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.

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                        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.

-------
 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

-------
                                                                             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

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                                                                              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.

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                                                                         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

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                                                                        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.

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                                                 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

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                                                                         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.

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                                                                             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"
58"
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

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                                                                        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

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                                                  94
Dermal and Respiratory Exposure  Studies
  of Adult and Juvenile F1eldworkers,
  1983-1984
        Research performed by

        Mississippi  State University

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                           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.

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                                                             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.

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                                                              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

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                                                            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

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                                                             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

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                                                           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.

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                                                             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

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                                                             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

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                                                                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.

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                                                               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.

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                                                              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

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                                                              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
*NDNone 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
*NDNone 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
*NDNone 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
*NDNone 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
*NDNone 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
*NDNone 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
*MBCMethyl-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
*NDNone 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
*NDNone 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
**NDNone 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

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                                       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

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                                      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

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                          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 SEndosulfan 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,

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                                                 210
D1siodgeable Captan  Residues  at Florida
  Strawberry Farms
        Research performed  by

        Florida State  University
        Lake Alfred, FL   33850

        May 1986

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                                                                        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

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                                                                      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

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                                                                          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

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                                  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

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                                                                             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"

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                                                                         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 -17C  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.

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                                                                               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 40C 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
 40C.   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  40C and brought up in 10 ml hexane for GLC
analysis.   Processed  samples were stored at -17C.   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 40C and 5 ml
 of  hexane was added for the Sep-pak sample cleanup described above,
 prior to GLC  analysis.  Processed samples were stored at -17C.
 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 210C, detector 270C, N2 50
ml/min, oven  temperature 170C 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.

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                                                                       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 -17C 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

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                                                                          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

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                                                                       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

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                                                                           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

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                                                                     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

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                                                                    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

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                                                                          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

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                                                                         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

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                                                                          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
 40C, 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

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                                                                        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

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                                                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

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                                                             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

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                                                                          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.

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                                                                      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.

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                                                                                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

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                                                                          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.-225C

                    Detector Temp. - 245C

                    Oven Temp. - 140C for  0.6  min., 10C/min. to

                                 180C 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

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                                  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

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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

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                                         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

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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

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                                                                          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

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                                                                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

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                                                                           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

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           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

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                                                                       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.

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                                                                         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.

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                                                                        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

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                                                                        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

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                                                                       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 (13C) 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 60F (J5*C) and soil temperature was  56F (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

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                                                                       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

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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

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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

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    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

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                                                               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

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                   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

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                                                                    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

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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

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                                                                             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

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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

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                                         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

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                                                 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

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                                                     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

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                               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

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                                                                           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

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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. - 225C



        Detector Temp. -  210C H3 EC



                          325C Ni63 EC



                          245C N-F



        Column Oven -     200*C
                                   12

-------
   Transfer-line Temp. - 235C                                     ._
                                                                   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 (X526nm) .  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
theSC 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

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                                                                                 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.

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                                                                         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).

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                                                  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

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                                                                          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-

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                                  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-

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                                                                           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-

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                                                                    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-

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                                                                 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-

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                                                                             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-

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            ^ 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

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                                                                                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

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                                                          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



8sii M 9-16



Resmrks

-



-

Brother of psrticif
1A "
1U.


Personal sir sanple
slfunctloned on
9-16*

I
oo
                                                                                                                   LM

                                                                                                                   Ul

                                                                                                                   r\)

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                                                                           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-

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          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-

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                                                                     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  196C; Injection port temp -  220C; 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.

RSULTSr
     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-

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                                  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-

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                                                                       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-

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                                                                     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. 660Q. 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 0F.  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. 10. 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

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                                     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

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                                                                          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


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                                                                          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

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                                                                          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-

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                                                              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-

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                                                                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-

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                                                             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-

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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-

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                          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-

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                                       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.

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                                                                              394
        thought to be too hot and  restrictive to the participants.   Due to  the
        temperature (95F+) 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-

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                                                                           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-

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                                                                      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-

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                                                                        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. = 225Cj detector temp  = 210C;  Column  oven = 200C;
          transfer section temp  = 230C; 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-

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                                                                       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      -     95F
                    2.  Relative  humidity        -     75%
                    3.  Barometric pressure      -   30.00
                    4.  Wind speed and  direction -     0
                    5.  Percent cloud cover      -     0
                    6.  Soil temperature         -     90F
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-

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                                                                         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-

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                                                                        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               -  90F
 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-

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                                     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-

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                                                                       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-

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                                        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-

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                                                                       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-

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                                  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-

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                                                      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

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                    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-

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                                     Appendix C
                                      Figure 1
      i*!*":-:^'-1:::;*:


/^  |: .-- . -. .-  	i	






                                                 /t   ,  RSD 7






                     llfii



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                                                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

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                                                         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

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                                                                        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

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                                                                   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

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                                                                            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

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      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

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                                         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|

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                        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)

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                                                                    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

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                                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.

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                                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.

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                                                                     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

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                                                                  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

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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

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                                                                    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

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                                                                          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. - 225C

         Detector Temp. -  210C  H3 EC

                           325C Ni63 EC

                           245C N-P

          Column Oven -    200C


                                 12

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                                                                     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

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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 Harvestr  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

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                                                                     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

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                                                             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

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                          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

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                                                                           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

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                          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

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                                                                     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

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                                                                        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

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                                                                       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

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                                                                     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

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                                                                      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

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                                  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

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                                                                          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

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                                                                                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

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                                               463
Youth 1n Agriculture:  Human Exposure Assessment
  and Medical  Records  Morbidity Study
        Research  performed  by

        Colorado  State  University
        Fort Collins. CO  80523

        January 1984

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                                                                              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.

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                                                                            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

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                                                                       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

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                                                         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

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                                                             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

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                                                                  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

-------
                                                                        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

-------
                                                                          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.

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                                                                      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

-------
                                                                          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

-------
                                   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

-------
                                                                     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.

-------
                                                                    484
                                   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

-------
                                                                    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:

-------
                                                                     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

-------
                                 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).

-------
                                   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  5Z 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

-------
                                                           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
-------
                                   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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                                                                     496
                                   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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                                   30
                                                                      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

-------
                                                                 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.

-------
                                         515
DAY 1
DAY 2
                             k   
                             I  
                             i	
                   FIELD A
                 FIELD B

-------
                                                         516
Figure 4.   Polyurethane foam plug air sampling module (top)
           and vacuum pump (bottom)  used  for  collecting
           field air samples.

-------
517

-------
                                                              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

-------
                                    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

-------
                                   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)

-------
                                                                   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

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                                                                          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

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                                                                          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.

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                                                                          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.

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                                      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

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                                   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

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                                                                             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.

-------
                                  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.

-------
                                 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

-------
                                                                      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

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                                 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

-------
                                                                            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

-------
                                                                           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.

-------
                                 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.

-------
                                 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

-------
                                                                            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

-------
                                                                     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

-------
                                 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.

-------
                                                                    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.

-------
                                 124





      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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     poisonings due to paraoxon residues.  J Occup Med 19:411-414.

 Spear RC.  1980.  Technical problems in determining safe reentry
     intervals.  J Environ Path Toxicol 4:293-304.

 Spear RC.  1982.  Farm worker exposure to pesticide residues:
     reflections on differential risk.  In:  Banbury Report 11.
     Environmental factors in human growth and development.  Hunt
     VR, Smith MK, Worth D, eds.  Cold Spring Harbor Laboratory,
     pp. 67-76.

 Spencer WF, Iwata Y, Kilgore WW, Kneak JB.  1977.  Worker reentry
     into pesticide-treated crops.  II.  Procedure for the deter-
     mination of pesticide residues on the soil surface.  Bull
     Environ Contam Toxicol 18:656-662.

 Staiff DC, Davis JE, Stevens ER.  1982.  Evaluation of various
     clothing materials for protection and worker acceptability
     during application of pesticides.  Arch Environ Contam Toxicol
     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.

Vessel ES.  1982.  Dynamically interactive genetic and environmental
     factors that affect the response of developing individuals to
     toxicants.  In:  Barbury Report 11.  Environmental Factors in
     Human Growth and Development.  Hunt VR, Smith MK, Worth D, eds.
     Cold Spring Harbor Laboratory, pp. 107-124.

Von Rumker R, Horay F.  1972.  Pesticide manual - part I:  safe
     handling and use of pesticides; part 11:  basic information
     on thirty-five pesticide chemicals.  Shawnee  Mission, Kansas:
     U.S. Dept. of State, Agency  for International Development.

Walker GM.  1979.  Utilization of health care:  the Laredo migrant
     experience.  Am J Public Health 69:667-672.

Walravens PA, Hambridge KM.  1975.  Growth of infants fed a zinc
     supplemented formula.  Pediat Res 9:310.

Ware GW.  1978.  The pesticide book.  San Francisco:  W. H. Freeman
     and Company, 197 p.

Weast RC, ed.  1971.  Handbook of chemistry and physics - a ready-
     reference book of chemical and physical data, 52nd ed.
     Cleveland:  The Chemical Rubber Company.

Weiss HB.  1981.  Human exposures to pesticides.  Wise Med J 80:
     12-15.

Wester RC, Maibach HI.  1976.  Relationship of topical dose and
     percutaneous absorption in rhesus monkey and man.  J Invest
     Dermatol 67:518-520.

Wicker GW, Williams WA, Guthrie FE.  1979.  Exposure of field
     workers to organophosphorous insecticides:  sweet corn and
     peaches.  Arch Environ Contain Toxicol 8:175-182.

Wilson DJ, Locker DJ, Ritzen CA,  Watson JT, Schnaffner W.   1973.
     DDT concentrations in human  milk.  Am J Dis Child 125:814-817.

Wofinden RC.  1966.  The health of agricultural workers.  WHO  Chron
     20:442-446.  :

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     insecticide metabolites.  Arch Environ Health 21:711-716.

-------
                                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 failia
enferwos durante este ano.i>
IS. Ha visto Ud. o miembros de su famllia
un ndico 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) MS 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*m2







Method
of App.
PlMM !
*)*. 
Gr*. ftm.O
Gt4. Afe.
ten -4
Inc. W/
lrrif*t. 5
OthosfiJ







Type of
Coverage
IBrtfcM lNC-1
ItrMMMM
1 IM. -t
:*M o
lnFurrDW4
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

200C

nitrogen, flow rate of 80 ml per
minute

275C

245eC

245C
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

                                   200C

                                   nitrogen,  rotameter setting of
                                   7 cc/min.

                                   275C

                                   210C

                                   235C
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      165C

            Carrier gas            nitrogen, rotameter setting of
                                   2.3 cc/min.

            Detector temperature   200C

            Inlet                  215C

            Transfer line          245C
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

-------
                       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  70C 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.

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                               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

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                                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

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                                               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

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                          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.

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                                                                         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

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                                                                      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

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                                                                        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:
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                                        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 (-18C).
     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 70C 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

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                                                                           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

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                                                                       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

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                                                                      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

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                             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

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                            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

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                                                                       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

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                                                                                  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

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                                                                    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

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                                                                          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

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                                  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

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                             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

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                                                                        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

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                                                                          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

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                                                                        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

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                                                                     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

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                                                                       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

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                                 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

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                                                                    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

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                                 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

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                                                                     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

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                                                                         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

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                                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

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                                 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

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                                 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

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                                                                    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

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                                 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

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                                                                    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

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                                                                      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

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                                                                      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

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                                 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

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                                                                     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  conta