.33
1,82
0.86
1.73
0.67
1.10
0.54
1.53
0.65
1.65
0.65
Diel-
drin
<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
<0.01
<0.01
<0.01
<0.01
o,p'
TDE
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
-------
Table No. 4:
Pesticide Residues in Frogs, Toads and Polliwogs From Pest Management Areas-, Filial County, Arizona, 1971
I/ 2/
Residue, ppm— ,—
Ui
GO
Site
No.
Sampling
Date
Sample
Material
Ethyl ,
Parathion-
e-
BHC
Heptachlor
Epoxide
o,p'-
DDE
P.P1-
DDE
Diel-
drin
o,p'-
TDE
P,P?-
TDE
IN PROGRAM
1A
2A
4A
5A
6A
7A
8A
9A
10A
7/13/71
10/14/71
10/14/71
10/12/71
7/26/71
10/12/71
7/26/71
10/12/71
7/13/71
10/18/71
10/19/71
7/12/71
10/15/71
10/15/71
7/20/71
10/20/71
10/20/71
7/18/71
10/21/71
10/21/71
Frogs
Frogs
Toads
Toads
Frogs
Frogs
Toads
Toads
Frogs
Frogs
Toads
Toads
Toads
Frogs
Frogs
Toads
Toads
Toads
Toads
Frogs
0.03
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.05
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.06
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
0.04
<0.01
0.12
<0.01
0.01
<0.01
<0.01
0.09
<0.01
<0.01
0.03
<0.01
<0.01
0.12
<0.01
<0.01
7.01
9.15
1.93
1.43
6.76
17.60
45.52
12.39
4.19
24.84
4.59
8.34
3.05
27.01
4.61
0.29
0.98
37.62
11.12
2.95
0.02
<0.01
<0.01
<0.01
0.01
<0.01
0.10
<0.01
<0.01
<0.01
0.01
0.01
<0.01
<0.01
0.03
<0.01
<0,01
0.55
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.02
<0.01
0.60
<0.01
0.01
<0.01
0.01
0.10
<0.01
<0.01
0.03
<0.01
<0.01
0.24
<0.01
<0.01
0.04
<0.01
<0.01
<0.01
0.21
<0.01
1.01
<0.01
0.02
<0.01
0.01
0.22
<0.01
<0.01
0.06
<0.01
<0.01
0.84
<0.01
<0.01
DDT
0.01
<0.01
<0.01
0.07
<0.01
0.32
<0.01
<0.01
<0.01
0.17
<0.01
<0.01
0.05
<0.01
0.36
<0.01
<0.01
P,P'
DDT
0.05
0.30
0.10
<0.01 0.20
0.39
1.47
2.50
1.46
0.02
0.99
0.01 0.51
0.53
0.63
0.26
0.38
0.03
<0.01 0.32
2.36
4.44
0.57
-------
Table No. 4 cont'd
I/ 21
Residue* ppm— ? ~
Site
No.
Sampling
Date
Sample
Material
Ethyl _, 3- Heptachlor o,p'-
Parathion— BHC Epoxide DDE
p,p'-
DDE
Diel-
drin
o,p'-
TDE
p.p1-
TDE
o,p'-
DDT
P.P1-
DDT
OUT OF PROGRAM
IB
2B
3B
4B
5B
6B
7B
8B
9B
10B
7/13/71
10/13/71
10/13/71
10/13/71
10/13/71
7/23/71
10/14/71
7/23/71
10/14/71
7/20/71
10/12/71
10/12/71
10/18/71
10/18/71
7/23/71
10/19/71
10/19/71
7/22/71
10/15/71
10/20/71
12/1/71
7/14/71
10/21/71
7/14/71
Toads
Toads
Frogs
Frogs
Toads
Frogs
Frogs
Toads
Toads
Frogs
Toads
Polliwogs
Toads
Frogs
Toads
Toads
Frogs
Toads
Toads
Toads
Toads
Toads
Toads
Toads
Frogs
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
0.02
<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
0.02
<0.01
<0.01
0.02
<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
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
<0.01
<0.01
0.03
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
0.17
<0.01
<0.01
0.26
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
0,04
27.70
3.66
5.35
7.93
3.83
0.87
2.76
7.32
1.76
1.60
1.80
24.84
3.03
8.69
12.02
0.73
0.97
19.22
2.13
0.99
1.79
8.90
15.67
5.71
9.72
4.68
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.07
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.18
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.04
<0.01
<0.01
0.16
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.01
0.25
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.17
<0.01
0.09
<0.01
<0.01
<0.01
<0.01
1.36
<0.01
<0.01
0.46
<0.01
<0.01
<0.01
<0.01
0.41
<0.01
0.82
0.04
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.06
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.09
<0.01
<0.01
0.31
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.02
1.12
1.15
0.32
0.29
0.34
<0.01
0.22
0.32
0.55
0.13
0.28
0.99
0.73
0.27
2.12
0.06
0.11
0.65
2.13
0.22
0.43
1.03
0.38
0.69
0.31
-------
Table No. 4 cont'd
— Corrected for pesticide recovery from fortified samples
21
— Lower limits of sensitivity = 0.01 ppm.
3/
— No detectable residues of other organophosphates were found.
Ul
Ui
-------
Ul
OS
Table No. 5:
Pesticide Residues in Fish and Fresh Water Clams From Pest Management Areas, Pinal County, Arizona, 1971
I/ 21
Residue, ppm— , —
Site
No.
1A
3A
5A
6A
IB
3B
7B
8B
Sampling
Date
7/13/71
10/14/71
10/15/71
7/13/71
7/18/71
10/19/71
7/13/71
10/13/71
7/23/71
10/14/71
10/15/71
7/16/71
10/20/71
10/20/71
10/20/71
Sample
Material
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Minnows
Sunfish
Ethyl 3/
Parathion—
1.24
<0.01
<0.01
<0.01
0.08
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
fresh water <0.01
3-
BHC
0.04
<0.01
<0.01
0.01
0.03
<0.01
OUT
0.04
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
Heptachlor
Epoxide
IN PROGRAM
0.06
<0.01
<0.01
0.02
0.06
<0.01
OF PROGRAM
0.04
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
o,p'-
DDE
1.19
<0.01
<0.01
1.24
1,52
<0.01
0.14
<0.01
0,04
<0.01
<0.01
0.21
<0.01
<0.01
<0.01
P,p'-
DDE
13.07
17.42
3.58
8.71
24.22
0.60
4.39
9.92
0.28
0.63
18.86
8.64
1.63
0.14
0.34
Diel-
drin
0.06
<0.01
<0.01
0.04
0.07
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
o,p'-
TDE
<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
<0.01
<0.01
p»p'-
TDE
1.73
<0.01
<0.01
1.02
2.30
<0.01
0.19
<0.01
0.04
<0.01
<0.01
0.14
<0.01
<0.01
<0.01
o,p'-
DDT
0.12
<0.01
<0.01
0.02
0.07
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
p,p'-
DDT
0.64
<0.01
<0.01
0.10
1.48
<0.01
0.08
<0.01
0.01
<0.01
<0.01
0.09
<0,.01
<0.01
<0.01
clams
— Corrected for pesticide recovery from fortified samples.
21
— Lower limits of sensitivity - 0.01 ppm.
3/
— No residues of other organophosphates exceeding detectable limits were found.
-------
Table No. 6:
Pesticide Residues in Birds From Pest Management Areas, Final County, Arizona, 1971
I/ 2/
Residue, ppm- . —
Ol
Site
No.
1A
2A
3A
5A
6A
7A
8A
Sampling
Date
7/13/71
10/14/71
7/19/71
10/12/71
7/19/71
7/17/71
10/14/71
10/14/71
7/17/71
7/18/71
10/18/71
10/18/71
10/18/71
10/19/71
10/19/71
10/19/71
7/12/71
10/15/71
7/12/71
10/15/71
10/15/71
7/20/71
7/20/71
12/2/71
10/20/71
10/20/71
Bird Organo-
Type phosphates
Mourning Dove
Mourning Dove
Mourning Dove
Mourning Dove
Nestlings
Whitewing Dove
Dove
Sparrow
Mourning Dove
Wren
Woodpecker
Sparrows
Mourning Dove
Owl
Mourning Dove
Sparrows
Dove
Mourning Dove
Wren
Mexican Dove
Finch
Wren
Sparrow
Inca Doves
Woodpeckers
Redheaded Wood-
pecker
,/ $- Heptachlor o,pf-
3- BHC Epoxide DDE
p,p'-
DDE
Diel-
drin
o.p1-
TDE
p,pf-
TDE
o,p'-
DDT
p,p'-
DDT
IN PROGRAM
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0101
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
•
-------
Table 6 cont'd
Site Sampling
No. Date
10A 7/18/71
10/21/71
IB 7/13/71
11/29/71
2B 10/13/71
10/13/71
3B 10/14/71
£ 5B 7/15/71
« 10/18/71
12/14/71
6B 10/19/71
10/19/71
11/30/71
11/30/71
11/30/71
7B 7/22/71
7/20/71
10/15/71
10/15/71
9B 7/20/71
7/20/71
10/21/71
10/21/71
12/71/71
10B 12/2/71
I/ 2/
Residue, ppm— , —
Bird Organo- ,,
Type phosphates—
Mourning Doves
Mourning Doves
Mourning Dove
(Eggs)
Gambel's White-
Crowned Sparrow
Mourning Dove
Sparrow
Mallard Duck
Wren
Mourning Dove
Fox Sparrow
Mourning Doves
Sparrows
House Finch
Cassin ' s Sparrow
Savanna Sparrow
Mourning Doves
Wren
Mourning Doves
Sparrows
Mourning Dove
Wren
Mourning Dove
Wren
Mourning Dove
Loggerhead
Shrike
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
e-
BHC
<0.01
<0.01
OUT OF
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
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Heptachlor
Epoxide
<0.01
<0.01
PROGRAM
<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
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01 :
o,p-
DDE
<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
<0.01
<0.01
<0.01
0.08
<0.01
-------
Table No. 6 cont'd
— Corrected for pesticide recovery from, fortified samples.
21
— Lower limits of sensitivity = 0.01 ppm.
3/
— Ethyl parathion, methyl parathion, malathion, methyl trithion, ethion.
Ui
VO
-------
Table No. 7:
Pesticide Residues in Lizards and Snakes From Pest Management Areas. Final County, Arizona, 1971
o>
o
Site Sampling Sample
No. Date Type
1A 7/13/71 Lizards
10/14/71 Lizards
2A 7/19/71 Lizards
10/12/71 Lizards
10/12/71 Lizards
10/12/71 Lizards
3A 7/17/71 Lizards
10/14/71 Lizards
10/14/71 Lizards
10/14/71 Rattle Snake
7A 7/12/71 Lizards
10/15/71 Lizards
9A- 7/13/71 Lizards
10/20/71 Lizards
12/1/71 Snake Skin
10A 7/18/71 Lizards
10/21/71 Lizards
IB 7/13/71 Lizards
10/13/71 Lizards
10/11/71 Snake
2B 7/26/71 Lizards
10/13/71 Lizards
10/13/71 Lizards
I/ 21
Residue, ppm— , —
Organo- _, B-
phosphates— BHC
Heptachlor o,p'-
Ep oxide DDE
P,P'-
DDE
Diel-
drin
o,p'-
TDE
p,p'-
TDE
o,p'
DDT
p,p'-
DDT
Toxa-
phene
IN PROGRAM
<0.01
<0.01
-------
Table No. 7 cont'd
I/ 2/
Residue, ppm— . —
Site
No.
3B
5B
6B
7B
9B
10B
Sampling
Date
7/23/71
7/23/71
7/23/71
7/23/71
10/14/71
10/14/71
7/15/71
7/23/71
7/22/71
7/22/71
10/15/71
10/15/71
10/15/71
7/20/71
7/21/71
7/14/71
10/20/71
Sample
Type
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Lizards
Organo-
Q/ 3-
Heptachlor o,p'-
phosphates^' BHC
<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
<0.01
<0.01
<0.01
<0.01
<0.
0.
0.
0.
<0.
<0.
0.
0.
0.
0.
<0.
<0.
<0.
0.
01
01
01
01
01
01
47
01
01
01
01
01
01
03
0.03
0.
<0.
01
01
Epoxide
<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
0.01
0.01
<0.01
<0.01
DDE
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
0.07
0.04
0.01
<0.01
<0.01
<0.01
<0.01
0.04
0.07
0.01
<0.01
P,P'-
DDE
0.12
0.02
3.16
9.30
3.56
0.21
8.68
57.62
6.84
0.11
0.85
25.61
0.94
16.05
20.29
10.62
21.21
Diel-
drin
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.02
0.04
0.01
0.01
<0.01
<0.01
<0.01
0.04
0.01
<0.01
<0.01
o,pf
TDE
<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
<0.01
<0.01
<0.01
<0.01
p,p'
TDE
<0.01
<0.01
0.01
0.05
<0.01
<0.01
0.10
0.05
0.01
<0.01
<0.01
<0.01
<0.01
0.08
0.19
0.02
<0.01
o,p'
DDT
<0.01
<0.01
0.01
0.01
<0.01
<0.01
0.04
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
0.01
<0.01
<0.01
p»p'
DDT
<0.01
<0.01
0.01
0.05
<0.01
<0.01
0.03
0.08
0.01
<0.01
0.05
1.34
0.05
0.02
0.34
0.02
1.06
Toxa-
phene
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
— Corrected for pesticide recovery from fortified samples.
21
— Lower limits of sensitivity = 0.01 ppm, except for toxaphene which was 0.05 ppm.
3/
— Ethyl parathion, methyl parathion, malathion, methyl trithion, ethion.
—Gamma BHC =0.01 ppm.
-------
Table No. 8:
Pesticide Residues in Insects From Pest Management Areas. Final County. Arizona, 1971
ISJ
I/ 2/
Residue, ppm— , —
Site
No.
4A
5A
6A
8A-
9A
Sampling
Date
10/12/71
7/13/71
11/23/71
11/23/71
10/18/71
10/19/71
11/30/71
11/30/71
11/30/71
12/2/71
12/2/71
10/20/71
7/13/71
12/1/71
12/1/71
10/20/71
12/1/71
Insect
Type
Hydrophilid
Beetles
Toebiters
Grasshoppers
Grasshoppers
Hydrophilid
Beetles
Fire Ants
Earwigs
Harvester
Ants
Darkling Ground
Beetles
Grasshoppers
Grasshoppers
Ground
Beetles
Grasshoppers
Grasshoppers
Crickets
Red Harvester
Ants
Grasshoppers
Organo- 3 ,
phosphates—
<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
<0.01
<0.01
<0.01
<0.01
B- Heptachlor
BHC Epoxide
IN PROGRAM
<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 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
<0.01 <0.01
o,p'-
TDE
<0.01
0.19
<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
<0.01
<0.01
p,p'-
TDE
0.84
8.12
0.02
0.03
3.24
0.05
0.17
0.02
0.06
<0.01
<0.01
0.77
0.04
0.04
0.05
0.06
0.02
Diel-
drin
<0.01
0.02
<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
<0.01
<0.01
o,p'
TDE
<0.01
0.03
<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
<0.01
<0.01
p,p'
TDE
<0.01
0.02
<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
<0.01
<0.01
o,p'
DDT
<0.01-
0.06
<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
<0.01
<0.01
p,p'
DDT
<0.01
0.02
<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
<0.01
<0.01
Toxar
phene
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.03
<{i).03
<0 . 03
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
-------
Table No. 8, cont'd
Site Sampling Insect
No. Date Type
10A 7/18/71 Fire Ants
7/18/71 Crickets
10/21/71 Field Crickets
10/21/71 Black Harvester
Ants
10/21/71 Hydrophilid
Beetles
IB 7/17/71 Crickets
10/13/71 Hydrophilid
Beetles
2B 10/13/71 Ground Beetles
3B 7/23/71 Backswimmers
7/23/71 Grasshoppers
7/23/71 Crickets
7/16/71 Harvester
Ants
4B 7/20/71 Toebiters
10/12/71 Grasshoppers
5B 7/15/71 Crickets
12/14/71 Grasshoppers
6B 7/16/71' Crickets
7B 7/22/71 Crickets
7/22/71 Grasshoppers
I/ 21
Residue, ppm— , —
Organo- „, g-
phosphates— BHC
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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0
<0
<0
<0
<0
OUT
<0
<0
<0
<0
0
<0
0
0
<0
0
<0
0
<0
<0
.01
.01
.01
.01
.01
OF
.01
.01
.01
.08
.01
.01
.01
.06
.01
.02
.01
.01
.01
.01
Heptachlor
Epoxide
0.01
<0.01
<0.01
<0.01
<0.01
PROGRAM
<0.01
<0.01
<0.01
<0.07
<0.01
<0.01
<0.01
0.01
<0.01
0.01
<0.01
0.01
<0.01
<0.01
o,p'-
DDE
0.02
0.08
<0.01
<0.01
<0.01
0.05
<0.01
<0.01
<0.31
0.01
0.02
0.01
0.24
<0.01
<0.01
0.02
<0.01
0.09
0.02
0.02
P,Pf-
DDE
0.75
1.93
0.04
0.18
0.12
1.20
1.22
0.34
0.58
0.82
0.10
0.54
0.88
0.40
0.13
0.20
0.02
1.70
0.23
0.23
Diel-
drin
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.19
0.02
<0.01
0.01
0.02
<0.01
<0.01
0.02
<0.01
0.20
<0.01
<0.01
o,p'
TDE
<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
<0.01
<0.01
0.02
<0.01
0.03
<0.01
0.01
PsP*
TDE
0.01
0.03
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.04
0.01
0.02
<0.01
0.02
<0.01
<0.01
0.02
<0.01
0.11
0.02
0.02
o,p'
DDT
<0.01
0.07
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.04
<0.01
0.01
<0.01
0.01
<0.01
<0.01
0.06
<0.01
0.02
0.02
0.02
P,P'
DDT
<0.01
0.02
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.07
0.01
0.01
0.01
<0.01
<0.01
<0.01
0.05
<0.01
0.06
0.02
0.02
Toxa-
phene
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.04
<0.05
<0.05
-------
Table No. 8, cont'd
I/ 2/
Residue, ppm— , —
Site
No.
7B
cont ' d
8B
9B
10B
Sampling
Date
10/15/71
10/15/71
10/15/71
7/21/71
10/20/71
12/1/71
10/21/71
10/21/71
10/21/71
10/21/71
7/21/71
7/21/71
10/2/71
10/21/71
10/21/71
Insect
Type
Toebiters
Hydrophilid
Beetles
Ground Beetles
Grasshoppers
Red Harvester
Ants
Darkling Ground
Beetles
Hydrophilid
Beetles ;
Toebiters
Ground Beetles
Grasshopper
Grasshoppers
Grasshoppers
Bandwing Grass-
hoppers
Hydrophilid
Beetles
Backswimmers
Organo- ,,
phosphates—
<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
<0.01
<0.01
6-
BHC
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
0.01
<0.01
<0.01
<0.01
Heptachlor
Epoxide
<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
<0.01
<0.01
o,p'
DDE
0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
0.01
<0.01
<0.01
<0.01
p.p1-
DDE
0.01
0.02
0.03
0.23
0.03
0.16
0.09
0.41
0.11
0.07
0.02
0.17
0.02
1.12
6.24
Diel-
drin
<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
<0.01
<0.01
o,p'
TDE
<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
<0.01
<0.01
p,p'
TDE
<0.01
<0.01
<0.01
0.01
<;0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0 . 01
0.02
<0.01
<0.01
<0.01
o,p'
DDT
<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
<0.01
<0.01
p,p'
DDT
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
0.02
<0.01
<0.01
<0.01
Toxa-
phene
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
-------
ACKNOWLEDGMENT
The authors wish to express gratitude to a number of workers who
furnished expert assistance in the sample collections and processing in
this study. Among these are: Dr. Leon Moore and Mike Lindsey for
technical assistance and advice, also Harry Richardson for capable
assistance in the processing, extraction and cleanup of samples. Without
this help the program could not have achieved the success it has reached.
Appreciation is also expressed to Dr. Stephen Warnick and staff,
Intermountain Laboratories, Inc., Salt Lake City, Utah, for his expert
assistance in performing residue analyses on some of the biological
samples.
165
-------
LITERATURE CITED
(1) Bowman, M. C. and M. Buroza. 1965. Extraction P-Values of
Pesticides and Related Compounds in Six Binary Solvent Systems.
J. Assoc. Offie. Agr. Chem. .48:943-952.
(2) Hawthorne, J. C. and L. H. Dawsey. 1972. Quantitative Deter-
mination of Combinations of Toxaphene in Soil, Sediment, Water
and Crop Residues by GLC Methods. Unpublished Manuscript.
(3') Schutzmann, R. L., D. W. Woodham and C. W. Collier. 1971.
Removal of Sulfur in Environmental Samples Prior to Gas Chroma-
tographic Analysis for Pesticide Residues. J. Assoc.. Of fie.
Agr. Chem. _54:1117-1119.
(4) Schutzmann, R. L., W. F. Barthel and J. A. Warrington. 1966.
Cleanup: and Confirmation of Identity of Pesticide Residues by
Thin-Layer Chromatography. Part I-Soil, Water and Sediment.
USDA, ARS. 81-12:13 pp.
(5) Woodham, D. W., C. D. Loftis and C. W. Collier, 1972. Identi-
fication of the Geo Chromatographic Dieldrin and Endrin Peaks
by Chemical Conversion. J. Agr. Food Chem. 20:163-165.
C6) Woodham, D. W., M. C. Ganyard, C. A, Bond and D. 0. Reeves.
1973. Monitoring of Agricultural Pesticides in USDA's Pest
Management Program in North Carolina, 1971, First Year Study.
Unpublished Report.
166
-------
MONITORING OF AGRICULTURE PESTICIDES IN A COOPERATIVE
PEST MANAGEMENT PROJECT IN NORTH CAROLINA, 1971,
FIRST YEAR OF STUDY
D. W. Woodham, M. C. Ganyard —, C. A. Bond and R. G. Reeves
Plant Protection and .Quarantine Programs
Brownsville, Texas 78520
INTRODUCTION
A cooperative tobacco pest management project was initiated in
three geographically distant locations in North Carolina in 1971 by the
United States Department of Agriculture, North Carolina Department of
Agriculture and the North Carolina Agricultural Extension Service.
The pest management area was 145 square miles which contained 685
tobacco farms, 1369 tobacco fields and 4244 acres with an average tobacco
acreage of 6.2 acres per farm and 3.1 acres of tobacco per field.
This pilot study was an attempt to establish a more ecologically,
economically, and socially acceptable system for protecting tobacco
crops from insect pests, as described by Ganyard>et al. (1).
Another purpose of the study was to monitor pesticide residues
in biotic and abiotic environmental components prior to application of
the chemicals and following harvest of the crops, both within and out-
side program areas. Twenty sampling sites were selected in Wayne and
Wilson Counties, ten of which were located within the pest management
project area and ten in a geographically adjacent area. Each site con-
sisted of a tobacco field with a farm pond located within 300 feet of
subject field and within the drainage area of the field. Ponds were
reasonably uniform in size; duplicate samples were collected at each
site according to standard sampling procedures, which will be discussed
later.
Samples were collected in the spring preceding initial pesticide
applications and again in the fall following termination of pesticide
treatments.
— USDA, APHIS, PPQ, Pest Management Project Specialist, Raleigh,
North Carolina 27607
167
-------
Biotic groups sampled in 1971 include: (1) Bluegill (LepQmis
machrochirus); (2) four species of turtles, (a) snapping turtles (Chelydra
serpentia), (b) musk turtles (Sternotherus odoratus), (c) painted turtles;
(Chrysemys pecta), (d) yellow-bellied turtles (Chrysemys scripta); (3)
large frogs (Bana sp); (4) Tiger beetles (Megacephala Carolina) and (5)
cured tobacco leaves. Abiotic groups sampled were: (1) pond sediment;
(.2) pond water and (3) tobacco field soil. Each biotic group was not
available from all sites, thus accounting for occasional omissions in
tables of results.
SAMPLE COLLECTION;
Turtles and fish were captured with a common fish trap constructed
of chicken wire, while tiger beetles were captured in pitfall traps lo-
cated at the soil surface within each tobacco field. Traps were ser-
viced daily and trappings for a given species were conducted simultan-
eously at all 20 sites. Bullfrogs were collected by gigging at night
from a boat.
Water samples were collected from a boat by attaching a small-mouth,
one-gallon bottle to a pole and slowly lowering to the bottom of the pond.
Ten samples were collected from dispersed positions within each pond,
mixed thoroughly and a one-gallon composite sample taken for analysis.
Ten random sediment samples, collected with an Eckman Dredge, from
each pond were composited and a representative half'-gallon sample taken
for analysis. A core sampling device was utilized to collect fifty 2"
x 5" soil cores from each tobacco field. The cores from each field were
mixed thoroughly and a representative half-gallon sample was taken for
analysis.
In a separate aspect of its study, cured tobacco leaves were ran-
domly collected from field research plots. These samples were analyzed
primarily for residue determinations following pesticide treatments with
certain known chemicals.
All biotic samples, except tiger beetles, were weighed in the field,
and placed in portable freezers containing dry ice. Tiger beetles were
immobilized by cooling and returned to the laboratory where accurate
weights were obtained on a Mettler^ balance. All samples, except water,
were stored at 25°F, until packed in styrofoam biomailers containing dry
ice for shipment to the USDA, Methods Development Environmental Quality
Laboratory in Brownsville, Texas for residue analysis. To avoid spoil-
age, these samples were shipped air mail, special delivery, normally
arriving in Brownsville within 24 hours, still in frozen condition. Water
samples were stored in one-gallon glass bottles at room temperature and
shipped to Brownsville approximately four days after collection. All of
the samples, except water, were maintained in a frozen condition until
they were analyzed. All samples were analyzed as soon as possible after
receipt.
168
-------
ANALYTICAL METHODS;
Extraction: Organochlorine and organophosphate pesticides were
extracted from soil essentially as described by Stevens»et al. (2): a
brief description is given below:
Representative 300 g subsamples of wet soil were transferred to
half-gallon Mason jars with 600 ml of a 3:1 mixture of hexane-isopropyl
alcohol solvent and 80 ml of distilled water, then rotated 4 hours on a
concentric rotator. After the soil had settled, the extracts were fil-
tered through glass wool into 1-liter separatory funnels, the isopropan-
ol and water removed by washing three times with equal volumes of distilled
water and the hexane layer filtered through a layer of glass wool and
anhydrous sodium sulfate into 500 ml graduated cylinders, collecting 300 ml
aliquots. The hexane extracts were then stored in capped, amber sample
bottles at ca. 40°F pending subsequent GLC analysis.
Sediment was extracted in an identical manner with the following
exceptions: excess water was drained from samples before subsamples
were weighed and 250 g of anhydrous sodium sulfate added to the jars
containing the solvent and samples.
Water samples were mixed thoroughly, then representative 500 g sub-
samples weighed into 1-liter separatory funnels. The samples were ex-
tracted three times with fresh 100 ml portions of Nanograde dichlorome-
thane, filtering the extracts through a funnel containing glass wool and
anhydrous sodium sulfate into 500 ml Erlenmeyer flasks. Glass beads and
1.0 ml of a 0.01% solution of Nujol in hexane were added and the solvent
evaporated to ca. 5 ml through Snyder columns on a warm (ca. 60°C) water
bath. One hundred milliliters of Nanograde hexane were then added slowly
through the Snyder columns and the solvent evaporated again on a hot
water bath to ca. 5 ml. The concentrated extracts were transferred to
stoppered 15 ml centrifuge tubes with Nanograde hexane, the solvent
volume adjusted to 12.5 ml and stored in a 40°F refrigerator pending
subsequent GLC analysis. Care was taken in the evaporation step to be
certain all traces of dichloromethane were removed.
Soil, sediment and water extracts did not normally require cleanup
before GLC residue analysis. Sediment samples occasionally contained
abnormally high concentrations of sulfur, which were removed by sub-
jecting the extracts to the sulfur removal procedure of Schutzmann.et al.
(3), when necessary.
Tobacco leaf samples were first thoroughly ground in a Hobart food
chopper, then representative 100 g samples weighed into half-gallon
Mason jars with 800 ml of Nanograde acetonitrile. The jars were sealed
with screw caps and Teflon liners and rotated concentrically at 30 rpm
for four hours. The extracts were then filtered through glass wool in-
to graduated cylinders, collecting 300 ml aliquots. The aliquots were
transferred into 500 ml Erlenmeyer flasks, 0.01% Nujol in hexane and
glass beads added and the acetonitrile evaporated through Snyder columns
to ca. 10 ml on hot plates. One hundred milliliters of Nanograde hexane
169
-------
were added slowly through the Snyder columns and the solvent again evapo-
rated to ca. 10 ml on a hot water bath. The preceding step was repeated
twice with fresh 100 ml portions of hexane, evaporating to ca. 10 ml
each time. Finally 100 ml of hexane was added to the flasks, the solution
brought to a boil on the hot water bath and the contents transferred to
500 ml separatory funnels with 10 ml Nanograde isopropyl alcohol and
10 ml of hexane. The water and alcohol were removed by shaking with
200 ml distilled water. The hexane layers were dried by filtering through
anhydrous sodium sulfate into 250 ml Erlenmeyer flasks, 1.0 ml of 0.01%
Nujol and glass beads added and the solvent evaporated through Snyder
columns to ca. 75 ml on a hot water bath. Volumes were adjusted to
exactly 100 ml with Nanograde hexane and the extracts stored in capped>
amber sample bottles pending subsequent cleanup of extract.
Fish and frogs were processed whole; shells were removed from turtles;
composite samples were throughly ground in a Hobart food chopper,
representative 25 g samples weighed into 1000 ml blender jars with 150
ml of a 3:1 mixture of Nanograde hexane-isopropyl alcohol and blended
at medium speed for two minutes. The blended samples were transferred
to half-gallon Mason jars with 250 ml of the hexane:alcohol solvent mix-
ture, the jars sealed with screw caps and Teflon^ liners and rotated
concentrically for four hours. The extracts were filtered through glass
wool into separatory funnels and the alcohol removed with three
successive washings of distilled water, discarding the aqueous layers.
The hexane was then filtered through anhydrous sodium sulfate into graduated
cylinders, measured aliquots collected and transferred to amber sample
bottles for storage under refrigeration pending cleanup of the extracts.
Samples of tiger beetles ranging in weights from 0.14 g to 6.58 g
each were placed in 100 ml blender jars with 50 ml of Nanograde isopro-
pyl alcohol and blended for 2 minutes at high speed. Samples were then
transferred to half-gallon Mason jars; blender jars were rinsed twice
with fresh 75 ml portions of Nanograde hexane, rinsings were added to
Mason jars. The jars sealed and rotated concentrically for four hours
at 30 rpm, then filtered into 500 ml separatory funnels. Alcohol was
removed from the extracts, the extracts dried, bottled and stored as
described previously.
Methemyl (Lannate) was extracted from soil, sediment, water and
tobacco as described in a previous paper by Reeves and Woodham (4).
Dichloromethane was utilized to extract the methomyl from soil, water and
sediment samples; a mixture of 97.5% dichloromethane and 2.5% benzene
was employed for extracting the insecticide from tobacco samples. The
extracts were filtered, dried over anhydrous sodium sulfate and stored
in sealed amber sample bottles in a refrigerator pending subsequent
cleanup procedure to remove interfering materials.
Carbaryl (.Sevin) and carbofuran (Furadan) were extracted from soil,
sediment, water and tobacco as described by Reeves and Woodham (5).
Briefly, the insecticides were extracted from sediment and tobacco with
dichloromethane in half-gallon Mason jars on a concentric rotator for
170
-------
4 hours while water samples were extracted in separatory funnels with
dichloromethane. Sample extracts were dried over anhydrous sodium sulfate,
the solvent evaporated to 50 ml and stored under refrigerator pending
subsequent cleanup, hydrolysis and derivation procedures.
Biological sample extracts to be analyzed for organochlorine and
organophosphate pesticide residues were purified by first partitioning
5 g aliquots between two immiscible solvents (hexane and acetonitrile)
as described by Wiersma ,et al. (6) to remove most of the fats and oils
in the samples. After concentrating the samples into hexane, a modifi-
cation of the Florisil column cleanup procedures of Mills,et al. (7),
Johnson (.8) and Wiersma,et al. (6) was utilized to further purify the
extracts. The following changes were made: 17 g of a mixture of 15 g
Florisil and 2 g anhydrous sodium sulfate was used in the columns; the
columns were eluted a third time with dichloromethane to remove some
of the more polar pesticides. Class beads and 1 ml of a 0.01% Nujol
in hexane were added and each of the three fractions were concentrated
through Snyder columns to ca. 5 ml on a hot water bath. The concentra-
ted extracts were quantitatively transferred to stoppered 15 ml centri-
fuge tubes with hexane and the solvent evaporated to exactly 12.5 ml.
Care was taken to ensure that all of the diethyl ether or dichloromethane
had been removed, then samples were stored under refrigeration pending
the subsequent GLC analysis.
Fraction 1 from the Florisil columns contained some of the less
popular pesticides, aldrin, heptachlor, DDT, DDE, TDE (o,p'~ and p,p'-),
toxaphene, strobane, chlorodane, mirex, BHC (gamma isomer), and PCB's
(when present) and others. Fraction 2 contained some of the moderately
polar pesticides such as dieldrin, endrin, heptachlor epoxide, methyl
and ethyl parathion, endosulfan, ethion and others. Fraction 3 contained
some of the highly polar pesticides, malathion, methyl trithion, endosulfan
isomers and others.
Soil, sediment, water and tobacco extracts were purified for
methomyl analysis as described by Reeves and Woodham (4); briefly, the
method involved concentration of the solvent to 10 ml, then transferring
the concentrated extract into Florisil chromatographic columns, where
the methomyl was eluted from the columns with a 90% dichloromethane:
10% acetone solution (v/v) from the soil, sediment and water. Chloroform
saturated with distilled water was used to elute the methomyl from the
Florisil columns for the tobacco extracts. Following column cleanup the
eluates were evaporated and transferred to 15 ml centrifuge tubes for
refrigerated storage pending GC analysis.
Soil, sediment, water and tobacco extracts for carbaryl and carbo-
furan analysis were purified utilizing a procedure described by Reeves
and Woodham (5), utilizing a Florisil chromatographic column cleanup.
The insecticides were eluted from the columns with dichloromethane for
the soil, water and sediment while a solution of 20% diethyl ether:80%
dichloromethane was used for tobacco. These eluates were evaporated and
transferred to centrifuge tubes and stored under refrigeration pending the
hydrolysis, derivation and coagulation steps.
171
-------
The purified extracts from the Florisil cleanup procedure were
hydrolyzed with an aqueous solution of sodium hydroxide, then carried
through the chloracetylation procedure as described by Argauer,et al. (9)
to form derivatives, detectable by electron capture gas chromatography.
The derivatized soil, sediment and water samples were stored in benzene
in centrifuge tubes with anhydrous sodium sulfate and analyzed by GC as
soon as possible. The derivatized tobacco extracts were further puri-
fied utilizing the coagulation procedure of Johnson (10). The derivatives
were extracted from the aqueous phase with dichloromethane, the solvent
filtered through anhydrous sodium sulfate and evaporated to ca. 5 ml on
a hot water bath. The extracts were transferred to centrifuge tubes with
benzene and stored in a refrigerator pending subsequent GC analysis.
Care was taken in the evaporation step to be certain all traces of
dichloromethane were removed.
Organochlorine pesticides were analyzed by gas-liquid chromatography
(GLC), utilizing a Tracer MT-220 gas chromatograph equipped with dual
Mi-63 electron capture detectors and four 6 foot glass columns with the
following packing materials: (1) 3% DC-200 mesh Gas Chrom-Q (Applied
Science Laboratories, State College, Penn.); (2) 3% OV-1 on 80-100 mesh
Chromosorb-W (Johns-Manville, Inc.); (3) 5% OP-1 on 100-120 mesh Gas
Chrom-Q (Applied Science Laboratories) and (4) 11% mixture of 1.95% OF-
1:1.5% OV-17 on 80-100 mesh Gas Chrom-Q. -Isothermal operating conditions
were as follows: nitrogen carrier gas flow rate, 80 ml/minute (120 ml/
minute for the mixed column); column temperatures, 200°C: injector
temperatures, 250°C: detector temperatures, 300°C. Recorder (1 mv)
chart speed was 30 inches per hour. Sensitivity was adjusted to produce
approximately half-full scale deflection of the recorder pen with a
0.50 ng injection of aldrin. Calculations (as ppm) were based on peak
heights of the pesticide peaks compared with a pesticide calibration
standard of known concentration and purity.
Organophosphate pesticides were also analyzed with a Tracor MT-220
gas chromatograph equipped with a dual Flame Photometric Detector (FPD)
with the phosphorous (526 mu) and sulfur (394 mu) interference filters
installed for simultaneous recordings of both phosphorous and sulfur
peaks from thiophosphate pesticides. The column used was a 6 foot by
1/4 inch glass tube packed with 3% DC-200 on 100-120 mesh Gas Chrom-Q.
Isothermal operating conditions were as follows: gas flow rates, 80,
40, 75 and 20 milliliters per minute for the nitrogen carrier gas, air,
hydrogen and oxygen, respectively; column temperature, 200 C; injector
temperature, 250 C, and detector temperature, 200°C. Recorder chart
speed was 30 inches per hour. Sensitivity was adjusted to obtain ap-
proximately half^full scale deflection with an injection of 1.5 ng ethyl
parathion. Calculations were based on peak height as described for
organochlorine pesticides.
Methomyl was analyzed as described in the organophosphate analysis
section, except the column temperature was decreased to 140°C, and a 10%
DC^200 on 100-120 mesh Gas Chrom-Q column was utilized in the gas chroma-
tograph. All other operating conditions were the same. Sensitivity of
the detector was adjusted to obtain half-full scale deflection of the
recorder pen with a 20 ng injection of methomyl.
172
-------
Carbaryl and carbofuran were analyzed by GLC as described for the
chlorinated hydrocarbons, except a 6 foot by 1/4 inch glass column
packed with 5% OV-210 on 100-120 mesh H.P. Chromosorb-W (Johns-Manville,
Inc.) was utilized. Sensitivity was adjusted to obtain ca. half-full
scale deflection with a 4 ng injection of the carbofuran or carbaryl
derivatives.
A series of controls consisting of a solvent check, non-fortified
sample and a sample fortified with known concentrations of pesticides
were included with each group of samples. The controls were extracted,
stored and analyzed simultaneously with samples containing unknown con-
centrations of pesticides. This was necessary to monitor possible con-
tamination and analytical and extraction efficiency. The following
average range of recoveries was obtained from the various sample types:
soil, 58.1% for aldrin to 117.0% for p,p'-DDT; sediment, 71.2% for diel-
drin to 103.6% for p,p'-DDE; water, 58.9% for carbaryl to 98.4% for p,p'-
DDE; tobacco, 47.6% for methyl trithion to 104.9% for ethion: frogs,
51,1% for malathion to 100.8% for o,p'-DDT: tiger beetles, 36.1% for
ethyl trithion to 112.5% for p,p'-DDT; turtles, 55.8% for lindane to 89.7
for ethion. All residues were corrected for appropriate recovery values.
Moisture content was determined on all soil and sediment samples by
drying a weighed 100 g sample in a 120°C oven for 24 hours, then re-
veighing the sample to determine moisture loss. Residues were* corrected
and reported on a dry weight basis.
RESULTS AND DISCUSSION;
Table 1 presents pesticide treatment histories for the sampling
sites selected for this project. The majority of pesticides applied
were either organophosphates or carbamates. The only exception was
the endosulfan treatments for site No's F-3137 and G-1135.
Table No. 2 presents residue data for soil and sediment collected
from areas inside and outside this program area. Residues ranging from
0.01 to 0.35 ppm o,p'-TDE and 0.02 to 1.15 ppm p,p'-TDE were detected in
sediment inside the program area and from 0.01 to 0.30 ppm o,p'-TDE and
0.02 to 0.87 ppm p,p'-TDE in sediment collected from ponds outside these
areas. No residues of organophosphates, carbaryl, methomyl (Lannate) or
carbofuran (Furadan) exceeding the lower limits of sensitivity of 0.01
or 0.05 ppm were detected in any of the sediment samples.
Soil samples collected inside the program area produced residues
ranging from 0.01 to 0.05 ppm o,p'-TDE, 0.04 to 0.19 ppm p,p'-TDE, 0.02
to 0.17 ppm o,p'-DDT and 0.06 to 0.54 ppm p,p'-DDT while outside the
program area soil residues ranging from 0.02 to 0.07 ppm o,p'-TDE, 0.04
to 0.14 ppm p,p'-TDE, 0.02 to 0.04 ppm o,p'-DDT and 0.04 to 0.14 ppm
p,p'-DDT were detected. Carbofuran (Furadan) was found in only one soil
sample from site No. H-238, 2.00 ppm, collected in the spring of 1971
inside the program area. With the exception of the single soil samples
showing carbofuran residues, soil residues were also below lower limits
of detectability of 0.05 ppm for the carbamates or methomyl.
173
-------
Generally soil and sediment residues were slightly higher within the
program areas, apparently a result of pesticide treatments from previous
years, with the exception of the H-238 soil with the carbofuran residues.
Table No. 3 shows residue patterns for harvest tobacco samples from
this pest management project area. Residues ranging from <0.01 to 0.31
ppm o,p'-TDE, <0.01 to 0.98 ppm p,p'-TDE, <0.01 to 0.28 ppm o,p'-DDT and
0.07 to 1.91 ppm p,p'-D0T were detected in these samples. No residues of
organophosphates, methomyl or carbaryl exceeding the lower limits of sen-
sitivity of 0.01 or 0.05 ppm were detected in this tobacco. Carbofuran
residues were found in samples from the following areas: Avcock No. 4,
0.96 ppm; Saul's No. 4, 0.47 ppm; R. Marsh No. 4, 0.08 ppm and W. Harbor
No. 4, 0.48 ppm.
Residue data for biologicals are presented in Table No. 4. Concen-
trations ranging from 0.03 to 1.14 ppm p,p'-DDE, <0.01 to 0.02 ppm p,p'-
TDE, and <0.01 to 0.04 ppm p,p'-DDT were detected in turtles collected
inside the project area. Turtles from outside these areas produced re-
sidues ranging from <0.01 to 0.01 ppm dieldrin, 0.03 to 3.81 ppm p,p'-
DDE, <0.01 to 0.08 ppm p,p'-TDE and <0.01 to 0.01 ppm p,p'-DDT.
Pesticide patterns in frogs inside and outside the project area were
similar to those found in the turtles. Residues ranging from <0.01 to
0.05 ppm dieldrin, <0.01 to 0.01 ppm o,p'-DDE, 0.01 to 0.14 ppm p,p'-DDE,
<0.01 to 0.13 ppm p,p'-TDE and <0.01 to 0-01 ppm p,p'-DDT were detected in
frogs from within, while ranges of <0.01 to 0.11 ppm dieldrin, <0.01 to
0.15 ppm p,p'-DDE, <0.01 to 0.33 ppm p,p'-TDE and <0.01 to 0.02 ppm p,p?-
DDT were detected in frogs from outside these areas.
Fish from within the project area produced residues ranging from
<0.01 to 0.16 ppm dieldrin, 0.02 to 0.09 ppm o,p'-DDE, 0.07 to 0.16 ppm
p,p'-DDE, <0.01 to 0.01 ppm o,p'-TDE, 0.05 to 0.15 ppm p,p'-TDE, <0.01 to
0.01 ppm o,p'-DDT and 0.02 to 0.04 ppm p,p'-DDT; outside these areas, re-
sidues in fish ranged from <0.01 to 0.16 ppm dieldrin, <0.01 to 0.12 ppm
o,p'-DDE, 0.01 to 0.80 ppm p,p'-DDE, <0.01 to 0.33 ppm p,p'-TDE, <0.01 to
0.09 ppm o,p'-DDT and <0.01 to 0.07 ppm p,p'-DDT.
Tiger beetles showed perhaps the greatest variety of pesticides of
all biologicals sampled. Inside the program area, residues ranging from
<0.01 to 0.05 ppm dieldrin, <0.01 to 0.05 ppm endrin, <0.01 to 0.11 ppm
o,p'-DDE, <0.01 to 4.44 ppm p,p'-DDE, <0.01 to 0.01 ppm o,p'-TDE, <0.01
to 0.02 ppm p,p'-TDE, <0.01 to 0.12 ppm o,p'-DDT and <0.01 to 0.03 ppm
p,p'-DDT were detected. Outside these areas, a similar pattern was ob-
served with residues ranging from <0.01 to 0.05 ppm dieldrin and endrin,
<0.01 to 0.14 ppm o,p'-DDE, 0.46 to 3.07 ppm p,p'-DDE, <0.01 to 0.02 ppm
p,p'-TDE, <0.01 to 0.12 ppm o,p'-DDT and <0.01 to 0.03 ppm p,p'-DDT being
detected in these beetles.
No residues of organophosphate pesticides exceeding the lower de-
tectable limits of 0.01 ppm were observed in any of the biological sam-
ples.
174
-------
Table No. 1:
Record of Foliar Insecticide Treatments of Tobacco in Sampling Sites
in Pest Management Areas North Carolina, 1971.J/
Sampling Sites
A-164
A-167
C-541
C-559
C-622
C-1513
D-822
E-3229
E-3231
F-1237
F-1281
F-3137
G-1135
G-1348
G-1425
G-1508
G-1509 (1)
G-1509 (2)
H-238
H-256
Insecticides Applied
Guthion
Methomyl (Lannate)
Carbaryl (Sevin), Endosulfan, Malathion
No treatment
Carbaryl (Sevin)
Guthion
Diazinon
Carbaryl (Sevin)
Guthion
No treatment
Endosulfan, Malathion
Endosulfan, Malathion
Azodrin
Methomyl (Lannate)
Azodrin
Carbaryl (Sevin)
Azodrin
Parathion, Carbaryl (Sevin)
Methomyl (Lannate)
-lanyard et al. 1972 (1),
175
-------
Table No. 2:
Organochlorine Pesticide Residues in Soil and Sediment from Pest Management
Areas in North Carolina, 1971.
Residue, ppnr^' -/J -1
Site Sampling
No. Series o,p'-DDE
j
P.p.1 -DDE
o.p'-TDE p,p'-TDE
o.p'-DDT
p,p'-DDT
Inside Program Area
SEDIMENT
A-164
A-167
C-1135
G-1348
G-1425
G-1508
G-1509
(1 - 2)
G-1509
(2 - 2)
H-238
H-256
C-541
C-559
C-622
C-1513
D-822
E-3229
E-3231
*
•
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
<0.01
<0.01
<0.01
<0.01
-------
Table No. 2 cont'd:
Site Sampling
No. Series
o>p*-DDE
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
— Corrected for pesticide recovery from fortified samples.
2/
— Residues calculated on dried basis.
3/
— Lower limits of sensitivity = 0.01 ppm.
F-1237
F-1281
F-3137
SOIL;
A-164
W-167
G-1135
G-1348
G-1425
G-1508
G-1509
(1 - 2)
G-1509
(2 - 2)
H-238
H-256
C-5541
C-559
C-622
C-1513
C-822
D-3229
F-1237
F-1281
F-3137
1
2
1
2
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
p,p'-DDE
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Residue, ppm-
o.p'-TDE
0.30
0.19
0.09
0.05
0.06
0.05
L/ j £.f 9 J/
p,p'-TDE
0.87
0.48
0;16
0.10
0.13
0.14
Inside Program Area
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
0.05
0.03
0.05
0.04
0.01
0.02
0.03
0.03
0.02
Outside Program
0.03
0.04
0.04
0.07
0.02
0.04
0.06
0.02
0.02
0.04
0.19
0.11
0.14
0.08
0.04
0.06
0.09
0.08
0.04
Area
0.08
0.06
0.06
0.14
0.04
0.07
0.12
0.07
0.04
o,p'-DDT p^'-DDT
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.04
<0.17
0.04
0.06
0.03
0.02
0.03
0.05
0.07
0.03
0.02
0.04
0.02
0.04
0.03
0.01
0.02
0.03
0.10
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.07
0.50
0.12
0.54
0.07
0.06
0.09
0.14
0.17
0.08
0.04
0.09
0.05
0.10
0.05
0.04
0.04
0.06
0.14
177
-------
Table No. 3;
Organochlorine Pesticide Residues iii Tobacco from Pest Management Areas in North Carolina,
y
2/
Residue, ^ *
Site o,p'-DDE p,p'-DDE o.p'^-TDE p.p'-TDE o.p'-DDT p,p'-DDT
Saul, No. 1
Saul, No. 2
Saul, No. 3
Ward, No. 1
Ward, No. 2
Ward, No. 3
Wilson, No. 1
Wilson, No. 2
Wilson, No. 3
Aycock, No. 1
Aycock, No. 2
Aycock, No. 3
Aycock, No. 4
W. Saul's
W. Harbor, No. 1
W. Harbor, No. 3
W. Harbor, No. 4
R. Marsh, No. 1
R. Marsh, No. 2
R. Marsh, No. 3
R. Marsh, No. 4
— Samples collected at harvest in the autumn 1971.
2/
— Corrected for pesticide recovery from fortified samples.
3/
— Lower limits of sensitivity = 0.01 ppm.
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.09
0.03
0.02
0.31
0.23
0.15
0.02
0.02
0.03
0.04
0.02
0.03
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.04
0.06
0.05
0.69
0.58
0.54
0.05
0.04
0.05
0.12
0.05
0.98
0.06
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.03
0.04
0.04
0.28
0.24
0.17
0.04
0.04
0.05
0.04
0.03
0.03
0.04
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.22
0.39
0.27
1.91
1.90
1..83
0.20
0.19
0.23
0,25
0.15
0.21
0.18
0.22
0.20
0.23
0.20
0.07
0.09
0.09
0.09
178
-------
Table No. 4:
Organochlorine Pesticide Residues in Biological Samples from Pest Management Areas in North Carolina, 1971.—
Organochlorine Pesticidi
Site
No.
TURTLES :
A-164
A-167
G-1135
G-1135
G-1348
G-1425
G-1425
G-1425
G-1425
G-1508
G-1509
G-1509
H-238
H-238
H-256
H-256
H-256
C-541
C-541
C-559
C-622
C-1513
C-1513
Species
Snapping
Yellow-Bellied
Musk
Yellow-Bellied
Yellow-Bellied
Painted
Yellow-Bellied
Snapping
Musk
Yellow-Bellied
Musk
Yellow-Bellied
Painted
Yellow-Bellied
Musk
Painted
Yellow-Bellied
Musk
Painted
Snapping
Snapping
Musk
Painted
I/
Dieldrin Endrin
<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
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
21 3/
Residue, pprn^'' -'
o.p'-DDE p,p'-DDE
<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
<0.01
<0.01
<0.01
<0.01
Inside Program
0.29
4/
0.11
0.04
0.14
0.05
0.03
0.08
0.33
0.08
0.21
0.12
0.09
0.24
0.78
1.14
0.20
Outside Program
<0.01
<0,01
<0.01
<0.01
<0.01
<;0.01
0.40
0.34
0.27
0.11
0.33
0,40
o,pt-TDE
Area
<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
<0.01
<0.01
<0.01
<0.01
Area
<0.01
<0.01
<0.01
<0.01
<0.01
<0,01
*-TDE o>pr-DDT p,p*-DDT
<0.01
0.02
<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
0.02
0.02
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.04
<0.01
<0.01
<0.02
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
0.04
<0.01
0.04
0.03
<0.01
0.02
<0.01
<0.01
<0.01
0.01
-------
Table No. 4 cont'd:
oo
o
Site
No.
D-822
D-822
D-822
D-822
E-3229
E-3229
B-3229
E-3231
E-3231
E-3231
E-3231
F-1237
F-1237
F-1237
F-1281
F-1281
F-1281
F-3137
FROGS ;
A-164
A-167
C-622
G-1135
G-1508
G-1509
H-256
Species
Snapping
Musk
Painted
Yellow-Bellied
Painted
Snapping
Yellow-Bellied
Musk
Painted
Snapping
Yellow-Bellied
Musk
Painted
Yellow-Bellied
Musk
Painted
Snapping
Painted
Dieldrin Endrin
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.05
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
2f 37
Residue, ppm— * —
p'-DDE
<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
<0.01
<0.01
<0.01
<0.01
<0.01
p , p-DDE o
0.18
0.26
0.13
0.03
0.26
0.04
0.11
0.35
0.75
0.15
0.70
3.81
1.99
1.99
0.17
0.18
0.20
1.08
Inside Program
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.04
0.04
0.03
0.01
0.10
0.01
0.14
,p'-TDE
<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
<0.01
<0.01
<0.01
<0.01
<0.01
Area
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
p, p *-TDE o,p *-DDT p,p'-DDT
<0.01
<0.01
0.01
<0.01
0.01
<0.01
0.01
<0.01
0.01
<0.01
0.01
<0.01
0.08
0.08
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.13
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
o.o-i
<0.01
0.01
<0.01
0.06
<0.01
0.01
<0.01
<0.01
0.07
<0.01
<0.01
<0.01
0.05
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
-------
Table No. 4 Cont'd
oo
Site
No.
FROGS:
C-1513
D-822
D-3229
D-3231
F-1237
F-1281
FISH:
A-164
A-167
G-1135
G-1348
G-1425
G-1508
G-1509
H-238
H-256
C-541
C-559
C-622
C-1513
D-822
E-3229
E-3231
F-1237
F-1281
F-3137
G-1435
Species
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Bluegills
Dieldrin Endrin
<0.01
<0.01
0.01
<0.01
0.11
<0.01
0.02
0.01
0.02
<0.01
0.08
0.02
0.01
0.01
0.16
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.11
0.06
0.16
0.05
<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
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
?/ 3/
Residue, ppro^'' -
o, p' -DDE p, p' -DDE o^'-TDE
Outside Program
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
0.04
0.15
0.05
0.03
0.03
0.02
0.03
0.03
0.09
0.02
<0. 01
0.06
0.01
0.15
0.01
Inside Program
0.19
0.87
0.11
0.11
0.07
0.16
0.14
0.16
0.12
Area
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Area
<0.01
0.02
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
Outside Program Area
0.03
0.01
0.01
0.06
0.02
0.03
<0.01
0.02
0.12
0.05
0.04
0.10
0.09
0.06
0.15
0.09
0.15
0,01
0.15
0.80
0.12
0.08
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
p,p'-TDE o.p'-DDT p,p'-DDT
<0.01
<0.01
<0.01
<0.01
0.33
<0.01
0.15
0.62
0.14
0.06
0.06
0.05
0.09
0.07
0.15
0.05
0.02
0.02
0.06
0.06
0.07
<0.01
0.33
0.32
0.19
0.06
<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
<0.01
0.01
0.01
<0.01
<0.01
0.09
<0.01
<0.01
<0.01
<0.01
0.02
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
0.03
0.09
0.02
0.02
0.02
0.04
0.02
0.04
0.04
0.01
<0.01
0.01
0.03
0.02
0.01
<0.01
0.02
0.07
0..04
0.01
-------
Table No. 4 Cont'd.
Species
Dieldrin Endrin
oo
to
TIGER BEETLES:
A-164
A-167
F-1281
F-3137
F-3231
G-1135
G-1348
G-1425
G-1508
G-1509 1-2
G-1509 2-2
H-238
H-256
<0.01
0.01
0.05
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.04
0.01
0.01
0.05
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
C-541 <0.01 <0.01
C-559 <0.01 <0.01
C-622 <0.01 <0.01
G-1513 <0.01 <0.01
L-3229 <0.01 <0.01
E-3231 <0.01 <0.01
E-3231 <0.01 <0.01
F-1237 <0.01 <0.01
F-1281 0.05 0.05
F-3137 0.01 0.02
— Sample collected at beginning of crop season.
2/
— Corrected for pesticide recovery from fortified samples.
37
— Lower limits of sensitivity = 0.01 ppm.
o,p'-DDE
Residue,
p,p'-DDE
ppro-'' -'
o,p'-TDE
Inside Program Area
0.11
0.04
0.04
0.06
0.14
<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
0.14
<0.01
<0.01
0.04
0.06
1.80
1.02
1.26
2.02
2.44
1.58
4.44
0.91
1.38
0.01
2.62
2.10
0.06
Outside
0.46
3.07
1.88
1.86
1.03
2.44
1.37
2.39
1.26
2.02
<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
Program Area
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
p, p'-TDE o, p'-DDT
0.01
0.02
0.01
0.02
<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
<0.01
<0.01
<0.01
<0.01
0.01
0.02
0.04
0.05
0.06
0.06
0.12
<0.01
<0.01
<0.01
-------
No residues exceeding the detectable limits of 0.01 ppb for the
organochlorine and organophosphate pesticides of 0.05 ppb for methomyl,
carbaryl and carbofuran were found in any of the pond water samples.
In general, the majority of residues in biological samples from pro-
gram areas were equal to or less than residues in samples collected out-
side these areas. Naturally there were some exceptions; p,p'-DDT on frogs
(0.01 ppm outside and 0.02 ppm inside), p,p'-DDE in tiger beetles (4.44
ppm inside and 3.07 ppm outside) to cite a few instances.
In conclusion, our study did not produce evidence attributing sig-
nificant residue accumulation in the environment by pesticide usage pat-
terns currently being utilized in Wayne and Wilson Counties in North
Carolina. We are of the opinion that this conclusion is valid and would
apply to the majority of the state of North Carolina, since chemicals
utilized for tobacco pest control are very similar throughout the state,
varying only in frequency of use.
Additional residue information must be accumulated to project more
definite trends and draw sound conclusions concerning the pest manage-
ment program in tobacco and other crops. Studies are now in progress to
continue these studies for several years to establish a more reliable
baseline as a means of projecting future trends.
ACKNOWLEDGMENT
The authors wish to express their appreciation for the expert
assistance of personnel involved in collecting the samples and to H.
Richardson for his competent assistance in processing these samples.
Appreciation is also expressed to Dr. Stephen Warnick and staff, Inter-
mountain Laboratories, Inc., Salt Lake City, Utah, for analysis of a
portion of the biological samples. We also thank Dr. Don W. Wayne,
Professor of Statistics and Ecology, North Carolina State University,
for a most beneficial critique.
Trade names are used in this publication solely to provide specific
information. Mention of a trade name does not constitute a guarantee or
warranty by the U. S. Department of Agriculture and does not signify that
the product is approved to the exclusion of other comparable products.
183
-------
LITERATURE CITED
1. Ganyard, M. C., Jr., M. C. Ellis and N. M. Singletapy, 1972. North
Carolina Tobacco Pest Management; First Annual Report, 1971.
2. Stevens, L. J., C. W. Collier and D. W. Woodham, 1970. Pesticides
in Soil: Monitoring Pesticides in Soils from Areas of Regular,
Limited and No Pesticide Use. Pestic. Monit. J. 4(3):145-166.
3. Schutzmann, P. L., D. W. Woodham and C. W. Collier. 1971. Removal of
Sulfur in Environmental Samples Prior to Gas Chromatographic Analysis
for Pesticide Residues. J. Assoc. Anal. Chem. 54:1117-1110.
4. Reeves, R. G. and D. W. Woodham. 1974. Gas Chromatographic Analysis
of Methomyl Residues in Soil, Sediment, Water and Tobacco Utilizing the
Flame Photometric Detector. J. Agr. Food Chem. 22(1):76-78.
5. Reeves, R. G. and D. W. Woodham. 1972. Unpublished Data. USDA,
Environmental Quality Laboratory, Brownsville, Texas 78520.
6. Wiersma, C. B., W. G. Mitchell and C. L. Stanford, 1972. Pesticide
Residues in Onions and Soil. 1969. Pestic. Monit. J. 5(4):343-347.
7. Mills, P. A., J. H. Owley and R. A. Collier. 1963. Rapid Method for
Chlorinated Pesticide Residues in Non-Fatty Foods. J. Assoc. Off.
Anal. Chem. 46:186-191.
8. Johnson, L. 1970. Separation of Dieldrin and Endrin from Other
Chlorinated Pesticide Residues. J. Assoc. Off, Anal. Chem. 45:363-365.
9. Argauer, R. J., H. Shimanuki and C. C. Alvarez, 1970. Fluorometric
Determination of Carbaryl and 1-Naphthol in Honeybees (Apis mellifera L.)
With Confirmation by Gas Chromatography. J. Agr. Food Chem. 18(4):
688-691.
10» Johnson, D. P. 1964. Determination of Sevin Insecticide Residues in
Fruits and Vegetables. J. Assoc. Off. Agr. Chem. 47(2)-.283-286.
184
-------
ENVIRONMENTAL EFFECTS MONITORING OF INSECTICIDES USED
IN FOREST INSECT SUPPRESSION PROGRAMS.
Roger E. Sandquist
U.S. Forest Service
The U.S. Forest Service has responsibility for the management, pro-
tection, and development of the 187 million acre National Forest System
to produce continuous crops of wood, water, forage, wildlife, and recre-
ation. Through cooperation with State Foresters, private owners of
forest lands, wood processors, and private and public agencies, the Forest
Service also helps extend the Nation's forest resources by improving
the quality and increasing the quantity of goods and services produced
through better management and utilization. Some Forest Service activities
necessitate an introduction of pesticides into an ecosystem to manipulate
a pest population to increase or protect the productivity of a site.
Since most pesticides are not species specific, non-target organisms
may also be affected. Environmental effects monitoring is one way of
determining the extent, if any, of significant adverse effects upon
non-target organisms.
Suppression projects dealing with damaging infestations of defoliating
insects are the most publicly visible and sometimes controversial use of
pesticides. The scope of our environmental effects monitoring is dependent
upon the base of information available on the effects of the pesticide on
the particular non-target organisms of concern. When a pesticide is
first registered with the U.S. Environmental Protection Agency, certain
laboratory data are gathered to determine the category of toxicity to
fish and wildlife and hence the precautionary labeling required.!.'
These data, in addition to the acute and subacute mammalian toxicity data,
include:
I. Basic Tests
A. The avian single dose oral LD-50 of the technical grade
material for one species of waterfowl, preferably the mallard, and either
bobwhite or native quail or the ring-necked pheasant.
B. The avian subacute LC-50, a dietary 5-day exposure of the
technical product to the above species.
C. The acute, 96-hour LC-50 data using the technical grade
product are required for a cold water and warm water fish, preferably
the rainbow trout and the bluegill,
D. Data similar to the above are required for a sensitive
aquatic invertebrate such as Daphnia.
— Paraphrased from the "Guidelines for Registering Pesticides in the
United States," U.S. Environmental Protection Agency, June 1975,
published in the Federal Register, 40(123):26802-26928.
185
-------
II. Conditional Tests
A. Acute, subacute, and chronic tests.
1. Acute toxicity, 96-hour LC-50, data may be required for shrimp,
crabs, and larval oysters if the pesticides will be used in, or may contaminate
estuarine or marine environments. Shell deposition data on a representative
marine mollusc may be substituted for the acute oyster data.
2. On a case-by-case basis, satisfactory evidence is required that,
under conditions of proposed use, the pesticide will not cause unreasonable
adverse effects on the flora and fauna in aquatic environments. Additional
toxicity and residue studies of typical species of bottom feeders (channel
catfish or carp); predator fishes (bass, bluegill, northern pike, walleye,
and brook or rainbow trout); molluscs (oysters or freshwater or saltwater clams);
and crustaceans (Daphnia, Gammarus, or crayfish) may be required.
3. A chronic reproductive study with fish or birds (bobwhite
quail and mallard duck) consisting of an up to 90-day feeding exposure of
young adults may be required. Offspring are to be observed for 14 days.
When the Forest Service proposes using an insecticide over large land
areas, we must consider the effects of this chemical beyond its immediately
apparent, laboratory elucidated, toxicity to non-target organisms. I shall
cite examples which indicate the diversity of this activity.
In conjunction with an operational program to suppress damaging popula-
tions of the spruce budworm, Choristdneura fumiferana, in Maine, we con-
tracted with the Lake Ontario Environmental Laboratory to study the effects
of carbaryl on non-target arthropods, aquatic invertebrates, and fish.
Although carbaryl was applied to relatively small deciduous tree covered
blocks in gypsy moth, Porthetria dispar, suppression projects, it was never
applied over entire watersheds in coniferous forests in the Northeast.
This project will provide the Forest Service an opportunity to check the
accuracy of the predictions made in our environmental impact statement
and to improve our predictive capabilities for future spruce budworm
suppression actions.
The study on non-target arthropods is attempting to determine whether
the pesticide selectively eliminates or reduces the numbers of certain
arthropod species, with special emphasis on hymenopterans and the recovery
pattern of any affected species. The study will be continued in the 1976
Spring season.
Drop cloths were checked prespray and for 5 days postspray to deter-
mine the immediate insecticidal effects upon flying insects and sedentary
canopy insects. Flying insects are sampled with framed Plexiglas panes
2% feet high by 3 feet wide. These are coated with "tanglefoot" and
sample flying insects from ground level up to about 20 feet. Sampling
began before the insecticide treatment and will continue through the
Summer. Pollinating hymenopterans associated with a productive blueberry
are are also being monitored with the Plexiglas traps.
196
-------
2
Soil arthropods are sampled by taking 0.25 m of forest litter and
also a 5-inch diameter core sample to 10 inches of soil depth. The core
is divided into 5-inch upper and lower samples. Samples are taken prespray
and throughout the Summer. Terrestrial arthropods are sampled by pit
traps which consist of number 10 cans placed in a metal sleeve with the
lip of the can at ground level.
Associated with this sampling for biological activity of the insecti-
cide, residue samples for persistence of the insecticide are collected
from foliage samples taken from trees, soil, and forest litter. Biological
effects, if any, will be correlated with available pesticide residues.
The short and long-term impacts of aerially applied carbaryl on
stream invertebrates and trout will be assessed. The short-term impacts on
lotic macroinvertebrates focus on detecting reductions in populations
after spraying. Detecting significant alterations in benthos community
populations is the long-term objective.
2
A 24-hour drift net sample plus 3 grabs with a 1 foot Surber sampler
are taken at each of 5 stations along a 10 mile section of stream within
the spray area. Sampling was done 7 and 3 days prespray and 1, 3, 7, 14.
and 28 days after spraying. Sampling continues at monthly intervals until
September.. Current velocity, water temperature, water depth, and substrate
composition are recorded with each sample.
Prespray assessments of fish productivity are taken and compared with
a subsequent study one year later to determine if any change in species
composition and numbers resulted. An electroshocking apparatus is used
along the sample areas of the stream to subdue the fish. The fish are
identified, their length and weight recorded, and then released.
At each sampling station, a seine is placed across the downstream area.
A second seine is moved toward the stationary seine. The brook trout are
identified, their weight and length recorded, the stomach and esophagus
removed and preserved in alcohol. In the laboratory, the stomach contents
are sorted, counted and identified.
Current velocity, water depth, temperature, dissolved oxygen, pH,
and alkalinity are determined at each station on each sampling date.
Water samples are taken to determine the persistence of carbaryl in the
streams under these conditions.
The stream invertebrate study, the fish food organism study, and the
fish productivity studies should help answer the question of whether
carbaryl disrupts the fish food organisms enough to provide a significant
adverse impact upon fish production in streams.
The environmental effects of aerial applications of trichlorfon and
Bacillus thuringiensis (B.t.) to suppress populations of forest tent
caterpillars, Malacosoma disstria, in the Mobile Basin Cyprus-Tupelo swamps
in Alabama are being assessed.
187
-------
The impact of trichlorfon and B.t. on non-target arthropods is measured
by collecting organisms falling from the canopy in the spray area. Perma-
nent collecting cloths of known area are established in each of the spray
areas. Information on the rate of recovery of treetop arthropods is obtained
by spraying a small area of forest with pyrethrin insecticides. These
chemicals have an immediate knockdown effect on most arthropods and are
frequently used for "total" samples of tree canopies. Samples were taken
at 1, 14 and 28 days postspray and will continue monthly until recovery of
the non-target arthropods has occurred.
Yearly floods with water about 10 feet deep occur in this swamp habitat
at the time of pesticide application in late April. Samples of aquatic
organisms are taken by dip netting. Sampling in the treatment and control
area comparing populations of large aquatic insects (dragonfly, mayfly,
water beetle, and other groups) continues.
Caged turkeys are force fed large quantities of caterpillars killed
by trichlorfon. If symptoms are noted, the birds would be sacrificed and
residue analyses made on the brain, fat, liver, and muscle tissues. Simi-
lar studies, feeding white tailed deer foliage from treated areas, are
also undertaken. Auburn University personnel are cooperating with the
U.S. Forest Service in the non-target aerial and aquatic arthropod studies
as well as the force feeding of turkeys and deer.
The Marine Resources Division of the Alabama Department of Conservation
and Natural Resources scheduled bioassays to determine the lethal concentra-
tion of trichlorfon to larvae of shrimp and blue crabs—crustaceans of
economic importance in the Mobile Bay. This will provide an idea of the
amount of pesticide residue that may be tolerated by this resource.
The studies in the Cyprus-Tupelo swamp in Alabama are an instance in
which insecticides have been registered for use on a particular insect and
host, but where insufficient information is available on the effects of
the chemicals on the non-target organisms in a unique habitat.
In many instances, precautions can be taken to protect aquatic areas
from effects of insecticides. Buffer zones or non-spray areas are the most
common examples of this protection. Because of the very nature of the
Tupelo swamp habitat, this approach is infeasible. Alleviating some of
the potential hazard of an insecticide application here is the yearly
occurrence of flooding. This occurs at the time of greatest larval
susceptibility to insecticide and at the optimum timing for application
of this insecticide to reduce defoliation. This coincidence provides
for a tremendous dilution of insecticide and therefore, conceptually,
of any effects due to the substance. However, some objective basis
must be available to the land manager to assess a benefit/risk question
before proceeding with protecting his resource from the defoliating
insect.
As part of the USDA expanded Douglas fir tussock moth research and
development program, the environmental impact of those insecticides which
are most promising for control of the moth is being studied. Representa-
tive of this activity is the study on the impact of carbaryl, acephate,
trichlorfon, dimilin, and fundal on beneficial insects.
188
-------
Specific questions to be answered in these studies performed by
Washington State University entomologists include:
1. What is the abundance, species composition, and variability in
occurrence of bumblebees, miscellaneous wild bees, yellow jackets,
tachinid flies, flesh flies, syrphid flies, tabanid flies, and black flies?
2. What is the natural mortality of honeybees and aerial-nesting yellow
jackets in the plot areas?
3. What is the immediate effect of the insects on the beneficial
organisms studied?
4. If beneficial organisms are affected, what longer range changes
in species composition and abundance of flora and fauna result?
5. What is the net value of the insecticides in terms of pest control
effectiveness/adverse effects on hymenopterous beneficial insects.
This is a 3 year study. The objective of the first year is to gather the
baseline data on abundance and species composition of the subject beneficial
insects. Nest locations, as well as growth rates, colony development and
activities, and mortality rates will be charted. The second year will
continue the collection of the above data, plus monitoring the effects of
the various pesticides introduced into the study areas. Again, the third
year will repeat the observations made in the first 2 years to determine
whether there are any short or long-term deviations from the baseline
information which can be attributed to the insecticide application.
I mention this beneficial insects study to show the type of information
that can be used to assess the relative hazards involved with candidate
insecticides. If there are significant differences between the insecticides,
in this respect, all other attributes being equal, a choice can be made as
to which insecticides warrant first consideration for further development.
These studies also provide a background of information to consider in a
benefit/risk equation used to determine whether the benefits of an insecti-
cide application outweigh the risks.
In summary, the laboratory data required for registration of insecti-
cides is contrasted with the field data obtained by environmental effects
monitoring to determine the extent of adverse effects upon non-target
organisms from insecticides used in forest insect suppression projects.
This monitoring activity is ongoing and of a dynamic nature dependent
upon the objectives for monitoring.
189
-------
190
-------
PESTICIDE USE IN FOREST PEST MANAGEMENT PROGRAMS-
SUPPRESSION ALTERNATIVES
Frederick W. Honing
U.S. Forest Service
ABSTRACT
The U.S. Forest Service provides nationwide forest insect and disease
management technical assistance to all forest land managers regardless of
ownership. Major insect and disease management problems include pine and
fir bark beetles, spruce budworm, gypsy moth, tent caterpillars, mistle-
toes, root rots, leaf and stem diseases, seed and cone, and nursery and
plantation pests.
Pest suppression decisions are based upon biological, benefit/cost,
environmental and social evaluations. Suppression action includes aerial
and/or ground applications of pesticides, cutting and burning or removing
infested trees by salvage logging, silvicultural practices including
thinning, and combinations of the above. Suppression alternatives are
selected which will provide the least detrimental environmental impact,
highest rate of return for dollars invested, and achieve the most desirable
results in meeting forest land managment objectives.
191
-------
192
-------
PHOTOCHEMICAL CONFIRMATION OF PESTICIDES
R. C. Hanisch and R. G. Lewis
Introduction
One of the most difficult aspects of a pesticide residue chemist's
function is the unequivocal identification of agricultural chemicals at
the trace level. Techniques which are routinely used for the confirmation
of pesticide residues include the comparison of unknown and standard
pesticide retention times on two or more dissimilar Gas Liquid chroma-
tography (GLC) columns, the use of multiple detection systems or specific
detectors, the comparison of the thin layer chromatographic Rp values
of the actual and unknown compound, p-value determinations, chemical
derivatization, and mass spectrometry.
Several criteria which are important in the choice of a confirmatory
method include the specificity of the method, its sensitivity, and cost.
With a few exceptions the techniques listed above usually fail in
one of these areas. The use of "dual column" confirmation in the GLC
analysis of pesticides never affords unequivocal results as many
organic compounds can exhibit retention times identical to those of
pesticides on both columns (.1). Microcoulometric and electrolytic
conductivity detection systems, which can be coupled with the electron
capture (EC) detector to compensate for its lack of selectivity, suffer
from a relative lack of sensitivity as compared to the EC. Thin layer
chromatography requires large samples since it is sensitive only to
10 ng for most chlorinated pesticides and 50 ng for organothiophosphates.
The use of p-values is not affected by sensitivity but is lacking in the
area of selectivity (2).
Mass spectrometry is a powerful tool in the assignment of molecular
identity; however, in certain cases, this technique is unable to
discriminate between different compounds due to the fact that the molecular
ion isomerizes to another structure after ionization and prior to final
bond rupture. Toluene (I), cycloheptatriene (II), 3-ethynylcyclopentene
(III), and methylfulvene (IV) are four examples of isomers of the
empirical formula C7H_ that exhibit identical mass spectra (3).
CHCH CHCH3
II III IV
193
-------
Chemical derivatization is a reasonably specific means of confirmation.
In a situation in which a variety of pesticides must be confirmed it
can be too specific. Each derivative formed is a product of a particular
chemical reaction and only a few pesticides can be determined by any
one procedure. In some cases the analytical method is less sensitive to
the derivative than to the parent compound (4, 5). In addition, background
interferences can arise from the reagents used in the derivatization
process.
Infrared and nuclear magnetic resonance spectroscopy are two ad-
ditional means of obtaining the identity of a compound. These two
methods are not routinely used in residue analysis due to their lack
of sensitivity and, in the case of NMR, also the cost.
It is apparent that a sensitive, selective and relatively inexpensive
confirmatory technique capable of handling a broad spectrum of pesticides
with a minimum of background interference is needed to complement existing
methods. A procedure involving the photochemical alteration of pesticides
could in many instances meet these criteria.
Photochemical Principles
For a molecule to undergo a photochemical process it must be able
to absorb light in the 185^800 nm region of the spectrum. Most organic
photochemistry arises from the absorption of light in the 250-400 nm
range of wavelengths (near ultraviolet). In order to absorb light in
this region, the structure of the molecule must include unsaturated
sites such as olefinic bonds or aromatic moieties which contain electrons
in bonding u-orbitals or heteroatoms such as nitrogen and oxygen with
electrons in nonbonding p-orbitals.
During the excitation process the molecule absorbs a photon of
light which promotes an electron in a bonding or nonbonding orbital to
a higher energy antibonding orbital. The process is illustrated below
by means of a Morse diagram in Figure 1. •
Excited State A*
Et
Ground State A.
Figure 1, The photoexcitation process
194
-------
The excitation energy acquired by the molecule can be dissipated by
any one of three general processes (6):
emission
A* > A + hv
o
radiationless
conversion
chemical
A* > products
reaction
If the lifetime of the excited state of the molecule is of sufficient
length and the rate of the desired chemical reaction rapid with respect
to the competing processes then a photolytic pathway to new products
is available.
Molecules with halogen atoms incorporated into their structure
exhibit an intramolecular heavy atom effect. The probability of
singlet-triplet transitions is enhanced resulting in longer-lived
excited states.
Molecules which are not capable of absorbing light directly can be
excited photochemically through a process called sensitization. In this
process a donor molecule absorbs the light, is excited and transfers
its excitation energy via collision to the acceptor molecule. The
latter can then undergo chemical reaction.
Discussion
Most organic pesticides possess the structural criteria for photo-
chemical alteration; i.e,, double bonds, aromatic moieties, heteroatoms
with nonbonding p-electrons, or heavy atoms. Compounds from virtually
every class of pesticide exhibit photochemical behavior. The photo-
chemistries of dieldrin, 2,4-D, metobromuron, pyrethrin, amiben, sevin,
diquat, diphenamide, and parathion have been extensively studied.
In general, photochemistry can.be used as a confirmatory tool
in either of two ways: (a) the pesticide of interest may be photolyzed
to produce a characteristic photodegradation pattern, or (b) compounds
which interfere with the determination of a given pesticide may be
eliminated by selective photodegradation.
Mitchell's work in 1961 (7) was the foundation for the use of
characteristic photodegradation patterns as a means of confirming
pesticides. His method involved the paper chromatographic analysis
of 141 pesticides that had been irradiated with ultraviolet light.
The paper was spotted with 10 pg quantities of the pesticide, exposed
to a lamp rich in 254 nm light, then the chromatogram was developed.
195
-------
His results indicated that it was possible to obtain recognizable
photodegradation patterns for 91 of the pesticides involved in the
study. Thirty of the remaining pesticides did not undergo photodegrada-
tion and 20 gave results unsuited for analysis by paper chromatography.
Banks and Bills C8) coupled the specificity of u.v. degradation
patterns with the sensitivity of the electron capture detector to
produce a method capable of confirming a number of chlorinated
insecticides, including heptachlor, heptachlor epoxide, dieldrin,
aldrin, DDD, DDE, and DDT. Standards of these pesticides were
irradiated in 1 mm quartz cuvettes positioned 14 cm from a Hanovia
Utility Ultraviolet Quartz Lamp. The radiation intensity of this
lamp at wavelengths of 313 nm and shorter was 250 yw/cm^ at a distance
of 50 cm. An optimum irradiation time (OIT) was determined for each
pesticide. The authors defined the OIT as irridation time required
to yield the most characteristic degradation pattern for a given
insecticide. For the pesticides used in this experiment the OIT's
ranged from 6-60 minutes. After irradiation the samples were analyzed
by EC-GLC and the retention times for the photodegradation products
were determined. In addition, the ratios of the size of the degradation
peaks to the size of the undegraded parent peak and the percent
destruction of the parent peak were calculated. As extra confirmation
p-values were determined for both parent compounds and degradation
products. Utilizing these parameters, the presence of dieldrin in a
meat sample was confirmed at the 10 ppb level.
A similar procedure was employed by Kaufman ,et_ al_. (9). In this
case individual components from a mixture of pesticides were trapped
in tetrafluoroethylene tubing as they eluted from the column of a gas
chromatograph. The tubing was crimped shut on one end, 50 yl of hexane
were added to the tube, and the other end of the tube was sealed.
The trapped sample was then positioned 14 cm from a 100W medium-
pressure mercury vapor lamp and irradiated for the OIT. Because of
the small diameter of the sample tube the OIT's ranged between
15 and 120 seconds. After irradiation the photodegradation patterns
of the insecticides were determined by EC-GLC. The degradation patterns
of several pesticides are shown in Figure 2. This method permitted the
confirmation of heptachlor, aldrin, heptachlor epoxide, dieldrin, DDD,
DDE, and DDT present at the low ppb level in a variety of sample
substrates including bacon, beets, hamburger, turnips, cucumbers, eggs,
carrots, and soil. The effect of co-extracted material on the
degradation pattern of the insecticides was determined by fortifying
extracts from food and soil samples with the seven pesticides and
carrying them through the procedure. No interferences from the sample
extracts were observed. The method was also able to discriminate
between aldrin and the artifact arising from elemental sulfur that
had been reported by Pearson (10).
Gulan and co-workers (.11) employed the technique of Kauf man, et al.
in the analysis of polychlorinated naphthalenes. In this instance the
photodegradation products made it possible to distinguish between multi-
component Halowax 1014 and the seven organochlorine pesticides previously
mentioned. The same method was used in a similar fashion by Hannan
196
-------
ALDMIN
MCLDftM
P.P-OOT
080|
Jr
080
038
DM.
r
O6«
y rr
QP'-BDD
0.48
039
0.69 080
I I
O.P'-DDE
"1 r
IT I.
O.P'-DOO
0.49 0«B
i I
MEPTACHLOft,
1r
Q8.j|."».i48
6 12
TIME (MIN)
18
Figure 2. Pesticide Photodegradation Patterns
The degradation patterns are presented as bar graphs of peak heights
vs. retention times. The parent compounds are labeled P and the GC
retention times of degradation peaks relative to parent compounds
are indicated by the numbers adjacent to the bars.
et al. (.12) to determine polychlorinated biphenyls (PCB's) in the presence
of heptachlor epoxide, aldrin, dieldrin, DDE, DDD, and DDT. In cases
where the concentration of the pesticide of interest was too low
for detection, it was possible to enhance the sensitivity by making
successive trappings of the component prior to irradiation.
Glotfelty (13) employed solid-phase photolysis in the photo-
chemical confirmation of pesticides. A 0.1 to 0.5 ml aliquot of a
hexane solution containing the pesticide was placed on the inside
vertical wall of a 10 x 10 x 35 mm standard quartz cell of the type
used in UV-visible spectrophotometry. While the cell was lying on
its side the solvent was allowed to evaporate at room temperature,
197
-------
thus depositing a thin film of the solid pesticide on one of the optical
faces of the cell. The cell was then irradiated for 30 minutes at a
distance of 1 cm from a 2537ft lamp. After exposure, the cell face was
washed down with hexane and the solution was analyzed by EC-GLC. This
procedure yielded photodegradation products which could be used for
the confirmation of heptachlor, heptachlor epoxide, trans-chlordane
1-hydroxychlordene, chlordene, nonachlor, dieldrin, aldrin, DDT, ODD,
and DDE in water, soil, and plant tissues. For comparison, liquid
phase photolysis of the same pesticides was accomplished simultaneously
using the method developed by Banks and Bills (8). Differences in
the degradation patterns were observed. In some cases, different
proportions of the same products were found, while in other cases,
products were formed only in the solid state. Liquid-phase photolysis
generally produced fewer products at higher yields, while solid-phase
photolysis yielded more products in many cases resulting in more
distinct degradation patterns.
An alternate view of the photochemical confirmation of pesticides
entails the photolytic elimination of interfering compounds. In this
approach one attempts to selectively degrade a given compound by
choosing the appropriate excitation energy or proper sensitizer.
Leavitt and co-workers used a Rayonet photochemical reactor
equipped with 3000A lamps displaying major emissions in the
range of 280-340 run to eliminate the interfering components of Aroclor
1254 in the analysis of dieldrin, DDT, and DDE. Samples and
individual pesticide standards were irradiated for a period of 16 hours
in borosilicate tubes capped with tetrafluoroethylene stoppers. After
exposure the samples and standards were analyzed by EC-GLC. The
chromatograms indicated a reduction in the total peak area of the FOB
and a shift to peaks of shorter retention times due to successive
photoelimination of chlorine. Losses of 28 and 10% were exhibited by
DDT and dieldrin respectively. Quantification of these pesticides was
based on the amount of residue remaining after photolysis. The losses
were compensated for by the simultaneous photolysis of standards. p,p'-DDE
underwent total photodegradation to p,p'-dichlorobenzophenone, 2,2-bis-
(p-chlorophenyl)-l-chloroethylene and 2-(p-chlorophenyl)-2-(dichlorophenyl)-
1-chloroethylene after two hours of exposure. The quantitative deter-
mination of p,p'-DDE was based on the p,p'-dichlorobenzophenone concen-
tration. For this reason the samples were saturated with oxygen prior
to irradation to enhance benzophenone production. Except for the over-
night exposure period, the total analysis time was less than one hour
per sample.
Research recently completed in this laboratory exploited the
selective sensitized degradation of Interfering PCB components in the
analysis of mirex in tissue samples. Initially, direct photolysis of
mixtures of mirex and Aroclor 1260 in hexane utilizing a Rayonet Photo-
chemical Reactor equipped with 2S37& lamps was attempted as means of
isolating mirex. However, the high energy radiation caused the photo-
degradation of both the mirex and the PCB. The PCB's were, however,
more rapidly photolyzed, so that after short exposure periods (10 min)
the interfering PCB component (a heptachlorobiphenyl) was completely
destroyed, leaving 70 to 80% of the mirex intact. A mirex photolysis
198
-------
product, resulting from the loss of one chlorine atom, was observed at
0.66 the retention time of mirex on gas chromatographic analysis. It
was found that the rate of photolysis of mirex was sensitized by
traces of benzene in the hexane solvent, so that yields of the mirex
photoproduct varied with solvent quality.
While information derived for the short-wavelength photolysis of
mirex proved valuable in establishing the identity of the compound,
it was difficult to determine quantitatively the amount of mirex in
the mixture.
Based on the results of the preliminary study, a method was
developed to selectively photolyze the interfering heptachlorobiphenyl
without affecting mirex. This method utilizes an inexpensive 275W
sunlamp of the type obtainable from retail drug outlets. The ultra-
violet energy output of the lamp is greatest at 366 nm, with no output
below 280 nm. Direct irradiation of mirex solutions for prolonged
periods with this lamp produces no detectable degradation. Solutions
of Aroclor 1260 undergo only slight photodegradation under the same
conditions. Through the use of diethylamine as a "sensitizer", however,
it was found that the heptachlorobiphenyl could be completely eliminated
with little or no loss of mirex.
In a typical experiment, a solution of 250 pg/yl of Aroclor 1260
in spectrograde hexane containing 5% (v/v) of diethylamine was irradiated
in a quartz vessel for 100 min at a distance of 10 cm from the lamp.
The gas chromatogram shown in Figure 3 illustrates the complete
destruction of the heptachlorobiphenyl peak which interferes with the
determination of mirex. Recovery of the mirex was 95 to 100%.
The procedure was applied as the extract of a 2 g sample of
adipose tissue which had been spiked with mirex at the 1 ppm level
and Aroclor 1260 at the 5 ppm level. No interferences from the
substrate were observed.
The mechanism of the sensitized photodegradation of heptachloro-
biphenyl is presently under investigation. It is believed that the
diethylamine enters into a radical anion reaction with the biphenyl or
serves a more efficient hydrogen donor than hexane.
Summary
The photochemistry of pesticides can be utilized to provide a
rapid, sensitive, and specific means of confirmatory analysis with
a minimum of sample handling. Photochemical methods have been shown
to be particularly useful for the qualitative and quantitative deter-
mination of mirex in the presence of polychlorinated biphenyls. The
technique can be employed alone or in conjunction with other confirmatory
methods. The minimal cost involved in the establishment of this capa-
bility makes it economically accessible to any laboratory.
199
-------
References
1. Glotfelty, D. E., Caro, J. H., Anal. Chem. 42, 282 (1970).
2. Ibid.
3. Budzikiewicz, H., Djerassi, C., Williams, D. H., Mass Spectrometry
of Organic Compounds, Holden-Day, Inc., San Francisco (1967) p. 6.
4. Chau, A.S.Y., Cochrane, W. P., J. Assoc. Offic. Anal. Chem. _52_
(5), 1092 (.1969).
5. Chau, A.S.Y., Cochrane, W. P., J. Assoc. Offic. Anal. Chem. 52_
C6), 1220 (1969).
6. Turro, N. J., Molecular Photochemistry, W. A. Benjamin, Inc.,
New York (1965), p. 7.
7. Mitchell, L. C., J. Assoc. Offic. Anal. Chem. _44 (4), 643 (1961).
8. Banks, K. A., Bills, D. D., J. Chroma tog. 33_, 450 (1968).
9. Kaufman, W. M., Bills, D. D., Hannan, E. J., J. Agr. Food Chem. 2Q
(3), 628 (1972).
10. Pearson, J. R., Aldrich, F. D., Stone, A. W., J. Agr. Food Chem. 15,
938 (1967).
11. Gulan, M. P., Bills, D. D,, Putnam, T. B., Bull. Environ. Contam.
& Toxicol. 11 (5), 438 (1974).
12. Hannan, E. J., Bills, D. D., Herring, J. L., J. Agr. Food Chem. 21
(1), 87 (1973).
13. Glotfelty, D. E., Anal. Chem. 44 (7), 1250 (1972).
14. Leavitt, R. A., Su, G.C.C., Zabik, M. J., Anal. Chem. 45 (12),
2130 (1973).
200
-------
AN INDUSTRIAL HYGIENE LOOK AT THE PLASTICS INDUSTRY
Bobby J. Gunter
National Institute for Occupational Safety and Health
ABSTRACT
The plastics industry is divided into three areas. The first area
comprises the raw material suppliers, who manufacture polymers and molding
compounds from intermediates which they may have also produced. The second
area is made up of the processors, who make saleable items from the raw
materials. This involves processes such as extruding and injection molding.
The third area is comprised of machinery manufacturers, who supply equipment
to the processors.
The size of the plastics industry is constantly growing. In 1969 it
was estimated that about 25 million tons of plastics were produced. This
has probably grown in 1974 to almost 50 million tons. By the mid-1980's the
production and use of plastics will be larger than that of iron and steel.
The plastics production in the United States and in other countries is
closely related to the gross national product. The highest production and
consumption comes from those countries being highly industrialized, and the
lowest production and consumption comes from developing countries.
Plastic materials fall into two categories: Thermo plastics and thermo
setting. Thermo plastics can be softened repeatedly by the application of
heat. However, thermo setting materials are permanently shaped and cannot
be re-shaped by the application of heat. Several hundred individual polymers
can be made. However, approximately 20 types make up at least 90 per cent
of the total world output of plastics. The thermo plastics are the largest
group, and their production rate is growing at a much faster pace than the
thermo setting. I will limit this discussion to the production of polyvinyl
chloride (PVC), which is one of the most used of the thermo plastics.
201
-------
Polyvinyl chloride is produced by the polymerization of vinyl chloride
in the presence of initiators such as benzoyl peroxide, Polymerization is
usually carried out continuously in rotating autoclaves. The properties of
commercial PVC may be modified by the addition of dyes, pigments, filling
agents, and stabilizers as well as by co-polymerization with other monomers.
The use of PVC is very broad. It is used to make such things as imitation
leather, floor coverings, electrical insulators, food wrapping, and water,
sewage, and oil pipes.
The scientific community was made aware of vinyl chloride's toxicity a
little over a year ago. Major emphasis was placed on vinyl chloride's
ability to produce angiosarcomas in workers with prolonged history of expo-
sure. This discovery led to the initiation of a new standard for vinyl
chloride of one part per million for an 8-hour day, 40-hour work week. It
also put the responsibility of industry using vinyl chloride or its polymer,
PVC, to monitor the work place to assure that their employees were not over-
exposed to this carcinogen. The NIOSH Region VIII office has conducted
surveys in numerous industries using PVC in extrusion and injection opera-
tions. The highest exposures encountered are approximately one-half part
per million. Even at these levels, NIOSH cannot say that a worker is
totally safe from ever developing cancer connected with exposure to vinyl
chloride. I can personally say that exposures to vinyl chloride coming from
extrusion operations and injection molding is far less than those found in
a plant where the monomer is polymerized. In 1974 and 1975 the NIOSH
Region VIII office received numerous hazard evaluation requests from indus-
tries to evaluate the possibility of vinyl chloride exposure. Most of these
surveys have been completed, while others are still in the developmental
stage. When we find any exposure to vinyl chloride, we recommend personal
protection and exhaust ventilation installed to eliminate any exposure to
this carcinogen.
202
-------
PULSE POLAROGRAPHIC ANALYSIS FOR SOME AUXIN HERBICIDES
Jeffrey Whittaker and Janet Osteryoung
Colorado State University
INTRODUCTION
The development of trace analytical methods for picloram and other
auxin herbicides is of interest because picloram (TORDON) is receiving
increasing use. This popularity is due to the fact that picloram is one
of the most potent broadleaf plant growth regulators known, yet it has
low toxicity to animals and man (LD^Q = 8 g/kg (1,2)). This herbicide
can be further characterized as a relatively strong, stable picolinic
acid which is persistent in the soil and resists metabolic and chemical
attack.
The soil persistence and mobility of the compound in the soil is a
subject of considerable interest and research in the pesticide field
because these factors show wide variation and strongly dictate the prac-
tical use of the herbicide. For example, such basic questions as the
quantity of the herbicide applied in a particular situation, possible
contamination of natural waters, or the time required between the appli-
cation of the herbicide and the introduction of sensitive crops on the
land critically depend upon the persistence or transport of the herbicide.
Picloram is not metabolized to readily identifiable compounds and
is excreted in the urine of mammals as the intact pesticide. This makes
it possible to determine exposure by direct analysis of urine by cleanup,
esterification and GLC determination (3-7). The need for esterification
precludes inclusion of picloram in any GLC multi-residue procedure.
A review of analytical chemistry of Tordon demonstrates that practical
methods for picolinic acid herbicides and their metabolites are needed
because of serious drawbacks in the existing methodology. The colorimetric
procedure of Cheng is not sensitive enough for trace work with a limit of
detection of ca 0.5 ppm.8 A gas chromatographic method using electron
capture detection of the methylester derivative has a reported sensitivity
of 0.01 ppm, but the extraction, sample clean-up using alumina column
chromatography, and esterification is time consuming and tedious.^ Further-
more, this method has no reported sensitivity toward the decarboxylation
product which is reported to be the principal metabolite.10 But, despite
these drawbacks, this method remains the procedure of choice for Tordon
analysis. Bioassay techniques are reported sensitive to 4 ppb,H but these
methods are generally unsuitable for rapid routine analysis,
Polarographic methods are underexploited in pesticide analysis despite
the fact that, in general, pulse polarographic methods are rapid (2-3 min.
per sample), require minimal sample preparation, are sensitive to as low as
10~9 M for some systems, and the instrumentation is relatively inexpensive.
Most work on electrochemical analysis for pesticides has been done by Nangniot
and coworkers. Nangniot has reviewed earlier work on pesticide residue
analysis (12) and has published a book on the broader topic of polarographic
analysis in agronomy and biology (13). In addition, the work of Gajan (14)
has led to some official AOAC methods (15). However, these methods do not
203
-------
use the most powerful electroanalytical technique .now available for
analysis of organics, pulse polarography. In the. following sections,
we briefly describe this technique and its application to some auxin
herbicides.
PULSE POLAROGRAPHY
Although description of the various electrochemical techniques
alluded to here may be found in standard works on the subject (16, 17),
a description of the main features of pulse polarography here may be
useful in understanding the reasons for the experiments described
below (18).
Normal pulse (NP) polarography gives an S-shaped wave for the
reduction (or oxidation) of an electroactive substance characterized by
its height (inp) and its position at half-height (E%). The position is
characteristic of the substance and the rate at which it is reduced
while if the limiting current is diffusion controlled the height is
rigorously proportional to concentration according to a determinate
equation whose only parameters are the electrode geometry, the diffusion
coefficient (D) of the diffusing species, and the number of electrons (n)
transferred. For typical parameters at the dropping mercury electrode
(DME) (D-7 x 10~6 cm2/s, m2/3^6 = 1.8 mg2/3s~l'2 where m is the mercury
flow rate in mg/s and t
-------
50/n yg/1. Slow processes give rise to decreased sensitivities and
increased detection limits. This corresponds to about 50/n ng of
material absolute. The greater sensitivity of DP makes it an
attractive technique, but far more detailed knowledge of the electro-
chemical processes are required than for NP, because of the dependence
of peak heights on matrix for slow reactions. Therefore, following
studies designed to give conditions of diffusion controlled NP currents,
one must investigate the effects of solvent, pH, supporting electrolyte,
and possible substrate contaminants on DP currents.
EXPERIMENTAL MATERIALS AND METHODS
Materials. In general, reagent grade chemicals have been used without
further purification. Analytical standards of plcloram and Dowco 290
(3,6-dichloropicolinic acid) were donated by Dow Chemical Company
(Ref: G. E. Holdeman, Manager of Product Standards, Agricultural Products,
Ag-Organics Department, Dow Chemical Company, Box 1706, Midland,
Michigan 48640).
0
Electrochemical cells used have been of the Brinkmann type or 150 ml
Berzelius beakers with Sargent plastic cell top. Either design provides
for deaeration of sample solution using a purging gas and for introduction
of working, reference, and auxiliary electrodes. Coulometry was carried
out using a Kontes Universal electrode vessel (250 ml) or a three compart-
ment cell with fine glass frit separators, a mercury pool working electrode
and carbon auxiliary electrode.
Prepurified nitrogen was used as the purging gas. It was further
purified by passing over hot (600°C) copper turnings. This oxygen removal
system includes a tube filled with copper turnings and a small tube
furnace. The entire assembly is available from Sargent. The copper
tube is regenerated (the copper oxide reduced) by passing forming gas
(15% H» in N2) through the hot tube.
The purging gas is brought to the cell via aluminum or Tygon tubing.
With organic solvents such as methanol, Tygon tubing must be lined with
polyethylene to prevent extraction of electroactive materials from the
Tygon. These materials are carried into the cell and cause large and
irreproducible background currents.
In general, the purging gas is presaturated with the solvent/supporting
electrolyte system being used.
The working electrode is a hanging mercury drop electrode (HMDE)
or a dropping mercury electrode (DME). Several different capillaries
have been used for the DME. Capillary characteristics are quoted in the
text where pertinent. A carbon rod auxiliary electrode was generally
employed, usually without a separator.
A variety of reference electrodes were used depending on the solvent
system. The necessity for accurate potential measurements in development
work and the desirability of being able to compare potentials in different
solvents make the choice of reference electrodes an important and
difficult problem.
205
-------
In methanol solvent systems three reference electrodes appear to
be satisfactorily reproducible and within 200 mv of an aqueous SCE,
these include a Ag/Ag C1(S) 10.1 M LiCl methanol electrode,
Hg/Hg2Cl2(S) 10.1 M NaCl aqueous electrode, and a Ag/AgCl(S) gel sat.
KC1// 0.1 M NaCl aqueous double junction electrode. In 100% methanol
solution the Ag/AgCl, 0.1 M LiCl methanol electrode is satisfactory.
The reference electrodes containing 0.1 M NaCl filling solution are
suitable when an aqueous filling solution is preferred because 0.1 M NaCl
is soluble even in 100% methanol and consequently does not precipitate
and clog the junction as 1 M or saturated chloride salts were found
to do. In aqueous solution and glacial acetic acid commercially pre-
pared saturated calomel electrodes (SCE) or Ag/AgCl electrodes were used.
We have not investigated the magnitude of junction potentials in
these solvents or attempted to estimate standard single ionic energies
of transfer from solvent to solvent. Therefore, the potentials quoted
in the text must be considered to be operationally defined by the mea-
surement and have no absolute thermodynamic significance.
pH measurements were carried out using a Fisher low-salt error glass
electrode and the appropriate reference electrode. pH values measured
in methanol were converted to the equivalent activity in aqueous solu-
tion by adding a potential correction for the solvent difference deter-
mined by Alfenaar and De Ligny. ' Thus all pH values reported are the
equivalent pH in water. This "solvent correction" for pH is a special
solution to the general problem mentioned above of relating potential
measurements in different solvents.
Mercury was triply distilled quality obtained from Bethlehem
Apparatus Company.
A general comment about choice of solvent systems is in order here.
The reactions studied to date involve pH dependent reduction at mercury
electrodes with probable involvement of adsorption of the reacting
species as an important feature of the reduction mechanism. Organic
electrochemistry is not sufficiently developed yet for comprehensive
theories of reaction mechanism to have been worked out. We only have
some general rules of thumb about the effects of solvent and supporting
electrolyte on rates of these processes. In all cases analytical utility
is maximized by maximizing the reduction rates of the species sought.
Because the systems of interest are pH dependent, we wish to use well-
buffered protic solvents. Because drying solvents is difficult and
electrochemical reaction rates are often influenced by trace amounts
of water, generally we want to work in water or in water/organic mixtures
rather than "pure" organic solvents. Our main efforts have been directed
toward water and the lower alcohols as solvents.
Equipment. A Princeton Applied Research Pulse Polarographic Analyzer
Model 174 with Model 172 drop timer was used in conjunction with a
Houston Omnigraphic Model 2000 X-Y recorder. The PAR 174 is a multi-
functional potentiostatic electrochemical instrument capable of operation
in DC, Tast, Normal Pulse (NP), and Differential Pulse (DP) Polarographic
modes. The drop timer is synchronized with the 174 and controls the
206
-------
drop time of the DME by mechanically dislodging the drop at some time
less than the natural drop time.
The PAR 174 and the similar Tacussel PRG 5 are excellent quality
equipment well suited to routine analysis and of modest cost (~$2500).
Readout is typically via recorder.
A Tacussel VOCTAN electrochemical system was also used. This
system consists of a PRT 30.01 Potentiostat, UAP 4 Pulse Unit, GSTP3
Triangular Wave Generator and UAP 3 AC Polarograph. Output is read on
an EPL2 strip chart recorder. The VOCTAN is an extremely flexible
electrochemical system which permits the investigation of chemical
systems using a variety of modern electrochemical techniques including
pulse polarography (various modes), AC polarography with phase sensi-
tive detection, cyclic voltammetry at stationary electrodes and the
DME, chronoamperometry, chronocoulometry, and chronopotentiometry.
This versatile capability is especially useful in determining the
overall features of an electrochemical reaction for the purpose of
optimizing parameters for analysis by DPP or NPP.
Other equipment available and used from time to time in these
experiments include a Hewlett-Packard 120B Oscilloscope, Fisher
Accumet Model 230 pH meter, Sargent 3007 Portable pH Meter, and Fluke
8000A and Keithley 168 Autoranging digital voltmeters.
Picloram is best viewed as a substituted picolinic acid. Volke
and Volkova^O and Jellinek and Urwin^l have investigated the electro-
chemistry of picolinic acid. Jellinek and Urwin employed a manual
polarograph and two-electrode cell with a dropping mercury electrode
and SCE reference. The limiting current for the reduction was found
to be a function of pH due to a slow chemical protonation reaction
preceding the electro-chemical step. The half-wave potential was also
a function of pH according to the equation Eu = -0.081 pH -0.741 V
from pH 2.25 to pH 9. The work of Volke and Volkova extended and
substantiated these results. It is interesting that the picolinamide
has substantially different pH dependence; this permits simultaneous
determination of the acid and the amide in the same solution by proper
pH adjustment.
The electrochemistry of picloram is almost embarrassingly rich,
for in addition to the well-characterized reduction waves discussed
above, there is a complex anodic electrochemistry associated with the
p-amino group. Weinberg and Weinberg have reviewed the large body of
work dealing with the anodic oxidation of primary aryl amines.^2
Although pyridine itself is oxidized.at +1.82 V vs Ag/0.1 M Ag~ in
acetonitrile on platinum, the oxidation of the primary amine is more
facile. Of particular interest is an investigation of the oxidation
of parasubstituted anilines in the presence of pyridine in
acetonitrile (23-27).
The oxidation is an overall two-electron process involving proton
transfer to pyridine and coupling to form Ar - N = N - Ar. In addition,
there is some coupling between the free radical intermediate, Ar - NHO,
and pyridine. Dauquis, &t^ al.^ have carried out the oxidation at platinum
207
-------
in acetonitrile at +0.55 V vs Ag/0.01 M Ag of compounds of the type
ArNHo in the presence of 2-picoline without finding substantial amounts
of non-tar products. This suggests that the electrochemical oxidation
of picloram should be distinguishable from the oxidation of other
primary amines which might be expected to appear as contaminants in
complex samples of biological origin.
Two electrochemical procedures for trace amounts of picloram have
been published, a classical DC polarographic method by Filimonova and
Gorbunova (28) and a method using the more sensitive pulsed polarographic
technique by Gilbert and Mann. The latter has a reported sensitivity of
0.02 ppm.
Filomonova employed regular dc polarography with a dropping mercury
electrode and saturated calomel reference electrode. At pH 2 in aqueous
solution there is one reduction wave which is pH dependent and corresponds
to a two-electron process. The pH dependence (AE^/ApH = -57 mv) indicates
a prior protonation reaction. The proposed mechanism is
CI
Cl
^2
r
'N>
COOH
+ H
COOH H+
COOH
Quantitative measurements suggest the wave is quasireversible.
Although a wide range of pH values was studied, the other solution
most promising from an analytical viewpoint was 0.05 M [(C2H5)AN]OH
where there is a single four-electron reduction wave at E, - - 1.59 v.
The proposed mechanism is: >z
LH
4e
COO
2H+
COO
_ 4- 2CI
The reduction potential for this wave is close to that for potassium
ion discharge at mercury, so potassium ion in large concentration would
constitute an interference. Since the wave involves four electrons,
however, it could give twice the sensitivity of the wave in acid. No
data are presented which show the reversibility of the wave.
208
-------
Procedures are presented for determination of picloram in water,
light sandy soil, heavy soil with high humus content, and dry corn
mass. Direct determination in filtered water with pH adjusted to 1 was
said to have a "sensitivity" of 0.2 mg/1. Using modern electrochemical
techniques, one ought to achieve a detection limit no larger than one-
tenth this value.
Gilbert and Mann (29) have, on the basis of incorrect and inadequate
experimentation, concluded that the picloram reduction wave is catalytic
in 0.01 M sodium acetate -0.026 M acetic acid (pH 4.3). They report
"detection limit" of 0.02 ppm for determination of picloram in water,
and survey various potential metal ion interferences.
RESULTS AND DISCUSSION
Because Filimonova1s method (28) was reported using classical DC
polarographic analysis, an investigation was made to check the suita-
bility of her conditions (aqueous pH 1 with t^SO^) for pulsed methods.
The observed DC Eu of -772 mv vs. S.C.E. agreed with her reported
Ej^ of -780 mv vs; S.C.E. but with the better wave resolution of dif-
ferential pulse polarography was found that the DC wave consisted in
fact of two waves with Ep = -813 and -867 mv vs. S.C.E. (pulse height
50 mv). Unfortunately, these processes give large maxima in the normal
pulse mode and a relative increase in the second peak height with
increasing pulse height in differential pulse mode. Consequently,
Filimonova1s conditions are unsuitable for pulse polarography.
Gilbert's conditions (29) (aqueous pH 4.35 buffered by 0.01 M HOAC)
were reevaluated in our laboratory. The DP peak potential, E = 1.126 v
vs. S.C.E., was slightly lower than E = r>1.30 v vs. S.C.E. reported by
Gilbert. The wave form was acceptable for differential pulse polarography
because no second wave was apparent and a well defined diffusion plateau
was observed in normal pulse experiments. But the observations by Gilbert
that the current varies non-linearly with pH by about a factor of 2 in
the pH region 4.0 - 5.0 and varies linearly with ionic strength, about
-40% per unit ionic strength increase, seriously detract from the
usefulness of the method. Also a number of metals interfere including
iron (III); this requires pretreatment with ethylenediaminetetracetic
acid (EDTA).
A controlled potential reduction of 2.7 * 10 mol picloram under
Gilbert's conditions yielded ca 8.5 * 10~7 mol NH^ as measured colori-
metrically by the Bertholot reaction (cf. Reaction 2). The 30% yield
can be explained because the products of the reduction experiment
exhibited a partial negative interference on the color development as
determined by the addition of known amounts of NH, to the reduced
mixture prior to color development. But despite the fact that the
analysis was not quantitative, the qualitative observation that
ammonia is produced in the electrochemical reduction of picloram casts
serious doubt on Gilbert's proposal that the mechanism of the reaction
is catalytic hydrogen evolution. Our observation agrees with
Filimonova's postulate that the mechanism involves cleavage of the
amino group. Her conclusion was based on the dependence of the half
209
-------
wave potential on pH. Neither of the postulated mechanisms are
consistent with the two peaks observed at lower pH, and it would be
surprising if both mechanisms are operational since the two peak currents
are comparable over a range of conditions.
Gilbert found n = 0.7 for the relationship i = Kh where i is
the DP" peak current, h is the mercury height and K is a constant, •*•'
and concluded from this that the reduction is catalytic. When n > 0.5
a catlytic mechanism is indicated in the case where i is the DC polaro-
graphic limiting current, but the same relation does not hold for DP.
We found for the DC experiment n = 0.36 which indicates a quasi-dif fusion
controlled process. Also the current-time curves do not show the
steadily increasing slope which is typical for catalytic curves. As
the drop time was varied from 0.5-3 sec the current increased as a 0.22
order parabola which is also consistent with a quasi-diffusion controlled
wave. These experiments indicate that the catalytic hydrogen evolution
mechanism is unlikely.
It is important to distinguish between a catalytic, kinetic or
diffusion controlled mechanism in this case because a wave which has
partial kinetic control — as the picloram wave appears to have — can be
significantly improved for analytical purposes if conditions are found
which increase the rate of the rate-limiting process. If the kinetic
process is made faster and the overall electrochemical reaction becomes
diffusion controlled, then both the sensitivity and reliability of the
method can be improved, Consequently, further investigations on the
nature of these two waves were carried out.
A study of the half-wave potential as a function of pH was made
using the differential pulse technique over the pH range 2.50 to 4.30.
As the pH was decreased the half-wave potential of the more anodic wave
shifted linearly by + 94 mv/pH which is in fair agreement with Filimonova's
observation of a shift of -109 mv/pH. This indicates that one proton
and one electron or two protons and two electrons are involved in the
electrochemical reduction. A reasonable explanation is that the acidic
proton of the picolinic acid functionality is involved. The exact
interpretation of pH dependence is made difficult by uncertainty over
the value of the pKa for the reaction
HP H+ +P~
where HP represents picloram, the undissociated uncharged acid. This
constant has been determined by titration by several workers with no
experimental details given. Not only do the values not agree, but also,
in the one case in which sufficient data are presented to check the
value, the data are internally inconsistent (30). The values reported
are 3.4 (30), 3.0 in 50/50 methanol/water (31), 3.1 (10), and 4.1 (32).
Because picloram is twice as soluble in alcohol as in water
450 mg/100 ml; EtOH 1.0 g/100 ml) we investigated alcohols as solvent
systems. Using 0.1 j{ LiCl as a supporting electrolyte and acetic acid
buffers, we found that picloram is much more easily reduced in methanol
than in water. The pH was measured in methanol with a glass electrode
and converted to the equivalent activity in aqueous solution for
210
-------
comparison by adding a potential correction for the solvent difference
determined by Alfenaar and DeLighy.1^ (All pR's reported are the equivalent
pH in H20). Thus, at pH 7.2 picloram gave a wave with EJj = -0.88 v vs.
S.C.E. which is several hundred millivolts anodic of the reduction in
aqueous solution at pH 4.3 with Ejg = -1.1 vs. S.C.E. The appearance of
the wave at -0.83 V shows a surprisingly large change in reactivity for
the solvent change from H20 to methanol.
A variety of supporting electrolytes, buffers and pH's were screened
in order to find a system suitable for picloram analysis. Alkaline
conditions using tartaric acid, ammonia, hexamethylenetetraamine and
sodium hydroxide in methanol were similar to aqueous systems at high
pH; no picloram wave was observed. A salicyclic acid buffer system at
pH 7.5 gave an ill-defined wave with Eij = -550 mv vs. S.C.E. Aqueous
phosphoric acid buffer adjusted to pH 3.5 with NaOH gave a wave with
large maxima and an aqueous phosphate buffer system adjusted to pH 10.5
gave a well-defined wave at Ejg = -1.6 V vs. S.C.E. The limiting current
for the latter conditions was unfortunately much less than the current
in acid solution so that those conditions were not further investigated.
Ethylenediamine and anhydrous glacial acetic acid were other
nonaqueous solvents which were investigated because of their particular
acidic or basic properties. Dicloram in ethylenediamine with 0.1 M LiCl
supporting electrolyte gave no measurable wave. Acetic acid containing
0.1 M acetic anhydride to remove water and 0.5 M NaOAc as a supporting
electrolyte gave a well characterized single wave with Eig = -955 mv vs.
S.C.E. Studies of the current dependence on mercury height and the
current-time behavior suggested that the wave was quasi-diffusion con- ,
trolled. Also, the polarographic constant I = 5.07 uA Mmol~l 1 mg~2/3 sec
was about half the sensitivity which we measured for Gilbert's conditions.
These facts, plus the unpleasantness of the solvent, made this system
less than desirable. Thus, aqueous or alcoholic media at high acidity
appear to afford the most likely systems for the development of a
picloram method.
The interference by the iron wave which required pretreatment with
EDTA in Gilbert's procedure is absent in methanol; 1 * 10~5 M Fe(III)
in 0.1 M LiCl with 2.4 * 10~3 F HC1 gave no measurable iron peak.
We have investigated a series of alcohols: methanol, ethanol,
iso-propanol and normal propanol. Each solution contained 0.1 M LiCl
as a supporting electrolyte and 2.4 * 10~3 F HC1. The two waves present
in methanol were not observed in the higher alcohols. Picloram dissolved
in ethanol displayed one wave at E^ = -787 mv vs. S.C.E. with about
66% the current observed under aqueous conditions. In the propanols,
the current was only ca 25% the current under aqueous conditions and
the closeness of the wave to the cathodic breakdown potential caused
the diffusion plateau to slope badly. Thus, it was decided to further
investigate only the ethanol solvent system.
The effect of water concentration in ethanol on the picloram wave
was evaluated because this parameter may vary between different
laboratories or from day to day. The current for the d.c. polarogram
is constant within ± 10%, but in pulsed modes the current increases
211
-------
steadily by about 27% from absolute ethanol (commercial absolute ethanol
contains between 0.2 - 0.5% H20) to 20% water. At higher water concen-
trations the current decreases; also the slope of the diffusion plateau
increases because the solvent breakdown potential becomes more anodic.
Thus, picloram reduced in ethanol-water mixture of ca. 20% more water
has currents comparable to aqueous systems. Furthermore, the large
amount of added water should make the minor fluctuation in the content
of water in absolute alcohol negligible.
Preliminary studies indicate that 1 M H3P04 and 0.1 M LiCl in
methanol may be satisfactory because only a single peak is observed.
The half wave potential is -1.18 V vs. 0.1 1? NaCl Calomel Electrode.
The concentration of phosphoric acid is sufficient to overcome the
buffering capacity of most natural samples.
Since many of the problems with the use of the above solvents,
buffers and supporting electrolytes are associated with the presence
of two picloram waves, a better understanding of the nature of the
electrochemical processes involved will allow a more scientific selection
of conditions suitable for a routine analytical method.
212
-------
1. Chang, I., and Foy, C. L., "Effect of picloram on germination and
seedling development of four species," Weed Sci.. 1£, 58-64 (1971).
2. Hamaker, J. W., Johnston, H., Martain, R. T. and Redemann, C. T.,
"A picolinic and derivative: a plant growth regulator," Science,
141. 363 (1968).
3. Getzin, L. W. and Shanks, C. H., "Persistence, degradation, and
bioactivity of Phorate and its oxidative analogues in soil,"
J. Econ. Entomol., 63, 52 (1970).
4. Hance, R. J., "Further observations of the decomposition of
herbicides in soil," J. Sci. Food Agr., ^0, 144-145 (1969).
5. Meikle, R. W., Williams, E. A., and Redemann, C. T., "Metabolism
of Tordon herbicide (4-Amino-3,5,6-Trichloropicolinic Acid) in
cotton and decomposition in soil," J. Ag. Food Chem., 14, 384-387
(1966).
6. Redemann, C. T., R. W. Meikle, P. Hamilton, V. S. Banks, and
C. R. Youngson, "The fate of 4-Amino-3,5,6-Trichloropicolinic
acid in spring wheat and soil," Bull. Environ. Contam. Toxicol.,
3_, 80-96 (1968).
7. Youngson, C. R., Goring, C. A. I., Meikle, R. W., Scott, H. H.
and Griffith, J. D., "Factors influencing the decomposition of
Tordon herbicide in soils," Down Earth, 23_, 3-11 (1967).
8. Cheng, H. H., "Extraction and colorimetric determination of
picloram in soil," J. Agr. Food Chem., L7, 1174-1177 (1969).
9. Bjerke, E. L., A. H. Kutschinski, and J. C. Ramsey, "Determination
of residues of 4-amino-3,5,6-trichloropicolinic acid in cereal
grains by gas chromatography," J. Agr. Food Chem., 15, 469-473
(1967).
10. Sargent, J. A. and G. E. Blackman, "Studies on foliar penetration,"
J. Exper. Bot.t 66, 219-227 (1970).
11. Scifres, C. J., R. W. Bovey, and M. G. Merkle, "Variation in bio-
assay attributes and quantitative indices of picloram in soils,"
Weed Res.. 12 58-64 (1972).
12. Nangniot, P., "L'Application des methodes electrochimiques a 1'etude
des residus de pesticides," Mededelingen Rijlesfaculteit Land-
bouwwetenschappen Gent, 31, 447-473 (1966).
13. Nangniot, P., La Polarographie en Engronomie et en Biologie, Vander,
Bruxelles, 1970.
14. Gajan, R. J., "Collaborative study of confirmative procedures by
single sweep oscillographic polarography for the determination of
organophosphorous residues in nonfatty foods," JAOAC, 52, 811-817
(1969).
213
-------
15. Pesticide Analytical Manual, Vol. I, USFDA, Section 12,F, pp. 1-6.
• 16. Meites, L., Polarographic Techniques, 2nd ed. John Wiley, Inc.
N.Y. 1965.
17. Zuman, P., "Some Techniques in Organic Polarography," in Organic
Polarography, P. Zuman and C. L. Perrin, Interscience, N.Y., 1969.
18. Osteryoung, J. and R. A. Osteryoung, "Pulse polarographic analysis
of toxic heavy metals," Amer. Lab., July 1972, pp. 8-16.
19. Alfenaar, M.. and C. L. Deligriy, "The universal pH-scale M methanol
and methanol-water mixtures,". Rec. Trav. Chem., 86, 1185-1190 (1967).
20. Volke, J. and Volkova, V., "Polarographic aromatischer heterocyclischer
verbindunger. II. Polarographisches verhalten der isonicotinsaure
und picolinsaure," Collec. Czech. Chem. Comm., 2£, 1332-1339 (1955).
21. Jellinek, H. H. G., and Urwin, J. R., "Polarography of picolinic and
isonicotinic acid and their amides," J. Phys. Chem., 5_8_, 168-173
(1954).
22. Weinberg, N. L. and Weinberg, H. R., "Electrochemical oxidation of
organic compounds," Chem. Rev., 68, 449 (1968).
23. Wawzonek, S. and Mclntyre, T. W., Jr., "Electrolytic oxidation of
aromatic amines," J. Electrochem. Soc., 114, 1025-1029 (1967).
24. Cauquis, G., Fauvelot, G., and Rigaudy, J., "L'oxydation electrochimique
de la triteriobutyl-2,4,6 aniline dans 1'acetonitrile," Compt. Rend.,
C, 264. 1758 (1967).
25. Ibid, "Les proprietes electrochimiques de la tritertiobutyl-2,4,6 aniline
en milieux organique et hydroorganique," Bull. Soc. Chim. Fr.. 4928 (1968),
26. Basselier, J. J., Cauquis, G. and Cros, J. L., "Synthesis of an pyrido
(1,2-x) benzimidazole and of an amidine by electrochemical oxidation of
2,4,6-Tri-t-butylaniline in the presence of pyridine," Chem. Commun.,
1171 (1969).
27. Cauquis, G., Coquand, J. P., Rigaudy, J., "L'oxydation electrochimique
de la tribromo-2,4,6 aniline dans 1'acetronitrile: resultats et
discussion de la nature de 1'etape primaire de la reaction,"
Compt. Rend.. 268, C_, 2265 (1969).
28. Filimonova, M. M. and V. E. Gorbunova, "Polarographic determination
of chloramp (Potassium 4-amino-3,5,6-trichloropicolinate) in water,
soil, and plants," Zhur. Anal. Khim.. ^8_, 1184-1187 (1973). (Russ.
J. Anal. Chem.. ^8, 1048-1051 (1973)).
29. Gilbert, D. D., and J. M. Mann, "Herbicide Analysis by Pulse
Polarography Picloram," Intern. J. Environ. Anal. Chem., 2_, 221-228
(1973).
214
-------
30. Cheung, M. W. and J. W. Biggar, "Solubility and molecular structure
of 4-amino-3,5,6-trichloropicolinic acid in relation to pH and
temperature." J. Agr. Food Chem., 22, 202-206 (1974).
31. Kefford, N. P., and 0. H. Caso, "A potent auxin with unique
chemical structure - 4-amino-3,5,6-trichloroplcolinic acid,"
Bot. Gaz., 127 (2-3), 159-163 (1966).
32. Hamaker, J. W., C. A. I. Goring, and C. R. Youngson, "Sorption and
leaching of 4-amino-3,5,6-trichloropicolinic acid in soils,"
Chap. 2, pp. 23-37, in Adv. Chem. Ser., 60 (1966).
215
-------
216
-------
FATE OF PESTICIDES IN THE ENVIRONMENT
Dallas E. Miller
U.S. Environmental Protection Agency
Approximately one billion pounds of pesticides are applied annually
in the United States. Yet there does not seem to be a continual loga-
rithmic build-up of pesticide residues in soil and water, although resi-
dues can accumulate from the repeated application of some persistent
pesticides. Several factors are responsible for the loss of applied
pesticides from the environment.
Pesticides can be lost to the application site by evaporation, co-
distillation, drift, runoff, leaching or removal by organisms. These
mechanisms represent transportation forms but not contribute to the
eventual loss from the total environment. However, the parent pesticide
compound can be lost to the environment via several degradation or
transformation routes.
Environmental pesticide degradation mechanisms can be categorized
into three reaction classes—chemical, photochemical, and biological.
Due to the diversity of pesticide chemical structures, soil or water
conditions that react with the pesticide to contribute to rapid breakdown
of one compound could retard the breakdown of another. Parathion hydrol-
ysis is more rapid under acidic or neutral conditions than paraoxon.
However, paraoxon hydrolysis proceeds more rapidly than parathion hydrolysis
under alkaline conditions. Also, alkaline or acid conditions do alter
the nature of the degradation products. Under acid conditions, the major
degradation product of parathion is p-Nitrophenol, a compound that has
approximately the same toxicity as parathion. Under alkaline conditions
the major parathion degradation products are paraoxon and 2,4-Dinitrophenol.
Paraoxon is more toxic than parathion and 2,4-Dinitrophenol is about
equally as toxic as parathion.
The speed of organophosphorus and carbamate pesticide breakdown in
soil and water is affected by pH, temperature and organic and mineral
media constituents. High temperatures increase the activation energy
levels of the pesticide and contribute to their rapid breakdown. Conse-
quently, pesticides in general can be expected to be more persistent
under cold conditions than under warm conditions. The pH of the media
contributes both to the speed of the degradation reaction and to the
products of degradation. Certain clay soils and soil organic matter can
bind to the pesticide making it unavailable for degradation or biological
activity.
Energy derived from the sun can degrade pesticides both thermally
and photochemically. The sun's radiation is commonly considered to exist
in the form of waves. These waves vary in length from extremely short
in the gamma and X-ray range to long in the microwave and radiowave
range. The energy supplied by a given wave length can be calculated
using the formula
hc
217
-------
-22
where h = planks constant (6.62 x 10 ergs/sec. )» c - the velocity of
light (3 x lO1 cm/see.) and X = the wavelength. Since both h and c
are constants, it is easy to see the energy provided by a light wave
decreases with increase in wave length. This light spectrum is very
broad; however, the total spectrum does not reach the earth's surface.
The ozone layer of our atmosphere effectively absorbs light waves shorter
than 'approximately 290 nm. The maximum total energy supplied to the
earth is at 540 nm. Above 540 nm, the energy scale begins to decline.
Open sky dispersion of U.V. light also affects the total energy provided
by a given portion of the light spectrum. The dispersion of U.V. light
may equal or surpass the energy provided by direct sun radiation. This
dispersion enhanced energy increase is more pronounced the shorter the
wave length.
Each chemical compound displays its particular wave length where it
absorbs maximum photochemical energy. This point of maximum absorbance
is bordered on both sides by areas of lesser absorbance. The radiant
energy actually available for photodecomposition is bounded by the ozone
barrier at ca. 300 nm at one end of the spectrum and the low energy
output at the other end. The absorbance maximums of some common pesti-
cides are:
Simazine-220 nm, 2, 4-D-230 nm, IPC-234 nm, Propanil 248 nm,
Amiben 297 nm, DNBP-375 nm, and Triflurolin-376 nm.
Of these compounds, only DNBP and Triflurolin have absorbance maximums
within the wave length range received by the earth's surface.
At first glance, it would seem that the compounds with low absorbance
maximums would not be subject to photochemical degradation. However,
substances termed sensitizers are capable of absorbing energy from longer
wave lengths and transferring the energy to other compounds. Sensitizers
act similar to catalysts. They remain unchanged through the energy ab-
sorbtion and transfer process and, consequently, are available for further
energy transfers. A few of the compounds known to exhibit sensitizer
activity are riboflavin, zinc oxide, ferric salts, mercury vapor, and
eosine.
The. actual extent of pesticide photodecomposition in nature is un-
known, although PGP and paroquat have been shown to completely degrade
via photodecomposition. At present, we can only assume that some portion
of pesticide loss in the environment is due to photochemical decomposition.
Certainly, most pesticides applied to our environment eventually
reach the soil surface or water. Much of the pesticides applied to the
soil surface leaches into the soil. Once in the soil, organic pesticides
are subjected to degradation by biological processes as well as chemical
processes. Dr. Alexander of Cornell University has stated "all organic
compounds are biodegradable, but some are more biodegradable than others."
218 '
-------
Blodegradation is decomposition by living organisms. Although
pesticide biodegradation is commonly considered a phenomena involving
microorganisms, pesticides can also be degraded by plants and animals.
Plants are greatly hampered in their ability to clear pesticides
because of their lack of an adequate excretory system. Consequently,
absorbed pesticides tend to be metabolized to more water soluble forms
and stored in cell vacuoles. The ability of a plant to metabolize
herbicides can determine the plant's susceptibility since herbicide
metabolism can either activate or deactivate the chemical. The herbicide
2, 4-D is metabolized by some resistant plants to nontoxic 2, 4-Dichloro-
phenol. Degradation of 2, 4-D can be by step-wise decarboxylation of
the side-chain with 2, 4-Dichloroanisole as an intermediate or via
cleavage at the ester linkage. Conjugation with a plant constituent is
another potential herbicide detoxification mechanism. 2, 4-D is known
to undergo esterification with glucose to form the corresponding 3-D-
glucose ester. Of course, plants exhibit many other degradation pathways
which vary depending on the pesticide, plant species and conditions.
Unlike plants, animals do possess efficient systems for excretion
and metabolism. Consequently, most xenobiotic compounds are cleared
quite rapidly. However, this is not true for many chlorinated hydro-
carbons. DDT may be metabolized or stored. The primary excreted
metabolite of DDT in man is DDA and DDE is the primary stored metabolite.
Metabolism in other animals can follow different pathways and result in
different metabolites.
Biodegradation by microorganisms is probably the most important
pesticide loss pathway. Microbial degradation is the most preferred
degradation mechanism because organic toxicants can be reduced to their
elemental components and made available as energy sources for other life
forms. Microbial processes, however, are not infallible. Microorganisms
can activate a relatively innocuous compound to a highly toxic poison.
Also, the pesticide structure, environmental conditions, species of
microbes present, and the availability of the pesticide to the microbes
all contribute to the microbial degradation process.
For microbial degradation to occur, the pesticide must be available
to the organism. Many pesticides are readily absorbed to soil particles
to soil organic matter making them unavailable to microorganisms. How-
ever, given the right conditions, the same pesticide can undergo de-
sorption and eventual degradation.
Several features of the pesticide's structure contribute to its
biodegradability. Substituents that can retard microbial degradation
include chloro, sulfonate, nitro and amino groups. The position of the
substituent on the molecule can also affect the ability of microbes to
degrade it. For example, phenol with a chlorine atom on the meta
position tends to be resistant to biodegradation but chlorine on the para
position tends to be susceptible.
Distinguishing between degradation via microbial action versus
chemical action is a relatively simple process. If degradation is as
rapid in sterile soil as in non-sterile soil, the degradation mechanism
219
-------
is probably chemical. Also, the disappearance curve can be a clue to
the agent responsible for degradation. If microbes-are responsible,
there should be an initial lag in disappearance followed by a progress-
ively rapid disappearance or chemical breakdown. The initial lag is due
to the time required for the microorganism population to adapt to the
pesticide. As the population adapts, progressively more of the pesticide
will degrade within a given time.
Understanding the various potential environmental fates of pesticides
can have several practical applications. Pesticides could be designed
to be rapidly biodegraded or photochemically degraded or to be persistent
in soil yet relatively immobile. Knowing how pesticides degrade in
nature can also aid in the search for methods to dispose of our unwanted
or waste pesticides.
At least two such research or demonstration projects are currently
being conducted in EPA Region VIII. The U.S. Air Force Academy is
conducting research on the soil biodegradation of 2, 4-D and 2, 4, 5-T.
This research has shown both compounds to readily degrade under natural
conditions. The 2, 4-D degradation was both rapid and complete.
The Montana Department of Health and Environmental Sciences is
investigating various pesticide disposal methods in an attempt to find
environmentally sound and economically feasible methods of disposing
of approximately 100 tons of unwanted pesticides currently being stored
by the State. The two methods given serious consideration are chemical
detoxification and biodegradation in soil. The investigators plan to
chemically detoxify all organophosphorus and carbamate pesticides.
Various detoxifying reagents will be tested to determine their ability
to hydrolyze these compounds. Two compounds, DNBP and Avadex BW will
be biodegraded in soil. These two compounds will be injected just
below the soil surface in two separate tests. The degradation will be
monitored to determine the time required for total disappearance of the
compounds under Montana conditions.
220
-------
ACUTE PESTICIDE POISONINGS
John D. Tessarl
Colorado State University
ABSTRACT
The Colorado Epidemiologic Pesticide Center is being developed as a
nucleus for study of an increasing number of synthetic chemicals in the
water, soil and air which may pose hazards to human and animal health.
Attention is given to the role of chemical environmental pollutants as
they relate to human and animal health both from the standpoint of acute
toxicity and for the possible chronic effects.
In the area of suspected pesticide poisoning cases, the function of
the laboratory is to aid in the confirmation or rejection of pesticide
involvement. Laboratory capabilities include:
1. Plasma, brain and red cell cholinesterase.
2. Gas chromatographic analysis of blood and urine for parent
compounds or metabolites.
3. Gas chromatographic analysis of tissues and other biological
substrates for parent compounds or metabolites.
4. Analysis of blood, urine and certain other substrates for
heavy metals.
The Center's laboratory has analyzed over 150 samples involving
acute poisonings. These include the analytical services provided for
the Diagnostic Laboratory of the College of Veterinary Medicine, and the
Colorado Poison Contol Center.
221
-------
222
-------
PESTICIDE USAGE STUDY
John W. Kliewer
Medical University of South Carolina
ABSTRACT
The Epidemiologic Studies Program of the Human Effects Monitoring
Branch, TSD, EPA is currently conducting a study of pesticide usage in the
United States. The study is being coordinated by the South Carolina
Epidemiologic Studies Center and this report deals with the objectives
and current status of our Study.
There are four categories of usage which must be taken into account
in order to arrive at a portrayal of pesticide dispersal in the United
States. These categories are (1) agriculture, (2) industry, (3) government,
and (4) home, lawn and garden. This report is concerned with the first
three usage categories.
The objectives of the pesticide usage study are:
1. to provide data relative to the occurrence of poisonings
and other health effects
2. to determine usage patterns which may assist in the
identification of potential areas of concern
3. to develop data which may assist in the evaluation of
economic impact of discontinuance of specific pesticides
4. to provide baseline data so that secular trends of usage
(e.g. from chlorinated hydrocarbons to organophosphates)
may be identified by subsequent studies
At the present time, a pilot survey of six selected states has been
completed and at least preliminary contact has been made in about 35
states with a completion date for all 50 states set for October 31, 1975.
223
-------
Study methods have been tested and, based on problems encountered,
refinements have been made, Data from the study are presently accumu-
lating for tabulation.
224
-------
APPLICATOR CERTIFICATION
David J. Combs
In October, 1972 Congress amended the Federal Insecticide, Fungi-
cide and Rodenticide Act of 1947 (FIFRA). One of the major changes in
the amended FIFRA is the requirement that certain pesticide applicators
must be certified. Within the next 1-1*5 years approximately 2 million
private and commercial applicators will have to be certified by state
authorities if they wish to use restricted use pesticides.
The environmental concern addressed by the '72 FIFRA is the safe
and proper use of pesticides. Congress recognized that pesticide use
presents both risks and benefits to man's health and environment. As
the House Committee on Agriculture explained in its report, the "theme"
behind the amended FIFRA was "a search for a balance between those risks
and benefits". The need for the continued use of pesticides is obvious
to us all. However, the need for "more carefully controlled use of
pesticides" was equally obvious to Congress. The '47 FIFRA was basically
a regulatory Act based on labeling and could not accomplish the needed
control. Therefore, the '47 FIFRA was changed from a labeling Act to a
broad regulatory program.
We must all realize that there are certain risks involved in con-
tinued pesticide use. Pesticides, unlike many other pollutants, includ-*
ing air and water pollutants, are intentionally placed into our environ-
ment to achieve certain benefits. Pesticides have helped increase agri-
cultural production, provided us with a healthier environment and have
protected our property and natural resources from unwanted pests. Through
these and other ways, all of us have benefited tremendously from pesti-
cide use in the past thirty years.
All of us have noticed these great number of benefits. But in the
past few years we have also learned a great deal more about the many
risks involved in pesticide usage. We have begun to learn more and more
about their acute toxic effects on animal and plant life. We have dis-
covered much more about chronic side effects, and we know certain pesti-
cides can be carried far from the application site and may accumulate
in the food chain. The environment has been unknowingly and unnecessarily
exposed to toxic and persistent chemicals. Label regulation simply was
not providing us with the necessary control and flexibility to prevent
misuse and the resultant environmental damage.
Under the '47 FIFRA, the only options available to EPA for control-
ling misuse of a registered pesticide were cancellation and suspension.
Anyone could buy a registered pesticide, and it was not illegal to misuse
it. Suspension and cancellation are broad actions and are not always
equitable. All users of a certain pesticide might be denied its future
use because of careless or improper use by a few individuals.
225
-------
The amended FIFRA, by means of pesticide classification and appli-
cator certification, helped eliminate most of this inequity. Through
classification and certification, we can more readily ensure the contin-
ued use of certain highly toxic and persistent pesticides. Thus, some
pesticides that may have been cancelled or suspended under the '47 FIFRA
can and will continue to be available to private and commercial applica-
tors .
The amended FIFRA requires the Administrator of EPA to classify all
pesticide uses as either "restricted" - "general" - or both. Pesticides
will be classified by use - not by active ingredient. Pesticides class-
ified as "restricted" will primarily be available only to certified
applicators or those working under their direct supervision. "General
Use" pesticides will normally be available to the general public.
A "general use" pesticide is defined in the Act as one which will
not "generally cause unreasonable adverse effects on the environment,
including injury to the applicator" when used according to its labeling
direction or widespread and commonly recognized practices. A "restricted
use" pesticide is one which "may generally cause unreasonable adverse
effects on the environment, including injury to the applicator" without
additional regulatory restrictions beyond labeling.
The Act provides two criteria for determining whether or not a
pesticide should be "restricted."
1. A "determination that the acute dermal or inhalation toxicity
of the pesticide presents a hazard to the applicator or other
persons." (Section 3(d)(1)(c)(i)) and
2. "A determination that its (the pesticide) use without additional
regulatory restriction may cause unreasonable adverse effects
on the environment." (Section 3(d)(1) (c)(ii)). Based on these
two criteria, EPA is now in the process of classifying all pesticide uses.
The first criteria for classifying a pesticide is its potential
hazard to the applicator or persons working around him. If a pesticide
is highly toxic, then it must be handled with extreme care, and the
applicator may be required to use specially designed protective equip-
ment. Specialized application equipment and techniques may also be
needed to minimize the pesticide's dangers. To use such a pesticide
safely and properly, applicators must be aware of the toxicity dangers
and ways of preventing exposure to himself and others.
The second criteria for classifying pesticides is the pesticide's
possible adverse effects on the environment. An example of such a
pesticide might be one that has a low toxicity and does not pose any
immediate danger to the applicator, but may pose a threat to the environ-
ment because of its certain characteristics. Such characteristics may
be persistence, bio-accumulation, mobility, leachability, etc. A number
of these environmental effects can and have been linked to improper 'use,
misuse, over use, and plain carelessness.
226
-------
Injury and death are readily seen and understood effects of
pesticides. Estimates on the numbers of deaths and injuries related
to pesticide use vary, but pesticides can and do kill. Not so well
understood is the long-term effects of a number of pesticides. How
does repeated or prolonged exposure to a low toxicity pesticide effect
an applicator or the environment? These and other questions are not
fully answered, but we must try to minimize our exposure and the environ-
ment's exposure to pesticides.
Not so obvious are environmental effects which may be linked to
pesticide usage. These effects include destruction of bees and other
pollinating insects, fish, wildlife and non-target plant kills, residues
in food, contamination of water, air and soils, resistance to pesticides
and accumulation in the food chain. Recent research findings have
potentially linked some pesticides to cancer.
Since only certified applicators or those working under his direct
supervision may apply "restricted use" pesticides, classification and
applicator certification are directly related. Section 4 of the amended
FIFRA provides for applicator certification.
Section 4 requires the Administrator of EPA to promulgate standards
for applicator certification. EPA published final certification standards
on October 9, 1974. These standards outlined ten categories of commercial
applicators as well as a broad general category for private applicators.
The standards also outlined certain competency requirements that each
category of applicator had to meet in order to become certified.
Section 4 also stipulated that "if any state, at any time, desires
to certify applicators of pesticides, the Governor of such state shall
submit a state plan" to EPA for approval. EPA shall approve the state
plan if the plan meets all the requirements of the Act. On March 12,
1975, EPA published final regulations outlining state plan requirements.
Each state plan must:
1. Designate a state agency as the agency responsible for adminis-
tering the plan throughout the state.
2. Contain satisfactory assurances that such agency has or will
have the legal authority and qualified personnel necessary to
carry out the plan.
3. Give satisfactory assurances that the state will devote adequate
funding to carry out the plan.
4. Provide that the state will make required reports to the Admin-
istrator of EPA and
5. Contains satisfactory assurances that the state standards for
certification conform to and are at least equal to those promul-
gated by EPA.
Any state certification program approved by EPA must be maintained in
accordance with the approved state plan.
State certification plans are to be submitted to EPA for review by
October 21, 1975. EPA will approve all plans which meet the minimum
requirements. All applicators of "restricted use" pesticides must be
certified by October 1976 or before they apply "restricted use" pesti-
cides after this date.
227
-------
It was Congress' intent, as outlined in the amended FIFRA, that EPA
and the states cooperate in the development and maintenance of state
certification plans. The EPA has and will continue to provide the states
with technical and financial assistance through their regional and head-
quarter staffs in developing needed statutory legislation and regulations.
Federal movies have also been made available to each state lead agency,
and in cooperation with USDA they have made approximately $5 million
available to the state extension services for applicator training.
Personnel of the EPA Region VIII have provided assistance to Colo-
rado, Montana, North Dakota, South Dakota, Utah and Wyoming. Examples
of this effort are the development and passage of new pesticide legisla-
tion in North and South Dakota, development of comprehensive regulations
in Montana, South Dakota and Wyoming, and development of a Regional
Private Applicator Manual.
The majority of states, not only those in Region VIII, but all
states, are now working towards a common goal, the development and main-
tenance of acceptable certification plans. There has been a great deal
of effort by Federal, State and private individuals and organizations
exerted towards reaching this goal.
Despite these efforts and the need for a certification program, EPA
has and is continuing to receive a great deal of criticism. This criti-
cism comes from not only private organizations but from a few state
officials. The majority of this criticism deals with private applicator-
farmer certification.
Many individuals feel that the private applicator-farmer will be
forced over a severe academic and administrative hurdle before being
certified. This is not true. Many states have designed programs that
will certify farmers through state training courses and manuals. These
training courses would be held during the winter months. Other states
have designed programs to certify the farmer through a short written
questionnaire administered by regulated dealers. An interim and emerg-
ency certification procedure has also been developed to ensure that no
farmer will be denied access to necessary pesticides.
Many individuals and farm groups believe that farmers have been
applying pesticides safely for years and do not need any governmental
program, either state or federal, telling them what they already know.
On the other hand, many of these same individuals insult the farmers
intelligence by demanding that the private applciator certification
program not tax the capabilities of the farmer. The EPA is by no means
implying that farmers are incompetent and need close scrutiny by regula-
tory agencies. On the contrary, we have the highest respect for the
American farmer. For without his ingenuity and productivity we would
not be the best fed country on Earth. The point is not that farmers
are incapable, but that we have learned a great deal about the bad side
of pesticides in the past few years. With this increased knowledge has
come new methods of application and use and the substitution of more
toxic substances for ones which were more persistent. An example of
228
-------
this substitution is Parathion for DDT. Many techniques, practices and uses
which were acceptable in the past are no longer acceptable. A well designed
certification program will help ensure that private, as well as commercial
applicators, will be kept up-to-date with modern techniques and uses.
Certification should help minimize acute hazards to applicators and
those around him, as well as minimize adverse effects on the environment.
Certification should make pesticide applicators and handlers more competent,
knowledgeable, responsible and aware of the need for the safe and proper
use of pesticides. If the certification program is to succeed, it must be
a total effort toward the education of applicators in all aspects of
pesticide handling and use.
An emphasis should be placed on applicator training. EPA has and is
continuing to develop a variety of training aids and materials. We are
also cooperating with the USDA Extension Service to provide funding to
each state for this training.
The certification process is more, much more, than an enforcement
program. It is an educational mechanism designed to help ensure the
safe and proper use of pesticides while trying to balance their risks
and benefits. It also provides a method of ensuring that needed pesticides
can and will remain available to the American farmer.
Hopefully all concerned parties will work together to develop and
maintain comprehensive certification programs. With a combined effort
we can all reach a common goal - the safe and proper use of pesticides.
In reaching this goal we will help ensure the continued use of pesticides
and enhance the environment.
229
-------
V>230
-------
THE CERTIFICATION OF PESTICIDE APPLICATORS
AND OPPORTUNITY FOR TRAINING
Gerald T. Weekman
North Carolina State University
ABSTRACT
The 92nd Congress, after careful consideration, selected a sophis-
ticated mechanism combining applicator certification at the state level
and restrictive federal labeling to solve pesticide problems.
In those states where applicator certification programs are being
implemented or are in an advanced stage of planning, training programs are
seen as a most essential element to satisfy the intent of Congress.
Training is seen not only as an essential step in achieving certification
but as an unparalleled opportunity to provide to pesticide applicators a
basic pesticide use foundation upon which to build pest management pro-
grams of the future.
Critical in these training-certification programs is the content of
the training offered and the success we must have in achieving transfer of
the content of the program to the applicator audience. We cannot afford
to miss this opportunity to make existing correct use technology available
to the pesticide users, nor can we afford not to follow through and assure
ourselves that the information transfer has been accomplished.
231
-------
232
-------
MONITORING OF SELECTED ECOLOGICAL COMPONENTS
. • i--'' ' .
OF THE ENVIRONMENT IN FOUR ALABAMA COUNTIES {1972-4974)
John Elliott
Auburn University
INTRODUCTION
A three year field study to determine some of the ecological impacts
of a typical commercial cotton insect control program on selected compo-
nents of the environment was conducted in accord with the Alabama Cotton
Pest Management Program from 1972 through 1974 in four Alabama counties.
The objectives of the study were (1) to determine if a buildup of
insecticide residue occurred in selected components of the environment
and (2) to identify potential insecticide residue problem areas in the
environment related to cotton insect control practices. This was ac-
complished by observing changes in the number of samples containing
residue and levels of residue occurring in soil, water, forage and wild-
life within the 4 county area for 3 years.
Guidelines for the project were developed by an advisory committee
comprised of Auburn University and Alabama State Agency representatives.
Sample sites were selected and valuable assistance given by County
Extension staff in the four counties, Pickens, Tuscaloosa, Autauga and
Elmore.
Samples were collected from five cotton fields and four farm ponds
located adjacent to or in the vicinity of cotton fields in each of the
four counties.
Samples were also collected from 3 cotton farms outside the 4 county
area and from 2 non farm sites as check areas for comparison of insecti-
cide residue levels in soils.
Environmental components selected for the study were: soil, forage,
pond water, fish, rats, mocking birds, quail and rabbits. The particular
environmental components were selected in order to acquire native species
of wildlife and other components which are readily available within the
sampling areas. Soil is subjected to insecticide application throughout
the insect control season, therefore, residue in soil indicates trends
of build up or decline. Forage from borders of cotton fields is sub-
jected to direct spray or drift of insecticides. Forage serves as food
for wildlife and livestock and is an indicator of residue levels in the
vicinity of cotton fields. Fish are highly sensitive to certain in-
secticides. It is of interest to know effects of cotton insecticides on
water, sediment and fish. The food supply for quail, mocking birds,
•^Published by the Alabama Cooperative Extension Service, Auburn University,
in cooperation with the U.S. Department of Agriculture. An Equal
Opportunity Employer.
233
-------
rats and rabbits is subjected to direct spray and drift of cotton
insecticides. Therefore, the various biological samples were selected
to determine trends in residue levels...
Samples were taken from each selected area as follows:
1. Prior to the time insecticides were applied on each farm -
June 15 through July 10.
2. At the end of the cotton insect control season - September 1
through October 15.
3. November 1 through December 30.
The sample periods were designated in order to collect samples before
pesticides were applied in early summer, again at the end of the insect
control season when residues were expected to be at the highest level and
the third samples were collected after insecticide degradation had begun.
770 samples of the various environmental components were collected
during the 3 year period. A majority of the samples were collected by
the writer with assistance from USDA, APHIS, Plant Protection and Quaran-
tine Division, Cotton Scout supervisors and County Extension Staff.
Samples were collected according to established procedure for the various
types of environmental components. A brief description of the sampling
procedure is given in the discussion for each type sample collected. All
samples were analyzed for insecticide residues, by the Alabama Pesticide
Residue Laboratory, utilizing "The FDA Analytical Manual" as the guide
for analytical procedures.
Five year records of pesticide use were taken from farms within the
four county area for correlation with monitoring results obtained from
the study. A general summary of insecticide use is as follows. A
majority of the farmers reported that 14 to 16 application of insecti-
cides were applied annually. From 1970 through 1972 the major insecti-
cides were (4.2.1) toxaphene, DDT and methyl parathion. Following the
ban on DDT in 1972 the use of azodrin, galecron, guthion, endrin, EPN,
ethyl and methyl parathion increased. From 1972 through 1974 the major
insecticides used were combinations of toxaphene, methyl and ethyl para-
thion, endrin - methyl parathion, guthion and azodrin. Approximately
75 percent of the insecticides were applied aerially.
RESULTS AND DISCUSSION
The selected environmental components contained various residues of
pesticides applied within the area. Interpretation of results for each
type is as follows: i
Soil Summary
Soil samples were taken from the designated sample sites at each of
three sample periods over the three years (1972-1974), Samples were taken
from 16 farms in 1972 and from 20 farms in 1973 and 1974. Soil cores were
234
-------
collected in a 3 gallon galvanized pail, air dried at the laboratory
and analyzed for residue content.
DDT in Soil (From Tables 1-3)
A definite decline of DDT and metabolites in soil occurred during
the three-year period (1972 through 1974). The average residue level
declined from .581 parts per million at the end of 1972 to .010 ppm at
the end of 1974. The decline was more apparent in the number of samples
containing DDT. In 1972, fourteen of sixteen samples contained DDT.
In 1974 only four of eighteen samples contained DDT. The decline was
the apparent result of the ban on the use of DDT in 1972. If this
trend continues, DDT should hardly be detectable by the end of 1975 in
soil. The highest level of DDT in soil in a single sample in 1972 was
1.82 ppm.
Toxaphene in Soil (From Tables 1-3)
Toxaphene was detected in approximately 90 percent of the samples in
all sample periods throughout the three-year period. The highest levels
of toxaphene were found at the end of the pesticide application season
each year; a majority of the samples contained less than 8 ppm. Toxaphene
residues degraded to less than one ppm from the third sample period each
year to the first sample period in June of the following year. Based
on the results of the study, there is no buildup of toxaphene in soil in
areas of heavy use.
Endrin in Soil (From Tables 1-3)
The number of samples containing endrin increased from 5 of 16 samples
in 1972 to 14 of 18 samples in 1974 as a result of increased use of the
material in cotton insect control. A slight increase in the residue
level was also noted. Endrin degraded to very low levels from the third
sample period to the first sample period of the next year. Based on this
study, there is no indication of endrin residue buildup in soils.
Methyl Parathion in Soil (From Tables 1-3)
The number of samples containing detectable levels of methyl parathion
increased from 3 of 16 samples in 1972 to 14 of 18 samples in 1974. The
residue levels were very low and degraded to non-detectable levels before
June of the following year. Methyl parathion was detected in soil for
the first time in the third sample period of 1974 at a very low level in
14 of 18 samples. Methyl parathion was one of the major pesticides used,
but rapid degradation apparently eliminated a residue buildup in soil.
Dieldrin in Soil (From Tables 1-3)
Very low levels of dieldrin ranging from .007 ppm to ,040 ppm were
found in about 50 percent of the samples. The dieldrin residue is
235
-------
INSECTICIDE RESIDUES IN SOIL 1972
MEM AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
§/
TOX.
ENDRIN
H. EPOX.
y
MEAN
.0726
.398
.002
.005
2/
RANGE
0 - .223
0 - 1.77
0 - .02
0 - .004
NUMBER 3/
SAMPLES
15
15
15
. 15
NUMBER 4/
RESIDUE
13
13
3
3
2ND SAMPLE PERIOD
DDT
TOX.
END.
§/
M.P.
DIELDRIN
.499
7.7
.008
.244
.0015
.03 - 1.82
0 - 50.2
0 - .008
0 - 2.01
0 - .014
16
16
16
16
16
14
12
' 3
3
4
3RD SAMPLE PERIOD i
DDT
TOX.
END.
DIELDRIN
.5815
1.64
.006
.001
0 - 1.65
0 - 6.9
0 - .089
0 - .007
16
16
. 16
16
14
14
5
8
KEY FOR ALL TABLES
i/ Mean - The average residue level expressed in parts per million.
2/ Range - High and low levels expressed in parts per million.
3/ Number of samples analyzed in each sample period.
4/ Number of samples containing residue.
5/ DDT includes metabolites DDE, DDD.
6/ TOX. - Toxaphene
7/ H. EPOX. - Heptachlor Epoxide
8/ M.P-. f Methyl Barathion plus Parathion
-------
TABLE #2
INSECTICIDE RESIDUES IN SOIL 1973
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
DIELDRIN
MEAN
.1077
.U07
.0023
.0022
RANGE
0 - .ifl8
0 - l.UO
o - .029
0 - .023
NUMBER
SAMPLES
20
20
20
20
NUMBER
RESIDUE
18
18
5
8
2ND SAMPLE PERIOD
DDT
TOX.
M.P.
.0218
1.1*9
.076
0 - .111.
0 - 6.8
0 - .1*7
20
20
20
5
15
6
3RD SAMPLE PERIOD
DDT
TOX.
END.
.127
1.22
.(&?
0 - .1*26
0 - 5.31
0 - .73
20
20
20
13
19
11
237
-------
TABLE #3
INSECTICIDE RESIDUES IN SOIL 197^
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
END.
DIELDRIN
MEAN
.028
1.^3
.0057
.004
RANGE
0 - .330
.05 - 7.5
0 - .029
0 - .040
NUMBER
SAMPLES
20
20
20
20
NUMBER
RESIDUE
k
20
10
9
2ND SAMPLE PERIOD
DDT
TOX.
DIELDRIN
.0165
1.52
.001*1
o - .236
0 - 3.3
0 - .037
16
16
16
2
13
6
3RD SAMPLE PERIOD
DDT
TOX.
END.
M.P.
DIELDRIN
.010
2.55
.Oik
.025
.001
0 - .123
0 - 8.88
0 - .084
0 - .076
0 - .016
18
18
18
18
18
h
18
•lU
lU
1
238
-------
probably from soil insect control of past years. Dates of application
were not obtained.
Check Area vs. Management Area Soils (From Table 4)
A comparison of residue levels in soils from the four county area
with soils outside the area was made to determine if a detectable trend
in the pesticide load existed between the areas.
Samples from three cotton farms in Lee County and a non-farm area
consisting of two State Parks and a residential area were taken in June
of 1973. At that time the 4 county area contained slightly higher
levels of residue than the check area and the non-farm area. Samples
were taken again in January of 1975 from the same areas for comparison.
At that time the check area contained slightly higher levels of residue
than the 4 county area. The non-farm area was considerably lower in
residue than the 4 county area and the check area.
Forage Summary
Forage samples were collected from the selected sites on 16 farms
at each sampling period. Samples were collected from borders or areas
adjoining cotton fields. Samples consisted of pasture grass, hay crops
and grass. Most were native grasses, Johnson grass, coastal bermuda,
crab grass and Fescue. A sample consisted of 1 to 3 pounds of grass
packed in a 12"xl8" plastic bag. All samples were taken within 50 feet
of cotton and were subjected to direct spray or drift from cotton
insect control. The objective was to determine the level of residues
in forage crops grazed by livestock or wildlife or cut for hay and silage
from areas near cotton fields.
DDT in Forage (From Tables 5-7)
DDT metabolites were found in a majority of samples ranging up to
55 ppm in 1972 and in the first sample period of 1973. Since that time
a rapid decline occurred. Some low level DDT residues occurred in the
spring forage sampling period of 1974. The probable source was rain
splashing from soil. Based on results of this study, DDT residue in
forage has been eliminated other than low levels which may occur in
early summer from environmental sources as rain splashing from soil.
Toxaphene in Forage (From Tables 5-7)
Toxaphene residue was found at varying levels ranging up to 1600 ppm
at the end of each pesticide application season. Toxaphene degraded to
less than 3 ppm from the third sampling period to the first sample period
of the following year. There appears to be no long-term buildup in
forage.
239
-------
TABLE
COTTON PEST MGT. AREA VS CHECK PLOTS
A COMPARISON OF RESIDUAL LEVELS IN SOIL
1ST SAMPLE PERIOD - JUNE 1973
j
INSECTICIDE
DDT
TOXAPHENE
ENDRIN
M. PARATHION
DIELDRIN
H. EPOXIDE
C. MGT. U
AREA
.1077
.1*07
.002
0
.002
0
CHECK &
AREA
.031
.068
0
0
0
0
NON-P'ARM "&
AREA
.01
0
0
0
0
.005
2ND SAMPLE PERIOD - JAN. 1975
DDT
TOXAPHENE
ENDRIN
M. PARATHION
DIELDRIN
H. EPOXIDE
.028 k-J
2.1*3
.013
.017
0
0
.o*a
3.05
.Ollf
.087
.001
0
.ooif
0
0
.(M
0
0
I/ Average levels from all farms in mgt. area
2/ 3 cotton farms - Lee County
3/ 2 Ala. State Parks and a residential area
k/ If farms from mgt. area
240
-------
Endrin in Forage (From Tables 5-7)
The number of forage samples and the residue level of endrin
increased from 1972 through 1974. A trend was not established since the
average level was lower in 1974 than in 1973. . The highest level detected
in a single sample was 10.37 ppm. Endrin appeared to degrade to very low
levels less than .1 ppm from one year to the next. Monitoring of endrin
levels in forage should be continued since a slight increase is indi-
cated in the study.
Methyl Parathion in Forage (From Tables 5-7)
Methyl parathion was detected in a majority of the forage samples at
the end of the pesticide application season in each of the three years.
Most samples contained less than 5 ppm. A few samples ranged as high
as 28 ppm. Methyl parathion degrades rapidly and in most cases had de-
graded to low levels by the third sample period. The chemical was not
detectable in June of the following year. No residue buildup is ex-
pected in forage.
Dieldrin in Forage (From Tables 5-7)
Dieldrin was found in about 50 percent of the samples at the first
sample period each year, A possible source was from fire ant control or
soil insect control in past years. Farmers reported none used in recent
years. Most samples contained less than .1 ppm. The highest level found
in a single sample was 1.17 ppm. The average level appeared to be
declining.
Forage from Gibson Pasture (From Table 8)
The Gibson pasture is in the Forest community in Pickens County.
Samples of forage from the pasture adjoining a cotton field were taken
within 50 to 75 feet of the cotton field at each of the sampling periods
during the three-year study. A summary of the results is presented in
Table 8. In 1972 and 1973 DDT levels ranged up to 43.6 ppm at the peak
application season and were eliminated in 1974. Toxaphene was found in
levels up to 40 ppm at peak application times in all three years. Toxa-
phene degraded to low levels each year. It appears that cattle should
be kept out of grazing areas adjoining cotton fields for at least two
months after pesticide application is completed or until residues decline.
Other insecticides did not appear to pose a problem although it is
assumed that rapidly degrading chemicals were present for short periods
of time after application.
Forage from Dean Hay Field (From Table 9)
The Dean hay field is located in the Deatsville community in Elmore
County. Samples were taken from the hay field adjoining a cotton field
to determine the levels of residue occurring in hay. A profile of the
results is shown in Table 9. During the peak pesticide application
season, toxaphene residue was detected at levels up to 725 ppm.
241
-------
TABLE
INSECTICIDE RESIDUES IN FORAGE 1972
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD .
INSECTICIDE
DDT
TOX.
DIELDRIN
H. EPOX.
MEAN
.531
3.M
.051
.05
RANGE
.01 - 5.72
0 - 37.^
o - .187
.86
NUMBER
SAMPLES
16
16
16
16
NUMBER1
RESIDUE
16
13 ".
9
1
2ND SAMPLE PERIOD
DDT
TOX.
M. P.
15.8?
11*9.28
3.6?
0 - 55.1
.08 - 725.9
.053 - 28.1
16
16
16
7
16
15
3RD 'SAMPLE PERIOD
DDT
TOX.
DIELDRIN
ENDRIN
M. P.
3.17
18. 3*4-
.071
.003
-.035
.07 - 15.66
.8 - 71. ^
.071
o - .025
o - .167
16
16
16
16
16
13
13
1
2
7
242,
-------
TABLE #6
INSECTICIDE RESIDUES IN FORAGE 1973
MEAN 'AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
END.
DIELDRIN
MEAN.
. 1.076
2.94
.008
.020
RANGE
.01 - 8.5U
.35- 13.66
0 - .017
0 - .08
NUMBER
SAMPLES
15
15
15
15
NUMBER
RESIDUE
14
11
2
9
2ND SAMPLE PERIOD
DDT
TOX.
END.
M. 9.
0
358.15
1.10
5.77
0
1.9-1636.
0 - 5.1*2
o - 26.9
16
16
16
16
0
16
7
. 15
3RD SAMPLE PERIOD
DDT
TOX.
END.
M. P.
DIELDRIN
0
195.23
1.97
.966
.033
.01
.9-102^.
0 - 10.
o - 5.87
0 - .27
16
16
16
16
16
1
15
9
6
3
243
-------
TABLE #7
INSECTICIDE RESIDUES IN FORAGE 1974
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
END.
DIELDRIN
MEAN. .
.370
1.34
.072
.002
RANGE
0 - 3.44
0 - 4.23
0 - 1.01
0 - .022
NUMBER
SAMPLES
16
16
16
16
NUMBER
RESIDUE
13
13
5
2
2ND SAMPLE PERIOD
DDT
TOX.
END.
DIELDRIN
M.P.
0
53.46
.360
.134
1.04
0
.69-150.0
.01 - 1.91
0 - 1.17
.01 - 4.61
16
16
16
16
16
0
16
14
5
12
3RD SAMPLE PERIOD
DDT
TOX.
END
DIELDRIN
M.P.
DEF.
0
33.65
.384
.0049
.227
.197
0
.24-101.5
.004- 2.72
0 - .056
.01 - 1.45
.01 - 1.37
16
16
16
16
16
16
0
15
13
2
15
7
244
-------
TABLE #8
GIBSON - FORAGE
INSECTICIDE
DDT
TOX.
END.
M. P.
1972
SAMPLE
PERIOD
1
.007
.20
0
0
2
5.09
7.42
0
.26
3
1.68
0
0
0
1973
SAMPLE
PERIOD
1
.01
1.43
0
0
2
43.6
M
0
T
3
17.2
0
.184
0
1974
SAMPLE
PERIOD
1
.93
1.37
.05
0
2
0
4o.
0
4.
3
0
17.4
0
1.45
TABLE #9
BEAN - FORAGE
INSECTICIDE
DDT
i
TOX.
END.
M. P.
1972
SAMPLE
PERIOD
1
•°?
.60
0
0
2
0
725.
0
18.12
3
0
51.7
0
0
1973
SAMPLE
PERIOD
1
.039
0
0
0
2
0
208.
0
4.16
3
0
3.58
0
0
1974
SAMPLE
PERIOD
1
0
.58
0
0
2
0
3.27
.012
0
3
0
L3.9
.149
T
245
-------
Toxaphene residue declined to low levels from one year to the next.
Forage samples with low levels of residue taken in June had not been
subjected to pesticide drift. Other insecticides used on nearby cotton
were detected occasionally. Hay crops located in the vicinity of
cotton fields should be monitored for pesticide residues.
Forage Samples Adjacent To and 100 Yards from Cotton (From Table 10)
Two samples were taken on the Wodsworth Farm in the Autaugaville
Community in Autuaga County. Forage samples were taken in a pasture
adjacent to and 100 yards from cotton at the same time to study effects
of distance on residue levels. The sample taken 100 yards from cotton
contained approximately 1/4 as much residue as the sample taken adjacent
to the cotton field. Many variables influence residue levels, however
it appears that the high levels are usually concentrated adjacent to
cotton fields.
Green vs. Dry Forage Residue Levels (From Table 11)
Forage samples were taken from the Walker Field in the Fosters
Community in Tuscaloosa County. Green oats were growing in a forage
sample area at the third sample period in 1974. A sample of the old
dry grass and one of the new green material was taken at the same time
to determine if a difference in residue levels occurred. The green
sample contained only 2.35 ppm of toxaphene compared to 30.9 ppm in
dry forage. The endrin level was .154 ppm in the dry sample and .006 ppm
in the green sample. The green sample was dried at the laboratory and
the analytical procedure was the same for both samples. The green
material probably did not receive an application of pesticide drift
whereas the old material had been subjected to pesticide drift.
Rat (Cricetidae Sigmodon) Summary
The Hispid cotton rat was selected for biological sampling as an
indicator of the pesticide load in the environment. An unsuccessful
attempt was made in 1972 to collect ground beetles for this purpose.
The Animal and Plant Health Inspection Service (APHIS) personnel
collected rat samples from the four county area before and after the
pesticide application season in 1973 and 1974. Rat samples were trapped
at each farm site as listed in Appendix B from perimeter of fields at
said sites. The agency was successful in collecting the required
number of rats at each sample period. The live Sherman type trap was
used. Rat samples were wrapped in aluminum foil, labeled and delivered
to the pesticide laboratory in frozen condition. A rat sample consisted
of five rats from each sample site.
DDT in Rats (From Tables 12-13)
All of the rat samples taken in 1973 contained DDT at an average
level of 4.12 ppm. At the first sample period in 1974 the average level
246
-------
TABLE #10
FORAGE - WADSWORTH FARM .
INSECTICIDE
TOXAPHENE
ENDRIN
M. PARATHION
SAMPLE LOCATION
ADJACENT TO COTTON
57.68 PPM
1.6k "
T
100 YARDS FROM COTTON
11.75 PPM
.452 "
,2»*9 "
TABLE #11
GREEN VS DRY FORAGE
WALKER FIELD - DEC. l$7k
INSECTICIDE
TOXAPHENE
M. PARATHION
/
ENDRIN
DEF.
DRY
30.9 PPM
T
,15k "
.10k "
GREEN
2.35 PPM
.066 "
.066 "
0
247
-------
was 5.6 ppm. DDT was not used on cotton in 1973 and 1974. Therefore,
it is assumed that the source of DDT was from an accumulation in the
food supply and a carry-over in body fat from previous years. At the
second sample period in 1974 the average DDT level declined sharply to
.89 ppm. Based on the result it appears that about one year is required
for a significant change in residue levels of a chemical such as DDT
to occur in biological samples. No attempt was made to determine the
age of the rats.
Toxaphene in Rats (From Tables 12-13)
Toxaphene was not detected in rats collected in June of 1973 at the
first sample period. At the second sample period in 1973, two of
eighteen samples contained toxaphene. In 1974 a significant increase
in the number of samples containing toxaphene occurred.
An increase in the number of applications of toxaphene combination
with methyl parathion is a possible cause of the increase in rats. A
detectable trend was established as toxaphene residue increased from
an average level of 3.66 ppra at the second sample period of 1973 to
an average level of 7.79 ppm at the second sample period of 1974,
probably as a result of more samples containing toxaphene.
Endurin in Rats (From Tables 12-13)
An increase in the number of samples and the level of endrin residue
occurred in rats from 1973 to 1974. This reflects increased use of the
material in the area. The highest level detected in a single sample
was 2 ppm in 1974. Although the residue levels were very low, there is
an indication of accumulation in biological samples as the use of the
material increases.
Dieldrin in Rats (From Tables 12-13)
The number of samples containing dieldrin and the level of residue
in rats increased from 1973 to 1974 which indicates an accumulation in
the food supply. Farmers report no aldrin or dieldrin has been used in
the area in recent years. In 1974, eleven of nineteen rat samples
contained dieldrin in levels ranging to 1.49 ppm in the second sample
period.
Heptachlor Epoxide in Rats (From Tables 12-13)
The number of samples and the level of heptachlor epoxide declined
from 1973 through 1974. This indicates a degradation of the material
in the food supply. Heptachlor probably was used within the rat feeding
area for the control of fire ants or other soil insects in previous years.
Quail (Colinus Virginianus) Summary
Quail samples were taken by shooting birds frequenting the perimeter
of sites in the four-county area listed in Appendix B. Quail lose some
248
-------
TABLE #12
INSECTICIDE RESIDUES IN RATS 1973
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
ENDRIN
H. EPOX
MEAN
4.12
.002
.481
RANGE
.01 - 15,45
0 - .008
.002 - 3.45
NUMBER
SAMPLES
12
1.2
12
NUMBER
RESIDUE
12
2
10
2ND SAMPLE PERIOD
DDT
TOX.
H. EPOX
DIELDRIN
3.83
3.66
.232
.08
.5 - 13.44
0 - 24.0
0 - 1.2
.15
18
18
18
18
18
2
9
1
249
-------
TABLE #13
INSECTICIDE RESIDUES IN RATS 1974
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
H. EPOX
DIELDRIN
MEAN
5.60
4.52
.083
.264
RANGE
0 - 51.6
0 - 21.2
0 - .50
0 - 1.80
SAMPLES
18
18
18
18
RESIDUE
14
11
4
4
2ND
DDT
TOX.
END.
H. EPOX
DIELDRIN
.894
7.79
.311
.023
.354
SAMPLE PERIOD
0 - 4.67
1.1 - 29.9
0 - 2.0
0 - .125
0 - 1.49
19
19
19
19
19
18
15
7
2
11
250
-------
predacious fears in the mating season and could be seen in many fields
in June. Samples were easy to collect at that time. In the fall quail
are in coveys and take cover making it much more difficult to collect
samples at that time. From observations during the three-year study,
it appeared that quail populations have not been affected by pesticides
in the area. Population studies would be useful regarding effects of
organophosphates or highly toxic materials on wildlife.
DDT in Quail (From Tables 14-16)
In 1972 quail samples contained up to 200 ppm of DDT on a fat
basis. In 1973 a marked decline in the level of DDT occurred and the
trend continued through 1974. The median level of DDT declined from
66.21 ppm in June of 1972 to 1.26 ppm at the third sample period in
1974. The level is well below the FDA tolerance for DDT in meats and
represents a significant decline.
Toxaphene in Quail (From Tables 14-16)
In 1972 one quail sample was taken at the end of the pesticide
application season containing 70 ppm of toxaphene. In 1973 toxaphene
was not found in quail. In 1974 it appears that the number of samples
containing toxaphene increased and the range remained fairly constant
in samples containing residue. Further studies of quail needs to be
done to determine if a trend for increased levels of toxaphene exist.
Endrin in Quail (From Tables 14-16)
Endrin was not detected in quail in 1972. In 1973 and 1974 endrin
residue occurred in some samples. The highest level detected in a single
sample was .72 ppm.
Heptachlor Epoxide in Quail (From Tables 14-16)
The number of samples containing heptachlor epoxide and the level
of residue in quail increased from 1972 through 1974. The highest level
of residue in a sample was 2.4 ppm. Heptachlor was not used on cotton
farms. A possible source is fire ant treatment within the feeding range
of quail. The increase probably merits the monitoring of quail to
determine if the trend continues.
Dieldrin in Quail (From Tables 14-16)
Low levels of dieldrin were found in some of the quail samples.
The highest level found was .79 ppm in one sample. This indicates that
aldrin or dieldrin was applied within the feeding range in past years^
Mirex in Quail (From Tables 14-16)
Mirex was also found in one sample in 1974 at 11.11 ppm. A feeding
area had probably been treated for fire ants.
251
-------
TABLE
INSECTICIDE RESIDUES IN QUAIL 1972
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
H. EPOX
DIELDRIN
MEAN
66.21
.31
.033
RANGE
.72 - 196.0
.93
.04 - .06
NUMBER
SAMPLES
3
3
3
NUMBER
RESIDUE
3
1
2
2ND SAMPLE PERIOD
DDT
TOX.
DIELDRIN
17.6
70.0
.56
17.6
70.0
.56
1
1
1
1
1
1
3RD SAMPLE PERIOD
DDT
H. EPOX
23.20
.095
1.6 - 44.7
.191
2
2
2
1
252
-------
TABLE #15
INSECTICIDE RESIDUES IN QUAIL 1973
. MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
ENDRIN
H. EPOX
DIELDRIN
MEAN
12.09
.01
.502
.058
RANGE
4.6 - 16.31
.04
.4 - .88
.06 - .17
NUMBER
SAMPLES
4
4
4
NUMBER
RESIDUE
4 ,
1
3
4 2
. 2ND SAMPLE PERIOD
DDT
ENDRIN
H. EPOX
5.73
.215
.79
2 - 8.4
.14 - .72
.28 - 2.4
4
4
4
4
2
4
253
-------
TABLE #16
INSECTICIDE RESIDUES IN QUAIL 1974
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
H. EPOX
DIELDRIN
MIREX
MEAN
10.54
8.28
.121
.663
.131
1.86
RANGE
3.9 - 39.5
2.1 - 31.25
.22 - .51
.14 - 1.3
.79
11.11
NUMBER
SAMPLES
6
6
6
6
6
6
NUMBER
RESIDUE
6
5
2
6
1
1
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
H. EPOX.
DIELDRIN
1.26
22.0
.3
.14
.165
.76 - 1.76
0- 44.0
.26 - .34
0 - .28
0 - .33
2
2
2
2
2
2
1
2
1
1
254
-------
Mockingbird (Passeres Mimidae) Summary
Mockingbirds are insect eaters and non-migratory and were selected
for study because of these particular characteristics. Mockingbirds
were collected from the edge of cotton fields by shooting from the
perimeter of said sites as listed in Appendix B. The birds were usually
sitting on fence rows and feeding in cotton fields when collected. A
sample consist of three birds. As a result of the feeding habits, mocking-
birds contained higher residue levels than other types of wildlife
samples. Mockingbirds appeared to be numerous and there was no problem
in collecting them at every sample period. Therefore, it is assumed that
cotton insecticides have not affected populations. Population studies
would be helpful.
DDT in Mockingbirds (From Tables 17-19)
DDT was found in all mockingbird samples in 1973 and 1974 in levels
up to 394 ppm. In 1974 a very noticeable decline occurred in the level.
The average level in all samples in the second sample period in 1972 was
101.8 ppm; and by the second sample period in 1974 the level declined :
to 13.2 ppm. The residue was probably an accumulation in body fat from
previous years.
Toxaphene in Mockingbirds (From Tables 17-19)
Toxaphene was found at high levels in mockingbirds in the second
sample period of 1972. In 1973 toxaphene was not found in birds. No
explanation is apparent for the 1973 result. In 1974 levels up to
117 ppm were found in the samples at both sample periods. Indications
are that a trend of high level accumulation of toxaphene occurred.
More sampling is needed in order to determine if a definite trend
occurred. There is some indication that high levels build up in mocking-
birds and decline rather rapidly when the toxaphene in the food supply
is removed.
Endrin in Mockingbirds (From Tables 17-19)
The number of samples containing endrin and the residue level
increased from 1972 through 1974. The highest level detected in a sample
was 2.52 ppm. Indications are that high levels of endrin do not occur
as with DDT or toxaphene. Approximately a 4 to 1 ratio of toxaphene
to endrin rate is applied and more applications of toxaphene are used
which may account for the difference in residue accumulation.
Heptachlor Epoxide in Mockingbirds (From Tables 17-19)
Heptachlor epoxide was found in mockingbirds at levels up to 28 ppm
in 1972 and 1973. A noticeable decline in the level occurred in 1974.
The average level declined from 8.82 in 1972 to an average level of
.636 ppm in 1974. The birds evidently feed on soil insects from areas
treated for fire ants or other soil insects since heptachlor is not
255
-------
TABLE #17
INSECTICIDE RESIDUES IN MOCKINGBIRDS ,1972
MEAN AND RANGE IN PARTS PER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
ENDRIN
H. EPOX
DIELDRIN
MEAN
41.16
.03
3.88
.61
RANGE
7 - 75.0
0 - .15
.6 - 14.95
.09 - 1.2
NUMBER
SAMPLES
M-
4
4
4
NUMBER
RESIDUE
4
1
2
4
2ND SAMPLE PERIOD
:DDT
TOX.
H. EPOX
DIELDRIN
101.88
20.0
8.82
.302
3.0 -27000
D02-100.0
.028-28.8
.005 -1.50
5
5
5
5
5
5
M-
3
256
-------
TABLE #18
INSECTICIDE RESIDUES IN MOCKINGBIRDS 1973
MEAN AND RANGE IN PARTS HER MILLION
1ST SAMPLE PERIOD
INSECTICIDE
DDT
ENDRIN
H. EPOX.
DIEIDRIN
MEAN RANGE
210.3
.2U
15.36
.522
35. - 39^.2
.18 - .78
3.^ - 23.98
.39 - .73
NUMBER
SAMPLES
U
U
h
k
NUMBER
RESIDUE
k
2
if
k
2ND SAMPLE PERIOD
DDT
H. EPOX.
DIELDRIN
6.27
l.lf
.53
1.6 - 11.2
.U2 - 2.1J-
1.6
3
3
3
3
2
1
257
-------
TABLE #19
INSECTICIDE RESIDUES IN MOCKINGBIRDS 1974
MEM AND RANGE IN PARTS PER MILLION.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
K. EPOX.
DIELDRIN
MEAN
1.51
83.8
.198
1.28
1.42
NUMBER NUMBER
RANGE SAMPLES RESIDUE
1.9 - 2.98
43. - 117.5
.132 - .6k
.36 - 3.09
.la - 6.19
5
5
5
5
5
3
5
3
5
3
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
H. EPOX.
DIELDRIN
13.21
36.75
.63
.636
.07
2.2 - 21.12
3^. - H3.
.01 - 2.52
.4i - 1.25
0 - .28
4
4
4
4
4
4
2
2
3
1
TABLE #20
PESTICIDE RESIDUES IN RABBITS
INSECTICIDE
DDT
TOX.
DIELDRIN
H. EPOX.
1972
MEAN LEVEL
SAMPLE PERIOD
1
1.17
0
0
0
2
NS
, 1973
MEAN LEVEL
SAMPLE PERIOD
1
1.72
0
0
0
2
.126
.68
0
.019
1974
MEAN LEVEL
SAMPLE PERIOD
1
1.79
29.5
.45
0
2
1.8
0
.039
0
258
-------
used on cotton. The decline in the level indicates no recent soil
treatment in the area.
Dieldrin in Mockingbirds (From Tables 17-19)
Dieldrin residue remained fairly constant in the number of mocking-
bird samples throughout the three years. One sample contained 6.19 ppm
in 1974 which indicates that a possible soil treatment occurred recently
within the project area. Cotton farmers report no aldrin or dieldrin
used in cotton fields. The average level declined from .302 ppm in
1972 to .07 ppm in 1974.
Rabbit (Leporidae Sylvilagus) Summary
Rabbit samples were collected from farms in the project area.
Samples were difficult to collect and valid treatments would be difficult
to establish based on the limited number of samples. From the samples
collected it appears that rabbits react similarly to other wildlife
sampled in the program. Indications are that rabbits accumulate residual
pesticides that are present in their food supply. No extremely high
levels of residue occurred. Rabbit samples contained about 2 ppm of
DDT throughout the sampling period and in 1974 there was some indication
of an increase in toxaphene residue.
Water from Farm Ponds Summary
Sixteen farm ponds as listed in Appendix B were selected near cotton
fields to determine the effects of cotton insecticides on water, pond
sediment and fish from the ponds. There are hundreds of farm ponds
ranging in size from 1 to 10 acres located in the vicinity of cotton
production in Alabama. When fish kills occur, legal problems occur.
Determination of the cause of fish kills are often very difficult. An
attempt was made to develop a profile of effects of pesticides on water
sediment and fish in areas of heavy pesticide use.
Some of the ponds were located adjacent to cotton fields planted
within 30 feet of ponds. Most of the ponds were within 100 to 150 yards
of cotton fields and subject to drift and runoff. Two ponds were fairly
well isolated from cotton production. Three ponds were fairly well
protected by vegetative cover and topographic features. Each sample
consists of three one gallon glass containers from water 1 to 3 feet
deep from each pond.
Fish are sensitive to certain pesticides in parts per billion;
therefore, residue levels were reported in parts per billion (PPB) in
water,
DDT in Farm Ponds (From Tables 21-23)
The average level of DDT in water declined from ,24 parts per billion
in 1972 to an average of .001 parts per billion in 1974. DDT levels
as high as 22 parts per billion were recorded in 1972, In 1974 DDT
was practically eliminated from farm ponds and a very marked decline
occurred in the number of samples containing DDT.
259
-------
Toxaphene in Farm Ponds (From Tables 21-23)
An increase in the number of samples containing toxaphene occurred
from 1972 through 1973 and 1974. The range of toxaphene residue appeared
to remain fairly stable in the samples containing residue. The highest
level recorded at any time in a single sample was 10.5 ppm. The highest
levels were recorded at the second sample period at the end of the
pesticide application season. Toxaphene declined to low levels in June
of each year. Results indicate that it does persist in water throughout
the year; however, there does not appear to be a serious buildup in water.
Endrin in Farm Ponds (From Tables 21-23)
A significant increase in the number of samples containing endrin oc-
curred from 1972 through 1974. In 1972 only one of the 15 samples con-
tained endrin. In 1974 the number increased to 15 of 16 samples. An
increase in the range and average level of endrin also occurred during
the three years. The highest level detected in a sample was 5.28 ppb.
Endrin appears to start degrading shortly after the insecticide appli-
cation season and occurred in a few samples at very low levels in June
of the following year. There is no. indication of a buildup from year to
year in fish ponds.
Methyl Parathion in Farm Ponds (From Tables 21-23)
Methyl parathion was found in a majority of the samples at the end
of each regular pesticide application season. The highest level found
at any time was 1.49 ppb. Methyl parathion breaks down rapidly and was
not detected in samples collected one to two months after the peak
spray season in 1973. In 1974 methyl parathion residue remained in
samples collected in December in 3 of 16 ponds at 0.83 ppm. There are
no indications of a buildup of methyl parathion in fish ponds.
Other Insecticides in Farm Ponds (From Tables 21-23)
Dieldrin and heptachlor epoxide were detected in a few of the samples
at very low levels throughout the three-year period. No history of the
use of dieldrin and heptachlor was available. There appears to be no
problem with the materials.
Fish from Farm Ponds
> Bream - Lepomis marcrochirus
Bass - Micropterus salmoides
Channel Catfish- Ictalurus punctatus
Fish were collected before and after cotton insect control each
year in fish baskets and by hook and line from fresh water ponds
located in the 4 county area as listed in appendix B. A fish sample
consists of one or more pounds of bream, bass or catfish. Fish kills
occurred in some of the ponds during the three-year period. Fish
disappeared from some of the ponds although fish kills were not
260
-------
TABLE
INSECTICIDE RESIDUES IN FARM PONDS 1972
MEAN AND RANGE EXPRESSED IN P.P.B.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
MEAN
.2^0
.5
RANGE
0 - 3.8
0 - 8.0
NUMBER NUMBER
SAMPLES RESIDUE
16
16
2
1 • .
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
M. P. .
1.53
.to
.01
.029
0 - 22.7
0 - l.lU
0 - .079
0 - .021
15
15
15
15
6
10
i
i*
3RD SAMPLE PERIOD
DDT
TOX.
EWDRIN
DIELDRIN
.13^
.972
. .00**
.006
0 - l.l*
0 - 10.5
0 - .028
o - .029
16
16
16
16
8
5
2
3
261
-------
TABLE #22
INSECTICIDE RESIDUES IN FARM PONDS 1973
MEAN .AND RANGE EXPRESSED IN P.P.B.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
H. EPOX.
DIELDRIN
MEAN
.llfl
.3^7
.007
.002
.001
NUMBER NUMBER
RANGE SAMPLES RESIDUE
0 - 1.77
0 - Z.k
0 - .Oh
0 - .Gik
0 - .012
16
16
16
16
16
9
7
2
2
2
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
M. P.
H. EPOX.
.69k
2.72
.101
.2^5
.038
o - 10.56
0 - 7.kk
o - 5.28
0 - 1.^9
o - .6
16
16
. 16
16
16
7
15
Ik
13
2
3RD SAMPLE PERIOD
DDT
TOX.
ENDRIN
M. P.
DIELDRIN
.017
1.78
.028
0
.001
o - .18
o - 6.6
0 - .OQk
0
0 - .01
16
16
16
16
•16
'k
10
7
0
2
262
-------
CABLE #23
INSECTICIDE RESIDUES IN FARM PONDS 1971*
MEAN AND RANGE IN P.P.B.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
MEAN
.003
.132
.0001
RANGE
0 - .020
0 - 1.20
0 - .001
NUMBER
SAMPLES
16
16
16
NUMBER
RESIDUE
2
h
l
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
M. P.
0
2.01
.053
.273
0
0 - 5. 6U
0 - .203
o - 1.19
16
16
16
16
0
15
15
k
3RD SAMPLE PERIOD
DDT
TOX.
ENDRIN
M. P.
H. EPOX.
DIELDRIN
.001
.606
.001
.083
0
.0018
0 - .01
0 - lt.2
0 - .012
o - .1*66
. Trace
0 - .Oik
16
16
16
16
16
16
2
3
2
10
1
3
263
-------
observed. Fishing remained good in some ponds. Distance from cotton
fields, vegetative borders and topographic features are very important
factors regarding fish production near cotton fields. Normal healthy
fish may be expected to contain residues of various residual pesticides
applied in the vicinity of ponds.
DDT in Fish (From Tables 24-26)
DDT residues were found in a majority of the samples throughout the
three-year study in levels ranging to 12 parts per million. A majority
contained less than 3 ppm. The average level of DDT in fish declined
from 1.43 parts per million in 1972 to .136 in 1974. The highest level
detected in 1974 was .54 parts per million.
Toxaphene in Fish (From Tables 24-26)
A majority of the samples contained toxaphene throughout the three
years. There was no indication of a significant change in the levels.
The highest level detected was 12 ppm. Most samples contained less
than 6 ppm.
Endrin in Fish (From Tables 24-26)
Endrin residue was found in about one-fourth of the samples at
various sampling periods. The highest level found was .1 ppm. There
is no indication of a buildup in numbers of samples or levels of endrin
in fish.
Dieldrin in Fish (From Tables 24-26)
Dieldrin residue was found in about one-fourth of the samples at
various times. One sample contained 1,24 ppm but a majority of samples
were below .03 ppm. There appears to be no problem of dieldrin residue
in fish.
Sediment From Farm Ponds Summary
Sediment samples from the bottom of farm ponds were taken at the
time water samples were collected to determine if residues were present
in detectable levels. Sediment samples consist of one pint of mud from
pond bottoms.
DDT in Farm Pond Sediment (From Tables 27-29)
DDT residue was found in about one-half of the samples throughout
the three-year study at low levels. In 1972 and 1973 the highest level
detected was 1.8 ppm. The levels appeared to be declining slightly in
1974.
264
-------
TABLE #24
INSECTICIDE RESIDUES IN PISH 1972
MEAN AND RANGE IN P.P.M.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
ENDRIN
DIELDRIN
MEAN
1.1*3
.834
.056
NUMBER NUMBER.
RANGE SAMPLES RESIDUES
.009- 6.4
o - 2.78
.0001
0 - .42
8
8
8
8
8
5
1
6
2ND SAMPLE PERIOD :
DDT
TOX.
ENDRIN
DIELDRIN
.37
2.58
.0033
.0009
0 - 1.2
0 - 12.0
0 - .012
0 - .002
6
6
6
6
5
3 .
4
4
DDT
TOX.
3RD SAMPLE PERIOD
.042
.142
.042
.142
.1
l
1
1
265
-------
TABLE #25
INSECTICIDE RESIDUES IN FISH 1973
MEM AND RANGE IN P. P.M.
1ST SAMPLE PERIOD
INSECTICIDE
DDT
TOX.
DIELDRIN
NUMBER NUMBER
MEAN RANGE SAMPLES RESIDUE
2.81
1.56
.oo46
.0^3 - 12.0
0-6.0
0 - .03
10
10
10
10
k
5
2ND. SAMPLE PERIOD
DDT
TOX.
ENDRIN
DIELDRIN
.273
1.67
.018
.002
.03 - l.UU
o - 6.0
0 - .10
0 - .008
7
7
7
7
6
5
2
3
266
-------
TABLE #26
INSECTICIDE RESIDUES IN FISH 197^
MEAN AND RANGE IN PPM
1ST SAMPLE PERIOD
NUMBER NUMBER
INSECTICIDE MEAN RANGE SAMPLES • RESIDUE
DDT
TOX.
ENDRIN
H. EPOX.
DIELDRIN
.137
1.57
.0027
.003
.126
.01 - .5U
0 - 6.0
o - .003
0 - .013
0 - l.2l*
10
10
10
10
10
9
9
k
3
h
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
H. EPOX.
DIELDRIN
.1367
.765
.035
.003
.006
.01 - .28
0 - 1.53
o - .071
0 - .002
o - .01 ;
h
k
h .
h
h
k
1
1
1.
1
267
-------
Toxaphene in Farm Pond Sediment (From Tables 27-29)
An increase in the number of samples containing toxaphene occurred
from 1972 through 1974. There was no significant change in the levels.
The highest level detected was .68 ppm.
Endrin in Farm Pond Sediment (From Tables 25-27)
An increase in the number of samples containing endrin occurred
reflecting an increased use of the chemical. The high range level of
endrin remained at about .01 ppm throughout the three years.
Methyl Parathion in Sediment (From Tables 27-29)
Methyl parathion was not detected until the third sample period of
1974 at which time 7 of 16 samples contained trace levels.
Pesticide Profile of Selected Farm Ponds 1972-1974
Water sediment and fish were collected from the 16 ponds in the
study area three times each year. A profile of selected ponds is a good
indicator of the condition of the pond. Information and residue summaries
for selected ponds are as follows.
Gibson Pond - Residue Profile (From Table 30)
The Gibson pond is in the Forest Community in Pickens County. The
pond is approximately six acres in size, and located within 50 feet of
a cotton field. The pond is located in an area that is subject to
drift and runoff from cotton insect control. The water level was low
in drought periods; therefore, the pond may have had low oxygen levels
at times. The pond was stocked with catfish and an adequate sample of
fish was collected in June of 1972. At various sample periods, water
from the pond contained toxaphene residue up to 10.56 parts per billion,
endrin at 5.28 ppb, DDT at 3.8 ppb and methyl parathion at 1.7 ppb.
A fish kill was not observed; however, samples could not be collected
after June of 1972. The owner stated that the pond is not in a desirable
location and plans to construct a fish pond away from his cotton fields.
Kirkpatrick Pond - Residue Profile (From Table 31)
The Kirkpatrick pond is in the Autaugaville Community in Autauga
County. The pond is located within 30 feet of a cotton field and is
completely encircled by the field. The pond is supplied by an artesian
well with an adequate supply of water, The pond is subject to drift
and runoff from the cotton field. Fish samples from the pond were
adequate in 1972 and 1973. A poor quality sample was collected at the
first sample period in 1974, but was unable to collect a sample in the
fall of 1974. Indications are that the fish population was greatly reduced.
Toxaphene residue ranged as high as 8,16 ppb and endrin as high as
.21 ppb in water samples from the pond.
268
-------
TABLE #2?
INSECTICIDE RESIDUE IN FARM POND SEDIMENT 1972
MEAN AND RANGE IN PPM
1ST SAMPLE PERIOD
NUMBER NUMBER
INSECTICIDE MEAN RANGE SAMPLES RESIDUE
DDT
TOX.
ENDRIN
DIELDRIN
.016
.0^5
o - .166
o - . .36
.001
.001
16
16
16
16
8
1
1
l
2ND SAMPLE PERIOD
DDT
TOX.
H. EPOX.
DIELDRIN
.1235
.001
0 - 1.75
0 - .01.
.005
.001
16
16
. 16
16
8
2
1
1
3RD SAMPLE PERIOD
DDT
TOX.
ENDRIN
.012
.051
.0009
0 - .OU
o - .ite
0 - .01
16
16
16
8
5
2
269
-------
TABLE #28
INSECTICIDE RESIDUE .IN FARM POND SEDIMENT 1973
.MEAN AND RANGE IN PPM
1ST SAMPLE PERIOD
NUMBER NUMBER
INSECTICIDE MEAN RANGE SAMPLES RESIDUE
DDT
TOX.
.115
.009
o - 1.8
0 - .037
16
16
6
3
2ND SAMPLE PERIOD
DDT
TOX.
.00k
.Ok
0 - .018
0 - .68^
16
16
6
2
3RD SAMPLE PERIOD
DDT
TOX.
ENDRIN
.0077
.0006
.0006
o - .oia
.01
.01
16
16
16
8
1 .
1
270
-------
TABLE
INSECTICIDE RESIDUE IN FARM POND SEDIMENT 197^
MEAN AND RANGE IN PPM
1ST SAMPLE PERIOD
NUMBER NUMBER
INSECTICIDE MEAN RANGE SAMPLES RESIDUE
DDT
TOX.
DIELDRIN
.073
.0013
0 - .06
.22
.018
16
16
16
6
1
1
2ND SAMPLE PERIOD
DDT
TOX.
ENDRIN
.0^5
•• .076
" ..001
0 - .57
0 - .60
0 - .01
16
3.6
16
10
6
2
3RD SAMPLE PERIOD
DDT
TOX.
ENDRIN
i
M. P.
.005
.027
.0022
.005
0 - .079
0 - .1^9
0 - .01
0 - .01
•16
16
16
16
h
6
6
7
271
-------
TABLE #30
j INSECTICIDE
DDT
TOX.
EMRIN
M. P.
GIBSON POND 1972
WATER (PPB)
SAMPLE PERIOD
1
3.8
8.0
2
.21*0
.92
0
.092
3
.teU
2.10
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
.020
0
0
0
2
.010
0
0
0
3
.012
0
0
0
GIBSON POND 1973
INSECTICIDE
DDT
TOX.
ENDRIN'
M. P.
WATER (PPB)
SAMPLE PERIOD
1
1.77
1.18
0
0
2
0
10.56
5.28
.53 .
3
0
5.60
.(ft
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
0
0
0
0
2
0
0
0
0
3
0
0 ,
0
0
GIBSON POND 197^
rTSECTICIDE
DDT
TOX.
ENDRIN
M. P.
WATER (PPB)
SAMPLE PERIOD
1
0
1.20
.001
0
2
0
M
0
1.7
3
0
0
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
..001
0
0
0
2
.001
.038
0
0
3
.. . 006 .
0
; 0
o'
279
-------
TABLE #31
KIRKPATRICK POND 1972
INSECTICIDE
DDT
TOX.
END.
M. P.
WATER (PPB)
SAMPL
1
0
o
0
0
E PERIOD
2
0
.2k
0
0
3
.07
.28
0
0
SEDIMENT (PPM) :
SAMP
1
.023
0
0
0
jE PERIOD
2
0
0
0
0
3
.020
..03U
.002
.001
'
INSECTICIDE
•DDT
TOX.
END.
M. P.
KERKPATRICK POND 1973
WATER (PPB)
SAMPLE PERIOD
1
.055
.60
0
0
2
0
8.16
.21
.3U
3
0
6.60
.078
0
SEDIMENT (PPM)
SAMP
1
T
0
0
0
LE PERIOD
2
0
0
0
0
3
.022
0
0
0
KERKPATRICK POND 197^
BJ'JECTICIDE
DDT
TOX.
.I^ID.
M. P.
WATER (PPB)
SAMPLE PERIOD
1
.020
0
0
0
2
0
5.16
,lU
0
3
0
U.2
0
.1*66
SEDIMENT (PPM)
SAMP]
1
.06
.22
.009
0
LE PERIOD
2
.012
.60
0
0
3
0
.1^9
.002
T •'
273
-------
Pearson Pond - Residue Profile (From Table 32)
The Pearson pond is in the Benevoli Community in Pickens County.
The pond is located within 100 yards of a cotton field. The topographic
features prevent runoff from the cotton field and there is some pro-
tection from drift by trees and other vegetation. Fish samples were
easy to collect from the pond. The pond is in excellent condition.
Some low level residues from drift were detected occasionally.
Parker Pond - Residue Profile (From Table 33)
The Parker pond is in the Pickensville Community in Pickens County.
The pond is located approximately 100 yards downhill from a large cotton
field. A border of trees and vegetation is located between the pond
and cotton. When heavy rains occur, some runoff could possibly reach
the pond. Toxaphene, endrin, and methyl parathion were detected oc-
casionally at low levels in water. Fish samples were fairly easy to
collect and the pond is considered to be in good condition. Fish of
various sizes are present in the pond,
Smelser Pond - Residue Profile (From Table 34)
The Smelser pond is in Tuscaloosa County within 3 miles of the city
of Tuscaloosa. The pond is isolated from cotton production. Soybean
fields are located within 100 yards of the pond. The pond is approxi-
mately 20 acres in size and was in good condition throughout the three^
year study. Fish samples were available at each sample period. In
1973 a considerable amount of residue was detected; however, there were
no harmful effects to fish in the pond. The pond is in excellent condition.
Taylor Pond - Residue Profile (From Table 35)
The Taylor pond is in Elmore County located on Highway 229 five
miles south of Tallassee. The livestock watering pond is located across
the road from a pesticide applicator operation. Empty containers were
piled on the side of the road and spray tanks were filled in the same
location. Very high levels of several pesticides were found in water
and sediment samples from the pond 2 months following pesticide
application.
SUMMARY AND CONCLUSIONS
The pesticide use pattern of cotton insecticides changed over the
threes-year period in the four-county area.
In 1972 DDT was banned eliminating its use in the area. As a result
of the ban, a subsequent decrease in DDT residue occurred in all environ^-
mental component samples from the four-county area. A significant
decline in the number of samples containing DDT residue samples occurred
during the three years.
The use of endrin increased in the four^-county area from 1972
through 1974, conversely an increase in the number of samples containing
endrin residue occurred, Very few samples contained endrin in 1972.
274
-------
TABLE #32
PEARSON POND 1972
»
INSECTICIDE
DDT
TOX.
END.
M. P.
KEPT. E.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0 _,
0
0
2
0
.ok
0
0
0
3
0
0 •
0
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
1 2 3
000
00 0
0 0 0
0 0
000
PEARSON POND 1973
INSECTICIDE
DDT
TOX.
END.
M. P.
HEFT. E.
WATER (PPB)
SAMPLE PERIOD
1
0
. 0
0
0
0
2
0
0
.078
T
• .60
3
.033
.3k
.022
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
122
000
000
000
000
000
•>
i
PEARSON POND 1974
INSECTICIDE
DD?
TOX.
END.
.
M. P.
KEPT. E.
WATER (PPB)'
SAMPLE PERIOD
1
0
0
. o
0
0
2
0
.70
.ok
0
0
3
0
0
0
0
0
SEDIMENT (PPM) .
SAMPLE PERIOD
123
0 0 .0
000
0 T 0.
00 0
000
275
-------
TABLE#33
PARKER POND 1972
INSECTICIDE
DDT
TOX.
•END.
M. P.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0
0
2
.02
0
0
0
3
0
0
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
NSR
0
0
0
2
1.75
0
0
3
.028
.059
0
0
PARKER POND 1973
INSECTICIDE
DDT
TOX.
. END.
••M. P.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0
0
2
0
1.9
.10
.51
3
.18
0
0
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
.010
0
0
0
2
.018
0
0
0
3
0
T
0
0
PARKER POND 197^
^
t f
INSECTICIDE
DDT
TOX.
END.
M. P.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0
0
2
0
2.0U
.023
0
3
0
0
.012
0
SEDIMENT (PPM)
SAMPLE PERIOD
1
.003
0
0
0
2
.080
0
0
0
3
. .005
0
0
0
276
-------
TABLE #3*+
SMELSER POND 1972
INSECTICIDE
DDT
TOX.
END.
M. P.
PCB.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0
0
.51
2
0
0
0
0
0
3
.011
0
0
0
0 .
SEDIMENT (PPM)
SAMPLE PERIOD .
1
0
0
0
0
0
2
0
0
0
0
0
3
0
0
0
0
0
SMELSER POND 1973
INSECTICIDE
DDT
TOX.
END.
"M. P.
WATER (PPB)
SAMPLE' PERIOD
i
0
0
0
0
2
.052
3.96
.026
.01
3
.028
0
0
0
SEDIMENT (PPM)
SAMPLE PERIOD "
1
0
0
0
0
2
0
0
0
0
3
0
0
0
0
. SMELSER POND 197^ •
LV'SSCTICIDE
1'DT.
TOX.
i END.
M. P.
WATER (PPB)
SAMPLE PERIOD
1
0
0
0
0
2
0
.01
.014
0
3
0
0
0
.40
SEDIMENT (PPM)
SAMPLE PERIOD
1
0
0
0
0
2
0
0
0
0
3
0
0
0
0
277
-------
TABLE #35
TAYLOR FARM POND
INSECTICIDE
TOXAPHERE
ENDRIN
M. PARATHION
DEC. 197^
WATER
21.00 PPB
3.36 PPB
2.56 PPB
SEDIMENT
6.00 PPM
O.U8 PPM
0.0 PPM
In 1973 and 1974 endrin residue appeared to stabilize at low levels in
environmental samples. Based on observations for two years—1973 and
1974—there appears to be no increase in endrin residue levels in environ-
mental samples. Additional monitoring of the impact of increased use of
endrin on biological samples would be of value in determining trends.
Toxaphene was used extensively in the four-county area during the
three years. Toxaphene residue was detected in a majority of soil forage
water and wildlife samples at each sample period. The highest levels
in soil forage and water occurred at the end of the insecticide applica-
tion season each year and degraded to low levels in June of the following
year. Therefore there is no indication of a residue build up in soil
water or forage as a result of the degradation pattern. A majority of
the biological samples also contained toxapherie residue at all sample
periods. The average residue level and the range remained fairly stable
in all sample periods throughout the three years indicating a residual
characteristic in biological samples.
Methyl parathion was found in a majority of the soil, forage and
water samples at the second sample period of each year. The residue
degraded to non detectable levels by or before the first sample period
of each year. Methyl parathion was not detected in biological samples.
Therefore, no environmental residue problems are indicated.
Low level dieldrin and heptachlor epoxide residue were found in
about one fourth of the samples throughout the three-year period. The
source of the residue was undetermined. A probable source is from the
treatment for soil insects in past years. Other insecticides were
applied to cotton within the four-county area but did not occur as
residues. Fewer applications probably accounts for the absence of
residue.
278
-------
Fish and wildlife appeared to accumulate the more residual insecti-
cides in proportion to the levels applied within the area. It also
appeared to require from one year to eighteen months for a significant
decline of high level residue to occur after the use of a chemical
has ceased.
Forage including hay and pasture and other crops adjacent to cotton
fields contain high levels of insecticide residue during the cotton
insect control season. Some of the residues persist for two months or
longer at high levels. Old forage which has been subjected to direct
spray or drift contains much higher levels than new or fall seeded
crops from the same area.
Fish ponds located adjacent to cotton fields are in danger of having
fish kills or fish populations greatly reduced. Key factors in
protecting fish ponds are: distance from cotton, trees and other vege-
tative cover, topographic features, proper application methods, and
water supply based on observations from the field study.
Population studies of wildlife in conjunction with residue studies
would be useful in determining effects of insecticides on wildlife.
An environmental monitoring program under commercial field conditions
possibly could prevent environmental problems from developing especially
as new chemicals enter the market or questions arrive regarding the use
of certain insecticides. It appears that the number of applications and
rate of application of residual insecticides has a direct bearing on
residue build up. Therefore, a temporary suspension rather than a
permanent ban on a product may be a more logical solution to residue
problems.
279
-------
280
-------
DESIGN FOR PLENUM HOUSING STUDY
Thomas M. Conway
Obj ective
The objective of this study was to estimate levels of cyclodiene
pesticides in air inside plenum houses and to determine if these levels
are significantly higher than the levels of cyclodiene pesticides in
air of conventional houses.
Background and Introduction
As early as 1950, plenum houses which were designed with underfloor
plenum air distribution systems were being constructed in Lincoln,
Nebraska. By 1970, a contractor in South Bend, Indiana, had built over
700 houses of this type and has continued to add to this number. A 1970
report indicated that more than 1300 plenum houses had been constructed
in Fresno, California. Others have been constructed in Pullman, Washing-
ton; Pierce Lake, Idaho; Hattiesburg, Mississippi; Nashville, Tennessee;
and other locations (Fasick, et al., 1970). Many plenum buildings are
protected from subterranean termite attack by chemical pretreatment of
the soil along the foundation. When cyclodiene insecticides (aldrin,
chlordane, dieldrin and heptachlor) are used in soil treatment the
possibility exists that under certain conditions of moisture and temper-
ature these insecticides may undergo sublimation. The houses constructed
with plenum heating systems usually utilize a polyethylene vapor barrier
between the soil and the crawl space under the house. If the polyethylene
barrier is not impervious to cyclodiene insecticide vapors, a possible
hazard may exist to the health of the occupants of plenum houses where
the soil under the house has been treated with a cyclodiene insecticide.
The forced air plenum system basically consists of a conventional
downflow furnace which discharges conditioned air directly into a clean,
dry, sealed underfloor space, creating a slightly elevated pressure
under the entire house. The air, thus distributed, is then introduced
to the room spaces through conventional floor or baseboard diffusers
connecting the underfloor space to the room space. Since the conditioned
air spreads out evenly and in continuous contact with the underside of
the floor, the floor itself acts as an agent of heat transfer which
creates a combined forced air and radiant panel system. The return air
is collected at one or two intake grills above the heating/cooling units.
The soil under the building is covered with a 6 mil polyethylene vapor
barrier, which is covered with two inches of washed sand as a ballast.
The polyethylene continues up the sides of the foundation and approxi-
mately two feet up the inside face of the studs. In some cases sand
ballast may not be used and the polyethylene may not be continued up
the studs. ,
j
Several papers discussing the design and economics of plenum
heating/cooling systems suggested using the same treatment for termite
control as recommended for building on a slab or with crawl spaces
(Applefield, 1970; Dickerhoof, 1971: Fasick, 1970). There appears to
be no hazard from soil pesticides to occupants of buildings utilizing
these conventional designs (Malina, 1959).
281
-------
The standard preconstruction termite treatment for crawl space
houses recommends application of 0.4 gallons of insecticide solution
per linear foot along the inside and outside of foundation walls, along
both sides of interior partition foundation walls, around piers, pipes,
conduits and any pathways from the ground to the house, and around
utility service entrances. According to the Approved Reference Procedures
for Subterranean Termite Control 1973, the most commonly used method is to
prepare a shallow trench to contain the top layer of chemical and to treat
the lower soil layers by rodding. In addition to the above treatment, the
standard slab pretreatment includes application of 0.1 gallon per
square foot under the slab and attached porches. Some subterranean ter-
mites have developed the ability to build free-standing mud tubes, in
which case the entire ground area under houses of all types are treated
similarly to slab houses.
The toxicities, vapor pressures, recommended formulations, and
recommended application rates of the cyclodiene insecticides are listed.
Unfortunately, quantitative data on cyclodiene insecticide residue levels
in air are quite scarce. In 1959, Malina, et al. took air samples in five
homes within four months after treatment with chlordane for termite control.
His results have been tabulated. All the data collected by Pimentel and
published in 1971 showing ambient levels to be in the nanogram range have
also been summarized. Tessari and Spencer in 1971 used a semi-quantitative
method employing a 1/4 square meter cloth screen and found chlordane and
dieldrin ranging from 1.50 to 3.36 yg/m and 0.04-2.96 yg/m2 respectively,
in the homes of five Colorado farmers. Considerably higher values were
found in the homes of five pesticide formulators. Also, Stanley in 1971
reported finding 19.2 ng/m^ of heptachlor and 8.0 ng/m-* of aldrin in the
ambient air of Iowa City, Iowa.
The maximum permissible air concentrations, the ;estimated amount of
active ingredient applied under a 2,000 square-foot house, the estimated
air concentration of the insecticide in a house of 0.01% of the amount
under the house was in the air at one time, the average known time for
which this application provides 100% protection from termites, and the
average air residue if all the insecticide under the house vaporized
during its lifetime and entered the house—have all been listed.
Also listed are several values for residue levels of dieldrin and hepta-
chlor epoxide found in samples of air and blood reported in past studies (Dale,
1966; Warnick, 1972; Wyllie, 1970). These reported values show a decrease
in levels of these pesticides during the time frame 1965 to 1970. This
decrease reflects the fact that chlorinated hydrocarbon insecticides have
not been used as extensively during these later years.
Relatively little research has been undertaken to determine the
levels of exposure and residues present in humans as a result of pesticide
applications to houses for termite control. Pesticide chemicals
registered for termite control and favored by structural pest control
operators are classified as very toxic or moderately toxic and have
relatively long residual effectiveness. For example, chlordane may
282
-------
remain 100% effective up to 23 years after application. The possibility
exists for permeation of these pesticide residues into the dwelling and
the resulting influence upon the residents may vary with building design
and construction. This study presents a unique opportunity to assess the
influence of different types of home construction and heating/air con-
ditioning systems on the translocation of pesticides in the home environ-
ment; and, concurrently, to assess the body burden of pesticides carried
by persons residing in homes that have been treated for termite control.
The optimum combination of conditions that would maximize the
concentration of cyclodiene insecticide vapors in the air of a plenum
house appears to occur when the house is located on a poorly draining
lot, and a cool fall or spring rain causes water to seep up through the
soil and holes in the polyethylene vapor barrier, bringing with it some
of the soluble pesticide. The heating system then vaporizes some of this
insecticide solution and circulates it through the house. Although
these conditions may occur with relative frequency, it is a specialized
case. A common or general set of conditions that would maximize the
household insecticide residues occurs during cold weather when the house
is sealed and the heating system is continuously circulating warm air
over the plenum vapor barrier. During the summer months a simular situa-
tion would exist except that the air circulating over the plenum vapor
barrier would be cool. It does not appear likely that the soil under
the vapor barrier would be as warm in the cooling case as in the heating
case, and for the purposes of this study, if significant or borderline
levels of cyclodiene air residues are found in the summer, the tests
should probably be repeated in the winter.
It appears that the next highest potential insecticide air residues
would occur in crawl space houses with ductwork forced air heating.
This is because the crawl space air will be heated by radiation from
the duct surfaces and some of this crawl space air will leak into the
house carrying cyclodiene residues. If the house has a partial basement
accessible from inside the house and open to the unsealed crawl space,
there would be a greater chance of cyclodiene residues entering the
house than if the house had only a crawl space without a basement.
Attempts were made to locate houses with partial basements and partial
crawl spaces for comparison to the plenum houses. All study, comparison,
and control houses were single story with approximately the same ratio
of living space air volume to area of soil under the house except
in crawl space houses where partial basements occupied some of the space.
Assuming that the polyethylene vapor barrier used in plenum houses is
not complelely impermeable to cyclodiene insecticide vapors, it would
seem likely that air sampling would show greater amounts of residues
in plenum houses than in conventional ductwork houses with a resultant
increase in blood serum levels among occupants of the plenum houses.
283
-------
Flan of; Studyi
The successive steps used in this study include: definition of
the study area, selection of houses to be sampled^ organization of field
work to collect air, soil and serum samples, tabulation of data, con-^
ducting statistical tests and estimating the precision and' significance
of the findings.
The study was initially planned to be conducted in Fresno, California.
However, a preliminary reconnaissance survey of the Fresno area revealed
that the majority of Fresno residents subscribe to commercial pest control
services. These services frequently and regularly include treatment of
the customers' homes and yards with cyclodiene insecticides. Since this
could lead to significant household residues not derived from the initial
soil treatment for termites nor related to the particular type of heating
system, the Fresno area was rejected as the study site. After verification
that similar interference problems were much less likely to occur, South
Bend, Indiana was chosen as the study site.
The study plan in South Bend, Indiana was as follows:
A) Selection of households to participate in the study.
1. ,Subdivisions of plenum and conventionally heated
homes in the age ranges of 1-3 years pld and
9-12 years old were located in the study area.
2. After location of subdivisions, a master list of all
addresses of single story homes of approximately
1000-1300 sq. ft. of floor space was made.
3. The master list was taken to the South Bend
City Building Department to verify the year of
construction and the size of each home.
4. The master list was then taken to the local exter-
minating company that treated the homes for the
construction company that built the homes to deter-
mine which homes on the list were or were not
treated with cyclodiene insecticides to control
termites.
5. A random selection of homes to be sampled was
drawn from the master list until enough homes
were selected according to the protocol. This
included: '
a- Six study, plenum homes 1-3 years old
b- Six study, plenum homes 9-12 years old
c— Three control, plenum homes 1-3 years old
d- Three control, crawl space homes l-?3 years old
e- Three control, plenum houses 9-12 years old
f^Three control, crawl space homes 9-12 years old
g- :Six conventional comparison, crawl space homes 1-3 years old
h- Six conventional comparison, crawl space homes 9-12 years old
284
-------
6. An alternative list of homes was randomly selected
as replacements in the event one of the households
selected in step 5 decided not to participate in
the study.
7. Each of the prospective participants from each house
was interviewed to determine:
a - willingness to participate in the study.
b - whether they were occupationally exposed to
cyclodiene insecticides.
8. Households that agreed to participate in the study:
a - signed consent forms enabling the sampling team to
collect air and soil samples, as well as blood
serum samples from two occupants.
b - received $75.00 for taking part in the study to
compensate them for inconveniences incurred
during the sampling.
B) Collection of samples from participating households.
1. Two soil samples were collected at each house
according to the method described under "Materials
and Methods."
2. A Mid-West Research Institute (MRI) impinger air
sampling unit was used to collect a 24-hour
air sample as described under "Materials and
Methods."
3. Concurrently with the collection of the air sample
by the MRI unit, one 1/4 square meter nylon chiffon
cloth screen air sampling device was used as
described under "Materials and Methods."
4. In addition, blood samples were taken from two
occupants of each house according to the method
described under "Materials and Methods."
C) Laboratory analysis of all samples collected was conducted
as described under "Materials and Methods for Laboratory
Analysis of Samples."
D) Statistical analysis of laboratory results was done
according to the methods described under "Statistical
Analysis of Data."
285
-------
286
-------
STATISTICAL DESIGN FOR A NATIONAL STUDY TO DETERMINE LEVELS
OF CHLORINATED HYDROCARBON INSECTICIDES IN HUMAN MILK
E. G. Johnson and T. J. Keefe
Colorado State University
Introduction
Concern over the levels of chlorinated hydrocarbon insecticides in
human milk has existed for many years. In 1951 Laug,,et al. reported
DDT in 30 of 32 human milk samples collected in the Washington, D.C.
area. Since that time, numerous references have appeared in the litera-
ture regarding the presence of chlorinated hydrocarbon insecticide
residues in human milk in many countries around the world; for example,
West (1964), Quinby,et al. (1965), Curley and Kimbrough (1969), Savage,
et al. (1973), Acker and Schulte (1970), Engst and Knoll (1972),
Hagyard.et al. (1973), Gracheva (1970), and Takeda.et al. (1973).
However, a nationwide study to determine the levels of organochlorine
insecticides in human milk has never been completed. Thus, we do not
currently have nationwide figures on pesticide levels in nursing mothers
in the U.S. The objective of this study is to estimate levels of organo-
chlorine pesticides in human milk among nursing mothers giving birth in
U.S. hospitals.
Data collected in this study will also be used as a basis to
determine secular and long-term trends in pesticide levels in human milk.
And finally, results collected in the study may be used for development
of improved regulations and standards.
Plan of Study '
Population to be Sampled: Selection of the population to be sampled
creates a problem because the population of inference, or the population
on which information is desired, and the population to be sampled are
not the same. Recall that the objective of the study is to determine
the levels of chlorinated hydrocarbon insecticides in human milk in '
nursing mothers giving birth in U.S. hospitals.
Ideally, we should have, on a continuously updated basis, a con-
ceptually realizable list of nursing mothers during the specified period.
From this list we could then select, according to some procedure, a
sample; and, from the sample, we could then estimate both the incidence
and average level of organochlorine insecticides. This, of course, is
not feasible. Instead, hospitals are the primary sampling units. That
is, from a list of the appropriate general hospitals in the United States,
a sample was selected according to the sampling scheme described below.
It is useful to think of each hospital (the primary sampling unit) as
representing a cluster of nursing mothers recently delivered in that
hospital; and once a hospital is selected, a subsample of nursing
mothers will be developed.
287
-------
The Sampling Frame
Recently a study has been completed by the Pesticides Study Center
at Colorado State University to develop the nationwide incidence rates
of hospitalized acute pesticide poisoning cases among the U.S. population.
Hospitals included in this study (a national sample) were randomly selected
from the list of general hospitals included in the American Hospital
Association's publication entitled, "The 1973 AHA Guide to the Health
Care Field". This list includes both hospitals registered by the
American Hospital Association and osteopathic hospitals listed by the
American Osteopathic Hospital Association, U.S. Government Hospitals,
and long-term care facilities. Any health care institution whose primary
function is to provide patient services, diagnostic and therapeutic, for
a variety of medical conditions both surgical and non-surgical is referred
to as a general hospital.
This list also includes a section entitled newborn nursery for each
hospital. Under this section, the total number of live births in the
hospital, excluding fetal deaths, are reported. The number of births
per hospital were used to allocate the sample proportionately. The
current hospital survey provides identification and access to a well-
defined source of nursing mothers. It was hoped that the previously
established cooperative relationship with the administration of these
hospitals would facilitate the development and execution of the proposed
study of pesticide residues in human milk.
Thus, the population that was sampled consisted of the approximately
595 hospitals which participated in the Acute Pesticide Poisoning Study
and which have nursery facilities. Of these, 150 hospitals were randomly
selected according to the scheme described below. In this scheme, each
general hospital is classified according to pesticide usage levels
(geographic area), state, Pesticide Study Center (Colorado, Iowa, and
South Carolina), and geographic region (see Figure 1). This heirarchical
classification scheme constitutes the sampling frame.
Selection of the Sample; Within each pesticide usage level within
each of the five geographic regions, the general hospitals with nursery
facilities were stratified according to the number of births in the
hospitals for the 1973 calendar year. The stratification plan would
then be as shown in the following diagram:
288
-------
Fxgure 1
(National Human Milk Study)
• * • e * • • • •*• * • • *"• «*W« •*• ***«•*• *• •***• •*• •"•
.v.v.v.v.v.v.v.vJ.v.v.'.v.w.v.v.v.
ALASKA
HAWAII
-------
Region (e.g., Southeast)
Usage Level
Low High
No. Births No. Births
(^Hospital 1 /'"Hospital 1
L, J I H, J I
<_ B! /yr. <•• . . <_ %.. /yr. < .
V^Hospital ^ \ Hospital N^
^Hospital 1 /^Hospital 1
L ) H 7
£.B /yr. < ! <. B /yr. <, I
\ Hospital N^ K V Hospital N"
V^ K V_ K
The stratum boundaries, i.e., B,, B-,..., B , and the allocation of
the number of hospitals sampled witnin each area were determined on the
basis of the actual distribution of the number of hospitals included in
the sampling frame. Within each pesticide usage level within each
geographic region, twenty percent of the hospitals included in the
sampling frame were selected. Once the number of hospitals to be
sampled in the usage level of the region was determined, the stratum
boundaries were determined in the following manner: the hospitals in
the sampling frame were ranked according to births and partitioned into
K quantiles, where K is the number of hospitals to be selected.
Each of these quantiles contains approximately the same number of
hospitals. One hospital was randomly selected within each of these
quantiles with the restriction that each state within the region
received no more than 30% and no less than 10% of the hospitals in the
sample. This procedure ensures that states with a large number of
hospitals are not over represented and ensures that states with a
smaller number of hospitals have an enhanced chance of being represented.
This sampling procedure produced a sample of 150 general hospitals for
the country. The proportional allocations of mothers to be sampled in
each hospital was based on the 1973 number of births in the sampled
hospitals and was constrained so that a minimum of 5 and a maximum of
100 nursing mothers would be interviewed in each hospital sampled. It
should be noted that this allocation procedure implicitly assumes that
the proportion of nursing mothers is constant from hospital to hospital.
As an example of the sample allocation, if the number of births in a
hospital was, one percent of the total of all births among the sampled
hospitals, then one percent of the 1,600 milk samples—that is, 16
samples—were drawn from that hospital. Starting at a specified point
in time, nursing mothers who agree to participate in the study were
290
-------
selected until the quota for the participating hospital was filled. If
for some reason an original study participant dropped out of the study,
the next willing participant was sampled.
Ideally, the allocation of nursing mothers to be sampled should be
based on the distribution of nursing mothers in 1975 within the sampled
hospitals. This, of course, is not possible since the study was to be
conducted during 1975. An alternative method would be to base the
allocation on the distribution of nursing mothers for a previous year.
However, even this information is not available.
This procedure created problems in application because the number
of births in a hospital in 1973" is not necessarily a reliable predictor
of the number of nursing mothers delivering in that hospital in 1975.
Several cases occurred where the number of births in 1975 were much
smaller than the number of births in 1973. Additionally, the proportion
of nursing mothers appears to be. subject to wide variation from hospital
to hospital. The result of this situation is that in several hospitals
the required sample could not be obtained within the time constraints of
the study. For example, use of 1973'"information might require a sample
of 50 nursing mothers from a particular hospital. Upon contacting the
hospital, it might be discovered that only 10 mothers who intend to
nurse will deliver in the hospital during 1975.
Another problem which arose was obtaining cooperation from the
hospitals. Previously established cooperation with hospitals for the
Acute Pesticide Poisoning study did not guarantee cooperation with the
milk study. Some of the reasons for this were the desire on the part
of the doctors to not have their patients disturbed and the unwilling-
ness on the part of administrators to allow nurses to cooperate.
Problems of patient confidentiality also arose.
Each of the above situations made it difficult to collect the
required number of samples from several hospitals within the time limita-
tions. In ordinary sampling schemes, once a sample is selected, every
effort should be made to obtain information on selected individuals.
In the case of refusal by hospital administrators, an effort was made to
contact local doctors in an attempt to locate women who had recently
delivered in the target hospital and who were nursing. Several doctors
were contacted with an effort made to reduce sources of bias. Ideally
the demographic composition of the women contacted in this manner should
be equivalent to the composition of all nursing mothers in the target
hospital. With the lack of available information on nursing mothers,
this of course is not verifiable.
In the event of refusal by hospital administrators, another approach
was to contact the La Leche League to obtain nursing women who had
delivered in the target hospital. If the membership of the La Leche
League involved the same type of woman in each community this would
introduce bias. However a preliminary examination of the data indicates
that the socioeconomic class of members of the League is not constant
across the country. The national membership of the League appears to
include all facets of society. This may not be true of a particular
chapter, however.
291
-------
If the required number of nursing mothers could be obtained by
either of these methods, the hospital was assumed contacted. On
occasion, local doctors would not cooperate; further, there was no La
Leche League in the area, or members of the League would not use the
target hospital for delivery. In this case a substitute hospital (or
hospitals) was selected. Substitutions were also made when the number
of mothers nursing was so small as to require a prohibitive period of
time to obtain the required sample size. This generally occurred when
much fewer births occurred in 1975 than in 1973 and/or when the propor-
tion of nursing mothers is smaller than predicted for that hospital.
Substitutions were obtained in the following manner. All hospitals
in the desired usage level of the milk region with about the same
number of births as the target hospital which had cooperated with the
Center on previous occasions were listed. An alternate hospital was
selected at random from this list. If no hospitals of equivalent size
of the target hospital were available, several hospitals were selected
so that their total number of births approximately equaled the births
in the target hospital in 1973. The sample was then proportionately
allocated among these alternates.
The Data to be Analyzed
It is very important to note that no effort was made to make the
sampled mothers representative of the population of nursing mothers.
The primary reason is that the demographic composition of nursing mothers
in the U.S. is not known (even something as simple as the proportion of
mothers that nurse does not appear to be readily available). Secondly,
if this demographic information were known by region, selection of a
representative sample would require the assumption that the composition
was the same for each hospital in the region, or would require knowledge
of the composition of the hospital. Therefore, data analysis will be
conditional to the observed sample.
Since this study was initiated to determine the levels of organo-
chlorine pesticides in the United States, it is imperative that as
complete data as possible be obtained from each study participant,
including information on past exposure to the organochlorine pesticides.
Another important aspect of this study is to determine time trends
of the levels of pesticides in milk from nursing mothers. A subsample
of approximately 40 women will be drawn in the Colorado Center area and
samples will be collected over a six month period to determine if pesti-
cides in milk remain constant, increase, or decrease over time.
Chemical analyses in this study will include the following pesticides
and metabolites: dieldrin, chlordane, heptachlor, and heptachlor epoxlde
oxychlordane. When sufficient milk is collected this milk will be frozen
and stored for future analyses for the polychlorinated biphenyls (PCB's).
Quanity Control
To check the quality of the survey work performed by the nurse
participants, a resample of 5% of the participants will be checked by
292
-------
telephone. This will serve as a check on thoroughness of the nurse
in obtaining pertinent data from the study participants. This activity
is extremely important since the hospital nurses will receive only the
training provided by the field epidemiologist at the time of the initial
contact with the hospital.
Further quality control of the data generated by this study will
be provided by the staff at the Colorado Pesticides Studies Center
through editing and coding the completed data sheet and in providing
the field epidemiologists with training on selection of the study
participants, completion of the participant survey form, and conducting
the field study on pesticide usage.
293
------- |