EPA 800/1-77-021
April 1977
Environmental Health Effects ftesearefi Series
EFFECTS OF FOOD PROCESSING ON RESIDUES OF
ETHYLENEBISDITHIOCARBAMATE FUNGICIDES AND
ETHYLENETHIOUREA
Health Effects Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL HEALTH EFFECTS RE-
SEARCH series. This series describes projects and studies relating to the toler-
ances of man for unhealthful substances or conditions. This work is generally
assessed from a medical viewpoint, including physiological or psychological
studies. In addition to toxicology and other medical specialities, study areas in-
clude biomedical instrumentation and health research techniques utilizing ani-
mals — but always with intended application to human health measures.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/1-77-021
April 1977
EFFECTS OF FOOD PROCESSING
ON RESIDUES OF TWO ETHYLENEBISDITHIOCARBAMATE (EBDC)
FUNGICIDES AND ETHYLENETHIOUREA (ETU)
by
W. F. Phillips and M. D. Grady
Technological Resources, Inc.
A Subsidiary of Campbell Soup Company
Camden, New Jersey 08101
and
Ralph Freudenthal
Battelle Memorial Institute
Columbus, Ohio 43201
Contract No. 68-02-1715
Project Officer
Ronald L. Baron
Criteria and Special Services Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
Health Effects Research Laboratory
Office of Research and Development
United States Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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DISCLAIMER
This report has been reviewed by the Health Effects Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
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FOREWORD
The many benefits of our modern, developing, industrial society are
accompanied by certain hazards. Careful assessment of the relative risk
of existing and new man-made environmental hazards is necessary for the
establishment of sound regulatory policy. These regulations serve to
enhance the quality of our environment in order to promote the public
health and welfare and the productive capacity of our Nation's population.
The Health Effects Research Laboratory, Research Triangle Park,
conducts a coordinated environmental health research program in toxicology,
epidemiology, and clinical studies using human volunteer subjects. These
studies address problems in air pollution, non-ionizing radiation,
environmental carcinogenesis and the toxicology of pesticides as well as
other chemical pollutants. The Laboratory develops and revises air quality
criteria documents on pollutants for which national ambient air quality
standards exist or are proposed, provides the data for registration of new
pesticides or proposed suspension of those already in use, conducts research
on hazardous and toxic materials, and is preparing the health basis for
non-ionizing radiation standards. Direct support to the regulatory function
of the Agency is provided in the form of expert testimony and preparation of
affidavits as well as expert advice to the Administrator to assure the
adequacy of health care and surveillance of persons having suffered imminent
and substantial endangerment of their health.
The significance of the occurrence of residues of pesticides or
metabolites of pesticides in or on plants destined for human consumption
must be considered with respect to its ultimate impact on human health.
The present study evaluates the occurrence of residues of a widely used
class of fungicide (ethylenebisdithiocarbamates) and the presence of a
biologically active metabolite (ethylenethiourea) as a residue in food.
The occurrence of the pesticide residue in several raw agricultural
crops and the effects of commercial and home processing for consumption
on the disappearance of the pesticide residue is evaluated with respect
to several major food commodities upon which this pesticide class finds
wide use.
John H. Knelson, M.D.
Director,
Health Effects Research Laboratory
m
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ABSTRACT
Tomatoes, carrots, and spinach were treated at application rates
recommended for good agricultural practice and at 4 times these rates
with two ethylenebisdithiocarbamate (EBDC) fungicides (Dithane M-45 and
®
Dithane M-22 ). These crops were grown in keeping with good agricultural
practice at two locations; East and West. The pesticide residues, the
presence of a metabolite, ethylenethiourea (ETU) and the effects of
standard food processing techniques on residues of both EBDC and ETU
were determined.
Methods sensitive to 0.1 ppm EBDC and to 0.01 ppm ETU were used.
All results were corrected for control values and for recovery of fortified
samples analyzed concurrently.
As a direct result of the analytical procedures, EBDC was found to
convert spontaneously to ETU during analysis. Average conversions of
EBDC to ETU in control samples of the three crops fortified with Dithane
M-4i> ranged from 7-16%; conversions were 19.9 and 7.3% for tomatoes and
a. —.
spinach, respectively, when fortified with Dithane M-22 .
On crops treated with Dithane M-4J> and grown in the East, low
levels of EBDC as a residue and of ETU were found in tomatoes and carrots;
residues from spinach were appreciably higher. Residues 1n the Western
crops, relative to those grown 1n the East, were higher on tomatoes and
lower on carrots; EBDC residues were much higher on spinach. In no case
were the tolerance levels of EBDC (Dithane M-45 ) exceeded on carrots or
tomatoes. With spinach, on which Dithane M-45 1s not registered for
1v
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use, up to 62 ppm EBDC was found on the unwashed product. (Dithane
M-45® was applied at the rate generally recommended for Dithane M-22
®
use on this crop). In the crops treated with Dithane M-22 (only at the
Western location), average residues of EBDC on tomatoes did not exceed
allowable tolerance levels. Again, residues on spinach were excessive
in the unwashed crop.
Residues of ETU were noted on unwashed crops resulting from the use
of both EBDC fungicides. The ETU residues were most notable on unwashed
spinach from the Western location.
Washing in all cases removed significant amounts of both EBDC and
ETU residues. However, residues of EBDC on western spinach exceeded
tolerance levels even after washing. Washing also removed significant
quantities of the ETU residue where it was noted on unwashed (Western)
spinach. Further commercial food processing techniques decreased residues
of EBDC significantly in all the crops and especially in spinach.
However, ETU residues tended to increase with commercial food processing.
Cooking of canned whole tomatoes for 5 and 60 minutes simulating home
preparation followed this same pattern (reduced EBDC content - increased
ETU content). While EBDC residues declined on normal commercial food
processing, ETU residue levels increased. In concentrating tomato juice
to tomato sauce and further to tomato paste (from crops treated with
®
Dithane M-22 ), ETU residues increased to an extent that appeared to be
proportional to the degree of concentration or water loss. With western
®
spinach treated with D1thane M-22 , average ETU residues were appreciable
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in all of the processed spinach. In cooking the spinach (again simulating
household preparation of both frozen or canned product) ETU residues did
not change appreciably.
The data, in part, further suggest that greater conversion of EBDC
to ETU may occur in laboratory-fortified samples than in field-weathered
samples.
This report was submitted by Technological Resources Inc., a sub-
sidiary of Campbell Soup Company in fulfillment of Subcontract to
Battelle Memorial Institute, Contract No. 68-02-1715 under the sponsor-
ship of the U.S. Environmental Protection Agency. This report covers
the period March 1, 1975 to July 31, 1976 and work was completed as of
December 31, 1976.
vi
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CONTENTS
Page
Forward 111
Abstract ™
Figures v111
Tab! es 1 x
Abbreviations x111
Acknowledgments xiv
I. Introduction 1
II. Materials and Methods 3
Growi ng and Treatment of Crops 3
Processing of Crops 3
Tomatoes 3
Carrots 7
Spinach 7
Additional Processing 8
Methods of Analysis 8
EBDC 8
ETU 8
Typical Analysis of Dithane for EBDC and ETU 9
Calculation of Data 10
Method of Fortification of Crops 10
III. Results and Discussion 12
Residues from Dithane M-45 13
Eastern Crops 13
Western Crops and Comparison with Eastern Crops 13
Effects of Washing and Canning 14
Conversion of added EBDC to ETU due to Analytical
Method and Matri ces 15
ETU formation from weathered residues and from
added Dithane M-45 15
Residues from Dithane M-22 18
Tomatoes, residues at the various processing
stages 18
Spinach, residues at the various processing
stages 19
Residues from whole tomatoes fortified
with EBDC and ETU 20
Conversion of added EBDC to ETU in tomatoes
and spinach 21
Confirmation of ETU by GC/MS 21
Summary Tables I and II. Residue Data from Field-
Treated Crops 23
IV. References 26
Appendices
A. Detailed Analytical Procedure Used to Determine ETU
Residues 27
B. Individual Data from Summary Table I (Dithane M-45) 53
C. Individual Data from Summary Table II (Dithane M-22) ... . 106
D. Tables III to VIII 139
E. GC/MS Confirmation 173
vii
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FIGURES
Number Page
1 Preparation of liquid chromatograph column 50
2 Typi cal chromatograms 51
3 Typical calibration curve 52
viii
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TABLES
Number
1 Conditions for Growing, Treatment, and Harvesting of Crops
Grown at Rancocas, New Jersey (Eastern Location) 4
2. Conditions for Growing, Treatment, and Harvesting of Crops
Grown at Davis, California (Western Location) 5
3. Summary of Data on Residues of EBDC and ETU at Various
Processing Stages from Crops Grown at East an$ West
Coast Locations and Treated with Dithane M-45 at 0,
1, and 4x Registered Rates 24
4. Summary of Data on Residues of EBDC and ETU at Various
Processing Stages from Crops Growruat West Coast Loca-
tion and Treated with Dithane M-22 at 0, 1, and 4x
Registered Rates 25
Appendix B - Individual Data From Summary Table 2
IA-1-A EBDC East Coast Tomatoes Unwash 54
IA-l -B EBDC East Coast Tomatoes Wash 55
IA-1-C EBDC East Coast Tomatoes Tailings 56
IA-1-D EBDC East Coast Tomato Juice Canned 57
IA-2-A ETU East Coast Tomatoes Unwash 58
IA-2-B ETU East Coast Tomatoes Wash 59
IA-2-C ETU East Coast Tomatoes Tailings 60
IA-2-D ETU East Coast Tomato Juice Canned 61
IA-3-A EBDC West Coast Tomatoes Unwash 62
IA-3-B EBDC West Coast Tomatoes Wash 63
IA-3-C EBDC West Coast Tomato Tailings 64
IA-3-D EBDC West Coast Tomato Juice Canned 65
IA-4-A ETU West Coast Tomatoes Unwash 66
IA-4-B ETU West Coast Tomatoes Wash 67
IA-4-C ETU West Coast Tomatoes Tailings 68
IA-4-D ETU West Coast Tomato Juice Canned 69
IB-1-A EBDC East Coast Carrots Unwash 70
IB-1-B EBDC East Coast Carrots Wash 71
IB-l-C EBDC East Coast Carrots Blanched, Diced 72
IB-l-D EBDC East Coast Carrots Diced, Frozen 73
IB-1-E EBDC East Coast Carrots Canned 74
IB-2-A ETU East Coast Carrots Unwash 75
IB-2-B ETU East Coast Carrots Wash 76
IB-2-C ETU East Coast Carrots Blanched, Diced 77
IB-2-D ETU East Coast Carrots Diced, Frozen 78
IB-2-E ETU East Coast Carrots Canned 79
IB-3-A EBDC West Coast Carrots Unwash 80
IB-3-B EBDC West Coast Carrots Wash 81
IB-3-C EBDC West Coast Carrots Blanched, Diced 82
IB-3-D EBDC West Coast Carrots Diced, Frozen 83
IB-3-E EBDC West Coast Carrots Canned 84
IB-4-A ETU West Coast Carrots Unwash 85
IB-4-B ETU West Coast Carrots Wash 86
IB-4-C ..ETU West Coast Carrots Blanched, Diced 87
IB-4-D ETU West Coast Carrots Diced, Frozen 88
IB-4-E ETU West Coast Carrots Canned 89
ix
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Page
IC-l-A EBDC East Coast Spinach Fresh Unwash 90
IC-l-B EBDC East Coast Spinach Fresh Wash 91
IC-l-C EBDC East Coast Spinach Blanched, Frozen 92
IC-1-D EBDC East Coast Spinach Canned 93
IC-2-A ETU East Coast Spinach Fresh Unwash 94
IC-2-B ETU East Coast Spinach Fresh Wash 95
IC-2-C ETU East Coast Spinach Blanched, Frozen 96
IC-2-D ETU East Coast Spinach Canned 97
IC-3-A EBDC West Coast Spinach Unwash 98
IC-3-B EBDC West Coast Spinach Wash 99
IC-3-C EBDC West Coast Spinach Frozen 100
IC-3-D EBDC West Coast Spinach Canned 101
IC-4-A ETU West Coast Spinach Unwash 102
IC-4-B ETU West Coast Spinach Wash 103
IC-4-C ETU West Coast Spinach Frozen 104
IC-4-D ETU West Coast Spinach Canned 105
Appendix C - Individual Data from Summary Table 3
IIA-l-A EBDC Unwash Tomatoes 107
IIA-l-B EBDC Wash Tomatoes 108
IIA-l-C EBDC Canned Whole Tomatoes 109
IIA-l-D EBDC Canned Whole Tomatoes Cook 5 Minutes 110
IIA-l-E EBDC Canned Whole Tomatoes Cook 60 Minutes Ill
IIA-l-F EBDC Canned Tomato Juice 112
IIA-l-G EBDC Tomato Sauce 113
IIA-l-H EBDC Tomato Paste 114
IIA-2-A ETU Unwash Tomatoes 115
IIA-2-B ETU Wash Tomatoes 116
IIA-2-C ETU Canned Whole Tomatoes 117
IIA-2-D ETU Canned Whole Tomatoes Cook 5 Minutes 118
IIA-2-E ETU Canned Whole Tomatoes Cook 60 Minutes 119
IIA-2-F ETU .Canned Tomato Juice 120
IIA-2-G ETU Tomato Sauce 121
IIA-2-H ETU Tomato Paste 122
IIB-l-A EBDC Unwash Spinach 123
IIB-l-B EBDC Wash Spinach 124
IIB-l-C EBDC Blanch Frozen Spinach 125
IIB-l-D EBDC Blanch Frozen Spinach Cook 5 Minutes 126
IIB-l-E EBDC Blanch Frozen Spinach Cook 5 Minutes
(drained water) 127
11B-1-F EBDC Canned Spinach 128
IIB-l-G EBDC Canned Spinach Cook 5 Minutes 129
IIB-l-H EBDC Canned Spinach Cook 5 Minutes (drained water) 130
IIB-2-A ETU Unwash Spinach 131
IIB-2-B ETU Wash Spinach 132
IIB-2-C ETU Blanch Frozen Spinach 133
IIB-2-D ETU Blanch Frozen Spinach Cook 5 Minutes 134
IIB-2-E ETU Blanch Frozen Spinach Cook 5 Minutes
(drained water) 135
IIB-2-F ETU Canned Spinach 136
IIB-2-G ETU Canned Spinach Cook 5 Minutes 137
IIB-2-H ETU Canned Spinach Cook 5 Minutes (drained water) 138
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Appendix D - Summary and Individual Data Tables
III. Effect of Washing and Canning on EBDC and ETU Residues 1n @
Tomatoes, Carrots, and Spinach Treated with D1thane M-45 140
IV. Conversion of EBDC (added as Dithane M-45®) to ETU on Control
Samples of Tomatoes, Carrots, and Spinach—at Various Process-
i ng Stages !41
V. Conversion of EBDC (added as Dithane M-22®) to ETU on Control
Samples of Tomatoes and Carrots—at Various Processing
Stages 144
VI. Rate of Formation and Breakdown of ETU from Technical EBDC
(6.2 ppm) in Boiling Distilled Water Buffered at pH 5.21 145
VII. Summary Table of Average Residues from Fortified Control Whole
Tomatoes and from Whole Tomatoes with Residues of the Same
Magnitude from field-applied Di thane M-22 4x Treatment—
at Various Stages of Processing 171
VII. Individual Data Tables 146
FORTIFICATION—WASHED TOMATOES—0.5 ppm EBDC
VII-l-A EBDC Wash Tomatoes 146
VII-l-B EBDC Canned Whole Tomatoes 147
VII-l-C EBDC Canned Tomato Juice 148
VII-l-D EBDC Tomato Sauce 149
VII-l-E EBDC Tomato Paste 150
VII-2-A ETU Wash Tomatoes 151
VII-2-B ETU Canned Whole Tomatoes 152
VII-2-C ETU Canned Tomato Juice 153
VII-2-D ETU Tomato Sauce 154
VII-2-E ETU Tomato Paste 155
FORTIFICATION—WASHED TOMATOES—0.07 ppm ETU
VII-3-A ETU Wash Tomatoes 156
VII-3-B ETU Canned Whole Tomatoes 157
VII-3-C ETU Canned Tomato Juice 158
VII-3-D ETU Tomato Sauce 159
VII-3-E ETU Tomato Paste 160
xi
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FORTIFICATION—WASHED TOMATOES—0.5 ppm EBDC AND 0.07 ppm ETU
VII-4-A EBDC Wash Tomatoes 161
VII-4-B EBDC Canned Whole Tomatoes 162
VII-4-C EBDC Canned Tomato Juice 163
VII-4-D EBDC Tomato Sauce 164
VII-4-E EBDC Tomato Paste 165
VII-5-A ETU Wash Tomatoes 166
VII-5-B ETU Canned Whole Tomatoes 167
VII-5-C ETU Canned Tomato Juice 168
VII-5-D ETU Tomato Sauce 169
VII-5-E ETU Tomato Paste 170
VIII. Summary of Recovery Data 172
Appendix E - 6C/MS Confirmatory Data
I. Standard Mass Spectra of S-rnButyl ETU (CI mode, CH4) 174
II. Mass Spectra of Control Canned Spinach (CI mode) 175
III. Mass Spectra of Canned Spinach, M-45, Ix, (CI mode) 176
IV. Mass Spectra of Canned Spinach, M-45, 4x, (CI mode) 177
V. Standard Mass Spectra of S-in-Butyl ETU (El mode) 178
VI. Mass Spectra of Control Canned Spinach, (El mode) 179
VII. Mass Spectra of Canned Spinach, M-45, Ix, (El mode) 180
VIII. Mass Spectra of Canned Spinach, M-45, 4x, (El mode) 181
xii
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LIST OF ABBREVIATIONS
A -- acre
ai -- active ingredient
avg -- average
C -- Centigrade
CC -- Closed Cup
CI -- Chemical impact
cm -- centimeter
EBDC -- ethylenebisdithiocarbamate
EC -- emu!sifiable concentrate
El -- Electron impact
ETU -- ethylenethiourea
F -- Fahrenheit
FP — Flash point
g -- gram
gal -- gallon
GC or GLC -- gas chromatograph
GC/MS -- gas chromatograph/mass spectrographic analysis
ft -- foot
ha -- hectare
in -- inch
kg -- kilogram
Ib -- pound
min -- minute
ml -- milliliter
mm -- millimeter
mv -- millivolt
ng -- nanogram
OC -- Open Cup
ppm -- parts per million
pt -- pint
yg or ug -- microgram
V -- volume
WP -- wettable powder
xiii
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ACKNOWLEDGMENT
The authors express sincere appreciation to:
Dr. Ronald Baron, EPA and Dr. Ralph Freudenthal, Battelle Memorial
Institute, for technical support and guidance of this project.
Mr. C. A. Scheib, Campbell Soup Company, for the GC/MS confirmation
analyses of ETU results on four samples of Dithane M-45-treated canned
spinach.
Rohm and Haas Company for permission to reproduce their analytical
method for ETU.
We also wish to acknowledge the assistance of Dr. Morton Beroza in
preparing this report.
x1v
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SECTION I
INTRODUCTION
This study was undertaken to determine the effects of food processing
on residues of two ethylenebisdithiocarbamate (EBDC) fungicides and a
metabolite, ethylenethiourea (ETU), common to this class of fungicides.
One of the fungicides was Dithane M-45* (zinc ion and manganese ethylene-
bisdithiocarbamate), a coordination product of manganese 16%, zinc 2%,
ethylenebisdithiocarbamate 62% (also called mancozeb and Manzate 200 ). The
second fungicide was Dithane M-22 , manganese ethylenebisdithiocarbamate
(maneb, Manzate", Chem Neb"). [The major difference in the chemicals
appears to be the presence of 2% zinc in Dithane M-45 and the absence
(R) -,
of zinc in Dithane M-22 J
Three crops grown at Eastern and Western U.S. locations were treated
with Dithane M-4{> . Residues of the parent compound and metabolite were
determined on the fresh and washed raw agricultural commodity, processed
canned and frozen products. In addition, a cooking experiment was
®
conducted to determine the stability of technical Dithane M-45 and the
rate of formation and degradation of ethylenethiourea in boiling water.
Tomatoes, carrots and spinach were grown on the East Coast of the
U.S. in Rancocas, New Jersey and on the West Coast at Davis, California.
Experimental plots, which were arranged in a Latin Square design, were
treated at two rates of application and included a control (untreated).
Treatments, replicated three times, were made in accordance with the
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current EPA Compendium of Registered Pesticide Uses (1976), where applica-
ble, and at four times the registered rates. Tolerances of EBDC on
tomatoes and carrots treated with Dithane M-45 are 4 and 2 ppm, respective-
ly; Dithane M-45 is not registered for use on spinach. Tolerances of
EBDC on tomatoes, carrots, and spinach treated with Dithane M-22* are
®
4, 7, and 10 ppm, respectively. Since Dithane M-45 is not registered
for use on spinach, the 1 and 4-fold rates of 1.6 pounds and 6.4 pounds
active ingredient per acre (1.79 and 7.17 kg/hectare) for Dithane M-22 ,
which is registered for use on spinach, were used to apply Dithane M-45*
to spinach. With this exception, crops were grown and processed in
accordance with good agricultural and manufacturing practices.
Two of the three crops, tomatoes and spinach, grown at Davis,
California were experimentally treated with Dithane M-22 to evaluate
the effects of processing on residues of this fungicide. The Dithane
M-22 study was conducted in essentially the same way as the Dithane
M-45 study except that additional processing parameters on residues of
EBDC and ETU were examined. The additional processing parameters included
canning of whole tomatoes, simmering of tomatoes for two time intervals,
preparation of tomato sauce and tomato paste, and cooking of frozen and
canned spinach. Experiments were also conducted to determine effect of
processing on conversion of residues of EBDC to ETU 1n whole tomatoes
field-treated 4x the registered rate vs. those 1n a control sample
laboratory-fortified with EBDC and ETU at the same level as in the
field-treated sample.
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SECTION II
MATERIALS AND METHODS
Each of the following treatments were replicated three times, and
each replicate was analyzed in duplicate. All residue values are reported
in ppm (parts per million). All results are corrected for control
values and data on recovery of fortified samples.
GROWING AND TREATMENT OF CROPS
The tomatoes, carrots, and spinach were grown at two locations--
Rancocas, New Jersey and Davis, California. After the plots were sub-
®
divided in a Latin Square design, they were treated with Dithane M-45 or
Dithane M-22 at 0, 1, and 4 times the registered application rate
(Note: Dithane M-45 is not recommended for use on spinach. The same
dosage levels were used for both products). Table 1 presents details
describing the growing, treatment, and harvesting of the three crops in
the Eastern location, and Table 2 gives similar data for the 3 crops
®
grown in the West. Samples from the Eastern Dithane M-22 applications
were not analyzed.
PROCESSING OF CROPS
The following conditions were employed for processing the crops.
Samples except for those canned, were frozen and stored at -20°F (-29°C)
until analyzed.
Tomatoes
Washed and Unwashed Samples--
Fresh harvested California tomatoes, both unwashed and cold-water-
washed, were frozen for shipment to the Camden, New Jersey laboratory
-------
Table 1. Conditions for Growing, Treatment, and Harvesting
of Crops Grown at Rancocas, New Jersey (Eastern location)
Treatment
Spinach*
Carrots
Tomatoes
1. Fertilizer
250 Ib/A 10-10-10 disced
before planting, 90 Ib/A
ammonium nitrate top-
dressed on 5/23 and
6/10/75.
Fumigant methyl
bromide 1 lb/
100 sq. ft.
2. Variety
3. Seeded
4. Herbicide
Long standing Bloomsdale Danvers 126
600 Ib/A 10-10-10
disced in before
planting.
Campbell 17
4/18/75
CIPC 0.5 lb ai/A and
Vegedex 2 lb ai/A
applied preemergence
4/22/75.
Insecticides Malathion 1 qt 57% EC/A,
Diazinon h pt of 4 lb/
gal EC/A. Combination
applied with air blast
sprayer 5/22 and 6/3/75.
6. Fungicide
D1thane applied 6/9/75
1.6 Ib ai/A (1.79
kg/ha) in 37 gal
(140 liters) water/A.
6.4 lb ai/A (7.17
in 50 gal (189 liters)
water/A.
7. Harvested 6/19/75
4/16 and 5/19/75 5/24/75
none
Sevin 2 lb ai/A
7/11 and 7/26/75
Pebulate 4 Ib ai/A
before planting.
Chloramben 4 lb ai/A
granular broadcast.
Azinphosmethyl 0.25 lb
ai/A on 5/10 5/26, 6/10
6/19/75. Carbaryl 1
lb ai/A plus endo-
sulfan 0.5 lb ai/A 7/1,
7/11/75. Carbaryl 1 Ib
ai/A 7/26/75.
Dithane 1.6 and 6.4 Dithane 1.6 and 6.4 lb
lb ai/A (1.79 and a1/A (1.79 and 7.17 kg/ha)
* ""- 7/8, 7/17, 7/24, 8/4, 9/16
applied in 50 gal (189
liters) water/A.
7.17 kg/ha) 7/17,
7/24, 8/4, 8/13,
8/27, 9/10/75.
9/30/75
9/22/75
Crop injured by smog during week of 5/19/75 (30 days prior to harvest).
-------
Table 2. Conditions for Growing, Treatment, and Harvesting
of Crops Grown at Davis, California (Western Location)
Treatment
Spinach
Carrots
Tomatoes
1. Fertilizer
20-10-10 at 150 Ib/A
broadcast preplant
none
Herbicide
Ro—neet (73.9%)
Cycloate 2/3 gal/A
broadcast preplant
Insecticides Spectracide (Diazinon
25%) h pt/A 1/13/76
none
none
4. Fungicides
Dithane applied 3/23/76. Dithane 1.6 and
1.6 Ib ai/A (1.79 kg/ha) 6.4 Ib ai/A
in 37 gal (140 liters)
water/A and 6.4 Ib ai/A
(7.17 kg/ha) in 50 gal
(189 liters) water/A.
(1.79 and 7.
kg/ha) 9/8,
9/15/75.
17
Nitrogen 70 Ib
(broadcast) preplant.
Starter (8-24-0) 15
gal (57 liters) water/A.
Two inches under seed.
Trefmid 8.0 Ib/A
broadcast preplant
Sevin (50% WP) 2.0 Ib
ai/A, Sulfur 40 Ib/A
7/10, 7/31, 8/21/75.
Dithane 1.6 and 6.4
Ib ai/A (1.79 and 7.17
kg/ha) 8/22, 8/29,
9/5/75.
5. Harvested 4/2/76
9/22/75
9/10/75
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for processing and analysis. Fresh-harvested New Jersey tomatoes were
shipped direct to the laboratory. Washed tomatoes were prepared by
cold-water washing for approximately three to five minutes with con-
tinuous flow of cold tap water with agitation. Washed and unwashed
samples were macerated with dry ice to maintain a free-flowing powder
and held at -20°F (-29°C) until analyzed for EBDC and ETU.
Canned Juice and Tailings—
In the pilot plant, approximately 35 pounds (15.9 kg) from each
treatment were cold-water washed twice, trimmed where necessary, and
then macerated in a Hobart mixer. The macerate was heated with stirring
to 180°F (82°C) in a steam-jacketed kettle. Heated tomatoes were passed
through a Langsenkamp extractor fitted with an 0.027 screen. Resultant
purees were heated to 200°F (93°C), canned, processed for 20 minutes in
boiling water, cooled, and cased. Tailings from each extraction (seeds
and skin) were collected and frozen.
Sauce--
Tomato juice-was evaporated at 60-70°C under 25-psi vacuum to yield
a product with about 15% solids.
Paste-
As in sauce above, but product was concentrated to 30-35% solids.
Canned Whole Tomatoes--
Washed tomatoes were immersed in hot water (ca. 70°C) for five
minutes. After the skins were removed, the tomatoes were transferred to
cans and processed at 240°F (116°C) for 45 minutes.
-------
Carrots
Unwashed—
Fresh-harvested carrots were vigorously washed with cold water to
remove dirt.
Washed—
Skins from the carrots above were removed by hand with a wire brush
and cold-water washed.
Diced—
Carrots were passed through a washer and abrasive peeler and diced
(1/4") in Pilot Plant.
Frozen-
Diced carrots from above were blanched for four minutes in 200°F
(93°C) water, drained and frozen.
Canned-
Diced carrots and hot 190°F (88°C) water were added to No. 1 cans,
sealed, and processed in a retort for 40 minutes at 240°F (116°C).
Spinach
Unwashed (rinsed)--
Unwashed, fresh-harvested spinach was cold-water rinsed to remove
dirt.
Washed—
Fresh spinach was washed with cold water.
Frozen--
Washed spinach from above was blanched for three minutes at 190°F
(88°C) in a steam-jacketed kettle, chopped, and frozen.
-------
Canned--
Washed spinach from above was blanched for three minutes at 190°F
(88°C) in a steam-jacketed kettle, chopped, canned, and processed for 55
minutes in a pressure cooker at 240°F (116°C).
Additional Processing
To determine the effect of cooking, canned whole tomatoes were
cooked for 5 minutes, and the resultant solids and drained water were
each analyzed for EBDC and ETU.
METHODS OF ANALYSIS
EBDC
The analytical method employed for determining residues of EBDC was
described by Keppel (1971). For the crops studied, the sensitivity is
0.1 - 0.2 ppm of EBDC with an average recovery of 85.6%. Standards for
calibration and recovery studies were prepared as described by Gordon,
et al. (1967).
ETU
The analytical method used for determining ETU, the Haines-Adler
t
Method (1973) (Rohm and Haas Test Method 1881-1), as modified by Technologi-
cal Resources Inc., is presented in detail in Appendix A. It is essential
that all sources of contact with rubber be eliminated. It was found
that the addition of a small amount of trichloroacetic acid to the
extraction solvent improved the recovery of ETU from spinach and carrot
matrices. The GC column packing and conditions for separation of ETU
were also modified. The major advantages of the modified packing are
more stable baseline, better separation of ETU from possible crop interfer-
ences, and improved GLC response to the S-butyl derivative. There
8
-------
should be no delay in processing samples from time of extraction to the
formation of the S-butyl derivative. Minimum time of exposure to DMF 1s
also critical. Samples may be held overnight for gas chromatography
after being dried. The sensitivity of the modified method is 0.01 ppm
for carrots, spinach, and tomatoes.
A number of samples of tomatoes and spinach were sent to Dr. Ralph
Nash of USDA, Beltsville, Maryland to determine the ETU residues by an
Independent method. Unfortunately, Dr. Nash separated and analyzed the
liquid and solid portions of the crops while the method used for this
report analyzed the entire sample. The results, however, while not
fully comparable, are quite similar:
Commodity Rep. No. ETU found (Nash) ETU found (TRI)
0.32
0.01
0.18
0.50
0.15
0.05
TYPICAL ANALYSIS OF DITHANE (M-45 or M-22®) for EBDC and ETU
The formulated Dithane M-45 was analyzed for EBDC (ai) and ETU
content. The results are shown below:
Product Sample No. % ai % ETU
D1thane M-45? 2-0530-1 86.9 0.05
D1thane M-45^ 2-0530-2 83.8 0.11
Dithane M-2ZT 2-4502-1 86.9 0.02
D1 thane M-2r 2-4502-2 89.7 0.01
Western spinach unwashed
Western spinach washed
Eastern spinach canned
Western spinach canned
Western tomato canned
Eastern tomato canned
II
II
II
II
I
II
0.26
0.07
0.16
0.77
0.07
0.05
Analysis of the same samples by Rohm and Haas gave 85.7% EBDC and
0.02% ETU for sample 2-0530-1, and 83.3% EBDC and 0.05% ETU for
sample 2-0530-2.
-------
CALCULATION OF DATA
The active ingredient (EBDC) was determined by CS2 generation and
expressed as Dithane M-45 through use of the following calculation
(assuming the M.W. of Dithane M-22 to be 265.38):
wt. CS2 x 1.78 = wt. Dithane M-45®
The residues of parent compound in this study were calculated as
EBDC (M.W. = 210):
wt. CS2 x 1.38 and 1.74 = wt. EBDC
The factors 1.78 and 1.38 were determined as follows:
M.W. D1thane M-45 _ M.W. Maneb + 2% In _ 265.38 + 5.31 .
2 x M.W. CS,
152.26
1.78
M.W. EBDC
2 x M.W. CS,
210
T52726
1.38
In a similar calculation for active ingredient of Dithane M-22 /CS2
(factor
V
38
'S = 1.74) was made. As shown in the following equations, the
/
theoretical yield of ETU from EBDC is 48.6%:
CH2 - NH -
CH2 - NH -
EBDC (M.W. 210)
CH2 - NH,
CH2 - NH
ETU (M.W. 102)
M.W. ETU
M.W. EBDC
102
ZTTT
0.486 or 48.6%
METHOD OF FORTIFICATION OF CROPS •
The following procedure was typically followed: Ten mg Dithane M-45'
(or Dithane M-22®) was added to lOOg starch and the mixture thoroughly
10
-------
dispersed by stirring and shaking. The starch mixture was analyzed for
percent active ingredient, and 60 yg EBDC/g starch was found. Based on
this concentration of EBDC, the appropriate weight of starch for fortifi-
cation was added to the sample. This standard method of fortification
is essentially the one described by Gordon et al. (1967), except that
starch was substituted for Attapulgite clay.
For fortification with ETU, the chemical was made up in water, and
the appropriate volume of the solution was added to the crop. A detailed
description of the preparation and procedures is given as part of the
ETU analytical procedure (Appendix A).
11
-------
SECTION III
RESULTS AND DISCUSSION
The application of the registered level of the fungicides (Ix
treatment) was designed to simulate good agricultural practice. Fungicide
treatments at 4 times the registered level (4x treatment) were designed
to expose effects that might be missed with the normal level of application.
In both cases (and in the untreated controls or checks) the processing
(excluding the home cooking experiment) simulated good commercial practice.
Results obtained from this study, which include analyses at each processing
point of the three crops from the time of harvest, should therefore
provide a realistic insight into the presence of EBDC and ETU at the
various processing stages.
Tables containing the analytical data have been assigned Roman
numerals, and these tables have been placed immediately following the
text or in the Appendices. A listing of the tables is presented ahead
of the Introduction (see Contents). Summary tables, which give data on
sub-studies, generally give average residue values. Individual analytical
values, which are given in tables in the Appendices, have the same Roman
numerals as the Summary Tables and are followed by additional figures.
For example, the individual data from the Summary Table I may be found
in Tables having I as the first letter of the Table Number.
12
-------
RESIDUES FROM DITHANE M-45
Eastern Crops
As shown in Table 3, low levels of the parent compound (EBDC) and
the metabolite, ETU, were found on carrots and tomatoes grown 1n the
East. After processing both crops at the Ix rate of treatment, virtually
none of the parent compound (0.1 ppm or less) remained. During heat
processing of the Ix-treated tomatoes and carrots, the concentration of
ETU increased from <0.01 ppm to an average of 0.03 ppm in canned tomato
juice and canned carrots; the ETU concentration did not increase in the
frozen samples of carrots and tomatoes. The 4x treatment of unwashed
tomatoes and carrots contained parent compound at a concentration of 0.8
ppm. The average ETU content of canned carrots and juice of tomatoes
grown in the East was 0.05 and 0.10 ppm, respectively, for the 4x rates.
Spinach grown in the East contained appreciably higher levels of EBDC
and ETU than those in carrots and tomatoes in both the Ix and 4x treatments.
Western Crops and Comparison with Eastern Crops
Table 3 also presents the residue data from crops grown in the
West. Residues of EBDC in West-grown tomatoes (up to 7.1 ppm at the 4x
rate) were greater than those on tomatoes grown in the East; on West-
grown spinach, EBDC residues (up to 219.3 ppm at 4x rate) were great,
although they were virtually absent in canned spinach and low (0.6 to
2.0 ppm at 4x rate) in frozen spinach. Residues of ETU in West-grown
tomatoes were about the same as those in the Eastern tomatoes except
that amounts in the canned tomatoes were somewhat greater (up to 0.13 ppm
at 4x rate); ETU residues in carrots were generally less than 0.01 ppm
13
-------
(less than in Eastern carrots); ETU residues in Western spinach (up to
3.74 ppm) were far greater than corresponding residues in the Eastern
spinach. Thus, the study shows that very low residues may be expected
on carrots, low residues on tomatoes, and relatively high residues on
spinach when Dithane M-45" is applied at the Ix rate.
Except for unwashed Western-grown tomatoes from the 4x rate,
residues of EBDC on tomatoes and carrots (East or West) from the Ix and
®
4x treatment with Dithane M-45 were far below their respective tolerances
of 4 and 2 ppm.
Effects of Washing and Canning
Analyses of EBDC and ETU of unwashed, washed, and processed canned
products are shown in Table III (Appendix D), along with percent of ETU
converted from EBDC during this processing. The value for percent
conversion is based upon the amount of ETU found in the sample relative
to the theoretical quantity of ETU which could be obtained from the
residue of EBDC present prior to processing. These data indicate that
washing removes a significant amount of residue of EBDC (up to 87%).
The data also indicate that some of the EBDC residue is converted to ETU
during heat processing with the percent conversion being higher for
East-grown than West-grown crops. Average conversions ranged from 2.6 -
70.4% with an overall average of 26.6%. However, levels of EBDC residues
on tomatoes and carrots appear to be too low to assign any real signifi-
cance to the conversion values obtained.
Residues in tomato tailings (East or West) at the normal application
rate were very low (Tables IA-1-C and IB-l-C in Appendix B); at the
14
-------
4-fold rate, respective residues of EBDC and ETU were 0.5 and 0.01 ppm
in the East and 1.4 and 0.04 in the West.
Conversion of EBDC (Added as Pi thane M-45® to ETU Owing to Analytical
Method and Matrices
In order to determine conversion of EBDC to ETU due to the analytical
method and different matrices, control samples fortified with EBDC and
ETU were analyzed for ETU and percent conversion calculated. The results
are shown in Tables IV (Appendix D). The individual conversions ranged
from 1.6% to 46.6%. These results indicate that on the average there is
7-16% conversion of added EBDC to ETU in the ETU analysis of the tomatoes,
carrots, and spinach grown in the East and West.
In these fortification experiments, 0.05 ppm ETU was added to all
samples to improve the detectability of low levels of ETU by the flame
photometric detector. Response of the detector is proportional to the
square of the concentration of sulfur-containing compounds, so response
increases appreciably as the ETU concentration is increased.
Conversion of EBDC to ETU due to the analytical method was determined
in tomato juice when fresh EBDC alone was added to a control sample.
The conversion of EBDC to ETU was 15.6%. This conversion is comparable
to the conversion found in control samples of tomato juice when both
EBDC and ETU are added to the control sample matrix.
ETU Formation from Weathered Residues and from Added Dithane M-45®
Analyses of treated crops indicate that there is much less conversion
of EBDC to ETU from weathered residues of technical Dithane M-45® than
from Dithane M-45 that is laboratory-fortified. The maximum theoretical
15
-------
concentration of ETU from EBDC found on washed crops was calculated
(EBDC x 0.48 = Max. ETU), and the ETU actually found was expressed as a
percentage of the 100% theoretical conversion. For Eastern- and Western-
grown tomatoes and carrots and for Eastern-grown spinach, the ETU residues
from weathered samples did not exceed 0.01 ppm, so significant values
for percent conversion could not be obtained for these crops. However,
for Western-grown spinach, residues of EBDC and ETU were large enough to
calculate percent conversions. These data on weathered residues and
similar data from Dithane M-22 applications (to be discussed later)
follow:
Crop
Washed Spinach
Washed Spinach
Washed Spinach
Washed Spinach
Loc.
West
West
West
West
Treat.
lx(M45)
4x M-45
Ix M-22
4x M-22
Amount
Found
EBDC
9.7
58.7
35.2
192.4
Theor. Max.
Amt. ETU
Obtainable
4.71
28.53
16.9
92.4
Amount
Found
ETU*
0.02
0.08
0.06
0.41
%
Conversion
0.4
0.3
0.4
0.4
*For sake of discussion, the values under "Amount Found ETU" are assumed
to arise from conversion of EBDC to ETU.
The above percent conversions of EBDC to ETU for weathered residues
on West Coast spinach (0.38% average) are far below the 7.3% conversion
of EBDC (added as Dithane M-45®) to ETU for the same crop (See Table
IV).
An experiment was conducted to determine the rate of formation (and
breakdown) of ETU from technical EBDC in hot water. Distilled water was
buffered to pH 5.21 with citric add/disodium phosphate. This pH 1s
16
-------
representative of the mid-range of acid foods. A portion of the buffer
solution served as a control. The two solutions were brought to a boil
in two-quart stainless-steel pots, and Dithane M-45* was added to one of
them (initial concentration EBDC 6.2 ppm). Aliquots were withdrawn from
the boiling Dithane M-45* water solution after ca. 0.5, 30, 60, and 90
minutes. Similar aliquots were withdrawn from the boiling control
solution at 0 and 60 minutes. The aliquots of water were placed in 4-oz
(113-ml) Nalgene bottles and rapidly frozen in a dry ice-acetone bath.
Time involved for complete freezing of the samples was about 10 minutes.
Samples were thawed for analyses of EBDC and ETU with a warm water bath.
The degradation of EBDC in boiling water and the formation of ETU
occurred very rapidly (Table VI in Appendix D). On continued boiling
for 60 minutes, about 50% of the ETU degraded. The apparent increased
conversion at 90 minutes is attributed to concentration factors of
boiling and withdrawal of aliquots.
17
-------
RESIDUES FROM DITHANE M-22 (maneb)
Tomatoes, Residues at the Various Processing Stages
Table 4 summarizes the average residue data obtained from tomatoes
grown in Davis, California and treated with Dithane M-22 at the Ix
(registered) and 4x levels. Untreated (check) samples were included as
controls. For the washed and unwashed tomatoes, levels of residues were
similar to those reported for Dithane M-45 West Coast tomatoes except
for the higher ETU residue (0.10 ppm) in the 4x treatment of the washed
tomatoes.
As with Dithane M-45, washing reduced the residues of EBDC. Canned
whole tomatoes had some residues (Ix treatment EBDC 0.3 ppm, ETU 0.02;
4x treatment EBDC 0.4, ETU 0.07). When this commodity was cooked for 5
and 60 minute intervals, the EBDC residue decreased to 0.1-0.3 ppm, and
the ETU residue increased to 0.06-0.07 ppm for the Ix treatment and was
0.06-0.11 for the 4x treatment.
Residues in canned tomato juice (ca. 6% solids) were similar to
those reported for the West Coast product in the Dithane M-45 study and
are slightly larger than those that were found in canned whole tomatoes.
For the Ix treatment, residues were EBDC 0.4 ppm, ETU 0.04; 4x treatment
EBDC 0.8, ETU 0.12.
The tomato sauce, which based on its solids content of about 15%
may be considered an approximately 2%-fold concentrate of tomato juice,
contained in the Ix treatment 0.8 ppm EBDC and 0.11 ppm ETU and in the
4x treatment 2.7 ppm EBDC and 0.22 ppm ETU. The increases in residues
18
-------
over those in the tomato juice samples appear to be mainly a concentration
effect; i.e., residues are about 2% times those in the juice.
The tomato paste (ca. 30-35% solids) may be considered a further 2-
fold concentrate of the tomato sauce. Again, the increase in residues
appears to be mainly a concentration effect. Residues in the Ix treatment
were EBDC 2.2 ppm and ETU 0.37; in the 4x treatment, EBDC 3.7 and ETU
0.46. These values are about double those found in the sauce.
The increase in ETU content, which appears to accompany the high
temperature (ca. 116°C) used in canning, probably occurs to a much
lesser extent in the lower-temperature concentration (ca. 70°C vacuum)
used to prepare tomato sauce and tomato paste.
Spinach, Residues at the Various Processing Stages
Table 4 summarizes the average residue data obtained from spinach
®
grown in Davis, California and treated with Dithane M-22 at the 0, Ix,
and 4x levels. As with Dithane M-45 -treated West Coast spinach, residue
levels were high (Ix treatment EBDC 35.2-86.6 ppm, ETU 0.05-0.24; 4x
treatment EBDC 186.8-192.4, ETU 0.05-0.24). In most cases, washing
reduced the residue levels.
Blanching and freezing greatly reduced the EBDC residues on the
washed spinach (1 and 4x treatments 0.4 and 0.9 ppm, respectively) but
increased the ETU residues (1 and 4x treatment 2.00 and 0.89, respectively)
After cooking and simmering the blanched frozen spinach for 5 minutes,
residues of EBDC were lowered (0.2-0.4 ppm); ETU residues remained about
the same (1 and 4x treatments 0.76 and 1.44, respectively). The water
19
-------
drained from the blanched frozen cooked spinach had no EBDC residue; ETU
residues were 0.65 and 0.58 ppm for the Ix and 4x treatments, respectively.
Canned spinach contained <0.1 ppm EBDC residues; ETU residues were
1.82 and 2.50 ppm for the 1 and 4x treatments. After cooking and simmering
the canned spinach for 5 minutes, ETU levels were 2.12 and 2.26 ppm for
the 1 and 4x treatments; ETU residues in the drained water from this
cooking were 1.03 and 0.58 ppm for the 1 and 4x treatments, respectively.
The pattern of increased levels of ETU and very low levels of EBDC
in canned products has continued with the spinach samples.
Residues from Whole Washed Tomatoes Fortified with EBDC and ETU
Control (untreated) whole washed tomatoes were fortified with
amounts of EBDC and ETU found in whole tomatoes from the 4x field treatment
®
with Dithane M-22 to compare residues from laboratory-fortified samples
with those from the 4x field treatment. Fortifications were made with
0.5 ppm EBDC alone, with 0.07 ppm ETU alone, and with 0.5 ppm EBDC and
0.07 ppm ETU together. The data are summarized in Table VII (Appendix
D) along with the residue data from whole tomatoes from the 4x treatment
in the field.
In general, the residue data from the samples fortified with both
EBDC and ETU agree reasonably well with the data from the field-treated
samples.
The sums of the EBDC and ETU residues from the individual fortifi-
cations with EBDC and ETU also appear to be reasonably similar in magni-
tude to the EBDC and ETU residues found in the samples fortified with
both chemicals.
20
-------
Conversion of Added EBDC to ETU in Tomatoes and Spinach
The conversion of EBDC to ETU owing to analytical method and different
matrices was determined as with Dithane M-45P (see Table IV in Appendix
D) by fortifying control samples with EBDC and ETU and analyzing for
EBDC and ETU to determine percent conversion. A summary of the data is
given in Table V.
Percent conversions of EBDC to ETU ranged from 1.7 to 50% for the
washed and unwashed tomatoes and canned whole tomatoes and tomato juice,
with an average conversion of 19.9%. This result agrees reasonably well
with the 16% average conversion for West Coast tomatoes found in the
Dithane M-45* study.
For the unwashed, washed, frozen, and canned spinach, the percent
conversion of EBDC to ETU ranged from 0.0 to 9.3% and averaged 5.4%.
Again, there is reasonably good agreement of this value with the 7.3%
®
average conversion for West Coast spinach found in the Dithane M-45 study.
Confirmation of ETU by GC/MS
In addition to the quantitative check performed by Dr. Nash, ETU
results on canned spinach control Rep III, Ix Rep I and 4x Rep III were
confirmed by GC/MS. These analyses were performed on different subsamples
than shown in Table 1C-4-D. Tlie Hewlett-Packard Model 5980A mass spectro-
meter with an all-glass GC interface was employed.
The spectra for a 50 n sample of S-n-Butyl ETU in the El mode
produced major clusters of ions around m/e 102 and 129. In the CI mode
with methane, major ions at 159 (P + 1) and 187 (P + 29) were produced.
These spectra along with those obtained for samples noted above are
21
-------
shown In Appendix E, Tables I thru VIII. The samples of treated spinach
contained a compound whose spectra and retention time matched the standard.
The same samples were also analyzed for ETU by the GLC method
described In Appendix A. The table below compares the quantitative GC
and GC/MS analyses performed.
ppm ETU
FPD CI EI_
Sample (FFAP) (OV-101) (FFAP) (FFAPJ
Canned Spinach, Control, Rep III <0.01 0.01 <0.01 <0.01
Canned Spinach Ix M-45, Rep I 1.03 0.83 1.04 1.02
Canned Spinach 4x M-45, Rep III 3.4 4.40 4.17
The MS quantitation was based ratios of single ion monitoring of
sample vs. standard Ions at mass 102 and 129 for El and mass 159 and 187
in CI mode.
An early unknown eluter was detected in the 4x spinach sample by
GC/MS in El mode. The major ions of the unknown were at mass 116. No
additional work toward identification of this compound was conducted.
However, we Intend to complete the Identification, if possible, in the
near future.
22
-------
RESIDUE DATA FROM FIELD TREATED CROPS
These data are presented in Tables 3 and 4.
A summary of the recovery data is given in Table VIII (Appendix D)
23
-------
Table 3. SUMMARY OF DATA ON RESIDUES OF EBDC AND ETU AT
VARIOUS PROCESSING STAGES FROM TOMATOES, CARROTS, AND SPINACH
GROWN AT EAST AND WEST COAST LOCATIONS AND TREATED WITH
DITHANE M-45 AT 0, 1, AND 4 TIMES THE REGISTERED RATES.
EACH RESULT IS AVERAGE OF AT LEAST SIX DETERMINATIONS.
Coirmodi ty
A. Tomatoes
B. Carrots
C. Spinach
Process
Stage
Unwash
Unwash
Unwash
Wash
Wash
Wash
Tailings
Tailings
Tailings
Juice Canned
Juice Canned
Juice Canned
Unwash
Unwash
Unwash
Wash
Wash
Wash
Diced
Diced
Diced
Frozen
Frozen
Frozen
Canned
Canned
Canned
Unwash
Unwash
Unwash
Wash
Wash
Wash
Frozen
Frozen
Frozen
Canned
Canned
Canned
Application
Rate
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
East
EBDC
<0.1
0.3
0.8
0.1
0.2
0.3
0.1
0.2
0.5
0.1
<0.1
0.1
<0.1
0.6
0.8
<0.1
0.3
0.7
<0.1
0.1
0.4
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.2
2.4
6.4
0.1
1.5
2.7
<0.1
0.1
0.4
0.1
<0.1
<0.1
Coast
ETU
<0.01
<0.01
0.02
0.01
<0.01
0.01
<0.01
<0.01
0.01
0.01
0.03
0.10
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.03
0.05
<0.01
<0.01
0.01
<0.01
<0.01
0.01
<0.01
0.04
0.07
0.01
0.18
0.44
West
EBDC
<0.1
2.1
7.1
<0.1
0.6
0.9
• -
0.4
1.4
<0.1
0.5
1.8
<0.1
0.1
0.4
<0.1
0.1
0.4
<0.1
0.1
0.1
<0.1
<0.1
<0.1
<0.1
0.1
0.1
0.3
61.9
219.3
0.2
9.7
58.7
0.1
0.6
2.0
0.1
0.1
0.1
Coast
ETU
<0.01
0.01
0.02
<0.01
0.01
0.01
<0.01
<0.01
0.04
0.01
0.11
0.13
<0.01
0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.34
1.41
<0.01
0.02
0.08
0.01
0.50
3.74
0.01
0.71
2.66
Dithane M-45 is not registered for use on spinach. R^tes of 1.6 and 6.4
Ib ai/acre were applied to match those of D1thane M-22 , which is registered
for use on spinach.
24
-------
Table 4. SUMMARY OF DATA ON RESIDUES OF EBDC AND ETU AT
VARIOUS PROCESSING STAGES FROM TOMATOES AND SPINACH GROWN IN THE
WESTERN U.S. AND TREATED WITH DITHANE M-22 AT 0, 1, AND 4 TIMES THE
REGISTERED RATES. EACH RESULT IS AVERAGE OF AT LEAST SIX DETERMINATIONS
Process Application
Commodity Stage Rate
A. Tomatoes Unwashed
Unwashed
Unwashed
Washed
Washed
Washed
Canned Whole
Canned Whole
Canned Whole
Juice Canned
Juice canned
Juice Canned
Canned Whole Tomatoes,
cooked and simmered
for 5 minutes
Canned Whole Tomatoes,
cooked and simmered
for 60 minutes
Sauce
Sauce
Sauce
Paste
Paste
Paste
B. Spinach Unwashed
Unwashed
Unwashed
Washed
Washed
Washed
Blanched Frozen
Blanched Frozen
Blanched Frozen
Blanched Frozen Spinach,
cooked and simmered
for 5 minutes
Drained Water from Blanched
Frozen Cooked Spinach
Canned
Canned
Canned
Canned Spinach, cooked
and simmered for
5. minutes
Drained Water from
Canned Spinach, cooked
and simmered for 5 minutes
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
Check
Ix
4x
EBDC
0.2
2.4
8.0
0.1
0.3
0.5
<0.1
0.3
0.4
<0.1
o!4
0.8
<0.01
0.2
0.3
<0 1
oil
0.3
<0.1
0.8
2.3
0.1
2.2
3.7
0.2
86.6
186.8
0.1
35.2
192.4
<0.1
o!4
0.9
<0.1
o!2
0.4
<0.1
<0.1
<0. 1
<0.1
<0.1
<0.1
-------
SECTION IV
REFERENCES
EPA Compendium of Registered Pesticides (from Food and Chemical News, Inc.,
Oct. 1, '1976). For Dithane M-45, authorities cited are 40 CFR 180.176;
180.319; 21 CFR 123.460; 561.410. For Dithane M-22, authority cited is
40 CFR 180.110.
Gordon, C. F., et al., Improved Method for the Determination of Ethylene-
bisdithiocarbamate Residues in Plants, Fruits, and Vegetables. J. AOAC
50: 1102-1108, 1967.
Haines, L. D., and I. L. Adler. Gas Chromatographic Determination of
Ethylene Thiourea Residues. J. AOAC 56: 333, 1973.
Keppel, G. E. Collaborative Study of the Determination of Dithiocarbamate
Residues by a Modified Carbon Disulfide Evolution Method. J. AOAC
54: 528-532, 1971.
26
-------
APPENDIX A
Detailed Analytical Procedure Used to Determine ETU
Modified Rohm & Haas Co. Procedure - Test Method 1881-1, July 29, 1975
27
-------
This test method is a comprehensive procedure for the determination
of trace levels (to about 0.01 ppm , minimum) of ethylenethiourea (ETU).
Ethylenethiourea (ETU, 2-1midazolidinethione) is a suspected carcinogen
and is a possible decomposition product of certain ethylene bisdithiocarbamate
fungicides* among them Dithane. This test method was first developed to
determine whether potatoes, including those treated with Dithane, were
free from ETU residue. It has since been extended to include all Dithane-
treated food crops. The method has also been successfully used to
determine ETU residue in urine.
Method
ETU is extracted from finely divided samples with methanol and
acetone; the resulting slurry is filtered and concentrated, then partially
purified by passing it through an alumina column. A chromatographable
S-butyl ETU derivative is prepared by mixing the column eluate with
dimethyl formamide (DMF), evaporating the more volatile solvents, and
then adding 1-bromobutane, sodium borohydride, and sodium hydroxide. A
portion of this solution is acidified, evaporated to dryness, and redis-
solved in sodium hydroxide solution. The derivative is extracted from
the basic solution with benzene, and the benzene extract is separated
gas chromatographically, using a 6-foot, glass column packed with [5%
KOH and 10% Carbowax 20M liquid phase on 80/100 Gas Chrom Q support.]
The ETU derivative is detected by a sulfur-sensitive, flame-photometric
detector.
The ETU content is determined by comparing peak heights of samples
and control samples to standard solutions of known S-butyl ETU content.
*As modified by MDG/WFP
28
-------
A recovery factor is used to correct the ETU content of samples and is
determined by adding known levels of ETU to portions of the untreated
control samples, and carrying these "spiked" controls through the entire
analysis.
Safety
Avoid contact with all toxic or corrosive liquids. In case of skin
contact, wash the affected area immediately with copious quantities of
water. In case of eye contact, similarly wash, and obtain medical
assistance.
Ethylenethiourea (ETU) is suspected of causing cancer. Scrupulously
avoid breathing ETU dust, or allowing skin contact with it or its solutions;
use rubber gloves when handling. In case of contact, immediately wash
the affected area with copious quantities of water, followed by soap and
water. After handling ETU or its solutions, and especially before
eating, drinking or smoking, wash the hands thoroughly with soap and
water. Remove and wash any contaminated clothing before using again.
S-Butyl Derivative of ETU—The toxicity of this material is unknown,
therefore, handle this material as though it were toxic; the same as
ETU.
Acetone—Flammable (FP 0°F, CC). Moderately toxic by inhalation
and causes skin irritation.
Benzene—Flammable (FP 12°F, CC). Highly toxic by ingestion,
inhalation, and skin absorption. Tolerance, 25 ppm in air.
1 -Bromobutane— Flammable (FP 75°F, OC). Probably toxic. Handle
this material in a hood; mild lachrymator.
29
-------
Dimethylformamlde (DMF)—Moderately flammable (FP 136°F, CC).
Highly toxic by skin absorption and ingestlon; irritant to skin, eyes
and mucous membranes.
Methanol—Flammable (FP 54°F, OC). Toxic by Ingestlon, skin absorption
and inhalation.
Hydrochloric acid—Corrosive liquid, highly toxic by ingestion and
inhalation; strong irritant to eyes and skin.
Sodium Borohydride--Reacts with water and solutions of acid or
metallic salts to produce hydrogen (a flammable gas) and sodium hydroxide
(a corrosive liquid). Dangerous fire risk. Store this material 1n a
desiccator. Toxic through Ingestlon and skin contact; avoid breathing
its dust.
Sodium hydroxide—This material and its solutions are corrosive.
Highly toxic by Ingestlon and inhalation; strong irritant to skin, eyes
and mucous membranes.
Petroleum Ether—Flammable (FP -40°F). Highly toxic by Ingestion,
inhalation, and skin absorption.
Hexane— Flammable (FP -9°F). Moderately toxic by inhalation and
Ingestlon.
Apparatus
Aluminum Dishes, throw-away—5 cm diameter x 1.5 cm depth.
Balance—Top-loading, 1200 g capacity. Mettler Model P-1200 or
equivalent.
Balance—Analytical.
Beakers—50 ml, 100 ml, 250 ml.
30
-------
Bottles, Amber Glass—with aluminum-foil-lined screw caps. Various
sizes.
Bottles, Plastic—Squeeze-type with capillary tip, 500 ml & 1000 ml.
Buchner Funnels, Coors size 4 (126 mm), Porcelain.
Burette, 50 ml with Teflon stopcock—Certified, NBS.
Centrifuge--Capable of 2000 rpm, with head capable of accepting
Mini Vials.
Desiccator—with moisture indicating desiccant.
Dropping Pipettes, Capillary, Disposable—2 and 4 ml. Kimble Cat.
No. 72020 and 72060, or equivalent.
Erlenmeyer Flasks—250 ml.
Erlenmeyer Flasks, with a f 24/40 joint. 500 ml, 1000 ml.
Erlenmeyer Flasks, Bantamware—with f 14/20 joint. 50 ml.
Filter Flasks-250 ml, 500 ml, 1000 ml.
Filter Funnel —Fine porosity, 30 ml.
Filter Paper--Whatman No. 1 & No. 541 or equivalent. To fit Buchner
funnel (11 cm).
Freezer—Set to -5°C or colder.
Gas Chromatographic Columns—6 ft x 1/4 in, glass, packed with (10%
Carbowax 20M + 5% KOH) liquid phase on Gas Chrom Q support.
*
Gas Chromatographic Instrument—(Micro-Tek 220,) with Tracer flame
photometric detector and 0-1 mV recorder.
Graduated Cylinders—25 ml, 50 ml, 100 ml.
Graduated Cylinders--with ground-glass stoppers, 10 ml.
*As modified by MDG/WFP
31
-------
High-Speed Blender--Waring Blender or equivalent, with 1-pint glass
container, screw-type metal lids. Replace all rubber gaskets
with Teflon.
Liquid Chromatographie Columns—2.2 cm diameter x 10 cm length
2.2 cm diameter x 40 cm length
1.0 cm diameter x 25 cm length,
with 200 ml reservoir and a 2 mm
bore Teflon stopcock.
Mini Vials, 5 ml, with Teflon-lined caps—Available from Alltech
Associates, 202 Campus Drive, Arlington Heights, Illinois 60004.
Oven—Forced draft, with settings of 80° and 130°C.
Polyethylene Sheet—3 mil, for Blender-jar cap liners.
Reflux Condenser—with s~ 24/40 joint. 300 mm Allihn or similar.
Rotary Vacuum Evaporator—? 24/40 joint, adaptor for Bantamware
joint, 5 24/40 to 14/20.
Round-Bottom Flasks—With f 24/40 joint. 300 ml, 500 ml, 1000 ml.
Rubber Stoppers, No. 6—bored to fit the Chromatographic Column
as illustrated in Fig. 1.
Separatory Funnels—250 ml.
Serological Pipettes—1 ml, 2 ml, 5 ml, 10 ml.
Shaker--Bench-type, lateral action, variable speed. Available
from A. H. Thomas.
Spatula—Hayman microspatula. A. H. Thomas Cat. No. 8340-H20.
Stirring Hot PIate--Corning Model PC-351 or equivalent.
Transfer Pipettes—Various sizes Including a 4 ml Class A.
32
-------
"T1 pets "—Automatic measuring with f 24/40 joint. 5 ml, 10 ml,
15 ml, 25 ml, 50 ml, 75 ml, 100 ml.
Volumetric Flasks—100 ml, 250 ml, 500 ml, 1000 ml.
Watch Glass—At least 90 mm in diameter.
Water Bath—Capable of adjustment within a range of 55° to 88°C.
Reagents
Acetone—Burdick & Jackson "Distilled-in-Glass" grade.
Aluminum Oxide—Baker "Analyzed" Reagent Grade or Fisher A-540
Adsorption Alumina. Wash each pound of this reagent with 1
liter of anhydrous methanol, filter with vacuum on No. 1 filter
paper, wash again with 100 ml of methanol, allow to air dry,
activate at 130°C for 2 to 3 hours, and store in a tightly
capped container in a desiccator.
Benzene—Burdick & Jackson "Distilled-in-Glass" grade.
1-Bromobutane—Matheson, Coleman & Bell, Cat. No. BX 1045. Purify
by passing 100 ml of the reagent through a 2.2 cm-diameter x 10
cm-long chromatographic column containing 40 grams of activated
aluminum oxide and capped with a glass-wool plug. Do this opera-
tion in a hood.
DimethyIformamide (DMF)—Burdick & Jackson "Distilled-in-Glass"
grade.
Ethylenethiourea (ETU)—Eastman Practical Grade, Cat. No. B 5950.
Toxic, see "Safety" section.
Methanol—Burdick & Jackson "Distilled-in-Glass" grade.
Hydrochloric Acid—Concentrated, reagent grade.
33
-------
Sea Sand, washed and 1gnited--F1sher Scientific Co.
Sodium Borohydride (NaBH4)--F1sher Scientific Co., Cat. No. S-678
(10 grams). This material 1s hydroscoplc; order the smallest
available containers, and avoid prolonged exposure to air. Store
in a desiccator.
Sodium Hydroxide Solution, 20%--Weigh 50 grams of reagent-grade
sodium hydroxide pellets into a 300 ml beaker, add 200 ml of
distilled water, and stir to dissolve. Store in a capped,
labelled, polyethylene container.
Wash Solution: 5% Acetone in Benzene—Prepared by mixing 50 ml
of acetone with 950 ml of benzene.
Elution solvent: 7% Methanol in Wash Solution—Prepared by mixing
70 ml of methanol with 930 ml of Wash Solution.
Petroleum Ether—Burdick & Jackson "Distilled-in-Glass" grade.
Hexane—Burdick & Jackson "Distilled-ln-Glass" grade.
Methanol/Water Solution, 50/50—prepare in convenient quantities by
mixing equal volumes of methanol and distilled water.
(Extraction Solvent—methanol, acetone, water, trichloroacetlc acid-
(250:127:37.5:1V/V)*
Special Reagents
Recrystall1zed ETU - Preparation:
Transfer 100 ml of methanol/water solution (50/50) into a 250 ml
Erlenmeyer flask. Add 5 grams of ETU to the flask and heat the contents
on a hot plate, swirling Intermittently, until the ETU has dissolved.
Place the flask in a pan of running tap water to cool for five minutes.
*As modified by WFP/MDG
34
-------
After cooling, add 5 ml of hexane, shake the flask vigorously, and
transfer it to a freezer. At the same time transfer a container with
100 ml of methano!/water to the freezer. Allow the ETU to recrystallize
overnight. Filter the ETU crystals using a fine-porosity filter funnel
under vacuum. Rinse the crystals with two 15 ml portions of chilled
methanol/water solution. Allow the crystals to air dry overnight, then,
transfer them to a watch glass, and finish drying them in an 80°C oven
for three hours. Determine the melting point range of the dried crystals;
if the melting range exceeds 1.2°C, or if the initial softening occurs
below 198°C, repeat the recrystallization using the dried crystals.
Store the finished, recrystallized ETU in a desiccator.
S-Butyl Derivative - Preparation:
Transfer 2 grams of recrystallized ETU to a 500 ml Erlenmeyer flask
with 5 24/40 joint. Separately mix 20 ml of 1-bromobutane with 180 ml
of methanol; add this mixture, plus 50 ml of 20% sodium hydroxide, and a
magnetic stirring bar to the contents of the Erlenmeyer flask. Connect
a reflux condenser to the flask, and place it on a stirring hot plate.
Stir the contents and heat them until the solution refluxes at a rate of
1 to 3 drops per second. Allow the refluxing to continue, adjusting the
hot plate setting as necessary to maintain this rate, for 10 minutes.
Allow the flask contents to cool, and transfer them to a 500 ml separatory
funnel. Add 100 ml of benzene, and shake the funnel vigorously for
about two minutes, venting the stopcock frequently to avoid pressure
increase. Allow the layers to separate; drain the lower layer into
another separatory funnel, and transfer the upper layer to a clean
35
-------
500 ml Erlenmeyer flask. Repeat the extraction with three additional
100 ml portions of benzene, adding the upper layers of each extraction
to the same 500 ml Erlenmeyer flask.
Transfer the benzene solution to a 2.2 cm chromatographic column
containing a 5 cm bed of anhydrous sodium sulfate; collect the column
effluent in a 1000 ml, round-bottom flask with 5 24/40 joint. After all
the benzene has passed through the column, wash the column with two 20
ml portions of benzene, adding this effluent to the round-bottom flask.
Connect this flask to a rotary evaporator, slowly evacuating the flask
while rotating it, and immerse it in a water bath adjusted to 65 ± 5°C.
Concentrate the solution to between 60 and 80 ml, transfer it to a 125
ml, round-bottom flask with s" 24/40 joint, and continue to concentrate
the solution until between 4 and 5 ml remain in the flask.
Remove the flask from the evaporator, and add 25 ml of water.
Swirl to dissolve the material, and transfer it to a 125 ml separatory
funnel. Add 25 ml of petroleum ether to the funnel, and shake vigorously.
Allow the layers to separate, and transfer the lower (water) layer to
another 125 ml separatory funnel. Pour the upper (petroleum ether)
layer into a 250 ml Erlenmeyer flask. Repeat the extraction of water
with two more 25 ml portions of petroleum ether, adding these upper
layers to the 250 ml Erlenmeyer flask. Transfer the solution from the
Erlenmeyer flask to a chromatographic column containing a fresh, 5 cm
bed of anhydrous sodium sulfate. Rinse the Erlenmeyer flask with 25 ml
of petroleum ether, and when the liquid in the column reaches the top of
the packing, transfer the rinse to the column. Collect the column
effluent in a 300 ml round-bottom flask with I 24/40 joint.
36
-------
Adjust the water-bath temperature to 55°C. Connect the 300 ml
flask to the rotary evaporator, immerse the flask in the bath, and
evaporate the petroleum ether without vacuum until only a few milliliters
of liquid remain. Apply vacuum to the flask for only a few seconds, to
remove the remaining petroleum ether. Place the flask in the freezer
overnight, then decant the supernatant liquid from the crystals, transfer
them to a sheet of filter paper, and allow them to air dry overnight.
Transfer the crystals to a 50 ml beaker and add about 10 ml of petroleum
ether; warm the beaker on a steam bath, and stir to dissolve the crystals.
Continue heating until most of the ether has evaporated. Transfer the
moist crystals to a clean sheet of filter paper on a watch glass, and
place the glass in the freezer until crystallization is complete.
Transfer the crystals to another 50 ml beaker, and repeat the recrystalli-
zation from 10 ml of petroleum ether. Store the recrystallized product
in the freezer in a capped, labelled container.
ETU Spiking Solutions - Preparation:
Weigh 0.0250 gram of recrystallized ETU into a 500 ml volumetric
flask. Dissolve and dilute to the graduation mark with distilled water,
and mix well. Label this Solution "A-l" (50 yg/ml ETU) and store in a
capped, amber bottle under refrigeration; allow this solution to warm
to room temperature before using. Prepare Working Solution "A-2"
(1 yg/ml ETU): pipette 5.0 ml of Solution "A-l" into a 250 ml volumetric
flask, dilute to the graduation mark with distilled water, and mix well.
Prepare Working Solution "A-3" (0.40 yg/ml ETU): pipette 100 ml of
Solution "A-2" into a 250 ml volumetric flask, dilute to the graduation
37
-------
mark with distilled water, and mix well. Store Working Solutions "A-2"
and "A-3" in capped, labelled, amber bottles at room temperature; retain
these solutions no longer than 3 months.
Standard Solutions - Preparation:
Weigh 0.0250 gram of recrystallized S-Butyl ETU derivative Into a
250 ml volumetric flask. Dissolve and dilute to the graduation mark
with benzene, and mix well. Label this Solution "B-l" (100 yg/ml of
derivative) and store 1n a capped, amber bottle under refrigeration;
allow the solution to warm to room temperature before using. Prepare
Solution "B-2" (10 yg/ml of derivative which is equivalent to 6.46 yg/ml
as ETU): pipette 10.0 ml of Solution "B-l" into a 100 ml volumetric
flask, dilute to the graduation mark with benzene, and mix well. Solution
"B-2" is used to prepare the eight Working Standard Solutions in the
following Table I. Using a 50 ml burette (Certified, NBS), transfer the
indicated volumes of Solution "B-2" Into 8 respective 100 ml volumetric
flasks, dilute to the graduation mark with benzene, and mix well. Store
•»
these solutions in tightly capped, labelled, amber bottles at room
temperature, and retain no longer than 4 months. Discard the remaining
Solution "B-2".
38
-------
Table I
Volume of Solution Micrograms/Milliliter
"B-2" in ml as ETU
3.1
6.2
7.8
9.3
10.9
12.4
14.0
15.6
0.2
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Procedure
A set of analyses requires at least 120 grams of a Control (untreated)
sample and 40 grams of each treated sample. By the term "treated" we
mean material which has been exposed to D1thane.
Because the procedure is lengthy, and because results may be decreased
by time delays during certain critical operations, a single operator
should not normally attempt to run more than five treated samples concur-
rently. This analysis normally requires two days; the first for preparation
of the samples for gas chromatography, and the second for the chromatographic
analyses.
Determine the volumes of ETU Spiking Solution (A-2 or A-3) required
for two "fortification" levels: one, approximately equal to the expected
ETU content of the treated samples, which is determined according to the
39
-------
following calculation; and the second twice the first. (NOTE: If no
detectable ETU content is expected in the treated samples, use fortification
levels of 0.02 and 0.04 ppm.)
(1) Volume of ETU Spiking Solution =
(Expected Sample ETU, ppm) x 40 g Sample
Spiking Solution Concentration, yg/ml
For example:
Volume = °'°? PP"!? 40 3 = 2 ml of Spiking Solution A-2
and, Volume of second Spike = 4 ml of Spiking Solution A-2.
Pipette the calculated fortification volumes of Spiking Solution A-2
or A-3 into Control samples when indicated by the procedure.
Sample Preparation
Carry each sample (one Control, two Controls for fortification, and
each treated sample) consecutively through the procedure in the following
two paragraphs, to the indicated point.
Weigh 40 grams ± 0.1 g of sample (use a top-loading balance) directly
into a 1-pint, glass Waring Blender jar. Add [167 ml of the extraction
mixture] to the jar. (NOTE: Add the required volume of Spiking Solution
to each of the two Controls reserved for fortification; these two samples
will now be referred to as "Spiked Controls".) Cover the jar with a
piece of polyethylene sheet, and tighten the metal screw cap over it.
Blend the mixture at low speed for two minutes. Transfer the blended
mixture quantitatively to No. 541 Whatman filter paper in a Buchner
funnel; rinse the plastic liner (into the funnel) with methanol, and
rinse the Blender jar twice with 30 ml portions of methanol, adding the
*
As modified by Technological Resources Inc.
40
-------
rinses to the funnel. Filter the mixture (with vacuum) into a 1000 ml
filter flask, rinsing the inside walls of the funnel and the filter cake
with about 25 ml of methanol. Transfer the filtrate quantitatively to a
500 ml round-bottom flask, rinsing the filter flask with small portions
of methanol (limit the total solution volume to about 300 ml). Mark
each round-bottom flask with the identity of its contents. (NOTE:
Bring all samples to this point before proceeding.)
Set the water bath temperature to 80°C. Connect the round-bottom
flasks (in groups of four) to the rotary evaporator (condenser stopcocks
in the open position) and immerse them in the water bath. Allow the
contents of each flask to distill (without vacuum) into the discard
trap; when the refluxing stops, close the condenser stopcock, and apply
vacuum. Concentrate the contents of the flask until approximately 3 to
5 ml remain; then remove the flask from the evaporator and immediately
.»
transfer its contents (use a 4 ml disposable, capillary pipette) to a 10
ml glass-stoppered graduated cylinder. Rinse the round-bottom flask
with two equal (1 to 2 ml) portions of distilled water and add both
rinses to the cylinder (Do not exceed 8 ml total volume in the cylinder).
Dilute the graduated cylinder to 8 ml with distilled water, stopper, and
mix well. (NOTE: Bring all samples to this point before proceeding to
the next section.)
Liquid Chromatographic Purification
NOTE: Complete all the following operations (up to the acidification
step in the "Derivative Formation" section) as quickly as possible; ETU
in the sample decomposes rapidly, especially in DMF solutions.
41
-------
Prepare a chromatographic column for each sample as shown in Figure 1.
Place a 250 ml vacuum filtration flask under the column outlet and
secure it tightly to the rubber stopper. NOTE: The column stopcock
remains fully open during all the following operations. Using a serological
pipette, transfer 1.0 ml of the aqueous extract from the 10 ml cylinder
directly to the top of the column packing. Add two 1 ml portions of
benzene to rinse the pipette and allow each of these rinses to drain
into the top of the column, about 1/4 inch below the surface of the
sand; then add 25 ml of benzene to the column. Allow the benzene to
fill the column by gravity, then apply vacuum to the filter flask (the
filtration rate is adjusted to about (4) ml/minute with a "C" clamp
which is attached to the vacuum line). NOTE: To this point, do not
allow the liquid level to fall below the column-packing surface during
any step; the packing will crack and channel if this happens. When the
liquid level at the top of the column falls to the sand surface, add 75
ml of "Wash Solution" (5% acetone/benzene); then when the liquid level
at the top of the column falls to the sand surface, disconnect the
vacuum line, discard the filtrate, and connect a fresh filtration flask
(250 ml) to the column outlet. Add (90)* of "Elution Solvent" (7%
methanol in Wash Solution) to the column and re-apply vacuum at the same
12 ml/minute rate. Allow the liquid to drain entirely from the column
into the flask; then transfer the eluate to a 300 ml round-bottom flask.
Rinse the filtration flask with 25 ml of methanol and add the rinse to
the round-bottom flask. Using a Tipet dispenser, add 10.0 ml of distilled
water and 5.0 ml of dimethylformamide (DMF) to the round-bottom flask.
*
As modified by Technological Resources Inc.
42
-------
Connect the flask to the rotary evaporator and Immerse the flask in a
water bath adjusted to 78 ± 3°C. Allow the more volatile solvents
(acetone and methanol) to evaporate; then apply vacuum and evaporate the
solution until the volume is reduced to between two and three milliliters.
Immediately transfer this solution to a 10 ml glass stoppered graduated
cylinder, using a 2 ml capillary dropping pipette. Rinse the flask
twice with 1 ml portions of DMF, adding both rinses to the cylinder.
Dilute the cylinder to 6.0 ml with DMF.
Derivative Formation
Using a 1 ml serological pipette, add 0.3 ml of 1-bromobutane to
the graduated cylinder and swirl to mix. Fill the scoop end of a Hayman
microspatula one-third full with sodium borohydride (about 0.01 g), and
add this reagent to the cylinder; stopper and shake vigorously for about
10 seconds. Pipette 1.0 ml of 20% sodium hydroxide solution into the
cylinder and shake it vigorously for 10 seconds, then allow it to stand
at room temperature for 5.0 minutes.
Transfer 4.0 ml (by transfer pipette) of the upper layer from the
cylinder to a 50 ml Bantamware Erlenmeyer flask. Add 1 drop of concentrated
hydrochloric acid, connect the flask through an adaptor to the rotary
evaporator, and mark the flask with the identity of its contents.
(NOTE: After the acid addition time is no longer critical.) Immerse
the flask in a water bath adjusted to 88 ± 3°C, apply vacuum and allow
the solution to evaporate to dryness. At this point, flasks containing
dried derivative may be removed from the evaporator, cooled, stoppered,
and retained until their gas chromatographic analysis is completed.
43
-------
Gas Chromatographic Analysis
Treat each dried derivative from the preceding section according to
the following procedure. Add 0.5 ml of distilled water to the Bantamware
flask, and swirl until the contents are dissolved. Add 0.5 ml of 20%
sodium hydroxide solution and 0.5 ml of benzene; stopper tightly, shake
the mixture for one minute, and allow it to stand for five minutes.
Pour the flask contents into a 5 ml Mini V1al, place the V1a1 in a
centrifuge, and counterbalance it. Centrifuge the Vial for 15 minutes
at approximately 1700 - 1800 rpm.
Set the gas chromatograph to the following conditions, and allow it
to stabilize:
Column 6 ft x 1/4 in, (10% Carbowax 20M
or Carbowax 20M Terephthalic add +
5% KOH)* on Gas Chrom Q
Column Temperature (195°C) Isothermal
Detector Temperature (180°C)
Injection Port Temperature (205°C)
Carrier Gas Nitrogen at 55 ml/minute
A1r Flow (30) ml/minute
Oxygen Flow 10 ml/minute
Hydrogen Flow (70) ml/minute
Photomultiplier Voltage 750 Volts
Attenuation Variable (approximately 64 x 10)
As modified by Technological Resources Inc.
44
-------
The following injection volume constraints apply to all samples:
1. Single injections are not to exceed 25 yl.
2. Injection volumes within the range 10 yl to 25 yl vary by
increments of 5 yl.
3. Injection volumes within the range 1 yl to 10 yl vary by
increments of 1 yl.
Trial Injections:
Inject 10 yl of the 0.8 yg/ml Standard Solution into the instrument,
and allow the ETU derivative peak to elute (Figure 2). Similarly inject
10 yl of the 0.2 yg/ml Standard; measure and record the peak heights, in
chart units, of each ETU derivative peak. The 0.8 yg/ml Standard must
produce a peak with about 70% chart deflection and the 0.2 yg/ml Standard
must produce a measurable peak; if either of these criteria cannot be
met, refer to the chromatographic instrument manual to correct low-
sensitivity problems and repeat the trial injections. From this point
on, sample peak height adjustments (to maintain on-scale chromatograms)
are made by varying the sample injection volumes only. Make no attenuation
adjustments.
Control Sample:
Inject 25 yl of the Control sample (from the upper layer in the
appropriate Mini Vial); allow the ETU derivative peak to elute, measure
and record the peak height (in chart units), and record the injection
volume (NOTE: If the ETU derivative peak is off scale with any injection,
reduce the injection volume until the peak remains on scale, and record
the injection volume used).
45
-------
Spiked Control Samples;
Determine and record the yg ETU added to the Spiked Control samples
using the following equation:
(2) yg ETU Added =
Volume of ETU Spiking
Solution Added, ml
(from Calculation 1)
Concentration of Spiking
Solution, yg/ml (Working
Solution A-2 or A-3)
Estimate an injection volume for the higher of the two Spiked
Control samples from the following equation:
Inaction Volume for (Std* Sol'n from Tr1al Injection (Dilution Factor)
(3) ' °-8 1"1 *
yg ETU Added to the Higher Spiked Control
(from Calculation 2)
Estimate an injection volume for the Lower Spiked' Control by doubling
the Injection volume of equation (3). NOTE: These estimated Injection
volumes are guides and may require adjustment because of instrument
sensitivity variation. Record the Injection volumes used for each
Spiked Control.
Make duplicate injections of the selected volume of each Spiked
Control sample (Mini V1al upper layer) into the chromatographic column,
allowing the ETU derivative peak to elute from the previous injection
before making the next injection. Measure and record the ETU derivative
peak heights, in chart units.
Standard Samples:
Run a series of three Standard samples to establish a Calibration
Curve. Adjust the Injection volumes of these standards so that they
produce peak heights within the range of about 5 to 70% chart deflection.
Measure and record the peak heights of each ETU derivative peak, in
chart units.
46
-------
Treated Samples:
Inject 25 pi of the Treated sample (Mini V1al upper layer) into the
chromatographic column, allow the ETU derivative peak to elute, measure
and record the peak height and injection volume. If the ETU derivative
peak height exceeds the peak height of the highest Standard used, reduce
the injection volume until re-injection produces a derivative peak
height within the range of the Standards (5 to 70% chart deflection).
Similarly inject the remaining Treated samples; read and record the
peak heights and injection volumes used. After approximately 10 samples,
re-inject the High Standard derivative solution, and after running the
last Treated sample, again repeat the High Standard injection. Measure
and record the ETU derivative peak heights.
Determine the ETU content of the S-butyl ETU derivative Standards
using the following calculation:
(4) Nanograms (ng) ETU = [injection Volume of Standard, x
L * J
Concentration of
Standard, ug.ml
[(as ETU)
On a sheet of 10 x 10 per centimeter graph paper plot the peak
height of each ETU derivative Standard versus its corresponding ETU
content (nanograms of ETU from Calculation 4). Draw the line that most
closely fits the set of points; this is the ETU calibration curve.
Using the calibration curve, determine the nanograms of ETU corres-
ponding to the peak heights for the two Spiked Control samples, and the
untreated Control sample. Record these values as "nanograms ETU from
Curve"; they represent the nanograms of ETU in the gas chromatographic
47
-------
injection. Determine the "total micrograms of ETU found" using the
following calculation which corrects for dilution and unit conversion;
these values represent the total micrograms of ETU in the original
sample:
0.5 ml in 6.95 ml 8.0 ml
,r > Total yg = ng ETU Mini Vial Dilution ¥ Dilution Y 1000 yl/ml
k ; ETU Found from Curve x yl Injected x 4.0 mlx 1.0 mlx 1000 ng/yg
in GLC Aliquot Aliquot
or
/ch\ Total yg _ (ng ETU from Curve) x 6.95
v ' ETU Found yl Injected into GLC
*
6.95 ml is the estimated volume of the organic phase 1n the 10 ml
graduated cylinder before the 4.0 ml aliquot portion 1s pipetted
from it.
Determine and record the "mocrograms of net ETU, Recovered" for
each Spiked Control sample using the following calculation; these values
represent the total micrograms of ETU found in the Spiked samples,
corrected for the total micrograms of ETU contributed by the untreated
Control sample:
(6) yg of net ETU, Recovered
Total yg ETU Found
for Spiked Control
Total yg ETU Found
for untreated Control
If this value is less than 0.8 yg, Ignore it and report the Total
yg ETU Found for the Spiked Control as the yg of net ETU, Recovered.
Determine and record the "percent recovery" for each Spiked Control
sample, using the following calculation; these values represent the
amount of ETU found in each Spiked Control, expressed as a percentage of
the amount of ETU actually added:
48
-------
(7) % Recovery = yg of net ETU, Recovered (from calculation 6) „ lnn
yg ETU added (from calculation 2)x IUU
The percent recovery must be 60% or greater for one or more Spiked
Controls (except at very low levels); if 1t Is not, repeat the entire
determination of the Control sample, Spiked Controls, and Treated Samples.
If the percent recovery for both Spiked Controls is 60% or greater,
determine the average of the two values; if only one value 1s 60% or
greater, use that value 1n later calculations, and disregard the value
below 60%.
Using the calibration curve, determine and record the nanograms of
ETU corresponding to the peak heights for the treated samples. Determine
and record the "total" micrograms of ETU found in the treated samples,
using the following calculation:
/cK\ Total yg (ng ETU from Curve) x 6.95
\*») ETU Fou|ld - yi injected Into 6LC
Correct the Total yg of ETU Found, for the % Recovery, using the
following calculation:
i*\ n FTII rnw**r+aA - Total yg ETU Found x 100
(8) yg ETU Corrected Average % Recovery
Determine and record the "parts per million ETU" in the Treated
Samples, using the yg ETU Corrected, and the following calculation:
(Q\ m cm ug ETU Corrected (from Calculation 8)
(9) ppm ETU = *x sample Height in grams
(Attached 3 Figures)
49
-------
Figure 1. Preparation of liquid chromatograph column
200 ml CAPACITY
Pour the specified quantities
of packing materials into the
column, and tap with the hand
to settle them. Do not vibrate
the column.
25 cm LONG
SEA SAND (1 ml)
ACTIVATED ALUMINA (10 g)
GLASS WOOL
TEFLON STOPCOCK ( 2 mm BORE)
NO.6 RUBBER STOPPER
50
-------
Figure 2. Typical chromatograms (ETU)
STANDARD 6
STANDARD 4/zl
0.5 Mg/mlasETU
0.5 jug/ml as ETU
INJECTION f
64x10 3ng:
INJECTION
64x17)
2 ng
STANDARD 5"Ml
0.2
64x10
INJECTION
1 ng
51
-------
180
160
140
120
E
E
Ul
Q.
80
60
40
20
Figure 3. Typical calibration curve
ngas ET U
52
-------
APPENDIX B
INDIVIDUAL DATA FROM SUMMARY TABLE 3
Residues of EBDC and ETU (from Dithane M-45®)
in Tomatoes, Carrots, and Spinach at Process Stages
53
-------
Table IA-1-A. Residues of EBDC (from M-45) 1n
East Coast Unwashed Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
Si:
<0.1,
0.2,
0.6,
0.9,
0.7,
0.8,
Si
0.1
0.2
0.6
0.9
0.6
0.8
Average
0.1
0.2
0.6
0.9
0.7
0.8
Corrected Average
for %
Check Recovery
0.1 108
0.2
0.6
0.9 108
0.7
0.8
Corrected
for Avg.
% Recovery
0.1
0.2
0.6
0.8
0.6
0.7
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
2.9 EBDC**
2.9 EBDC**
2.9 EBDC**
Amount Found
1.2, 1.2
1.7
1.0, 1.1
3.1, 3.3
4.2
2.7
Corrected
for Check
1.2, 1.2
1.7
1.0, 1.1
3.1, 3.3
4.2
2.7
%
Recovery
100, 100
142
83, 92
107, 114
145
93
Average %
Recovery
108
Corrected by subtraction of amount found In check sample.
**Amount added has been corrected for % activity of 57.6.
54
-------
Table IA-1-B. Residues of EBDC (from M-45) in
East Coast Washed Tomatoes
Corrected Average Corrected
Sampl e
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1, <0.1
o.r, o.i
0.2, 0.2
0.3, 0.3
0.3, 0.2
0.2, 0.2
0.4, 0.4
0.4, 0.4
0.4, 0.4
Average
<0.1
0.1
0.2
0.3
0.3
0.2
0.4
0.4
0.4
for
Check
0.3
0.2
<0.1
0.4
0.3
0.2
% for Avg.
Recovery % Recovery
97.3 0.3
0.2
<0.1
97.3 0.4
0.3
0.2
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
2.9 EBDC**
2.9 EBDC**
2.9 EBDC**
Amount Found
1.1, 1.2
1.0, 1.1
1.6, 1.6
2.7, 2.9
2.4, 2.7
3.5, 3.8
Corrected
for Check
1.1, 1.2
0.9, 1.0
1.4, 1.4
2.7, 2.9
2.3, 2.6
3.3, 3.6
%
Recovery
92, 100
75, 83
117, 117
93, 100
79, 90
114, 124
Average %
Recovery
97.3
*Corrected by subtraction of amount found 1n check sample.
**Amount added has been corrected for % activity of 57.6.
55
-------
Table IA-1-C. Residues of EBDC (from M-45) 1n
East Coast Tomato Tailings
Corrected Average Corrected
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount
EBDC
<0.1,
<0. 1,
0.1,
0.1,
0.2,
0.3,
0.6,
0.5,
0.4,
Found
(ppm)
<0.1
<0. 1
0.2
0.1
0.3
0.3
0.7
0.5
0.5
Average
<0.1
<0.1
0.2
0.1
0.3
0.3
0.7
0.5
0.5
for
Check
0.1
0.3
0.1
0.7
0.5
0.3
% for Avg.
Recovery % Recovery
94.7 0.1
0.3
0.1
94.7 0.7
0.5
0.3
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount Corrected
Added Amount Found for Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
2.9 EBDC**
2.9 EBDC**
2.9 EBDC**
1.0
1.0
1.2
3.1
3.0
3.4
1.0
1.0
1.0
3.1
3.0
3.2
%
Recovery
83
83
83
106
103
110
Average %
Recovery
94.7
*Corrected by subtraction of amount found In check sample.
**Amount added has been corrected for % activity of 57.6.
56
-------
Table IA-1-D. Residues of EBDC (from M-45) in
Canned Juice from East Coast Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
0.1, 0.1
0.1, 0.1
<0.1, 0.1
<0.1, <0.1,
0.1, 0.2
<0. 1 , <0. 1
<0.1, <0.1
0.2, 0.3
0.2, 0.2
0.1, 0.1
Average
0.1
0.1
0.1
0.1
<0.1
<0. 1
0.3
0.2
0.1
Corrected Average Corrected
for % for Avg.
Check Recovery % Recovery
<0.1 90.1 <0.1
<0. 1 <0.1
<0.1 <0.1
0.2 90.1 0.2
0.1 0.1
<0.1 0.1
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
2.9 EBDC**
2.9 EBDC**
2.9 EBDC**
Amount Found
1.0, 1.1
0.9, 1.1
1.2, 1.4
2.6, 2.8
2.8, 3.0
3.0, 3.2
Corrected
for Check
0.9, 1.0
0.8, 1.0
1.1, 1.3
2.5, 2.7
2.6, 2.8
2.9, 3.1
%
Recovery
75, 83
67, 83
92, 108
86, 93
90, 97
100, 107
Average %
Recovery
90.1
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 57.6.
57
-------
Table IA-2-A. Residues of ETU (from M-45) 1n
East Coast Unwashed Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I lx
Rep II lx
Rep III lx
Rep I 4x
Rep II 4x
Rep III 4x
Amount
ETU
:o.oi,
:o.oi,
:o. 01 ,
:o.oi,
0.01,
:o. 01 ,
0.01,
0.01,
0.02,
Found
(ppm)
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.02
0.02
0.02
Average
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.02
0.02
0.02
Corrected
for
Check
<0.01
0.01
<0.01
0.02
0.02
0.02
Average
%
Recovery
86.7
86.7
Corrected
for Average
% Recovery
<0.01
0.01
<0.01
0.02
0.02
0.02
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.07
0.03
0.03
Corrected
for Check
0.07
0.03
0.03
Recovery
140
60
60
Average %
Recovery
86.7
Corrected by subtraction of amount found 1n check sample.
58
-------
Table IA-2-B. Residues of ETU (from M-45) 1n
East Coast Washed Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
0.01, 0.01
0.01, 0.01
0.01, 0.01
0.02, 0.01
<0.01, <0.01
0.01, 0.01
0.01, 0.01
0.02, 0.02
0.02, 0.02
Average
0.01
0.01
0.01
0.02
<0.01
0.01
0.01
0.02
0.02
Corrected
for
Check
0.01
<0.01
<0.01
<0.01
0.01
0.01
Average
Recovery
80
80
Corrected
for Average
% Recovery
0.01
<0.01
<0.01
<0.01
0.01
0.01
Recovery Studies ETU (ppm)
Rep ,1 check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount
Found
0.06
0.05
0.04
Corrected
for Check
0.05
0.04
0.03
Recovery
100
80
60
Average
% Recovery
80
Corrected by subtraction of amount found 1n check sample.
59
-------
Table IA-2-C. Residues of ETU (from M-45) in
East Coast Tomato Tailings
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, 0.01
0.01, 0.03
0.01, <0.01
Average
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
0.01
Corrected
for
Check
0.01
<0.01
<0.01
<0.01
<0.01
0.01
Average Corrected
% for Average
Recovery % Recovery
46.7 0.02
<0.01
<0.01
46.7 <0.01
<0.01
0.02
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.06 ETU
0.05 ETU
Amount
Found
0.04
0.01
0.02
Corrected
for Check
0.04
0.01
0.02
%
Recovery
80
20
40
Average
% Recovery
46.7
k
Corrected by subtraction of amount found in check sample.
60
-------
Table IA-2-D. Residues of ETU (from M-45) in
Canned Juice from East Coast Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
0.01, 0.01
0.01, <0.01
0.05, 0.05
0.04, 0.04
0.02, 0.02
0.11, 0.10
0.11, 0.14
0.11, 0.08
Average
Corrected
for
Check
<0.01
0.01
0.01
0.05
0.04
0.02
0.11
0.13
0.10
0.05
0.03
0.01
0.11
0.12
0.09
Average
%
Recovery
106.7
106.7
Corrected
for Average
% Recovery
0.05
0.03
0.01
0.10
0.11
0.08
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added .
0.05 ETU
0.05 ETU
0.05 ETU
Amount
Found
0.05
0.08
0.05
Corrected
For Check
0.05
0.07
0.04
Recovery
100
140
80
Average
% Recovery
106.7
Corrected by subtraction of amount found in check sample.
61
-------
Table IA-3-A. Residues of EBDC (from M-45) from
West Coast Unwashed Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1, <0.1
<0. 1, <0. 1
<0.1, <0.1
1.6, 1.4
1.8, 2.3
2.2, 2.1
5.4, 6.9
4.8, 5.8
8.1, 9.6
Average
<0. 1
<0. 1
<0. 1
1.5
2.1
2.2
6.2
5.3
8.9
Corrected
for
Check
1.5
2.1
2.2
6.2
5.3
8.9
Average Corrected
% for Avg.
Recovery % Recovery^
96.2 1.6
2.2
2.3
96.2 6.4
5.5
9.3
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount Corrected
Added Amount Found for .Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 tBDC**
3.1 EBDC**
1.2
0.9
1.3
2.9
2.8
3.4
1.2
0.9
1.3
2.9
2.8
3.4
Recovery
100
75
108
94
90
110
Average %
Recoyery
96.2
Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
62
-------
Table IA-3-B. Residues of EBDC (from M-45) from
West Coast Washed Tomatoes
Corrected Average Corrected
Amount
Sampl e
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
I check
II check
III check
I Ix
II Ix
III Ix
I 4x
II 4x
III 4x
EBDC
<0.1
<0. 1
<0.1
0.5
0.4
0.5
0.8
0.8
0.9
,
»
>
>
»
,
>
»
Found
(ppm)
<0.1
<0. 1
<0.1
0.4
0.4
0.5
0.8
0.8
0.8
for
Average
<0.
<0.
<0.
0.
0.
0.
0.
0.
0.
,
1
1
5
4
5
8
8
9
Check
0.
0.
0.
0.
0.
0.
5
4
5
8
8
9
% for
Avg
*
Recovery % Recovery
88.7 0
0
0
88.7 0
0
1
.6
.5
.6
.9
.9
.0
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
1.0
1.4
0.7
3.1
3.3
2.1
Corrected
for Check
1.0
1.4
0.7
3.1
3.3
2.1
% Average :
Recovery Recovery
83
117
58
100
106
68 88.7
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
63
-------
Table IA-3-C. Residues of EBDC (from M-45) from
West Coast Tomato Tailings
Sample
Rep I check
Rep II check
Rep III check
Amount Found
EBDC (ppm)
Values from
East Coast used
Average
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.7, 0.4
0.4, 0.4
0.1, 0.1
0.7, 0.6
1.5, 1.4
1.9, 1.4
0.6
0.4
0.1
0.7
1.5
1.7
Corrected Average
for %
Check Recovery
0.6
0.4
0.1
0.7
1.5
1.7
94.7
94.7
Corrected
for Avg.
% Recovery
0.6
0.4
0.1
0.7
1.6
1.8
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount Corrected % Average 5
Added Amount Found for Check Recovery Recovery
Recovery studies from East Coast sample used
due to lack of adequate sample.
*Check samples assumed to be <0.1 ppm.
**Average % Recovery from East Coast used.
64
-------
Table IA-3-D. Residues of EBDC (from M-45) from
Canned Juice from West Coast Tomatoes
Corrected Average
Sampl e
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount
EBDC
<0.1,
<0. 1,
<0.1,
0.4,
0.3,
0.4,
1.3,
0.8,
1.5,
Found
(ppm)
<0.1
<0. 1
<0.1
0.4
0.3
0.4
1.3
0.7
1.6
Average
<0.1
<0.1
<0.1
0.4
0.3
0.4
1.3
0.8
1.6
for
Check
0.4
0.3
0.4
1.3
0.8
1.6
%
Recovery
67.8
67.8
Corrected
for Avg.
% Recovery
0.6
0.4
0.6
1.9
1.2
2.4
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
0.8
0.8
0.8
1.8
2.3
2.3
Corrected
for Check
0.8
0.8
0.8
1.8
2.3
2.3
Recovery
67
67
67
58
74
74
Average %
Recovery
67.8
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
65
-------
Table IA-4-A. Residues of ETU (from M-45) from
West Coast Unwashed Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep
Rep
Rep
Rep
Rep
Rep
I Ix
II Ix
III Ix
I 4x
II 4x
III 4x
Amount Found
ETU (ppm)
0.
<0.
<0.
0.
0.
0.
0.
0.
0.
01,
01,
01,
01,
01,
02,
02,
<0.
<0.
<0.
<0.
0.
<0.
0.
0.
0.
01
01
01
01
01
01
01
02
05
Average
0.01
<0.01
<0.01
0.
0.
0.
0.
0.
0.
01
01
01
01
02
04
Corrected Average
for %
Check Recovery
<0.
0.
0.
<0.
0.
0.
01 86.7
01
01
01 86.7
02
04
Corrected
for Average
% Recovery
<0.
0.
0.
<0.
0.
0.
01
01
01
01
02
05
Rep I check
Rep II check
Rep III check
Recovery Studies ETU (ppm)
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount
Found
0.03
0.05
0.05
Corrected
for Check
0.03
0.05
0.05
Recovery
60
100
100
Average
% Recovery
86.7
Corrected by subtraction of amount found In check sample.
66
-------
Table IA-4-B. Residues of ETU (from M-45) from
West Coast Washed Tomatoes
Sample
Amount Found
ETU (ppm)
Rep I check <0.01, <0.01
Rep II check 0.01, <0.01
Rep III check <0.01, <0.01
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
<0.01, <0.01
0.01, 0.01
0.01, <0.01
<0.01, 0.01
<0.01, <0.01
<0.01, <0.01
Average
<0.01
0.01
<0.01
<0.01
0.01
0.01
0.01
<0.01
<0.01
Corrected
for
Check
<0.01
<0.01
0.01
0.01
<0.01
<0.01
Average
%
Recovery
60
60
Corrected
for Average
% Recovery
<0.01
<0.01
0.02
0.02
<0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.01
0.04
Corrected
for Check
0.04
0.01
0.04
Recovery
80
20
80
Average 5
Recovery
60
*Corrected by subtraction of amount found in check sample.
67
-------
Table IA-4-C. Residues of ETU (from M-45) from
West Coast Tomato Tailings
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.02, 0.02
0.03, 0.03
<0.01, <0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
0.03
<0.01
Corrected
for
Check
<0.01
<0.01
<0.01
0.02
0.03
<0.01
Average
Recovery
36.7
36.7
Corrected
for Average
% Recovery
<0.01
<0.01
<0.01
0.05
0.08
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.10 ETU
0.10 ETU
0.05 ETU
Amount Found
0.04
0.05
0.01
Corrected
for Check
0.04
0.05
0.01
Recovery
40
50
20
Average %
Recovery
36.7
*Corrected by subtraction of amount in check sample.
68
-------
Table IA-4-D. Residues of ETU (from M-45) from
Canned Juice of West Coast Tomatoes
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
0.02, 0.02
0.01, 0.01
0.01, 0.01
0.15, 0.11
0.09, 0.09
0.07, 0.07
<0.01, 0.28
0.08, 0.13
0.08, 0.06
Average
0.02
0.01
0.01
0.13
0.09
0.07
0.14
0.11
0.07
Corrected
for
Check
0.11
0.08
0.06
0.12
0.10
0.06
Average
Recovery
73.3
73.3
Corrected
for Average
% Recovery
0.15
0.11
0.08
0.16
0.14
0.08
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.05
0.07
0.03
Corrected
for Check
0.03
0.06
0.02
Recovery
60
120
40
Average %
Recovery
73.3
Corrected by subtraction of amount found in check sample.
69
-------
Table IB-l-A. Residues of EBDC (from M-45) in
East Coast Unwashed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1,
<0.1,
<0.1,
0.2,
0.5,
0.7,
0.4,
0.7,
0.9,
<0.1
<0.1
<0.1
0.3
0.5
0.7
0.4
0.7
0.9
Average
<0.1
-
-------
Table IB-l-B. Residues of EBDC (from M-45) 1n
East Coast Washed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0. 1, <0. 1
<0.1, <0. 1
<0. 1, <0. 1
0.5 0.5
0.1, <0.1
0.8, 0.7
0.4, 0.4
0.3, 0.3
Average
0.5
0.1
0.8
0.4
0.3
Corrected
for
Check
0.
0.
0.8
0.4
0.3
Average
%
Recovery
70.5
70.5
Corrected
for Average
% Recovery
0.7
0.1
1.1
0.6
0.4
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
1.0
0.7
0.9
2.5
1.8
2.1
Corrected
for Check
1.0
0.7
0.9
2.5
1.8
2.1
Recovery
83
58
75
81
81
68
Average %
Recovery
70.5
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
71
-------
Table IB-l-C. Residues of EBDC (from M-45) in
East Coast Blanched Diced Carrots
Sample
Amount Found
EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
<0.1 ,
<0.1 ,
<0.1 ,
0.2,
0.1,
0.1,
0.4,
0.4,
0.3,
<0.1
<0.1
<0.1
0.1
0.1
0.1
0.4
0.4
0.3
Average
0.2
0.1
0.1
0.4
0.4
0.3
Corrected
for
Check
0.2
0.1
0.1
0.4
0.4
0.3
Average
%
Recovery
87
87
Corrected
for Average
% Recovery
0.
0.
0,
0.5
0.5
0.3
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
0.8
0.9
1.5
2.7
2.6
2.6
Corrected
for Check
0.8
0.9
1.5
2.7
2.6
2.6
Recovery
67
75
125
87
84
84
Average %
Recovery
87
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
72
-------
Table IB-l-D. Residues of EBDC (from M-45) in
East Coast Frozen Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
Average
Corrected
for
Check
Recovery Studies EBDC (ppm)
Average
%
Recovery
81.5
81.5
Corrected
for Average
% Recovery
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
0.8
0.9
1.1
2.7
2.6
2.6
Corrected
for Check
0.8
0.9
1.1
2.7
2.6
2.6
Recovery
67
75
92
87
84
84
Average %
Recovery
81.5
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62.2.
73
-------
Table IB-l-E. Residues of EBDC (from M-45) in
East Coast Canned Carrots
Sample
Rep I check
Rep II check
Rep HI check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount
EBDC
<0.1 ,
<0.1 ,
0.1,
<0.1 ,
<0.1 ,
o!ii
Found
(ppm)
s
0.1
<0.1
<0.1
<0.1
0.1
Average
0.1
-------
Table IB-2-A. Residues of ETU (from M-45) in
East Coast Unwashed Carrots
Sampl e
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
i
Amount Found
ETU (ppm)
<0.01 , <0.01
<0.01, <0.01
<0.01, <0.01
<0.01 , <0.01
<0.01, <0.01
<0.01, <0.01
0.01, 0.01
<0.01, <0.01
0.01, <0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.01
Corrected
for
Check
<0.01
<0.01
<0.01
0.01
<0.01
0.01
Average
01
h
Recovery
80
80
Corrected
for Average
% Recovery
<0.01
<0.01
<0.01
0.01
<0.01
0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.05
0.04
0.03
Corrected
for Check
0.05
0.04
0.03
Recovery
100
80
60
Average %
Recovery
80
*Corrected by subtraction of amount found in check sample.
75
-------
Table IB-2-B. Residues of ETU (from M-45) in
East Coast Washed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
Si;
0.01,
<0.01,
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
Average
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
0.01
<0.01
<0.01
Corrected
for
Check
0.01
<0.01
<0.01
0.01
<0.01
<0.01
Average Corrected
% for Average
Recovery % Recovery
73.3 0.01
<0.01
<0.01
73.3 0.01
<0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.03
0.04
Corrected
for Check
0.04
0.03
0.04
Recovery
80
60
80
Average %
Recovery
73.3
*Corrected by subtraction of amount found in check sample.
76
-------
Table IB-2-C. Residues of ETU (from M-45) 1n
East Coast Blanched Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (pom)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Corrected
for
Check
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Average
%
Recovery
73.3
73.3
Corrected
for Average
% Recovery
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.03
0.04
0.04
Corrected
for Check
0.03
0.04
0.04
Recovery
60
80
80
Average %
Recovery
73.3
Corrected by subtraction of amount found in check sample.
77
-------
Table IB-2-D. Residues of ETU (from M-45) in
East Coast Frozen Diced Carrots
Sample
Rep I check
Rep II check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, 0.01
0.01, 0.01
<0.01, <0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
<0.01
Corrected
for
Check
<0.01
<0.01
<0.01
0.01
0.01
<0.01
Average Corrected
% for Average
Recovery % Recovery
80 <0.01
<0.01
<0.01
0.01
0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.04 ETU
Amount Found
0.04
0.04
0.04
Corrected
for Check
0.04
0.04
0.04
Recovery
80
80
80
Average %
Recovery
80
*Corrected by subtraction of amount found in check sample.
78
-------
Table IB-2-E. Residues of ETU (from M-45) in
East Coast Canned Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, 0.01
0.01, 0.01
0.01, 0.01
0.02, 0.02
0.02, 0.02
0.02, 0.02
Average
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.02
0.02
0.02
Corrected
for
Check
0,
0,
01
01
0.01
0.02
0.02
0.02
Average
%
Recovery
40
40
Corrected
for Average
% Recovery
0.03
0.03
0.03
0.05
0.05
0.05
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.01
0.02
0.03
Corrected
for Check
0.01
0.02
0.03
Recovery
20
40
60
Average /
Recovery
40
*Corrected by subtraction of amount found in check sample.
79
-------
Table IB-3-A. Residues of EBDC (from M-45) in
West Coast Unwashed Carrots
Amount Found
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
*c
Rep I 4x
Rep II 4x
Rep III 4x
EBDC
<0.1
<0.1
0.1
0.2
0.1
0.1
0.3
0.4
0.3
(ppm)
, <0.1
, <0.1
, 0.1
, 0.2
, 0.1
, 0.1
, 0.3
, 0.4
, 0.4
Average
<0.1
<0.1
0.1
0.2
0.1
0.1
0.3
0.4
0.4
Corrected
for
Check
0.2
0.1
<0.1
0.3
0.4
0.3
Average Corrected
% for Average
Recovery % Recovery
81.8 0.2
0.1
<0.1
81.8 0.4
0.5
0.4
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
2.9 EBDC**
2.9 EBDC**
2.9 EBDC**
1.1
1.0
1.0
1.9
2.8
2.5
Corrected
for Check
1.1
1.0
0.9
1.9
2.8
2.4
Recovery
92
83
75
61
97
83
Average %
Recovery
81.8
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 57.7.
80
-------
Table IB-3-B. Residues of EBDC (from M-45) in
West Coast Washed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
oil!
oil',
0.2,
0.3,
0.3,
0.2,
oil
oil
0.2
0.2
0.4
0.2
Average
oil
<0.1
<0.1
0.1
0.2
0.3
0.4
0.2
Corrected Average
for %
Check Recovery
<0.1 79.3
<0.1
0.2
0.3 79.3
0.3
0.2
Corrected
for Average
% Recovery
<0.1
<0.1
0.3
0.4
0.4
0.3
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1 .4 EBDC**
1 .4 EBDC**
1.4 EBDC**
3.4 EBDC**
3.4 EBDC**
3.4 EPDC**
1.0
1.0
1.3
2.4
2.5
3.6
Corrected
for Check
1.0
0.9
1.3
2.4
2.4
3.6
Recovery
71
64
93
71
71
106
Average %
Recovery
79.3
Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 67.6.
81
-------
Table IB-3-C. Residues of EBDC (from M-45) in
West Coast Blanched Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I lx
Rep II lx
Rep III lx
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1,<0.1
<0.1 , <0.1
0.1, 0.1
0.1, 0.1
0.1, 0.1
0.1, 0.1
0.1, 0.1
0.1, 0.2
0.1, 0.1
Average
<0.1
<0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.1
Corrected
for
Check
0.1
0.1
<0.1
0.1
0.2
<0.1
Average Corrected
% for Average
Recovery % Recovery
81.2 0.1
0.1
<0.1
81.2 0.1
0.2
<0.1
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.4 EBDC**
1.4 EBDC**
1.4 EBDC**
3.4 EBDC**
3.4 EBDC**
3.4 EBDC**
0.8
1.1
1.3
2.4
3.5
3.2
Corrected
for Check
0.8
1.1
1.2
2.4
3.5
3.1
Recovery
57
79
86
71
103
91
Average %
Recovery
81.2
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 67.6.
82
-------
Table IB-3-D. Residues of EBDC (from M-45) in
West Coast Frozen Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1 , <0.1
<0.1 , <0.1
<0.1 , <0.1
o!i! o!i
o.'i! o!i
Average
<0.1
<0.1
<0.1
0.1
o!i
Corrected
for
Check
<0.1
<0.1
0.1
<0.1
0.1
Average
Recovery
87.8
87.8
Corrected
for Average
% Recovery
o!i
OJ
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.4 EBDC**
1.4 EBDC**
1.4 EBDC**
3.4 EBDC**
3.4 EBDC**
3.4 EBDC**
1.0
1.1
1.0
3.3
3.4
3.7
Corrected
for Check
1.0
1.1
1.0
3.3
3.4
3.7
Recovery
71
79
71
97
100
109
Average %
Recovery
87.8
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 67.6.
83
-------
Table IB-3-E. Residues of EBDC (from M-45) in
West Coast Canned Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.1 , <0.1
<0.1 , <0.1
<0.1 , <0.1
0.2, 0.2
0.2, 0.2
0^2! 0^2
0.2, 0.2
Average
<0.1
<0.1
0.2
0.2
0^2
0.2
Corrected
for
Check
<0.1
0.2
0.2
<0.1
0.2
0.2
Average
Recovery
82.8
82.8
Corrected
for Average
% Recovery
0.*2
0.2
<0.1
0.2
0.2
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.4 EBDC**
1.4 EBDC**
1.4 EBDC**
3.4 EBDC**
3.4 EBDC**
3.4 EBDC**
0.9
0.9
1.3
3.0
3.2
3.3
Corrected
for Check
0.9
0.9
1.3
3.0
3.2
3.2
Recovery
64
64
93
88
94
94
Average 1
Recovery
82.8
*Corrected by subtraction of amount found In check sample.
**Amount added has been corrected for % activity of 67.6.
84
-------
Table IB-4-A. Residues of ETU (from M-45) in
West Coast Unwashed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01S
0.01,
<0.01 ,
<0.01 ,
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Average
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Corrected Average
for %
Check Recovery
0.01 60
<0.01
<0.01
<0.01 60
<0.01
<0.01
Corrected
for Average
% Recovery
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
Rep I check
Rep II check
Rep III check
Recovery Studies ETU (ppm)
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.03
0.04
0.02
*
Corrected
for Check
0.03
0.04
0.02
Recovery
60
80
40
Average %
Recovery
60
*Corrected by subtraction of amount found in check sample.
85
-------
Table IB-4-B. Residues of ETU (from M-45) 1n
West Coast Washed Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
Average
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Corrected
for
Check
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Average
%
Recovery
66.7
66.7
Corrected
for Average
% Recovery
0.02
<0.01
<0.01
<0.01
<0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.03
0.03
0.04
Corrected
for Check
0.03
0.03
0.04
Recovery
60
60
80
Average %
Recovery
66.7
"Corrected by subtraction of amount found in check sample.
86
-------
Table IB-4-C. Residues of ETU (from M-45) in
West Coast Blanched Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Corrected
for
Check
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Average
Recovery
53.3
53.3
Corrected
for Average
% Recovery
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.02
0.02
Corrected
for Check
0.04
0.02
0.02
Recovery
80
40
40
Average %
Recovery
53.3
*Corrected by subtraction of amount found in check sample.
87
-------
Table IB-4-D. Residues of ETU (from M-45) 1n
West Coast Frozen Diced Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Rep I check
Rep II check
Rep III check
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01r<0.01
0.01, <0.01
<0.01, <0.01
<0.01, <0.01
Recovery
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
Studies ETU
Amount
Added Amount Found
0.05 ETU
0.05 ETU
0.05 ETU
0.05
0.05
0.04
Corrected
for
Check
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
(ppm)
*
Corrected
for Check
0.05
0.05
0.04
Average Corrected
% for Average
Recovery % Recovery
93.3 <0.01
<0.01
<0.01
93.3 0.01
<0.01
<0.01
% Average %
Recovery Recovery
100
100
80 93.3
^Corrected by subtraction of amount found in check sample.
-------
Table IB-4-E. Residues of ETU (from M-45) in
West Coast Canned Carrots
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4X
Amount Found
ETU (ppm)
Average
<0.01,
<0.01 ,
<0.01,
<0.01,
<0.01 ,
<0.01,
0.01,
0.01,
0.01,
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.01
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
Corrected
for
Check
<0.01
<0.01
0.01
0,01
0.01
0.01
Average
%
Recovery
86.7
86.7
Corrected
for Average
% Recovery
<0.01
<0.01
0.01
0.01
0.01
0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.05
0.04
Corrected
for Check
0.04
0.05
0.04
Recovery
80
100
80
Average %
Recovery
86.7
*Corrected by subtraction of amount found in check sample.
89
-------
Table IC-l-A. Residues of EBDC (from M-45) in
East Coast Fresh Unwashed Spinach
Sampl e
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Amount Found
EBDC (ppm)
I check 0.1,
II check 0.2,
III check 0.1,
I Ix
II Ix
III Ix
I 4x
II 4x
III 4x
0.2
1.1,
1.9,
1.3
2.4,
3.2,
5.6,
5.3,
0.2,
0.3,
0.1,
0.9,
1.9,
2.3,
3.2
5.0,
6.1
0.
0.
0.
2.
2.
2.
4.
2
2
1,
1
0,
5
8
Average
0
0
0
1
1
2
3
5
5
.2
.2
.1
.4
.8
.4
.2
.1
.7
Corrected
for
Check
1.
1.
2.
3.
4.
5.
2
6
3
0
9
6
Average Corrected
% for Average
Recovery % Recovery
68.2 1
2
3
68.2 4
7
8
.8
.3
.4
.4
.2
.2
Recovery Studies EBDC (ppm)
Amount
Added
Rep
Rep
Rep
Rep
Rep
Rep
I check
II check
III check
I check
II check
III check
1.
1.
1.
3.
3.
3.
5
5
5
7
7
7
EBDC**
EBDC**
EBDC**
EBDC**
EBDC**
EBDC**
Corrected
Amount Found for
0
1
1
3
3
2
.8,1
.0,
.4,1
.3,
.5,
.8,
.0,1.4,1.0
1.5, 0.9
.0,1.1,1.2
3.1
2.8
3.7
0
1
0
0
1
0
3
3
2
% Average %
Check Recovery Recovery
.6,
.7,
.8,
.7
.2,
.9,
.1,
.3,
.6,
0.8,
0.8
1.3,
0.8,
1.0
2.9
2.6
3.5
56
62
65
81
80
83 68.2
Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 74.7.
90
-------
Table IC-l-B. Residues of EBDC (from M-45) in
East Coast Fresh Washed Spinach
Sampl e
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
I check
II check
III check
I Ix
II Ix
III Ix
I 4x
II 4x
III 4x
Amount Found
EBDC (ppm)
0.1,
0.2,
<0.1,
<0.1,
1.0,
0.9,
1.2,
2.2,
2.4,
2.6,
0.1,
0.1,
<0.1
1.1,
1.4
2.6,
2.1
2.2,
2.6,
0
0
1
1
2
2
.1.
.2
.1
.1
.1
.2
Average
0.
0.
<0.
1.
1.
1.
2.
2.
2.
1
1
1
1
2
6
2
2
5
Corrected
for
Check
1.
1.
1.
2.
2.
2.
0
1
6
1
1
5
Average Corrected
% for Average
Recovery % Recovery
84.5 1
1
1
84.5 2
2
3
.2
.3
.9
.5
.5
.0
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added
1.5
1.5
1.5
3.7
3.7
3.7
EBDC**
EBDC**
EBDC**
EBDC**
EBDC**
EBDC**
1
1
1
3
3
3
Amount Found
.0,
.8,
.0,
.2,
.9,
.1,
1.2,
1.6
1.0,
3.6
3.4
2.9,
1
1
1
.5
.6
.7
Corrected %
for
0.9,
1.7,
1.0,
3.3,
3.8,
3.1,
Check
1.1,1
1.5
1.0,1
3.7
3.3
2.9,1
Recovery
.4
.6
.7
75
107
80
95
96
69
Average %
Recovery
84.5
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 74.7.
91
-------
Table IC-l-C. Residues of EBDC (from M-45) in
East Coast Frozen Blanched Spinach
Sample
Amount Found
EBDC (ppm)
Average
*Corrected
for
Check
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
oii^o'.ilo.i1!
0.41
0.1 ,0.2,0.1,
0.1,0.1,0.2
<0. 1,0. 2, 0.2
0.2,0.1
0.3,0.2,0.2
0.3, 0.3
0.5, 0.5
0.2, 0.4
<0.1
<0.1
0.1
0.1
0.2
0.2
0.3
0.5
0.3
0.1
0.2
0.1
0.3
0.5
0.2
Average
%
Recovery
88.4
88.4
Corrected
for Average
% Recovery
0.
0.
0.
0.4
0.6
0.2
Recovery Studies EBDC (ppm)
Amount
Added
Amount Found
*Corrected
for Check
Rep I check 1.5 EBDC** 0.9,1.4,1.5, 0.9,1.4,
Rep II check 1.5 EBDC**
Rep III check 1.5 EBDC**
Rep I check 3.7 EBDC**
Rep II check 3.7 EBDC**
Rep III check 3.7 EBDC**
1.6
1.2,1.2,1.6
1.1,1.1,1.4,
1.3,1.9,1.7
4.3,3.1
3.9,3.3,3.8,
2.9,3.7
2.4
1
Recovery
90
5,1.6
1.2,1.2,1.6
1.0,1.0,1.3,
1.2,1.8,1.6
89
4.3,3.1 100
3.9,3.3,3.8, 95
2.9,3.7
2.3 62
Average %
Recovery
1.4
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 74.7.
Results excluded from calculation of average due to contamination.
92
-------
Table IC-1-D. Residues of EBDC (from M-45) in
East Coast Canned Spinach
Sampl e
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
Rep
I check
II
III
I 1
II
III
check
check
X
Ix
Ix
I 4x
II
III
4x
4x
Amount Found
EBDC (ppm)
0.
0.
0.
0.
0.
<0.
0.
0.
<0.
1,
1,
2,
1,
1,
!»
1,
2,
1,
0.
0.
0.
0.
0.
<0
0.
0.
0.
1, 0.1
1
2
1
1
-1
1, 0.1
2
1, 0.1
Average
0.
0.
0.
0.
0.
<0.
0.
0.
0.
1
1
2
1
1
1
1
2
1
Corrected Average Corrected
for % for Average
Check Recovery % Recovery
<0.1 89.7 <0.1
<0.1 <0.1
<0.1 <0.1
<0.1 89.7 <0.1
0.1 0.1
<0.1 <0.1
Recovery Studies EBDC (ppm)
Amount
Added
Rep
Rep
Rep
Rep
Rep
I check
II check
III check
I check
II check
1
1
1
3
3
.5
.5
.5
.7
.7
EBDC**
EBDC**
EBDC**
EBDC**
EBDC**
Amount
1
1
1
1
1
3
2
.7,1.4
.2,1.4
.2,1.4
.3,1.3
.5
.8,4.0
.8,3.7
Found
,1.8,
,1.3,
,3.8
,3.9,
Corrected
% Average %
for Check Recovery Recovery
1.6,1
1.2,1
1.1,1
1.1,1
1.3
3.7,3
2.7,3
.4,1.
.4
.3
.1,1.
.9,3.
.6,3.
8,
1,
7
8,
99
80
77
99
94
Rep III check 3.7 EBDC**
3.4
3.1
3.3
2.9
78
89.7
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 96.4%.
93
-------
Table IC-2-A. Residues of ETU (from M-45) 1n
East Coast Unwashed Fresh Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
<0.01, 0.01
0.01, 0.01
0.01, 0.01
0.01, 0.01
Recovery
Average
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
0.01
0.01
0.01
Studies ETU
Amount
Added Amount Found
Rep I check
Rep II check
Rep III check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.03
0.04
*Corrected
for
Check
<0.01
<0.01
0.01
0.01
0.01
0.01
(ppm)
*Corrected
for Check
0.03
0.03
0.04
Average
%
Recovery
73.3
73.3
Corrected
for Average
% Recovery
<0.01
<0.01
0.01
0.
0.
01
01
0.01
Recovery
60
60
80
Average %
Recovery
73.3
^Corrected by subtraction of amount found in check sample.
94
-------
Table IC-2-B. Residues of ETU (from M-45) in
East Coast Washed Fresh Spinach
Sample
Amount Found
ETU (ppm)
Rep I check <0.01, <0.01
Rep II check <0.01, <0.01
Rep III check <0.01, <0.01
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, 0.01
<0.01, 0.01
0.01, 0.01
Average
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
.01
.01
0.01
Corrected
for
Check
<0.01
<0.01
<0.01
,01
,01
0.01
Average
%
Recovery
80
80
Corrected
for Average
% Recovery
<0.01
<0.01
<0.01
,01
,01
0.01
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.04
0.07
Corrected
for Check
0.04
0.04
0.07
Recovery
80
80
140
Average %
Recovery
80
*Corrected by subtraction of amount found in check sample.
95
-------
Table IC-2-C. Residues of ETU (from M-45) in
East Coast Frozen Blanched Spinach
Sampl e
Amount Found
ETU (ppm)
Rep I check <0.01, <0.01
Rep II check <0.01, <0.01
Rep III check <0.01, <0.01
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.02, 0.02
0.03, 0.02
0.03, 0.03
0.02, 0.03
0.04, 0.06
0.08, 0.08
Average
Corrected
for
Check
<0.01
<0.01
<0.01
0.02
0.03
0.03
0.03
0.05
0.08
0.02
0.03
0.03
0.03
0.05
0.08
Average
%
Recovery
73.3
73.3
Corrected
for Average
% Recovery
0.03
0.04
0.04
0.04
0.07
0.11
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.03
0.04
0.04
Corrected
for Check
0.03
0.04
0.04
Recovery
60
80
80
Average %
Recovery
73.3
^Corrected by subtraction of amount found in check sample.
96
-------
Table IC-2-D. Residues of ETU (from M-45) in
East Coast Canned Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
0.01, 0.01
0.02, 0.01
0.01, 0.01
0.11, 0.12
0.14, 0.14
0.14, 0.14
0.30, 0.26
0.31, 0.38
0.28, 0.30
Average
0.01
0.02
0.01
0.12
0.14
0.14
0.28
0.35
0.29
Corrected
for
Check
0.11
0.12
0.13
0.27
0.33
0.28
Average
%
Recovery
66.7
66.7
Corrected
for Average
% Recovery
0.16
0.18
0.19
0.40
0.49
0.42
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.05
0.05
0.04
Corrected
for Check
0.04
0.03
0.03
Recovery
80
60
60
Average %
Recovery
66.7
*Corrected by subtraction of amount found in check sample.
97
-------
Table IC-3-A. Residues of EBDC (from M-45) 1n
West Coast Unwashed Spinach
Sampl e
Rep I check
Rep II check
Rep III check
Rep I lx
Rep II lx
Rep III lx
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
0.3,
0.4,
0.3
0.5
23.7, 23.5
42.8, 41.5
122,5, 70.7
204.8, 172.3
201.3, 180.0
180.6, 206.9
Average
0.3
0.5
23.6
42.2
96.6
188.
190.
Corrected
for
Check
23.
41.
96,
193.8
188.6
190.4
193.3
Average
%
Recovery
87
87
Corrected
for Average
% Recovery
27.1
48.
110.
216.8
218.9
222.1
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added
1.0 EBDC**
1.0 EBDC**
1.0 EBDC**
*
2. 5^ EBDC**
2.5 EBDC**
2.5 EBDC**
Amount Found
0.6
1.0
1.5
2.0
2.4
3.7
Corrected
for Check
0.6
0.7
1.0
2.0
2.1
3.2
Recovery
60
70
100
80
84
128
Average /
Recovery
87
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 49.8.
98
-------
Table IC-3-B. Residues of EBDC (from M-45) in
West Coast Washed Spinach
Sample
Amount Found
EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.1, 0.1
0.1, 0.1
0.4, 0.4
8.6, 6.9
5.6, 5.5
6.6, 6.7
38.5, 44.1
43.8, 45.3
30.0, 34.3
Average
0.1
0.1
0.4
7.8
5.6
6.7
41.
44.
Corrected
for
Check
7.7
5.5
6.3
41.
44.
Average
%
Recovery
66.7
66.7
Corrected
for Average
% Recovery
32.2
31.8
11.5
8.2
9.4
61.8
66.7
47.7
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.0 EBDC**
1.0 EBDC**
1.0 EBDC**
2.5 EBDC**
2.5 EBDC**
2.5 EBDC**
0.8
0.9
0.9
2.0
1.6
2.0
Corrected
for Check
0.7
0.8
0.5
1.9
1.5
1.6
Recovery
70
80
50
76
60
64
Average 5
Recovery
66.7
Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 49.8.
99
-------
Table IC-3-C. Residues of EBDC (from M-45) in
West Coast Frozen Spinach
Sample
Amount Found
EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.2, 0.2
0.1, 0.1
0.1, 0.1
0.3, 0.3
0.7, 0.7
0.6, 0.8
1.4, 1.4
2.0, 2.0
1.7, 1.6
Average
0.2
0.1
0.1
0.3
0.
0,
1.4
2.0
1.7
Corrected
for
Check
0.1
0.6
0.6
1.2
1.9
1.6
Average
%
Recovery
79.3
79.3
Corrected
for Average
% Recovery
0.1
0.8
0.8
1.5
2.4
2.0
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
Amount
Added Amount Found
1.0 EBDC**
1.0 EBDC**
1.0 EBDC**
2.5 EBDC**
2.5 EBDC**
2.5 EBDC**
0.7
0.9
1.0
2.1
2.0
2.7
Corrected
for Check
0.5
0.8
0.9
1.9
1.9
2.6
Recovery
50
80
90
76
76
104
Average %
Recovery
79.3
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 49.8.
100
-------
Table 1C-3-D. Residues of EBDC (from M-45) in
West Coast Canned Spinach
Sampl e
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount
EBDC
<0.1,
o!i!
0.1,
<0.1,
0.1,
0.1,
0.2,
0.1,
0.1,
Found
(ppm)
<0.1
O.'l
0.1
0.1
0.1
0.2
0.1
0.1
0.1
Average
<0.1
o!i
0.1
0.1
0.1
0.2
0.2
0.1
0.1
Corrected
for
Check
0.1
<0.1
0.1
0.2
<0.1
<0.1
Average
%
Recovery
Corrected
for Average
% Recovery
76.0
76.0
Recovery Studies EBDC (ppm)
Rep I check
Rep II check
Rep III check
Rep I check
Rep II check
Rep III check
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 49.8.
0.1
0.1
0.1
0.2
Amount
Added Amount Found
1.0 EBDC**
1.0 EBDC**
1.0 EBDC**
2.5 EBDC**
2.5 EBDC**
2.5 EBDC**
0.9
0.8
0.5
2.3
2.0
2.4
Corrected
for Check
0.9
0.7
0.4
2.3
1.8
2.3
Recovery
90
70
40
92
72
92
Average
Recovery
76.0
101
-------
Table IC-4-A. Residues of ETU (from M-45) in
West Coast Unwashed Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
0.02, 0.01
0.01, 0.01
0.09, JO.11
0.20, 0.14
0.19, 0.28
0.48, 0.62
0.43, 0.43
0.89, 1.16
Average
Corrected
for
Check
<0.01
0.02
\0.01
0.10
0.17
0.24
0.55
0.43
1.03
0.10
0.15
0.23
0.55
0.41
1.02
Average
%
Recovery
46.7
46.7
Corrected
for Average
% Recovery
0.21
0.32
0.49
1.18
0.88
2.18
Rep I check
Rep II check
Rep III check
Recovery Studies ETU (ppm)
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.03
0.03
0.04
*
Corrected
for Check
0.03
0.01
0.03
Recovery
60
20
60
Average %
Recovery
46.7
*Corrected by subtraction of amount found in check sample.
102
-------
Table IC-4-B. Residues of ETU (from M-45) 1n
West Coast Washed Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
<0.01, <0.01
0.01, 0.01
0.01, 0.01
0.02, 0.02
0.05, 0.05
0.04, 0.03
0.07, 0.08
Average
<0.01
<0.01
<0.01
Corrected
for
Check
0.01
0.01
0.02
0.05
0.04
0.08
0.01
0.01
0.02
0.05
0.04
0.08
Average
%
Recovery
66.7
66.7
Corrected
for Average
% Recovery
,01
,01
0.03
0.07
0.06
0.12
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.04
0.03
0.03
Corrected
for Check
0.04
0.03
0.03
Recovery
80
60
60
Average 5
Recovery
66.7
*Corrected by subtraction of amount found in check sample.
103
-------
Table IC-4-C. Residues of ETU (from M-45) in
West Coast Frozen Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
0.01, 0.01
<0.01, <0.01
0.01, 0.01
0.13, 0.17
0.39, 0.27
0.31, 0.36
0.33, 0.45
2.84, 3.28
2.67, 2.42
Average
Corrected
for
Check
0.01
<0.01
0.01
0.15
0.33
0.34
0.39
3.06
2.55
0.14
0.33
0.33
0.38
3.06
2.54
Average
%
Recovery
53.3
53.3
Corrected
for Average
% Recovery
0.26
0.62
0.62
0.71
5.74
4.78
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.02
0.04
0.04
Corrected
for Check
0.01
0.04
0.03
Recovery
20
80
60
Average %
Recovery
53.3
^Corrected by subtraction of amount found in check sample.
104
-------
Table IC-4-D. Residues of ETU (from M-45) in
West Coast Canned Spinach
Sample
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
ETU (ppm)
<0.01, <0.01
<0.01, <0.01
0.02, 0.02
0.67, 0.80
0.54, 0.51
0.97. 1.06
2.35, 2.31
2.71, 3.84
2.67, 3.16
Average
Corrected
for
Check
<0.01
<0.01
0.02
0.74
0.53
1.02
2.33
3.28
0.74
0.53
1.00
2.33
3.28
Average
%
Recovery
106.7
106.7
Corrected
for Average
% Recovery
2.92
2.90
0.69
0.50
0.94
«
2.18
3.07
2.72
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
0.05
0.05
0.08
Corrected
for Check
0.05
0.05
0.06
Recovery
100
100
120
Average 5
Recovery
106.7
Corrected by subtraction of amount found in check sample.
105
-------
APPENDIX C
INDIVIDUAL DATA FROM SUMMARY TABLE 4
Residues of EBDC and ETU (from Dithane M-22®)
In Tomatoes and Spinach at Process Stages
106
-------
Table IIA-l-A. Residues of EBDC (from M-22) from
West Coast Unwashed Tomatoes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I 1x
Rep II 1x
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
*Corrected
for
Check
Avg. Corrected
% for Avg.
Recovery % Recovery
0.2
0.1
0.2
2.0
1.8
2.1
7.5
4.3
6.8
0.2
0.1
0.2
2.3
1.5
2.1
7.9
4.8
6.6
0.2
0.1
0.2
2.2
1.7
2.1
7.7
4.8
6.7
2.0
1.6
1.9
7.5
4.7
6.5
77.8
77.8
2.6
2.1
2.4
9.6
6.0
8.4
Recovery Studies EBDC (ppm)
Corrected for %
Amount Added Amount Found Check Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.0 EBDC**
3.0 EBDC**
3.0 EBDC**
1.2
1.1
1.1
2.6
2.3
2.5
1.0
1.0
0.9
2.4
2.2
2.3
Avg. %
Recovery
83
83
75
80
73
77
77.8
*Corrected by subtraction of amount found in check sample,
**Amount added has been corrected for % activity of 60.
107
-------
Table IIA-l-B. Residues of EBDC (from M-22) from
West Coast Washed Tomatoes
Sample
Rep I Check <0.1
Rep II Check 0.1
Rep III Check 0.1
Rep I 1x 0.3
Rep II Ix 0.3
Rep III Ix 0.3
Rep I 4x 0.4
Rep II 4x 0.6
Rep III 4x 0.4
Amount Found EBDC (ppm) Average
Corrected
for
Check
Avg.
%
Recovery
Corrected
for Avg.
% Recovery
0.1
0.3
0.3
0.3
0.4
0.6
0.4
0.1
0.1
0.3
0.3
0.3
0.4
0.6
0.4
0.3
0.2
0.2
0.4
0.5
0.3
81.3
81.3
Recovery Studies EBDC (ppm)
Corrected for %
Amount Added Amount Found Check Recovery
Rep I Check 1.2
Rep II Check 1.2
Rep III Check 1.2
Rep I Check 3.0
Rep II Check 3.8
Rep III Check 3:0
1.0
1.0
1.0
3.0
3.2
2.1
1.0
0.9
0.9
3.0
3.1
2.0
0.4
0.2
0.2
0.5
0.6
0.4
Avg. %
Recovery
83
75
83
100
79
67
81.3
Corrected by subtraction of amount found 1n check sample.
108
-------
Table IIA-l-C. Residues of EBDC (from M-22) 1n
West Coast Canned Whole Tomatoes
Sample
Rep I Check <0.1
Rep II Check 0.1
Rep III Check <0.1
Rep I Ix 0.2
Rep II Ix 0.1
Rep III Ix 0.2
Rep I 4x 0.3
Rep II 4x 0.2
Rep III 4x 0.3
Amount Found EBDC (ppm) Average
Corrected
for
Check
0.1
0.3
0.2
0.2
0.4
0.2
0.3
0.1
0.3
0.2
0.2
0.4
0.2
0.3
0.3
0.1
0.2
0.4
0.1
0.3
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check 1.2
Rep II Check 1.2
Rep III Check 1.2
Rep I Check 3.0
Rep II Check 3.0
Rep III Check 3.0
0.9
0.9
0.9
2.0
2.0
2.0
Corrected for
Check
0.9
0.8
0.9
2.0
1.9
2.0
Avg.
%
Recovery
Corrected
for Avg.
% Recovery
67.5
67.5
0.4
0.1
0.3
0.6
0.1
0.4
Recovery
75
67
75
67
63
67
Avg. %
Recovery
67.5
*Corrected by subtraction of amount found in check sample.
109
-------
Table IIA-l-D. Residues of EBDC (from M-22) in
West Coast Canned Whole Tomatoes Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm)
*Corrected Avg.
for %
Average Check Recovery
0.1
0.2
0.1
0.4
0.3
0.3
0.2
0.2
0.1
0.4
0.3
0.3
0.2
0.2
0.1
0.4
0.3
0.3
0.2
0.2
0.1
0.4
0.3
0.3
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
1.3
1.3
2.6
2.6
*Corrected for
Check
1.3
1.3
2.6
2.6
0.2
0.2
0.1
0.4
0.3
0.3
Corrected
for Avg.
% Recovery
Recovery
108
108
84
84
0.2
0.2
0.1
0.4
0.3
0.3
Avg. %
Recovery
91
*Corrected by subtraction of amount found in check sample.
110
-------
Table IIA-l-E. Residues of EBDC (from M-22) in
West Coast Canned Whole Tomatoes Simmered for 60 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
*Corrected
for
Check
0.1
0.2
0.1
0.2
0.2
0.3
0.1
0.2
0.1
0.2
0.3
0.3
0.1
0.2
0.1
0.2
0.3
0.3
0.1
0.2
0.1
0.2
0.3
0.3
Recovery Studies EBDC (ppm)
Corrected
for %
Recovery
Amount Added Amount Found
*Corrected for %
Check Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC** 1.1
0.6 EBDC*** 0.6
0.6 EBDC*** 0.4
3.1 EBDC** 2.9
1.6 EBDC*** 1.4
1.6 EBDC*** 0.9
1.1
0.6
0.4
2.9
1.4
0.9
92
100
67
94
88
56
0.1
0.2
0.1
0.2
0.4
0.4
Avg. %
Recovery
83.9
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
***Amount added has been corrected for % activity of 30. EBDC in fortified
starch had suddenly degraded.
Ill
-------
Table IIA-l-F. Residues of EBDC (from M-22) 1n
West Coast Tomato Juice
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I 1x
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Avg.
*Corrected
for
Check
Avg.
%
Recovery
Corrected
for Avg.
% Recovery
0.3
0.2
0.2
0.6
0.4
0.7
0.2
0.3
0.2
0.5
0.4
0.7
0.3
0.3
0.2
0.6
0.4
0.7
0.3
0.3
0.2
0.6
0.4
0.7
67
67
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check 1.2
Rep II Check 1.2
Rep III Check 1.2
Rep I Check 3.0
Rep II Check 3.0
Rep III Check 3.0
0.9
0.8
0.9
1.8
2.0
2.0
Corrected for
Check
0.9
0.8
0.9
1.8
2.0
2.0
Recovery
75
67
75
60
67
67
0.4
0.4
0.3
0.9
0.6
1.0
Avg. %
Recovery
67
•"Corrected by subtraction of amount found in check sample.
112
-------
Table IIA-l-G. Residues of EBDC (from M-22) 1n
West Coast Tomato Sauce
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.8
0.9
1.0
2.3
2.8
2.7
0.8
0.9
1.0
2.3
2.8
3.0
0.8
0.9
1.0
2.3
2.8
2.9
Recovery Studies EBDC (ppm)
*Corrected
for
Check
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
1.8
1.4
0.9
*Corrected for
Check
1.8
1.4
0.9
0.8
0.9
1.0
2.3
2.8
2.9
Corrected
for %
Recovery
Recovery
150
117
75
0.7
0.8
0.9
2.0
2.5
2.5
Avg. %
Recovery
114
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
113
-------
Table IIA-l-H. Residues of EBDC (from M-22) in
West Coast Tomato Paste
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
0.1
o!i
1.7
1.7
1.9
4.1
2.7
2.6
1.7
1.7
1.9
3.0
2.7
2.6
1.7
1.7
1.9
3.6
2.7
2.6
1.6
1.7
1.8
3.5
2.7
2.5
2.1
2.2
2.3
4.5
3.5
3.2
Recovery Studies EBDC (ppm)
Corrected for %
Amount Added Amount Found Check Recovery
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
1.0
1.0
1.0
0.0
1.0
0.9
75
83
75
Avg. %
Recovery
78
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
114
-------
Table IIA-2-A. Residues of ETU (from M-22) in
West Coast Unwashed Tomatoes
Sample
Amount Found EBDC
(ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.01
0.02
0.01
0.02
0.01
0.03
<0.01
0.03
0.04
0.01
0.01
0.01
<0.01
0.02
0.01
0.02
0.04
0.03
0.01
0.02
0.01
0.01
0.02
0.02
0.01
0.04
0.04
<0.01
<0.01
0.01
<0.01
0.02
0.03
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.04
0.06
0.04
Corrected for
Check
0.03
0.04
0.03
Recovery
60
80
60
<0.01
<0.01
0.01
<0.01
0.03
0.04
Avg. %
Recovery
67
*Corrected by subtraction of amount found in check sample.
115
-------
Table IIA-2-B. Residues of ETU (from M-22) 1n
West Coast Washed Tomatoes
Sample Amount Found EBDC (ppm)
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.01
0.02
0.01
0.01
0.01
0.07
0.07
0.03
0.01
0.03
0.01
0.01
0.01
0.01
0.10
0.15
0.02
Average
0.02
0.02
0.01
0.01
0.01
0.08
0.11
0.03
Corrected
for
Check
<0.01
<0.01
<0.01
0.07
0.09
0.01
Corrected
for %
Recovery
<0.01
<0.01
<0.01
0.12
0.14
0.01
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.06
0.04
0.04
*Corrected for
Check
0.05
0.02
0.02
Recovery
100
40
40
Avg. %
Recovery
67
Corrected by subtraction of amount found 1n check sample.
116
-------
Table IIA-2-C. Residues of ETU (from M-22) in
West Coast Canned Whole Tomatoes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.02
<0.01
0.01
0.02
0.02
0.01
0.07
0.04
0.07
0.01
0.01
0.02
0.03
0.05
0.01
0.08
0.04
0.07
0.02
0.01
0.01
0.03
0.04
0.01
0.08
0.04
0.07
Recovery Studies ETU (ppm)
Corrected
for
Check
0.01
0.03
<0.01
0.06
0.03
0.06
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.04
0.06
0.04
*Corrected for
Check
0.02
0.05
0.03
Corrected
for %
Recovery
0.01
0.04
<0.01
0.09
0.04
0.09
Recovery
40
100
60
Avg. %
Recovery
67
*Corrected by subtraction of amount found in check sample,
117
-------
Table IIA-2-D. Residues of ETU (from M-22) 1n
West Coast Whole Tomatoes Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
<0.01
<0.01
0.04
0.03
0.03
0.06
0.03
0.04
<0.01
<0.01
<0.01
0.03
0.12
0.03
0.05
0.03
0.04
<0.01
<0.01
<0.01
0.04
0.08
0.03
0.06
0.03
0.04
Recovery Studies ETU (ppm)
*Corrected
for
Check
0.04
0.08
0.03
0.06
0.03
0.04
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.05
0.02
*Corrected for
Check
0.03
0.05
0.02
Corrected
for %
Recovery
0.05
0.10
0.04
0.08
0.04
0.05
Recovery
60
100
40
Avg. %
Recovery
80
Corrected by subtraction of amount found in check sample.
118
-------
Table IIA-2-E. Residues of ETU (from M-22) in
West Coast Canned Whole Tomatoes Simmered for 60 minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I 1x
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
<0.01 <0.01
<0.01
<0.01
0.06
0.04
0.01
0.06
0.07
0.04
0.03
0.01
0.06
0.05
0.06
<0.01
<0.01
<0.01
0.06
0.04
0.01
0.06
0.06
0.05
Recovery Studies ETU (ppm)
*Corrected
for
Check
0.06
0.04
0.01
,06
06
0.05
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.02
0.02
*Corrected for
Check
0.03
0.02
0.02
Corrected
for %
Recovery
0.12
0.08
0.02
0.12
0.12
0.10
Recovery
60
40
40
Avg. %
Recovery
60
Corrected by subtraction of amount found in check sample,
119
-------
Table IIA-2-F. Residues of ETU (from M-22) in
West Coast Tomato Juice
Sample
Amount Found EBDC
(ppm)
Average
Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.01
0.02
0.02
0.05
0.04
0.03
0.05
0.11
0.11
0.02
0.02
0.03
0.05
0.05
0.03
0.04
0.12
0.11
0.01
0.02
0.03
0.05
0.05
0.03
0.05
0.12
0.11
0.04
0.03
<0.01
0.04
0.10
0.08
0.07
0.05
<0.01
0.07
0.17
0.13
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.05
0.05
0.05
*Corrected for
Check
0.04
0.03
0.02
Recovery
80
60
40
Avg. %
Recovery
60
^Corrected by subtraction of amount found in check sample.
120
-------
Table IIA-2-G. Residues of ETU (from M-22) in
West Coast Tomato Sauce
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I 1x
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.09
0.04
0.04
0.23
0.01
0.05
0.25
0.12
0.19
0.25
0.08
0.12
0.29
0.21
0.20
0.09
0.04
0.04
0.24
0.05
0.09
0.27
0.17
0.20
Recovery Studies ETU (ppm)
*Corrected
for
Check
0.15
0.01
0.05
0.18
0.13
0.16
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.15
0.06
0.07
*Corrected for
Check
0.06
0.02
0.03
Corrected
for %
Recovery
0.20
0.01
0.12
0.25
0.18
0.22
Recovery
120
40
60
Avg. %
Recovery
73.3
Corrected by subtraction of amount found in check sample.
121
-------
Table IIA-2-H. Residues of ETU (from M-22) in
West Coast Tomato Paste
Sample
Amount Found EBDC (ppm)
Average
Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I 1x
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.03
0.03
0.05
0.38
0.15
0.06
0.16
0.28
0.26
0.03
0.35
0.24
0.05
0.40
0.07
0.34
0.03
0.03
0.05
0.37
0.20
0.06
0.28
0.18
0.30
0.34
0.17
0.01
0.25
0.15
0.25
0.72
0.36
0.02
0.53
0.32
0.53
Recovery Studies ETU (ppm)
Corrected for %
Amount Added Amount Found Check Recovery
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.06
0.05
0.07
0.03
0.02
0.02
60
40
40
Avg. %
Recovery
47
^Corrected by subtraction of amount found in check sample.
122
-------
Table IIB-l-A. Residues of EBDC (from M-22) in
West Coast Unwashed Spinach
Sample
Amount Found EBDC
(ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.5
0.2
58.3
70.1
67.8
119.3
155.6
151.1
0.5
0.2
59.6
71.7
70.6
123.4
158.9
154.4
0.5
0.2
59.0
70.9
69.2
121.4
157.3
152.8
58.
70.
69.
120.9
157.1
152.8
78.0
91.8
89.9
157.0
204.0
199.4
Recovery Studies ETU (ppm)
Amount Added Amount Found
*Corrected for %
Check Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.5 EBDC**
1.2 EBDC**
1.2 EBDC**
7.5 EBDC**
3.1 EBDC**
3.1 EBDC**
1.6
1.0
1.2
6.3
2.2
2.7
1.1
0.8
1.2
5.8
2.0
2.7
73
67
100
77
65
77
Avg. %
Recovery
77
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
123
-------
Table IIB-l-B. Residues of EBDC (from M-22) 1n
West Coast Mashed Spinach
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.2 0.2
*Corrected
for
Check
26.2
25.4
26.6
104.1
157.2
155.8
26.9
25.5
25.5
106.2
154.4
165.4
26.6
25.5
25.1
105.2
155.8
160.6
26
25
.4
.5
25.1
105.0
155.8
160.6
Recovery Studies EBDC (ppm)
Corrected
for %
Recovery
36,
34,
34,
143.8
213.4
220.0
*Corrected for %
Amount Added Amount Found Check Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.5 EBDC**
1.2 EBDC**
1.2 EBDC**
7.5 EBDC**
3.1 EBDC**
3.1 EBDC**
3
0
1.0
6.3
2.2
2.7
1.1
0
,0
6.1
2.2
2.7
73
83
83
81
71
87
Avg. %
Recovery
73
*Corrected by subtraction of amount found in check sample,
**Amount added has been corrected for % activity of 60.
124
-------
Table IIB-1-C. Residues of EBDC (from M-22) in
West Coast Frozen Blanched Spinach
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
Corrected
for
Check
0.3
0.2
0.4
0.6
0.5
0.8
0.3
0.2
0.4
0.6
0.5
0.8
0.3
0.2
0.4
0.6
0.5
0.8
0.3
0.2
0.4
0.6
0.5
0.8
Recovery Studies EBDC (ppm)
Corrected
for %
Recovery
0.4
0.3
0.6
0.9
0.7
1.1
Amount Added Amount Found
Corrected for %
Check Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
3.1 EBDC**
3.1 EBDC**
3.1 EBDC**
0.9
0.9
0.9
2.1
2.1
2.1
0.9
0.9
0.9
2.1
2.1
2.1
75
75
75
68
68
68
Avg. %
Recovery
70
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
125
-------
Table IIB-l-D. Residues of EBDC (from M-22) 1n
West Coast Frozen Blanched Spinach Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.1
0.2
0.1
0.3
0.3
0.3
0.1
0.2
0.1
0.3
0.3
0.3
0.1
0.2
0.1
0.3
0.3
0.3
Recovery Studies EBDC (ppm)
*Corrected
for
Check
0.
0.
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
0.9
0.9
0.9
0.1
0.3
0.3
0.3
*Corrected for
Check
0.9
0.9
0.9
Corrected
for %
Recovery
,1
.3
.1
Recovery
75
75
75
0.4
0.4
0.4
Avg. %
Recovery
75
*Corrected by subtraction of amount found 1n check sample.
**Amount added has been corrected for % activity of 60.
126
-------
Table IIB-l-E. Residues of EBDC (from M-22) in
Drained Water from West Coast Frozen Blanched Spinach
Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
*Corrected
for
Check
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC**
1.2 EBDC**
0.9
0.9
0.9
*Corrected for
Check
0.9
0.9
0.9
Corrected
for %
Recovery
<0.1
<0.1
<0.1
<0.1
Recovery
75
75
75
Avg. %
Recovery
75
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
127
-------
Table IIB-l-F. Residues of EBDC (from M-22) from
West Coast Canned Spinach
Sampl e
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
*Corrected
for
Check
Corrected
for %
Recovery
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC** 0.9
1.2 EBDC** 0.9
1.2 EBDC** 0.9
3.1 EBDC** 1.8
3.1 EBDC** 2.1
3.1 EBDC** 2.0
*Corrected for
Check
0.9
0.9
0.9
1.8
2.1
2.0
Recovery
Avg. %
Recovery
67
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
128
-------
Table IIB-l-G. Residues of EBDC (from M-22) in Canned
West Coast Spinach Cooked for 5 Minutes
Sample
Amount Found EBDC (ppm)
Average
Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.1
0.1
0.1
0.1
0.1
0.1
).l
1.1
1.1
0.1
0.1
0.1
0.1
Recovery Studies EBDC (pom)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC** 0.9
1.2 EBDC** 0.9
1.2 EBDC** 0.9
*Corrected for
Check
0.8
0.8
0.9
Recovery
67
67
75
Avg. %
Recovery
69
Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
129
-------
Table IIB-l-H. Residues of EBDC (from M-22) in
Drained Water from West Coast Canned Spinach
Cooked for 5 Minutes
Sample
Amount Found EBDC (ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I lx
Rep II lx
Rep III lx
Rep I 4x
Rep II 4x
Rep III 4x
0.7
0.7
0.7
0.9'
Recovery Studies EBDC (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
1.2 EBDC**
1.2 EBDC*
1.2 EBDC**
0.9
0.9
0.9
*Corrected for
Check
0.9
0.9
0.9
%
Recovery
75
75
75
Avg. %
Recovery
75
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
Value excluded from summary table.
130
-------
Table IIB-2-A. Residues of ETU (from M-22) 1n
West Coast Unwashed Spinach
Sample
Amount Found EBDC
(ppm)
Average
*Corrected
for
.Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.02
<0.01
<0.01
0.13
0.03
0.07
0.21
0.69
0.18
<0.01
<0.01
<0.01
0.08
0.04
0.18
0.18
0.52
0.53
0.01
<0.01
<0.01
0.21
0.04
0.13
0.20
0.61
0.36
0.20
0.04
0.13
0.19
0.61
0.36
0.38
0.08
0.25
0.36
1.15
0.68
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.04
0.03
0.02
*Corrected for
Check
0.03
0.03
0.02
Recovery
60
60
40
Avg. %
Recovery
53
*Corrected by subtraction of amount found in check sample.
131
-------
Table IIB-2-B. Residues of ETU (from M-22) in
West Coast Washed Spinach
Sample
Amount Found EBDC (ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
<0.01
0.01
<0.01
0.03
0.04
0.03
0.01
0.44
0.08
<0.01
<0.01
0.03
0.04
<0.01
0.01
0.67
0.06
<0.01
<0.01
<0.01
0.03
0.04
0.02
0.01
0.57
0.07
0.03
0.04
0.02
0.01
0.57
0.07
0.06
0.08
0.04
0.02
1.08
0.13
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.02
0.03
*Corrected for
Check
0.03
0.02
0.03
Recovery
60
40
60
Avg. %
Recovery
53
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
132
-------
Table IIB-2-C. Residues of ETU (from M-22) in
West Coast Frozen Blanched Spinach
Sample
Amount Found EBOC
(ppm)
Average
Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.01
0.01
<0.01
0.37
0.46
0.34
0.65
0.36
0.90
0.01
0.01
<0.01
0.34
0.55
0.09
0.17
1.42
1.33
0.01
0.01
<0.01
0.36
0.51
0.22
0.41
0.89
1.12
0.35
0.50
0.22
0.40
0.88
1.12
.88
.25
0.55
1,
2,
00
20
2.80
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.03
0.02
*Corrected for
Check
0.02
0.02
0.02
Recovery
40
40
40
Avg. %
Recovery
40
*Corrected by subtraction of amount found in check sample.
133
-------
Table IIB-2-D. Residues of ETU (from M-22) 1n
West Coast Frozen Blanched Spinach
Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.01
<0.01
<0.01
0.65
0.62
<0.01
0.71
0.68
0.30
0.25
0.34
<0.01
0.70
0.62
0.48
<0.01
0.45
<0.48
<0.01
0.71
0.66
0.39
Recovery Studies ETU (ppm)
*Corrected
for
Check
0.44
0.47
0.01
0.70
0.65
0.38
Corrected
for %
Recovery
1.10
1.18
0.01
1.75
1.63
0.95
Amount Added Amount Found
*Corrected for %
Check Recovery
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.02
0.02
0.02
0.02
0.02
40
40
40
Avg. %
Recovery
40
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 60.
134
-------
Table IIB-2-E. Residues of ETU (from M-22) 1n
Drained Water from West Coast Frozen Blanched Spinach
Simmered for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
<0.01
0.01
<0.01
0.22
0.30
0.59
0.55
0.34
0.01
0.40
0.32
0.51
0.55
0.59
0.02
0.31
0.31
0.55
0.55
0.47
0.02
Recovery Studies ETU (ppm)
Corrected
for
Check
0.31
0.31
0.55
0.55
0.47
0.02
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.03
0.03
*Corrected for
Check
0.03
0.03
0.03
Corrected
for %
Recovery
Recovery
60
60
60
0.52
0.52
0.92
0.92
0.78
0.03
Avg. %
Recovery
60
*Corrected by subtraction of amount found in check sample.
135
-------
Table IIB-2-F. Residues of ETU (from M-22) 1n
West Coast Canned Spinach
Sample
Amount Found EBDC (ppm)
Average
*Corrected
for
Check
Corrected
for %
Recovery
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
0.01
0.01
0.01
0.67
0.78
0.78
1.29
1.31
0.83
0.01
0.01
0.01
0.66
0.78
0.73
0.61
1.54
0.47
0.01
0.01
0.01
0.67
0.78
0.76
0.95
1.43
0.65
0.66
0.77
0.75
0.94
1.42
0.64
Recovery Studies ETU (ppm)
Amount Added Amount Found
Rep I Check
Rep II Check
Rep III Check
0.05 ETU
0.05 ETU
0.05 ETU
0.03
0.03
0.03
1.65
1.93
1.88
2.35
3.55
1.60
*Corrected for
Check
0.02
0.02
0.02
Recovery
40
40
40
Avg. %
Recovery
40
^Corrected by subtraction of amount found In check sample.
136
-------
Table IIB-2-G. Residues of ETU (from M-22) in
West Coast Canned Spinach Cooked for 5 Minutes
Sample
Rep I Check
Rep II Check
Rep III Check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found EBDC (ppm) Average
0.01
0.01
0.01
0.33
1.33
1.16
1.13
1.26
0.31
0.36
0.70
1.23
1.08
1.39
0.29
0.35
1.02
1.20
1.11
1.33
0.30
Recovery Studies ETU (ppm)
*Corrected
for
Check
0.34
1.01
1.19
1.10
1.32
0.29
Corrected
for %
Recovery
0.85
2.
2.
2.
3.
53
98
75
30
0.73
Amount Added Amount Found
Corrected for %
Check Recovery
Rep I Check
Rep II Check
Rep III Check
.05 ETU
0.05 ETU
0.05 ETU
0.03
0.03
0.03
0.02
0.02
0.02
40
40
40
Avg. %
Recovery
40
*Corrected by subtraction of amount found in check sample.
137
-------
Table IIB-2-H. Residues of ETU (from M-22) in
Drained Water From West Coast Canned Spinach
Sampl e
Rep I check
Rep II check
Rep III check
Rep I Ix
Rep II Ix
Rep III Ix
Rep I 4x
Rep II 4x
Rep III 4x
Amount Found
EBDC (ppm)
<0.01
<0.01
<0.01
0.59 0.14
1.11 1.09
0.12 0.19
0.25 0.23
0.28 0.26
0.54 0.27
Average
0.37
1.10
0.16
0.24
0.27
0.41
*Corrected
for
Check
0.37
1.10
0.16
0.24
0.27
0.41
Corrected
for %
Recovery
0.70
2.08
0.30
0.45
0.51
0.77
Recovery Studies ETU (ppm)
Rep I check
Rep II check
Rep III check
Amount
Added
0.05 ETU
0.05 ETU
0.05 ETU
Amount Found
.03
0.02
.03
Corrected
for Check
0.03
0.02
0.03
%
Recovery
60
40
60
Average %
Recovery
53
Corrected by subtraction of amount found in check sample.
138
-------
APPENDIX D
Tables III to VIII
Additional Summary and Individual-Data Tables
139
-------
Table III. Effects of Washing and Canning on EBDC and ETU Residues
in Tomatoes, Carets, and Spinach Treated with D1 thane M-45
.®
Conversion
Unwashed Washed % EBDC Canned to ETU
Commodity EBDC ETU EBDC ETU Removed EBDC ETU in Canning*
East Coast
Check
Ix
4x
West Coast
Check
Ix
4x
East Coast
Check
Ix
4x
West Coast
Check
Ix
4x
East Coast
Check
Ix
4x
West Coast
Check
Ix
4x
Tomatoes
<0.
0.
0.
Tomatoes
<0.
2.
7.
Carrots
<0.
0.
0.
Carrots
<0.
0.
0.
Spinach
0.
2.
6.
Spinach
0.
61.
219.
1
3
8
1
1
1
1
6
8
1
1
4
2
5
6
3
9
3
<0.01
<0.01
0.02
<0.01
0.01
0.02
<0.01
<0.01
0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.01
0.01
0.34
1.41
0.1
0.2
0.3
<0.1
0.6
0.9
<0.1
0.3
0.7
<0. 1
0.1
0.4
0.1
1.5
2.7
0.2
9.7
58.7
0.
<0.
0.
<0.
0.
0.
<0.
<0.
<0.
<0.
<0.
<0.
<0.
<0.
0.
<0.
0.
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
02
0.08
--
33
50
--
76
87
—
50
13
--
none
none
—
40
59
--
73
0.
<0.
0.
0.
0.
1.
<0.
<0.
<0.
<0.
0.
0.
0.
<0.
<0.
0.
<
0.
1
1
1
1
5
8
1
1
1
1
1
1
1
1
1
1
1
0.01
0.03
0.10
0.01
0.11
0.13
<0.01
0.03
0.05
<0.01
<0.01
0.01
0.01
0.18
0.44
0.01
0.71
2.66
40.8
100.0
Avg. 70.4
30.9
25.2
Avg. 28T
20.6
14.7
Avg. TT7
N.D.
5.1
Avg. 276"
24.5
33.5
Avg. 29.0
14.7
9.0
Avg. TT9"
Calculations:
EBDC wash (Ix or 4x) - EBDC wash (check) x 0.486 = A
ETU canned (Ix or 4x) - [ETU canned (check) + ETU wash
(Ix or 4x)] = B
Conversion due to processing = B/A
Example:
East Coast tomatoes Ix
A = (0.2 - 0.1) 0.486 = 0.049
B => 0.03 - (0.01 + <0.01) = 0.02
B/A =T™= 0.408 x 100
\J • \J*U
40.8%
140
-------
Table IV. Conversion of EBDC1 (Added as Dithane M-45®)
to ETU on Control Samples of Tomatoes, Carrots,
and Spinach—at Various Processing Stages
Commodity Process
(Location) Stage Replicate
Tomatoes Unwashed
(East Coast)
Mashed
Frozen
Canned
Tomatoes Unwashed
(West Coast)
Washed
Frozen
Canned
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
ETU
Found
0.19
0.07
0.04
0.04
0.11
0.11
0.10
0.08
0.15
0.17
0.20
0.32
0.17
0.10
0.11
0.17
0.09
0.06
0.10
0.28
0.04
0.08
0.16
0.18
ETU in
check +
0.05 ETU
0.07
0.03
0.03
0.04
0.03
0.04
0.01
0.02
0.05
0.07
0.05
0.03
0.05
0.05
0.04
0.01
0.04
0.04
0.05
0.01
0.03
0.06
0.02
ETU % Conversion
from of EBDC
EBDC to ETU
0.12
0.04
0.01
0.04
0.07
0.08
0.06
0.07
0.13
0.12
0.13
0.27
Avg.
0.14
0.05
0.06
0.13
0.08
0.02
0.06
0.23
0.03
0.05
0.10
0.16
20.1
6.9
1.7
6.9
11.1
13.8
10.3
12.1
22.4
20.1
22.4
46.6
16.3
24.1
8.6
10.3
22.4
13.8
3.4
10.3
40.0
5.2
8.6
17.2
27.6
Avg. 16.0
141
-------
Table IV. (Continued)
Commodity
(Location)
Carrots
(East Coast)
Carrots
(West Coast)
Process
Stage Replicate
Unwashed I
II
III
Washed
Diced
Frozen
Canned
Unwashed
Washed
Diced
Frozen
Canned
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
ETU
Found
0.12
0.13
0.11
0.13
0.14
0.14
0.10
0.07
0.10
0.09
0.11
0.04
0.14
0.14
0.09
0.06
0.11
0.10
0.12
0.03
0.12
0.11
0.11
0.12
0.12
0.12
0.13
0.12
0.16
0.13
ETU in
check +
0.05 ETU
0.05
0.04
0.03
0.04
0.03
0.04
0.03
0.04
0.04
0.04
0.04
0.01
0.02
0.03
0.03
0.04
0.02
0.03
0.04
0.04
0.02
0.02
0.05
0.05
0.04
0.04
0.05
0.04
ETU % Conversion
from of EBDC
EBDC to ETU
0.07
0.09
0.08
0.09
0.11
0.10
0.07
0.03
0.06
0.05
0.07
0.04
0.13
0.12
0.06
Avg.
0.03
0.07
0.08
0.09
0.03
0.08
0.07
0.09
0.10
0.07
0.07
0.11
0.08
0.11
0.09
12.1
15.5
13.8
15.5
19.0
17.2
12.1
5.2
10.3
8.6
12.1
6.9
22.4
20.7
10.3
13.4
5.2
7.0
13.8
15.5
5.2
13.8
12.1
15.5
17.2
12.1
12.1
19.0
13.8
19.0
15.5
Avg. 13.1
142
-------
Table IV. (Continued)
Commodity Process ETU
(Location) Stage Replicate Found
Spinach Unwashed I
(East Coast) II
III
Washed
Frozen
Canned
Spinach Unwashed
(West Coast)
Washed
\
Frozen
Canned
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
I
II
III
0.14
0.10
0.11
0.11
0.06
0.21
0.11
0.13
0.13
0.16
0.20
0.16
0.04
0.06
0.04
0.06
0.04
0.04
0.07
0.07
0.07
0.13
0.08
0.14
ETU in
check +
0.05 ETU
0.03
0.03
0.04
0.04
0.04
0.07
0.03
0.04
0.04
0.04
0.04
0.03
0.03
0.01
0.03
0.04
0.03
0.03
0.01
0.04
0.03
0.05
0.05
0.06
ETU % Conversion
from of EBDC
EBDC to ETU
0.11
0.07
0.07
0.07
0.02
0.14
0.08
0.09
0.09
0.12
0.16
0.13
Avg.
0.01
0.05
0.01
0.02
0.01
0.01
0.06
0.03
0.04
0.08
0.03
0.08
19.0
12.1
12.1
12.1
3.4
24.1
13.8
15.5
15.5
20.7
27.6
22.4
16.5
2.0
10.2
2.0
4.0
2.0
2.0
12.2
6.1
8.2
16.3
6.1
16.3
Avg. 7.3
1
1.2 ppm EBDC (except 1.0 ppm for West Coast spinach) and 0.05 ppm ETU were
added to each sample. Theoretical ETU added is 1.2 x 0.486 + 0.05 = 0.63 ppm;
(1.0 x 0.486 + 0.05 = 0.54 ppm for West Coast spinach). ETU in checks, fortified
only with 0.05 ppm ETU, were subtracted from ETU found to give ETU from EBDC.
Percent conversion was calculated by dividing values in the "ETU from EBDC"
column by 0.58 (or 0.49 for West Coast spinach) x 100.
143
-------
Table V. Conversion of EBDC1 (Added as Dithane M-22®)
to ETU on Control Samples of Tomatoes and
Spinach—at Various Processing Stages
Commodity
(Location)
Tomatoes
(West Coast)
Spinach
(West Coast)
Process ETU
Stage Replicate Found
Unwashed I
II
III
Washed I
II
III
Canned Whole I
II
III
Juice I
II
III
Unwashed I
II
III
I
II
III
I
II
III
I
II
III
0.08
0.09
0.05
0.20
0.13
0.31
0.16
0.17
0.13
0.19
0.20
0.15
0.08
0.03
0.06
0.06
0.06
0.08
0.04
0.05
0.05
0.07
0.04
0.07
ETU in
check +
0.05 ETU
0.04
0.06
0.04
0.06
0.04
0.04
0.04
0.06
0.04
0.05
0.05
0.05
0.04
0.03
0.02
0.03
0.02
0.03
0.03
0.03
0.02
0.03
0.03
0.03
ETU % Conversion
from of EBDC
EBDC to ETU
0.04
0.03
0.01
0.14
0.09
0.27
0.12
0.11
0.09
0.14
0.15
0.10
Avg.
0.04
0.04
0.03
0.04
0.05
0.01
0.02 '
0.03
0.04
0.01
0.04
7.4
5.6
1.7
25.9
16.7
50.0
22.2
20.3
16.7
25.9
27.8
18.5
19.9
7.4
7.4
5.6
6.9
9.3
1.9
3.7
5.6
7.4
1.9
7.4
1
Avg. 5.4
1.2 ppm EBDC and 0.05 ppm ETU were added to each sample. Theoretical ETU
added 1s 1.1 x 0.486 + 0.05 = 0.59 ppm. ETU 1n checks, fortified only
with 0.05 ppm ETU, were subtracted from ETU found to give ETU from EBDC.
Percent conversion was calculated by dividing values in the "ETU from EBDC"
column by 0.54 x 100.
144
-------
Table VI. Rate of Formation and Breakdown of ETU from
Technical EBDC (6.2 ppm ai) in Boiling
Distil led-Water Buffered at pH 5.21
Sampl
Corrected Corrected Conversi<
Amt. Found for Amt. Found for of EBDI
e EBDC (ppm) % Recovery Avg. ETU (ppm) % Recovery Avg. to ETU
0.5 min. 2.6, 2.6 3.9, 3.9 3.9 1.01,1.39 1.01,1.39 1.20 107
30. min. 0.2, 0.2 0.3, 0.3 0.3 1.78, 1.75, 1.78, 1.75, 1.77 61
60. m1n. 0.1, 0.2 0.2, 0.3 0.3 1.72, 0.631 1.72, 0.631 1.72 59
90. min. <0.1, <0.1 <0.1, <0.1 <0.1 2.51, 2.92 2.51, 2.92 2.72 90
Recovery Studies EBDC (ppm)
Amount Amount Corrected
Sample Added Found for Check* % Recovery
0 min. control none <0. 1
11 none <0.1
0.6** 0.4 0.4
0.6** 0.4 0.4
60 min. control none <0. 1
" none <0. 1
0.6** 0.4 0.4
0.6** 0.4 0.4
Recovery Studies ETU (ppm)
Amount Amount Corrected
Sample Added Found for Check* %
0 min
60 mi
67
67
67
67
Recovery
. control none <0.01
0.05 0.05 0.05 100
n. control none <0.01
0.05 0.05 0.05 100
*Corrected by subtraction of amount found in check sample.
**Amount added has been corrected for % activity of 62%.
Determination done 1 week following other determinations.
Value excluded from subsequent calculations.
Calculation of conversion of EBDC to ETU:
Amt. EBDC fortified - amt. EBDC found x 0.486 = A
Amt. ETU found - amt. ETU (Check) = B
B/A = Conversion EBDC to ETU
Exampl e :
0.5 min. A = (6.2 - 2.6) 0.486 = 1.12
B = 1.20
B/A = y^| = 1.07 x 100 = 107%
145
-------
Table VII-l-A. Residues of EBDC (from M-22) 1n West Coast
Washed Tomatoes Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.2
0.2
0.2
0.1
0.2
0.2
Corrected
for
Check
Corrected
for
Recovery
0.2
0.2
0.2
0.1
0.2
0.2
0.2
0.2
0.2
0.1
0.2
0.2
Check
Laboratory Recovery Studies EBDC (ppm)
Amount Added
^Corrected
Amount Found for Check
1.2 EBDC'
1.0
1.0
% Recovery
83
Average recovery of fortification with 0.5 ppm added EBDC to washed
tomatoes was 40%.
^Corrected by subtraction of amount found In check sample.
1
Fortified with 0.5 ppm EBDC after washing 1n the pilot plant.
Amount added has been corrected for 60% activity.
'Fortified with 1.2 ppm EBDC 1n the laboratory. Amount added
has been corrected for 60% activity.
146
-------
Table VII-l-B. Residues of EBDC (from M-22) in West Coast
Canned Whole Tomatoes Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
<0.1, <0.1, <0.1, <0.1, <0.1
0.1
0.1
0.1
0.1
0.1
0.1
Corrected
for
Check
Corrected
for
Recovery
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
Check
Laboratory Recovery Studies EBDC (ppm)
Amount Added
*Corrected
Amount Found for Check % Recovery
1.2 EBDC'
0.9
0.9
75
Average recovery of EBDC in canned tomatoes which were prepared
from washed tomatoes containing added EBDC at 0.5 ppm was 20%.
Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
'Fortified with 1.2 ppm EBDC in the laboratory. Amount added
has been corrected for 60% activity.
147
-------
Table VII-l-C. Residues of EBDC (from M-22) in West Coast
Tomato Juice Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.3
0.3
0.3
0.3
0.3
0.3
*Corrected
for
Check
Corrected
for
Recovery
0.3
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.4
0.4
Check
Laboratory Recovery Studies EBDC (ppm)
*Corrected
Amount Added Amount Found for Check % Recovery
,2
1.2 EBDC
0.9
0.9
75
The average % recovery of EBDC In canned tomato juice prepared
from washed tomatoes containing added EBDC at 0.5 ppm was 80%.
*Corrected by subtraction of amount found 1n check sample.
Certified with 0.5 ppm EBDC after washing 1n the pilot plant.
Amount added has been corrected for 60% activity.
2Fort1f1ed with 1.2 ppm EBDC 1n the laboratory. Amount added
has been corrected for 60% activity.
148
-------
Table VII-l-D. Residues of EBDC (from M-22) in West Coast
Tomato Sauce Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.3 0.3
1.5
1.5
1.9
1.7
1.8
1.5
*Corrected
for
Check
1.2
1.2
1.6
1.4
1.5
1.2
Corrected
for
Recovery
1.3
1.3
1.7
1.5
1.6
1.3
Check
Check
Laboratory Recovery Studies EBDC (ppm)
Amount Added Amount Found
1.2 EBDC'
1.2 EBDC
1.4
1.4
*Corrected
for Check
1.1
1.1
% Recovery
92
92
Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC after washing 1n the pilot plant.
Amount added has been corrected for 60% activity.
2
Fortified with 1.2 ppm EBDC in the laboratory. Amount added
has been corrected for 60% activity.
149
-------
Table VII-l-E. Residues of EBDC (from M-22) in West Coast
Tomato Paste Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
2.7
2.7
2.7
2.9
2.8
2.8
*Corrected
for
Check
2.7
2.7
2.7
2.9
2.8
2.8
Corrected
for
Recovery
2.4
2.4
2.4
2.6
2.5
2.5
Check
Check
Laboratory Recovery Studies EBDC (ppm)
Amount Added Amount Found
1.2 EBDC'
1.2 EBDC
1.3
1.4
*Corrected
for Check
1.3
1.4
% Recovery
108
117
^Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
'Fortified with 1.2 ppm EBDC in the laboratory. Amount added
has been corrected for 6056 activity.
150
-------
Table VII-2-A. Residues of ETU (from M-22) in West Coast
Washed Tomatoes Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
Corrected
for
Check
0.02, 0.02, 0.01, 0.03, 0.03, 0.03
0.09
<0.01
0.02
0.04
0.02
0.02
Corrected
for
Recovery
0.07
<0.01
<0.01
0.02
<0.01
<0.01
0.09
<0.01
<0.01
0.03
<0.01
<0.01
Check
Laboratory Recovery Studies ETU (ppm)
*Corrected
Amount Added Amount Found for Check % Recovery
,2
0.05 ETU'
0.06
0.04
80
*Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
2
Fortified with 0.05 ppm ETU in the Laboratory.
151
-------
Table VII-2-B. Residues of ETU (from M-22) 1n West Coast
Canned Whole Tomatoes Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
*Corrected
for
Check
0.03, 0.02, 0.03, 0.03, 0.03, 0.02
0.05
0.03
0.06
0.05
0.05
0.05
Corrected
for
Recovery
0.02
<0.01
0.03
0.02
0.02
0.02
0.03
<0.01
0.05
0.03
0.03
0.03
Check
Laboratory Recovery Studies ETU (ppm)
*Corrected
Amount Added Amount Found for Check % Recovery
0.05 ETU'
0.06
0.03
60
^Corrected by subtraction of amount found 1n check sample.
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
Fortified with 0.05 ppm ETU in the Laboratory.
152
-------
Table VII-2-C. Residues of ETU (from M-22) in West Coast
Tomato Juice Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
*Corrected
for
Check
<0.01, 0.03, 0.03, 0.02, 0.04
0.09
0.09
0.07
0.10
0.09
0.09
Corrected
for
Recovery
0.07
0.07
0.05
0.08
0.07
0.07
0.09
0.09
0.06
0.10
0.09
0.09
Check
Laboratory Recovery Studies ETU (ppm)
Corrected
Amount Added Amount Found for Check % Recovery
,2
0.05 ETU'
0.06
0.04
80
Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
'Fortified with 0.05 ppm ETU in the Laboratory.
153
-------
Table VII-2-D. Residues of ETU (from M-22) in West Coast
Tomato Sauce Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
Corrected
for
Check
0.03, 0.02, 0.01, 0.03, 0.03, 0.03
0.07
0.09
0.09
0.07
0.09
0.08
Corrected
for
Recovery
0.04
0.06
0.06
0.04
0.06
0.05
0.05
0.07
0.07
0.05
0.07
0.06
Laboratory Recovery Studies ETU (ppm)
Amount Added Amount Found
Check
Check
Check
0.05 ETU2
0.05 ETU
0.05 ETU
0.07
0.07
0.08
*Corrected
for Check
0.04
0.04
0.05
% Recovery
80
80
100
Avg.
87
Corrected by subtraction of amount found 1n check sample.
1
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
'Fortified with 0.05 ppm ETU in the Laboratory.
154
-------
Table VII-2-E. Residues of ETU (from M-22) in West Coast
Tomato Paste Fortified with 0.5 ppm EBDC
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.01, 0.04, 0.40
0.20
0.03
0.18
0.13
0.13
0.19
Avg.
0.03
Corrected
for
Check
0.17
<0.01
0.15
0.10
0.10
0.16
Corrected
for
Recovery
0.25
<0.01
0.22
0.15
0.15
0.24
Laboratory Recovery Studies ETU (ppm)
Corrected
Amount Added Amount Found
Check
Check
Check
0.10 ETU2
0.05 ETU
0.05 ETU
0.11
0.06
0.06
for Check
0.08
0.03
0.03
% Recovery
80
60
60
Avg.
67
*Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC after washing in the pilot plant.
Amount added has been corrected for 60% activity.
2Fortified with 0.05 ppm ETU in the Laboratory.
155
-------
Table VII-3-A. Residues of ETU (from M-22) in West Coast
Washed Tomatoes Fortified with 0.07 ppm ETU1
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.03
0.02
0.01
0.02
0.03
0.03
Corrected
for
Check
0.01
0.01
0.01
0.01
0.01
0.01
Corrected
for
Recovery
0.
0.
0.
0.
01
01
01
01
0.01
0.01
See Table VII-2-A for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
Fortified with 0.07 ppm ETU after washing In the pilot plants.
156
-------
Table VII-3-B. Residues of ETU (from M-22) in West Coast
Canned Whole Tomatoes Fortified with 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.03
0.05
0.02
0.02
0.02
0.02
*Corrected
for
Check
<0.01
0.02
<0.01
<0.01
<0.01
<0.01
Corrected
for
Recovery
<0.01
0.03
<0.01
<0.01
<0.01
<0.01
See Table VII-2-B for Recovery Studies.
Corrected by subtraction of amount found in check sample.
Fortified with 0.07 ppm ETU after washing 1n the pilot plants,
157
-------
Table VII-3-C. Residues of ETU (from M-22) in West Coast
Tomato Juice Fortified with 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.05
0.03
0.09
0.08
0.06
0.04
Corrected
for
Check
0.03
0.01
0.07
0.06
0.04
0.02
Corrected
for
Recovery
0.04
0.01
0.09
0.08
0.05
0.03
See Table VII-2-C for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
1
Fortified with 0.07 ppm ETU after washing in the pilot plants.
158
-------
Table VII-3-D. Residues of ETU (from M-22) in West Coast
Tomato Sauce Fortified with 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.17
0.19
0.14
0.19
0.18
0.18
*Corrected
for
Check
0.14
0.16
0.11
0.16
0.15
0.15
Corrected
for
Recovery
0.18
0.20
0.14
0.20
0.19
0.19
See Table VI1-2-D for Recovery Studies.
*Corrected by subtraction of amount found in check sample.
Fortified with 0.07 ppm ETU after washing in the pilot plants.
159
-------
Table VII-3-E. Residues of ETU (from M-22) in West Coast
Tomato Paste Fortified with 0.07 ppm ETU1
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.16
0.18
0.13
0.21
0.18
0.25
*Corrected
for
Check
0.13
0.15
0.10
0.18
0.15
0.22
Corrected
for
Recovery
0.19
0.22
0.15
0.27
0.22
0.33
See Table VII-2-E for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
1
Fortified with 0.07 ppm ETU after washing in the pilot plants,
160
-------
Table VII-4-A. Residues of EBDC (from M-22) in West Coast Washed
Tomatoes Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.1
0.2
0.3
0.2
0.2
0.2
"Corrected
for
Check
Corrected
for
Recovery
0.1
0.2
0.3
0.2
0.2
0.2
0.1
0.3
0.4
0.3
0.3
0.3
Check
Laboratory Recovery Studies EBDC (ppm)
Corrected
Amount Added Amount Found for Check % Recovery
,2
1.2 EBDC'
0.9
0.9
75
The average % recovery of added EBDC to washed tomatoes was 60%.
*Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC +0.07 ppm ETU after washing in the
pilot plant. EBDC added has been corrected for 60% activity.
"Fortified with 1.2 ppm EBDC in the laboratory. Amount added has
been corrected for 60% activity.
161
-------
Table VII-4-B. Residues of EBDC (from M-22) in West Coast Canned
Whole Tomatoes Fortified with 0.5 ppm EBDC + 0.07 ppm ETU1
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.1
0.1
0.1
0.1
0.1
0.1
Corrected
for
Check
Corrected
for
Recovery
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
Check
Laboratory Recovery Studies EBDC (ppm)
*Corrected
Amount Added Amount Found for Check % Recovery
,2
1.2 EBDC
1.3
1.3
108
The average % recovery of added EBDC from canned whole tomatoes
prepared from fortified washed tomatoes was 20%. The prepara-
tion step calls for removal of skins.
Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in the
pilot plant. EBDC added has been corrected for 60% activity.
'Fortified with 1.2 ppm EBDC in the laboratory. Amount added has
been corrected for 60% activity.
162
-------
Table VII-4-C. Residues of EBDC (from M-22) in West Coast Canned
Tomato Juice Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
1
Sampl e
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
0.4
0.3
0.4
0.4
0.4
0.4
Corrected
for
Check
Corrected
for
Recovery
0.4
0.3
0.4
0.4
0.4
0.4
0.4
0.3
0.4
0.4
0.4
0.4
Check
Laboratory Recovery Studies EBDC (ppm)
Amount Added
Corrected
Amount Found for Check % Recovery
1.2 EBDC'
1.3
1.3
108
The average recovery of added EBDC from tomato juice prepared from
fortified washed tomatoes was 80%.
Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in the
pilot plant. EBDC added has been corrected for 60% activity.
'Fortified with 1.2 ppm EBDC in the laboratory. Amount added has
been corrected for 60% activity.
163
-------
Table VII-4-D. Residues of EBDC (from M-22) in West Coast Tomato
Sauce Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
1.9
1.9
1.9
1.9
1.8
1.9
*Corrected
for
Check
1.6
1.6
1.6
1.6
1.5
1.6
Corrected
for
Recovery
1.7
1.7
1.7
1.7
1.6
1.7
See Table VII-2-D for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in the
pilot plant. EBDC added has been corrected for 60% activity.
164
-------
Table VI1-4-E. Residues of EBDC (from M-22) in West Coast Tomato
Paste Fortified with 0.5 ppm EBDC + 0.07 ppm ETU1
Sample
Check
1
2
3
4
5
6
Amount Found EBDC (ppm)
3.1
4.8
4.8
4.2
4.4
4.5
Corrected
for
Check
3.1
4.8
4.8
4.2
4.4
4.5
Corrected
for
Recovery
2.7
4.2
4.2
3.7
3.9
4.0
See Table VII-2-E for Recovery Studies.
*Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in the
pilot plant. EBDC added has been corrected for 60% activity.
165
-------
Table VII-5-A. Residues of ETU (from M-22) in West Coast Washed
Tomatoes Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.05
0.01
0.02
0.03
0.03
0.02
Corrected
for
Check
0.03
<0.01
<0.01
0.01
0.01
<0.01
Corrected
for
Recovery
0.04
<0.01
<0.01
0.01
0.01
<0.01
See Table VI1-2-A for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
1
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in
the pilot plant. EBDC added has been corrected for 60%
activity.
166
-------
Table VII-5-B. Residues of ETU (from M-22) in West Coast Canned
Whole Tomatoes Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
:1
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.06
0.07
0.07
0.07
0.05
0.08
Corrected
for
Check
0.03
0.04
0.04
0.04
0.02
0.05
Corrected
for
Recovery
0.05
0.07
0.07
0.07
0.03
0.08
See Table VII-2-B for Recovery Studies.
*Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in
the pilot plant. EBDC added has been corrected for 60%
activity.
167
-------
Table VII-5-C. Residues of ETU (from M-22) in West Coast Tomato
Juice Fortified with 0.5 ppm EBDC + 0.07 ppm ETU1
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.08
0.14
0.13
0.12
0.06
0.07
Corrected
for
Check
0.06
0.12
0.11
0.10
0.04
0.05
Corrected
for
Recovery
0.08
0.15
0.14
0.13
0.05
0.06
See Table VI1-2-C for Recovery Studies.
Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in
the pilot plant. EBDC added has been corrected for 60%
activity.
168
-------
Table VII-5-D. Residues of ETU (from M-22) 1n West Coast Tomato
Sauce Fortified with 0.5 ppm EBDC + 0.07 ppm ETU
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.40
0.26
0.29
0.36
0.24
0.56
*Corrected
for
Check
0.37
0.23
0.26
0.33
0.21
0.53
Corrected
for
Recovery
0.46
0.29
0.33
0.41
0.26
0.66
See Table VI1-2-D for Recovery Studies.
Corrected by subtraction of amount found 1n check sample.
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing in
the pilot plant. EBDC added has been corrected for 60%
activity.
169
-------
Table VII-5-E. Residues of ETU (from M-22) in West Coast Tomato
Paste Fortified with 0.5 ppm EBDC + 0.07 ppm ETU1
Sample
Check
1
2
3
4
5
6
Amount Found ETU (ppm)
0.62
0.19
0.63
0.41
0.51
0.22
Corrected
for
Check
0.59
0.16
0.60
0.38
0.48
0.19
Corrected
for
Recovery
0.88
0.24
0.90
0.57
0.72
0.28
See Table VII-2-E for Recovery Studies.
^Corrected by subtraction of amount found in check sample.
Fortified with 0.5 ppm EBDC + 0.07 ppm ETU after washing 1n
the pilot plant. EBDC added has been corrected for 60%
activity.
170
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Table VII. Summary Table of Average Residues (ppm) from Fortified Control
Whole Tomatoes and from Whole Tomatoes with Residues of the Same
Magnitude from Field-Applied Dithane M-22®
4x Treatment—at Various Stages of Processing
Fort, with 0.5
Fort, with . Fort, with ppm EBDC and 4x treatment
0.5 ppm EBDC 0.07 ppm ETU 0.07 ppm ETU in field
Process Stage
Washed
Canned
Canned
Tomato
Tomato
Tomatoes
Whole Tomatoes
Tomato Juice
Sauce
Paste
EBDC
0.2
0.1
0.4
1.5
2.5
ETU
0.
0.
0.
0.
0.
02
03
09
06
17
ETU
0.
0.
0.
0.
0.
01
01
05
18
23
EBDC
0
0
0
1
3
.3
.1
.4
.8
.8
ETU
0.02
0.06
0.10
0.40
0.60
EBDC
0.5
0.4
0.8
2.7
3.7
ETU
0.10
0.07
0.12
0.22
0.46
Results for EBDC have been corrected for % activity, all results
have been corrected for check values and recovery data.
171
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Table VIII. Summary of all Recovery Data
(DUhane M-45® and D1 thane M-22®)
Recoveries From Dithane M-45
.®
Tomatoes
Unwashed
Washed
Tailings
Canned
(Average)
Carrots
Unwashed
Washed
Diced
Frozen
Canned
(Average)
Spinach
Unwashed
Washed
Frozen
Canned
(Average)
Average %
East Coast
EBDC
108
97
95
90
95.2
EBDC
82
71
87
82
80
80.9
EBDC
68
85
88
90
86.7
Recovery East
ETU
87
80
47
107
80
ETU
80
73
73
80
40
69.3
ETU
73
80
73
67
70.9
Coast All
West
Tomatoes
Unwashed
Washed
Tailings
Canned
(Average)
Carrots
Unwashed
Washed
Diced
Frozen
Canned
(Average)
Spinach
Unwashed
Washed
Frozen
Canned
(Average)
Commodities
Coast
EBDC
96
89
--
68
84.2
EBDC
82
79
81
88
83
82.6
EBDC
87
67
79
76
77.3
ETU
87
60
37
73
64.2
ETU
60
67
53
93
87
72
ETU
47
67
53
107
68.3
EBDC ETU
87.9 73.2
Average % Recovery West Coast All Commodities
EBDC
ETU
81.2 65.9
Average % Recovery East and West Coast All Commodities
EBDC ETU
n=211 85.6 n=77 70.8
Average % Recovery by Commodity
EBDC ETU
Tomatoes 91.8 72.0
Carrots 81.8 70.7
Spinach 84.3 69.6
Recoveries From Pi thane M-22® (West Coast only)
Spinach
Tomatoes
EBDC
72.5
72.2
ETU
47.5
63.5
172
-------
APPENDIX E
GC/MS Confirmatory Data
173
-------
APPENDIX E TflBLE I
HflS-S- SPECTRfl OF STflNDRRD ETU
SflMPLE-: S-NBUTYL DERIVflTIVE OF ETU
CI MODE
.j,
1........II .-.).„.,
109
ISO
ZOO
FRN 8799 SPEC! 22
249
174
-------
flPPENDIX E TflBLE II
.hflSS SPECTRR OF CRNNED SPINRCH
5RMP.LE: CONTROL R€P III FOR S-N BUTYL ETU
£1 MODE (CH4)
I
.i
81
100
150
200
207
FRN 8404 SPE.CT
1
175
-------
flPPENDIX E TflBLE III
MflSS' SPECTRA OF CflNNED SPINRCH. M-45
SAMPLE-* IX. R€P I FOR S-N BUTYL ETU
£T MODE
llllllllj.illll.llllllllllljllll'
t
.lllllllll.l.lll
li|iili'iii.jliii'.lil|liii'iiinlili'iii»|iiiiiiiil|iiii ii.i
~
109
i^
ISO
200
249
FRN 8801 SPECT 21
176
-------
HPPENDIX. E TflB-LE IV
ttflSS SPECTRfl. FOR. CflNNED SPINflCH M-45
-SflMPLE: 4-X. R-EP III "FOR. S'-NBUTYL ETU
109
ISO
ZOO
FRN 8800 SPECT 21
239
177
-------
APPENDIX. E Tfl'BLE V
HflSS SPECTRfl OF STflNOflRO ETU
SflttPLE: S-NBUTYL DERIVATIVE OF ETIT
1 MODE
I 1 1'lll
'
I .
. , II ,. II 1 1 . .. 1 1.
SO 101
1,,
I
1
Ull H
1
ll 't II | I1! 1 '111 1 Itl 'lull 1 1 1 1 1
ISO 200
30
FRN 8557 SPECT
178
-------
APPENDIX. E TflBLE VI
SPECTRA OF CANNED SPINflCH CONTROL
CONTROL REP HI FOR S-N8UTYL ETU
El MODE
vo
FRN 8556 SPECT
-------
flPPENDIX E TflBLE VII
\
MflS-S SPECTRfl OF CflNNED SPINflCH M-45
SflMPLE: IX REP I FOR S'-NBUTYL ETU
fl MOUE
ILL
.1..
..lull.
30
SO
100
FRN 8555 SPECT
ISO,
200
180
-------
APPENDIX. E TRB.LE. VIII
KlflSS .SPECTRfl OF. CflNNED SPINflCH M-45
iSflMPLE-: 4-X. REP III FOR S-NBUTYL ETU
El MODE
..t.i ,'liiiii t.-. iiilll'iiii.i ii j
SO
100
ISO
ZOO
FRN 8554 SPECT 1
181
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/1-77-021
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Effects of Food Processing on Residues of
Ethylenebisdithiocarbamate Fungicides and
Ethylenethiourea
5. REPORT DATE
April 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
W.F. Phillips, M.D. Grady and *Ralph Freudenthal
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Technological Resources, Inc.
Campbell, New Jersey 08101,
Battelle Memorial Institute
Columbus, Ohio 43201 (*)
1EA615
and
11. CONTRACT/GRANT NO.
68-02-1715
12. SPONSORING AGENCY NAME AND ADDRESS
Health Effects Research Laboratory HERL-RTP
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA 600/11
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Tomatoes, carrots, and spinach were treated at application rates recommended
for good agricultural practice and at 4 times these rates with two
ethyl enebisdithiocarbamate (EBCD) fungicides (Dithane M-45[R] and Dithane M-22[R])
locations6 Fa??Sflnri?!hOWnThn keeE1.n? ,w1th ?ood agricultural practice at two
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
C. COSATI Field/Group
vegetable crops
food processing
fungicides
residues
EBCD
ETU
06 F
^DISTRIBUTION STATEMENT
TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
196
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
182
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