540/09-88-037
                     PESTICIDE HAZARD ASSESSMENT PROJECT:

                 Harvester Exposure Monitoring Field Studies

                               (1980 - 1986)

                                 VOLUME 2
                    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
540/09-88-037

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                                                      540/09-88-037
                PESTICIDE HAZARD ASSESSMENT PROJECT:

            Harvester Exposure Monitoring Field Studies

                          (1980 - 1986)

                            VOLUME 2
               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*

Youth in Agriculture: Pesticide Exposure to Strawberry       10
  Pickers, 1981

Youth in Agriculture: Dermal Exposure to Carbaryl by        124
  Strawberry Harvesters, 1982

Youth in Agriculture: Dermal Exposure to Vinclozolin        168
  by Strawberry Harvesters, 1982

Simultaneous Dermal Exposure to Captan and Benomyl by       214
  Strawberry Harvesters, 1983

The Relationship between Dermal Pesticide Exposure by       240
  Fruit Harvesters and Dislodgeable Foliar Residues,
  1981-1983

Reentry Simulation Study, Phase I and Phase II              274

Pesticide Exposure of Harvesters of Blueberries, Black-     475
  berries and  Raspberries

An Assessment  of Exposure of Okra Harvesters to Carbaryl    643

An Assessment  of Exposure of Cucumber Harvesters to         677
  Azinphos-Methyl

An Assessment  of Exposure of Tomato Harvesters  to           744
  Chlorothalonil

An Assessment  of Exposure of Cucumber Harvesters  to         799
  Methomyl

An Assessment  of Exposure of Turnip and Mustard Green       845
  Harvesters to Phosdrin
 *  Please note that  the  pagination  of  the  studies  in  the Table
   of  Contents correlates  to  the  page  numbering  located in the
   top right hand  corner of  each  page.

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                                                         :      4

                         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 DDL and  EPA would
jointly fund these studies, and these resources were then  used to
fund research projects with appropriate in.sti tutions (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 toxicol ogical 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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                                                           If?
                    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.
!•    Age Differences in Acute Oral Toxicity;
      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., 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. et al.  Dermal Absorption of Pesticides
      Calculated by Deconvolution. J. Appl. Toxicol. 5:162-
      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.   In Vivo and  In Vitro Dermal
       Penetration of 2,4,5,2T74T,5'-Hexachlorobiphenyl  in
       Young and Adult Rats.  HERL Developmental  and Cell
       Toxicology  Division Report.

       Shah, P.V.  e_t al.   Dermal  Penetration of Carbofuran
       in Young and Adult Fischer 344  Rats.  J. Toxicol.  Environ.
       Health (Accepted for publication).

       Shah, P.V.  et al.   Penetration  of Fourteen Pesticides
       Through the SkTn of Young  and Adult Rats:  A Preliminary
       Screen: (Abstract  in the Toxicologist 5:264, 1985).  J.
       Toxicol. Environ.  Health 21_:353-366,  1987.


III.   Age Differences in Serum Chemistry Changes Following
       Pesticide Exposure;


       MacPhail, R.C., Pad ilia, 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).

       Pad ilia, 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 Exposurej


       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. e_t 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. §2:127-136, 1985.

        Gray, L.E., Jr.  Compound-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^t6"7-BQt 1982.


 VII.   Development of a Male Rat Fertility Model;


        Carter, S.D. et  al.  Effect of Benomyl 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.
        15.: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.


VIII.   Susceptibility to Renal Toxic Effects During Lactational  and
        Prepubertal Period:


        Daston, G.P. et  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. et al.  Toxicity of Mercuric  Chloride  to  the
        Developing  Rat Kidney. III.  Distribution  and  Elimination of
        Mercury  during Postnatal Maturation. Toxicol.  Appl. Pharmacol,
        £5:39-48, 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 41_:279-288, 1982.

        Kavlock, R.J., and Gray, J.A.  Morphometric, Biochemical,  and
        Physiological Assessment of Perinatally-Inducted Renal
        Dysfunction. J. Toxicol. Environ. Health j^:l-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 Endpoints 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 1_1_: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/
Toxaphene/Tref 1 an- peas ,
Carbofuran- sugar cane
Carbaryl-cucumbers ,Aldicarb-
peas , Tbxaphene/Methyl
parathion- peanuts
End osul fan- peas , End osul fan-
corn ,Benomyl-grapes
Captan-strawberries
Acephate (methamidophos)-
tobacco
Aid ic arb/ Chi or othal on il/
Dinoseb/biquat/Endosul fan/
Linuron/Polyram/Mancozeb/
Methamidophos/Methomyl/
Metribuzin/bemeton-potatoes
Ethyl parathion/Malathion/
Benomyl-blueberries
D inoseb-potatoes
Endosulf an- tomatoes
ULV Malathion-blueberries
Toxaphene/Malathion/para-
thion( ethyl & methyl )-onions
Mai ath ion/Me thiocarb/
C aptof ol- blueberries
Captan/Guthion/Imidan- apples
Captan-strawberries
Carbaryl-strawberries
V inclozol in- s trawberr ies
Captan/Benomyl- 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 thy 1- cucumber
Chlorothalon i 1- tomato
Lannate (methomyl )-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(ISII)
s Harvester Expos
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.
Harvester Expos.

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                                                    10
Youth 1n Agriculture:  Pesticide  Exposure  to
  Strawberry Pickers,  1981
        Research  performed  by

        University  of California
        Richmond, CA  94804

        September 1982

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                            Abstract
During five field studies in 1981, 78 field workers on three
different strawberry farms in California and one in Oregon were
monitored for dermal exposure to captan.  Lower arms and hands
were by far the areas of greatest dermal exposure.  A comparison
of dermal dose rate among children (- 11 years) or youths (- 13
years) and adults revealed lower doses to children and youths
than adults.  Age and productivity correlate positively with
dermal dose.  An increase in age results in higher productivity
and consequently higher dermal exposure.  A positive correlation
was found between dislodgeable residues of captan on foliage and
dermal exposure.

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                          TABLE OF CONTENTS
                                                                          12
                                                            Revision No.   -  l
                                                            Date:  September,  1552
                                                            Page  1  of   1
SECTION


1.0
2.0
                                          PAGE  NO.
3.0
 SUMMARY
 INTRODUCTION
 EXPERIMENTAL PROCEDURES
 2.1  Field Studies
 2.2  Sampling Procedures
 2.3  Chemical Analyses
 RESULTS AND DISCUSSION
 3.1  Dermal Exposure by All Subjects
 3.2  Captan Dermal Exposure by Different
     Age Groups
 3.3  Individual Variability of Dermal
     Exposure
 3.4  Captan Exposure by Kale and Female
     Strawberry Harvesters
 3.5  Distribution of Dermal Exposure by
     Different Parts of the Body
 3.6  Dislodgeable Foliar Residues and
     Dermal Exposure
 3.7  Dislodgeable Foliar Residue
     Decay Studies
 3.8  Captan Aerosol Concentrations
 3.9  Captan Soil Residues
 3.10 Miscellaneous Correlations
 References
Appendix
 2-20
 9-20
18-20

 2-48
 3-48

 5-48

 6-48

 7-48

 8-48

 9-48

 11-48
 13-48
 15-48
              PAGES

                1
                1
               20
33
                                                                      1
                                                                     43

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                                                                              13
                                                           Section No..
                                                           Revision No.   - 1
                                                           Date: September 1982
                                                           Page ' 1    of   .1
                                   SUMMARY


      During five field studies  in  1981, 78 field workers on three different
 slrawberry farms in California  and one in Oregon were monitored for dermal exposure
 to captan.  Based on these  results and a statistical analysis of these, the
 following conclusions were  reached:

      l.  Lc/.'er arms and hands were by far the areas of greatest dermal exposure,
 ranging from 7-21 % and 60-88* of total dermal exposure, respectively.

      2.  While a positive correlation was observed between aerosol concentration
 of captan and dermal exposure,  the ratio of dermal and aerosol concentration doses
 was found to be approximately 100, suggesting that aerosols do not constitute
 a significant route of exposure.

      3.  The average hourly dermal exposure by strawberry pickers  to captan ranged
 from 4.70 mg/hr to 17.41 mg/hr.  Normalized for body weight,  this  exposure
 calculates to 0.082 mg/kg/hr and 0.310 mg/kg/hr, respectively.  The standard
 deviations for these exposures  were  high, indicating large variability of dermal
 exposure among harvesters.

      4.  In terms of absolute dermal dose rate (mg/hr), a comparison between children
 (ill  years old)  or youths  (i 13)  and corresponding adult groups  revealed a trend
 toward lower doses to children  and youths than adults, but a  statistically significant
 difference in only one field.   When  dermal doses are adjusted for  body weight/mass
 (mg/kg/hr), the corresponding dose rates appear even more equal with higher doses  only
 to youths in one field.

      5.  Age and productivity of strawberry pickers appear to correlate positively
 with  dermal  exposure;  age and productivity are also cross correlated.  Thus, one
 may conclude that increasing age results in higher  productivity  (experience and
 motivation);  higher productivity results in higher  dermal exposure,  and consequently,
 increasing age of pickers results  in higher dermal  exposure.

      6.   No  difference was  found between dermal exposure by  female and male
 strawberry harvesters.

      7.   A positive correlation  was  found between dislodgeable residues of captan on
 foliage  and  dermal  exposure by  strawberry pickers,  suggesting that dislodgeable
 foliar  residues  represent an important route  of dermal  exposure of pesticides  by
 strawberry pickers.

     8.   Dermal  exposure of weeders  in strawberry fields  averaged 94.13  mg/hr, a
 concentration  considerably  higher  than that observed  for  pickers.  The distribution
 of dermal  concentration on  the  body  of weeders was  extremely variable, the hands,
 however,  receiving  the lowest dermal dose,  in contrast to the distribution found
among pickers.   While  this  operation is much  less  frequent than harvesting,  the
cause for this higher  exposure  is  only speculative  at this time.


                                     .       of

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                                                                                   14
                                                        Section No.	1_
                                                        Revision No. -
                                                        Date -  cop^pnKfr  1Qg2
                                                        Page _J	pf_J__
                 Pesticide Exposure to Strawberry  Pickers
                  ^
                              1981 Studies
1.0  INTRODUCTION
      In order to assess the exposure to pesticides by fruit harvesters of all
 ages and both sexes, the California Project  of  the National Pesticide Hazard
 Assessment Project (PHA?) of the EPA undertook  s. series cf field studies during
 1981 involving strawberry harvesters.   These studies have now been completed,
 and the results are given in this report.  In order to simplify the chemical
 analyses and interpretation of data during the  first year's studies, we chose the
 fungicide captan (N-trichloromethylthio-4-cyclohexene-l,2-dicarboximide) for
 detailed investigation.  Statistical  methods were applied to find significance of
 difference and linear correlations between several variables like age, sex,
 productivity, and groups of individuals, e.g.,  children (10-11 years old), youths
 (less than 13 years of age) and adults.
                                               02

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                                                        Section No.   2
                                                        Revision No.  -  1
                                                        Date:  SepteTnhpr''°s?
                                                        Page  1    of.   20   _
2.0  EXPERIMENTAL PROCEDURES
     All of the field studies which will be described in detail below were
 designed to monitor the dermal exposure of strawberry pickers during actual
 harvesting of the berries in the early spring (first fruit), middle and late
 summer in several locations in California and one location in Oregon.  An atter.pt
 was made to select volunteers representing both sexes and children under the age
 of thirteen.  This was not always successful (see Study No. 5) due to the lack o*
 appropriate subjects in a particular field situation.  Environmental samples like
 aerosols, dislodgeable residues on foliage and fruit, and soil residues were also
 taken in some of the field experiments.  Sampling procedures and analytical methods
 will be described in later sections.
                                           03

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                                                                             16
                                                    Section No.    2	
                                                    Revision No.  _J	  	
                                                    Date:   September 1982"
                                                    Page   2	of_  20
 2.1   Field  Studies
      During the Summer of 1981,  five  pesticide residue studies on strawberry
 crops were conducted;  four in the  Salinas Valley of California  and one in
 Corvallis, Oregon.   The California  studies were conducted on May 9, July 21,
 and two on August 21, 1981  and the  Oregon study on June 22, 1981.
 The study dates had to be chosen in order not to  inconvenience  the  cooperat-
 ing growers and to obtain data from a variety of post-application dates.
      In each of these field studies attempts were made to obtain the volunteer
 services of about 20 workers,  including  children and adults of both sexes.
 Due to the lateness in harvesting in  August, the number of cooperating
 pickers was considerably lower,  but the  results of these studies will
 nonetheless be reported here.
      For each study, the subjects'  weight and height were measured  before
 the pickers entered the field  on that particular day.  Personal  dosimeters
 and some personal  air samplers were placed on the subjects, as will be  described
 in  the next section, 2.2.     Observations were made throughout  the work  day
 on  personal  clothing (removal  of outer garments, etc.), work  habits and
 peculair traits which might explain abnormal exposure  values  of individual
 pickers.   At the end of the work day, each picker reported  the  total  number of
 crates  he  harvested.  The crates in California  picked  for market contain
 about  11  Ibs of berries, while the  Oregon  crates, mostly  picked for canning
 and  processing, contained 13 Ibs of strawberries.   Distances  covered by each
 picker  throughout the day were estimated for Studies  1 and  3.  Dosimeters
 (pe.tches and gloves) were removed from the workers  and stored in dry ice for fjiure
analysis.                           -

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                                                   Section No. 	f
                                                   Revision No.	i"
                                                   Date:     September 19S2
                                                   Page   3	of	,
The following field  experiments will now be described in greater detail:
           Study Number
      Site       Days  Post-
                 Application
             Number of Sj?je:ts
             Youths      Acults
             2
             3

             4

             5
Salinas, CA
Farm A
Corvallis, OR
Salinas, CA
Farm A
Salinas, CA
Farm B
Salinas, CA
Farm C
10

26
 3

 3

48
 8

12 .
 8

 3

 0
li

11
 7

 3

10
Youth defined as 13 years old or younger
                                           05

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                                                                              18
                                                         Section No.	2
                                                         Revision No.	_
                                                         Date :___SepteiTiber_ 1982
                                                         Page   4   of    20
 A. Field Study No. 1
      A Mexican-American farm cooperative  located near Salinas, CA, consisted  of  tv.c
 40-60 acre plots, one of first year  and the other of second year strawberry plants.
 This cooperative farm is owned and operated by member families who each maintain
 a designated section of the fields.   Family members including children under  the
 age of ten to eleven work in these fields during harvest time, which in
 California extends from about mid April until October-November.
      The field study was conducted on a Saturday, May 9, 1981, in order to
 observe 10-11 year old pickers, who  would be working in the fields only during
 the weekend because of school  attendance.  Ten days prior to the  study date, the
 fields had been sprayed with several  pesticides:  captan, benonyl, and
 malathion as is shown in Table A-2.   The  fields on this farm are  irrigated by
 drip irrigation and furrowed irrigation,  and the study area included both sections
 of the farm.   The study population was composed of 4 subjects age 11 and under
 and 16 subjects,  12 years of age and older.
      Temperature  was taken at mid-day and measured 73°F in the shade;  humidity
 was 66%,  and the  wind speed ranged from 5.7 to 9.1 mph with a few gusts of
 13  mph.

B.  Field  Study No.  2
     The object of our studies on strawberry workers and  their  possible
exposure to  pesticides was to observe strawberry  pickers  in  two  divergently
                                                   06

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                                                                               19
                                                        Section No.	2_
                                                        Revision No.	1_
                                                        Date -.^September 19E2
                                                        Page  5    "of"   20
 different  locations.  The growing of strawberries in Oregon  is  quite different
 from the practices in California.  For example,  Oregon  varieties  of berries,
 Benton are usually harvested for about three weeks in June-July.   Secondly,
 weather conditions might be quite diffrent from those encountered in California.
 For  example  rain fall during the Oregon harvest season  is not uncommon.   Also,
 heavy dew  in the morning is much heavier in Oregon than might be  found in
 California.  Furthermore, strawberry harvesters in Oregon are hired hands and
 do not necessarily belong to the family which owns the  farm.  Many school
 children work on the strawberry farms during their summer vacation.
     The particular site which was chosen for our study in Oregon was
 a privately owned strawberry farm in Corvallis,  Oregon, and   consisted of
 15 acres of strawberries on leased land.  The berries were of the Benton variety
 and  two years old when the study was conducted.
     The date of our Oregon-study was Monday, June 22, 1981.   The  fields had
 been previously sprayed on May 27, 1981 with captan, benomyl, and carbaryl,
 resulting  in a 26-day post application date(see Table A-10). Twenty-three volunteer
 subjects ranging in age  from 11 to 38  of both sexes were outfitted with  dermal
 dosimeters as described in  Section 2.2 of this  reonrt.   In  addition
 to all other observations made in the California studies, the hands of the
 subjects were traced on graph paper in order to estimate their  surface area.
The temperature during the day was cool (61-67°F), and  some  rain  fell during
parts of the  work  day.  There was very  little wind during the day  ranging
 from 1.3 to 2.1 mph.  Humidity ranged  from  77 to 93» RH.
     A map of this farm is shown in fig. 1   ; field observations were conducted
 in Areas A and C.
                                        07

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                                                                                              20

                                                                            Section No.   2
                                                                            Revision No.  i
                                                                            Date:     September 1952
                                                                            Page   6  of  20






















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	  FOOT PATH
       TRUCK PATH
                         FIGURE  1.  STRAWBERRY PLOTS  FIELD STUDY NO. 2, CORVALLIS. OREGON
                                                      08

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                                                                           21
                                                    Section No.       2	
                                                    Revision No.	   J_   	
                                                    Date:	September 19E2
                                                    Page       7    of     20
 C.   Field Study  No.  3
     This  study was conducted on July 21,  1981  on  the  same  cooperative  strawberry
 farm as  in Study No. 1.  The study population consisted  of  15  pickers  (several
 other workers discarded their gloves or patches before the  end of the  workday
 and  were  thus removed from the study) and  four weeders.   Their ages  ranged
 from 8 to  42 as is shown in Table    (Appendix).   One  of the "pickers" who
 was  six years of  age and who only picked  less than one  crate  of berries
 during 3 1/2 hours was not included in the evaluation  of harvesters' exposure
 and  will be discussed  separately  under Results and Discussion, Section  3.
     The weather early in the morning, from about  0730 until 0930, was
 foggy with the temperature increasing from 53°F to 59° with the relative
 humdity  decreasing from 28% to 86%.  During the early afternoon (1300),
 the  temperature rose to 76°F and dropped back to 71eF  at 1505 hours, the
 end  of the work day.  The wind speed in the morning ranged from 2.'3-3.0 mph,
but  later during the day gusts of wind as  high as  16-20  nph were recorded.
                         «
     Different pesticides had been applied on various  dates prior to this
study,  as is shown in Table A-2, and the latest captan application occurred
three days prior to our investigation on July 21,  1981.
                                     09

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                                                                              22
                                                        Section No.	f	
                                                        Revision No.	 _]_	
                                                        Date:    September'1582
                                                        Page    8   of     20
 D.  Field Study No. 4
      This study was conducted during the  morning of August 21, 1981 on Cooperative
 Farm B near Salinas, California.   Due to  the  lateness in the season, there
 were few berries and only several  families were in the fields picking berries.
 Six harvesters were monitored for  the same length of time (3.5 hours); their
 ages ranged from 8 to 41.  The temperature stayed fairly constant during the
                                                                      •
 time of the study (65 - 69.5°F) with the  relative humidity"ranging from
 75 to BB'.>.   Wind speed was recorded at 4.5 to 15 rcph, and the day could best
 be described as "cool and windy".
      Pesticide applications were made according to the schedule found in Table A-Z1,
 and the last application of captan had been made three days prior to the day
 of the  study.
 E.  Field Study No. 5
       Due  to the shortage of volunteer subjects found on  Cooperative  Farm B,
 the study  team was split up on August 21, 1981, and another group moved to
 Cooperative  Farm C to perform an additional  study on the  same day. This
 farm was located just a few miles away from Farm B.  Ten  subjects were studied,
but no youths  or children were working on that day.  The  weather conditions were
 very similar to those recorded for Study No.  4.  Pesticide applications had
been made  throughout  the season as is shown in Table A-28.  The interval between
the day of last application of captan and the 21st of August, 1981 was 48 days.

                                       10

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                                                                             23
                                                    Section  No. 	2
                                                    Revision No.	-	
                                                    Date:     2 August  \m
                                                    Page      9      of_  ZO
2.2  Sampling Procedures
 Dermal Exposure to Pesticides -
      This project employs  a  gauze pad as a dermal dosimeter for all areas of
 the worker's body except the hands  (see Figure 2 and 3).  This dosimeter consists
 of a 12-ply 3x3 inch  gauze surgical sponge.  A polyethylene "moisture barrier"
 is placed on the side of the pad facing the skin of the subject.  All of this is
 held in a glossy paper  envelope.  The side of the envelope facing away from the
 skin has a circular hole 60  mm  in diameter exposing 28 cm2 of the gauze pad.  -
      Body locations for mounting the gauze pad dosimeters are as follows:
      Head -- mounted on the  side of the head, roughly over one ear, either stapled
              to a stretchable head band or taped to the inside of the brim of the
              subject's  hat (1);
      Chest — mounted over sternum between the pectoral muscles (1);
      Back ~ mounted over backbone between the scapulae (1);
      Upper Arm  -- mounted over the deltoid muscles (2);
      Lower Arm  — mounted roughly midway between the elbow and wrist on the
                   dorsal surface (2);
     Lower Leg  —  mounted roughly midway between the knee and the ankle on the
                   anterior surface (2).
     For  ease of  mounting and dismounting the patches, the chest, back and upper
arm dosimeters are stapled to T-si.irts which are dispensed to the subjects at the
beginning of the work period and collected at the end.  The T-shirts are
worn next to the skin of the subject so that the dosimeters will be exposed to
only that portion of the residues that would eventually reach the skin.  Lower arm
TT

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                                                                       24
                                                      Section  No.    2
                                                      Revision No.   ]

                                                      Date:    September 19E2
                                                      Page  10  of  2D
                          FIGURE 2
         Photograph of Strawberry  Picker Outfitted with
Dosimeters on chest, head,  upper and  lower arms, and gloves
                  Farm A,  Salinas,  CA, 21 July, 1981
                             12

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                                                                   25
                                                    Section No.    2
                                                    Revision No.   '
                                                    Date   September T9E2
                                                    Page   11  of  20
                            FIGURE  3
              Photograph of Family and Friend Outfitted
                     with Dosimeters
from left  to  right:  father (42yrs old) son(16), son (8), friend (11),
                    daugh:er(12)
                                 13

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                                                                                      26
                                                     Section  No.
                                                     Revision No."
                                                     Date:     September 1982
                                                     Page      12    of  2"
 and lower leg patches are taped directly  to the skin in the appropriate location
 after the T-shirt is donned.   The subjects then wear whatever clothing they would
 normally wear while working,  except that  if they were to strip to the waist
 (which some male workers in California  do) they would continue to wear the
 T-shirt bearing the dosimeters.
      A hand dosimeter consists of a light-weight cotton glove.  For those subjects
 who feel uncomfortable wearing gloves picking strawberries, the finger tips of
 the thumb and first two fingers will be cut from the glove worn on the picking
 hand.   This will allow stemming or other  delicate manipulations the subject feels
 might   be hindered by even the light-weight glove employed in this study.
 Personal Aerosol Monitors —
     Personal  breathing zone  air samples  will be taken on at least two subjects
 each working period for two hours.   An  open-face, 37 mm Millipore cassette
 (0.8 v pore size)  is mounted  on a subject's breathing zone and is aspirated at
 2.0 ±  0.2 Lpm with a belt-mounted portable pump (Figures 4 and 5).
 Foliar Samples —
     Foliar sampling is  accomplished by  using a leaf punch equipped with a
 3 cm diameter die  (see  Figure 6).   The  punch-through action of the device pushes
 the  leaf disk  into a 4-oz wide-mouth jar  which is attached to the punch and which
 subsequently  serves  as  the sample  storage container.  The punch is also equipped
 with a  resettable  counter.
     Sample collection  is  accomplished  by striking out diagonally across the aree
to be  sampled, stopping  every three or  four rows to take a single leaf sample.
The sampling  points  are  to  be distributed throughout the areas of the planis
that the  harvester *fill  actually  contact.  For strawberries, this includes all

                                   ...     14

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                                          Section No.  2
                                          Revision No.  1
                                          Date:    September
                                          Page  13  of  20
      ^Uyr^-..V,^^^.v  ,   .-   .,<>>
                 FIGURE 4
Photograph of Strawberry Picker Equipped with
       Personal Air Sampler
   Farrc A, Salinas,  CA; 21 July, 1981
                  15

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                                                             28
                                            Section No.  2
                                            Revision No. 1
                                            Date:    September 1982
                                            Page 14  of  20

                FIGURE  5
      Air Sampler,  Stationary  Position
For Measuring Aerosol  Concentrations  (July 21, 1981)
                      16

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              FIGURE 6
                                                          29
                                         Section  No.   2
                                         Revision No.  1
                                         Date:     September 19£2
                                         Page  15 of'20
Mechanical  Leaf Punch Being Operated by
          Field Personnel
                 17

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                                                                               30
                                                    Section No. 	2	
                                                    Revision No._     1
                                                    Date:	September  195?
                                                    Page       16    of    20
 parts of the plant, both  outer  and  inner canopy leaves, from either side  of the
 row, and from the center.   The  standard sample size is 48 disks.  If the  edge of
 the field is reached before the full complement of leaf disks has been obtained,
 the person collecting the sample merely reflects back into the field on a new
 diagonal.
 Soil Samples -
      The soil  sampling device has two parts: a three-sided form 10 endlong by
 8 cm wide and 8 cm high,  which  when pressed into the soil surface blocks  out
              2
 an area  80 cm; and a small  rectangular shovel which fits just inside the form
 and has  a 1  cm high rim around  the  sides and back (see Figure 7).
      Sampling is accomplished by first shoving the form  into the soil several
 centimeters.   The shovel  is  then inserted vertically into the soil at the open
 face of  the  form, likewise,  several centimeters; and the soil is scraped  away
 from the form with it to  a depth of several centimeters.  The shovel is then
 run  into the  form horizontally  so that it picks up a layer of surface soil the
 area  of  the  form and 1  cm deep.  The sampling pattern utilized for taking soil
 samples  is the same as  for taking foliage samples, being collected on a diagonal
 across the area  being harvested by  the cooperating pickers.  However, since
 there are only six "scoops"  taken,  rather than the 48 sampling  sites  for  the leaf
punches,  samples  are taken every 8  to 10 rows.  Furthermore, samples  are  taken
in the area between the planted burms, which is where pickers  are  physically
located, and where they contact the soil.   Soil samples  are  held in  a paper sack
 (*4 lunch bag) which is in turn placed in a plastic  bag  to  reduce  moisture less
in frozen storage.                    i n

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                                   Section  No.   2
                                   Revision No.   1
                                   Date:     September
                                   Page    17  of  2C
FIGURE 7   SOIL SAMPLER
        19

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                                                                            ff'
                                                                                   32
                                                      Section No. 	2	
                                                      Revision No.      I       ~
                                                      Date:September I9s^
                                                     Page      IB    of_   25 _
 2.3  Chemical Analyses
 Dosimeters -
      Samples consist  of one or two pads (one for main  trunk or two for limb
 sample  sites)  stapled inside paper application packs stored in an RRE Zip-
 lock bag  in  the  freezer.  After the samples were removed', the pad together with
 the plastic  moisture  barrier was transferred to a 125  ml LPE wide-mouth bottle.
 Thirty  ml of toluene  some of which is used to rinse the  bag, were added and the
 sample  shaken  at about 200 Hz for one hour.  Ten mL aliquot of the analysate
 was reserved in  a glass polyseal vial, and an auto-sampler vial was prepared
 from the  remainder.
      The  gloves were  treated in a manner similar to that used  for the patches
 and were  also  frozen,  one pair to a sample bag.  100  mL of toluene was used
 to extract eech pair.  If a subject wore more than one pair, the solvent was
 increased only to the extent that an aliquot could easily  be removed and the
 actual  amount of solvent was noted.
      Aliquots  of the  extracts were  analyzed on  a Tracer 222 gas-liquid chromato-
graph, using  a  mixture of  argon-methane as  carrier gas (65 ml/min), OVI (10«) on
Supelcoport  (80/100  mesh),  3' x  2mm (i.d.)  column at a column temperature of
210°C, using  a  63Ni-electron  capture  detector.   Captan under these conditions elutes
at 1.27  minutes.  Quantification was  performed by area-integration and expressed
as "rr.icrograms  per sample."   To  calculate  dose rate per  person, the following
calculations  were made:
          *» / U «» £    *^ DC J W ' W ' *••» A \ VI'  J W • i b WC U ' t 6
          */n      '        (cmipatcnj x nr  x  1,000
                                       2
                        pesticide x (cm  surface area of body part)x F
                                                                                      \
         ?              22
where  cm patch a 28 err; "cm  surface area, body part", see Table A-l  ,  and
                                 r   A indiv.       *
                                     1.92
* Body surface of 50-percentile r,an is 1.92 r-(Popendorf and Leffingwell, 1SS2)
                                              20

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                                                                                  33
                                                         Section No.   2	
                                                         Revision No._j	
                                                         Date:     September_JL=52
                                                         Page  19   of   20
 Strawberry Leaf Punch  and  Fruit Samples -
      The standard  leaf punch  sample consisted of 48 3cm leaf disks frozen in
 a glass jar with a water-tight plastic cap.  Berries were also kept frozen until
 being analyzed.  After a half-hour thawing period, the leaves or fruit were placed
 into a one-pint square Mason  jar with the standard lid and ring closure.  Six
 drops of a 20  mg/L solution of dioctyl sodium sulfosuccinate was added to the
 sample jar.  The surfactant and dust from the leaves were also transferred quan-
 titatively to  the  Mason jar with 100 ml of distilled water.  The samples were
 shaken for 30  min.  on  a mechanical shaker platform at about 140 Hz and the liquid
 decanted into  50 ml methylene chloride (dichloromethane) in a 500 ml separatory
 funnel,  using  a  narrow stemmed funnel to avoid transferring the plant samples.  The
 process  of washing the samples with surfactant and water was repeated twice.
 The  separatory funnel  was  shaken 30 times and the organic  layer was  drained  through
 a  small  funnel  plugged with glass wool and filled with anhydrous  sodium  sulfate into
 a  500 ml round-bottomed 24/40 flask.  The extraction process was  repeated  twice more
 with  fresh  50  mL aliquots  of  solvent and the combined solvent was  rotary evaporated
 to about 1 ml.   Ten ml of  toluene was added and evaporated.  This  process  was  repestei
 twice  more.  The final residue was quantitatively transferred  to  a 10 ml volumetric
 flask.   The sample was then ready for gas chromatographic  analysis.
     The  dust  which was washed from the leaf surfaces remained in the  interfacial
 layer  in  the separatory funnel.  This material was  filtered onto  a pre-weighed
 glass filter,  dried at 110°C  overnight and cooled  in  a  desiccator.  Post-weighing o*
                                       •
the filter yielded the foliar dust weight.
                                      21

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                                                                                34
                                                         Section No.	2_
                                                         Revision No._ 3	
                                                         Date:    September  1982
                                                         Page JO   of   20   _

 Soil Samples -
      The samples were sifted through a  #10  sieve to break up lumps and remove rocks
 twigs and leaves.  The sifted sample was  mixed and a 250 ml portion was taken,
 placed in an ambient vacuum desiccator  and  dried for 24 hours or more until  the
 residual moisture was less than 0.5X.   A  glass soxhlet thimble was prepared  by
 placing  1.5 cm of acetone washed sand  in the bottom to protect the extra-coarse
 frit from fouling by soil  fines.   The thimble was tared and., about 30 gm of soil was
 added,  the weight being taken to  four significant figures.  The thimble was  then"
 pieced  in a 250 ml soxhlet extractor and  cycled for four hours.  The solvent used
 is  an azeotropic acetone-hexane mixture (59% - 41%).  After extraction, the solvent
 was  removed by rotary evaporation and replaced by a solvent compatible with the
 analytical  method to be used - toluene  for  GC only, acetonitrile for GC plus HPLC.

 Aerosol  Samples -
      Aerosol  samples consisted of Millipore disposable cassettes with 37-rrcn
 membrane filters.   The filters were  dropped from the cassette directly into
 a 500-ml  Nalgene LPE wide-mouthed rectangular bottle without the need for manual
 transfer.   Loose dust was  washed  off the  cassette with hexane which  is allowed tc
evaporate on  the bottom of the bottle.   Captan was  then extracted with 30 ml of toluene
by a one-hour  shake  as is  described  under "Chemical Analyses -  Dosimeters".  The
extract was concentrated or diluted, whichever was  necessary,  and  analyzed  by
GLC as described above.
                                            22

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                                                                             35
                                                     Section No.  	3_
                                                     Revision No.    1
                                                     Date:     September 1982
                                                     Page    1      of  46
 3.0  RESULTS AND DISCUSSION
      The primary aim of these  studies was estimation of dermal exposure to
 pesticides by strawberry pickers of different ages.  These studies were to
 be conducted under varying environmental conditions, different pesticide
 application schedules,  and at  two geographic locations on the West Coast.
 In the five studies reported here no attempt was made to conduct analyses of
 urinary excretion of pesticides or their metabolites.  This will be the subject
 of subsequent studies.   An effort was made to examine a broad spectrum of field
 workers and to determine if dermal exposure was related to their age. -The
 exposures reported here are estimates for the fungicide captan as experienced
 by strawberry harvesters.  Extrapolating these data to "dose" can be performed
 quantitatively only when the pharmacokinetics and dermal absorption of captan
 have been studied.   If  someone wishes to use these results to calculate absorbed
 "dose", he may be able  to make an approximation by using generally accepted
 absorption rates  (about 10»).  Quantitative studies on the dermal absorption of
 C-14-captan in rats are being  conducted presently by Dr. James  Knaak at U.C.
 Davis  in  association with the  California PHAP.  Once these results have been
 reported,  it may  be possible to derive better quantitative data  for  dose  of
 captan  from dermal  exposure.
     Of the five  studies on captan exposure conducted during  1981, four  were
 performed  on  three  different strawberry cooperatives in  California and one  farm
 in Oregon.   The studies  in California were run early in  the  season  (May), during
mid-summer  (July) and late summer (August).  The temperatures on the study days
were moderate  (61°  to 76°F) at relative humidities  ranging  from 77  to  98«.
Conditions  during the Oregon study provided an interesting  contrast  to those
encountered  in California.  The strawberry harvest  season  in Oregon  lasts three

                                        23

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                                                     Section No.     3	   36
                                                     Revision No.    1
                                                     Date:    September 1982
                                                     Page    2     of  48	
 weeks  compared  to 4-5 months in California.   The temperature at the Oregon site
 in mid-June was about 10°F cooler than that  found at  the  California study sites
 and rain  fell at the Oregon site.  Another difference which was found was the
 pesticide usage pattern (see Appendix).
      In the five studies, a total of 73 strawberry pickers were monitored for
 dermal concentration of captan.  Four weeders and one other atypical subject
 were included.
      All five field studies were conducted under actual harvesting conditions.
 No arrangements for special pesticide applications or type of workers were
 made.   Although this approach had the advantage of spontaneity, the disadvantage
 was that no control could be exerted on the  choice of pesticides  used or the
 number of children and adults who were harvesting fruit on a particular day.  As
 a  consequence, in Field Study No. 5, no subjects below the age of 13 yrs. were
 found,  but this study, never-the-less, provided additional data points for over-
 all  correlations and comparisons.
 Dermal  Exposure by All Subjects
      Comparing dermal  exposure to captan by  strawberry pickers in all five studies,
 it may  be  seen in Table 1  that the exposures ranged from  4.70 mg/hr to 17.41  mg/hr;
 or 0.082 mg/kg/hr to 0.31  mg/kg/hr.  The standard deviations from the means are
 very high, clearly illustrating the variability in exposure  among different  sub-
 jects on a particular harvest day.  In Study No. 4, the  standard  deviation was
 much lower than  in the other four studies, 16.37 mg/hr (S.D.  3.78).   The  smaller
 variability amoung subjects in this study might have been due  to  their  small
 number  (six),  having the same working hours  and being equally  divided among  males
and females.
     Dermal exposure to captan experienced by four weeders (Table II) showed an
average concentration  of 94 mg/hr (S.O. 120) or 1.7 mg/kg/hr.   The variability
                                    24

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                                                                              37
                                                     Section  No.       3	
                                                     Revision No.1
                                                     Date:      Septemoer  1982
                                                     Page    3     of   48
 among these four workers was very high as seen in Table II.   Worker No.  20  has
 a dermal  dose of 267 mg/hr compared to the next highest subject, No.  16  with
 72 mg/hr.  These results will be discussed below under "Dermal  Exposure
 Distribution."
 Captan Dermal  Exposure  by Different Age Groups
      In order to deal with the small target population of children under 12 years
 of age, while assessing the importance of age in exposure, three statistical
 approaches  were  used in the analyses of the results: (a) parallel comparison
 between children (age - 11) and "adults"*; "youth" (age -13) and "adults"*;
 and (c) correlation analyses of different variables, e.g., exposure/age, exposure/
 productivity,  etc.  The first approach is somewhat arbitrary but is mandated by
 law.   The second classification results in a more equally divided group.   Further
 statistical  support of  the 13-year cutoff point will be explored by examining
 the effect  of  age on weight, body surface area, productivity, and exposure (as
 is  addressed  by  the third approach).  The third approach is more general and
 permits qualitative interpretations from viewing the x-y plots and quantitative
 evaluations by calculating the correlation coefficients.
     A comparison of dermal dose rates and age groups  1s shown  in Tables III and
 IV; a  detailed statistical treatment of the data may be found in the  respective
 tables  in the  Appendix.  To demonstrate that real differences existed between
exposure  by age  groups, three statistical tests were applied: (1)  student's
t-test; (2) the  same test on log-transformed data (environmental  data is commonly
log-normally distributed, i.e., skewed), and (3) the Wilcoxon nonparametric  test.
* "Adults" are classified as being above the age  of  "children"  or "youth",
                                      25

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                                                                                38
                                                     Section No.      3	
                                                     Revision No.     1
                                                     Date :__sJyiifimter_12S2___
                                                     Page   A      of  4g	
      The p-value is the probability .that  there is no difference between the
 two groups.  (A probability of 0.05 or 5% is a common decision criteria.)  By
 and large, all three statistical  tests yielded similar trends, as may be seen
 in the respective Appendix tables.
      Table III shows that a significantly lower total dermal exposure exists
 for children versus adults in Field Study No. 3.  Although a similar trend is
 evident in the results from Studies 1, 2, and 4 (i.e., lower exposure by children),
 a statistically significant difference could not be ascertained for these data.
      It is noted, however, that all trends indicating any differences between
 children and adult exposures disappear when the exposure data are normalized for
 body weight (mg/kg/hr) (see bottom  of Table III).
      Comparing dermal  exposure in youths  and adults  (Table  IV), a similar trend
 of lower exposure by youths is observed in all four field studies analyzed,  but
 in only one study (No. 1) is the  difference between the groups statistically
 significant.   Again, when the exposure data are normalized  for body weight
 (bottom of Table IV),  the difference  in exposure between the two groups are not
 significant with the exception of Field Study 4, in which the dermal exposure
 for youth  was  higher.   This result, however, must be tempered by the smallness of
 the study  population (six subjects).
     The conclusion one may draw  from these results and their statistical analysis
 is that children and youths have  lower dermal body exposure during  strawberry
 harvesting,  probably due to the smaller body weight and body  surface compared to
those of adults.   This hypothesis is  proven by positive linear correlations in
three out of five studies.   As is shown in Table V,  the correlation coefficients
in these three  studies for exposure/body surface and exposure/body weight are
all above 0.5 and p =  0.05.   The  fact that Field Study No.  5  has a negative

                                            26

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                                                    Section No.      3	^°
                                                    Revision No.     1	
                                                    Date:    SpntPmhcr 1QR?
                                                    Page    5     of   48	
 has  a  negative correlation can be explained on  the  basis  that the population
 consisted  only of a small group of ten adults.
     Further evidence for age-related exposure  may  be  found  in Table  5.  A
 positive linear correlation is found in all five studies  comparing  age and
 productivity (expressed in crates harvested per hour). The  plot shown in Figure
 8 depicts  the data for all subjects in Field Study  No. 1  along with the  best-fit
 straight line; and, the correlation coefficient is  0.67.   The correlation between
 age  and dermal exposure is less clear and significant  only for  Study No. 1; this
 is also graphically shown in Figure 9, depicting age versus  total  dermal exposure
 of all subjects in this study with the best-fit straight  line.   A linear correla-
 tion was found in three of the five field studies for dermal exposure versus
 productivity as seen in Table V and Figure 10.
     Although the field results are not completely consistent for all five  studies,
 we can advance a possible explanation for adults being dermally exposed to  greater
 concentrations of captan than youths or children.  When one compares productivity
      •                                                           *"
 (number of strawberry crates harvested per hour) and age of workers, the product-
 ivity appears to increase with greater age (or experience) of pickers.  Thus,
 a  possible explanation for higher dermal exposure by adults might be that  greater
 productivity results in more contact with  dislodgeable pesticide residues  on
 foliage and fruits.  Further evidence for  this  hypothesis will  be  discussed in
 greater detail under "Dislodgeable Residues and  Dermal Exposure).

 Individual  Variability of Dermal Exposure
     As previously discussed and seen from the  data in Table 1, large  variability
 in dermal  exposures among individuals is found even during  one  particular  study.
The individual  variability might be  due to age, productivity,  and work  habits.
These factors are very difficult to  separate and study out  of  context.   However,
the 1981  field studies provided  some, a2$ough  limited, data on the intrapersonal

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                                                     Section No.      3	40
                                                     Revision No.     1        ~~
                                                     Date:    September 1982
                                                     Page    6     of  48	
 variability of strawberry harvesters.   The way  this came about was that Field
 Studies 1 and 3 were conducted on the  same cooperative, and that fortuitously
 three pickers participated in both studies.   These three individuals were monit-
 ored for captan dermal exposure on two separate dates  (May and July).  In Table
 IV, the dermal exposure for each of the three pickers  is shown for Experiments
 1  and 3.  The ratio of the two sets of exposures was calculated for each worker,
 and two of the subjects had about the  same ratio (2.51 and 2.56, respectively).
 while Subject "B.O." had a higher ratio.   An  explanation for the ratio being
 greater than 1 is that the post-application periods for Experiments 1 and 3 were
 13 and 3 days respectively, and the resultant foliar dislodgeable residues were'
 2,36 vg/cm2 and 3.85 ug/cm2, respectively (see  later discussion on page	).
 It is highly speculative at this time  to conclude that the fact that two workers
 had the sane exposure ratio provides evidence that intrapersonal variability  is
 smaller than interpersonal variability.  Extensive field experiments are in
 progress during 1902 to study the variability of exposures among strawberry
 pickers.
 Captan  Exposure Experienced by Male and Female  Strawberry Harvesters
      The field studies reported here provided a basis  to demonstrate whether  the
 sex  of  harvesters is a factor in dermal exposure to  pesticides.  Table  VII
 summarizes  the results from these studies and shows  that in one of  the  Studies
 (No.  1),  the  six  females received significantly higher exposure than the corres-
ponding  13 male workers (10.04 y£. 4.87 mg/hr). This  difference  could  not  be
demonstrated  in subsequent studies.  It is concluded,  therefore,  that  exposure
differences due to the sex of the picker is probably not a  general  occurrence.
                                     28

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                                                                               41
                                                     Section No.       3
                                                     Revision No.	1
                                                     Date:    September 1982
                                                     Page    7     of   48
 Distribution of Dermal  Exposure  Over  Different Parts of the Body
      The agricultural  practice of  strawberry picking is a hand operation in which
 the harvester squats,  kneels, and  sometimes sits between rows of strawberry plants
 and picks with two hands.   When  berries are picked for the fresh-fruit market,
 the picker will grab the fruit at  the stem about 2 cm below the crown and twist
 the fruit off with j fast  wrist  action.  The experienced picker can perform this
 operation equally with  both hands.
      Fruit picked for canning or processing is handled in a different manner.
 The harvester will pick the fruit  with one hand and pluck the stem off with the
 other hand.   Strawberries  harvested in Oregon went mostly to canneries, while
 in California during the early season, the berries were delivered to the fresh-
 fruit market.  From these  observations it appears reasonable to expect that
 different parts of the  body receive varying concentrations of pesticides  depend-
 ing on the mode of picking as described above.
      Table VIII clearly shows that the hands received the greatest amount of
 dermal  exposure, ranging from 60 to 85* of total dermal  body exposure.  The  next
 highest exposure was seen  on the lower arms  (7% to 21% of total) and  the  lower
 legs  (1* to  10% of total).  The  remainder of the dermal  dose was unevenly
 distributed  with great  variability among the other parts of the  body  which were
 monitored (head, chest,  back and upper arms).
     The sum of hand and lower arm exposure calculated to 81-98* of  the total
 for all  field experiments  (see Table  IX).  From these  results  one  may conclude
 that the  major  dermal exposure from hand-harvesting  crops grown  close to the
 ground  (e.g., strawberries)  occurs on the hands,  lower arms  and  legs of the
 harvesters.   If  one  wanted to minimize pesticide  exposure to these field workers,
one could provide  suitable gloves  with gauntlets  and reduce  dermal exposure
considerably.

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                                                     Section No.      3
                                                     Revision No.     1
                                                     Date:    September 1 Qfl?
                                                     Page    e     of  48
42
      A possible explanation for the observation that the lower legs of the
 harvesters receive an appreciable concentration of pesticides is the occurrence
 of dew during the early morning hours  which causes the lower pant legs to become
 water soaked and contaminated with dislodgeable pesticide residues.
      An atypical case of abnormally high  dermal exposure was found on one six-
 year old male picker (see Table X). Although classified as a picker, this
 young subject probably was playing in  the strawberry plants and was becoming
 exposed to all parts of his body.  Eighty-six percent  (86») of dermal exposure
 was concentrated on his chest and stomach.
      Also atypical is the pesticide distribution  on the body of the four weeders,
 previously discussed (see Table II).  These subjects had small amounts of captan
 on  their hands; Subjects 12 and 16 had the greatest amount on head and neck;
 Subject 20 en his head, neck and lower arm.  This last subject also had, by far,
 the largest dermal exposure of all 78  subjects  studied.
      Weeders, as a group, exhibited about five  times the dermal exposure found
 amoung  the highest group of strawberry pickers  (see Table 1).  The possible
 explanation for this high exposure and atypical pesticide distribution on their
 bodies  may be found in the finding of  pesticide soil residues of  6.29 ppm in
 the  fields where the weeders were employed.  The  stirring up of contaminated soil
 by weeders and playful children will stir up an aerosol which will  settle on all
 parts of  the  body resulting in dermal  exposure  to pesticides adsorbed  onto
the  dust  particles.

Dislodgeable  Foliar Residues and Dermal Exposure
     A  possible  source of dermal exposure among strawberry pickers might be the
dislodgeable  pesticide residues found  on  foliage  and fruit.   As may be seen
from the  data in Table XI and Figure 11,  a positive linear correlation exists
between dislodgeable foliar residue and total  dermal  exposure (mg/hr).  The data
                                           30

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                                                                               43
                                                     Section No. 	3_
                                                     Revision  No.    1
                                                     Date:    September 1982
                                                     Page    9     of   48
 were obtained  from the five sites where the studies were conducted and the
 exposures  are  the mean volues of all  subjects monitored; thus,  large experimental
 variability  is to be expected and, indeed, was found.  The  plot in Figure 11
 includes S.E.M.'s for all data points.  A reasonably  high correlation coefficient
 (r2 = 0.32)  indicates that the two variables, dislodgeable  residues and  dermal
 exposure,  are  dependent.
      This  correlation is compatible with those of the resuspension of dislodge-
 able residues  from foliage.  In fact, the average ratio  of  foliar residue  (yg/cm2)
 to dermal  exposure rates (mg/hr) of 5.8 is quite comparable to that  for  other
 crops (Popendorf and Leffingwell, 1982).  However, the major deposition  onto
 the hands  of strawberry harvesters (with the subsequent  build-up of a  detritus
 layer on the hands or gloves) and the probable differential absorption  among
 various body parts may mitigate the health impact of these findings.
      Dislodgeable captan residues on strawberry fruit, as shown in Table XII,
 range from non-detectable to 1.20 ppm.  The residues appear to be indirectly
 correlated with time after last pesticide application; i.e., the shorter the
 time period, the higher the dislodgeable residues.  At 3 days  after last applica-
 tion of captan, the residues were about 1 ppm; at 26 days they were non-detectable
 or  0.35 ppm, and at 48 days after the last application, the residues were 0.09
 and 0.49 ppm.  These findings are in agreement with  the concept  of pesticide
 degradation  in the field due to biological and environmental  factors.

 Dislodgeable Foliar Residue Decay Studies
      In three  of the field studies,  leaf  punches  from strawberry plants were taken
 at  several post-application intervals.   Dislodgeable foliar residues were deter-
mined and  expressed both as concentration  per unit  leaf area  (vg/cm2)  and per
dust weight  (ppm in dislodgeable  dust)  and were  plotted against time  (days).

                                      31

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                                                                             44
                                                     Section  No. 	3_
                                                     Revision No.	i
                                                              September 1QR?
                                                     Page   in    of   48
 Figures 12 through 17 and Tables  XIII  -  XV  show the dislodgeable residue decline
 as straight lines on semi log plots  with  high correlation coefficients
 (-0.68 to -0.88).  Extrapolation  to "0:  dislodgeable residues resulted in
 approximately 16, 26. and 26 days,  respectively, for Field Studies Nos. 1,
 2, and 3.  There is no ready explanation for the shorter estimated time interval
 for Experiment 1. except to consider that weathering and decline of dislodge-
 able residues are complex processes, and that field experiments cannot be
 expected to be exactly replicable.
      Similar observations have been made by Maddy  and co-workers (197.7) who
 studied the decline of total and  surface captan residues from leaves of
 strawberry plants following pesticide  treatment.   In one experiment from
 Ventura County,  surface residue decay  was practically linear from 118 ppm
 on day-1  to 35.1  ppm on Day-9, following application.  Another field observation
 near Watsonville (Santa Cruz County) resulted in a rapid decline of captan
 residues  during  the first 26 hours  after application of captan, followed by
 an almost indiscernible decay during the next six  days of observation.  This
 latter  observation is akin to our own  Field Study  No. 2 (see figure 14), except
 that  a  slow decline was observed  during  the second phase.
      A  comment regarding pesticide  application  practices  In Oregon and
 California  1s  1n  order at this point.  Strawberries  are continuously  harvested
 in  California  from about May until  sometime in  October or November,  and
 pesticides  must be used continuously throughout this period, averaging about
 one application every two weeks.   In Oregon, on the  other hand,  all  pesticide
 applications are  made prior to harvest,  and rarely do  additional  applications
occur during the  short, three-week  harvest  period.
                                      32

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                                                                    -••     45
                                                     Section  No.        3
                                                     Revision No.       ]_
                                                     Date:     September  1982
                                                     Page   11      of 48
      For Oregon conditions, therefore, one might be able to establish  a
 practical reentry period for harvesters based on the time interval  at  which
 dislodgeable residues  have disappeared, assuming dislodgeable residues are
 the major source of dermal exposure.  This restriction would result in
 negligible pesticide exposure for strawberry harvesters.  This approach,
 however, may not be feasible without additional safety factors, as is  borne
 out by actual  field observations (Experiment No. 2).  The extrapolated reentry
 interval of 26 days (figs. 14 and 15) is contrasted with the occurence of
                                                   2
 measurable dislodgeable captan residues (o.71 vg/cm ) and an average dermal
 exposure by 23 harvesters of 4.70 mg/hr 26 days post application (See  Table  XI).
      The reason that this approach may not be feasible for California  is
 that insect and disease infestation and a longer harvest period in California
 require  the continuous application of pesticides; so that a negligible residue
 level  may never be  reached before another application is made.
 Captan. Aerosol  Concentrations
      For particulate aerosols, the manual harvester is the proximate  source of
 his  own  hazard.   Measurements in a quiescent field, such as those  by  Carman,
 et j*l. (1952)  found no aerosol and very low vapor levels shortly after
 application  of pesticides to orange groves.  However, the action of harvesters
who may  disturb  the  dust-laden foliage 20 to 30 days post-application,  can
generate  locally high concentrations of pesticide contaminate  aerosols.   The
spatial concentration gradient of such an aerosol near  its  source  is  so large
that for a sample to accurately represent the  hazard, it must  be  collected
in the immediate breathing zone of the harvester.   Concentrations  measured  by
general area samplers show the effect of dilution  by  ambient breezes  and
                                           33

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                                                                             46
                                                     Section No.      3	
                                                     Revision No.     1
                                                     Date'     September
                                                     Page     19   of  48
 and particle fallout.  Therefore,  "breathing zone" personal  air samplers are
 the logical choice to avoid these  interfering effects.  Even then,  the  personal
 samplers are limited in their ability  to  collect all airborne participates,
 but they do collect efficiently the small  suspended particles which may be
 inhalable and respirable.
      Unlike the harvesters of tree-borne  crops, whose dermal exposure derives
 mainly from larger particles of dust falling on him, the harvester of
 hand-picked fruit grown close to the ground, like strawberries, is  probably
 not exposed to these aerosols to a great  extent.  Yet it is surprising that
 there appears to be a good correlation between aerosol concentration and
 dermal  exposure (see figure 18 and 19  and Table XVI).  When dose was normalized
 for weight of harvester (mg/kg/hr), a  linear correlation was retained, as
 shown in fig.  13.   In these studies, eleven strawberry harvesters were equipped
 with personal  air samplers with the filter holder positioned in a horizontal
 manner in order to collect mostly  aerosol  particles  (see fig. 4).  Fixed site
 samplers were positioned about 5 ft. above ground as shown  in fig. 5.  As
 shown in Table XIII, captan aerosol concentrations  ranged from 2.7 yg/m  to
 260.  yg/m3.   Stationary sites for Field  Studies 3  and 5 also had measurable
 concentrations of captan,  but in Field Study No. 1,  captan  concentration in
 aerosols was  nondectable.
     Assuming  that a strawberry harvester works  at  a moderate  physical activity
level and inhales  about 1  n»3/hr, and assuming  that  all aerosol  particles are
inhalable,  the average dermal concentration  (see Table 1)  is two to three
orders of magnitude higher than the maximum  inhalable  amount.   This observation
is consistent  with other crops, and assuming  even  a moderately low level  of
                                  34

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                                                                               47
                                                     Section  No. 	3	
                                                     Revision No.       1      '
                                                     Date:     September 1982
                                                     Page    -n     of   43
 dermal  absorption, clearly demonstrates that pesticide exposure  through dermal
 contact is  much more important than exposure due to inhalation for strawberry
 pickers.  Obviously, exposure to highly volatile or gaseous pesticides would
 alter this  ratio drastically.
 Captan  Soil Residues
      Residues  of Cuptan on sieved soil taken from the strawberry plots  on
 the days  that  the monitoring studies were performed, ranged from nondetectable
 to 10 ppm,  as  shown in Tables XVII - XIX.
      A  detailed soil degradation study of captan was conducted on the'Corvallis
 strawberry  plot (Field Study No. 2).  Soil samples were taken on days 0,  1, 3,
 7,  14,  21,  23, 26 (date of field study), and 29 post-application.  Residues
 on  Day  1 were  0.57 ppm and on Day 7, 6.56 ppm, and on all other sampling dates
 non-detectable.  Leaving out the Day-7 sample as an aberration, one may conclude
 that  the degradation of captan in Oregon soil proceeds rapidly within days of
 its application to strawberry plants.  (See Table XVII)
      Degradation studies on the California plots were complicated by the fact
 that  pesticides were periodically re-applied, approximately at two week-intervals
 during  the entire growing season.  Thus, captan residues of soil  samples from
 Coop  A  near Salinas, California, as may be seen from Table XVIII, appeared
 not to  decline appreciably, with the exception of exhibiting some degree of
 variability, probably due to sampling techniques  (x=3.32 - 2.91).   Keeping  in
mind  that only a single application was made over this period,  no trend  for
 residue decline could be discerned within the first 13 days.  During a second
sampling period, no decline of residues in the soil could  be  seen,  as  well;
although it is possible that an additional pesticide  application was made  just

                                         35

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                                                                                48
                                                     Section  No.
                                                     Revision No .
                                                     Page   14  :  of   43
 Prior to July 31, 1981.  Verification  of  the spray schedule is being made  at
 this time.  Table XIX shows that captan residues in soil did decline after 48
 days at Coop C, which is located just  a few miles north of Coop A.  An attempt
 is being made to characterize the soils in both farms.
      The literature on the decline of  captan in soils of various types is
 in conflict.  Munneck (1958) claims that  fungicidal activity of captan in  soil
 remained almost unchanged for 65 days, suggesting that little or no decline
 occurred during this period.  Kluge (1969) partially confirmed this finding by
 demonstrating that the biological  activity of  captan did not decrease
 appreciably during the first six weeks in two  different soils of "H's 7.4  and
 5.1.   After that, there was a rapid decline observed but unexplained
 resurgence of activity at 12 weeks. Griffith  and Mathews  (1969) using
 bioassays, showed a rapid decline of captan within 4 days  after it had been
 mixed with soil.   By applying captan as a simulated seed dressant on glass
 beads,  the fungicidal  activity was almost quantitatively retained even after
      •
 21  days.
      In  the experiments reported here, behavior of captan  in soil varied  from
 relatively high persistence in one soil (Coop  A, Salinas,  CA) to  a rapid  decline
 in  the Oregon soil  and a slower rate in another Salinas soil.  Based on the
 few foil  samples  which were analyzed,  it  cannot be ascertained whether soil
 residues  of captan  represent a major source of dermal exposure to pickers.
 It  is conceivable that weeders (see discussion above) who  showed  the  greatest
 dermal exposure of  captan of all the subjects  studies,  might be  receiving some
of  their  dermal  dose from these soil residues. Weeding activity  undoubtedly
stirs up  a  large  amount of dust which  will  settle on  all  parts  of the body
of  the person  present  in the cloud.

                                   1      36

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                                                                      1   ?    49
                                                     Section No. 	
                                                     Revision No.	]_
                                                     Date     September  1982
                                                     Page    15    of   48
 Miscellaneous  Correlations
      In order  to  understand the major source of dermal  exposure of strawberry
 harvesters  to  pesticides, several other attempts were made to perform regression
 analyses on a  number of variables other than those already discussed above.
 Thus,  for example, one might expect that the person who works longer hours
 picking fruit  might receive a higher dermal dose.  As seen in Table V, a trend
 for negative correlation is obtained for the relationship "hours worked" and
 dermal  exposure (mg/hr).  How can this be explained?  We believe that the longer
 a  person works in the field without changing his body dosimeters (patches and
 gloves), the more saturated they become and do not truly measure an accumulative
 daily  exposure.  Since this measure is expressed as an hourly rate, one might
 reason  that a  negative correlation would be predicted by this mechanism.  In
 order  to determine the linearity of dermal dosimeters used throughout these
 studies,  detailed experiments are in progress during this growing season to
 investigate  the "saturation points" of these devices.
     It  is  reasonable to hypothesize that if such a saturation phenomenon
 affects  the  dosimeter then it may also affect the skin deposit.  Studies
 incorporating  urinary excretion monitoring next year may be useful  in clarifying
 this year's  results.
     Another hypothesis to be tested by regression analysis  is  that daily
 exposure  to  pesticides might correlate with distance covered  during a work  day.
 In only  two  field studies (2 and 3) were measurements made of how  many  rows of
 strawberry plants each harvester covered during  his working  period.  No such
 correlation  could be found (Table V), and we must  conclude,  therefore,  that
distance covered is probably not a factor  in dermal  exposure.
                                      37

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                                                            Section No.   3
                                                            Revision No.  1
                                                            Date:  September 13E2
                                                            Page  16  of 43
                             REFERENCES
1.  Popendorf, W. J. and Leffingwell, J. T.  Regulating OP Pesticide
    Residues for Farmworker  Protection.  Residue Reviews 82, 125 (1982).

2.  Carman, G. E., Gunther,  F. A.,  Blinn, R. C., and Garmus, R. D.  The
    Physical Fate of Parathion Applied  to Citrus.  J. Econ. Entomol. 45  (5),
    767  (1952).                                    	

3.  Spear, R. C., Popendorf, W.  J.,  Leffingwell, J. T., Milby, T. H.,
    Davies, J. E., and  Spencer,  W.  F.   Field Workers' Response to Weathered
    Residues of  Parathion.  jj. Occup. Med.  1_9_,  406 (1977).

4.  Popendorf, W. J.  Exploring  Citrus  Harvesters' Exposure to Pesticide
    Contaminated Foliar Dust.  J. Amer.  Industr. Hygiene Assoc. 41,  652
    (1980).                    ~
                                           38

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                                                              51
                                     Section  No.       3	
                                     Revision No.      I
                                     Date:  September 1982	
                                     Page  n     o f    48
THIS PAGE LEFT  INTENTIONALLY BLANK
                          39

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                                                Table I



                 Mean Dermal  Exposure to  Captan by Strawberry  Pickers and Weeders
                                          »


                                       (1981  - Field Studies)
( ) - standard deviation.
No. of
Experiment /
Occupation
1 Pickers
2 Pickers
3 Pickers
3 Weeders
4 Pickers
5 Pickers
Days after last
application
3
26
4
4
3
48
Numbers of Subjects
^11 yrs.
4
2
5
2
2
0
-12 yrs.
16
21
10
2
4
10
Dermal Exposure
mg/hr
6.50 (5.08)
4.70 (4.11)
17.41 (14.53)
94.13 (118.4)
16.37 (3.78)
5.88 (3.70)
mg/kg/hr
0.108 (0.079)
0.082 (0.077)
0.310 (0.200)
1.784 (2.177)
0.411 (O.U8)
0.104 (0.072)
O 70  n n
     «t> -*•«-!•
                                                                                                                —. o
                                                                                                                O 3
                                                                                                            00 a,

                                                                                                             CD

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                                      Table  II

Physical  Characteristics and  Exposure Results  of Strawberry  Workers (Weeders)

                              (Field Study No.  3  - 1981)
Worker
l.D.
12
16
20
26
Sex
M
M
M
F
Age
8
13
11
12
Weight
kg
39
49
54
54
Hours
Worked
2.5
2.5
2.5
2.5
Captan Dermal Exposure
mg/hr
Head +
Neck
0.06
56.68
93.53
0.90
Back f
Shoulders
0.13
0.10
0.49
0.55
Chest
2.21
3.01
7.32
28.83
Lower
Leg
0.43
0.70
0.29
2.21
Upper
Ami
0.37
5.53
5.57
0.16
Lower
Arm
0.14
0.39
157.35
0.41
Hands
0.58
5.52
2.17
0.90
Total
3.91
71.92
266.72
33.96
MEAN 94.13
S.O. 118.38
                                                                                                      TJO 73 V>
                                                                                                      Q> CU rD CD
                                                                                                      n> -••«-••
                                                                                                        • u» -*•
                                                                                                          _.. o
                                                                                                          O 3

                                                                                                        in   2
                                                                                                        n> z o
                                                                                                        a o •
                                                                                                      00
vo
CD
ro

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Section No.
Revision No."	
Date:   September  IQg?
Page   to     of   48
                                                             1
                                                                         54
                          Table  III

    Comparison of Dermal  Exposure  to  Captan Experienced by
            Adult and Children Strawberry Pickers

                     (1981 - Field Studies)
Expt.
No.
1
2
3
4
1
3
4
Children
No. of Subjects
4
2
5
2
4
5
2
±11)
Exposure
mg/hr
4.04
1.96
7.74+
12.64
Exposure
mg/kg b.w./hr
0.112
0.240
0.483
Adults (>J2)
No. of Subjects
15
21
10
4
Exposure
mg/hr
7.16
4.97
22.25*
18.24
Exposure
mg/kg b.w./hr
15
10
4
0.107
0.345
0.376
"""Statistically signficiant at p <_ 0.05.
                                 42

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                                                   Section No. 	3
                                                   Revision No.T
                                                   Date:  September 1982
                                                   Page   21     of  48
                                                                             55
                                 Table IV

           Comparison of Dermal Exposure  to  Captan  Experienced by
                   Adult" and Youth Strawberry  Pickers

                            (1981 - Field Studies)
Expt.
No.
1
2
3
A

1
2
3
4
No. of
Subjects
n
n
7
3

n
n
7
3
Group
Adults (>. 14)







Exposure
mg/hr
8.67*
4.91
22.03
18.15
Exposure
mg/kg b.w./hr
0.126
0.072
0.300
0.320'''
No. of
Subjects
8
12
8
3

8
12
8
3
Group
Youths (<. 13)
-






Exposure
mg/hr
3.53+
4.53
13.37 i
14.59

0.084
0.091
0.319
0.503*
Significant at p <_ 0.05.
                                         43

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                                                    Section  No. 	3.
                                                    Revision No.   1
                                                    Date:   September  1982
                                                    Pa g e    22    o f   48
56
                                 Table V

              Linear Correlations Between Selected Variables
                          (1981 - Field Studies)
Variables
Age vs. productivity (crates/hr)
Exposure (mg/hr) vs. productivity
Log exposure vs. productivity
Age vs. exposure
Hours worked vs. exposure
Total daily exposure vs.
distance covered
Exposure vs. body surface area
Exposure Vs. body weight
Correlation Coefficients
Experiment Number
1
0.67+
0.76+
0.72*
0.62*
-0.37
(p-0.12)
__
0.51*
0.50*
2
0.30+
0.13

0.12
-0.39+
-0.22
0.13
0.11
3
0.59+
0.28
0.28
0.15
-0.14
0.15
0.70*
0.70+
4
0.72
0.96*
0.96*
0.83
n/a
__
0.79+
0.81 +
5
0.7*
(p=0.09)
0.83+
i
0.25
-0.64+
..
-0.21
-0.33
"""Statistically significant, p=0.05.

-------
                                          Section No.    3	
                                          Revision No.   1
                                          Date:    September 1982
                                          Page
                                                                    57
23
of   48
                        Table VI

Individual Worker's Variability of Dermal Captan Exposure
Subject's
Initials
D.R.
B.O.
J.R.
Dermal Exposure
mg/hr
Expt. 1
3.87
2.23
1.70
Expt. 3
9.70
9.32
4.36
Ratio
Expt. 3 /Expt. 1
2.51
4.17
2.56
                      45

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                                                     Section  No.   3
                                                     Revision No.__l
                                                     Date:   ^pn
                                                             24
Page_
of   48
                                                                                  58
                                  Table  VII

Dermal Exposure to Captan Experienced  by Male and Female Strawberry Harvesters
Experiment
No.
1
2
3
4
5
No. of Subjects
6 females
13 males
11 females
12 males
3 females
12 males
3 females
3 males
3 females
7 males
Dermal Concentration
(mg/hr)
10.04 ( 6.63)*
4.87 ( 3.35)
3.83 ( 3.32)
5.51 ( 4.71)
12.29. ( 3.74)
18.69 (16.04)
18.15 ( 2.63)
14.59 ( 4.38)
8.43 ( 4.55)
4.79 ( 3.00)
                  Standard Deviation.

                 "^Statistically significant at p <. 0.05.
                                            46

-------
Section No.     3
Revision No.     '
Date :     ^
Pag e   26
                                                          o f  48
                                                                      59
                         Table IX
Hand and Lower  Arm  Exposure to Captan by Strawberry  Pickers
Expt. No.
1
2
3
' 4
5
Exposure
Total
mg/hr
6.51
4.71
17.41
16.37
5.88
Hand + Lower Arm
mg/hr
6.15
3.29
15.13
16.04
5.04
% of Total
(Weighted av.)
92.93
80.80
_80.82
97.87
86.00
       Hand  Exposure to Captan by Strawberry Pickers

                   (1981 - Field Studies)
Expt. No.

1
2
3
4
5
No. of
Subjects

19
23
15
6
10
Exposure
Total
mg/hr
6.51
4.71
17.41
16.37
5.88
Hand
mg/hr
5.53
2.83
11.16
14.32
4.38
% of Total
(Weighted av.)
85.73
67.52
59.55
87.69
76.07
                           47

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                                                Section No.    3
                                                Revision No._  i
                                                Date:    Septembe
                                                Page   27     of
                                                                              60
                              Table  X

Distribution of Captan Dermal  Residues  on  Various Parts of the Body

                 Worker No.  29,  Field Study No. 3
Body Part
Head + neck
Back + shoulders
Chest * stomach
Lower legs
Upper arms
Lower arms
Hands
TOTAL
Concn. Captan
mg/hr
0.39
0.30
55.96
0.90
0.47
1.42
5.23
64.67
% of Total
0.60
0.46
86.53
1.39
0.73
2.20
8.09
100.00
          Note:   Subject  is  a  six-year old  male  who worked  for
                 3.5  hours  in  the field and picked one  crate of
                 strawberries.

-------
                                             Section No.  	3_
                                             Revision No.	l_
                                             Date'  SgDtgTibgr Ij
                                             Page   23      of •
                                                                        61
                         Table XI

Relationship Between  Hourly  Dermal Exposure and Dislodgeable
            Foliar  Residues  on Strawberry Plants

                  (1981 - Field Experiments)
Experiment
No.
1
2
3
4
5
Dermal Exposure
mn/hr
6.50 ( 5.08)
4.70 ( 4.11)
17.41 (14.53)
16.37 ( 3.78)
5.88 ( 3.70)
Dislodgeable Residue
ug/cm2
2.36 (0.60)*
0.71 (0.32)
3.85 (2.84)
**
1.42 !
1.72 (1.04)
            **
( ) Values are standard deviations.

Only two values reported; no standard deviation
calculated.
                                       49

-------
Section No.
Revision No.
Date:
Page_
                                               29
                     Table XII

                      Summary

Dislodgeable Captan  Residues From Strawberry Fruits

                (1981  - Field Studies)
                                                                    62
of  48
Study
No.
2
2
3
3
4
5
5
Days Since Last
Application
26
26
4
4
3
48
48
Sample
No.
1
2
1
2
1
1
2
PPM
Captan
Nondetectable
0.35
1:11
1.20
1.13
0.49
0.09
                             50

-------
                                              Section No.     3
                                              Revision No.    l
                                              Date:  September 19B2
                                              Pag e    30     o f  AS
                                                                          63
                           Table  XIII
         Decline of Foliar  Dislodgeable Captan Residues
                     Field  Experiment No. 1
Date of Harvester Monitoring:
Place:
Temp.:
Wind Speed:
Pesticide Treatment:
May 9, 1981
Coop A, Salinas,  CA
73°F, 66S RH
5.7 - 9.1 mph
2 Ib captan, April  15-18,  23,  and'26,  1981
Days Post-Application
2
i &
12
13 (1)
(2)
(3)
(4)
(5)
Date
April 23, 1931
May 4, 1981
May 8, 1981
May 9, 1981




Dislodqeable Residue
ug/cm2
9.75
3.03
0.21
2.05
1.71
2.04
2.85
3.13
PPM on Dust
63,500
15,500
1,360
13,600
9,870
11,000
13,900
20,700
                                     51

-------
Section No.  	3_
Revision No.	]_
Date:     Sentpirr-.or
Page   3T
                                                          IOC?
                                                    Of  48
                                                                    64
                   Table XIV

Decline of Foliar Dislodgeable  Captan  Residues

          Field Experiment No.  2

Date of Harvester Monitoring:   June  22,  1981
Place:  Strawberry Farm, Corvallis,  OR
Temperature:  61-67eF; some rain
Pesticide Treatments:   2.5 Ib captan on  May 4,
                       21, and  27, 1981.
Days after Treatment
0
0
1
1
3
Date
(1981)
May 27
May 27
May 28
May 28
May 30
3 May 30
7
7
• 14
14
19
21
21
23
23
26
26
26
26
June 3
June 3
June 10
June 10
June 15
June 17
June 17
June 19
June 19
June 22
June 22
June 22
June 22
Dislodgeable Residue
vg/cm2
7.02
6.90
9.84
14.70
4.84
6.31
6.42
5.07
1.55
0.65
0.06
4.91
0.75
2.18
0.41
0.34
0.58
0.84
1.08
PPM on dust
j
306,600
330,100
237,100
502,700 ;
15,663 :
68,143 :
113,428 |
72,222 !
20,182 !
9,924 j
904
69,252
9,665
26,170
4,795
4,509
7,733
12,727
19,285
                      52

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Section No. 	3
Revision No.	1
Date:   September 1982
Page
                                             32
Of	48
                                                                65
                   Table  XV

Decline of Foliar Dislodgeable  Captan Residues

          Field Experiment No.  3

Date of Harvester Monitoring:   July 21, 1981
Place:  Co-op A,  Salinas, CA
Temperature:   53-76°F
Pesticide Treatment:   2 Ib captan on April 15-18,
                      April 23, April 26, May 10,
                      May 17, May 31, June 7, July 17, 1981
Days Post-Application
4
4
4
21
21
Date
(1981)
July 21
July 21
July 21
Aug. 11
Aug. 11
Dislodgeable Residue
ug/cm2
6.70
3.39
5.22
0.97
1.77
PPM on dust
21,300
8,627
18,514
3,688
6,756

-------
                                              Section No. 	3
                                              Revision No.	1
                                              Date:	
                                              Page    33     of  48
                                      September 1932
                                                            66
                           Table XVI
       Pesticide Aerosol Concentration (Captan)  Vs.  Dermal
           Exposure of  Individual Strawberry Pickers
Subject No./
Experiment *.'o.
6/1
13/1
17/1
18/1
1/3
11/3
•13/3
22/3
27/3
3/5
6/5
Aerosol Concn.
ug/m2
2.74
6.84
8.41
1
Dermal Exposures j
mg/hr
2.23
4.51
8.44
70.30 14.14
258.2
127.6
109.9
210.3
175.5
22.4
26.9
56.32
9.32
17.67
16.16
7.61
3.62
2.53
mg/kg/hr (
0.050 '
0.070
0.084
0.179
0.655
i
0.211
0.260
0.351
0.152
0.075
0.029
fixed Sites
Expt. 1
Expt. 3
Expt. 5
  0
155.1
144.4
                                   54

-------
                                                                        67
                                             Section No.        3
                                             Revision No.        1
                                             Date:     September I
                                             Page    34     of  48
                          Table XVII

           Captan Soil  Residue Decay: Corvallis, OR
Days Since Last Application
0
1
3
7
14
21
23
26
20
Date
(1981)
May 27
May 28
May 30
June 2
June 9
June 17
June 19
June 22*
June 25
PPM Captan
0
0.57
•
" o !
6.56
0
i
0
0
0
0
* date of human monitoring  (Field  Experiment No. 2)
                                55

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                                                                    68
                                           Section No.
Revision No. 1
Date:
Page
Table XVIII
Seotenber 1932
35 of 43

Captan Soil Residue Decay: Co-op A, Salinas, CA
Days Since Latest Application
2
2
8
9
13
Date
(1981)
April 28
April 28
May 4
May 5
May 9*
13 I May 9*
i
4 July 21*'
10
?
?
July 27
July 31
August 7
PPM Captan
3.47
1.58


3.40
0
8.63 1
i
2.89
6.29
3.77
9.16
7.93

i
1


 * date of human monitoring (Field  Study No. 1)
** date of human monitoring (Field  Study No. 3)
                             56

-------
Section  No.      3	
Revision No.     1
Date:     September J9£r
Page   36    of  A8
                                                                           69
                        Table XIX

      Captan Soil  Residue Decay. Co-op C,  -Salinas, CA
Days Since Latest Application
27
34
48
Date
(1981)
July 31
August 7
August 21*
PPM Captan
4.10
0
0
*Date of human monitoring (Field  Experiment No. 5)
                           57

-------
1  «_>
  rs
  o
  o
  oe
  o.

cn

09
 6.0




 5.5





 5.0





 4.5





 4.0





 3.5





 3.0





 2.5
   •




 2.0





 1.5





 1.0





0.5






0.0
                                                                                            I   I   T
             -  O  • 1  OBSERVATION-
                                                  O   O
                     46   8  10   12  14  16 10   20  22  24  26  28 30' 32   34  36  38  40  42 44  46



                                                       AGE



                                          8.   AGE  VS  PRODUCTIVITY
                                                                                                                  •o o :	
                                                                                                                  cu o> rt> n>
                                                                                                                  id r+ < O
                                                                                                                  . n> at -».«-»
  -•. o
t/i o 3
n> 3
o   3
  r± o
ro o
                                                                                                             IT

-------
C/l
       18
       16
       14
       12
   g  10
   UJ
   a:

   to    _

   £    8
   X
•  p   0
                       •   i    i   i
                                                                                   i   i
                                                                                               i    i
               O « 1 OBSERVATION
                      OBSERVATIONS
                       I
I    1    I    I    »    »    »	t    I    I    I    I    I	I    I   I    I   I   I
         0    2   4   6   8   10   12  14  16   10  20  22 24   26  20  30  32 '34  36  30  40  42  44  46

                                                       AGE

                                         o.   AGE vs TOTAL EXPOSURE
                                                                                                                        Ti O 70 tn
                                                                                                                        D> Of CD ft)
                                                                                                                        to r« < O
                                                                                                                        fD fb -•• r»
                                                                                                                          .. in -1.
                                                                                           <0 3
                                                                                           rt)   ;-r
                                                                                           ii i'-r o
                                                                                           , • o •
                                                                                           (0
                                                                                            I
                                                                                           ri
                                                                                           in

-------
     18
     16
     14
    12


 i_
.c
^v.
 o>

3  10
o
O
     8
01
      0.0
              O «  1  OBSERVATION
           0.5
1.0
                                                        J_
1.5      2.0        2.5      3.0


                      PRODUCTIVITY
3.5
4.0
4.5      5.0
                                    FIGURE 10.  PRODUCTIVITY  VS TOTAL EXPOSURE
5.5
6.0
                                                                                                                            SO t/>


                                                                                                                       £5*8
                                                                                                                       '££-'•«-»
                                                                                                                        n> n> 1/1 .j.
                                                                                                                            -i. o
                                                                                                                            o 3
                                                                                                                        •.o
                                                                                                                     X? 3
                                                                                                                     s   =
                                                                                                                     o ^ o
                                                                                                                     r+ o •
                                                                                                                             P^-J

                                                                                                                              r^

-------
                                                                Section  No.	3

                                                                Revision No.    1

                                                                Date:   Seote^ser
                                                                                   73
                                                                Page   AQ    of  .13
s


I
V*
s

S

i
w

I

§
i — i — i — i — i
                                                             i — i — i — i — i —
                                                         I	0    I
                     I    I   I    I   I   I   I   I   I   I    I   I   I   I   I   I   I   '   I
        01   23   <   S   678   9 JO  11  \2  13  1<  15   U  17  IE  19  2:  ?'•  2:
                                       £XPOS'JBE (ng/hr)
           FIGURE  11.   DISLODGEABLE FOLIAR RESIDUE VS, DERMA'. EXPOSURE

-------
o

o.
3
cc
t;
« .•
LU
O
tJ
a.
         FIGURE  12.
                         8          10


                    DAYS POST-APPLICATION
    *            t

FIELD  EXPERIMENT  NO.  1.  CAPTAN DISLODGEABLE RESIDUE  DECLINE
                                                                                                              -o o ixx/i
                                                                                                              Q> O> (T> fl>
                                                                                                              U3 r* < O
                                                                                                              0> (O -'• r*
   _•. o
   O 3
t/> 3
,n>  2
n z o
r+ O
CD
13
O

-------
                                                                                                                                                        is
                                                                                                                                                      *;.»
                                   3        4        56         789



                                                            PATS Pt>ST-M>niCMim


                                 I  IGUtt 13.   riUD CXPtRIHTNl NO. I.   OlSlOPCr/Mll f fM MR RrSlfHlf MCI IW
                                                                                                       n
                                                                                                               I?
                                                                                                                        13
                                                                                                                                14
                                                                                                                                         IS
C7N
                                                                                                                                                                  Ol

-------
 0


 cn
«_>

o


z
«t
»—
ex.

u
            nnimr. 14.
  6        9        12         15        10.      21         21



                   RAYS POST-APPLICATION



FIELD EXPERIMENT NO. 2.  CrtPTAN DFSIODGFARLE  RESIDUE  DECLINE
                                                                                             27
30

-------
                                                                          PPM ON  DUST x  10
                                                                                                -3
              cr>
              cr
              TO
              tn
               x
               -o
               n
               o
               •


               r>o
Ul
O
»—«
CO
•—
o
o
cr>
m
»>
oo
               70
               m
               c.
               m
                        I
                       f»
                       -o
                       o
                       o
                                                                                                                                                   -oo TO ui
                                                                                                                                                   o> o> rt>  it>
                                                                                                                                                  U3 rt <  O
                                                                                                                                                   n> re -*• rf
                                                                                                                                                        _.. o

                                                                                                                                                     toO  3
                                                                                                                                                                    ro P

-------
0
  0
     CK
                                DAYS POST-APPLICATION



FIGURE 16.  FIELD EXPERIMENT NO. 3.  CAPTAN DISLODGEABLE RESIDUE DECLINE
                                                                                                                  oo

-------
o


 X





a

jri,
o
a"
a.
       0
   O\
                             FIGURE 17.
                   11         .               16


                     DAYS POST-APPLICATION


FIELD  EXPERIMENT NO.  3.  OISLODGEABLE  FOLIAR RESIDUE DECLINE
                                                                                                                21
26
                                                                                                                              -o o TO in
                                                                                                                              a* 01 at a>
                                                                                                                              «o «-» < o
                                                                                                                                re -••«-«•
                                                                                                                                01 O 3

                                                                                                                                
-------
                                                                       80
                                                      Section  No.   3
                                                      Revision  No..  1
                                                      Date:  September 1982
                                                      Page 47   of
                  AEROSOL  CONCENTRATION  (ug/ m3)
FIGURE 18.   AEROSOL CONCENTRATION  VS.  DERMAL EXPOSURE  (mg/hr)
                                                                  68

-------
Section No.3
Revision No.  i
                                                                           81
1
                                                       Date:  SeDtembern'?Err
                                                                 of  £S
              100                    200                     300


                AEROSOL CONCENTRATION (yg/ n3)



FIGURE 19.'  AEROSOL COriCENTRATION VS. DERMAL EXPOSURE (mg/kg b.w./hr)
                                                                     69

-------
                                                                                         a
                                                            Section No.  Ref.
                                                            Revision No.  1
                                                            Date:   September 1982
                                                            Page 1  of 1
                                  REFERENCES


 1.  Carman, G. E., Sunther, F. A., Blinn, R.  C.  and Garmus, R.  D.   The
        Physical Fate of Parathion Applied to  Citrus.  J..  Econ.  Entomol.
        45. (5), 767 (1952).

 2.  Griffith, R. L. and Mathews,. S.   The Persistence in Soil  of the
        Fungicidal Seed Dressings of Captan and Thiram.   Ann.  Appl.  Biol.  64.
        113-118 (1969).

 3.  Kluge, E.  Der Einfluss der Bodenreaktion auf den Abbau und die Wirkungsdauer
        von Thiuram, Ferbam, und Captan im Boden.   Arcji. Pflanzenschutz,  5_,
        263-271 (1969).

4a.  Maddy, Keith, T., Kahn, C. S., Riddle, L., and Alexander, J.   A Breakdown
        Study of Captan (Orthocide) on Strawberry Foliage and Fruit in
        Ventura County, California, April, 1977.   Worker Health and Safety
        Unit, Div. of Pest Managementf Environmental Protection and Worker
        Safety, CDFA, Sacramento, California,  Report No. HS-372 (June 20,  1977).

4b.  Maddy, Keith, T., Edminston, S., Kahn, C. S., Jackson,  T.," and Frederickson,
        A. Scott.  A Study of the Decay of Captan on the Foliage and Fruit of
        Strawberries in Santa Cruz County, May 1977.  Ibid., ACF 59-376
        (June 16, 1977).

 5.  Munnecke, Donald E.  The Persistence of Nonvolatile Diffusible Fungicides
        in Soil.  Phytopathology. 48, 581-585  (1958).

 6.  Popendorf, W. J.  Exploring Citrus Harvesters' Exposure to Pesticide
        Contaminated Foliar Dust.  J_. Amer. Industr. Hygiene As sot:.  41,
        652 (1980).                                   "•"            ~~

 7.  Popendorf, W. J. and  Leffingwell,  J. T.   Regulating OP  Pesticide Residues
        for Farmworker Protection.  Residue Reviews 82,  125  (1982).

 8.  Spear, R. C., Popendorf, W.  J.,  Leffingwell,  J. T., Milby, T.  H.,
        Davies, J. E., and Spencer, W.  F.  Field Workers'  Response to
        Weathered Residues of Parathion.   J_. Occup. Med. J9_, 406 (1977).
                                                                     70

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                                                      83
                         Section No.  Aooendix
                         Revision No.	Draft -  1
                         Date:	September  1982
                         Page    j	of   43
      APPENDIX

Body Surface of the 50-Percentile  Man
Data From Field Study 1
Data From Field Study 2
Data From Field Study 3
Data From Field Study 4
Data From Field Study 5
                  71

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                                                                               84
                                                 Section No.   Aooendix
                                                 Revision  No.Drafti
                                                 Date:      September .1382
                                                 Page      't>      of  43 ~
                           Table A-l


             Body Surface of the 50-Percentile Man
       Body Parts                      Surface Area
Head and neck                            1300
Back and shoulder                        2190
Chest and stomach                        2190
Upper leg                                3460
Lower leg                                2590
Feet                                     1230
Upper arm                                1860
Lower ann                                1290
Hands                                    1075*
1
 Popendorf and Leffingwell, 1982

*
 Hand surface was not used for total  body exposure because glove dosimeter
covered entire surface of hand (see text for details).
                                         72

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                                                                           85
                                               Section No. Appendix
                                               Revision No.   Draft 1
                                               Date:	-  Seftamper 1982
                                               Page _3	of	53	
                   Field Study No.  }

Site and Location:  Cooperative Fam  A,  Salinas, California

Date of Study: May 9, 1981

Weather: temp.: med.  73°F;  humidity:  66;J R.H.; wind  speed: 5.7-9.1 mph

Number and aae_of subjects:  age 11  and  under: £; age 12 and over: ^6_
                                       73

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                          86
Section No.  Appendix
» Revision No. Draft 1
Table A-2

Date:
Page
Pesticide Spray History, 1981, Cooperative A, Cal
ApSl1«?'on Pesticides
*
2/7/81 Lannate SP (90%)
Thiodan 2E
Di thane Z 78
(75%)(ziram)
2/25/31 Sevin Bait (5%)
3/23 - 3/24/81 Plictran SOW
Diazinon SOW
Tops in M 70W
3/25/81 Tops in M 70W
Plictran SOU
Diazinon SOW
Bufferol ,
Spray Film B
Cytrol (amitrole)
(2 Ib./gal.)
4/15 - 4/18/81 Ortho Plictran
SOW
Ortho Malathion
25WP
Dupont Benlate
SOW
Ortho Orthocide
SOW
4/23/31 Orthocide SOW
Benlate DP 50
Bufferol
i/25/£l Crthocide 5GW
Benlate SOW
Kalathion 25
Eufferol
Product/A
1.0 Ib.
1.0 gal.
3.25 Ib.

1.5 Ib.
1.5 Ib.
2.0 Ib.
1.0 Ib.
1.0 Ib.
2.0 Ib.
1.0 Ib.


1.0 gal
2.0 Ib.

3.0 Ib.
1.0 Ib.
4.0 Ib.

4.0 Ib.
1.0 Ib.

4.0 Ib.
1.0 Ib.
4.0 Ib.
1.0 pt.
AI/A
0.9 Ib.
2.0 Ib.
2.4 Ib.

0.075 Ib.
0.75 Ib.
1.0 Ib.
0.7 Ib.
0.7 Ib.
1.0 Ib.
0.5 Ib.


1.0 Ib.
1.0 Ib.

0.75 Ib.
0.5 Ib.
2.0 Ib.

2.0 Ib.
0.5 Ib.

2.0 Ib.
0.5 Ib.
1.0 Ib.
1.0 pt.
September 1982
A Of 43

ifornia
Method of
Application/
Final Volume
Ground
3-400 gal /A

•
Ground
Ground
3-400 gal /A
•
Ground
3-400 gal /A




Ground

3-400 gal /A



Air
20 gal/A

Air
20 gal /A
us
/

                       74

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                            87
Section No.  Appendix
Table A-2 (continued)
Date of
Application
5/10/81



5/17/81



5/31 /SI




6/7/81



6/27 - 6/28/81


6/23/81

'Pesticides •
Mevinphos 4E
Benlate DP
Orthocide SOW
Bufferol
Dibrom 8E
Benlate SOW
Orthocide SOW
Bufferol
Plictran SOW
Difarom 8E
Tops in M (70W)
Orthocide (SOW)
Bufferol
Dibrom 8E
Benlate SOW
Orthocide SOW
Bufferol
Diazinon SOW
Dicofol 4E
Tops in M 70W
Bufferol
Dibrom 8E
Oxyflow Sulfur
(6 Ib./gal-)
Bufferol
Product/A
1.5 pt.
1.0 Ib.
4.0 Ib.
1.0 pt.
1.0 pt.
1.0 Ib.
4.0 Ib.
1.0 pt.
2.0 Ib.
1.0 pt.
1.0 Ib.
3.0 Ib.
1.0 gal.
1.0 pt.
1.0 Ib.
4.0 Ib.
1.0 pt.
2.0 Ib/A
2.0 qt.
1.0 Ib.
1.0 gal.
1.0 pt.
1.0 qt.
1.0 gal.
Revisi
Date:
Page
AI/A
0.75 Ib.
0.5 Ib.
2.0 Ib.
1.0 pt.
1.0 Ib.
0.5 Ib.
2.0 Ib.
1.0 pt.
1.0 Ib.
1.0 Ib.
0.7 Ib.
1.5 Ib.
1.0 gal.
1.0 Ib.
0.5 Ib.
2.0 Ib.
1.0 pt.
1.0 Ib.
2.0 Ib.
0.7 Ib.
1.0 gal.
1.0 Ib.
1.5 Ib.
1 .0 gal.
on r;o. Draft 1
Seotember 1982
5 Of 4^

Method of
Application/
Final Volume
Air
20 gal /A

,
Air
20 gal/A
•

Ground
3-400 gal /A



Air
20 gal /A


Ground rig
3-400 gal /A


Air
10-20 gal /A

75

-------
Section No.
Revision No.

Date:
Page _ '5
                                         Appendix
                                          of   43
Table A-2  (continued)
Date of
Application
7/7/81



7/17/81


Pesticides •
D'cofol 4E
Dibrom 8E
Thiram 65W
Sufferol
Phosdrin 4E
Oxyflow Sulfur
(6 Ib./gal)
Orthocide BOW
Product/A
2.0 qt.
1.0 pt.
2.0 lb.
1.0 gal.
1.0 qt.
1.0 qt.
4.0 lb.
AI/A
2.0 Ib.
1.0 Ib.
1.3 Ib.
1.0 gal.
1.0 Ib.
1.5 Ib.
2.0 lb.
Method of
Application/
Final Volume
Ground
3-400 gal /A


Air
20 gal /A

                     76

-------
                                                                                      89
                                                        Section No. Appendix
                                                        Revision No. Draft	]_
                                                        Date:	September  198
                                                        Page    7	of  43
                              raDVe A-3
           Physical Characteristics and Work Habits of Strawberry  Pickers
Worker
 I.D.
Sex
                        field Study No.  1  -  1981
Age     Weight
Productivity
  crates/hr
           Hours Worked
            Body  Surface
                 m
  1
  3
  4
  6
  7
  8
  9
 10
 n
 12
 13
 14
 15
 15
 17
 18
 19
 22
 23
 24
 M
 M
 F
 M
 M
 M
 F
 M
 M
 M
 M
 F
 • «
 :*i
 M

 M
 M
 p
10
9
11
13
n
12
14
14
12
20
20
24
22
31
19
46
16
21
13
50
34
34
39
44'
36
52
54
66
59
61
64
66
73
75
100
79
70
52
66
66
    1.54
    0.82
    0.82
    4.27
    1.88
    n/a
               5.50
               9.78
      76
      03
      46
    2.57
    1.
    5.
    3.
    3.
98
39
10
73
    4.72
     ,76
     .55
     .80
     .82
               9.
               6,
               5.
  78
  33
  33
               4.0
6.25
4.92
8.25
8.17
  58
  42
  17
  83
  42
  25
  25
                               4.09
               4.17
               5.50
               5.62
                                                       1.2
                                                       1.1
                                                       1.2'
                                                       1.4
                                                       1.2
                                                       1.5
                                                       1.6
                                                       1.7
                                                       1.6
                                                       1.7
                                                       2.0
                                                       2.0
                                                       1.8
                                                       1.9
                                                       2.1
                                                       1.9
                                                       1.9
                                                       1.5
                                                       1.7
                                                        1.6
                                                  77

-------
                                                                      90
Worker
   I.D.
                                            Section  No.   Appendix
                                            Revision No.   Draft 1
                                            Date:	 September J982
                                            Page     8 '     of    43
                        Table A-4
Exposure  Results of Strawberry Pickers

      Field  Study No. 1-1981

                  Dermal Exposure (Captan)

                Total     	    Hands Only
                   mg/kg
                   /hr*   mg/hr    mg/hr   ?>Total
1
3
4
6
7
3
9
10
n
12
13
H
15
15
17
18
19
22
23
MEANS
S.D.
0.099
0.050
0.099
0.050
0.200
0.076
' 0.139
0.045
0.035
0.075
0.070
0.209
0.080
0.102
0.084
0.179
0.045
0.356
0.059
0.108
(0.079)
3.37
1.70
3.87
2.23
7.20
3.94
7.53
2.98
2.04
4.50
4.51
18.00
5.86
7.64
8.44
14.14
3.14
18.51
3.39
6.50
(5.08)
3.09
1.53
3.30
1.98
6.39
3.62
6.41
2.85
1.93
3.71
4.07
12.88
5.37
6.67
8.06
11.25
1.56
17.27
3.02
5.53
(4.25)
91.79
90.15
85.32
88.47
88.74
91.91
85.14
95.67
94.46
80.65
90.34
71.50
91.63
87.32
95.44
79.61
49.54
93.30
77.75
85.73
(10.89)
kg of body weight
                                   78

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                                                                                  91
                                                         Section No.  Appendix
                                                         Revision No.  Draft  1
                                                         Date:	Sep±anber_19£2_
                                                         Page    9	of  43
                                    Table A-5
     Comparison of Captan Exposure By Different Groups  of  Strawberry Pickers

                           Total Dermal Exposure (per hour)

                             Field Study No.  1  - 1981
     Group
Average     No.  of       Captan  Concentration
  Age     Subjects             (mg/hr)
   Statistics
     p-Values*
Adults (^12)
Children (=11)
Adults
Youths

Female
Male
                                             Mean
S.D.
19.8
10.25
22.5
11.4

15
4
11
8
6
13
7.16
4.04
8.67+
3.53+
10.04+
4.87+
5.46
2.31
5.67
1.74
6.63
3.35
(1)
(2)
                                                             (3)
0.286  0.250   0.211
0.015  0.008   0.012
0.120  0.036   0.059
*
 (1) Assuming normal distribution of data
 (2) Assuming nat. log normal cistribution of data (skewed)
 (3) Wilcoxon nonparametric test
Vo.05 is considered significantly different (95% probability)
                                                     79

-------
                                                                                92
                                                        Section No.  Appendix
                                                        Revision No.DraftT
                                                        Date:     September ;1957"
                                                        Page     10     of   A3
                                  Table A-G



  Comparison of Captan Exposure  by  Different Groups of Strawberry Pickers

                    Total  Dermal  Exposure Normalized for Body Weight (mg/kg/hr)

                         Field Study No. 1 - 1981
     broup
No.  of Subjects
Adults (*12)
Children (*11)
Adults (214)
Youths (-13)
Female
Male
15
4
n
8
6
13
Captan Concentration
     (mg/kg/hr)
                                           Mean

                                          0.107
                                          0.112

                                          0.126
                                          0.084

                                          0.158
                                          0.085
                                  S.D.

                                 0.085
                                 0.063

                                 0.093
                                 0.053

                                 0.110
                                 0.051
                     (D

                  0.915


                  0.262


                  0.174
   Statistics
    p-Values*

 (2)     (3)


0.690   0.582


0.231   0.302


0.057   0.059
T
 (1)  Assuming  normal  distribution of data
 (2)  Assuming  nat.  log normal distribution
 (3)  Wilcoxon  nonparametric  test
                                                80

-------
                                                                           93
                                               Section  No.    Appendix
                                               Revision No.
                                               Date:	
                                               Page      n      oi
                          Table  A-7
 Captan Dermal Exposure to Various Parts of the  Body

               Field Study No. 1-1981   (19 subjects)
    Body Part
                               Mean
       Exposure
mg/hr
    S.D.
                                                           Weighted average
                                                          Percent of total *
Head + neck
Back + shoulder
Chest + stomach
Lower leg
Upper arms
Lower arms
Hands
Total
Other than hands
- 0.032
0.084
0.044
0.165
0.034
0.622
5.525
6.505
0.981
(0.040)
(0.186)
(0.078)
(0.179)
(0.054)
(1.179)
(4.243)
(5.080)
(1.202)
0.65%
1.37
1.17
3.30
0.59
7.20
85.73
100.00
14.27
  Note:  Average percentages are calculated as averages of individual
percentages which explains the discrepancy between these values shown
in the table and calculated percentages based on the means.
                                       81

-------
                                       Section No.   Appendix
                                       Revision No.   Draft  1
                                       Date:	  September 1982,
                                       Page      12    of	43.
                  Table A-8
  Aerosol  Concentration  of Captan  on  Individual Workers

          Field Study No.  1  -  1981
Subject No.
Aerosol  Conen.
       .3
  Dermal  Exposure
                                               mg/hr
                                    mg/kg/hr
    6
   13
   17
   18
   2.74
   6.84
   8.41
  70.3
 2.23
 4.51
 8.44
14.14
0.050
0.070
O.OS4
0.179
                                 82

-------
                             Taole A-9
                                                                               95
                                                 Section No.   Appendix
                                                 Revision No.	DraftJ	
                                                 Date:	SrO-erpe'r 1 ?£2
                                                 Page	13	"of	43	
          Pearson Correlation Coefficients for Variables
                   Field Experiment No. 1 - 1981
          Variables
 Age vs productivity
 Total exposure vs oroductivity
 Log total exposure vs productivity
 Age vs. total exposure
 Hours worked vs total exposure
Correlation Coefficients
       0.669*
       0.755*
       0.715
       0.515*
     - 0.369 (p=0.12)
Statistically significant at P-0.05
                                                 83

-------
                                                                 96
                                     Section No.  Appendix
                                     Revision No.
                                     Date : _ .Seplembe^-l Qg?
                                     Page    u  of    &V
          Field Study  No. 2
Site and Location:  Farm  in Corvallis, Oregon
Date of Study:  June 22,  1981
Weather: temp.: 61-67°F; some rain; 77-93% R.H.; no wind (1.3^2.1  mph)
Number and age  of subjects: 23 (ages 11-38)
                               84

-------
                              Taole A-9
                                                                               95
                                                  Section  No.   Anpendix
                                                  Revision  No.	Draft j	
                                                  Date:	S=o-.erp°'-  1?S2
                                                  Page	i_3	"of	43	
          Pearson Correlation Coefficients for Variables
                   Field Experiment No. 1 - 1981
          Variables
 Age vs productivity
 Total exposure vs productivity
 Log total exposure vs productivity
 Age vs. total exposure
 Hours worked vs total exposure
Correlation Coefficients
       0.669*
       0.755*
       0.715*
       0.515*
     - 0.359 (p*0.12)
Statistically significant at P-0.05
                                                 83

-------
                                                                 96
                                     Section No.  Appendix
                                     Revision No.
                                     Date : _ 5optamhor_1 QP-?
                                     Page    u of    flV
          Field Study  No. 2
Site and Location:  Farm  in Corvallis, Oregon
Date of Study:  June 22,  19C1
Weather: temp.:  61-67°F; some rain; 77-93% R.H.; no wind (1.3r2.1  mph)
Number and age  of subjects: 23 (ages 11-38)
                              84

-------
                                                Section Ho.    Appendix
                                                Revision No.    Dra^t  "*	
                                                Date:      Sen ten-jag r 19S2
                                                Page     15     of    A3
                           Table A-10
Pesticide Spray History,  Strawberry Farm in CrovaTMs, Ore. During 1981
                                                                              97
 Crop:

 Acres:

 Application Equip:
                     Strawberries  (Benton)

                     15

                     Side delivery air blast sprayer
                     @ 20 gallons finished spray/acre
 Date
May  4
               Pesticide
         Thiodan
         Captan
         + B-1956  (spr-stick)
                                                       Rate
Fomulation

  50% WP
  50% W?
    Fora
2 Ib/ac
5 Ib/ac
   AI
PHI
1.0 Ib/ac
2.5 ib/ac  «i9 days
Kay 11   Benlate
         + Ag-98  (spr-stick)
                                  50% WP
             1 Ib/ac
               0.5 Ib/ac  42 days
Kay 21   Captan
                                  50% WP
             5 Ib/ac
               2.5 Ib/ac  32 days
May 27
         Captan
         Benlate
         KSR
         •f AG-98  (spr-stick)
  50% WP     5 Ib/ac        2.5 Ib/ac  26 days
  50% WP     1 Ib/ac        0.5 Ib/ac
  80% WP     1 1/3 Ib/ac    1.0 Ib/ac
  2 0/G      1 1/2 pts/ac   0.38 Ib/ac
June 22  Harvest
                                                                         0 days
                                       85

-------
                                                                    98
                                          Section No.   Appendix
                                          Revision No.   Draft  1
                                          Date     Septerrper i9gT"
                                          Page    16      of	41.
                     Table A-ll
     Captan Dermal  Exposure  By Various parts of the Body

                   Field  Study No. 2 - 1981 (23 subjects)
Body Part
                   ma/hr
               [•lean
S.O.
Exposure

 Weighted Average
Percent of Total
Head + neck
Back + shoulder
Chest + stomach
Lower legs
Upper arms
Lower arms
Hands
Total
Other than hands
0.174
0.247
0.047
0.503
0.452
0.460
2.825
4.707
1.882
0.573
0.982
0.106
1.565
1.800
0.594
2.862
4.107
2,806
2.92
3.36
1.15
6.96
4.82
13.28
67.52
100.00
32.48
                                  86

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                                                                        99
                                                           ^Appendix
Section No.
Revision No/	
Date:	September 1962
Page
                                                     17
of   43
                        Table A-12



Physical  Characteristics and Work Habits of Strawberry Pickers

                 Field Study No. 2 - 1981
Worker
I.D.
1
2
3
4
5
6
7
8
9
10
n
12
13
U
15
16
17
18
19
20
El
22
23
Sex
r
F
F
F
H
F
M
M
M
M
F
^
F
M
M
M
r
F
F
H
M
M
H
Age
25
15
38
13
38
37
13
17
13
13
13
13
20
17
13
12
25
38
13
11
11
12
14
Weight
kg
57
60
60
41
68
82
49
71
70
70
42
79
70
72
60
43
93
67
48
35
44
45
61
Productivity
crates/hr
1.45
1.01
1.59
1.28
1.90
1.65
0.85
1.26
0.92
0.92
0.71
0.31
1.57
1.04
1.20
0.64
0.97
1.73
0.82
0.64
0.54
0.83
1.36
Distance
covered
ft
202
225
225
180
324
324
180
270
174
180
90
59
239
180
ISO
119
130
225
225
180
90
130
324
lours
worked
6.92
5.92
5.92
6.25
6.85
6.85
6.57
6.33
5.50
6.50
6.50
6.50
6.37
6.25
5.75
6.38
6.53
6.92
6.50
6.25
6.28
6.50
6.85
Body Surface
nr
1.6
1.6
1.5
1.3
1.8
1.9
1.4
1.9
1.2
1.8
1.4
. 1-8
1.8
1.9
1.7
1.4
2.1
1.8
1.5
1.2
1.4
1.4
1.6
                                   87

-------
                                                                  100
                                            Section  No.    Appendix
                                            Revision No.  .Draft  1
                                            Date:	Se£temberJ 982
                                            Page     18      of   43"
                       Table A-13
           Exposure  Results of Strawberry Pickers


               Field Study No. 2 - 1981
Worker
I.D.


1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
MEANS
S.D.
Dermal Exoosure(Captan)

Total
tug/kg / hrw
0.104
0.038
0.073
0.011
0.155
0.058
0.240
0.019
0.055
0.041
0.293
0.027
0.061
0.205
0.154
0.076
0.011
0.053
0.021
0.033
0.063
0.077
0.020
0.082
(0.077)



Hands Only
mg/hr
5.94
2.26
4.39
0.45
10.51
4.72
11.77
1.37
3.86
2.37
12.32
2.16
4.27
14.73
9.24
3.26
1.05
3.53
1.00
1.16
2.77
3.45
1.19
4.70
(4.11)
ng/nr
2.86
1.72
4.34
0.30
* 1.18
2.48
4.43
1.32
2.36
1.53
3.09
1.65
3.75
13.38
6.00
2.31
0.70
3.07
0.87
0.93
0.64
3.06
0.93
2.83
(2.86)
:» Total
48.14
76.18
98.80
66.16
11.22
52.70
37.64
95.80
61.23
55.20
25.09
78.45
87.94
90.80
86.44
70.80
66.58
86.98
87.00
30.14
23.09
88.65
77.77
67.52
(24.68)
kg of body weight

-------
                                                                                1U
                                                          Section  No.  Appendix
                                                          Revision No"!   Draft
                                                          Date:
                                                          Page:"
79
September 1982
  o?   23
                                 Table A-14
             Comparison  of  Captan Exposure by Different Groups of

                              Strawberry Pickers

                           Field Study No. 2 - 1981


                     Permal  Exposure Expressed in ma/hr
Group

Adults (*12)
Children («11)
Adults (414)
Youths (f.13)
Females
Males
Adults (>12)
Children (*11)
Adults (>14)
Youths (<13)
Females
Males
Average Age No. of subjects Captan Cone.
mg/hr

19.71 21
11.00 2
26.00 11
12.50 12
11
12
Dermal Exposure Expressed



Mean
4.97
1.96
4.91
4.53
3.83
5.51
in mg/kg/hr
0.085
0.048
0.072
0.091
0.068
0.095
S.D.
4.20
1.14
4.24
4.16-
3.32
4.71
0.080
0.021
0.060
0.091
0.080
0.075
(1)
0.33
0.83
0.34
0.52
0.57
0.42
Statis
p-Val
(2)
0.35
0.67
0.36
0.76
0.74
0.24
tics
ues *
(3)
0.25
0.48
0.56
0.79
0.74
0.65
(1) Assuming normal distribution of data
(2) Assuming natural log normal distribution
(3) Wilcoxon nonparametric test
                                              89

-------
                                                                            102
                                                 Section No.  Appendix,
                                                 Revision No.  Craft
                                                 Date:    Sestemper 1982
                                                 Page     ,20     of	43,

                            Table A-15
            Pearson Correlation Coefficients  for  Variables
                           Field Experiment No. 2-1981

          Variables                Correlation Coefficient
      Age vs Productivity                0.795 *
      Hours worked vs total  excosure     -0.394
      °roductivity vs total  exposure      0.127
      Productivity vs log total  exposure 0.173
             Age    vs  total  exposure      0.120
4-
 Statistically significant  at  pi" 0.05
                                           90

-------
                                                                        103
                                               Section  No._Append1x
                                               Revision No._ Draft 1  .
                                               Date     September.1982
                                               Page   21  of   &i
                     Field Study No.  3

 Site and Location:  Cooperative  Farm  A,  Salinas, California

 Daie of Study:  July 21,  1981

 learner: fog early morning;  temp.  53-59°F, early morning, rising to 76°
          in the afternoon,  little  wind  in the morning (2,3-3.0 mph).
          gusts  of wind in the  afternoon (16-20 mph).

Number and age of subjects:  15  pickers  (ages  3-42); 4 weeders, 1 extra (6 yrs)

-------
                                                                          104
                                                Section No.   Appendix
                                                Revision No.   Draft  1
                                                Date:.    September  1982
                                                Page
           22
Of  A3
                           Table A-16
    Physical  Characteristics and Work Habits of Strawberry  Picksrs
                      rield Study No.  3 - 1981

Worker  Sex   Age      Weight Distance  Productivity    Hours   Body Surface
 I.D                   kg   covered       crates/hr  Worked      m2
                               ft
1
3
4
5
7
9
10
11
13
14
15
17
18
19
21
22
23
£7
25
29
M
M
F
F
M
M
M
M
M
F
M
M
M
F
M
M
F
M
M
M
21
42
n
n
9
10
17
13
18
27
15
27
41
23
n
•• •}
i *>
27
17
12
6
36
68
41
32
27
35
61
44
68
71
51
84
73
50
36
46
60
50
54
22
n/a
1800
3000
1200
600
1500
2700
1800
2400
675
1800
1200
6000
1200
n/a
1300
1500
1200
600
600
                                           3.49
                                           2.23
                                             04
                                             84
                                             02
                                           1.69
                                           2.
                                           2.
                                           2.
                                           1,
79
02
51
82
                                           1.57
                                             75
                                             69
                                             20
                                           n/a
                                             71
                                             15
                                             61
                                             14
                                           0.29
5.73
6.70
5.92
7.17
3.92
5.90
7.17
6.42
7.17
5.50
7-17
4.80
6.50
3.75
4.67
7.00
6.50
3.83
3.50
3.42
2.00
1.75
1.30
1.10
1.00
1.00
1.70
1.40
1.80
1.80
1*50
1.95
1.80
1.45
1.20
1.35
1.55
1.50
1.50
0.90
                                       92

-------
                                                                          105
                                                            Aooendi x
           Section No.
           Revision No."__   	
           Date:	September 1982
           Page     23     of   43
                                                             Draft  1
                          Table  A-17
          Exposure Results of Strawberry  Pickers
                     Field Study No.  3 -  1981
    Worker
      I.D.
           M
                            Total
Dermal  Exposure  (Captan)

                    Hands Only
                     rag/kg b.w./nr
    mg/hr
mg/hr
Total
      1                  0.655
      3                  0.169
      4                  0.237
      5                  0.331
      7                  0.470
      9                  0.125
     10                  0.360
     11                  0.211
     13                  0.250
     14                  0.233
     17                  0.270
     21                  0.038
     22                  0.351

     27                  0.152
     23                  0.791
    (29                  2.940

            MEAN VALUES  0.310
                 S.D.   (0.2CO)
    56.32
    11.53
     9.70
    10.59
    12.70
     4.36
    21.91
     9.32
    17.67
    16.57
    22.62
     1.37
    16.16

     7.61
    42.74
    64.67

    17.41
   (14.53)
36.82
5-. 19
7.04
3.29
8.14
3.00
13.84
6.35
13.95
4.62
14.65
0.36
11.33
4.86
33.43
5.23
11.16
(10.65)
65.38
45.04
72.61
31.09
64.10
63.80
63.15
73.50
78.91
27.87
64.74
25.95
70.09
63.79
78.22
8.09 )
59.55
(13.03)
Subjects 15, 19, and 23 were deleted due to failure to wear gloves throughout
trie study.  Subject 29 was deleted as explained in tne text.
                                         93

-------
                                                                                 106
                                              Section No.  Appendix
                                              Revision No.  Draft  1
                                              Date: _ September 1982
                                              Page    "24"    of  43


                         Table A-18


      Comparison of Captan Dermal Exposure by Different Groups

               of Strawberry Pickers

                Field Study No. 3-1981


               Exposure expressed in milligrams/hour
Group

Adults (*12)
Children (HI)
Adults (*14)
Youths (*13)
Females
Males
Average Age No. of
subjects

20.7 10
10.4 5
24.14 7
11.25 8
3
12
Captan Cone Statistics
mg/hr p-Values*
Mean
22.25*
7.74*
22.03
13.37
12.29
18.69
S.D. (1) (2) (3)
15.52 0.07 0.01 0.03
4.70
16.04 0.26 0.13 0.09
12.72
3g7J4 0.52 0.90 0.72
  (1) Assuming normal distribution of data
  (2) Assuming log normal distribution of data
  (3) Wilcoxon nonparametric test
 Statistically different at p^O.05


               Exposure Expressed in mg/kg b.w./hour
Adults (*12)                                     0.345     0.213   n «   n ?n   n  /n
Ch1ldren(*n)                                    0.240     0.170   °'35   °'2°   °'43

Adults fi!4)                                     0.300     0.171   n Rfi   n 77   n  Qc
Youths Ul3)                                     0.319     0.234   °'86   °'77   °'95

Females                                          0-267     0.055   ft CQ   ...
Males                                            0.321     0.223   °'69   °'91   °-94

-------
                                                                            107
                                                 Section No.   Appendix
                                                 Revision No.  Draft   i
                                                  Date :     September 1982
                                                  Page     26     of   &3
                             Table A-20
         Correlation Coefficients for Variables  of Strawberry Pickers
                         Field Experiment No.  3  -  1981
            Variables                       Correlation  Coefficient*
Age vs. Productivity                                 0.59+  (S)
Hours  vs. total hourly exposure                     -0.14
Productivity vs. total hourly exposure               0.28
Productivity vs log total hourly exposure            0.28
Age vs. total hourly exposure                        0.15
Total  daily exposure vs. distance covered            0.15
*
 (S)= Spearman correlation coefficient; all others are Pearson's
+
 Significant at * 0.05 p
                                       95

-------
                                                      108
                                      Section  No.   Appendix
                                      Revision No._ Draft " _.
                                      Date:       Sestsrcper  ]9S2
                                      Page ~TT  of    43
               rield  Study  No. 4
Site and Location:  Cooperative Farm B, Salinas, California
Date of Study:  August 21, 1981
Weather: Temp.:  65-69.5'F;  75-38c» R.H.; wind speed; 4.5-15 mph.
.Number and age  of subjects: 6 harvesters (ages 8-41)

-------
                                                                      109
                                             Section  No.   Appendix
                                             Revision No.  praft  1 _
                                             Date : __ SeptemDer'1932
23
                                                            of   43
                        Table A-21
Pesticide  Spray History, Cooperative Farm B, California, 1981
Date of
Application
4/25/31,



6/24/81


3/5/81


8/ IS/81



S/1S/81


Pesticides
*
Diazinon
Orthocide
Benlate SOW
Kel thane
Mai a th ion 25W
Benlate SOW
Orthocide SOW
Ma lath ion 25W
Benlate SOW
Orthocide SOW
Plictran SOW
Ma lath ion 25W
Benlate SOW
Orthocide SOW
Kel thane 25W
Malathion 25W
Benlate SOW
Orthocide SOW
Product/A




4.0 Ib.
0.75 Ib.
4.5 Ib.
4.0 Ib.
0.75 Ib.
4.5 Ib.
2.5 Ib.
4.0 Ib.
0.75 Ib.
4.5 Ib.
6.75 Ib.
4.0 Ib.
1.0 Ib.
4.0 Ib.
AI/A
24 oz
4.5 Ib
12 oz
24 oz
1.0 Ib.
0.37 Ib.
2.25 Ib.
1.0 Ib.
0.37 Ib.
2.25 Ib.
1.25 Ib.
1.0 Ib.
0.37 Ib.
2.25 Ib.
1.7 Ib.
1.0 Ib.
0.5 Ib
2.0 Ib.
Method of
Application/
Final Volume .
300 gal water



Hand rig
300 gal /A

Hand rig
300 gal /A

Hand rig
300 gal/A


Hand
Applied only to
2nd year berries

                                      97

-------
                                  Section No.   Appendix
                                  Revision No. _urart   I
                                  Date : _    September '
                                  Page
                                                29
                                                                  of   43
                            Table A-22


    Physical  Characteristics and  dork Habits of Strawberry Workers

                       Field Stuay No. 4 - 1981
Worker  Sex   Age    Weight
 I.D.                   kg
                              Productivity    Hours  Body Surface
                                crates/hr     worked     m2
  2
  9
 10
 12
 15
 16
M
F
M
F
M
41
 3
14
 9
15
13
72
25
50
27
50
34
1.44
0.57
1.15
0.57
1.15
1.44
3.48
3.48
3.48
3.48
3.48
3.48
  70
  00
  50
  00
1.50
1.30
                                       98

-------
                                                                     111
                                             Section No.   Appendix
                                             Revision No.  Draft  1
                                             Date:	September 198T"
                                             Page    30      of	43
                        Table  A-23




         Exposure Results of Strawberry Pickers

                Field Study No.  4 -  1981
   Worker
    I.D.
     2
     9
    10
    12
    15
    16
                   Total
mg/kg b.w./hr

     0.294
     0.394
     0.330
     0.571
     0.335
     0.544
                 Dermal  Exposure  (Captan)
mg/hr

  21.18
   9.84
  16.52
  15.44
  16.75
  18.49
                                      Hands On!
mg/hr

  18-. 71
   9.17
  13.62
  12.84
  14.57
  17.01
niy
% Ti
otaT

88.32
93.14
82.45
83.21
86.97
92.01
MEANS
 S.D.
     0.411
    (0.118)
  16.37
  (3.78)
  14.32
  (3.34)
   87.69
  ( 4.40)
                                           99

-------
                                                 Section No.   Appendix
                                                 Revision No.  Dra^t  ',
                                                 Date:    "September 1982
                                                 Page    31	of   43
                            Table A-24
    Comparison of Captan Exposure  by  Different Groups of Strawberry Pickers

                     Dermal  Exposure in milligrams/hour

Group

Adults (*12)
Children (»11)
Adults (-14)
Youths (*13)
Females
Males
Study No
Average Age

20.8
8.5
23.3
10.0

. 4 - 1981
No. Of
subjects

4
2
3
3
3
3


Captan Concn
mg/hr
Mean
18.24
12.64
18.15
14.59
18.15
14.59
S.D.
2.15
3.96
2.63
4.38
2.63
4.38

_ Statistics
p-Values*
(1) (2) (3)
0.08 0.08 0.11
0.29 0.30 0.38
0.29 0.30 0.38
                   Dermal  Exposure  in mil 1 ig^ams/kg'/hour
  Adults (il2)
  Children
0.376
0.483
0.113
0.126
0.35   0.32  0.25
  Adults  (*14)
  Youths  (*13)

  Females
  Kales
0.320*
0.503

0.320*
0.503*
0.022
0.096
0.032  0.024 0.03
      0.032  0.024 0.03
   (1) Assuming  normal  distribution  of  data
   (2) Assuming  log normal  (natural  log)  cistribution  of  data
   (3) Wilcoxcn  nonparametric  test
                                                                 100
" Kq of body weight

"Statistically  significantly Different at


-------
                                                                   113
                                                          Appendix
        Section No.
        Revision No.
        Date:     Sgpjfiniasr 1S82
                32     or    43
                                                          Draft
                       Table A-25




Captan Exposure  by  Various Parts of the  Body of Strawberry

       Pickers.   Field Study No. 4  (6 subjects)
  Body Part
                        mg/hr
Exposure

 S.D.
 % of total
(weighted  average)
Head + neck
Back + snoulder
Chest + stomach
Lower leg
Upper arms
Lower arms
Hands
Total
Other than hanos
0.057
0.067
0.035
0.161
0.038
1.691
14.320
16.370
2.050
0.056
0.073
0.017
0.169
0.037
0.801
3.340
3.776
0.828
0.32
0.39 '
0.25
0.95
0.24
10.18
87.69
100.00
12.31
                                101

-------
                                                                 114
                                           Section No.    Aooendix
                                           Revision No.  Dra-t  1"
                                           Date:      September'1982
                                           Page     33     of   43
                       Table A-26
     Spearman Correlation  Coefficients for Different Variables
                        Field Experiment No.  4-1981

           Variables               Correlation Coefficient
    Age vs productivity                    0.717
    Age vs total  dose                      0.829"1"
    Productivity  vs  total  dose             0.956+
    Log (In)  total dose  vs  productivity    0.956
Significant at   0.05  p
                                      102

-------
                                                             115
                                       Section No.  Appendix
                                       Revision No. Draft 1
                                       Date : _ September 1982
                                            _
                                       Page     34      of


                   Table A-27




Dislodgeable  Captan Residues from Strawoerry Leaves


               Field Study No.  4 - 1981
       Sample  No.              Captan Concentration

                            ug/cm         PPM on dust

         3.1                 2.74             8867

         3.2                 0.10              376
                        103

-------
                                         Section  No.  Appendix
                                         Revision No. _ Draft	]_
                                         Date:    Seotenper ]Q82_
                                         Page   35   of    43
               Field Study No.  5

Site and Loacat^on:  -Cooperative Farm  C,  Salinas, California

Date of Study:  August 21,  1981

Weather:  Temp.:  65-6915°F;  75-88f=  R.H.; wind speed: 4.5-15 mpn,

Number and age  of subjects:  10  pickers (aoove age 11)
                                104

-------
                                                      117
                                Section No.   Aooendix
cide Spray Kist
Data of
Application
3/31 - 4/1/81




4/17/81


5/17/31



6/7/81



7/4/31

7/30/31



*• •• i .• ~ i
W 1 •»/ O 1

Table A-28
OPV. Coooerative Farm C, Calif
Pesticides
Plictran SOW
Oiazinon SOW
Tops in M (70W)
Thiodan 2E
Moretrol 4E
Ben! ate SOW
Orthocide SOW
Bufferol
Dibron 8£
Oxyflow Sulfur
Tops in M
Bufferol
Dibrom 8E
Benlate SOW
Orthocide SOW
Bufferol
Phosdrin 4
Benlate
Orthocide 50
Bufferol
Phcsdrin 4
Cxyflow Sulfur
Tops in M (70W)
Eufferol
Encosuifan 2E
Thy! ate SEW
Product/A
2 Ib.
1 Ib.
1 Ib.
1 gal.
1 qt.
1 Ib.
4 Ib.
1 pt.
1 pt.
1 qt.
1 Ib.
1 pt.
1 pt.
1 Ib.
4 Ib.
1 pt.
1 qt.
1 Ib.
2 Ib.
1 pt.
1 pt.
1 qt.
1 Ib.
1 pt.
1.5 gal.
2.5 Ib.
Revisii
Date:
Page
ornia, 1981
AI/A
1.0 Ib.
0.5 Ib.
0.7 Ib.
2.0 Ib.
1.0 -lb.
0.5 Ib.
2.0 lb.
1.0 pt.
1.0 Ib.
1.5 Ib.
0.7 lb.
1.0 pt.
1.0 Ib.
0.5 Ib.
2.0 Ib.
1.0 pt.
1.0 Ib.
0.5 lb.
1.0 Ib.
1.0 pt.
1.0 lb.
1.5 Ib.
0.7 Ib.
1.0 pt.
3.3 Ib.
1.6 lb.
an NO. Draft 1
	 Seotember T9S2
36 Of 43

Method of
Application/
Final Volume
Ground
600 gal /A


.
Air
20 gal /A

Air
20 gal /A


Air
20 gal/A


40 Acres
sprayed by air
20 gal /A

Helicopter
20 gal/A


Ground
600 gal /A
 (th-irarc)

Oxyflow  Sulfur

Bufferol. Sorav-
2.0 qts.    3.0 lb.
32 acres were-
treated
                                         105

-------
                                                  Section No.   Appendix
                                                   Revision No.  Draft  	
                                                   Date:    September 1_982_
                                                   Paga    37	6T"  43
                              Table A-28 (continued)
   Date cf
 Application
  Pesticides
Product/A    AI/A
 Method of
Application/
Final Volume
*» ' 1 7 ' - 1
W( I // l> I
Thiodan 2E

Thy!ate 65W

Oxyflow Sulfur

Sufferol
Sprayfilm B
1.5 gal.    3.0 Ib.

2.5 Ib/A    1.6 Ib.

2.0 qts.    3.0 Ib.
 Ground

 500 gal/A

 3 acres were
 treated (see
 8/14/81 appli-
 cation)
                                         106

-------
                                                                    119
                                             Section No.  Apoendix
                                             Revision No. Draft
                                             Date:     September
                                             Page     38      of   43
                         Table A-29
Physical  Characteristics  and Work Habits of Strawberry Workers

                 Field Study No. 5 - 1981
Worker
I.D.
1
3
6
8
13
14
17
18
25
30
Sex
M
F
M
M
F
F
M
M
M
M
Age
19
16
24
28
34
18
17
19
27
17
Weight
kg
64
48
86
57
48
51
59
66
66
54
Productivity
crates/hr
n/a
n/a
•1.53
1.40
2.73
n/a
1.09
1.53
n/a
1.68
Hours
worked
3.33
3.53
4.58
3.58
4.40
3.58
4.58
4.58
2.92
3.58
Body Surface
m2
1.80
1.40
2.00
1.60
1.40
1.50
1.60
1.70
1.80
1.60
                                  106

-------
                                                             120
                                           Section No.  Appendix
                                           Revision No._&raft  1
                                           Date:     September 1982
                                           Page    39      of   43
                     Table A-30


     Exposure Results of Strawberry Pickers

                  Field Study No.5 - 1981
    Worker
     I.D.
                    Total
             Dermal  Exposure  (Captan)
             mg/kg
       /hr
 mg/hr
                                                     Hands Only
      1
      3
    • 6
      8
     13
     1A
     17
     18
     25
     30
0.151
0.075
0.029
0.081
0.188
0.248
0.057
0.032
0.126
0.055
 9,
 3,
 2,
 4.
 9.
66
62
53
60
01
12.66
   38
   10
   31
4.
1,
1.
3.
7,
9.
2,
1,
92
43
91
80
18
27
60
89
 2.95
                8.01
                2.82
50.96
39.41
75.68
82.52
79.68
73.26
76.94
90.00
96.49
95.71
MEANS
S.D.
0.104
(0.072)
5.88
(3.70)
4.39
(2.83)
76.07
(18.36)
kg of body weight
                                   107

-------
                                                                   121
                                        Section No.   Appendix
                                        Revision No.Draft1
                                        Date:_  September 1982
                                        Page    an      of 43
                    Table  A-31
Captan Exposure  of Various Parts of the  Body of Strawberry

          Pickers.  Field Study No. 5  -  1981 (10 subjects)
        Body  Part
    Exposure
ir.g/hr
                                          S.D.
  3  of  total
(weighted average)
Head + neck
Back •*• shoulder
Chest + stomach
Lower leg
Upper arms
Lower arms
Hands
Total
Other than hands
0.130
0.203
0.231
0.132
0.091
0.659
;.2£4
5.382
1.493
0.189
0.216
0.247
0.170
0.087
0.320
2.832
3.698
1.543
3.66
3.26
3.68
1.93
1.47
9.93
76.07
100.00
23.93
                                  108

-------
                                                                  122
                                                Section No.  Acoendix
                                                Revision No.  Draft  1	
                                                Date:	Septemoer T982
                                                Page    41       of  43
                            Table A-32
          Comparison of Dermal Exposure  of Captan by Sex

                of Strawberry Pickers

                  Field Study No.  5 -  1981
Sex No. of
subjects

F 3
M 7

r 3
M 7
Caotan Exoosure
Mean
mg/
8.43
4.79
mg/kg
0.170
0.076
S.D.
'hr
4.55
3.00
b.w./hr
0.088
0.047
Statistics
n-Values*

(1) (2)
0.16 0.19 0.

0.05 O.OS 0.


(3)
17

11
(1)  Assuming  normal distribution of data
(2)  Assuming  log normal distribution of data
(3)  Wilcoxon  nonparametric test
                                  109

-------
                                                                            123
                                                    Section No. ^Acpendix
                                                    Revision No."
                                                    Date :    September
                                                         _
I                                                   Page     42     of
Jl                                                           ~ "   ~"~     J
                               Table A-33

            Correlation Coefficients for Different Variables
                         Field Study No. 5 - 1981

              Variables                       Correlation Coefficient*
   Age  vs  productivity                            0.74 (P) (p»0.09)
   Productivity  vs total dermal exposure          0.83 (P)
   Total dermal  exposure vs hours worked         -0.54 (S)
   Age  vs  total  exposure                          0.25 (P)
   P=Pearson correlation coefficient
   SsSpearman correlation coefficient
   Significant at* 0.05 p

-------
                                                  124
Youth in Agriculture:  Dermal Exposure to
  Carbaryl by Strawberry Harvesters 1982
        Research performed  by

        University of California
        Richmond, CA  94804
                              i

        December 1983

-------
                         Abstract
                                                               125
Dermal exposure to carbaryl of 18 fieldworkers harvesting
strawberries was measured on three consecutive days in June
1982 on a farm in Corvallis, Oregon.  The study was designed to
measure productivity vs age, exposure vs productivity, exposure
vs age and to test for exposure by different age groups and
gender.  A significant difference in productivity was detected
between youth and adults.  Age and productivity exhibited
significant positive correlations.  Dermal exposure for youths
(14 years and younger) was lower than adults for all three days.
No significant correlations were observed between dermal dose
rate and physical characteristics of the harvesters, e.g. sex,
body weight, and height.

-------
                                                                 126
                         1.0  INTRODUCTION



*"     In  order  to  complement  the  1981-studies  on the assessment of



pesticide  exposure  by  strawberry pickers,  an  additional detailed



field study  was conducted  during June  of  1982 in Oregon. The site



o-f the study,  a commercial strawberry  farm near Cor vail is, OR,



was  the  same as that chosen  for  Study  2 in 1931.



      The design of  this study was to measure  dermal exposure to



several  pesticides  which had been used on  this plot. Since in the



 1981-studies it was shown  that dermal  exposure among strawberry



pickers  mainly consisted of  pesticide  deposits to hands, forearms



and  lower  legs, only these three anatomical regions were monit-



ored.  Observations  were made in  the morning and afternoon of



three consecutive harvesting days.  Of  the  23  ^volunteers who



started  out, only 18 completed the three-day  course. The 'statist-



ical  analyses  presented in this  report, therefore, deal with



"these 18 subjects.



      The major aim  of  this study was to examine the variance of



dermal exposure among  individuals and  the  group as a whole.



Results  of such studies might aid in the   experimental design of



future field studies.  There  was  some anticipation that the find-
                                                               •


ings of  this study  might elucidate whether dermal exposure is



affected by  individual  work  characteristics or environmental



factors  or both.



      Two approaches for the  statistical analysis of the results



were applied.  The first considered the variance of individuals



and  the  group. In the  second approach, each of the six monitoring



periods  
-------
                                                                127

experiments. Similar to the 1981-studies the -following correlat-

ions were tested: age vs. productivity;  exposure vs. producti-

vity; exposure vs. age; t-test -for exposure by different age

groups and gender.
 */
     This is the -first report of a series and deals exclusively

with the results obtained -from exposure to carbaryl.



                     2.0 EXPERIMENTAL DESIGN

2.1  Field Stud.*..

       A privately owned strawberry farm near Corvail is, OR was

chosen as the site o-f the field experiment. The dates of the

study were June 22-24, 1982. The field had been sprayed prior to

the study date with 3 pesticides as follows: carbaryl, 2 Ibs/A, 7
                                            *
June , 1982; vinclozolin, 1 lb/A, 3 applications on 5, 15. and 22

May, 1982; endosulfan. 1 lb/A, 15 May, 1982.

     Twenty-three harvesters volunteered to participate in the

study initially, but only IS workers completed the three-day

exercise. At the beginning of each workday  (between 0600 and 0800

hr) , the workers were outfitted with dermal monitors*, light

cotton gloves for the hands and cotton patches on the forearms

and ankles. A description of these dermal monitors has been given

in the 1982-final report on the 1981-studies. Patches were kept
• The term "monitor" as used throughout this report,  refers to
cotton gloves and gauze pads which measure dermal exposure. These
devices  are  intended to yield information on  the  quantity  of
pesticide  residue  deposited  on the skin surface  but  does  not
address the issue of percutaneous absorption.

-------
                                                                   128


on the subjects during the entire working period (About 6 to 8
             I

hrs). Gloves, however, were removed in the morning after the


•first or second crate of strawberries had been brought to the


weighing station. Another set o-f gloves was issued after the


lunch break to be worn till the end of the workday. The morning


gloves were usually worn -for one to two hours, depending on the


work efficiency of individ-ual harvesters, while the afternoon


gloves were worn for a slightly longer period. Since the time


periods during which the gloves and patches were worn might be


critical in the estimation of hand-exposure to pesticides, this


information is given in the Appendix.


     The procedure for hand monitoring was changed on the second


day of the study when it was observed that a large amount of dew
                                            •

on the strawberry foliage appeared to contribute a great deal of


moisture to the glove.  It was believed that the moist condition


o-f the gloves might possibly impair the absorptive capacity of


the cotton cloth. Consequently, on the second day the volunteers


were provided with patches at the beginning of their workday and


gloves about one to two hours later after the initial dew on the


leaves had dried.


     At  the  completion  of the monitoring  period,  gloves  and


patches  were removed from each subject,  stored individually  in


plastic  Zip-closure type bags over dry-ice,  transported to  the


laboratory  ,  and  placed in the deep-freeze until  the  samples


could be extracted and analysed.  The gloves were peeled from the


hands inside—out in order to minimize contamination.


     Forty-eight leaf disks from strawberry plants were sampled

-------
                                                                   129
with a mechanical punch, designed so that  the l«af disks dropped



directly into a glass storage bottle. The punch was equipped with



a mechanical counter to -facilitate the sampling. The procedures



•for sampling and collecting leaf disk*  and the analysis of



dislodgeable foliar pesticide residues have been described in the



1982-Report to EPA (Popendorf, et al. 1982).



2.2 S.amgl.e, EjiiMcSiSQ arig; Analysis..



     Gloves were thawed to room temperature placed into a 500-mL



wide-mouthed LP-plastic bottled -fitted with a screw cap and



extracted with 100-mL acetonitrile by shaking on a reciprocal



shaker 
-------
                                                                130



directly analysed -for carbaryl as will be described below.



     Leaf dust, originally washed off with the surfactant, re-



mained in the interfacial »olvent-water  layer in the separatory



•funnel and was quantitatively transferred after the last solvent-



extraction to a pre-weighed glass -filter. A-fter drying at  110"



overnight, the -filter was reweighed, and the weight o-f the -foliar



dust was calculated by difference in weights.



     Carbaryl residues were analyzed by  reverse-phase HPLC using



a Waters 6OOOA Solvent Delivery  System,  WISP Automatic Sample



Processor, Waters Data Module with  Automatic Integrator, and



Model 45O Variable Wave  Length Detector. The chromatographic



column was ufiondapac'k C».. The experimental conditions were:



mobile phase  , acetonitrile - water (40:60)) flow rate 2 mL/min,



and detection at 230 nm. Under these conditions, carbaryl  has a



retention time o-f 4.61 min and its  metabolite, 1-naphthol,  5.1



min; absolute sensitivity as limited by  background noise and



automatic integration was 2 ng.



     Laboratory recovery studies for carbaryl and 1-naphthol were



performed with cotton patches and detergent extracts as follows:



Known amounts of carbaryl   (69 to 173 ug) and 1-naphthol  (76 to



152 ug) were  added to "control"  patches  which were extracted as



described above. Known amounts of carbaryl  (628 ug) were added to
                                                          •


100 mL of the aqueous Surten* solution containing 48 leaf  disks,



and the aqueous phase was then extracted as described above.



Recoveries of added carbaryl and 1-naphthol were almost quantita-
                                               v


tive. as may  be seen in  Table 1.

-------
2.3 Sit£ii£ica.l Ana.Iy.iis
     Statistical  analyses  of experimental data   were  performed
using SAS,  a statistical computer software program  developed by
Statistical Analysis Systems, Inc.

                   3.0 RESULTS AND DISCUSSION
3.1  Qfrmal gxEQSyre.
     Eighteen strawberry harvesters were monitored -for the entire
course o-f the study consisting o-f three days, morning  and  after-
noon. Physical characteristics (sex, age, weight,  height,  and
body sur-face CSendroy and Cecchini, 19323) were recorded (Table
2-1). Individual productivity, expressed as crates o-f  strawber-
ries harvested per hour, as shown in Table 2-2, is further broken
down into productivity in the morning  (AMPROtH, a-fternoon
(PftPROD), and all-day (DAYPROD). As will be discussed  later,
these data were used in an attempt to  correlate productivity  with
dermal exposure, age, sex, and other variables.
     Tables 3-1, 3-1, and 3-3 show individual daily  exposures to
carbaryl, mean values, standard deviations  (S.D),  maxima and
minima, and coe-f-ficients o-f variation  (C.V). Hand  exposures were
broken down into morning  (AM), a-fternoon  (Pfl), and all-day
(HANDS). Furthermore, left and right hand and lower  arm exposures
were measured or calculated and are listed  in these  tables.
1     A three—day summary o-f these data may  be found  in Table 4-1.
All exposure values are expressed as mg carbaryl/hr/person. 1-
Naphthol was not detected in any of the -field samples  and was not
reported. Dermal pesticide concentration o-f  lower  legs (ankles)
was low or nondetectable and was excluded,  therefore,  from estim-

-------
                                                                  132

ations of total body exposure.



     By visual inspection of Table 3-1, 3-2, and 3-3, it appears



tn*t dermal exposure on Day-1 was generally higher than was -found



on subsequent days. This impression is supported by statistics,



demonstrating that the daily mean exposure variables -for the



three days differ significantly  (see Table 4-2), with the



possible exception of lower arm  exposures (ARMS).



     The experimental protocol was changed due to observations



while the experiment was in progress. Whereas gloves were placed



on the workers* hands on Day—1 and Day—3 as soon as the workers



entered the field early in the morning, gloves on Day-2 were



supplied two hours after the harvest had begun. The reason for



this change is our observation that early morning dew on the



leaves of the strawberry plants  caused the cotton gloves to



become saturated quickly with water and fruit juice. It was then



reasoned that wet gloves might no longer possess linear absorp-



tive capacity for dislodgeable residues from foliage and, there-



fore, would no longer serve as a suitable monitor for dermal



exposure. Since on the third day the morning dew did not appear



to be a serious problem, the original procedure was followed by



placing gloves on the workers" hands as soon as they began to



harvest.
 i


 i.    Contrary to what we believed might happen with a "saturated,



wet glove", namely the loss of its absorptive capacity, it is  the



gloves of Day-1 which exhibit a  higher carbaryl Concentration



than either Day-2 or Day-3 gloves. It appears, therefore, that



wet gloves may be more "efficient"  exposure monitors by being more

-------
                                                                133
absorptive than dry gloves, perhaps due to the partitioning of
the pesticides -from the dislodgeable -foliar residues into the
aqueous phase contained in the cotton cloth. This transfer due to
water solubility of pesticide residues might be an alternative or
additional explanation to the current view  expressed by
Popendorf and Leffingwell  (1982) that dermal exposure is the
result of contact-transfer -from dislodgeable -foliar residues,
mainly composed o-f pesticide residues absorbed or adsorbed on
dust.
     With patch monitors, dislodgeable pesticide residues are
presumably entrapped or absorbed by the cloth mesh o-f the multi-
layered gauze o-f which the patches are composed. Cotton gloves,
on the other hand, are made o-f smooth cotton material, and the
partitioning theory o-f the pesticide transfer from -foliage to
                                            .
cloth seems more plausible.
     Indirect evidence for the partitioning theory may be found
in the experimental finding that dose rates for hands were signi-
ficantly higher in the morning  (AM) than afternoon (PM> on Days-1
and -3 (T 3.5; df-34; p , but that no such differences
existed on Day-2. It was that day that the gloves were placed on
the workers' hands after the dew had dried, and the gloves re-
mained relatively dry during the monitoring period.
3.2 CgmBiCiaSQ gf BtCMl Sxp.gSu.Cf &v. Wgrkfrj SCSyfifi fey. A2S gr
     figs'* w«iflh£
     One of the goals of this study was to determine if the age
of strawberry harvesters affected dermal exposure to pesticides.
Since there were no subjects in this study  11 years and younger,
the 18 pickers were divided into two separate groups, youths

-------
                                                                 134


««14 years of age) and adultm  (>»15 years of age).



     Comparing these two age group*, the only difference in



dermal exposure was the right-hand exposure rate   SO kg).




3.3 i.tf£= Versus 5ifltL£rH*QSi E*B2!UC1



     In a study with captan and benomyl exposure  by strawberry



pickers  (Zweig, et al., 1983), it was found that  right- or left-



handed preference  by pickers could be observed by measuring



individual hand and lower arm exposures. Similar  studies have now



been made with carbaryl, as is shown.in Tables 3-1, 3-2, and 3-3.



However, in this study no significant differences were found



between exposure rates for the left and right hands in tbe morn-



ing, afternoon, the combination of mornings and afternoons, or



for lower arm patches worn all day.  This finding indicates that
                                10

-------
                                                             135
there is no particular hand preference among this group of straw-



berry harvesters, even though come of them might demonstrate



handed preference -for some other manual activity. The only  sig-



nificant correlation was demonstrated with worker height  (r» -



0.404; N«53; p<0.01), as is shown in -Figure 1, indicating that



left arm carbaryl exposure was predominant among shorter straw-



berry harvesters in this study. The significance o-f this curious



correlation is not within the scope of this study.



3.4 Wgrker ExBgjure Va.riab.U.i£y.



     One  o-f the objectives o-f this study was to investigate  the



variability  o-f worker dermal exposure (in mg/hr) as affected  by



environmental   and  other  factors. To  determine  the



significance of individually consistent behavioral patterns,



which may have influenced the pattern of derm/al exposure of the



individual., an analysis of variance was performed. The models



used were intended to predict AM, PM, HANDS, and TOTAL exposures.



Models including only DAY as a categorical predictor variable



were compared to models incorporating both DAY and individual



identity 
-------
                    E "sly!    Slants gf Friigga   a
          AM         12. 7O            2,31         O.0001
  H       PM          3.06            2,31         O.OO99
          HANDS      10.60            2,31         0.0001
          TOTAL      10.88            2,30         O.OOO1
Prom this analysis it is apparent that DAY is a highly signific-
ant predictor for these exposure variables.
     Adding the individual (ID) as a categorical predictor
variable did not significantly improve exposure predictions for
any of these variables according to F-tests comparing the
•iapler, nested model with the more complex model:
                     £=₯iluis   Staciti gf Ecttsac    B
An
PM
HANDS
TOTAL
0.922
1.415
- . 0.302
0.803
17,34
17,34
17,34
17,33
>0.03
>O.05
>0.03
>O.03
The above tabulation illustrates the predominant influence of
factors other than individual behavioral patterns on dermal expo-
sure as measured in this study.
     Another analysis Mas performed to investigate the variance
of hand exposures (as measured in mg/hr) of individual pickers
ov«r the three days of the study. There are six values for each
worker (AM and PM for three days). The analysis was performed
with and without normalising'hand exposure for the influence of
picking time period (AM or PM) or day. A summary of the results
from this analysis may be found in Table 6.
     Comparing the individual variances of the unnormalized  indi-
vidual dermal exposures  (Table 6), it is seen that the exposure

                               12

-------
o-f Picker No. 14 was more consistent than that of the  group  as  a

whole, and Picker No. 22's exposure was more variable  than that

o-f„the group. Primarily as a result o-f these two cases,  the

exposure variabilities o-f the individual pickers cannot  be consi-

dered homogeneous (Bartlett's X9*41.63, df-17, p <0.01).  It  is

noted that Picker No. 22 had the highest AM hand exposure on  Days

1 and 3 o-f the study, compared to that o-f the other workers.

     The exposures were normalised by subtracting the  correspond-

ing time- and day—speci-fic  hand exposure means. It is seen  -from

Table 10 that the variance o-f the normalized hand exposure o-f

Picker No. 22 remains significantly greater than that  o-f the

group. The variances o-f the group, despite this one high value,

can be considered homogeneous (Bartlett's X*«22.60, df»17,
                                             •
p 0.10). Thus, by controlling for day- and time-specific exposure

variability, intrapersonal exposure variabilities are  rendered

statistically homogeneous for the pickers in this study.
  i
  3.5 PrsdaStiyiiy.

     Productivity, expressed as crates harvested/hr, of  all work-

ers over the three days may be seen in Table 2-2. The  mean values

for  A.M., P.M. and daily productivity for the three days are not

significantly different, respectively  (Kruskal-Wallis
  i
X*«O.63-4.18; df » 2;  p >O.10). When examining the two  age

groups «14 and >15 yrs old), however, it was found that  the

daily productivity of youths was lower than that of the  adult

group (0.72 cr/hr vs. 0.89 cr/hr; F-11.36; df»l,48; p»0.0014).

This is in agreement with the finding that over the 3  days of the

study, each worker's daily productivity was positively correlated
                               13

-------
                                                                    1
•  » 0.4S9)  with his/her age to a significant degree (N « 51;  p

>.0007).  However,  age did not correlate significantly with

ther morning productivity (AnpRQD) or afternoon productivity

1PROD),  which are the productivity variables associated with

• times  during which the gloves were worn.

   3.6 eiil2d99*&l9 EsLiar. Rssiduss

     Samples of leaf disks to determine dislodgeable carbaryl

•idues were taken 3,7,14,15,16, and 17 days post application (2

•/A carbaryl), and the results of the analyses may be found in

ble 7m From these data and a plot of log. concn. vs time (see

g. 2), it appears that the decline of foliar dislodgeable

sidue obeys first-order kinetics. Days-15, 16 and 17 of the

cline study are identical with Days-l,2,and 3 of the exposure
                                             •
udy. It  is possible, therefore, to calculate the transfer
                                              •       •

tfficients of strawberry harvesters from their dermal exposure

ceived on these days.

   The  transfer coefficient (k«) may be considered to represent the
    ">j
action  of  dislodgeable foliar residue transferred to  the  exposed

in  of field workers during normal work activity in unit  time.  The

nensions  of  k« are area (cma) per time.  The larger  the  k«,  the
                                                           •
•ater the transfer efficiency.

   The calculated  k« values for Days-1,2..and 3 are 4.34,2,82,

d 6.17 x 10* cma/hr, respectively ( see Tables 3-3 and 7 for

P«rimental  data).  Table 8 is a comparison of transfer coeffic-

rtts -from this and  other studies. It may be seen that the trans-

r  coefficients for pickers are similar regardless of chemical

d  crops.  This observation  further tends to support the current

•w that  dermal exposure by fruit harvesters arises from foliar


                             14

-------
                                                                139
contact with plants which have been previously sprayed with



pesticides.



     Mail en et al. (1962) have studied the dermal  exposure to



carbaryl by pesticide applicators and thinners in  apple orchards.



From their reported values of hand exposure and total  extractable



carbaryl residues, the calculated k* is about 600,  which is



considerably lower than our values found in Table  8.  This appar—



ent discrepancy can be explained by the -fact that  these workers



measured total and not dislodgeable -foliar residues which would



result in a lower transfer coefficient.

-------
                                                                 140
                         Literature Cited
 ?


Iwata, Y.; Spear, R.C.;  Knaak,  J.B;  Foster,  R.J.  Bull. Environm.


     Contain. Toxicol.  1977,18,  649-53.
                                     ^
                                                   •

Gunther, F.A.I Westlake,  W.E.;  Barkley,  J.H.I  Winterlin, W.;


     Langbehn, L. Bull.  Environm.  Contam.  Toxicol.  1973. 9, 243-49-


Gunther, F.A.; Barkley,  J.H.I  Westlake,  W.E. Bull.  Environn.


     Contam. Toxicol.  1974,,  12,  641-44.


Haitian,  J.C.;S«11,   R.C.{   McDonough,  L.M.;  and Fcrtig, S.N. in


   •  "Pesticide Residues and Exposure*(Piimmer,  J.R.,  ed.); ACS


     Symp. Series 182> A«er. Chem.  Soc., Washington,


     D.C.,12S2,pp.83-103


Pop end or-f, W.J. and Le-Ff ing well,  J.T.  Bui 1. .Environm.  Contam.


     Toxicol.  1977, 18,  787-98.


Popendor-f, W.J.; Le-f-f ingwell,  J.T.  Residue Reviews 12S2. 82, 123-


     201.


Popendor-f, W.J.; Le-f-f ingwell,  J.T.f  McLean,  H.R.; Zweig, 6.;


     Witt, J.M. "Youth in Agriculture.  Pesticide Exposure to


     Strawberry Pickers  —1981  Studies", Final Report, 2nd Dra-ft, EPA


     0-f-fice of Pesticide Programs,  Washington, D.C.  20460, Sept.



     1982.


Sendroy, J. Jr.; Cecchini, L.P-  J.  Appl. Physiol. 19S4, 7, 1-12.


Zweig, Gunteri Gao, Ru-yul Popendor-f,  W.J. J.  Agric.  Food Chem.



     12S2.31,  1109-1113.
                                   16

-------
                     SUMMARY AND CONCLUSIONS
     Dermal exposure to the insecticide carbaryl experienced  by
 18  fieldworkers  harvesting strawberries,  was measured on  3
 consecutive days in Junef 1982  on a commercial farm in Corvallis,
 OR.  Left and right hand  exposures were measured by means  of
 cotton gloves. Lower arm and lower leg.exposures were measured  by
 the  use  of cotton gauze pads. Gloves were changed for the after-
 noon work  period, while gauze  pads remained on the  persons for
 the  entire work day.  Leaf  disks from strawberry plants were
 sampled  randomly on several  dates  prior to the study days and  on
 the third day of the study and were analyzed-for  carbaryl  dislod-
 geable residues.
     The experimental  data  associated with  glove and lower arm
 patch exposure  measurements  were analyzed statistically,  and the
  i
 following conclusions were reached:
     1.  Dose  rates, expressed in mg/hr, for  hands from Day-1 and
Day-3 were significantly  higher in the morning than afternoon.
The  higher  morning  values  may have been  caused  by ' the
accumulation  of  morning dew on the plants which might have either
facilitated the  transfer of  dislodgeable residues from leaves  to
the gloves  and/or rendered the  gloves more absorptive or  retentive.
     2.  No  significant  correlations were observed between dermal
dose rate and physical characteristicss of the harvesters, e.g.
sex,  body weight, and height.
                          17

-------
   '  l                                                                 I 4?
     3.  Right-hand exposure  of  youths of age 14 or younger was
significantly lower  than that of adults (15 years and older) when
analyzing data  for  all three days. The  corresponding exposure
values were 0.54 mg/hr and 0.74  mg/hr,  respectively.
     4.  The mean afternoon hand  exposure of pickers  weighing less
than 50 kg was lower  than that  of the group of heavier persons
(0.80  mg/hr vs.  1.27  mg/hr,  respectively).
     5.  Left- and right mean  exposure  values  for  hands and lower
arms did not differ significantly. However,  a trend  towards left
band and left lower arm exposures was discerned among the workers
regardless  of  age.  Left lower arm exposure did correlate
negatively with  body height,  reflecting the predominance of left-
band and -arm exposures among shorter  workers in comparison with
their taller  counterparts in  this  study.
                                             4
     6.  The statistical analyses revealed that the particular day
on which exposure occurred had a highly significant  influence on
most types of exposure measured, including morning hand exposure,
afternoon hand  exposure, total hand  exposure, and total (hand
plus arm) .exposure.   In contrast,  individual  worker  identity did
not explain exposure variability to any significant degree, indi-
cating strongly  that  variables  other  than  those  associated with
the individual  (e.g., age, picking behavior) bad a predominant
influence on exposure  in this study.   No significant difference
could be  shown  between intra-  and inter-personal hand exposure
variabilities in this study, again suggesting that individual
picker characteristics and picking behavior  are  not influential
determinants  of  dermal exposure.

                                          18

-------
     7.  The  calculated transfer coefficient  (kg)  (relating dermal  ] 43
exposure to  dislodgeable  foliar residues) for strawberry harves-
ters exposed to carbaryl was  of the same order  of magnitude as
those previously  determined for captan and benomyl exposures and
0-P  exposure  in tree  crops   (citrus and peaches).  Due to the
similarity of  values  for  kd for various  pesticides and crops,  it
appears  that the  main source of dermal exposure  of fruit harves-
ters is  the  pesticide present as dislodgeable foliar residues.
     8.  Productivity of the group of strawberry  harvesters stu-
died was found not to be significantly  different on different
days or  times  of day.  A significant difference  in productivity
was detected between youths and adults  (0.72 crates/hr vs. 0.89
cr/hrf  respectively). Age and  productivity  also exhibited a sig-
nificant positive  correlation.

-------
*
                                   ft   ft
                      »
                      »
                      t
                                      ;vr--"-  "
                                    '"

-------
LO
       CM
     0.6

     O.S

     0.4

     0.3

     0.2

     0.1

      .0
        I
        i
        4/1      «
        S    -.4
              -.5
              -.6
              -.7
in
«—•
a
               I	I
I	I
                                                        8
                                                     9  10   11    12    13   14    15    16   17
                                                  DAYS POST-APPLICATION
                          FIGURE
                            CARBARYL DISLODGEABLE FOLIAR RESIDUE DECLINE - STRAWBERRY LEAVES

-------
                                                                 146
              GLOSSARY OF TERMS USED IB
      SEX
      WEIGHT
      HEIGHT
      AREA
      AMPROD
      PMPROD
      DAYPROD
      AMHOORS

      PMEOURS

      DAYHOORS

      ID
      Explanation

      0«female, l«nnale
      individual body weight
      individual height
      body surface area
      productivity, morning
      productivity, afternoon
      productivity, all day
      hours monitored, a.m.
                   (gloves)
      hours monitored, p.m.
                   (gloves)
      total hours monitored
               (arm patches)
leg
cm
crates/hr
crates/hr
crates/hr

hr

hr

br
      worker identification number
   AMLEFT
   PMLEFT
   AMRIGHT
   PMRIGHT
   AM
   PM
   LEFT
   RIGHT
   HANDS
   ARMLEFT
   ARMRIGHT
   ARMS
   TOTAL
             Explanation

left glove (hand), a.m.
left glove (hand), p.m.
right glove  (hand), a.m.
right glove  (hand), p.m.
AMLEFT + AMRIGHT
PMLEFT + PMRIGHT
(AMLEFT*AMHODRS + PMLEFT*PMHODRS)/(AMHOURS*PMHOURS)*
(AMRIGHT*AMHOORS + PMRIGHT*PMHOORS)/(AMHODRS*PMHODRS)
LEFT •»• RIGHT
left arm patch (all day)
right arm patch  (all day)
ARMLEFT + ARMRIGBT
BAUDS + ARMS
      In Tables  6-9, simple averages were used in place of
ese time-weighted averages; e.g., LEFT » (AMLEFT+PMLEFT)/2.
                                         22

-------
                                                   147
                .  Table 1

Recovery Studie* for Caroaryl and 1-Naphthol
             a*A.
                      added   -found
                            /Q
Carbaryl Patch-l

Patch-2

Patch-3
Patch-4
L«a-f punch-1

L»a-f punch-2

Leaf punch-3

L«a-f punch-control
1-Naphthol Patch-3-1
Patch-3-2
Patch-3-3
69.0

69.0

172.5
172.5
828.0

828.0

828.0

O
76.0
152.4
152.4
62.2
65.5
67.2
62.4
184.2
180.0' -
70O.8
705.6
828.0
782.4
679.2
734.2
2.0
77.2
153.1
150.7
92.6

93.9

106.7
104.3
84.9

97.3

B«i. -^

n/a *
101.5
106.5
98.9
                          23

-------
                                                       148
                  Table 2-1
    lw SbX fc&fc HEIGHT HEIGHT AfcfcA
     i  0  40   b<».5   l*b 1,77
     7  C  12   42.3   163 1.52
     C  0  IB   63.6   175 1.78
     S  0  :9   56.7   1M 1.56
    1«  0  13   43.1   149 1.35
    11  0  :2   61.3   17h 1.72
    11  0  15   ?9.0   If'G 1.64?
    12  0  16   50.4   173 1.36
    14  1  13   63.6 .  17fc i.76
    li  1  13   7w.4   i^b 1.7b
    17  0  12   »5.4   1^7 l.«2
    i:  0  12   49.9   163 1.5£
    20  1  14   56.7   1*0 1.70
    21  C  14   54.5   1*5 1.5V
    22  0  37   49.9   1*2 l.*6
    2Z  0  16   49.9   !*•* l.*3
    25  1  12   45.4   iMi i.o
    21  1  :5   63.6
1 tO«FtCAL£i  WT  1M KC,  HT  IN CM)fArea in  if.
                                24

-------
                              Table   2-2
ID
              MMIIS/IIK)
               DAY-1
        OAY-2
AMPROO I'MPRGU  OAYPKOO
         OAY«3
AHPROO PHPtiDD OAYPKOD












ro
ui





6
7
8
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26
Mean
1.4?
0.61
0.64
0. 70
0.3S
0.99
0.9C
0.61.
0.99
U.97
1.00
0.6f.
2.50
o.&i;
0.99
1.25
0.63
0.^7
0.94
1.33
0.47
1.00
1.30
0.63
1.05

1.35
O.ilU
0.55
0.92
0.72
0.06
u.4 7
0.61
0.56
O.U4

0.%88
1.17
O.Sto
O.H5
G.B«>
0.9L"
l.Oo
1.0'j
0.79

C . f»0
t
0.63

O.*»4
t
1.06
0.8o

0*85
1.01
0.70
0. 99
1.0?
1.17
1* 1&
0.33
0.77
1.09
0.76
0.6?
0.5?
0.45
0.67
0.31
1.2f.
0.67
0.83
0.85
0.42
1.40
0.92
0.52
0,22
1.11
0.41
0.56
0*67
0.00
0.62
0.25
0.65
0.50
0.8b *
1.25'
0.62
0.74
0.70
1.03
O.i»7
0.07
1.00
0.75
1.05
0.9u
0.7U
l.OU
0.62
O.S5 "
0.42
0.111
O.HC
0.77
0.71
0.60
0.74
0.78
0.90
0.86
0.95
0.37
0.7R
0.97
1.00
0.61
1.0?
1.54
1.16
0.95
1.04
0.37
1.01
1.5f»
0.711
0.7?
0.92
0.68
1.03
1.23
1.17
0.4b
0.79
1.37
0.6B
1.43
0.74
0.96
0.30
0.64
0.64
1.03
1.94
0.90
0.50
0.92
0.03
0.82
0.**!
I.JO
0.67
O.WJ
0.03
0.!»U
1.00
0.53
0.02
0.74
1.03
0.71
1.01
1.09
O.tt>
0.71
0.85
Note: "." - Missing value

-------
      DATA SUMMARY!  DOSE RATES, IN HG/HR
      LEFT, RIGHT  t  HANDS ARE TIME-HEIGHTED AVERAGES
      DAY«1
    ro
    ON
aan
.D.
in.
IX.
.V.
           10  AHLEFT AHR1GHT PMLEFT WIGHT ARMS  AH    PM   LEFT RIGHT HANDS TOTAL ARMLEFT ARMRIQIT
6
7
0
9
10
11
12
13
14
15
17
ID
20
21
22
23
25
26





1.49
3.82
1.00
1.38
0.39
0.42
1.36
4.12
0.99
2.35
0.76
0.36
0.81
1.74
3.80
2.36
1.57
2.26
1.72
1.19
0.36
4.12
69.07
0.99
o.ei
1.22
1.69
0.18
0.60
0.86
0.84
0.33
1.91
1.50
0.44
1.09
2.18
3.20
2.52
0.69
1.61
1.29
0.78
o.ia
3.20
60.79
' 1.01
0.26
0.19
1.52
0.34
0.57
0.59
1.07
0.58
1.37
0.71
0.05
0.46
1.15
0.60
0.33
0.89
0.75
0.69
0.41
0.05
1.52
59.22
0.99
0.4R
0.16
1.20
0.51
0.56
0.51
2.10
1.08
9.56
0.57
0.27
0.49
1.25
0.50
0.32
0.34
LIB
0.73
0.48
0.16
2.10
66.56
0.35
0.33
0.66
1.74
0.23
0.20
0.27
0.77
0.59
0.63
0.55
0.19
1.47
0.84
0.97
0.65
0.77
0.55
0.66
0.41
0.19
1.74
62.93
2.46 2.00
4.63 0.74
2.22 0.35
3.07 2.72
0.57 0.85
1.02 1.13
2.22 1.10
4.96 3.17
1.B2 1.66
4.26 1.93
2.26 1.26
O.BO 0.32
1.90 0.95
3.92 2.40
7.00 1.10
4.88/0.65
2.26 1.23
3.87 1.93
3.01 1.42
1.70 0.80
0.57 0.32
7.00 3.17
56.49 56.57
1.25 0.99
1.47 0.59
0.53 0.61
1.47 1.38
0.36 0.37
0.52 0.57
0.95 0.67
2.60 1.47
0.77 0.96
1.73 1.05
0.73 0.94
0.22 0.36
0.57 0.60
1,37 1.60
1.51 1.27
0.80 0.83
1.20 0.50
1.51 1.40
1.09 0.90
0.59 0.39
0.22 0.36
2.60 1.60
54.51 43.20
2.24
2.06
1.14
2.85
0.73
1.09
1.62
4.07
1.74
2.73
1.67
0.58
1.25
2.98
2.77
1.63
1.70
2.91
1.99
0.92
0.58
4.07
46.15
2.59
2.39
1.80
4.59
0.96
1.37
1.09
4.84
2.33
3.41
2.22
0.77
2.72
3.62
3.74
2.28
2.47
3.46
2.65
1.14
0.77
4.84
43.14
0.14
0.17
0.29
0.08
0.14
0.04
0.12
0.22
0.29
0.19
0.36
0.09
0.48
0.50
0.73
0.27
0.24
0.28
0.30
0.22
0.04
0.88
73.38
0.21
0.16
0.37
0.86
0.09
0.24
0.15
0.55
0.30
0.44
0.19
0.10
0.99
0.34
0.24
0.38
0.53
0.27
0.36
0.25
0.09
0.99
69.30
                                                                                                 LTI
                                                                                                 O

-------
                       Table 3-2
DAY-2
    10 AMLEFT ANRICHT PMLEFT PMUGHT  ARKS  AN    PM   LFFT RIGHT  HANDS  TOTALARMLEFT  ARMR1GHT







!


f\>







Mean
S.D
Minimun
Maximum
C.V.
6
7
a
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26





0.98
0.12
0.21
0.6R
0.83
0.19
1.03
1.12
1.07
0.69
0.74
0.47
1.96
0.37
0.20
0.84
1.26
0.57
0.74
0.47
0.12
1.96
62.79
0.83
0.14
0.16
0.82
0.53
0.12
0.78
0.54
0.74
0.78
o.eo
0.23
0.29
0.61
0.15
0.89
0.12
0.34
0.49 *
0.30
0.12
0.89
59.89
0.52
0.09
0.54
1.15
0.65
0.55
0.67
0.97
1.30
0.10
0.16
0.27
0.27
0.27
0.90
0.10
1.78
0.77
0.62
0.47
0.09
l."78
76.28
0.38
0.10
0.42
1.37
0.35
0.86
0.47
0.53
0.13
0.08
9.14
0.51
1.83
0.00
0.91
0.13
0.38
0.48
0.50
0.48
0
1.83
94.73
0.21
0.16
0.41
.
0.97
0.10
0.30
0.95
0.47
0.00
0.26
0.64
0.32
0.34
0.57
0.31
0.33
0.70
0.41
0.27
0
0.97
66.18
1.81 0.90 0.76 0.61
0.26 0.19 0.10 0.12
0.37 0.96 0.43 0.33
1.50 2.52 1.01 1.20
1.36 1.00 0.76 0.46
0.31 1.41 0.36 0.48
1.81 1.14 0.85 0.62
1.66 1.50 1.04 0.53
1.81 1.43 1.19 0.42
1.47 0.18 0.40 0.44
1.54 0.30 0.49 0.52
0.70 0.78 0.40 0.32
2.25 2,. 10 1.04 1.13
0.98 0.27 0.30 0.21
0.35 1.89 0.65 0.59
1.73 0.23 0.47 0.51
1.38 2.16 1.51 0.24
0.91 1.25 0.65 0.40
1.23 1.12 0.69 0.51
0.62 0.73 0.36 0.28
0.26 0.18 0.10 0.12
2.25 2.52 1.51 1.20
50.13 65.08 52.40 54.53
1.37
0.22
0.76
2.21
1.22
0.84
1.47
1.58
1.61
0.84
1.01
0.73
2.17
0.51
1.25
0.98
1.75
1.05
1.20
0.54
0.22
2.21
44.78
1.58
0.33
1.17
.
2.19
0.94
1.77
2.53
2.08
0.84
1.27
1.37
2.49
0.85
1.82
1.29
2.08
1.75
1.55
0.61
0.38
2.53
39.54
0.14
0.03
0.23
.
0.75
O.07
0.23
0.76
0.18
0.00
0.20
0.64
0.15
0.18
0.37
0.12
0.21
0.37
0.27
0.23
0
0.76
86.09
C.07
0.13
0.18
1.21
0.22
C.03
0.07
0.19
0.29
0.00
0.06
0.00
0.17
0.16
0.20
0.19
0.12
0.33
0.20
0.27
0
1.21
133.3

-------
                                     Table 3-3
CO
       DATA SUMMARY I DOSE  RATES.  IN  HG/HR
       LEFT, RIGHT  t HANDS  ARE  TIME-HEIGHTED AVERAGES
       OAY-3
           ID AHLEFT AMR IGMT  PHLEFT  PHRIGHT ARMS  AH   PN  LEFT RIGHT HANDS TOTAL ARMLEFT ARKRICHT


















Mean
S.D.
Minimum
Maximum
C.V.
6
7
8
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26





1.09
0.49
1.09
0.16
1.41
1.08
0.71
0.45
0.80
0.29
0.28
0.81
0.56
2.03
1.22
0.46
0.24
0.47
0.76
0.49
0.16
2.03
64.32
1.25
0.69
1.10
0.14
1.15
0.63
0.81
0.20
0.59
0.56
0.59
0.30
0.59
0.21
1.68
1.86
0.16
0.15
0.71
0.54
0.14
1.88
76.14
0.42
0.46
0.39
0.24
0.32
0.29
0.27
0.39
0.33
0.20
0.20
0.11
0.26
0.20
0.70
0.19
0.30
0.36
8.31
0.13
0.11
0.70
42.65
0.59
0.63
0.33
3.25
0.14
1.5?
0.27
0.26
0.74
0.1R
0.27
0.14
0.28
0.80
0.20
0.22
0.10
0.35
0.40
0.35
0.10
1.52
86.24
0.44
0.60
0.58
0.23
0.33
0.14
0.26
0.26
0.83
0.07
0.05
0.71
0.20
1.01'
0.78
0.24
0.10
Q.33
0.43
0.30
0.05
1.01
71.46
2.34 1.01 0.82 0.98
1.18 1.09 0.47 0.65
2.19 0.72 0.66 0.63
0.30 0.49 0.20 0.19
2.56 0.46 0.74 0.52
1.71 1.81 0.65 1.12
1.52 0.54 0.52 0.58
0.65 0.65 0.43 0.22
1.39 1.07 0.50 0.69
0.85 0.38 0.22 0.27
0.87 0.47 0.23 0.39
1.11 0.25 0.50 0.23
•1.15 0.54 0.33 0.35
2.24 1.00 1.04 0.53
3.10 0.90 0.89 0.82
2.32 0.41 0.26 0.65
0.40 0.40 0.27 0.13
0.62 0.71 0.41 0.26
1.47 0.72 0.51 0.51
0.82 0.38 0.25 0.28
8.30 0.25 0.20 0.13
3.10 1.81 1.04 1.12
55.80 52.76 48.80 55.06
1.79
1.12
1.30
0.39
1.26
1.77
1.11
0.65
1.18
0.49
0.62
0.73
0.68
1.57
1.72
0.91
0.40
0.67
1.02
0.47
8.39
1.79
46.41
2.23
1.72
1.88
0.62
2.09
1.91
1.37
0.91
2.01
0.56
0.67
1.44
0.88
2.58
2.50
1.15
0.50
1.00
1.45
0.69*
0.58
2.58
47.69
0.20
0.51
0.31
0.13
0.57
0.00
0.21
0.21
0.34
0.00
0.05
0.16
0.05
1.01
0.54
0.22
0.10
0.12
0.26
0.26
0
1.01
97.41
0.24
G.09
0.27
0.10
0.26
0.14
0.05
C.05
0.49
0.07
0.00
0.55
0.15
0.00
0.24
0.02
0.00
0.21
0.16
8.16
8
0.55
98.38
                                                                                             en

-------
 DATA NUMMARY: DUSE RATES* IN-MG/HR
 LEFT. RIGHT I HANDS ARE TIME-WlIGHTED AVERAGES
 VARIADLC
DAYHGUKS
AMHOURS
PMM'JUKS
DAYPRCJU
AHPkOU
PHPROO
ARHLEFT
ARMRluHT
AKHS
AMLEFT
AMKIGIIT
AM
PMLEFT
PMR1GHT
PM
LEFT
RIGHT
HANDS
TOTAL
>4
54
54
51
54
53
53
54
53
54
54
54
54
54
54
54
54
54
53
            HEAII
5.664
1.364
1.776
O.fl31
0.907
0.032
0.279
0.240
0.501
1.073
0.031
1.904
0.541
0.545
1.006
0.761
0.641
1.402
1.0 68
STANDARD
DEVIATION

    1.049
    0.476
    0.596
    0.201
    0.343
    0.365
    0.234
    0.241
    0.350
    0.902
    0.65D
   .1.377
    0.398
    0.453*
    0.712
    0.4B3
    0.366
    0.784
    1 .-300
                            MINIMUM
                             VALUE
MAXIMUM
 VALUE
                                                                                   C.V.
2.950
0.550
0,730
0.420
0.370
0.220
0.000
0.000
0.000
0.120
0.120
0.260
0.050
0.000
0.180
0.101
0.115
0.216
0.376
7.420
2.710
3.180
1.290
2.500
1.940
1.010
1.210
1.740
4.120
3.200
, 7.000
1.700
2.100
3.170
2.595
1.602
4.065
4.835
10. £30
34.C64
33.53U
24.130
37.1:76
43. 1:04
63.165
100. 2S4
69.b38
64. CIO
7V . 1 b9
~ti . 261
73.961
b3» 210
65.613
63.413
57.CJ3
55.S21
52.SS9
                                                                                             (Jt

-------
                        Table 5
                                                                    154


      Dermal Exposure by Age and Weight of Strawberry Harvesters.
           Dermal Exposure    Type

               mg/hr
Youths «14)   0.54         RIGHT               4.94          0.026
                            (3 days)
Adults (>15)   0.74
Small  «50 kg) 0.80         PN                 -5.87          0.015
                            (3 days)
Big    (>50 kg) 1.27


Small          0.88         PN
                            (Day-1)
Big            1.76                                   p-0.0076
                                       30

-------
                                                                  155
                                  Table 6

          Analysis  o-f  Variance  o-f Dermal Exposure to Carbaryl»

                         by  Strawberry Harvesters


                                              BfCSsl
  IB

6
7
8
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26
mg/hr
1.76
1.35
1.14
1.77
1.13
1.23
1.39
2.10
1.53
1.51
1.12
0.66
1.48
1.80
2.39
1.70
1.31
1.55

0.443
2.752
0.739
1.405
0.591
0.300
0.350
2.817
0.084-
2.244
0.532
0.104
0.485
1.746
6.01-
3.085
0.658
1.52
mg/hr
0.26
-0.15
-O.36
0.27
-0.36
-O.26
-O.ll
0.6O .
0.04
0.02
-O.38
-0.84
-o.ot
0.31
0.90
0.21
-O.19
0.05

0.286
0.997
0.455
0.941
1.356
1.161
0.206
1. 138
0.4O6
0.652
O. 186
0.532
0.718
0.536
3.Q55-
1.138
0.547
0.365
Group Mean     1.50             1.359       0.00            0.836

aLe*t * Right Hands, all day  (time averaged)
•Average o-f six monitoring periods (AM,PM -for 3 days)
-signi-ficantly di-f-ferent -from corresponding group variance  at  p<0.01,
i-f tested individually.

                                            31

-------
                                                         .    156
                        Table 7


Dislodgeable Foliar Residues o-f Carbaryl on Strawberry Leaves
     §«Q!elt 1C
                                 j*q / cm*   PPM (dust)
8202.3.1 P
8202.3.2 P
8202.3.3 P
8202.7.1 P
8202.14.1 P
8202.14.2 P
8202.15.1 P
8202.13.2 P
8202.16.1 P
8202.16.2 P
8202.17.1 P
8202.17.2 P
3
3
3
7
14
14
15
15
16
16
17
17
3.36
2.98
1.35
1.32
0.56
0.51
0..77
0.45
0.41
0.69
0.32
0.15
57.10
56.53
16.45
22.55
8.30
12.43
16.06
6.53
9.42
14.57
2.92
1.67
               S  2 Ibs c«rb*ryl/A (Sevin*4F Flowable)

 on June 7, 1982
                                     32

-------
                            Table  8
      Dermal  Exposure Trans-fer Coe-f-ficients -for Fruit Harvesters
                                                                  157
  Carbaryl(Day-1)



  Carbaryl



  Carbaryl(Day-3)



  Captan



  Captan



  Captan



  Cap tan



  Captan



  Captan



  Benomyl



  OP Compound*



  OP Compounds
Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Strawberries



Citrus



Peaches
4.34    This study



2.82    This study



6.17    This study



8.57  Zweig et al.,1983



2.90  Popendor-f ,et al.,1982



8.00  Popendor-f et al.,1982



2.62  Popendor-f et al.,1982



5.97  Pop*ndor-f et al.,1982



4.73  Popendorf et al.,1982



7.19  Zweig et al.,1983



5.1*   Popendorf and



1.9—      Le-f-fingwell,1982
'geometric  means  -from 14 observations



""geometric means -from 9 observations
                                      33

-------
           Hour* Monitored for Individuals on Bach of Three Days
QUA SUHHAKYl HOOKS HUNtlUkkb, tt DAY
UY»1
OAY*2
OAV-3
    10 AHMOUkS PHMULKS UAVHUUKS   AWUMJkS PHllOUKS I) AY HOURS A MM OURS PHHUUKS DAVtiOUKS
1 6
2 I
3 B
4 9
5 10
6 11
7 12
b 13
9 14
10 15
11 11
li IB
13 20
14 21
It 22
16 23
11 25
IB 26
•ean
9.D.
ana:
S.D.)

1.36
1.63
1.46
1.40
1.15
1.01
1.12
1.15
2.01
1.03
1.00
1.50
O.fcO
1.30
1.01
O.fcO
1.46
1.75
1.28
0.33


'
1.36
3.16
1.9b
2.50
1.56
l.Vil
1.30
1.15
2.25
l.UO
1.53
1.26
l./J
2.1*
2.55
2.66
1.76
1.73
1.91
0.55


I
5.36
?.16
5.90
6.41
5.41
5.65
5.07
5.07
•3.9!*
6.15
5.11
4.77
5.15
5.51
5.0tt
6.00
4.6k
5.5B
5.60
0.62
AN
PM
MY
1.96
1.43
1.10
0.96
2.41
l.VJ
1.21
1.30
I.tf3
1.31
1.61
l.VU
1.2B
1.4B
1.23 ,*
1.60
1.48
if. 41
1.59
0.42
1.36 +
1.78 T
5.66 +
1.05
2.36
2.16
2.20
1.56
' l.BO
1.23
1.33
1.96 .
1.25
1.21
0.96
1.53
2.B1
1.71
1.60
1.33
1.66
1.70
0.47
0.48
0.60
1.05
3.90
7.42
6.45
7.05
7.30
6.60
3.32
3.b5
-6*47
6.43
4.97 x
2.95
6.U5
6.95
6.50
3.75
6.11
5.b3
5.71
1.49



1.05
1.16
1.05
2.71
1.20
1.03
1.00
1.63
0.9B
0.65
0.67
1.05
0.96
2.65
0.66
0.55
1.28
1.3B
1.23
0.58
.
|

0.73
2.46
1.63
2.56
2. OB
1.26
0.73
0.73
1.75
2.03
1.53
O.tt3
3.11
3.10
1.46
1.55
1.66
1.71
1.72
0.74


t
4.1)2
7.2b
5.4B
6.3b
5.B7
6.16
~ m "^
4.32
4.->0
5.50
5*. 62
5.42
4.;»B
7.01
7.01
5.43
6.40
5.37
5.63
5.69
0.90


•«
                                                                                 Ln
                                                                                 oo

-------
                                 APPENDIX: 2

                     ARM PATCH 8ZPOSURZS (IB MG/PATCB)
                                                       159
            DAT 1
                        DAY 2
                        DA? 3
ID  ARMLEFT ARMRIGHT  ARMS   ARMLEFT ARMRIGHT  ARMS   ARMLEFT ARMRIGBT  ARMS
6
7
a
9
10
11
12
13
14
15
17
IS
20
21
22
23
25
26
0.034
0.065
0.078
0.290
0.046
0.011
0.031
0.053
0.080
0.053
0.105
0.023
0.118
0.141
0.239
0.086
0.063
0.069
0.052
0.061
0.100
0.284
0.029
0.064
0.038
0.145
0.082
0.124
0.056
0.026
0.244
0.096
0.079
0.121
0.139
0.067
0.086
0.126
0.178
0.574
0.075
0.075
0.069
0.208
0.162
0.177
0.161
0.048
0.362
0.237
0.317
0.207
0.202
0.136
0.025
0.012
0.068
•
0.330
0.022
0.038
0.152
0.054
0.0
0.057
0.101
0.049
0.064
0.134
0.024
0.073
0.095
0.013
0.052
0.053
0.439
0.097
0.009
0.012
0.038
0.087
0.0
0.017
0.0
0.056
0.057
0.072
0.038
0.042
0.085
0.038
0.063
0.121
•
0.426
0.031
0.050
0.191
0.140
0.0
0.074
0.101
0.105
0.121
0.206
0.062
0.115
0.180
0.044
0.199
0.078
0.043
0.201
0.0
0.046
0.047
0.086
0.0
0.016
0.037
0.017
0.362
0.163
0.075
0.031
0.030
0.053
0.035
0.068
0.033
0.092
0.041
0.011
0.011
0.124
0.018
0.0
0.129
0.050
0.0
0.073
0.007
0.0
0.052
0.097*
0.234
0.145
0.075
0.293
0.041
0.056
0.058
0.211
0.018
0.016
0.166
0.067
0.362
0.236
0.082
0.031
0.082
mean 0.088
S.D. 0.073
0.1001  0.189    0.076
0.070   0.128    0.077
0.0651  0.119    0.082
0.098   0.098    0.093
                 0.0441  0.126
                 0.040   0.102
               Grand Mean
                     S.D.
                             ARMLEFT ARMRIGHT  ARMS
                 0.082
                 0.080
0.072
0.076
0.145
0.113
     1 Statistically non-homogeneous (Xruskal-Wallis X2*10.07, df»2, p».0065)

     NOTE:  Due to rounding,  ARMS does not always equal the sum of ARMLEFT
tnd  ARMRIGBT.   In the table/ ".' refers to a missing value.

-------
                       Appendix Table 3-1
DAT* SUMMAKYI HllUS ARL  IN  TOTAL ACCUMULATED MC
LtFI, K1GII1 I MAUDS ARfc  SIHPLt  AVLRAGtSI  DV DAY

OAY'l

ObS IU AMLEM AMklCHl  t'HLCFT  PWllGHl   AXHS  AN   PH  LtFI KIGHT HANDS 101AL
ARML2FI nkMklGHT







1


Osl
^•^^
ON






1 6
2 7
3 J
4 9
5 U
&
7
a
9
10
11
12
1
2
j
4
5
7
• «
U
1'J 2J
14 21
i* *.:
1!. i3
1? 25
13 20
2,0.1
6.2.1
l.^u
1.V3
0.*
l.Ub
0.77
1.23
1.31
2.17
1.09
O.O6
o.uo
2.15
1.^3
0.38
l.^tt
I.JO
1.35
1.53
0.32
3.00
0.01
1.06
0.66
2.*2
.'..43
1.01
0.07
0.34
O.A5
2.66
l..40
1.64
5.11
2.81
1.73
2.19
3.34
1.70
3.53
0.92
2.07
0.49
0.75
1.15
2.9b
1.65
2.44
0.92
0.30
0.72
2.36
2.6U
1.3B
1.95
2.63
1.35
1.42
1.05
2.66
0.51
0.04
0.01
1.69
2.05
1.49
1.19
0.50
0.86
2.75
2.25
1.43
0.01
2.43
3.05
4.95
1.97
5.55
1.00
1.59
1.96
4.67
3.70
3.93
2.11
0.80
1.50
5.10
4.94
2.82
2.77
5.06
4.92
7.31
5. 86
16.70
2.24
3.17
3.33
8.58
7.21
7.81
4.92
1.71
9.15
9.73
10.64
6.72
6.32
8.12
0.75
1.22
1.71
5.64
0.76
0.23
0.61
1.1?.
1.7.1
1.17
1.34
0.43
2.47
2.7:.
4.29
1.6.*!
1.11
1.5ii
1.13
1.15
2.18
5.51
0.49
1.36
0.76
2.79
1.79
2.71
0.97
0.48
5. 1C
1.87
1.41
2. 20
2.45
1.51
                                                                                             ON
                                                                                             O

-------
DAY*?
                            Appendix Table 3-2
DBS \l AhLtn AMR I Gill PHlLH  PMRIGHI  ARMS  AM   PM  LEFT  RIGHT HANDS 101AL  ARMLFF1
19
20
21
22
23
24
25
26
27
26
29
30
31
32
33
34
35
36
It
7
o
•1
10
i:
it
i j
14
15
17
lw
2 J
21
2J
23
2I»
«0
1.S4
0.17
0.23
H.67
2.33
0.37
1.25
1.4.'.
1.9;.
0.90
1.19
0.93
2.51
0.55
0.25
1.34
1.3u
1.37
1.64
0.20
O.lll
0.80
1.28
0.13
0.94
O.7O
1.35
1.02
1.29
O.4O
0.37
0.90
0.16
1.42
U.lb
0.62
0.96
0.21
i.lt
2.53
1.03
C.99
O.U2
1.29
2.57
0.13
0.19
O.J6
O.'il
G.76
1.68
0.16
2.37
l.J!9
0.70
0.24
0.92
3.01
0.55
1.55
0.5rt
0.70
0.26
0.10
0.17
0.50
:.oo
0.00
1.56
0.21
0.51
O.lil
0.62
1.19
2.64
.
7.08
t.66
1.00
3.66
3.04
0.00
1.29
1.89
i'.19
2.36
3.71
1.16
2.02
4. 09
3.58 1.67 1.45
0.37 0.45 0.19
0.41 2.09 0.70
1.47 5.54 1.60
3.28 1.58 1.51
0.60 2.54 0.68
2.19 1.40 1.04
2.16 2.00 1.37
3.31 2.83 2.27
1.93 0.23 0.51
2.48 0.36 0.69
1.39 0.76 0.60
2.88 3.21 1.46
1.45 0.76 0.65
0.43 3.23 0.46
2.77 0.37 0.75
2.C4 2*87 2.12
2.19 2.10 1.33
1.17
0.22
0.55
1.91
0.*»2
0.89
0.76
0.70
0.81
0.56
0.73
0.48
1.59
0.45
0.87
0.82
0.34
0.81
2.62
0.41
1.25
3.51
2.43
1.57
1.60
2.08
3.07
1.08
1.42
1.08
3.05
l.iO
1.83
1.57
2.46
2.15
3.44
1.60
3.89
•
9.51
2.23
2.79
5.73
6.11
1.08
2.71
2.96
5.24
3.47
5.54
2.73
4.47
6.23
0.55
0.2.1
1.43
,
5.4i1
0.4u
0.76
2.93
1.16
0.00
0.99
1.89
1.0.1
1.25
2.41
0.45
1.2ii
2.16
0.27
0.96
1.16
8.53
1.61
0.20
0.23
0.73
1.80
O.OC
0.30
0.00
1.16
1.11
1.3C
0.71
0.73
1.9Z

-------
                          Appendix   Table 3-3
DAIA UUMHAKYI DUSKS ARt IN TOTAL ACCUMULATED MC
LtH, M Mil £ JlAhOi ARL S1MPU AVLKAGL&S 3Y DAY

DAY-3

DBS 13 AHLcFl AURICHI PKLLFl PHK1GMT ARHS  AM   PH  LEFT HIGMT HANDS 10TAL
                                                                              ARMLCFT  AKHKIGHT
97
38
39
40
41
42
43
44
45
46
47
46
49
50
51
52
53
54
6
7
C
9
10
11
1J
13
14
1:.
17
13
2J
21
2J
23
23
26
1.14
0.57
1.14
0.43
1.90
1.11
0.71
0.73
0.72
0.19
0.24
0.83
0.54
*>.i.l
1.01*
0.2:,
0.31
0.63
1.31
0.30
l.lb
0.3b
1.47
0.65
0.81
0.33
•J.5B
0.36
0.51
0.32
0.57
0.56
1.62
1.02
0.20
0.21
0.31
1.13
0.64
O.il
0.67
O.J7
0.2C
0.2B
0.56
0.41
O.J1
0.09
0*81
Q.i2
1.02
0.29
0.50
0.62
0.43
1.55
0.54
0.64
0.29
1.92
0.20
0.19
1.30
0.37
0.41
0.12
0.07
1.48
0.29
0.34
0.17
0.60
2.12
4.47
3.18
1.47
4.217
0.87
1.12
1.12
4.57
0.39
0.27
3.11
1.40
7.08
4.24
1.54
0.54
1.36
2.46 0.74 0.73 0.87
1.37 2.68 0.65 1.16
2. JO 1.17 0.89 0.85
O.tl 1.25 0.52 0.51
3.28 0.96 1.24 0.80
1.76 2.26 0.74 1.20
1.52 0.39 0.45 0.50
1.06 0.47 0.51 0.26
1.36 1.87 0.68 0.94
0.55 0.77 0.30 0.36
0.76 0.72, 0.27 0.46
1.17 0.21 0.41 0.22
1.10 1.66 0.67 0.72
5.94 3.10 3.0C 1.52
2.67 1.31 1.04 0.95
1.23 0.64 0.27 0.66
0.51 0.66 0.40 0.19
0.86 1.21 0.63 0.40
1.60
2.03
1.74
1.03
2.12
2.02
0.96
0.77
1.62
0.66
0.74
0.69
1.39
4.52
1.99
0.96
0.59
1.03
3.72
6.39
4.91
2.50
6.99
2.09
2.08
1.89
6.18
1.06
1.01
3.80
2.79
11.60
6.23
2.49
1.13
2.89
0.9(»
3.71
1.70
0.93
3.35
tf 9 ^ ^
0.03
*r w " *•
O.91
** 9 f A
0.90
1.37
O.OO
0.27
^* 9 •» •
O. 70
O.35
7*00
2.93
1.41
M w » A
0.54
0.60
1.16
4 V 4 *f
0*66
• *f^j
1.48
0.64
i .HI
M • J ^
0.1)7
^f 9 W V
0.22
^f 9 9* &
0.22
2.7C
0.39
^f • «^ m
O.OC
• ^/ V
2.41
» • * •
1.05
O.OC
I. HO
0.11
. A J
0.00
1.16

-------
                  AppendixTable 4: Overall Data And Averages (TOTAL DOSE - MG)
         DATA SUMMARY* COSES ARE IN TOTAL ACCUMULATED MC
         LtFT, KIGII1 I HANDS ARE SIMPLE AVERAGES
         VAR1ADLE
                  N
            HEAII
            STANDARD
            DEVIATION
            MINIMUM
             VALUE
                                                                              MAX1MUM
                                                                               VALUE
                                                                                    C.V.
vQ
ARMLEFT
ARMRICHT
ARMS
AMLEFT
AMR1 CUT
AM
FMLEFT
PMRICIIT
PM
LEFT
RIGHT
HANDS
1UTAL
53
54
53
54
54
54
54
54
54
54
54
54
53
1.579
1.362
2.026
1.449
1.018
2.467
0.958
0.961
1.919
1.203
0*990
2.193
4.995
1.472
1.489
2.128
1.303
0.722
1.769
0.766
O.U25
1.390
0.836
0.614
1.355
3.131
0.000
0.000
0.000
0.172
0.176
0.372
0.063
0.000
0.207
0.193
0.105
0.412
1.009
7.080
8.530
11.153
6.227
3.232
7.547
3.000
3.014
6.800
3.527
2.748
5.549
16.702
93.229
107.735
75.27U
U9.9C7
vo.evo
71. Ill
79.S09
85.777
72 . 394
69.460
62.C02
61.767
62.691
                                                                                              ON

-------
                             Appendi*rable5 -
OA1A JU:mAKYl (KlStS  AHL  IfJ 101AL UC/KGt BY DAY
UH, KIGill L !I/.HDS  ARL  SlMPU AVbKAGtS
DAY'l
    ID AhLcfl  AMMGH1  PHUFf FMMGHl   ARMS     AM      PM IbFT  KIGHl  HANDS  10TAL    AKMLfFl  AKHK1GHJ
1 i
2 7
3 J
•^4 9
•^5 1 J
^ 11
7 1C
^ tt 1*
9 14
10 IS
11 17
12 13
13 2J
14 ii
15 i*.
15 23
17 25
IB 2u
29.16
147. TO
22.75
.14.07
ID. 41
i.92
25.32
94..M
31. .^9
.-H.3B
li.?4
1J.S2
11.43
41.50
7i.91
17 .o4
51.18
62.19
19.-J?
31.21
2H.01
tl.73
4. HO
9.89
16.33
19.17
26.23
J7.V4
33.04
13.23
15.30
'.»2 .00
!»4 .77
40.40
22.49
44.30
IS. 76
19.55
5.92
67.U2
1^.46
17.07
13.00
14.41
20.5k
J5.03
23.93
i.26
14 .'J4
44 .94
3006
11.59
34 .09
20.40
19.37
36.09
4.9H
52.91
1U.70
17.36
11.24
47.92
3h.21
14.32
19.21
6.62
1 ^ t^ ^*
• W ^ Cv ^
*5.55
17.06
13.33
32.10
26.99
55.86
61.23
196.71
23.07
25.dl
23.20
77.46
55.20
55.04
61.91
Itt.lu
133.52
b4 .92
114.30
Ib.lo
73.36
4d.25
48.53
1711.41
50. V6
75.60
15.21
16.61
42.14
113.17
57.52
62.33
49.711
24.05
26. bl
93.50
141. toll
7U.14
73.67
106.49
39.14
55.63
10.90
119.93
31*16
35.02
24.24
72.33
5(1.73
49.35
. 43.14
• fc.OB
28.99
93.60
56.21
34.65
46.22
52.50
24.46 19.37
83.37 33.6t>
14.44 16.49
50.55 47.32
11.44 11.75
12.29 13.62
19.41 13.78
,59.21 33.54
25.90 32.22
34.71 21.13
20.33 26.12
6.04 10.02
12.73 15.16
43.22 50.43
£3.79 45.16
27.71 2U.73
43.04 17.91
41.29 3U.20
43.03
117.02
30.93
97.07
23.10
25.92
33.19
92.75
58.12
55.04
46.46
16.06
27.90
93.65
98.95
56.44
60.95
79.49
70.83
172.88
92.16
294.57
52.05
51.72
56.39
170.21
113.32
110.87
108.36
34.23
161.42
170.58
213.25
134.60
139.31
127.75
10. ao
23.76
26.90
99.49
17.57
3.69
13.. 11
22.13
27.13
16.M)
43.52
0.60
43.uO
53.55
hi.. 12
32.46
24.42
24.57
16.20
27. UO
34.32
97.22
11.30
22.12
12. U';
55.33
21-.07
3JJ.44
21.39
9.5t
W9.92
34.37
2b.28
45.69
53.93
23.69
                                                                                                  O\

-------
                             Appendix Table S-2
DAY -2



OB5 13 AhLEPI MtRIGHf PHUFT  PMK1GHT   AKMS    AH     PK    LIFT   ftlGHf  HANDS  TOTAL    AKNir.PT AKMK1GM1
19
20
21
22
23
24
25
26
27
28
29
30
,31
'32
33
34
35
36
u 27.92
7 4.06
G 3.63
9 11.75
10 46.41
11 5.93
12 ?1.K!
1J 2H.B9
14 30.79
15 12.84
17 26.24
IS Jb.65
2J 44. 25
2i lo.os
2J 4.9.1
23 26.9.1
25 41.07
26 21.60
23.65
4.73
2,77
14.17
29.64
3.78
16.00
13.93
21.29
14.51
2M.37
9.13
6.55
16.57
3. 70
2U.54
3.91
12. bB
13.64
5.06
16.51
4^ *t»2
23.03
16.15
13.97
£5.60
40.47
1.76
4.26
5. JO
7.J9
13.92
33.5ti
3.21
52.15
20.34
10.12
5.63
14.40
53.16
12.03
i!5.25
9.80
13.99
4.05
1.42
3.73
10.02
49.3tt
0.00 -
31.lt
4.17
11.13
1?.6B
• 11.70
26.07
41. 5d
,
164.29
10.77
16.88
72.57
47.81
0.00
2b.4o
37.84
38. Ou
43. 3u
74.25
23.30
44.41
64.17
51.57
3.79
6.40
25.93
76.05
9.76
37.12
42.82
52.08
27.35
54.61
27.78
50.7V
26.6-1
3.63
55.47
44.99
34. 4b
23.96
10.69
32.91
97.78
36.66
41.40
23.77
39.58
44.52
3.20
d.OO
15.32
56.67
13.92
64.77
7.37
(.3.28
33.02
20.88
4.56
11.07
2B.19
35.12
11.07
17.55
27.24
35.63
7.31
15.25
11. *»0
25.77
11.98
19.26
15.07
46.61
20.97
I6.btt 37.76
5.18 9.74
8.58 19.65
33.66 61.85
21.23 56.35
14.52 25.50
12.90 30.44
13.96 41.20
12.67 48.30
7.97 15.27
16.05 31.30
9.57 21.55
27.96 53.73
8.28 20.27
17.44 36.70
16.35 31.42
7.52 54.13
12.78 33.75
49.55
37.81
61.23
,
220. £5
36.35
47.32
113.77
96.11
15.27
59.77
59.38
92.39
63.62
110.95
54.72
90.54
97.92
7.36
5..?6
23.33
,
127.03
7.54
12.94
53.06
13.31
3.00
21.09
37.114
13.12
22.95
43.rO
9.02
23.. -.6
33.92
3.93
22.00
lb.25
150.45
37.26
3.23
3.94
14.51
29.50
0.00
to. ^1
0.00
20.54
20.40
26. 05
14. 2(1
16. in
3o.2!c
                                                                                             en

-------
                            Appendix Table 5-3
DATA GUtlhAKYl tXISES AKL  IN  1UTAL UG/XGl  »Y  DAY
LtFi» kir.;n t HANDS AKL  SIMPLL  wtkAGLS                         \

DAY-3

DBS |J AMLEFT AMK1GHI PNUEFT PtWIGHl   ARMS     AH  I'M    LtFT   RIGHT  HANDS  TOTAL  ARNLfFI ARMK1G
37
38
39
40
41
42
43
44
45

47
4b
49
50
51
52
53
54


~ 16.47
7 13.4*
J 16.00
9 7.63
10 41.97
11 !*».!!»
li 12.03
13 li.55
14 12.3.1
15 2.6.1

lw ivloi
20 9.4.1
21 9h.7i
22 21.03
23 5.07
21* «'. 77
i'w 10.2.1


ib.OO
1U.92
it). 16
6.69
34.15
10.59
13.73
6.47
9.09
•>.17
11.31
6.31
9.99
in. 21
32.40

4.M


i
4.41
26.75
10.00
10.64
1H.44
S.9f>
3.3-i
H.65
9.00
f>./7
6.74
I.c3
14.26
11.33
20.44
5.90
10.97
S.6J

i
6.20
36.64
«.46
11.29
l«. 76
31.24
3.34
3.77
.H>. 36

9.10
^.33
15.36
45.5C
5.85
6.63
3.66
V.41

,
30.52
103. 2u
49.97
25. bt)
113.04
14.11
19 .04
2^. Ill
71.7o

5.97
52.32
24.73
129.91
14.8(1
30.70
11.83
29.2*


35.35
32. 36
36.16
14.34
76.03
28.73
25.76
21*02
21.42
7.b5
16.67
23.36
19.47
108.92
53.43
25.57
11. 2b
13.45


10.61
63.39
10.45
22.12
22.20
37.20
6.68
9.41
29.44
10.96
15.84
1.16
29.62
56.66
26.33
12.74
11.63
19.09


10.44
20.09
14.00
9.24
2b.66
12.05
7.69
1C. 10
10.70
4.22
6.05
9.44
11.07
55.04
20.75
5.49
8.87
9.94


12.54
27.78
13.31
8.99
20.45
20.91
8.53
5.12
14.73
5.18
1C. 20
4.32
12.67
27.86
19.13
13.6?
4.00
6.33
•
1
22.98
47.0?
27.30
18.23
49.11
32.97
16.22
15.22
25.43
9.40
16.26
13.76
24.54
82.90
39.08
19.15
12.95
16.2?


53.90
151.14
77.28
44.11
162.16
47.08
35.26
37.40
97.21
14.99
22.22
76.08
49.27
212.81
124.76
49.93
24.78
45.48

I
13.87
37.77
26.71
14.63
77.63
0.00
Ib.JU
17.92
29.40
0.00
a.97
14.04
6. IS
129.91
58.76
28.22
11*83
10.6.;

..
16.64
15.49
23.26
11.25
35.41
M.ll
3.66
4.27
42.37
5.59
0.00
43. 2fc
18.54
O.OG
26.12
2.57
O.OC
111.51
ON
ON

-------
               Appendix Table *>i Overall Data and Averages (MICRQGRAM/KG)
          DAIA SUMMARY*  C'JSES  ARE  IN  101At UG/KG
          LEFT. RIGHT 1  HANDS  ARE  SIMPLE  AVERAGES
          VARIABLE
           MEAII
            STANDARD
            DEVIATION
             MINIMUM
              VALUE
             MAXIMUM
              VALUE
          ARNLEFT
          AKMRIoHT
          AKMS
          AMLEFT
          AMR ICUT
          AM
          PMLEFT
          PMR1GIIT
          PM
          LEFT
          RIGHT
          HANDS
          TOTAL
53
54
53
54
54
54
54
54
54
54
53
30.255
25.076
52.965
27.068
18.606
45.694
17.507
17.466
34.973
22.298
18.036
40.334
92.892
29.920
26.457
41.199
26.854
13.308
35.257
13.854
14.856
25.073
16.648
11.149
25.692
60,. 676
 0.000
 0.000
 0.000
 2.678
 2.767
 6.399
 1.263
 0.000
 3.196
 4.222
 4.004
 9.403
14.991
129.910
150.450
196.709
147.201
 64.770
178.414
 67.019
 53.157
119.929
 83.374
 50.427
117.022
294 .575
Ul
                                                                                               ON
                                                                                               -si

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                                                    168
Youth in Agriculture:  Dermal Exposure to
  Vinclozolin by Strawberry Harvesters
  1982
        Research performed by

        University of California
        Richmond, CA  94804

        December 1983

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                            Abstract
                                                               169
Dermal exposure to vinclozolin of 18 harvesters of strawberries
was studied on three consecutive days in June at a commercial
farm in Corvallis, Oregon.  The study was designed to provide
correlations among dermal exposure,  age of workers, body size or
weight of workers and productivity.   Statistical analyses of the
data showed a significant correlation between exposure rate and
age and productivity.  Also age appeared to correlate positively
with productivity, e.g., older workers seemed to receive higher
dermal exposures than younger ones in the same occupational setting,

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edited: February 24, 1984
                                          Page    1    ef   1
                                          Section No.	1	
                                          Revision No.	Q	
                                          Date;  February 29. 1984
170
                      Youth in Agriculture
      Dermal Exposure to Pesticides by Strawberry Harvesters
                           1982 Studies
                         II. Vinclozolin
          Gunter Zweig, B. McClean, C. Truman, K. Bogen,
                     and John T. Leffingwell
            Pesticide Hazard Assessment Program (PHAP)
                     University of California
                     School of Public Health
Sanitary Engineering and Environmental Health Research Laboratory
                      Richmond Field Station
                    Richmond, California 94804
                                     01

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                                          Pugg    1
                                          Section No.
                                          Revision No.
                                                       Of
                                                                    171
                                                February 29.  1984
                         TABLE OF CONTENTS
3.0    Introduction
4.0    Experimental Design
       4.1 Field Study
       4.2 Sample Extraction
       4.3 Analysis of Vinclozolin
       4.4 Statistical Analysis
5.0    Results and Discussion
       5.1 Dermal Exposure
       5.2 Comparison of Exposure Rates
       5.3 Correlation Between Exposure/ Age, and Productivity
6.0    Dislodgeable Foliar Residues
       6.1 Decline of Vinclozolin Residues
       6.2 Transfer Coefficients
       6.3 Carbaryl:Vinclozolin Ratios
Table 1:
Table 2:
Table 3:
Table 4-1:
Table 4-2:
Table 4-3:
Table 5:
Table 6-1:

Table 6-2:
Table
Table
Table
Table
      7-1 i
      7-2:
      8:
      9:
Table 10:
Recovery Studies of Vinclozolin
Physical Characteristics of Strawberry Harvesters
Productivity of Strawberry Harvesters
Vinclozolin Dose Rates — Day-1
Vinclozolin Dose Rates — Day-2
Vinclozolin Dose Rates — Day-3
Summary  of Dose Rates  (3 Days)
Statistical Analysis of Exposure of Workers Grouped by
Weight
Statistical Analysis of Exposure of Workers Grouped by
Body Surface
Correlation Between Exposure and Age
Correlation Between Exposure and Productivity
Decline of Dislodgeable Foliar Residues
Transfer Coefficients for Vinclozolin for Strawberry
Harvesters
Carbaryl:Vinclozolin Ratios
Literature References                                 j
 *>                                                    /
Figure 1:   Capillary GC Trace of Standard Vinclozolin
Figure 2:   Exposure Rate versus Age of Strawberry  Harvesters
Figure 3:   Exposure versus Productivity of  Strawberry  Harvesters
Figure 4:   Productivity of Strawberry Harvesters versus  Age
Figure 5:   Vinclozolin Dislodgeable Decay Curve
                                       02

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                                          Page    1    off	2	
                                          Section No.	3	
                                          Revision No.	Q	
                                          Date; February 29. 1984
                         3.0 INTRODUCTION
        In order to complement the 1981-Btudies  on the assessment
of pesticide exposure among strawberry pickers,  an additional,
detailed field study was conducted during the month  of June  1982.
The site of the study was the same commercial strawberry farm used
for one of our studies in 1981, located near Corvallis,  Oregon.
        The design of the 1982-study was  aimed at measuring dermal
exposure to several pesticides which had been applied to this.
strawberry field. Since in earlier studies  it had been demonstrated
that the major dermal exposure to pesticides by  strawberry pickers
occurred on hands, forearms, and to a lesser degree  on lower legs,
only these three anatomical regions were monitored in this study.
Observations were made on three consecutive days in  the mornings
and afternoons on 18 volunteers who were experienced strawberry
harvesters.
        The major aim of this study was to  gain  further insight
into the mechanism of pesticide transfer from foliage and  fruit  to
the skin of strawberry harvesters. Correlations  between dermal
pesticide exposure and work or physiognomic characteristics and  age
would be attempted. Finally, correlation between dermal exposure,
age of workers, body size or weight would  be tested.
        This is the second report of this  series and deals
exclusively with dermal exposure to the fungicide vinclozolin
(RONILAN).  The first report of this series, submitted to EPA in
                                     03

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                                          Page___2__of _ 2 _
                                          Section  No. _ 3 _
                                          Revision  No.
                                                 ebruar   29.  1984
December 1983, dealt with the exposure to the insecticide

carbaryl.

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                                         Pagg    1    of	6	  < -j *
                                         Section No.	4       ' ' n
                                         Revision No.	Q	
                                         Date* February 29. 1984
                     4.0 EXPERIMENTAL DESIGN
        4.1 Field Study
     A privately owned strawberry farm near Corvallis, OR was
chosen as the site of the field experiment. The  dates of the study
were June 22, 23, and 24, 1982. The field had  been  sprayed prior to
the study dates with three pesticides as follows:  carbaryl, 2
Ibs/A, 7 June, 1982; vinclozolin, 1 Ib/A, three  applications each
on 5,15,  and 22 May 1982; endosulfan, 1 Ib/A,  15 May,  1982.
        Vinclozolin, or  RONILAN,  l3-(3,5-dichlorophenyl)-5-ethenyl-
5-methyl-2,4-oxazolidinedione], produced by BASF, was used on
strawberries to control  Botritia cinera and must be applied several
times during the flowering period to achieve best results. Based on
the spray history of the field, Day 1 of the study represented Day
31 post-application date, and so on.  Initially,  23  harvesters
volunteered to participate in the study, but only  18 workers
completed the three day  course.
        At the beginning of each work day (between 0600 and 0800
hr),  the  workers were outfitted with dermal monitors,  consisting  of
light cotton gloves for  the hands and cotton patches on the
forearms and lower legs. A description of these  monitors has  been
reported previously (1982 Report to  EPA,  PHAP-California).  Patches
were worn throughout the work day ( about 6 to  8 hrs)  and gloves
for a shorter period of  time during  the morning. A new set of
                                         05

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                                                                  175
                                          Page____2____of_
                                          Section No.	4	
                                          Revision No.	Q	
                                          Date -  February  29. 1984

 gloves was issued to the workers after the lunch break  to be kept
  T                                                               .
 on until  the  end  of  the work day (about 3 hrs).  The tine  periods
 during which  gloves  and patches were worn are found in  the  Appendix
 of the Carbaryl Report  (Draft Report to EPA, December 1983).
        The procedure for hand monitoring was modified  on the
 second day of the  study after it had been discovered on the first
 day that  a large amount of dew on the strawberry foliage
 contributed a great  deal of moisture to the gloves. This  condition
 seems to  interfere with the proper behavior of the gloves as
 absorptive monitors. Therefore/ gloves were provided about  2 hrs
 after  the harvesters had entered the field in the morning by which
 time the  dew  on the  foliage had dried. On Day 3, the original
 experimental  procedure was resumed.
        At the completion of the monitoring period for  each worker/
 gloves and patches were removed from each subject, stored
 individually  in Zip-Lock type bags over dry ice, transported  to the
 laboratory/ and placed in the deep-freeze until the samples could
 be extracted  and analyzed. Glove monitors were peeled  from the
  X
 hands  of the workers inside-out in order  to minimize field
  -^
 contamination.
        For the purpose of measuring dislodgeable foliar residues
of vinclozolin,  48 leaf disks from strawberry plants were sampled
 in a random design by walking  across  the  plot diagonally and taking
leaf samples  from  different plants  at  different heights. Leaf disks
were collected by  means of a mechanical punch which was  designed so
                                     06

-------
                                          Page_J_of	6	   * 7 6
                                          Section  No.	4	
                                          Revision No.	Q	
                                          Date!  February 29. 1981
that  the disks dropped directly into a glass storage bottle. The
mechanical  punch was also equipped with a counter  to minimize
errors during sampling. The procedures for sampling, collecting and
extraction  of samples for the analysis of dislodgeable residues
have  been described in a previous report from this laboratory
(Popendorfr et al. 1982).
        4.2 Sample Extraction
            Gloves and cotton patches were extracted with  100 mL
and 30 mL of acetonitrile per sample, respectively, by shaking on  a
reciprocal  mechanical shaker for two hours. Ten mL aliquotB  were
filtered through 0.22 u Nillipore filters and directly analyzed by
gas chromatography as described below. If the concentration of
vinclozolin, particularly of gloves, was too high to be within  the
linear range of the detector ( see below), aliquots of the sample
were  diluted in appropriate volumes of  acetonitrile.
        Dislodgeable residues of pesticides on foliage and dust
were  extracted from leaf punches according to methods developed by
Gunther et  al. (1973, 1974), Iwata  (1977), and Popendorf and
Leffingwell (1977).  The leaf punches were surface extracted with
three portions, successively, of 100 mL each  of 60 ppb aqueous
  t
solution of SURTEN (dioctyl sodium sulfosuccinate) for 30 min.  The
  t.
liquid phase was carefully decanted and extracted 3 times
successively with 50 mL each of dichloromethane in a 500 mL
separatory  funnel. Emulsion that might form were  broken up with a
few drops of a saturated solution  of  sodium sulfate.

                                       07

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                                                         I    Ml
                                          Page___4_of	6	
                                          Section No.	4	
                                          Revision No.	Q	
                                          Date;  february 29. 198A

        The combined organic extracts (bottom phases)  were filtered
 through glass wool and a bed of anhydrous sodium sulfate and
 evaporated on a rotary evaporator in XA&UQ. to about two mL. The
 flask was washed down with  ten milliliters of acetonitrile and
 again evaporated down to a  couple of milliliters. This procedure
 was  repeated twice more, and the residue was finally taken up in
 either 10.0 or 25.0 mL  of acetonitrile.  Aliquots of this solution
 were analyzed by capillary  GC, as will be described below.
        To isolate and determine the weight of leaf dust,
 which remains in the separatory funnel at the interfacial layer
 and  suspended in the aqueous phase, was quantitatively transferred
 to a pre-weighed glass filter. After drying at 110° overnight, the
 filter was weighed and the weight of foliar dust calculated by
 difference. The foliar dust is presumed to be the vehicle for the
 transfer of pesticides from the crop to the worker.
        4.3 Analysis of Vinclozolin
           Analytical grade vinclozolin (F 696)  was obtained from
 the EPA Reference Standard Repository, Research Triangle Park, NC
 27711.  Acetonitrile used throughout was "Baker Resi-Analyzed*, or
equivalent.
        There are several reports in the literature on  the  analysis
of vinclozolin residues by High Performance Reversed Phase  Liquid
Chromatography  (HPLC) (Cabras et al., 1982, 1983). For  our
purposes,  however, a method was chosen  capable  of analyzing
vinclozolin and endosulfan  simultaneously; the  latter pesticide

                               _..    08

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                                          Page - 5 - of - .6 - 1 7 Q
                                          Section  No. _ 4
                                          Revision No. _ flL _
                                          Date t February 29. 1984
having been applied to the same strawberry plot for the control of
mites, aphids, and other insects. Endosulfan  isomers and the
sulfate metabolite cannot be conveniently analyzed by  HPLC, and gas
chromatography is the method of  choice.
     A capillary GC method was,  therefore, developed for the
analysis of vinclozolin and endosulfan. A Hewlett-Packard  5880A
instrument, equipped with an H-P 7672A Automatic  Sampler was  used.
The column was a 12.5 m WCOT silica capillary column with an I.D.
of 0.2 mm, coated  with cross-linked dimethyl silicone (OV-1), and
deactivated  with siloxane. The splitless injection mode was
selected, and detection was accomplished by electron  capture
        Experimental conditions for the complete resolution of a
mixture of vinclozolin, endosulfan I and II, and endosulfan sulfate
were the following (see  fig. 1):
  ;   Carrier gas (He);  flow § 15 psi; " 4 mL/min.
     Septum Plush; 3 mL/min.
     Split Vent* 55 mL/min.
     Make-up yae (5% methane, in argon); 20 mL/min  at  the  detector.
     Temperature programs  Time/rise           Temperature (°c)
                             1 Bin                 62
                             30°/nin               62  - 250
                             1 min                 250
                             30°/min               250 - 260
                             5 min                 260
                                     09

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                                                                 179
                                          Pagg    6    of	6	
                                          Section  No.	4	
                                          Revision No.	Q	
                                          Datet  February 29. 1984

     Under these conditions, vinclozolin  had  a retention time of
6.54 min.
        One microliter injections of standard and  sample solutions
were made automatically. All samples were run in triplicate.
Results were accepted when  the relative standard deviation (RSD)
was <5% for standards and <10% for field and laboratory  samples.
Standard solutions ranged from 8.7 ng/mL to 870.8  ng/mL. Over this
100-fold range, the EC response was found to be  linear. Whenever
the concentration of unknown was outside this range,  appropriate
dilutions with acetonitrile or evaporation were  made.
     The practical limit of detection was 8.7 ng/mL.  Although
concentrations  of one half this level could be  integrated with
almost equal precision, it  was not necessary  to achieve  a
sensitivity greater than the stated value for most samples.
        Recovery studies of vinclozolin for gloves,  patches, and
  £
SDRTEN solutions (simulated dislodgeable residue extract), as  may
be seen in Table 1, ranged from 70% to over 100% of added
vinclozolin.
   4.4 Statistical Analysis
     Statistical analyses were performed using SAS, a statistical
  j
computer software program developed by Statistical Analysis
Systems, Inc.
                                       10

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                                          Page     1    of	5	
                                          Section  No.	5
                                          Revision No.	Q	
                                          Date;  February 29, 1984
                    5.0 RESULTS AND DISCUSSION
     5.1 Dermal Exposure
     Physical characteristics  (sex, age, weight, and height) and
body surface, calculated by the method of Sendroy and Cecchini
(1954), are shown  in Table 2. Individual productivity,  listed in
Table 3, is expressed as crates of strawberries harvested  per hour
for the morning,  afternoon and all-day  observation periods.
     Tables 4-1, -2, and -3 show exposure rates of individual
workers for morning,  afternoon and all day, expressed in mg/hr  for
left and right hands and lower-arms.  Exposure rates  for  AM- and PM
hands and lower-arms were directly calculated from dermal
concentrations and hours monitored. Daily exposure rates for  hands
are time-weighted averages.
     Lower-leg exposure concentrations were mostly nondetectable
  £x
and were, therefore, not considered to contribute significantly to
total dermal body  exposure to  vinclozolin. Since only one
subject,No.7,exhibited  a  lower-leg exposure rate of about 10% of
total on Day-1, it was decided not to include lower-leg exposure
values for subsequent  analyses.
     Table 5 is a three-day summary of  exposure rates of  all 18
  *
volunteers for six observation  periods  (N-108). Judging by these
results, it appears that hand exposure  is the major  target of
dermal exposure of strawberry harvesters.  Mean hand exposure rate,
0.251  mg/hr,  may be compared with 0.027 mg/hr  for  lower arms.  This
observation is consistent with  results  from  previous studies on
                                ...    11

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                                          Page___2_of	
                                          Section No.	5.
                                          Revision No..
                                                      .	
                                          Date -  February 29.  1984

 strawberry  harvesters exposed to captan (Final Report to EPA,  1982)
 and  carbaryl  (Carbaryl Report to EPA, 1983).
      It also appears that vinclozolin exposure was considerably
 lover for the  same  group of workers than corresponding carbaryl
 exposure  (0.28 mg/hr vs.  1.89  mg/br,  respectively).  A probable
 explanation for this finding nay be the fact that vinclozolin had
 been  applied 15 days earlier than carbaryl, and lower dislodgeable
 vinclozolin residues were found on corresponding study dates (see
 below).
      By statistically analyzing the date for six observation
 periods, hand exposures for  the  AM-observation period were shown to
 be greater  than  those  in the afternoon, (Z=2.157;  N=54;  p<0.016).
 Similar results were found  in the carbaryl study and may be
 related to  dew formation on foliage during the  early morning hours.
 This  may cause glove monitors to become quickly saturated with
 water. In contrast  to the transfer of dislodgeable residues on tree
 crops, as discussed by Popendorf and Leffingwell  (1982), the
 results reported here may reflect the effect of water-saturated
glove monitors which may enhance the transfer of dislodgeable
residues from  foliage.
  -•   By applying Duncan's Multiple Range Test,  it can be shown
that mean dermal exposure rates for all 18 workers were  not
significantly different on  any  of the three days  of  the  study.  One
exception to this finding were  afternoon  exposure rates for  hands,
which were  significantly  lower  on the third day than on the  other

                                      12

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                                          Page    3    of   S       1 82
                                          Section No.	5	
                                          Revision No.	Q	
                                          Date;  February 29. 1984
 two  days  (0.210, 0.252, 0.125  mg/hr for  Days-1,-2, and  -3,
 respectively).
     5.2 Comparison of Dermal Exposure Rates of  Workers Grouped by
         Physical Factors
     One of the primary goals of these exposure  studies, sponsored
 jointly by EPA and DOL, was the investigation of possible
 differences in dermal exposure between two groups of workers, 10-11
 year old (Group I) and 12 years of age and above (Group II). As may
 be seen in Table 2, none of the volunteers were  below 12 years of
 age. It is possible that the cooperating grower  purposely  excluded
 volunteers from this age group. Due to the absence  of  10-11 year
 old  subjects, physical characteristics other than age  had  to  be
 chosen for purposes of comparison. Body weight and body surface
 were selected as appropriate physiognomic properties characterizing
 these two age groups.
     Dividing the workers  into two groups according to body weight
 (<50 kg and >50 kg),  it was shown by the application of chi-square
 statistics that afternoon exposure rates to hands were larger among
 the subject group whose weight was >50  kg (0.24 mg/hr  vs. 0.12
 mg/hr; see Table 5-1). Other exposure rates tested by  these
 statistics were found  not  to be different. These results are
consistent with those  found for carbaryl  exposure in the same group
of workers (Carbaryl Report, 1983)
     When the subjects were grouped  by  body surface  (<1.52 m2 an(j
>1.52 ffl2)r  it could be demonstrated that  three  types of exposure
                                         13

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                                                                 183
                                          Page__4	of	5	
                                          Section  No.	5	
                                          Revision  No.	0
                                          Date«  February 29. 1984

rates were lower  among  the  <1.52 m2-group, hands-PM, hands-all  dayr
and  total.
     There appears to be logic in dividing the  group according   to
their physiognomic properties for testing exposure differences.  For
example, six out of seven subjects with smaller body weight also
had smaller body surface. One exception to this rule seemed to  be
Subject No. 23 whose body surface was  slightly larger (1.53 m2)
than the cutoff point,  so that No. 23 was placed in the "bigger"
group.  However, the method of estimating body surface by  nomograph
(Sendroy and Cecchini, 1954)  may not  warrant making this
distinction.
     All 12-year old subjects belonged to the groups  of "smaller"
and "lighter weight" persons. (Six out  of seven subjects  in  either
group were female.)  One  may conclude, therefore, that  younger
strawberry pickers are subject to lower dermal exposure than a
group of older pickers in the same occupational setting.
     5.3 Correlation Between Exposure, Age, and Productivity
     In previous studies on dermal exposure to captan and benomyl
by strawberry harvesters (Final Report to EPA, 1982;  Zweig et  al.,
1983),  evidence was presented that exposure, productivity, and age
of workers correlated in some cases. In the studies on vinclozolin
reported here,  additional evidence for these correlations is
presented through regression analyses. Linear regressions are
shown in figs.  2,3,  and  4.  Although the experimental data were  not
ideal for statistics due to uneven distribution of ages,

                                      14

-------
                                          Section No. _ 5
                                          Revision No.
                                                       of _ 5 _      1 8 4
                                          Date;  February 29.  1984
statistical analyses did reveal a significant correlation between
exposure rates and age  (Table 7-1) and productivity (Table 7-2). A
possible interpretation of these results is that dermal exposure is
positively affected by  the  individual's productivity.  Age also
seems to correlate positively with productivity, indicating that
older workers might be  more experienced and motivated.
Consequently, the older workers seem to receive higher dermal
exposure than the younger ones in the same occupational and
environmental setting. A detailed analysis of the variability of
workers' exposure to carbaryl showed that intrapersonal variability
is larger than interpersonal variability, and, therefore, age alone
of an individual worker does not necessarily  serve as a reliable
predictor of his exposure (Carbaryl Report, 1983), and no
conclusion may be drawn from the exposure rate  of one  individual
and his age.
                                      15

-------
                                                  1     Of	1»	
                                          Section No.	6—'     \ 8 J
                                          Revision No.	0
                                                 ebruar 29.  1984
 r               6.0  DISLODGEABLE FOLIAR RESIDUES
     6.1 Decline of Vinclozolin Residues
     There is increasing evidence that the major  source of  dermal
exposure to pesticides by fruit pickers is dislodgeable foliar
residues of pesticides resulting from the application of pesticides
to the field prior to the entry of harvesters.  It was important,
therefore, to study the decline of dislodgeable foliar residues of
vinclozolin for a period of several weeks after the last
application date. The first sampling date of strawberry leaves for
vinclozolin represented Day-17 post-application and corresponded to
Day-1 for carbaryl.  The days on which the harvesters were monitored
were Days-31f -32, and -33 post-application. A semi-log plot of
vinclozolin dislodgeable residues vs. days post-application, shown
in fig. 5, indicates first-order kinetics with a half-life of
vinclozolin estimated at 4.3 days on  strawberry  foliage.
     6.2 Transfer Coefficient  for Strawberry Harvesters
     The transfer coefficient  is an expression of transfer
efficiency of dislodgeable residues from  foliage to the  skin of  the
field worker or harvester. The transfer coefficient is calculated
according to Equation  (1) :
 (1)      k<3 •  _ (dermal deep rate) _
               .  (Dislodgeable foliar  residues)
                  (k<] has the dimensions  of  c
     The transfer coefficient may be  considered to represent the
                                      16

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                                          Page    2     of
                                          Section No._
                                          Revision No..
                                          Date*  February 29. 1984
ideal area of foliage "contacted" by the  worker  if the residue were
quantitatively removed from  the  foliage and deposited on his skin.
In reality, much  less than quantitative transfer is  effected. For
example, it has been shown that  during harvesting of citrus,
approximately one-half of parathion and paraoxon residue was
removed during harvesting activity  by  pickers  (Spear et al., 1977).
Furthermore, in tree crops it is unlikely that all of the  dry
residue removed from the foliage will  be deposited onto the person,
independent of dermal absorption. Thus, the value of k
-------
                                                                  I"
                                          Page__3__of	*»	      1 8/
                                          Section No.	fi	
                                          Revision No.	Q	
                                          Date;  February 29f 1984

carbaryl and vinclozolin residues may be their respective "age";
vinclozolin was applied 14 days before carbaryl,  and therein might
lie the difference in the type of residue found.  Based  on  previous
observations, it does not appear that physio-chemical properties
of a compound had a  large effect on its transfer efficiency, and
one must speculate that there exist other factors which explain
this behavior.
     6.3 Carbaryl-Vinclozolin Ratios
     From the data presented here and those previously reported for
carbaryl (Carbaryl Report,  1983),  it is possible to calculate  the
ratio of carbaryl and vinclozolin existing as dislodgeable foliar
residues and dermal  concentrations  (dermal dose rates). The ratios
for carbaryl:vinclozolin from dislodgeable foliar residues range
from 46-98, as shown in Table 10,  while the corresponding values
from dermal dose rates are considerably lower, with the possible
exception of lower-arms' on Days-1 and -3. If one were to
hypothesize that dislodgeable foliar residues represented the major
source of dermal exposure,  one would have expected these two
pesticides to appear in similar proportions on leaves  (dislodgeable
residues)  and skin (dermal exposure).  This was indeed demonstrated
in our previous study dealing the the simultaneous exposure by
strawberry harvesters to captan and  benomyl (Zweig et al., 1983).
The fact that the carbaryl:vinclozolin ratios are significantly
smaller on the skin  than leaves suggests  two possibilities: one,
that vinclozolin dislodgeable foliar residues behave differently  than

                                   18

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                                                       of
                                          Section No. _ fi
                                          Revision No. _
                                          Date ». February
29. 1984
carbaryl residues and/or secondly, that there may be an additional
source of vinclozolin contributing to dermal exposure (fruit or
soil?),  thus resulting in lower ratios. The fact, however, that
vinclozolin transfer coefficients  (see 6.2)  were larger than
•normal" supports the first view that vinclozolin dislodgeable
foliar residues behave differently than most other pesticide
residues which have been studied by us under field  conditions.

-------
                                         Page    1
                                         Section No.
                                         Revision No
189
                                               Februar  15  1984
                              TABLE  1

                  Recovery  Studies on VInclozolIn
Substrate


300 ml Surten*
300 mL Surten*
Patch tl
Patch §2
Patch *3
Patch 14
Glove /I
Glove 12
YI
Added

239.0
218.0
218.0
218.0
218.0
239.0
218.0
218.0
nc I ozo 1 1 n
Found
(ug)
196.7
177.9
155.6
152.5
157.3
174.7
230.5
233.4
Par Cent Recovery


82.3
81 .6
71 .4
69.9
72.2
80.2
105.7
107.1
Surten* Is the trade mark for sodium  dloctyl suIfosucclnate

surfactant.  The  Surten*  solution for this experiment vas a 60-ppb

aqueous solution and vas used to simulate surface  extraction of

dTslodgeable vinclozolln residues  from  strawberry  leaf  disks.
                                      20

-------
                                     Page    1     of
                                     Section No.	
                                                                190

Phys
ID
6
7
8
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26


leal Character!
*.
F
F
F
F
F
F
F
F
M
M
F
F
M
F
F
F
M
M
Age
40
12
18
29
13
32
15
16
13
13
12
12
14
14
37
16
12
15
TABLE
Istlcs of
Height
kg
69.5
42.3
63.6
56.7
43.1
61.3
59.0
50.4
63.6
70.4
45.4
49.9
56.7
54.5
49.9
49.9
45.4
63.6
2
RAvtetnn No. 0
Dat»> February 29. 1984

Strawberry Harvesters
Height
cm
168
163
175
164
149
175
160
173
178
168
157
163
180
165
152
165
160
183
Surface Area
.2
1.77
1 .52
1.78
1 .58
1 .35
1 .72
1 .62
1 .56
1.76
1 .78
1.42
1.52
1.70
1.59
1 .46
1.53
1.43
1.84
Determined by  the  method of Sendroy and Ceddhtnt  (1954).
                            21

-------
CO
ro
                              TABLE 3


          Productivity of Strawberry Harvesters (crates/hour)
ID
6
7
8
9
10
11
12
13
14
15
17
18
20
21
22
23
25
26
Mean
AM3*r.D
1.47
0.61
0.6'.
0.7 1)
0.3!.
U.9T
0.9C
0 . 66
0.99
0.97
l.OC
o.&r.
2.50
0.6';.
0.99
1.2T
0.60
0.57
0.94
OAY*1
r'HPftOD T
1.33
0.47
1.00
i .00
0.63
1 .05
1.15
1.35
0.36
0.55
0.92
0.72
U.'ib
u.47
0.6t
0.56
0.94
0.88
AYPKCJ
1.17
O.So
O.J<5
0 , Bo
0.9;:
i.Ob
I.Ob
0.79
O.ft'i
O.^'J
0.*3
1.79
0 . f»4
1.06
O.Bb
0.*85
0 AMPR^O
1.0]
0,70
0.99
1.02
1.17
1.1&
0.33
0.77
1.09
' 0.76
0.6?
0.5?
0.45
0.67
0.31
l.2f.
0.57
0.33
0.85
DAY=2
f'MPRGl)
0.42
1.40
0.92
0.32
0.22
1.11
0.41
0.56
0.67
0.60
0.62
0.25
0.65
0.50
0.3b
1.25
0.62
0.74
0.70
DAYPROD
1.03
0.^7
0.«»7
1.00
0,75
1.05
0.9b
0.7b
1.00
0.62
O.S5
0.42
O.ftl
O.fiO
0.77
0.71
0.60
0.7«»
0.78
AMPROO
0.95
0.66
0.95
0.37
0.7S
0.97
1.00
0.61
1.02
1.54
1.1 f>
0.95
1.04
0.37
1.01
1.5?
0.70
0.7?
0.92
DAY*.
PMPROD
0.68
1.03
1.23
1.17
0.4b
0.79
1.37
0.66
1.43
0,74
0.98
0.30
0.64
0.64
1.03
1.94
0.90
0.58
0.92
3 AVERAGE (3 d)
nAYPKOD
0,93 1.04
0.82
O.«l
1.10
0,67
0 . H9
0.93
o.?u
1.00
• o.to
0.92
0.70
1.1U
0.71
1.01
1.P9
0.65
0.71
0.85
0.68
0.91
0.99
0.78
1.00
1.00
0.72
0.97
0.57
0.74
0.60
1.04
0.60
0.89
0.96
0.70
0.72
0.83
Note: "." = missing value
Page 1 of 1
Section No. 9
Revision No. 0
Date: February 29,1984

-------
lean
!.  D.
                                                TABLE 4-1
                 Vinclozolin  Dose  Rates for Strawberry Harvesters — Day-1
                                                  (mg/hr)

        1C AKMLtFT AKI.K1GHT AKMS  AMLEKT AHklGHT  AM   PMLCFT PMR1GHT  PM   LEFT  RIGHT HANDS llilAL
6
7
6
rt
10
11
12
13
14
15
17
IS
20
j>l
22

25
26














O.'JiO
0.004
0.013
C.074
0.042
0.014
0.004
0.003
0.007
O.C04
O.C06
0.000
0.007
C.015
0.020
0.010
0.009
O.OOb
0.014
0.01B













0.014
C.OCO
C.014
0.060
0.065
0.017
0 .006
O.OC&
0.005
0.002
0.007
O.OC2
0.020
0.016
0.009
0.017
0.021
0.009
0.016
0.018













0.024 0.563
G.004 0.201
0.027 0.101
0.134 0.229
0.106 0.246
0.031 0.117
0.010 0.105
0.011 0.129
0.012 0.065
0.006 0.092
0.013 0.077
O.C02 0.051
0.027 O.llt
0.031 0.106
0.029 0.000
0.026 0.175
0.030 0.082
0.017 0.147
0.030 0.145
0.035 0.121













0.31H
0.096
0.119
0.199
0.11H
0.220
0.075
0.074
O.Od?
0.137
0.128
0.044
0.208
0.162
0.292
0.112
0.048
0.133
0.143
0.078








-




O.bbO
0.297
O.i:21
0.429
0.364
0.337
0.161
0.203
0.152
0.229
0.205
O.C95
0.324
0.2' 1-.176
0.235 0.119 0.110 C.//V 0.255
0.393 0.218 O.lbb C.406 0.540
0.245 0.160 0.135 C.295 0.-»03
0.332 0.132 0.201 0.334 0.365
0.121 0.064 0.065 0.149 0.156
0.250 0.121 0.105 G.226 0.237
0.120 0.065 0.070 0.135 0.147
0.07d 0.057 0.077 0.133 0.140
0.071 0.051 0.073 C.124 0.137
0.045 0.036 0.036 0.072 0.074
0.437 0.1 02 0.239 0.401 0.428
0.229 0.122 0.122 0.244 0.275
0.127 0.051 0.123 0.174 0.203
0.216 0.135 0.099 G.234 0.260
0.126 0.076 0.050 C.12B 0.159
0.220 0.116 0.134 0.250 0.267
0.210 0.122 0.121 0.242 0.273
0.123 0.081 0.065 0.140 0.157
O 50 W »d
p) (0 fl> 0»
ft < O«O
n H- r* n>
.. 0) H-
•»! H-O
(D O 3 M
n z
d zo
fu O • O
M • Mi
<
*-• . ,
K) O O P*
U3
**

-------
                                        TABLE 4-2




              Vinclozolin Dose Rates  for  Strawberry Harvesters — Day-2


                                         (mg/hr)
ID AkHLtM  AKMRIGHT ARMS  AMUFT  AMR1GHT   AM   PMLEFT PMklGHT  PM    LEFT   KlGHT  HANDS TUTAL
6
7
6
9
10
11
12
13
14
15
17
18
20
2\
22
23

26


0.009
0.001
O.Olb
O.G44
0.025
0.003
0.033
O.Obl
0.016
O.OOti
0.002
0.013
O.OOS
0.011
0.026
O.OC5
0.006
0.009
0.018
0.020
0.010
0.009
O.C16
0 .067
0.011
O.C03
0.005
0.067
0.016
0.015
0.005
0.002
0.006
0.022
0.029
0.006
0.005
0.013
0.017
0.020
O.C19 C.309
0.010 0.027
0.034 0.127
0.111 0.236
0.035 0.149
0.006 0.081
0.038 0.474
0.14B 0.24b
0.034 0.134
0.023 0.121
0.007 0.160
0.014 0.078
0.015 0.172
0.033 0.105
0.055 0.115
0.011 0.41b
0.011 0.115
0.022 0.050
0.035 0.173
0.037 0.121
0.329
0.102
0.151
0.214
0.104
0.076
0.295
0.184
0.245
O.lOb
0.184
0.042
0.159
0.159
0.073
0.51U
0.044
0.026
0.167
0.122
0.638
0.129
0.276
0.452
0.253
0.157
0.769
0.432
0.379
0.228
0.344
0.120
0.331
0.265
0.168
0.936
0.159
0.077
0.341
0.234
0.409
0.022
0.085
0.124
0.043
0.066
0.400
0.321
0.294
0.041
0.032
0.015
0.150
0.077
0.232
0.023
0.127
0.118
0.148
0.141
0.209
0.036
0.105
0.158
o.oe?
0.120
0.242
0.147
0.147
0.060
0.060
0.032
0.169
0.003
0.133
0.025
0.097
0.052
0.105
0.066
C.bl7
0.05b
0.190
0.262
0.130
0.186
0.722
0.4ob
0.442
0.100
0.093
0.048
G.31b
0.080
0.365
0.048
0.224
0.171
0.253
0.201
0.357
0.024
0.099
0.159
0.107
0.073
0.477
0.285
0.21B
0.0b2
0.105
0.057
0.160
0.087
0.183
0.220
0.121
0.078
0.161
0.116
0.271 0.62d
0.061 C.0b5
0.120 0.220
C.175 0.334
0.097 0.204
0.097 0.171
0.2bt) 0.745
0.165 0.450
C.iSH 0.112
0.0b4 0.166
0.131 0.236
0.039 0.096
0.164 0.324
0.057 0.144
0.106 0.291
Q.ili 0.492
0.069 0.190
0.037 0.115
0.134 0.295
0.078 0.187
0.647
0.095
0.253
0.446
0.239
0.177
0.783
0.598
0.446
0.189
0.243
0.110
0.340
0.177
0.346
0.503
0.201
0.137
0.329
0.200
                                                                                          oro tn t>
                                                                                          m H-ft»
                                                                                          •• n H-
                                                                                          0*3
                                                                                          M  z
                                                                                          c. zo
                                                                                          pi O •
                                                                                          n •
                                                                                             4

-------
                                       TABLE 4-3



                 Vinclozolin Dose Rates  for Strawberry Harvesters — Day*3



                                         (mg/hr)
10 ARMLtM  ARhKllihl AUKS  AMLEH  AMKIGHT  AM   PMLEFT PMRlGrU  PM    LEFT   Rl&Hl  HANDS  llJTAL
6 0.008
7 G.015
6 0.005
9 G.019
10 0.005
11 C.OG1
12 0.002
13 0.014
14 0.007
15 0.002
17 0.001
Ifa 0.001
fVj 20 0.011
(_n 21 0.030
<2 0.028
23 0.003
25 0.012
26 0.005
Mean 0.009
S.D. 0.009


















0.011
0.002
0.003
0.006
O.OC6
0.011
O.OC2
0.009
0.016
G.003
0.001
O.OC6
0.005
0.013
0.006
0.003
0.004
0.009
0.007
0.004


















0.019 0.331
0.017 0.069
O.OOtJ 0.152
0.027 0.036
0*012 O.G9t
0.012 0.115
0.004 0.032
0.022 O.CB2
0.024 0.054
O.C05 0.037
0.003 0.029
0.006 0.110
0.016 O.Olh
0.043 0.223
0.035 2.471
0.006 0.137
0.016 0.056
0.014 0.181
0.016 0.235
0.011 0.564


















0.456 0.768 0.186 0.227 0.414 0.272 0.362 0.634 0.653
0.063 0.133 0.043 0.065 0.107 0.051 U.OC4 0.115 0.132
0.112 0.265 0.066 0.066 0.132 0.100 O.Otii O.lti4 0.192
0.031 0.067 0.026 0.025 0.053 0.032 O.GiiiJ 0.061 O.Obti
0.063 0.179 0.044 0.038 0.062 0.064 0.0*5 0.119 0.131
0.128 0.243 0.041 0.138 0.179 0.074 0.134 0.207 0.219
0.113 0.145 0.052 0.035 O.G87 0.041 O.ObO O.l.'l 0.124
0.02b 0.110 0.062 0.035 0.097 0.076 0.030 0.106 0.128
0.049 0.102 0.054 0.070 0.124 0.054 0.062 0.116 0.140
0.051 0.068 0.026 0.028 0.054 0.029 0.034 0.063 0.068
0.052 O.ObO 0.030 0.039 0.070 0.030 0.014 0.074 0.076
0.064 0.174 0.016 0.044 0.062 0.070 0.055 0.125 0.131
0.025 0.043 0.102 0.125 0.226 0.0*2 0.102 O.lt4 0.200
0.057 0.2BO 0.050 0.094 0.144 0.130 0.077 0.2U7 0.249
0.434 2.905 0.081 0.034 0.115 0*967 0.1U2 1.149 1.163
0.070 0.2G6 0.061 0.047 0.108 0.061 0.053 0.134 0.141
0.033 0.099 0.046 0.015 0.064 0*052 0.023 0.075 0.091
0.116 0.297 0.068 0.060 0*146 0.130 0.065 0.215 0.228
0.109 0.344 0.060 0.066 0.126 0.130 0.086 0.216 0.232
0.126 0.660 0.038 0.052 0.085 0.216 0.079 0.266 0.271
W
o 50 ID *o
o* ro o o»
r* < rtvQ
n> H- H- n
•• n o
*\ H- 3
(DO UJ
tr a z
H 0
c z •
fu o
n • o
"^ nT
K)
VO
vo o o LJ
00

-------
                                       TABLE  5
                 Summary of Dose Rates for  Strawberry  Harvesters  (3  Days)
                                       (mg/hr)
       VARIABLE
ro
ox
       t.t


\-l




o
t-*
                                                                                                  en

-------
                              TABLE 6-1

Statistical Analysis of Dermal Exposure Rates for Strawberry Harvesters
             Grouped by Weight — Three Days1 Observation
»g/hr X2
>50
r ~
; <50
ro
<50
>50
<50
>50
<50
>50
<50
*sl
**t
kg
kg
kg
kg
kg
kg
kg
kg
kg
33
21
33
21
33
21
33
21
33
21
0
0
0
0
0
0
0
0
0
0
.03
Lower arms 2.36 0.12
.02
.30
Hands, AM 1.08 0.3
.36
.24
Hands, PM* 11.19 0.0008
.12
.27
Hands, al 1 day** 3.44 0.06
.22
.30
Total** ' 3.71 0.05
.24
gnlf leant
Ime-welghted average
o
•n
7
1
<
K»
to
O
th
TO
«*
o"
3
Z
o
*
0
o <
-+•
o*
9
Z
O
*

-------
                                          TABLE  6-2
ro
CO
           Statistical  Analysis  of  Dermal  Exposure Rates  of  Strawberry  Harvesters


                     Grouped  by  Body  Surface —  Three Days'  Observation


         Jabjfl    H  Daraal Exposure  Rat*    Type   Knjsjcaf |  Wq I | (s        £
                                mg/hr
>1 .52 m2

<1 .52 m2
>t.52 w2

<1 .52 m2
>1.52 m2

-------
                                                                  198
                                         Paga    1     of	2	
                                         Section No.	13
                                         Revision No.	JJ	
                                         Data; February 29f 1984
                             TABLE  7-1

Correlation Between Dermal  Exposure Rates of Vlnclozolln and Age of

                       Strawberry Harvesters
Type of
Exposure
Left hand*
Right hand*
Hands, AM
Hands, PM
Hands, al 1 day*
Arms
Total*
Pearson
Corre 1 at Ion
Coef f leleqf
0.48
0.56
0.46
0.42
0.55
0.21
0.55
»
0.003
0.0001
0.0005
0.0016
0.0001
0.13
0.0001
Spearman
Cor re 1 at 1 on
Ceef f Iclent
0.50
0.57
0.46
0.53
0.57
0.37
0.58
JL
0.0001
0.0001
0-.0005
0.0001
0.0001
0.0056
0.0001
•Time-weighted averages for hands
                                        29

-------
                                                      .of.
                                                           13
Page___2__
Section No..
Revision No.	D	
Date;  February 29r 1 984
                                                                    199
                               TABLE  7-2



         Correlation  between Dermal  Exposure  Rates  and

              Productivity of Strawberry  Harvesters
Type of
Ex DOS Lire
Left hand*
Right hand*
Hands, AH
Hands, PM
Hands, al I day*
Arms
Tota 1 *
Pearson
Corre 1 at I on
Coef f lelant
0.31
0.44
0.23
0.47
0.39
0-14
0.39
£
0.0268
0.0011
0.0987
0.0005
0.0046
0.32
0.0046
•Time-weighted average for hands
                                         30

-------
                                                  1
             _of.
                                                           1 4
Page_
Section No..
Revision No.	Q	
Data* February 29r 1 984
                                                                  200
                                TABLE 8
 Decline of Dfslodgeable Residues of VInclozolln on Strawberry Leaves
        Days Post-AppI feat Ion*
D tsIodgeabI a RasI dues

 (Geometric  Means)

         ng/cm2
17
19
23
30
31
32
33
2
3
1
2
2
2
2
91 .2
41.7
18.2
7.41
8.91
5.37
5.24 *
•1 Ib/A each on May 5,15, and 22 May, 1982;

 first sampling date: June 8, 1983

-------
                                              1     of
                                      Section  No
                                      Revision No.
                                            Februar   29   1 QB4
                            TABLE 9
Transfer Coefficients for Vlnclozolln for Strawberry Harvesters



 Day of Study            Days Post-AppIleatlon       kg

                                                  
-------
                          TABLE 10
CarbaryIiVInclozolIn Ratios for D|sIodgeabIe Foliar Residues
                 and Dermal Exposure Rates

Day-1
Hands
Arms
Total
Day-2
Hands
Arms
Total

pay-3
Hands
Arms
Total






ug/cm? mg/hr
Carharvl Vlnclozolln C/V Carharvl V
0.61 0.009 67
1.99
0.66
2.65
0.55 0.0056 98
1.20
0.41
1.61

0.24 0.0052 46
1.02
0.43
1.45






1 nc | ozo 1 In

0.242
0.030
0.262

0.295
0.035
0.330

0.216
0.016
0.232






C/ V

6.2
22
*>~i

4
12
4.9
P"« 51 trm
4.7
26
,





J) 9 9 IV
•+ < run
ID — -HB
>. W —
— O
•n o 3
- o •
• •
2 o
^ 1 hj
0 3 -JM O
^ ^ r\j
o
u

-------
                                                      Of
                                         Section No. _ 17        OH7
                                         Revision MQ.     0         £-w-'
                                         Date y February 29. 1984
                       LITERATURE CITATIONS

Cabras, P., Paolo, P., Meloni, M.,  Pirisi, P.M. J. Agric. Food
Chem. 1982, 30, 569-572.

Cabras, P., Paolo, D., Meloni, M.,  Pirisi, P.M., and Pirisi, R.
J. Chromatogr. 1983,  256,  176-181.

Gunther, F.A., Westlake, W.E., Barkley, J.B., Winterlin, W.,
Langbehn, L. Bull. Environm.  Contain. Toxicol. 1973, 9, 243-249.

Gunther, F.A., Barkley, J.H., Westlake, W.E. Bull. Environm.
Contain. Toxicol. 1974, 12, 641-644.

Iwata, 7., Spear, R.C., Knaak, J.B., Foster, R.J. Bull. Environm.
Contain. Toxicol. 1977, 18, 649-653.

Popendorf,  H.J. and Leffingwell, J.T.  Bull.  Environm.  Contain.
Toxico. 1977, 18, 787-788.

Popendorf, W.J., Leffingwell, J.T., McLean, H.R., Zweig, G., and
Witt, J.M.  Youth in Agriculture. Pesticide Exposure by Strawberry
Pickers.  Captan. 1981-Studies. PHAP-Dniversity  of Calif .-Berkeley,
Final Report to OPTS, EPA, September,  1982.

Sendroy,  J., Jr.and Cecchini, L.P.  J.  Appl.  Physiol. 1954, 7,  1-12.

Spear, R.C., Popendorf, W.J., Spencer, W.F. and Milby, T.B.  J.
Occup. Med. 1977, 19, 411-414.

Zweig, G.,  Gao, Ru-yu, and Popendorf,  W. J. Agric. and Food Chem.
1983, 31, 1109-1113.

Zweig, G.,  Gao, Ru-yu, Witt, J.M.,  Popendorf, W., and Bogen, K.
Youth in  Agriculture. Dermal  Exposure  to Pesticides by Strawberry
Harvesters. 1982-Studies.  I.  Carbaryl.  PBAP University of Calif.-
Berkeley, Draft Report Submitted to OPTS, EPA,  December,  1983.
                                    34

-------
                                                               204
                                          Page    1     of   10
                                          Section No.      is
                                          Revision No.	0
                                          Datet  February  29. 1984
                             FIGURE 1
Capillary GLC of mixture of standards of vinclozolin (retention
time: 6.53 min); endosulfan I  (7.44 min); endosulfan II  (7.80 min);
endosulfan sulfate  (8.16 min);  experimental dtails described in
text.
                                  35

-------
                                                            205
               -of	10.
                  18
                                     Page	2.
                                     Section No..	
                                     Revision  No.	Q	
                                     Date: February 29. 1984
                            in
                             •
                            M)
i
*i
 •
I-
o  ••[>
O.n  .•
 •   •
t.  ff>
in

                     f*'
                           36

-------
                                       Page    3     of   10

                                       Section No. _ LB
                                       Revision No. _ 0
                                             February  29. 1984
                          FIGURE 2


Linear regression of exposure rates versus age of strawberry


             harvesters exposed to vinclozolin.
                                    37

-------
(VINCLOZOLIN) EXPOSURE VS. AGE
                               D   2  POINTS
                                y « 0.0132X + 0.0326
                                r • 0.82
                                p • <0.0005
             20
                                     30
                                                            40

-------
                                        Page     5    of   10
                                        Section  No.     IB
                                        Revision No.
                                        Pat A.  February 29. 1984
                           FIGURE 3

Linear regression of exposure versus productivity of strawberry

              harvesters exposed to vinclozolin.
                                       39

-------
                                                            EXPOSURE VS. PROOUCTIVin
     0.7
     O.i
  ^•^

  !M
  g
  jg 0.4
  19
  ft
     0.3
     0.2
o  OJ
       0.5
                            0.6
                                                                      J_
0.7
                                                                                                               o
                                                   y • 0.571 . 0.19S

                                                   r-O.M

                                                   p • <0.005
        0.8

PRODUCTIVITY (crttM/tir)
                                                                                           0.9
                                                              1.0
                                                                                                                                  D> *
                                                                                                                                  ft < O«Q
                                                          -1—
                                                           1.05
.. 01 !•*•
  H-O
*OO 3
V 9
T  SB
i S50
BO*
                                                                                                                                         O
                                                                                                                                         H»
                                                                                                                                      u  ^

                                                                                                                                           VO

-------
                                      Page    7    of   10

                                      Section No.	L8	
                                      Revision No.	Q	   _ . _
                                      Date* february 29. 19B4   2 I 0
                         FIGURE 4                  :
                                                   I

Linear regression of productivity of strawberry harvesters


                        versus age
                                        41

-------
    1.2
    1.0
     .8
ae.
x
2
O
.6
     .4
     .2
                                                AGE - PRODUCTIVITY
O   O

   O
                              10
                                                 20
                                                                    y « .01X + 0.645

                                                                    r « 0.55
                                          30
                                                             AGE
                                                                                                                  rt
-------
                                                               212
                                                     ef   10   t~
                                         Section No.     18
                                         Revision No. _ Q
                                         Pa tie- february 29. 1984
                             FIGURE 5
Semi-log plot of decline of dislodgeable vinclozolin foliar
residues on strawberry plants; vertical bars are confidence
                        intervals; r—0.96.
                               43

-------
                                                   DISLOOGEMU RESIDUE
s
••*
i
                                                                                                                                       t» l» A »
                                                                                                                                       ft 4O 9
                                                                                                                                        D 9
                                                                                                                                        T   Z
                                                                                                                                        •« sso
                                                                                                                                        s o •
                                                                                                                                               Ml—••
                                                                                                                                             r

-------
                                                  214
Simultaneous Dermal Exposure to Captan
  and Benomyl by Strawberry Harvesters
  1983
        Research performed by

        University of  California
        Richmond, CA  94804

-------
                                                               215
                            Abstract








     Ten strawberry harvesters were monitored during work-




ing hours for dermal exposure due to captan C3a,4,7,7a-




tetrahydro-IM- (trichloromethanesul-f enyl)  phthal imide] and




benomyl Cmethyl 1-C(butylamino) carbonyl3-lH-benzimidazol-




2-ylcarbamate]. The average dermal exposure was found to be




39.01 mg/hr/person -for captan and 5.39 mg/hr/person for




benomyl. The ratio of the dermal concentration of captan




and benomyl was found to be similar to the ratio for




dislodgeable foliar residues of the same two pesticides




from strawberry plants in the same plot. Productivity, as




measured by the quantity of fruit picked,  and dermal expos-




ure of individuals to benomyl correlate positively. The




study was designed to measure left- and right handed dermal




exposure and to determine dextral preference among



strawberry pickers.
                              2_

-------
                                                                      216

     The determination  of  dermal  exposure to pesticides by

harvesters  o-f  -Fruit  and field crops -forms the basis  -for

establishing reentry intervals.  These intervals  are

designed to permit agricultural  -field workers to reenter

pesticide-treated plots without  su-f-fering any ill  e-f-fects.  The

regulation  o-f  organophosphorus insecticide residues  -for

•farmworker  protection has  been recently discussed  by Popendor-f

and Leffingwell  (1982).  Most  o-f  the previous attempts to corre-

late dermal human exposure with  dislodgeable -foliar  pesticide

residues have  dealt  with a single pesticide 
-------
                                                              217
Each volunteer was also provided with dermal dosimeters fastened

to the outer side of the -forearm, 6-in. above the wrist, with

surgical tape. This dosimeter consisted o-f a 12-ply 3x3 in

surgical gauze placed into a slightly larger glacine—paper

envelope with a circular 60-mm diam hole -facing the outside  (away

•from the skin) and a piece o-f polyethylene -film placed on the

other side o-f the gauze nearer the skin to serve as a moisture
                           2
barrier. In this way, 28 cm  o-f the gauze pad was exposed to the

environment. The workers were not required to wear any special

protective clothing other than those normally worn early in the

morning, like slacks and long-sleeve shirts. Subjects were

measured -for height and weight; age, sex and manual preference

were recorded.

     Subjects went about their normal work, picking

strawberries in a bending or squatting position. For the corn-fort

o-f the workers, the gloves and -forearm dosimeters were removed

•from the subjects after about two hours and stored in plastic

bags, packed with "dry-ice" during transport and kept in freezers

until the extraction and analyses could be performed.

Productivity for each subject was recorded as "number of crates

harvested" during the monitoring period.

     Forty—eight strawberry leaf disks for dislodgeable

residue analyses were taken from different plants diagonal-

ly across the strawberry plot with a mechanical leaf punch.

This tool is equipped with a 3-cm diam circular die and

attached with a screw cap to a 4-oz wide-mouth glass jar.

Details of this and other sampling techniques are described

-------
                                                                   218
by Popendorf, et al.(1982b).

     In-formation obtained  from  the commercial  pesticide

applicator showed that the latest application  prior to the

study took place on May  15,  1982  ( 4  days prior to the

study) and consisted of  the -following given as active

ingredient (a.i.):  1.5  gal  EC  dico-fol  (2.4 Ib a.i.); 1  Ib

benomyl; 4 Ib captan.

     Materi.al.5 and Anal.yti.cal. Instrument at i.on. Analytical-

grade captan, benomyl, and carbendazim (methyl 1H-

benzimidazol -2-ylcarbamate)  were obtained -from the EPA

Re-ference Standard Repository,  Research. Triangle  Park, NC

27711: carbendazim was also obtained  -from duPont  Nemours &

Co. All solvents used throughout were HPLC-Grade  ("Baker

Analyzed" or equivalent).  Water -for HPLC solvents was

passed through a Milli-Q Water  Purification System. Mobile

phases for HPLC were degassed by filtration through

Millipore FHUP filters and stirring under a watei—pulled

vacuum for 30 min.

     A Tracer—222 Gas Chromatography  Apparatus, equipped
       63
with a   Ni-EC detector  and Hewlett-Packard electronic

integrator (HP 3390A) was  used  for captan analysis. The

chromatographic column was a 3  ft x 2 mm  (i.d.) glass

column packed with OV-1O (1O7.)  on Supelcoport  (SO/1OO

mesh).

     For the analysis of benomyl and  carbendazim  the

fallowing HPLC apparatus was used: Waters Model 6OOOA

Solvent Delivery System; WISP Automatic Sample Processor;

Model  450 Variable Wave  Length  Detector; Water Data Module;

-------
                                                                219

RP-18 Spheri 5 Brownlee Labs, bonded reversed-phase column

(25 cmx 2 mm i.d.). A Bausch & Lomb Spectronic 20OO record-

ing spectrophotometer was employed -for confirmatory analy-

sis o-f benomyl and carbendazim.



     iM.lr.§cti.on. Gauze patches were individually extracted with

5O to 60 mL o-f acetonitrile by placing the sample and solvent

into a 125-mL wide-mouth LPE bottle -fitted with a screw cap and

shaking the contents on a mechanical platform for one hour.

Gloves were extracted in a similar manner by using 100 mL of

solvent and 5OO mL-plastic bottles.The solvent layer was decanted

and passed through a Millipore BD  (O.6 Jim) filter. Al i quots of

the filtrate were analyzed for captan and benomyl by GLC and

HPLC, respectively. In order to maintain the linearity of the

electron-capture detector for captan analysis, up to 20-fold

dilutions of extracts containing high concentrations of this

pesticide were necessary.

     Dislodgeable foliar pesticide residues and dust were

isolated from leaf punches according to methods developed by

Gunther (1973,1974), Iwata (1977) and Popendorf and Leffingwell

(1977). Leaf punches were surface-extracted with 10O mL of a 60 -

ppb aqueous solution of dioctyl sodium sulfosuccinate by agita-

tion on a reciprocal-action mechanical shaker for 30 min. The

liquid phase was carefully separated from the plant tissue and

extracted three times successively with 50 mL each of dichlorome-

thane in a 500-mL separatory funnel. If an emulsion formed, the

addition of a few mLs of sat. aqueous Na SO  was usually
                                        2  4

-------
                                                                 220
sufficient to separate  the  phases.  The  combined  organic  extracts

(bottom phase) were  -filtered  through  glass  wool  and  a  bed  o-f  anh.

Na SO  and evaporated in  vacuo to complete  dryness.  The  residue
  <2  4
was -finally taken  up in 10.0  ml_ o-f  acetoni tri le.  Aliquots  o-f  this

solution were directly  analyzed -for captan  and benomyl as  will  be

described below.

     Lea-f dust, originally  washed o-f-f with  the sur-factant,

remained in the inter-facial solvent-water layer  in the separatory

•funnel and was quantitatively trans-ferred a-fter  the  last solvent-
                                                              o
extraction to a pre-weighed glass -filter. A-fter  drying at  110

overnight, the -filter was weighed again,  and  the weight  o-f  the

•foliar dust calculated  by di-f-ference.



     Analysis of Caftan and Benomyl. One to  5  ML  of the

•final extract or appropriate  dilutions  thereof,  were ana-

lyzed -for captan by  gas-liquid chromatography. Chromatogra-

phic conditions were the  -following: argon-methane carrier
                                                      o
gas -flow rate — 65  mL/min; column temperature — 210  .

Under these conditions, captan eluted as a  sharp peak  at

1.27 min. No interfering  peaks were observed  in  any  of the

field samples. Quantification was performed by area-integt—

ation using an electronic integrator  and an external stand-
f
ard calibration curve.  Results were reported  as  Wg/sample
                                 2
for patches and gloves  and  tig/cm  leaf  surface  or Ug/mg  of

dust for dislodgeable residues.

     The analytical  method  for benomyl  is based  on  the

spontaneous conversion  of benomyl to  carbendazim in

acetonitrile and subsequent analysis  of carbendazim  by HPLC

-------
                                                                    221
 (Zweig and Gao,  1983).  Twenty— five microliters o-f the -final

extracts was analyzed  by  reversed-phase HPLC on a C-18

bonded column using  as mobile  phases acetoni tri le-water in

the proportions  o-f 65:35  or  5O:5O,  v/v and a solvent -flow

rate o-f 1.3 or 1.5 mL/min, respectively.  Benomyl  and

carbendazim were detected at 286 nm.  The elution  time -for

carbendazim with both  mobile phases was -found to  be 3.4

min. The retention times  -for benomyl ,  stabilized  by the

addition o-f n-butyl isocyanate  (Chiba,  1977), were 7.8 and

15.8 -for the two mobile phases,  respectively. Quantifica-

tion was accomplished  by  an  electronic integrator, using

the external standard  method.  The minimum detectable quan-

tity -for both compounds as limited by instrumental noise

and detector sensitivity  was -found to be 5 ng.
                Q9£*=-  All  extracts must be kept at room temper a-
                     o
ture -for 3 hrs or  4O  -for  1  hr  prior  to the analysis. The purpose

o-f this waiting period is  to permit the quantitative conversion

o-f benomyl to carbendazim  in acetoni tri le, which is -fully

discussed by Zweig and Gao (1983).]

     All results are reported as  benomyl.  I-f carbendazim was

chosen as external standard,  the  molecular weight conversion

•factor o-f 1.52 was applied.

   §§ti.matign of Dermal, iiiESSyr.!      To estimate dermal

exposure on the -forearm, the -following calculations were

made: The concentration o-f pesticide  on the patch was
                            2
multiplied by 645/28,  28 cm  being the exposed sur-face area
                        2
o-f the patch and 645 cm the sur-face  area o-f the -forearm o-f

-------
                                                                    222
the 50-percentile  man  (Popendor-f,  1982).  This  was  further



corrected  -for  individual  body  surface  differing from that

                                 2

of the 50-percentile man,  1.92 m ,  by  estimating individual
                     •

body surface from  a  body  weight-height nomograph (Sendroy



and Cecchini,  1954). Because gloves cover the  entire ex-


posed area of  the  hands,  total  manual  exposure was estim-



ated without transformations.  All  exposure data were


normalized for  an  hourly  exposure  rate.



     B§£overy  Studies  for  Caftan and Bengmyl..  Control


samples of patches,  gloves, and strawberry leaves  were



spiked with known  amounts  of captan, benomyl,  and


carbendazim. For recovery  purposes,  benomyl  was stabilized



by the addition of excess  n-butylisocyanate  (Chiba, 1977).



Strawberry leaves  from a non-treated field were not



available  when  benomyl-carbendazim recovery  studies were



conducted,  and, therefore, a dilute aqueous  solution of



dioctyl sodium  sulfosuccinate  served as surrogate  for "dis-



lodgeable  foliar residue samples".  All spiked  samples were



processed  by the same  procedures as described  above under



"Extraction" and analyzed  by appropriate  instrumental



methods, GLC or HPLC.  As shown  in  Table I, recoveries were



almost quantitative  for all compounds  studied.



     C°DfiJHmsSti°D Qf Q§r.bendazim Bssi.dues. The identity of


suspected  carbendazim  residues  from field samples  was con-



firmed by  two independent  methods:  The solvent extract of a



field sample (left-handed  glove. Subject  No. 2) was .chroma-



tographed  by HPLC and  the  eluant collected at  the  previous-



ly determined retention time of carbendazim.The uv-scan of

-------
                                                                  223
this solution was identical to the spectrum o-f authentic

carbendazim with characteristic absorption peaks at 286.1

nm and 28O.O nm and a shoulder at 294.1 nm. Ths uv-spectrum
                                                              3
o-f this sclution containing n-butyl i socyanate  (final concn.  10

ppm) was identical to one of authentic benomyl with absorption

peaks at 292.6 nm and 286.1 nm and the absence of the absorption

maximum at 28O nm, belonging to carbendazim.

     A second confirmatory method involved the demonstra-

tion of quantitative conversion of suspected carbendazim to

benomyl following the addition of excess n-butylisocyanate.  The

extracts of two representative field samples (gloves belonging to

Subject No. 7) were .first analyzed for carbendazim by HPLC and,

after the addition of n-butylisocyanate, for benomyl. The reten-

tion times for carbendazim and converted benomyl from the field

samples were identical with those of reference standards. As

shown in Table II, quantitative conversion of carbendazim to

benomyl had taken place., demonstrating that carbendazim was

indeed the compound isolated from field samples.



RESULTS AND DISCUSSION

     P.srmal_ Exposure to Bengmv.1. and Caftan.  The ten

volunteers for this study <7 male and 3 females) were

experienced strawberry pickers and ranged in age from 19 to

55 years of age (Table III). Pickers 1 an 2 were most

productive as judged by the number of crates picked per

hour. Each crate consisted of twelve 1-pint baskets with a

total net weight of fruit of about 5 kg.
                               10

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                                                                   224
     Popendor-f et al. < 1982, a, b) and Everhart  and Holt




(1982) have shown that the major dermal exposure o-f straw-




berry harvesters to  captan and benomyl occurred on hands




and lower -forearms.  Dermal body exposure could, there-fore,




be estimated by monitoring only these two anatomical




regions, hands and -forearms. This assumption  may not be




valid -for harvesters o-f other crops, like tree-grown




•fruits, where Popendor-f  (198O) observed a more uni-form




total body exposure.  Row crops, like strawberries, are




hand-picked -from a stooped or squatting position which




determines the dermal  distribution -found by Popendor-f




(1982,a,b) and Everhart and Holt  (1982).




     Forearm exposure was estimated -from the  gauze




dosimeter placed in  a position where greatest exposure -from




contact with plant -foliage would most likely  be expected,




i.e. the region o-f the -forearm above the wrist. Using the




concept o-f the 5O—percenti le man and the proportional




sur-face allocation -for each anatomical region, an estimate




to that particular region  (-forearm) was made, notwithstanding  the




possibility of non-uni-form pesticide distribution, leading to




possible error in the -final estimate.




     Table III shows that dermal exposure by  the ten




subjects studied ranged -from 1.2 mg/hr to 15.5 mg/hr -for




benomyl and 13.2 mg/hr to 51.3 mg/hr -for captan.




Corresponding means  were calculated to be 5.39 mg/hr/person




(86.4%) and 39.Ol mg/hr/person  (38.0%), respectively, with




the percent relative standard deviations in parentheses.




Subject No. 1 exhibited an inexplicably high  le-ft-handed






                               11

-------
                                                                  225
captan exposure  
-------
                                                                    226
The ratio o-f average di slodgeable residues of captan and

benomyl is 6.1. The corresponding ratio -for dermal exposure

is 7.2  (see Table  III). These two ratios are similar, suggesting

that dislodgeable  -foliar residues o-f several pesticides are

trans-ferred from -foliage in the same proportion to the exposed

skin sur-face o-f -field workers. Popendor-f and Le-f-fingwel 1  (1982)

and Popendor-f et al.  (1982,a,b) have already shown that a

positive correlation between dislodgeable foliar residues and

dermal concentrations o-f pesticides exists.

     Using the data -from Tables III and VI, transfer coef-

ficients^,) for captan and benomyl were be calculated and found
             32'           32
to be 8.57x10  cm  /hr and 7-19x10  cm /hr, respectively,  ("k " is
                                                            d
defined as the ratio of dermal concentration to dislodgeable

foliar residue and assumes the units of area over time). The

transfer coefficients from this study are similar to those

reported by Popendorf and Leffingwell  <1982c> for citrus  and

peach harvesters exposed to organophosphorus insecticides.
                                              2
Converting the k.*s to minutes  (143 and 120 cm /min), it would

appear that strawberry harvesters are contacting a small foliar

surface thereby receiving maximum pesticide exposure. This

reason-ing is based on the unlikely situation that foliar pesti-

cide residues are transfered quantitatively to skin.

     In prior studies by this laboratory  (Popendorf, et al.,

1982a,b), surface captan residues of about 1 ppm were found  on

strawberries,, and these residues may, therefore, be a

contributory factor of dermal exposure, especially to hands  of

fruit harvesters.  The relative contribution to dermal exposure

from foliar dislodgeable residues and surface residues from  fruit

-------
                                                                   227
remains.to be the subject o-f a -future  study.






     Cgmearisgn of Left- and Right_Handed  ExD,gsure.  Since




left— and right-handed gloves were  individually  analyzed,




it Mas possible, there-fore, to compare dermal  pesticide




exposure o-f each worker on his le-ft and right  hand.  At




least eight out o-f these ten workers pro-fessed to  be right-




handed, and the remaining two workers  did  not  express a



pre-ference. As may be seen in Tables IV and V, it  appears




that Subject 5 exhibits right-handed pre-ference  as shown  by




the data -for both captan and benomyl.  In addition. Subjects




3, 6 , and 1O also showed right-handed preference, based  on




the data -from one o-f the pesticides. The remaining subjects




appear to be ambidextrous in picking strawberries  as manif-




ested by hand exposure data. These  findings suggest  that




analyses of chemical exposure on the left  and  right  hand




might be a suitable method for conducting  time-motion stud-




ies of farm workers harvesting row  crops.






     Prgducti.vi_ty. and Exposure. A positive correlation  was




found between productivity, expressed  as crates  harvested




per hour, and dermal exposure of benomyl per hour  (fig.l)




(r = 0.812; p = 0.0043) which might explain why  workers




with the greatest productivity (Subjects 1 -and 2)  receive




the highest benomyl exposure (Table III).  The  worker who




picks a large amount of fruit may be subject to  more skin




contact with fruit and foliage bearing dislodgeable




pesticide residues than the worker  who is  less productive.

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                                                                 228



A similar correlation between productivity and dermal



exposure to captan was not -found.



REMARKS




     The toxicological consequence of dermal exposure to



pesticides by crop harvesters remains uncertain until



percutaneous absorption rates for these pesticides have



been determined.  Although there are -few compounds which



are quantitatively absorbed through the skin, a conserva-



tive estimate o-f body dose may be made by assuming 100%-



absorption o-f the dermal dose. In the absence of the



experimentally derived data, this hypothetical dose may



serve as a first basis for estimating potential toxicological



hazard to crop harvesters.



     Another uncertainty, as illustrated by the present



study, is the estimation of daily exposure based on a rela-



tively short observation period  (less than two hours). It



has been observed in this and previous studies (Popendorf, et



al., 1982 a,b) that gloves became quickly saturated with fruit



juice and dew, especially in the early morning hours when most of



our observations were made. It seems reasonable to assume that



once gloves have become moisture-laden, the absorptive capacity



of the cotton cloth might be impeded. The techniques for measur—



ing average dermal exposure during a workday may, therefore, not



represent actual dermal exposure. This concern has prompted the



initiation of a series of studies by this laboratory investigat-



ing, comparing, and improving presently used techniques for mea-



suring dermal exposure to pesticides (Noel, et al., 1983).

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                                                             229
                         Literature Cited




Baude, F.J.;  Gardiner,  J.A.; Han,J.C.Y. J._  BSCiEi E°2d




Chem.. 1973., 21,  1084-90.




Chiba, M. J.  Agri.c._ Food  Chem.. 1977, 25, 368-73.




Everhart.L.P.;  Holt,R.F.  J.. Agric._ Food Chem..  1982,  30,222-7.




Grubbs, F.E.  lechngmetrics 1969, I.J.,  1-21.




Gunther, F.A.;Westlake,  W.E.; Barkley, J.H.; Winterlin, W.;




Langbehn. L. Byiii Environ^ Cgntam.. Igxicgl^  1973,  9,  243-9.




Gunther, F.A.;  Barkley,J.H.; Westlake,W.E.  Bui.!...  iDyiC°Di




QeDtam.. Tgxicgl... 1974,  12, 641-4.




Iwata, Y. ; Spear, R.C. ;  Knaak, J. B. j Foster, R.J. Bul.1... Environ^




CgntaiDi !gxi.cgl.... 1977, JLS, 649-53.




Noel, M.E.; Zweig,  G. ;  Popendor-f, W.J. "Abstracts o-f Paper",




185th National  Meeting o-f the American Chemical  Society, Seattle,




WA, March, 1983;  American Chemical Society,  Washington, D.C. CHAS




27.




Popendor-f, W.J.  Amer.. !nd._ H^g.. J._ 1980, 41.,  652-9.




Popendorf, W.J.;  Le-f-fingwel 1, J.T. By!!._ Environ.. Contam..




Joiiicol.. 1977,  18,  787-8.




Popendorf, W.J. 5  Le-f-f ingwel 1, J.T. Residue  Reviews 1982,




82,125-201.




Popendor-f, W.J. ;Le-f-f ingwel 1, J. T.; Zweig, G. "Abstracts of




Papers", 184th  National  Meeting o-f the American  Chemical




Society, Kansas City,  MO, September,  1982;  American




Chemical Society,  Washington, D.C. CHSA 33.




Popendor-f, W. J. ;Le-f-f ingwel 1, J. T. ; McLean, H. R. , j Zweig,  G. ;

-------
                                                                230
Witt, J.M.  "Youth  in  Agriculture"—Pesticide Exposure to
Strawberry  Pickers;  1981-Studies",  Final Report submitted
to O-f-fice o-f Pesticide Programs,  EPA,  Washington, D. C.
(Sept.1982b).
Sendroy, J., Jr.;  Cecchini,  L.P-  J.. ABB!... Ph^sigli. 1954, 7,
1-12.
Zweig, G. >  Gao,  Ru-yu.  Accepted by Anal... Chem.. 19B3j see
also  "Abstracts  o-f Papers", 185th National Meeting o-f the
American Chemical  Society, Seattle, WA, 19S3;American
Chemical Society,  Washington,  D.C.; PEST 29.
                                .17

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                                                              231
EiD.anci.al. SuEBgrt: Supported by EPA Cooperative Agreement



between- EPA and the University o-f California, Berkeley,  CR




SO9343-01 and a UNESCO Fellowship to one of us  (R.-y.B).




This paper has not undergone Agency Review and, therefore,




represents the views of the authors and not necessarily




those of EPA.
                  Captan analyses were performed by Mr.  .Hugh  R. McLear




of this laboratory. The assistance of Leonore Dionne during  the




field study and as interpreter is acknowledged.

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                                                             232
                       Legends to Figures











Figure  1:  Linear regression curve of "productivity"  vs.  total




          dermal dose o-f benomyl -for ten strawberry harvesters.
                         IC\

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                                                              233
                               Table I



       Summary o-f Recovery Studies for Carbendazim, Benomyl, and

                             Captan




       .             ComEQund     Added    Found    Per cent Recovery
Gauze pad (6O ml_)
Gloves (1OO mL)
Gloves (1OO mL)
b
DOSSS (100 mL)
DOSSS (100 mL)
DOSSS (10O mL)
Gauze pad (SO mL)
Gauze pad (SO mL)
Gauze pad (50 mL)
Gauze pad (50 mL)
Gauze pad (60 mL)
Gloves (10O mL)
Leaf disks #1
Leaf disks #2
a
carbendazim
carbendazim
carbendazim
carbendazim
carbendazim
carbendazim
c
benomyl
benomyl
benomyl
benomyl
captan
captan
captan
captan

51.0
102.0
204. 0
16O.O
160.0
160.0
127.5
127.5
255. O
255.0
27.5
27.5
5.5
2.8

49.5
97.5
194.3
152.9
153.3
151.7
126.6
125.0
252.2
250.0
30.2
31.6
5.3
2.7

97.0
95.6
95.3
95.6
95.8
94.8
99.3
98.0
98.9
98.0
103.3
108.4
95.6
96.4

  volume of extract
b
 aqueous solution of O.06 ppm dioctyl sodium sulfosuccinate
c
 To a standard solution of benomyl in acetonitrile  (50.0  ing/100  mL)
                                                           3
was added n-butylisocyanate to a final concentration  of  10 ppm.

-------
                                                                   234
                               Table II
           Confirmation of Carbendazim and Benomyl Residues
                                       a                 b
                            Qarbendazi.m           lengm^l.     Per   cent
                                                               Recovery


Left glove (Sub. No. 7)
Right glove (Sub. No. 7)
Found Theory Found
ng ng
115.2 158.9 162.7 102.6
137.1 189.4 189. O 10O.O
a
 Sample  extracted  with  6O ml_  of  acetoni tri le:  diluted   1:5  with

solvent;  25-uL aliquots analyzed in duplicate by HPLC.


b                                               4
 To  20.0  mL  o-f diluted extract,  0.2 ml_ of 10  ppm  solution  of  n-

butylisocyanate  was  added;   25-pL  aliquots  analyzed  by  HPLC   in

duplicates.

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                                                                   235
                               Table III
     Hand- and Lower Arm Dermal Exposure by Strawberry Harvesters
                           Product i. v i^t y
Exposure

. 1 M 36

2 M 45
3 M 29
4 M 19
5 F 55
6 M 22
7 M 30
8 M 23
9 F 51
1O F 20



(crates/hr)
7.36
(
7.36
5.45
5.38
3.OO
3.40
4.0O
3.25
4.65
2.96
Mean
rel . std.dev.
Cap tan /Ben 1
(mg/hr )
Captan Benomyl
52
a
180.9)
37.4
35.0
49.8
13.2
25.0
51.3
62.1
28.9
35. 1
39.O1
(38.07.)
ate = 7.
15.5

12. 1
4.2
2.8
1.2
1.9
4.2
4.9
2.7
4.4
5.39
(86.47.)
23
a
 The  experimental -figure has been deleted as  an outlier  according  to

the procedure o-f Grubbs  (1969) and substituted by  an  estimate o-f

52 mg/hr. See also -footnote, Table IV.

-------
                                                                .  236
                               Table  IV
        Left  and  Right  Hand and Forearm Exposure to  Captan

                      by  Strawberry  Harvesters
                No._               Derma
Fore
left

1 15.22


2 13.81
Z 3.05
4 0.31
5 0.50
6 0.68
7 4. 13
8 1.75
9 0.95
1O 0.95
arm
right
•
4.82


4.55
2.59
1. 18
3.81
0.64
3.60
2. 18
0.24
2.49
Han
left

16. 14

(144.79)
8.96
3.39
22.69
2.75
12. 14
20.32
27.32
8.67
16.67
ds
right

16. 14
a

10.00
25.94
25.62
6. 10
11.57
23.20
30.81
19.06
15.04
a
 This  -figure  is deleted according to procedure by Grubbs  (1969)  -for

outlying  observations  and  is  replaced  by  value  -for   right-hand

exposure, assuming ambidexterity o-f Worker No. 1.

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                     Table V








Le-ft and Right Hand and Forearm Exposure  to  Benomyl




              by Strawberry Harvesters
                                                    237
Worker No.
Exggsure
Forearm
left right
1 1.
2 1.
3 0.
4 0.
5 O.
6 0.
7 0.
8 0.
9 0.
10 0.
25
16
42
0
0
07
28
19
07
09
0.
0.
0.
0.
0.
0.
0.
0.
O.
0.
32
31
18
06
21
O4
29
17
04
21

Har
left
6.
5.
1.
1.
0.
O.
1.
2.
0.
1.
93
30
66
36
30
83
65
04
88
13
ids

right
6.
5.
1.
1.
0.
0.
2
2.
1.
2.
96
23
94
38
67
97
00
46
67
94

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                                                         238
                       Table VI
  Dislodgeable Foliar Residues From Strawberry Plants
       No..
                   2                     2
              yg/cm   yg/mg dust     pg/cm    yg/mg dust
               4.21     10.4         0.73       1.79
               4.89     13.9         0.78       2.19
Mean           4.55     12.2          O.75       1.99
                      Captan/Benornyl  =  6.06

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I
                 £
                 M4
                 CO
16
15
14
13
12
11
10
 9
 8
 7
 6
 5
 4
 3
 2
 1
 0
I       I
                                 J	L
                                     I       i
                                                                                             O
                                                                                                         O
                                                                                     o_
                                                                                                                                      er
      J	I	I	I	I	1	I	L
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                         0.0     0.5     1.0    1.5    2.0    2.5     3.0     3.5     4.0    4.5    5.0     5.5     6.0    6.5     7.0     7.5
                                                                    PRODUCTIVITY   fcritis/lr)


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                                                      240
The Relationship between Dermal Pesticide
  Exposure by Fruit Harvesters and Dislodgeable
  Foliar Residues 1981-1983
        Research performed by

        University of California
        Richmond, CA  94804

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                                                                     241
      THE REUTICRSHIP BHWKfcW DERMAL PESTICIDE KUHJKittE BT
        PRUT HARVESTERS AID DISLGDGEABI£ FOLIAR
£gy_ Holds.:  Pesticides,  captan, vinclozolin, methiocarb,
            carbaryl, Dermal Exposure, Strawberry Harvesters,
            Blueberry Harvesters, Dislodgeable Foliar Residues

      Gunter Zweig1, J. T. Leffingwell,  and Wm. Popendorf2
    Sanitary Engineering and Environmental Health Laboratory
               University of California, Berkeley
                      Richmond, CA 94804
     Dermal  pesticide exposure rates, expressed in mg/hr, by
strawberry and blueberry harvesters and dislodgeable foliar pest-
icide residues were  determined in 7 separate field  experiments
during 1981  - 1983 in California and Oregon.  The pesticides
which were studied  included captan,  vinclozolin, carbaryl, and
methiocarb.  A positive correlation between these  two parameters
was found and compared with literature  values involving different
^Office of Pesticide Programs,  EPA,  Washington,  D.C. 10460
2Inst.  of Agricultural Medicine, University of Iowa, Iowa City IA
                                     1

-------
 pesticides and tree crops.  The ratio between dermal exposure            c. 4 
-------
                                                                       243
 (N-tr ichloromethy lthio-4-cyclchexene-l,2-dicarboximide) .  later
 experiments involved strawberry harvesters exposed simultaneously
 to the fungicide vinclozolin  [3-(3,5-dichloroFhenyl)-5-ethenyl-5-
 methyl-2,4-oxazolidinedioneJ and the insecticide carbaryl (1-
 naph thy 1-N-me thy lea r hamate) and blueberry harvesters exposed to
 methiocarb [4-(methylthio)-3,5-xylyl-methylcarbamate] used as a
 bird repellent.  Some of the latter studies were simplified by
 limiting the number of personal  monitoring sites without sacri-
 ficing the accuracy for the estimation of total dermal exposure.
     The  studies reported here took place during the harvesting
 seasons of 1981 - 1983 at several  locations  in California and
 Oregon.  Details on sites,  study  dates,  pesticides  applied,
 dosage, crops, and meteorological  information may be found in
 TABLE 1.
     The  experimental plan was to recruit for each study at least
 twenty fruit harvesters to include males,  females, adults and
 children  (10  - 11 years old) to be monitored for dermal exposure
 to pesticides during regular working ours  and under normal
 working  conditions, resulting  in minimal interference in their
assigned  duties.   Due  to the  sparser harvest of strawberries in
August,  there were fewer subjects  for  Studies 4 and  5 (see
TABLE 1).
     Monitoring devices  for dermal exposure consisted of 12 -
ply, 3 x 3 in. surgical gauze  pads.   A polyethylene  moisture
barrier was placed on the side  of the pad facing the skin of the

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                                         TAWJK 1

                                  Summary of Field Studies
Study
No.a
1
2
3
4
5
6
6a
7
Date
5/9/81
6/22/81
7/21/81
8/21/81
8/21/81
6/22 - 24/81
6/22 - 24/81
7/24 - 28/83
Crop Compound Dosageb
^ (kg/ha)
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Blueberries
Captan
Captan
Captan
Captan
Captan
Carbaryl
Vinclozolin
Methiocarb
2.5
2.8
2.2
2.2
1.1
1.1
1.1
1.65
Days0 No. of
Post Appl. Workers
13
26
4
3
48
15,16,11*
31,32,33
3,4,6
19
23
15
6
10
18
18
25
Heather
°c
23
16-19
12-24
18-21
18-21
12-32
12-32
18-21
Ppt
0
~4mn
0
0
0
0
0
e
a 1 « Cooperative farm near Salinas,CA
  2 « Private farm near Corvallis, OR
  3-5 « Cooperative farms near Salinas, OR
  6 - Private farm near Corvallis, OR
  7 * Private farm near Salem, OR
bDosage of active ingredient (a.i)
c Days after last treatment.
d Observations were made on each day.
e Heavy rainfall on Day-5, post-application.

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                                                                   245
subject.  The container of the monitor is a hand-folded glossy
envelope with a circular hole 60 mm in diam. on the side facing
away from the skin, thus exposing 28 cm2 of the gauze pad.
     Patch monitors are placed at various body sites, the head
(fastened to a head band or brim of a cap); chest, back, upper
arms  (stapled to a tightly fitting cotton T-shirt); lower arms
and lower legs  (fastened to skin with surgical tape).  Light-
weight cotton gloves, similar  to those worn in photographic
darkrooms and electronic assembly plants serve  as hand monitors.
     The subjects were not required to wear special clothing;
their garments usually consisted  of denim jeans and long-sleeved
cotton shirts.  On hot days, male workers might remove their
shirts but continued to  wear the specially supplied T-shirts
outfitted with  monitoring patches.  The cotton gloves did not
seem to impede the work efficiency of  the harvesters and offered
no unusual discomfort.  Dermal monitors were worn throughout the
workday with the exception of gloves, which were removed earlier
in Studies 6 and 6a because they became saturated  with moisture
and fruit juice.  The exact time  of monitoring body or hand
monitors was recorded for each subject.
DislodcpahlP Foliar Rpfii^lPfi
     Foliar samples consisted of  3 cm diam.  leaf disks collected
with a mechanical punch first  described by Smith and Little
(1954). The device  is fashioned from a parallel-action paper
punch modified by the installation of a 3 cm diameter metal punch
and die. Each stroke of the punch cuts a leaf  disk and pushes it

-------
 into a 4 oz wide-mouth glass jar which is directly attached to
 the punch and at  the same time serves as convenient sample         £46
 storage container.  A resettable counter activated by each stroke
 of  the device records  the number of leaf disks collected.
     Samples were collected from plants on a random diagonal line
 across the study fields in which the subjects were harvesting
 fruit.   For each 48-leaf disk sample, foliage was randomly col-
 lected from the outer  and inner canopy of the plants.
 Soil Spnplffi
     Soil  samples were taken  in a similar  pattern as  that
 described for leaf disks, by  sampling along  diagonal  lines
 across the plot of land which was being studied.  Samples were
 taken every 8 to  10 rows until six replicates had been  collected.
 The soil sampling device consisted ofalOx8x8cm metal frame
 which, when pressed into the soil, outlined an 80 cm2 area.  A
 flat, rectangular shaped metal  shovel with a 1-cm high rim that
 just fitted inside the metal form, was then inserted into the
 soil, pushed forward until a  soil surface layer of the same area
 could be scooped up.
            of SflmpIPP and Analysis
     All samples taken in the field were kept frozen over dry-ice
or in a deep-freeze until they could be extracted prior to ana-
lysis.  Dermal  monitors and gloves were extracted with 30 and
100   mL of  a  suitable solvent,  respectively, (e.g.  toluene,
methanol, or acetonitrile)  by agitation on a reciprocal  shaker.
If the final analysis was to be performed by high performance

-------
                                                                       247
liquid chromatography (HPLC),  toluene could not be used as an
extracting solvent due to interference with the DV detector.
These  solutions had to be filtered through Durapore (0.45 pm)
filters.
     Dislodgeable foliar residues were washed from the leaf disks
with a 60 ppb aqueous solution  of  dioctyl sodium  sulfosuccinate
(SURTEN) and subsequently extracted into dichloromethane via
liquid-liquid extraction (Gunther, filal.,  1973;  Iwata, fit al.f
1977).  With a rotary evaporator,  the dichloromethane was con-
verted to the solvent of choice for  chromatography  (toluene for
gas chromatography  and acetonitrile for HPLC).   Results are
expressed in weight (pg or ng) per  area.  The area  is one side of
the 3 cm diam. disk,  namely 7.1  cm2.
     Soil samples were sifted through a flO sieve to  remove
gravel and plant debris and dried  In sasuo. at room temperature
overnight.   The  sample was  weighed and then exhaustively extrac-
ted in a Soxhlet apparatus  for  4 hrs with an azeotropic mixture
of acetone-hexane (59:41,  v/v).   As with the dichloromethane
above,  the acetone-hexane was converted to  the solvent suitable
for the particular analytical technique.  Results are reported as
ppm of pesticide in air-dried (less than 0.5% moisture)  soil.
Analysis  of Pesticide Residues
    Captan residues were analyzed by GC on a  packed  column
TOACDR 222 GC under the following operating conditions:

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                                                                         248
     Carrier Cas?  5% Argon in methane
     Carrie^ Zlox:  65 ml/miru
     Inlet Tenperaturei  220°C.
     Cclujnn:   0.9  m x  2 mm  ID Pyrex  packed with 10%  OV-1
          silicone coated on 80/100 mesh SDPELOOPGRT
     Column Tenperaturei   210°C.
     Detector:  63Ni electron capture
     Makeup fias:  Argon-methane, 35 mL/min.
     Detector Temperature;  275°C.
Under  these conditions,  captan eluted at 1.27 min.  Quantifi-
cation was performed automatically by area-integration (H-P
3390A)  and expressed as micro- or  milligrams/sample.  Recoveries
of added captan ranged from 96  to  103%  (Zweig, 1983).
     Vinclozolin residues have been analyzed previously by HPLC
(Cabras, fit al., 1982, 1983).   An  improved capillary GC method
was developed for the analysis  of vinclozolin, the two isomers of
endosulfan (6,7,8,9,10,10-toexachloro-l,5,5a,6,9,9a-hexahydro-6f9-
methano-2,4,3-benzodioxathiepin-3-oxide) and endosulfan sulfate
and was  employed for the analyses of vinclozolin field samples
generated in Study 6b.  The  instrument used was a Hewlett-Packard
5880A equipped with an H-P 7672  Automatic Sampler and Level Pour
Computer and Terminal  (automatic  integrator). The  column was a
12.5 m WOOT silica  capillary column  (0.2 mm, i.d.) coated with
CV-1 silicone  and deactivated with  siloxane.  The splitless in-
jection  mode and a 63Ni electron capture detector (BCD) were
employed.  Experimental conditions for the complete resolution of
                                         8

-------
a mixture of vinclozolin, endosulfan I and II, and endosulfan       249
sulfate were the following.
     Carrier gas (He);  flow § 15 pei; -4 mL/min.
     Septum Flush? 3 mL/min.
     Split Ventt  55 mL/min.
     Make-up yas (5%  methane in  argon); 20  mL/min.  at the
     detector.
     Temperature programi  Time/rise          Temperature (°Q
                            1 min.               62
                            30°/min.             62 - 250
                            1 min.               250
                            30°/min.             250 - 260
                            5 min.               260
     Dnder these conditions, vinclozolin had a retention  time of
6.53 min. (see FIGURE 1).
        One microliter aliguots of standard and sample solutions
were automatically injected.  All  samples were run in triplicate.
Results were accepted when the relative  standard deviation (RSD)
was <5% for standards and <10% for field  and  laboratory samples.
Standard  solutions ranged from 8.7 ng/mL to  870.8 ng/mL.  Over
this 100-fold range,  the ECD response was found to  be  linear.
Whenever the concentration of unknown was outside this range,  the
sample was concentrated in xacjio. or diluted with appropriate
volumes of acetonitrile.  The practical limit of detection was
4.3 -  8.7  ng/mL.

-------
                                                              250
                                  e
                                  •H
                       MINUTES




                        FIGURE  1



Capillary Gas Chromatography of  Vinclozolin Standard  (expe-

rimental  details in text).
                             10

-------
        Recovery studies of vinclozolin foe gloves, patches, and         o c ^
SURTEN solutions (simulated dislodgeable residue extracts)  ranged
from 70% to over 100% of added vinclozolin.
     Carbaryl and methiocarb  residues  were analyzed by  reverse-
phase HPLC using a Waters 6000A Solvent Delivery System, WISP
Automatic Sample Processor, Waters Data  Module and Automatic
Integrator,  and a Model 4530 Variable Wave Length Detector.  A
pBondapak  C-18  reverse-phase  column (25 cm z 2 mm i.d.) was
capable of  separating each of  these compounds without  appreciable
interference  from extraneous  materials originating in the field.
The mobile phase was a mixture of acetonitrile and water, and the
optimum chroroatographic conditions for each compound are  listed
in TABLE 2.
Calculation of Dermal Dose
     Calculation of dose rate per person is made by the following
equation:
             (pg Pesticides)  x [Surface Area of Body Part (cm2)]
    mg/hr « 	
                        [Patch Area (on2)] x Hr x 1000
where "Hr" is hours monitored,  and Vg Pesticide" is obtained
from chemical analyses.  Surface area of body parts is calculated
according  to Popendorf  and  Leffingwell  (1982) using the 50-
percentile  man and adjusting the individual total body surface
from a nomograph linking body weight and height with body surface
(Sendroy and Cecchini, 1954).  "Patch area" is 28  cm2 as ex-
plained above.  Band exposure rates are obtained from pesticide
concentrations on gloves, normalized for "hours worn," because
                                       11

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                                          TARTJ: 2

                     Conditions for HFLC Analysis of Several Pesticides
                           (pBONDAPAK C-18 Reverse-Phase Colum)
Pesticide
Benonyl*
Carbendaziro
Carbaryl
1-Naphthol
Nethiocarb
Acetonitrile:
Water
50:50
50:50
40:60
40:60
65:35
Solvent Flow
(ml/min)
1.5
1.5
2.0
2.0
0.8
Detection
(ran)
286
286
230
230
265
Ret. Tine
(min)
15.8
3.5
4.6
5.1
6.3
% Recovery
98.0
87.0
85.3
98.9
88.2
- 99. 3b
- 100.4b
- 106.7°
- 106 .5C
- 109.1
abenonyl in acetonitrile is stabilized by the addition of 1000:1 (w/w) 1-butylisocyanate
     (Chiba, 1977).
^Zwelg and Gao, 1983.
cZweig, £tal., 1985.
                                                                                           LH

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                                                                     253
gloves,  unlike patches, cover the entire exposure surface area.
                               DJSQESICH
Dermal Exposure £Q ffrp*"*"
     As may be seen in TABLE 3,  the exposure rates of strawberry
harvesters  in Studies 1-5, ranged from 4.70 mg/hr to 17.41
mg/hr or,  normalized to body  weight,  0.082 mgAg/nr to 0.31
mg/kg/hr.  These results compare favorably with those obtained in
previous studies on dermal exposure by strawberry harvesters
(Zweig, fit al., 1983; Winterlin, filiL, 1984).    Dermal expo-
sure rates of  four subjects who were engaged in weeding (Study 3)
were much higher than for harvesters in any of the studies.  We
observed that the four weeders  were stirring up a considerable
amount of dust during their  work activities indicating that dust
                  Mean Dermal Captan Exposure
             by Strawberry Harvesters and Weeders
Expt.No.
1
2
3
3
4
5
Days
Subjects
Post Appl. Occup.
13
26
4
4
3
48
Pickers
Pickers
Pickers
Weeders
Pickers
Pickers
Nos.
20
23
15
4
6
10
Dermal Exposure
mg/hr mgAg b.w./hr
6
4
17
94
16
5
.50(5.08)
.70(4.11)
.41(14.53)
.13(118.4)
.37(3.78)
.88(3.70)
0
0
0
1
0
0
.106(0
.082(0
.310(0
.784(2
.079)
.077)
.200)
.177)
.411(0.118)
.104(0
.072)
                                 13

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 rather than foliar contact and transfer was the source of their       254
 dermal exposure.  This assumption is based on the finding that
 soil samples at  or near the weeding site contained 6.29 ppm
 extractable captan residues.

                            TART.F ±
       Decay of Captan Soil Residues in Strawberry Fields
                        (Studies 1 and 3)
Days Since Last Application*
2
2
8
9
13
13
4
10
Date
(1981)
April 28
April 28
May 4
May 5
May &
May 9
July 21C
July 27
Captan Residues
ppm
3.47
1.58
3.40
0
8.63
2.89
6.29
3.77
aPesticide treatment,  captan 22 - 2.5 kg active ingredient
(a.i.)/ha on April 15  -  18, April 23, April 26, May 10, May 17; 1.7
kg/ha on May 31; 2.2 kg/ha on June 7 and July 17.
b/cStudy dates for Studies 1 and 3, respectively.
     As may be seen in TABLE 4, captan soil residues appear  to be
stable for at least  13 days post application.  The literature on
the decline of captan in soils of  various types is  in conflict.
Munnecke (1958)  claimed that fungicidal activity of captan in
                                       14

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soil  remained  almost unchanged  for 65 days.   Kluge  (1969)         255
confirmed this finding by demonstrating that  the biological acti-
vity of captan did not decrease appreciably during the first six
weeks in two different soils at pH 7.4 and 5.1.  On the other
hand, Griffith and  Ma thews (1969),  using bioassays, showed a
rapid decline of captan within four days after it had been nixed
with  the soil.  On glass beads, the fungicidal activity was
almost quantitatively retained after 21 days.  These results
suggest that  microbiological  degradation in  soil plays a major
role  in the  dissipation of  this compound,  and that different
soils may harbor  different microbiological populations.
     The agricultural practice of strawberry picking is a hand
operation in which the harvester squats,  kneels, and  sometimes
sits between the rows of strawberry plants.  When berries are
picked for the fresh fruit market, the picker will grab the fruit
at the stem about 2 cm from the calix and twist the fruit off the
stem  with a  fast wrist action.  The experienced picker can
perform this operation equally  well with both hands.
     When fruit is  picked for  canning or processing,  it is
handled in a  different manner.  The harvester will pick the fruit
with one hand and pluck the  stem off the berry with the other.
Strawberries harvested in Oregon (Field Study 2) were picked
mostly for canning,  while  in California during the early season
(Field Studies  1 and 3),  for  the fresh fruit market.   Due to
these  work practices, it is possible that the harvesters receive
varying concentrations of pesticides on different parts of the
                                15

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           Anatomical Distribution of Dermal Exposure                      256
               to Captan by Strawberry Harvesters

Ppropnt of Tnfcfll Dermal Rrnosure*
Study 1
Head+Neck
Back+Shoulders
Qiest+Stanach
Lower Legs
Upper Anns
Lower arms
Hands
0
1
1
3
0
7
.65
.37
.17
.30
.59
.20
85.73
2
2
3
1
6
4
13
67
.92
.36
.15
.96
.82
.28
.52
3
1
2
1
10
2
21
59
.90
.81
.78
.33
.46
.17
.55
4 5 Average
0
0
0
0
0
10
87
.32
.39
.25
.95
.24
.18
.69
3
3
3
1
1
9
76
.66
.26
.68
.93
.47
.93
.07
1.89
2.24
1.61
4.69
1.92
12.35
75.31
 aWeighted average.
body.  The distribution of whole-body dose  rates found in the
first five studies in which the major anatomical regions of the
subjects were monitored,  may be seen in TABLE 5.  Harvesters
consistently had the highest exposure on hands (60 - 86%),  lower
arms (7 - 21%),  and lower legs  (1 - 10%), compared  to other parts
of the body.   A possible explanation for  captan residues found on
the lower legs of the workers is that dew during the early
morning hours caused the  lower  pants legs to become water soaked
and contaminated with dislodgeable pesticide  residues.  When the
fields are dry,  dust may  also move up the pants'  legs and deposit
on the skin.
     The dermal distribution of captan among  the four weeders as
                                         16

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shown  in TABLE 6,  demonstrated a different, but not totally
                                                                    257
unexpected distribution pattern of captan exposure.  The highest
dermal exposures were not found on hands,  but on the chest,  head
and neck, and lower arms.  The variability of the anatomical
distribution, however,  was too large to make the type of general-
ization that was made in the case of strawberry harvesters.
                           TARTJ! £
to Captan by Weeders
Bodv Part
Subject
Head+Neck
Back+Shoulders
Ghest+Stanach
Lower Legs
Upper Arms
Lower arms
Hands
aAverage.
Percent of Total Dermal Exposure*
1
1.53
3.32
56.38
10.97
9.43
3.57
14.79

2
78.80
0.13
4.18
0.97
7.69
0.54
7.67

3
35.07
0.18
2.74
0.10
2.09
58.99
0.81

4
2.65
1.62
84.89
6.51
0.47
1.21
2.65

Dermal Exposure to Carbaryl
     On the basis of the results from Studies 1-5, it was
decided that in  subsequent experiments  with strawberry
harvesters, the study  should be limited to three anatomical
regions for the estimation of total body exposure of harvesters,
namely hands, lower arms, and lower legs.
                                         17

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        A summary of  the simultaneous exposure to carbaryl  and        o c o
                                                                        c. JO
>  vinclozolin  may be  found in TABLE  7.   Detailed results on
   carbaryl exposure are reported elsewhere (Zweig, fit Al»r 1984,
   1985). Because dermal exposure on lower legs was found to be
   less than  4% of total exposure, with the exception of one worker
   out of 18, our following conclusions were based solely on hand
   and lower  arm exposures.  Exposure rates on the first day of the
   study were greater than on the next two days.  It was observed
   that morning dew and relative humidity on Day-1 were  considerably
   higher than on either of the other two days of the study.  Pesti-
   cide exposures on Days-1 and -3 in the morning were also found to
   be higher than in  the afternoon.   It was concluded that high
   humidity may have a positive  effect on pesticide transfer from
   foliage or adherence to the cloth monitors.  Two recent investi-
   gations have  been suggestive that dermal  exposure obtained from
   cotton gloves may yield higher values than  would be obtained from
   hand rinses  (Noel,  fit Al., 1983;  Davis,  fit Al»r 1983).  Both
   monitoring methods, however, have their limitations as discussed
   by Popendorf (1985); a comparison of rinse and glove monitors
   with "true" values must await further research for validation.
   Examining TABLES 3 and 7, it is seen that carbaryl dermal expo-
   sure rates are lower than, but of the  same order of  magnitude as
   those found for captan.
   Dermal Ryppfllire to Vinclozolin
       TABLE 8 also has a summary of exposure rates for vinclozolin
   for six observation periods  in Field Study 6b.   Lower leg
                                      18

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                            TART.B 2.

          Mean Denned Exposure by Strawberry Harvesters
                          to Carbaryl
259
Day of Study
1
1
1
1
2
2
2
2
3
3
3
3
Means
Means
Means
Means
Time of Day
AM
PM
All Day
All Day
AM
PM
All Day
All Day
AM
PM
All Day
All Day
AM
PM
All Day
All Day
Body Part
Hands
Hands
Lower Anns
Hands+Anns
Hands
Hands
Lower Arms
Hands+Anns
Hands
Hands
Lower Arms
Hands+Anns
Hands
Hands
Lower Arms
Hands+Anns
Dermal Exposure
(mg/hr)
3.01(1.70)
1.42(0.80)
0.66(0.41)
2.65(1.14)
1.23(0.62)
1.12(0.73)
0.41(0.27)
1.55(0.61)
1.47(0.82)
1.09(0.71)
0.43(0.30)
1.45 (0.69)
1.90(1.38)
1.09(0.71)
0.50(0.35)
1.89(1.00)
aData from Zweig, fit Al.»  (1984, 1985).
                                      19

-------
 exposure concentrations were, again, mostly nondetectable and
 could be considered to contribute insignificantly to total dermal            p < n
 exposure to vinclozolin.  Only one subject exhibited a lower leg
 exposure rate of about 10% of the total, and then only on Day-1.
 Judging front these results, it appears that hand exposure is the
 major target of dermal exposure among strawberry harvesters.  The
 mean hand exposure rate, 0.251 mg/hr,  may be compared  with
 0.027 mg/hr for lower arms.  This observation is consistent with
 results on strawberry harvesters exposed to captan and carbaryl.
     Quantitatively,  however,  it appears  that vinclozolin expo-
 sure was considerably lower for the same group of workers than
 corresponding carbaryl exposures  (0.28  mg/hr 33. 1.89 ng/hr,
 respectively).  A probable explanation for this finding may be
 the  fact that vinclozolin had been applied 14 days earlier than
 carbaryl,  and that lower dislodgeable vinclozolin  residues were
 found (see TABLE 11).
     Band exposure rates for vinclozolin in the morning  observa-
 tion periods were shown to be greater than those found in the
 afternoon (Z = 2.157; N * 54; p < 0.016; large N, unequal vari-
 ances).  Similar  results were  reported  in the carbaryl study
 (Zweig,  fit al., 1984) and are probably related to to the  presence
 of dew on foliage during the early morning hours, which caused
 glove monitors to become quickly saturated with  water.  These
findings are in contrast to the transfer of dislodgeable  residues
on tree crops,  as discussed by Popendorf and Leffingwell (1982).

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                                                               261
Mean Dermal Exposure by Strawberry Harvesters
                to Vinclozolin
Day of Study
1
1
1
1
2
2
2
2
3
3
3
3
Means
Means
Means
Means
Tine of Day
AM
PM
An Day
All Day
AM
PM
All Day
All Day
AM
PM
All Day
All Day
AM
PM
All Day
All Day
Body Part
Bands
Bands
Lower Arms
Bands+Anns
Bands
Bands
Lower Anns
Bands+Anns
Bands
Hands
Lower Anns
Bands+Anns
Bands
Bands
Lower Anns
Bands+Anns
Dermal Exposure
(mg/hr)
0.29(0.17)
0.21(0.12)
0.03(0.04)
0.27(0.16)
0.34(0.23)
0.25(0.20)
0.04(0.04)
0.33(0.20)
0.34(0.66)
0.13(0.09)
0.02(0.01)
0.23 (0.27
0.32(0.41)
0.20(0.15)
0.03(0.03)
0.28(0.21)

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     By the use of Duncan's Multiple Range Test, it can be demon-
 strated that  mean dermal exposure rates for all 18 workers were            262
 not significantly different on any of the three days of the
 study.  The  exceptions to this finding were the afternoon expo-
 sure rates for hands, which were significantly lower on the third
 day than on either of the other two days.
 Dermal  Exposure to
     As is seen in TffiLE 9, anatomical distribution of methiocarb
 exposure by  blueberry  pickers is  quite different  than was
 observed for  strawberry harvesters,  namely that body parts other
 than hands and lower arms showed considerable amounts of pesti-
 cide residues.  The blueberries cultivated on the farm chosen for
 Study 7 is a variety that grows on busies four to six feet high,
 and the chance  of total  body  contact by  harvesters with foliage
 and concomitant pesticide residues was  much greater than that
 experienced during  harvesting strawberries growing close to the
 ground.  Hand exposure on Day-4 post application was signifi-
 cantly higher than on Day-5; a heavy rainfall on the later day
 presumably washed significant amounts of  pesticide residues from
 the foliage and possibly from the body and glove monitors,  which
had become soaked.  The overall total exposure rate for methio-
 carb was comparable with that observed among strawberry harves-
ters exposed to carbaryl.
             foliar Residues
     Dislodgeable foliar residues of pesticides may consist of
pesticide residues absorbed or adsorbed onto foliage or dust
                                        22

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                             TART.E £
           Anatomical Distribution of Dermal Exposure
              to Hethiocarb by Blueberry Harvesters
Days Post ADD! i cation
Body Part
HeadfNeck
Back+Shoulders
Chest+Stonach
Lower Legs
Upper Arms
Lower arms
Bands
Total


4
formal
mg/hr %
0
0
0
0
0
0
2
3
N
.28(0
.13(0
.23(0
- 12
.19) 7.4
.05) 3.4
.09) 6.0
.23(0.10) 6.0
.22(0
.64(0
.05(1
.80(1
.13) 5.8
.49) 16.8
.29) 53.9
.96) —


5
Dosiire


mg/hr %
0
0
0
0
0
0
0
2
N - 6
.13(0.05)
.19(0.09)
.23(0.07)
.34(0.08)
.20(0.07)
.74(0.72}
.31(0.09)
.14(0.85)
6.2
8.8
10.6
15.9
9.7
34.6
14.3
—
particles which  are residing on the leaf surface.  Fractions of
these residues may be transferred to the skin or clothing of
field workers either by direct contact with foliage or by fall-
out of dust aerosols resuspended by work activities.  An earlier
study by Zweig,  £t al., (1983) demonstrated that the ratio of two
pesticides,  captan  and benomyl,  present as a dislodgeable resi-
due, was similar to the ratio found on gloves and patch monitors
worn by strawberry  harvesters.  This was taken as evidence that
the dislodgeable foliar  residue was  being transferred from leaf
surfaces to the  workers either partially or entirely.
                                '

-------
     In order  to determine the  dislodgeable residues on the
day(s) when field workers were monitored for dermal exposure,  it
was important to study the decline of the foliar residues for
several day  or even weeks prior to the beginning  of  a  study.
FIGURES 2,  3  and 4 depict the decline of dislodgeable residues  of
captan and  vinclozolin on strawberry foliage and methiocarb  on
blueberry  foliage.   All  plots are semi-log and fall on straight
lines, indicating first-order kinetics for the decay  of these
pesticides.  Similar conclusions have been propounded for dis-
lodgeable  foliar residue declines  of carbaryl on strawberry
leaves  (Zweig,  fit al.r 1984, 1985).  From the slopes of these
plots, the  half-lives of these compounds existing as dislodgeable
residues can  be calculated  (TABLE 10).
             Half-Lives of Some Pesticides Present
                as Dislodgeable Foliar Residues
Pesticide
Captan
Carbaryl
Vinclozolin
Methiocarb
Crop
Strawberries
Strawberries
Strawberries
Blueberries
Half-Life
(days)
7.1
4.1
4.0
1.7
Reference
Field Expt.
Zweig, fit Al.
Field Expt.
Field Expt.

2
, 1984
6b
7
                                       24

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                                                                265
                             y-0.937-0.042x
                             r-0.850
      -0.2
                       10          20           30
                    DAYS POST-APPLICATION

                          FIGURE 2

Decline of Captan Dislodgeable Residues from Strawberry Foliage
(Field Study 2); log Dislodgeable Residue vs. Days, Post-Applic-
ation. Each plot is  the geometric  means of  2-4  replicates; this
also refers to FIGURES  3 and  4.

-------
 o
2.8





2.4
w

o  2.0
   1.6
   1.2
o
o
   0.8
   0.4
                                    y-3.134-0.0715x

                                    r-0.96
                                                                 266
                 10          20          30          40


                        DAYS POST-APPLICATION



                             FIGURE  3



    Decline of Vinclozolin Dislodgeable Residues from Strawberry

    Foliage (Field  Study 6b); note units of DFR are in ng/cm .
                                  26

-------
The Ratio of Dermal Exposure Rate and nialodymK\» Foliar Bggidue          2 6 /
   Popendorf and Lef fingwell (1982) have reviewed the results of
their field work on the exposure by citrus and  peach harvesters
to organophosphorous insecticides. They concluded that log-log
regression analyses were essentially linear between dislodgeable
foliar  residues and dermal dose rates.  He have now  extended
these regression analyses to include the results for strawberry
and blueberry harvesters exposed to captan, benomyl, vinclozolin,
carbaryl and methiocarb.  The anatomical distribution of dermal
exposure to pesticide by field workers harvesting row or bush
crops may be quite different than that of harvesters of tree
crops,  probably due to the operation of different exposure mech-
anisms.  Nevertheless, the regressions of 43 separate observa-
tions fell on the same straight line (FIGURE 5), and the ratios
of dermal exposures and dislodgeable foliar residues were essen-
tially within an order of magnitude (TABLE 11). The mean value
of 43 observations  [16 from  these studies and 23  from  Popendorf
and Lef fingwell (1983)] was 7.84 x 103 (S.D. 12.2 x 103).  The
ratios for vinclozolin appeared  to be  significantly higher than
the values for carbaryl observed simultaneously.  Since the vin-
clozolin residues  were two weeks older than  the concomitant
carbaryl residues (see above) and considerably lower than all the
others  listed in TABLE 11, it  could be speculated  that the
anomalous ratio derived for vinclozolin is related to aging of
its residues.
                                 m
27

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                                                             268
 u
•-.
 eo
 3.
V)
a
Cd
1
a  -0.2
s
   -0.4
                                   y-1.045-0.176x
                                   r-0.844
                          I
I
I
                                            i
                          3456

                        DAYS POST-APPLICATION
                       8
                             FIGURE 4
    Decline of Methiocarb Dislodgeable Residues from Blueberry

    Foliage (Field Study 7).
                          28

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                                                                269
    (M
     w
     .J
     GO
     CO
          1.5
          1.0
          0.5
      E
      o
tt
I  -0.5
IS

<  -1.0

o
u.
   -1.5
        -2.0
        -2.5
        -3.0
                                       O   O
                                     y-l.OOx-0.603
                                     r-0.904
             -2.0     -1.0      0          1.0      2.0

                       LOG DERMAL  EXPOSURE RATE  (mg/hr)

                             FIGURE 5

Regression Line of Ratios Between  Dermal  Exposure Rates and
Dislodgeable Foliar Residues  of  Various Pesticides and Crops;
data are from this report and Popendorf and  Leffingwell (1982)
  • -2 points with same coordinates.
                                    29

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 Al
O
                                                        TABLE 11

                            Ratio Between Dermal Dose Rate and  Dislodgeable Foliar Residues
Stud/ No. or
Lit. Citation
Study 1
Study 2
Study 3
Study 4
Study 5
Study 6a
Study 6a
Study 6a
Study 6b
Study 6b
Study 6b
Study 7
Study 7
Study 7
Zveig,1983
Zweig,1983
Pesticide
Captan
Captan
Captan
Captan
Captan
Carbaryl
Carbaryl
Carbaryl
Vinclozolin
Vinclozolin
Vinclozolin
Hethiocarb
Methiocarb
Hethiocarb
Captan
Benomyl
Crop
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Strawberries
Blueberries
Blueberries
Blueberries
Strawberries
Strawberries
Dermal Dose
Rate
(mg/hr)
6.50
4.70
17.41
16.37
5.88
2.65
1.55
1.45
0.273
0.329
0.232
6.037
3.80
1.06
39.01
5.39
Dislodgeable
Foliar Residue
(pg/cm2)
2.36
0.71
7.76
2.74
1.72
0.61
0.55
0.24
0.00891
0.00537
0.00524
7.83
2.42
0.59
4.55
0.75
Ratio
xlO~3
2.754
6.620
2.244
5.974
3.418
4.344
2.818
6.042
30.64
61.27
44.27
0.771
1.570
1.802
8.574
7.187
                                                                                                              -vl
                                                                                                              O

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     The units of this ratio are area per tine (viz. cn^hr"1),         271
but the significance of this  relationship is not clearly under-
stood.  The "area" expression may represent the foliar surface
with which the field worker actually comes into contact, or it
may be the hypothetical area of the foliage given quantitative
transfer of the dislodgeable residue  on its surface.
     We subscribe to the  concept put forth by Fopendorf and
Leffingwell  (1982) and Nigg, filal., (1984) to use this ratio as
an empirical factor for the estimation of dermal  exposure by
field workers without involving the workers, themselves, but
measuring, instead,  the dislodgeable foliar  residues in the par-
ticular combination of pesticide and crop under consideration.
The fact that this factor is relatively constant for  a variety of
crops as diverse as citrus and strawberries and holds for dif-
ferent pesticides, suggests that a  constant fraction  of dislodge-
able residues is transferred to the skin or clothing  of personnel
during manual activities  in treated  fields.  Nigg, fit Al.,  (1984)
have recommended that an empirical constant  of 10* be  used to to
make this estimate, but these  researchers calculate  dislodgeable
residues on the basis of two leaf surfaces.  In our work, only a
single leaf surface (projected area) is considered, making the
value of our  ratio about one-half that derived by Nigg's group.
As recently stated by Zweig (1984),  a  rough first approximation
of dermal exposure rate for fruit harvesters based  on dislodge-
able foliar residues  (DFR) may be calculated using the following
                                        31

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expression:                                                              272
         Dermal Exposure Rate (ing hr'1) * 5 x 103 x DFR
This simple transformation suggests a  method for obtaining expo-
sure rates of fruit harvesters in order to establish safe reentry
periods without involvement  of human  subjects.  Experiments are
needed on additional crop/pesticide combinations to further vali-
date the use of this factor.
     Analytical analyses were performed  by H.R.  McLean, C.F.
Truman, R.D. Mills and Ru-Yu Gao, whose valuable contributions
are gratefully acknowledged.   Although the  research described in
this  article has been funded wholly or in part by the United
States  Environmental Protection Agency,  Hazard Evaluation Divi-
sion, through Cooperative Agreement # CR80-9343-01-0 to the Uni-
versity of California at Berkeley, it has not been subjected to
the Agency's  required peer and policy review and, therefore, does
not necessarily reflect the views  of the agency, and no official
endorsement should be inferred.
Cabras,  P., Paolo,  P., Meloni, M.,  Pirisi, P.M., J. Agric. Food
     Chero., 3J&, 569 - 572 (1982).
Cabras,  P.r Paolo, D., Meloni, M., Pirisi, P.M., and Pirisi, R.,
     J. Chromatogr., 256. 176 - 181  (1983).
Davis, J.E., Stevens, E.R., Staiff, D.C., Bull. Environm. Contain.
     Toxicol., 31f 631 -  638 (1983).
Griffith,  R~L. and Ma thews, S., Ann. Appl. Biol., fil, 113 - 118
     (1969).
                                             32

-------
                                                                             273
Gunther,  F.A., Westlake,  W.E.,Barkleyr J.H.,  Winterlin, W. and
     Langbehn, L., Bull. Environ. Contain. Toxicol., A, 243 -249
     (1973) .

Gunther,  F.A., Barkley, J.B. and Westlake, W.E.r Bull. Environ.
     Contain. Toxicol., 12, 641 - 644 (1974).

Iwata,  Y.,  Spear,  R.C.,  Knaak, J.B. and  Foster, R.J., Bull.
     Environ.  Contain. Toxicol., IB,  649 - 655 (1977).

Kluge, E., Arch. Pflanzenschutz, i/  263 - 271  (1969).

Munnecke, DJL, Phytopahtology, 4fi/  581 - 585  (1958).

Nigg, H.N., Stamper, J.B., and Queen, R. M.,  Amer.  Ind. Hyg.
     ABSOC. J., &, 182 - 186  (1984).
Noel, M.E., Zveig, G., and Popendorf, W.J., Abstr. Papers, 185th
     Nat. Meeting Amer. Chem. Soc., CHAS 27  (1983).

Popendorf,  W.J. and Leffingwell,  J.T., Residue  Reviews, fi2/ 125 -
     201 (1982).

Popendorf, W., Accepted for publication in "Proc. Symposium on
     Risk Assessment  of Agricultural Field  Workers Due to Pesti-
     cide Dermal Exposure," Amer. Chem. Soc., Washington,  D.C.
     (Scheduled in 1985).

Sendroy, J., Jr., Cecchini, L.P., J. Appl. Physiol., 2/1-12
     (1954) .

Smith,  G.L., and Little, D.E.,  Cal. Agric., fi, #6, 13 (1954).

Winterlin, W.L., Kilgore, W.W.,  Mourer, C.R., and Schoen, SJU,
     J. Agric. Food Chem., 12.,  664 -  672 (1984).

Zveig, G.,  Gao, Ru-Yu, and Popendorf, W.,  J.  Agric. Food Chem.,
     1L,  1109- 1113  (1983).

Zweig, G.,  Gao,  Ru-Yu, Witt, J.M.,  Popendorf, W., and Bogen,  K.
     Accepted for publication in J. Agric. Food Chem. (1984) and
     •Proc. Symposium on Risk Assessment of Agricultural Field
     Workers Due  to Pesticide Dermal Exposure," Amer. Chem. Soc.,
     Washington,  D.C  (Scheduled  in 1985).
                                               33

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                                                  274
Reentry Simulation Study, Phase I and Phase  II
        Research  performed by

        University of Iowa
        Iowa City, Iowa  52240

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  REENTRY SIMULATION STUDY, PHASE I

                by
     William Popendorf, Ph.D.
        University of Iowa,
Pesticide Hazard Assessment Project
           November 1985

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                                                                         276
                        TABLE OF CONTENTS
SECTION                                                          PAGE

Introduction                                          .              1
Methods                                                             3
Results                                                            11
Conclusions                                                        24
Text References                                                    26

LIST OF TABLES

  I Chemicals with current reentry intervals                        8
 II Literature search logic         _                               10
III Literature search temporal coverage                            10
 IV Summary of reentry recommendations                             23
  V Comparison of current intervals with recommendations            25

LIST OF FIGURES

1  - 20 Residue hazard versus time                                 27
21 - 25 Initial residue deposition versus application rate          54

LIST OF APPENDICES:                                             PAGES

A. Standardized data sheet                                          1
B. Bibliography of selected and related references                   9
C. Computer residue database format                                 3
D. Computer library of chemical coefficients                        2
E. Computer library of crop coefficients                            1
F. Generalized pesticide decay model computer program              22
G. Reentry calculation and tabulation computer program              9
H. Residue hazard tabulation                                       34

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                            Abstract
277
Phase I of this study consisted of retrieval of reported foliar
residue data, chemical toxicity and crop related parameters for
selected organophosphate pesticides, calculation of cholinesterase
inhibition corresponding to the residues and recommend appropriate
reentry intervals based on a Unified Field Model.

Phase II conducts computer simulation studies testing the effect
of both mean residue hazard (dACHE) and its variability upon
harvesters health status in order to define an appropriate criteria
(daily inhibition of cholinesterase or %dACHE) for recommending
reentry intervals.

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                     REENTRY SIMULATION STUDY, PHASE I
                          DRAFT REPORT, Nov. 1985                       278
          University of Iowa, Pesticide Hazard Assessment Project

INTRODUCTION;  •

     "Reentry interval" is the terra given to the time period (usually days)

necessary for a pesticide residue to become safe for a subsequent activity.

The activity of interest in this report is harvesting (although any similar

activity with prolonged, substantial contact with the foliage or other

repository of the residue would be covered within this context).  The

pesticides of interest are those currently regulated by either the U.S.

Environmental Protection Agency (EPA) or the state of California and a

small number of OPs which are not currently regulated by either agency;

these chemicals are predominantly organophosphate pesticides (OPs) many of

which have been historically associated with sporadic incidents of

harvester acute poisonings (Quinby and Lemmon, 1958; Milby et al, 1964;

Spear et al 1975; Spear et al, 1977; and Gunther et al, 1977).

     The precedent for this review and synthesis was a report submitted to

the EPA in 1981 entitled "A Model for Farmworker Protection from

Organophosphate Pesticide Residues"; an only slightly modified version of

this report was subsequently published in Residue Reviews (Popendorf and

Leffingwell, 1982).  These documents outlined a concept and model for

unifying the aspects of pesticide application, pesticide decay, exposure to

the residue during harvest, dose dermal deposition and absorption, and the

harvester's biological response (this submodel was specific to the

inhibition of the neural enzyme acetyl cholinesterase (AChE)), respectfully

called the Unified Field Model by its author.  A subsequent publication

(Popendorf, 1984) outlined some useful applications for the model, further

examples, and some of its limitations.

     Of particular interest in these reports were two needs, (1) to examine
                                          1

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                                                                            279
the necessity for and adequacy of current reentry intervals in comparison
to intervals using the Unified Field Model and reported residue,
toxicologic, and exposure data, and (2) to establish an appropriate
criterion for setting the reentry interval based on an allowable change in
AChE (dAChE) given the natural variability in residues and exposure
patterns intrinsic to real agricultural practices.  Therefore, two phases
of this study were undertaken: (Phase I) to assemble all reported foliar
residue data for the pesticides of interest with the necessary chemical
toxicity and crop related parameters, to calculate the cholinesterase
inhibition corresponding to these residues, and to recommend appropriate
reentry intervals based on the Unified Field Model, and (Phase II) to
conduct computer simulation studies testing the effect of both the mean
residue hazard (dAChE) and its variability upon harvesters health status in
order to define an appropriate criterion (daily inhibition of
cholinesterase or % dAChE) for recommending reentry intervals.
     While these two phases of the study are related, much of each of them
could be and was conducted separately.  Unfortunately, they were not well
synchronized in time, and this draft report of Phase I was completed
without benefit of input from Phase II.  The particular point at which such
input will be important is when selecting the % dAChE criterion for an
assumed 8-hour harvesting workday.  Due to time constraints, a draft report
was prepared using a criterion of 4% as guided by the earlier reports by
Popendorf and Leffingwell (1982), discussed in the Results section, and
presented in Table IV.

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                                                                       280
METHOD;

     The data base for the study was developed through a computerized

literature search initially conducted in October 1981 (supervised  by Norma

Kobzina at the University of California, Berkeley,  Natural Resources

Library).  A subsequent search was conducted in April 1984 (by E.  Rumsey  at

the University of Iowa, Health Sciences Library).   Four data bases were

used:

          1) CHEMLINE    (Chemical Dictionary online) which supplied
                    synonyms and registry numbers for various chemicals,
                    and also named data bases (files) within the National
                    Library of Medicine Computer System (MEDLARS)  where
                    articles on the chemicals were listed.

          2) TOXLINE     (Toxicology Information online) which contains  an
                    indexed file of abstracts relating to human and animal
                    toxicity studies.  This data base is also part of
                    MEDLARS.

          3) AGRICOLA    (Bibliography of Agriculture)

and       4) BIOSIS      (Biological Abstracts) are both owned by the
                    Dialog Information Retrieval Service, and lists by
                    title the articles related to agriculture and life
                    sciences, respectively.
     The object of the literature search was to find articles containing

decay data on dislodgeable foliar residues of organophosphate pesticides

currently subject to either EPA and/or CDFA reentry restrictions.  The

first step was to obtain a list of chemicals and their synonyms and

registry numbers through CHEMLINE.  These names and numbers were then used
                           i
to search TOXLINE, AGRICOLA, and BIOSIS using selected keywords.  At that

time it appeared that some registry numbers had more than one chemical

assigned to them (mixtures); as a result, several chemicals were listed in

the literature search which were not organophosphates.
IhllllSSdw

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                                                                      281
     There were some differences in the cross-referenced keywords  used

within the various bibliographic data base  searches  because of  their unique

structures and features.  TOXLINE was searched for each of the  chemicals

listed in Table I when used with the words  in list (a)  of Table II.   For

AGRICOLA and BIOSIS the list of chemicals was cross-referenced  twice, once

when used with those words in lists (a) and (b)  of Table II, and the other

when used with list (a) but without list (c), i.e. with no mention of

soil/soils.  The period of time encompassed by each  literature  search is

listed in Table III.

     From the printout of references selected through the TOXLINE,

AGRICOLA, and BIOSIS searches, those articles whose  titles were clearly

unrelated to the objective of the study were deleted.  All references even

possibly applicable to the study were located and further screened to those

that did indeed meet the following criteria:

          1)   Article contained data on dislodgeable foliar residue decay,
               as opposed to dislodgeable fruit residues, penetrated
               residues, soil residues or total residues.  In cases where
               authors used organic solvents for removal of residue (as
               opposed to the more established "dislodgeable" method
               using an aqueous solution) but still  claimed that the data
               represented dislodgeable foliar residues, this data was
               included in the data base but the extraction solvent was
               noted.

          2)   Residue data were available  at more than one point in time
               as part of either a table or plot. Decay data with less
               than two points in time were not used for this study,
               although the articles are included in a secondary
               bibliography.



     A standardized data sheet (Appendix A) was used to record the

experimental parameters and methodology of each study, the actual data  set

was copied, attached to the data sheet, and filed.  A bibliography of the

selected references for the study is enclosed (Appendix B) along with

references which may be useful in related studies.

Ihllll85dw

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                                                                         282
     Information from the standardized data sheets and the  original  data

sets were entered into the computer in the format  shown in  Appendix  D.

Each set of decay data, given in days post application and  residue levels,

is preceded by the corresponding ID number and coded variables.  Where only

a graph of data was provided, residue and interval values were determined

by measurement of the graph.  If only an equation  was given in the original

reference, values were interpolated from the equation for days 1, 2,  5, 10,

20, and 30 (days -) post application (as permitted by the duration of the

reported data) and inserted into the residue data  file.

     Other application, environmental, and sampling factors were determined

from each report where possible and included within the library  file as

explained in Appendix C.  Among these factors are:

               - location (by country or state or  area within large  states)

               - crop (see also Appendix E)

               - formulation (WP, EC, etc)

               - application rate (Ib active ingredient/acre)

               - pesticide dilution (gal water/acre)

               - primary extraction solvent (generally water with
                   surfactant)

               - reporting procedure within publication (e.g. 1  or  2 sides
                   of leaf, units, graphical results only)

               - application date

Computer library data files were established for other model variable such

as pesticide toxicitles (LD,Q) as shown in Appendix D and crop dosing

coefficients (k.) as shown in Appendix E.
               a
     These residue data were then used with the other above library data

files and unified field reentry model to assess the anticholinesterase

potential of reported residues.  Two approaches to interpret these  data

                               5

IhllllSSdw

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                                                                       283
were explored.  The first approach relied upon a generalized pesticide

decay model coefficient-fitting program (Appendix F)  in order to

interpolate between and extrapolate from scattered sampling intervals as

reported in the literature to intervals preset by EPA or California and/or

to intervals corresponding to "acceptable" cholinesterase inhibitions.

This approach found only moderate success because the algorithm was not

efficient at establishing the best fit for the twelve coefficients without

assuming certain "simplifying" constraints on the coefficients (which can

effectively reduce the number of coefficients); much operator interaction

was required to establish the range of these coefficients and the

appropriate constraints for each chemical.

     A second approach was not as elegant in that no decay model was used

to interpolate between or extrapolate from reported intervals.  This second

program (Appendix G) merely uses the crop and chemical coefficient library

with other elements of the unified field model to tabulate the resulting

residues in consistent units (pg/cm2, 1-sided) and health effects (percent

AChE inhibited).  Several further simplifying assumptions were made within

the Unified Field Model as follows when used with the second approach:

          1)   Harvest practices for a particular crop in different studies
               or regions are assumed to be not significantly different.
               Therefore, a single crop dose coefficient, k,, was used for
               those crops which have an established k..  Wften necessary
               and possible, crops without a k, are given the k, of a
               similar crop (e.g. peaches and plums, see Appendix E).

          2)   To estimate the dose rate for crops without an established
               k, and without a similar crop (e.g. apples) a default crop
               k, equal to 5000 cm2/hr was assumed.

          3)   The enzyme coefficient K  was fixed at 6.0 (ref. Popendorf &
               Leffingwell, 1982).     e

          4)   Harvester mass (weight) was assumed to be 70 kg.
Ihllll85dw

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                                                                         284
          5)   The ratio of ppm to ng/cm2  was  assumed  to be  the same for
               all studies of a particular crop,  e.g.  1 ppm  »  25 ng/cm2 as
               established by Leffingwell  et al  (1975) for grapes, see
               Appendix E.
     Although several variables affect the decay  process,  only one reentry

interval is currently established for each combination  of  pesticide except

in California for certain crops.  Hence,  to estimate  a  safe  reentry

interval for the majority of harvest settings the data  has been analyzed

only by pesticide.  The remaining variables are noted but  are not listed

separately.  Differences between manually harvested crops  have so far been

found to differ mainly by application rate; machine harvesting or non-

harvesting practices may certainly cause  differences in the  residue-dose

relationships not otherwise reflected in  Appendix E.   Future comparisons

might be done, for instance, among states or regions to examine the

feasibility of separate reentry intervals for different parts of the

country, dependent on the area's climate; however, the  available data base

currently appears too limited in most cases to be used  for comparisons

between such other variables.
IhllllSSdw

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                                                                                     285
                                          Table  I.
          Chemicals with  currently  assigned reentry intervals specified by either  the
          U.S.  Environmental  Protection Agency3  (EPA), the California Department of
          Food  and Agriculture   (CDFA), or both.  Asterisk (*) indicates chemicals for
          which residue data  was reported  (see also Appendix E, chemical coefficients).
CHEMICAL NAME
(see footnote g)

    &



* Azodrin

* Metasystox-R
  Bidrin [Dicrotophos]

* Carbophenothion
    (Trithion)

  Demeton (Systox)

  Endrin

  EPN

*' Ethion

* Ethyl Parathion
    [Parathion-ethyl]
* Guthion
    [ Az inpho sine thy 1J

* Methyl Parathion
    [Parathion-methyl]
* Dialifor (Torak)

  Diazinon

* Dimecron
    (Phosphamidon)

* Dimethoate (Cygon)

* Dioxathion (Delnav)

          Ihl02985dw
V^A3 V K1E,^3 V

Pesticides Regulated
6923-224 TC43750
301-122 TG14200
Pesticides Regulated
141-662 TC38500
786-196 TD52500
8065-483 TF31500
72-208 ID15750
2104-645 TB19250
563-122 TE45500
56-382 TF45500

86-500 TE19250
298-000 TG01750
Pesticides Regulated
10311-849 TD51650
333-415 TF33250
13171-216 TC28000
60-515 TE17500
78-342 TE33500
	 J.INIC.KVA^ 	 r —
EPA3 CDFA
(aoc) Cit P&N G
by EPA Only
2
2
by EPA and California Intervals
2
2 14 14 14
2 577
2
1(2)C 14 14 14
1(2)C 30 14 14
2 30d 21 21
4Se
60f
1 30 14 21
2 21 14
by California Intervals Only
- 75
555
(2)C 14
4-4
(1)C 30 30 30

A





-
-

14
-
14

14
14

-
-
-
-
_
                                             008

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                                                                                   286
LMUUCAL NAMF
(see footnote g)
Disufoton (Di-syston)
* Endosulfan (Thiodan)
Imidan
* Malathion
* Methidathion
(Supracide)
Methomyl (Lannate,
Nudrin)
* Mevinphos (Phosdrin)
Naled (Dibrom)
Phorate (Thimet)
* Phosalone (Zolone)
Sulphur
TEPP
CAS //
298-044
115-297
732-116
121-755
950-378
16752-775
7786-347
300-765
298-022
2310-170
7704-349
107-493
RTF.CS #
TD92750
RB92750
TE22750
WM84000
TE21000
AK29750
GQ52500
TB94500
TD94500
TD51750
WS42500
UX68250

EPAac
(aoc)C
(2)C
(2)C
(2)C

(2)
(DC
(2)C

(2)C
(I)

(2)C
	 INTE
Cit

-
1
30
2
4
1

7
1
4
RVAL
P&N

5
1
_
2
4
1

7
1
4

CDFAb
G

5
1
_
2
4
1

7
1
-

A

-
-
_
_
-
-

-
-
-
Footnotes:
  a 40CFR 170.3 Worker Protection Standards  for Agricultural Pesticides.  Federal Register
       39:16888-16891, Friday, May 10 (1974), which apply to all crops for which registered.

  b 3 Cal Adm Code.   Chp 4, Section 2479.  California Regulations include a 48 hour interval
       for a somewhat different list of  chemicals applied to any crop than are listed by EPA
       (see footnote c).  In addition, a list is included of reentry intervals by specific
       crop abbreviated as follows:
               Cit » citrus
               P&N = peaches and nectarines
                 G = grapes
                 A = apples
               aoc « all other crops, see  footnote c below

  c Numbers in parentheses indicate reentry  intervals for "all other crops" in
       California which differ from EPA  intervals.

  d For application mixtures of not more than 2 Ib AI/100 Gal and rates not more than
       8 Ib AIA.

  e For application mixtures of not more than 2 Ib AI/100 Gal but rates more than 8 Ib AIA.

  f For application mixtures of more than  2  Ib AI/100 Gal.

  g Chemical names in [ ] indicates name as  listed in California; chemical names in ( )
       indicates a second name in California listing.
            jcl!0485dw
                                             OG9

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                                                                      287
     Table II:  Keyword lists searched with "pesticides"  from Table I

                                (b)                 (c)
     degradation                   crop                not  soil
     deterioration                 foliar              not  soils
     dissipation                   leafy
     persistence                   leaves
     residues
     volatilization
     Table III:  Period of time encompassed  by  each  literature search


                                               initially      finally
                                   from           to           to

     CHEMLINE                      1966        Sept  1981      Jan 1984

     TOXLINE                     Jan  1975       Sept  1981      Jan 1984

     AGRICOLA                    Jan  1970       Sept  1981      Jan 1984

     BIOSIS                      Jan  1977       Sept  1981      Jan 1984
Ihl0985dw
                                     010

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RESULTS:                                                                     288

     The  numeric  results of the Phase I studies of the potential impact of

reported  residue  data  is tabulated in Appendix H.  In an effort to focus

the attention  of  this  review on the many different chemicals regulated by

reentry intervals and  to provide a visual overview of Appendix H, the

cholinesterase inhibition  (% delta-AChE, abbreviated dAChE in the computer

programs  and hereafter) potentially resulting from harvester exposure to

residues  of the various chemicals at reported days-postapplication are

plotted in Figures 1 through 20, listed alphabetically.   These values will

often  be  referred to as measures of "residue hazard" herein.

     The  most  striking first impression of these plots is the variability

of those  with  many studies.  This variability stems from both the initial

residues  as well  as their  decay rates.  Before discussing further each of

these  plots and their  significance, the general issue of variability of

application conditions and initial residue level affecting nearly all

chemicals will be addressed.

     Among the more prominent variables affecting initial deposition are

application rate,  mixture  concentration, crop, and method of application.

The "ideal" uniform deposition of 1-lb of chemical applied to a flat 1-acre

plot of land (or  foliage)  can be calculated to be 11 ug/cm2.   Different

crops  and crop spacing will result in different amounts (cm2) of foliage

per acre; for  instance, Turrell (1961) measured the number and size of

leaves on orange  trees of  different ages, from which it can be calculated

that the  area  of  citrus foliage will vary from about 1.5 to 4 times the

land area of the  grove.  Thus, if the 1-lb application were uniformly

distributed upon  only  the  foliage of a citrus grove, the initial deposition

would  be  between  3 and 7 Mg/cm2-  Crops with more or less foliage per acre

would  be  expected to have  a less or more density of initial residue,

respectively.
   jcll0185pc                       Oil

-------
                                                                              289
     All initial depositions included in Appendix H for which application

rate was reported in the literature, are summarized in Figure 21 as a

function of application rate (AIA, Ib active ingredient per acre).  Subsets

of these values are summarized in Figures 22-25 for citrus, peaches,

grapes, and cotton, respectively.  For 1-lb applications these initial

depositions range from 0.1 to 7 pg/cm2.   There is a general tendency in

Figure 21 for the deposition to increase with increasing rates of

application, but a number of other factors affect this pattern.  For

instance, high rates of application are most often associated with lower

mixture concentrations, high gallons of water per acre, more thorough crop

coverage, and higher rates of runoff; all mitigating toward lower levels of

initial deposition.  The additional affects of crop planting practices,

foliage anatomy, and application methods increase the apparent variability.

     Attempts to control for these other factors were considered but found

not appropriate at this time in comparison to application rate, and even

application rate is not a good predictor in all cases.  For instance, when

attempting to isolate the influence of application, rate on deposition

(the slope of the X-Y regression indicated in Figures 22-25), it became

apparent that only for some crops can a reasonable quantitative

relationship be found.  It appears (from admittedly sketchy data) that

initial residues on grapes and peaches increase respectively by 1.9 and 3.3

gg/cm2 per pound of additional material applied; cotton may have a slope

right in this region (circa 3 pg/cm2 per Ib/acre) but there is too little

range in its application rates to tell.   Citrus residues, on the other

hand, increase in a highly variable manner with a mean near 0.75 pg/cm2 per

pound; selecting citrus applications further by chemical did not improve

the scatter.



   jc!10185pc                         012

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                                                                           290
      Incorporating  application rate into future reentry regulations may be

a viable  consideration.  To date the only chemical so regulated is

parathion on  citrus in California.  At first glance this regulation seems

ironic  based  on  the relatively poor correlation between application rate

and  hazard for citrus (Figure 9) in comparison to  the relatively straight

forward application-deposition association for most other crops.  It is

this author's considered opinion (based on experience and the pattern of

decay characterized in Figure 22) that the reason reentry intervals for

parathion on  citrus are based on application rate, was the result more of

the  coincidental typical application of parathion at high application rates

during  seasonal  weather patterns conducive to the formation of persistent,

high hazard residues, than of the only somewhat higher initial residues,

per  se.   Further consideration of incorporating application rate into other

crop-pesticide combinations seems prudent but would require more

information concerning label application recommendations and restrictions.

      In the final analysis, the reentry hazard interpretations summarized

in Table  IV were made on the data as reported, incorporating agricultural

practices  implicitly as reflected in the residues reported.  The one

exception  to  this rule was the residues reported by Gehrich et al (1976,

ref.  //12).  Their study was specifically commissioned to examine the

residue levels and  decay patterns among different pesticides, seasons,

crops,  and regions  following equal applications at the maximum rates

possible.   It is a  landmark report, but the conditions studied are not

necessarily representative of common agricultural practices in all cases.

Therefore,  Figures  1-20 were interpreted in Table IV on the basis of

three factors:

-------
         (I)  the initial mean dAChE as estimated by the Unified            L' *
              Field Model from all reports; thus the initial dAChE
              reflects both the inherent toxicity of the parent-
              pesticide (and any reported metabolites) as well
              as application conditions.  Both the typical hazard
              (mode) and maximum hazard were considered.

         (.2)  the half-life of the cholinesterase inhibition
              hazards estimated from the pattern of decay.
              Note that in Table IV the half-life is sometimes
              preceded by "ca" to indicate "circa" when the decay
              pattern does not appear to fit an exponential model;
              in this case an effective half-life is listed
              corresponding to the rate of decay in the 1 to 10%
              dAChE per day region.

         (3)  optional reentry intervals determined by the days
              necessary for the dAChE 8-hour workday to fall below
              4%.  Two versions of this reentry interval are listed:
              one is the time for the typical residue (mode) to
              fall below the 4% criterion (combining factors 1 and
              2, above), the second is the time for the maximum
              reported residue to decay below the 4% criterion.


1. Azinphosmethyl (Guthion) has been quite well studied with fourteen

references cited covering  4 crops.  The initial residue depositions span

nearly two orders of magnitude.  It is not unexpected that studies of

relatively low residues may not have been pursued for as long a time as

studies of higher residues; thus, residues appear to become more consistent

at longer intervals post-application.  Thereafter, residue hazards appear

to decay exponentially rather slowly, with a half-life of about 3 weeks.

The presence of its oxon was reported in only one study (Iwata, 1980); in

this one case the initial deposition, its hazard, and its half-life all

appear to be outliers, but not more than 25% of the dAChE hazard at any

point is attributable to its oxon.  The recommended reentry interval of 16

to 23 days is consistent with California's standard but much longer than

EPA's 1 day.
   jcll0185pc

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                                                                               292
2. Carbaryl (Sevin) residues were only marginally reported,  but  its  very

low acute toxicity (not to mention its less cumulative dAChE effect  as a

carbamate) result in maximum dAChE hazards of <0.1Z.   Neither agency has

current reentry requirements for this pesticide and no additional

requirements are suggested by this data.



3. Carbophenothion (Trithion) residues have been reported only modestly.

Its typical initial dAChE hazard was near 4%; its maximum initial  residue

hazard did not exceed 10% and was below 4% in 2 days except  when applied at

unusually high rates (studies by Gehrich et al (12) were applied at  8

Ib/acre to match high parathion applications, an apparently  uncommon

practice with Trithion).  Given the apparent agricultural usage

(.application rates) of this pesticide, the recommended reentry interval of

0 to 2 days is consistent with EPA's current standard and much less  than

the California requirement of 14 days; On the other hand,if  the  pesticide

were used at or near 8 Ib AIA, this data would suggest reentry requirements

near 60 days.



4. Chlorthiophos has not been well reported in the literature.  The  only

citation does not report initial depositions, but dAChE responses  in excess

of 15% per day are expected.  It may decay in a biphasic pattern (fast then

slow) and in the one report required about 7 weeks for the hazard  to decay

below the 4% criterion.  Reentry intervals for this pesticide are  not

currently required by either agency but are highly suggested by these data.



5. Dialifor (Torak) residues have again been reported only modestly,

despite the fact that the chemical has been implicated in at least one
   jc!10185pc
015

-------
                                                                                 293
harvester residue poisoning incident (Winterlin, 1982 (ref. 83) and in
California is regulated by a 75 reentry interval.   Reported residues
indicate initial hazards range generally from 3 to 10% and decay at a
moderate rate.  A second set of hazard predictions were made for dialifor
assuming a 10-fold increase in the toxicity of its oxon versus the parent;
this assumption affected very long-term residues several fold, but their
cholinesterase responses were still projected to be circa only 1% per day.
In order to explain the poisoning incidents on the basis of these residues,
either the incorrect portions of the field were sampled, not all the
residue was detected, the dosing coefficient for grape harvesters is
significantly higher than for peach or citrus harvesters, or the toxicity
of the oxon is very much greater than expected.  Even the highest residues
reported were below the 4% dAChE criterion  within 15 days.  EPA currently
requires no reentry for this pesticide, but the data only supports a
recommendation in the range of 4 to 15 days.


6. Dimethoate (Cygon) residues appear to represent a low hazard under all
use conditions reported.  Its highest initial hazard is projected to
represent a 1% dAChE per day response and its half-life is 9 days.  No
further requirement is recommended for this pesticide (California currently
requires a 4 day interval on citrus and grapes).


7. Dioxathion (Delnav) presents a modestly low (1  - 10% dAChE per day) but
unusually long residue hazard (a half-life near 48 days).  Thus, the
typical initial residue hazard would just comply with the 4% per day
criterion but the maximum residue reported would require approximately 70
days to reach this criterion.  A final recommendation concerning the


   jc!10185pc

-------
                                                                              294
adequacy of any reentry interval for this chemical would require more

information on use and exposure patterns, and on any chronic noncholinergic •

health effects associated with the chemical.


8. Ethion residues have been studied and reported in a reasonable number  of

studies.  In most of these studies one or more of its oxons have been

reported, but no acute dermal toxicologic information was found for  either

its monoxon or its dioxon.  Therefore, two interpretations (Figures  8 and

8a and Table IV entries) were made: (1) assuming all metabolites have

toxicities equal to the parent pesticide, and (2) assuming its monoxon is

ten-fold more toxic than the parent (in the range of the oxons of

azinphosmethyl (30x), ethyl parathion (lOx),  methidathion (3x), and

phosalone (5x)) and its dioxon is twenty-fold more toxic (based on the

number of active sites).  Inclusion of the assumed oxon toxicity increased

the typical initial hazard from about 1.5% to 6%, neither of which is

capable of causing an acute clinical poisoning.  This inclusion also

increased the hazard's half-life from 10 to 16 days, respectively.

However, the maximum residue hazards for this chemical when applied  at high

rates in the range of 40%.  The reentry intervals corresponding to the

typical or maximum residues (other than by Gehrich et al (1976) range from

9 to 23 days, intervals considerably higher than the current EPA standard

(1 day) but very much in the range of the current 14 to 30 day California

requirement.


9. Ethyl Parathion residues are no doubt the best reported organophosphate

pesticide.  At the same time the amount of data makes their interpretation

difficult.  As an aid in interpretation, a number of sub-Figure 9's  are


   jcll0185pc                          017

-------
                                                                               295


included in this report, each one isolating the residue hazards by region


(i.e. California, Texas, Arizona, Washington, and Florida).   The apparent


lack of consistency of the residue hazards, particularly between regions


but also within some regions is notable.  But also of particular note is


the similarity among the residues reported by Gehrich et al  for similar


applications within four of these regions.  Thus, most (but  not all) of the


apparent differences among regions appears attributable to and to different


application rates and initial deposits on different crops (parathion


application rates on most crops other than citrus (and even  on citrus in


Florida) are 1-1 Ib/acre or less.  Secondarily, the half-lives of the


residue hazard from more common agricultural applications seem to differ


among the regions and to vary inversely with moisture (rainfall) associated


with the various regions.  The suggested reentry intervals (see Table IV)


closely parallel those currently regulated in California but often greatly


exceed those currently set by EPA (2 days).





10. Malathion has one of the lowest acute toxicities of the  pesticides


studied.  Its residues have not been reported often, but its residue hazard


is well below 0.1% dAChE under all conditions reported.  Thus, no further


reentry requirement is recommended based on acute toxicity.





11. Methyl Parathion residues have been reported on a fairly wide range of


crops; it should be pointed out, however, that lacking other experimental

                                                      2
information, the default dosing coefficient of 5000 cm /hr was assumed for


exposures in cotton.  Considerable variability is apparent in the rate of


hazard decay, more clearly varying inversely with moisture and possibly
   jcl!0185pc
016

-------
                                                                           296
with application rate.  The presence of its oxon was reported in about 20%

of the studies, but only under the high application conditions reported by

Gehrich et al did  the oxon eventually become the predominant residue

hazard.  Thus,  the assumed toxicity of the oxon was rarely important to the

overall dAChE hazard, but in the high application rate condition the two

optional toxicity  assumptions caused the recommended reentry interval to

range from 17 to 27 days.  The highest other residue hazard was on apples

and fell below  the U7. criterion after 8 days.  The generally low

application  rates  kept typical initial hazards in the range of 67.

(depending upon the onon toxicity assumption), and its half-life ranged

from 1-2 days depending upon the crop and climate.  Thus, various

recommended  reentry intervals could be made for this chemical ranging from

1 to 8 days  depending upon crop, region, and application rate.  The longer

intervals are consistent with California's standards of 14 and 21 days;

only the shortest  is consistent with EPA's but it is not inclusive of all

non-California  conditions reported.



12. Methidathion (Supracide) residues were well studied in a small number

of reports.  Application rates in the two citrus growing regions were quite

comparable,  but the initial residue hazards were strongly affected by

sometimes quite different application mixture concentrations (ranging from

a nominal 3  to  6 lb/1000 gal/acre tested in both regions, up to 6 lb/100

gal/acre tested only in California).  Decay patterns were biphasic but did

not differ widely  either among or within studies.  Only in the relatively

dry region was  the oxon consistently found in significant quantities.  The

recommended  reentry times differ among the studies from none to 30 days

primarily because  of the initial deposits and secondarily because of oxon
   jcll0185pc
                                         019

-------
                                                                               297


formation.  These values are generally consistent with California (which


requires either 30 days on citrus or 2 days on all other crops) while EPA


has no current reentry interval for this pesticide.




13. Mevinphos (Phosdrin) residues were very sparsely reported.   Because of


their high toxicity, initial hazards were often quite high,  typically circa


25% dAChE, but their very short half-life under the-conditions  reported


results in recommended reentry intervals similar to California  regulations


of 2 to 4 days (EPA has no additional requirements for this  chemical).


                                            /

14. Monocrotophos (Azodrin) residues were only reported in a few studies.


The inherent toxicity of its initial deposition is sufficient to present


modest dAChE hazards at the outset (typically 8%).  Estimates of its


half-life are limited by the short span of reported studies  but appear to


be circa 2.5 days.  Thus, its recommended reentry intervals  of  3 - 5 days


is about double the EPA standard (California has no additional  requirements


for this chemical).




15. Oxydemeton (Metasystox-R) residues have been reported hardly at all.


The one report listed two widely divergent studies.   The initial deposits


of this otherwise moderately toxic pesticide were quite low,  creating a


maximum dAChE hazard of 1.57..  EPA currently regulates a 2 day  reentry


interval.  Based on this limited data, no further reentry interval can be


recommended.




16. Phenthoate again has been only weakly reported.   It has  a fairly low


toxicity, and its highest residue hazard was only 2% (but on the second
   jc!10185pc
                                        020

-------
                                                                              298
     the earliest reported in that particular study).   This pesticide is


currently regulated by neither EPA nor California and would appear to


satisfy the  4%  criterion without additional requirements.




17. Phosalone (Zolone) residues have been modestly studied. Both the parent


and its oxon have fairly low toxicity, resulting in typical (and


consistent)  initial depositions hazards of only 1.5%.   EPA has no reentry


requirement  for this pesticide, but California requires 7  days for several


fruit crops.  Despite its long half-life of about 11 days, there appears  to


be little justification for adding additional reentry requirements for this


chemical.





18. Phosphamidon (Dimecron) residues have been studied a fair number of


times, but nearly all of these studies have reported the data in units of


ppm on crops for which conversion to ug/cm2 was not possible.  In the one


study interpretable, its initial dAChE hazard was projected (back from the


earliest sample of 2 days) to be about 10%, with a half-life of about 3.5


days.  Thus, recommended reentry intervals are in the range of 4 - 5 days,


twice the current California standard (EPA has no current  requirement for


this pesticide).




19. Phosmet  (Imidan) residues have been studied in 3 cases.  Its initial


depositions were in the expected range, but its low acute  toxicity resulted


in a negligible dAChE hazard (<0.1%) in all cases.
   jcll0185pc

                                      021

-------
                                                                             299
20.  Trichlorfon  (like phosmet) has been only weakly  reported, has somewhat

high initial  depositions, but its maximum dAChE  hazard was just under 1%

with a 1.5 day half-life.  Reentry intervals are not currently required by

either agency and no further requirements are justified by this data.
  jc!10185pc
                                       022

-------
Table IV. Summary of reentry parameters  extracted from reported residue
dAChE hazard analysis via the Unified  Field Model.  Initial dAChE was
estimated from all reports; thus it reflects  both inherent toxicity as well
as application conditions.  The half-life  is  estimated from the pattern of
decay and is preceded by "ca" [circaJ  when the decay pattern does not
appear to be exponential.  Recommended reentry intervals are the days
necessary for the initial dAChE hazard (inhibition expected from 8-hours
working exposure) to fall below 4%; values are listed based both on the
typical residue (mode) as well as on the maximum residue reported.
                                                                            300
Pig.
// Pesticide Name
1 Azinphosmethyl (Guthion)
2 Carbaryl (Sevin)
3 Carbophenothion (Trithion)
4 Chlorthiophos
5 Dialifor (Torak)
5a Dialifor (Torak) *
6 Dimethoate (Cygon)
7 Lioxathion (Delnav)
8 Ethion
8a Ethion *
9 Ethyl Parathion
9a Ethyl Parathion (AZ, citrus)
9b Ethyl Parathion (CA)
9c Ethyl Parathion (TX)
9c Ethyl Parathion (FL.dry)
9c Ethyl Parathion (WA)
9c Ethyl Parathion (AZ, cotton)
9c Ethyl Parathion (FL.wet)
10 Malathion
11 Methyl Parathion
11 thigh appl. rate]
lla Methyl Parathion *
lla [high appl. rate] *
12 Methidathion (conc.,CA)
12 Methidathion (dilute, CA)
12 Methidathion (dilute, FL)
13 Mevinphos (Phosdrin)
14 Monocrotophos (Azodrin)
15 Oxydemeton (Metasystox-R)
16 Phenthoate
17 Phosalone (Zolone)
18 Phosphamidon (Dimecron)
19 Phosmet (Imidan)
20 Trichlorfon
Initial
typical
dAChE
2.57.
<0.1
0.9%
>15. %
5. 7.
5. 7.
0.6%
4. %
1.5%
6. %
18. %
(90) %
60. %
(90) %
15. %
10. %
20. %
5. %
<0.1%
2. %
(60) %
4. %
(62) %
15. %
4. %
2. %
25. %
8. %
1.5%
2.5%
1.5%
10. %
0.1%
1. %
Est.
1/2 Life
days
23.
ca 2.
7.6
19.
12.
* 12. *
9.
ca 48.
10.
* 16. *
10.
12.
7.
7.
7.
4.
2.
2.
ca 1.
2.
4
* 3. *
* 6. *
ca 4.
ca 4.
ca 2.
0.8
2.3
ca 6.
ca 3.
11.
ca 3.6
6.
1.4
Days until
dAChE=4%
mode max
na
na
na
36
4
4
na
na
na
9
22
54
27
21
14
5
5
1
na
na
16
na
24
8
na
na
2
3
na
na
na
5
na
na
16
na
ca 2
36
15
* 14 *
na
70
15
* 23 *
60
60
60
21
ca 45
21
8
5
na
8
17
* 8 *
* 27 *
30
ca 12
na
3
5
na
2
na
4
na
na
   jcllOlSSpc
                                     023

-------
CONCLUSION:                                                                    ^

     A review of the reported foliar residue data has revealed a number of

deficiencies in the reentry intervals currently regulated by both the EPA

and California, as well as some dificiencies in the available information
necessary to recommend better reentry intervals.  One of the most fund-
amental deficiencies is the basic criterion of cholinesterase inhibition

allowed during a workday, on the basis of either acute or chronic in-
hibion.  The former is known to have been associated with harvester
clinical poisoning (e.g. Spear et al, 1977); the latter is hypothesized to

be a potential problem (milby et al, 1964).  For the purposes of this
report, an allowable daily inhibition of 4% was assumed.
     Based on this criterion and the available data, EPA reentry intervals
for eight pesticides appear inadequate in comparison to the Unified Field

Model assessment (not within the range of the optional recommendations in
Table IV); four are marginal (within the low range of the optional recom-
mendations in Table IV); eight are adequate; and none may be excessive.  A

similar balance for California indicates three are inadequate; five are
marginal; eight are adequate; and four appear excessive.

     These conclusions are based on a considerable amount of residue data
not equally distributed among all pesticides listed, nor has the model
been confirmed in all the conditions examined.  However, the model has

been developed under realistic field tests, most of its premises have been

confirmed in a limited number of tests, and its recommendations appear to

parallel experience and regulations in California where pesticide use and

decay conditions may have been most severe.  The conclusions definitely

suggest that improved levels of protection are needed in other regions.
   jcllOA85pc
                                       024

-------
     Table V. A comparison between  the current reentry intervals regulated

by the EPA and by California (as  listed  in Table I) with recommendations

based on the Unified Field Model  with a  4% daily inhibition threshold

(Table IV).
                                                                              302
                                                EPA
                      California
 1  Azinphosmethyl (Guthion)
 2  Carbaryl (Sevin)
 3  Carbophenothion (Trithion)
 4  Chlorthiophos
 5  Dialifor (Torak)
 6  Dimethoate (Cygon)
 7  Dioxathion (Delnav)
 8  Ethion
 9  Ethyl Parathion
10  Malathion
11  Methyl Parathion
12  Methidathion (Supracide)
13  Mevinphos (Phosdrin)
14  Monocrotophos (Azodrin)
15  Oxydemeton (Metasystox-R)
16  Phenthoate
17  Phosalone (Zolone)
18  Phosphamidon (Dimecron)
19  Phosmet (Imidan)
20  Trichlorfon
Marginal
Adequate
Adequate
Inadequate
Inadequate
Adequate
Inadequate
Marginal
Inadequate
Adequate
Marginal
Inadequate
Inadequate
Adequate
Adequate
Inadequate
Marginal
Inadequate
Adequate
Adequate
Adequate
Adequate
Excessive
Inadequate
Marginal
Excessive
Marginal
Adequate
Marginal
Adequate
Adequate
Marginal
Adequate
Inadequate
Marginal
Inadequate
Excessive
Excessive
Adequate
Adequate
   jcllOA85pc
025

-------
TEXT REFERENCES;

California Administrative Code:  Title 3 (Agriculture),  Article 23
(Pesticide Worker Safety), Parts 2479 Field Worker Safety.  Sacramento CA,
(Rev. Jan 1979).

EPA: Reinstatement of certain existing standards.  Fed.  Reg.  39:  16888 (10
May 1974).

Gunther, F.A., et al: The citrus reentry problem:  Research  on  its  causes
and effects, and approaches to its minimization.   Residue Reviews  67:1
(1977).

Milby, T.H., F. Ottoboni, and H. Mitchell:  Parathion  residue poisoning
among orchard workers. J.Amer.Med.Assoc. 189:  351, (1964).

Popendorf, W.J. and J.T.  Leffingwell: Regulating  OP pesticide  residues for
farmworker protection. Residue Reviews 82:  125 (1982).

Quinby, G.E., and A.B. Lemmon: Parathion residues as  a  cause of  poisoning
in crop workers.  J.Amer.  Med. Assoc.  166:740 (1958).

Spear, R.C., T.H. Milby,  and D.I. Jenkins:  Pesticide  residues  and  field
workers. Env.Sci.Technol. 9:308 (1975).

Spear, R.C., W.J. Popendorf, J.T. Leffingwell,  and T.H.  Milby: Worker
poisoning due to paraoxon residue. J. Occup.Med.  19:411  (1977).

Turrell, F.M.: Growth in  the photosymthesis area  of citrus.  Bot.Gaz.
122: 284 (1961).
303
   jcl!0485pc
                                        02G

-------
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                                                                  »»fi ri t lim  of *
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                            10
                              15
                           20
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 i
35
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45
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*> . ''lot of
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                                               i ca t i on , T»»A^  for  Carharvl

-------
Fle««re  T.  i»1.or of rcsirfnr hazard fcor»rion lo»»arithn of T rfAThr)  as  a  function

           of tine fHavs nosr-annl f ca t i on, ^"M  for  Carhonhenoth i on
                                                                                                o
                                                                                                ON

-------
 2 i
 1 -
 0 -
-1 -
-2-
                    —T
                     10
—T
 15
                           —T
                           20
—T
 25
—T
 30
—T
 35
—T
 40
—T
 45
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 50
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 5
'\ . ^lot of
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-------
o
CO
                                                                                                    50
                                                                                    function
                                                                                                      O

-------
o
CO
to
-1 -
                             10
                                                                                             50
                    Sa. W1ot of  residue hazard fconnon logarithm  of T dAChr^ as a function

                       of tine  f#avK  nos t-aonl i ca t i on,  r»"A^ for  nialifor (""oraV.1 v»ith
               the  T.n
                              c;p
                                 of the oxon
to  he 1/inth  that of the parent.
                                                                                                    O
                                                                                                    sO

-------
o
GO
         -2 -
                                                                                                           50
                                                           DPA
                        n1ot of rcsiHiio ba?:ar<* ^connon loparithn of  *

                        of  tlfp  (rfavs nos t-annl i ra t i on ,  nn^>  for   Mrn
as a function
                                                                                                        O

-------
    LDACHE
         2 1
         1 -I
         0 i
CO
        -2 -
                                               -9-
                    i
                    5
 i
10
15
20
25

DPA
30
35
 i
40
45
50
                  7. "lot of  roslrlue hnxnrH  fronton lorarlthn of * rfATh")  as a function
                     of tine  fHav* nost-annllcntion,  n"A>  for  "loxntMon

-------
CO
         -2H
                                                             DPA
<*. "lot nf
   of  Mne
p hn*fir<» ^con-ion  lo«nrlthn  of  T
no.q t -nnnli en t i on ,  r»n/v>  for   rti,
                                                                                           funrtion
                                                                                                            LM

-------
Fl«»ure fta. Plot  of  residue hazard  (common logarithm  of T f1AHhP> as a function
           of  tl«»e  (ftavs post-application, r»i»A> for  Fthion  with tbe T."^o  of
           the nonoxon assune'' to ho 1 / 1 "th  that of  the parent anH the ^toxon
                    to he 1/'Oth  that of  the  parent.

-------
    -0
              50
°a . Mot of residue  hazard (common logarithm
    of tine (Havs  post-nnnl tea 1 1 on, nPA) for
    reported  fron  raltfornia.
of 7 <
-------
                            DPA
f
                                for

                                                                          LH

-------
                                                                35
40
                                                                                 —r
                                                                                 45
                 —T
                  50
                                              DPA
pieure "(c.  plot  of residue hazard  (conmon logarithm  of  T dACbF) as a function
            of  tine Mavs post-application,  ""A) for  Fthvl  ^arathlon as
            reported fron  1'ashi npton, ^ont>< Carolina  and Tpxas.
                                                                                          C7\

-------
o
*-
o
       -2-
                           —T
                           10
—T
 15
—T
 20
—r~
 25
 DPA
—r
 30
—T
 35
—T
 40
—T
 45
—T
 50
          ririire  °rf.  "lot of resl^no  hazard (connon  logarithm of T
                      of M*
-------
 1 -
 o-
-1 -
-2 -
                     10
                    15
20
25

DPA
 I
30
35
40
 i
45
 T
50
*>e . "lot  of  residue* ^azarrf fconiwon  logarithm
    of  tl"e  '''nvs nost-annl icat Ion,  ""A)  for
                                                                        as a function
                                                            Tthyl "arathlon as
                                                                                                   CO

-------
 2 i
 1 -
 0-
-2-
   T
   0
 T
 5
—r
 10
—r
 15
—r
 20
—r
 25
—r
 30
—r
 35
—r
 40
—r
 45
—r
 50
10. i»lot of  residue bar.art*  fconnon  logarithm of  *
    of tlr»e  (<*avn nost-ap»»Mcn t f on,  I'M)  for  ''alathion.
                                                                        ns a function
                                                                                                 •sO

-------
DPA
1?. "lot  of

    of  ti"ie
(connon 1o»»arithn of

                for
                         ns a function
                                              Lsl
                                              r>o
                                              o

-------
-2 -
                            0
—T
 30
—T
 35
—T
 40
—T
 45
—r
 50
                    —r
                    10
—r
 15
—r
 20
—i—
 25
 DPA
           lla.  "lot  of residue hazard  (cornon logarithm  of f dA^hr) as n function
                 of  tlr»p fdavB nos t-annl i cfi t i on,  T"»A) for  Methvl  "arathiop wftfi  an
                         Tnn  for  Its  oxon iM^th  that  of  Its parent.

-------
-2
45       50
                    10
                                                           of
                                                                       ns fl  Function
                                                                                             ro

-------
 1 -
 0-
-1 -
   i
   0
i
5
     i
    10
                          15
 i
20
25
 i
30
 i
35
 i
40
45
 T
50
Pt«»ure  1
"lot of
of ti»ie
                      h/irar^  fcoi-»p»on  toparfthn  of ^
                    nos t-apnl 1 ra t ton ,  "''A)  for   "evlnnhos
                                                                              a  function
                                                                                  i n>.
                                                                                                   04

-------
 2 1
 1 -
 0-
-1 -
-2-
    k*
            r
           5
10
15
20
25      30      35       40
 T

45
 T

50
     Ptpure 1'•. i*lot of roslHnp  bazar** fconnon lo»»arithn of ""  ^AChr) ns a Function
               of tfmp ^Havs pos f-n nnl f ca t ton, n"A) for  *'onocrotonho«s  f
                                                                                     LM
                                                                                     fV)

-------
 21
 H
-H
-21
   I
   0
5
 I
10
 I
15
20
25
30
35
40
45
50
          1 S. "lot of  rrsfHue hazard fcownon loirarlthn  of * d.Ar'hr) as a function
              of ttnr  f^avs nos t-annT i ca t f on, ^"M for   "xv^eneton (Metasvs
                                                                                            rv>
                                                                                            c_n

-------
o
its-
CD
         -2 H
1ft. "lot  of rosier h.izarf'  fconnon  loparltfin  of » HAChr)  as

    of  ttr»p Mavs nost-annl f cntion,  HT»A> for   "lienthoate.
                                                                                        function
                                                                                                                ON

-------
o
c
c.
        -2H
                                                        DPA
17. i>1ot of  rflsfrfue hazar^  (rr»inr»on logarithm  of f

    of tine  f^avjs oost-anol \ ca 1 1 on , ^^M  for   ^hosalone
                                                                               as a  function
                                                                                                      ro

-------
     LDACHE
          2H
          1 -
cn
         -1 •
         -2 H
                     T
                     5
—T
 10
—r
 15
—r
 20
—i—
 25

 DPA
—r
 30
—r
 35
—r
 40
45
50
                        "lot  of  rpsl^tie bazar''  (common  logarithm of  *  flAfhP) as a function
                        of  tine  f-*avs  nop t-annt lea t ion,  r»PA)  for  Pnosnhani rton f^
                                                                                                       CO

-------
o
C:
         2 1
         1 -
         o-
        -2-
                             10

—T
 15
—T
 20
                                             25
—T
 30
35
40
45
50
pl«Mire 1°.  W1ot  of
            of  tfr»p
                                        hnznrH  fronnon  logarithm of  *  ^^rhr) as a function
                                       DOB t-a nnl f ra t ton ,  nf»A)  for  T"iosnet fT

-------
 21
  H
 o-t
-H
-24
                                      20
25
35
40
45
30
50
                    of

-------
to
20-
15-
io:

5
0

: •
1 i
c c
B
3 ^ 3 1 ° D
A B ? F3 CCB c
\ ?BA|B B C "•
U8»IB ce B * i, §
li i i I i I
0123456
§
B
§
B
B
B
B
i°l '
6 B •
i i 1 i
7 8 9 10
                                                                                               in
                                                AIA
       Figure 21.  Plot of initial residue deposition (ug/cm2) as a function
                  of application rate (Ib AIA) for all chemicals and all  crops.

-------
C\J
    RES
     20
     15
     10H
                     T
                      2
                             A
                                  B
                                  B
                                    3
                                    A
                                    A
            1
            B
            B

            B
                                                     *
               8Bi
                                                                 e
                             A
                       A
                       r-\

                       A
                                                                 n
                                                                 •X-
T
4
 5

AIA
T
6
T
7
                                                                                  ID
                                                                                  LO
10
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9

-------
  RES
   20 H
   15-
   10-
   5 -
LT1
    0-
         A
         A
A
A
            B
                                                —I—
                                                  5
                                                 AIA
                                   T
                                   7
T
 9
T
 2
T
 3
T
 4
"T
 6
10
       Figure 2.1. Plot of  Initial  residue deposition (ug/cm2) as a function
                  of application rate  (Ib  AIA)  for  all  chemicals on  peaches,

-------
  15-
  10-
Ln
   5 -
   0-
              A A
                                        ~T
                                        4
—I—
  5

 AIA
 r
10
     Figure 24. ^lot  of  initial  residue deposition (ug/cm ) as a function
                of application rate  (Ib  AIA)  for  all  chemicals on grapes.
                                                                                            CM

-------
00
5 :
o-

1
>
A
^
.— .
A
A
a *
i I I
0 1 2

i t i i i i i 	 r
3456789 10
                                               AIA


     Figure 25. Plot of Initial  residue  deposition  (ug/cmO as  a  function
                of application rate (Ib AIA) for all chemicals  on cotton.
                                                                                           O4

-------
  ioH
en
\O
   oi
         A
         A
              *
                      T
                       2
T
 3
T
4
 5
AIA
~T
 6
~T
7
T
 9
—T
 10
      FiRure 25. Plot of initial  residue  deposition  (uR/cm2)  as  a  function
                 of application rate (Ib AIA) for all chemicals  on cotton.
                                                                 Osl
                                                                 L/-J
                                                                 ON

-------
APPENDIX A: Standardized Data Sheet  for
            recording pertinent data from
            published report.
  LOCATION OF  STUDY	
  DATE OF STUDY
  TYPE OF CROP(s)	
  CHEMICAL(s)  APPLIED (Check one)
  Single Chemical  Applied	
  Multiple Chemicals Applied	
  Multiple Chemicals Applied Separately
  Multiple Applications  of Chemical(s)	
  CHEMICAL(s)  APPLIED        |
                              APPENDIX A


                    Space for
                    citation information.
                                                                               337
  FORMULATION  (Fill  in  the  blank)
   	 WP  	 EC  	 LF    ! 	 WP
       G   Other            j     G
	 EC
Other
LF
  APPLICATION RATE  (Active  Ingredient per 	 )
  1.	 Total/tree  J2.	 Total/tree
    	 Kg/Ha      j  	 Kg/Ha
    	 Ibs/acre   j  	 Ibs/acre
  FORMULATION ADDITIVES  OR  COMMENTS
  1.	 J2.	
                                                     3.
WP
G
	 EC
Other
LF
                3.
                Total/tree
                Kg/Ha
                Ibs/acre
                3.
  MIXTURE (gallons  per  acre)  	
  SAMPLING PROCEDURE  (check one)
    Dislodgeable  residue	   Other residue_
    Leaf Punch 	  Whole Leaf	   Other
    Leaf Area Calculated  as: (check)   One Side
  EXTRACTION SOLVENT  Aqueous	
    Organic (circle one)  Hex     Cloro     Tol
                         (1)      (2)      (3)
  WEATHER     Data  Present ( Amount, if given)
  Rainfall     	   	
  Temperature  	   	
  Humidity	   	
  Ozone         	   	
  Other         	   	
                     Units
            	   Two Sides  	

             MeCl     Benz     Other
             (A)       (5)      (6)
              Residue data presented
                   in Tables 	
                      Graph   	
                    Equation 	
              Leaf Dust Measured:
                   YES / NO
                Form  completed by
                   Date
                           APPENDIX A:  page  1 of  1
                                                                    60

-------
APPENDIX B: Bibliography for Residue Decay-Response Database.
            Not every one of the following citations either
            contained residue data or was included within the
            data base summarized in Appendix H.

 1. Awasthi,M.D., et al:
    Dissapation of metasystox and monocrotophos in or on
    soybean crop residues.
    Indian J Agric Sci. 48(4): 245-247, 1978.

 2. Berck,B., Iwata.Y., Gunther,F.A.:
    Worker environment research: rapid field method for
    estimation of organophosphorus insecticide residues on citrus
    foliage and in grove soil.
    J. Agric. Food. Chem. 29(2): 209-216, 1981.

 3. Bowman, A.U., Oiler,W.L., Kendall,D.C.,  Gosnell.A.B., Oliver,K.H.:
    Determination of foliar residues for safe reentry of agricultural
    workers in the field.
    Arch.Environ.Contain.Toxicol.  11(4):  447-455, 1982.

 4. Charmillot, P.J. and  Blaser, C.:
    Study of the persistance of acephate, phosmet and deltamethrin used
    for the control of the summer fruit tortrix Adoxpphyes orana F.v.R.
    CA/099/065875C
    Rev Suisse Vitic, Aboric. Hortic.  15(3): 195-201, 1983.

 5. Chen.Z. and Yue.R.:
    Degradative dynamics of pesticides in tea leaves  and the selective
    parameters of safe pesticide design.
    CA/099/138268U
    Zhonggo Nongye Kexue (Beijing). 1: 62-70, 1983.

 6. Davis,J.:
    Potential Exposure to Dislogable Residues of Two Formulations
    of Methyl Parathion to Apple Trees.
    Bull Environ Contam & Tox.  27: 95-100 (1981).

 7. Davis,J.E.,  Staiff.D.C.,  Butler,L.C.,  and Stevens,E.R.:
    Potential exposure to dislodgable residues after application of two
    formulations of methyl parathion to apple trees.
    NTIS/PB82-247537
    Govt Reports Announcements & Index (GRA&I), 23: 1982.

 8. Dikshit.A.K. and  Bhattacharjee.N.S.:
    Residues of carbofuran and malathion in  or on soybean crop.
    Indian J Agric Sci.  New Delhi,  Indian  Council of  Agricultural
    Research. 50(5): 441-443, 1980.
                                                                 APPENDIX B

                                                                     :     338
                       APPENDIX B: page 1 of 9          . 1
                                                        6 I

-------
 9.  Everhart.L.P. and  Holt.R.F.:
    Potential benlate exposure during mixer/loader operations, crop
    harvest, and home use.                                                    339
    J.Agric.Food.Chem.  30(2): 222-227, 1982.

10.  Fitzpatrick.G.E. and  Began,M.D.:
    Residue dynamics of acephate and methamidophos in urban dooryard
    citrus foliage. Pompano Beach Florida, August-September 1978.
    Pestic.Monit.J. 14(1): 3-6, 1980.

11.  Gegenava.N.G.,  Klisenco,M.A., and  Pis'mennaya.M.V.:
    Dynamics of carbophos and phosalone decomposition in grape leaves
    and grapes.
    CA/098/067078Y
    Khim. Sel'sk. Khoz. 12:45-47, 1982.

12.  Gehrich, John L., John A. Burkart, Dennis Y. Takade, Eugene R. Turner,
    Stanley D. Allen.  Final Report:  Assessment of Leaf Surface Residues
    for Selected Organophosphorus Insecticides.  University of Utah
    Research Institute, Salt Lake City, Utah (1976).

13.  Gehrich,J.L.,  Burkart,J.A., Takade,D.Y.,  Turner,E.R., and  Allen,S.D:
    Assessment of leaf surface residues for selected oganophosphorus
    insecticides.  NTIS/PB82-230046
    Govt Reports Announcements & Index (GRA&I), 21: 1982.

14.  Habeebullah.B. and Balasubramanian,M.:
    Dissapation and persistance of certain insecticides on/in cowpea pods
    (var. C. 152)
    CA/097/067761V
    Madras Agric. J. 68(8): 517-526, 1981.

15.  Hafner.M. and  Michel,H.G.:
    Investigations on the drift of sulfur and its residues in plants
    (red clover and apple leaves from the variety "golden delicious").
    Nachrichtenbl Dtsch Pflanzenschutzd. 27(2): 24-27- [Eng. Sum.] 1975.

16.  Iwata, Yutaka, Margarete Dusch, Glenn Carman, and Francis Gunther:
    Worker Environment Research*  Residues from Carbaryl,
    Chlorobensilate, Dimethoate, and Trichlorfon Applied to Citrus Trees.
    J. Agricultural and Food Chemistry, 27:1141-1145 (1979).

17.  Iwata, Yutaka, Glenn E. Carman, and Francis A. Gunther:
    Worker Environment  Research:  Methidathion Applied to Orange Trees.
    J.Agricultural Food Chemistry 27:119-129 (1979).

18.  Iwata, Yutaka:
    Minimizing Occupational Exposure to Pesticides:  Reentry Field
    Data- a Recapitulation.
    Residue Reviews 75: 127-147 (1980).

19.  Katiha.S.M. and Nath.A.:
    Persistance of oxydemeton methyl residues in cauliflower
    CA/099/135479C
    J Entom Res. 5(1): 47-9, 1981.


                       APPENDIX B: page 2 of 9

                                                             62

-------
20. Keil, Julian E., C. Boyd Loadholt, Bob L. Brown, Samuel H. Sandifer,
    and Wayne R. Sitterly:  Decay of Parathion and Endosulfan Residues on
    Field-Treated Tobacco, South Carolina-1971.
    Pesticides Monitoring Journal, 6:73-75 (1972).

                                                                              340
21. Keil, J.E., C.'B. Loadholt, S.H. Sandfer, W.R. Sitterly,
    and B.L. Brown: Decay of Parathion Residues on Field-Treated
    Tobacco South Carolina - 1972.
    Pesticides Monitoring Journal, 6:377 (1973).

22. Kido, H., J.B. Bailey, N.F. McCalley, W.E. Yates, and R.E. Cowden.
    The Effect of Overhead Sprinkler Irrigation on Methyl Parathion
    Residue on Grape Leaves.
    Bull. Environmental Contamination and Toxicology 14:209-213 (1975).

23. Kilgore, Wendell W., Ming-yu Li, Ronald L. Mull, Wray Winterlin,
    Nemat Borhani, Jess Draus, Peter Kurtz, Norman Akesson, and
    Wesley Yates:
    Human Physiological Effects of Organophosphorus Pesticides in a
    Normal Agricultural Field Labor Population, A Preliminary Report,
    II.  Scientific Aspects. Food Protection and Toxicology Center,
    University of California, Davis.   56 pages (1977).

24. Knaak, J.B., K.T. Maddy, M.A. Gallo, D.T. Lillie, E.M. Craine,
    and W.F. Serat:  Worker Reentry Study Involving Phosalone
    Application to Citrus Groves.
    J.Toxicology and Applied Pharmacology 46:363-374 (1978).

25. Knaak, J.B., S.A. Peoples, T.J. Jackson, A.S. Fredrickson, R. Enos,
    K.T. Maddy, J.B. Bailey, M.E. Dusch, F.A. Gunther, and W. L.
    Winterlin:
    Reentry Problems Involving the Use of Dialifor on Grapes in the San
    Joaquin Valley of California.
    Arch. Environmental Contamination and Toxicology 7:465-481 (1978).

26. Kraus,J.F. et al:
    Monitoring of grape harvesters for evidence of cholinesterase
    inhibition.
    J.Toxicol.Environ.Health. 7(1): 19-31, 1981.

27- Leffingwell, J. T., R.C. Spear, and David Jenkins.
    The Persistence of Ethion and Zolone Residues on Grape Foliage in
    the Central Valley of California.
    Arch. Environmental Contamination and Toxicology 3:49-53 (1975).

28. Lynch,V.P., Hudson,H.R., and Pianca.M.
    Identification and determination of mecarbam and its major
    degradation products in water and crops.
    PESTAB/81/1797
    Pestic Sci. 12(1): 65-73 1981.
                       APPENDIX B: page 3 of 9

-------
29. Maddy et al:
    CDFA Report //HS-181  (ACF 59-181)
    Worker Health and Safety Unit. A Study of Parathion and Paraoxon        7 *
    Residue in Citrus Groves Following Applicaton of Parathion at           ^^
    Various Dosage and Dilution Rates (Report //HS-181). California
    Department of Food and Agriculture, Sacramento, CA (ca 1975).

30. Maddy, Keith T., and Clifford Smith:
    A Study of the Decay Rates of Ethyl-Metyl Parathion and Endosulfan
    Applied as a Foliar Spray to a Tomato Field in the Sacramento
    Valley of California.  Report //HS-293.
    Worker Health and Safety Unit, California Department of Food and
    Agriculture, Sacramento, California.

31. Maddy, Keith T., G. Sprock, A. Scott Fredrickson, and T. Jackson.
    Parathion Residue on Orange Tree Foliage in Riverside County,
    California, May-June, 1975,  Report //318.
    Worker Health and Safety IfaiLt, California Department of Food and
    Agriculture, Sacramento, California (ca 1976).

32. Maddy, Keith T., Susan Edmiston, Charles Kahn, Lilia Rivera, and
    Terry Jackson.  A Study of Parathion on the Foliage of Peach Trees in
    Stanislaus County, California, June-July, 1977.  Report // HS-395.
    Worker Heath and Safety Unit, California Department of Food and
    Agriculture,  Sacramento, California (ca 1977).

33. Misra.S.S.,  Verma,S.,  Handa.S.K., and Lal.R.:
    BHC and parathion residues on crop of yellow-sarson (brassica).
    Indian J of Agric Sci. 41(3): 276-279, 1971.

34. Nigg, H.N., J.C. Allen, R.F. Brooks, G.J. Edwards, N.P. Thompson,
    Roy W. King, and A.H. Blagg.  Dislodgeable Residues of Ethion in
    Florida Citrus and Relationships to Weather Variables.
    Arch. Environ. Contam. and Toxicology     :257-267 (1977).

35. Nigg, H.N., J.C. Allen, R.W. King, N.P. Thompson, G.J. Edwards,
    and R.F. Brooks: Dislodgeable Residues of Parathion and
    Carbophenothion in Florida Citrus:  A Weather Model.
    Bull. Environmental Contamination and Toxicology 19:578-588 (1978).

36. Nigg, Herbert N:
    Comparison of Pesticide and Particulate Recoveries with the Vacuum
    and Dislodgeable Surface Pesticide Residue Techniques.
    Arch. Environmental Contamination Toxicology 8:369-381 (1979).

37. Nigg.H.N.,  Reinert,J.A.,  Stamper,J.H., and Fitzpatrick,G.E.:
    Dissapearance of acephate, methamidophos, and malathion from citrus
    foliage.     PESTAB/81/1555
    Bull Environ Contam Toxicol  26(1): 267-272, 1981.

38. Nigg, H.N. and J. H. Stamper:
    Comparative Disappearance of Dioxathion, Malathion,
    Oxydemetonmethyl and Dialifor from Florida Citrus leaf and Fruit
    Surfaces.
    Arch. Environmental Contamination Toxicology 10(4):497-504 (1981).


                       APPENDIX B: page 4 of 9

-------
39. Nigg, Herbert N., Leo G. Albrigo, Harold E. Nordby, and James H.
    Stamper:  A Method for Estimating Leaf Compartmentalization of
    Pesticides in Citrus.                                                 -7/10
    J. Agricultural and Food Chemistry 29:750-756 (1981).                 $ 4 
-------
50. Prasad, Rajendra-P. and  Ramasubbaiah.K.:
    Persistance of phosphamidon in bhendi crop Insecticide.
    Pesticides. Bombay: Colour Publications. 16(6): 25-26, 1982.

51. Pree.D.J.,  Butler,K.P.,  Kimball.E.R., and Stewart,D.K.R.:           343
    Persistance of foliar  residues of dimethoate and azinphosmethyl
    and their toxicity to the apple maggot rhagoletis pomonella.
    J Econ Entomol. 69(4): 473-478, 1976.

52. Rajput,G.B.,  Khaire.J.T., and Dethe.M.D.:
    Influence of dimethoate and endosulfan sprays on level of residues
    in/on brinjal fruits.
    CA/100/019264U
    J. Maharashtra Agric Univ.  8(3): 289-290, 1983.

53. Ramasubbaiah.K. and Lal.R.:
    Studies of residues of phophamidon in okra crop insecticides.
    Indian J Entomol. 36(4): 344-351, 1974 (Pub. Aug 1976).

54. Ramasubbaiah.K. and Lal.R.:
    Studies on residues of phosphamidon in cowpea crop
    drosophilamelanogaster, test insect.
    Indian J of Entomol.  37(2): 179-184, 1975.

55. Ramasubbaiah.K. and Lal.R.:
    Residues of phosphamidon insecticide in cabbage crop.
    Indian  J  Entomol. [New Delhi] 40(2): 182-186, 1978.

56. Ramasubbaiah.K. and  Lal.R.:
    Residues of phosphamidon insecticide in mustard crop.
    Indian  J  Entomol. [New Delhi] 40(3): 285-289, 1978.

57- Scheunert,!.  et al:
    Fate of 14C-allylalcohol herbicide in soils and crop residues.
    J.Environ.Sci.Health [B]. 16(6): 719-742, 1981.

58. Sharma.P.B. and Chopra,S.L.:
    Persistance of malathion residues on the cauliflower crop.
    Punjab Agr Univ J Res. 7(2): 216-220, 1970.

59. Shetgar.S.S., Pawar.V.M., Puri.S.N., Raodeo,A.K. and Patil,V.K.:
    Residues and residual toxicity of monocroptophos in/on okra leaves.
    CA/100/019262S
    J. Maharashtra Agric Univ. 8(3): 260-262, 1983.

60. Shinde,V.K.R. and Yadava.C.P.S.:
    Effect of crop stage on phosphamidon residues dissapation from some
    vegetables Eggplants, chilis, peas.
    Pesticides.  Bombay.  Colour Publications.  15(1): 20-21, 1981.

61. Shpirt.M.B. et al:
    Establishment of differential "wating times" in treating fruit and
    vegetable crops with organophosphate pecticides.
    Vopr-Pitan.  (1): 70-72, 1982.
                       APPENDIX B: page 6 of 9

                                               66

-------
62. Shpirt, M.B., Salpagarof,N.S., and Genis.V.I.:
    Predicting the waiting period for harvesting pesticide-treated
    agricultural crops.
    CA/099/018077J
    Zashch. Rast..(Moscow) 4: 19-20, 1983.                                344

63. Singh,M. and Yadav.P.R.:
    Persistance of dimethoate and methyl-demeton on and on pea pod
    shells and their movement into pea grains.
    KEEP/83/09586
    Indian J Entomol. 43(3): 306-311, 1981.

64. Singh,M. and Gupta,D.S.:
    Dissapation of monocroptophos in/on chickpea crop.
    CA/097/176960E
    Indian J Entomol. 43(4): 373-377, 1981

65. Smith,C.N.  et al:
    The persistance and dissapearance by washoff and dryfall of
    metoxychlor from soybean foliage.--a prelimanary study.
    J.Environ.Sci.Health [B].  16(6): 777-794, 1981.

66. Spear, R. C., T. H. Milby, J. T. Leffingwell and W. J. Popendorf.
    Some Findings on the Exposure and Response of Pickers in Parathion-
    Treated Orange Groves.  Delivered at the Annual Meeting of The
    American Chemical Society, Los Angeles.  April 3, 1974.

67- Spear, Robert C., William J. Popendorf, John T. Leffingwell, and
    David Jenkins.  Parathion Residues on Citrus Foliage.  Decay and
    Composition as Related to Worker Hazard.  Journal of Agricultural
    and Food Chemistry 23:808-810 (1975).

68. Spear,R.C., Lee.Y.S., Leffingwell,J.T., and Jenkins,D.:
    Conversion of organophosphate insecticide parathion to paraoxon in
    toxic foliar residues: effect of dust level and ozone
    concentration.
    J. Agric Food Chem. 26(2): 434-436, 1978.

69. Spencer,W.F., Cliath.M.M., and Davis,K.R.:
    Persistance of parathion and its oxidation to paraoxon on the soil
    surface as related to worker reentry into treated crops.
    Bull Environ Contam Toxicol. 14(3): 265-272, 1975.

70. Staiff, D.C., S. W. Comer, and R. J. Foster.
    Residues of Parathion and Conversion Product on Apple and Peach
    Foliage Resulting from Repeated Spray Applications.
    Bull. Environmental Contamination and Toxicology 14:135-9 (1975).

71. Strankowski.K.J. and  Stanley,C.W.:
    Determination of residues of Mesurol and its sulfoxide and sulfone
    in plant, animal and soil samples.
    HEEP/82/04059
    J Agric Food Chem.  29(5): 1034-1037. 1981.
                       APPENDIX B:  page 7 of 9

                                                 67

-------
72. Thompson, Neal P., Herbert N. Nigg, and Robert F. Brooks.
    Dislodgeable Residue of Supracide on Citrus Leaves.
    J. Agricultural and Food Chemistry 27:589-592 (1979).
                                                                        345
73. Verma.S. and Dikshit.A.K.:
    Persistance of different insecticides against pea leaf-miner,
    Phytomyza atricornis Meige
    Indian J. Agric Sci. 52(1): 4-6, 1982.

74. Ware, G.W., Betty Estesen, and W. P. Cahill:
    Organophosphate Residues on Cotton in Arizona.
    Bull. Environmental Contamination and Toxicology 8:361-2 (1972).

75. Ware, G.W., Betty Estesen, and W. P. Cahill:
    Establishment of Reentry Intervals for Organqphosphate-Treated
    Cotton   Fields Based on Human  Data:  I. Ethyl and Methyl
    Parathion.
    Arch. Environmental Contamination and Toxicology 1:  48-59 (1973).

76. Ware, G. W., Betty Estesen, and W. P. Cahill:
    Dislodgeable Leaf Residues of Insecticides on Cotton.
    Bull. Environmental Contamination and Toxicology 2:434-7 (1974).

77. Ware et al:
    Dislodgeable Leaf Residues of Insecticides on Cotton.
    Bull Env Contam & Tox.  11(5):       1974.

78. Ware, G.W., Betty Estesen, and W. P- Cahill.
    Establishment of Reentry Intervals for Organophosphate-Treated
    Cotton   Fields Based on Human Data:  II. Azodrin, Ethyl and Methyl
    Parathion.
    Arch. Environmental Contamination and Toxicology 2:117-129 (1974).

79. Ware, G.W., D.P- Morgan, Betty Estesen, and W. P. Cahill.
    Establishment of Reentry Intervals for Organophosphate-Treated
    Cotton   Fields Based on Human Data:  III. 12 to 72 Hours Post-
    Treatment   Exposure to Monocrotophos, Ethyl- and Metyl Parathion.
    Arch. Environmental Contamination and Toxicology 3:  289-306 (1975).

80. Westlake, W.E., F.A. Gunther, and G.E. Carman:
    Worker Environment Research: Dioxathion (Delnav) Residues On and In
    Orange Fruits and Leaves, in Dislodgeable Particulate Matter, and
    in   the Soil Beneath Sprayed Trees.
    Arch. Environmental Contamination and Toxicology  1(1): 60-83 (1973).

81. Westlake,W.E., Ittig.M., Ott.D.E., and Gunther,F.A.:
    Persistance of residues of the insecticide phosphamidon on and in
    oranges, lemons, and grapefruit, and on and in orange leaves and in
    dried citrus pulp cattle feed.
    J Agric Food Chen. 21(5): 846-850, 1973.

82. Winterlin, Wray, J. Blair Bailey, L. Langbehn, and C. Mourer:
    Degradation of Parathion Applied to Peach Leaves.
    Pesticides Monitoring Journal 8:263-269 (1975).
                       APPENDIX B: page 8 of 9
                                                         68

-------
83. Winterlin, W., W. Kilgore, C. Mourer, R. Mull, G. Walker, J. Knaak
    and K. Maddy:  Dilodgeable Residues of Dialifor and Phosalone and
    Their Oxygen Analogs Following a Reported Worker-Injury Incident in
    the San Joaquin Valley, California.                                    346
    Bull. Environmental Contamination and Toxicology 20:255-260 (1978).

84. Winterlin, Wray, Gregory Hall, Charles Mourer, and Glen Walker:
    Dissipation of Parathion and Paraoxon on Citrus Foliage Dust and
    Dry Soil Surfaces in a Treated Orchard.
    Arch. Environmental Contamination & Toxicology.  11(1):11-121 (1982).

85. Winkler.V.W.  et al:
    Determination of norflurazon residues in mixed crop matrices.
    J.Assoc.Off.Anal.Chem. 64(6): 1309-1311, 1981.

86. Woodham,D.W., Reeves,R.G., Williams,C.B., Richardson,H.,and Bond.C.:
    Residues of dimethoate and its oxygen analog on and in citrus leaves
    following a helicopter treatment of the trees with dimethoate ultra-
    low volume concentrate and high volume spray.
    J Agric Food Chem. 22(4): 731-733, 1974.

87. Woodrow et al:
    Airborne and Surface Residues of Ethyl Parathion and its Conversion
    Products in a Treated Plum Orchard Environment.
    Arch Env Contam & Tox. 6:175-191 (1977).
                       APPENDIX B: page 9 of 9
                                                             69

-------
                                                              APPENDIX C
Appendix Q: Computer database format for reported residues as
            corresponds to INPUT FILE SPECIFICATION (as used by
            program "REEN1").

                                                         format  column
 LINE "1" (precedes each set of residues)

     chem  = name of chemical (abbreviated)                 A8      1-8
             (see "chemco" file for abbreviation code)
     nart  « article number (within reference system)       12    10-11
     ndset = dataset number (within article)                12    13-14
     nox   = number of oxons or other metabolites           II       16
             reported (one line nameing each oxon
             required after optional comments); nox
             cannot be larger than nor can names differ
             in sequence from those specified in the
             library file "chemco".
     loc   = location by state [and within state]           A3    18-20
               AK = Arkanas
               AZ = Arizona
               CA « California
                  CAi = Imperial Valley. CA
                  CAs - Southern CA
                  CAv « Central Valley, CA
               FL • Florida
               GA = Georgia
               IND- India
               SC = South Carolina
               TX = Texas
               WA = Washington
     crop  = crop code (see "cropco" library file);         A6    22-27
             selective searching by crop is an option
             in some programs, e.g. reen2.
     igph  « blank (0) if data are from a table;            II       29
             1 if data points are taken from a graph.
     form  = formulation (eg. SEC, 25WP, etc.)              A4    31-34
               CP = encapsulated, n * % active by weight
               EC = emulsifiable concentrate, n = pounds
                    active per gallon
               WP = wettable powder, n = % active by
                    weight
     aia   = mixture active ingredient per acre             F5.2  36-40
             (Ibs./acre) [1 Liter/hectare =
             0.892 gal/acrej
     gpa   = gallons water per acre                         F4.0  42-45
     ex    = extraction solvent used:                        II      47
               blank/default = aqueous with surfactant
               1 * hexane      4 » Methylene chloride
               2 s chloroform  5 = benzene
               3 « toluene     6 = other (see comments)
                Appendix C, page  1 of 3

                                                                 70

-------
   unit  = units reported                                  II      49
             blank/default = ug/cm2                                      348
             1 = ng/cm2      3 = ppm
             2 = mg/m2       4 = other
   nside = number of sides of leaf used to calculate       II      51
             residue
             1=1 side      2=2 sides
   dapp  = day of application                              12   53-54
   mapp  = month of application                            A3   56-58
   yapp  = year of application                             12   60-61
   ncomm = number of comment lines [optional up to 6]      II      63
   npun  = number of punches total [if unusual]            13   65-67
   isd   = blank if standard deviation not given;           II      69
           1 if given.

LINE  "2" (comments as specified by "ncomm")
   comm  = [optional] 1-6 comment line(s)                A79    1-79
           usually used to cite source reference
           or observations on application, data, etc.

LINE "3"
   lox   = metabolite name(s), one per line;               A30    1-30
           the number of names is not optional but
           must match "nox" as listed in LINE 1.

LINE "4"
   nsam  = number of residue intervals measured;           12     1-2
           1 line [manditory] corresponding to the
           number of residue lines which follow.

LINE "5" (Residue data)
   dpa   = days post application                          F4.0    1-4
   res   = residue value, in units as given in            F6.0   6-11
           original data set, unless transformed
           to standard units (ng/cm2) by REEN1 or
           similar calculation.
   sd    = standard deviation, if reported;               F6.0  13-18
           negative values are % relative deviation
           (coefficient of variation).
           An example is provided on the following page:
              Appendix C, page  2 of 3
71

-------
          example from file "pholon":
11
column

c see
h che-
e mco
m

1
0
n |n
a |d
r |s
t |e
It


n
0
X


2
0
1
o
c


3 4
0 0
c see |ijf |A Jg
r cro-|g|o |I jp
o pco|p|r |A |a
P Xm I 1
it i i
ii i i
i
(
e|u
x|n
s|i
o!t
1|
> 6
) 0
n|d |m Jy
s|a |a |a
i!p IP IP
d|p IP IP
e| 1 I


njn
c!p
o|u
m|
11

C
i
s
d


                                                                                      349
          ethion  :34.01:1:FL :orgval:  :  4EC: 3.00:1200: :l:2:29:may:75:4:160:1.
          Nigg, et al: Dislodgeable Residues of Ethion in Florida Citrus and
            Relationships to Weather Variables.
          Arch Env Contam & Tox.   6:  257-267,  1977.
          wet season
          ethion monoxon
           6
0: 99.4: 5.5:
1: 61.2: 26.3:
3: 7.4: 5.4:
5: 3.0: .9:
7: 2.8: 2.0:
14: 2.0: .9:
ethion :34.02:1:FL
dry season
ethion monoxon
9
0: 141.6: 25.8:
1: 32.8: 8.7:
3: 23.3: 1.8:
5: 16.6: 2.3:
7: 17.1: .9:
14: 16.7: 4.3:
21: 5.1: 1.1:
28: 3.4: 1.7:
35: 4.1: .7:
ethion :34.03:1:FL
wet season
ethion monoxon
6
0: 284.6: 142.9:
1: 124.6: 52.4:
etc. . .
4.1:
6.0:
3.9:
2.7:
1.7:
1.3:
:orgval:



12.0:
2.5:
3.2:
4.0:
5.1:
4.8:
3.9:
2.2:
2.2:
:orgval:



42.2:
21.7:

2.3:
3.6:
1.4:
.8:
1.1:
.5:
: 4EC: 4.50:1200:



1.9:
.2:
.2:
1.1:
.1:
.5:
.5:
1.5:
.3:
: 4EC: 4.50:1200:



3.2: : :
AD.
*t . O . . .

                                                         :l:2:10:nov:75:1:160:1.
                                                         :l:2:29:may:75:l:160:l.
                          Appendix C,  page   3 Of 3
                                                                          72

-------
                                                             APPENDIX D
Appendix D: Computer library of Unified  Field Model Chemcial Coefficients.

            "CHEMCO" is a tabulation of  chemical codes, their
            dermal LD50 values, the number  of metabolites
            possible for each chemical,  common or trade names,
            and whether the reentry interval is regulated by EPA
            (E) or California (C)  or both.  Data for dial,
            ethion, and mep are replicated  in a second set of
            parameters with the suffix "2"  in which 1D50 values
            for the metabolites were assumed to be different from
            the parent.
                                                                            350
columns allocated to each parameter are as follows:
1-8 10-13 15 17-41(=25) 42-66(=25)

azinme

carbaryl
car bop



chlort



dcroto
demet
dial

dia!2

diaz
dimeth

dioxat
endrin
epn
ethion


ethio2


etp

malat
mep

mep 2

i i
220 1
7
4000
40 3
40
40
40
58 3



42
11
124 1

124 1
12
640
610 1

120
15
127
153 2


153 2
15
7
14 1
1
4444
67 1

67 1
7
i
azinphosmethyl
azinphosmethyl oxon
carbaryl
carbophenothion
carbophenothion oxon
carbopheno. sulfoxide
carbophenothion sulfone
chlorthiophos
chlorthiophos sulfoxide
chlorthiophos sulfone
chlor. oxon sulfoxide
dicrotophos
demeton or demeton-s
dialifor
dialifor oxon
dialifor
dialifor oxon
diazinon
dimethoate
dimethoxon
dioxathion
endrin
epn
ethion
ethion monooxon
ethion dioxon
ethion
ethion monooxon
ethion dioxon
ethyl parathion
ethyl paraoxon
malathion
methyl parathion
methyl paraoxon
methyl parathion
methyl paraoxon

[Guthion]

[Sevin] 63-252 FC59500
[Trithion]



21923-239 TF15900



[Bidrin]
[Systox]
[Torak]

[Torak]

[Spectracide]
[Cygon],[De-Fend]

[Delnav]
-chlorinated HC-
[EPN-300]
[Ethion], [Nialate]


[Ethion], [Nialate]


[Phostox] , [Thiophos]

[Carbophos]
[Metron]

[Metron]

69 71
i i _ i _ i
i i i i
E C
n ii

E C
ii n
n ii
n ii




E C
E C
C
n
C
II
C
C
It
C
E C
E C
E C
n n
n n
E C
n n
ft ti
E C
n n
C
E C
n n
E C
n n
                Appendix D,  page  1  of 2
73

-------
methom
met ion

mevin
monoos
naled
oxyme
phenth
pholon

phorat
phosam
phosmet
tepp
trie

73 1
20
4.5 1
119
800
165
700 1
1530 1
380
4
124
1550
2.4
2000
endosulf
                methomyl
                methidathion
                 methidathion  oxon
                mevinphos
                 beta isomer
                monocrotophos
                naled
                oxydemeton-methyl
                phenthoate
                 phenthoate oxon
                phosalone
                 phosalone oxon
                phorate
                phosphamidon
                phosmet
                tetraethyl pyrophosate
                trichlorfon
  carbosulfan
  chlorpyrifos
  disulfoton
2 endosulfan
   alpha isomer
   beta isomer
  propargite
  oxymyl
  sulphur
[Lannate],[NudrinJ
[SupracideJ

[PhosdrinJ

[Azodrin]                  E
[Dibrom]
[Metasystox-R]             E
Fenthoate 2597-037 AI78750

[Zolone]

[Thimet]
[Dimecron]
[Imidan]
[TEPP],[Vapotone]
[Dylox] 52-686  TA07000

[Advantage]

[Di-syston]
[Thiodan]
                                                       C
                                                       C
                                                             351
                                                       c
                                                       II
                                                       c
                                                       c
                                                       c
                                                       c
c
II
                                         [Omite]
                                         [Vydate]
                chemical requested not on  file
                Appendix D, page  2 Of 2
                                              74

-------
                                                                APPENDIX E
Appendix E: Computer library of Unified Field Model Crop Coefficients.      352

            "CROPCO" is a tabulation of crop codes, their dosing
            coefficient (K,), the full name of the crop, and the
            leaf density (estimated (as noted by ?) when
            otherwise unknown) to be used to convert residue
            reported as ppm to ng/cm2.  For purposes of
            calculation, when the K. was unknown,  a conservative
            (high) default value corresponding to  5.0 (5000
            cm2/hr) was assumed.  Some replicated  crop codes were
            included to match on crops coded within the data base
            which were sometimes right-justified.

            columns allocated to each parameter are as follows:
            1-6        12-15      23-42(=20)           45-48 49
1 1
apple
apple
artchk
cabbag
chili
chili
citrus
cotton
cowpea
grape
grape
graper
grapet
grapew
grapfr
lemon
lemon
lettuc
mustar
okra
okra
orange
orgnav
orgval
peach
peach
plum
plum
sobean
tobaco
tomato
wheat
kd
i i i i i
3.5
3.5




5.1


3.5
3.5
3.5
3.5
3.5
5.1
5.1
5.1
5.1



5.1
5.1
5.1
1.9
1.9
1.9
1.9




=
i i i i i i i
apple
apple
artichoke
cabbage
chili
chili
citrus
cotton
cowpea
grape-unclassified
grape-unclassified
grape-raisin
grape-table
grape-wine
grapefruit
lemon
lemon
lettuce-unclassified
mustard
okra
okra
orange-unclassified
orange-navel
orange- Valencia
peach
peach
plum
plum
soybean
tobacco
tomato-unclassified
wheat
crop not on file

20. ?
20. ?




27.5
25. ?

21.
21.
21.
21.
21.
27.5
27.5
27.5




27.5
27.5
27.5
20. ?
20. ?
20. ?
20. ?

20. ?
17. ?

=
                                                              ug/cm2
                Appendix E,  page  1  of 1
                                                            75

-------
APPENDIX F: A Generalized Pesticide Decay Model Computer Program.        _    353

     In order to interpolate, extrapolate, and tabulate two-component (parent
and one metabolite) residue data from any single study to a preselected
criterion for re-entry days of specific interest to this report, a generalized
four compartment submodel was investigated.  This submodel is depicted
diagrammatically in Figure Fl.  Conceptually, this submodel assumes that
the initial parent residue is partitioned on the leaf into fast and slow
decay compartments.  Each of these compartments can decay by two routes; it
can either become a metabolite (e.g. oxon) or become nonmeasureable (e.g.
by vaporization, hydrolysis, leaf absorption, etc).  One additional route
attributable to material in the fast decay compartment is a transition by
various mechanisms from the relatively unstable (fast) compartment into the
environmentally protected (slow) decay compartment.  The metabolite is also
partitioned into two parallel fast and slow compartments both initially and
as a result of decay from the parent, and both metabolite compartments are
susceptable to transitional pathways identical to their corresponding
parent compartments.
     In nature, the partitioning is dictated by natural forces.  In a model,
the partitioning is accomplished by fitting coefficients of the equations
characterizing each compartment and pathway to the experimental data .
Pesticide decay is most commonly characterized by first-order differential
equations, i.e. that the rate of decay is proportional to the amount material
present (e.g. Popendorf and Leffingwell, 1978).  The subscript numbers
assigned in Figure Fl were chosen pragmatically to permit the modelling of
single component pesticides (those without measureable metabolites) by only
the first 5 coefficients, versus 12 for two component (four compartmet)
residues.  Thus, the amount of material present in each compartment is
designated as follows:
                   fast compartment      slow compartment
     parent              a1                    a^
     metabolite          a..                   a..

The corresponding kinetic coefficients were designated as follows:
                   fast compartment      slow compartment
     parent to           a.                    a,
       nonmeasureable
     parent fast         a..
       to slow
     parent to           a&                    a._
       metabolite
     metabolite  fast    a7
       to slow
     metabolite  to      a.                    a.
       nonmeasureable

     A generalized pesticide decay FORTRAN computer program was developed
during this study to fit the coefficients to the reported data.  A number of
difficulties were encountered with this approach, among which were that it was
time consuming (requiring considerable operator interaction), the data was
often sparse or did not include initial residues, and the improvements in
smoothing the variability among reported residues within any one study was
outweighed by the much larger variability between studies for any given
pesticide.  Nonetheless, the following program can estimate the coefficients of
the model described above.

                                                            76
                     APPENDIX F: page  1 of 22

-------
                                              354
APPENDIX F: page  2 of  22        -      ' '

-------
                                                              355
  "fast"
  Parent
  "fast"
Metabolite

    An
                               Y
                   nonmeasureable
  "slow"
  Parent
   "slow"
Metabolite

    A12
   Figure Fl.   Schematic diagram of generalized pesticide
   decay model with zero or one metabolite.  Coefficients
   defined as  used in accompaning algorithm.
                                                  78

-------
      program REPAID
APPENDIX  F
       356
C	 EPA version of Rose MAIN LINE PROGRAM
C	 originally adapted from ROSENBROCK HILLCLIMB program in
C                'OPTIMIZATION TECHNIQUES WITH FORTRAN'
C                   J.L. KUESTER & J. MIZE PG 386.
C	 THIS SPECIAL HILLCLIMB PACKAGE WAS WRITTEN FOR RESIDUE DECAY ANALYSIS
C     with a model of 10 coefficients.
C	 MODIFICATIONS FOR IBM 1130 BY W. POPENDORF (1974)
C	 further modifications in lower case for FORTRAN 77 by W. Popendorf (1984)
C     USE IN GOOD HEALTH.


C	 THE FOLLOWING VARIABLES can be read from a special RPRAM file
C             [defaults are provided for in all cases following line 36]:
C     LOOPY = MAXIMUM NUMBER OF STAGES TO BE CALCULATED  (10 to 20 IS GOOD)
C     NCOEF = NUMBER OF COEFFICIENTS (UNKNOWNS) WITH FIRST GUESSES
C             [usually set to 0 to use defaults]
C     NOASK = an index setting logical LASK to bypass user options after
C             selecting filenames, thus operating in an unattended batch mode
C     NSTEP - STEP SIZE CONTROLER: 0 FOR ORIGINAL STEP SIZE AFTER ROTATION
C                                  1 FOR RETENTION OF SIZE PRIOR TO ROTATION
C     PR      NUMBER OF STAGES BETWEEN PRINTED OUTPUTS  [3 is default];
C             A stage is when all E's have reversed direction twice.
C             Because 2 is an even number, this routine has a tendancy to
C             overestimate all coefficients (which for pesticide decay tends
C             to underestimate especially oxons); so it is better to
C             underestimate the value of each first guess.
C     delF  = THE ACCEPTABLE LIMITING DIFFERENCE IN THE OBJECTIVE FUNCTION
C             BETWEEN PRESENT AND PRIOR STAGE  [l.OE-6]
C     EV      Sets VECTOR OF INITIAL STEP SIZES [ 0.01 ];
C             original ROSE permitted setting individual E's.
C	 the following are PROGRAMMED VARIABLES
C     DA    = A GENERAL STORAGE VECTOR (MAX LENGTH LIMITED BY DIMENSION)
C     DELE  = THE MINIMUM STEP SIZE BEFORE PLOTTING RESULTS FOR USER
C     LA      MAXIMUM NUMBER OF NCOEF PERMITTED BY ARRAY LIMITS AS WRITTEN
C     MM    = +1 FOR MAXIMIZATION	 -1 FOR MINIMIZATION
C     NCC   = NUMBER OF VARIABLES PLUS IMPLICIT CONSTRAINTS (SPECIFIED BY CX)
C     N     = NCC (see line 40-2)
C     NinDA = NUMBER OF DATA POINTS TO BE READ AND STORED IN DA
C     NIV   = NUMBER OF INPUT VARIABLES (KNOWNS) WITHIN STORED DATA SET
C     NPAR  = MAXIMUM NUMBER OF DA PERMITTED BY ARRAY LIMITS AS WRITTEN
C     X       MULTIPLICATION or Sealer FACTORS UPON FIRST GUESSES;
C             these are the variables actual optimized.
C
C	 INPUT FILE SPECIFICATION (same file as for "REEN1)
C     chem  = name of chemical (abbreviated)                  A8
C             (see LDvals file for abbreviation code)
C     nart  = article number                                  12
C     ndset - dataset number                                  12
C     nox   = number of oxons or other metabolites reported   II
C     loc   = location by state (except for CA: location by   A3
C               region within state, eg.


                     APPENDIX F:  page  3 of 22               79

-------
C               AZ = Arizona
C               CA « California                                         357
C                  CAi • Imperial Valley, CA
C                  CAs « Southern CA
C                  CAv = Central Valley, CA
C               FL = Florida
C               SC = South Carolina
C               TX = Texas
C               WA « Washington
C     crop  = crop code (see cropco file)                     A6
C     igph  * blank (0) if data are from a table,             II
C              1 if data points are taken from a graph
C     form  » formulation (eg. SEC, 25WP: etc.)               A4
C               CP = encapsulated
C               EC * emulsifiable concentrate
C               WP = wettable powder
C     aia   * active ingredient per acre (Ibs./acre)          F5.2
C     gpa   = gallons water per acre                          F4.0
C     ex    = extraction solvent used:                        II
C               blank/default * aqueous
C               1s hexane      4 « Me chloride
C               2     - chloroform  5 » benzene
C               3     - toluene     6 = other (see comments)
C     unit  = units reported                            *     II
C               blank/default « ug/cm2
C               1     * ng/cm2      3 * ppm
C               2     « mg/m2       4 « other
C     nside = number of sides of leaf used to calculate       II
C               residue
C               1=1 side      2 « 2 sides
C     dapp  = day of application                              12
C     mapp  = month of application                            A3
C     yapp  = year of application                             12
C     ncomc «= number of comment cards, up to 6                II
C     npun  = number of punches total                         13
C     isd   = blank if standard deviation not given,          II
C             1 if given
C     comm  = comment line                                    A80
C     lox   = metabolite name                                 A30
C     nsam  = number of residue intervals measured            12
C     dpa   = days post application                           F4.0
C     res   = residue value, in units as given in             F6.0
C             original data set
C     sd    * standard deviation, if given                    F6.0
C

      INTEGER      PR.NE(IO)
      REAL         LC,DA(120)
      real         AL(10),B(10t10).BX(10),D(10),E(10),EINT(10).H(10)(
     +             PH(10),V(10,10),W(10,10),X(10),Z(10)
      integer      ex, unit, dapp, yapp
      real         dpa(15), res(15,3), sd(15,3), adif(3),pdif(3)
      character*!  file
      character*3  loc, mapp
      character*4  form
                     APPENDIX F: page  4 of 22
80

-------
       character*6   crop
       character^S   chem
       character'" 12  input, output, newin
       character*30  lox(2)
       characterise  spec, comro(6), data(15)
       logical      lfile,lask,init,term

 C	  ni = unit specifier for input filename
 C	  no =  "      "       "  output   "  various fit results
 C....  nu =  "      "       "  user (screen and console)
 C	nx =  "      "       "  new input file with coefficients
 C	npram =      "       "  rpram  "    "  (rose parameters)
       NU    =0
       NI    =2
       NO    =3
       NX    = 4
       NPRAM = 5
       maxc  = 8
       open (npram,file='rpramlO')

     2  write  (nu,1003)
  1003  format (' Type pesticide INPUT filename, up to 12 characters:1)
 C....  (for code, see LDvals library file)...
       read   (nu.lOOA) input
  1004  format (a!2)
       if     ((input .eq. 'quit').or.(input .eq. 'exit').or.
     +       (input .eq. 'stop').or.(input .eq. 'end')) go to 30000
  1006  format (al)
       open   (ni, file=input)
       rewind ni
       xv    =0.0

       write  (nu,1007)
  1007  format (/,' A duplicate inputfile SHALL be created herein with new
     + model coefficients',/,' Type NEW filename, up to 12 characters:')
       read   (nu,1004) newin
       open   (nx, file=newin, status='new')

       write  (nu.1008)
  1008  format(/,' Do you want model results also written to disk? Y/N ')
       read   (nu,1006) file
       call yes(file.lfile)
       if      (.not. Ifile) go to 20

       write  (nu,1009)
  1009  format  (' Type general OUTPUT filename,  up to 12 characters:1)
       read    (nu,1004) output
       open    (no, file=output, status='new*)
       rewind  no

   20 continue
C.... reading data specification line
      read   (ni,2001,end=24) chem,nart,ndset,nox,loc,crop,igph,form,
     +                      aia,gpa,ex,unit,ns ide,dapp,mapp,yapp,ncomc,
     +                      npun.isd
        358
                     APPENDIX F: page  5 of 22
81

-------
      write  (nu,2001      ) chem,nart,ndset,nox,loc,crop,igph,form,
     +                      aia.gpa,ex,unit,nside.dapp.mapp,yapp,ncomc,
     +                      npun.isd
 2001 format (a8,Ix,2(12,Ix),il,lx,a3,Ix.a6,Ix,il,lx,a4,lx,f5.2,Ix.f4.0
     +        ,lx,3-(il, Ix),i2,lx,a3,Ix,i2,lx.il,Ix,i3,lx.il)
      backspace ni
      read   (ni,2002) spec
      nres  = nox+1
      NCOEF « 4+(2*nox)
      if     (nsam .eq. 2 .and. nox .eq.  0) NCOEF=2

C.... reading up to 6 comment lines
      read   (ni,2002) (comm(i),i=l,ncomc)
      write  (nu,2002) (comm(i),i=l,ncomc)
 2002 format (a80)
C.... reading the name of the oxons or other metabolites
C.... and model coefficients 9 and 10
      read   (ni,2003) lox,da(9),da(10)
      write  (nu,2003) lox,da(9),da(10)
 2003 format (2a30,2el0.4)
C.... reading the number of samples in the following set of data,
C.... also the number of previous runs and goodness of  fit  indices
      read   (ni,2004) nsara,nruns,(pdif(kj.k*!,nres),(adif(k),k=l,nres)
      write  (nu,2004) nsam,nruns,(pdif(k),k=l,nres),(adif(k),k=l,nres)
 2004 format (I2,i3,6el0.4)
C.... reading residue data ...
      do 21 j = l.nsam
      read   (ni,2005) dpa(j),(res(j,k),sd(j,k),k=l,nres)
      write  (nu,2005) dpa(j),(res(j,k),sd(j,k),k=l,nres)
      backspace ni
      read   (ni,2002)   data(j)
   21 continue
 2005 format (f4.0,lx,6(f6.0,lx))
C.... reading model coefficients 1-8
C.... do-loop sets da s previous A (or Z)
C.... unless this is the first run of program with new  data  (pesticide)  file
C.... then loop sets da = 0 in preparation for subroutine "TX".
      DO 22 i = l.maxc
      if     (xv .ne. 1.0) z(i)=0.0
      da(i) = z(i)
   22 continue
      if     (nruns .eq. 0) go to 23
      READ   (NI.2006) (DA(i),i=l,maxc)
      write  (nu,2006) (DA(i),i=l,maxc)
 2006 FORMAT (8E10.4)

   23 if     ((nsam*nres) .ge. ncoef) go  to 35
      write  (no,1013) nart.ndset
      write  (nu,1013) nart.ndset
 1013 format ('  The data for article1,i3,' dataset',i2,
     +       '  are insufficient to model!1)
      go to 20
   24 write  (nu,*) 'Reading end of old input datafile.'
      go to 2
                     APPENDIX F:  page  6 of 22              Q2

-------
 C....  subroutine  to convert data to ug/cm2 projected area
 C....  units  may be nonstandard and must be individualy converted.
    35  call units(res,sd,nsam.nres,unit,nside,crop)
       if      (unit  .It. 4) go to 36
       write   (no,1014) nart, ndset
       write   (nu,1014) nart, ndset
  1014  format (' Nonstandard units in article1,i3,' dataset',i3,/,
     +        ' - further calculations are discontinued!1)
       go  to  20
    36  continue

       CALL tx(DA,dpa,res,nsam.nres,ncoef)

       lask  = .true.
       rewind npram
       read   (npram,4001) loopy,nco,noask,nstep,pr.delF.ev
  4001  format (5i2,2fl0.9)
if
if
if
if
if
if
if
LA
dele
MM
NCC
next
niv
NinDA
(loopy .eq.
(nco .ne.
(noask .eq.
(nstep .ne.
(pr .eq.
(delF.eq. 0
(ev .eq. 0
= 10
= l.e-8
= -1
= ncoef
= 1
= 2+nox
0)
0)
0)
0)
0)
.0)
.0)






loopy =
ncoef =
lask •
nstep =
pr
delF -
ev =






20
nco
.false.
1
3
l.e-6
0.01






= NCOEF+(nsara*niv)

                                                                        *
                                                                        *
   37 CONTINUE                                                          *
      XV    = 1.0                                                       *
      DO 200 K = l.maxc                                                 *
      E(K)  = EV                                                        *
      X(K)  = XV                                                        *
      Z(K)  =0.0                                                       ft
  200 CONTINUE                                                          *
  300 CONTINUE                                                          *
      WRITE  (nu,3013) nart, ndset,ncoef,nsam,chem,crop                 *
 3013 FORMAT (///,' Article Number1,13,', data set #',I3,/,f Results of1*
     +,i3, ' coefficient decay model for ',i2,lx,a8,' sample points on '*
     +,a6, '.')                                                         *
      if     (.not. Ifile) go to 39                                     *
      write  (no,3013) nart, ndset,ncoef,nsam,chem,crop                 *

C	 pseudoORIGINAL ROSE BEGINS HERE
   39 INIT   - .true.
      TERM  . = .false.
      LAP    =0
      LOOP   « 0
      KOUNT  = 0
      Fl     = 0.0

                                                              :       83
                    APPENDIX F: page  7 of 22

-------
      DO 40 K= l.NCC
   40 AL(K)  = (CH(X,DA,NCC,NinDA,K)-CG(X.DA,NCC,NinDA,K))*.001
      DO 60 J= l.NCOEF                                                   361
      DO 60 1= l.NCOEF
      V(I,J) = 0.0
      IF       (I-J) 60,61,60
   61 V(I,J) = 1.0
   60 CONTINUE
      DO 62 K= l.NCOEF
      EINT(K)= E(K)
   62 CONTINUE
C...
   64 continue
      write  (nu,1020)                                                  *
 1020 format (' Stage/Limit Stage/Print_Limit  #_F._Evals.   Avg._F_Error*
     +     Avg. Step Size1)            ~        ~                       *
   65 DO 70 K  = l.NCOEF
C.... line 65 starts new stage
C	 Nstep=0 means return to original step size (EINT) after rotation
      IF     (NSTEP-0) 67,66,67
   66 E(K)     - EINT(K)
   67 NE(K)    = 0
   70 D(K)     « 0.0
      FBEST    - Fl
C.... an implicit loop on I from 1 to ncoef starts here, ends line 441.  .  .
   80 I        =1
      IF     (INIT)  go to 120
   90 DO 95  K = l.NCOEF
   95 X(K)     = X(K) + E(I)*V(I,K)
  100 DO 110 j " 1,ncoef
      XC       • CX(X,DA,NCC,NinDA,J)
      LC       = CG(X,DA,NCC,NinDA,J)
      UC       = CH(X,DA,NCC,NinDA,J)
      if (xc .le. Ic) go to 420
      if (xc .ge. uc) go to 420
  110 continue

  120 Fl       = MM * F(X,DA,NCOEF,NinDA.NIV.dpa,res,nres.nsam)
      KOUNT    • KOUNT + 1
      IF (INIT) FO=MM*l.E+38
      IF (ABS(FBEST-Fl) .le. delF) go to 125
  122 TERM     - .true.
      GO TO 450
  125 CONTINUE

C.... an implicit loop on J from 1 to ncoef starts here, ends line 211.  .  .
      J        - 1
  130 h(j)     - fO
*     the following section preceded by * was bypassed from the original prog.
*     BW    '   • AL(J)
*     XC       • CX(X,DA,NCC,NinDA,J)
*     LC       - CG(X,DA,NCC,NinDA,J)
*     UC       = CH(X,DA,NCC,NinDA,J)


                     APPENDIX F: page  8 of 22
                                                                   84

-------
C ---- remember, F1=MM*F. FO=lastFl, and MM=-1 for minimum error fit;
C ---- thus, it is desired that Fl be .gt. FO; else, change direction.
      IF (Fl .It. FO) go to 420
*     IF (XC .It. (LC+ALU))) go to 160
*     IF (XC .gt. (UC-AL(J))) go to 170
*     GO TO 210
* 160 PW    = (LC+BW-XO/BW
*     GO TO 180
* 170 PW    = (XC-UC+BVO/BW
* 180 PH(J) = 1.0-3.0*PW+4.0*PW**2-2.0+PW**3
* 190 Fl    = H(J)+(F1-H(J))*PH(J)

* 210 CONTINUE
*     IF (J-NCC)        211,220,211
* 211 J     -  J+l
*     GO TO 130
C.... end of implicit J loop ..................
  220 INIT  = .false.
            = 3.0*E(I)
      FO    = Fl
      IF (NE(I) .EQ. 0) NE(I) » 1

  230 DO 240  K - l.NCOEF
      IF (NE(K) .LT. 2) GO TO 440
C.... note a "stage" is when ALL X advances have changed direction twice.
  240 CONTINUE
C	 AXES ROTATION  . . to line 420 ...
C	 BMAG » progress
C	 BBMAG = lateral progress
      DO 250 Kl = l.NCOEF
      DO 250 K2 = l.NCOEF
  250 W(K1,K2) = 0.0
      DO 260 Kl = l.NCOEF
      DO 260 K2 - l.NCOEF
      DO 265 K3 = Kl.NCOEF
  265 WU1.K2) = D(K3)*V(K3,K2)+W(K1,K2)
  260 B(K1,K2)  = W(K1,K2)
      BMAG      = 0.0
      DO 280 K '= l.NCOEF
      BMAG      = BMAG+B(1,K)**2
  280 CONTINUE
      BMAG      = SQRT(BMAG)
      BX(1)     = BMAG
      DO 310 K  = l.NCOEF
  310 V(1,K)    = B(1,K)/BMAG

      DO 340 Kl = 2.NCOEF
      DO 340 K2 = l.NCOEF
      SUMVM     » 0.0
      DO 330 K3 = 1.K1-1
      SUMAV     - 0.0
      DO 320 K4 « l.NCOEF
  320 SUMAV     = SUMAV+W(K1,K4)*V(K3,K4)
                     APPENDIX F: page  9 of 22       '       05

-------
  330 SUMVM     = SUMAV*V(K3,K2)+SUMVM
  340 BCK1.K2)  = W(K1,K2) -SUMVM

      DO 360 Kl = 2.NCOEF                                                 363
      BBMAG     = 0.0
      DO 350 K2 = l.NCOEF
  350 BBMAG     = BBMAG+B(K1,K2)**2
      BBMAG     - SQRT( BBMAG)
      DO 360 K2 = l.NCOEF
  360 V(K1,K2)  - B(K1,K2)/BBMAG

      EA        = 0.0                                                   *
      DO 399  k = l.ncoef                                               *
      EA        - EA + abs(E(k))                                        *
  399 continue                                                          *
      EA        » EA / ncoef                                            *
      Ferr      = FO / (nsam*nres)                                      *
      LOOP      * LOOP+1
      LAP       = LAP+1
      write  (nu,1021) loop, loopy, lap, pr.kount, Ferr, EA                  *
 1021 format (3x,i2,' / ',i2,5x,i3,' /' ,i2,10x,i5,8x, Ipel2.5,5x,lpel2.5)*
      IF (LAP-PR)               65,450,65
C. . . . line 420 etc either (1) lists coefficients and indicates starting point
C. . . . has violated constraints if INIT is true, or
C. . . . (2) undoes array step advance (E) and reverses E(I) 2/3 of a step.
  420 IF (INIT) go to 450
  421 DO 430 K = l.NCOEF
  430 X(K)     « X(K) - E(I)*V(I,K)
      IF (abs(E(I» .It. DELE)   go to 122
      IF (NE(I) .ge. 1)          NE(I) » 2
      GO TO 230

  440 CONTINUE
      IF (I-NCOEF)        441,80,441
  441 I        = 1+1
      GO TO 90
C.... end of implicit I loop ..............
  450 continue
      DO 455 I * l.NCOEF                                                *
  455 Z(I)     « X(I)*DA(I)                                             *
C ____ PRINT CURRENT VALUES OF X AND Z (COEFFICIENTS)
      WRITE  (nu,3005)
 3005 FORMAT (/,'  Sealers to 1st Guesses,  Model Coefficients,     and S*
     +tep Sizes')
      WRITE  (nu,3006) (I.X(I).I.Z(D.I.E(I), 1=1, NCOEF)
 3006 FORMAT (: ,4X,2HX( ,I1,4H) - ,OpF10.6,5X,2HA( ,I1,4H) = ,  1PE11.4,
     +                                    3X,2HS(,I2,4H) - .  1PE12.4)

      LAP      • 0
  461 IF (INIT)        go to 470
  462 IF (TERM)        go to 480
  463 IF (LOOP-LOOPY)  64,480,480
                     APPENDIX F: page  10 of 22

-------
  470 WRITE  (nu,007)
    7 FORMAT (///, 2X,
     + 'THE STARTING POINT APPEARS TO HAVE VIOLATED THE CONSTRAINTS')
               -o.o                                                        354
      go to 37

  480 CONTINUE
      if (.not. Ifile) go to 601
      WRITE  (NO,3003)
 3003 FORMAT (' At exit1, /,2X,5HSTAGE,4X,8HFUNCTION,5X,8HPROGRESS,5X,
     +         16HLATERAL PROGRESS,3X,'# of F EVALS.1  )
      WRITE  (NO,3004) LOOP,FO,BMAG,BBMAG,KOUNT
 3004 FORMAT (1H .I4.3E15.5,10x,I5)
      WRITE  (NO,3005)
      WRITE  (NO,3006) (I,X(I),I,Z(I).I,E(I),  I=1,NCOEF)                 *

C	This section TO LIST AND PLOT THE MEASURED AND PREDICTED VALUES.
C	THE TELL SUBROUTINE WAS DEVELOPED DURING THE INITIAL PLANNING (1974),
C	BUT RPI WAS DEVELOPED FROM 'DKRP1 DURING 1976.   SEE PROGRAM DK.

  601 continue
  605 CALL RPI  (   z.ncoef,dpa,res,nsam,nres,nart,ndset,next,lfile)
      CALL TELL (da,z,ncoef,dpa,res,nsam,nres.nart.ndset,next,Ifile,
     +           adif.pdif)

C.... ask if coefficients are OK,  then
C.... recalulate if necessary or go on to next set of  data
      if (lask) go to 611
  607 write  (nu,3021)
 3021 format (' Type ''//'' of any coefficient you wish to reset,',
     +      /,'    a ''II11 if you wish to reoptimize  from here,  or1,
     +      /,'    a "0" if this is OK and to continue:1  )
      read   (nu,*) next
      next = next +1
      go to  (611,612,612,612,612,612,612,612,612,612,612,619),  next

C—. the following write statements  recreate the specification line,
C.... comment line(s), metabolite-name line,  sample-number line,
C.... residue lines, and coefficient  lines,  respectively.
  611 nruns = nruns+1
      write  (nx,2002)  spec
      write .(nx,2002) (comm(i),i=l,ncomc)
      write  (nx,2003) lox,z(9),z(10)
      write  (nx,2004) nsam,nruns,(pdif(k),k=l,nres),(adif(k),k=l,nres)
      write  (nx,2002) (data(i),i=l,nsam)
      write  (nx.2006) (z(j),j=l,maxc)
      next  = 0
      CALL RPI  (   z.ncoef,dpa,res,nsam,nres.nart.ndset,next,Ifile)
      CALL TELL (da,z.ncoef,dpa,res,nsam,nres.nart.ndset,next,Ifile,
     +           adif.pdif)
      go to 20

 612 next  = next - 1
      write  (nu,3023) next.z(next)
 3023 format ('  The current value  of  coef(',i2,') = MpelO.4,/,


                     APPENDIX F: page  11  of 22

-------
     +        '  Type the desired new value; minus value to end1)
      read   (nu,*) z(next)
C.... a "backdoor" exit with filesave is provided here for user to manually     _
C.... set any coefficient to a MINUS value.  Use it in good health.             365
      if     (z(next))   615,613,614
  613 z(next) = da(next)*x(next)
      go to 607
  614 da(next)= z(next)
      x(next) =0.0
      write  (nu,3024)
 3024 format ('  Type "//" of another coefficient you wish to reset,1,
     +      /,'     a "11" to see fit with reset coefs, or1,
     4-      /,'     a "0" to reoptimize from here,1  )
      read   (nu,*) next
      next = next +1
      go to (619,612,612,612,612,612,612,612,612,612,612,605), next

  615 z(next) * da(next)*x(next)
      nruns   = nruns+1
      write  (nx,2002)  spec
      write  (nx,2002) (comm(i),i=l,ncomc)
      write  (nx,2003) lox,z(9),z(10)
      write  (nx,2004) nsam,nruns,(pdif(k),k=l,nres),(adif(k),k=l,nres)
      write  (nx,2002) (data(i),i=l,nsam),
      write  (nx,2006) (z(j),j=l,maxc)
      next * 0
      CALL RP1  (   z,ncoef,dpa,res,nsam,nres,nart,ndset,next,Ifile)
      CALL TELL (da,z,ncoef,dpa,res,nsam,nres.nart.ndset,next,Ifile,
     +           adif.pdif)
      go to 2

  619 next = 1
      DO 620 j = l.ncoef
  620 if (x(j) .ne. 0.0) da(j)-da(j)*x(j)
      go to   37

C	 A few notes on the logic of "next"
C     initially set next * 1 at line 36+7.
C     in RP1  line 130+2: if next=0 (and other conditions) the plot is copied
C                      onto file NO for later examination.
C     in TELL line 1+2: unless next=0, results will not be written to file NO;
C             line 96: if next=0, model error is not typed to the screen (in
C                      otherwords, next should = 0 only on last pass thru TELL)
C     in REPA line 607+1: read next from screen, il, therefore -Knext<10;
C                  607+2: next=next+l and used in computed goto;
C        if next=0, next reset=0,
C                   call TELL (for final output),
C                   goto 20 and on to 36+7 as initially run;
C        if 0
-------
      subroutine units (res,sd.nsam.nres,unit,sides,crop)
C	 to convert residue units to ug/cm2 and 1-side (projected area)         "^ 6 6
C       unit   = units reported
C                  blank/default = ug/cm2
C                  1       ng/cm2      3 = ppm
C                  2     = mg/m2       4 = other
      integer     sides, unit
      real        res(15,3), sd(15,3)
      character*6 crop

      if (unit .eq. 0) go to 17
       do 16 k=l,nres
          do 15 j=l,nsam
             if (unit.gt.l) go to 12
             res(j,k) = res(j,k)/1000.
             go to 15
   12        if (unit.gt.2) go to 13
             res(j.k) = res(j,k)/10.
             go to 15
   13        if (unit.gt.3) go to 20
             call conppm (res,sd,crop,unit,nsam.nres)
   15        continue
   16     continue
   17  if (sides.ne.2) go to 20
       do 19 k=l,nres
          do 18 j=l,nsam
             res(j.k) = res(j,k)*2.
   18        continue
   19     continue
   20  continue
       return
       end
C	
      Subroutine conppm (res,sd,crop,unit,nsam.nres)
C.... to convert ppm to ng/cm2
      integer     unit
      dimension   res(15,3), sd(15,3)
      character*6 crop
C.... for now, hand calc...
      write (nu,*) ' residue data must be converted from ppm1
      unit * 9
      return
      end
C	
      subroutine tx (da,dpa,res,nsam,nres,ncoef)
C.... to provide preset guesses into DA as a first starting point
C     if the coefficients in input datafile were zero (previously
C     estimated coefficients will be used after the first dset), and
C	 to copy dpa and residue data into remaining DA array expected by ROSE;
C     in the process, it is assumed that any dpa-0 (exactly) can in reality
C     be no less than 0.1 (or two hours post application).

      real da(120),dpa(15),res(15,3),wag(10)
      data wag/1.,.3,.3,.3,.05,.1,.3,.05,.05,.1/

                                                               89
                     APPENDIX F: page  13 of 22

-------
      if (da(l) .ne.  0.0) go to 20
      do 10  k = l.ncoef
      da(k)    = wag(k)
   10 continue                                                          '      7 £ 7
   20 do 30  j = l.nsam                                                       ^ ° '
      k        = ncoef+l+((l+nres)*(j-l))
      da(k)    = dpa(j)
      do 30  i = l.nres
      da(k+i)  = res(j.i)
   30 continue
      if (dpa(l) .eq. 0.0) da(ncoef+l)=0.1
      return
      end
C	
      FUNCTION  F(X,DA,N,NinDA,NIV,dpa,res,nres,nsam)
      DIMENSION X(10),DA(120),A(10),dpa(15),res(15,3)
      DO 2 I - 1,N
      A(I)   = DA(I)*X(I)
    2 CONTINUE
      FX     = 0.
O»»USER WORKING AREA	««««««««««««««««««
   27 CONTINUE
      A23    = a(2)+a(3)
      A234   = A23 +a(4)
      A56    = a(5)+a(6)
      A78    = a(7Ha(8)
      Alx3   = a(l)*a(3)
      A13d6  = Alx3/(A56-A234)
      AlxA   = a(l)*a(4)
      A14d8  - AlxA/(A78-A23A)
      if (nres .gt. 3) STOP 'NRES error in FUNCTION F1
      DO 70 i= l.nsam
      di     = dpa(i)
      if (dpa(i) .eq. 0.0) di=0.1
      go to (55,53,51),nres
   51 Stop 'No model is provided for 2 metabolites!1
   53 F2     =                (A14d8*(exp(-A234*di)-exp(-A78 *di)))      XI
     + +(((a(7)*A14d8)+(a(6)*A13d6))*(exp(-A234*di)-exp(-a(9)*di))/
     +                                                     (a(9)-A23A))  X2
     + +(((a(7)*AUd8/(a(9)-A78)))  *(exp(-A78 *di)-exp(-a(9)*di)))      X2
     + +((a(6)*(a(10)-A13d6))       *(exp(-A56 *di)-exp(-a(9)*di))/
     +                                                     (a(9)-A56))   X2
      IF (res(i,2) .gt. 0.0 .and. F2 .gt. 0.0)
     +    FX = FX + exp(ABS(alog(res(i,2)/F2))) -1.

   55 Fl     = (a(l) *exp(-A234*di))
     + +   (A13d6*exp(-A234*di)) + ((a(10)-A13d6)*exp(-A56*di))
      IF (res(i.l) .gt. 0.0 .and. Fl .gt. 0.0)
     +    FX - FX + exp(ABS(alog(res(i,l)/Fl))) -1.
   70 continue
O»»USER WORKING AREA	«««««««««««««««««««
    1 CONTINUE
      F  « FX
      RETURN
      END


                     APPENDIX F: page  14 of 22

                                                                    90

-------
      FUNCTION CX(X,DA,N,NinDA,K)                                          368
      DIMENSION X(10). DA(120)
      CX = X(K)
      RETURN
      END
C	
      FUNCTION CG(X,DA,N,NinDA,K)
      DIMENSION X(10),DA(120)
      CG = 0.0
      RETURN
      END
C	
      FUNCTION CH(X,DA,N,NinDA,K)
C—. to limit the upper bounds of X
      DIMENSION X(10),DA(120)
      GO TO (10,10,50,50,100,50,100,10,50,10),K
   10 CH = 10.
      RETURN
   50 CH = 50.
      RETURN
  100 CH = 100.
      RETURN
      END
C	
      SUBROUTINE RP1 (a.ncoef,x,yor,nsam,nres,nart,ndset,next,lfile)
      character*! MARK(8). LINE(62,16)
      real x(15),y(15,3),yor(15,3),a(lO),vx(7)
      logical Ifile
C	            12345678
      DATA MARK/' + Vo1,'//',' ', '*'.'.'.'-', 'x'/
      TLOG(X)=ALOG(X)12.30258

      NU    =0
      NO    =3
C.... on the last pass thru RP next will = 0,
C	 resulting in plot printed onto 'output'  instead of user screen.
      if (( next .eq. 0) .and. Ifile ) nu - no
C.... line marks for Blank, Asterisk,  Dot, hyphen, etc.
      LB    = A
      LA    =5
      LD    =6
      LH    =7
      LT    =8
C.... limits of vertical Y axis and horizontal X axis are set and arrays + 1
      Ix    = 50
      ly    = 15
      Ipx   = lx+1
      Ipy   = ly+1

      WRITE  (nu,205) nart, ndset
  205 FORMAT (//,'  PLOT:   article1,i3,',  set ',i2,
     +':   Parent  Ist-Metab.  2nd-Metab.      Other1,/,llx,
     ^'SYMBOLS Measured:     +         o           f/       * = Overlay',/
     + ,19x,  'Modelled:     -         .           x       x = initial +')


                     APPENDIX F: page   15 of 22

                                                               91

-------
C.... the following finds max and min (greater than zero) residues reported
      YMAX    = -1.0E30
      YMIN    =  1.0E30
      DO A7 L = l.nsam
      DO A 7 M • l.nres
      y(l,m)  = 0.0
      if (yor(l.m) .le. 0.0) go to A7
      y(l,ra)  = tlog(yord.m))
   A3 IF (y(l,ra) .gt. YMAX) YMAX - y(l,m)
   A5 IF (y(l,m) .It. YMIN) YMIN «= y(l,m)
   A 7 CONTINUE
      yy      = tlog(a(l)+a(7))
      if (yy .gt. YMAX)     YMAX • yy

      xll     • 0.
      xul     = fnext2(x(nsam) )
      YUL     - FLOAT(IFIX(YMAX+1.))
      YLL     = FLOAT(IFIX(YMIN))
      if (YMIN .It. 0.0)     YLL = YLL-1.
C ---- we want yul-yll to be either I,3,or5 orders-of-magnitude (logs of Y)
C.... to be spaced conveniently on the screen.
   50 logy    = ifix(yul-yll+.0001)
   51 if (logy - 1)                    5A,59,52
   52 if (logy - 3)                    5A.60.53
   53 if (logy - 5)                    5A.60.59
   5A IF (ABS(YUL-YMAX)-ABS(YMIN-YLL)) 55,57,57
   55 YUL     = YUL+1.
   56 GO TO 50
   57 YLL     - YLL-1.
   58 GO TO 50
   59 logy    = 5
   60 continue
      kl      - ly/logy

      YI      = (YUL-YLL)/ly
      XI      = (XUL-XLD/lx
   63 continue
w • * • • •   •   •   •   •   •   •   »   •   •    •   •    •    *    •    •    •
C     The following bigins plotting array "line"
C     with i subscript for row
C          i subscript for column
C          k index  for X and Y labels
C          L subscript for samples
C          M subscript for residues within samples
C     characters start blank
C     borders are added (dots and pluses) in lines 6A-68
C     reported data are scanned and added in lines 68-91
C     the model is run and dots are added when in plot in lines 91-110
C         MARK   1   2   3   A   5   6   7   8
C               l + 'lnlly/ltl
w • * • •            T f  w y If f

      DO   6A I  « l.lpx
      DO   6A J  - l.lpy
      LINE(I.J)  •  MARK(LB)
                     APPENDIX F: page  16 of 22                    Q2

-------
   64 CONTINUE
      DO   65 I  = l.lpx
      LINE(I.l)  -  MARK(LD)                                              37Q
      LINE(I.lpy)-  MARK(LD)
   65 continue
      DO   66 I  *'l,lpx,5
      LINE(I.l)  =  MARK(l)
      LINE(I.lpy)»  MARK(l)
   66 continue
      DO   67 J  = l.lpy
      LINE(l.J)  *  MARK(LD)
      LINE(lpx.J)-  MARK(LD)
   67 continue
      DO   68 J  * l.lpy.kl
      LINE(l.J)  =  MARK(l)
      LINE(lpx,J)=  MARK(l)
   68 continue
C.... mark the model initial parent with an x
      yy         * (yy-YLL)/YI
      J          » lpy-ifix(round(yy,0))
      LINE(l.J)  =  MARK(LT)

      DO  91 L   = l.nsam
      xx         * (x(L)-XLL)/XI
      I          = 1 + ifix(round(xx,0))
      if ((I .It. 1) .or. (I .gt.  Ipx)) go to 91
      DO  90 M   ,= l.nres
      if (yor(L.M) .le. 0.0) go to 90
      LM         = M
      vy         = (y(L,M)-YLL)/YI
      J          = Ipy-ifix(round(yy,0))
      if ((J .It. 1) .or. (J .gt.  Ipy)) go to 90
      IF (LINE(I.J) .ne. MARK(LB)) LM=LA
      LINE(I.J)  = MARK(LM)
   90 continue
   91 continue

C.... find values of model
C....   DI = x interval (i.e. day post-application)
C	  PYn = plotted value of model at DI
   27 CONTINUE
      A23  = a(2Ha(3)
      A234 • A23 +a(4)
      A56  * a(5)+a(6)
      A78  = a(7)H-a(8)
      Alx3 = a(l)*a(3)
      A13d6* Alx3/(A56-A23A)
             Alx4/(A78-A234)
      DO 110 I = l.lpx
      DI   = XI*FLOAT(I-1)
      go to (155,153,151),nres
  151 Stop 'No model is provided for 2 metabolites!'
  153 F2   =                 (A14d8*(exp(-A234*di)-exp(-A78 *di)))      XI
     + -l-(((a(7)*AlAd8)+(a(6)>*A13d6))*(exP(-A234*di)-exp(-a(9)*di))/


                     APPENDIX F: page  17 of 22

-------
     +                                                     (a(9)-A234))  X2
     + +(((a(7)*A14d8/(a(9)-A78)))  *(exp(-A78 *di)-exp(-a(9)*di)))      X2
     -t- +((a(6)*(a(10)-A13d6))       *(exp(-A56 *di)-exp(-a(9)*di))/
     +                                                     (a(9)-A56))   X2     37]

  155 Fl  = (a(l) *exp(-A234*di))
     + +    (A13d6*exp(-A234*di)) + ((a(10)-A13d6)*exp(-A56*di))
      if (Fl .le. 0.0) go to 100
      PY1 - TLOG(Fl)
      yy  = (PY1-YLD/YI
      J   - lpy-ifix(round(yy,0))
      if ((J .It. 1) .or. (J .gt. Ipy))  go to 100
      IF (LINE(I.J) .eq. MARK(LB)) lined,J)  - mark(LD)
  100 if (DI .le. 0.0 .or. F2 .le. 0.0)  go to 110
      PY2 - TLOG(F2)
      yy  « (PY2-YLD/YI
      J   « Ipy-ifix(round(yy,0))
      if ((J .It. 1) .or. (J .gt. Ipy))  go to 110
      IF (LINEd.J) .eq. MARK(LB)) lined,J)  - mark(LH)
  110 CONTINUE
  111 CONTINUE

      k   = kl-1
      nkl - 0                                                           !
C	 DUMMY K STARTS«kl-l AND PUTS unit  labels
C	 ON EVERY  3RD or 5TH Y, AND 10TH X
      DO 125  J = l.lpy
      k   - k+1
      if (k-kl)           121,123,121
  121 if (J .le. ncoef+nkl) go to 122                                   !
      WRITE  (nu,206) (LINE(I,J),I=l,lpx)
      go to 125
  122 nc  - j-nkl
      WRITE  (nu,209) (LINE(I,J),I=l,lpx),nc,a(nc)
      go to 125
C	 VY IS MANTISSA AND iPY IS CHARACTERISTIC ON BASE  10  LOG  (TLOG)
  123 k   - k-kl
      nkl = nkl + 1
      YY  = YLL + (float(lpy-j)*yi)
      iPY = IFIX(ROUND(YY,0))
      VY  • 10.**(YY-iPY)
      VY  • ROUND(VY,2)
      WRITE  (nu.207) VY.iPY,(lined.J),I-l,lpx)
  125 CONTINUE
  206 FORMAT (1H ,12X,61A1)
  209 FORMAT (1H ,12X,51A1,  2x,'A',11,'•'.elO.A)
  207 FORMAT (1H .1X.F5.2,1  E1,13,lx,61al)
      DO 130 I - 1,7
      VX(I)    « XLL+(XI*10.*float(I-l))
      VX(I)    = ROUND(VX(I),1)
  130 CONTINUE
      WRITE  (nu,208)  (VX(I),I»1,6)
  208 FORMAT (1H ,  4X,7(5x,F5.D)
  150 RETURN
      END
                     APPENDIX F:  page  18  of  22
94

-------
c	  372
      function fnext2 (x)
C	 to find the next smallest multiple of x among 2,4,6,8,orlOx
      xd     = (10.**ifix(aloglO(x)))
      do 1 n = 1,5
      fnext2 = 2.*float(n)*xd
      if (fnextZ .ge. x) go to 2
     1 continue
     2 return
      end
C	
      function round(r,i)
C	 where r=number to be rounded and
C....       i=intergers remaining after decimal
      round = 0.0
      n     = 1
      rO    = 10.**i
      if (i .eq. 0)          rO = 1.
      if (r)                 11,9,1
   11 n     = -1
     i rl    = r*rO*float(n)
     2 il    = ifix(rl)
     3 r2    = rl-float(il)
     4 if (r2-0.5)             8,5,7
     5 r3    = float(il)/2.
     6 if (r3-ifix(r3)-.25)    7,7,8
     7 il    = il+1
     8 round = float(il*n)/rO
     9 return
      end
C	
      SUBROUTINE TELL (da.a.ncoef,dpa,res,nsam,nres,nart,ndset,next,
     +                 lfile.adif.pdif)

C	 ROUTINE WILL LIST PREDICTED POINTS AND COMPARE THEM TO INPUTS
C	 IT IS IDEALLY SUITED TO TIME SERIES DATA IN WHICH TIME IS FIRST
C	 USER MUST SUPPLY DEFINITIONS OF Fl, F2, F3, IN USER'S WORKING AREA

      DIMENSION X(10), DA(120), A(10), dpa(15), res(l5,3)
      integer nnzr(3)
      real pred(3),dif(3),pdif(3),chi2(3),adif(3)
      logical Ifile.lhold,match

      nu      =0
      NO      =3
      do 1 i  = l.nres
      PDIF(i) - 0.
      CHI2U) = 0.
      ADIF(i) = 0.
      nnzr(i) = 0
     1 CONTINUE

C	 a Holding status is introduced into file to hold printing of model results
C	 until the last pass through TELL.
      Ihold = Ifile
                     APPENDIX F: page  19 of 22              >-      Q _

-------
      if (next .ne. 0) Ifile - .false.
      if (.not. Ifile) go to 23
      WRITE  (NO, 100)
  100 FORMAT (/,' MODEL RESULTS',7('.'),'parent',12('.').lx,12('.'),
     +          'metabolite(s)',10('.' ),'>',
     +  /,'  TIME   ',2(   9HPREDICTED,2X,8HMEASURED,3X,9HPCT.DIFF. ),
     +  /,'  days',   2(5x.'ug/cm2',4x,'ug/cm2I.8x,'%',lx))
C.... format 100 will currently only accept 2 residues; 3 OK on wide paper.

   23 CONTINUE
      list   = 61
C	 PROGRAM REQUIRES INPUT DATA TO BE CHRONOLOGICALLY ORDERED
C	 lastd SET AT 1.5 TIMES THE LAST INPUT TIME
C.... but list of days shall not exceed 61
      lastd  - IFIX(dpa(nsam)*1.5)
      NT     = 1
   15 IF ((lastd/NT)-list)  17,17,16
   16 NT     = 2*NT
      GO TO 15
   17 CONTINUE

      i      =0
      A23    - a(2)+a(3)
      A234   = A23 +a(4)
      A56    = a(5)+a(6)
      A78    - a(7)+a(8)
      Alx3   = a(l)*a(3)
      A13d6  » Alx3/(A56-A234)
      AlxA   = a(l)*a(4)
      AlAdS  « Alx4/(A78-A234)
C.... This is a BIG 'double' (i and j) do loop down to line 90
      DO 90 j-NT.lastd,NT
   18 match  = .false.
      DI     = FLOAT(j-NT)
      if (i+1 .gt. nsam) go to 20
      if (dpa(i+l) .gt. float(j)-(.5*float(nt))) go to 20
      i      = i+1
      DI     = dpa(i)
      if (dpa(i) .eq. 0.0) di=0.1
      match  = .true.
   20 CONTINUE
O»»THIS IS THE USER'S WORKING AREA...««««««««««««««««
O»»WITHIN ITS BOUNDS, DEFINE pred(l)=OP. pred(2)=metabolite, etc.««
   27 CONTINUE
      go to (55,53,51),nres
   51 Stop 'No model is provided for 2 metabolites!'
   53 F2      -               (A14d8*(exp(-A234*di)-exp(-A78 *di)))      XI
     + +(((a(7)*A14d8)+(a(6)*A13d6))*(exp(-A234*di)-exp(-a(9)*di))/
     +                                                     (a(9)-A234))  X2
     + +(((a(7)*A14d8/(a(9)-A78)))  *(exp(-A78 *di)-exp(-a(9)*di)))      X2
     + -l-((a(6)*(a(10)-A13d6))       *(exp(-A56 *di)-exp(-a(9)*di))/
     •••                                                     (a(9)-A56))   X2
      ored(2)  = F2

   55 Fl      = (a(l) *exp(-A23A*di))


                     APPENDIX F:  page   20 of 22

-------
     + +   (A13d6*exp(-A234*di)) + ((a(10)-A13d6)*exp(-A56*di))
      pred(l) = Fl
                                                                           374
C	 THIS model WAS DEVELOPED TO ESTIMATE 7 COEFFICIENTS
C     PARENT     P. =     PI +    PI
C         d(P)/d(t) = -(a2+a3+a4)*Pl + (a3*Pl) - (a5+a6)*P2
C     METABOLITE X  =     XI +    X2
C         d(X)/d(t) =  a4*Pl -I- a6*P2 + (a3*Xl) - a2*Xl - a5*X2
C
C     AT  t = 0.
C     Pl(0) = Al
C     P2(0) = A7
C     Xl(0) = X2(0) = 0.
C     TO model parent only, SET DA(4)=0.0
C                               DA(6)=0.0
O»»THIS IS THE END OF THE USER'S WORKING AREA. ..<««««««««««
   80 CONTINUE

      if (.not. match) go to 86
C.... the following composite values are determined and reported
C.... pdif - percent error in observed over expected
C.... chi2 = sum of squares of dif (Chi-squared)
C.... adif = percent absolute error in observed over expected
      do 82 k = l.nres
      if     (res(i.k) .eq. 0.0) go to 82
      if     (pred(k)  .le. 0.0) go to 82
      dif(k)  = (pred(k)- res(i,k))/pred(k)
      chi2(k) = chi2(k) -t- (dif(k)**2)
      dif(k)  = dif(k) * 100.
      pdif(k) = pdif(k) + dif(k)
      adif(k) = adif(k) + abs(dif(k))
      nnzr(k) = nnzr(k) + 1
   82 CONTINUE

      if     (.not. Ifile) go to 18
      WRITE  (NO,102) di.(pred(k),res(i,k),dif(k),k=l,nres)
  102 FORMAT ( F7.2,2x,3(:,lpe9.3,2x,lpE9.3.1X,Opf7.2,3x))
      go to 18
   86 if     (.not. Ifile) go to 90
      WRITE  (NO,101) DI,(pred(k),k=l,nres)
  101 FORMAT (F7.2,2x,3(:, lpE9.3,:,22X))
   90 CONTINUE

      do 92 k = l.nres
      if     (nnzr(k) .le. 0) go to 92
      pdif(k) = pdif(k)/FLOAT(nnzr(k))
      adif(k) = adif(k)/FLOAT(nnzr(k))
   92 CONTINUE

      if     (.not. Ifile) go to 96
      WRITE  (NO,103) (chi2(k),k=l,nres)
      WRITE  (NO,104) (pdif(k),k=l,nres)
      WRITE  (NO,105) (adif(k),k=l,nres)
  103 FORMAT (/,14X,         'CHI SQUARE =  ' ,2x,3(IpElO.3,:,20X))
  104 FORMAT (   8X,   'MEAN   %   ERROR =',     3(2pE12.4,:,18x))


                     APPENDIX F: page  21 of 22                *

-------
  105 FORMAT (   8X,    'MEAN Z ABS ERROR « ',     3(2pE12.4,:,18X))

   96 if     (next .eq.  0) go to 98
      write  (nu,106)  (k.pdif(k),k«l,nres)
  106 format ('  MEAN   %  ERROR: Res(',il,')»',f6.1,
     +                    2(:,' ResC.il,')='.f6.1))
      write  (nu,107)  (k.adif(k),k«l,nres)
  107 format ('  MEAN  |%J  ERROR: Res(',il,')=',f6.1,
     +                    2(:,' ResC.il.')-'.f6.D)

   98 Ifile « Ihold
      RETURN
      END
C
      subroutine yes  (letter,choice)
      character*! letter
      logical choice
      choice ** .false.
      if (letter .eq.  'y') choice = .true.
      if (letter .eq.  'Y') choice = .true.
      return
      end
                     APPENDIX F:  page  22 of 22
                                                               98

-------
                                                                 APPENDIX G


Appendix G: Computer Program to Standardize Residues and Tabulate Responses    376
            Using the Unified Field Model.
            A short description of each symbol is given at the end of this •
            appendix (see also Appendix C).

      program REEN

c.... version 3 (to create a one- line/sample file containing
c         chem,nart,ndset,loc,crop,aia and form [as sped],
c         dpa , ( res ( i ) , i=l , 4 ) , den , dAChE , kdcom , Idass

c**************ft****************^
c                                                                             c
c     Purpose: To estimate AChE inhibition [optionally for a                  c
c              given crop and pesticide] for a given level(s) of              c
c              residue.   Estimations are determined using the                 c
c              'unified field model':                                         c
c                                                                             c
c              A compilation of dislodgeable foliar residue                   c
c              studies serves as the data base, along with                    c
c              various other coefficient and toxicity files.                  c
c                                                                             c
c     Dose:  D = kd*t*R/m                                                     c
c                where D    = dose, mg/kg                                     c
c                      kd   = crop specific dosing constant                   c
c                      t    = duration of exposure (hrs)                      c
c                      R    = residue, ug/cm2                                  c
c                      m    = body mass, = 70  kg (50 %ile man)                c
c                           .                                                  c
c     Response: dAChE = 1 - exp(-ke*D/LD50)                                   c
c                where dAChE = a fraction (Z/100) of RBC cholinesterase       c
c                              inhibited                                      c
c                       LD50 = acute toxicity, mg/kg                          c
c                       ke   = enzyme constant, =6.0                         c
c                                                                             c
c                                                                             C
      integer      ex, unit,  dapp,  yapp,
     +             fileO, filel,  fileZ,  file3,  file4,  fileS,  file6
      real         dpa(30) ,res(30,4),sd(30,4) ,LD50(A) ,dAChE(30) .kd.leafd
      character*!  file, den, kdcom
      character*3  loc, locrq,  mapp
      character*4  form
      character*6  crop.croprq
      character*8  chem,chemrq
      character*12 input, output, spec!
      character*20 cropname
      character*25 chemname(4),comname
      character*30 lox(3)
      character*79 comm(6)
      logical      crmat.chmat


                                                                  99
                     Appendix G,  page   1   of 9                     ' '

-------
c.... file 1 = user screen and console...format 1000 series reserved I/O.
c              (PC assumes this device to be "0")                             "^77
c	 file 2 = pesticide residue data base (filename =  'INPUT')              J ' '
c              (filename specified by user)
c	file 3 = the output file             (  "      =  'OUTPUT')
c              (filename specified by user)
c	 file 4 = crop coefficient library     (   "      =  'cropco.lib1)
c.... file 5 = chemical coefficient library (   "      =  'chemco.lib1)

       fileO=0
       file2=2
       file3=3
       file5=5
       file6=6

c     limits set for max number of requested effects (array),  coefficients,
c     number of samples and residues within each sample.
      maxr   «= 4
      maxs   = 30
      crmat  = .false.
    1 continue

      DO 3 i = l.maxs
         DO  2  j = l.maxr
            res(i.j) =0.0
            sd(i,j)  « 0.0
            Id50(j)  = 0.0
    2       continue
    3    continue

      chmat  = .false.
      write  (fileO,1003)
 1003 format (' Type residue INPUT filename, up to 12 characters:')
      read   (fileO.1004) input
 1004 format (a!2)
      if     ((input .eq. 'quit*).or.(input .eq. 'exit').or.
     +        (input .eq. 'stop1).or.(input .eq. 'end'))  goto  30000

      open   (file2, file = input)
      open   (file4, file='cropco.lib')
      open   (fileS, file=lchemco.lib1)
      rewind file2
      rewind file4
      rewind fileS

    5 continue
      write  (fileO.1005)
 1005 format (' A specific chemical (coded) can be requested;',/,
     +        ' type chemical (a8) or ''all11  for all crops:')
      read   (fileO,1006) cherarq
 1006 format (a6)
      write  (fileO,1007)
 1007 format (' A specific location (coded) can be requested;',/,


                     Appendix G, page  2  of 9

                                                           .     100

-------
     +        '  type location (a3) or ''all11  for  all  locations:')
      read   (fileO,1008) locrq
 1008 format (a3)
      write  (fileO,1009)
 1009 format ('  A specific crop (coded)  can be requested;1,/,
     +        '  type crop (a6) or "all"  for  all  crops:')
      read   (fileO.1010) croprq
 1010 format (a6)

      write  (fileO.1011)
 1011 format ('  Type data OUTPUT filename,  up  to 12  characters:1)
      read   (fileO,1004) output
      write  (fileO,1012)
 1012 format ('  Type 0 to show input data  on screen',/,
     +        '    or 1 to exclude this option:1)
      read   (fileO.1013) filel
 1013 format (il)
      if     (filel .eq.  0) goto 7
      open   (filel)
      rewind  filel
    7 open   (file3, file = output,  status='new')
      rewind  file3

c	 READ DATA SPECIFICATION FILE 	
   51 read  (file2,2001,end=85) chem,nart,ndset,nox,loc,crop,igraph,
     +form,aia,gpa,ex,unit,nsides,dapp.mapp,yapp,ncomm,npunpr.isd
 2001 format(a8,lx,2(I2,lx),il,lx,a3,lx,a6,lx,il,lx,a4,lx,f5.2,lx,f4.0,
     +      Ix,3(il,lx),i2,lx,a3,lx,i2,lx,il,lx,i3,lx.il)
      write (filel,2001      ) chem,nart,ndset,nox,loc,crop,igraph,
     +form,aia,gpa,ex,unit,nsides,dapp.mapp,yapp,ncomm,npunpr.isd
      backspace file2
      read  (file2,2011)  spec!
 2011 format(34x,a!2)
      call chemck (chem.noxa,Id50,chemname,comname,chmat,file5)
c.... the above subroutine searches  to match chemical  with  data  in  chemco file
      nres = nox + 1
      Idass = 0

c.... reading up to 6 comment lines
   52 if    (ncomm .le. 0) goto 53
      read  (file2,2002,end=9002) (comm(i),i=l,ncomm)
      write (filel,2002)           (comm(i),i=l,ncomm)
 2002 format(a79)

c.... reading the name of the oxons  or other metabolites
   53 if    (nox .le. 0)  goto 54
      read  (file2,2003,end=9003) (lox(i),  i=l,nox)
      write (filel.2003)           (lox(i),  i=l,nox)
 2003 format(a30)

c	 reading the number  of samples  in the following set of data
   54 read  (file2,2004,end=9004) nsam
      write (filel,2004)           nsam
 2004 format(i2)
                     Appendix G,  page  3  of 9
101

-------
c.... reading residue data ...
      if       (nsam .le. 0) goto 56
      DO 55 j=l,nsam
         read  (f Ue2,2005,end=9005) dpa( j ),(res( j ,k),sd( j ,k),k=l,nres)
         write (filel.2005)          dpa(j),(res(j,k),sd(j,k),k=l,nres)
   55    continue
 2005 format(f4.0,lx,8(f6.0,lx))

C.... QC-tolerance checks follow (line 56 to line 71):
   56 continue
      if    (chemrq .ne. chem .and. chemrq .ne.  'all     ')  goto 51
      if    (croprq .ne. crop .and. croprq .ne.  'all   '   )  goto 51
      if    (locrq  .ne. loc  .and. locrq  .ne.  'all1      )  goto 51
      if    ( nox   .gt. noxa)  goto 9015
      if    ( nres  .gt. maxr)  goto 9016
      if    ( nsam  .gt. maxs)  goto 9017
      if    (.not. chmat)       gotti 9018
      if    (Id50(l) .le. 0.01  goto 9019
      if    (nox .le. 0) goto 64
      do 58 k=2,nres
         if (Id50(k) .ne. 0.0) goto 58
         write  (fileO.1021) chemname(k),nart,ndset
 1021    format (' The LD50 for ',a25,' in article ',12,'  data set ',i2,
     +         /,' is unknown but asssamed * parent.1)
         Idass » Idass + 1
         Id50(k)=ld50(l)
   58    continue

   64 kdcom • ' '
      call cropck (crop,kd.cropname,leafd,den,crmat,file4)
c.... the above subroutine searches to match crop with data  in cropco file
      if    (.not. crmat) goto 9028
   65 if    (kd .ne. 0.0) goto 66
      write (fileO,1026) crop,nart,ndset
 1026 format(' Dosing coefficient (kd) for ',a6,'  in article ',i2,
     +' dataset ',i2,/, '  not listed in cropco library!  Default value e
     + 5000 cm2/hr.')
      kd = 5.0
      kdcom = '?'
   66 continue

   70 call units (res,sd,nsam,nres,unit,nsides,crop,leafd)
c.... above subroutine to convert to ug/cm2 projected area
c     units may be nonstandard and must be individualy converted.
      if    (unit  .ge.   4) goto 9014
      if    (leafd .le. 0.0) goto 9029

   71 call dosres  (dpa,res,LD50,dAChE,nres,nsam,kd)
c.... above subroutine to convert from residue to dose and AChE...
                     Appendix G, page  4  of 9

                                                                   102

-------
C.... the following write statements create the modified (one-line)
C     "output" file
      DO 75 j=l,nsam
C                                 spec! equivalent to :aia:gpa:
         write  (file3,3005) chem,nart,ndset,loc,crop,specl,
     +                       dpa(j),(res(j,k),k=l,maxr),den,dAChE(j),
     +                       kdcom.ldass
c	            V       V       V  <-- potentially removable delimiters
 3005 format(a8,':',2i2,':',a3,a6,a!2,fA.I.':',
     +       4(f6.3,':l),al,f7.3,al,il)
         do 74 k=l,maxr
C           arrays reset to avoid carry-over of "oxon" values between data sets
            res(j.k) * 0.0
            sd(j,k)  = 0.0
   74       continue
   75    continue
      goto 51

   85 write (fileO,*) 'Reading end of requested chem.-input datafile.'
      goto 1

C.... The following lines are various error and data-set reject  modes:
 9002 write (*,*)  '  Unexpected End-of-file  while reading comment lines!1
      goto 1
 9003 write (*.*)  '  Unexpected End-of-file  while reading "oxon"  lines!1
      goto 1
 9004 write (*,*)  '  End-of-file while reading number-of-samples  lines!1
      goto 1
 9005 write (*,*)  '  End-of-file while reading sample-data lines!1
      goto 1
 9014 write (fileO,1014) nart, ndset
 1014 format('  Nonstandard units in article ',i2,' dataset ',i2,/,
     +       '  - no further calculations are made on this data.')
      goto 51
 9015 write (fileO,1015) nart,ndset
 1015 formatC  More metabolites in article  ',12,' dataset ',i2,
     +       '  than listed in chemco.1)
      goto 1
 9016 write (fileO,1016) nart,ndset,maxr
 1016 format('Metabolites in article ',i2,' dataset ',i2,' exceed array
     •KLimit of ',il)
      goto 1
 9017 write (fileO.1017) nart,ndset,maxs
 1017 format('Samples in article ',i2,' dataset ',i2,' exceed array limi
     +t of «.i2)
      nsam = maxs
      goto 64
 9018 write (fileO,1018) chem,input,input
 1018 formatdx.aS,1  as listed in ',al2,
     +' was not found within chemco library.',/,
     +' Please check ',al2,'  for proper code or update cheraco.lib.')
      goto 51
 9019 write (fileO.1019) chem
 1019 format(Ix,a8,'  found within chemco library but without LD50!1)
                     Appendix G,  page  5  of 9
103

-------
 9028 write (filed,1028) crop
 1028 format(Ix,a6,'  not found within cropco library.  Please  check  listi
     +ng for proper code.1)
      goto 51
 9029 write (fileO,1029) crop,nart,ndset
 1029 format('  Unable to convert ppm for ',a6,'  in article  ',12,
     +       '  dataset ',12,' toug/cm2')                                      381
      goto 51

30000 STOP 'Have a good day1
      END
C	
      subroutine units (res,sd,nsam,nres,unit,nsides,crop,leafd)
c ... to convert residue units to ug/cm2 and 1-side (projected area) values
C       unit   = units reported
C                0/blank = ug/cm2 [default]
C                1       « ng/cm2      3 * ppm
C                2       = mg/m2       4 * other
      integer     unit
      real        res(30,4),  sd(30,4),leafd
      character*6 crop

       if (unit .eq.  0) goto 17
       do 16 k=l,nres
          do 15 j^l.nsam
             if (unit .gt. 1) goto 12
c....        to convert from ng/cm2
             res(j.k) • res(j,k)/1000.
             goto 15
   12        if (unit .gt. 2) goto 13
c....        to convert from mg/m2
             res(j.k) - res(j,k)/10.
             goto 15
   13        if (unit .gt. 3) goto 20
c....        to convert from ppm
             if (leafd .eq. 0.0) goto 20
             res(j.k) « res(j,k)*leafd/1000.
   15        continue
   16     continue
       unit = 0
   17  if (nsides .ne. 2) goto 20
c....  to convert from residues per 2 sides of a leaf
       do 19 k=l,nres
          do 18 j=l,nsam
             res(j.k) • res(j,k)*2.
   18        continue
   19     continue
       nsides « 1
   20  continue
       return
       end
                     Appendix G,  page  6  of 9
                                                                  104

-------
      Subroutine cropck (crop,kd,cropname,leafd,den,crmat,file4)
c—.  to find crop match and transfer pertinent parameters
      character*!  den
      character*6  .crop,code,stdcode
      character*20 cropname
      integer      fileA
      logical      crmat
      real         kd.leafd

      crmat - .false.
      rewind fileA
    1 read  (file4,4001,end=10) code,kd,cropname,leafd,den,stdcode
 4001 format(a6,5x,f4.1,7x,a20,2x,f4.1,al,2x,a6)
      if (crop .ne. code) goto 1
      crmat = .true.
      crop  = stdcode
   10 return
      end
c
      Subroutine chemck (chem,noxa,ld50,chemname,comname,chmat,fileS)
c....  to find chemical match and transfer pertinent parameters
      character*8  chem.code
      character*25 chemname(A),comname
      integer      fileS
      logical      chmat
      real         Id50(4)

      chmat = .false.
      rewind fileS
    1 read  (file5,5001,end=10) code,ld50(l),noxa,chemname(l),comname
 5001 format(a8,Ix,f4.0,Ix,il,Ix,a25,a25,2x,al,lx,al)
      if (chem .ne. code) goto 1
      do 3 i - l.noxa
         read  (file5,5002,end=10)   Id50(i+l),   chemname(i+l)
 5002 format(   9x,f4.0,      3x,a25                )
    3    continue
    9 chmat = .true.
   10 return
      end
c
      Subroutine dosres (dpa,res,LD50,dAChE,nres,nsam,kd)
c....  to convert residue to dose (mg/kg) and dAChE (%) ...
      real dpa(30),res(30,4),LD50(4),dAChE(30),kd,mass
c....  kd   = crop specific dose rate, from cropco.lib file
c	  LD50 = dermal toxicity(s),      from chemco.lib file
c....  mass = 70 kg for 50Zile man
      mass = 70.
c....  workday = 8 hours
      work =8.0
c....  ke   = enzyme constant =6.0
      ke   = 6.0"

      do 35 i=l,nsam
         sum =0.0
                     Appendix G, page  7  of 9                        105

-------
         do 30 j«=l,nres
            if (mass .eq. 0.0 .or.
     +           mass, j, Id50(j)
            D=kd*work*res(i,j)/mass
            sum - sum + (D/ld50(j))
   30       continue
         dAChE(i)=100.*(1.-exp(-ke*sum))
   35    continue
       return
       end
                            Id50(j) .eq. 0.0) write (*,*)
                                                                   383
Name   Type
AIA
CHEM
CHEMNA
CHEMRQ
CHMAT
COMM
COMNAM
CRMAT
CROP
CROPNA
CROPRQ
DACHE
DAPP
DEN
DPA
EX
FILED
FILE1
FILE2
FILE3
FILE4
FILES
FILE6
FORM
GPA
I
IGRAPH
INPUT
ISO
J
K
KD
KDCOM
LD50
LDASS
LEAFD
LOG
LOCRQ
LOX
MAPP
MAXR
REAL
CHAR
CHAR
CHAR
LOGI
CHAR
CHAR
LOGI
CHAR
CHAR
CHAR
REAL
INTE
CHAR
REAL
INTE
INTE
INTE
INTE
INTE
INTE
INTE
INTE
CHAR
REAL
INTE
INTE
CHAR
INTE
INTE
INTE
REAL
CHAR
REAL
INTE
REAL
CHAR
CHAR
CHAR
CHAR
INTE
Variables use in main program REEN1

Active Ingredient per Acre
coded CHEMical name
full CHEMical NAme
CHEMical ReQuested by user
CHemical MATch
COMMents (up to 6 lines)
COMmon chemical NAMe
CRop MATch
coded CROP name
full CROP NAme
CROP ReQuested by user
delta AChE (%)
Date of Application
symbol for surety of leaf DENsity
Days Post-Application
coded foliar residue Extraction solvent
input/output device
input file on disk
output file on disk
input file on disk
input file on disk
input file on disk
input file on disk
FORMulation of parent chemical
Gallons mixture Per Acre applied
subscript
code for Input data originally from a GRAPH or equation
INPUT file name
code designating statistical parameters on residues
subscript
subscript
Dosing coefficient
symbol for surety of Dosing coefficient
dermal Lethal Dose 50%
number of metabolite LDSOs assumed equal to parent
LEAF Density (mg/cm2)
coded LOCation
coded LOCation ReQuested by user
name of metabolites [Label of OXon]
Month of Application
MAXimum number of Residues permitted by array definition
                     Appendix G, page  8  of 9
                                                                      106

-------
MAXS   INTE      MAXimum number of Samples permitted by array definition
NART   INTE      citation Number of ARTicle                                _ o  .
NCOMM  INTE      Number of COMMent lines                                   384
NDSET  INTE      Number of DataSET within cited article
NOX    INTE      Number of metabolites (OXons)  in study
NOXA   INTE      maximum Number of "OXons" Already in chemco.lib
NPUNPR INTE      Number of PUNches within sample (if not nominal  48-60)
NRES   INTE      Number of RESidues reported in study [= NOX+1]
NSAM   INTE      Number of SAMples in study
NSIDES INTE      Number of SIDES used to calculate ug/cm2
OUTPUT CHAR      name of OUTPUT file
RES    REAL      RESidue values
SD     REAL      Standard or relative Deviation of residues
SPEC1  CHAR      dummy array to avoid write errors
UNIT   INTE      UNITs of residue reported
YAPP   INTE      Year of Application
                     Appendix G,  page  9   of  9

                                                              107

-------
                                                               APPENDIX H
Appendix H: Compilation of Reported Residue and  Calculated Response Data.

            Tabulation format includes the chemical name  (coded),
            the article (citation)  number, the study number
            within the article (sequential),  the location
            (coded), crop (coded),  application rate (Ib AIA),
            mixture (gallons/acre), the day post-application, 4
            residues (ug/cm ), an optional "?" when the residues
            were converted from ppm with only estimated leaf
            density, the calculated 8-hour cholinesterase
            response (% dAChE), a second optional "?"  for crops
            for which the default dosing coefficient was  assumed
            (default = 5000 cm /hr), and a single digit
            indicating the number of metabolites whose dermal
            toxicity was assumed equal to the parent.
385
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
azinme
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
: 2
: 2
: 2
: 2
: 2
: 2
: 2
: 2
: 2
: 2
: 2
: 2
1 : CAsOrange
1 : CAsOrange
1 : CAsOrange
1 : CAsOrange
1 : CAsOrange
1 : CAsOrange
2: CAsOrange
2 : CAsOrange
2 : CAsOrange
2 : CAsOrange
2 : CAsOrange
2: CAsOrange
3 : CAsOrange
3 : CAsOrange
3 : CAsOrange
3 : CAsOrange
3 : CAsOrange
3 : CAsOrange
4 : CAsOrange
4 : CAsOrange
4 : CAsOrange
4 : CAsOrange
4 : CAsOrange
4 : CAsOrange
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
1 : CAvPeach
2 : CAvPeach
2 : CAvPeach
2 : CAvPeach
2 : CAvPeach
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:06.00
:02.00
:02.00
:02.00
:02.00
:02.00
:02.00
:01.00
:01.00
:01.00
:01.00
:01.00
:01.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:03.00
:0100:
:0100:
:0100:
:0100:
:0100:
:0100:
:1200:
:1200:
:1200:
:1200:
:1200:
:1200:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0500:
:0105:
:0105:
:0105:
:0105:
:0105:
:0105:
:0105:
:0105:
:0100:
:0100:
:0100:
:0100:
3.0:20.200:
10.0:11.400:
17.0:10.600:
31.0:10.400:
44.0:
59.0:
3.0:
10.0:
17.0:
31.0:
44.0:
59.0:
3.0:
10.0:
17.0:
31.0:
44.0:
59.0:
3.0:
10.0:
17.0:
31.0:
44.0:
59.0:
.0:
4.0:
6.0:
10.0:
13.0:
14.0:
16.0:
20.0:
.0:
1.0:
3.0:
4.0:
9.400:
7.600:
9.200:
3.200:
2.600:
1.860:
2.000:
1.600:
4.000:
1.400:
1.240:
.940:
.760:
.600:
1.560:
.600:
.560:
.400:
.280:
.240:
5.800:
3.600:
2.000:
1.360:
.960:
4.600:
4.000:
3.000:
5.000:
5.200:
5.600:
5.800:
.078:
.066:
.106:
.090:
.076:
.012:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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30.
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237 0
280 0
865 0
964 0
088 0
909 0
605 0
960 0
049 0
913 0
129 0
511 0
161 0
201 0
952 0
483 0
201 0
949 0
449 0
949 0
886 0
634 0
444 0
381 0
376 0
109 0
177 0
802 0
567 0
687 0
341 0
761 0
918 0
033 0
262 0
376 0
                     Appendix H,  page  1
                                                             108

-------
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0100:11.0: 4.400: .000: .000: .000:? 2.572 0
0100:14.0: 4.200: .000: .000: .000:? 2.457 0
0100:17.0: 3.600: .000: .000: .000:7 2.109 0
0100:20.0: 4.200: .000: .000: .000:? 2.457 0
0009: .0: .843: .000: .000: .000:? 1.30570
0009: 1.0: .568: .000: .000: .000:7 .88170
0009: 2.0: .289: .000: .000: .000:7 .44970
0009: 3.0: .229: .000: .000: .000:7 .35670
0009: 4.0: .149: .000: .000: .000:7 .23270
: .0: 1.920: .000: .000: .000:7 2.073 0
: 3.0: .968: .000: .000: .000:? 1.050 0
: 7.0: .392: .000: .000: .000:? .427 0
:10.0: .380: .000: .000: .000:7 .414 0
:14.0: .224: .000: .000: .000:? .244 0
:21.0: .144: .000: .000: .000:7 .157 0
: .0: 3.720: .000: .000: .000:7 3.977 0
: 3.0: 1.364: .000: .000: .000:7 1.477 0
: 7.0: 1.228: .000: .000: .000:7 1.331 0
:10.0: .560: .000: .000: .000:7 .609 0
:14.0: .464: .000: .000: .000:? .505 0
:21.0: .148: .000: .000: .000:7 .161 0
: .0: 1.440: .000: .000: .000:7 1.559 0
: 3.0: .712: .000: .000: .000:7 .774 0
: 7.0: .532: .000: .000: .000:7 .579 0
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: .0: 2.940: .000: .000: .000:? 3.156 0
: 3.0: 1.932: .000: .000: .000:? 2.086 0
: 7.0: 1.228: .000: .000: .000:7 1.331 0
:10.0: 1.176: .000: .000: .000:7 1.275 0
:14.0: .652: .000: .000: .000:7 .709 0
:21.0: .348: .000: .000: .000:? .379 0
:28.0: .196: .000: .000: .000:7 .214 0
: .0:17.000: .000: .000: .000:7 16.927 0
: 3.0:13.200: .000: .000: .000:7 13.411 0
: 7.0: 7.200: .000: .000: .000:7 7.554 0
:10.0: 4.600: .000: .000: .000:7 4.894 0
:14.0: 3.600: .000: .000: .000:7 3.851 0
:21.0: 2.400: .000: .000: .000:7 2.584 0
:28.0: 1.800: .000: .000: .000:? 1.944 0
:35.0: 1.400: .000: .000: .000:? 1.516 0
:42.0: 1.200: .000: .000: .000:7 1.301 0
: .0:11.000: .000: .000: .000:? 11.308 0
: 3.0: 9.000: .000: .000: .000:7 9.352 0
: 7.0: 5.400: .000: .000: .000:? 5.721 0
:10.0: 3.000: .000: .000: .000:? 3.220 0
:14.0: 2.000: .000: .000: .000:? 2.158 0
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Appendix H, page  2
                               109

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                     Appendix H, page  3
                                                             110

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2






3
3
3
2
1
1

4
2
2
2
1





1










1



1



1




.105:
.081:
.064:
.029:
.026:
.011:
.011:
.400:
.800:
.360:
.140:
.150:
.044:
.000:
.800:
.200:
.140:
.540:
.860:
.260:
.740:
.200:
.540:
.660:
.260:
.340:
.660:
.400:
.214:
.199:
.121:
.200:
.922:
.650:
.500:
.384:
.330:
.200:
.134:
.080:
.054:
.036:
.680:
.640:
.122:
.048:
.680:
.360:
.040:
.000:
.112:
.460:
.300:
.104:
.088:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.780:
.840:
.440:
.720:
.600:
.340:
.134:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
.000:
.043:
.052:
.045:
.000:
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.000:
.000:
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.000:
.062:
.080:
.076:
.000:
.044:
.042:
.028:
.000:
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.000:
.000:
.000:
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.000:
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.340:
.260:
.164:
.140:
.116:
.086:
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.000:
.000:
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.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
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.914
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19.279
11.061
5.931
6.169
5.453
3.040
.805
7.091
6.006
5.896
4.797
3.536
2.409
1.422
7.807
4.797
5.018
4.280
2.560
1.269
.771
.497
.486
.321
3.328
2.567
1.816
1.400
1.077
.926
.562
.377
.225
.152
.101
.959
.402
.116
.071
.959
.231
.047
.016
.437
.181
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0
0
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0
0
0
0
3
3
3
3
3
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
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1
1
1
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
0
0
0
0
0
Appendix H, page  4
                                      111

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dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
'dimeth
dimeth
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dimeth
dimeth
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dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dimeth
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
:51
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:51
:51
:51
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:80
:80
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l:CANApple
2:CANApple
2:CANApple
2:CANApple
2:CANApple
2:CANApple
2:CANApple
3:CANApple
3:CANApple
3:CANApple
3:CANApple
3:CANApple
3:CANApple
3:CANApple
4:CANApple
4:CANApple
4:CANApple
4:CANApple
4:CANApple
4:CANApple
4:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
5:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
6:CANApple
1:TX Orange
1:TX Orange
1:TX Orange
1:TX Orange
2:TX Orange
2:TX Orange
2:TX Orange
2:TX Orange
1 : CAsOrange
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5: 1.0:
5: 2.0:
5: 7.0:
5:14.0:
0: 1.0:
0: 2.0:
0: 7.0:
0:14.0:
100: 4.0:
100:10.0:
100:18.0:
100:31.0:
100:46.0:
100:59.0:
100: 4.0:
100:10.0:
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2.456:
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.476:
.264:
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1.028:
.600:
.332:
.136:
.100:
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2.256:
1.616:
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1.922:
1.274:
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2.600:
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1.400:
1.600:
1.600:
1.200:
2.600:
2.000:
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.005 0
.962 0
.368 0
.187 0
.104 0
.127 0
.016 0
.404 0
.236 0
.131 0
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.020 0
.027 0
.884 0
.634 0
.222 0
.171 0
.124 0
.033 0
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.009 0
.003 0
.003 0
.002 0
.077 0
.053 0
.038 0
.017 0
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.003 0
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.254 1
.148 1
.007 1
.000 1
1.106 1
.750 1
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.002 1
7.297 0
6.210 0
3.998 0
4.556 0
4.556 0
3.437 0
7.297 0
5.662 0
                                             385
Appendix H, page  5
                              112

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dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
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dioxat
dioxat
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dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
:80 2:
:80 2:
:80 2:
:80 2:
:80 3:
:80 3:
:80 3:
:80 3:
:80 3:
:80 3:
:80 A:
:80 A:
:80 A:
:80 A:
:80 A:
:80 A:
:80 5:
:80 5:
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:80 9:
:8010:
:8010:
:8010:
:8010:
:8011:
:8011:
:8011:
:8011:
:38 1:
CAsOrange :
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5.00:
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5.00:
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5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
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5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
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5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
5.00:
A. 00:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
1250:
100:
100:
100:
100:
100:
100:
100:
100:
750:
18.0:
31.0:
A6.0:
59.0:
A.O:
10.0:
18.0:
31.0:
A6.0:
59.0:
A.O:
10.0:
18.0:
31.0:
A6.0:
59.0:
A.O:
10.0:
18.0:
31.0:
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59.0:
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10.0:
18.0:
31.0:
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59.0:
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10.0:
18.0:
31.0:
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59.0:
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10.0:
18.0:
31.0:
A6.0:
59.0:
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10.0:
18.0:
31.0:
A6.0:
59.0:
7.0:
13.0:
27.0:
35.0:
A.O:
10.0:
38.0:
A6.0:
1.0:
1.200:
l.AOO:
1.000:
1.600:
3.200:
2.600:
1.600:
l.AOO:
1.200:
l.AOO:
1.800:
2.000:
1.800:
1.600:
1.800:
1.000:
2.200:
2.000:
1.600:
l.AOO:
l.AOO:
1.000:
1.800:
1.600:
2.000:
l.AOO:
1.200:
.600:
1.000:
.800:
.600:
.800:
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1.200:
1.000:
.AOO:
.600:
.600:
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1.000:
.800:
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.200:
2.600:
2.200:
1.800:
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2.800:
1.600:
2.000:
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.000:
.000:
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.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
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.000:
.000:
.000:
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.000:
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.000:
.000:
.000:
.000:
.000:
3.A37
3.998
2.872
A. 556
8.90A
7.297
A. 556
3.998
3.A37
3.998
5.111
5.662
5.111
A. 556
5.111
2.872
6.210
5.662
A. 556
3.998
3.998
2.872
5.111
A. 556
5.662
3.998
3.A37
1.733
2.872
2.30A
1.733
2.30A
1.159
1.159
3.A37
2.872
1.159
1.733
1.733
1.159
2.872
2.30A
1.159
1.159
1.159
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7.297
6.210
5.111
3.998
7.836
A. 556
5.662
3.998
1.733
0^
0390
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
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Appendix H, page  6
                                    113

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dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
dioxat
ethion
ethion
ethion
ethion
ethion
ethion
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ethion
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ethion
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ethion
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ethion
ethion
ethion
ethion
:38
:38
:38
:38
:38
:38
:38
:38
:38
:38
:38
:27
:27
:27
:27
:27
:27
:27
:27
:27
:27
:27
:27
:27
:27
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:47
:12
:12
: 12
:12
:12
:12
:12
:12
:12
:12
:12
:12
1:FL Orange:
1:FL Orange:
1:FL Orange:
1:FL Orange:
1:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
1 : CAvGrapes :
1 : CAvGrapes :
1 : CAvGrapes :
1 : CAvGrapes :
1 : CAvGrapes :
1 : CAvGrapes :
1 : CAvGrapes :
2 : CAvGrapes :
2 : CAvGrapes :
2 : CAvGrapes :
2: CAvGrapes:
2 : CAvGrapes :
2 : CAvGrapes :
2 : CAvGrapes :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
1: CAvOrange:
1 : CAvOrange:
2 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
2: CAvOrange:
2 : CAvOrange :
2: CAvOrange:
3 : CAvOrange :
3 : CAvOrange :
3: CAvOrange:
3: CAvOrange:
3 : CAvOrange :
3 : CAvOrange :
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
1:AZ Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
1.0:
1.0:
1.0:
1.0:
1.0:
1.0:
1.0:
1.25:
1.25:
1.25:
1.25:
1.25:
1.25:
1.25:
3.0:
3.0:
3.0:
3.0:
3.0:
3.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
4.0:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
4.00:
4.00:
4.00:
750: 2
750: 5
750:10
750:20
750:30
750: 1
750: 2
750: 5
750:10
750:20
750:30
30:
30: 1
30: 3
30: 7
30:14
30:21
30:28
200:
200: 1
200: 3
200: 7
200:14
200:21
200:28
500: 2
500: 5
500: 9
500:16
500:23
500:33
500: 2
500: 5
500: 9
500:16
500:23
500:33
500: 2
500: 5
500: 9
500:16
500:23
500:33
350:
350: 1
350: 3
350: 5
350: 7
350:14
350:21
350:28
350:42
350:
.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:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
350: 1.0:
350: 3
.0:
.460:
.326:
.250:
.192:
.164:
.080:
.056:
.036:
.024:
.018:
.014:
.800:
.600:
.200:
.065:
.021:
.019:
.015:
.900:
.700:
.350:
.070:
.032:
.020:
.012:
1.102:
.475:
.236:
.149:
.078:
.037:
.516:
.754:
.342:
.548:
.298:
.230:
1.771:
.834:
.669:
.268:
.176:
.127:
18.136:
17.612:
15.848:
10.392:
12.040:
9.420:
7.398:
4.442:
2.356:
10.252:
9.072:
7.856:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.070:
.072:
.078:
.055:
.025:
.011:
.007:
.080:
.092:
.105:
.058:
.030:
.019:
.010:
.100:
.087:
.064:
.048:
.024:
.011:
.028:
.054:
.034:
.090:
.042:
.034:
.110:
.076:
.112:
.063:
.044:
.034:
.172:
.548:
.930:
.944:
1.220:
1.386:
1.412:
1.238:
1.006:
.122:
.130:
.142:
.uuu:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.005:
.020:
.048:
.060:
.050:
.035:
.004:
.004:
.011:
.039:
.045:
.039:
.032:
.000:
.029:
.041:
.032:
.028:
.029:
.008:
.012:
.011:
.047:
.039:
.044:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.022:
.070:
.066:
.106:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
. uuu .
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
^ . _/...-
.946
.726
.558
.477
.233
.163
.105
.070
.052
.041
1.356
1.057
.466
.263
.166
.125
.089
1.532
1.241
.728
.262
.168
.122
.085
2.710
1.340
.777
.523
.297
.175
1.255
1.858
.881
1.554
.862
.702
4.207
2.058
1.769
.754
.501
.369
34.195
34.005
31.962
22.942
26.325
21.885
18.239
12.175
7.397
21.111
18.969
16.708
0
°391
0
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Appendix H, page  7
                                     114

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U2
:12
:12
:12
:12
:12
:12
:12
:12
-.12
: 12
:12
: 12
: 12
:12
: 12
:12
:12
:12
: 12
:34
:34
:34
:34
:34
:34
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:34
:34
:34
:34
:34
:34
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:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
:34
2:FL
2:FL
2:FL
2:FL
2:FL
2:FL
3:TX
3:TX
3:TX
3:TX
3:TX
3:TX
3:TX
3:TX
3:TX
4:CA
4:CA
4:CA
4:CA
4:CA
4:CA
4:CA
4:CA
4:CA
1:FL
1:FL
1:FL
1:FL
1:FL
1:FL
2:FL
2:FL
2:FL
2:FL
2:FL
2:FL
2:FL
2:FL
2:FL
3:FL
3:FL
3:FL
3:FL
3:FL
3:FL
4:FL
4:FL
4:FL
4:FL
4:FL
4:FL
4:FL
4:FL
4:FL
5:FL
Orange:
Orange:
Orange:
Orange:
Orange :
Orange:
Orange :
Orange :
Orange:
Orange:
Orange:
Orange :
Orange:
Orange :
Orange:
Orange:
Orange :
Orange :
Orange:
Orange :
Orange:
Orange:
Orange :
Orange :
Orange:
Orange:
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Orange :
Orange :
Orange :
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Orange:
Orange:
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Orange :
Orange :
Orange :
Orange :
Orange:
Orange:
Orange:
Orange:
Orange:
Orange :
Orange:
Orange:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
3.00:
3.00:
3.00:
3.00:
3.00:
3.00:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
350: 5
350: 7
350:14
350:21
350:28
350:42
350:
350: 1
350: 3
350: 5
350: 7
350:14
350:21
350:28
350:42
350:
350: 1
350: 3
350: 5
350: 7
350:14
350:21
350:28
350:42
1200:
1200: 1
1200: 3
1200: 5
1200: 7
1200:14
1200:
1200: 1
1200: 3
1200: 5
1200: 7
1200:14
1200:21
1200:28
1200:35
1200:
1200: 1
1200: 3
1200: 5
1200: 7
1200:14
1200:
1200: 1
1200: 3
1200: 5
1200: 7
1200:14
1200:21
1200:28
1200:35
1200:
.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:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
5.498:
3.024:
1.954:
.844:
.726:
.368:
6.776:
4.534:
3.846:
2.952:
1.968:
.420:
.226:
.126:
.030:
4.336:
3.900:
3.504:
2.894:
2.274:
.988:
.476:
.290:
.072:
.199:
.122:
.015:
.006:
.006:
.004:
.283:
.066:
.047:
.033:
.034:
.033:
.010:
.007:
.008:
.569:
.249:
.050:
.009:
.003:
.005:
.265:
.116:
.079:
.061:
.059:
.053:
.020:
.015:
.008:
.505:
.124:
.092:
.072:
.076:
.062:
.044:
.102:
.090:
.092:
.092:
.084:
.062:
.048:
.042:
.012:
..104:
.110:
.106:
.126:
.116:
.072:
.082:
.064:
.026:
.008:
.012:
.008:
.005:
.003:
.003:
.024:
.005:
.006:
.008:
.010:
.010:
.008:
.004:
.004:
.084:
.043:
.010:
.009:
.005:
.004:
.033:
.005:
.008:
.010:
.013:
.012:
.011:
.010:
.006:
.024:
.000:
.001:
.001:
.008:
.007:
.006:
.000:
.000:
.000:
.000:
.003:
.007:
.013:
.014:
.007:
.000:
.000:
.000:
.005:
.006:
.005:
.015:
.032:
.021:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
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.000:
.000:
.000:
.000:
12.059 2
6.876 2
4.527 2
2.100 2
1.800 2
.952 2
14.548 2
10.030 2
8.608 2
6.722 2
4.589 2
1.112 2
.653 2
.416 2
.111 2
9.651 2
8.759 2
7.921 2
6.681 2
5.329 2
2.405 2
1.300 2
.878 2
.273 2
.472 1
.307 1
.052 1
.026 1
.021 1
.015 1
.700 1
.161 1
.121 1
.094 1
.101 1
.098 1
.041 1
.026 1
.029 1
1.483 1
.667 1
.138 1
.041 1
.018 1
.020 1
.678 1
.277 1
.199 1
.163 1
.165 1
.148 1
.071 1
.057 1
.031 1
1.203 1
                                            392
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                              115

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:34 5
:34 5
:34 5
:34 6
:34 6
:34 6
:34 6
:34 6
:34 6
:34 6
:34 6
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:3410
:3410
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:FL Orange:
:FL Orange:
:FL Orange:
:FL Orange:
.•CAsOrange:
: CAsOrange :
: CAsOrange:
: CAsOrange :
: CAsOrange:
: CAsOrange :
: CAsOrange :
: CAsOrange:
: CAsOrange:
: CAsOrange:
: CAsOrange:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
4.50:
9.00:
9.00:
9.00:
9.00:
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9.00:
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9.00:
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9.00:
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12.50:
12.50:
12.50:
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1200: 1.
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2000: .
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0:
0:
0:
0:
0:
0:
.126:
.034:
.027:
.022:
.009:
.468:
.203:
.103:
.058:
.021:
.044:
.010:
.009:
.007:
.416:
.095:
.048:
.024:
.015:
.011:
.405:
.190:
.222:
.108:
.041:
.028:
.014:
.016:
.009:
.635:
.275:
.116:
.018:
.016:
.009:
.752:
.316:
.237:
.262:
.164:
.042:
.024:
.024:
.016:
4.200:
3.600:
2.400:
2.800:
2.600:
1.940:
1.420:
1.400:
1.620:
1.540:
1.160:
.014:
.006:
.003:
.009:
.005:
.049:
.005:
.004:
.009:
.008:
.011:
.008:
.007:
.005:
.032:
.019:
'.016:
.018:
.012:
.006:
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.003:
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.014:
.009:
.009:
.009:
.007:
.006:
.020:
.024:
.018:
.008:
.005:
.005:
.089:
.008:
.007:
.019:
.022:
.016:
.016:
.016:
.008:
.000:
.000:
.032:
.000:
.056:
.086:
.066:
.068:
.090:
.086:
.070:
.000:
.000:
.000:
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.000:
.000:
.000:
.000:
.000:
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.000:
.000:
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.000:
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.000:
.000:
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.000:
.000:
.000:
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.000:
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1








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64
59
50
50
57
54
44
44
51
49
41
.320 1
.093 1
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.173 1
.473 1
.245 1
.154 1
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.036 1
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.261 1
.146 1
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.976 0
.313 0
.905 0
.313 0
.058 0
.404 0
.318 0
.430 0
.296 0
.613 0
.407 0
                                                 39
Appendix H, page  9
                                 116

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CA Orange:
CA Orange:
CA Orange:
CA Orange:
CA Orange:
CA Orange:
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                    Appendix H, page  10
                                                               117

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1:SC tobaco:0.375: : 3.0:
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2:SC tobaco: 0.375: : 1.0:
2:SC tobaco: 0.375: : 3.0:
2:SC tobaco:0.375: : 5.0:
3:SC tobaco: 0.375: : 1.0:
3:SC tobaco: 0.375: : 3.0:
3:SC tobaco:0.375: : 5.0:
4:SC tobaco:0.375: : 1.0:
4:SC tobaco:0.375: : 3.0:
1:FL Orange: 0.75: 100: 1.0:
1:FL Orange: 0.75: 100: 6.0:
1:FL Orange: 0.75: 100: 8.0:
2:FL Orange: 0.75: 100: 1.0:
2:FL Orange: 0.75: 100: 2.0:
2:FL Orange: 0.75: 100: 3.0:
2:FL Orange: 0.75: 100: 7.0:
2:FL Orange: 0.75: 100: 9.0:
3:FL Orange: 2.00: 100: 1.0:
3:FL Orange: 2.00: 100: 3.0:
3:FL Orange: 2.00: 100: 6.0:
3:FL Orange: 2.00: 100; 8.0;
4:FL Orange: .75: 100: 1.0:
4:FL Orange: .75: 100: 3.0:
4:FL Orange: .75: 100: 6.0:
4:FL Orange: .75: 100: 8.0:
l:CAsPeach : 2.00: 400: .0:
l:CAsPeach : 2.00: 400: 3.0:
l:CAsPeach : 2.00: 400: 7.0:
l:CAsPeach : 2.00: 400:14.0:
l:CAsPeach : 2.00: 400:21.0:
l:CAsPeach : 2.00: 400:28.0:
l:CAsPeach : 2.00: 400:70.0:
2:CAsPeach : 1.00:0400: .0:
2:CAsPeach : 1.00:0400: 3.0:
2:CAsPeach : 1.00:0400: 7.0:
2:CAsPeach : 1.00:0400:14.0:
2:CAsPeach : 1.00:0400:21.0:
2:CAsPeach : 1.00:0400:28.0:
2:CAsPeach : 1.00:0400:70.0:
3:CAsPeach : 1.00:0400: .0:
3:CAsPeach : 1.00:0400: 3.0:
3:CAsPeach : 1.00:0400: 7.0:
3:CAsPeach : 1.00:0400:14.0:
3:CAsPeach : 1.00:0400:21.0:
3:CAsPeach : 1.00:0400:28.0:
3:CAsPeach : 1.00:0400:70.0:
1:AZ Cotton: 1.00: 9: .0:
1:AZ Cotton: 1.00: 9: .5:
1:AZ Cotton: 1.00: 9: 1.0:
1:AZ Cotton: 1.00: 9: 2.0:
1:AZ Cotton: 1.00: 9: 3.0:
1:AZ Cotton: 1.00: 9: 4.0:
l:CAvplum : 2.47: 330: .0:
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                                     118

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119

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Appendix H, page  13
                              120

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8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
100:
350:
350:
350:
350:
350:
350:
350:
350:
350:
350:
350:
350:
350:
350:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
1450:
.0:
1.0:
3.0:
5.0:
7.0:
14.0:
21.0:
28.0:
35.0:
.0:
1.0:
3.0:
5.0:
7.0:
14.0:
21.0:
28.0:
35.0:
1.0:
3.0:
5.0:
7.0:
14.0:
.0:
1.0:
3.0:
5.0:
7.0:
14.0:
21.0:
28.0:
42.0:
.0:
1.0:
3.0:
7.0:
14.0:
28.0:
42.0:
.0:
1.0:
3.0:
7.0:
14.0:
28.0:
42.0:
.0:
1.0:
3.0:
5.0:
7.0:
14.0:
21.0:
28.0:
42.0:
.440:
.040:
.025:
.021:
.011:
.008:
.008:
.003:
.002:
2.719:
.551:
.174:
.102:
.041:
.023:
.019:
.008:
.002:
14.086:
3.604:
2.102:
.836:
.286:
11.246:
8.590:
6.126:
4.130:
3.832:
1.832:
.674:
.186:
.086:
3.642:
2.036:
.890:
.272:
.060:
.010:
.004:
3.212:
1.924:
.974:
.218:
.064:
.012:
.006:
3.280:
2.552:
.786:
.540:
.286:
.112:
.034:
.026:
.004:
.022:
.015:
.013:
.011:
.005:
.002:
.004:
.000:
.000:
.085:
.034:
.030:
.016:
.006:
.006:
.003:
.000:
.000:
.262:
.170:
.134:
.094:
.092:
.038:
.134:
.222:
.228:
.302:
.152:
.122:
.090:
.090:
.034:
.052:
.114:
.090:
.050:
.014:
.006:
.034:
.058:
.064:
.036:
.022:
.008:
.006:
.018:
.048:
.024:
.028:
.026:
.008:
.006:
.012:
.004:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
17.097
5.988
4.906
4.272
2.135
.821
1.517
.085
.060
62.386
22.728
13.798
7.880
3.147
2.569
1.640
.195
.055
98.814
77.570
62.979
41.583
32.509
94.724
92.679
90.040
83.943
86.646
62.812
44.845
30.316
28.554
64.251
49.864
46.259
31.797
17.291
5.016
2.174
60.198
49.512
37.319
16.502
8.874
3.050
2.223
58.616
55.306
24.442
20.770
14.987
5.442
2.905
4.730
1.488
0
0
0
0
o 39C
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
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
                     Appendix H, page  14
121

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etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
12 6:CA
12 6:CA
12 6:CA
12 6:CA
12 6:CA
12 6:CA
   6:CA
:12
:12  6
:12  6
:12
:12
:12
:12
:12
:12
:12
:12
:12
     :CA
     :CA
     lAZ
     :AZ
     ;AZ
     :AZ
     :AZ
     :AZ
     :AZ
     :AZ
     :AZ
   7
   7
   7
   7
   7
   7
   7
   7
   7
12 8:CA
12 8:CA
12 8:CA
12 8:CA
12 8:CA
12 8:CA
12 8:CA
12 8:CA
12 9:CA
12 9:CA
12 9:CA
12 9:CA
12 9:CA
12 9:CA
12 9:CA
1210:FL
1210:FL
1210:FL
1210:FL
1210:FL
1210:FL
1210:FL
1210:FL
1210:FL
    :TX
    :TX
    :TX
    :TX
    :TX
    :TX
    :TX
    :TX
    :TX
    :AZ
    :AZ
    :AZ
:75
:75
:75
:75 1:AZ
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Grapes:
Grapes:
Grapes:
Grapes:
Grapes:
Grapes:
Grapes:
Grapes:
Apple  :
Apple  :
Apple  :
Apple  :
Apple  :
Apple  :
Apple  :
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Cotton:
Cotton:
Cotton:
Cotton:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
  .50:
  .50:
  .50:
  .50:
                       350:
  5:
  5:
  5:
  5:
350
350
350
350
350
350:14.0:
350:21.0:
350:28.0:
350:42.0:
350
350
350
350
                            7.0
350: 7.0:
350:14.0:
350:21.0:
350:28.0:
350:42.0:
350
350
350
350
350
350:14.0
350:28.0
350:42.0
350
350
350
350
350
350:14.0
350:42.0
350
350
350
350
                             .0:
                            1.0:
                            3.0:
                            5.0:
                            7.0:
                       350:14.0:
                       350:21.0;
                       350:28.0:
                       350:42.0:
                       350
                       350
                       350
                       350
                       350
                       350:14.0
                       350:21.0
                       350:28
                       350:42
                            7.0
  0;
  0:
 .0:
 .5
1.0:
     7.440:
     5.396:
     2.102:
     1.346:
      .792:
      .202:
      .068:
      .024:
      .004:
    11.200:
     6.646:
       826:
       642:
       918:
      .578:
      .270:
      .156:
      .040:
    15.378:
    14.086:
 3.
 2.
 1.
                                 3,
                                 2.
   604:
   102:
  .836:
  .286:
  .052:
  .008:
18.690:
11.970:
 3.892:
 1.636:
 1.286:
  .056:
  .010:
10.276:
   508:
   342:
   624:
   964:
  .560:
  .226:
  .128:
  .048:
11.530:
   426:
   490;
   668:
   166:
   098:
   024:
   010:
   004:
   020:
   750:
   580:
     5.
     3.
     2,
     1.
          7.
          2.
          2.
          1,
                                 4.
                                 2.
                                 2.
                            2.0:  1.960
.030:
.118:
.050:
.060:
.038:
.010:
.006:
.008:
.004:
.126:
.216:
.212:
.274:
.274:
.134:
.110:
.080:
.034:
.188:
.262:
.170:
.134:
.094:
.092:
.030:
.004:
.162:
.292:
.382:
.230:
.176:
.040:
.012:
.056:
.034:
.058:
.072:
.078:
.042:
.038:
.026:
.014:
.070:
.104:
.074:
.104:
.060:
.016:
.008:
.006:
.002:
.020:
.040:
.040:
.050:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:?
.000:?
.000:?
.000:?
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.000:?
.000:?
.000:
.000:
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.000:
.000:
.000:
.000:
.000:
.000:
.000:?
.000:?
.000:?
.000:?
85. yo/ 0
82.805 0
50.338 0
42.077 0
28.160 0
8.188 0
3.726 0
3.340 0
1.488 0
96.077 0
91.068 0
81.679 0
80.174 0
76.244 0
45.828 0
36.373 0
27.294 0
12.093 0
95.438 0
95.233 0
64.150 0
49.437 0
30.852 0
23.649 0
7.773 0
1.091 0
97.248 0
93.625 0
79.485 0
56.502 0
47.421 0
10.022 0
3.005 0
93.688 0
77.570 0
64.571 0
59.637 0
53.391 0
24.931 0
17.250 0
11.565 0
5.913 0
95.606 0
89.125 0
58.554 0
64.305 0
39.413 0
7.728 0
3.340 0
2.321 0
.796 0
65.11370
55.54170
53.65170
47.87070
             Appendix  H,  page   15
                                                        122

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:75
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:75
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:79
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1:AZ Cotton:
2:AZ Cotton:
2:AZ Cotton:
2:AZ Cotton:
2:AZ Cotton:
2:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
l:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
2:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
3:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
4:CAvCitrus:
5:CAvCitrus:
5:CAvCitrus:
5:CAvCitrus:
.50:
.50:
.50:
.50:
.50:
.50:
1.00:
1.00:
1.00:
1.00:
1.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
5: 3.
5: .
5: .
5: 1.
5: 2.
5: 3.
9: 1.
9: 1.
9: .
9: 1.
9: 2.
100: .
100: 1.
100: 2.
100: 3.
100: 7.
100:10.
100:14.
100:21.
100:28.
100: .
100: 1.
100: 2.
100: 3.
100: 5.
100: 7.
100:10.
100:14.
100:21.
100:28.
100:57.
100:63.
100: .
100: 1.
100: 2.
100: 3.
100: 5.
100: 7.
100:10.
100:14.
100:21.
100:28.
100:35.
100:63.
100: .
100: 1.
100: 3.
100: 7.
100:10.
100:14.
100:21.
100:28.
100: .
100: 1.
100: 3.
0:
0:
5:
0:
0:
0:
0:
5:
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:
0:
0:
0:
0:
0:
0:
0:
0:
0:
0:
0:
0:
1.240:
.920:
.760:
.590:
.440:
.380:
.350:
.370:
2.330:
.270:
.150:
9.000:
.000:
3.200:
1.400:
.000:
.360:
.120:
.060:
.036:
8.000:
.000:
4.000:
3.000:
1.700:
.900:
.520:
.300:
.066:
.000:
.020:
.000:
7.000:
.000:
5.000:
1.800:
1.040:
.600:
.240:
.140:
.044:
.000:
.034:
.014:
.780:
3.200:
1.600:
.340:
.180:
.060:
.030:
.018:
8.000:
4.400:
1.400:
.040:
.000:
.010:
.010:
.010:
.010:
.004:
.002:
.000:
.017:
.012:
.110:
.380:
.000:
.300:
.340:
.320:
.200:
.140:
.104:
.044:
.200:
.000:
.540:
.540:
.400:
.440:
.360:
.160:
.110:
.000:
.080:
.050:
.120:
.000:
.280:
.180:
.220:
.240:
.220:
.044:
.032:
.000:
.012:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
35
20
19
16
13
11
9
9
43
11
7
92
73
55
75
69
70
51
39
31
88
50
63
92
90
80
81
73
43
31

24
85
34
71
76
58
60
59
55
15
10

4
17
55
32
8
4
1


86
66
29
.649?0
.173?0
.78170
.37170
.24170
.95770
.46570
.22570
.48270
.69870
.49270
.813 0
.524 0
.038 0
.312 0
.548 0
.151 0
.780 0
.625 0
.113 0
.378 0
.313 0
.182 0
.848 C
.105 0
.283 0
.150 0
.655 0
.787 0
.934 0
.498 0
.404 0
.389 0
.273 0
.320 0
.041 0
.905 0
.118 0
.313 0
.262 0
.199 0
.587 0
.846 0
.444 0
.703 0
.038 0
.946 0
.142 0
.397 0
.488 0
.747 0
.449 0
.444 0
.683 0
.511 0
                                            400
Appendix H, page  16
                              123

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:84 5:CAvCitrus:
:8A 5:CAvCitrus:
:8A 5:CAvCitrus:
:8A 5: CAvCitrus:
:8A 5
:8A 5
:8A 6
:8A 6
:8A 6
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: CAvCitrus:
:CAvCitrus:
:CAvCitrus:
:CAvCitrus:
: CAvCitrus:
: CAvCitrus :
:CAvCitrus:
: CAvCitrus:
:CAvOrange:
: CAvOrange :
: CAvOrange :
: CAvOrange :
: CAvOrange :
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: CAvOrange:
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: CAvOrange :
: CAvOrange:
: CAvOrange :
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: CAvOrange :
: CAvOrange:
: CAvOrange :
: CAvOrange :
: CAvOrange :
: CAvOrange:
: CAvOrange:
: CAvOrange :
: CAvOrange:
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
8.00
6.0
6.0
6.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
2.25
2.25
2.25
2.25
2.0
2.0
2.0
2.0
2.0
2.0
2.5
2.5
2.5
1.5
1.5
1.5
1.5
1.5
1.5
1.3
1.3
1.3
2.0
2.0
2.0
2.0
3.1
3.1
3.1
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
: 100
:1200
:1200
:1200
:1000
:1000
:1000
:1000
:1000
:1000
:1000
:1000
: 900
: 900
: 900
: 900
: 300
: 300
: 300
: 300
: 300
: 300
:1000
:1000
:1000
: 750
: 750
: 750
: 600
: 600
: 600
: 500
: 500
: 500
: 200
: 200
: 200
: 200
:1250
:1250
:1250
: 5.0:
: 7.0:
:10.0:
:1A.O:
:21.0:
:28.0:
: .0:
: 1.0:
: 3.0:
: 5.0:
: 7.0:
: 9.0:
:13.0:
:20.0:
:3A.O:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
:23.0:
: 2.0:
: 9.0:
:16.0:
:23.0:
: 2.0:
: 9.0:
:16.0:
:23.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
: 2.0:
: 9.0:
:16.0:
:22.0:
: 2.0:
: 9.0:
:16.0:
.500:
.300:
.090:
.056:
.020:
.020:
5.000:
A. 800:
1.200:
.800:
.A20:
.130:
.120:
.OAO:
.036:
.26A:
.030:
.010:
.398:
.055:
.025:
.008:
.A13:
.095:
.050:
.011:
1.A3A:
.311:
.11A:
.OA2:
.181:
.023:
.007:
.171:
.017:
.009:
.150:
.006:
.006:
.191:
.013:
.003:
.050:
.007:
.001:
.252:
.027:
.010:
.187:
.021:
.007:
.003:
.10A:
.023:
.008:
.000;
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.019:
.013:
.007:
.032:
.033:
.009:
.006:
.030:
.012:
.010:
.006:
.109:
.065:
.050:
.020:
.090:
.025:
.007:
.071:
.020:
.008:
.109:
.026:
.010:
.011:
.003:
.002:
.006:
.001:
.001:
.03A:
.020:
.010:
.053:
.017:
.007:
.005:
.021:
.009:
.007:
.C!OG;
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
• v>l/"w •
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
7.220
2.223
1.389
.A98
.A98
71.320
69.851
25.900
18.114
9.960
3.195
2.953
.994
.895
12.289
5.027
2.635
19.079
12.122
3.684
2.316
18.695
6.262
4.669
2.250
52.293
26.250
18.395
7.650
30.128
9.040
2.698
25.362
7.295
2.938
34.179
8.816
3.572
8.102
1.293
.638
3.378
.622
.255
16.552
7.348
3.703
20.654
6.253
2.425
1.830
9.582
3.745
2.717
0*401
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
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Appendix H, page  17

-------
etp     :6713:CAvOrange:  1.9: 750: 2.0:  .175:  .035:  .000:  .000:  15.337 0
etp     :6713:CAvOrange:  1.9: 750: 9.0:  .028:  .014:  .000:  .000:   5.449
etp     :6713:CAvOrange:  1.9: 750:16.0:  .011:  .009:  .000:  .000:   3.491
etp     :6714:CAvOrange:  2.5: 300: 2.0:  .295:  .034:  .000:  .000:  17.431 0
etp     :6714:CAvOrange:  2.5: 300: 9.0:  .033:  .012:  .000:  .000:   5.034 0
etp     :6714:CAvOrange:  2.5: 300:16.0:  .006:  .007:  .000:  .000:   2.467 0
etp     :6715:CAvOrange:  3.0:1200: 2.0:  .089:  .023:  .000:  .000:   9.779 0
etp     :6715:CAvOrange:  3.0:1200: 9.0:  .020:  .006:  .000:  .000:   2.624 0
etp     :6715:CAvOrange:  3.0:1200:16.0:  .013:  .002:  .000:  .000:    .977 0
etp     :6716:CAvOrange:  2.0: 500: 2.0:  .241:  .021:  .000:  .000:  12.471 0
etp     :6716:CAvOrange:  2.0: 500: 9.0:  .044:  .018:  .000:  .000:   7.161 0
etp     :6716:CAvOrange:  2.0: 500:16.0:  .008:  .007:  .000:  .000:   2.691 0
etp     :6717:CAvOrange:  1.9: 750: 2.0:  .688:  .025:  .000:  .000:  22.974 0
etp     :6717:CAvOrange:  1.9: 750: 9.0:  .048:  .011:  .000:  .000:   4.972 0
etp     :6717:CAvOrange:  1.9: 750:16.0:  .011:  .007:  .000:  .000:   2.731 0
etp     :6718:CAvOrange:  1.9: 750: 2.0:  .229:  .052:  .000:  .000:  21.168 0
etp     :6718:CAvOrange:  1.9: 750: 9.0:  .058:  .025:  .000:  .000:   9.681 0
etp     :6718:CAvOrange:  1.9: 750:16.0:  .012:  .012:  .000:  .000:   4.232 0
etp     :6719:CAvOrange:  2.0: 300: 2.0:  .483:  .167:  .000:  .000:  50.491 0
etp     :6719:CAvOrange:  2.0: 300: 9.0:  .012:  .054:  .000:  .000:  17.388 0
etp     :6719:CAvOrange:  2.0: 300:16.0:  .005:  .021:  .000:  .000:   7.338 0
etp     :6720:CAvOrange:  7.5:1800: 2.0: 1.297:  .227:  .000:  .000:  67.336 0
etp     :6720:CAvOrange:  7.5:1800: 9.0:  .120:  .135:  .000:  .000:  39.492 0
etp     :6720:CAvOrange:  7.5:1800:16.0:  .039:  .021:  .000:  .000:   8.011 0
etp     :6720:CAvOrange:  7.5:1800:21.0:  .009:  .017:  .000:  .000:   6.095 0
etp     :6721:CAvOrange:  2.0: 300: 2.0:  .173:  .328:  .000:  .000:  69.551 0
etp     :6721:CAvOrange:  2.0: 300: 9.0:  .021:  .066:  .000:  .000:  20.967 0
etp     :6721:CAvOrange:  2.0: 300:16.0:  .033:  .021:  .000:  .000:   7.698 0
etp     :6722:CAvOrange:  2.0: 300: 2.0:  .439:  .396:  .000:  .000:  77.570 0
etp     :6722:CAvOrange:  2.0: 300: 9.0:  .043:  .072:  .000:  .000:  23.060 0
etp     :6722:CAvOrange:  2.0: 300:16.0:  .002:  .018:  .000:  .000:   6.146 0
etp     :6723:CAvOrange:  1.9: 750: 3.0:  .170:  .001:  .000:  .000:   4.582 0
etp     :6723:CAvOrange:  1.9: 750:10.0:  .015:  .004:  .000:  .000:   1.660 0
etp     :6723:CAvOrange:  1.9: 750:17.0:  .005:  .003:  .000:  .000:   1.139 0
etp     :6724:CAvOrange:  1.9: 750: 2.0:  .153:  .016:  .000:  .000:   8.875 0
etp     :6724:CAvOrange:  1.9: 750: 9.0:  .008:  .005:  .000:  .000:   1.768 0
etp     :6724:CAvOrange:  1.9: 750:16.0:  .004:  .002:  .000:  .000:    .965 0
etp     :6725:CAvOrange:  2.5:1000: 2.0:  .417:  .025:  .000:  .000:  17.439 0
etp     :6725:CAvOrange:  2.5:1000: 9.0:  .038:  .016:  .000:  .000:   6.474 0
etp     :6725:CAvOrange:  2.5:1000:16.0:  .004:  .005:  .000:  .000:   1.806 0
etp     :6726:CAvOrange:  2.0: 250: 2.0:  .771:  .366:  .000:  .000:  77.026 0
etp     :6726:CAvOrange:  2.0: 250: 9.0:  .069:  .051:  .000:  .000:  17.821 0
etp     :6726:CAvOrange:  2.0: 250:16.0:  .021:  .025:  .000:  .000:   8.994 0
etp     :6727:CAvOrange:  4.6:1850: 2.0:  .387:  .011:  .000:  .000:  12.768 0
etp     :6727:CAvOrange:  4.6:1850: 9.0:  .043:  .016:  .000:  .000:   6.289 0
etp     :6727:CAvOrange:  4.6:1850:16.0:  .012:  .005:  .000:  .000:   1.928 0
etp     :6728:CAvOrange:  7.5:1500: 2.0:  .618:  .321:  .000:  .000:  72.081 0
etp     :6728:CAvOrange:  7.5:1500: 9.0:  .067:  .115:  .000:  .000:  34.296 0
etp     :6728:CAvOrange:  7.5:1500:16.0:  .024:  .058:  .000:  .000:  18.848 0
etp     :6728:CAvOrange:  7.5:1500:22.0:  .010:  .018:  .000:  .000:   6.373 0
etp     :6729:CAvOrange:  2.3: 900: 2.0:  .363:  .032:  .000:  .000:  18.360 0
etp     :6729:CAvOrange:  2.3: 900: 9.0:  .020:  .013:  .000:  .000:   4.981 0
etp     :6729:CAvOrange:  2.3: 900:16.0:  .004:  .007:  .000:  .000:   2.535 0
etp     :6730:CAvOrange:  1.9: 750: 2.0:  .200:  .145:  .000:  .000:  42.706 0
etp     :6730:CAvOrange:  1.9: 750: 9.0:  .024:  .022:  .000:  .000:   8.088 0
                     Appendix H, page  18
125

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etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
etp
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etp
etp
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etp
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etp
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:o/ -JU:uvvurange:
:45 0:CAvOrange:
:45 0:CAvOrange:
:45 OrCAvOrange:
:45 0:CAvOrange:
:45 OrCAvOrange:
:45 0:CAvOrange:
:45 0:CAvOrange:
:45 0:CAvOrange:
:45 0:CAvOrange:
:45 OrCAvOrange:
:45 OrCAvOranger
:45 OrCAvOranger
:45 OrCAvOranger
:45 0:CAvOrange:
:46 IrCAvOranger
:46 IrCAvOrange:
:46 l:CAvOranger
:46 IrCAvOrange:
:46 IrCAvOranger
:46 2:CAvOranger
:46 2:CAvOrange:
:46 2:CAvOrange:
:46 2rCAvOrange:
:46 2rCAvOrange:
:46 2rCAvOrange:
:46 3:CAvOrange:
:46 SrCAvOrange:
:46 SrCAvOrange:
r46 3:CAvOrange:
:46 SrCAvOrange:
:46 SrCAvOrange:
:46 4:CAvOrange:
:46 4:CAvOrange:
:46 4rCAvOranger
r46 4:CAvOranger
r46 4rCAvOrange:
:46 5:CAvOrange:
:46 5:CAvOrange:
:46 SrCAvOrange:
:46 5:CAvOrange:
:46 5:CAvOrange:
:46 SrCAvOranger
:46 6rCAvOrange:
:46 6rCAvOranger
:46 6:CAvOrange:
:46 6:CAvOranger
:46 6:CAvOrange:
:46 6rCAvOrange:
:46 6:CAvOrange:
:46 7:CAvOrange:
:46 7:CAvOrange:
:46 7:CAvOrange:
:46 7:CAvOrange:
:46 7:CAvOrange:
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71.624
56.547
20.727
27.288
11.117
11.910
8.864
12.306
11.716
11.604
5.983
13.609
9.210
8.104
37.081
21.662
10.432
7.751
2.752
69.611
39.167
29.272
6.850
1.028
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23.934
7.244
2.614
2.406
1.162
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13.093
3.660
1.607
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52.966
28.611
11.289
7.320
3.359
1.332
71.673
61.165
46.971
41.692
15.768
12.083
4.291
81.947
72.534
63.215
46.284
25.580
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0
0
0
0
0
0
0
0
0
0
0
Appendix H, page  19                      1 O^
                                          I CO

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:4613:CAvOrange:
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:4615:CAvOrange:
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6.3:
6.3:
7.5:
7.5:
7.5:
7.5:
7.5:
2.0:
2.0:
2.0:
2.0:
2.0:
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4.0:
4.0:
4.0:
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                     Appendix H, page  20
                                                      127

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10.788
50.881
61.257
50.064
37.178
15.832
8.349
7.301
46.366
43.237
13.742
18.928
12.150
3.904
2.642
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0
0
0
0
0
0
0
Appendix H, page  21
                                  128

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8:CA Grapes: .75: 100: 3.0:
8:CA Grapes: .75: 100: 7.0:
9:CA Grapes: .75: 25: .0:
9:CA Grapes: .75: 25: 1.0:
9:CA Grapes: .75: 25: 3.0:
9:CA Grapes: .75: 25: 7.0:
9:CA Grapes: .75: 25:14.0:









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1:AZ Cotton: 1.00: 9: .0:
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1:AZ Cotton: 1.00: 9: 2.0:
1:AZ Cotton: 1.00: 9: 3.0:
1:AZ Cotton: 1.00: 9: 4.0:
l:CAvtomato: .019: 10: .0:
l:CAvtomato: .019: 10: 1.0:
l:CAvtomato: .019: 10: 2.0:
l:CAvtomato: .019: 10: 3.0:
1:AZ Orange: 8.00: 350: .0:
1:AZ Orange: 8.00: 350: 1.0:
1:AZ Orange: 8.00: 350: 3.0:
1:AZ Orange: 8.00: 350: 5.0:
1:AZ Orange: 8.00: 350: 7.0:
1:AZ Orange: 8.00: 350:14.0:
1:AZ Orange: 8.00: 350:21.0:
1:AZ Orange: 8.00: 350:28.0:
1:AZ Orange: 8.00: 350:42.0:
1:AZ Cotton: .50: 5: .0:
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1:AZ Cotton: .50: 5: 3.0:
2:AZ Cotton: .50: 5: .0:
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                                            406
Appendix H, page  22
129

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280 0
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611 0
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496 0
291 0
132 0
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                                               407
Appendix H, page  23
                                  130

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3.75
7.00
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5.63
5.63
5.63
5.63
5.63
5.63
11.30
11.30
11.30
11.30
11.30
11.30
5.63
5.63
5.63
5.63
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5.63
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11.30
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11.30
11.30
11.30
11.30
11.30
5.63
5.63
5.63
5.63
5.63
5.63
5.63
5.63
5.63
:1500
:1500
:1500
:1500
:1500
:1500
:1500
:1500
: 100
: 100
: 100
: 100
: 100
: 100
: 100
:2250
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: 100
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: 100
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:2250
:2250
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:2250
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:2250
:2250
: 100
: 100
: 100
: 100
: 100
: 100
: 100
:2250
:2250
:31.0:
: .0:
: 3.0:
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:17.0:
:31.0:
:45.0:
:60.0:
: .0:
: 3.0:
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: .0:
: 3.0:
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: .0:
: 3.0:
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: .0:
: 3.0:
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: 1 7 . 0 :
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: .0:
: 3.0:
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: .0:
: 3.0:
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:17.0:
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: .0:
: 3.0:
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: 17.0:
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:60.0:
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: 3.0:
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2.200:
.900:
.340:
.120:
.034:
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4.200:
1.700:
.460:
.140:
.078:
.058:
.036:
1.980:
1.080:
.260:
.108:
.050:
.000:
2.600:
2.000:
.440:
.200:
.140:
.010:
8.800:
6.800:
1.540:
.620:
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.060:
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.800:
.340:
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.042:
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1.500:
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4.200:
1.820:
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.178:
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10
4
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18
8
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11
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34
29
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.286 0
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.964 0
.277 0
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.283 0
.702 0
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.673 0
.360 0
.201 0
.616 0
.368 0
                                             408
Appendix H, page  24
                               131

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: 1719: CAvOrange: 5.63:2250:10.0
: 1719: CAvOrange: 5.63:2250:17.0
: 1719: CAvOrange: 5.63:2250:31.0
: 1719: CAvOrange: 5.63:2250:45.0
: 1720: CAvOrange: 11. 30: 2250: .0
: 1720: CAvOrange: 11. 30: 2250: 3.0
: 1720: CAvOrange: 11.30:2250: 10.0
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: 1720: CAvOrange: 11. 30: 2250: 31.0
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: 1721: CAvOrange: 5.63: 100: .0
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: 1722: CAvOrange: 5.63:2250: .0
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: 1722: CAvOrange: 5.63:2250:45.0
: 1722: CAvOrange: 5.63:2250:60.0
:1723:CAvOrange:ll. 30:2250: .0
: 1723: CAvOrange: 11. 30: 2250: 3.0
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: 1723: CAvOrange: 11. 30: 2250: 17.0
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: 1 723 : CAvOrange : 1 1 . 30 : 2250 : 45 . 0
: 1723: CAvOrange: 11. 30: 2250: 60.0
: 1724: CAvOrange: 5.63: 100: .0
: 1724: CAvOrange: 5.63: 100: 3.0
: 1724: CAvOrange: 5.63: 100:10.0
: 1724: CAvOrange: 5.63: 100:17.0
: 1724: CAvOrange: 5.63: 100:31.0
: 1724: CAvOrange: 5.63: 100:45.0
: 1724: CAvOrange: 5.63: 100:60.0
: 1725: CAvOrange: 3.63:1450: .0
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: 1725: CAvOrange: 3.63:1450:31.0
: 1725: CAvOrange: 3.63:1450:45.0
: 1726: CAvOrange: 7.25:1450: .0
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: 1726: CAvOrange: 7.25:1450:31.0
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: 1727: CAvOrange: 3.63: 100: .0
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Appendix H, page  25
                              132

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2.30:
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100:
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.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
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.000:
.000:
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.628 0
.210 0
3.760 0
1.157 0
1.233 0
.454 0
.029 0
4.586 0
1.023 0
.973 0
.821 0
.077 0
.754 0
.478 0
.478 0
.153 0
.030 0
.056 0
.020 0
1.332 0
.764 0
.535 0
.325 0
.115 0
.030 0
.034 0
2.647 0
1.804 0
1.143 0
.830 0
.134 0
.059 0
.041 0
1.427 0
.354 0
.096 0
.077 0
.066 0
.040 0
.057 0
1.332 0
.316 0
.079 0
.067 0
.057 0
.057 0
.045 0
2.890 0
.512 0
.152 0
.176 0
.093 0
.115 0
.205 0
.239 0
                                            410
Appendix H, page  26
                              133

-------
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
metion
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metion
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metion
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metion
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metion
metion
metion
metion
metion
monoos
monoos
monoos
monoos
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monoos
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monoos

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18
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2
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74
74
74
74
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78
78
77
77
77
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77

7:FL Orange: 2.30:1200: 1.0:
7:FL Orange: 2.30:1200: 3.0:
7:FL Orange: 2.30:1200: 5.0:
7:FL Orange: 2.30:1200: 7.0:
7:FL Orange: 2.30:1200:14.0:
7:FL Orange: 2.30:1200:21.0:
8:FL Orange: 4.60:1200: .0:
8:FL Orange: 4.60:1200: 1.0:
8:FL Orange: 4.60:1200: 3.0:
8:FL Orange: 4.60:1200: 5.0:
8:FL Orange: 4.60:1200: 7.0:
8:FL Orange: 4.60:1200:14.0:
8:FL Orange: 4.60:1200:21.0:
9:FL Orange: 6.90:1200: .0:
9:FL Orange: 6.90:1200: 1.0:
9:FL Orange: 6.90:1200: 3.0:
9:FL Orange: 6.90:1200: 5.0:
9:FL Orange: 6.90:1200: 7.0:
9:FL Orange: 6.90:1200:14.0:
9:FL Orange: 6.90:1200:21.0:
1:CA Orange: 5.60: 100: .0:
1:CA Orange: 5.60: 100: 3.0:
1:CA Orange: 5.60: 100:10.0:
1:CA Orange: 5.60: 100:17.0:
1:CA Orange: 5.60: 100:30.0:
1:CA Orange: 5.60: 100:45.0:
1:CA Orange: 5.60: 100:59.0:
2:CA Orange: 5.60:2250: .0:
2:CA Orange: 5.60:2250: 3.0:
2:CA Orange: 5.60:2250:10.0:
2:CA Orange: 5.60:2250:17.0:
2:CA Orange: 5.60:2250:30.0:
2:CA Orange: 5.60:2250:45.0:
3:CA Orange: 7.50:1500: .0:
3:CA Orange: 7.50:1500: 3.0:
3:CA Orange: 7.50:1500:10.0:
3:CA Orange: 7.50:1500:17.0:
3:CA Orange: 7.50:1500:30.0:
1:CA Citrus:003. 5:0100: 7.0:
1:CA Citrus:003. 5:0100:14.0:
2:CA Citrus:003. 5:1000:11.0:
2:CA Citrus:003. 5:1000:14.0:
1:AZ Cotton: 1.00: 9: .0:
1:AZ Cotton: 1.00: 9: .5:
1:AZ Cotton: 1.00: 9: 1.0:
1:AZ Cotton: 1.00: 9: 2.0:
1:AZ Cotton: 1.00: 9: 3.0:
1:AZ Cotton: 1.00: 9: 4.0:
1:AZ Cotton: 1.28: 9: 1.0:
1:AZ Cotton: 1.28: 9: 1.5:
1:AZ Cotton: 1.00: 9: .0:
1:AZ Cotton: 1.00: 9: 1.0:
1:AZ Cotton: 1.00: 9: 2.0:
1:AZ Cotton: 1.00: 9: 3.0:
1:AZ Cotton: 1.00: 9: 4.0:
Appendix H, page 2




















9
6
1




1
1




1








4
3
3
3
2
1


1
1
1


7
.010:
.015:
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.038:
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.032:
.022:
.024:
.192:
.054:
.074:
.056:
.044:
.050:
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.200:
.800:
.540:
.660:
.220:
.066:
.020:
.960:
.120:
.260:
.110:
.052:
.010:
.760:
.920:
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.030:
.240:
.080:
.320:
.100:
.900:
.950:
.750:
.125:
.750:
.792:
.460:
.560:
.420:
.480:
.100:
.770:
.700:

.000:
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.000:
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34










































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029 0
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4V

-------
monoos
monoos
monoos
monoos
oxyme
oxyme
oxyme
oxyme
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oxyme
oxyme
oxyme
oxyme
oxyme
phenth
phenth
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pholon
pholon
pholon
pholon
pholon
pholon
pholon
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pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
:79
:79
:79
:79
:38
:38
:38
:38
:38
:38
:38
:38
:38
:38
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:18
:24
:24
:24
:24
:24
:24
:24
:24
:24
:24
:24
:24
:48
:48
:48
:48
:48
:48
:48
:48
1:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
1:AZ Cotton:
1:FL Orange:
1:FL Orange:
1:FL Orange:
1:FL Orange:
1:FL Orange:
1:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
2:FL Orange:
1 : CAsOrange :
l:CAsOrange:
1: CAsOrange:
1 : CAsOrange :
1 : CAsOrange :
1: CAsOrange:
1 : CAsOrange :
1 : CAsOrange :
2 : CAsOrange :
2 : CAsOrange :
2: CAsOrange:
2: CAsOrange:
2: CAsOrange:
2: CAsOrange:
2 : CAsOrange :
3 : CAsOrange :
3: CAsOrange:
3 : CAsOrange :
3: CAsOrange:
3: CAsOrange:
3 : CAsOrange :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
1 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
2 : CAvOrange :
l:CAvPeach :
l:CAvPeach :
l:CAvPeach :
IrCAvPeach :
l:CAv Peach :
l:CAvPeach :
l:CAvPeach :
2:CAvPeach :
1.00:
1.00:
1.00:
1.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
4.00:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
7.50:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
6.00:
4. :
4. :
4. :
4. :
4. :
4. :
4. :
4. :
9
9
9
9
750
750
750
750
750
750
750
750
750
750
100
100
100
100
100
100
100
100
1500
1500
1500
1500
1500
1500
1500
1500
1500
1500
1500
1500
1500
600
600
600
600
600
600
600
600
600
600
600
600
30
30
30
30
30
30
30
375
: .0:
: 1.0:
: 2.0:
: 3.0:
: 1.0:
: 2.0:
: 5.0:
:10.0:
:20.0:
:30.0:
: 1.0:
: 2.0:
: 5.0:
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: 2.0:
: 9.0:
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: 2.0:
: 3.0:
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: .0:
: 3.0:
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: 1.0:
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:19.0:
:21.0:
:23.0:
: 1.0:
: 8.0:
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:23.0:
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n*
• • \J •
1.280:
1.060:
.630:
.430:
.400:
.274:
.164:
.112:
.076:
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.006:
.003:
.001:
.000:
4.000:
.000:
.860:
.400:
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.016:
.660:
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.140:
.048:
.000:
.010:
.000:
1.800:
.660:
.140:
.046:
.010:
.000:
7.000:
4.300:
5.100:
3.800:
3.800:
2.800:
6.500:
4.800:
4.100:
2.600:
3.200:
2.400:
6.484:
5.358:
3.094:
2.024:
4.026:
4.326:
5.518:
10.906:
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.088:
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.058:
.032:
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.000:
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.000:
.068:
.058:
.000:
.028:
.000:
.010:
.014:
.066:
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.062:
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3.621?0
3.00870
1.79970
1.23170
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2.029
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1.587
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1.159
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1.475
1.091
.933
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0
0
0
0
0
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1
1
1
1
1
1
1
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1
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1
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0
0
0
0
0
0
0
0
0
0
                                               41;
Appendix H, page  28
                               135

-------
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
pholon
phosam
phosam
phosam
phosam
phosam
phosam
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
phosmet
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 2:CAvPeach
:48 3:CAvPeach
:48 3:CAvPeach
:48 4:CAvPeach
:48 4:CAvPeach
:48 4:CAvPeach
:48 4:CAvPeach
:48 4:CAvPeach
:48 5:CAvPeach
:48 5:CAvPeach
:48 5:CAvPeach
:48 5:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 6:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:48 7:CAvPeach
:81 l:CAsOrange
:81 l:CAsOrange
:81 l:CAsOrange
:81 l:CAsOrange
:81 l:CAsOrange
:81 l:CAsOrange
: 3 1:AR Peach
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: 3 2:AR Peach
: 3 2:AR Peach
: 3 2:AR Peach
: 3 2:AR Peach
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4. :
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Appendix H, page  29
                                     136

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         Appendix H, page  30

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3.998 0
3.012 0
2.114 0
1.774 0
2.207 0
3.519 0
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5.540 0
3.544 0
3.455 0
6.399 0
3.611 0
4.056 0
2.060 0
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36.532 0
41.802 0
45.884 0
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39.243 0
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25.053 0
23.108 0
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16.361 0
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10.359 0
8.508 0
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1.947 0
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11.605 0
10.845 0
9.950 0
9.337 0
7.875 0
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3.680 0
3.684 0
1.803 0
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Appendix H, page  31
                                138

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Appendix H, page  32
                                   139

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                                           417
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Appendix H.  page 33
14Q

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mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
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mep2
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mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
mep2
map 2
mep2
mep2
mep2
mep2
:2210:CA
:2210:CA
:2210:CA
:2210:CA
:74
:74
:74
:74
:74
:74
:30
:30
:30
:30
:12
:12
:12
:12
:12
:12
:12
:12
:12
:75
:75
:75
:75
:75
:75
:75
:75
:75
:75
:78
:78
:79
:79
: 6
: 6
: 6
: 6
: 6
: 6
: 6
: 6
: 6
: 6
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
liAZ
Grapes:
Grapes:
Grapes:
Grapes :
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
1 : CAvtomato :
1 : CAvtomato :
l:CAvtoraato:
1 : CAvtomato :
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:AZ
2:AZ
2:AZ
2:AZ
2:AZ
2:AZ
1:AZ
1:AZ
1:AZ
1:AZ
1:WA
1:WA
1:WA
1:WA
1:WA
2:WA
2:WA
2:WA
2:WA
2:WA
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Orange:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Cotton:
Apple :
Apple :
Apple :
Apple :
Apple :
Apple :
Apple :
Apple :
Apple :
Apple :
.75:
.75:
.75:
.75:
1.00:
1.00:
1.00:
1.00:
1.00:
1.00:
.019:
.019:
.019:
.019:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
8.00:
.50:
.50:
.50:
.50:
.50:
.50:
.50:
.50:
.50:
.50:
1.00:
1.00:
1.00:
1.00:
01.50:
01.50:
01.50:
01.50:
01.50:
01.50:
01.50:
01.50:
01.50:
01.50:
100:
100: 1
100: 3
100: 7
9:
9:
9: 1
9: 2
9: 3
9: 4
10:
10: 1
10: 2
10: 3
350:
350: 1
350: 3
350: 5
350: 7
350:14
350:21
350:28
350:42
5:
5:
5: 1
5: 2
5: 3
5:
5:
5: 1
5: 2
5: 3
9: 1
9: 1
9:
9:
0400:
0400: 1
0400: 2
0400: 3
0400: 7
0400:
0400: 1
0400: 2
0400: 3
0400: 7
.0:
.0:
.0:
.0:
.0:
.5:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
.0:
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.0:
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.5:
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.5:
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.5:
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.0:
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.0:
.0:
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.155:
.055:
.015:
.004:
2.650:
.498:
.250:
.153:
.127:
.098:
.242:
.151:
.064:
.010:
18.162:
14.550:
9.208:
6.158:
4.392:
.846:
.204:
.070:
.014:
5.610:
3.310:
2.840:
1.890:
1.090:
1.370:
1.090:
.810:
.560:
.490:
.150:
.060:
2.370:
1.630:
4.740:
1.704:
1.042:
.710:
.284:
5.600:
4.396:
3.136:
3. 080:
1.400:
.000:
.000:
.000:
.000:
.014:
.015:
.007:
.002:
.002:
.000:
.000:
.004:
.000:
.000:
.072:
.186:
.244:
.238:
.226:
.192:
.128:
. 096 :
.014:
.050:
.120:
.070:
.060:
.050:
.020:
.020:
.010:
.010:
.010:
.004:
.002:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.000:?
.. 418
.554 0
.197 0
.054 0
.014 0
13.278?0
3.23070
1.60970
.87770
.74570
.50070
1.23170
.96470
.32770
.05170
62.617 0
57.360 0
45.257 0
35.617 0
28.976 0
13.071 0
7.188 0
5.031 0
.770 0
26.77070
20.40070
16.44170
11.84870
7.71370
7.67970
6.34770
4.52970
3.30070
2.95370
.95970
.40470
11.42170
8.00370
15.616 0
5.921 0
3.664 0
2.511 0
1.012 0
18.176 0
14.570 0
10.625 0
10.446 C
4.891 0
Appendix H, page  34
                              141

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                                                         419
      The Effects of Organophosphate Pesticide
     Residue Variability Upon Reentry Intervals

             Preliminary Phase II  Report
                      July 1986

                          by
               William Popendorf,  Ph.D.
University of Iowa,  Institute of Agricultural Medicine

-------
Table of Contents;
                                                                          420
Abstract
Introduction
Background
Methods
Results and Discussion
                                                                     2
                                                                     2
                                                                     4
                                                                    10
Conclusion ............................   13
References ...........................  '•   14
Table I
Table II
Table III
Table IV
Table V
Table VI

Figure  1
Figure  2
Figure  3
Figure  4
Figure  5
Figure  6

Appendix A:
Appendix B:
Appendix C:
Appendix D:
            parameter notation and subscripts  	   16
            parameter mean and variability	17
            cross-sectional variability of foliar residues  ....   18
            simulated chronic response 	  ....   19
            simulated acute response 	   20
            parathion use history  	   22
            AChE activity versus
            AChE activity versus
            AChE activity versus
            AChE activity versus
            AChE activity versus
            AChE activity versus
time for  1% daily delAChE  ...   23
time for  27. daily delAChE  ...   24
time for  4Z daily delAChE  ...   25
time for  8Z daily delAChE  ...   26
time for 167. daily delAChE  ...   27
time for 0 residue variability  .   28
            Wylber simulation program  	  A-l
            PC simulation program  	  B-l
            PC health analysis summary program 	  C-l
            Example results of PC health analysis summary program  D-l

-------
                 The Effects of Organophosphate Pesticide                  ^ *- '
                Residue Variability Upon Reentry Intervals
Abstract;
     A stochastic simulation program was written to study the importance of
residue   variability   in  preventing  anti-cholinesterase   overexposure,
excessive  chronic AChE inhibition,  or acute illness.   A range  of  daily
inhibitions and residue variability were explored, and the simulated cohort
response  was compared to the historical record of chronic and acute  data.
The  resulting  chronic  and  acute  AChE  response  patterns  are  largely
displayed in Tables IV and V, respectively.

     It  was concluded that residue variability has only a slight effect on
the  mean  AChE health status of a working cohort,  in comparison  to  mean
daily  inhibition.   Residue variability has a slightly  stronger  although
still  secondary  effect upon the overall variability of the cohort's  AChE
activity.   The  fraction  of  the cohort whose  seasonal  AChE  inhibition
exceeded  a relatively arbitrary chronic threshold of 50% was again largely
controlled  by  the  daily mean inhibition,  but at 4% per  day  and  above
virtually  the  entire  cohort exceeded that limit and  below  4%  per  day
residue variability had an increasing important role.

     On  the other hand,  residue variability appears to have a very strong
effect  upon the uniformity of the AChE activity within the  cohort.   This
nonuniformity has both chronic and acute AChE implications.   For instance,
for residue variability even below a geometric deviation of 2.0,  the crews
seasonal  AChE  inhibitions are not expected to  be  statistically  uniform
(with 997. confidence) until half way through a season;  and for variability
of  3.0  and  above,  the crews will be dissimilar throughout  the  season.
Thus,  it  is possible to have several crews below an  administrative  AChE
inhibition  threshold (or even potentially with clinical symptoms) while the
cohort  mean is only marginally different from normal.   This  pattern  has
similar implications to both the design and interpretation of epidemiologic
surveys among this population.

     Acute  responses,  in terms of individual and group AChE responses  in
excess of potential clinical symptoms, exhibit a fairly clear boundary as a
function  of both residue mean and variation.   In the low mean range of 1%
to  2% per day,  no acute individual or group incidents were predicted  for
geometric  variations  below  2.5;  however,  a  set  of  random  parathion
commercial application residues collected on days 2,  9,  and 16 all showed
variations  of  around  2.6,  just  sufficient  to  induce  sporatic  acute
responses.

     This pattern of acute effects under conditions of low chronic response
and  the  practical  boundary of a geometric deviation  of  2.5  (+  150%),

suggest  that consideration to both the mean anti-cholinesterase effect and
the  variability of the foliar residues should be considered  when  setting
administrative reentry intervals.
                                Draft                            ph2.doc

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                                                                            422
Introduction;

     The 35 year history of harvesters being poisoned while working in a
field "recently"-sprayed with an organophosphate (OP) insecticide has been
sporatically documented from scattered case reports during their earliest
use beginning circa 1950 [1-4] to whole summaries in the last 10 years
[5-10].  The consensus of opinion is that these poisonings have resulted
from excessive field residues, most likely on the foliage of the plants
being harvested rather than on the crop, per se.  The focus of interest for
the control of this occupational health hazard has been to require an
adequate time period between insecticide application and crop harvest (or
other activity) for the residue to "decay" to levels not harmful to the
harvest workers.  This time period has come to be referred to as the
"reentry interval".

     One particular review of the history and development of reentry
intervals for OP pesticides [9] resulted in a conceptual and quantitative
model which will be the basis for the study described herein.  This
"Unified Field Model" could predict short-term anti-cholinesterase effects
from either single exposures or a series of uniform exposures to
insecticides of known dermal toxicity, and was proposed to be used to set a
foliar residue limit or "reentry interval" associated with a preselected
and acceptable anti-cholinesterase threshold.  One of the key limitations
of this original proposal was the uncertainty of setting an "acceptable"
administrative threshold for daily cholinesterase inhibitions, given the
fact that real exposures are neither daily nor uniform.

     This report describes a study using this Unified Field Model to
explore the effects of variations in both the levels and frequencies of OP
exposure upon the cholinesterase activity of a harvesting cohort throughout
a harvest season.  The method used in this exploration has been Monte Carlo
simulation.  This report first reviews the background of the model; then
the methods used in these explorations; and finally their findings and
implications.

Background;

     A comprehensive report describing the reentry problem and integrating or
"unifying" the major factors controlling it, was first published in 1982 as
the Unified Field Model [9].  This basic model originally had three submodels
[9 p.132], as shown below.   Later elaborations and clarifications of this
model [11] broke out a fourth submodel [9 p.180, 11], essentially Equation
3 as follows:

                                             —k T
     Residue Decay:                R « R  exp  r                     (1)

     Dose Deposition:             D1 = k.Rt                          (2)

     Dose Absorption-Distribution: D = k  D1 / m                     (3)

     Toxic Response:         delAChE « 1 - exp"keSum(Di/LD50:i)      (4)
                                     2         2
     where R  = foliar residue, ug/cm  or ng/cm , at some point in time T
                after application.
                  Draft Report Page 2 of 28                     ph2.doc

-------
     R  = initial foliar residue, ug/cm  or ng/cm  at the time of      423
      0   application.                                 ,
     k  « pesticide exponential decay coefficient, day  ; in
          practice, multiple coefficients may be used [12], or other
          than exponential submodels or a non-mathematical (e.g.
          graphical) method may be used [9].
     T  * the time (usually in days) after application of the
          pesticide; viz. the reentry interval.
     D1 • topical dermal dose, ug of pesticide (which in a mixture
          would be subscripted i).
     k , = a crop (and possibly activity) dependent dosing
          coefficient, whose units are dependent upon those of R, D,
          and t; e.g. if units of R were ug/cm , D were ug, and t
          were hours, then k. would be cm /hr [see ref. 11],
     t  = the length of exposure, hours (assumed herein to be a
          nominal 8 -hour workday).
     k  = a dermal absorption coefficient presented in most
          pesticide literature as a percent of deposited dose [9]
          but is toxicologically more related to a permeation rate
          coefficient [13]; however, use of the latter would require a
          more detailed scenario of the total time the dose would
          remain unwashed upon the skin.  Use of the model herein
          (with submodel Equation 4 and k =6) assumes k «1.
     m  = the mass of the exposed person, kg (nominally 70 kg).
     D  = the toxicological, dermally deposited dose, mg/kg.
     k  = an enzyme coefficient relating the degree of red blood
      e   cell (RBC) acetylcholinesterase (AChE) activity to the LD5Q
          of an OF-  This submodel is an extension of an original
          finding by Grob and Harvey [14].  K  » 6 was used herein
          with a rat dermal LDcn-            e
     cg * the dose (mg/kg) of cnemical necessary [or sufficient] to
          kill 50% of the exposed animals; this submodel expects the
          use of a dermal LDcn> the subscript i for LDcn and dose D
          implies that the ACRE response to multiple, simultaneous
          OPs is additive in this fashion.
deLAChE = the fractional, acute change in AChE enzymatic activity
          relative to a pre-exposure baseline, i.e.

              delAChE = (E  . - E ) / E  .                     (5a)
                          n-l    n     n-l

                      " <*n-l 'W  -(En/En-l>           (5b)
              delAChE •      1         - (E  / E  .)           (5c)
                                           n    n~l
          and

              E /E  . - 1 - delAChE                            (5d)
               n  n-l

where E • the measurable AChE enzyme activity on post-exposure day n
          and the pre-exposure activity on day n-l.  Note also that
          the previous day (n-l) may or may not necessarily be the
          person's unexposed baseline (see later discussion circa
          Equations 12-16).
            Draft Report Page 3 of 28                      ph2.doc

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                                                                             42'
     While not essential to the development of this particular study, a
number of alternative submodels were discussed in the original document [9]
and its later elaboration [11].  For instance, exponential decay (submodel
1) is a very common temporal pattern of environmental decay for pesticides,
but it may not always apply; procedures were in fact outlined therein for
dealing with graphical or even tabular decay data.  A more complex (and
potentially far-reaching) variation upon submodel 4 may be necessary to
deal with non-cholinergic effects; one suggestion to extend the Unified
Field Model to non-cholinesterase pesticides was to use the allowable
absorbed daily or chronic dose which is typically established for all
pesticides [11 p.337].  While the quantitative Dose-Response submodel for
risk assessment might employ any of several criteria, such as a
carcinogenic extrapolation risk assessment, a generalized submodel for
acceptability (replacing Equation 4) could be viewed as follows:


     _  .  _               .  ,.,..      dermally absorbed            /•,>.
     Toxic Response:  acceptability «	*	           (.o)

                                          allowable

     where acceptability is simply the ratio of actual to allowable daily
           dose (e.g. its NOEL) for each pesticide (or analogue subscripted
           i as above); this approach is equivalent to the ACGIH TLV and
           OSHA's PEL procedure for mixtures [15,16].

     Of more direct relevance herein are the consequences of repeated
variable residues upon AChE and the associated incidents of clinical
poisoning.  The consequences of daily repeated equal residues and of
variability in single daily residues upon AChE were originally discussed
separately on pages 137-140 and 186-191 [9].  A later manuscript [11]
described the temporal pattern of chronic (seasonal) AChE response in more
detail but was still restricted to constant residues and doses.  As it is
the purpose of this report to describe the effects of repeated, variable
residues and doses, the mathematical description of the methods used herein
shall begin with the model and terminology as developed in the original
report and presented above.

Methods;

     The historical focal point of health studies on people exposed to
anti-cholinesterase chemicals has been the enzymatic activity of AChE in the
body, which is most conveniently and routinely measured in the blood by
various laboratory procedures [17].  In health research settings, the effect
on a person's AChE is commonly expressed as a change relative to the study
subject's individual baseline activity, viz. delAChE as shown in Equation 5a
or 100 x delAChE expressed as a percent [6-8].  This concept reflects the
fact that individuals differ in their enzymatic activity but that health
effects accrue from changes in their activity relative to either their
normal (unexposed E ) or pre-exposure baseline (E  ,).  Note also that a
"pre-exposure baseline" implies that there may have been exposures with some
enzyme inhibition prior to the exposure in question and that normal and pre-
exposure levels are only equal for the first exposure (dose) of the season.

     An alternative to delAChE which is mathematically and biochemically
more convenient, is to look directly at the individual's relative activity
En^En-l °r En^Eo where En» En-l' and Eo are the Person's current, pre-


                  Draft Report Page 4 of 28                     ph2.doc

-------
                                                               29 Jul 86
exposure, and personal normal baseline activities, respectively [14,17].
One might think of this ratio as the person's health status (in fact this
shall later be called "H").  The relationship defined in Equation 5d
permits the direct use of the basic Unified Field Model Equations 1-4 to
also predict E /E _..  Thus, Equations 2 through 5 may be combined into one
complete equation, as follows:
     E /E   . - exp'W s^V" ^50, i)  - 1 - delAChE             (7)
      n  n~l

It may be convenient at this time to introduce the fact that values of many
of the model's variables and coefficients will differ among the chemical
components  within a residue (i), among the people within the cohort (j),
and from day to day (n).  These values are subscripted in the following
rewrite of  Equation 7:

      E.  /E.   . - wtp^duWn suffl(Ri,n ' nj LD50:i)              (8)
       j »n  j ,n i
     where  the following subscripts when used with subscripted coefficients,
     follow a colon:
            i = chemical component of the residue,
            j » person within the cohort,
            n = day within the season

     As noted above in Equations 5d, 7 and 8, the enzyme "health" status
ratio E.  /E,   . is relative to a generalized pre-exposure E  1 enzyme
activity 'valuenwnich may be either a true "baseline" (E ) or an already
partially inhibited level of activity.  Clinical health°effects are often
related to  this acute change in activity [14,17], but focus for standards
requiring infrequent biological monitoring of AChE is chronic or cumulative
seasonal changes relative to a person's unexposed baseline, E  [9].  As a
notational  convenience to aid the reader, the acute fraction E.  /E.   , for
a given person "j" on a given day "n" as defined by Equation 8Jw?llJ '
hereafter be noted by K,   (similar to a K notation without subscripts
used in the original repdrt [9]), as follows:
                                                     »J LD50:i)      (9)
Thus,

     EJ.n ' KJ.n EJ.n-l
And as another notational convenience, the fractional activity relative to a
normal baseline E.  /E,   will be noted by H.    which can easily be related
to the acute pre-exposufi effect K,   via Eqia?ion 10, as follows:
                                  j»n
     Hj.n-EJ.n/I!J.o   ' «,.„ WVo  -  KJ.n (Ej.n-l'Ej.o>
     But before using Equations 9-11 to predict long-term (i.e. cumulative
seasonal) changes in E, two biochemical and physiologic processes must be
included within the model.  These are (a) reversible inhibition or
reversion, the fact that recently inhibited enzymes are bound somewhat
reversibly, and that over a few hours a generally small fraction of the
enzymes will revert or return to their active state; and (b) regeneration,
the normal process of erythropoiesis (red blood cell production) which will
result in the generation of new RBC AChE and the accompanying process of


                  Draft Report Page 5 of 28                     ph2.doc

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                                                                            126
removal of a proportional fraction of inhibited RBC AChE.  In the original
report [9], these two processes were termed o1 and o, respectively.

     Although the detailed process and temporal pattern of reversion is not
completely understood, it may proceed for 6 to 30 hours or so after
exposure.  Values for o1 range from 0 to 10% for the strong inhibitors such
as TEPP and Sarin studied by Grob [14], to circa 15 to 20% for parathion
[9], to nearly 100% for most carbamates [15].  The modeled effect of
reversion is that the post-exposure enzyme activity E/E  is increased
after one day (24 hours) to a new fraction E'/E  by the reversion of a
certain fraction of the recent acute inhibition:

     reversion = o1 (1 - KR) - c-' delAChE                            (12)

     where o1  * the fraction of recently inhibited enzymes which becomes
                  unbound.

     The process of regeneration of RBCs is believed to be independent of
exposure and inhibition, as is the accompanying process of removal of old
RBC by the liver which is assumed to remove cells with both active and
inactive AChE indiscriminately.  Values of o for man range from 0.008 to
0.012 per day (average RBC life times of 85 to 130 days) [18].  In the
context of enzyme activity, the overall effect is one of replacement of
some old, inhibited enzymes with fresh, uninhibited enzymes.  The net effect
on the long-term model is that each day a fraction (o) of new RBC and
associated AChE are produced and an equal fraction of old RBC are removed
along with a somewhat lesser amount of active AChE proportional to the bulk
blood activity (or o x E /E ).  Here a mathematical approximation is made to
the model to account for the fact that E /E  may be changing throughout the
day due to the on-going process of reversion of recently inhibited enzymes.
As a convenient first-order approximation, the linear average relative
enzymatic activity over this period is assumed.  Thus,

     regeneration = o - (o/2 (E /E  + E'/E ))                        (13)
                    \\nono

     where E1 - E  + a slight improvement after 24 hours by virtue
            n    of reversion, see Equation 12.

     These processes were modeled within the original report only to
predict the net effect of repeated equal exposures [9 p.137-140].  Herein,
they are used to predict the entire pattern of the cumulative seasonal
response (E.  /E.  ) which would result from a random series of
variable reslaues'?R.  ).  To predict the cumulative effect of variations
in repeated unequal occupational exposures, one begins with responses
(K.  ) predicted from Equation 9 and the post-exposure enzyme health status
predicted by Equation 11.  Subsequent to each exposure and predicted acute
response, the body will undergo a level of recovery so that the next day's
"pre-exposure" baseline is slightly improved over that at (or shortly
after) the end of the previous day's work.  This improved enzyme activity
shall be defined as H' n (or E'. n/E.  ).  Therefore, to the initial post-
exposure health status'predicted by^Equation 11 shall be added the effects
of reversion (Equation 12) and regeneration (Equation 13) with the
appropriate person subscripts "j" inserted as needed:
                  Draft Report Page 6 of 28                     ph2.doc

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     Ej.n/Ej.o
Or.
     Ej.n/Ej.o - "WE3.o(1 - */2> + Vj<> * Kj,n>
                                                  2 (Ej.n/Ej,o>
And now solving for E*  /E.   which appears on both sides of Equation 14:
                     J »n  j ,o
     EJ.n"j.o(1 + ?/2) - Ej,n/Ej,o(1 -
  /E.  (1 - o/2) + o!(l - K.
*S.J*2 ..... i ...... & ...... 4iD
                                                   ) +
      J'n  J'°                   (1 +o/2)

     As indicated circa Equation 5d, it is this slightly recovered enzyme
activity level of Equation 16 which becomes the pre-exposure value for
succeeding exposures (E.   ./E.   in Equation 11), or
                       J»n-i  j,o

     H. n-1 - E. n.1/E. Q - E! n/E. Q - H'n_1                        (17)


     The above iterative sequence of daily inhibition (Equation 9-11) and
partial recovery (Equation 16) lends itself nicely to a digital program
which re-iterates this calculation, day-by-day throughout the season.  A
stochastic or Monte Carlo simulation computer program was written to permit
the parametric random variation of many of the factors described above (see
Appendices A-C).  In principle, the Monte Carlo simulation process could
create a heterogeneous population of values for any model parameter
distributed about a mean value with virtually any specified variability [19J.
Table I summarizes the terms within this study which are varied and fixed,
their notation within the text, and the subscripts assigned to those
parameters permitted to vary during this study.

     A number of modeled factors were either not varied or not used at
all, in particular, the residue application and decay coefficients.  The
initial plan for this project intended to begin these variations from the
point of residue application, i.e. to randomize R  and the decay
coefficients (k ) as used in a multicomponent decay model [12].  The
intended decay model for paraoxon follows:

                   K|K-                 Ky K«
     R         , —_i.±i9_- exp-klT + —S-fi2. exp-k3T +
      paraoxon    .     ,                .     .
                  K5 " Kl              K5 " *3


                       (R_	*---	12__) exp-k5T        (18)
                         3'°    k  - k      k  - k
                                K5    1      5    3
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     where the subscripts it to                                              "eg
            k,, indicate one of five k  coefficients used in this particular
             " model [12], and       r
          R..   indicate one of two portions of the initial paraoxon residue
           ff'° [12].

Considerable difficulty with this approach resulted from the existence of a
"pole" in these equations (i.e. when the denominator approaches zero, the
value of the  residue becomes impossibly large).  When the residue at
selected points in time was calculated using the above decay submodel with
randomly varying coefficients based on field data [12], such impossibly and
unrealistically high  values sporadically resulted.  To avoid this
difficulty, the residue at initial reentry R was randomized directly;
therefore neither k  nor T was used within this simulation, as noted in
Table I.           r

     For other reasons k  was also not used within this simulation (since a
dermal LD_Q value was aslumed, the absorption coefficient k  would have been
set to unity as intended by the original Unified Field Model.  Various
other parameters in the Unified Field Model were used but not permitted to
vary.  For example, Values for dermal toxicity were not varied since only
one generic OP was examined and variations in interpersonal susceptibility
was already accounted for by k  ., m., o1, and o.  As a first approximation
and to obtain a more clear understanding of the effects of variability
caused only by people and their daily residue, the length of the workday
was assumed constant.  Later elaborations of this study could include more
daily variations or even an interaction as from a hypothetical effect of
decreased enzyme activity upon the harvester's physical ability to sustain
an 8-hour workday (t) and a uniform work-rate (equivalent here to the
dosing coefficient k,).

     The concept of Monte Carlo simulation is that any factor can be varied
at random in any of a wide range of possible distributions [19].  This
particular study assumed that the factors listed as "varied" in Table I
were assumed to be either normally or log-normally distributed (the
logarithms of log-normally distributed values are themselves normally
distributed).  The mean and variability of each of the varied terms is
listed in Table II.  Most of these factors are assumed to be log-normal,
although for small deviations (equivalent coefficients of variation less
than 50%) it makes little difference whether normal or log-normal
variability is assumed.

     The particular form and magnitude of the parametric characterization of
R was selected from experimental experience with environmental samples
generally and foliar residue samples in particular [9],  Such samples are
invariably distributed in a skewed manner approximating a log-normal
distribution.  The largest available set of multiple foliar residue samples
collected on the same day(s) post-application but from a variety of
commercial applications is listed in Table III.  It is clear from the
relative size of the standard deviations compared to the arithmetic mean
values, that these data are not normally distributed.  The acceptability of
fit of these data to a log-normal distribution was confirmed by a Univariate
Analysis on the pooled data.  The pooled geometric deviation for all six
sets of samples is 2.6 or 160%, a point of reference for later comparisons.
                  Draft Report Page 8 of 28                     ph2.doc

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                                                                    --  429
     Two versions of the simulation program (Appendices A and B) were
utilized during this study.  Version A was designed to run on a large
mainframe computer (viz. an IBM 370/168 (with VM/CMS operating system)) and
utilized two commercially available subroutines (IMSL).  This version can
only be operated- in the batch mode and generates its model parameters by
randomly drawing separate sets of personal characteristics and field
residues for each crew from pseudo-infinite, parametrically distributed
universes for each respective model parameter.  The benchmark runs were made
with Version A, primarily because of its earlier availability.

     To expand portability to other computers and add further flexibility to
the exposure patterns which could be simulated, a second version was written
for Fortran-77 which can be (and was) run on an IBM - PC.  It utilizes two
published subroutines [20-21] to create parametrically distributed sets of
personal characteristics for the entire cohort and all field residues, then
randomly distributes this cohort and field residues among the crews.

     There are a number of differences between these two approaches: the
latter version consistently creates an entire study population of harvesters
or residues which fits the desired parametric distribution virtually exactly
(versus an F(°°,n) sampling error in the cohort created by the former version
which is a function of the cohort size, n; for 216 harvesters the 99%
confidence limit on achieving the parameter variability requested is + 15%
and for 916 field residues is + 6%).  At the same time, the variability of
each crew created by the latter method is only slightly larger than the
former (a sampling error which is a function of both the cohort and crew
sizes; for the population cohort of 216 and crew size of 12 used within
this study, the crew sampling error for both approaches is about 2-fold
(+ 98% versus + 99%, respectively)).

     Operationally, the simulation program (Appendix B) first creates a
cohort of harvesters.  Each harvester is randomly characterized in terms of
work habits (k.), weight (m), enzyme susceptibility (k ), and reversion-
regeneration coefficients.  This population is then distributed among
"ncrews" with "npersons" per crew.  An array of parametrically distributed
residues at reentry is also created and randomly assigned to each field.
For this series of simulations, each harvest crew works alternately two or
three days for 8 hours within two fields each week (five days per week).
Initially H.   • H.   • 1.  Each day the acute K.   is determined by
Equation 9,J4nd H.J'°by Equation 11.  At the startnof the next exposure day,
H1.   is determined'By Equation 16; and the process, beginning with acute
inhibition, is repeated.  Non-exposure days are handled in much the same
manner (except of course K  =1.0 for all j).  The program records the
enzyme health status (H) fcr each harvester within each crew from field to
field for a 26 week (six month) harvest season.

     Finally a second program (Appendix C) was written to analyze this
detailed personal health history to determine the following:

     0AM and OGM = the overall arithmetic and geometric mean delAChE of the
         cohort, respectively.
     PSD and PGD = the pooled standard and geometric deviations of the
         cohort, respectively.
     F * an analysis of variance F test statistic characterizing the
         uniformity or dispersion of delAChE within the crews versus among


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                                                                              43C
         the crews.  It was expected that the crews will be significantly
         different from each other as a function of residue variability but
         will become more uniform with passing time.
     Poi// * the daily incidence of individual OP "poisoning" cases based on
         one of four threshold criteria:
          (1) acute response, a delAChE of at least 507. in 1 day,
          (2)   "      "      "   "     "  at least 65%  " 2 days,
          (3)   "      "      "   "     "  at least 75%  " 3 days,
          (4) chronic  "      "   "     "  at least 50% versus E.  .
                                                                J»°
An example of the print-out from this program is shown in Appendix D.  The
first three of the above poisoning counters are also summarized by the total
number of poisoning cases, the number of days (nominal number of fields) in
which the above cases occurred, and the number of potentially reportable
incidents (assumed here to require at least one-half of the crew to have
exceeded one of the above criteria in one day).  In practice the 1-day acute
and seasonal chronic "poisoning" will be the primary focus of discussion.

Results and Discussion;

     A depiction of the cohort mean delAChE response throughout the season
is presented in Figures 1-5 grouped by daily mean inhibition (with residue
variability as a co-factor) and in Figure 6 grouped by variability equal to
1.0 (with daily mean inhibition as a co-factor).  A summary of the end-of-
season (chronic) AChE conditions are tabulated in Table IV.  By comparing
the vertical spread in the cohort mean response lines within Figures 1-5
with those in Figure 6, it can be stated that variations in the daily mean
inhibition (l-K ) have a greater impact on the chronic state of inhibition
than does residue variation, per se.  The rate at which these simulated
cohorts approached their seasonal lows varied from "half-response" times of
about 2 months for low daily inhibitions (1%) to about 2 weeks for high
daily inhibitions (16%).

     These chronic response patterns are similar to earlier predictions [11,
p. 330] except that they assumed uniform exposures 7-days per week.
Another feature not seen before is the weekly cycle of inhibition and
partial recovery as the level of inhibition approaches 60% or greater; for
relatively high daily inhibitions (circa 8 to 16%), the combination of
reversion and regeneration results in recoveries of as much as 4% of the
baseline normal over a weekend, which becomes more visible on the expanded
scale near the bottom of these figures.

     Based on the first row of data in Table IV, it appears that the only
practical daily inhibition (i.e. residues with any variability at all) for
which seasonal inhibition will be less than 50% is 1% per day.  This is
similar to the prediction in reference 9 (p. 140) of 1 to 2% per day for
40% seasonal inhibition given a 7-day per week exposure pattern.  The
variability in the seasonal inhibition is indicated by the second row of
data, the geometric deviation.  It appears that the relative variability in
the seasonal low AChE activity is reduced primarily as the daily
inhibitions increase and secondarily as the variability in the residues
increases.  This pattern is explainable by the overwhelming importance of
the magnitude of the daily inhibition in relationship to the speed of
enzyme reversion and replacement.  The impact of variability on the
fraction of the cohort whose seasonal inhibition exceeds 50% is indicated


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                                                               29 Jul 86


by the third row of data  in this table: the trade-off between low levels or -^ '
daily inhibition and relatively high levels of variability causes there to
be some fraction of the cohort which exceeds 50% under all conditions,
although again this fraction increases primarily with increasing levels of
daily inhibition.

     As it will be discussed in relation to acute responses, the
significance of these simulated chronic responses in relation to future
human experience is best  judged in relation to past experience.
Unfortunately the history of past chronic cholinesterase studies among
harvesters has hardly been reported.  One rather unique study of one East
coast migrant crew by Owens and Owens [24] was referenced in the
elaboration of the Unified Field Model [11] showed seasonal inhibitions of
30 to 40%, but the more detailed analyses of their data has not been
accomplished.  Another known report was a student master's thesis of some
822 California central valley harvesters in 1970 which showed seasonal
inhibition of 5 to 8Z [25].  In both studies neither the intensity nor
frequency of residue exposure was known; therefore, direct comparisons of
the chronic response between this simulation and human experience is barely
possible.

     In general, such chronic longitudinal studies are difficult to
initiate, organize, maintain and analyze.  Of practical importance is the
effect on data analysis of the relative size (and numbers) of individual
crews into which the whole cohort is distributed.  Included in the results
printed by the data summary program is the analysis of variance F statistic
indicating the uniformity between the crews versus within the crews (and
the cohort as a whole).   Initially these test statistics are quite large,
indicating statistically  greater variation between crews than within crews
(except of course, when the variability in the residues is 0 (geometric
deviation of 1.0).  Over  time, the crews become more and more consistent,
and the daily F statistic decreases.  A value of about 2.0 indicates
statistical uniformity with 99% confidence.  The fourth row of Table IV
indicates the number of days into the season necessary for such inter-crew
uniformity to be established.  From this data it is clear that residue
variability is the dominant factor characterizing inter-crew uniformity and
that statistical uniformity is not achieved within a six-month season for
levels of variability of  3 or more.  This conclusion implies that an
adequate interpretation of harvester cholinesterase survey data must take
into account the grouping of that data by crew; similarly, some crews
should be expected to be  significantly more inhibited than others or than
the group as a whole.

     The preceding discussion of chronic response variability is directly
relatable to acute "clinical" responses which represent the high "tails" of
the daily statistical distribution.  A summary of acute response data are
depicted in Table V only  (rather than in figures).  The first row of this
table indicates the frequency with which individual harvesters might have
RBC AChE shifts sufficient to induce clinical symptoms.  It appears that
while the incidence of chronic seasonal inhibition is high under many of
the scenarios investigated, the incidence of clinically acute responses is
undetectable under a much broader range of residue conditions.  Practical
conditions without incidents begin at 8% per day if the variability can be
kept at or below 1.5; at  4% per day, below 1.5; 27. per day of at or below
2.0; and 1% per day if variability approaches 3.0.  It also appears that


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once conditions of daily mean or residue variability are sufficiently
to cause one individual acute case, multiple cases (the second row) and
incidents involving at least half the crew (the third row) begin to occur;
this pattern is relatable to the inter-crew versus intra-crew uniformity
discussed above.•  Therefore, a reasonable administrative target is to
prevent any individual cases of anti-cholinesterase poisoning sufficient to
cause clinical symptoms.

     Fortunately the significance of these simulated acute responses in
relation to future human experience is more readily judged in relation to
past experience than was true for chronic cholinesterase effects.  Several
tabulations of "reported" poisoning incidents from the literature are
available to provide a first estimate of past field experience [3,6,8].
These data indicate an incidence of about 25 harvesters and 1 "incident"
reported in California per year from 1948 to 1977; although two other
independent reports indicate the above values "represent perhaps 1% of of
the persons who suffered less severe symptoms, received medical treatment,
but remained unreported" [9].  Most (but not all) of these reported cases
involved parathion.

     The denominator for these cases can be estimated from the roughly
74,000 acres of Valencia oranges in California [26] (the variety harvested
during the April-September prime parathion application period; see Table VI)
and reported individual harvest rate data [27], which indicate about 7400
harvesters are actively engaged in harvesting the seasonal crop most
commonly involved in reported residue poisoning incidents [3,6,8].  The
denominator for these incidents can be closely approximated from California
Pesticide Use Reports, Table VI, which for the early 1970s was about 2000
fields and circa 60,000 acres of oranges (of which about 50% was summer
valencias) sprayed per year [28].  Thus, on an annual average over the
thirty year history, about 25/7400 = 0.34% of the orange harvesters in
California have been involved in a reported residue poisoning per year and
1/1000 = 0.1% of the field applications have resulted in reported incidents.

     Recall also that the variability in parathion residues on citrus was
2.6 (Table III); furthermore, the equivalent anti-cholinesterase power of
the residues on day 9 was about 8% and on day 16, about 4%.  Since
California had, prior to 1970, an administrative harvest - reentry interval
for parathion of 14 days, a mean daily inhibition of 4% is the worst
expected scenario to simulate historical experience.  Although it is
unlikely that every field was harvested as soon as its reentry interval had
elapsed, it is possible that a great many of these fields could have been
harvested between that time and 2 weeks later (or about 2 half lives and
l/4th the AChE effect later).

     Locating these conditions in Table V indicates a reasonably good
agreement between the simulation and historical record.  The simulation
indicates a somewhat higher incidence of individual overexposures than the
historical record shows, but well within the higher range estimated by the
"critics" of the established reporting system.  On the other hand, the
simulation indicates an incidence of "potentially reportable" group
incidents somewhat lower than reported.  There are many possible
explanations for this latter difference, among them are (1) a difference in
the ratio of number of crews and crew size from that modeled, (2) an overly
conservative definition of "incident" (i.e. at least 50% of the crew having


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an AChE shift of 50% or more), and (3) other than a log-normal distribution  A ? 7
of foliar residues (i.e. a bimodal distribution with unexpectedly more
frequent high residues under some relatively unique combination of
environmental and/or application conditions, or possibly some combination of
the above.  Whatever the reason, the differences are relatively slight;
proving the value of this stochastic simulation procedure.

Conclusion;

     A stochastic simulation program was written to study the importance of
residue variability in preventing anti-cholinesterase overexposure,
excessive chronic AChE inhibition, or acute illness.  A range of daily
inhibitions and residue variability were explored, and the simulated cohort
response was compared to the historical record of chronic and acute data.
The resulting chronic and acute AChE response patterns are largely displayed
in Tables IV and V, respectively.

     It was concluded that residue variability has only a slight effect on
the mean AChE health status of a working cohort, in comparison to mean daily
inhibition.  Residue variability has a slightly stronger although still
secondary effect upon the overall variability of the cohort's AChE activity.
The fraction of the cohort whose seasonal AChE inhibition exceeded a
relatively arbitrary chronic threshold of 50% was again largely controlled
by the daily mean inhibition, but at 4% per day and above virtually the
entire cohort exceeded that limit and below 4% per day residue variability
had an increasing important role.

     On the other hand, residue variability appears to have a very strong
effect upon the uniformity of the AChE activity within the cohort.  This
nonuniformity has both chronic and acute AChE implications.  For instance,
for residue variability even below a geometric deviation of 2.0, the crews
seasonal AChE inhibitions are not expected to be statistically uniform (with
99% confidence) until half way through a season; and for variability of 3.0
and above, the crews will be dissimilar throughout the season.  Thus, it is
possible to have several crews below an administrative AChE inhibition
threshold (or even potentially with clinical symptoms) while the cohort mean
is only marginally different from normal.  This pattern has similar
implications to both the design and interpretation of epidemiologic surveys
among this population.

     Acute responses, in terms of individual and group AChE responses in
excess of potential clinical symptoms, exhibit a fairly clear boundary as a
function of both residue mean and variation.  In the low mean range of 1% to
2% per day, no acute individual or group incidents were predicted for
geometric variations below 2.5; however, a set of random parathion
commercial application residues collected on days 2, 9, and 16 all showed
variations of around 2.6, just sufficient to induce sporatic acute
responses.

     This pattern of acute effects under conditions of low chronic response
and the practical boundary of a geometric deviation of 2.5 (or + 150%),
suggest that consideration to both the mean anti-cholinesterase effect and
the variability of the foliar residues should be considered when setting
administrative reentry intervals.
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                                                                             434
References;

 1. Abrams, H.K., and A.R. Leonard: Toxicology of Organic Phosphate
    Insecticides. Calif. Med. 73:183-186, 1950.
 2. Ingrain, F.R.: Health Hazards Associated with Use of Airplanes for
    Dusting Crops with Parathion.  Amer. Ind. Hyg. Assoc. Quart. 12:165-
    170, 1951.
 3. Quinby, G.E., and A.B. Lemmon: Parathion Residues as a Cause of
    Poisoning in Crop Workers.  J. Amer. Med. Assoc. 166:740-746, 1958.
 4. Milby, T.H., F. Ottoboni, and H. Mitchell: Parathion Residue Poisoning
    Among Orchard Workers.  J. Amer. Med. Assoc. 189:351-356, 1964.
 5. Milby et al.: Occupational Exposure to Pesticides.  A Report of the
    Federal Working Group on Pest Management, Washington DC, 1974.
 6. Spear, R.C., W.J. Popendorf, J.T. Leffingwell, and D. Jenkins:
    Parathion on Citrus Foliage: Decay and Composition as Related to Worker
    Hazard.  J. Agr. Food Chem. 23:808-810, 1975.
 7- NIOSH: Proceedings; Pesticide Residue Hazards to Farm Workers. U.S.
    Dept. HEW Pub. No. (NIOSH) 76-191, 1976.
 8. Gunther, F.A., Y. Iwata, G.E. Carman, C.A. Smith: The Citrus Reentry
    Problem: Research on its Causes and Effects, and Approaches to its
    Minimization.  Residue Reviews 67:1-139, 1977.
 9. Popendorf, W. and J.T. Leffingwell: Regulating OP Pesticide Residues
    for Farmworker Protection.  Residue Reviews 82, 125-201, 1982.
10. Dermal Exposure Related to Pesticide Use; Discussion of Risk
    Assessment, ed. by R.C. Honeycutt, G. Zweig, N.C. Ragsdale. American
    Chemical Society, Washington DC, 1985.
11. Popendorf, W.P.: Advances in the Unified Field Model for Reentry
    Hazards, p. 323-341, op cit., 1985.
12  Popendorf, W. and J.T. Leffingwell: Natural Variations in the Decay and
    Oxidation of Parathion Foliar Residues.  J. Agric. Food Chem. 26:437-
    441, 1978.
13. Scheuplein, R.J.: Percutaneous Absorption After Twenty-five Years: or
    "Old Wine in New Wine Skins." J. Invest. Dermat. 67:31-38, 1976. (not
    his latest).
14. Grob, D. and A.M. Harvey: Effects in Man of the Anti-cholinesterase
    Compound Sarin (Isopropyl Methyl Phosphonofluoridate). J. Clin. Inv. "
    37:350-368, 1958.
15. ACGIH Threshold Limit Values and Biological Exposure Indices for 1985-
    86. TLV for Mixtures, p. 47, Amer. Conf. Governmental Industr. Hyg.
    Cincinnati, OH, 1986.
16. OSHA Safety and Health Standards (29 CFR 1910.1000) U.S. Dept. Labor
    Pub. No. (OSHA) 2206, Washington DC, 1983.
17. Wills, J.H., and K.P. Dubois: The Measurement and Significance of
    Changes in the Cholinesterase Activities of Erythrocytes and Plasma in
    Man and Animals. CRC Critical Reviews in Toxicol. 1:153-202,1972.
18. Geigy Scientific Tables Vol. 3, 8th Ed., edited by C. Lentner, Ciba-
    Geigy, W. Caldwell NJ, 1984.
19. Rubinstein, R.Y.: Simulation and the Monte Carlo Method. John Wiley &
    Sons, New York, 198T~~
20. Odeh, R.E. and J.O Evans: The Percentage Points for the Normal
    Distribution, AS 70. Appl. Statist. 23:96-97, 1974.


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                                                               29 Jul 86


21. Wichmann, B.A. and I.D. Hill: An Efficient and Portable Pseudo-random     435
    Number Generator, AS 183. Appl. Statist. 31:188-190, 1982.
22. Gage, J.G.: The Significance of Blood Cholinesterase Activity
    Measurements.  Residue Reviews 18:159-173, 1967.
23. Gaines, T.B.: Acute Toxicity of Pesticides. Toxicol. Appl. Pharmacol.
    14:515-534. 1969.
24. Owens, E.W. and S.Y. Owens. Science, submitted 1984.
25. Ray, R. Occupational Exposure to Organophosphate Pesticides among
    Agricultural Workers and their Families.  MS Thesis, University of
    California, Berkeley CA, 1972.
26. California Crop and Livestock Reporting Service, 1981.
27. Popendorf, W. and R.C. Spear: Preliminary Survey of Factors Affecting
    the Exposure of Harvesters to Pesticide Residues.  Amer. Industr. Hyg.
    Assoc. J. 36:374-380, 1974.
28. Pesticide Use Reports, California Dept. Food and Agriculture,
    Sacramento CA, for the years noted (1972-1982).
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                                                                             436
Table I.  Equivalence of the terms and notation used in the text of this
report versus the notation used in the programs listed in Appendix B and C.
Terms are listed according to the subscript by which they were varied (or
if in parentheses, by which they could have been varied).
Terms not used:
  initial residue
  reentry interval
  absorption coef.
                          m
                    text subscript
                          text
                         notation
terms varied:
  reentry residue
  daily field residue
  dosing coef.
  body weight
  enzyme coef.
  reversion coef.
  regeneration rate
terms not varied:    .
  residue decay coef.
  work day
  dermal tox.
  enzyme measurement
                           r
                          LD
                            50 :
                          T
                          k.
                                    chem.
                                     i
                                    (x)
                                            crew
(x)a

(x)



(x)a

(x)
                  program subscript  mm
                                    chem.
               person
                 j
                                             x
                                             x
                 X
                 X
                 X
                 X
                 X
                                             i
                                            crew
 (x)

  j
person
         day
          n
          x
          xa
         (x)
         (x)a
                         k
                        day
program
notation

  res
   r
   kd
   wt
   ke
   PP
   P

(x)

(x)

(x)

xb
half
hwpd
Id50
vlab
 program
 notation
  footnote:
     a) term effectively varied by variations in R  above.
     b) capability to vary laboratory measurement technique was built in to
        program, but unused throughout the majority of the  study.
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                                                                            437
Table II.  A summary of the mean and deviation for each model parameter
used within this study.  Deviations followed by "x" denote geometric
deviations (multipliers and dividers of the mean); those with units are
geometric deviations (the normal distribution).
terms varied:

  reentry residue

  dosing coef.
  body weight
  enzyme coef.
  reversion coef.
  regeneration rate

terms not varied:    .
  residue decay coef.
  work day
  dermal tox.
  enzyme measurement
                           i.n
                           ., ,

                           '"
                          t
                          LD
                                   mean
                            50:i
5.1 cm
70  kg
6.0
0.15 day-1
.893 Z/day
  7  days
  8  hours
 10. mg/kg
            deviation
1.0 to 4.0 x

 1.41  x
+ 7 kg
"1.3   x
 1.01  x
 1.046 x
                reference
[6,12]

[9]
[9]
[9]
[9,14,15]
[18]
                  [12]
                  [15,16]
                  [9,22]
                  [9,17,23]
  footnote:
     a) initial mean reentry residue levels were determined from the Unified
        Field Model based upon the mean daily delAChE response specified by
        the user of the program; each of the following combinations of mean
        residue and residue variability were investigated:
        geometric deviation 1.0
                            1.5
                            2.0
                            3.0
                            4.0
                                  mean delAChE
                                   1%   2%   4Z
               8Z   16Z
                  Draft Report Page 17 of 28
                              ph2.doc

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Table III .  Summary of foliar-dislodgeable parathion (thion) and paraoxon
(poxon) concentrations, ng/cm  from commercial citrus groves sampled on the
same day post-application [reference 6].
                                                                              438
       day  thion    poxon
day  thion    poxon
day  thion    poxon








































arth
std.

geom
geom
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
.mean =
dev. =
N =
.mean =
. dev . =
264.1
398.5
412.6
1434.
180.8
170.9
149.7
190.7
49.75
252.3
186.7
103.5
174.7
294.7
89.13
240.5
688.5
229.2
483.4
1297.
172.6
438.6
152.8
417.3
771.0
386.7
617.8
363.1
199.7
482.8
893.0
562.9
216.0
1724.
303.6
327.2
418.5
193.9
234.6
607.1
419.3
365.1
40
316.0
2.12
18.63
32.07
29.71
109.2
89.60
71.44
108.9
10.54
6.272
33.72
52.82
21.41
35.13
33.72
23.06
20.91
25.46
51.64
166.5
227.3
327.7
396.1
15.66
24.99
365.5
11.44
320.7
32.07
145.0
325.7
276.8
38.02
24.70
92.55
159.7
262.6
62.19
90.48
96.08
210.7
111.2
114.6
40
63.31
3.08
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9











29.94
55.17
95.49
311.2
22.85
17.38
6.319
13.49
7.451
26.64
20.77
22.73
27.59
32.77
19.64
43.62
48.34
57.77
12.05
119.8
21.06
42.68
7.710
38.20
69.32
42.91
67.20
20.30
24.05
15.51
45.39
15.59
92.84
80.76






46.31
54.40
34
31.65
2.33
12.61
33.01
11.67
64.84
25.46
20.42
25.94
2.759
1.252
19.92
16.98
9.290
14.05
12.43
6.201
18.13
11.13
24.99
53.76
135.1
65.78
71.91
4.551
16.41
51.17
15.51
115.3
13.16
22.40
65.31
95.79
9.549
27.62
40.67






33.38
32.75
34
21.16
2.83
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16










9.526
24.52
49.75
113.9
7.474
9.148
5.965
3.466
1.250
9.785
7.144
7.946
10.87
6.272
13.46
8.205
11.48
11.95
5.376
39.14
32.54
2.358
3.843
3.631
20.84
11.93
24.05
4.409
8.583
13.03
10.49
3.773
18.04
35.96
24.73





16.42
20.44
35
10.51
2.52
6.956
8.983
10.12
49.99
7.286
7.875
9.974
1.582
.6413
10.09
6.508
7.309
9.384
6.696
1.846
7.215
7.097
11.51
21.41
21.08
20.58
17.97
2.499
4.951
25.46
4.716
58.00
7.026
13.16
90.19
19.54
4.362
20.45
26.23
29.77





15.96
18.04
35
10.00
2.76
Pooled geometric deviation = 2.61
                  Draft Report Page 18  of 28
                                  ph2.doc

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                                                               29 Jul 86
                                                                         439
Table IV. Chronic Response to exposures 5 days per week distributed among 18
crews of 12 persons each working alternately 2 and 3 days per field (see
also Figures 1-6):
   1) The typical mean pseudo-equilibrium AChE activity expressed as a
      percent of normal baseline of each individual for the harvester cohort
      as a whole  in mid- to late in the last week of the season.
   2) The geometric deviation for the above data, expressed as a percent +
      of the mean.
   3) The prevalence (expressed as percent) of harvesters who have exceeded
      50% inhibition of RBC AChE by the end of the season.
   4) The number of days into the 182 day (26 week) season necessary for
      the analysis of variance F statistic to decrease to or below 2.00
(the critical F
                     ._
                     ii i
Geometric

Deviation
1.0
1.5
           2.0
           3.0
4.0
                            test statistic for 99% confidence of uniformity).
          1%

          35
         +30*
         "6-7%
           0

          37
         +29%
         "6-8%
          38

          40
         +27%
         12-18%
         117
  54
 +17%
 69-74%
>182
                               Daily    Mean   delAChE
                               27.        4%        87.
            50
           +20%
           53-56%
             0

            52
           +19%
           58-63%
            39
            65
           +12%
           "97-99%
             0

            66
           +11%
           98-99%
            38
                                                   75
                                                 +7%
                                                 "lOO%
                                                    0

                                                   76
                                                 +6%
                                                 100%
                                                   37a
55
+17%
69-74%
119
68
+10%
> 9g%
140b
77
+ 6%
100%
>182
47
+22%
41-46%
175
61
+13%
90-94%
>182
71
+ 8%
> 98 %
>182
78
+ 5%
100%
>182
  66
 +10%
 95-97%
>182
                                         74        80
                                        +6%    +4%
                                        99-100% " 100%
                                       >182      >182
                                                                  167.

                                                                   82
                                                                  +4%
                                                                  "lOO%
                                                                    0

                                                                   82
                                                                  +3%
                                                                  1002
                                                                   35°

                                                                   83
                                                                  +3%
                                                                  100%
                                                                 >182

                                                                   84
                                                                  + 3%
                                                                  100%
                                                                 >182

                                                                   85
                                                                  3%
                                                                  100%
                                                                 >182
      footnotes:
         a) not consistently uniform thereafter.
         b) infrequently uniform thereafter.
            Draft Report Page 19 of 28
                                                                 ph2.doc

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                                                                       440
Table Va. Acute Response (in absolute numbers)  to exposures 5 days per week
distributed among 18 crews of 12 persons each working alternately 2 and 3
days per field:
   1) The number of harvesters experiencing  a 1-day AChE inhibition of >50%
      (believed capable of inducing clinical symptoms);  values in excess of
      216 indicate individuals multiply exposed to high  levels of residue.
   2) The number of days throughout the season  in which  the above
      inhibitions occurred (this will be between 1 and 2 times the number
      of fields, depending upon the frequency and severity  of the
      "poisoning").
   3) The number of sprayed fields  per season in which the  above
      inhibitions were clustered into potentially reportable "incidents"
      (involving at least one-half  of the crew).
    Geometric

    Deviation
1.0
                 1.5
                 2.0
                 3.0
                 4.0
                              Daily   Mean   delAChE
                           1Z        2%        4%
 0
 0
 0

 0
 0
 0

 0
 0
 0

 1
 0
 0

20
 5
 2
 0
 0
 0

 0
 0
 0

 0
 0
 0

12
 5
 1

82
22
 5
  0
  0
  0

  0
  0
  0

  1
  1
  0

 84
 26
  6

288
 36
 18
 8Z

  0
  0
  0

  0
  0
  0

 39
 16
  2

383
 48
 32
                                                        42
16Z

  0
  0
  0

 46
 22
  3

317
 79
  5

 *
 *
"76

 ft
 ft
 ft
                 2.6
           0
           0
           0
           2
           2
           0
          28
          10
           1
                  Draft  Report Page 20 of 28
                                                ph2.doc

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                                                                  JUJ. OO
                                                                  .      441


Table Vb. Acute Responses (in rates per hundred) to exposures 5 days per
week distributed among 18 crews of 12 persons each working alternately 2 and
3 days per field:

   1) The incidence (percent of 216) of harvesters experiencing a 1-day
      AChE inhibition of >50Z (believed capable of inducing clinical
      symptoms); values in excess of 100% indicate individuals multiply
      exposed to high levels of residue.
   2) The percent of 182 days throughout the season in which the
      above inhibitions occurred (this will be between 1 and 2 times the
      number of fields, depending upon the frequency and severity of the
      "poisoning").
   3) The percent of the 916 sprayed fields per season in which the  above
      inhibitions were clustered into potentially reportable "incidents"
      (involving at least one-half of the crew).

                              Daily    Mean   delAChE
                           1%        2%        4Z        8Z       16Z

    Geometric    1.0        0         0         0         0         0
                            00000
    Deviation               00000

                 1.5        0         0         0         0        21%
                            0         0         0         0        12%
                            0         0         0         0        .3%

                 2.0        0         0        .5%       18Z      147Z
                            0         0        .5Z        9Z       43Z
                            0         0         0        .2%       .5%

                 2.6        0        .9%       13%
                            0         1Z        5Z
                            0         0        .17.

                 3.0        .1Z       6%       39Z      177Z       *
                            0         37.       14%       26%       *
                            0        .1%       .7Z      3.5Z     "8.3%

                 4.0        9Z       38Z      133Z       *         *
                            3%       12Z       20Z       *         *
                           .2Z       .5Z      2.0Z     ~4.6%       *
    footnote *) frequencies become unreliably too high to be representative.
                  Draft Report Page 21 of 28                     ph2.doc

-------
                                                                        442
Table VI. Reported use history of  parathion on oranges in California
[Source Pesticide Use Reports, California Dept. Food and Agriculture, for
the years noted}.
     Year
 Number of
Applications
Founds
Acres
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
Tulare County
Jan
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
1982
2206
2135
1554
921
1000
744
638
443
476
681

548
Use Report,
0
1
271
128
165
260
182
158
83
67
21
5
160 377
194 061
161 233
124 049
77 956
90 240
57 111
69 722
50 051
55 677
54 171

49 848
Oranges, 1972.
0
1
22 045
6 867
15 640
25 335
11 975
11 174
20 778
6 462
1 520
559
52 855
65 777
63 574
45 189
30 742
29 106
21 765
23 314
14 199
14 446
21 845

17 579

0
1
9 905
3 092
4 662
7 086
4 357
3 682
2 919
1 900
1 520
155
Pounds/Acre
                                                      2.84
                                                      2.23
                                                      2.22
                                                        .35
                                                        .58
                                                        ,75
                                                        .03
                                                        ,12
                                                        .40
                                                      3.55
                                                      3.60
                                     3.
                                     3.
                                     2.
                                     3.
                                     7.
                                     3.
           totals   1444
               122  737   38  199
                       3.21
                  Draft  Report Page 22 of 28
                                               ph2.doc

-------
I
NJ
     o
     
                                                                                                                      f-60  -
                                                                                                 to
                                                                                                 ac.

                                                                                           f-BO  u.
                                                                                                 o
                                                                                                                             o:
                                                                                                                             UJ
                                                                                                                             Q-
                                                                                                                        •90
                                                                                                                182

-------
                   DAYS
WITHIN    SEASON
Figure 2.  Plot of AChE activity on the Y axis versus seasonal time in
           days on the X axis for 2% daily delAChE, with residue geometric
           deviation increasing progressively from the top to bottom line
           from 1.0 to 1.5, 2.0, 3.0, and 4.0, respectively.

-------
100-

 BO-

 60-


 4O-
    rt

    UJ
I    UJ
N)   v>
        10
                 —T
                  14
                   —T
                    28
—T
 42
—T
 56
70
                                               DAYS
—T
 B4
98
—T~
 112
126
140
154
—I—
 168
                                                   WITHIN   SEASON
                            Figure 3.  Plot of AChE  activity on the Y axis versus  seasonal time in
                                       days on the X axis for 4% daily delAChE, with residue geometric
                                       deviation increasing progressively from the top to bottom line
                                       from 1.0 to 1.5, 2.0, 3.0, and 4.0 respectively.
                                                                                                                   •o

                                                                                                                   •20

                                                                                                                  -4O
                                                                                                                  _     OQ
                                                                                                                        I
                                                                                                                  -60  -
                                                                                                                         X
                                                                                                                         o
                                                                                                                        CO
                                                                                                                        Of

                                                                                                                  •BO  u.
                                                                                                                        o
—T
 182
                                                                                                             go
                                                                                                                 CD

-------
                                                                                         30
                                                                                      182
                    DAYS
MlTHIN    SEASON
Figure 4.  Plot of AChE activity on the Y axis versus seasonal time in
           days on the X axis for 8% daily delAChE, with residue geometric
           deviation increasing progressively from the top to bottom line
           from 1.0 to 1.5, 2.0, 3.0, and 4.0, respectively.

-------
1CM
                                        DAYS
WITHIN    SEASON
                      Figure 5.  Plot of AChE activity on the Y axis versus seasonal time in
                                 days on the X axis for 16% daily delAChE, with residue geomtric
                                 deviation increasing progressively from the top to bottom line
                                 from 1.0 to 1.5, 2.0, 3.0, and A.O, respectively.

-------
                   DAYS
WITHIN    SEASON
Figure 6.  Plot of AChE activity on the Y. axis versus seasonal time in days
           on the X axis for 0 residue variability, with daily delAChE
           increasing progressively from the top to bottom line from 1% to 2%,
           4%, 8%, and 16%, respectively.
                                                                                           00

-------
                                                               25 Jul 86

                                                                           449
Appendix A: listing of Fortran simulation program (with comments) to be run
            on an IBM 370 with VS operating system.  Lines following
            //GO.FT01F001 DD *  are input data for batch mode operation.

// JOB (,25),'F1-FREY',TIME=(002),MSGLEVEL-(1,1)
/'PASSWORD PPSU8
/*ROUTE PRINT WYLBUR
// EXEC FORTVCLG,FVREGN«1200K,GOREGN-1024K
//FORT.SYSIN DD *
c
c Reentry Simulation Program , IBM 360 Version 1
c
c input used for this simulation problem:
c
c  i.   means and sd (geometric means and sd for kd,p,pl,res.eq.coeff.)
c       1. rmp, regeneration of rbc and their enzymes [usually 1-2%]
c          rmpl, reversion of rbc  [usually 0-15]:
c          rmp,sdp,rmpl,sdpl                            (4F10.5)

c       2. kd dose coefficient, ke enzyme coefficient:
c          rmkd.sdkd, rmke.sdke                         (4F10.5)

c       3. mass (body weight) of workers:
c          rmwt,sdwt                                    (2F10.5)

c
c  ii.  parameters determing pattern of field exposure
c       1. nf = number of fields worked per crew:       (i3)
c       2. nc = number of crews to be placed in fields:  (i3)
c       3. nm = number of members per crew:             (20i3)
c       4. te « time (days) of initial re-entry into each field
c               after spraying:                         (flO.5)
c       5. tw * time (hours) worked per day :           (flO.5)
c       6. Id50 = LD50 for parent and each oxon:        (4fl0.5)
c       7. nd = number of days to complete each field:  (i3)
c
c  iii. input residues of parent [and oxon]:
c       1. read mean and geometric deviation of parent and ditto for oxons
c                                                       (4F10.5).
c
c  iv.  other input variables
c       1. dseed = an integer value (1-2147483647) typed in double
c                  precision, to be used to generate random number:
c                                                       (flO.O)
c
      CHARACTERS  NMC(20)
      CHARACTER*40 INPUT,OUTPUT,RESDUE
      DOUBLE PRECISION DSEED
      REAL  P(18,12),P1(18,12),KK(18,12,100),LD50(10),
     +     KD(18,12),KE(18.12),WT(18,12),DEL(18,12,100),
     +     RP(301),RKE(301),RKD(301),RWT(301),RAA(301),RP1(301),
     +     R(18,18),H(18,12,100),H1(18,12,101),HE(12),
     +     HM(18,100),HSD(18,100)

c     lun is a vestigal parameter from a F77 version directing output:
      LUN -  4
      READ  (1,10) RMP,SDP,RMP1,SDP1
      READ  (1,10) RMKD.SDKD,RMKE.SDKE


                   Appendix A  Page 1 of 6

-------
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
   READ  (1,10) RMWT.SDWT

   print means and sd

   WRITE (LUN.20)  RMKE,SDKE,RMWT,SDWT,RMP,SDP,RMP1,SDP1,RMKD,SDKD
20 FORMATdX,/,
  +   IX,'MEANS AND DEVIATIONS GIVEN ON INPUT'   /
  +   7X,'FOR NORMALLY DISTRIBUTED VARIABLES'    /
  +  1OX,'ENZYME COEFFICIENT KE1,    T45.2F10.5  /
  +  10X,'WORKERS WEIGHT',           T45.2F10.5  /
  +   7X,'FOR LOGNORMALLY DISTRIBUTED VARIABLES '/
  +  1OX,'REGENERATION, P1,          T45.2F10.5  /
  +  1OX,'REVERSION,PI1,             T45.2F10.5  /
  +  10X,'DOSING COEFFICIENT KD',    T45.2F10.5  /)

   input other parameters describing field
   READ  (1,25) NF
   READ  (1,25) NC
   READ  (1,30) NM
   READ  (1,10) TE
   READ  (1,10) TW
   READ  (1,10) LD50(1)
   READ  (1,30) ND
   READ  (1,10) RESSS,REGED
   READ  (1,40) DSEED
   input formats
10 FORMAT(4F10.5)
15 FORMAT(8F10.5)
25 FORMAT(I3)
30 FORMAT(20I3)
40 FORMAT(FIO.O)

   output parameters describing field
   WRITE (LUN.35) NC.NF.ND.TW.TE,DSEED,LD50(1),RESSS,REGED
35 FORMAT( IX,'OTHER PARAMETERS GIVEN ON INPUT1,
  +       lOX.'NO. OF CREWS',
  +       lOX.'NO. OF FIELDS PER CREW',
  +       lOX.'NO. OF DAYS TO COMPLETE FIELD1,
  +       10X,'NO. OF HOURS WORKED PER DAY',
  +       10X,'TIME OF RE-ENTRY INTO FIELDS',
  +       10X,'INPUT VALUE FOR DSEED1,
  •f       10X,'LD50 FOR PARENT1,
  +       10X,'MEAN RESIDUAL VALUE1,
                                                                        450
                                                             .I3
                                                             .I3
                                                             .I3
                                                             .F10
                                                             .F10
                                                             .E13
                                                             .F10
                                                      T41
                                                      T41
                                                      T41
                                                      T40.
                                                      T40.
                                                      T60.
                                                      T40.
                                                      T60.F10.5 /
                                                                    /
                                                                    /
                                                                    /
                                                                    /
                                                                 .5 /
                                                                  5 /
                                                                  7 /
                                                                  5 /
             1 OX, 'GEOMETRIC DEVIATION FOR RESIDUAL VALUE1 ,T60,F10.5)

      notation and documentation of arrays
     i.  for crew i, member j
           P  (i,j)  per cent regeneration
           pi (i,j)  per cent reversion
           rkd(i.j)
           rke(i.j)
           wt
ii.
         for crew i, member j, day 1 (field k)
         del(i,j,l)  represents the percent of enzyme activity inhibited
                   Appendix A  Page 2 of 6

-------
                                                               25 Jul 86


c                    after one dose
c        kk (i,j,l)  ratio of active enzyme after 1 dose « 1- del(i,j,k)
c        h  (i,j,l)  health (ratio to initial of enzyme remeaining after
c                    the kth dose)
c        hi (i,j,l)  ratio of enzyme after recovery of 1-1 doses
c                    and therefore also the ratio before the 1th dose
c                    and health at beginning of the kth day
c
c   iii. for coefficients of residue equation
c        cf(n,k)  n coefficients for the k fields worked per crew
c        r(i,l)  is residue to parent (i-1) or oxon (i»no. oxon+1)
c                 for day 1
c
c     get characteristics for each individual from using either a
c     lognormal or normal random no generator (imsl routine)
c
c     get random values for wt, and ke using the normal dist.,  imsl ggmnl
c
c
      DO 500 1=1,NC
         CALL LGNM (DSEED.NM.RMP, SDP, RP)
         CALL LGNM (DSEED,NM,RMP1,SDP1,RP1)
         CALL LGNM (DSEED,NM,RMKD,SDKD,RKD)
         CALL GGNML(DSEED.NM.RWT)
         CALL GGNML(DSEED.NM.RKE)
c
c        now assign each member of field a random no.  chosen above
c
         DO 400 J « l.NM
            KD(I,J) - RKD(J)
            KE(I,J) « RKE(J)*SDKE+RMKE
            WT(I,J) - RWT(J)*SDWT+RMWT
            P (I,J) - RP (J)
            P1(I,J) - RP1(J)
  400       CONTINUE
  500    CONTINUE
c
c     for each crew member get the ratio of the percent of active
c     enzyme to the initial amount of active enzyme after nf fields
c     have been harvested.
c
c     parameters used here
c
c     h(i,j,l) fraction of depleted enzyme after 1 days (in kth field)
c        for crew i,member j, field 1 (health after 1 days in kth field)
c     hl(i,j,l) fraction of active enzyme 24 hours after the 1th dose
c        or the fraction of active to start the (l+l)th day (kth field)
c        for crew i, member j, 1 days in field k
c
c     set health for initial to 1  (i.e. hli.j.lM for all i,j)
      DO 700 I • l.NC
         DO 710 J • l.NM
            H1(I,J,1) «= 1
  710       CONTINUE
  700    CONTINUE
                   Appendix A  Page 3 of 6
451

-------
                                                               25 Jul 86


c                                                                        452
c     print table discribing events
c
      DO 1000 I i l.NC
         WRITE (LUN.1001) I
         WRITE (LUN.1010) (WT(I,J),J=1,NM)
         WRITE (LUN.1020) (KE(I,J),J=1,NM)
         WRITE (LUN.1030) (KD(I,J),J=1,NM)
         WRITE (LUN.1040) (P(I,J),J-1,NM)
         WRITE (LUN.1050) (Pl(I.J),J=1,NM)
 1001 FORMATUX ,////,
     +
     +  5X,
     +  T33, 'l',T42,
     +  TlOZ.'S'.TllZ,
 1010 FORMAT(T28,'WT«
 1020 FORMAT(T28,'KE=
 1030 FORMAT(T28,'KD=
 1040 FORMAT(T28,'  P*
 1050 FORMAT(T28,'P1«
 RESULTS OF ANALYSIS FOR CREW ',13,
 WHERE INFRACTION OF ENZYME INHIBITED1,//
 FIELD CONDITIONS',T28,'CREW MEMBERS'/
2',T52, '3',T62 ,'4',T72/ '5',T82, '6',T92,
9',T122,'10I // )
 F6.2.T41.F6.2,  8(4X,F6.2))
 F7.3.T41.F7.3,  8(3X,F7.3))
 F7.3,T41,F7.3,  8(3X,F7.3))
 F9.5.T41.F9.5,  8(1X,F9.5))
 F9.5.T41.F9.5,  8(1X,F9.5))
         DO 850 K = l.NF
            NIII = 50
            CALL LGNM (DSEED,NIII,RESSS,REGED,RAA)
            IF (RAA(l).GE.RESSS) FPER=3
            IF (RAA(l).LT.RESSS) FPER=2

            DO 777 L «= l.ND
c     calculate dose for each residue (from parent and oxon)
c     note r(mm,l) is residue for 1th day for parent(mm=l) or
c                             oxon number mm-1
c
c     determine residue for each of parent and oxons
               DO 803 MM » 1,1
                  IDDD    - L*5+MM
                  R(MM,L) = RAA(IDDD)
                  IF (L.EQ.3) R(MM,L)*R(MM,2)*EXP(-0.074)
                  IF (L.EQ.4.AND.FPER.EQ.3) R(MM,L)-R(MM,2)*EXP(-0.148)
                  IF (L.EQ.5.AND.FPER.EQ.2) R(MM,L)=R(MM,4)*EXP(-0.074)
                  IF (L.EQ.6.AND.FPER.EQ.2) R(MM,L)=R(MM,4)*EXP(-0.148)
                  IF (L.EQ.6.AND.FPER.EQ.3) R(MM,L)=R(MM,5)*EXP(-0.074)
                  IF (L.EQ.l) R(MM.L) - 0.
                  IF (L.EQ.7) R(MM,L) - 0.
  803             CONTINUE

               DO 800 J = l.NM
                  SUM = 0
                  DO 801 MM - 1,1
                     D   = (KD(I,J)*R(MM,L)*TW)/(WT(I,J)*1000.)
                     SUM - (D/LD50(MM))+SUM
  801                CONTINUE
                  DEL(I,J,L) = 1-EXP(-KE(I,J)*SUM)
                  KK(I.J.L)  = l-DEL(I.J.L)
                  H(I.J.L)   = KK(I,J,L)*H1(I,J,L)
                  P2         - l.
                   Appendix A  Page 4 of 6

-------
                                                               25 Jul 86
                  P3
                  Rl
                  R2
                  TOP
   800
                  H(I,J.L)
                  HE(J)
                  CONTINUE
                               H(I,J,L)*P2
                               P1(I,J)*DEL(I,J,L)
                               R1+R2+P(I,J)
                               TOP/P3
                               l.-H(I.J.L)
                               H1(I,J,L-H)
                                                                          453
   802
               SUMH   - 0.
               SUMH2  = 0.
               DO 802 J - l.NM
                  SUMH  - SUMH+H(I,J,L)
                  SUMH2 « SUMH2+H(I,J,L)*H(I,J,L)
                  CONTINUE
               HM(I,L)  - SUMH/NM
               HSD(I.L) = ((SUMH2-HM(I,L)*SUMH)/(NM-1))**0.5
               WRITE (LUN,1060)K,L,R(1,L),(H(I,J,L),J=1,NM).
                               HM(I,L),HSD(I,L)
  1060
  777
               FORMATUX, 'W ,13, 'D1,13,Til, 'RESIDUE-1 ,F8.3,T28, 'H=',
                      F6.4,T37,F6.4,12(1X,F6.4))
               CONTINUE
            DO 888 J « l.NM
               H1(I,J,1) - HE(J)
  888          CONTINUE
  850       CONTINUE
 1000    CONTINUE
      END

      SUBROUTINE LGNM(DSEED,NF,A,B,X)
      DOUBLE PRECISION DSEED
      DIMENSION X(301)
      S  - ALOG(B)
      XM « ALOG(A)
      CALL GGNLG(DSEED,NF,XM,S,X)
      RETURN
      END

//GO.FT04F001 DD DSN=WYL.CMD.SIM.AAA,UNIT=DISK,VOL*SER=WYLB02,
// DCB=(RECFM=FB,LRECL«133,BLKSIZE«6118),
// SPACE=(TRK,(27,2)),DISP=(NEW,CATLG)
//GO.FT01F001 DD *
                       0.15000   1.01000
                       6.00000   1.30000
 0.0089286
   5.10000
  70.00000
026
018
012
   7.00000
   8.00000
  10.00000
007
 119.00000
3857100000
 1.0457
1.41000
7.00000
             2.00000
                   Appendix A  Page 5 of 6

-------
Appendix B: Listing of the simulation program run on the IBM-PC with       454
            Microsoft Fortran compiler.  Lines following the last "end" are
            a separate input file called "simlib" .

      program simS
c     unified field model simulation program , "version 5.2" [23 Jul 86]
c     comprising submodels 2-3 with variability in the H measurement added
c        submodel 1: R   * Ro exp(-Kr T)
c        submodel 2:D   = R Kd t / m
c        submodel 3: del « 1 - exp(Ke sum(D / LD50))
c     therefore      R   « -LD50 ln(l - del) m / Kd Ke t
c     This version groups and prints (with no option) all crews by day to
c        facilitate operation of summary program pp5, and staggers the working
c        pattern experienced by each crew.

c  batch file input for this simulation program in a file to-be-named:
c
c  i. input the field residue conditions: mean daily inhibition,
c     geometric deviation of that residue, and short-term decay rate:
c      1. percent daily inhibition "delbar"                            (flO.2)
c      2. geometric deviation of the residue "gdres"                   (flO.2)
c      3. half-life [days] of residue during harvest "half"            (flO.2)
c      4. AChE measurement (interday intraperson) variability          (flO.2)
c  ii. means and sd of worker parameters:
c      5. gmp, regeneration of rbc and their enzymes, usually 1-2%
c         gmpp, reversion of rbc, usually 0-15%:
c         "gfflpV'gdpV'gmppV'gdpp"                                   (AflO.5)
c      6. kd dose coefficient, ke enzyme coefficient:
c         "gmkd","gdkd","gmke","gdke"                                 (4fl0.5)
c      7. arithmetic mean and standard deviation of mass of worker:
c         "rmwtV'sdwt"                                               (2fl0.5)
c  iii. parameters determing field exposure
c      8. nw    = number of weeks worked per crew:                        (13)
c      9. nc    • number of crews to be placed in fields:                 (i3)
c     10. nm    = number of members per crew:                           (2013)
c     11. dpa   = time (days) of initial re-entry into
c                 each field after (post) spraying:                       (13)
c     12. hwpd  = time (hours) worked per day :                           (13)
c     13. nd    = number of days to complete each field
c                 (a repeatable pattern of from 1-10 values
c                  ending in 0; any negative values are accepted
c                  as specifying days with no additional exposure):     (1013)
c     14. Id50  = LD50 for parent (and each of up to 3 oxons):        (4fl0.5)
c  iv.  other input variables
c     14. iseed = three integer values (1-2147483647)
c                 to be used to generate random numbers:
c  to input and output data to and from this program:
c     1) the program will ask the user the name of the file which has
c        data for input (assigned as file 1);
c     2) the program asks the user if output is to be written on the
c        termianal or to be saved as an output file;
c     3) the file number and name are then given by the user.
c        If user enters 0 then the terminal receives the output;
c        If  "     "    1 and a file name, health only output is saved  f6.4


                   Appendix B  page 1 of 10

-------
                                                              23 Jul 86

                                                                           455
         If  "     '     2 and a file name, more complete output is saved f5.3

      character*14 input, output
      integer      iseed(3),nd(10),dpa,hwpd,filel,file2,
                   ipat(18),ires(18),m(18),noff(18)
      real         res(2000),    r(4),ld50(4),
                    p(18,12),pp(18,12),wt(18,12),kd(18,12),ke(18,12),
                   rp(216), rpp(216), rwt(216), rkd(216),  rke(216),
                   kk(18,12),
      filel  « 1
      file2  - 2
c     indicate the name of the file to find input data
      write  (*,101)
  101 format ( ' Enter name of input file :   '  )
      read   (*,102) input
  102 format (a)
c     indicate the name of the file to receive the worker health output.
*     write  (*,103)
* 103 formatC Enter either 0 for the output to return to the terminal1,
*    +  /,8x,' or 1 if health status  only  is to be saved as a file1,
*    +  /,8x,' or 2 if more complete output is to be saved as a file:1)
*     read   (*,104) lun
      lun    - 1
  104 format (il)
      if     (lun .eq. 0) go to 106
      write  (*,105)
  105 format (' Enter the name of the health status output file :  '  )
      read   (*,102) output
      open   (file2,file»output, status* 'new1 )
      rewind  file2
  106 open   (filel, file=input)
      rewind  filel

c     read average daily inhibition, its variability, and
c     the within field residue decay rate (half life);
c     followed by other means and deviations
c     (geometric for lognormal distributions p, pp, kd, ke, and (arith) wt);
c     and finally other input parameters describing field.
      nr     « 1
      mnp    • 10
      read  (1,10) delbar,gdres,half , gdlab
      read  (1,10) gmp,   gdp,  gmpp, gdpp
      read  (1,10) gmkd, gdkd,  gmke, gdke
      read  (1,10) rmwt, sdwt
      read  (1,25) nw
      read  (1,25) nc
      read  (1,30) nm
      read  (1,25) dpa
      read  (1,25) hwpd
      read  (1,30) nd
      read  (1,10) (Id50(nres),nres=l,nr)
      read  (1.45) iseed
   10 fonnat(4f!0.5)
   25 format(i3)
                   Appendix B  page 2 of 10

-------
   30 fonnat(20i3)
   40 fonnat(flO.O)
   45 format(4ilO)

      npp   = 0  '
      ndinp = 0
      do 50 i « l,mnp
         ndinp  * ndinp + abs(nd(i))
         if     (nd(i) .gt. 0) npp * npp + 1
         if     (nd(i) .eq. 0) go to 51
   50    continue
   51 np    = i-1
      nf    = nc * (npp * (nw * 5) / ndinp)
      npop  = nm * nc
*     nlab  = npop * (nw * 7)
      gmres = -Id50(l)*alog(l.-(delbar/100.))*nnwt / (gmke*gmkd*hwpd)
      if    (gdlab .le. 1.0) gdlab -1.0
      do 53 i - l.nc
         ipat(i) - mod(i.np) + 1
         ires(i) = i
         m(i)    = 1
         noff(i) * 0
   53    continue
c     internal variables defined above:
c     mnp   = maximum number of "within field harvest" patterns.
c     nd    - (array) repeatable pattern of the number of days to complete
c             each field.  Note nd<0 means to work in field with no anti-AChE
c             residues; weekends (iday = 6 and 7) are also no-exposure days.
c     np    = number of patterns specified by user.
c     npp   = number of positive pattterns (fields with residues) per  cycle.
c     ndinp = total number of working days within all patterns.
c     nf    = total number of fields required to be simulated.
c     npop  - total size of population (cohort) required to be simulated.
c     ires  = (array) residue (or field) counter stepping res() up to  nf.
c     nlab  = number of simulated laboratory measurements (assumed to  be each
c             day of season) and associated measurement variations.
c     noff  * (array) number of weekend days (off) during which residue decays
c     gmres = geom. mean residue corresponding to the mean delta AChE  specified

c     get characteristics for each individual in population and
c     field in the entire season by using
c     either a lognormal or normal random number generator (subroutine) :
  500 write (*,*) 'Creating body weights'
      call   nml  (iseed,npop,rwt,rmwt,sdwt)
      write (*,*) 'Creating dosing coefficients'
      call  Ignml (iseed,npop,rkd,gmkd,gdkd)
      write (*,*) 'Creating enzyme coefficients'
      call  Ignml (iseed,npop,rke,gmke,gdke)
      write (*,*) 'Creating RBC regeneration rates'
      call  Ignml (iseed,npop,rp ,gmp ,gdp )
      write (*,*) 'Creating RBC reversion rates'
      call  Ignml (iseed,npop,rpp,gmpp,gdpp)
      write (*,*) 'Creating residues'
      call  Ignml (iseed.nf,res, gmres,gdres)
                   Appendix B  page 3 of 10

-------
                                                              23 Jul 86


      if    (lun .eq. 0) go to 600                                     457
      write (*,*) 'Beginning simulation:'                               < ------
      write (*,*) 'Day     of     Crew     Residue      of
c
c  notation and documentation of subsequent arrays
c    for crew i, member j (day k in season, day m(i) in field)
c     P  (i»j) " per cent regeneration / 100.
c     pp (i,j) « per cent reversion  / 100.
c     rkd(i,j) » dosing coefficient
c     rke(i,j) = enzyme response coefficient
c     wt (i,j) = body weight (mass)
c
c     kk (i,j) « enzyme activity after any one dose • 1- del(j),
c                relative to pre-dose activity
c     h  (i,j) * health (enzyme activity remaining after the kth dose
c                relative to initial activity)
c     hi (i,j) « relative enzyme activity after 24 -hr recovery of kth dose
c                and therefore also the pre-dose activity before the k+lth
c                dose
  600 CONTINUE
      k    - 0
      do 1000 iwk - l.nw                                                WEEKS

c        A "pattern" do loop could not be constrained either internal to
c        or external from the week loop (used to define weekends off).
c        Thus, each new ipat is set prior to line 870 to another field
c        (ires) whose initial reentry residue (day m-1 in the field) is
c        selected from the random array of nf residues created earlier
c        but which also undergoes decay after each (m) harvest-working
c        day in that field plus any intervening (noff ) days off at the
c        half-life specified until the harvest has been completed
c        (m » number of days in nd(ipat(i))).

         do 880 iday « 1,7                                              DAYS
            k  • k + 1
            do 870 i - l,nc                                             CREWS
               if ((iday .eq. 6). or. (iday .eq. 7)) noff(i) » noff(i) + 1
*              if (lun .eq. 0) go to 630
               write (*,1065) k,nw*7,i.ires(i),nf
  630          do 800 j - l,nm                                          MEMBERS
                  if ((iwk  .ne. 1) .or. (iday .ne. 1)) go to 700
                        ) = rwt(((i-l)*nm)+j)
                        ) « rkd(((i-l)*nm)+j)
                        ) = rke(((i-l)*nm)+j)
                  P (i.j) »  rp(((i-l)*nm)+j)
                  pp(i,j) • rpp(((i-l)*nm)+j)
                  set initial health to 1  (i.e. hl(i,j) « 1 for each j)
  700             sum     * 0.0
                  if      ((iday .eq. 6) .or. (iday .eq. 7)) go to 702
                  if      (nd(ipat(i)) .It. 0) go to 702
                  r(l)    = res(ires(i)) / (2.**((m(i)+noff (i)-
                  do 701 mm * l,nr                                      CHEMRES
                     d       - (kd(i,j)*r(mm)*hwpd) /
                     sum     * (d/ld50(mm)) + sum
                   Appendix B  page 4 of 10

-------
  701                continue
  702             kk(i,j) « exp(-ke(i,j)*sum)
                  p2
                  p3
                                     I p3
c                 process validation print test
*                 write (*,739) k,i,j,m(i),nd(ipat(i))
*    6            ,ipat(i),noff(i),ires(i),res(ires(i))
*    6            ,r(l),d,sum,kk(i,j),h(i,j),hl(i,j)
*    6            ,p2,p3,p(i,j),pp(i,j),wt(i,j)
*    6            ,kd(i,j),ke(i,j)
*739              format(/lx
*    6            , 'day, cr//, mem//, m,nd(i),i,,noff, ires -' ,/lx,8i3,/lx
*    6            ,'res,r(l),d,sum,kk,h,hl «'       ,/lx,7f 11.7,/lx
*    6            ,'p2,p3,p,pp,wt,kd,ke «'          ,/lx,7fll.7)
c                 end print test

c                 an expected level of laboratory AChE measurement variability
c                 has been integrated into version 4 and later updates, which
c                 affects output via "h" but not the actual health via "hi".
                  vlab    * gauinv(random(iseed),ifault)
                  if     (ifault .eq. 1) stop 'ifault error in lab var. '
                  h(i,j)  - 1. - (h(i,j)*(gdlab**vlab))
  800             continue
* 820          if    (lun .eq. 1) go to 821
*              write (lun,  1060) i,iwk,iday,r(l),(h(j), j-l,nm)
*              go to 830
  821          write (file2,1061) i,iwk,iday,r(l),(h(i, j),j-l,nm)
  830          if    ((iday .eq. 6) .or. (iday .eq. 7)) go to 870
               m(i)    • m(i) + 1
               if    (m(i) .le. abs(nd(ipat(i))))       go to 870
               ipat(i) = ipat(i) + 1
               if    (nd(ipat(i)) .It. 0)               go to 870
               if    ((ires(i)+nc) .le. nf) ires(i) = ires(i) + nc
               m(i)    « 1
               noff(i) - 0
               if    (ipat(i) .gt. np) ipat(i) - 1
  870          continue
  880       continue
 1000    continue
c     print residue and toxicologic means and deviations
c     followed by other parameters describing field
      write (file2,1054) rmwt,sdwt,gmkd,gdkd,gmke,gdke,
     +                   gmp , gdp , gmpp , gdpp , delbar , gdlab , gmres , gdres
      write (file2,1055) nm,nc,npop,nw,nf .nd.hwpd.half ,(ld50(i),i=l,3),
     +                   iseed
c     print individual crew descriptors unless the condensed
c     output file (lun=l) was requested.
      if (lun .eq. 1)  go to 2000
      do 1100 i • l,nc
         write (file2,1001) i, ( j , j=l,nm)
         write (file2,1010) (wt(i, j) ,j=l,nm)
         write (file2,1020) (ke(i,j), j=l,nm)


                   Appendix B  page 5 of 10

-------
                                                              23 Jul 86


         write (file2,1030) (kd(i,j),j-l,nm)
         write (file2,1040) ( p(i,j),j=l,nm)
         write (file2,1050) (pp(i,j),j=l,nm)
 1100 continue
 2000 stop ' Normal termination of Sim5'

c --- THE LAST PORTION OF THIS PROGRAM SPACE IS RESERVED FOR FORMAT STATEMENTS
 1054 format(lx,/,lx,' Means and deviations given on input1/
     +   7x,'for normally distributed variables:1/
     +  lOx,'workers weight1,                 t45,2f!0.5/
     +   7x,'for lognormally distributed variables:  '    /
     +  lOx,'dosing coefficient kd1,          t45,2f!0.5/
     +  lOx,1enzyme coefficient ke1,          t45,2f!0.5/
     +  1Ox,'regeneration, p1,                t45,2f!0.5/
     +  lOx,1reversion, pp1,                  t45,2f!0.5/
     +  lOx,'mean daily inhibition, X1,       t45,lfl0.5/
     +  lOx,'variability in AChE measurement1,t55,If10.5/
     +  lOx,'reentry residue, ug/cm2',        t45,2f!0.5)
 1055 formatdx,1 Other parameters given on input:',    /
     +  lOx,'number of members per crew ',    t46,i3    /
     +  lOx,'number of crews',                t46,i3    /
     +  lOx,'total size of population    ',   t46,i3    /
     +  10x,'no. of weeks worked per crew',   t46,i3    /
     +  lOx,'total no. of fields sprayed1,    t39,ilO    /
     4-  lOx.'no. of days to complete field',  t46,10i3  /
     +  lOx.'no. of hours worked per day1,    t46,i3    /
     +  lOx,'subsequent half-life, days',     t45, flO.5/
     +  10x,'LD50 for OP pesticide(s)',       t45,3f!0.5/
     +  lOx,'input values for iseed',         t39,3ilO  )
 1001 formatdx ,//lx,
     +'Fraction Acetyl Cholinesterase inhibition for crew *,i3,
     +/lx,'Field conditions:',t22,'Crew members:',
     +/,t22,36(i2,3x)
1010 formate tlS.'wt*
1020 formate t!8,'ke-
1030 formate t!8,'kd=
1040 formate t!8,'p «
1050 formate t!8,'pp«
1060 formate'C',i2,'W
1061 formate'C',i2,'W
                           36ef5.1,0x))
                           36ef5.2,0x))
                           36(f5.2,0x))
                           36ef5.4,0x))
                           36ef5.4,0x))
                                            f6.4,tl9,'H«',14ef5.3,Ox))
                                            f6.4,tl9,'H-',14ef6.4,lx))
 1065 formatei+Day'ti4,' of',i4,' Crew'.iS,1  Residue',i5,'  of',i5)
      end
^^^ — ^ — — — — — — — — — — — «•• • • • • V • V • V •• V * V • V • V • V • •*• •
      subroutine nml (iseed,nx,x,a,b)
      dimension  iseed(3),x(2000)
      s    - b
      xm   -a
      call mcarloeiseed,nx,x,xm,s)
      return
      end
*                         ••••••
      subroutine Ignml (iseed,nx,x,a,b)
      dimension  iseed(3),x(2000)
      s    * alog(b)
      xm   = alog(a)
                   Appendix B  page 6 of 10

-------
      call mcarlo(iseed,nx,x,xm,s)
      do 1 i = l.nx
         x(i) = exp(x(i))
    1    continue.
      return
      end
C [[[
      subroutine mcarlo (iseed,nx,x,a,b)
c     creates a random sequence of 'nx1 values of 'x* which taken as a whole
c     are EXACTLY normally distributed between 0 and 1 in steps of 1/nx
c     (see line 001 taken from U.S. HEW (NIOSH) Publ. //77-173)
      real      x(2000),  y(2000)
      integer   iseed(3),iy(2000)

      do 10 i - l,nx
         y(i) - random(iseed)
   10    continue
      call    rankc (nx,y,iy)
      do 20 i = l,nx
  001    p    = (float(i) - 0.5) / nx
         y(i) = gauinv(p.ifault)
         if    (ifault .eq. 0) go to 20
         write (*,1001)  i.a.b
         stop 'Due to fault error in INVGAU from MCARLO1
   20    continue
      do 30 i = l.nx
         x(i) - a + (b*y(iy(i)))
   30    continue
      return
 1001 format  (' A fault error resulted when processing the ',15,
     +     'th value with mean of ',gl2.4,' and deviation of ',g!2.4)
 1002 format  (' A no-match error resulted when searching for "min"1
     +         ,/,' of ',15,' values with mean of ',g!2.4,
     +            ' and deviation of ',gl2.4)
      end
C [[[
      FUNCTION RANDOM(iseed)
*      FUNCTION RANDOM(IX,IY,IZ)

C     ALGORITHM AS 183 modified FROM B.A. WICHMANN and I.D. HILL
C     An Efficient and Portable Pseudo-random Number Generator.
C     APPL. STATIST. 31:188-190, 1982.
C     incorporating the amendment proposed by A.I. McLeod
C     APPL. STATIST. 34:198-200, 1985.

C     On input IX.IY.IZ are seed integers between 1 and 30,000
C     RETURNS A PSEUDO -RANDOM NUMBER RECTANGULARLY DISTRIBUTED
C     BETWEEN 0 AND 1.


-------
  -                                                           ^J JUl 86


       iz *  iseed(3)

       IX =  171 * MOD(IX,177)  -  2*(IX/177)
       IY -  172 * MOD(IY,176)  - 35*(IY/176)
       IZ -  170 * MOD(IZ,178)  - 63*(IZ/178)

       IF (IX  .LT. 0) IX - IX  + 30269
       IF (IY  .LT. 0) IY - IY  + 30307
       IF (IZ  .LT. 0) IZ - IZ  + 30323

C      IF INTEGER ARITHMATIC UP OT 5212632 IS AVAILABLE,
C      THE PRECEDING 6 STATEMENTS MAY BE REPLACED BY

*      IX -  MODU71 * IX, 30269)
*      IY -  MOD(172 * IY, 30307)
*      IZ -  MOD(170 * IZ, 30323)

C      ON SOME MACHINES THIS MAY SLIGHTLY INCREASE THE SPEED,
C      THE RESULTS WILL BE IDENTICAL.

       iseed(l)=ix
       iseed(2)=iy
       iseed(3)=iz
       RANDOM  = AMOD(FLOAT(IX)/30269.+FLOAT(IY)/30307.+FLOAT(IZ)/30323.,
     +             1.0)
C      McLeod  amendment follows:
       IF (RANDOM.GT.0.0) RETURN
       RANDOM  * DMOD(DBLE(FLOAT(IX))/30269.DO + DBLE(FLOAT(IY))/30307.DO
     +             + DBLE(FLOAT(IZ))/30323.0DO,1.0DO)
       IF (RANDOM.GE.1.0) RANDOM - 0.999999
       RETURN
       END
C	
       FUNCTION GAUINV (P, IFAULT)

C      ALGORITHM modified FROM R.E. ODEH and J.O. EVANS
C      The Percentage Points of the Normal Distribution. AS 70
C      APPL. STATIST. 23:96-97. 1974.

C      Note  the additional following reference provides a polynomial
C           for (0.8 .le. p .It. infinity) if needed:
C      M.E.  Tarter:
C      Inverse Cumulative Approximation and Applications.
C      Biometrika 55:29-41, 1968.
C      See also AS 111, APPL.  STATIST. 26:118-121, 1977 for an alternative form.

C     AS 70 was originally called GAUINV:
C      GAUINV  FINDS PERCENTAGE POINTS OF THE NORMAL DISTRIBUTION
C       P on  input is the lower tail area p
C       IFAULT is a fault indicator :
C         ?' - 1 and gauinv «  0 if (E-20 .le. p .le. 1.- E-20)
C             (ERROR: the requrested x exceeds the outer limits of p
C                     for which the inverse is accurate to within E-7)
C         " « 0 and gauinv *  0 if (p .eq. 0.5)
C             (the true value but not calculable from the polynomial)


                   Appendix B page 8 of 10

-------
                                                                        462
          " = 0 in all other cases.

      DATA            PO,   PI,             P2,                 P3
     +   /-.322232431088, -1.0, -.342242088547,  -.204231210245E-1/
      DATA       "        P*,               QO,             Ql
     +   /-.453642210148E-4, .993484626060E-1,  .588581570495/
      DATA            Q2,            Q3,               Q4
     +   I .531103462366, .103537752850,  .38560700634E-2/
      IFAULT - 1
      GAUINV =0.0
      PS     = P
      IF     (P .GT. 0.5)      PS - 1.  - PS
      IF     (PS .LT. l.OE-20) RETURN
      IFAULT - 0
      IF     (PS .EQ. 0.5)     RETURN
      YI     • SQRT(ALOG(1./(PS*PS)))
      GAUINV • YI + ((((YI*P4+P3) *YI+P2) *YI+P1)  *YI+PO)
     f            / ((((YI*Q4+Q3) *YI+Q2) *YI+Q1)  *YI+QO)
      IF     (P .LT. 0.5)      GAUINV - -GAUINV
      RETURN
      END

      subroutine rankc (nx,x,ix)
      dimension x(2000),ix(2000)

      do 1 i = l,nx
         ix(i) - 0
         continue
      do 3 j = l,nx
         ilast - 2000
         xmin  - 10.**30
         do 2 i * l,nx
            if ((x(i) .It. xmin) .and.  (ix(i)  .eq.  0))  then
            ix(ilast) « 0
            xmin      * x(i)
            ilast
            end if
    2       continue
    3    continue
      return
      end
Input file, typically called simlib:
      4.00      3.00      7.00      1.0 >delbar,gdres,half,gdlab
  .0089286    1.0457       .15      1.01>gmp (regen.),gdp,gmpp (revers.),gdpp
      5.10      1.41      6.00      1.30>kd,gdkd,ke,gdke
     70.        7.                      >wt,sdwt
 26>nw eeks
 18>nc rews
 12                           >nm embers per crew
 14>dpa (days post-application)
                   Appendix B  page 9 of 10

-------
                                                          23 Jul 86

                                                                      463
8>hwpd (hours worked per day)
2-3  3-2                 >nd (pattern of number of days in each field)
   10.00                             >LD50
   25784       985     12919          Mseed
                 Appendix B  page 10 of 10

-------
                                                                           464
Appendix C: Listing of the daily health status analysis and summary program
            written to be run on an IBM-PC with Microsoft Fortran compiler.
            Lines following last "end"  are an external input file typically
            called "pplib" .
C
C
C
C
C
C
C
C

C
*
*
*
ft
*
*
ft
ft
ft
ft
ft
ft
*
ft
ft
*
ft
ft
ft
A
ft
ft
ft
ft
*
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
*
*
Program PP2
Phasell Program 2, Version 5
to read simulation (SIMS) output option //I files;
  (1) scan daily through all crews for "illness" using four
      threshold criteria as specified in a separate "pplib" file,
  (2) tabulate and calculate daily summary health statististics, and
  (3) conduct analysis of variance among crews for health status
      in both arithmatic and geometric modes, optional to do
      every day or only on each clinic day of each week (see inclin)

Defined variable list follows:
CPOI   counter for poisoning cases within day (see also fpoi and inpoi)
DEL    delta AChE
F      F test statistic for arithmatic distribution
FILEO  assigned file: keyboard and screen
FILE1     "      "  : input data
FILE2     "      "  : output of analysis of variance
FILE3     "      "  : input library of run parameters (pplib)
FILE4  unused
FPOI   counter for fields in which poisoning cases occurred
G      F test statistic for geometric distribution
GD     geometric deviation for group
GM     geometric mean for group
GX     log-transformed values of x
H      health (enzyme activity) = 1-x
I      index for days
IDAY   day of week within input sequence
II     "del" counter
IWK    week within input sequence
INCLIN (from pplib) day of the week crews are in clinic for "h" samples
INPOI  counter for incidents of poisoning (defined as .gt. 1/2 of crew)
INPUT  character name of input file
J      index for crew
K      index for person within crew
LINE   line of narrative text; a maximum of 79 characters
M      index for running cumulative days, equivalent to nthres
Nl     degrees of freedom for numerator   of arithmatic F
N2     degrees of freedom for denominator of arithmatic F
N3     degrees of freedom for numerator   of geometric  F
N4     degrees of freedom for denominator of geometric  F
NCREW  crew number as listed within data
NCREWS (from pplib) number of crews included within the study design
       (from pplib) day of the programmed "week" exposure starts
       total number of days in study = nwks*7
       overall number of geometric  data points
NDAYO
NDAYS
NG
NLINE1 (from pplib) number of narrative lines to be copied at end
        of input file
NLINE2 (from pplib) number of narrative lines to be skipped at end
        of input file
NN     overall number of arithmatic data points
                Appendix C  page 1 of 7

-------
                                                              23 Jul 86
*
ft
ft
ft
ft
*
*
*
*
ft
*
*
*
ft
ft
*
*
ft
*
*
ft
ft
ft
NPERC
NTHRES
NWKS
NX
0AM
OGM
OUTP2
PDAY
PGD
PINC
PSD
RES
S2SG
S2SX
SD
SIMAN
SSG
SSG2
SSX
SSX2
TCPOI
THRES

X
XM
(from pplib) number of people per crew
(from pplib)
(from pplib) number of weeks in study
                                                                          465
overall arithmatic mean
overall geometric  mean
character name of anova output file » file2
integer number of previous days within study (max=nthres)
pooled geometric deviation
counter for poisoning cases within a crew-day (see also cpoi)
pooled arithmatic deviation
residue for each exposure day (not manipulated)
(see anov)
(see anov)
standard deviation for group (array)    >
external library of program run parameters
(see anov)
(see anov)
(see anov)
(see anov)
counter for seasonal total cases of poisoning within each  category
(from pplib) quantitative poisoning criteria for 1-AChE (see
 "Parameters from pplib" description below)
level of inhibition (read from input)
arithmatic mean for group (array)
      character*14 input,outp2
      character*79 line
      dimension
      dimension
      integer
      integer
      logical
             h(4,18,12),x(12).gx(12),thres(4)
             xm(18), sd(18),gm(18), gd(18)
             fileO,filel,file2,file3,day,pday
             cpoi(4),fpoi(4),inpoi(4),tcpoi(4),pinc(4)
             negx
C»>»   INPUT FORMAT FROM SIMS option 1
 1000 format (a79)
 1001 format (4x,i2,lx,il, 3x,f6.4,3x,14(f6.4,lx))
*     +      ,(/,20x,14(f6.4,lx)),(/.20x,14(f6.4,lx)))
C 1W.1D1 R« .1986 H- .0817  .0781 -.0195  .0429  .2360
                                                  .1964  .1505  .0969  .304
      fileO
      filel
      file2
      file3
      file4
        0
        1
        2
        3
        4
                                                           user
                                                           input
                                                           output
                                                           pplib
                                                           unused
C.... ask for and read the name of input and output files.
  100 continue
      write  (fileO.1005)
      read   (filed,1004) input
      if     ((input .eq. 'quit').or.(input .eq. 'exit').or.
     +       (input .eq. 'stop').or.(input .eq. 'end')) go to 999
      write  (fileO,1007)
      read   (fileO,1004) outp2
                Appendix C  page 2 of 7

-------
      open   (filel, file=input)
      rewind  filel
      open   (file2, file=outp2, status='new')
      rewind  file2
      open   (file3, file-'pplib')
      rewind  file3
      write  (fileO,1009) input,outp2

C	 READ the operating PARAMETERS FROM PPLIB (file3)
C     ncrews • number of crews included within the study design;
C     nperc  = number of people per crew;
C     nwks   « total number of weeks expected to be read from "input";
C     ndayO  « day of the week exposure starts, assuming 1 equals Monday;
C     inclin » day of the week blood samples are taken in the clinic (0=all);
C     thres  - criteria for 1-AChE ( or x(k) within this program) at
C              which person i considered "overexposed".  Criteria are
C              initially set based on    Daily Inhibition
C                    Simple      day 1  .5     .4     .35
C                    Cumulative  day 2  .75    .64    .58
C                    Effect      day 3  .875   .78    .725
C              therefore, respective values of thres in array
C              (1) a single daily inhibition, x .ge. 0.5
C              (2) a 2-day cumulative  "    , x .ge. 0.65
C              (3) a 3-day     "       "    , x .ge. 0.75
C              (A) a cumulative reduction in h below 0.5
C               m subscript used
C               to store h      and    to calculate del h
C               1: today's h              single daily inhibition (h2-hl/h2),
C               2: yesterday's h          2-day cumulative  "     (h3-hl/h3),
C               3: two day's ago h        3-day     "       "     (h4-hl/h4),
C               4: three day's ago h      cumulative reduction in h
C     nlinel = number of narrative lines to be copied at end of file (input)
C     nlineZ = number of crew narrative lines to be skipped

      read   (file3,3001) ncrews,nperc,nwks,ndayO,inclin,nthres,thres
     +                   ,nlinel,nline2,nline3

C     type input parameters, output table, and screen headers
      write  (file2,3001) ncrews,nperc,nwks,ndayO,inclin,nthres,thres
     +                   ,nlinel,nline2,nline3
      write (file2,2002) 'Wk','Day1,'0AM1,'PSD','F','nl1,'n2','OGM',
     +                   'PGD','G','n3','n4','pol','po2','po3','po4'
      write (file2,2002) •--•,• —•.• — •, • —', •-•, •„•, t__. f ,___i §
     J.                   t___l l_l l__l l__l •___! I	I I   II   I
     T                        »•»»»»   ~ ,
      write (*,*) 'now on crew//    and day     of

C	 set health array (m,j,k) equal to 1.0 (each individual's "normal")
C     subscript i = day within study (season)            limit : ndays = nwks*7
C               j - crew                                         ncrews
C               k = person within crew                           nperc
C               m = running day (1 = today, 2 = yesterday, etc)  nthres
      do 152 j = 1,ncrews
         do 151 k = 1,nperc
            do 150 i « 1,nthres
               h(i,j,k) = 1.0


                Appendix C  page 3 of 7

-------
                                                              23  Jul  86

                                                                        467
  150          continue
  151       continue
  152    continue
      do 153 m « .1 .nthres
         fpoi(m)  - 0
         tcpoi(m) • 0
         inpoi(m) - 0
  153    continue

C - - Begin daily analysis of all crews: ----------------
      iday     - 7
      ndays    • nwks * iday
      do 450 i - 1,ndays                                               DAY >
         negx  » .false.
         iday  • iday + 1
         if    (iday .gt. 7) iday - 1
C        zero the poisoning cases for that day counter
  210    do 215 m » 1,nthres
            cpoi(m)  « 0
  215       continue
C        initialize anova arrays if anova is to be run for the day
         if    ((iday .ne. inclin)  .and. (inclin .ne. 0)) goto 220
         call  anovO (ssx,ssx2,s2sx,nn,ngpn)
         call  anovO (ssg,ssg2,s2sg,ng,ngpg)
C        day i for crew "j" read "k»l,nperc" daily health values
  220    do 300 j * l.ncrews                                           CREW >
            write (*,1111) j,i,ndays
  222       read  (filel,1001,end=501) iwk,iday,res,(x(k),k«l,nperc)
*           write (*,    1001        ) iwk,iday,res,(x(k),k=l,nperc)
            do 223 m « l.nthres
               pinc(m) * 0
  223          continue
C           talley cases in 'Poisonings IN Crew* counter.
            do 6 k = l.nperc                                           MEMB.>
               if  (negx)     goto 1
               if  (x(k) .le. 0.0) then
                   negx = .true.
                   goto 1
                   endif
               gx(k)  = alog(x(k))
    1          do 2 m * l,nthres-l
                  h(nthres-m+l,j,k) « h(nthres-m,j,k)
    2             continue
    3          h(l,j,k) - 1. - x(k)
               do 4 m • l,nthres-l
                  del « (h(mfl,j,k)-h(l,j,k))/h(m+l,j,k)
                  if (del .gt. thres(m)) pinc(m) « pinc(m)+l
    4             continue
    5          del -    (1. -     h(l,j,k))/l.
               if (del  .ge. thres(nthres)) pinc(nthres) » pinc(nthres)+l
    6          continue                                                 
-------
                                                                 Jui oo
            do 7 m = l.nthres
               cpoi(m) * cpoi(m) + pinc(m)
               if (pinc(m) .gt. 0) fpoi(m) • fpoi(m) + 1
               if (float(pinc(m))/nperc .ge. .5) inpoi(m) - inpoi(m) + 1
    7          continue
C           if desired (inclin .ne. 0) anova may be run only on clinic days
            if ((iday .ne. inclin) .and. (inclin .ne. 0)) goto 300
            call  anovl (x, nperc,xm,sd,ssx,ssx2,s2sx,nn,ngpn)
            if    (negx) goto 300
            call  anovl (gx,nperc,gm,gd,ssg,ssg2,s2sg,ng,ngpg)
  300       continue                                                    
-------
                                                              23 Jul 86


 2003 format (13,i2,lx, 2(2x,2f8.5,2x,f5.2,i3,i4), 2x,4i4)
 2004 format (i3,12,lx, I(2x,2f8.5,2x,f5.2,i3.i4),34x,4i4)
 2005 format (13,i2,lx, 2(32x                   ), 2x,4i4)
 2006 format (lx///,39x,'Total number of poisoning cases: '. 3i4,/,
     +              36x,'Days on which a poisoning occurred: ',3i4,/,
     +              38x,'Potentially reportable incidents: *,3i4)
 3001 format (6i4,4f4.2,3i4)
      end
c	
      subroutine anovO ( ssx,ssx2,s2sx,nn,ngp)
c     sx   » sum of x within group
c     sx2  « sum of x**2 within group
c     ssx  * sum of sums of x within group
c     ssx2 » sum of sums of x**2 within group
c     s2sx *
c     nn   • cumulative number of observations in groups l,ngp
c     ngp  * cumulative number of groups
      ssx  - 0.
      ssx2 » 0.
      s2sx - 0.
      nn   - 0
      ngp  « 0
      return
      end
C	
      subroutine anovl (x,nx,xm,sd,ssx,ssx2,s2sx,nn,ngp)
      dimension  x(nx),xm(ngp),sd(ngp)
c     x (i)= array of x values within group ngp
c     nx   = number of observations within group j
c     xm(j)= mean within group j
c     sd(j)« std. dev. within group j
c     sx   * sum of x within group
c     sx2  = sum of x**2 within group
c     ssx  * sum of sums of x within group
c     ssx2 = sum of sums of x**2 within group
c     s2sx =
c     nn   * cumulative number of observations in groups l.ngp
c     ngp  = cumulative number of groups
cccccccccccccccccccccccccccccccccccccccccccccccccccccccccccc
c                                                          c
c  Note :  it is possible for nx (no. of prsons) to equal  c
c          zero, which in turn would cause division by     c
c          zero in mean and s2sx variables.  If there is   c
c          such a possibility, if could be fixed with an   c
c          "IF...THEN"  statement.                         c
c                                                          c
cccccccccccccccccccccccccccccccccccccccccccccccccccccccccccc
c
      sx   - 0.
      sx2  * 0.
      do 1   i • 1, nx
         sx    = sx+x(i)
         sx2   - sx2+(x(i)**2)
    1    continue
      nn   • nn+nx
                Appendix C  page 6 of 7

-------
      ngp   = ngp + 1
      fn   - float(nx)                                                 47Q
      ssx   « ssx+sx
      ssx2  * ssx2+sx2
      s2sx  - s2sx+((sx**2)/fn)
      xm(ngp)* sx/fn
      sd(ngp)» sqrt((sx2-((sx**2)/fn))/(fn-l.))
     2 return
      end
C	
      subroutine anov2  (ssx,ssx2,s2sx,nn,k,oam,psd,f,nl,n2)
c     k     « total number of groups  [ngp in anovl]
c     ssx   * sum of sums of x within group
c     ssx2  = sum of sums of x**2 within group
c     s2sx  *
c     oam   = over-all-mean
c     psd   «= pooled standard deviation
c     f     » F statistic
c     nl    = numerator  degrees of freedom, k - 1 * ngp - 1
c     n2    = denominator degrees of freedom, nn - k
      oam    « ssx/float(nn)
      totss - ssx2-((ssx**2)/float(nn))
      betss » s2sx-((ssx**2)/float(nn))
      witss - totss-betss
      betms = betss/float(k-l)
      witms » witss/float(nn-k)
      psd    • sqrt(witms)
      f      = 9999.99
      if (witms  .ne. 0)  f = betms/witms
      nl     • k-1
      n2     « nn-k
      return
      end
Listing of input file pplib:
  18  12  26   1   0   4 .50 .65 .75 .50  23 114
ncrwnpernwksdayOinclnthrthrs   2   3   41inllin2
                Appendix C  page 7 of 7

-------
                                                             27 Jul 86
Appendix D:  listing of a typical output  from  the health analysis summary
            program (Appendix C); this particular run was for a daily mean
            response of 4% with a residue variation of 3.0 (plotted as the
            second line from the bottom  in Figure 3).
                                                                                 471
 Wk Day    0AM
PSD
nl  n2
OGM
PGD
G   n3  n4   pol po2  po3  po4
1 1
1 2
1 3
1 4
1 5
1 6
1 7
2 1
2 2
2 3
2 4
2 5
2 6
2 7
3 1
3 2
3 3
3 4
3 5
3 6
3 7
4 1
4 2
4 3
4 4
4 5
4 6
4 7
5 1
5 2
5 3
5 4
5 5
5 6
5 7
6 1
6 2
6 3
6 4
6 5
6 6
6 7
7 1
7 2
7 3
7 4
7 5
7 6
.03603
.06132
.11174
.17631
.24283
.22551
.22351
.26962
.29544
.32077
.34635
.36641
.35558
.35241
.36939
.37835
.39645
.45244
.47523
.45783
.45376
.48126
.49771
.52123
.54419
.55989
.54372
.53889
.56026
.56846
.57354
.58424
.59814
.58172
.57654
.59733
.60104
.61392
.62627
.63371
.61678
.61130
.63185
.63794
.64973
.65380
.65166
.63887
.01988
.03254
.05850
.08352
.09752
.08994
.08917
.10039
.10221
.10551
.11053
.11393
.10940
.10843
.11314
.11392
.11553
.12241
.12176
.11608
.11506
.11940
.11983
.12135
.12285
.12216
.11613
.11511
.11840
.11741
.11612
.11670
.11592
.11036
.10938
.11272
.11036
.11063
.10989
.10823
.10310
.10220
.10590
.10426
.10203
.10062
.09948
.09625
19.65
20.37
15.86
16.32
19.88
18.86
18.85
24.60
28.26
23.56
18.18
16.26
17.06
17.06
15.42
15.14
16.38
13.06
15.79
14.34
14.34
15.06
14.55
14.76
9.83
9.14
9.61
9.61
9.11
8.94
8.80
8.20
8.29
8.23
8.23
9.78
9.98
8.90
7.70
7.14
6.97
6.97
5.26
5.11
7.78
8.59
6.67
6.31
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
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.02608
.04489
.08421
.13742
.19112
.17892
.17733
.21348
.24231
.27309
.30271
.32424
.31452
.31172
.32915
.33864
.35519
.41731
.43807
.42399
.42022
.44724
.46482
.48866
.51783
.53540
.52029
.51567
.53713
.54613
.55204
.56371
.57812
.56301
.55800
.57701
.58135
.59574
.60978
.61842
.60248
.59712
.61861
.62536
.63620
.64034
.63942
.62734
1.57011
1.55964
1.53532
1.50343
1.47487
1.47140
1.47139
1.45621
1.44281
1.42929
1.41401
1.40100
1.39808
1.39808
1.39214
1.38479
1.37696
1.35599
1.34167
1.33822
1.33822
1.33211
1.32171
1.30919
1.29359
1.28051
1.27598
1.27597
1.27244
1.26592
1.26034
1.25225
1.24382
1.23949
1.23946
1.23727
1.23152
1.22561
1.21847
1.21168
1.20741
1.20741
1.20606
1.20067
1.19554
1.19174
1.18870
1.18619
28.68
28.68
31.22
31.56
38.00
36.97
36.97
40.27
29.99
23.58
20.31
19.20
19.64
19.64
18.57
18.37
19.31
12.68
14.83
13.91
13.91
13.07
12.72
12.96
9.11
8.55
8.87
8.87
8.48
8.36
8.16
7.82
8.10
7.96
7.96
9.41
9.60
8.31
7.06
6.44
6.46
6.46
4.81
4.57
6.24
6.60
5.63
5.39
17 198
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0 0
0 1
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0 17
0 10
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0 22
0 25
1 33
0 38
0 44
0 42
0 40
0 44
0 48
0 54
1 80
5 92
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0 102
0 114
0 126
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0 144
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                Appendix D  page 1 of 4

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.63318
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.63861
.65286
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.67431
.65403
.64821
.65964
.66059
.67096
.67860
.68954
.66900
.66305
.67675
.68077
.68229
.68312
.68311
.66969
.66373
.67367
.67417
.68439
.68765
.68540
.67174
.66576
.67827
.68072
.68977
.69414
.69613
.68074
.67469
.68659
.68713
.68651
.68931
.69022
.67655
.67054
.67358
.67428
.67816
.68484
.68636
.67134
.66537
.68046
.68286
.68617
.69337
.69376
.09541
.09654
.09585
.09750
.09723-
.09480
.08864
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.09082
.08973
.08978
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.08815
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.08111
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.07696
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.07109
.07047
.07308
.07204
.07193
.07235
.07170
.06818
.06760
.06914
.06914
.07026
.07160
.07072
.06626
.06569
.07031
.07002
.07002
.07022
.06930
6.31
6.57
6.52
7.25
7.31
8.05
6.62
6.62
6.78
6.84
6.90
5.96
7.65
6.51
6.51
8.59
8.73
7.50
7.49
7.63
7.28
7.27
6.60
6.55
7.45
8.13
7.21
7.32
7.31
4.66
4.29
3.52
3.10
3.53
2.99
2.99
3.57
4.59
2.87
3.05
3.38
3.10
3.10
3.27
3.43
3.71
4.14
5.05
4.23
4.23
2.68
3.29
3.75
4.10
4.82
17 198
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.62175
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.64448
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.65091
.66130
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.68012
.66085
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.67386
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.65625
.66600
.66666
.67647
.67974
.67810
.66494
.65902
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.68413
.68883
.69084
.67601
.66999
.68149
.68190
.68177
.68451
.68540
.67216
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.67334
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.68117
.66684
.66090
.67599
.67829
.68151
.68858
.68891
1.18620
1.18639
1.18477
1.18097
1.17597
1.17004
1.16466
1.16465
1.16609
1.16346
1.16089
1.15713
1.15319
1.14835
1.14835
1.14998
1.14807
1.14577
1.14411
1.14249
1.13967
1.13968
1.14198
1.14017
1.13925
1.13649
1.13373
1.13020
1.13021
1.13209
1.12985
1.12901
1.12653
1.12442
1.12094
1.12094
1.12278
1.12105
1.12061
1.12061
1.11946
1.11609
1.11611
1.11798
1.11794
1.11904
1.11945
1.11789
1.11374
1.11376
1.11789
1.11652
1.11576
1.11543
1.11394
5.39 17
5.54 17
5.53 17
6.15 17
5.95 17
6.41 17
5.44 17
5.44 17
5.57 17
5.65 17
5.93 17
5.25 17
6.61 17
5.72 17
5.72 17
7.25 17
7.38 17
6.57 17
6.53 17
6.62 17
6.36 17
6.35 17
5.94 17
5.95 17
6.74 17
7.31 17
6.72 17
6.72 17
6.72 17
4.37 17
4.10 17
3.31 17
2.89 17
3.24 17
2.80 17
2.80 17
3.24 17
3.99 17
2.69 17
2.81 17
3.09 17
2.86 17
2.86 17
3.01 17
3.18 17
3.47 17
3.89 17
4.66 17
3.96 17
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2.57 17
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Appendix D  page 2 of 4

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.67845
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3.99
5.39
3.80
3.77
A. 58
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A. 25
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3.95
A. 50
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11.00
7.55
7.53
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8.56
10.18
11. 5A
1A.A6
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9.23
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10.12
10.18
7.36
7.81
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6.92
7.08
7.1A
6.39
6.62
5.82
5.81
6.2A
7.06
7.06
7.A7
7.79
6.78
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.68594
1.11009
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1.11328
1.11369
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1.11167
1.10990
1.10551
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1.10941
1.10842
1.10826
1.10828
1.10476
1.10061
1.10064
1.10376
1.10324
1.10453
1.10567
1.10218
1.09475
1.09476
1.09836
1.09742
1.09700
1.09658
1.09590
1.09309
1.09311
1.09606
1.09584
1.09655
1.09836
1.09787
1.09401
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1.09855
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1.09242
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1.09788
1.09730
1.09700
1.09596
3.76 17
3.76 17
4.89 17
3.43 17
3.40 17
4.02 17
4.84 17
3.77 17
3.76 17
3.51 17
3.98 17
A. 32 17
8.00 17
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6.68 17
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12.98 17
10.19 17
10.19 17
8.91 17
9.05 17
9.92 17
9.38 17
6.93 17
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6.50 17
6.7A 17
6.75 17
5.78 17
5.90 17
5.28 17
5.27 17
5.60 17
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5.99 17
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7.84
9.64
17.02
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1.09628
1.09321
1.09324
1.09772
1.09803
1.09737
1.09684
1.09650
1.09308
1.09311
1.09814
1.09742
1.09724
1.09839
1.09694
1.09200
1.09203
1.09655
1.09523
1.09504
1.09489
1.09422
1.09072
1.09075
5.49
5.55
5.54
6.25
7.01
6.14
5.32
5.18
5.23
5.23
7.36
8.87
13.18
12.69
13.08
8.35
8.34
.9.75
10.24
10.30
9.15
9.48
9.22
9.21
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
17 198
0
0
0
0
0
0
0
0
0
0
2
0
12
0
0
0
0
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
12
0
0
0
0
1
0
0
0
0
0
0 213
0 213
0 213
0 213
0 213
0 213
0 213
0 213
0 213
0 212
0 212
0 211
8 213
8 214
7 214
0 214
0 214
0 214
0 213
0 213
0 213
0 213
0 213
0 213
                                      Total number of poisoning cases:
                                   Days on which a poisoning occurred:
                                     Potentially reportable incidents:
Means and deviations given on input
     for normally distributed variables:
        workers weight
     for lognormally distributed variables:
        dosing coefficient kd
        enzyme coefficient ke
        regeneration, p
        reversion, pp
        mean daily inhibition, %
        variability in AChE measurement
        reentry residue, ug/cm2
Other parameters given on input:
        number of members per crew
        number of crews
        total size of population
        no. of weeks worked per crew
        total no. of fields sprayed
        no. of days to complete field
        no. of hours worked per day
 70.00000   7.00000
5.10000
6.00000
.00893
.15000
4.00000

.11673
1.41000
1.30000
1.04570
1.01000

1.00000
3.00000
 12
 18
216
 26
936
  2
  8
332000000
              Appendix D  page 4 of 4

-------
Pesticide Exposure of Harvesters  of Blueberries,
  Blackberries, and Raspberries
        Research performed by

        University of California
        Richmond, CA  94804

        October 15, 1985

-------
                                                               476
                            Abstract
During the 1983 growing season in California three field studies
were conducted on the exposure of harvesters of berry crops to
pesticide residues.  These studies were designed to compare dermal
exposure to children (10-12 years old) and adults harvesting
these crops.  In all three studies, methiocarb on blueberries,
benlate on blackberries and benlate on raspberries, a consistent
relationship between age and exposure was observed.  When exposure
is measured as total weight of pesticide deposited per hour
worked, there is an increase of exposure with age.  When the
exposure measure is normalized by body weight there is no
difference in exposure as a function of age.  One study where
work rate was available, provided evidence that differences in
total exposure with age are attributable to differences in work
rate.

-------
                                              Section No. 2
                                              October  15, 1985
                                              Page  1 of  2
                      2.  TABLE OF CONTENTS
Section                                    Page Reference
   1.  Title  page	1  page
   2. Table of contents	2  pages
   3. Project description and
        administrative summary	2  pages
   4. Harvester Exposures in Blueberries	19  pages
       4.1 Introduction	1  of 19
       4.2 Study site and experimental  design....2  of 19
       4.3 Sample storage/  handling  and
           preparation	5  of i9
       4.4 Analytical procedures	5  of 19
       4.5 Crew characteristics	7  of 19
       4.6 Results	9  of 19
   5. Harvester Exposures in Blackberries	18 pages
       5.1 Introduction	1  of 18
       5.2 Study site and experimantal  design....2  of 18
       5.3 Sample storage,  handling  and
           preparation	6  of 18
       5.4 Analytical procedures	«	7  of 18
       5.5 Crew characteristics	8  of 18
 c
       5.6 Results	10  of 18
   €. Harvester Exposures in Raspberries	17  pages
       6.1 Introduction	1  of 17
       6.2 Site and  experimental design	2  of 17
       6.3 Sample storage,  handling  and
           preparation	8  of 17

-------
                                                            478

                                               Section  2
                                               October  15,  1985
                                               Page  2 Of  2
       6.4 Analytical procedures	..8  of  17

       6.5 Crew characteristics	8  of  17

       6.6 Results	9  of  17


Appendices

   A. Methods: Quality Assurance Project  Plan....52 pages

   B. Correspondence regarding  urinary
      metabolite analyses	17 pages
   C. Data files	22
pages
   D. Consent forms and  participant
      instructions	.... .9 pages

-------
                                                                 479
                                               Section  No.  3
                                               October  15,  1985
                                               Page 1 of  2
        3. PROJECT DESCRIPTION AND ADMINISTRATIVE  SUMMARY
     During the 1983 growing season the California PHAP Project
conducted three field studies on the exposure of the harvesters
of berry crops to pesticide residues.  These studies were design-
ed to compare the dermal exposure of children (10-12 years  old)
and adults harvesting these crops.  Secondly an attempt was to be
made to compare dermal exposures as measured by the patch techni-
que and glove monitors with exposures quantified by the urinary
excretion of the pesticides and their metabolites.

     The scope of these studies was limited, where possible, to
the analyses of exposures to the pesticides  applied to  the  crops
most recently before harvesting commenced.  These  pesticides
turned out to be methiocarb on  blueberries and  benomyl  on black-
berries and raspberries.   Approximately twenty  workers  were in-
volved  in each of these studies.  In addition to the collection
of data on dermal exposures, foliar residue  data were also  col-
lected.
                                          *

     The principal failure in achieving the  goals of these
studies is that no urinary metabolite data can  be reported. The
background behind this failure is detailed in the correspondence
included here as Appendix B.  At this time these  samples  remain
in storage awaiting analysis by EPA or its designee. As a result,
the individual study reports, Sections 4,  5,  and  6, deal  with  the
patch, glove and foliar  residue data only.  Included as Appendix

-------
                                                              480
                                               Section No.  3
                                               October 15,  1985
                                               Page 2 of 2
C is the information needed for  subsequent  analysis of the  meta-
bolite results when they become  available.

     A consistent relationship between exposure and age was
observed in all  three  studies.  When exposure is measured as
total weight of pesticide deposited per hour worked, e.g. mg/hr,
there is an increase of exposure with age.   When the exposure
measure is normalized by the body weight of the worker,  i.e.
mg/kg/hr, then there is no difference in exposure as a function
of age.   The blueberry study,  where  information  related to  work-
rate was available, provided some evidence that the differences
in total exposure with age are attributable to  differences  in
workrate between children and adults.
     The staff of the  California PHAP was assisted  in all phases
of the field studies by Dr. James M.  Witt of the Department of
Agricultural Chemistry, Oregon State  University, Corvallis, Ore-
gon,  and Ken Brown, Extension Agent,  Oregon State  University,
Salem, Oregon.  Through  their  knowledge  of  the agriculture  in the
region and their  liason with many growers,   they and their  staffs
were able to locate suitable field sites and enlist the coopera-
tion of the owners.  John Reinhold,  working under Dr. Witt's
aegis, took foliar samples prior to  our  arrival in Oregon and
assisted the PHAP staff in conducting the monitoring studies.  We
are grateful for their  assistance.

-------
                                                             481
                                               Section No. 4
                                               October 15, 1985
                                               Page 1 of 19
*       4.  HARVESTER EXPOSURES TO METHIOCARB  IN BLUEBERRIES
>*
 4.1 Introduction

      In a continuing effort to develop experimental data on the
 exposure to pesticides of fruit harvesters of different ages, a
 study was conducted involving the exposure of blueberry har-
 vesters to residues of the pesticide methiocarb  (Mesurol).  The
 volunteers for this study were divided into  two groups, one
 provided with cotton gloves and dermal patches to measure dermal
 exposures and the other not so provided so that there would be no
 unnatural barrier to their exposure.   Urine samples were  collect-
 ed from all subjects to be analyzed for metabolites of the
 pesticide.

      The purpose of the study was two-fold.  The primary intent
 was to measure the worker's dermal  exposures and determine
 whether a significant difference exists between the exposures
 experienced by children and adults.  Second, an attempt was to be
 made to correlate dermal exposure to methiocarb as determined by
;patch and glove monitors with that  determined by the concentra-
"L
-tion of the metabolite of the pesticide excreted in the urine of
 the exposed workers.   An  additional,  but secondary goal,  was to
 contrast the  absorbtion of the pesticide, as measured by the
 urinary metabolite concentration, between the group wearing
gloves with that not so protected with the object of determining
 the degree of protection afforded.

-------
                                               Section No. 4
                                               October 15, 1985
                                               Page 2 of 19
4.2 Study site and experimental  design

     A fifteen acre plot of the  Bluecrop variety of blueberries,

located about two miles north of Salem, Oregon, was chosen as the

site of the study.   Twenty  five  harvesters,  including men, women

and children, participated  in  the study on a voluntary basis.

They were paid $20 for completing the five day  course of monitor-

ing and urine collection.   Detailed consent  forms and instruc-

tions were handed to each participant before the study began.

The participation of all  minors  required the signed consent of

the parents.


     On Friday,  22  July 1983, methiocarb had been applied to the

blueberries between 0800 and 0900 hours by fixed wing aircraft.
                                                          -—~" ""*"" ~~ *
A 75% wettable powder formulation was applied  at a rate/or 1.5
                                                       ^^^^•^^^^^^
Ib/A.   This plot had been previously  treated with methiocarb at

the same  rate on 5  July 1983.  The harvesters were permitted to

enter the field on Monday,  25 July, the day that the study

commenced.   Weather  conditions were recorded and are given in

Table 4.1.


     The  study was designed to last five days.  None of the

subjects,  as far as  could be ascertained, picked blueberries on

the preceding Saturday or Sunday.  All subjects were instructed

to collect a urine specimen before they entered the field on

Monday to serve as a pre-exposure control.   On  Monday the workers

were divided into two groups,  A  and B.  Group A was provided

light-weight cotton gloves, similar  to those used  in photographic

-------
                                                              483
                                               Section  No.  4
                                               October  15,  1985
                                               Page  3 of  19
                            Table 4.1
                       Meterological Data
           Blueberry Site, 2 miles N of Salem,  Oregon
  Date
DPA
Time
     Temp.  C
RH
Weather
7/22/83
7/25/83
 0
 3
7/26/83   4

7/27/83   5
7/28/83   6
    0925
    0730
    0918
    1105
    1325
    1508
          21.0      70%
          18.0      80
          18.5      70
          19.0      80
          21.2      60
          22.0      60
          18.3      80
1128      21.0      58
    not recorded
0800      18.0      90
1115      21.0      50
              partly cloudy
              heavy overcast
              heavy overcast
              partly sunny
              partly sunny
              sunny
              partly sunny
              partly sunny
              heavy rain
              sunny
              sunny
                                                                   8

-------
                                                               484
                                              Section No. 4
                                              October 15, 1985
                                              Page 4 of 19
darkroom work, to be worn  throughout the workday while picking
berries. During the lunch  break  the gloves were removed and new
gloves  issued after the break.  Also, new gloves were provided if
a pair  became too soiled or wet.
     On Tuesday Group A was outfitted with cotton gauze-patch
monitors, in addition to the cotton gloves, to measure total
dermal  exposure.  Details  of the placement and handling of the
patches and gloves are contained in  Appendix A. Group b wore
neither gloves  nor patches at any  time  during  the study.

     The collection of urine specimens was scheduled to begin on
Wednesday when it was assumed  excretion would have reached some-
thing near steady state.   Starting Tuesday after work all sub-
jects were provided with 1-liter plastic specimen bottles and
intructed to collect their urine for the reminder of the 72 hours
of the study in  the following regimen: night samples to go from
the termination of work to through the next morning's void;  day
samples from that point through  the  termination of work.  On
Wednesday, 26 July,  about  half the subjects did not pick berries
due to a heavy rainfall that commenced about 8 AN and lasted for
about one hour.   The subjects  from group A who did harvest
berries despite the rain were  provided with gloves  ana patches.

     On Thursday, 27 July, all participants worked  in the field.
Group A was provided with  gloves only, but not patches.  None of
the subjects picked  on Friday, 28 July but they did  deliver their

-------
                                                                 485
                                              Section No. 4
                                              October 15, 1985
                                              Page 5 of 19
final overnight urine sample that morning.
     Throughout the study foliar  residue samples were collected
according to the procedures detailed in Appendix A. On three
occasions participants were also  outfitted with personal air
samplers to measure pesticide residues existing as aerosols.
These procedures are also detailed in Appendix A.
4.3 Sample storage handling and preparation
     Urine samples were stored on ice for no more than 4-6 hours
and transported to the laboratory the same day as they were
received from the subjects.   Individual  urine sample volumes were
measured and duplicate 20 mL aliquots  were pipetted into glass
ampules to which 1.5 mL of concentrated hydrochloric acid was
added as a preservative resulting in a final pH of less than
0.5).  The ampules  were sealed and  stored at room  temperature.
     Gloves and patches were collected from participants by  pro-
ject personnel and stored in zip-loc plastic bags. (See section
6.7 of  the  QA  Plan  for sample preservation  procedures.)

4.4 Analytical procedures
     Extraction of samples was as detailed in section 9 of the
Quality Assurance Plan.
     Methiocarb residues were analyzed by reverse-phase HPLC
using a  Waters 6000A dual  pump Solvent Delivery System, a WISP
Model 710A Automatic Sample Processor, a Waters Model 720 System
                                                         1     10

-------
                                                                 486
                                               Section No.  4
                                               October 15,  1985
                                               Page 6 of 19

Controller with a Mode 730 Data Module and a Model  4530  Variable
Wave-length Detector.  A Supelco C^g reverse-phase column (25 cm
x 4.2 mm ID) was  capable  of separating each of  the  three com-
pounds reported to be associated  with methiocarb residues
{methiocarb:  3,5  dimethyl-4-(methylthio)phenyl-N-methyl  carbarn-
ate; methiocarb sulfoxide: 3,5 dimethyl-4-(methylsulfonyl)phenyl-
N-methyl carbamate; methiocarb sulphone:  3,5 dimethyl-4-(methyl-
sulfonyl)phenyl-N-methYl  carbamate} without appreciable interfer-
ence from extraneous materials originating in  the field. The
mobile phase was a mixture of acetonitrile and water and the
optimum chromatographic conditions  for each compound  are listed
in Table 4.2.
                            TABLE 4.2
                   Chromatographic  Parameters
                             for  the
                       Analysis of  Mesurol
                               and
                        Related Compounds

         Column              25 cm  X 4.6  mm C,« Supelco  LC-18-DB
                             with a C^g Guard-PAK precolunm
         Mobile Phase        65%  Acetonitrile,  35%  Water
         Flow Rate           0.9  ml/min
         Detecrtor           Wavelength:   265  nm
         Parameters          Sensitivity:  0.02 AUFS
         Integration         Peak Width:   20
         Parameters          Noise  Rejection:   7.5
                             Chart  Speed:  0.5  cm/min
                             Run  Time:  10 min
                                                       tr
                                                             11

-------
                                                                 487
                                               Section No. 4
                                               October 15, 1985
                                               Page 7 of 19
4.5 Crew characteristics
     The crew characteristics, including sex, height, weight,  age
and computed body surface area are given in Table 4.3.  In additon,
the crew included six Asian workers in Group A and two in Group B.
     The owner of the blueberry farm selected his harvesters
individually, and allowed only approved personnel to work in his
plots; because of this procedure, he maintained a relatively
stable work crew, year-to-year.  The owner adhered to this prac-
tice because the blueberry bush is a perenial that is not cut
back heavily each year like the other types of berries included
in this series of studies; and damage caused by careless workers
could cause long-term losses in productivity for the plants.

     Upon arrival at the study site it was discovered that the
grower had preselected the crew for the exposure study.   These
individuals came from the growers regular crew, and included
relatives and friends of his family.  The entire crew was com-
prised of 24 individuals, ranging in age from 10 to 47 years old.
Four (17%)  were at the age of ten, while ten of the subjects
(42%)  were between 11 and 15 years, and the remaining ten were 16
years or older.  In Group A (the 13 individuals wearing gloves
and patches), three (23%) were ten years old; five (39%) were
between 11 and 15 years; and the remaining five were over 15.
                                                12

-------
                                               488
                              Section No.  4
                              October 15,  1985
                              Page 8 of 19
            Table 4.3

         Blueberry Study

Physical  Characteristics of Crew
IDI
2
3
4
5
6
7
8
9
10
11
12
17
26
1
14
15
16
18
19
20
21
22
23
25
Group
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
B
B
Sex
F
F
M
F
M
M
F
F
M
M
F
M
F
F
F
F
M
M
M
F
M
F
M
M
Age weight (kg)
15
10
14
10
14
20
18
14
16
10
47
11
28
40
14
16
14
15
11
30
17
37
14
10
52.2
31.8
48.5
36.3
54.4
63.5
45.4
45.4
53.5
34.0
45.4
35.8
60.0
61.2
54.4
61.7
47.6
59.4
27.2
61.2
49.9
72.6
79.4
37.6
Height (cm)
160
114
152
147
170
165
152
152
163
140
152 ~*
137
162
168
168
168
168
146
137
165
160
175
187
127
Area (m2)
1.50
1.00
1.45
1.20
1.60
1.65
1.40
1.40
1.55
1.15
1.40
1.15
1.60
1.65
1.65
1.65
1.50
1.55
1.05
1.65
1.50
1.85
2.00
1.15
                                             13

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                                                              489
                                               Section No. 4
                                               October 15, 1985
                                               Page 9 of 19
4.6 Results
     As noted above, only on Tuesday was there a complete set of
both patch data and glove data.  On all four days, however, glove
data was collected.  Au important issue then, is the degree of
correlation between the glove exposure and total exposure.  Fig-
ure 4.1 shows the scatterplot of patch exposure vs. glove expo-
sure.  The two variables are positively correlated and the re-
gression is significant, but  the r2 value of 0.40 is not parti-
cularly impressive. However, as will be discussed below, about
50% of the total exposure is to the hands.  Hence, glove exposure
will be a much better predictor of total exposure than of patch
exposure alone.
     It is clear that the degree of exposure to foliar residues
is a function of the residue level and the activity of the work-
er.  Because of the method of payment of the workers in blue-
berries, it was possible to obtain data on the mean daily har-
vesting rate in Ibs/hr for each worker.  Because all workers were
engaged in harvesting it seems reasonable to hypothesize that the
                                           *
mean daily yield should provide a good index of the activity
related effect on exposure. It seems highly likely, however, that
yield is a strong function of age.  Indeed, it seems likely that
the principal effect of age on exposure among workers carrying
out the same task will be through the workrate variable.
                                                                14

-------
                                               Section  No.  4         490
                                               October  15,  1985
                                               Page 10  of  19
     Figure 4.2 and 4.3 show the mean  yield  rate  for  the  entire
period of the experiment vs. age for males and  females  respec-
tively. In both cases there is an increase of yield with  age.
                                                                  15

-------
                                                                                                     491
                                                                          Section 4
                                                                          October 15, 1985
                                                                          Page  11 of 19
                                       Figure  4.1

nsoa s.oo    BunsENur SWOT, FKKH DUOS, us GUVE EXPOS.  («yw)« DM 2   nut B««303-2P  REV* 7

ODttMNDt ILOT
mssac VALUE IMMXMTI uswxss
             0.00000     0.900000     1.60000     2.40000      3.20000     4.00000      4.80000
                  0.400000      1.20000      2.00000     2.80000     3.60000     4.40000
       4.80000  4
       4.70000  4
       4.60000  4
       4.50000  4
       4.40000  4
       4.30000  4
       4.20000  4
       4.10000  f
       4.00000  *
       3.90000  +
       3.80000  +
       3.70000  4
       3.60000  4
       3.50000  4
       3.40000  4
       3.30000  4
       3.20000  4
       3.10000  4
       3.00000  4
       2.90000  4
       2.80000  4
       2.70000  4
       2.599*9  4
       2.49999  4
       2.39999  4
       2.29999  4
       2.19999  4
       2.09999  4
       1.99999  4
       1.69999 4
       1.79999  4
       1.69999  4
       1.59999  4
       1.49999 4
       1.39999 4
       1.29999 4
       1.19999 4
       1.09999 4
      0.999994 4
      0.899994 4
      0.799994 4
      0.699994 4
      0.599994 4
      0.499994 4
      0.399994 4
      0.299994 4
      0.199994 4
   9.99938E-02 4
       0.00000 4
            0.00000    0.800000      1.60000      2.40000      3.20000     4.00000     4.80000
                  0.400000     1.20000     2.00000     2.80000     3.60000      4.40000


                                   c cuvn
                                                                                                      16

-------
                                                                   Section  4
                                                                   October  15, 1985
                                                                   Page 12  of 19
                                                                     492
ABSTAT 3.00

COMMAND: PLOT
                                    Figure 4.2
BLUEBERRY STUDY, MEAN YIELD  (KG/HR) VS AGE> MALES
                                                                            FILE:  8303-PH
0
4
M
E
A
N
Y
L
D
              0.00000     8.33333      16.6667      25.0000      33.3333      41.6667      50.0000
                     4.16667      12.5000      20.8333      29.1667      37.5000     45.8333
20.0000
19.5833
19.1667
18.7500
18.3333
17.9167
17.5000
17.0833
16.6667
16.2500
15.8333
15.4167
15.0000
14.5833
14.1667
13.7500
13.3333
12.9167
12.5000
12.0833
11.6667
11.2500
10.8333
10.4166
9.99998
9.58332
9.16665
8.74998
8.33331
7.91665
7.49998
7.08331
6.66665
6.24998
5.83331
5.41665
4.99998
4.58331
4.16664
3.74998
3.33331
2.91664
2.49998
2.08331
1.66664
1.24998
0.833311
0.416644
0.00000

4
4
4
4
4
4
4
4
4
4
4
4
4 1
4
4
4 1
4
4 1
4
4
4
4
4
4
4
4 1
4
4
4 1
4 1
4
4
4
4
4 11 1
4
4 1
4
4
4 11
4
4
4
4
4
4
4
4
4
_4 	 4 	 4 	 4 	 4 	 4 	 4 	 4 	 4 	 4 	 4 	 4 	
               .00000      8.33333      16.6667      25.0000      33.3333      41.6667      50.0000
                    4.16667      12.5000      20.8333      29.1667      37.5000      45.8333


                                      2 ACE
                                                                             r-
                                                                                     17

-------
                          Section  4
                          October  15, 1985
                          Page 13  of 19
                                            493
Figure 4.3
ABSTAT 3.00
COMMAND: PLOT
0

















0
4


H
C
A
N
T
L
D
























20.0000
19.5633
19.1667
18.7500
18.3333
17.9167
17.5000
17.0833
16.6667
16.2500
15.8333
15.4167
15.0000
14.5833
14.1667
13.7500
13.3333
12.9167
12.5000
12.0833
11.6667
11.2500
10.8333
10.4166
9.99998
9.58332
9.16665
8.74998
8.33331
7.91665
7.49998
7.08331
6.66665
6.24998
5.83331
5.41665
4.99998
4.58331
4.16664
3.74998
3.33331
2.91664
2.49998
2.08331
1.66664
1.24998
0.833311
* 0.416644
0.00000

0.

BLUEBERRY STUDY, MCAH YIELD (KC/BR) VS ACE, FEMALES PILEi 8303-PP
.00000 6.33333 16.6667 25.0000 33.3333 41.6667 50.0000
4.16667 12.5000 20.8333 29.1667 37.5000 45.8333
4
4
4
+
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4 1
4
4
4
4
4
4
4 1
4
4 111 1
4
4
4 1
4 1
4 1 1
4
4 1
4
4
4 1
4
4
4
4
4
4
4
-4— 	 4 	 -4-- 	 4 	 4-- 	 4 	 4- — — 4 	 4 	 4 	 4 	 4 	 4
00000 8.33333 16.6667 25.0000 33.3333 41.6667 50.0000
4.16667 12.5000 20.8333 29.1667 37.5000 45.8333
  2 ACE
                                               18

-------
                                                               494
                                               Section No. 4
                                               October 15, 1985
                                               Page 14 of 19
The age range for females is sufficient to suggest a paateau in
the neighborhood of 8 kg/hr, but no such plateau is seen for
males because of the limited age range of the workers. In any
case there is clear evidence that yield rate is a function of age
and sex.
     If, then, we consider exposure a function of residue level
and yield rate, age and sex are taken into account through their
non-linear effect on yield rate.  Table 4.4 contains the results
of a multiple linear regression of the log of residue and the log
of the yield rate against the log of the glove exposure rate
which we use here as a surrogate of the total exposure rate.  The
logarithmic relationship is suggested by the fact that without
residue there can be no exposure as is the case with work rate.
Hence a multiplicative relation is plausible and the logarithmic
transform appropriate.

     As can be seen in Table 4.4 the F value indicates that both
regression coefficients are non-zero and that these two variables
account for about 60% of the variability in the data.  The foliar
residue is the more important predictor of exposure as indicated
by the standardized coefficients.  These numbers indicated the
change in the dependent variable resulting from a change in the
independent variable of one standard deviation.  Hence, a one
standard deviation change in the log of the yield rate changes
the log of the glove exposure by 0.376 as contrasted with a
change of 0.745 with a one standard deviation change in the log
                                                                19

-------
                                 Table 4.
ABSTAT 3.00   BLUEBERRY STUDY, MULTIPLE REGRESSION, GLOVE VS RESIDUE  &  YIELD

COMMAND: REGR

MISSING VALUE TREATMENT: LISTWISE

                     *** MULTIPLE LINEAR REGRESSION  ***

DEPENDENT VARIABLE:  10 LNGLRATE               34  VALID CASES
COEFP OF DETERMINATION:    0.578869
MULTIPLE CORR COEFF:       0.760835
                        ESTIMATED CONSTANT TERM:      -1.61601
                        STANDARD ERROR OF ESTIMATE:   0.717036
ANALYSIS OF VARIANCE  FOR  THE  REGRESSION:
                      DEGREES OF      SUM OF
SOURCE OF VARIANCE      FREEDOM      SQUARES
      REGRESSION
      RESIDUALS
      TOTAL
           2
          31
          33
VARIABLE
12 LNYLDRAT
13 LNRES

DURBIN-WATSON
 REGRESSION
COEFFICIENT
   0.853255
   0.759902

    2.26362
 MEAN OF
 SQUARES
 10.9541
0.514140
       21.9082
       15.9383
       37.8465
              CORRELATION
STANDARDIZED      WITH
 COEFFICIENT    DEPENDENT
    0.376589     0.218159
    0.745907     0.665919
 F TEST
21.3057
                                  -o o t/>
                                  o» n rt>
                                  to n- o
                                  n> o r»-
                                    cr -*•
                                  —< o> o
                                  01 1 3
                                  o —• .&
                                  -h en
                                                                                     vo
                                                                                     oo
                                                                                     en
                                                                                      LTI

-------
                                                               496
                                               Section No. 4
                                               October 15, 1985
                                               Page 16 of 19
of the residue level.
     A second regression was carried out with the log of age
included as a third predictor variable to see if there was evi-
dence of any independent influence of age other than through work
rate. As shown in Table 4.5 the result is essentially unaffected
as measured by the coefficient of determination (r2).  The appro-
priate F test applied to the residuals in the two  variable vs.
the three variable case indicates that the small increase in r
is only what one would expect from random variation. Here age and
yield rate have a similar influence on the outcome as might be
expected because of the high correlation between the two as
evidenced by Figure 4.2.  Hence, we conclude that there is no
evidence that age is an important variable except thru its in-
fluence on work rate.

     This conclusion is supported by a different analysis in
which each individual's average glove exposure,  normalized for the
weight of the individual (mg/kg/hr), is calculated over the course
of the experiment and regressed against age.  Figure 4.4 shows
the scatter plot.  The F-value is 0.009 and r2 about 10~^
indicating an almost totally random relationship between these
variables.  That is, exposure rate on a per unit weight basis is
virtually unrelated to the age of the worker. This finding sup-
ports the interpretation that workrate is the important variable
and that younger workers, who tend to be smaller, work at lower
rates and thus receive less total exposure than adults.
                                                                 21

-------
                                                                        Section 4
                                                                        October 15,  1985
                                                                        Page  17 of 19               497
                                          Figure  4.4
ABSTAT 3.00      BLUEBERRY BTDDY, WEIGHT NORMALISED CLOVE EXPOSURE VS ME      PILEi Bi8303-Cl   REV! 7

OOmARDl PLOT

NI8SIRG VALUE TREATMBTt LI6WISC

             0.00000      1.33333      I«.«f7     25.0000     33.3333      41.Hit      50.0000
                   4.1CC67     12.5000      20.8333      29.HC7      37.5000      4S.B333
                •4——4-—-4——4——4——4——4——4—--4———4« -—4——4——4
   •.OOOOOE-02  4
   7.87500E-02  4
   7.75000E-02  4
   7.C2499E-02  4
.













































P.49999E-02
.37499E-02
.24999E-02
.12499E-02
.99999E-02
.B7499E-02
.74999E-02
.C2499E-02
.49999E-02
.37499E-02
.24999E-02
.12499E-02
.99999E-02
.87499E-02
.74999E-02
.62499E-02
.49999E-02
.37499E-02
.24999E-02
.12499E-02
.99999E-02
.87499E-02
.749991-02
.C2499E-02
.49999E-02
.37499E-02
.24999E-02
.12499E-02
.99999E-02
.87499E-02
.74998E-02
.62498E-02
.49998E-02
.37498E-02
.24998E-02
.12498E-02
.99998E-02
.87498E-02
.74998E-02
.(2498E-02
.49998E-02
.37498E-02
.24998E-02
.12498E-02
.OOOOOE-02
0.
4
4 1
4
4
4
4
4
4
4
4
4
4
4
4
4 1
4 11
4
4
4 1
4
4 11
4
4 1
4
4
4 1
4 1
4
4 1
4 1
4
4
4
4
4
4
4
4
4
4
4
4
4
4 1
4
00000 B. 33333 1C.CCC7 25.0000 33.3333 41.CCC7 50.0000
                   4.1C6C7     12.5000      20.B333      29.1M7      37.5000     45.8333


                                    3 ACE
                                                                                                   22

-------
ADSTAT 3.00

COMMAND: REGR
                                         Table 4.5
                            BLUEBERRY STUDY,  MULT.  REGR. ,  GLOVE VS RESIDUE,  YIELD & AGE
             MISSING VALUE TREATMENT:  LISTWISE

                                 *** MULTIPLE LINEAR REGRESSION ***
             DEPENDENT VARIABLE:  10 LNGLRATE

             COEFF OF DETERMINATION:   0.595609
             MULTIPLE CORR COEFF:      0.771757
                                             34 VALID CASES

                                       ESTIMATED CONSTANT TERM:
                                       STANDARD ERROR OF ESTIMATE:
                                        -2.24593
                                        0.714256
             ANALYSIS OF VARIANCE FOR THE REGRESSION:
             SOURCE OF VARIANCE
                   REGRESSION
                   RESIDUALS
                   TOTAL
                      DEGREES OF
                       FREEDOM
                          3
                         30
                         33
        SUM OF
       SQUARES
       22.5417
       15.3048
       37.8465
            VARIABLE
            11  LNAGE
            12  LNYLDRAT
            13  LNRES

            DURBIN-WATSON
                REGRESSION
               COEFFICIENT
                  0.348166
                  0.679906
                  0.749882

                   2.37323
STANDARDIZED
 COEFFICIENT
    0.149566
    0.300080
    0.736071
      MEAN OF
      SQUARES
      7.51390
     0.510161

CORRELATION
    WITH
  DEPENDENT
   0.267307
   0.218159
   0.665919
 F TEST
14.7285
                •o o to
                o» o n
                 O ct-
                  cr -••
                —• ro o
                oo -i a
                o —• *>
                -»• tn
                                                                                             vo
                                                                                             oo
                                                                                             en
rv>
                                                                                              oo

-------
                                                               499
                                               Section No. 4
                                               October 15, 1985
                                               Page 19 of 19
     Table 4.6 shows the anatomical distribution of methiocarb
exposure.  Here less of the exposure was to the hands than was
the case in the strawberry studies reported previously.  Since
the blueberry variety involved in these studies grew on bushes as
tall as 1.7 meters, there was a substantially greater potential
for body contact than is the case with strawberries.  There is a
considerable difference in the data for the two different days,
presumably  because of the substantial rainfall on the third  day
of  the  study.   The data on day 4  post-application  should  be
regarded as more representative of the normal exposure situation.
                            Table 4.6
          Anatomical Distribution of Dermal Exposure to
               Methiocarb on Blueberry Harvesters

                                   Days Post-Application
Body Part                             4            5
Head+Neck                        0.28  (7.4)*    0.13 (6.2)
Back+Shoulders  "                 0.13  (3.4)     0.19 (8.8)
Chest+Stomach                    0.23  (6.0) •    0.23 (10.6)
Lower Legs                       0.23  (6.0)     0.34 (15.9)
Upper Arms                       0.22  (5.8)     0.20 (9.7)
Lower Arms                       0.64  (16.8)    0.74 (34.6)
Hands                            2.05  (53.9)    0.31 (14.3)
Total                            3.80           2.14
*Tabled numbers are exposure rates in mg/hr followed by the
percent of the total in parentheses.

-------
                                             Section  5
                                             October 15,  1985
                                             Page 1  of  18         5QQ

       5.  HARVESTER EXPOSURES TO BENLATE IN BLACKBERRIES

5.1  Introduction
     In a continuing effort to develop experimental data on the
exposure to pesticides of fruit harvesters of different ages,  a
study was conducted involving the exposure of blackberry harves-
ters to residues of the pesticide Benlate (benomyl).   The volun-
teers for this study were divided into two groups,  one provided
with cotton gloves and dermal patches to measure  dermal exposures
and the other not so provided so that there would be no unnatural
barrier to their exposure.   Urine samples were  collected  from  all
subjects to be analyzed for metabolites of the pesticide.
     The purpose of the study was two-fold.   The  primary  intent
was to measure the worker's dermal  exposures  and  determine wheth-
er a significant difference exists  between the  exposures  experi-
enced by children and adults.  Second, an attempt was  to  be made
to correlate dermal exposure to benlate  as  determined  by  patch
and glove monitors with that determined by the  concentration  of
the metabolite of the pesticide excreted in the urine  of  the
                                              •
exposed workers;  An additional, but secondary  goal, was  to
contrast the absorption of  the  pesticide,  as  measured  by  the
urinary metabolite concentration, between the group wearing
gloves with that not so protected with the  object of determining
the degree of protection afforded.
                                                                    25

-------
                                             Section   5             501
                                             October  15,  1985
                                             Page  2   of   18
5.2 Study Site and Experimental Design
     The site chosen for an exposure study among blackberry
harvesters was located within a plot of about 30 acres of the
Marion variety near Independence,  Oregon.   Over the growing sea-
son this field had been treated with a variety of  insecticides,
herbicides and fungicides;  and the spray history is delineated in
Table 5.1.  The most  recent treatment  had  been with Lannate and
Thylate applied to various portions of the plot on 6  and  9 July.
However, for several practical reasons,  the 1 July treatment was
chosen as the pesticide application to follow with our measure-
ments.  First,  the entire plot was treated in  one day, offering
the possibility of more homogeneous foliar residues.   Second, in
addition to  Lannate and Thylate,-benomyl had  been applied on
1 July, and this happened to be the same compound followed in the
raspberry study conducted the  previous week, meaning  that the
same residue and metabolite analytical methodology could  be uti-
lized for both  studies.  Third,  no readily detectable  urinary
metabolites  could be expected  from Lannate, and we did not know
what dermal  adsorption and  urinary excretion patterns might be
expected from Thylate;  whereas,  we did know some of the pertinent
toxicological and  metabolic  information  regarding benomyl.
     The study  lasted for five days, running from Monday, 18 July
1983 through  Friday,  22 July 1983.  On-site weather observations
for the study site covering 19 through 22  July are found  in
Table 5.2.  There was one heavy  rainfall early in the  study,
having come  during Monday night.  Although the field was wet on
                                                                   26

-------
                                             Section  5
                                             October 15,  1985
                                             Page 3  of  18
                                        502
                            TABLE 5.1

                      1983 Spray Schedule*
                     Marion Blackberry Field
      Date
 Product
Application Rate
    and Mode	
     3 March

     17-18 March
     28 March

     13 April


     15 April
     6-9 May
     13-16 May

     14 May

     5 June

     1 July

     6, 9 July
   Lime Sulfur
    Spray-Aid
    Parathion
 Karmex (diuron)
    Paraquat
    X77 (sic)
     Dinitro
   WDX77 (sic)
     Roundup
     Guthion
     Dinitro
   WDX77 (sic)
     Ronilan
     Thiraro
     Benlate
     Lannate
     Benlate
     Thiram
     Lannate
Thylate (thiram)
 7.5 gal/A in 100 gal
 0.25 gal/A
 1 Ib/A
 2.4 Ib in 4* band
 1.1 pt
 3.2 oz
 2.0 qt/100 gal
 50 gal/A
 1 pt
 General Burn-back
 0.5 gt on centers
 0.5 Ib/A
 Burn-back
 1 pt
 1.75 lb/100 gal
 1.3125 Ib
 on West 1/2
 8 oz
 3- lb/100 gal
 1 Ib
 0.5 gal/100 gal
 1 Ib
 3 Ib
 0.5 gal
 3.0 Ib
* This table does not contain all  of  the
terminates at the time of the study.
                 1983 spray history,  but
                                                                  27

-------
                                             Section   5
                                             October  15,  1985
                                             Page  4   of   18
                                                     503
                            TABLE 5.2

                      Weather Observations
                     Marion Blackberry Field
   Date
Time
Dry Bulb
  (QC.)
Wet Bulb
  (QC.l
% RH    Description
19. July
1430
   22.8
   19.4     73    Cloudy and
                  partly sunny;
                  had rained
                  the night
                  before.
20 July
21 July
22 July
1300
1408
0730
1008
0925
21.1
23.3
14.2
21.1
21.1
15.8
20.0
13.1
17.2
17.8
57
74
89
67
72
Sunny with
spotty clouds.
*
*
*
* Although no information was recorded for  these days, the
weather was generally clear  and  sunny  for the duration of the
study.

Tuesday morning,  relatively  warm weather that day dried the
foliage within a  reasonable  time, allowing  the crew to work
without dealing with very wet gloves.
     Consent  forms approved  by the Committee for the Protection
of Human Subjects at the  University  of California at Berkeley
(see  Appendix  D) were distributed to each participant along with
detailed instructions  for their  particular  subgroup  (Appendix
D).   in order  for anyone to be allowed to join the Study, they
were  required to  return their consent  form  signed; and if they
were minors, their form had to be signed by their parents, as
                                                                    28

-------
                                             Section  5           504
                                             October 15, 1985
                                             Page 5  of  18
well.  Each participant was paid a bonus of $20.00 for  the  com-
pletion of the study if all urine samples were collected as
instructed.  This was done, not as an inducement to participate,
but to offset the inconvenience and potential aggravation of
providing total urine collection for up to 72 hours.
     As with  the blueberry  study  (See Section 4.2), the volun-
teers were divided into two subgroups.   The first,  Group A,  was
assigned to wear patch monitors and gloves,  while the second were
to have no unusual  impediments to exposure,  which the gloves
might constitute.  Thus,  Group B wore neither gloves nor patches
at any time during the study.   All subjects were instructed to
collect a urine specimen before they entered the field on Monday
to serve as a pre-exposure control.   On  Monday Group A  was  pro-
vided light-weight cotton gloves to be  worn throughout  the  work-
day while picking berries.  During the  lunch break the  gloves
wer.e removed and new gloves issued after the break.   Also,  new
gloves were provided if a pair became too soiled or wet.
     On Tuesday Group A was outfitted with cotton gauze-patch
monitors, in addition to the cotton gloves,  to  measure total
dermal exposure.  Details of the placement and handling of  the
patches and gloves  are contained in Appendix A.
   *
     The collection of urine specimens was scheduled to begin on
Wednesday when it was assumed excretion would have reached  some-
thing near steady state.   Starting Tuesday after work all sub-
jects were provided with 1-liter plastic specimen bottles and
instructed to collect  their urine for the remainder of the  72
                                                                  29

-------
                                            Section  5
                                            October 15, 1985
                                            Page 6  of  18
hours of  the study in the following regimen:  Night samples to go
from the  termination of work to through the next morning's void;
day samples from that point  through the termination of work.
     The  owner of this plot  did not select individuals for his
crew, but allowed anyone who wished to do so to come and pick; he
merely decided which portions of  the  field would be harvested
each day.   In  spite of the fluid nature of the work force,  there
were a number  of family groups that either came from the sur-
rounding  area  or  followed the  hand harvest crops through Oregon
and Washington as migrants,  and these groups made up a relatively
stable population at the study site for the  duration of the
experiment.  This characteristic of the work force also meant
that there were  children available for inclusion in the study who
                              •
were younger than the 12-year  old legal age  limit for children
who can be hired directly by a grower.  Also, the task of re-
cruiting  the participation of  youngsters with parental approval
was greatly simplified when  the parents were also participating.

5.3 Sample  Storage Handling  and Preparation
     Drine samples were stored on ice for no more than 4-6 hours
and transported  to the laboratory the  same day as they were
received  from  the subjects.   Individual urine sample volumes  were
measured  and duplicate 20 mL aliquots  were pipetted into glass
ampules to which 1.5  mL of concentrated hydrochloric acid was
added as  a  preservative  (resulting in a final pH of less than
0.5).  The ampules were sealed and stored at room temperature.
                                                            "     30

-------
                                             Section  5
                                             October 15,  1985     5Q6
                                             Page 7   of   18
     Gloves and patches were collected from participants  by  pro-
ject personnel and stored in zip-loc plastic bags.  (See  section
6.7 of the QA Plan for sample preservation procedures.)

5.4 analytical Procedures
     Extraction of samples was as detailed in Section 9 of the
Quality Assurance Plan.
     Benomyl residues were analyzed by reverse-phase HPLC using a
Waters 6000A dual pump Solvent Delivery System, a  WISP Model 710
A automatic sample processor, a Waters Model 720  System Control-
ler with a Model 730 Data Module  and a Model 4530  Variable Wave-
length Detector.  A nBondapak C18 reverse-phase column (25 cm X 2
mm ID) was capable of separating  benomyl from interference by
substances originating in the field.   The mobile  phase found to
be most effective was 65% acetonitrile and  35% water.  Chromato-
graphic conditions for benomyl analysis are  in Table 5.3.
   ?
     Since benomyl spontaneously  converts to  Carbendazim in  the
environment, it is the latter compound that is found in all per-
sonal and environmental samples,  if present at all.  Benomyl has
a substantially longer retention  time than  does Carbendazim  under
the chromatographic conditions describe above, and it is desir-
   s
able to convert the Carbendazim back to benomyl in order to
better separate the analyte  of interest from interferences.  This
was accomplished by the addition  of 20 microliters of butyl
isocyanate to each sample as  it was  prepared  in its autosampler
vial.   This treatment assured a large,  stable benomyl peak,  in

                                                              '     31

-------
                                             Section  5            en-?
                                             October 15, 1985      ~>U/
                                             Page 8  of  18
standards,  spiked blanks and samples, alike.

                            TABLE 5.3
                   Chromatographic Parameters
                             for the
                       Analysis of Benomyl
          Column              25 cm X 2.0 mm C18 pBondapak with
                              a Ci8  Guard-PAK precolumn
          Mobile Phase        65% Acetonitrile, 35% Water
          Flow Rate           2.0 ml/min.
          Detector            Wavelength:  292 run
          Parameters          Sensitivity:  0.02 ADFS
          Integration         Peak Width:  30
          Parameters          Noise Rejection:  3.0
                              Chart Speed  0.5 cm/min
                              Run Time:   10 min
5.5 Crew Characteristics
   \  Nearly thirty  volunteers  were recruited  from  among the  work
force of more  than  80 which was found already working at the
site.   Twenty-two subjects completed enough of the study to be
included in the  data set;  although,  only sixteen lasted through
the entire study.   The  physical characteristics of the partici-
pants in the blackberry study  are contained in Table 5.4.  As  can
be seen, five  (22.7%) of the volunteers  were  ten years old or
below, and another  five were between ten and fifteen.  Of the
twelve people  in Group  A (wearing gloves and patches), there were
three (25%) who  were ten or less, while  two  (16.7%)  were between
ten and fifteen.
                                                                   32

-------
                                                               Section 5
                                                               October 15, 1985
                                                               Page  9  of 18
                                                                         508
                                      Table 5.4
ABSTAT 3.00
BLACKBERRY STUDY, PERSONAL CHARACTERISTICS OP THE CREW
                                                                        FILE: 8302-1      ftEVI 4
COMMAND* PRINT DATA
VARIABLES*
CASE
1
2
3
4
5
6
7
8
9
10
11
12
13
14
IS
16
17
18
19
20
21
22
1 SUBJECT
1.00000
2.00000
3.00000
4.00000
5.00000
6.00000
7.00000
8.00000
9.00000
10.0000
11.0000
12.0000
13.0000
14.0000
15.0000
16.0000
21.0000
22.0000
23.0000
24.0000
28.0000
29.0000
2 GROUP
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
3 SEX
1.00000
1.00000
2.00000
2.00000
2.00000
2.00000
1.00000
1.00000
1.00000
2.00000
2.00000
2.00000
2.00000
1.00000
1.00000
2.00000
2.00000
2.00000
1.00000
2.00000
1.00000
2.00000
4 AGE
37.0000
31.0000
49.0000
25.0000
10.0000
7.00000
11.0000
9.00000
21.0000
39.0000
19.0000
15.0000
11.0000
8.00000
33.0000
30.0000
45.0000
11.0000
42.0000
28.0000
12.0000
10.0000
5 HGBTKG
113.400
68.0000
93.4000
56.2000
22.7000
20.4000
31.8000
34.0000
68.9000
57.2000
117.900
94.8000
36.3000
31.3000
99.8000
73.0000
68.0000
49.0000
56.7000
59.0000
68.0000
58.1000
6 BEIGHTCM
180.003
190.000
170.000
168.000
128.000
118.000
140.000
143.000
170.000
153.000
162.000
154.000
141.000
129.000
175.000
173.000
170.000
157.000
187.000
162.000
154.000
159.000
7 AREAM2
2.35000
1.85000
2.05000
1.60000
0.900000
0.800000
1.20000
1.20000
1.80000
1.55000
2.30000
2.00000
1.20000
1.05000
2.20000
1.85000
1.75000
1.45000
1.70000
1.60000
1.70000
1.60000
                                                                                       33

-------
                                             Section  5            rrn«
                                             October 15, 1985      JU9
                                             Page 10 of  18
5.6 Results
     All of the dermal patch data was below the limit of detec-
tion for benomyl.  Foliar residues and amounts of benomyl in the
gloves of the workers were, however,  sufficient  to guantitate.
Foliar residues were collected on days 17, 19 and 20 post appli-
cation.  Figure 5.1 is a scatter-plot of these residue values
versus day post-application.   The corresponding regression ana-
lysis, Table 5.5, results in an F value of 4.21 which indicates
that the regression is significant at the 90% level.
     Dsing the regression equation to estimate the decay curve
for all five days allows an investigation of  the  relation between
hand exposure,  as measured by the glove residues, and the residue
on the foliage.   Figure 5.2 shows  a  scatter-plot  of  the  daily
exposure rate,  averaged across the entire crew, and  the  estimated
residue level for that day.   Table 5.6 shows  the  result  of  the
corresponding regression which is significant at above the 95%
level.
     Table 5.7 contains  the glove  exposure rate,  in  mg/hr,  by day
and individual  worker.   The average  exposure  rate was calculated
                                              •
for each worker.  These values are  also  given in Table  5.7.
Figure 5.3 is a  scatter-plot of the  average individual  glove
exposure rate vs.  age which suggests that the hand exposure rate
is less for  young workers than for adults.  Taking age twelve as
the dividing line between children and adults,  for present  pur-
poses,  a Mann-Whitney U test  was  performed to test the  hypothesis
that the distribution  of hand  exposures was the same for children

                                                                    34

-------
                                              Section   5
                                              October 15,  1985
                                              Page 11 of   18            510
and  adults  against  the  alternate  hypothesis that the exposure  of
the  children was less.  The 0 value was calculated to  be  5 which,
for  4 children and 8 adults,  would be observed with probability
0.036 under BQ<  Hence, we conclude that the  children  do  have  a
lower  average  hand  exposure than  the  adults.  In contrast to the
blueberry study,  the absence of yield data makes it impossible to
verify that differences in workrate account for this difference
in exposure, but it seems highly  likely that  this is the  case.
     As was done in the case of blueberries,  the average glove
exposure for each individual was  normalized by body weight,
resulting in a exposure rate expressed in mg/kg/hr.   This value
was  regressed  against age with the corresponding scatter-plot
shown as Figure  5.4.  The value of the F  statistic was 0.355  with
the  corresponding r2 equal to 0.0034,  indicating an  essentially
random relation  between these variables.  Hence, as  in the blue-
berry study, adults have a higher total exposure than children?
but,  on a mg/kg/hr basis, there is no evidence of differences in
exposure as a function of age.
                                                                   35

-------
                                                                   Section  5
                                                                   October  15, 1985
                                                                   Page 12  of 18
                                       Figure  5.1


                    BLACKBERRY  STUDY, RESIDOE DECAY (NG/CM2)  VS  DPA
                                                                              PILE: PDNCH2
XBSTAT 3.00

COMMAND: PLOT

HISSING VALUE TREATMENT: LXSTVISE

             15.0000      16.6667      18.3333      20.0000      21.6667      23.3333       25.0000
                    15.8333      17.5000      19.1667      20.8333      22.5000      24.1667

       500.000  *
       497.917  +
       495.833  +
       493.750  +
       491.667  +
       489.583  +
       487.500
       485.417
       483.333
       481.250
       479.167
       477.083
                                 1
                                                                                        REVI12
I
G
C
H
2
                +
                •f
475.000
472.917
470.833
468.750
466.666
464.583
462.500
460.416
458.333
456.250
454.166
452.083
450.000
447.916
445.833
443.750
441.666
439.583
437.500
435.416
433.333
431.250
429.166
427.083
425.000
422.916
420.833
418.750
416.666
414.583
412.500
410.416
408.333
406.250
404.166
402.083
400.000
             15.0000      16.6667      18.3333       20.0000      21.6667       23.3333       25.0000
                    15.8333      17.5000      19.1667      20.8333      22.5000      24.1667


                                      1 DPA
                                                                                            36

-------
                                 Table 5.5


ABSTAT 3.00          BLACKBERRY STUDY, RESIDUE DECAY  (NG/CM2) VS DPA

COMMAND: REGR

MISSING VALUE TREATMENT: LISTWISE

                    *** MULTIPLE LINEAR REGRESSION  ***

DEPENDENT VARIABLE:  4 NGCM2                  6 VALID CASES
                                                                               FILE:  PUNCB2
COEFP OF DETERMINATION:    0.513016
MULTIPLE CORR COEFF:       0.716252
                                       ESTIMATED CONSTANT TERM:        741.793
                                       STANDARD ERROR OF ESTIMATE:     22.8753
ANALYSIS OF VARIANCE FOR THE REGRESSION:
                      DEGREES OF      SUM OF
SOURCE OF VARIANCE     FREEDOM       SQUARES
      REGRESSION
      RESIDUALS
      TOTAL
                                                 MEAN OF
                                                 SQUARES
                                                 2205.00
                                                 523.277
VARIABLE
 1 DPA

DURBIN-WATSON
                REGRESSION
               COEFFICIENT
                  -15.3704

                   2.71818
1         2205.00
4         2093.11
5         4298.11
                 CORRELATION
   STANDARDIZED      WITH
    COEFFICIENT    DEPENDENT
      -0.716251    -0.716251
 F TEST
4.21383
                                                                                 -O O
                                                                                 U3 c* O
                                                                                 fl> O r*
                                                                                   «T -••
                                                                                 —• n> o
                                                                                 <*> -I 3
                                                                                 o —• in
                                                                                   to
                                                                                   oo
                                                                                   en
                                                                                        U1

-------
                                                                    Section 5                     tr i
                                                                    October 15,  1985             ^ '
                                                                    Page 14 of 18
                                        Figure 5.2
ABSTAT 3.00   BLACKBERRY STUDY, AVERAGE EXPOSURE RATE VS ESTIMATED RESIDOE5    FILEi  PUNCH 3      REVI16

COMMAND: PLOT

HISSING VALUE TREATMENT! LISTWISE

             400.000      416.667      433.333      450.000      466.667      483.333      500.000
                   408.333      425.000      441.667     458.333      475.000      491.667

















0
7


A
V
E
I
P
0
s





















0.300000
0.295833
0.291667
0.287500
0.283333
0.279167
0.275000
0.270833
0.266666
0.262500
0.258333
0.254166
0.250000
0.245833
0.241666
0.237500
0.233333
0.229166
0.225000
0.220833
0.216666
0.212500
0.208333
0.204166
0.200000
0.195833
0.191666
0.187500
0.183333
0.179166
0.174999
0.170833
0.166666
0.162499
0.158333
0.154166
0.149999
0.145833
0.141666
0.137499
0.133333
0.129166
0.124999
0.120833
0.116666
0.112499
0.108333
0.104166
l.OOOOOE-01
*
+
+
+
+
+
+
•f
•+
+
+
+
+
+
+
+
4
+
+
•»•
+
4
+
+
+
+
•f
+
+
+
•f
+
•f
+
+
+
+
+
+
+
+
4.
+
+
+
+
4.
•f
4
             400.000      416.667      433.333      450.000      466.667      463.333      500.000
                   408.333      425.000      441.667     458.333      475.000      491.667
                                     6 EST
                                                                                         38

-------
                                     Table 5.6

ABSTAT 3.00   BLACKBERRY STUDY, AVERAGE EXPOSURE RATE VS ESTIMATED RESIDUES

COMMAND: REGR

MISSING VALUE TREATMENT: LISTWISE

                    *** MULTIPLE LINEAR REGRESSION ***

DEPENDENT VARIABLE:  7 AVEXPOS                5 VALID CASES
                                                                FILE: PUNCH3
COEFF OF DETERMINATION:   0.776790
MULTIPLE CORR COEFF:      0.881357
                        ESTIMATED CONSTANT TERM:
                        STANDARD ERROR OF ESTIMATE:
      -0.839192
      3.423E-02
ANALYSIS OF VARIANCE FOR THE REGRESSION:
                      DEGREES OF     SUM OF
SOURCE OF VARIANCE     FREEDOM      SQUARES
      REGRESSION
      RESIDUALS
      TOTAL
                                  MEAN OF
                                  SQUARES
                                1.223E-02
                                1.171E-03
VARIABLE
 6 EST

DURBIN-WATSON
 REGRESSION
COEFFICIENT
  2.285E-03

    1.33459
1       1.223E-02
3       3.515E-03
4       1.574E-02
                 CORRELATION
   STANDARDIZED      WITH
    COEFFICIENT    DEPENDENT
       0.881357     0.881357
 F TEST
10.4403
                      "O O l/»
                      o> o n
                      10 r* O
                      (D O it
                        cr -••
                      —•mo
                      on 3
                      O —'01
                      -n 01
                                                                                     Co —•
                                                                                      vo
                                                                                      CO
                                                                                      01
                                                                                         c_n

-------
                                          Table 5.7
ABSTAT 3.00
BLACKBERRY STUDY,  GLOVE EXPOSURE DATA, ALL DAYS
                                                                              FILEi  CtB302-P    REVC12
COHHANDi PRINT DATA
HISSING VALUE TREATMENTi INCLUDE
VARIABLES i
CASE
1
2
3
4
5
6
7
8
9
10
11
12


1 SUBJECT
1.00000
2.00000
3.00000
4.00000
5.00000
6.00000
7.00000
8.00000
9.00000
10.0000
11.0000
12.0000



0
0
0
0
0
0
0
7 GL1
.549846
.342769
.223716
.198595
.161276
.245500
.120154
8.4S896E-02
9.240S3B-02
0.604182
0.251091
0.139273




8 GL2
0.469895
0.230706
0.382164
0.214153
0.232982
0.258432
0.161390
0.210842
0.163817
0.432267
0.255733
0.139733


9 GL3
0.342956
0.261391
0.244348
0.130957
6.92174E-02
0.128522
9.79131E-02
6.50435E-02
9.65000E-02
0.207500
8.45000E-02
8.85000E-02


10 GL4
0.139692
0.203692
0.162000
0.143077
0.129231
0.167692
9.92308B-02
7.75385E-02
HISSING
HISSING
HISSING
HISSING


11 GL5 12 AVGLRATB
0.113778
0.231556
0.179755
0.120444
0.109778
0.183778
7.93334E-02
7.95556E-02
HISSING
HISSING
HISSING
HISSING


0.323233
0.254023
0.238396
0.161445
0.140497
0.196785
0.111604
0.103514
0.117574
0.414649
0.197108
0.122502


2
3
2
2
6
9
3
3
1
7
1
1


13 WGLRATB
.85038E-03
.73563B-03
.55242E-03
.87269E-03
.18929E-03
.64631E-03
.50957E-03
.04452E-03
.70644E-03
.24912E-03
.67182E-03
.29221E-03











•o O  O fD
(O r* O
n o rt-
a- -••
— i a> o
Oh 1 3
o — • in
-h in
00 —•
00
en

-------
                                                                      Section  5
                                                                      October  15, 1985
                                                                      Page 17  of 18
                                                                                                  516
                                           Figure 5.3
 ABSTAT 3.00      BLACKBERRY STUDY, AVERAGE EXPOSURE RATE  (MG/HR) VS AGE       FILE: Cz8302-P    REVI12

 COMMAND:  PLOT

 HISSING VALUE TREATMENT: LISTKISE

               4.00000      12.0000      20.0000      28.0000      36.0000      44.0000      52.0000
                     8.00000      16.0000     24.0000      32.0000      40.0000      48.0000

        0.440000  4
        0.432500  4
        0.425000  4
        0.417500  4
        0.410000  -I-                                                        1
        0.402500  4
        0.395000  +
        0.387500  4
        0.380000  4
        0.372500  4
        0.365000  4
        0.357500  4
        0.350000  4
        0.342500  4
        0.335000  4
        0.327500  4
        0.320000  4                                                     1
 1       0.312500  4
 2       0.305000  4
        0.297500  4
        0.290000  4
 A       0.282499  4
 V       0.274999  4
 G       0.267499  4
 L       0.259999  4
JL       0.252499  4                                           1
 A       0.244999  4
 T       0.237499  4                                                                       1
 E       0.229999  4
        0.222499  4
        0.214999  4
        0.207499  4
        0.199999  4
        0.192499  41                  1
        0.184999  4
        0.177499  4
        0.169999  4
        0.162499  4
        0.1S4999  4                                 1
        0.147499  4
        0.139999  4          1
        0.132499  4
        0.124999  4
        0.117499  4                  11
        0.109999  4           1
        0.102499  4        1
    9.49993E-02  4
    8.74993E-02  4
    8.00000E-02  4

               4.00000      12.0000      20.0000      28.0000      36.0000      44.0000      52.0000
                     8.00000      16.0000     24.0000      32.0000      40.0000      48.0000


                                       3  AGE

-------
                                                                                             517
                                                                   Section  5
                                                                   October  15, 1985
                                                                   Page  18  of 18
                                      Figure 5.4
llBSTAT 3.00   BLACKBERRY STUDY, AVERAGE EXPOS. NORMALIZED FOR WIEGBT VS ACE    FILEt C:8302-P   REVI12

BMARDi PLOT

IISSING VALUE TREATMENT: LISTWISE

            4.00000      12.0000      20.0000      26.0000      36.0000     44.0000      52.0000
                   8.00000     16.0000      24.0000      32.0000      40.0000      48.0000












I
J


II
5
L
K
It
I
E





















l.OOOOOE-02
9.81249E-03
9.62499E-03
9.43749E-03
9.24999E-03
9.06249E-03
8.87499E-03
8.68749E-03
8.49999E-03
6.31249E-03
8.12499E-03
7.93749E-03
7.74999E-03
7.56249E-03
7.37499E-03
7.18749E-03
C.99999E-03
C.81249E-03
6.62499E-03
6.43749E-03
6.24999E-03
6.06249E-03
5.87499E-03
S.68749E-03
S.49999E-03
S.31249E-03
5.12499E-03
4.93749E-03
4.74999E-03
4.56249E-03
4.37499E-03
4.18749E-03
3.99999E-03
3.81248E-03
3.62498E-03
3.43748E-03
3.24998E-03
3.06248E-03
2.87498E-03
2.68748E-03
2.49998E-03
2.31248E-03
2.12498E-03
1.93748E-03
1.74998E-03
1.56248E-03
1.37498E-03
1.18748E-03
l.OOOOOE-03
4
*
+
+
+
•«•
+
•*•
+
4
+
+
^
•f
4-
+
4.
4.
•f
+
4
4
4
4
4
4
4
4
4
4-
4
4
4.
4
4
4
4
4
4
4
4.
4
4
4
4

                                                   _ _+ ______ + _____ + ______ + _____ + ______ + _____ +

              00000    *"l27oOOO     20.0000      28.0000      36.0000      44.0000      52.0000
                   8.00000      16.0000      24.0000     32.0000      40.0000     48.0000
                                     3 ACE
                                                                                         42

-------
                                             Section  6
                                             October 15, 1985
                                             Page 1  of  17
       6.  HARVESTER EXPOSURES TO BENLATE IN RASPBERRIES

6.1 Introduction
     In a continuing effort to develop experimental data on the
exposure to pesticides of fruit harvesters of different ages,  a
st.udy was conducted involving the exposure of raspberry harves-
ters to residues of the pesticide Benlate (benomyl).   The volun-
teers for this study were divided into two groups,  one provided
with cotton gloves and dermal patches to measure dermal exposures
and the other not so provided so that there would be no unnatural
barrier to their exposure.   Urine samples were collected from  all
subjects to be analyzed for metabolites of the pesticide.
     The purpose of the study was two-fold.   The primary intent
was to measure the worker's dermal  exposures  and determine wheth-
er a significant difference exists  between the exposures experi-
enced by children and adults. Second, an attempt was  to be made
to correlate dermal exposure to  benlate  as  determined  by patch
and glove monitors with that determined by the concentration of
the metabolite of the pesticide  excreted in the urine  of the
exposed workers;  An additional, but secondary goal, was to
contrast the absorption of the pesticide, as  measured  by the
urinary metabolite concentration, between the group wearing
gloves with that not so protected with the  object of determining
the degree of protection afforded.
                                                                43

-------
                                             Section   6            5 1 Q
                                             October 15, 1985
                                             Page 2  of  17
6.2 Site and Experimental Design
     The site chosen for an exposure study among raspberry har-
vesters was a 50 acre plot of the Canby variety located on a
berry farm in Troutdale, Oregon. It was  late in the season for
this variety, and the plot had  been  picked over  at least one time
prior to the commencement of the study.  This field had been
treated with very few insecticides,  herbicides or fungicides; but
the spray history up to the study date, such  as  it was, is
delineated in Table 6.1.  The most recent  treatment had been with
Lannate on the first and second of June,  some 40 days prior to
our crew's entry.   Even  though  it was 60  days post application,
the benomyl treatment was chosen as the one to use in the moni-
toring study, since no readily  detectable  urinary metabolites
could be expected from Lannate.  However,  we  did know some of the
pertinent metabolic information regarding benomyl.
                            TABLE 6.1

                      1983 Spray Schedule*
                      Canby Raspberry Plot
Date
25 February
5-7 April
15-18 Hay
1-2 June
Product
Orthrex (sic)
Karmex (diuron)
Paraquat
Benlate
Lannate
Application Rate
3 gal/A
1.6 Ib/A
1 qt/A
2 Ib/A
25 gal/A



(sic)
  This table  does  not  contain  all  of  the 1983 spray history, but
terminates at the  time of the study.
                                                                    44

-------
                                             Section   6            con
                                             October 15, 1985      ^u
                                             Page  3  of  17
     The study lasted for four days,  running  from  Monday, 11 July
1983 through Thursday, 14 July 1983.  On-site weather  observa-
tions for the study site covering 11  through  14 July are found in
Table 6.2.   This particular  study was plagued with frequent
rains, cutting the workdays short and keeping the  foliage, the
subjects, and the glove and patch monitors wet much of the time.
Table 6.2 also includes  information about the crew in  addition to
weather data.  For a number of reasons, individual times for
entry to and exit from the field were not recorded, obviating the
assignment of individual exposure times.  This arose,  in large
part, due to the fact that  as part of a school bus operation this
group arrived at the field  all at one time, and the PBAP staff
was obliged to conduct its  business  (collection of forms, taking
down; personal information,  applying patch monitors and gloves,
etc.) to  all  the  subjects at once and in as  small  a time span as
possible; therefore, movement into and  out  of the  field was taken
for the group, altogether.
     On Thursday, July 14th,  the Canby plot had been completely
harvested out soon after the crew began working in it; so the
entire operation was moved to a plot  adjacent to the Canbies that
happened to be the Meriam variety.  This plot was made up of
considerably older plants than the Canbies  and had considerably
less foliage.  Less  foliage  resulted  in lowering the potential
for the workers to contact  and pick up  residues.   In addition, it
was impossible to determine whether this particular plot had
received the same pesticide regimen as  the  Canby plot.
                                                                    45

-------
                                                     Section   6         521
                                                     October  15,  1985
                                                     Page 4   of   17
                                   TABLE 6.2
                        Weather and General Observations
                               of Conditions in the
                               Canby Raspberry Plot

   Date     Time     Dry Bulb   Wet Bulb   % RH       Description of Weather
	(PC.)	(PC.)	and Other Observations
11 July     0630                                  Rain the night before, heavy
                                                  dew on leaves.  School bus
                                                  arrived, collected evening
                                                  (pre-exposure) urines.
            0730                                  Completed patching Group A.
            0735        15.3        14.2     91    Sunny and
                                                  clear, light wind.
            0855                                  Dew beginning to dry.  Workers'
                                                  shirts are wet from dew.
            1200                                   Crew left field.
        r
12 July     0640                                   Crew arrived. Sunny with
                                                  spotty clouds. Heavy dew.
            0655                                   Group A completely patched.
            0915        18.9
            0945                                   Heavy Clouds have moved in.
                                                  Worker 11 arrived.
            1000                                   Drizzle begun.
         1010-1015                                Crew leaves field for 1/2 hour
   v                                              lunch.  Gloves are very wet;
                                                  Lower legs dry; Lower arms wet.
            1250                                   Crew leaves field.
Table 6.2 continued on Page 5.

-------
                                                                  522
                                             Section  6
                                             October 15,  1985
                                             Page 5  of  17
 TABLE 6.2
Weather and General Observations of Conditions in the Canty Raspberry Plot oont.
Date Time
13 July 0640
0947
1020
14 July 0630
0700
0800
0845
1000

r
1115
1130

Dry Bulb Wet Bulb t PS Description of Weather
(°C.) (°C.) and Other Observations
Crew into field. Drizzle.
18.6
Drizzle turns to heavy rain;
crew leaves field for the day.
Crew into field.
Worker 21 arrived.
Canty plot picked out; Crew
moved to an adjacent plot,
Heriaro variety.
15.0 10.0 53 Good weather, no clouds.
Crew leaves field for 1/2 hour
lunch.

18.1 14.7 72 No clouds.
Meriams picked out; crew leaves
and will not return Friday.
     Consent forms approved by the Committee for the  Protection
of Human Subjects at the University of California at  Berkeley
(see Appendix D)  were distributed  to each participant along with
detailed instructions for their particular  subgroup (Appendix D).
In order for anyone to be allowed to join the Study, they were
required to return their consent form signed; and if they were
minors, as was this entire crew, their form had to be signed by
their parents, as well.  Each  participant was paid  a  bonus of
$20.00 for the completion of the study if all urine samples were

-------
                                             Section  6
                                             October 15,  1985
                                             Page 6  of  17
collected as instructed.   This  was done,  not  as  an inducement to
participate, but to offset the  inconvenience  and potential aggra-
vation of providing total urine collection for up to 72 hours.
     As with the blueberry study  (See Section 4.2),  the volun-
teers were divided into two subgroups.  The first,  Group  A,  was            M
assigned to wear patch monitors and gloves, while the second were
to have no unusual  impediments  to exposure, which the gloves
night constitute.  Thus,  Group  B wore neither gloves nor  patches
at any time during the study.   All subjects were instructed to
collect a urine specimen  before they entered  the field on Monday
to serve as a pre-exposure control.   On Monday Group A was pro-
vided light-weight cotton gloves to be worn throughout the work-
day while picking berries.  During the lunch  break the gloves
were removed and new gloves issued after  the  break.   Also,  new
gloves were provided if a pair  became too soiled or  wet.  How-
ever, adhering  to this  policy was difficult in this  particular
study,  because  of the heavy moisture on the foliage  due to the
great deal of dew,  drizzle and  rain experienced  during the week
of 11 to 14 July.
     On Tuesday Group A was outfitted with cotton gauze-patch
monitors, in addition to  the cotton gloves, to   measure total
dermal exposure.  Details  of the  placement and handling of the
patches and gloves  are  contained in Appendix  A.   The initial
distribution of subjects  between the two  groups  was sufficiently
imbalanced (14  to 10) that one  person (Subject 13) was  moved from
Group A to Group B on Tuesday.   Table 6.3  does not reflect this
                                                                         48

-------
                                            Section  6
                                            October 15, 1985
                                            Page 7  of  17
 shift of one subject from one group to another,  but  simply shows
 Subject 13 as part  of Group 2 or B.
     The collection of urine  specimens was scheduled to begin on
 Wednesday when it was assumed excretion would have reached some-
 thing near  steady state.  Starting Tuesday after work all sub-
 jects were  provided with 1-liter plastic specimen bottles and
 instructed  to collect their urine for  the remainder of the 72
 hours of the study in the following regimen:  Might  samples to go
 from the termination of work to through the next morning's void;
 day samples from that point through the termination of work.
     The owners of the raspberry farm  had both a drive-up work
   ;
 force and a school bus operation.  The former is much the same as
 was described for the Marion  blackberry field,  where just about
 anyone who wished to do so could come and pick.  These people
 were kept segregated from the monitoring study and did not work
 in the same plot with our crew at any time.
     The school  bus  crew  was designated to work  with the monitor-
 ing study and was constituted the same as the crews  that had
 worked with this organization in strawberries in Corvallis,  Ore-
 gon,  during 1981  and 1982.  The  grower  contracts with a  Crew Boss
 for a crew.  The  Crew Boss recruits a school bus driver  who
 contracts with the school district to  rent one of  the district's
busses for the summer.  A crew of thirty to forty children is
 recruited from the local  school(s)  (with parental consent,  and/or
urging).  On work days the Crew Boss and Driver  go to  each
 child's house and picks them up  before  work  and returns  them home

-------
                                             Section  6
                                             October 15, 1985       525
                                             Page 8  of  17
 after work.   In  the  field,  the  harvesters are paid piece rate,
 and the  Crew Boss is credited for the produce harvested.
 6.3 Sample Storage Handling and Preparation
     Drine samples were stored on ice for no more than 4-6 hours
 and transported to the laboratory the same day as they were
 received from the subjects.  Individual urine sample volumes were
i
 measured and duplicate 20 mL aliguots were pipetted into glass
 ampules  to which 1.5  mL  of  concentrated hydrochloric acid was
 added as a preservative  (resulting in a final pB of less than
 0.5).   The ampules were  sealed and stored at room temperature.
   •  Gloves  and patches were collected from participants by pro-
 ject personnel and stored in  zip-loc  plastic bags.  (See section
 6.7 of the QA Plan for sample preservation  procedures.)
 6.4 Analytical Procedures
     Extraction of samples was as detailed in Section 9 of the
 Quality  Assurance Plan.  A description of the chromatographic
 analysis of  benomyl  is contained  in Section 5.4, including a
 listing  of the chromatographic  conditions in Table  5.3.

 6.5 Crew Characteristics
     This group,  because of  the  fact that it was a school bus
 operation, was made up almost exclusively of youngsters;  only two
 individuals were older than 16 years, and they were friends or
 related to the Crew Boss.  Table 6.3 shows the  physical  charac-
 teristics of  the entire crew of volunteers for  the monitoring
                                                                 .-»•
                                                                       50

-------
                                             Section  6               526
                                             October 15, 1985
                                             Page 9  of  17
 study which consisted of 24 individuals,  of which 13 were
 assigned to Group A (wearing glove and patch monitors) while 11
 made up Group B.
      Taking the crew as a whole,  the ages distributed as follows:
 Ten years or less, 1 (4%); 11 and 12 years, 6 (25%); 13 - 15
 years, 12 (50%); and 16 years and older, 5 (21%).  They were
Ndivided evenly between the sexes, and ranged in weight from 31 to
 86 kg with the bulk  (54%) falling into the 40 - 60 kg range.
      The group wearing patches  (Group A),  numbering 13, ranged in
 age from 9 to 16 and were distributed thus:  Ten years or less, 1
 (8%); 11 and 12 years, 4 (31%); 13 - 15 years, 5 (38%); and 16
 years, 3 (23%).  This subgroup was made up of seven  males and six
 females.  Weights ranged from 32 to 77 kg, again with the great-
 est number of subjects (69%) falling into the 40 to 60 kg range.
 6.6 Results
      Because this field had been treated with benomyl 60 days
 prior to entry,  the  foliar residues  were much lower  than was the
 case in the blackberry study.  As in that  case,  all  of the  dermal
 patch data was below the limit of detection fof  benomyl.   The
 foliar residue data  is shown in Table 6.4.   No clear time trend
 would be expected in this case since  the sampling  interval  was
 over only two days and sampling variability is high  when residue
 levels are very low.   Hence, the residue environment is best
 characterized by the  mean of all sample values which was
 175 ng cm~^»
                                                                      51

-------
                 ABSTAT 3.00
                                         RASPBERRY STUDY, PERSONAL DATA ON THE CREW
FILEI 0301-1
                                                                                                                  REVt 4
                 COMMANDI PRINT DATA
Ln
VARIABLESi
CASE
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
1 SUBJECT
1.00000
2.00000
3.00000
4.00000
6.00000
7.00000
12.0000
15.0000
16.0000
17.0000
18.0000
19.0000
20.0000
5.00000
8.00000
9.00000
10.0000
11.0000
13.0000
14.0000
21.0000
22.0000
23.0000
24.0000
2 GROUP
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
1.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
2.00000
3 SEX
1.00000
2.00000
1.00000
1.00000
1.00000
2.00000
1.00000
2.00000
1.00000
1.00000
2.00000
2.00000
2.00000
1.00000
2.00000
2.00000
1.00000
1.00000
2.00000
2.00000
2.00000
2.00000
1.00000
1.00000
4 AGE
12.0000
9.00000
IS. 0000
15.0000
16.0000
13.0000
13.0000
16.0000
16.0000
15.0000
12.0000
12.0000
12.0000
15.0000
15.0000
13.0000
14.0000
14.0000
11.0000
14.0000
12.0000
28.0000
19.0000
13.0000
5 MGHTKG
43.1000
31.8000
77.1000
61.2000
77.1000
58.1000
44.0000
52.2000
56.7000
59.0000
48.5000
51.3000
54.0000
45.4000
61.7000
63.5000
43.1000
81.6000
35.4000
49.0000
36.3000
86.2000
77.1000
52.6000
6 HEIOHTCM
142.000
135.000
176.000
175.000
175.000
162.000
157.000
157.000
170.000
173.000
160.000
170.000
165.000
168.000
150.000
160.000
152.000
183.000
141.000
156.000
152.000
162.000
180.000
164.000
7 ARBAM2
1.30000
1.10000
1.90000
1.70000
1.90000
1.60000
1.40000
1 .50000
1.60000
1.65000
1.50000
1.55000
1.55000
1.50000
1.60000
1.65000
1.35000
2.00000
1.20000
1.45000
1.25000
1.95000
1.90000
1.55000















ti O 
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aa «-•• o
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-------
                                             Section  6
                                             October 15, 1985
                                             Page 11 of  17
528
                            TABLE 6.4
                       Foliar Residue Data
                         Raspberry Study
Sample
Number
8301-P-61.1
. 8301-P-61.2
8301-P-62.1
8301-P-62.2
Total
Micrograms
66.6
45.1
43.0
68.8
Number of
Leaf Disks*
43
43
47
48
Average
s
% RSD
Residue
ng/cm2**
219
148
129
203
175
43
25
* 3.0 cm diameter.
** Single side basis.
     As in the blackberry study, the measure of exposure is the
residue found in the gloves.  Table 6.5  contains  the  glove expo-
sure rate, in pg/hr, by day and individual worker.  The average
glove exposure rate was calculated for each worker for the entire
course of the study. These values are also  shown in  Table 6.5.
Figure 6.1  is a  scatterplot  of  this  average exposure  rate vs age,
which is mildly suggestive of the same positive correlation
between exposure and age which was seen in both the blackberry
and blueberry studies.   The regression results are given in Table
6.6  and  indicate an F value  on  the verge  of  significance,  but a
very low r2 value  of 0.27.
     As  in the blueberry and blackberry studies,  even this weak
correlation between exposure and age disappears if the exposure
measure is normalized by the body weight of the individual

-------
                                            Section  6
                                            October 15f 19B5
                                            Page 12 of  17
worker.   Figure 6.2 shows the scatterplot of exposure in
ng/kg/hr, versus  age.  As expected, the F value  declines to  0.40
with an  r2  of  0.17 as shown  in Table  6.7.  Note  that these
exposure  values are given in micrograms rather than in milligrams
as in the previous studies.  Therefore, despite the very low
foliar residues and the adverse weather conditions encountered in
this study, the conclusion is the same:  Older workers tend to be
exposed to  a greater total residue than younger workers, but when
exposure is measured on a mg/kg basis, there is no evidence of an
age-related difference  in  exposure.
                                                                       54

-------
                                                          Table  6.5
                 ABSTAT 3.00
                                       RASPBERRY STUDY,  GLOVE EXPOSURE DATA, ALL DAYS
riLEs 8301-P     REVI22
                 COMMANDi PRINT DATA
                 MISSING VALUE TREATMENTi INCLUDE
VARIABLESi
CASE
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1 SUBJECT
1.00000
2.00000
3.00000
4.00000
6.00000
7.00000
12.0000
13.0000
15.0000
16.0000
17.0000
18.0000
19.0000
20.0000
7 GL1
51.2000
27.2000
22.0000
112.200
83.0000
145.000
34.0000
53.8000
92.0000
72.4000
23.2000
37.8000
67.8000
38.6000
8 GL2
19.4445
7.11111
21.8519
30.7408
MISSING
22.0370
23.3333
MISSING
0.00000
0.00000
22.7778
14.0000
21.1111
HISSING
9 GL3
37.0270
20.3514
25.4324
33.5135
35.1351
14.0541
17.6487
HISSING
73.2433
79.1892
22.3243
25.3514
22.2703
47.2973
10 GL4
32.0000
35.5556
82.0000
22.8889
54.0000
28.4444
28.8889
MISSING
40.6667
32.8889
71.5556
26.4444
49.5556
36.6667
11 AVGLRATE
34.9179
22.5545
37.8211
49.8358
57.3784
52.3839
25.9677
53.8000
51.4775
46.1195
34.9644
25.8990
40.1842
40.8547
12 NGLRATE
0.810160
0.709262
0.490546
0.814310
0.744207
0.901616
0.590175
1.51977
0.986159
0.813395
0.592617
0.533999
0.783319
0.756568








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10
00
en

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-------
                                                                     Section  6
                                                                     October  15,  1985
                                                                     Page 14  of 17        531
                                          Figure 6.1


ISTAT 3.00         RASPBERRY STUDY, MEAN EXPOSURE RATE  (UU/HR)  VS AGE         PILE:  8301-P      REV«22

HWANDi PLOT

;SSIHG VALUE TREATMENT] LISTWISE

           • .00000      9.50000      11 .'0000      12.5000       14.0000       15.SOOO      17.0000
                  8.75000      10.2500      11.7500      13.2500     14.7500       16.2500

   .  SB.0000  4
     57.2500  *                                                                      1
     56.5000  4
     55.7500  *
     55.0000  4
     54.2500  4
     53.5000  *                          1
     52.7500  4
     52.0000  4                                            1
     51.2500  +                                                                      1
     50.5000  4
     49.7500  4                                                              1
     49.0000  4
     48.2500  4
     47.5000  4
     46.7500  4
     46.0000  4                                                                      1
     45.2500  4
     44.5000  4
     43.7500  4
     43.0000  4
     42.2500  4
     41.5000  4
     40.7500  4                                   1
     40.0000  4                                   1
     39.2500  4
     38.5000  4
     37.7500  4                                                              1
     37.0000  4
     36.2500  4
     35.5000  4
     34.7500  4                                   11
     34.0000  4
     33.2500  4
     32.5000  4
     31.7500  4
     31.0000  4
     30.2500  4
     29.5000  4
     28.7500  4
     28.0000  4
     27.2500  4
     26.5000  4
     25.7500  4                                   11
     25.0000  4
     24.2500  4
     23.5000  4
     22.7500  4
     22.0000  4         1

           8.00000      9.50000      11.0000      12.5000       14.0000       15.5000      17.0000
                  8.75000      10.2500      11.7500      13.2500     14.7500       16.2500
                                    3 AGE
                                                                                                56

-------
                               Table 6.6


ABSTAT 3.00              RASPBERRY  STUDY,  MEAN EXPOSURE RATE VS AGE


COMMAND: REGR

MISSING VALUE TREATMENT:  LISTWISE


                     ***  MULTIPLE LINEAR REGRESSION ***


DEPENDENT VARIABLE:  11 AVGLRATE               14 VALID CASES
COEFF OF DETERMINATION:    0.270291
MULTIPLE CORR COEFF:       0.519896
ANALYSIS OF VARIANCE  FOR THE  REGRESSION:
                      DEGREES OF      SUM  OF      MEAN OF
SOURCE OF VARIANCE      FREEDOM       SQUARES      SQUARES
      REGRESSION           1          447.116      447.116
      RESIDUALS          12          1207.08      100.590
      TOTAL              13          1654.20
                                            CORRELATION
                REGRESSION   STANDARDIZED      WITH
VARIABLE       COEFFICIENT   COEFFICIENT    DEPENDENT
 3 AGE             2.70261       0.519895     0.519895
                                               8301-P
ESTIMATED CONSTANT TERM:       4.91215
STANDARD ERROR OF ESTIMATE:    10.0295
                        F TEST
                       4.44492
                                                                                •o o v>
                                                                                0> O rt>
                                                                                »Q r* O
                                                                                rt> O rt-
                                                                                  O" -••
                                                                                —« CD O
                                                                                O1 -1 =>

                                                                                O —* 
-------
                                                                   Section 6
                                                                   October 15,  1985
                                                                   Page  16 of 17                 533
                                        Figure 6.2


ABSTAT 3.00   RASPBERRY STUDY, EXPOS. RATE NORM. FOR WGHT. (OG/KG/HR)  VS AGE   PILE.  8301-P      REVI22

COMMAND* PtOT

MISSING VALUE TREATMENTI LISTWISE

             8.00000      9.50000      11.0000      12.5000      14.0000      15.5000      17.0000
                    8.75000      10.2500      11.7500      13.2500      14.7500      1C.2500

       l.COOOO  4
       1.S7500  4
       1.55000  4
       1.52500  4
       1.50000  *                          1
       1.47500  4
       1.45000  4
       1.42500  *
       1.40000  4
       1.37500  4
       1.35000  4
       1.32500  4
       1.30000  4
       1.27500  4
       1.25000  4
       1.22500  4
       1.20000  4
1      1.17500  4
2      1.15000  4
       1.12500  4
       1.10000  4
W      1.07500  4
C      1.05000  4
I      1.02500  4
It     0.999998  4
A     0.974998  4                                                                    1
T     0.949998  4
B     0.924998  4
      0.899998  4                                           1
      0.874998  4
      0.849998  4
      0.824998  4
      0.799997  4                                   1                         11
      0.774997  4                                   1
      0.749997  4                                   1
      0.724997  4                                                                    1
      0.699997  4         1
      0.674997  4
      0.649997  4
      0.624997  4
    .  0.599997  4
    :  0.574997  4                                           11
      0.549997  4
      0.524997  4                                   1
      0.499997  4
      0.474997  4                                                             1
      0.449997  4
      0.4249*7  4
      0.400000  4

             8.00000      9.50000      11.0000      12.5000      14.0000      15.5000      17.0000
                    8.75000      10.2500      11.7500      13.2500      14.7500      16.2500
                                      3  AGE
                                                                                            58

-------
                                          Table 6.7

         ABSTAT  3.00    RASPBERRY STUDY,  EXPOS. RATE NORM.  FOR WGHT.  (UG/KG/HR)  VS AGE

         COMMANDS REGR

         MISSING VALUE  TREATMENT: LISTWISE

                              *** MULTIPLE LINEAR REGRESSION ***

         DEPENDENT  VARIABLE:  12 WGLRATE               14 VALID CASES
                                        FILE: 8301-P
         COEFP OF  DETERMINATION:   3.226E-02
         MULTIPLE  CORR COEFF:       0.179615
ESTIMATED CONSTANT TERM:       1.06819
STANDARD ERROR OF ESTIMATE:   0.258549
         ANALYSIS  OF VARIANCE FOR THE REGRESSION:
                                DEGREES OF     SUM OF      MEAN OF
         SOURCE  OF VARIANCE     FREEDOM      SQUARES      SQUARES
               REGRESSION          1       2.674E-02    2.674E-02
               RESIDUALS          12        0.802173    6.684E-02
               TOTAL              13        0.828915
                                                     CORRELATION
                          REGRESSION   STANDARDIZED      WITH
         VARIABLE        COEFFICIENT    COEFFICIENT    DEPENDENT
          3 AGE           -2.090E-02      -0.179615    -0.179615
                        F TEST
                      0.400043
                                                                                         "OO 
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                                                                                         IO r+ O
                                                                                         fl> O «-»•
                                                                                           cr -*.
                                                                                         —•mo
                                                                                         -•4 -J 3
                                                                                         o —• o*
                                                                                         -•> 01
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-------
                                                     535
         APPENDIX A
QUALITY ASSURANCE PROJECT PLAN
                                                   60

-------
                                                          •w W I J I VII  I1U «
                                                         Date:   'November  10. 1982^
                                                         Page      1     "bT
                                                                        536
                  PESTICIDE EXPOSURE BY HARVESTERS
                   OF BUSHBERRIES, TRAILING-  AND
                             CANEBERRIES
                                by

                        John T.  Leffingwell
                          Hugh R.  McLean
                          Gunther  Zweig
                   Quality Assurance Project  Plan
                 Pesticide Hazard Assessment  Project
                       University of California
                        Berkeley, California
Approval:
Principal Investigator:	Date
Project QA Officer:	Date
EPA Project Officer:	Date_
EPA QA Officer:	Date
                                                                             61

-------
                                                                       re-
                                                      Section No.	2
                                                      Revision No.	0
                                                      Date:    November 10.  1982
                                                      Page    i     of    3
                      2.  TABLE OF CONTENTS

Section                                                       Page Reference
    1.  TITLE PAGE	   1 page
    2.  TABLE OF CONTENTS	
    3.  PROJECT DESCRIPTION	   2 pages
    4.  PROJECT ORGANIZATION	   2 pages
    5.  QUALITY ASSURANCE OBJECTIVES 	   3 pages
    6.  SAMPLING PROCEDURES                                      6 pages
        6.1  Dermal Exposure to Pesticides	   1 of 6
        6.2  Personal Aerosol Monitors   	   2 of 6
        6.3  Area Aerosol and Vapor Monitors	   2 of 6
        6.4  Foliar Samples	   2 of 6
        6.5  Soil Samples	   3 of 6
        6.6  Urine Samples	   4 of 6
        6.7  Sample Preservation	   5 of 6
        6.8  Forms, Notebooks,  Recordkeeping 	   6 of 6
    7.  SAMPLE CUSTODY                                           5 pages
        7.1  Field Sampling Operations 	   1 of 5
        7.2  Laboratory Operations	   4 of 5
    8.  CALIBRATION PROCEDURES  AND FREQUENCY                     4 pages
        8.1  Field Equipment	   1 of 4
        8.2  Laboratory Equipment	   2 of 4
    9.  SAMPLE PREPARATION                                       4 pages
        9.1  All Samples	   1 of 4
        9.2  Gauze Pads	   1 of 4
        9.3  Glove Samples	   1 of 4        62

-------
Section No.
538



Section
9 4 Aerosol Samples 	
9 5 Leaf Punch Samples 	
9 6 Soil Samples 	
9.7 Urine Analysis 	
10. DATA REDUCTION, VALIDATION AND REPORTING .
11. INTERNAL QUALITY CONTROL CHECKS 	
12. PERFORMANCE AUDITS 	
13. PREVENTIVE MAINTENANCE
13.1 Field Equipment 	
13.2 Laboratory Equipment 	
13.3 Spare Parts Inventory 	
14. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
PRECISION, ACCURACY AND COMPLETENESS
14.1 Field Sampling 	
14.2 Laboratory Analyses 	
14.3 Further Reduction 	
15. CORRECTIVE ACTION 	
16. QUALITY ASSURANCE REPORTS MANAGEMENTS . .
APPENDICES
A. Field Personnel Sampling Form 	
B. UCB Sample Identification Code 	
C. Laboratory Sample Log 	
D. Dermal Data Sheet 	
E. Monthly Laboratory Status Report 	
F. Study/ Investigation Monthly Status Report
G. Aerosol Data Form 	
Revision No. 0
Date: November 10, 1982
Page 2 of 3
Page Reference
	 1 of 4
	 2 of 4
	 2 of 4
	 3 of 4
	 5 pages
	 2 pages
	 1 page
2 pages
	 1 of 2
	 1 of 2
	 2 of 2
DATA -
2 pages
	 1 of 2
	 1 of 2
	 2 of 2
	 1 oaae
	 1 page
	 1 oaae
	 l nage


.... 1 oaae
	 1 page
	 1 cage

-------
Section
APPENDICES (Continued)
    H.  Leaf Punch Data Sheet .
    I.  Soil Sample Data Sheet
    J.  Crop Sample Data Sheet
    K.  Meteorology Data Sheet
                                                                        2
                                                                        0
Section No._
Revision No.."	
Da te:   	November 10, 19R2
Page	3     of   3
     Page Reference

        1 page
        1 page
        1 page
        1 page
53'
                                                                             64

-------
                                                                                    54(
                                                          Section No.	
                                                          Revision No.
                                                          Date: November 10, 1982
                                                          Page   1   of	2
                          3.  PROJECT DESCRIPTION
     The purposes of the proposed field studies to be conducted by the
California PHAP during the summer of 1983 are several fold:  1) The harvesting
activities of children in the cane-, bush- and trailing berry crops in all
likelihood presents a different pesticide exposure pattern to pesticides than
does strawberries because of substantial differences in the physical charac-
teristics between the former set of crops and strawberries.  Therefore, as an
extension of the "youth- in-agri culture" line of monitoring studies we will
attempt to determine the nature and extent of pesticide exposure suffered by
children or youths harvesting these crops.  This information will be compared
and contrasted with like information for corresponding groups of adults.
2) It is of considerable general interest to compare the excretion of pesticide
metabolites with whatever measures of dermal exposures that can be made on
workers.  Toward that end, two groups of subjects will be monitored in each
crop type.  One group will be monitored for dermal exposure to one or more
pesticides, while the other group will give urine samples for metabolite analy-
sis.  In each study both groups will engage in both activities so that they will
act as their own controls.  As usual cognizance will be taken of age, height,
weight and sex of the individual subjects in these studies.
     Since the pesticides under consideration are generally compounds with low
volatility (e.g., captan), exposures are expected to result from dermal contact;
consequently, this route of exposure will be given major emphasis in the con-
templated field studies.  Dermal dosimeters currently in use in this laboratory
consist of 12-ply, 3x3 inch surgical sponge (gauze pad) backed by a polythylene
                                                                                    65

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                                                                                  541
                                                          Section No.      3	
                                                          Revision No.     0
                                                          Date:  November 10,  1982
                                                          Page   2   of   2	
moisture shield enclosed in a paper envelope that has a circular face  opening
               2        2
to expose 28 cm  (4.3 in ) of the gauze pad.  This configuration allows for
rapid assembly of the dosimeter and easy attachment to carrier garments such
as T-shirts.  The potential for inhalation exposure will not be ignored,
however.  Both aerosol and vapor samplers will be placed in the field  for
general  monitoring.   At least two of the subjects will carry "breathing zone"
personal aerosol monitors.  These monitors will  be rotated among the subjects
at two hour.intervals.
     Since urine grab samples are of limited utility in interpreting metabolite
outputs, complete urine collections will be requested of the cooperating sub-
jects over the desired monitoring period.  These will be done in as close to
12 hour blocks ("day" and "night") as the subjects can manage.
     Environmental  samples will be comprised of foliar leaf discs (48  x 3 cm
diameter punches per sample), soil samples (6 scoops of 8 x 10  x 1 cm  deep
making in all  some 600-800 g of soil) representative crop samples and  area
aerosol  collections  which are backed up with charcoal tube vapor traps.  All
environmental  samples will be collected in the vicinity of the  workers  who are
being monitored.
     All samples will be placed on dry ice immediately after they have  been
collected.   At the completion of sample collection they will be transported on
dry ice  to the laboratory, transferred to a freezer and maintained at  -10°C or
colder until just prior to extraction.
                                                                                  66

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                                                          Section No.
                                                                                542
                                                                             o
                            Revision No.
                            Date:   November 10, 1982
                            Page   l
                                                                        of
                          4.   PROJECT ORGANIZATION
     The following chart shows the organizational  structure  for  developing and
implementing QA Project Plans within the Berkeley PHAP.   Acceptable  QA  procedures
will be developed in cooperation with, and under the supervision of, the OPP Quality
Assurance Officer.  It is understood that the EPA project officer (Dr.  C.W. Miller)
will function as the Quality  Assurance Officer in  terms  of:
     1)  providing guidance to the project on QA,
     2)  facilitating interlaboratory QA, and,
     3)  approving QA project plans.
The responsibility for the design and implementation of  acciptable QA procedures
lies with the Project Director of the Berkeley PHAP.
                             Quality Assurance
                              Officer OPP/HEB
                            EPA  Project Officer
                                NPHAP/HEB
                            Project Director
                             Berkeley PHAP
       Committee for the
 Protection  of Human Subjects
     Chief Chemist
Statistician
Field Studies
  Supervisor
                                                                                    67

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                                                          Section No.       4
                                                          Revision No.      0
                                                          Date;   November 10, 1982
                                                          Pa ge    2     of    2
        The Chief Chemist,  with  guidance  and concurrence of the Project Director,
is responsible for the design  and  implementation of QA procedures within the
laboratory.  He is responsible for supervising the laboratory's participation
in any inter!aboratory quality control  programs.  He also must design, schedule
and evaluate interlaboratory QA  procedures  to  insure confidence in the methodology
and facilities used for all  analyses.
                                                                                     68

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                                                                            544
                                                          Section No.      5	
                                                          Revision No.     0
                                                          Date;  November 10,  1982
                                                          Page  1    of    3
                       5.  QUALITY ASSURANCE OBJECTIVES
     The measurements to be attempted in this study center on the estimation
of dermal exposure of pesticides undergone by workers harvesting cane-, bush-
and trailing berries.  Since there is no standardized methodology for accom-
plishing this task, it is impossible to estimate accuracy.  However, components
of the method can be tested for precision and accuracy by employing the device
of spiked blanks.  These components include recovery of pesticide from gauze
patches, gloves, aerosol and vapor samplers, and the analytical  procedures used
to assay the recovered residues.
     For environmental samples, accuracy can be gauged by the taking of repli-
cate samples.  Spiked blanks are required here, as well, to determine precision
and accuracy.  Table 1.5 shows the best current estimates for the QA objectives
for the measurements to be made during the berry harvester studies.
     In reference to Table 1.5, since this study does not focus  on only one
pesticide or class of pesticides, the detailed methods of extraction and
analysis cannot be foretold, and, in fact, can be developed and  validated only
after the exact combination of pesticides applied to a given field (to be
monitored) have been reported.  In general, however, the following references
are applicable to Dermal Dosimeters:
     1)  McLean, H. R.; Futagake, S.; and Leffingwell, J. T.
         Loss of Paraoxon in aqueous acetonitrile extractions.  Bull.
         Environ.  Contam. & Toxicol.  18:247, 1977.
     2)  Popendorf, W.
         Exploring citrus harvesters exposure to pesticide contaminated
         foliar dust.  Am. Industr. Hyg. Assoc. 0.  41:652, 1980.

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                                                                           545

                                                         Section No.      5
                                                         Revision No.     o
                                                         Date; November 10, 198?
                                                         Page    2   of    3
to Aerosol  Monitors and Vapor Traps (for total  dust  and  various  pesticides):

     National  Institute for Occupational Safety &  Health
     NIOSH  Manual  of Analytical  Methods, 2nd Ed.

         vol.  1   DHEW (NIOSH) Publ.  No. 77-157-A
               2     "            "       77-157-B
               3     "            "       77-157-C
               4     "            "       78-175
               5     "            "       79-141
               6     "            "       80-125

to Soils:

     1)  Spencer,  W.  F., Cliath, M. M.,  Davis,  K.  R., Spear, R.C., and
        Popendorf, W.  J.
        Persistence of Parathion and its oxidation  to paraoxon  on the soil
  ?      surface as related to worker reentry into treated crops.  Bull.
        Environ.  Contain. Toxicol. 14:265,  1975.

     2)  Spencer,  W.  F., Iwata,  Y., Kilgore,  W.  W.,  and  Knaak, J. B.
        Worker reentry into treated  crops II:   Procedure for the deter-
        mination  of pesticide residues  on the  soil  surface.  Bull.  Environ.
        Contam.   Toxicol.   18:656, 1977.

to Foliar Surface  Residues:

 *   1)  Iwata, Y., Knaak,  J.  B., Spear, R.  C.,  and  Foster, R. J.
        Worker reentry into pesticide treated  crops I:  Procedure for the
        determination  of dislodgeable pesticide residues.  Bull.  Environ.
        Contam. Toxicol.  18:649, 1977.

     2)  Popendorf, W.  J.,  and Leffingwell,  J.  T.
        Procedures for the determination of dislodgeable dust on foliage as
        related to worker reentry hazards.   Bull.   Environ.  Contam.  Toxicol,
        18:787, 1977.

to Body  Surface Area:

     1)  Popendorf, W.  and  Leffingwell,  J. T.
        Regulating OP  pesticide residues for farmworker protection.  Residue
        Reviews 82:125, 1982.
                                                                                   70

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             TABLE  1.5

Quality Assurance of Objectives
Measurement EPA Experimental
Parameter Reference Conditions
Dermal
Dosimeters
Gauze
Gloves
Aerosol Monitors
Vapor Traps
Soils
Foliar Surface
Residues
Urine
Body Surface
Area
Time Of
Exposure

Spiked Blanks
Spiked Blanks
Spiked Blanks
Spiked Blanks
Spiked Blanks
Spiked Dust
Spiked Blanks


Pr(RSD)°n Accuracy Completeness

±5%
+ 5%
t 5%
is*
i 10% - 10%
+ 5*
i 10%
1 20%
1 5 Min. - 15 Min.
(2%) (5%)
                                                                                     •O O 30 t/>
                                                                                     Dl OJ  (T> 
                                                                                    U3 <-<• < O
                                                                                     (T> fD  —'• r*
                                                                                          -i. O
                                                                                          O 3

                                                                                       z   z
                                                                                       O Z O
                                                                                       < O •
                                                                                       tt>
                                                                                       n>
                                                                                              C_T

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                                                                                 b4/
                                                           Section  No.	6	
                                                           Revision No.       0
                                                           Date:    November  10, 1982
                                                           Pa ge    1     o f   6	
                          6.  SAMPLING PROCEDURES

6.1  Dermal  Exposure to Pesticides
     This project employs a gauze pad as  a  dermal  dosimeter for all areas of
the worker's body except the hands.   This dosimeter consists of a  12-ply 3x3
inch gauze surgical  sponge.  A polyethylene "moisture  barrier" is  placed on the
side of the pad facing the skin of the subject.  All of this is held  in a glossy
paper envelope.  The side of the envelope facing away  from the skin has a circular
                                     2
hole 60 mm in diameter exposing 28 cm  of the gauze pad.
     Body locations for mounting the gauze pad dosimeters are as follows:
     Head — mounted on the side of the head, roughly  over one ear, either stapled
             to a stretchable head band or taped to the inside of  the brim of the
             subject's hat (1);
     Chest — mounted over sternum between the pectoral muscles  (1);
     Back — mounted over backbone between the scapulae (1);
     Upper Arm ~ mounted over the deltoid muscles (2);
   l'  Lower Arm ~ mounted roughly midway between the elbow and wrist  on the
                  dorsal surface (2);
     Upper Leg — mounted roughly midway between the hip and the knee on the
                  anterior surface (2);
     Lower Leg — mounted roughly midway between the knee and  the  ankle on the
                  anterior surface (2).
     For ease of mounting and dismounting the patches, the  chest,  back and  upper
arm dosimeters are stapled to T-shirts which are dispensed  to  the  subjects  at
the beginning of the work period and collected at  the  end.   The  T-shirts  are to
be worn next to the skin of the subject so that the dosimeters will  be exposed to
                                                                                     72

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                                                                                548
                                                           Section No.__6____
                                                           Revision No.       0
                                                           Date:    November 10.  1982"
                                                           Page    2     of    6.

only that portion of the residues that would eventually reach the skin.  Lower
arm and upper and lower leg patches are taped directly to the skin in the appro-
priate location after the T-shirt is donned.  The subjects then wear whatever
clothing they would normally wear while working, except that if they were to strip
to the waist (which some male workers in California do) they would continue to
wear the T-shirt bearing the dosimeters.  A hand dosimeter consists of a light-
weight cotton glove.
6.2  Personal Aerosol Monitors
     Personal breathing zone air samples will be taken on at least two subjects
each working period of two hours.  An open-face, 37 mm Milltpore cassette
(0.8 y pore size) is mounted in a subject's breathing zone and is aspirated at
2.0 t 0.2 Lpm with a belt-mounted portable pump.
6.3  Area Aerosol and Vapor Monitors
     An open face 37 mm Millipore cassette (0.8 w pore size) will be stationed
centrally in an area of the field under harvest by our cooperative subjects.
This cassette will be backed up by a charcoal tube vapor trap as insurance against
vapor break-through from the filter.*
6.4  Foliar Samples
     Foliar sampling is accomplished by using a leaf punch equipped with a 3 cm
diameter die.  The punch-through action of the device pushes the leaf disk into
a 4-oz wide-mouth jar which is attached to the punch and which subsequently serves
as the sample storage container.  The punch is also equipped with a resettable
counter.
*It should be noted that the experience of this laboratory is that Millipore filters
possess an appreciable capacity for absorption of pesticide vapors.  However, since
the vapor retention characteristics of the filter for the particular pesticides1'
being studied here are unknown, a back-up charcoal tube (#226-01, SKC-West, Inc.)
is employed.

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                                                           Section No.	6_
                                                           Revision No.       0
                                                           Date:    November 10.  1982
                                                           Page    3     of   6
     Sample collection is accomplished by striking out diagonally across the area
to be sampled, stopping every three or four rows to take a single leaf sample.
The sampling points are to be distributed throughout the areas of the plants
that the harvester will actually contact.  This includes all parts of the plant,
both outer and inner canopy leaves, from either side of the row, and from the
center.   The standard sample size is 48 disks.  If the edge of the field is reached
before the full complement of leaf disks has been obtained, the person collecting
the sample merely reflects back into the field on a new diagonal.
6.5  Soil  Samples
     The soil sampling device has two parts: a three-sided form 10 cm long by
8 cm wide and 8 cm high, which when pressed into the soil surface blocks out an
          2
area 80 cm ; and a small rectangular shovel which fits just inside the form and
has a 1  cm high rim around the sides and back.  See Figure 6.1
     Sampling is accomplished by first shoving the form into the soil several
centimeters.  The shovel is then inserted vertically into the soil at the open
face of the form, likewise, several centimeters; and the soil is scraped away
from the form with it to a depth of several centimeters.  The shovel is then run
into the form horizontally so that it picks up a layer of surface soil the area
of the form and 1 cm deep.  The sampling pattern utilized for
taking soil samples is the same as for taking foliage samples, being collected
on a diagonal across the area being harvested by the cooperating pickers.  How-
ever, since there are only six "scoops" taken, rather than the 48 sampling sites
for the leaf punches, samples are taken every 8 to 10 rows.   Furthermore, samples
are taken in the area between the planted rows, which is where pickers are
physically located, and where they contact the soil.  Soil samples  are held in
a paper sack (#4 lunch bag) which is in turn placed in a plastic bag  to  reduce ___
moisture loss in frozen storage.

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                                                          Section  No.
                      550
                                                                             o
Revision No.
Date:    November 10, 1982"
Page	A
                                                                         of
Figure 6.1:  Soil Sampler
6.6  Urine Samples
     Subjects are requested to give all  of their urine in  approximately 12  hour
segments for at least 72 hours after exposure has terminated.   Initially they  are
supplied with three wide-mouth, 500 ml Nalgene bottles:  1) One  for the first period
of collection; 2) one for the next 12 hour period; 3)  and  one back-up for the  event
that it is ever needed.  The bottles are labeled with  the  subject's name, and
those that are intended for a specific time period have  the proper date and the
designation "day" or "night" on them.  In addition, there  is label  space for the
subject to write the actual times of first and last use  on the  label.  Thus, each
subject should have a full 24 hour's worth of bottles  and  a back-up to start out.
     The subjects are instructed to fill out the label on  each  bottle as it is
used in its appropriate time period and to either bring  the bottle to project
staff or to store it .refrigerated until  they can do so.  Each subject is given
a new set of bottles to replace the ones brought in to project  personnel  until -

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                                                           Section  No.	6	
                                                           Revision No.       0
                                                           Date:    November 10,  198T
                                                           Page     5     of   6
the 72 hour time  period is exhausted.
     Bottles are prepared by washing fn hot water with a strong laboratory
detergent.   After appropriate water rinsing, the bottles may be rinsed with
dilute hydrochloric acid if visual Inspection shows deposits.  Finally, they
are rinsed with acetone to remove traces of soluble organic material, air-dried
and returned to service.
6.7  Sample Preservation
     All  samples, regardless of type, are placed on dry ice as sampling is
completed.   They are kept thus in ice chests until they are delivered to the
laboratory, where they are transferred to a standard freezer chest maintained
at -10°C.   Samples are generally hand delivered to the laboratory by the field
study personnel  (which often includes laboratory personnel).   If the samples
cannot be  inventoried by the laboratory personnel  immediately upon arrival, the
samples are stored until the next working day in a different freezer from the
one customarily used for sample storage.  This procedure minimizes the possibility
of not logging a sample entering the sample storage freezer.
     In the unexpected event that samples are shipped by common carrier rather
than being  hand carried by project personnel, arrangements will be made between
the person(s)  shipping the samples and the laboratory to reduce the chance of
losing samples en route.  For short distances, our laboratory has found that
the "next bus  out" service of Greyhound Package Express is reliable and provides
overnight  (cool) service from anywhere in Northern California.  For longer distances
an appropriate air courier service is chosen.  Once the shipment has been made  and
the laboratory has been telephoned to confirm that face, the Chief Chemist arranges
for someone to meet the shipment at its expected time of arrival.
i
                                                                                     76

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                                                                                   55
                                                           Section  No.	6" '
                                                           Revision No.       0
                                                           Date:    November TO.  1982^
                                                           Page    6      of   6
     Samples are removed from the storage freezer only for the purpose of
inventorying and analysis.  During inventories, small numbers of samples are
removed at one time to prevent their thawing during identification and counting.
When samples are removed for analysts, they are withdrawn from the freezer in
groups only the size of the numbers of samples to be extracted, allowing the
minimum thawing time needed for room temperature equilibration.
6.8  Forms, Notebooks, Recordkeeping
     A form has been developed in this laboratory to record pertinent field
data on cooperating harvesters, and is included here as Appendix A.   This form
records a subject's personal data such as age, height, weight, his/her clothing,
work habits, and production (yield).  The form also provides for accumulation of
exposure data (contact time, times and flow rate for air samplers, and for
comments on irregularities in sampling, or subject's work).
     A field notebook is maintained as well  as individual  data sheets on the
subjects.  This book records the time, location, and quantity of all  environmental
samples taken, including data on all foliar, soil, and area air samples, regardless
of whether they were taken before, during, or after a harvester exposure study.
                                                                                77

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                                                          Section No.       7    553
                                                          Revision No.      0
                                                          Date:   November 10, 1982
                                                          Pa ge    1     of    5
                             7.   SAMPLE  CUSTODY
7.1   Field  Sampling Operations
     A.   Preparation of Sampling Supplies
         1)  Preparation of the  dermal dosimeters is described in Section 3
             of this document.   The  gauze sponges are preextracted by soxhlet
             in order to eliminate possible  interferences which this laboratory
             has previously encountered  with some batches of the sponges.  Once
             the samplers are assembled  they are labeled with their sample identify-
             ing code and stapled, when  appropriate, to the T-shirt carrier.   All
             head,  lower arm, and leg patches must be attached to the subject as
             he/she is about to  enter the study.  Lower arm and leg patches are
             taped  in place. Head patches are either taped to the subject's  hat,
             if one is worn, or  stapled  to a project-supplied hat or head band
             which  is worn as a  carrier.
         2)  The Millipore filters used  both for personal samplers and for area
             monitoring are prepared as  follows;
             Pre-weighing Procedure
             —Prior to use in the field, the filters are weighed in order to
             establish initial weights.  Six control filters are weighed at the
             same time in order  to quantify  weight gained due to moisture in the
             laboratory.
             —The  test filters  are  removed  from the sealed packaging and allowed
             to sit out on the laboratory bench for approximately 10 to 20 minutes,
             in order to equiibrate  with room moisture.  A paper is placed over
                                                %
             the filters to prevent any dust  from settling on them.  The control
             filters are prepared for weighing in the same manner.  The cassette
                                                                                    78

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                                              Section No.	7    554
                                              Revision No.	0
                                              Date:    November 10, 1982^
                                              Pa ge   2      o f    5
holders are prepared at this time and an identification number is
assigned to each one.  Once the filters are placed in the cassettes
they will be referenced by this number.
—An automatic electro balance having a digital readout in milli-
grams with four significant figures is used to weigh the filters to
1 5 micrograms.  The balance is calibrated using a standard 20 mg
weight prior to any filter weighing.  The calibration is repeated
intermittently during the weighing of both the control and test
filters to assure an accurate reading.  The filters are handled with
blunt-tipped forceps.  The weights for both the test and the control
filters are recorded and logged into a laboratory notebook.  The
test filters are entered and referenced by the number given to the
cassette in which they will be placed.  The control filters are
referenced by a number on the petri dish in which they are stored.
After the weight has been recorded the filters are assembled into
the cassettes and are then ready for field use.
Transport From Field
--At the completion of aerosol sampling the cassettes are placed
upright in a styrofoam holder to prevent Toss of dust from the
filter.  The holder is placed fn an ice chest with dry ice which
is then transported to the laboratory.
Post Weighing
—The post-weighing procedure is identical to the pre-weighing
procedure with the exception that the filters are placed in
individual, dessicating jars which contain anhydrous calcium sulfate.
                                                                    79

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                                                                           ;     55l
                                                      Section No.	7
                                                      Revision No.       Q
                                                      Date;    November 10,  1982~
                                                      Pa ge     3     of    5
        After removal of the moisture caused by the refrigeration process,
        the filters are placed on the laboratory bench and allowed to equili-
        brate with the room moisture.  The control  filters are prepared in
        the same manner.  The difference in weight  between pre- and post-
        weighing are logged into the notebook for each filter.  The same is
        done for the control filters.  The resulting dust weights are obtained
        by the difference in the pre- and post-weight minus the average weight
        gain for the six control filters.  The filters are then placed back
        in their cassettes and held in the freezer  to await chemical  analysis.
    3)  Leaf punches are cleaned of the build-up of leaf debris and dirt
        which accumulates on the punch and die while a sample is being
        collected.  This cleaning is performed with a household scouring pad
        made of either copper or stainless steel turnings.  Cleaning  is per-
        formed between samples and reduces chances  of any cross contamination
        between samples.
    4)  Vapor samplers are obtained commercially and are opened only  as they
        are to be used.  They are resealed immediately after sampling with
        the caps provided by the supplier.
B.  Procedures and forms for Recording Sample Acquisition Data
    This information  is put forth in Section 6.
C.  Documentation of Specific Sample Preservation Methods      ^  ^7
    Sample preservation methods are described in SectionsS of this document.
D.  Sample Labeling
    Each study is preassigned a "field" or study number.  This number,
    combined with the year, yields a unique study number.  Appendix B is
    the document supplied to the field personnel describing label generation.
                                                                                  80

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                                                          Section No.       7   556
                                                          Revision No.	0
                                                          Date    November  10, 198T
                                                          Page    4     of   5
     E.  Field Tracking Forms
         The subject data sheet and the field notebook act  as  field tracking
         devices.
7.2  Laboratory Operations
     A.  Laboratory Sample Custodian
         The Chief Chemist is the laboratory sample  custodian  and  as such  is
     responsible for inventorying samples  held for analysis or other processing
     and for maintaining all  necessary documents  pertaining to sample custody.
     These documents include  any shipping  receipts or  bills of lading and  a
     sample log book (see Appendix C).
         The sample log book  provides  for  the notation of sample identity,  date
     of sampling if known, date recieved,  date extracted, and  date analyzed.
     Sample numbers used within the laboratory are those assigned  in the field
     since those identifiers  are unique and  specify  useful  and pertinent data
     about the sample as well  (i.e., days  post application, sample type).
         Sample flow through  our laboratory,  and  thereby sample custody, follows
     the general pattern discussed hereinafter: when samples first arrive  at the
     laboratory they are placed in a specified freezer, "A", until  they can be
     logged into the laboratory log book.  After  they  are logged in they are trans-
     ferred to a second freezer, "B".   The  person responsible for extraction pulls
     batches of samples from  freezer "B",  noting  this  in the log book, performs the
     appropriate extraction procedure,  prepares the  sample  for analysis, and turns
     the batch over to the analyst.  The analyst  is  responsible for proper documenta-
     tion of the chromatograms and maintenance of sample integrity while he/she
     has possession of them.   The anaylst  also must  note the date  of analysis in
     the log book.   When analysis of the batch is complete, the samples are  r
                                                                                   8

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                                                     Section No.	7
                                                     Revision No.      0
                                                     Date:   November 10, 1982
                                                     Page    5     of   5
returned to the person who performs  the extraction and the samples are

prepared for archival  storage  and  replaced in freezer "B".
                                                                            82

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                                                          Section  No.	8    558
                                                          Revision NoT0
                                                          Date:    November 10, 1982
                                                          Page    1     of    4
                  8.  CALIBRATION PROCEDURES AND FREQUENCY

8.1  Field Equipment
     A.  Personal Sampling Pumps
         The personal sampling pump shall  be calibrated  before  and  after each
     day of sampling.
     1)  Allow the pump to run 5 minutes prior to voltage  check and calibration.
     Check the voltage.
     2)  Assemble the polystyrene cassette filter holder using  the  appropriate
     filter for the sampling method.   Ensure that the  luer adaptor  does  not come
     in contact with the back-up pad.
     3)  Connect the collection device,  tubing,  pump and calibration apparatus.
     The length of hose should be the  same as that used  in the  sampling  train
     (approximately 1 meter).
     4)  Check the seals on all Tygon  tubing connections.
     5)  Wet the inside of a 1-liter buret with  a soap solution.
     6)  Turn on the pump and adjust the pump rotometer  to the  appropriate flow
     rate setting.
     7)  Momentarily submerge the opening  of the buret in  order to  capture a
     film of soap.
   ;  8)  Draw two or three bubbles up  the  buret  in order to ensure  that  the
     bubbles will complete their run.
     9)  Visually capture a single bubble  and time the bubble from  0 to  1000 ml.
    10)  The timing accuracy must within t 1  second of the time corresponding to
     the desired flow rate.
                                                                              83

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                                                          Section No.        8       559
                                                          Revision No.       0
                                                          Date:   November  10,  1982~
                                                          Page   2	o f   4	
    11)   If the time is not within the range of  accuracy, adjust the flow  rate
    and  repeat steps 9 and 10 until  the correct  flow  rate is achieved.
    12)   Steps 9 and 10 shall be performed at least twice.
    13)   While the pump is still  running,  mark the position of the pump rotometer
    14)   A calibration curve can then be calculated.  The flow rate in LPM is
    placed on the x-axis and the rotometer reading on the y-axis.
     B.   Other Field Equipment
         In general, the relatively crude  measurements taken in the field, such
     as  height and weight of subjects, and time  worked, are effected with  devices
     whose calibration are not checked.  This includes carpenter's rule, a bath-
  ;   room scale, and various researchers'  wrist  watches.  The thermometers of the
     psychrometers, the thermo-anemometer  and any other meterological instruments
     are used generally uncalibrated, as well, since their data is used only for
     background information to describe the quality of the working conditions.
8.2   Laboratory Equipment
     A.  Balances
     1)   Electrobalance: the electrobalance used to weigh membrane filters for
     aerosol  monitoring is calibrated as described in Section 7 of this document.
                                                      •
     2)   Analytical  Balance:  the balance used to weigh analytical standards and
     smaller samples (SlOg),  when necessary,  is  a Mettler Model B-6 which  is good
  v*
     on  its vernier to at least 0.02 mg.   It  is  kept in a balance room out of
     normal  traffic flow and  laboratory activities.  The laboratory which  houses
     PHAP activities contracts for an annual  cleaning and calibration from a
     private  contractor.
     B.   Volumetric Glassware
         Whenever practical or necessary,  volumetric  glassware  is  Class  A or
     Class A serialized quality.  Further  calibration is  not  attempted.   In

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                                                                         _    56C
                                                      Section No.	8	
                                                      Revision No.       0
                                                      Date;    November 10,  1982
                                                      Pa ge    3     o f   4
non-critical applications such devices as tilt-dispensers and graduated
cylinders are employed.
C.  Analytical  Instruments
    The chromatographs are checked continually as they are used by injection
of standards.   When manual injections are done, more frequent standardization
is required (every three to five samples) than when a mechanical injection
device is used.  Furthermore, the analyst  is  required to choose standards
that clos:ely match the samples being injected.  When automatic injection is
being done,less frequent standardization is called for (every ten samples).
D.  Calibration Standards
    Chromatographic standards are obtained, whenever possible, from the
EPA repository  at Research Triangle Park, NC.  Failing that, they are
obtained from the following sources in the order of preference listed:
1)  Commercial  suppliers (e.g., Chem. Services, Westchester, PA) as
    crystalline solids or neat liquids.
2)  Pesticide manufacturers as crystalline solids or neat liquids.
3)  Commercial  suppliers as a solution in organic solvent (e.g., Nanogens,
    Supelco, Van'an Associates, etc.).
4)  Pesticide manufacturers as technical grade materials.
5)  Pesticide manufacturers as formulated pesticides.
    Standards,  unless obtained as a solution, are weighed out with an accuracy
sufficient to give at least four significant figures.  Dilutions are made in
hydrocarbon solvents, at least for the concentrated standards.  This is done
to minimize the possibility of chemical reactions between solvent and solute.
If reactive solvents, such as ketones, alcohols, or nitrogen containing
compounds, are  required by the analytical method being used, they are used
only to make up the working standard.

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                                                     Section No.	8   56 I
                                                     Revision No.       0
                                                     Date;    November 10, 1982"
                                                     Pa ge    4     o f   4	
    As few dflution  steps as possible are used to obtain a working standard,

thus reducing errors inherent  in such operations.
                                                                           86

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                                                                                   56;
                                                           Section No.	9
                                                           Revision No.      0
                                                           Date;    November 1o, 1982"
                                                           Page    1     of   4
                      9.  SAMPLE PREPARATION PROCEDURE

9.1  All Samples
     Sample preparation date and extraction volume are entered in the spaces
provided in the sample log book.
9.2  Gauze Pads
     Samples consist of one or two pads (one for main trunk or two for limb sample
sites) stapled inside paper application packs and stored in an RPE Zip-lock bag
in the freezer.  After the staples are removed, the pad together with the plastic
moisture barrier is transferred to a 125 ml LPE wide-mouth bottle.  Thirty ml of
toluene, some of which is used to rinse the bag, are added and the sample is
shaken at about 200 Hz for one hour.  A ten ml aliquot of the analyte  is reserved
in a glass polyseal vial and an auto-sampler vial is prepared from the remainder.
9.3  Glove Samples
     These are treated in a manner similar to the patches.   The gloves are frozen
one pair to a sample bag and 100 ml of toluene is used to extract a pair.  If a
subject wore more than one pair, the solvent is increased only to the extent that
an aliquot can be easily removed and the actual amount of solvent is noted.
9.4  Aerosol Samples
  S  These are Millipore disposable cassettes with 37 mm membrane filters.  An
extraction bottle is chosen so that the filter can be dropped directly in from
the cartridge without handling.  Loose dust is washed off the cassette with hexane
because the plastic is soluble in toluene.  The hexane is allowed to evaporate and
the pesticide extracted with 30 mL of toluene.  The sample is stored as above
under the procedure for gauze pads.
                                                                              87

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                                                           Section No.       9
                                                           Revision No.      0
                                                           Date:    November 10, 1982
                                                           Pa ge    2     o f   4
9.5  Leaf Punch Samples
     The standard leaf punch sample consists of 48 - 3 cm leaf disks frozen in
a glass jar with a water-tight plastic cap.  After a half-hour thawing period,
the leaves are dumped into a one pint square Mason jar with the standard lid and
ring closure.  Six drops of a 20 mg/L solution of dioctyl sodium sulfosuccinate
is added to the sample jar.  The surfactant and dust are transferred quantitatively
to the Mason jar with 100 ml of distilled water.  The leaves are shaken for 30 min.
on a shaker table at about 140 Hz and the liquid decanted into a 500 ml separatory
funnel containing 50 ml methylene chloride (dichloromethane), using a narrow-stemmed
funnel to avoid transferring leaves.  The process of washing the leaf disks with
surfactant and water is repeated twice more.   Then the leaves are counted and
discarded.  The separatory funnel is shaken 30 times and the organic layer is
drained through a small funnel plugged with glass wool and filled with anhydrous
sodium sulfate into a 500 ml round-bottomed f 24/40 flask.  The extraction proced-
ure is repeated twice more with fresh 50 ml aliquots of solvent and the combined
solvent is rotary evaporated to about 1 ml.  Ten ml of toluene is added and
evaporated.   This process is repeated twice more.  The final residue is quantita-
tively transferred to a 10 mL volumetric flask and made up to volume.  The sample
is ready for gas chromatographic analysis.
     The dust which was washed from the leaf surfaces remains in the interfacial
layer in the separatory funnel.  This material is filtered onto a pre-weighed
glass fiber  filter, dried at 110°C overnight and cooled in a dessicator.  Post-
weighing of  the filter yields the foliar dust weight.
9.6  Soil  Samples
     The sample is weighed and sifted through a #10 sieve (2 mm hole size) to break
up lumps and remove rocks, twigs and leaves.   The trash is weighed. The sifted    Qg

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                                                           Section  No.        9
                                                           Revision No.       0
                                                           Date:    November 10.  198
                                                           Pa ge     3     o f   4
sample is mixed and a 250 ml portion 1s transferred to a tared beaker and weighed;
the beaker is then placed in an ambient-temperature vacuum desiccator and dried
for 24 hours or more and reweighed until the residual  moisture is less than 0.5%.
A glass soxhlet thimble is prepared by placing 1.5 cm of acetone washed sand in
the bottom to protect the extra-course frit from fouling by soil fines.  The
thimble is tared and about 30 gm of desiccated soil is added, the weight being
taken to four significant figures.  The thimble is then placed in a 250 mL soxhlet
extractor and cycled for four hours.  The solvent is azeotropic acetone-hexane
C59* - 41%).  After extraction the solvent is removed by rotary evaporation and
replaced by a solvent compatible with the analytical method to be used - toluene
for GC only, acetronitrile for GC plus HPLC.  This method is applicable only to
those low-volatility chemicals expected to be found during this study.
9.7  Urine Analysis
     A.  Captan
         Tetrahydrophthalimide (THPI) is the major urinary metabolite of captan,
     with tetrahydrophthalamic acid being a closely related minor metabolite.
     There are two analytical methods for THPI.  The former Idaho PHAP project
     developed a method (Brokopp, c.D.   Annual Progress Report, Idaho Epidemiologic
     Studies Program, EPA Cooperative Agreement, #78-CX-0363, April 1980) and a
     newer version is being published by Schoen and Winterlin (Schoen, S.R. and
     W.L.  Winterlin. "Gas Chromatographic Determination of the Captan Metabolite
     Tetrahydrophthalimide (THPI)in Urine," submitted for publication, 1982.
         The major difference between the methods is the fact that the THPI is
     derivatized for EC analysis in the former, while in the latter, the metabolite
     is analyzed as underivatized THPI on a nitrogen-phosphorous detector equipped
     gas chromatograph.  The clean-ups for the two methods diverge somewhat due to

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                                                      Section No.	9      565
                                                      Revision No.       0
                                                      Date     November 10,  1982
                                                      Page     4     of   4
the facts that they were developed for analysis on different detectors and
that they were developed in different laboratories.  We will develop the
Shoen-Winter!in method in our laboratory first, given that the elimination
of a derivatization step simplifies the procedure.
B.  Organophosphate Insecticides
    There are six alkyl phosphate metabolites commonly observed as a
consequence exposure organophosphate pesticide.  One or two of these are
possible from any given OP compound, depending on its structure.  Reid
and Watts have published a method for derivatizing these metabolites without
the use of the explosive and powerfully carcinogenic reagents (diazoalkanes)
required by older methods [Reid, S.J. and R.R. Watts.  "A Method for
Determination of Dialkylphosphate Residues in Urine."  J. Anal. Toxicol.,
5, 126 0981)].
                                                                              90

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                                                                                   c//
                                                            Section No.       10    JOD
                                                            Revision No~0
                                                            Date:    November 10,  1982
                                                            Page     i     of   5
                         10.  DATA REDUCTION, VALIDATION
                                   AND REPORTING
 10.]. Agricultural Chemical Samples
     Most samples yield four (4) data items:
     1)  Sample vol., is the final  amount of  solvent in which the
         entire amount of analyte from the sample is contained.  This
         number is determined by the technician who prepares  the sample
         and records it with the extraction date in the sample log.
     2)  Injection vol., is the amount of sample actually injected
         into the GC or HPLC.   This number is recorded  by the instrument
         operator along with the sample number on the recording tape of
         the HP3390A (GC) or the Water's Data Module (LC) Integrator,
         i.g., 2 yL of a 1:1000 dilution are  injected,  the operator
         records, inj.  vol. = 0.002 yL.
     3)  Counts per injection:  This is the area under  the peak in yV-sec.
         as determined by the integrator for  each injection.
     4)  Response factor:  This is  an arithmetical  expression of the sensitivity
         of the entire analytical system to the injection of  a standard of
         known volume and concentration and has the units- R  = C/ng.   If C~  is
         the average count for 2 or more identical  standard injections with a
         RSD < 5% then R = C~ * inj. vol. * std. cone, proof:
                          __L-x   M  v ML  = J_
                            inj  *    yL  * ng    ng
     At the conclusion of a day's run the integration record  is logged in thus:
The values for each standard are entered, averaged  and  the RSD verified.  The
response value is calculated.
                                                                                  91

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                                                            Section  No.    10
                                                            Revision No.       0
                                                            Date:    November  10.  1982
                                                            Pa ge      2    o f   5
    The sample  number,  Injection volume and the replicate peak areas are
recorded,  then the sample number 1s looked up 1n the sample log and the analysis
date recorded there, finally the extraction volume 1s transferred from the log
to the laboratory notebook.  Since we want the final result to be 1n yg of
analyte per sample the following formula 1s used:
                                                                ug
                T inj volume  T  resp factor x ext volume =   sample
Note that prior to multiplication by the extraction volume ngA± convert £§r_
acidens to yg/mL.  Proof:
     The principal criteria used to validate data integrity will be agreement
 between the records and calculations and transfer checks done by the analytical
 chemist on randomly selected samples,
     For the purpose of this study, an outlier  is defined as an analytical
 data set with a relative standard deviation greater  than 10%.  Because  several
 samples are taken from different parts of each  subject's body, the  unacceptable
 sample is held until the rest are completed and the  whole body dose calculated.
 The effect of the uncertainty on the whole body dose can then be estimated  and
 a proper decision made as  to whether the sample must be cleaned and concentrated.
     The following data flow and reporting scheme refers to  the Sample/Data
 Flowchart, Figure 10.1.
                                                                                 92

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Figure 10.1:    Sample/Data Flowchart
                                                                            568
                                                                    ro
                                                                      0
                                 Section No.
                                 Revision No."	
                                 Date: November 10. 1982
                                 Page    3     of   5
    Subject
     Data
    Sheets

    Field
  Notebooks
Sample Collection
       and
Number Assignment
        I
                  Sample
                 Storage
                 Sample
                Extraction
               Chemical
               Analysis
               Chemical
             Calculations
              Industrial
              Hygiene
              Evaluation
            Statistician
                  JL
                Samples
                              Sample
                              Log
                                              Laboratory
                                               Notebook
                            Data
                            Sheets
                              J
                          Computer

                          Work-up
                                 1
                            Final Report
Laboratory
 Archives
                                                                          93

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                                                            Section No.     10
                                                            Revision No"!       5
                                                            Date : _ November 10, 1982
                                                            Page      4    of  5
     The process begins in the field when the Industrial hygienist fills
out a field data sheet on each worker and assigns a subject number to him/her.
A specimen field data sheet is in Appendix A.  As each sample is collected a
number is assigned to it in accordance with the protocol described in Appendix
B.  The samples are placed in dry-ice chests for the trip to the laboratory.
The field data sheets and the spray history are given to the senior scientist
for later use.
     Upon arrival at the laboratory, the samples are transferred to the deep-
freeze for storage and the sample log is filled out through the storage date
column.  The Chief Chemist and the analytical chemist later verifying the log
against the samples with a physical inventory.  The samples are turned over to
the technician who organizes them by type for extraction.  As each sample is
extracted the date and volume is entered in the log and the extracts are turned
over to the analyst.  After the extracts have been run, they are returned to the
technician for storage.   The raw data is transferred from the instrument print-
out to the laboratory notebook,and the printout is dated, coded and filed.  The
extraction volume and any special data (e.g. crop weight) are entered into the
laboratory notebook from the sample log and the analysis date entered in the log
book.  The calculations are performed and the results entered in the laboratory
notebook and the data sheets (see Appendix D).  The data sheets are checked
against the laboratory notebook by the analytical chemist and given to the senior
scientist who uses the field data sheets to perform additional calculations.  The
completed data sheets are turned over to the statistician who enters  the data
on the computer and does the statistical work-ups.  The computer output and all
the data sheets finally go to the Project Director for use in preparing the
final report.                                                                _(
                                                                                   94

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                                                                              570

                                                          Section No.    10	
                                                          Revision No.      0
                                                          Date:    November  10, 1982]
                                                          Page     5     of  5	
     The field notes, data sheets, and laboratory notebooks are retained by

the senior project chemist or/and project director for seven years.
                                                                             95

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                                                            Section  No.   n     g 7 i
                                                            Revision No"!       o^ ' '
                                                            Date:    November 10.  1982"
                                                            Page       i   of  ?
                      11.  INTERNAL QUALITY CONTROL CHECKS

     As  many samples as possible are collected in duplicate.  However, the
majority of the personal monitoring samples are unique.  Leaf punch, and soil
and airborn pesticide samples are regularly collected in duplicate or more.
     In  the laboratory, method checks are conducted by analysis of replicated
spiked samples and blanks.  These method checks are employed during routine
analysis, as well  as regular calibrations described in Sections 7 and 8 of
this document.  Reagent (solvent blanks) are also a regular feature of the
internal checks employed by this laboratory.
     Replicates and frequent calibrations are the backbone of our quality
assurance program  for chromatographic analysis.  At least duplicate injections
are used whether manual or automatic sample introduction is used.  The analyst
is required to check results for each sample for reproducibility and if the
relative standard  deviation exceeds 10% (5% is the laboratory goal) then
additional  injections are required until satisfactory results are achieved.
     Spiking leaf  punches, soil  samples, and to some extent, dermal dosimeters,
will be  accomplished by the use  of pesticide-laden dust.  This material will
be formulated by dosing a quantity of pre-sieved soil dust which has been
checked  for freedom from residues of the compound(s) of interest.  In this way
a supply of dust carrying a known and verified concentration of pesticide(s)
can be kept on hand for spiking  into the various substrates which will be analyzed.
A supply of unspiked dust from the same source will  be kept on hand for blanks.
     This technique offers advantages over spiking pesticides carried in organic
solvent, especially in the case  of checking foliar dislodgeable residue
methodology.
                                                                                  95

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                                                                                  572
                                                           Section No.    n
                                                           Revision NoT      0
                                                           Date :   November 10, 198
                                                           Page _ 2_of__2
     The schedule of internal quality assurance samples to be run varies
for different types of samples.  The bulk of the samples to be analyzed are
dermal pads.  They are run in batches of 30 samples at a time and two of
those samples will be either a blank and a spiked blank or two spikes.  Since
aerosol samples are extracted and analyzed in an identical fashion as gauze
pads, they will be included with the gauze pads for quality assurance purposes.
     Since soil sample processing is not consistently a batching process,  a
target of 10% of those processed will be QA samples.   Leaf punches are run in
batches of up to fifteen samples in number, and one of each batch, at least,
will be either a blank or a spiked blank.  Since only two or three vapor traps
are extracted at a time, at least one spiked blank will  have to be included in
the process.
     The results of these quality assurance sample analyses will  be accumulated
in a laboratory notebook especially set aside for this purpose.   A summary of
these results will be reported monthly along with the regular monthly reports
forwarded to the EPA project officer.
                                                                                  96

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                                                                           573
                                                          Section No.    12
                                                          Revision No.      0
                                                          Date:    November 10.  198T
                                                          Pa ge	]_p f   i	
                            12.  PERFORMANCE AUDITS

     A plan  for external performance audits 1s currently being developed
with the  cooperation of the chemists at the Pesticide Hazard Assessment Project
located at the University of Iowa, and under the guidance of our Project
Officer.  When this plan 1s complete*it will be forwarded for inclusion in
this document.
                                                                                  97

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                                                           Section No.     13     574
                                                           Revision No.      0
                                                           Date;   November  TO, 1982"
                                                           Pa ge	L__° f_2	
                           13.  PREVENTIVE MAINTENANCE
13.1  Field Equipment
     Generally, cleaning and recalibration (for air sampler pumps) provides
project personnel an opportunity to inspect field sampling equipment for
deficiencies before use.  Leaf punches require sharpening at long intervals
(dnce every two or three seasons) in order that they continue to cut the tough
fibers in xeomorphic leaves (e.g., citrus).  This is performed  on an as
needed basis.
13.2  Laboratory Equipment
     The analytical balance used by the project received an annual cleaning
and recalibration (see Section 8).
     Gas chromatographs are maintained in the following ways:  All carrier
gases are passed through moisture and oil traps to prevent fouling the columns
and detectors, and the trap elements are changed every four (250 SCF) cylinders.
Carrier gas intended for electron capture detectors is passed through an oxygen
scrubber, as well, which is changed after six cylinders of gas have passed
through it.  Electronics are checked by performing an electrometer zero and
noise check monthly or whenever a new method is set up.  The voltage profile
for the ECD is also checked and recorded.
     The digital integrator-printer-plotters used by the project perform a self
check every time they are turned on.  They require a cleaning of paper debris
each time a new role of plotter paper is installed.
     The auto sampler is operated on compressed air which is passed through
a particulate and water trap before use.  The performance of the auto sampler
is checked daily by careful examination of results obtained from calibration
standards and solvent blanks which are interspersed among samples.           •-

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                                                           Section No.   13
                                                                               I	71"
                                                           Revision No.      o J / J
                                                           Date:   November 10, 1982"
                                                           Pa ge     2    o f2	
     The liquid chromatograph automatically does a self diagnostic test when
powered up.   Solvents are prefiltered through a 0.22 y filter to prevent
particulate  damage to the system.
13.3  Spare  Parts Inventory
     Air monitoring pumps use rechargeable battery packs, which periodically
fail, so spare battery packs are kept on hand.
     The gas chromatographs have spare EC power supplies (3), a fan motor,
                                                                     \
heater cartridges for detectors, and injectors and an FPD igniter coil.   There
are three spare tritium ECD cells of unknown condition.  Regular supplies such
as septa, columns, and packings, are procured as necessary on an ongoing basis.
     The integrators have ho spare parts, except the thermal  printer/plotter
paper they consume.
     The auto sampler is backed up with extra syringes and needles, air filter
cartridges and consumable (vials, caps, and septa).
     The liquid chromatograph has a spares kit supplied by the manufacturer
which is kept up when pieces are used.
                                                                                99

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                                                                               576
                                                           Section No.   14	
                                                           Revision No.      0
                                                           Date:   November 10. 198T
                                                           Pa ge	L__° f   ?	
              14.  SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA
                       PRECISION, ACCURACY AND COMPLETENESS

14.1  Field Sampling
     Standardized sampling procedures are employed to assure accurate
environmental monitoring (i.e., respirable dust and pesticides,  dislodgeable
residues, soil residues, crop residues, and meteorological  conditions).   The
patch technique used as a dermal dosimeter is unproven, although it is^ generally
accepted as the best technology available at present.   Therefore, the accuracy
of the data generated by the technique is unknown.
14.2  Laboratory Analyses
     All chromatographic analyses are run at least in duplicate.  Relative
standard deviations are calculated and any samples giving greater than 10% RSD
are re-analyzed.  At the discretion of the analyst, a lower RSD  criterion may
be used.  The general precision goal for the laboratory is  five  percent.
Standards are weighed by the most experienced chemist in the group.  Working
standards are cross-checked against one another.
     Calculations are recorded in the laboratory .notebook  assigned to the
project and are double checked by the analyst as he/she performs them by  re-
calculating every third or fourth sample.  The data is then triple-checked by
another person by their recalculating 10% of the samples.
     An absolute quality criteria is used independent of any statistical  test,
viz., any recovery and duplicate analyses not meeting the objectives specified
in Section 5 will cause the corrective actions described in Section 15 to be
initiated.
                                                                             100

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                                                           Section No.   14     577
                                                           Revision No.       0
                                                           Date:    November 10,  1982
                                                           Page    2      of   2
14.3  Further Data  Reduction
     Results  1n  term of mass of target chemical  (pesticide)  reported  by  the
laboratory are then transcribed into computer-readable  format  for  further
calculations.  This operation is also double  checked  either  on a 10%  or  100%
basis depending  upon the computer employed.   Finally,the  results are  tran-
scribed onto  appropriate data sheets and forms  as  indicated  by Appendices F
through J  for aerosol,  leaf punch, soil, crop,  and meteorology data,
respectively.  The  dermal  data reduction sheet  was previously  shown in
Appendix D.
                                                                            101

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                                                           Section No.    15       578
                                                           Revision No.      0
                                                           Date:   November 10. 198JT
                                                           Page	i   of   i	
                              15.  CORRECTIVE ACTION
     Whenever any evidence appears to indicate trouble or insufficiency  1n
sampling, analytical or data reduction activities or equipment,  efforts  are
mounted to trouble shoot and correct any problem to the satisfaction  of
responsible project personnel.   Specific procedures depend upon  the nature
of the problem and the ability of the personnel  dealing with  it  to interpret
the symptons.
     Acceptable limits for the performance of equipment, and  thereby  the data
produced by it, is described in other sections of this document.  The res-
ponsible person for initiating corrective action is that person  who detects
the problem, be it malfunctioning equipment or data that does not appear
correct or consistent.   Of course,  the ultimate  responsibility lies in the
hands of the Chief Chemist and  the Project Director.
                                                                                  102

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                                                           Section  No.    16      579
                                                           Revision No.      0
                                                           Date:    November 10. 1982
                                                           Pa gei	of    i	
                16.   QUALITY ASSURANCE REPORTS TO MANAGEMENT

    Quality  assurance  results will be accumulated  1n a QA notebook.  These
results will  be  summarized  1n the  Monthly  Report format which  1s sent to the
PHAP Project  Officer (see Appendix E).  Monthly reports are prepared jointly
by the Project Director and the  Chief Chemist.
    The  final report will  Include a QA section which summarizes the Monthly
Reports and discusses any QA Issues which  come from an analysis of the'QA
data.
I
                                                                             103

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                                                                    Date:   10 November  1982
                                                                    Page      1     of   1
                                   University of California
                                   School of Public Health
                        Biomedical  and  Environmental Health Sciences
                                    Berkeley, CA  94720
                                                                                        580
                                Field  Personnel Sampling Form
une and Number of Experiment:

tte of Experiment:

             Subject  Name
                                             Subject  Number     Sex    Age    Weight    Height
iration  of Exposure:

      Time In:           Time Out:
                                           Time  In:
                                                            Time Out:
Total Hours:
lothing Description  (type,  parts  of body not covered, hat, etc.):
    Habits:   (Working  position, observed foliar contact, etc.)
lusual  Observations:
amp!ing Patches (Nos.):
                                                              Pump No.:
ead       	
hest
ack       	
pper arm  	
Dwer arm  	
pper leg  	
Dwer leg
jnds (glove?]
ther
                (L)
                (L)
                          (R)
                          (R)
                                                              Collector Type

                                                              Flow Rate:
                (L)        (R)
                                                                                      m3/hr
                                                       Name of Recorder (Observer)

                                                                   .     104

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                                                           section HO. Appendix  B
                                                           Revision No.     0
UCB SAMPLE IDENTIFICATION CODE                             Date:  10 November 1982
                                                           Page     1     of   1
                                                                                  581,
Year (a)      Plot (b)       Sample  Type  (c)     Days Post-     Replicate (e)
                                               Appl. (d)
(a)  Last two digits  of year,  e.g.,  80,  81, or 82
(b)  Plot number (2 digits)  assigned by  project supervisor
(c)  Sample Type
     A = aerosol
     C = crop sample
     P = punch sample
     S = soil
     V = charcoal  or  other vapor collector

     Patches, etc.
     H = head                     Ch =  chest
    UA = upper arm                UL =  upper leg
    LA = forearm                  LL =  lower leg
    St = stomach                  Sh =  shoulder
                                  LB =  lower back
(d)  Days post application,  0  =  day  of application, 1 * first day after,  etc.,
     (PA is preapplication).
{e)  Replicate number for  duplicate  sample, different people, etc., as necessary
     and recorded  in  field notes.
                                                                           105

-------

               O   %=
               t—i

               S   J3
              Laboratory Sample
0) 0>
•U O)
 u.   o  •
<-i o
• r j "-








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go/31

%DI3£

%OI3fl




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:

















MS

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.

on

w F

HA*\























Z

IH

2£OL





















••••

1-12

7-/z

T-/2.





















.

7~/3
-
7-7?

7-/S























$-£

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$-/(,






















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$-7

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-------
                                                               Section No.  Appendix  p
                                                               Revision No.     0
                                                               Date:  10_Noyember 1982
                                                               Page _
1
of   1
(7/81) DERMAL DATA SHEET
                                                                                   583
STUDY:
DATE:
LAB LOG:
(b)
chen. mass



*
pads



(c)
time
COMPOUND:

Pad Area:
(d)=(a)(c) (e=(b)/(d)
hr-cm2 rate density

cm2 (a)
(f)
LOC AREA

(h)=(e)(f)
rate
{cation/ ID
• HD
• neck
*
' SH
• BA
**BA
' CH
St
**CH
hips
UL
LL
«>
*
feet
UA
LA
GL
( 9)

















n

















hours



































( q/hr.cm2)

















cm2
1075
230
*1300
1305
1540
**2190
1540
720
**2190
1750
3460
2590
*6050
1230
1860
1290
1075
( 9/hr)
•
















    Indicates area as  sum of previous two locations.

    Areas to be used where no shoulder or stomach pads included.
                                                                               107

-------
                                                                   Date:  10 November 1982
                                                                   Page     1     of   1
                                               Date Report Prepared:
                             MONTHLY LABORATORY STATUS REPORT
                                                                                          584
-ticipating  Pesticide  Hazard Assessment Projects
ile of Study/Investigation:	
-1od of Report:	
to
Substrate
(List chemical residue
to be analyzed for
or
test to be performed)







Number
of
Samples
on
Hand






\
Number
of
Samples
Received
or
Collected
During

Report
Period


Total
Number
of
Samples
to be
Analyzed






Number
of
Sampl es
Completely
Analyzed
During
Report
Period




Numbers
of
Samples
Remaining
to be
Analyzed





j

-------
                                                                 section no. appendix
                                                                 Revision No.     0
                                                                 Date:  10 November  1982
                                                                 Page     1     of   1
                      STUDY/INVESTIGATION MONTHLY STATUS REPORT


*Title of Study/Investigation:	
 Participating  Pesticide Hazard Assessment Project
 Period of Report	to .	Prepared by

 Cognizant HEB  Staff Member	
iI.  Ltst Tasks  Completed During Report Period:
II.  List Tasks Started on Schedule During Report Period:
 II.  Tasks Behind Schedule:
 IV.  Why are Tasks  Behind Schedule? - Account for each Task:
 V.  Action  or Assistance Needed to Complete Tasks - Include New Start and/or
    Completion Dates.
                                               Date Report Prepared:	585
I
                                                                                      109

-------
                                                     	10IX
                                           Revision  No.	
                                           Date:   10 November 1982
                                           Page      1     of
                          1
          University of California
          School of Public Health
Biomedical  and  Environmental Health Sciences

            Aerosol Data Form
                           586
Study ID#
/Chemical
VOL
PERSONAL ID# SAMPLE ID# TIME AIR (L)
"







































DUST
CONC.
Wt(mg) mg/m3




















PESTICIDE
CONC.
Wt( g) g/m3




















POOLED
GROUPS

>








                                                             110

-------
                                                                Section No.  Appendix  H
                                                                Revision No.     0
                              University of California           Date:   10 November 1982
                              School  of Public  Health            Page
                     Biomedical  and Environmental Health Sciences
                                       T
     of    1
                                                   587
                                 Leaf Punch  Data  Sheet
                    Study ID*
                          /Chemical
                             (Area of 3 cm punch  =  7.07 cm)
I.  Preapplication Samples:

                        f OF
    SAMPLE ID#   DATE  PUNCHES
AMOUNT OF              99
PESTICIDE  CONC.  yg/cirT   DUST mg/cnT
CONC. ON
DUST, ppm
II. Post Application
1. Interim Decay Samples
# OF AMOUNT OF ? ? C0fi;c- ON
SAMPLE ID# DATE PUNCHES PESTICIDE CONC. pg/cnT DUST mg/cnT DUST, ppm




























2. Field Study Samples
f OF AMOUNT OF 22 CONC' OI>!
SAMPLE ID# DATE PUNCHES PESTICIDE CONC. yg/cuT DUST mg/cirf DUST, ppm













•














3. Post- Field Study Samples
f OF AMOUNT OF 22 CONC* ON
SAMPLE ID# DATE PUNCHES PESTICIDE CONC. yg/cnT DUST mg/cm DUST, ppip



	 	























11

-------
                                                                                         T
                                                                   Revision No.      0
                                    University of California       Date:   10 November 1982
                                    School of Public Health        Page
                          Biomedical and Environmental Health Sciences
                                        1
                                    of
                          Study  ID#_
                                       Soil Sample Data Sheet
                                     (Area per scoop = 77.4 cm )
. Pre Application Samples
NO. OF SOIL * AMOUNT OF CONC.
SAMPLE ID# DATE SCOOPS WT.(g) H20 PESTICIDE vg/cm2 PPM











,




'II.  Post Application
     1.  Interim Decay Samples
                            NO. OF   SOIL
     SAMPLE  ID#       DATE  SCOOPS  WT. (g)
            %
           H20
       AMOUNT OF
       PESTICIDE
                 CONC.
                vg/cm2
                  PPM
      2.  Field Study Samples

                            NO. OF
     SAMPLE ID#      DATE   SCOOPS
 SOIL
WT. (g)
 %
H20
AMOUNT OF
PESTICIDE
 CONC.
yg/cm2
PPM
      3.  Post Field Study Samples
NO. OF SOIL % AMOUNT OF CONC.
SAMPLE ID# DATE SCOOPS WT. (g) H20 PESTICIDE vg/cm2 PPM





-


























                                                                                        112

-------
                                                             Section No.  Appendix  j
                                                             Revision No.      0
                           University of California          Date:   10 November 1982
                           School of Public Health           Page     1      of    1
                  Biomedical and Environmental Health Sciences
                              Crop Sample Data Sheet

                    Study  ID#	/Chemical
589
Preapplication  Samples

                         NO.  OF
SAMPLE ID#       DATE     FRUITS     FRUIT WT.  (g)     PESTICIDE (  g)  yg/cm2
 PPM
Post Application
1.  Interim Decay Samples
NO. OF
SAMPLE ID# DATE FRUITS FRUIT WT. (g) PESTICIDE ( g) yg/cm2 PPM




























2.  Field Study Samples
NO. OF
SAMPLE ID* DATE FRUITS FRUIT WT. (g.) PESTICIDE ( g) yg/cm2 PPM




























                                                                              113

-------
                       University of California
                       School of Public Health
           Biomedical and Evironmental Health Sciences
                    Meteorology Data Form
                                                                          0
           Study ID#
           Section No._
           Revision No.
           Date:    November 10.  198T
           Page	
                                                                      of
                                590
      M     D    Y

DATE     /    /
                         Wind
Temperature
AVG.
TIME *DIRECTION SPEED





















RANGE
FPM







HUMIDITY
WET F .DRY F %














\






SUN CON-
DITION







    *NOTE  relation to work operation
                                                                      114

-------
          APPENDIX B



CORRESPONDENCE REGARDING URINARY



      METABOLITE ANALYSES

-------
                                                                592
                                      14 December 1984
Dr. Geraldine Fristrom
FSSP Laboratory Coordinator
EAB/HED/OPP  (TS-769-C)
United States Environmental Protection Agency
401 N Street, SW
Washington, D.C.  20460                           RE:  CR-810691-02-0

Dear Gerrie:

      Your letter of 10 October 1984 was appreciated; it is essen-
tially correct.    Here is a summary of progress to date.

      Save for  some  ironing out of a few  minor  quality assurance
issues, I feel  that we have run the benomyl environmental  and person-
al samples in sufficient numbers to  know exactly  what  we have.  All
of the 8301 and 8302 glcve samples were positive, though low.  The
8301 samples ranged  from about 50 to 1000 micrograms,  while the 8302
?loves were 200 to 2000.  Recall  that the gloves from  the  strawberry
 ields where benomyl was  applied ran in the vicinity of 10 to 30
milligrams.   A selection of 48  patches from the 8302 study  (40%)
resulted  in  no detectable (not  "too low to quantitate") residues.
All the air  samples from  both  the  studies  gave the same result.
Finally,  all the  leaf punch samples from  the two benomyl studies
(8301 and 8302) have been completed, along with all the  associated
quality assurance  samples.

      I feel  that we could safely expect that  there is  no  further use
in analyzing any more of the patches.  The indications  to  me are that
there will probably be no detectable metabolites in  the urines, as
well.  However, as we have discussed by telephone,  John Tessari's
laboratory  will select a few samples based  on  the glove data and
verify this prediction.

     The  mesurol urinary  metabolite method that we have been putting
together  has proved itself reasonably reliable with spikes and stan-
dards, so far; and, although it  is getting  close  to the deadline, I
remain optimistic  that we will be able to complete that  task satis-
factorily.  Only one experiment  remains to be  done before the actual
samples go into  the system.  That one is  to  determine whether or not
we must hydrolyze  conjugates as  a first step in the sample work-up.

      I looked into  the  issue of instrument rentals.   It turns out
that there is one major purveyor of rental equipment  in this area,


                                                               116

-------
                                                                  593
Dr.  Geraldine  Fristrom
Page 2
14 December  1984
named USI;  and they handle most major manufacturers.   When one  looks
at short-term  rentals, as opposed to leases of a year or more (usual-
ly with purchase options),  there are some interesting,  though  logi-
cal,  restrictions applied.  If one goes into a long-term arrangement,
you can get a  system configured any way you want,  because  the lessor
will go out and buy exactly what you stipulate.  On the other  hand,
the short-term renter takes what they have "on the shelf."   What they
stock for rental customers  is the  top of the line equipment.  This
way, they minimize their inventory; the fanciest equipment is the
most versatile,  and that minimizes their  capital outlay. Anyway, the
upshot of all  this is that it would cost us approximately  $1700 per
month to rent  a High Pressure Liquid Chromatograph to do the analyses
we presently are carrying out. That is at the academic rate of  5% of
the retail price per month instead of the 10% charged to industrial
clients.

      That is  generally quite a  bit more than I have been  paying in
for the upkeep of the present  equipment.   I do not see  being able to
afford such an expense,  and  the machines have hung in there the last
few months with only minor troubles.

      I spoke  with Dr.  Zweig some time back,  now,  and he informed me
that he will  not be working under Dave Severn;  rather,  he is now
assigned to a one-year project in Registrations.   That  creates a
problem here in the final report department, because, as I pointed
out previously, there  is no way of our  getting these analyses all
completed in time to have final reports written prior  to  the termina-
tion date.  I  am sure that no one has a taste for these data  to go
uninterpreted.  Dr. Spear and I have discussed this issue,  and we
have agreed to submit a request  for a no-cost extension under sepa-
rate  cover.

     Bowever,  the funds are,  in fact,  coming out close to the budget,
and it certainly would  improve the  situation here if there could be
some supplementary  funding from  the PHAP program to facilitate the
last steps of  finishing the reports  and seeing to the transfer of
equipment to Jim Seiber's shop.

                             Sincerely
                             John T. Leffingwell, Manager
                             California PHAP
cc   B.C. Spear
                                                               117

-------
                                                                 594
                                       17 December  1984

Dr. Geraldine FriStrom
FSSP Laboratory Coordinator
EAB/HED/OPP  (TS-769-C)
United States Environmental Protection Agency
401 M Street, SW
Washington, D.C.  20460                        RE: CR-810691-02-0
Dear Gerrie:
      Attached  is a preprint of a manuscript titled, "The Rela-
tionship Between  Dermal  Pesticide  Exposure  By Fruit Harvesters
And Dislodgeable Foliar  Residues."  It will  be appearing shortly
in The. Journal o_f Environmental Science and Health. P_ajLt B.  It
contains a wrap-up of much of the work that  we have conducted
under the aegis of the Youth in Agriculture program, summarizing
most  of  the dermal exposure data collected over  the last four
years.
      Incidentally,  the Mesurol  (methiocarb) dermal  data  is
included in this paper, and the write-up will  serve as the basis
of our final report on the 1983 blueberry study.
                             Sincerely
                             John T. Leffingwell, Manager
                             California PHAP
                                                                118

-------
                                                                  595
                                      11 January 1985
Dr.  Geraldine Fristrom
FSSP Laboratory Coordinator
EAB/HED/OPP   (TS-769-C)
United States Environmental Protection Agency
401  M Street, SW
Washington, D.C.  20460                       RE: CR-810691-02-0

Dear Gerrie:

     Developments in the matter of mesurol metabolite analysis
are  such that I deem it desirable to report them to you in some
detail and seek relief in the deadlines we  face at present.

     As you know from previous telephone conversations and cor-
respondence, we were required in 1983 to change the proposed work
plans which we had submitted to the NPHAP staff to  drop the idea
of doing more  work  on strawberry harvesters in favor of workers
in three other berry crops.  This meant that we would have to
focus on populations of workers and  crops that  were quite distant
from our laboratory and of which we knew  almost nothing.  The
consequence was that  almost all control  over  such  critical fac-
tors as the  choice of the field site  and the  timing of  our
studies in relationship to pesticide applications  was lost  to  us.
In fact, when we  left for Oregon in July 1983, we even had not
been able to determine what pesticides we would be working  with.

     As good fortune  would have it, the blueberry grower who was
cooperating with us happened to be treating one plot of his farm
with mesurol just days before we were to begin our  study, and he
allowed our group of  harvesters to work in that newly treated
plot (it was  a legal  reentry).  In  due  course we collected the
urine samples according  to the approved  protocol,  along with
other personal and environmental samples needed  to complete the
study.

     Since we did not  know what pesticide(s) to expect, we could
not  have methods of  analysis developed and  in place at our labor-
atory before  the  collection of samples.  Consequently, we pre-
served the  urine samples in a manner consistent with our previous
experience; namely, we took 20 mL aliquots of the urines, dosed
them with  1.5  mL  of concentrated hydrochloric acid and sealed
them in 25  mL ampules.  This  style of preservation had worked
excellently for urines containing p-nitrophenol.
                                                             119

-------
                                                                596
 Dr. Geraldine Fristrom      Page 2              11 January 1985


      Alternate methods of preserving  urine samples were  not
 acceptable to roe.  The use of  sodium fluoride would cause severe
 problems  with subsequent acid  hydrolysis of conjugates.   The  use
 of .thymol promised  to give  massive  interference in the analysis
 of  phenolic metabolites  (such  as  those of mesurol).  And, we
 could not handle the  logistics of  freezing, shipping and storing
 the hundreds of urine samples that  were to be  generated in  the
 1983  studies.

      This last Fall, as you already know, we began development
 work  on an analytical method to deal with the realities  of roes-
 urol metabolism  {It leads  to three related phenols:  3,5-dimethyl-
 4-methylthiophenol,  3,5-dimethyl-4-methylsulfinylphenol  (the
 sulfoxide) and 3,5-dimethyl-4-methylsulfonylphenol  (the sulfone),
 reflecting step-wise oxidation of  the  sulfur.} and  the  (acid)
 state of  the one hundred plus samples on hand.  My approach was
 to oxidize the three metabolites all to  the last one and analyze
 for it by HPLC.

      The development process started  from  the  sulfone; with
 standards from the manufacturer in hand,  we first  confirmed that
 we  could analyze that compound by HPLC.  then,  we worked on
 oxidation procedures that  would take the methylthioether  and  the
 sulfoxide to the sulfone.   Finally, having done that, we had to
 anticipate that these phenols could be present in the urines as
 conjugates with  glucose or  sulfate and would require  hydrolysis
 prior to analysis.   This is the stage where we were just prior to
 the Christmas break.

      It  was possible that  conjugate hydrolysis had already  oc-
 curred spontaneously during the samples' standing for over one
 year at a pH of less than 0.1.  The only way we could test for
 the necessity of a  hydrolysis step was to heat an aliquot  of one
 or more actual samples and compare them  to aliquots that had not
 been subjected to this treatment.  The results of that  experiment
 was zero  in all  samples, even the spikes run  for quality assur-
ance.   Subsequent experiments  with  spiked  samples,   including p-
 nitrophenyl-p-D-glucuronide  and  p-nitrophenyl sulfate as  surro-
 gates, showed that  the hydrolysis of the conjugates works per-
 fectly;  however, serious,  if not complete, loss of  the sulfoxide
and sulfone occurred (0 to 40% recoveries,  respectively).

      A review of the chemistry of this  type of sulfur compound
 indicates that  treatment  with strong acid causes the aromatic
 carbon-sulfur bond to  be hydrolyzed,  such that we could expect to
have 3,5-dimethylphenol as  a product  (either conjugated or not).
To confirm this hypothesis, samples of  acid-treated standards
have been submitted to the analytical services laboratory  of  the
College  of Chemistry  on the Berkeley Campus for GC-MS analysis.
We are expecting results back by the  middle of this  month.
                                                                  120

-------
Dr. Geraldine Fristrom       Page  3               11 January 1985


     The set-back that this development represents means that  we
are nearly back  to  square one in the analysis of the mesurol
metabolite  samples.   If our  hypothesis holds,  and 3,5-dimethyl-
phenol  is our analyte,  there is a whole new set of parameters  to
pin down.   What method  of chromatography (gas or liquid)?   If
capillary gas chromatography is the separation method of choice,
what  detector?  This compound has  no substituents that are amena-
ble to detection with the BCD, FPD or NPD,  and would require
privatization with  a  halogen  or  phosphorous containing reagent.
Will  clean-up be required to  remove interferences?

     To resolve these questions and  run the pending  samples,  we
will need time beyond our current  ending date of 31 January  1985,
as well as  salary and supply  money  for  the laboratory personnel
who will be needed to complete the work.   If all  the steps fell
into place, the minimum time  to implement a method would be a
month form now.   Analysis of the  samples would take another
month.  A reasonable estimate of  completion of these  tasks  would
be the  end  of March 1985.

                            Sincerely
                            John T. Leffingwell, Manager
                            California PHAP
cc  R.C. Spear
    Marion Lentz
                                                                   121

-------
                                                                598
                                       24 January 1985
 John Tessari, Manager
 Colorado Pesticide Hazard Assessment Project
 Colorado State University
 Fort Collins, CO
 80523

 Dear John:

      Enclosed are three standards for your use in working with
 the analysis of Benomyl urinary metabolites:   Carbendazim and
 benomyl from the  EPA Standards Repository,  and 5-hydroxy-2-benz-
 imidazolecarbamate from du Pont.   The  later is  the metabolite of
 interest,  although,  I am  surprised that the carbamate moiety is
 still intact at the 2 position.

      The first two are different forms of  the active  fungicide;
 benomyl  decomposes  rapidly in  the environment and  in protic
 solvents,  as well, to carbendazim.   Carbendazim  can be converted
 to  benomyl by reacting  it with  n-butylisocyanate. This technique
 is  useful  in manipulating  these compounds for HPLC analysis;
 benomyl elutes substantially later  than carbendazim on a reverse
 phase C18 column, and  changing the elution time of the analyte
 has been useful  in eluding interfering  peaks.   I  presume  that the
 same reaction would go with the 5-hydroxy-2-benzimidazolecarbam-
 ate.  For  the carbendazim/benomyl analysis, we use an acetoni-
 trile-water mixture (65:35) @ 2.0  ml  per minute on a 25 cm Cj
 column.  The butylisocyanate has to be present in the sample a
 about 2 to 5 ppm  to maintain the compound as benomyl.  Detection
 is by UV at  292 nro.
                                             •
     Good  luckl

                             Sincerely
                             John T. Leffingwell, Manager
                             California PHAP
cc:  G. Fristrom
Tessari2.1tr                                                     122

-------
                                                                  599
                                       25 January 1985
Dr. Geraldine  Fristrom
FSSP Laboratory  Coordinator
EAB/HED/OPP  (TS-769-C)
United States  Environmental Protection Agency
401' M Street,  SW
Washington, D.C.  20460           RE:  Mesurol Metabolite Analysis

Dear Gerrie:

      The answer has come back from  the GC/MS  lab that the only
thing found in the  treated standard we took them was a dimethyl-
phenol.   Given that we started with 3,5-dimethyl-4-methylsulfin-
ylphenol,  it is  reasonably  safe to  infer that the product of the
decomposition  is 3,5-dimethylphenol.

      Since we have been following  Reed  and Watts'  method for
urinary  alkyl  phosphates  using pentafluorobenzylbromide  (PFBB) as
a derivatizing reagent in conjunction with our work on the fluor-
escent tracer  project, and  since  PFBB is reputed to be an excel-
lent derivatizing  agent  with  phenols  for electron capture detec-
tion, we  have undertaken  to develop a  method utilizing  this
reagent.

  •  As way of background, 10 mL of the acidic urine samples will
be diluted with 5 mL of  water and heated to liberate any conju-
gates.   The 3,5-dimethylphenol will be extracted into methylene
chloride.   The derivatization  reaction is carried out in a polar
solvent, such  as an alcohol, acetone or acetonitrile; so, we will
convert the methylene chloride to acetonitrile.  Catalysts for
the reaction are solid anhydrous potassium carbonate and 18 crown
6 ether; the former generates the potassium salt of the phenol,
while the  later  solvates the  potassium ion  away from the phenol-
ate ion, promoting its reactivity  toward the benzylbromide.

      Before he  started,  Mr.  McLean contacted a technical person
at Supelco, our  supplier  of PFBB, to  obtain advice on approaches
to removing the  unused derivatizing  reagent from a sample after
reaction with  the analyte of  interest has  been  completed.   PFBB
is a  neutral molecule; and,  as such,  cannot be separated from the
derivative of  the phenol by commonly employed  extraction tech-
niques,  such as  manipulation of  pH or use of adsorbents to dif-
ferentiate  between  polar  and  non-polar species.   Furthermore, it
is highly  electron  capturing  (response factor of about 10 counts
                                                                    123

-------
                                                                    600
Dr. Geraldine Fristrom       Page  2               25  January 1985


per femptogram on our GC at present), and it will be present in
great excess over the analyte of interest.  Therefore, an unusual
approach is needed in order to  utilize this reagent with an BCD
that was not needed with the alkyl phosphate analyses using the
flame photometric detector.

     The Supelco person  recommended that we use a strong cation
exchange resin in the acid form.  The free PFBB would react with
the benzene sulfonate  groups on the resin and would  be, thereby,
removed from the sample.  The Supelco person had in mind that we
would use that company's disposable solid phase  extraction/clean-
up cartridges loaded with HPLC-type strong cation exchange pack-
ing.   Since  we  did not have this item  in  hand ($2.00  ea.  in
packages of 50), but  did have a  good quality cation  exchange
resin  (Bio-Rad AG  50W-X8).  For ease  of  sample handling,  we
decided to  try the resin as a slurry, rather than  in  a column.

     It did not work.   No matter  how much resin was put in the
sample, no reduction in the quantity of PFBB was seen.  We even
set up a resin column,  and saw no reduction.  So,  back  to our
contact at  Supelco, and his reaction was that he had assumed that
we would be working in an aqueous medium.  Now,  he and another
person at Supelco have given us  a  new procedure.

     The treated sample in  acetonitrile  is to be diluted  with
water and extracted with hexane.  The hexane  extract  is to be put
onto a silica gel  extraction/clean-up cartridge,  eluted  with
additional hexane to remove all  PFBB and then eluted with 20%
hexane in toluene to elute the derivatized phenol.  Mr. McLean is
attempting  this new procedure as of this writing.

     If you think that  there is  a particularly knowledgeable
person within EPA or the NPHAP group,  I would be glad to  talk
with them by telephone.  I am afraid that by the  time copies of
this letter get around, and interested  parties take time  to
respond *ith their  ideas,  it will be  much too  late for  us to
effectively put them into practice. Give me a call when you have
read through this  and have an idea or  two about  people I might
contact directly for additional  suggestions.   Thanks.

                             Sincerely
                            John T. Leffingwell, Manager
                            California PHAP
                                                                 124

-------
                                                                601
                                       14 March 1985
Dr. Geraldine Fristrom
FSSP Laboratory Coordinator
EAB/HED/OPP   (TS-769-C)
United States Environmental Protection Agency
401 M Street, SW
Washington,  D.C.  20460                       RE: CR-810691-02-0

Dear Gerrie:

      It has been some time,  now, since we last talked by tele-
phone.   I did promise you an update on the Kesurol  urinary meta-
bolite methods development work.

      As explained  in  earlier correspondence,  we had developed a
method  for  the  analysis of  mesurol metabolites  based on the
literature,  which indicated that the compounds to be anticipated
were threefold:   Mesurol phenol (3,5-dimethyl-4-methylthiophe-
nol),  the sulfoxide (3,5-dimethyl-4-methylsulfinylphenol) and the
sulfone (3,5-dimethyl-4-methylsulfonylphenol).  The  last step in
the method development showed that not only did real samples lack
any of these phenols, but spiked blanks  lacked  them,  as well.  A
review of the chemical literature on sulfur containing phenols
led us to believe  that  the strong acid  conditions we used to
preserve the samples  cleaved  the  sulfur-carbon bond at the ring.
Subsequent GC/MS analysis of  a  treated spike  confirmed that
hypothesis.

      Work on a second method was undertaken during January, but
had to be terminated when Mr. McLean had to be  laid off due to
lack of funds. The  approach we were taking was to derivatize the
3,5-dimethylphenol with something  that would  allow  it  to be
analyzed  with a  gas chromatograph equipped with an element-
specific  detector, eg. electron  capture or flame photometric
detectors.   The ultra-violet  spectrum of  3,5 dimethylphenol did
not give any distinct peaks at  which we could set the variable
wavelength detector for the HPLC,  rendering that analytical tech-
nique of  questionable applicability for  this problem.

     Since we have  had relatively good success  with the use of
pentafluorobenzylbromide in conjunction with the malathion uri-
nary metabolite work  that we have been doing of late, we decided
to give that a try; we were fairly familiar with its chemistry
and we had a stock  of  the necessary  reagents on  hand.  However,
                                                                  125

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                                                           V  602

Dr. Geraldine Fristrom       Page  2                 14 March 1985


contrary to the malathion metabolite work,  which was done on the
flame photometric detector,  this work would be done on the elec-
tron capture detector; and we would have to devise a scheme to
purge the samples,  once treated, of  excess reagent,  which, itself
is extremely electron capturing, and renders the detector useless
for hours if passed through it in  any  quantity.

      As described in earlier correspondence, we sought advice
from our supplier  (Supelco) on approaches to handling this prob-
lem, since they tout the material as a good derivatizing agent
for phenols.   Most  of  the  problems  were  worked out successfully
using blanks and spikes, and we had a reasonably  good clean-up
for clean  samples  with about a 90% recovery.  However, at the
point where we had to terminate our work we were experiencing
disturbing  occurrences of excessive contamination in  a large
proportion  of our blanks.   The few  spiked urines we had attempted
to run through the procedure had chroroatograms similar to the
contaminated blanks making it impossible  to tell whether  the
urines were contaminated  as well, or whether the  procedure was
simply inadequate for treating urine samples.

      Under the circumstances, the only position that  I  could
take was that we might have a usable method, but that it is quite
possible that  more or different  clean-up  would  be necessary.
Worse yet,  an entirely new approach  to the problem might be
required i_f what we saw in the spiked urine was not an artifact
similar to what had appeared in many of the blanks.

      At this point, I think it is  urgent  that we discuss whether
or not I will be taking  the  samples to John Tessari in Colorado.
Time is running short for  me in the near  future, since  I  will be
leaving  for  a field study  late  in May.   I  have most of  the
reagents in hand for continuation  of the  Mesurol methodology, if
the chemists at the Colorado PHAP  wish  to  continue along  that
line.

                             Sincerely
                            John T. Leffingwell, Manager
                            California PHAP
cc:  John Tessari
                                                               126

-------
                                                               603
                                       26 April 1985

John Tessari,  Manager
Colorado Pesticide  Hazard Assessment Project
Colorado State University
Fort Collins,  CO
80523
Dear John:
      Enclosed is a copy of the provisional mesurol metabolite
method, as it stood at the  point where we had to quit working on
it.  If it works out that I shall bring the samples to you, I do
have PFBB and 18 crown 6 ether (hexaoxacyclooctadecane)  that I
could bring along, as well as potassium carbonate and the phenol,
itself.  However, as my letter to Gerri Fristrom points out,  this
method may yet be a blind alley, and an entirely new approach may
be required,  to include  the  possibility of running  these samples
on a capillary/FID set-up.  I do not think that the uv spectrum
of the 3,5-dimethylphenol  is good  enough to  do it by HPLC;  al-
though, I would not shy away from re-running  the spectrum of it
again, just in case my crew blew it in preparing the standard for
the spectrophotometer.
                             Sincerely
                             John T.  Leffingwell
                             University of California
                             Bldg.  112, Richmond Field Station
                             47th & Hoffman Blvd.
                             Richmond, CA  94804
                                                                   1 27
Tessari3.1tr

-------
                 Mesurol Urinary Metabolite Meth
                                                                604
                    MESUROL URINARY METABOLITES

 fifltfifi

      The pertinent analytical methods in the literature were for the
 simultaneous determination of Mesurol and its two oxidized forms as
 Mesurol sulfone.  Our goal was to apply this type of analysis to
 Mesurol phenol and its two oxidized forms as they would be found in
 urine.

      Our first findings indicate that the potassium  permanganate
 oxidation method used by Mobay quantitatively destroys  MP  (mesurol
 phenol), MPX (mesurol phenol sulfoxide)  and MFN (mesurol phenol
 sulfone).

      We next found that the m-chloroperoxybenzoic acid (mCPBA) oxi-
 dation  method recovered both MP and MPX as MPN.   The  recovery was
 low,  but no  lower than for MPN, itself, which led us to suspect the
 extraction rather than the oxidation.

      The pH  of the extraction solution turned out to be the problem.
 Mesurol has  no ionizable molecular site,  so that  drastic methods
 could be used to prevent co-extraction of unwanted acidic  materials.
 Up to 40% of the  MPN can be lost at the high pH values used for
 extraction of oxidized mesurol.   By using magnesium  sulfate solution
 to slightly  lower the pH, recoveries very close to 100% have now
 been  obtained.

 Analytical Method

      Equipment and Reagents

 a)  Tilt dispensers:  1 X 10 mL
                      1 X 15 mL   •
                      2 X 20 mL
                      1 X 25 mL
 b)  1 mL high speed pipettor (Brand).
 c)  Rotary evaporator with water  bath.
 d)  13 X 100 mm screw-top culture tube with teflon lined cap (1 per
    sample).
 e)  Test tube rack for 13 mm tubes.
 f)  125 mL separatory funnel with LPE stopper and teflon plug (1 per
    sample).
 g)  Separatory funnel rack.
 h)  250 mL, S 24/40 Round-bottom  flasks  (2 per  sample).
 i)  « 24/40 Stoppers (2 per  sample).
 j)  117 mm OD X 60 mm ID Cork rings  (1 per sample).
 k)  35 mm Polypropylene analytical funnel (2 per  sample).
 1)  Small volumetric flasks with LPE stoppers (1 X 10 mL Qi 1 X 5 mL
    per sample).
m)  4 Dram vials  with teflon lined caps  (1 per  sample).


                               Page  1              6 September 1984

-------
                         Urinary Metabolite  Method


n)   10 mL Volumetric pipefcs (1 per  sample).                 "~
o)   Wash bottle for methylene chloride.
p)   Wash bottle and dropper bottle  for acetonitrile.
q)   Glass wool.
r)   Pasteur pipets (2 per sample).

    Reagents

All solids ace Analytical Grade; all  liquids are HPLC Grade.

a)   CH2Cl2 ~ Methylene Chloride.
b)   CH3CN - Acetonitrile.
c)   H20 - Class ?? Reagent Grade Water  (Milli-Q).
d)   mCPBA - 1% in CH2C12-
e)   MgS04 - 250 g/L In H20.
f)   NaHCC>3 - Aqueous Saturated Solution.
g)   Na2sc>3 - Aqueous Saturated Solution.
h)   Na2SC>4 - Anhydrous crystals.
i)   Dry ice and coolant (2-propanol)  for rotary evaporator.

Prpcedure

     Pipet 10 mL of prepared urine* into a 125 ml separatory funnel;
then add 15 ir.L MgS04 and 20 ml NaHC03. Extract sequentially with 3
X 25 mL portions of CH2Cl2r filtering each through a 35 mm funnel
plugged with glass wool and containing Na2SC>4 into a 250  round
bottom flask, stopper and set aside for rotary  evaporation.

     Rotovap sample to ~  0.25  to 0.50  mL final  volume.  Transfer  to
a culture tube with a pasteur pipet using 4  X 1 mL portions of 1%
mCPBA to rinse the flask.   Seal  the tube and allow the contents to
react at room temperature for at least 20 minutes, but no more than
30  minutes.

     Quantitatively  transfer  the tube contents to a 125 mL separa-
tory funnel containing  20 mL Na2SC>3 solution and shake well to
destroy any  remaining  organo-peroxide.  Then add 15 mL saturated
Na2S04 and 20 mL NaHC03.   Extract with CH2C12 as described above.

     Rotovap  to * 0.5 mL and add 10 mL CH^CN.  Repeat twice more.
Transfer  with CHjCN and pasteur  pipet  to a small volumetric flask (5
or  10 mL)  and make up  to volume. Shake well and put in a 4 dram
vial with proper label.  Turn  the sample over to the HPLC operator
for analysis  of total  MPN.
                              Page 2               6 September 19

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DRAFT                     Page 1
                   Mesurol Urinary Metabolite
                        Analytical Method

                   A Provisional Method Using
                    Pentafluorobenzylbr oroide
                         to Derivatize
                       3 , 5-Dimethy Iphenol
 introduction
      While  at the field  study site,  I  decided to store  the
urines in a fashion that had served us well in the past when we
were dealing with phenolic urinary metabolites:  We placed dupli-
cate 20  roL aliguots of  each  subject's  urine  samples in 20 mL
ampules,  adding 1.5 mL of concentrated hydrochloric acid as  a
preservative.   This approach to storage obviates the need  for
refrigeration/  eliminates leak-prone screw-cap closures,  and sets
the sample up for future  hydrolysis of conjugates.  However, good
evidence  exists to show  that the storage  of urine samples con-
taining metabolites of mesurol  [mesurol phenol  (3,5-dimethyl-4-
methylthiophenol) ,  the sulfoxide (3,5-dimethyl-4-methylsulf inyl-
phenol)  and the sulfone (3,5-dimethyl-4-methylsulfonylphenol)J in
strong acid  causes these compounds  to undergo a reaction that
cleaves the sulfur-carbon bond,  leaving the product,  3,5-dimeth-
y Iphenol.

      In an attempt to produce an analyte that could be quanti-
tated by gas chromatography,  I  decided to derivatize  with  penta-
fluorobenzylbromide (PFBB)  and utilize the electron  capture  de-
tector.   I recognize that this approach  is fraught with many
pitfalls;  ECD's are notoriously sensitive to many extraneous
materials that might be  present in the urine samples, and rea-
gents used to hang a handle on an otherwise non-capturing mole-
cule usually derivatize many unwanted compounds,  as  well.  It is
possible  that a  good quality flame ionization detector coupled
with a capillary column  would give sufficient sensitivity  for
underivatized  3,5-dimethylphenol to eliminate the need for  the
BCD and its attendant hypersensitivities.   I did  not  have  such  a
set-up;  so, decided to press on with the  PFBB procedure.

Materials and Methods

      The first step is taken to hydrolyze any remaining conju-
gates of the phenol.  Ten mL of urine is transferred to a 20 mL
ampule and 5 mL of water  is added.  The ampule is sealed  and
heated under pressure (15 Ib. in a standard household pressure
cooker  or 20 Ib.  in a laboratory or clinical autoclave) for 2  hr.
The ampule is opened and the contents are quantitatively  trans-
ferred to a 125 mL separatory funnel with about 40 mL of  water.
Extract  three times with  about 25 mL of methylene chloride.

     At  this point the  methylene  chloride can  be removed  and
replaced  with acetonitrile by rotary evaporation.  (With  care  not
to let the  solvent go completely  dry,  good recoveries of  the


Mesurol  Urinary Metabolite Analytical Method       26 April 1985

-------
                                                         DRAFT


relatively volatile  phenols can  be  realized doing  a  solvent
volume  reduction on  a rotary  evaporator.)   It has not  been
tested, yet,  to determine  whether or not the  derivatization
reaction can be carried out in  the roethylene chloride, either
with or without a prior drying step.  At this  point, the conver-
sion to acetonitrile  is compatible with the subsequent  clean-up
procedure utilizing hexane/water  partitioning.

     Whether the  reaction is to  be  carried out in  methylene
chloride or in acetonitrile (It will also go equally  well in
acetone.),  the  volume of  the sample should be brought to about
1 roL.  Add  20  pL of pentafluorobenzylbromide, 20 mg  potassium
carbonate and 20 mg 18 crown 6 ether.  Seal (We use Teflon-lined,
screw-capped culture  tubes.)  and heat 2 hours at  100° c.   Add
10 mL of hexane and shake well.   Add 5 mL of  water and, again,
shake thoroughly; then allow to settle.

     Pre-clean a silica gel Sep-Pak by running 10 roL of HPLC or
pesticide grade hexane through  it.  Draw off a 3 mL aliquot of
the hexane  layer of the sample with a gas tight syringe and push
very slowly through  the pre-cleaned  silica gel Sep-Pak.   Follow
it with 5 mL of clean hexane. Discard the eluate;  it contains
about 90% of the  residual PFBB.   Finally,  elute the Sep-Pak  with
5 mL of a toluene/hexane  mixture  (70/30 v/v).  Collect  the el-
uate; bring it to a convenient volume; and analyze for the deriv-
ative of the phenol by EC gas chromatography.   We found the HP-
5880A, using a 50 micron Megabore capillary  column,  gave us a
very nice peak with 4 to 10 feroptograms of the derivative.   Un-
fortunately, the same holds true  for the PFBB,  as  well; so, it is
important to have most  of  the  reagent removed before the sample
hits the BCD.
Mesurol Urinary Metabolite Analytical Method        26 April 1985       _.

-------
                                             608
       APPENDIX C
   DATA FILES  RELEVANT TO.
URINARY METABOLITE ANALYSES
                                                 132

-------
                                                                   609
                                         Section  Appendix C
                                         October 15,  1985
                                         Page  1   of  22
                       APPENDIX C

                      Drine Volumes
                         TABLE 1

       Raspberry  Study, Pre-Exposure Urine Samples*

Sample ID        Subject ID          Group           Volume
8301-U-60.
8301-U-60.
8301-0-60.
8301-D-60.
8301-D-60.
8301-D-60.
8301-D-60.
8301-0-60.
8301-D-60.
8301-D-60.
8301-U-60.
8301-U-60.
8301-U-60.
8301-U-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
8301-0-60.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
A
A
A
A
B
A
A
B
B
B
B
A
A
B
A
A
A
A
A
A
B
B
B
170
208
630
230
380
300
177
190
209
480
680
310
186
230
630
380
310
252
186
214
300
146
210
     morning void prior to entry  into the field, 11 July 1983.
                                                                   133

-------
                                             Section  Appendix C    / 1 n
                                             October 15, 1985       61 U
                                             Page 2  of  22
                 -.            TABLE 2

         Raspberry Study, First Urine Sample Collection*

   Sample ID        Subject ID          Group            Volume
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
"8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
8301-0-61/62.
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
A
A
A
A
B
A
A
B
B
B
B
A
B
A
A
A
A
A
A
B
B
790
305
790
620
380
680
550
234
530
740
740
730
710
450
380
515
620
415
290
290
335
* Overnight samples, Day Two to Day three, 12 to 13 July 1983.

-------
                                             Section  Appendix C      611
                                             October 15, 1985
                                             Page 3  of  22
                             TABLE 3

       Raspberry Study, Second Urine Sample Collection*

  Sample  ID        Subject ID          Group            Volume
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
A
A
A
A
B
A
A
B
B
B
B
A
B
A
A
A
A
A
A
B
B
194
104
216
100
124
N/S
N/S
N/S
N/S
224
280
172
114
150
410
175
N/S
N/S
N/S
N/S
N/S
* Samples collected during working hours of Day Three, 13 July 1983.


                                                                       135

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                                            Section  Appendix C
                                            October 15,  1985
                                            Page 4  of  22

                            TABLE 4

         Raspberry Study, Third Drine Sample Collection*

   Sample ID        Subject ID          Group            Volume
612
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
8301-0-62/63.
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
A
A
A
A
B
A
A
B
B
B
B
A
B
A
A
A
A
A
A
B
B
770
345
710
270
470
221
153
138
300
700
570
655
435
550
285
730
865
240
281
274
Lost by Subject
* Overnight sample,  13  to 14 July 1983.
                                                                   136

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                                            Section   Appendix C     & 1 7.
                                            October  15,  1985         ° 'J
                                            Page 5   of   22
                           TABLE  5

      Raspberry Study, Fourth Urine Sample Collection*

 Sample ID        Subject  ID          Group             Volume
8301-U-63.
8301-0-63.
. 8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
8301-0-63.
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
A
A
A
A
B
A
A
B
B
B
B
A
B
A
A
A
A
A
A
B
B
123
190
280
92
138
400
265
80
170
430
380
72
232
156
190
170
250
132
170
214
218
Samples collected during working hours of Day Four, 14 July 1983.


                                                       137

-------
                                             Section  Appendix  C
                                             October  15,  1985        L \ A
                                             Page 5   of   22         ° ' H

                             TABLE 5

        Raspberry Study, Fourth Drine Sample Collection*

   Sample ID        Subject ID          Group             Volume
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
8301-0-62.
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
A
A
A
A
B
A
A
B
B
B
B
A
B
A
A
A
A
A
A
B
B
123
190
280
92
138
400
265
80
170
430
380
72
232
156
190
170
250
132
170
214
218
* Samples collected during working hours of Day Four, 14 July 1983.
                                                                  138

-------
                                            Section  Appendix C      , ,  ,_
                                            October 15, 1985         6 I  5
                                            Page 6  of  22
                            TABLE  6

          Blackberry  Study, Pre-Exposure Urine Samples*

   Sample ID       Subject ID          Group            Volume
8302-D-17.
8302-0-17.
8302-D-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-18.**
8302-0-18.**
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-18.**
8302-0-17.
8302-0-17.
8302-0-17.
8302-0-17.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
21
22
23
24
28
29
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
***
***
B
B
B
B
B
B
615
390
740
235
277
306
224
275
930
950
515
178
264
204
335
450
110
254
395
255
430
366
260
390
* First morning  void prior to entry  into the field, 18 July 1983
** Subjects  15,16,  and  22 joined the study on Day 2.
*** Subjects 17  and 18  were dropped  from the study.
                                                                  139

-------
                                             Section Appendix C
                                             October 15,  1985
                                             Page  7   of   22

                             TABLE 7

        Blackberry Study, First Urine Sample Collection*

   Sample ID        Subject ID          Group           Volume
8302-0-18/19.
8302-U-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19.
8302-0-18/19*
8302-0-18/19.
8302-0-18/19.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
21
22
23
24
28
29
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B .
B
B
B
B
B
B
930
780
750
400
148
266
182
224
800
584
1040
242
130
160
720
380
470
580
960
326
455
480
* Overnight samples,  Day Two to  Day  Three,  19 to 20 July 1983
6\i
                                                                    140

-------
                                             Section  Appendix C      £ 1 7
                                             October 15, 1985         ° ' '
                                             Page 8  of  22
                             TABLE 8

       Blackberry  Study,  Second Urine Sample Collection*
                  \
  Sample ID         Subject ID          Group            Volume
8302-D-19.
8302-U-19.
8302-D-19.
8302-D-19.
8302-0-19.
8302-U-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
8302-0-19.
1
2
3
4
5
6
7
8