MEASUREMENT OF HYDROLYSIS .RATE CONSTANTS
FOR EVALUATION OF HAZARDOUS WASTE LAND DISPOSAL
Volume I
by
J. Jackson Ellington, Frank E. Stand 1, Jr., and William D. Payne*
Measurements Branch
Environmental Research Laboratory
Athens, GA 30613
*Technology Applications, Inc.
Environmental Research Laboratory
Athens, GA 30613
ENVIRONMENTAL RESEARCH LABORATORY
-OFFICE OF RESEARCH AND DEVELOPMENT
-U.S. ENVIRONMENTAL PROTECTION AGENCY
ATHENS, GEORGIA 30613
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DISCLAIMER
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency. It has been subject to
the Agency's peer and administrative review, and it has been approved for
publication as an EPA document. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use by the U.S. Environ-
mental Protection Agency.
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FOREWORD
As environmental controls become more expensive and penalties for judg-
ment errors become more severe, environmental management requires more precise
assessment tools based on greater knowledge of relevant phenomena. As a part
of this Laboratory's research on occurrence, movement, transformation, impact,
and control of chemical contaminants, the Measurements Branch determines the
occurrence of unsuspected organic pollutants in the aquatic environment and
develops and applies techniques to measure physical, chemical, and microbial
transformation and equilibrium constants for use in assessment models and for
development of property reactivity correlations.
In implementing the land banning provision of the 1984 Hazardous and
Solid Waste Amendments to PL 98-616 (RCRA), a mathematical model was developed
to estimate potential groundwater contamination from chemicals in land disposal
sites. Application of the model requires as input the hydrolysis rate constant(s)
for the chemical of concern. This report documents the laboratory measurement
of hydrolysis rate constants for 26 compounds regulated under RCRA. Approximately
three thousand chemical analyses were required on 29 different organic compounds
(including standard reference compounds) to perform the rate constant measure-
ments. Experimental conditions were selected and carefully controlled to
provide sufficiently precise rate constants to meet the requirements resulting
from model sensitivity tests.
Rosemarie C. Russo, Ph.D.
Di rector
Environmental Research Laboratory
Athens, Georgia
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ABSTRACT
To provide input data for a mathematical model to estimate potential
groundwater contamination from chemicals in land disposal sites, hydrolysis
rate constants were determined for 26 regulated chemicals under carefully
controlled conditions. Hydrolysis rates were measured under sterile conditions
at precisely controlled temperatures and at three pH levels (3,7, and 11).
Conditions were adjusted to provide sufficiently precise rate constants to meet
modeling requirements determined through model sensitivity tests. In addition
to close monitoring of temperature and pH, precautions were taken to minimize
impact of adventitious processes. Chemical concentrations as a function of
incubation time were measured by gas chromatography, liquid chromatography, or
ion exchange chromatography. Identities and purities of the chemicals were
determined by mass spectrometry supplemented, in some cases, by infrared spec-
trometry-
Hydrolysis rates for three standard reference compounds (chlorostilbenene
oxide for acid, 2,4-D methyl ester for base, and benzyl chloride for neutral
conditions) were measured repetitively to assess the effect of undetected
changes in experimental conditions. Pseudo-first order rate constants determined
for benzyl chloride at 28.0°C over 8 months had a coefficient of variation
(C.V.) of 9.0%. Values determined at higher temperatures (36.4, 45.0, and
52.9°C) and extrapolated back to 28.0°C had a C.V. of 18.0%. Second-order rate
constants for the 2,4-D methyl ester and for 4-chlorostilbenene oxide determined
under similar conditions (28.0°C, 8 mo.) had C.V.'s of 14.7% and 14.0%, respec-
tively.
Hydrolysis rate constants were determined experimentally for the following
26 compounds: warfarin, aldrin, brucine, dieldrin, disulfoton, endosulfan I,
endosulfan II, fluoroacetic acid sodium salt, 2-methyllactonitrile, famphur,
acrylamide, acrylonitril e, cis-l,4-dichloro-2-butene, trans-1,4-dichloro-2-
butene, 4,4-methylene-tv[s-(2-chloroaniline), pentachloronitrobenzene, pronamide,
reserpine, thiourea, uracil mustard, ethyl carbamate, 2,3-dichloropropanol, 1,3-
dichloropropanol, 1,2,3-trichloropropane, 1,2,3-trichlorobenzene, and 1,2,4-
trichlorobenzene. Rate data was reported for: nitrobenzene, mitomycin C,
chloromethyl methyl ether, 1,2-dibromo^-chloropropane, and ethylene dibromide.
All compounds except thiourea were hydrolyzed to some extent under the
varying conditions of pH and temperature employed. Hydrolysis rate constants
reported at 25°C ranged from approximately 1 hr"1 to 1 x 10~7 hr~i. Half-lives
correspondingly ranged from a few minutes to centuries.
This report covers a period from October 1985 to July 1986, and work was
completed as of July 1986.
IV
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CONTENTS
Foreword i i i
Abstract 1v
List of Tables and Illustrations vii
Acknowledgments viii
1. Introduction 1
1.1 Purpose 1
1.2 Background 1
1.3 References for Section 1 4
2. Hydrolysis Kinetics 6
2.1 Hydrolysis Mechanism 6
2.2 Rate Laws 6
2.3 Contributing Factors to Hydrolysis Rates 7
2.3.1 Temperature 7
2.3.2 pH, Buffer Catalysis 7
2.3.3 Ionic Strength 7
2.3.4 Sterility 8
2.3.5 Sorption 8
2.4 References for Section 2 8
3. Laboratory Determinations 9
3.1 Standard Reference Compounds (SRC) 9
3.1.1 Acid SRC . 9
3.1.2 Neutral SRC . 9
3.1.3 Base SRC 9
3.2 Rate Studies-OSW Chemicals 9
4. Experimental 14
4.1 Chemicals and Solvents 14
4.1.1 Source 14
4.1.2 Identity and Purity 14
4.1.3 Solvents 14
4.2 pH Measurements 14
4.3 Buffers 14
4.4 Temperature Control 15
4.5 Sterile Water 15
4.6 Methods of Analysis 15
5. Data Analysis and Presentation 16
5.1 Data Compilation Methods 16
5.2 Standard Reference Compound Data 16
5.3 Summary Sheets for OSW Chemicals 16
5.3.1 Warfarin 23
5.3.2 Aldrin 25
5.3.3 Brucine 27
5.3.4 Dieldrin -. . . . 29
5.3.5 Disulfoton 32
5.3.6 Endosulfan I 34
5.3.7 Endosulfan II 37
5.3.8 Fluoroacetic Acid, Sodium salt 39
5.3.9 2-Methyllactonitrile -...". 40
5.3.10 Nitroglycerine 41
5.3.11 Famphur ...-,.._ 42
-------
5.3.12 Acryl amide 44
5.3.13 Acrylonitrile 45
5.3.14 Mitomycin C 47
5.3.15 Chloromethyl methyl ether ... 50
5.3.16 l,2-Dibromo-3-Chloropropane 51
5.3.17 Ethylene dibromide 52
5.3.18 £21-l,4-Dichloro-2-butene 54
5.3.19 trans-1,4-Dichloro-2-butene 57
5.3.20 4,4-Methylene-bis-(2-chloroaniline) 60
5.3.21 Pentachloronitrobenzene 63
5.3.22 Pronamide 65
5.3.23 Reserpine 67
5.3.24 Thiourea 69
5.3.25 Uracil Mustard 70
5.3.26 Ethyl carbamate 72
5.3.27 l,3-Dich1oro-2-propanol 74
5.3.23 2,3-Dichloro-l-propanol 75
5.3.29 1,2,3-Trichloropropane 77
5.3.30 1,2,3-Trichlorobenzene 79
5.3.31 1,2,4-Trichlorobenzene 82
Appendix A 85
Appendix B 118
VI
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LISTS OF TABLES AND ILLUSTRATIONS
Tables Page
1. Chemicals from OSW "First Third" List 3
2. Hydrolysis Data for DL-trans-4-Chlorostllbene Oxide 10
3. Hydrolysis Data for Benzyl Chloride 11
4. Hydrolysis Data for Methyl-2,4-Dichlorophenoxy Acetate .... 12
5. Hydrolysis Rate Constants and Half-Lives at 25°C 17
Illustrations
1. Hydrolysis of DL-trans-4-Chlorosti1bene Oxide at 28°C,
pH 3.13 19
2. Hydrolysis of Benzyl Chloride at 52.9°C, pH 7 20
3. Hydrolysis of Methyl-2,4-Dichlorophenoxy Acetate at 28°C,
pH 9.06 21
4. Dependence of Benzyl Chloride Hydrolysis on Temperature .... 22
VII
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ACKNOWLEDGMENTS
This work was conducted at the Athens Environmental Research Laboratory
through the combined efforts of EPA, Technology Applications, Inc. (TAI), and
University of Georgia (UGA) personnel. The technical assistance of Ms. Cheryl
Trusty (UGA) and Miss Sarah Patman (UGA) is gratefully acknowledged. Mr- Alfred
Thruston, Dr. John McGuire, and Dr. Timothy Collette generated the chemical
spectral data (Appendices A and B) needed to verify identity and estimate
purity. The assistance of Mr. Heinz Kollig in literature searches for hydrolysis
data and methods of analysis was very helpful in the initial stages of the
project. The assistance of Dr. Lee Wolfe and Mr. Lee Mulkey throughout the
project and including review of this report is gratefully acknowledged. Discus-
sions with Mr. William Donaldson were always fruitful and are so acknowledged.
Mrs. Elaine McGarity's effort in typing the draft and subsequent revisions was
exempl ary.
vm
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SECTION 1
INTRODUCTION
1.1 Purpose
In implementing the 1984 Hazardous and Solid Waste Amendments to the
Resource Conservation and Recovery Act (RCRA), EPA's Office of Solid Waste
(OSW) will apply a decision rule based on a mathematical model to chemicals
under consideration that considers horizontal underground movement of a
chemical based on advection, dispersion, sorption, and chemical hydrolysis.
Application of the model requires as input the second-order or first-order
hydrolysis rate constants for chemicals containing hydrolyzable functional
groups. A total of 362 compounds, divided into three groups, are to be
regulated initially. This report provides first- and second-order hydrolysis
rate constants for those organic compounds in the first group for which
satisfactory values were not developed in an earlier evaluation process and
describes the laboratory experiments conducted to measure hydrolysis rate
constants (1).
1.2 Background
The Hazardous and Solid Waste Amendments of 1984 to PL 98-616 (RCRA)
stipulate that land disposal of "hazardous wastes" is prohibited unless the EPA
Administrator determines that prohibition of some wastes is not required to
protect human health and the environment because those particular wastes are
not likely to reach unacceptable levels in groundwater as a result of land
disposal. The amendments define hazardous waste as any of 362 specific compounds
(either part of or inclusive of Appendix VIII compounds). In compiling this
list, major considerations were toxicity of the material and quantity of waste
material generated annually.
To provide a practical tool for determining which listed hazardous
materials may be disposed of by land disposal and under what conditions, the
use of a relatively simple model was suggested that would estimate potential
groundwater contamination for each listed chemical. The model considers hori-
zontal movement based on advection, dispersion, sorption, and transformation."
Hydrolysis is the only transformation process specifically considered. Although
other transformation processes, such as microbial degradation and chemical
reduction, may take place, they are not presently included in the model. The
model assumes no unsaturated zone for groundwater and assumes saturated ground-
water "zones" ranging from 3 meters to 560 meters in depth. The mean depth of
those considered is 78.6 meters. Organic carbon contents used in the model
will range from 1% to 0.1%. The point at which the groundwater must meet
standards may vary but was orignally set at 150 meters horizontally from the
point of introduction.
For each chemical considered, the maximum allowable concentration for the
receiving groundwater, 150 meters "downstream," is entered into the model,
which assumes environmental characteristics for selected subterranian systems.
The concentration of leachate leaving the disposal site is computed for various
conditions of rainfall, soil type, pH, etc. A computed leachate concentration
that would cause unacceptable groundwater cond4tions is selected by OSW as the
-------
maximum allowable concentration 1n leachates. A chemical may be disposed of by
land only If treatment brings the leachate concentration down to the level
selected that would not cause groundwater to exceed the acceptable concentration.
The modeling approach applies to landfills, surface impoundments, waste piles,
and land treatment operations. Land treatment operations may be addressed in a
different manner to allow for reduction in concentrations resulting from the
land treatment process.
It is necessary to acquire octanol/water partition coefficients and
hydrolysis rate constants for each of the 362 chemicals except for solvents
("fast track" in the list), which will be treated as non-degrading, non-sorbing
constituents and chemicals already banned by the State of California (listed as
"California"). These two groups comprise 21 and 44 chemicals, respectively.
The remainder of the 362 chemicals were separated into 3 groups by OSW: 81 in
the "first third," 121 in the "second third," and 95 in the "third third."
Rate constant and partition coefficient data are required for these three groups
by 7/86, 5/87, and 4/88, respectively. Partition coefficient data are reported
in a companion document and have corresponding delivery dates.
Hydrolysis of the organic compounds on the OSW list of chemicals was
addressed by a working group of four experts assembled at the Environmental
Research Laboratory, Athens, GA, on April 25 and 26, 1985. The experts were
chosen for their extensive theoretical and experimental knowledge and experience
in the area of chemical reactivity of organic compounds in water. The work
group consisted of Dr. N. Lee Wolfe, U.S. Environmental Protection Agency,
Athens, GA; Dr. Robert Taft, University of California, Irvine, CA; Dr. Clifford
Bunton, University of California, Santa Barbara, CA; and Dr. William Mabey,
Kennedy/Jencks Engineers, San Francisco, CA.
The panel addressed only the organic compounds on the list of 362 chemicals
provided by OSW. The inorganics included on the list were not addressed. The
inorganics will be examined by another group and reported under a separate
task. For the organometallie compounds on the list, the panel did not attempt
to estimate data, but did provide experimental rate data where available.
The evaluative procedure the panel followed was to divide the compounds
into three categories: those that had no hydrolyzable functional groups, those
that would hydrolyze with half-lives greater than a year, and those that woul'd
hydrolyze with half-lives of less than a year. Hydrolysis rate data were provided
for some of the chemicals on the list. The present report was concerned with
developing hydrolysis rate data for the remainder.
Of the 81 compounds in the "first third," 54 are either inorganic, contain
no hydrolyzable functional group, contain a hydrolyzable functional group that
was judged by experts to be non-labile, or have acceptable literature values
for hydrolysis reported by Wolfe (1). The determination of acceptable first-
or second-order hydrolysis rate constants for the remaining 27 compounds is
described in the text of this report.
Table 1 lists the chemical name and Chemical Abstract Number (CAS) as
supplied by OSW in the same order as in the OSW listing. The CAS number was
used as the definitive chemical descriptor when there was any ambiguity in
relating the name of the chemical to the structure of the compound. The expert
-panel did not have time to conduct an extensive search of the literature because
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TABLE 1. CHEMICALS FROM OSW "FIRST THIRD" LIST
CAS Number
Chemical
81-81-2
309-00-2
357-57-3
60-57-1
298-04-4
115-29-7
62-74-8
75-86-5
55-63-0
52-85-7
79-06-1
107-13-1
50-07-7
107-30-2
106-93-4
764-41-0
101-14-4
82-68-8
92-12-8
23950-58-5
50-55-5
62-56-6
66-75-1
51-79-6
616-23-9
96-18-4
12002-48-1
Warfarin
Aldrin
Brucine
Dieldrin
Disulfoton
Endosulfan3
Fluoroacetic Acid, Sodium Salt
2-Methyl1 actonitri1e
Nitroglycerine
Famphur
Ac rylamide
Acrylonitrile
Mitomycin C
Chloromethyl Methyl Ether
Ethylene Dibromide
1,4-Di chloro-2-Buteneb
4,4-Methylene-bis-(2-Ch1 oroani line)
Pentachloroni trobenzene
1,2-Di bromo-3-chl oropropane
Pronamide
Reserpine
Thiourea
Uracil Mustard
Ethyl Carbamate
2,3-Dichloro-l-propanol and Dichloropropanols0 N.O.S.
1,2,3-Trichloropropane
Trichlorobenzene^
a Rate determined for Endosulfan I and Endosulfan II
b Rate determined for cis and trans isomers
c Rate determined for l,3-Dichloro-2-propanol
d Rate determined for 1,2,3-Trichlorobenzene and 1,2,4-Trichlorobenzene
-------
of the number of compounds and short time period. Before beginning laboratory
measurements, we,. therefore, conducted a three-pronged search of the literature.
The literature was searched for methods of chemical analysis, laboratory generated
hydrolysis values, as well as protocols to follow in laboratory generation of
hydrolysis data. The literature searches were conducted either manually or
electronically through use of DIALOG, a database management system that yield
access to over 200 databases. Acceptable hydrolysis data was found for nitro-
glycerine (2), chloromethyl methyl ether (3), ethylene dibromide (4), 1,2-di-
bromo-3-chloropropane (5), and mitomycin C (6). Data are summarized in the
data sheets (Section 5.3).
Suggested screening protocols and detailed test protocols for hydrolysis
of chemicals in water were reported by Mabey et
-------
3. Van Duurerv, B. L., C. Katz, B. M. Goldschmidt, K. Frenkel, and A.
Sivak. 1972. Carcinogenicity of Halo-Ethers. II. Structure-Activity
Relationships of Analogs of Bte(Chloromethyl)ether. J. Natl. Cancer Inst. 48,
(5) 1431-1439.
4. Personal Communication. Stuart Z. Cohen, Office of Pesticides
Programs EPA and G. A. Jungclaus, Midwest Research Institute.
5. Burlinson, N. E., L. A. Lee, and D. H. Rosenblatt. 1982. Kinetics
and Products of Hydrolysis of l,2-Dibromo-3-chloropropane. Environ. Sci.
Technol. 16., 627-632.
6. McClelland, R. A. and K. Lam. 1985. Kinetics and Mechanism of the
Acid Hydrolysis of Mitomycins. J. Am. Chem. Soc. 107. 5182-5186.
7. Mill, T., W. R. Mabey, D. C. Bomberger, T. W. Chou, D. G. Hendry,
and J. H. Smith. 1982. Laboratory Protocols for Evaluating the Fate of Organic
Chemicals in Air and Water. U.S. Environmental Protection Agency, Athens, GA.
EPA/600/3-82/022.
8. Suffet, I. H., C. W. Carter, and G. T. Coyle. 1981. Test Protocols
for the Environmental Fate and Movement of Toxicants: Proceedings of a Symposium
of the Association of Official Analytical Chemists (AOAC), October 21, 1980,
Washington, DC, Edited by G. Zweig and M. Beroza, Published January 1981 by the
AOAC.
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SECTION 2
HYDROLYSIS KINETICS
2.1 Hydrolysis Mechanism
Hydrolysis of organic compounds refers to reaction of the compound with
water in which bonds are broken and new bonds with HO- and H- are formed. A
common example is the reaction of an alkyl halide with the loss of halide ion
(-X):
RX + HOH - > ROH + HX (or H+, X~)
The rate of the reaction may be promoted by the hydronium ion (H+, or H^O"1")
or the hydro xyl ion (OH~). The former is referred to as specific acid catalyis
and the latter as specific base catalysis. These two processes together with
the neutral water reaction were the only mechanisms considered in this study.
This allowed direct measurement of the:H30+ or OH" concentration through accurate
determination of solution pH.
Some chemicals show a pH dependent elimination reaction:
H X
! ! H+ or
- C - C -- > C = C + HX
OH-
In this study only the disappearance of substrate was monitored with no attempts
to identify mechanisms.
2.2 Rate Laws
If all processes referred to in Section 2.1 are included where the rate of
hydrolysis is given by the equation,
d[C]
-- = kn[C] = kA[H+][C] + kB[OH-][C] + kN'[H20][C] (2,1)
U I*
where [C] is the concentration of reactant and kn is the pseudo-first-order rate
constant at a specific pH and temperature, kA and kB are second-order rate
constants and kN' the pseudo-first-order rate constant for the acid base and
neutral promoted processes, respectively. The water concentration is essen-
tially not depleted by the reaction and much greater than [C], thus kwTHoOl is
a constant (k^). n *• J
Equation 2.1 assumes each individual rate process is first order in
substrate, thus kn can be defined as:
kn = kA[H+] + kB[OH-] + k
N
-------
Using the autoprotolysis equilibrium expression
!(„ = [H+][OH~] (2.3)
equation 2.2 may be rewritten as
kBKw
kh = kA[H+] + - + kN (2.4)
n A -- IN
Equation 2.4 shows the dependence of k^ on [H+] and on the relative values of k^,
kg, and k^.
As a good approximation, the second-order rate constants for acid hydrolysis
and for base hydrolysis can be calculated by dividing the pseudo-first order
rate constant obtained at the appropriate pH by the hydronium ion or hydroxyl
ion concentration, respectively. The half-life of a chemical at a given pH and
temperature can be calculated from equation 2.5, where k^ is the observed rate.
(2.5)
Data evaluation methods and calculations are discussed in more detail in Section
5.1.
Excellent discussions of the hydrolysis rate laws are provided by Mabey and Mill
(1,2).
2.3 Contributing Factors to Hydrolysis Rates
2.3.1 Temperature
Water and oil baths that precisely held temperature were used when
experimentally determining rates of hydrolysis (Section 4.4). This removed the
contribution of temperature as a variable during the actual experiments.
2.3.2 pH, Buffer Catalysis
NBS calibrations standards were used to calibrate the pH meter
before measurements. The pH was usually measured at the temperature of analysis.
In regions where only k^ contributes to hydrolysis, Kn will decrease by a factor
of 10 for each unit increase in pH. Similarly where only kg contributes to
hydrolysis, K^ will increase by a factor of 10 for each unit increase in pH.
kfl is for the pH-independent hydrolysis rate measurement. Buffers (0.005 MJ
were used to control pH and avoid buffer catalysis (3).
2.3.3 Ionic Strength
Ionic strength, depending on the chemical,-can lead either to
acceleration or retardation. For this reason concentrations of buffer solutions
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were set as low as possible yet high enough to maintain constant pH over the
course of the hydrolysis determination. The compound concentration was corres-
pondingly set low, usually 10-4 M or less.
2.3.4 Sterility
Sterile conditions was maintained for all studies to prevent
microbial degradation of the chemical (Section 4.5).
2.3.5 Sorption
Chemicals analyzed by gas chromatography were extracted from the
aqueous layer and glass surfaces with iso-octane. Samples analyzed by liquid
chromatography were checked for sorption by emptying the sample container,
rinsing the container with acetonitrile, and analyzing the acetonitrile in the
same manner as the sample.
2.4 References for Section 2
1. Mabey, W. and T. Mill. 1978. Critical Review of Hydrolysis of
Organic Compounds in Water Under Environmental Conditions. J. Phys. Chem. Ref.
Data. 7(2): 383-415.
2. Mill, T., W. R. Mabey, D. C. Bomberger, T. W. Chow, D. G. Hendry,
and J. H. Smith. 1982. Laboratory Protocols for Evaluating the Fate of Organic
Chemicals in Air and Water. U.S. Environmental Protection Agency, Athens, GA.
EPA/600/3-82/022.
3. Perdue, E. M. and N. L. Wolfe. 1983. Prediction of Buffer Catalysis
in Field and Laboratory Studies of Pollutant Hydrolysis Reactions. Environ.
Sci. Technol. 17, 635-642.
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SECTION 3
LABORATORY DETERMINATIONS
3.1 Standard Reference Compounds
Three compounds were chosen as candidate standard reference compounds,
one each for acid, base, and neutral hydrolysis. The SRC hydrolysis rate
constants were determined before analysis of samples and interspersed with
laboratory determination of hydrolysis rates of the compounds in Table 1.
Because values and experimental conditions for SRC's were being developed
concurrently with measurement of the regulated compounds, the interspersion of
SRC's was not as uniform as will be the case in future use of SRC's. Pertinent
information as to concentration, pH, temperature, and instrument for analysis
is tabulated in Tables 2 through 4. The rate values for all three SRCs are in
good agreement with literature or calculated values.
3.1.1 Acid SRC
DL-trans-4-Chlorosti1bene oxide was selected as a SRC for acid
hydrolysis studies. Operating conditions and calculated rates are in Table 2.
The chlorine was essential for analysis by the electron capture detector.
3.1.2 Neutral SRC
Benzyl chloride was selected as a SRC for neutral hydrolysis
conditions, since the rate is known to be independent of pH below 13. Also,
the degradation rate at room temperature is fast enough to allow easy sampling.
Table 3 tabulates analytical parameters. Of particular interest is the last
column of KI values extrapolated from three elevated temperatures.
3.1.3 Base SRC
Methyl-2,4-dichlorophenoxy acetate (2,4-D methyl ester) served as
the base SRC candidate. Table 4 contains rate values and corresponding
analytical parameters. Data are reported as calculated from analytical runs.
3.2 Rate Studies-OSW Chemicals
Literature values were found for five of the chemicals in Table 1, reducing
the number requiring measurement to 22. The CAS No. for four of these compounds,
however, was either for a mixture of isomers or nonspecific isomers. Therefore,
Endosulfan I and II: cis- and trans-l,4-dich1oro-2-butene; l,3-dichloro-2-
propanol; 2,3-dichloro-l-propanol; 1,2,3-trichlorobenzene; and 1,2,4-trichloro-
benzene were merged into the list to yield the final 31 chemicals reported on
in the data sheets (includes five from literature).
A general description of laboratory operations will be given in the
remainder of this section. A tyrical hydrolysis experiment consisted of pre-
paring a spiking solution of the compound of interest, preparing buffer solutions,
transferring spiked buffer to individual "rate point tubes" (15-ml Tef4on
lined, screw cap, or sealed ampules), therr monitoring degradation by sacrificing
individual tubes and determining percentage of the substrate 'remaining.
-------
TABLE 2. HYDROLYSIS DATA FOR DL-TRANS-4-CHLOROSTILBENE OXIDE
Date
11/1/85
11/6/85
11/6/85
11/6/85
11/6/85
11/6/85
11/15/85
11/15/85
11/15/85
11/15/85
11/15/85
3/11/86
3/11/86
3/11/86
3/11/86
5/14/86
a Every
Initial
Cone.
(ppm)
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2
2
2
2
2
PH
3.13
3.10
3.10
3.07
3.07
3.63
3.01
3.01
3.59
3.59
3.01
3.06
3.06
3.06
3.06
2.99
listing in column
b Pseudo-first-order
c Second
rate
Temp,
°C
28
28
28
28
28
38
28
28
38
38
28
28
28
28
28
23
must be
constant
order constant calculated
d Extrapolation to 28
e Standard deviation
°C, based on
of the slope
Method of
. , Analysis
LC
LC
LC
LC
GC
GC
LC
LC
LC
LC
GC
LC
GC
LC
GC
LC
multiplied by 10"3
from the slope of
103a
(mi
17.4
14.4
14.9
14.3
14.6
16.9
20.8
23.7
23.5
24.5
21.1
16.9
14.3
16.9
14.3
13.8
n
+
±
±
±
±
+
+
±
+
+
+
±
+
+
+
±
Klb
K2C
~1) (M~l min
0.
0.
0.
0.
1.
0.
1.
2.
1.
1.
0.
1.
0.
1.
1.
1.
3e
2
6
8
1
6
7
2
0
9
9
0
6
3
0
5
23.
18.
18.
16.
17.
72.
21.
24.
91.
95.
21.
19.
16.
19.
16.
12.
5
2
8
7
1
3
3
2
4
3
6
4
4
4
5
5
K2
-1) Extrapolatedd
22
28
29
22
to retrieve K
the
1
from pseudo-first-order
a 10-fold change i
n rate
ine
In %
Remaini
rate constant
for 20°
C change
ng
i
vs. Time
n temperature
-------
TABLE 3. HYDROLYSIS DATA FOR BENZYL CHLORIDE
Date
Initial
Cone.
pH
Temp . ,
°C
Method of
Analysis
I03a Kl (min-1)
Extrapolated0
11/26/85
11/26/85
11/26/85
11/26/85
11/27/85
11/27/85
11/27/85
11/27/85
11/29/85
11/29/85
12/2/85
12/2/85
5/21/86
5/21/86
7/2/86
7/3/86
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.31
1.0
1.0
1.0
1.3
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
53
53
53
53
28
28
28
28
45
45
36
36
53
53
54
54
LC
LC
LC
LC
LC
LC
LC
LC
GC
LC
GC
LC
GC
GC
GC
GC
20.3 ± 0.9d
19.1 ± 1.8
21.1 ± 0.9
21.6 ± 0.7
1.0 ± 0.0
1.2 ± 0.0
1.1 ± 0.0
1.0 ± 0.0
7.2 ± 0.2
7.2 ± 0.0
3.1 ± 0.2
3.4 ± 0.1
14.0 ± 0.1
13.6 ± 0.3
15.4 ± 0.1
16.0 ± 0.1
1.15
1.08
1.20
1.22
1.03
1.02
1.21
1.28
.75
.73
.82
.85
a Every listing in column must be multiplied by 10~3 to retrieve K
b Pseudo-first-order rate constants from the slope of the line Ln % Remaining
vs. Time
c Extrapolation to 28°C based on a 10-fold change in rate for each 20°C change
in temperature
d Standard deviation of the slope
11
-------
TABLE 4. HYDROLYSIS DATA FOR METHYL-2.4-DICHLOROPHENOXY ACETATE
ro
Initial
Date Cone. pH
(ppm)
10/7/85 5
10/7/85 5
10/8/85 5
10/8/85 5
10/9/85 5
10/9/85 5
10/11/85 5
10/11/85 5
10/11/85 5
10/11/85 5
3/6/86 5
3/6/86 5
3/6/86 5
3/6/86 5
5/12/86 5
5/13/86 5
5/12/86 5
5/13/86 5
7/2/86 5.4
7/3/86 5.4
a Every listing
9.06
9.06
9.65
9.65
7.11
7.11
9.14
9.14
8.00
8.00
8.87
8.87
9.10
9.10
9.38
9.38
9.45
9.45
8.75
8.72
Method of
Temp., Analysis
°C
28
28
28
28
70
70
28
28
48
48
25
25
25
25
25
25
25
25
31
31
in column must be multi
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
GC
LC
LC
pled by 10~3
b Pseudo-first-order rate constants from the slope
c, Second order
constant
d Extrapolation to 28°C
e Standard deviation of
calculated from
based on 10-fol
the slope
103a Klb
(min-1)
8.1 ± 0.3e
7.0 ± 0.4
26.2 ± 0.6
27.7 ± 1.2
11.4 ± 0.5
10.0 ± 0.3
12.0 ± 0.5
10.3 ± 0.1
10.3 ± 0.4
8.4 ± 0.2
5.7 ± 0.2
4.9 ± 0.2
9.0 ± 0.2
8.0 ± 0.4
23.0 ± 1.0
22.4 ± 0.9
24.9 ±1.4
22.4 ± 0.8
9.1 ± 0.4
7.9 ± 0.2
to retrieve K
of the line In %
pseudo-first-order constant
d change in
rate for each 20°
fi
K2C K2 (M-l, min-1)
(M-1, min-1) (Extrapolated**)
703
613
586
621
88300
77400
855
744
10300
8600
770
564
755
627
959
934
883
794
1600
1500
Remaining
C change i
678
594
974
811
1100
796
1100
886
1400
1300
1200
1100
1100
1000
vs. Time
n temperature •
C^tc'^^^r
-J£
//7 =-
-------
Spiking solutions were prepared by dissolving the substrate in acetonitrile,
methanol, or water. The concentration was such that 0.1 ml diluted to 100 ml
with buffer gave a substrate concentration that was Ixl0~5f4 or was 50% of the
water solubility or less.
Initial hydrolysis runs were performed at pH 3, 7, and 11. Buffers were
prepared at these pHs then measured at the temperature of the hydrolysis run.
Each run consisted of five or six tubes. Immediate analysis of one tube estab-
lished the 100% response peak (T0). Analysis of a second tube within 3 to 6
hours gave a good estimate of sampling frequency for the remaining tubes.
The initial hydrolysis runs were used to set pH and temperature condi-
tions for subsequent rate determinations. The rate determinations were normally
performed in triplicate; however, some compounds required more replicates
(aldrin, dieldrin) and some less (2-methyllactonitrile).
13
-------
SECTION 4
EXPERIMENTAL
4.1 Chemicals and Solvents
4.1.1 Source
The EPA repositories at Research Triangle Park, NC, and Las Vegas,
NV, were the first choice for chemicals on which hydrolysis rates were measured.
Commercial chemical companies were the second sources. The supplier of each
chemical is listed on the data sheets in the Section 5.3.
4.1.2 Identity and Purity
Stated purities are listed on the data sheets. The chemicals were
analyzed by mass spectrometry for confirmation of the stated identity. The
generated mass spectral data are in Appendix A. GC/FTIR was used to characterize
the 1,2,3- and 1,2,4-isomers of trichlorobenzene.
4.1.3 Solvents
Solvents were "distilled in glass," Burdick and Jackson solvents
either gas chromatograph or HPLC grade, as required by the method of analysis.
4.2 pH Measurement
An Orion Research EA920 pH meter equipped with an Orion Research A810300
Ross combination electrode was used for all pH measurements. National Bureau
of Standards (NBS) reference standards were used to calibrate and check the pH
meter. The pH meter had a stated accuracy of +0.02 units. The temperature
compensation prode was used for all measurements. The pH was measured at the
temperature of the hydrolysis rate measurement and adjusted with base or acid
to obtain the desired pH.
4.3 Buffers
Buffer stock solutions were prepared at 0.1 M_ using sterile water as
described above. To prepare pH 3 buffer, 0.1 M potassium hydrogen phthalate
was diluted to 0.005 M_ and final pH adjustment made with 0.1 fl HC1. The pH 7
buffer was prepared from 0.1 M potassium dihydrogen phosphate~diluted to 0.005 M
with final pH adjustment using 0.1 N NaOH. Buffers for pHs 9 and 11 were made
by diluting 0.1 M_ sodium phosphate heptahydrate to 0.005 M with final pH adjust-
ment using 0.1 M NaOH. ~
Buffer stability was tested initially at 0.001 M. Thus, pH 5 and oH 7
buffers held their respective pH's for the test periocf. The pH 9 buffer (0.001 M)
decreased to pH 8.07 after 24 hours and to pH 7.50 after 96 hours. Buffer at a ~
concentration of 0.005 M_ remained constant at 9.10 +_ 0.03 pH units for 25 days
Containers for the experiment were screw cap test tubes using autoclaved (CO?
free) water was used. v *•
14
-------
4.4 Temperature Control
Forma Scientific refrigerated and heated baths (Model 2095) were used for
temperatures in the range of 2 to 70°C (±0.02°C). A Lauda C-20 oil bath with a
stated control accuracy of ±0.01°C and a fine control range of ±0.2°C was used
for temperatures above 68°C. Temperatures were measured with American Society
for Testing and Materials (ASTM) thermometers, are calibrated by NBS procedures
and NBS certified masters. The thermometers were calibrated in 0.1°C increments.
4.5 Sterile Water
Water used in the experiments was unchlorinated ground water that was
first processed through a high capacity reverse osmosis unit and a deionizer
unit. This "house" deionized water was further purified by passage through a
Barnstead Nanopure II deionizer, 4-Module unit with Pretreatment, High Capacity,
and Z-Ultrapure cartridges. Water obtained from this unit had a resistance of
greater than 16 meg ohms. This double deionized water was autoclaved for 30
min/liter and allowed to cool before use. The sterile water was stored in a
sterile-cotton-plugged container until;used. All hydrolysis runs were conducted
in screw cap tubes. Data from smear plate counts on agar indicated growth as
being less than 1 colony per milliliter through 9 days at 25°C and pH of 5, 7,
and 9. Sterility checks on the water were performed intermittently.
Buffer solutions were checked for bacterial growth. Buffer solutions,
prepared as described above, were transferred at room temperature to screw cap
test tubes. One-half were flame transferred, the other half without flaming.
A sample (1 ml) from each tube was plated daily, for nine concurrent days on
TGE agar. After a 48-hour incubation, no growth was found. This confirmed
sterility. Control checks during hydrolysis runs showed no growth.
4.6 Methods of Analysis
Details of the methods of chemical analysis are listed on the data sheet
for each compound. Generally gas chromatography was the first method of choice
for four reasons:
1) sensitivity and specificity of detectors
2) solvent extraction stopped hydrolysis and allowed multiple
injections over extended periods of time
3) solvent extraction also lessened problems caused by compound
sorption to glass
4) direct aqueous injection of water soluble compounds that were
not amenable to other methods of analysis
High performance liquid chroTnatography (HPLC) was used extensively-, ion
chromatography and the diode array UV-detector were used in the analysis of
sodium fluoroacetate and thiourea, respectively. Hydrogen cyanide released by
the decomposition of 2-methyllactonitrile was monitored by EPA Method 335.
Linearity of detector .response in the concentration range of analysis for
each chemical was established to ensure reliable concentration versus time plots.
15
-------
SECTION 5
DATA ANALYSIS AND PRESENTATION
5.1 Data Compilation Methods
Raw data consisted of time of sampling and percentage substrate remaining.
The measured concentration at time zero was considered 100% and was the reference
point for the remaining points. The data were processed on a Lotus 1-2-3/IBM
PC-XT using a data entry/linear regression program. The raw and calculated
data were entered in a notebook. Graphs were made by using personal computers
to plot In (% remaining) vs. time and to calculate statistical values.
Values obtained from the linear regression program include the slope
(pseudo-first-order rate constant), Y-intercept. variance, SD of Y-intercept,
SD of slope, and the correlation coefficient (r2).
5.2 Standard Reference Compound Data
All the laboratory data on the SRCs are summarized in Tables 2, 3, and 4.
Figures 1, 2, and 3 are representative graphical presentations of hydrolysis
data for each compound. Figure 4 is an Arrhenius plot for hydrolysis of
benzyl chloride at four temperatures. An energy of activation of 22.4 ± 2.3
Kcal/mole for benzyl chloride was calculated from the data associated with Figure
4. An error of 10% in the slope was assumed. The change in the hydrolysis rate
constants for benzyl chloride and the methyl ester of 2,4-D after March 1986
illustrates how susceptible rate determinations are to slight changes in the
controlled parameters. No plausible explanation has been found for either the
increased 2,4-D rate or the decreased benzyl chloride rate.
5.3 Summary Sheets for OSW Chemicals
A summary sheet was prepared for each chemical. The summary sheet contains
information pertinent to the analysis of each chemical, and includes source,
purity, and analytical method. Also included on the sheet is information on
pH, temperature, pseudo-first-order and second-order rate constants, half-lives,
and correlation coefficients (r2). Sample identity was confirmed by mass
spectrometry and infrared spectrometry as reported in the Appendices. Where a
literature reference for the hydrolysis of a compound was obtained, the summary
sheet contains the second-order rate constant if applicable and first-order
rate constants at 25°C. For several of the compounds, lab data were generated
in this study to fill in gaps in the literature.
Data from all the summary sheets were used to derive the rate values in
Table 5. These values are the calculated rate constants at 25°C. The rate
constants were assumed to vary a factor of 10 for each 20°C change in tempera-
ture (Ref. 1, Section 1). This corresponds to an activation energy of about 20
kcal/mole. When statistical tests of the data indicated the hydrolysis was
independent of pH, hydrolysis values from the extremes of pH (acid and/or base)
were used to calculate the neutral hydrolysis rates reported in Table 5.
Confidence limits were-calculated from the mean and standard deviation values
and are the values reported in Table 5.
16
-------
TABLE 5. HYDROLYSIS RATE CONSTANTS AND HALF-LIVES AT 25°C
Warfarin1
Aldrin
Brucine
Dieldrin
Disulfoton
Endosulfan I
Endosulfan II
Thiodan
Fluoroacetic Acid
Sodium Salt
2 -Met hyll act on it rile
Nitroglycerine3
Famphur
Ac ryl amide
Acrylonitrile
Mitomyci'n Ca
Chloromethyl methyl ether3
1 ,2-Di bromo-3-chl oropropane3
Ethyl ene1 Di bromide3
ci s-1 ,4-Di chl oro-2-butene
trans-l,4-Dichloro-2-butene
4,4-Methylene-bis-(2-chloroaniline)
Pentachloroilitrobenzene
Pronamide
'Reserpine
Thiourea
Uracil Mustard
Ethyl Carbamate
'2,3-Dichloro-l-propanol
l,3-Dichloro-2-propanol
1,2, 3-Trichl oropropane
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
Acid
1.4 x ID'4
5.9 x ID'3
(5. 2±1. 2^x10-3
(7.4±3.9)xlO-3
(6.2±0.6)xlO-3
-J
<3. 6x10^
(4.2±0.3)xlO-2
(2.9±3)xiO-4
4.3 x lO-3
0.82
Rate Constants
Neutral
hr-1
4.9 x 10-6
(3.9±2.4)xlO-5
(7.5±2.0)xlO-7
(2.8±0.4)xlO-4
(3.2±2.0)xlO-3
(3.7±2.0)xlO-3
(3. 3±0. 8)xlO-3
<1. 7x10-6
4.47
(2.5±.9)xlO-4
<(2.1±2.1)xlO-6
3.7xlO'4
21
9.9xlO-6
(9.1±l.l)xlO-3
(9.0±0.5)xlO-3
<9xlO-8
(2.8±0.7)xlO-5
<1. 5x10-5
(4.5±1.8)xlO-5
<5.3xlO-7
0.57±0.08
<2.6xlO-7
(5.3±0.8)xlO-5
(3.1±0.2)xlO-3
(1.8±0.6)xlO-6
/"i c. 1 ^ ^ i n *• B
^l»uJ.l»OjAJLU
f 71 1 1 r\\ i n — 5
[L. J± .3 JAIL) J
Base
0.026
2.2 x lO-2
21.8±11.9
2.6±2.1
3.8±2.5
2.8±0.6
77±11
29.6±0.7
6.5±6.5
45.6±11.4
20.6
1.1
148±114
(2.05±0.2)xl05
2xlO-3
20.6±2.2
854±87
1.5xlO-4
< O- 9 *"
47yr
0.15hr
lOyr
115d
38yr
frggyr"
78hf
2 min
38±4yr
Syr
3.2d
3.2d
>800yr
2. Syr
>700yf^c
1.7yr
>150yr
1.2hr
>300yr
1.4yr
9.3d
4.9yr Z
3^yr-
3 Values were extracted from the references in Section 1, the second-order alkaline hyrolysis rate
constant for Mitomycin C was determined at Athens ERL.
ib Calculated from alkaline second-order rate constant assuming zerio neutral contribution.
-------
Constraints of .time, personnel, bath space, and availability of instruments
of analysis dictated that rate determinations be confined to shorter periods of
time (note the half-lives and temperatures in summary sheets). The ideal rate
determination is monitored through at least three half-lives (<12% remaining);
as seen in the summary sheets, the half-lives covered a wide range of time.
An illustrative plot on semi-log paper of % Remaining vs. Time is included
with applicable data sheets. Included on the sheet is the pseudo-first-order
rate constants, half-life, and r2.
18
-------
O)
c
o
£
0)
T1/2
R2
10
0
= 1.74 x 1CT2 min
= 39.8 min.
= 0.999
~1
50 100 150
Time (min)
200
Figure 1. Hydrolysis of DL-trcms-4-Chlorostilbene
Oxide at 28°C, pH 3.13
19
-------
o>
c
*c
'a
£
Q)
KI
T1/2
R2
10%]
10
0
2.04 x 10~2 min
34 min.
0.994
-1
50 75
Time (min)
100
125
Figure 2. Hydrolysis of Benzyl Chloride at 52.9°C,
pH 7.0
20
-------
0)
c
D
E
CD
KI
T1/2
R2
8.07 x 10'
85 min.
0.994
mn
~1
I
50
100 150
Time (min)
200
Figure 3. Hydrolysis of Methyl-2,4-Dichlorophenoxy
Acetate at 28°C, pM 9.0
21
-------
4.0H
3.OH
1.0
3.0
1000/T (°K)
Figure 4. Dependence of Benzyl Chloride
Hydrolysis on Temperature
22
-------
5.3.1 Warfarin
CAS No. 81-81-2
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: _ . 7
pH Temp, °C lO^K^hr'1) K2(M-1hr'i) t1/2(d) r^
3.17 87.0 6.0 4.8 0.999
3.09 68.0 2.2 12.9 0.961
7.17 87.0 3.2 9.1 0.997
7.11 68.0 0.5 57.4 0.931
10.18 68.0 1.2 23.9 0.889
9.69 87.0 3.1 9.2 0.998
Comment: Warfarin has an ionizable functional group that may affect the neutral
hydrolysis rate constant. The data indicate, however, this effect is quite
small over the pH range studied. Activation energies calculated at the three
pH's and assuming an error of 10% were 12.9 ± 2.5 Kcal/mole for the acid, 22.2
± 1.2 Kcal/mole for the neutral, and 26.7 ± 2.5 Kcal/mole for the base hydrolyses,
respectively.
Water Solubility: 170 mg/L
Source: RTP Repository
Listed Purity: 95%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 3 ppm
Analytical Procedure: Warfarin was analyzed by direct injection of 20 micro-
liters of neutralized buffer solution onto a Resolvex C-18 column
Extraction Solvent: NA
Instrumentation: GC HPLC X 1C Diode Array UV
Detector: UV at 282 nm
Column: Resolvex C18, 10 micron, 25 cm x 4.6 mm
Temperature Program: NA
Mobile Phase: 58% 0.005M Tetrabutyl ammonium phosphate
(Pic-A), 42% acetonitrile
Internal Standard: NA
Ltnear Range of Analysis: 0.32 - 3.2 ppm
23
-------
5.3.1 Warfarin
K! = 6.0 x 10"3 hr"1
T-j/2 = 4-8 days
R2 = 0.999
o>
c
0
£
Q)
101-
10'
0.0
2.0 4.0
Time (days)
l 1
6.0
Figure 5.3.1 Hydrolysis of Warfarin at 87°C, pH 3.17
24
-------
5.3.2 Aldrin
CAS No. 309-00-2
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C lO^d'1) K^M^d'1) t1/2(d)
3.03
3.20
2.83
6.99
7.19
10.70
10.19
10.26
10.49
10.64
68.0
69.0
72.5
68.0
72.5
68.0
69.0
69.0
69.0
72.5
36. Oa
2.7
20.0
24.0
15.0
26.4
4.1
7.3
8.4
10.0
1.9 0.960
25.9 0.995
3.5 0.991
2.9 0.825
4.6 0.632
2.5 0.991
16.8 0.651
9.5 0.973
8.2 0.953
7.0 0.702
a Note units of Kj are d"1
Water Solubility: 0.01 mg/1
Source: EPA
Listed Purity: 99%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 3 ppb
Analytical Procedure: The hydrolysis sample (10 ml) is extracted with 2 ml of
a 31 ppb solution of dieldrin in iso-octane. The extract is injected without"
dilution.
Extraction Solvent: Dieldrin 31 ppb in iso-octane
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: ECD
Column: 30 M DB-5, 1 micron film, 0.32 mm ID
Temperature Program: 200°C Isothermal
Mobile Phase: NA
Internal Standard:~ Dieldrin 31 ppb
Linear Range of Analysis: 0.1 - 10 ppb
25
-------
5.3.2 Aldrln
T1/2
R2
= 8.3 x 10~3 hr"1
= 3.5 days
= 0.991
o>
c
D
£
Q)
a:
101H
0.0
0.5 1.0 1.5
Time (days)
2.0
Figure 5.3.2 Hydrolysis of Aldrin at 72.5°C, pH 2.8
26
-------
5.3.3 Brucine
CAS No. 357-57-3
HYDROLYSIS AND ANALYSIS DATA
U 1 V 1 J -J 1
pH
3.10
10.20
10.20
7.08
7.16
o uu u u •
Temp, °C
68.0
68.0
68.0
68.0
87.0
104K1(hr-1)
6.6
4.9
4.8
<0.5
6.0
K2(M'1hr'1)
0.8
3.1
3.1
t1/2(d)
43.7
59.5
59.5
>570
46.0
r2
.999
.925
.977
—
.959
Comment: The extrapolated half-life is calculated based on the acid and alkaline
contribution. The values at pH 7 and elevated temperatures appear too high for
amide hydrolysis and were not used in the calculations.
Water Solubility: 758 mg/L
Source: Aldrich
Listed Purity: 98%
Identity-Purity by Spectral Analysis: Appendix. A
Analysis Concentration: 8.7 ppm
Analytical Procedure: Aliquots (20 microliters) were injected onto the HPLC and
eluting peaks passed through a UV detector. Quantisation was by peak height.
Extraction Solvent: NA
Instrumentation: GC HPLC X 1C Diode Array UV
Detector: UV at 263 nm
Column: Resolvex CN or Ultrasphere ODS
Temperature Program:
Mobile Phase: 50/50 methanol/0.005M 1 octanesulfonic acid, pH 3
Internal Standard:
Linear Range of Analysis: 1-10 ppm
27
-------
5.3.3 Brucine
K1 = 6.2 x 10~4 hr~1
TI /2 = 46.6 days
R2 = 0.959
io^e
o>
c
"c
*o
£
CtL
ioH
•&
•e-
•e-
•e-
0.0 20.0 40.0 60.0 80.0 100.0
Time (hr)
Figure 5.3.4 Hydrolysis of Brucine at 87°C, pH 7.
28
-------
5.3.4
CAS No.
Dieldrin
60-57-1
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp,
3.13
3.13
3.09
3.18
2.88
69.0
69.0
69.0
69.0
72.5
103K1(d~1)
3.6a
2.3
3.8
4.6
2.8
t1/2(d)
19.5
29.7
18.7
15.1
24.3
0.884
0.762
0.673
0.635
0.669
.01
.22
.22
.10
.18
7.24
68.0
69.0
69.0
69.0
69.0
72.5
1.8
5.9
1.8
4.0
1.6
4.4
38.7
11.6
39.5
17.4
42.7
15.9
0.534
0,963
0.980
0.589
0.952
0.796
10.16
10.45
10.47
10.65
10.16
10.51
69.0
69.0
69.0
69.0
69.0
72.5
Note units of K are d
-1
3.8
2.4
2.9
2.0
2.2
1.3
18,3
29.2
24.0
35.3
30.9
54.2
0.705
0.951
0.605
0.784
0.988
0.969
Water Solubility: 0.1 mg/1
Source: RTP Repository
Listed Purity: 99%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 10 ppb or 50 ppb
Analytical Procedure: The hydrolysis sample (10 ml) is extracted with 2 ml of
iso-octane containing 100 ppb of aldrin. The extract is diluted 1:5 with iso-
octane and analyzed by GC.
Extraction Solvent: Iso-octane 100 ppb aldrin
Instrumentations GC X HPLC 1C
Di ode Array UV
29
-------
5.3.4 Dieldrin (Continued)
Detector: EC
Column: 30 M DB-5 0.25 micron film, 0.32 mm ID
Temperature Program: 200°C Iso
Mobile Phase: N/A
Internal Standard: Aldrin
Linear Range of Analysis:
30
-------
5.3.4 Dieldrin
K! = 2.5 x 10~3 hr~1
^1/2 = 11-6 days
R2 = 0.963
D)
C
0
E
-------
5.3.5 Pi sulfoton
CAS No. 298-04-4
HYDROLYSIS AND ANALYSIS DATA
Hydrolysi s Data:
pH Temp, °C
102K1(hr-1) K2(M-1hr-1) t1/2(d)
3.03
3.08
3.07
6.99
6.97
6.96
11
10.5
10.3
69.0
69.0
69.0
69.0
69.0
69.0
48.0
64.5
64.5
4.8
4.0
4.0
4.8
4.0
4.0
24.0
71.0
45.0
240
2519
2057
0.60
0.72
0.72
0.61
0.71
0.73
0.12
0.04
0.06
0.989
0.998
0.994
0.989
0.919
0.995
0.994
0.978
0.993
Water Solubility:
Source: RTF Repository
Listed Purity: 98.9%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.25 ppm
Analytical Procedure: At the time of analysis 10 ml of the buffered solution
of disulfoton is extracted with 2 ml of iso-octane that contained chloropyrifos
at 1.25 ppm. The iso-octane was diluted 1:5 to yield final concentrations 0.25
ppm disulfoton and 0.42 ppm chloropyrifos.
Extraction Solvent: iso-octane
Instrumentation: GC X HPLC
1C
Diode Array UV
Detector: Nitrogen-phosphorus
Column: 5M, OV-1, 2.65 micron film
Temperature Program: 185°C~tsothermaT
Mobile Phase:
Internal Standard: Chloropyrifos (1.25 ppm in iso-octane)
Linear Range of Analysis:
32
-------
5.3.5 Disulfoton
T1/2
R2
= 0.24 hr~1
= 2.8 hr
= 0.994
o>
jc
*c
*D
E
Q>
10
1 I ' I ' I ' \
0.0 1.0 2.0 3.0 4.0
Time (hr)
Figure 5.3.5 Hydrolysis of Disulfoton at 48°C, pH 11.00
33
-------
5.3.6 Endosulfan I1 -» C/fc
CAS No. 415 29 7-
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: 71 11 ,^
pH Temp, °C lO^K^hr'1) K2(M-1hr-1) t1/2(d)
3.12
3.24
3.23
6.89
7.22
7.23
8.69
8.89
9.05
87.0
87.0
87.0
68.0
69.5
69.5
38.0
38.0
38.0
6,
5
6
300
570
580
360
1200
1300
4.3 .951
5.0 .924
4.2 .801
0.10 .995
0.05 .977
0.05 .978
7.4 0.08 .984
15 0.02 .961
12 0.02 .990
Water Solubility: 0.53 mg./L
Source: RTP Repository
Listed Purity: 100%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 10 ppb
Analytical Procedure: Tubes containing 10 ml Endosulfan I or II, at the desired
buffered pH (3, 7, or 11), were heated at a predetermined temperature. Tubes
were sacrificed and the contents extracted with 1 ml iso-octane that contained
100 ppb Aldrin (internal standard). Dilution with iso-octane gave final
concentrations of 10 ppb each Endosulfan and Aldrin.
Extraction Solvent: Iso-octane
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: EC
Column: DB-5, 15M, 0.25 micron film 0.32 mm ID
1
OSW.CAS No. 115-29-7 refers to Thiodan a mixture of Endostilfarr I and
£ndosulfan II.
34
-------
5.3.6 Endosulfan I1 (Continued)
Temperature Program: 170°C - 220°C at 25°/min
Mobile Phase:
Internal Standard: Aldrin (100 ppb in iso-octane)
Linear Range of Analysis:
35
-------
5.3.6 Endosulfan I
K! = 0.58 hr"1
"l"i/2 = 0.05 days
R2 = 0.978
D)
C
.E
*o
E
a>
a:
101-
10
0.0
a
2.0 4.0
Time (hr)
Figure 5.3.6 Hydrolysis of Endosulfan I
at 69.5°C, pH 7.23
36
-------
5.3.7 Endosulfan II? C/fc W
CAS No. 115 29 7'
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
U 1 W 1 J «9 1
pH
3.03
3.40
3.33
3.32
6.89
7.24
7.23
8.69
8.82
8.81
o u*u u u .
Temp, °C
68.0
87.0
87.0
87.0
68.0
69.5
69.5
38.0
38.0
38.0
103K1(hr-1)
4
7
10
11
400
670
740
680
1480
1110
K2(M~ hr~ ) tj^M)
7.2
4.1
2.9
2.7
0.07
0.04
0.04
14 0.04
22 0.02
15 0.03
r2
0.582
0.579
0.970
0.980
0.997
0.975
0.964
0.993
0.854
0.800
Water Solubility: 0.28 mg/L
Source: RTP Repository
Listed Purity: 100%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 10 ppb
Analytical Procedure: Same as Endosulfan I
Extraction Solvent:
Instrumentation: GC X HPLC 1C
Detector: EC
Column: DB 5, 15M, 0.25 micron film, 0.32 mm ID
Temperature Program:
Mobile Phase:
Internal Standard:
Linear Range of Analysis:
Di ode Array UV
OSW CAS No. 115-29-7 refers to Thiodan a mixture of Endosulfan I and II,
37
-------
5.3.7 Endosulfan II
K1 = 0.68 hr~1
T}/2 = 0.04 days
R2 = 0.993
O)
c
O
£
-------
U 1 \J • J -3 1
PH
3.14
7.25
9.99
o u/u u a .
Temp, °C
87.0
68.7
68.7
104K1(hr~1)
2.4
4.0
0.8
K2(M~1hr"1)
5.3.8 Fluoroacetic Acid. Sodium Salt
CAS No. 62-74-8
HYDROLYSIS AND ANALYSIS DATA
t1/2(d) r2
120 0.425
72 0.915
365 0.395
Comment: The pKa of fluoroacetic acid is 2.66. Thus, the rate constant at pH
3.14 includes hydrolysis contributions of the associated and disassociated
species. Over most environmental conditions hydrolysis occurs in media >pH 4,
thus the neutral and alkaline constants were used to determine tj/2 at PH 7«
Water Solubility: Freely soluble
Source: RTF Repository
Listed Purity: 100%
Identity-Purity by Spectral Analysis:
Analysis Concentration: 4.8 ppm
Analytical Procedure: The analysis consisted of direct injection of 100
micro!iters directly onto the anion exchange column. Quantisation was by peak
height comparison to the initial time zero height.
Extraction Solvent: NA
Instrumentation: GC HPLC 1C X Diode Array UV
Detector: Conductivity
Column: AS-3 Dionex Anion Column
Temperature Program: NA
Mobile Phase: 0.0025 M Sodium Carbonate, 0.003 M Sodium Bicarbonate
Internal Standard: NA
Linear Range of Analysis: 0.2 - 7.7 ppm
39
-------
5.3.9 Z-Methyllactonitrile
CAS No. 75-86-5
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: -
pH Temp, °C K^hr'1) K2(M'1 -1) t1/2(d) r^
7.02 26.0 4.47 6.5xlQ-3 .976
Comment: This is an equilibrium reaction between acetone and hydrogen cyanide
to form a cyanohydrin.
Water Solubility: Disassociates
Source: Aldrich
Listed Purity: 99%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 1.5 ppm
Analytical Procedure: Direct analysis on UV after use of modified EPA
Wastewater Procedure 335 (Barbituric Acid/Pyridine/Chloramine T method)
detects HCN formed by hydrolysis of compound of interest.
Extraction Solvent: NA
Instrumentation: GC HPLC 1C Diode Array UV X
Detector: UV at 578 nm
Column: NA
Temperature Program: NA
Mobile Phase: NA
Internal Standard: NA
Linear Range of Analysis: 0.02 ppm - 10 ppm (as CN~)
40
-------
5.3.10 Nitroglycerine
CAS No. 55-63-0
HYDROLYSIS AND ANALYSIS DATA
a
Literature Data :
Temp, °C
25 2.36
25 1.94
18 0.83
18 0.61
10 0.22
10 0.15
10 0.12
Capellos, C., e^ al_., Int. J. Chem. Kinet. 16, 1027-1051 (1984).
Authors reported activation energy as 27.53 Kcal/mole
Water Solubility: 1800 mg/1
Source:
Listed Purity:
Identity-Purity by Spectral Analysis:
Analysis Concentration:
Analytical Procedure: See Ref. 1 in Section 1.3.
Extraction Solvent:
Instrumentation: GC HPLC 1C Diode Array UV
Detector:
Column:
Temperature Program:
Mobile Phase:
Internal Standard:
Linear Range of Analysis:
41
-------
5.3.11
CAS No.
Famphur
52-85-7
Hydrolysis Data:
pH Temp, °C
HYDROLYSIS AND ANALYSIS DATA
K2(M~1hr-1)
t1/2(d)
3.09
3.09
3.03
6.99
7.01
7.02
11.0
10.78
10.79
68.0
69.0
69.0
68.0
69.0
69.0
48.0
69.0
69.0
1.4
4.7
4.7
4.7
3.0
5.0
42
297
303
425
4929
4914
2.1
0.61
0.62
0.61
0.95
0.57
0.07
0.010
0.009
0.722
0.993
0.985
0.926
0.865
0.928
0.989
0.994
0.999
Water Solubility:
Source: RTP Repository
Listed Purity: 98.1%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.53 ppm
Analytical Procedure: At the time of analysis 10 ml of a buffer solution of
famphur is extracted with 2 ml of iso-octane that contains chloropyrifos IS.
Dilutions before analyses yield a chloropyrifos concentration of 0.42 ppm.
Extraction Solvent: Iso-octane
Instrumentation: GC X HPLC
1C
Diode Array UV
Detector: Nitrogen-phosphorus
Column: OV-1, 5M, 2.65 micron film, 0.53 mm ID
Temperature'Program: 185° Isothermal
Mobile Phase: NA
Internal Standard: Chloropyrifos (0.42 ppm in iso-ectane)
Linear Range of Analysts:
42
-------
5.3.11 Famphur
K! = 3.03 hr~1
T1//2 = 0.01 days
R2 = 0.999
D)
C
o
£
-------
5.3.12 Acrylamide
CAS No. 79-06-1
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis
pH
2.99
2.99
7.04
7.04
7.04
, Data:
Temp, °C
88.0
88.0
88.0
88.0
88.0
104K1(hr-1)
17
<125
.3
26
49
K2(M'1hr'1) *l/2(d) p2
0.9 0.389
<4.6 2.3 0.890
96.3 0.017
11.1 0.470
6.0 0.925
11.54 (See comments)
Comments: Samples at pH 11.54 became cloudy followed by the appearance of
globules. Less than 10% of the acrylamide disappeared during the time of the
hydrolysis experiment, this contributed to the scatter in the data.
Water Solubility: 2050 g/1
Source: Chem. Serv.
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 2 ppm
Analytical Procedure: Direct aqueous injections of on microliter aliquots were
made on column. Ethyl carbamate was added to each tube before analysis.
Extraction Solvent: NA
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: FID
Column: DB Wax+, 30 m, 1 micron film, 0.53 mm ID
Temperature Program: 95°C to 190°C
Mobile Phase: NA
Internal Standard: Ethyl carbamate at 8 ppm
Linear Range of Analysis:
44
-------
5.3.13 Acrylonitrile
CAS No. 107-13-1
HYDROLYSIS AND ANALYSIS DATA
jr \4 i \s i j *j i
pH
2.87
2.87
7.19
7.19
7.19
10. .76
11.10
10.86
Temp, °C
68.0
68.0
68.0
68.0
68.0
68.0
24
2
104K1(hr'1)
64
71
No measurable
4000
9100
8900
K2(M'1hr'1)
disappearance
500
1150
1130
t1/2(d)
4.5
4.1
after two
0.07
0.03
0.03
r2
0.811
0.533
days
0.991
0.964
0.977
Comments: The failure to observe hydrolysis is consistent with the reported
hydrolysis pathways for nitriles, and with J. Going (1978) Environmental
Monitoring Near Industrial Sites: Acrylonitrile, EPA 560/6-79-003 (PB 295-928).
Going reported zero degradation after 23 days at room temperature and pH's 4,
7, and 10.
Water Solubility: 73.5 g/1
Source: Aldrich
Listed Purity: +99%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 5.79 ppm
Analytical Procedure: Keep light from solutions of acrylonitrile to prevent
polymerization. One microliter aliquots of the buffer solution were injected
onto a DB Wax+ capillary column. A one meter section of blank tubing was placed
between the injection port and inlet end on the column to trap the buffer salts.
Extraction Solvent: NA
Instrumentation: GC X
Detector: FID
HPLC
1C
Diode Array UV
Column: DB Wax+, 30M, 1 micron film, 0.53 mm ID
45
-------
5.3.13 Acrylonitrile (Continued)
Temperature Program: 30°C isothermal
Mobile Phase: NA
Internal Standard: Propionitrile at 6 ppm
Linear Range of Analysis:
46
-------
5.3.14
CAS No.
Mitomycln C
50-07-7
Hydrolysi s Data:
pH Temp,
7.54
9.25
9.42
8.64
68.7
69.0
69.0
69.0
a,b
Literature data:
pH Temp, °C
2.1
3.2
3.3
3.6
3.9
4.3
25
25
25
25
25
25
135.0
46.0
19.0
15.6
11.5
3.3
HYDROLYSIS AND ANALYSIS DATA
102K1(hr~1)
1.7
9.6
19.0
3.9
5381
7356
8964
4.86
1.66
0.68
0.56
0.41
0.12
1.7
0.3
0.15
0.74
t1/2(d)
0.006
0.017
0.042
0.052
0.070
0.24
0.999
0.987
0.992
0.984
Extrapolation of the literature data to pH 7 gave a half-life of 18 days at
38°C.
McClelland, R. A. and K. Lam. 1985. Kinetics and Mechanism of the Acid
Hydrolysis of Mitomycin. J. Am. Chem. Soc. 107, 5182-5186.
b
Beijnen, J.H., et_a]_. J. Pharm. Biomed. Anal. _3, 59-69 (1985).
Uater Solubility:
Source: Aldrich
Listed Purity:
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 1 ppm
Analytical Procedure: The Mitomycin C is sold as 2 mg sorbed to 48 mg sodium
chloride. A stock solution was prepared by dissolving total contents of package
in 5 ml of HPLC mobile phase. Dilution of stock solution with buffers gave the
final solutions for hydrolysis determinations.
Extraction Solvent: NA
47
-------
5.3.14 Mitomycln C (Continued)
Instrumentation: GC HPLC X 1C Diode Array UV
Detector: UV at 360 nm
Column: u Bondapak CIS, 4.6 mm x 30 cm
Temperature Program:
Mobile Phase: Methanol/0.05 M KH2P04, pH 7 (35:65)
Internal Standard: None
Linear Range of Analysis: 0.055 - 1.1 ppm
48
-------
5.3.14 Mitomycin C
O)
£
*c
*D
E
0)
o:
K! = 1.7 x 10~2 hr~1
T^ = 40.7 hr
R2 = 0.999
0.0
30.0 60.0 90.0
Time (hr)
120.0
Figure 5.3.14 Hydrolysis of Mitomycin C
at 68.7°C, H 7.54 ~
49
-------
5.3.15 Chloromethyl Methyl Ether
CAS No. 107-30-2
HYDROLYSIS AND ANALYSIS DATA
a
Literature Data : Reference 2 in Section 1.3
kh = 21 hr"1 Tj/2 = 1-99 min
3Van Duuren, B.L., et al_. J. Natl. Cancer Inst. 48(5) 1431-1439 (1972)
Water Solubility:
Source:
Listed Purity:
Identity-Purity by Spectral Analysis:
Analysis Concentration:
Analytical Procedure: See ref. 2 in Section 1.3
Extraction Solvent:
Instrumentation: GC HPLC 1C Diode Array UV
Detector:
Column:
Temperature Program:
Mobile Phase:
Internal Standard:
Linear Range of Analysis:
50
-------
5.3.16 l,2-Dibromo-3-Ch1/oropropane (DBCP)
CAS No. 92-12-8
HYDROLYSIS AND ANALYSIS DATA
a
Literature Data :
Literature Values: The kinetic data for hydrolysis of DBCP suggests a
rate law that is first order in DBCP and first order in hydroxide down to pH 7.
Below pH 7 the rate depends in part on hydrolysis by water. The energy of
activation for the pH 6.8 Arrhenius pltft was 22.34 Kcal/mole.
o
KQH = 20.6 M'V'1 (At 25°C and pH 7 data predict a half-life of 38 ± 4
years)
a
Burlinson, N. E., L. A. Lee, and D. H. Rosenblatt. 1982. Kinetics and Products
of Hydrolysis of l,2-Dibromo-3-Chloropropane. Environ. Sci. Technol. 16, 627-
632.
Water Solubility: 1 g/1
Source:
Listed Purity:
Identity-Purity by Spectral Analysis:
Analysis Concentration:
Analytical Procedure: See ref. 4, Section 1.3
Extraction Solvent:
Instrumentation: GC HPLC 1C Diode Array UV
Detector:
Column:
Temperature Program:
Mobile Phase:
Internal Standard:
Linear Range of Analysis:
51
-------
5.3.17 Ethylene Pibromide
CAS No. 106-93-4
HYDROLYSIS AND ANALYSIS DATA
a
Hydrolysis Data :
pH Temp, °C No. of 104K1(hr-1) t1/2(d) r2
Sample Points
5
5
5
7
7
7
9
9
9
30
45
60
30
45
60
30
45
60
38
69
59
51
66
63
56
66
65
1.6 (17%)
10
32
0.7
5.0
26.9
1.7
10.6
42.2
180
29
9
410
57
11
170
28
6.9
0.475
0.916
0.946
0.460
0.717
0.975
0.582
0.963
0.991
The activation energies determined from the slopes of pH 5, 7, and 9 plots were
19.9, 24.1, and 21.1 Kcal/deg-mole, respectively. At pH 7, the hydrolysis half-
life extrapolated from the data to 20°C is 15 years.
1. % Relative standard deviation
a
Cohen, S. Z. (Office of Pesticides, EPA) and G. A. Jungclaus (Midwest Research
Institue). Hydrolysis of Ethylene dibromide, Manuscript in review.
Water Solubility:
Source:
Listed Purity:
Identity-Purity by Spectral Analysis:
Analysis Concentration:
Analytical Procedure: See ref. 3, Section 1.3.
Extraction Solvent:
Instrumentation: GC HPLC 1C Diode Array UV
52
-------
5.3.17 Ethylene D1bromide (Continued)
Detector:
Column:
Temperature Program:
Mobile Phase:
Internal Standard:
Linear Range of Analysis:
53
-------
5.3.18 cis-l,4-Dich1oro-2-butene
CAS No. Reference 764-41-01
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C
2.98
3.04
3.12
68.0
69.0
69.0
1.09
1.37
1.34
K2(M-
ti/2(hr)
0.64
0.51
0.52
0.994
0.990
0.984
7.04
7.16
7.18
68.0
69.0
69.0
1.07
1.33
1.40
0.65
0.52
0.50
0.998
0.993
0.990
6.99
7.00
57.0
57.0
0.50
0.47
1.38
1.43
0.966
0.997
9.74
9.96
10.62
a Note t
j/2
69.0
69.0
68.0
1S nr-
1.40
1.26
1.46
0.50
0.55
0.47
0.998
0.964
0.999
Water Solubility:
Source: Aldrich
Listed Purity: cis purity = 95%, trans purity = 85%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.27 ppm
Analytical Procedure: Ten (10) ml of hydrolysis solution was extracted with 2
ml of 14.4 ppm 1,2,3-trichloropropane in iso-octane. The extract was diluted
1:50 before analysis.
Extraction Solvent: Iso-octane
Instrumentation: GC X HPLC
1C
Diode Array UV
1 CAS No. for trans isomer is 110-57-6.
54
-------
5.3.18 cis-1,4-Dichloro-2-butene (Continued)
Detector: EC
Column: OV-1, 5 M, 2.65 micron film, 0.53 mm ID
Temperature Program: 45°C isothermal
Mobile Phase: NA
Internal Standard: 1,2,3-Trichloropropane (14.4 ppm in iso-octane)
Linear Range of Analysis:
55
-------
5.3.18 cis-1 .4-Dlchloro-2-butene
D)
C
*C
"a
E
-------
5.3.19 trans-1,4-Dichloro-2-butene
CAS No. Reference 110-57-6
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C K^hr"1) K2(M~1hr~1) t1/2(nr)
2.96
3.02
3.00
7.01
7.03
7.03
10.51
9.90
9.90
68.0
69.0
69.0
68.0
69.0
69.0
68.0
69.0
69.0
1.47
1.28
1.36
1.30
1.42
1.33
1.30
1.49
1.45
0.47 0.996
0.54 0.997
0.51 0.996
0.53 0.970
0.49 0.998
0.52 0.998
0.54 0.999
0.47 0.993
0.48 0.999
a Note tj/2 unit is hr.
Water Solubility:
Source: Aldrich
Listed Purity: 85%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.27 ppm
Analytical Procedure: See 5.3.18
Extraction Solvent: Iso-octane
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: EC
Column: OV-1, 5M, 2.65 micron film, 0.53 mm ID
57
-------
5.3.19 trans-1,4-Dichloro-2-butene (Continued)
Temperature Program: 45°C Isothermal
Mobile Phase:
Internal Standard: 1,2,3-Trichloropropane (14.4 ppm in iso-octane)
Linear Range of Analysis:
58
-------
5.3.19 trons-1,4—Dichloro—2-butene
K1 = 1.45 hr"1
Ti/2 = °-°2 days
R2 = 0.999
D>
£
[c
*O
E
0)
101-
10'
0.0
0.4
I
0.8
Time (hr)
I
1.2
Figure 5.3.19 Hydrolysis of trans-1,4-Dichloro
-2-butene at 69°C, pH 9.90
59
-------
5.3.20 4,4-Methylene-bls-(2-Chloroanl1i ne)
CAS No. 101-14-4
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C lO^hr"1) ^(H^hr'1) t1/2(d) r2
3.00 67.8 8.7 33 0.562
3.10 87.0 5.4 51 0.928
3.10 87.0 3.5 83 0.993
3.10 87.0 2.2 131 0.702
7.62 87.0 <1.1 250 NA
9.78 87.0 <1.1 250 NA
Comment: Protonation of the amine at pH 3 may lead to enhanced hydrolysis of
the chloro groups. The data at pH 7 and 9 are based on three runs at each pH
with very limited reaction.
Water Solubility: 25 mg/1
Source: Pfaltz and Bauer
Listed Purity: 97%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 3.2 ppm
Analytical Procedure: Direct injection of 20 microliters with HPLC and UV or
electrochemiccal detection. Diluted the tube contents 1:10 with mobile phase
at the time of analysis. HPLC separation followed by UV or electrochemical
detection.
Extraction Solvent: NA
Instrumentation: GC HPLC _X_ 1C Diode Array UV
Detector: Kratos 757, 248 nm or BAS Electrochemical 0.9V, 10 nA
Column: Zorbax ODS, 5 micron or Resolvex C18, 10 micron
Temperature Program:
Mobile Phase: 80% acetonltrile/20% water with Zorbax col.
50_% aceton1tr1Te/50% 0.05M KHP04 with Resolvex col.
60
-------
5.3.20 4,4-Methvlene-bis-(2-Chloroani 1 ine) (Continued)
Internal Standard:
Linear Range of Analysis:
61
-------
5.3.20 4,4>-Methylene-bis-(2"Chloroaniling
T1/2
R2
= 5.6 x 10"4 hr~1
= 51 days
= 0.928
D>
C
E
-------
5.3.21 Pentachloronitrobenzene
CAS No. 82-68-8
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
PH
3.10
3.02
3.11
7.01
7.09
7.17
10.50
10.43
10.62
Temp, °C
68.0
69.0
69.0
68.5
•69'.0
69.0
68.0
69.0
69.0
103K1(hr"1)
5.0
3.7
6.3
2.6
2.9
3.9
6.4
3.4
4.2
K2(M-1hr-1) t1/2(d) r2
5.7 0.995
7.8 0.997
4.6 0.918
11 0.947
9.9 0.906
7.5 0.912
4.5 0.996
8.5 0.930
6.9 0.918
Water Solubility: 0.43 mg/L
Source: Aldrich
Listed Purity: 96%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.03 ppm
Analytical Procedure: Same as pronamide.
Extraction Solvent: iso-octane
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: EC
Column: DB-5, 30M, 0.25 micron film, 0.32 mm ID
Temperature Program: 140° isothermal
Mobile Phase:
Internal Standard: Methyl ester^of 2,4-D (52.5 ppb in iso-octane)
Linear Range of Analysis:
63
-------
D>
C
•••>
SI
*o
E
-------
5.3.22 Pronamide
CAS No. 23950-58-5
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C
104K1(hr-1)
1/2
(d)
3.10
7.11
7.06
10.20
68.0
68.0
49.0
68.0
7.9
240.0
0.6
149.1
36.6
>138
>138
1.2
0.930
n/a
n/a
0.987
Comment: Neutral hydrolysis errors ignored in calculating half-life since
contribution from neutral rate was neglible.
Water Solubility: 15 mg/L
Source: RTF Repository
Listed Purity: 98.7%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.1 ppm
Analytical Procedure: At the time for analysis of each tube, the buffered solu-
tion (10 ml) of pronamide (0.1 ppm) was extracted with 1 ml of iso-octane that
contained 2,4-D methyl ester (5.25 ppm). The extract is diluted 1:100 with
iso-octane to yield 10 ppb pronamide and 52.5 ppb 2,4-D methyl ester.
Extraction Solvent: iso-octane
Instrumentation: GC X HPLC
Detector: EC
1C
Diode Array UV
Column: DB-5, 30M, 0.25 micron film, 0.32 mm ID
Temperature Program: 140°C isothermal
Mobile Phase:
Internal Standard: Methyl ester of 2,4-D (52.5 ppb in iso-octane)
Linear Range of Analysis: 1 - 10.1 ppb
65
-------
5.3.22 Pronamide
K! = 7.9 x 10"4 hr"1
^1/2 = 36.6
R2 = 0.930
1 \S U
D>
C
C
1 io1-
-------
5.3.23 Reserpine
CAS No. 50-55-5
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C lO^hr'1) K2(M'1hr~1) t1/2(d)
3.02 70.0 0.93 0.97 31.0 0.623
2.99 70.0 0.70 0.68 41.0 0.566
7.01 68.0 6.8 4.3 0.700
7.06 70.0 8.1 3.6 0.986
7.01 70.0 9.5 3.0 0.941
10.21 68.0 181 11,160 0.016 0.991
10.02 70.0 227 21,678 0.013 0.995
9.79 70.0 197 31,950 0.015 0.976
Water Solubility:
Source: Aldrich
Listed Purity: 99%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 1.5 ppm
Analytical Procedure: At the time of analysis each tube at pH 3 or pH 11 is
neutralized with 0.5M sodium biphosphate buffer. Twenty microliters of the
neutralized solutions is then injected into the HPLC for analysis.
Extraction Solvent:
Instrumentation: GC HPLC _X_ 1C Diode Array UV
Detector: Kratos 757 UV, 216 nm
Column: Waters Nova-Pak C18, 15 cm x 4.6 mm, 5 micron
Temperature Program:
Mobile Phase: 50% acetonitrile, 5% 0.05M sodium diphosphate
Internal Standard:
Linear Range of Analysis:
67
-------
5.3.23 Reserpine
K! = 2.27 hr"1
T1/2 = °*01 days
R2 = 0.995
o>
o
E
-------
5.3.24 Thlourea
CAS No. 62-56-6
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: Degradation was monitored at pH 3, 7, and 11 at 70° fr 6, 10,
and 6 days, respectively. Zero degradation was observed.
Assuming 2% degradation over 10 days would give Ki = 2.02 x 10" d"1 and ti/2 =
300d at 70°C.
Water Solubility: 91.8 g/1
Source: Chem. Serv.
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 1.1
Analytical Procedure: Individual hydrolysis run tubes were sacrificed and
the contents absorbance measured by scanning 200-270 nm referenced to the buffer
blank. The diode array detector was used for the analysis.
Extraction Solvent: NA
Instrumentation: GC HPLC 1C Diode Array UV X
Detector: UV
Column: NA
Temperature Program: NA
Mobile Phase: NA
Internal Standard:
Linear Range of Analysis:
69
-------
5.3.25 Uracil Mustard
CAS No. 66-75-1
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C K^hr'1) K2(M-1hr'1 t1/2(d) r2
5.04
5.07
5.08
7.03
7.08
7.31
9.00
9.04
9.01 3 o
22.2
31.7
31.7
22.2
31.7
31.7
22.2
23.0
> 23.0
0.35
1.16
1.09
0.40
1.38
1.53
2.13
2.13
2.02
2.09 x 105
2.09 x 105
1.98 x 105
0.08
0.025
0.027
0.072
0.021
0.019
0.014
0.014
0.014
0.999
0.999
0.996
0.996
0.999
0.997
0.999
0.994
0.997
Water Solubility:
Source: Upjohn Company
Listed Purity: Assumed 100%
Identity-Purity by Spectral Analysis:
Analysis Concentration: 5.2 ppm
Analytical Procedure: Direct injection of 20 microliter of the hydrolysis sample.
Extraction Solvent: NA
Instrumentation: GC HPLC _X_ 1C Diode Array UV
Detector: UV 257
Column: Waters Nova-Pak C18 5 micron (15 cm x 4.6 mm)
Temperature Program: NA
Mobile Phase: 20% acetonitrile/80% water
Internal Standard:
Linear Range jof Analysis:- fl.21 - 10.5 ppm
70
-------
5.3.25 Uracil Mustard
K! = 0.40 hr"1
T"l/2 = 0.07 days
R2 = 0.996
1 U~t
D)
C
]c
*O 1
£1 ^J """"
-
-------
5.3.26 Ethyl Car-hamate
CAS No. 51-79-6
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
.-!'
pH Temp, °C lO^hr'1) K
3 (see below)
7 (see below) a
9.50 87.0 10.44 3.30 2.8 0.867
9.77 68.0 2.44 0.41 11.8 0.936
Note 19°C temperature differential.
pH 3: Assuming a loss of 2% during 13 day run at 87°C yields
K! = 1.55 x 10"3d~1 and tj/2 = >447 days.
pH 7: Assuming a loss of 10% during 13 day run at 87°C yields
K! = 8.1 x lO'^d"1 and ty2 = >85 days.
Water Solubility: 2000 g/1
Source: Chem. Serv.
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 8 ppm
Analytical Procedure: Direct aqueous injections of on microliter aliquots were
made on-column. Acrylamide was added to each tube before analysis.
Extraction Solvent: NA
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: FID
Column: DB Wax+, 30M, 1 micron, 0.53 mm ID
Temperature Program: 95°C to 190°C
Mobile Phase: NA
Internal Standard: Acrylamide at 6.8 ppm
Linear itenge of Analysis:
72
-------
5.3.26 Ethyl Carbamate
C
*C
*O
E
-------
5.3.27 1.3-Dich1oro-2-propano1
CAS No. Reference
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C
1/2
(hr)
7.02
7.02
7.02
10.04
10.04
10.04
10.04
68.0
68.0
68.0
25.0
11.0
11.0
11.0
43.5
46.8
41.9
37.1
32.5
30.6
29.6
976
855
805
780
1.58
1.48
1.65
1.87
2.14
2.26
2.33
0.994
0.997
0.927
0.914
0.973
0.972
0.984
Water Solubility: 1 in 10 parts water
Source: Aldrich
Listed Purity: 95%
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 19.3 ppm
Analytical Procedure: Direct aqueous cool on-column injections of the buffered
solutions.
Extraction Solvent: NA
Instrumentation: GC X
Detector: FID
HPLC
1C
Diode Array UV
Column: DB Wax+, 30M, 1 micron film, 0.53 mm ID
Temperature Program: 95°C to 140°C
Mobile Phase: NA
Internal Standard: 2,3-Dichloro-l-propanol at 19.6 ppm
Linear Range of Analysis:
74
-------
5.3.28 2,3-Dichloro-l-propanol
CAS No. Reference 616-23-9
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C
7.02
7.02
7.02
7.02
11.00
11.00
11.00
11.00
68.0
68.0
68.0
68.0
26.0
26.0
26.0
26.0
8.1
8.2
7.4
6.2
19.3
19.9
20.1
23.1
-1/2
(d)
19.3
19.9
20.1
23.1
3.6
3.5
3.9
4.7
1.5
1.5
1.4
1.3
0.959
0.985
0.981
0.931
0.728
0.999
0.996
0.934
Water Solubility: 1 part in 10 parts water
Source: Kodak
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 19.6
Analytical Procedure: Same as l,3-Dichloro-2-propanol
Extraction Solvent: NA
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: FID
Column: DB Wax+, 0.53 mm 1.0 u film thickness
Temperature Program: 95° - 140°C
Mobile Phase:
Internal Standard: l,3-Dichloro-2-propanol 19.3 ppm
Linear Range of Analysis:
75
-------
C
*C
*O
E
Q)
5.3.28 2.5-Dichloro-1 -propanol
T1/2
R2
= 1.12 x 10"2 hr"1
= 2.6 days
= 0.999
101-
0.0
50.0
100.0
150.0
Time (hr)
Figure 5.3.28 Hydrolysis of 2,3-Dichloro-1-propanol
at 24°C, pH 11.0
76
-------
5-3.29 1.2,3-Trlchloropropane
CAS No. 96-18-4
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
PH
3.04
3.07
7.12
7.11
10.53
9.63
9.71
Temp, °C
87.0
87.0
87.0
87.0
68.0
87.0
87.0
102K1(hr-1)
0.18
0.14
0.24
0.34
9.6
97
105
^(M'^hr"!) tj^d)
16.0
21.1
12.1
8.5
765 0.30
22,700 0.03
20,470 0.03
r*
0.987
0.876
0.969
0.997
0.998
0.991
0.999
Comment: An activation energy of 30.2 ± 7.6 Kcal/mole was calculated for the
base hydrolysis of pronamido. \-J^-~L\^c4^-io^^^jju^Jl , lo-tifl' 30'7d~l &• 5-
Water Solubility:
Source: Chem. Serv.
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendix A
Analysis Concentration: 0.9 ppm
Analytical Procedure: Ten (10) ml of the buffered hydrolysis sample is extracted
with 2 ml of iso-octane (0.7 ppm in cls-l,4-dichloro-2-butene). The extract is
diluted 1:5 before analysis by GC.
Extraction Solvent: Iso-octane
Instrumentation: GC X HPLC _ 1C _ Diode Array UV _
Detector: EC
Column: OV-1, 5M, 2.65 micron film, 0.53 mm ID
Temperature Program: 45°C isothermal
Mobile Phase: NA
Internal Standard: cj[s-l,4-DichTt>ro-2-batene (0.7 ppm in iso-octane)
Linear Range of Analysis:
77
-------
5.3.29 1.2.5-Trichloropropcme
K! = 1.05 hr"1
Tj/2 = 0.03 days
R2 = 0.999
-------
5.3.30 1.2.3-Tri chlorobenzene
CAS No. Reference 12002-48-1
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data: 01 11 o
pH Temp, °C 103K1(hr'1) K2(M"ihr"i) t1/2(d) rd
3.03 68.0 7.80 3.7 0.755
3.08 70.0 0.79 36.6 0.420
3.07 70.0 1.50 19.2 0.933
3.07 70.0 0.88 32.8 0.691
6.99 68.0 3.28 8.8 0.688
7.13 70.0 0.80 36.1 0.740
7.13 70.0 1.93 15.0 0.867
7.10 70.0 1.90 15.2 0.691
10.70 68.0 3.81 7.6 0.533
9.80 70.0 0.84 34.4 0.626
9.74 70.0 3.0 9.6 0.603
Water Solubility: 12 mg/1
Source: Aldrich
Listed Purity: 99%
Identity-Purity by Spectral Analysis: Appendices A and B
Analysis Concentration: 146 ppm
Analytical Procedure: At the time of analysis of each tube, the buffered
solution of TCB was extracted with iso-octane made to 635 ppb with 2,4-dichloro-
toluene (IS). Dilution 1:5 with iso-octane gave final concentrations of 127 ppb
IS and 10 ppb of TCB.
Extraction Solvent: iso-octane
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: EC
Column: DB-5, 30M, .32 mm, .25 u film thickness
1 _
CAS No. 12002-48-1 in OSW"list references~J1trichlorobenzenes"
79
-------
5.3.30 1,2,3-Trichlorobenzene (Continued)
Temperature Program: 100°C Iso
Mobile Phase: NA
Internal Standard: 2,4-Dichlorotoluene (635 ppb in iso-octane)
Linear Range of Analysis:
80
-------
5.3.30 1.2.3-Trlchlorobenzene
o>
c
*c
*o
£
0)
K! = 1.5 x 10~3 hr
Ti/2 = 19-2 days
R2 = 0.933
0.0
50.0 100.0
Time (hr)
I
150.0
Figure 5.3.30 Hydrolysis of 1,2,3-Trichlorobenzene
at 70°C, pH 3.07
81
-------
1
5.3.31 1.2,4-Trlchlorobenzene
CAS No. Reference 12002-48-1
HYDROLYSIS AND ANALYSIS DATA
Hydrolysis Data:
pH Temp, °C 103K1(hr1) K2(M-1hr1) t1/2(d) r2
6.5 0.593
11.1 0.636
10.0 0.628
18.4 0.773
8.1 0.551
6.6 0.888
4.3 0.530
14.5 0.471
6.9 0.693
5.9 0.999
7.7 0.811
11.5 0.813
Water Solubility: 19 mg/1
Source: Chem. Serv.
Listed Purity: Unknown
Identity-Purity by Spectral Analysis: Appendices A and B
Analysis Concentration: 155 ppm
Analytical Procedure: See 1,2,3-Trichlorobenzene
Extraction Solvent:
Instrumentation: GC X HPLC 1C Diode Array UV
Detector: EC
Cotumn: DB-5, 30M, .32mm, .25 m filnrthickness
Temperature Program: 100°C Iso
3.03
3.09
3.09
3.10
6.99
7.11
7.11
7.09
10.70
9.77
9.81
9.81
68.0
70.0
70.0
70.0
68.0
70.0
70.0
70.0
68.0
70.0
70.0
70.0
4.4
2.6
2.9
1.6
3.6
4.4
6.7
2.0
4.2
4.9
3.7
2.5
-1
CAS No. 12002-48-1 in OSW 1 ist_references "TricMorobenzenes"
82
-------
5.3.31 1.2,4-Trichlorobenzene (Continued)
Mobile Phase: NA
Internal Standard: 2,4-Dichlorotoluene (635 ppb in iso-octane)
Linear Range of Analysis:
83
-------
O)
E
Q>
01
5.3.31 1.2.4-Trichlorobenzene
T1/2
R2
= 4.4 x 1CT3 hr"1
= 6.6 days
= 0.888
D
0.0
50.0 100.0
Time (hr)
150.0
Figure 5.3.31 Hydrolysis of 1,2,4-Trichlorobenzene
at 70°C, pH 7.1_1
84
-------
APPENDIX A
MASS SPECTROMETRIC ANALYSIS
The objective of this MS work is to determine the purity and check the
identity of selected chemicals from those shown in Table 1. These compounds
are used as standards for determining the OSW First Third hydrolysis rate
constants. The mass spectrum of each standard was determined by either GC/MS
or probe/MS.
Reagents — A 300 ppm standard solution in methylene chloride of each
chemical except brucine was made for GC/MS analysis.
The brucine standard was available only as the sulfate. Since
brucine will not chromatograph as the sulfate, a portion was dissolved in water,
made basic with sodium hydroxide, and extracted with methylene chloride, giving
a solution of the free brucine in methylene chloride.
Apparatus and Conditions -- Analyses were carried out with a Finnigan
Model 4500 gas chromatograph mass spectrometer interfaced to the Finnigan Incos
Data System. The mass spectral matching program used the "1984 EPA/NIH Incos
Compatible Library Containing 42,197 Mass Spectra" obtained from W. L. Budde
of EMSL-Ci (EPA/NIH Library). The 1983 version of the bound "EPA/NIH Mass
Spectral Database" and the 1985 version of the "Eight Peak Index of Mass Spectra"
were also used as references. GC column was a DB-5 fused capillary 30m x 0.25mm;
most chemicals were run 3 min e 45°C, 45-280°C 3 10°/min. Acrylonitrile,
acrylamide, and 2-methylacetonitrile, because of their volatility, were held
for 2 min at 30°C, then temperature programmed to 100°C at 10°/min. Reserpine
and warfarin were analyzed from a direct probe at 75-200°C/
RESULTS
Standard Reference Compounds
Benzyl chloride - The GC mass spectrum was a good match to the standard.
spectrum of benzyl chloride in the EPA/NIH Library. There are several chloro-
toluene isomers that mass spectrometry cannot distinguish from benzyl chloride.
The chromatogram showed no other compounds.
2,4-D methyl ester - The GC mass spectrum was a good match to the standard
spectrum of 2,4-D methyl ester in the EPA/NIH Library. The chromatogram showed
an additional small impurity peak (lower boiling but well separated from the
major compound); the impurity spectrum had no database match but was very
similar to the 2,4-D methyl ester spectrum, apparently an isomer. Judging by the
total ion current of each peak, it 1s estimated the chemical is 97% 2,4-D methyl
ester with a 3% impurity.
trans-4-Chlorostilbene oxide - The GC mass spectrum was not in any
available database. However, the fragmentation pattern shows characteristics
expected for trans-4-chlorostilbene oxide. There is a prominent molecular ion
at m/z 230, with a chlorine isomer pattern Indicating only one chlorine. The
base peak is m/z 89, representing a phenyl^C group; ions at m/z 212, 201, and
85
-------
195 represent fragmentation corresponding to losses of HOH, COH, and a chlorine,
respectively. This fragmentation pattern is what one would expect for trans-4-
chlorostilbene oxide. The chromatogram showed no other compounds.
OSW Chemicals
1. Warfarin - The probe mass spectrum was a good match to the standard
spectrum of warfarin in the EPA/NIH Library. An overall estimate of the purity
of the chemical could not be determined (except to say the chemical is mostly
warfarin) since the analysis was by probe/MS.
2. Aldrin - The GC mass spectrum was a good match to the standard
spectrum of aldrin in the EPA/NIH Library. The chromatogram showed no other
compounds.
3. Brucine - The GC mass spectrum was a good match to the standard
spectrum of brucine in the EPA/NIH Library. The chromatogram showed no other ,
compounds (GC-pure). It must be remembered that the sample preparation would
remove any highly polar impurities present in the starting sulfate.
4. Dieldrin - The GC mass spectrum was a good match to the standard
spectrum of dieldrin in the EPA/NIH Library. The chromatogram showed no other
compounds.
5. Pisulfoton - The GC mass spectrum was a good match to the standard
spectrum of disulfoton in the EPA/NIH Library. The chromatogram showed no
other compounds.
6. Endosulfan I - The GC mass spectrum was a good match to the standard
spectrum of endosulfan in the EPA/NIH Library. However, mass spectrometry by
itself is unable to distinguish between the two isomers, endosulfan I and
endosulfan II. The GC retention times of the endosulfan I and II both match
established pesticide retention times. Endosulfan I elutes first and is well
separated from endosulfan II. The chromatogram showed no other compounds.
7. Endosulfan II - The GC was a good match to the standard spectrum of
endosulfan in the EPA/NIH Library. However, mass spectrometry by itself is '
unable to distinguish between the two isomers, endosulfan I and endosulfan II.
The GC retention times of endosulfan I and II both match established pesticide
retention times. Endosulfan I elutes first and is well separated from endosulfan
II. The chromatogram showed no other compounds.
8- 2-Methy 11actoni tri1e - There is no standard spectrum of 2-methyl -
lactonitrile in the EPA/NIH Library. However, a good match was found in the
1983 EPA/NIH Mass Spectral Database; The chromatogram showed no other compounds.
9. Famphur - The GC mass spectrum was an excellent match to the standard
spectrum of famphur in the EPA/NIH Library. The chromatogram showed an additional
small impurity peak (higher boiling but well separated from the major compound);
the impurity spectrum had no database match but was very similar to the famphur
spectrum, apparently an isomer. Judging by the total 1on current of each peak,
it is estimated the chemical is 96% famphur with a 4% impurity.
86
-------
10. Acrylamide - The GC mass spectrum was an excellent match to the
standard spectrum of acrylamide in the EPA/NIH Library. The chromatogram
showed no other compounds, indicating the sample is pure with regard to impurities
that will pass through a gas chromatograph.
11. Acrylonitrile - The GC mass spectrum was a good match to the standard
spectrum of acrylonitrile in the EPA/NIH Library. The chromatogram showed no
other compounds.
12. cis-1,4-Dichloro-2-butene - The GC mass spectrum was a good match
to the standard spectrum of dichlorobutene in the EPA/NIH Library. However,
mass spectrometry is unable to distinguish among the more than twenty possible
isomers. The chromatogram showed no other compounds when the standard was
first run, but a repeat run made after the solution had stood for more than a
month showed some trans isomer.
13. trans-1,4-DichlI oro-2-butene - The GC mass spectrum was a good match
to the standard spectrum of dichlorobutene in the EPA/NIH Library. However,
like its cis isomer, mass spectrometry is unable to distinguish among the more
than twenty possible isomers. The chromatogram showed no other compounds when
first run, but a repeat run made after the solution had stood for more than a
month showed some cis isomer.
14. 4,4'-Methylene-bis-(2-chloroani1ine) - The GC mass spectrum was a
good match to the standard spectrum of 4,4'-methylene-bis-(2-chloroaniline) in
the EPA/NIH Library. The chromatogram showed no other compounds. There are
several other potential isomers of methylene-bis-(chloroaniline). Mass spectrom-
etry by itself can not distinguish among these isomers.
15. Pentachloronitrobenzene - The GC mass spectrum was a good match to
the standard spectrum of pentachloronitrobenzene in the EPA/NIH Library. The
chromatogram showed no other compounds.
16. Pronamide - The GC mass spectrum was a good match to the standard
spectrum of pronamide in the EPA/NIH Library. The chromatogram showed no other
compounds.
17. Reserpine - The probe mass spectrum was a poor match to the standard
spectrum of reserpine in the EPA/NIH Library; the reference spectrum is poor
because it lacks the logical base peak of m/z 195. A good match was found in
the 1983 EPA/NIH Mass Spectral Database. An overall estimate of purity of the
chemical could not be determined (except to say the chemical is mostly reserpine)
since the analysis was by probe/MS.
18. Thiourea - The GC mass -spectrum was a good match to the standard
spectrum of thiourea in the EPA/NIH Library. The chromatogram showed no other
compounds.
19. Ethyl carbamate - The GC mass spectrum was an excellent match to
the standard spectrum of ethyl carbamate in the EPA/NIH Library. The chromatogram
showed no other compounds.
20. 1,3-Dichloro-2-propanol - The GC mass spectrum was an excellent
match to the standard spectrum of 1.3-dich1oro-2-prQpanol in~the EPA/NIH Library.
87
-------
The chromatogram showed an additional small Impurity peak higher boiling but
well separated from the major compound; the spectrum of this small peak was an
excellent match to the standard spectrum of 2.3-dichloro-l-propanol in the
library. Judging by the total ion current of each peak, it is estimated that
the chemical is 97% l,3-dichloro-2-propanol and 3% 2,3-dichloro-l-propanol.
21. 2.3-Dichloro-l-propanol - The GC mass spectrum was a good match to
the standard spectrum of 2,3-dichloro-l-propanol in the EPA/NIH Library. The
chromatogram showed no other compounds.
22. 1.2,3-Trichloropropane - The GC mass spectrum was a good match to
the standard spectrum of 1,2,3-trichloropropane 1n the EPA/NIH Library. The
mass spectra of the trichloropropanes are distinctive, and there is no mistaking
identification. The chromatogram showed no other compounds.
23. 1.2.3-Trichlorobenzene - The GC mass spectrum was a good match to
the standard spectrum of trichlorobenzene in the EPA/NIH Library. However,
mass spectrometry by itself is unable to distinguish among the three possible'
isomers. The chromatogram showed no other compounds.
24. 1.2,4-Trichlorobenzene - The GC mass spectrum was a good match to
the standard spectrum of trichlorobenzene in the EPA/NIH Library. However,
mass spectrometry by itself is unable to distinguish among the three possible
isomers. The chromatogram showed no other compounds.
88
-------
MASS SPECTRUI1
63/28^66 13i50:00 * 6116
SAMPLE! BENZYL CHLORIDE STD <300PPM> 3'17'86
CONDS.t El
CC TEMPt 162 DEC. C
ENHANCED
BENZYL «37e
CALIt C«L32O «3
BASE MxZi 91
RICI lieeee.
91
00
vo
so.e-
65
.V, ill
69
78
rT-~
ee
66
-t-»-*-
Benzyl chloride
H
c—ci
H
63168.
126
97
1C
• i'
ne
128
-------
MASS SPECTRUM
03/29x86 12ie6iOe * 9i39
SAMPLEi 2.4-D METHYL ESTER <300PPH> 3x3x86
CONOS. I El
CC TEMPt 192 DEC. C
ENHANCED
OATAl ME240 K373
CALIi CM.328 »3
BASE
RICl
199
7S13S.
tee. a-
ID
o
so. e
199
43
73
2,4-0 Methyl ester
-CHaCOOCH3
175
63
3.9
se
161
83
L 10,1.
se
133
ll M? 'if.?
11.. '.?s
I- 8688.
234
isa
-------
hftSS SPCCTRUH
ea/2e/«e 12186160 * sii4
SAMPLEI 2/4-D METHYL ESTER <3B0PPM> 3x3^86
CODS. I El
CC TEMPI 167 DEC. C
ENHANCED tS 15B 2N CT>
DATA: MC24D
CALIl CAL328 «3
BASE M/2i 199
RICi 3128.
se. eH
199
2,4-0 Hethgl ester isoHier
(iHpurity)
43
173
73
se
iee
133
161
E28.
234
-------
lee.e
1C
ro
se.e-
MASS SPECTRUM
63x26x86 Ul3Sl6e + 12l26
SAMPLEi 4-CHLOROSTILBENEOKIDE <366PPM> 3x.16x86
COUDS.I El
CC TEMPI 226 DEC. C
ENHANCED
69
DATftl CHLOROSO »746
CALIl CAL326 «3
bHSE.
RICi
24768.
77
m
82
3536.
trans-g-chloFDstilbene oxide
195
281
167
11
ee
JH
e
i:
lie
r^
120
139
140
' I '
160
178
236
160
**
iiv
r^-
220
240
-------
CO
MASS SPECTRUM
64x83x86 14i 21 tee + 3i41
SAMPLE t UARFARIN . 1?...i..
260 238
C1766.
398
f7? . .^.t-
see
-------
100.8-
MASS SPECTRUM
83x28x86
SAMPLEl ALDRIN STD <300PPM> 3x6x86
COHDS.I El
CC TEMPI 225 DEC. C
ENHANCED
66
DATAI ALDRIN *988
CALIl CAL320 «3
BASE MxZi 66
RICi 73088.
se.e-
188.8-
58.8-
Si
..I,. 57 ,,|,
68
-^ 1 pl'I'I'i-inTi-'
228
Cf
T s, T Cl
Ulll 186 19g
||.,,fh,. ...mill, 1,111,1,1,. ft1. ..T,,..1.??, . . M3..,.1,!?! ..».??. 167 .If?.,,!!.,. 2?3.
• I • • • ' I ''-'I I'l'l'l'l I'l ,i|»|i|i|i|i.i[i |i,i|i|i|i|i|i.i,. ,1,1,11111111 [i 1,1, ji.iiiin.,!.!!!!..
88 188 123 148 168 188 288
263
~, *33
255 Ml
.2?7.. '^ijlllllllll,., ??7 2971,1,11,1.1.1., *fi 364
248 ' 268 288 380 328 348 368
9360.
9366.
-------
CD
MASS SPECTRUM
e4'0S'B5 Sl25lC0 •» 20(43
SAttPLEl BRUCINE -NAOH. EXT TO HECL2
COHDS.I El
CC TEMPI 261 DEC. C
ENHANCED
DATAi BRUCIH3 *1243
CALli CAL49 «3
BASE rt'Zi 394
RICt 3B60.
100.8-1
s0.e-
36E.
Brucine
107
55
IfZ
iee.0-i
. , . . .
ee
SI
Uil
80
i T
197
134
1E2
Hllill'ji'illi.T
190
i ,T'f I il
263
2e
120
MO
ie0
220
394
S0.8-
379
240
2E0
3
366.
zee
300
320
340
see
380
40e
-------
100.8-
58. e-
«£>
cn
MASS SPECTRUM
83x-28/^6 9183188 + 14141
SftMPLEi DIELDRIN STD <30QPPM> 2^28^86
CONDS. I El
CC TEMPI 254 DEC. C
ENHANCED
7a
DATftl DIELDRIN #861
CALIt CAL320 «3
BASE M'Zl 79
RICi 59264.
9328.
Dicldrin
MIL,?
...a9,..
nsz
lea.e
68
88
...
188
\,'fi.W .ffi.M..X,i.
?.T« i1?3.
128
148
168
168
58.e-
9328.
29?
399
248
260
200
3&B
32f>
340
360
-------
ieo.e-1
wass SPECTRUM
O3^2e--ee istsotee * 17134
SPMPLEi D1SOLFOTOH (300PPM) 3x19^85
CONDS.I El
CC TEMPI 162 DEC. C
trIHAHCED
88
DISOL It 1074
CALIi CAL328 «3
BASE
RICi
Jl 88
15760.
IO
se.e-
ES
47
-Ul
73
ei
4280.
Disulfoton
97
93
142
125
109
30
Tee
133
186
—r
ise
138
A-
168
274
212
200
—I—
250
-------
ID
MftSS SPECTRUM
63^20/66 9|29100 •
SAMPLEi EHD01 STD C300PPrt> 2'26x86
CONDS.i El
CC TEMPI 249 DEC. C
ENHANCED CS 158 2N 0T>
DATfli END01 «608
CALIi CAL320 *3
BASE M/-Zi 195
RJCi 44460.
se. e-
195
Endosulfan 1
75
63
50
6.9
78
as
109
133
137
ee
80
160
128
T
140
144-
170
1220.
207
229
iee.e-
se.e-
241
160 180 200 220
CJ
1226.
265
277
339
ny.iL .m
.
ivz
-------
VD
100.0-
MASS SPECTRUM
03x26x86 9i50<00 + 11 105
SftMPLEi EHD011 STD <300PPM> 2x28x86
CONDS.t El
CC TEMPI 260 DEC. C
ENHANCED
Endosulfan
50.0-
4
,9
Ik,
HXZ
100.0-
-
- 2
50.0-
•
37
|
240
*^
I
e:
|,
)
75
69 n
ml
»
|i! .1,1.
• * ' • ' i '
80
89
85
li nil
99
|
1
ll
I
i
K
U
19
III., 1
i;
: i
133
ll III
ze
i
\
"t
1'
140
C
II
.3
llll
jS
1
<
D&TA:
CALJi
160
K
III
;0
Cl _
-^-X*0*
ENDOll *665
CAL320 «3
17
L*»
0
183
l«,'| k'l'l
•180
15
!
)5
1
BRSE Mxz, 195
RICt 71608.
2
||
200
07
2
|I,|||||I.U!
1 1 ' ' ' ' 1 ' ' ' '
220
29
1
"TL^^
ii
, 1
flu
267
1U|4*H
260
277
ll
280
V
29
289 | 1
,.1
7
. i .
^
"
3:
T
300 320
9
. .1 358
^V"
340
11 1 • •••''••• 1 '••
368 380
40S
. 1 i .
i . I f 1 | . ,
400
2180.
•
2180.
-
T
420
-------
MASS SPECTRUM
63^26x66 15il9>00 + 2i51
SAMPLEl ACETONE CYANOHYDRJN <38aPPM> 3x12x85
COHDS. I El
CC TEMPI E2 DEC. C
ENHANCED
DATA: ACECY «171
CALIi CAL320 «3
BASE MxZt 76
RICt 34048.
lee.e
o
o
50.0-
2-Methyllactonifrile
58
.?. i ,f., .T.
68
6.3
I
43
SS
65
I- 26728.
4-
CH3
71
7S
-------
MASS SPECTRUM
B3'2e^86 11t11:00 + 15.41
SAMPLEl FAMPHUR STD <3BBPPM> 3X6^86
COHDS.I El
CC TEMPI 2G5 DEC. C
ENHANCED
DATAI FAMPHUR «941
CALIi CAL320 «3
BASE
RICi
Z: 218
46528.
iee.c-i
218
Famphur
50.8-
93
125
63
47
1 9
JL-^i
rvz
S8
'El
158
12688.
282
JE.
256
see
-------
MASS SPECTRUM
03x20x66 iiiiiiee +
SAMPLEl FAMPHUR STO <300PPM> 3x6x86
COHOS.I El
CC TEMPI 277 DEC. C
ENHANCED
DATAi FAMPHUR «998
CALIl CAL320 *3
BASE M'Zl 218
RICl 1668.
IW.0
O
ro
58.0-
2 8
Faraphur isoner
125
47
79
92
50
100
139
T
506.
281
158
7 PICT
T
-------
O
CO
se.e-
43
41
•tf
MOSS SPECTRUM DATAI
e4'lB'86 J2l37te0 + 5i14 CALli
SAMPLE: ftCRYLAMIDE ***************************
COHOS.i El
CC TEMP: 73 DEC. C
EMHAMCED
71
AMIOE2 «314
CAU41B *5
BASE
RICi
44
6312.
r »980.
55
47
54
70
5.6
45
53
65
72
75
85
-------
iee.0
5C. e-
26
MASS SPECTRUM
04^03/-86 ieise>ee + it33
SAMPLEI ACRYLONITRILE
COMDS. I El
CC TEMPI 42 DEC. C
ENHANCED
DATAi ACRYL2 «99
CALlt CAL43 «t3
BASE M'Zt 2G
RICt 661504.
25
J
170240.
53
52
51
27
28
37
~T—'
30
i
^42-,
40
AcrylonHrile
H
;s=c—CN
50
60
-r—•
78
80
-------
100.0-1
MASS SPECTRUM
.04x04x86 13:02:00 + 5:40
^AMPLEt CIS-l,4-DICHLORD-2-BUTENE <3-19-86>
COHDS.t El
CC TEMPI 75 DEC. C
ENHANCED
75
DATAt DCBCIS «340
CALIi CAL44 «3
BASE Mx2i 75
RICt 10832.
S3
O
cn
50.0-
51
G2
* • • • • i
r 2576.
cis-M-Dichloro-2-butene
H H
:HZ CH;
CH
I
Cl
88
77
-r—<—r
f-^-L
124
• I • ' • • I
ne
• i •
120
-------
iee.e-i
MASS SPECTRUM
e3'20'8S 14:34tee 4- 4133
SAMPLEi 1.4-DICHLORO-2-BUTENE <3e0PPM> 3'17xB6
CONDS.I El
CC TEMPt 85 DEC. C
ENHANCED
75
DATAi DCB14 4)293
CALIl CAL32e «3
BASE M'Et 75
RIO 78336.
53
se.e-
51
49
45
62
64
r 18272.
trans-l,4-DichlDro-2-butene
C=C
-»*
I *
a
«•—
cfc,
83
77
ee
7e
'...*•!
9.1
4^?^.
ee
lie
1 I •
128
126
r
138
-------
MASS SPECTRUM
83^20x86 18i41i80 + 16i48
SAMPLE! METHYLENE-BIS-<2-CHLOROANILINE> 386PPI1
.COHOS. s El
CC TEMPi 279 DEC. C
ENHANCED
DAT A i tiBCA
CALIi CAL320 «3
108.8-1
4,4-MethyIene-bis-(2-chlopoaniline)
se. e-
98
77
51
63
! 69
In illUi
iik
84
90
140
U5
184
M/'Z
38
127
193
167
-niw*
283
.••'•.
BASE MxZi 231
RICi 71808.
231
i- 18816.
256
158
288
250
-------
lee.e-
sa. eH
MASS SPECTRUM
83x28/66 12i37i8e 4- 11.86
SAMPLEi PENTACHLOROHITROBENZENE STD OBBPPM) 2/*28'86
COHDS.l El
CC TEMPI 218 DEC. C
ENHANCED
Pentachloronitrobenzene
1«2
7
47
68
95
U8
se
188
138
ir
165
156
. li
DATAt PCNB «666
CALIi CAL328 «3
237
BASE M/Zt 237
RICl 37184.
1S8
238
249
263
I- 2232.
295
Il
2S8
Ae
-------
iee.6
MASS SPECTRUM
e3'2exes isieiiee •» me?
SAflPLEl PROHonlDE STO O6BPPn> 2/28x86
COHOS.I El
CC TEMPI 21B DEC. C
ENHANCED
DATAi PROH
CALIt CAL320 13
173
Pronamide
0 CH3
II 1 3
C — NK— C — C=£H
84
.
,
tea
«
.T
•
i., y '?
,„
rvz se
i6e
260
BASE
RICi
173
779C6.
r »•
TOT
240
230
-------
MASS SPECTRUM
84X83X66 13i4Gl88 + 4|35
SAMPLEl RESERPIME PROBE
CONDS.I El
DATAi RESER «275
CALIl CAL49 «3
BASE
RICl
Zt 19S
95744.
ieo.e->
195
SB.e-
69
49
IL
83
18
37
174
|i1i|l|ii!|iiiiiiliiiii|liii[lil|iiii|i4i|ll).J
Reserpine
21
25
^1
.jtiflllli -iJlllili^j
I 279
.oilltL i-^..li,.
M'Z 390
5364.
5384.
-------
MASS SPECTRUM
64x03x66 14iB9ie0 + 11.24
SAMPLEI THIOUREA
DATAi THIOU «864
CALIi CAL43 *3
BASE M/E:
RICl
76
290.
iea.e-1
76
Thiourea
se.e
59
205.
45
55
ea
75
-------
MASS SPECTRUM
B3'2e/-86 14t52t00 4- 3i40
SAMPLE i ETHYL CARBAMATE STD
COMDS.i El
CC TEMPI 72 DEC. C
ENHANCED
C300PPM>
DATA: ECAR «220
CftLIi CAL326 «3
BASE M/'Z: 62
RICi 17O24.
iee.e-i
62
45
ro
50. e-
46
El
60
I- 7680.
Ethyl carbamate
H H o
i I if
H-C-C-O-C-WH
i I
H H
74
71
-M-
89
H'Z
45
35
65
75
• I • I • I
85
-------
iee.e-1
50.6
MASS SPECTRUM
03/26/8S 14i0Si00 » 4i29
SAMPLE I 1.3-DICHLORO-2-PROPANOL <300PPM>
CONDS.I Et
CC TEMPI 82 DEC. C
ENHANCED
79
DATA: DCPI3 «269
CALIi CAL320 «3
BASE
RICi
Z: 79
74240.
43
44-
33
73
44736.
1,3-Dichloro-2-propanol
H H H
I I I
H-C— C — C-
Cl OH Cl
81
91
se
ne
120
1 i •
130
-------
50.0-
MASS SPECTRUM
e3'20'86 14i22tB0 * 4i53
SAMPLE! 2,3-DICHLORO-l-PROPANOL
CONDS.t El
CC TEMPI 66 DEC. C
ENHANCED
62
<300PPt1> 3x12^-86
DATA! DCP23
CALIi CAL320 «3
RICi
63872.
a
57
53
29824.
64
2,3-Dichloro-l-propanol
H H H
H-C-C-C-OH
d H
E6
92
T
70
73
77
61
80
-r-*-
90
94
lie
lie
• i'
128
-------
iee.e-i
MASS SPECTRUM
84x03x86 13iS2tee + Si 57
SAMPLEi 1,2,3-TRICHLOROPROPANE
CONDS.I El
CC TEMPI 79 DEC. C
ENHANCED
73
DATAi TCPRO *357
CALIi CAL43 *3
BASE
RICt
H, 75
164832.
SB.e
ei
39
27
49
SI
S3
63
48448.
1,2,3-Trichloropropane
H— C— C— C—
H
ci ci ci
77
97
63
lie?
99
ee
t
" I '
120
1 I '
140
146
-------
MASS SPECTRUM
03x20x65 13i27ie0 + 5(87
SAMPLEi 1.2,3-TRICHLOROBENEENE STD <300PPM> 3'3'86
COMDS.i El
CC TEMPt 138 DEC. C
ENHANCED
DATAi TCB #387
CALIt CAL320 *3
iee.e-i
BASE M/Zi 182
RICi 88132.
182
1,2,3-Trichlorobenzene
50.8-
145
189
74
rvz
84
-TT"
80
91
i. Ijy,
119
128
II.
140
• I '
168
28768.
188
-------
MASS SPECTRUM
63x28x65 ISt34100 * 8i22
SAMPLEI 1.2.4-TRICHLDROBENZENE <300PPM> 3x19x86
CONDS.t El
CC TEtlPi 128 DEC. C
ENHANCED
DATAt TCB124 «502
CALIi CAL320 «3
iee.e-i
BASE tl'Z: 182
RICt 17344.
182
l^-Trichlorobenzene
50. B-
143
74
IPS
55
47
61
60
84
91
97
88
iee
119
128
' I •
148
1 I '
iee
4288.
180
-------
APPENDIX B
GC/FTIR ANALYSIS
Figures Bl and B2 are taken from the vapor-phase IR spectral library (EPA-
LIB). The IR spectra for the positional isomers are quite different and this
difference allowed verification of the 1,2,3- and 1,2,4-trichlorobenzene samples.
Figures B3 and B4 contain the reference spectra and the spectra generated from
the GC/FTIR analysis of the respective trichlorobenzene. From comparison of
spectra a and b in Figures B3 and B4, identities are confirmed.
118
-------
Figure Bl. Reference Spectra of 1,2,3-Trichlorobenzene.
119
-------
mTTTTF Fff FFTfFffifHTRTFl
Figure B2. Reference Spectra of 1,2,4-Trichlorobenzene.
120
-------
0.0250
0.0160 .
0.0110 .
I
0.0040 .
-B.B03fl
b. Reference
15B0I3SO12
0 900 7S0
Figure B3. Infrared Spectra of 1,2,3-Trichlorobenzene.
121
-------
0.0650 1
0.0400 1
|
B.BISfl 1
-e.Bioa
b. Reference
H 1 1 1 —*-
a. Sample
1650 J500 13S0 Tcaa idea&£a~
WAVCMJMfSCRS
».2M TC6
Figure B4. Infrared Spectra of 1,2,4-Trichlorobenzene.
122
------- |