vvEPA
United States
Environmental Protection
Agency
Research and Development
Health Effects
Laboi ato' •/
Research Triar.iie Park NC 27711
EPA-600/4-79-077
A One Step
Method for the
Determination of
Carbamate
Pesticides by
Derivatization with
a-Bromo-2,3,4,5,
6-Pentafluorotoluene
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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 MONITORING series
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161
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EPA-600/4-79-077
September 1979
A ONE STEP METHOD FOR THE DETERMINATION OF CARBAMATE PESTICIDES
BY DERIVATIZATION WITH o-BROMO-2,3,4,5,6-PENTAFLUOROTOLUENE
by
Merrill D. Jackson, Stephen D. Soileau, G. Wayne Sovocool
and Richard A. Sachleben
Environmental Toxicology Division
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
HEALTH EFFECTS RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
U.S. Environmental Protection ARency
Region 5, Library (PL-12J)
77 West Jackson Boulevatd. 12th Floor
Chicago, IL 60604-3590
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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 consti-
tute 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 participates in the development
and revision of 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 primarily responsible for providing 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.
Pursuant to the mission of the laboratory to investigate the effects
of pesticide and toxic substances on human health, this project was
undertaken to investigate an analytical method which would permit the
analysis of many of the carbamate pesticides using the standard Environ-
mental Protection Agency gas chromatographic parameters already set for
the organochlorine pesticides. The method and analytical parameters for
the carbamate pesticides tested by this method are presented.
F. G. Hueter, Ph.D.
Director
Health Effects Research Laboratory
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ABSTRACT
A procedure was developed for the determination of trace quantities
of a broad range of carbamate pesticides. The carbamates were hydrolyzed
and derivatized in a single step, using alkali and orbromo-2,3,4,5,6-
pentafluorotoluene (PFBB), and were subsequently analyzed using electron
capture gas chromatography. This one step derivatization method created
a novel derivative in which one fluorine on the PFB ring was displaced
by an ethoxide ion via aromatic nucleophilic substitution.
IV
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CONTENTS
Page
DISCLAIMER ii
FOREWORD iii
ABSTRACT iv
LIST OF FIGURES vi
LIST OF TABLES v.i
ACKNOWLEDGMENTS vii
SECTIONS
I. CONCLUSION 1
II. INTRODUCTION 2
III. EXPERIMENTAL 4
IV. DISCUSSION 8
V. REFERENCES 20
APPENDIX 23
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LIST OF FIGURES
No. Page
1. General Mechanism of Fluorine Displacement by
Ethoxide Ion 14
2. Thiophanate Methyl Derivative 16
3. General Derivatization Route of Substituted Phenoxide
Forming Carbamates 17
4. Aldicarb Derivative 19
LIST OF TABLES
No. Page
1. Carbamate Pesticides Evaluated 9
2. PFBB Reaction Products and Major MS Fragments 13
VI
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ACKNOWLEDGMENTS
The cooperation of Dr. Lynn Wright in running the CI mass spectra
and Dr. Dan Zehr for helpful suggestions is gratefully acknowledged.
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SECTION I
CONCLUSIONS
A method has been evaluated for the general analysis of carbamate
pesticides. This method involves the hydrolysis of the intact carbamate
pesticide to a substituted phenoxide ion which is then derivatized by
the addition of crbromo-2,3,4,5,6-pentafluorotoluene (PFBB). The method
provided chromatographiable peaks using the standard EPA gas chromatographic
parameters with 18 of the 23 carbamate pesticides tested.
Mass spectra were run on selected carbamate derivatives. It was
determined from these that those carbamates which would hydrolyze to
form phenolic intermediates formed derivatives with one fluorine displaced
by an ethoxy group in the PFBB characterized by an abundant fragment ion
of m/z 179, while those carbamates which would not form the phenolic
irtermediates followed no discernible pattern.
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SECTION II
INTRODUCTION
Since the introduction of carbaryl in 1956, carbamate pesticides
have become widely used in agricultural pest control programs. With the
advent of this wide use, problems of analysis have become evident.
Carbamates generally give poor electron capture response and are too
thermally unstable to be analyzed by conventional gas chromatography.
However, many methods have been developed to overcome these problems. A
large number of these methods involve some type of chemical derivatization.
Three basic types of derivatization procedures have been developed;
derivatization of the intact carbamate, derivatization of the subsequent
substituted phenol or phenol analog generated through hydrolysis, or
derivatization of the subsequent amine generated through hydrolysis.
There have been several methods developed for the direct conversion
of carbamates to chromatographiable compounds. Silylation, acetylation,
alkylation, transesterification, ' and perfluorination ' of
various carbamates have been accomplished. Other methods involve hydrolysis
14
of phenol generating carbamates and subsequent bromination, chloro-
15~20 21 23
acetylation, thiophosphorylation, and silylation ' of the phenolic
intermediates. Other reagents used for the derivatization of phenolic
22~25
intermediates include dinitrophenyl reagents, and crbromo-2,3,4,5,6-
26~ 30
pentafluorotoluene (pentafluorobenzyl bromide). Not all carbamates
form phenols during hydrolysis. For those carbamates which hydrolyze to
give amines, methods have been developed for derivatization of the
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31 32 33
amines. Bromination, iodination, and p-bromobenzoylation of the
intermediate amines are several of the methods used. Also, as with the
34 35
phenolic intermediates previously mentioned, dinitrophenyl, ' and
pentafluorobenzyl ' reagents have been used.
While all of these methods are relatively sensitive by electron
capture detection, no single procedure covered a wide range of carbamate
pesticides.
39
The EPA Pesticide Analytical Manual contains general procedures
for the organochlorine and organophosphorus pesticides. The purpose of
i»
this study was to determine if one of the carbamate derivatization
methods could be extended to a wide range of carbamate pesticides at the
residue level and still use the standard gas chromatographic columns and
39
operating conditions described in the EPA manual.
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SECTION III
EXPERIMENTAL
Reagents and Solvents
Alcoholic potassium hydroxide: Dissolved 1.0 g of solid potassium
hydroxide in 100 ml of 95% ethanol (1% w/v).
Derivatizing reagent: Diluted 0.1 ml of a-bromo-2,3,4,5,6-penta-
fluorotoluene (Aldrich Chemicals, Milwaukee, WS) in 10 ml of 95% ethanol
(CAUTION: This reagent is a strong lacrymator).
Carbamate Standards: Analytical grade pesticides (Pesticide Repository,
U.S. Environmental Protection Agency, Research Triangle Park, NC) were
dissolved in either benzene, n-hexane or toluene (1 mg/ml). Appropriate
dilutions were prepared.
n-Hexane: pesticide quality
Benzene: pesticide quality
Toluene: pesticide quality
Ethanol: 95%
Equipment
Gas chromatograph: Model MT-220 equipped with a nickel electron
capture detector (Tracer, Inc., Austin, TX). Glass columns (182 x 0.2
cm i.d.) containing either 1.50% 0V-17/1.95% OV-210 or 4% SE-30/6%
OV-210 on Gas Chrom Q, 80-100 mesh were used. All columns were pre-
conditioned at 225°C for 24 hours prior to use. Operating parameters
were: inlet, 220°C; column oven, 220°C; detector, 350°C; nitrogen
carrier gas, 100 ml/min.
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Mass spectrometers: Model HP-5930A equipped with an HP-5700A gas
chromatograph and a 5933A data system was used in the electron impact
mode (Hewlett Packard, Palo Alto, CA). Standard 70 eV conditions were
used with a filament emission of 120 pa and an ion source temperature of
190°C. All samples were scanned from m/z 50 to 550 at m/z 160 per sec.
The gas chromatograph was equipped with a 182 x 0.2 cm i.d. glass column
packed with 1.50% 0V-17/1.95% OV-210 on Gas Chrom Q, 80-100 mesh. The
operating parameters were: helium flow, 40 ml/min; inlet temperature,
200°C; transfer line temperature, 210°C; and the oven and membrane
separator were temperature programmed from 80°C (2 min) to 230°C at
8°C/min. Model 3200 quadrupole mass spectrometer equipped with a CI
source, Model 9500 gas chromatograph and Model 6100 data system (Finnigan
Corp., Sunnyvale, CA). The experimental conditions were: ionization
source temperature 120°C; source pressure 130 Pa; reagent and carrier
gas, (ultra pure) methane, 20 ml/min; separator oven 220°C and transfer
lines 200°C; injection port temperature 225°C. The 182 x 0.2 cm i.d.
glass GC column contained 1.50% 0V-17/1.95% OV-210 on Gas Chrom Q,
80-100 mesh and was operated at 210°C.
Tube block heater: CRC Rubber Co., Cleveland, OH
Tube rotator: Kraft Apparatus, Inc., Mineola, NY
Culture tube: 15 ml, screw capped, teflon lined caps
Centrifuge tube, 15 ml graduated, glass stoppered
Teflon tape, 1 cm wide
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Procedure
Pipet 1 ml of alcoholic potassium hydroxide, 0.1 ml of derivatizing
reagent and 1 ml of carbamate standard into a 15 ml culture tube with a
teflon lined screw cap. Place the culture tube in a pre-heated (95 ±
1°C) tube block heater for two hours. The length of time and temperature
are critical, for overheating can cause an increase in the formation of
OO
extraneous gas chromatographic peaks. Remove, allow to cool at room
temperature, and add 5 ml of distilled water and 4 ml of n-hexane to the
culture tube. Place the culture tube on the tube rotator (60 rpm) for
two minutes and at the end of this time transfer the n-hexane layer to a
15 ml centrifuge tube. Add an additional 4 ml of n-hexane to the culture
tube, and place in the tube rotator for an additional two minutes.
Combine the n-hexane layer with the previous n-hexane extract. Bring
the final volume of the centrifuge tube to 10 ml with n-hexane. The
sample is now ready for further cleanup or gas chromatographic analysis.
Characterization
The PFB derivative was characterized by electron capture gas chroma-
tography and the derivatization procedure evaluated utilizing the following
criteria:
1. G.C. Retention Time Relative to Aldrin
2. Derivatization Linearity. Linearity was checked over a concen-
tration range from 0.1 ng/pl to 1,000 ng/ul, if possible, or
to the limits of detection. Allowances of ± 15% were tolerated
in determining the range of derivatization linearity.
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3. Linearity of Electron Capture Detector Response. The response
linearity of the derivatives were determined on two gas chroma-
tographic columns. A concentration of the derivative was
selected so that a 5 [jl injection would produce a peak height
of approximately 40-45% full scale deflection (FSD). Injections
of 2 to 8 ul» at 1 pi increments, were made, with an allowance
of ± 10% tolerated in determining linearity.
4. Minimum Detectable Level. Minimum detectable level was defined
to be 10% full scale deflection, provided that this was at
least twice the background noise. (This might be a combination
of gas chromatographic baseline and background from the derivati-
zation procedure.) The theoretical concentration for this
response was calculated and the proper concentration prepared.
5. Quantity p_f Derivative Required to Give 50% Full Scale Deflection.
This quantity is not necessarily five times the minimum detectable
level, since this level was determined using a "clean" baseline.
A clean baseline was achieved by preparing a derivative at a
sufficient concentration such that dilution by a factor of 100
was necessary to bring the derivative peak(s) on scale. In
this way, blank interference peaks were negated.
6. Storage of Derivatized Samples. One sample was stored at 4°C
(refrigeration) and a second sample was stored in the dark at
ambient conditions. These samples were chromatographed at 0,
1, 2, 4, and 8 days to determine their stability under storage
conditions.
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SECTION IV
RESULTS AND DISCUSSION
Derivatization
The derivatization procedure used is similar to that of Coburn and
40
Chau. The hydrolysis and the derivatization steps have been combined
into one step, to save time and minimize chances for error.
All of the pesticides which were tested with this method are given
in Table 1. Of the 23 carbamate pesticides tested, only five (asulam,
pebulate, propham, trial late and vernolate) did not form a gas chromato-
graphable derivative.
The characterization data on the derivatives is located in the
appendix. During the course of the characterization of the carbamate
derivatives, two main difficulties were encountered. These difficulties
were a decrease in the extent of reaction at low concentrations (i.e.,
> 10 ng/ul) and large background interference caused by the derivatization
reagent (this interference is discussed in the Mass Spectrometric Identifi-
cation section). It is not clear why the extent of the reaction decreases
at low concentrations, but it could be caused by competing reactions of
the PFBB with ethoxide ions, or a small loss of derivative in the extrac-
tion procedure, which becomes a large percentage of the derivative at
low concentrations. With some of the carbamate derivatives, the back-
ground interference was so great that dilution of the final extract by a
factor of 100 to quantitate the gas chromatographic peaks was required.
8
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Table 1. Carbamate Pesticides Evaluated
Chemical Name
Common Name
Aldicarb (Temik)
Aminocarb (Matacil)
Asulam (Asulox)
Barban (Carbyne)
Benthiocarb (Bolero)
Carbaryl (Sevin)
Carbofuran (Furadan)
CDEC (Sulfallate)
Chlorpropham (CIPC)
Desmedipham (Betanex)
Formetanate Hydrochloride (Carzol SP)
Kabutilate (Tardex)
Meobal
Methiocarb (Mesurol)
2-Methyl-2-(methylthio)propional=
dehyde-0-(methylcarbamoyl)oxime
4-Dimethylamino-m-tolyl methyl
carbamate
Methy1(4-amino benzenesulfonyl)
carbamate
4-Chlorobut-2-ynyl-3-chloro-
phenyl carbamate
S-4-Chlorobenzyl diethyl-
thiocarbamate
1-Naphthyl N-methylcarbamate
2,3,-Dihydro-2,2-dimethylbenzo=
furan-7-yl methylcarbamate
2-Chlorallyl diethyldithio-
carbamate
Isopropyl N-(S-chlorophenyl)
carbamate
3-Ethoxy carbonyl amino-phenyl
phenylcarbamate
m-((Dimethyl amino)methylene)
amino)phenyl methylcarbamate
hydrochloride
m-(3,3-Dimethylureido)phenyl
tert-butylcarbamate
3,4-Dimethylphenyl N-methylcarbamate
4-(Methylthio)-3,5-xylyl
N-methylcarbamate
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Table 1.
Common Name
Methomyl (Lannate)
Pebulate (Tillam)
Phenmedipham (Betanal)
Promecarb (Carbamult)
Propham (IPC)
Propoxur (Baygon)
Thi ophanate-Methyl
Trial!ate
Vernolate (Vernam)
Carbamate Pesticides Evaluated
(Continued)
Chemical Name
S-Methyl N-((methylcarbamoyl)
oxy)thioacetimidate
S-Propyl butyl ethylthiocarbamate
3-Methy1oxy-carbony1 ami no-pheny1 N-
(3'-methylphenyl)carbamate
3-Isopropy1-5-methy1phenyl
methylcarbamate
Isopropy1-N-pheny1carbamate
o-Isopropoxyphenyl N-methyl-
carbamate
1,2-Di(3-methoxycarbony1-2-
thioureido)benzene
S-(2,3,3-Trichloroallyl)di=
i sopropylthi ocarbamate
S-Propyl-N,N-dipropylthiocarbamate
10
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This interference was especially troublesome when retention times of the
derivatives were short (less than 0.6 relative to aldrin), or when
retention times were near 1.2. The level of interference can be expected
to increase when samples from environmental media are used instead of
analytical standards. Hence, the value of this method is limited unless
a suitable cleanup procedure can fie found. Another limiting factor was
that unless the carbamate can form a substituted phenoxide ion in the
alkaline reaction mixture, the structure of the derivative may be difficult
to determine. However, this appears to be a fairly sensitive method for
the determination of carbamates which can form a substituted phenoxide
ion in the reaction mixture.
During the course of this project, it was found that the sensitivity
of the carbamate derivatives fell into two categories. One group had
minimum detectable levels of approximately 200 pg, while the other group
generally had minimum dectable levels of greater than 5 ng. This suggested
that there were multiple routes of derivatization.
Mass' Spectrometric Identification
Carbaryl, meobal, promecarb, thiophanate-methyl, CDEC, aminocarb,
and barban derivatives were analyzed by gas chromatography-mass spectrom-
etry. The mass spectra of these derivatives along with the spectra of
the reagent blank products are located in the appendix.
In many of the recorded mass spectra (exceptions--CDEC, aldicarb
and two minor peaks which appear in the spectra of carbaryl and aminocarb),
two ions were found; m/z 207 and m/z 179. The pentafluorobenzyl (PFB)
ion at m/z 181, found by Coburn et aj_. to be the significant fragment
in the mass spectrum of the normal unsubstituted PFB derivative of mobam
11
-------
(4-Benzothienyl-N-methylcarbamate) and which would be expected in all
unsubstituted derivatives, was not generally found. The exceptions were
the presence of this ion in the mass spectra of the minor (ca 10% based
on peak heights) gas chromatographic peaks in the chromatograms of
carbaryl and aminocarb and the main peak of the aldicarb derivative.
The m/z 207 fragment, assigned as an ethoxytetrafluorobenzyl ion,
was designated as originating in the mass spectral fragmentation reactions
of an ethoxide displacement product of PFB, with one of the fluorines
being displaced. A logical ethylene loss of 28 mass units from the m/z
207 fragment yielded the intense m/z 179 fragment, and in certain cases,
a further loss of CHO yielded a m/z 150 fragment, and a further fluorine
loss yielded a m/z 131 fragment. These fragments were initially recognized
in the gas chromatographic-mass spectrometric analysis of a reagent
blank. See Table 2 for the structures of the compounds formed in the
reagent blank mixture.
Considering the alkalinity of the reaction mixture and the electro-
negativity of the fluorines, the likely mechanism for the ethoxide
displacement of the fluorine is aromatic nucleophillic substitution.
This mechanism involves attack by the nucleophile CpHrO , upon the PFB
ring to form a carbanionic intermediate, and subsequent expulsion of the
corresponding fluoride ion from the carbarn'on to yield the final product.
The outline for this mechanism is found in Figure 1.
Of the carbamates analyzed, four (carbaryl, promecarb, aminocarb,
and meobal) are capable of forming the substituted phenoxide ions in the
alkaline reaction mixture. The mass spectra of the resulting products
are consistent with the expected ether derivative.
12
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Table 2. PFBB Reaction Products and Major MS Fragments
Mass
Structure
Mass
Structure
179
207
OC2H5
224
226
OC2H5
Product ill
252
C2H5
Product II
H5C20
278
OC2H5
Product IV
(The exact position of the OC2H5 group on the ring is not known. The
ethoxy groups are placed arbitrarily.)
13
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0-Ar
F OC2H5
Ar=Aromatic ring system
of carbamate pesticide
The position of the ethoxy group
on the ring is not known
OC2H5
Figure 1. General mechanism of fluorine
displacement by ethoxide ion.
14
-------
The derivative resulting from the reaction of thiophanate-methyl,
although the most sensitive of the carbamate derivatives analyzed, did
not follow this route of derivatization. The derivative, of mass 414,
was determined to be a di-ethoxytetrafluorobenzyl sulfide (see Figure
2). It should be noted that thiophanate-methyl cannot form a phenoxide
ion, and hence does not form a derivative consistent with Figure 3. The
structure of what we call the thiophanate-methyl derivative was confirmed
by independent synthesis through reaction of sodium sulfide and PFBB in
alcoholic KOH. The gas chromatographic retention times, and mass spectrum
of the synthesized compound were identical to that of the thiophanate-
methyl derivative. Thiophanate-methyl may be degraded to yield the
sulfide ions for the reaction mixture, or the sulfide may have come from
an impurity in our thiophanate-methyl standard..
The spectra of aminocarb and carbaryl proved to be particularly
interesting. Two derivatives were found; the minor (approximately 10%
by relative peak height) derivative formed contained the m/z 181 penta-
fluorobenzyl fragment, while the major (90%) derivative formed contained
the m/z 207 fragment from the ethoxy substituted PFBB. This could mean
that the replacement of a fluorine by the ethoxy group takes place after
formation of the ether linkage between the substituted phenoxide ion and
pentafluorobenzyl group. The general scheme of the derivatization route
of substituted phenoxide ion forming carbamates is located in Figure 3.
The derivatization of aldicarb proved to be another exception of
the scheme outlined in Figure 3. Although it is impossible for aldicarb
15
-------
F F
F F
C2H50
CH2-S-CH2
2H5
F F
F F
Figure 2. Thiophanate-Methyl Derivative.
Di-ethoxytetrafluorobenzyl sulfide
16
-------
The position of the ethoxy group
on the ring is not known
Figure 3. General derivatization route of
substituted phenoxide forming carbamates.
17
-------
to form a substituted phenoxide ion, aldicarb cleaved at the C-0 ester
linkage and formed the normal PFB type derivative (unsubstituted by an
ethoxide ion). The structure of the aldicarb PFB derivative is given in
Figure 4.
Certain carbamates wnich had the ability to form substituted phenoxide
ions did not form derivatives which were very sensitive to gas chromatog-
raphy (i.e. karbutilate, desmedipham). Possible reasons for this were a
very slow rate of formation or rapid destruction of substituted phenoxide
ions, attack of substituent groups on the phenolic ring by PFBB, resulting
in derivatives with prohibitively long retention times, or competing
reactions of the carbamate with ethoxide ions.
The mass spectra of barban derivative seems to support some of
these hypotheses. Several compounds were created in the derivatization
reaction. Of these, two were found to be ethoxy replacement products of
barban and one was found to be the m/z 207 ethoxy PFB addition derivative
of 3-chloroaniline (which was formed during hydrolysis).
The structure of the CDEC derivatives proved to be the most difficult
to determine. Three peaks were found in the total ion chromatogram, the
largest of which was determined to be underivatized CDEC. Structures
(see Appendix) have been proposed which seem to fit the mass spectra of
the remaining two peaks.
18
-------
CH3
I
CH,S — C — C = I
3 I I
CH3 H
F F
— O — CH2
F F
Figure 4. Aldicarb derivative.
19
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SECTION V
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34. Holden, E. R., Jones, W. M., and Beroza, M., J. Agr. Food Chem.,
17, 56, 1969.
35. Cohen, I. C., and Wheals, B. B., J. Chromatog., 43, 233, 1969.
36. Moffat, A. C., and Hornig, E. C., Anal. Letters, 3, 205, 1970.
37. Hartvig, P., and Vessman, J., Anal. Letters, 7, 223, 1974.
38. Agemian, H., and Chau, A.S.Y., Analyst, 101, 733, 1976.
39. Thompson, J. F., Analysis of Pesticide Residues in Human and
Environmental Samples, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1977.
40. Coburn, J. A. and Chau, A.S.Y., Environm. Letters, 10, 225, 1975.
22
-------
APPENDIX
For each carbamate pesticide, the following information is given:
1. Gas chromatographic retention time (aldrin = 1)
2. Derivatization Linearity
3. Linearity of electron capture detector response
4. Minimum Detectable Level
5. Quantity of derivative required to give 50% full scale deflection
6. Storage of derivatized samples
7. Mass spectra and comments as applicable
Page
Aldicarb 25
Aminocarb 29
Barban 34
Benthicarb 40
Carbaryl 43
Carbofuran 48
CDEC 50
Chloropropham 56
Desmedipham 59
Formetanate Hydrochloride 62
Karbutilate 65
Meobal 68
Methiocarb 72
23
-------
Page
Methomyl 75
Phenmedipham 78
Promecarb 81
Propoxur 85
Thiophanate-methyl 88
Reagent blank (mass spectra) 92
24
-------
ALDICARB
DERIVATIZATION LINEARITY
Linear from 1 to 100 (jg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-21Q SE-3Q/OV-210
0.080 ng 0.040 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
0.080 ng 0.070 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
0.56 0.60
COMMENTS
Must be diluted 100 fold due to background interference
DECAY
Stable under test conditions
25
-------
12.0
10.0
E
u
I-'
I
1 6.0
UJ
Q.
2.0
0 .010
.070
.030 .050
AMOUNT INJECTED, ng
Column Linearity Check of Aldicarb Derivative on OV-17/OV-210.
26
-------
14,0
12.0
10.0
E
o
h-"
I
LU
CL
8.0
6.0
4.0
2.0
0
0 .010 .030 .050 .070
AMOUNT INJECTED, ng
Column Linearity Check of Aldicarb Derivative on SE-30/OV-210.
27
-------
MO CO E
X I X (o
o—o—o J=
I <-
CO
CO
u
I I
o
o
CM
8
CM
8
«M
_co o _co
i- §
E- 8
-tO
T
— 0 "
X
o
o
= o
— oo
Mill! 1 ! 1
o
3
-
CO
_N
O
CD
U
U
03
0>
C
'«>
3
8
0)
o
CD
u.
a.
<
»*—
O
= o
CO
o
o
o
o
oo
o
CM
O
00
o
CM
28
-------
AMINOCARB
DERIVATIZATION LINEARITY
Linear from 1 to 100 jjg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
1.6 ng 0.49 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
2.7 ng 2.6 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
2.0 1.9
COMMENTS
The standard is very light sensitive. Must handle with care.
DECAY
Stable under test conditions.
29
-------
01234
AMOUNT INJECTED, ng
Column Linearity Check of Aminocarb Derivative on OV—17/OV—210.
30
-------
01 234
AMOUNT INJECTED, ng
Column Linearity Check of Aminocarb Derivative on SE— 30/OV—210.
31
-------
en
8
CM
= o
O
CM
CM
=- §
^ CM
O
00
O
(O
— o
= o
• CM
— O
— o
o
co
o
3
= o
= o
— n
= o
o
o
o
00
o
(O
o
CM
§
O
CO
§
o
CM
32
-------
00
O
(O
CM
— o
= o
o
CM
CM
- o
- CM
O
oo
o
00
CO
o
tO
CO
I
o
O
CM
— O
— O
O
o
o
oo
o
(O
O
CM
= o
- oo
o
= o
L a
- co
0>
•ft
CO
CO
LL.
0.
n
m
O
E
a
CO
= o
- CM
s
O
00
8
o o o
* CM
33
-------
BARBAN
DERIVATIZATION LINEARITY
Linear from 100 to 1000 \iq
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
20 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
34 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
2.0
COMMENTS
None.
DECAY
Stable under test conditions.
SE-30/OV-210
33 ng
SE-30/OV-210
100 ng
SE-30/OV-210
3.0
34
-------
0 33 67 100 133 167 200 233 267 300
AMOUNT INJECTED, ng
Column Linearity Check of Barban Derivative on OV—17/OV—210.
35
-------
0 33 67 100 133 167 200 233 267 300
AMOUNT INJECTED, ng
Column Linearity Check of Barban Derivative on SE—30/OV—210.
36
-------
N
1
CO
o
to
CM
O
•*
CSI
t= p
O
CM
O
CM
CM
O
O
CM
O
o
= o
O
IO
o
(O
CO
o
^~
CO
CB
CO
<5
Q
CQ
u.
o.
c
^
CO
CQ
*-
O
CO
a.
05
_ o
o
CM
CO
_ o
• o
o
oo
CM
o
o
o
oo
o
CM
:z_ O
oo
o
o
o
o
00
o
(O
o
CM
3AI1VT3U
37
-------
I
o
CM
I
O
CO
\
o
CO
CM
§
CM
O
00
E- §
= : I
o
o
o
o
o
CO
o
CM
= O
• co
o
"it
o
CM
= CO
o>
CO
o oQ
O
c
re
-B
CO
CD
— CO
= o
— o
~
§
o
00
o
-------
=•-- 8
CO
I
(J
CM
I
o
o
I
I I I I I I I I I I
o
00 _
0>
'•p
CD
O I
52 CQ
u.
Q.
Ji §
5
CO
I
CO
QQ
E
4-"
p
-------
BENTHIOCARB
DERIVATIZATION LINEARITY
Linear from 10 to 1000 ug
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
0.65 ng 0.48 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
1.8 ng 2.0 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
0.91 1.00
COMMENTS
Must be diluted 100 fold due to background interference.
DECAY
Stable under test conditions.
40
-------
14
13
12
11
10
9
o 8
I
LU
Q.
6
5
4
3
2
1
0
0.25 0.5 0.75 1.0 1.25 1.5 1.75 2.0
AMOUNT INJECTED, ng
Column Linearity Check of Benthiocarb Derivative on OV—17/OV—210.
41
-------
16
15
14
13
12
11
10
9
O 8
ui
X
6
5
4
3
2
1
0
0.25 0.5 0.75 1.0 1.25
AMOUNT INJECTED, ng
1.5
1.75
2.0
Column Linearity Check of Benthiocarb Derivative on SE—30/OV—210.
42
-------
CARBARYL
DERIVATIZATION LINEARITY
Linear from 1 to 1000 (jg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-21Q SE-30/OV-210
0.20 ng 0.18 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-21Q
1.0 ng 0.89 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
4.7 3.6
COMMENTS
None.
DECAY
Stable under test conditions.
43
-------
0.2
0.6
0.3 0.4 0.5
AMOUNT INJECTED, ng
Column Linearity Check of Carbaryl Derivative on OV-17/OV-210.
0.7
0.8
44
-------
10
u
LLJ
0.1 0.2
0.6 0.7 0.8
0.3 0.4 0.5
AMOUNT INJECTED, ng
Column Linearity Check of Carbaryl Derivative on SE—30/OV—210.
45
-------
f= o
L_ • co
= CM
O
3
- o
o
o
i- §
o
o
M
O
to
— o
O
(M
O
O
o
oo
— o
— o
= o
ra
"C
-------
(O
in
o
(O
CM
= o
o
•*
CM
o
CM
CM
o
o
CM
o
CM
i- o
o
00
o
tO
z o
+^
LL
I
I
O
CM
=- §
o
8
o
to
CO
o
^~
CO
o
CM
CO
o
s
O
00
CM
0)
CO
OQ
u.
a.
CO
&
CO
O
"5
E
a
CO
a
o
o
o
CO
o
to
o
CM
o
00
o
o
o
(O
o
CM
aoisivaiMnav
47
-------
CARBOFURAN
DERIVATIZATION LINEARITY
Linear from 2 to 1000 ug
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
0.70 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
3.1 ng
RELATIVE RETENTION TIME (ALDRIN = l.QO)
OV-17/OV-210
2.1
COMMENTS
SE-30/OV-210
See comments
SE-30/OV-210
SE-30/OV-210
Must be diluted 100 fold due to background interference. Characteri-
zation was not attempted on the SE-30/OV-210 column due to high
background interference.
DECAY
Stable under test conditions.
48
-------
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
AMOUNT INJECTED, ng
Column Linearity Check of Carbofuran Derivative on OV—17/OV—210.
49
-------
CDEC
DERIVATIZATION LINEARITY
Linear from 0.1 to 1000 |jg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
0.024 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
0.15 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
0.64
COMMENTS
SE-30/OV-210
0.024 ng
SE-30/OV-210
0.15 ng
SE-30/OV-210
0.62
The derivative was difficult to quantitate due to the variability of
length of derivatization time. This made decay studies impossible and
the error was greatly increased in the other studies.
DECAY
Not applicable.
50
-------
0.025
0.05
0.15
0.075 0.1 0.125
AMOUNT INJECTED, ng
Column Linearity Check of CDEC Derivative on OV-17/OV-210.
0.175
0.2
51
-------
0.025
0.05
0.075 0.1 0.125
AMOUNT INJECTED, ng
0.15
0.175
Column Linearity Check of CDEC Derivative on SE—30/OV—210.
52
-------
u
o
I I I I I I I I I I
o
tO
CM
O
CM
CM
EL §
- CM
O
00
o
-------
O
(O
CM
CM
O
5t
CM
00=
- CM
in
CM
U
/V _
§
CM
in
CM
U
U
U
O
00
c
I
(5
E- s
O
LU
Q
O
CO
is
a
CO
E- S
O
O
O
O
O
00
O
(O
O
CM
oo
3DNvai\inav
54
-------
CN
I o .
O — O I
\/\
\
co= O
I I
AI
in in ^
o
CO
CN
= o
§
CM
o
oo
_N
E
«
§
o
i
^
*•>
c
CO
c
CO
ID
OJ
O
LU
O
*S
— o
i-8
o
o
o o o o o o
O 00
-------
CHLOROPROPHAM
DERIVATIZATION LINEARITY
Linear from 10 to 1000 |jg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
0.72 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
3.1 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
0.39*, 2.9
COMMENTS
SE-30/OV-210
0.72 ng
SE-30/OV-210
3.0 ng
SE-30/OV-210
0.40*, 3.0
Must be diluted 100 fold due to background interference.
DECAY
Stable under test conditions.
*Major peak
56
-------
17
16
15
14
13
12
11
£ 10
u
LU
I
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
AMOUNT INJECTED, ng
Column Linearity Check of Chlorpropham Derivative on OV—17/OV—210.
57
-------
12
11
10
u
2
Hi
X
< 6
LLJ
O_
1 T
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
AMOUNT INJECTED, ng
Column Linearity Check of Chlorpropham Derivative on SE—30/OV—210.
58
-------
DESMEDIPHAM
DERIVATIZATION LINEARITY
Linear from 100 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
6. 3 ng 8.4 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
32 ng 42 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
2.8 1.8
COMMENTS
None
DECAY
Stable under test conditions.
59
-------
12
11
10
9
CM
§ 7
in
LU
Q.
4
3
2
1
0
5.6 11.1 16.7 22.2 27.8 33.3 38.9 44.4
AMOUNT INJECTED, ng
Column Linearity Check of Desmedipham Derivative on OV—17/OV—210.
60
-------
15
14
13
12
11
10
I 9
I 8
LLJ
X
HI
Q.
7
6
5
4
3
2
1
0
5.6 11.1 16.7 22.2 27.8 33.3 38.9 44.4
AMOUNT INJECTED, ng
Column Linearity Check of Desmedipham Derivative on SE—30/OV—210.
61
-------
FORMETANATE, HCL
DERIVATIZATION LINEARITY
Linear from 100 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-21Q
4.7 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
23 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
1.7
COMMENTS
None
DECAY
Stable under test conditions.
SE-3Q/OV-210
4.1 ng
$E-30/OV-210
20 ng
SE-30/OV-210
2.2
62
-------
24
28
12 16 20
AMOUNT INJECTED, ng
Column Linearity Check of Formetanate-HCI Derivative on OV—17/OV—210.
32
63
-------
2.5 5.0 7.5 10.0 12.5 15.0 17.5
AMOUNT INJECTED, ng
Column Linearity Check of Formetanate-HCI Derivative on SE-30/OV-210.
20.0
64
-------
KARBUTILATE
DERIVATIZATION LINEARITY
Linear from 100 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
9.7 ng 9.9 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
49 ng ,i 49 ng
RELATIVE RETENTION TIME (ALDRIN = l.OQ)
OV-17/OV-210 SE-30/OV-210
2.5 2.1
COMMENTS
None
DECAY
Stable under test conditions.
65
-------
10
20
70
30 40 50 60
AMOUNT INJECTED, ng
Column Linearity Check of Karbutilate Derivative on OV-17/OV-210.
80
66
-------
24
22
20
18
16
i 14
H
I
2 12
LLJ
LU
Q.
6
4
2
0
10 20 30 40 50 60 70
AMOUNT INJECTED, ng
Column Linearity Check of Karbutilate Derivative on SE-30/OV-210.
80
67
-------
MEOBAL
DERIVATIZATION LINEARITY
Linear from 10 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-21Q SE-30/OV-210
0.091 ng 0.096 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
0.46 ng 0.48 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
1.2 1.0, 1.2*
COMMENTS
Confirmation of derivatization linearity below 10 |jg was impossible
because of background interference.
DECAY
Stable under test conditions.
*Major peak
68
-------
0.07 0.13 0.20 0.27 0.33 0.40 0.47
AMOUNT INJECTED, ng
Column Linearity Check of Meobal Derivative on OV-17/OV-210.
0.53
69
-------
u
I
UJ
I
<
a.
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0.07 0.13 0.20 0.27 0.33 0.40 0.47
AMOUNT INJECTED, ng
Column Linearity Check of Meobal Derivative on SE—30/OV—210.
0.53
70
-------
71
-------
METHIOCARB
DERIVATIZATION LINEARITY
Linear from 1 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
0.35 ng »' 0.30 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
1.8 ng 1.5 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
3.7 3.1
COMMENTS
None.
«
DECAY
Stable unaer test conditions.
72
-------
10
LU
CC.
LLJ
a. 4
0 0.25 0.50 0.75 1.0 1.25 1.50 1.75
AMOUNT INJECTED, ng
Column Linearity Check of Methiocarb Derivative on OV-17/OV-210.
2.0
73
-------
0.25 0.50
0.75 1.0 1.25
AMOUNT INJECTED, ng
1.50 1.75
Column Linearity Check of Methiocarb Derivative on SE—30/OV— 210.
74
-------
METHOMYL
DERIVATIZATION LINEARITY
Linear from 1 to 100 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
0.031 ng 0.026 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/QV-210 SE-30/OV-210
0.16 ng 0.13 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
0.37, 0.71, 1.3* 0.25, 0.40, 1.5*
COMMENTS
Measurements were made on the third peak.
DECAY
Stable under test conditions.
*Major peak
75
-------
0.025 0.05 0.075 0.1 0.125 0.15 0.175 0.2
AMOUNT INJECTED, ng
Column Linearity Check of Methomyl Derivative on OV—17/OV—210.
76
-------
0.025
0.15 0.175
0.05 0.075 0.1 0.125
AMOUNT INJECTED, ng
Column Linearity Check of Methomyl Derivative on SE—30/OV—210.
0.2
77
-------
PHENMEDIPHAM
DERIVATIZATION LINEARITY
Linear from 100 to 1000 ug
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210 SE-30/OV-210
18 ng 14 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210 SE-30/OV-210
88 ng 68 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
1.8,2.3*, 2.8 1.5, 1.6*, 1.8
COMMENTS
Measurements were made of the second peak.
DECAY
Stable under test conditions.
*Major peak
78
-------
u
SE
o
LLJ
UJ
Q-
12
11
10
9
s
7
6
5
4
3
2
1
0
10 20 30 40 50 60 70 80
AMOUNT INJECTED, ng
Column Linearity Check of Phenmedipham Derivative on OV—17/OV—210.
79
-------
10 20 30 40 50 60 70 80
AMOUNT INJECTED, ng
Column Linearity Check of Phenmedipham Derivative on SE—30/OV—210.
80
-------
PROMECARB
DERIVATIZATION LINEARITY
Linear from 10 to 1000 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
0.14 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-210
0.68 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
1.4
COMMENTS
SE-30/OV-210
0.14 ng
SE-30/OV-210
0.70 ng
SE-30/OV-210
1.4
Confirmation of derivatization linearity below 10 ug was impossible
because of background interference.
DECAY
Stable under test conditions.
81
-------
16
15
14
13
12
11
10
•
8
7
6
5
4
3
2
1
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
AMOUNT INJECTED, ng
Column Linearity Check of Promecarb Derivative on OV—17/OV—210.
82
-------
15
14
13
12
11
10
E 9
u
LJJ
I
01
Q.
8
7
6
5
4
3
2
1
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
AMOUNT INJECTED,ng
Column Linearity Check of Promecarb Derivative on SE—30/OV—210.
83
-------
£
o>
I
o
in
co
co
© 6-0
o
CD
CM
O
«•
CM
O
a
O
O
CM
O
oo
o
tD
N
"E
to
u
- o
o
CM
- o
• o
= o
• co
P o
eg
5-8
= o
— o
o
s
(U
•4=
(0
Q)
Q
CO
u.
a.
a.
"5
E
Q.
(O
= co
t O
o
o
o
CO
o
CM
O
O
o
CO
s °
3AI1VT3U
84
-------
PROPOXUR
DERIVATIZATION LINEARITY
Linear from 10 to 1000 |jg
AMOUNT NEEDED TO PRODUCE 10% FSD
QV-17/OV-210 SE-3Q/QV-210
0.080 ng 0.081 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-21Q SE-30/OV-210
0.24 ng 0.24 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210 SE-30/OV-210
1.2 1.2
COMMENTS
Must be diluted 100 fold due to background interference.
DECAY
Stable under test conditions.
85
-------
0 .04 .08 .12 .16 .20 .24 .28 .32 .36
AMOUNT INJECTED, ng
Column Linearity Check of Propoxur Derivative on OV—17/OV—210.
86
-------
LLJ
Q.
16
15
14
13
12
11
10
7
6
5
4
3
2
1
0
I
I
I
I
I
0 .04 .08 .12 .16 .20 .24 .28 .32 .36
AMOUNT INJECTED, ng
Column Linearity Check of Propoxur Derivative on SE—30/OV—210.
87
-------
THIOPHANATE METHYL
DERIVATIZATION LINEARITY
Linear from 10 to 100 pg
AMOUNT NEEDED TO PRODUCE 10% FSD
OV-17/OV-210
0.0087 ng
AMOUNT NEEDED TO PRODUCE 50% FSD
OV-17/OV-21Q
0.044 ng
RELATIVE RETENTION TIME (ALDRIN = 1.00)
OV-17/OV-210
3.0
COMMENTS
SE-30/OV-210
0.012 ng
SE-30/OV-210
0.057 ng
SE-30/OV-210
3.3
Confirmation of derivatization linearity below 10 ug was impossible
because of blank peak interference.
DECAY
Stable under test conditions.
88
-------
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20
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< 10
HI
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8
6
4
2
0
0.01
0.02
0.06
0.07
0.03 0.04 0.05
AMOUNT INJECTED, ng
Column Linearity Check of Thiophanate Methyl Derivative on OV—17/OV—210.
0.08
89
-------
12
11
10
9
8
£ 7
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LU R
OC 6
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UJ
Q.
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3
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
AMOUNT INJECTED, ng
Column Linearity Check of Thiophanate Methyl Derivative on SE—30/OV—210.
90
-------
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/4-79-077
. TITLE AND SUBTITLE
2.
3. RECIPIENT'S ACCESSIOP+NO
A One Step Method for the Determination of Carbamate
Pesticides by Derivatization with a-Bromo-2,3,4,5,6-
Pentafluorotoluene
5. REPORT DATE
September 1979
6. PERFORMING ORGANIZATION CODE
AUTHOFUS)
Merrill D. Jackson, Stephen D. Soileau, G. Wayne
Sovocool and Richard A. Sachleben
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Analytical Chemistry Branch
Environmental Toxicology Division
Health Effects Research Laboratory
Research Triangle Park. NC 27711
10. PROGRAM ELEMENT NO.
1EA615
11. CONTRACT/GRANT NO.
N/A
12 SPONSORING AGENCY NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
RTP, NC
Final
14. SPONSORING AGENCY CODE
EPA 6007*11
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A procedure was developed for the determination . \ce q'
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