540/09-88-036
PESTICIDE HAZARD ASSESSMENT PROJECT:
Harvester Exposure Monitoring Field Studies
(1980 - 1986)
VOLUME 1
A collection of 25 studies submitted to
U.S. Environmental Protection Agency
Office of Pesticide Programs
Hazard Evaluation Division
Washington, D.C. 20460
In conjunction with an interAgency Agreement
with the Department of Labor (DOL)
Research Projects performed by
Mississippi State University
Medical University of South Carolina
Colorado State University
University of Iowa
University of California
Texas Tech University
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540/09-88-036
PESTICIDE HAZARD ASSESSMENT PROJECT:
Harvester Exposure Monitoring Field Studies
(1980 - 1986)
VOLUME 1
A collection of 25 studies submitted to
U.S. Environmental Protection Agency
Office of Pesticide Programs
Washington, D.C. 20460
In conjunction with an InterAgency Agreement
with the Department of Labor (DOL)
Research Projects performed by
Mississippi State University
Medical University of South Carolina
Colorado State University
University of Iowa
University of California
Texas Tech University
DISCLAIMER. The information in this document has been funded
wholly or in part by the Environmental Protection Agency (EPA).
The opinions, findings, conclusions, and recommendations
expressed herein are those of the author(s) and do not
necessarily reflect the views of the EPA. Mention of trade
names or commercial products does not constitute endorsement
or recommendation for use.
-------
TABLE OF CONTENTS
Page
Introduction 4*
Dermal and Respiratory Exposure Studies of Adult and 10
Juvenile Vegetable Harvesters and Fieldworkers 1981
Dermal and Respiratory Exposure Studies of Adult and 32
Juvenile Vegetable Harvesters and Fieldworkers 1982
Dermal and Respiratory Exposure Studies of Adult and 94
Juvenile Vegetable Harvesters and Fieldworkers 1983-
1984
Dislodgeable Captan Residues at Florida Strawbwerry 210
Farms
Assessment of Dermal and Respiratory Exposure of Adult 243
and Juvenile Tobacco Harvesters to Acephate, Duplin
County, North Carolina
Studies of Pesticide Residues Present in the Soil of 276
Three Potato Farms at the Time of Harvest, Aroostock
County, Maine 1982
Assessment of Dermal and Respiratory Exposure of Adult 303
and Juvenile Blueberry Harvesters to Ethyl Parathion,
Malathion and Benomyl, Duplin County, North Carolina
1982
Youth in Agriculture: Dermal and Respiratory Exposure 342
Assessment of Juvenile Potato Harvesters, Aroostock
County, Maine
Youth in Agriculture: Dermal and Respiratory Exposure 384
Assessment of Adult and Juvenile Tomato Harvesters
to Endosulfan, Charleston County, South Carolina 1981
Assessment of Dermal and Respiratory Exposure of Adult 421
and Juvenile Blueberry Harvesters to ULV Malathion,
Duplin County, North Carolina 1982
Youth in Agriculture: Human Exposure Assessment and 463
Medical Records Morbidity Study
Study of Pesticide Exposure of Child and Adult Blueberry 660
Harvesters in Southwestern Michigan in July 1982
Youth in Agriculture: Farmworker Safety in Apple Orchards 888
at Sturgeon Bay, Wisconsin 1981
* Please note that the pagination of the studies in the Table
of Contents correlates to the page numbering located in the
right hand corner of each page.
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INTRODUCTION
On March 17, 1980, the Environmental Protection Agency (EPA)
and the Department of Labor (DDL) entered into an Interagency
Agreement (IAG) to study the effects of pesticides on youth working
in agriculture. The research was needed to provide information
and data about specific pesticides and crops in relation to waiver
requests anticipated from growers which would authorize employment
of 10 and 11 year-old children in activities normally under the
Fair Labor Standards Act. The IAG provided that DOL and EPA would
jointly fund these studies, and these resources were then used to
fund research projects with appropriate institutions (universities
and research firms).
The two major areas of EPA research, the Office of Health
Research laboratory animal toxicology studies and the Office of
Pesticide Program's harvester exposure field studies, were conducted
to provide exposure/toxicity information necessary to evaluate
the possible increased hazard of pesticides to young workers.
Results of the toxicological research are available as published
journal articles. (See attached listing of articles)
Regarding the field studies, the Office of Pesticide Programs
funded worker exposure studies through university cooperative
research agreements in California, Colorado, Florida, Iowa, Texas,
Mississippi and South Carolina. Studies on monitoring pesticide
exposure to children and adults during harvesting were conducted
in California, Colorado, Florida, Maine, Mississippi, Michigan,
North Carolina, South Carolina, Oregon, Texas and Wisconsin. The
studies involved seventeen different crops, including: cucumbers,
peas, sugarcane, peanuts, corn, grapes, strawberries, onions,
tobacco, potatoes, blueberries, tomatoes, apples, blackberries,
raspberries, okra and turnips. Thirty different chemicals were
also involved in the studies. (See Matrix)
The following studies consist of the reports generated by the
various university agreements. It should be noted that some of
this data is also available as published journal articles.
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HEALTH EFFECTS RESEARCH
FOR YOUTH IN AGRICULTURE PROGRAM
Office of Health Research
Health Effects Research Laboratory
Office of Research and Development
U.S.E.P.A.
I- Age Differences in Acute Oral Toxicityt
Gaines, T.B. and Linder, R.E. Acute Toxicity of
Pesticides in Adult and Weanling Rats. Fund Appl.
Toxicol. 7:299-308. 1986.
MacPhail, R.C.r Padilla, S., and Reiter, L. Age-
Related Effects of Pesticides. Presented at Second
International Symposium on the Performance of
Protective Clothing, Tampa, Florida, January 18-22,
1987 (In Press).
Padilla, S., MacPhail, R., and Reiter, L. Age-
Related Effects of Pesticides Relevant to Youth in
Agriculture. HERL Neurotoxicology Division Report,
1985.
II. Age Differences in Dermal Absorption of Pesticides;
Carter, S.D. et al. A Comparison of the Dermal
Absorption of 2-T*C-Benlate in the Young and Adult
Male Rat. Unpublished Research Report.
Fisher, H.L. jet _al. Dermal Absorption of Pesticides
Calculated by Deconvolution. J. Appl. Toxicol. ^:162-
177, 1985.
Hall, L.L. e_t al. Age-Related Percutaneous Penetration
of Dinoseb in Rats. HERL Developmental and Cell Toxi-
cology Division Report.
Hall, L.L. e_t al. Dermal Absorption and Disposition of
Chlordecone in Young and Adult Rats. The Toxicologist
5^:266, 1985 (Abstract only).
Hall, L.L. et al. Dose Response of Skin Absorption in
Young and Adult Rats. HERL Developmental and Cell
Toxicology Division Report.
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II- Age Differences in Dermal Absorption of Pesticides;
Hall, L.L. et al. Jin Vivo and ^n Vitro Dermal
Penetration of 2,4/5,2*,4',5'-Hexachlorobiphenyl in
Young and Adult Rats. HERL Developmental and Cell
Toxicology Division Report.
Shah, P.V. et al. Dermal Penetration of Carbofuran
in Young and Adult Fischer 344 Rats. J. Toxicol. Environ.
Health (Accepted for publication).
Shah, P.V. jet al. Penetration of Fourteen Pesticides
Through the Skin" of Young and Adult Rats: A Preliminary
Screen: (Abstract in the Toxicologist 5:264, 1985). J.
Toxicol. Environ. Health 2^:353-366, 1987-
III. Age Differences in Serum Chemistry Changes Following
Pesticide Exposure;
MacPhail, R.C., Padilla, S., and Reiter, L. Age-
Related Effects of Pesticides. Presented at Second
International Symposium on the Performance of Protective
Clothing, Tampa, Florida, January 18-22, 1987 (In press).
Padilla, S., MacPhail, R., and Reiter, L. Age-Related
Effects of Pesticides Relevant to Youth in Agriculture.
HERL Neurotoxicology Division Report, 1985.
IV- Age Differences in Motor Activity Following Pesticide Exposure;
MacPhail, R.C., Padilla, S., and Reiter, L. Age-
Related Effects of Pesticides. Presented at Second
International Symposium on the Performance of Protective
Clothing, Tampa, Florida, January 18-22, 1987 (In press).
Padilla, S., MacPhail, R., and Reiter, L. Age-Related
Effects of Pesticides Relevant to Youth in Agriculture.
HERL Neurotoxicology Division Report, 1985.
V. Age Differences in Metabolism of Foreign Compounds;
Chadwick, R.W. et al. Antagonism of Chlorobenzene-Induced
Hepatoxicity by Lindane. Pest. Biochem. Physiol. 21;
148-161, 1984.
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7
V. Age Differences in Metabolism of Foreign Compounds;
Copeland, M.F. et al. Use of y-Hexachlorocyclohexane
(Lindane) to Determine the Ontogeny of Metabolism in the
Developing Rat. J. Toxicol. Environ. Health. 18:527-542,
1986. —
VI. Effect of Pesticides on Behavioral Sex Differentiation;
Gray, L.E., Jr. Alteration of Behavioral Sex Differen-
iation by Exposure to Estrogenic Compounds During a
Critical Neonatal Period; Effects of Zearalenone,
Methoxychlor, and Estradiol in Hamsters. Toxicol. Appl.
Pharmacol. 8_0:127-136, 1985.
Gray, L.E., Jr. Com pound-Induced Developmental Reproductive
Abnormalities in Man and Rodents: A Review of Effects in
Males. Repro. Toxicol. (Accepted for publication).
Gray, L.E., Jr. Neonatal Chlordecone Exposure Alters
Behavior Sex Differentiation in Female Hamsters.
Neurotoxicology 3^:67-80, 1982.
VII. Development of a Male Rat Fertility Models
Carter, S.D. et al. Effect of Bencmyl on the Reproductive
Development of Male Rats. J. Toxicol. Environ. Health. 13;
53-68, 1984.
Laskey, J.W. et al. Assessment of the Male Reproductive
System in the Preweanling Rat. J. Toxicol. Environ. Health.
!5_:339-350, 1985.
Rehnberg, G.L. e_t _al. Age-Dependent Changes in Gastro-
intestinal Transport and Retention of Particulate Manganese
Oxide in the Rat. J. Toxicol. Environ. Health. 16;887-899,
1985.
VI11. Susceptibility to Renal Toxic Effects During Lactational and
Prepubertal Periodi
Daston, G.P- e_t al. Toxicity of Mercuric Chloride in the
Developing Rat Kidney. II. Effect of Increased Dosages on
Renal Function in Suckling Pups. Toxicol. Appl. Pharmacol.
74:35-45, 1984.
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8
VIII. Susceptibility to Renal Toxic Effects During Lactational and
Prepubertal Period;
Daston, G.P. £t al. Toxicity of Mercuric Chloride to the
Developing Rat Kidney. III. Distribution and Elimination of
Mercury during Postnatal Maturation. Toxicol. Appl. Pharmacol
8^:39-48, 1985.
Kavlock, R.J., and Daston, G.P. Detection of Renal Dysfunc-
tion in Neonatal Rats: Methodologies and Applications in
Abnormal Functional Development of the Heart, Lungs
and Kidneys.
Kavlock, R.J., and Gray, J.A. Evaluation of Renal Function
in Neonatal Rats. Biology of the Neonate 4_l:279-288, 1982.
Kavlock, R.J., and Gray, J.A. Morphometric, Biochemical, and
Physiological Assessment of Perinatally-Inducted Renal
Dysfunction. J. Toxicol. Environ. Health 11^1-13, 1983.
Kavlock, R.J. The Ontogeny of the Hydropenia Response in
Neonatal Rats and Its Application in Developmental Toxicology
Studies. Banbury Report, Cold Spring Harbor Laboratory, 1982.
XI. Development of Biochemical Indicators of Prenatal Organ
Differentiation;
Kavlock, R.J. et al. An Analysis of Fetotoxicity Using
Biochemical EndpoTn~ts of Organ Differentiation. Teratology
26_: 183-194, 1982.
Kavlock, R.J., and Gray, J.A. Morphometric, Biochemical
and Physiological Assessment of Perinatally-Inducted Renal
Dysfunction. J. Toxicol. Environ. Health JJ^:1-13, 1983.
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Table of Harvester Exposure Monitoring Field Studies Sites
STUDY
REF.#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
PROJECT NAME (UNIV . )
Mississippi State Univ.
Mississippi State Univ.
Mississippi State Univ.
University of Florida
Medical Univ. of
South Carolina
Medical Univ. of
South Carolina
Medical Univ. of
South Carolina
Medical Univ. of
South Carolina
Medical Univ. of
South Carolina
Medical Univ. of
South Carolina
Colorado State Univ.
Univ. of Iowa
Univ. of Iowa
Univ. of California
Univ. of California
Univ. of California
Univ. of California
Univ. of California
Univ. of California
Univ. of California
Texas Tech Univ.
Texas Tech Univ.
Texas Tech Univ.
Texas Tech Univ.
Texas Tech Univ.
STUDY SITE(S)
Mississippi
Mississippi
Mississippi
Florida
North Carolina
Maine
North Carolina
Maine
South Carolina
North Carolina
Colorado
Michigan
Wisconsin
California
Oregon
Oregon
Oregon
California
California
California
California
Texas
Texas
Texas
Texas
Texas
CHEMICAL/CROP
Carbaryl- cucumbers , Carbaryl/
Tbxaphene/Tre flan-peas ,
Carbofuran-sugarcane
Carbaryl-cucumbers ,Aldicarb-
peas ,Tbxaphene/Methyl
parathion-peanuts
Endosul fan- peas , Endosul fan-
corn ,Benomyl-grapes
C aptan- s trawberr ies
Acephate (methamidophos)-
tobacco
Aid ic arb/ Chi or o thai onil/
Dinoseb/Diquat/Endosul fan/
Linur on/Pol yr am/Manco zeb/
Me tham idophos/Me thomyl/
Me tribuz in/Deme ton-potatoes
Ethyl parathion/Malathion/
Benomyl-blueberries
D inoseb- potatoes
Endosulf an- tomatoes
ULV Malathion-blueberries
Tbx aphe ne/Mal athion/par a-
thion( ethyl & methyl )-onions
Mai athion/Me thiocarb/
Captofol- blueberries
Captan/Guthion/Imidan- apples
Captan- strawberries
Carbaryl- strawberries
Vinclozolin-strawberries
Captan/feenomyl-strawberries
Captan-strawberr ies ,Vinclo-
zol in/Me thiocarb/Carbaryl-
blueberries
N/A
Me thiocarb-blueberr ies , Ben-
late-blackberries , raspberries
Carbaryl-okra
Az inphosme thyl- cucumber
Chlorothalon i 1- tomato
Lannate (me thomyl )-cucumber
Phosdr in ( mev inphos ) - turn ip/
mustard greens
TYPE OF EXPOSURE
Harvester Expos.
Harvester Expos.
Harvester Expos.
Foliar Residues
Harvester Expos.
Soil Residues
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Foliage Residues
Reentry Simula-
tion Study(I&II)
5 Harvester Expos
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
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10
Dermal and Respiratory Exposure Studies
of Adult and Juvenile Vegetable
Harvesters and Fieldworkers 1981
Research performed by
Mississippi State University
October 15, 1982
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11
Abstract
During 1981 five field studies were conducted in Mississippi to
determine the actual exposure of adult and juvenile harvesters
working in pesticide-treated fields. Mississippi State
personnel conducted field studies to assess the dermal and
inhalation exposure of juvenile/adult pairs of field workers
to pesticides while hand picking peas and cucumbers, and
harvesting sugar cane. A total of 26 workers (ages 12-40)
were monitored (15 were 16 years old or less). Foliar and
soil sampling was also done to characterize the source of
exposure. Pesticides analyzed for were carbaryl, treflan,
toxaphene, and carbofuran.
In all these studies, dermal exposure to the workers' hands was
generally much higher than other body surface areas. Inhalation
exposure was low and, in most cases, non-detectable.
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12
1981 DERMAL AND RESPIRATORY EXPOSURE STUDIES
OF ADULT/JUVENILE VEGETABLE HARVESTERS
AND FIELD WORKERS
On March 17, 1980, an Interagency agreement between the Environmental
Protection Agency (EPA) and the Department of Labor (DOL) was finalized which
provided framework for cooperative studies between the Agencies, hopefully
resulting in development of pesticide protection programs for farmworkers.
The responsibility of assessing hazards to workers who are exposed to pesti-
cides in the environment lies with the Office of Pesticide Programs, EPA;
while the DOL is responsible, by law, for assuring that no adverse health
effects occur in certain children exposed to agricultural chemicals when
special exemptions are granted allowing them to work. The specific question
quickly arose concerning what safe re-entry intervals were for Juveniles
entering fields which had been treated with pesticides. Since traditional
toxicology data bases and "accepted assumptions" are designed for adult
workers, it is very likely that the data and resulting methodologies are not
adequate for assessing risk to children involved in agriculture. This ap-
parent discrepancy may become a serious problem, particularly with the
realization that the potential for exposure of children to toxic chemicals is
widespread. The EPA and DOL have until now, assumed that juveniles were more
sensitive to pesticide exposure and were more susceptible to resulting toxic
effects than were adults. These assumptions were supported by the belief
that children possess a potential for greater rates of dermal and/or gas-
trointestinal uptake and decreased capacity for detoxification. Unfortu-
nately, no substantiating data exists from actual field studies that can
prove the assumptions are valid. In an attempt to gather such data, the
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13
recently finalized mutual agreement between the Agencies calls for the co-
operative development of scientifically based re-entry intervals for juve-
niles and the assessment of potential health effects from pesticide exposure
to children currently employed in agriculture. To determine the actual
exposure of children working in pesticide-treated fields, the agencies de-
cided that studies should be conducted which would assess the degree of
exposure by the principal potential routes of dermal and inhalation uptake.
Field studies should be done to establish the relationship between the ex-
posure of field workers (juveniles) to pesticides and the residue levels at
the re-entry site which are responsible for the exposure. These levels may
be in the form of dislodgeable residues on foliage and soil and in air.
Exposure studies should also be conducted only in fields which have a known
pesticide treatment history for the current growing season.
During 1981, several studies were conducted by the Mississippi Pesticide
Hazard Assessment Project in an effort to answer some of the questions con-
cerning exposure of children to certain agricultural chemicals. The Project
conducted field studies in Mississippi designed to assess the dermal and
inhalation exposure of juvenile/adult pairs of field workers to pesticides
while hand picking cucumbers and peas, and harvesting sugar cane. Particular
emphasis was given to detecting measurable differences in exposure between
juvenile field workers and adults. The studies were designed to monitor
exposure during normal working conditions, where pesticides had been applied
according to label specifications.
To assess dermal exposure, disposable "Tyvek" jackets were worn by study
participants, to which cellulose adsorption pads were attached. Cotton
gloves were also worn to determine the potential for dermal exposure via the
hands. Inhalation, or respiratory exposure was monitored for each worker
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14
utilizing DuPont Personal Air Samplers Which pulled air at a precalibrated
rate through cartridges containing adsorption media (XAD-4 Resin).
The measurement of superficial pesticide residues (Including dislodge-
able residues on foliage and soil) was also made for each worksite. Com-
posite samples of foliage and soil were collected for pesticide residue
analyses. More detailed descriptions of monitoring and sampling procedures
which were used are presented later in this report. Information in Table 1
identifies the five 1981 monitoring studies, the monitoring sites and dates,
the crops being harvested, the specific pesticides that had previously been
applied to the crops, the dates of pesticide applications and corresponding
application rates.
The monitoring and sampling procedures that were used during the studies
specified in Table 1 are described in the following paragraphs.
Dermal Exposure
Each participant wore a long-sleeve disposable paper jacket (Tyvek).
Affixed to each jacket were several 4" X 4" alpha-cellulose pads with glas-
sine backing; one on each forearm, chest and shoulder, and one on the center
of the upper back. The purpose of the cellulose pads was to trap dislodge-
able residues from the plants and soil that were released as a result of the
workers physical activity in the field. The glassine backing prohibited
contamination of pads by skin oils and perspiration absorbed through the
jacket. The cellulose squares were extracted with acetone, methylene chlo-
ride and hexane prior to use. At the completion of the monitoring period,
the jackets were removed, wrapped in aluminum foil and stored in a freezer
until the pads were analyzed. The seven exposure pads from each jacket were
analyzed individually.
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TABLE 1
1981 YOUTH IN AGRICULTURE STUDIES
Study Mississippi
No. Sites
D-l Louisville
D-2 Louisville
D-3 Fayette
D-4 Fayette
D-5 Fayette
Date Crop Pesticide
Monitored Harvested Applied
9-18-81 Cucumbers Carbaryl
9-21-81 Cucumbers Carbaryl
10-10-81 Peas Treflan
Roundup
Carbaryl
Carbaryl
Toxaphene
Toxaphene
Toxaphene
10-10-81 Peas Treflan
Toxaphene
Toxaphene
Toxaphene
Toxaphene
Toxaphene
Carbaryl
Carbaryl
Toxaphene
Toxaphene
Toxaphene
10-11-81 Sugar Cane Atrazlne
Roundup
Roundup
Dalapon
Carbofuran
Formulation
Carbaryl, 5% Dust
Carbaryl, 10% Dust
Treflan
Roundup
Sevin SOW
Sevin SOW
Toxaphene 6E
Toxaphene 6E
Toxaphene 6E
Treflan
Toxaphene 6E
Toxaphene 6E
Toxaphene 6E
Toxaphene 6E
Toxaphene 6E
Sevin SOW
Sevin SOW
Toxaphene 6E
Toxaphene 6E
Toxaphene 6E
Aatrex 4L
Roundup
Roundup
Dowpon M
Furadan 10G
Application
Date
9-2-81
9-20-81
5-2-81
5-9-81
8-9-81*
9-5-81*
9-12-81*
. 9-26-81*
10-3-81*
5-3-81
6-15-81
6-20-81
6-27-81
7-3-81
7-11-81
8-29-81*
9-5-81*
9-12-81*
9-26-81*
10-3-81*
3-14-81
5-23-81
6-27-81
9-12-81
9-14-81
Application Rate
(Ibs/acre )**
1.0
1.0
0.75
3.0
0.5
0.5
3.0
3.0
3.0
0.75
3.0
3.0
3.0
3.0
3.0
0.5
0.5
3.0
3.0
3.0
3.0
3.0
3.0
3.0
15.0
*
**
First crop disked on July 25. Second crop not planted
Active ingredient
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16
The potential for transfer of translocated residues from foliage, soil
and vegetable surfaces to the workers' hands was assessed through the ana-
lysis of cotton gloves worn by the participants during their exposure moni-
toring periods. Prior to use, the gloves were laundered and also extracted
with acetone. At completion of the monitoring period, the workers' gloves
were removed, wrapped in aluminum foil and frozen. The gloves from each par-
ticipant were also analyzed individually.
Respiratory Exposure
Each participant wore a DuPont P-2500 Personal Air Sampler with the
flow-rate precalibrated at 2 liters/minute throughout his monitored expo-
sure. The adsorbant medium, XAD-4 Resin, was contained in a cartridge at-
tached to the sampler by Tygon tubing. Start and stop times of the samplers
were recorded for subsequent air volume calculations and the flow control
light-emitting diodes of the samplers were monitored to insure proper flow
had been maintained. At the end of the monitoring period, each air sampling
medium was wrapped in aluminum foil and frozen prior to analysis.
Foliage Sampling
Foliage samples were collected by Field Investigators during the har-
vesting activity (potential exposure period) according to the sampling scheme
outlined below. Leaf samples were collected in amber colored glass jars
which were pre-rinsed with acetone. Jar lids were lined with aluminum foil,
and samples were frozen prior to analyses.
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17
Sampling points for the five composite foliage samples were selected as
illustrated in the following diagram.
12345
A
B
c
X
D
* * X A
E
Key
- crop rows: A, B, C, D & E
•*• • sampling path direction
X - sampling points for Foliage and Soil
1,2,3,4,5 - spacing of 5 sampling points
After the middle row was selected at each field site (Row C in diagram)
foliage samples were collected at five points as the investigator moved in a
path parallel to the row. Sampling point #3 was at mid-field, while sampling
points #1 & #2, and #4 and #5 were respectively on each side of point #3 and
equidistant from each other and the end of the corp row. Ten leaf samples
were collected from each plant at the five sampling points in the sampling
path; two from the top foliage, two from opposite sides of the plant at
mid-height, and two from opposite sides at the lowest foliage point.
Soil Sampling
Five composite soil samples were collected at each monitoring site
during the harvesting activity. As indicated in the previous diagram, soil
samples were collected at each of the plant sampling points. Approximately
10 grams was collected at each point (for each of the five sampling points)
from the top half-inch of soil using a stainless steel scoop. Samples were
placed in amber colored glass jars which had been pre-rlnsed with acetone.
Lids were lined with aluminum foil and samples were frozen prior to analyses.
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Studies D-l & D-2. Louisville, Mississippi 1 8
On jvo occasions in September, 1981, the Project monitored a total of
four pairs of juvenile/adult workers during harvesting of fall cucumbers at a
site near Louisville, Mississippi. The cucumbers had been treated previously
with Carbaryl which was the only insecticide used on the crop. Prior to
Study D-l which was conducted on 9-18-81, an application of Carbaryl, 5% Dust
(at 1.0 Ib/acre A.I.) had been made on 9-2-81. The two juvenile/adult pairs
involved in harvesting (la, Ib, Ic, and Id) were monitored as previously
described for dermal and inhalation exposure,to residual levels of Carbaryl,
possibly still present on the surface of foliage and soil and in the air.
Another application of Carbaryl, 10% Dust (at 1.0 Ib/acre AI) was made to the
cucumbers on 9-20-81 and on the following day two juvenile/adult pairs of
workers (2a, 2b, 2c and 2d) were monitored for dermal and inhalation exposure
during the second crop harvest(Study D-2). Samples collected for residue
analysis during both monitoring periods (D-l & D-2) consisted of cellulose
exposure pads (seven per individual) cotton gloves (analyzed individually),
XAD-4 Resin from DuPont Personal Air Samplers, leaves from cucumber plants
and soil. Analytical results for Carbaryl residues on exposure pads, cotton
gloves and X4D-4 Resin are presented in Table 2. Results from analyses of
cucumber foliage and soil collected during each monitoring study are pre-
sented in Table 3. Since leaf samples were analyzed by surface wash only,
2
results are expressed in micrograms per square centimeter (yg/cm ).
Studies D-3, D-A and D-5, Fayette, Mississippi
As previously specified in Table 1 (1981 Youth In Agriculture Studies),
three exposure studies were conducted by the MS PHAP in October, 1981, at
Fayette, Mississippi, involving a total of 12 juveniles and 6 adults. The
limited availability of DuPont Personal Air Samples resulted in fewer adult
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19
participants than juveniles since the latter were considered more critical to
the studies. Two studies (D-3 and D-4) involved monitoring dermal and in-
halation exposure of juvenile/adult workers While hand-picking two varieties
of peas; Pink-eye Purple Hull (October 10, 1981 AM) and Mississippi Purple
Hull, (October 10, 1981 PM). A third study (D-5) involved dermal and inhala-
tion monitoring of juvenile/adult workers while harvesting Canal Point 5248
sugar cane on October 11, 1981.
Dermal and inhalation monitoring of field workers was performed as
described previously in this report using cellulose adsorption pads (on Tyvek
jackets) and DuPont Personal Air Samplers. In studies D-3 and D-4, juvenile
and adult workers were monitored for exposure to three pesticides (Carharyl,
Toxaphene and Treflan) which had been applied previously (see Table 1) to the
crop. Samples collected during hand-picking of peas at the two sites con-
sisted of cellulose adsorption pads (seven for each worker), cotton gloves,
XAD-4 Resin from the Personal Air Samplers, crop foliage and soil. All
samples were analyzed for Treflan, Carbaryl and Toxaphene residues and the
results for studies D-3 and D-4 are presented in Tables 4, 5, 6, 7.
-------
Table 2
Dermal and Respiratory Exposure of Juvenile/Adult
Cucumber Harvesters to Carbaryl
Louisville, Mississippi
Carbaryl Results
Study
Number
D-l
D-l
D-l
D-l
Participant ID
Juvenile
la
Ib
-
Adult
Ic
Id
Exposure
Time
Minutes
47
47
47
47
Cellulose-Pads*
ng/cm
Back
ND**
ND
ND
ND
RS
ND
ND
ND
ND
LS
ND
ND
ND
ND
RC
ND
ND
ND
ND
LC
ND
ND
ND
ND
RA
ND
ND
ND
ND
LA
ND
ND
ND
ND
Cotton
Total
R Hand
380
405
440
301
Gloves Personal, Air***
"8
L Hand
360
440
615
181
ng/m
603
ND
104
ND
D-2
D-2
D-2
D-2
2a
2b
2c
2d
31 7.0 5.6 2.6
31 13.2 5.0 4.9
31 24.8 11.6 12.5
31 10.9 6.1 5.4
Total mg
ug/m
2.2
4.4
8.2
7.5
4
2
5
5
.2
.5
.0
.8
3.
5.
7.
15.
4
1
7
0
4
9
10
20
.6
.9
.4
.7
35
56
31
.42
.02
.92
i»
7.
20.
16.
11.
90
40
87
0
46.95
0.35
14.54
4.32
**
Pad Locations
RS/LS - Right or Left Shoulder
RC/LC - Right or Left Chest
RA/LA - Right or Left Forearm
ND - None Detected
*** DuPont 2500 Air Samplers with XAD-4 Resin
rv>
o
-------
Table 3
Analyses of Soil and Cucumber Leaves
From Monitoring Site at Louisville, Mississippi
STUDIES D-l and D-2
21
MSCL
LAB NO.
647,848
647,849
647,850
647,851
647,852
SAMPLE
POINT
1
2
3
4
5
SAMPLE
TYPE
Leaves*
Leaves
Leaves
Leaves
Leaves
CARBAR|L
ND
ND
ND
ND
ND
D-2
D-2
D-2
D-2
D-2
647,853
647,854
647,855
647,856
647,857
1
2
3
4
5
Leaves*
Leaves
Leaves
Leaves
Leaves
0.78
1.94
0.87
0.71
3.28
D-l
D-l
D-l
D-l
D-l
644,595
644,596
644,597
644,598
644,599
1
2
3
4
5
Soil
Soil
Soil
Soil
Soil
pg/gram (ppm)
0.012
0.020
0.038
0.031
0.027
D-2
D-2
D-2
D-2
D-2
644,600
644,601
644,602
644,603
644,604
1
2
3
4
5
Soil
Soil
Soil
Soil
Soil
8.90
1.77
1.02
1.82
1.95
* Each leaf sample composite consists of 10 punched circles with total area
of 79.6cm .
Analysis by extraction of surface only, so results expressed as jug/cm .
-------
Table 4
Dermal and Respiratory Exposure of Juvenile/Adult
Pea Harvesters to Treflan
Fayette, Mississippi
Treflan Results
Study
Number
D-3
D-3
D-3
D-3
D-3
D-3
D-3
Exposure
Participant ID Time
Juvenile Adult Minutes Back
3a
3b
3c
3d
3e
120
120
120
120
120
3f 120
3g 120
ND**
ND
ND
ND
ND
ND
ND
RS
ND
ND
ND
ND
ND
ND
ND
Cellulose.
ng/cm
LS RC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Pads*
LC
ND
ND
ND
ND
ND
ND
ND
RA
ND
ND
ND
ND
ND
ND
ND
LA
ND
ND
ND
ND
ND
ND
ND
Cotton Gloves Personal, Air***
Total ^g ng/m
R Hand L Hand
0.125
0.068
0.092
ND
0.207
0.087
0.078
0.088
0.051
1.05
0.051
0.076
0.051
0.051
ND
ND
ND
ND
ND
ND
ND
D-4
D-4
D-4
D-4
D-4
D-4
D-4
4a
4b
4c
4d
4e
4f
50
50
50
50
50
50
50
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.02
ND
0.02
0.01
ND .
0.02
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
**
Pad Locations
RS/LS - Right or Left Shoulder
RC/LC - Right or Left Chest
RA/LA - Right or Left Forearm
ND - None Detected
*** DuPont 2500 Air Samplers with XAD-4 Resin
-------
Table 5
Dermal and Respiratory Exposure of Juvenile/Adult
Pea Harvesters to Carbaryl
Fayette, Mississippi
Carbaryl Results
Study
Number
D-3
D-3
D-3
D-3
D-3
D-3
D-3
Participant ID
Juvenile
3a
3b
3c
3d
3e
Adult
-
-
3f
3g
Exposure
Time
Minutes
120
120
120
120
120
120
120
Cellulose2Pads*
ng/cm
Back
0.32
0.77
ND
ND
ND
ND
1.06
RS
0.63
0.56
0.42
ND
ND
ND
ND
LS
0.27
ND**
ND
ND
0.32
ND
ND
RC
0.27
0.28
1.95
ND
0.22
ND
ND
LC
0.49
0.63
1.53
ND
ND
ND
ND
RA
0.43
ND
ND
ND
0.43
ND
0.25
LA
0.49
0.29
0.40
ND
0.54
ND
ND
Cotton
Total
R Hand
3.00
2.57
2.04
0.50
1.73
1.06
2.34
Gloves Personal,Air***
/>g
L Hand
2.72
1.68
1.54
0.30
0.75
0.86
1.54
ng/ra
ND
ND
ND
ND
ND
ND
ND
D-4
D-4
D-4
D-4
D-4
D-4
D-4
4a
4b
4c
4d
4e
4f
50
50
50
50
50
50
50
ND
ND
ND
0.13
ND
ND
ND
ND
ND
ND
ND
0.74
ND
ND
ND
ND
ND
ND
0.43
0.30
ND
ND
ND
ND
ND
0.25
ND
ND
ND
ND
ND
0.23
ND
0.21
ND
ND
ND
ND
ND
0.74
0.17
ND
ND
ND
ND
ND
ND
0.21
ND
1.01
0.06
0.27
0.06
ND
ND
2.55
2.
0.
0.
ND
0.
0.
0.
98
03
31
31
36
79
ND
ND
ND
ND
ND
ND
ND
**
Pad Locations
RS/LS - Right or Left Shoulder
RC/LC - Right or Left Chest
RA/LA - Right or Left Forearm
ND - None Detected
*** DuPont 2500 Air Samplers with XAD-4 Resin
04
-------
Table 6
Dermal and Respiratory Exposure of Juvenile/Adult
Pea Harvesters to Toxaphene
Fayette, Mississippi
Toxaphene Results
Study
Number
D-3
D-3
D-3
D-3
D-3
D-3
D-3
Participant ID
Juvenile Adult
3a
3b
3c
3d
3e
-
-
-
3f
3g
Exposure
Time
Minutes Back
120
120
120
120
120
120
120
ND**
ND
ND
ND
ND
ND
ND
RS
ND
ND
ND
ND
ND
ND
ND
Cell
LS
ND
ND
ND
ND
ND
ND
ND
UiOSC r\
ng/cm
RC
ND
ND
ND
ND
ND
ND
ND
Pads*
LC
ND
ND
ND
ND
ND
ND
ND
RA
ND
ND
ND
ND
ND
ND
ND
LA
ND
ND
ND
ND
ND
ND
ND
Cotton Gloves
Total jig
R Hand L Hand
160
95
120
205
165
245
218
162
130
154
195
146
170
255
Personal ,Air***
ng/m
ND
ND
ND
ND
ND
ND
ND
D-4
D-4
D-4
D-4
D-4
D-4
D-4
4a
4b
4c
4d
4e
4f
50
50
50
50
50
50
50
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
39.1
47.5
35.9
50.7
25.7
36.1
15.2
21.
15.
12.
17.
7.
8.
77.
3
9
8
8
5
8
4
ND
ND
ND
ND
ND
ND
ND
* Pad Locations
RS/LS - Right or Left Shoulder
RC/LC - Right or Left Chest
RA/LA - Right or Left Forearm
** ND - None Detected
*** DuPont 2500 Air Samplers with XAD-4 Resin
-------
Table 7
Analyses of Soil and Pea Leaves
From Monitoring Sites at Fayette Mississippi
Studies D-3 and D-4
25
STUDY
NO.
D-3
D-3
D-3
D-3
SAMPLE
POINT
1
2
3
4
5
SAMPLE
TYPE
Leaves*
Leaves
Leaves
Leaves
Leaves
Treflan
jug/cm
_.***
Carbaryl-
ng/cm
2.76
1.98
2.15
0.82
2.31
Toxapheae
ug/cm
2.11
1.09
2.51
2.48
1.29
D-4
D-4
D-4
D-4
D-4
1
2
3
4
5
Leaves*
Leaves
Leaves
Leaves
Leaves
0.15
0.15
0.67
0.58
4.22
1.35
2.08
3.57
2.67
D-3
D-3
D-3
D-3
D-3
1
2
3
4
5
Soil**
Soil
Soil
Soil
Soil
0.04
0.10
0.09
0.07
0.05
fig/gm
0.02
0.05
0.05
0.02
0.02
Aig/gm
16.52
25.36
23.17
14.65
12.67
D-4
D-4
D-4
D-4
D-4
1
2
3
4
5
Soil
Soil
Soil
Soil
Soil
0.07
0.06
ND
0.07
ND
0.05
0.06
0.03
0.03
0.09
31.22
13.08
19.50
5.64
13.10
* Each leaf.sample composite consists of 10 punched circles with total area
of 79.6cm . Analysis was b,y surface extraction only so results are ex-
pressed as /ig/cm or ng/cm •
** Soil results are expressed as /ig/gm (ppm).
*** Samples lost in analysis
-------
26
As specified earlier in this report, Study D-5 was also conducted at
Fayette, Mississippi on October 11, 1981. The monitoring study involved the
assessment of dermal and Inhalation exposure of two juveniles and two adults
while harvesting sugar cane which had previously received applications of
Atrazine, Roundup, Dalapon and Carbofuran. Samples collected at the harvest
site to be analyzed for Carbofuran residues only consisted of cellulose
adsorption pads, cotton gloves, XAD-4 Resin from DuPont Personal Air Samples,
crop foliage and soil. Analytical results for the four workers, foliage and
soil are presented in Tables 8 and 9.
Table 8
Analyses of Soil and Sugar Cane Leaves
From Monitoring Site at Fayette, Mississippi
Study D-5
STUDY
NO
D-5
D-5
D-5
D-5
D-5
D-5
D-5
D-5
D-5
D-5
SAMPLE
POINT
1
2
3
4
5
1
2
3
4
5
SAMPLE
TYPE
Leaves
Leaves
Leaves
Leaves
Leaves
Soil
Soil
Soil
Soil
Soil
CARBOFURAN
RESIDUES
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-------
Table 9
Dermal and Respiratory Exposure of Juvenile/Adult
Sugar Cane Harvesters to Carbofuran
Fayette, Mississippi
Carbofuran Results
Study
Number
D-5
D-5
D-5
D-5
Participant ID
Juvenile Adult
5a
5b
5c
5d
Exposure
Time
Minutes Back
105
105
105
105
ND**
ND
ND
ND
RS
ND
ND
ND
ND
Cellulose.
ng/cm
LS RC
ND
ND
ND
ND
ND
ND
ND
ND
Pads*
LC
ND
ND
ND
ND
RA
ND
ND
ND
ND
LA
ND
ND
ND
ND
Cotton Gloves Personal-Air***
Total ng ng/m
R Hand L Hand
ND
ND
ND
ND
_****
ND
ND
ND
ND
* Pad Locations
RS/LS - Righr or Left Shoulder
RC/LC - Right on Left Chest
RA/LA - Right or Left Forearm
** ND - None Detected
*** DuPont 2500 Air Samplers with XAD-4 Resin
**** 5a & 5b only wore gloves
-------
28
Quality Control
Specific procedures that were utilized throughout this study for monitor-
ing dermal and inhalation exposure of field workers and collecting environmen-
tal samples for residue analysis have been described previously in the appro-
priate sections in this report. All were done as specified by established
EPA protocol. Analytical residue methods that were used for Carbaryl,
Treflan, Toxaphene and Carbofuran were thoroughly evaluated by Mississippi
and other Project chemists. Various modifications were made in analytical
procedures as were required for our particular situation. The specific
methods with modifications that were used for various substrates will be
included in the MS PHAP Annual Progress Report No. 14.
General quality control procedures adopted by our laboratory concerning
record keeping, analytical reference standards, instrument maintenance and
purity of solvents and reagents are described In the MS PHAP QA Project Plan
for Dermal and Respiratory Pesticide Exposure Assessment of Adult and Juve-
nile Vegetable Harvesters and Field Workers.
As indicated in Table 10 - Recovery of Pesticides from Adsorption Media,
Leaves and Soil - the residue methods used for analyses of cellulose pads,
cotton gloves, XAD-4 Resin, leaves and soil produced results of acceptable
accuracy and precision. Appropriate "spiked" substrates and "blanks" (sample
and reagent) were analyzed with sets of each type sample. The numbers of
"spiked" samples that were analyzed for each type are presented in Table 10
as "replicates". With each number of replicates are presented the corres-
ponding mean recovery, standard deviation and coefficient of variation.
-------
TABLE 10
Pesticide
Carbaryl
Treflan
Toxaphene
Carbofuran
Recovery of Pesticides from Adsorption Media, Leaves and Soil
% Recovery
Sample Type
Cellulose Pads
Gloves
XAD-4 Resin
Leaves
Soil
Cellulose Pads
Gloves
XAD-4 Resin
Soil
Cellulose Pads
Gloves
XAD-4 Resin
Leaves
Soil
Cellulose Pads
Gloves
XAD-4 Resin
Leaves
Soil
Spiking
Level
1 yg
i yg
1 yg
i yg
0. 1 ppm
5 ppm
0.5 yg
1 yg
0.5 yg
0.5 yg
0.05 ppm
10 yg
10 yg
10 yg
10 yg
1 ppm
1 yg
i yg
i yg
i yg
0. 1 ppm
Replicates
18
7
10
5
2
4
10
2
2
6
2
10
4
6
5
2
6
4
4
4
4
Mean
90.5
94.5
99.0
93.0
103.0
91.3
98.1
97.8
82.8
86.0
99.5
95.5
100.1
93.0
94.9
92.8
94.6
89.6
88.3
92.1
84.5
Std. Dev.*
5.8
9.0
18.4
6.7
__
6.1
7.7
—
__
14.4
—
3.1
2.8
4.7
4.0
—
2.9
3.4
7.2
4.3
3.9
Coeff. Var.**
6.4
9.5
18.6
7.2
—
6.7
7.8
—
—
16.7
—
3.2
2.8
5.1
4.2
—
3.1
3.4
8.2
4.7
4.6
*Standard Deviation
**Coefficient of Variation
-------
The lower limits of detection for each pesticide and substrate (deter-
mined by the appropriate residue method) are presented in Table 11.
TABLE 11
Lower Limits of Detection
Pesticide
30
Substrate
Cellulose Pads
Cotton Gloves
Leaves
Soil
XAD-4 Resin
Weather Data
Carbaryl
0.005 yg
0.03 yg
0.01 ppm
0.01 ppm
0.05 yg
Treflan
0.005 yg
0.01 yg
0.01 ppm
0.02 yg
Toxaphene
0.2 |jg
5-Oyg
1.5 ppm
1.5 ppm
0.5 yg
Carbofuran
0.03 yg
0.1 yg
0.02 ppm
0.005 ppm
0.02 yg
For each sampling period, the following data were recorded:
1. Maximum temperature
2. Relative humidity
3. Wind speed, direction and condition
4. Rainfall
5. Cloud cover
Table 12 presents the significant weather conditions/data that existed
during each of the five studies.
TABLE 12
Weather Data
Maximum Relative Wind Speed/
Temperature Humidity Direction/ Cloud
Date *F I _ Condition, mph Rainfall Cover
Bright
Bright
Cloudy
Cloudy
Cloudy
D-l
D-2
D-3
D-4
D-5
9-18-81
9-21-81
10-10-81
10-10-81
10-11-81
74
85
77
89
75
62
54
95
81
85
E-NE, 5-7
Calm
<5
<5
<5
None
None
Misting
None
None
-------
31
Various physical characteristics for the juveniles and adults who par-
ticipated in the five studies are presented in Table 13.
TABLE 13
Physical Characteristics of Study Participants
Participant
Study No.
D-l
D-l
D-l
D-l
D-2
D-2
D-2
D-2
D-3
D-3
D-3
D-3
D-3
D-3
D-3
D-4
D-4
D-4
D-4
D-4
, D-4
D-4
D-5
D-5
D-5
D-5
la
Ib
Ic
Id
2a
2b
2c
2d
3a
3b
3c
3d
3e
3f
3g
4a
4b
4c
4d
4e
4f
*g
5a
5b
5c
5d
M
M
M
F
M
M
F
M
M
M
M
M
M
M
F
M
M
M
M
M
M
M
M
M
M
M
16
16
38
35
16
16
26
32
16
15
16
14
12
40
23
16
13
16
14
12
40
36
16
13
40
36
5 '8"
5 '8"
5 '10"
5 '2"
5' 5"
5 '8"
514-1
5 '6"
5 '4"
5 '6"
5'5"
5'1"
4'8"
6'1"
5 '4"
5'4"
5'0"
5151,
5'1"
4'8"
6'1"
5 '10"
5 '4"
5'0"
6*1"
5 '10"
160
150
175
200
145
150
135
145
120
121
125
93
90
175
150
120
91
125
93
90
175
165
120
91
175
165
B
B
B
B
B
B
B
B
B
B
B
B
B
U
W
B
B
B
B
B
W
W
B
B
W
W
-------
32
Dermal and Respiratory Exposure Studies
of Adult and Juvenile Vegetable
Harvesters and Fieldworkers 1982
Research performed by
Mississippi State University
-------
Abstract
During the summer of 1982, ten field studies were conducted,
which involved a total of 100 workers at five sites in Mississippi
All were designed to assess the dermal and inhalation exposure
of juvenile/adult pairs of field workers to pesticides while
harvesting cucumbers, purple hull peas, and peanuts. These
studies were designed to monitor exposure during normal working
conditions where pesticides had been applied according to label
specifications. Pesticides of interest were carbaryl, aldicarb,
toxaphene and methyl parathion. Samples collected during these
studies included urine, gauze pads, cotton gloves, XAD-4 resin,
ethanol rinses, foliage and soil.
Results were similar to the 1981 studies with dermal exposure
to workers' hands being the primary route of exposure and
inhalation exposure was not significant.
-------
34
STUDY - I.E
1982 DEHMAL AND RESPIRATORY EXPOSURE STUDIES
01 ADULT AND JUVENILE VEGETABLE HARVESTERS
Introduction
During the summer of 1982, ten studies were conducted by the Mississippi
Pesticide Hazard Assessment Project (MS/PHAP) in a continuation of the effort
to answer some of the questions concerning exposure of children to certain
agricultural chemicals. The MS/PHAP conducted field studies involving 100
workers at five sites in Mississippi. All were designed to assess the dermal
and inhalation exposure of juvenile/adult pairs of field workers to pesti-
cides while harvesting cucumbers, purple hull peas, and'peanuts. Five sim-
ilar studies were conducted by the Project in 1981 (Study I.D-1 through 5)
involving the harvest of cucumbers, peas and sugar cane. As in these pre-
vious studies, particular emphasis was given in 1982 to detecting measurable
differences in exposure between juvenile field workers and adults. These
studies were designed to monitor exposure during normal working conditions,
where pesticides had been applied according to label specifications.
Cotton gauze pads were attached to study participants at specific loca-
tions on the body to assess dermal exposure. Cotton gloves were also worn
and alcohol hand rinses were collected to determine the potential for dermal
exposure via the hands. Respiratory exposure was monitored for each worker
utilizing DuPont Personal Air Samplers which pulled air at a precalibrated
rate through cartridges containing adsorption media (XAD-4 resin).
Superficial pesticide residues (including dislodgeable residues on foli-
age and soil) were determined for each worksite. Composite samples of each
-------
35
substrate were collected during each monitoring period for pesticide residue
analyses. More detailed descriptions of monitoring and sampling procedures
used are presented later in this report. Table 1 identifies the ten 1982
monitoring studies, monitoring sites and dates, crops harvested, specific
pesticides that were previously applied to the crops, the dates of pesticide
applications, and corresponding application rates.
Monitoring and sampling procedures used during the studies specified in
Table 1 are described below.
Dermal Exposure
Participants did not wear long-sleeve disposable Tyvek jackets as in
previous worker exposure studies. Instead, four-inch square gauze pads were
attached to the forearms with elastic bands and pinned to workers clothing at
knee level. No pads were attached to the chest, shoulders or back. The
purpose of the gauze pads was to trap dislodgeable residues from foliage and
soil that were released as a result of the workers' physical activity in the
field. Glassine backing on each pad prohibited contamination by skin oils
and perspiration that might be absorbed through the pads.
Prior to use, all gauze pads were extracted with acetone and hexane. At
the completion of the monitoring period, pads were removed, wrapped in alumi-
num foil and stored In a freezer until analyzed. The four exposure pads from
each worker were analyzed as two samples, one composite arm and one composite
leg sample.
The potential for transfer of dislodgeable residues from foliage, soil
and vegetable surfaces to the workers' hands was assessed by analyses of
cotton gloves worn by the participants during their periods of exposure and
ethanol hand rinses obtained Immediately following the harvesting activity.
-------
TABLE 1
1982 Youth In Agriculture Studies
Application History
Study
No.
I.E-l
I.B-2
I.E-3
I.E-4
I.E-5
I.E-6
I.E-7
I.E-8
I.E-9
I.E-10
Sites
Heraanvllle
McCool
McCool
McCool
Louisville
Louisville
Noxapater
Fayette
Fayette
Fayette
Date
Monitored
6-18-82
6-23-82
6-28-82
7-7-82
8-4-82
8-11-82
9-1-82
9-2-82
9-9-82
9-23-82
Crop
Harvested
Cucumbers
Cucumbers
Cucumbers
Cucumbers
Purple Hull Peas
Purple Hull Peas
Purple Hull Peas
Peanuts
Peanuts
Peanuts
Acres
3
0.3
1
1
1
1.5
2.5
0.1
0.1
0.1
Pesticides
Applied
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Carbaryl
Toxaphene
Toxaphene
Toxaphene
Toxaphene
Toxaphene
Toxaphene
Aid lea rb
Aid lea rb
Methyl
Parathlon
Appl. Rate A
Formulation (Lbs.per Acre)
Sevln 80 WP
Sevln 80 WP
Sevln 5Z Dust
Sevln 5% Dust
Sevln 5Z Dust
Sevln 5Z Dust
Seven 5Z Dust
Sevln 51 Dust
Sevln 5% Dust
Sevln 5Z Dust
Sevln 5Z Dust
59Z EC
59Z EC
59Z EC
59Z EC
59Z EC
59Z EC
15Z Temlk Granules
15Z Temlk Granules
EC
„ *
0.50
0.50
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.44
0.44
0.44
0.44
0.44
0.59
15.0
15.0
4.0
Date
Applied
5-22-82
6-2-82
6-17-82
6-22-82
6-17-82
6-22-82
6-27-82
6-17-82
6-22-82
6-27-82
7-6-82
7-22-82
7-31-82
7-22-82
7-31-82
8-7-82
8-31-82
5-15-82
5-15-82
5-15-82
* Active Ingredient (calculated by MS PHAP group)
ON
-------
37
Prior to use, gloves were laundered and then extracted with acetone and
hexang. At completion of the monitored period, the workers' gloves were
removed, wrapped in aluminum foil, transported on ice and frozen in the
Laboratory. Gloves from each participant were analyzed as one composite
sample. Ethanol hand rinses were collected in solvent-rinsed bottles fol-
lowing the monitored period, and were stored under refrigeration until ana-
lyzed. A composite sample of approximately 50 mis/ hand rinse was obtained
from each worker.
Respiratory Exposure
Each adult/juvenile participant wore a DuPont P-4000 Personal Air Samp-
ler throughout his monitored exposure. All personal air samplers were pre-
calibrated at a flow rate of 2 L/min. prior to transport to the field. The
adsorbant medium, 0.5 grams of XAD-4 resin, was contained in a glass car-
tridge attached to the sampler by Tygon tubing. Start and stop times of the
battery powered constant flow pumps were recorded for subsequent air volume
calculations; flow control light-emitting diodes on the samplers were moni-
tored to insure proper flow had been maintained. At the end of the monitored
period, each subject's air sampler cartridge was wrapped in aluminum foil-,*
transported on ice, and frozen in the Lab until analyzed.
Foliage Sampling
Foliage samples were collected by Field Investigators during the har-
vesting activity (potential exposure period) according to the sampling scheme
outlined on the following page. Leaf samples were collected In amber colored
glass jars which were pre-rlnsed with acetone. Jar lids were lined with
aluminum foil; all samples were transported on ice to the Lab and frozen
until analysis.
-------
Sampling points for the five composite foliage samples vere selected as38
Illustrated in the following diagram.
12345
9
A
*
a *
9 V
at
*
-S X X X-
Key: • crop row
4, - sampling path direction
X - sample points for Foliage and Soil
1,2,3,4,5 - sampling paths
Foliage samples were collected as the investigator moved in a path
across the field perpendicular to the crop rows. Sampling path §3 was at
mid-field, while sampling paths #1 and #2 and 14 and 15 were respectively on
each side of path #3 and equidistant from each other and the end of the crop
row. Five leaf punches (each 2.54 on in diameter) were taken from each plant
in the sampling path; one punch from the top foliage, two punches from oppo-
site sides (towards row middles) of the plant at mid-height, and two punches'
from opposite sides at the lowest foliage point. The total number of plant
discs in each composite sample obviously depended on the number of crop rows.
This sampling scheme provided the flexibility required to fit any site, while
insuring that representative samples were obtained for residue analyses.
Soil Sampling
Five composite soil samples were collected at each monitoring site
during the harvesting activity. As Indicated In the previous diagram, soil
-------
39
samples were collected at each of the plant sampling points. Approximately
10 grams was collected with a stainless steel scoop at each point (for each
of the five sampling paths) from the top half-inch of soil. In Studies
I.E-8,9 and 10," involving harvesting of peanuts, soil samples were collected
from the roots of the plants rather than from the soil surface. The collec-
tion procedure will be described in more detail later in this report. Sam-
ples were placed in amber colored glass jars which had been pre-rinsed with
acetone in the Lab prior to field sampling. Lids were lined with aluminum
foil. Samples were frozen in the Lab until analyzed.
Urine Sampling
Urine samples were collected from each adult/juvenile study participant
for three days following each agricultural activity that was monitored. The
first morning and last nightly voids were collected for the three day period.
Attempts were made to collect pre-exposure urine samples from workers when
possible. In several studies, previous harvesting activities of subjects
prohibited collection of pre-exposure samples. Individual urine samples were
provided by participants in bottles furnished by the Project. These bottles
had been prerinsed with acetone and petroleum ether. Screw caps contained
Teflon disks to prevent sample contact with plastic. Participants were
Instructed to store collected urine samples under refrigeration until they
were picked up by Project personnel. When delivered to the laboratory,
samples were frozen until analyzed for the parent compounds and/or urinary
metabolites.
The numbers of each type sample (urine, gauze pads, cotton gloves, XAD-4
resin, ethanol hand rinses, foliage and soil) which were collected for pesti-
cide residue analyses from the ten 1982 studies are summarized in Table 2.
-------
TABLE 2
1982 DOL/EPA Youth in Agriculture Studies
Samples Collected for Analysis
Study Nos.: I.E-1/I.E-2
I.E-3, I.E-4
Crop/Pesticide: Cucumbers/Carbaryl
Adult/Juvenile Pairs: 20
Samples
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
Personal Air
(XAD Resin)
Hand Rinse
TOTAL
Number
Collected
228
80
40
20
20
40
40
468
Study Nos.: I.E-8, I.E-9
Crop/Pesticide: Peanuts/Aldicarb
Adult/Juvenile Pairs: 10
Samples
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
Personal Air
(XAD Resin)
Hand Rinse
TOTAL
Number
Collected
138
40
20
10
10
20
20
258
Study Nos.: I.E-5, I.E-6
I.E-7
Crop/Pesticide: Peas/Toxaphene
Adult/Juvenile Pairs: 15
Samples
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
Personal Air
(XAD Resin)
Hand Rinse
TOTAL
Number
Collected
210
60
30
15
30
30
30
405
Study Nos.: I.E-10
Crop/Pesticide: Peanuts/
Methyl Parathion
Adult/Juvenile Pairs: 5
Samples
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
Personal Air
(XAD Resin)
Hand Rinse
TOTAL
Number
Collected
70
20
10
5
5
10
10
130
TOTAL Adult/Juvenile Pairs Monitored: 50
TOTAL Samples Collected for Analyses: 1,261
-------
41
Study I.E-1, Hermanville. MS
On June 18, 1982 MS PHAP Field Investigators monitored five pairs of
juvenile/adult workers during harvesting of three acres of cucumbers at
Hennanville, Mississippi. As indicated in Table 1, the crop had previously
received two applications of carbaryl at a rate of 0.5 pounds (active ingre-
dient) per acre. The last application was made approximately two weeks prior
to the study. Samples collected for carbaryl residue analyses consisted of
cotton gauze pads (two composites per individual), cotton gloves (one compo-
site per worker), one composite hand rinse, XAD-4 resin from DuPont air
samplers, soil, and leaves from cucumber plants. Three-day urine samples
were also collected as previously described for analysis for a-naphthol, the
urinary metabolite of carbaryl. Analytical results for carbaryl residues on
exposure pads, gloves, XAD-4 resin and in ethanol hand rinses are presented
in Table 3. Nanogram levels were present on pads, while microgram quantities
were found on gloves and in hand rinses. No carbaryl was detected in any air
samples. Lower levels of detection (LLDs) are presented in Table 3 for
carbaryl in or on each of the four substrates. Each LLD is expressed in the
appropriate units of measure for each substrate. An absolute value is also*
reported for each substrate (in parentheses) on which the LLD is based. For
example, the lowest carbaryl level that can be detected on a composite gauze
2
pad sample is 15 ng, which represents 0.3 ng/cm (for a total surface area of
2
50 cm ). LLDs are reported similarly for the other substrates. Results from
analyses of soil and foliage surfaces (surface wash) are presented in
Table 4. No carbaryl residues were detected in either substrate. Results for
urine analyses for a-naphthol are presented in Table 5. Workers harvested
cucumbers on a Monday, Wednesday. Friday schedule, so the presence of a-naph-
thol in pre-exposure urine samples is not surprising since workers had been
exposed to carbaryl during harvest two days prior to the study.
-------
42
Studies I.E-2, I.E-3 and I.E-4; McCool. MS
On three dates in June and July, 1982, a total of fifteen pairs of
juvenile/adult workers were monitored for carbaryl exposure (dermal and
inhalation) during harvesting of cucumbers at a site at McCool, Mississippi.
The number of acres harvested on each date and the applicable pesticide
application history for the monitored field site are presented in Table 1.
Notice in the table that a carbaryl application was made to the cucumber crop
one day prior to each day of harvest. Analytical results for carbaryl on/in
gauze pads, gloves, XAD-4 resin and ethanol hand rinses, for each of the
three studies (I.E-2, 3 & 4) are presented in Tables 6, 9 and 12 respec-
tively. Results for soil and foliage samples collected during each of the
three monitored periods are presented in Tables 7, 10 and 13 respectively.
Carbaryl levels on gauze pads did not vary appreciably between Studies E-2 and
2
E-4. Levels on pads from Study E-3 were present at lower ng/cm quantities.
Milligram levels of carbaryl were found on gloves from workers in Studies E-2
and E-4; lower concentrations in the microgram range were present on gloves
from workers in Study E-3. Rain in the early morning prior to Study E-3
probably was responsible for the decrease, which also was reflected by tfie"
presence of considerably lower levels of carbaryl on foliage samples col-
lected during monitoring at Study Site E-3. Most of the air samples col-
lected by DuPont P-4000 samplers during Study E-4 contained detectable levels
of carbaryl; essentially none was detected in air collected during Studies
E-2 and E-3. These higher levels in air from Study E-4 might be expected,
since higher foliage levels of carbaryl were also found in Study E-4.
Analytical results for a-naphthol, the urinary metabolite of carbaryl,
are presented in Tables 8, 11 and 14 respectively, for urine samples col-
lected from each worker for three days following Studies I.E-2, 3 and 4.
-------
43
Juveniles (a,b,c,d and e) and adults, (f, g and h) were the same In all three
studies. Adult "g" was the owner of the farm where the three studies were
conducted. He also applied the insecticides to the crops on the specified
dates (Table 1) .•» Applications were made by hand with a Cyclone spreader.
His increased exposure resulting from the carbaryl applications on the day
prior to each monitored harvest is reflected by the presence of alpha-
naphthol in his pre-ezposure urine samples, particularly in Studies E-2 and 3
(Tables 8 and 11). The higher alpha-naphthol urine levels for workers in
Studies E-2 and E-4 (Tables 8 and 14) suggest increased exposure to carbaryl
was experienced, compared to workers in Study E-3 (who actually experienced
the longest exposure time of 135 minutes). As previously pointed out, higher
carbaryl levels found on pads, gloves and foliage for Studies E-2 and -E-4
indicate a greater exposure potential probably existed during these two
studies.
Studies I.E-5 and I.E-6, Louisville, MS
On two dates in August, 1982 a total of ten pairs of juvenile/adult
workers were monitored for dermal and inhalation exposure to Toxaphene while
harvesting purple hull peas. These two studies were conducted at the same
Louisville, MS site one week apart, and Involved the same five juveniles
(a,b,c,d, & e) and adults (f,g,h,i, & j). As specified in Table 1, the crop
had received two previous applications of Toxaphene (59Z EC) on July 22 and
31, 1982. Analytical results for Toxaphene residues on or In gauze pads,
gloves, XAD-4 resin and ethanol hand rinses are presented in Tables 15 and
18, respectively, for studies I.E-5 and I.E-6. Results from analyses of soil
and foliage samples (surface wash) collected during each monitored activity
are presented in Tables 16 and 19. Urine samples collected from each worker
-------
44
for three days following each of the two harvest periods were analyzed for
Toxaphene residues. Analytical results are presented In Tables 17 and 20.
The levels of Toxaphene residues found In adsorptlve media (i.e. gauze
pads, gloves and "XAD-4 resin), hand rinses, soil and foliage did not vary
appreciably for the two studies, even though an additional week of weathering
transpired between harvests. The longer exposure period experienced by field
workers in Study I.E-6 (by 33 minutes) compared to Study I.E-5 likely re-
sulted in the slightly higher levels on pads and gloves. Levels in the
2
ng/cm range were present on gauze pads from both studies. Mlcrogram quan-
tities of Toxaphene were found in gloves and hand rinses, and fractional yg/m
levels were present in air samples. No Toxaphene residues were detected in
any urine samples from either study. This finding, though indicative - of
apparent low exposure of field workers, more likely suggests metabolism
and/or degradation of Toxaphene residues to compounds that appear
uncharacteristic of Toxaphene by conventional quantitative electron capture
gas chromatographic (EC/GC) techniques.
Study I.E-7, Noxapater, HS
On September 1, 1982, Project investigators monitored the dermal and
inhalation exposure of five pairs of juvenile/adult workers to Toxaphene
while harvesting purple hull peas at Noxapater, Mississippi. The crop had
received one previous Toxaphene application on August 31, 1982 (Table 1).
Gauze pads, gloves, hand rinses and XAD-4 resin were collected for Toxaphene
residue analysis; results appear in Table 21. Soil and foliage samples
collected during this monitored period were also analyzed for Toxaphene
residues. Results are presented in Table 22. Three-day urine samples col-
lected by each juvenile/adult field worker were analyzed for Toxaphene.
Results are given in Table 23.
-------
45
Toxaphene residues found on gauze pads worn by field workers in Study
I.E-7 were la the same approximate ng/cm range as those found in Studies
I.E-5 and 6. Slightly higher mlcrogram levels were present in gloves, hand
rinses and air samples from Study I.E-7 compared to the two previous studies.
Soil and foliage residue levels of Toxaphene from Study I.E-7 were also
slightly higher than those in the earlier studies. The elevated levels in
the latter study certainly would be expected, since the crop received an
application of Toxaphene one day prior to the day of harvest. As in the
earlier Toxaphene studies, no Toxaphene residues were detected In any urine
samples collected by field workers in Study I.E-7.
Studies I.E-8 and I.E-9, Fayette, MS
On two separate dates in September, 1982 a total of ten pairs of juve-
nile/adult workers were monitored for dermal and inhalation exposure to
aldicarb (Temik) while harvesting peanuts. The crop site at Fayette, MS,
where both studies were done, had received a previous application of aldicarb
(152 Granules) at a rate of 15 Ib/A. Peanuts were harvested by pulling
plants out of the ground, shaking soil off roots and pulling peanuts from the
roots by hand. Since the insecticide-nematocide was applied to the soil as
an in-furrow treatment at planting, the potential did exist for dermal expo-
sure during harvest, particularly to the hands. The same five juveniles
(a,b,c,d & e) and five adults (f,g,h,i, & j) participated in both studies
performed one week apart. All had been involved In harvesting the peanut
crop for approximately three weeks. Therefore, no pre-exposure urine samples
were collected. Participants in Study I.E-8 (conducted on September 2) were
also' scheduled to harvest peanuts the following day, so urine collection was
not started until the evening of September 3. These ten workers were sched-
-------
46
uled to harvest peanuts on two days the following week, September 8 and 9,
1982. The second study (I.E-9) was conducted on the 9th, with urine col-
lection starting that evening. Analytical results for gauze pads, gloves,
hand rinses and* air samples (XAD-4 resin) are displayed in Table 24 (Study
i
I.E-8) and Table 27 (Study I.E-9). Results for soil and foliage samples are
presented in Tables 25 and 28. Since there was appreciable dermal (hand)
contact with soil around the plant roots, samples were collected by shaking
soil from the roots into shallow pans. Five composite samples were then
obtained from the loose soil in the pans. Essentially no aldicarb residues
were detected in adsorptive media from either study. Part per billion levels
were present In soil samples from both studies, and nanogram quantities of
aldicarb were found on foliage collected during Study I.E-8. Foliage samples
collected one week later during Study I.E-9 had no detectable residues.
Urine samples collected by field workers for three days following each mon-
itored harvest were analyzed for the urinary metabolites aldicarb nitrile
sulfone and aldicarb sulfone. Only part per billion levels of the nitrile
sulfone metabolite were found In urine from several workers in Study I.E-8,
as seen in Table 26.
Study I.E-10. Fayette, MS
On September 23, 1982, Project Investigators monitored the dermal and
Inhalation exposure of five juveniles and five adults while hand-harvesting
peanuts which had received a previous application of methyl parathion. The
insecticide was Incorporated Into the soil at planting at a rate of four
pounds per acre (AI). As in the previous peanut harvests, plants were pulled
from the ground, shaken to remove soil from the roots, and peanuts were
removed from the roots by hand. All workers had been Involved in peanut
-------
47
harvests prior to the study, so pre-exposure urine samples were not col-
lected. Urine collection began on the evening of the monitored activity and
continued for three days.
Analytical, results for methyl parathion in/on gauze pads, gloves, hand
rinses and air samples (XAD-4 resin) are presented in Table 30. Nanogram
levels were present on pads, gloves and in air samples. Results for soil and
foliage samples appear in Table 31. Soil samples were collected from around
plant roots as described previously for Studies I.E-8 and 9, since workers
typically experienced prolonged dermal exposure to soil. Part per billion
levels of methyl parathion were found in three of the five composite samples.
No methyl parathion residues were detected on foliage samples. Urine samples
were analyzed for the major urinary metabolite, p-nitrophenol. Samples-from
eight of the ten workers contained part per million levels of the phenolic
metabolite, as presented in Table 32. This result suggests that dermal
contact with soil probably generates the major exposure potential for harvest
workers to methyl parathion. The presence of residues in soil and on gloves
(and absence of residues on foliage) substantiates this conjecture.
-------
Quality Control 48
Specific procedures that vere used throughout this study for monitoring
dermal and inhalation exposure of field workers and collecting environmental
samples for residue analyses have been described previously in appropriate
sections of this report. All were done as specified by established EPA/MSCL
QA protocols. Analytical residue methods used for carbaryl, Toxaphene,
aldicarb and methyl parathion have been thoroughly evaluated by our Missis-
sippi- PHAP and other NFHAP chemists. Various modifications were made in
analytical procedures as required for particular situations. Specific meth-
ods, with modifications used for various substrates, are included later in
this Progress Report.
General quality control procedures adopted by our laboratory concerning
record keeping, analytical reference standards, Instrument maintenance and
purity of solvents and reagents are described in the MS PHAP QA Project Plan
for Dermal and Respiratory Pesticide Exposure Assessment of Adult and Juve-
nile Vegetable Harvesters and Field Workers submitted to EPA and approved by
the EPA/OPP/QAO.
As indicated in Table 33 - Recovery of Pesticides from Adsorption Media,
Urine, Leaves and Soil - the residue methods used for analyses of gauze pads,
cotton gloves, XAD-4 resin, urine, leaves and soil produced results of accep-
table accuracy and precision. Appropriate spiked substrates and blanks
(sample and reagent) were analyzed with sets of each type sample. The num-
bers of spiked samples that were analyzed for each substrate type are listed
in Table 33 as replicates. With each set of replicates are presented the
corresponding mean recovery, standard deviation and coefficient of variation.
-------
Table 3
Dermal and Respiratory Exposure of
Cucumber Harvesters to Carbaryl
Hermanvllle, Mississippi
June 18. 1982
Carbaryl Results
Participant
Study I.D.
Number Youth Adult
I.E-
I.E-
I.E-
I.E-
I.E-
.E-
.E-
.E-
la
Ib
1C
Id
le
—
-
-
.E-l
.E-l
-
-
-
-
-
If
lg
Ih
11
U
Exposure
Time
Mln
154
154
154
154
154
154
154
154
154
154
Gauze
ng per
Arm
ND
1.86
NO
ND
ND
1.56
2.31
0.72
1.30
ND
Padj
cm
Leg
0.85
ND
3.45
0.94
ND
0.82
1.13
0.93
0.65
1.85
Gloves
Total ug
1.48
0.45
3.0
2.19
3.98
2.34
0.96
1.84
0.12
0.53
Hand Rinse
Total pg
ND
1.01
3.28
ND
ND
4.11
3.13
ND
1.17
2.14
Air
Pg per
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3
m
Lower Level of Detection
Absolute
0.3 ng/cm'
(15 ng)
0.12 ug 0.25 ug 0.26 ug/a
(0.12 ug) (0.25 ug) (0.08 ug)
-------
50
Table 4
Analyses of Soil and Cucumber Foliage
From Monitoring Site at Hermanvllle, MS
June 18, 1982
Study No. I.E-1
MSCL
Lab No.
656,764
656,765
656,766
656,767
656,768
Sample
Type
Soil
Soil
Soil
Soil
Soil
Sample
Point
1
2
3
4
5
Carbaryl
ppn
ND*
ND
ND
ND
ND
Lover Level of Detection
0.005
656,747
656,748
656,749
656,750
656,751
Foliage
Foliage
Foliage
Foliage
Foliage
1
2
3
4
5
Lover Level of Detection
Absolute
ng per cm
ND
ND
ND
ND
ND
0.12**
(10 ng)
* ND - None Detected .
** LLD for Foliage is based on surface wash of 83.1 cm
total surface area
-------
Table 5 51
Urine Analytical Results for Alpha-Naphthol
Fron Juvenile/Adult Cucumber Harvesters
Study No. I.E-1
MSCL
Lab No.
659,801
659,802
659,803
659,804
659,805
659,806
659,807
659,808
659,809
659,810
659,811
659,812
659,813
659,814
659,815
659,816
659,817
659,818
659,819
659,820
659,821
659,822
659,823
659,824
659,825
659,826
659,827
659,828
659,829
659,830
659,831
659,832
659,833
659,834
659,835
659.836
659,837
659,838
659,839
659,840
659,841
659,842
Worker
ID
la
la
la
la
la
la
la
Ib
Ib
Ib
Ib
Ib
Ib
Ib
Ic
Ic
Ic
Ic
Ic
Ic
Ic
Id
Id
Id
Id
Id
Id
Id
le
le
le
le
le
le
le
If
If
If
If
If
If
If
Date
Collected
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6*18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
Time
Volume
Collected ml
AH*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
52
61
111
32
164
81
65
71
78
116
66
104
146
66
54
78
170
66
116
100
65
66
66
181
78
146
56
80
62
116
118
146
118
104
72
77
56
100
56
116
100
49
Alpha-Naphthol
ppo Total u8
ND
0.046
0.055
0.054
ND
0.03
ND
ND
ND
ND
ND
ND
ND
ND
0.064
0.057
ND
0.035
0.040
0.064
ND
0.036
0.042
0.033
STD
0.045
0.058
ND
0.034
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.038
ND
ND
ND
0
2.8
6.1
1.7
0
2.4
0
0
0
0
0
0
0
0
3.4
4.4
0
2.3
4.6
6.4
0
2.4
2.8
6.0
0
6.6
3.2
0
2.1
0
0
0
0
0
0
0
0
0
2.1
0
0
0
-------
52
MSCL
Lab No.
659.843
659,844
659,845
659.846
659,847
659,848
659,849
659,850
659,851
659,852
659,853
659,854
659,855
659,856
659,857
659,858
659,859
659,860
659,861
659,862
659,863
659,864
659,865
659,866
659,867
659,868
659,869
659,870'
Worker
ID
lg
18
lg
lg
U
lg
lg
Ih
Ih
Ih
Ih
Ih
Ih
Ih
11
11
11
11
11
11
11
U
1J
U
U
U
U
1J
Date
Collected
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
6-18
6-18
6-19
6-19
6-20
6-20
6-21
Time
Collected
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
Volume
ml
88
118
146
56
81
118
100
59
36
181
66
81
104
48
72
21
100
66
160
61
88
54
100
61
85
100
116
66
Alpha-Naphthol
PPa
ND
0.040
ND
ND
ND
ND
ND
ND
0.030
ND
ND
ND
0.059
0.052
ND
0.037
ND
ND
ND
0.400
0.111
0.108
ND
0.059
0.054
ND
ND
ND
Total u8
0
4.7
0
0
0
0
0
0
1.0
0
0
0
6.1
2.5
0
0.8
0
0
0
24.4
9.8
5.8
0
3.6
4.6
0
0
0
Lover Level of Detection
* Pre-erposure Samples
0.030
-------
Table 6
Dermal and Respiratory Exposure of
Cucumber Harvesters to Carbaryl
Me Cool, Mississippi
June 23, 1982
Carbaryl Results
Participant
Study
Number
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I.E-2
I
Youth
2a
2b
2c
2d
2e
_
-
-
_
-
.0.
Adult
-
-
_
-
-
2f
2g
2h
21
2J
Exposure
Time
Mln
45
45
45
45
45
45
45
45
45
45
Gauze Pad 9
ng per
Arm
4.1
26.7
12.9
2.2
20.4
7.3
38.5
2.3
8.8
3.8
cm
Leg
25.8
384.8
21.8
16.1
20.9
32.8
113.5
26.3
18.2
2.9
Gloves
Total |ig
4.38
3.53
4.03
2.07
3.98
3.37
2.35
1.75
1.46
1.75
Hand Rinse
Total tig
ND
ND
ND
ND
ND
ND
1.5
18.2
76.6
63. B
Air 3
ug per m
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Lower Level of Detection
Absolute
0.8 ng/cm'
(40 ng)
0.12 |jg
(0.12 ,«)
0.25 pg
(0.25
0.88 ug/m
(0.08 pg)
-------
54
Table 7
Analyses of Soil and Cucumber Foliage
From Monitoring Site at McCool, MS
June 23, 1982
Study No. I.E-2
MSCL
Lab No.
656,769
656,770
656,771
656,772
656,773
Sample
Type
Soil
Soil
Soil
Soil
Soil
Sample
Point
1
2
3
4
5
Carbaryl
ppm
2.66
0.31
0.55
0.26
0.82
Lover Level of Detection
0.005
656,752
656,753
656,754
656,755
656,756
Foliage
Foliage
Foliage
Foliage
Foliage
1
2
3
4
5
ng per em
1,996
103
681
932
50
Lower Level of Detection
Absolute
0.12*
(10 ng)
LLD for Foliage is based on surface wash of 83.1 cm
total surface area.
-------
Table 8
Urine Analytic*! Results for Alpha-Naphthol
From Juvenile/Adult Cucumber Harvesters
Study No. I.E-2
MSCL Worker Date Time Volume Alpha-Naphthol
Lab No. ID Collected Collected ml ppm Total u8
•55$,8712a 6-23 AM* 100 ND 0
659,872 2a 6-23 PM 62 0.278 17.2
659,873 2a 6-24 AM 42 0.181 7.6
659,874 2a 6-24 PM 42 NO 0
659,875 2a 6-25 AM 34 ND 0
659,876 2b 6-23 AM* 62 NO 0
659,877 2b 6-23 PM 187 0.342 63.9
659,878 2b 6-24 AM 195 0.065 12.7
659,879 2b 6-24 PM 160 0.046 7.4
659,880 2b 6-25 AM 108 0.099 10.7
659,881 2c 6-23 AM* 62 ND 0
659,882 2c 6-23 PM .30 0.017 3.2
659,883 2c 6-24 AM 22 0.088 1.9
659,884 2c 6-24 PM 79 0.055 4.3
659,885 2c 6-25 AM 100 0.084 8.4
659,886 2d 6-23 AM* 100 NO 0
659,887 2d 6-23 PM 30 0.040 1.2
659,888 2d 6-24 AM 100 0.034 3.4
659,889 2d 6-24 PM 112 ND 0
659,890 2d 6-25 AM 34 ND 0
659,891 2e 6-23 AM* 79 ND 0
659,892 2e 6-23 PM 173 0.169 29.2
659,893 2e 6-24 AM 173 0.071 12.3
659,894 2e 6-24 PM 232 0.050 11.6
659,895 2e 6-25 AM 222 0.054 12.0
659,896 2f 6-23 AM* 84 ND 0
659.897 2f 6-23 PM 200 0.203 40.6
659,898 2f 6-24 AM 84 0.151 12.7
659,899 2£ 6-24 PM 120 0.151 18.1
659,900 2£ 6-25 AM 222 0.076 16.9
659,901 2g 6-23 AM* 100 0.223 22.3
659,902 2g 6-23 PM 84 0.185 15.5
659,903 2g 6-24 AM 84 0.120 10.1
659,904 2g 6-24 PM 100 0.081 8.1
659,905 2g 6-25 AM 92 0.056 5.2
-------
56
MSCL
Lab Ho.
659,904
659,907
659,908
659,909
659,910
Worker
ID
Zh
2h
2h
2h
2h
Date
Collectad
6-23
6-23
6-24
6-24
6-25
Tin*
Collectad
AM*
PM
AM
PM
AM
Volume
•I
108
22
84
118
141
Alpha-Naphthol
ppm
ND
0.042
0.061
0.040
0.030
Total yg
0
0.9
5.1
4.7
4.2
659,911
659.912
659.913
659.914
659.915
21
21
21
21
21
6-23
6-23
6-24
6-24
6-25
AM*
PM
AM
PM
AM
112
132
100
30
160
ND
ND
ND
0.125
0.052
0
0
0
3.8
8.3
659.916
659,917
659,918
659,919
659,920
2J
2J
2J
2J
2J
6-23
6-23
6-24
6-24
6-25
AM*
PM
AM
PM
AM
158
195
187
200
187
0.036
ND
ND
ND
ND
5
0
0
0
0
Lower Level of Detection
* Pre-exposure Samples
0.030
-------
Table 9
Dermal and Respiratory Exposure of
Cucumber Harvesters to Carbaryl
McCool, Mississippi
June 28. 1982
Carbaryl Results
Study
Number
.E-3
.E-3
.E-3
.E-3
.E-3
.E-3
.E-3
.E-3
.E-3
.E-3
Participant
I.D.
Youth Adult
3a
3b
3c
3d
3e
-
-
-
-
-
-
-
.
-
-
3£
3g
3h
31
3J
Lover Level of Detection
Absolute
Exposure
Time
Mln
135
135
135
135
135
135
135
135
135
135
Gauze Pads
ng per cm
Am Leg
1.76 2.10
4.02 2.64
1.48 1.64
1.80 ND
ND ND
ND ND
ND 14.4
ND 2.4
ND ND
ND ND
2
0.8 ng/cm
(40 ng)
Gloves
Total |ig
35.2
104.3
7.2
48.4
37.3
26.9
6.0
20.9
59.7
34.3
0.12 pg
(0.12 pg)
Hand Rinse
Total MB
1.38
1.53
0.77
ND
ND
3.02
ND
1.91
0.97
1.18
0.25 Pg
(0.25 Pg)
Air 3
pg per •
ND
ND
ND
ND
ND
ND
ND
ND
0.24
ND
0.07 pg/m3
(0.02 pg)
01
-------
58
Table 10
Analyse* of Soil and Cucumber Foliage
From Monitoring Site at McCool, MS
June 28, 1982
Study Ho. I.E-3
MSCL
Lab No.
656,774
656,775
656.776
656,777
656,778
Sample
Type
Soil
Soil
Soil
Soil
Soil
Sample
Point
1
2
3
4
5
Carbaryl
ppm
0.26
0.30
0.11
0.12
0.22
Lower Level of Detection
0.005
656,757
656,758
656,759
656,760
656,761
Foliage
Foliage
Foliage
Foliage
Foliage
1
2
3
4
5
ng per em
8.9
12.3
10.4
7.2
17.7
Lower Level of Detection
Absolute
0.12*
(10 ng)
LLD for Foliage is based on surface wash of 83.1 cm
total surface area
-------
Table 11
Urine Analytical Results for Alpha-Naphthol
From Juvenile/Adult Cucuaber Harvesters
Study No. I.E-3
MSCL
Lab No.
659,941
659,942
659.943
659,944
659,945
Worker
ID
3a
3a
3a
3a
3a
Date
Collected
6-28
6-28
6-29
6-29
6-30
Time
Collected
AM*
PM
AM
PM
AM
Volume
ml
37
25
33
18
49
Alpha-N
aphthol
ppm Total ug
ND
ND
ND
ND
ND
0
0
0
0
0
659,946 3b 6-28 AM* 77 ND 0
659,947 3b 6-28 PM 106 ND 0
659,948 3b 6-29 AM 111 ND 0
659,949 3b 6-29 PM 121 ND 0
659,950 3b 6-30 AM 10 ND 0
659,951 3c 6-28 AM* 55 ND 0
659,952 3c 6-28 PM 115 ND 0
659,953 3c 6-29 AM 69 ND 0
659,954 3c 6-29 PM 33 0.042 1.4
659,955 3c 6-30 AM 69 ND 0
659.956 3d 6-28 AM* 23 0.036 0.83
659,957 3d 6-28 PM 3 0.030 0.09
659,958 3d 6-29 AM 93 ND 0
659,959 3d 6-29 PM 77 ND 0
659,960 3d 6-30 AM 195 ND 0
659,961 3e 6-28 AM* 92 ND 0
659,962 3e 6-28 PM 121 ND 0
659,963 3e 6-29 AM 90 ND 0
659,964 3e 6-29 PM 111 ND 0
659,965 3e 6-30 AM 140 ND 0
659,966 3f 6-28 AM* 90 ND 0
659,967 3f 6-28 PM 93 ND 0
659,968 3f 6-29 AM 144 ND 0
659,969 3f 6-29 PM 172 ND 0
659,970 3f 6-30 AM 144 ND 0
-------
MSCL
Lab No.
659,971
659,972
659,973
659,974
659,975
659,976
659,977
659,978
659,979
659,980
659,981
659,982
659,983
659,984
659.985
659,986
659,987
659,988
659,989
659,990
659,991
659,992
659,993
659,994
Worker
ID
3g
3g
3g
3g
3g
3h
3h
3h
3h
3h
31
31
31
31
31
31
31
3J
3j
3J
3J
3J
3j
3J
Date
Collected
6-28
6-28
6-29
6-29
6-30
6-28
6-28
6-29
6-29
6-30
6-28
6-28
6-29
6-29
6-30
6-30
7-1
6-28
6-28
6-29
6-29
6-30
6-30
7-1
Time
Collected
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
Volume
ml
55
111
69
49
100
90
111
100
144
93
95
212
209
144
195
195
88
100
115
195
83
186
76
99
Alpha-Naphthol
ppm Total us
0.102
0.049
0.046
0.042
0.288
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.6
5.4
3.2
2.1
28.8
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Lover Level of Detection
* Pre-exposure Samples
0.030
-------
Table 12
Dermal and Respiratory Exposure, of
Cucumber Harvesters to, Carbaryl
McCool, Mississippi
July 7. 1982
Study
Number
I.E-4
I.E-4
I.E-4
.B-4
.E-4
.E-4
.E-4
.E-4
.E-4
Participant
I.D.
Youth Adult
4a
4b
4c
4d
4e
4f
4g
41)
41
4J
Carbaryl Results
Exposure
Time
Mln
94, "
94
94.
94
94
94
94
94
94
.94,
Gauze Pads
ng per cm
Arm Leg
8.6
115.6
2.2
9.1
21.1
5.7
5.0
5.8
23.5
7.9
134.4
20.6
41.3
90.2
96.0
4.3
25.0
77.4
22.7
14.8
Gloves
Total mg
1.51
3.24
3.26
3.91
1.68
2.29
a. 98
4.41.
2.50
0.79
Hand Rinse
Total pg
55.3
78.9
19. f
55.7
MD
ND
54-7
59.0
82. J
142.1
•rpar •
1*.* '
0.78
7.51
0.97
ND
5.01
0..73
0.47
Lower Level of Detection
Absolute
0.8 ng/cm'
(40 ng)
0.12
(0.12
0.25
(0.25
pg)
0.11 ug/«3
(0.02 pg)
-------
Table 13
Analyses of Soil and Cucumber Foliage
From Monitoring Site at McCool, MS
July 7, 1982
Study No. I.E-4
MSCL
Lab No.
656,779
656,780
656,781
656,782
656,783
Sample
Type
Soil
Soil
Soil
Soil
Soil
Sample
Point
1
2
3
4
5
Carbaryl
ppn
0.34
0.99
0.26
0.16
0.11
Lover Level of Detection
0.005
663,366
663,367
663,368
663,369
663,370
Foliage
Foliage
Foliage
Foliage
Foliage
1
2
3
4
5
ng per cm
240
1,274
1,450
401
680
Lower Level of Detection
Absolute
0.12*
(10 ng)
LLD for Foliage Is based on surface wash of 83.1
total surface area
-------
Table 14
Urine Analytical Results for Carbaryl
From Juvenile/Adult Cucumber Harvesters
Study No. I.E-4
63
660,047
660,048
660,049
660,050
660,051
660,052
660,053
660,054
660,055
660.056
660,057
660,058
660,059
660,060
660,061
660.062
660,063
660,064
660,065
660,066
660,067
660,068
660,069
660,070
660,071
660,072
660,073
660,074
660,075
660,076
Worker
ID
4a
4a
4a
4a
4a
4b
4b
4b
4b
4b
4c
4c
4c
4c
4c
4d
4d
4d
4d
4d
4e
4e
4e
4e
4e
4f
4f
4f
4f
4f
4g
4g
4g
4g
4g
Date
Collected
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
Time
Collected
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
AM*
PM
AM
PM
AM
Volume
ml
21
27
21
20
39
90
70
56
56
43
20
25
27
21
20
35
31
55
17
35
81
70
41
78
78
131
70
70
66
112
45
49
20
43
56
ppm Total us
0.197
0.216
0.159
0.199
0.210
0.287
0.159
0.115
ND
0.041
0.171
0.188
0.176
0.167
0.163
0.075
0.135
0.092
0.165
0.116
0.418
0.540
0.234
0.110
0.106
0.502
0.063
0.065
0.065
0.060
0.657
0.280
0.324
0.336
0.344
4.1
5.8
3.3
4.0
8.2
25.8
11.1
6.4
0
1.8
3.4
4.7
4.8
3.5
3.3
2.6
4.2
5.1
2.8
4.1
33.9
37.8
9.6
8.6
8.3
65.8
4.4
4.6
4.3
6.7
29.6
13.7
6.5
14.5
19.3
-------
64
MSCL
Lab No.
660,077
660.078
660,079
660,080
660,081
660,082
660,083
660,084
660.085
660,086
660,087
660,088
41
41
41
41
41
41
41
660,089
660,090
660,091
660,092
660,093
660,094
660,095
Worker
ID
4h
4h
4h
4h
4h
41
41
41
41
41
41
41
4J
4j
4j
4j
4j
4j
41
Date
Collected
7-7
7-7
7-8
7-8
7-9
7-7
7-7
7-8
7-8
7-9
7-9
7-10
7-7
7-7
7-8
7-8
7-9
7-9
7-10
Time Volume Alpha-Naphthol
Collected ml ppm Total yg
AM*
PM
AM
PM
AM
20
20
70
103
84
0.452
0.433
0.261
0.095
0.137
9.0
8.7
18.3
9.8
11.5
AM*
PM
AM
PM
AM
PM
AM
139
39
70
112
66
20
112
0.297
0.304
0.111
0.040
ND
ND
ND
41.3
11.9
7.8
4.5
0
0
0
AM*
PM
AM
PM
AM
PM
AM
205
102
102
86
81
56
112
0.118
0.236
0.086
0.031
0.037
ND
0.031
24.2
24.1
8.8
2.7
3.0
0
3.5
Lover Level of Detection
* Pre-exposure Samples
0.030
-------
Table 15
Deraal and Respiratory Exposure of
Pea Harvesters to Toxaphene
Louisville, Mississippi
August 4, 1982
Toxaphene Results
Study
Number
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
I.E-5
Participant
I.D.
Youth Adult
5a
5b
5c
5d
5e
-
-
-
-
-
-
-
-
-
-
5f
5g
5h
51
5J
Lower Level of Detection
Absolute
Exposure
Tine
Mln
95
95
95
95
95
95
95
95
95
95
Gauze Pads
ng per en
Am Leg
2.7 14.5
1.7 10.8
5.5 13.7
25.8 23.4
14.5 12.9
13.3 19.1
4.5 13.1
11.6 68.5
13.6 19.8
25.7 38.4
1.0 ng/cn2
(50 ng)
Gloves
Total pg
258
76
124
326
235
204
455
117
232
273
5.0 yg
(5.0 yg)
Hand Rinse
Total pg
6.9
2.6
ND
11.9
3.7
19.1
9.2
23.9
11.0
15.8
2.0 yg
(2.0 Mg)
Air 3
P8 per •
0.50
0.28
0.36
0.65
0.38
0.33
0.53
0.48
0.46
0.49
0.26 Mg/«
(50 ng)
ON
LH
-------
Table 16
Analyses of Soil and Pea Foliage
From Monitoring Site at Louisville, MS
August A, 1982
Study No. I.E-S
MSCL Sample Sample Toxaphene
Lab No. Type Point ppm
665,570 Soil 1 1.31
665,571 Soil 2 0.86
665,572 Soil 3 1.34
665,573 Soil 4 1.40
665,574 Soil 5 2.0
Lower Level of Detection 0.05
ng per cm
668,375 Foliage 1 75
668,376 Foliage 2 471
668,377 Foliage 3 337
668,378 Foliage 4 166
668,379 Foliage 5 340
Lover Level of Detection 18*
Absolute (3.75 ug)
2
* LLD for Foliage is based on surface wash of 207.6 cm
total surface area.
-------
Table 17
Urine Analytical Results for Toxaphene
FTOB Juvenile/Adult Pea Harvesters
Study No. I.E-5
MSCL
Lab No.
668,449
668,450
668,451
668,452
668,453
668,454
668,455
Worker
ID
5a
5a
5a
5a
Sa
5a
5a
Date
Collected
8-4
8-4
8-5
8-5
8-6
8-6
8-7
Tine
Collected
AM*
PM
AM
PM
AM
PM
AM
Volume
al
85
97
138
51
30
30
Toxaphene
ppm
ND
ND
ND
ND
ND
ND
ND
Total i£
0
0
0
0
0
0
0
668,456 5b 8-4 AM* 87 ND 0
668,457 5b 8-4 PM 59 ND 0
668,458 5b 8-5 AM 78 ND 0
668,459 5b 8-5 PM 129 ND 0
668,460 5b 8-6 AM 92 ND 0
668.461 5b 8-6 PM 115 ND 0
668,462 5b 8-7 AM 92 ND 0
668,463 5c 8-4 AM* 68 ND 0
668,464 5c 8-4 PM 95 ND 0
668,465 5c 8-5 AM 120 ND 0
668,466 5c 8-5 PM 83 ND 0
668,467 5c 8-6 AM 68 ND 0
668,468 5c 8-6 PM 67 ND 0
668,469 5c 8-7 AM 59 ND 0
668,470 5d 8-4 AM* 53 ND 0
668,471 5d 8-4 PM 55 ND 0
668,472 5d 8-5 AM 85 ND 0
668,473 5d 8-5 PM 85 ND 0
668,474 5d 8-6 AM 120 ND 0
668,475 5d 8-6 PM 80 ND 0
668.476 5d 8-7 AM 74 ND 0
668,477 5e 8-4 AM* 205 ND 0
668,478 Se 8-4 PM 195 ND 0
668,479 5e 8-5 AM 211 ND 0
668,480 5e 8-5 PM 95 ND 0
668,481 5e 8-6 AM 103 ND 0
668,482 5e 8-6 PM 100 ND 0
668,483 5e 8-7 AM 106 ND 0
-------
68
668,491
668,492
668,493
668,494
668,495
668,496
668,497
668,498
668,499
668,500
668,501
668,502
668,503
668,504
668,505
668,506
668,507
668,508
668,509
668,510
668,511
668,512
668,513
668,514
668,515
668,516
668,517
668,518
Worker
ID
5f
5f
5£
5f
5£
5f
5f
5g
5g
5g
5g
5g
5g
5g
5h
5h
5h
5h
5h
5h
5h
51
51
51
51
51
51
51
5J
5J
5J
5J
5J
5J
5J
Date
Collected
8-4
8-4
8-5
8-5
8-6
8-6
8-7
8-4
8-4
8-5
8-5
8-6
8-6
8-7
8-4
8-4
8-5
8-5
8-6
8-6
8-7
8-4
8-4
8-5
8-5
8-6
8-6
8-7
8-4
8-4
8-5
8-5
8-6
8-6
8-7
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
111
159
29
16
94
33
29
51
45
100
122
170
94
106
80
113
64
85
77
64
52
17
15
40
18
10
24
15
ppm
ND
KD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total U£
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Lover Level of Detection
0.05
-------
Table 18
Dermal and Respiratory Exposure of
Pea Harvesters to Toxaphene
Louisville, Mississippi
August 11, 1982
Toxaphene Results
Study
Number
l.E-6
l.E-6
l.E-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
Participant
I.D.
Youth Adult
6a
6b
6c
6d
6e
-
^m
-
-
—
-
-
-
6f
6g
6h
61
6J
Exposure
Tlae
Min
128
128
128
128
128
128
128
128
128
128
Gauze Pads
ng per en
An Leg
17.5 12.2
9.1 42.8
7.1 165.5
10.6 22.2
13.5 58.5
12.8 18.3
15.2 85.4
13.6 224.6
10.2 6.2
11.3 17.1
Gloves
Total pg
709
515
643
553
886
838
1,088
660
832
342
Hand Rinse
Total pg
15.3
6.7
12.2
9.6
20.4
20.1
44.0
10.8
13.8
5.7
Air 3
pg per •
0.75
0.75
0.36
0.34
0.41
0.29
0.35
0.39
0.29
0.34
Lower Level of Detection
Absolute
1.0 ng/cm
(50 ng)
5.0 pg
(5.0 pg)
2.0
(2.0
0.20 pg/m
(50 ng)
-------
70
Table 19
Analyses of Soil and Pea Foliage
From Monitoring Site at Louisville, MS
August 11, 1982
Study No. I.E-6
MSCL Sample Sample Tozaphene
Lab No. Type Point ppm
665,575 Soil 1 2.21
665.576 Soil 2 2.61
665,577 Soil 3 1.78
665,578 Soil 4 2.11
665,579 Soil 5 3.28
Lover Level of Detection 0.05
ng per cm
668.381 Foliage 1 992
668,382 Foliage 2 701
668,383 Foliage 3 288
668,384 Foliage 4 336
668.385 Foliage 5 420
Lover Level of Detection 18*
Absolute (3.75 yg)
* LLD for Foliage is based on surface wash of
207.6 cm total surface area
-------
Table 20
Urine Analytical Results for Tozaphene
From Juvenile/Adult Pea Harvesters
Study No. I.E-6
71
668,526
668,527
668,528
668,529
668,530
668,531
668,532
668,533
668,534
668,535
668,536
668,537
668,538
668,539
668.540
668,541
668,542
668,543
668,544
668,545
668,546
668,547
668,548
668,549
668,550
668,551
668,552
668,553
Worker
ID
6a
6a
6a
6a
6a
6a
6a
6b
6b
6b
6b
6b
6b
6b
6c
6c
6c
6c
6c
6c
6c
6d
6d
6d
6d
6d
6d
6d
6e
6e
6e
6e
6e
6e
6e
Date
Collected
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
Time
Collected
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
Volume
ml
42
12
32
27
25
29
25
84
96
69
43
84
74
92
74
84
84
80
107
74
69
103
56
69
92
155
140
146
153
136
157
107
102
153
153
ppm
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total u£
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-------
72
668,561
668,562
668,563
668,564
668,565
668.566
668,567
668,568
668,569
668,570
668,571
668,572
668,573
668,574
668,575
668,576
668,577
668,578
668,579
668,580
668,581
668,582
668,583
668,584
668,585
668,586
668,587
668.588
Worker
ID
6f
6f
6f
6f
6f
6f
6f
6g
6g
6g
6g
6g
6g
6g
6h
6h
6h
6h
6h
6h
6h
61
61
61
61
61
61
61
6J
6J
6J
6J
6J
6J
6J
Data
Collected
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-1 1
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
8-11
8-11
8-12
8-12
8-13
8-13
8-14
AM*
m
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
AM*
PM
AM
PM
AM
PM
AM
102
96
24
132
136
116
84
132
146
51
120
172
162
155
56
38
32
69
29
8
25
21
24
21
6
24
17
17
ppa
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total u8
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Lower Level of Detection
* pre-expo8ure sample
0.05
-------
Table 21
Deraal and Respiratory Exposure of
Pea Harvesters to Toxaphene
Noxapater, Mississippi
'September 1, 1982
Toxaphene Results
Study
Number
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
Participant
I.D.
Youth Adult
7a
7b
7c
7d
7e
-
-
-
_
-
-
-
-
-
-
7f
7g
7h
71
7J
Exposure
Time
Mln
90
90
90
90
90
90
90
90
90
90
Gauze Padg
ng
Ana
19.0
29.5
19.6
39.3
17.6
10.4
6.7
21.8
10.8
ND
per cm
l**K
86.0
16.5
72.8
96.7
64.9
25.4
28.1
72.8
95.3
36.8
Gloves
Total ug
492
507
981
1.699
577
534
519
1.375
1.160
789
Hand Rinse
Total ug
14.8
17.5
66.0
145.9
147.9
50.9
31.8
207.0
199.2
79.4
Air 3
Ug per •
6.29
2.69
1.94
2.64
1.91
1.48
2.47
2.46
1.98
2.32
Lower Level of Detection
Absolute
1.0 ng/ca
(50 ng)
5.0 pg
(5.0 yg)
2.0
(2.0
0.28
(50 ng)
-------
74
Table 22
Analyses of Soil And Pea Foliage
From Monitoring Site at Noxapater, MS
September 1, 1982
Study No. I.E-7
MSCL Sample Sample Tozaphene
Lab Ho. Type Point ppm
1 5.05
2 7.74
3 10.90
4 6.99
5 6.17
Lover Level of Detection 0.05
per cm
665,580
665,581
665,582
665,583
665,584
Soil
Soil
Soil
Soil
Soil
668,387 Foliage 1 463
668,388 Foliage 2 -
668,389 Foliage 3 546
668,390 Foliage 4 416
668,391 Foliage 5 523
Lower Level of Detection 18*
Absolute (3.75 yg)
* LLD for Foliage is based on surface wash of 207.6 cm
total surface area.
-------
75
Table 23
Urine Analytical Results for Tozaphene
From Juvenile/Adult Pea Harvesters
Study Ho. I.E-7
MSCL
Lab No.
668.591
668,592
668,593
668.594
668,595
668.596
668,597
Worker
ID
7a
7a
7a
7a
7a
7a
7*
Date
Collected
9-1
9-2
9-2
9-3
9-3
9-4
9-4
Time
Collected
PM*
AM
PM
AM
PM
AM
PM
Volume
ml
57
91
70
57
28
170
37
Toxaphene
PPB
ND
ND
ND
ND
ND
ND
ND
Total ug
0
0
0
0
0
0
0
668.598 7b 9-1 PM* 65 ND 0
668,599 7b 9-2 AM 78 ND 0
668,600 7b 9-2 PM 174 ND 0
668,601 7b 9-3 AM 160 ND 0
668,602 7b 9-3 PM 48 ND 0
668,603 7b 9-4 AM 113 ND 0
668,604 7b 9-4 PM 65 . ND 0
668,605 7c 9-1 PM* 54 ND 0
668,606 7c 9-2 AM 142 ND 0
668,607 7c 9-2 PM 73 ND 0
668,608 7c 9-3 AM 160 ND 0
668,609 7c 9-3 PM 65 ND 0
668,610 7c 9-4 AM 160 ND 0
668,611 7c 9-4 PM 65 ND 0
668,612 7d 9-1 PM* 109 ND 0
668,613 7d 9-2 AM 175 ND 0
668,614 7d 9-2 PM 48 ND 0
668,615 7d 9-3 AM 85 ND 0
668,616 7d 9-3 PM 104 ND 0
668,617 7d 9-4 AM 81 ND 0
668.618 7d 9-4 PM 116 ND 0
668,619 7e 9-1 PM* 25 ND 0
668,620 7e 9-2 AM 52 ND 0
668,621 7e 9-2 PM 25 ND 0
668,622 7e 9-3 AM 37 ND 0
668,623 7e 9-3 PM 57 ND 0
668,624 7e 9-4 AM 57 ND 0
668,625 7e 9-4 PM 43 ND 0
-------
MSCL
Lab No.
668,626
668,627
668,628
668,629
668,630
668.631
668,632
Worker
ID
7f
7£
7f
7£
7f
7f
7f
Date
Collected
9-1
9-2
9-2
9-3
9-3
9-4
9-4
Time
Collected
PM*
AM
PM
AM
PM
AM
PM
Volume
ml
109
139
131
164
174
126
148
76
Toxaphene
PPn
ND
ND
ND
ND
ND
ND
ND
Total ug
0
0
0
0
0
0
0
668,633
668,634
668.635
668,636
668,637
668,638
668,639
668,640
668,641
668,642
668,643
668,644
668,645
668,646
668,647
668,648
668,649
668,650
668,651
668,652
668,653
668,654
668,655
668,656
668,657
668,658
668,659
668,660
Worker
ID
7f
7£
7f
7£
7f
7f
7f
7g
7g
7g
7g
7g
7g
7g
7h
7h
7h
7h
7h
7h
7h
71
71
71
71
71
71
71
7J
7J
7J
7J
7J
7J
7J
Date
Collected
9-1
9-2
9-2
9-3
9-3
9-4
9-4
9-1
9-2
9-2
9-3
9-3
9-4
9-4
9-1
9-2
9-2
9-3
9-3
9-4
9-4
9-1
9-2
9-2
9-3
9-3
9-4
9-4
9-1
9-2
9-2
9-3
9-3
9-4
9-4
PM*
AM
PM
AM
PM
AM
PM
PM*
AM
PM
AM
PM
AM
PM
PM*
AM
PM
AM
PM
AM
PM
PM*
AM
PM
AM
PM
AM
PM
70
94
56
116
91
118
104
68
81
139
43
104
154
109
52
109
85
139
148
48
57
97
68
56
113
107
109
48
76
Tozaphene
Ppm
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total ug
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Lover Level of Detection
* Pre-exposure sample
0.05
-------
Table 24
Dernal and Respiratory Exposure of
Peanut Harvesters to Aldlcarb
Fayette, Mississippi
September 2, 1982
Aldicarb Results
Study
Number
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
I.E-8
Participant
I.D.
Youth Adult
8a
8b
8c
8d
8e
-
:
^
—
-
~
-
-
8f
8g
8h
81
8J
Exposure
Tlae
Min
120
120
120
120
120
120
120
120
120
120
Gauze Pads
ng per en
Am Leg
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
Gloves
Total ug
1.22
ND
ND
1.70
ND
ND
ND
ND
ND
ND
Hand Rinse
Total pg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Air 3
ug per •
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Lower Level of Detection
Absolute
1.6 ng/cm
(40 ng)
0.15 pg
(0.15 ug)
0.10 ug
(0.10 ug)
0.33 ug/i
(40 ng)
-------
Table 25
Analyses of Soil and Peanut Foliage
From Monitoring Site at Fayette, MS
September 2, 1982
Study No. I.E-8
78
MSCL
Lab No.
676,041
676,042
676,043
676,044
676,045
SampIf
Type
Soil
Soil
Soil
Soil
Soil
Sample
Point
1
2
3
4
5
Aldicarb
PPb
142
60
123
25
61
Lover Level of Detection
1.5
676,115
676,116
676,117
676,118
676,119
Foliage
Foliage
Foliage
Foliage
Foliage
1
2
3
4
5
ng per em
39.1
NT)
5.0
1.3
ND
Lower Level of Detection
Absolute
0.61*
(51 ng)
LLD for foliage la based on surface wash of 83.1
total surface area
-------
79
Table 26
Urine Analytical Results for Aldicarb
From Juvenile/Adult Peanut Harvesters
Study No. I.E-8
Aldicarb
MSCL
Lab No.
678,261
678,262
678,263
678,264
678,265
678,266
678,267
Worker
ID
8a
8a
8a
8a
8a
8a
8a
Date
Collected
9-3
9-4
9-4
9-5
9-5
9-6
9-6
Tine
Collected
PM
AM
FM
AM
PM
AM
PM
Volume
ml
29
141
148
15
148
135
125
Sulfone Nitrile*
ppb Total u2
ND 0
ND 0
23.6 3.5
15.2 0.2
18.0 2.7
ND 0
ND 0
678,268 8b 9-3 FM 69 ND 0
678,269 8b 9-4 AM 120 ND 0
678,270 8b 9-4 FM 14 ND 0
678,271 8b 9-5 AM 48 ND 0
678,272 8b 9-5 PM 72 ND 0
678,273 8b 9-6 AM 78 ND 0
678,274 8b 9-6 PM 41 ND 0
678,275 8c 9-3 PM 104 12.4 1.3
678,276 8c 9-4 AM 40 ND 0
678,277 8c 9-4 PM 75 ND 0
678,278 8c 9-5 AM 150 ND 0
678,279 8c 9-5 PM 28 ND 0
678,280 8c 9-6 AM 18 ND 0
678,281 8c 9-6 PM 122 ND 0
678,282 8d 9-3 PM 101 ND 0
678,283 8d 9-4 AM 115 ND 0
678,284 8d 9-4 PM 110 ND 0
678,285 8d 9-5 AM 126 ND 0
678,286 8d 9-5 PM 137 14.0 1.9
678,287 8d 9-6 AM 156 9.2 1.4
678,288 8d 9-6 PM 119 ND 0
678,289 8e 9-3 PM 156 ND 0
678.290 8e 9-4 AM 162 ND 0
678,291 8e 9-4 PM 108 ND 0
678.292 8e 9-5 AM 121 21.6 2.6
678,293 8e 9-5 PM 148 ND 0
678,294 8e 9-6 AM 146 ND 0
678,295 8e 9-6 PM 112 ND 0
-------
80
678,303
678,304
678,305
678.306
678,307
678,308
678.309
678,310
678,311
678,312
678,313
678,314
678,315
678,316
678,317
678,318
678,319
678,320
678,321
678,322
678,323
678,324
678,325
678,326
678,327
678,328
678,329
678,330
Worker
ID
8f
8f
8f
8f
8f
8f
8f
8g
8g
8g
8g
8g
8g
8g
8h
8h
8h
8h
8h
8h
8h
81
81
81
81
81
81
81
8J
8J
8J
8J
8J
8J
8J
Date
Collected
9-3
9-4
9-4
9-5
9-5
9-6
9-6
9-3
9-4
9-4
9-5
9-5
9-6
9-6
9-3
9-4
9-4
9-5
9-5
9-6
9-6
9-3
9-4
9-4
9-5
9-5
9-6
9-6
9-3
9-4
9-4
9-5
9-5
9-6
9-6
FM
AM
PM
AM
FM
AM
PM
FM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
VoluOM
ml
Sample
81
64
61
61
68
62
117
126
63
79
170
95
151
30
20
29
56
65
72
41
13
17
20
18
12
13
14
24
65
32
41
58
50
50
Aldicarb
Sulfone Nitrlle*
ppb
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
28.0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total ug
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.5
0
0
0
0
0
0
0
0
0
0
0
0
Lover Level of Detection 4.0
* All urine samples were also analyzed for aldlcarb sulfone and none was detected
at LLD of 4.0 ppb.
-------
Table 27
Dermal and Respiratory Exposure of
Peanut Harvesters to Aldlcarb
Fayette, Mississippi
September 9, 1982
Aldlcarb Results
Study
Number
I.E-9
I.E-9
.E-9
.E-9
.E-9
.E-9
.E-9
I.E-9
I.E-9
I.E-9
Participant
I.D.
Youth Adult
9a
9b
9c
9d
9e
-
-
-
•»
-
-
-
-
-
-
9f
9g
9h
91
9J
Exposure
Time
Mln
120
120
120
120
120
120
120
120
120
120
Gauze Pads,
ng per
Arm
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
••
cm
Leg
ND
ND
ND
1.4
ND
ND
ND
ND
ND
ND
Gloves
Total pg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Hand Rinse
Total pg
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Air ,
U8 per m
' ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Lower Level of Detection
Absolute
1.2 ng/cm'
(30 ng)
0.15 pg
(0.15 pg)
0.10 pg
(0.10
0.33 pg/i
(40 ng)
oo
-------
op
Table 28 °^
Analyses of Soil and Peanut Foliage
From Monitoring Site at Fayette, MS
September 9, 1982
Study No. I.E-9
MSCL Sample Sample Aldlcarb
Lab No. Type Point ppb
676.046 Soil 1 33.4
676,047 Soil 2 39.9
676,048 Soil 3 7.6
676,049 Soil 4 4.0
676,050 Soil 5 1.6
Lower Level of Detection 1.5
2
qg per cm
676.120 Foliage 1 ND
676,121 Foliage 2 ND
676.122 Foliage 3 ND
676,123 Foliage 4 ND
676.124 Foliage 5 ND
Lover Level of Detection 0.61*
Absolute (51 ng)
LLD for Foliage Is based on surface wash of 83.1 cm
total surface area
-------
Table 29
Urine Analytic*! Result* for Aldicarb
From Juvenile/Adult Peanut Harvesters
Study No. I.E-9
83
678,338
678,339
678,340
678,341
678,342
678.343
678,344
678,345
678,346
678,347
678,348
678,349
678,350
678,351
678,352
678,353
678,354
678.355
678,356
678,357
678.358
678.359
678,360
678,361
678,362
678,363
678,364
678,365
Worker
ID
9a
9a
9a
9a
9a
9a
9a
9b
9b
9b
9b
9b
9b
9b
9c
9c
9c
9c
9c
9c
9c
9d
9d
9d
9d
9d
9d
9d
9e
9e
9e
9e
9e
9e
9e
Date
Collected
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
PM
AM
FM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
FM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
Volume
ml
40
155
85
7
117
139
35
48
85
74
98
105
53
50
93
103
49
152
145
145
54
61
102
144
115
156
110
117
Sample
137
138
34
139
146
144
Sulfone
ppb
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
wOS «
ND
ND
ND
ND
ND
ND
Nltrile*
Total ug
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-------
Aldlcarb
678,373
678,374
678,375
678.376
678,377
678,378
678,379
678.380
678,381
678,382
678,383
678,384
678,385
678.386
678.387
678.388
678.389
678,390
678,391
678,392
678,393
678,394
678,395
678,396
678,397
678.398
678,399
678,400
Worker
ID
9f
9f
9f
9f
9f
9f
91
9g
9g
9g
9g
9g
9g
9g
9h
9h
9h
9h
9h
9h
9h
91
91
91
91
91
91
91
9J
9J
9J
9J
9J
91
9J
Date
Collected
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
9-9
9-10
9-10
9-11
9-11
9-12
9-12
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
155
147
143
140
138
136
129
52
41
20
20
31
34
29
22
18
25
20
18
22
18
13
18
24
21
22
50
51
ppb
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total u2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Lover Level of Detection 4.0
* All urine samples were also analyzed for aldlcarb sulfone at LLD of 4.0 ppb
and none was detected.
-------
Table 30
Dermal and Respiratory Exposure of
Peanut Harvesters to Methyl Parathlon
Fayette, Mississippi
September 23, 1982
Methyl Parathion Results
Participant
Study
Number
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I
Youth
lOa
lOb
lOc
lOd
lOe
_
-
_
-
-
.D.
Adult
—
-
-
-
_
lOf
lOg
lOh
lOi
10J
Exposure
Time
Min
90
90
90
90
90
90
90
90
90
90
Gauze Pad 9
ng
Arm
0.11
ND
0.26
ND
ND
ND
ND
ND
ND
ND
per cm
Leg
0.46
ND
0.42
1.4
ND
ND
ND
ND
0.21
ND
Gloves
Total ng
2.420
24.6
1.960
44.1
278
24.2
30.4
ND
79.4
8.6
Hand Rinse
Total pg
0.61
ND
2.31
ND
0.32
ND
ND
ND
ND
ND
Air ,
ng per •
12.8
ND
65.6
ND
ND
ND
ND
ND
ND
ND
Lower Level of Detection
Absolute
0.06 ng/cm
(3.0 ng)
2.0 ng 0.10 pg 11.0 ng/m
(2.0 ng) (0.10 pg) (2.0 ng)
oo
LH
-------
86
Table 31
Analyses of Soil and Peanut Foliage
From Monitoring Site at Fayette, MS
September 23, 1982
Study No. I.E-10
MSCL Sample Sample Methyl Parathion
Lab No. Type Point ppb
665,690 Soil 1 15.1
665,691 Soil 2 4.5
665,692 Soil 3 ND
665,693 Soil 4 2.2
665,694 Soil 5 ND
Lover Level of Detection 1.9
2
ng per em
1 ND
2 ND
3 ND
4 ND
5 ND
Lower Level of Detection 0.06*
Absolute (5 ng)
2
LLD for Foliage is based on surface wash of 83.1 cm
total surface area.
668,442
668,443
668,444
668,445
668,446
Foliage
Foliage
Foliage
Foliage
Foliage
-------
Table 32
Urine Analytical Result* for Para-Nitrophenol
From Juvenile/Adult Peanut Harvesters
Study No. I.E-10
87
MSCL
Lab No.
665,603
665,604
665,605
665,606
665,607
665.608
665,609
Worker
ID
lOa
lOa
lOa
lOa
lOa
lOa
lOa
Date
Collected
9-23
9-24
9-24
9-25
9-25
9-26
9-26
Time
Collected
PM
AM
PM
AM
PM
AM
PM
Volume
ml
42
131
95
104
132
13
120
Para-NJ
ppo
0.029
0.451
ND
ND
ND
0.056
0.026
Ltrophenol
Total u8
1.2
59.1
0
0
0
0.7
3.1
665.610 lOb 9-23 PM 46 ND 0
665,611 lOb 9-24 AM 134 ND 0
665,612 lOb 9-24 PM 56 ND 0
665,613 lOb 9-25 AM 77 ND 0
665,614 lOb 9-25 PM 65 ND 0
665,615 lOb 9-26 AM 118 ND 0
665,616 lOb 9-26 PM 54 ND 0
665,617 lOc 9-23 PM 42 0.036 1.5
665,618 lOc 9-24 AM 100 0.022 2.2
665,619 lOc 9-24 PM 30 0.017 0.5
665,620 lOc 9-25 AM 136 0.088 11.9
665,621 lOc 9-25 PM 132 0.071 9.4
665,622 lOc 9-26 AM 132 0.046 6.1
665,623 lOc 9-26 PM 132 0.090 11.9
665,624 lOd 9-23 PM 21 ND • 0
665,625 lOd 9-24 AM 77 ND 0
665,626 lOd 9-24 PM 44 0.011 0.05
665,627 lOd 9-25 AM 118 ND 0
665,628 lOd 9-25 PM 113 ND 0
665.629 lOd 9-26 AM 98 0.051 5.0
665.630 lOd 9-26 PM 121 ND 0
665.631 lOe 9-23 PM 137 ND 0
665,632 10e 9-24 AM 56 0.364 20.4
665,633 10« 9-24 PM 69 0.007 0.5
665,634 10* 9-25 AM 73 0.009 0.7
665,635 lOe 9-25 PM 102 ND 0
665,636 lOe 9-26 AM 125 0.020 2.5
665,637 10« 9-26 PM 61 ND 0
-------
88
665,645
665,646
665.647
665,648
665,649
665,650
665,651
665,652
665,653
665,654
665,655
665,656
665,657
665,658
665,659
665,660
665,661-
665,662
665.663
665,664
665,665
665.666
665.667
665,668
665.669
665,670
665,671
665,672
Worker
ID
10f
lOf
lOf
lOf
lOf
lOf
lOf
lOg
lOg
lOg
lOg
lOg
log
lOg
lOh
lOh
lOh
lOh
lOh
lOh
lOh
101
101
101
101
101
101
101
10J
10J
10J
10J
10J
10J
10J
Date
Collected
9-23
9-24
9-24
9-25
9-25
9-26
9-26
9-23
9-24
9-24
9-25
9-25
9-26
9-26
9-23
9-24
9-24
9-25
9-25
9-26
9-26
9-23
9-24
9-24
9-25
9-25
9-26
9-26
9-23
9-24
9-24
9-25
9-25
9-26
9-26
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
PM
AM
PM
AM
PM
AM
PM
96
127
36
116
78
105
99
26
12
13
15
23
9
31
11
19
8
20
8
9
11
50
19
75
70
131
95
59
Para-Nl trophenol
ppa
ND
ND
0.018
ND
9.167
0.441
0.008
ND
ND
ND
ND
3.448
0.082
0.124
ND
0.016
ND
0.060
ND
0.131
ND
ND
ND
0.021
ND
0.040
0.006
0.015
ND
ND
ND
ND
ND
ND
ND
Total ug
0
0
1.1
0
595.8
27.3
0.4
0
0
0
0
268.9
8.6
12.3
0
1.3
0
0.9
0
1.2
0
0
0
0.2
0
0.3
0.5
0.2
0
0
0
0
0
0
0
Lover Level of Detection
0.005
-------
T*bl« 33
Recovery of Pesticide* fron Adsorption Media,
Urine, Leaves and Soil
1982 Youth in Agriculture Studies
89
Pesticide
Carbaryl
a-Naphthol
Toxaphene
Aldicarb
Nitrile
Sulfone
Sulfone
Methyl
Parathlon
Para
Nitrophenol
Sample Type
Gauze Pads
Cotton Gloves
Hand Rinses
XAD-4 Resin
Soil
Foliage
Urine
Gauze Pads
Cotton Gloves
Hand Rinses
XAD-4 Resin
Soil
Foliage
Urine
Gauze Pads
Cotton Gloves
Hand Rinses
XAD-4 Resin
Soil
Foliage
Urine
Urine
Gauze Pads
Cotton Gloves
Hand Rinses
XAD-4 Resin
Soil
Foliage
Urine
Spiking
Level
1.0 yg
1.0 yg
1.0 yg
1.0 yg
1.0 ppm
1.0 yg
5.0 ppm
10.0 yg
10.0 yg
5.0 yg
1.0 yg
1.0 ppm
10.0 yg
3.0 ppm
10.0 yg
10.0 yg
2.0 yg
5.0 yg
0.2 ppm
4.0 yg
0.1 ppm
0.1 ppm
1.0 yg
1.0 yg
1.0 yg
1.0 yg
0.1 ppm
1.0 yg
0.5 ppm
Repli-
cates
9
8
4
6
4
5
24
11
3
6
4
3
3
24
4
2
3
5
2
1
15
15
4
3
2
4
2
4
7
*Standard deviations and means were calculated
TI-40 calculator programmed
Mean
%
84.9
95.0
99.5
90.0
90.0
110.6
86.8
91.8
94.0
94.3
97.3
97.3
98.7
92.9
95.1
100.0
115.7
82.2
101.0
103.0
79.9
88.8
98.6
97.8
106.0
97.9
107.5
98.8
74.5
using a
for various statistical
used for obtaining standard deviations
was:
-• f
Recovery
Standard*
Deviation
13.5
10.8
10.3
6.8
7.7
2.4
9.0
11.4
4.5
5.0
2.0
8.4
2.1
7.1
10.4
—
3.1
9.0
—
— .
8.9
12.8
5.6
7.4
—
1.3
—
7.1
11.2
Coeff. of
Variation
15.9
11.4
10.4
7.6
8.6
2.2
10.4
12.4
4.8
5.3
2.1
8.6
2.1
7.6
10.9
—
2.7
10.9
__-
—
11.1
14.4
5.7
7.6
—
1.0
—
7.2
15.0
Texas Instruments Model
functions. The
(Xi-X)2
n
formula
-------
90
Weather Data
For each of the ten studies, the following data were recorded:
1. Maximum temperature
2. Relative humidity
3. Wind speed, direction and condition
4. Rainfall
5* Cloud cover
Table 34 presents the significant weather conditions that existed during each
study.
Table 34
Weather Data
Studies I.E-1 Through I.E-10
Date
6/8/82
6/23/82
6/28/82
7/7/82
8/4/82
8/11/82
9/1/82
9/2/82
9/9/82
9/23/82
Temp. *P
95
86
82
84
95
84
99
95
98
76
Relative
Humidity Z
78
73
87
85
78
92
74
63
66
68
Wind Speed/
Direction/
Condition/mph
Calm
E-SE, 5
SW, 6
Calm
Calm
Calm
S, 5
Calm
S. 5
Calm
Rain-
Fall
None
None
None
None
None
None
None
None
None
None
Cloud
Cover
None -
None
Cloudy
None
None
None
Cloudy
None
Cloudy
None
Study
Number
I.E-i
I.E-2
I.E-3
I.E-4
I.E-5
I.E-6
I.E-7
I.E-8
I.E-9
I.E-10
Physical characteristics of each juvenile and adult field worker are presented
in Table 35.
-------
fez
M
M
M
M
F
F
F
M
F
M
Age
9
12
15
13
19
20
42
50
56
69
Height
3 '6"
5f
5 '3"
5»8"
5'8"
5'8"
5'6"
6'
5'5"
5*9"
Weight Lbs
50
80
150
120
140
207
230
200
170
135
91
Table 35
Physic*! Characteristics of Study Participants
1982 Youth In Agriculture Studies
Participant
ID Number
a
b
e
d
e
f
g
h
1
J
I.E-2 a M 17 5'5" 132
I.E-2 b F 19 5'5" 115
I.E-2 c M 16 5'6" 130
I.E-2 d M 15 5'8" 130
I.E-2 e F 13 5* 100
I.E-2 f F 24 6' 170
I.E-2 g M 55 5'11" 160
I.E-2 h M 47 S'lO" 190
I.E-2 1 F 25 5'3" 125
I.E-2 J M 41 6*1" 170
I.E-3 a M 17 5'5" 132
I.E-3 b F 19 5'5" 115
1.1-3 c M 16 5*6" 130
I.E-3 d M 15 5'8" 130
I.E-3 • F 13 5* 100
I.E-3 f F 24 6* 170
I.E-3 g M 55 5'11" 160
I.E-3 h M 47 S'lO" 190
I.E-3 1 F 33 5'1" 155
I.E-3 J F 28 5'10' 130
I.E-4 a M 17 5'5" 132
I.E-4 b F 19 5'5" 115
I.E-4 c M 16 5'6" 130
I.E-4 d M 15 5'8" 130
I.E-4 • F 13 5' 100
I.E-4 f F 24 6' 170
I.E-4 g M 55 5'11" 160
I.E-4 h M 47 S'lO" 190
I.E-4 1 F 25 5'3" 125
1.2-4 J M 50 5'8" 200
-------
92
I.E-5
Participant
ID Number
a
b
c
d
•
f
g
h
1
j
Sex
M
F
F
M
M
F
M
M
F
F
Age
15
13
17
12
13
41
21
63
22
46
Height
6
5'5"
5 '4"
5 «4«
5'4"
5'4"
6'
S'S"
5'8"
5.4n
Weight Lbs
143
180
185
105
145
225
235
165
255
250
I.E-6
I.E-6
1.1-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
I.E-6
a
b
c
d
•
f
g
h
1
J
M
F
F
M
M
F
M
H
F
F
15
13
17
12
13
41
47
63
22
46
6'
5'5H
514-
5.4«
5'4"
5'4"
5'10"
5f5"
5'8"
5f4"
143
180
185
105
145
225
190
165
255
250
I.
I.
I.
I.E-7
I.E-7
.E-7
.E-7
.E-7
I.E-7
I.E-7
I.E-7
I.E-7
I.E-7
a
b
c
d
e
£
g
h
1
J
F
F
F
F
M
F
F
F
M
M
10
11
13
18
19
36
33
38
28
47
41
4'8"
5'6"
5'2"
5'11"
5'8"
5'4M
5'4"
6*
5'10"
50
85
100
108
145
115
138
168
165
190
I.
I.
I.
I.
I.
I.
I.
.E-8
.E-8
.E-8
.E-8
.E-8
.E-8
,E-8
I. E-8
I.E-8
I. E-8
b
c
d
•
f
g
h
1
J
M
M
M
M
M
F
F
F
F
F
15
13
14
16
17
68
70
62
77
44
5'4"
5'
5f2"
5'8"
5'6"
5'5"
5'5"
5'3"
5f
5'5"
100
92
95
125
125
153
150
138
150
151
-------
93
Participant
IP Number
a
b
c
d
•
f
g
h
1
J
Sex
M
M
M
M
M
F
P
P
P
P
Age
15
13
14
16
17
68
70
62
77
44
Height
5 '4"
51
5'2M
5*8"
5 '6"
5'5"
5'5n
513-
5*
5'5"
Weight Lbs
100
92
95
125
125
153
150
138
150
151
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
I.E-10
a
b
c
d
e
£
g
h
i
J
M
M
M
M
M
15
13
14
16
17
68
70
62
77
20
5f4n
5'
5'2"
5'8"
5 «6"
515*
S'S"
5'3"
5'
5*8"
100
92
95
125
125
153
150
138
150
150
-------
94
Dermal and Respiratory Exposure Studies
of Adult and Juvenile F1eldworkers,
1983-1984
Research performed by
Mississippi State University
-------
Abstract 95
During the summers of 1983 and 1984 a total of twelve field
studies were conducted which involved a total of 50 pairs of
adult and juvenile workers. As in the other Mississippi studies
these were also designed to assess the dermal and inhalation
exposure of workers to pesticides while harvesting sweet corn,
purple hull peas, and grapes. Pesticides of interest were
endosulfan and benomyl. Samples collected included urine,
exposure pads, cotton gloves, XAD-4 resin (air), ethanol hand
rinses, foliage, and soil.
Dermal exposure to the workers' hands was shown to be the
primary route of exposure as in the other Mississippi studies.
Inhalation exposure was not a significant route of exposure
in these studies. Overall, worker exposure to endosulfan and
benomyl was low and, in almost all cases, juvenile exposure was
less than the adults.
-------
96
STUDY II
1983/1984 DERMAL AND RESPIRATORY EXPOSURE STUDIES
OF ADULT AND JUVENILE VEGETABLE HARVESTERS
Introduction
In a continuation of the study of dermal and inhalation
pesticide exposure experienced by juvenile and adult field
workers during vegetable harvesting activities, the Missis-
sippi Pesticide Hazard Assessment Project conducted twelve
monitoring studies during the summer months of 1983 and
1984. Six studies were conducted each summer involving
monitoring of dermal and inhalation exposure of juvenile/
adult pairs of workers while hand picking purple hull peas,
sweet corn and white Niagara grapes.* Monitoring activities
were carried out during normal working conditions where
pesticides had been applied according to label specifica-
tions and at recommended rates.
As in previous monitored worker exposure studies, cotton
gauze pads were worn by participants at various anatomical
sites to assess dermal exposure. Selection of specific
sites for pad location depended on the potential for expo-
sure during harvesting of a particular crop. Cotton gloves
were also worn to determine the potential for dermal expo-
sure via the hands. Respiratory exposure was monitored for
each worker utilizing DuPont Personal Air Samplers and XAD-
4 resin as the trapping medium.
-------
97
Superficial pesticide residues were determined for each
worksite by collecting foliage and soil saaples for residue
analyses. More detailed descriptions of monitoring and sam-
pling procedures used are given later in this report. Table
1 identifies the six 1983 monitoring sites and study dates,
crops harvested, previous pesticide applications on the
crops, with dates of application and corresponding applica-
tion rates. Table 2 presents similar data for the six stu-
dies in 1984.
Monitoring and sampling procedures used during the 1983/
1984 studies are described below.
Dermal Exposure
To assess dermal exposure of vegetable harvesters, cot-
ton gauze pads were worn by each worker on sites including
forearms, legs, shoulders and head. The actual site de-
pended on the crop harvested. Three inch square pads backed
with glasslne paper were stapled to gabardine bands which
had Velcro strips sewed at each end. Bands were then easily
attached to workers of different sizes by wrapping a band
around an arm or leg with sufficient tightness to prevent
movement out of position during physical activity in the
field. Pads were pinned to clothing at the chest and shoul-
ders and to each side of caps provided each worker by
Project Scientists. Glassine backing on pads prevented con-
tamination by skin oils and perspiration that might be
absorbed through the pads. Prior to use as adsorbant expo-
sure pads, gauze bundles were Soxhlet extracted for 12-16
-------
98
hours with methylene chloride to remove potential interfer-
ences that night appear during electron capture gas chroma-
tographic analyses. At completion of monitored activities,
pads were removed, wrapped in hexane-rinsed aluminum foil
and placed in an ice chest for transport to the laboratory.
Samples were stored in a freezer until analyzed for pesti-
cide residues of interest. Exposure pads from various sites
(i.e. two arm pads, two leg pads, etc.) were analyzed as
composite samples.
To determine the potential for transfer of translocated
or adhering residues from foliage, soil, and vegetable sur-
faces to the workers' hands, cotton gloves were worn by the
participants during their exposure periods and ethanol hand
rinses were obtained Immediately following the harvesting
activity. Prior to use, gloves were laundered and then
extracted with acetone. At completion of the monitored pe-
riod, the workers' gloves were removed, wrapped in aluminum
foil, transported to the Lab, and frozen. Gloves from each
participant were analyzed as one composite sample. Ethanol
hand rinses were collected in solvent rinsed bottles follow-
ing the monitored period, and were stored under refrigera-
tion until analyzed. A composite sample of approximately 50
mis/hand rinse was obtained from each worker.
Respiratory Exposure
During harvesting activities, each adult/juvenile parti-
cipant wore a DuPont P-4000 Personal Air Sampler with the
-------
99
cipant wore a DuPont P-4000 Personal Air Sampler with the
flow-rate precalibrated at 2 liters/minute. The adsorbant
medium, 0.5 grams of XAD-4 resin, was contained in a car-
tridge attached to the sampler by Tygon tubing. Start and
stop times of the samplers were recorded for subsequent air
volume calculations; flow control light-emitting diodes of
the samplers were monitored to insure -that proper flow had
been maintained. At the end of the monitored period, each
air sampling medium was wrapped in aluminum foil, transfer-
red to the Lab on ice, and frozen.
Foliage Sampling
Five composite foliage samples were collected by Field
Investigators at each site during the harvesting acti-
vity according to the following schenre.
Sampling points for the five composite foliage samples
were selected as illustrated in the following diagram.
1234 5
I x x x x x
4. x x x X -X
4. -_-x--------x--- x — X---------X—
+ x x x x x
Key: - crop row
+• sampling path direction
x- sample points for Foliage and Soil
1,2,3,4,5, - sampling paths
Samples were collected as the investigator moved in a
path across the field perpendicular to the crop rows. Sam-
pling path i3 was at mid-field, while sampling paths II & 12
-------
too
Five leaf punches (each 2.54 cm in diameter) were taken from
each plant in the sampling path; one punch from the top
foliage, two punches from opposite sides of the plant at
mid-height, and two punches from opposite sides at the
lowest foliage point. Leaf samples were collected in amber
colored glass jars which were pre-rinsed in the laboratory
with acetone and petroleum ether. Jar lids were lined with
aluminum foil. The total number of plant discs in each
composite sample obviously depended on the number of crop
rows. This sampling scheme provided the flexibility re-
quired to fit any site while insuring that representative
samples were obtained for residue analyses. Samples were
transported to the lab on ice and stored under refrigeration
(not frozen) until analyzed for surface residues of inter-
est.
Samples of vegetables (i.e. corn and peas) which were
being harvested were also collected at each monitoring site.
Pea shells and corn husks were analyzed for surface residues
by the same procedures used for determining dislodgeable
residues on foliage.
Soil Sampling
Five composite soil samples were collected at each moni-
toring site during the harvesting activity. Samples were
collected at each of the plant sampling points as designated
in the diagrammed sampling scheme. Approximately 10 grams
was collected with a stainless steel scoop at each point
-------
101
(for each of the five sampling paths) from the top half inch
of soil. Samples were placed in amber colored glass jars
which had been pre-rinsed with acetone. Lids were lined
with aluminum foil; samples were transported on ice and kept
frozen until analyzed.
Urine Sampling
Urine samples were collected from each adult/juvenile
study participant prior to (pre-exposure sample) and for
several days (depending on pesticide of interest) following
each agricultural activity that was monitored. All urine
voids each day were collected by each worker. Individual
samples were collected in bottles which were furnished by
the Project and had been rinsed previously with acetone and
petroleum ether. Screw caps containe'd Teflon disks to pre-
vent sample contact with plastic. Participants were in-
structed to store collected urine samples under refrigera-
tion until they were picked up by Project personnel. When
delivered to the laboratory on ice, the samples were stored
in a freezer until analyzed for the parent compounds and/or
urinary metabolites. Prior to analyses, samples were compo-
sited according to schemes agreed upon between Project che-
mists and EPA/OPP personnel.
The numbers of each type sample (urine, gauze pads,
cotton gloves, XAD-4 resin, ethanol rinses, foliage and
soil) which were collected for pesticide residue analyses
from the six 1983 studies are summarized in Table 3. Simi-
-------
102
lar numbers for samples collected from the six 1984 studies
are presented in Table 4.
-------
103
1983 Studies
Studies 1-83, 11-83 and 111-83: On three dates in July and
August, 1983, a total of fifteen pairs of juvenile/adult
workers were monitored for endosulfan exposure (dermal and
inhalation) while harvesting purple hull peas at a site at
Louisville, Mississippi. The number of acres harvested on
each date and the applicable pesticide application history
for the monitored field site are presented in Table 1. The
total acres harvested on each day of monitoring (i.e. 2, 2
and 4 acres for Studies 1, 11 and 111 respectively) repre-
sent work performed in two adjacent fields over one con-
tinuous period of time. Notice in Table 1 that endosulfan
applications were made to the site 11, 3 and 4 days prior to
Studies I, II and III respectively. The longer interval
between application and harvest for Study I (11 days), com-
pared to 3 and 4 days for Studies II and III should be
reflected in exposure data for the three studies. Analyti-
cal results for endosulfan on/in gauze pads, cotton gloves,
ethanol hand rinses and XAD-4 resin, for each of the three
studies (I, II and III) are presented in Tables 5, 11 and 17
(pads); 6, 12 and 18 (gloves); 7, 13 and 19 (rinses); and 8,
14 and 20 (XAD resin). All tables of endosulfan data pre-
sent values for the two isomers, endosulfan I and II, as
well as for the degradatlve product endosulfan sulfate. A
total endosulfan value appears in each table and is the sum
of reported endosulfan I, II and sulfate levels. Lower
levels of detection (LLDs) are presented in each table of
-------
104
data for each of these three compounds, and are expressed
in the appropriate units of measure for the particular sub-
strate. LLDS for each of the three compounds are based on
absolute values of 1, 2 and 5 nanograms respectively for the
I and II isomers and the sulfate. The absolute value for
each represents the lowest level of the particular compound
that can be detected on or in any substrate (i.e. gauze
pads, glove, XAD resin, etc.).
Analytical results for gauze pads from Studies 1, II and
III (Tables 5, 11 and 17 respectively) show endosulfan (I
and II) levels in the nanogram per square centimeter range
for both anatomical sites (i.e. forearm and thigh). Levels
on arm and leg pads from Study I were noticeably lower than
those from Studies II and III, where comparable levels were
found. In all three studies, levels found on leg pads were
typically higher than those on arm pads for a particular
worker, whether adult or Juvenile. This finding suggests
that the potential is greater for dermal exposure to the
thigh area of workers (i.e. pea harvesters) than to the
forearm.
Results for gloves from the three studies shown in
Tables 6, 12 and 18 indicate endosulfan was present in nano-
gram quantities as the I and II isomers and as the sulfate.
Comparable levels were found on gloves from Studies II and
III and were considerably higher than levels on gloves from
Study I. Endosulfan residues in ethanol hand rinses from
Studies II and III (Tables 13 and 19 respectively) appeared
-------
105
to be present at slightly higher nanogram levels than from
Study I (Table 7). Residues in air samples from Studies II
and III (Tables 14 and 20) were in the nanogram per cubic
meter range and were noticeably higher than those from Study
I (Table 8) where no residues were detected.
As stated previously. Studies I, II and III were con-
ducted at the same site at Louisville, MS and each involved
harvesting activity in two adjacent fields. Since two
fields were involved in each study, five composite foliage
samples (i.e. leaf punches) and five soil samples were col-
lected from each field. Analytical results for the ten com-
posite foliage samples collected during each of the three
studies are presented in Tables 9, 15 and 21 for Studies I,
II and III respectively. The results obviously indicate
that Field 12 was treated at very low application rates, or
not at all. Analytical results for the five composite
foliage samples collected from Field ll during each of the
three studies show endosulfan I, II and sulfate present at
nanogram per square centimeter levels. Higher levels were
found on foliage from Studies II and III (Tables 15 and 21)
than were found on foliage from Study I (Table 9). As
pointed out previously, endosulfan applications were made to
the field site for Studies II and III only three and four
days prior to the monitored harvest, while an application
was made to the site for Study I eleven days prior to har-
vest. Apparently, the additional 7-8 day period between
application and harvest for the Study I site resulted in
-------
106
greater degradation of endosulfan residues or loss due to
rain and other environmental factors. The higher endosulfan
levels on foliage from Studies II and III compared to Study
I, likely resulted in higher residues on absorptive media
worn by workers in Studies II and III (i.e. gauze pads,
gloves, XAD resin) and in ethanol hand rinses. Another
factor should be considered. The longer periods of expo-
sure experienced by workers in Studies II and III (130
minutes in each study) compared to 91 minutes for workers in
Study I would also be expected to contribute to increased
levels of endosulfan on adsorptive media and in hand rinses.
Analytical results for soil samples presented in Tables
10, 16 and 22 show endosulfan residues at comparable levels
(ppb) in Field #1 for all three studies. The absence of re-
sidues in samples from Field #2 for Studies I and II (Tables
10 and 16) again suggest the fields were treated at very low
application rates or not at all. Residue values for soil
from Field £2 in Study III (Table 22) show endosulfan pre-
sent, but at very low levels (ppb) compared to Field 11 for
the same study.
Individual urine voids were collected by each juvenile
and adult worker for three days following the harvesting
activity. All collected samples were composited for each
worker into two daily samples (i.e. one morning and one
evening sample). A total of 210 composites were analyzed
for residues of endosulfan I, II and sulfate. No residues
were detected in any samples.
-------
107
Studies IV-83 and V-83; On two dates in August, 1983 four
pairs of juvenile/adult workers were monitored for dermal
and respiratory exposure to endosulfan while harvesting
sweet corn at a site at Louisville, Mississippi. The two
studies were conducted three days apart, and as specified in
Table 1, the 0.75 acre field had received four previous
applications of endosulfan (Thiogard 3) at a rate of 0.11
pounds active Ingredient per acre. The last application was
made two weeks prior to Study IV-83. Since harvesting corn
involved the potential for dermal contact of workers to
foliage In the head, face and neck area as well as arms and
legs, cotton gauze pads were worn by each worker on the
shoulders, head, forearms and thighs. Pads for the head
were pinned to each side of baseball caps which were fur-
nished each worker. Pads for shoulders were pinned to
workers' clothing and pads for forearms and thighs were
attached to adjustable bands to fit arms and legs of varying
sizes. Other samples collected for endosulfan residue ana-
lyses were cotton gloves, ethanol hand rinses, XAO resin
from DuPont air samplers, soil, foliage from corn stalks,
and urine. Pairs of samples such as gauze pads, gloves and
hand rinses were analyzed as composite samples. All indivi-
dual urine voids were collected by each worker for three
days following each harvesting activity, but were composited
into two daily samples (one morning and one evening sample)
for each collection day. Analytical results for gauze pads
from Studies IV and V are presented in Tables 23 and 29.
-------
108
Low levels of endosulfan I, II and sulfate (ng/cm ) were
found on pads from all four anatomical sites in both stu-
dies. Higher levels appeared to be present on pads from
Study IV. A similar result was obtained for gloves, as
shown in Tables 24 and 30, where mlcrogram quantities were
detected. Nanogram levels of endosulfan I and II were found
in hand rinses from both studies (Tables 25 and 31); again,
slightly higher levels resulted from Study IV. Results for
air samples are presented in Tables 26 and 32, which also
show higher levels (ng/m ) in the XAD resin from Study IV.
Five composite foliage and soil samples were collected
during each study for residue analyses, and foliage results
are shown in Tables 27 and 33 for Studies IV and V. Soil
results appear in Tables 28 and 34. As seen in Tables 27
and 28, endosulfan residue levels were higher on foliage and
soil from Study IV than from Study V. Apparently the higher
levels, particularly on foliage, were responsible for ele-
vated endosulfan residues on absorptive media (pads, gloves
and XAD resin), and in hand rinses from workers in Study IV
even though the exposure time (45 minutes) was considerably
shorter than that for Study V (78 minutes). Urine samples
collected by each worker for three consecutive days fol-
lowing harvest were composited into two samples for each
day. Samples were analyzed for endosulfan I, II and sulfate
residues. None were detected in any urine samples.
Composite foliage and soil samples were collected from
Study site V for several months after the study to observe
-------
109
the rate of degradation of endosulfan residues in the
environment. Since no additional insecticide applications
were to be made to the crop, sampling began on August 17.
Sampling was completed on November 21, 1983 for foliage and
February 10, 1984 for soil. Analytical results for foliage
samples shown in Table 35 indicate that endosulfan was
present primarily as isomer II and the sulfate in the ini-
tial samples collected August 17, taken 18 days after the
final insecticide application. By August 26 (27 days post
application) almost no endosulfan I was present; endosulfan
sulfate was the primary residue found. This trend continued
through the final sampling in November 1983, where total
endosulfan levels remained about the same as those found in
late August and early September.
Analytical results for soil samples collected for the
endosulfan degradation study are presented in Table 36.
Initial samples collected on August 17 contained endosulfan
I and II at comparable part per billion levels, with essen-
tially no sulfate present. By September 2 (34 days post
application) endosulfan I levels had decreased such that
endosulfan II was the major compound present. During the
succeeding month this decrease continued, with a corre-
sponding appearance of endosulfan sulfate residues. By
October 7 (69 days post application) almost no endosulfan I
was found In soil samples, at which time endosulfan II and
endosulfan sulfate appeared to be present at equivalent lev-
els. Results for samples collected in November and December
-------
no
appeared erratic. Some contained relatively high levels of
endosulfan compared to Initial sample levels. Indicating
little decrease In total endosulfan. Three of five compo-
site soil samples collected in December 1983 and February
1984 contained no traces of endosulfan residues.
Study VI-83; Study VI-83, Table I, Involved monitoring the
dermal and inhalation exposure of 3 pairs of adult and
juvenile workers while harvesting white Niagara grapes at a
Starkville, MS vineyard which had received applications of
several insecticides and fungicides. Gauze exposure pads
were worn on forearms and thighs of each worker. Cotton
gloves were also worn during harvesting. Ethanol hand rin-
ses were collected at completion of the monitored activity.
Inhalation exposure of each worker was monitored with
DuPont P-4000 air samplers, using XAD resin as the adsor-
bant. Urine composites were collected by workers for three
days following the rape harvest. Composite foliage and soil
samples were also collected at the vineyard during the
monitored activity. Since our scientists and EPA personnel
(OPP/Exposure Assessment Branch) were primarily interested
in exposure of grape harvesters to Benomyl, collected expo-
sure samples were analyzed for residues of the parent com-
pound as well as its primary degradation product methyl-2-
-benzimidazole carbamate (MBC). As indicated in Tables 37
and 38, no residues of either compound were found on gauze
pads or cotton gloves, nor in hand rinses. Since no resi-
-------
dues were detected in any of these samples Indicating dermal
exposure to benomyl, the remaining collected samples (XAD
resin, urine, foliage and soil) were not analyzed. Appar-
ently, benomyl and MBC residues had decreased to nondetect-
able levels during the three month period following appllca
tion in early May, 1983*
Physical characteristics of all juvenile and adult wor-
kers in Studies I through VI-83 are given in Table 39. An
indication of the productivity of each worker is also given
in the table as an estimate of the buckets harvested during
each monitored activity.
-------
1 12
1984 Studies
Study 1-84; On June 21, 1984. field investigators conducted
the first study of the summer at Louisville, Mississippi.
Five pairs of juvenile/adult workers were monitored for
dermal and respiratory exposure to endosulfan while hand
picking sweet corn from a 1.5 acre field which had received
two previous applications of Thiogard-3 (see Table 2). Sam-
ples collected for endosulfan residue analysis included
gauze exposure pads (four composite samples from each wor-
ker), cotton gloves (one composite sample from each worker),
ethanol hand rinses (one composite rinse per worker), and
XAD resin (One sample from each worker's DuPont P-4000 air
sampler). Composite foliage and soil samples were collected
from the monitored site as described previously in this
report. All individual urine voids were collected by each
worker for three days following the harvest activity.
Prior to analysis, urines were composited into two daily
samples from each worker for each collection day. Analyti-
cal results for gauze exposure pads presented in Table 40
show nanogram per square centimeter levels of endosulfan 1
and II on pads from all four anatomical sites (i.e. forearm,
thigh, head, shoulder). Higher total endosulfan levels on
arm and leg pads compared to levels from shoulder and head
sites for all workers indicate less potential exists for
dermal exposure in the face and shoulder area. Only a few
exposure pads contained detectable levels of endosulfan sul-
fate. Analytical results for cotton gloves worn by workers
-------
113
while picking corn are presented In Table 41. Endosulfan I,
II and sulfate were found in microgram quantities. The
concentration ratio of II to I in all 10 samples was approx-
imately 2:1, with considerably lower levels of the sulfate
present. Analyses of hand rinses, Table 42, indicate micro-
gram levels of endosulfan I and II were present at much
lower concentrations than on the workers' gloves. Air sam-
ples collected by each worker during the harvesting activity
contained nanogram per cubic meter levels of endosulfan I
and II at a concentration ratio of 1:2. Table 43 shows that
no residues of the sulfate were found on the XAD resin
adsorbant used in the DuPont air samplers. Five composite
foliage and soil samples were collected from the field site
during the harvest operation, and on each of the following
three days. Analytical results for the foliage and soil
samples are presented in Tables 44 and 45 respectively.
Nanogram per square centimeter levels of endosulfan I, II,
and sulfate were found on foliage discs from each of the
four days of collection. Levels on day four appeared un-
changed from those of day one (i.e. day of harvest). Analy-
tical results for composite soil samples (Table 45) col-
lected on the same four days show part per billion levels of
endosulfan I, II, and sulfate. An approximate four-fold
increase in total endosulfan levels on June 23 suggests that
an endosulfan application might have been made that day, but
the farm owner confirmed that none was made. Rain that
•orning prior to collection of samples resulted in an in-
-------
114
crease In soil moisture In samples (from 2Z to approximately
10Z), which apparently facilitated the extraction of resi-
dues from soil. Under dry conditions (e.g. 2Z), residues
would likely not have been removed as easily. This ob-
served effect serves as a reminder that dlslodgeable resi-
dues are being determined, and that exhaustive extractions
would likely result in higher endosulfan values. Urine
samples collected by all workers were composited into two
daily samples for each day of collection (three days), and
then were analyzed for residues of endosulfan I, II and sul-
fate. No residues of the three compounds were detected in
any urine samples.
Studies II and 111-84: On two dates in June, 1984, a total
of ten pairs of juvenile/adult field* workers were monitored
for dermal and inhalation exposure to endosulfan while hand
picking sweet corn at a Louisville, MS site. As indicated
in Table 2, the 1.5 acre corn plot received three applica-
tions of Thiogard-3 that month. Studies II and III were
conducted three and two days respectively, following sepa-
rate insecticide applications. Samples collected for endo-
sulfan residue analysis included gauze pads, cotton gloves,
ethanol hand rinses, XAD-4 resin, urines, corn foliage and
soil. Analytical results for exposure pads from Studies II
and III are presented in Tables 46 and 52 respectively.
Slightly higher levels of endosulfan (i.e. totals for I, II
and sulfate) were found on pads from workers in Study III
-------
115
than Study II. Residues were in the nanogram per square
centimeter range, and were present primarily as endosulfan
II. Results for gloves for Studies II and 111-84 presented
in Tables 47 and 53 respectively, show endosulfan I, II and
sulfate were found at microgram levels with endosulfan II
present at the highest concentration. Total endosulfan val-
ues in Table 53 (Study 111-84) also appear to be approxi-
mately twice those values for Study 11-84 (Table 47). Simi-
lar results were obtained for ethanol hand rinses from Stu-
dies II and III, shown in Tables 48 and 54 respectively.
Lower microgram levels were found in hand rinses compared to
levels on gloves, and endosulfan II was present at higher
concentrations than endosulfan I and sulfate. Analytical
results for air samples (XAD resin) from Studies II and
111-84, presented in Tables 49 and 55 respectively, show the
presence of nanogram per cubic meter levels of only endosul-
fan I and II. Total endosulfan levels for Study III in
Table 55 also appear to be higher than total endosulfan air
levels for Study II. As described earlier in this report.
five composite foliage and soil samples were collected on
the day of the monitored harvest, and each of the following
three days. Results from analyses of foliage samples for
Studies II and 111-84 are presented in Tables 50 and 56
respectively. They are expressed in nanograms per square
centimeter for endosulfan I, II and sulfate. As indicated
in the tables, total endosulfan values for foliage discs
collected during Study III harvest (June 30, 1984) appear
-------
116
generally higher than total levels for samples collected
during Study II harvest (June 26. 1984). Since exposure
times for workers in Studies II and III differed by only
five minutes (105 and 110 minutes respectively), the appa-
rent higher endosulfan levels on foliage during Study III
likely resulted in the higher levels found on pads, gloves,
XAD resin and in hand rinses of its workers compared to
those in Study II. Higher foliage levels seen during Study
III would certainly be expected, since the crop had received
three endosulfan applications by that time compared to two
applications at the time of Study 11-84 (see Table 2). The
effects from the third endosulfan application are readily
seen in Table 50 for foliage samples collected on June 28,
1984. The significant increase in residue levels from June
27 to 28 is the obvious result of an insecticide application
made on the morning of June 28. Analytical results for com-
posite soil samples collected at the field site during the
two studies and for three days following are presented in
Tables 51 and 57. These show higher part per billion levels
of endosulfan in soil samples collected during Study III (on
6/30/84) than during Study II (on 6/26/84). These higher
levels on soil likely contributed to the higher levels found
in exposed media in Study III compared to those for Study
II. The effects from the June 28 application of endosulfan
to the crop are seen in Table 51 for samples collected that
day* The Increased soil residue levels from the previous
day are obvious, though such Increases were not as dramatic
-------
117
as those on foliage. Urine samples voided by each worker
for three days following the harvest were composited Into
two daily samples and analyzed for endosulfan residues. No
residues were detected in any urine samples.
Study IV-84t On July 12, 1984 the MS PHAP conducted the
fourth EPA/DOL Youth in Agriculture Study of the summer at
Louisville, Mississippi. Investigators monitored the dermal
and Inhalation exposure of five pairs of juvenile/adult
workers while harvesting sweet corn from a 1.5 acre field
which had received three previous applications of endosulfan
(Thiogard-3). Application rates and rates (Ibs. active
ingredient per acre) are specified in Table 2. Exposure me-
dia for workers, foliage, soil and urine samples were col-
lected as previously described in thi's report and analyzed
for endosulfan I, II and sulfate residues. Analytical re-
sults for gauze exposure pads presented in Table 58 show le-
vels of endosulfan I and II (ng/cn? ) on pads from all four
anatomical sites. Microgram quantities of endosulfan I, II
and sulfate were found on workers' gloves worn during har-
vest (Table 59). The endosulfan II isomer was the major
compound found on gloves. Ethanol hand rinses also con-
tained microgram levels of endosulfan I and II (Table 60).
Results for air samples in Table 61 show only endosulfan I
trapped on XAD resin at fairly low levels (ng/m ). Foliage
samples collected on the day of harvest and for three
successive days contained low levels of endosulfan I, II and
-------
1 18
sulfate (ng/cm2 ), shown In Table 62. As in previous stu-
dies, significant degradation of foliage residues was not
apparent over the four day period. Analytical results for
composite soil samples collected for the four day period are
presented in Table 63. Part per billion levels of endosul-
fan I, II and sulfate were found. As with the dislodgeable
residues on foliage, little degradation or loss was evident
over the four day period. Urine the harvest contained no
detectable levels of endosulfan I, II or sulfate.
Study V-84; On July 25, 1984 field investigators monitored
the dermal and respiratory exposure of six pairs of juve-
nile/adult workers while hand picking purple hull peas from
a three acre field at Louisville, Mississippi. As specified
in Table 2, endosulfan (Thiogard-3) 'was applied to the crop
three times in July. The final application was made three
days prior to the monitored harvest. Exposure media (i.e.
gauze pads, cotton gloves and XAD-4 resin), foliage discs,
soil and urine samples were collected and analyzed for
residues of endosulfan I, II and sulfate. Analytical re-
sults for gauze exposure pads are shown in Table 64. Pads
were worn by workers at two anatomical sites, forearms and
legs (placed slightly above the knee). Endosulfan I and II
were found at nanogram per square centimeter levels. No re-
sidues of endosulfan sulfate were detected on exposure pads.
Microgram quantities of endosulfan I, II and sulfate were
found on gloves worn by Study V workers (Table 65). Equiva-
-------
119
lent levels of I and II appeared to be present at higher
concentrations than the sulfate. Hand rinses contained only
endosulfan I and II in microgram quantities (Table 66).
Analytical results for personal air samples shown in Table
67 indicate the presence of endosulfan I and II (on XAD re-
sin) at fairly low levels in the ng/m3 range. Results from
analyses of foliage samples collected during harvest (7-25-
84) and for three successive days are seen in Table 68.
Analytical results are also given in the table for dislodge-
able residues on five composite samples of purple hull peas
collected at the field site during harvest. As reported,
equivalent levels (ng/cnO of endosulfan I, II and sulfate
were found on pea hulls and foliage. No appreciable degra-
dation nor loss of residues on foliage was apparent over the
four day sampling period. Similar results were obtained for
composite soil samples collected on the day of harvest and
for three successive days. As seen in Table 69, part per
billion concentrations of endosulfan I, II and sulfate on
soil remained fairly constant over the sampling period of
four days. Urine samples collected by workers for three
days following the harvest were combined into two composites
per worker per day, and analyzed for endosulfan I,II and
sulfate. No residues were detected in any samples.
Study VI-84; On August 9, 1984 Project personnel conducted
the sixth study of the summer. This involved the monitoring
of dermal and respiratory exposure of four adults and five
-------
120
juveniles to Benomyl while picking grapes at a Starkvllle,
MS vineyard (1.75 ares). As specified In Table 2, Benomyl
(50Z WP) had been applied to the vineyard on two dates, May
14 and July 2. Slightly over five weeks then elapsed bet-
ween the final application and the monitoring study. Gauze
exposure pads were worn on the forearms, shoulders and chest
of each worker. Composites were made for each anatomical
site prior to analysis. Cotton gloves were worn by each
worker during harvest; ethanol hand rinses were collected
from each worker at the end of the picking time. All parti-
cipants wore DuPont P-4000 air samplers (with XAD resin
adsorbant) to assess respiratory exposure while working.
Each worker collected all his/her urine voids for three days
following the grape harvest. These were composited into two
samples per day per orker. Foliage and soil samples were
also collected from the harvest site. Gauze exposure pads,
cotton gloves and ethanol hand rinses were analyzed for
residues of Benomyl and its major environmental metabolite,
methyl-2-benzimldazole carbamate (MBC). As indicated in
Tables 70 and 71, no residues of either compound were found
on gauze pads, cotton gloves, or in hand rinses. Since no
residues of Benomyl or MBC were found on these media, which
would indicate a potential for dermal exposure, the re-
maining samples (XAD resin, urine, foliage and soil) were
not analyzed.
Physical characteristics of all juvenile and adult wor-
kers for Studies I through VI-84 are presented in Table 72.
-------
121
The table also shows the relative productivity (and presum-
ably exposure) of workers by the bushels (I.e. corn, peas,
grapes) that each harvested.
Weather Data
For each of the 12 exposure studies conducted in 1983 and
1984, the following data were recorded:
a. Maximum temperature
b. Relative humidity
c. Wind speed, direction and condition
d. Rainfall
e. Cloud cover.
Table 73 presents the significant weather conditions found
during these 1983 and 1984 studies.
Quality Control
Specific procedures used in these 1983/1984 studies to moni-
tor dermal and inhalation exposure of field workers and to
collect environmental samples for residue analyses have been
described previously in appropriate sections of this report.
All procedures were conducted as specified by established
EPA/MSCL QA/QC protocols. General quality control proce-
dures adopted by our laboratory (record keeping, analytical
reference standards, Instrument maintenance and purity of
solvents and reagents) are described In the MS PHAP QA
Project Plan for Dermal and Respiratory Pesticide Exposure
Assessment of Adult and Juvenile Vegetable Harvesters and
Field Workers submitted to EPA and approved by the EPA/OPP/
-------
122
QAO.
Analyses for endosulfan (i.e. I, II and sulfate) an
adsorption media (i.e. gauze pads, cotton gloves, XAD
Resin), ethanol hand rinses, urine, foliage and soil were
performed by residue methods used for toxaphene, described
in the Analytical Methods Development Sections of MS PHAP
Annual Progress Reports 114 and _1_5 (March 9, 1983 and May
29, 1984, respectively). Analyses for benomyl and MBC were
performed by modifications of the following published me-
thods :
a) Singh, R.P. and M. Chiba (1985) J. Agri. Food Chem.
32 63-67.
b) Gonzales, S.A., FDA Laboratory Information Bulletin
No. 2454, December 17, 1980, p. 1-5.
Prior to HPLC analysis, sample extracts and benomyl standard
solutions were allowed to stand overnight to insure complete
conversion to MBC.
Analytical results for quality control samples analyzed
during 1983 and 1984 Youth In Agriculture monitoring studies
are presented in Tables 74-77. Data were obtained from
analyses of spiked substrate which were included in sets of
each type sample analyzed. Results for recoveries of endo-
sulfan (I, II and sulfate) from adsorption media, hand
rinses and foliage are shown in Tables 74 and 75 for 1983
and 1984 studies respectively. Since soil and urine
samples from 1983 and 1984 endosulfan studies were ana-
lyzed simultaneously, the two studies had one common set of
quality control samples. These results are presented in
-------
123
Table 76. Samples collected from 1983 and 1984 benomyl
studies were also analyzed at the same time. Table 76 also
contains QC data for 1983 and 1984 recoveries of MBC
(Me thyl-2-benzimidazole carbaaate, the primary benomyl meta-
bolite) from adsorptive media. As indicated in Tables 74-
76, results of acceptable accuracy and precision were ob-
tained for endosulfan and benomyl (MBC). Sample standard
deviations (on-l)* were calculated using a Casio fx-85
scientific calculator.
Recoveries of endosulfan from spiked adsorption media
(i.e. gauze pads, gloves and XAD resin) stored in laboratory
freezers for varying lengths of time (34-44 weeks) are
presented in Table 77. As indicated, little loss of resi-
dues was evident over the extended storage period at -18 C.
* an-l *
n-1
-------
Table 1
1983 Youth in Agriculture Studies
Study
No
1-83
11-83
111-83
IV-83
V-83
VI-83
Date
Site Sample
Louisville 7/29
Louisville 8/1
Louisville 8/5
Louisville 8/13
Louisville 8/16
Starkvllle 8/18
Crop Acres
Type Harvest
Peas 2
Peas 2
Peas 4
Corn 0.75
Corn 0.75
Grapes 0.6
Pesticide
Bndosulf an
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Benomyl
Mancozeb
Carbaryl
Folpet
Formulation
Thiogard 3*
(9.7Z AI)
Thiogard 3
Thiogard 3
Thiogard 3
Thiogard 3
Benlate-
50 WP
Dithane-
M-43
Sevln 80 WP
Phaltan 50 UP
Appl.
Rate**
I/A
0.03
0.03
0.03
0.11
0.11
0.75
2.0
2.0
5.0
Appl
Date
7/16
7/18
7/16
7/18
7/29
7/16
7/18
7/29
8/1
7/2
7/16
7/23
7/30
7/2
7/16
7/23
7/30
5/6
5/6
5/6
6/24
*Thiogard-3, Thiodan Insect Spray, Security Brand, Woolfolk Chemical Works
Inc., Ft. Valley, GA
**Active Ingredient
r\>
-------
Table 2
1984 Youth In Agriculture Studies
Study
No.
1-84
11-84
111-84
IV-84
V-84
VI-84
Date
Site Saaple
Louisville 6/21
Louisville 6/26
Louisville 6/30
Louisville 7/12
Louisville 7/25
Starkvllle 8/9
Crop Acres
Type Harvest
Corn 1.5
Corn 1.5
Corn 1.5
Corn 1.5
Peas 3'.0
Grapes 1.75
Pesticide
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Benoayl
Zolone
Captan
Benoayl
Formulation
Thiogard-3
(9. 71 AI)
Thlogard-3
Thiogard-3
Thlogard-3
Thlogard-3
50Z WP
34. 41 EC
50Z HP
50Z WP
Appl.
Rate**
*/A
0.095
0.095
0.19
0. 19
0.19
0.19
0.19
0.095
0.190
0.095
0.095
0.095
0.095
0.50
0.19
1.0
0.75
Appl
Date
6/5
6/19
6/15
6/23
6/15
6/23
6/28
6/27
7/3
7/10
7/8
7/11
7/22
5/14
7/2
7/2
7/2
*Active Ingredient
ro
-------
126
Table 3
1983 DOL/EPA Youth In Agriculture Studies
Samples Collected For Analysis
Study Nos.: 1-83, 11-83,
111-83 Crop/Pesticide:
Peas/Endosulfan Adult/
Juvenile Pairs: 15
Study No.: VI-83 Crop/
Pesticide: Grapes/Benomyl
Adults/Juveniles: 3
Samples
Collected
Number
Collected
Samples
Collected
Number
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
XAD Resin (Air)
Hand Rinse
Total
405
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
XAD Resin (Air)
Hand Rinse
Total
82
Study Nos: IV-83, V-83
Crop/Pesticide: Corn/Endosulfan
Adult/Juvenile Pairs: 4
Samples
Collected
Number
Collected
Urine 52
Exposure Pads 32
Cotton Gloves 8
Foliage 10*
Soil 10*
XAD Resin (Air) 8
Hand Rinse 8
Total
128
* An additional 70 soil samples and 55 foliage samples
were collected for Endosulfan residue degradation
study; 740 samples total
-------
Table 4
1984 DOL/EPA Youth In Agriculture Studies
Samples Collected For Analysis
127
Study Nos.: I, II, III
and IV-84 Crop/Pesticide:
Corn/Endosulfan Adult/
Juvenile Pairs: 20
Study No.: VI-84 Crop/
Pesticide: Grapes/Benomyl
Adults/Juveniles: 4/5
Samples
Collected
Number
Collected
Samples
Collected
Number
Collected
Urine
Exposure Pads
Cotton Gloves
Foliage
Soil
XAD Resin (Air)
Hand Rinse
Total 1,077
Urine 113
Exposure Pads 27
Cotton Gloves 9
Foliage 20
Soil 20
XAD Resin (Air) 9
Hand Rinse 9
Total 207
Grand Total
1 .469
Study No.: V-84
Crop/Pesticide: Peas/Endosulfan
Adult/Juvenile Pairs: 6
Samples
Collected
Number
Collected
Urine 105
Exposure Pads 24
Cotton Gloves 12
Foliage 10
Soil 10
XAD Resin (Air) 12
Hand Rinse 12
Total
185
-------
Table 5
Analytical Results For Gauze Pads
Study No. 1-83
128
Endosulfan
Lab No.
688963
688964
688965
688966
688967
688968
688969
688970
688971
688972
688973
688974
688975
688976
688977
688978
688979
688980
688981
688982
Worker I.D. Pad
Youth Adult Site
1-83-1 Arm
Leg
1-83-2 Arm
Leg
1-83-3 Arm
Leg
1-83-4 Arm
Leg
1-83-5 Arm
Leg
1-83-6 Arm
Leg
1-83-7 Arm
Leg
1-83-8 Arm
Leg
1-83-9 Arm
Leg
1-83-10 Arm
Leg
I
ND*
0.06
ND
ND
ND
ND
ND
0.02
0.04
ND
ND
ND
ND
ND
0.06
0.02
ND
ND
ND
ND
ng per
II
ND
0.44
ND
ND
ND
ND
ND
0. 17
0.06
0.04
ND
ND
ND
ND
0.19
0.12
ND
0. 14
ND
0.10
cm*
S
ND
0.11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
0.61
ND
ND
ND
ND
ND
0. 19
0. 10
0.04
ND
ND
ND
ND
0.25
0. 14
ND
0. 14
ND
0.10
*ND-None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
129
Table 6
Analytical Results For Gloves
Study No. 1-83
Endosulfan
Lab No.
689043
689044
689045
689046
689047
689048
689049
689050
689051
689052
Worker
Youth
1-83-1
1-83-2
1-83-3
1-83-4
1-83-5
I.D.
Adult
1-83-6
1-83-7
1-83-8
1-83-9
1-83-10
I
ND*
313
51
37
120
45
ND
452
ND
ND
Total
II
110
819
363
165
421
161
289
1,110
194
121
ng
S
ND
83
80
ND
ND
ND
43
102
31
ND
Total
110
1 ,220
494
202
542
205
332
1,660
225
121
*ND=None Detected
Lower Level of Detection
1.0
2.0
5.0
-------
Table 7
Analytical Results For Hand Rinses
Study No. 1-83
130
Endosulfan
Lab No.
685570
685571
685572
685573
685574
685475
685576
685577
685578
685579
Worker
Youth
1-83-1
1-83-2
1-83-3
1-83-4
1-83-5
I.D.
Adult
1-83-6
1-83-7
1-83-8
1-83-9
1-83-10
I
ND*
262
93
ND
ND
ND
ND
550
517
ND
Total
II
ND
581
97
ND
ND
ND
ND
851
ND
ND
ng
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
843
190
ND
ND
ND
ND
1,400
517
ND
*ND»None Detected
Lower Level of Detection
1.0
2.0
5.0
-------
Table 8
Analytical Results For Air Samples
Study 1-83
Endosulfan
Lab No.
685560
685561
685562
685563
685564
685565
685566
685567
685568
685569
Worker
Youth
1-83-1
1-83-2
1-83-3
1-83-4
1-83-5
I.D.
Adult
1-83-6
1-83-7
1-83-8
1-83-9
1-83-10
I
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ng per ms
II
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*ND=None Deteceded
Lower Level of Detection
5.5
11.0
27.5
-------
132
Table 9
Analytical Results For Foliage
Study No. 1-83
Endosulfan
ng per cm2
Lab No.
684455
684456
684457
684458
684459
684460
684461
684462
684463
684464
Sample site
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
1
1
1
1
1
2
2
2
2
2
I
0.06
0. 19
0.01
0.07
0.11
ND*
ND
ND
ND
ND
II
0.39
0.89
0.08
0.31
0.65
ND
ND
ND
ND
ND
S
0.72
3.04
0.13
0.39
1.29
ND
ND
ND
ND
ND
Total
1.17
4.12
0.22
0.77
2.05
ND
ND
ND
ND
ND
*ND-None Detected
Lower Level of Detection
0.012 0.024 0.06
-------
Table 10
Analytical Results For Soil
Study No. 1-83
133
Endosulfan
Lab No.
696713
696714
696715
696716
696717
696718
696719
696720
696721
696722
Sample Site
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
1
1
1
1
1
2
2
2
2
2
parts per bi
I II
9.6
27.5
8.8
15.0
6.3
ND
ND
ND
ND
ND
27.1
46.7
31.2
16.3
18.9
ND
ND
ND
ND
ND
llion (ppb)
S Total
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
36.7
74.1
40.0
31.3
25.2
ND
ND
ND
ND
ND
*ND»None Detected
Lower Level of Detection
0.5
1.0
2.5
-------
Table 11
Analytical Results for Gauze Pads
Study No. 11-83
134
Endosulfan
Lab No.
688983
688984
688985
688986
688987
688988
688989
688990
688991
688992
688993
688994
688995
688996
688997
688998
688999
689000
689001
689002
Worker I.D. Pad
Youth Adult Site
II-83-1 Arm
Leg
II-83-2 Arm
Leg
II-83-3 Arm
Leg
II-83-4 Arm
Leg
II-83-5 Arm
Leg
II-83-6 Arm
Leg
II-83-7 Arm
Leg
II-83-8 Arm
Leg
II-83-9 Arm
Leg
11-83-10 Arm
Leg
I
ND*
0.11
ND
0.12
ND
0.04
ND
0. 16
ND
0.06
ND
0.03
0.03
0.10
0.04
0.06
ND
0.06
ND
ND
ng per
II
0.12
0.99
0.18
1.31
0.29
0.60
0.12
3.13
0.28
0.31
0. 12
0.30
0.43
0.84
0.28
0.89
0.04
0.89
0.20
0.67
cm2
S
ND
ND
ND
ND
ND
ND
ND
.22
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.12
1.10
0. 18
1.43
0.29
0.64
0. 12
3.51
0.28
0.37
0.12
0.33
0.46
0.94
0.32
0.95
0.04
0.95
0.20
0.67
*ND=None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
Table 12
Analytical Results For Gloves
Study No. 11-83
135
Endosulfan
Lab No
689053
689054
689055
689056
689057
689058
689059
689060
689061
689062
Worker I.D.
Youth Adult I
II-83-1 110
II-83-2 1,010
II-83-3 740
II-83-4 170
II-83-5 370
II-83-6 240
II-83-7 580
II-83-8 4,880
II-83-9 720
11-83-10 100
Total ng
II S
1
6
6
1
4
2
3
14
6
2
,290
,610
,930
,840
,600
,500
,720
,400
,530
,300
150
480
800
100
620
340
210
830
840
40
Total
1
8
8
2
5
3
4
20
8
2
,550
,100
,470
,110
,590
,080
,510
.110
,090
,440
Lower Level of Detection
1.0
2.0
5.0
-------
136
Table 13
Analytical Results For Hand Rinses
Study No. 11-83
Endosulfan
Lab No
685580
685581
685582
685583
685584
685585
685586
685587
685588
685589
Worker
Youth
II-83-1
II-83-2
II-83-3
II-83-4
II-83-5
l.D.
Adult
II-83-6
II-83-7
II-83-8
II-83-9
11-83-10
I
ND*
ND
10
ND
ND
79
43
5,250
ND
ND
Total
II
ND
ND
23
73
94
72
230
9,670
191
85
ng
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
ND
33
73
94
151
273
14,930
191
85
*ND-None Detected
Lower Level of Detection
1.0
2.0
5.0
-------
Table 14
Analytical Results For Air Samples
Study No. 11-83
137
Endosulfan
Lab No
685590
685591
685592
685593
685594
685595
685596
685597
685598
685599
Worker I.D.
Youth Adult
11-83-
11-83-
11-83-
11-83-
11-83-
1
2
3
4
5
I
ng per
II
ND*
3.
3.
8
8
11
16
ND
II-83-6
II-83-7
I
1-83-8
II-83-9
I
1-83-10
7.
7
28
ND
7.
8.
6.
7
5
2
24
7
17
ND
.2
.9
ND
ND
.5
ND
.6
.7
.3
ND
mj
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
11
20
3
36
32
16
23
.2
.7
.8
ND
.2
ND
.3
.2
.5
ND
*ND=None Detected
Lower Level of Detection
3.8
7.7 19.2
-------
Table 15
Analytical Results For Foliage
Study No. 11-83
138
Endosulfan
ng per cm2
Lab No.
684467
684468
684469
684470
684471
684472
684473
684474
684475
685576
Sample S
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
ite
1
1
1
1
1
2
2
2
2
2
I
0.42
0.92
0. 10
2.61
2.70
ND*
ND
ND
ND
ND
II
0.61
2.39
0.24
6.58
7.49
ND
ND
ND
* ND
ND
S
1.35
0.69
0.34
7.03
3.89
ND
ND
ND
ND
ND
Total
2.38
4.00
0.68
16.2
14. 1
ND
ND
ND
ND
ND
*ND-None Detected
Lower Level of Detection
0.012
0.024 0.06
-------
Table 16
Analytical Results For Soil
Study No. 11-83
Endosulfan
part per billion (ppb)
Lab No.
696725
696726
696727
696728
696729
696730
696731
696732
696733
696734
Sample
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
Site
1
1
1
1
1
2
2
2
2
2
I
24.9
ND*
13.4
7.2
42.0
ND
ND
ND
ND
ND
II
34.0
ND
5.4
11.7
52.6
ND
ND
ND
ND
ND
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
58.9
ND
18.8
18.9
94.6
ND
ND
ND
ND
ND
*ND=None Detected
Lower Level of Detection
0.5
1.0
2.5
-------
140
Table 17
Analytical Results For Gauze Pads
Study No. 111-83
Endosulfan
Lab No.
685610
685611
685612
685613
685614
685615
685616
685617
685618
658619
685620
685621
685622
685623
685624
685625
685626
685627
685628
685629
Worker I.D.
Youth Adult
III-83-1
III-83-2
III-83-3
III-83-4
III-83-5
III-83-6
III-83-7
III-83-8
III-83-9
111-83-10
Pad
Site
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
I
ND*
0.06
ND
0.03
0.02
0.05
ND
0.04
ND
ND
ND
ND
ND
ND
0.04
0.22
ND
0.03
ND
0.03
ng per
II
0.05
0.77
ND
0.28
0.24
0.64
0.03
0.56
ND
0.20
- o. 10
0.53
0. 19
0.54
0.26
0.54
0.05
0.47
0.06
0.32
cm2
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.05
0.83
ND
0.31
0.26
0.69
0.03
0.60
ND
0.20
0. 10
0.53
0. 19
0.54
0.30
0.76
0.05
0.50
0.06
0.35
*ND»None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
141
Table 18
Analytical Results For Gloves
Study No. 111-83
Endosulfan
Lab No.
689063
689064
689065
689066
689067
689068
689069
689070
689071
689072
Worker I.D.
Youth Adult - I
III-83-1 82
III-83-2 370
III-83-3 1,680
III-83-4 270
III-83-5 480
III-83-6 650
III-83-7 900
III-83-8 2,040
III-83-9 94
111-83-10 1,070
Total ng
II S
2
5
1
2
4
4
-5
3
3
740
,530
,010
,370
,930
,120
,450
,920
,060
,020
180
890
830
220
1,030
1,030
1,700
760
770
280
Totaj.
1,000
3
7
1
4
5
7
8
3
4
,790
,520
,860
.440
,800
,050
,720
,920
,370
Lover Level of Detection
1.0
2.0
5.0
-------
142
Table 19
Analytical Results For Hand Rinses
Study No. 111-83
Endosulfan
Lab No.
685600
685601
685602
685603
685604
685605
685606
685607
685608
685609
Worker
Youth
III-83-1
III-83-2
III-83-3
III-83-4
III-83-5
I.D.
Adult
III-83-6
III-83-7
III-83-8
III-83-9
111-83-10
I
13
40
65
ND
32
44
18
1,870
44
190
Total
II
80
100
130
190
120
160
52
•3,940
180
470
ng
S
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
93
140
195
190
152
204
70
5,810
224
660
*ND»None Detected
Lower Level of Detection
1.0
2.0
5.0
-------
143
Table 20
Analytical Results For Air Samples
Study No. 111-83
Endosulfan
Lab No.
685646
685647
685648
685649
685650
685651
685652
685653
685654
685655
Worker I.D.
Youth Adult
III-83-1
III-83-2
III-83-3
IH-83-4
III-83-5
III-83-6
III-83-7
III-83-8
III-83-9
111-83-10
I
ND*
ND
ND
ND
ND
8.5
5.8
3.8
3.8
ND
ng per
II
ND
ND
ND
ND
8.1
11.2
26.5
5.4
12.7
ND
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
ND
ND
ND
8. 1
19.7
32.3
9.2
16.5
ND
*ND-None Detected
Lower Level of Detection
3.8
7.7
19.2
-------
144
Table 21
Analytical Results For Foliage
Study No. 111-83
Endosulfan
Lab No.
684477
684478
684479
684480
684481
684482
684483
684484
684485
684486
Sample Site
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
1
1
1
1
1
2
2
2
2
2
I
1.55
1.79
1.97
0.79
0.46
ND*
ND
ND
ND
ND
ng pe
II
9.58
9.50
7.64
3.81
2.70
ND
ND
ND
ND
ND
r cm*
S
18.7
15.1
9.18
5.26
5.84
ND
ND
ND
ND
ND
Total
29.8
26.4
18.8
9.86
9.00
ND
ND
ND
ND
ND
*ND=None Detected
Lower Level of Detection 0,012
0.024
0.06
-------
145
Table 22
Analytical Results For Soil
Study No. 111-83
Endosulfan
parts
Lab No.
696735
696736
696737
696738
696739
696740
696741
696742
696743
696744
Sample Site
I/Field
2/Field
3/Field
4/Field
5/Field
6/Field
7/Field
8/Field
9/Field
10/Field
1
1
1
1
1
2
2
2
2
2
I
52.
22.
15.
11.
15.
0.
0.
1.
0.
0.
0
7
3
9
8
8
8
5
8
6
per
II
101
46
30
20
30
1
1
2
1
0
.0
.9
.4
.7
.1
.3
.5
.1
.7
billion <
S
42.4
21.2
12.4
ND*
7.5
ND
ND
ND
ND
ND
>pb)
Total
195
89
58
32
54
1
2
4
1
1
.9
.6
.3
.0
.9
. 1
.0
.9
.3
*ND»None Detected
Lower Level of Detection 0.5
1.0
2.5
-------
146
Table 23
Analytical Results For Gauze Pads
Study No. IV-83
Endosulfan
ng per cm2
Worker I.D.
Lab No. Youth Adult
689003 IV-83-1
689004
689005
689006
689007 IV-83-4
689008
689009
689010
689011 IV-83-6
689012
689013
689014
689015 IV-83-8
689016
689017
689018
Pad
Site
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
I
0.16 '
0.47
0.13
0.12
0.29
1.31
0.04
0.24
0.39
0.32
0. 11
0.32
0.8-6
0.45
ND
0. 19
II
1.33
4.10
0.71
0.91
2.48
10.4
0.44
1.33
3.63
2.22
0.40
2.70
6.29
2.57
2.75
1. 16
S
0.25
0.49
ND*
ND
0.20
1.46
0.04
ND
0.50
0.20
ND
0.12
0.75
0.28
ND
ND
Total
1.74
5.06
0.84
1.03
2.97
13.1
0.52
1.57
4.52
2.74
0.51
3. 14
7.90
3.30
2.75
1.35
*ND=None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
147
Table 24
Analytical Results For Gloves
Study No. IV-83
Endosulfan
Lab No
689073
689074
689075
689076
Lower
Worker I.D.
Touth Adult
IV-83-1
IV-83-4
IV-83-6
IV-83-8
Level of Detection (ng)
Table
Analytical Results
Study No.
I
1.48
0.78
8.42
18.9
1.0
Total ug
II
7.78 1.
11.7 1.
41.7 6.
64.3 5.
2.0 5.
S
43
52
40
37
0
Total
10.7
14.0
56.5
88.6
25
For Hand- Rinses
IV-83
Endosulf an
Lab No
685630
685631
685632
685633
Worker I.D.
Youth Adult
IV-83-1
IV-83-4
IV-83-6
IV-83-8
I
69
151
815
5,520
Total ng
II
149
429
1.020
11,360
S
ND*
ND
ND
ND
Total
218
580
1,830
16,880
*ND-None Detected
Lover Level of Detection
1.0
2.0 5.0
-------
148
Table 26
Analytical Results For Air Samples
Study No. IV-83
Endosulfan
Lab No.
685657
685658
685659
685660
Worker
Youth
IV-83-1
IV-83-4
I.D.
Adult
IV-83-6
IV-83-8
I
90
70
73
53
ng per i
II
193
204
162
151
S
ND*
ND
ND
ND
Total
283
274
235
204
*ND-None Detected
Lower Level of Detection
11.1
22.2 55.6
-------
149
Table 27
Analytical Results For Foliage
Study IV-83
Endosulfan
ng per cm2
Lab No. Sample Site
684487
684488
684489
684490
684491
684492
1
2
3
4
5
*
I
3.9
7.6
6.4
23.2
8.1
0.7
II
16.3
38.7
48.2
95.0
21.0
2.6
S
8.0
18.5
14.5
30.7
19.5
1.7
Total
28.2
64.8
69.1
149
48.6
5.0
*Composite Corn Husk Sample
Lower Level of Detection 0.012
0.024
0.06
-------
Table 28
Analytical Results For Soil
Study No. IV-83
150
Endosulfan
parts per billion (ppb)
Lab No.
696745
696746
696747
696748
696749
Sample Site
1
2
3
4
5
26
21
28
53
47
I
.6
.1
.9
.7
.9
II
51.
34.
38.
81.
67.
6
1
5
7
0
S
4.9
ND*
8.1
ND
3.8
Total
83.1
55.2
75.5
135
119
*ND»None Detected
Lover Level of Detection
0.5
1.0
2.5
-------
151
Table 29
Analytical Results For Gauze Pads
Study No. V-83
Endosulfan
ng per cm'
Worker I.D.
Lab No. Touth Adult
689019 V-83-1
689020
689021
689022
689023 V-83-4
689024
689025
689026
689027 V-83-6
689028
689029
689030
689031 V-83-8
689032
689033
689034
Site
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
Arm
Leg
Head
Shoulder
I
0.06
0.44
ND
ND
0.03
0.16
ND
NO
0.07
0.14
ND
ND '
0.32
0. 23
ND
0.03
II
0.78
2.27
0.12
0.51
0.42
0.94
ND
0.09
0.62
0.45
ND
ND
3.45
0.88
0.18
0.34
S
0.23
ND
ND*
ND
0.05
ND
ND
ND
0.06
ND
ND
ND
0.55
ND
ND
ND
Total
1.07
2.71
0.12
0.51
0.50
1.10
ND
0.09
0.75
0.59
ND
ND
4.33
1.08
0.18
0.37
*ND=None Detected
Lower Level of Detection
0.02 0.04 0.10
-------
152
Table 30
Analytical Results For Gloves
Study No. V-83
Endosulfan
Lab No
689077
689078
689079
689080
Lower
of Det
Worker I.D.
Youth Adult I
V-83-1 0.72
V-83-4 0.77
V-83-6 0.90
V-83-8 2.07
Level
ectlon (ng) 1.0
Total yg
II
4.75 1.
3.45 0.
4.20 1.
12.1 2.
2.0 5.
S
13
31
04
34
0
Total
6.60
4.53
6.14
16.5
Table 31
Analytical Results For Hand Rinses
Study No. V-83
Endosulfan
Lab No
685634
685635
685636
685637
Worker I.D.
Youth Adult 1
V-83-1 37
V-83-4 80
V-83-6 66
V-83-8 403
Total ng
II
282
286
356
1,060
S
ND*
ND
ND
ND
Total
319
366
422
1,460
*ND-None Detected
Lower Level of Detection
1.0
2.0
5.0
-------
Table 32
Analytical Results For Air Samples
Study V-83
Endosulfan
Lab No.
685661
685662
685663
685664
Worker
Youth
V-83-1
V-83-4
I.D.
Adult
V-83-6
V-83-8
I
ND*
11.5
7.7
ND
ng per
II
14.1
57.1
ND
ND
S
ND
ND
ND
ND
Total
14.1
68.6
7.7
ND
153
*ND-None Detected
Lower Level of Detection
6.4
12.8
32.1
-------
Table 33
Analytical Results For Foliage
Study No. V-83
Endosulfan
ng per cm'
Lab No. Sample Site
684493
684494
684495
684496
684497
684498
1
2
3
4
5
*
I
1.4
1.3
1.2
0.1
0.2
0.2
II
20.8
11.8
7.3
1.4
1.0
0.8
S
11.5
14.9
8.1
7.1
8.8
1.9
Total
33.7
28.0
16.6
8.6
10.0
2.9
154
*Composite Corn Husk Sample
Lower Level of Detection 0.012 0.624
0.06
-------
155
Table 34
Analytical Results For Soil
Study No. V-83
Endosulfan
parts per billion (ppb)
Lab No.
696750
696751
696752
696753
696754
Sample Site
1
2
3
4
5
I
7.2
32.3
11.7
4.6
13.6
II
2.9
41.8
17.3
2.9
23.8
S
ND*
ND
ND
ND
ND
Total
10.1
74.1
29.0
7.5
40.8
*ND=None Detected
Lower Level of Detection 0.5
1.0
2.5
-------
Table 35
Endosulfan Degradation Study
on Corn Foliage
Louisville, MS
156
Endosulfan
Lab No.
684499
684500
684501
684502
684503
684504
684505
684506
684507
684508
684509
684510
684511
684512
684513
684514
684515
684516
684516
684518
Sample
Site
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Collection
Date
8-17-83
8-18-83
8-19-83
8-26-83
ng per cm2
I
2.9
0.3
0.9
0.1
ND*
0.3
1.5
0.2
0.1
ND
0.3
0.5
0.2
0.2
ND
0.1
0. 1
0.1
ND
ND
II
30.5
10. 1
10.9
2.7
ND
5.0
25.6
2.6
0.3
0.1
14.8
33.5
6.3
7.4
0.9
1.8
2.7
0.6
0.7
ND
S
7.6
13.5
21.0
4.7
1.0
7-9
23.7
9.4
3.0
0.4
21.8
29.5
13.1
18.4
5.9
14.3
15.7
5.8
3.0
3.9
Total
41.0
23.9
32.8
7.5
1.0
13.2
50.8
12.2
3.4
0.5
36.9
63.5
19.6
26.0
6.8
16.2
18.5
6.5
3.7
3.9
*ND=None Detected
Lower Level of Detection
0.012 0.024 0.06
-------
157
Table 35
(Continued)
Endosulfan
og per cm'
Sample Collection
Lab No.
684519
684520
684521
684522
684523
684524
684525
684526
684527
684528
684529
684530
684531
684532
684533
684534
684535
684536
684537
684538
Site Date
26 9-2-83
27
28
29
30
31 9-9-83
32
33
34
35
36 9-16-83
37
38
39
40
41 9-23-83
42
43
44
45
I
0.04
ND
0.01
ND
ND
ND
ND
ND
ND
ND
0.02
0.02
ND
ND
ND
ND
ND
ND
ND
ND
II
1.04
0.31
1.08
0.05
0.11
0.10
1.42
0.77
0.10
0.14
0.17
0.40
'0.13
ND
ND
0.22
0.53
0.11
ND
ND
S
4.77
11.74
6.82
0.95
1.41
2.29
7.70
1.48
3.26
0.55
3.15
9.41
3.13
0.89
0.26
8.53
7.29
4.55
1.06
1.49
Total
5.85
12.05
7.91
1.00
1.52
2.39
9.12
2.25
3.36
0.69
3.34
9.83
3.26
0.89
0.26
8.75
7.82
4.66
1.06
1.49
*ND-None Detected
Lower Level of Detection
0.012 0.024 0.06
-------
158
Table 35
(continued)
Endosulfan
ng
per cm'
Sample Collection
Lab No.
685539
684540
684541
684542
684543
684544
684545
684546
684547
684549
684550
684551
684552
684553
Site Date
46 10-7-83
47
48
49
50
51 10-21-83
52
53
54
56 11-3-83
57
58
59
60** 11-21-83
I
ND
0.02
ND*
ND
ND
0.01
ND
0.04
0.02
0.02
0.03
ND
ND -
0.02
II
0.33
0.93
0.19
ND
0.11
0.13
0.18
0.75
0. 13
0.42
4.16
0.02
0.05
0.22
S
2.05
3.66
3.32
3. 18
4.72
3.86
1.99
8.64
1.37
3.72
10.3
0.45
0.94
1.07
Total
2.38
4.61
3.51
3. 18
4.83
4.00
2.17
9.43
1.52
4.16
14.5
0.47
0.99
1.31
*ND-None Detected
Lower Level of Detection
**Sample Site 60 represents
one
0.012 0.024 0.06
field composite sample
-------
Table 36
Endosulfan Degradation Study on Soil
Louisville, MS
159
Endosulfan
Lab No.
696755
696756
696757
696758
696759
696760
696761
696762
696763
696764
696765
696766
696767
696768
696769
696770
696771
696772
696773
696774
Sample
Site
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Collection
Date
8-17-83
8-18-83
8-19-83
8-26-83
parts per billion
I
28.5
38.2
22.7
17.5
5.4
15.7
10.6
14.9
10.8
1.8
14.4
21.0
3.6
8.9
6.8
10.6
14.1
12.1
4.1
2.2
II
41.6
67.5
44.9
18.3
8.3
23.7
9.1
27.9
18.4
4.2
20.5
40.4
• 78.2
20.1
15.4
21.3
31.3
25.4
3.9
8.4
S
ND*
10.3
ND
ND
ND
ND
ND
3.8
ND
ND
ND
3.7
ND
ND
ND
ND
ND
3.4
ND
ND
Total
70.1
116
67.6
35.8
13.7
39.4
19.7
46.6
29.2
6.0
34.9
65.1
81.8
29.0
22.2
31.9
45.4
40.9
8.0
10.6
-------
Table 36
(continued)
160
Endosulfan
Lab No.
696775
696776
696777
696778
696779
697780
696781
696782
696783
696784
696785
696786
696787
696788
696789
696790
696791
696792
696793
696794
Saaple
Site
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Collection
Date
9-2-83
9-9-83
9-16-83
9-23-83
parts per billion
I
8.3
7.0
13.7
2.4
7.5
7.2
12.3
9.9
3.6
2.4
9.6
2.7
14.9
2.5
ND
ND
4.1
2.4
ND
ND
II
19.5
18.6
33.8
7.8
18.2
30.0
34.6
28.8
13.2
12.4
58.1
18.7
86.9
- 15.2
NO
16.2
19.6
25.6
6.7
5.3
S
ND
6.8
ND
2.0
ND
20.0
19.9
10.8
ND
ND
52.9
27.6
74.9
ND
ND
28.5
34.7
34.2
ND
ND
Total
27.8
32.4
47.5
12.2
25.7
57.2
66.8
49.0
16.8
14.8
121
49.0
177
17.7
ND
44.7
58.4
62.2
6.7
5.3
*ND-None Detected
Lower Level of Detection
0.5
1.0 2.5
-------
Table 36
(continued)
161
Endosulfan
Lab No.
696795
696796
696797
696798
696799
696800
696801
696802
696803
696804
696805
696806
696807
696808
696809
696810
696811
696812
696813
696814
696815
696816
696817
696818
696819
696820
696821
696822
696823
696824
Sample
Site
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
Collection
Date
10-7-83
10-21-83
11-3-83
11-21-83
12-16-83
2-10-84
parts per billion
I
ND*
1.7
ND
ND
ND
2.1
3.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.4
ND
ND
II
35.7
16.9
14.2
7.8
ND
21.5
17.4
12.6
ND
ND
11.7
7.2
9.1
' 9.7
8.3
8.4
17.7
6.7
ND
ND
ND
9.8
5.7
ND
ND
3.3
ND
19.5
ND
ND
S
49.4
41.2
29.7
9.2
ND
49.8
32.7
19.2
ND
ND
46.1
28.3
ND
9.2
ND
36.2
38.2
16.8
ND
ND
ND
37.0
21.6
ND
ND
11.3
ND
38.2
ND
ND
Total
85.1
59.8
43.9
17.0
ND
73.4
54.0
31.8
ND
ND
57.8
35.5
9.1
18.9
8.3
44.6
55.9
23.5
ND
ND
ND
46.8
27.3
ND
ND
14.3
ND
59.1
ND
ND
-------
Table 37
Analytical Results For Gauze Pads
Study No. VI-83
162
Worker I.D.
Lab No. Youth Adult
707965 VI-83-1
707966
707967 VI-83-2
707968
707969 VI-83-3
707970
707971 VI-83-6
707972
707973 VI-83-7
707974
707975 VI-83-8
707976
Pad
Site
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Arm
Leg
Benomyl
Wg
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
MBC'
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*MBC»Methyl-2-benzimidazole carbamate (Benomyl degradation
product)
**ND-None Detected
Lower Level of Detection For MBC » 0.25 pg/cm2
-------
163
Table 38
Analytical Results For Gloves and Hand Rinses
Study No. VI-83
Benomyl and MBC*
Gloves Hand Rinse
Lab No.
707926
707927
707928
707929
707930
707931
Worker
Youth
VI-83-1
VI-83-2
VI-83-3
I.D.
Adult
VI-83-6
VI-83-7
VI-83-8
ug
ND**
ND
ND
ND
ND
ND
MI-
ND
ND
ND
ND
ND
ND
*MBOMethyl-2-benzimidazole carbamate
**ND-None Detected
Lower Level of Detection (MBC) 12.5 12.5
-------
Table 39
1983 Participant Data
Study No. Worker I.D. Sex Age Height Wt
Exposure
(Ibs.) Time (min)
1-83
1-83
1-83
1-83
1-83
1-83
1-83
1-83
1-83
1-83
11-83
11-83
11-83
11-83
11-83
11-83
11-83
11-83
11-83
11-83
1-83-1
1-83-2
1-83-3
1-83-4
1-83-5
1-83-6
1-83-7
1-83-8
1-83-9
1-83-10
II-83-1
II-83-2
II-83-3
II-83-4
II-83-5
II-83-6
11-83-7
11-83-8
II-83-9
11-83-10
M
M
M
F
M
F
M
M
M
F
M
M
M
F
M
F
M
M
M
F
«_^b__
9
17
16
17
16
48
19
50
48
29
9
17
16
17
16
48
19
50
19
29
4'6"
6'0"
5'9"
5'7"
6'3"
5'5"
5'9"
5 '9"
5' 10"
5'3"
4 '6"
6'0"
5 '9"
5 '7"
6" 3"
5 '5"
5'9"
5 '9"
5'8"
5'3"
70
165
125
130
180
165
140
165
190
125
70
165
125
130
180
165
140
165
141
125
91
91
91
91
91
91
91
91
91
91
130
130
130
130
130
130
130
130
130
130
Productivity*
0.5
1.5
1.0
0.75
1.0
0.75
1.0
1.5
1.0
1.0
1.0
1.5
1.5
1.25
1.5
2.0
1.5
1.5
1.5
1.5
* Bushels harvested by each worker
ON
-------
Table 39
(cont inued)
Study No* Worker I.D. Sex Age Height
Exposure
Wt(lbs) Time (min)
111-83
ILI-83
111-83
111-83
111-83
111-83
111-83
tII-83
111-83
LII-83
IV-83
IV-83
IV-83
IV-83
V-83
V-83
V-83
V-83
VI-83
VI-83
VI-83
VI-83
VI-83
VI-83
III-83-1
III-83-2
III-83-3
III-83-4
III-84-5
III-83-6
I1I-83-7
III-83-8
III-83-9
111-83-10
IV-83-1
IV-83-4
IV-83-6
IV-83-8
V-83-1
V-83-4
V-83-6
V-83-8
VI-83-1
VI-83-2
VI-83-3
VI-83-6
VI-83-7
VI-83-8
M
M
M
F
M
F
M
M
M
F
M
F
F
M
M
F
F
M
M
F
M
M
F
M
~-
9
17
16
17
16
48
19
50
19
29
9
17
48
50
9
17
48
50
14
12
14
37
35
51
4 '6"
6'0"
5'9"
5'7"
6' 3"
5'5"
5'9"
5 '9"
5'8"
5'3"
4'6"
5'7"
5'5"
5'9"
4'6"
5'7"
5 '5"
5'9"
5' 10"
5'2"
5'10"
5'9"
5 '2"
5'5"
70
165
125
130
180
165
140
165
141
125
70
130
165
165
70
130
165
165
125
85
1 12
148
260
200
130
130
130
130
130
130
130
130
130
130
45
45
45
45
78
78
78
78
149
149
149
149
149
149
*Bushels harvested by each worker
Product ivi ty*
0.5
1.0
1.0
1.0
1.0
1.0
1.0
0.75
1.25
0.75
1.5
2.5
3.0
3.0
2,
2,
3.0
4.5
2.5
2.0
2.5
2.5
3.0
3.0
0\
cn
-------
166
Table 40
Analytical Results For Gauze Pads
Study No. 1-84
Endosulfan
ng per cm2
Worker I.D.
Lab No. Youth Adult
699822 1-84-1
699823
699824
699825
699826 1-84-2
699827
699828
699829
699830 1-84-3
699831
699832
699833
699834 1-84-4
699835
699836
699837
699838 1-84-5
699839
699840
699841
Pad
Site
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
I
4.54
6.72
1.64
0.32
12.0
0.79
0.45
0.15
5.70
12.8
0.50
0.29
3.63
2.18
0.41
0.32
2.88
0.90
0.74
0.42
II
11.8
13.6
3.24
0.73
28.4
188
1.27
0.21
16.6
17.0
0.94
0.31
8.96
5.38
1.19
0.40
6.30
2.82
1.27
0.84
S
ND*
ND
ND
ND
1.12
ND
ND
ND
ND
0.39
ND
ND
ND
0.22
ND
ND
ND
ND
ND
ND
Total
16.3
20.3
4.88
1.05
41.5
189
1.72
0.36
22.3
30.2
1.44
0.60
12.6
7.78
1.60
0.72
9.18
3.72
2.01
1.26
*ND*None Detected
-------
167
Table 40
(continued)
Endosulfan
Worker I.D. Pad
Lab No. Youth Adult Site
699842
699843
699844
699845
699846
699847
699848
699849
699850
699851
699852
699853
699854
699855
699856
699857
699858
699859
699860
699861
1-84-6 Ar«
Leg
Shoulder
Head
1-84-7 Ara
Leg
Shoulder
Head
1-84-8 Arm
Leg
Shoulder
Head
1-84-9 Aria
Leg
Shoulder
Head
1-84-10 Arm
Leg
Shoulder
Head
9
1
0
0
12
2
0
0
13
6
1
0
5
0
0
0
1
0
0
0
I
.08
.40
.66
.15
.9
.56
.62
.19
.8
.56
.37
.27
.68
.63
.44
. 20
.74
.58
.38
.18
ng per cm2
20
3
1
0
27
8
0
0
41
16
3
0
12
I
0
0
5
1
0
0
II
.8
.44
.20
.20
.5
.16
.98
.32
.2
.8
.28
.53
.8
.64
.89
.31
.04
.72
.37
.33
S
1.16
ND*
ND
ND
1.58
ND
ND
ND
2.78
0.53
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
31.
4,
1.
0,
42.
10.
1.
0.
57,
23,
4.
0,
18,
2,
1,
0,
6,
2,
0,
0,
,0
,84
,86
.35
,0
,7
,60
,51
,8
,9
.65
.80
,5
.27
,33
,51
,78
,30
.75
.51
*ND-None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
168
Table 41
Analytical Results For Gloves
Study No. 1-84
Endosulfan
Lab No.
699761
699762
699763
699764
699765
699766
699767
699768
699769
699770
Worker I.D.
Youth Adult I
1-84-1 29.
1-84-2 28.
1-84-3 72.
1-84-4 28.
1-84-5 33.
1-84-6 24.
1-84-7 43.
1-84-8 61.
1-84-9 15.
1-84-10 12.
Total yg
II
3
8
6
0
0
7
7
0
6
3
70.
60.
148
69.
92.
66.
95.
158-
45.
34.
2
6
2
5
8
6
5
8
4
3
6
6
7
4
5
11
2
1
S
.2
.0
.9
.1
.0
.7
.8
.3
.7
.6
Total
104
92
228
103
133
97
145
230
63
49
.4
.2
.8
.7
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
169
Table 42
Analytical Results For Hand Rinses
Study No. 1-84
Endosulfan
Lab
698
698
698
698
698
698
698
698
698
698
No.
100
101
102
103
104
105
106
107
108
109
Worker
Youth
1-84-
1-84-
1-84-
1
2
3
I.D.
Adult
1-84-4
1-84-
5
1-84-6
1-84-7
1-84-8
1-84-9
1-84-10
1
2
1
0
1
1
6
3
1
0
I
.1
.2
.6
.8
.3
.2
.9
.9
.0
.6
Total
II
3.
10.
5.
3.
5.
2.
17.
13-.
4.
1.
9
4
4
3
7
9
0
1
4
1
yg
s
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
5
12
7
4
7
4
23
17
5
1
.0
.5
.0
.1
.0
.1
.9
.0
.4
.7
*ND=None Detected
Lover Level
of Detection (ng)
1.0
2.0
5.0
-------
170
Table 43
Analytical Results For Air Samples
Study No. 1-84
Endosulfan
Lab No.
698038
698039
698040
698041
698042
698043
698044
698045
698046
698047
Worker
Youth
1-84-1
1-84-2
1-84-3
1-84-4
1-84-5
l.D.
Adult
1-84-6
1-84-7
1-84-8
1-84-9
1-84-10
I
93
129
167
179
117
210
152
135
161
120
ng per
II .
78
47
82
83
62
110
65
•88
72
60
cm3
S
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
171
176
249
262
179
320
217
223
233
180
*ND-None Detected
Lower Level of Detection
5.3
10.5 26.3
-------
171
Table 44
Analytical Results For Foliage
Study No. 1-84
Endosulfan
ng per car'
Lab No.
696953
696954
696955
696956
696957
696958
696959
696960
696961
696962
696963
696964
696965
696966
696967
696968
696969
696970
696971
696972
696973
Sample
Site
1
2
3
4
5
*
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
6-21-84
6-21-84
6-21-84
6-21-84
6-21-84
6-21-84
6-22-84
6-22-84
6-22-84
6-22-84
6-22-84
6-23-84
6-23-84
6-23-84
6-23-84
6-23-84
6-24-84
6-24-84
6-24-84
6-24-84
6-24-84
I
15.8
3.9
3.9
24.1
5.2
7.2
14.0
2.8
2.3
2.6
0.8
11.6
1.6
1.2
0.6
0.8
11.0
7.2
4.0
3.2
8.5
II
67.2
24.1
24.4
81.8
28.2
25.4
82.5
20.0
25.4
16.7
8.5
67.2
•10.4
17.7
7.3
7.2
61.7
45.9
24.4
32.8
28.3
S
15.4
5.5
7.0
17.5
3.6
9.4
15.5
10.8
14.8
15.6
9.1
20.6
7.1
8.9
5.9
7.1
45.1
23.2
17.1
13.7
7.9
Total
98.4
33.5
35.3
123
37.0
42.0
11.2
33.6
42.5
34.9
18.4
99.4
19.1
27.8
13.8
15.1
118
76.3
45.5
43.9
44.7
*0ne composite corn husk sample
Lower Level of Detection 0.012
0.024 0.06
-------
Table 45
Analytical Results For Soil
Study No. 11-84
172
Endosulfan
Lab No.
696825
696826
696827
696828
696829
696830
696831
696832
666833
696834
696835
696836
696837
696838
696839
696840
696841
696842
696843
696844
Sample
Site _
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
6-21-84
6-21-84
6-21-84
6-21-84
6-21-84
6-22-84
6-22-84
6-22-84
6-22-84
6-22-84
6-23-84
6-23-84
6-23-84
6-23-84
6-23-84
6-24-84
6-24-84
6-24-84
6-24-84
6-24-84
parts
I
327
174
287
279
237
253
83
16
72
138
606
439
466
337
397
187
87
104
54
33
per billion
II
427
256
446
277
289
307
115
220
104
159
1 ,250
255
- 892
691
716
249
142
166
92
54
S
ND*
ND
ND
17
31
ND
ND
ND
ND
ND
159
127
120
122
51
ND
ND
ND
18
ND
(ppb)
Total
799
430
736
573
557
560
198
382
176
297
2,020
1,420
1,480
1 ,150
1,160
436
229
270
164
87
*ND-None Detected
Lower Level of Detection
0.5
1.0
2.5
-------
Table 46
Analytical Results For Gauze Pads
Study No. 11-84
173
Endosulfan
Worker I.D. Pad
Lab No. Youth Adult Site
699862 II-84-1
699863
699864
699865
699866 II-84-2
699867
699868
699869
699870 II-84-3
699871
699872
699873
699874 II-84-4
699875
699876
699877
699878 II-84-5
699879
699880
699881
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
44
25
03
04
22
09
ND
ND
3
18
ND
ND
67
71
ND
ND
18
29
11
05
ng per
II
1.
3.
0.
0.
0.
0.
1.
0.
2.
3.
0.
0.
0.
0.
0.
70
94
23
10
68
53
ND
ND
49
66
ND
ND
62
51
ND
09
81
96
13
09
0.
1.
0.
0.
0.
0.
0.
0.
cm2
S
57
39
ND*
ND
18
ND
ND
ND
25
11
ND
ND
29
54
ND
ND
ND
18
ND
ND
Total
2.
6.
0.
0.
1.
0.
2.
0.
3.
4.
0.
0.
1.
0.
0.
71
58
31
14
08
62
ND
ND
11
95
ND
ND
58
76
ND
09
99
43
24
14
-------
174
Table 46
(continued)
Endosulfan
Worker I.D. Pad
Lab No. Youth Adult Site
698882
698883
698884
698885
698886
698887
698888
698889
698890
698891
698892
698893
698894
698895
698896
698897
698898
698899
698900
698901
II-84-6 Arm
Leg
Shoulder
Head
II-84-7 Arm
Leg
Shoulder
Head
II-84-8 Arm
Leg
Shoulder
Head
II-84-9 Arm
Leg
Shoulder
Head
11-84-10 Arm
Leg
Shoulder
Head
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
36
01
ND*
ND
19
87
06
04
28
50
06
ND
29'
39
ND
ND
44
50
11
ND
ng per cm2
1
2
0
2
0
1
2
0
1
1
0
0
2
2
0
II
.58
.73
ND
ND
.76
.88
.04
ND
.09
.44
.09
ND
.34
.40
. 10
.09
.44
.20
.11
ND
S
0.23
0.45
ND
ND
ND
0.42
ND
ND
ND
0.45
ND
ND
0.23
0.26
ND
ND
0.42
0.38
ND
ND
Total
2.
4.
0.
5.
0.
0.
1.
3.
0.
1.
2.
0.
0.
3.
3.
0.
17
19
ND
ND
95
12
10
04
37
39
15
ND
86
05
10
09
30
08
22
ND
*ND=None Detected
Lower Level of Detection
0.02 0.04 0.10
-------
175
Table 47
Analytical Results For Gloves
Study No. 11-84
Endosulf an
Lab No.
699771
699772
699773
699774
699775
699776
699777
699778
699779
699780
Worker I.D.
Youth Adult
II-84-1
II-84-2
II-84-3
II-84-4
II-84-5
II-84-6
II-84-7
II-84-8
II-84-9
11-84-10
I
1.01
0.61
2.09
1.50
1.72
2.32
1.55
1.63
0.67
0.79
Total
II
4.55
1.68
4.53
4.03
3.10
5.73
3.42
4'. 04
2.61
2.79
yg
S
2.45
0.31
0.58
0.76
0.33
1.78
0.58
0.93
0.89
1.42
Total
8.01
2.60
9.80
6.29
5.15
9.83
5.55
6.60
4.17
5.00
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
176
Table 48
Analytical Results For Hand Rinses
Study No. 11-84
Endosulfan
Lab
6981
6981
6981
6981
6981
6981
6981
6981
6981
6981
No.
10
11
12
13
14
15
16
17
18
19
Worker
Youth
11-84-
11-84-
11-84-
11-84-
1
2
3
4
I.D.
Adult
II-84-5
II-84-6
11-84-7
II-84-8
II-84-9
11-84-10
0.
0.
0.
0.
2.
0.
0.
0.
0.
0.
I
14
09
21
15
16
21
58
55
08
35
Total
II
0
0
0
0
5
0
1
1
0
0
.58
.37
.72
.89
.07
.45
.36
.13
.29
.49
tig
S
0.15
ND*
NO
0.51
ND
ND
ND
ND
ND
ND
Total
0.
0.
0.
1.
7.
0.
1.
1.
0.
0.
87
46
93
55
23
66
94
68
37
84
*ND»None Detected
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
V77
Table 49
Analytical Results For Air Samples
Study No. 11-84
Endosulfan
Lab No.
698048
698049
698050
698051
698052
698053
698054
698055
698056
698057
Worker
Youth
II-84-1
II-84-2
II-84-3
II-84-4
II-84-5
I.D.
Adult
•
II-84-6
II-84-7
T T— R&-R
II-84-9
11-84-10
I
13.8
ND*
ND
ND
ND
13.3
12.8
13.8
67.1
ng pe
II
19.0
ND
ND
ND
ND
ND
ND
ND
ND
•r mj
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
32.8
ND
ND
ND
ND
13.3
12.8
13.8
67.1
*ND-None Detected
Lower Level of Detection
4.8
9.5
23.8
-------
178
Table 50
Analytical Results For Foliage
Study No. 11-84
Endosulfan
ng per cm2
Lab No.
696974
696975
696976
696977
696978
696979
696980
696981
696982
696983
696984
696985
696986
696987
696988
696989
696990
696991
696992
696993
696994
Sample
Site
1
2
3
4
5
*
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
6-26-84
6-26-84
6-26-84
6-26-84
6-26-84
6-26-84
6-27-84
6-27-84
6-27-84
6-27-84
6-27-84
6-28-84
6-28-84
6-28-84
6-28-84
6-28-84
6-29-84
6-29-84
6-29-84
6-29-84
6-29-84
I
0.5
0.5
0.4
2.6
1.6
0.1
0.6
0.3
0.8
0.4
0.2
65.3
45.5
86.6
2.5
63.4
12.5
9.5
17.8
5.7
2.6
II
2.6
1.3
2.0
13.1
6.2
0.7
4.4
1.2
3.9
1.3
1.3
147
127
206
9.4
38.3
36.9
38.6
80.4
24.1
12.7
S
3.8
1.8
3.7
14.7
9.0
1.7
3.4
4.0
2.9
2.7
1.4
19.7
12.1
30.1
0.4
6.8
14.8
19.8
12.2
17.7
4.6
Total
6.9
3.6
6.1
30.4
16.8
2.5
8.4
5.5
7.6
4.4
2.9
232
185
323
12.3
109
64.2
67.9
110
47.5
7.2
*0ne composite corn husk sample
Lower Level of Detection 0.012
0.024 0.06
-------
Table 51
Analytical Results For Soil
Study No. 11-84
179
Endosulfan
Lab No.
696845
696846
696847
696848
696849
696850
696851
696852
696853
696854
696855
696856
696857
696858
696859
696860
696861
696862
696863
696864
Sample
Site
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
parts per billion
Collection
Date
6-26-84
6-26-84
6-26-84
6-26-84
6-26-84
6-27-84
6-27-84
6-27-84
6-27-84
6-27-84
6-28-84
6-28-84
6-28-84
6-28-84
6-28-84
6-29-84
6-29-84
6-29-84
6-29-84
6-29-84
I
13.4
24.2
30.1
27.0
23.9
4.6
15.9
39.3
56.6
53.0
310
463
597
504
254
304
227
321
564
166
II
41.6
86.9
74.7
65.2
44.7
19.3
51.8
117
170
140
409
595
704
634
353
416
388
469
819
290
S
15.1
28.4
17.4
ND*
10.9
ND
17.7
27.3
33.2
28.3
16.4
12.4 1
12.0 1
22.3 1
18.6
34.3
30.4
22.7
59.3 1
41.2
Total
70.1
140
122
92.2
79.5
23.9
85.4
185
260
221
735
,070
,313
,160
626
755
645
813
.440
497
Lower Level of Detection
0.5
1.0
2.5
-------
180
Lab No.
699902
699903
699904
699905
699906
699907
699908
699909
699910
699911
699912
699913
699914
699915
699916
699917
699918
699919
699920
699921
Analytical
Study
Worker I.D.
Youth Adult
III-84-1
III-84-2
III-84-3
III-84-4
III-84-5
Table 52
suits For
Gauze
Pads
y No. 111-84
Endosulf an
ng per cm2
Pad
Site
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
I
ND*
ND
0.05
0.06
0.55
ND
0.04
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
II
0.94
1.75
0.14
0.34
4.98
1.74
0.21
0.23
0.79
0.94
0.13
0.08
0.67
1.98
0.08
0.13
2.48
0.88
ND
0.15
S
1.48
1.56
ND
ND
ND
1.50
ND
ND
0.76
0.58
ND
ND
0.58
2.65
ND
ND
0.62
0.62
ND
ND
Total
2.42
3.31
0. 19
0.40
5.53
3.24
0.25
0.23
1.55
1.52
0.13
0.08
1.25
4.63
0.08
0. 13
3. 10
1.50
ND
0. 15
*ND-None Detected
-------
18!
Table 52
(continued)
Endosulfan
Lab No.
699222
699223
699224
699225
699226
699227
699228
699229
699230
699231
699232
699233
699234
699235
699236
699237
699238
699239
699240
699241
Worker I.D. Pad
Youth Adult Site
III-84-6 Arm
Leg
Shoulder
Head
III-84-7 Arm
Leg
Shoulder
Head
III-84-8 Arm
Leg
Shoulder
Head
III-84-9 Arm
Leg
Shoulder
Head
111-84-10 Arm
Leg
Shoulder
Head
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
75
ND*
05
ND
ND
ND
05
ND
12
04
09
10
15-
ND
18
ND
ND
37
05
05
ng
per cm2
II
19.
7.
0.
0.
4.
9.
0.
0.
9.
3.
0.
0.
1.
6.
1.
0.
15.
9.
0.
0.
6
08
08
06
90
17
08
11
46
37
18
30
09
09
20
07
8
46
09
11
0.
1.
0.
1.
0.
0.
0.
0.
0.
1.
1.
s
58
02
ND
ND
73
31
ND
ND
87
58
ND
15
11
95
ND
ND
60
24
ND
ND
Total
22.
8.
0.
0.
5.
10.
0.
0.
10.
3.
0.
0.
1.
7.
1.
0.
17.
11.
0.
0.
0
10
13
06
63
5
13
11
5
99
27
55
35
04
38
07
4
1
14
16
*ND=None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
182
Table 53
Analytical Results For Gloves
Study No. 111-84
Endosulfan
Lab
699
No.
781
699782
699
783
699784
699
699
699
699
699
699
785
786
787
788
789
790
Worker I.D.
Youth Adult
III-84-1 2
III-84-2 2
III-84-3 5
III-84-4 2
III-84-5 1
III-84-6 1
III-84-7 4
III-84-8 2
III-84-9 1
111-84-10 2
I
.44
.58
.89
.27
.40
.88
.25
.95
.47
.19
Total yg
II
10
1
1
1
1
i
4
1
7
3
26
rs
i
i
1
0
.7
.0
.9
.6
.34
.5
.2
.0
.3
.6
4.
2.
1.
2.
0.
3.
3.
3.
2.
3.
S
14
06
77
72
77
80
97
01
14
01
Total
17
15
22
16
9
19
34
21
14
15
.3
.6
.6
.6
.51
.2
.4
.0
.9
.8
Lower Level of Detection (ng) 1.0
2.0
5.0
-------
183
Table 54
Analytical Results For Hand Rinses
Study No. III-8A
Endosulfan
Lab No.
698121
698122
698123
698124
698125
698126
698127
698128
698129
698130
Worker
Youth
III-84-1
III-84-2
III-84-3
III-84-4
III-84-5
I.D.
Adult
III-84-6
III-84-7
III-84-8
III-84-9
111-84-10
I
0.16
0.47
0.56
0.67
0.39
0.38
1.33
1.49
0.14
0.27
Total
II
0.85
2.64
2.54
4.36
1.90
2.01
4.84
"4.00
0.89
0.88
wg
S
ND*
ND
0.30
ND
ND
ND
0.26
ND
ND
ND
Total
1.01
3.11
3.40
5.03
2.29
2.39
6.43
5.49
1.03
1.15
*ND-None Detected
Lower Level of Detection (ng) 1.0
2.0
5.0
-------
184
Table 55
Analytical Results For Air Samples
Study No. 111-84
Endosulfan
Lab No.
698058
698059
698060
698061
698062
698063
698064
698065
698966
698067
Worker I.D.
Youth Adult
III-84-1
III-84-2
III-84-3
III-84-4
III-84-5
III-84-6
III-84-7
III-84-8
III-84-9
111-84-10
I
18.6
15.5
24.1
9.5
12.7
22.7
9.5
ND*
18.6
25.4
ng per
II
42.7
ND
ND
ND
ND
ND
ND
" ND
30.5
63.2
m3
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
61.3
15.5
24.1
9.5
12.7
22.7
9.5
ND
49. 1
88.6
*ND-None Detected
Lower Level of Detection
4.5
9.0
22.5
-------
185
Table 56
Analytical Results For Foliage
Study No. 111-84
Endosulfan
ng per cm2
Lab No.
696995
696996
696997
696998
696999
697000
697001
697002
697003
697004
697005
697006
697007
697008
697009
607010
697011
697012
697013
6970U
697015
Sample
Site
*
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
6-30-84
6-30-84
6-30-84
6-30-84
6-30-84
6-30-84
7-1-84
7-1-84
7-1-84
7-1-84
7-1-84
7-2-84
7-2-84
7-2-84
7-2-84
7-2-84
7-3-84
7-3-84
7-3-84
7-3-84
7-3-84
I
0.1
15.3
5.1
2.8
2.3
1.6
1.6
1.5
1.7
1.0
2.5
0.5
1.2
5.8
2.2
4.9
3.0
1.6
4.5
4.4
3.3
II
0.6
11.1
40.3
17.3
18.6
11.1
16.1
20.9
19.3
10.9
23.9
4.5
9.6
32.3
19.7
41.6
40.0
15.9
29.6
32.0
31.2
S
0.5
3.5
11.7
16.0
7.2
5.5
5.3
6.3
5.3
8.7
6.5
5.9
8.6
7.3
18.5
21.7
10.2
5.9
16.5
17.4
16.1
Total
1.2
29.9
57.1
36.1
28.1
18.2
23.0
28.7
26.3
20.6
32.9
10.9
19.4
45.4
40.4
68.2
53.2
23.4
50.6
53.8
50.6
*0ne composite corn husk sample
Lower Level of Detection 0.012
0.024 0.06
-------
Table 57
Analytical Results For Soil
Study No. 111-84
186
Endosulfan
Lab No.
696865
696866
696867
696868
696869
696870
696871
696872
696873
696874
696875
696876
696877
696878
696879
696880
696881
696882
696883
696884
Sample
Site
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
6-30-84
6-30-84
6-30-84
6-30-84
6-30-84
7-1-84
7-1-84
7-1-84
7-1-84
7-1-84
7-2-84
7-2-84
7-2-84
7-2-84
7-2-84
7-3-84
7-3-84
7-3-84
7-3-84
7-3-84
parts
I
162
282
185
185
159
31
37
23
104
57
28
41
69
122
115
176
113
137
171
97
per billion
II
304
442
296
361
279
50
67
39
146
127
64
91
104
257
169
317
205
258
379
229
S
81
74
32
80
56
14
15
3
31
34
41
21
23
83
49
94
34
54
161
90
(ppb)
Total
547
798
513
626
494
95
119
65
281
218
133
153
196
462
333
587
352
449
711
416
Lower Level of Detection
0.5
1.0
2.5
-------
Table 58
Analytical Results For Gauze Pads
Study No. IV-84
187
Lab No.
699942
699943
699944
699945
699946
699947
699948
699949
699950
699951
699952
699953
699954
699955
699956
699957
699958
699959
699960
699961
Worker I.D.
Youth Adult
IV-84-1
IV-84-2
IV-84-3
IV-84-4
IV-84-5
Endosulf an
Pad
Site
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
03
18
04
ND*
59
21
79
07
12
12
07
ND
ND
18
05
16
44
30
11
03
ng
per
II
0.
0.
0.
0.
0.
0.
2.
0.
1.
1.
0.
0.
0.
0.
1.
1.
0.
0.
0.
18
96
12
24
58
82
02
12
00
08
20
16
ND
96
15
25
69
60
25
06
cm*
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.
1.
0.
0.
1.
1.
2.
0.
1.
1.
0.
0.
1.
0.
1.
2.
0.
0.
0.
21
14
16
24
17
03
81
19
12
20
27
16
ND
14
20
41
13
90
36
09
*ND-None Detected
-------
Table 58
(continued)
188
Endosulfan
Lab No,
699962
699963
699964
699965
699966
699967
699968
699969
699970
699971
699972
699973
699974
699975
699976
699977
699978
699979
699980
699981
Worker I.D.
Youth Adult
IV-84-6
IV-84-7
IV-84-8
IV-84-9
Pad
Site
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
Arm
Leg
Shoulder
Head
0
0
0
0
0
0
0
0
0
0
0
0
0
0
I
.08
.10
.08
ND
.19
.19
.09
ND
.65
.36
ND
.05
.94'
.08
ND
.04
.14
.50
ND
ND
ng
per
II
0.
0.
0.
1.
1.
0.
0.
1.
2.
0.
0.
0.
0.
1.
1.
0.
13
73
58
ND
67
00
13
05
67
08
ND
46
48
35
ND
17
48
65
14
ND
cm2
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.
0.
0.
1.
1.
0.
0.
2.
2.
0.
5.
0.
0.
1.
2.
0.
21
53
66
ND
86
19
22
05
32
44
ND
51
42
43
ND
21
62
15
14
ND
*ND-None Detected
Lower Level of Detection
0.02
0.04
1.0
-------
Table 59
Analytical Results For Gloves
Study No. IV-84
189
Endosulfan
Lab No.
699791
699792
699793
699794
699795
699796
699797
699798
699799
699800
Worker I.D.
Youth Adult
IV-84-1 0.
IV-84-2 4.
IV-84-3 4.
IV-84-4 1.
IV-84-5 5.
IV-84-6 1.
IV-84-7 2.
IV-84-8 2.
IV-84-9 1.
IV-84-10 0.
I
24
65
28
86
72
49
27
17
43
79
Total
II
1.
13.
12.
7.
10.
3.
9.
•7.
5.
3.
25
1
1
78
7
87
29
23
80
68
Mg
S
0
2
1
0
1
1
0
ND*
.67
.30
.34
ND
.42
.12
.15
ND
.48
Total
1.
18.
18.
11.
16.
5.
12.
10.
7.
4.
49**
4
7
0
4
78
7
6
23
95
*ND-None Detected
**0nly one glove analyzed
Lower Level
of Detection (ng)
1.0
2.0 5.0
-------
190
Table 60
Analytical Results For Hand Rinses
Study No. IV-84
Endosulfan
Lab
698
698
698
698
698
698
698
698
698
698
1
1
1
1
1
1
1
1
1
1
No.
31
32
33
34
35
36
37
38
39
40
Worker
Youth
IV-84-1
IV-84-2
IV-84-3
IV-84-4
IV-84-5
I.D.
Adult
IV-84-6
IV-84-7
IV-84-8
IV-84-9
IV-84-10
0
4
0
0
6
0
0
0
0
0
I
.03
.44
.31
.08
.11
.11
.31
.22
.03
.05
Total
II
0
10
1
0
13
0
1
0
0
.18
.4
.75
.66
.0
.22
.10
.66
.18
ND
vg
S
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.
14.
2.
0.
19.
0.
1.
0.
0.
0.
21
8
06
74
1
33
41
88
21
05
*ND-None Detected
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
Table 61
Analytical Results For Air Samples
Study No. IV-84
Endosulfan
Lab No.
698068
698069
698070
698071
698072
698073
698074
698075
698076
698077
Worker
Youth
IV-84-1
IV-84-2
IV-84-3
IV-84-4
IV-84-5
I.D.
Adult
IV-84-6
IV-84-7
IV-84-8
IV-84-9
IV-84-10
I
ND*
6.2
9.0
9.0
ND
10.5
ND
10.0
ND
12.9
ng
II
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
per a1
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
6.2
9.0
9.0
ND
10.5
ND
10.0
ND
12.9
*ND-None Detected
Lower Level of Detection
4.7
9.5
23.8
-------
192
Table 62
Analytical Results For Foliage
Study No. IV-84
Endosulfan
ng per cm2
.Lab No.
698120
697016
697017
697018
697019
697020
697021
697022
697023
697024
697025
697026
697027
697028
697029
697030
697031
697032
697033
697034
697035
Sample
Site
*
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
7-12-84
7-12-84
7-12-84
7-12-84
7-12-84
7-12-84
7-13-84
7-13-84
7-13-84
7-13-84
7-13-84
7-14-84
7-14-84
7-14-84
7-14-84
7-14-84
7-15-84
7-15-84
7-15-84
7-15-84
7-15-84
I
0.7
0.7
1.9
1.7
1.7
2.6
0.1
0.2
0.1
0.4
0.6
0.1
0.1
0.4
0.5
2.4
0.1
0.2
0.2
0.1
0. 1
II
1.0
4.5
16.1
8.7
7.5
14.0
0.5
1.7
0.6
3.4
4.0
0.9
- 0.8
0.3
2.7
16.5
0.2
2.4
2.5
0.8
1.0
S
0.7
9.0
14.0
9.5
7.0
10.7
1.1
4.0
4.0
25.0
10.9
3.2
1.2
1.9
8.0
29.1
1.0
5.4
7.0
10.0
8.0
Total
2.4
14.2
32.0
19.9
16.2
26.6
1.7
5.9
4.7
28.9
15.5
4.2
2. 1
2.6
11.2
48.0
1.3
8.0
9.7
10.9
9. 1
*0ne composite corn husk sample
Lower Level of Detection
0.012 0.024 0.06
-------
Table 63
Analytical Results For Soil
Study No. IV-84
193
Endosulfan
Lab No.
696885
696886
696887
696888
696889
696890
696891
696892
696893
696894
696895
696896
696897
696898
696899
696900
696901
696902
696903
696904
Sample
Site
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Date
7-12-84
7-12-84
7-12-84
7-12-84
7-12-84
7-13-84
7-13-84
7-13-84
7-13-84
7-13-84
7-14-84
7-14-84
7-14-84
7-14-84
7-14-84
7-15-84
7-15-84
7-15-84
7-15-84
7-15-84
parts
I
23.1
54.4
44.9
65.4
129
33.7
34.0
36.9
53.1
104
30.4
21.4
32.9
66.7
110
10.2
17.7
25.5
47.7
108
per
II
23.1
55.6
53.5
189
199
41.9
42.0
73.4
115
218
46.8
27.6
-51.7
141
187
17.6
32.4
52.4
92.2
227
billion
S
ND*
ND
ND
10.2
16.3
12.6
14.8
5.4
11.4
41.3
46.8
6.0
10.3
22.2
15.1
8.6
14.9
11.0
29.1
51.9
(ppb)
Total
46.2
110
98.4
265
344
88.2
90.8
116
180
363
94.0
55.0
94.9
230
312
36.4
65.0
88.9
169
387
*ND»None Detected
Lower Level of Detection
0.5
1.0
2.5
-------
194
Table 64
Analytical Results For Gauze Pads
Study No. V-84
Endosulfan
ng per cm2
Lab No.
700002
700003
700004
700005
700006
700007
700008
700009
700010
700011
700022
700023
700012
700013
700014
700015
700016
700017
700018
700019
700020
700021
700024
700025
Worker I.D. Pad
Youth Adult Site
V-84-1 Arm
Leg
V-84-2 Arm
Leg
V-84-3 Arm
Leg
V-84-4 Arm
Leg
V-84-5 Arm
Leg
V-84-1 1 Arm
Leg
V-84-6 Arm
Leg
V-84-7 Arm
Leg
V-84-8 Arm
Leg
V-84-9 Arm
Leg
V-84-10 Arm
Leg
V-84-12 Arm
Leg
I
ND*
0.19
1.64
0.75
0.06
0.12
0.13
0.27
0.35
0.22
0.07
0.14
0.02
0.12*
0.07
0. 18
0. 11
0.21
ND
0.05
0.06
0. 16
0.03
0.24
II
ND
1.28
3.37
1.17
0.19
0.75
0.41
0.92
0.61
0.61
0.50
0.70
0.13
1.04
0.35
1.45
0.34
0.85
0.19
0.35
0.22
2.27
ND
1.23
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0. 16
ND
ND
Total
ND
1.47
5.01
1.92
0.25
0.87
0.54
1.19
0.96
0.83
0.57
0.84
0.15
1. 16
0.42
1.63
0.46
1.06
0.19
0.40
0.28
2.59
0.03
1.47
*ND-None Detected
Lower Level of Detection
0.02
0.04 0.10
-------
195
Table 65
Analytical Results For Gloves
Study No. V-84
Endosulfan
Lab No.
699801
699802
699803
699804
699805
699811
699806
699807
699808
699809
699810
699812
Worker I.D.
Youth Adult
V-84-1
V-84-2
V-84-3
V-84-4
V-84-5
V-84-11
V-84-6
V-84-7
V-84-8
V-84-9
V-84-10
V-84-12
I
0.42
11.5
1.97
0.81
16.2
0.98
1.17
0.85
11.0
1.11
0.47
1.78
Total
II
2.18
22.4
8.38
3.96
18.6
7.34
6.54
5.48
12.2
6.92
5.39
3.51
US
S
ND*
0.76
0.64
ND
ND
0.82
ND
ND
ND
ND
ND
ND
Total
2.60
34.7
11.0
4.77
34.8
9.14
7.71
6.33
23.2
8.03
5.86
5.29
*ND-None Detected
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
196
Table 66
Analytical Results For Hand Rinses
Study No. V-84
Endosulfan
Lab No.
698141
698142
698143
698144
698145
698151
698146
698147
698148
698149
698150
698152
Worker I.D.
Youth Adult I
V-84-1 0.04
V-84-2 5.70
V-84-3 0.08
V-84-4 0.16
V-84-5 21.4
V-84-11 0.10
V-84-6 0.12
V-84-7 0.25
V-84-8 3.24
V-84-9 0.29
V-84-10 0.08
V-84-12 0.32
Total yg
II S
0.26
16.4
4.22
1.38
43.2
1.03
0.59
1.33
9.22
0.88
1.50
0.71
ND*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
0.30
22.1
5.02
1.54
64.6
1.13
0.71
1.58
12.5
1.17
1.58
1.03
*ND-None Detected
Lower Level
of Detection (ng)
1.0
2.0
5.0
-------
197
Table 67
Analytical Results For Air Samples
Study No. V-84
Endosulfan
Lab No.
698088
698089
698090
698091
698092
698098
698093
698094
698095
698096
698097
698099
Worker
Youth
V-84-1
V-84-2
V-84-3
V-84-4
V-84-5
V-84-11
I.D.
Adult
V-84-6
V-84-7
V-84-8
V-84-9
V-84-10
V-84-12
I
ND*
42.7
ND
2.9
8.4
ND
5.3
6.0
5.6
ND
4.7
2.7
ng per
II
ND
32.9
ND
ND
9.5
ND
ND
ND
ND
ND
7.3
ND
ms
S
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
ND
75.6
ND
2.9
17.9
ND
5.3
6.0
5.6
ND
12.0
2.7
*ND-None Detected
Lower Level of Detection 2.2
4.4
11.1
-------
Table 68
Analytical Results For Foliage
Study No. V-84
198
Endosulfan
Lab No,
698006
698007
698008
698009
698010
698001
698002
698003
698004
698005
698011
698012
698013
698014
698015
698016
698017
698018
698019
698020
698021
698022
698023
698024
698025
Sample
Site
1*
2*
3*
4*
5*
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
Collection
Date
7-25-84
7-25-84
7-25-74
7-25-84
7-25-84
7-25-84
7-25-84
7-25-84
7-25-84
7-25-84
7-26-84
7-26-84
7-26-84
7-26-84
7-26-84
7-27-84
7-27-84
7-27-84
7-27-84
7-27-84
7-28-84
7-28-84
7-28-84
7-28-84
7-28-84
ng per cm2
I
1.14
0.95
1. 10
1.08
0.84
0.84
1.61
0.50
0.58
0.66
0.57
0.61-
0.75
0.23
0.49
0.57
0.93
0.39
0.27
0.69
0.12
0.37
0.24
0.25
0.38
II
5.35
4.22
4.34
5.35
4.05
2.79
5.81
2.21
2.24
3.44
2.00
2.38
3.09
" 1.31
2.14
2.20
3.59
1.41
1.48
3.47
0.64
1.04
1.04
1.42
2.33
S
2.48
3.42
3.33
3.23
3.61
4.06
3.74
3.78
3.45
3.06
2.91
4.08
4.41
3.45
4.42
4.71
8.06
3.28
4.09
6.71
1.71
1.26
1.92
3.86
7.21
Total
8.97
8.59
8.77
9.66
8.50
7.69
11.2
6.49
6.27
7.16
5.48
7.07
8.32
4.99
7.05
7.48
12.6
5.08
5.84
10.9
2.47
2.67
3.20
5.53
9.92
*Pea shell samples
Lower Level of Detection
0.012 0.024 0.06
-------
Table 69
Analytical Results For Soil
Study No. V-84
199
Endosulfan
Lab No.
696905
696906
696907
696908
696909
696910
696911
696912
696913
696914
696915
696916
696917
696918
696919
696920
696921
696922
696923
696924
Sample Collection
Site Date
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
7-25-84
7-25-84
7-25-84
7-25-84
7-25-84
7-26-84
7-26-84
7-26-84
7-26-84
7-26-84
7-27-84
7-27-84
7-27-84
7-27-84
7-27-84
7-28-84
7-28-84
7-28-84
7-28-84
7-28-84
parts per billion
15
15
13
40
25
11
17
8
23
22
11
12
7
21
17
9
13
7
13
31
I_
.4
.9
.1
.6
.4
.7
.5
.3
.9
.9
.1
.1
.1
.4
.3
.8
.1
.3
.8
.6
II
42
67
51
108
53
52
49
62
67
34
85
- 55
53
73
74
75
84
55
71
47
.3
.3
.5
.4
.4
.2
.1
.1
.6
.1
.4
.4
.1
.5
.8
.7
.1
.9
.8
S
44.
57.
45.
59.
44.
58.
54.
81.
101
32.
135
74.
61.
83.
100
110
142
67.
108
67.
1
1
0
9
2
5
5
9
7
9
8
2
7
9
(ppb)
Total
102
140
110
206
123
122
121
152
192
90.2
231
142
122
178
209
196
240
130
194
147
Lower Level of Detection
0.5
1.0
2.5
-------
Table 70
Analytical Results For Gauze Pads
Study No. VI-84
200
Lab No.
707977
707978
707979
707980
707981
707982
707983
707984
707985
707986
707987
Worker I.D.
Youth Adult
VI-84-1
VI-84-2
VI-84-3
Pad
Site
Arm
Shoulders
Chest
Arm
Shoulders
Chest
Arm
Benomyl
UK
ND*
ND
ND
ND
ND
ND
ND
Shoulders ND
VI-84-4
Chest
Arm
Shoulders
ND
ND
ND
MBC*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
707988
707989
707990
707991
707992
707993
707994
707995
707996
707997
707998
707999
708000
708001
708002
708003
*ND-None Detected
**MBOMethyl-2-benzlmidazole carbamate
Lower Level of Detection for MBC-0.25 yg/cm2
VI-84-6
VI-84-7
VI-84-8
VI-84-9
VI-84-12
Chest
Arm
Shoulders
Chest
Arm
Shoulders
Chest
Arm
Shoulders
Chest
Arm
Shoulders
Chest
Arm
Shoulders
Chest
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-------
201
Table 71
Analytical Results For Gloves and Hand Rinses
Study No. VI-84
Benomyl and MBC*
Lab No.
707932
707933
707934
707935
707936
707937
707938
707939
707940
Worker I.D.
Youth Adult
VI-84-1
VI-84-2
VI-84-3
VI-84-4
VI-84-6
VI-84-7
VI-84-8
VI-84-9
VI-84-12
Gloves
Total yg
ND**
ND
ND
ND
ND
ND
ND
ND
ND
Hand Rinses
Total yg
ND
ND
ND
ND
ND
ND
ND
ND
ND
*MBC=Methyl-a-benzimidazole carbamate
**ND»None Detected
Lower Level of Detection (MBC) 12.5
12.5
-------
Table 72
1984 Participant Data
Study No. Worker I.D. Sex Age Height
Exposure
Wt(lbs) Time (min)
1-84
1-84
1-84
1-84
1-84
1-84
1-84
1-84
1-84
1-84
11-84
11-84
11-84
11-84
11-84
11-84
11-84
11-84
11-84
11-84
1-84-1
1-84-2
1-84-3
1-84-4
1-84-5
1-84-6
1-84-7
1-84-8
1-84-9
1-84-10
II-84-1
H-84-2
II-84-3
II-84-4
II-84-5
II-84-6
II-84-7
II-84-8
II-84-9
11-84-10
M
H
M
M
M
F
M
M
F
F
M
M
M
M
M
F
H
M
F
F
^Bi^K__
10
17
18
17
16
49
31
52
19
29
10
17
18
17
16
49
31
52
19
29
4'8"
6'0"
5' 10"
5'H"
6'3"
5'5"
6'0"
5'9"
5*7"
5*3"
4'8"
6'0"
5'10"
5'11"
6'3"
5'5"
6'0"
5'9"
5*7"
5'3"
80
157
204
159
190
175
205
165
155
125
80
157
204
159
190
175
205
165
155
125
95
95
95
95
95
95
95
95
95
95
105
105
105
105
105
105
105
105
105
105
Productivity*
10
15
13
12
13
13
14
10
9
9
11
12
9
7
8
7
9
7
5
6
*Buckets harvested by each worker
o
-------
Table 72
(continued)
Exposure
Study No,
111-84
111-84
111-84
111-84
111-84
111-84
111-84
111-84
111-84
111-84
IV-84
IV-84
IV-84
IV-84
IV-84
IV-84
IV-84
IV-84
IV-84
IV-84
. Worker I.D.
III-84-1
III-84-2
III-84-3
III-84-4
III-84-5
III-84-6
III-84-7
III-84-8
III-84-9
111-84-10
IV-84-1
IV-84-2
IV-84-3
IV-84-4
IV-84-5
IV-84-6
IV-84-7
IV-84-8
IV-84-9
IV-84-10
Sex
M
M
M
M
M
F
M
M
F
F
M
M
M
M
M
F
M
M
F
F
Age
10
17
18
17
16
49
31
52
19
29
10
17
17
17
16
49
31
52
19
29
Height
4'8"
6'0"
5' 10"
5'H"
6'3"
5'5"
6'0"
5 '9"
5*7"
5 '3"
4 '8"
6'0"
5*7"
5,' 11"
6' 3"
5'5"
6'0"
5 '9"
5'7"
5 '3"
Wt(lbs) Time (nln)
80
157
204
159
190
175
205
165
155
125
80
157
125
159
190
175
205
165
155
125
110
110
110
110
110
110
110
110
110
110
105
105
105
105
105
105
105
105
105
105
Productivity*
5
9
9
8
9
13
13
10
12
12
4
5
8
5
5
10
8
8
5
8
^Buckets harvested by each worker
-------
Table 72
(contInued)
Study No. Worker I.p. Sex Age Height Wt(lbs)
Exposure
Time (min)
V-84
V-84
V-84
V-84
V-84
V-84
V-84
V-84
V-84
V-84
V-84
V-84
VI-84
VI-84
VI-84
VI-84
VI-84
VI-84
VI-84
VI-84
VI-84
V-84-1
V-84-2
V-84-3
V-84-4
V-84-5
V-84-11
V-84-6
V-84-7
V-84-8
V-84-9
V-84-10
V-84-12
VI-84-1
VI-84-2
VI-84-3
VI-84-4
VI-84-6
VI-84-7
VI-84-8
VI-84-9
VI-84-12
M
M
M
M
M
M
F
M
M
F
M
M
F
M
M
F
F
F
F
M
F
W-^^w
10
17
17
17
16
16
49
31
52
19
29
25
13
15
17
17
27
26
20
52
35
4'8"
6'0"
5'7"
5'H"
6 '3"
5'7"
5*5"
6'0"
5 '9"
5*7"
5'3"
5-10"
5'2"
5-11"
6'0"
5'5"
5'6"
5'2"
5'6"
5'8"
5'2"
80
157
125
159
190
130
175
205
165
155
125
150
95
130
210
105
160
131
121
203
235
225
225
225
225
225
225
225
225
225
225
225
225
225
225
225
225
225
252
225
225
225
Productivity*
5
8
8
9
6
10
9
11
7
5
10
6.5
6
6
5
5
5
7
5
6
7.5
*Buckets harvested by each worker
r\>
o
-fcs.
-------
Table 73
Weather Data For 1983/1984 Studies
Study
Number
1-83
11-83
111-83
IV-83
V-83
VI-83
1-84
11-84
111-84
IV-84
V-84
VI-84
Study
Date
7/29/83
8/1/83
8/5/83
8/13/83
8/16/83
8/18/83
6/21/84
6/26/84
6/30/84
7/2/84
7/25/84
8/9/84
Temp
°F
83
77
95
94
85
94
80
75
78
85
103
89
Relative
Humidity, Z
70
94
75
76
68
60
88
89
91
79
58
80
Wind Speed/
Direction
mph
N-NE/5-10
NE/0-5
Calm
NE/0-5
SE/0-5
E/0-7
N-NE/0-5
Cain
SW/0-5
Calm
Calm
SW/0-8
Rainfall
None
None
None
None
None
None
None
None
None
None
None
None
Cloud
Cover
Clear
Fog
Clear
Hazy
Cloudy
Hazy
Cloudy
Clear
Overcast
Overcast
Overcast
Cloudy
o
un
-------
Table 74
Recovery Of Pesticides From Adsorption Media and Foliage
1983 Youth In Agriculture Studies
Range Found
(No. Analyzed)
(0.171-0.205) (12)
(0.433-0.509) (12)
(0.876-1.00) (12)
(0.155-0.196) (7)
(0.369-0.461) (7)
(0.751-0.951) (7)
(16.7-19.1) (8)
(40.7-51.6) (8)
(81.3-110) (8)
(0.086-0.101) (7)
(0.218-0.249) (7)
(0.429-0.497) (7)
(0.035-0.040) (11)
(0.067-0.097) (11)
(0.168-0.210) (11)
Pesticide
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Endosulf an
Endosul fan
Endosulf an
Endosulf an
Endosulfan
Endosulf an
Endosulfan
Endosulfan
Endosulfan
I
II
S*
I
II
S*
I
II
S*
I
II
S*
I
II
S*
Substrate
Gauze Pads
Gauze Pads
Gauze Pads
Gloves
Gloves
Gloves
Hand Rinses
Hand Rinses
Hand Rinses
XAD Resin
XAD Resin
XAD Resin
Foliage
Foliage
Foliage
Spiking
Level
0.200 yg
0.500 yg
1.00 yg
0.200 yg
0.500 yg
1.00 yg
20 ng/ml
50 ng/ml
100 ng/ml
0.100 yg
0.250 Mg
0.500 yg
0.040 yg
0.100 yg
0.200 yg
Std.
Mean
0.
0.
0.
0.
0.
0.
18
46
99
0.
0.
0.
0.
0.
0.
184
462
940
173
422
882
.3
.7
.0
091
232
463
037
089
186
Dev.
0.
0.
0.
0.
0.
0.
0.
3.
9.
0.
0.
0.
0.
0.
0.
009
022
032
017
032
077
742
56
53
005
Oil
028
002
008
014
Coef .
Var., I
4.
4.
3.
9.
7.
8.
4.
7.
9.
5.
4.
6.
5.
8.
7.
89
76
40
83
58
73
05
62
63
49
74
05
41
99
53
*Endosulfan S-Endosulfan Sulfate
ro
o
ON
-------
Table 75
Recovery Of Pesticides From Adsorption Hedla and Foliage
1984 Youth In Agriculture Studies
•
Pesticide
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Bndosulfan
Bndosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
I
II
S*
I
II
S*
I
II
S*
I
II
S*
I
II
S*
Substrate
Gauze Pads
Gauze Pads
Gauze Pads
Gloves
Gloves
Gloves
Hand Rinses
Hand Rinses
Hand Rinses
XAO Resin
XAD Resin
XAD Resin
Foliage
Foliage
Foliage
Spiking
Level
0.200 pg
0.500 pg
1.00 pg
0.200 pg
0.500 pg
1.00 pg
20 ng/ml
50 ng/ml
100 ng/ml
0.100 gg
0.250 pg
0.500 yg
0.020 yg
0.050 yg
0.100 yg
Range Found
(No
(0.
(0.
(0.
(0.
(0.
(0.
(14
(39
(96
(0.
(0.
(0.
(0.
(0.
(0.
. Analyzed)
180-0
419-0
823-1
150-0
472-0
938-1
.2-17
.2-44
.8-11
084-0
215-0
424-0
016-0
046-0
088-0
.223)
.528)
.12)
.218)
.534)
.06)
.6) (
.3) (
1.3)(
.097)
.247)
.492)
.021)
.070)
.157)
(20)
(20)
(20)
(6)
(6)
(6)
6)
6)
6)
(7)
(7)
(7)
(10)
(10)
(10)
Mean
0.204
0.481
0.993
0.190
0.494
0.997
16.0
41.9
105
0.089
0.225
0.449
0.020
0.059
0.123
Std.
Dev.
0
0
0
0
0
0
1
1
4
0
0
0
0
0
0
.011
.025
.073
.024
.026
.051
.30
.92
.75
.004
.012
.024
.002
.007
.020
Coef .
Var., X
5.39
5.20
7.35
12.6
5.26
5.11
8.13
4.58
4.54
4.49
5.33
5.35
10.0
11.9
16.3
*Endosulfan S-Endosulfan Sulfate
rsj
o
-------
Table 76
Recovery Of Pesticides From Soil, Urine And Adsorption Media
1983 and 1984 Youth In Agriculture Studies
Spiking
Pesticide
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
Endosulfan
MBC**
MBC
MBC
MBC
MBC
I
II
S*
I
II
S*
I
II
S*
Substrate
Soil
Soil
Soil
Soil
Soil
Soil
Urine
Urine
Urine
Gauze Pads
Gloves
Gloves
Gloves
Hand Rinse
Level
20
50
100
10
25
50
100
250
500
250
250
83.
125
250
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
Ug
yg
3 yg
yg
yg
Range Found
(No. Analyzed)
(19.1-22.4) (11)
(44.3-56.8) (11)
(116.1-142) (11)
(8.9-11.3) (11)
(19.0-26.7) (11)
(44.1-59.4) (11)
(73.0-120.8) (65)
(195-252) (14)
(407-647) (14)
(248.9-259.2) (4)
(196-218) (2)
64.1
92.2
(194-276.6) (5)
Std.
Mean
20.
51.
123
10.
23.
52.
97.
230
511
253
207
-
-
239
7
2
2
6
2
1
Dev.
1.
3.
11
0.
2.
4.
11
19
59
4.
29
03
54
.0
77
42
75
.6
.6
.7
38
-
-
-
.8
Coef .
Var., I
4.
6.
8.
7.
10
9.
11
8.
11
1.
12
98
91
94
55
.3
10
.9
50
.7
73
-
-
-
.4
*Endosulfan S-Endoaulfan Sulfate
**MBC-Methyl-2-benzimidazole carbamate from spontaneous breakdown of Benomyl in
organic solvents
CD
CO
-------
Table 77
Recovery Of Endosulfan From Freezer Stored Adsorption Media
1984 Youth In Agriculture Studies
Spiking
Pesticide Substrate Level
Endosulfan 1 Gauze Pads 200 ng
Endosulfan II Gauze Pads 500 ng
Endosulfan S* Gauze Pads 1,000
Endosulfan I Gloves 200 ng
Endosulfan II Gloves 500 ng
Endosulfan S* Gloves 1,000
Endosulfan I XAD Resin 100 ng
Endosulfan II XAD Resin 250 ng
Endosulfan S* XAD Resin 500 ng
*Endosulfan S«Endosulfan Sulfate
**Splked substrates were stored In
Range Found
(No. Analyzed)
(141-178) (3)
(296-353K3)
ng (713-884) (3)
233 (1)
412 (1)
ng 982 ( 1)
(127-130) (2)
(244-260) (2)
(455-462) (2)
laboratory freezers
Mean
Recovery,
78.0
63.8
78.7
116.5
82.4
98.2
129
101
91.7
Weeks**
Stored
44
44
44
34
34
34
38
38
38
at -18*C for 34-44 weeks,
-------
210
D1siodgeable Captan Residues at Florida
Strawberry Farms
Research performed by
Florida State University
Lake Alfred, FL 33850
May 1986
-------
211
CONTENTS
Abstract lii
Acknowledgment Ill
Figures 1v
Introduction 1
Experimental Design and Sampling 2
Application of Compound 4
Materials and Methods 5
Extraction
Leaves 5
Soil 6
Gas-Liquid Chromatography 6
Results and Discussion 7
Conclusions 14
Recommendations 16
References 17
Tables
1. Application history of captan to commercial farm 4
2. Captan residues on leaf and soil surfaces (commercial farm). . 8
3. Captan residues on leaf surfaces (private farm) 10
4. Residue dissipation half-lives from a first-order
regression analysis 11
5. Storage loss study 14
Appendix
A. Weather data (Table) 18
B. Quality assurance aspects 21
Tables
B-l Technician captan recoveries from fortified
exposure pads, prior to experiment 22
B-2 Technician captan recoveries from fortified gloves,
prior to experiment 24
B-3 Captan GLC control chart (Data, by technician) ... 25
B-4 Captan residue samples lost prior to GLC analysis . . 27
B-5 Comparison of non-N-evaporation extraction 29
11
-------
212
ABSTRACT
Dislodgeable leaf and soil surface residues of captan were
collected from a large commercial Florida strawberry farm during the
entire growing/harvesting season. The season extended from November
1984 to March 1985. Captan applications to the farm with a boom sprayer
o
maintained a level of 1 to 3 ug/cm on leaves. An estimate of the leaf
surface residue transfer rate to Florida strawberry harvester clothing
gave 1.44 to 4.33 mg/h. Soil residues ranged from trace amounts to 25
ppm. At a private strawberry farm, captan dissipation followed first-
order decay with half-life 5.82 + 0.35 days over a 7-week, April to June
1985, period.
This report was submitted in fulfillment of grant CR-810743 by the
Florida Pesticide Hazard Assessment Project, University of Florida,
under the sponsorship of the U.S. Environmental Protection Agency. This
report covers a period from May 1, 1983 to April 30, 1984 and work was
completed as of November 30, 1985.
ACKNOWLEDGMENT
We wish to thank the owners of the commercial and private
strawberry farms for their kind cooperation throughout the course of
this study.
iii
-------
213
FIGURES
Number Page
1. Captan dislodgeable residue dissipation from strawberry
leaves (private farm) 13
2. Captan dislodgeable dissipation half-lives from strawberry
leaves vs. mean air temperature prevailing during each
dissipation (commercial farm) 15
iv
-------
NOTICE 2 1 4
This docunent Is a preliminary draft. It has not been formally released
by the U.S. Enviroraoental Protection Agency and should not at this stage
be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications. Mention of
trade names or commercial products does not constitute endorsement or
recommendation for use.
INTRODUCTION
Captan [N-((trichloromethyl)thio)-4 cyclohexene-1,2-dicarboximide]
is a fungicide widely used by central Florida strawberry growers.
Normally, it is applied weekly throughout the entire November to March
growing season with a tractor-drawn boom sprayer. Only occasionally is
application made aerially. Workers are present in the fields during the
growing periods: harvesting later in the season, but pruning and
generally maintaining the fields earlier. Our original intent was to
2
determine the "transfer coefficient" (cm /h) between foliar dislodgeable
2
captan residues (ug/cnr) and harvester dermal exposure (ug/h), the
latter to be estimated by captan contamination of exposure pads placed
externally on the harvesters. Strawberry growers in this area, however,
unanimously declined to participate in any study directly involving
their harvesters. However, one large commercial grower did agree to
allow a foliage and soil captan residue study. What follows is a
description of that study.
Some evidence exists (cf., e.g., Stamper et al., 1986; Nigg and
Stamper, 1984; Zweig et al., 1983) that transfer coefficients are
invariant to geographical area and chemical applied, depending primarily
upon harvester work practices (usually dictated by general crop type,
e.g., tree crops, low-lying vegetables, etc.) and secondarily on worker
productivity rate. Several California studies relating strawberry
harvester exposure to foliar captan residues have been published
(Winterlin et al., 1984; Zweig et al., 1983; Popendorf et al., 1982).
Using transfer coefficients reported by these researchers, estimates of
Florida harvester exposure to captan can be made with some confidence
from Florida foliar captan residues. It should be noted that
-------
215
researchers concerned with this problem typically use varying numbers of
exposure pads and locations for them on the harvester, not to mention
varying numbers of harvesters and exposure periods. Furthermore,
although a total body estimate of harvester exposure is often made,
estimates of exposure to those specific regions of the body directly
monitored by the researcher (e.g., forearms, hands, thighs, etc.) are
undoubtedly more reliable.
EXPERIMENTAL DESIGN AND SAMPLING
Two locations for the residue study were selected. Leaf and soil
residue levels were monitored over the entire growing season at a large
commercial strawberry farm in eastern Hillsborough county of central
Florida. It was important to monitor residue levels over the entire
season because workers are present in the field and subject to captan
exposure during the entire season. Since a captan dissipation half-life
could not be reliably determined from a commercial farm to which captan
is applied so frequently, a second location was selected. It was a
private residential farm in western Polk County, 10 miles east of the
commercial farm.
At both locations, strawberry plants had been planted in long
parallel two-row beds. The beds themselves were elevated about 20 cm.
The soil of the beds was covered with dark green plastic sheeting,
allowing no contact between fruit or foliage and bed soil. Exposed soil
lay between the beds. The strawberry plants were of the Douglas
variety.
Each daily sample of soil and/or leaves was replicated six times.
Surface soil was collected by drawing it upward through a 40-mesh screen
with a commercial grade "mini-vac" vacuum device. Leaf samples were
2
collected by excising a 5.067 cm circular punch from the center of the
leaf. These sampling methods, as well as general guidelines for the
extraction of dislodgeable residues from foliage and soil, are described
by Gunther et al. (1977) and Iwata et al. (1977). The sampling region
for a single replicate consisted of two parallel, two-row beds of
plants, 31 m and 90 plants long. This region formed what can be
envisioned as a rectangular matrix of individual plants with four "rows"
-------
216
and 90 "columns." The first post-spray leaf sample replicate Included
one excision from the following plants, designated by matrix site:
(1,1). (2,1), (3,1). (4,1); (1,11), (2,11), (3,11), (4,11); ...; (1,81),
(2,81), (3,81). (4,81). Thus, one replicate contained 36 leaf punches
and constituted a total leaf surface area (both sides counted) of 364.8
2
cm . Soil was sampled between leaf sample sites at matrix columns 1,
11, ..., 81, and combined as one replicate. The second replicate for
this day was taken in the same way, but from rows 5-8; the third from
rows 9-12; and so on through rows 21-24. The second post-spray daily
sample came from matrix sites (1,2), (2,2), (3,2), (4,2); (1,12),
(2,12), (3,12), (4,12); ...; (1,82), (2,82), (3,82), (4,82) for the
first replicate, and similarly as above for the remaining replicates for
that day. Continued sampling adhered to this pattern. Following a
fresh application of captan, these 24 sampled rows were abandoned in
favor of rows 25-48, which were sampled in the same way as were rows
1-24, until the next application. This sampling scheme, while not
random, provided a thorough coverage of the sampling area and guaranteed
that no soil site would be sampled twice and also that soil samples
would be gathered from sites precisely between leaf sampling sites. All
samples were placed in an ice chest after collection and transported to
the laboratory. Leaf samples were extracted immediately; soil was
stored at -17°C prior to extraction. Weather data were taken at both
farms in the hope that they might explain any residue dissipation rate
differences found within this study or between those of this study and
other similar studies. Temperature and humidity were monitored with a
Bendix hygrothermograph enclosed in a ventilated, white, wooden
structure 2.5 m above ground. Solar radiation intensity was monitored
with a mechanical pyranograph. Rainfall data were taken, but were
overwhelmed by the irregular yet vigorous irrigation regimen employed by
the commercial farm, both to provide water to the plants and to minimize
freeze damage. Weather data from both farms appear in Appendix (A) of
this report. Appendix (B) provides a summary of the quality assurance
(QA) aspects of all procedures used for this study.
-------
217
APPLICATION OF COMPOUND
Application of captan was made to the commercial strawberry farm
about once per week throughout the entire growing/harvesting season of
November 1984 to March 1985. Except for one aerial application, a
tractor-drawn boom sprayer was used. The application rate varied from
2.3 to 11.3 kg a.i./500 gal/5A. Captan (0.0456 kg a.i. wettable
powder/2 gal) was applied to runoff with a 2-gal hand-pump garden
sprayer at the private farm on April 29, 1985 and not at all thereafter.
The application rate history of both experimental areas appears in TABLE
1. Samples were taken of the liquid formulation at the commercial farm
and of the tank mixture containing a wettable powder formulation at the
private farm.
TABLE 1. APPLICATION HISTORY OF CAPTAN TO THE EXPERIMENTAL
PLOTS.
Date
applied
11/06/84
11/17/84
11/19/84
11/27/84
12/04/84
12/11/84
12/28/84
01/09/85
01/16/85
01/24/85
01/31/85
02/18/85
02/25/85
04/29/85
Rate
Commercial Farm
2.3 kg (a.i.)/500 gal/5A
2.3
11.3
11.3
11.3
11.3
11.3
4.5
4.5
4.5
4.5
11.3
11.3
Private Farm
0.0456 kg (a.i.)/2 gal
Formu-
lation
50 WP
50 WP
50 WP
50 WP
50 WP
50 WP
50 WP
4 L
4 L
4 L
4 L
50 WP
50 WP
50 WP
Method
Boom sprayer
it
ii
H
a
H
H
H
H
Aerial
Boom sprayer
H
H
Hand sprayer
-------
MATERIALS AND METHODS 2 1 8
EXTRACTION
Leaves
Each leaf disk sample was agitated at 200 cpm for 10 min with 50 ml
of Surten solution. The Surten solution used was a 1:12,500 dilution of
a 70% solution of sodium dioctyl sulfosuccinate (Surten, ICN
Pharmaceuticals, Plainview, NY). This wash was then decanted into a
separatory funnel and the leaves shaken for an additional 10 min with 50
ml of Surten solution. The second wash was combined with the first,
extracted in a separatory funnel with 50 ml methylene chloride, and
drained into a 500 ml boiling flask. The combined wash was decanted
back into the separatory funnel and extracted with 50 ml ethyl acetate.
The combined extracts (methylene chloride and ethyl acetate) were taken
to dryness on a rotary evaporator at 40°C and brought up in 10 ml of
ethyl acetate for GLC analysis.
Initially, the GLC analysis of exposed leaf sample extracts
contributed too much interference near the captan peak and also reduced
column life. Additional sample preparation was therefore required.
Sep-pak® (Waters Assoc., Milford, MA) sample cleanup was used. The
samples in ethyl acetate were taken to dryness using a Ng evaporator at
40°C. Ten ml of hexane was added to the evaporation vial. The Sep-pak*
silica cartridge was prepared for sample addition by eluting the blank
cartridge with 10 ml of methylene chloride, followed by 10 ml of hexane.
The sample was then slowly applied in hexane to the cartridge. The
sample vial was rinsed with 10 ml hexane and this was slowly applied to
the same cartridge. The sample was eluted off the column with 10 ml
methylene chloride into a 50 ml boiling flask. The hexane fractions
prior to elution were discarded. The sample was taken to dryness on a
rotary evaporator at 40°C and brought up in 10 ml hexane for GLC
analysis. Processed samples were stored at -17°C. Unexposed leaves
were not available to fortify or to use as blanks. Consequently, Surten
solution alone was fortified with 10 ug and 100 ug captan. These served
as a surrogate fortified "leaf" sample for quality control and methods
-------
219
development. Unfortified Surten served as a blank. One of each of
these QA/QC samples was extracted and analyzed with each set of six
exposed leaf sample replicates. Recoveries of captan (10 ug)
fortifications of the Surten solution were 75.4 +_ 0.6% (SEM).
Soil
Ten grams of each soil sample was weighed into a 100 ml beaker and
50 ml of ethyl acetate was added. The beaker was covered with a watch
glass and stirred with a magnetic stirrer, creating a vortex, for 10
min. The sediment was allowed to settle and a 30 ml aliquot was taken.
This aliquot was reduced to dryness on a N« evaporator at 40°C and 5 ml
of hexane was added for the Sep-pak® sample cleanup described above,
prior to GLC analysis. Processed samples were stored at -17°C.
Unexposed soil used for preparing blank and fortified (10 ug) samples
was collected at the Citrus Research and Education Center in Lake
Alfred, FL. The soil was washed with acetone and dried on a rotary
evaporator. One blank and one fortification was extracted and analyzed
with each set of six exposed soil sample replicates. Recoveries from
fortified (1 ppm) blank soil were 58.7 +. 2.6% (SEM).
GAS-LIQUID CHROMATOGRAPHY
GLC was performed on a Hewlett-Packard 5730A chromatograph equipped
with an electron-capture detector and a 91 cm x 2 mm silanized glass
column packed with 4% SE-30/6% SP 2401 on 100/120 Supelcoport*.
Operating conditions were: injection port 210°C, detector 270°C, N2 50
ml/min, oven temperature 170°C isothermal. Quantification of samples
was by input of a sample peak height into a model developed from a daily
standard curve (peak height vs. concentration). The minimum detection
limit, defined here as ten times the GLC baseline noise level, was 15 pg
from the standard 5 ul injection, or 3 ppb. For 10 ml of leaf sample
2
extract from 364.8 cm of leaf area, the minimum detection limit was
2
0.0001 ug/cnr. The presence of the metabolite of captan (THPI) was not
assessed. Analytical standards of captan (99% pure) were provided by
Ortho Chevron Chemical Co., Richmond, CA. Stock standard solutions were
1 mg/mL in toluene.
-------
220
RESULTS AND DISCUSSION
The analysis of the liquid formulation of captan (Captec 4L),
sampled February 6, 1985 at the commercial farm, gave 39% a.1., while
the label read 38% a.i. Laboratory analyses of the tank mixture,
sampled at the private farm April 29, 1985, averaged 0.024% a.i.,
whereas the measured mixture was 0.6% a.i. Thorough mixing of this tank
mixture was probably not achieved at the private farm.
TABLE 2 summarizes the residue and quality control data taken from
the commercial farm. Mean dislodgeable residues from six replications,
followed by the standard error of the mean, are presented for leaf and
soil surfaces. The 90% confidence interval is twice that given by the
standard error. The coefficient of variation (relative standard
deviation) among the six replicates averaged 33% for leaves and 74% for
soil. For ease in comparing with exposed leaf samples, blank leaf
2
sample results have been normalized to ug/cm units, even though no
P
actual leaves were used. Leaf residues below 0.01 ug/cm and soil
residues below 0.1 ppm, while detectable, are not statistically
important to this study and are reported as "Trace." Mean recovery from
fortifications was 50% for leaves and 59% for soil.
TABLE 3 summarizes the residue and quality control data from the
private farm. The coefficient of variation among the six leaf
replicates averaged 43%. The surprisingly large pre-spray residue found
on leaves from a plot unsprayed for 81 days probably resulted from
captan applied by the grower at the commerical facility who supplied
plants to the private farm. Low levels of captan detected in blanks are
evidence of some cross-contamination, although not enough to affect
conclusions drawn here. They resulted, we feel, from laboratory needle
and syringe contamination. Mean (leaf) recovery from Surten solution
fortifications was 52%. This mean recovery and the 50% mean recovery
from TABLE 2 are some 25 percentage points lower than methods
development recoveries. We have no explanation for this result.
Residue levels appearing in TABLES 1 and 2 have not been corrected
for recovery. A separate analysis of all data using recovery-corrected
residue levels led to no appreciable change in the overall conclusions
reached.
-------
221
TABLE 2. CAPTAN RESIDUES ON LEAF AND SOIL SURFACES (COMMERCIAL STRAWBERRY FARM).
Days post
last
Date applicatioi
11/14/84
15
16
20
21
26
27
28
29
30
12/03/84
04
05
06
07
10
11
12
13 ,
14
01/10/85
,,11
14
15
16
17
18
25
(Continued)
8
9
10
1
2
7
0
1
2
3
6
7
1
2
3
6
0
1
2
3
1
2
5
6
7 .
1
2
1
Leaf
Residue Recovery
i (ug/cm2) (%)
0.04 +. 0.01a
0.17 ^0.03
0.08 +_ 0.029
1.06 +,0.10
1.75 +_0.519
0.79 +_0.09
1.56 +_0.14
0.82 +_ 0.08
0.56 +_0.09
0.58 +_0.07
0.66 +_ 0.13
0.51 +.0.11
0.86 +_ 0.08
0.85 +_ 0.08
0.87 +_ 0.08
0.68+0.11
0.65 +_0.15
1.36 +_0.29
0.84 +_0.18
0.43 + 0.03
0.71 +_0.07
0.54 +_0.03
0.50 +0.05
0.58 +_0.08
0.42 +_0.11
0.74 +_0.07
0.61 +_0.03
0.62 +_0.06
68
" 68
64
48
68
49
55
45
62
54
51
45
57
37
71
50
62
77
56
59
57
46
42
39
24
38
49
32
Blank
2
(ug/cm )
NDd
ND
ND
ND
ND
ND
ND
ND
ND
ND
Tr
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Soil
Residue Recovery0
(ppm) (*)
Tr6'9
ND
Tr
14.9 + 3.5a
14.5 +4.7
1.6 +_ 0.5
11.8 i 1.6
12.0 +_2.9
0.9 +_0.2
1.0 _+ 0.7
1.4 +.0.4
1.4 +_0.5
7.5 + 1.3
13.9+2.8
10.5 +_ 1.2
3.1 +_ 1.4
14.7 +_ 3.6
12.6 +_ 3.2
10.2 +3.1
3.3 +_0.9
8.5 + 1.2
2.0 +_0.6
1.4 +_0.5
1.0 +_0.39
0.4 +_ 0.1
5.0 +_0.4
0.4 +_ 0.1
h
Lost
75
95
80
78
93
47
60
17
89
38
105
80
105
65
78
70
98
60
70
60
51
56
114
63
47
47
h
Blank
(ppm)
ND
ND
Tr
Tr
Tr
Tr
Tr
Tr
ND
Tr
Tr
Tr
Tr
0.1
Tr
Tr
ND
Tr
Tr
Tr
Tr
Tr
Tr
Tr
Tr
ND
0.2
h
-------
222
TABLE 2. (Continued)
Days post
last
Date applicatior
29
30
31
02/01/85
04
06
07
11
12
13
14
18
19
20
.21
22
25
26
27
28
03/01/85
6
7
8
1
4
6
7
11
12
13
14
18
1
2
3
4
7
1
2
3
4
Leaf
Residue Recovery
i (ug/cm2) (%)
0.34 +_ 0.04
0.54 4- 0.06
0.62 +_ 0.07
0.99 + 0.08f
0.64 + 0.08f
0.41 + 0.04
0.40 +_ 0.05
0.16 +_ 0.01
0.17 j+0.03
0.23 +_ 0.04
0.15 +_0.02
0.13 +0.02
1.31 4-0.30
0.44 +_0.05
0.69 +_0.10
0.49 +_0.04
0.19 +_ 0.01
0.49 +_ 0.04
0.78 iO.ll
0.66 *_ 0.109
0.70 i 0.07
22
61
57
64
43
29
48
37
34
29
41
35
49
35
53
38
49
53
60
76
81
Blank
2
(ug/cm )
ND
Tr
ND
ND
ND
ND
ND
ND
ND
ND
Tr
ND
ND
Tr
ND
ND
Tr
Tr
Tr
Tr
Tr
Soil
Residue Recovery0 Blank
(ppm) (%) (ppm)
0.3 +_0.1
0.5 +0.2
0.3 +_0.1
3.8 4- 1.0
0.2 +.0.1
Tr
Tr
0.5 +_0.19
Tr
h
h
Tr
3.0 +0.6
0.3 +0.0
1.4 +_0.5
0.8 +_0.2
h
6.9;+ 4.7
1.8 +0.5
0.4 ;+ 0.3
1.6 +_0.8
51
33
42
31
ND
25
22
53
55
h
h
76
63
54
47
42
h
44
44
53
51
ND
Tr
ND
ND
ND
ND
ND
0.4-
0.1
h
h
Tr
0.4
Tr
0.1
Tr
h
Tr
Tr
Tr
Tr
aMean +^ standard error of the mean (six replications).
Recovery from 100 ug fortification.
cRecovery from 10 ug fortification.
dNone detected (< 0.0001 ug/cm2. leaves; < 0.003 ppm, soil)
€Trace (< 0.01 ug/cm2f leaves; < 0.1 ppm, soil).
replications (two replicates lost).
replications (one replicate lost).
hSoil too damp to sample.
-------
223
TABLE 3. CAPTAN RESIDUES ON LEAF SURFACES (PRIVATE STRAWBERRY FARM).
Date
4/29/85
29
30
5/01/85
02
03
06
07
08
09
10
13
21
30
6/10/85
18
Days post
last
application
81
0
1
2
3
4
7
8
9
10
11
14
22
31
42
50
Residue
2
(ug/cm )
0.07 +_ 0.01a
0.82 ^0.12
0.57 +_ 0.13
0.53 +_ 0.07
0.78 +_ 0.07
0.43 +_ 0.03
0.58 +_ 0.14
0.86 4- 0.09
0.56 +_ 0.08
0.25 +_ 0.03
0.21 +_ 0.03
0.31 ^0.03
0.09 +_ 0.01
0.02 +,0.01
(0.005 +_ 0.001)
(0.003 +_ 0.001)
b
Recovery
(«)
32
61
44
41
35
46
37
62
61
52
30
41
136
67
46
37
Blank
2
(ug/cm )
Trc
Tr
Tr
0.04
0.01
Tr
Tr
Tr
Tr
Tr
NDd
ND
Tr
Tr
ND
ND
aMean +_ standard error of the mean (six replications) from a pre-spray
sample.
Recovery from 100 ug fortification.
cTrace (< 0.01 ug/cm2).
dNone detected (< 0.0001 ug/cm2).
Captan applications to the commercial farm were so frequent
(TABLE 1) and its disappearance so gradual that reliable decay rates
were difficult to ascertain from the commercial farm data. Four
periods, uninterupted by a captan application and containing five or
more sampling days, did occur. Dissipation half-lives and their
standard errors, taken from a regression analysis of the natural
logarithm of residue concentration vs. time, are presented in TABLE 4
10
-------
TABLE 4. RESIDUE DISSIPATION HALF-LIVES FROM A FIRST-ORDER REGRESSION ANALYSIS.
Leaf
Soil
Half-life*
Period (days)
First-order3
corr. coeff.
No. Half-life3
points (days)
First-order No. Mean dally
corr. coeff. points avg. temp.(*C)
11/27/84- 6.83 +_ 3.59 0.69
12/04/84
Commercial strawberry farm
6 2.46 + 1.48 0.64
18 * I1
01/10/85- 12.66 +_ 6.62 0.74
01/16/85
02/01/85- 5.50^0.67 0.95
02/18/85
02/19/85- 2.53+0.75 0.89
02/25/85
Mean 6.88 +_ 1.89
04/29/85- '5.82 + 0.35 0.98
06/18/85
5 1.74 + 0.42 0.92
9 5.59 + 5.44 0.42
5 3.05 + 7.11 0.29
3.21 +2.27
Private strawberry farm
15
11
15
20
25 + 0.3
aFrom a regression analysis of In (concentration 1n ug/cmz or ppm) on time, taken from the data of
TABLES 1 and 2.
bMean + standard error of the mean.
-------
225
for each of these four periods. Correlation coefficients are low and
standard errors large. A mean half-life taken over all four periods
yields a somewhat longer half-life for dislodgeable captan on leaf
surfaces than on soil surfaces, but the difference is not statistically
significant. At the private farm, however, only the Initial application
of captan was made during the sampling period, permitting construction
of a 15-point dissipation curve (Figure 1) extending over a 7-week
period. The results of a regression analysis for first-order half-life
from this sampling period also appear in TABLE 4. Only 4.4% of the
private farm data is unexplained by its fit to first-order decay. The
resulting half-life of 5.82+^0.35 days is statistically quite precise.
It does not differ significantly from the dislodgeable dissipation
half-life of 9.0 +_ 3.5 days (standard error, our calculation) reported
by Winterlin et al. (1984) from a California strawberry foliage study
which included 7 sampling days over a 2-week period. It is interesting
that the half-lives measured at the commercial farm show a general
decrease with increasing air temperture (Figure 2). While most
physico-chemical processes critical to dissipation should intensify with
increasing temperature, leading to a shorter half-life, the Figure 2
data contain far too much uncertainty to warrant this conclusion.
On April 2, 1985, 20 sample bottles, each containing 10 ml of ethyl
acetate, were fortified with 500 ug of 99% pure captan. They served as
samples for a captan storage loss study. Except when being analyzed,
they were stored in the same -17°C freezer as were exposed leaf and soil
sample extractions. No such extraction was stored more than 204 days.
The results of this study appear in TABLE 5. A statistical test of the
slope of the regression line of "mean storage sample recovery" vs. "time
stored" shows that the statistical hypothesis "slope * 0" cannot be
rejected, even at the 80% confidence level. Hence, no significant
variation in captan level was validated by the storage loss study. The
August 26, 1985 analysis gave much larger and somewhat more variable
result than the others. We cannot explain this, except to note that a
less experienced technician operated the GLC for this analysis.
12
-------
CO
03
-------
TABLE 5. STORAGE LOSS STUDY FROM 20 SAMPLES, EACH
FORTIFIED WITH 500 ug OF 99% PURE CAPTAN.
227
Date
analyzed
4/02/85
4/15/85
5/06/85
6/03/85
6/27/85
8/26/85
9/04/85
10/23/85
11/20/85
11/27/85
Days post
preparation
0
13
34
62
86
146
155
204
232
239
Mean +_ standard
recovery error
498^8
506 + 9
503 +_ 8
501 ^6
502 ^9
626 +_ 23
525 ^8
563 +_ 11
492 + 3
548 +_ 3
CONCLUSIONS
The weekly application frequency generally followed at the
commercial farm maintained a dislodgeable foliar captan residue level of
2
1-3 ug/cm , using both leaf sides and correcting for recovery. This
level existed throughout the entire growing season with little variation
(TABLE 2) and represents the foliar residue to which Florida strawberry
field workers are typically exposed. As an example of the use of
transfer coefficients, we employ the total-body dose to California
strawberry harvesters of 55.35 mg captan over an 8 h workday, reported
recently by Winterlin et al. (1984). This dose resulted, it is
p
presumed, from harvester contact with foliage upon which 4.79 ug/cm of
dislodgeable captan resided the day harvesters were monitored. The
transfer coefficient of (55.35 * 8) mg/h * 4.79 ug/cm2 - 1.44 x 103
2
cm /h, when applied to Florida harvesters occupying fields where the
r\
dislodgeable captan residue on foliage is 1-3 ug/cm » leads to a Florida
total-body captan accumulation rate of 1.44-4.33 mg/h. The actual
dermal dose received by the Florida strawberry harvester is reduced by
the extent to which he is protected by clothing.
14
-------
20r-
CO
%
CO
TJ
0
= 10
Commercial Farm Half-lives
0
0
0
1
0
1
12
i
14
i
16
i
18
i
20
Mean temp ( °C)
Figure 2. Captan dislodgeable dissipation half-lives from
strawberry leaves vs. mean air temperature prevailing during
each dissipation (commercial farm).
15
-------
229
Soil residues, which doubtless also play a role in harvester
exposure, were more variable, ranging from trace amounts to 25 ppm,
corrected for recovery.
Under the conditions prevailing from April 29, 1985 to June 18,
1985, captan exhibited first-order dissipation from strawberry leaves
with half-life 5.82 ^ 0.35 days.
RECOMMENDATIONS
This study leaves little doubt as to the captan levels on leaf and
soil surfaces to which Florida strawberry harvesters are typically
exposed, as well as the dissipation rate of captan from strawberry leaf
surfaces. No repeat of this experiment is therefore recommended.
Should Florida strawberry growers later allow their harvesters to
participate in a study assessing harvester exposure, this should be
undertaken ... as a test of the geographical invariance of the
foliage-to-worker transfer coefficient.
Future experiments should always employ sufficient sample
replications that, given the large sampling and analysis variability
attendant to studies of this type, meaningful statistical results are
likely. For the present study, built-in design features such as six
replications per leaf and soil sample and a 15-point dissipation curve
were crucial.
Parenthetically, we recommend that future transfer coefficient
experiments adhere as closely as is feasable to a uniform design so that
comparisons among them for invariant features can be made.
Specifically, we suggest uniformity in exposure pad placement and
number, number of subjects, and number of sampling periods per subject.
Finally, regarding quality assurance, we suggest that laboratory
supervisors consider devising some method for assessing which of their
technicians might have erred, and in which procedure, when a final
result (e.g., fortification or blank) shows clearly that an error was
made. Often the error's source is obscured by the circumstance, e.g.,
that one technician extracted while another operated the chromatograph
for that sample.
16
-------
230
REFERENCES
1. Gunther, F. A., Y. Iwata, G. E. Carman, and C. A. Smith. The citrus
reentry problem: research on its causes and effects, and approaches
to Its minimization. Res. Rev., 67:1-139, 1977.
2. Iwata, Y., J. B. Knaak, R. C. Spear, and R. J. Foster. Worker
reentry into pesticide-treated crops. I. Procedure for the
determination of dislodgeable pesticide residues on foliage. Bull.
Environ. Contam. Toxicol., 18:649-655, 1977.
3. Nigg, H. N., and J. H. Stamper. The development and use of a
universal model to predict tree crop harvester pesticide exposure.
Am. Ind. Hyg. Assoc. J., 45:182-186, 1984.
4. Popendorf, W. J., J. T. Leffingwell, H. R. McLean, G. Zweig, and
J. M. Witt. Youth in agriculture - pesticide exposure to strawberry
pickers; 1981 studies; final report submitted to Office of Pesticide
Programs, EPA, Washington, DC, Sept. 1982.
5. Stamper, J. H., H. N. Nigg, and R. M. Queen. Prediction of
pesticide dermal exposure and urinary metabolite level of tree crop
harvesters from field residues. Bull. Environ. Contam. Toxicol.,
36:693-700, 1986.
6. Winterlin, W. L., W. W. Kilgore, C. R. Mourer, and S. R. Schoen.
Worker reentry studies for captan applied to strawberries in
California. J. Agric. Food Chem., 32:664-672, 1984.
7. Zweig, G., R. Gao, and W. Popendorf. Simultaneous dermal exposure
to captan and benomyl by strawberry harvesters. J. Agric. Food
Chem., 31:1109-1113, 1983.
17
-------
231
APPENDIX (A). WEATHER DATA
Temperature (°C)
Max. Min.
Hours daily
rel. hum. > 90%
Rainfall3
(cm)
Solar rad.
(cal/cm2)
11/14/84
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
12/01/84
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
(continued)
22
25
26
26
28
27
22
20
12
18
22
23
24
28
25
20
23
23
27
26
26
28
23
13
18
21
21
24
23
24
25
24
26
25
24
27
26
24
25
26
26
26
27
27
Commercial strawberry farm
3
9
9
11
13
17
17
11
7
7
10
12
12
14
11
6
5
14
13
16
16
19
7
1
1
2
4
12
10
7
14
14
13
17
14
12
12
12
12
11
12
12
16
18
7
6
11
9
11
9
9
15
13
1
0
10
7
6
12
3
9
7
16
14
8
11
8
2
5
13
14
7
14
8
1
2
13
9
5
12
9
6
6
12
9
7
11
12
Tr
Tr
Tr
378
355
334
343
290
284
161
138
103
155
340
264
217
308
199
393
287
293
229
240
220
229
161
352
343
357
325
237
302
308
211
179
226
243
252
316
311
243
281
270
284
261
287
214
18
-------
232
APPENDIX (A), (continued)
Temperature (°C) Hours daily Rainfall3
Max. Min. rel . hum. > 90% (cm)
Solar rad.
(cal/cm2)
28 27
12/29/84 26
30 27
31 26
01/01/85 27
02 26
03 21
04 17
05 12
06 16
07 20
08 18
09 21
10 24
11 23
12 9
13 16
14 14
15 15
16 20
17 26
18 17
19 18
20 21
21 2
22 8
23 14
24 19
25 21
26 13
27 20
28 21
29 20
30 23
31 28
02/01/85 29
02 28
03 24
04 24
05 27
06 27
07 19
08 13
09 19
(continued)
Commercial strawberry farm
19
13
13
14
16
17
18
14
7
2
2
7
3
4
11
3
2
8
2
2
9
9
6
3
-6
-5
0
4
13
1
1
7
8
9
16
16
19
15
15
16
14
10
4
2
9
10
8
8
4
8
22
0
0
5
11
12
10
8
3
0
0
9
4
6
7
11
13
8
0
4
10
2
12
5
8
9
2
1
0
8
14
8
0
12
14
8
0
8
0.25
0.86
0.89
0.51
0.25
Tr
1.55
0.89
205
199
290
299
264
196
64
105
237
378
355
349
369
302
293
149
325
147
401
384
296
103
360
275
440
413
363
357
234
413
404
255
390
270
384
360
255
314
305
299
144
226
314
428
19
-------
233
APPENDIX (A), (continued)
Temperature (°C) Hours dally Rainfall3
Max. Min. rel . hum. > 90% (cm)
10
11
12
13
14
02/15/85
16
17
18
19
20
21
22
23
24
25
26
27
28
03/01/85
04/29/85
30
05/01/85
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
(continued)
21
21
13
12
16
13
17
23
24
26
26
24
27
27
28
27
28
28
27
28
31
28
29
30
28
28
29
30
31
31
31
31
33
32
33
34
33
33
30
b
b
Commercial
6
12
8
3
3
3
2
4
8
10
11
11
15
13
17
12
16
13
15
14
Private
19
17
13
17
19
18
17
15
14
17
20
17
18
17
18
19
18
19
18
b
b
strawberry farm
7
8
0 1.52
1
3
3 0.76
6
0
5
10
8
7
0
5
6
9
10
9
9
9
strawberry farm
9
5
3
0
2 1.07
8
6
5
8
1
0
7
9
8
5 Tr
7
6
6
5 Tr
a
a
Solar rad.
(cal/cm2)
431
149
290
454
431
179
425
349
357
349
343
437
434
319
398
322
372
440
396
346
_•
319
437
481
331
369
501
583
489
481
542
407
428
527
481
516
437
522
483
607
425
20
-------
234
APPENDIX (A), (continued)
Temperature (°C) Hours daily Rainfall3
Max. Min. rel . hum. > 90% (cm)
20
21
22
23
24
25
26
27
28
05/29/85
30
31
06/01/85
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
b
b
33
32
28
31
31
31
32
32
33
35
34
34
37
37
36
36
34
36
32
33
33
31
29
23
29
32
34
33
Private
b
b
20
21
21
20
18
14
15
17
17
18
20
20
22
22
23
21
22
21
20
22
22
22
20
20
19
23
21
22
strawberry farm
a
a
8
6
6 Tr
8
6
6
3
3
4
3
4
7
7
8
3
7
2
5
8
8 3.10
5
9
13
19 4.32
12
9
7
6 3.61
Solar rad.
(cal/cm2)
457
448
437
530
311
460
478
472
527
501
475
501
560
586
571
504
542
516
407
440
422
413
507
404
316
167
229
387
466
501
aRainfall data at the commercial farm overwhelmed by unmonitored
irrigation practices.
Hygrothermograph malfunction.
APPENDIX (B). QUALITY ASSURANCE
While harvester exposure pads and gloves were ultimately not
employed in this experiment, preliminary recovery studies were carried
out. Technician recoveries from captan-fortified exposure pads
21
-------
235
TABLE B-l. TECHNICIAN CAPTAN RECOVERIES FROM FORTIFIED EXPOSURE PADS,
PRIOR TO EXPERIMENT.
Technician
Robert Queen
Robert Queen
Robert Queen
Thomas Bailey
Thomas Bailey
Thomas Bailey
Thomas Bailey
Fortification Individual
level recoveries
(ug) (%)
1 76.8
78.3
98.5
88.4
10 83.9
92.3
100.0
99.2
100 84.1
81.3
83.2
86.6
1 95.4
95.4
113.0
150.1
10 92.0
92.0
100.0
107.0
100 95.0
93.3
85.0
89.5
1 100.0
96.3
81.5
96.3
Mean +_ SEM
(%)
85.5 ±5.1
93.9 ± 3.7
83. 8 i 1.1
113.5 ± 12.8
97.8 ±3.6
90.7 ±2.2
93.5 + 4.1
(continued)
22
-------
236
TABLE B-l. (continued)
Technician
Robert Williams
Robert Williams
Robert Williams
Fortification Individual
level recoveries
(us) (%)
1 88.0
97.0
89.0
98.0
10 92.4
86.4
90.9
96.2
100 92.0
92.7
91.4
92.9
Mean +_ SEM
(%)
93.0 _+ 2.6
91.4 ±2.0
92.2 ±0.3
extracted prior to the experiment are given in TABLE B-l. Technician
recoveries from captan-fortified gloves extracted prior to the
experiment are given in TABLE B-2. Mean percentage recovery for each
technician taken over four replications using three fortication levels
(1, 10, 100 ug), followed by the standard error of the mean, are given.
Recoveries yielding means not within laboratory limits (usually ± 10%)
were repeated. Each technician involved in the study ran the recoveries
to establish a laboratory recovery range. Preliminary recoveries of
captan from fortified (100 ug) Surten washes taken through Sep-pak*
sample preparation had a mean ± SEM of 75.4% ± 0.6%. Recoveries from
captan fortified (10 ug) soil were 58.7% ± 2.6%.
Laboratory precision and accuracy were monitored as follows. A
control chart (TABLE B-3) of all personnel involved in the experiment
was developed. Periodically, all technical personnel who operated the
23
-------
237
TABLE B-2. TECHNICIAN CAPTAN RECOVERIES FROM FORTIFIED GLOVES, PRIOR TO
EXPERIMENT.
Technician
Thomas Bailey
Thomas Bailey
Thomas Bailey
Robert Queen
Robert Queen
Robert Queen
Fortification Individual
level recoveries
(ug) (%)
1 71.2
108.7
108.7
105.0
10 111.7
132.4
120.0
132.4
100 93.0
93.0
75.0
96.0
1 87.0
79.5
79.5
10 89.5
93.3
93.3
100 96.2
90.0
98.6
Mean +_ SEM
(*)
98.0 ^9.1
124.1 4-5.1
89.3 ^4.1
82.0 ^4.3
92.0 ^2.2
94.9 + 4.4
24
-------
238
TABLE B-3. CAPTAN GLC CONTROL CHART (DATA, BY TECHNICIAN)
Fort . No . Mean
Subject/date level (T) samples (x)
Darlene Williams
03/13/85
Charles Bryan
03/28/85
Robert Williams
03/28/85
Darlene Williams
04/3/85
Darlene Williams
04/18/85
Darlene Williams
04/2/85
Darlene Williams
04/15/85
Robert Williams
05/6/85
Darlene Williams
05/31/85
Darlene Williams
06/27/85
Sheryll Queen
08/26/85
Darlene Williams
09/4/85
Sheryll Queen/
Thomas Bailey
10/23/85
Darlene Williams
11/20/85
Sheryll Queen
11/27/85
0.5 ppm
2.5 ppm
10.0 ppm
0.5 ppm
2.5 ppm
10.0 ppm
0.5 ppm
2.5 ppm
10.0 ppm
1.0 ppm
5.0 ppm
10.0 ppm
1.0 ppm
5.0 ppm
10.0 ppm
500 ug
500 ug
500 ug
500 ug
500 ug
500 ug
500 ug
500 ug
500 ug
500 ug
4
4
4
4
4
4
4
4
4
4
4
4
• 4
4
4
20
20
20
20
20
20
20
20
20
20
1.01
3.34
11.10
0.51
2.82
8.35
0.52
2.53
10.47
1.42
5.03
10.91
1.06
4.54
9.35
497.89
506.19
503.74
501.34
502.23
626.20
525.25
563.33
491.55
548.50
Std.
dev. (s)
0.964
0.761
1.309
0.0334
0.1299
0.6074
0.0170
0.1185
0.9004
0.6530
0.6074
1.2093
0.1749
0.1737
0.4170
35.67
38.24
35.19
26.10
39.10
104.80
35.51
51.42
13.15
3.36
Prec.
(f 100) (
95%
23%
12%
7%
5%
7%
3%
5%
9%
46%
12%
11%
2%
4%
5%
7.16%
7.55%
6.99%
5.21%
7.78%
16.74%
6.76%
9.13%
2.67%
3.06%
Ace.
£f- 100)
+102%
+ 34%
+ 11%
+ 2%
+ 13%
- 16%
+ 4%
+ 1%
+ 5%
+ 42%
+ 0.5%
+ 9%
+ 6.4%
- 9.2%
- 6.5%
- 0.42%
+ 1.24%
+ 0.75%
+ 0.27%
+ 0.45%
+ 25.24%
+ 5.05%
+ 12.66%
- 1.69%
+ 9.70%
25
-------
239
GLC were given tests for precision and accuracy. Each was presented
with 12 blind, spiked samples. The 12 samples contained four samples at
each of three fortification levels. TABLE B-3 lists the mean percentage
recovery (x) for each technician for the three fortification levels (T),
followed by the standard deviation(s), precision (s/x) 100%, and
accuracy [(x - T)/T] 100%. If a technician's precision or accuracy was
below general laboratory standards for the chemical being analyzed, the
reason for the substandard result was determined, corrective action
taken, and another set of samples was given to the technician for
analysis. This type of test uses individually derived results. Any
error is unambiguously attributable to only one technician. The captan
storage loss study was added to the control chart because it also
contained individually derived results for a fortified material with 20
replications at a single fortification level. A second test of
precision and accuracy represents group-derived results. These include
collection, extraction, and analysis by several different technicians in
the laboratory. TABLES 2 and 3 contain leaf and soil recovery values
for individual daily recoveries. Precision values (relative standard
deviation) among the six replicates averaged 33% for leaves and 74% for
soil at the commercial farm (TABLE 2). Mean recovery from
fortifications was 50.4 +_ 14.0% for leaves and 58.8 +_ 26.4% for soil.
At the private farm, the relative standard deviation among the six leaf
replicates averaged 43%. Mean recovery from fortifications was 51.8+^
25.2% for leaves at the private farm. Precision values for the
laboratory analysis of fortified samples were 27.8% for leaves and 44.9%
for soil at the commercial farm. The precision was 48.7% in the
laboratory analysis of fortified samples for leaves at the private farm.
TABLE B-4 lists the samples that were lost and the reason for each
loss. With nearly 1000 samples analyzed, a loss of 12 samples
constitutes a 1.2% loss rate. No corrective action was taken for the
dropped samples. Corrective steps were taken, however, to limit the
number of samples accidentally combined during the Sep-pak* sample
preparation procedure. One technician (RW) was fired due to a
consistent inability to follow procedures.
26
-------
240
An external QA audit for FY '85 was performed on May 2-3, 1985 by
Anne Keller, Chemist, U.S. EPA. She primarily addressed dislodgeable
captan residues in Florida commercial strawberries, the study presented
here. Specific recommendations included: 1) documenting changes in the
project plan to accommodate no harvester participation, 2) addition of
sample calculations to the SOP manual, 3) adherence to the expiration
date of standards along with documentation of the method of storage and
disposal, 4) expanding the instrument log to include more information
about instrument problems and recalibration, and 5) addition of a log
book of inspections and technician checks. These recommendations have
been adopted. The Florida NPHAP received an overall grade of 96% on the
FY '85 QA audit.
TABLE B-4. CAPTAN RESIDUE SAMPLES LOST PRIOR TO GLC ANALYSIS.
Sampl e
No.
1PF4
1PFS
3PF3
SI
6PF4
26PF6
34PF1
34PF3
35PF1
35PF2
38PF5
50PF1
Sampl e
type
Soil
Soil fort.
Leaves
Soil fort.
Leaves
Soil
Leaves
Leaves
Leaves
Leaves
Soil
Leaves
Date
taken
11/14/84
11/14/84
11/16/84
02/13/85
11/21/84
01/15/85
02/01/85
02/01/85
02/04/85
02/04/85
02/11/85
02/28/85
Reason for loss
Accidentally combined with 1PF5 during
Sep-pak" procedure
Sample lost or never prepared
Dropped into water during drydown
Dropped into water during drydown
Vial cracked
Generator malfunction; did not take
sample
Vial dropped taking samples out of
freezer
Vial dropped taking samples out of
freezer
Vial contents spilled in laboratory
Vial contents spilled in laboratory
Vial dropped/cracked in laboratory
Vial contents spilled in laboratory
27
-------
241
A final quality assurance experiment was undertaken in April 1986.
Samples which had not been discarded were removed from storage and
from these, 17 were randomly chosen. Five ml of each sample was
transferred to a vial, evaporated to dryness on a nitrogen evaporator at
40°C, and 5 ml of hexane was added. Two sets of samples thus resulted:
one N-evaporated and the other non-N-evaporated. Three individual
aliquots of each sample from each set were analyzed under the same GLC
conditions as previously described except that an autosampler made the
injections. The non-N-evaporated samples were analyzed first and
sequentially.
This experiment was designed to determine whether, by chance, the
methylene chloride originally used for eluting from the Sep-packs* may
not have been taken to dryness and could therefore have led to variable
GLC results with electron capture detection. The object here was to
compare the variability of the two sample sets. There could be no
comparison with the original sample analyses as more than one year of
storage had intervened. The results are reported in TABLE B-5.
No significant difference (p < 0.05) existed in variability between
the two sample sets. This was confirmed by a correlated t-test on the
coefficients of variation. Viewed as uncorrelated groups, the mean
coefficient of variation of the non-N-evaporated set was 5.7 +_ 1.4%
(SEM) and 5.0 _+ 1.0% (SEM) for the N-evaporated set. We consequently
conclude that no variability was originally introduced by evaporating
methylene chloride on a rotary evaporator, i.e., samples had actually
been taken to dryness or any possible residual methylene chloride had
not led to variable GLC analyses.
The mean residues (TABLE B-5) do differ significantly (p < 0.05)
individually, but the difference is small with no significant trend
toward higher values for one set over the other. This was confirmed by
a correlated t-test (p < 0.05) on the mean values themselves. The mean
ratio of non-N-evaporated residue to N-evaporated residue was 1.18, but
with a 95% confidence interval of + 0.38.
28
-------
242
TABLE B-5. COMPARISON OF NON-N-EVAPORATION EXTRACTION METHOD WITH
N-EVAPORATION.
Date
collected
11/20/843
21
26
26
29
29
12/12/84
01/09/85
10
14
16
30
31
02/01/85
12
18
27
Replicate
number
4
2
3
4
3
5
1
1
2
4
1
4
3
5
2
1
5
Non-N-evap.
residue (ug)
18.69 +_ 0.26 (2)b
203.27 .+ 1.14 (1)
25.95 +_ 1.64 (11)
2.92 +0.36 (21)
3.44 +_ 0.07 (4)
4.57 +_ 0.16 (6)
12.03+0.11 (2)
0.80 +_ 0.01 (1)
43. 27 +_ 0.85 (3)
5.55 +_ 0.22 (7)
0.63+0.01 (3)
0.77+_0.02 (5)
0.67+0.01 (3)
38. 45 +_ 0.70 (3)
0.51+_0.00 (0)
1.51 +_0.14 (16)
1.08 +_ 0.05 (9)
N-evap.
residue (ug)
13.33 + 1.09 (14)b
77.86 i 1.81 (4)
19.33+1.00 (9)
5.26+^0.20 (7)
6. 19 +_ 0.08 (2)
2.87 +_ 0.06 (3)
8.46+0.06 (1)
1.35 +_0.08 (10)
30. 58 +_ 1.63 (9)
5. 39 +_ 0.07 (2)
0.86+0.01 (2)
1.13+_0.04 (6)
1.37+_0.03 (3)
28.99 +_ 0.03 (0)
0.17 +_ 0.01 (10)
2.44 +_ 0.02 (1)
1.64 +_ 0.02 (2)
Leaf residues at the commercial farm, date collected.
bMean of three measurements +_ standard error of the mean, with coefficient of
variation (%) in parentheses.
29
-------
243
Assessment of Dermal and Respiratory
Exposure of Adult and Juvenile Tobacco
Harvesters to Acephate, DupUn County,
North Carolina
Research performed by
Medical University of South Carolina
April 27, 1984
-------
244
Table of Contents
Title Page
Abstract 11
List of Tables Ill
I. Objective . . 1
II. Background 1
III. Methods 2
IV. Analytical Procedures , 9
V. Quality Assurance 10
VI. Results 15
VII. Discussion 27
VIII. References 29
-------
245
Abstract
Seven juvenile and ten adult tobacco harvesters were monitored on two
consecutive days for their dermal and respiratory exposure to acephate and Its
.metabolite methamldophos. The objective of the study was to determine If there
were any differences between the exposure patterns of these two groups. Assess-
ment of dermal exposure consisted of cotton gloves for the hands and gauze
squares attached to the forearms, chest, shoulders and back of each worker.
Each participant also wore a personal air sampler during monitoring. Urine
samples were collected from each worker in order to determine whether exposure
resulted in the absorption and excretion of the chemical of study.
Statistical analyses of acephate and methamidophos residues recovered from
the sampling media found only one significant difference between the adults and
juveniles. This was the methamidophos residues observed in the first day's
chest gauze square samples and the adults were observed to have higher average
residues. Average residues declined by more than 90% between the two days of
study. Absorption and excretion of acephate and its metabolite by the partici-
pants was not demonstrated.
Environmental monitoring consisting of soil, foliage and high volume air
sampling was performed to document residue levels present during participant
monitoring.
-------
246
List of Tables
Table No. Title Page
1 Pesticides Recommended for Plant Bed and Field
Use on Flue-Cured and Burley Tobacco ..... 3
2 Participant Data 5
3 Intralaboratory Quality Assurance . 12
4 Intel-laboratory Quality Assurance . . - » ...... 13.
5 Day 1 Participant Results . . »,^-«,,-*•; ^-., . *.*.-*.. 17
6 Day 2 Participant Results . »T^-*<> » . . . > . 19
7 Statistical Analyses(t-test) of Juvenile vs.
Adult Sample Media for Each Day of Study ... 20
8 Results of Tobacco Leaf Residue Analyses .... 22
9 Results of Soil Residue Analyses 23
10 Meterological Observations 25
11 Results of High Volume Air Residue Analyses ... 26
ill
-------
I. Objective; *-^ '
The objective of this study was to assess the difference, if any,
between the dermal and respiratory exposure patterns of juvenile and
adult tobacco harvesters who, under normal working conditions, had
post application exposure to acephate.
II. Background:
The U.S. Environmental Protection Agency (EPA) and the U.S.
Department of Labor (DOL) finalized an interagency agreement on
March 17, 1980. This agreement, "Youth in Agriculture", provided
for the development of pesticide protection programs for farm workers.
The employment of children during the harvest of hand picked crops is
of special concern to the DOL. This agency has the authority to waive
restrictions to permit children to work, however it also must assure
that there are no adverse health effects to the children for which the
exemption was granted. One goal of the interagency agreement is the
determination of scientifically based reentry intervals for children
and the assessment of potential health effects of pesticides on
children working in agriculture.
The EPA and DOL have assumed that the potential for the exposure
of children to toxic chemicals in agriculture is widespread and that
children are generally nore sensitive to chemical exposure. Further-
more, children possibly have greater rates of dernal and/or gastro-
intestinal uptake and have decreased capacity for detoxification. Yet,
little or no data exists to support these assumptions as it applies to
field workers. In order to bridge this data gan, it is necessary to
perform studies which measure the pesticide exposure of adult and
juvenile workers to various pesticides during the harvest of a variety
of hand picked crops.
-------
248
Tobacco has traditionally been a hand harvested crop, although in
recent years mechanical systems have been slowly replacing human labor.
This trend toward mechanization is expected to continue. At the present
time approximately 70Z of the North Carolina tobacco crop is harvested by
hand (Wicker, 1980). Mechanical harvesters are used predominantly by
large farm operations while the smaller tobacco farms ( < 100 acres)
rely on human labor composed of both adult and juvenile workers.
Pesticides recommended for use on North Carolina flue-cured and
burley tobacco are listed in Table 1.
III. Methods;
Site - The site of study was a 60 acre flue-cured tobacco farm located in
Duplin County, North Carolina. The farm was representative of other
tobacco farms in the area in that it was average size, used ground boom
equipment for pesticide applications, and employed a harvest crew
composed of local, seasonal workers. The farmer gave his permission to
recruit and monitor his harvest crew for their dermal and respiratory
exposure to acephate and to collect environmental samples from his
tobacco field selected for study. Acephate was selected for monitoring
because it was the last pesticide applied to the crop prior to harvest.
Acephate (0,5-Diroethyl acetylphosphoranidothioate) is an organophosphate
insecticide which provides both contact and systemic control. Its only
metabolite of toxicological significance is methamidophos (0,5-Dimethyl
phosphoramidothioate). Approximately 5-102 of the acephate degrades into
methamidophos while 90-95% degrades into innocuous salts. Methamidophos was
of special interest since the metabolite is 40 times more toxic than the
parent compound (Barlas, 1984).
The tobacco field used for environmental monitoring was the same
field which was harvested by the participants over a two day period.
The field was seven acres in size, approximately 900' x 350", and
consisted of 120 crop rows which vere planted in groups of eight.
-------
Table 1
Pesticides Recommended for Plant Bed and Field Use on
Flue - Cured and Burley Tobacco
Insecticides
Fungicides
Acephate Ferbam
Azlnphosmethyl Maneb
Bacillus thuringiensls Poly ram
Carbaryl
Endosulfan
i:thyl parathion
Halathlon
Metaldehyde
Methidathlon
Me thorny 1
Methyl parathion
ilonocrotophos
Trlchlorfon
Streptomycin
Zlneb
Nematlcldes
Dlchloropropane
Dichloropropene
Ethoprop
Ethylene dlbromlde
Fenamlphos
Fensulfothlon
Methyl bromide
Oxamyl
Herbicides & Growth Regulators
Benefln
Dlphenamld
Fatty Alcohol
Fonofos
Isopropalln
Malelc hyrazlde
Napropamlde
Oryzalln
Pebulate
Pendlmethalln
North Carolina Agricultural Chemicals Manual
-------
250
This field was treated with Ortho Orthene Tobacco Insect Spray (EPA
Reg. No. 239-2419) on July 12 at a rate of 0.75 PAI/acre. Twenty days
prior (June 20) the field was also sprayed with the same product at
the same rate. Environmental sampling consisting of soil, tobacco leaf
and high volume air occurred immediately prior to the application on
July 12 and continued each day through July 15. Dermal and respiratory
exposure monitoring of the harvest crew took place on July 13 and 14.
Worker reentry into a tobacco field treated with acephate is permitted
after the spray deposit has dried.
Participants - The farmer's entire harvest crew of seventeen workers was
recruited for study. The crew consisted of seven juveniles (age 10 - 16,
six males and one female) and ten adults (age 17 to 71, seven males and
three females). Participant data is listed in Table 2.
The harvesters began work around 7:00 in the morning. Two of the
eight row groups of tobacco were harvested concurrently with workers
assigned to each of the row groups. Tobacco leaves mature first at the
bottom of the plant, thus only several of the lowest leaves are removed
from a plant. The remaining leaves are picked at successive harvests.
The harvester usually picked the mature leaves with his right hand and
then placed the leaves under his left arm which held the leaves against
his side. A tractor pulled wagon moved slowly down the alley between the
row groups. As the workers accumulated an armload of tocacco leaves.
the leaves were then placed on the wagon. This required walking between
the olants of up to seven tobacco rovs.
The participants were monitored, under normal working conditions,
for their dermal and respiratory exposure to acepahte for tvo hours on
July 13 (Day 1) and again for two hours on July 14 (Day 2).
Assessment of Dermal Exposure - Each participant wore a long sleeve
disposable paper jacket (Tyvek 14). Affixed to each jacket were seven
-------
Table 2
Participant Data *
Dermal and Respiratory Exposure Assessment of Adult and
Juvenile Tobacco Harvesters to Acephate-Duplin County, N.C. 1982
251
•Participant
Study
No.
J
U
V
E
N
I
L
E
S
A
D
U
L
T
S
3
4
5
6
7
6
10
1
2
9
11
12
13
14
15
16
17
Age
15
15
15
15
15
16
10
17
19
24
71
50
41
19
31
49
39
Sex
M
F
M
M
M
M
M
M
M
M
H
M
F
:-i
F
F
M
Height
(cm)
170
170
173
170
157
183
142
173
185
188
180
157
157
160
163
152
180
Weight
(kg)
64
62
66
54
41
54
41
63
83
68
72
68
86
50
59
72
83
Work Clothing
Jeans, long sleeve shirt, shoes & hat
Jeans, long sleeve shirt, shoes & hat
Jeans, long sleeve shirt, shoes & hat
Pants, long sleeve shirt,sneakers&ha
Jeans, long sleeve shirt, shoes & hat
Pants, long sleeve shirt, shoes & hat
Pants f long sleeve shirt, shoes & hat
Pants, long sleeve shirt, shoes & hat
Jeans, long sleeve shirt, shoes L hat
Pants, long sleeve shirt, shoes & hat
Pants, long sleeve shirt, shoes & hat
Pants, long sleeve shirt, shoes & hat
Pants, long sleeve shirt, shoes & hat
Jeans, long sleeve shirt, shoes L hat
Short sleeve dress and shoes
Jeans, long sleeve shirt, shoes S hat
Pants, short sleeve shirt, boots&hat
participants were black. Work gloves are not usually worn during harvest.
-------
252
2" x 2" - 8 ply gauze squares (pre-extracted with acetone) with glassine
backing; one on each forearm, breast and shoulder and one square on the
center of the back. The purpose of the gauze squares was to trap dislodge-
able residue from the bushes and soil that were released as a result of the
workers' physical activity in the field. The glassine backing prohibited
gauze contamination from skin oils and perspiration absorbed through the
jacket. The gauze squares were removed from the jackets at the completion
of the monitoring periods and were pooled Into three samples (forearms,
chest and shoulder) with the back square remaining separate. All samples
were wrapped in aluminum foil, labeled and frozen prior to analyses.
Translocated residue to the workers' hands was assessed through the
analyses of 100Z cotton gloves worn by the participants during their
exposure monitoring periods. Affixed to the back of each glove was a
2" x 2" - 8 ply gauze square with glassine backing. It was anticipated
that the gauze would avoid much of the contamination expected from dirt,
skin oils, etc. The gloves were laundered, rinsed in distilled water and
then acetone extracted with the gauze pads prior to use. At the completion
of monitoring, the gauze squares were removed from the gloves. The gloves
and glove gauze of each participant were pooled separately, wrapped in
aluminum foil, labeled and frozen prior to analyses.
Assessment of Respiratory Exposure - Each participant wore a DuPont P-4000
Personal Air Sampler, precalibrated at 2.0 liters/minute, during the two
monitoring periods. The sampling train consisted of a 37 mm cassette with
a Millipore glass fiber filter (.3 micron pore size) followed by a custom
made XAD-4 resin sorbent tube (500 mg). The sampling media were chemically
extracted with hexane, acetone and diethylether prior to use. Start and
stop times of the air samplers were recorded for subsequent air volume
calculations and the flow control light-emitting diodes of the air samplers
were monitored to insure that proper flow had been maintained. At the
-------
253
end of the monitoring periods, each air sampling medium was wrapped
in aluminum foil, labeled and frozen prior to analyses.
Assessment of Absorption - Urine samples were collected from each
participant to document whether the individual's exposure resulted in
absorption and excretion of the chemical of study. The participants
were requested to collect first morning voids after each day of exposure
monitoring. The first morning voids were collected on June 14 and 15.
Samples were collected in polyethylene bottles which had been washed
and rinsed with organic free water. All specimens were labeled and
frozen prior to analysis.
Environmental Sampling - Collection of soil, tobacco leaf and high
volume air samples was performed each day from July 12 through July 15.
The purpose of the environmental sampling was to document the level of
acephate present at the times of participant monitoring and also to
demonstrate degredation over time.
Ten composite soil samples were collected each day from the field
of study. Each composite sample was fron one row of the field and the
ten rows selected for sampling were determined as follows:
1. The row in the center of the field was located.
2. Sanpling rows 1 through 5 were the rows to the right
of mid-field which were equidistant from each other
to the last crop row on the right.
3. Sampling rows 6 through 10 were the rows to the left
of the row of mid-field and were equidistant from each
other to the last crop row on the left.
Along the length of each row selected for sampling, five ''collection
points", all equidistant from each other, were designated. Each
collection point was a tobacco plant. At the base of the first plant
collection point, approximately 100 rag of soil was collected fron the
-------
254
top half-inch of soil using a stainless steel scoop. Soil was then
collected in the same manor from the remaining four points. Thus,
each composite soil sample contained approximately 500 mg of soil.
All composite samples were collected in amber colored glass jars which
had been pre-rinsed with acetone. The jar lids were lined with aluminum
foil. All samples were labeled and frozen prior to analysis.
Ten mature tobacco leaf samples were also collected on each day
of study. One whole leaf sample was collected from each of the previously
designated sampling rows. For sampling rows 1 through 5, the leaf sample
was from the plant which was designated as the same sample collection
point as the row number. For example, leaf sample f 3 was from collection
point number 3 of row 3. This scheme was repeated for sampling rows 6
through 10. Leaf sample # 6 was from collection point number 1 of row
6, leaf sample 7 was from collection point number 2 of row 7, etc.
Samples were individually wrapped in aluminum foil, labeled and frozen
prior to analysis.
iligii volune air sanpling (20 f /^) was performed for one hour each
day in the field of study. Two Staplex High Volume Air Samplers ("odel
TF1A), calibrated prior to use, were placed side by side approximately
50 feet into the field. The purpose for placing the high volume air
samplers next to each other was to have one serve as a quality control
check for the other. AC power was supplied frora the farmer's house.
Sampling trains consisting of 4.0" diameter glass fiber filters for
particulates followed by approximately 100 ml of XAD-4 resin for vapors
were used. Both media were chemically extracted (hexane/acetone/
diethylether) prior to use. After sarpling, the filters were indivi-
dually wrapped in aluminum foil, labeled and frozen prior to analysis.
The resin was transferred to amber colored glass jars, capped with
alurinu:- fell lined lids, labeled and froze:;.
-------
255
Meteorological Data - During each day of study, the following obser-
vations were made: 1) maximum temperature, 2) relative humidity, 3)
barometric pressure, 4) wind speed, direction and condition, 5) percent
cloud cover and 6) rainfall.
IV. Analytical Methodology;
All samples were analyzed on a Varian Vista 600 series gas
chromatograph equipped with a Thermal Specific Detector, specific
for nitrogan and phosphorus. Qualitative and quantitative analyses
were performed on a 2 foot glass column packed with 1Z Reoplex 400
on Gas Chrom Q 80/100 Mesh (Altech Associates, Inc.).
GLC operating conditions were as follows:
Injection Fort Temp.-225°C
Detector Temp. - 245°C
Oven Temp. - 140°C for 0.6 min., 10°C/min. to
180°C for 10 min.
Retention times:
Methamidophos - 1.6 min.
Acephate - 3.1 min.
Samples were extracted into ethyl acetate, concentrated, rediluted
to appropriate volumes and injected onto G.C. Analytical procedures
and instrument conditions throughout this study were adapted from the
method of J.B. Leary "Gas-Liquid Chromatographic Determination of
Acephate and Ortho 9006 Residues in Crops," JAOAC 57 (1): 189-191; 1974.
The samples analyzed in this study did not require the additional
cleanup procedures explained in the Leary method.
Urine samples were extracted and analyzed for methanddophos and
acephate following an unpublished procedure by Chevron Chemical Company,
Agricultural Division, Research and Development Department, Richmond,
California; "The Determination of Methamidophos ar.cl Acephate in Urine "
(March 6, 1981).
-------
V. Quality Assurance; The preceeding paragraphs have described, in detail, tnfe
procedures utilized for the collection and analysis of samples in support of
this study. These procedures follow those which were outlined in the "SC
PHAP QA Plan for Extramural Project-Dermal and Respiratory Exposure Assess-
ment of Adult and Juvenile Harvesters" which was submitted to the EPA in
March 1982 and subsequently approved by the EPA QA Officer. Also included
in the QA Plan and adhered to by the SC PHAP were general quality control
procedures such as peer and EPA'review of the study protocol, evaluation of
analytical methodologies, record keeping (field tracking reports, laboratory
sample log books, instrument maintenance logs, etc.), scheduled routine
maintenance, checks of the gas chromatographic system, use of analytical
reference standards obtained from the EPA Environmental Monitoring Systems
Laboratory (DISL) and participation in the EPA Quality Control Program under
the direction of the EMSL.
Specific QA analytical procedures utilized by the SC PHAP laboratory in
support of this study were:
Intralaboratory
1. One fortified sample was analyzed with every ten study samples to
document the extraction efficiency and reproducibility of the
analytical methodology.
2. Blanks, sample media and reagent, were also analyzed with every ten
study samples to demonstrate the purity of reagents and cleanup
procedures of the sample media.
3. Sample media were fortified in the field at the time of sample
collection and were freezer stored along with the study samples.
The purpose of the field spikes was to provide data on stability and
sample degradation over time.
10
-------
257
Interlaboratory
Blind analyses of fortified samples which were split between
the SC FHAF and the Maine Public Health Laboratory (MPHL)
which served as procedural checks.
Intralaboratory quality assurance results for acephate and methanldophos
are listed in Table 3. Average recoveries for the various media ranged from
92% to 103.52 for acephate and methamidophos ranged from 83.92 to 103%.
Analyses of media and reagent blanks demonstrated the absence of inter-
fering contaminants. The results of the intralaboratory quality assurance
procedures indicated that no corrections to study data were required for
analytical methodology.
The intralaboratory quality assurance procedure of spiking sample media
in the field at the time of study was unsuccessful. This was a result of
selecting levels of fortification which were later found to be below the
lower limit of detection for the analytical methodology.
Interlaboratory quality assurance results are reported in Table 4.
All average recoveries for acephate and methamidophos samples split \:ith
the MPHL were within the +20% agreement which was the pre-establish
acceptable range for Intel-laboratory quality control.
11
-------
Table 3
Intralaboratory Quality Assurance
1
Medium
Gauze Squares'
Glass Fiber
Filters
XAD-4 Resin
it
Soil
it
Leaves
Urine
Chemical
acephate
methamidophos
acephate
methamidophos
acephate
methamidophos
acephate
me thamidophos
acephate
me thamidophos
acepajfite
methamidophos
Recovery
Level of
Fortification
20.0 ug
2.0 ug
4.0 ug
2.0 ug
4.0 ug
2.0 ug
20.0 ug
10.0 ug
20.0 ug
10.0 ug
6.4 ppm
.32 ppm
Replicates
(n)
21
21
4
4
4
4
4
4
4
4
6
6
Standard
\ £ Deviation
19.6 98.0
1.70 85 .0
4.05 101.3
2.06 103.0
4.08 102.0
1.78 89.0
18.4 92.0
8.39 83.9
19.5 97.5
7.02 87.8
6.63 103.5
.298 93.1
1.31
.197
.098
.102
.165
.266
.711
.165
.582
.840
.422
.046
Coefficient of
Variation
6.68
11.6
2.44
4.93
4.05
14.9
3.87
1.97
2.99
11.9
6.36
15.4
if All analyses of blanks, sample media and reagent, were negativeJ
21 Gauze squares served as quality control for cotton gloves.
12
en
oo
-------
Table 4
Interlaboratory Quality Assurance
Results of Fortified Samples Split Between
the SC PHAP Laboratory and the Maine Public Health Laboratory
Recovery
Spikins ACEPHATE
Sample
Gauze Square
it
»
Glass Fiber
Filter
"
n
XAD-4 Resin
"
it
Level SC PHAP
20.0 ug 21.27
" 19.82
" ' 20.06
X - 20.38
% - 101.9
20.0 ug 18.98
" 18.49
" 16.88
X - 18 . 12
7, - 90.6
20.0 ug 20.06
" 20.78
20.65
>(- 20.49
% - 102.5
MPHL
20.31
21.87
20.31
20.83
104.1
20.46
20.57
19.53
20.19
100.9
20.58
20.78
20.56
20.64
103.2
METHAMIDOPHOS
SC PHAP
18.06
17.58
16.79
17.48
87.4
17.48
17.28
15.20
16.65
83.3
17.32
18.20
17.10
17.54
87.7
MPHL
15.53
16.43
16.13
16.03
80.2
16.79
16.37
15.05
16.07
80.4
15.77
16.05
15.80
15.87
ro
79.4 <~n
vO
13
-------
TableA(continued)
Recovery
Spiking ACEPHATE
Sample
Soil
"
ii
Leaves
"
'•
Urine
»
"
Level SC PHAP
8.00 ng/mp acephate 6.97
0.40 ng/mg mothamidophos
8.54
8.07
x" = 7.86
Z - 98.2
0.620 ug/cn£ acephate
0.031 ug/cm methamidophos .646
.634
.562
7 - .614
"i. - 99.0
8.0 ug acephate 7.53
0.4 ug methamidophos
" 8.57
7.77
?- 7.95
% - 99.3
MPHL
6.53
7.00
6.85
6.79
97.0
.556
.539
.550
.548
88.4
5.72 (
6.90
6,20
6.27
78.4
METHAMIDOPHOS
SC PHAP
0.32
0.39
0.36
0.36
90.0
.034
.035
.036
.035
112.9
.315
.318
.404
.345
86.2
MPHL
0.33
0.35
0.36
0.35
87.5
.030
.030
.027
.029
93.5
.244
.245
.308
.266
66.5
ro
O
14
-------
VI. Resulrsf
26 1
Results of Day 1 (July 13) participant monitoring are listed in Table 5.
All cotton glove samples contained residues of acephate and methamidophos.
Acephate residues in the juvenile group averaged 1,240 ug per pair of gloves while
the adult average was over three times higher at 4,150 ug. Average methamidophos
residues detected in the gloves were found to be approximately 21 of the observed
acephate levels. The adults averaged 102 ug per pair of gloves as compared to
21.1 ug for the juveniles. Gauze squares attached to the back of the gloves also
demonstrated higher average residues in the adult group. The adults averaged
2
.495 and .004 ug/cm for acephate and methamidophos as compared to the juvenile
2
averages of .346 and .003 ug/cm .
Five juvenile and five adult participants lost gauze square samples which
were attached to their disposable jackets. Seven forearm samples and one sample
each for the chest, shoulders and back were lost in the field at the time of
study. The samples were torn from the jackets as the participants walked between
the plants and as a result of loading the wagon with armloads of tobacco.
All gauze square samples for the four body locations contained quantifiable
acephate residues. Quantifiable methanidophos residues were found to be less
than 2Z of the corresponding acephate levels. The adults experienced higher
average acephate and methanidophos exposure to their forearms, chests and
backs. Respectively, the average acephate levels were .023, .117 and .47 ug/cm
greater then the average residues observed in the juveniles. Methamidophos
2
residues for these three locations averaged .002, .003 and .019 ug/cra in the
2
adults as compared to .0003, .001 and .013 ug/cm in the juvenile group. The
juveniles were found to have slightly higher exposure to their shoulders. Their
2
average acephate and methamidophos residues were .15 and .002 ug/cm greater than
the average adult residues. Of the four body regions, the back represented the
highest source of exposure to the juveniles and adults. Following the back, in
descending order, were the shoulders, chest and forearms.
IS
-------
It is difficult to compare the residues observed in the glove samples
with the gauze squares since the results of the two media are expressed in
different units. Davis (1980) reported the surface area of the hands to be
2
820 cm . Since the juvenile and adult participants wore the same size cotton
gloves for exposure assessment, this figure has been used to adjust the glove
results to units of square centimeters. Therefore, the dermal exposure to the
2
hands of the juveniles averaged 1.51 and .026 ug/cm for acephate and raethamidophos
2
and the adults averaged 5.06 and .124 ug/cm .
All personal air samples contained quantifiable acephate residues. No
methamidophos was detected in the glass fiber filter or XAD-4 resin samples at
the .125 ug/m lower limit of detection. Acephate residues ranged from 2.32
ug/m observed in the juvenile group to a level of 137 ug/m found in the adult
3 3
group. The juveniles averaged 31.8 ug/m and the adults equaled 35.7 ug/m .
The slightly higher average respiratory exposure observed in the adults is
attributed to participant 16 whose level was twice as great as the next highest
participant.
No quantifiable residues of acephate or methamidophos were observed in any
of the Juvenile or adult urine samples. The lower limit of detection in urine
was .05 ppm.
Day 2 (July 14) participant results are reported in Table 6. All average
acephate residues recovered fron the juvenile and adult sample media were found
to be less than 10% of the average residues observed on Day 1. Except for the
back gauze squares, no methamidophos residues were detected. As seen on Day 1,
no acephate or methamidophos residues were detected in any of the participants'
urine samples.
Acephate recovered from the Day 2 glove samples was observed to be less than
22 of the Day 1 averages for both the juveniles and adults. Again the adults
were found to have greater exposure to their hands with an average of 36.8 ug
as compared to 19.4 ug in the juvenile group. Adjusted to square centir.eters,
16
-------
Assessment of
Tobacco
tiay I I'rtrt Iclpniit l
-------
as demonstrated with the Day 1 results, these levels equal .045 and .0,24 u
Acephate recovered from the glove gauze samples demonstrated slightly higher
2
exposure in the adults who averaged .001 ug/cm more than the Juveniles.
Day 2 average acephate residues for the body regions, expressed in percentages
of the Day 1 results, ranged from >1Z to 5Z for the Juveniles and >1Z to 7% for
the adults. As observed on Day 1, the back gauze squares contained the highest
residues of the four body regions. The Juveniles demonstrated higher average
2
exposures to their backs and chests. These levels were .006 and .004 ug/cm
greater than the adult averages. The methamidophos recovered in the back gauze
squares also demonstrated slightly higher exposure in the Juveniles. The adults
were found to average more exposure to their forearms and shoulders: .017 and
2 2
.011 ug/cm as compared to .006 to .008 ug/cm in the Juveniles.
The average acephate residue recovered from the personal air samples on
the second day of study was only 5% of the Juvenile concentration on Day 1 and
less than 2Z for the adults. Higher respiratory exposure to acephate was observed
3
in the Juveniles, whose average of 1.57 ug/m was almost three tines greater than
the adult level of .560 ug/m .
Statistical Analyses of Participant Exposure
Statistical analyses (t-test) comparing the acephate and methanidophos
residues recovered from the Juvenile and adult sample media on the two days of
study are reported in Table 7. Only one significant difference between the
Juvenile and adult exposure patterns was observed: day 1 methamidophos chest
gauze squares (P<.02). In this instance, the trend of higher average residues
is found in the adults.
Environmental Results
Acephate and methamidophos residues recovered from the surface area of
tobacco leaves are reported in Table 8. Results of the baseline sampling on
July 12 demonstrated the presence of residues from an acephate application
which took place 20 days prior to sampling. All post application sarnies
-------
Day 2 Participant Results
Assessment of Dermal and Respiratory Exposure of Adult and Juvenile
Tobacco Harvesters to Acephate-Duplin County, N.C. 1982
I.D.
Ho.
J
U
V
E
N
I
L
E
S
A
D
U
L
T
S
3
A
5
6
7
8
10
X
SO
1
2
9
11
12
13
14
15
16
17
x"
SD
COTTON
(ug
A
7.80
ND
53.8
5.40
29.7
19.5
19.3
19.4
18.2
GLOVES
)
M
ND2
it
it
it
it
U
ii
—
—
GAUZE SQUARES (tig/cm?)
GLOVES
A
.010
.003
.021
.002
.005
.014
.005
.009
.007
M
ND
U
ii
ii
ii
U
ii
—
—
19.5
9.30
45.9
40.7
4.20
7.80
48.9
43.3
62.0
86.0
36.8
26.5
ND
ii
ii
ii
ii
ii
U
U
ii
U
—
—
.010
.012
.007
.014
.029
.004
.003
.007
.003
.007
.010
.008
ND
ii
ii
U
U
U
M
ii
M
ii
—
—
FOREARMS
A
NSJ
.007
NS
.003
.010
NS
.006
.006
.003
M
NS
ND
NS
ND
U
NS
ND
—
—
CHEST
A
.057
.003
NS
.006
.010
003
.001
.013
022
M
ND
U
NS
ND
ii
ii
ii
—
—
SHOULDERS
A
.007
.005
.013
.011
.010
.005
.004
.008
.003
M
ND
n
ii
M
ii
n
M
—
BACK
A
.071
.132
.045
.082
.030
.033
.040
.062
.037
M
ND
.005
.003
.003
.002
ND
M
.002
.002
PERSONAL
AIR SAMPLE
(ug/m3)
A only
1.15
.478
1.99
.154
3.19
4.01
ND
1.57
1.56
.019
.011
NS
.038
NS
.009
NS
U
.007
.018
.017
.011
ND
U
NS
ND
NS
ND
NS
M
ND
U
—
—
014
010
NS
003
.004
005
007
007
018
010
009
005
ND
ii
NS
ND
it
it
n
ii
ii
ii
—
—
.016
.005
.004
.016
.007
.012
.009
.005
.013
.020
.011
.006
ND
n
n
ii
ii
n
it
ti
ii
ii
—
—
.065
.041
.072
.073
.069
.116
.059
.021
.024
.023
.056
.030
.006
.003
.003
ND
ii
ii
ii
n
it
n
.001
.002
.706
ND
.330
.145
.613
.649
ND
2.30
.703
.158
.560
.674
URINE
7/15/82
A
ND
ii
n
ii
ii
n
it
—
—
ND
ii
ii
n
H
H
ii
ii
n
n
—
—
M
ND
ii
it
M
n
it
n
—
—
ND
n
ii
ii
n
ii
ti
it
it
ii
—
—
II A • Acephate, M - Methamidophos: Lower limits of detection; gloves - 0.75 ug, gauze - .001 ug/cm , personal
— _j_ ____1« _ 19^ .m/m3 and urine • .OS nnm
air sample - .125 ug/m
21 ND - None Detected
3/ NS • No Sample
and urine - .05 ppm
ON
U1
19
-------
266
Table 7
Statistical Analyses (t-test) of Juvenile vs.
*
Adult Sample Media for Each Day of Study
Day 1 Day 2
Sample Media Acephate Methamidophos Acephate Methamidophos
Cotton Gloves NS NS NS NR
Gauze Squares:
Gloves " " " "
Forearms " " " "
Chest " t -2.695(P<.02) " "
Shoulders " NS " "
Back " " " NS
Personal Air Sanples " " " NR
Urine NR NR NR "
*Statistically significant at P <_ 0.05
NS • No significance, P > 0.05
NR • No residues detected in sample media
20
-------
267
contained quantifiable levels of acephate and methamidophos. At 12 hours post
2
application, acephate residues averaged .449 ug/cm and methamidophos equaled
2
.022 ug/cm . At 36 hours, average acephate residues declined by one-third to
2 2
.155 ug/cm and methamidophos by half to .012 ug/cm . A small increase in
residue levels was observed in the samples collected at 60 hours post application.
The Increase was not significant (paired t-test, P > 0.5). The increase in
residues is thought to be a result of the method of application. Each leaf
sample was obtained from the bottom of the tobacco plant selected for sampling.
This was done in order to have samples representative of the leaves being
harvested. Since the tobacco plants were sprayed from the top, the uppermost
leaves of each plant would receive more direct spray than the bottom leaves and
would be expected to have higher residues. The leaf samples were collected
after the day's harvest was completed. Thus, the samples were obtained from a
level closer to the top of the plant which is assumed to have higher residue
concentrations.
Results of the soil residue analyses are listed in Table 9. No methanidophos
was detected in any of the samples at the 5.3 ppb lover licit of detection.
Acephate averaging 24.8 ppb was observed in the pre-application samples. An
average concentration of 185.6 ppb was seen 12 hours after application which
declined by 75% to 47.0 ppb at 36 hours. As observed in the leaf samples, a
non-significant increase (paired t-test, P > 0.5) to 57.6 ppb was observed at
60 hours. The increased is believed to be a result of a light rain, >.l"
(Table 10), during the 24 hour period prior to sampling on July 15. This
rainfall and the .2" of rain for July 13/14 would be expected to wash a portion
of the acepahte residues off the leaves.
Results of the high volume air sampling are reported in Table 11. No
methamidophos residues were detected in any of the samples while acephate was
only recovered in the glass fiber filters of the 12 hours post application
-------
Table 8
Results of Tobacco Leaf
Analyses
ug/cmz
12 Hours 36 Hours
Pre Application Post Application Post Application
7/12/82 7/13/82 7/14/82
Sample
1
2
3
4
5
6
7
8
9
10
X
SD
i/
I/
No. A
.006
.216
.109
.005
.059
.060
.021
.020
.006
.017
.052
.067
A-Acepahte and
M
ND2
.029
.015
Nl>
.008
.007
.001
.002
ND
.004
.007
.009
A
197
459
611
176
152
858
316
626
240
356
449
274
M-Methamidophos, lower
M
.026
.026
.028
.011
.022
.024
.025
.023
.015
.022
.022
.005
limit
A
.116
.061
.092
.173
.105
.441
.032
.135
.055
.345
.155
.133
of detection •
M
.010
.006
.006
.012
.010
.037
.003
.007
.009
.017
.012
.010
.001 ug/cm .
60 Hours
Post Application
7/15/82
A
.308
.067
.201
.143
.201
.377
.118
.154
.048
.058
.167
.108
H
.019
.005
.012
.011
.011
.046
.008
.009
.010
.007
.014
.012
ND - None detected
rv>
00
22
-------
Results of Soil Residue Analyses1
Sample No.
1
2
3
4
5 .
6
7
8
9
10
3C
SD
Acephate (ppb)
Pre Application
7/12/82
37.7
ND2
36.7
ND
13.2
31.0
29.9
30.0
69.9
ND
24.8
22.1
12 Hours
Post Application
7/13/82
69.7
45.8
43.4
280.0
18.3
79.9
ND
778.3
279.6
260.8
185.6
236.1
36 Hours
Post Application
7/14/82
48.7
16.6
23.0
30.5
36.1
ND
46.2
52.1
148.6
67.9
47.0
40.7
60 Hours
Post Application
7/15/82
34.1
40.9
19.4
16.5
28.2
46.4
70.0
60.1
24.4
236.0
57,6
65.0
If Lower limit of detection - 5.0 ppb
No methand.dophos was detected in any of the 40 soil samples.
2/ ND-None detected
ro
ON
23
-------
sampling. These results suggest that any acephate in the ambient air'were 2» U
dislodgeable residues from the plants and soil which were released by the physical
activity of the harvesters. If the residues observed at 12 hours were a
result of volatilization of acephate from the leaf and soil surfaces, then the
baseline, 36 and 60 hour high volume air sampling would likely have detected
residues on those days since leaf and soil residues were present (Tables 8
and 9). Additionally, the harvesters worked around the high volume air samplers
during the 12 hour post application sampling. On July 14 (36 hours post applica-
tion) , the high volume air samplers were placed in the same location used for the
12 hours sampling, however the workers picked tobacco several rows away. The
final argument for dislodgeable residues are the personal air samples which had
a lower limit of detection almost 200 times greater than the high volume air
3 3
samples (.125 ug/m as compared to .7 ng/m ). These "breathing zone" sanples
were from the ambient air surrounding each participant as he worked. Average
personal air sample results on July 13 were one thousand times greater than the
.036 ug/m seen in high volume air sample //I and quantifiable residues were
observed in the personal air sanples of July 14 when no residues were detected
in the high volume air sample.
24
-------
Table 10
Meteorological Observations
Assessment of Dermal and Respiratory Exposure of
Adult and Juvenile Tobacco Harvesters to
Acephate-Duplin County, N.C. 1932
Observation July 12 July 13 July 14 July 15
Rainfall"1"
Temperature F*
Barometric Pressure
Relative Humidity
Wind
2 Cloud Cover
0
97°
29.98"
70*
S(5-7mph)
20
0
81°
29.93"
84%
S(l-2mph)
40
0.2"
84°
29.97
80Z
E(l-2raph)
90
<.l"
74°
29.97
96Z
S(l-2raph)
90
4- Rainfall is for 24 hour period ending at tine of sampling. After sampling
on July 13, 0.2" of rain fell prior to the sampling of July 14 and <.l" fell
after the sampling of July 14 but prior to s?-plins on July 15.
25
-------
Table 11
Results of High Volume Air Sampling
Pre Application
7/12/82
High Volume
Air Sample II
Glass Fiber Filter
XAD-4 Resin
Total
ND
NO
Acephate (ug/m )
12 Hours
Post Application
7/13/82
.036
ND
.036
36 Hours
Post Application
7/14/82
ND
ND
60 Hours
Post Application
7/15/82
ND
ND
High Volume
Air Sample 9 2
Class Fiber Filter
XAD-4 Resin
Total
ND
ND
.018
HD
.018
ND
ND
ND
ND
I/ Lower limit of detection • .7 ng/m
No methanidophos was detected in any of the samples
21 ND • None Detected
ro
-^j
ro
26
-------
Discussion: O 7 7
Results of the environmental sampling demonstrated the participants of study
had potential exposure to acephate and methamidophos when harvesting tobacco at
12 and 36 hours post application (0.75 PAI/acre). Average dermal exposure to
methamidophos was found to be less than 2Z of the observed acephate levels on
day 1. Average acephate residues decreased by more than 90% on the second day of
study while most methamidophos residues fell below the level of quantification.
The study did not document absorption and excretion of acephate by the
participants. This may be a result of acephate being poorly absorbed by the
dermal and respiratory tracts at residue levels observed in this study. Also
residues may have been present in the urine samples of the workers, but were at
concentrations below the level of detection of .05 ppm.
Results of the participant exposure monitoring demonstrated the hands of
the workers were the primary source of dermal exposure. This observation was not
unexpected, since Davis (1980) reported that in nearly all studies of occupational
exposure to pesticides, approximately 90% of the dermal exposure was found in the
hands. Wicker and Guthrie (1980) employed the industrial technique of time and
motion studies to determine standardized times of exposure for anatomic regions
of workers during the harvest of a variety of crops. Tobacco harvesters were
filmed at 5 consecutive 3.5 minute intervals for a total of 17.5 minutes.
Analysis of the filn found the right and left hand were in contact with the tobacco
leaves for an average of 13.3 and 16.0 minutes respectively. Right and left arm
contact accounted for 2.6 and 15.9 minutes while the trunk of the body was in
contact for 15.9 minutes.
The objective of this study was to assess the difference, if any, between the
dermal and respiratory exposure patterns of Juvenile and adult tobacco harvesters
who had post application exposure to acephate. No significant differences were
observed between the juveniles and adults in respiratory exposure, exposure to
27
-------
274
the hands and dermal exposure to the forearms, shoulders and back. The one
exception was the methamidophos residues in the first day's chest gauze squares
and the trend toward higher residues was seen in the adults.
-------
VIII. References:
275
Barlas, S. The Silent Spring Lab: What's it up to now? Industrial Chemical News.
Vol. 5, No. 2 (Feb. 1984).
Davis, J.E. Minimizing Occupational Exposure to Pesticides: Personal Monitoring.
Res. Rev. 75: 33-50 (1980).
Wicker, G.W. and F.E. Guthrie. Worker-Crop Contact Analyses as a means of
Evaluating Reentry Hazards. Bull. Environ. Contarn. Roxicol. 24 (1): 161-167
(1980).
-------
276
Studies of Pesticide Residues Present 1n
the Soil of Three Potato Farms at the
Time of Harvest, Aroonstock County,
Maine 1982
Research performed by
Medical University of South Carolina
March 29, 1984
-------
277
Table of Contents
Title Page
Abstract 11
List of Tables Ill
I. Objective 1
II. Background 1
III. Methods 5
IV. Analytical Procedures 12
V. Quality Assurance 7 14
VI. Results and Discussion ..... 18
VII. References 23
-------
278
Abstract
Five composite soil samples were systematically collected at the time of
harvest for each pesticide applied during the 1982 growing season at three potato
farms in Aroostock County, Maine. Two herbicides (linuron and oetribuzin), five
insecticides (aldicarb, demeton, endosulfan, methamidophos and methomyl), three
fungicides (chlorthalonil, mancozeb and polyram) and two desiccants (dinoseb
and diquat) were identified from the spray schedules of the three study sites.
Quantifiable soil residues were observed for nine of the twelve pesticides.
Average residue levels ranged from .030 ppm for demeton up to 1.37 ppm for
endosulfan. Study results agreed with persistence and half-life data reported
in the literature. Residues of methamidophos, methorny1 and mancozeb were not
detected, however these pesticides have been reported to rapidly degrade under
most environmental conditions.
The results of this study suggest the juvenile harvesters employed by the
three farms had potential dermal and respiratory exposure to the pesticide
residues observed at each farm.
11
-------
List of Tables
Table No. Title Page
1 Approved Pesticides for Maine Potatoes, 1982. . 4
2 1982 Pesticide Usage History 6
3 Climatological Data 7
4 Intralaboratory Quality Assurance 16
5 Intel-laboratory Quality Assurance 17
6 Results of Soil Analyses (ppm) 21
7 Soil Persistence Data for the Pesticides of Study 22
111
-------
Study of Pesticide Residues Present in the Soil of 280
Three Potato Farms at the Time of Harvest-Aroostock County,
Maine 1982
I. Objective;
The objective of this study was to identify and quantify pesticide
residues present in the soil of three potato farms at the time of harvest.
II. Background;
The U.S. Environmental Protection Agency (EPA) and the U.S. Department
of Labor (DDL) finalized an interagency agreement on March 17, 1980. This
agreement, "Youth in Agriculture", provided for the development of pesticide
protection programs for farm workers. The employment of children during
the harvest of hand picked crops is of special concern to the DOL. This
agency has the authority to waive restrictions to permit children to work,
however it also must assure that there are no adverse health effects to the
children for which the exemption was granted. One goal of the interagency
agreement is the determination of scientifically based reentry intervals
for children and the assessment of potential health effects of pesticides
on children working in agriculture.
The EPA and DOL have assumed that the potential for the exposure of
children to toxic chemicals in agriculture is widespread and that children
are generally more sensitive to chemical exposure. Furthermore, children
possibly have greater rates of dermal and/or gastrointestinal uptake and
have decreased capacity for detoxification. Yet, little or no data exists
to support these assumptions as it applies to field workers. In order to
bridge this data gap, It is necessary to perform studies which measure the
pesticide exposure of adult and juvenile workers to various pesticides
during the harvest of a variety of hand-picked crops.
Juveniles (10-17 years of age) are commonly employed as stoop laborers
during Maine's potato harvest. Although mechanical harvesters are slowly
replacing the hand-picking crews, those potatoes grown for seed will
-------
281
continue to require harvesting by hand in order to avoid bruising which is
found on mechanically harvested potatoes. Aroostock County, located in
northeast Maine, is the state's predominant potato region and children
comprise the majority of labor for hand-picking operations. Harvest
begins in mid-September and is usually completed during the first week of
October. School is recessed, for "spud vacation", for approximately three
weeks to accommodate the employment of children. Few adults (>_18 years old)
work as pickers because their age alone qualifies them for higher pay
positions such as drivers and equipment operators. Also, the adult labor
supply available for employment is low and migrant workers are not commonly
employed.
The study "Assessment of Dermal and Respiratory Exposure of Juvenile
Potato Harvesters to Dinoseb-Aroostock County, Maine 1981" (4/5/82, revised
8/11/82) reported almost all of each worker's dermal exposure was found to
be via the hands and that respiratory exposure accounted for little of the
total exposure. This finding was not surprising. The actual process of
harvesting potatoes requires the worker to have extensive contact with the
•oil by removing the potato vines from the top of the soil and by picking up
the potatoes which lay in the soil. Thus, if pesticide residues are present
in the soil, then the harvester's hands will have the greatest exposure
to those residues. This study was performed over a two day period. Results
of the first day monitoring found the dermal dinoseb residues on the hands
of the ten Juvenile participants averaged 10.09 ug while the soil samples
averaged 951 ppb. The average exposure to the hands on the second day of
study was 3.56 ug as compared to an average residue of 803 ppb in the soil.
-------
282
The University of Maine Cooperative Extension Service recommends 19
insecticides, 9 herbicides and desiccants and 6 fungicides for use on
potatoes (Table 1). Many of the insecticides have pre-harvest application
restrictions which range from 14 to 75 days and post emergent herbicides
used to control late weed and grasses have restrictions of 45 to 60 days.
Recommended fungicides have no such restrictions and may be applied weekly
throughout the season. Usually the last pesticide application to potato
fields is a desiccant (dinoseb or diquat) which is applied from 14 to 21
days prior to harvest.
The study described herein was a cooperative effort between the South
Carolina Pesticide Hazard Assessment Program (SC PHAP) and the Maine Public
Health Laboratory (MPHL). The MPHL was responsible for the field and
analytical phases of the study. The SC PHAP was responsible for the develop-
ment of the study protocol, interlaboratory quality assurance and prepara-
tion of the final report.
-------
Table 1
Approved Pesticides for Maine Potatoes. 1982
2
Insecticides Herbicides Fungicides
Aldicarb Alachlor Chlorothalonil
Azinphosmethyl Chlorbromurom Difolatan
Carbaryl Dalapon Duter
Carbofuran Dinoseb Mancozeb
Demeton Diquat Maneb
Diazinon EPIC Polyram
Dimethoate Linuron
Disulfoton Metribuzin
Endosulfan Paraquat
Imidan
Malathion
Me thamidophos
Methomy1
Mevinphos
Oxydemeton-methyl
Parathion
Phorate
Phosalone
Piriaicarb
^/Co-operative Extension Service, University of Maine.
_2/Does not include fungicides recommended for potato seed
piece treatments.
-------
284
III. Methods;
Selection of Study Sites
The Area Potato Specialist of the Cooperative Extension Service assisted
the on-site investigator by identifying local potato farmers who would be
more likely to participate in the proposed soil sampling study. Only three
criteria were required for recruitment: (1) 1982 pesticide usage in compliance
with recommendations of the Cooperative Extension Service, (2) accurate
records of rates and dates of applications and (3) the employment of juveniles
as harvesters. Three Aroostock County potato farmers agreed to cooperate in
the study. The cooperators were thought to be representative of the area's
potato farmers and agricultural practices as they Included one large farm,
identified herein as Farm 1, and two smaller farms (Farms 2 and 3). Their
1982 pesticide usage along with the dates and rates of application are listed
in Table 2. Climatological data for the 1982 growing season is listed in
Table 3.
Soil Collection Procedure
Five composite soil samples were collected for each pesticide applied
to the fields of the three farms selected for study. Each composite sample
was from one row of the potato field under harvest and the five rows selected
for sampling at each site were determined as follows:
1. The first 52 of the rows on each side of the study field were
eliminated from the sampling scheme. Sampling rows 1 and 5
were the respective rows which were located next to the 5Z
boundary lines at each end of the field.
2. The center row of the field was designated sampling row number 3.
3. Sampling row 2 was established at the mid point between rows 1
and 3 and sampling row 4 was equidistant between rows 3 and 5.
Each numbered sampling row was divided linearly into as many sampling
points as there were chemicals used in the spray schedule for the field of
-------
Table 2
1982 Pesticide Usage History
285
Study of Pesticide Residues Present in the Soil of
Three Potato Farms at the Time of Harvest- Aroostock County, Maine 1982
SITE
Farm 1
it
ti
•i
it
it
ti
Farm 2
it
it
«i
n
Farm 3
it
n
n
n
ti
*(«-
(f) -
(h) -
(1) -
+
PESTICIDE APPLICATIONS
Linuron (h)
Aldicarb (i)
Polyram (f)
Chlorthalonil (f)
Endosulfan (i)
Me thorny 1 (i)
Dinoseb (d)
Metribuzin (h)
Endosulfan (i)
Polyram (f)
Methamidophos (i)
Diquat (d)
Linuron (h)
Mancozeb (f)
Demeton (i)
Methamidophos (i)
Diquat (d)
Dinoseb (d)
deslccant
fungicide
herbicide
insecticide
1
1
2
12
1
1
1
1
1
7
1
2
1
9
3
3
1
1
APPLICATION RATE
DATES PAI/ACRE
May 27
June 1
June 16; Sept. 4
June 22,31
July 8,14,19,23,30
Aug. 6,12,20,24,31
Aug. 20
Aug. 24
Sept. 1
June 10
June 15
June 28
July 6,13,20,27
Aug. 3, 10
July 20
Aug 25; Sept 1
June 12
June 28; July 10,18,28
Aug. 10,18,25;Sept.5,14
July 28; Aug. 10,18
Aug. 28; Sept. 5,14
Sept. 1
Sept. 8
0.50
1.95
1.20
0.45
0.45
0.45
0.50
0.23
1.50
0.50
0.50
1.20
1.20
1.20
0.25
0.25
0.50
0.80
1.60
0.25
0.25
0.25
1.50
-------
Table 3
Climatological Data 286
Summary of Weather Observations from First Pesticide
Application (May 27) through Soil Sampling (September 19)
1982 Season by Month
Observations
Maximum Average Temperature
Minimum Average Temperature
Average Temperature *F
Total Precipitation (inches)
Average Barometric Pressure
Average Sky Cover (tenths)
May June July August
27-31 1-30 1-31 1-31
*F 78 71 79 69
*F 51 50 . 54 49
65 60 66 59
0 3.08 4.25 4.78
29.30 29.25 29.22 29.26
4.0 7.4 6.8 7.4
September
1-19
65
48
57
2.78
29.35
6.8
Listing of Days with Measurable Rainfall
June 2/.9S
June 147. 21
June 16/.69
June 20/.35
June 21/.17
June 22/. 01
June 23/.43
June 287 .06
June 297.21
July :27-t)7
July 37.07
July 197.02
July 22/2.42
July 257.40
(Date/Inches)
July 277.25 Aug. 25/1.15
July 28/.19 Aug. 26/.50
July 29/.S3 Aug. 27/.63
Aug. 57.39 Aug. 29/.03
Aug. 7/.08 Aug. 31/.07
Aug. 9/.24 Sept. 2/.9S
Aug. 10/.33 Sept. 3/.23
Aug. '137 .40 Sept. 6/.37
Aug. 14/.44 Sept. 9/.01
Aug. 15/.01 Sept. 11/.04
Aug. 19/.11 Sept. 14/.21
Aug. 20/.10 Sept. 15/.07
Aug. 22/.01 Sept. 16/.85
Aug.:24/.29 Sept. 18/.02
+ Data obtained from the National Weather Service Office-Caribou, Maine
-------
287
study. The first and last sampling points were positioned 25 feet from each
end of the row. The remaining sampling points were established at equidistant
points along the length of the row.
Each sampling point was given a letter designation. Hence, since site
No. 1 used 7 chemicals, there were seven equidistant sampling points (A
through G) in each of the five sampling rows. Site No. 2 which used five
pesticides, had 5 sampling points per row lettered A through E. Site No. 3
used 6 chemicals on the crop and therefore had equidistant 6 sampling points
per row lettered A through F.
Each sampling point was a two foot lineal section of the row selected
for sampling. The two foot section excluded the furrow of compressed soil
from tractor wheels. Soil was collected from the elevated portion of the
row which contained the potato plants, dead vine tops and mature potatoes.
Approximately one kilogram of soil was collected at each sampling point.
Using a stainless steel laboratory scoop, the centerline of the 24 inch
section of potato row was scratched in the soil. Five 100 gram soil samples
were taken equidistantly along a 4 inch line on each side of the centerline.
Dead plant tops and large rocks were removed from the sampling point. The
scoop, which measured 4 inches in length, was plunged into the soil to a
depth of about 4 inches and the hundred gram sub-sample was withdrawn and
placed In a pre-cleaned plastic pail. Nine similar sub-samples were taken
from the sampling point and were composited in the pall.
After the soil from all sampling points in a row were combined in one
pall, the container was capped with its lid and labeled as to farm site
and sampling row number. The sampling scheme was continued for the remaining
sampling rows at the particular study site.
At the end of sampling at a study site, each pail was processed so as to
end up with a representative soil sample ready for pesticide residue analysis.
Soil from each pail was sifted through a mesh sieve (USA Standard Testing
8
-------
288
Sieve ASTM E - 11 #8 mesh, 2.36mm) to remove vegative debris
and rocks. i T"6 debris, representing about 332 of the sample, were
discarded. The soil which passed through the sieve was collected, throughly
homogenized by hand mixing and then weighed into 500 gram sub-samples which
were then wrapped in heavy-duty aluminum foil, taped shut and labelled as to
site and row number.
At the completion of the sample preparation procedures itemized above,
the samples were placed in a deep freezer at - 4 F- At the completion of
the project, the frozen samples were packed in s tyro foam freezer chests and
transported to the Maine Public Health Laboratory where they were stored at
-40*F until analysis.
Description of Study Sites
Sept. 18, 1982 - Farm 1;
Farm 1 is located 1.5 mile north of Fort Fair field, Maine and about
2.5 miles west of the U.S. - Canadian international boundary. It was the
same farm used for the 1981 field testing and human monitoring for dinoseb
which was previously discussed. The study site was an 89.5 acre potato
field measuring 2,000 feet in length by 1,950 feet in depth. Weather conditions
for harvesting were marginal. The pickers started work under fair and sunny
skies, but the weather deteriorated to a light rain which increased in
intensity during the afternoon until operations ceased due to rain at 3:00
FM. Soil temperature, measured with a 6 inch dial thermometer was 54*F
(12*C). Soil conditions during the soil sampling period (10:00 AM to 3:00
FM) were wet, but not considered muddy until 2:30 FM when standing water
started to appear.
The harvest crew consisted of 40 workers aged 9-17 years. Twenty
eight pickers (70Z) were male and 12 (30Z) female. Dressed for dirty work,
most wore denim pants and flannel shirts under sweat shirts or wind breakers
and either the typical 4 inch leather work boots or tennis shoes. Observation
-------
289
revealed that 38 of 40 (952) wore light duty cotton or leather work gloves?
The study field contained 700 rows of potatoes. Soil sampling rows 1
and 5 were 35 rows (^ 100') from each end of the field. The five sampling
rows were approximately 150 rows (450*) apart and equidistant.
Sept. 19, 1983 - Farm 2;
This farm ±a located in Easton,Maine, four miles from the international
boundary and almost exactly half way between farms 1 and 3. The harvest
crew commenced work at 6:30 AM. The weather was clear and sunny and the
soil was drying after the rain of the previous afternoon and evening. Soil
temperature was 56*F (13°C) with small amounts of standing water in the
furrows between the rows. The actual potato hills were moist, but were
draining well. Air temperature was 40*F when sampling started 6:45 AM and
raised to 54" by the time sampling was completed at 8:30 AM.
The crew consisted of 35 workers aged 10 to 17 years. All were dressed
in denim pants and work boots or sneakers and all but one wore light-duty
work gloves.
The potato field under harvest measured 945* by 389* and contained
8.4 acres in 80 long rows. The five sampling rows were established with
rows 1 and 5 approximately 30* (10 rows) from each edge of the field. Rows
2, 3, and 4 were set about 80* (15 rows) apart and equidistant.
Sept. 19, 1983 - Farm 3:
The third farm sampling site is located about 5 miles south of Presque
Isle, Maine and 8 miles west of the international boundary. When sampling
commenced at 9:00 AM the weather was clear with full sun and no rain in sight.
The soil was drying from the previous day's rain with no standing water in
the potato rows. Air temperature was 60°F (J5*C) and soil temperature was 56°F (13*C
The harvest crew consisted of 48 workers ranging in age from 10 to 18
years. All harvesters were observed to be wearing light-duty cotton work
gloves or leather gloves. Most wore denim trousers, work snirts, sweat
10
-------
290
shirts and either sneakers or low work boots.
The potato field of study measured 972* by 483' and contained 10.8
acres of potatoes in 158 rows. Sampling rows 1 and 5 were located approxi-
mately 24' (8 rows) from each edge of the field. Rows 2, 3 and 4 were
established 100* (about 35 rows) apart and equidistant.
Soil Profile
The Soil Conversation Service of the U.S. Department of Agriculture
has classified the soil of each of the three fields of study as belonging
to the soil series designated as Caribou. Characterized as gravelly loam,
•
the Caribou series soil was formed in glacial till derived from calcareous
slate and limestone and is located in northern Maine (mostly in Aroostock
County). Clay content ranges from 20-25 percent.
A diverse variety of internal and external environmental conditions
affect the stability of pesticides in soil. Soil type, pH, organic matter and
clay content and amount of moisture and microorganisms are but a few of the
internal conditions which determine the fate of pesticides in soil. External
conditions include such factors as wind, sun, temperature, rain, humidity
and amount of cultivation and plant growth. Ultimately, pesticides in
soil are either degraded or removed from the soil by volatilization,
leaching and plant and animal uptake.
11
-------
IV. Analytical Procedures;
ALDICARB
291
Determination of total toxic aldicarb residue in soil by gas chromotography.
Union Carbide Corporation Agricultural Products Company, Inc., Research and
Development Department, P.O. Box 8361 South Charleston, West Virginia
25303, 1979.
CHLOROTHALONIL. ENDOSULFAN AND LINDRON
Luke, M.A. et. al. Extraction and cleanup of organochlorine, organophosphate,
organonitrogen and hydrocarbon pesticides in produce for determination by gas
liquid chromatography. JAOAC 58 (5): 1020-1026; 1975.
As seen in -
Pesticide Analytical Manual - Volume 1 section 232.4-, U.S. Department of
Health and Human Services, Food and Drug Administration, Washington, D.C.,
Transmlttal No 82-1, Dated 01/82.
Modification:
Eight hour aoxhlet extraction of 100 gram soil sample with prescribed
acetone as solvent extractant.
DEMETON
Zwelg, 6. and J. Sherma. Analytical Methods for Pesticides and Plant
Growth Regulators; Volume VI-Gas Chromatographic Analysis (New York:
Academic Press, 1972), 483-487.
DINOSEB
Gardner, R.C. and R.L. McKellar* A method to determine dinoseb residues in
crops and soil by gas chromotography. J. of Agric. and Food Chem. 28 (2):
258; 1980.
DIQUAT
Determination of low level dlquat residues In soil. Chevron Chemical Company,
Agricultural Chemicals Division, Research and Development Department (Richmond,
California). File No: 741-11 (1980).
12
-------
This procedure was the second of two methods which were utilized for diqua
analysis. The first procedure (King, R.S. Gas chroma to graphic determination
of diquat residues in potato tubers. J. Agric. Food Chem. 26 (6): 1460-1463;
1978) was discarded after unsatisfactory levels of recovery were observed
in fortified samples. Both methods used the same approach: the reduction
of the diquat cation with sodium borohydride prior to measurement by gas
chromatography using a N/P detector. The King procedure was found to be unac
ceptable because of poor recoveries and analytical sensitivity (high minimum
level of detection) with the 2 gram sample recommended. Various modifica-
tions were attempted, however Improvement in recovery and sensitivity was
not obtained. Chevron Chemical Company was then contacted and the above
procedure was utilized. The Chevron method, using a 50 gram sample, proved
to offer little advantage over the King procedure as equally poor recoveries
(x - 52) were produced after repeated analyses. Anticipated Improvement in
the Chevron method was not observed after modifications to the procedure
were made.
MANCOZEB AND POLYRAM
Cullen, T.C. Spectrophotometric determination of dlthiocarbamate residues
in crops. Analyt. Chem. 36 (1): 221-224; 1964. Keppel, G.E. Modification
of carbon disulfide evolution method for dithlocarbamate residues. JAOAC
52 (1): 162-167; 1969.
METHAMIDOPHOS
Leary, J. Gas liquid chromatographic determinations of acephate and ortho
9006 residues in crops. JAOAC 57 (1): 189-191; 1974.
METHOMYL
Reeves, R.G. and D.W. Woodham. Gas chromatographic analysis of me thorny1
residues in soil, sediment, water and tobacco utilizing the flame photometric
detector. J. Agr. Food Chem. 25(1): 76-78; 1974.
13
-------
METRIBUZIN
293
Thornton, J.S. and C.W. Stanley. Gas chromotographic determination of
sencor and metabolites in crops and soil. J. Agrlc. Food Chem. 25 (2):
380-386; 1977.
V. Quality Assurance;
The pesticide residue section of the Maine Public Health Laboratory is
certified under the EPA Drinking Water Laboratory Certification Program.
The MPHL has been a participant in this interlaboratory quality assurance
program for the past ten years.
The preceeding sections of this report have described, in detail, the
procedures utilized for the collection and analysis of samples in support
of this study. These procedures follow those which were outlined in the
SC PHAP Quality Assurance Plan which was submitted to the EPA in March
1982 and subsequently approved by the EPA QA Officer.
Specific QA analytical procedures utilized by the MPHL in support
of this study were:
Intralaboratory
1. Fortified samples were analyzed with every
five study samples for each pesticide studied to
document the extraction efficiency and reproducibllity
of the analytical methodology.
2. Blanks, reagent and soil, were also analyzed with each
pesticide analyis set to demonstrate the purity of
reagents and soil clean up procedure.
3. Confirmation was provided by dual column analyses.
14
-------
294
Interlaboratory
The extract from the first sample of each pesticide soil
series (except for the EBDC analyses for polyram and mancozeb )
was split with the SC PHAP Laboratory for confirmation.
The MPHL proceeded with the analyses of the pesticide
•oil series when the SC PHAP result was within + 20Z.
Table A reports the KPHL intralaboratory quality control results and
Table 5 lists the results of the interlaboratory quality assurance.
Acceptable levels of accuracy and precision for the analytical methodology
were achieved for all except one of the pesticides of study. The analytical
procedure for diquat produced recoveries of 3Z to 7Z from fortified samples.
thus only a fraction of the diquat residues were recovered from the study
samples. Repeated attempts, with and without procedure modification,
failed to improve upon the recovery level.
15
-------
Intralaboratory Quality Assurance
295
Recovery
Pesticide
Soil Spike
Aldicarb
tt
it
Chlorthalonil
it
it
Dene ton
Dinoseb
it
Diquat
ii
ti
EBDC1
Endosulfan
ii
Linuron
ii
it
Me thami dopho s
Me thorny!
n
Metribuzin
n
Level of
Fortification
(ppm)
.011
.033
.055
.15
.30
.40
0.1
0.5
1.0
2.0
8.0
40.0
4.0
.25
.50
.25
.35
1.50
0.5
1.0
5.0
0.6
0.8
Replicates
1
1
1
1
2
1
2
1
1
1
1
1
5
1
1
1
1
1
3
1
1
2
2
Level
•^••^•^•w
(ppm)
.010
.027
.043
.12
7- .29
,41
X- .056
0.48
0.71
.06
.54
2.80
I- 3. 2
.27
.53
.25
.34
1.88
X-0.42
0.86
4.84
X-0.48
X-0.74
I
90.9
81.8
78.2
80.0
96.7
102.5
56.0
96.0
71.0
3.0
6.8
7.0
80.0
108.0
106.0
100.0
97.1
125.3
84.0
86.0
96.8
80.0
92.5
Lover Limit
of Detection
(ppm)
.008
.001
.006
.013
.05
.1
.001
.008
.008
0.1
.003
\J Ethylenebisdithiocarbamate - for mancozeb & polyram
16
-------
296
Table 5
Interlaboratory Quality Assurance
MPHL
Sample No.
447
423
475
407
483
413
428
437
451
486
s of Sample Extracts Split
c Health Laboratory & the
Pesticide
aldicarb
chlorthalonil
d erne ton
dinoseb
diquat
endosulfan
linuron
methamidophos
me thorny 1
metribuzin
MPHL
.145
.776
.034
.779
.418
2.14
.724
ND1
ND
.025
Between the
SC PHAP Laboratory
Results (ppm)
SC PHAP
.153
.800
.035
.773
.358
1.95
.763
ND
ND
.024
I/ ND - None Detected
17
-------
VI. Results and Discussion 297
Table 6 lists the results of the soil analyses by study site. Results are
reported in parts per million (ppm). Table 7 presents soil persistence data
with literature citations for the pesticides of study. The study results are
supported by the half-life and persistence data reported in the literature.
Aldicarb, a granular, soil insecticide, was only applied at Farm 1. The
application occurred 110 days prior to harvest and residues recovered from the
five soil samples were found to be at anticipated levels of< 1.0 ppm (Union
Carbide, 1970). The average aldicarb residue equaled .273 ppm which fell within
the range of .12 to .36 ppm (X - 0.2) at 118 days post application reported by
Iwata (1977).
Chlorthalonil, also used only at Farm 1, was applied on twelve occasions
with the last spray taking place 19 days prior to harvest. An average concen-
tration of .657 ppm was observed. Chlorthalonil is a moderately persistent
organic foliar fungicide. Fifty percent of an application persisted for 21-35
days and was primarily retained in a layer 1 cm. below the soil surface (Hir.
Prof., 1978).
Endosulfan, an organic hydrocarbon insecticide, was applied at Farms 1 and
2. Residues averaging 1.37 ppm were observed at Farm 1 thirty days after
application and Farm 2 averaged .458 ppm at 96 days post application. The
average residue at Farm 2 was one-third the level at Farm 1, however the
application to harvest period of Farm 2 was three times longer than at Farm 1.
Rao (1980) reported residues of 0.4 to 2.0 ppm at 30 days post application and
0.1 to 0.6 ppm at 90 days for both dry and wet soils.
Linuron was applied at Farms 1 and 3. The Farm 1 application occurred
115 days prior to harvest and soil residues were found to average .728 ppm.
The Farm 3 application was 99 days prior to harvest and residue levels were
found to be lower at an average of .211 ppm. Linuron, a substituted urea
herbicide, is relatively persistent. Sukhoparova (1978) reported soil contained
18
-------
298
60 to 100% of the application one month after application while Walkee (1977)
estimated the half-life to range from 22 to 86 days.
Ethylenebisdithiocarbanate fungicides (polyram and tnancozeb) rapidly degrade
under most environmental conditions (Geunzi, 1974). The last polyram application
at Farm 1 was 14 days prior to harvest and only one of the five soil samples was
found to contain residue (2.89 ppa). Polyram was also used at Farm 2 with the
final application occurring 40 days prior to harvest. Here only two samples
contained residues and both equaled 2.01 ppm. The final mancozeb application at
Farm 3 took place five days prior to harvest and no residues were recovered from
the soil samples of this farm.
Methamidophos, an organophosphate insecticide, was sprayed at Farm 2 sixty
one days prior to harvest and at Farm 3 five days prior'to harvest. No residues
were recovered from the soil samples at either faro. Methamidophos has a short
half-life range of 2 to 6 days and it degrades rapidly in wet soil* For example,
soil moisture of 12.9% and 20.3% reduces the half-life to .5 and .25 days (Chevron,
1973). Although soil moisture data for the two study sites is not available,the
measurable rainfall for the area (Table 3) was significant.
Methorny1, a carbamate insecticide, was used only at Farm 1. The application
took place 25 days prior to harvest and no residues were recovered from the samples
of this farm. Harvey (1973) reported 1.8% of the applied dose was present after
one month and that decomposition was more rapid in sand and loam soils. The soil
of the study sites have been characterized as gravelly loam.
yetribuzin is a persistent triazine herbicide with an estimated half-life of
90-115 days (Webster 1978). This pesticide was applied at Farm 2 at 101 days prior
to harvest and the soil samples were found to have residues which averaged .031 ppm.
Smith (1982) found that variable persistence data for tnetribuzin is reported in the
literature, but agreed that 5-20% of the spring application can be recovered at the
end of the growing season. On the other hand, Lafleur (1980) reported that 90% of
19
-------
of the dose is lost in 23 days. 299
Desiccants, chemicals sprayed on the potato vines to cause drying and
withering of the plants to facilitate harvest operations, were used at the three
sites of study. Dinoseb was used at Farm 1, diquat at Farm 2 and both chemicals
were sprayed at Farm 3. Dinoseb residues recovered from the Farm 1 samples 18
days after application averaged .418 ppm while the Farm 3 samples averaged .041
ppm 11 days after application. Average persistence for dinoseb under normal
conditions at recommended usage rates is two to four weeks (Herbicide Handbook,
1970). An average diquat level of .535 ppm was observed at Farm 2 eighteen days
after application while no residues were recovered in the Farm 3 samples at 11
days post application. The difficulty encountered with the diquat analytical
methodology has previously been discussed. However, another contributing factor
is that diquat is very rapidly and completely inactivated by soil. This is a
result of the reaction between the double positively charged diquat cation
with the negatively charged sites on the clav minerals to form stable
complexes (Herbicide Handbook, 1970). Thus, the more clay content a parti-
cular soil has, the more complete inactivation would be expected. The clay
content of the soil of this study was reported to range from 20-25%.
The final pesticide of study, demeton, a systemic organophosphate insecti-
cide was applied, three times at Farm 3 with the final spray occuring 32 days
prior to harvest. Each of the soil samples contained quantifiable levels of
demeton. An average residue of .03 ppm was observed. No reports of demeton
persistence in soil were found in the literature.
20
-------
Table 6
Results of Soil Analyses (ppm)
300
Study of
Farms
Pesticide residues Present in the Soil of Three Potato
at the Time of
Harvest-Aroostock County, Maine 1932
FAKi 1
Sample 1
Sample 2
Saaple 3
Sample 4
i Sample 5
X
SD
Aldicarb
.711
.175
.114
.206
.159
.273
.247
Chlorthalonil
.493
.790
.767
.596
.640
.657
.123
Dinoseb Endosulfan Linuron Polyran Methc-"i
.303 .916 .807 2.69 ^
.779 1.70 .603 SD ND
.604 1.20 .734 SD SD
.335 1.70 .743 SD SD
.067 1.32 .752 SD SD
.418 1.37 .723 .578 -=-
.278 .337 .075 1.29 —
FARM 2
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
X
SD
2
Ditjuat
.263
.069
.418
.113
1.81
.535
.726
Endosulfan
.582
.203
.454
.599
.452
.458
.158
Methamidophos Metribuzin Polvrara
SD .025 2.01
ND .027 NT)
ND .033 SD
•SD .029 ND
ND .040 2.01
— .031 .80
— .006 1.10
FAKI 3
Sanple 1
Sample 2
Sample 3
Sample 4
Sample 5
x"
SD
Dinoseb
.044
.053
.038
.014
.054
.041
.016
2
Diauat
SD
ND
ND
ND
ND
—
—
Linuron Mancozeb Methamidophos Demeton
.295 ND ND .045
.253 ND ND .027
.253 ND ND .013
ND ND ND .031
.253 ND ND .034
.211 — — .030
.119 — — .012
\l SD » Sone Detected, See Intralaboratory QA Results for Lower Licit of Detection
2J The analytical procedure for diquat produced less than 102 recovery for spike samples
fortified at three different levels (Table 4). Thus, the residues recovered from the
Farm 2 samples are less than 10% of the actual residues believed to be present. Like-
wise, diquat residues may have been present in the Farm 3 samples, but were not recovered
when analyzed. ^
-------
K>
K)
PESTICIDE
Aldicarb
i<
Chlorthalonil
Dinoseb
Diquat
Endosulfan
it
Linuron
tlancozeb/
Polyram
Methamidophos
tte thorny1
Metribuzin
Table 7
Soil Persistence Data for the Pesticides of Study
i LIFE (DAYS)
^ 32
14-35
22-86
12-16
2-6
PERSISTENCE
Average of 0.2 ppm at 118 days
< 1.0 pptn at 100 days
50% of dose persistent at 21-35 days
persistent for 2-4 weeks at recommended rates
very rapid & complete inactlvatlon by soil
•v- 0.4 - 2.0 ppm at 30 days
^ 0.1 - 0.6 ppm at 90 days
REFERENCE
Iwata (1977)
Union Carbide (1970)
Illr. Prof. (1978)
Herbicide Handbook (1970)
Herbicide Handbook (1970)
Rao (1980)
M
Wallcce (1977)
Sukhoparova (1978)
60-100% of dose persistent at 30 days
phytotoxic concentrations disappear within 4 months Herbicide Handbook (1970
Geu-zi (1974)
rapidly degrades under most environmental
conditions
^ 2% of dose persistent at 30 days
5-20% of dose persistent after 22 weeks
10% of dose persistent at 23 days
90-115
Chevron (1973)
Uarvey (1973)
Smith (1982)
LaFleur (1980)
Webster (1978)
-------
VII. References;
Chevron Chemical Corporation. The impact of orthene on the environment., p. 5
(1973).
Geunzi, W.D. (ed) . Pesticides in soil and water (Madison: Soil Science Society
of America, Inc., 1974), p. 153
Harvey, J. Jr. and H.L. Pease. Decomposition of methonyl in soil J. Agric.
Food Chem. 21: 784 (1973).
Herbicide Handbook of the Weed Science Society of America, WSSA Monograph 3,
2nd. ed. (Urbana: WSSA, University of Illinois, 1970), pp. 54, 170 and 186.
Investigation of Pesticide Residues in Soil. Annual Report of the Hiroshima
Prof. Agric. Exp. Stn. , p. 24 (1978).
Iwata, Yutaka et. al. Aldicarb residues in orange leaves and soil after an
aldicarb soil application in an orange grove. J. Agric. Food Chem. 25 (4):
933-936 (1977).
LaFleur, R.S. Loss of pesticides from congaree sandy loam with tine character-
ization. Soil Sci. 130(2): 83-87 (1980).
Rao, D.M.R. and A.S. Murty. Persistence of endosulfan in soils. J. Agric.
Food Chem. 28 (6): 1099-1101 (1980).
Smith, A.E. and B.J. Hayden. Comparison of the persistence of EPIC, metribuzin
and propanil in Saskatchewan field soils. Bull. Environ. Contam. Toxicol. 29,
243-247 (1982).
Sukhoparova, V.P. and M.A. Ryzhaya. Degredation of linuron in soil and flax
plants. Khim. Selsk. Khoz. 15 (5): 68-72 (1978).
Union Carbide Corporation. Technical information to temik 10G aldicarb
pesticide, pp. 39-40 (1970).
Walkee, A. and J.A. Thompson. The degredation of simazine, linuron and
propyzamide in different soils. Weed Res. 17 (6): 399-405 (1977).
Webster, G.R.B. et. al. Nonbiological degredation of the herbicide metribuzin in
manitoba soils. Bull. Environ. Contam. Toxicol. 20 (3): 401-408 (1978).
23
-------
303
Assessment of Dermal and Respiratory
Exposure of Adult and Juvenile Blueberry
Harvesters to Ethyl Parathlon, Malathlon,
and Benomyl, DupUn County, North Carolina
1982
Research performed by
Medical University of South Carolina
-------
304
Table of Contents
Title Page
Abstract 11
List of Tables ill
I. Objective 1
II. Background 1
III. Methods 2
IV. Analytical Methodology 12
V. Quality Assurance 14
VI. Results 20
VII. Discussion . 33
VIII. References 35
-------
Abstract 305
Ten Juvenile (age 12-16) and ten adult (age 22-66) blueberry harvesters
were monitored for their dermal and respiratory exposure to ethyl parathlon,
malathlon and benomyl In order to determine If there were any differences
between the exposure patterns of these two groups. The three chemicals had
been respectively applied 22, 15 and 21 days/prior to harvest. Assessment of
dermal exposure consisted of cotton gloves for the hands and gauze squares
attached to the forearms, chest, shoulders and back of each worker. Each
participant also wore a personal air sampler during monitoring. Urine samples
were collected from each worker in order to determine whether exposure resulted
in the absorption and excretion of the chemicals of study.
Exposure to ethyl parathion was below levels of quantification as only
three samples contained measurable residues (2 juvenile and 1 adult pair of
gloves) . Statistical analyses of malathion and benomyl residues recovered
from the sampling media revealed four significant differences between the
exposure patterns of the adults and juveniles: chest and back gauze samples
for malathion and glove gauze and forearm gauze for benomyl. The juveniles
accounted for only one of the significant differences which was the trend of
higher average residues in the malathion back gauze. Malathion and benomyl
metabolites recovered from the participants' urine samples demonstrated the
juveniles had higher average concentrations than the adults, however no
statistical differences were observed.
Environmental sampling of air, soil, foliage and blueberries was performed
to document the presence of ethyl parathion, malathion and benomyl during
participant monitoring.
ii
-------
306
List of Tables
Table No. Title Page
1 Pesticides Recommended for Use on North
Carolina Blueberries. .... . 4
2 Juvenile Participant Data 6
3 Adult Participant Data 7
4 Intralaboratoty Quality Assurance 17
5 Interlaboratoxy Quality Assurance 18
6 Halathion Results-Juvenile Participants. ... 21
7 Malathion Results-Adult Participants 22
8 Benomyl Results-Juvenile Participants 24
9 Benomyl Results-Adult Participants 25
10 Statistical Analyses (t-test) of Juvenile vs.
Adult Sample Media for Malathion and Benonyl. . 27
' 11 Results of Environmental Analyses 29
12 High Volume Air Sample Results 31
iii
-------
I. Objective;
The objective of this study was to assess the difference, if any,
between the dermal and respiratory exposure patterns of juvenile and
adult blueberry harvesters who, under normal working conditions, had
potential expbsure to ethyl parathion, malathion and benomyl.
II. Backgroundi
The U.S. Environmental Protection Agency (EPA) and the U.S.
Department of Labor (DOL) finalized an interagency agreement on
March 17, 1980. This agreement, "Youth in Agriculture", provided
for the development of pesticide protection programs for farm workers.
The employment of children during the harvest of hand picked crops is
of special concern to the DOL. This agency has the authority to waive
restrictions to permit children to work, however it also must assure
that there are no adverse health effects to the children for which the
exemption was granted. One goal of the interagency agreement is the
determination of scientifically based reentry intervals for children
and the assessment of potential health effects of pesticides on
children working in agriculture.
•
The EPA and DOL have assuned that the potential for the exposure
of children to toxic chemicals in agriculture is widespread and that
children are generally more sensitive to chemical exposure. Further-
more, children possibly have greater rates of dermal and/or gastro-
intestinal uptake and have decreased capacity for detoxification. Yet,
little or no data exists to support these assumptions as it applies to
field workers. In order to bridge this data gap, it is necessary to
perform studies which measure the pesticide exposure of adult and
juvenile workers to various pesticides during the harvest of a variety
of hand-picked crops. The harvest of North Carolina blueberries requires
extensive hand labor and juveniles (age j> 12) are conaonly hired as
-------
pickers and work along with adults.
308
North Carolina is a major East Cost producer of blueberries.
During 1981, approximately 7.2 million pounds of blueberries were
harvested from 3,200 acres. Blueberries grown for fresh market sales
accounted for 80% of the harvest while the remaining 20% were processed
(canned and frozen). Harvest usually begins in late May and continues
through June. Figure 1 displays the principal blueberry region of
North Carolina. The soil of this area, fine sandy loam, is ideal for
the cultivation of blueberries.
Several varieties of blueberries, which mature at different intervals
throughout the harvest period, are cultivated in order to have a continuous
supply of fresh berries for market. The later ripening varieties are
grown almost exclusively for processing. The blueberry bushes range in
height from four to over six feet and are grouped in rows by variety.
The School of Agriculture and Life Sciences of North Carolina State Univer-
sity recommends seven insecticides, three fungicides and four herbicides
for use on blueberries. Table 1 lists these pesticides along with the
minimum intervals between application and harvest.
III. Methods;
Site - Duplin County is in the center of North Carolina blueberry belt
(Figure 1) and in 1981 produced 12% of the total state harvest. A
Duplin County farmer with approximately 100 acres of blueberries agreed
to cooperate with the study and assisted in the recruitment of partici-
pants. His 1982 harvest of early maturing blueberries commenced on
May 26. Application of ethyl parathion, benomyl and malathion occurred
22, 21 and 15 days prior to harvest:
Date of X Active EPA Reg. PAI/
Application Pesticide Ingredient No. Acre
May 4 Helena Parathion 4E 46.2 5905-82 0.15
May 5 Dupont Benlate
Fungicide 50.0 352-354 0.50
May 11 Helena Cythion 56.44 5905-196 1.00
-------
NORTH CAROLINA
Counties/ County Scats, Mountains, M<|
I
•a*
i
•i*
I
I
7*-
FIGURE 1
North Carolina Blueberry Belt
COUHtV M*l
CD -1
I
•4*
I
•i-
Ml-
III!
19 7H >•» 74
-------
Table 1
Pesticides Reco"™gnded for Use on
North Carolina Blueberries^
Minimum Interval (Days)
Pestieide Between Application and Harvest
Insecticides:
azinphosmethyl 3
carbaryl 0
endosulfan (not to be used after buds are formed)
•thion (post harvest-spray)
malathion 1
malathion ULV 0
oil - type 70 second superior (dormant use only)
parathion 14
Fungicides:
benomyl 21
captafol 21
triforine 40
Herbicides:
dichlobenil (not for use after mid-February)
paraquat (spot control prior to harvest)
simazine (prior to budding & post harvest)
terbacil (post harvest application)
+ 1981 North Carolina Agricultural Chemicals Manual
(Prepared by The School of Agriculture and Life
Sciences of North Carolina State University)
-------
.. 311
the applications were made by tractor pulled spray rigs. Each spray rig
had two inverted "L" Booms which were attached to the rear of the holding
tank. Six Tee-Jet even flat spray pattern nozzles were attached to each
boom: three 8003E nozzles on the horizontal portion of the boom and equally
spaced'on the vertical portion of the boom from top to bottom - one 8003E,
one 8004E and one 8006E.
Participants - All blueberry harvesters were seasonal workers and were
residents of the surrounding area. Due to the availability of local
workers, migrant laborers were not required. Participants were recruited
from one of the several harvest crews employed by the cooperating
farmer. The participants recruited for this study are thought to be
representative of the harvester population. It was observed that each
harvest crew was composed predominantly of female workers and approxi-
mately one-half of the workers of each crew were 18 or younger.
Ten juveniles (age 12 - 16, three males and seven females) and ten adults
(age 22 - 66,' all females) were recruited for participation in the
study (Tables 2 and 3). According to DOL regulations, a child under age
12 can not be hired to pick blueberries. The farmer was careful in
complying with this regulation as labor officials routinely checked the
fields for underage workers.
The blueberry harvesters began work around 7:00 in the morning.
Each person was assigned a row or a section of a row for picking.
When rows were completed, the crew would move to other rows ready for
harvest. The worker picked each rippened blueberry individually
which was then placed into a container tied to the individual's waist.
As the container filled, it was dumped into a wooden pail. Several
times throughout the workday, each worker's wooden pails were weighed
and cash payment was made to the worker.
-------
Table 2
Juvenile Participant Data
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Blueberry Harvesters to Ethyl Parathion, Malathion and
Benomyl-Duplin County, North Carolina 1982
312
PARTICIPANT
STUDY
NO.
1
2
8
9
14
15
16
17
18
19
AGE
13
15
15
14
14
12
12
15
14
16
, SEX
M
F
F
F
F
M
M
F
F
F
HEIGHT
(cm)
157
157
167
161
163
150
152
170
173
155
WEIGHT
(kg)
52
50
63
50
61
41
45
63
63
57
WORK CLOTHING2
4
1
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
Jeans, sweat shirt, sneakers &
bat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, sneakers
& hat <
Jeans, long sleeve shirt, sneakers :
& hat i
\
t
Jeans, long sleeve shirt, shoes •
& hat ;
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
If Juveniles (Age 12-16) n » 10. All participants were black and were
recruited from a single harvest crew led by participant tf 20.
2f None of the study participants or other harvesters wore work gloves,
-------
Adult Participant Data
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Blueberry Harvesters to Ethyl Parathion, Malathion and
Benomyl-Duplin County, North Carolina 1982
313
PARTICIPANT
STUDY
NO.
3
4
5
6
7
10
11
12
13
20
AGE
66
22
23
41
48
34
39
56
43
49
, SEX
F
F
F
F
F
F
F
F
F
F
HEIGHT
(cm)
160
167
152
152
157
173
162
152
157
168
WEIGHT
(kg)
59
63
66
74
72
58
83
57
86
99
WORK CLOTHING2
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt &
sneakers
Pants, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
If Adults (Age 22-66), n - 10. All participants were black and were
recruited from a single harvest crew led by participant 9 20
2f None of the study participants or other harvesters wore work gloves.
-------
The twenty participants were monitored twice on May 26, under
314
normal working conditions, for their dermal and respiratory exposure
to the chemicals of study. Each monitoring session was two hours in
duration. The samples collected from the first session (7:30 - 9:30)
vere -analyzed "for ethyl parathion and malathion residues and the samples
from the second session (10:00 - 12:00) were analyzed for benomyl.
Assessment of Dermal Exposure - Each participant wore a long sleeve
disposable paper jacket (Tyvek 14) during the two monitoring sessions.
Affixed to each jacket were seven 2" x 2" - 8 ply gauze squares
(pre-extracted with acetone) with glassine backing: one on each forearm,
breast and shoulder and one square on the center of the back. The pur-
pose of the gauze squares was to trap dislodgeable residue from the
bushes and soil that were released as a result of the workers* physical
activity in the field, the glassine backing prohibited gauze contamina-
tion from skin oils and perspiration absorbed through the jacket. The
gauze squares were removed from the jackets at the completion of each
monitoring session and were pooled into three samples (forearms, chest
and shoulder) with the back square remaining separate. All samples were
wrapped in aluminum foil, labeled and frozen prior to analyses.
Translocated residue to the workers' hands was assessed through
the analyses of 100% cotton gloves worn by the participants during their
exposure monitoring sessions. Affixed to the back of each glove was a
2" x 2" - 8 ply gauze with glassine backing. It was anticipated that
the gauze would avoid much of the contamination expected from dirt, skin
oils, etc. The gloves were laundered, rinsed in organic free water and
then acetone extracted with the gauze pads prior to use. At the
completion of each monitoring session, the gauze squares were removed
from the gloves. The gloves and glove gauze of each participant were
pooled seperately, wrapped in aluminum foil, labeled and frozen prior
to analyses.
8
-------
Assessment of Respiratory Exposure - Each participant wore a DuPont
P-4000 Personal Air Sampler, precalibrated at 2.0 liters/minute,
during the two monitoring sessions. The sampling train consisted of a
37 mm cassette,with a Millipore glass fiber filter (.3 micron pore
size)followed by a custom made XAD-4 resin sorbent tube (500 mg).
The sampling media were chemically extracted with hexane, acetone
and diethylether prior to use. Start and stop times of the air
samplers were recorded for subsequent air volume calculations and
the flow control light-emitting diodes of the air samplers were
monitored to insure that proper flow had been maintained. At the
end of the sessions, each air sampling medium was wrapped in aluminum
foil, labeled and frozen prior to analysis.
Assessment of Absorption - A urine sample was collected from each parti-
cipant to document whether the individual's exposure resulted in absorption
and excretion of the chemicals of study. The participants were requested
to collect first morning voids on May 27 (the day after exposure monitoring).
Samples were collected in polyethylene bottles which had been washed and
rinsed with organic free water. Upon receipt, the samples were split for
subsequent ethyl parathlon/malathion and benomyl analyses. All specimens
were labeled and frozen prior to analysis.
It was anticipated that the ingestion of blueberries could provide
another potential source of exposure to the participants. After monitoring,
the participants were asked if they had eaten blueberries and if so, an
estimate of the quantity was requested. All participants admitted to and
were observed eating blueberries, however efforts to quantify the amount
ingested by participant were unsuccessful. Through observation, the
three on site investigators have estimated that, on the average, adult
participants ate at least one cup of blueberries while the juvenile rate
was estimated to be slightly higher at l\ to 1% cups.
-------
Environmental Sampling - Collection of soil, blueberry, foliage and 7 4 /
high volume air samples was performed to document the level of ethyl
parathion. malathion and benomyl present at the time of participant
monitoring. A .ten acre field close to the center of the blueberry
farm was selected for sampling. The field consisted of 60 rows which
were approximately eight feet apart. The rows were planted north to
south and the blueberry bushes were spaced about every five feet along
the length of the row.
Two sets of environmental samples were collected: one set for
subsequent ethyl parathlon/malathion analyses and the second set for
benomyl.
Ten composite samples for each substrate (except air) were
collected for each set of samples. Each composite sample was from
one row of the field and the ten rows selected for sampling were
determined as follows:
1. The row in the center of the field was located.
2. Sampling rows 1 through 5 were the rows to the right
of mid-field which were equidistant from each other
to the last crop row on the right.
3. Sampling rows 6 through 10 were the rows to the left
of the row of mid-field and were equidistant from each
other to the last crop row on the left.
Along the length of each row selected for sampling, five "collection
points", all equidistant from each other, were designated. Each
collection point was a blueberry bush and samples were collected as
follows:
10
-------
1. Blueberries - Ac each collection point (bush), five
berries were collected; one from the top of the bush,
two from mid-height and two from the bottom of the bush.
Thus, 25 berries were collected from the sampling row to
constitute one composite blueberry sample.
2. Foliage - The same collection points used for the blueberry
samples were also used for the sampling of blueberry leaves.
At each bush selected for sampling, four leaves were collected;
one from the top, two at mid height and one from the bottom.
Thus, 20 blueberry leaves composed one composite foliage
sample.
3. Soil - The same collection points of the ten sampling rows
were again used for composite soil sampling. At the base
of each sample bush, approximately 100 g of soilwere collected
from the top half-inch of soil using a stainless steel scoop.
Each composite soil sample contained approximately 500 g of
soil.
All composite samples were collected in amber colored glass jars which
had been pre-rinsed with acetone. The jar lids were lined with aluminum
foil. All samples were labeled and frozen prior to analysis.
High volume air sampling (20 f3/m) was performed in the same field of
study. Two Staplex High Volume Air Samplers (Model TF1A), calibrated
prior to use, were placed side by side approximately 50 feet into the
field. The purpose for placing the high volume air samplers next to
each other was to have one serve as a quality control check for the
other. AC power was supplied from a nearby packing shed. The ambient
air was sampled for ethyl parathion/malathion and benomyl during two
one hour periods. The sampling trains consisted of 4.0" diameter glass
fiber filters for participates which were followed by approximately 100
ml of XAD-4 resin for vapors. Both media were chemically extracted
11
-------
31 8
After sampling, the filters were individually wrapped
in aluminum foil, labeled and frozen prior to analysis. The resin was
transferred to amber colored glass jars, capped with aluminum foil lined
lids, labeled and frozen.
Meteorological Data - The following observations were made on the day of
studv: 1) maximum temperature, 2) relative humidity, 3) barometric
pressure, 4) wind speed, direction and condition, 5) percent cloud
cover,and 6) rainfall.
IV. Analytical Methodology:
Ethyl Farathion and Malathion -
Analyses of all sample extracts, except urines, were performed
either on a Tracor 220 gas chromatograph, equipped with a Model 702
Nitrogen-Phosphorus detector and a Tritium Electron Capture detector,
or on a Varian Vista 6000 series gas chromatograph equipped with a
Thermal Specific Detector (N and F) and dual Nickel Electron Capture
Detectors . Qualitative and quantitative analyses were performed on
Column I and confirmed on Column II as follows:
Column I: 4mmI.D. x6mmO.D. x 183 cm. Glass, packed with 1.5%
OV-17/1.95Z OV210 on 80/100 gas chrom Q, carrier N£ or He at
60 cc/min.
Column II: 4 mm I.D. x 6 mm O.D. x 183 cm. Glass, packed with 42
SE30/6Z OV210 on gas chrom Q, carrier N£ or He at 80 cc/min.
GLC operating conditions were as follows:
Inj. Fort Temp. - 225°C
Detector Temp. - 210°C H3 EC
325°C Ni63 EC
245°C N-F
Column Oven - 200*C
12
-------
Transfer-line Temp. - 235°C ._
3/9
Chart Speed - 0.5 in/mln or 1 cm/mln.
Electrometer Attenuation - 10 x 16 Tracor EC
1x8 Tracor N-P
Quantitative analysis was performed on peak height and/or peak
area comparisons using external standards and accepting no more than
a 10Z variance between sample and standard peak size.
Samples were extracted into 30/70 dichloromethane /hexane,
concentrated, rediluted to appropriate volume with hexane, and then
injected onto the GLC column.
The reference for the analytical procedure throughout this study
was "The Manual of Analytical Methods for the Analysis of Pesticides
in Human and Environmental Samples" (EPA 600/8-80-038) June 1980.
Urine Samples were analyzed for alkyl phosphate metabolites by
the Benzyl Alkyl Phosphate Method of the University of Miami School
of Medicine, using a Tracor 220 Gas Chromatograph equipped with a Flame
Photometric Detector in the phosphorus mode (X»526nm) . Analyses were
performed on Column III and confirmed on Column II.(as previously described)
Column III: 4 mm I.D. x 6 mm O.D. x 183 cm. Glass, packed with 5Z
OV210 on 80/100 mesh gas chrom Q, carrier N£ at 25 cc/min.
GLC conditions were as follows:
Column temp 175*C
Detector temp. 215*C
Hydrogen 100 cc/min
Air 80 cc/min
Electrometer Attenuation - 32 x
13
-------
Benomyl - 320
All analyses were performed on a Waters Model 6000 A High Performance
Liquid Chromatograph equipped with a Model 440 Absorbance Detector at 254 and
290 nm. All samples, -except urine, were extracted and analyzed following the
method of Zweig et. al. (J. Agric. Food Chem., 31 (2) 1109-1113, 1983).
Operating conditions were as follows:
Column: C-18
Mobile Phase: acetonitrile/water (50:50)
Flow Rate: 1.0 ml/min.
Urine samples were extracted and cleaned up according to the procedure published
by J.A. Kirkland (J. Agric. Food Chem., 21 (2) 171-177, 1973). Analyses for
methyl 2-benzemidazolecarbamate (known as carbendazim or MBC) and 5-hydroxy-
2-benzimidazole carbamate (5-OH MBC), as recommended by Gardiner et. al.
(J.Agric. Food Chem. 22 (3) 419-427, 1974) were performed using the Waters
660 solvent programmer with the following conditions:
Column: C-1S
Mobile Phase: A - 0.15 N sodium acetate/0.15 N acetic acid (7:3)
B - Acetonitrile
Program: Curve # 5 (10Z - 30% B at 1.4 ml/min for 10 min.,
hold 10 min.)
V. Quality Assurance: The preceeding paragraphs have described, in detail, the
procedures utilized for the collection and analysis of samples in support of
this study. These procedures follow those which were outlined in the "SC PHAP
QA Plan for Extramural Project-Dermal and Respiratory Exposure Assessment of
Adult and Juvenile Harvesters" which was submitted to the EPA in March 1982
and subsequently approved by the EPA QA Officer. Also included in the QA
Plan and adhered to by the SC PHAP were general quality control procedures
such as peer and EPA review of the study protocol, evaluation of analytical
methodologies, record keeping (field tracking reports, laboratory sample log
14
-------
books, instrument maintenance logs, etc.). scheduled routine maintenance,
o c. \
checks of the gas chromatographic system, use of analytical reference standards
obtained from the EPA Environmental Monitoring Systems Laboratory (EMSL) and
participation in the EPA Quality Control Program under the direction of the
EMSL.
Specific QA analytical procedures utilized by the SC PHAP laboratory in
support of this study were:
Intralaboratory
1. One fortified sample was analyzed with every ten study samples to
document the extraction efficiency and reproducibility of the
analytical methodology.
2. Blanks, sample media and reagent, were also analyzed with every ten
study samples to demonstrate the purity of reagents and cleanup
procedures of the sample media.
3. Dual column confirmation by GC/NP and GC/EC for parathion and malathion
and dual wavelength confirmation for benomyl.
A. Sample media were fortified in the field at the time of sample
collection and were freezer stored along with the study samples.
The field spikes, when analyzed, provided data on stability and
sample degradation over time.
Interlaboratory
Blind analyses of fortified samples which were split between the
SC PHAP and the Iowa PHAP (NPHAP Quality Assurance Project) which
served as procedural checks.
Intralaboratory quality assurance results for ethyl parathion, malathion
and benomyl are listed in Table 4. The majority of average recoveries for each
pesticide by media and spiking level fall within the range of 90% to 1002.
Field spikes of sample media made on the day of study demonstrated little or
no degredation over time. Analyses of media and reagent blanks demonstrated
the absence of interfering contaminants. The results of the intralaboratory
15
-------
quality assurance procedures indicated that no corrections to study data were j L L.
required for analytical methodology or storage losses.
Intel-laboratory quality assurance results are reported in Table 5. All
average recoveries for ethyl parathion and malathion samples split with the
Iowa PHAP laboratory ranged from - 9Z to 45Z of the corresponding recoveries
reported by the South Carolina PHAP Laboratory. Benomyl average recoveries,
except for soil, were well within the range of +20% agreement which was pre-
established range for interlaboratory quality control. Benomyl recoveries for
the spiked soil samples differed by an average of 22Z between the two labora-
tories. As the benomyl analyses progressed, increased proficiency in sample
extraction and analysis led to increased accuracy and precision as indicated by
the intralaboratory data.
16
-------
Table 4
323
Intralaboratory Quality Assurance
Recovery
Pes ticide/Medium
Ethyl Parathion
Gauze Squares
G.F. Filters
XAD-4 Resin
Urine2(DEP)
Soil
Blueberries
Leaves
Field Spikes:
G.F. Filters
XAD-4Resin
Malathion
Gauze Squares
G.F. Filters
ii
XAD-4 Resin
2
Urine (DMP)
Soil
Blueberries
Leaves
Field Spikes:
G.F. Filters
it
«t
XAD-4 Resin
Spiking
Level ,
0.3 ug
150 ng
1.2 ug
1.2 ug
300 ppb
100 ng
100 ng
100 ng
2.0 ug
3.0 ug
4.0 ug
3.0 ug
5.0 ug
100 ng
2.0 ug
2.06 ug
100 ng
103 ng
100 ng
350 ppb
100 ng
100 ng
100 ng
2.0 ug
3.0 ug
4.0 ug
3.66 ug
6.1 ug
Number of
Replicates
12
1
1
3
8
1
,1
1
3
1
1
1
1
31
6
12
9
3
9
8
5
5
5
3
1
1
1
1
X (Z)
0.29(96.7)
136.0(90.6)
1.13(94.2)
1.18(97.9)
355.3(118.0)
96.0(96.0)
99.8(99.8)
99.7(99.7)
1.56(78.0)
2.28(76.0)
3.67(91.8)
3.21(107.0)
5.30(106.0)
96.2(96.2)
1.95(97.5)
1.92(93.2)
97.4(97.4)
97.7(94.9)
91.0(91.0)
242.5(69.3)
93.0(93.0)
97.6(97.6)
100.8(100.8)
1.24(62.0)
2.54(84.6)
3.72(93.0)
3.70(101.0)
5.40(88.5)
Standard
Deviation
0.01
-
-
0.07
28.2
-
-
-
0.15
-
-
-
•«.
6.1
0.09
0.14
12.0
2.9
7.7
10.5
14.1
6.1
11.6
0.03
-
-
-
-
Coetficient.
of
Variation
3.4
-
-
5.9
7.9
-
-
- -
9.6
-
-
-•
—
6.3
4.6
7.3
12.3
3.0
8.5
4.3
15.2
6.3
11.5
2.4
—
-
-
_
17
-------
Pesticide/Medium
Benomyl
Gauze Squares
G.F. Filters
ft
XAD-4 Resin
XAD-4 Resin
MBC
Urine:
5-OH MBC
Spiking
Level
Soil
Leaves/Blueberries
Field Spikes:
G.F. Filters
tt
XAD-4 Resin
Number of
Replicates
X(Z)
Recovery
Standard
Deviation
324
20.0 ng
0.6 ug*
2.0 ug
1.0 ug
6.0 ug
0.4 ppm
0.4 ppm
20.0 u,g
66.7 ug
0.6 ug
2.0 ug
1.0 ug
6.0 ug
15
4
2
2
1
6
6
4
3
4
2
2
1
17.5(87.5)
0.6(100.0)
2.1(105.0)
0.99(99.0)
5.97(99.5)
0.29(72.5)
0.29(72.5)
15.8(79.0)
57.2(85.8)
0.6(100.8)
2.1(105.0)
0.99(99.0)
5.97(99.5)
1.56
0.06
-
-
.037
.066
0.76
5.8
0.07
-
-
-
Coefficient
of
Variation
8.9
10.9
12.8
22.7
4.8
10.1
11.7
jj All analyses of blanks, sample media and reagent, were negative. Gauze squares
served as quality control for cotton gloves.
21 Provided by the EPA Environmental Monitoring Systems Laboratory (Las Vegas)
18
-------
325
Table 5
Intel-laboratory Quality Assurance
Pesticide/Medium
Ethyl Farathion:
Gauze Squares
G.F. Filters
XAD-4 Resin
Soil
Leaves
Halathion:
Gauze Squares
G.F. Filters
XAD-4 Resin
Soil
Leaves
Benomyl:
Gauze Squares
G.F. Filters
XAD-4 Resin
Soil
Leaves
,ts o_f Fortified Samples Split Between
the»SC and IA PHAP Laboratories
Recovery
Spiking
Level
1.2 ug
1.2 ug
1.2 ug
4.0 ug
4.0 ug
1.2 ug
1.2 ug
1.2 ug
4.0 ug
4.0 ug
20.0 ug
20.0 ug
20.0 ug
20.0 ug
20.0 ug
Number of
Replicates
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
SC
X
1.31
1.24
1.24
3.90
3.98
1.26
1.29
1.27
3.93
4.01
11.6
16.1
9.3
17.4
16.1
IA
% X Z
109
103
103
98
99
105
108
106
98
100
58
81
47
87
81
1.35
1.19
1.30
3.75
3.94
1.21
1.23
1.17
3.86
4.22
9.72
17.1
12.0
12.9
19.5
113
99
108
94
98
101
102
97
97
105
49
86
60
65
98
-------
VI. Results;
Participant Exposure to Ethyl Parathion
No detectable ethyl parathion residues were observed in the participants'
gauze square and^personal air samples and no dialkyl phosphate metabolites
i
(diethyl phosphate and diethy1 thiophosphate) were observed in their urine
samples. Only three of the twenty pairs of cotton gloves contained quanti-
fiable residues. Juvenile participants 14 and 19 accounted for two of the
positive samples with ethyl parathion residues of 429 ng and 525 ng. Adult
participant 20 had the third positive glove sample with a residue of 1,670 ng.
Participant Exposure to Malathion
Tables 6 and 7 respectively report the malathion residues recovered from
the sample media of the juvenile and adult participants.
All cotton glove samples contained malathion residues. The Juveniles
averaged 1,857 ng per pair of gloves while the adult group's average was 752
greater at 3,246 ng. This difference between the adults and juveniles is
attributable to adult participant 11, whose cotton glove residues totaled
18,000 ng. If this outlier is omitted, the average glove residue for the
remaining nine adults would equal 1,607 ng. The gauze squares attached to
the back of the gloves also demonstrated a higher average residue in the"~adult
group, 0.55 ng/cm as compared to 0.46 ng/cm^ of the juveniles.
All gauze square samples representing various body locations contained
quantifiable malathion residues except for one juvenile chest sample and four
adult back samples. Results of the analyses indicate juveniles, on the average,
had slightly higher exposure to their forearms (.32 ng/cm2) and backs (.37
ng/cm2) than was experienced by the adults (.26 and .22 ng/cm2). The adults
were slightly higher for their chest and shoulders: .26 and .27 as compared
to the juvenile averages of .15 and .24 ng/cm2.
20
-------
Table 6
Malathion Results-Juvenile Participants
Dermal and Respiratory Exposure Assessment of Adult and Juvenile Blueberry
Harvesters to Ethyl Parathlon, Malathion and Benomyl-Duplin County, North Carolina 1982
Participant
I.D.
No.
1
2
8
9
14
15
16
17
18
19
X
SD
COTTON
GLOVES
(ng)
2,000
1,550
772
1,310
1,740
1,740
870
2,720
5,300
571
1,857
1,368
GAUZE SQUARES (ng/cm2)
Glove*
0.82
0.70
0.32
0.38
0.33
0.32
0.32
0.44
0.63
0.36
0.46
0.19
Forearms
0.42
0.18
0.24
0.17
0.18
0.24
0.36
0.24
0.18
0.95
0.32
0.24
Chest
0.26
0.19
0.13
ND
0.15
0.20
0.10
0.14
0.14
0.19
0.15
0.07
Shoulders
0.27
0.27
0.19
0.26
0.19
0.26
0.24
0.30
0.12
0.29
0.24
0.05
Back
0.48
0.32
0.36
0.54
0.26
0.26
0.26
0.39
0.39
0.48
0.37
0.10
PERSONAL
(na/m3)
52.5
35.0
ND
ND
ND
ND
ND
ND
ND
ND
' 8.8
18.9
URINE (ppb)
DMTP
HD2
ND
91.4
116.1
14.7
120.6
162.8
42.2
ND
36.2
58.4
59.7
DMP
31.8
ND
57. L,
50.0
28.6
68.1
80.5
49.5
ND
37.1
40.3
26.5
DMDTP
ND
ND
72.2
51.6
22.3
99.1
109.0
29.7
ND
29.7
41.4
40.4
DMPTh
ND
ND
70.2
103.3
15.0
58.5
134.6
35.1
ND
20.7
43.7
47.0
1 23
Lower Limit of Detection: Gloves-500.ng/palr, Gauze-O.lOng/cm , Personal Atr Sample-15.Ong/m and Urine • lO.Oppb
ND-None Detected
-------
1
Table 7
Halathion Results-Adult Participants'
Dermal and Respiratory Exposure Assessment of Adult and Juvenile Blueberry
Harvesters to Ethyl Parathion, Malathion and Benomyl-Duplln County, North Carolina 1982
Participant
I.D.
No.
3
4
5
6
7
10
11
12
13
20
X
SD
COTTON
GLOVES
(ng)
888
1,120
1,390
888
888
656
18,000
1,300
2,170
5,160
3,246
5,350
GAUZE SQUARES (ng/cm2)
Gloves
0.43
0.52
0.60
0.69
0.37
0.38
0.65
0,23
0.86
0.79
0.55
0.20
Forearms
0.24
0.31
0.28
0.18
0.27
0.11
0.39
0.32
0.26
0.24
0.26
0.08
Chest
0.19
0.26
0.32
0.26
0.33
0.19
0.31
0.20
0.26
0.24
0.26
0.05
Shoulders
0.27
0.26
0.39
0.39
0.19
0.19
0.26
0.26
0.19
0.29
0.27
0.07
Back
m.2
0.32
0.48
ND
ND
ND
0.26
0.39
0.39
0.36
0.22
0.20
PERSONAL
fnt/m3)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
„
--
URINE (ppb)
DMTP
ND
40.6
36.3
159.6
ND
ND
ND
29.4
39.2
18.1
32.3
48.0
—
DMP
ND ,
60.0
50.0
78.6
ND
ND
ND
45.7
45.7
31.0
31.1
29.3
DHDTP
ND
57.8
51.6
113.5
ND
ND
ND
22.3
29.7
39.6
31.5
36.4
DMPTh
ND
29.5
42.1
140.4
ND
ND
ND
10.3
30.1
17.6
1
27.0
42.7
1 23
Lower Limit of Detection: Gloves-500.ng/pair, Gauze-0.lOng/cm , Personal Air Sample-lS.Ong/m and Urine-lO.Oppb
ND-None Detected
00
-------
329
It is difficult to compare the glove residues to the gauze squares
representing various body regions because the results of the two media are
expressed in different units. Davis (1980) reported the surface area of
the hands-to be 82*0 cm . Since the adult and juvenile participants wore
the same size gloves, this figure has been used to adjust the average
glove residue results to units of square centimeters. Therefore, the
dermal exposure to the hands of the juveniles averaged 2.6 ng/on* and
the adults averaged 3.9 ng/cm .
Eighteen of the twenty personal air samples were found to have no
detectable malathion residues. The two positive samples (52.5 and 35.0
ng/m ) were from the juvenile group and approached the lower limit of
detection (15.0 ng/m ).
Absorption and excretion of malathion by the participants was confirmed
through the analyses of urine samples for malathion metabolites. Urine
samples were analyzed for four dialkyl phosphate residues: 1. dimethyl
thiophosphate (DMDTP), 2. dimethyl phosphate (BMP), 3. dimethyl dithiophos-
phate (DMDTP) and dimethyl phosphorothioalate (DMPTh). Two juveniles and
four adults had no quantifiable residues in their urine samples. For each
of the four metabolites, the juveniles were found to have higher average
concentrations than the adults. This ranged from 9.2 ppb more for DMP to
26.1 ppb for DMTP.
Participant Exposure to Benomyl
Tables 8 and 9 list the results of benomyl residues recovered from the
juvenile and adult participant sampling media.
All cotton glove samples contained benomyl residues. The juveniles
averaged 348,000 ng per pair of gloves while the adult average was 1% higher
at 352,000 ng. When converted to hand surface area as was demonstrated with
2
the malathion residues, these figures would equate to 424 and 429 ng/cm .
23
-------
1
Table 8
Benomyl Results - Juvenile Participants'
Dermal and Respiratory Exposure Assessment of Adult and Juvenile Blueberry
Harvesters to Ethyl Parathion, Malathion and Benomyl-Duplin County, North Carolina 1982
Participant
I.D.
No.
1
2
8
9
H
15
16
17
18
19
X
SD
Cotton
Gloves .
(ng)
787,000
203,000
527,000
291,000
241,000
297,000
213,000
300,000
393,000
227,000
348,000
183,000
GAUZE SQUARES (ng/cm2)
Gloves
14.3
18.1
92.6
44.7
28.5
31.8
15.5
10.6
26.3
25.4
30.8
23.9
Forearms
11.1
ND2
ti
it
6.6
8.2
ND
H
M
II
2.6
4.3
Chest
16.1
10.6
5.7
ND
7.3
13.1
ND
5.0
ND
8.4
6.6
5.6
Shoulders
8.5
8.5
ND
6.0
ND
12.4
6.5
31.4
ND
n
7.3
9.6
Back
ND
n
8.5
ND
14.6
8.8
ND
9.9
ND
ND
4.2
5.6
Personal
Air
Sample
ND
n
n
n
ii
n
M
M
n
ii
—
—
URINE (ppb)
KBC
ND
NS3
ND
n
ii
24.3
ND
9.2
ND
14.5
5.3
8.9
5-OH MBC
ND
NS
23.5
ND
17.9
63.4
95.0
24.9
34.0
30.6
32.1
30.3
" 3°
" 5'° n
' Personal Alr
1.2
ND - None Detected
I IV. - HII r.nmtili'
o
and Urine -
-------
table 9
flenomyl Results - Adult Participants*
Dermal and Respiratory Exposure Assessment of Adult and Juvenile Blueberry
Harvesters to Ethyl Parathion, Malathion and Benomyl-Duplln County, North Carolina 1982
Participant
I.D.
Mo.
3
4
5
6
7
10
11
12
13
20
X
SD
Cotton
Cloves
(ng)
647,000
273,000
264,000
386,000
429,000
327,000
276,000
437,000
294,000
191,000
352,000
130,000
GAUZE SQUARES (ng/cm2)
Gloves
107.8
51.4
49.4
66.3
66.0
43.7
66.7
45.5
95.2
20.9
61.3
25.4
Forearms
49.0
13.8
15.1
43.2
19.5
8.7
ND
13.0
43.3
ND
20.6
18.1
Chest
8.7
12.2
7.6
5.4
28.1
5.8
ND
6.1
7.8
ND
8.2
7.9
Shoulders
ND 2
it
11.7
9.9
5.5
ND
it
ii
ii
6.2
3.3
4.6
Back
ND
H
II
II
21.8
ND
11.4
6.8
ND
ND
4.0
7.4
Personal
Air
Sample
ND
H
H
H
H
H
H
ii
H
H
—
URINE (ppb)
KBC
ND
5.5
ND
NS
ND
ii
u
H
J0.7
ND
1.8
3.8
5-OH MBC
31.0
" 'ND
58.0
NS
ND
n
ii
44.8
28.1
ND
18.0
22.9
Lower Limit of Detection: Gloves - 30 ug/pair. Gauze - 5.0 ng/cm2, Personal Air Sample "1.2 ug/m^ and Urine
o 5 ppb MBC and 10 ppb 5-OH MBC
ND -None Detected
-------
332
The adults also were found to have higher benomyl residues in the gauze
2
squares attached to the back of the gloves with an average of 61..3 ng/cm
2
as compared to the juveniles' 30.8 ng/cm .
Results of the gauze square analyses for the four body locations
indicate the juveniles had slightly higher average benomyl residues than
the adults for two of the locations: shoulders and back.
2
Respectively, these levels were 4.0 and 0.2 ng/on greater than the
corresponding adult average residues. Benomyl residues recovered from
2
the adult forearm and chest samples averaged 20.6 and 8.2 ng/cm which were
18.0 and 1.6 ng/cm higher than the level observed in the juveniles.
None of the adult or juvenile personal air samples were found to
contain benomyl residues. The lower limit of detection for these samples
/ 3
was 1.2 ug/m .
Absorption and excretion of benomyl by the participants was confirmed
through the analyses of urine samples for benomyl metabolites. The urine
samples were analyzed for two residues: carbendazim (MBC) and 5-OH MBC.
Two juveniles and four adults had no detectable levels of either metabolite
in their samples. Three of the adults, participants 7, 10, and 11, were
also the same participants who had no malathion metabolites in their urine "
samples. Results of the analyses for benomyl urinary..metabolites demonstrated
the juveniles again had higher average concentrations than the adults. The
average MBC level in the juveniles was 3.5 ppb greater than the adult average
while the 5-OH MBC concentration was 14.1 ppb higher.
Statistical Analyses of Participant Exposure
Statistical analyses (t-test) comparing the malathion and benomyl
residues recovered from the juvenile and adult sample media are reported in
Table 10. Significant differences between the two groups of study for
malathion exposure were observed in the gauze square locations for the
chest (P< .01) and back (P< .05-). The P-values are two sided. The adult
26
-------
333
Table 10
Statistical Analyses (t-test) of Juvenile vs.
Adult Sample Media for Malathion and Benomyl
Sample Media
Cotton Gloves
Gauze Squares
Gloves
Forearms
Chest
Shoulders
Back
Personal Air Samples
Urinary Metabolites:
DMTP
DMP
DMDTP
DMPTh
Malathion
NS
tlg- -3.857(P<.01)*
NS
t. - 2.195(P<.05)*
io
NS
NS MBC NS
" 5-OH MBC "
Benomyl
NS
t - -2.764(P<.02)*
lo
tl8- -3.049(P<.01)*
NS
NS - No Significance, (all P values were > .20)
*Statistically Significant at P<0.05
27
-------
334
trend was toward significantly higher malathion residues in their chest
gauze samples while the juveniles tended to have significantly higher
concentrations in their back gauze square samples. No significant
differences in malathion exposure between the juveniles and adults were
observed in the cotton gloves, personal ait samples, glove, forearm and
shoulder gauze and urinary metabolites.
Two significant differences, forearm gauze (P< .01) and glove gauze
( P< .02), were observed between the benomyl exposure patterns of the'adults
and juveniles. In both cases, the trend of significantly higher residues
vas observed in the adults. No other statistical differences were found
In the benomyl exposure measurements.
Environmental Results
Ethyl parathion, malathion and benomyl residues recovered from the
blueberry* foliage and soil composite samples are reported in Table 11•
Only malathion residues were found on the foliage samples. Both malathion
and benomyl were detected on the blueberries. All three pesticides were
observed in the soil.
Although no detectable levels of parathion were observed on the blue-
berries and foliage, an average concentration of 0.03 ppm was seen in the
soil. However, only five of the ten samples contained parathion residues
and the levels observed were at the lower limit of detection (0.02 ppm).
Five blueberry samples, seven foliage samples and seven soil samples
were found to have quantifiable malathion residues which respectively
averaged 2.31 ng/cm2, 0.30 ng/cm2 ana- Q.22 ppm. As seen with the parathion
soil analyses, the reported malathion residues for each substrate also
approached or were at the lower limit of detection.
28
-------
Dermal and Respiratory Exposure Assessment of Adult
and Juvenile Blueberry Harvesters to Ethyl Parathlon, Malathion
and Benomyl-Duplin County, North Carolina 1982
Composite
Sample
No.
1
2
3
4
5
6
7
8
9
10
X
SD
Bl
Parathion
ND*
II
II
II
II
II
II
II
II
II
.ueberriesl
ng/cm2)
Malathion
2.82
4.26
5.79
ND
M
it
ii
2.84
7.37
ND
2.31
2.76
Be no my 1
41.2
33.3
33.6
28.6
25.7
63.1
29.0
99.7
34.0
32.8
42.1
22.8
Foliage2
(ng/cm2)
Parathion
ND
ii •
ii
ii
M
ii
ii
n
ii
n
—
—
Malathion
0.41
0.45
ND
0.51
0.43
ND
0.38
0.36
ND
0.48
0.30
0.21
Benomyl
ND
n
M
n
n
n
M
n
n
n
—
—
Soil3
(ppm)
Parathion
0.04
ND
ND
0.04
0.14
0.02
ND
0.07
ND
ND
0.03
0.05
Malathion
0.08
0.12
ND
ND
0.32
ND
0.09
0.20
0.39
0.95
0.22
0.29
Benomyl
0.15
0.12
0.26
0.34
0.17
6.25
0.23
0.34
0.35
0.52
0.27
0.12
I/ 2
— Analysis was by surface extraction, lower limit of detection: Ethyl Parathion -1.6 ng/cm , Malathion -
2.50 ng/cm2, Benomyl • 5 ng/cm2
2/ 2
— Analysis was by surface extraction, lower limit of detection: Ethyl Parathion - 0.18 ng/cm , Malathion -
0.30 ng/cm2, Benomyl - 5 ng/cm
— Lower Limit of Detection: Ethyl Parathion » 0.02 ppra, Malathion - 0.04 ppm, Benomyl « 0.1 ppm
4/ ND - None Detected
UV
-------
All blueberry and soil samples collected for benomyl analyses contained
quantifiable levels of this chemical. An average benonyl concentration of -77,
42.1 ng/cn2 was observed on the blueberries which was twenty times higher
than the average malathion residue. Although no quantifiable benomyl residues
were observed on the foliage, it is reasonable to assume that residues were
present, but were at levels below the lower limit of detection
(5 ng/cm2). Approximately, only 10% of the malathion concentration observed
on the blueberries was found on the leaves. Assuming the relationship
between benomyl residues on blueberries and foliage would be the same as
malathion, then benomyl foliage residues would be expected to average 4-5
ng/cm2. The average benomyl soil residue (0.27 ppm) was found to be the
highest soil level among the three pesticides of study.
Results of the high volume air sampling are listed in Table 12 .
Quantifiable residues of the three pesticides were recovered from the sample
media. Average concentrations reported for malathion (.253 ug/ia^) and
benomyl (.267 ug/m ) were found to be less than 15Z of the ethyl parathion
average of 1.79 ug/m .
The relatively high level of parathion in the high volume air samples,
as compared to benomyl and malathion is explained by drift from an ethyl
parathion application to the blueberry fields of an adjacent farm which was
located to the southwest and within a quarter mile of the blueberry field
of study. The application occurred immediately prior to or during the parti-
cipant and environmental monitoring. This was determined by the onsite
investigations, who observed the posted warning signs around the treated
fields, as they left the study farm after sampling was completed. The signs
were not in place when the investigators arrived on site early that morning.
30
-------
Table 12 337
1
High Volume Air Sample Results
Dermal and Respiratory Exposure Assessment of Adult
and Juvenile Blueberry Harvesters to Ethyl Parathion,
Malathion and Benomyl-Duplin County, North Carolina 1982
ug/m
Ethyl Parathion:
G.F. Filter
XAD-4 Resin
Total
X - 1.79 ug/m3
Malathion:
G.F. Filter
XAD-4 Resin
Total
X - .253 ug/m3
Benomyl:
G.F. Filter
XAD-4 Resin
Total
Sample #
ND2
2.05
2.05
.005
ND
.005
ND
.308
.308
1 Sample # 2
ND
1.52
1.52
.004
.497
.501
ND
.226
.226
X - .267 ug/m
— Lower Limits of Detection: ethyl parathion » 0.5 ng/m3,
malathion « 0.5 ng/m3 and benomyl • 0.1 ug/m3
2/
— ND - None Detected
31
-------
Weather observations during sampling were as follows:
77Q
Wind - West and Southwest JJ°
Windspeed - 4 to 7 mph
Barometric Pressure - 29.98
Temperature - 758F
Relative Humidity - 86Z
Cloud Cover - 20 to 30 %
Rain- 0
32
-------
339
VII. piscussion;
Results of the environmental analyses confirmed the participants of study had
potential exposure to ethyl parathion, malathion and benomyl which were respectively
sprayed 22, 15 and 21 Says prior to monitoring. Statistical analysis of the dermal
and respiratory exposure results demonstrated four significant differences between
the exposure patterns of the adult and juvenile participants:
1. No differences in exposure to ethyl parathion were observed since
the sampling media of the participants was uniformly negative (except
for two juvenile and one adult glove samples).
2. Two statistical differences in the exposure patterns to malathion
vere observed. Juveniles were found to have higher average residue
in the back gauze square samples and the adults demonstrated higher
average residues in the chest gauze square samples.
3. Two significant differences were seen in the benomyl exposure patterns
(glove gauze and forearm gauze) and in both cases the trend of higher
average residues was observed in the adults.
Thus, three of the four significant differences identified between the exposure
patterns of the adult and juvenile participants are attributed to the trend of
higher average residues observed in the adult media.
Results of the participant exposure monitoring demonstrated the hands of the
workers were the primary sources of exposure and no statistical differences in
glove residues were found between the juvenile and adult participants. This
observation was not unexpected, since in nearly all studies of occupational
exposure to pesticides, approximately 90% of the dermal exposure is found in the
hands, Davis (1980). It is the hands which have the most contact with pesticide
surface residues remaining on the blueberries and leaves. Wicker and Guthrie
(1930) employed the industrial technique of time and motion studies to determine
standardized times of exposure for anatomic regions of workers during the harvest
33
-------
340
of a variety of crops. Blueberry pickers were filmed at 5 consecutive 3.5 minute
intervals for a total of 17.5 minutes. Analysis of the film found the right and
left hand were in contact with the fruit and foliage for an average of 16.2 (92%)
and 16.3 (93%) minutes respectively. Right and left arm contact accounted for
3.5 (20%) and 4.9 (28%) minutes while the trunk of the body was in contact for
only 1.1 (6%) minutes.
Absorption and excretion of malathion and benomyl by the participants was
demonstrated. Although there were no statistical differences between the juveniles
and adults for urinary metabolites, the juveniles were found to have higher
average residues for the four alkyl phosphate metabolites and for MBC and 5-OH MBC.
Two explanations for the trend of higher juvenile urinary metabolites are available.
First, the juveniles, as estimated by the three \ Investigators, were thought to
have a slightly higher rate of blueberry consumption than the adults (1^ to 1%
cups as compared to one cup). This alone may explain the trend since no major
differences were observed in the respiratory and dermal (especially the hands)
exposure pattern between the adults and juveniles. Another contributory explana-
tion is that children tend to have higher metabolic rates than adults for various
compounds (Rane, 1976). Thus, it might be anticipated that juveniles would
metabolize and excrete malathion more quickly than adults when both groups
experienced similar exposure doses.
-------
341
VIII. Tleferer.c&s:
Davis, J.E. Minimizing Occupational Exposure to Pesticides:
Personal Monitoring. Res. Rev. 75; 33-50 (1980).
Rane, A. and J.T. Wilson. Clinical P'.iarnacokinetics in
Infants and Children. Clin, Paarmaco. 1: 2-24 (1976).
Wicker, G.W. and F.E. Guthrie. Worker-Crop Contact Analyses
as a ceans of Evaluating Reentry Hazards. Bull. Environ.
Contaa. Toxicol. 24 (1): 161-167 (1980).
-------
342
Youth In Agriculture: Dermal and Respiratory
Exposure Assessment of Juvenile Potato
Harvesters, Aroonstock County, Maine
Research performed by
Medical University of South Carolina
August 11, 1982
-------
343
Table of Contents
Abstract 11
Objective 1
Background 1
Methods 4
Results 12
Discussion 17
Conclusions 24
References 26
Appendices
A - Approved Pesticides for Maine Potatoes, 1981
B - Cinoseb Analytical Methodologies
C - Quality Assurance Plan and Results
-1-
-------
ABSTRACT
344
Ten male juveniles, ages 10-17, were monitored on two consecutive
days for their dermal and respiratory exposure to dlnoseb during the hand
harvest of potatoes. Environmental sampling documented small but measureable
levels of dlnoseb 1n the soil and ambient air of the fields of study. Results
of the participant monitoring showed that respiratory exposure contributed
little toward total exposure while the hands accounted for almost all of the
dermal exposure. No detectable levels of dlnoseb were observed 1n the parti-
cipants' urine'samples following exposure. Estimates of dermal toxic doses for
each of the ten participants revealed that on the average, they received .0001*
of the toxic dosage per hour of exposure. Data presented 1n this study suggest
that juvenile workers are not. being unduly exposed to dlnoseb during harvest.
-11-
-------
345
Assessment of Dermal and Respiratory Exposure of Juvenile Potato
Harvesters to Dinoseb - Aroostock County, Maine 1981
OBJECTIVE:
The original objective of this study was to assess the difference, 1f
any, between the exposure patterns of adult and juvenile harvesters to potato
fields treated with dlnoseb. The objective was modified during the field phase
of the study because a mixed crew of adult and juvenile workers could not be
located. This contingency was anticipated and the study protocol permitted the
recruitment and monitoring of an all juvenile cohort. The purpose in monitoring'
an all juvenile cohort was to document and assess potential dermal and
respiratory exposure to dlnoseb during hand harvest operations.
BACKGROUND:
The U. S. Environmental Protection Agency and U. S. Department of Labor
finalized an interagency agreement on March 17, 1980. This agreement, "Youth 1n
Agriculture", provides for the development of pesticide protection programs for
farm workers. One goal 1s the determination of scientifically based reentry
Intervals for children and the assessment of potential health effects of pesticides
on children working in agriculture. The agreement assumes that the potential for
the exposure of children to toxic chemicals in agriculture is widespread and that
children are generally more sensitive to chemical exposure. Furthermore, children
possibly have greater rates of dermal and/or gastrointestinal uptake and have
decreased capacity for detoxification. Yet, little or no data exist to support
these assumptions as they apply to field workers. In order to bridge this data
gap, it is necessary to conduct studies which measure the pesticide exposure of
adult and juvenile workers to various pesticides during the harvest of a variety
of hand-picked crops.
-1-
-------
346
Juvenile Potato Harvesters - Juveniles (10-17 years of age) are commonly
employed as stoop laborers during Maine's potato harvest. Although
mechanical harvesters are slowly replacing the hand-picking crews, those
potatoes grown for seed will continue to require harvesting by hand
in order to avoid bruising which is found on mechanically harvested
potatoes. Aroostock County, located in northeast Maine, is the state's
predominant potato region,and children comprise the majority of labor
for hand-picking operations. Harvest begins 1n mid-September and is
usually completed during the first week of October. School is recessed,
for "spud vacation", for approximately three weeks to accommodate the
employment of children. Few adults (>18 years old) work as pickers
because their age alone qualifies them for higher pay positions such as
drivers and equipment operators. Also, the adult labor supply available
for employment is low and migrant workers are not commonly employed.
A child must be at least 10 years old to work in the fields
and those juveniles 10 to 13 years of age must have written parental
consent. All workers on moving equipment must be 18 years old. The
work day begins around 6:30 a.m. and ends in late afternoon round 5:00
p.m. A 30-minute lunch break is taken at midday. All workers are
placed 1n line along the first potato row to be picked. Each worker
1s assigned a section of the row to harvest and he maintains the
corresponding section across all the rows of the field. The length of
each section is determined by the speed and efficiency of the picker.
A tractor pulled mechanical digger 1s used to scoop up two rows of
potatoes at a time onto a conveyor belt of steel rods. As the digger
moves along, soil and small stones fall through the gaps between the
rods while the potatoes, larger stones and vines drop from the end of
the conveyor to the ground.
-2-
-------
347
The worker then removes the vines from his section to facilitate picking.
The potatoes are gathered from the ground and placed in a split ash
wicker basket .25 to .5 bushel 1n. size. When the basket 1s full, the
potatoes are then deposited Into a large wooden barrel which 1s appro-
ximately the size of a 55 gallon drum. Each picker fills his own
barrels which he identifies with numbered tickets. The worker is paid
50 cents per barrel and usually averages between 20 to 35 barrels per
day. As the worker finishes picking his section, the digger has made
another pass and two more potato rows are ready for harvest. A flat
bed truck mounted with a hoist Is used to pick up the filled barrels
each containing about 165 pounds of potatoes.
•
Potato Pesticide Usage - The University of Maine's Cooperative
Extension Service recommends approximately 20 Insecticides,-10 herbicides
and 6 fungicides for use on potatoes prior to and throughout the growing
season (Appendix A). Many of the Insecticides have pre-harvest applica-
tion restrictions ranging from 14 to 75 days, while other insecticides
are not recommended for use during cooler weather. Likewise, post-
emergent herbicides for late weeds and grasses have application restric-
tions of 45 to 60 days prior to harvest. Recommended fungicides have
no such restrictions and may be applied weekly throughout the season.
Generally, the last pesticide application to potato fields 1s either
a defoliant or deslccant applied for vine control 14 to 21 days prior
to harvest. Dow General Weed Killer commonly known as DN8P or dinoseb
(2-sec-butyl-4,6 dinltrophenol) is overwhelmingly the deslccant of
choice. An estimated 138,561 gallons of DNBP were sold in Aroostock
County during 1977 (Powell, 1979). Dinoseb was selected for monitoring
in this study because of Its vast and heavy usage in Aroostock County
-3-
-------
348
and because it Is usually the last pesticide applied prior to harvest.
Dow General Weed Killer' is the phenolic form of DNBP,
introduced by the Dow Chemical Company in 1940. The phenolic form is
most frequently used as a contact herbicide and for killing potato
vines and desiccating seed crops to facilitate harvest, DNBP is a
moderately to highly toxic herbicide with oral LDgo of 20 me/kg for
mice and guinea pigs, 25 mg/kg for rats, and 40 mg/kg for chickens
(NIOSH, 1977). Dinoseb is also absorbed through the skin, dermal
LD50 ranging from 80 mg/kg for rats and rabbits to 500 mg/kg for
guinea pigs (NIOSH, 1977). Yellow staining of the skin and clothing
usually occurs after contact.
METHODS:
Site - The cooperation of a seed potato fanner was secured through
the assistance of the Area Potato Specialist, University of Main Cooperative
Extension Service. The farmer employed approximately 40 children to hand-pick
his crop of Katahdin potatoes, the harvest commencing on September 16, 1981.
•
The last pesticide applications to his potato fields occurred on August 20 and
6)
28. This was a "split" application of Dow General Weed Killer0'(EPA Reg. No.
464-98-AA) which 1s an emulsifiable concentrate containing 55% dinoseb and 45%
Inert ingredients. The application rate per acre for each application was 2
quarts of the product mixed with 5 gallons of diesel oil and approximately 20
gallons of water. No further chemical applications were made to his crop prior
to harvest. Two of his fields identified herein as the "east field" and the
"west field", each 8 acres in size, were selected for participant and environ-
mental monitoring (see Figure 1).
-4-
-------
^ 1,200'
Forest
Figure 1
Monitoring Sites - September 16 & 17, 1981 - Aroostock County, Maine
House
Barn
I Shed
Shed
I Shed I
Hi Vol Air>
Samplers
9-17-81
West Field
(8 acres)
I
Rows
1
•<•* 350'
N
East Field
(8 acres)
t
Rows
I
Hi Vol Air]
Samplers
9-16-81
Forest
iU
-------
350
Participants - Ten white male juveniles, ages 10 to 17, were recruited
for participation in the study (Table 1). Each participant signed a voluntary
informed consent agreement which was also consigned by a parent. The ten parti-
cipants were monitored for 2 hours on September 16 while harvesting the east
field and again for 2 hours on September 17 while harvesting the west field. The
monitoring design was intended to produce two replicate sets of data based upon
sampling conducted under identical conditions. Monitoring was conducted for
only 2 hours each day in order to avoid gross contamination of the monitoring
media by the dust and soil of the fields.
Assessment of Dermal Exposure - Affixed to each participant's clothing
were six 2"x 2"-eight ply gauze squares (acetone extracted) with glassine backing:
one on each forearm, thigh and calf. The purpose of the gauze squares was to
trap dislodgeable dinoseb residues released from the soil as a result of the
harvest equipment operations and the workers' physical activity in the field.
'The glassine backing prohibited gauze contamination from skin oils, perspiration
or existing clothing contamination. The gauze squares were removed from each
participant at the completion of his monitoring period. The six gauze squares
• .
were then pooled into 3 samples (forearm, thigh and calf), wrapped in aluminum
foil, and frozen prior to analyses.
- Residue translocated to the workers' hands was assessed through the
analyses of white 100% cotton gloves worn by the participants during their expo-
sure monitoring periods. Affixed to the back of each glove was a 2" x 2"- eight
^v *
ply gauze pad with glassine backing. It was anticipated that the gauze pads would
avoid much of the glove contamination expected from moisture, dirt, skin oils,
etc. The gloves were laundered, rinsed in distilled water and extracted with
acetone prior to use. At the request of the participants, they were given the
option of wearing the cotton gloves either in place of or underneath their work
gloves. At the completion of monitoring, the participants' gloves were removed,
wrapped In aluminum foil and frozen.
-------
Table 1
Assessment of Dermal and Respiratory Exposure of Juvenile Potato
Harvesters to*Dinoseb - Aroostock County, Maine 1981
Participant
1.
2.
3.
4.
5.
6.
Age
10
14
17
11
13
14
Sex
M
M
M
M
N
M
Race
C
C
C
C
C
C
Height
(Inches)
50
60
69
60
67
66
Weight
(pounds)
65
i
90
110
60
120
no
Work Clothing
9-16-81
Denim Jeans, short
sleeve shirt, leather
shoes & cotton work
gloves .
Denim Jeans, long
sleeve shirt, leather
shoes & cotton work
gloves.
Denim jeans, short
sleeve shirt, tennis
shoes & cotton work
gloves .
Denim Jeans, sweat-
shirt, tennis shoes
6 cotton work gloves.
Denim Jeans, short
sleeve shirt, leather
boo to, baseball cap
and cotton work p.lovc
Denim Jeans, short
sleeve shirt, tennis
shoes and cotton
work gloves.
9-17-81
Same as 9-16
Corduroy pants,
sweatshirt, leather
shoes & cotton work
gloves .
Corduroy pants,
short sleeve shirt,
tennis shoes and
cotton work gloves.
Denim Jeans, sweat-
shirt, leather boot
and cotton work
gloves.
Same as 9-16
i»
Denim Jeans, sweat-
shirt,, tennis shoes
and cotton work
gloves .
Remarks
Participants 1,2 and
3 are brothers*
At the end of work
day 9-16-81, he had
developed irritation
of the eyes; reddenit
of the sclera and li<
tearing and swelling
On 9-16, he wore the
dermal exposure glov<
with gauze pads facii
palms.
On 9-16, his persona!
i air ssmpler was remo-
ved after 45 minutes
and placed on ground
next to him while he
worked.
Lr4
Ul
-------
Table i (Cont'd.)
Participant
7.
8.
9.
10.
Age
IS
12
13
11
Sex
H
M
M
N
Race
C
C
C
C
Height
(inches)
35
55
53
50
Weight
(pounds)
w
100
100
00
Work Cl
9-16-81
Denia jesns, long
sleeve shirt, lea the
boots 4 cotton work
gloves.
Denitt jeans , short
sleeve shirt, tennis
shoes, bssebell csp
t cotton work gloves
Denia jesns, long
sleeve shirt, leethe
boots, bssebsll csp,
6 cotton work gloves
Denia Jesns, short
sleeve shirt, lesthe
boots, bssebsll csp,
& cotton work gloves
3 thin*
9-17-81
SSM ss 9-16
,
SSM ss 9-16
SSM M 9-16
8«sii M 9-16
Resmrks
-
-
Brother of psrticif
1A "
1U.
Personal sir sanple
•slfunctloned on
9-16*
I
oo
LM
Ul
r\)
-------
353
The gauze pads attached to each pair of gloves were removed, pooled and stored
separately for subsequent analyses.
Assessment of Respiratory Exposure - Available to the Investigators
*
were four DuPont P-4,000 personal air samplers and four MSA personal air samplers.
All were p recall bra ted at 2liter$/m1nute. The sampling medium consisted of a
37 mm cassette with a Millipore glass fiber filter (.3 micron pore size). Start
and stop time for each participant's monitoring were recorded for subsequent air
volume calculations. The flow control light-emitting diodes of the samplers
were monitored to Insure that proper flow had been maintained. At the completion
of air sampling, the glass fiber filters were wrapped 1n aluminum foil and frozen
prior to analysis.
High volume air samples were also collected at each field during the
2 days of study. Two Midwest Research Institute liquid 1mp1nger air samplers
were used and were placed side by side in a an Indented comer of each field
during the respective monitoring periods (Figures 1). The purpose for placing
the high volume air samplers next to each other was to obtain duplicate readings
and to have one Instrument serve as a back-up 1n case of a mechanical failure.
• r
The air samplers were precallbrated with sampler II drawing 32.3 liters/minute
and sampler 12 drawing 32.0 1 Hers/minute. Entrapment medium for each air sample
consisted of approximately 100 mllHHters of pre-extracted 0.1 normal sodium
hydroxide. After the completion of air sampling, the samples were transferred
to acetone rinsed glass bottles and frozen prior to analyses.
On both monitoring days, an MSA personal air sampler (2 1/m) employing
0.12 normal sodium hydroxide in a mini-impinger was placed in the field. The
purpose of this experiment was to compare capture efficiency of the sodium hydro-
xide to the glass fiber filters of the personal air samplers worn by the participants
-9-
-------
Assessment of Absorption - Potential absorption of dlnoseb by the
participants was assessed through residue analyses of urine samples. Each parti-
cipant provided a pre-exposure and post-monitoring urine samples. The post-
monitoring samples were the first morning voids and were collected on September
17 and 18. Samples were collected 1n' polyethylene bottles which had been p re rinsed
with acetone. Samples were frozen prior to analyses. It Is noted that plasma,
not urine, 1s. the biological sample of choice for monitoring exposure to dlnoseb
(Idaho PHAP Annual Report, 1981), however, obtaining blood samples from the
juvenile'participants was thought to be Inadvisable.
Soil Residue - Three composite soil samples were collected from the
east field on September 16 and three from the west field on September 17. The
three rows equidistant from each other across the width of each potato field
were selected as sampling points. At each sampling point, no less than 10 grams
of soil were collected from the.row at five sampling segments equidistant from each
other along the entire length of th« row* Thus, a minimum of 50 gut of so1T were
collected for each composite sample* Samples were collected from the top Inch
of soil using a stainless steel scoop and placed 1n an amber colored glass jar
••
prerlnsed with, acetone. L1ds were lined with aluminum foil and samples were
\
frozen prior to analyses. At the time of analysis* each sample was well mixed
and a 50 gm (wet weight) subsample was allquoted for residue determination.
In addition to the soil samples, two standing water samples were collect-
ed from the west field on September 17. Runoff from a light rain of September
14 had been trapped 1n several locations between the potato rows of the west
field. No standing water was observed 1n the east field on September 16, although
the soil was noticeably damp 1n ground depressions. The standing water was a vivid
bright yellow 1n color. This visual observation strongly suggested the presence
-10-
-------
355
of dinoseb In the fields.
Meteorological Data - The following observations were made during the
two monitoring periods: 1) maximum temperature, 2) relative humidity, 3) baro-
metric pressure, 4) wind speed, direction and condition, 5) percent cloud cover
and, 6) soil temperature.
Dinoseb Residue Analyses - The Maine Public Health Laboratory performed
the analyses of all samples collected 1n this study.
Analyses of all sample extracts were conducted on a Hewlett Packard
Model 5880 A Gas Chromatograph equipped with a dual column, dual 63 N1 Electron.
Capture Detector oven and a dual Integrator printout recording system. Quali-
tative and quantitative analyses were carried out on Column I with all extracts
being relnjected simultaneously onto Column II for second column confirmation
of the presence or absence of dinoseb.
Gas chromatographic columns used 1n the analysis were:
Column I: 4 mm ID x 6 mm 00 x 6 ft (183 cm). Glass packed with 10%
DC - 200 coated on gas chrom Q (100/120 mesh). Carrier
gas flow rate set at 120 ml/m1n.
Column II: 4 mm ID x 6 mm OD x 6 ft (183 cm). Glass packed with 1.5%
0V - 17/1.95% QF-1 coated on gas chrom Q (100/120 mesh).
Carrier gas flow rate set at 60 ml/m1n.
Other GLC parameters were as follows:
Oven temp « 196°C; Injection port temp - 220°C; EC detector temp « 300°;
chart speed • 0.50 cm/m1n; Integrator attenuation 2 x 108; Carrier gas,
5% methane in Argon (electron capture grade).
Quantitative analysis was performed by averaging duplicate 5 micro!iter
injections of each sample and comparing peak height of the sample to that of
an analytical standard whose peak height was +. 25% of the sample. Electron
-11-
-------
356
capture response of the detector was shown to be linear over a range of 1 to
10 nanograms of dinoseb methyl ether derivative with a one Inch (2.54 on) peak
detector response equal ..to -one nanogram of dlnoseb methyl ether.
Appendix B provides the details of the analytical methodologies by
substrate followed 1n the analyses of the samples collected 1n this stucjy.
Quality Assurance - The Quality Assurance (QA) plan and results a
reported In Appendix C.
R£SULTSr
Table 2 lists the results of the participant monitoring for the two
1 *
days of study. The ten participants'were monitored for two hours each
day. Table 3 lists the results of the environmental monitoring of the
east and west fields.
DAY 1
£ach of the ten pairs of cotton gloves contained measureable levels
»
of dlnoseb residue ranging from 1.65 micrograms (jig) to 31.13 ug with a
group mean of 10.09.jig. Participants 9 and 10 wore the cotton gloves
underneath their work gloves throughout the monitoring period. No
detectable levels of dlnoseb were found 1n the gauze squares attached to
the back of the cotton gloves. Twenty-six of the 30 pairs 01* gauze
•
squares which were attached to the participants' forearms, tMghs and
calves had no detectable levels of dlnoseb residue. The four positive
gauze square samples (forearms, thighs and calves of participant 9 and
calves of participant 10) contained minimal levels of dlnoseb which
9
approached the lower limit of detection of 0.76 ng/cra. •• No dlnoseb was
recovered from the glass fiber filters of the personal air samples nor
were residues detected 1n the urine samples of September 16 and 17.
-12-
-------
357
The environmental samples of Day 1 demonstrated the presence of dinoseb
in the soil and ambient air of the field of study. All three soil samples
were positive for dinoseb with an average concentration of 952.0 parts
per billion (ppb). Both high volume air samples were also positive al-
though results approached the minimum level of detection of 4.5 ng/m .
Sample fl contained 43.25 ng/m3 while air sample #2, contained only half
as much dinoseb (20.37 ng/m3). No dinoseb residue was found in the MSA
raini-impinger air sample.
-13-
-------
Table 2
Assessment of Dermal and Respiratory Exposure of Juvenile
Potato Harvesters to Dinoseb - Aroostock County, Maine 1981
358
Results - Day 1 (9-16-81) Participant Monitoring:
Participant
I.D.
1
2
3
4
5
6
7
8
9
10
Cotton,
Gloves
(uo)
24.25
7.04
3.88
8.09
31.19
4.77
6.96
1.65
10.80*
2.32*
2 2
Gauze Squares (nq/cm )
Gloves
ND5
M
M
ii
H
M
II
II
II
II
Forearms
ND
ii
H
n
ii
ii
n
n
1.01
n
Thighs
ND
n
n
ii
n
u
n
n
4.94
ND
Cal ves
ND
n
u
n
H
n
n
n
1.60
2.30
Personal
Air 3
Sample
ND
n
n
n
ii
H
II
II
II
II
Urine*
Baseline
9-16-81
ND
n
n
u
u
u
II
II
II
II
9-17-8
ND
u
n
n
n
u
II
II
II
II
Results - Day 2 (9-17-81) Participant Monitoring:
1
* 2
3
4
5 -
6
7
8
9
10
1.32*
3.15*
ND*
2.90*
9.08*
3.03*
ND*
10.83
4.53*
0.77*
ND
"
«
«
3.31
ND
"
2.78
ND
M
ND
u
n
«
n
n
n
"
«
n
ND
NT6
ND
»
0.97
ND
»
0.97
14.86
1.70
ND
«
«
«
1.94
"
"
n
n
3.99
ND
u
n
n
u
u
n
n
n
M
9-18-81
ND
"
••
n
u
••
«
"
•'
11
Lower limit of detection
2
Lower limit of detection
Lower limit of detection
Lower limit of detection
5ND * None Detected
0.2 yg/pair; results adjusted for 87.35% average QA recover
2
.76 ng/cm ; results adjusted for 87.87% average QA recover
750 ng/nf
90.0 ppb
-14-
= Not Analyzed (sample lost)
Cotton gloves worn underneath work gloves
-------
359
Assessment of Dermal and Respiratory Exposure of Juvenile
Potato Harvesters to Dinoseb • Aroostock County, Maine 1981
Environmental Monitoring Dlnoseb Results
Soil (ppb)1:
Sample 1
Sample 2
Sample 3
* 2
A1r (ng/m3) :
High Volume 11
High Volume 12
MSA m1n1-1mp1nger
Standing Water (ppm) :
Sample 1
Sample 2
Day 1- East field Day 2 -
(9-16-81) (9-17-81]
955.0
988.0
912.0
43.25
20.37
ND
-
-
919.0
752.0
738.0
ND4
16.34
ND
4.13
2.51
Lower limit of detection * 4.5 ppb; results not adjusted as average QA
recovery » 101.IX
2H1gh Volume lower limit of detection »~4.5 ng/m3; results adjusted for 119.331
average QA recovery
H1n1-1mp1nger lower limit of detection « 750 ng/m3
Lower limit of detection * .001 ppm; results not adjusted as average QA recover
98.5%
*ND * None detected
-15-
-------
360
Meteorologic observations during Day 1 monitoring were as follows:
1. Maximum temperature- 65° F
2. Relative humidity- 771
3. Barometric pressure- 29.75
•
4. Wind speed & direction- 0
5. Percent cloud cover- 1001
6. Soil temperature 64° F
DAY 2
Eight of the ten pairs of cotton gloves contained quantifiable levels
of dlnoseb which averaged 3.56 ug for the group. All participants, except
18, wore the cotton gloves underneath their work gloves. Two pairs of the
gauze squares attached to the back of the gloves were also positive. No
detectable levels of dlnoseb were.'observed 1n the forearm gauze samples
worn by the participants. The thfgh and calf samples of pattctpants"5~
and 10 and thighs only of participants 8 and 9 contained small but measure-
able quantities of dlnoseb. No dlnoseb was recovered from the glass fiber
filters of the personal air samples nor from the urine samples of September 18.
All soil samples collected from the west field contained dlnoseb
residue which averaged 803.0 ppb. No dlnoseb was detected In the high volume
air sample fl or In the MSA nrtn1-1mp1nger although 16.34 ng/m was recovered
from high volume air sample f2. The results of the high volume air sampling
may be explained by the wind from the northeast, 0-5 miles per hour. Although
the wind was not constant, when blowing It would have carried the ambient air
of the west field away from the air samplers (Figure 1). The two standing
water samples collected from the west field were positive for dlnoseb and
contained 4.13 and 2.51 parts per million.
-16-
-------
361
Meteorologic observations during Day 2 monitoring were as follows:
1. Maximum temperature- 76° F
2. Relative humidity- 622
3. Barometric pressure- 25.90
4. Wind speed & direction- 0-5 mph from the NE
5. Percent cloud cover- 302
6. Soil temperature- 64° F
DISCUSSION
The environmental sampling results of the east and west fields docu-
mented the presence of dinoseb in the soil and ambient air during the two
days of study, thus there was the potential for worker-exposure. The
assessment of a worker's exposure to a particular pesticide irust Include
measurements of the dermal and respiratory levels to which he is exposed.
Results of these measurements (ie. gauze squares attached to v&risus body
locations, cotton gloves, personal air sample, etc.) may then be used to
calculate a worker's potential total exposure on a hourly basis as recommended
by Davis (1981). Data from participant 9's Day 1 monitoring will be used
to illustrate these calculations.
ASSESSMENT OF DERMAL EXPOSURE. The total hourly dermal exposure of a
i
worker 1s the sum of the hourly exposures for the worker's unprotected body
regions (ie.face, neck, forearms if wearing short sleeve shirt, etc.) plus
the hourly exposure of the hands. The gauze pads attached to workers during
monitoring 'are used to represent the unprotected regions of the worker's
body. The residue per unit area of the gauze squares selected to represent
an unprotected body area is then multiplied by the surface area of that
-17-
-------
362
body region. It is assumed that clothing, except for gloves, provides
1002 protection to the worker, thus calculations are made only for unpro-
tected body regions. In this study the face and neck (estimated surface
area of 910 on2) of all participants were unprotected as well as the
forearms of those who wore short sleeve shirts. The average residue per
cm2 recovered from each participant's forearm, thigh and calf gauze
squares will be used to calculate the estimated exposure of.the head and
neck. The forearms will not be Included 1n calculations because all
forearm gauze square samples were negative except for participant 19 on
the first day of monitoring who wore a long sleeve shirt. The following
example Illustrates the calculations to derive the total.hourly dermal
exposure to dlnoseb of participant 19 from the results of his Day 1
monitoring:
1. Face and neck (estimated from 7 residue/car of forearms, thighs
and calves)
a. 1.01 ng/cm2 + 4.94 ng/cm2 * 1.60 ng/on2 * 3 • 2.52 ng/cm2
b. 2.52 ng/cm2 <• 2 hour monitoring period • 1.26 ng/cm2 per hour
c. 1.26 ng/cm2 x 910 cm2 head and neck surface area * 1,146.6 ng/hour
2. Hands (estimated from total residue recovered from the glove
extract adjusted for one hour)
a. 10.8 ug » 10,800 ng recovered
b» 10,800 ~ 2 hour monitoring period » 5,400 ng/hour
3* Total dermal exposure » 1,146.6 ng/hour face and neck
+ 5.400.0 ng/hour hands
6,546.6 ng/hour - TOTAL
ASSESSMENT OF RESPIRATORY EXPOSURE. It 1s necessary to calculate
respiratory exposure from the high volume air sampling as all personal air
samples had no detectable levels of dlnoseb. The negative results of the
personal air sampling are thought to* be due to the volume of air sampled.
-18-
-------
36:
The high volume air samplers sampled air at a rate 16 times greater than
the personal air samplers. The high volume air sample residues recovered
approached the lower limit of detection which demonstrated the minimal
levels of dinoseb in the ambient air of the fields.
Estimates of the participants' lung ventilation for light to moderate
work are required in order to calculate hourly respiratory exposure. Rates
for adults by occupation are available, however, data for normal children
are scarce and when available the rates are reported for "resting" conditions.
Minute ventilation for adult male and female fruit thinners or pickers have
been reported as 29.0 - 30.0 1/m and 16.0 1/m respectively (EPA-600/8-80-038
(1980)). The same EPA publication reports the resting ventilation rate for
adult males at 7.0 1/m which coincides with data summarized by Polgar and
Promadhat (1971) for males age 10-17. Young male athletes performing light
work have been reported to average 28.6 1/m (Hayes, 1975) which approximates
the lung ventilation of adult male pickers. The rate of 28.6 1/m will be
used in the calculation of the potato harvesters' respiratory exposure. The
following calculations are presented to show the hourly respiratory exposures
' of Day 1 and Day 2.
Day 1:
a. Volume of Air Sampled:
32.0 1/m x 372-minutes = 11,904 liters
b. Dinoseb concentration in air: As both air samples were posi-
tive the mean will be used in the calculation.
619.72 Total ng recovered from Sample #1
+ 292.74 Total ng recovered from Sample #2
912.46 -f 2 = 456.23 ng (3T)
456.23 ng 7 11,904 liters = .038 ng/liter
c. Hourly ventilation of potato picker:
28.6 1/m x 60 m/hour = 1,716 I/hour
d. Hourly respiratory exposure:
.038 ng/1 x 1,716 I/hour = 65.21 ng/hour
-19-
-------
Day 2:
a. Volume of air sampled:
32.0 1/m x 351 minutes « 11,232 liters
b. Dinoseb concentration in air:
218.99 ng • Total recovered in Sample 12
218.99 ng f 11,232 liters « .019 ng/1
c. Hourly ventilation of potato picker:
28.6 1/m x 60 n/hour = 1,716 I/hour
d. Hourly respiratory exposure:
.019 ng/1 x 1,716 I/hour = 32.6 ng/hour
TOTAL HOURLY EXPOSURE. Participant 9 during Day 1 monitoring has been
shown to have a total dermal exposure of 6,546.6 ng/hour. His total hourly
exposure would be this total plus the Day 1 hourly respiratory exposure:
6,546.60 ng/hour (Dermal)
+ 65.21 ng/hour (Respiratory)
6,611.81 ng/hour TOTAL
These figures demonstrate that dermal exposure is generally much greater
than respiratory exposure (Hayes, 1975). In the case of participant 9,
respiratory exposure accounted for only 0.99% of the total hourly estimate.
Wolfe et al. (1967) reported that respiratory exposure ranged from 0.02%
to 5.8% (7 = 0.75%) of the total exposure for a number of pesticides.
Table 4 (Day 1) and Table 5 (Day 2) lists the estimated dermal, respiratory
and total hourly exposures for the ten participants. The participants'
exposure to dinoseb is shown to be predominantly dermal with the hands
being the primary route of exposure. This is not surprising as Davis (1981)
reported that 1n nearly all studies of occupational exposure to pesticides,
approximately 90% of the dermal exposure is found in the hands.
The potential hazard of exposure to a pesticide is a function of the
toxicity of the chemical, the route of exposure and dosage. An objective
method to relate these factors to data reported in exposure studies is to
express exposure as a percentage of the toxic dose. Estimates for the
-------
Table 4
Dermal, Respiratory* and Total Hourly Exposure to Dinoseb - Day 1
Juvenile Potato Harvester Study - Aroostock County, Maine 1981
I
r\j
Participant
I.D.
1
2
3
4
5
6
7
8
9
10
Hourly Dermal Exposure
Face & Neck
(nc/hr)
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1,146.6
348.8
4-
Hands
(ng/hr)
12,125.0
3,520.0
1,940.0
4,045,0
15,595.0
2,385.0
3,480.0
825 0
5,400.0
1,160.0
Total
(ng/hr)
12,125.0
3,520.0
1,940. (
4,045.0
15.595.0
2,385.0
3,480.0
825.0
6,546.6
1,508.
Hourly
Respiratory
Exposure
(ng/hr)
65.21
65.21
65.21
65.21
65.21
65.21
65.21
65.21
65.21
65.21
Total
Hourly
Exposure
(ng/hr)
12,190.21
3,585.21
2,005.21
4,110.21
15,660.21
2,450.21
3,545.21
890.21
6,611.81
1,574.01
Estimation of Toxic Dose
Participant
body, weight
29.25
40.50
49.50
27.00
54.00
49.50
42.75
45.00
45.00
36.00
Toxic
es
2,340.5
3,240.0
3,960.0
2,160.0
4,320.0
3,960.0
3,420.0
3,600.0
3,600.0
2,880.0
Z of Toxic
Dose/hr.
.0005
.0001
<.000l
.0002
.0004
<.0001
.0001
<.000l
.0002
<.0001
Assuming 100% absorption; dermal LD_Q • 80 mg/kg (80,000,000 ng/kg) calculated for each participant based upon
body weight (kg). Example - participant lit 29.25 kg x 80 mg/kp- 2,340 tug. 12.125.0 nn/hr. nnn_.
the estimated toxic dose per hour. 2,340.0 mg " 'UUU3* of
Osl
CN
-------
Table 5,
Dermal, Respiratory and Total Hourly Exposure to Dinoseb - Day Z-
Juvenile Potato Harvester Study - Aroostock County, Maine 1981
Participant
I.D.
1
2
3
4
5
6
7
8
9
10
Hourly Dermal Exposure
Face & Nee
(ng/hr)
0.0
0.0
0.0
0.0
441.4
0.0
0.0
147.1
2,253.8
862.9
i
1 j
Hands
(ng/hr
660,0
1,575.0
0.0
1,450.0
4,540.0
1,515.0
0.0
5,415.0
2,265.0
385.0
a
Total
(ng/hr)
660.0
1,575.0
0.0
1,450.0
4,981.4
1,515.0
0.0
5,562.1
4,518.8
1,247.9
dose per hour.
Hourly
Respiratory
Exposure
(nR/hr)
32.6
32.6
32.6
32.6
32.6
32.6
32.6
32.6
32.6
32.6
a
80,000,000 ng/kg)
g x 80 rag/kg - 2,
Total
Hourly
Exposure
(np,/hr)
692.6
1,607,6
32.6
1,482.6
5,014'.0
1,547^6
32.6
5,594.7
4,551.4
1,280.5
Estimation of Toxic Dose
Participant
body, weight
29:25
40.50
49.50
27.00
54.00
49.50
42.75
45.00
45.00
36.00
calculated fo,r each participat
340 me. 660»Q. ng/hr nnmv
2,340 mg
Toxic
Dose
(mgj
2,340.0
3,240.0
3,960.0
2,160.0
4,320.0
3,960.0
3,420.0
3,600.0
3,600.0
2,880.0
% of Toxli •;
Dose/hr.
<.0001
<.000i
<.0001
<.0001
.0001
<.0001
<.0001
.0002
.0001
<.0001
it based upon his body
)% of the estimated toxic
ON
ON
-------
participants of this study have been made and are included in Tables 4 and 5.
These are estimates-of the dermal toxic dosage based on the lowest reported
dose of 80 mg/kg in rabbits (NIOSH, 1977). It must be stressed that these
figures are estimates only because of the various parameters involved.
For example, it is assumed that 100% absorption occurs and an animal model
is used to extrapolate the toxic dosages for humans. Results of the extra-
polations are reported in percent of the toxic dose per hour of exposure.
During both days of study the participants received from 0.0005% to less
than 0.0001% of the toxic dose per hour. Assuming that 100% of the dose
is required for a toxic reaction, this equals a safety margin of 200,000
to greater than 1,000,000 times per hour for the various participants of
study.
Participant 1 (Day 1) had the highest percentage (0.0005) of the toxic
dose per hour among the ten participants during the two days of study.
If this percentage is adjusted for a ten hour work day (0.0005% x 10
hours), he would have received only 0.005% of the toxic dose which
equates to a safety factory of 20,000.
Statistical Analysis - Linear regression was employed to determine
if the participants' percent toxic dose was related to body weight (independent
variable = body weight, dependent variable = percent toxic dose). Analysis of
Day 1 data (workers 9 and 10 wore their cotton gloves underneath their work
gloves) detected no significant relationship F. 0= 0.812 (P=.39). Analysis of
1,0
Day 2 data (all participants except worker 8 wore the cotton gloves underneath
their work gloves) also found no significant relationship F, 0= 0.37 (P=.56).
1,0
The participants' Day 1 and Day 2 dinoseb exposures were added together
and the additional independent variable of glove wearing was examined. A parti-
cipant could have worn his cotton gloves underneath his work gloves 0, 1, or 2
days. Thus, slightly more workers were involved in different glove wearing
-23-
-------
368
procedures. For example,.seven participants wore their cotton gloves under-
neath work gloves one day only while one participant wore only the cotton
gloves on two days and two participants wore their cotton gloves underneath
work gloves on two days. Multiple.regression analysis again showed no
relationship with percent toxic dose. Both variables together showed no
relationship, F, , • 0.179 (P-.84). Likewise weight alone F. . * 0.360
£,/ . A,/
(P-.57) or gloves alone F. 7 • 0.10 (P».94) produced null.results.
Dlnoseb degradation 1s suggested by the data between Days 1 and 2
monitoring. For each participant 1, yi was computed, where yl • log (T^/Tg)
and T. » percent toxic dose for day j. The t-test was used because the log
transform causes the data to follow more nearly a normal distribution. Nine
yl's out of ten were positive, pointing to the suspected degradation (sign
test, P-.011). The t-test also verified this, tq - 2.226 (P-.Q27). Both-
P-values are one-sided.
CONCLUSIONS
Data presented 1n this report documented the minimal exposure of the
participants to dinoseb 19 and 20 days after application to the potato
fields of study. Respiratory exposure contributed little to the total
exposure of the participants. As expected, the hands accounted for almost
all of the dermal exposure. When exposures were compared to estimated
toxic dosages, 1t was seen that the participants were receiving less than
a few ten thousandths of one percent of the doses per hour.
Absorption of the chemical by the participants was not demonstrated,as all
urine samples were negative for dinoseb residue.
-24-
-------
369
These observations, within the constraints of this study, strongly
suggest that juvenile potato pickers are not being unduly exposed to
dinoseb during harvest operations.
-25-
-------
REFERENCES 370
Agricultural Chemicals and Pesticides: A subfile of the Registry of Toxic
Effects of Chemical Substances. 1977. DHEW (NIOSH) Publication No. 77-180.
Davis, J.E. Minimizing Occupational Exposure to Pesticides: Personnel Monitoring.
Residue Reviews, 75:33-50 (1981).
Hayes. W.L. Toxicology of Pesticides. Baltimore: The Williams and W1lk1ns and
Company (1975).
Idaho Pesticide Hazard Assessment Project. Final Report August 1979 - April 1931.
EPA Cooperative Agreement CR 806930-01/02.
Manual of Analytical Methods for the Analysis of Pesticides 1n Humans and Environ-
mental Samples, U.S. EPA, Health Effects Research Laboratory, Research
Triangle Park. N.C. EPA - 600/8-80-038 (1980).
Polgar, G. and V. Promadhat. Pulmonary Function Testing In Children: Techniques
and Standards. Philadelphia: W. B. Saunders Company (1971).
Powell, O.J. "A Literature Review of Methods for the Analysis of D1n1trophenles and
a Survey of their use 1n Maine." A thesis 1n partial fulfillment for the
Degree of Bachelor of Science, Bates College, 1979.
Wolfe, H. R., Durham, W. F. and Armstrong,-J. F. Exposure of Workers to Pesticides.
Arch. Environ. Health, 14: 622-623 (1967).
-26-
-------
Appendix A 37]
Pesticides tor Maine Potatoes, 1981
Herbicides Fungicides
Aldicazb Alachlor
tori nptv jMimtJ'iyl CblOTbT
Duter
Qotofuran Dinoseb Ifanoozeb
llBUeb
Polyrao
Dimetboate Ifetrlbuzin
Disulloton Paraquat
Endosulfan
lialathion
Metfaaaddophos
Metbonyl
Ifevlnpbos
Parathion
Phorate •
Phosalone
Pirinicarb
OQ0027
-------
Appendix B
770
Dinoseb Analysis ^ ' e-
Sample Extraction - Pads, Filters
Field samples are presumed to be stored at 0°F. and wrapped
1n aluminum foil. The samples should be removed and allowed to come
to room temperature.
A. Place the sample to be extracted 1n a chromatography
column that has a stopcock (Kontes 420530, size 241).
Push the sample to the bottom of the column until 1t
is 1n position above the stopcock.
B. Pour 1n 50 ml of acetone. Stopcock Is In closed
position.
C. Allow the acetone to stand on the sample for 3-4
minutes.
D. Drain the acetone from the sample into a round bottom
flask suitable for attachment to a rotary evaporator
(or a KG concentrator may be used). Adjust the flow to
5 ml per minute.
E. Repeat the extraction two more times, collecting and
combining extracts.
F. Reduce the volume of the sample extract and replace the
acetone with hexane. Make volume to 2 ml.
G. Proceed with derivatization.
Sample Extraction - Gloves
A. Allow frozen samples to come to room temperature.
B. Place the sample (1 pair) 1n a soxhlet apparatus and
extract for about eight hours with acetone.
C. Reduce the volume of the sample extract and replace the
acetone with hexane. Make volume to 2 ml.
D. Proceed with derivatization.
Sample Extraction - Water
Follow the procedure in Section 10A, Manual of Analytical
Methods for the Analysis of Pesticides in Human and Environmental Samples,
Health Effects Research Laboratory, Environmental Protection Agency, R.R.
Watts, Ed. (1980).
000028
-------
Appendix B
373
DOW CHEMICAL U.S.A.
... _ inat MMANO. MCHKtAN
October 6, 1981
Mr. Ernie Richardson
Maine Public Health Laboratory
Department of Human Services
State House
Augusta, HE 04333
cc: Fred Lang ley, Dow Chemical U.S.A., Boston, Massachusetts
Dear Mr. Richardson:
Regarding your Inquiry for a procedure for dlnoseb 1n urine, please
find enclosed a method published 1n the Journal of Agricultural and
Food Chemistry. Vol. 28, pg. 258 (1980), which has been extensively
used for many substrates. I am also enclosing some procedural
changes that I have used for the analysis of urine. If you have
further questions, please contact me.
Since you already have a standard of dlnoseb, I will send you the
analytical calibration standard dlnoseb methyl ether.
Sincerely*
Robert C. Gardner .
Residue/Environmental /Metabolism Research
Agricultural Products Department
90QT Building
(517) 636-5707
11
000029
-------
253
J. Agrtc. Food C/wm. 1»»0. 28. 258-261
Turrell, F. M., "Tables of Surfaces and Volumes of Spheres and
of Prolate and Oblate Spheroids, and Spheroidal Coefficients",
University of California Press, 1946.
Veith, G. D., Kiwus, L. M., Bull. Environ. Contam. ToxicoL 17,
631 (1977).
Winell, B., Analyst (London) 101, 883 (1976).
Yatsu, L., Cornell (Univ.) Agric. Erp. St. Mizneo. S-457. Itfeaca,
NY. 1956.
Received for review February 28,1979. Accepted October 30,1979.
A Method to Determine Dinoseb Residues in Crops and Soil by Gas
Chromatography
Robert C. Gardner4 and Richard L. McKellar
A method is described for the determination of residues of dinoseb (2-cec-butyl-4,6-dinitrophenol) in
alfalfa, corn, cottonseed, field beans, almonds, peanuts, peas, potatoes, soybeans, grapes, oranges, peaches,
pears, barley, wheat, and soil at levels ranging from 0.05 to 100 ppra. Dinoseb is first extracted by hot
hydrolysis in methanol-sulfuric acid and subsequently partitioned into diethyl ether and adsorbed onto
basic alumina. After elution with sodium bicarbonate, ether partition, and diazomethane methylation,
the dinoseb methyl ether is adsorbed onto acidic alumina and eluted with ether. Electron-capture gas
Chromatography provides a sensitive means of quantifying residues of diooseb down to 20 pg. Average
recoveries ranged from 77 to 99%.
Dinoseb (2-sec-butyl-4,6-dinitrophenol) is the active
ingredient in several herbicides which are formulated as
the alkanolamine salts of the ethanol series, as the am-
monium salt, or as the free phenol [Typical formulations
include PREMERGE 3 Dinitro Amine Herbicide, DOW
Selective Week Killer, and DOW General Weed Killer,
which are products of The Dow Chemical Company.]
These herbicides are valuable and effective in the control
of many broadleaf weeds in crops and have been used
extensively for many years by fanners and state and fed-
eral experiment station investigators. The lack of trans-
location of dinoseb in plants (Bandal and Casida, 1972)
together with its short residual life on plants and in soil
allow its use in many crop situations without risk of res-
idues.
The literature is deficient in extensive and well-validated
methodology for dinoseb determination in crops. Yip and
Howard (1968) reported work on several dinitrophenols
in some fruits and legumes. McKellar (1971) reported a
method for dinoseb determination in milk and cream.
Guardigli et al. (1971) developed a TLC procedure for
dinoseb residues. Dekker and Selling (1975) in the
Netherlands presented a method for dinoterb (2-tert-bu-
tyl-4,6-dinitrophenol) in soil Edgerton and Moseman
(1978) applied the methodology of McKellar to determine
dinoseb in feed and rat tissues and excreta.
The method described here has been practiced for 10
years by four analysts in some 32 projects on 16 different
crops plus soil, involving 37 substrates which were succu-
lent, oily, dry fibrous, cellulosic, highly carbohydrate, or
ionic (soil). Large numbers of recovery determinations
validating the method in these substrates have been con-
densed into tables of average values.
EXPERIMENTAL SECTION
Gas Chromatograph. A Tracer Model 222 equipped
with a linearized nickel-63 electron-capture detector (ECD)
was used and operated at 95:5 argon/methane flow of 70
mL/min through the column plus 20 mL/min as detector
purge, with temperatures of 200-220 °C (column), 350 °C
Residue/Environmental/Metabolism Research, Agri-
cultural Products Department, The Dow Chemical Com-
pany. Midland, Michigan 48640. fi O D H
(detector), and 250 °C (injector). Earlier work utilized a
Barber Colman Model 5000 equipped with a strontium-90
ECD, which was operated at 90 mL/min nitrogen flow,
with temperatures of 200 °C (column), 250-350 °C (de-
tector), and 225 °C (injector). In both instruments, a 1.8
m X 3 mm i.d. glass U-column packed with 5% DC-200
on 80-100 mesh Gas-Chrom Z was used. An alternate
packing would be 3% OV-101. In these instruments, 20
pg of dinoseb methyl ether produced a 5-10% FSD, with
a base line noise of 0.1-0.2%. Retention time was typically
3-4 min.
Reagents. Solvents used were either distilled in glass
or pesticide residue quality.
Basic and acidic alumina, Woelm type, obtained from
Waters Associates as activity grade 1, were stored con-
tinually in an oven at 130 °C. Prepared columns were
cooled before use.
Standards of dinoseb and dinoseb methyl ether were
obtained from the Agricultural Products Department of
Dow Chemical U.S.A. in 99+% purity. Solutions of di-
noseb were kept in the dark, and those of dinoseb methyl
ether were refrigerated except just prior to use, when they
were allowed to come to room temperature.
Diazomethane methylating solution was prepared in
ether from Diazald according to the directions on the bottle
from Aldrich Chemical Co., Milwaukee, WI. Caution
should be exercised in the preparation and use of diazo-
methane because it is toxic and can cause skin sensitivity
and is potentially explosive under certain conditions.
Sample Preparation and Extraction. Crops should
receive a preliminary chopping (Hobart Food Cutter) or
grinding (Wiley Laboratory Mill), as appropriate, and be
thoroughly mixed to provide a homogeneous sample.
Weigh 10 g of pulverized sample (5 g of low-density sam-
ples such as straw or fodder) into a 4-oz square bottle and
add 40 mL of methanol containing 2 mL of 6 N sulfuric,
acid. (More methanol may be required to cover straw or'
fodder.) Prepare a recovery sample by spiking a duplicate
control sample with 1 mL of the appropriate concentration
of dinoseb in methanol and letting stand 15 min. After
heating the bottles for 1 h at 70 °C in a water bath or oven
and cooling to the touch, blend each sample using a
Lourdes MM-1 multimixer or Brinkmann Polytron PT-
7 p20ST homogenizer for 3 or 1 min, respectively. Add 5 g
-------
375
Analytical Procedure
a. Weigh 0.5 or 1.0 g sample into a 12 dram vial. Add 1 ml
of spiking solutions for recovery studies.
b. Add 1 ml of 6N H-SO., bring volume to 5 ml with
water, add 4 g NaCl and 20 ml ether.
c. Cover* the vial with a Poly-seal.cap and shake for
7 min., then centrifuge for 3 min at highest speed.
d. Transfer the ether phase to a 10 x 300 mm column con-
taining 2.5 cm of basic alumina, on top of which is
a small wad of glass wool. Let the ether trickle
through to waste and gently blow out residual ether.
e. Elute the column into a 12' dram vial with 15 ml
of 0.025M NaHCC>3, using 0.5 psi air pressure for
flow control (2 ml/min).
f. Add 1 ml of 5% H,PO. and 10 ml ether. Cover with
a Poly-seal cap und shake for 3 min, then
centrifuge for 3 min at highest speed.
g. Transfer the ether phase to a 40 ml centrifuge tube
having a 5 19 joint. Add 1 ml diazomethane
reagent and let stand 15 to,30 min.
h. Add a boiling chip and 3 ml of hexane. Insert a
Vigreux distilling head having a 5 19 joint.
tEvaporate on steam bath to 2.5 - 3 ml.
1. Transfer the hexane solution to a 2.5 cm. column
of acidic alumina in a disposable pipet. Rinse
the centrifuge tube with 3/4 ml hexane and add to the
•column. Discard the hexane effluent.
j. Elute the column into the centrifuge tube again with
5 ml of ether, add a boiling chip and 3 ml of
hexane. Insert the Vigreux distilling head.
•
k. Evaporate the ether on the steam bath to about
3 ml.
1. Bring to a volume of 5.0 or 10.0 ml with trimethyl-
pentane to give a final concentration of 0.1 g sample
per ml.
m. Inject 4 ul onto the 5% DC-200 column.
000031
-------
Appendix B
of Johns-Manville Hyflo-SuperCel filtering aid, cap the
bottle with a Poly-Seal cap, and shake vigorously for 15
fflin. Filter the sample through a 0.5-cm pad of Hyflo-
SuperCel in a Buchner fritted disc funnel, washing the
bottle and filter cake with methanol to 100 mL of filtrate.
Process soils through the Wiley Mill while frozen, using
dry ice to prevent thawing. Weigh 50 g of roil into a
200-mL centrifuge bottle (Corning 1261) and add the di-
noseb spike in the case of recovery determinations and 100
mL of methanol solution containing 5 mL of 6 N sulfuric
acid. Cap the centrifuge bottle and heat at 70 °C for 30
min, shake immediately for 15 min and then cooled the
bottle to room temperature before centrifuging.
Cleanup and Derivatization. Transfer 10 mL of fil-
trate to an 11-dram capsule vial containing 15 mL of water
and 8 g of NaCL Partition twice with 10 mL of diethyl
ether, pipetting the ether after each partition onto a 3-cm
column of basic alumina in a 1-cci Ld. chromalographic
tube. A layer of glass wool above the alumina surface will
prevent its disturbance when adding ether. Elute the
residue from the column into an 11-dram vial with 15 mL
of 0.025 M sodium bicarbonate. Air pressure of 0.5 psi will
keep the column flowing at 2-3 mL/min. Add 0.1 mL of
concentrated phosphoric acid and 5 mL of diethyl ether
and shake 2 min. Transfer the ether to a 40-mL conical
centrifuge tube having a T 19 joint (Kimble 45201), add
1 mL of diszomethane solution, and let stand 15-30 min.
Add 3 mL of hexane. Evaporate the excess diazomethane
and ether on a steam bath to 2.5-3 mL using a Vigreaux
distilling column (Kontes 2S6710). Clean up the residue
further on a 2.5-cm column of acidic alumina contained
in a disposable transfer pipet and elute the dinoseb methyl
ether into the conical centrifuge tube with 5 mL of diethyl
ether. Evaporate the ether on a steam bath with 3 mL of
trimeihylpentane present as a keeper, then dilute to 10 mL
with trimethylpentane. If 5 g of straw or 50 g of soil was
weighed out initially, final volume should be 5 or 50 mL,
respectively, to provide a substrate concentration of 0.1
g/mL (or 0.005 Mg of dinoseb methyl ether /mL at 0.05
ppm).
If after gas chromatographing the sample, interferences
are found to be present in some substrates, they may be
removed by partitioning the trimethylpentane solution
with a few millfliters of 0.1 N NaOH and reinjecting the
sample.
. Gas Chromatography. Injection volume is 4 jtL. The
dinoseb peak height of the sample is compared to a
standard curve prepared from peak heights of solutions
of the dinoseb methyl ether primary standard weighed out
and diluted with trimethylpentane over the range of 0.005
to 0.10 pg/mL. Treated samples out of this range were
diluted.
It should be noted that dinoseb methyl ether is chro-
matographed but results are reported in dinoseb equiva-
lents. This is done automatically by weighing out 1.058
times as much of dinoseb methyl ether as of dinoseb, but
labeling the solutions at the concentrations of dinoseb.
Calculations. Once the sample concentration in raig-
rograms/milliliter has been determined from the standard
curve, ppm dinoseb is obtained by multiplying the sample
concentration by 10 and by any dilution factor. Parts per
million dinoseb in the sample should be corrected for the
degree of recovery by the following formulas:
ppm(sarople) - ppm(control)
7o recovery = ,...-.-.» X 100
j. Agric. Food Cham., Vol. 26. No. 2.1980 259
ft
Table I. Recovery of Dinoseb from Various Substrates
substrate
alfalfa
green forage
dry forage
almonds
hulls
nutmeats
barley
green forage
straw
grain
beans, field
green forage
stover
beans
com, field and sweet
green forage
fodder
kernels plus cobs
kernels
cotton seed
field trash
cottonseeds
oil
grapes
oranges
peaches
peanuts
green forage
hay
hulls
nutmeats
pears
peas, English
green forage
peas
peas, Southern
vines and pods
peas
potatoes
soil
soybeans
green forage
straw
soybeans
wheat
green forage
straw
grain
all substrates
ppm added,
range
0.1-1.0
0.1-1.0
0.1-1.0
0.1-0.5
0.1-1.0
0.1-1.0
0.05-0.5
0.1-1.0
0.1-1.0
0.05-0.5
0.1-0.5
0.1-0.5
0.05-0.1
0.05-0.1
0.1-1.0
0.1-0.5
0.1-0.5
0.05-0.5
0.1-0.5
0.05-0.5
0.1-1.0
0.1-1.0
0.1-0.5
0.05-0.5
0.05-0.5
0.1-1.0
0.05-0.5
0.1-1.0
0.05-0.5
0.05-0.5
0.1-1.0
0.1-1.0
0.1-1.0
0.05-0.5
0.1-1.0
0.1-1.0
0.05-0.5
no. of
determ
14
17
24
8
9
8
9
14
13
11
14
12
9
12
10
6
5
28
6
6
25
23
20
42
-6
23
19
7
10
27
53
43
34
33
7
7
11
626
% recovered
range
80-110
70-100
65-103
82-96
86-103
79-90
83-102
84-104
80-95
81-100
70-93
65-108
66-90
78-108
80-105
85-107
83-95
82-110
84-9 §
92-106
71-110
72-93
63-102
62-110
87-102
77-94
80-95
80-94
80-96
79-102
64-116
66-105
72-92
63-108
85-93
83-101
81-108
av
98
85
77
89
95
84
89
94
87
90
83
84
79
88
93
98
86
95
90
99
86
86
89
85
97
86
88
85
86
93
88
87
82
85
90
93
90
88
376
ppm corr :
ppm (added)
ppm(sarople) - ppm(control)
% recovery
XI
tiooo
RESULTS AND DISCUSSION
The method described above has found extensive use
in obtaining much of the analytical data needed to support
petitions to EPA for establishing tolerances for dinoseb
in crops. The recovery determinations validating the
method in these crops are summarized in Table I. The
overall average of 626 determination is 88%.
Space does not permit inclusion of chromatograms for
all the substrates; however, typical chromatograms of
analyses using the Barber Colroan and Tracer instruments
are shown in Figure 1. The shape of the solvent peak
detected by the Barber Colman has always been broad and
gets broader as the detector gets dirtier. This did become
a problem in time, even with detector cleaning, resulting
in the dinoseb peak being high upon the solvent tail The
design of the newer detectors permits rapid clearing of
solvent from the cell, leaving a sharp solvent tail. Thus,
it is seen that the same substrates later produced sharper
looking chromatograms.
_ The recovery averages can be grouped according to type
JcJFsubstrate: succulent (fruits and potatoes), 90-977e; oily
-------
Table II. Recovery of Dinoseb in Green Forage at
Various Spiking Levels
spiking level,
ppm
0.1
0.5
1.0
5.0
10.0
20.0
50.0
100.0
no. of
delerm
3
3
5
3
2
1
2
1
»v %
recov
91
94
89
94
95
98
98
96
(nutmeats and cottonseeds and oil), 85-98%; dry fibrous
(dry forage, fodder, straw and hulls), 77-93% cellulosic
(green forage), 85-98%; highly carbohydrate (grains, beans
and southern peas), 84-90%; and soil, 88%. There is not
a significant variation in degree of recovery vs. type of
substrate.
Dinoseb recovery is not concentration dependent over
the range of 0.1 to 100 ppm. Average recovery in soybean
forage for one project is shown in Table II. In this case,
the average of 20 determinations was 93%.
Stability of dinoseb residues in samples in freezer storage
was examined for the case of soybean forage. Samples were
spiked at two levels at the time of initial crop grinding and
then were maintained frozen with the treated samples for
21 months until all the samples were analyzed. The re-
coveries were 74% at 0.1 ppm and 90% at 1.0 ppm. The
control sample used for these storage recoveries contained
0.04 ppm apparent residue.
The effectiveness of the initial crop extraction procedure
was also examined by successively (exhaustively) extracting
the filter cake from a treated sample with fresh portions
of the methanol-sulfuric acid solution by shaking 15 min,
filtering, and washing the filter cake to 100-mL volume.
The original and two successive extractions were analyzed
as individual samples. Data produced over a 5-year period
indicate that dinoseb residues in field treated soybean and
pea forage were 90-99% removed in the original extraction.
Standard curves of peak height vs. concentration were
prepared each day and used to quantitate the residue in
treated'samples. Using the Barber Colman instrument,
the curve could always be drawn smoothly through all
points in the range of 0.005 to 0.10 ng/mL, but the cur-
vature and slope did vary with time as the detector lost
sensitivity and required higher polarizing voltage. The
detector could be cleaned manually or by high temperature
(400 °C), after which former conditions would return. The
Tracer linearized detector system has been much more
stable to dinoseb, permitting the use of the same standard
curve for several days. Sensitivity has remained essentially
the same for 4 years, without cleaning the detector. The
detector has been continually operated at 350 °C.
Confirmation of dinoseb methyl ether can be made by
gas chromatographing the sample on a column more polar
than DC-200, such as OV-17. An alternative approach is
p value determination, which utilizes the solubility of the
molecules under observation in two differing solvents.
Once the treated sample in trimethylpentane (or hexane)
has been chromatographed, the solution is shaken with
60:40 acetonitrile/water and the trimethylpentane layer
is rechromatographed. The p value is calculated by the
equation of Bowman and Beroza (1966).
The determination is performed in duplicate on the
treated sample and a suitable recovery sample, and per-
haps a standard. It is important that the solvent system
composition during partitioning be very similar, or the
solubility of the dinoseb methyl ether will be altered in an
1 I I I I 1
Wu
u_
JL
0 1 2 3 4 ft 0246
MINUTES
Figure 1. Typical chromatograms from the analysis for dinoseb
(f R a 3-4 min) in various substrates obtained on (I) the Barber
CoLman GC equipped with a *°Sr ECD: (A) soil + 1 ppm, (B)
wheat grain + 0.05 ppm, (C) green pea forage + 0.1 ppm, (D)
soybean stover + 0.1 ppm, (E) peanut meats + 0.05 ppm, (F)
grapes + 0.05 ppm and (II) the Tracer GC equipped with a "Ni
ECD: (A) soil + 0.1 ppm, (B) com grain + 0.05 ppm, (C) corn
forage + 0.1 ppm, (D) soybean stover + 0.1 ppm, (E) peanut meats
+ 0.05 ppm, (F) potatoes + 0.05 ppm.
uncalibrated manner, leading to erroneous conclusions.
A modification was made during the analysis of corn and
peanuts, which are oily substrates. Normally, the ether
extraction of dinoseb from the methanolic extract is carried
out in the presence of acid. However, if the extract is made
alkaline with 15 mL of 1 N sodium hydroxide or sodium
acetate, cleanup is improved and recovery is comparable
with the general expectation of the method. When the
modification was attempted for soil, recovery decreased
significantly.
During the course of analysis of soil, it is desirable to
determine the moisture content of each sample so that
residues found can be normalized. Values reported in the
literature will be more meaningful if they can be related
on a "dry-weight" basis. Moisture in the soil samples used
in recovery determinations can be neglected, but a cor-
rection for moisture content should be made for all other
-------
determinations.
SUMMARY
Residues of dinoseb have been determined in many
substrates to a lower limit of sensitivity of 0.05 ppm.
Recovery experiments have been performed validating the
method in nearly every crop for which there is an estab-
lished EPA tolerance. An average percent recovery in the
high 80's can be expected from the method when per-
formed by e qualified analyst. Utilizing adsorption onto
alumina and the selectivity and sensitivity of the elec-
tron-capture detector, quantities of 20 pg of dinoseb
methyl ether and less have been quantitated in the pres-
ence of substrate extract.
Appendix B '3/8
LITERATURE CITED
Bandal, S. K, Casida, J. E., J. Agrie. Food Chem. 20,1235 (1972).
Bowman, M. C., Beroza, M., Anal. Chem. 38,1427 (1966).
Dekker, W. H., Selling, H. A., J. Agric. Food Chem. 23, 1013
(1975).
Edgerton, T. R.f Moseman, R. F., J. Agric. Food Chem. 26,425
(1978).
Guardigli, A^ Chow, W, Lefar, M, J. Agrie. Food Chem. 19,1181
(1971).
McKellar, R. L., J. Agrie. Food Chem. 19, 85 (1971).
Yip, G, Howard, S. Fn J. Auoe. Off. Anal. Chem. fil, 24 (1968).
Received for review March 22,1979. Accepted September 19.
1979. The Dow Chemical Company No. B-600-029-79R.
000034
-------
379
APPENDIX C
QUALITY ASSURANCE
The SC PHAP contracted with the Maine Public Health Laboratory
(MPHL) for dinoseb residue analysis of the samples (n * 163) collected
in this study. Quality Assurance (QA) was established prior to analysis
and was maintained throughout the analytical period.
It was first anticipated that QA would be established by randomly
splitting 10* of the samples (or sample extracts) with dual analysis pro-
vided by the SC PHAP laboratory. After completion of the field phase of
the study, it was felt that expected residues would be too low to split
sample extracts and that the procedure would reduce by half the concentra-
tion of the samples selected for QA. To overcome this problem, an alternate
QA program was developed as discussed below.
The revised QA plan was directed by the Iowa PHAP with the approval
of the QA Officer/Health Effects Branch. The Iowa PHAP was responsible
for the spiking of sample media for QA analysis by the MPHL. The SC and
IA PHAP's also participated in the QA plan to serve as a check for the
analytical methodologies used by the MPHL. This plan established inter-
laboratory quality control among the three laboratories and the in-house
quality control for the MPHL. The following table lists the number of
samples collected in the field study by medium along with the total number
of QA samples analyzed by laboratory.
000035
-------
Appendix C
QA SAMPLE PLAN
SAMPLES COLLECTED MPHL INTERLABORATORY QA
SpIKe fromIn-House
n. Medium IA + Spikes - TOTAL SC JA
20 pairs Gloves 2 2422
80 pairs Gauze Squares 6 4 10 22
20' Fiber Filters — —-...—
30 Urines 5 2721
6 Soil 5 0511
6 NAOH 3 1411
2 Water J_ _2 .3. J. J[
164 22 11 33 9 8
To establish Quality Assurance for each medium at least the first two QA
samples of the particular medium were analyzed by the MPHL as unknowns.
Results of the analysis were reported (telephone) to the Iowa PKAP QA
administrator for his approval of compliance and for permission to precede
with the analysis of the field samples of the particular substrate. Addi-
tional QA samples of known concentration provided by the Iowa PKAP were
analyzed along with QA spikes made up by the MPHL for In-house QA. Further-
more* the MPHL analyzed a reagent blank for every ten field samples.
Results of the MPHL QA program'are reported 1n Table 1. Table 2 reports the
SC and Iowa Interlaboratory QA.
In an effort to demonstrate the completeness of extraction of the
gauze squares and personal air sample glass fiber filters using the, Iowa
column extraction method, the MPHL pooled the previously extracted 80 pairs
of gauze squares and 20 filters Into three large samples and re-extracted
them for eight hours with acetone using the soxhlet extraction apparatus
used in the analysis of the participants' gloves. The total residues re-
extracted from the three pooled samples are shown below. The data shows a total
of 508 nanograms (0.5 mlcrograms) was not extracted from the 180 pieces
previously analyzed. This amounts to an average of 2.9 ng per piece (5.8
ng/pair) which is far below the minimum level of detection of 40 ng per
-------
Appendix C
381
sample for the column extraction analysis.
Pooled Gauze Squares Total Pieces Total Dinoseb
and Glass Fiber Filters Extracted Recovered (ng)
Sample 11. (Participant 48 Gauze 208
samples 1A through 3B) 6 Filters
Sample #2. (Participant 48 Gauze 104
samples 4A through 6B) 6 Filters
Sample #3. (Participant 64 Gauze 208
samples 7A through 10B) 8 Filters
TOTAL 180 520 ng
In addition to the QA plan, spikes of the glove, gauze and glass
fiber filter media were made at the time of the field study and were frozen
along with the collected samples. The purpose of this procedure was to
demonstrate the stability of these spiked samples (fortified with microgram
-levels of dinoseb) as a standard to the stability of the collected samples.
Five of the six field spikes demonstrated good to excellent stability when
percent recoveries are coirpared to those observed recoveries from the
analysis of the Iowa QA samples. The low recovery of the high spike glove
i
sample is unexplained.
t FIELD SPIKES
Gloves Gauze Filters
Low Spike High Spike Low Spike High Spike Low Spike High Spike
Spike (ug) 2.50 25.00 2.50 25.00 2.50 25.00
Recovered 2.31 11.40 '1.88 21.40 2.06 21.20
% Recovery 92.4% 45.6X 75.2% 85.6% $2.4% 84.82
37
-------
Table 1
QA RESULTS - MAINE PUBLIC HEALTH LABORATORY
QA Substrate
Gloves
Spike (yg)
Recovered (yg)
Z Recovery
X Z Recovery -87.35
Gauze Pads
Spike (yg)
Recovered (yg)
Z Recovery
X % Recovery "87.87
NaOH
Spike (yg)
Recovered (yg)
% Recovery
X" Z Recovery- 119.'
Water
Spike (yg)
Recovered (yg)
Z Recovery
X Z Recovery -98.50
Soil
Spike (yg)
Recovered (yg)
Z Recovery
)C Z Recovery » 101. 1(
Urine
Spike (yg)
Recovered (yg)
Z Recovery
H Z Recovery - 51.00
n
1.00
1.22
122.00
3.00
2.36
78.70
1.00 mg
1.30 "
130.00
3
100.00
105.75
105.75
1000.00
1047.00
104.70
1.00
0.45
45.00
#2
1.00
0.82
82.00
3.00
2.36
78.70
l.OOmg
1.30"
130.00
30.00
26.48
88.26
1000.00
1008.00
100.80
1.00
0.61
61.00
93
40.0
29.1
72.8
3.00
2.78
92.70
25JOOyg
25.07 "
100.30
200.00
203.00
101.50
1000.00
1037.00
103.70
1.00
0.41
41.00
*4
4.0
2.9
72.6
3.00
2.77
92.30
l.OOmg
1.17"
117.00
-
1000.00
1071.00
107.10
1.00
0.57
57.00
05
-
3.00
1.88
62.70
-
~ l
-
1.00
0.39
39.00
O-
//6
-
3.00
3.13
104.00
-
-
-
1.00
0.59
59.00
38
91
-
50.00
39.85
79.70
-
-
-
1.00
0.47
47.00
#8
-
10.00
9.07
90.70
«
-
-
1.00
0.59
59.00
19
-
50.00
51.4
102.8
-
-
-
1.00
0.24
24.00
no
-
100.00
97.4
97.4
-
-
-
1.00
0.46
46.00
#11
t
-
-
-
-
1.00
0.92
92.00
1H2
-
-
-
-
-
•
1.00
0.42
42.00
-------
Appendix C
Table 2
Interlaboratory QA
Spike
Iowa PHAP
Recovered
% Recovery
SC PHAP
Recovered
% Recovery
Gloves .
01
1.0 yg
0.65
65.0%
0.86
86. 0%
#2
1.0 yg
0.70
70. 0*
0.62
82. 0%
Gauze Squares
01
3.0 yg
2.79
93.1%
2.7
90.0%
n
3.0 yg
2.84
94.7%
2.77
92.3%
Urine
in
0.1 yg/gm
-
-
0.058
58.0%
#2
1.0 yg/gfl
0.79
79.0%
0.848
85.0%
Roll
rfl
i 1000.0 yg
759.0
75.0%
1.006.7
100.7%
NaOH
#1
1.0 mg
85.0
85.0%
108.8
108.8%
Water
//I
100.0 yg
90.5
90.5%
92.6
92.6%
Usl
CA!
CD
-------
384
Youth in Agriculture: Dermal and Respiratory
Exposure Assessment of Adult and Juvenile
Tomato Harvesters to Endosulfan, Charleston
County, South Carolina 1981
Research performed by
Medical University of South Carolina
-------
•7 QC
Table of Contents J
Abstract ii
Objective 1
Background 1
Methods 4
Results 11
Discussion 17
Conclusions 23
References 25
Appendices
A - Approved Pesticides for South Carolina Tomatoes, 1981 1
B - Foliage and Soil Sampling Scheme 2A-2B
C - Quality Assurance Plan and Results 3A-3E
-------
386
Abstract
Ten participants, five males and five juveniles, were monitored on
two consecutive days for their dermal and respiratory exposure to endosulfan
during the harvest of tomatoes. Environmental sampling documented the presence
of endosulfan in the soil, foliage and ambient air of the fields of study.
Results of the participant monitoring showed that respiratory exposure contri-
buted little toward total exposure while the hands accounted for almost all
of the dermal exposure. Estimates of dermal toxic doses for each of the ten
participants revealed they were receiving only a few parts per thousandths
of one percent of the doses per hour. Data presented in this study suggest
that juvenile workers are not being unduly exposed to endosulfan during harvest.
11
-------
387
Dermal and Respiratory Exposure Assessment of Adult and
Juvenile Tomato Harvesters to Endosulfan -
Charleston County, South Carolina 1981
OBJECTIVE:
The dermal and respiratory exposure of adult and juvenile field work-
ers during harvest to the ambient air, foliage and soil of endosulfan treated
tomato fields was monitored to discern what differences, if any, exist between
the exposure patterns of these workers.
BACKGROUND:
' The U. S. Environmental Protection Agency and U. S. Department of Labor
finalized an interagency agreement on March 17, 1980. This agreement, "Youth- in
Agriculture", provides for the development of pesticide protection programs for
farmworkers. One goal is the determination of scientifically'based reentry
intervals for children and the assessment of potential health effects of pesti-
cides on children working in agriculture. The agreement assumes that the poten-
tial for the exposure of children to toxic chemicals in agriculture is widespread
and that children are generally more sensitive to chemical exposure. Furthermore,
children possibly have greater rates of dermal and/or gastrointestinal uptake
and have decreased capacity for detoxification. Yet, little or no data exists
to support these assumptions as it applies to field workers. In order to bridge
this data gap, it is necessary to conduct studies which measure the pesticide
exposure of adult and juvenile workers to various pesticides during the harvest
of a variety of hand-picked crops.
Charleston County, S.C. - Each year in Charleston County, approximately
3.5 thousand acres of tomatoes are harvested which requires the employ-
ment of local, seasonal workers and over two thousand migrant laborers.
The majority of local workers, whether adults or juveniles, are hired
as packers at tomato sheds. In South Carolina, a juvenile 10 to 14
-1-
-------
388
years of age must be accompanied by a parent or guardian in the field
to be eligible for employment as a picker. Those juveniles >. 14 years
old can work in the harvest only with signed parental consent. Adults,
however, account for the bulk of the field labor force. Records of
the South Carolina Employment Commission indicate that between 2,200
and 2,300 migrant workers were hired for the Charleston County tomato
harvest in 1980. Of these, 146 (approximately 6%) were juveniles <_ 16
years of age. An estimated 95% of the migrant work force is Hispanic
and the remaining 5% is predominately black. The few local harvest
crews are also black and are composed of both juveniles and adults.
A portion of the migrant labor force arrives in Charleston
during late April and early May. Adults work in the fields pruning
and staking the tomato plants. Their school age children attend public
school until summer recess which occurs in early June. The tomato
harvest is usually underway by the first week of June and those chil-
dren desiring employment join the harvest crews. The harvest is typi-
cally completed during the first week of July.
The work day usually begins in mid to late morning as soon
as the dew evaporates from the tomato plants. Each worker is assigned
a section of a row to harvest and is also told at which level to pick
the tomatoes. The rows are staked every four feet with two levels of
double strand twine connecting the stakes. The twine levels are
approximately two and 'four feet off the ground and the tomato vines
are supported between the strands of twine. The worker is issued a
5 gallon bucket by the farmer or crew chief to place the tomatoes in.
Once the bucket is filled, the picker carries the bucket to a flat
bed truck where the tomatoes are dumped in large wooded crates. The
worker receives 35 cents for each bucket and the average worker picks
-2-
-------
389
approximately 50 buckets per day. Staked tomatoes are picked at least
twice and as many as four times. Pickings usually occur in seven day
intervals and applications of fungicide/insecticide combinations take
place during the intervals.
Tomato Pesticide Usage - Clemson University's Cooperative Extension
Service recommended a total of 16 insecticides, 2 nematocides, 6 herbi-
cides and 6 fungicides for use on commercial tomatoes during 1981
(Appendix A). Most local farmers use methyl bromide as a soil fumigant
on tomatoes for weed control. After application, the rows are covered
with airtight plastic tarpaulins and the rows remain virtually free of
weeds throughout the season. Various combinations of insecticides;
and fungicides are applied throughout the season, however, as harvest
approaches, the chemicals of choice are more limited. The most frequent-
ly used fungicides prior to harvest are maneb and fixed copper while
the regularly used insecticides include endosulfan, bacillus thuringiensis,
methamidophos, methomyl and toxaphene. Endosulfan was selected for
monitoring in this study because of its longer residual properties and
because of the sensitivity and proficiency of available methodology for
residue analyses.
Endosulfan, an organic hydrocarbon contact and stomach poison,
is moderately to highly toxic with oral LD50 ranging from 18
mg/kg for rats to 118 mg/kg for hamsters. Dermal LD_n range from 74
mg/kg for rats to 167 mg/kg for rabbits (MIOSH, 1977). Systemic absorp-
tion may also occur via the respiratory tract. A threshold limit value
(TLV) for occupational exposure to concentrations of endosulfan in the
air has been established at 100 yg/m3 (NIOSH, 1977).
-3-
-------
390
approximately 50 buckets per day. Staked tomatoes are picked at least
twice and as many as four times. Pickings usually occur in seven day
intervals and applications of fungicide/insecticide combinations take
place during the intervals.
Tomato Pesticide Usage - Clemson University's Cooperative Extension
Service recommended a total of 16 insecticides, 2 nematocides, 6 herbi-
cides and 6 fungicides for use on commercial tomatoes during 1981
(Appendix A). Most local farmers use methyl bromide as a soil fumigant
on tomatoes for weed control. After application, the rows are covered
with airtight plastic tarpaulins and the rows remain virtually free of
weeds throughout the season. Various combinations of insecticides,
and fungicides are applied throughout the season, however, as harvest
approaches, the chemicals of choice are more limited. The most frequent-
ly used fungicides prior to harvest are maneb and fixed copper while
the regularly used insecticides include endosulfan, bacillus thuringiensis,
methamidophos, methomyl and toxaphene. Endosulfan was selected for
monitoring in this study because of its longer residual properties and
because of the sensitivity and proficiency of available methodology for
residue analyses.
Endosulfan, an organic hydrocarbon contact and stomach poison,
is moderately to highly toxic with oral LDcQS ranging from 18
mg/kg for rats to 118 mg/kg for hamsters. Dermal LD_Q range from 74
mg/kg for rats to 167 mg/kg for rabbits (NIOSH, 1977). Systemic absorp-
tion may also occur via the respiratory tract. A threshold limit value
(TLV) for occupational exposure to concentrations of endosulfan in the
air has been established at 100 yg/m3 (NIOSH, 1977).
-3-
-------
METHODS:
Site - A Charleston County farmer with approximately 100 acres of staked tomatoes
agreed to cooperate in the study. Each year, this fanner employs a
migrant labor crew and also a local crew composed of black laborers to
harvest his crop. The 1981 harvest commenced on June 9 with the first
picking of a 14.7 acre tract identified herein as the "shed field".
On June 10, the 18.8 acre "north field" was picked for the first time.
Both fields, 24 hours prior to harvest (June 8 and 9 respectively)
received the following pesticide treatment (pounds active ingredient per
acre) applied by a tractor pulled spray rig: endosulfan - 0.4, methomyl -
0.25, bacillus thuringiensis - 0.5, and maneb - 1.5. These two fields
were selected for participant and environmental monitoring (see Figure 1).
Participants -Participants were recruited from a local black crew because of the
availability of juvenile workers in the crew and to avoid potential
language barriers with the Hispanic migrant workers. Also, the few
juvenile workers observed in the migrant crew appeared to be in their
late teens.
Five adults (ages 20-63, four female and one male) and five juveniles
(ages 13-17, all male) were recruited for participation in the study
(Table 1). Each participant signed a voluntary informed consent agreement,
The ten participants were monitored for one hour on June 9 (Day 1) while
harvesting the shed field and again for one hour on June 10 (Day 2) while
harvesting the north field. The repetitive design of the monitoring was
intended to produce two sets of data based upon sampling conducted under
identical conditions. The monitoring of the participants lasted for only
one hour each day because the media employed for the assessment of
dermal exposure (disposable paper jackets and white cotton gloves) were
-4-
-------
Figure 1
Monitoring Sites - June 9 and 10, 1981; Charleston County, S.C.
392
PAVED ROAD
JNorth Field]
(18.8 acres)
Hi-Vol
Air Samplers
'XX
-5-
-------
Table 1
Participant Data: Dermal and Respiratory Exposure Assessment of Adult and
Juvenile Tomato Harvesters to Endoaulfan - Charleston County, South Carolina 1981
Jar
ADULTS
i/i
w
M
icipant
1
2
3
4
5
6
7
8
9
10
Age
50
63
22
20
28
14
15
17
16
13
Sex
F
F
F
M
F
M
H
M
M
M
Race
B
B
B
B
B
B
B
B
B
B
Height
(cm)
170
178
163
173
163
165
168
170
168
165
Weight
(kg)
74
74
63
70
59
54
56
61
56
54
Work Cloth InR
6-9-81
Long sleeve shirt,
pants, hat and shoes.
Long sleeve shirt,
pants, hat and shoes.
Short sleeve shirt,
short pants and tennis
shoes.
Short sleeve shirt,
short pants, hat
and tennis shoes.
Short sleeve shirt,
pants and shoes.
Short sleeve shirt,
pants and tennis shoes
Short sleeve shirt,
pants, hat and shoes.
Short sleeve shirt,
pants, hat and tennis
shoes.
Short sleeve shirt,
pants and tennis shoes
Short sleeve shirt,
pants, hat and shoes.
6-10-81
same as 6-9-81
same as 6-9-81
same as 6-9-81
same as 6-9-81
same as 6-9-81
same as 6-9-81
same as 6-9-81
same aa 6-9-81
same as 6-9-81
same as 6-9-81
Remarks
Sleeves of shirt
rolled up.
Sleeves of shirt
rolled up.
-
-
Refused to wear white
cotton gloves on
6-9-81.
-
Participants 7 and 10
are brothers.
—
-
Personal air sampler
on 6-10-81 malfunctioned
after 30 minutes.
-------
394
thought to be too hot and restrictive to the participants. Due to the
temperature (95°F+) and humidity (70**) during the two days of study, the
paper jackets and gloves were saturated with perspiration after one hour.
Assessment of Dermal Exposure - Each participant wore a long sleeve disposable paper
jacket (Tyvek 14). Affixed to each jacket were seven 2"x 2" -8 ply gauze
(pre-extracted with acetone) with glassine backing; one on each forearm,
breast and shoulder and one square'on the center of the back. The pur-
pose of the gauze squares was to trap dislodgeable residue from the plants
and soil that were released as a result of the workers physical activity
in the field. The glassine backing prohibited gauze contamination from
skin oils and perspiration absorbed through the jacket. The gauze squares
were removed from the jackets at the completion of the monitoring periods
and were pooled into three samples (forearms, chest and shoulder) with
the back square remaining separate. All samples were wrapped in aluminum
foil and were frozen prior to analyses.
Translocated residue from tomato surfaces to the workers' hands was
assessed through the analyses of 1002 cotton gloves worn by the partici-
pants during their exposure monitoring periods. Affixed to the back of
each glove was a 2" x 2"-8 ply gauze square with glassine backing. It
was anticipated that the gauze would avoid much of the contamination
expected from tomato resin, dirt, skin oils, etc. The gloves were laun-
dered, rinsed in distilled water, and then extracted with the gauze pads
(acetone) prior to use. At the completion of monitoring, the participants'
gloves were removed, v/rapped in aluminum foil and frozen. The gloves
and gauze pads from each participant were combined separately for analyse^.
-7-
-------
395
Assessment of Respiratory Exposure - Each participant wore a DuPont P-2500
Personal Air Sampler, precalibrated at 1.5 liters/minute, or a Si pin
103 Personal Air Sampler, precalibrated at 1.5 liters/minute, through-
out his monitored exposure. A sampling train consisting of a 37 mm
cassette with a Millipore glass fiber filter (.3 micron pore size)
followed by a custom made XAD-4 resin sorbent tube (500 mg) was utilized.
The sampling media were chemically extracted (hexane/acetone/diethyl
ether) prior to use. Start and stop times (plus stroke counter readings
for the Sipins) of the air samplers were recorded for subsequent air
volume calculations. The flow control light-emitting diodes of the
samplers were monitored to insure that proper flow had been maintained.
At the end of the monitoring period, each air sampling medium was
wrapped in aluminum foil and frozen prior to analysis.
High volume air sampling (20 f /m) was also conducted at each
field during the two days of study. Two Staplex High Volume Air Samplers
(Model TF1A), calibrated prior to use, were placed side by side in each
field to sample air for one hour each day of study. This sampling
occurred immediately after the participant monitoring. The purpose for
placing the high volume air samplers next to each other was to have
one serve as a quality control check for the other. The air samplers
were positioned approximately 100 feet into the fields (Figure 1). AC
power was supplied by a 1700 watt Homelite portable generator. The
sampling train consisted of a 4.0" diameter glass fiber filter for
particulates followed by approximately 100 ml of XAD-4 resin for vapors.
Both media were chemically extracted (hexane/acetone/diethyl ether)
prior to use. After sampling, the filters were individually wrapped
in aluminum foil and frozen prior to analyses.
-8-
-------
396
The resin was transferred to amber colored glass bottles, capped with
aluminum foil lined lids and frozen.
Assessment of Foliage Residues - Ten composite foliage samples were collected,
five from the shed field and five from the north field. The samples
were collected immediately after the participant monitoring periods.
Samples were obtained by leaf punch (Norman F. Willett, Colonial Beach,
Va. - patent pending) and were collected in amber colored glass jars
prerinsed with acetone. Each composite sample was composed of 50 discs
(each 2.54 cm in diameter) punched from the tomato leaves in a pre-
determined manner as outlined in Appendix B. This sampling scheme
provided the flexibility needed to fit any site and yet insure repre-
sentative samples for pesticide residue analyses. As each sample was
completed, the glass jar was removed from the leaf punch and capped
with an aluminum foil lined lid. All samples were frozen prior to
analyses.
Assessment of Soil Residue - Five composite soil samples were collected from the
shed field on June 9 and five composite samples were collected from
the north field on June 10. The same alley sampling points as used
for the foliage collection (Appendix B) were selected for soil sampling.
At each alley sampling point, no less than 10 grams of soil were collect-
ed from the center of the alley at each of the five sampling segments.
Thus, a minimum of 50 grams of soil was collected for each composite
sample. Samples were collected from the top half-inch of soil by a
stainless steel scoop and placed in an amber colored glass jar prerinsed
with acetone. Lids were lined with aluminum foil and all samples were
frozen prior to analyses. At the time of analysis, each sample was well
mixed and a 20 gram subsample was separated for residue determination.
-9-
-------
397
Meterological Data - The following observations were recorded during the two
monitoring periods: 1) maximum temperature, 2) relative humidity,
3) barometric pressure, 4) wind speed, direction and condition, 5)
percent cloud cover and, 6), soil temperature.
Endosulfan Residue Analysis - Analyses of all sample extracts were conducted on
Tracer Model 220 Gas Chromatographs equipped with dual column, dual
Tritium Electron Capture detectors with dual pen strip chart recorders.
Qualitative and quantitative analyses were carried out on Column I with
all extracts being reinjected simultaneously on Column II for second
Column confirmation of the presence or absence of endosulfan.
Gas chromatographic columns used in the analysis were:
Column I: 4 mm ID x 6 mm 00 x 183 cm. Glass packed with 1.57% OV-17/
1.95% OV-210 on 80/100 mesh gas chrom Q, Carrier N2 at
60 cc/min.
Column II: 4 mm ID x 6 mm OD x 183 cm. Glass packed with 4% SE-30/
6% OV-210 on 80/100 mesh gas chrom Q, carrier Ng at 80 cc/min.
GLC operating parameters were as follows:
Injection port temp. = 225°Cj detector temp = 210°C; Column oven = 200°C;
transfer section temp = 230°C; chart speed 0.25 in/min; electrometer
attentuation (Tracer E-2) 10 x 16.
Quantitative analysis was performed by comparing sample peak height
to analytical standard peak height that was t_ 10% of the sample.
The reference for the analytical procedures throughout this study
was the "Manual of Analytical Methods for the Analysis of Pesticides
in Human and Environmental Samples (EPA-600/8-80-038) June 1980".
Quality Assurance - Appendix C reports the quality assurance plan and results.
-10-
-------
398
RESULTS;
Day 1. The results of the Day 1 participant monitoring are listed in Table 2.
All cotton glove samples contained endosulfan residue which ranged from
a low of 42,708 nanograms (ng) in the adult group to a high of 228,741
ng observed in the juvenile participants. The juvenile cohort averaged
twice as much residue (X= 117,234 ng) in their cotton gloves as compared
to the gloves worn by the adults (X= 76,072 ng). Likewise, the gauze
•
squares attached to the backs of the juvenile gloves were found to
contain over three times the average residue recovered from the samples
of the adult participants.
Nine of the 40 gauze square samples which were attached to the fore-
arms, chests, shoulders and backs of the disposable paper jackets worn by
the participants had no detectable endosulfan residues. The back gauze
squares suggest that the surface area of the back has the least potential
for dermal exposure as four of the five juvenile samples and two of the
five adult samples had no detectable residues. The average residues of
the forearm, chest and back gauze square samples of the adult group were
respectively 11, 8, and 5 times greater than the corresponding juvenile
samples. The shoulder gauze squares represented the only body surface
2
samples of the juveniles (7=2.02 ng/cm ) which exceeded the average
__ . 2
residue found in the adult group (X=0.36 ng/cm ).
The results of the Day 1 personal air sampling suggest the adults
had greater potential for respiratory exposure. The adults wore the
DuPont P-4,000 personal air samplers and the juveniles wore the Si pin 103
personal air samplers and all were calibrated at 1.5 1/m. The combined
-11-
-------
Table 2
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Tomato Harvesters to Endosulfan - Charleston County, South Carolina 1981
Results -Day 1 (6-9-81) Participant Monitoringt
Participant
I.D.
1
2
H 3
5 ft
" 5
6
w 7
W g
j 8
£2 9
| 10
Cotton
Gloves
(ng)
47,962
87,101
126,515
42,708
NS
X-76,072
94,311
77,159
228,741
97,122
88,838
X-117,234
2 2
Gauze Squares (ng/cm )
Gloves
62.35
128.29
38.30
71.80
—
X- 75.19
590.47
104.09
436.71
15.97
155.77
£-260.60
Forearms
4.06
1.58
23.64
ND
15.86
X- 9.03
3.08
ND
0.57
0.17
0.26
X- 0.82
Shoulders
0.65
0.12
0.41
0.32
0.29
X- 0.36
1.12
0.19
3.2g
SC°
3.50
X- 2.02
Chest
3.93
0.51
24.46
0.77
13.66
X- 8.67
ND
0.84
0.77
1.03
2.49
X- 1.03
Back
ND
2.05
0.30
ND
0.77
7- 0.62
ND
0.53
ND
ND
ND
X~= 0.12
3 *""
Personal Air Sample
GF Filte
(ng/ni )
103.32
68.10
45.92
14.35
64.16
X-59.17
181.54
22.18
81.92
22.83
81.34
X- 77.96
XAD-4 Resin
(ne/m3)
63.01
157.71
117.51
13.50
107.41
X-91.83
39.5
ND
28.67
ND
30.08
X- 19.65
Tot^l
(ng/m )
166.33
225.81
163.43
27.85
171.57
7-151.00
221.04
22.18
110.59
22.83
111.42
3C- 97.61
Total
(ng/D
0.17
0.23
0.16
0.03 ,
0.17
X~ - 0.15
0.22
0.02
0.11
0.02
0.11
x" - o.io
limit of detection - 5-0 ng/pair
2Lower limit of detection - 0.1 ng/cm ; Results adjusted for X QA of 66%
3Lower limit of detection - 5.0 ng/m3; Results adjusted for jf QA of 89% for GF filter and X QA of 69% for XAD-4 Resin.
NS - No Sample, participant refused to wear gloves
ND - None Detected
SC - Sample Contaminated
sO
-------
400
residues recovered from the glass fiber filters and XAD-4 sorbent tubes
of the adults averaged 151.0 ng/m while the juvenile participants
average was 35% lower (97.61 ng/m ).
Table 4 lists the results of the Day 1 environmental sampling.
Endosulfan was detected in the soil, foliage, and air of the tomato
field in which the participants were working. All samples contained
measureable quantities of endosulfan except for one soil sample. The
average residue of the high volume air samples (82.44 ng/m ) was less
than the averages reported for the personal air samples of the adults
and juveniles.
Meteorologic observations during Day 1 monitoring were as follows:
1. Maximum temperature - 95°F
2. Relative humidity - 75%
3. Barometric pressure - 30.00
4. Wind speed and direction - 0
5. Percent cloud cover - 0
6. Soil temperature - 90°F
Day 2. The results of the Day 2 participant monitoring are reported in Table 3.
All samples contained quantifiable levels of endosulfan. Residues
recovered from the cotton gloves ranged from 92,943 ng (adult) to 394,560
ng (adult). As observed on Day 1, the juvenile cotton gloves averaged
a greater residue (271,027 ng) than the adult gloves (234,173 ng). It
is interesting to note that on both days of study, the juvenile average
glove residue exceeded the adult glove residue by approximately 40,000 ng.
The greater glove residues observed on Day 2 may be explained by the
fact that the participants entered the field earlier in the morning while
-13-
-------
Table 3
Dermal and Respiratory Exposure Assessment of Adult and Juvanile
Tomato Harvesters to Endosulfan - Charleston County, South Carolina 1981
Results - Day 2 (6-10-81) Participant Monitoring
Participant
I.D.
1
2
H 3
d 4
3 5
6
nj 7
g 8
5 9
^ 10
Cotton
(ng)
92,943
259,980
118,399
304,981
394,560
X-234,173
164,130
284,727
238,676
360,679
306,923
X-271,027
2 2
Gauze Squar
-------
402
Table 4
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Tomato Harvesters to Endosulfan - Charleston County, South Carolina 1981
Environmental Monitoring Endosulfan Results
Day 1 Day 2
(6-9-81) (6-10-81)
Shed Field North Field
Soil (ng/mg) ;
Sample 1 ND* 6.37
.Sample 2 0.65 1.53
Sample 3 5.32 7.17
Sample 4 4.80 10.55
Sample 5 7.01 (X - 3.56) 18.13 (X- 8.75)
2
Foliage (ng/mg) ;
Sample 1 12.70 19.39
Sample 2 7.52 14.04
Sample 3 5.07 14.65
Sample 4 35.18 20.31
Sample 5 17.64 (X-15.62) 14.25 (X-16.53)
Air (ng/m3)3;
High Volume #1
GF Filter 14.82 161.30
XAD-4 Resin +77.32 + 437.30
Total 92.14 598.60
High Volume 02
GF Filter 17.81 93.21
XAD-4 Resin +54.92 + 555.85
Total 72.73 (X-82.44) 649.06 (X-623.83)
Lower limit of detection * 0.50 ng/mg; Results not adjusted as X QA « 100%
2Lower limit of detection « 0.50 ng/mg; Results adjusted for X" QA - 83%
3 3 —
Lower limit of detection « 0.50 ng/m ; Results not adjusted as X QA * 99%
L
ND » None Detected
-15-
-------
403
the tomato plants were still damp with dew. Thus, the gloves were absorb-
ing moisture from the tomatoes, leaves and vines which provided a poten-
tially greater source of exposure than would be obtained from the same
plants under dry conditions.
The gauze squares representing the participants' forearms, shoulders,
chests and backs averaged higher residues than were observed on Day 1
except for the adult group's forearm and chest samples. The back gauze
squares again suggest that the surface area of the back has the least
potential for dermal exposure as they represented the lowest average
2 2
residues for the juveniles (1.29 ng/on ) and the adults (1.36 ng/cm ).
The juveniles averaged greater forearm and chest residues than the adults
while the latter group was shown to have higher shoulder and back residues.
The forearm gauze square average residues were the highest of the body
2
surface samples for the adults (5.64 ng/cm ) and also for the juveniles
2
(6.21 ng/cm ). This would not be unexpected as the workers' forearms
have more frequent contact with the foliage.
The personal air sampling results of Day 2 document a higher respiratory
exposure for the participants than they experienced during Day 1 monitoring.
Again the adults appear to have had a potential for greater respiratory
exposure than the juveniles: 312.81 ng/m as compared to 247.64 ng/m ,
a 25% difference. The personal air samplers were recalibrated prior to
use on Day 2 and the adults utilized the DuPont P-4,000s while the juveniles
wore the Sipin 103's.
Table 4 reports the results of the Day 2 environmental sampling with
endosulfan being detected in all soil, foliage and air samples. Slightly
higher residues were recovered in the soil and foliage samples as compared
to Day 1, however, the high volume air samples averaged almost eight times
-16-
-------
404
the amount of residue as was observed in the first day sampling.
Meteorologic observations during Day 2 monitoring were as follows:
1. Maximum temperature - 96 F
2. Relative humidity - 72%
3. Barometric pressure - 30.00
4. Wind speed and direction - 0
'5. Percent cloud cover - 0
6. Soil temperature - 90°F
DISCUSSION:
The assessment of a worker's exposure to a particular pesticide must
include measurements of the dermal and respiratory levels to which he is exposed.
Results of these measurements (gauze squares attached to various body locations,
cotton gloves and personal air samples) are used to calculate a worker's potential
total exposure on an hourly basis as recommended by Davis (1981). Calculations
derived from the total hourly exposure estimate may then be used to express
^the exposure in terms of an estimated toxic dosage (Durham and Wolfe, 1962).
Assessment of Dermal Exposure. The total hourly dermal exposure of a worker is
the sum of the hourly exposures for the worker's unprotected body regions (face,
neck, forearms if wearing a short sleeve shirt, etc.) plus the hourly exposure
of the hands. The gauze squares attached to the worker during monitoring are used
to represent the unprotected regions of the worker's body. The residue per unit
area of the gauze squares selected to represent an unprotected body area is then
multiplied by the surface area of that body region. Estimates of total body
surface area and unprotected body regions are listed for each participant in
Table 5.
It is assumed that clothing, except gloves, provides 100* protection
to the worker. In this study, total dermal exposure is considered to be the total
-17-
-------
Table 5 4Q5
Estimated Body Surface Areas and Minute Ventilation Rates
Participant
1
2
10 3
=* 4
•* 5
6
7
CO p
UJ O
1
z 9
UJ
= 10
-3
Total BSA1
(cm2)
19,000
19,500
17,000
18,000
16,000
15,500
16,000
17,000
16,000
15,500
Face & Neck2
(cm2)
1,045
1,072
935
990
880
1,008
1,040
1,105
1,040
1,008
3
Forearms
(cm2)
1,140
1,170
1,020
1,080
960
930
960
1,020
960
930
Minute Ventilation4'5
(1/m)
16.0
16.0
16.0
30.0
16.0
28.6
28.6
28.6
28.6
28.6
BSA = Body Surface Area. Estimated for each participant based upon height and
weight from surface area nomogram by Gehan and George (1970).
2
5.5% of BSA for adults and 6.5% of BSA for a 15 year old (juvenile estimates).
From Lund and Browder chart for estimating extent of burns - Artz and Moncrief (IS
6% of BSA for adults and juveniles (Artz and Moncrief)
A
Adult male and female fruit thinners or pickers: 30.0 1/m and 16.0 1/m respectively.
EPA-600/8-80-038 (1980).
28.6 1/m for young male athletes peforming light work. Hayes (1975).
-18-
-------
406
of the estimated exposure to the face and neck, forearms and hands. The average
residue recovered from each participant's shoulder, chest and back gauze square
samples are used to calculate the estimated exposure of the head and neck.
The forearm gauze squares are ' used for the estimation of that body region
while the total residue from each participant's gloves are used for the esti-
mate of exposure to the hands. Although participants 3 and 4 wore short pants
during monitoring, no estimates of lower leg exposure are made. This is neces-
sary in order to avoid bias when their exposure is compared to the other workers
who did not wear short pants.
The following example illustrates the calculations to derive the total
hourly dermal exposure to endosulfan of participant #1 from the results of his"
Day 1 monitoring:
_ 2
1. Face and neck (estimated from X residue/cm of shoulder, chest and
back gauze squares):
222 2
a) 0.65 ng/cm + 3.93 ng/cm + 0.0 ng/cm i. 3 = 1.53 ng/cm
2 2
b) 1.53 ng/cm x 1,045 cm surface area = 1,599 ng/hour
2. Forearms:
2 2
4.06 ng/cm x 1,140 cm surface area = 4,628 ng/hour
3. Hands:
47,962 ng received from the cotton gloves
4. Total dermal exposure for participant #l/Day 1:
1,599 ng/hour face and neck
4,628 ng/hour forearms
47,962 ng/hour hands
54,189 ng/hour
Assessment of Respiratory Exposure. The hourly respiratory exposure is the sum
of the endosulfan residues recovered from the glass fiber filter and XAD-4 sorbent
-19-
-------
407
media of the participant's personal air sample (converted to residue per liter
of air sampled) multiplied by the estimated ventilation rate for the participant.
Estimates of the participant's lung ventilation for light to moderate
work are required in order to calculate hourly respiratory expsoure. Rates for
adults by occupation are available, however, data for normal (healthy) children
are scarce and when available the rates are reported for "resting" conditions.
Minute ventilation for adult male and female fruit thinners or pickers have been
reported as 29.0 - 30.0 1/m and 16.0 1/m respectively (EPA-600/8-80-038 (1980)).
The same EPA publication reports the resting ventilation rate for adult males at
7.0 1/m which coincides with data summarized by Polgar and Promadhat (1971) for
males age 10-17. Young male athletes performing light work have been reported-to
average 28.6 1/m (Hayes, 1975) which approximates the lung ventilation of adult
male pickers. The rate of 28.6 1/m will be used in the calculations of the male
juvenile potato harvester's respiratory exposure. Table 5 lists the estimated rates
for the ten participants of study.
The following calculations demonstrate the estimated hourly exposure of
participant #1 as a result of the Day 1 monitoring:
1. Endosulfan recovered from the participant's personal air
sample = 0.17 ncj/1.
2. Hourly ventilation of participant #1 (adult female):
16.0 1/m x 60 m/hour = 960 I/hour
3. Hourly endosulfan respiratory exposure:
0.17 ng/1 x 960 I/hour = 163 ng/hour
Total Hourly Exposure. Participant #1 during Day 1 monitoring has been shown to
have a total dermal exposure of 54,189 ng/hour. The total hourly exposure would
be this total plus her Day 1 respiratory exposure:
-20-
-------
54,189 ng/hour (dermal)
+ 163 ng/hour (respiratory)
54,352 ng/hour Total
These figures demonstrate that dermal exposure is generally much greater than
respiratory exposure which is in agreement with Hayes (1975). In the case of
participant #1, respiratory exposure accounted for only 0.3% of her total hourly
estimate. Wolfe et al. (1967) reported that respiratory exposure ranged from
0.02% to 5.8% (T = 0.75%) of the total exposure for a number of pesticides.
Table 6 lists the dermal, respiratory and total hourly exposures of the
ten participants during the two days of study. The participants' exposure to
endosulfan is shown to be predominantly dermal with the hands being the primary
route of exposure. This is not surprising as Davis (1981) reported that in nearly
all studies of occupational exposure to pesticides, approximately 90% of the
dermal exposure is found in the hands.
The potential hazard of exposure to a pesticide is limited by the toxicity
of the chemical, the route of exposure and dosage. An objective method to relate
these factors to data reported in exposure studies is to express exposure as a
percentage of the toxic dose (Durham and Wolfe, 1962). Estimates for the parti-
cipants of this study have been made and are included in Table 6. These are
estimates of the dermal toxic dosage based on the lowest reported dose of 74 mg/kg
in rats (NIOSH, 1977). It must be stressed that these figures are estimates only
because of the various parameters involved. For example, these calculations assume
that 100% absorption occurred. The use of animal models to extrapolate toxic dosages
for humans must similarly be viewed with reservations.
Results of the extrapolations are reported in percent of the toxic dose
per hour of exposure. Each of the juveniles and all of the adults, except for
-21-
-------
Table 6
409
Dermal, Respiratory and Total Hourly Exposure of Adult and
Juvenile Tomato Harvesters to Endosulfan - Charleston County, S.C. 1981
Day 1 (6-9-81):
Participant
I.D.
1
co 2
3 3
g 4
53 5
CO 6
a 7
55 8
§ 9
s| 10
Hourly Dermal
Face
& Neck
1,599
954
7,845
359
4,312
376
541
1,481
357
2,006
+
Fore-
arms
4,628
1,849
24,113
0
15,226
2,864
0
581
163
242
+
Exposure (ng/hr)
Hands
47,962
87,101
126,515
42,708,
76,072"
94,311
77,159
128,741
97,122
88,838
-
Total
54,189
89,904
158,473
43,067
95,610
97,551
77,700
230,803
97,642
91,086
Day 2 (6-10-81);
CO
i
co
u
M
Ed
3
1
2
3
4
5
6
7
8
9
10
2,842
2,637
3,684
2,148
3,071
1,976
3,318
4,166
3,276
3,780
Hourly
Resp.
Exposure
(ng/hr)
163
221
154
54
163
378
34
189
34
189
«
Total
Hourly
Expos.
(ng/hr)
54,342
90,125
158,627
43,121
95,773
97,929
77,734
230,992
97,676
91,275
-
Percent
of Tori
Dose
Per Hr.
0.0010
0.0017
0.0034
0.0008
0.0022
0.0025
0.0019
0.0052
O.OQ24
0.0023
4,059
3,030
13,311
6,458
2,890
2,344
4,627
2,877
1,008
12,034
92,943
159,980
118,399
304,981
394,560
164,130
284,727
238,676
360,679
306,923
99,844
265,647
135,394
313,587
400,521
168,450
292,672
245,719
364,963
322,737
240
250
250
504
499
326
463
463
429,
420
100,084
265,897
135,644
314,091
401,020
168,776
293,135
246,182
365,392
323,157
0.0019
0.0049
0.0029
0.0062
0.0093
0.0043
0.0072
0.0055
0.0089
0.0082
Calculated by formula of Durham and Wolfe (1962) for each participant:
% Toxic dose /hour
Dermal Exposure (mg/hr)+CRespiratory Exposure (mg/hr) x
Dermal LDen (mg/kg) x Body weight (kg)
X 100
The factor of 10 is used empirically as respiratory toxicity data are imprecise. This
adjustment factor is employed to adjust for the more rapid and complete absorptioi
of respiratory doses. The dermal LD - 74 tag/kg (NIOSH, 1977).
"JC hourly hand exposure of participants 1, 2, 3, and 4 Day 1.
^f hourly respiratory rate of participants 6, 7, 8, and 9 Day 2.
-22-
-------
410
for participant #3, are shown to have received a slightly higher toxic dose per
hour on Day 2 than on Day 1. During both days of study, the adults received from
0.00102 to 0.0093% of the toxic dose per hour while the juveniles received from
0.0019% to 0.0089%. Assuming that 100% of the dose is required for a toxic
reaction, the adults had a safety margin ranging from 10,000 to 100,000 while the
juveniles ranged from 10,000 to 50,000 per hour of exposure. Participant #5 of the
adult group and participant #9 of the juveniles had the highest estimated toxic
doses both of which occurred on Day 2. If their doses are adjusted for a ten hour
work day (.0093% x 10 = .093% and .0089% x 10 - .089%), their safety factors would
equate to approximately 1,000.
In order to compare the exposures of juveniles and adults to endosulfan,
the two-sample t-test was employed. Measurements taken were the average percent
of the toxic dose per hour, over the two days of study. Although the average
percent toxic dose per hour appeared to be higher in juveniles, X" » 0,0048% as
compared to 7=0.0034% in adults, the difference was not statistically significant
(t = 1.89, df = 8, p = 0.096). Reanalysis for each day separately, comparing the
two groups, is even less significant (t = 1.38, t = 1.19). A possible reason for
lack of significance-1s the substantial variability observed between individuals
(s • 0.0012 on Day 1 and s « 0.0024 on Day 2).
CONCLUSIONS;
Data presented in this report documented the minimal exposure of the adult
and juvenile harvesters to endosulfan 24 hours after application to the tomato
fields of study. .Respiratory exposure contributed little to the total exposure of
the participants. As expected, the hands accounted for almost all of the dermal
exposure. When exposures were compared to estimated toxic dosages, it was seen
that the participants were receiving less than a few parts per thousandths of one
-23-
-------
A\\
percent of the doses per hour. No statistical difference was observed between
the juvenile and adult toxic doses per hour.
The findings of this study suggest that juvenile tomato harvesters are
not being unduly exposed to endosulfan during harvest.
-24-
-------
412
REFERENCES:
Agricultural Chemicals and Pesticides: A subfile of the Registry of Toxic
Effects of Chemical Substances, 1977. DREW (NIOSH) Publication No. 77-180.
Davis, J.E. Minimizing Occupational Exposure to Pesticides: Personnel Monitoring.
Residue Reviews, 75:33-50 (1981).
Hayes, W.L. Toxicology of Pesticides. Baltimore: The Williams and Wilkins and
Company (1975).
Durham, W.F. and H.R. Wolfe. Measurement of the Exposure of Workers to Pesticides,
Bull. WHO, 26, 75, 1962.
Manual of Analytical Methods for the Analysis of Pesticides in Humans and Envi-
ronmental Samples, U.S. EPA, Health Effects Research Laboratory, Research
Triangle Park, N.C. EPA-600/8-80-038 (1980).
Polgar, G. and V. Promadhat. Pulmonary Function Testing in Children: Techniques
and Standards. Philadelphia: W. B. Saunders Company (1971).
Wolfe, H. R., Durham, W. F. and Armstrong, J. F. Exposure of Workers to Pesti-
cides. Arch. Environ. Health, 14:622-623 (1967).
Gehan and George. Cancer Chemotherapy Reports, 54:225,(1970).
Artz, C. P. and J. A. Moncrief. The Treatment of Burns, ed. 2. W.B. Saunders
Company, (1969).
-25-
-------
Appendix A
413
Approved Pesticides for South Carolina Tomatoes, 1981
Insecticides
Azinphosmethyl
Bacillus thuringiensis
Carbaryl
Demeton
Diazinon
Dicofol
Disulfoton
Endosulfan
Ethion
Methamidophos
Me thorny!
Monocrotophos
Oxamyl
Parathion
Toxaphene
Trichlorfon
Fungicides
Anilazine
Benomyl
Chiorothaionil
Fixed Copper
Mancozeb
Ma neb
Herbicides
Diphenamid
Methyl bromide
Metribuzin
Napropamide
Pebulate
Trifluralin
Nematocides
DD Soil Funrigant
Ethylene Di bro-
mide
26
-i-
-------
414
APPFNDIX D
FOLIAGE SAMPLING:
1. The field selected for sampling will be diagramed show-
ing the length and width in approximate dimensions. The
number of crop rows will be determined as well as the
spacing between rows, the spacing between the plants and
plant height.
2. Dependent upon the number of crop rows in the field of
study, five alleys(one for each composite sample) will
be designated as sampling points. Sampling point #3
will be the alley of midfield while sampling points #1 &
#2 and #4 & #5 will respectively be on each side of 13
and equidistant from each other to the end row.
3. At each of the five sampling points(alleys) leaf punches
from foliage on each side of the alley along the length
of the crop rows will be collected as shown:
-X X K 'ri-
-X-
KEY: > = alley sampling point
—— = crop row
x = sample plant
The rows will be divided into five equal segments and
one plant in the center of each segment from the rows
on each side of the sampling alley will be selected for
collection as follows: I
alley row ^* "^ row alley
27 7
sampling' point
Five leaf punches will be taken from each plant. One punch
from the top foliage, tv/o punches on each side of the plant
at mid height and two punches on each side of the plant
-------
Appendix B
415
at the lowest foliage point. Thus for each segment
of the alley sampling point, ten leaf punches will
be collected and ten leaf punches x five segments =
fifty leaf punches per composite sample.
Soil Sampling: Five composite soil samples will be collected
at the monitoring site on each sampling day from the same alley
sampling points selected for foliage sampling. At each sampling
point, no less than 10 grams of soil will be collected from the
center of the alley at each of the five sampling segments. Thus,
a minimum of 50 gm of soil will be collected for each composite
sample. Samples will be collected from the top half inch of
soil by a stainless steel scoop and placed in an amber colored
glass jar prerinsed with acetone. Lids will be lined with alu-
minum foil. Samples will be frozen prior to analyses. At the
time of analysis, each sample will be well mixed and a 20 gm
sub-sample will be separated for residue determination.
28
-2B-
-------
416
Appendix C
Laboratory Quality Assurance - Quality Assurance for this study was
established through three procedures. First, blanks and spikes of the
sample media (gauze squares, XAD-resin and glass fiber filters) were pre-
pared at the time of the field studies and were frozen along with the
collected samples until analysis. The purpose of this procedure was to
demonstrate the stability of the spike-samples fortified with nanogram
levels of endosulfan as a reference to the stability of the collected
samples.
The second and third procedures, approved by the QA Officer/HEB,
established interlaboratory quality control between the SC and MS PHAP
laboratories and provided the in-house quality control for the SC PHAP.
The MS PHAP laboratory was responsible for spiking several substrates for
endosulfan QA analyses by the SC PHAP laboratory. Additionally, the SC
PHAP analyzed a reagent blank for every 10 field samples. The following
table lists the number of field samples, the type of samples and the number
of QA samples analyzed.
Samples Collected Endosulfan QA Samples
n
99
20
20
4
10
10
19
4
Description
Gauze squares
PAS XAD-4
PAS GF filters
Hi-Vol 6F filters
Leaves
Soil
Cotton gloves
Hi-Vol XAD-4
Spiked
SC
13
3
4
2
2
2
-
-
Samples
MS Split*
1
1
1
1
2
2
4
2
186 26 8 6
*Randomly selected sample extracts were split and forwarded by SC to the
* MS PHAP for dual analyses.
" -3A-
-------
Appendix C 4 i '
The first spiked sample of each medium (except those being split
for dual analyses) were analyzed as an unknown by both laboratories.- The
remaining QA samples of each medium, spiked at the same level as the unknown,
were used by the SC PHAP laboratory for in-house quality control and by
the MS PHAP laboratory for inter-laboratory quality control.
Table 1 lists the results of study QA analyses and Table 2
reports the findings of the inter-laboratory analyses. Included in Table
1 are the average percent recovery and relative standard deviation for
each substrate. These are also plotted in Figure 1. The split samples
(cotton gloves and Hi Vol XAD-4) are also listed in Table 1.
Table 3 lists the results of field spikes. All six samples
demonstrated excellent stability during freezer storage.
30
-3B-
-------
Appendix C
Table 1
QA Results
418
QA Substrate
Gauze Squares
Spike Gig)
Recovered
PAS XAD-4
Spike big)
Recovered
FAS GF Filters
Spike Gig)
Recovered
Hi-Vol GF
Filters
Spike Gig)
Recovered
110
6.50
6.50
6.50
4.56
6.50
4.04
6.50
6.50
4.34
6.50
4.07
X Rec
RSD •
6.50
4.28
6.50
4.26
- 66Z
6.50
4.39
6.50
3.99
6.50
4.24
4.49
4.56
4.02
svery
4.81
3.50
3.50
3.50
2.50
• 69%
2.22
2.52
X Rec
>very
7.30
RSD
3.00
2.21
3.00
3.00
3.11
2.70
X Rec
Dvery
16.6
RSD
-
7.00
6.88
7.00
6.90
X Rec
RSD
5 very
0.50
8.00
6.70
8.00
6.55
X Rec
RSD -
>very
3.55
12.0C
12.00
12.37
X Rec
RSD -
11.64
100Z
>veryl
3.06
0.78
1.09 1.90
1.83
0.79
2.12
1.86
1.08
9.23
7.68
Leaves
Spike Gig)
Recovered
Spike Gig)
Recovered
Split Samples
Cotton Cloves
SC Recovery
bg>
MS Recovery
dig)
Hi-Vol XAD-4
SC Recovery
0>g)
MS Recovery
Gig)
1.87
1.91
-------
Appendix C
Table 2
Inter!aboratory QA Results
419
Spiking Level
SC PHAP
* Recovered
% Recovery
MS PHAP
Recovered
% Recovery
Gauze
Squares
6.50 yg
4.07
63
4.11
63
PAS
XAD-4
3.50 yg
2.22
63
2.50
71
PAS GF
Filter
3.00 yg
2.70
90
2.73
91
Hi-Vol
Filter
7.00 yg
6.90
99
6.72
96
Lei
n
8.00 yg
6.55
82
6.40
80
ves
#2
8.00 yg
6.70
84
6.80
85
Soil
#1
12.00 yc
12.37
103
11.76
98
#2
12.00 yc
11.64
97
11.52
96
Table 3
Field Spikes
Medium
PAS GF Filter #1
" " " #2
Gauze Square #1
#2
Hi-Vol GF Filter rfl
% Recovery
89.93
95.51
89.05
83.38
95.23
95.14
32
-30-
-------
Appendix C
Figure 1
i*!*":-:^'-1:::;*:
/^ |:— .-- . -. .- i
/t , • RSD 7
llfii
-------
421
Assessment of Dermal and Respiratory Exposure
of Adult and Juvenile Blueberry Harvesters
to ULV Malathlon, Duplln County, North
Carolina 1982
Research performed by
Medical University of South Carolina
January 16, 1984
-------
422
Table of Contents
Title Page
Abstract 11
List of Tables Ill
I. Objective 1
II. Background . 1
III. Methods 2
IV. Analytical Procedures 12
V. Quality Assurance 14
VI. Results 18
VII. Discussion 37
VIII. References 38
-------
423
Abstract
Sixteen juvenile (age 12-15) and fourteen adult (age 19-66) blueberry
harvesters were monitored on two consecutive days for their dermal and
respiratory exposure to ULV malathion in order to determine if there were
any differences between the exposure patterns of these two groups.
Assessment of dermal exposure consisted of cotton gloves for the hands
and gauze squares attached to the forearms, chest, shoulders and back of
each worker. Each participant also wore a personal air sampler during
monitoring. Urine samples were collected from each worker in order to
determine whether exposure resulted in the absorption and excretion of
the chemical of study.
Statistical analyses of malathion residues recovered from the sampling
media found no significant differences between the dermal and respiratory
exposure patterns of the juveniles and adults. Significant differences
were observed in the alkyl phosphate metabolites recovered from the parti-
cipants' urine samples. The average residues of the juveniles were
approximately three times greater than those of the adults. Reasons for
this difference include higher metabolic rates for juveniles as compared
to adults and the observation that the juveniles of study ingested more
blueberries than the adults. The surface area of the blueberries were
found to have quantifiable malathion residues.
Environmental monitoring consisting of high volume air sampling and
composite sampling of soil, leaves and blueberries was performed to
document the presence of malathion during participant monitoring.
ii
-------
424
List of Tables
Table No. Title Page
1. Pesticides Recommended for Use on N.C. Blueberries. . . 4
2. Juvenile Participant Data 6
3. Adult Participant Data 7
4. Intralaboratory Quality Assurance 16
5. Interlaboratory Quality Assurance 17
6. Day 1 (June 7) Juvenile Participant Results 20
7. Day 1 (June 7) Adult Participant Results 21
8. Day 2 (June 8) Juvenile Participant Results 22
9. Day 2 (June 8) Adult Participant Results 23
10. Summary of Participant Results 24
11. Statistical Analyses (t-test) of Juvenile vs.Adult
Sample Media for Each Day of Study 27
12. Statistical Analyses of Juvenile Day 1&2 Results vs.
Adult Day 1&2 Results 28
13. Statistical Analyses of Day 1 vs. Day 2 Participant
Results 30
14. Blueberry Residue Analyses 32
15. Foliage Residue Analyses 33
16. Soil Residue Analyses 34
17. High Volume Air Sample Analyses . .35
IS. Meteorological Observations 36
iii
-------
425
I. Objective;
The objective of this study was to assess the difference, if any,
between the dermal and respiratory exposure patterns of juvenile and
adult blueberry harvesters who, under normal working conditions, had
post application exposure to ultra low volume (ULV) malathion.
II. Background;
The U.S. Environmental Protection Agency (EPA) and the U.S.
Department of Labor (DOL) finalized an interagency agreement on
March 17, 1980. This agreement, "Youth in Agriculture", provided
for the development of pesticide protection programs for farm workers.
The employment of children during the harvest of hand picked crops is
of special concern to the DOL. This agency has the authority to waive
restrictions to permit children to work, however it also must assure
that there are no adverse health effects to the children for which the
exemption was granted. One goal of the interagency agreement is the
determination of scientifically based reentry intervals for children
and the assessment of potential health effects of pesticides on
children working in agriculture.
The EPA and DOL have assumed that the potential for the exposure
of children to toxic chemicals in agriculture is widespread and that
children are generally more sensitive to chemical exposure. Further-
more, children possibly have greater rates of dermal and/or gastro-
intestinal uptake and have decreased capacity for detoxification. Yet,
little or no data exists to support these assumptions as it applies to
field workers. In order to bridge this data gap, it is necessary to
perform studies which measure the pesticide exposure of adult and
juvenile workers to various pesticides during the harvest of a variety
of hand-picked crops. The harvest of North Carolina blueberries requires
extensive hand labor and juveniles (age j> 12) are commonly hired as
-------
pickers and work along with adults. 426
North Carolina is a major East Coast producer of blueberries.
During 1981, approximately 7.2 million pounds of blueberries were
harvested from 3,200 acres. Blueberries grown for fresh market sales
accounted for 80% of the harvest while the remaining 20Z were processed
(canned and frozen). Harvest usually begins in late May and continues
through June. Figure 1 displays the principal blueberry region of
North Carolina. The soil of this area, fine sandy loam, is ideal for
the cultivation of blueberries.
Several varieties of blueberries, which mature at different
intervals throughout the harvest period, are cultivated in order to
have a continuous supply of fresh berries for market. The later
rlppening varieties are grown almost exclusively for processing. The
blueberry bushes range in height from four to over six feet and are
grouped in rows by variety. The School of Agriculture and Life Sciences
of North Carolina State University recommends seven insecticides, three
fungicides and four herbicides for use on blueberries. Table 1 lists
these pesticides along with the minimum intervals between application
and harvest.
III. Methods;
Site - Duplin County is in the center of the North Carolina blueberry
belt (Figure 1) and in 1981 produced 12Z of the total state harvest.
A Duplin County farmer with approximately 100 acres of blueberries
agreed to cooperate with the study and assisted in the recruitment of
participants. His 1982 harvest began on May 26 and eight days later all of
-------
NORTH CAROLINA
Coufttici, County Suit, Mountain*, and Rivtn
I
I
77-
I
FIGURE 1
North Carolina Blueberry Belt
-»*v_
•I-
I
79
?•
-JL.
_>*•-
O
s|
-------
Table 1
428
Pesticides Recommended for Use on
North Carolina Blueberries
Minimum Interval (Days)
Pesticide Between Application and Harvest
Insecticides:
azinphosmethyl 3
carbaryl 0
endosulfan (not to be used after buds are formed)
ethion (post harvest spray)
malathion 1
malathion ULV 0
oil - type 70 second superior (dormant use only)
parathion 14
Fungicides:
benomyl 21
captafol 21
triforine 40
Herbicides:
dichlobenil (not for use after mid-February)
paraquat (spot control prior to harvest)
simazine (prior to budding & post harvest)
terbacil (post harvest application)
+ 1981 North Carolina Agricultural Chemicals Manual
(Prepared by The School of Agriculture and Life
Sciences of North Carolina State University)
-------
429
his fields were sprayed for the control of blueberry maggots.
Application was made by a fixed wing aircraft which sprayed 91Z
active ingredient nalathion (CYTHION - EPA Reg. No. 241-208 AA)
at an ultra low volume rate of 10 ounces per acre.
The spraying took place on Thursday afternoon, June 3, between
the hours of 5:00 - 6:00. It is important to note that a light rain,
about five minutes in duration* occurred at 7:00 P.M. which was followed
by 4.0 inches of rain during the next two days. Friday's rain totaled
1.7" and on Saturday (heavy thunderstorms) the total was 2.3". The
rainfall was recorded from a rain gauge located at the farm.
Participant monitoring took place the following Monday and Tuesday,
June 7. and 8.
Participants - All blueberry harvesters were seasonal workers and were
residents of the surrounding area. Due to the availability of local
workers, migrant laborers were! not required. Participants were recruited
from one of the several harvest crews employed by the cooperating
farmer. The participants recruited for this study are thought to be
representative of the harvester population. It was observed that each
harvest crew was composed predominantly of female workers and approxi-
mately one-half of the workers of each crew were 18 or younger.
Sixteen juveniles (age 12 - 15, five male and eleven female) and
fourteen adults (age 19 - 66 , one male and thirteen female) were
recruited for participation in the study (Tables 2 and 3). According
to DOL regulations, a child under age 12 can not be hired to pick
blueberries. The farmer was careful in complying with this regulation
as labor officials routinely checked the fields for underage workers.
The blueberry harvesters began work around 7:00 in the morning.
Each person was assigned a row or a section of a row for picking.
When rows were completed, the crew would move to other rows ready for
5
-------
Table 2
Juvenile Participant Data
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Blueberry Harvesters to ULV Malathion-Duplin County, North Carolina 1982
430
PARTICIPANT
STUDY
NO.
1
2
4
6
9
14
16
17
18
19
21
22
24
25
26
30
AGE
13
12
12
14
14
12
14
15
14
15
15
14
14
12
12
14
SEX
M
F
F
F
F
M
M
F
F
F
F
F
F
M
F
M
HEIGHT
(cm)
157
150
147
160
160
155
170
170
173
154
155
163
163
150
157
165
WEIGHT
(kg)
52
49
37
50
50
47
69
63
63
59
52
59
61
41
53
77
WORK CLOTHING2
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt & shoes
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt & shoes
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, sneakers
& hat
Jeans, long sleeve shirt, sneakers
& hat
\l Juveniles (Age 12-15) n • 16. All participants were black and were recruited
from a single harvest crew led by participant I 29.
2] None of the study participants or other harvesters wore work gloves.
-------
Table 3
Adult Participant Data
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Blueberry Harvester* to ULV Malathlon-Duplin County, North Carolina 1982
431
PARTICIPANT
STUDY
NO.
3
5
7
8
10
11
12
13
15
20
23
27
28
29
AGE
29
19
26
33
34
23
44
22
66
41
48
59
41
49
SEX
M
F
F
F
F
F
F
F
F
F
F
F
F
F
HEIGHT
(cm)
178
152
165
175
173
152
157
170
160
152
157
163
152
168
WEIGHT
(kft)
79
70
59
78
57
65
86
62
59
73
72
95
104
99
WORK CLOTHING2
Jeans, short sleeve shirt & shoes
Pants , long sleeve shirt & sneakei
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt & shoes
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
Pants, long sleeve shirt, shoes
& hat
Jeans, long sleeve shirt, shoes
& hat
I/ Adults (Age 19-66), n - 14. All participants were black and were recruited
from a single harvest crew led by participant I 29
2J None of the study participants or other harvesters wore work gloves.
-------
432
harvest. The worker picked each ripened blueberry individually
which was then placed into a container tied to the individual's
waist. As the container filled, it was dumped into a wooden pail.
Several times throughout the workday, each worker's wooden pails
were weighed and cash payment was made to the worker.
The thirty participants were monitored, under normal working
conditions, for their dermal and respiratory exposure to malathion
for two hours on June 7 (Day 1) and again for two hours on June 8
(Day 2).
Assessment of Dermal Exposure - Each participant wore a long sleeve
disposable paper jacket (Tyvek 14). Affixed to each jacket were
seven 2" x 2" - 8 ply gauze squares (pre-extracted with acetone) with
glasslne backing; one on each forearm, breast and shoulder and one
square on the center of the back. The purpose of the gauze squares
was to trap dislodgeable residue from the bushes and soil that were
released as a result of the workers1 physical activity in the field.
The glassine backing prohibited gauze contamination from skin oils and
perspiration absorbed through the jacket. The gauze squares were
removed from each Jacket at the completion of monitoring
and were pooled into three samples (forearms, chest and shoulder) with
the back square remaining separate. All samples were wrapped In
aluminum foil, labeled and frozen prior to analyses.
Translocated residue to the workers' hands was assessed through
the analyses of 100% cotton gloves worn by the participants during
their exposure monitoring periods. Affixed to the back of each glove
was a 2" x 2" - 8 ply gauze square with glassIne backing. It was
anticipated that the gauze would avoid much of the contamination
expected from dirt, skin oils, etc. The gloves were laundered,
rinsed in distilled water and then acetone extracted with the gauze
8
-------
433
pads prior to use. At the completion of monitoring, the gauze squares
were removed from the gloves. The gloves and glove gauze of each
participant were pooled separately, wrapped in aluminum foil, labeled
and frozen prior to analyses.
Assessment of Respiratory Exposure - Each participant wore a DuPont
P-4000 Personal Air Sampler, precalibrated at 2.0 liters/minute,
during the two monitoring periods. The sampling train consisted of a
37 mm cassette with a Millipore glass fiber filter (.3 micron pore
size) followed by a custom made XAD-4 resin sorbent tube (500 mg).
The sampling media were chemically extracted with hexane, acetone
and diethylether prior to use. Start and stop times of the air
samplers were recorded for subsequent air volume calculations and
the flow control light-emitting diodes of the air samplers were
monitored to insure that proper flow had been maintained. At the
end of the monitoring periods, each air sampling medium was wrapped
in aluminum foil, labeled and frozen prior to analysis.
Assessment of Absorption - Urine samples were collected from each parti-
cipant to document whether the individual's exposure resulted in absorption
and excretion of the chemical of study. The participants were requested to
collect first morning voids after each day of exposure monitoring. The
first morning voids were collected on June 8 and 9. Samples were collected
in polyethylene bottles which had been washed and rinsed with organic free
water. All specimens were labeled and frozen prior tc analysis.
It was anticipated that the ingestion of blueberries could provide
another potential source of exposure to the participants. After each two
hour monitoring period, the participants were asked if they had eaten
blueberries and if so, an estimate of the quanity was requested. All
participants admitted to and were observed eating blueberries, however
efforts to quantify the amount ingested by participant were unsuccessful.
9
-------
Through observation, Che three on site investigators estimated
that, on the average, adult participants ate at least one cup of
blueberries per monitoring session. The Juvenile rate was estimated
to be slightly higher at Ik to 1% cups.
Environmental Sampling - Collection of soil, blueberry, foliage and
high volume air samples was performed each day from June 5 (Saturday)
through June 8 (Tuesday). The purpose of the environmental sampling
was to document the level of malathion present at the times of partici-
pant monitoring and also to demonstrate degredation over time. A ten
acre field close to the center of the blueberry farm was selected for
sampling. The field consisted of 60 rows which were approximately
eight feet apart. The rows were planted north to south and the blueberry
bushes were spaced about every five feet along the length of the row.
This field was harvested by the participants during the Day 1 exposure
monitoring.
Ten composite samples for each substrate (except air) were
collected each day from the field of study. Each composite sample
was from one row of the field and the ten rows selected for sampling
were determined as follows:
1. The row in the center of the field was located.
2. Sampling rows 1 through 5 were the rows to the right
of mid-field which were equidistant from each other
to the last crop row on the right.
3. Sampling rows 6 through 10 were the rows to the left
of the row of mid-field and were equidistant from each
other to the last crop row on the left.
Along the length of each row selected for sampling, five "collection
points", all equidistant from each other, were designated. Each
collection point was a blueberry bush and samples were collected as
follows:
10
-------
435
1. Blueberries - At each collection point (bush), five
berries were collected; one from the Cop of the bush,
two from mid-height and two from the bottom of the bush.
Thus, 25 berries were collected from the sampling row to
constitute one composite blueberry sample.
2. Foliage - The same collection points used for the blueberry
samples were also used for the sampling of blueberry leaves.
At each bush selected for sampling, four leaves were collected;
one from the top, two at mid height and one from the bottom.
Thus, 20 blueberry leaves composed one composite foliage
sample.
3. Soil - The same collection points were again used for composite
soil sampling. At the base of each sample bush, approximately
100 g of soil were collected from the top half-inch of soil using
a stainless steel scoop. Each composite soil sample contained
approximately 500 g. of soil.
All composite samples were collected in amber colored glass jars which
had been pre-rinsed with acetone. The jar lids were lined with aluminum
foil. All samples were labeled and frozen prior to analysis.
High volume air sampling (20 f /m) was performed each day in the
same field of study. Two Staplex High Volume Air Samplers (Model TF1A),
calibrated prior to use, were placed side by side approximately 50 feet
into the field. The purpose for placing the high volume air samplers
next to each other was to have one serve as a quality control check for
the other. AC power was supplied from a nearby packing shed. Duration
of air sampling was one hour on June 5 and 6. On June 7 and 8 air was
sampled for two hours in order to coincide with the participant monitoring.
Sampling trains consisting of 4.0" diameter glass fiber filters for
participates followed by approximately 100 ml of XAD-4 resin for vapors
11
-------
436
were used. Both media were chemically extracted (hexane/acetone/
diethylether) prior to use. After sampling, the filters were
individually wrapped in aluminum foil, labeled and frozen prior
to analysis. The resin was transferred to amber colored glass jars,
capped with aluminum foil lined lids, labeled and frozen.
Meteorological Data - During each day of study, the following obser-
vations were made: 1) maximum temperature, 2) relative humidity, 3)
barometric pressure, 4) wind speed, direction and condition, 5)
percent cloud cover and 6) rainfall.
IV . Malathion Analytical Methodology:
Analyses of all sample extracts, except urines, were performed
either on a Tracer 220 gas chroma tograph, equipped with a Model 702
Nitrogen-Phosphorus detector and a Tritium Electron Capture detector,
or on a Varian Vista 6000 series gas chromatograph equipped with a
Thermal Specific Detector (N and P) and dual Nickel Electron Capture
Detectors. Qualitative and quantitative analyses were performed on
I and confirmed on Column II as follows!
Column I: 4 mm I.D. x 6 mm O.D. x 183 cm. Glass, packed with 1.57.
OV-17/1.95Z OV210 on 80/100 gas chrom Q, carrier N2 or He at
60 cc/min.
Column II: 4 mm I.D. x 6 mo O.D. x 183 cm. Glass, packed with 4%
SE30/6X OV210 on gas chrom Q, carrier N2 or He at 80 cc/min.
GLC operating conditions were as follows:
Inj. Port Temp. - 225°C
Detector Temp. - 210°C H3 EC
325°C Ni63 EC
245°C N-P
Column Oven - 200°C
12
-------
437
Transfer-line Temp. - 235*C
Chart Speed - 0.5 in/nln or 1 cm/uin.
Electrometer Attenuation - 10 x 16 Tracor EC
1x8 Tracor N-P
Quantitative analysis was performed on peak height and/or peak
area comparisons using external standards and accepting no more than
a 10Z variance between sample and standard peak size.
Samples were extracted into 30/70 dlchloromethane/ hexane,
concentrated, rediluted to appropriate volume with hexane, and then
injected onto the GLC column.
The reference for the analytical procedure throughout this study
was "The Manual of Analytical Methods for the Analysis of Pesticides
in Human and Environmental Samples" (EPA 600/8-80-038) June 1980.
Urine Samples were analyzed for alkyl phosphate metabolites by
the "Benzyl Alkyl Phosphate" Method of the University of Miami School
of Medicine, using a Tracor 220 Gas Chroma tograph equipped with a
Flame Photometric Detector in the phosphorus mode (X-526nm). Analyses
were performed on Column III and confirmed on Column II (as previously
described).
Column III: 4 mm I.D. x 6 mm O.D. x 183 cm. Glass, packed with 5Z
OV210 on 80/100 mesh gas chrom Q, carrier ^ at 25 cc/mln.
GLC conditions were as follows:
Column temp. 175*C
Detector temp. 215*C
Hydrogen 100 cc/mln
Air 80 cc/mln
Electrometer Attenuation - 32 x 10
13
-------
V. Quality Assurance - The proceeding paragraphs have described, in detail, the /i 7 n
4 jo
procedures utilized for the collection and analysis of samples in support of
this study. These procedures follow those which were outlined in the "SC PHAP
QA Flan for Extramural Project-Dermal and Respiratory Exposure Assessment of
Adult and Juvenile Harvesters" which was submitted to the EPA in March 1982
and subsequently approved by the EPA QA Officer. Also included in the QA
Plan and adhered to by the SC PHAP were general quality control procedures
such as peer and EPA review of the study protocol, evaluation of analytical
methodologies, record keeping (field tracking reports, laboratory sample log
books, instrument maintenance logs, etc.), scheduled routine maintenance,
checks of the gas chromatographic system, use of analytical reference standards
obtained from the EPA Environmental Monitoring Systems Laboratory (EMSL) and
participation in the EPA Quality Control Program under the direction of the
EMSL.
Specific QA analytical procedures utilized by the SC PHAP laboratory in
support of this study were:
Intralaboratory
1. One fortified sample was analyzed with every ten study samples to
document the extraction efficiency and reproductability of the
analytical methodology.
2. Blanks, sample media and reagent, were also analyzed with every ten
study samples to demonstrate the purity of reagents and cleanup
procedures of the sample media.
3. Sample media were fortified in the field at the time of sample
collection and were freezer stored along with the study samples.
The field spikes, when analyzed, provided data on stability and
sample degradation over time.
14
-------
Interlaboratory
Blind analyses of fortified samples Which were split between the
SC PHAP and the Iowa PHAP (NPHAP Quality Assurance Project) which
served as procedural checks.
Acceptable levels of accuracy and precision for the analytical methodology
were achieved and are reported in Table 4 - Intralaboratory Quality Assurance
and Table 5 - Interlaboratory Quality Assurance. Analysis of blanks, sample
media and reagent, confirmed the absence of contaminants. The results of the
quality assurance procedures indicated that no corrections to study data were
required for analytical methodology or storage losses.
15
-------
Table 4
Intralaboratory Quality Assurance
440
Medium
Intralaboratory — ;
21
Gauze Squares-
Gauze Squares
Gauze Squares
G.F. Filters
G.F. Filters
XAD-4 Resin
Urine (DMP)-
Soil
Blueberries
Leaves
Field Spikes:
G.F. Filter
G.F. Filter
G.F. Filter
XAD-4 Resin
XAD-4 Resin
Malathion
Spiking
Level
i
i
100 ng
2.0 ug
2.06ug
100 ng
103 ng
100 ng
350 ppb
100 ng
100 ng
100 ng
1.22 ug
1.71 ug
2.44 ug
244 ng
488 ng
Number
of
Replicates
31
6
12
9
3
9
8
5
5
5
4
4
3
6
5
Recovery
X (%)
96.2(96.2)
1.95(97.5)
1.92(93.2)
97.4(97.4)
97.7(94.9)
91.0(91.0)
242.5(69.3)
93.0(93.0)
97.6(97.6)
100.8(100.8)
1.12(91.8)
1.58(92.5)
2.17(88.9)
255.2(104.5)
558.7(114.5)
Standard
Deviation
6.1
0.09
0.14
12.0
2.9
7.7
10.5
14.1
6.1
11.6
0.13
0.22
0.11
37.4
60.9
Coefficient
of Variation
6.3
4.6
7.3
12.3
3.0
8.5
4.3
15.2
6.3
11.5
11.6
13.9
5.1
14.7
10.9
JY All analyses of blanks, sample media and reagent, were negative.
21 Gauze Squares served as quality control for cotton gloves.
3/ Provided by the EPA Environmental Monitoring Systems Laboratory (Las Vegas) .
16
-------
Table 5
Interlaboratory Quality Assurance
Sample
Type
Glass Fiber Filter
Glass Fiber Filter
Glass Fiber Filter
Gauze Square
Gauze Square
Gauze Square
XAD-4 Resin
XAD-4 Resin
XAD-4 Resin
Soil
Soil
Soil
Leaf
Leaf
Leaf
jrtified Samples Split Between
the SC
and LA
jratories for Malathion Residue Analyses
Spiking
Level
1.20 ug
• 1.20 ug
1.20 ug
Average
1.20 ug
1.20 ug
1.20 ug
Average
1.20 ug
1.20 ug
1.20 ug
Average
4.00 ug
4.00 ug
4.00 ug
Average
4.00 ug
4.00 ug
4.00 ug
Average
SC PHAP
Lab No.
82Q0524
82Q0525
82Q0526
Recovery
82Q0521
82Q0522
82Q0523
Recovery
82Q0527
82Q0528
82Q0529
Recovery
83Q0750
83Q0751
83Q0752
Recovery
83Q0756
83Q0757
83Q0758
Recovery
Recovery
SC
1.29
1.33
1.27
108%
1.29
1.27
1.21
1051
1.29
1.35
1.16
106Z
3.87
3.98
3.95
98%
4.03
3.97
4.03
100%
LA
1.19
1.25
1.24
102%
1.27
1.23
1.14
101%
1.14
1.08
1.28
97%
3.71
3.92
3.95
97%
4.26
4.04
4.35
105%
441
17
-------
442
VI. Results;
Prior to presenting the analytical results of the study, it is important
to note that an increase in average malathion residues for all environmental
substrates is observed on June 8 (five days post application). This same
trend is also seen in most of the participant sample media, except for the
cotton gloves and the back gauze squares of the juveniles. These findings
strongly suggested a malathion application had taken place after the partici-
pant and environmental sampling of June 7 and prior to the sampling of June 8.
The cooperating farmer was recontacted to determine if his fields had received
a malathion application during that 24-hour period which had not been reported
to the investigators. The farmer stated there were no pesticide applications
to his fields during the time period in question, however he did recall that
an adjacent blueberry farm had been sprayed while the study was in progress.
The fields of the adjacent farm were south of and within three hundred yards
of the blueberry field from which the environmental samples had been collected.
The adjacent farmer was contacted and he confirmed malathion was applied via
air blast sprayer during the afternoon of June 7. Thus, the increase in the
residues reported for June 8 are attributed to drift from the malathion
application at the neighboring farm.
Participant Results
Tables 6 through 10 report the malathion residues recovered from the
sample media of the juvenile and adult participants. Tables 6 and 7
respectively list the juvenile and adult results from Day 1 participant
monitoring (June 7). Day 2 (June 8) juvenile results are reported in Table
8 and the adult results are found in Table 9. Table 10 summarizes the
participant results from the two days of study.
All cotton glove samples worn by the participants during the two days
of study contained malathion residue. Results are reported in total nanograms
(ng) recovered from each pair of gloves. On Day 1, the juveniles averaged
92,700 ng while the adult average was slightly higher at 113,000 ng. The
18
-------
443
results of the Day 2 analyses show a 90% decline in the average residues
found In the two groups. Again, the adult glove average residue was
greater than the average observed in the Juveniles, 12,100 ng as compared to
7,300 ng. The malathion residues recovered from the gauze squares attached
to the back of the gloves also demonstrated higher average residues in the
adult group during the two days of study.
Results of the gauze square analyses demonstrate the juveniles had
slightly higher malathion exposure to their forearms and chests than the
adults experienced on both days of study. Juvenile Day 1 average forearm
2
and chest residues (ng/cm ) were 2.50 and 1.95 as compared to the adult
averages of 1.41 and 1.62. On Day 2 the juveniles averaged 5.46 and 3.50
while the adults were found to have 4.18 and 3.13. Also on both days of
study, the juveniles* shoulders and backs tended to have less exposure
than the adults. The single exception to this trend is seen on Day 2 when
the average juvenile shoulder concentration is 0.48 ng greater than the
2
adults' average of 1.30 ng/cm .
It is difficult to compare the glove residues to the gauze squares
representing various body regions because the results of the two media are
expressed in different units. Davis (1980) reported the surface area of
2
the hands to be 820 cm . Since the adult and juvenile participants wore
the same size gloves, this figure has been used to adjust the average
glove residue results to units of square centimeters. Therefore, on Day 1
2
the dermal exposure to the hands of the juveniles averaged 113 ng/cm and
2 2
the adults averaged 137 ng/cm . Day 2 results respectively were 8.9 ng/cm
2
and 14.8 ng/cm .
A descending rank order of average body region exposure for juveniles
and adults on each day of study would be as follows: 1. hands, 2. forearms,
3. chest, 4. shoulders and 5. back. The only exception to the rank order
is the Day 1 adult chest residue which is 0.21 ng higher than their average
19
-------
Table 6
Day 1 (June 7) Juvenile Participant Results
Assessment of Dermal and Respiratory Exposure of Adult and
Juvenile Blueberry Harvesters to ULV Malathlon-Duplln County, N.C. 1982
Participant
I.D.
Mo.
1
2
4
6
9
14
16
17
18
19
21
22
24
25
26
30
X
8D
COTTON
GLOVES
(UK)
119,000
46,200
31,200
61,300
113,000
151,000
142,000
37,800
221,000
117,000
103,000
70,200
98,700
66,700
28,000
76,700
92,700
51,400
GAUZE SQUARES (ng/cm2)
Gloves
35.50
2.31
8.70
5.43
2.77
16.20
6.50
4.62
9.51
4.45
3.94
5.51
9.78
8.00
3.33
7.61
8.39
8.02
Porearma
2.38
5.02
0.52
0.52
0.46
2.56
1.52
2.01
0.66
4.34
1.07
0.42
14.70
1.01
0.27
NS3
2.50
3.67
Cheat
3.60
2.07
1.91
0.61
1.30
0.86
1.02
1.83
2.93
1.85
1.52
1.97
0.44
1.01
0.02
7.52
1.95
1.71
Shoulders
0.39
0.62
0.23
0.45
0.22
0.22
0.30
0.34
0.69
1.05
0.23
1.22
0.56
1.77
0.13
0.30
0.55
0.45
Back
0.46
0.92
0.78
ND2
ND
0.11
0.20
0.24
0.63
0.20
0.24
ND
0.34
0.13
1.27
0.13
0.35
0.37
PERSONAL
SAftpLE
(na/m3)
54.8
114.0
19.9
26.0
48.7
29.6
49.8
ND
38.8
ND
ND
28.3
18.9
34.5
ND
30.1
30.8
28.7
URINE (ppb)
DHTP
ND
ND
65.3
53.8
43.1
525.0
42.2
78.5
12.6
62.8
245.0
44.7
ND
124.0
29.1
18.8
84.1
132.2
DMP
ND
ND
46.6
ND
36.6
134.0
17.9
54.7
12.2
33.4
90.7
32.0
ND
50.9
29.1
ND
33.6
37.1
DMDTP
ND
ND
42.9
31.8
38.1
147.0
30.2
101.0
23.0
27.7
143.4
22.6
ND
66.7
11.1
ND
42.8
48.0
DMPTh
ND
ND
58.9
54.0
37.4
491.0
35.4
58.7
11.7
52.8
284.0
42.0
ND
50.9
29.1
ND
75.4
129.5
1Lower Limits of Detection: Gloves - 500.ng/pair, Gauze -0.10 ng/cm , Personal Air Sample - 15.0 ng/m and Urine • 10.0 ppb
ND - None Detected _£*.
JN8 • No Sanpl*
-------
Day 1 (June 7) Adult Participant Results*
Assessment of Dermal and Respiratory Exposure of Adult
Juvenile Blueberry Harvesters to ULV Malathlon-Duplln County,
and
H.C. 1982
Participant
I.D.
Mo.
3
5
7
8
10
11
12
13
15
20
23
27
28
29
X
••»—•——•——
8D
— •— — — ^— — •
'Lower Limits
COTTON
GLOVES
(na)
102.000
27.500
10.700
189,000
67,100
246,000
91,900
83.000
146.000
110,000
201.000
96.000
119.000
92.300
113.000
64.700
GAUZE SQUARES (ng/cm2)
Gloves
51.00
7.25
6.12
26.60
68.00
3.46
2.81
14.50
9.69
12.00
27.40
1.73
6.27
7.16
17.43
19.77
Forearms
0.88
1.09
0.75
1.10
5.70
2.03
1.46
0.94
0.78
1.90
0.41
0.67
0.65
NS
1.41
1.38
Cheat
2.07
0.99
1.38
5.72
3.33
0.48
1.67
0.65
0.92
3.58
0.51
0.99
0.38
ND
1.62
1.59
Shoulders
0.19
0.24
0.34
0.43
0.57
5.56
0.25
0.46
0.46
1.33
0.14
0.23
0.18
0.16
0.75
1.42
Back
0.30
0.23
ND2
ND
ND
ND
0.78
0.17
0.27
6.41
ND
ND
ND
ND
0.58
1.69
(na/.3)
24.5
33.2
ND
35.2
22.5
21.3
ND
16.9
ND
SC*
24.4
ND
17.5
44.1
18.4
14.8
URINE (ppb)
DMTP
ND
56.0
NS
ND
ND
46.9
86.0
93.8
24.1
56.5
ND
ND
13.4
26.8
31.0
33.8
DMP
ND
18.3
NS
ND
ND
16.7
33.3
41.7
ND
33.4
ND
ND
12.7
ND
12.0
15.5
DMDTP
ND
22.2
NS
ND
ND
11.1
33.3
50.0
ND
41.5
ND
ND
ND
10.3
13.0
18.0
DMPTh-
ND
58.9
NS
ND
ND
34.0
68.0
75.6
11.8
50.0
ND
ND
ND
ND
23.0
29.9
2 3
of Detection: Gloves - SOO.ng/pair, Cause • 0.10 ng/cm . Personal Air Sample • 15.0 ng/m . Urine • 10.0 ppbj^
ItfD - None Detected ^
„_ - No Sample
*SC • Sample Contaminated
-------
Day 2 (June 8) Juvenile Participant Results1
Assessment of Dermal and Respiratory Exposure of Adult and
Juvenile Blueberry Harvest«r« to ULV Malathion-Duplin County, N.C. 1982
Participant
I.D.
Mo.
1
2
4
6
9
14
16
17
18
19
21
22
24
25
26
30
I
SO
COTTON
CLOVES
(nc)
35,400
2,350
2,220
2,610
2,500
4,580
5,760
4,840
3,650
1,090
20,400
1,450
12,500
9,460
1,700
6,190
7,300
9,000
GAUZE SQUARES (ng/caz)
Glove*
7.09
15.20
4.46
2.94
2.84
3.68
2.38
5.59
ND
1.84
3.25
3.05
1.42
2.39
2.54
2.16
3.80
3.46
Forearms
NS2
3.64
11.00
7.92
6.89
7.64
1.45
7.35
2.07
7.08
1.05
3.06
6.00
1.37
11.40
3.98
5.46
3.38
Chest
3.59
4.01
2.78
3.73
2.69
13.79
0.40
7.17
3.75
3.27
5.93
1.58
ND
0.54
1.29
1.55
3.50
3.37
Shoulders
5.09
2.99
2.64
0.40
0.46
3.58
4.04
2.24
0.61
2.10
0.28
1.32
0.36
0.33
2.05
ND
1.78
1.56
Back
ND3
0.29
0.42
1.04
ND
1.95
0.13
0.10
0.34
0.13
0.50
ND
0.10
ND
0.15
ND
0.32
0.51
PERSONAL
CaVWDT 0
OAfUr w&
(no/a3)
60.2
59.1
126.0
74.3
74.3
59.6
73.3
67.6
78.5
41.6
233.0
73.3
76.3
ND
75.5
69.3
77.6
48.3
DUMB (ppb)
DMTP
ND
ND
211.0
ND
36.7
658.0
38.4
125.0
ND
273.0
88.8
124.0
24,8
161.0
348.0
ND
130.5
176.8
DMP
ND
31.4
84.9
ND
61.5
263.0
37.7
69.2
39.0
181.0
68.2
66.7
38.1
127.0
124.0
28.6
76.3
69.0
DMDTP
ND
ND
74.4
ND
48.8
313.0
28.6
142.0
ND
162.0
75.0
75.0
ND
78.1
163.0
ND
72.5
86.8
DMPTh
ND
ND
164.0
ND
45.6
452.0
25.6
104.0
ND
197.0
65.7
61.6
ND
107.0
238.0
ND
91.3
122.9
1 23
Lower Limits of Detection: Gloves - 500.ng/palr, Cause • 0.10 ng/cm , Personal Air Sample - 15.0 ng/nt and Urine • 10.0 pp
• No Sample
3ND • Nona Detected
ON
-------
Pay 2 (June 8) Adult Participant Results
1
Assessment of Dermal and Respiratory Expoaure of Adult and
Juvenile Blueberry Harveatera to ULV Malathion-Duplin County, N.C. 1982
Participant
I.D.
Mo.
3
5
7
8
10
11
12
13
15
20
23
27
28
X
—•———•——
8D
•*
COTTON
GLOVES
5,180
2,170
3,390
7,120
22,000
7,200
7,300
37,900
19,600
4,800
4,890
9,900
21,400
17.100
12,100
10,100
GAUZE SQUARES (ng/cm2)
Gloves
5.20
4.01
2.25
4.37
4.73
4.93
2.89
4.68
1.42
1.59
5.25
11.70
7.03
6.40
4.75
2.61
Forearms
4.50
6.02
1.27
1.97
5.03
NS3
4.99
1.92
2.13
2.13
2.15
5.02
4.67
12.50
4.18
2.97
Cheat
5.85
5.01
1.39
1.47
2.43
8.84
4.30
2.69
1.74
1.95
0.96
4.15
1.37
I.fi2
3.13
2.25
Shoulders
1.84
0.91
0.42
0.37
1.51
2.92
0.28
1.79
2.06
0.28
ND
ND
4.98
0.85
1.30
1.38
Back
1.01
3.58
ND2
1.29
0.22
1.28
0.28
0.60
0.45
0.10
0.22
ND
0.12
0.28
0.67
0.95
fna/m3)
80.0
61.5
66.6
98.9
94.3
85.0
216.0
27.3
68.8
sc4
70.1
57.5
46.8
ND
74.8
50.2
DHTP
ND
211.0
122.0
ND
ND
24.0
38.4
ND
ND
19.2
ND
31.0
ND
ND
31.8
61.1
URINE (ppb)
DMP
ND
66.7
54.6
ND
ND
30.2
45.3
37.5
ND
30.8
ND
39.0
ND
28.6
23.8
23.5
DMDTP
ND
97.0
87.5
ND
ND
ND
28.6
ND
ND
50.6
ND
37.5
ND
BD
21.5
34.4
DMPTTv
ND
173.0
90.4
ND
ND
19.2
32.0
ND
ND
19.6
ND
20.5
ND
MIL-
25.3
49.1
A *
1Loirar Limits of Detection: Gloves
2ND • None Detected
- No Sample
• flamola Contaminated
2
0.10 ng/cm
Sample -15.0 ngfa and Urine • 10.0 pp
-------
Table 10
Summary of Participant Results
Assessment of Dermal and Respiratory Exposure of Adult
and Juvenile Blueberry Harvesters to ULV Malathion-Duplln County, N.C. 1982
Day 1 (June 7
Juveniles: X
SD
Adults: X
SD
Day 2 (June 8
Juveniles: X
SD
Adults: X
SD
COTTON
CLOVES
(na)
92,700
51,400
113,000
64,700
7,300
9,000
12,100
10,100
GAUZE SQUARES (ng/caZ)
Gloves
8.39
8.02
17.43
19.77
3.80
3.46
4.75
2.61
ForeanM
2.50
3.67
1.41
1.38
5.46
3.38
4.18
2.97
Cheat
1.95
1.71
1.62
1.59
3/50
3.37
3.13
2.25
Shoulders
0.55
0.45
0.75
1.42
1.78
1.56
1.30
1.38
Back
0.35
0.37
0.58
1.69
0.32
0.51
0.67
0.95
PERSONAL
fna/a3)
30.8
28.7
18.4
14.8
77.6
48.3
74.8
50.2
UUME (ppb)
DHTP
84.1
132.2
31.0
33.8
130.5
176.8
31.8
61.1
BMP
33.6
37.1
12.0
15.5
76.3
69.0
23.8
23.5
DMDTP ,
42.8
48.0
13.0
18.0
72.5
86.8
21.5
34.4
DMPTh
75.4
129.5
23.0
29.9
92.3
122.9
25.3
49.1
CD
-------
449
forearm residue. The gloves, when adjusted to square centimeters, demonstrate
the hands are the primary source of dermal exposure. This observation is not
unexpected, since in nearly all studies of occupational exposure to pesticides,
approximately 90% of the dermal exposure is found in the hands,Davis (1980).
The order of the remaining body regions also appear to follow a logical
exposure pattern. Body surface areas having greater contact with or which
are closer to the source of exposure (dislodgeable residues from the foliage
and berries) would be expected to have higher dermal exposures. Wicker and
Guthrie (1980) employed the industrial technique of time and motion studies
to determine standardized times of exposure for anatomic regions of workers
during the harvest of a variety of crops. Blueberry pickers were filmed
at 5 consecutive 3.5 minute intervals for a total of 17.5 minutes. Analysis
of the film found that the right and left hand were in contact with the fruit
and foliage for an average of 16.2 (92%) and 16.3 (93Z) minutes respectively.
Right and left arm contact accounted for 3.5 (20%) and 4.9 (28%) minutes.
The trunk (chest) of the body was in contact for only 1.1 (6%) minutes.
Standardized times were not reported for the shoulders and back.
Media of the personal air samples consisted of glass fiber filters
followed by XAD-4 sorbent tubes. All results reported are residues
recovered from the glass fiber filters. None of the 60 XAD-4 resin
samples from the two days of participant monitoring had quantifiable
calathion residues. Day 1 results show the juvenile personal air samples
(30.8 ng/m ) averaged 60% more malathion than recovered from the adult
samples (18.4 ng/m ). No explanation is available for this difference.
During monitoring, the sample media were attached to the front collars of
the disposable jackets worn by the participants in order to obtain air
samples from their breathing zones. Significant height differences between
the adults and Juveniles would provide a potential explanation, however
the average juvenile height was 159.3 cm and the adult was 162.4 cm. Results
25
-------
450
of the Day 2 personal air sampling further discount height as a contributing
factor since the juvenile and adult average, residues are almost identical,
77.6 ng/m and 74.8 ng/m . Drift from the malathion application at the adja-
cent farm accounts for the higher concentrations observed on Day 2.
Absorption and excretion of malathion by the participants was confirmed
through the analyses of urine samples for malathion metabolites. Urine
samples were analyzed for four dialkyl phosphate residues: 1) dimethyl
thiophosphate (DMTP), 2) dimethyl phosphate (DM?), 3) dimethyl dithio-
phosphate (DMDTP) and 4) dimethyl phosphorothiolate (DMPTh). Analyses
for malathion monocarboxylic acid (MCA) and malathion dlcarboxylic acid
(DCA) were not performed because the Intended purpose of the urine sampling
was to determine if the exposure of the participants resulted in observable
excretion levels. This purpose was fulfilled through the dialkyl phosphate
analyses.
Three juvenile and five adult participants had no quantifiable residues
in their Day 1 urine samples. Results of Day 2 analyses show two juveniles
and six adults without urinary metabolites. The average juvenile residue for
each of the four metabolites on both days of study was approximately three
tiaes higher than the average residues observed in the adults.
Statistical analyses of the participants' dermal and respiratory sampling
media found no significant differences between the exposure patterns of the
adult and juvenile blueberry harvesters. No differences were observed between
the juveniles and adults on each day of study (Table 11) or when juvenile Day 1
and 2 results were compared to adult Day 1 and 2 results (Table 12). The
purpose of the square root transformation analyses listed in Table 12 was to
make the data follow a more normal distribution, however this procedure failed
to identify any differences in the exposure patterns.
Significant differences were observed in the metabolites recovered from
the participants' urine samples. Table 11 reports observed differences between
26
-------
451
Table 11
Statistical Analyses (t-test) of Juvenile
vs. Adult Sample Media for Each Day of Study
Sample Media
Cotton Gloves
Gauze Squares:
Gloves
Forearms " "
Chest
Shoulders " "
Back
Personal Air Samples " "
Urinary Metabolites:
DMTP t2?-1.546(P- .134) t2g-2.095(P- .045)*
DMP t2?-2.115(P- .044)* t2g-2.860(P- .008)*
DMDTP t27-2.293(P- .029)* t28-2.164(P- .039)*
DMPTh t27"1.571(P- .128) t28-1.975(P- .058)
*Statistlcally significant at P £ 0.05
NS - Mo significance, P > 0.05
27
-------
Table 12
Statistical Analyses of
Juvenile Day 1&2 Results vs. Adult Day 1&2 Results
Repeated Measurements Analysis of Variance
Without and With Square Root Transformation
A52
Sample Media
Cotton Gloves
Gauze Squares:
Gloves
Forearms
Chest
Shoulders
Back
Personal Air Samples
Urinary Metabolites:
DMTP
DMP
DMDTP
DMPTh
Without Transformation Square Root Transformation
NS NS
Fl 27"3*63(P" '067)
Fl 27"6'84(P" 'OU)*
- .024)*
2?
-3.35(P- .078)
- 5.03 (P- .033)*
-7.06 (P- .013)*
-6.10 (P- .020)*
- 4.47 (P- .044)*
*Statistlcally significant at P £ 0.05
NS - No significance, P > 0.05
28
-------
453
juveniles and adults on Day 1 for DMP (P-.044) and DMDTP (P-.029), while
Day 2 results show three of the four metabolites as significantly different:
(1) DMTP (P-.045), (2) DMP (P-.008) and (3) DMDTP (P-.039). The square root
transformation analyses listed in Table 12 demonstrate a significant differ-
ence between the juveniles and adults for each of the four metabolites.
Urinary metabolite means listed in Table 10 demonstrate the Juvenile trend
toward higher urinary residues.
Table 13 lists the results of the statistical analyses which confirm
that the Day 1 juvenile and adult exposure was significantly different from
their Day 2 exposure. All sample media, except the back gauze squares, were
found to be significant.
Environmental Results
Tables 14 through 17 report the analytical results for oalathion residues
recovered from the environmental samples. Composite sampling of blueberries,
foliage and soil and high volume air sampling was performed daily from June
5 through June 8. Quantifiable malathion residues are reported for each
substrate on all sampling days with average residues decreasing from June 5
through June 7- On June 8, however, the average concentrations for all
substrates increased as a result of malathion drift from the malathion
application at the adjacent farm.
Blueberry residue analyses are reported in Table 14 and foliage results
are listed in Table 15- . Foliage residues for each day of study are consider-
ably higher than the corresponding blueberry residues. On June 5 and 6,
the average foliage residues are twice the amounts observed on the blue-
berries. On June 7 and 8, the foliage residues are 20 times greater. The
higher residues of the foliage samples are not surprising because the leaves
of blueberry bushes are typically dense and provide a degree of cover for
the berries. Thus, the foliage serves as a partial barrier between the
berries and the spray of pesticide application.
29
-------
Table 13
454
Statistical Analyses of
Day 1 vs. Day 2 Participant Results
Repeated Measurements Analysis of Variance
Without and With Square Root Transformation
Sample Media
Cotton Gloves
Gauze Squares:
Gloves
Forearms
Chest
Shoulders
Back
Personal Air Samples
Urinary Metabolites:
DMPTP
DMP
DMDTP
DMPTh
Without Transformation Square Root Transformation
F. ,0-75.80(P-.OOO)* -154.97 (P-.OOO)*
1,40
Fl 28"9*88(P"'004)*
F. -10.81(P-.003)*
28
(P-.028)*
-8.22 (P-.008)*
NS
1.27
NS
•14.34 (P-.001)*
NS
-14.41 (P-.001)*
-18.90 (P-.OOO)*
- 6.94 (P-.014)*
-7.85 (P-.009)*
MS
F, _ -10.81(P-.003)* -18.90 (P-.OOO)*
1,24
HS
-18.65 (P-.OOO)*
MS
n
*Statistically Significant at P £ 0.05
MS - No significance, P > 0.05
30
-------
455
A 5% increase in average foliage residue is observed from June 6
2 2
(227.7 ng/cm ) to June 7 (238.1 ng/cm ). Although this minor increase may be
attributable to sampling technique, it is thought the increase is more likely
a result of dislodgeable soil residues being released by the activity of the
workers during Day 1 participant monitoring. The average foliage residue
2
increased to 292.6 ng/cm on June 8 (Day 2 participant monitoring) which is
explained by the malathion drift from the adjacent farm and also by dislodgable
soil residues.
Composite soil analyses are reported in Table 16 . Each sample through
the four sampling days contained quantifiable malathion residues. The average
residue declined from 1.97 ppm on June 5 to 1.21 ppm on June 7. The average
concentration increased by 11% to 1.35 ppm on June 8 as a result of the spray
drift.
High volume air sampling results are reported in Table 17. Residues
recovered from the XAD-4 resin approach the lower limit of detection or, as
previously seen with the personal air samples, are nondetected. Average
3 3
airborne concentrations declined from 254 ng/m on June 5 to 50.6 ng/m
on June 7 and increased to 75.9 ng/m on June 8.
Table 18 lists the meteorological observations recorded during the
study. Four inches of rain fell during the first two days of environmental
sampling. Drops in temperature and relative humidity were noted on June 7,
but increased on June 8 to levels previously observed. Wind conditions on
June 7 at 9:00 AM were reported to be 8-10 mph from the north. Later that
afternoon, malathion was sprayed at the neighboring farm which was within 300
yards south of the study site. The wind vrculd have to have shifted to the
south for the drift to have occurred, however documentation for wind direc-
tion and speed is not available for the afternoon and evening of June 7.
31
-------
456
i/
Table 14
Blueberry Residue Analyses —'
Assessment of Dermal and Respiratory Exposure of Adult
and Juvenile Blueberry Harvesters to ULV Malathion-Duplin County, N.C. 1982
Composite
Sample
No.
1
2
3
4
5
6
7
8
9
10
X
Si)
2
MALATHION (ng/cm )
June 5
133.1
36.7
17.3
234.7
92.6
168.4
487.0
293.3
119.6
162.4
174.5
137.7
June 6
72.7
92.2
386.7
4.1
20.0
78.1
32.8
158.2
125.0
154.6
112.4
110.1
June 7
11.6
36.3
ND2
ND
ND
4.5
ND
ND
53.0
5.2
11.1
18.5
June 8
13.1
4.0
43.2
7.6
16.2
6.7
63.2
6.4
3.8
12.1
17.6
19.7
\J Analysis was by surface extraction, Lower Limit of Detection
1.5 ng/cm^
21 ND - None Detected
32
-------
457
Table 15
Foliage Residue Analyses
Assessment of Dermal and Respiratory Exposure of Adult
and Juvenile Blueberry Harvesters to ULV Malathion-Duplin County, N.C. 1982
Composite
Sample
No.
1
2
3
4
5
6
7
8
9
10
It
S3
MALATHION (ng/cm2)
June 5
855.6
27.7
153.5
1,205.3
200.2
30.7
270.3
156.8
422. 4
178.7
350.1
384.7
June 6
102.4
355.3
15.4
17.3
22.2
180.7
415.5
331.2
24.7
812.2
227.7
257.0
June 7
1,327.2
301.5
117.7
114.8
66.0
14.9
137.8
16.7
264.6
19.6
238.1
395.4
June 8
55.8
402.1
11.7
152.0
38.9
6.9
747.6
55.0
1,347.7
107.8
292.6
437.6
Analysis was by surface extraction, Lower Limit of Detection
0.3 ng/cm2
33
-------
458
Table 16
Soil Residue Analyses
Assessment of Dermal and Respiratory Exposure of Adult
and Juvenile Blueberry Harvesters to ULV Malathion-Duplin County, N.C. 1982
Composite
Sample
No.
1
2
3
4
5
6
7
8
9
10
X
SI)
MALATHION .(ppm)
June 5
2.04
0.95
3.98
1.61
1.00
0.26
2.12
1.50
3.37
2.84
1.97
1.16
June 6
1.51
3.10
2.68
2.41
0.41
0.51
2.76
1.88
1.52
0.73
1.75
6.98
June 7
0.80
0.35
1.67
1.66
0.64
1.44
1.38
0.94
1.67
1.51
1.21
0.48
June 8
0.54
1.61
1.19
0.75
0.38
3.06
3.22
1.15
1.46
0.12
1.35
1.06
Lower Limit of Detection - 0.04 ppm
34
-------
459
Table 17
High Volume Air Sample Analyses
Assessment of Dermal and Respiratory Exposure of Adult
and Juvenile Blueberry Harvesters to ULV Malathion-Duplin County, N.C. 1982
Malathion (ng/m3)l
June 5
Sample # 1
Sample # 2
X
Glass
Fiber
Filter
251.5
246.8
249.2
XAD-4
Resin
1.9
7.8
4.9
Total
253.4
254.6
254.0
June 6
Sample # 1
Sample # 2
142.2
139.4
140.8
ND
6.1
3.1
142.2
145.5
143.9
June 7
Sample /
Sample i
f 1
f 2
45.7
55.5
50.6
ND
ND
45.7
55.5
50.6
June 8
Sample # 1
Sample // 2
94.8
55.0
74.9
ND
1.9
1.0
94.8
56.9
75.9
If Lower Limit of Detection - 0.5 ng/m
2/ ND - None Detected
35
-------
Table 18
METEOROLOGICAL OBSERVATIONS'*'
Dermal and Respiratory Exposure Assessment of Adult and Juvenile
Blueberry Harvesters to ULV Malathion-Duplin County, North Carolina 1982
460
Observation
June 5
June 6
June 7
June 8
Rainfall
Temperature (F)
Barometric Pressure 30.00
Relative Humidity 65%
Wind
% Cloud Cover
1.7"
82C
30.00
65Z
SE(5-7mph)
90
2.3"
82°
29.90
67%
NW(6-7mph)
0
0
74°
30.00
55%
N(8-10mph)
0
0
82°
29.99
65%
0
0
Observations were recorded at approximately 9:00 AM each day.
Rainfall is for 24 hour period ending at that time.
36
-------
461
VII. Discussion:
The objective of this study was to assess the difference, if any,
between the dermal and respiratory exposure patterns of juvenile and adult
blueberry harvesters who, under normal working conditions, had post application
exposure to ULV malathion. The statistical analyses of the participant data
demonstrated there were no significant differences between the exposure
patterns of the juvenile and adult workers. Thus, the study objective was
achieved.
Although there were no statistical differences in exposure between the
two groups of harvesters, there were significant differences between juvenile
and adult urinary metabolites. The average juvenile residue for each of the
four dialkyl phosphate residues on both days of study was approximately three
times higher than the average residues observed in the adults. On Day 1, two
metabolites (DMP and DMDTP) were significantly different while three (DMTP,
DMP and DMDTP) were significant on Day 2 (Table 11).
The observed differences in urinary metabolites have two explanations.
The juveniles, as estimated by the on site investigators,had a slightly higher
rate of blueberry consumption than the adults. Since there were no statistical
differences in exposure patterns between the Juveniles and adults, the higher
consumption rate (l*t to 1-5 cups as compared to one cup) may alone explain
the urinary metabolite differences.
Another contributing explanation is that children tend to have higher
metabolic rates than adults for various compounds (Rane, 1976). Thus, it
might be anticipated that juveniles would metabolize and excrete malathion
more quickly than adults when both groups experienced similar dermal and
respiratory doses.
37
-------
462
VIII. Re ferences:
Davis, J.E. Minimizing Occupational Exposure to Pesticides:
Personal Monitoring. Res. Rev. 75: 33-50 (1980).
Rane, A. and J.T. Wilson. Clinical Pharmacokinetics in
Infants and Children. Clin, Pharmaco. 1: 2-24 (1976).
Wicker, G.W. and F.E. Guthrie. Worker-Crop Contact Analyses
as a means of Evaluating Reentry Hazards. Bull. Environ.
Contam. Toxicol. 24 (1): 161-167 (1980).
38
-------
463
Youth 1n Agriculture: Human Exposure Assessment
and Medical Records Morbidity Study
Research performed by
Colorado State University
Fort Collins. CO 80523
January 1984
-------
464
PREFACE
This study was conducted under Cooperative Agreement CR-810734-01 with
the Exposure Assessment Branch, Hazard Evaluation Division. Office of
Pesticides and Toxic Substances, U.S. Environmental Protection Agency (EPA).
The contents of this report have been submitted to Colorado State University
as a Ph.D. dissertation by Susan Munn under the direction of Drs. Eldon P.
Savage and Thomas J. Keefe. Completion of this study was facilitated by
the assistance of the following personnel of the Epidemiologic Pesticide
Studies Center at Colorado State University:
Aaronson, Michael J., Ph.D.
Bergin, Sharon
Bonilla, Barbara
Keefe, Thomas J., Ph.D.
Munn. Susan
Savage, Eldon P., Ph.D.
Tessari, John D.
Wheeler, H. William
We wish to thank the onion growers and the many farm workers and their
families whose cooperation and participation made this study a success.
We also wish to thank employees of the Ft. Lupton Salud Clinic for their
cooperation and especially Mr. Ferrell Drewry for his time in preparing the
computer tapes which were used in the medical records study. We also acknow-
ledge the assistance provided by Charles W. Miller, Ph.D. (Field Studies
Coordinator, Exposure Assessment Branch, EPA), who maintained liaison and
continuity of support from the sponsor.
-------
465
Abstract
YOUTH IN AGRICULTURE: EXPOSURE ASSESSMENT
AND MEDICAL RECORDS MORBIDITY STUDY
The exposure assessment phase of this study provided data on pesti-
cide exposures received by youth (less than 16 years of age) and adults
(±16). Human exposure samples (gloves and urine) and environmental sam-
ples (soil, foliage, and field air) were collected during the onion
harvesting season of 1982. All samples were analyzed for toxaphene,
ethyl parathion, methyl parathion, and malathion. Differences between
youth and adults were found to be statistically significant for toxa-
phene residues on gloves on each sampling day, and for ethyl parathion
residues on gloves on one sampling day. Detectable levels of alkyl
phosphates were found in only 2 of 44 urine samples.
Questionnaires were administered to farm worker families to pro-
vide data on work practices, personal hygiene practices, and the mor-
bidity experience among family members. The results indicated that
youth work significantly fewer hours per day, fewer days per week, and
fewer months per year than adults. No statistically significant differ-
ences In personal hygiene practices were found between youth and adults.
Few positive responses were noted for illnesses or symptoms associated
with pesticide poisoning.
The medical records phase was conducted to determine the frequency
of certain illnesses in migrant children less than 16 years of age.
The study consisted of 26,206 medical records of youth visiting the Ft.
ii
-------
466
Lupton Salud Clinic for the three year period 1979-1981. Four disease
groupings were selected for indepth study: respiratory illnesses;
dermatologic disorders; eye diseases; and symptoms of possible pesti-
cide poisoning.
Multiple logistic regression analysis was performed on each
disease grouping utilizing four variables: age; sex; migrant status
(migrant, seasonal, and non-farm); and growing season. Respiratory
illnesses were found to have the most noticeable trends. Migrant chil-
dren in the 10-15 age group experienced more respiratory illness than
non-farm children in the late-growing season (25.82 vs. 17.82), but less
in the non-growing season (13.72 vs. 21.92). For the other disease
groupings, several trends were observed, but due to the small propor-
tions in each stratum, limited inferences could be made from these
results.
111
-------
467
TABLE OF CONTENTS
Page
INTRODUCTION 1
LITERATURE REVIEW 4
A. Youth in Agriculture 4
1. Population at Risk 5
2. Labor Laws 6
3. Epidemiological Considerations 7
4. Health Status 10
B. Health Effects Associated With Exposure to
Toxaphene and Organophosphate Pesticides . . 12
1. Toxaphene 12
a. Product Chemistry 12
b. Acute Exposure 14
c. Chronic Exposure 15
2. Organophosphate Pesticides 17
a. Product Chemistry 17
b. Acute Exposure 21
c. Chronic Exposure 24
3. Special Toxicological Problems
Associated with Children 26
4. Sources of Exposure 27
C. Assessing Exposure to Pesticides 30
1. Environmental Sampling 30
2. Human Exposure Studies 32
PURPOSE AND SCOPE 39
MATERIALS AND METHODS 41
A. Exposure Assessment Study 41
1. Selection of the Study Area and Sample . 41
2. * Development and Pretesting of the Study
Questionnaire 42
3. Field Preparation 43
4. Collection of Environmental and Human
Exposure Samples 49
5. Laboratory Analyses 51
6. Administering the Questionnaire .... 57
iv
-------
468
TABLE OF CONTENTS (cont'd)
7. Statistical Analysis 59
a. Observational Data 59
b. Human Exposure Data 59
c. Questionnaire Data 61
B. Medical Records Morbidity Study 62
1. Acquisitions of Medical Records .... 62
2. Data Analysis 65
RESULTS 67
A. Exposure Assessment Study 67
1. Environmental Data 67
2. Results of the Data Analysis 70
a. Observational Data 70
b. Human Exposure Data 72
c. Questionnaire Data 79
B. Medical Records Morbidity Study 88
1. Respiratory Diseases 93
2. Dermatologic Diseases 99
3. Eye Diseases 103
4. Symptoms of Possible Pesticide
Poisoning 103
DISCUSSION AND CONCLUSIONS 107
A. Exposure Assessment Study 107
1. Observational Data 107
2. Human Exposure Data 109
3. Questionnaire Data 114
B. Medical Records Morbidity Study 117
1. Respiratory Diseases 118
2. Dermatologic Diseases 120
3. Eye Diseases 121
4. Symptoms of Possible Pesticide
Poisoning 121
5. Confounding Variables 122
C. Conclusions 124
BIBLIOGRAPHY 127
APPENDIX A 139
APPENDIX B 150
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469
TABLE OF CONTENTS (cont'd)
Page
APPENDIX C 153
APPENDIX D 155
APPENDIX E 157
APPENDIX F 180
APPENDIX G 182
vi
-------
470
INTRODUCTION
The extent to which farm workers are adversely affected by exposure
to pesticides is a controversial subject. Although much knowledge has
been accumulated regarding the adverse health effects due to acute expo-
sure to pesticides, information is limited on the long-term human health
effects from low-level exposure to pesticides among adults. Less infor-
mation is available on pesticide exposure and the potential for chronic
health effects among youth (under 16 years of age) working in agricul-
ture. Studies are currently being conducted to increase our knowledge
in this important area.
Although agriculture is the world's largest industry, the health of
agricultural workers has received little attention. Agricultural workers
are exposed to conditions quite dissimilar to those found in other
industries. These conditions include exposure to harsh weather condi-
tions, toxic chemicals, zoonoses, and high accident rates (Wofinden,
1965).
Agriculture employs a large number of workers and In some areas
depends on the availability of seasonal workers. This demand is par-
tially fulfilled by the use of migrant farm workers. A migrant farm
worker is a person employed in agriculture whose work necessitates
traveling within a state or across several different states to obtain
work in planting and harvesting labor intensive crops. Epidemlological
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471
studies focusing on Che health of migrant farm workers and exposure to
pesticide residues are difficult to design and carry out due to the vide
diversity of migrant labor streams, geographic mobility, education,
income, attitudes, and health conditions.
The size of the migrant farm worker population is difficult to
estimate. The United States Department of Agriculture (USDA) (as cited
by Goldfarb, 1981) estimated that in 1974, migrants accounted for 8 per-
cent of all farm wage earners (209,000 out of a. total of 2.7 million).
In 1981, Goldfarb noted that when illegal Mexican workers and seasonal
workers are included, the percentage may be as high as one-fifth of all
farm wage earners. Neither of these worker estimates include the thou-
sands of children who contribute to this workforce.
The plight of migrant farm workers, as well as seasonal farm workers
and their families, has been an issue for years. Fuentes (1974) reported
that the occupational disease rate among migrant workers in California
was 11.9 per 1,000 workers. This is the highest rate in California and
more than twice the rate of all other industries combined. Compounding
the problem of the migrant farm worker is the emotional issue of young
children working in the fields alongside their parents and the potential
for ill health effects due to exposure to agricultural chemicals. In
addition, in many areas small children accompany their parents to the
fields. In these instances the children play, sleep, and eat in the
field.
Although the toxic effects of pesticides on the young are poorly
understood, it is recognized that there are certain physiological, meta-
bolic, and other differences between youth and adults. There is also a
general assumption that children are proportionately more susceptible to
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472
toxicants than adults. The significance of these differences on the
long-term health of youth exposed to pesticides is unknown. Furthermore,
it is not known whether differences exist between the responses of youth
and those of adults when both are exposed to agricultural chemicals.
The United States Department of Labor (USDOL) has major responsibil-
ity for carrying out legislation designed to protect adult workers and
.children who are allowed to work. The Environmental Protection Agency
(EPA) has been assigned responsibilities by Congress for administering
laws that regulate pesticides, including the application of pesticides
and the reentry by agricultural workers into fields following pesticide
applications.
Due to the lack of knowledge concerning children working in agri-
culture, the USDOL and the EPA have coordinated their efforts to reduce
this knowledge gap. The resulting Youth in Agriculture project was
undertaken to provide additional information on the health status of
youth engaged in agriculture, and to provide data on the level of pesti-
cide exposure among children working in the fields.
-------
473
LITERATURE REVIEW
A. Youth in Agriculture
The use of migrant farm workers has accompanied the development of
agriculture in the United States. For example, historians have traced
what they identified as the first migrant farm workers back to the 15th
century, when the Spanish and Mexican explorations left behind many of
the explorers who helped settle these areas. As the Southwestern states
developed, several noticeable waves of migrant Mexicans entered the U.S.
as a result of turmoil in Mexico, and they gained employment as migrant
field laborers. Since the 1940*s there has been a constant immigration
of farm laborers into the U.S. despite the increased attempts to control
their entry by the federal government and border patrols (McVilliams,
1968).
Today in the U.S. there are three main geographic streams of migrant
agricultural workers. An Atlantic Coast stream runs from Florida to
Maine and is composed principally of Blacks, but more recently, Puerto
Rlcans and West Indians have entered this stream. In the central U.S. a
Mid-Continental stream is based in the Rio Grande Valley in southern
Texas. This migrant stream includes the area between the two coasts and
is composed primarily of Mexican-Americans. The West Coast migrant
stream encompasses California, Oregon, and Washington and today is
-------
474
relatively ethnically homogeneous, being composed primarily of Mexican-
Americans (Siegel, 1966; Delgado, 1980).
1. Population at Risk
The actual population of migrant farm workers is difficult to esti-
mate. The number varies depending on whether one counts illegal aliens,
families, and the unemployed. A recent report by Rural America, Inc.
(1977) analyzed and criticized the standard government data regarding
farm workers. They noted that government representatives who collect
these data use different criteria to define farm workers and the term
"migrant". Consequently, the actual number given for migrant workers is
very confusing.
A 1976 study of migrant farm workers estimated that there were
830,000 migrants. This included 200,000 that were eligible for federal
programs, 630,000 illegal Mexican farm workers, and 10,000 to 20,000
Puerto Ricans (Dunbar and Kravitz, 1975). The USDA estimated that in 1974,
migrants comprised 8 percent of farm wage earners (209,000 out of a total
of 2.7 million). However, the USDA survey also found 927,000 "seasonal"
workers, defined as people (including migrants) who did farm work for
25-149 days. Fuentes (1974) reported that more than 800,000 U.S. chil-
dren make up almost one-fourth of the nation's paid farm labor force.
make up almost one-fourth of the nation's paid farm labor force.
The Colorado Migrant Council (CMC) estimates that in Colorado there
are 17,000 migrant farm workers (that come from outside the state) and
15,000 seasonal farm workers (personal communication, CMC, 3-2-83). The
Colorado Department of Labor provides services to seasonal and migrant
farm workers and reported a total for new applicants and renewals for
-------
6 475
seasonal farm workers of 1,317 and 1,125 for migrant farm workers for the
fiscal year (Colorado Department of Labor, 1982). In Colorado, and in
most states, many farm workers do not use employment services.
Most data available to government agencies that collect census data
on migrants are supplied by employers and do not include illegal aliens,
workers that are not on official payrolls, and available workers who are
not hired (Goldfarb, 1981). The thousands of children of farm workers
who are allowed to work in field labor are not included in these esti-
mates.
2. Labor Laws
Agriculture child labor laws are more lenient than industry labor
laws. Consequently, many children are allowed to work in agriculture at
ages when working in a factory would be illegal. There are special child
•
labor requirements in agriculture under the Fair Labor Standards Act set
by the USDOL. This act states that children under 12 years of age may
be employed outside of school hours in any agricultural occupation not
declared hazardous by the Secretary of Labor, and with written parental
consent on farms whose employees are exempt from the federal minimum
wage provisions (USDOL, Bulletin #102).
The Colorado Department of Labor, Division of Child Labor, has pro-
visions that allow children at age nine and older to be employed in non-
hazardous agricultural work, except during school hours on school days.
The Colorado Youth Employment Opportunity Act has more stringent stan-
dards than the federal laws and therefore the higher standards must be
observed in Colorado (Colorado Child Labor Law, Title 8, Article 12, CRS
1973).
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476
3. Epidemiological Considerations
In the 1960's public health workers increased their activities in
promoting improvements in the health of farm workers. During the late
1960's and early 1970*s, numerous reports were published which alluded
to the poor health status of both the migrant and seasonal farm worker
populations (Wofinden, 1965; Lindsay and Johnston, 1966; Gilbert and
O'Rourke, 1968; Harper, 1969; Dean et al., 1971; Afek and Hickey, 1972;
Ramirez, 1976). It was also during this time period that reports ap-
peared which focused on the health problems of children of migrant farm
workers. Siegel (1966) was among the first to recognize the interrela-
tionship of the social and economic status and the health needs of these
people. Socio-economic and cultural factors include: mobility, minority
status, low income, poor living conditions, inadequate nutrition, and
lack of'education.
Demographic data are not readily available on migrant and seasonal
farm workers. Perhaps the most recent description of farm workers comes
from a project directed by the Colorado Migrant Council (Delgado, 1980).
This study constructed a "profile" on farm workers in 14 states and con-
sidered 45 variables. Colorado was one of the states selected to parti-
cipate in the study. Of the farm workers interviewed in Colorado, 46
percent Identified Texas as their home base (Table 1). Of the ethnic
composition of the farm workers shown in Table 2, 85 percent were His-
panic. The mean yearly income of those interviewed was $2,957 (Table 3).
The mean education level for the male farm workers interviewed was 7.2
years.
There are considerably less descriptive data on children of farm
workers. A major concern related to the health of these children is the
-------
8 477
TABLE 1
Home base state for farm workers interviewed in Colorado.
State Percent
Texas 46
Colorado 21
New Mexico 6
Arizona 6
Other 22
Total 100
Source: Delgado (1980).
TABLE 2
Ethnic status of farm workers interviewed in Colorado.
Percent
Hispanic 85
Native American 7
Anglo 6
Black <1
Other <1
Total 100
Source: Delgado (1980).
-------
TABLE 3
Total family IncoM of fan vorkori la Colorado.
IneaM <$)
0- 999
1,000-1.9*9
2,000-2,999
3,000-3,999
*, 000-4.000
5,000-5,9*9
6.000-6,999
7,000-7.999
8,000-*. 999
9.000-9,999
>10,000
Fcrcnt (X)
12
It
IB
16
11
16
3
4
I
1
1
100
478
Sourea: D*l|>do (1980).
PERCENT (I)
U-M
It-M
MX
CT •
Figure 1. Age at which farm workers began
working in fields. Delgado (1980)
-------
10
477
early age at which they enter into farm work. Figure 1 Illustrates that
the majority of farm workers begin field work between the ages of 12 and
18.
4. Health Status
The health status and medical care facilities available to children
of migrant and seasonal farm workers have received increased attention
during the past two decades. Nutrition has been a major concern of sev-
eral studies involving children of Mexican-American migrant farm workers
(Chase et aL, 1971; Chase et aL, 1973b; Larson et aL, 1974; Chase et al.,
1980). The above studies noted low serum vitamin A Levels in approximate-
ly one-third of the preschool children studied. The children with low
vitamin A levels were found to have more frequent skin and upper respira-
tory tract infections. This is not surprising since vitamin A is consid-
ered important in the maintenance of epithelial membranes in the body.
A 1980 study by Chase et al. focused on zinc nutritional status in
Mexican-American migrant children with growth retardation. In this
study, correlations were not significant between either zinc or vitamin
A concentrations and growth percentiles. Earlier studies have noted the
diminished height attainment In infants and children with poor zinc nu-
triture (Walravens and Hambridge, 1976; Hambridge and Walravens, 1978).
The California State Department of Public Health (1960) reported
that among migrant children under three years of age, only one-third
were found to be adequately immunized against diptheria, smallpox, or
tetanus. Untreated medical conditions commonly observed Included skin
infections, diarrhea, tonsillitis, iron deficiency anemia, and pregnancy
without prenatal care. The lack of medical care prior to and following
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480
delivery is likely reflected in the high mortality in the first year of
life. Chase et al. (1971) found the migrant Mexican-American infant
mortality to be 63 deaths per 1,000 live births. This compared to 20
deaths per 1,000 live births for overall infant mortality in the United
States. This 1971 Mexican-American rate was comparable to the overall
infant mortality rate for the United States in 1930.
Fuentes (1974) listed the major health problems among migrant
workers as follows: malnutrition, dental problems, and upper respiratory
diseases. Injuries, skin ailments, chronic diseases, and inadequate pre-
natal care also predominate among adult migrants. It appears that mi-
grant farm workers do not fully utilize the clinic services available to
them; of the total migrant clinic visits, 80 percent are spouses and
children of migrant workers. Rudd (1975) evaluated the records of a
rural health clinic in California and described the patient visits by
age, sex, ethnicity, and types of treatment. The frequency (rate per
1,000 visits) for certain diseases was listed. The disease groups with
the highest percent of total visits were: miscellaneous (skin tests,
prescription refills), infectious, other (preventive medicine, family
planning), genitourinary, and cardiovascular. The health of children (2
months to 16 years) of Mexican-American migrant farm workers was evalu-
ated in a study by Smith et al. (1978). The five most frequent health
problems were: 1) anemia, 2) ear-nose-throat, 3) skin, A) eye, and 5)
acute respiratory infections.
Several studies have reported on the medical utilization patterns
of migrant farm workers. Walker (1979) studied the kinds of medical
care used by Mexican-American migrant labor families in their home base
(Laredo, Texas) and in travel areas. It was found that the study
-------
12
481
population used ambulatory services about one-half as much as the general
U.S. population while hospital use approached regional norms. Walker
(1979) also reported that few services were used during the periods of
migration. A study conducted in Wisconsin by Slesinger and Cautley
(1981) found similar utilization patterns by Hispanic migrant agricul-
tural workers. In general, the use by migrant workers of health ser-
vices, especially preventive care, was low when compared with other
populations. Also, women were more likely to have seen a physician in
the preceding year, and the self-perceived health status of migrant
workers was much lower than that of other populations.
B. Health Effects Associated With Exposure To Toxaphene and Organo-
phosphate Pesticides
1. Toxaphene
a. Product Chemistry
Toxaphene is an organochlorine insecticide and as such, is fre-
quently categorized with DDT, aldrin, dieldrin, heptachlor, lindane, and
chlordane. Toxaphene is the least familiar of this group to the general
public even though most of these insecticides became commercially impor-
tant at about the same time. Although the least familiar, toxaphene has
been the most heavily used insecticide in the United States for many
years. In 1966, the usage of toxaphene, DDT, aldrin, and chlordane were
34, 27, 14, and 0.5 million pounds respectively. In 1971, toxaphene
usage for U.S. agriculture exceeded 37 million pounds, while the second
highest quantity of insecticide (methyl parathion) used by American
farmers was 28 million pounds. Even before the use of DDT and aldrin
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13
were restricted, toxaphene had a much higher use in pounds than the
other organochlorines (Andrilenas, 1974). Toxaphene was the most heavily
used agricultural pesticide in California in 1975 and 1976 (California
Dept. of Food and Agriculture, 1976).
Toxaphene was discovered in 1944 when two Russian workers found
that the toxicity of terpenes contained in turpentine could be increased
by chlorination. The insecticidal properties of toxaphene were first
reported in 1947, and the product was marketed by the Hercules Powder
Company in 1948 under the name Hercules 3756* (Martin, 1971). Its
discovery was probably the result of the intense interest in chlorinated
cyclic hydrocarbons caused by the earlier findings of lindane and chlor-
dane.
Toxaphene is the common name given to the isomeric mixture of cam-
phenes containing from 67-69 percent chlorine. Chlorinated camphene is
the chemical name given to this mixture. This pesticide is normally
considered to have a molecular weight of 413.8, and an empirical formula
of C10H10Clg (Smith and Cooke, 1980). Hooper et al. (1979) reported
that this complex substance is a mixture of at least 177 polychlorinated
compounds. Only 10 components have been identified, including the most
toxic ingredients, and these 10 make up less than one-fourth of the mass
of the mixture.
Two of the most toxic components of toxaphene have been described
by Turner et al. (1977). They are 2,2,5-endo, 6-exo, 8,9,10-hepta-
chlorobornane and a -mixture of the 8-chloro and 9-chloro derivatives of
the above compound. The precursor for these toxicants is 2-exo, 10-
dichlorobornane, which is a product at an early stage in the chlorina-
tion of camphene.
482
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483
Brooks (1974a) described the technical or insecticidal grade toxa-
phene as an amber colored, waxy solid with a mild pine-like odor. This
compound melts in the range of 70-95 C. Toxaphene has a low volatility,
the vapor pressure at 25° C is 0.17 to 0.40 mm Hg, which is much higher
than the organochlorines mentioned earlier. Its solubility in water is
also higher than that of the other organochlorines, except lindane, with
a value of about 3 ppm at ambient temperature. Toxaphene is extremely
soluble in acetone, benzene, carbon tetrachloride, ethylene dichloride,
toluene, and xylene. Toxaphene dechlorinates on heating above 120 C or
when exposed to ultraviolet light or strong sunlight.
The EPA restricted the use of toxaphene in October of 1982. This
decision was based on studies which indicated that exposure to toxaphene
poses: 1) chronic effects to wildlife, particularly to fish, birds, and
mammals; 2) acute toxicity to aquatic organisms; and 3) population reduc-
tions in non-target animal species. Also, animal tests suggested that
toxaphene could pose an oncogenic risk to humans (Chemical and Engineer-
ing News, 1982; Janzen, 1982).
b. Acute Exposure
As early as 1952, Stormont and Conley reported on the effects due
to acute exposure to toxaphene. Toxaphene causes diffuse stimulation of
the brain and spinal cord resulting in hyperexcitability, salivation,
vomiting, tremors, clonic convulsions, followed by tetanic contractions
of the skeletal muscles and possibly culminating in death by respiratory
failure. These symptoms are similar to those caused by DDT and other
chlorinated hydrocarbon insecticides.
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15
The mechanism of action of toxaphene and the cyclodiene insecti-
cides is not clearly understood. It is known that they act on neurons
causing an Imbalance in sodium and potassium ions, but beyond this gen-
eral concept very little is known. When the mode of action of these
compounds is fully understood, it will provide much information about
the structure and function of the nervous system (Brooks, 1974b).
Estimates of the acute toxicity of toxaphene to human beings are
based on either information obtained from actual poisoning cases or the
assumption that humans are as sensitive as the most sensitive mammal.
Stormont and Conley (1952) estimated the lethal dose to be between two
and seven grams, based on records of poisonings. Guyer et al. (1971),
using the second assumption, estimated the lethal dose of toxaphene for a
70-kg man would be 2 to 3.5 grams. It appears that toxaphene may be one
of the more toxic organochlorine insecticides to humans. However, toxa-
phene is classified as moderately toxic since most oral LD-0 values fall
within the range of 50-500 mg/kg.
Johnston and Eden (1953) found that, when administered dermally,
toxaphene is somewhat less toxic than by oral ingestion. The LD-n value
for dermal exposure of rats was between 1025 and 1075 mg/kg. Without
providing documentation, one report cited by Hayes (1963) estimated the
hazardous dermal dose for humans to be 46 grams. For a 70 kg man this
dose would be approximately 660 mg/kg.
c. Chronic Exposure
Guyer et al. (1971) reported that in conventional two-year chronic
tests, rats fed 100 and 400 ppm of toxaphene experienced slight liver
changes, and at 25 ppm, liver enlargement was observed. Degenerative
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485
16
liver changes also occurred in dogs fed 40 and 200 ppm for two years. It
should be mentioned that no cases of chronic human intoxication have been
reported. Studies using unexposed and exposed workers (to a toxaphene-
methyl parathion mixture) showed no differences in heme synthesis or
adrenal related activities (Embry et al., 1972). Frequently, the expla-
nation of occupational poisoning reports is difficult and inconclusive
because only a few select parameters are measured and often there is
exposure to more than one compound.
The carcinogenic and mutagenic potential of toxaphene is of interest
because of its long history of use, and complex composition. An EPA
study in 1978 (cited by the National Cancer Institute, 1979) reported
that no significant differences were found in the rates of chromosomal
aberrations in leukocytes of individuals occupationally exposed to toxa-
phene compared to groups with no occupational exposures to toxaphene.
In 1979 the National Cancer Institute (NCI) completed an evaluation
of data from a carcinogenicity bioassay of toxaphene. Toxaphene dosages
were calculated as a time-weighted average since the dosages were lowered
during the course of the bioassay. The dosage amounted to 1,112 ppm
(high dose) and 556 ppm (low dose) for male rats, 1,080 and 540 ppm for
female rats, and 198 and 99 ppm for both male and female mice. The
toxaphene was mixed with feed and fed to the test animals for 80 weeks.
Matched control groups were also used in this study.
A significant increase was noted in the Incidence of follicular-cell
carcinomas or adenomas of the thyroid in male rats in the high dose
group. Two of the nine thyroid tumors were carcinomas. In both the
male and female groups, the development of thyroid tumors was dose
related. Based on the results of this study, the NCI concluded:
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486
17
"Toxaphene is carcinogenic in male and female B6C3F. mice, causing
increased incidences of hepatocellular carcinomas. The test results
also suggest carcinogenicity of toxaphene for the thyroid of male and
female Osborne-Mendel rats" (National Cancer Institute, 1979).
2. Organophosphate Pesticides
a. Product Chemistry
Research in the field of organic chemistry began over 160 years ago
when Lassaigne, in 1820, prepared phosphate esters. It was not until
the mid 1930's that the insecticidal properties of organophosphorous
compounds were observed. The discovery of parathion in 1944 by Schrader
lead to advancements in agricultural practices and the structure-
activity relationship of organophosphorous insecticides (Eto, 1974).
Organophosphorous insecticides gradually replaced organochlorine
compounds during the 1950's and 1960's in agriculture, horticulture, home
use, etc. Fowler and Mahan (1973) estimated that 15,259,000 pounds of
parathion were produced in the U.S. during 1970. Derache (1977) summa-
rized organophosphorous pesticides as being generally more toxic to
vertebrates than the organochlorines and also being less persistent in
the environment. The fact that the organophosphates are non-persistent
is a desired characteristic and has lead to their replacement of many
organochlorines. However, due to the high acute toxicity of organophos-
phates to mammals, some are more hazardous to exposed populations.
All organophosphates are derived from phosphoric acid. Eto (1974)
grouped the esters of phosphorous into nine subclasses, but Ware (1978)
simplified the subclasses into six groups shown in Figure 2. The sub-
classes have varying combinations of oxygen, carbon, sulfur, and nitrogen
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18
487
:P - o
:P - o
Phosphate
Phosphonate
'xll
,P - 0
P - S
Phosphorothioate
Phosphorothiolate
P - S
;p - N
Phosphorodithioate
Pho sp ho r am idat e
Figure 2. Subclasses of organophosphorous pesticides,
Ware (1978).
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19
488
attached to the phosphorous, thus producing the different characteristics
for each compound. Table A summarizes the physical properties of three
commonly used organophosphates; parathion, methyl parathlon, and mala-
thion. Due to the higher vapor pressures of these three compounds, they
are much more volatile than most chlorinated hydrocarbons (including DDT,
lindane, and aldrin). This property contributes to these compounds
being less persistent in the environment.
The organophosphorous insecticides produce their acute toxicity by
inhibiting acetylchollnesterase (both plasma or pseudocholinesterase,
and true or erythrocyte cholinesterase). Many authors have described
this action (O'Brien, 1967; O'Brien, 1969; Koelle, 1970; Aldridge and
Johnson, 1971). The mechanism of reactivity of organophosphates with
acetylcholinesterase is as follows:
Kl K2 *3
EOH + AX 5£Z± EOH.AX -^** EOA > EOH + A* + H
X~+ H H20
The enzyme and acetylcholine initially form a complex (EOH.AX) which
then acetylates the enzyme (EOA) with the release of choline (X).
Organophosphorous compounds react with the enzyme in a similar manner as
that of the normal substrate. The inhibitory effect results from the
relatively long life of the phosphorylated enzyme compared with the
acetylated enzyme of the physiological reaction. The deacetylation or
dephosphorylation step (K3) is the slowest. The number of molecules
hydrolyzed per minute by one molecule of enzyme have been estimated at
300,000 for acetylcholine and .008 for dimethyl phosphates (i.e., methyl
parathion and dichlorvos).
Parathion and methyl parathion are both in the phosphorothioate sub-
class and as such have only slight direct inhibitory action on plasma
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Table «
Physical properties of parathlon, Methyl psrsthlon, and utathlon.
Property
Parathlon
Methyl Parathlon
Malsthlon
Chealcsl nas*>(s)
Molecular weight
•oiling point
He Iting point
Odor
Color
Vapor pressure
Specific gravity
Solubility
Phosphorothlotlc acid. O.O-diethyl
O-(P-nItrophenyl) ester; O.O-
dlethyl O-p-nItrophenyl phosphoro-
thloste; O.P-dlethyl O-(*-nitro-
phenyl) thlophosphste; dlethyl
p-nItrophenyl thlonophosphate.
Psrsthlon or sthyl parathlon
291.3
375° C at 7(0 SB Hg
6.1° C
Pungent, garlic-like
Straw yellow or saber
0.003 BB Hg at 24° C
1.27 at 25° C
Para tli ton la •faclble with acetone.
alcohol, benzene, CCl^. CIIClj.
ethyl acetate, toluene, Kylene.
o-dlchloro-benxene.
O,O dlaethyl 0-p-nltrophenyl
phosphorothloate; dlsiethyl p-
nltrophenyl thlonophosphate
Hethyl parathlon
263.3
Therully unstable
37° C (pure); 29° C (technical)
Garlic-like (technical)
Tan to brown (technical); whit*
(pure)
0.000097 BB Mg at 20° C
1.3)8 at 20° C (pure);
1.22 at 20° C (technical)
55-60 ppa In water at 25° C;
soluble In moat other organic
solvents.
0.0-dlaethyl S-O.2-
dlcsrboethoxy ethyl)
dlthlupnosphsts
Hslsthlon
330.36
156-157° C at 0.7 •• Hg
2.85° C
Penetrating (garlic)
Colorless to saber
0.00004 BB Hg st 30° C
1.232 st 25° C
US pp*. In wster st 2$° C;
• Isclble with Mny organic
solvent*.
K)
O
Source: Monssnto Agricultural Division (1967); Hstlonul Agricultural Chmlcats Asuoclatlon (1968); Steelier (1968);
CcMiJense
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21
490
and red blood cell cholinesterase as described by Diggle and Gage (1951)
and Murphy et al. (1968). However, the active metabolites, paraoxon and
methyl paraoxon, are potent inhibitors of these enzymes. The resultant
phosphorylated enzyme is stable, so that hydrolysis leading to reactiva-
tion of the enzyme occurs slowly. Koelle (1970) also described a spon-
taneous reaction known as aging, which leads to a stable phosphorylated
cholinesterase unresponsive to spontaneous or induced hydrolysis. Mala-
thion is a member of the phosphorodithioate subclass. Diggle and Gage
(1951) and Murphy et al. (1968) also reported that malaoxon, a metabo-
lite, is the active inhibitor of acetylcholinesterase.
Many authors have published reports on the reactivation of active
acetylcholinesterase (Childs et al., 1955; Hobbiger, 1963; O'Brien,
1967). The most successful compounds are the oxime derivatives. A
standard part of organophosphate poisoning therapy is the administration
of 2-pyridine aldoxime methiodide (2-PAM) which accelerates the dephos-
phorylation of acetylcholinesterase.
Kahn (1976) reviewed the pesticides involved in reported episodes of
poisoning in California field workers exposed to organophosphate resi-
dues. The compound most frequently implicated was parathion. Since the
increased use of parathion as an agricultural pesticide, there have been
recurrent, and occasionally mass poisonings in harvest crews.
b. Acute Exposure
The signs and symptoms of cholinesterase inhibiting insecticide
exposure have been discussed in many reviews and texts (Residue Reviews
1980, Vol 75; Doull et al., 1980; NIOSH Criteria Documents-Malathion,
Methyl Parathion, Parathion, 1976). Signs and symptoms of acute
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22
organophosphate poisoning are similar from case to case due to the same
biochemical mode of action. The inhibition of acetylcholinesterase
results in the accumulation of acetylcholine in nerve tissue and effector
organs which imitate the muscarinic, nicotinic, and central nervous
system actions of acetylcholine.
Namba et al. (1971) summarized each of these responses. Muscarinic
effects refer to the action of the organophosphorous compound on the
autonomic effector cells of the eyes, heart, lungs, stomach, blood
vessels, and other organs. The nicotinic actions of organophosphates
refer to the effects on autonomic ganglion cells and the neuromuscular
junction, the actions are comparable to those of nicotine. The central
nervous effects include: anxiety, ataxia, confusion, convulsions, and
can lead to depression of respiratory and circulatory centers. Table 5
summarizes the above effector organs and signs and/or symptoms.
Doull et al. (1980) listed the oral LD^ values in male rats (mg/kg)
for parathion, methyl parathion, and malathion as: 13, 14, and 1,375,
respectively. Dermal administration of the above compounds are less
toxic with the LD50 values being 21, 67, and >4,444, respectively.
IXiring the past twenty years many reports involving field worker
poisoning due to exposure to organophosphate residues have been pub-
lished. Tabershaw and Cooper (1966), Peoples and Maddy (1978), and
McClure (1978) presented cases of organophosphate poisoning which listed
weakness, vomiting, nausea, and blurred vision as symptoms experienced
by the affected field workers. Also, blood cholinesterase values were
determined to be lower than normal values.
Two national studies of hospitalized pesticide poisonings were con-
ducted by Savage et al. (1975b, 1980) for the years 1971-1973 and
491
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23
492
TABLE 5
Signs and symptoms associated with «cut« and subacute exposures to
organophosphate pesticides
Effector Organ
Sign or Symptom
1. Miscerinic manifestiations
•) Gastrointestinal
b) Sweat glandi
c) Salivary glands
d) Lacrlaal glands
•) Cardiovascular system
f) Bronchial tree
g) Pupili
h) Ciliary body
1) Bladder
2. Hicotinic manifestations
a) Striated muscle
b) Sympathetic ganglia
and adrenals
3. Central Nervous System
Manifestations
Anorexia; nausea; vomiting; cramps;
diarrhea; teaesanis; involuntary
defecation; eructation; "heartburn";
substernal pressure
Increased sweating
Increased salivation
Increased lacrlaation
Bradycardia, fall in blood pressure
Tightness in chest; wheezing sugges-
tive of broncho-constriction;
dyspnea; cough; Increased bronchial
secretion; pulmonary edema
Pinpoint (meiosis) and nonreactive
Blurring of vision
Increased urinary frequency;
involuntary urination
ttiacular twitching; fasciculation;
cramping; weakness
Pallor; tachycardia; elevation of
blood pressure
Uneasiness; restlessness; anxiety;
trsmulousness; tension; apathy;
giddiness; withdrawal and depression;
headache; ataxia; slurred slow speech;
drowsiness; confusion; emotional
lability; coma with absence of re-
flexes; Cheyne-Stokes respirations;
convulsions; hyperpyrexia; depres-
sion of respiratory and circulatory
centers (with dyspnea and fall in
blood pressure)
Source: Hamba (1971); K10SH Criteria Documents for Occupational Exposure
to Malathion, Methyl Parathlon and Parathion (1976).
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493
1974-1976. Organophosphates were most often Involved in occupationally
related, hospital-admitted poisonings. Farmers accounted for the highest
number of hospital-admitted pesticide poisonings of any occupationally
exposed group. The EPA Region IV had the highest incidence rate for
hospital-admitted poisonings among the occupationally exposed population.
Eight southeastern states comprise Region IV. In the non-occupational
exposure group, children under 10 years of age accounted for the greatest
number of hospitalized cases. The overall estimated rate of hospital
admitted pesticide poisonings per 100,000 hospital admissions in the
United States ranged from 8.2 in 1971 to 9.6 in 1975.
c. Chronic Exposure
Delayed neurotoxic effects, as reported by Bidstrup et al. (1953),
may result as a consequence of exposure to organophosphorous compounds.
The precise biochemical action that leads to the paralytic effect and
axonal degeneration produced by organophosphorous triesters remains to
be determined. Aldridge and Johnson (1971) conducted structure-activity
studies with homologs of known paralytic compounds. They reported that
neuro-toxicity and the specific antiesterase potency increased with
diethyl, dipropyl, and dibutyl derivatives of diisopropyl fluorophos-
phate (DFP) and mipafox.
There is an indication that electromyographic methods can detect
altered peripheral nerve and muscle function in organophosphate-exposed
workers who did not exhibit other detectable signs and symptoms of
poisoning nor measurable decreases in blood chollnesterase activity
(Jager et al., 1970; Drenth et al., 1972). Studies of workers In an
organophosphorous pesticide factory indicated that measurements of
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25
494
altered electromyograph patterns and nerve conduction velocities may pro-
vide a more meaningful index of excessive occupational exposure to these
compounds than measurements of plasma or erythrocyte cholinesterase
(Roberts, 1976; 1977).
Abnormal electroencephalograms (EEGs), similar to those obtained
from epileptic patients, have been observed by several investigators in
individuals following acute pesticide intoxications (Grob and Harvey,
1953; Brown, 1971). Less dramatic abnormalities in the EEGs after recov-
ery from acute poisoning were described by Metcalf and Holmes (1969).
Duffy et al. (1979) suggested that the persistence of known short-term
organophosphate effects, when taken in conjunction with the reported
long-term behavioral effects of organophosphate exposure can lead to
brain function alterations.
Although a number of authors have reported the above findings,
several other investigators have disagreed with these conclusions
(Tabershaw and Cooper, 1966; Clark, 1971). Stroller et al. (1965) con-
ducted an epidemiologic analysis of patients following acute organo-
phosphate intoxication which did not reveal increased incidence of
psychiatric disorders. A case-control study of chronic neurological
sequelae of acute organophosphate pesticide poisoning was completed by
Savage et al. in 1980. The cases included individuals with previously
documented acute organophosphate pesticide poisonings. No significant
differences between the cases and control cohorts were found in the
physical examination. The results for both neurological and neuro-
psychological examinations were evaluated. Only a few of the .differ-
ences between the two cohorts in the neurological examination were
significant. However, several major differences between the case and
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495
26
control cohorts were found through the neuropsychological evaluations.
Individuals in the case cohort performed significantly worse than the
controls on four of five summary measures from the neuropsychological
tests. These tests included Intellectual functioning, academic skills,
abstraction and flexibility of thinking, and simple motor skills (speed
and coordination).
The NIOSH Criteria Document for Occupational Exposure to Parathion
(1976) stated that no papers had been found which reported the production
of carcinomas or other malignancies by this compound. However, due to
the continuing importance of malathion, methyl parathlon, and parathion
these compounds may undergo extensive carcinogenesis bioassays.
3. Special Toxicological Problems Associated with Children
Health effects related to, or caused, by xenobiotics depend to a
large extent on genetic make-up, nutrition, life-style, and most impor-
tantly on age and developmental maturity of an individual. Although few
studies involving humans have been conducted, there is growing interest
in the changes which occur with age in the metabolism of toxicants.
Vesell (1982) reported that age-related changes in drug metabolizing
capacity may be difficult to predict because of multiple forms of the
hepatic drug-metabolizing enzyme, cytochrome P-450. Rates of enzyme
activity, usually low in the fetus and higher in the neonate, reach
their peak in pre-adolescence. Alvarez et al. (1975) found that children
two to eight years .of age were able to metabolize two environmental
chemicals, antipyrene and phenylbutazone, with approximately twice the
capacity of adults.
Little is known about percutaneous absorption in children and the
infant. When a compound comes in contact with the skin the amount of
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27
absorption will depend primarily on the concentration of applied dose and
surface area. Wester and Maibach (1976) found that, as the concentration
of applied dose was increased, the total amount absorbed into the body
also increased. Noonan and Wester (1980) reported that increasing the
surface area of applied dose increased the absorption.
Spear (1982) discussed the "practical" problems associated with
children working in agricultural settings. Children work as part of a
family group, they often play in this field environment if too young to
work, and from approximately the age of eight they begin to work and con-
tribute to the family income. In addition to possible differences in
exposure rates between children and adults, one must consider the dif-
ference in hours worked. It appears that the highest estimation of
exposure for children working in harvesting of crops would be approxi-
mately that of adults in the same circumstances. It is possible that
children -may obtain a higher absorbed dose from an equivalent total
exposure when differences in body weight and an increased potential for
dermal absorption are considered. Spear emphasized that the differential
risk to children is probably more dependent on their toxicological sus-
ceptibility than on exposure related parameters.
A. Sources of Exposure
The classical routes of pesticide exposure are: 1) inhalation,
2) ingestion, and 3) skin absorption. Frequently, in tabulating data,
categories are used which Indicate the type of illness. The common
categories include: systemic, eyes, skin, and a combination of eyes and
skin (Maddy et al., 1979; Weiss, 1981). Iwata (1980) discounted air-
borne residues, which can lead to inhalation and oral exposures, as a
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497
significant source of exposure for agricultural workers. Dermal exposure
occurs due to the transfer of pesticide residues, remaining on the foliar
surfaces of the crop, to the skin and clothing of workers and is consid-
ered to be the primary source of exposure of farm workers (Gunther et
al., 1977).
Many reports have been published which focused on pesticide exposure
and poisoning as a result of dermal contact with foliage bearing pesti-
cide residues (Bogden et al., 1975; Kahn, 1976; Spear et al., 1977a;
Spear et al., 1977b). Pesticides are adsorbed onto foliar dust parti-
cles which are then dislodged by the workers' activity and fall out onto
the clothing and exposed body surfaces. In addition, it has been demon-
strated that harvesting crops that require prolonged contact with dense
foliage (such as citrus, grapes, and peaches) are more often related to
farm worker poisonings (Popendorf and Spear, 1974; McClure, 1978;
Popendorf et al., 1979).
Chase et al. (1973a) conducted a study focusing on pesticides and
migrant farm workers. It was brought to attention that children of farm
workers may have elevated serum pesticide levels since they frequently
play near sprayed fields and have bodily contact with parents coming
home from working in the fields. In 1975, the Colorado Epidemiologic
Pesticide Studies Center (CEPSC) investigated the sources of pesticide
exposure among residents of high pesticide usage areas (Savage, 1975a).
Both inside and outside air samples were analyzed; surprisingly, the
highest levels of p.,p'-DDT were detected in the inside air and in house-
dust samples. Morse et al. (1982) reported that migrant farm workers
may risk exposure to pesticides by living within spray areas. This is
of special concern since farm workers resided in the labor camps during
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498
29
the spray season and almost 20 percent of the persons living in such
camps were less than six years old. Increased contamination of food and
drinking water may be another source of exposure.
Placental transfer of pesticides in humans has been studied for
more than 15 years. O'Leary et al. (1970) found a relationship between
DDT and DDE in maternal blood, cord blood, and amniotic fluid, with the
maternal levels being the highest. Such early studies lead to concern
regarding the effects upon the fetus due to chronic exposure from the
mother, possible mutagenic or teratogenic effects, and the effect of
such agents on the infant's microsomal hepatic enzyme systems. Saxena
et al. (1981) reported on the transfer of organochlorine pesticides from
mother to fetus. A correlation was found between the pesticide concen-
tration and age, dietary habits, and area of residence.
Nursing infants can be exposed to higher than background levels of
fat soluble chemicals. Rogan et al. (1980) discussed pollutants in
breast milk. In general, the chemical contaminants that appear in breast
milk have high lipid solubility, resistance to physical degradation or
biologic metabolism, wide distribution in the environment, and slow or
absent excretion rates. Numerous papers have been published which
reported the presence of various chlorinated compounds in breast milk
(Quinby et al., 1965; Curley and Klmbrough, 1969; Kuratsune et al., 1972;
Hagyard et al., 1973; Wilson et al., 1973; Savage, 1976). However, long
term clinical studies on reproductive capacity, enzyme induction, or
carcinogenesis have not been carried out. Newborn babies, who may be
more susceptible than adults to such toxic effects, have not been
studied at all.
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499
C. Assessing Exposure To Pesticides
The hazard to fieldworkers from pesticide residues is a classical
occupational and environmental health issue. The exposure of agricul-
tural laborers to chemicals in the workplace has received increasing
regulatory and scientific attention. Laborers who harvest crops by hand
comprise a substantial proportion of exposed workers who come in contact
with pesticide treated foliage and pesticide laden dust from the soil
surface. The legal reentry interval is defined as the period of time
between pesticide application and worker entry in the field involving
prolonged foliar contact. The reentry concept is not new, having been
practiced shortly after organophosphorous compounds were introduced into
agriculture. Since that time, reentry regulations to protect workers
have increased the scientific interest in the extent of exposure of
agricultural fieldworkers to pesticide residues and in methods to assess
that exposure (Popendorf and Leffingwell, 1982).
1. Environmental Sampling
Soil surface residues are an important source of exposure to agri-
cultural fieldworkers. Soil residues provide a source for direct worker
exposure and for transfer of these residues to plant surfaces. Pesti-
cides are much more persistent in dry soil than moist soil, and soil
dust residues may be particularly Important in crops which do not re-
ceive irrigation water or rain on the soil surface between pesticide
application and worker exposure (Spencer et al., 1977). In addition,
organophosphates decay more slowly under hot, dry weather conditions
than hot, wet weather conditions due to the influence of temperature
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31
500
and moisture on the vaporization rates of soil incorporated pesticides
(Haque and Freed, 1975).
To protect workers during reentry, Spencer et al. (1977) recommended
two types of methodologies for monitoring soil pesticide residues within
the work environment. The first method involves vacuuming the soil sur-
face to obtain soil dust. This is done by passing the vacuum nozzle
over a 3-layered screen to collect easily dislodgable material less than
150 urn. The second method entails sampling and analyzing 1-cm deep soil
plugs instead of loose dust from the soil surface. This procedure is
best suited in areas where the soil remains moist or is moist during the
worker reentry period. The sampling pattern and number of individual
cores per sample depends on the crop grown, irrigation method, etc. All
samples should be frozen until processed in the laboratory.
The importance of pesticide residues absorbed onto foliage as a
source of fieldworker exposure has already been discussed. It is Imper-
ative to accurately estimate foliar surface residues to estimate worker
safety reentry time (Nigg, 1980). The protocol for obtaining dislodgable
residues involves sampling of foliage using a leaf punch sampler to ob-
tain samples of known surface area. The dislodgable residues are then
extracted from the leaf disk by shaking with an organic solvent to trans-
fer the residues into the organic solvent for subsequent analysis. The
technique usually preferred is that described by Iwata et al. (1977).
Spear (1980) discussed several of the problems encountered when
attempting to determine safe reentry intervals. The residues to which
workers are exposed can be comprised of several toxic species.. This is
important in the conversion of the thiophosphates to their oxygen analogs
on foliage and on the soil surface under normal climatic conditions. It
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501
32
should be emphasized that residue data may vary due to the confounding
factors in an agricultural setting (Iwata, 1980). These factors include
the method and equipment used in the application, the type and amount of
foliage of the crop, and the geographical area. The methods of irriga-
tion and weed control, and the amount of rainfall are also important
factors. Air temperature, wind movement, and sunlight will affect
insecticide vaporization and photodegradation. In addition, the type of
formulation used, such as wettable powders, emulsiftable concentrates,
and time-release formulations can influence residue levels. Bigley et
al. (1981) showed that the persistence of methyl parathion can be in-
creased by the addition of toxaphene. The authors also concluded that
it should be possible to produce increased surface residues of methyl
parathion by using substitutes of appropriate properties, thus avoiding
the hazards associated with the use of toxaphene.
Equipment and methods exist to collect volatile pesticides from air.
Gunther (1980) reported that appropriate filters, absorbents, and ad-
sorbents may be used as collectors. The research of Goes (1979)
supported earlier findings that the use of polyurethane foam plugs was
an efficient medium for the collection of pesticide vapors in air.
2. Human Exposure Studies
It was recognized over 30 years ago that parathion-laden dust in a
citrus grove could be hazardous to citrus workers (Carman et al., 1952).
As previously mentioned, the primary route of exposure of fieldworkers
is dermal with smaller respiratory and oral components. Fieldworkers
"dislodge" pesticide-laden particulate matter from foliage, fruit, and
soil surfaces. These pesticide containing particles settle on the
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5C2
33
worker's skin and clothing. Human exposure studies are divided into two
categories: the monitoring of human subjects at various time intervals
after a pesticide application to aid in determining safe reentry levels;
and the monitoring of human subjects at the legal reentry time.
Dermal exposure has been estimated by using dermal pads or patches
affixed to various body locations. Although research is continuing in
this area, the best available method appears to be the use of a multi-
layered gauze pad attached to the skin as originally reported by Durham
and Wolfe in 1962. The use of gauze pads to estimate dermal exposures
to dry pesticide residues in field studies has been utilized and dis-
cussed by Popendorf (1976), Spear et al. (1977a), Popendorf (1980), and
Davis (1980).
Popendorf et al. (1979) studied the exposures of peach harvesters
and 'found the highest exposures to the hands, forearms, and head; and
the lowest exposures to the hips and feet. A study of citrus workers in
California by Knaak et al. (1978a) found that exposures were highest on
the thigh, back, and shoulder; and lowest on the chest, based on exposure
pad analyses. In the U.S. the minimization of exposure to pesticides
through protective clothing has become an important issue. Several
authors have recently published articles comparing types of fabrics and
their effectiveness in preventing pesticide absorption (Kawar et al.,
1978; Staiff et al., 1982; Davies et al., 1982). Davies et al. (1982)
reported that 100 percent cotton coveralls provided significantly greater
protection than did-regular clothing and the use of respirators. A
recent publication by Serat et al. (1982) emphasized that pesticide
collections on fabric materials cannot be assumed to represent impinged
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503
34
amounts. This is due to the varying and unstable field conditions and
the contact of the workers hands and the dermal pads.
Assessment of hand exposure is important since the hands comprise
only 6.9 percent of the human dermal surface area but in many situations
receive the highest exposures (Popendorf and Leffing well, 1982). Davis
(1980) reported that, in nearly all studies of occupational exposure to
pesticides, approximately 90 percent of the dermal exposure was found
on the hands.
Durham and Wolfe (1962) described the bag rinse technique which is
generally used to remove residues from the hands with a solvent such as
ethanol. The use of gloves presents several attractive advantages as
discussed by Davis (1980); they do not slow the worker's productivity,
solvents are not necessary, and the amount of toxicant absorbed into the
hands during the exposure period is not included in the exposure esti-
mate. On the other hand, gloves often contain materials, such as
sizing agents, that may interfere with analyses and are difficult to
remove. Workers may object to wearing even thin cotton gloves for a
certain period of time. And as Maibach and Feldman (1974) pointed out,
covering residues already on the hands with gloves may result in in-
creased exposure of the test subjects due to increased penetration
because of occlusion. The use of gloves to entrap pesticide residues
before they reach the hands is a practical and efficient method which,
to date, requires improved methodology.
Many studies have focused on correlating dermal exposure to organo-
phosphate pesticides and cholinesterase depression (Spear et al., 1977a;
Spear et al., 1977b; Knaak et al., 1978b; Richards et al., 1978;
Fopendorf et al., 1979; Kraus et al., 1981). These studies concluded
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504
that the primary route of exposure was dermal and that the oxidation pro-
duct of parathion (paraoxon), if present, was the principle intoxicant.
Kraus et al. (1981) reported a higher cholinesterase activity for usual
farm workers than for the control group (student volunteers). Richards
et al. (1978) reported a decline in cholinesterase activity for workers
in a plot treated with azinphosmethyl and workers in a plot free of
organophosphate residues. This decline in both groups may have been due
to exposure to an unknown cholinesterase inhibitor present on the ranch.
In contrast, Quinones et al. (1976) found that Puerto Mean farm workers
had significantly lower cholinesterase activity than Puerto Mean or
non-Puerto Mean controls during a nonexposure period.
Methods used for estimation of respiratory exposure to pesticides
can be divided according to whether the monitoring is by the direct
method, which utilizes respirator pads, or by measuring concentrations
of the toxicant in air (Davis, 1980). The technique currently used for
direct measurement of respiratory exposure is essentially the same as
described by Durham and Wolfe (1962). This method is preferred because
of its simplicity. The major disadvantage of the direct method is that
the gauze-faced pads (designed to fit in normal respiratory protection
devices) may not be an efficient trapping medium for the chemicals of
interest.
Investigations of respiratory exposure to pesticides using personal
monitors have utilized a large variety of sampling and analytical devices
and collection media. In general, personal monitors consist of a small,
battery operated pump connected to a collection device, which is posi-
tioned as near as possible to the workers breathing zone (Davis, 1980).
Although midget impingers filled with ethylene glycol or other liquids
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505
to trap the toxicant have frequently been used in the past, new tech-
nologies are evolving.
Fairchild and Tillery (1977) reported that although filters trap
aerosols, they do not retain pesticide vapors; while solid sorbents
retain pesticide vapors, they may not efficiently collect aerosol forms.
Hill and Arnold (1979) described a personal air sampler which consisted
of a small filter followed by a small tube filled with solid sorbent.
This sampler was found to be a reliable alternative to the standard
midget impinger method. It is fortunate that dermal, rather than respi-
ratory exposure, is considered to be the principle route of exposure to
agricultural workers since improvement of methodology to measure respi-
ratory exposure may be the most difficult, when occupational exposures
to pesticides are considered.
It is of special importance to be aware of the multitude of external
variables which influence the exposure of pesticide residues by the
worker as well as environmental factors. In 1974, Popendorf and Spear
conducted one of the first studies of farm workers which looked into
intervening factors. Some of these factors were: age and sex distribu-
tion, type of clothing worn, hours of work, and work rate. The authors'
results demonstrated the difficulty in quantifying exposure, even in a
single crop in one area, due to differences in work practices.
Choiinesterase depression as an indicator of pesticide exposure is
not satisfactory In many Instances. Not all pesticides are cholines-
terase inhibitors and it is possible that some exposure will result in
deleterious biological effects at levels of exposure lower than those
necessary to elicit cholinesterase depression (Davis et al., 1981).
Urinary metabolite levels may be sensitive, although semiquantitative,
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506
37
indicators of exposure (Franklin et al., 1981). However, methodology is
not currently available for sensitive detection of urinary metabolites
from all pesticides.
Morgan et al. (1977) determined that the alkyl phosphates and thio-
phosphates are not excreted rapidly after ingestion (8 to 24 hours, 10
to 39 percent total recovery), so 24 hour urine samples are the best
analytical substrate. However, major excretion of these compounds does
occur within 4 to 8 hours. Analytical results are variable due to
methodology and to human subject (biological) variability. Two major
advantages of urinalysis as a monitoring tool are that sample collection
does not require medical supervision and it is not subject to the reluc-
tance associated with venapuncture.
Indirect estimates of pesticide exposure have been measured in
field workers (Richards et al., 1978; Wicker et al., 1979; Knaak et al.,
1979; Kraus et al., 1981; Franklin et al., 1981). Richards et al.
(1978) found that the group-mean urinary metabolite excretion levels for
workers exposed to azinphosmethyl residues were highly correlated with
their daily group-mean percent change in blood cholinesterase activity.
Wicker et al. (1979) showed that field workers exposed to ethyl and
methyl parathion and who wore gloves had lower urinary para-nitrophenol
levels than workers not wearing gloves. Franklin et al. (1981) observed
a high correlation (r » 0.77, p < 0.01) between the 48-hour alkyl phos-
phate excretion and the amount of active ingredient (azinphosmethyl)
sprayed.
Due to the criticism of human studies on ethnical grounds, several
authors have suggested the use of animal models to replace human studies
(Guthrie et al., 1974; Serat et al., 1975; Skinner and Kilgore, 1978).
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507
38
Serat et al. (1975) discussed the need for alternative methods to those
now used for reentry studies, so that direct human exposure might be
eliminated. The technique used was to apply kinetic constants of the
compounds of interest, dermal LD50 values for selected strains of mice,
and arbitrarily chosen levels of cholinesterase activity loss, in an
equation which yielded the pesticide levels in parts per million.
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508
PURPOSE AND SCOPE
Numerous Incidents have occurred in which agricultural workers have
become acutely ill from exposure to pesticides remaining on crops. As
previously indicated in Chapter II. knowledge is limited on the chronic
effects of pesticide exposure among adults, and even less information
exists on the extent of pesticide exposure among youth (less than 16
years of age). It is desirable to reduce this knowledge gap if the
youth of the U.S. are to continue working in agricultural settings. If
potential adverse health effects are found among youth in agriculture,
changes may be required in reentry procedures, work procedures, and/or
application schedules. There is perhaps universal agreement that pro-
tection against occupational hazards should begin the moment employment
begins.
This investigation of youth in agriculture consisted of two parts:
the assessment of potential exposure to pesticide residues among youth
working in agriculture; and a migrant clinic medical records morbidity
study. The exposure assessment phase of this study provided data on the
exposure received by youth when working in the fields, as well as infor-
mation on the work practices of youth in the field, including hygiene
practices, hours spent in the field, and types of clothing worn while
working. In order to assess the exposure of youth Involved in field
labor, a single crop was chosen. In Colorado, the growing of onions is
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509
40
a significant labor intensive crop. The primary area of study was the
Flatte River Valley in northeast Colorado, a region which has the largest
concentration of onions and employs more seasonal and migrant labor than
any other region in the state. Chemical usage data were obtained from
the growers for each field in which study subjects worked. Human and
environmental samples were analyzed for toxaphene, ethyl parathion,
methyl parathion, and malathion.
Since little Information was available on the health status of youth
engaged in agriculture, the medical records morbidity study was included
as part of this research. Medical records were examined for the occur-
rence of selected illnesses in children of farm workers and non-farm
workers. Knowledge obtained from this morbidity study may help to iden-
tify health problems which may be more prevalent in children of farm
workers. Findings of certain adverse health effects among youth may
suggest the need for further epidemiologic studies.
The primary objective of this study was to determine whether youth
under 16 years of age who work in agriculture are significantly at risk
to potential adverse health effects from exposure to pesticides. Spe-
cific objectives of this study were to: 1) assess the exposure among
youth working in onions to agricultural chemicals; 2) compare this
potential exposure among youths to that of adults working in onions;
3) determine the incidence of certain illnesses in the children of farm
workers via migrant health clinic records; and 4) compare this incidence
to that for children of non-farm workers.
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510
MATERIALS AND METHODS
A. Exposure Assessment Study
The pesticide exposure assessment study was composed of two parts.
The first part of this research dealt with assessing the pesticide ex-
posure among youths and adults working in a single crop, and comparing
the youth exposures to the exposures of adults working in the sane
fields. The second part of this study involved administering a ques-
tionnaire to farm worker families. The questionnaire included data on
personal hygiene and work practices as well as morbidity information
on each family memeber.
1. Selection of the Study Area and Sample
In order to assess the exposure to pesticides among youth Involved
in field labor, a single labor intensive crop was chosen. In Colorado,
onions is a labor intensive crop, and youth significantly contribute
to the labor effort during onion harvesting. The area selected for study
is located in the Platte River Valley in northeastern Colorado. Growers
in this geographic area employ more seasonal and migrant farm laborers,
and plant more acres in onions, than any other region in the state
(Colorado Dept. of Labor, 1983; Colorado Dept. of Agriculture, 1983).
An initial step in implementing this study was to obtain the co-
operation of both labor contractors and onion growers. Although
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w 1
42
several growers who were initially contacted refused to participate,
a number of onion growers did agree to cooperate. Of this group only
two growers planted onions which required hand labor during harvesting.
The labor contractor associated with this group of growers was contact-
ed and was very cooperative in keeping personnel from the Colorado
Epidemiologic Pesticide Studies Center (CEPSC) informed regarding
workers1 activities in harvesting particular crops of onions. All
the workers who participated in the sampling phase were associated
with this particular labor contractor.
2. Development and Pretesting of the Study Questionnaire
The study questionnaire used in this effort (Appendix A) con-
sisted of family work practices and past health experience. The work
practices of each family member included types of clothing worn while
working, number of hours worked per day. number of days worked per
week, and similar data. The past health experience data included symp-
toms commonly associated with mild and acute pesticide poisoning. In
addition to these two major areas, personal hygiene practices were also
ascertained for each family member. Approximately 50 percent of the
questions were selected from the questionnaire used in the National
Pesticide Exposure Assessment Study of the Citrus Industry (Miami
Pesticide Hazard Assessment Program, 1981). The questionnaire was
translated into Spanish to aid in administering the questions to
families who spoke only Spanish.
The questionnaire was field tested in August of 1981. A bi-
lingual employee from the Colorado Migrant Council in La Salle,
Colorado administered the questionnaire to farm worker families
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512
43
living in migrant housing projects in Weld County, Colorado. Follow-
ing the pretest, any questions that were ambiguous were corrected and
questions that were not answered by the interviewees were deleted.
The information obtained through this questionnaire was used to assess
the work practices, personal hygiene practices, and health experience
of youth (younger than 16 years of age) and adults (16 years or older).
3. Field Preparation
During the spring of 1982, information regarding pesticides ap-
plied to onions that would be hand harvested was obtained. These data
were used to test laboratory analytical procedures. The pesticides
of interest in this study were: toxaphene, ethyl parathion, methyl
parathion, and malathion.
A questionnaire was also developed to obtain pesticide usage data
from growers (Appendix B). This questionnaire was administered, after
all pesticide applications had been completed during the 1982 season,
to the person responsible for applying pesticides to the fields used
in this study.
An observation form was also developed to record pertinent field
data on each worker that participated in the study (Appendix C). Prior
to collecting field samples, this form was field tested to insure that
it was adequate for obtaining the desired information on each study
participant. In addition, a field data form was prepared in order
to record field conditions on each sampling day (Appendix D).
The environmental samples (soil, foliage, and field air) were
collected during the actual harvesting of onions. The hand harvest-
ing of onions in 1982 took place during late August. Each field was
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513
44
divided into grids consisting of three sections (Figure 3). Twenty
samples of soil and foliage were collected from each section of the
field. Field A consisted of approximately 10 acres and Field B of 12
acres. Soil, foliage, and field air samples were collected from each
field on each day of sampling. Soil samples were collected using a
core sampler and taking only surface soil (1 inch in depth). Foliage
samples were obtained by using a leaf punch (diameter of 15 mm). Both
soil and foliage samples were placed in glass jars (foliage in 3 oz.
jars, soil in 7 oz. jars). All jars had been rinsed two times with
acetone and three times with hexane prior to sample collection. All
jar lids were lined with teflon liners rinsed with acetone and hexane.
Field air samples were collected by the method described by Goes
(1979). The polyurethane foam plug air sampler was composed of a sam-
pling -module, flow controller, rotameter, and vacuum pump. The sam-
pling module consisted of two glass housings mounted in series. Each
glass housing had a central chamber (2.0 inches in diameter) separated
in the center and fitted with an air tight 0-ring seal. The housings
tapered to 0.5 inches at each end and were fitted with 0-ring seals.
Each housing contained one polyurethane foam plug (Figure 4). The
rotameter/flow meter (Brooks Sho-Rate 8900-1335) was located down-
stream from the sampling modules. A portable, electric vacuum pump
(Bell and Cosset Model SYC 21-1) supplied vacuum to the sampling de-
vice. The methods for cutting and cleaning the plugs are described
in Appendix E section IV. C.
Human exposure samples, consisting of urine and gloves, were
also collected during the actual days of field harvest. The urine
samples, collected for use as indicators of body absorption and body
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514
Figure 3. Air, soil, and foliage sampling sites in the
study fields.
• - denotes sampling site of soil and foliage.
- denotes placement of air sampler.
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515
DAY 1
DAY 2
• k •
• I •
«i«
FIELD A
FIELD B
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516
Figure 4. Polyurethane foam plug air sampling module (top)
and vacuum pump (bottom) used for collecting
field air samples.
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517
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518
49
burden of pesticides, were obtained from youth and adult field workers
prior to the workers leaving the field. Workers that agreed to parti-
cipate were paid five dollars for the urine samples. Obtaining urine
samples eliminated the need for assistance from the local migrant
health clinics in collecting human samples, such as blood. Each par-
ticipant was provided a three ounce glass jar that had been rinsed
two times with acetone and three times with hexane. Teflon liners
were also rinsed and inserted into the lids of each jar.
The analysis of woven gloves worn by workers in the field was
also used in assessing dermal exposure. Initially, thin cotton gloves
were purchased for the study, but these gloves were extremely difficult
to "clean-up" prior to analysis by gas chromatography. Therefore,
thin, nylon, lint-free gloves were purchased from VWR Scientific, Inc.
These gloves were machine washed twice and soxhlet extracted twice
(Appendix £ IV.D.). This procedure eliminated peaks which interferred
with the pesticides of interest when the extracts were injected into
gas chromatographs fitted with an electron capture detector and a
nitrogen-phosphorous detector.
4. Collection of Environmental and Human Exposure Samples
Samples were collected on August 25th (Day 1), August 26th (Day 2),
and August 31st (Day 3), 1982. On Days 1 and 2, samples were collected
in Field A; on Day 3, samples were collected in Field B. At the be-
ginning of each sampling day, the field data forms were completed.
Personnel from the CEPSC asked field workers if they would participate
in the study. It was explained to the workers that if they wore the
gloves and gave a urine sample at the end of the work day, they would
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50
519
receive five dollars for the effort. If the worker agreed to wear the
gloves and/or give a urine sample, an observation form was filled out
on the worker. The participating workers were observed for the period
of time that they remained in the field, and the observation forms
were completed during this time.
Initially, the gloves were to be worn for four hours. However,
due to various reasons, the time that the gloves were worn ranged from
two to four hours. The time that the gloves were put on by each worker
and the time the gloves were collected from each worker were recorded
on the observation form.
If the worker agreed to give a urine sample, & pre-rinsed jar was
handed to the participant. When the sample was brought to the field
assistants, a label was completed and directly attached to the sample.
The sample was then kept in a styrofoam cooler with blue ice. The
participant then signed a form which acknowledged receipt of five
dollars for participation in the Youth in Agriculture Project. As
the glove samples were collected they were tightly wrapped in pre-
rinsed aluminum foil, labelled, and kept in a styrofoam container
with blue ice. Labels included the following information: sample
ID, name, age, sex, date, field location, and the number of hours
the gloves were worn.
The air sampler was placed in operation as soon as possible after
arriving at the field and located in that part of the field where the
majority of harvesting was to take place. The sampling train was set
approximately two feet above ground, and the pump was located upstream
from the sampling train. The flow rate was set at 18.82 liters per
minute. Figure 3 depicts the air sampler placement in Field A. Field
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51 520
air samples were collected only in Field A due to the breakdown of
the vacuum pump on Day 3. After the air samples were collected, the
two foam plugs were tightly wrapped in pre-rinsed aluminum foil.
Field assistants collected the foliage and soil samples according to
the previously described sampling scheme (Figure 3). All environmental
samples were labelled and placed in styrofoam containers with blue ice.
Upon arrival at the Pesticide Center Laboratory, all samples were
logged in, labelled, and stored in a freezer at -4eC.
5. Laboratory Analyses
Operating parameters for the gas chromatograph are found in Section
I of Appendix E. The solvents and reagents utilized in this study are
listed in Section II of Appendix E. Each of these solvents met purity
standards outlined in the Manual of Analytical Methods (Environmental
Protection Agency, 1980). A description of the pesticide standards
used in this investigation is found in Section III of Appendix E.
Methodology for analysis of each sample type (soil, foliage, field
air, and gloves) is detailed in Appendix E (Sections IV.A.-IV.D).
Levels of the pesticides of interest were calculated using the follow-
ing method:
1) A sample factor was calculated using the formula -
finjection volume"! „ {"concentration ofl
[of standard (yl)J [standard (pg/uPJ ,
* pg/mm
[peak height (mm)]
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521
52
2) Next the total nanograms in the sample were calculated -
T peak height T x ["factor "j x ffinal volume "I x F dilution 1
[of sample (am)J L(P8/mm)J Lof sample (ml)J Lfactor (if any)J m
[injection volume of sample (yl)]
3) If parts per billion (ppb) were desired, the nanograms in the
sample were divided by the sample weight (in grams).
The urine samples were analyzed for toxaphene and three major
dialkyl phosphates: diethyl phosphate (DEP), diethylthiophosphate
(DETP), and dimethyl phosphate (DMP). These three dialkyl phosphates
are the chronic exposure metabolites resulting from exposure to ethyl
parathion, methyl parathion, and malathion. Appendix E section IV.E.
describes the laboratory methodology for the urine samples.
Since toxaphene is a mixture of isomers of chlorinated camphene,
the chromatograph for toxaphene is composed of more than 20 peaks. In
calculating toxaphene levels in the various substrates, 16 major peaks
were numbered and used in determining the total nanograms of toxaphene.
A chromatogram of the 800 pg/pl toxaphene standard and the peaks used
in calculations are shown in Figure 5. Peak number one was not used
in the calculations due to possible interference with para,para1-
dichloro diphenyl dichloro ethylene (DDE). Also peak number 16 was not
used since it was present in only some of the samples. All peak heights
(numbers 2 through'15) were summed to obtain a peak height for each
sample and standard. Toxaphene levels were then calculated according
to the above method. A chromatogram of the 100 pg/pl organophosphate
standard is found in Figure 6. This standard was used in quantifying
-------
Figure 5. Chromatograa of the 800 pg/ul tqxaphene standard Injected into a gas
chronatograph equipped with a Ni electron capture detector.
r\j
-------
E
E
12
16 20
Tim* (minute*)
24 28 32 36
U1
-------
524
Figure 6. Chromatogram of the 100 pg/ul organophosphate
standard injected into a gas chromatograph
equipped with a nitrogen-phosphorous detector.
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525
0
o.
0
0.
E
E
o»
flS
o
a.
8
Time (minutes)
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526
57
organophosphate levels in the soil* foliage, field air, and glove
samples. Samples were injected at an appropriate dilution so chat peak
heights between sample and standard did not vary more than 50 percent.
A laboratory report form (Appendix F) was completed as each sample was
analyzed.
The quality assurance objectives are listed in Table 6. The pre-
cision standard deviation and accuracy were set at ± 20 percent which
is the actual spiking quantity ± 2 standard deviations.
6. Administering the Questionnaire
After the questionnaire was pretested and revisions were made, a
female bilingual employee of the Sunrise Health Clinic in Greeley,
Colorado was employed and trained to administer the questionnaire to
Spanish-speaking farm worker families during 1982. The purpose of
the study and the importance of minimizing interviewer bias were fully
explained to her. An employee of the CEPSC accompanied her during
the administration of all questionnaires.
The questionnaires completed during 1983 were administered by a
female, bilingual farm worker who was familiar with the Youth in Ag-
riculture project from the previous year. The purpose of the study
and the importance of minimizing interviewer bias were also explained
to her.
As the questionnaires were completed, they were checked for com-
pleteness and accuracy in coding. All questionnaires were administered
to the female head of household.
-------
Quality assurance objectives for
Colorado. 1982-1983.
TABLE 6
•asurement data in terms of precision and accuracy,
Measurement
Parameter
Toxaphene
Precision
Method Experiment Standard
Reference Conditions Deviation Accuracy
Appendix E Soil samples spiked with + 20% + 20Z
Ethyl Parathion
Methyl Parathion
Malathion
Dlalkyl phosphates-
DEP, DMP. DETP
Appendix E
Appendix E
Appendix E
Appendix E
toxaphene, ethyl parathion,
methyl parathion, and
malathlon
Foliage samples spiked with + 20Z
toxaphene, ethyl parathion,
methyl parathion, and
malathlon
Field air samples spiked with + 20Z
toxaphene, ethyl parathion,
methyl parathion, and
malathlon
Gloves spiked with toxaphene, + 20%
ethyl parathion, methyl para-
thion, and malathlon
Urine samples spiked with ± 20Z
toxaphene, DEP, DMP, DETP
20Z
In
00
20Z
20Z
20Z
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528
59
7. Statistical Analysis
The data collected in the exposure assessment study consisted of
three types: observational data; human exposure data; and questionnaire
data. Due to the inherent differences in each data type, the statisti-
cal analyses for each data type are described separately.
a. Observational Data
The data collected on the observation forms were tabulated to
compare males to females and youths to adults with respect to the
clothing worn while working (such as long or short pants, shoes, hats).
Clothing types were summed for male youth, female youth, male adults,
and female adults. Chi-square tests were computed for each clothing
type and for various combinations of youth, adults, males, and females.
No other statistics were calculated since no protective equipment
(other than the study gloves) was worn by the workers.
b. Human Exposure Data
Laboratory results from the glove analyses were transferred to a
form which included the laboratory identification number, age of the
participant, sex of the participant, field (A or B), day (1, 2, or 3).
hours that the gloves were worn, and micrograms of toxaphene, ethyl
parathion, methyl parathion, and malathion. The data were submitted
to further quality control by a second person. The data were then
keypunched on computer cards. Keypunching accuracy was insured by full
re-key verification and a visual comparison of a computer printout of
the data and the data forms.
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60 529
Toxaphene levels In Field A.and Field B and ethyl parathion and
methyl parathion levels in Field A were analyzed using yg/hr as the
dependent variable. The correlation of the yg/hr value for each of
the above pesticides with its normal score was calculated. The cor-
relation of the data with its normal score provides a measure of
normality with a very high correlation being consistent with normali-
ty (Filliben, 1975). The yg/hr values did not appear to be normally
distributed, and since the natural logarithm of the yg/hr values and
their normal scores were highly correlated! the logged values were
used as the dependent variables.
The method of statistical analysis was analysis of variance
utilizing a regression model with each main effect and all possible
interactions (excluding any field by day interactions due to the
confounding of the day and field effects). The main effects used
in the toxaphene analysis were: age (youth vs. adults), sex (male
vs. female), field (Field A vs. Field B), and day (Day 1 vs. Day 2).
The main effects examined in the statistical analysis of ethyl para-
thion and methyl parathion levels were: age (youth vs. adults), sex
(male vs. female), and day (Day 1 vs. Day 2). The main effect or
interaction entered into the regression equation first was the one
most highly correlated with the dependent variable. The remaining
main effects and interactions were entered into the regression
equation according to Which variable was most highly correlated
A
with the residuals (y. - y.) from each previous regression.
Due to the number of values below the detection limit (200 ng)
in Field B for ethyl parathion, methyl parathion, and malathion,
the statistical method used was chi-square analysis. Chi-square
-------
530
61
tests were computed to compare youth to adults with respect to pesti-
cide levels: zero (less than 100 ng), trace (100-200 ng), and above
detection (greater than 200 ng). The laboratory results were reported
in such a manner that values less than one-half of the detection limit
were reported as zero, and values between one-half of the detection
limit and the actual detection limit were reported as trace. This
was to insure that values less than the detection limit are not re-
ported as true values since the error associated with such values in-
creases and the actual value is questionable. Malathion values for
Field A were not statistically analyzed since all values were zero.
Since only two urine samples had detectable levels of alkyl phos-
phate metabolites, no comparative statistical analysis was performed
on these data. Thus, the results of the urine samples are simply des-
cribed by age, sex, field, and day distributions only.
c. Questionnaire Data
The questionnaire responses were computer coded by one individual
in an effort to reduce possible coding bias. The coding was thoroughly
rechecked by the same person. These data were then entered directly
into a computer file. The accuracy of the newly created computer file
was checked by comparing 10 percent of the responses on the original
questionnaire with the computer printout.
The primary objective of statistical analysis of the questionnaire
responses was to determine whether or not work practices differed be-
tween the youth and adult cohorts. A second objective was to describe
the past health experience of the two groups. The statistical method
explored was that of chi-square analysis to test the significance of
-------
531
various associations. Two other.groups were used in describing the
health experience of migrant families; these groups consisted of youth
(<16) and adults (_>16) who did not work in the fields.
B. Medical Records Morbidity Study
Fort Lupton, Colorado is an agricultural community located on the
Colorado front range. Major crops grown in the area include sugar
beets, onions, cucumbers, alfalfa, corn, and hay. The farm labor in
this area is supplied by seasonal and migrant farm worker families.
A large proportion of the farm workers in this area receive their health
care at a migrant health clinic operated in Fort Lupton. Five satel-
lite clinics, associated with the Fort Lupton Salud Clinic, are located
in Dacono, Frederick, Longmont, Brighton, and Platteville, Colorado.
The Fort Lupton Salud Clinic serves migrant and seasonal farm workers,
as well as those not involved in agriculture. The clinic users include
both farm worker and non-farm worker populations.
1. Acquisitions of Medical Records
The medical records for all the clinics are centralized at the
Fort Lupton Salud Clinic. All medical records at the Fort Lupton
Salud Clinic for the three year period 1979-1981 were examined in this
study. The medical records for the study period had been stored on
computer tapes. One computer tape included all patient visits during
1979 for a total of 13,731 patient visits; a second computer tape
consisted of 58,662 patient visits for the two year period 1980-1981.
These data tapes were received from the Fort Lupton Salud Clinic in a
format that could be read by the computer at Colorado State University.
-------
532
A computer print-out was obtained from the health clinic which cross-
referenced the diagnosis codes and their descriptions.
Upon receipt of the two tapes, copies were made and stored on the
Colorado State University high speed computer (CDC CYBER 172). Fre-
quencies on case characteristics accounted for all patient visits, a
total of 72,393. The two large data files were arranged into workable
subfiles in order to study only selected diseases. All cases diagnosed
as having a disease of interest to this study were included in the
created subfiles.
The information contained in the computer files included the fol-
lowing data on each patient visit: sex, age, ethnic group, disease
code, farm worker status (migrant, seasonal, or other), and date of
visit. The subfiles consisted of four groups of illnesses: respira-
tory illnesses, dermatological disorders, eye diseases, and symptoms
of possible pesticide poisoning (Table 7). The last group included
symptoms which have been associated with exposure to pesticides.
This category was included since the diagnostic code for poisoning
was not available.
The Fort Lupton Salud Clinic classified a patient as a migrant
if the Fort Lupton area was not considered the patient's home base.
The seasonal status cohort was comprised of those persons who listed
Fort Lupton or the proximate area as their home and were engaged in
farm labor for part of the year. The 'other' status cohort included
those patients who^resided in the area of the Fort Lupton clinics
but did not work in the fields for any portion of the year. For the
purposes of this study, the 'other' status was used as the non-migrant,
non-farm comparison group.
-------
TABLE 7
Disease groupings used in the Medical Records Morbidity Study, Colorado, 1979-1981.
Respiratory Diseases:
Asthma
Bronchitis and bronchiolitis, acute
Laryngitis and tracheitls, acute
Emphysema, bronchlectasis
Hay fever
Hype rventilation
Influenza
Pneumonia
Tuberculosis
Strep throat, scarlet fever
Acute upper respiratory tract infection
Acute otitis media
Sinusitis, acute and chronic
Bronchitis, chronic
Other respiratory system diseases
Dyspnea
Painful respiration and pleurodynla
Eye Diseases:
Viral conjunctivitis
Conjunctivitis and opthalmia
Eyelid infections and chalazion
Dermatologic Diseases:
Contact and other dermatitis
Chronic skin ulcers
Eczema and allergic dermatitis
Dermatophytosls and dermatomycosls
Pruritis and related conditions
Rash
Seborrhoeic dermatitis
Urticaria, allergic edema
Other Infections skin/subcutaneous
Symptoms of Possible Pesticide Poisoning:
Dizziness and giddiness
Convulsions
Headache
Disturbance of sensation
Parklnsonlsm
Syncope, faint, blackout
Blocked tear duct
Abnormal involuntary movement
Blurred vision
Chest pain
Malaise, fatigue, tiredness
Nausea, vomiting
Stress Incontinence
Cough
Excessive sweating
en
o-i
-------
65
53A
2. Data Analysis
The medical records of youths between the ages of 5 and 15, inclu-
sively, were the main focus of this study. The frequency of each
selected disease grouping was calculated for the youth of migrant farm
workers, the youth of seasonal farm workers, and the youth of non-farm
workers. In addition, these youth study cohorts were categorized by
age group and sex. A total of 26,216 patient visits for children less
than 16, categorized by status and sex, were recorded during 1979-1981.
Since month of disease occurrence was an important variable, the created
data files included this factor, resulting in 26,206 patient visits.
Each disease grouping was then analyzed to take into account four epi-
demic logic variables: status, sex, age, and month of year (season).
The total number of patient visits in each status, sex, age, and season
group was the denominator used in calculating subclass proportions for
each disease grouping.
The age groupings used in this study were 0-4, 5-9, and 10-15.
The time periods consisted of a non-growing season (November through
April), early growing season (May through July), and a late growing
season (August through October). In addition, the number of patients
in each status, season, sex, and age classification was tabulated for
each disease grouping.
In order to obtain an understanding of any interrelationships
among the four variables of interest, multiple logistic regression
analysis was performed on the data for each disease grouping. This
statistical analysis is especially useful in identifying significant
epidemiologic variables and possible interactions among variables
(Kleinbaum et al., 1982). For the purposes of this study, a p-value
-------
535
of .10 or less was necessary for.the variable to be retained In the
final analysis. Odds ratios on selected comparisons were calculated
using standard methods (Fleiss, 1981).
-------
536
RESULTS
A. Exposure Assessment Study
1. Environmental Data
Pesticide usage information (including common name of pesticide,
type of pesticide, date of application,' method of application, and
amount applied per acre) for Field A and Field B is provided in Table
8. A total of seven pesticides were applied to the fields during the
1982 onion planting and growing season. The pesticides of interest to
this study included only the insecticides. Although methyl parathion
was not listed by the growers as a pesticide of use, all samples were
analyzed for this compound since it is not uncommon for methyl para-
thion to be found in small quantities as a contaminant in ethyl para-
thion preparations.
Table 9 summarizes the results of the laboratory analyses of the
soil, foliage, and field air samples. Samples were collected in Field
A on August 25th and 26th, 1982 (Days 1 and 2); and in Field B on
August 31st. 1982 (Day 3). Thus, the shortest time period between ap-
plication and sampling (of insecticides of interest) was approximately
six weeks in Field B. Surprisingly, the toxaphene levels in soil and
foliage in Field A were higher than in Field B. As mentioned in
Chapter IV, field air samples were collected only in Field A due to
-------
68
537
TABLE 8
Pesticide usage data for Field A and Field B during the 1982 growing season. "Youth in
Agriculture: Exposure Assessment and Medical Records Morbidity Study." Colorado.
1982-1983.
Date of Method of
Field Application Application
A 6-8-82 Plane
A 7-5-82 Ground Boom
Spray
B 6-10-82 Ground Boom
Spray
B 7-7-82 Ground Boom
Spray
B 7-18-82 Plane
B 8-8-82 Plane
Type of
Pesticide
Insecticide
Insecticide
Insecticide
Insecticide
Fungicide
Insecticide
Insecticide
Insecticide
Insecticide
Fungicide
Fungicide
Insecticide
Insecticide
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide
Cotanon Name
of Pesticide
Ethyl Parathion
Toxaphene
Malathion
Toxaphene
Maneb
Malathion
Toxaphene
Malathion
Toxaphene
Sulfur
Maneb
Ethyl Parathion
Toxaphene
Sulfur
Mancozeb
Ory-Cop
Sulfur
Oxy-Cop
Amount Applied
per Acre
0.5 pints /acre***
3.0 pints/acre**
1.3 pints/acre*
2.0 pints/acre**
2.0 pints /acre
1.0 pint /acre*
2.0 pints/acre**
0.5 pints /acre*
1.0 quart /acre**
1.0 pint/acre**
2.75 pints /acre
0.5 pints /acre***
2.67 pints/acre**
1.0 quart/acre**
2.0 Ibs./acre
1.0 quart /acre
0.5 gal. /acre**
0.5 gal. /acre
* Contains 5 pounds of actual chemical per gallon.
** Contains 6 pounds of actual chemical per gallon.
*** Contains 8 pounds of actual chemical per gallon.
-------
TABLE 9
A summary of the laboratory analyses of soil, foliage, and field air samples. "Youth in Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado, 1982-1983.
*Soil
Field A
Day 1
Day 2
Field B
Day 3
Fol lage
Field A
Day 1
Day 2
Field B
Day 3
Field Air
Field A
Day 1
Day 2
Toxaphene
2.1 ppm
3.9 ppm
2.1 ppm
17.5 ppm
15.0 ppm
1.3 ppm
0.0
0.0
Ethyl Para tli ion
0.0
0.0
0.0
0.0
100.5 ppb
0.0
0.0
0.0
Methyl Paration
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Ma lath ion
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Pesticide levels in soil are given as the mean value for the three sections in each field.
CO
-------
539
70
the malfunction of the air sampler vacuum pump on Day 3. Due to the
low weights of the foliage samples, samples collected on the same day
were combined to allow for increased weight of the foliage disks.
Toxaphene was found in both soil and foliage samples from both fields.
The toxaphene levels ranged from 1.3 to 17.5 ppm. None of the air
samples were positive for any of the insecticides. Ethyl parathion
was found on the foliage samples from one field at a level of 100.5
ppb. The quality assurance objectives, as outlined in Table 6, were
met for the foliage and soil samples. Analysis of the air samples met
the quality assurance objectives for toxaphene and malathion, but not
for ethyl parathion and methyl parathion.
2. Results of the Data Analysis
a. Observational Data
Sixty-nine individuals were observed while harvesting onions.
These harvesters wore normal type work pants, shirts, shoes, and head
coverings. None wore any type of protective equipment (goggles, res-
pirator, or rubber suit). The workers wore the gloves provided by the
study. Table 10 presents the number and percent of male and female
vouth and adults and the type of clothing they wore while doing field
work. The most noticeable difference between youth and adults was in
the wearing of hats, with 53.8 percent of adults wearing hats compared
to 16.7 percent of youth (this difference was statistically signifi-
cant at P-.002). All of the observed youth and adults wore long pants
except one female youth. A larger percentage of male youth and adults
wore shoes compared to their female counterparts.
-------
TABLE 10
A sunmary of the number (N) and percent (Z) of Male and female youth and male and female adults for each
clothing type. "Youth in Agriculture: Exposure Assesment and Medical Records Morbidity Study,"
Colorado, 1982-1983.
Males
N Z
Pants
Shirt
Shoes
Hat
Long
Short
Long-sleeved
Short-sleeved
Yes
No (including
thongs)
Yes
No
19
0
13
6
18
1
4
15
100.0
0.0
68.4
31.6
94.7
5.3
21.1
78.9
Youth
Females
N Z
10
1
5
6
9
2
1
10
90.9
9.1
45.4
54.6
81.8
18.2
9.1
90.9
Adults
Total
N Z
29
1
18
12
27
3
5
25
96.7
3.3
60.0
40.0
90.0
10.0
16.7
83.3
Males
N Z
16
0
6
10
16
0
10
6
100.0
0.0
37.5
62.5
100.0
0.0
62.5
37.5
Females
N Z
23
0
19
4
16
6
11
12
100.0
0.0
82.6
17.4
69.6
23.4
47.8
52.2
Total
N Z
39
0
25
14
32
7
21
18
100.0
0.0
64.1
35.9
82.0
IB.O
53.8
46.2
-------
72
541
On Day 3 in Field B there were approximately 47 adult males, 30
adult females, 20 male youth, and five female youth involved in the
harvesting of onions. There were approximately 20 non-working children
in the field. The youngest worker from whom information was obtained
was a seven year old male, the oldest was a 53 year old female.
Chi-square tests were calculated for each clothing type for youth
vs. adults (males and females combined), youth vs. adults (males and
females separate), female youth vs. female adults, and male youth vs.
male adults. There was a significant association (p».026) between
female age and type of shirt worn, with a higher percentage of females
less than 16 wearing short-sleeves than adult females. All four tests
showed an association between age and the wearing of a hat (p<.03)
with a smaller percentage of the youth cohort wearing hats than the
adult group. There was no significant association between age and
type of pants worn, and between age and the wearing of shoes. However,
a greater percentage of females (youth and adults) did not wear shoes
compared to the male group.
b. Human Exposure Data
A total of 64 glove samples and 44 urine samples were collected
and analyzed. The numbers of human exposure samples are shown in
Table 11.
The geometric mean values of toxaphene from Fields A and B and of
ethyl parathion and methyl parathion from Field A in glove samples are
provided in Table 12. A large number of glove samples had values less
than the detection limit of 200 ng for ethyl parathion, methyl para-
thion, and malathion. Therefore, the results are presented as number
-------
73
542
TABLE 11
Numbers of human exposure samples for youth and adult study participants.
"Youth in Agriculture: Exposure Assessment and Medical Records Morbidity
Study," Colorado, 1982-1983.
Youth (<16)
Females
Males
Adults (^16)
Females
Males
Gloves
9
19
21
15
Urine
3
17
11
13
Total 64 44
-------
543
TABLE 12
A summary of the geometric means (G.M.) and geometric standard deviations
(G.S.D.) for selected main effects generated from the analysis of
variance for the glove samples. "Youth in Agriculture: Exposure
Assessment and Medical Records Morbidity Study." Colorado, 1982-1983.
G.M. G.S.D.
(ug/hr)
Toxophene (Field A and Field B)
Age *
Youth 16.56 1.87
Adults 22.72 1.83
Sex *
Males 21.64 1.87
Females 17.88 1.87
Field *
Field A 32.34 1.57
Field B 13.50 1.58
Ethyl Parathion (Field A)
Day *
Day 1 0.84 1.58
Day 2 0.36 1.73
Age
Youth 0.37 1.58
Adults 0.48 2.08
Methyl Parathion (Field A)
Day *
Day 1
Day 2
Age
Youth
Adults
0.42
0.15
0.16
0.21
1.60
1.88
1.83
2.25
* - significant at p<.05
-------
544
of Individuals in each age and sex cohort with pesticide levels in the
zero, trace, or above detection level group (Table 13).
Based on the analysis of variance of pesticide residues in gloves,
the field variable was most highly correlated with the toxaphene values
while the day variable was most highly correlated with both ethyl para-
thion and methyl parathion. The main effects of field, age, and sex
were found to be significant (p<.05) for the toxaphene levels in gloves.
Gloves worn by adults had higher geometric mean toxaphene levels than
those worn by youth (22.72 ug/hr vs. 16.56 ug/hr). The geometric mean
toxaphene levels for males who wore gloves was higher than the geo-
metric mean level for females (21.64 ug/hr vs. 17.88 ug/hr). Field
A had a higher geometric mean toxaphene level than Field B (32.34 ug/hr
vs. 13.50 ug/hr).
The analysis of variance of the ethyl parathion and methyl para-
thion levels in gloves from Field A both resulted in only the day var-
iable being significant (p<.05). The geometric mean for ethyl parathion
in gloves from Field A was 0.84 ug/hr for Day 1, and 0.36 ug/hr for Day
2. The methyl parathion values were also higher on Day 1 than Day 2
(0.42 ug/hr vs. 0.15 ug/hr).
The main effect of age for both ethyl and methyl parathion values
was not significant. The geometric mean ethyl parathion level of gloves
worn by adults was higher than gloves worn by youth (0.48 ug/hr vs.
0.37 ug/hr). The same trend was observed for the geometric mean methyl
parathion values with the gloves worn by adults having higher levels
than those worn by youth (0.21 ug/hr vs. 0.16 ug/hr). Table 12 sum-
marizes the geometric means and geometric standard deviations for
selected main effects.
-------
TAHLR 13
Raaulta of the clil-square tact* for ethyl paratnlon, Methyl parathlon. and ••lathton residues found In
glo»« aaaplea tram Field I. "Touth In Agriculture I Exposure Assessment and Medical Record* Horbldltv
Study." Colorado. 1982-1983.
Touth rcaal*
Hale
Adult* Female
(tale
Totala
Youth
Mult*
Totala
O
4
(1.8)*
6
(4.0)
n
(4.3)
3
(2.9)
13
x' -
10
(5.8)
3
(1.2)
13
x' -
Ethyl Parathlon
T AO Totala
1 0 5
(2.2) (1.0)
4 1 II
(4.9) (2.1)
9 3 12
(5.3) (2.3)
238
(3.6) (1.6)
16 7 36
15.18 "
5 1 16
(7.1) (3.1)
II 6 20
(8.9) (3.9)
16 7 36
•*
«.26
.
O
5
(*.6)
9
(10. 1)
II
(II. 0)
8
(7.3)
33
xl -
14
(14.7)
19
(18.3)
33
X1 -
Hethyl Parathlon
T AD Totala
005
(0.3) (O.I)
2 0 II
(0.6) (0.3)
0 1 12
(0.7) (0.3)
008
(0.4) (0.2)
2 1 36
••
6.77
2 0 16
(0.9) (0.4)
0 1 20
(I.I) (0.6)
2 1 36
3.35
0
2
(2.8)
6
(6.1)
10
(6.7)
2
(*.*)
2Q
x1 -
8
(8.9)
12
(II. 1)
20
x' -
Main
T
3
(1.5)
2
(3.4)
2
(3.7)
4
(2.4)
II
.1.44"
5.
(4.9)
6
(6.1)
II
0.65
it h Ion
AD
0
(0.7)
3
(1.5)
0
(1-7)
2
(I.I)
5
3
(2.2)
2
(2.8)
5
— . — -
Totala
5
II
12
8
36
16
20
36
• - expected frequeuele* are printed below observed frequencies
•» - significant at p<.05
O - pesticide levels less than 100 ng.
T - pesticide levels between IOO-2OO ng.
AD - pesticide levels grrnter than 7OO ng.
LTI
•fc*
LT1
-------
77 546
The results of the chi-square tests for ethyl parathion, methyl
parathion, and malathion in Field B are presented in Table 13. The
test was computed for male youth, female youth, male adults, and female
adults using three levels of each pesticide: zero (less than 100 ng);
trace (100-200 ng); and above detection (greater than 200 ng). A
second test was calculated for youth vs. adults taking into account the
three pesticide levels. It is important to note that some of the cells
in the chi-square tests resulted in expected frequencies less than one.
However, the zero, trace, and above detection level groups were main-
tained to allow for a more complete description of these data. The
chi-square tests for ethyl parathion were significant (p<.01). There-
fore, an association between the level of ethyl parathion and age
(youth vs. adults) exists. It can be seen in Table 13 that a higher
proportion of youth have zero and trace levels of ethyl parathion than
do adults. The chi-square tests for methyl parathion and malathion
were not significant (i.e., p>.05), when youth were compared to adults.
None of the urine samples had measurable levels of toxaphene.
Only 10 of the 44 urine samples had trace (<50 ppb) or levels above
the detection limit (>50 ppb) of alkyl phosphates (Table 14). It is
of interest that the only environmental sample with a detectable level
of an organophosphate was collected on Day 2 in Field A. The nine
year old male with 92 ppb of DETP detected in his urine was working
on this day.
The .quality assurance objectives, as outlined in Table 6, were met
for the glove samples. Analysis of the urine samples for toxaphene
and alkyl phosphates also met the quality assurance objectives.
-------
78
TABLE U
A summary of the age, sex, field, and day characteristics for partici-
pants with alkyl phosphate levels detected in urine. "Youth in
Agriculture: Exposure Assessment and Medical Records Morbidity Study,"
Colorado, 1982-1983.
547
Alkyl Phosphate
Age
9
40
13
45
44
16
47
41
23
19
Sex
M
M
M
M
F
F
M
F
F
M
Field
A
A
A
A
B
B
B
B
B
B
Day
2
2
2
2
3
3
3
3
3
3
DEP
T
T
T
0
T
0
T
T
0
T
DETP
92 ppb
0
T
T
0
0
0
0
T
0
DMP
0
0
0
0
0
50 ppb
0
0
0
0
T - trace levels (<50 ppb).
-------
Questionnaire Data
79
5A8
A total of 50 questionnaires were administered to farm worker
families. Five questionnaires were administered during the field
testing of the questionnaire; 18 and 27 questionnaires were adminis-
tered during the summers of 1982 and 1983, respectively. A total of
48 questionnaires were used in the data analyses, since two of the
questionnaires obtained during the questionnaire field test had sever-
al missing items. The questionnaires contained information on 269
individuals. The sex, age (<16 or _> 16 years), and work status
of these individuals are provided in Table 15.
All of the families interviewed were Mexican-American. Of the 48
families, 47 were considered migrant farm workers, and one family was
described as seasonal. The age and sex distributions of the families'
working members are provided in Table 16.
In order to determine if work practices differed between the youth
and adult cohorts, three variables were closely examined: time vari-
ables; personal hygiene practices; and types of clothing worn while
working. Table 17 depicts the time variables for working youth and
adults. Chi-square tests were computed for three time variables
(months worked per year, days worked per week, and hours worked per
day) and youth vs. adults, male youth vs. male adults, and female
youth vs. female adults. All of the above computed chi-square statis-
tics were significant at p<.05. Thus, there is an association between
age and number of months worked per year, days worked per week, and
hours worked per day. In every case, workers less than 16 years of
age worked for shorter time periods than the adults. The total number
-------
80
549
TABLE 15
Sex, age composition, and work status of study participants. "Youth in
Agriculture: Exposure Assessment and Medical Records Morbidity Study,"
Colorado, 1982-1983.
Working Youth (<16)
Working Adults (^16)
Non-working Youth (<16)
Non-working Adults (M.6)
Total
Male
34
73
29
1
127
Female
38
71
19
4
142
Total
72
144
48
5
269
TABLE 16
Age and sex of workers. "Youth in Agriculture: Exposure Assessment
and Medical Records Morbidity Study." Colorado, 1982-1983.
Age Group
(years)
5-9
10-12
13-15
16-19
20-24
25-34
35-44
I45
Unknown
Total
Male
3
15
16
23
7
8
21
13
1
107
Female
5
14
19
18
5
19
17
12
0
109
Total
8
29
35
41
12
27
38
25
1
216
-------
TABLE 17
Percentage of male and female youth and adults working in fields who completed a field questionnaire.
"Youth in Agriculture: Exposure Assessment and Medical Records Morbidity Study," Colorado, 1982-1983.
Total Years Worked
10
Months Worked per Year
<3
4-6
7-12
Days Worked per Week
1-3
4-5
I6
Hours Worked per Day
<4
4-8
>9
Male
17.6
58.9
17.7
5.8
0.0
68.2
27.2
4.5
14.7
17.6
67.7
6.0
51.5
42.5
Youth
Female
25.0
61.1
5.6
8.3
0.0
73.1
26.9
0.0
13.2
28.9
57.9
13.1
34.3
52.6
Total
21.4
60.0
11.5
7.1
0.0
70.8
27.1
2.1
13.9
23.6
62.5
9.8
42.3
47.9
Male
11.0
16.4
24.7
23.2
24.7
11.3
86.4
2.3
0.0
19.1
80.8
0.0
32.9
67.1
Adult
Female
7.0
32.4
19.7
19.7
21.2
7.0
90.7
2.3
2.8
18.3
78.9
0.0
38.0
62.0
Total
9.0
24.3
22.2
21.5
23.0
9.1
88.6
2.3
1.4
18.8
79.8
0.0
35.4
64.6
oo
c_n
-------
82
of years worked was not included in the calculations since this vari-
able is confounded with age of the worker.
Personal hygiene practices were examined by analyzing three
variables: 1) how often work clothes were changed, 2) number of times
a worker bathed per week, and 3) number of times a worker washed his/
her hair per week. Table 18 provides the percentage of male and fe-
male youth and adults for each of the above characteristics. None of
the variables were statistically significant using a p-level of .10.
It is of interest that a higher proportion of adults bathed (88.9
percent vs. 77.8 percent) and washed their hair (82.6 percent vs.
77.8 percent) every day than did the youth cohort. Also, a slightly
smaller percentage of youth changed their clothes every day than did
the adults (81.9 percent vs. 88.9 percent).
Table 19 oresents the percentage of working youth and adults wear-
ing various types of clothing when working in the fields. Chi-square
tests calculated for each of the seven clothing types resulted in a
significant association (p<.03) for only age and head covering, and
a?e and length of sleeves. The youth cohort covered their heads less
while working than the adults (84.7 percent vs. 93.8 percent) and also
wore long sleeves less frequently than the adults (80.6 percent vs.
91.0 percent).
The health experience of the working youth and adult cohorts was
analyzed by looking at differences between the two groups and various
symptoms associated with pesticide poisoning. Due to the small num-
ber of positive responses to questions 14-18 and 26 (Appendix A),
responses from males and females were combined within each group and
the data were analyzed for youth vs. adults only. The number and
-------
TABLE 18
Percentage of male and female youth and adults changing work clothes, bathing, and washing hair.
"Youth in Agriculture: Exposure Assessment and. Medical Records Morbidity Study," Colorado,
1982-1983.
Change work clothes
every day(s)
1
2
3
4
Completely bathe
times per week
1
2
3
4
7
Wash Hair
times per week
1
2
3
4
7
Male
88.2
2.9
5.9
2.9
5.9
2.9
11.8
0.0
79.4
5.9
2.9
11.8
0.0
79.4
Youth
Female
76.3
21.1
2.6
0.0
0.0
0.0
23.7
0.0
76.3
0.0
0.0
21.1
2.6
76.3
Total
81.9
12.5
4.2
1.4
2.8
1.4
18.1
0.0
77.8
2.8
1.4
16.7
1.4
77.8
Male
89.0
4.1
5.5
1.4
2.7
0.0
8.2
0.0
89.0
2.7
0.0
8.2
5.5
83.6
Adult
Female
87.7
7.0
2.8
1.4
1.4
0.0
8.5
1.4
88.7
1.4
0.0
12.7
4.2
81.7
Total
88.9
5.6
4.2
1.4
2.1
0.0
8.3
0.7
88.9
2.1
0.0
10.4
4.9
82.6
oo
en
en
ro
-------
84
553
TABLE 19
Percentage of working youth and working adults wearing various types
of clothing. "Youth in Agriculture: Exposure Assessment and Medical
Records Morbidity Study," Colorado, 1982-1983.
Clothing Type
Head Covered
Yes
No
Long Sleeves
Yes
No
Lontt Pants
Yes
No
Respirator
Yes
No
Rubber Boots
Yes
No
Gloves
Yes
No
Other
Yes
No
Youth
(%)
84.7
15.3
80.6
19.4
98.6
1.4
0.0
100.0
0.0
100.0
45.8
52.8
(1 unknown)
0.0
100.0
Adults
(Z)
93.8
6.2
91.0
9.0
100.0
0.0
0.0
100.0
2.8
97.2
49.3
50.7
0.0
100.0
-------
554
85
percentage of youth and adults responding to the above questions is
provided in Table 20. None of the chi-square statistics for these
questions were significant at a p-level of .10.
The positive responses to question 29 (Appendix A) are provided
in Table 21. The results are presented for working youth and adults
as well as non-working youth and adults. Due to the small number of
positive responses, male and female responses were combined within
each category. The only significant association (p<.05) found between
work status and illness was for Other Allergies (working youth vs.
working adults). For seven of the 12 conditions (chronic cough,
emphysema, hepatitis, hay fever, severe infections, tuberculosis,
and ulcers) none of the four groups had a positive response.
Question 28 (Appendix A) asked for a brief pregnancy history from
women who participated in this study. Forty-seven of the 142 females
for whom information was obtained stated that they had been pregnant.
There were a total of 303 pregnancies (twins were counted as one preg-
nancy), 269 live births, and 37 miscarriages. This resulted in 12.2
miscarriages per 100 pregnancies.
The remaining questions in the Youth in Agriculture questionnaire
were designed to collect information on basic living conditions and to
determine if farm workers are aware of pesticides used around them.
Of the families interviewed, 18 percent do laundry one time per week,
72.4 percent do laundry two to three times per week, and 9.8 percent
do laundry more than three times per week. More than half of the
families were living on farm property (56.3 percent vs. 43.8 percent).
Three of the 48 families were living in households without running
water. None of the heads of households interviewed knew of any
-------
555
TABLE 20
Number (N) and percent (%) of symptoms associated with pesticide
poisoning for working youth and adults. "Youth in Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado,
1982-1983.
Youth
Sick (during last year)
Yes
No
Seen doctor during past year
Yes
No
Trouble with itching
Yes
No
Rash with itching
Yes
No
Trouble with coughing
Yes
No
Felt dizzy during last month
Yes
No
Experienced muscle tremors
Yes
No
Prolonged weakness or paralysis
Yes
No
N
2
70
6
66
3.
69
2
70
3
69
0
72
1
71
0
72
(%)
2.8
97.2
8.3
91.7
4.2
95.8
2.8
97.2
4.2
95.8
0.0
100.0
1.4
98.6
0.0
100.0
Adults
N
4
140
10
134
10
134
3
141
5
139
3
141
1
143
3
141
(%)
2.8
97.2
6.9
93.1
6.9
93.1
2.1
97.9
3.5
96.5
2.1
97.9
0.7
99.3
2.1
97.9
-------
556
87
TABLE 21
Percentage of working and non-working youth and adults with selected
illnesses. "Youth in Agriculture: Exposure Assessment and Medical
Records Morbidity Study," Colorado, 1982-1983.
Has a doctor ever told you
that you had any of the
following conditions?
Anemia
Yes
Arthritis
Yes
Asthma
Yes
Food Allergies
Yes
Other Allergies
Yes
Working
Youth Adults
(%) (Z)
1.4
0.0
1.4
1.4
8.3
2.1
2.1
2.8
2.1
1.4
Non-working
Youth
(%)
4.2
0.0
0.0
2.1
0.0
Adults
(*)
20.0
0.0
0.0
0.0
0.0
-------
88
pesticide related incidents among their family or fellow workers. 5 J /
Surprisingly, only a small percentage of those interviewed were aware
of pesticide usage in their immediate surroundings. Table 22 provides
the results of questions 19, 20, 22, and 23 (Appendix A).
B. Medical Records Morbidity Study
The Fort Lupton Salud Clinic serves migrant and seasonal farm
workers, as well as those not involved in agriculture. The salud
clinics are used almost exclusively by Whites (approximately 45 per-
cent) and Hispanics (approximately 49 percent). Most of the user
copulation are of a low socioeconomic status; the users include both
farm worker and non-farm worker populations. The exact percentage
of the farm worker population that uses the Fort Lupton Clinic is not
known.-
Initially, chi-square analyses for two-way contingency tables
were tabulated on youth (<16 years of age) for each disease grouping
according to status of the patient (Tables 23-26). These tables in-
clude the total number of patient visits by status for youth, the
number of patient visits diagnosed as having one of the illnesses
in the group, and the percent of each status group with the illness.
Table 23 shows that the non-farm status group for youth had the highest
percentage of respiratory illness while the seasonal group had the
lowest. Typically, migrant farm workers begin to arrive in Colorado
in May (for the planting season) and remain in the state through
October (the end of harvesting season).
Table 27 presents the number of patient visits for youth by
status, season, and age group. These numbers were used as the
-------
89
558
TABLE 22
Percent (%) of families responding positively to questions concerning
basic living conditions and pesticide awareness. "Youth in Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado,
1982-1983.
Questions 19, 20, 22, and 23 Z of Families
Are pesticides, such as weed killers,
insecticides, fungicides, and other
chemicals used for pest control:
a. in your home? Yes 36.1
b. on your yard? Yes 11.1
c. at your place of employment? Yes 5.6
Unknown 2.8
To your knowledge, are any
pesticides used around you? Yes 12.5
During the past 12 months, has your
home been treated for pest control Yes 3.5
by a commercial company? Unknown 2.8
During the past 12 months, has your
place of employment been treated
for pest control by a commercial Yes 6.3
c ompany ? Unknown 4.6
-------
559
90
TABLE 23
Number of patient visits with a diagnosis of a respiratory disease.
"Youth in Agriculture: Exposure Assessment and Medical Records
Morbidity Study," Colorado, 1979-1981.
Migrant
Seasonal
Non-farm
Total
No.
Visits
1,798
3,924
20,494
Youth (<16)
Number with
Respiratory
Illness
538
1,034
6,295
X2 - 29.89 (p<.01)
Percent
29.9
26.3
30.7
TABLE 24
Number of patient visits with a diagnosis of a dermatologic disease.
"Youth in Agriculture: Exposure Assessment and Medical Records
Morbidity Study," Colorado, 1979-1981.
Migrant
Seasonal
Non-farm
Total
No.
Visits
1,798
3,924
20,494
Youth (<16)
Number with
Dermatologic
Illness
48
106
595
Percent
2.7
2.7
2.9
(2 - .73 (N.S.)
-------
91 560
TABLE 25
Number of patient visits with a diagnosis of an eye disease. "Youth
in Agriculture: Exposure Assessment and Medical Records Morbidity
Study," Colorado, 1979-1981.
Youth (<16)
Total
No.
Visits
Migrant 1,798
Seasonal 3,926
Non-farm 20,494
Number with
Eye
Diseases
51
78
368
Percent
2.8
2.0
1.8
X2 - 9.84 (p<.01)
TABLE 26
Number of patient visits with a diagnosis of a symptom of possible
pesticide poisoning. "Youth in Agriculture: Exposure Assessment and
Medical Records Morbidity Study," Colorado, 1979-1981.
Migrant
Seasonal
Non-farm
Total
No.
Visits
1,798
3,924
20.494
Youth (<16)
Number with
Possible Pesticide
Poisoning Symptoms
9
14
58
Percent
0.5
0.4
0.3
X2 - 2.88 (N.S.)
-------
561
92
TABLE 27
Number of patient visits by status, season, and age group. "Youth in
Agriculture: Exposure Assessment and Medical Records Morbidity Study,"
Colorado, 1979-1981.
Age
Age
Age
group 1 (0-4)
Migrant
Seasonal
Non-farm
Total
group 2 (5-9)
Migrant
Seasonal
Non-farm
Total
group 3 (10-15)
Migrant
Seasonal
Non-farm
Non- growing
301
1,154
5,407
6,862
152
397
2,398
2,947
190
554
3,025
Early- growing
457
526
2,228
3,211
206
188
1,152
1,546
276
276
1,474
Late- growing
118
462
2,335
2,915
36
156
1,105
1,297
62
211
1,360
Total
876
2,142
9,970
12,988
394
741
4,655
5,790
528
1,041
5,859
Total 3,769 2,026 1,633 7,428
-------
562
93 J
denominators in the analyses of each disease grouping. The study
population consisted of 26,206 patient visits for children less than
16 years of age. The ratio of female to male patient visits was
approximately one (Table 28). The difference in female to male
patient visits was most noticeable in the migrant children in the
five to nine and ten to 15 year old age groups.
The analyses did not include the variable of ethnicity because
the ethnic code was deleted from the medical records during part of
the 1980-1981 period. Analysis of the data for 1979, in which the
ethnic code was retained, showed that most of the total patient visits
by migrants were Hispanic (92 percent).
Several patterns of illness by status were noted during analysis
of the results. Since results shown in these tables were not adjusted
for age, sex, or time of year; no inferences were made based on these
results. The number of visits by patients less than 16 years of age
were evaluated according to status, age, sex, and time of year.
The results for each disease grouping will be discussed separately.
1. Respiratory Diseases
Table 29 presents the data for illnesses of the respiratory system.
Migrant children in the zero to four age group experienced a greater
percentage of respiratory illness than children in either the seasonal
or non-farm cohorts. This increase was evident for each of the three
seasons. This pattern of a higher percentage of migrant children with
-------
TABLE 28
Number of patient visits by age group, sex, and status (migrant, seasonal, and non-farm).
"Youth in Agriculture: Exposure Assessment and Medical Records Morbidity Study,"
Colorado, 1982-1983.
Age:
Sex:
Migrant
Seasonal
Non-farm
Total
0
Female
422
980
5,015
6.417
- 4
Male
454
1,162
4,955
6.571
5
Female
243
402
2,017
1,662
- 9
Male
151
339
2,638
3,128
10 -
Female
337
548
2,929
3.814
15
Male
191
493
2,930
3.614
Total
Female Male
1,002
1,930 1,
9,961 10,
12.893 13,
796
994
523
313
en
o\
-------
95
TABLE 29
Percent of patient visits with a diagnosis of a respiratory disease
by age, status (migrant, seasonal, and non-farm), and growing season.
"Youth in Agriculture: Exposure Assessment and Medical Records
Morbidity Study," Colorado, 1979-1981.
564
Non-growing
Age Group 1 (0-4)
Migrant
Seasonal
Non-farm
Age Group 2 (5-9)
Migrant
Seasonal
Non-farm
Age Group 3 (10-15)
Migrant
Seasonal
Non-farm
46.2
34.5
38.7
38.3
23.0
28.5
37.4
35.4
13.7
16.1
21.9
20.6
Early-growing
38.3
25.9
27.2
28.6
23.0
17.5
23.4
22.8
13.8
15.9
14.5
14.6
Late-growing Total
45.0
31.4
41.0
39.6
19.4
23.7
31.9
30.6
25.8
18.5
17.8
18.2
41.9
31.7
36.7
36.2
23.1
24.7
32.6
. 31.0
15.1
16.5
19.1
18.5
TABLE 30
Percent of patient visits with a diagnosis of a respiratory disease by
sex and age group. "Youth in Agriculture: Exposure Assessment and
Medical Records Morbidity Study," Colorado, 1979-1981.
Age Group:
Female
Male
0-4
36.7
35.8
5-9
29.3
32.4
10-15
16.0
21.0
Total
29.0
31.0
36.2
31.9
18.5
30.0
-------
96
respiratory illness did not occur in the five to nine age group.
Children in the non-farm category had the highest percentage of res-
piratory illness for all three seasons. Those ten to 15 years of age
comprise an important age group since migrant children of these ages
are most likely to work in the fields with their families. In this
age group, there was an increase in the percent of illness in the
late-growing season with 25.8 percent of the migrant youth having
respiratory illnesses compared to 17.8 percent in the non-farm children.
The migrant youth in this age group also experienced an increase in
illness by season (13.7 percent in the non-growing season to 25.8
percent in the late-growing season) whereas the non-farm children
showed a decrease in illness by season (21.9 percent in the non-growing
season to 17.8 percent in the late-growing season). Figure 7 presents
these results graphically.
The percentage of respiratory diseases by sex and age group is
summarized in Table 30. The largest difference between females and
males was in the ten to 15 year old group where the males showed a.
higher percentage of respiratory illness (21 percent for males com-
pared to 16 percent for females).
Odds ratios comparing the migrant to the non-farm children in
the ten to 15 age group were calculated (Figure 8). During the non-
growing season, the migrant children appeared to be at a decreased
risk of respiratory disease with an odds ratio of 0.57 (95 percent
C.I., .33, .81). To the contrary, in the late-growing season the
migrant children had an Increased risk of respiratory disease compared
to the non-farm children with an odds ratio of 1.61 (95 percent C.I.,
565
-------
PERCENT CD
N(D-4) SCO-4) 0(0-4)
N(S-g)
STATUS
SChfl) 0(5-9) N(IO-IS) SOO-15) 0(10-15)
/ ACE GROUPING
Figure 7. Percent of patient visits with a diagnosed respiratory disease by season, status
(M - migrant, S - seasonal, and 0 - non-farm), and age. "Youth in Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado, 1979-1981.
c_n
ON
ON
-------
98
567
30
•2 20
d>
o
&.
o
CL
10
Non-farm
*••..
0-0.57
0-1.61
Migrant
Figure 8.
Non- Early- Late-
growing growing growing
Odds ratios comparing migrant children to non-farm
children in the 10-15 age group during the non-
growing and late-growing seasons. "Youth in
Agriculture: Exposure Assessment and Medical
Records Morbidity Study," Colorado, 1979-1981.
50
o
o
25
0-1.36
0-1.17
Non-farm
Figure 9.
Non- Early- Late-
growing growing growing
Odds ratios comparing migrant children to non-farm
children in the 0-4 age group during the non-
groving and late-growing seasons. "Youth in
Agriculture: Exposure Assessment and Medical
Records Morbidity Study," Colorado, 1979-1981.
-------
568
.67, 2.55). Approximately 35 percent of the visits by male migrant
children ten to 15 years of age had one of the respiratory diseases
in the late-growing season. However, when females were included in
this stratum, the percentage of respiratory illness for migrant children
was reduced to 25.8 percent.
In contrast to the ten to 15 age group, the zero to four age group
showed the migrant children at a slightly increased risk of respiratory
illness for all three seasons (Figure 9). In the non-growing season the
odds ratio of migrant children compared to the non-farm children was
1.36 (95 percent C.I., 1.05, 1.67). In the late-growing season the
odds ratio was 1.17 (95 percent C.I., .74, 1.60).
Multiple logistic regression analysis was performed on data for
this disease grouping utilizing the four main variables (status,
season, sex, and age) plus all interactions. The following factors
and interactions were found to be statistically significant (p<_. 10):
age, season, sex, sex by age, status, status by season, and status by
season by age. Appendix G contains a summary of the results from the
multiple logistic regression analysis. The T-ratios presented in
Appendix G were used in examining the statistical significance of the
variables and interactions for each disease grouping.
2. Dermatologic Diseases
The percentage of youths with dermatologic diseases by status,
season, and age is shown in Table 31. In the youngest age group,
the highest percentage of dermatologic diseases occurred during the
early-growing season with no consistent difference between migrant
and other children during the three seasons. In the five to nine
-------
100
569
TABLE 31
Percent of patient visits with a diagnosis of a dermatologic disease
by age, status (migrant, seasonal, and non-farm), and growing season.
"Youth in Agriculture: Exposure Assessment and Medical Records
Morbidity Study," Colorado, 1979-1981.
Non-growing
Age Group 1 (0-4)
Migrant
Seasonal
Non-farm
Age Group 2 (5-9)
Migrant
Seasonal
Non-farm
Age Group 3 (10-15)
Migrant
Seasonal
Non-farm
1.33
3.03
2.44
2.49
0.00
2.02
3.79
3.36
3.68
0.90
2.38
2.23
Early-growing
4.38
3.99
3.59
3.77
2.43
4.26
2.78
2.91
2.54
1.45
1.90
1.92
Late-growing
0.85
3.03
3.08
2.98
5.56
5.13
4.34
4.47
-
3.23
1.42
2.94
2.76
Total
2.85
3.27
2.85
2.92
1.78
3.24
3.67
3.49
3.03
1.15
2.39
2.26
TABLE 32
Percent of patient visits with a diagnosis of a dermatologic disease by
sex and age group. "Youth in Agriculture: Exposure Assessment and
Medical Records Morbidity Study," Colorado, 1979-1981.
Age Group:
Female
Male
0-4
2.79
3.04
5-9
2.74
4.12
10-15
2.12
2.41
Total
2.58
3.12
2.92 3.49 2.26 2.86
-------
101 ..,
570
age group* the percentage of skin illnesses was highest during the late-
growing season (4.34 percent in the non-farm status, 5.13 percent in
seasonal youths, and 5.56 percent in migrant youths) with migrant
children showing the greatest increase from the non-growing to the
late-growing season. The migrant children in the ten to 15 age group
had the highest percentage of skin illnesses in each of the three
seasons while the seasonal children experienced the lowest incidence
of dermatologic diseases (Figure 10).
The number of youth with dermatologic illness was tabulated by
status, season, age, and sex. In the ten to 15 year old age group,
the percentage of illness in male migrant children increased over the
three seasons (late-growing season having the highest percent). The
males had a higher percentage of dermatologic illness than females
for all three age groups. Male children also had a higher percent
of skin diseases than female children in the early and late-growing
seasons. The percentage of dermatologic diseases by sex and age is
summarized in Table 32.
Multiple logistic regression analysis was performed on this dis-
ease grouping using the same variables and interactions that were
considered with the respiratory disease grouping. The following
factors were found to be statistically significant (p^. 10): season,
season by age, sex by season, status by age, status by sex, and status
by sex by age. Appendix G contains a summary of the results from
the multiple logistic regression analysis.
-------
PERCENT CD
ixx/r
&»3
Y/////A
45
ifl
4L5
40
as
10
25
20
f.5
J.O
.5
ao
\\
NOM) S0h4) 00^-4) N<5-0
STATUS
SG-W 0(5-» M(IO-I5) SdO-15) OUO-I5)
/ AGE GROUPING
o
ts>
Figure 10. Percent of patient visits with a diagnosed dermatologlc disease by season, status
(M • migrant, S - seasonal, and 0 - non-farm), and age. "Youth In Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado, 1979-1981.
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103
572
3. Eye Diseases
Only a small number of patients visiting the clinic were diag-
nosed with eye diseases. Table 33 presents the percentage of youths
with eye illnesses by status, season, and age. Disregarding the time
of the year, the migrant children had the highest percentage of eye
diseases for each age group. No obvious trends by season for this
disease grouping are apparent. However, one should be reminded that
few patient visits for each status and age group were recorded. The
sex by age group percentages are shown in Table 34.
Multiple logistic regression analysis was performed on this
disease grouping with the following factors found to be statistically
significant (p_<. 10): age, season, status, status by age, status by
sex, status by sex by age, status by sex by season, and status by sex
by season by age. Appendix G presents a summary of the results from
the multiple logistic regression analysis.
4. Symptoms of Possible Pesticide Poisoning
This disease grouping was selected in order to study symptoms
that have been associated with poisoning by pesticides. Of course,
these symptoms may also be associated with other illnesses (Table 7).
The percentage of symptoms of possible pesticide poisoning was
very small for each cross classification of status, season, and age
group (Table 35). The migrant and seasonal youths in the two older
age groups had higher percentages of this disease grouping than did
the non-farm youths. The percentages by sex and age group are shown
in Table 36.
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104
573
TABLE 33
Percent of patient visits with a diagnosis of an eye disease by age,
status (migrant, seasonal, and non-farm), and growing season. "Youth
in Agriculture: Exposure Assessment and Medical Records Morbidity
Study," Colorado, 1979-1981.
Non-growing
Age Group 1 (0-4)
Migrant
Seasonal
Non-farm
Age Group 2 (5-9)
Migrant
Seasonal
Non-farm
Age Group 3 (10-15)
Migrant
Seasonal
Non-farm
2.99
2.17
2.03
2.10
3.29
1.26
1.75
1.76
1.05
0.90
1.16
1.11
Early -growing
2.63
3.42
2.33
2.55
5.83
1.60
1.91
2.39
2.17
0.36
1.97
1.78
Late-growing
3.39
3.46
1.88
2.20
2.78
0.64
1.36
1.31
0
1.42
1.32
1.29
Total
2.85
2.75
2.07
2.23
4.57
1.21
1.70
1.83
1.52
0.86
1.40
1.33
TABLE 34
Percent of patient visits with a diagnosis of an eye disease by sex and
age group. "Youth in Agriculture: Exposure Assessment and Medical
Records Morbidity Study," Colorado, 1979-1981.
Age Group
Female
Male
0-4
2.12
2.34
5-9
1.88
1.79
10-15
1.63
1.02
Total
1.92
1.86
2.23
1.83
1.33
1.89
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574
105
TABLE 35
Percent of patient visits with a diagnosis of a symptom of possible
pesticide poisoning by age, status (migrant, seasonal, and non-farm),
and growing season. "Youth in Agriculture: Exposure Assessment and
Medical Records Morbidity Study," Colorado, 1979-1981.
Non-growing
Age Group 1 (0-4)
Migrant
Seasonal
Non-farm
Age Group 2 (5-9)
Migrant
Seasonal
Non-farm
Age Group 3 (10-15)
Migrant
Seasonal
Non-farm
0.33
0.09
0.11
0.12
1.32
0.25
0.29
0.34
0.53
0.90
0.60
0.64
Early-growing
0.22
0.19
0.09
0.12
0
0.53
0.09
0.13
1.45
0.36
0.20
0.39
Late-growing
0
0
0.39
0.31
0
1.28
0.45
0.54
0
0.95
0.51
0.55
Total
0.23
0.09
0.17
0.16
0.51
0.54
0.28
0.33
0.95
0.77
0.48
0.55
TABLE 36
Percent of patient visits with a diagnosis of a symptom of possible
pesticide poisoning by sex and age group. "Youth in Agriculture:
Exposure Assessment and Medical Records Morbidity Study," Colorado,
1979-1981.
Age Group:
Female
Male
0-4
0.12
0.20
0.16
5-9
0.34
0.32
0.33
10-15
0.81
0.28
0.55
Total
0.37
0.25
0.31
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106 575
Multiple logistic regression analysis performed on this disease
grouping found the following factors to be statistically significant
(p^. 10): age, sex by age, and status by sex by season by age. Ap-
pendix G contains a summary of the results from the computer analysis.
Due to the small frequencies, limited inference can be made from these
results.
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576
DISCUSSION AND CONCLUSIONS
A. Exposure Assessment Study
1. Observational Data
In eastern Colorado onions are grown as a seasonal row crop, and
are planted as seeds or transplants. All onion fields included in
this study were composed of transplanted onions, as the seeded onion
fields owned by the participating growers were all machine harvested.
The transplanted onions are hand harvested because they are more easily
damaged by harvesting equipment than the seeded onions. Hand harvest-
ing begins in late August and extends into September. Onion harvest-
ing is a simple process employing men, women, and children. The
onions are harvested by mechanically uprooting them several days prior
to workers entering the field. The workers' Job is to top the onions,
fill individual buckets with onions, and then empty the buckets into
large burlap sacks. The workers are paid according to the number of
large burlap sacks filled. In the actual work assignments, each family
unit is assigned a row of onions. Children work alongside their
parents topping the onions, while the adults usually empty the buckets
into the sacks. The worker may be exposed to residues on foliage
during the process of topping the onions, which requires the worker
to pick up a handful of onions and cut the foliage off both ends.
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108
Although all of the Individuals 'observed in this study wore gloves
provided by the study, it is estimated that under normal working con-
ditions only approximately one-third of onion harvesters wear gloves
(either the rubber-vinyl type or the heavy cotton-garden type glove).
Gloves are probably worn to protect the hands from the shears used to
top the onions.
The observations of onion harvesters in this study were somewhat
limited due to data being recorded for only three days. Observations
were limited to working individuals and therefore did not address
observations of non-working children who accompanied their parents
to the fields. It was not surprising that none of the observed indi-
viduals utilized goggles, respirators, or rubber suits for protection
from pesticides, since these types of protective equipment are geared
towards those who handle or apply pesticides. From an exposure stand-
point, our observations indicate that migrant, non-working children
may be exposed to levels of pesticide residues comparable to those
of their parents or working siblings. Often these children remain
in the field for the enitre work day. Non-working children were ob-
served riding bicycles through the field and playing in the irrigation
ditches next to the field being harvested.
A higher percentage of the youth cohort wore short pants, short-
sleeved shirts, and no hats than the adult cohort. This may be due
to children being less concerned than adults about protecting their
exposed skin from the sun. Interestingly, the adult females wore
shoes less than adult males or the youth group. The dermal surface
area of the forearm (6.7 percent), hands (6.9 percent), calves (13.5
percent), feet (6.4 percent), and head (5.7 percent) comprise
577
-------
109
39.2 percent of the skin area of the human body (Popendorf and
Leffingwell, 1982). Although these percentages are based on an
average adult male, it can be seen that a field worker wearing short
pants, short sleeves, no hat, no gloves, and no shoes would have an
increased potential for exposure to pesticide residues. However,
based on these data, the only significant difference between youth and
adults was in the wearing of hats, with a smaller percentage of youth
wearing hats than adults. Thus, the possibility of increased exposure
to pesticide residues for those not wearing hats may exist. But as
Popendorf and Leffingwell (1982) and Davis (1980) reported, the hands
receive the highest pesticide exposures, perhaps up to 90 percent of
the total dermal exposure.
A study recently completed by the California Pesticide Hazard
Assessment Program (1983) surveyed vegetable crops for harvest prac-
tices, worker characteristics, and other pertinent items. Of the 11
vegetable crops surveyed, three crops were found to utilize children
in harvest crews (approximately 10 percent of the crew). These crops
were snap beans, radishes, and green onions, all of which are row
crops. Usually, when children are involved in crop harvesting, com-
plete family units work together, the harvesting is a simple procedure,
and the workers are paid a piece rate (so much per sack or crate). In
this way, children can substantially Increase the family income.
2. Human Exposure Data
This research was designed to provide data to aid In determining
whether youth under 16 years of age who work in agriculture are at
risk to potential adverse health effects from exposure to pesticides.
578
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110
579
One phase of the exposure assessment study was to assess the exposure
among youth working in onions to selected pesticides and to compare
this exposure to that of adults working in the same fields. This was
accomplished by collecting and analyzing human exposure samples (gloves
and urine) and comparing the pesticide levels for youth to those of
adults.
It was interesting to find toxaphene values above the detection
limit in all glove samples, soil samples, and foliage samples. The
levels of organophosphates in the environmental substrates and in the
glove samples were not consistent, as values above detection limit
were found on some days and not on other days. As mentioned in Chapter
V, the toxaphene levels were higher in foliage and soil in Field A
than in Field B even though the time between insecticide application
and sampling was longer in Field A than in Field B. This could be
due to drift of pesticides applied to fields adjacent to Field A.
It was noted on the field observation forms on Day 1 and Day 2 that
aerial spraying of corn fields was taking place upwind from the field
during sampling of Field A. This could also account for the value of
100.5 ppb of ethyl parathion on foliage on Day 2 in Field A (Table 9).
It is of interest that both ethyl parathion and toxaphene are recom-
mended for use on corn for control of grasshoppers and that ethyl
parathion is recommended for control of several other insect pests
(Hantsbarger, 1982).
The results of the glove analyses suggest that youth (<16 years
of age) harvesting onions received less exposure to the insecticides
of interest than did adults (>_ 16 years of age) even though not all
the differences proved to be statistically significant at the .05
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580
level of significance (Tables 12 and 13). For the toxaphene values,
the adults had statistically higher geometric mean levels than did
the youth.
No significant difference between youth and adults (for ethyl
parathion) was observed in Field A. However, in Field B an association
between age and ethyl parathion levels was described (p<.01) with youth
having more zero and trace levels than the adults. No association
between age and methyl parathion levels or malathion levels was found
in Field B.
One explanation why the gloves worn by the youth cohort had lower
insecticide values than those worn by adults is that the more youthful
workers may not handle as many onions as the adults in the same time
period. This factor was not taken into account in this study. And
since child and parent worked side by side filling the same container
with onions, a measurement such as number of containers each person
filled could not be used in the analysis to account for such differ-
ences. It should also be mentioned that exposures received while
harvesting onions would result from less extensive and less prolonged
contact with foliar surfaces than harvesting of citrus crops or grapes.
However, the hot and dry climatic conditions in Colorado are such
that pesticides degrade more slowly than in high moisture areas. So
exposure to toxicant-containing dust may last for a longer period of
time, which may help to explain why certain substrates had detectable
insecticide levels'after such a lengthy period between application
and sampling.
A study conducted by the California Pesticide Hazard Assessment
Program (1982) compared the dermal dose of Captan received by youth
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112
581
(less than 14 years of age) and adults (14 years of age or greater)
while picking strawberries. The researchers concluded that youths
have lower dermal body exposure during strawberry harvesting, probably
due to the smaller body weight and body surface compared to adults.
When the exposure data were normalized for body weight (mg/kg/hr),
the trends indicating differences between children and adult exposures
were removed. It is important to note that in the California study
the surface area of the body part (i.e., hands, forearms, calves)
was used to calculate mg/hr. Body pads were mounted on the partici-
pants' head, chest, back, upper arm, lower arm, and lower leg. Light
weight cotton gloves were also worn by participants. In the present
Youth in Agriculture study, only gloves were worn by onion harvesters
and no attempt was made to account for body surface area. It was
felt that the length of time that the gloves were worn was the most
important factor when determining ug/hr exposure of workers to selected
pesticides.
Popendorf et al. (1979) reported that in crops where no gloves
are worn, the hand contact dose to the whole-body dose is approximately
two-thirds of the total (even though the hands receive up to 90 percent
of the total dermal exposure). Maibach and Feldman (1974) reported on
the low anatomical site-specific rate of absorption into the hand which
would reduce the actual absorbed dose. Furthermore, Popendorf and
Spear (1974) reported that the build-up of a heavy, possibly protec-
tive layer of fruit juices, oils, dirt, and other detritis may also
reduce the amount of pesticide absorbed by the hands.
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113
582
Urine was chosen as a substrate for measuring pesticide exposure
due to the comparative ease of collecting urine over blood samples.
Drine also requires less careful handling in the field and transport
than do blood samples. According to Morgan et al. (1977), the major
excretion of alkyl phosphates and thiophosphates occurs within four
to eight hours after exposure. The peak excretion time for toxaphene
was not found in the literature, but Wolfe et al. (1970) reported that
DDA (a metabolite of DDT) reached peak levels in urine 10.0 hours post-
exposure. A 24-hour specimen is the best analytical substrate but
due to the added difficulty in obtaining such samples, samples were
collected from study participants prior to their leaving the field.
The lack of toxaphene and the small number of samples with de-
tectable organophosphate metabolites being detected in urine is most
probably due to four reasons. First of all, the nylon gloves probably
reduced the amount of organophosphate residues that reached the hands
by as much as 90 percent. Popendorf et al. (1979) inferred that the use
of nylon knit gloves prevented the penetration of 90 percent to 95
percent of the phosalone "contact" residue from reaching the hands.
The second reason is that the urine samples were collected prior to
workers leaving the field, thus not all of the samples were collected
at the major excretion time of four to eight hours post exposure.
Thirdly, in the case of toxaphene, only a small percentage of toxa-
phene is excreted as unmetabolized toxaphene (Casida et al., 1974).
Finally, the levels in the field may have been low enough that no
measurable amounts of the pesticides were absorbed.
The four male workers who did have detectable DEP and DETP levels
were working in Field A on Day 2 which also had 100.5 ppb of ethyl
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583
parathion in the foliage sample collected on that day. It is of inter-
est that the workers with detectable levels were two pairs of father
and son.
If a sufficient quantity of urine had been available, it would
be of interest to know if detectable levels of chloride ion were
excreted. Casida et al. (1974) reported that approximately 50 percent
of metabolized toxaphene was excreted as chloride ion when toxaphene
labelled with 3SC1 was administered orally to rats and the rate of
elimination and the extent of dechlorination were studied over a 14-day
period. The urine samples collected in this study were analyzed for
unmetabolized toxaphene and none of the samples had detectable levels
of toxaphene.
A study conducted by the Iowa Pesticide Hazard Assessment Program
(1982) obtained pre and post-exposure urine samples from four youth
and three adult apple pickers. The pesticides of interest to this
study were Captan, Imidan, and Guthion. The post-exposure levels of
dimethylthiophosphate (DMTP) for youth and adults were not statisti-
cally different (p<.05). However, the mean DMTP level for youth was
higher than for adults.
3. Questionnaire Data
A primary purpose of administering the questionnaire to farm
worker families was to provide data to determine if work practices
differed between youth and adults. Another objective was to gather
information concerning the basic health experience of these families.
For those 16 years of age or older, 96.7 percent were involved in field
labor while 86.4 percent of youth aged ten to 15 worked in the fields.
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115
For all three time variables analyzed in this study (months worked
per year, days worked per week, and hours worked per day), the youth
cohort worked for shorter periods of time than the adults. It is very
likely that a large proportion of working youth attend school and
therefore work only during the summer months. Interestingly, the
percent of youth working eight hours per day or less did not consider-
ably differ for those less than ten years of age compared to those
13 to 15 years of age (50.0 percent vs. 56.5 percent; p>.20). However,
the percent of youth working five days per week or less differed
considerably for those less than ten compared to those 13 to 15 years
old (75.0 percent vs. 41.7 percent; p«.087). Therefore, it appears
that the younger children work comparable hours per day compared to the
older youth but do not work as many days per week.
No statistically significant differences were noted between youth
and adults concerning personal hygiene practices. This area consist-
ed of only three questions, and the questions were addressed to the
female head of household and not to each family member. The person
answering the questionnaire may have been self-conscious about answer-
ing those questions which she perceived to be personal.
In contrast to the observational data, the youngest worker in-
volved in field labor was reported as a five year old female, and the
oldest was reported as a 65 year old male. The major discrepancies
between the observational data and the questionnaire data in regards
to the type of clothing worn while working was whether the worker
covered his/her head when working and whether long or short sleeves
were worn (Tables 10 and 19). In the questionnaire results, a much
higher percentage of both youth and adults wore long sleeves than we
584
-------
116
585
observed in field workers; also, the questionnaire responses indicated
that a much higher percentage of both youth and adults covered their
heads when working than was found from the observational data.
It is apparent from the responses to the questions concerning
symptoms associated with pesticide poisoning that few of the workers
experienced such symptoms. It is also of interest that only a small
percentage of working youth and adults were sick during the last year
or had seen a doctor during the past year. This could point out that
farm workers seek or obtain little medical care. The results of ques-
tion 29 (Table 21) further illustrate the small percentage of working
youth and adults with selected illnesses. This could be due to lack
of medical care so that these illnesses remain undetected. The high
percentage of non-working adults with anemia is probably due to the
small number of individuals in this category (only five of the total
269).
The pregnancy information in this questionnaire was brief and
not validated. It is of interest to note that the self-reported rate
of 12.2 miscarriages per 100 pregnancies is in the lower range of ten
to 20 spontaneous abortions per 100 pregnancies or women as reported
by Bloom (1981). It is likely, however, that these women received
less medical care and may have been less likely to accurately recall
any spontaneous abortions.
It was surprising to find that only a very small percentage of
farm working families were aware of pesticides used around them
(Table 22). However, the questions were very general and the respon-
dent may have been somewhat hesitant to answer positively to the
questions concerning pesticides and their place of employment.
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117
The data obtained from the questionnaires were descriptive and
intended to provide some background information on farm worker fam-
ilies. It should be made clear that the data obtained from the
families in this study are not representative of all farm workers
or farm workers in northeastern Colorado. It is important to recog-
nize several problems in obtaining data from farm workers in a field
setting. First of all, the questionnaires were administered to the
female head of household in the field environment. The interviewee
may have felt the need to hurry through the answers so she could
return to her field work as soon as possible. The questionnaire
relied totally on the recall of the female head of household, which
may have introduced not only recall bias but subjective bias since
this person answered questions which concerned all family members.
There is also the possibility that farm workers are more reluctant
to answer personal questions truthfully and to voice opinions con-
cerning pesticides due to fear of losing a Job.
B. Medical Records Morbidity Study
Gathering health data on highly mobile populations such as mi-
grant farm workers is difficult. In order to somewhat alleviate
this difficulty, medical record data from a migrant health clinic in
Fort Lupton, Colorado were obtained and evaluated. This research
project was designed to Investigate the frequency of certain ill-
nesses among youth in agriculture. The children of migrant farm
workers, seasonal farm workers, and non-farm workers were compared
using variables such as migrant status, sex, age of the patient,
586
-------
587
118
and month of patient visit. A total of 26,206 patient visits by youth
under 16 years of age were included in the study for the three year
period 1979-1981.
A review of the literature indicated that this medical records
study was one of the most thorough studies conducted using migrant
clinic records, not only because of the large number of patient visits
available for analysis, but more importantly because of the ability
to stratify the patient visits by migrant status (migrant, seasonal,
or non-farm). The variables of interest were available for each
patient visit used in the final analyses.
1. Respiratory Diseases
Migrant children under five years of age had a higher percentage
of patient visits for a respiratory disease than the non-farm children
of the same age. In particular, the migrant children of this age
group experienced more respiratory illness than the non-farm children
during both the non-growing season (46.2 percent vs. 38.7 percent)
and the late-growing season (45.0 percent vs. 41.0 percent, Table 29).
As a result, the multiple logistic analysis found the status by sea-
son by age interaction to be highly significant (p-.0008, Appendix G).
This pattern was quite different for the ten to 15 year age group.
For this age group, the migrant children experienced considerably less
respiratory illness than the non-farm group during the non-growing
season (13.7 percent vs. 21.9 percent), but in the late-growing sea-
son, migrant children in this age group had a considerably higher
percentage of respiratory illness than children in the non-farm cate-
gory (25.8 percent vs. 17.8 percent, Table 29). Thus, the migrants
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588
showed an Increase by season whereas the non-farm children showed a
decrease in percentage of respiratory illness (highest in the non-
growing season and lower in the early and late-growing seasons) .
Further, these results for the ten to 15 age group were found to be
statistically different (p<.05) from the corresponding results for
the less than five age group (T-ratio • 2.46, Appendix G). It should
be noted that this pattern was not seen for the migrant children in
the five to nine age group.
It was interesting to find that when only male migrant children
were considered in the ten to 15 age group, 34.6 percent of the clinic
visits were diagnosed with a respiratory illness, compared to 19.4
percent for female migrant children in the ten to 15 age group. It
was also observed that the female to male ratio increased most notably
in the older migrant cohort (Table 28) . Since the older male migrant
children visited the clinic less often than males of the same age in
the non-migrant status groups, there may be an under-estimated per-
centage of males in the ten to 15 age group being diagnosed with a
disease of interest. Alternatively, if male migrants in this age
group visit the clinic only when a specific illness is present, an
increased proportion of disease in this stratum may be seen. Also,
it is likely that male migrant children work more days in field labor
than females. Exposure to chemical residues or other environmental
conditions (dusts, allergens) have been associated with the etiology
of respiratory illness (Rasmus sen and Cole, 1976). This may partially
explain the higher percentage of respiratory illness among male mi-
grant compared to female migrant children in the ten to 15 age group.
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120
2. Dennatologic Diseases 589
The results of the dermatologic disease grouping demonstrated a
pattern different from that for the respiratory diseases. As can be
seen in Tables 31 and 32 most differences were due to status and age
group. Although dermatologic disease increased by season for both
migrant and seasonal children in the five to nine age group, no other
seasonal patterns were apparent. Male migrant children in the ten to
15 age group showed a higher percentage of dermatologic disease than
female migrant children in the same age group. Work practices may
have contributed to this higher percentage of dermatologic diseases
among male migrant children. However, the numbers for each combination
of status, sex, season, and age were so small that meaningful trends
were difficult to determine statistically. Males in the ten to 15
age group may work longer hours in the fields, more days in the fields,
or perhaps tend to wear protective clothing (i.e., gloves) less often
than females.
Nutritional and other deficiencies may be responsible for many
of the skin manifestations; unfortunately, it was not possible to
take these factors into account in this study. In the health study
conducted by Rudd in 1975, contact dermatitis and eczyma were the
two most common integumentary ailments listed. A study conducted in
1971 by Chase et al. considered the nutritional status of Mexican-
American migrant children. A deficiency in vitamin A was found to
be the major nutritional problem; further, those children with low
vitamin A levels also had more frequent skin and upper-respiratory
tract infections. This finding is important since vitamin A is
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590
necessary for the maintenance of epithelial membranes in the body.
A 1974 study conducted by Larson et al. found that, although the
dietary intake of vitamin A was adequate, a biochemical deficiency
was found in one-third to one-half of the Mexican-American migrant
children.
3. Eye Diseases
The eye disease grouping was included since this was listed as
one of the most frequent health problems of migrant farm workers
(Smith et al., 1978). Also, pesticide illnesses are often reported
by site; and the number of eye, or eye and skin cases are commonly
used as groups to classify type of illness (Maddy et al., 1978; Weiss,
1981). The number of patient visits diagnosed as having one of the
three eye diseases of concern to this study was very small. The
patient's age was the key epidemiologic variable in explaining the
variation in percentage of eye diseases. In particular, children
less than five years old within each status group showed a higher
percentage of eye disease than the corresponding older age group
(except for migrant children five to nine years old).
4. Symptoms of Possible Pesticide Poisoning
As previously mentioned, less than 1 percent of patient visits
among youth were diagnosed as having possible pesticide poisoning
symptoms. It was interesting to note that multiple logistic regres-
sion analysis found the four-way interaction of status, sex, season,
and age to be statistically significant. As seen in Appendix G, the
statistical significance of design variables 5 and 8 explain this
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122
591
significant interaction (T-ratios equal to 2.73 and 2.04, respectively).
Design variable 5 compares the differences between migrant children to
non-farm children, females to males, non-growing season to late-growing
season and the children less than five to those aged five to nine.
Design variable 8 compares the differences between migrant children
and seasonal children, females to males, non-growing season to early-
growing season, and less than five to the five to nine years olds.
Although the migrant children had the highest percentage of these
symptoms for all three age groups, the overall differences among mi-
grant, seasonal, and non-farm children were not statistically signif-
icant. Also, seasonal trends were not apparent in these data.
5. Confounding Variables
A major limitation of this study was the use of the total number
of patient visits in each age, sex, season, and status group as the
denominator in calculating proportions in each subclass for each
disease grouping. It is not known whether each child visited the
clinic only once or made multiple visits. If a few children made
multiple visits to the clinic, this may indicate chronic conditions
among a small percentage of children. The most important point to
remember when comparing results among the migrant, seasonal, and non-
farm categories is that the results are presented as proportions of
illness in each age, status, season, and sex stratum. Rates were
not calculated since the "population at risk" was not known. To
obtain an accurate estimate of the population of migrant farm workers
would prove to be a very difficult and time-consuming study in itself.
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592
123
The sex and age variables may affect the results since less
clinic visits were attributed to the older male migrant children than
females in the same age and status group. However, in the non-farm
status group the male to female ratio of clinic visits remained
fairly constant for the three age groups. This observation could
lead to an under-estimated proportion of the older male migrants
having a disease of interest to this study.
Socio-economic status and lifestyle may affect the development
of one or many of the diseases used in this study, as discussed in
Chapter II. Furthermore, the number of clinic visits may reflect
parental attitudes towards health care. That migrant farm workers
utilize medical care less often than other populations has been dis-
cussed by several authors (Walker, 1979; Slesinger and Cautley, 1981).
The very real possibility exists that migrant farm workers who are in
this country illegally may not seek health care for fear of being
reported to immigration authorities. It is also possible that a
smaller percentage of migrant farm workers are aware of the health
clinic and its services, which could lead to smaller numbers in this
status group visiting the clinic.
Season plays an important role in this study due to the fact that
migrant farm workers are present in the study area for only a portion
of the year. Certain illnesses may predominate by month or season.
Illnesses which are generally considered to be seasonal (i.e., respira-
tory infections) and which are observed to increase in the "off"
months, may indicate other causes or indirect associations with the
illness.
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Several of the respiratory illnesses and symptoms of possible
pesticide poisoning may have a long latent period and not become
evident until ages greater than 16 years. The three status groups
have the potential for different environmental exposures (i.e., pesti-
cides, dust, differences in geographic areas) and thus differing po-
tentials for development of one or all of the illnesses analyzed in
this study. It should be noted that most of the illnesses investigated
in this study are either acute or have short latent periods.
Chemical exposure, either occupational or non-occupational, may
have played an important role in these illnesses. However, due to the
limitations of a cross-sectional study of this type, many important
etiological factors are not present in the analyses but should be
considered when interpreting the results. Since a multitude of con-
founding factors are encountered when attempting to study children
of migrant farm workers, caution should be exercised when searching
for causes of health problems. It is most likely that several factors
play a role in the compromised health status, as reported in the lit-
erature, of these children.
C. Conclusions
The results of this Youth in Agriculture project support the
hypothesis that youth involved in field labor receive less exposure
to pesticide residues than do working adults. It is also apparent
from the exposure assessment phase of this study that the youth co-
hort worked fewer months per year, fewer days per week, and fewer
hours per day than the adults. Furthermore, all environmental samples
593
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125
had very low levels of toxaphene and only one foliage sample had a
detectable level of organophosphates, which was 100.5 ppb of ethyl
parathion. No pesticide residues were detected in the air samples
which were collected in the same field with the above ethyl parathion
value. The risk of adverse health effects due to acute exposure to
very low levels of pesticide residues appears to be minimal.
Reentry intervals have been set for many pesticides in association
with different crops. The reentry approach uses the known toxicity
and the estimated environmental behavior of the chemical after an
agricultural application to aid in field worker protection from pesti-
cide residues. The reentry time for ethyl parathion in onions was
not found in the literature. However, the reentry interval for appli-
cation of ethyl parathion (less than 8 Ibs. of actual parathion per
acre per application but no more than 10 Ibs. per acre, in the past
12 months) varies from 14 days for apples to 30 days for citrus
(Gunther, 1977). Another approach that could be used to determine
reentry times would be to monitor residue levels on foliage and soil
surfaces by means of a field kit (Gunther, 1980). A technician using
such kits can determine organophosphate levels in approximately 20
minutes.
Few groups receive greater exposure to a wider variety of agri-
cultural chemicals than do migrant and seasonal farm workers. The
adverse health effects due to long term, low-level pesticide residue
exposure are not known. The available literature contains no studies
addressing this issue. Furthermore, the social and economic character-
istics of farm workers would make a long term health study extremely
difficult, costly, and time-consuming. Of special importance are the
594
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126
development, if any, of chronic health effects in the children involved
in field labor due to their early age of exposure. Most pesticides do
not have adequate toxicological data regarding exposures of pre-
adolescents and adolescents. Since a large number of children
accompany their parents to the field, future studies should include
these children to determine their exposures while accompanying their
parents in the fields.
The medical records morbidity phase of this study indicated that
the youngest migrant children had a higher percentage of respiratory
disease than the seasonal or non-farm children in all three seasons,
while the ten to 15 year old migrant children had a higher percentage
than the other groups only in the late-growing season. A different
trend was observed for the dermatologic disease grouping. The migrant
children in the ten to 15 age group had a higher percentage of derma-
tologic disease than the seasonal or non-farm children in all three
growing seasons. Due to the nature of a cross-sectional study of this
type, the etiology of such diseases cannot be elucidated but it is
likely that lifestyle, rather than pesticide exposure, contributed to
much of the increase seen in the migrant cohort.
Due to the continued research in the area of pesticides and health
effects, and more and more pesticides being restricted in use, reentry
times should be strictly enforced. Since nylon gloves are known to
reduce exposure to pesticides, perhaps it would be possible to require
children to wear long sleeves and gloves at all times when working in
the fields. Also, the amount of time that children spend in the fields
could be set so that the working hours do not exceed eight hours per
day, and the working days do not exceed five days per week.
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596
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11:391-398.
Stecher PG, ed. 1968. The Merck Index - an encyclopedia of
chemicals and drugs. 8th ed. Rahway, New Jersey: Merck
and Co., Inc., p. 639.
Stormont RT, Conley BE. 1952. Pharmacologic properties of toxa-
phene, a chlorinated hydrocarbon insecticide. JAMA 149:1135.
Stroller A, Krupinski J, Christophers AJ, Blanks AK. 1965.
Organophosphorous insecticide and major mental illness.
Lancet 1:1387-1388.
Tabershaw IR, Cooper WC. 1966. Sequelae of acute organic phosphate
poisoning. J Occup Med 8:5-20.
-------
138
Turner WV, Engel XL, Casida JE. 1977. Toxaphene components and
related compounds: preparation and toxicity of some hepta-. 607
octa-, and nonachlorobornanes, hexa- and heptachlorobornenes,
and a hexachlorobornadiene. J Agric Food Chem 25:1394.
U. S. Department of Labor. Employment Standards Division, Wage and
Hour Division. Child Labor Bulletin No. 102.
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Walravens PA, Hambridge KM. 1975. Growth of infants fed a zinc
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Weast RC, ed. 1971. Handbook of chemistry and physics - a ready-
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Weiss HB. 1981. Human exposures to pesticides. Wise Med J 80:
12-15.
Wester RC, Maibach HI. 1976. Relationship of topical dose and
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Dermatol 67:518-520.
Wicker GW, Williams WA, Guthrie FE. 1979. Exposure of field
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Wolfe HR, Durham WF, Armstrong, JF. 1970. Urinary excretion of
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-------
608
APPENDIX A
-------
INTERVIEW DATE:
LOCATION:
FAMILY 10: _
MONK CATEGORY:
Family Neater: _
Sex: _
Btrthdate: _/_/_
Ethnicity:
1. How long have you worked as a farmworker?
(Years and Months)
2. How Many days per week do you work In the
field?
3. How Many hours per day do you usually
work In the field?
4. How long have you worked for this grower?
(Years and Months)
5. Do you and your faulty live on farm property?
(I) Yes (2) No
6. Does your household have running water?
(1) Yes (2) No
7. How many months per year do you work In
the field?
8. How often do you change the clothes you
work In? Every day(s) (>9 « 9)
9. How often do you do your laundry?
times per week.
10. On a weekly basts, how often do family
members completely bathe? times
per week.
I t
/
I !
I
__7 /__
/
t
OS
O
-------
-2-
FAHILY 10:
11. How often does each family member wash his/
her hair, on a Meekly basis? times per
Meek.
12. When you are working In the field:
13.
14.
IS.
a. Is your head covered?
b. Do you wear a long-
sleeved shirt?
c. Do you wear long
pants?
d. Do you wear any of
the following pro-
tective equipment?
1. respirator
2. rubber boots
3. safety glasses
4. gloves
5. other
(1) Yes (2) No
(1) Ves (2) No
(1) Yes (2) No
(I) Yes (2
U) Yes (2
1) Yes (2
0) Yes (2
U) Yes (2
No
No
No
No
No
Do you know of any pesticide related
Incidents among you, your family, or
your fellow workers within the past
12 months? (I) Ves (2) No
If yes, please describe on the attached
form.
Have you or members of your family been
sick during the past year?
(1) Yes (2) No
Have you or members of your family seen
a doctor during the past year?
(1) Yes (2) No
16. a. Have you had trouble with
Itching all over your
body? (1) Ves (2) No
b. Has there a rash with
the Itching? (1) Ves (2) No
-------
FAMILY ID:
-3-
17.
18.
19.
20.
21.
22.
23.
a. Do you have trouble with coughing?
(I) Yes (2) No
b. Do you notice this coughing More:
1. in the morning
2. after work
3. at night
a. Have you felt dizzy during the
past Month? (1) Yes (2) No
b. Have you experienced Muscle
twitching (Muscles Making short
jerking Movements) In the past
Month? (1) Yes (2) No
Are pesticides, such as weed killers.
insecticides, fungicides, and other
chemicals used for pest control:
a. in your home?
b. on your yard?
c. at your place of
employment?
Yes
Yes
(2) No
(2) No
(I) Yes (2) No
To your knowledge, are any pesticides
used around you? 0) Yes (2) No
During the past 12 months, has anyone
in your family had pesticide poisoning
diagnosed by a doctor? (I) Yes (2) No
During the past 12 months, has your
home been treated for pest control by
a commercial company? (1) Yes (2) No
During the past 12 months, has your
place of employment been treated for
pest control by a commercial company?
(1) Yes (2) No
-------
FAMILY ID:
24. Which members of the family smoke?
(1) Smoker (2) Non-smoker
25. For those that smoke, what Is the
average use?
fl) < 1 pack per day
2) > 1 pack per day
26. Have you ever had prolonged weakness
or paralysis of your body?
(1) Ves (2) No
27. a. Has a doctor ever told you that you
have cancer (a malignant growth or
tumor)? (1) Ves (2) No
b. Was it In the past
year? (1) Ves (2) No
c. Was It treated by a
doctor? (1) Ves (2) No
d. What type was It?
1. lung 4. leukemia
2. liver 5. lip. mouth, nose, ear
3. bladder 6. other, specify
28. TO BE ASKED OF FEMAILS ONLY
a. Have you ever been pregnant?
(1) Ves (2) No
b. What is the total number of pregnancies
you have had?
c. What Is the total number of miscarriages
you have had?
d. What is the total number of live births
you have had?
e. Are you pregnant now? (1) Ves (2) No
f. Have you had a pregnancy which ended
within the last 12 months?
(1) Ves (2) No
*-
OJ
ON
-------
-B-
FAMILY ID:
29. Has a doctor ever told you that you had
any of the following conditions?
a. Anemia
b. Arthritis
c. Asthma
d. Allergies to food(s)
e. Other allergies
f. Chronic cough
g. Emphysema
h. Hepatitis
I. Hay fewer
j. Severe infections
k. Tuberculosis
1. Ulcers (peptic, stomach, duodenal)
*>
*•
ON
-------
INTERVIEW DATE: _J J _
LOCATION:
FAMILY II):
WORK CATEGORY:
Nimbro de U fan!Ha: __
Sexo:
Fecha nacimlento: f_J
Ethnicity: _
I. Que tanto tlenpo a Ud. trabajado en
trabajos de labor?
2. Que tantos dfas de la sauna Ud. trabaja
en la labor?
3. Que tantos boras por dfa Ud. trabaja en
la labor?
4. Que tanto Uempo a Ud. trabaja para este
ranchero (anos y weses)?
5. Vive Ud. y su fanilia en propIdad del
ranchero? (1) SI (2) No
6. Tlene su casa agua Instalada?
(I) SI (2) No
7. Que tantos meses por ano ha trabajado
Ul. en la labor?
8. Que tantas veces se caMbla Ud. la ropa
en que trabaja? Cada d(a(s).
9. Que tantas veces por semana lava Ud. su
ropa?
10. Por semana, que tantas veces se banan
los miembros de su fami I la?
/ _
/ I
__7 /_„
/
*•
tn
ON
-------
FAMILY ID:
-2-
11. Que tantas weces se lava Ud. el pelo
por semana y cada mlembro de la famllla?
12. Cuando Ud. trabaja en la labor:
a. Se cubre Ud. su cabeza? (1) SI (2) No
• b. Usa Ud. camisas de
mangas largas? (1) Si (2) No
c. Usa Ud. patalones
largos? (1) SI (2) No
d. Usa Ud. uno de los
segutentes equipos de
protecto'n?
1. resplrador (1) Si (2) No
2. betas de agua (1) Si (2) No
3. antiojos de pro tec -
(on (1) Si (2) No
4. guantes (1) SI (2) No
5. otros equipos (1) SI (2) No
13. Sabe Ud. de algun accidente relaclonado
con Insec tit Idas en su faniilia o algun
otro trabajador durante este anb?
(1) SI (2) No /
SI llabia, nos puede dar Informacion en
forma que acompana este questlonario.
14. Ha estado Ud. o miembros de su fa«ilia
enferwos durante este ano.i>
IS. Ha visto Ud. o miembros de su famllia
un n£dico durante este a no.'
16. a. Ha tenldo Ud. problema con comezon
en su cuerpo? (1) Si (2) No
b. Tuvo uria roncha con su comezon?
(1) SI (2) No
—
—
—
—
—
—
—
—
ON
-------
FAMILY ID:
-3-
17. a. Ttene problem con tocer?
(1) Si (2) No
b. Ha notado Ud. MS tocer:
1. en la naTiana
2. despues del trabajo
3. en la noche
18. a. Se ha sentldo verttglnoso durante
este ws? (1) Si (2) No
b. Se ha sentldo contractions en los
•usculos durante este MS?
(I) SI (2) No
19. Son Insecticldas o otros qufmicos
usados para controllar Insectas:
20.
21.
22.
23.
a. en su casa
b. en su patio
c. en trabajo de empleo
(1) Si (2) No
(1 Si 2 No
(I) Si (2) No
En su conocimlento, ha visto insecticidas
usados cerca de Ud.? (I) Si (2) No
Durante este ano, ha estado un
de su familla envenenado por insect Jclda
confirmado por un nidlco? (1) Si (2) No
Durante este ano, ha estado su casa
funigada con insecticidas por una
conpania cwmercial? (1) Si (2) No
Duranti? este aTJo, ha sido el lugar de
eopleo funigada con insecticidas por
una convania cotimercial? (I) Si (2) No
ON
-------
-4-
FAH1LV ID:
24. Caul Mtewbros de su f ami Ha fuma?
(I) fuMar (2) no fumar
25. Para aquellos que fuman. como que
tantos paquetes fumn por dfa?
11) Meiios de un paquete por dfa
2) M£S do un paquete por dfa
26. Ha tenldo Ud. deblltdad o paraltsls en
su cuerpo? (1) Si (2) Ho
27. a. Le ha dicho un Medico si tlene
cancer, durante este a*no?
(1) SI (2) No
b. Que tipo de cancer, ha sldo
encontrada?
1. teucemta 4. vejlga
2. pulmones 5. labtos, boca
3. higado narlz. oldas
6. otros, mas claro
28. PARA HUJERtS SOLAHENTE
a. Ha estado en ctnta?
(1) SI (2) No
b. Que es el numero total clnta?
c. Que es el numero total de •IsparCos?
d. Que es el numero total de los
partos vlvos que ha tendto?
e. Esta en clnta ahora?
f. Ha estado en ctnta que he
teralnado durante este ano?
(I) 51 (2) No
*>
oo
-------
-5-
FAMILY 10:
29. Le ha dlcho on Medico s< ha tentdo
algunos de lo$ slguientes?
a. Anew! a
b. Arthritis
c. Asma
d. Alergia a cmtdos
e. Otras alerglas
f. Tos cronico
g. Enftsema
h. Hepatitis
i. Fiebre del heno
j. Infecciones severos
k. Tuberculosis
1. Otceras
0\
00
-------
619
APPENDIX B
-------
151
620
DATE: _/_/_
GROWER'S NAME:
ADDRESS:
Crop:
Under Contract?
Name:
Firm:
Address:
GROWER NUMBER:
PHONE NUMBER:
Variety:
Tes
No
Describe each pesticide used, the acres treated, application charac-
teristics, and reasons for applying each pesticide.
Crop
Name of
Chemical Applied
Concen-
tration
Formula-
tion
Active
Ingredients
-------
152
621
Who
Applied
fen -i
Cuti*m«2
Method
of App.
PlMM •!
*•)*••. •»
Gr*. ftm.O
Gt4. Afe.
•ten -4
Inc. W/
lrrif*t. «5
Otho—sfiJ
Type of
Coverage
IBrtfcM lNC-1
ItrMMMM
1 IM. -t
:*M« o
lnFurrDW»4
Spot •»
When was
pest, applied
«•<*•
IPtoMinfl -1
Al
PtoMMf •*
|Ah*r
Plcniint "3
.
Date
Applied
Primary
Reason for
app. pest.
How many acres of the above crop were planted in 1982?
-------
622
APPENDIX C
-------
154
623
WORKER OBSERVATIONS
Name:
Age:
Sex:
Date:
Location:
Protective Equipment;
Goggles
Gloves
Respirator
Rubber Suit
Clothing Type;
Pants
Shirt
Shoes
Hat
Time Period Observed:
Breaks;
Hours Worked;
Work Description;
Other Activities;
Smoking:
Eating:
Washing Facilities;
-------
624
APPENDIX D
-------
156
625
FIELD OBSERVATIONS
DATE:
FIELD LOCATION:
FIELD ACREAGE:
CROP:
WEATHER CONDITIONS:
WIND:
TEMPERATURE:
SUN CONDITION:
HUMIDITY:
TOTAL NUMBER OF WORKERS:
ADULTS (> 16)
FEMALES
MALES
YOUTH (< 16)
FEMALES
MALES
-------
626
APPENDIX E
-------
158
Operating Parameters, Reagents, Standards, and Methods
for Gas Chromatographic Analyses of Pesticide Residues
627
63,
I. Gas Chromatography - Operating Parameters
A. Tracer MT-220 gas chromatograph equipped with a w"Ni elec-
tron capture detector operated with the following parameters:
Column
Liquid phase
Column temperature
Carrier gas
Detector temperature
Inlet
Transfer line
borosilicate glass 1.8 meters x
4 mm i.d.
1.5% OV-17/1.95% OV-210 - liquid
phases premixed and coated on
silanized support, 80/100 mesh
200°C
nitrogen, flow rate of 80 ml per
minute
275°C
245eC
245°C
B. Tracer MT-220 gas chromatograph equipped with a nitrogen-
phosphorous detector operated with the following parameters:
Column
Liquid phase
Column temperature
Carrier gas
Detector temperature
Inlet
Transfer line
borosilicate glass 1.8 meters x
4 mm i.d.
5% OV-210 - coated on silanized
support, 100/120 mesh
200°C
nitrogen, rotameter setting of
7 cc/min.
275°C
210°C
235°C
C. Tracor MT-220 gas chromatograph equipped with a flame photo-
metric detector operated with the following parameters:
-------
159
628
Column borosilicate glass 1.8 meters x
A mm i.d.
Liquid phase 5% OV-210 - coated on silanized
support, 100/120 mesh
Column temperature 165°C
Carrier gas nitrogen, rotameter setting of
2.3 cc/min.
Detector temperature 200°C
Inlet 215°C
Transfer line 245°C
II. Reagents
1. Acetone, pesticide quality.
2. Hexane, pesticide quality.
3. Diethyl ether, pesticide grade.
4. Eluting mixture, 6% (6% diethyl ether with 2% ethanol in
hexane).
5. Eluting mixture, 15% (157. diethyl ether with 2% ethanol in
hexane).
6. Eluting mixture, 100Z (diethyl ether with 27. ethanol).
7. Florisil 60/100 mesh, PR grade, stored at 130CC a minimum
of three days.
8. Aluminum oxide (Alumina) reagent grade. Prepared for use
by shaking with 10Z distilled water for partial deactivation.
9. Anhydrous sodium sulfate, reagent grade, granular. All
Na.SO, used in the following procedures was rinsed three
times with acetone, oven dried, again rinsed three times
with acetone, oven dried, then cooled to room temperature
before use.
-------
629
160
10. Benzene, pesticide quality.
11. 3-Benzyl-l-p-tolytriazene, a cancer suspect angent.
III. Standards
Standards were prepared from primary reference standards
obtained from the Quality Assurance Section, Pesticides and
Industrial Chemicals Repository, EPA (Research Triangle Park,
North Carolina). Standards used for quality control spiking
purposes were prepared in acetone. Standards used for the
determination of sample pesticide concentrations by GC analy-
sis were prepared in iso-octane.
The following standard concentrations were used:
Spiking Gas Chromatograph
Standards Standards
Toxaphene 4 ug/ml 400, 600, 800 pg/ul
Ethyl Parathion 4 ug/ml 50, 100 pg/ul
Methyl Parathion 4 ug/ml 50, 100 pg/ul
Malathion 4 ug/ml 50, 100 pg/ul
IV. Methods - All samples collected in the field were kept cool using
blue ice until transported to the laboratory where they were
frozen.
A. Soil
1. Detection Limits:
The calculation of the detection limits in parts
per billion (ppb) for the pesticides of interest in
soil was as follows:
-------
161
630
_ [sample weight (g)] _ • x [""injection H m sample weight
[volume of sample at plugging (ml)] [volume (yl^J " injected (mg)
l/2 concentration of j [Injection volume!
l [°
.owest standard used (pg/uHl °f standard (yll ,
[sample weight"!
[injected (mgjj
The detection limit was calculated to be 62.5 ppb for ethyl
parathion, methyl parathion, and malathion. For toxaphene, the
detection limit was 1.0 ppm.
2. Sample Collection and Preparation:
a. Soil samples were collected in 7 oz. pre-rinsed jars
using a core sampler and taking only surface soil
(no greater than 1 in. in depth). The core sampler
was rinsed with hexane after samples were collected
from each section in a field.
b. Soil samples were removed from the freezer and air-
dried overnight on hexane washed aluminum foil.
c. The samples were then sifted on a U.S. standard #20
sieve with top covers and bottom pans 8 in. in diam-
eter by 2 in. in depth to remove stones and other
foreign material. The sieved soil samples were stored
in their original jars and re-frozen until analyzed.
3. Sample Extraction:
a. Glassware and other accessories (aluminum foil,
forceps, etc.) used to handle, process or store
samples for pesticide residue analysis were rinsed
two times with acetone and three times with hexane
prior to use.
-------
162
631
b. The soil samples to be analyzed were removed from
the freezer and allowed to equilibrate to room
temperature.
c. Two grams of soil were placed into a pre-cleaned
thimble which was placed in a 500 ml soxhlet ex-
traction apparatus.
d. Two hundred and fifty ml of 1:1 hexane-acetone in
a 500 ml boiling flask was attached to the soxhlet
extractor. This apparatus was attached to a water-
cooled condenser and heated using an electric
heating mantle.
e. Samples were extracted for A.5 hours (4 cycles per
hour).
f. The soxhlet extraction apparatus was cooled and
disassembled. All interior parts of the soxhlet
extractor were rinsed three times with hexane. All
washings were transferred to the 500 ml solvent
flask.
g. The sample extracts were transferred to a 500 ml
separatory funnel and 125 ml of , Na.SO, solution
was added to each funnel.
h. Each separatory funnel was gently shaken for one
minute, allowed to stand and then the lower,
. aqueous layer was discarded.
i. Another 125 ml of 2% Na.SO, solution was added to
2 4
each separatory funnel and each funnel was gently
shaken for one minute.
-------
163
632
j. The lower aqueous layer was discarded. Each funnel
was then gently swirled and tapped to remove all
remnants of the aqueous phase.
k. The organic phase was drained into a 250 ml flask
and each funnel rinsed with hexane, adding rinse
to the flask.
1. The solvent flask was transferred to a rotory vacuum
evaporator and concentrated to approximately 3-5 ml.
If necessary, acetone washed Na.SO, was added to
remove any residual aqueous phase.
m. The samples then were transferred quantitatively
to graduated glass centrifuge tubes with three
rinses of hexane.
n. The final extraction volume was adjusted to 5 ml
for samples and 10 ml for spikes, using an N-Evap
concentrator (Organomation, model number 111).
o. A 5 ul aliquot of the extract was injected into a
gas chromatograph equipped with a nitrogen-phos-
phorous detector to analyze for the organophosphate
compounds.
4. Alumina Clean-up:
a. The extracts were transferred quantitatively to the
top of activated alumina columns, which had been
rinsed with hexane. The columns were eluted with
85 ml of hexane into 250 ml flasks.
b. All samples were transferred to a rotary vacuum
evaporator and concentrated to approximately 3-5 ml.
-------
164
5. Florisil Fractional ion:
a. The sample then was transferred quantitatively to
a column of activated Florisil and eluted with 200
ml of 6X elution mix (diethyl ether in hexane) for
Fraction I, followed by 200 ml of 15% elution mix
for Fraction II. Each fraction was collected in a
separate, rinsed 500 ml flask.
b. Each eluate was concentrated on a rotary vacuum
evaporator to a volume of 2-3 ml and transferred
quantitatively to a graduate glass centrifuge tube
with three rinses of hexane.
c. The final extraction volume was adjusted to 10 ml
using an N-Evap concentrator.
6. Gas Chromatography for Toxaphene:
a. A 5 ul aliquot of the final extraction volume was
injected into a MT-220 gas chromatograph fitted
with a 63Ni EC detector.
b. Identification of sample compounds and determination
of concentrations were made by comparison of reten-
tion times and peak heights of sample chromatograms
with those of pesticide standards.
7. Quality Control:
The quality control procedure consisted of collect-
ing a soil sample from an area with no known history of
pesticide use. This sample was spiked with pesticide
standards immediately prior to the 4.5 hour soxhlet
extraction. In addition the same soil was analyzed
-------
165
634
as a control to indicate interferring peaks due to
pesticides or reagents used in analysis.
B. Foliage
1. Detection Limits:
The calculation of the detection limits for the
pesticides of interest in foliage samples was identical
to the soil calculations (Methods A.I.). The detec-
tion limits for ethyl parathion, methyl parathion and
malathion in foliage samples was 62.5 ppb. The detec-
tion limit for toxaphene in the foliage samples was
1.0 ppm
2. Sample Collection and Preparation:
a. A leaf punch 15 mm in diameter was used to collect
foliage samples. The leaf punch was rinsed with
hexane after samples were collected from each
section in a field. These samples were placed
in pre-rinsed jars.
b. Foliage samples were removed from the freezer and
air-dried overnight on hexane rinsed aluminum foil.
3. Sample Extraction:
a. Glassware and other accessories (aluminum foil,
forceps, etc.) were cleaned as described for soil
(Methods A.3.a).
b. Due to the low weights of the foliage samples,
samples collected on the same day were combined
to allow for increased weight of the foliage disks.
c. Each composite sample was then weighed (the weight
recorded) and placed into a pre-cleaned thimble
-------
166
which was placed in a 500 ml soxhlet extraction 635
apparatus.
d. Extraction was identical to that of soil (Methods
A.3.d.-l.).
e. The samples then were transferred quantitatively
to graduated glass centrifuge tubes with three
rinses of hexane.
A. Florisil Fractionation:
a. The samples were quantitatively transferred to a
column of activated florisil and eluted with 200
ml of 62 elution mix (diethyl ether in hexane) for
Fraction I, followed by 200 ml of 15% elution mix
(diethyl ether in hexane) for Fraction II, follow-
ed by 200 ml of 100% diethyl ether for Fraction III.
Each fraction was collected in a separate rinsed
-500 ml flask.
b. Each eluate was evaporated on a rotary vacuum
evaporator to a volume of 2-3 ml and quantita-
tively transferred to a graduate glass centrifuge
tube with three rinses of hexane.
c. The final extraction volume was adjusted to 10 ml
for Fraction I and all spikes, and 5 ml for
Fractions II and III using an N-Evap concentrator.
5. Gas Chromatography:
a. A 5 ul aliquot of Fraction I was injected into a
MT-220 gas chromatograph fitted with a Ni EC
detector. Five ul aliquots of Fractions II and
-------
167
III were injected into a gas chrotnatograph equipped 6 JO
with a nitrogen-phosphorous detector.
b. Identification of sample compounds and determina-
tion of concentrations were made by comparison of
sample chromatograms with those of pesticide
standards.
6. Quality Control:
As quality control measures, green onion tops
(obtained from a local grocery store) were cut into
small pieces and air-dried overnight. Two grams then
were weighed and placed into a pre-cleaned thimble. A
two gram sample was spiked with pesticide standards
immediately prior to the 4.5 hour soxhlet extraction.
Another 2 gram sample served as a control to indicate
interferring peaks due to substances in the foliage
or reagents used in analysis.
C. Field Air
1. Detection Limits:
The detection limits for the pesticides of inter-
est in the air samples were determined in nanograms/m
of air sampled. To calculate this detection limit,
the level in the spiking standard (4000 ng) was di-
vided by the volume of air sampled (in m ). The de-
tection limit for a 4-hour sample was 885 ng/m , and
for an 8-hour sample was 443 ng/m .
2. Polyurethane Foam Plug Clean-up:
Open-cell, polyether type polyurethane foam
•
3
(density range: 1:3 to 1.5 Ib/ft ; indentation load
-------
168
deflection: 28 Ib) was purchased from the Carpenter /77
Company (Denver, Colorado) in 12 in. x 12 in. x 3 in.
pieces. These pieces of foam were cut into the 2.25
in. in diameter cylindrical plugs with the use of a
plywood template and steel cutter developed by Goes
(1979).
Eight to 16 plugs were placed in a clean Nalgene
container filled with tap water. Each plug was sub-
merged and squeezed by hand until no air bubbles were
released from the plugs. Each plug was then squeezed
to remove the water and set aside. After all the plugs
were washed in this manner, the water was discarded
and fresh tap water was added. This procedure was
repeated until five tap water rinses and five dis-
tilled water rinses were completed. The plugs then
were loosely wrapped in aluminum foil and allowed to
dry for at least 48 hours.
Individual plugs were placed in a hexane-rinsed
400 ml beaker. Acetone was poured slowly into the
beaker until it reached approximately the 75 ml mark
on the side of the beaker. The plug was then sub-
merged and squeezed against the side of the beaker
with the aid of hexane-rinsed forceps. The acetone
was then decanted and discarded. The plug was then
squeezed against the side of the beaker to remove any
residual acetone. Each plug was rinsed with three
separate volumes of acetone.
-------
169 638
Two plugs were placed inside a soxhlet extractor
and extracted with 500 ml of 1:1 hexane-acetone for
24 hours at a rate of 4 cycles per hour. The washed
and solvent extracted foam plugs were removed from
the extractors and squeezed dry with hexane-rinsed
forceps. The pair of plugs was then wrapped in
hexane-rinsed aluminum foil and stored until needed.
3. Sample Collection
Air samples were collected using a flow rate of
18.82 liters per minute. The sampling time was re-
corded, and the foam plugs were wrapped tightly in
hexane-rinsed aluminum foil and kept on blue ice
until transported to the laboratory where they were
frozen.
4. Sample Extraction:
a. Glassware and other accessories (aluminum foil,
forceps, etc.) were cleaned as described for soil
(Methods A.3.a.).
b. The air samples were removed from the freezer and
allowed to equilibrate to room temperature.
c. Each pair of polyurethane foam plugs was placed
into a 1000 ml soxhlet extraction apparatus using
hexane-rinsed forceps.
d. Jive hundred milliliters of 1:1 hexane acetone in
a 1000 ml boiling flask was attached to the ex-
tractor.
-------
170
F 639
e. Plugs were soxhlet extracted as described pre-
viously for 4.5 hours (4 cycles per hour).
f. Following the extraction, the plugs were squeezed
dry with hexane-rinsed forceps. The interior of
the soxhlet extractor was rinsed three times with
hexane and transferred to the 1000 ml solvent flask.
g. The sample extracts were transferred to a 1000 ml
separatory funnel and 250 ml of 2% Na^SO, solution
was added to each funnel.
h. Each separatory funnel was gently shaken for one
minute, allowed to stand and then the lower
aqueous layer was discarded.
i. Another 250 ml of 2% Na_SO. solution was added to
2 4
each separatory funnel and each funnel was gently
shaken for one minute.
j. The lower aqueous layer was discarded. Each fun-
nel was then gently swirled and tapped to remove
all remnants of the aqueous phase.
k. The separatory funnel was drained into a 500 ml
flask and each funnel rinsed with hexane, adding
the rinse to the 500 ml flask.
1. The solvent flask was transferred to a rotary
vacuum evaporator and evaporated to approximately
3-5 ml.
5. Florisil Fractionation:
a. Identical to that described for foliage (Methods
B.4.a. and b.)•
-------
171 640
b. The final extraction volume was adjusted to 10 ml
for Fraction I and all spikes and 5 ml for Fractions
II and III using an N-Evap concentrator.
6. Gas Chromatography:
a. A 5 yl aliquot of Fraction I was injected into a
MT-220 gas chromatograph fitted with a Ni EC
detector. Five ul aliquots of Fractions II and
III were injected into a gas chromatograph equipp-
ed with a nitrogen phosphorous detector.
b. Identification of sample compounds and determina-
tion of concentrations were made by comparison of
sample chromatograms with those of pesticide
standards.
7. Quality Control:
To insure adequate quality control, a clean poly-
urethane foam plug was spiked with pesticide standards
prior to the 4.5 hour soxhlet extraction. In addition,
one clean polyurethane foam plug was analyzed with the
samples. This clean plug served as a control to indi-
cate interferring peaks due to the polyurethane or
reagents used in analysis.
D. Gloves.
1. Detection Limits:
. Since the glove samples were not weighed, the
detection limit was determined in total nanograms.
The levels of toxaphene in the glove samples were
very high, therefore the detection limit for toxaphene
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172
was that of the spiking standard (4000 ng). To the ^
contrary, OF compounds were very low in many cases.
For ethyl parathion, methyl parathion, and malathion,
the detection limit was determined by obtaining
average recoveries of greater than 75% for the lowest
spiking standard. The detection limit for these com-
pounds was found to be 200 ng.
2. Glove Clean-up:
Nylon, lint-free gloves were purchased from VWR
Scientific, Inc. To remove interferring chemicals,
the gloves were machine washed three times in hot
water with detergent. The gloves were then machine
rinsed two times in hot water. Further clean-up was
accomplished by placing two gloves inside a soxhlet
extractor and extracted with 250 ml of 1:1 hexane-
acetone for A.5 hours. The solvent was squeezed from
the gloves with hexane rinsed forceps and the iden-
tical soxhlet extraction procedure was repeated.
The washed and soxhlet extracted goves were removed
from the soxhlet extractors and squeezed dry with
hexane rinsed forceps. The gloves were then loosely
wrapped in hexane-rinsed aluminum foil to air dry.
When dry, the gloves were tightly wrapped in foil and
stored until needed.
3. Sample Collection:
a. Study participants were asked to wear a pair of
clean nylon gloves during their normal work
-------
173
642
practices. The amount of time that a participant
wore the gloves was recorded. Each pair of gloves
was collected from the participant and tightly
wrapped in hexane-rinsed aluminum foil.
b. All samples were kept on blue ice until transported
to the laboratory where they were frozen until
analyzed.
4. Sample Extraction:
a. Glassware and other accessories (aluminum foil,
forceps, etc.) were cleaned as described for soil
(Methods A.3.a.).
b. The gloves to be analyzed in a set were removed
from the freezer and allowed to warm to room temp-
erature .
c. Each set of gloves was placed in a 500 ml soxhlet
extraction apparatus using hexane-rinsed forceps.
d. Extraction was identical to that of soil (Methods
A.3.d.-l.).
e. If emulsions occurred, the funnel was gently
shaken. If the emulsion did not break, several
drops of ethanol or saturated NaCl were added
(to all samples, spikes and blanks in the set).
Addition of ethanol or NaCl was noted on the
laboratory report forms.
5. Florisil Fractionation:
a. Identical to that described for foliage (Methods
B.U.a. and b.).
-------
174
b. The final extraction volume was adjusted to 10 ml £ / 7
for Fraction I and 5 ml for Fractions II and III
using an N-Evap concentrator.
6. Gas Chromatography:
a. A 5 ul aliquot of Fraction I was injected on a
MT-220 gas chromatograph fitted with a Ni EC
detector. Five ul aliquots of Fractions II and
III were injected on a gas chromatograph equipped
with a nitrogen phosphorous detector.
b. Identification of sample compounds and determina-
tion of concentrations were made by comparison of
sample chromatograms with those of pesticide
standards.
7. Quality Control:
The quality control measures included spiking a
clean pair of gloves with pesticide standards immedi-
ately prior to the 4.5 hour soxhlet extraction. One
spiked pair of gloves was analyzed with each set of
samples. In addition, a total of three clean pairs
of gloves were analyzed with different sample sets.
These clean gloves served as controls to indicate
interferring peaks due to chemicals in the gloves or
reagents used in analysis.
E. Urine
1. Detection Limits for Toxaphene:
The calculation of the detection limit for toxa-
phene in urine was identical to the soil calculations
-------
175
644
(Methods A.I.) except that a sample volume was used
instead of sample weight. The detection limit for
toxaphene was calculated to be 200 ppb.
2. Sample Collection:
Urine samples were collected from study partici-
pants at the end of the work day. All samples were
collected in 3 oz glass jars rinsed two times with
acetone and three times with hexane. Teflon liners
were also rinsed and inserted into the lids.
3. Toxaphene Analysis:
a. Sample Extraction:
i. Glassware and other accessories were cleaned
as described for soil (Methods A.3.a.).
ii. The urine samples to be analyzed in a set
were removed from the freezer and allowed
to warm to room temperature.
iii. The urine samples were shaken and 5 ml of
urine was added to 30 ml glass, screw-top
tubes.
iv. Ten ml of hexane were added to each tube.
v. The samples then were placed on a Fisher
Roto-Rack for five minutes (on setting 6).
vi. The samples were removed and allowed to
settle. The samples then were centrifuged
for three minutes at 3500 rpm.
vii. The hexane layer was removed and placed in
a 250 ml flask.
-------
176
viii. Steps iy - vii were repeated two more
times. £45
b. Florisil Fractionation:
1. All samples were transferred to a rotary
vacuum evaporator and concentrated to
approximately 3-5 ml.
ii. The sample was then quantitatively trans-
ferred to a column of activated Florisil
and eluted with 200 ml of 6% elution mix
(diethyl ether in hexane). Each sample was
collected in a 500 ml flask.
iii. Each eluate was evaporated on a rotary vacuum
evaporator to a volume of 2-3 ml and quanti-
tatively transferred to a graduate glass
centrifuge tube with three rinses of hexane.
iv. The final extraction volume was adjusted to
5 ml (if 5 ml of urine was the initial
volume) or 3 ml (for samples with less total
volume only 3 ml were used) using an N-Evap
concentrator.
c. Gas Chromatography for Toxaphene:
i. A 5 yl aliquot of the final extraction
volume was injected on a MT-220 gas chroma-
tograph fitted with a Ni EC detector.
ii. Identification of sample compounds and con-
centrations was made by comparison of sample
-------
177
chromatograms with those of pesticide stan- ^ " ^
dards.
4. Detection Limits for Alkyl Phosphates:
The calculation of the detection limit in parts
per billion (ppb) for the alkyl phosphates was as
follows:
[sample weight (g)] F . . . ~1 . . ,
^ e * J „ injection sample weight
[volume of sample at plugging (ml)] volume (ul)I injected (mg)
I concentration of lowest! I injection volume
(standard used (pg/ul) I of standard (ul)I
sample weight
(injected (mg)J
pg/mg - ppb
The detection limit for the alkyl phosphates was
calculated to be 50 ppb.
5. Alkyl Phosphate Analysis:
a. Sample Extraction
i. One ml each of the control urine, urine
containing standards, urine used as spikes,
and urine samples to be analyzed was added
to 15 x 150 mm culture tubes.
ii. The tubes were shell-frozen using a solution
of acetone and dry ice. The tubes were
stored in the freezer until they were ready
to be freeze-dried.
iii. After freeze-drying, the samples were either
stored in a freezer or the next step was
continued.
-------
647
iv. To each tube 1 ml of acetone, three glass
beads, and 0.1 ml of a 10% solution of 3-
benzyl-1-p-tolytriazine in acetone was
added.
v. The tubes were tightly capped and placed in
the heating block at 70°C for two hours.
vi. The tubes were then cooled using a wet-ice/
water bath, and one drop of 6 N HC1 was
added to each tube and mixed.
vii. Ten ml of saturated sodium chloride solu-
tion was added to each tube.
viii. One ml of benzene was added to each tube,
the tubes were then mixed on a Vortex for
one minute.
ix. The tubes were then centrifuged, the ben-
zene layer was transferred to a tube con-
taining a small amount of sodium sulfate,
up to about the 0.2 or 0.3 ml mark.
x. The solvent was decanted into another tube
and analyzed by gas chromatography.
b. Gas Chromatography for Alkyl Phosphates:
i. A 5 yl aliquot of the final extraction
volume was injected on a MT-220 gas chroma-
tograph equipped with a flame photometric
detector.
ii. Identification of sample compounds and con-
centrations was made by comparison of sample
-------
179
chromatograms with those of pesticide
standards. The major chronic exposure
metabolites of ethyl paration, methyl
parathion, and malathion were used as
standards. The standards consisted of DEF
(diethylphosphate), DMP (dimethylphosphate),
and DETP (diethylthiophosphate).
6. Quality Control:
During the time period that the urine samples were
collected, two urine samples were spiked with known
amounts of pesticides and frozen with the other urine
samples. One ml each of ethyl parathion (4 yg/ml) and
methyl parathion (4 ug/ml) was added to 3 ml of a study
participant's urine and to 3 ml of a control (blank)
urine. Also 1 ml of toxaphene (4 yg/ml) was added to
3 ml of the study participant's urine and to 3 ml of
the control (blank) urine. These QC samples were
analyzed at the same time as the toxaphene analysis and
the alkyl phosphate analysis.
Two controls, three standards, and two QC sample
were analyzed with each set of urine samples. The
three standards consisted of: DMP, DEF, and DETP at
50 ng, 100 ng, and 200 ng.
-------
649
APPENDIX F
-------
181
650
YOUTH IN AGRICULTURE - LABORATORY REPORT
ID:
LOCATION:
SAMPLE DATE: _/__/_
WEIGHT OR AMI.:
METHYL PARATHION
MALATHION
ETHYL PARATHION
TOXAPHENE
DEP
DMP
DETP
TYPE OF SAMPLE:
DATE OF ANALYSIS: _/__/_
CHEMIST:
ppm
ppb
RECOVERY: METHYL PARATHION
MALATHION
ETHYL PARATHION
TOXAPHENE
DEP _
DMP _
DETP
REMARKS:
-------
651
APPENDIX G
-------
183
652
Terms and design variables utilized in the multiple logistic
regression analyses of the four disease groupings (respiratory dis-
eases, dermatologic diseases, eye diseases, and symptoms of possible
pesticide poisoning).
Term Design Variables
(1) (2)
Status
Sex
Season
Age
Migrant
Seasonal
Non-farm
Female
Male
Non-growing (Nov. -April)
Early-growing (May-July)
Late-growing (Aug. -Oct.)
< 4
5-9
10-15
-1
0
1
-1
1
-1
0
1
-1
0
1
-1
1
0
-1
1
0
-1
1
0
-------
184
Summary of the multiple logistic regression analysis for respir-
atory diseases: tests of significance for terms entered in the final
model.
653
Term
Age
Season
Sex
Sex by Age
Status
Status by Age
Status by Season
Status by Season by Age
d.f.*
2
2
1
2
2
4
4
8
Approx.
F-test
151.56
29.26
19.76
12.61
9.90
5.50
3.08
3.34
P-value
.0000
.0000
.0000
.0000
.0001
.0002
.0150
.0008
* The degrees of freedom for the denominator approach infinity.
-------
185
654
Summary of the multiple logistic regression analysis for respir-
atory diseases: coefficients, standard errors of coefficients (S.E.),
and T-ratios for terms entered in the final model.
Term
Age
Season
Sex
Sex by Age
Status
Status by Age
Status by Season
Status by Season
Constant
Component
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(3)
(4)
(1)
(2)
(3)
(4)
by Age (1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
Coefficient
.516
-.016
-.116
.244
-.068
-.093
.010
-.079
.146
.034
-.094
-.148
-.010
.014
.050
.094
-.024
.102
.016
-.067
-.109
.031
-.046
.030
.131
1.068
S.E.
.040
.041
.041
.034
.015
.023
.023
.031
.040
.044
.058
.044
.059
.046
.063
.039
.056
.041
.092
.042
.084
.040
.095
.041
.086
.029
T-ratio
12.852
-.381
-2.810
7.250
-4.448
-4.011
.453
-2.574
3.668
.782
-1.612
-3.321
-.161
.297
.788
2.411
-.423
2.463
.177
-1.579
-1.305
.786
-.489
.725
1.514
37.108
-------
186
655
Summary of the multiple logistic regression analysis for derma-
tologic diseases: tests of significance for terms entered in the
final model.
Term d.f.* Approx. P-value
F-test
Season 2 3.96 .0190
Season by Age 4 3.46 .0078
Sex by Season 2 3.90 .0204
Status by Age 4 4.74 .0008
Status by Sex 2 3.01 .0493
Status by Sex by Age 4 2.07 .0822
* The degrees of freedom for the denominator approach infinity.
-------
18? 656
Summary of the multiple logistic regression analysis for derma-
tologic diseases: coefficients, standard errors of coefficients (S.E.),
and T-ratios for terms entered in the final model.
Term Component Coefficient S.E. T-ratio
Season
Season by Age
Sex by Season
Status by Age
Status by Sex
Status by Sex by Age
Constant
(1)
(2)
(1)
(2)
(3)
(4)
(1)
(2)
(1)
(2)
(3)
(4)
(1)
(2)
(1)
(2)
(3)
(4)
-.154
.042
-.088
.160
-.095
.124
.063
.077
.184
.335
-.173
-.165
-.102
.114
.087
-.104
-.108
.309
3.532
.060
.061
.089
.093
.088
.093
.058
.057
.067
.129
.067
.135
.045
.088
.065
.129
.065
.138
.041
-2.566
.694
-.987
1.716
-1.084
1.341
1.089
1.343
1.745
2.588
-2.590
-1.227
-2.253
1.295
1.339
-.804
-1.670
2.235
85.898
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188
657
Summary of the multiple logistic regression analysis for eye
diseases: tests of significance for terms entered in the final
model.
Term
d.f.*
Approx.
F-test
P-value
Age
Season
Status
Status by Age
Status by Sex
Status by Sex by Age
Status by Sex by Season
Status by Sex by Season
by Age
2
2
2
4
2
4
4
41
25
60
96
64
3.60
2.65
2.18
.0006
.0143
.0101
.0185
.0712
.0043
.0316
.0261
* The degrees of freedom for the denominator approach infinity.
-------
189
Summary of the multiple logistic regression analysis for eye
diseases: coefficients, standard errors of coefficients (S.E.),
and T-ratios for terms entered in the final model.
658
Term
Age
Season
Status
Status by Age
Status by Sex
Status by Sex
Status by Sex
Status by Sex
by Age
Constant
Component
(1)
(2)
(1)
(2)
(1)
(2)
(1)
(2)
(3)
(4)
(1)
(2)
by Age (1)
(2)
(3)
(4)
by Season (1)
(2)
(3)
(4)
by Season
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
Coefficient
.520
-.174
.162
-.210
-.002
.359
-.264
.086
.144
.289
.141
-.043
.132
-.154
-.117
.618
.116
-.508
-.194
.159
-.026
-.664
-.193
.029
-.060
.720
.008
-.117
4.093
S.E.
.151
.128
.085
.073
.098
.132
.160
.209
.137
.196
.062
.133
.093
.203
.092
.204
.096
.223
.086
.169
.144
.360
.132
.271
.144
.336
.129
.249
.095
T-ratio
3.443
-1.359
1.910
-2.901
-.024
2.720
-1.651
.413
1.053
1.479
2.276
-.327
1.414
-.759
-1.273
3.023
1.207
-2.274
-2.243
.942
-.181
-1.845
-1.469
.108
-.416
2.143
.062
-.469
43.105
-------
190
659
Summary of the multiple logistic regression analysis for symptoms
of possible pesticide poisoning: tests of significance for terms
entered in the final model.
Term d.f.* Approx. P-value
F-test
Age 2 8.84 .0001
Sex by Age 2 3.84 .0215
Status by Sex by Season
by Age 8 1.72 .0885
* The degrees of freedom for the denominator approach infinity.
Summary of the multiple logistic regression analysis for symptoms
of possible pesticide poisoning: coefficients, standard errors of
coefficients (S.E.), and T-ratios for terms entered in the final model.
Term Component Coefficient S.E. T-ratio
Age
Sex by Age
(1)
(2)
(1)
(2)
-.668
-.022
.423
.041
.170
.194
.162
.192
-3.939
-.115
2.622
.213
Status by Sex by Season
by Age (1) .081 .249 .327
(2) .150 .496 .303
(3) -.191 .251 -.761
(4) -.394 .435 -.905
(5) .898 .328 2.733
(6) -1.073 .632 -1.696
(7) -.150 .321 -.466
(8) 1.128 .552 2.043
Constant 5.996 .144 41.552
-------
660
Study of Pesticide Exposure of Child and
Adult Blueberry Harvesters 1n Southwestern
Michigan 1n July 1982
Research performed by
University of Iowa
Iowa City, IA 52240
August 1984
-------
Abstract 6 ^ 1
Three sets of exposure studies in different fields were conducted
using 21 youth (9-16 years) and 21 adult harvesters. Samples
from field one were analyzed for malathion, field two for
methiocarb and captafol, and field three for captafol. Each
study consisted of monitoring harvesters for two hours on three
consecutive days. Personnel air samplers, gloves, body patches,
urine, foliage leaf punches and soil samples were taken. Data
are given for each day's monitoring for environmental samples
and averaged youth and adult personal exposure samples. Overall
exposure in children was not remarkably different than adults.
Predominant exposure was to the hands and forearms. Metabolites
of malathion and methiocarb were detected in the urine, however
pre-exposure urine samples of subjects not exposed to these
pesticides in the study also showed metabolites of these
pesticides.
-------
662
TABLE OF CONTENTS
PAGE
Background and Organization of the Study , 1
The Southwestern Michigan Blueberry-Growing Region 2
The Harvester Monitoring Study of 1982 3
Study Summary 6
Field Pesticide Treatment Histories 9
Characteristics of Participants 10
Methods of the Study 12
Environmental and Personal Contact Samples 13
Urine Samples 18
Analytical Methods (Synopsis) 18
Results of the Study •-. 22
Environmental Samples 22
Soil 22
Air 26
Foliage 28
Personal Exposure Samples 35
Urine Metabolites 55
Interpretations 60
Dosage Estimates 60
Environment-Harvester Relationships 67
Urine Metabolites 71
Quality Control 74
Conclusions 77
Appendices
A. Field Data 82
B. Methods and Calculations 92
C. Measures of Personal Contact With Pesticides 116
D. Urinary Pesticide Metabolites 144
E. Quality Control 180
F. Forms Used in Study 216
Ih8184dv
-------
663
BACKGROUND AND ORGANIZATION OF THE STUDY
In 1978, state and federal agencies became aware that some
agricultural work involved exposure of children to residues of applied
pesticides. Concern about adverse effects on health arose partly from the
supposition that children would be more vulnerable to the effects of toxic
substances than adults, and partly from suggestions that the work habits of
children would be conducive to greater personal exposure to foliage
residues.
The Health Effects Branch of the Hazard Evaluation Division of the
Office of Pesticides, U.S. Environmental Protection Agency was asked to
undertake studies addressing the second of these concerns, specifically,
the exposure of young people to pesticides in the course of agricultural
work regularly performed by them. This research has been jointly supported
by the U.S. Department of Labor and the Environmental Protection Agency.
Harvest of fruit and berries has long been done by children as well as
adults. Currently, manual harvesting of all such produce is disappearing,
as mechanical methods prove more economic. There are still, however, some
regions where hand-picking of produce is done by adults and children.
In 1981, the Iowa Pesticide Hazard Assessment Project carried out a
limited study of apple harvesters in Wisconsin. At this location, it was
possible to contact only a few subjects at a time, and their work schedules
were so irregular that little systematic information could be gained.
Attempts to find other sites for study of harvesters in Iowa and
neighboring states were unsuccessful. In the midwestern U.S., there
are very few remaining agricultural operations that involve scheduled
harvesting of crops by children working alongside adults.
Ih8184dw l
-------
664
In 1982, the field investigator for the Iowa PHAF succeeded in
locating several blueberry plantations in southwestern Michigan where some
of the crop is still harvested manually, and the harvesters include
children.
The cooperation of the Michigan Blueberry Growers' Association was
requested and obtained for a study of adult and adolescent harvesters
during the summer of 1982.
The Southwestern Michigan Blueberry Growing Region
Soil conditions in the South Haven, Michigan area are favorable for
the commercial production of blueberries. Many local residents cultivate
blueberries in plots of one to thirty acres. Most of these growers are
members of the Michigan Blueberry Growers Association. The association
is well managed, providing members with specialized services, including
marketing assistance, advice on pesticide application, aerial application
service, development of new varieties of berries and processing equipment,
and research on irrigation, insect pests, and blights. Advice given to
growers on pesticide application is based partly on weather station data
from terminals located on several plantations. The association's Director
of Research was helpful to the Iowa Project in locating cooperative
growers.
Many blueberry growers in this area were contacted during April and
May of 1982. Only three growers would allow the Iowa Project to monitor
their berry harvesters for exposure to pesticides. Although most growers
would not allow the monitoring of their employees for pesticide exposure,
they did readily discuss their use of pesticides. From these
conversations, It would appear that with a few exceptions similar
pesticides and similar application rates are used by the majority of
growers in this area.
Ih8184dv 2
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665
The blueberries grown in southwestern Michigan ripen in phases through
most of the summer. Although certain varieties 'ripen earlier than others,
nearly all varieties produce harvestable fruit throughout the summer and
into early fall. Presently, about 702 £f_ all Michigan blueberries are
harvested mechanically. New varieties are being developed with shotter
ripening periods, thus facilitating mechanical harvesting.
Telephone conversations with the growers late in June indicated that
the crop would be in full harvest by July 15. Arrival at the plantations
on July 13 was during a period of cold wet weather which delayed the
ripening of large quantities of berries for a few days. Some berries were
being picked, but harvesters worked only intermittently. Because weather
conditions affect ripening, the study was delayed by one week. On the
Friday night (July 16) of that week, the area was deluged with six to eight
inches of rain. One plantation recorded six and one-half inches and
another nearly eight inches of rain. The weather then turned warm and
humid, with light rain falling four times in the following two weeks,
during which the present study was done.
This area of Michigan is nearly flat, with poor drainage. Fields
not under cultivation are heavily wooded with much underbrush. The soil
pH is acid, boggy and sandy and contains a large amount of organic
material. Mosquitoes are large and vicious. Therefore, harvesters
sometimes spray themselves heavily with repellents.
The Harvester Monitoring Study of 1982
The economics and mechanics of harvesting blueberries are relevant to
the study. Blueberry harvesters who work in the Michigan blueberry fields
are paid a piecework rate based upon the amount of berries that the
individual picks. They therefore try to harvest the largest amount of
lh818Adw 3
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666
berries possible with the least amount of movement. Experienced harvesters
wear a shoulder harness to support a container (pail) into which they place
the harvested berries. The harness also keeps the pail in a location that
can easily be reached with either hand. The pail is centered on the front
of the body with the top slightly below the level of the belt. Harvesters
usually work in pairs with one person working on each side of the row of
bushes.
Blueberry bushes range from three to six feet tall and vary from two
to four feet in width depending on variety, age and pruning. Harvest
season runs from July through early September with both ..green and ripe
berries on the bushes during this time. The harvester is required to pick
all of the ripe berries from each bush.
While picking berries from the outer branches of the bush the
harvester keeps the pail under the hands as much as possible. Berries are
picked with both hands simultaneously with the hands moving independently
to deposit picked berries in the pail. When picking the berries from the
inner branches the movements are the same with the exception that the body
pushes the pail into the bush and the outer branches are held out of the
way with the forearms while the hands are removing the ripe berries and
placing them in the pail.
The pesticide exposure study reported herein was done with several
objectives in mind. First, it was designed to determine whether harvesters
of blueberries are exposed to residues of pesticides previously applied to
the crop. Second, measurements were made to assess the relative importance
of inhalation and dermal routes of exposure by measuring airborne pesticide
and by measuring surface residue uptake on adsorbent patches and gloves.
Fourth, urinary metabolites of some pesticides were measured to confirm
absorption of pesticide. Finally, equal numbers of adults and young people
Ih6184dw 4
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667
(under 16 years) working together as harvesters were studied, so that
relative exposure levels, patterns of bodily exposure, and degree of
pesticide absorption could be compared.
Two plantations were selected for this study. A third was rejected
because nearly all employees were youngsters and no comparison of adult to
youth exposures could be made. On the first plantation, hereafter
designated VK, ten youths, sixteen years and younger, and ten adults were
recruited. (Results from this part of the project were first reported in
the 1983 Iowa PHAP Progress Report Series No. 53). Monitoring of adults
and youth engaged in harvesting was continued in two separate fields of a
second plantation (GC-1 and GC-2). Details of the three series of field
studies are presented in Table I. Each series consisted of monitoring the
harvesters for 2 hours on three successive days. Thus, a total of nine
"studies" were completed. Because the fields had been treated with more
than one pesticide, it was sometimes possible to assemble more than one
pesticide data set from a given study. From studies IV, V and VI, for
example, useful information could be obtained with respect to methiocarb
and captafol residues (last column, Table I). "Data sets" are therefore
designated by a study number (Roman numeral, left hand column, Table I)
followed by the name of the pesticide whose residues were the basis for
evaluating harvester exposure (right hand column, Table I).
Twenty-one youth and 21 adults served as subjects. •xfhe 18 subjects
participating in studies IV-VI also served in studies VII-IX. Two
additional youth and two additional adults were recruited for studies
VII-IX.
lhB184dv
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668
TABLE 1
Summary of Studies of Blueberry Harvesters in S.W. Michigan, July 1982
Study
No.
1
II
HI
IV
V
VI
VII
Time * of Subjects Pesticides
Date of Day Field Youth Adults Applied
7/20/82 12:00-2:00 PM VK 10 10 Malathion
Guthion
Triforine
7/21/82 1:30-3:30 PM VK 10 10 Ms lath ion
Guthion
Triforine
7/22/62 12:00-2:00 PM VK 10 10 Malathion
Guthion
Triforine
7/19/82 8:00-10:00 AM CC-1 9 9 Malathion
Guthion
Methiocarb
Captafol
Triforine
Terbacil
Simazine
7/20/82 8:30-10:30 AM CC-1 9 9 Melathion
Guthion
Methiocarb
Captafol
Triforine
Terbacil
Simazine
7/21/82 8:
-------
TABLE 1 (Cont'd)
Summary of Studies of Blueberry Harvesters in 5.W. Michigan, July 1962
669
Study
No.
Date
Time * of Subjects Pesticides
of Day Field Youth Adults Applied
Principal
Pesticide
Residues
Encountered
VIII
7/28/B2 6:00-10:00 AM
CC-2
11
11
Me lathi on
Cuthion
Methiocarb
Captafol
Triforine
Terbacil
Simazine
Captafol
IX
7/29/82 7:20-9:30 AM
CC-1
11
11
Ma lath ion
Cuthion
Methiocarb
Captafol
Triforine
Terbacil
Simazine
Captafol
lhB184dv
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670
Weather and soil conditions were recorded for each study (Appendix A -
Field Data). In general, weather was warn and humid, and it rained several
tines in the course of the investigation.
The insecticides malathion, guthion, and nethiocarb, and the
fungicides, captafol and triforine, had been applied to the fields. The
herbicides sinazine and terbacil had been applied to the soil. Specific
pesticide application histories of the fields are given in Table 2. Table
3 reports the ages and other characteristics of the study participants.
Surprisingly few youths were enployed by these growers. All of the
children working on the VK plantation and nearly all of those on the GC
plantation were recruited for these studies.
Clothing worn by the workers varied sonewhat. While nost workers
wore trousers and shoes, a few wore shorts and thongs. During all of
the GC studies the fields were wet, with sone nuddy areas. The workers'
shoes and trouser legs were usually wet. The VK field was.damp but
trouser legs stayed nearly dry. Shoes were usually wet.
The work habits of the harvesters in all studies were similar. There
were no mid-morning or mid-afternoon rest breaks. At mid-day they took
about an hour lunch break. The lunch was eaten while sitting on the ground
at the edge of the field near the work area. Very little drinking water
vas carried into the field. The workers usually had a drink of water at
mid-morning, at noon, and mid-afternoon. No in-field source of water was
available for drinking or washing of the hands. Very few of the harvesters
were seen to eat berries. Those who did, probably ate no more than a
handful per day.
All migrant workers were cooperative and eager to comply with the
instructions given them. Eight of the youth participating in studies I,
Hi III were from a nearby town. They followed instructions but were not
as industrious and cooperative as the migrant youngsters.
Ih8184dv 8
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671
Field
VK
CC-1
CC-2
TABLE 2
Pesticide Application Histories of the
Blueberry Fields
Pesticides Appl
-
Chemical
Triforine (16.2% EC)
Cuthion
Ague Ha lath ion
Aqua Halathion
ULV Ma lath ion
Sinbar
Simazine
Triforine
Oifolatan 4F
Difolatan 4F
Cuthion
Halathion
Methiocarb (WP)
Sinbar
Simazine
Triforine
Oifolatan 4F
Difolatan 4F
Cuthion
Ma lathi on
Methiocarb (WP)
ied
Date
4-30-82
6-06-82
6-18-82
7-01-82
7-20-82
4-04-62
4-04-82
5-04-82
5-20-82
6-09-82
6-09-82
6-22-82
7-13-82
4-05-82
4-05-82
5-05-82
5-21-82
6-10-82
6-10-82
6-23-82
7-14-82
Dosage
24 oz/A
1 qt/A
1 qt/A
1 qt/A
9.6 oz/A
1 Jb/A
1 Ib/A
24 oz/A
2 qt/A
2 qt/A
1 qt/A
1 pt/A
2 Ib/A
1 Ib/A
1 Ib/A
24 oz/A
2 qt/A
2 qt/A
1 qt/A
1 pt/A
2 Ib/A
Active
Ingredient,
1b Per Acre
0.3
0.5
2.0
2.0
0.6
0.8
0.8
0.3
2.0
2.0
0.5
1.0
1.5
0.8
0.6
0.3
2.0
2.0
0.5
1.0
1.5
Application
Method
Air
Air
Air
Air
Air
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Cnd
Days from
Appl i cation to the
Harvester Studv
81
44
32
19
4 1/2 hours
105
105
75
59
39
39
26
6
113
113
83
67
47
47
34
14
•f Cround applications were made with a low-volume air blast sprayer.
Ih8184dv
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672
TABLE 3
Age and Sex of Participants in Blueberry Harvesting
Studies I, II, III, July 20-23, 1982
VK Plantation
I.D.
Adults
Sex
Age
I.D.
Age
1.
2.
3.
A.
5.
6.
7.
8.
9.
10.
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
M
M
M
M
F
F
F
M
M
M
38
18
30
19
58
36
22
23
62
20
1. BRB
2. MEB
3. PAB
A. AMD
5. JEK-
6. DEL
7. BVK'
8. JVK'
9. CIH
10. GLH
M
F
M
F
F
F
M
F
F
F
13
11
9
13
12
13
13
11
12
15
Twelve participants were white migrant workers. Eight white youth,
numbers one through eight, were local Michigan youth. BVK and JVK are
children of the owners of the VK plantation and reside on the plantation.
Studies IV, V, VI, July 19-22, 1982
GC Plantation
I.D.
Adults
Sex
Age
I.D.
Age
1. WAG
2. KAY
3. JAM
A. JIY
5. MAT
6. DAG
7. EAG
8. JIJ
9. BIG
M
F
M
M
M
M
M
M
M
22
19
19
20
22
19
A3
25
A6
1. FRH
2. EGJ
3. RMG
A. AMG
5. TIS
6. DES
7. TOS
S. ROG
9. CHG
M
M
F
F
M
M
M
M
M
16
16
15
10
15
15
15
12
13
These subjects were all white migrant workers from Arkansas,
lh818Adv
10
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TABLE 3 (Cont'd)
Studies VII, VIII, IX, July 27-29, 1982
GC Plantation
673
I.D.
1. BIG
2. JIJ
3. EAG
4. DAG
5. JID
6. MAT
7. JIY
8. JAM
9. KAY
10. WAG
11. AND
Adults
Sex
M
M
M
M
M
M
M
M
F
M
F
Age
46
25
43
19
39
22
20
19
19
22
45
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
I.D.
CHG
ROG
TOS
DES
TIS
AMG
RMG
EGJ
JAH
LAH
FRH
Youth
Sex
M
M
M
M
M
F
F
M
F
F
M
Age
13
12
15
15
15
10'
15
16
15
14
16
All of these participants were white migrant workers. They were the
sane as participants in studies IV, V and VI, except for the addition of
four subjects.
Mean ages (years) of study participants were as follows:
Studies I, II, III
Studies IV, V, VI
Studies VII, VIII, IX
Adults
32.6
26.1
29.0
Ih8184dw
11
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674
METHODS OF THE STUDY
The following samples were taken to assess harvester exposure to
pesticide residues in the blueberry fields.
Environmental
1. Air - High Volume Sampler - 1 sample per study (45 minutes)
Personal Samplers - 1 per subject per study (2 hours)
2. Foliage Leaf Punches
3. Soil
Body Surface
4. Gloves
5. Body Patches
Forearms
Chest
Shoulders
Back
Inside forearms
Inside chest
Inside back
5 samples per study
5 samples per study
1 pair per subject
per study (worn 1 hour)
One set per subject
per study (worn 2 hours)
Absorption-Excretion Estimation
6. Urine Samples
Two specimens per study, one pre-work, one post-work.
Some potentially relevant variables were not measured in this study:
1) berries harvested by each worker per two hour period, 2) pesticide
residues on the berries themselves, and 3) height and weight of
participants.
IhBlSAdw
12
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671
Synopsis of Procedures Used in Preparing, Utilizing and Storing Sampling
Matrices, and in Extracting Matrices for Analysis (Detailed methods are
described in Appendix B)
General
Sampling matrices and materials for field spikes were prepared and
packaged in the laboratory before the field study. Amber jars for
storage of urine and foliage were mechanically precleaned in detergent
solution, rinsed in deionized water, then in acetone, and air dried.
Tops of all jars were fitted with aluminum liners. Utensils used in the
field (spatulas, leaf punch, and forceps) were rinsed with acetone
before collection of samples.
Zip-lock bags were not precleaned before use.
Cold storage in the field was accomplished by putting samples in
styrofoam containers, each supplied with dry ice. These were maintained
at dry ice temperature until samples were transferred to freezers at the
Iowa PHAP, maintained at 0*F (-18°C).
Climatic data, including air temperature, soil temperature, wind
conditions, humidity and sky conditions were recorded at each study site
(See Field Data forms - Appendix A).
Pesticide application histories were determined by interview of
grower-owners.
Air Sampling
1. High Volume Air Sampler
Four-inch diameter glass-fiber filter discs were used in staplex units
for high-volume air sampling without chemical preparation.
Ih8184dw 13
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676
XAD-4 resin (Rohm and Haas) was subjected to extensive cleanup:
washed in distilled water, then in methanol and acetone; soxhlet extracted
in a mixture of hexane:acetone (10:2). washed in acetone, then vacuum dried.
Forty-gram portions of clean resin were packaged in chemically clean vials, to
be layered over the glass-fiber filters before air sampling.
A previously calibrated Staplex High Volume Air Sampler was suspended
from a tripod in the field approximately in the center of the area being
harvested. The glass-fiber filter was put in place in the sampler, then 40
grains of the XAD-A resin were distributed over the filter surface. The
filter retaining ring was reattached. The sampler was operated for A3
minutes while the harvesters were at work. At the end of the sampling
period, the resin from the sampler was poured back into the original sample
container, which was tightly capped, labelled, and put into cold storage.
The filter itself was removed from the sampler. The exposed surface was
folded in upon itself. The filter was stored in a plastic zip-lock bag,
labelled, and kept cold until analysis.
Resin samples were analyzed separately. Each was soxhlet extracted
for 8-hours into hexane. The extract was dried by passage through
sodium sulfate, then was analyzed for specific pesticides.
Glass-fiber filters were gently pushed to the bottom of a glass
column (22 mm ID x 30 cm), having fritted glass and a stopcock at the
bottom. Seventy-five ml of hexane were poured into the column, where
the filter soaked for 20 minutes. Hexane was then drawn off slowly, and
dried with sodium sulfate.
2. Personal Air Samplers.
Each subject wore a Dupont P-4000 Personal Air Sampler, carrying the
pump on a belt. A Tygon tube extended from the pump over the shoulder to a
Ih8184dw 1A
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677
sampling tube pinned to the collar, so the open end rested in the
harvester's breathing zone.
The glass sampling tube was 7 cm long and 0.5 cm diameter, plugged
at either end with chemically clean glass wool, just sufficient to
retain 0.7 gm of XAD-4 resin in place. The resin column was 5.5 cm
long. Each pump was calibrated at a stable air flow (sampler in place)
before the study, and was rechecked after each study.
Each personal air sampling pump was operated for two hours while the
harvester worked. At the end of this period, the sampling tube was
detached, and the ends were occluded with Farafilm. Each tube was then
labelled and stored cold until analysis.
Analysis commenced with 8-hour soxhlet extraction of the resin into
hexane. This extract was dried with sodium sulfate, then subjected to
analysis for multiple pesticides.
Foliage Leaf Punches
Pesticide residues on foliage in harvested fields were estimated by
collecting leaf punch samples from five locations in the field. The
punch designed to make a clean section of leaf material was used to
collect fifty 2.86 cm2 (3/4 in. diameter) discs at each of the five sites.
Discs were delivered by the punch into a chemically clean glass jar.
Foliage samples were collected from the outer portions of the blueberry
plants, most likely to be contacted by harvesters. Each sample was
collected from several plants at each of the five locations.
Discs were transferred into amber jars, which were capped and
stored cold until analyzed.
Samples from each site were analyzed separately. Analysis began by
placing 25 leaf discs in a flask with 100 ml 2% aqueous solution of Sur-
Ih8184dw 15
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678
Ten (sodium dioctyl sulfosuccinate, a detergent). The flask was agitated
on a wrist-action shaker for 20 minutes. This was repeated twice with
fresh quantities of detergent solution, thus removing "dislodgeable
residues" of pesticides. The combined volumes of detergent washwater
were extracted with methylene chloride. The extract was then analyzed
for various pesticides.
Soil
Soil concentrations of pesticides were estimated from samples
(approximately 500 gm) taken from the upper 2-3 cm of soil, just below
the drip lines of several plants growing in the region where foliage
samples were taken. The area of soil sampled averaged about 120 cm2. Five
specimens were taken per study, the sampling sites corresponding to those
used in taking foliage samples. Samples were collected with a small
precleaned garden shovel. They were placed in zip-lock plastic bags, and
stored frozen until analysis.
Analysis commenced with shaking the 30 gm soil sample for 20 minutes
in acetone. Acetone extract was then filtered through scintered glass,
concentrated, and analyzed for various pesticides.
Gloves
White cotton gloves to be used for estimating hand contact with
pesticides were precleaned by washing twice in detergent solution,
then dried. They were then cleaned by refluxing in hexane:acetone
(10:2, v/v), rinsed in acetone, and allowed to air dry.
Gloves were worn by study participants during the first hour of the
study period. When collected they were placed in zip-lock bags, labelled,
and stored cold until analysis.
16
Ih8184dw
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679
Analysis commenced with eight-hour soxhlet extraction of each glove
pair into hexane. This extract was filtered, dried over sodium sulfate,
concentrated, and analyzed for various pesticides.
Body Patches
Body surface contact with pesticides was evaluated by the use of 4"
x 4" adsorbent pads attached by wire staples to a -paper jacket (Tyvek-
14) worn by each participant. Each pad consisted of an alpha-cellulose
square covered by 9-ply gauze, and backed with glassine. One pad was
attached over each forearm, each shoulder and on both sides of the chest.
A seventh patch was placed in the center of the back. Additional
alpha-cellulose pads, without the gauze overlay, were attached to the
inner surfaces of each jacket: right forearm, chest, and back.
The jacket and pads were worn by each participant during the entire
two-hour study period. At the end of the study, individual patches (or
patch pairs from opposite sides of the body) were detached and put into
zip-lock bags, which were labelled and stored cold until analyzed.
To limit the burden of analytical work, patches from opposite sides
of the body were analyzed together. There were, therefore, eight sampling
sites on the body surface: hands, forearms, chest, shoulders, back, inside
forearms, inside chest, and inside back.
Analysis began by extracting a randomly selected 2" x 2" quadrant of
each patch (quadrants from patch pairs were combined) into hexane (50-75
ml). The patch was placed at the bottom of a 30 cm x 22 mm ID glass
t Handling and attachment of body patches was done according to a protocol
developed as part of the Five Year Implementation Plan for the DOL/EPA
Interagency Agreement on Youth in Agriculture dated February 2, 1981. A
subsequent protocol for study of Ground Boom Spray exposure to
pesticides (April 20, 1981) prescribes the same procedures.
Ih8184dw 17
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680
column, with fritted glass and a stopcock on the lover end, into which the
volume of hexane was poured. After 20 minutes of soaking, hexane was
slowly drained from the column, contacting the patch enroute. This hexane
extract was dried over sodium sulfate, concentrated and used for subsequent
pesticide analyses.
Urine Samples
Two urine samples (complete voids) were collected from each participant
on each study day, one consisting of the first morning void (pre-work),
the second representing the first void after completion of the harvesting
exposure. A final sample was collected on the morning following the last
exposure study day. Samples were collected in chemically clean wide-mouth
amber glass jars of one pint capacity. Screw top covers were lined with
aluminum foil. Jars were labelled and stored frozen until analysis.
These urine specimens cannot be assumed to represent all urine formed
while harvesters were exposed to pesticide, nor can the metabolite
excretions calculated from the collections be assumed to reflect total
absorption during exposure. Metabolite excretions do identify minimum
levels of pesticide absorption. Volumes of urine samples collected
were, therefore, measured and recorded, so that total metabolite contained
in the samples could be calculated. Prework samples served to indicate
whether the subjects experienced exposure to pesticides other than that
associated with the study situation itself.
Urine samples were completely thawed and mixed before portions were
taken for measurement of specific pesticide metabolites.
Analytical Methods for Pesticide Residues and Urine Metabolites (Synopsis)
Complete details of methods are given in Appendix B.
18
Ih8184dv
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681
1. Malathion, guthion and captafol
A. In glass-fiber filters and body patches
Hexane extracts of the matrices were dried over anhydrous sodium
sulfate, concentrated by a stream of dry nitrogen, and then subjected to
gas-liquid chromatographic analysis.
Pesticides were identified by retention times determined from pure
standards. Quantities of pesticides were measured by comparing peak
heights from sample extracts with peak heights from standards.
B. In XAD-4 resins and
The 8-hour soxhlet extract into hexane was dried over sodium
sulfate, concentrated by a stream of dry nitrogen, and analyzed by the
same GLC procedure described in A, above.
C. In foliage
The methylene chloride extract of the detergent wash of leaf discs
was first dried by passage through sodium sulfate, then reduced to
dryness in a concentrator tube. The residue was taken up in hexane and
analyzed by the GLC procedure described in A, above.
D. In soil
The filtered acetone extract of soil was reduced to a convenient
volume by flash evaporator and the concentrate was analyzed by the GLC
procedure described in A, above. Rarely was it necessary to clean up the
extract on Norit-A.
2. Methiocarb in environmental matrices
Analysis for methiocarb utilized the same dried, concentrated organic
extracts of environmental samples that were used for malathion, guthion and
captafol analyses. However, it was necessary to derivatize this pesticide
to accomplish chroma tography.
Ih8184dw 19
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682
Concentrates were first reduced to a fraction of one ml. To the
remaining concentrate, 0.5 ml acetone solution of fluorodinitrobenzene
(FDNB) reagent, plus 5.0 ml sodium borate buffer, were added. Mixture
was held at 70°C for one hour. Five ml hexane were added to the cooled
tube, and mixed for two minutes, after which the hexane layer was
transferred to a clean centrifuge tube. Derivatized methiocarb was
analyzed by GLC without concentration.
Urine Metabolites
A. Alkyl phosphates and thiophosphates
One ml of urine was frozen in a glass sample tube, using dry ice in
acetone. Specimens were then freezedried in vacuo.
To the solid remaining in each tube were added one ml acetone, three
carborundum chips, and 0.1 ml of a 102 solution of 3-benzyl-l-p-tolyltria-
zine in acetone. Capped tubes were held at 70eC. for two hours.
After cooling, one drop of 6N HC1, 10 ml saturated NaCl solution,
and one ml benzene were added and mixed. Benzene layer was separated by
centrifugation, dried through sodium sulfate, and subjected to GLC
analysis.
The various alkyl phosphates and thiophosphates were identified by
retention times. Quantities were estimated by comparing peak heights of
sample extracts with peak heights of pure standards.
B. Malathion carboxylic acids
Urine was acidified and extracted into acetonitrile:diethyl ether
(1:1, v/v). Derivatization was accomplished with diazomethane. Derivatives
were extracted into hexane, which was subjected to cleanup on a silica gel
column. Elution was accomplished with benzene and ethyl acetate. The
concentrated eluate was analyzed by gas-liquid chromatography.
Ih8184dw 20
-------
683
The individual mono- and di- carboxylic acids (methylated) were
identified by their respective retention times, and quantities were
determined by comparing derivatized sample peak heights with peak
heights of derivatized standards.
C. Methiocarb phenol
Concentrated HC1 and water are added to one ml of urine and the
mixture was subjected to heat in a pressure cooker (150) for 15 minutes.
This step is intended to hydrolyze conjugates of phenolic compounds.
Cooled contents of the tube were extracted into methylene chloride.
Extract was washed with sodium bicarbonate solution, separated and dried
with sodium sulfate. Acetone was added, and methylene chloride was blown
off with a stream of dry nitrogen. The concentrate was derivatized,
subjected to Column cleanup, and analyzed by GLC.
The derivatized methiocarb phenol was identified by the retention time
of derivatized standard, and quantities present were calculated by
comparing peak areas from samples with peak areas from standards.
D. Urine Metabolite of Captafol
Strenuous efforts were made in 1983 to identify human urinary
metabolites of captafol, particularly tetrahydrophthalimide. No
satisfactory method was developed. There are strong indications that
tetrahydrophthalimide is not a major mammalian metabolite of captafol nor
of captan. It was not possible to identify urinary products consistently
excreted after captafol ingestion.
Ih8184dw 21
-------
684
RESULTS OF THE STUDY
These are discussed in the following order: 1) residues in environ-
mental samples (soil, air, foliage), 2) residues measured in matrices
designed to assess personal exposure (gloves, body patches, personal air
samples), and 3) urinary pesticide metabolites. Correlations and interpre-
tations of results (including quality control considerations) are presented
in the following section of the report.
Environmental Samples
Soil
Soil pesticide residue results are presented in Table 4. The
highest levels were residues of methiocarb (up to 6 yg per gm) in the GC-1
field, which had been treated with methiocarb six days previously. Most
other residues were in the range of one pg per gram, or less. Correction
for recoveries from soil (only laboratory spikes are available) might
double or triple this estimate of actual soil concentrations (Appendix E).
Even so, soil content of pesticide would not seem to represent a
significant source of exposure, even if the harvesters were barefoot, which
they were not.
Minute amounts of triforine were apparently detected in three soil
samples. Quantities were not sufficient to permit analytical confirmation.
During Study III, July 22, 1982, a sample of water was taken from each
of two pools that had accumulated in low spots of the VK field after a
night and morning of light rain. Samples were analyzed for pesticides:
Concentrations Expressed in parts per billion
Pesticide:
Pool #1
pool n
Malathion
3.2
0
CaptifoJ.
0
0
Methiocarb
0
0
Guthion
0
0
lh818Adw
22
-------
685
TABLE 4
Soil Pesticide Residues in the VK Field
Concentrations Are Expressed in ug per gn
Date,
Study
July 20,
1982
I
Sample Malathion Guthion Methiocarb Captafol Triforine
1
2
3
4
5
Means
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.003
July 21,
1982
II
1
2
3
4
5
0
0.470
0
0
0
0
0
0
0
0
0.1
0
0
0
0
0
0
0
0
0.003
July 22,
1982
III
Means
1
2
3
4
5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.002
Means
- indicates that samples were not analyzed.
Ih71184dv
23
-------
TABLE 4 (Cont'd)
Soil Pesticide Residues in the GC-1 Field
Concentrations Are Expressed in ug per gm
686
Date,
Study
July 19,
1982
IV
Sample Malathion Guthion Methiocarb Captafol Triforine
1
2
3
4
5
Means
0
0
0
0
0
0.78
5.5
5.6
4.3
5.7
4.3
5.1
0.78
July 20,
1982
V
1
2
3
4
5
Means
0
0.01
0.03
0
0.8
0.6
0.3
0.2
0.5
0.5
0.03
0.02
0.01
0.01
0.01
0.02
July 21.
1982
VI
1
2
3
4
5
Means
0.4
0.3
0.2
0.0
0.1
0.2
0
0.01
0.01
0
0
0.00
July 29,
1982
IX
1
2
3
4
5
Means
0.8
0.5
1.2
0.6
1.3
0.9
0.02
- indicates that samples were not analyzed.
Ih71184dw
24
-------
TABLE 4 (Cont'd)
Soil Pesticide Residues in the GC-2 Field
Concentrations Are Expressed in Vg per gn
687
Date,
Study
July 27.
1982
VII
Sample
1
2
3
A
5
Means
Methiocarb
0.2
1.7
0
0
0
Captafol
0
1.30
0
0
0
July 28,
1982
VIII
1
2
3
4
5
Means
0.02
0.90
0
0
0.11
0.21
- indicates that samples were not analyzed.
Ih71184dw
25
-------
688
Air Sampling
High-volume air sampling in a field-harvesting situation has little
or no relevance to worker exposure because results are so strongly
dependent on location of the sampler, wind conditions, etc.
Results of the high-volume air sampling effort are presented in
Table 5. In no case did airborne residues detected by this method
exceed 0.4 yg per m .
Ih8184dw 26
-------
689
TABLE 5
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 19B2
Airborne Pesticide Residues by High Volume Sampling
Sampler Volume « 0.538 m'/min Sampling Time » 45 minutes
Date,
Study
7-20-82
1
7-21-82
.11
7-22-82
III
7-19-62
IV
7-20-82
V
7-21-82
VI
7-27-82
VII
7-28-82
VIII
7-29-82
IX
Pesticide
Malathion
Captafol
Cuthion
Methiocarb
Malathion
Captafol
Cuthion
Methiocarb
Malathion
Captafol
Cuthion
Methiocarb
Malathion
Captafol
Cuthion
Methiocarb
Malathion
Captafol
Cuthion
Methiocarb
Malathion
Captafol
Cuthion
Methiocarb
Captafol
Methiocarb
Captafol
Methiocarb
Captafol
Methiocarb
Filter, uq
.
-
-
-
2.50
0
0
0.06
8.00
0
0
0
0
0.10
0
0
.
0
-
0.13
.
0.08
-
0.60
0.02
0
0
•
0
0
XAD-4
Resin, pq
•
-
-
-
.
-
-
5.90
0
1.40
0
8.90
0
0
0
0
0
4.10
0
0
_
0
-
0
0.51
0
0
•
0.39
0
Total, yg
.
-
-
-
2.50
-
-
5.96
8.00
1.*0
0
8.90
0
0.10
0
0
.
4.10
-
0.13
.
0.08
-
0.60
0.53
0
0
•
0.39
0
yg per mj
.
-
-
•
0.103
•
•
0.25
0.33
0.06
0
0.37
0
0.004
0
0
.
0.17
-
0.01
-
0.003
-
0.03
0.02
0
0
*
0.02
0
Specimens designated - not analyzed
Ih71184dv
27
-------
690
Air sampling by personal sampling devices offered a much more realis-
tic indication of harvester inhalation exposure. In general, more residue
is found, because the sampler is closer to the source of pesticide (the
foliage) than is the high volume sampler. Individual measurements are
reported in Appendix C. Table 6 compares the results of personal air
sampler measurements (mean values from 20 samplers per study) with
high-volume air sampler measurements.
The highest pesticide air concentration was that of malathion (average
198 yg/ms) in the VK field four and one-half hours after it had been
sprayed by ultra- low- volume application. This was determined by personal
air sampling. Assuming a pulmonary ventilation of 1.5 m9 per hour (25
liters per minute) and total retention of inhaled pesticide, this highest
air concentration would project an inhalation exposure of 300 yg per hour.
Although this level of exposure to malathion probably has little
«
toxicologic significance, similar exposure to a more toxic pesticide could
very well be hazardous.
Most measurements of airborne pesticide, even by personal sampler,
were in the 0.2 - 10.0 yg per m9 range. In these cases, inhalation
exposure was a small component of the overall exposure pattern. In a few
instances, high volume sampling appeared to detect low concentrations of
pesticide that were missed by personal air sampler. The much larger air
volume passed through the high-volume filter (about 270 times that moved
through the individual resin sampler) may have been a factor in detecting
very low concentrations.
Foliage Residues
Foliage residue measurements on the VK and GC fields are presented
in Table 7. Amounts of residues measured were in accord with expectations.
Ih8184dw 28
-------
691
TABLE 6
Comparison of Airborne Pesticide Concencrations
in Harvested Fields, as Determined by
High Volume and Personal Air Samplers
Uncorrected for Storage and
Analytical Losses
Air Pesticide Concentration, lig/m3
Studv Pesticide
I Malathion
Methiocarb
jGuthion
Captafol
II Malathion
Methiocarb
Guthion
Captafol
III Malathion
Methiocarb
Guthion
Captafol
IV Malathion
Methiocarb
Guthion
Captafol
V Methiocarb
Captafol
VI Methiocarb
Captafol
VII Methiocarb
Captafol
VIII Methiocarb
Captafol
IX Methiocarb
Captafol
High Volume
Sampler
^
-
-
-
0.10
0.25
-
-
10.00
0.37
0
0.06
0
0
0
0.004
0.01
0.17
0.030
0.003
0
0.02
0
0
0
0.02
Personal
Sampler
198
0
0
0
4.0
Ot
0
0
10.3
0
0
0.70
0
0
0
1.60
0
0.90
0
0.20
0.20
1.1
_
1.2
_
0.7
t One of twenty samples from personal air samplers positive at 0.34 yg
29
per m9.
Ih8184dw
-------
TABLE 7
Foliage Pesticide Residue in the VK Field
in Micrograms per 100 cm2 Leaf Surface
Uncorrected for Storage and Analytical Losses
692
Date,
Study
Sample Malathion Guthion Methiocarb Captafol Triforine
July 20,
1982
I
July 21,
1982
II
July 22,
1982
III
1
2
3
4
5
Means
Means
Means
50
36
208
73
80
21
0
0
0
0.2
0
1
2
3
4
5
40
14
4
14
32
0
0
0
0
0
1
2
3
4
5
3
13
12
5
4
0
0
0
0
0
- indicates that samples were not analyzed,
0.01
0.01
0.01
0.01
0
0
0.01
0
0.01
0
0
0
0
0
0
0
0
0.05
0
0
0
0
0
0
0
Ih8184dw
30
-------
TABLE 7 (Cont'd)
Foliage Pesticide Residues in Che GC-1 Field
in Micrograms per 100 cm2 Leaf Surface
Uncorrected for Storage and Analytical Losses
693
Date,
Study
July 19,
1982
IV
Sample Malathion Guthion Methiocarb Captafol Triforine
July 20,
1982
V
July 21.
1982
VI
July 29,
1982
IX
1
2
3
4
5
Means
1
2
3
4
5
Means
1
2
3
4
5
Means
1
2
3
4
5
Means
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1.6
0
0.7
0.1
0.5
0
0
0
0
1.1
0.2
16.0
37.7
18.9
21.4
48.2
5.4
26.3
27.3
19.0
1.2
1.9
3.8
10.6
0
-
-
-
-
6.5
49.6
69.8
10.2
16.9
30.6
7.0
10.6
8.5
13.4
8.0
9.5
- indicates that samples were not analyzed.
Ih8184dv
31
-------
694
TABLE 7 (Cont'd)
Foliage Pesticide Residue in the GC-2 Field
in Micrograms per 100 cm2 Leaf Surface
Date,
Study Sample Methiocarb Captafol
July 27. 1 1.3 6.2
1982 2 4.3 16.0
VII 3 0 12.1
4 2.0 7.4
5 0 9.1
Means 1.5 10.2
July 28, 1 0
1982 2 0
VIII 3 0
4 0
5 0
Means 4.2
In the light of negative findings in the GC-1 field which had been
treated with malathion, guthion and triforine at the sane time, no
analyses for these chemicals were done on the GC-2 samples.
Ih8184dw 32
-------
695
Malathion residues four and one-half hours after low-volume
application to the VK field were the highest values recorded (average 80 ug
per 100 en2, uncorrected). Residues decayed rapidly in the course of three
days post-application. No malathion was detectable on the GC field foliage
26 days after application to GC-1 or 34 days after application to GC-2
fields.
There were no detectable residues of guthion on VK or GC foliage 39-47
days after application.
Minute residues of methiocarb and captafol on the VK foliage probably
reflected drift from nearby fields. No intentional application of these
pesticides to the VK field was reported.
There were readily measurable residues of methiocarb on the GC-1
foliage 6 days after application (studies IV, V, VI). and minute amounts on
the GC-2 foliage 14 days after application (studies VII and VIII). Apparent
day-to-day variations in residue values probably reflected non-uniformity
of application and/or degradation. Methiocarb was definitely taken up by
harvesters' gloves and patches in both fields.
The remarkable persistence of captafol on foliage was borne out by the
foliage residue measurements. Despite repeated rainstorms in the 39-67 day
intervals between application and harvest, residues of this fungicide were
consistently measurable on the GC-1 and GC-2 foliage at harvest time.
Residues were sufficient to generate significant amounts of captafol in
gloves and patches, and even in a few air samples.
Several attempts were made to identify triforine on foliage, but
none was found. Because the method for triforine residues was not well
tested, a high level of confidence should not be attached to this negative
finding.
lh818Adw 33
-------
696
Personal Contact Exposure Samples
Basic personal exposure data are reported in detail in Appendix C for
all nine studies. Summary tables 8 through 25 following this page display
mean values for personal exposure determinations, together with relevant
summary statistics for environmental samples and urine metabolite
measurements. The pesticide measurements reported in these tables have not
been corrected for storage and analytical losses based on recoveries from
matrices spiked in the field.
Ih8184dw 34
-------
697
TABLE 8
Summary of Study No. I - Malathion
Date: July 20, 1982
Youth: 10 Adults: 10
Environmental Residues
Foliage
Soil
Air, High Volume
Field: VK
80
0 - 0.01
sample lost
ug per 100 cm2
ug per gm
tig per m3
Measures of Personal Contact
with Pesticide Residues
Youth Adults
Gloves, yg per pair,
one hour exposure 1958 6030
Body Patches, pg per 100 cm2,
two hours exposure
Forearms 76 308
Shoulders 20 96
Chest 21 45
Back 14 74
Ins. forearm 32 76
Ins. chest 4 7
Ins. back 2 2
Personal Air, yg per m' 163 232
Urine Metabolite
Malathion equivalents in
two samples following
exposure, pg 78 720
Combined
3994
192
58
33
44
54
6
2
198
399
Ih71184dw
35
-------
698
TABLE 9
Summary of Study No. II - Malathion
Date: July 21, 1982
Youth: 10 Adults: 10
Environmental Residues
Foliage
Soil
Air, High Volume
Field: VK
0 -
21
0.5
ug per 100
pg per gm
cm'
0.10 vg per nr
Measures of Personal Contact
with Pesticide Residues
Gloves, ug per pair,
one hour exposure
Body Patches, ug per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, ug per o9
Urine Metabolite
Malathion equivalents
in two samples following
exposure, ug
Youth
2067
238
40
29
19
98
3
3
Adults
6448
182
22
14
9
52
3
3
Combined
4258
210
31
22
14
75
3
3
104
274
189
Ih71184dw
36
-------
TABLE 10
Summary of Study No. Ill - Malathion
699
Date: July 22, 1982
Youth: 10 Adults: 10
Environmental Residues
Foliage
Soil
Air, High Volume
Field: VK
7 ug per 100 cm*
0 ug per gm
0.3 ug per ms
Measures of Personal Contact
with Pesticide Residues
Gloves, ug per pair,
one hour exposure
Body Patches, ug per cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, ug per m3
Urine Metabolite
Malathion equivalents in
two samples following
exposure, ug
Youth
152
20
Adults
146
0.4
Combined
149
56
17
18
11
4
14
7
26
25
8
7
5
14
10
41
21
13
9
5
14
9
10
137
259
198
Ih71184dw
37
-------
700
TABLE 11
Summary of Study No. IV - Malathion
Date: July 19, 1982
Youth: 9 Adults: 9
Environmental Residues
Foliage
Soil
Air, high volume
Field: GC-1
0 pg per 100 cm2
0.8 ug per gm
0 pg per m3
Measures of Personal Contact
with Pesticide Residues
Gloves, ug per pair,
one hour exposure
Body patches, pg per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, pg per m9
Urine Metabolite
Malathion equivalents in
two samples following
exposure, pg
Youth
Adults
Combined
0.02
0
0
0
0.04
0.06
0.08
0
0
0
0
0.01
0.01
0
0.01
0
0
0
0.03
0.04
0.04
139
88
114
- sample not analyzed
Ih71184dw
38
-------
TABLE 12
Summary of Study No. V - Malathion
701
Date: July 20, 1982
Youth: 9 Adults: 9
Environmental Residues
Foliage
Soil
Air, High volume
Field: GC-1
0 pg per 100 cm3
0.005 pg per gm
- pg per m9
Measures of Personal Contact
with Pesticide Residues
Gloves, pg per pair,
one hour exposure
Body Patches, pg per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, pg per m9
Urine Metabolite
Malathion equivalents in
two samples following
exposure, pg
Youth
0
0
0
0
0
0
0
Adults
0
0
0
0
0
0
0
Combined
0
0
0
0
0
0
0
171
70
121
- sample not analyzed
Ih71184dw
39
-------
702
TABLE 13
Summary of Study No. VI - Malathion
Date: July 21. 1982
Youth: 9 Adults: 9
Field: GC-1
Environmental matrices were not analyzed for malathion in
light of findings from previous two studies.
Urine Metabolite
Malathion equivalents in
two samples following
exposure, ug
Youth Adult Combined
134
69
102
IhSlSAdw
-------
703
TABLE 14
Summary of Study No. IV - Methiocarb
Date: July 19, 1982 Field: GC-1
Youth: 9 Adults: 9
Environmental Residues
Foliage 0.5 yg per 100 cm2
Soil 5.1 yg per gn
Air, High volume 0 yg per ms
Measures of Personal Contact
with Pesticide Residues
Youth Adults Combined
Gloves, yg per pair,
one hour exposure 225 196 211
Body Patches, yg per 100 cm2,
two hours exposure
Forearms 3.3 2.1 2.7
Shoulders 1.5 0.6 1.1
Chest 2.0 0.5 1.3
Back 0.8 0 0.4
Ins. forearm 0.3 0.3 0.3
Ins. chest 1.6 0.3 1.0
Ins. back 0.4 0.1 0.2
Personal Air, yg per m9 000
Urine Metabolite
Methiocarb equivalents in
two samples following
exposure, yg 42 67 55
Ih71184dw
-------
TABLE 15
Summary of Study No. V - Methiocarb
704
Date: July 20, 1982
Youth: 9 Adults:
Environmental Residues
Foliage
Soil
Air, High volume
Field: GC-1
0.2 ug per 100 cm2
0.5 ug per gm
0.01 ug per m9
Measures of Personal Contact
with Pesticide Residues
Gloves, ug per pair,
one hour exposure
Body Patches, ug per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, vg per ms
Urine Metabolite
Methiocarb equivalents in
two samples following
exposure, ug
Youth
459
Adults
651
Combined
555
5.7
0.5
0.4
0.4
0
0
0
0.9
0
0
0.1
0.5
0
0
3.3
0.3
0.3
0.3
0.3
0
0
37
57
47
Ih8184dw
42
-------
TABLE 16
Summary of Study No. VI - Methiocarb
705
Date: July 21, 1982
Youth: 9 Adults: 9
Environmental Residues
Foliage
Soil
Air, High Volume
Field: GC-1
10.6
0.2
Ug per 100 cma
yg per gm
0.03 ug per m9
Measures of Personal Contact
with Pesticide Residues
Gloves, yg per pair,
one hour exposure
Body Patches, yg per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, yg per m9
Urine Metabolite
Methiocarb equivalents in
two samples following
exposure, yg
Youth
243
Adult
400
Combined
272
2.6
0.7
1.0
0.5
0.3
0.3
1.3
1.7
0.4
0.4
0
1.3
0
2.6
2.2
0.6
0.7
0.3
0.8
0.2
2.0
45
49
47
Ih71184dw
43
-------
TABLE 17
Summary of Study No. VII - Methiocarb
706
Date: July 27, 1982
Youth: 11 Adults:
Environmental Residues
Foliage
Soil
Air, High Volume
11
Field GC-2
1.5
0.4
yg per 100 cm5
yg per gm
0 ug per m9
Measures of Personal Contact
with Pesticide Residues
Youth Adults Combined
Gloves, yg per pair
one hour exposure 33 24 29
Body Patches, yg per 100 cm2,
two hours exposure
Forearms 2.2 2.5 2.4
Shoulders 0.3 0.5 0.4
Chest 0.3 0.5 0.4
Back 0.3 0 0.3
Ins. forearms 00 0
Ins. chest 0.3 0 1.3
Ins. back 00 0
Personal Air, ug per m3 0 0.4 0.2
Urine Metabolite Only two Only two 0
Methiocarb equivalents samples samples
in two samples following positive: positive:
exposure, yg Trace, 32
Trace Trace
Ih71184dw
44
-------
TABLE 18
Summary of Study No. VIII - Methiocarb
707
Date: July 28, 1982
Youth: 11 Adults:
Environmental Residues
Foliage
Soil
Air, High Volume
11
Field: GC-2
0 yg per 100 cm5
- yg per gm
- yg per m3
Measures of Personal Contact
with Pesticide Residues
Gloves, yg per pair,
one hour exposure
Body Patches, ug per 100 cm2,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearms
Ins. chest
Ins. back
Personal Air, yg per m9
Urine Metabolite
Methiocarb equivalents
in two samples following
exposure, yg
Youth
Adults
Combined
0
-------
TABLE 19
Summary of Study No. IX - Methiocarb
708
Date: July 29, 1982
Youth: 11 Adults:
Environmental Residues
Foliage
Soil
Air, High Volume
11
Field: GC-1
0 ug per 100 cm2
0.9 ug per gm
0 ug per m3
Measures of Personal Contact
with Pesticide Residues
Gloves, yg per pair,
one hour exposure
Body Patches, ug per 100 cm3,
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearms
Ins. chest
Ins. back
Personal Air, ug per m'
Urine Metabolite
Methiocarb equivalents in
two samples following
exposure, ug
Youth
89
0.8
0.8
1.0
Adults
72
1.0
0.3
0.3
0(13) 0(16)
Trace(7) Trace(3)
Pos (2) Pos (3)
Combined
81
1.0
0.5
0.8
0
Median
Ih71184dw
-------
709
TABLE 20
Summary of Study Bo. IV - Captafol
Date: July 19, 1982
Youth: 9 Adults: 9
Environmental Residues
Foliage
Soil
Air, High Volume
Field: GC-1
16.00
0.78
yg per 100 cm2
yg per gm
.004 ug per nr
Measures of Personal Contact
with Pesticide Residues
Gloves, yg per pair,
one hour exposure
Body Patches, yg per 100
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins. chest
Ins. back
Personal Air, yg per m9
cm2,
Youth
1559
19
7
11
3
3
1
3
2.2
Adults
1478
19
5
6
2
1
1
1
0.9
Combined
1519
19
6
8
2
2
1
2
1.6
Ih8184dw
47
-------
TABLE 21 ' I 0
Summary of Study No. V - Captafol
Date: July 20, 1982 Field: GC-1
Youth: 9 Adults: 9
Environmental Residues
Foliage 26.30 yg per 100 cm2
Soil 0.01 yg per gm
Air, High Volume 0.17 yg per in3
Measures of Personal Contact
with Pesticide Residues
Youth Adults Combined
Gloves, yg per pair,
one hour exposure 836 764 800
Body Patches, yg per 100 cm2,
two hours exposure
Forearms 24 21 22
Shoulders 76 7
Chest 8 22 15
Back 31 2
Ins. forearm 22 2
Ins. chest 11 1
Ins. back 12 1
Personal Air, yg per m9 1.5 0.3 0.9
Ih71184dw
-------
711
TABLE 22
Summary of Study No. VI - Captafol
Date: July 21, 1982
Youth: 9 Adults: 9
Environmental Residues
Foliage
Soil
Air, High Volume
Field: GC-1
30.60
0 - 0.01
yg per 100 cm2
yg per gm
.003 ug per nr
Measures of Personal Contact
with Pesticide Residues
Youth Adult Combined
Gloves, yg per pair,
one hour exposure 1572 2082 1827
Body Patches, ug per 100 cm2,
two hours exposure
Forearms 20 22 21
Shoulders 978
Chest 878
Back 323
Ins. forearm 222
Ins. chest 11 1
Ins.back 111
Personal Air, yg per m9 0.3 0.1 0.2
Ih71184dw
-------
712
TABLE 23
Summary of Study No. VII - Captafol
Date: July 27, 1982 Field: GC-2
Youth: 11 Adults: 11
Environmental Residues
Foliage 10.20 yg per 100 cm2
Soil 0 yg per gm
Air, High Volume 0.02 yg per o9
Measures of Personal Contact
with Pesticide Residues
Youth Adults Combined
Gloves, yg per pair,
one hour exposure 1406 1132 1269
Body Patches, ug per 100 cm2,
two hours exposure
Forearms 61 58 60
Shoulders 12 12 12
Chest 18 8 13
Back 43 4
Ins. forearm 21 2
Ins. chest 10 1
Ins. back 10 1
Personal Air, yg per o9 1.5 0.6 1.1
Ih71184dw 50
-------
713
TABLE 24
Summary of Study No. VIII - Captafol
Date: July 28, 1982
Youth: 11 Adults: 11
Environmental Residues
Foliage
Soil
Air, High Volume
Field: GC-2
4.20
0.21
yg per 100 cms
yg per gm
0 yg per m3
Measures of Personal Contact
with Pesticide Residues
Youth Adults Combined
Gloves, yg per pair,
one hour exposure 867 1452 1160
Body Patches, pg per 100 cm2,
two hours exposure
Forearms 47 33 40
Shoulders 13 12 13
Chest 13 6 10
Back 77 7
Ins. forearm 24 3
Ins. chest 11 1
Ins. back 11 1
Personal Air, yg per m* 1.5 0.9 1.2
Ih71184dv
51
-------
TABLE 25
Summary of Study No. IX - Captafol
714
Date: July 29. 1982
Youth: 11 Adults: 11
Environmental Residues
Foliage
Soil
Air, High Volume
Field: GC-1
9.50
0.02
ug per 100 or.5
ug per gm
0.02 ug per m*
Measures of Personal Contact
with Pesticide Residues
Gloves, ug per pair,
one hour exposure
Body Patches, ug per 100
two hours exposure
Forearms
Shoulders
Chest
Back
Ins. forearm
Ins', chest
Ins. back
Personal Air, ug per ns
cm2.
Youth
911
25
7
12
2
2
1
1
0.9
Adults
1083
29
6
5
2
2
1
1
0.5
Combined
997
27
7
9
2
2
1
1
0.7
Ih71184dv
52
-------
715
Gloves and Body Patches
Not unexpectedly, manual contact with the residue-bearing blueberries
was the principal mechanism of harvester exposure to pesticide. Some
degree of correlation would be expected between residue levels (assuming
proportionality of residue per unit area on foliage and berries) and
quantities accumulated on gloves. Table 26 lists average foliage and glove
residues from the 9 studies for inspection and analysis. Correction
factors based on field spike recoveries have been applied to uncorrected
measurements. The Pearson correlation coefficient (v) for the corrected
foliage vs. glove pesticide relationship is a statistically non-
significant 0.47.
Many factors could account for the poor correlation. Residues of
three different chemicals are involved; apart from probable differences in
adsorption characteristics on berries and glove fabric, losses (based on
field spikes) were generally large and variable. The data are of
questionable value in testing the relationship between field residues and
glove accumulations.
Comparison of glove pesticide accumulations among adults with those of
young harvesters (Table 27) reveals no consistent differences. In 7
studies, the values for adults exceed those for youth, while in the
remaining 7, the opposite is true. In seven studies, glove contents of
either malathion or captafol after one hour of harvesting exceeded one
milligram of pesticide.
Levels of body surface contamination declined dramatically as distance
from the blueberry bush increased. Back patches showed very low levels of
contamination.
Further analysis of surface pesticide contamination is presented in
the Interpretations Section.
Ih8184dw 53
-------
TABLE 26
Relationship of Foliage Residues to Clove Pesticide Contents in Harvesters
716
Foliage Residues.
I
II
III
IV
V
VI
VII
VIII
IX
IV
V
VI
VII
VIM
IX
Pesticide
Malathion
Ma lath ion
Malathion
Methiocarb
Hethiocarb
Methiocarb
Methiocarb
Methiocarb
Methiocarb
Captafol
Captafol
Captafol
Captafol
Captafol
Captafol
ug
Jncorr
80.0
21.0
7.0
0.5
0.2
10.6
1.5
0.0
0.0
16.0
26.3
30.6
10.2
4.2
9.5
per 100 cm2
t
Recovery
0.16
0.16
0.16
0.05
0.05
0.05
0.05
0.05
0.05
0.39
0.39
0.39
0.39
0.39
0.39
Corr
500
131
44
10
4
212
30
0
0
41
67
78
26
11
24
Clove Contents.
Ug per pair
Uncorr Recovery
3,994
4,258
149
211
555
272
29
0
81
1,517
800
1,827
1,267
1,160
997
0.44
0.44
0.29
0.29
0.29
0.29
0.29
0.29
0.22
0.22
0.22
0.22
0.22
0.22
Corr
9,077
9,677
339
728
1,914
938
100
0
279
6,895
3,636
8,305
5,759
5,273
4,532
t Recovery « average recoveries from field spikes (Appendix E)
* Averages from all subjects, youth and adult, in each study.
IhSlSAdv
-------
717
Airborne Pesticide
Airborne pesticide estimated from personal air samplers was measurable,
but of small magnitude, in nine studies (Table 28). Measurements from
young harvesters exceeded those from adults in eight of the studies. A
plausible explanation of this is the greater proximity of younger (smaller)
harvesters to the residue-bearing foliage, which, when disturbed, releases
pesticide into the breathing zone air of the workers.
The exposure variable measurements recorded in Appendix C have been
further analyzed to provide estimates of pesticides dosage by various
routes of absorption. These calculations are presented and discussed under
Interpretations.
Urine Metabolite Measurements
Participants in this study excreted fractional milligram amounts
of the metabolites of malathion and methiocarb in specimens of urine.
Considering the dermal absorbability of these insecticides, it would seem
reasonable to conclude that absorption during the scheduled harvest
operations—particularly from exposure of the harvesters' hands—accounted
for the appearance of metabolites in the urine.
Several sets of assembled data indicate that pesticides contacted
in the course of this study's harvest operations could not have been
the exclusive source of urinary pesticide metabolites in study participants:
1) metabolites of malathion and methiocarb were present in substantial
concentration in initial pre-exposure samples (Appendix D, Tables 1,15,22),
2) urinary malathion metabolites were present in urine specimens collected
from participants working in the GC-1 field, where foliage residues of
malathion were absent, and personal exposure measurements (gloves, patches,
air) failed to identify malathion (Tables 11 and 12).
Ih8184dw 55
-------
718
TABLE 27
Youth-Adult Comparisons of Glove Pesticide
Contamination, ug per pair
(Not Recovery Corrected)
Study Pesticide Youth (N) Adult (N)
I
II
III
IV
V
VI
VII
VIII
IX
Malathion
Malathion
Malathion
Methiocarb
Captafol
Methiocarb
Captafol
Methiocarb
Captafol
Methiocarb
Captafol
Captafol
Methiocarb
Captafol
1,958
2,067
152
225
1,559
459
836
243
1,572
33
1,406
867
89
911
(10)
(10)
(10)
(9)
(9)
(9)
(9)
(9)
(9)
(11)
(ID
(11)
(11)
(11)
6,030
6,448
146
196
1,478
651
764
400
2,082
24
1,132
1,452
72
1,083
(10)
(10)
(10)
(9)
(9)
(9)
(9)
(9)
(9)
(11)
(11)
(11)
(ID
(11)
Ih8184dw 56
-------
719
TABLE 28
Youth-Adult Comparison of Personal Air Sample Contents
of Pesticide, ug per m3 (Not Recovery Corrected)
Study Pesticide Youth (N) Adult (N)
I Malathion 163.0 (10) 232.0 (10)
II Malathion 6.0 (10) 2.0 (10)
III Malathion 20.3 (10) 0.4 (10)
IV Captafol 2.2 (9) 0.9 (9)
V Captafol 1.5 (9) 0.3 (9)
VI Captafol 0.3 (9) 0.1 (9)
VII Captafol 1.5 (10) 0.6 (10)
VIII Captafol 1.5 (8) 0.9 (11)
IX Captafol 0.9 (10) .0.5 (8)
Ih8284dw 57
-------
720
This striking discrepancy between pesticide exposure and metabolite
excretion would not have been discovered if initial pre-exposure samples
had not been collected, and if urine specimens unlikely to contain
metabolites had not been analyzed. The finding is, of course,
disappointing, because it invalidates any correlation of metabolite
excretion with exposure variables. It may, however, reveal features of the
living and work environment of these harvest workers which will be crucial
to the development of measures to minimize their exposure to pesticides.
First, it is important to recognize that the amounts of pesticide
represented by these urine metabolites are small, usually in the range of
0.05 to 0.50 mg in two combined specimens. Twenty-four hour excretions of
malathion metabolites eight have been as much as 3 mg. There are probably
a number of circumstances in the working and living environments of the
harvesters that would generate this level of pesticide dosage.
Harvesters in the GC fields may well have been working in other local
fields during early morning and evening hours, although this was not freely
admitted. It seems less likely that this explanation would apply to the VK
field workers, most of whom resided on or near the VK plantation, and
customarily did harvesting only in VK fields.
Although harvesters were urged not to eat unwashed berries, it is
possible that this advice was not always heeded.
t Experiments in man have shown that an average of 2% of dermally applied
malathion is excreted as urinary metabolite. (Hayes, W.J., Jr. et al.
Safety of malathion dusting powder for louse control. Bull. WHO 22:503-
514 (I960)). Harvester exposures as high as 19 mg per hour are
estimated to have occurred in study I (vide infra). As exposure
extended
over 8 hours, excretion of 3 mg (0.02 x 152) malathion equivalents might
have been expected.
Ih8284dw 58
-------
721
Application of pesticides by airplane or ground-based air-blast
sprayer cannot be done without generating drift. As this type of
application was done over large areas of the blueberry growing region,
drift may have contaminated cars or trailers occupied by the harvesters.
The source(s) of malathion and methiocarb in the initial preexposure
urines, and in the urines of the GC field crews are not known, and we
will probably not be able to determine what they were. The clear evidence
of pesticide exposure in addition to that generated in the course of the
scheduled harvest does, however, emphasize the need for a very broad
definition of "work environment" in the case of personnel engaged in this
kind of agricultural operation.
Ih8284dw 59
-------
722
Total Pesticide Exposure and Dosage
Total pesticide exposure (mg per person per hour) and exposure dosage
(ug per kg body weight per hour) have been estimated for groups of adults
and youth significantly exposed to malathion, methiocarb and captafol.
Starting with measurements of pesticides trapped in gloves, 4" x 4"
patches, and on personal air filters operated for standard times,
calculations have been applied to estimate exposure per hour to hands,
various parts of the body (forearms, shoulders, chest, back) and also
inhalation exposure. The sum of these partial exposures has been
calculated as each picker's total exposure. Dosage is the total exposure
divided by each picker's body weight.
Multiple correction factors were applied to sample matrix measurements
to arrive at personal exposure estimates. These are as follows.
Time Corrections
Gloves were worn just one hour, so no time correction was needed.
Patches were worn two hours; therefore measured pesticide was divided by
two. Inhalation exposure was based on an average moderate-activity-level
pulmonary ventilation of 1.5 m9 per hour in adults and children (25 liters
per minute x 60 * 1000), and the assumption that all inhaled pesticide was
retained.
Area Corrections
Pesticide trapped in the gloves was assumed to represent total hand
exposure.
Patches were 103 cm2 in area. In the case of forearms, shoulders and
chest, patches on the two sides of the body were analyzed together (206
on2). Only one patch was used on the back (103 cm2). Pesticide trapped in
patches was extrapolated to average areas of the respective body regions,
jr42485dw - A60 -
-------
723
according to ages and sexes of the young participants (Table 29A). For
adults, regional area estimates for adult man, published by Popendorf and
Leffingwell, were used. (Eighty percent of the adult pickers were men.)
Table 29B shows the body area correction factors used, by age and sex.
jr42485dw - A61 -
-------
724
Age,
yrs
9
10
11
12
13
14
15
16
wt,a
kg
28.1
31.4
35.3
39.8
46.0
50.8
56.7
62.1
Table 29 A
Estimated Weights and Body Areas of
Male Youth And Adults
2
Estimated Surface Areas, cm
Forearms Shoulders Chest
Adults 68.9
523
563
616
650
710
777
851
904
1,286C
530
571
626
660
721
789
864
918
1,306(
624
672
736
776
848
928
1,016
1,080
Back
624
672
736
776
848
928
1,016
1,080
1,536C 1,536C
Age,
Yrs
9
10
11
12
13
14
15
16
Wt,a
kg
28.5
32.6
37.0
41,
46.
50.
53.
.5
,1
.3
.7
55.9
Estimated Weights and Body Areas of
Female Youth and Adults
2
Estimated Surface Areas, cm
Forearms Shoulders Chest
523
566
616
670
730
770
804
837
Adults 68.9
1,286C
530
575
626
680
741
782
816
850
1,306C
Back
624
676
736
800
872
920
960
1,000
624
676
736
800
872
920
960
1,000
1,536*
a. Fiftieth percentile values from weight-stature growth curves based on
U.S. national child development statistics. Obtained from Department
of Pediatrics, University of Iowa Hospitals.
b. Total body surface areas determined from the Boothby and Berkson Food
Nomogram, Division of Biometry and Medical Statistics, Mayo Clinic,
Rochester, Minnesota. Areas of body regions (as Z of total) taken from
"Estimation of Area of Burn and Diagram" used by University of Iowa
Hospitals burn care unit.
c. Popendorf, W.J., Leffingvell, J.T. Regulating Organophosphate
Pesticide Residues for Farm Worker Protection. Residue Reviews 82:
p. 157, 1982.
jr42385dw
- A62 -
-------
jr«2385dv - A63 -
725
Table 29B
Body Area Correction Factors
Age Forearms Shoulders Chest Back
M F M F M F M
9
10
11
12
13
14
15
16
2.54
2.73
2.99
3.16
3.45
3.77
4.13
4.39
2.54
2.75
2.99
3.25
3.54
3.74
3.90
4.06
2.57
2.77
3.04
3.20
3.50
3.83
4.19
4.46
2.57
2.79
3.04
3.30
3.60
3.80
3.96
4.13
3.03
3.26
3.57
3.77
4.12
4.50
4.93
5.24
3.03
3.28
3.57
3.88
4.23
4.47
4.66
4.85
6.06
6.52
7.15
7.53
8.23
9.01
9.86
10.49
6.06
6.56
7.15
7.77
8.47
8.93
9.83
9.71
Adults 6.24 6.34 7.46 14.90
-------
726
Analytical Corrections
Analytical recovery factors (Table 29C) were based on field spikes of
matrices, using measured volumes of solvents containing the pesticides of
interest. The validity of this method of estimating analytical loss is
uncertain. Most field residue is dry as it attaches to gloves and patches.
Table 29C
Analytical Corrections Factors
Matrix
Gloves Patches Air Filters
Avg Corr Avg Corr Avg Corr
Rcvy Factor Rcvy Factor Rcvy Factor
Malathion
Methlocarb
Captafol
44Z
29Z
22Z
2.27
3.45
4.55
69Z
56Z
33Z
1.45
1.78
3.00
61Z
36Z
58Z
1.64
2.78
1.72
This recovery data has been taken from Table El, Appendix E.
Pesticide Dosage Estimation
Dosage is defined as total exposure divided by body weight (ug per kg
per hour).
Body weights of participants were not measured, but have been
estimated from tables of average body weights of males and females ages 9
to 16 years (Table 29A, second column from left).
Statistical Treatment
Medians and ranges have been determined for the various sets of
pesticide exposure data. The Wilcoxon rank sum test has been applied to
test significance of differences between medians characterizing adult and
youth harvesters.
The statistical significance of ranges of measurement has been
evaluated according to the tables published by P.N. Somerville "Tables for
1r42385dw - A64 -
-------
727
Obtaining Non-Parametric Tolerance Limits" in Annals of Mathematical
Statistics, p. 599, 1958.
Results
Table 30 shows median hourly pesticide exposures to various regions of
the body, and by inhalation, for adult and youth groups of pickers.
The three serial days of malathion exposure are listed individually
because the foliage residue levels differed widely. Foliage residues of
methiocarb and captafol were similar on the three respective serial days of
observation, so these data were pooled.
Tables 31A and 31B identify medians and ranges of total exposure and
exposure dosage, respectively, within adult and youth groups of harvesters.
Median values for total exposure are sometimes less than medians for glove
exposure. This, of course, is a reflection of the strongly skewed
distributions of the data. Only in the case of the first malathion study
were medians for youth and adults significantly different. Both exposure
and dosage were lower in the youth.
Table 32A pools the methiocarb total exposure measurements and the
measurements within the two series of captafol exposures. There were no
significant differences between medians for total exposure of adults and
youth, despite the greater statistical power. The larger numbers of
observations do make possible a more useful statement as to the likely
range of total exposures under the conditions of this field study. Table
32B lists medians and ranges for dosage, according to the same format.
Again, only the initial malathion study yielded a statistically significant
difference between medians for youth and adults.
jr42385dw - A65 -
-------
Table 30
Median Body Region Exposures to Pesticides (mg per hour) on the Part,of Adults and Youth
Engaged In Blueberry Picking
Pesticide,
Date
Malathlon
Jul 20
21
22
Hethtocarb
Jul 19,
20,21
Captafol
Jul 19,
20,21
Captafol
Jul 27,
28,29
Fol 1 age
Residue
lig/100 cm*
80
21
7
4
2%
8
Number of
Testst
Adult
9
10
10
26
25
26
Youth
9
10
9
2%
2%
30
G1 oves ,
Big/hour
Adult Youth
16.6 ** 4.6
9.7 2.0
0.4 0.3
1.00 0.50
4.75 4.32
4.85 4.03
Forearms,
mg/hour
Adul t Youth
2.1 ** 0.3
1.5 1.1
0.2 0.1
0.017 0.013
0.289 0.210
0.647 0.620
Shoulders,
mg/hour
Adult Youth
1.00 0.04
0.20 0.08
0.30 0.05
0 0.004
0.099 0.074
0.171 * 0.114
Chest
mg/hour
Adult Youth
0.40 0.12
0.08 0.17
0.10 0.08
0 ** 0.010
0.107 0.109
0.112 0.144
Back
mg/hour
Adult Youth
0.05 0.02
0.04 0.06
0.06 0.04
0 0
0.022 0.014
0.060 0.033
Personal Air
mg/hour
Adult Youth
0.250 0.230
0.001 0.003
0.001 0.025
0 0
0.0003 ** 0.001
0.0010 ** 0.002
t The numbers recorded here are the 2-hour tests done, for which complete sets of data were available. Multiple tests were performed on each subject
on serial days.
•"Significantly different at the p<0.01 level, by the Nilcoxon rank sum test.
Significantly different at the p<0.05 level, by the Nilcoxon rank sum test.
-vl
rv>
CO
-------
729
Table 31A
Total Exposure to Pesticides on the Part of Adults and Youth
Engaged in Blueberry Picking
sticide,
te
Lathion
Jul 20
21
22
ihiocarb
:ul 19
20
21
tafol
ul 19
20
21
tafol
ul 27
28
29
Average
Foliage
Residue,
Ug/100 cm2
80.0
21.0
7.0
0.5
0.2
10.6
16.0
26.3
30.6
10.2
4.2
9.5
Number of
Subjects (N)
Adults Youth
Total Exposure,
mg per person per hour
Medians and Rangest
Adults Youth
9
10
10
8
9
9
8
8
9
9
9
8
9
10
9
9
8
7
9
8
7
10
11
9
23.3 (5.0-30.0)
12.9 (0.7-55.0)
1.0 (0.6-1.4)
0.4 (0.3-1.4)
1.1 (0.3-2.0)
1.0 (0.5-5.2)
6.0 (2.3-11.8)
3.9 (2.5-9.9)
9.1 (0.9-31.8)
6.8 (3.5-8.9)
6.9 (3.1-20.7)
5.5 (1.2-9.7)
5.5 (0.7-9.2)
4.1 (2.0-23.4)
1.0 (0.4-1.9)
0.5 (0.1-3.4)
0.5 (0.1-1.7)
1.0 (0.3-2.1)
4.7 (1.8-27.8)
4.1 (1.9-6.8)
7.2 (2.7-14.8)
7.0 (3.0-15.5)
4.8 (1.6-9.1)
4.0 (1.6-9.2)
Significance
of Difference
<0.01
Ranges include 75Z of the population of observations, at the following levels of
confidence: If N - 7, Y • 0.58 If N - 9, Y • 0.70
If N - 8, Y • 0.63 If N - 10, Y - 0.76
Jr42385dw
- A66a -
-------
Table 3IB
Pesticide Exposure Dosage on the Fart of Adults and Youth
Engaged in Blueberry Picking
730
Pesticide,
Date
Malathion
Jul 20
21
22
Methiocarb
Jul 19
20
21
Captafol
Jul 19
20
21
Captafol
Jul 27
28
29
Average
Foliage
Residue,
ug/100 cm2
80.0
21.0
7.0
0.5
0.2
10.6
16.0
26.3
30.6
Number of
Subjects (N)
Adults Youth
10.
4.
9.5
9
10
10
8
9
9
8
8
9
9
9
8
9
10
9
9
8
7
9
8
7
10
11
9
Exposure Dosage in
yg per kg body weight
per hour
Medians and Rangest
Adults Youth
339.0 (72.7-385.0)
187.0 (10.8-798.4)
13.8 (9.1-19.6)
6.1 (3.9-20.3)
15.9 (3.8-29.2)
14.7 (6.9-75.5)
85.8 (33.4-172.0)
56.2 (35.6-144.4)
131.2 (12.6-461.0)
99.1 (50.5-128.7)
99.8 (45.4-300.8)
79.3 (17.1-140.9)
121.4 (13.5-248.1)
99.1 (42.6-435.3)
17.0 (10.9-43.1)
9.4 (2.3-62.5)
11.2 (3.7-38.5)
17.8 (5.4-65.0)
75.1 (49.9-617.3)
80.7 (48.5-120.4)
123.7 (82.0-261.0)
145.0 (74.4-290.7)
77.9 (48.0-151.1)
81.4 (28.9-161.9)
Significant
of Differei
<0.05
t Ranges include 75Z of the population of observations, at the following levels of
confidence: If N - 7, y - 0.58 If N - 9, y - 0.70
If N • 8, Y - 0.63 If N - 10, y • 0.76
Ih42285dw
- A66b -
-------
731
Table 32A
Total Exposures to Methiocarb and
Captafol on the Part of Adults and Youth
Engaged in Blueberry Picking
Mean
Foliage Nos. of ug per person per hour Significance
Pesticides, Residue Subjects (N) Medians and Rangesa of
Dates ug/100 cm2 Adults Youths Adults Youths Differences
Methiocarb,
July 19-21 3.8 26 24 1.0(0.3-5.2) 0.5(0.1-3.4) N.S.
Captafol
July 19-21 24.3 25 24 6.0(0.9-31.8) 4.9(1.6-27.8) N.S.
Captafol
July 27-29 8.0 26 30 6.7(1.2-20.7) 5.5(1.6-15.5) N.S.
a At N » 25, ranges include:
- at least 90Z of the population of observations,
at a confidence level of 0.73.
- at least 75Z of the population of observations,
at a confidence level of 0.99
jr42485dw " A66° "
-------
732
Table 32B
Exposure Dosages of Methiocarb and
Captafol on the Part of Adults and Youth
Engaged in Blueberry Picking
Pesticide,
Dates
Methiocarb,
July 19-21
Captafol
July 19-21
Captafol
July 27-29
Mean
Foliage
Residues.
ug/100 cm
3.8
24.3
8.0
Nos. of
Subjects(N)
Adults Youth
26
25
26
24
ug per kg body
weight per hour Significat
Medians and Ranges of
Adults Youth Difference
13.7(3.8-75.5) 10.2(2.3-65.0) N.S.
24 77.0(12.6-461.0) 86.2(48.5-617.3) N.S.
30
97.5(17.1-300.8) 104.8(28.9-290.7) N.S.
At N • 25, ranges include:
- at least 902 of the population of observations,
at a confidence level of 0.73.
- at least 752 of the population of observations,
at a confidence level of 0.99
jr42485dw
- A66d -
-------
733
Table 32C pools all the measurements of total exposure and dosage
from the two series of captafol exposure studies (51 measurements in
adults and 54 in children). Adult-youth differences between medians are
still not significantly different. Ranges of exposure and dosage are
indeed wide. There is no reason to believe that this is not an accurate
reflection of the true variation when workers engage in so complex an
activity as harvesting.
jr42485dw - A66e -
-------
Table 32C
Total Pesticide Exposure to, and Dosage of,
Captafol Among Adults and Youth Engaged in
Picking Blueberries
734
Dates
July 19,20,
21,27,28,29
Mean
Foilage
Residues.
ug/100 cm
16.1
No. of
Tests(N)
Adults Youth
51
54
Total Exposure
mg per person
per hour
Medians and Ranges
Adults Youth
6.0
(0.9-31.8)
4.8
(1.6-27.8)
Ranges which include 75%
of populations of observations,
with 0.90 confidence
3.3-9.9
2.7-9.2
Dates
July 19,20
21,27,28,29
Mean
Foliage
Residue,
;/100 an
No. of
Tests (N)
Adults Youth
16.1
51
54
Exposure Dosage
ug per kg body
weight per hour
Medians and Ranges
Adults Youth
86.6
(12.6-461.0)
95.6
(28.9-617.3)
Ranges which include 752
of populations of observations, 47.2-144.4
with 0.90 confidence
59.7-162.9
a The differences between medians for adults and youth with respect to total
exposure and exposure dosage are not statistically significant.
jr42485dw
- A66f -
-------
735
Residue - Harvester Relationships
Table 33 displays corrected foliage residue data (column 6 from left)
in relation to applied dosage (column 4 from left) and accumulated residues
in gloves (right hand column). Malathion decayed rapidly as expected; the
behavior of methiocarb residues is unexplained except possibly as sampling
variation in a field where residues were not evenly distributed. Clearly,
the gloves accumulated pesticide from substantial areas of surfaces
contaminated with the pesticides.
To compare harvester exposures in fields having widely divergent
residue levels, it may be useful to calculate the ratio of a personal
exposure measurement (such as cumulative exposure per hour) to the average
foliage residue concentration (weight of pesticide per unit area). The
result is a virtual area of residue-bearing surface "cleared" of pesticide
per unit time. A value of one m2 per hour could mean that all the
pesticide was picked up from one m3, or, more likely, that 102 of the
residue was taken up from 10 m2. In any event, the "residue clearance"
ratio reflects the efficiency of worker uptake of residue irrespective of
absolute residue level. The ratio is obviously a function of many features
of the exposure situation, ranging from accessibility of the residue to
intimacy of contact between workers and residue-bearing surfaces. There
may be some merit in calculating the ratio in various residue-exposure
situations as an indicator of overall efficiency of residue uptake.
In examining citrus harvester data from Florida and California, Kigg,
t 4
Stamper and Queen concluded that a constant of 10 was suitable in
relating worker exposure (yg per hour) to residue (ug per cm2). This
indicates a clearance of one meter (10,000 cm2) per hour.
t A.I.H.A.J. 41:652-659 (1984)
Ih8284dw 67
-------
736
Table 34 reports residue clearance ratios for the 12 blueberry
harvester studies wherein foliage residues were readily measurable. The
rates vary over a wide range (0.12 to 7.09), but averages are not far
removed from the value of 1.0 meter per hour reported by Nigg et al. The
grand mean for youth is 132 below that for adults, but the difference is
.not significant statistically.
Ih8284dw 68
-------
737
TABLE 33
Dosages of Applied Pesticides, Intervals to Harvest, and
Measured Foliage and Clove Residues (Corrected)
Applied Dosage,
Average Average Two-"
Interval to Foliage Residue hour Accumulation
Study
1
II
III
1
II
III
IV
V
VI
IV
V
VI
IV
V
VI
VII
VIII
IX
Field
VK
VK
VK
VK
VK
VK
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-1
CC-2
Pesticide
ULV Ma lath ion
ULV Ma lathi on
ULV Malathion
Cuthion
Cuth i on
Cuthion
Methiocarb
Methiocarb
Methiocarb
Captafol
Captafol
Captafol
Cuthion
Cuthion
Cuthion
Captafol
Captafol
Captafol
uq/100 cm*
670
670
670
561
561
561
1,680
1,680
1,680
2,244
2,244
2,244
561
561
561
2,244
2,244
2,244
Harvest. Days pg/100 on2
0.19 (41s hrs) 500
1.19 131
2.19 44
44 m
if __ i^^i
45 TTT
46 +tt
6 10
7 4
8 212
39 41
40 67
41 78
39 ttt
40 -W
41 m
47 26
48 11
48 24
on Cl oves , Ug
18,154
19,354
677
3
0
2
1,455
3,828
1,875
3,038
1,600
3,654
0
0
0
2,538
2,320
1,994
* Average active ingredient per 100 cm2 field area.
t Corrected for analytical loss, as reflected in field spikes.
U Mean of youth and adult values, corrected for analytical loss, as reflected in field spikes.
•H-f Field spike recoveries too low -.0 yield valid estimates.
69
-------
TABLE 34
Pesticide Residues Clearances in Twelve Harvester Studies
Wherein Finite Foliage Residues Were Measured
738
Total Worker Exposure,
mg per hour
(corrected)
Study
Pesticide
Youth
Adult
I
II
III
IV
V
VI
IV
V
VI
VII
VI I I
IX
Halathion
Malathion
Me lath ion
- Methiocarb
Methiocarb
Methiocarb
Captafol
Captafol
Captafol
Captafol
Captafol
Captafol
6.0
7.9
1.4
0.9
0.9
0.9
7.8
4.0
7.9
9.0
5.6
5.3
19.0
16.8
1.0
0.7
1.2
1.4
7.3
3.9
10.2
6.5
7.8
5.5
Foliage Residue,
yg per em*
(corrected)
Residue Clearance
mz per hour
5.00
1.31
0.44
0.10
0.04
2.12
0.41
0.67
0.78
0.26
0.11
0.24
Youth
0.12
0.60
0.32
0.90
2.25
0,04
1.90
0.60
1.01
3.46
5.09
2.21
Adult
0.36
1.2B
0.23
0.70
3.00
0.07
1.78
0.58
1.31
2.50
7.09
2.29
Mean Residue
Clearances
m2 per hour
Youth Adult
0.35 0.63
1.06 1.26
1.17 1.22
3.59 3.96
1.5*
1.77
. * 0.23
(N.S.)
Ih8284dw
70
-------
739
Urinary Metabolites of Malathion and Methiocarb
Measurement of Che urinary metabolites of malathion and methiocarb in
the course of harvester exposure to these compounds was more useful in
demonstrating the limitations of metabolite monitoring than in
strengthening the observational base of the study itself.
The only indications that pesticide absorption in the course of
scheduled harvesting contributed to the excreted metabolite were the maxi-
mum values of 399 ug and 321 ug per void from adults working in the VK
field within 24 hours of ULV malathion application (Table 35). Apart from
this observation, there was no correspondence between urinary metabolite
excretion and various measures of exposure: foliage residue, glove
contamination, etc. Indeed, malathion metabolites were excreted by some VK
and GC field harvesters before they started work (Tables D-l, 2 and D-15,
16), and were consistently excreted by GC field harvesters even though:
1) the field had not been sprayed with malathion for 3 1/2 weeks, 2) the
foliage showed no malathion residue, and 3) gloves, surface patches and air
were essentially free of malathion.
There appeared to be a baseline level of alkyl phosphates and
malathion acids in subjects' urines, equivalent to about 20-50 micrograms
per sample, that was present whether the subjects were working in fields
previously sprayed with malathion or not. Both alkyl phosphates and the
malathion acids were represented in the calculation, discounting the like-
lihood that the alkyl phosphates came from some other pesticide. Also, the
alkyl phosphates in the urine were almost entirely of the methyl type
(consistent with malathion), and neither foliage nor glove residues
included guthion - the only other organophosphate recently applied to the
fields.
lh828Adw 71
-------
TABLE 35
Comparison of Pre- and Post-Exposure Urinary Metabolites
(Pesticide - Equivalents per Void)
740
Adult Youth
Study
Field
1
II
III
IV
V
VI
IV
V
VI
- VK
- VK
- VK
- CC-1
- CC-1
- CC-1
- CC-1
- CC-1
- CC-1
Pesticide
Malathion
Malathion
Malathion
Malathion
Malathion
Malathion
Methiocarb
Methiocarb
Methiocarb
Pre-work
Void. UQ
9
321
78
119
Means 132
57
66
17
29
Means 42
21
21
15
21
Means 20
Post-work
Void. U9
399
196
140
245
22
53
40
~38
46
42
34
~4?
Pre-work
Void. UP
21
55
58
70
51
140
84
64
60
87
23
21
8
33
21
Post-work
Void, Uq
23
46
67
~45
55
107
74
~79
21
29 '
37
~29
Ih8284dw
72
-------
741
Occasionally, the urine of a person not occupaCionally exposed to
organophosphates does contain what appears to be a small amount (<10 ng per
ml) of dimethyl phosphate. But urines from the harvesters shoved other
expected alkyl phosphates as well, which are rarely present in urines from
non-exposed subjects. Also, the malathion acids appear to be highly
specific indices of exposure to malathion. It would seem likely that the
observed baseline excretion of metabolite was small but "real".
Two alternative sources of malathion exposure come to mind:
harvesting activity in other fields, and consumption of pesticide-contam-
inated berries. It is possible that both factors were responsible for the
appearance of the low levels of metabolite in urine samples from GC field
harvesters. Exposure and/or consumption would not have had to be very
substantial to generate the small metabolite excretions exhibited in this
study.
Excretions of methiocarb phenol were no more easily interpreted than
excretions of malathion products. Only a few urines from the VK crew were
positive for this metabolite - a finding generally consistent with the fact
that no methiocarb had been sprayed there. In the GC field, urines from
eleven of eighteen participants were positive for the metabolite before
they went to work in the GC field. Average excretions were somewhat lower
in magnitude than excretions of malathion products. This is at least
consistent with the generally lower foliage residues of methiocarb on the
fields harvested, and lower accumulations on patches and gloves.
Some generalizations may be drawn from the urine metabolite monitoring
experience in this study.
First, it is significant that pesticides widely applied to the
regional crop were, in fact, absorbed by harvesters, even though there were
Ih8284dw 73
-------
742
indications from this study that exposure was not limited to the scheduled
field harvest. Any contemplated regulatory control of pesticide exposure
on the part of harvesters will have to take into account widespread
distribution of the pesticide, and multiple routes of absorption.
As expected, urinary metabolite excretion reflected only a small
fraction of total body exposure.
Post-exposure specimens did not consistently contain more metabolite
than pre-exposure samples, as is to be expected when the chemicals absorbed
are rapidly metabolized and excreted. There is obviously very little
advantage in monitoring worker exposure by metabolite excretion if no
differences related to exposure can be demonstrated. Failure to collect
all excreted urine did reduce the likelihood that significant correlations
would be discovered. Even so, if differences in metabolite excretion pre-
and post- exposure are not sufficient to appear regularly in grab samples,
it is not likely that urine monitoring under these circumstances will be a
practical method of assessing chemical uptake.
Quality Control
Quality control procedures were of three kinds: 1) various matrices
(pads, foliage, resin, etc.) were spiked with known quantities of the
pesticides of interest in the field, as the monitoring study progressed,
then stored and analyzed along with the field samples, 2) matrices were
spiked in the laboratory, then analyzed together to determine
reproducibility (accuracy and precision) of the method.
Field spike and blank results are displayed in Tables E-l and E-2.
•
Recoveries of some pesticides from particular matrices were distressingly
low. It should be recalled that the addition of pesticide to the matrix
was done by means of an organic solution. This was not the physical form
Ih8284dw 7*
-------
743
in which the pesticide residue in the field existed when it cane in contact
with patches, gloves, etc., as dry material on foliage and berries. There
is no practical way to determine how this discrepancy affects comparability
of degradation in spiked and test specimens. Possibly it is an important
factor.
Soil samples were collected and spiked, but the level of fortification
was too low for analysis by presently available methods.
Field spikes of urine with metabolites of the pesticides of interest
were not prepared. When this oversight was discovered in September 1983,
samples of urine from eight local personnel were collected, spiked at 300
ppm of alkyl phosphates, MCA, DCA, and methiocarb phenol. To simulate
conditions applicable to the blueberry harvester specimens, the specimens
were frozen for two weeks, then thawed for measurement of volumes. Each
specimen was then divided into three portions, and all samples were
refrozen. The first set was analyzed for all metabolites in June 1984 (9
months). Another set will be analyzed in September 1984 (12 months) and
March 1985 (18 months). These intervals between storage and analysis span
the period that was required for completion of the analytical phase of the
blueberry harvester study. Results of this study should provide a basis
for judging the stability of excreted metabolites during prolonged cold
storage.
None of the basic data recorded in Appendix C or in the summary tables
have been corrected to reflect the losses indicated by the field spikes.
In estimating exposure dosage, however, (see Interpretations) field spike
losses have been used as correction factors.
To insure adequate performance of analytical procedures, spiked
matrices are routinely analyzed along with field samples in the laboratory.
Ih8284dw 75
-------
744
The data from these laboratory spikes and blanks are summarized in Tables
E-3 to E-ll, and E-13 to E-17. Tables E-3, E-5, E-7, E-9 and E-13 are
summaries. Findings in blanks are summarized in E-ll.
Tables E-12 and E-18 represent special quality control studies under-
taken to determine the precision of methods for four unmetabolized
pesticides, and for urinary alkyl phosphates.
For the most part, laboratory recoveries were substantially better
than recoveries from field spikes, implying that significant degradation of
pesticide occurred during storage. This is not unexpected.
An interfering substance led to misidentification .of captafol in some
blank matrices, and to sorae over-recoveries of captafol. Interferences
rarely complicated measurement of the other pesticides and pesticide
metabolites.
Ih8284dw
-------
745
CONCLUSIONS
The conclusions which follow have validity only in the specific
context of this study. For example, the disappearance of pesticide from
foliage following application was no doubt accelerated by heavy rain, which
might or might not occur in other harvest situations. Uptake of pesticide
by children younger than those studied here might be substantially
different from that reported. The study can be regarded as one recorded
experience wherein pesticide exposure of children and adults during harvest
work was observed and compared. Conclusions drawn from the experience
contribute to an information base that may be helpful in assessing hazard
of worker contact with pesticide residues. But the specific findings of
this study cannot be freely generalized to the many diverse situations that
involve contact of workers with pesticide residues.
1. Harvesters of blueberries - children and adults alike - were exposed
to residues of previously applied pesticides on berries and foliage in
the course of berry picking.
2. Overall levels of pesticide exposure of children were not remarkably
different from exposures of adults. There was no indication from this
study that exposure of children regularly exceeded that of adults.
Child exposure could be somewhat less, on the average, due to smaller
body surface area and possibly less vigorous harvesting activity.
3. Malathion, applied ULV aerially at 0.6 Ib a.i. per acre, four-and-one-
half hours before harvest work, generated the highest foliage
residues, glove and patch accumulations, airborne pesticide concentra-
tions, end urine metabolite excretions observed in this study. Total
Ih8284dw 77
-------
746
harvester exposure under these circumstances probably amounted to
several milligrams per hour. Halathion was applied to another field
by ground air blast sprayer, at a dosage of 1.0 Ib a.i. per acre, 26
days before harvest. No residues of malathion were found on foliage
or in gloves or patches worn by harvesters in this field.
4. The predominant sites of pesticide contamination in all studies were
the hands and forearms. Airborne pesticide exposure was barely
measurable in most studies, and body patches on chest, shoulders and
back generally accounted for only a few percent of total exposure.
5. Body surface exposure pattern may have been somewhat different in
children in relation to adults. In children, there tended to be
relatively more contamination of forearm and chest patches than in
adults. This is understandable in terms of the shorter arms of young
people.
6. Small but significant residues of methiocarb were found on foliage and
in harvesters' gloves 6 days after ground application of methiocarb at
1.5 Ib a.i. per acre. Lower levels were detected inconsistently 14
days after application.
7. Residues of guthion were found on only one of fifteen foliage samples
44-47 days after aerial application of guthion at 0.5 Ib a.i. per
acre. Eight of sixty glove pairs showed minute amounts of guthion at
this tine.
78
Ih8284dw
-------
747
6. Captafol (Difolatan) residues exhibited remarkable persistence.
Despite repeated rainstorms, foliage (and presumably berry) residues
were consistently measurable as long as 67 days after application of 2
Ib a.i. per acre by ground sprayer. (Residues from this application
may have supplemented those from a similar application one month
previously.) Glove accumulations of captafol often amounted to
several milligrams per two hours. Sufficient residue was present to
generate small but detectable amounts of captafol in the respired air.
9. Metabolites of malathion and methiocarb were detected in urine
specimens from the harvesters. Amounts excreted were somewhat smaller
than might have been expected from some of the exposure levels
encountered. Presence of metabolites in pre-exposure samples, and in
urines from harvesters not currently exposed to residues of the
pesticide in question, indicated strongly that the harvesters had
access to the pesticides from sources other than the fields under
observation. Harvesters may have been working off-hours in other
fields in the region. It is also possible that the metabolites could
have come from occasional ingestion of contaminated berries from other
fields. Correlations with foliage and glove residues were poor. No
method was available for a metabolite of captafol in the urine.
10. Analytical quality control was reasonably good in some areas,
inadequate in others. Recoveries of pesticides applied to foliage as
field spikes were very poor. Recoveries of captafol were low from all
matrices except the air sampler resin. Measurement precision was
inadequate in many cases. To some extent, the effects of these
Ih8284dw 79
-------
748
shortcomings were mitigated by the large numbers of samples analyzed,
and by the study design (equal impact on samples from youth and
adults, for example). Even so, the value of the study would have been
enhanced substantially by a higher level of analytical performance.
This would have been possible only if the Iowa PHAP laboratory had
been given several months to prepare and test specific methods for the
pesticides in question on the matrices required by the study.
11. There are now several studies showing the predominance of hand contact
1 2
in pesticide exposure patterns of harvesters. ' To the extent that
hand harvesting operations continue to be practiced, therefore,
methods for protecting workers should focus on protection of the
hands, and perhaps forearms. Impervious or adsorbent gloves, or
perhaps protectant (silicone) creams, would serve to reduce contact
and absorption. Development of practical protective measures for
routine use in agricultural work situations is admittedly difficult,
but research aimed at hand protection is now a much more appropriate
undertaking than yet one more study to show that hand exposures are
indeed paramount in manual harvesting operations.
References
1. Davis, J.E., Stevens, E.R., Staiff, D.C.: Potential Exposure of Apple
Thinners to Azinphosmethyl and Comparison of Two Methods for Assess-
ment of Hand Exposure. Bull. Environ. Contain. Toxicol. 31:631-638,
(1983).
Ih8284dw 80
-------
749
2. Putnam, A.R., Willis, M.D., Binning, L.K., Boldt, P.F.: Exposure of
Pesticide Applicators to Nitrofen; Influence of Formulation, Handling
Systems, and Protective Garments. J. Ag. and Food Chem. 31:645-650,
(1983).
3. Nigg, H.N., Stamper, J.H. and Queen, R.M.: .The Development and Use of
a Universal Model to Predict Tree Crop Harvester Pesticide Exposure.
Am. Ind. Hyg. Assoc. J. 45:182-186, (1984).
4. Popendorf, W. and Leffingwell, W.: Regulatory OP.Exposure. Residue
Reviews 82:125-201, (1982).
Ih8284dw 81
-------
750
APPENDIX A
IOWA PHAP
Blueberry Harvester Study
Field Data
TABLE OF CONTENTS
Field Date
VK July 20, 1982
VK July 21. 1982
VK July 22. 1982
GC-1 July 19, 1982
GC-1 July 20, 1982
GC-1 July 21, 1982
GC-2 July 27, 1982
GC-2 July 28. 1982
GC-1 July 29, 1982
Ih71084dw 82
-------
751
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Investigator
/e,
Workers in Field /Z.'fP •">>'
Field location So^lk
to
»-l* rasen
Assigned I.D.
Date 7-Z.e -8Z
Pesticide History
24 oz/j •M-3o'j.
) a+A fL-C.\
U'l \J
^^
'All p&
c^tlic.ez-r io» by
Acres
Row spacing
Number of rows E p £o** height 4-
Number of- workers 1n field 2.4 Number of participatns in field 2, O
Temperature 7Z F ^Humidity SZ Sun condition Pa<—ly
High Volume Air Start 12: /DM Stop I2:sc PM cFm y? £?#>•*
Sketch of Field:
.^©1
o o
^ i
$
4
ft
.
Open
r.eld
EPA Registration Numbers
Sampling Symbols
High Vol Air X
Soil & foliage 0
50,/
(
A-l
-------
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Assigned I.D._
Investigator
Workers in Field I'.lo ?M
Field location
752
Date 7-Zf-ftz.
to
&£
Co*.?-* H*- AT •* , /i/ -r .•
Pesticide History £/,
Acres
Row spacing
. £'J-«>f*
Number of rows J6
height 4 -(a ft
Number of- workers in field 2.4 Number of participatns in field 20
Temperature &4 ° F ^.Humidity vT6> Sun condition #tr-f// (.I
High Volume Air Start /.'45
Sketch of Field:
Stop
Ope*
r, e. &
M
A
__r.. _ _ 3.
Jo
EPA Registration Numbers
cf m /<) c fan = O.S32 >
Sampling Symbols
<*i ; 4. High Vol Air X
£3£- Soil & foliage 0
£ree-2.£.
Sod Te»,p
A-2
-------
753
Investigator
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Workers in Field )2:OO
Field location to-j-'
c«.s- 3r
Assigned I.D. V K 3
Date 7-ZZ- 82.
to
3 ' /5
-k' .-ay**,
M,c.
Pesticide History *yj,&/»>e*
, &vttuon l>^ Stop r.it PM
Sketch of Field:
Wood's
Sampling Symbols
High Vol Air X
Cr«t& So11 & f0i1age
0 p
/A At
EPA Registration Numbers
A-3
85
-------
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Assigned I.D.
754
Investigator
Date 7-/9-S2
Workers in Field r?:oc X '/
to £'.
Field location Co^-U 'J^ci- of- Csj-i-k
•>«
Pesticide History
Z4o*fA ff-?> .'Litol
tf
T /
gy /e
ear >
Acres
Row spacing
Number of rows
height 3-sp;
Number of- workers in field Jo Number of participatns in field
Temperature TP " ^ % Humidity ?£? Sun condition Ci
High Volume Air Start &:'£/.?* Stop y/gc.-.v cFm / ^ r^;r ^*Sl? m
Sketch of Field:
: \e> • o
: i
EPA Registration Numbers
Sampling Symbols
High Vol Air X
Soil & foliage 0
No UL'i»4
So<\ few. li,'t
A-4
86
-------
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Assigned I.D. & C
Investigator
Date
Workers in Field
Field location
to 4:0? 9M
n.>c.
:~ cf~ ^'^."-> ••k'yv,
755
Pesticide History fam^s* Z4oeJb(5-4^. L,
-------
756
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Investigator /yj/e.
Assigned I.D. GC 3
Date 7-2 (-^2.
Workers 1n Field 8: 45"
to
Field location S
^- &f Soa-u l-»
Jfi
Pesticide History
fc-- ^V
fr-9}. JU*
Je
Cur
Acres
Row spacing J 0 Ft- Number of rows ^5*0
height
Number of-workers in field 3o Number of participatns 1n field
r/^ ^Humidity.
Temperature
Sun
High Volume Air Start 1:ooflh Stop f.'lfAM cFm y tf-Mi aQ.z'l
Sketch of Field:
Sampling Symbols
High Vol Air X
Soil & foliage 0
EPA Registration Numbers
-------
757
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Assigned I.D._
Investigator
Date 7- 27 SZ
Workers 1n Field
Field location ,
to
. licit:* -*.-/
Pesticide History
2.4oi/Af.S-3-8$). 7^,to[,+*.,
, /i»/>J
-} I id A
-
. A r>r>Le.o-
Acres /^ Row spacing l£> £/• Number of rows 9Z. iassT height
Number of-workers in field 38> Number of participatns in field 22.
Temperature 12'^ ^Humidity ^/ Sun condition
High Volume Air Start £-'/? £h Stop ft:55/iAf cFm/f^^z^
V
Sketch of Field:
Sampling Symbols
High Vol Air X
Soil & foliage 0
EPA Registration Numbers
A-7
-------
758
Investigator
Workers in Field
Field location
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
U/g>grt
tjy~«
* £**.* e(-
Assigned I.D._
Date 7-28
to 4 : g c
'<>•
Pesticide History fI»tg.-»aA &• o*fA (s-S-&h . 2t>iVJof»-fe>H ^ rs//
y c
Acres
Rw spacing
Number of rows f 2L
height ^-gfr
Number of -workers 1n field 72. Number of participatns 1n field 2 2. _
Temperature 76.-' F % Humidity 70 Sun condition Cloudy _
__^___^^_ _ ^__ ___^ — /
High Volume Air Start II'.ID PM Stop 12'.6SW cFm /
Woog/
Sketch of Field:
Sampling Symbols
High Vol Air *
Soil & foliage 0
-KJ
EPA Registration Numbers
A-8
90
-------
759
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Investigator lysis,
Workers in Field 7:30
Field location 5»^-A
(*•
Assigned I.p. GC
Da te 7-2 ?-gZ
to
Pesticide History
Z4 o*./A
'*/ A 6<-/'-
«P g(/-r^;t i-h/fi
Acres /5"
Row spacing )o f-f- Number of rows So
height 3-f<=f.
Number of-workers in field_
Tempera ture_
^Humidity
Number of participatns in field 2Z.
* Sun condition (.
High Volume Air Start T.4SJM Stop 8'W AH cFm
Sketch of Field:
EPA Registration Numbers
o \ \
A/etu
Sampling Symbols
High Vol Air X
Soil & foliage 0
Ho UW
A-9
91
-------
760
APPENDIX B
METHODS
TABLE OF CONTENTS
Page
Malathion, guthion, methiocarb and captafol on foliage B-l
Malathion, guthion, methiocarb and captafol in soil B-2
Malathion. guthion, methiocarb and captafol in gloves and
XAD-4 resin B-4
Malathion, guthion, methiocarb and captafol in patches and
glass fiber filters B-6
Malathion carboxylic acids in urine B-8
Methiocarb phenol in urine B-10
Alkylphosphates in urine B-12
Standard of laboratory practice B-14
Calculations and statistics B-16
Factors used in estimating regional and total pesticide
exposures
Malathion B-20
Methiocarb B-21
Captafol B-22
Summary B-23
92
Ih8284dv
-------
761
METHOD FOR EXTRACTION OF FOLIAGE FOR RESIDUES OF
MALATHION, GUTKION, METHIOCARB AND CAPTAFOL
1. Add 100 ml of distilled water and one drop of a 1:50 dilution of
Suf-Ten vetting agent to a 500 ml 24/40 Erlenmeyer containing
25 leaf punches.
2. Cap the flask and shake on a wrist action shaker at 200 strokes
per min for 20 min.
3. Decant the liquid into a 500 ml separatory funnel retaining the
leaf punches in the flask and paying particular attention to
transferring the associated leaf dust to the separatory funnel.
4. Repeat the above procedure two more times, adding the liquid
from each to the first.
5. Add 50 ml of CH.C1. and shake for 1 min.
6. Drain the lower layer through a column containing about 3-4 inches
of Na.SO, into a 300 ml evaporating flask.
7. Repeat with 50 ml of CH-C1. and 1 min shaking.
8. Wash the column and Na«SO^ with about 10 ml of CH2C12.
9. Reduce the CH-C1- on the flash evaporator to 2-3 ml, transfer to a
centrifuge tuoe and evaporate to dryness on N-Evap.
10. Take up to 2 ml in hexane for GC analysis.
Reference:
Iwata, Y., R.C. Spear, J.B. Knaak, and R.J. Foster: Worker Reentry
into Pesticide Treated Crops. I. Procedure for the Determination of
Dislodgeable Pesticide Residues on Foliage. Bull. Environ. Contain.
Toxicol. 18, 649 (1977).
Ih6784dw
B-l
93
-------
762
SOIL PROCEDURE FOR MALATHIOK, CAPTAFOL, GUTHION
1. Weigh 30g. of soil into a 125 ml glass-stoppered erlenneyer flask.
2. Add 75 ml of acetone.
3. Attach flask to Burrell shaker and shake for 20 minutes.
4. Filter contents through scintered glass filter attached to a 250 ml
sideanned flask.
5. Rinse 125 ml erlenmeyer with acetone and add to filter; rinse until
all of the contents have been transfered.
6. Transfer the solution in the side-armed flask to a 250 ml evaporating
flask.
7. Attach to flash evaporator and reduce solution to 5 ml.
8. Transfer to 13-15 ml centrifuge tube. If additional clean-up is
necessary, clean the extract up on a aluminum oxide-Norit A column.
Soil Procedure for Methiocarb
1. Reduce solution from step 7 of Soil Procedure above to 0.5 ml in a
25 ml concentrator tube. Be sure it is in acetone. (If sample
cannot be satisfactorily reduced to 0.5 ml, clean sample on an
aluminum oxide-Norit A column.)
2. Add 0.1 ml of carbamate derivatizing reagent and 200 mg of K.CO.
crystals.
3. Stopper tightly, mix gently, and place tubes in heating block at
100eC for 1.5 hours.
4. Remove from heating block and allow to cool to room temperature.
5. Gently evaporate to 0.2 ml of solution with nitrogen.
6. Add water (distilled H.O 2X extracted with benzene) to 5 ml mark,
mix on vortex until solution clears, then extract 2X with 5 ml of
hexane, mixing for two minutes each time.
7. Concentrate hexane extracts to 1 ml.
8. Prepare silica gel non-stop column using 2 g of silica gel that has
been in 170eC oven for 48 hours, deactivated with 400 microliters of
water and rotated on the Roto-rack for 2 hours. Add 1.5 g of
Na.SO, to the column.
2 4
Ih6784dw B"2
-------
763
SOIL PROCEDURE FOR METHIOCARB (Continued)
9. Prevet the column with 10 ml of hexane.
10. Pipet the 1 ml of the hexane extractant from step 7 onto the column.
11. Elute with 10 ml of hexane, discard. Then with 10 ml of 12 benzene
in hexane, discard.
12. Elute with 10 ml of 202 benzene in hexane (fraction 3), save.
13. Concentrate to 1 ml for methiocarb.
Column Clean-up for Soil Extract Using Aluminum Oxide-Norit A
1. Mount a 19ramx30cm column with scintered glass filter on a suction
flask.
2. Add 12 g aluminum oxide, acid washed.
3. Add 3 g activated charcoal (Norit A) mixed with 2 g celite.
4. Add 12 g aluminum oxide, acid washed.
5. Apply suction and add sample in 100 ml of ethyl acetate to the column,
discard eluent.
V
6. When the meniscus reaches the top layer of the packing, elute the
column with 175 ml of 25Z benzene in ethyl acetate and collect the
eluent in a 300 ml evaporating flask.
7. Evaporate just to dryness.
8. Take up to 5 ml with acetone.
Preparation of Norit A for Aluminum Oxide-Norit A Clean-up Procedure
1. Slurry 100 g of Norit A with 175 ml of concentrated HC1 in a 1000 ml
beaker and boil gently for 1 hour.
2. Add 500 ml of a 502 aqueous ethanol solution and boil for an
additional 3 hours.
3. Filter through a Buchner funnel and wash with distilled water until
no longer acid.
4. Dry at 250eC for at least 3 hours. (Longer heating has no effect.)
5. Store in a tightly capped bottle.
Ih6784dw 3
-------
764
SOXHLET EXTRACTION OF GLOVES AND XAD-4 RESIN
FOR MALATHION, GUTHI.ON, METHIOCARB AND CAPTAFOL
1. Add ca 500 ml of hexane to a 1 liter evaporating flask, I 29/42, if
24/40 flask is used, an adapter has to be used.
2. Add a half dozen boiling stones.
3. Place sample to be extracted in a 55mm x 150mm glass thimble.
4. Assemble soxhlet extractor, turn water on to the condenser and then
turn the variac (Powerstat) to the on position.
5. Allow to cycle for 6 hours, checking frequently to be sure it is
cycling.
6. At the end of the six hours, turn the variac off and allow the
assembly to cool for 10-15 min.
7. Turn the water to the condenser off.
8. Disassemble the soxhlet, removing the thimble with a wire handle, if
solvent in thimble, allow to drain before removing thimble. Pour
what solvent remains in soxhlet into the liter flask.
9. If no water is visible in the extract, pass the contents of the flask
through a 3 in. sodium sulfate* column and collect solvent in a I
24/40 liter flask. If water is visible in the extract, empty the
flask into a 500 ml separately funnel, then drain the hexane through
the sodium sulfate column.
10. Concentrate to ca 5 ml and transfer to a 15 ml centrifuge tube.
Rinse the flask twice with ca 3 ml of hexane and add to the tube. Add
1 ml of hexane to the tube and mix.
11. Concentrate to ca 1 ml while rinsing down the sides of the tube with
hexane three times. Adjust volume in the tube to ca 10 ml, centrifuge
if necessary to remove any precipitate, and transfer extract to clean
centrifuge tube and adjust volume to 10 ml.
12. Analyze by GLC.
*Use sodium sulfate washed with methylene chloride.
Reference:
Iowa PHAP, unpublished
B-4
Ih6764dw
-------
765
GAS CHROMATOGRAPHIC CONDITIONS FOR INTACT MALATHION, CAPTAFOL AND CUTHION
Instrument - Micro-Tek MT 220 Instrument #5
Column - V O.D. x 4 mm I.D. x 2' glass packed with 5Z OV-210
on 80/100 Gas Chrom. Q Pretested E.P.A. packing SP-1786
Column temp. - 200°C.
Carrier flow - 50 ml/min. N-
Inlet temp. - 225'C.
Transfer temp. - 235°C.
Detector - Electron Capture H.
Detector temp. - 210°C.
Electrometer - E-2
GAS CHROMATOGRAPHIC CONDITIONS FOR INTACT METHIOCARB
Instrument - Micro-Tek MT 220 Instrument #1
Column V O.D. x 4 mm I.D. x 2' glass packed with 5Z OV-210
on 80/100 Gas Chrom. Q Pretested E.P.A. packing SP-1786
Column temp. 210°C.
Carrier flow 60 ml/min. N«
Inlet temp - 220"C.
Transfer temp. - 235°C.
Detector - Electron Capture Ni,« (Tracer)
Detector temp 250°C.
Detector purge flow - N- @ 15 ml/min.
Electrometer E-2
Tracer model 770 autosampler
H.P. 3390 A integrator
Ih6784dw
-------
766
EXTRACTION PROCEDURE FOR RESIDUES Or
MALATHION, GUTHION, METHIOCARB AND CAPTAFOL
IN PATCHES AND GLASS FIBER FILTERS
1. From a 4" x 4" cellulose pad (sometimes a gauze patch is attached)
cut a 2" x 2" section.
2. Loosely roll the portion of pad to be analyzed and stuff it into a
chromatography column that has a stopcock (Kontes 420530, size 241).
3. Pour 50 ml of hexane into the column with the stopcock closed. Use
75 ml of hexane if two 2x2 sections are being extracted.
4. Allow the pad to soak in the hexane for 5-10 minutes.
5. Elute the acetone from the column at a rate of 5 ml per minute into
a 250 or 300 ml evaporating flask.
6. Rinse the walls of the column with an additional 15-20 ml of hexane.
7. Reduce volume of extract to about 5 ml on a rotary evaporator.
8. Transfer extract to a 12-15 ml centrifuge tube. Rinse flask 2X with
small amounts of hexane and add to tube.
9. Concentrate to 1 ml on N-Evap and analyze on GC.
Reference:
Iowa PHAP, unpublished
Ih62984dw B-6
98
-------
767
PATCH METHODOLOGY FOR METHIOCARB
1. Commence with step 9 from PATCH EXTRACTION PROCEDURE, concentrate
extract to 0.1 ml if other than acetone. If acetone 0.5 ml is
sufficient.
2. Add 0.5 ml of FDNBacetone reagent and 5.0 ml of sodium borate
buffer solution to the tube.
3. Cap tightly and heat at 70°C. for one hour.
4. Cool tubes and add 5.0 ml of hexane.
5. Mix for two minutes on Vortex mixer.
6. Allow layers to separate and carfully transfer hexane layer to
a centrifuge tube and stopper tightly. Be sure not to transfer
any of aqueous solution.
7. Do not concentrate any of the hexane extract.
Reference:
Carbamate derivatization method from Manual of Analytical Methods
for the Analysis of Pesticides in Humans and Environmental Samples,
EPA 600/8-80-038 June 1980, Section 10, A, page 10 & 11.
Ih6784dw
-------
768
METHOD FOR MALATHION CARBOXYLIC ACIDS IN URINE
1. Plpet 2 ml of urine into a 15 ml centrifuge tube.
2. Add 2 grams of NaCl and pipette 4 ml of extracting solvent
(acetonitrile diethyl ether 1:1) into the tube.
3. Add 1 ml of 6 N HC1, stopper tubes and mix on Vortex for 1 min.
4. Centrifuge at setting 40 for 1 minute.
5. With a dispo pipet transfer 2.0 ml of the organic solvent layer to
a graduated (12-15 ml) glass stoppered centrifuge tube.
6. Using the glove box, add ca 2 ml of diazomethane and let stand
for 20 minutes.
7. Concentrate solution to 0.3 ml using the concentrator. Dilute to
5 ml with distilled H.O, add ca 5 grams NaCl and 3 ml of hexane,
stopper and mix vigorously on the vortex for 1 minute. Allow layers
to separate.
8. Prepare silica gel column using 2.4 grams of silica gel that has
been heated 130°C for 48 hrs., deactivated with 0.5 ml distilled
H.O and rotated on Rotorack for 2 hrs. Add 1.5 g of sodium sulfate.
9. Prevash column with 10 ml hexane.
10. Transfer hexane extract (step 7) to the silica gel column.
Re-extract aqueous layer with 2 ml of hexane and add to column.
Extract with another 2 ml hexane and add to column. All eluate to
this point is discarded.
11. Elute column with 10 ml of benzene followed by 10 ml of 10% ethyl
acetate in benzene collected as one fraction.
12. Concentrate to 0.5 ml under a gentle stream of nitrogen.
TUBES REQUIRED FOR PROCEDURE:*
12 12-15 ml glass stoppered centrifuge tubes for step 1.
12 12-15 ml glass stoppered centrifuge tubes for step 5.
12 25-50 ml centrifuge tubes for step 11.
12 12-15 ml glass stoppered centrifuge tubes for transferring
eluate from step 11 after concentrating to 3-4 ml.
13. The 0.5 ml extract is analyzed on GC equipped with flame photometric
detector, a glass U-shaped column, 6 ft X 1/4 in. packed with 3%
OV-1 on 80/100 mesh chromosorb W High Purity. The gas chromatographic
column was operated under the following parameters: nitrogen carrier
gas flow rate 60 ml/min; column temperature, 168°; inlet 220e,
detector, 170°, transfer line, 240°. Standards MCA, 500 pg/ul;
DCA, 500 pg/ul.
^Required when analyzing 10 samples, 1 blank, and 1 spike.
Ih6784dw B-8
100
-------
769
(Continued)
Gas Chromatographic Conditions for Malathion Metabolites in Urine
Instrument - Micro-Tek MT 222 Instrument 14
Column - 32 OV-1 on 80/100 Chromosorb W HP, Tracer packing
GC 8725
Column temp. 180°C.
Carrier flow N
-------
770
METHOD FOR CARBAMATE PHENOLS (INCLUDING METHIOCARB PHENOL) IN URINE
1. Pipet 1.0 ml urine into 12-15 ml glass stoppered centrifuge
tube, 2 ml benzene-extracted distilled H.O, 1 ml of cone.
HC1, cap securely and mix.
2. Place in pressure cooker and heat to 15 Ibs. pressure and
hold there for 16 minutes.
3. Cool cooker to allow pressure to drop to zero.
A. Remove tubes and place in ice water to cool.
5. Add 5 ml methylene chloride to each tube.
6. Mix contents vigorously on Vortex mixer for 1 min, centrifuge,
and transfer methylene chloride layer (lower) to a 12-15 ml
centrifuge tube.
7. Repeat steps 5 and 6. Adjust volume to 10 ml with methylene
chloride. Pipet ml into a 12-15 ml centrifuge tube.
8. Vash extract 3 times with 3 mis of 52 NaHCO., mixing on a
Vortex mixer for 30 sec., and discarding aqueous layer.
Centrifuge after last wash and carefully remove all of the
aqueous layer.
9. Add a small amount of sodium sulfate to tube to dry extract.
10. Decant extract into 25 ml concentrator tube.
11. Add 1 ml acetone and mix, cone, to 0.5 ml and during the
concentrating rinse the sides of the tube with a small
amount of acetone three times to remove the methylene chlor.
12. Remove tubes from concentrator and add 0.1 ml of alpha-
bromopentafluorotoluene solution (0.1 ml of reagent to 9.9 ml
of abs. alcohol) and add 200 mg of K-CO- crystals.
13. ' Stopper tightly, mix gently, and place tubes in heating block
at lOO'C for 1 1/2 hours.
14. Remove from heating block and allow to cool to room temp.
15. Gently evaporate with nitrogen to about 0.2 ml of soln.
16. Add water to 5 ml mark, mix on vortex, then extract 2X with
5 ml hexane, mixing for two minutes each time.
17. Adjust hexane extracts to 10 ml.
Ih6784dw B~10
-------
771
CARBAMATE PHENOL PROCEDURE (Continued)
18. Prepare silica gel col. using 2 grains that has been in 170°C
oven for 48 hours, deactivated with 400 microliters of water
and rotated on Roto-rack for 2 hrs. Add 1.5 grams of Na.SO,.
19. Prevash column with 10 ml hexane.
20. Pipet 1.0 ml of the hexane extract onto the column.
21. Elute with 10 ml hexane, discard; 10 ml 12 benzene in hexane,
Fract. 11; 10 ml 202 benzene in hexane, discard; 10 ml 60Z
benzene in hexane, Fract. IV; and 10 ml 80Z benzene in hexane,
Fract. V.
22. Fraction II which contains the alpha-naphthol is cone, to
0.5 ml, fraction IV containing isopropoxyphenol and carbo-
furan phenol, is concentrated to 5 ml and Fract V; containing
3-ketocarbofuran phenol, is concentrated to 2 ml.
23. The fractions are analyzed on BC equipped with trituim foil
electron-capture Detector, a glass U-shaped column, 6 ft. X
1/4 in. packed with 3* S E-30/4.5Z QF1 on 80.100 mesh Gas Chrom
Q. The column was operated under the following parameters:
nitrogen carrier gas flow rate, 65 ml/min; column temperature,
168°; inlet 225°; detector, 210°, transfer line, 235°.
Standards— 1-Naphthol 2* pg/ul; isopropoxyphenol, 4 pg/yl;
carbofuran phenol, 4 pg/wl; 3-Ketocarbofuran phenol, 25 pg/wl.
Gas Chromatographic Conditions for 3, 5-dimethyl - 4 (methylthio) phenol,
metabolite of Methiocarb in urine
Instrument - Varian Vista 401 (Vista 6000 GC)
Column Q" O.D. x 2 mm I.D. x 6' glass packed with 4Z SE-30/6Z
OV-210 on 80/100 Gas Chrom Q (Varian M2088)
Column temp. 195°C.
Carrier flow N, g 36 ml/min.
Inlet temp. 220'C.
Detector ECD Ni,. (Varian
Detector temp. 300*C.
Reference:
Sullivan and Shafik
Primate and Pesticide Effects Lab (unpublished)
EPA
Ih6784dw -
105
-------
THE BENZYL ALKYL PHOSPHATE METHOD OF ' ' ^
THE UNIVERSITY OF MIAMI SCHOOL OF MEDICINE
1. Using 15 x 150 mm culture tubes, add 1 ml of control urine, urine
containing standards, urine used as spikes and urine samples to
be analyzed.
2. Using a solution of acetone and dry ice, shell-freeze the tubes.
Store in freezer until ready to be f reeze-dried.
3. After freeze-drying, store in freezer or proceed to the next step.
4. To each tube add 1 ml or acetone, 3 carborundum chips and 0.1 ml of
a 10% solution of 3-benzyl-l-p-tolytriazine in acetone.
5. Cap the tubes tightly and place them in the heating block at 70°C
for two hours.
6. Cool, using a vet-ice/water bath, add 1 drop of 6 N HC1 and mix.
7. Add 10 ml of saturated sodium chloride solution.
8. Add 1 ml of benzene, mix on Vortex for 1 minute.
9. Centifuge, transfer the benzene layer to a tube containing a small
amount of sodium sulfate, up to about the 0.2 or 0.3 ml mark.
10. Decant solvent into another tube and analyze by FPD.
A Tracer Model 222 gas chroma tograph (or equivalent) equipped
with a flame photometric detector (FPD) is operated in the phosphorus
mode (i.e., employs a 526 nm filter). The instrument is operated
isothermally.
Glass U-type gas chromatographic columns, 6 ft x 0.25 in.,
packed with 52 OV-210 on Gas Chrom Q, 80/100 mesh, prepared
according to Thompson et al. (1) and treated with carbowax
20M according to Ives and Giuffrida (2).
The gc operating parameters include:
Instrument - Micro-Tek MT 222 Instrument *4
Column V O.D. x 4 mm I.D. x 6* glass, packed with
52 OV-210 on 80/100 Gas Chrom. Q, Pretested E.P.A.
packing SP-1786
Column temp. 173*C.
Carrier flow N. @ 60 ml/min.
Inlet temp. 230°C.
Transfer temp. 235*C.
Detector F.P.D. , phosphorus filter
H- 150 ml/min.
Q 20 ml/min.
Ih6784dw B_12
lot
-------
K, 20 ml/min. ' ' ^
Detector temp. 220°C.
Make up gas flow 60 ml/min. N,
Electrometer Tracor Solid State
References:
Thompson, J.F., A.C. Walker and R.F. Moseoan: Evaluation of Eight
Gas Chromatographic Columns for Chlorinate'd Pesticides. Journal of
the AOAC, Volume 52, No. 6, 1969, pp. 1263-1277.
Ives, N.G., and L. Gioffrida: Gas Liquid Chromatographic Column
Preparation for Adsorptive Compounds. Journal of the AOAC, Volume
53, No. 5, 1970, pp. 973-977.
B-13
lh678Adw 105
-------
774
STANDARDS OF LABORATORY PRACTICE
Sources of analytical standards
The chemical calibration standards employed were obtained from the
Environmental Protection Agency. Standards Repository. If the requested
standard is not available from EPA, pure substances are obtained from
manufacturer's laboratories. The latter pertains particularly to
metabolites or degradation products. Among these manufacturers were the
American Cyanimid Co. and Mobay Chemical Co.
Sources of analytical procedures
A number of sources are employed as references for pesticide
analytical procedures including the following:
Manual of Chemical Methods for Pesticides and Services. Environmental
Protection Agency, OPF, TSD, Chemical and Biological Investigations
Branch, Published by A.O.A.C., July, 1976. 13th Edition, A.O.A.C.,
1980.
NIOSH Manual of Analytical Methods. Second Edition, USDHEW, David
G. Taylor, Coordinator, Cincinnati, Ohio, April, 1977.
Manual of Analytical Methods for the Analysis of Pesticides in
Human and Environmental Samples. Environmental Protection Agency,
Health Effects Research Laboratory. Research Triangle Park, N.C., J.F.
Thompson, Ed., June, 1980.
Manual of Analytical Quality Control for Pesticides and Related
Compounds 'in Human and Environmental Samples. Environmental Protection
Agency. EPA 600/2-81-059, April, 1981.
Standards of laboratory practice
Laboratory practices which include calibration and maintenance of
field and laboratory equipment and instrumentation are performed according
Ih62984dv
-------
775
to the procedures described by Dr. Joseph Sherma, Manual of Analytical
Quality Control for pesticides and related Compounds in Human and
Environmental Samples, 60012-81-059, April, 1981 Environmental Protection
Agency. These procedures include but are not limited to:
Section Page
Analytical Balances 3 74
Cleaning of Glassware 3 84
Housekeeping 3 84
Gas Chromatograph Calibration and
Maintenance 3 101
Gas Chromatography 4 107
Gas Chromatography 5 140
Gas Chromatography 6 220
Storage of Samples 8 289
Corroborative Measures 10 381
Other laboratory practices are described in the approved Iowa PHAP
Standard Operating Procedure manual, operative from January 1984.
Ih62984dw B.
1*7.
-------
77C
Calculations and Statistics
High volume air samples
3
The air sampler operated at a flow of 0.538 m per minute for 65
minutes. Therefore, pesticide residue trapped on the filter disc, plus
that captured by the resin, (in ug) was divided by 24.21 to yield air
concentration of pesticide in ug per m .
Personal air samples
Pumps vere individually calibrated. They operated for two hours
continuously. Flow rate in liters per minute was multiplied by 120
minutes to yield the air volume sampled. Therefore, weight of pesticide
3
trapped on the resin (ug) was divided by the sample air volume in m
(one m - 1000 liters) to yield air concentration of pesticide in ug
per m .
Foliage
Twenty-five leaf discs, each 3/4 inch (1.91 cm) diameter, were
extracted as a sample. Area of each disc, counting both sides, was 5.70
2
cm . Weight of extracted pesticide (ug) was therefore multiplied by
2
17.54 to yield ug of pesticide per 100 cm of leaf area.
Soil
Weight of extracted pesticide (ug) from 30 gm sample was divided by
30 to yield ug per gm soil.
Patches
Pesticide (ug) was measured in a four-inch square quadrant of a 16-
square-inch patch. Weight per four square inches was therefore multiplied
by four to yield weight per total 16 square-inch patch. Results are
2
reported as ug per patch pairs (206 cm ) for forearms, shoulders and
chest, and as ug per patch (103 cm ) for back and "inside jacket"
measurements.
Ih62984dw B-16
-------
777
Factors to convert pesticide per patch to pesticide per standard
surface area (wg per 100 cm") are therefore:
Forearms, shoulders, chest 0.485
Back and "inside jacket" sites 0.971
Further conversions to pesticide per average areas of body surface (yg
per total surface area) utilize the following values :
Area, % of Total
cm Body Area
Forearms 1286 6.7%
Shoulders 1306 6.8%
Chest 1536 8.0%
Back 1536 8.0%
Gloves
No area conversion has been used in the case of gloves. Reported
units, based on pesticide extracted from each pair, are, therefore, ug per
pair. Gloves were worn for just one hour of the two hour exposure period.
Therefore, the one hour value is multiplied by two to yield the estimated
two-hour hand exposure.
Urinary Pesticide Metabolites
Three of the pesticides to which the harvesters were exposed are
metabolized to measurable urinary metabolites: malathion, guthion and
methiocarb.
There were no measurable residues of guthion in the GC or VK fields,
which had been treated with it about six weeks before harvest.
Neither patches nor gloves contained measurable amounts. We have
assumed, therefore, that urinary alkyl phosphates found in the urine of
harvesters came exclusively from the metabolism of malathion, and not
from guthion.
tWm. J. Popendorf and J.T. Leffingwell. Regulating OF pesticide residues
for the protection of farm workers. Residue Reviews 82:125-20, 1982.
Ih62984dv B-17
109
-------
778
The maamalian metabolism of malathion is complex, preceding by two
alternative pathways: 1) de-ethylation of one or both of the succinic acid
carboxyl groups, or 2) hydrolysis of the molecule at the ester linkage of
methyl phosphoric acid and the entire succinic acid leaving- group.
Usually the first degradative pathway predominates. Principal end products
are:
De-ethylation Hydrolysis
Mono-carboxylic (MCA) and Dimethyl phosphate (DMP)
di-carboxylic (DCA) acids Dimethyl phosphothioate (DMPTh)
of malathion Dimethyl dithiophosphate (DKDTP)
Each molecule of each of these five metabolites must represent
degradation of one molecule of malathion. (There are additional minor
metabolites not readily measured by presently available methods).
However, it is legitimate (and certainly convenient) to calculate a
"malathion equivalent," reflecting the sum total of malathion that would
have to be metabolized to generate the full load of urinary end-products.
Based on molecular weight ratios, a "malathion equivalent" has been
calculated from the five metabolites in urine.
Malathion Equivalent -1.09 (MCA) +1.20 (DCA)
+2.62 (DMP) +2.32 (DMPTh)
+2.09 (DMDTP)
Similarly, the methiocarb phenol content of urine has been converted
to a "methiocarb equivalent" using the molecular weight ratio.
Methiocarb M.W. 225 m . .,
Methiocarb Phenol M.W. " 168 "
In assessing post-exposure excretion of pesticide metabolites, the
pesticide equivalent in the immediate post-exposure urine has arbitrarily
been added to that in the specimen collected the following morning. Not
enough is known of the pharmacokinetics of these pesticides and their
Ih62984dw B-18
MO.
-------
77
metabolites to confirm or challenge the wisdom of this addition, but it
would seem to be a reasonable "best estimate" of excretion, utilizing
available data.
Statistical Procedures
When finite measurements are available in reasonable proportion and
appear fairly veil distributed, means and standard deviations have been
calculated, and the means have been compared statistically, using Student's
t test.
Ih62984dw B-19
ll/
-------
Multipliers for Converting Exposure Measurements to
Corrected Regional Two-Hour Dosage Estimates
780
Studies: I, II, III - Malathion
Inhalation Exposure
Air Cone (pg/m3)
Pers Air Sampler
Resp.t
Volume
Factor
3.00
Analyt.
Recovery
Factor
1.64
Overall
Factor
4.92
Body Surface Exposure
Gloves (pg per pair) x
Time
Factor
2.00
Analyt.
Recovery
Factor
2.27
4.54
Patches
Forearms (ug/patch pr) x 6.24
Shoulders (pg/patch pr) x 6.34
Chest (ug/patch pr)
Back (pg/patch)
Area
Factor
6.24
6.34
7.46
14.90
Analyt.
Recovery
Factor
x 1.45
x 1.45
x 1.45
x 1.45
Overall
Factor
9.05
9.19
10.82
21.61
t Assumes pulmonary ventilation of 25 liters per minute for 2 hours, and
complete absorption of inhaled pesticide.
Ih8284dw
112
-------
Multipliers for Converting Exposure Measurements to
Corrected Regional Two-Hour Dosage Estimates
781
Studies: IV. V, VI - Methiocarb
Inhalation Exposure
Air Cone (ug/ms)
Pers Air Sampler
Resp.t
Volume
Factor
Analyt.
Recovery
Factor
Overall
Factor
3.00
2.78
8.34
Body Surface Exposure
Gloves (yg per pair) x
Time
Factor
2.00
Analyt.
Recovery
Factor
3.45
6.90
Patches
Forearms (yg/patch pr) x 6.24
Shoulders (yg/patch pr) x 6.34
Chest (yg/patch pr)
Back (yg/patch)
Area
Factor
6.24
6.34
7.46
14.90
x
x
X
X
Analyt.
Recovery
Factor
1.78
1.78
1.78
1.78
Overall
Factor
11.04
12.29
13.28
26.52
i Assumes average pulmonary ventilation of 25 liters per minute for 2
hours, and complete absorption of inhaled pesticide.
Ih8284dv
113
-------
Multipliers for Converting Exposure Measurements to
Corrected Regional Two-Hour Dosage Estimates
Studies: IV. V, VI, VII, VIII, IX - Captafol
782
Inhalation Exposure
Air Cone (ug/m9)
Pers Air Sampler
Resp.t
Volume
Factor
3.00
Analyt.
Recovery
Factor
1.72
Overall
Factor
5.17
Body Surface Exposure
Gloves (yg per pair) x
2.00
Analyt.
Recovery
Factor
4.55
9.09
Patches
Forearms (ug/patch pr) x 6.24
Shoulders (pg/patch pr) x 6.34
Chest (yg/patch pr)
Back (vg/patch)
Area
Factor
6.24
6.34
7.46
14.90
Analy t.
Recovery
Factor
x 3.00
x 3.00
x 3.00
x 3.00
Overall
Factor
18.72
19.02
22.38
44.70
t Assumes average pulmonary ventilation of 25 liters per minute for 2
hours, and complete absorption of inhaled pesticide.
Ih8284dv
-------
783
Summary of Multipliers Used in Converting Air, Glove, and Patch
Measurements into Dosage Estimates
Malathion Methiocarb Captafol
Air Cone (ug/2 hr) A.92 8.34 5.17
(Pers Air Sampler)
Gloves (ug/2 hr) 4.54 6.90 9.09
Patches (ug/2 hr)
Forearms
Shoulders
Chest
Back
Average Areas of Regions of the Body of the Adult Male
Total Body Area 19,200 cm2
Hands ' 1,075 cm2
Forearms 1,286 cm2
Shoulders 1,306 cm2
Chest 1,536 cm2
Back 1,536 cm2
t From: Popendorf, W. et al. Residue Reviews 82:125-201, 1982.
9.05
9.19
10.82
21.61
11.04
12.29
13.28
26.52
18.72
19.02
22.38
44.70
Ih8284dw
-------
Section A
Pages AC116 through AC143
APPENDIX C
MEASURES OF PERSONAL CONTACT WITH PESTICIDE -
GLOVES, PATCHES, PERSONAL AIR
784
Studies I, II, III - VK Field
Malathion
Guthion
Methiocarb
Captafol
Table
C 1-3
C 4-6
C 7-9
C 10-12
Page
AC117
AC120
AC123
AC126
Studies IV, V, VI - GC-1 Field
Malathion
Methiocarb
Captafol
C 13-15
C 16-18
C 19-21
AC 129
AC132
AC135
Studies VII, VIII - GC-2 Field
Methiocarb
Captafol
C 22-23
C 24-25
AC 138
AC140
Study IX - GC-1 Field
Methiocarb
Captafol
C
C
26
27
AC142
AC 143
Ih82884dw
AC 116
-------
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Malathion
Table C-1
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
785
Reported in Units of Micrograms, Not Recovery Corrected,
Per' Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Youth
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
CLH
Forearm
(pair)
240
1344
352
1640
440
488
16
808
696
336
320
184
120
14
134
50
208
448
77
20
Chest
(pair)
18
152
5
200
10
216
10
128
160
19
47
11
63
11
52
30
104
104
2
3
Shoulder
(pair)
58
384
264
392
2
160
11
360
326
11
54
144
20
10
26
14
10
120
2
2
Back
0.8
2.5
7.2
15.2
16.4
1.6
56.0
2.9
276.0
2.5
4.8
2.4
7.6
2.9
2.8
1.4
44.0
3.2
0.4
1.6
Inside
Forearm
52
44
92
128
20
104
72
6
5
264
5
4
5
6
5
232
4
38
25
5
Inside
Chest
2.6
21.2
2.8
12.0
12.4
6.4
2.3
2.4
1.8
2.3
5.2
0.8
1.9
3.4
1.3
3.9
1.1
20.8
0.8
2.9
Inside
Back
0.8
4.0
0.7
3.4
2.0
2.6
2.6
2.6
2.4
3.2
0.8
0.5
2.6
2.8
1.9
3.7
2.2
3.6
1.5
2.0
C1 oves
(pair)
1511
7200
9631
-
3822
3049
7300
7566
7812
12390
1867
2578
1362
2289
3125
2162
1600
3200
1136
210
Personal
Air (m )
75
232
1067
154
150
80
105
90
170
200
73
220
140
100
229
No Sample
100
240
267
100
Forearm Chest Shoulder
Adult
Mean
Youth
Mean
AMean
t
d.f.
P
(pair
636
157
+478
2
18
<0
L
.0
.5
.5
.87
.01
(pair)
. 91.8
42.8
+49.0
1.62
18
NS
(pair
197
40
+156
2
18
<0
L
.0
.2
.8
.84
.02
Back
38.1
7.1
+31.0
1.13
18
NS
Forearm
78
32
+45
1
18
NS
.7
.9
.8
.38
Chest
6
4
+2
0
18
NS
.6
.2
.4
.85
Back
2.4
2.2
+0.2
0.57
18
NS
Inside Inside Inside Cloves Personal
(pair) Air (a3)
6697.9 234.3
1954.9 163.2
44743.0 +71.1
4.26 0.69
17 17
<0.001 NS
in
-------
Table C-2
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
786
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Malathion
Samples: Patches, Cloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
322
176
860
800
352
476
388
120
18
232
860
124
228
1108
664
364
772
620
116
60
374.4
491.6
-117.2
0.8
18
NS
Chest
(pair)
52.0
1.6
22.4
64.0
13.2
96.0
6.8
15.6
4.4
15.6
72.0
52.0
44.0
132.0
76.0
72.0
76.0
40.0
12.4
12.0
29.2
58.6
-29.6
2.0
18
NS
Shouldei
(pair)
21.0
1.9
92.0
64.0
22.4
72.0
48.0
8.8
17.2
108.0
76.0
19.2
19.2
228.0
180.0
224.0
37.6
30.8
3.2
14.4
45.5
83.2
-37.7
1.2
18
NS
p
Back
18.4
0.4
18.0
3.6
3.2
34.4
7.6
1.8
0.7
0
39.2
9.6
3.6
7.2
64.0
34.4
20.8
13.2
0.8
5.2
8.8
19.8
-11.0
1.5
18
NS
Inside
Forearm
96.0
148.0
3.7
108.0
76.0
5.2
48.0
44.0
0
3.0
2.8
3.2
4.4
244.0
408.0
112.0
208.0
16.0
5.2
3.6
53.2
100.7
-47.5
1.0
18
NS
Inside
Chest
3.0
2.4
2.9
12.0
1.4
3.5
3.3
0
0
0
3.7
4.4
0
5.2
3.1
4.0
4.8
3.1
2.9
1.8
2.8
3.3
-0.5
0.4
18
NS
Inside
Back
0.6
0.6
2.5
6.0
1.9
15.6
2.8
0
0
0
2.4
2.3
3.4
2.5
3.1
2.8
4.0
2.8
1.1
0.9
3.0
2.5
*0.5
0.3
18
NS
Cloves
(pair)
4596
9149
22195
3957
10426
3171
8634
1609
242
261
1160
3415
695
2298
417
5
792
964
738
10170
6444
2067
+4377
1.9
18
NS
Personal
Air (m3)
0.5
0.3
0.5
12.5
0.8
0.4
1.2
1.5
1.5
0.4
0
1.7
2.1
1.4
1.8
1.9
2.7
48.3
0.2
0.4
2.0
6.0
-4.0
0.8
18
NS
1h11485dw
AC118
-------
Table C-3
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
787
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Malathion
Samples: Patches, Cloves, Personal Air
Collection: 7/22/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAM
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
cm
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
84.0
88.0
41.6
29.6
84.0
39.6
56.0
32.0
38.4
31.2
452.0
3.1
184.0
60.0
48.0
36.0
184.0
37.6
44.0
104.0
52.4
115.3
-62.9
1.5
18
NS
Chest
(pair)
33.2
22.4
27.6
1.2
18.4
18.0
3.0
11.6
3.0
18.8
20.4
3.3
80.0
0
34.4
80.0
80.0
1.8
2.4
72.0
15.7
37.4
-21.7
1.8
18
NS
Shoulder
(pair)
80.0
64.0
38.8
48.0
52.0
64.0
76.0
64.0
0.8
23.2
48.0
25.6
16.4
2.1
19.2
128.0
80.0
2.6
2.8
22.8
51.1
34.7
•••16.4
1.1
18
NS
Back
5.2
13.6
3.5
16.0
8.0
1.8
3.5
8.8
1.2
6.0
8.8
0
10.0
24.0
4.8
39.2
17.6
2.1
1.7
3.8
6.8
11.2
•4.4
1.1
18
NS
Inside
Forearm
0
3.2
4.8
9.6
4.4
0.8
10.0
1.*
12.8
6.4
7.6
0.8
1.7
7.6
4-.0
1.9
13.2
1.8
3.1
3.3
5.3
4.5
40.8
0.4
18
NS
Inside
Chest
8.0
14.4
5.6
13.6
31.2
8.8
15.2
18.4
22.0
2.6
12.4
1.6
26.0
44.0
7.2
8.4
0.8
1.4
21.2
16.0
14.0
13.9
•KJ.1
0.01
18
NS
Inside
Back
6.4
0.7
2.5
20.4
20.8
22.0
12.8
4.0
13.2
3.3
14.0
4.8
1.5
9.6
5.2
14.8
2.6
0.7
15.2
0.6
10.6
6.9
+3.7
1.1
18
NS
Cl oves
(pair)
161
116
82
190
111
174
73
149
185
219
249
136
187
264
123
45
135
116
139
125
146.0
152.0
-6.0
0.2
18
NS
Personal
Air (m )
0.6
No sample
0.5
0.7
0
0.4
0.2
0.7
0.5
0.3
6.1
13.6
16.7
No sample
17.9
1.3
35.7
75.8
15.3
0.3
0.4
20.3
-19.9
2.6
16
<0.01
1h11485dw
AC119
-------
Table C-*
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
788
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Guthion
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LOH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Chest
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.12
Shoulder
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Back
0
0
0
0
0
0
0
0
0.92
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cloves
(pair)
0
0
0
0
0
0
0
5.0
0
11.0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
IMUSSdw
AC120
-------
Table C-5
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
789
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Cuthlon
Samples: Patches, Cloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
Reported Units 1n Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
cm
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Chest
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Shoulder
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cloves
(Pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.0
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1h11485dw
AC121
-------
Table C-6
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
790
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1962
Pesticide: Cuthion
Samples: Patches, Cloves, Personal Air
Collection: 7/22/82
Method: See Analytical Methods (Appendix B)
Reported Units in Klcrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAM
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
NEB
PAB
AMD
JEK
DEL
BVK
JVK
cm
CLH
Mean
Adult
Mean
Child
Means
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
1.*
0
0
0
0
0
0
0
0
0
Chest
(pair)
0
0
0
0
0
0
0
0
0
0
1.*
0
0
0
0
0
0
0
0
0
Shoulder
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cl oves
(pair)
3.4
0
0
*.3
0
0
0
1.8
2.8
0
0
0
0
0
0
1.6
0
0
*.3
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
IhlUBSdw
AC122
-------
Table C-7
YOUTH IN AGRICULTURE
IOWA PHAP, 1962
791
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Methiocarb
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82 PM
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
'jAH
JYH
JSH
LIH
TAH
LOH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
~
Chest
(pair)
0
0
0
0
0
0
0
0
0.38
0
0
0
0
0
0
0
0
0
0
•
Shoulder
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
•
Back
0
0
0
0
0
0
0
0
0.32
0
0
0
0
0
0
0
0
0
0
•
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
C1 oves
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1h11485dw
AC 123
-------
Table C-8
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
792
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1962
Pesticide: Methiocarb
Samples: Patches, Gloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
NEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
GLH
Mean
Adult
Mean
Child
AMeani
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
0
Chest
(pair)
0.89
0
0.34
0.37
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
0
Shoulder
(Pair)
0
0
0
0.31
0
0
"o
0
0
0
0
0
-
0
0
0
0
0
0.25
0
Sack
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
«— ^B^Kl^^^W
0
0
0
0
0
0
0
0
0.46
0
0
0
0
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0.35
0
0
0
0
0
0
0
0
0
0
0
Gl oves
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0.34
0
0
0
0
0
0
0
0
0
1h1U85dw
AC124
-------
Table C-9
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
793
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesfricide: Methiocarb
Samples: Patches, Cloves, Personal Air
Collection: 7/22/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAM
JYH
JSH
LIH
TAH
LOH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(Pair)
-
0
-
-
0
-
0
0
0
0
-
-
-
-
-
0
.
.
.
0
Chest
(pair)
-
0
-
-
0
-
0
0
0.39
0
-
-
-
0
-
0
.
-
.
0
Shoulder
(pair)
-
0
-
-
0
-
0
0
0.27
0
-
-
-
0
-
0
.
.
•
0
Back
-
0
-
-
0
-
0
0
0
0
-
-
-
-
•
0
-
-
-
0
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
Inside
Chest
0
0
0
0
•0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
G1 oves
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
1h11485dw
AC125
-------
794
Table C-10
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Captafol
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
cm
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
0.40
0.2%
0.16
0.16
0.12
0.12
0.32
0.68
0.36
0
0.16
0.40
0.08
0.20
0.20
0
0.28
0.28
0
0
0.25
0.16
+0.09
1.27
18
NS
Chest
(pair)
0.40
0.60
0
0.36
0.12
0.24
1.36
0.66
0.32
0
0.12
0.24
0.08
0.16
0.32
0
0
0.28
0
0
0.40
0.12
+0.28
2.15
18
<0.05
Shoulder
(pair)
0.28
0.20
0.16
0.16
0.12
0.08
0.32
0.68
0.24
0
0.16
0.32
0
0.20
0.28
0
0.24
0.28
0
0
0.22
0.14
+0.08
1.04
18
NS
Back
0.28
0.28
0.05
0.28
0.16
0.24
0.05
0.32
0.24
0
0.16
0
0
1.72
0.20
0
0
0.28
0
0
0.19
0.23
-0.04
0.26
18
NS
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
J.
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Cl oves
(pair)
0
0
0
0.06
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
0.03
0
0
0
0
0
0
0
0
0
0
0
0 t
Not
Analyzed
0
0
0
0
Air sampler malfunctioned
AC126
-------
Table C-11
YOUTH IN AGRICULTURE
IOMA PHAP, 1982
795
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Captafol
Samples: Patches, Cloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
cm
CLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
0
0.5
0
1.2
0
0
0
0
0
0
0.3
0
1.7
0
0
0
0
0.6
0
0
Chest
(pair)
0
0.8
0
0
0
0
0.8
0
0
0
0.9
0
2.4
0.9
0
0
0
0.4
0
0
Shoulder
(pair)
0
1.0
0
0
0
0
0
0
0
0
0.6
0
0.9
0
0
0
0
0.5
0
0
Back
0
0.4
0
0
0
0
0
1.3
0
0
1.8
0
0.3
0
0
1.5
2.7
0.3
0
0
Inside
Forearm
0
1.0
0
0
0
0
0
0
0
0
0
0
0.8
0
0
0
0
0
0
0
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0.7
0
0
0
0
0
0
1.2
Gl oves
(pair)
0
5.9
0
0
0
0
0
0
0
0
0
0
4.3
0
0
0
0
0
0
0
Personal
Air (m3)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1h11485dw
AC127
-------
Table C-12
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
796
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Captafol
Samples: Patches, Cloves, Personal Air
Collection: 7/22/82
Method: See Analytical Methods (Appendix B)
Reported Units in Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Child
Subjects
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
CIH
GLH
Mean
Adult
Mean
Child
AMeans
t
d.f.
P
Forearm
(pair)
0
0.3
0
0
0
0
0
0
0
0
0.4
0
2.5
0.7
0
0
0
0
0
0
Chest
(pair)
0
1.3
0
0
0
0
1.4
0
0
0
0.4
0
0
0
0
0
0
0
0
0
Shoulder
(pair)
0
0
0
0
0.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Back
0
0.5
0
0
0
0
0
0
0
0
0
0
0
0
0
0.4
0
0
0
0
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.7
0
0
Inside
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
1.5
0
0
0
0
0
0
Gl oves
(pair)
0
0
0
1.2
0
0
0
0.9
0
0
0
0
0
0
0
2.6
0
0.9
1.2
0
Personal
Air (m )
0
0
0
0
1.5
0
0.8
1.1
0.8
0
0
1.4
2.5
0
0
1.4
1.5
1.4
1.5
0
0.4
1.0
-0.6
1.63
18
MS
AC128
-------
797
Site: CC-1 Field
Crop: Blueberries, Study IV
Study Date: July 19, 1982
Pesticide: Malathion
Table C-13
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/19/82
Method: See Analytical Methods (Appendix B)
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
Child
Subjects
FRH
ECJ
RMC
AMG
TIS
DES
TOS
ROC
CHG
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
0
0
0
0
0
0
0
0
0
0
0
0.44
0
0
0
0
0
0
Forearm
(pair)
0
0.05
Chest
(pair)
0
0
0
0
0
0
0
0
0
•0
0
0
0
0
0
0
0
0
Chest
(pair)
0
0
Shoulder
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Shoulder
(pair)
0
0
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Back
0
0
Inside
Forearm
0
0.08
0
0
0.16
0
0
0
0
0.16
0
0
0.52
0.44
0
0
0.28
0
Inside
Forearm
0.02
0.15
-0.13
Inside
Chest
0
0
0
0
0.24
0
0
0
0
0
0
0.16
0.75
0.16
0
0
0.96
0
Inside
Chest
0.02
0.22
-0.20
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0.60
1.08
0
0
1.04
0
Inside
Back
0
0.30
-0.30
Gloves
(pair)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
G1 oves
(pair)
0
0
Personal
Air (m )
0
0
0
0
-
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
Specimens designated - were not collected due to malfunction.
1h11485dw
AC 129
-------
Site: CC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1982
Pesticide: Malathion
Table C-1*
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
798
Adult
Subjects
MAC
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
Forearm
(pair)
-
-
-
-
-
-
-
-
Chest
(pair)
-
-
-
-
-
-
-
-
Shoul der
(pair)
-
-
-
-
-
-
-
-
-
Back
-
-
-
-
-
-
-
-
-
Inside
Forearm
0
-
0
-
-
0
0
0
0
Inside
Chest
0
-
0
-
-
0
0
0
0
Inside
Back
0
-
0
-
-
0
0
0
0
Gl oves
(pair)
0
0
-
0
0
-
0
0
0
Personal
Air (m )
0
0
0
0
0
-
0
0
0
Child
Subjects
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
0
0
0
0
-
0
-
-
.
0
0
0
-
-
0
-
-
-
0
0
0
-
-
0
-
-
.
0
0
-
-
0
0
0
0
.
0
0
0
-
0
0
0
0
0
Forearm Chest Shoulder
(pair) (pair) (pair)
Inside Inside
Back Forearm Chest
Inside Gloves
Back (pair)
Personal
Air (m )
Specimens designated • were not analyzed
1h11*85dw
AC130
-------
Table C-15 799
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: GC-1 Field Samples: Patches, Cloves, Personal Air
Crop: Blueberries, Study VI Collection: 7/21/82
Study Date: July 21, 1982 Method: See Analytical Methods (Appendix B)
Pesticide: Malathion
No Analyses Done
lh11485dM AC131
-------
Site: GC-1 Field
Crop: Blueberries, Study IV
Study Date: July 19, 1982
Pesticide: Methiocarb (Mesurol)
Table C-16
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/19/82
Method: See Analytical Methods (Appendix B)
800
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
Child
Subjects
FRH
EGJ
RMG
AMG
TIS
DES
TOS
ROC
CHC
-
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
4.8
3.6
0
15.4
8.4
0
3.3
1.2
2.2
5.2
9.2
22.0
0
9.2
4.4
5.2
4.8
0
Forearm
(pair)
4.3
6.7
-2.4
0.85
16
NS
Chest
(pair)
2.0
2.6
0
0
2.6
0
0
1.7
1.5
1.5
6.4
3.8
3.9
10.8^
3.0
3.7
3.7
0
Chest
(pair)
1.1
4.1
-3.0
2.68
16
<0.02
Shoulder
(pair)
1.4
2.0
0
0
2.4
0
2.6
3.5
0
0
2.9
5.6
2.8
7.6
2.7
5.2
1.6
0
Shoulder
(pair)
1.3
3.1
-1.80
1.89
16
NS
Back
0
0
0
0
0
0
0
0
0
0
1.5
1.2
0
1.2
0
1.4
2.1
0
Back
Inside
Forearm
2.3
0
0
0
0
0
0
0
0
0
0
0
0
1.0
0
0
1.0
1.0
Inside
Forearm
Inside
Chest
0
0
0
2.7
0
0
0
0
0
0
10.8
0
0
2.3
0
0
0
1.7
Inside
Chest
Inside
Back
0
0
0
1.0
0
0
0
0
0
0
1.1
0
0
1.2
0
0
0
1.1
Inside
Back
Gl oves
(pair)
111
80
122
380
337
164
68
110
396
202
183
938
98
255
140
135
18
52
Gl oves
(pair)
196
225
-29
0.27
16
NS
Personal
Air (m )
0
0
0
0
-
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
Specimen designated - was not collected due to malfunction.
1h11485dw
AC132
-------
Site: GC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1982
Pesticide: Hethiocarb (Mesurol)
Table C-17
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
Reported in Units of Micrograms, Not Recovery Corrected
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
Child
Subjects
FRH
ECJ
RMC
AMC
*TIS
OES
TOS
ROC
CHC
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
1.92
0
5.12
0
1.68
1.4*
0
1.64
4.68
2.64
6.56
1.44
0
26.72
2.20
5.00
3.60
2.00
Forearm
(pair)
1.83
5.57
-3.74
1.33
16
NS
Chest
(pair)
0
0
0
0
0
0
0
0
0
0
2.68
0
0
3.32
0
2.40
1.20
0
Chest
(pair)
0
1.05
-1.05
Shoulder
(pair)
0.88
0
0
0
0
0
0
0
0
0.96
3.04
0
0
0
0
3.60
1.20
0
Shoul der
(pair)
Back
0
0
0
0
0
0
0
0
1.32
0
0
0
0
0
0
3.76
0
0
Back
Inside
Forearm
0
4.12
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
Inside
Chest
0
0
Inside
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
0
0
G1 oves
(pair)
219
381
574
105
523
287
462
74
304
469
103
63
35
600
176
348
96
174
Cl oves
(pair)
325.4
229.3
+96.1
1.08
16
NS
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m3)
0
0
801
Specimen designated - was not analyzed
1h11485dw
AC133
-------
Site: GC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1982
Pesticide: Hethiocarb (Mesurol)
Table C-18
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
802
Reported in Units of Mfcrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
NAT
DAG
EAG
JIJ
BIG
Child
Subjects
FRH
EGJ
RMG
AMG
TIS
DES
TOS
ROC
CMC
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
3.08
6.16
2.12
3.72
3.72
2.80
2.96
3.20
4.28
8.80
2.96
2.04
19.76
2.28
3.56
1.8
6.0
1.52
Forearm
(pair)
3.56
5.41
•1.85
0.92
16
NS
Chest
(pair)
0
1.96
0
0
0
0
3.44
1.48
0
0
3.44
0
5.60
1.04
2.48
0
3.52
1.88
Chest
(pair)
0.76
1.99
-1.23
1.59
16
NS
Shoulder
(pair)
0
0.96
0
0
0
0
4.60
1.28
0
0
4.60
0
5.84
1.80
1.52
0
0
•
Shoulder
(pair)
0.76
1.72
-0.96
1.02
15
NS
Back
0
0
0
0
0
0
0
0
0
0
0
0
3.56
0
0
1.24
0
0
Back
a
0.53
-0.53
Inside
Forearm
1.00
1.44
0
0
0
1.36
2.84
2.44
2.72
0
2.84
0
0
0
0
0
0
0
Inside
Forearm
1.31
0.31
+1.00
Inside
Chest
0
0
0
0
0
0
0
0
0
0
1.00
0
1.72
0
0
0
0
0
Inside
Chest
0
0.3
-0.30
Inside
Back
0
0
0
0
0
0
7.40
0
3.28
0
7.40
3.04
1.20
0
0
0
0
0
Inside
Back
2.69
1.29
+1.40
Gloves
(pair)
222
324
134
250
185
393
308
283
1500
-
308
97
585
119
356
84
276
123
Gloves
(pair)
400
243
+157
0.97
15
NS
Personal
Air (m )
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Personal
Air (m )
0
0
Specimens designated - were not analyzed.
1h11485dw AC134
-------
Site: CC-1 Field
Crop: Blueberries, Study IV
Study Date: July 19, 1982
Pesticide: Captafol (Difolatan)
Table C-19
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/19/82
Method: See Analytical Methods (Appendix B)
803
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JU
BIG
Child
Subjects
FRH
ECJ
RMG
AMG
TIS
DES
TOS
ROC
CHG
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
32.8
15.2
148.0
28.0
80.0
14.8
14.4
16.4
2.8
28.0
44.0
24.4
6.0
64.0
44.0
40.0
60.0
35.6
For ears
(pair)
39.1
38.4
+0.7
0.04
16
NS
Chest
(pair)
7.6
17.2
9.6
17.6
24.8
6.4
2.7
13.6
0.7
18.4
22.4
4.4
12.4
60.0
14.4
12.8
44.0
17.6
Chest
(pair)
11.1
22.9
-11.8
1.83
16
NS
Shoulder
(pair)
4.8
7.6
8.4
5.2
10.4
9.6
1.7
30.4
8.4
1.3
12.4
9.6
4.8
28.0
13.2
33.2
8.4
18.4
Shoulder
(pair)
9.6
14.4
-4.8
1.06
16
, NS
Back
1.0
1.2
3.7
1.8
2.7
0.4
0.5
2.0
0.5
0.5
1.1
0.6
3.5
5.2
2.0
7.6
3.8
1.1
Back
1.53
2.82
-1.29
1.44
16
NS
Inside
Forearm
1.1
0.7
2.1
0.4
1.3
0.7
0.5
0.7
0.2
0.6
1.0
0.8
0.5
2.6
0.5
5.2
14.0
4.8
Inside
Forearm
0.85
3.33
-2.48
1.67
16
NS
Inside
Chest
0.32
0.08
0.48
0.56
3.64
0.52
0.28
2.56
3.08
0.24
3.80
0.20
0.60
2.92
0.68
0.96
0.92
0.60
Inside
Chest
1.27
1.21
+0.06
0.09
16
NS
Inside
Back
0.36
0.32
0.40
0.44
0.40
0.40
0.08
3.08
0.08
0.24
0.80
0.24
0.48
0.96
3.96
1.24
18.80
0.80
Inside
Back
0.61
3.05
-2.44
1.20
16
NS
Cl oves
(pair)
1120
1280
2240
935
4029
1390
464
1310
535
949
1630
536
374
872
2600
739
320
6016
Cl oves
(pair)
1478
1560
-82
0.11
16
NS
Personal
Air (m )
0.78
2.96
0.68
0.35
-
0.45
0
1.90
0
0.90
1.06
0
0
• 8.00
2.39
3.33
3.54
0.83
Personal
Air (m3)
0.89
2.22
-1.33
1.39
15
NS
Specimen designated - was not collected due to malfunction.
Ih11485dw
AC135
-------
804
Site: CC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1982
Pesticide: Captafol (Olfolatan)
Table C-20
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/20/82
Method: See Analytical Methods (Appendix B)
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIG
Child
Subjects
FRH
EGJ
RMG
AMC
TIS
DES
TOS
ROC
CHC
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
19.2
85.2
50.6
32,8
62.7
20.7
31.2
24.0
30.9
22.8
24.6
26.4
56.2
158.8
81.0
44.7
36.3
6.3
Forearm
(pair)
39.7
50.8
•11.1
0.65
16
NS
Chest
(pair)
3.84
357.20
12.56
13.52
3.76
2.72
2.76
7.12
5.80
1.84
10.80
11.92
14.84
16.52
13.00
17.16
23.28
21.72
Chest
(pair)
45.5
14.6
+30.9
0.79
16
NS
Shoulder
(pair)
19.2
12.8
15.3
15.6
16.2
4.2
8.5
11.8
3.7
5.0
11.3
2.9
18.08
34.40
14.72
11.76
11.28
17.72
Shoulder
(pair)
11.9
14.6
-2.7
0.62
16
NS
Back
0.84
1.36
4.40
1.28
0.84
0.20
0.52
1.72
0.12
0.40
0.32
1.72
7.60
3.64
0.48
7.20
1.16
2.16
Back
1.25
2.29
-1.04
1.21
16
NS
Inside
Forearm
0.68
6.76
1.96
1.36
0.96
0.44
0.80
1.64
0.80
0.32
0.20
1.64
16.80
0.64
2.12
3.36
3.96
0.40
Inside
Forearm
1.71
3.27
-1.56
0.83
16
NS
Inside
Chest
0.24
0.20
0.64
2.68
0.64
0.12
0.20
0.84
3.44
0.84
0.68
0.16
-
0.12
0.44
0.40
0.64
1.52
Inside
Chest
1.00
0.60
+0.40
0.88
16
NS
Inside
Back
0.12
0.16
0.72
0.88
0.32
0.12
0.12
10.96
0.32
0.20
0.20
0.20
3.12
0.12
0.64
0.76
0.92
0.72
Inside
Back
1.52
0.76
+0.76
0.62
16
NS
G1 oves
(pair)
450
1098
821
653
989
-
623
808
670
636
-
959
402
713
1297
1371
342
725
Gloves
(pair)
764
806
-42
0.27
14
NS
Personal
Air (m )
0
1.40
0.17
0.17
0.36
0.15
0
0.22
0.31
3.92
0.50
0.35
1.50
4.44
0.17
0.75
0.83
0.82
Personal
Air (m )
0.30
1.47
-1.17
2.13
16
<0.05
Specimens designated - were not analyzed
Ih11485dw
AC136
-------
Site: CC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1982
Pesticide: Captafol (Difolatan)
Table C-21
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/21/82
Method: See Analytical Methods (Appendix B)
805
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
WAG
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIG
Child
Subjects
FRH
EGJ
RMC
AMG
TIS
DES
TOS
ROC
CHC
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
69.56
65.28
63.40
52.16
12.32
14.76
12.16
100.00
22.96
19.56
40.84
32.24
20.76
79.04
85.72
59.08
27.76
•
Forearm
(pair)
45.8
45.6
+0.2
0.01
15
NS
Chest
(pair)
10.00
27.64
14.32
26.96
13.92
2.04
2.08
29.52
1.48
3.08
16.48
5.88
11.60
29.12
23.20
16.64
17.28
46.56
Chest
(pair)
14.2
18.9
•4.7
0.80
16
NS
Shoulder
(pair)
23.28
10.56
10.72
11.44
34.00
2.40
1.40
27.68
1.84
2.20
32.08
11.08
7.24
29.84
5.80
8.56
7.32
37.08
Shoulder
(pair)
13.7
15.7
•2.0
0.33
16
NS
Back
0.46
4.84
0.92
1.12
1.88
0.48
0.36
3.08
0.28
0.48
0.64
0.92
0.84
19.60
0.72
5.12
1.20
0.92
Back
1.5
3.4
•1.9
0.88
16
NS
Inside
Forearm
3.04
1.52
1.20
2.36
2.20
0.36
0.40
3.88
1.20
0.60
1.44
2.20
0.44
2.12
1.28
2.52
1.64
8.68
Inside
Forearm
1.8
2.3
-0.5
0.57
16
NS
Inside
Chest
0.32
1.60
0.56
1.72
0.32
0.36
0.44
0.44
0.88
0.08
0.52
0.36
0.52
1.00
0.88
0.92
0.92
1.16
Inside
Chest
0.7
0.7
0
Inside
Back
0.36
0.44
0.28
0.44
0.68
0.32
0.36
0.76
1.80
0.16
1.44
0.64
0.24
0.36
1.00
0.40
0.44
0.24
Inside
Back
0.6
0.5
+0.1
0.47
16
NS
G1 oves
(pair)
2178
1232
2551
2713
1857
566
882
6630
135
-
1440
1392
548
2468
2409
3116
917
186»
G1 oves
(pair)
2082.7
1768.7
+314
0.42
15
NS
Personal
Air (m )
0.19
0.25
0.31
0.15
0.08
0.05
0.04
0.17
0.04
0.04
0.13
0.44
0.28
0.42
0.24
0.17
0.39
0.25
Personal
Air (m3)
0.14
0.26
-0.12
2.14
16
<0.05
Specimens designated - not analyzed
137
-------
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 27, 1982
Pesticide: Hethlocarb
Table C-22
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/27/82
Method: See Analytical Methods (Appendix B)
806
Reported in Units of Micrograms, Not Recovery C&rrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JID
NAG
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIG
AND
Child
Subjects
FRH
ECJ
RMG
AMG
TIS
DES
TOS
ROC
CHG
JAH
LAH
Mean
Adult
Mean
Child
Forearm
(pair)
1.20
6.16
0.4
0
0
1.2
0
2.52
10.0
0
15.08
14.76
8.7
0
0
0 '
2.76
5.16
0
1.20
2.40
15.3
Forearm
(pair)
3.5
4.6
Chest
(pair)
0
0
0
0
0
0
0
1.6
1.9
0
7.12
0
0
0
0
1.0
0
1.72
6
0
0
2.3
Chest
(pair)
1.0
0.4
Shoulder
(pair)
0
0 -
0
0
0
0
0
0
1.4
0
7.36
0
0
0
0
0
1.9
0
0
0
0
1.6
Shoulder
(pair)
Back
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.0
0
0
0
0
0
1.0
Back
Inside
Forearm
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
Inside
Chest
0
0
0
0
0
0
0
0
0
0
0
2.68
0
0
0
0
0
0
0
0
0
0
Inside
Chest
Inside
Back
0
0
0
0
0
0
0 '
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Inside
Back
Gl oves
(pair)
12.8
52.0
1.8
0
0
0
0
69.0
127.8
0
39.2
21.2
0
0
2.4
28.0
34.6
79.8
4.6
5.8
38.0
150.8
Gl oves
(pair)
27.5
33.2
Personal
Air (uoYm )
No Sampler
0
0
0
0
0
0
0
4.52
0
No Sampler
0
0
0
0
0
No Sampler
0
0
0
0
0
Personal
Air (m )
AMean
-1.1
+0.6
•5.7
1h11485dw
AC 138
-------
Site: CC-2 Field
Crop: Blueberries, Study VIII
Study Date: July 28, 1982
Pesticide: Methlocarb
Table C-23
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Gloves, Personal Air
Collection: 7/28/82
Method: See Analytical Methods (Appendix B)
807
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Glove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JID
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
AND
0
0
0
0
0
0
0
Chest
(pair)
0
0
0
0
Shoulder
(pair)
0
0
0
0
Back
0
0
0
0
Inside
Forearm
Inside
Chest
Inside
Back
Gloves
pair)
0
0
0
0.1
0
0
0
0
0
0
Personal
Air (m )
Child
Subjects
FRH
EGJ
RMG
AMG
TIS
DES
TOS
ROC
CHG
JAH
LAH
0
0
-
-
-
-
0
0
0
-
-
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.1
0
0
Samples designated - were not analyzed
1h11*85dw
AC139
-------
Table C-24
808
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 27, 1982
Pesticide: Captafol
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1962
Samples: Patches, Cloves, Personal Air
Collection: 7/27/82
Method: See Analytical Methods (Appendix B)
Reported In Unfts of Mlcrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of A1r
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JID
NAC
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIG
AND
Child
Subjects
FRH
EGJ
RMG
AMG
TIS
DES
TOS
ROC
CHC
JAM
LAH
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
69.1
81.7
160.9
197.9
85.4
146.7
204.2
36.0
90.8
97.4
150.5
201.6
217.9
138.9
54.2
103.6
91.7
119.3
30.0
140.7
151.4
121.5
Forearm
(pair)
120.0
124.6
-4.6
0.19
20
NS
Chest
(pair)
21.3
7.2
21.0
15.6
21.1
4.4
31.6
3.5
18.1
5.9
30.4
39.2
29.3
20.0
26.7
85.4
20.1
29.0
16.7
14.0
86.4
31.5
Chest
(pair)
16.4
36.2
-19.8
2.39
20
<0.05
Shoulder
(pair)
25.1
15.6
22.4
13.9
22.8
43.2
67.2
8.4
19.4
4.8
27.2
24.1
17.4
19.2
7.8
57.8
25.8
24.9
7.6
17.0
35.0
31.2
Shoulder
(pair)
24.5
24.3
+0.2
0.02
20
NS
Back
2.8
3.6
1.4
8.0
1.2
1.3
12.0
1.6
0.7
1.4
3.2
7.8
1.4
1.2
1.0
5.0
8.3
5.4
0.6
5.6
3.2
9.1
Back
3.4
4.4
-1.0
0.73
20
NS
Inside
Forearm
0.6
0.4
2.2
0.5
1.4
0.2
1.2
1.5
0.5
4.7
0.4
6.6
0.4
1.2
1.0
1.1
0.6
1.2
0.5
0.7
2.3
6.0
Inside
Forearm
1.23
1.98
-0.75
0.96
20
NS
Inside
Chest
0.1
0.5
0.4
0.2
0.1
0.2
0.8
0.4
0.2
0.3
0.5
0.2
0.5
1.1
1.0
1.2
0.4
0.9
0.5
0.4
0.7
0.4
Inside
Chest
0.33
0.66
-0.33
2.73
20
<0.02
Inside
Back
0.4
0.5
0.6
0.3
0.5
0.2
0.8
0.2
0.2
0.2
0.2
0.7
0.4
0.3
0.4
1.0
0.4
0.2
0.3
0.4
0.6
0.4
Inside
Back
0.37
0.46
-0.09
0.99
20
NS
G1 oves
(pair)
2412
1264
1065
1220
1667
429
951
656
1036
795
963
2983
1035
1684
1055
1248
457
713
589
652
2108
2946
G1 oves
(pair)
1132
1406
-274
0.85
20
NS
Personal
Air (m )
No Sampler
0.45
1.33
0.22
1.17
0.26
0.83
0.45
0.59
0.21
No Sampler
1.00
0.40
1.11
1.25
2.17
No Sampler
2.64
1.41
0.89
2.16
1.51
Personal
Air (m )
0.61
1.45
-0.84
3.19
17
<0.01
1h11485dw
AC1AO
-------
Table C-25
809
Site: CC-2 Field
Crop: Blueberries, Study VIII
Study Date: July 28, 1982
Pesticide: Captafol
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/28/82
Method: See Analytical Methods (Appendix B)
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JIO
MAC
KAY
JAM
JIY
MAT
OAC
EAC
JIJ
BIG
AND
Child
Subjects
FRH
ECJ
RMC
AMG
TIS
DES
TOS
ROC
CMC
JAH
LAH
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
39
35
46
170
82
97
40
23
52
96
56
89
21
145
19
170
130
100
76
150
130
25
Forearm
(pair)
66.9
95.9
-29.0
1.38
20
NS
Chest
(pair)
6
5
23
33
11
10
10
2
10
6
16
9
7
25
9
88
U
26
18
37
29
23
Chest
(pair)
12.0
25.9
-13.9
1.89
20
NS
Shoulder
(pair)
12
18
23
77
39
18
36
5
12
U
20
17
20
42
8
81
26
50
8
23
11
13
Shoulder
(pair)
24.9
27.2
-2.3
0.25
20
NS
Back
4.6
5.3
2.8
37.2
5.2
3.0
4.4
1.6
9.6
3.0
5.5
3.8
1.0
11.4
1.8
20.6
6.9
16.6
2.2
2.9
4.6
3.6
Back
7.5
6.8
+0.7
0.17
20
NS
Inside
Forearm
0.8
0.4
23.8
3.4
2.7
0.4
0.9
0.9
1.5
3.5
1.6
3.0
1.2
3.5
2.1
2.3
2.3
1.0
1.8
2.1
1.2
1.9
Inside
Forearm
^^•^^^^^•••w-
3.6
2.0
+1.6
0.77
20
NS
Inside
Chest
0.12
0.20
0.52
1.60
1.48
0.40
0.24
0.52
0.24
1.12
0.12
0.44
0.96
0.52
1.08
3.96
0.36
1.96
0.36
0.60
0.24
0.28
Inside
Chest
0.59
0.97
-0.38
1.02
20
NS
Inside
Back
0.28
0.44
0.44
0.56
0.72
0.20
0.32
0.20
0.72
0.96
0.48
0.36
0.20
0.72
0.68
0.88
0.44
1.24
0.56
0.68
0.44
0.16
Inside
Back
0.48
0.57
-0.09
0.79
20
NS
Gl oves
(pair)
1310
539
2171
737
2059
1320
1602
349
640
4298
950
1817
988
1045
312
750
692
485
461
1009
1543
439
Gl oves
(pair)
1452
867
+585
1.59
20
NS
Personal
Air (m )
0.42
0.21
0.90
No Sample
0.75
No Sample
1.22
No Sample
2.50
0.73
0.30
0.67
1.08
2.50
1.53
3.00
0.67
2.13
1.75
0.76
0.96
0.96
Personal
A1r (m )
0.87
1.45
-0.58
1.60
17
NS
1h11485dw
AC141
-------
Site: CC-1 Field
Crop: Blueberries, Study IX
Study Date: July 29, 1982
Pesticide: Methiocarb
Table C-26
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/29/82
Method: See Analytical Methods (Appendix B)
810
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JID
NAG
KAY
JAM
JIY
MAT
DAG
EAG
JU
BIG
AND
Forearm
(pair)
3.0
1.28
4.20
3.52
1.72
3.32
2.40
0.72
1.04
3.08
0
Chest
(pair)
0
0
0.48
1.24
0.84
0.24
0
0
1.12
0
0
Shoulder
(oair)
2.72
0.76
0.72
0
0
0
0
0
0
0.36
0
Back
0
0
0
0
0
0
0
0
0
0
0
Inside
Forearm
-
-
-
-
-
-
-
-
-
-
0
Inside
Chest
-
-
-
-
-
-
-
-
-
-
0
Inside
Back
-
-
-
-
-
-
-
-
-
-
0
Gloves
(pair)
45
53
113
49
71
125
59
59
72
91
51
Child
Subjects
FRH
ECJ
RMG
AMG
TIS
DES
TOS
ROC
CHC
JAM
LAH
3.60
1.13
5.28
1.40
8.60
1.60
3.40
2.72
12.64
3.80
8.64
1.16
0
2.16
0.52
2.32
0
2.32
1.48
3.80
2.24
8.16
0
0
2.60
0.28
4.20
0
2.12
0.76
3.20
1.88
1.28
1.64
0
0
0
0.84
0
0.60
0
0
0
0
-
-
-
-
0
-
-
-
0
-
-
Mean
Adult
Mean
Child
120
105
170
9
59
44
172
27
119
67
Forearm Chest Shoulder
Inside
2.2
4.8
0.3
2.2
0.4
1.5
AMean
t
d.f.
P
+2.6
2.2
20
<0.05
-1.9
2.6
20
<0.02
-1.1
2.1
20
<0.05
71.6
89.2
-17.6
0.91
19
MS
Samples designated - were not analyzed
Personal
Air (m )
Inside Inside Gloves Personal
pair) (pair) (pair) Back Forearm Chest Back (pair) Air (m )
AC142
-------
Site: CC-1 Field
Crop: Blueberries, Study IX
Study Date: July 29, 1982
Pesticide: Captafol
Table C-27
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Samples: Patches, Cloves, Personal Air
Collection: 7/29/82
Method: See Analytical Methods (Appendix B)
811
Reported in Units of Micrograms, Not Recovery Corrected,
Per Patch Pair, Patch, Clove Pair or Cubic Meter of Air
\ of Patch Sample Analyzed. Reported Results Reflect Extrapolation to Total Sample.
Adult
Subjects
JID
WAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
AND
Child
Subjects
FRH
ECU
RMG
AMG
TIS
DES
TOS
ROC
CHG
JAH
LAH
Mean
Adult
Mean
Child
AMean
t
d.f.
P
Forearm
(pair)
129.8
81.3
53.6
58.2
63.5
62.0
53.4
24.8
80.0
13.2
35.8
42.0
24.4
14.3
15.4
147.7
118.0
20.4
28.9
103.3
36.7
128.8
Forearm
(pair)
59.6
61.8
-2.2
0.12
20
NS
Chest
(pair)
11.6
10.4
9.5
9.1
26.8
5.3
5.9
2.7
18.5
1.0
8.3
9.0
3.8
3.7
3.5
43.1
9.9
5.4
21.6
31.8
20.6
128.2
Chest
(pair)
9.9
25.5
-15.6
1.39
20
NS
Shoulder
(pair)
22.4
30.3
12.5
5.8
20.0
5.9
18.0
2.4
22.4
3.1
12.6
17.1
6.7
2.6 "
2.6
32.3
17.9
6.4
7.0
24.3
12.8
29.2
Shoulder
(pair)
14.1
14.4
-0.3
0.07
20
NS
Back
1.5
1.5
1.2
0.6
1.5
0.6
1.5
0.9
5.1
0.6
2.7
2.1
0.5
0.9
0.7
3.1
2.2
0.9
0.8
1.7
1.4
2.4
Back
1.6
1.5
+0.1
0.19
20
NS
Inside
Forearm
0.3
0.8
1.8
2.2
2.9
2.9
1.7
3.4
4.4
1.2
4.8
1.0
1.3
8.6
3.3
1.8
1.2
0.8
2.8
1.0
3.5
1.1
Inside
Forearm
2.4
2.4
0
Inside
Chest
0.4
0.6
0.5
0.4
0.4
0.1
0.2
0.2
0.5
2.4
0.3
0.4
0.2
0.3
1.1
1.2
0.8
0.4
2.0
0.4
0.4
0.5
Inside
Chest
0.5
0.7
-0.2
0.61
20
NS
Inside
Back
0.5
0.4
2.7
0.1
0.4
0.4
0.3
0.2
1.6
0.2
0.3
0.3
0.6
0.2
0.4
0.4
1.0
0.3
0.3
0.1
0.4
0.2
Inside
Back
0.6
0.4
+0.2
1.05
20
NS
Gl oves
(pair)
785
1486
1645
758
1284
1110
1516
767
1851
220
492
1608
788
310
406
1044
1808
740
645
LOST
775
984
Gl oves
(pair)
1083.1
910.8
+172.3
0.78
20
NS
Personal
Air (m )
0.83
No Sampler
0.19
No Sampler
0.86
0
No Sampler
0.28
0.83
0.62
0.41
0.72
No Sampler
0.69
0.55
3.20c
0.83
0.50
2.08
1.21
0.50
3.09
Personal
Air (m )
0.5
1.3
-0.8
2.12
16
<0.05
Ih11485dw
AC143
-------
812
APPENDIX D
URINARY PESTICIDE METABOLITES IN HARVESTERS
Studies I, II, III - VK Field Table
Malathion D 1-7
Methiocarb D 8-14
Studies IV, V, VI - GC-1 Field
Malathion D 15-21
Methiocarb D 22-28
Studies VII, VIII
Methiocarb D 29-35
-------
813
Table D-1
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1962
Site: V K Field
Crop: Blueberries, Study I
Study Date: July 20. 1982
Pesticide: Malathion
Samples: Urine
Collection: July 20 AM, Pre-expo»ure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradnay and Shafik, 1977
Miami AP Procedure, 1980
Adults
Children
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
200
84
44
184
80
90
56
104
118
192
0
0
0
190
22
239
0
0
225
22
Pesticide
Equivalent, Malathion
ng/ml Eg. Wt.yg
0
' 0
0
35
2
22
0
0
27
4
cm
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
46
77
106
72
144
300
82
96
344
46
Pesticide
Equivalent,
ng/ml
33
22
329
22
0
268
300
635
0
0
Malathion
Eg. Kt.uq
2
2
35
2
0
80
25
61
0
0
Mean
Mean
21
AMean • 12
1.14
d.f.
18
<0.3
Ih7284dw
145
-------
814
Table D-2
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1962
Site: V K Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Ma lathion
Samples: Urine
Collection: July 20 PM, Post-exposure
Metabolites: Alkyl Phosphates and Ma lathion Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
Children
Vol.^ml
Pesticide
Equivalent,
ng/ml
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
118
124
172
190
84
150
117
98
194
236
22
529
2178
4529
365
445
2912
2996
5091
4081
Malathion
Eg. Wt.yq
30
66
375
861
31
67
301
294
988
963
cm
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
Vol..ml
16
59
234
SO
44
90
110
78
70
120
Pesticide
Equivalent, Ma lathion
ng/ml Eg. Wt.pg
1023
.78
0
46
33
1116
388
308
577
0
16
5
0
2
1
100
43
24
40
0
Mean
399
Mean
23
&M«an * 376
t « 2.99
d.f. « 18
P - <0.01 **
Ih7284d«
146
-------
815
Table D-3
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: V K Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Ma lathion
Samples: Urine
Collection: July 21 AM, Pre-exposure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradnay and Shafik, 1977
Miami AP Procedure, 1980
Adults
Children
HOD
HAH
JAM
JYH
JSH
LIH
TAH
LDH
LVH
RVH
220
96
126
230
72
376
156
170
169
232
Pesticide
Equivalent,
ng/rnl
139
478
972
772
750
2001
592
1562
4353
4033
Malathion
Eg. Wt.yg
31
46
122
178
54
752
92
266
736
936
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
Vol. ..ml
60
64
286
60
68
126
130
102
66
120
Pesticide
Equivalent,
ng/ml
1344
1223
600
350
22
68
765
70
0
702
Malathion
Eg. *t.yg
81
78
172
21
1
9
99
7
0
84
Mean • 321
Mean - 55
AMean • 266
t " 2.39
d.f. » 18
P - <0.05 *
lh72B4dw
147
-------
816
Table D-4
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: V K Field
Crop: Blueberries, Study II
Study Date: July 21, 1962
Pesticide: Malathion
Samples: Urine
Collection: July 21 PM, Post-exposure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradnay and Shafik, 1977
Miami AP Procedure, 1980
Adults
Children
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Vol..ml
154
130
204
196
178
208
106
142
218
144
Pesticide
Equivalent,
ng/ml
46
264
442
2551
683
310
1255
621
2394
2742
Ma lath ion
Eg. wt.yg
7
34
90
500
122
64
133
86
522
395
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
Vol.
12
84
58
60
70
96
104
100
120
120
Pesticide
Equivalent,
ml ng/ml
! 265
( 331
I 54
) 315
) 131
1 653
> 601
) 1460
) 427
) 420
Ma lath ion
Eq. Wt.yg
3
28
3
19
9
64
63
146
51
50
Mean
196
Mean
46
AMean - 150
t - 2.34
d.f. " 16
P - <0.05 *
1h7284dw
-------
Table D-5
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 19B2
Site: V K Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Malathion
Samples: Urine
Collection: July 22 AM, Pre-exposure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradway and Shafik, 197?
Miami AP Procedure, 1980
Adults
Pesticide
Equivalent, Malathion
Vol..ml ng/ml Eg. Wt.pg
91
57
84
70
120
95
17
57
82
106
Children
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
156
130
246
232
260
294
54
162
122
208
583
440
342
300
463
323
324
351
672
508
CIH
Ctrl
BRB
MEB
.PAB
AMD
JEK
DEL
BVK
JVK
Vol..ml
94
64
220
32
144
266
96
90
474
66
Pesticide
Equivalent, KB lath ion
ng/ml Eg. Wt.yg
1062
576
171
104
106
255
922
347
284
651
100
48
38
3
15
68
89
31
135
56
Mean
78
Mean
58
AMean
20
t • 1.23
d.f.
16
<0.3
1h7264d«
149
-------
818
Table D-6
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: V K Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Malathion
Samples: Urine
Collection: July 22 PK, Post-exposure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradnay and Shafik, 1977
Miami AP Procedure, 1980
Adults
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
156
196
104
245
180
98
234
206
126
172
Pesticide
Equivalent,
ng/ml
387
1371
1111
745
409
834
320
639
1903
1000
Malathion
Eg. *t.yg
60
269
116
183
74
82
75
132
240
172
Children
Pesticide
Equivalent, Malathion
Vol..ml ng/ml Eg. Wt.Ug
131
36
62
53
45
126
71
0
53
95
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
^•^•^W^B^M^
124
60
245
210
170
190
102
38
93
1BO
1057
602
252
253
263
662
700
0
569
528
Mean • 140
Mean
67
AMean - 73
2.75
d.f. « 18
<0.02
1h?284d«r
150
-------
Table D-7
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: V K Field
Crop: Blueberries, Study III
Study Date: July 23, 1982
Pesticide: Malathion
Samples: Urine
Collection: July 23 AM,.Pre-exposure
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
Pesticide
Equivalent, Malathion
Vol.,m1 ng/ml Eg. Wt.yg
233
161
125
93
86
35
73
100
1*5
143
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
182
252
340
270
285
128
130
202
174
214
1280
639
369
346
301
271
560
497
636
670
Children
Pesticide
Equivalent, Malathion
Vol.jml ng/ml Eg. Wt.Ug
64
112
13
33
8
304
44
2*
37
62
CIH
CLH
BRB
MEB
PAB
AtC
JEK
DEL
BVK
JVK
126
124
254
42
64
246
140
98
360
124
507
901
52
796
131
1235
317
249
103
504
Mean
119
Mean
70
A»ean « 49
t « 1.50
d.f.
18
<0.2
Ih7264d»
151
-------
820
Table D-8
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1982
Pesticide: Methiocarb (Hesurol)
Samples: Urine
Collection: AM 7/20/82 Pre-exposure
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
200
84
44
184
80
90
56
104
118
192
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. Ug
Children
Methiocarb Phenol
0
0
0
0
0
0
0
0
130
70
0
0
0
0
0
0
0
0
15
13
Equiv.
Mt. UQ
0
0
0
0
0
0
0
0
21
IB
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
46
77
106
72
144
300
82
96
344
46
0
60
0
0
0
0
0
70
0
0
0
5
0
0
0
0
0
7
0
0
0
6
0
0
0
0
0
9
0
0
1h7284dw
152
-------
Table D-9
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: VK Field
Crop: Blueberries, Study I
Study Date: July 20, 1962
Pesticide: Methiocarb (Mesurol)
Samples: Urine
Collection: PH 7/20/B2
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
Urine
Vol . ml
118
124
172
190
84
150
117
98
194
236
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. pg
.Children
0
0
0
70
0
0
0
0
0
0
0
0
0
13
0
0
0
0
0
0
Equiv.
Wt. ug
0
0
0
18
0
0
0
0
0
0
cm
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
16
59
234
50
44
90
110
78
70
120
Methiocarb Phenol
Cone.
ng/ml Wt. uq
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Equiv
•t. in
0
0
0
0
0
0
0
0
0
0
Ih7284dw
153
-------
Table D-10
YOUTH IN AGRICULTURE STUDY
I OKA PHAP, 1982
822
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Methiocarb (Hesurol)
Samples: Urine
Collection: AM 7/21/82
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
220
96
126
230
72
376
156
170
169
232
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. Ug
.Children
Methiocarb Phenol
0
0
50
0
0
0
0
0
100
0
0
0
6
0
0
0
0
0
17
0
Equiv.
»t. UQ.
0
0
8
0
0
0
0
0
23
0
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
60
64
286
60
68
126
130
102
86
120
0
0
0
50
0
50
0
0
0
0
0
0
0
3
0
6
0
0
0
0
0
0
0
4
0
8
C
0
0
C
Ih728
-------
Table D-11
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
823
Site: VK Field
Crop: Blueberries, Study II
Study Date: July 21, 1982
Pesticide: Methiocarb (Mesurol)
Samples: Urine
Collection: PM 7/21/82
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
Subject
HOD
HAH
JAH
'JYH
JSH
LIH
TAH
LDH
LVH
RVH
Urine
154
130
204
196
178
208
106
142
218
144
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. Uq
0
0
0
140
0
0
0
0
50
70
0
0
0
27
0
0
0
0
11
10
Children
Methiocerb Phenol
Equiv.
Wt. UQ
0
0
0
37
0
0
0
0
15
14
Subject
CIH
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
Urine
Vol. ml
12
84
58
60
70
98
104
100
120
120
Cone.
ng/ml
50
0
0
0
0
0
0
0
0
0
»t. U9
1
0
0
0
0
0
0
0
0
0
Equiv,
ftj
1
0
0
0
0
0
0
0
0 i
0
Ih7284dw
155
-------
824
Table D-12
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1962
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Methiocerb (Mesurol)
Samples: Urine
Collection: AM 7/22/82
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
HOC
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
156
130
2i»6
232
260
294
54
162
122
206
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. Uq
Children
70
0
0
0
0
0
0
100
0
11
0
0
0
0
0
0
12
0
Equiv.
Wt. us
15
0
0
0
0
0
o'
16
0
Urine
Subject Vol. ml
cm
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
94
84
220
32
144
266
96
90
474
86
Methiocarb Phenol
Cone.
no/ml Wt. Ug
150 12
0 0
120 26
0 0
0 0
80 21
60 5
0 0
0 0
0 0
Equi-
Wt.
17
C
35
C
C
Ih7284dw
156
-------
Table D-13
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
825
Site: VK Field
Crop: Blueberries, Study 111
Study Date: July 22, 1962
Pesticide: Methiocarb (Mesurol)
Samples: Urine
Collection: PM 7/22/82
Metabolite: Methiocarb phenol
Method: Sullivan and Shefik (unpubl)
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
156
196
104
245
180
98
234
206
126
172
Adults
Methiocarb Phenol
Cone.
nq/ml Wt. Ug
Children
0
0
0
0
0
0
0
0
110
90
0
0
0
0
0
0
0
0
14
15
Equiv.
Wt,
0
0
0
0
0
0
0
0
19
21
Methiocarb Phenol
Cone.
no/ml
CIH 124 80
CLH 60 0
BRB 245 0
MEB 210 0
PAB 170 0
AMD 190 0
JEK 102 70
DEL 38 0
BVK 93 0
JVK 180 0
10
0
0
0
0
0
3
0
0
0
Egul
Ih7284dw
157
-------
826
Table D-14
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Site: VK Field
Crop: Blueberries, Study III
Study Date: July 22, 1982
Pesticide: Methiocarb (Mesurol}
Samples: Urine
Collection: AM 7/23/82 No exposure
Metabolite: Methiocarb phenol
Method: Sullivan and Shafik (unpubl)
HOD
HAH
JAH
JYH
JSH
LIH
TAH
LDH
LVH
RVH
182
252
340
270
285
126
130
202
174
214
Adults
Methiocarb Phenol
Cone.
ng/ml Wt. yg
Children
Methiocarb Phenol
0
0
0
0
0
0
0
0
70
0
0
0
0
0
0
0
0
0
12
0
Equiv.
»t. yg
0
0
0
0
0
0
0
0
16
0
cm
CLH
BRB
MEB
PAB
AMD
JEK
DEL
BVK
JVK
126
124
254
42
64
246
140
96
360
124
0
0
0
0
0
0
90
0
0
0
Wt. yg
0
0
0
0
0
0
13
0
0
0
1h7284dt»
158
-------
TABLE 0-15
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
827
Site: CC-1 Field
Crop: Blueberries, Study IV
Study Date: July 19, 1982
Pesticide: Halathion
Samples: Urine
Collection: 7/19/82 AK, Pre-work
Metabolites: Alkyl Phosphates and Malathion Acios
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
Children
Subject
MAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
Vol., ml
320
175
195
95
180
360
75
280
210
Ma lath ion
Equivalent
Cone.
ng/ml
251
654
168
217
251
168
141
292
324
Ma lath ion
Ma lath ion
•Equivalent
Equivalent
wt.. u^
60
114
33
21
45
60
11
82
68
Subject
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
Vol., ml
355
135
255
355
165
180
300
190
175
Cone.
ng/ml
175
216
33
1092
2495
273
444
666
308
Malathion
Equivalent
Wt., ug
62
29
8
388
412
49
133
126
54
Mean
57
Mean
140
AMean « 83.0
t - 1.59
d.f. « 16
P - <0.2
Ih7284dw
159
-------
TABLE D-16
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
828
Site: CC-1 Field
Crop: Blueberries, Study IV
Study Date: July 15, 1982
Pesticide: Ms lathion
Samples: Urine
Collection: 7/19/82 PK
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
WAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIG
Vol.. ml
220
200
94
282
224
345
174
252
98
Malathion
Equivalent
Cone.
ng/ml
178
332
170
22
HI
0
0
70
231
Mean «
Malathion
Equivalent
39
66
16
6
32
0
0
18
22
22
Subject Vol.. ml
Children
Malathion
Equivalent Malathion
Cone. Equivalent
ng/ml Wt.. yg
FRH
EGJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
178
94
81
208
136
222
126
118
132
659
77
84
•0
1972
160
332
198
0
Mean
117
7
7
0
268
35
42
23
0
55
AMean - 33
t « 1.08
d.f. - 16
P « <0.3
1h7284dw
160
-------
TABLE D-17
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1962
829
Site: CC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1962
Pesticide: Malathi on
Samples: Urine
Collection: 7/20/82 AM, Pre-work
Metabolites: Alkyl Phosphates and Ma lath(on Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
MAC
KAY
JAM
JIY
MAT
DAC
EAC
JU
BIC
Vol.. ml
205
200
245
335
220
310
245
75
350
Ma lathi on
Equivalent
Cone.
ng/ml
185
418
344
202
398
228
223
162
280
Mean «
Ma lath ion
Equivalent
Wt.. U9
38
84
84
68
68
71
55
12
98
66
Children
Ma lathion
Equivalent Ma lath ion
Cone. Equivalent
ng/ml Wt.. U9
FRH
ECJ
RMC
AMC
TIS
DES
70S
ROC
CHC
200
160
205
300
225
290
290
175
210
459
224
276
450
843
118
267
578
175
Mean
92
36
57
135
190
34
77
101
37
84
AMean - 18
t - 0.90
d.f. » 16
P « <0.4
lh72B4dw
161
-------
830
TABLE D-18
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
Site: GC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1982
Pesticide: Malathion
Samples: Urine
Collection: 7/20/82 PM
Metabolites: Alky] Phosphates and Ma lathion Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, I960
Adults
Children
NAG
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
Vol., ml
116
77
152
204
122
248
238
276
228
Malathion
Equivalent
Cone.
ng/ml
819
916
282
413
387
22
22
79
454
Mean •
Malathion
Equivalent
95
70
43
84
47
5
5
22
103
53
Vol., ml
Malathion
Equivalent
Cone.
ng/ml
Malathion
Equivalent
*t.. ug
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CMC
192
188
78
160
214
166
158
264
336
454
383
323
618
767
1481
348
647
131
Mean
87
72
25
99
164
246
55
171
44
107
AMean * 54.4
t « 2.0
d.f. « 16
P * <0.1
Ih7284dw
162
-------
TABLE D-19
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
831
Site: GC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1962
Pesticide: Malathi on
Samples: Urine
Collection: 7/21/82 AM, Pre-work
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradway and Shaflk, 1977
Miami AP Procedure, 1980
Adults
MAC
KAY
JAM
• JIY
MAT
DAC
EAC
JIJ
BIC
Vol.. ml
170
75
165
270
2
-------
TABLE D-20
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
832
Site: CC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1982
Pesticide: Malathion
Samples: Urine
Collection: 7/21/82 PM
Metabolites: Alkyl Phosphates and Malathion Acids
Method: Bradway and Shafik, 1977
Miami AP Procedure, 1980
Adults
WAG
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIG
Vol.. ml
200
no
190
235
185
305
260
150
80
Malathion
Equivalent
Cone.
ng/ml
567
283
53
46
934
0
0
0
147
Mean •
Malathion
Equivalent
113
40
10
11
173
0
0
0
12
40
FRH
ECJ
RMG
AMC
TIS
OES
TOS
ROC
CHC
Vol.. ml
180
130
130
145
100
90
200
135
90
Children
Malathion
Equivalent Malathion
Cone. Equivalent
ng/ml Wt.. yig
2070
170
22
122
1139
339
22
318
652
Mean
373
22
3
18
114
30
4
43
59
74
AMean - 34
t « 0.77
d.f. « 16
P « <0.5
Ih7284dn
164
-------
833
Site: CC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1982
Pesticide: Methiocarb (Mesurol)
TABLE D-24
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
Samples: Urine
Collection: 7/20/82 AM, Pre-work
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik (unpubl.)
Adults
Methiocerb Phenol
Subject
WAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
Vol.
ml
205
200
245
335
220
310
245
75
350
Cone.
ng/ml
60
60
120
0
230
0
50
60
60
Wt.; yg
12
12
29
0
51
0
12
5
21
Methiocarb
Equivalent
Wt.; U9
16
16
39
0
68
0
16
7
28
Children
Methiocarb Phenol
Subject
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
Vol.
ml
200
160
205
300
225
290
290
175
210
Cone.
ng/ml
180
112
0
0
0
0
210
90
60
lethiocarb
Equivalent
*t.; yg
36
18
0
0
0
0
61
16
13
«t.; yg
48
24
0
0
0
0
82
21
17
Mean
21
Mean
21
AMean - 0
t «
d.f. «
P -
1h7264dn
168
-------
TABLE D-25
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1962
.834
SUe: CC-1 Field
Crop: Blueberries, Study V
Study Date: July 20, 1962
Pesticide: Methiocarb (Mesurol)
Samples: Urine
Collection: 7/20/82 PM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik (unpubl.)
Adults
nethiocarD
Subject
NAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
Vol.
ml
116
77
152
204
122
248
238
278
228
Cone.
ng/ml
210
180
280
80
150
180
220
0
320
Equivalent
Wt.; ug
24
14
43
16
18
45
52
0
73
Wt.; UQ
32
19
58
21
24
60
70
0
98
Vol.
Subject ml
Children
Methiocarb Phenol
*t.; UQ
FRH
ECJ
RMC
AMC
TIS
OES
TOS
ROC
CHC
192
188
78
160
214
166
158
264
336
0
270
130
160
120
190
90
130
0
0
51
10
26
26
32
14
34
0
Mean
42
Mean
Methiocarb
Equivalent
Wt.; Ug
0
68
13
35
35
43
19
46
0
29
AMean - 13
t « 1.06
d.f. " 16
P * <0.40
Ih7284dw
169
-------
835
TABLE D-26
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
Site: CC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1982
Pesticide: Methiocarb (Mesurol)
Samples: Urine
Collection: 7/21/82 AM, Pre-work
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik (unpubl.)
Adults
Methiocarb Phenol
Vol.
Subject ml
NAG
KAY
JAM
JIY
MAT
DAG
EAC
JIJ
BIC
170
75
185
270
2
-------
TABLE D-27
YOUTH IN AGRICULTURE STUDY
IONA PHAP 1962
836
Site: CC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1962
Pesticide: Methiocarb (Hesurol)
Samples: Urine
Collection: 7/21/82 PM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik (unpubl.)
Vol.
Subject ml
MAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
200
140
190
235
185
305
260
150
80
Adults
Methiocarb Phenol
Cone.
no/ml Wt.; yig
12
7
10
19
57
40
55
0
27
Mean
Methiocarb
Equivalent
16
9
13
26
76
54
74
0
36
34
Vol.
ml
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
180
130
130
145
100
90
200
135
90
470
380
260
0
460
140
0
0
240
Children
Methiocarb
Cone.
ng/ml »
470
380
260
0
460
140
0
0
240
Phenol
»t.; UQ
85
49
34
0
46
13
0
0
22
Mean
Methiocarb
Equivalent
Wt.; ug
114
66
46
0
62
17
0
0
30
37
AMean * 3
t « 0.21
d.f. « 16
P - 0.50
1h7284dw
171
-------
TABLE D-2P
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
837
Site: CC-1 Field
Crop: Blueberries, Study VI
Study Date: July 21, 1982
Pesticide: Methiocarb (Hesurol)
Samples: Urine
Collection: 7/22/82 AM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik (unpubl.)
NAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
220
85
170
340
205
350
100
145
235
Adults
Methiocarb
Cone.
ng/ml <
200
50
0
0
250
100
60
0
190
Phenol
"t.; Vg
44
4
0
0
5
35 .
6
0
45
Methiocarb
Equivalent
59
5
0
0
7
47
8
0
60
Children
Methiocarb Phenol
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
Vol.
ml
240
225
180
270
280
150
250
135
255
Cone.
ng/ml
230
60
0
50
180
80
270
120
»t.;
55
11
0
14
27
20
36
31
Mean
21
Mean
Methiocarb
Equivalent
Wt.s U9
74
15
0
19
36
27
46
42
33
AMean « 12
t « 0.99
d.f. • 15
P - <0.4
Ih7284dw
172
-------
838
TABLE D-29
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 19B2
Site: CC-2 Field
Crop: Blueberries, Study Vtl
Study Date: July 27, 1982
Pesticide: Methiocarb
Samples: Urine
Collection; 7/27/82 AM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Adults
Methiocarb Phenol
Conc.t
3/ml Wt.; Uq
MAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
JID
AND
260
335
US
267
3<*5
225
220
270
265
150
US
0
0
81
Q
0
0
0
0
0
0
0
0
0
11.7
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
0
0
15.7
0
0
0
0
0
0
0
0
Children
Methiocarb Phenol
Vol.
ml
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
JAH
LAW
190
230
190
390
215
252
270
235
285
-
-
0
60
0
0
-
Trace
0
0
0
-
-
0
13.8
0
0
0
0
0
Methiocarb
Equivalent
0
16.5
0
0
0
0
0
t Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
Ih726
-------
TABLE D-30
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1962
839
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 27, 1982
Pesticide: Metro ocarb
Samples: Urine
Collection: 7/27/82 PM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Vol.
Subject ml
Adults
Methiocarb Phenol
WAG
KAY
JAM
JIY
MAT
DAG
EAC
JU
BIG
JID
AND
260
HO
H5
95
300
225
205
160
225
-
-
0
0
0
0
60
0
0
0
0
-
-
0
0
0
0
2k
0
0
0
0
Methiocarb
Equivalent
*t.; ug
0
0
0
0
32.2
0
0
0
0
Children
Methiocarb Phenol
Subject
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
JAH
LAH
Vol.
ml
250
230
10S
390
215
165
255
125
240
-
.
Conc.t
ng/ml
0
0
Trace
0
0
0
0
0
0
-
-
wt.s ug
0
0
0
0
0
0
0
0
.
-
netni ocarb
Equivalent
Wt.: ug
0
0
0
0
0
0
0
0
-
.
Specimens denoted - not analyzed.
Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as trace.
Ih7284d»r
174
-------
TABLE D-31
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
840
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 26, 1982
Pesticide: Methiocarb
Samples: Urine
Collection: 7/28/82 AM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Vol.
Subject ml
Adults
Methi'oearb Phenol
»t.; wg
VAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
JID
AND
268
110
158
282
360
300
216
252
206
305
215
Trace
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
*t.; yg
0
0
0
0
0
0
0
0
0
0
Children
Me'thiocerb Phenol
Vol.
ml
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
JAM
LAH
180
165
182
326
192
202
338
260
222
252
208
0
0
0
0
Trace
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
*t.; uq
0
0
0
0
0
0
0
0
0
0
t Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
lh7284dH
175
-------
8A1
TABLE D-32
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 28, 1982
Pesticide: Methtocarb
Samples: Urine
Collection: 7/26/82 PM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Adults
Methiocarb Phenol
Subject
NAG
KAY
JAM
JIY
MAT
DAG
EAG
JIJ
BIG
JID
AND
Vol.
ml
272
128
214
220
242
150
150
314
214
206
156
Conc.t
ng/ml
0
0
0
0
0
0
0
0
0
0
0
ethiocerb
Children
Methioearb Phenol
Equivalent
*t.; yg
0
0
0
0
0
0
0
0
0
0
0
Wt.j yg
0
0
0
0
0
0
0
0
0
0
0
Subject
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHG
JAH
LAW
Vol.
ml
220
144
232
294
136
210
158
88
84
230
194
Conc.t
ng/ml
0
0
0
0
0
0
0
0
0
0
0
*t.; ug
0
0
0
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
Wt.; ug
0
0
0
0
0
0
0
0
0
0
0
t Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
Ih7284dw
176
-------
TABLE D-33
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
842
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 29, 1982
Pesticide: Methiocarb
Samples: Urine
Collection: 7/29/82 AM
Metabolites: Methiocarb.phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Adults
Methiocarb Phenol
Subject
WAG
KAY
JAM
JIY
MAT
OAC
EAC
JIJ
BIC
JID
AND
Vol.
ml
242
196
380
256
230
355
254
325
206
270
176
Conc.t
ng/ml
0
0
0
0
0
0
0
0
0
0
0
ethiocarb
Children
Methiocarb Phenol
Equivalent
Wt.; U9
0
0
0
0
0
0
0
0
0
0
0
*t.; yg
0
0
0
0
0
0
0
0
0
0
0
Subject
FRH
EGJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
JAH
LAH
Vol.
ml
168
214
180
250
222
315
212
224
268
113
168
Conc.t
ng/ml
0
0
0
0
0
0
0
0
0
0
0
"t.; Ug
0
0
0
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
Wt.; Ug
0
0
0
0
0
0
0
0
0
0
0
t Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
Ih7284dw
177
-------
TABLE D-34
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1962
843
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 29, 1982
Pesticide: Methiocarb
Samples: Urine
Collection: 7/29/82 PM
Metabolites: Methiocarb phenol
Method: Sullivan and Shefik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Adults
Methiocarb Phenol
Subject
WAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIC
JID
AND
Vol.
ml
255
178
214
308
210
254
325
184
184
268
176
Conc.t
ng/ml
Trace
0
90
0
195
0
0
Trace
0
Trace
0
Methiocarb
Equivalent
Wt.: ug
0
19.3
0
40.9
0
0
0
0
Wt.; pg
0
25.8
0
55.3
0
0
0
0
Subject
FRH
ECJ
RMC
AMC
TIS
DES
TOS
ROC
CHC
JAH
LAH
Vol.
ml
112
46
180
198
118
154
255
185
125
150
108
Children
Methiocarb Phenol
Conc.t
ng/ml
130
0
Trace
0
90
0
0
0
0
0
0
Wt.; pg
14.6
0
0
10.6
0
0
0
0
0
0
Methiocarb
Equivalent
Wt.; UP
19.5
0
0
14.2
0
0
0
0
0
0
Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
1h7284dn
178
-------
TABLE D-35
844
YOUTH IN AGRICULTURE STUDY
IOWA PHAP 1982
Site: CC-2 Field
Crop: Blueberries, Study VII
Study Date: July 30, 1962
Pesticide: Methiocarb
Samples: Urine
Collection: 7/30/82 AM
Metabolites: Methiocarb phenol
Method: Sullivan and Shafik
Carbamate Phenol Method (unpubl.)
(See Analytical Methods)
Vol.
Subject _ml
Adults
Methiocarb Phenol
Wt.;
MAC
KAY
JAM
JIY
MAT
DAC
EAC
JIJ
BIG
JID
AND
202
257
210
260
285
235
297
253
230
290
64
Trace
0
0
0
Trace
Trace
0
0
Trace
0
0
0
0
0
0
0
0
0
Methiocarb
Equivalent
*t.; Wq
0
0
0
0
0
0
0
Children
Methiocarb Phenol
Subject
FRH
EGJ
RMC
AMG
TIS
DES
TOS
ROC
CHC
JAH
LAH
Vol.
ml
194
126
196
204
190
182
325
211
132
150
160
Conc.t
ng/ml
90
0
Trace
0
Trace
0
0
0
0
0
0
Wt.; uq
1.7
0
0
0
0
0
0
0
0
Methiocerb
Equivalent
23.4
0
0
0
0
0
0
0
t Minimum detection limit for this method is 50 ng/ml.
Peaks representing less than this are recorded as Trace.
1h72B4dw
179
-------
Appendix £
Laboratory Quality Control for
Blueberry Harvester Study
Table of Contents
845
Field Quality Control Determinations
Summary of Field Spike and Blank Data
Field Spike and Blank Data - Individual
Determinations
Table
E-l
E-2
Laboratory Quality Control Determinations Table
Unmetabolized Pesticides
Summary of Recoveries from Spiked Matrices-
Malathion E-3
Recoveries of Malathion from Spiked Matrices-
Individual Determinations E-4
Summary of Recoveries from Spiked Matrices-
Guthion E-5
Recoveries of Gution from Spiked Matrices-
Individual Determinations E-6
Summary of Recoveries from Spiked Matrices-
Methiocarb E-7
Recoveries of Methiocarb from Spiked Matrices-
Individual Determinations E-8
Summary of Recoveries from Spiked Matrices-
Captafol E-9
Recoveries of Captafol from Spiked Matrices-
Individual Determinations E-10
Pesticides Apparently Detected in Laboratory
Blanks E-ll
Precision Studies for Reroducibility of
Pesticide Measurements E-12
Ih7384dw
180
-------
846
Urinary Pesticide Metabolites
Summary of Recoveries of Pesticide Metabolites
from Urine Spiked in the Laboratory E-13
Recoveries of Alkyl Phosphates from Spiked
Urine E-14
Recoveries of Malathion Monocarboxylic Acid
from Spiked Urine E-15
Recoveries of Malathion Di-carboxylic Acid
from Spiked Urine E-16
Recoveries of Methiocarb Phenol from Spiked
Urine E-17
Precision Study for Reproducibility of Urinary
Alkyl Phosphate Measurements E-18
181
Ih8284dw
-------
Tabe E-1
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
Summary of Field Quality Control Samples
Coefficient
Highest
00
Matrix
Gauze
Cellulose
Pads
Gloves
Chemical
Malathlon
Methlocarb
Captafot
Guthion
Matathion
Methlocarb
Captafol
Guthion
Malathion
Methlocarb
Captafot
Spike or
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Number
of Tests
16
13
39
38
41
38
16
13
19
18
39
36
JJ
19
18
10
7
11
8
12
9
Spiking
Level , pg
10
0
to
0
10
0
10
0
to
0
10
0
10
0
10
0
10
0
10
0
10
o
Standard
Mean Deviation
6.9 2.9
5.5 . 1.9
3.5 1.5
7.1 1.3
7.3 2.7
5.8 2.7
3.1 2.5
7.9 3.0
4.4 3.2
2.9 2.7
2.2 1.6
of
Variation, % Range
42% 1.8-12.0
34% 1.1- 8.7
42% 0.6- 9.1
18% 4.5- 8.7
37% 1.0-11.1
47% 0.0- 9.4
79% 0.4-14.0
38% 3.3-13.3
75% 1.8-12.9
97% 0 - 6.5
78% 0.3- 5.5
Average
Recovery
69%
55%
35%
71%
73%
58%
31%
79%
44%
29%
27%
Zero Blanks
Total Blanks
7/13
31/38
21/38
13/13
11/18
34/36
28/41
14/18
5/7
7/8
*/9
Positive
Blank
1.7
1.7
0.2
None
4.7
0.9
0.2
0.2
8.6
0.3
19. O
CO
-------
Table E-1 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
Summary of Field Quality Control Samples
Coefficient
Highest
Matrix Chemical
Cloves Cuthlon
Resin- Malathlon
Personal Air
Samplers
Hethlocarb
(£ Captafol
Cuthlon
Resin- Malathion
High Volume
Air Samplers
Hethlocarb
Captafol
Cuthlon
Filter-High Malathlon
Volume Air
Samplers
Methiocarb
Spike or
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Number
of Tests
10
10
10
9
14
14
13f
"
10
9
5
5
9
8
9
9
5
5
19
16
23
19
Spiking Standard of
Level. |Jg Mean Deviation Variation, %
10 5.8 1.7 30%
0
10 6.1 2.6 43%
0
10 3.6 3.3 91%
0
10 5.8 2.5 43%
0
10 6.5 1.9 30%
0
10 3.3 3.2 97%
0
10 4.6 2.6 56%
0
10 6.5 2.2 34%
0
10 7.0 4.2 60%
0
10 4.7 3.4 73%
0
10 6.4 2.6 41%
0
Average Zero Blanks
Range Recovery Total Blanks
2.5- 8.5 58%
9/10
1.5-10.1 61%
9/9
0.6-12.2 36%
14/14
1.9-10.4 58%
13/14
2.0- 9.2 65%
9/9
0 - 7.8 33%
4/5
1.7- 8.9 46%
8/8
1.4- 8.8 65%
5/9
0 -10.0 70%
5/5
0.4-16.1 47%
0/16
1.0- 9.4 6<»%
13/19
Positive
Blank
0.3
None
None
0.02
None
0.2
None
9.4
None
0.3
0.4
CO
-------
Table E-1 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
Sunmary of Field Quality Control Samples
Coefficient
Highest
oo
Matrix
Filter-High
Volume Air
Samplers
Foliage
Samples
Chemical
Captafol
Guthfon
Malathion
Methlocarb
Captafol
GutMon
Spike or
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Spike
Blank
Number
of Tests
23
20
19
16
2
2
7
6
6
*
*
2
Spiking
Level, im
10
0
to
0
10
0
10
0
10
0
10
0
Mean
O.«i
7.2
1.6
0.5
3.9
0.2
Standard
Deviation
0.8
1.8
1.3
0.5
3.8
0.1
of
Variation, *
205*
25*
85*
108*
98*
65*
Range
0 - 3.1
3.6-11.0
0.6- 1.3
0.2- 1.5
0.3- 8.7
0 - 0.2
Average
Recovery
4*
72*
16*
5*
39*
2*
Zero Blanks
Total Blanks
15/20
11/16
1/2
4/6
2/«
1/2
Positive
Blank
0.3
0.1
2.1
0.7
3I».2
.005
t An additional field spike yielded a value of 106 pg. This was probably due to Inadvertent contamination of the sample at some
stage of collection or analysis.
CD
-------
Table E-2
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intra Laboratory Quality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
850
Pesticide: Malathion
Spiking Level : 10
Study Spike
Number
Cauze 1 2.7
6.9
6.6
8.1
10.9
Mean 7.0
II 12.0
7.3
5.1
8.2
-__
Mean 8.2
III 6.9
7.9
6.<«
8.3
9.3
Mean 7.8
IV 2.0
1.8
-
us
Blank
0.2
-
-
-
-
0.2
1.0
0.7
1.0
1.6
1.7
1.5
0
0
0
0
0
0
0
0
-
Methiocarb
10
Spike
5.5
5.0
4.7
3.4
3.6
4.4
5.5
3.7
5.5
4.4
4.8
4.8
7.5
8.4
7.3
7.1
7.4
7.5
6.4
1.1
8.5
ug
Blank
0
0
0
0
.
~~0~
0
0
0
0
0
0
0.2
0.1
0
0
0
0.1
0
0
-
Captafol
10
Spike
3.6
4.9
4.6
5.4
9.1
5.5
1.6
1.7
1.6
0.6
-
1.4
3.5
4.5
4.2
4.2
4.2
4.1
2.3
2.1
-
ug
Blank
0
.
-
.
.
0
0 .
0
0
0
0
0
0
0
0
0
0
0
0.0
0.0
-
Cuthion
10
Spike
5.6
6.6
6.9
7.B
8.7
7.1
8.0
6.0
7.2
7.7
-
TTF
7.0
8.5
7.7
8.5
7.5
7.6
4.5
4.8
-
ug
Blank
0
-
-
-
.
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
Mean 1.9
5.3
2.2
Mean
VI
Mean
Specimens designated - were not analyzed.
4.6
1.4
5.7
5.7
6.6
.
4.9
6.7
7.7
8.7
5.2
3.S
6.4
1.7
0.3
0.1
0.3
0.7
0.6
0
0
0
0
0
0
3.1
2.7
3.2
3.0
-
3.0
3.6
1.5
1.5
4.3
1.7
2.5
0.1
0.0
0.0
0.0
0.1
0
0.1
0
0
0
0
0
lh73B4dw
185
-------
Table E-2 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intra Laboratory Quality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
85
Pesticide:
Spiking Level:
Study
Number
Cauze VII
Melathion
10 yg
Spike Blank
Mean
VIII
Mean
IX
Cellulose
Pad
Mean
7.4
7.7
7.2
7.1
6.8
Mean 7.2
It
Mean
III
Mean
7.5
9.6
8.1
8.3
11.1
6.9
8.8
9.9
7.9
9.0
8.4
8.6
4.7
4.7
0
0
0.3
0
0.2
0.1
0
0.5
0.2
0.1
0.1
0.2
Methiocarb
10
Spike
6.7
4.7
6.8
7.2
6.7
6.4
5.4
6.8
ITT
4.1
7.3
4.6
1.7
3.3
4.2
5.3
0.4
5.3
5.6
0.5
3.4
7.1
4.9
6.6
5.6
7.1
6.3
7.2
7.9
7.3
7.1
7.9
7.5
P9
Blank
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
-
-
0
0
0
0
0
0
0
0
0
0.4
0
0.9
0.3
Captafol
10
Spike
3.6
4.5
3.7
3.3
3.2
3.7
5.1
4.0
3.0
4.3
4.4
4.2
3.1
4.0
3.3
3.8
3.3
3.5
4.5
5.7
5.2
5.7
6.8
5.6
5.0
5.0
5.0
5.0
6.7
5.3
3.6
3.0
2.6
2.7
2.5
2.9
US
Blank
0.2
0.1
0.1
0
0.0
0.1
0.1
0.1
0.1
0.1
0
0.1
0
0
0
0
0
0
0
-
-
-
.
0
0
0
0
0
0
0
0
0.2
0
0
0.1
0.1
Cuthion
10
Spike
.
-
-
-
-
.
-
-
-
-
.
-
-
-
-
7.8
7.5
7.2
6.9
6.9
7.3
12.5
11.9
11.7
12.5
13.3
12.4
7.5
6.9
7.5
6.9
5.6
6.9
Mg
Blank
_
-
-
-
-
.
-
-
-
-
.
-
-
-
-
0
-
-
-
-_
0
0.2
0.2
0
0
0.1
0.1
0
0.1
0
0
0
0
Specimens designated - were not (nalyzed
Ih7384dw
-------
Table E-2 (Cont'd)
852
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1962
Intra Laboratory Duality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
Pesticide:
Spiking Level:
Study
Mum
Cellulose IV
Pads
VI
VII
IX
iy
Kmr
per
Mean
Mean
Mean
1
II
Mean
M« lath ion
10 vg
Spike Blank
1.1 0
1.0 0
0
0
- 0
1.1 0
5.9 0
5.7 0
-
-
-
5.8 0
. .
.
-
-
-
• •
.
.
.
.
.
.
.
.
.
„
-
-
-
-
Methioearb
10 j
Spike
8.7
-
-
-
-
6.7
0
9.4
0
3.5
1.7
1.4
2.7
6.7
7.7
8.7
5.2
3.5
6.4
8.0
6.1
9.3
7.3
6.4
7.4
7.8
9.4
6.4
6.7
7.6
8.4
4.1
3.1
-
5.2
jg
Blank
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
0
0
0
0
0
-
0
0
0
0
0
0
0
0
0
0
-
0
Captafol
10
Spike
0.4
0.6
-
-
-
0.5
2.5
3.7
4.1
2.9
3.8
2.9
3.3
1.1
0.5
0.7
0.8
0.6
0.7
2.9
3.5
3.2
13.9
2.2
5.1
2.0
1.5
1.9
1.9
0.7
1.6
1.0
1.2
1.3
1.2
1.5
1.2
wg
Blank
0.0
0.0
0.0
0.0
0.0
0
0.0
OJO
0
0.0
0.0
0
0
o .
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.2
0
0
Cuthion
10 ug
Spike Blank
3.3 0
3.4 0
0
0
-_ 0
3.4 0
5.5 0
5.9 0
-
-
-
5.7 0
.
-
-
-
.
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Specimens designated - not analyzed
187
Ih7384dw
-------
Table E-2 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intre Laboratory Duality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
853
Pesticide: Melathion
Spiking Level : 10
Study Spike
Number
Cloves 1 4.6
4.7
Mean 4.7
II 3.1
3.0
Mean 3.1
III 1.9
1.8
Mean 1.9
IV 2.7
4.4
Mean 3.6
V 3.6
12.9
Mean 6.3
ug
Blank
6.6
0
4.3
0
-
0
.
^_
-
0
0
0
0
4.5
2.3
Methiocarb
10
Spike
5.2
6.5
5.9
3.1
5.5
4.3
5.8
4.4
5.1
0
0
0
0
0
Ug
Blank
0
0.3
0.2
0
-
0
_
•__
-
0
"~0~
0
0
0
Captafol
10
Spike
5.5
5.3
5.4
1.4
1.6
1.6
2.5
1.7
2.1
0.8
0.3
0.6
1.3
2.9
2.1
ug
Blank
0
0
0
0.2
-
0.2
_
-
-
0
0
0
19.0
11.0
15.0
Gutnion
10
Spike
7.5
e.s
6.0
5.6
6.6
6.3
6.1
4.8
5.5
5.7
6.6
6.3
2.5
3.9
3.2
ug
Blank
0
0
0
0
0
0
0
0
0
0.3
0
0.2
0
0
0
VI
VII
Mean
VIII
0.6
0
0.3
1.4
1.7
1.6
0.1
0.1
0.1
IX
Personal Air
XAD-4 Resin
1 10.1
10.0
Mean 10.1
II 5.3
5.2
Mean 5.3
0
0
0
0
0
0
4.6
4.7
4.7
3.5
3.2
3.4
0
0
0
0
0
0
10.4
9.4
9.9
.
-
0
0
0
-
9.2
8.7
9.0
6.2
5.8
6.0
0
0
m^^^m
0
0
0
••••^
0
Specimens designated - not analyzed
1h7384dw
186
-------
Table E-2 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intra Laboratory Quality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
854
Pesticide:
Spiking Level :
Study
Number
Personal Air III
XAD-* Resin
Mean
IV
Mean
V
Mean
VI
Mean
VII
Mean
VIII
Mean
IX
Mean
High Volume 1
Air Resin
Malathion
10 pg
Spike Blank
6.0 0
6.0 -
6.0 0
1.5 0
3.6 0
2.6 0
6.3 0
7.3 0
6.8 0
.
-
.
-
. .
-
.
-
5.3 0
-
Methiocarb
10 l
Spike
3.3
3.2
3.3
0.9
2.7
1.6
5.9
3.0
4.5
0.6
1.0
0.8
12.2
6.3
9.3
.
-
,
-
4.3
-
'9
Blank
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.
-
.
-
0
•
Captafol
10 l
Spike
-
-
106.0
5.5
55.8
5.5
6.8
6.2
2.1
1.9
2.0
6.4
8.7
7.6
4.9
5.0
5.0
5.2
4.3
4.8
6.5
•
jg
Blank
-
-
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-
Cuthion
10
Spike
6.7
7.5
7.1
2.0
6.6
4.3
6.3
6.7
6.5
.
-
.
-
.
-
.
-
6.3
-
ug
Blank
0
0
0
0
0
0
0
0
0
.
.
.
-
.
-
.
-
0
-
II
III
IV
Mean
0
1.7
1.6
1.7
0.2
0
0
0
5.9
8.9
3.4
3.2
3.3
0
0
0
0
1.4
7.7
8.3
8.0
0
0
0
0
0
9.6
10.0
9.B
0
0
0
0
Specimens designated - not analyzed
Ih7384dw
189
-------
Table E-2 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 19B2
Intra Laboratory Quality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
855
Pesticide:
Spiking Level:
High Volume
Air Resin
VI
VII
VIII
IX
High Volume
Air Filter
Mean
III
Us lath ion
10 ug
Spike Blank
7.8 0
Mean
16.1
4.5
4.7
3.8
4.0
3.7
8.1
4.7
3.9
5.5
5.0
5.4
5.0
5.3
3.2
3.4
TTi"
1.0
0.4
3.9
3.4
3.5
2.4
0.2
0.2
0.2
0.2
Methiocarb
10 pg
Spike Blank
1.7 0
3.4 0
8.4 0
2.2
3.3
7.8
6.4
8.6
8.5
7.3
1.1
8.4
8.8
6.7
6.3
7.2
6.2
6.6
9.4
6.7
7.4
7.3
6.8
2.9
1.0
2.7
5.2
3.7
0
0
0
0
0
0
0
0
0
0
0
0
0.4
0.3
0.4
0.3
0.14
0
0.1
Captafol
10 i
Spike
8.6-
7.7
5.4
6.3
6.1
0.0
0.4
0.0
3.1
0.1
0.9
0.0
0.9
0.1
2.6
0.0
0.7
0.0
0.2
0.0
0.0
"oTo
0.0
0.2
0.3
0.1
0.0
0.1
'9
Blank
0
0.1
0.2
9.4
0.4
0.0
0.3
0.2
0.3
0.2
0.2
0
0.2
0
0
0
0
0
0
0
0
0
0
0
-
-
.
0
Cuthion
1C
Spike
9.1
-
-
-
-
6.9
7.1
7.3
4.7
6.0
6.4
11.0
6.8
6.9
7.6
6.9
7.8
6.8
10.2
7.0
7.5
T9
5.7
3.6
8.1
8.0
8.6
6.6
ug
Blank
0
-
-
-
-
0
0.05
0
0
0
0
0
0
0
0
0
0
0.1
0.1
0.1
0.1
"oTT
0
0
-
-
-_
0
Specimens designated - not analyzed
1h7384dw
190
-------
Table E-2 (Cont'd)
YOUTH IK AGRICULTURE STUDY
Iowa PMAP, 19B2
Intra Laboratory Duality Control
Field Spike Recoveries of Pesticide Residues
Individual Determinations
856
Pesticide:
Spiking Level:
High Volume
Air Filter
Study
Number
VI
Melethion
10 ug
Spike Blank
Methiocarb
10 ug
Spike Blank
6.3
0.1
Captafol
10 ug
Spike Blank
0.4 0
Cuthion
10 Ug
Spike Blank
VI
8.5
0.1
VIII
0.2
IX
6.3
0.1 0
Foliage
I
II
III
IV
V
VI
VII
VIII
IX
2.5
0.6
0
.
2.1 0.2 0.0
0 1.5
0 0
0.6 0
0.2 0
0.2 0
0.9 0.7
0.3
-
0.5 0
-
3.3
•
6.5 3
-------
Table E-3
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
857
SUMMARY
Pesticide: Malathion
Methods: See Analytical Methods (Appendix 6)
Sample
Cellulose and
Gauze Pad
Nos. of
Spiked Spiking
Samples Level. U9
Recovered. W9
Recovery. %
20
1.5
1.0
0.001
Mean
17.32
1.21
0.56
0.00094
Standard
Deviation
6.16
0.22
0.29
0.00016
Mean
87
81
56
Standard
Deviation
31
15
29
16
Coefficient of
Variation, V
36
19
52
17
Cloves
3 20.0
3 0.001
8.67
0.00066
4.01
0.00006
43
66
20
7
46
11
Resin
20.0
21.05
2.71
106
13
13
Soil
10.0
13.05
7.64
131
76
59
lh73B4dn
192
-------
Table E-4
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
858
Pesticide: M«lathion
Method: See Analytical Methods (Appendix B)
Sample
Cellulose and
Gauze Pad
Spiking
Level. ug
20
Recovered, Recovery,
9.7
11.8
21.B
19.8
23.5
49
59
109
99
118
1.5
1.13
1.12
1.05
103
75
75
70
1.0
1.32
0.496
0.459
0.397
0.456
0.414
0.393
0.590
0.521
132
50
46
40
46
41
39
59
52
0.001
Cloves
Resin
I
20.0
I
0.001
20.0
0.00076
0.00104
0.00102
12.8
8.4
4.8
0.00069
0.00059
0.00071
19.8
24.8
18.5
21.1
76
104
102
64
42
24
69
58
71
99
124
93
106
Soil
20.0
10.0
21.4
6.9
3.2
3.6
16.6
11.8
14.6
18.0
15.8
27.0
107
69
32
36
166
118
146
180
156
270
-------
Table E-5
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
859
SUMMARY
Pesticide: Cuthion
Methods: See Analytical Methods (Appendix B)
Matrix
Cellulose and
Gauze Pad
Cloves
Resin
Soil
Nos. of
Spiked Spiking
Samples Level. yg
Recovery, yig
Recovery,
5
4
9
3
30.00
2.00
1.50
0.0015
3 30.00
3 1.50
4 30.00
6 15.00
3 10.00
Mean
21.56
1.71
0.91
0.00154
16.20
1.43
24.15
20.00
7.87
Standard
Deviation
5.92
0.16
0.25
0.00017
6.87
0.15
6.47
5.52
2.37
Jlean
72
66
61
103
61
96
81
133
79
Standard
Deviation
20
9
16
12
23
10
22
37
24
Variation.
2B
11
27
11
38
11
27
26
30
1h7384dw
194
-------
Pesticide: Cuthion
Table E-6
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Duality Control
Laboratory Spfke Recovery
Method: See Analytical Methods
860
Sample
Cellulose and
Gauze Pad
Spiking
Level. U9
30.00
Cloves
Resin
Foliage
Soil
2.00
1
1.50
0.0015
I
30.00
J
1.5
J
30.00
10.00
15.0
10.0
1
Recovered,
UQ
17.8
21.0
26.1
28.7
14.2
1.86
1.7*
1.80
1.44
1.380
0.817
0.717 '
0.877
0.785
0.831
0.623
1.059
0.926
0.00155
0.00171
0.00137
25.4
17.*
11.8
1.6
1.3
1.4
24.8
32.6
17.1
22.1
10.2
15.0
30.0
20.6
18.8
20.6
15.0
10.6
6.5
6.5
Recovery,
\
59
70
87
96
47
93
87
90
72
92
54
48
SB
52
55
42
71
62
103
114
91
85
58
39
107
87
93
83
109
57
74
102
100
200
137
125
137
100
106
65
65
Ih7384dw
195
-------
Table E-7
YOUTH IK AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
SUMMARY
Pesticide: Methiocarb
Methods: See Analytical Methods (Appendix B)
Matrix
Cellulose and
Cauze Pad
Cloves
NOS. OT
Spiked
Samples
4
4
16
4
3
7
3
10
2
Spiking
Level , lag
10.00
5.00
2.50
1.00
0.50
0.25
10.00
5.00
1.50
Mean
4.90
2.37
1.40
0.58
0.49
0.26
3.13
4.76
1.15
Standard
Deviation
0.55
0.26
0.55
0.13
0.10
0.12
1.59
1.36
0.07
Mean
49
47
56
58
99
105
31
95 '
76
Standard
Deviation
6
5
22
13
21
51
16
28
5
Co-efficient of
Variation, ^
11
11
39
22
21
48
52
29
6
Resin
(Personal Air)
Resin (High
Volume Air)
2
2
1
2.50
10.00
5.00
0.92
1.75
5.13
Class Fiber Filter
(High Volume Air)
Soil
3
6
1
1
1
2.50
10.00
5.00
2.50
1.25
0.25
1.88
6.16
2.38
2.43
1.13
0.16
0.12
0.35
0.34
3.15
1.64
36
17
75
62
48
14
31
33
14
18
19
51
69
Foliage
10.00
2.50
3.40
2.01
0.27
80
11
lh73S4dw
196
-------
862
Table E-8
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1962
Intra Laboratory Quality Control
Laboratory Spike Recovery
Pesticide: Hethiocarb
Matrix: Cellulose and Cauze Pad
Method: See Analytical Methods
Spiking
Level, yg
10.00
"V
1.00
Recovered, Recovery,
.
4
5.00
I
I
V
0.50
1
4
0.25
2.50
4.70
4.40
4.80
5.70
0.39
0.66
0.69
0.59
2.10
2.20
2.60
2.60
0.49
0.60
0.39
0
0.27
0.30
0.43
0.28
0.29
0.26
0.97
2.22
1.05
0.57
2.57
1.50
1.91
1.15
1.06
1.43
1.43
0.75
1.08
1.06
2.06
1.72
47
44
48
57
39
66
69
59
42
44
52
52
98
120
78
0
108
120
172
112
116
104
39
69
42
23
103
60
76
46
43
57
57
30
43
42
82
69
197
-------
Pesticide: Methiocerb
Table E-8 (Cont'd)
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
Method: See Analytical Methods
Sample
Resin (High Volume Air)
Resin (Personal Air)
Class Fiber Filter
(High Volume Air)
Soil
Foliage
Cloves
Spiking Recovered,
Level .
UQ UQ
10.00 1.50
I
2.00
5.00 5.13
2.5 1.01
1
.63
2.5 1.48
J
2.05
2.11
10.00 3.10
\
6.00
9.40
5.00 2.00
*
3.50
1.60
0.50
1.60
^ 5.10
2.50 2.43
1.
•
10.
2.
«
10.
25 1.13
25 0.16
00 3.40
50 1 .86
1 1.79
2.00
1 2.40
00 4.20
1 3.90
1 1.30
Recovery,
%
15
20
103
40
33
59
82
84
31
60
94
40
70
32
10
32
102
97
90
64
34
74
72
60
96
42
39
13
Ih7384dw
198
-------
864
Table E-8 (Cont'd)
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 19B2
Intra Laboratory Quality Control
Laboratory Spike Recovery
Pesticide: Hethiocarb
Method: See Analytical Methods
Sample
Cloves (Cont'd)
Spiking
Level. ug
5.00
1.5
I
Recovered,
PS
1.55
5.70
€.58
5.84
4.20
4.77
5.00
5.00
3.80
5.20
Recovery,
%
31
1H
132
117
84
95
100
100
76
104
1.10
1.20
73
80
Ih7384dw
199
-------
Table E-9
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
865
SUMMARY
Pesticide: Captefol
Methods: See Analytical Methods (Appendix B)
Matrix
Cellulose and
Cauze Pad
Cloves
NOS. OT
Spiked
Samples
6
18
4
8
77
3
4
4
7
3
Spiking
Level , ug
10.00
2.50
1.00
0.50
0.25
0.0005
10.00
5.00
0.50
0.0005
Mean
6.97
2.45
0.96
0.37
0.22
0.000048
5.52
5.07
0.49
0.00066
Standard
Deviation
2.12
0.64
0.12
0.21
0.02
0.000003
2.07
0.61
0.03
0.00047
Mean
70
' 95
96
75
89
97
55
102
98
131
Standard
Deviation
21
19
12
42
9
8
21
12
7
95
Coefficient
Variation,
30
20
13
56
10
6
38
12
7
72
Resin
(Personal Air)
Resin (High
Volume Air)
Filter (High
Volume Air)
Soil
Foliage
2
6
3
4
2
4
0.25
10.00
0.50
0.25
10.0
5.0
0.50
0.25
2.50
0.25
88
65
97
99
103
171
93
78
71
77
15
26
25
5
61
36
42
4
18
17
40
26
5
36
39
54
6
23
Ih7384dn
200
-------
Table E-10
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
866
Pesticide: Captafol
Method: See Analytical Methods (Appendix B)
Cellulose and
Cauze Pad
Spiking
Level. US
10.00
Recovered,
UQ
5.50
5.50
6.50
8.70
10.40
5.20
Recovery,
55
55
65
87
104
52
2.5
1.0
I
0.5
1.77
2.24
2.50
2.02
1.72
2.78
2.49
4.34
3.04
1.98
2.23
2.36
2.29
3.40
1.79
2.62
2.09
2.30
0.91
0.88
1.14
0.90
0.275
0.300
0.275
0.236
0.261
0.253
0.580
0.812
71
90
100
81
69
111
99
130
113
79
88
94
92
135
71
104
83
92
91
88
114
90
55
60
55
47
52
51
116
162
201
Ih7384dw
-------
Pesticide: Captafol
Table E-10 (Cont'd)
YOUTH IN AGRICULTURE STUDY
I DMA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
Method: See Analytical Method* (Appendix B)
867
Cellulose and
Cauze Pad
Spiking Recovered,
Level, UQ U9
0.25 0.30
0.22
0.27
0.23
0.19
0.24
0.16
0.20
0.20
0.21
0.23
0.22
0.25
0.26
0.22
0.21
0.22
0.23
0.22
0.21
0.21
0.26
0.25
0.24
0.24
0.19
0.23
0.23
0.21
0.24
0.20
0.24
0.18
0.21
0.19
0.23
0.21
0.25
0.24
0.23
0.23
Recovery,
\
116
88
106
90
77
96
6*
80
80
85
92
88
100
104
88
84
68
92
68
64
84
112
100
96
96
76
92
92
64
96
80
96
72
64
76
92
84
100
96
92
92
202
1h7384dw
-------
Pesticide: Captafol
868
Table E-10 (Cont'd)
YOUTH IK AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
Method: Sue Analytical Methods (Appendix B)
Cellulose and
Gauze Pad
Spiking Recovered, Recovery,
Level, yg yg
0.25 0.22
0.23
0.21
0.23
0.21
0.21
0.21
0.22
0.21
0.24
0.20
0.22
0.20
0.23
0.21
0.22
0.23
0.22
0.22
0.20
0.24
0.24
0.22
0.22
0.24
0.25
0.23
0.25
0.23
0.21
0.22
0.21
0.21
0.21
0.20
, 0.23
0.0005 0.000047
1 0.000053
«L 0.000046
%
88
92
84
92
84
84
84
88
84
96
80
88
80
92
84
88
92
88
88
80
96
96
88
88
96
100
92
100
92
84
88
84
84
84
80
92
94
106
92
203
-------
Table E-10 (Confd)
Pesticide: Captafol
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
Method: See Analytical Methods (Appendix B)
869
Spiking
Level. U9
10.00
Recovered, Recovery,
I
5.00
7.84
6.30
5.00
2.94
4.18
5.33
5.22
5.57
78
63
50
29
84
107
104.
111
0.50
0.49
0.56
0.45
0.48
0.48
0.49
0.47
99
112
90
96
96
98
94
Cellulose and
Cauze Pad
Resin
(Personal Air)
0.0005
0.50
0.25
0.00120
0.00032
0.00045
0.486
0.178
0.170
0.270
0.200
0.220
0.230
0.200
0.280
0.210
240
64
90
97
71
68
108
80
88
92
80
112
84
Resin (High
Volume Air)
10.00
1
7.00
10.00
4.10
5.00
70
100
41
50
0.50
0.62
0.45
0.38
124
90
76
204
Ih7384dn
-------
Pesticide: Captafol
Table E-10 (Cont'd)
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
Method: See Analytical Methods (Appendix 6)
870
Sample
Filter (High
Volume Air)
Soil
Foliage
Spiking Recovered,
Recovery,
Level f yo yq %
2.5 2.38
I 2.38
0.25 0.26
I 0.24
4 0.24
10 9.9
J
10.6
5 7.5
*
14.5
8.4
6.8
6.4
5.8
2.5 2.24
0.50 0.264
1 0.540
4r 0.598
0.25 0.045
10.210
0.230
0.290
95
95
10
-------
Table E-11
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
Laboratory Blanks
SUMMARY
871
Methods: See Analytical Methods (Appendix B)
Pesticide: Malathion
Cellulose and
gauze pad
Pesticide: Cuthion
Cellulose and
gauze pad
Pesticide: Methiocarb
Number
of blank
samples
6
6
phenol
Urine 43
Pesticide: Captafol
Cellulose and
gauze pad 110
Cloves 10
Resin 8
Filter (High Volume
Air) 8
Soil . 6
Foliage 6
Highest
Zero blanks Positive
Total blanks Blank
6/6 None
6/6 None
43/43 None
89/110 108
3/10 0.26
7/6 0.004
8/8 None
2/6 0.76
5/6 0.03
Units
yg per pad
yg per pad
yg per ml
yg per pad
yg per glove pair
yg per 40 gm
yg per filter
yg per 30 gm
yg per 25 discs
Ih7384d»r
206
-------
Table E-11 (Cont'd)
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
Laboratory Blanks
SUMMARY
872
Methods: See Analytical Methods (Appendix B)
Number
of blank
samples
Pesticide: Methiocarb
Cellulose and
gauze pad 84
Cloves 10
Resin 5
Filter (High Volume
Air) 5
Soil 5
Fol i age 6
Zero blanks
Total blanks
84/84
10/10
5/5
5/5
5/5
6/6
Highest
Positive
Blank
None
None
None
None
None
None
Units
yg per pad
pg per glove pair
V8 per 40 gm
lag per filter
yg per 30 gm
ug per 25 discs
1h7384dw
207
-------
Table E-12
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
Intralaboratory Quality Control
PRECISION STUDIES
873
Pesticide:
Spiking Level
Recovery :
Cel 1 ul ose
and
Cauze
Pad
Range
Mean
St. Dev.
Coef .Var. ,%
Recovery
tl
«2
*3
*4
*5
«6
#7
*6
#9
*10
*1 1
#12
Mai athion
250 yg
kS
149
149
140
158
149
132
184
211
246
228
219
263
132-263
185.7
+45.6
24.6
74%
Meth i ocarb
5.0 yg
US
5.1
6.3
5.3
5.0
3.9
5.0
4.1
4.2
4.2
4.4
3.9-6.3
4.7
+0.7
14.9
94%
Captaf ol
500 yg
Efl
526
471
522
599
551
693
533
566
635
628
555
599
471-693
582.6
+62.3
10.7
117%
Cuthi on
1500 yg
ta
1157
1319
1193
1337
1337
1265
1554
1717
2060
2024
1717
1880
1157-2060
1546.7
+324.2
21 .0
103%
Ih7384dw
208
-------
Table E-12 (Cont'd)
YOUTH IN AGRICULTURE STUDY
low* PHAP, 1982
I ntralaboratory Quality Control
PRECISION STUDIES
874
Pesticide:
Spiking Level :
Recovery:
Personal Air,
Resi n (Study 1 )
Range
Hean
St. Dev.
Coef.Var., %
Recovery
Personal'Air,
Resin (Study 2)
Range
Hean
St. Oev.
Coef.Var.. %
Recovery
Methiocarb
2.50 yg
MS
1 .26
1 .87
2.30
2.00
2.60
2.10
2.00
1 .26-2.60
2.01
+ 0.41
21 .0
80%
1.60
0.70
2.70
2.20
1 .00
1.40
0.70-2.70
1 .fO
+0.74
46.3
64%
P-iEiilil
0.25 yg
Ha
0.24
0.25
0.29
0.25
. 0.28
0.30
£iI2
0.24-0.30
0.27
+0.02
7.4
108%
0.31
0.26
0.25
0.25
0.27
0.27
0.25-0.31
0.26
+0.02
7.7
104%
1h7384dw
209
-------
Table E-13
YOUTH IN AGRICULTURE STUDY
IOWA PHAF, 19B2
Intra Laboratory Quality Control
Laboratory Spike Recovery
875
SUMMARY
Pesticide Metabolites in
Urine
Alkyl Phospates
Methiocerb Phenol
Ma lathion Carboxylic Acids
Methods: See Analytical Methods (Appendix B)
Nos. of
Spiked Spiking
Samples Metabolites Level. ppb
Recovered, ppb
Recovery. \
U
14
U
14
U'
14
DMP
DEP
DMPTh
DEPTh
DMDTP
DEDTP
too
400
400
400
400
400
Mean
353.1
363.1
369.7
400.7
438.3
442.6
Standard
Deviation
79.7
81.8
80.2
64.8
145.8
125.7
Mean
Standard
Deviation
88.2
90.2
92.4
100.2
109.5
110.6
21.6
20.6
20.0
17.7
36.4
31.5
Coefficient of
Variation. »
24.2
22.7
21.6
18.3
33.2
28.4
47
Methiocarb
Phenol
300
219.2
96.2
72.1
33.0
46.2
26
28
DCA
MCA
500
500
430.5
446.6
119.7
98.0
86.1
85.3
23.8
24.1
27.8
28.2
Ih7384dw
210
-------
Table E-14
YOUTH IN AGRICULTURE
IOWA PHAP, 1982
Intra Laboratory Duality Control
Laboratory Spike Recovery
876
Pesticide Metabolites in
Urine
Alkyl Phosphates
Spiking Level: 400 ppb
Method: University of Miami
(Carl Pfaffenberger)
Sample No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Mean
S.D.
299
333
408
313
410
320
230
390
360
280
430
550
310
310
75
83
102
78
103
80
58
98
90
70
108
138
78
78
288
377
380
308
410
340
280
370
350
300
400
610
330
340
72
94
95
77
103
85
70
93
88
75
100
153
83
84
237
246
360
303
460.
420
400
420
380
370
350
540
370
320
59
62
90
76
115
105
100
105
95
93
88
135
93
79
295
381
355
308
450
410
410
410
380
370
370
580
370
310
74
95
89
77
113
103
103
103
95
93
93
145
93
78
230
254
539
203
540
510
410
490
530
570
251
580
620
410
58
64
135
51
135
128
103
123
133
143
63
145
155
103
244
277
507
300
570
530
410
510
540
580
259
520
560
390
61
69
127
75
143
133
103
128
135
145
65
130
140
97
353.0 89.4 363.1 90.8 369.7 92.5 400.7 96.7 438.3 109.9 442.6 110.8
±79.7 ±21.6 ±81.8 ±20.6 ±80.2 ±20.0 ±64.8 ±17.7 ±145.8 ±36.4 ±125.7 ±31.5
1h7384dw
211
-------
Table E-15
YOUTH IN AGRICULTURE STUDY
IOKA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
877
Pesticide Metabolite in Urine
Melathion
Monocarboxylic
Acid
Method: Bradwey and Shaflk
J. Agr. Food Chew
Vol. 25, No. 6, 1977
- ... Recovery
Spiking
Metabolite Level, ppb . ppb
Ma lath ion 500 570
monocarboxyl ic
acid
(MCA)
«
506
522
494
500
588
229
229
458
226
465
599
542
428
449
599
524
428
161
255
428
396
420
437
333
389
, 366
394
%
114
101
104
99
100
118
46
46
92
45
93
120
108
86
90
120
105
86
32
51
86
79
84
87
67
78
73
79
c.
447
85
212
Ih7384dw
-------
Table E-16
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Quality Control
Laboratory Spike Recovery
878
Pesticide Metabolite in Urine
Ma lathi on Oicarboxylic
Acid
Method: Bradway and Shafik
J. Agr. Food Chetn
Vol. 25-, No. 6, 1977
. ., . Recovery
Spiking
Metabolite Level, ppb ppb
Malathion 500 454
dicarboxylic
acid
(DCA)
604
507
417
185
168
462
458
423
474
351
402
378
414
563
512
508
488
500
572
260
239
470
228
470
604
"" 525
417
%
91
121
101
83
37
34
92
92
85
95
70
80
76
83
113
102
102
98
100
114
52
48
94
48
94
121
105
83
431
86
1h7384dw
213
-------
Table E-16
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
lntr» Laboratory Quality Control
Laboratory Spike Recovery
879
Pesticide Metabolite in Urine
M* lathi on Dicarboxylic
Acid
Method: Bradway and Shafik
J. Agr. Food Chem
Vol. 25, No. 6, 1977
.... Recovery
Spiking
Metabolite Level, ppb ppb
Ma lath ion 500 454
dicarboxylic
acid
(OCA)
604
507
417
185
168
462
458
423
474
351
402
378
414
563
512
508
488
500
572
260
239
470
228
470
604
525
417
%
91
121
101
63
37
34
92
92
85
95
70
60
76
83
113
102
102
98
100
114
52
48
94
48
94
121
105
63
431
86
1h7364dw
213
-------
Table E-17
YOUTH IN AGRICULTURE STUDY
IOWA PHAP, 1982
Intra Laboratory Duality Control
Laboratory Spike Recovery
• 880
Pesticide Metabolite in Urine
Methiocarb Phenol
Method: Sullivan and Shafik (unpubl.)
Metabolite
3,5 Dimethyl
(4-methylthio)
phenol
(Methiocarb phenol)
Spiking
Level, ppb
300
Recovery
PP"—
108
101
75
92
411
248
190
336
217
366
300
302
347
359
268
334
275
281
258
292
222
290
284
285
306
295
283
243
158
73
66
108
101
72
92
55
89
221
213
166
252
186
87
317
179
128
133
219
%
36
34
25
31
137
83
63
112
72
122
100
101.
116
120
89
111
92
94
86
97
74
97
95
95
102
98
94
81
53
24
23
36
34
24
31
18
30
74
71
55
84
62
29
106
60
43
44
72
1h7384dw
-------
Table E-18
YOUTH IN AGRICULTURE STUDY
Iowa PHAP, 1982
I ntralaboratory Quality Control
PRECISION STUDIES
Pesticide Metabolites: Alkyl phosphates
Matrix: Urine
Method: University of Miami
(Carl Pfeffenberger)
Spiking Level: 400 ppb
DMP
I~6
376
365
393
398
434
393
344
333
305
327
DEP
356
413
413
434
448
471
439
396
382
364
378
DMPTh
~399
460
473
487
453
473
453
453
412
433
393
OEPTh
~436~
436
454
471
445
463
436
436
428
436
386
DEDTP
~420
410
410
420
420
391
342
410
391
400
391
Range
Mean
St.Dev
Coef.Var.%
Recovery
305-434 356-471
370 414
+17.5% +14%
4.7
93%
3.4
104%
393-487
440
+10.7%
2.4
110%
386-471
429
+ 10%
2.3
107%
369-462
416
+11.3%
2.6
104%
342-420
381
+10.2%
2.7
95%
Ih7384dn
215
-------
Iowa PHAP 882
Youth in Agriculture
Blueberry Harvester Study
APPENDIX F
FORMS USED IN STUDY
TABLE OF CONTENTS '
Page
Field Data Form F-l
Participant Data Form F-2
Subject Consent Form - Adult F-3
Subject Consent Form - Minor F-4
Description of Study Read to
Participants F-5
Ih71084dw 216
-------
883
1982 YOUTH IN AGRICULTURE STUDY
FIELD DATA
Investigator
Workers in Field_
Field location
Assigned I.D.
Date
to
Pesticide History
Acres
Row spacing
Number of workers in field_
Temperature %
Number of rows
P|or>fheight_
Humidity
High Volume Air
Sketch of Field:
Start
Number of participants in field_
Sun condition
cFm
Stop_
Sampling Symbols
High Vol Air X
Soil & foliage 0
Ih71084dw
F-l
217
-------
1982 YOUTH IN AGRICULTURE STUDY
PARTICIPANT DATA
884
s.s.#
Interviewer
Dace
Participant: Name_
D.O.B.
Wt.
Address
Studv A.M.
Assigned I.D.
Start Stop
Telephone (
Clothing
Type:
Tyvek jacket Yes
Personal Air Sampler
Sun tan lotion
Shirt Shoes
Total_
No
Field I.D.
Urine Sample A.M. P.M.
Rate. ml/min Medium
Jacket
Gloves
Pants
Socks
Head Covering_
Protective Equipment:_
NOTES:
Ih71084dw
F-2
218
-------
885
IOWA PESTICIDE HAZARD ASSESSMENT PROGRAM
RESEARCH INVOLVING NO MORE THAK MINIMAL RISK
CERTIFICATION OF SUBJECT CONSENT
Project Title
Investigator
I, , hereby certify that I have been told by
(subject's name)
of about the
(investigator) (department)
research on
(description of project)
and its purposes. I have been told about the procedures to be followed, which
of them are experimental and how much time is involved. I understand the
possible risks and discomforts I may experience and the possible benefits to
me and to others from the research. I have also been told the extent to which
any records which may identify me will be kept confidential.
A written summary of what I have been told is attached. I have been
given adequate opportunity to read it.
I understand that I have the right to ask questions at any time and that
I should contact
___^_______________^_________^___^______^___ for answers
about the research and my rights.
I understand that my participation is voluntary, that I may refuse to
participate or withdraw my consent and stop taking part at any time without
penalty or loss of benefits to which I may be entitled.
I hereby freely consent to take part in this research project.
Signature of Subject
I, the undersigned, certify that I was present during the oral presenta-
tion of the written summary attached when it was given to the above subject.
Signature of Auditor-Witness
Ih71084dw F-3
219
-------
IOWA PESTICIDE HAZARD ASSESSMENT PROGRAM
rt^-.
RESEARCH INVOLVING NO MORE THAN MINIMAL RISK 886
CERTIFICATION OF SUBJECT CONSENT
BY LEGALLY AUTHORIZED REPRESENTATIVE
Project Title_
Investigator
I, , the of
(relationship or legal status)
of , hereby certify that I have been told by
(subject's name)
of about
(investigator) (department)
the research on
(description of project)
and its purposes, in which my has been asked to take part.
I have been told about the procedures to be followed, which of then are
experimental and how much time is involved. I understand the possible risks
and discomforts the subject may experience and the possible benefits to the
subject and to others from the research. I have also been told the extent to
which any records which may identify the subject will be kept confidential.
A written summary of what I have been told is attached. I have been
given an adequate opportunity to read it.
I understand that I have the right to ask questions at any time and that
I should contact
about the research and our rights.
I understand that I have the right to withdraw my consent for him/her to
take part in the project at any time and withdraw him/her from the project
without penalty or loss of benefits to which he/she may be entitled.
I hereby freely consent to taking part in this
research project. (subject's name)
(Signature of Legally Authorized Representative)
I, the undersigned, certify that I was present during the oral presenta-
tion of the written summary attached when it was given to the above legally
authorized representative of the subject.
(Signature of Auditor-Witness)
Ih71084dw F~4
220
-------
QQ7
Iowa Pesticide Hazard Assessment Project
1982 YOUTH IN AGRICULTURE STUDY
Purpose of Study
The purpose of this study is to determine to what extent young fane
workers are being exposed to pesticides.
It is recognized that youths 16-years-old and younger are clearly in
the more formative stages of their maturing process and the effect of
exposure to agricultural poisons on these processes raises concerns for
future health considerations in the youth.
Assumptions have been made that the potential for exposure of youth to
agricultural pesticides is significant. Data are needed to establish what
exposures do exist, to quantitate the exposure, and to evaluate and assess
the potential health effects on young people.
Study Plan
Participants will be sampled for a two-hour period on each of three
days.
Participants will submit a pre-exposure urine sample collected at the
first morning void on the first day of work.
Subjects will be studied for absorption of pesticides and dermal
exposure via the hands. Absorption will be measured by. urinalysis for
pesticide residues and/or metabolites. Dermal exposure of the hands,
representing residues transferred from the crop, will be measured by
analyzing 'cotton gloves worn for one hour each study period.
Each study period, participants will wear a fresh disposable paper
jacket to which absorption pads have been attached, and a personal air
sampler. Pads and air sampler cartridges will be analyzed for pesticide
absorption.
Two post exposure urine samples will be submitted daily throughout the
study. The first sample to be collected at the first voiding after the
work day. The second sample is to be collected at the first void on the
day following the work day. Participants are asked to freeze, or keep cold
as possible, the after work samples.
Samples of soil, foliage, and field air will be collected during both
phases of the study and photographs may be taken while participants are
working, by the investigator.
There is no risk involved in this study. On hot humid days some dis-
comfort may be caused by the paper jackets. The personal air sampler is a
battery operated pump which attaches to the belt. This unit weighs about
two pounds.
You will be provided a release form to sign to allow samples to be
collected and photographs taken.
Data derived from the study will be given to the participant and/or
designated physician only. Collective data will not indicate any specific
individual by name, but will be provided to the government and to a family
or corporate group involved in the study.
You will be paid by the University of Iowa $15.00 for each day that
you fully participate in the study.
You have the right to withdraw your consent and stop taking part in
this study and/or ask questions at any time without penalty or loss of
benefits to which you may be entitled. Questions should be directed to:
Lysle R. Waters Donald P. Morgan, M.D., Ph.D.
Research Assistant Project Director
(319)353-5558 (319)353-5558
Ih71084dw F-5
221
-------
888
Youth in Agriculture: Farmworker Safety in
Apple Orchards at Sturgeon Bay, Wisconsin
1981
Research performed by
University of Iowa
Iowa City, IA 52240
February 15, 1982
-------
WISCONSIN APPLE PICKERS
889
Contact was made with apple growers 1n the Sturgeon Bay, WI area on
August 10, 1981 to recruit youths aged sixteen and under for participation
in the 1981 Youth in Agriculture Study. Seven youths agreed to partici-
pate. These young people, two males and five females, ranged in age from
seven to sixteen. On arrival at the orchards on October 2, 1981 three
adults, two males and one female, and four youths, two males and two
females were available to participate in the study. The ages of the fe-
male youths were eleven and sixteen. The male youths were thirteen and
sixteen years old.
These studies were made in a sixty acre apple orchard where several
varieties of apples are grown. The orchard is owned and operated by two
families. With the exception of employing a small number of local people
for harvesting, all phases, including storage, washing, waxing, packaging
for retail sale, and delivery of the crop are performed by family members.
The young people work in all facets of apple production except application
of pesticides. The pesticides Captan, Imidan and Guthion were applied to
the orchards on August 9 and August 23, Captan and Guthion were applied on
September 6, 1981. On the two days proceeding the study this area ex-
perienced approximately 2" of rain and high winds which caused many apples
to fall from the trees.
These pesticides were applied using a low volume air blast sprayer
calibrated to apply 12.5 gallons of tank mix per acre. The tank mix
applied on September 6, 1981 was:
242
-------
Abstract *' Q9Q
Three adult and four juvenile (under 16 years) harvesters were
monitored for exposure to captan, imidan, and guthion residues.
Captan residues were found on all patches, gloves and in the air
samplers. Imidan and guthion residues were found on gloves, but
on only a few random patches. Gloves had the highest residue
levels. The greatest difference in exposures among the six
harvesters was that of a female adult actually picking apples
from the trees. Her exposure to all three pesticides was much
greater than that of the other harvesters who were picking apples
from the ground, washing and packing them in pallet boxes. Four
harvesters had organophosphates in pre-harvest urine samples.
All had measurable organophosphates in post-harvest urine samples.
-------
Guthion 2 ounces actual Ingredient
Benlate 1 ounce actual Ingredient 891
Captan 8 ounces actual Ingredient
per gallon of water all were 50% wettable powder. Methodology and sensi-
tivity were not suitable for analysis of Benlate at the rate which Benlate
was applied to the orchard.
Sampling Methods
All participants wore personal air samplers and Tyvek semi-disposable
jackets with 4" x 4" alpha cellulose pads with glassine backing to which
2« x 2" - 9 ply gauze pads were attached with staples in the center of the
square, and white cotton gloves. An alpha cellulose 4" x 4" square was
attached to the Inside of the jacket arm, chest and back adjacent to the
corresponding pad on the outside. These trapping mediums were solvent
extracted before use.
Gauze pads and the 2" x 2" square of alpha cellulose pad directly
beneath the gauze were analyzed for adsorbed pesticides. A pre-exposure
urine sample was collected the morning of the study and a post-exposure
sample collected the morning following the study. These were collected
and stored in brown glass bottles. Soil samples were collected under the
"drip line" of the trees and stored in brown glass containers. Foliage
samples were taken with a leaf punch. Fifty 3/4" diameter leaf punchings
constituted each foliage sample. These too were stored In brown glass
containers. Dry samples were wrapped in aluminum foil. During the process-
Ing of apples, before packaging for retail sale, they are washed with
recirculated water and rinsed with clean water. Rinse water, as well as
wash water, flows into a common sump from which the wash water is pumped.
An overflow pipe maintains the proper water level in the sump. Two
samples were collected in brown glass bottles from the wash water spray
nozzles. A high volume air sample was collected from approximately the
243
-------
center of the orchard work area. Aluminum foil lines were used under all
container caps. All samples were placed 1n a styrofoam ice chest, con-
taining dry 1ce. Immediately after collection. On arrival at the Iowa
Project Laboratory samples were stored In a freezer.
During this study DHF, the adult female, picked apples from the
trees; placing these apples 1n a "picking bag" worn over the shoulders,
hanging In front, which was later emptied from the bottom into pallet
boxes. One adult male and four youths picked up fallen apples and handled
them in a similar manner. The remaining adult picked up apples for a
shorter period of time. The fallen apples were In grass approximately six
inches tall. JHF an adult male and HEP a female youth occasionally
operated a tractor moving pallet boxes from tree to tree and often adjusted
these pallets by hand to align them with the tractor 11ft fork. ERF and
HEF, both female youths, submitted a post-exposure urine sample collected
late in the day of the study. HEF submitted an additional morning after
exposure sample.
Results
All environmental samples contained pesticides but, not all samples
contained all three pesticides. Three of the five soil samples did not
contain Guthion (azinphos) and the high volume air samples, both filter
and resin, contained only Captan. The apple wash water contained measurable
amounts of Captan, Imidan and Guthion as did the five foliage samples.
Six of the seven personal air resin samples contained Captan. Imidan was
detected in two samples and Guthion in one. Only one personal air resin
sample contained Captan, Imidan and Guthion, that of DHF, the lady who
picked apples from the trees. Although not reflected by excreted residues
detected in the urine; the jacket pads of DHF adsorbed more pesticides than
did any of the other participants who worked on the ground. All three
244
-------
00?
pesticides were detected on DHF's jacket pads. 07j
Captan was detected on all alpha cellulose and gauze pads of all
jackets. Imi dan was detected on the gauze pads but, not on the alpha
cellulose pads of six jackets. Guthion was detected on one outside alpha
cellulose pad of one jacket and on two gauze pads of another jacket.
A surprising anomaly presents itself when one examines the quantity
of pesticide residues excreted by HEF and ERF. These female youths per-
formed the same type of work at the same time with the exception of HEF
occasionally operating a tractor. During those times ERF rode sitting in
the pallet while it was being moved to another tree. HEF picked up nearly
twice as many apples as-ERF but, residue excretion by HEF is.several times
greater between the urine samples collected during the same time period.
Also HEF excreted three pesticide residues while ERF excreted only one.
HEF excreted more organophosphate residue than did any other, participant.
Pre-exposure urine samples submitted by JHF, DHF, HEF, and TOF all
contained organophosphate residues. These findings indicate absorption
of pesticides previous to the day of the study. The adults JHF and DHF
probably absorbed them while working in the orchard and processing plant
on days prior to the study. The young people were possibly exposed to
the pesticides from contaminated work clothing and jackets, or from work-
ing on the apple processing line or from eating unwahsed apples. They were
observed picking apples from the trees and eating the unwashed fruit and
wearing their work jackets while not working.
Pre- and post-exposure urine samples submitted by JHF contained
diethy! phosphate, an organophosphate metabolite which one would not ex-
pect to be present after absorption of any of the pesticides applied to
the orchard. The source of absorption of the pesticide(s) creating this
245
-------
metabolite is unknown. It could conceivably be from the area where hjs .
8/4
unused pesticides are stored, contaminated clothing such as leather shoes
or contaminated equipment.
Although pesticides had not been applied to the orchard since
September 6, 1981, four weeks before the study, it is evident from the en-
vironmental sample data that there was Captan, Imi dan and Guthion present
on leaves, grass and fruit in the orchard. Patch and excreted residue
data confirm that orchard workers can and do absorb these pesticides
from contact with the leaves and fruit even after observing label re-
quirements of application to harvest time. In this case seven days
for both Guthion and Imidan.
246
-------
Interviewer;
Date lo-
895
Participant: Name
Weight
DOB Jo 1171
Address
» LA/1
Site:
Protective
Equipment:
Assigned I.D. A U E SSI
Work Activity f\dB Jr»» *Bta/^ Start
^ r
Crop A^}*±
Telephone ( )
Location
Crop Height
Row Spacing
P-4OOO
goggles
gloves
respirator
rubber suit/coveralls
Clothing
Type:
Stop
Acres
pants
Long Sleeved sh1rt/jaefc»t
«i ""
shoes/bftftis
hat
Weather: Wind
Su/ Wind Condition S f C
Temperature SI* F t Humidity £8 % Sun Condition C-
Field History:
ip^tt.y«.^/ u>HU
j*.ri a tt *
a-f- C
on
Field Drawing:
*
7?.
^9
*€>
247
House
Sampling Site
Symbols
X
o
0=
High
Volume Ai
Foliage
-------
1981 YOUTH EXPOSURE STUDY
896
Interviewer;
R.
Date 10-2-61
Participant: Name
Weight
DOB // / 27/24
Site:
Protective
Equipment:
Address
fxJl
Assigned I.D. £?HF SSI _
Work Activity ficking g.pp|e*
Crop /4f ple5
./_/.
Start
Telephone (
9:30 ou>n
Stop to: so a.*
Location
Ba.v,Lui
Crop Height
Row Spacing
Acres
4 o
V
goggles
gloves
respirator
rubber suit/coveralls
Clothing
Type:
pants
sfcfft/jacket
shoes/beott
A/o hat
Weather:
Wind 1-3
row».
Wind Condition
Temperature
-------
1981 YOUTH EXPOSURE STUDY
Date
Participant: Name
Weight
DOB & US I 81
Site:
Protective
Equipment:
Address
Assigned I.D.
SSI
Telephone ( )
Work Activity ?rk,^ ,.r jfa* «.Tyk* Start ?:^5*^^ Stop /0: 3
Crop >4»p>AS Location //.of <-K/r«gg;. 3«-/. ;ir
Crop Height
Row Spacing
0»r
Acres LO
P-40OO
Mo goggles
_\ gloves
respirator
rubber suit/coveralls
Clothing
Type:
897
-.-r- sh1rt/j*e*»«t
W g r- shoes/boo*s
//o hat
Weather:
Wind i-3
Temperature
. u;. Wind Condition
% Humidity && _ Sun Condition c
Field History: 5e«. ^ VA
Field Drawing:
Sampling Site
Symbols
249
X >
o >
©•
Soil
High
Volume Ai
Foliage
-------
1981 YOUTH EXPOSURE STUDY
' 898
viewer: lya/e. £. UAx+*rS Date / 0' 3-S1
dpant: Name Weight DOB IP/ S /
Address S^r^eon "bay 1
Assigned I.D. TO F SSI
Work Activity fiJeiwa i>» $lr»f a.o^«*.
Crop Apple*
Crop Height Row Spacing
•ctive
xnent: Nlo goggles
I gloves
I respirator
' rubber suit/coveralls
\JJ\
1 / Telephone ( )
Start 9<^£*a.i>»i Stop y0;3£«.»*
Location /V/. or J^VCttf*. Soy- '^ '
Acres /» o
Clothing
Type: Oea.^-, pants
Lone, Sfeet/c^ aMfit/jacket
(^^..-i-Ufti- shoes /hosts
A/o - hat
ler: Wind >- 3 >on»/i fro^ ^. UU. Wind Condition
Temperature Si ° F X Humidity ££ Sun Condition Clear
History: 5e.e A B F
I Drawing:
250
Sampling Site
Symbols
X • Soil
o « High
Volume Ai
0« Foliage
-------
1981 YOUTH EXPOSURE STUDY
899
Interviewer; *•/*'* K.W*S*r* Date /p-3-&f
Participant: Name Weight DOB // / /?/
Address ^•fyroeo^ OOLV . Lul
Assigned I.D. ERF SSI / / Telephone ] J_
Work ActivityP
••^^•^^.^••^^••^W^i^^-^H^BV^^-^^l^-^H^—^^^^^^^ ^—^•^^_»_B^H^^-^V»~_^^^i*^^^Wi^^^^M^B*
Crop Height Row Spacing Acres LO
Protective Clothing
Equipment: Mo goggles Type: ^e^.^ pants
gloves io«f» 5tef<^J sMrt/jacket
respirator Tk>»/T/< shoes/bowfes
rubber suit/coveralls /Vo hat
Weather: Wind v5~-£ m»/r /^^ S UX Wind Condition
Temperature c 7 F t Humidity So Sun Condition ^
Field History: 5eg JSHF
Field Drawing:
251
Sampling Site
Symbols
X = Soil
o - High
Volume Ai
Q* Foliage
-------
1981 YOUTH EXPOSURE STUDY
900
Interviewer-., tya/c. R, lVa.ter*_ Date 10-1- " '
Participant:
Site:
Protective
Equipment:
Name
Address
Assigned I.
Work Activi
Crop Af<
Crop Height
No
i
j
Weight DOB S / Z? / £5"
S' O till
•*e.o*> L<>r LuT.
Row Spacing Acres ^ 0
Clothing
goggles Type: iftft.»ia pants
gloves Lone Sldci/a* sWK/jacket
respirator T£JU" i shoes/bccls
rubber suit/coveralls Yp hat
Weather: Wind ^T-^ r.tr>» f*-^ - uy Wind Condition
Temperature £7*r % Humidity fo Sun Condition
field History: S&e. ^ H f
field Drawing:
252
Sampling Site
Symbols
X * Soil
0 « High
Volume Ai
0« Foliage
-------
1981 YOUTH EXPOSURE STUDY
901
I-Y*I* ?>
Date /0-3- 81
Participant: Name
Weight
DOB
f /_
Site:
Protective
Equipment:
Cedo.r
*&tas
. \ A
Address
Assigned I.D. K"U//< SSI
Work Activity ftdfei«« ^Iwp AfJaa Start
Crop A*n\*± Location
Crop Height
Row Spacing
¥-4000
goggles
gloves
respirator
rubber suit/coveralls
Clothing
Type:
Telephone
Stop .Slt&p* ___
5-f»/n»&g>»
Acres
- X A t> -
pants
f CLD-
Weather:
Wind 3-L
temperature
Wind Condition
% Humidity
Sun Condition C Ho
Field History: 5ee ^ U F
Field Drawing:
Sampling Site
253
X * Soil
o * High
Volume />
0= Foliage
-------
1981 Farm Worker Safety
Youth in Agriculture
Sturgeon Bay. MI - Apple Picker Samples
f\>
in
Jacket Pads
with
Gauze Pad
Q
•o
01
c
I/I
«*:
JHF
DHF
JDF
TOF
HEF
ERF
KWK
X
01
CO
M
F
M
M
F
F
M
Ol
o>
Adult
Adult
16
13
16
11
Adult
i
I
X
X
X
X
X
X
X
Ol
3
o
to
X
X
X
X
X
X
X
».C
^_ ^_ r-«->>UWI
t |_ O O ^ *r- 01 «
5 =3 U- l/> 3C 3C DC 3T
X
X
X
X
X X
X X
X
Environmental Samples
Pesticides Used on Orchard: Captan, Guthlon, Imldan
o
INJ
-------
ro
en
en
1981 Youth In Agriculture Exposure Study
Apple Orchards - Sturgeon Bay. HI
Guthlon(azlnphos) in Jacket Patches. Gloves and Inspired Air
Results expressed In
Q
.
t~*
•o
at
c
01
•r-
l/l
I/I
**
JIIF
OHF
JOF
TOF
HEF
ERF
KWK
JC
u
s.
6
0
0
0
0
0
0
0
at
N
3
•a
Ol
at
TJ
3
O
01
0
1.2
0
0
0
0
0
^j
a
VI
at
JC
o
0
0
0
0
0
0
0
at
N
3
•a
Ol
•M
I/I
01
JC
CJ
0
1.4
0
0
0
0
0
mlcrograms
JC
u
-------
ro
en
cn
1981 Youth In Agriculture Exposure Study
Apple Orchards - Sturgeon Bay. MI
Imldan in Jacket Patches. Gloves and Inspired Air
Results expressed In mtcrograms
0
>— i
-o
01
c
en
IO
JHF
DHF
JOF
TOF
HEF
ERF
KUK
u
id
ft
E
0
1.2
0
0
0.1
1.0
0
JC
0
ex
4J
I/)
Ol
JC
0
0
0
0
0
0
0
0
01
3
id
en
(/)
Ol
JC
o
0.2
2.4
0.1
0
0.1
0
0
JC
u
id
ex
j*
u
CO
0
0
0
0
0
0
0
Ol
N
3
en
\s
u
40
u
t.
Ol
c
c
•— «
0
0
0
0
0
0
0
M
01
^
0
r—
C9
110
310
100
90
150
50
40
c
•r-
«O
*«d
O
1/1
Ol
o.
0
0.3
0
0
0
0
0.1
Gauze pads - 9 ply 2"x2" analyzed
a - Cellulose pads - 2"x2" analyzed
.ii
-------
ro
in
1981 Youth In Agriculture Exposure Study
Apple Orchards - Sturgeon Bay, WI
Captan In Jacket Patches, Gloves and Inspired Air
Results expressed In mlcrograms
0
•a
Ol
c
en
•r-
W
in
U
1.6
1.7
1.4
0.3
0.7
0.3
2.2
u
4-»
-------
1981 Youth In Agriculture Exposure Study
Apple Orchards - Sturgeon Bay, WI
Urine Analysis Data
Alkyl
Phosphates In Urine
Parts per million (mlcrograms/ml ) found n^inA
volume
I.D.
JHF
OHF
ro
tn
00 JOF
TOF
HEF
ERF
KWK
Sample THPI
Pre-study
Post-study
Pre-study
Post-study
Pre-study
Post-study
Pre-study
Post-study
Pre-study
Post-study PM
Post-study AM
Pre-study
Post-study PM
Pre-study
Post- study
Pre-study Urine Samples -
Post- study Urine Samples,
Post-study Urine Samples.
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
DMP
0
0
0.12
0.10
0
0.07
0
0
0
0.08
0
0
0
0
0
collected
PM -
AM -
OEP
0.78
0.03
0
0
0
0
0
0
0
0
0
0
0
0
0
at first
OMDTP DEDTP
0.15
0.12
0.10
0.07
0
0.16
0
0
0.12
0.54
0.10
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
morning voiding
collected approximately
collected approximately
5:00
DMPTh
0.
0.
0.
0.
0
0.
0.
0.
0.
1.
0.
0
0.
0
0.
at
PM.
7:30 AM,
36
33
20
21
16
03
05
17
00
17
07
03
OEPTh mil
0
0
0
0
0
0
0
0
0
0
0
< 0
0
0
0
approximately 7:30
1 inters
91
209
140
329
259
253
215
253
236
276
282
334
137
179
315
AM October 3, 1981
October 3, 1981
October 4, 1981
O
O\
-------
Orqanophosphate Pesticide Urinary Metabolites QQ7
DCP - 01ethyl phosphate
DEDTP - 01ethyl phosphorodlthloate
DEPTH - 01ethyl phosphorothlolate
DMP - Dimethyl phosphate
OMDTP - Dimethyl phosphorothloate
OMPTh • - Dimethyl phosphorothloate
Cap tan Urinary Metabolites
THP1 - Tertrahydrophthallmlde
-------
1981 Youth 1n Agriculture Exposure Study
Apple Orchards - Sturgeon Bay, HI
Miscellaneous Sample Data
All values parts per million (mlcrograms per gram)
908
Apple Wash
Water
Foliage
Soil
High Volume
A1r
11
*2
1
2
3
4
. 5
1
2
3
4
5
Glass
Fiber
_ Filter
jtesln
Cap tan
0.057
0.309
11.0
12.7
23.9
8.5
19.8
0.2
0.5
0.1
5.2
0.8
70.2ng/m air
30.2ng/m air
Imldan
••^••l^MMM^HB
0.012
0.032
n.o .
10.1
21.2
8.6
20.2
1.0
0.4
0.2
6.3
0.6
0
0
Guthloi
0.045
0.051
6.0
11.0
27.7
5.2
21.9
0 .
0
0
11.0
0.4
0
0
259
-------
QUALITY CONTROL FOR 909
WISCONSIN YOUTH IN AGRICULTURE
The Iowa PHAP quality control procedure 1s to analyze a spiked
sample and a blank In conjunction with an unknown or group of unknowns
at the rate of at least 10%. Instruments are calibrated dally and
standards are Injected Into the Instrument with each sample or group
of samples. Spike and standard chemicals are obtained either from
RTP or the manufacturer.
LABORATORY SPIKED SAMPLES vs. EXPOSED SAMPLES
Number
Sample ExposedSpiked % Spikes
Alpha-cellulose pad and
gauze pad 167 24 14
Apple wash water 6 3 50
XAD-4 Resin 24 3 12
Foliage
Cotton gloves
Soil
Urine
15
63
15
45
3
3
3
6
20
5
20
13
260
-------
910
LABORATORY QUALITY CONTROL
Captan
Substrate
Pad
Apple wash water
XAD-4 Resin
Foliage
Gloves
Soil
Spiking Level
1 vg
1 ug
1 vg
1 ug
1 ug
1 ug
1 ug
1 ug
l ug
1 ug
1 ug
5 ug
5 ug
Amount Recovered
1.1 ug
1.13 ug
1.12 ug
1.07 ug
1.22 ug
1.18 ug
1.11 ug
0.99 ug
1.01 ug
1.16 ug
1.15 ug
4.8 ug
2.0 ug
% Recovery
110
113
112
107
122
118
111
99
101
116
115
96
40
261
-------
Imi dan
Substrate
Pad
Apple Wash Water
XAD-4 Resin
Foliage
Gloves
Soil
Spiking Level
1 u9
1 u9
1 yg
1 u9
1 yg
1 u9
1 v9
1 yg
1 yg
1 yg
1 yg
5 yg
5 yg
Amount Recovered
1.0 yg
1.16 yg
1.03 yg
0.94 yg
1.05 yg
0.85 yg
1.08 yg
1.01 yg
0.94 Mg
1.10 yg
1.0 yg
4.2 yg
5.4 ug
7 I i
% Recovery
100
116
103
94
105
85
108
101
94
110
100
84
108
262
-------
912
Azlnphos
Substrate
Pad
Apple Wash Water
XAD-4 Resin
Foliage
Gloves
Son
THPI
Urine
Urine
Spiking Level
5 ug
5 ug
5 ug
5 u9
5 ug
5 ug
5 ug
5 ug
5 ug
5 ug
5 ug
25 ug
25 ug
300 ppb
400 ppb
Amount Recovered
3.90 ug
4.97 ug
4.30 ug
4.23 ug
4.70 ug
3.57 ug
4.78 ug
4.10 ug
4.1 ug
6.0 ug-
5.3 ug
20.5 ug
27.5 ug
346 ppb
181 ppb
% Recovery
78
99
86
85
94
71
96
82
82
120
106
82
110
115
45
263
-------
Substrate Spiking level Amount Recovered % Recovery
DMP
PEP
DMDTP
DEDTP
DMTP
DETP
Urine
Urine
Urine
Urine
Uri ne
Urine
Urine
Uri ne
Urine
Urine
Urine
Urine
500
500
1000
1000
760
760
800
800
800
800
800
800
ppb
ppb
PPb
PPb
ppb
ppb
ppb
ppb
ppb
PPb
ppb
ppb
•
820
610
1883
1507
780
847
900
503
436
1186
368
1521
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
ppb
164
122
188
151
118
126
113
63
55
148
46
190
913
Recoveries reflect typical problems encountered with current alkyl phosphate procedure
264
-------
Supplies taken to Sturgeon Bay, WI
914
Disposable paper jackets c patches
Brown glass urine sample bottles
Foliage collection punch
Foliage collection bottles
Brown foliage sample storage bottles
Personal air samplers
Personal air sampler XAD-4 collection medium tubes
White cotton gloves
High volume air samplers
Tripod for high volume sampler
High volume air XAD-4 collection medium (100ml)
High volume glass fiber filters
Brown soil sample bottles
Gasolene driven 110 volt generator
Study forms
Consent forms
Aluminum foil
Self adhesive labels
Plastic garbage bags
Thermometer (wet & dry bulbs)
Styrofoam shipping ice chests (large)
Dry ice
125
24
1
4
15
10
26
25 pr.
2
1
6
6
15
1
12
12
4
248
12
1
2
50 Ibs.
265
------- |