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Transformations of ethylene dibromide in aqueous systems and groundwater

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Transformations of ethylene dibromide in aqueous systems and groundwater
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Weintraub, Randy Alan, 1958-
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viii, 190 leaves : ill. ; 29 cm.

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Bromides ( jstor )
Chemicals ( jstor )
Dibromides ( jstor )
Groundwater ( jstor )
Incubation ( jstor )
Ions ( jstor )
Pesticides ( jstor )
pH ( jstor )
Soils ( jstor )
Sulfides ( jstor )
Dissertations, Academic -- Food Science and Human Nutrition -- UF
Food Science and Human Nutrition thesis Ph. D
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1989.
Bibliography:
Includes bibliographical references (leaves 179-188).
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Typescript.
General Note:
Vita.
Statement of Responsibility:
by Randy Alan Weintraub.

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TRANSFORMATIONS OF ETHYLENE DIBROMIDE IN AQUEOUS SYSTEMS
AND GROUNDWATER














By

RANDY ALAN WEINTRAUB


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


1989




TRANSFORMATIONS OF ETHYLENE DIBROMIDE IN AQUEOUS SYSTEMS
AND GROUNDWATER
By
RANDY ALAN WEINTRAUB
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1989


ACKNOWLEDGMENTS
For valuable advice and guidance on this work, I thank
Dr. H. Anson Moye, Chairman of my Supervisory Committee, and
the other members of the Committee: Dr. Willis B. Wheeler,
Dr. Ross D. Brown, Jr., Dr. Joseph J. Delfino, and Dr. Lori
0. Lim.
I appreciate the knowledgeable assistance from Dr.
Gabriel Bitton, Dr. John P. Toth in collecting mass spectra,
and Kenneth M. Jones in advising me on organic synthesis. I
thank Dr. Barbara Ameer for editorial advice and assistance,
Mrs. Elaine M. Peeples for construction of tables of data,
and Ms. Susan Scherer for professional drawings. Collection
of groundwater samples was made possible through
collaboration with Mr. Dennis Bacon and Mr. Geoffrey Herr,
hydrogeologists with the Water Quality Division of the South
Florida Water Management District. I also thank Dr.
Geoffrey Watts of the Florida Department of Environmental
Regulation for his helpful discussion and interest in the
reactions of ethylene dibromide and hydrogen sulfide.
ii


TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS ii
KEY TO SYMBOLS AND ABBREVIATIONS v
ABSTRACT vii
INTRODUCTION 1
LITERATURE REVIEW 5
Groundwater Contamination by Pesticides 5
Ethylene Dibromide 7
Commercial Use 7
Toxicity 8
Chemical and Physical Properties 11
Ethylene Dibromide in Florida
Groundwater and Soil 11
Sorption to Soil 17
Degradation in Soil and Water 19
Risk Factors for Groundwater Contamination 27
MATERIALS AND METHODS 29
Materials 33
Methods 3 3
Ethylene Dibromide and Product
Identification and Quantitation
by Gas Chromatography and
Spectrophotometry 3 3
Liquid Scintillation Counting of
rtC-ethylene Dibromide 37
Gas Chromatography and Mass Spectrometry
for Sulfur Product Identification 38
Oxygen, Redox, and pH Measurements 3 9
Hydrolysis Reactions 40
Kinetics: Temperature and pH Dependence 4 0
Product Identification 43
iii


page
Reactions with Aqueous Hydrogen Sulfide 44
Kinetics: Temperature and pH Dependence 4 4
Product Identification 48
Ethylene Dibromide in
Sulfate Groundwater 48
Organic Synthesis of a Sulfur Product 50
RESULTS 51
Hydrolysis Reactions 51
Verification of Assay for Hydrolysis
Products 51
Kinetics: Temperature and pH Dependence 51
Product Identification 67
Reactions with Aqueous Hydrogen Sulfide 77
Kinetics: Temperature and pH Dependence 77
Product Identification 108
Ethylene Dibromide in
Sulfate Groundwater 129
DISCUSSION 138
Analytical Methods 138
Hydrolysis Reactions 138
Reactions with Aqueous Hydrogen Sulfide 141
SUMMARY AND CONCLUSIONS 150
APPENDIX A ANALYSES OF GROUNDWATER FOR
HYDROLYSIS STUDIES 154
APPENDIX B ANALYSES OF GROUNDWATER FOR HYDROGEN
DEGRADATION SULFIDE STUDIES 156
APPENDIX C MASS SPECTRA OF SULFUR-CONTAINING COMPOUNDS
IN STUDY 158
APPENDIX D MICROTOX ASSAY EVALUATION OF PRODUCTS.... 175
REFERENCES 179
BIOGRAPHICAL SKETCH 189
iv


KEY TO SYMBOLS AND ABBREVIATIONS
ACS American Chemical Society
aq aqueous phase
BDS butyldisulfide
C degrees Celsius
1AC- carbon 14 isotope labeled chemical
ca. approximately
CHT cyclohexylthiol
cm centimeter
cpm counts per minunte
d day
dpm disintegrations per minute
DT 1,4-dithiane
DTT 1,3-dithiolane-2-thione
EDB ethylene dibromide
EPA Environmental Protection Agency
ET 1,2-ethanedithiol
eV electron volts
g gram
hr hour
H2S hydrogen sulfide
i.d. inside diameter
K degrees Kelvin
v


KEY TO SYMBOLS AND ABBREVIATIONS
(Continued)
L liter
M mole per liter
m meter
mCi microcurie
m/e mass-to-charge ratio
min minute
mL milliliter
mol mole
ND none detected
pg picogram
T temperature
TT 1.3.5-trithiane
TTCD 1,4,7,10-tertathiacyclododecane
TTCH 1,2,5-trithiacycloheptane
TTCO 1,2,5,6-tetrathiacyclooctane
TTCP 1,2,3-trithiacycolpentane
U- uniformly radiolabeled chemical
nq microgram
fj. M micromole
yr year
vi


Abstract of Dissertation Presented to the Graduate School
at the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
TRANSFORMATIONS OF ETHYLENE DIBROMIDE IN AQUEOUS SYSTEMS
AND GROUND WATER
By
Randy Alan Weintraub
December 1989
Chairman: Hugh Anson Moye, Ph.D.
Major Department: Food Science and Human Nutrition
Registration of a chemical for use as a pesticide today
requires thorough study of the compound's environmental fate
in water, soil, and air to determine if classification re
stricting its use is needed. During the 30-year history of
"successful" soil fumigation with ethylene dibromide (EDB,
1,2-dibromoethane), its environmental fate was not closely
studied. This nematicide was not recognized as environ
mentally persistent or a public health risk until 1983, when
its agricultural use was suspended in the United States.
In this research, the transformations of EDB were
examined both in buffered aqueous solutions and in ground-
water from several locations in Florida. Experiments were
conducted between 25 and 70C to establish temperature-
dependent rate constants and to expedite the reactions.
The ethylene dibromide and products were analyzed by packed
vii


and capillary gas chromatography (GC), liquid scintillation
counting, and a colorimetric assay. The EDB is converted to
ethylene glycol and bromide ion in aqueous solutions and in
abiotic aerobic groundwaters. The rate of degradation of
EDB is dependent upon temperature but independent of pH
between 5 and 9. Extrapolating experimental results to the
average ground- water temperature in Florida of 22C, the
degra- dation half-life of EDB in the tested groundwaters is
1.5 to 2 years.
An alternative transformation of EDB occurs under
anaerobic reducing conditions in groundwater where aqueous
hydrogen sulfide (H2S(aq)) is commonly present. Transfor
mation by H2S(aq) was not previously recognized as a poten
tially important reaction with pesticides. The rate of
degradation of EDB under these conditions is increased and
dependent upon temperature, pH, and H2S(aq) concentration.
The sulfur-containing products are 1,2-ethanedithiol and
saturated cyclic rings of one, two or four ethylene units
and two, three, or four sulfur atoms. Their structural
identity was elucidated with mass spectrometry (MS) and GC
retention times of products relative to known analytical
standards. One commercially unavailable cyclic disulfide
compound was synthesized and used to positively confirm the
MS and GC findings. Toxicity assessment of sulfur-products,
by Microtox screening assay, suggests increased toxicity
relative to parent compound or to its hydrolysis products.
viii


INTRODUCTION
The reported episodes of groundwater contamination by
landfills and septic tanks, hazardous waste sites,
petroleum-based hydrocarbons, halogenated hydrocarbons, and
pesticides have dramatically increased in the United States
in recent years (Pye and Patrick, 1983). These reports were
followed by efforts to address the problem at both the
federal and state levels. An official report from the U.S.
Environmental Protection Agency (EPA) in 1984 stated that
"significant achievements have been made nationally in the
protection and enhancement of water guality" by controlling
the many point sources of pollution (U.S. EPA, 1984a, p. 2).
This report also recognized the contributions of nonpoint
sources to contamination of groundwater. The later term
refers to pollutants which originate principally from
agricultural activities, runoff from urban lands, and mining
activities. In an Association of State and Interstate Water
Pollution Control Administrator's Nonpoint Source Pollution
Survey, 78% of the states indicated that the magnitude of
nonpoint source pollution problems was at least as great as
that of point source problems (U.S. EPA, 1984b). In all
regions studied by the EPA, agricultural activities in
particular were identified as the most widespread nonpoint
1


2
source of groundwater contamination, affecting 50% of the
waters in 72% of states (U.S. EPA, 1984b). The severity of
the problem depends to a large extent upon local factors
including the hydrogeology of the region, agricultural
practices, rainfall, terrain, and the particular chemicals
that are dispersed into the environment.
Of all the agricultural pollutants of water, pesticides
are the compounds posing the greatest toxicologic hazard.
Of particular interest recently, and the focus of this
research, is the nematicide fumigant, 1,2-dibromoethane or
ethylene dibromide (EDB). It had been widely used in many
states. By 1984, the chemical had been detected in the
groundwater of at least six states. While EDB was first
registered for agricultural use by the U.S. Department of
Agriculture in 1948, only relatively recently has extensive
information been available on the toxicological properties
of this chemical.
The literature review which follows presents current
knowledge of the persistence, fate, and transport of EDB in
the environment and the evolution of the discovery of this
problem. The state of Florida has had particular interest
in this episode for several reasons that will be discussed.
Close study of the history of EDB usage underscores the
urgency of evaluating and amending current practices that
may lead to groundwater contamination, especially from
unexpected nonpoint sources such as pesticides. Prior to


3
discoveries of EDB in groundwater, the chemical was thought
to be sufficiently volatile and of sufficiently low water
solubility to not present an environmental hazard. This
belief is reflected in a report prepared for EPA in 1975
which states "ethylene dibromide is not believed to
accumulate in the environment. Limited information suggests
that it degrades at moderate rates in both water and soil"
(Going and Long, 1975, p lb). Review of the literature
suggests that only until relatively recently was the
movement and accumulation of EDB in the subsurface of
interest. Beckman et al. attributed increased bromide
content in various crops to soil pre-treatment with nemato-
cidal compounds, EDB and 1,2-dibromo-3-chloropropane, which
were "readily degradable," liberating inorganic bromide into
the soil (Beckman et al., 1967, p 138).
The detection of EDB in groundwater came about through
increased sensitivity of modern analytical chemistry
instrumentation and a renewal of concern for environmental
contamination by man's daily practices. In the 1960s,
residual EDB was determined by measuring inorganic bromide
in soil and plant tissue (Beckman et al., 1967; Mapes and
Shrader, 1957). These indirect methods involved combustion
or oxidation of EDB followed by assay of bromide by
titration or polarography. Determination of greater than 1
to 10 parts per million (ppm) was possible; however, these
values were highly dependent upon the care taken to


4
establish the background halide content. In the 1980s, EDB
is detected directly in agricultural commodities (Rains and
Holder, 1981; Morris and Rippon, 1982) and environmental
matrices (Amin and Narang, 1985; Marti et al., 1984) at
concentrations below 10 parts per billion (ppb). These
methods employ purge and trap gas chromatography and mass
spectrometry for achieving lower detection limits and
identity confirmation.
With the benefit of modern analytical chemistry
instrumentation, this study was designed to achieve the
following goals; (1) to describe the kinetics of
degradation of EDB in buffered aqueous systems and in
groundwater, (2) to elucidate the major products of EDB
degradation in groundwater, and (3) to investigate EDB
degradation occurring in buffered aqueous systems and
groundwater in the presence of aqueous hydrogen sulfide
(H2S(aq)) a reactive, natural component in groundwater.


LITERATURE REVIEW
Groundwater Contamination by Pesticides
The Environmental Protection Agency recognized the need
for investigation of groundwater contamination by pesticides
in 1979. The first pesticides discovered in groundwater of
various states were 1,2-dibromo-3-chloropropane (DBCP) and
aldicarb, the later occurring mostly as the sulfone or
sulfoxide (Cohen et al., 1984). Over 50 different
pesticides were found in ground-water basins of California,
one of the largest users of pesticides in the nation. One
of the best known incidences was the discovery of DBCP in
hundreds of wells in the San Joaguin Valley (Litwin et al.,
1983). In 24 other states, a total of 19 pesticides were
detected in groundwater (U.S. EPA, 1987b).
The importance of the safety of groundwater is evident
when faced with the fact that it provides at least half the
potable water to the U.S. population (Pye and Patrick,
1983). The gravity of the situation may be even more acute
in locations such as Florida, where groundwater provides 92%
of the population's potable water supply (Fernald and
Patton, 1984; U.S. EPA, 1987a).
The state of California, in collaboration with the U.S.
EPA in the early 1980s, studied the extent and mechanism of
5


6
groundwater contamination by four widely used pesticides:
DBCP, EDB, simazine, and carbofuran. EDB was found at
concentrations between 0.1 and 31.1 ppb in soils at depths
greater than three meters. Numerous wells were also found
to be contaminated (Zalkin et al., 1983). Meanwhile, in the
summer of 1982, irrigation wells in Georgia were found to
contain EDB at levels as high as 100 ppb (Marti et al.,
1984). The greatest extent of contamination, however, was
not uncovered until the state of Florida began monitoring
groundwater wells in the summer of 1983. In Florida,
contamination was found to exist throughout much of the
heavily farmed regions of the state. Concentrations in
private wells as high as 900 ppb were reported1. Florida
responded rapidly by suspending the use of this agrochemical
in July, 1983 (Florida Statutes, 1983). The EPA followed
this action two months later by imposing a nationwide ban on
all agricultural uses of EDB (Fed. Regist., 1983). State
environmental regulatory agencies of South Carolina,
Washington, Arizona, Massachusetts, and Connecticut have
subsequently reported EDB contamination of groundwater. The
range of typical EDB concentrations in these states as well
as California, Georgia, and Florida is 0.05 20 ppb (U.S.
EPA, 1987b).
:Aller, C. Bureau Chief, Groundwater Protection Division,
Florida Department of Environmental Regulation, personal
communication, March 12, 1985.


7
Ethylene Dibromide
Commercial Use
The EPA estimates that of the 750 to 790 thousand
metric tons (one metric ton equals one thousand Kg) of EDB
formerly produced annually in the United States, only 29 to
33 thousand metric tons were used in agriculture (U.S. EPA,
1983). The major industrial use was as an anti-knock lead
scavenging additive to leaded gasoline, constituting
approximately 0.03% by weight of leaded gasoline. The major
agricultural use (about 90%) was as a soil fumigant. Other
registered agricultural uses included post-harvest
fumigation, spot fumigation of grain milling machinery, and
several other low volume uses (U.S. EPA, 1983). Its
insecticidal and nematocidal properties were known in the
mid-1920s. Federal pesticide registration for its use as a
soil and grain fumigant was granted in the 1950s. EPA
estimates that approximately one million acres in the U.S.
were treated annually for nematode control with nearly 57
thousand metric tons of EDB. The largest portion of this
was employed in farming of soybean, cotton and peanuts, with
lesser amounts used in farming other crops. The greatest
amounts of EDB have been used in the southeastern United
States, where these crops predominate. EDB application
increased somewhat when a closely related fumigant, DBCP,
was banned in 1978.


8
Toxicity
The National Cancer Institute in 1973 first reported
that EDB produces stomach cancer in rats and mice with a
very short latent period (Olson et al., 1973). The chemical
was mutagenic at relatively high doses (0.60, 0.092
revertants/nmol) in the Ames Salmonella reversion assay.
The mutagenicity is not enhanced by addition of rat liver
microsomal extract (McCann et al., 1975; Moriya et al.,
1983). EDB induced lethal point mutations in fruit flies
(Buselmaier et al., 1974) and was acutely toxic in all
animals tested, with LD50 values ranging from 50 mg/Kg in
rabbits to 450 mg/Kg in female mice (National Cancer
Institute, 1978).
The toxic effects of EDB have been postulated to
originate via either of its two known metabolic routes. A
mixed function oxidase (P-450) mediated mechanism through
the intermediate, bromoacetaldehyde, is followed by
conjugation with glutathione (GSH) which is further
metabolized to the water-soluble mercapturic derivative.
The second route involves direct conjugation to GSH, to
produce the half-mustard, S-2-bromoethyl-glutathione. This
reaction is followed by formation of the highly reactive
thiiranium ion, which may also be further metabolized to the
mecapturic acid water-soluble form (van Bladeren et al.,
1980; Shih and Hill, 1981). The later route has been
implicated in producing the most profound toxic effects.


9
Genotoxic damage involves irreversible binding to DNA (Hill
and Shih, 1978) and more specifically, as a S-[2-(N7-
Guanyl)ethyl]glutathione adduct (Inskeep et al., 1986).
These reactions are dependent on cytosolic components and
reduced glutathione (Ozawa and Guengerich, 1983; Inskeep and
Guengerich, 1984).
Early indications of the toxicity of EDB prompted the
Rebuttable Presumption Against Registration (RPAR)
proceedings by EPA in December, 1977 (Fed. Regist., 1977).
The EPA's final decision to suspend usage of this chemical
was based in part upon the subseguent toxicologic findings
and estimates of cancer risks associated with discoveries of
EDB residues in the diet and drinking water. EPA's Cancer
Assessment Group evaluated the increased cancer risk from
EDB-contaminated drinking water using a one-hit model with
"Weibull" timing (U.S. EPA, 1983, p 79). The resulting
risks are shown in Table 1.
In one of two human epidemiological studies published,
mortality data from workers exposed to the chemical in two
EDB production plants were inconclusive in defining the
relationship between EDB and human cancer (Ott et al.,
1980). One notable conclusion, however, was that far fewer
human neoplasms were observed than what was extrapolated
from animal carcinogenicity studies (Ott et al., 1980).
In the second study, a decrease in fertility of men
occupationally exposed to EDB was significant in one of four
workplaces studied (Wong et al., 1979).


Table 1. U.S. EPA estimates of cancer risk for EDB
groundwater contamination.
10
CONCENTRATION
of EDB, ppb
Lua/L)
0.02
0.1
5.0
100.0
LIFETIME CANCER RISK3
0.00005
0.00015
0.0075
0.15
Source: U.S. EPA, 1983.
%
3 Assumes consumption of 2 L of water per day, 60 Kg adult,
for 70 years. These probabilities of observation of cancer
are the additional risks estimated for a lifetime exposure.


11
Evaluating the evidence for EDB carcinogenicity, the
International Agency for Research on Cancer and the American
Medical Association find sufficient evidence from animal
data but inadequate evidence for humans (O'Neill, 1985;
Council on Scientific Affairs, 1988). EPA classifies EDB as
a probable human carcinogen (group B2). Group B2 compounds
are compounds with limited human epidemiologic studies and
sufficient evidence from animal studies.
Chemical and Physical Properties
EDB is the saturated vicinal dibrominated product of
ethylene. It is moderately soluble in water (4300 ppm or
22.9 mM at 30C), compared to most pesticides and is fairly
volatile (11.6 mm Hg, 1.5 x 10"2 atm at 20C). Having a
Henry's law constant (6.6 x 10'4 atm-m3/mol) which is
considered mid-range among commonly occurring chemical
contaminants (Lyman, 1982a) combined with a relatively low
affinity for the organic fraction of soil (organic carbon
coefficient, 66 mg/g, as reported by Rogers and Mcfarlane,
1981; 44 mg/g, as cited in Lyman, 1982b), makes the chemical
suspect to move freely through the underground compartment
where it is introduced intentionally as a fumigant or unin
tentionally from leaking underground gasoline storage tanks.
Ethylene Dibromide in Florida Groundwater and Soil
The locations and levels of EDB in contaminated
groundwater are related to dry and wet time periods and to


12
topography of the land. This pattern presumably reflects the
halting and restarting of dilution of EDB in the aquifer.
For example, a sharp rise in EDB content in the Floridian
aquifer in the eastern part of the Florida panhandle
paralleled the onset of the drought of mid-1986 in the
southeastern United States. In one location studied, the
proximity of sinkholes to areas of EDB application favored
the contamination of underlying limestone aquifers.
As noted earlier, after the initial discoveries of EDB
in groundwater in California, Georgia and Florida, at least
five other states reported finding the compound in their
groundwater. The situation in Florida, however, appeared
the most severe.
Responding to an early indication of the problem, the
state of Florida assembled a multi-departmental task force
headed by the Department of Environmental Regulation. Its
goals were to oversee and implement a state-wide groundwater
surveillance program, to gather available related
information and initiate necessary research, and to offer
assistance to residents of affected areas. Monitoring of
public and private wells since June 1983 has shown that of
the 67 counties in Florida, 22 counties had wells delivering
water contaminated with EDB. Concentrations of EDB detected
have ranged from 0.02 to about 900 ppb (Aller, C., personal
communication, see footnote, p 6). Figure 1 represents the
location of State EDB applications and well water sites


13
known to be contaminated with EDB as of March 1985. The EDB
surveillance program database indicates that by June 1989,
1,703 wells of 13,441 tested (12.7%) were positive for EDB
contamination. Approximately 86% of the positives found
were in the counties of Highlands, Jackson, Polk, Lake, and
Orange. With the exception of Jackson, most of the
contamination (80 to 100%) resulted from the State nematode
eradication program. Ninety percent of the wells tested in
these counties are private wells. Less than 0.1% of wells
tested had EDB concentrations greater than 10.00 ppb. The
majority of the positives were between 0.01 and 1.00 ppb
(Florida Groundwater Protection Task Force Meeting Minutes,
1989).
EDB has been used in Florida by horticultural and
agricultural concerns and in golf course maintenance. Since
EDB was not classified as a restricted use pesticide by the
EPA, users were not required to maintain records. This lack
of record keeping makes it difficult to predict areas at
high risk for contamination and therefore difficult to make
decisions about remediation of this contamination.
Starting in 1960, the Florida Department of Agriculture
documented its use of EDB in their Spreading Decline Control
Program. The disease known as spreading decline is
the result of microbial infection of crops transmitted by
the burrowing nematode. Practices included the
establishment of barriers or buffer zones to prevent the


Figure 1. State of Florida nematode eradication program: application sites of EDB
and EDB-contaminated wells as of March 1985.




16
Feldman, 1965). State records indicate that the EDB
application rate had been about 60,000 to 70,000 liters per
year or an estimated total of 660,000 to 770,000 liters
applied since initiation of the program. The application
rate of EDB in this nematode eradication program was 25 to
50 lbs/acre1. Approximately 9600 cumulative acres were
treated as barriers, which mainly consist of retreated land
which average 417 acres treated per year. EDB was applied
by injection at least eight inches beneath the soil surface
through tubes behind coulter openers or chisels. The
resulting furrows were closed by hilling soil over them, by
press wheels or other means, to prevent loss of the EDB
fumes from the soil (Florida Dept. Agrie., 1984). State-
sponsored application of EDB correlates well with cumulative
contamination data, as shown in Figure 1, with the exception
of the northwestern region of the State. The use of EDB in
soil by the State was estimated to be only about 10 percent
of all the EDB applied. Records of non-State-sponsored
applications are scant, making reliable estimates of usage
impossible (Shankland, 1985). Generally, contaminated areas
are consistent with records compiled by inspectors from
information volunteered by agricultural growers for the last
two years of EDB application around the State, with at least
Written correspondence dated May 9, 1984 from D.Conner,
Florida Secretary of Agriculture, responding to the
information requested by Florida Senator P. K. Neal,
regarding State EDB soil application.


17
one notable exception. Records from Dade county in south
Florida indicate that EDB had been applied in the greatest
quantity, yet no contamination has been found. There is no
explanation for this observation; however, more rapid
groundwater flow compared to other areas of the State may
have contributed to faster dilution of the chemical.
Sorption to Soil
Despite the dispersal of significant amounts of EDB
into the environment from pesticide application, emissions
from gasoline-engine combustion and leakage of underground
tanks, little was known about the persistence, fate and
transport of the compound in the natural environment,
especially, in soil and water. Values as divergent as five
to 10 days (Johns, 1976; Leinster et al., 1978) and 14 years
(National Institute of Occupational Safety and Health, 1977)
were cited as half-lives due to hydrolysis in neutral
aqueous solutions at ambient temperature. Early
investigations focused primarily on residual EDB on crops
and on processed or stored agricultural products (Heuser,
1961; Sinclair et al., 1962; Beckman et al., 1967).
The diffusability of EDB through soil is a crucial
factor affecting its ability to reach and destroy soil-borne
pests. An important factor that influences the diffusion is
the adsorptive capacity of the soil for the fumigant vapor.
Early work indicated that there is little penetration into
soil mass above the point of injection of undisturbed soil


18
after treatment. Sorption was found to be primarily due to
colloidal organic matter and therefore affected greatly by
the amount of organic content of the soil (Siegal and
Erickson, 1953). Sorption was rapid with very little, if
any, irreversible sorption. A sharp drop in sorption
followed small increases in moisture content of soils (i.e.,
from 15 to 17% moisture) with sorption leveling at about 25%
soil moisture content. Temperature decreased the amount of
EDB sorbed on soils by about 5% per degree between 10 and
25C (Wade, 1954). The sorption capacity of soil was
closely related to the observed concentration ratio in the
soil-water phase to the vapor phase (Henry's law constant),
with a three-fold decrease in sorption accompanying a
temperature increase from 5 to 25 C (Thomason et al.,
1974). For up to twenty days after simple line injection,
there was very little loss of EDB to the atmosphere through
an undisturbed soil profile. A loss of less than 5% of EDB
was measured after a chisel shank hole injection at a
commonly employed depth of 30.5 cm, during which time a
constant air stream at a rate of 0.80 Km/hr was passing over
the surface of the soil.
In contrast, investigators fit their experimental data
to the Brunauer, Emmett, and Teller (BET) multi-molecular
isotherm adsorption equation. They found that EDB sorption
potentials to soils were essentially restricted to the
external surface of the soil particle and not organic


19
material (Jurinak and Volman, 1957) The BET adsorption
theory is based primarily on the assumption that Van der
Waal's forces between molecules play the predominant role in
adsorption after the mono-layer is formed. The ability of
EDB to penetrate water structure in close proximity to soil
surfaces is greatly inhibited by increased moisture content
(Call, 1957). The competition between water and EDB for
sites on soil surfaces is also a function of soil type
(Phillips, 1964) .
Under field conditions, two or more interacting edaphic
factors in soil were found to determine the overall
diffusion behavior. Penetration in coarse soil was largely
dependent upon moisture content and temperature; medium-
textured soil penetration was dependent upon moisture,
temperature and bulk density; no movement occurred in fine-
textured soil (Townsend et al., 1980). In closely related
studies, sorption of neutral organic compounds was shown to
be essentially a partitioning-controlled process rather than
a physical adsorption process (Choiu and Peters, 1979;
Rogers and McFarlane, 1981).
Degradation in Soil and Water
Evaluation of the ability of microbes to degrade EDB
has been reported by two laboratories. Bacterial batch
cultures of primary sewage effluent incubated under anoxic
denitrifying conditions failed to degrade EDB (Bouwer and
McCarty, 1983). It was found, however, to be rapidly


20
transformed under anoxic methanogenic conditions in batch
cultures and in a continuous-flow methanogenic fixed-film
column (Bouwer and McCarty, 1985). Anaerobic suspensions
of sewage sludge, activated by percolating oxygen through
the sewage, gave similar findings. The gaseous product in
this case was confirmed to be ethylene (Weintraub et al.,
1986). This laboratory also found that similar suspensions
incubated under aerobic conditions resulted in rapid
degradation to a non-volatile, debrominated and highly
water-soluble product (Jex et al., 1985). Separation of
this product was achieved by high performance liquid and
thin layer chromatography plus chemical derivatization for
gas chromatography and mass spectrometry analysis.
Analytical results suggested a single product which probably
is a condensation or complexation with organic materials or
microbial cells.
The ability of natural microbiota to degrade EDB from
contaminated areas has been reported by two laboratories.
In the first study, soil was obtained from three Florida
farming regions where the chemical was used extensively for
many years. Soil samples from depths of one and three
meters, which were assumed to be anaerobic, were incubated
as such in aqueous suspensions. Only inorganic nutrients
were added and incubated for seven months. The
investigators found that EDB was either not degraded or only
marginally degraded by organisms in Florida soil (Weintraub


21
et al., 1986). In contrast, the second study found EDB to
be rapidly mineralized to carbon dioxide and bromide ion by
organisms in surface soils under aerobic incubation
conditions. Soil and water were sampled from an EDB-
contaminated groundwater discharge area in Connecticut. The
conversion of EDB to these products was almost complete with
the exception of only small amounts of an unidentified
unextractable product (Pignatello, 1987).
Wilson et al. (1986) found that EDB was rapidly
degraded in aquifer material known to support
methanogenesis. The equilibrium redox potential of the
material used was -272 mV. Concentrations of 200 ppb of EDB
in the aquifer matter-pore water used declined to 27% of the
control concentration by seven weeks of incubation at 17C.
No carbon dioxide was detected as a degradation product.
Although no product was identified, a peak observed by gas
chromatography with flame ionization detection coincided
with the disappearance of EDB; subsequent GC/MS was not
successful in identifying this peak. The report made no
mention of the presence of hydrogen sulfide, commonly
present in the material described and possibly a very
important reactant in the incubation material.
Steinberg, et al. (1987) have reported residual EDB in
soils from Connecticut farmlands highly resistant to
degradation or mobilization. The EDB was released with heat
and organic solvent treatments. Central Florida soils that


22
were treated approximately bi-annually, but had not received
EDB treatment for at least 5 years, had EDB residues up to
60 ng/g of dry soil (Moye and Weintraub, 1988). The EDB in
these soils was released with 75C acetonitrile incubation.
About 1 ngEDB/g dry soil was released from some of the soils
after exposure to 45C dry heat for 8 hr followed by and
aqueous washing. The importance of a fraction of "soil-
bound" EDB in contaminated areas is still being evaluated.
Other modes of degradation of EDB have also been
investigated recently. EDB in aqueous solution is rapidly
photohydrolyzed upon irradiation with a 450-W medium
pressure mercury lamp to yield ethylene glycol and bromide
ion. The rate enhancement for this process was estimated to
be 105 times greater than that of the nonphotolytic pathway
(Castro and Besler, 1985). In another study, EDB was shown
to undergo complete heterogeneous photocatalyzed
transformation to carbon dioxide and hydrogen bromide
(Nguyen and Ollis, 1984). This conversion was catalyzed on
titanium dioxide when illuminated with near-UV radiation.
The titanium dioxide surface is suggested as the site of
formation of hydroxyl radicals which promote the reaction.
Other investigators have found that the superoxide ion
dioxygenates EDB to yield formaldehyde and bromide ion in
aprotic solvents (Calderwood and Sawyer, 1984) The later
three modes of degradation of EDB have been suggested by the
authors as useful ways to dispose of halogenated pesticide


23
wastes such as EDB. Finally, oxidation of EDB to
formaldehyde in aqueous solution has been reported to occur
at high temperatures (i.e. greater than 80C). The
conversion, however, was not found to be significant under
environmental conditions. In this same laboratory, EDB at
concentrations of 300 and 700 ppb was found to be stable
over a two-week period at 25C in solutions of aqueous
chlorine which are commonly attained during disinfectant
processes in municipal water facilities. Total concen
trations of one and 10 ppm of the two species, hypochlorous
acid (H0C1) and hypochlorite ion (OC1), were varied by
buffering the solutions from pH 6.5 to 9 (Moye et al.,
1986). It is important to note that the above mentioned
studies are laboratory modes of reaction that do not
necessarily reflect reactions in the field.
An additional route of degradation of EDB in the
environment may have been uncovered by recent work by
Schwarzenbach et al. (1985). These investigators detected
numerous dialkyl sulfides and other volatile sulfur-
containing compounds while sampling wells in an area
contaminated seven years earlier by commercially produced
volatile halogenated hydrocarbons. In laboratory studies it
was revealed that at least for a representative test
compound, 1-bromohexane, under highly reducing conditions in
the presence of hydrogen sulfide, nucleophilic substitution
reactions proceed quite readily. A recent report by Watts


24
and Brown (1986) describing the findings of organics in
contaminated well fields in Palm Beach county, Florida,
includes the sulfur-containing compounds ethyl mercaptan,
triethyl disulfide, and diethyl disulfide, as well as
bromoethane. Although the components of gasoline were also
found in the well water, no EDB was reported. The
possibility of a similar reaction occurring with EDB in
anaerobic groundwater has recently been reported by
Weintraub and Moye (1987).
Vogel and Reinhard (1986) identify the reductive
dehalogenation product of EDB, vinyl bromide, as a major
product in their hydrolysis study of EDB. If, in fact,
vinyl bromide (Moye and Weintraub, 1986), is the major
product, than EDB's degradation in groundwater does not
decrease toxicity (Henschler, 1985).
Summaries of the modes of degradation of EDB discussed
here are presented in Tables 2 and 3. Ongoing and future
work may enable scientists to understand the variations and
relative importance of these and possibly other modes of
degradation in relation to the persistence and hazard
presented by this chemical in the environment.


Table 2. Summary of microbial transformation of EDB.
CONDITIONS
HALF-LIFE
PRODUCTS
REFERENCE
Field crops
"rapid"
1
Br ?
Beckmann et al.
(1968)
Soil-water
cultures
ca. 30
d
Br- + ethylene
Castro, Besler
(1968)
Anaerobic
(denitrifying)
N.D.

Bouwer, McCarty
(1983)
Anaerobic
(methanogenic)

Br- + ethylene
Bouwer, McCarty
(1985)
Florida soils
(methanogenic)
N.D.

Weintraub et al.
(1986)
Activated-sludge
(methanogenic)
ca. 21
d
Br- + ethylene
Jex et al. (1985)
Activated-sludge
(aerobic)
5-10 d
Br-, Biomass
Jex et al. (1985)
CT stream-sedi
ment (aerobic)
35-350
d
Br-, C02, biomass
Pignatello (1986)
Aquifer material
(methanogenic)
ca. 21
d
Unidentified
Wilson et al.
(1986)
N.D.
None observed


Table 3. Summary of chemical transformations of EDB.
MODE
CONDITIONS
HALF-LIFE
PRODUCTS
REFERENCE
HYDROLYSIS
Neutral, aq
2 5 C
5-10 d
Not Reported
John (1986)
Neutral, aq
2 0 C
14 yr
Not Reported
NIOSH (1977)
Neutral, 'Zero
buffer' 20C
8 yr
Br Unident-
f ied
Cohen,Jungclaus
(1986)
FL groundwater
abiotic, 22 C
1.5-2 yr
Ethylene glycol +
Br'
Weintraub et
al. (1986)
PHOTOLYSIS
UV, aq
10 d
Ethylene glycol +
Br'
Castro et al.
(1985)
SULFIDE
SUBSTITUTION
Buffer-aq,
5-75 ppm
H,S, 25 C
2-4 mo.
Cyclic-alkyl and
dialkyl- sulfides
Weintraub et
al. (1987)
REDUCTIVE
DEHALOGENATION
Aq, 20 C
2.5 yr
vinyl bromide +
Unidentified
Vogel, Reinhard
(1986)


27
Risk Factors for Groundwater Contamination
Florida's citrus, soybean and peanut farming areas,
where EDB was commonly used, are located on predominantly
sandy and well-drained soils with very low organic matter
content (i.e., less than 1%). The soils are mostly entisol,
spodosol, alfisol and ultisol types. Together with a
relatively high mean annual rainfall and high recharge to
the Floridian aquifer in these regions (Fernald and Patton,
1984), the potential for movement of certain chemicals
through the unsaturated subsurface zone is great. As
previously explained, EDB has this ability to be quite
mobile as well as persistent.
There have been a number of attempts in recent years to
develop comprehensive groundwater protection strategies.
The main goal has been to establish criteria upon which to
base regulatory and monitoring decisions to guard against
groundwater contamination. The EPA began such an effort in
1979 to identify pesticide characteristics, nitrate levels,
and soil pH that would likely result in groundwater
contamination (Cohen et al., 1984). Another approach
currently proposed by the EPA makes use of a numerical
rating scheme for evaluating the potential for groundwater
contamination in a specific site given its geohydrological
setting. The scheme is called DRASTIC, an acronym for (i)
depth to groundwater, (ii) recharge rate, (iii) aquifer
media, (iv) soil media, (v) topography, (vi) impact of the


28
vadous zone, and (vii) conductivity of the aquifer (Rao et
al., 1985).
More recently, researchers at the University of Florida
have developed a simple scheme for ranking the relative
potentials of different pesticides to intrude into
groundwater (Rao et al., 1985). The index, referred to as
the attenuation factor (AF), is intended for use by
regulatory agencies in a preliminary evaluation of a large
number of pesticides to target chemicals for groundwater
monitoring programs or to initiate site-specific studies.
Of the 40 chemicals evaluated, the top 5 ranking pesticides
were EDB, bromacil, picloram, DBCP, and diuron. Not
surprisingly, EDB ranked as having the greatest potential
for groundwater intrusion in the soils tested.


MATERIALS AND METHODS
Materials
The following is a list of materials used in this study
along with the supplier and stated purity or grade when
provided by the manufacturer. The supplier's location is
listed only the first time it is mentioned.
Analytical Standards
Bromoacetic acid (Aldrich Chemical: Milwaukee, WI; 98%)
Bromoethane (Aldrich Chemical; 99+%)
2-Bromoethanol (Eastman Kodak; Rochester, NY 98%)
1-Butanethiol (Eastman Kodak; 99+%)
Butyldisulfide (Aldrich Chemical: Milwaukee, WI; 98%)
Cyclohexylthiol (Aldrich Chemical; 95+%)
1,2-Dibromoethane (Aldrich Chemical; Gold Label; 99+%)
1.2-Dibromoethane (ethylene dibromide, EDB; EPA Pesti
cides and Industrial Chemical Repository: Research
Triangle Park, NC; 99+%)
1,4-Dithiane (Aldrich Chemical; 97%)
1.3-Dithiolane-2-thione (Aldrich Chemical; 99%)
1,2-Ethanedithiol (Eastman Kodak; 99.5%)
Ethanethiol (Eastman Kodak; 98%)
Ethyl disulfide (Aldrich Chemical; 99%)
Ethylene glycol (Eastman Kodak; 99+%)
29


30
37% Formaldehyde solution (Fisher Scientific: Fair
Lawn, NJ; ACS Certified, 36.6%)
Paraformaldehyde (Fisher Scientific; 95%)
Potassium bromide (Mallinckrodt: Paris, NY; analytical
grade)
1,4,7,10-Tetrathiacyclododecane (Aldrich Chemical: West
Chester; 97%)
1,4,7-Trithiacyclononane (Aldrich Chemical; 98%)
1,3,5-Trithiane (Chem Service: West Chester; 99%)
Vinyl bromide (Aldrich; 98%)
Radiolabeled Chemicals
uC-Formaldehyde (4.4 mCi/mmoL, Pathfinders: St. Louis,
MO; 98%)
U-^C-Toluene (1.8 nCi/mh, New England Nuclear:
Boston, MA)
U-uC-Ethylene dibromide (55 mCi/mmoL, Amersham:
Arlington Heights, IL; 95+%)
U-uC-Ethylene dibromide (U-25 mCi/mmoL, Amersham; 95+%)
U-14C-Ethylene glycol (U-4.23 mCi/mmoL, Pathfinders;
98%)
Solvents and Reagents
Agua-Sol 2 (New England Nuclear)
Buffer solutions, pH 4, 7, 10 (Fisher Scientific;
ACS Certified)
Chloroamine T (Fisher Scientific; ACS Certified)
Chloroform (Fisher Scientific; HPLC-grade)


31
Chromotropic acid disodium (Fisher Scientific; ACS
Certified)
N,N-Dimethyl-p-phenylenediamine dihydrochloride
(Aldrich Chemical; 99%)
Ferric chloride hexahydrate (Aldrich Chemical; 97%)
Ferric ammonium sulfate (Fisher Scientific, ACS
Certified)
Hexanes (Fisher Scientific; pesticide grade)
Iodine (Fisher Scientific; Certified ACS)
2-Nitrophenylhydrazine (ICN Pharmaceuticals, Plainview,
NY)
Periodic acid (Mallinckrodt; ACS analytical grade)
Potassium nitrate (Fisher Scientific; Certified ACS)
Potassium fluoride (Fisher Scientific; Certified ACS)
Potassium ferrocyanide (Fisher Scientific; Certified)
Potassium ferricyanide (Fisher Scientific; Certified
ACS)
ScintiVerse II (Fisher Scientific)
Sodium sulfide, 9-hydrate (Eastman Kodak; ACS reagent,
98.0-103.0%)
Sodium sulfite (Fisher Scientific; Certified ACS)
Sulfuric acid (Fisher Scientific; Certified ACS)
Triethylamine (Aldrich Chemical; 97%)
Water (Fisher Scientific; HPLC-grade)


32
Components of Buffers
All of the following chemicals were Fisher Scientific,
ACS Certified grade unless otherwise indicated.
Borax (sodium tetraborate, Sigma Chemical: St. Louis,
MO; 99.9%)
Disodium dihydrogen phosphate hepta hydrate
Disodium borate decahydrate
Disodium carbonate
Glacial acetic acid (reagent ACS)
Hydrochloric acid (reagent ACS)
Monopotassium phosphate
Potassium acetate
Potassium phthalate
Potassium chloride
Sodium monohydrogen phosphate monohydrate
Sodium citrate
Sodium hydroxide
Sodium monohydrogen carbonate
Sodium borate
Sodium carbonate decahydrate
Sodium succinate
Titanium trichloride solution (20%/80% water stabilized
with 3% phosphoric acid)


33
Gas Chromatographic Materials and Columns
5% Carbowax 20M (Supelco: Bellefonte, PA)
Gas Chrom Q 80/100 mesh (Supelco)
15% OV-17 on Gas-Chrom Q (Alltech Assoc.: Deerfield,
IL)
4% OV-225 on Chromosorb Q (Supelco)
Phenylmethylsilicone crosslinked coated capillary
column (DB-5, J & W Scientific: Folsom, CA)
Polymethylsiloxane crosslinked coated capillary column
(Ultra 1, Hewlett-Packard: Palo Alto, CA)
Polyphenylmethylsiloxane coated wide bore column
(RSL-300, Alltech Assoc.)
Polypropylene glycol (Supelco)
10% Squalane on Chromosorb W (Supelco)
Methods
Ethylene Dibromide and Product Identification and Quantita
tion bv Gas Chromatography and Spectrophotometry
Gas chromatography of EDB and related brominated metabolites
Gas chromatograhpic (GC) conditions were established for
the simultaneous analysis EDB and other closely related
bromominated metabolites (bromoethane, bromoacetic acid and
2-bromoethanol) on a Hewlett-Packard Model 5840A gas
chromatograph (GC) equipped with a 63Ni electron capture
detector (EC) and a Hewlett-Packard Model 7671 A
autoinjector. The 2 m x 0.32 cm i.d. glass column used was


34
packed with 15% polypropylene glycol (PPG) on Gas Chrom Q
80/100 mesh solid support which was coated in this
laboratory. The solid support was coated by slow
rotoevaporation of 50 mL of acetonitrile in which the 3 g of
PPG was dissolved and 17 g of solid support was added. The
resulting stationary phase achieved superior separation of
the analytes compared to others tested. The column packings
which were used perviously EDB and similar analytes and
tested include 5% Carbowax 20M (polyethylene glycol, Dumas
and Bond, 1982), 15% OV-17 (Rains and Holder, 1981), 4% 0V-
225, and 10% squalane. The PPG was used for the
determination of ethylene chrorohydrin (2-chloroehtanol) by
Heuser and Scudamore (1967).
The PPG column prepared was used with a 5% methane/95%
Ar carrier gas at a flow of 52 mL/min. Temperatures
maintained during analysis were 100C for the column, 300C
for the detector and 225C for the injector.
EDB was extracted from aqueous solutions by parti
tioning into hexane upon mixing. For experiments in which
solutions were incubated in 100 mL serum bottles, the
following procedures were followed. Using a 10 mL syringe a
10 ml aliquot was withdrawn through the Teflon-coated rubber
septa, and slowly delivered to a 10 mL volumetric flask to
assure a precise volume. This volume was transferred to a
15 mL screw-top test tube to which 1.0 mL of hexane was
added and the tube immediately capped. It was inverted 5


35
more times and allowed to stand for at least 5 min. A
portion of the hexane layer was pipetted into a 1 mL vial
for automated gas chromatographic analysis. In subsequent
experiments where solutions were incubated in 10 mL sealed
ampules or where the partitioning of uC-activity was
analyzed, 2 mL of soltions were transferred with a tranfer
pipet to test tubes containing 2.0 mL of hexane. All
extractions of aqueous samples were performed in duplicate.
Extracts were injected in duplicate into the GC. Standard
curves of detector response ranging from 2 0 to 1500 pg//iL of
EDB were prepared daily and used for quantitation using
linear regression least squares analysis.
Determination of ethylene glycol
Ethylene glycol concentrations in water were determined
by GC analysis of the 2-nitrophenylhydrazine derivative of
formaldehyde, formyl 2-nitrophenylhydrazone. The method of
Fishkind (1987) for the analysis of formaldehyde in water
was adapted by including a preliminary oxidation step. To 2
or 4 mL of the water sample, a 20 /L aliquot of 5 x 106 M
periodate and the sample was then allowed to stand at room
temperature in the dark for 20 hours. Periodic acid
oxidizes ethylene glycol into two molecules of formaldehyde
(March, 1985). Excess periodic acid was precipitated by the
addition of 50 fiL of a saturated solution of potassium
nitrate? the mixture was allowed to stand for 1 hr in an ice
bath (Hillenbrand, 1952).


36
Standard aqueous solutions of ethylene glycol prepared
from analytical grade ethylene glycol were assayed by the
same procedure each day of analysis to construct a standard
curve for quantitation. Aqueous formaldehyde, which was
either formed by the oxidation of ethylene glycol or was
present in standard solutions, was quantitated by the
addition of 640 of a 2 M aqueous solution of 2-nitrophen-
ylhydrazine, which had been recrystallized from hexane to
remove background formaldehyde. After the addition of this
derivatizing reagent, the reaction mixture was incubated in
a water bath at 40C for 1 hr. The derivative 2-
nitrophenylhydrazone was extracted by the addition of 5 mL
of hexane to the tube, which was then mixed on a vortex-
mixer for 1 min. A portion of the hexane layer was pipetted
into a 1 mL vial for automated analysis on a Hewlett-Packard
Model 5890 GC. This instrument was equipped with a Hewlett-
Packard Model 7671 A autosampler, a 63Ni electron capture
detector, and a 2 m x 0.32 column packed with 4% OV-225 on
Chromosorb Q 80/100 mesh. A 5% methane/95% Ar carrier gas
at 30 mL/min, a column temperature of 173"C, a detector
temperature of 300C, and an injector temperature of 225C
were employed.
The method was validated with use of 14C-ethylene
glycol (specific acitivity 4.23 mCi/mmol) and UC-
formaldehyde (specific activity 4.4 mCi/mmol). Unlabeled
stock standard formaldehyde solutions made from para-


37
stock standard formaldehyde solutions made from para
formaldehyde were standardized against accurately made
solutions of bisulfite formaldehyde and 37% formaldehyde
solution using the chromatropic acid spectrophotometric
method of Houle et al. (1970). Other supporting data used
for optimization of these procedures are described by
Fishkind (1987) .
Determination of bromide
Bromide ion concentrations in water were analyzed by
Standard Water and Watsewater Methods Procedure No. 405 C
(American Public Health Association, 1980, p 261). Bromide
ion was oxidized by Chloroamine T to bromine which bro-
minates phenol red. The brominated product was measured by
absorbance of the reaction mixture at 590 nm on a Beckman
DU-8 spectrophotometer. Standard agueous solutions of
bromide prepared from potassium bromide were assayed to
construct a standard curve over a range of 50 to 1000 /ig/L.
Samples were diluted as needed with deionized water to final
concentrations which fell within the linear quanitative
range.
Liquid Scintillation Counting of 14C-ethvlene Dibromide
Total HC-activity was measured by liquid scintillation
counting of 1.0 mL of sample pipetted into 15 mL of liquid
scintillation fluid. Either Aqua-Sol 2 or Scinti Verse II
liquid scintillation fluids were used. There was no
difference in results using either of these reagents.


38
Counting was done on a Searle Analytical 92 liquid scintil
lation counter with a Silent 700 electronic data terminal.
Quenching was evaluated both by comparing additions of
the fortified waters or hexane extracts to additions of
known amounts of 1AC-toluene (4xl06 dpm/mL) and by external
addition of 20 /xL of 1AC-toluene to fortified waters or
hexane extracts. The dpm/mL in aqueous solutions or hexane
extracts was determined by dividing the measured cpm/min by
the counting efficency. Efficiency and precision of
extraction of EDB from the waters were evaluated in a
similar fashion.
Gas Chromatography and Mass Spectrometry
for Sulfur Product Identification
Analyses were performed on a GC with a flame
photometric detector with a 394 nm filter for sulfur-
containing compound selectivity (FPD/S). With this filter,
the predominant chemiluminesence bands of emmision of
sulfur-containing analytes are detected (Farwell and
Barinaga, 1986). Analyses were performed on a 5840A Hewlett
Packard GC equipped with a Hewlett Packard 7671A autosampler
and a 15 M x 0.53 mm i.d. wide bore column with 1.2 /xm
polyphenylmethylsiloxane film (RSL-300). The oven
temperature was programmed as follows: it was held at 40'C
for 2 min, then increased at a rate of S'C/min to 90C, then
25C/min to 200C. The carrier gas flow of nitrogen at 10
mL/min. FPD/S conditions were as follows: injector


39
temperature 170C, detector temperature 225C, hydrogen 80
mL/min, oxygen 14 mL/min and air 55 raL/min.
Extracts from aqueous incubations, usually a 5:1 ratio
water to hexane, and the sulfur-containing standards in
hexane also were analyzed by GC/MS on a Finnigan 4021 GC/MS.
This instrument was equipped with a 30 M x 0.25 mm i.d.,
0.33 nm phenylmethylsilicone crosslinked film coated
capillary column (DB-5). The GC oven temperature was
programmed to begin at 60C and increase at a rate of
12C/min to 280C. Mass spectra were obtained in electron
impact (El) and chemical ionization (Cl) modes, both at 70
eV and a source temperature of 150C. The Cl spectra were
collected with isobutane reagent gas at 0.2 torr.
Oxygen, Redox, and pH Measurements
Dissolved oxygen was measured with a membrane oxygen
electrode (model 97-08, Orion Research, Cambridge, MA). The
electrode was calibrated in water-saturated air and zeroed
in a 5% sodium sulfite solution. Measurements were made in
a 100 mL BOD bottle without headspace.
Redox potential (Eh) was measured with a platinum redox
electrode (model 97-80, Orion Research Inc., Cambridge, MA).
This electrode was calibrated using the following solutions:
(1) 0.1 M potassium ferrocyanide with 0.05 M potassium
ferricyanide, (2) 0.01 M potassium ferrocyanide, 0.05 M
potassium ferricyanide, and 0.36 M potassium fluoride, and
(3) a standard ferrous-ferric solution composed of 0.1 M


40
ferrous ammonium sulfate, 0.1 M ferric ammonium sulfate, and
0.1 M sulfuric acid (Light, 1972).
The pH was measured with a glass body combination
electrode (model EA-2, Fisher Scientific, Fair Lawn, NJ) and
calibrated in standard pH 4, 7, and 10 buffer electrode
standardization solutions. All of the above mentioned
electrodes were connected to an Orion model 601A digital
ionanalyzer for operation.
Hydrolysis Reactions
Kinetics: Effects of Temperature and pH
Preparation and incubation of solutions
Groundwater was obtained from shallow wells in three
counties in northcentral and northwestern regions of the
State: Polk, Highlands, and Jackson. Water samples were
characterized by analyses either on-site, at this
laboratory, or at the Extension Soil Testing and Analytical
Research Laboratory, University of Florida (Appendix A).
The water was collected in five-gallon polypropylene
containers and kept on ice during transport to this
laboratory. Water was assayed for residual EDB by the
packed colunm GC analysis.
One hundred ml aliquots of these water samples and of
laboratory deionized water were fortified with EDB to con
centrations of 10 or 100 ppb with a methanol/water stock
solution of the chemical. Glass serum bottles (100 mL,


41
Wheaton, Millville, NJ) were filled with the solutions, the
headspace purged with nitrogen and the bottles tightly
capped with Teflon-coated rubber septum seal crimp caps
(Supelco, Beliefonte, PA). Before sample preparation, the
serum bottles, seals, and caps were autoclaved (121C, 15
psi, 20 min) and the waters were either autoclaved (same
conditions) or vacuum-filtered through a 0.20 /urn filter
(Millipore, Bedford, MA) to eliminate microbial activity.
Sets of samples prepared in duplicate were incubated in
an inverted position in a darkened water bath. Since EDB
was relatively stable in water at ambient temperatures in
preliminary experiments, incubations were performed at 40,
50, 60, 70 and 80C 0.5'C. Serum bottles were
periodically taken out of the water bath and allowed to
equilibrate to room temperature before sampling. The time
interval between samplings was determined by the observed
rate of disappearance of EDB.
The apparent first-order rate constants for EDB
degradation were obtained by linear regression least squares
analysis of the log percent EDB remaining vs time plot.
Arrhenius temperature dependence was assumed, whereby a plot
of log rate constant vs 1/T K provides a convenient graphic
method to evaluate the activation energy, Ea, and to
estimate the rate constant of the reaction at any desired
temperature.
At least two samples in each incubation trial were
fortified with a U-UC-EDB (25 mCi/mmol) by addition from a


42
by addition from a 5 xCi/mL methanolic stock solution to a
final concentration of ca. 5000 dpm/mL. These samples were
periodically sampled to check the integrity of the system by
measuring the containment of the KC-activity. The
radiochemical purity was reported to be 98% (Amersham) and
confirmed in this laboratory to be within 5% of the stated
value as measured by gas chromatography and liquid
scintillation counting. To check the efficiency of hexane
extraction of EDB and its losses during the analysis
procedure, solutions of UC-EDB were analyzed by identical
procedures.
The degradation of EDB was evaluated as a function of
pH in the three groundwaters and deionized water. A series
of 5 mM buffer systems (Diem, 1962) were used to maintain
groundwater and deionized water fortified with EDB at pH
values ranging from 4.0 to 9.0. The buffers and
concentrations of the components added for the resulting pH
as indicated were as follows: borax/succinic acid: 0.89
mM/4.11 mM pH 4.0, 1.98 mM/3.02 mM pH 5.2; potassium
phthalate/NaOH: 5.00 mM/0.04 mM pH 4.0, 5.00 mM/0.12 mM pH
4.6; borate/KCl/NaOH: 5.00 mM/5.00 mM/0.40 pH 8.0, 5.00
mM/5.00 mM/0.87 mM pH 9.0; borax/monopotassium phosphate:
0.28 mM/4.50 mM pH 8.0, 4.50 mM/0.13 mM pH 9.0; and sodium
carbonate/disodium bicarbonate: 0.40 mM/4.26 mM pH 9.2, 4.60
mM/0.76 mM pH 10.6).
Incubations of the EDB-fortified buffered solutions
were conducted at 62C. The remaining EDB at approximately


43
3 day intervals was determined by hexane extraction and GC
analysis on the PPG packed column. Rate constants for EDB
degradation were derived from data collected over 17 days.
Product Identification
Polk, Highlands, and Jackson County groundwater samples
and deionized water were fortified with EDB to a
concentration ca. 3.5 mg/L, including 1AC-EDB with a
resulting concentration of ca. 3500 dpm/mL. Incubations
were conducted at 73C until essentially all the EDB had
disappeared. At approximately 2 day intervals, analyses of
EDB, ethylene glycol, and bromide ion were performed. In
addition, samples were analyzed for purgeables by gas
chromatography/mass spectrometry (GC/MS). Within a purge
and trap device (Tekmar model ALS, Cincinatti, OH), helium
gas was bubbled at 8 mL/min through a 25 mL aliquot of a
sample for 22 min at ambient temperature and the effluent
directed onto Tenax adsorbent. The Tenax adsorbent was
heated to direct the purgeables into a GC, with a PPG column
and GC onditions used for EDB analysis. The GC was
interfaced with a Finnigan Model 4021 quadrupole GC/MS for
analysis. Mass spectra, scanning from m/e 50 to m/e 400,
were obtained in electron impact mode with an ionization
energy of 70 eV.
To measure the partitioning of ^C-activity of the
initial 1aC-EDB and its 1<1C-products, 1 mL aliquots of the
hexane and aqueous phases, after extraction, were pipetted
into 15 mL of scintillation liquid and counted. In


44
addition, 1 mL of the unextracted sample was analyzed in the
same manner.
Reactions with Aqueous Hydrogen Sulfide
Kinetics: Temperature and pH Dependence
Preparation of solutions
Experimental solutions were in 10 mM buffers prepared
with HPLC grade water. Before use, glassware and water were
autoclaved (121 C, 15 psi, 20 min) The buffers providing
solutions of pH 5, 7 and 9 consisted of the following
components: potassium acetate/acetic acid: 6.40 mM/0.360 mM
pH 5.0, potassium phthalate/sodium hydroxide: 2.36 mM/7.64
mM pH 5.0, sodium monohydrogen carbonate/hydrochloric acid:
8.17 mM/1.83 mM pH 7.0, disodium dihydrogen phosphate
heptahydrate/sodium monohydrogen phosphate monohydrate: 3.81
mM/6.19 mM pH 7.0, disodium borate decahydrate/hydrochloric
acid: 3.65/6.35 mM pH 9.0, disodium carbonate
decahydrate/hydrochloric acid: 0.53 mM/9.47 mM pH 9.0). The
resulting calculated ionic strengths of the solutions were
adjusted to n = 15 mM using 4.8 M KC1. The solutions were
deoxygenated by bubbling a stream of oxygen-free nitrogen
through them for at least 2 hr. The redox buffer, Titanium
(III) citrate of Zehnder and Wahrmann (1976), was used in
the experimental solutions to maintain an oxygen-free water
phase with high electron activity to inhibit oxidation of
sulfides. The redox buffer stock solution was perpared by
adding 3.5 mL of Titanium trichloride solution (20%/80%


45
water) to a final volume of 50 mL made up in 0.2 M sodium
citrate. One mL of the redox buffer stock solution was
added to each 99 mL of experimental preparation.
All subsequent manipulations of solutions and filling
of sample containers were done in an AtmosBag (Aldrich
Chemical) which contained an nitrogen atmosphere. The
oxygen concentration inside the Atmosbag remained below 0.05
mg/L. Oxygen concentration was monitored with an oxygen
sensor (Bio-Tek Instruments, Inc., Winooski, VT, Model
74223) .
Five hundred mL portions of the six buffer solutions
were fortified with methanolic stock solutions of 26.5 mM
EDB and 500 iCi/mL of 1AC-EDB (specific activity 55
mCi/mmol) to achieve final concentrations of 6.0 /M ca. EDB
and 5000 dpm/mL. Crystals of disodium sulfide nonane
hydrate were washed with deionized water and suction dried
on filter paper before being weighed and dissolved in the
buffered solutions. The final concentrations of total
sulfide were quantitated to be 500 140 and 1000 300 /M
(17 and 34 mg/L H2S(aq)) .
Using a 10 mL Repeat-o-syringe pipet (Fisher
Scientific) with a 20 gauge needle, 9 mL of the fortified
buffer solution were slowly transferred to sterile 10 mL
glass ampules (Wheaton, Millville, NJ). Each filled ampule
was purged with a stream of nitrogen, then quickly sealed by
an oxygen and natural gas flame. During this procedure, the
fortified solutions were kept chilled in an ice bath.


46
Analysis of solutions
Duplicates of each buffer and H2S(aq) concentrations were
analyzed for EDB concentration, uC-activity, pH, Eh, and
oxygen concentration. Sets of 14 ampules of each buffer and
H2S(aq) concentration were incubated at 25, 40, and 60C
1.0C in the dark. Ampules were analyzed at time intervals
based upon EDB degradation rates determined in preliminary
experiments.
At each time interval, ampules were allowed to come to
room temperature before being opened. Two mL of the sample
was withrawn for hexane extraction. One mL aliquots of both
the hexane phase and the aqueous phase were transferred to
separate scintillation vials containing 15 mL of liquid
scintillation fluid and counted. The remaining 1.0 mL of
hexane was transferred to a serum bottle for GC analysis of
EDB. The GC analysis was performed on a Hewlett Packard
5890 GC with a model 3392 integrator/plotter and a 7671A
autosampler and an 63Ni electron capture detector. Grob
technique injections were made onto a 25 m x 0.20 mm (film
thickness, 0.33 /M, HP ULtra 1) capillary column temperature
programed with an initial oven temperature of 40C for 2
min, then increased to 90C at 8C/min, and finally
increased at 30C/min to 200C. A carrier gas flow of
Argon/5% methane was maintained at 1 mL/min. A column purge
flow of 2 mL/min was activated at 1 min and a column make-up
was 30 mL/min. In addition, 1.0 mL of the original


47
incubated solution was transferred to 15 mL of liquid
scintillation fluid, shaken well, and then analyzed.
Total sulfide concentration was determined by the
procedure of Cline (1969), as modified by Millero (1987).
The method involves the formation of methylene blue from the
sulfide and reagent solution of N,N-dimethyl-p-phenylene-
diamine dihydrochloride and ferric chloride hexahydrate in
acidifided solution. Color was developed in 30 min and
absorbance was read at 670 nm with a Beckman DU8 spectro
photometer. Calibration solutions of concentrations ranging
from 4 fiM to 4 0 /nM H2S(aq) were prepared from a sodium sulfide
stock solution for each analysis. Stock solutions of soduim
sulfide were prepared by dissolving ca. 0.5 g of sodium
sulfide crystals that were washed with deionized water and
suctioned dry, in 100 mL of degassed deionized water. The
stock solutions were standardized by the iodometric
titration Standard Water snd Wastewater Method No. 427D
(American Public Health Association, 1980, p 476).
Concentrations of H2S(aq) in experimental solutions were
determined by comparison to a standard curve generated by
least-squares regression analysis of the assay response vs.
H2S(aq) concentration.
EDB apparent first-order degradation rate constants
were obtained by linear regression least squares fit of
plots of In percent EDB remaining vs time. The partitioning
of KC-activity of the initial UC-EDB and its 14C-products
were plotted versus time.


48
Product Identification
Hexane extracts from incubated of EDB and H2S{aq) in
buffered solutions from kinetic experiments and the same
buffer systems containing higher concentrations of
reactants, i.e., 60 /M EDB and 1000 or 2000 /M H2S(aq) were
subjected to GC and GC/MS analyses. Standard solutions of
11 commercially available sulfur-containing compounds in
hexane were chromatographed and subjected to mass
spectrometry for comparison with products formed in
experimental reaction solutions. Molecular formulae,
structure and suppliers of these standard compounds are
presented in Table 4.
Ethylene Dibromide in Sulfate Groundwater
Groundwater from wells in the Florida Ambient
Groundwater Network, which are known to have relatively
moderate to high concentrations of sulfate, were obtained
from officials of the South Florida Water Management
District. Clean 1 L brown-glass screw-top bottles with
Teflon-lined caps were filled in a manner which avoided
excessive contact with the air and were kept on ice in an
insulated cooler while being transported to the laboratory.
The pH, Eh and oxygen concentration of the samples were
measured. Three mL aliquots were then extracted with 1.0 mL
of hexane and the extracts analyzed by GC to determine if
any detectable compounds were initially present.
Three sets of EDB-fortified solutions were prepared
from each well water sample. Before fortification, one


Table 4. Commercially available sulfur-containing compounds used for product identification
COMPOUND
ABBREVIATION
CHEMICAL FORMULA/
FORMULA WEIGHT
STRUCTURAL
FORMULA
SUPPLIER/
PURITY
Ethanethiol
CAS #75-08-1
ET
c2h6s
62.13
CH3CH2SH
Kodak
(98%)
1-Butanethiol
CAS #109-79-5
BT
CH10S
90.16
CH3(CH2)3SH
Kodak
(95+%)
1,2-Ethanedithiol
CAS #540-63-6
EDT
C2H6S2
94.20
hsch2ch2sh
Kodak
(99.5%)
Cyclohexyl thiol
CAS #1569-69-3
CHT
C6H12S
116.23
1 1
CH2(CH2)4CHSH
Aldrich
NA
1,4-Dithiane
CAS #505-29-3
DT
C,H8S2
120.24
1 1
ch2ch2sch2ch2s
Aldrich
(97%)
Ethyl disulfide
CAS #110-81-6
EDS
cahioS2
122.25
ch3ch2ssch2ch3
Aldrich
(99%)
1,3-Dithiolane-2-
thione
CAS #822-38-8
DTT
C3H4Sj
136.26
1 1
ch2scssch2
Aldrich
(99%)
1,3,5-Trithiane
CAS #291-21-4
TT
CjH6S3
138.27
1 1
ch2sch2sch2s
Chem Service
(99%)
Butyldisulfide
CAS #629-45-8
BDS
C8H18S2
178.36
CH3(CH2)3SS (CH2)3CH3
Aldrich
(98%)
1,4,7-Trithiacy-
clononane
CAS #6573-11-1
TTCN
C6ll12S3
180.36
1 1
CH2CH2S (CH2) 2S (CH2) 2S
Aldrich
(98%)
1,4,7,10-Tetrathi-
acyclododecane
CAS #25423-56-7
TTCD
C8H16S4
240.47
1 1
CH2CH2S ( ch2 ) 2S ( ch2 ) 2S ( ch2 ) 2s
Aldrich
(97%)
NA = Data not available


50
portion of each groundwater sample was autoclaved for 20 min
(121C, 15 psi), another portion was degassed by bubbling
purified nitrogen gas through the water for approximately 2
hr, and a third portion of each water was left untreated.
Each portion of groundwater was fortified with a stock
solution of unlabeled EDB to give 1.5 mg/L EDB and also with
a stock solution of UC-EDB to give a concentration of
approximately 3000 dpm/mL. Sets of 10 mL ampules were
filled with about 8 mL of solution, the air space in the
ampule purged with a stream of purified nitrogen, and then
sealed by flame. The ampules were kept at 25"C in the dark
and periodically analyzed by GC for EDB concentration and
the appearance of extractable products. In addition, the
partitioning of UC-EDB and uC-products after hexane
extraction was determined using the method previously
described. One mL aliquots of the solutions were also
analyzed by liquid scintillation counting to check
containment of the EDB during incubation.
Organic Synthesis of a Sulfur Product
The aliphatic cyclic sulfur-containing compound,
1,2,5,6-tetrathiacyclooctane is not commercially available,
but its synthesis has been described by Goodrow et al.
(1982). The procedure involves slowly reacting a dilute
concentration of 1,2-ethanedithiol in chloroform with iodine
and triethylamine (reagents concentration of approximately
10 /iM, Goodrow et al., 1981).


RESULTS
Hydrolysis Reactions
Verification of Assay for Hydrolysis Products
Determination of EDB
Using the conditions previously described, EDB in
hexane extracts was quantitated using GC/EC by comparison of
unknowns to calibration curves consisting of four or five
standard solutions of EDB in hexane. The GC/EC response was
linear and reproducible over a range of 10 to 1200 pg of EDB
injected. Figure 2 shows a sample chromatogram and
calibration curve. The efficiency of extraction of EDB from
aqueous solutions into hexane was 95 to 100% over the
concentrations range using both labeled and unlabeled EDB.
Determination of ethylene glycol
Procedures for quantitation of formaldehyde and
ethylene glycol were validated using standard solutions para
formaldehyde and 37% formaldehyde solution or ethylene
glycol preparated in deionized water. In addition, UC-
labeled analytes were employed (formaldehyde 150 mCi/mg,
ethylene glycol 68 mCi/mg) for verifying the assay.
Since both analytes are very water-soluble and their 2-
nitrophenylhydrazone derivatives formed in the analysis are
extractable into hexane, partitioning of uC-activity was
51


Figure 2. Gas chromatogram, typical calibration curve and conditions for analysis of
EDB.


1,2-DIBROMOETHANE
63n¡ electron capture
15/o POLYPROPYLENE GLYCOL
95C 45 mL / MIN
750 pg/uL
d I I
0 2 4
MIN.
Ul
w


54
used to test efficiency of the assay. Because 14C-activity
can be measured at extremely low concentrations of labeled
material, a very sensitive assessment of efficiency was used
to test efficiency of the assay. Because 14C-activity can
be measured at extremely low concentrations of labeled
material, a very sensitive assessment of efficiency was
possible.
After derivatizing six solutions ranging from 17 to 689
/xg/L of 14C-formaldhyde, 86 to 98% was recovered in the
hexane extract. Performing the ethylene glycol procedure on
four solutions containing 288 to 2878 /ng/L of the compound
resulted in the recovery of 89% to 100% of the labeled
compound in the hexane extract.
Calibration curves for ethylene glycol were typically
constructed over a concentration range of 60 to 1500 /xg/L.
Resulting correlations of determination (r2) of linear
regression least squares analyses were larger than 0.99.
Figure 3 shows chromatograms of blanks and results of the
assay of ethylene glycol. Background concentrations of
formaldehyde between 10 and 50 /xg/L are common and must be
used to correct the results derived from the analysis of
unknown samples.
Kinetics: Temperature and pH Dependence
The disappearance of EDB in fortified groundwaters and
deionized water was followed over 22 days for incubation at
40, 50 and 60C, 17 days for incubation at 70C, and 6 days


Figure 3. Gas chromatograms after the 2-nitrophenylhydrazine derivatization assay of
unoxidized blank, oxidized blank and ethylene glycol (199 nq/h).


EC D RESPONSE
BLANK BLANK
(NO OXIDATION) (OXIDIZED)
199 ng / mL ETHYLENE
GLYCOL ASSAYED
ui


57
for incubations at 80C. These changes correspond to
decreases greater than 90% of initial concentrations of EDB
in the 80C incubations and approximately 20% decreases of
EDB at 40C. At intermediate temperatures, the degree of
degradation fell within this range. Linearity in plots of
the log % EDB concentration remaining vs. time demonstrated
apparent first-order degradation rates. The least-squares
regression coefficients of determination (r2) were greater
than 0.99 at higher temperatures and greater than 0.90 at
lower temperatures. The rate data from the Polk County
groundwater sample initially fortified to a concentration of
100 M9/L EDB are shown in Figure 4. If EDB degradation in
solution was an acid- or base catalyzed reaction, non-linear
semi-logarithmic plots of observed rate constants vs pH
should result. Figure 5 shows the observed rate constants
for the degradation of EDB in the groundwaters and deionized
water as a function of pH while incubated at 63C. Table 5
shows the observed rate constants for the laboratory EDB-
fortified waters. The rate constants differ only slightly
between the waters and indicate neither acid- nor base-
catalyzed degradation. The larger rate constants observed
at pH 5 and pH 8 as compared to those of pH 7 are not con
sistent with a pH dependent degradation process. The boric
acid buffer at pH 7.8 to 8.3 may have participated in EDB
degradation, thereby increasing the observed rate constant.
Buffers can catalyze hydrolysis even when present at low mM


Figure 4. Disappearence of EDB at elevated temperatures in Polk County groundwater
initially containing 100 ug/L EDB.


/o EDB Remaining
EDB Degradation in Groundwater at Various Temperatures


Figure 5. Observed EDB degradation rate constants as a function of pH in buffered
solutions (0.005 M 63C) Buffers are identified in Table 5.


log k (obs)
Polk water
+
Highlands water

Jackson water
Q
Deionized water
a- -
4 5 6 7 8 9
PH
CTi


62
Table 5. The effect of pH on the EDB degradation rate at 63"C
and initial EDB concentration of 100 /ig/L.
PH
Buffer3
103k (hr1)b
(t1/2, hr)
103kSD
Polk
Hiahlands
Jackson
Deion.
4.0-4.4
a
2.31
2.31
2.34
2.48
2.360.13
(301)
(302)
(298)
(280)
4.0-4.9
b
2.94
2.61
2.45
2.54
2.6310.29
(236)
(266)
(283)
(273)
4.7-5.3
b
2.84
2.56
3.46
3.10
3.2310.45
(208)
(225)
(200)
(225)
5.3-5.6
a
2.41
2.44
3.47
3.10
2.4010.10
(288)
(288)
(287)
(295)
6.1-6.5
c
2.45
2.98
2.64
2.83
2.7310.23
(283)
(233)
(263)
(285)
7.6-7.7
d
2.68
2.68
2.52
2.63
2.9510.62
(259)
(259)
(275)
(263)
7.8-7.9
e
4.39
3.96
3.83
4.17
4.1710.38
(158)
(175)
(181)
(166)
8.0-8.3
f
3.76
2.81
3.56
3.62
3.4410.44
(266)
(247)
(195)
(191)
8.6-9.0
g
3.07
2.61
2.41
2.95
2.9510.48
(224)
(267)
(288)
(235)
a0.005 M buffers: a = borax/succinic acid
b = potassium phthalate
c = borax/succinic acid
d = borax/phosphate
e,f = boric acid
g = carbonate
aApparent First-order rate constant for degradation of EDB
Average of replicate kinetic runs with 6 data points each
Half-life, t1/2 = 0.693/k
CA11 samples in pH range, n=8


63
concentrations (Perdue and Wolfe, 1983). The observed
first-order EDB degradation rates were used to construct
Arrhenius plots like the one shown in Figure 6. The data
shown are from EDB degradation in Polk County groundwater.
The least-squares regression coefficients of determination
(r2) for these plots ranged from 0.97 to 0.99 for all the
EDB-fortified waters tested. The resulting Arrhenius
kinetic parameters were used to make estimates of EDB
degradation rates at ambient groundwater temperatures. In
Table 6, the extrapolated kinetic parameters derived from
these data are shown for 22C, a common groundwater
temperature in Florida. The kinetic parameters do not
significantly vary with the source of the water or with the
initial concentration of EDB. At 22C in the waters tested,
the predicted half-life (t 1/2) ranges from 259 to 772 days.
The activation energy ranges from 19.1 to 24.3 kcal mol'1.
The variation among the data is fairly large, with standard
deviations generally ranging from 12 to 20% of their
respective means, except for J10 where the standard
deviation is 58% of the mean. Since the extrapolated values
for rate constants at ambient temperatures are derived from
relatively few data points a fair degree of error is
expected. Sources of error in rate constant may arise from
small deviations in temperature of experimental incubations
and random error (Harris, 1982; Maybey and Mill, 1978).


Figure 6. Arrhenius plot illustrating hydrolysis of EDB in Polk County groundwater
initially containing 100 ug/L EDB.


Arrhenius Plot for Hydrolysis of EDB
CTi
(J1


66
Table 6. EDB degradation kinetic parameters in
solutions studied as predicted by Arrhenius kinetics plots.
Extrapolated values for 22C are shown.
Samle3
10 k
22C. id'1}
22 C
,'(d'1)
Ea (kcal
mol'1}
Log i
di
)
P10
2.76
0.41
259
+
35
19.6
0.2
12.2
+
0.5
P100
1.61
0.19
434
+
47
20.9
0.4
12.7
+
0.2
H10
0.64
0.38
772
+
94
24.2
0.8
14.9

0.6
H100
2.33
0.57
309
+
67
19.1
0.6
11.6
+
0.4
J10
1.52
0.65
547
317
21.1
2.2
12.1
+
0.3
J100
1.93
0.36
369
+
69
19.7
0.6
11.9
+
0.4
DW10
2.15
0.25
326
+
38
19.6
0.6
11.8
+
1.7
DW100
2.15
0.25
326
+
38
19.6
0.6
11.7
+
1.7
aP=Polk county groundwater
H=Highlands county groundwater
J=Jackson county groundwater
DW = deionized water
10 = 10 ng/li, concentration of EDB fortification
100= 100 /g/L, concentration of EDB fortification
b Mean of four replicate runs, except for two replicates
of DW samples;
mean of pseudo-first order rate constant standard
deviation, except DW is mean range of replicates
c Mean standard deviation of half-lives of EDB in days,
except DW is mean range of replicates
d Mean standard deviation of Arrhenius activation energy,
except DW is mean range of replicates
Mean standard deviation of frequency factor, except DW
is the mean range of replicates
e


67
Product Identification
In experiments using 14C-EDB conducted at elevated
temperatures, the decline in 14C-activity in the hexane
phase, determined after extraction of incubated solutions,
closely paralleled the degradation of EDB, as quantitated by
GC/EC (Figure 7). These observations are highly
reproducible, as shown in the results from simultaneous
quantitation and partitioning of C-EDB and C-products
during incubation at 80C (Table 7) At the completion of
the experiment, the total l4C-activity in the solutions
ranged from 92 to 99 percent of the initial activity. This
finding indicates that no EDB or product was lost during the
experiment and that no products volatilized. The next
experiments employed solutions containing higher initial
concentrations of EDB (ca. 3.5 mg/L) than in the prior
experiments for the purpose of quantitating the water-
soluble products formed, i.e., bromide ion and ethylene
glycol (Figures 8a, 8b and 8c). Total 14C-activity was also
quantitated along with the hexane/aqueous partitioning of
14C-activity during incubation of the EDB-fortified
groundwater and deionized water. During the 17 day
incubations conducted at 73C, the amounts of bromide ion
and ethylene glycol together accounted for 60 to 70% of the
initial EDB present. The extent of EDB degradation in these
incubation was approximately 8 or 9 half-lives. As in
previous experiments, the partitioning of 14C-activity into


Figure 7. Partitioning of uC-activity (UC-EDB and UC-
products by liquid scintillation counting) during EDB
degradation at 80C.


PERCENT EDB OR 14C-ACTIVITY REMAINING
69
EDB CONCENTRATION 1
EDB CONCENTRATION 2
0
TOTAL 14C-ACTIVITY 1
*
TOTAL 14C-ACTIVITY 2
HEXANE 14C-ACTIVITY 1
HEXANE 14C-ACTIVITY 2
B
AQUEOUS 14C-AQUEOUS1
AQUEOUS 14C-AQUEOUS 2
A


70
Table 7. Simultaneous quantitation of EDB (GC/EC) and partitioning
of 14C-activity (UC-EDB and 14C-products by liquid scintillation
counting) in dilute solution during degradation at 80 C.
Time/Samole3
[EDB]
(liq/Ll.
KC
in Hexane
(dom/mL)
UC
in Aqueous
(dom/mL)
UC
Total
(dom/mL)
0
Hour
A1
56.4
150774(85)
19815(11)
177950
A2
59.8
150740(84)
23425(13)
178550
B1
28.9
77950(86)
10535(12)
90700
B2
29.1
78221(88)
10495(12)
88970
18
Hour
A1
41.5(74)b
114456(64)
55464(31)
178230(100)
A2
41.9(70)
115752(64)
55860(31)
181680(102)
B1
21.0(73)
53918(60)
30415(34)
89940(99)
B2
20.1(69)
58349(65)
28965(32)
89270(100)
44
Hour
A1
29.5(52)
83216(48)
83315(48)
175190(98)
A2
29.5(49)
82673(47)
84900(48)
176560(99)
B1
14.5(50)
42196(48)
43405(49)
88590(98)
B2
13.8(47)
41330(47)
42765(49)
87360(96)
80
Hour
A1
16.3(29)
51285(30)
117290(68)
172890(97)
A2
16.5(28)
48424(28)
117025(67)
175880(99)
B1
8.1(28)
23402(27)
59705(69)
87110(96)
B2
7.8(26)
23942(29)
56695(69)
82050(92)
EDB Degradation Kinetic Data (first-order plot)
Apparent rate
Regression Equation constant (hr'1)
A1
y=
-0.00667X
+
2.00
r=
-.9990
1.54
X
10
A2
y=
-0.00689X
+
1.99
r2=
-.9989
1.59
X
10
B1
y=
-0.00679X
+
1.99
r2=
-.9994
1.56
X
10
B2
y=
-0.00699X
+
1.99
r2=
-.9983
1.61
X
10
a10 mL aliquots of 100 mL samples are taken for each analysis
interval; samples 1 and 2 are duplicates
bPercent of 0 hour measurement in parenthesis


Figure 8. Partitioning of UC-EDB and 14C-products and
guantitation of EDB, ethylene glycol, and bromide during
incubation in Florida groundwater and deionized water.
Each point is an average of replicate measurements.
8a. EDB-fortifed Polk and Highlands groundwater incubated
at 73C.
EDB
TOTAL 14C
--0--
14C-HEXANE
*
14C-WATER
A
ETHYLENE GLYCOL
BROMIDE ION


CONCENTRATION (ng/mL) or 14C (dpm/mL)
72


Figure 8 continued.
8b. EDB-fortified Jackson groundwater and deionized water
incubated at 73C.
EDB
TOTAL14C
*-e~-
14C-HEXANE
*
14C-WATER
A
ETHYLENE GLYCOL
BROMIDE ION


CONCENTRATION (ng/mL) or 14C (dpm/mL)
74
JACKSON CO. GROUNDWATER


Figure 8 continued.
8c
EDB-fortified deionized water incubated at 80C


CONC. (ppb), C ACTIVITY (cpm/mL)
DEGRADATION IN AQUEOUS SOLUTION AT 80 C
BROMIDE ION
A 14C LEFT IN WATER
ETHYLENE GLYCOL
A 14C IN HEXANE PHASE
O 1,2-DI BROMOETH ANE
TIME (DAYS)
cr\


77
the aqueous phase after extraction closely paralleled the
decline in EDB concentration. Similar patterns of trans
formation of EDB were seen in all three fortified ground-
waters and in deionized water. Figure 8c shows the pattern
of EDB transformation during an incubation at a higher
temperature (80C) which was observed for a longer time
period (27 days) in deionized water. In this experiment,
the extent of conversion of EDB to bromide ion and ethylene
glycol ranged between 70 and 90%. Further examination of
extractions of aliquots from solutions in this experiment
did not reveal either additional brominated products of EDB
or intermediates in the conversion of EDB to bromide ion and
ethylene glycol. Purge-and-trap GC/MS analyses of aqueous
aliquots detected only trace quantities of 3- and 5-member
hydrocarbon compounds and remaining EDB.
Vinyl bromide could be formed from EDB if EDB were
reductively dehalogenated. This compound was found by Vogel
and Reinhard (1986) in pentane extracts of incubated aqueous
EDB solutions. Although it could not be detected in any of
the solutions or extracted by GC/EC or by purge-and-trap
GC/MS in this study. Under the GC/EC conditions used in
this study, the detection limit is at least 1000 times less
sensitive for vinyl bromide compared to EDB. If vinyl
bromide were formed in the present study, however, 14C-vinyl
bromide would have partitioned into hexaxe upon extraction.
There was no indication that this occurred. Injections on


78
GC/EC were made of the hexane phase and aqueous phases of
three replicate extractions of deionized water containing
1000 mg/L vinyl bromide. Vinyl bromide was only found in
the hexane phase and not in the aqueous phase.
Extraction of 2-bromoethanol from dilute aqueous
solutions was 30 to 40% efficient. Furthermore, GC/EC
detection of this compound was also much less sensitive than
EDB; at least 100 times less than EDB.
Reactions with Aqueous Hydrogen Sulfide
Kinetics: Temperature and pH Dependence
During incubations at 25, 40 and 60C, the
disappearance of EDB from pH and redox buffered solutions
was examined along with the partitioning of KC-EDB and UC-
products after hexane extraction (Figures 9a, 9b and 9c).
These control solutions, which did not contain H2S(aq), were
studied over 237 days at 25C, 194 days at 40C and for 105
days at 60C. At 25C, neither the concentration of EDB nor
the partitioning of the 14C-EDB between the hexane and
aqueous phases changed noticeably at pH 5, 7, or 9. At 40
and 60C, the disappearance of EDB was paralleled by the
changes in partitioning of the uC-activity. This trans
formation of EDB to water-soluble products in pH and redox
buffered solutions was also observed in the groundwater and
deionized water experiments discussed previously.


Figure 9. Degradation of EDB and partitioning of UC-
products in buffered reducing solutions as a function of pH
and temperature. Each point is the average of duplicate
analyses.
9a. Solutions buffered at pH 5.
PHTHALATE BUFFER
EDB

ACETATE BUFFER
EDB
PHTHALATE BUFFER
HEXANE C-14

ACETATE BUFFER
HEXANE C-14
PHTHALATE BUFFER
AQUEOUS C-14

ACETATE BUFFER
AQUEOUS C-14


TIME (DAYS)
PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
1
CD
o
6 uM EDB
pH 5


Figure 9 continued.
9b. Solutions buffered at pH 7.
CARBONATE BUFFER
EDB
PHOSPHATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14

PHOSPHATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14

PHOSPHATE BUFFER
AQUEOUS C-14


PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
03
to
6 uM EDB
pH 7


Figure 9 continued.
9c. Solutions buffered at pH 9.
CARBONATE BUFFER
EDB

BORATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
BORATE BUFFER
HEXANE C-14
A
CARBONATE BUFFER
AQUEOUS C-14

BORATE BUFFER
AQUEOUS C-14


PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
:>
IT
§
o
O
oo
6 uM EDB
pH 9


85
The type of pH buffer system (phthalate versus acetate;
carbonate versus phosphate) had little effect on the
results. One exception to this trend was the pH 9 buffer
system (borate versus carbonate). A rate enhancement-effect
of borate (but not carbonate) on the degradation of EDB was
also observed in the previous study of the effect of pH on
EDB hydrolysis.
Where EDB was monitored through more than one half-
life, its degradation followed apparent first-order decay.
EDB, initially present in a concentration of 6 M, was no
longer detectable at 100 days in each of the three pH
buffering systems held at 60C. In solutions also
containing ca. 500 or 1000 M H2S(aq)/ very different patterns
of EDB's transformation emerged (Figures 10a lOf) and are
described below. These solutions contained the same
composition of pH and redox buffers as the controls
described above. These solutions were held at 25C and
monitored for 254 days at pH 5 and 7 and for 150 days at pH
9. At 40C, solutions of pH 5 and 7 were monitored for 93
days and for 82 days at pH 9. At 60C, the solutions at pH
5 and 7 were watched for 62 days and for 19 days at pH 9.
At the start of the incubation of these solutions, the
dissolved oxygen was less than 0.07 ppm. The initial redox
potentials for the solutions buffered at pH 5, 7 and 9
ranged from -240 to -258 mV, -238 to -291 mV and -284 to -
345 mV, respectively. The first notable difference produced
by the addition of H2S(aq)
was that EDB was transformed in


Figure 10. Degradation of EDB and partitioning of 14C-
products in buffered reducing solutions containing H2S(aq)
as a function of pH and temperature. Each point is the
average of duplicate analyses with relative differences less
than 3%.
10a. Solutions buffered at pH 5 with an H2S(aq) concentration
of ca. 500tM.
PHTH ALATE BUFFER
EDB
ACETATE BUFFER
EDB
PHTHALATE BUFFER
HEXANE C-14

ACETATE BUFFER
HEXANE C-14
PHTHALATE BUFFER
AQUEOUS C-14

ACETATE BUFFER
AQUEOUS C-14


PERCENTAGE EDB REMAINING
OR
14C PARTITIONING
03
^0
6 uM EDB, 500 uM
pH 5


Figure 10 continued.
10b. Solutions buffered at pH 7 with an H2S(aq)
of ca. 500/uM.
CARBONATE BUFFER
EDB
PHOSPHATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
A
PHOSPHATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14
PHOSPHATE BUFFER
AQUEOUS C-14
concentration


PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
CO
CD
6 uM EDB, 500 uM
pH 7


Figure 10 continued.
10c. Solutions buffered at pH 9 with an H,S, ,
of ca. 500/xM. 2 (aq)
CARBONATE BUFFER
EDB
BORATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
BORATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14

BORATE BUFFER
AQUEOUS C-14
concentration


TIME (DAYS)
PERCENTAGE EDB REMAINING
OR
14C PARTITIONING
SS8ogSS8
cn
6 uM EDB, 500 uM
pH 9


Full Text
TRANSFORMATIONS OF ETHYLENE DIBROMIDE IN AQUEOUS SYSTEMS
AND GROUNDWATER
By
RANDY ALAN WEINTRAUB
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1989

ACKNOWLEDGMENTS
For valuable advice and guidance on this work, I thank
Dr. H. Anson Moye, Chairman of my Supervisory Committee, and
the other members of the Committee: Dr. Willis B. Wheeler,
Dr. Ross D. Brown, Jr., Dr. Joseph J. Delfino, and Dr. Lori
0. Lim.
I appreciate the knowledgeable assistance from Dr.
Gabriel Bitton, Dr. John P. Toth in collecting mass spectra,
and Kenneth M. Jones in advising me on organic synthesis. I
thank Dr. Barbara Ameer for editorial advice and assistance,
Mrs. Elaine M. Peeples for construction of tables of data,
and Ms. Susan Scherer for professional drawings. Collection
of groundwater samples was made possible through
collaboration with Mr. Dennis Bacon and Mr. Geoffrey Herr,
hydrogeologists with the Water Quality Division of the South
Florida Water Management District. I also thank Dr.
Geoffrey Watts of the Florida Department of Environmental
Regulation for his helpful discussion and interest in the
reactions of ethylene dibromide and hydrogen sulfide.
ii

TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS ii
KEY TO SYMBOLS AND ABBREVIATIONS v
ABSTRACT vii
INTRODUCTION 1
LITERATURE REVIEW 5
Groundwater Contamination by Pesticides 5
Ethylene Dibromide 7
Commercial Use 7
Toxicity 8
Chemical and Physical Properties 11
Ethylene Dibromide in Florida
Groundwater and Soil 11
Sorption to Soil 17
Degradation in Soil and Water 19
Risk Factors for Groundwater Contamination 27
MATERIALS AND METHODS 29
Materials 33
Methods 3 3
Ethylene Dibromide and Product
Identification and Quantitation
by Gas Chromatography and
Spectrophotometry 3 3
Liquid Scintillation Counting of
rtC-ethylene Dibromide 37
Gas Chromatography and Mass Spectrometry
for Sulfur Product Identification 38
Oxygen, Redox, and pH Measurements 3 9
Hydrolysis Reactions 40
Kinetics: Temperature and pH Dependence 4 0
Product Identification 43
iii

page
Reactions with Aqueous Hydrogen Sulfide 44
Kinetics: Temperature and pH Dependence 4 4
Product Identification 48
Ethylene Dibromide in
Sulfate Groundwater 48
Organic Synthesis of a Sulfur Product 50
RESULTS 51
Hydrolysis Reactions 51
Verification of Assay for Hydrolysis
Products 51
Kinetics: Temperature and pH Dependence 51
Product Identification 67
Reactions with Aqueous Hydrogen Sulfide 77
Kinetics: Temperature and pH Dependence 77
Product Identification 108
Ethylene Dibromide in
Sulfate Groundwater 129
DISCUSSION 138
Analytical Methods 138
Hydrolysis Reactions 138
Reactions with Aqueous Hydrogen Sulfide 141
SUMMARY AND CONCLUSIONS 150
APPENDIX A ANALYSES OF GROUNDWATER FOR
HYDROLYSIS STUDIES 154
APPENDIX B ANALYSES OF GROUNDWATER FOR HYDROGEN
DEGRADATION SULFIDE STUDIES 156
APPENDIX C MASS SPECTRA OF SULFUR-CONTAINING COMPOUNDS
IN STUDY 158
APPENDIX D MICROTOXâ„¢ ASSAY EVALUATION OF PRODUCTS.... 175
REFERENCES 179
BIOGRAPHICAL SKETCH 189
iv

KEY TO SYMBOLS AND ABBREVIATIONS
ACS American Chemical Society
aq aqueous phase
BDS butyldisulfide
°C degrees Celsius
1AC- carbon 14 isotope labeled chemical
ca. approximately
CHT cyclohexylthiol
cm centimeter
cpm counts per minunte
d day
dpm disintegrations per minute
DT 1,4-dithiane
DTT 1,3-dithiolane-2-thione
EDB ethylene dibromide
EPA Environmental Protection Agency
ET 1,2-ethanedithiol
eV electron volts
g gram
hr hour
H2S hydrogen sulfide
i.d. inside diameter
°K degrees Kelvin
v

KEY TO SYMBOLS AND ABBREVIATIONS
(Continued)
L liter
M mole per liter
m meter
mCi microcurie
m/e mass-to-charge ratio
min minute
mL milliliter
mol mole
ND none detected
pg picogram
T temperature
TT 1.3.5-trithiane
TTCD 1,4,7,10-tertathiacyclododecane
TTCH 1,2,5-trithiacycloheptane
TTCO 1,2,5,6-tetrathiacyclooctane
TTCP 1,2,3-trithiacycolpentane
U- uniformly radiolabeled chemical
nq microgram
fj. M micromole
yr year
vi

Abstract of Dissertation Presented to the Graduate School
at the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
TRANSFORMATIONS OF ETHYLENE DIBROMIDE IN AQUEOUS SYSTEMS
AND GROUND WATER
By
Randy Alan Weintraub
December 1989
Chairman: Hugh Anson Moye, Ph.D.
Major Department: Food Science and Human Nutrition
Registration of a chemical for use as a pesticide today
requires thorough study of the compound's environmental fate
in water, soil, and air to determine if classification re¬
stricting its use is needed. During the 30-year history of
"successful" soil fumigation with ethylene dibromide (EDB,
1,2-dibromoethane), its environmental fate was not closely
studied. This nematicide was not recognized as environ¬
mentally persistent or a public health risk until 1983, when
its agricultural use was suspended in the United States.
In this research, the transformations of EDB were
examined both in buffered aqueous solutions and in ground-
water from several locations in Florida. Experiments were
conducted between 25 and 70°C to establish temperature-
dependent rate constants and to expedite the reactions.
The ethylene dibromide and products were analyzed by packed
vii

and capillary gas chromatography (GC), liquid scintillation
counting, and a colorimetric assay. The EDB is converted to
ethylene glycol and bromide ion in aqueous solutions and in
abiotic aerobic groundwaters. The rate of degradation of
EDB is dependent upon temperature but independent of pH
between 5 and 9. Extrapolating experimental results to the
average ground- water temperature in Florida of 22°C, the
degra- dation half-life of EDB in the tested groundwaters is
1.5 to 2 years.
An alternative transformation of EDB occurs under
anaerobic reducing conditions in groundwater where aqueous
hydrogen sulfide (H2S(aq)) is commonly present. Transfor¬
mation by H2S(aq) was not previously recognized as a poten¬
tially important reaction with pesticides. The rate of
degradation of EDB under these conditions is increased and
dependent upon temperature, pH, and H2S(aq) concentration.
The sulfur-containing products are 1,2-ethanedithiol and
saturated cyclic rings of one, two or four ethylene units
and two, three, or four sulfur atoms. Their structural
identity was elucidated with mass spectrometry (MS) and GC
retention times of products relative to known analytical
standards. One commercially unavailable cyclic disulfide
compound was synthesized and used to positively confirm the
MS and GC findings. Toxicity assessment of sulfur-products,
by Microtox screening assay, suggests increased toxicity
relative to parent compound or to its hydrolysis products.
viii

INTRODUCTION
The reported episodes of groundwater contamination by
landfills and septic tanks, hazardous waste sites,
petroleum-based hydrocarbons, halogenated hydrocarbons, and
pesticides have dramatically increased in the United States
in recent years (Pye and Patrick, 1983). These reports were
followed by efforts to address the problem at both the
federal and state levels. An official report from the U.S.
Environmental Protection Agency (EPA) in 1984 stated that
"significant achievements have been made nationally in the
protection and enhancement of water guality" by controlling
the many point sources of pollution (U.S. EPA, 1984a, p. 2).
This report also recognized the contributions of nonpoint
sources to contamination of groundwater. The later term
refers to pollutants which originate principally from
agricultural activities, runoff from urban lands, and mining
activities. In an Association of State and Interstate Water
Pollution Control Administrator's Nonpoint Source Pollution
Survey, 78% of the states indicated that the magnitude of
nonpoint source pollution problems was at least as great as
that of point source problems (U.S. EPA, 1984b). In all
regions studied by the EPA, agricultural activities in
particular were identified as the most widespread nonpoint
1

2
source of groundwater contamination, affecting 50% of the
waters in 72% of states (U.S. EPA, 1984b). The severity of
the problem depends to a large extent upon local factors
including the hydrogeology of the region, agricultural
practices, rainfall, terrain, and the particular chemicals
that are dispersed into the environment.
Of all the agricultural pollutants of water, pesticides
are the compounds posing the greatest toxicologic hazard.
Of particular interest recently, and the focus of this
research, is the nematicide fumigant, 1,2-dibromoethane or
ethylene dibromide (EDB). It had been widely used in many
states. By 1984, the chemical had been detected in the
groundwater of at least six states. While EDB was first
registered for agricultural use by the U.S. Department of
Agriculture in 1948, only relatively recently has extensive
information been available on the toxicological properties
of this chemical.
The literature review which follows presents current
knowledge of the persistence, fate, and transport of EDB in
the environment and the evolution of the discovery of this
problem. The state of Florida has had particular interest
in this episode for several reasons that will be discussed.
Close study of the history of EDB usage underscores the
urgency of evaluating and amending current practices that
may lead to groundwater contamination, especially from
unexpected nonpoint sources such as pesticides. Prior to

3
discoveries of EDB in groundwater, the chemical was thought
to be sufficiently volatile and of sufficiently low water
solubility to not present an environmental hazard. This
belief is reflected in a report prepared for EPA in 1975
which states "ethylene dibromide is not believed to
accumulate in the environment. Limited information suggests
that it degrades at moderate rates in both water and soil"
(Going and Long, 1975, p lb). Review of the literature
suggests that only until relatively recently was the
movement and accumulation of EDB in the subsurface of
interest. Beckman et al. attributed increased bromide
content in various crops to soil pre-treatment with nemato-
cidal compounds, EDB and 1,2-dibromo-3-chloropropane, which
were "readily degradable," liberating inorganic bromide into
the soil (Beckman et al., 1967, p 138).
The detection of EDB in groundwater came about through
increased sensitivity of modern analytical chemistry
instrumentation and a renewal of concern for environmental
contamination by man's daily practices. In the 1960s,
residual EDB was determined by measuring inorganic bromide
in soil and plant tissue (Beckman et al., 1967; Mapes and
Shrader, 1957). These indirect methods involved combustion
or oxidation of EDB followed by assay of bromide by
titration or polarography. Determination of greater than 1
to 10 parts per million (ppm) was possible; however, these
values were highly dependent upon the care taken to

4
establish the background halide content. In the 1980s, EDB
is detected directly in agricultural commodities (Rains and
Holder, 1981; Morris and Rippon, 1982) and environmental
matrices (Amin and Narang, 1985; Marti et al., 1984) at
concentrations below 10 parts per billion (ppb). These
methods employ purge and trap gas chromatography and mass
spectrometry for achieving lower detection limits and
identity confirmation.
With the benefit of modern analytical chemistry
instrumentation, this study was designed to achieve the
following goals; (1) to describe the kinetics of
degradation of EDB in buffered aqueous systems and in
groundwater, (2) to elucidate the major products of EDB
degradation in groundwater, and (3) to investigate EDB
degradation occurring in buffered aqueous systems and
groundwater in the presence of aqueous hydrogen sulfide
(H2S(aq)) , a reactive, natural component in groundwater.

LITERATURE REVIEW
Groundwater Contamination by Pesticides
The Environmental Protection Agency recognized the need
for investigation of groundwater contamination by pesticides
in 1979. The first pesticides discovered in groundwater of
various states were 1,2-dibromo-3-chloropropane (DBCP) and
aldicarb, the later occurring mostly as the sulfone or
sulfoxide (Cohen et al., 1984). Over 50 different
pesticides were found in ground-water basins of California,
one of the largest users of pesticides in the nation. One
of the best known incidences was the discovery of DBCP in
hundreds of wells in the San Joaguin Valley (Litwin et al.,
1983). In 24 other states, a total of 19 pesticides were
detected in groundwater (U.S. EPA, 1987b).
The importance of the safety of groundwater is evident
when faced with the fact that it provides at least half the
potable water to the U.S. population (Pye and Patrick,
1983). The gravity of the situation may be even more acute
in locations such as Florida, where groundwater provides 92%
of the population's potable water supply (Fernald and
Patton, 1984; U.S. EPA, 1987a).
The state of California, in collaboration with the U.S.
EPA in the early 1980s, studied the extent and mechanism of
5

6
groundwater contamination by four widely used pesticides:
DBCP, EDB, simazine, and carbofuran. EDB was found at
concentrations between 0.1 and 31.1 ppb in soils at depths
greater than three meters. Numerous wells were also found
to be contaminated (Zalkin et al., 1983). Meanwhile, in the
summer of 1982, irrigation wells in Georgia were found to
contain EDB at levels as high as 100 ppb (Marti et al.,
1984). The greatest extent of contamination, however, was
not uncovered until the state of Florida began monitoring
groundwater wells in the summer of 1983. In Florida,
contamination was found to exist throughout much of the
heavily farmed regions of the state. Concentrations in
private wells as high as 900 ppb were reported1. Florida
responded rapidly by suspending the use of this agrochemical
in July, 1983 (Florida Statutes, 1983). The EPA followed
this action two months later by imposing a nationwide ban on
all agricultural uses of EDB (Fed. Regist., 1983). State
environmental regulatory agencies of South Carolina,
Washington, Arizona, Massachusetts, and Connecticut have
subsequently reported EDB contamination of groundwater. The
range of typical EDB concentrations in these states as well
as California, Georgia, and Florida is 0.05 - 20 ppb (U.S.
EPA, 1987b).
:Aller, C. Bureau Chief, Groundwater Protection Division,
Florida Department of Environmental Regulation, personal
communication, March 12, 1985.

7
Ethylene Dibromide
Commercial Use
The EPA estimates that of the 750 to 790 thousand
metric tons (one metric ton equals one thousand Kg) of EDB
formerly produced annually in the United States, only 29 to
33 thousand metric tons were used in agriculture (U.S. EPA,
1983). The major industrial use was as an anti-knock lead¬
scavenging additive to leaded gasoline, constituting
approximately 0.03% by weight of leaded gasoline. The major
agricultural use (about 90%) was as a soil fumigant. Other
registered agricultural uses included post-harvest
fumigation, spot fumigation of grain milling machinery, and
several other low volume uses (U.S. EPA, 1983). Its
insecticidal and nematocidal properties were known in the
mid-1920s. Federal pesticide registration for its use as a
soil and grain fumigant was granted in the 1950s. EPA
estimates that approximately one million acres in the U.S.
were treated annually for nematode control with nearly 57
thousand metric tons of EDB. The largest portion of this
was employed in farming of soybean, cotton and peanuts, with
lesser amounts used in farming other crops. The greatest
amounts of EDB have been used in the southeastern United
States, where these crops predominate. EDB application
increased somewhat when a closely related fumigant, DBCP,
was banned in 1978.

8
Toxicity
The National Cancer Institute in 1973 first reported
that EDB produces stomach cancer in rats and mice with a
very short latent period (Olson et al., 1973). The chemical
was mutagenic at relatively high doses (0.60, 0.092
revertants/nmol) in the Ames Salmonella reversion assay.
The mutagenicity is not enhanced by addition of rat liver
microsomal extract (McCann et al., 1975; Moriya et al.,
1983). EDB induced lethal point mutations in fruit flies
(Buselmaier et al., 1974) and was acutely toxic in all
animals tested, with LD50 values ranging from 50 mg/Kg in
rabbits to 450 mg/Kg in female mice (National Cancer
Institute, 1978).
The toxic effects of EDB have been postulated to
originate via either of its two known metabolic routes. A
mixed function oxidase (P-450) mediated mechanism through
the intermediate, bromoacetaldehyde, is followed by
conjugation with glutathione (GSH) which is further
metabolized to the water-soluble mercapturic derivative.
The second route involves direct conjugation to GSH, to
produce the half-mustard, S-2-bromoethyl-glutathione. This
reaction is followed by formation of the highly reactive
thiiranium ion, which may also be further metabolized to the
mecapturic acid water-soluble form (van Bladeren et al.,
1980; Shih and Hill, 1981). The later route has been
implicated in producing the most profound toxic effects.

9
Genotoxic damage involves irreversible binding to DNA (Hill
and Shih, 1978) and more specifically, as a S-[2-(N7-
Guanyl)ethyl]glutathione adduct (Inskeep et al., 1986).
These reactions are dependent on cytosolic components and
reduced glutathione (Ozawa and Guengerich, 1983; Inskeep and
Guengerich, 1984).
Early indications of the toxicity of EDB prompted the
Rebuttable Presumption Against Registration (RPAR)
proceedings by EPA in December, 1977 (Fed. Regist., 1977).
The EPA's final decision to suspend usage of this chemical
was based in part upon the subseguent toxicologic findings
and estimates of cancer risks associated with discoveries of
EDB residues in the diet and drinking water. EPA's Cancer
Assessment Group evaluated the increased cancer risk from
EDB-contaminated drinking water using a one-hit model with
"Weibull" timing (U.S. EPA, 1983, p 79). The resulting
risks are shown in Table 1.
In one of two human epidemiological studies published,
mortality data from workers exposed to the chemical in two
EDB production plants were inconclusive in defining the
relationship between EDB and human cancer (Ott et al.,
1980). One notable conclusion, however, was that far fewer
human neoplasms were observed than what was extrapolated
from animal carcinogenicity studies (Ott et al., 1980).
In the second study, a decrease in fertility of men
occupationally exposed to EDB was significant in one of four
workplaces studied (Wong et al., 1979).

Table 1. U.S. EPA estimates of cancer risk for EDB
groundwater contamination.
10
CONCENTRATION
of EDB, ppb
Lua/L)
0.02
0.1
5.0
100.0
LIFETIME CANCER RISK3
0.00005
0.00015
0.0075
0.15
Source: U.S. EPA, 1983.
%
3 Assumes consumption of 2 L of water per day, 60 Kg adult,
for 70 years. These probabilities of observation of cancer
are the additional risks estimated for a lifetime exposure.

11
Evaluating the evidence for EDB carcinogenicity, the
International Agency for Research on Cancer and the American
Medical Association find sufficient evidence from animal
data but inadequate evidence for humans (O'Neill, 1985;
Council on Scientific Affairs, 1988). EPA classifies EDB as
a probable human carcinogen (group B2). Group B2 compounds
are compounds with limited human epidemiologic studies and
sufficient evidence from animal studies.
Chemical and Physical Properties
EDB is the saturated vicinal dibrominated product of
ethylene. It is moderately soluble in water (4300 ppm or
22.9 mM at 30°C), compared to most pesticides and is fairly
volatile (11.6 mm Hg, 1.5 x 10"2 atm at 20°C). Having a
Henry's law constant (6.6 x 10'4 atm-m3/mol) which is
considered mid-range among commonly occurring chemical
contaminants (Lyman, 1982a) combined with a relatively low
affinity for the organic fraction of soil (organic carbon
coefficient, 66 mg/g, as reported by Rogers and Mcfarlane,
1981; 44 mg/g, as cited in Lyman, 1982b), makes the chemical
suspect to move freely through the underground compartment
where it is introduced intentionally as a fumigant or unin¬
tentionally from leaking underground gasoline storage tanks.
Ethylene Dibromide in Florida Groundwater and Soil
The locations and levels of EDB in contaminated
groundwater are related to dry and wet time periods and to

12
topography of the land. This pattern presumably reflects the
halting and restarting of dilution of EDB in the aquifer.
For example, a sharp rise in EDB content in the Floridian
aquifer in the eastern part of the Florida panhandle
paralleled the onset of the drought of mid-1986 in the
southeastern United States. In one location studied, the
proximity of sinkholes to areas of EDB application favored
the contamination of underlying limestone aquifers.
As noted earlier, after the initial discoveries of EDB
in groundwater in California, Georgia and Florida, at least
five other states reported finding the compound in their
groundwater. The situation in Florida, however, appeared
the most severe.
Responding to an early indication of the problem, the
state of Florida assembled a multi-departmental task force
headed by the Department of Environmental Regulation. Its
goals were to oversee and implement a state-wide groundwater
surveillance program, to gather available related
information and initiate necessary research, and to offer
assistance to residents of affected areas. Monitoring of
public and private wells since June 1983 has shown that of
the 67 counties in Florida, 22 counties had wells delivering
water contaminated with EDB. Concentrations of EDB detected
have ranged from 0.02 to about 900 ppb (Aller, C., personal
communication, see footnote, p 6). Figure 1 represents the
location of State EDB applications and well water sites

13
known to be contaminated with EDB as of March 1985. The EDB
surveillance program database indicates that by June 1989,
1,703 wells of 13,441 tested (12.7%) were positive for EDB
contamination. Approximately 86% of the positives found
were in the counties of Highlands, Jackson, Polk, Lake, and
Orange. With the exception of Jackson, most of the
contamination (80 to 100%) resulted from the State nematode
eradication program. Ninety percent of the wells tested in
these counties are private wells. Less than 0.1% of wells
tested had EDB concentrations greater than 10.00 ppb. The
majority of the positives were between 0.01 and 1.00 ppb
(Florida Groundwater Protection Task Force Meeting Minutes,
1989).
EDB has been used in Florida by horticultural and
agricultural concerns and in golf course maintenance. Since
EDB was not classified as a restricted use pesticide by the
EPA, users were not required to maintain records. This lack
of record keeping makes it difficult to predict areas at
high risk for contamination and therefore difficult to make
decisions about remediation of this contamination.
Starting in 1960, the Florida Department of Agriculture
documented its use of EDB in their Spreading Decline Control
Program. The disease known as spreading decline is
the result of microbial infection of crops transmitted by
the burrowing nematode. Practices included the
establishment of barriers or buffer zones to prevent the

Figure 1. State of Florida nematode eradication program: application sites of EDB
and EDB-contaminated wells as of March 1985.


16
Feldman, 1965). State records indicate that the EDB
application rate had been about 60,000 to 70,000 liters per
year or an estimated total of 660,000 to 770,000 liters
applied since initiation of the program. The application
rate of EDB in this nematode eradication program was 25 to
50 lbs/acre1. Approximately 9600 cumulative acres were
treated as barriers, which mainly consist of retreated land
which average 417 acres treated per year. EDB was applied
by injection at least eight inches beneath the soil surface
through tubes behind coulter openers or chisels. The
resulting furrows were closed by hilling soil over them, by
press wheels or other means, to prevent loss of the EDB
fumes from the soil (Florida Dept. Agrie., 1984). State-
sponsored application of EDB correlates well with cumulative
contamination data, as shown in Figure 1, with the exception
of the northwestern region of the State. The use of EDB in
soil by the State was estimated to be only about 10 percent
of all the EDB applied. Records of non-State-sponsored
applications are scant, making reliable estimates of usage
impossible (Shankland, 1985). Generally, contaminated areas
are consistent with records compiled by inspectors from
information volunteered by agricultural growers for the last
two years of EDB application around the State, with at least
Written correspondence dated May 9, 1984 from D.Conner,
Florida Secretary of Agriculture, responding to the
information requested by Florida Senator P. K. Neal,
regarding State EDB soil application.

17
one notable exception. Records from Dade county in south
Florida indicate that EDB had been applied in the greatest
quantity, yet no contamination has been found. There is no
explanation for this observation; however, more rapid
groundwater flow compared to other areas of the State may
have contributed to faster dilution of the chemical.
Sorption to Soil
Despite the dispersal of significant amounts of EDB
into the environment from pesticide application, emissions
from gasoline-engine combustion and leakage of underground
tanks, little was known about the persistence, fate and
transport of the compound in the natural environment,
especially, in soil and water. Values as divergent as five
to 10 days (Johns, 1976; Leinster et al., 1978) and 14 years
(National Institute of Occupational Safety and Health, 1977)
were cited as half-lives due to hydrolysis in neutral
aqueous solutions at ambient temperature. Early
investigations focused primarily on residual EDB on crops
and on processed or stored agricultural products (Heuser,
1961; Sinclair et al., 1962; Beckman et al., 1967).
The diffusability of EDB through soil is a crucial
factor affecting its ability to reach and destroy soil-borne
pests. An important factor that influences the diffusion is
the adsorptive capacity of the soil for the fumigant vapor.
Early work indicated that there is little penetration into
soil mass above the point of injection of undisturbed soil

18
after treatment. Sorption was found to be primarily due to
colloidal organic matter and therefore affected greatly by
the amount of organic content of the soil (Siegal and
Erickson, 1953). Sorption was rapid with very little, if
any, irreversible sorption. A sharp drop in sorption
followed small increases in moisture content of soils (i.e.,
from 15 to 17% moisture) with sorption leveling at about 25%
soil moisture content. Temperature decreased the amount of
EDB sorbed on soils by about 5% per degree between 10 and
25°C (Wade, 1954). The sorption capacity of soil was
closely related to the observed concentration ratio in the
soil-water phase to the vapor phase (Henry's law constant),
with a three-fold decrease in sorption accompanying a
temperature increase from 5 to 25° C (Thomason et al.,
1974). For up to twenty days after simple line injection,
there was very little loss of EDB to the atmosphere through
an undisturbed soil profile. A loss of less than 5% of EDB
was measured after a chisel shank hole injection at a
commonly employed depth of 30.5 cm, during which time a
constant air stream at a rate of 0.80 Km/hr was passing over
the surface of the soil.
In contrast, investigators fit their experimental data
to the Brunauer, Emmett, and Teller (BET) multi-molecular
isotherm adsorption equation. They found that EDB sorption
potentials to soils were essentially restricted to the
external surface of the soil particle and not organic

19
material (Jurinak and Volman, 1957) . The BET adsorption
theory is based primarily on the assumption that Van der
Waal's forces between molecules play the predominant role in
adsorption after the mono-layer is formed. The ability of
EDB to penetrate water structure in close proximity to soil
surfaces is greatly inhibited by increased moisture content
(Call, 1957). The competition between water and EDB for
sites on soil surfaces is also a function of soil type
(Phillips, 1964).
Under field conditions, two or more interacting edaphic
factors in soil were found to determine the overall
diffusion behavior. Penetration in coarse soil was largely
dependent upon moisture content and temperature; medium-
textured soil penetration was dependent upon moisture,
temperature and bulk density; no movement occurred in fine-
textured soil (Townsend et al., 1980). In closely related
studies, sorption of neutral organic compounds was shown to
be essentially a partitioning-controlled process rather than
a physical adsorption process (Choiu and Peters, 1979;
Rogers and McFarlane, 1981).
Degradation in Soil and Water
Evaluation of the ability of microbes to degrade EDB
has been reported by two laboratories. Bacterial batch
cultures of primary sewage effluent incubated under anoxic
denitrifying conditions failed to degrade EDB (Bouwer and
McCarty, 1983). It was found, however, to be rapidly

20
transformed under anoxic methanogenic conditions in batch
cultures and in a continuous-flow methanogenic fixed-film
column (Bouwer and McCarty, 1985). Anaerobic suspensions
of sewage sludge, activated by percolating oxygen through
the sewage, gave similar findings. The gaseous product in
this case was confirmed to be ethylene (Weintraub et al.,
1986). This laboratory also found that similar suspensions
incubated under aerobic conditions resulted in rapid
degradation to a non-volatile, debrominated and highly
water-soluble product (Jex et al., 1985). Separation of
this product was achieved by high performance liquid and
thin layer chromatography plus chemical derivatization for
gas chromatography and mass spectrometry analysis.
Analytical results suggested a single product which probably
is a condensation or complexation with organic materials or
microbial cells.
The ability of natural microbiota to degrade EDB from
contaminated areas has been reported by two laboratories.
In the first study, soil was obtained from three Florida
farming regions where the chemical was used extensively for
many years. Soil samples from depths of one and three
meters, which were assumed to be anaerobic, were incubated
as such in aqueous suspensions. Only inorganic nutrients
were added and incubated for seven months. The
investigators found that EDB was either not degraded or only
marginally degraded by organisms in Florida soil (Weintraub

21
et al., 1986). In contrast, the second study found EDB to
be rapidly mineralized to carbon dioxide and bromide ion by
organisms in surface soils under aerobic incubation
conditions. Soil and water were sampled from an EDB-
contaminated groundwater discharge area in Connecticut. The
conversion of EDB to these products was almost complete with
the exception of only small amounts of an unidentified
unextractable product (Pignatello, 1987).
Wilson et al. (1986) found that EDB was rapidly
degraded in aquifer material known to support
methanogenesis. The equilibrium redox potential of the
material used was -272 mV. Concentrations of 200 ppb of EDB
in the aquifer matter-pore water used declined to 27% of the
control concentration by seven weeks of incubation at 17°C.
No carbon dioxide was detected as a degradation product.
Although no product was identified, a peak observed by gas
chromatography with flame ionization detection coincided
with the disappearance of EDB; subsequent GC/MS was not
successful in identifying this peak. The report made no
mention of the presence of hydrogen sulfide, commonly
present in the material described and possibly a very
important reactant in the incubation material.
Steinberg, et al. (1987) have reported residual EDB in
soils from Connecticut farmlands highly resistant to
degradation or mobilization. The EDB was released with heat
and organic solvent treatments. Central Florida soils that

22
were treated approximately bi-annually, but had not received
EDB treatment for at least 5 years, had EDB residues up to
60 ng/g of dry soil (Moye and Weintraub, 1988). The EDB in
these soils was released with 75°C acetonitrile incubation.
About 1 ngEDB/g dry soil was released from some of the soils
after exposure to 45°C dry heat for 8 hr followed by and
aqueous washing. The importance of a fraction of "soil-
bound" EDB in contaminated areas is still being evaluated.
Other modes of degradation of EDB have also been
investigated recently. EDB in aqueous solution is rapidly
photohydrolyzed upon irradiation with a 450-W medium
pressure mercury lamp to yield ethylene glycol and bromide
ion. The rate enhancement for this process was estimated to
be 105 times greater than that of the nonphotolytic pathway
(Castro and Besler, 1985). In another study, EDB was shown
to undergo complete heterogeneous photocatalyzed
transformation to carbon dioxide and hydrogen bromide
(Nguyen and Ollis, 1984). This conversion was catalyzed on
titanium dioxide when illuminated with near-UV radiation.
The titanium dioxide surface is suggested as the site of
formation of hydroxyl radicals which promote the reaction.
Other investigators have found that the superoxide ion
dioxygenates EDB to yield formaldehyde and bromide ion in
aprotic solvents (Calderwood and Sawyer, 1984) . The later
three modes of degradation of EDB have been suggested by the
authors as useful ways to dispose of halogenated pesticide

23
wastes such as EDB. Finally, oxidation of EDB to
formaldehyde in aqueous solution has been reported to occur
at high temperatures (i.e. greater than 80°C). The
conversion, however, was not found to be significant under
environmental conditions. In this same laboratory, EDB at
concentrations of 300 and 700 ppb was found to be stable
over a two-week period at 25°C in solutions of aqueous
chlorine which are commonly attained during disinfectant
processes in municipal water facilities. Total concen¬
trations of one and 10 ppm of the two species, hypochlorous
acid (H0C1) and hypochlorite ion (OC1), were varied by
buffering the solutions from pH 6.5 to 9 (Moye et al.,
1986). It is important to note that the above mentioned
studies are laboratory modes of reaction that do not
necessarily reflect reactions in the field.
An additional route of degradation of EDB in the
environment may have been uncovered by recent work by
Schwarzenbach et al. (1985). These investigators detected
numerous dialkyl sulfides and other volatile sulfur-
containing compounds while sampling wells in an area
contaminated seven years earlier by commercially produced
volatile halogenated hydrocarbons. In laboratory studies it
was revealed that at least for a representative test
compound, 1-bromohexane, under highly reducing conditions in
the presence of hydrogen sulfide, nucleophilic substitution
reactions proceed quite readily. A recent report by Watts

24
and Brown (1986) describing the findings of organics in
contaminated well fields in Palm Beach county, Florida,
includes the sulfur-containing compounds ethyl mercaptan,
triethyl disulfide, and diethyl disulfide, as well as
bromoethane. Although the components of gasoline were also
found in the well water, no EDB was reported. The
possibility of a similar reaction occurring with EDB in
anaerobic groundwater has recently been reported by
Weintraub and Moye (1987).
Vogel and Reinhard (1986) identify the reductive
dehalogenation product of EDB, vinyl bromide, as a major
product in their hydrolysis study of EDB. If, in fact,
vinyl bromide (Moye and Weintraub, 1986), is the major
product, than EDB's degradation in groundwater does not
decrease toxicity (Henschler, 1985).
Summaries of the modes of degradation of EDB discussed
here are presented in Tables 2 and 3. Ongoing and future
work may enable scientists to understand the variations and
relative importance of these and possibly other modes of
degradation in relation to the persistence and hazard
presented by this chemical in the environment.

Table 2. Summary of microbial transformation of EDB.
CONDITIONS
HALF-LIFE
PRODUCTS
REFERENCE
Field crops
"rapid"
1
Br', ?
Beckmann et al.
(1968)
Soil-water
cultures
ca. 30
d
Br- + ethylene
Castro, Besler
(1968)
Anaerobic
(denitrifying)
N.D.
—
Bouwer, McCarty
(1983)
Anaerobic
(methanogenic)
—
Br- + ethylene
Bouwer, McCarty
(1985)
Florida soils
(methanogenic)
N.D.
—
Weintraub et al.
(1986)
Activated-sludge
(methanogenic)
ca. 21
d
Br- + ethylene
Jex et al. (1985)
Activated-sludge
(aerobic)
5-10 d
Br-, Biomass
Jex et al. (1985)
CT stream-sedi¬
ment (aerobic)
35-350
d
Br-, C02, biomass
Pignatello (1986)
Aquifer material
(methanogenic)
ca. 21
d
Unidentified
Wilson et al.
(1986)
N.D.
None observed

Table 3. Summary of chemical transformations of EDB.
MODE
CONDITIONS
HALF-LIFE
PRODUCTS
REFERENCE
HYDROLYSIS
Neutral, aq
2 5 ° C
5-10 d
Not Reported
John (1986)
Neutral, aq
2 0 ° C
14 yr
Not Reported
NIOSH (1977)
Neutral, 'Zero
buffer' 20°C
8 yr
Br , Unident¬
ified
Cohen,Jungclaus
(1986)
FL groundwater
abiotic, 22 °C
1.5-2 yr
Ethylene glycol +
Br'
Weintraub et
al. (1986)
PHOTOLYSIS
UV, aq
10 d
Ethylene glycol +
Br'
Castro et al.
(1985)
SULFIDE
SUBSTITUTION
Buffer-aq,
5-75 ppm
H,S, 25 °C
2-4 mo.
Cyclic-alkyl and
dialkyl- sulfides
Weintraub et
al. (1987)
REDUCTIVE
DEHALOGENATION
>
&
fO
o
o
o
2.5 yr
vinyl bromide +
Unidentified
Vogel, Reinhard
(1986)

27
Risk Factors for Groundwater Contamination
Florida's citrus, soybean and peanut farming areas,
where EDB was commonly used, are located on predominantly
sandy and well-drained soils with very low organic matter
content (i.e., less than 1%). The soils are mostly entisol,
spodosol, alfisol and ultisol types. Together with a
relatively high mean annual rainfall and high recharge to
the Floridian aquifer in these regions (Fernald and Patton,
1984), the potential for movement of certain chemicals
through the unsaturated subsurface zone is great. As
previously explained, EDB has this ability to be quite
mobile as well as persistent.
There have been a number of attempts in recent years to
develop comprehensive groundwater protection strategies.
The main goal has been to establish criteria upon which to
base regulatory and monitoring decisions to guard against
groundwater contamination. The EPA began such an effort in
1979 to identify pesticide characteristics, nitrate levels,
and soil pH that would likely result in groundwater
contamination (Cohen et al., 1984). Another approach
currently proposed by the EPA makes use of a numerical
rating scheme for evaluating the potential for groundwater
contamination in a specific site given its geohydrological
setting. The scheme is called DRASTIC, an acronym for (i)
depth to groundwater, (ii) recharge rate, (iii) aquifer
media, (iv) soil media, (v) topography, (vi) impact of the

28
vadous zone, and (vii) conductivity of the aquifer (Rao et
al., 1985).
More recently, researchers at the University of Florida
have developed a simple scheme for ranking the relative
potentials of different pesticides to intrude into
groundwater (Rao et al., 1985). The index, referred to as
the attenuation factor (AF), is intended for use by
regulatory agencies in a preliminary evaluation of a large
number of pesticides to target chemicals for groundwater
monitoring programs or to initiate site-specific studies.
Of the 40 chemicals evaluated, the top 5 ranking pesticides
were EDB, bromacil, picloram, DBCP, and diuron. Not
surprisingly, EDB ranked as having the greatest potential
for groundwater intrusion in the soils tested.

MATERIALS AND METHODS
Materials
The following is a list of materials used in this study
along with the supplier and stated purity or grade when
provided by the manufacturer. The supplier's location is
listed only the first time it is mentioned.
Analytical Standards
Bromoacetic acid (Aldrich Chemical: Milwaukee, WI; 98%)
Bromoethane (Aldrich Chemical; 99+%)
2-Bromoethanol (Eastman Kodak; Rochester, NY 98%)
1-Butanethiol (Eastman Kodak; 99+%)
Butyldisulfide (Aldrich Chemical: Milwaukee, WI; 98%)
Cyclohexylthiol (Aldrich Chemical; 95+%)
1,2-Dibromoethane (Aldrich Chemical; Gold Label; 99+%)
1.2-Dibromoethane (ethylene dibromide, EDB; EPA Pesti¬
cides and Industrial Chemical Repository: Research
Triangle Park, NC; 99+%)
1,4-Dithiane (Aldrich Chemical; 97%)
1.3-Dithiolane-2-thione (Aldrich Chemical; 99%)
1,2-Ethanedithiol (Eastman Kodak; 99.5%)
Ethanethiol (Eastman Kodak; 98%)
Ethyl disulfide (Aldrich Chemical; 99%)
Ethylene glycol (Eastman Kodak; 99+%)
29

30
37% Formaldehyde solution (Fisher Scientific: Fair
Lawn, NJ; ACS Certified, 36.6%)
Paraformaldehyde (Fisher Scientific; 95%)
Potassium bromide (Mallinckrodt: Paris, NY; analytical
grade)
1,4,7,10-Tetrathiacyclododecane (Aldrich Chemical: West
Chester; 97%)
1,4,7-Trithiacyclononane (Aldrich Chemical; 98%)
1,3,5-Trithiane (Chem Service: West Chester; 99%)
Vinyl bromide (Aldrich; 98%)
Radiolabeled Chemicals
uC-Formaldehyde (4.4 mCi/mmoL, Pathfinders: St. Louis,
MO; 98%)
U-^C-Toluene (1.8 nCi/mL, New England Nuclear:
Boston, MA)
U-uC-Ethylene dibromide (55 mCi/mmoL, Amersham:
Arlington Heights, IL; 95+%)
U-uC-Ethylene dibromide (U-25 mCi/mmoL, Amersham; 95+%)
U-1AC-Ethylene glycol (U-4.23 mCi/mmoL, Pathfinders;
98%)
Solvents and Reagents
Agua-Sol 2 (New England Nuclear)
Buffer solutions, pH 4, 7, 10 (Fisher Scientific;
ACS Certified)
Chloroamine T (Fisher Scientific; ACS Certified)
Chloroform (Fisher Scientific; HPLC-grade)

31
Chromotropic acid disodium (Fisher Scientific; ACS
Certified)
N,N-Dimethyl-p-phenylenediamine dihydrochloride
(Aldrich Chemical; 99%)
Ferric chloride hexahydrate (Aldrich Chemical; 97%)
Ferric ammonium sulfate (Fisher Scientific, ACS
Certified)
Hexanes (Fisher Scientific; pesticide grade)
Iodine (Fisher Scientific; Certified ACS)
2-Nitrophenylhydrazine (ICN Pharmaceuticals, Plainview,
NY)
Periodic acid (Mallinckrodt; ACS analytical grade)
Potassium nitrate (Fisher Scientific; Certified ACS)
Potassium fluoride (Fisher Scientific; Certified ACS)
Potassium ferrocyanide (Fisher Scientific; Certified)
Potassium ferricyanide (Fisher Scientific; Certified
ACS)
ScintiVerse II (Fisher Scientific)
Sodium sulfide, 9-hydrate (Eastman Kodak; ACS reagent,
98.0-103.0%)
Sodium sulfite (Fisher Scientific; Certified ACS)
Sulfuric acid (Fisher Scientific; Certified ACS)
Triethylamine (Aldrich Chemical; 97%)
Water (Fisher Scientific; HPLC-grade)

32
Components of Buffers
All of the following chemicals were Fisher Scientific,
ACS Certified grade unless otherwise indicated.
Borax (sodium tetraborate, Sigma Chemical: St. Louis,
MO; 99.9%)
Disodium dihydrogen phosphate hepta hydrate
Disodium borate decahydrate
Disodium carbonate
Glacial acetic acid (reagent ACS)
Hydrochloric acid (reagent ACS)
Monopotassium phosphate
Potassium acetate
Potassium phthalate
Potassium chloride
Sodium monohydrogen phosphate monohydrate
Sodium citrate
Sodium hydroxide
Sodium monohydrogen carbonate
Sodium borate
Sodium carbonate decahydrate
Sodium succinate
Titanium trichloride solution (20%/80% water stabilized
with 3% phosphoric acid)

33
Gas Chromatographic Materials and Columns
5% Carbowax 20M (Supelco: Bellefonte, PA)
Gas Chrom Q 80/100 mesh (Supelco)
15% OV-17 on Gas-Chrom Q (Alltech Assoc.: Deerfield,
IL)
4% OV-225 on Chromosorb Q (Supelco)
Phenylmethylsilicone crosslinked coated capillary
column (DB-5, J & W Scientific: Folsom, CA)
Polymethylsiloxane crosslinked coated capillary column
(Ultra 1, Hewlett-Packard: Palo Alto, CA)
Polyphenylmethylsiloxane coated wide bore column
(RSL-300, Alltech Assoc.)
Polypropylene glycol (Supelco)
10% Squalane on Chromosorb W (Supelco)
Methods
Ethylene Dibromide and Product Identification and Quantita¬
tion bv Gas Chromatography and Spectrophotometry
Gas chromatography of EDB and related brominated metabolites
Gas chromatograhpic (GC) conditions were established for
the simultaneous analysis EDB and other closely related
bromominated metabolites (bromoethane, bromoacetic acid and
2-bromoethanol) on a Hewlett-Packard Model 5840A gas
chromatograph (GC) equipped with a 63Ni electron capture
detector (EC) and a Hewlett-Packard Model 7671 A
autoinjector. The 2 m x 0.32 cm i.d. glass column used was

34
packed with 15% polypropylene glycol (PPG) on Gas Chrom Q
80/100 mesh solid support which was coated in this
laboratory. The solid support was coated by slow
rotoevaporation of 50 mL of acetonitrile in which the 3 g of
PPG was dissolved and 17 g of solid support was added. The
resulting stationary phase achieved superior separation of
the analytes compared to others tested. The column packings
which were used perviously EDB and similar analytes and
tested include 5% Carbowax 20M (polyethylene glycol, Dumas
and Bond, 1982), 15% OV-17 (Rains and Holder, 1981), 4% 0V-
225, and 10% squalane. The PPG was used for the
determination of ethylene chrorohydrin (2-chloroehtanol) by
Heuser and Scudamore (1967).
The PPG column prepared was used with a 5% methane/95%
Ar carrier gas at a flow of 52 mL/min. Temperatures
maintained during analysis were 100°C for the column, 300°C
for the detector and 225°C for the injector.
EDB was extracted from aqueous solutions by parti¬
tioning into hexane upon mixing. For experiments in which
solutions were incubated in 100 mL serum bottles, the
following procedures were followed. Using a 10 mL syringe a
10 ml aliquot was withdrawn through the Teflon-coated rubber
septa, and slowly delivered to a 10 mL volumetric flask to
assure a precise volume. This volume was transferred to a
15 mL screw-top test tube to which 1.0 mL of hexane was
added and the tube immediately capped. It was inverted 5

35
more times and allowed to stand for at least 5 min. A
portion of the hexane layer was pipetted into a 1 mL vial
for automated gas chromatographic analysis. In subsequent
experiments where solutions were incubated in 10 mL sealed
ampules or where the partitioning of uC-activity was
analyzed, 2 mL of soltions were transferred with a tranfer
pipet to test tubes containing 2.0 mL of hexane. All
extractions of aqueous samples were performed in duplicate.
Extracts were injected in duplicate into the GC. Standard
curves of detector response ranging from 2 0 to 1500 pg//iL of
EDB were prepared daily and used for quantitation using
linear regression least squares analysis.
Determination of ethylene glycol
Ethylene glycol concentrations in water were determined
by GC analysis of the 2-nitrophenylhydrazine derivative of
formaldehyde, formyl 2-nitrophenylhydrazone. The method of
Fishkind (1987) for the analysis of formaldehyde in water
was adapted by including a preliminary oxidation step. To 2
or 4 mL of the water sample, a 20 /¿L aliquot of 5 x 10‘6 M
periodate and the sample was then allowed to stand at room
temperature in the dark for 20 hours. Periodic acid
oxidizes ethylene glycol into two molecules of formaldehyde
(March, 1985). Excess periodic acid was precipitated by the
addition of 50 /¿L of a saturated solution of potassium
nitrate? the mixture was allowed to stand for 1 hr in an ice
bath (Hillenbrand, 1952).

36
Standard aqueous solutions of ethylene glycol prepared
from analytical grade ethylene glycol were assayed by the
same procedure each day of analysis to construct a standard
curve for quantitation. Aqueous formaldehyde, which was
either formed by the oxidation of ethylene glycol or was
present in standard solutions, was quantitated by the
addition of 640 of a 2 M aqueous solution of 2-nitrophen-
ylhydrazine, which had been recrystallized from hexane to
remove background formaldehyde. After the addition of this
derivatizing reagent, the reaction mixture was incubated in
a water bath at 40°C for 1 hr. The derivative 2-
nitrophenylhydrazone was extracted by the addition of 5 mL
of hexane to the tube, which was then mixed on a vortex-
mixer for 1 min. A portion of the hexane layer was pipetted
into a 1 mL vial for automated analysis on a Hewlett-Packard
Model 5890 GC. This instrument was equipped with a Hewlett-
Packard Model 7671 A autosampler, a 63Ni electron capture
detector, and a 2 m x 0.32 column packed with 4% OV-225 on
Chromosorb Q 80/100 mesh. A 5% methane/95% Ar carrier gas
at 30 mL/min, a column temperature of 173"C, a detector
temperature of 300°C, and an injector temperature of 225°C
were employed.
The method was validated with use of 14C-ethylene
glycol (specific acitivity 4.23 mCi/mmol) and UC-
formaldehyde (specific activity 4.4 mCi/mmol). Unlabeled
stock standard formaldehyde solutions made from para-

37
stock standard formaldehyde solutions made from para¬
formaldehyde were standardized against accurately made
solutions of bisulfite formaldehyde and 37% formaldehyde
solution using the chromatropic acid spectrophotometric
method of Houle et al. (1970). Other supporting data used
for optimization of these procedures are described by
Fishkind (1987) .
Determination of bromide
Bromide ion concentrations in water were analyzed by
Standard Water and Watsewater Methods Procedure No. 405 C
(American Public Health Association, 1980, p 261). Bromide
ion was oxidized by Chloroamine T to bromine which bro-
minates phenol red. The brominated product was measured by
absorbance of the reaction mixture at 590 nm on a Beckman
DU-8 spectrophotometer. Standard agueous solutions of
bromide prepared from potassium bromide were assayed to
construct a standard curve over a range of 50 to 1000 /ig/L.
Samples were diluted as needed with deionized water to final
concentrations which fell within the linear quanitative
range.
Liquid Scintillation Counting of 14C-ethvlene Dibromide
Total KC-activity was measured by liquid scintillation
counting of 1.0 mL of sample pipetted into 15 mL of liquid
scintillation fluid. Either Aqua-Sol 2 or Scinti Verse II
liquid scintillation fluids were used. There was no
difference in results using either of these reagents.

38
Counting was done on a Searle Analytical 92 liquid scintil¬
lation counter with a Silent 700 electronic data terminal.
Quenching was evaluated both by comparing additions of
the fortified waters or hexane extracts to additions of
known amounts of 1AC-toluene (4xl06 dpm/mL) and by external
addition of 20 /xL of 1AC-toluene to fortified waters or
hexane extracts. The dpm/mL in aqueous solutions or hexane
extracts was determined by dividing the measured cpm/min by
the counting efficency. Efficiency and precision of
extraction of EDB from the waters were evaluated in a
similar fashion.
Gas Chromatography and Mass Spectrometry
for Sulfur Product Identification
Analyses were performed on a GC with a flame
photometric detector with a 394 nm filter for sulfur-
containing compound selectivity (FPD/S). With this filter,
the predominant chemiluminesence bands of emmision of
sulfur-containing analytes are detected (Farwell and
Barinaga, 1986). Analyses were performed on a 5840A Hewlett
Packard GC equipped with a Hewlett Packard 7671A autosampler
and a 15 M x 0.53 mm i.d. wide bore column with 1.2 /xm
polyphenylmethylsiloxane film (RSL-300). The oven
temperature was programmed as follows: it was held at 40 °C
for 2 min, then increased at a rate of S'C/min to 90°C, then
25°C/min to 200°C. The carrier gas flow of nitrogen at 10
mL/min. FPD/S conditions were as follows: injector

39
temperature 170°C, detector temperature 225°C, hydrogen 80
mL/min, oxygen 14 mL/min and air 55 raL/min.
Extracts from aqueous incubations, usually a 5:1 ratio
water to hexane, and the sulfur-containing standards in
hexane also were analyzed by GC/MS on a Finnigan 4021 GC/MS.
This instrument was equipped with a 30 M x 0.25 mm i.d.,
0.33 /im phenylmethylsilicone crosslinked film coated
capillary column (DB-5). The GC oven temperature was
programmed to begin at 60°C and increase at a rate of
12°C/min to 280°C. Mass spectra were obtained in electron
impact (El) and chemical ionization (Cl) modes, both at 70
eV and a source temperature of 150°C. The Cl spectra were
collected with isobutane reagent gas at 0.2 torr.
Oxygen, Redox, and pH Measurements
Dissolved oxygen was measured with a membrane oxygen
electrode (model 97-08, Orion Research, Cambridge, MA). The
electrode was calibrated in water-saturated air and zeroed
in a 5% sodium sulfite solution. Measurements were made in
a 100 mL BOD bottle without headspace.
Redox potential (Eh) was measured with a platinum redox
electrode (model 97-80, Orion Research Inc., Cambridge, MA).
This electrode was calibrated using the following solutions:
(1) 0.1 M potassium ferrocyanide with 0.05 M potassium
ferricyanide, (2) 0.01 M potassium ferrocyanide, 0.05 M
potassium ferricyanide, and 0.36 M potassium fluoride, and
(3) a standard ferrous-ferric solution composed of 0.1 M

40
ferrous ammonium sulfate, 0.1 M ferric ammonium sulfate, and
0.1 M sulfuric acid (Light, 1972).
The pH was measured with a glass body combination
electrode (model EA-2, Fisher Scientific, Fair Lawn, NJ) and
calibrated in standard pH 4, 7, and 10 buffer electrode
standardization solutions. All of the above mentioned
electrodes were connected to an Orion model 601A digital
ionanalyzer for operation.
Hydrolysis Reactions
Kinetics: Effects of Temperature and pH
Preparation and incubation of solutions
Groundwater was obtained from shallow wells in three
counties in northcentral and northwestern regions of the
State: Polk, Highlands, and Jackson. Water samples were
characterized by analyses either on-site, at this
laboratory, or at the Extension Soil Testing and Analytical
Research Laboratory, University of Florida (Appendix A).
The water was collected in five-gallon polypropylene
containers and kept on ice during transport to this
laboratory. Water was assayed for residual EDB by the
packed colunm GC analysis.
One hundred ml aliquots of these water samples and of
laboratory deionized water were fortified with EDB to con¬
centrations of 10 or 100 ppb with a methanol/water stock
solution of the chemical. Glass serum bottles (100 mL,

41
Wheaton, Millville, NJ) were filled with the solutions, the
headspace purged with nitrogen and the bottles tightly
capped with Teflon-coated rubber septum seal crimp caps
(Supelco, Beliefonte, PA). Before sample preparation, the
serum bottles, seals, and caps were autoclaved (121°C, 15
psi, 20 min) and the waters were either autoclaved (same
conditions) or vacuum-filtered through a 0.20 /urn filter
(Millipore, Bedford, MA) to eliminate microbial activity.
Sets of samples prepared in duplicate were incubated in
an inverted position in a darkened water bath. Since EDB
was relatively stable in water at ambient temperatures in
preliminary experiments, incubations were performed at 40,
50, 60, 70 and 80°C ± 0.5'C. Serum bottles were
periodically taken out of the water bath and allowed to
equilibrate to room temperature before sampling. The time
interval between samplings was determined by the observed
rate of disappearance of EDB.
The apparent first-order rate constants for EDB
degradation were obtained by linear regression least squares
analysis of the log percent EDB remaining vs time plot.
Arrhenius temperature dependence was assumed, whereby a plot
of log rate constant vs 1/T “K provides a convenient graphic
method to evaluate the activation energy, Ea, and to
estimate the rate constant of the reaction at any desired
temperature.
At least two samples in each incubation trial were
fortified with a U-UC-EDB (25 mCi/mmol) by addition from a

42
by addition from a 5 ¿xCi/mL methanolic stock solution to a
final concentration of ca. 5000 dpm/mL. These samples were
periodically sampled to check the integrity of the system by
measuring the containment of the KC-activity. The
radiochemical purity was reported to be 98% (Amersham) and
confirmed in this laboratory to be within 5% of the stated
value as measured by gas chromatography and liquid
scintillation counting. To check the efficiency of hexane
extraction of EDB and its losses during the analysis
procedure, solutions of UC-EDB were analyzed by identical
procedures.
The degradation of EDB was evaluated as a function of
pH in the three groundwaters and deionized water. A series
of 5 mM buffer systems (Diem, 1962) were used to maintain
groundwater and deionized water fortified with EDB at pH
values ranging from 4.0 to 9.0. The buffers and
concentrations of the components added for the resulting pH
as indicated were as follows: borax/succinic acid: 0.89
mM/4.11 mM pH 4.0, 1.98 mM/3.02 mM pH 5.2; potassium
phthalate/NaOH: 5.00 mM/0.04 mM pH 4.0, 5.00 mM/0.12 mM pH
4.6; borate/KCl/NaOH: 5.00 mM/5.00 mM/0.40 pH 8.0, 5.00
mM/5.00 mM/0.87 mM pH 9.0; borax/monopotassium phosphate:
0.28 mM/4.50 mM pH 8.0, 4.50 mM/0.13 mM pH 9.0; and sodium
carbonate/disodium bicarbonate: 0.40 mM/4.26 mM pH 9.2, 4.60
mM/0.76 mM pH 10.6).
Incubations of the EDB-fortified buffered solutions
were conducted at 62°C. The remaining EDB at approximately

43
3 day intervals was determined by hexane extraction and GC
analysis on the PPG packed column. Rate constants for EDB
degradation were derived from data collected over 17 days.
Product Identification
Polk, Highlands, and Jackson County groundwater samples
and deionized water were fortified with EDB to a
concentration ca. 3.5 mg/L, including 1AC-EDB with a
resulting concentration of ca. 3500 dpm/mL. Incubations
were conducted at 73°C until essentially all the EDB had
disappeared. At approximately 2 day intervals, analyses of
EDB, ethylene glycol, and bromide ion were performed. In
addition, samples were analyzed for purgeables by gas
chromatography/mass spectrometry (GC/MS). Within a purge
and trap device (Tekmar model ALS, Cincinatti, OH), helium
gas was bubbled at 8 mL/min through a 25 mL aliquot of a
sample for 22 min at ambient temperature and the effluent
directed onto Tenax adsorbent. The Tenax adsorbent was
heated to direct the purgeables into a GC, with a PPG column
and GC onditions used for EDB analysis. The GC was
interfaced with a Finnigan Model 4021 quadrupole GC/MS for
analysis. Mass spectra, scanning from m/e 50 to m/e 400,
were obtained in electron impact mode with an ionization
energy of 70 eV.
To measure the partitioning of 14C-activity of the
initial 1aC-EDB and its 1<1C-products, 1 mL aliquots of the
hexane and aqueous phases, after extraction, were pipetted
into 15 mL of scintillation liquid and counted. In

44
addition, 1 mL of the unextracted sample was analyzed in the
same manner.
Reactions with Aqueous Hydrogen Sulfide
Kinetics: Temperature and pH Dependence
Preparation of solutions
Experimental solutions were in 10 mM buffers prepared
with HPLC grade water. Before use, glassware and water were
autoclaved (121 °C, 15 psi, 20 min) . The buffers providing
solutions of pH 5, 7 and 9 consisted of the following
components: potassium acetate/acetic acid: 6.40 mM/0.360 mM
pH 5.0, potassium phthalate/sodium hydroxide: 2.36 mM/7.64
mM pH 5.0, sodium monohydrogen carbonate/hydrochloric acid:
8.17 mM/1.83 mM pH 7.0, disodium dihydrogen phosphate
heptahydrate/sodium monohydrogen phosphate monohydrate: 3.81
mM/6.19 mM pH 7.0, disodium borate decahydrate/hydrochloric
acid: 3.65/6.35 mM pH 9.0, disodium carbonate
decahydrate/hydrochloric acid: 0.53 mM/9.47 mM pH 9.0). The
resulting calculated ionic strengths of the solutions were
adjusted to n = 15 mM using 4.8 M KC1. The solutions were
deoxygenated by bubbling a stream of oxygen-free nitrogen
through them for at least 2 hr. The redox buffer, Titanium
(III) citrate of Zehnder and Wahrmann (1976), was used in
the experimental solutions to maintain an oxygen-free water
phase with high electron activity to inhibit oxidation of
sulfides. The redox buffer stock solution was perpared by
adding 3.5 mL of Titanium trichloride solution (20%/80%

45
water) to a final volume of 50 mL made up in 0.2 M sodium
citrate. One mL of the redox buffer stock solution was
added to each 99 mL of experimental preparation.
All subsequent manipulations of solutions and filling
of sample containers were done in an AtmosBag (Aldrich
Chemical) which contained an nitrogen atmosphere. The
oxygen concentration inside the Atmosbag remained below 0.05
mg/L. Oxygen concentration was monitored with an oxygen
sensor (Bio-Tek Instruments, Inc., Winooski, VT, Model
74223) .
Five hundred mL portions of the six buffer solutions
were fortified with methanolic stock solutions of 26.5 mM
EDB and 500 ¿iCi/mL of UC-EDB (specific activity 55
mCi/mmol) to achieve final concentrations of 6.0 /¿M ca. EDB
and 5000 dpm/mL. Crystals of disodium sulfide nonane
hydrate were washed with deionized water and suction dried
on filter paper before being weighed and dissolved in the
buffered solutions. The final concentrations of total
sulfide were quantitated to be 500 ± 140 and 1000 ± 300 /¿M
(17 and 34 mg/L H2S(aq)) .
Using a 10 mL Repeat-o-syringe pipet (Fisher
Scientific) with a 20 gauge needle, 9 mL of the fortified
buffer solution were slowly transferred to sterile 10 mL
glass ampules (Wheaton, Millville, NJ). Each filled ampule
was purged with a stream of nitrogen, then quickly sealed by
an oxygen and natural gas flame. During this procedure, the
fortified solutions were kept chilled in an ice bath.

46
Analysis of solutions
Duplicates of each buffer and H2S(aq) concentrations were
analyzed for EDB concentration, uC-activity, pH, Eh, and
oxygen concentration. Sets of 14 ampules of each buffer and
H2S(aq) concentration were incubated at 25, 40, and 60°C ±
1.0°C in the dark. Ampules were analyzed at time intervals
based upon EDB degradation rates determined in preliminary
experiments.
At each time interval, ampules were allowed to come to
room temperature before being opened. Two mL of the sample
was withrawn for hexane extraction. One mL aliquots of both
the hexane phase and the aqueous phase were transferred to
separate scintillation vials containing 15 mL of liquid
scintillation fluid and counted. The remaining 1.0 mL of
hexane was transferred to a serum bottle for GC analysis of
EDB. The GC analysis was performed on a Hewlett Packard
5890 GC with a model 3392 integrator/plotter and a 7671A
autosampler and an 63Ni electron capture detector. Grob
technique injections were made onto a 25 m x 0.20 mm (film
thickness, 0.33 /¿M, HP ULtra 1) capillary column temperature
programed with an initial oven temperature of 40°C for 2
min, then increased to 90°C at 8°C/min, and finally
increased at 30°C/min to 200°C. A carrier gas flow of
Argon/5% methane was maintained at 1 mL/min. A column purge
flow of 2 mL/min was activated at 1 min and a column make-up
was 30 mL/min. In addition, 1.0 mL of the original

47
incubated solution was transferred to 15 mL of liquid
scintillation fluid, shaken well, and then analyzed.
Total sulfide concentration was determined by the
procedure of Cline (1969), as modified by Millero (1987).
The method involves the formation of methylene blue from the
sulfide and reagent solution of N,N-dimethyl-p-phenylene-
diamine dihydrochloride and ferric chloride hexahydrate in
acidifided solution. Color was developed in 30 min and
absorbance was read at 670 nm with a Beckman DU8 spectro¬
photometer. Calibration solutions of concentrations ranging
from 4 fiM to 4 0 /nM H2S(aq) were prepared from a sodium sulfide
stock solution for each analysis. Stock solutions of soduim
sulfide were prepared by dissolving ca. 0.5 g of sodium
sulfide crystals that were washed with deionized water and
suctioned dry, in 100 mL of degassed deionized water. The
stock solutions were standardized by the iodometric
titration Standard Water snd Wastewater Method No. 427D
(American Public Health Association, 1980, p 476).
Concentrations of H2S(aq) in experimental solutions were
determined by comparison to a standard curve generated by
least-squares regression analysis of the assay response vs.
H2S(aq) concentration.
EDB apparent first-order degradation rate constants
were obtained by linear regression least squares fit of
plots of In percent EDB remaining vs time. The partitioning
of KC-activity of the initial UC-EDB and its 14C-products
were plotted versus time.

48
Product Identification
Hexane extracts from incubated of EDB and H2S{aq) in
buffered solutions from kinetic experiments and the same
buffer systems containing higher concentrations of
reactants, i.e., 60 /¿M EDB and 1000 or 2000 /¿M H2S(aq) were
subjected to GC and GC/MS analyses. Standard solutions of
11 commercially available sulfur-containing compounds in
hexane were chromatographed and subjected to mass
spectrometry for comparison with products formed in
experimental reaction solutions. Molecular formulae,
structure and suppliers of these standard compounds are
presented in Table 4.
Ethylene Dibromide in Sulfate Groundwater
Groundwater from wells in the Florida Ambient
Groundwater Network, which are known to have relatively
moderate to high concentrations of sulfate, were obtained
from officials of the South Florida Water Management
District. Clean 1 L brown-glass screw-top bottles with
Teflon-lined caps were filled in a manner which avoided
excessive contact with the air and were kept on ice in an
insulated cooler while being transported to the laboratory.
The pH, Eh and oxygen concentration of the samples were
measured. Three mL aliquots were then extracted with 1.0 mL
of hexane and the extracts analyzed by GC to determine if
any detectable compounds were initially present.
Three sets of EDB-fortified solutions were prepared
from each well water sample. Before fortification, one

Table 4. Commercially available sulfur-containing compounds used for product identification
COMPOUND
ABBREVIATION
CHEMICAL FORMULA/
FORMULA WEIGHT
STRUCTURAL
FORMULA
SUPPLIER/
PURITY
Ethanethiol
CAS #75-08-1
ET
c2h6s
62.13
CH3CH2SH
Kodak
(98%)
1-Butanethiol
CAS #109-79-5
BT
C«H10S
90.16
CH3(CH2)3SH
Kodak
(95+%)
1,2-Ethanedithiol
CAS #540-63-6
EDT
C2H6S2
94.20
hsch2ch2sh
Kodak
(99.5%)
Cyclohexyl thiol
CAS #1569-69-3
CHT
C6H12S
116.23
1 1
CH2(CH2)4CHSH
Aldrich
NA
1,4-Dithiane
CAS #505-29-3
DT
C,H8S2
120.24
1 1
ch2ch2sch2ch2s
Aldrich
(97%)
Ethyl disulfide
CAS #110-81-6
EDS
cahioS2
122.25
ch3ch2ssch2ch3
Aldrich
(99%)
1,3-Dithiolane-2-
thione
CAS #822-38-8
DTT
C3H4Sj
136.26
1 1
ch2scssch2
Aldrich
(99%)
1,3,5-Trithiane
CAS #291-21-4
TT
CjH6S3
138.27
1 1
ch2sch2sch2s
Chem Service
(99%)
Butyldisulfide
CAS #629-45-8
BDS
CaH18S2
178.36
CH3(CH2)3SS (CH2)3CH3
Aldrich
(98%)
1,4,7-Trithiacy-
clononane
CAS #6573-11-1
TTCN
C6ll12S3
180.36
1 1
CH2CH2S (CH2) 2S (CH2) 2S
Aldrich
(98%)
1,4,7,10-Tetrathi-
acyclododecane
CAS #25423-56-7
TTCD
C8H16S4
240.47
1 1
CH2CH2S ( ch2 ) 2S ( ch2 ) 2S ( ch2 ) 2s
Aldrich
(97%)
NA = Data not available

50
portion of each groundwater sample was autoclaved for 20 min
(121°C, 15 psi), another portion was degassed by bubbling
purified nitrogen gas through the water for approximately 2
hr, and a third portion of each water was left untreated.
Each portion of groundwater was fortified with a stock
solution of unlabeled EDB to give 1.5 mg/L EDB and also with
a stock solution of UC-EDB to give a concentration of
approximately 3000 dpm/mL. Sets of 10 mL ampules were
filled with about 8 mL of solution, the air space in the
ampule purged with a stream of purified nitrogen, and then
sealed by flame. The ampules were kept at 25"C in the dark
and periodically analyzed by GC for EDB concentration and
the appearance of extractable products. In addition, the
partitioning of UC-EDB and uC-products after hexane
extraction was determined using the method previously
described. One mL aliquots of the solutions were also
analyzed by liquid scintillation counting to check
containment of the EDB during incubation.
Organic Synthesis of a Sulfur Product
The aliphatic cyclic sulfur-containing compound,
1,2,5,6-tetrathiacyclooctane is not commercially available,
but its synthesis has been described by Goodrow et al.
(1982). The procedure involves slowly reacting a dilute
concentration of 1,2-ethanedithiol in chloroform with iodine
and triethylamine (reagents concentration of approximately
10 /iM, Goodrow et al., 1981).

RESULTS
Hydrolysis Reactions
Verification of Assay for Hydrolysis Products
Determination of EDB
Using the conditions previously described, EDB in
hexane extracts was quantitated using GC/EC by comparison of
unknowns to calibration curves consisting of four or five
standard solutions of EDB in hexane. The GC/EC response was
linear and reproducible over a range of 10 to 1200 pg of EDB
injected. Figure 2 shows a sample chromatogram and
calibration curve. The efficiency of extraction of EDB from
aqueous solutions into hexane was 95 to 100% over the
concentrations range using both labeled and unlabeled EDB.
Determination of ethylene glycol
Procedures for quantitation of formaldehyde and
ethylene glycol were validated using standard solutions para
formaldehyde and 37% formaldehyde solution or ethylene
glycol preparated in deionized water. In addition, UC-
labeled analytes were employed (formaldehyde 150 mCi/mg,
ethylene glycol 68 mCi/mg) for verifying the assay.
Since both analytes are very water-soluble and their 2-
nitrophenylhydrazone derivatives formed in the analysis are
extractable into hexane, partitioning of uC-activity was
51

Figure 2. Gas chromatogram, typical calibration curve and conditions for analysis of
EDB.

1,2-DIBROMOETHANE
63n¡ electron capture
15°/o POLYPROPYLENE glycol
95“c , 45 mL / MIN
750 pg/uL
\L
d i i
0 2 4
MIN.
ui
w

54
used to test efficiency of the assay. Because 14C-activity
can be measured at extremely low concentrations of labeled
material, a very sensitive assessment of efficiency was used
to test efficiency of the assay. Because 14C-activity can
be measured at extremely low concentrations of labeled
material, a very sensitive assessment of efficiency was
possible.
After derivatizing six solutions ranging from 17 to 689
/xg/L of 14C-formaldhyde, 86 to 98% was recovered in the
hexane extract. Performing the ethylene glycol procedure on
four solutions containing 288 to 2878 /ng/L of the compound
resulted in the recovery of 89% to 100% of the labeled
compound in the hexane extract.
Calibration curves for ethylene glycol were typically
constructed over a concentration range of 60 to 1500 /xg/L.
Resulting correlations of determination (r2) of linear
regression least squares analyses were larger than 0.99.
Figure 3 shows chromatograms of blanks and results of the
assay of ethylene glycol. Background concentrations of
formaldehyde between 10 and 50 /xg/L are common and must be
used to correct the results derived from the analysis of
unknown samples.
Kinetics: Temperature and pH Dependence
The disappearance of EDB in fortified groundwaters and
deionized water was followed over 22 days for incubation at
40, 50 and 60°C, 17 days for incubation at 70°C, and 6 days

Figure 3. Gas chromatograms after the 2-nitrophenylhydrazine derivatization assay of
unoxidized blank, oxidized blank and ethylene glycol (199 ¿ig/L) .

EC D RESPONSE
BLANK BLANK
(NO OXIDATION) (OXIDIZED)
199 ng / mL ETHYLENE
GLYCOL ASSAYED
Ui

57
for incubations at 80°C. These changes correspond to
decreases greater than 90% of initial concentrations of EDB
in the 80°C incubations and approximately 20% decreases of
EDB at 40°C. At intermediate temperatures, the degree of
degradation fell within this range. Linearity in plots of
the log % EDB concentration remaining vs. time demonstrated
apparent first-order degradation rates. The least-squares
regression coefficients of determination (r2) were greater
than 0.99 at higher temperatures and greater than 0.90 at
lower temperatures. The rate data from the Polk County
groundwater sample initially fortified to a concentration of
100 M9/L EDB are shown in Figure 4. If EDB degradation in
solution was an acid- or base catalyzed reaction, non-linear
semi-logarithmic plots of observed rate constants vs pH
should result. Figure 5 shows the observed rate constants
for the degradation of EDB in the groundwaters and deionized
water as a function of pH while incubated at 63°C. Table 5
shows the observed rate constants for the laboratory EDB-
fortified waters. The rate constants differ only slightly
between the waters and indicate neither acid- nor base-
catalyzed degradation. The larger rate constants observed
at pH 5 and pH 8 as compared to those of pH 7 are not con¬
sistent with a pH dependent degradation process. The boric
acid buffer at pH 7.8 to 8.3 may have participated in EDB
degradation, thereby increasing the observed rate constant.
Buffers can catalyze hydrolysis even when present at low mM

Figure 4. Disappearence of EDB at elevated temperatures in Polk County groundwater
initially containing 100 ug/L EDB.

’/o EDB Remaining
EDB Degradation in Groundwater at Various Temperatures

Figure 5. Observed EDB degradation rate constants as a function of pH in buffered
solutions (0.005 M 63°C) . Buffers are identified in Table 5.

log k (obs)
Polk water
+
Highlands water
—©—
Jackson water
Q
Deionized water
—a- -
4 5 6 7 8 9
PH
cri

62
Table 5. The effect of pH on the EDB degradation rate at 63"C
and initial EDB concentration of 100 /ng/L.
PH
Buffer3
103k (hr’1)b
(t1/2, hr)
103k±SD
Polk
Hiahlands
Jackson
Deion.
4.0-4.4
a
2.31
2.31
2.34
2.48
2.36±0.13
(301)
(302)
(298)
(280)
4.0-4.9
b
2.94
2.61
2.45
2.54
2.6310.29
(236)
(266)
(283)
(273)
4.7-5.3
b
2.84
2.56
3.46
3.10
3.2310.45
(208)
(225)
(200)
(225)
5.3-5.6
a
2.41
2.44
3.47
3.10
2.4010.10
(288)
(288)
(287)
(295)
6.1-6.5
c
2.45
2.98
2.64
2.83
2.7310.23
(283)
(233)
(263)
(285)
7.6-7.7
d
2.68
2.68
2.52
2.63
2.9510.62
(259)
(259)
(275)
(263)
7.8-7.9
e
4.39
3.96
3.83
4.17
4.1710.38
(158)
(175)
(181)
(166)
8.0-8.3
f
3.76
2.81
3.56
3.62
3.4410.44
(266)
(247)
(195)
(191)
8.6-9.0
g
3.07
2.61
2.41
2.95
2.9510.48
(224)
(267)
(288)
(235)
a0.005 M buffers: a = borax/succinic acid
b = potassium phthalate
c = borax/succinic acid
d = borax/phosphate
e,f = boric acid
g = carbonate
aApparent First-order rate constant for degradation of EDB
Average of replicate kinetic runs with 6 data points each
Half-life, t1/2 = 0.693/k
CA11 samples in pH range, n=8

63
concentrations (Perdue and Wolfe, 1983). The observed
first-order EDB degradation rates were used to construct
Arrhenius plots like the one shown in Figure 6. The data
shown are from EDB degradation in Polk County groundwater.
The least-squares regression coefficients of determination
(r2) for these plots ranged from 0.97 to 0.99 for all the
EDB-fortified waters tested. The resulting Arrhenius
kinetic parameters were used to make estimates of EDB
degradation rates at ambient groundwater temperatures. In
Table 6, the extrapolated kinetic parameters derived from
these data are shown for 22°C, a common groundwater
temperature in Florida. The kinetic parameters do not
significantly vary with the source of the water or with the
initial concentration of EDB. At 22°C in the waters tested,
the predicted half-life (t 1/2) ranges from 259 to 772 days.
The activation energy ranges from 19.1 to 24.3 kcal mol'1.
The variation among the data is fairly large, with standard
deviations generally ranging from 12 to 20% of their
respective means, except for J10 where the standard
deviation is 58% of the mean. Since the extrapolated values
for rate constants at ambient temperatures are derived from
relatively few data points a fair degree of error is
expected. Sources of error in rate constant may arise from
small deviations in temperature of experimental incubations
and random error (Harris, 1982; Maybey and Mill, 1978).

Figure 6. Arrhenius plot illustrating hydrolysis of EDB in Polk County groundwater
initially containing 100 ug/L EDB.

Arrhenius Plot for Hydrolysis of EDB
CTi
U1

66
Table 6. EDB degradation kinetic parameters in
solutions studied as predicted by Arrhenius kinetics plots.
Extrapolated values for 22°C are shown.
Samóle8
10 k
22°C. id'1}
22 ° C
' (d~1)
Ea (kcal
mol'1}
Log ,
(h.
)
P10
2.76
±0.41
259
+
35
19.6
±0.2
12.2
+
0.5
P100
1.61
±0.19
434
+
47
20.9
±0.4
12.7
+
0.2
H10
0.64
±0.38
772
+
94
24.2
±0.8
14.9
±
0.6
H100
2.33
±0.57
309
+
67
19.1
±0.6
11.6
+
0.4
J10
1.52
±0.65
547
±317
21.1
±2.2
12.1
+
0.3
J100
1.93
±0.36
369
+
69
19.7
±0.6
11.9
+
0.4
DW10
2.15
±0.25
326
+
38
19.6
±0.6
11.8
+
1.7
DW100
2.15
±0.25
326
+
38
19.6
±0.6
11.7
+
1.7
aP=Polk county groundwater
H=Highlands county groundwater
J=Jackson county groundwater
DW = deionized water
10 = 10 ng/li, concentration of EDB fortification
100= 100 /¿g/L, concentration of EDB fortification
b Mean of four replicate runs, except for two replicates
of DW samples;
mean of pseudo-first order rate constant ± standard
deviation, except DW is mean ± range of replicates
c Mean ± standard deviation of half-lives of EDB in days,
except DW is mean ± range of replicates
d Mean ± standard deviation of Arrhenius activation energy,
except DW is mean ± range of replicates
Mean ± standard deviation of frequency factor, except DW
is the mean ± range of replicates
e

67
Product Identification
In experiments using 14C-EDB conducted at elevated
temperatures, the decline in 14C-activity in the hexane
phase, determined after extraction of incubated solutions,
closely paralleled the degradation of EDB, as quantitated by
GC/EC (Figure 7). These observations are highly
reproducible, as shown in the results from simultaneous
quantitation and partitioning of C-EDB and C-products
during incubation at 80°C (Table 7). At the completion of
the experiment, the total l4C-activity in the solutions
ranged from 92 to 99 percent of the initial activity. This
finding indicates that no EDB or product was lost during the
experiment and that no products volatilized. The next
experiments employed solutions containing higher initial
concentrations of EDB (ca. 3.5 mg/L) than in the prior
experiments for the purpose of quantitating the water-
soluble products formed, i.e., bromide ion and ethylene
glycol (Figures 8a, 8b and 8c). Total 14C-activity was also
quantitated along with the hexane/aqueous partitioning of
14C-activity during incubation of the EDB-fortified
groundwater and deionized water. During the 17 day
incubations conducted at 73°C, the amounts of bromide ion
and ethylene glycol together accounted for 60 to 70% of the
initial EDB present. The extent of EDB degradation in these
incubation was approximately 8 or 9 half-lives. As in
previous experiments, the partitioning of 14C-activity into

Figure 7. Partitioning of uC-activity (UC-EDB and UC-
products by liquid scintillation counting) during EDB
degradation at 80°C.

PERCENT EDB OR 14C-ACTIVITY REMAINING
69
EDB CONCENTRATION 1
EDB CONCENTRATION 2
—-0—
TOTAL 14C-ACTIVITY 1
•*
TOTAL 14C-ACTIVITY 2
HEXANE 14C-ACTIVITY 1
HEXANE 14C-ACTIVITY 2
—B—
AQUEOUS 14C-AQUEOUS1
AQUEOUS 14C-AQUEOUS 2
—A

70
Table 7. Simultaneous quantitation of EDB (GC/EC) and partitioning
of 14C-activity (14C-EDB and 14C-products by liquid scintillation
counting) in dilute solution during degradation at 80 °C.
Time/Samole3
[EDB]
(Mq/Ll
14C
in Hexane
(dom/mL)
14C
in Aqueous
(dom/mL)
14C
Total
(dom/mL)
0
Hour
A1
56.4
150774(85)
19815(11)
177950
A2
59.8
150740(84)
23425(13)
178550
B1
28.9
77950(86)
10535(12)
90700
B2
29.1
78221(88)
10495(12)
88970
18
Hour
A1
41.5(74)b
114456(64)
55464(31)
178230(100)
A2
41.9(70)
115752(64)
55860(31)
181680(102)
B1
21.0(73)
53918(60)
30415(34)
89940(99)
B2
20.1(69)
58349(65)
28965(32)
89270(100)
44
Hour
A1
29.5(52)
83216(48)
83315(48)
175190(98)
A2
29.5(49)
82673(47)
84900(48)
176560(99)
B1
14.5(50)
42196(48)
43405(49)
88590(98)
B2
13.8(47)
41330(47)
42765(49)
87360(96)
80
Hour
A1
16.3(29)
51285(30)
117290(68)
172890(97)
A2
16.5(28)
48424(28)
117025(67)
175880(99)
B1
8.1(28)
23402(27)
59705(69)
87110(96)
B2
7.8(26)
23942(29)
56695(69)
82050(92)
EDB Degradation Kinetic Data (first-order plot)
Apparent rate
Regression Equation constant (hr'1)
A1
y=
-0.00667X
+
2.00
r‘=
-.9990
1.54
X
10
A2
y=
-0.00689X
+
1.99
r2=
-.9989
1.59
X
10
B1
y=
-0.00679X
+
1.99
r2=
-.9994
1.56
X
10
B2
y=
-0.00699X
+
1.99
r2=
-.9983
1.61
X
10
a10 mL aliquots of 100 mL samples are taken for each analysis
interval; samples 1 and 2 are duplicates
bPercent of 0 hour measurement in parenthesis

Figure 8. Partitioning of UC-EDB and 14C-products and
guantitation of EDB, ethylene glycol, and bromide during
incubation in Florida groundwater and deionized water.
Each point is an average of replicate measurements.
8a. EDB-fortifed Polk and Highlands groundwater incubated
at 73°C.
EDB
TOTAL 14C
14C-HEXANE
*
14C-WATER
— A—
ETHYLENE GLYCOL
BROMIDE ION

CONCENTRATION (ng/mL) or 14C (dpm/mL)
72

Figure 8 continued.
8b. EDB-fortified Jackson groundwater and deionized water
incubated at 73°C.
EDB
TOTAL14C
*-e~-
14C-HEXANE
•*
14C-WATER
— A—
ETHYLENE GLYCOL
BROMIDE ION

CONCENTRATION (ng/mL) or 14C (dpm/mL)
74

Figure 8 continued.
8c
EDB-fortified deionized water incubated at 80°C

CONC. (ppb), C ACTIVITY (cpm/mL)
DEGRADATION
IN AQUEOUS SOLUTION AT 80 C
TIME (DAYS)
CT\

77
the aqueous phase after extraction closely paralleled the
decline in EDB concentration. Similar patterns of trans¬
formation of EDB were seen in all three fortified ground-
waters and in deionized water. Figure 8c shows the pattern
of EDB transformation during an incubation at a higher
temperature (80°C) which was observed for a longer time
period (27 days) in deionized water. In this experiment,
the extent of conversion of EDB to bromide ion and ethylene
glycol ranged between 70 and 90%. Further examination of
extractions of aliquots from solutions in this experiment
did not reveal either additional brominated products of EDB
or intermediates in the conversion of EDB to bromide ion and
ethylene glycol. Purge-and-trap GC/MS analyses of aqueous
aliquots detected only trace quantities of 3- and 5-member
hydrocarbon compounds and remaining EDB.
Vinyl bromide could be formed from EDB if EDB were
reductively dehalogenated. This compound was found by Vogel
and Reinhard (1986) in pentane extracts of incubated aqueous
EDB solutions. Although it could not be detected in any of
the solutions or extracted by GC/EC or by purge-and-trap
GC/MS in this study. Under the GC/EC conditions used in
this study, the detection limit is at least 1000 times less
sensitive for vinyl bromide compared to EDB. If vinyl
bromide were formed in the present study, however, 14C-vinyl
bromide would have partitioned into hexaxe upon extraction.
There was no indication that this occurred. Injections on

78
GC/EC were made of the hexane phase and aqueous phases of
three replicate extractions of deionized water containing
1000 mg/L vinyl bromide. Vinyl bromide was only found in
the hexane phase and not in the aqueous phase.
Extraction of 2-bromoethanol from dilute aqueous
solutions was 30 to 40% efficient. Furthermore, GC/EC
detection of this compound was also much less sensitive than
EDB; at least 100 times less than EDB.
Reactions with Aqueous Hydrogen Sulfide
Kinetics: Temperature and pH Dependence
During incubations at 25, 40 and 60°C, the
disappearance of EDB from pH and redox buffered solutions
was examined along with the partitioning of UC-EDB and UC-
products after hexane extraction (Figures 9a, 9b and 9c).
These control solutions, which did not contain H2S(aq), were
studied over 237 days at 25°C, 194 days at 40°C and for 105
days at 60°C. At 25°C, neither the concentration of EDB nor
the partitioning of the 14C-EDB between the hexane and
aqueous phases changed noticeably at pH 5, 7, or 9. At 40
and 60°C, the disappearance of EDB was paralleled by the
changes in partitioning of the uC-activity. This trans¬
formation of EDB to water-soluble products in pH and redox
buffered solutions was also observed in the groundwater and
deionized water experiments discussed previously.

Figure 9. Degradation of EDB and partitioning of ’Co¬
products in buffered reducing solutions as a function of pH
and temperature. Each point is the average of duplicate
analyses.
9a. Solutions buffered at pH 5.
PHTHALATE BUFFER
EDB
•
ACETATE BUFFER
EDB
PHTHALATE BUFFER
HEXANE C-14
â–²
ACETATE BUFFER
HEXANE C-14
PHTHALATE BUFFER
AQUEOUS C-14
â– 
ACETATE BUFFER
AQUEOUS C-14

TIME (DAYS)
PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
1
CD
o
6 uM EDB
pH 5

Figure 9 continued.
9b. Solutions buffered at pH 7.
CARBONATE BUFFER
EDB
PHOSPHATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
â–²
PHOSPHATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14
â– 
PHOSPHATE BUFFER
AQUEOUS C-14

PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
03
to
6 uM EDB
pH 7

Figure 9 continued.
9c. Solutions buffered at pH 9.
CARBONATE BUFFER
EDB
•
BORATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
BORATE BUFFER
HEXANE C-14
A
CARBONATE BUFFER
AQUEOUS C-14
â– 
BORATE BUFFER
AQUEOUS C-14

PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
I
§
o
O
oo
6 uM EDB
pH 9

85
The type of pH buffer system (phthalate versus acetate;
carbonate versus phosphate) had little effect on the
results. One exception to this trend was the pH 9 buffer
system (borate versus carbonate). A rate enhancement-effect
of borate (but not carbonate) on the degradation of EDB was
also observed in the previous study of the effect of pH on
EDB hydrolysis.
Where EDB was monitored through more than one half-
life, its degradation followed apparent first-order decay.
EDB, initially present in a concentration of 6 ¿¿M, was no
longer detectable at 100 days in each of the three pH
buffering systems held at 60°C. In solutions also
containing ca. 500 or 1000 /lx.M H2S(aq), very different patterns
of EDB's transformation emerged (Figures 10a - lOf) and are
described below. These solutions contained the same
composition of pH and redox buffers as the controls
described above. These solutions were held at 25°C and
monitored for 254 days at pH 5 and 7 and for 150 days at pH
9. At 40°C, solutions of pH 5 and 7 were monitored for 93
days and for 82 days at pH 9. At 60°C, the solutions at pH
5 and 7 were watched for 62 days and for 19 days at pH 9.
At the start of the incubation of these solutions, the
dissolved oxygen was less than 0.07 ppm. The initial redox
potentials for the solutions buffered at pH 5, 7 and 9
ranged from -240 to -258 mV, -238 to -291 mV and -284 to -
345 mV, respectively. The first notable difference produced
by the addition of H2S(aq)
was that EDB was transformed in

Figure 10. Degradation of EDB and partitioning of 14C-
products in buffered reducing solutions containing H2S(aq)
as a function of pH and temperature. Each point is the
average of duplicate analyses with relative differences less
than 3%.
10a. Solutions buffered at pH 5 with an H2S(aq) concentration
of ca. 500¿tM.
PHTH ALATE BUFFER
EDB
ACETATE BUFFER
EDB
PHTHALATE BUFFER
HEXANE C-14
â–²
ACETATE BUFFER
HEXANE C-14
PHTHALATE BUFFER
AQUEOUS C-14
â– 
ACETATE BUFFER
AQUEOUS C-14

PERCENTAGE EDB REMAINING
OR
14C PARTITIONING
03
6 uM EDB, 500 uM
pH 5

Figure 10 continued.
10b. Solutions buffered at pH 7 with an H2S(aq)
of ca. 500/uM.
CARBONATE BUFFER
EDB
PHOSPHATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
A
PHOSPHATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14
PHOSPHATE BUFFER
AQUEOUS C-14
concentration

PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
CO
CD
6 uM EDB, 500 uM
pH 7

Figure 10 continued.
10c. Solutions buffered at pH 9 with an H,S, ,
of ca. 500/xM. 2 (aq)
CARBONATE BUFFER
EDB
BORATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
BORATE BUFFER
HEXANE C-14
a
CARBONATE BUFFER
AQUEOUS C-14
â– 
BORATE BUFFER
AQUEOUS C-14
concentration

TIME (DAYS)
PERCENTAGE EDB REMAINING
OR
14C PARTITIONING
¿SS8og¿SS8
tn
6 uM EDB, 500 uM
pH 9

Figure 10 continued.
10d. Solutions buffered at pH 5 with an H2S.
of ca. 1000/xM. aq
PHTHALATE BUFFER
EDB
ACETATE BUFFER
EDB
PHTHALATE BUFFER
HEXANE C-14
•••A
ACETATE BUFFER
HEXANE C-14
PHTHALATE BUFFER
AQUEOUS C-14
â– 
ACETATE BUFFER
AQUEOUS C-14
concentration

PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
u>
6 uM EDB, 1000 uM
pH 5

Figure 10 continued.
10f. Solutions buffered at pH 9 with an H2S(aq)
of ca. 1000/iM.
CARBONATE BUFFER
EDB
•
BORATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
BORATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14
â– 
BORATE BUFFER
AQUEOUS C-14
B
concentration

PERCENTAGE EDB REMAINING
OR
14C PARTITIONING
8 S 8 S 8
O
6 uM EDB, 1000 uM H S
pH 7 2

Figure 10 continued.
10e. Solutions buffered at pH 7 with an H2S{a
of ca. lOOOjiM. aq
CARBONATE BUFFER
EDB
PHOSPHATE BUFFER
EDB
CARBONATE BUFFER
HEXANE C-14
PHOSPHATE BUFFER
HEXANE C-14
CARBONATE BUFFER
AQUEOUS C-14
â– 
PHOSPHATE BUFFER
AQUEOUS C-14
concentration

TIME (DAYS)
PERCENTAGE EDB REMAINING
OR
14 C PARTITIONING
VO
6 uM EDB, 1000 uM H S
pH 9 2

98
incubations at a temperature as low as 25°C. Furthermore,
degradation rates of EDB were greater at pH 7 and 9 compared
to pH 5 at all temperatures. The time at which the initial
6 ¿xM EDB was no longer detected was much shorter in the
presence of H2S(aq), ranging between 3 2 days (at pH 5,
60°C,and 500 ¿xM H2S(aq)) and 4 days (at pH 9, 60°C, and 1000
MM H2S(aq)).
Secondly, the partitioning of 14C-products in the
presence of H2S(aq) was not into the aqueous phase, as in
previous experiments. The recovery of the uC-activity
(initially 14C-EDB tracer) in the individual ampules
analyzed during the incubation period was between 95 and
105%. The 14C-activity found in the hexane and aqueous
phases after extraction was also between 95 and 105% of the
amount of tracer in the original solution.
Apparent first-order disappearance rate constants were
derived from plots of the In percent EDB remaining vs. time
for each of the pH- and redox-buffered deionized water
control solutions and solutions containing H2S(aq) (Tables 8,
9, 10) . The initial concentrations of EDB (ca. 6 /xM) and
H2S(aq) (500 or 1000 /xM) were determined immediately after
filling and sealing the incubation ampules. In general,
greater than half the initial concentration of H2S(aq)
remained by the midpoint of incubations. By the end of the
incubations amounts of H2S(aq) remaining ranged from 65% of
the initial concentration to none detectable.

99
Table 8. Apparent first-order rate constants for the degradation
of EDB in solutions at 25, 40 and 60°C and with pH 5 to 9.
Temp
Buffer3/
CQ
data Dts.
25
PHT/6
ACE/6
PHOS/6
CARB/6
BOR/6
CARB/6
40
PHT/15
ACE/15
PHOS/15
CARB/15
BOR/13
CARB/15
60
PHT/13
ACE/13
PHOS/13
CARB/13
BOR/7
CARB/13
pHb
Initial
[EDB],
/XM
5.01
5.61
5.04
8.22
6.84
6.35
7.13
5.62
9.10
5.47
8.89
5.78
5.01
5.61
5.04
8.22
6.84
6.35
7.13
5.62
9.10
5.47
8.89
5.78
5.01
5.61
5.04
8.22
6.84
6.35
7.13
5.62
9.10
5.47
8.89
5.78
Initial
[H2S],
lo3^-
¡i M
d-1
0
-0.33
0
-0.20
0
-0.57
0
-0.57
0
-0.57
0
-0.41
0
5.14
0
2.82
0
5.40
0
3.81
0
5.60
0
5.53
0
65.02
0
62.67
0
61.62
0
66.53
0
80.45
0
68.45
C.D.J
(r)
±
0.30
0.2232
±
0.26
0.1258
±
0.33
0.4329
±
0.33
0.4356
0.57
0.4959
±
0.18
0.5742
±_
0.33
0.9490
±
0.26
0.8977
0.26
0.9703
±
0.25
0.9449
±
0.46
0.9320
0.26
0.9728
±
3.78
0.9641
±
2.51
0.9827
±
3.40
0.9676
±
5.22
0.9366
6.02
0.9728
2.62
0.9709
3 Buffers: 0.010 M; PHT= phthalate, ACE= acetate, PHOS= phosphate, CARB= carbonate,
BOR= borate; /i= 0.015 M, adjusted with KC1; 0.001 M Ti (III) citrate redox buffer.
b pH deviated < 1.0 unit during incubation; change with temperature < 2% (Covington et al, 1985).
c Calculated as pseudo-first order reaction with EDB, [H20] >> [EDB]. Uncertainties represent the
standard error in the slope of the linear least-squares fit plots of In [EDB] remaining vs. time.
d Coefficient of determination; where r is the correlation coefficent in linear least-square regression analysis.

100
Table 9. Apparent first-order rate constants for the degradation
of EDB in solutions containing initial concentrations of ca. 500
/iM H2S(aq) at 25, 4 0 and 60°C and with pH 5 to 9.
Temp
Buffer2/
CQ
data pts.
25
PHT/14
ACE/15
PHOS/15
CARB13
BOR/12
CARB/12
40
PHT/14
ACE/14
PHOS/14
CARB/13
BOR/16
CARB/16
60
PHT/6
ACE/6
PHOS/3
CARB/3
BOR/10
CARB/10
pHb
Initial
[EDB],
UM
4.58
5.99
5.00
5.45
6.58
5.90
6.90
5.37
9.10
5.96
8.95
5.99
4.58
5.99
5.00
5.45
6.58
5.90
6.90
5.37
9.10
5.96
8.95
5.99
4.58
5.99
5.00
5.45
6.58
5.90
6.90
5.37
9.10
5.%
8.95
5.99
Initial
[H2S]T,
103 kob>‘
UM
d1
384.2
0.04
400.2
0.06
494.6
3.15
561.2
4.01
599.1
2.76
637.0
3.04
384.2
7.48
400.2
14.02
494.6
32.81
561.2
28.20
599.1
19.42
637.0
16.71
384.2
117.55
400.2
182.21
494.6
591.26
561.2
606.39
599.1
300.43
637.0
471.79
C.D.d
(rV
0.12
0.0119
0.33
0.2076
±
0.20
0.9517
±
0.16
0.9837
0.37
0.8476
■±
0.41
0.8431
0.27
0.9847
0.10
0.9368
3.54
0.8776
±
0.60
0.9951
±
0.72
0.9810
±
0.74
0.9729
±
8.17
0.9811
■±
15.20
0.9728
1.30
1.0000
±
45.75
0.9943
±
16.28
0.9886
±
39.32
0.9770
a Buffers: 0.010 M; PHT= phthalate, ACE= acetate, PHOS= phosphate, CARB= carbonate,
BOR= borate; /i= 0.015 M, adjusted with KCI; 0.001 M Ti (III) citrate redox buffer.
b pH deviated < 1.0 unit during incubation; change with temperature < 2% (Covington et al., 1985).
c Calculated as pseudo-first order reaction with EDB, [H2S(aq)] > > [EDB]. Uncertainties represent the
standard error in the slope of the linear least-squares fit plots of In [EDB] remaining vs. time.
d Coefficient of determination; where r is the correlation coefficent in least square linear regression analysis.

101
Table 10. Apparent first-order rate constants for the degradation
of EDB in solutions containing initial concentrations of ca. 1000
¿iM H2S(ag) at 25, 40 and 60°C and with pH 5 to 9.
Temp
Buffer3/
ro
data Dts.
25
PHT/15
ACE/14
PHOS/15
CARB/15
BOR/12
CARB/12
40
PHT/14
ACE/13
PHOS/11
CARB/11
BOR/16
CARB/14
60
PHT/6
ACE/5
PHOS/3
CARB/3
BOR/7
CARB/4
r>Hb
Initial
[EDB],
fiM
5.00
5.99
5.72
5.85
6.95
5.52
7.73
5.34
8.98
5.74
9.05
6.03
5.00
5.99
5.72
5.85
6.95
5.52
7.73
5.34
8.98
5.74
9.05
6.03
5.00
5.99
5.72
5.85
6.95
5.52
7.73
5.34
8.98
5.74
9.05
6.03
Initial
[HjSfo
10' iw
/iM
d'1
706.1
1.18
748.2
2.53
929.3
6.83
1193.9
11.54
1309.3
9.22
1189.7
13.35
706.1
14.35
748.2
28.72
929.3
71.22
1193.9
78.30
1309.3
63.05
1189.7
78.10
706.1
357.52
748.2
214.19
929.3
988.17
1193.9
1074.16
1309.3
1746.87
1189.7
1624.96
C.D.d
(r2)..
0.28
0.5806
±
0.38
0.7877
0.44
0.9488
1.07
0.8993
±
1.33
0.8269
1.03
0.9439
±
0.68
0.9735
1.20
0.9811
3.84
0.9745
±
9.05
0.8926
±
3.13
0.9666
±
4.41
0.9631
±
65.20
0.8827
11.43
0.9915
67.48
0.9954
±
43.33
0.9984
±
185.92
0.9464
343.06
0.9182
3 Buffers: 0.010 M; PHT= phthalate, ACE= acetate, PHOS= phosphate, CARB= carbonate,
BOR= borate; /i= 0.015 M, adjusted with KC1; 0.001 M Ti (III) citrate redox buffer.
b pH deviated < 1.0 unit during incubation; change with temperature < 2% (Covington et al., 1985).
c Calculated as pseudo-first order reaction with EDB, [H,S(a<))] > > [EDB]. Uncertainties represent the
standard error in the slope of the linear least-squares fit plots of In [EDB] remaining vs. time.
d Coefficient of determination; where r is the correlation coefficent in least square linear regression analysis

102
Buffered solutions incubated at 25°C (Table 8) had poor
coefficients of determination for the least-squares
regression line and slopes not significantly different then
zero, i.e., a large standard error of the slope compared
tothe slope. At 40 and 60°C, coefficients of determination
(r2) ranged from 0.90 to 0.98 and the experimental
uncertainty, represented by the standard error of the slope,
was no greater than 10 percent in these plots. The
linearity of these plots indicate first-order degradation or
pseudo-first order hydrolysis kinetics with EDB. In
agreement with the experiment carried out in buffered
groundwater and deionized water, the degradation rate of EDB
in these reducing solution controls (without H2S(aq)) was
independent of pH, within experimental error.
In the solutions incubated with H2S(aq), the EDB
degradation first-order plots were linear (i.e.,
coefficients of determination (r2) between 0.88 and 1.00),
at all three incubation temperatures and all three pH values
with one exception. The coefficients of determination
ranged from 0.1 to 0.8 for solutions buffered at pH 5
incubated at 25°C, the rate of EDB degradation was
indistinguishable from experimental error, i.e., EDB
degradation did not occur under these conditions through the
duration of the experiment. All other first-order plots had
standard errors of the slopes less than 10 percent. The
observed EDB degradation rate constants in these solutions
with H2S(aq), ranged from approximately 1.5 to more than 2 0

103
times the greater than rate constant for the corresponding
pH and temperature control incubation. The effect of the
initial concentration of H2S(aq) on the EDB degradation
observed rate constants, kobs, as a function of pH at 40°C is
shown in Figure 11. The dashed boxes in the figure
correspond to the common initial H2S(aq) concentrations.
Relative to their respective pH values, in control reducing
solutions containing concentrations of ca. 500 or 1000 ¿xM
H2S(aq), the EDB degradation rate constants were approximately
an order-of-magnitude greater.
The speciation of the total H2S(aq), [H2S]T, as H2S(aq) or
HS' is a function of both pH and temperature. Temperature
has a marked effect on the first dissociation constant of
H2S(aq), ka1, as described by Barbero et al. (1982). By
measuring apparent molar heat capacities and volumes for
NaHS and H2S(aq) the following expression was derived:
log Ka1(T) = 19.840 + 930.8/T - 2.800 In T,
where Ka1 (T) is the first-acidic dissociation constant at
temperature, T (°K) . The resulting temperature-corrected ka1
values were derived and the sulfide speciation was
determined using the Henderson-Hasselbach equation as
follows:
pH = pka1 + log [HS-]/[H2S(aq)]
The calculated values of pka1 for all the incubations
are shown in Tables 11 and 12. The pKa fsecond-acidic
dissociation constant of H2S(aq) is 12.90 at 25°C (Dean,
1985). Between pH 5 and 9, the concentration of S"2 is very

Figure 11.
function of
First-order EDB degradation rate constants as a
pH, buffer and H2S(aq) concentration at 40°C.

Wx1000> d'
105
50
30
20
10
5
3
2
PS
PSn
C7
C7
A
P
P â–¡
P
PS
O
o
C7 •
C9 â–²
B A
C9
â–¡
B
C9 • O
6 7
pH
REDUCING SOLUTION
o •
500 uM ca. H2S
â–¡ â– 
1000 uM ca. H2S
A â–²
P = PHTHALATE
A = ACETATE
PS = PHOSPHATE
C7 = CARBONATE
B = BORATE
C9 = CARBONATE

106
small; at pH 9.0 and 25°C, the concentration of S"2 in a
solution of 1000 /¿M H2S(aq) would be 0.13 /xM. Furthermore,
the lower concentration of this species present in solution
at pH 7 (0.0013 ¿xM) is not reflected in changes in the
observed EDB degradation rates. Therefore, it is probably
not an important reactant.
The second-order rate constants, kH2s and kHS_, for EDB
degradation were then derived (Tables 11 and 12). They were
calculated as follows:
^h2s = ^obs/ t^2^» ] t and kHS_ = kobs/[HS-],
where [H2S]T is the total initial molar concentration of
sulfide as H2S(aq), and [HS-] is the initial molar
concentration of sulfide present as HS-.
The values of kH2s are consistent with the corresponding
observed first-order rate constants, kobs in Tables 9 and 10.
The rate of EDB degradation increases both with temperature
and H2S(aq) concentration. Buffering the solutions at pH 5
resulted in values of kH2s at least one-half less than the
values in solutions buffered at pH 7 or 9. On the other
hand, the values of kHS_ are not consistent with the
corresponding first-order rate constants, kobs. The kH2s
values from corresponding pH buffers and temperature
incubations obtained for the initial concentrations of 500
and 1000 /xM H2S(aq) are good agreement, within experimental
error, exception for solutions buffered at pH 9 and
incubated at 60°C. In the latter solutions, kH2s values at

107
Table 11. Second-order rate constants for degradation of EDB,
calculated for initial concentrations of ca. 500 /¿M H2S(aq).
Initial
Initial
Temp
pK,,c
[HjSJ*
[HS],
k d
kH2S>
CQ
Buffer3
nHb
HM
HM
M-‘ d1
M1 d’1
25
PHT
4.58
7.01
384.2
1.4
0.12
32.14
ACE
5.00
400.2
4.0
0.15
15.50
PHOS
6.58
494.6
241.6
6.38
13.06
CARB
6.90
561.2
248.6
7.15
16.15
BOR
9.10
599.1
594.4
4.60
4.60
CARB
8.95
637.0
629.9
4.77
4.82
40
PHT
4.58
6.73
384.2
2.7
21.48
2770.75
ACE
5.00
400.2
7.4
35.02
1894.05
PHOS
6.58
494.6
206.4
66.34
158.97
CARB
6.90
561.2
336.4
50.26
83.84
BOR
9.10
599.1
596.6
27.41
32.55
CARB
8.95
637.0
633.2
26.24
26.40
60
PHT
4.58
6.37
384.2
6.1
304.53
19269.84
ACE
5.00
400.2
16.3
455.30
11178.59
PHOS
6.58
494.6
305.7
1195.43
1934.12
CARB
6.90
561.2
432.7
1080.53
1401.41
BOR
9.10
599.1
598.0
501.15
502.39
CARB
8.95
637.0
635.3
740.64
742.63
3 Buffers: 0.010 M; PHT= phthalate, ACE= acetate, PHOS= phosphate, CARB= carbonate,
BOR= borate; H= 0.015 M, adjusted with KC1; 0.001 M Ti (III) citrate redox buffer.
b pH deviated < 1.0 unit during incubation; change in pH with temperature < 2%
(Covington et al., 1985).
c Temperature dependence of the first ionization constant of H,S(aq), pK^,, is described by Barbero et al.
(1982). Speciation was calculated by the Henderson-Hasselbalch equation, pH = pk^ + log [HS]'/[H;S(aq)].
d Second-order rate constant, koby[H,S(aq)]T; [H,S(aq)] > [EDB].
* Second-order rate constant, k^jHS']; [HS] > [EDB].

108
Table 12. Second-order rate constants for degradation of EDB,
calculated for initial concentrations of ca. 1000 jlíM H2S(aq).
Temp
pK,,c
£!Q
Buffer3
pHb
25
PHT
5.00
7.01
ACE
5.72
PHOS
6.95
CARB
7.73
BOR
8.98
CARB
9.05
40
PHT
5.00
6.73
ACE
5.72
PHOS
6.95
CARB
7.73
BOR
8.89
CARB
9.05
60
PHT
5.00
6.37
ACE
5.72
PHOS
6.95
CARB
7.73
BOR
8.98
CARB
9.05
Initial
Initial
[H,S]t,
[HS],
k d
kH2S>
UM
ÃœM
M-1 d1
M-1 d1
706.1
7.0
1.67
261.43
748.2
37.3
3.38
67.77
929.3
459.3
7.35
14.87
1193.9
1006.5
9.67
11.47
1309.3
1295.8
7.04
7.12
1189.7
1179.2
11.22
11.32
706.1
13.1
29.33
1095.57
748.2
67.3
38.38
426.70
929.3
582.4
76.64
122.29
1193.9
1086.0
65.60
72.10
1309.3
1302.0
48.15
48.42
1189.7
1184.1
65.65
65.96
706.1
28.7
506.33
12436.02
748.2
136.1
286.27
1573.78
929.3
734.7
1063.35
1344.99
1193.9
1143.7
899.71
939.20
1309.3
1306.0
1334.20
1337.57
1109.3
1187.1
1464.87
1368.85
3 Buffers: 0.010 M; PHT= phthalate, ACE= acetate, PHOS= phosphate, CARB= carbonate,
BOR= borate; /f= 0.015 M, adjusted with KC1; 0.001 M Ti (III) citrate redox buffer.
b pH deviated < 1.0 unit during incubation; change in pH with temperature < 2%
(Covington et al., 1985).
c Temperature dependence of the first ionization constant of H,S(aq), pK_,,, is described by Barbero et al.
(1982). Speciation was calculated by the Henderson-Hasselbalch equation, pH = pl^, + log [HS']/[H2S(aq)].
d Second-order rate constant, koba/[H:S(aq)]x; [H,S(aq)] > [EDB],
e Second-order rate constant, koba/[HS ]; [HS] > [EDB].

109
1000 /iM H2S(aq) exceed values with 500 H2S(aq) by a factor of
two or three. In addition, at all temperatures and all
H2S(aq) concentrations, the kH2s values at pH 7 were greater
than those at pH 9. These kinetic observations suggest that
the reactions involved in the degradation of EDB in presence
of H2S(aq) do not simply involve the attack of HS' on the EDB
molecule.
Product Identification
In an effort to identify the majority of the products
resulting from the transformation of EDB in solutions with
H2S(aq), initial concentrations of 60 /¿M EDB and 1000 or 2000
MM H2S(aq) in buffered solutions were incubated and examined
as described before in the kinetic experiments.
The number and size of peaks in GC/EC chromatograms of
hexane extracts increased during the progression of the
kinetic experiments. Experiments employing greater initial
reactant concentrations for the purpose of identifying
transformation products, however, were more informative.
Use of GC/FPD-S provided information for selectively
identifying sulfur-containing products, while GC/MS gave
valuable compound structural information.
To aid in identifying the sulfur-containing
transformation products of EDB, conditions were established
for separation and detection of ten standard sulfur-
containing compounds described earlier (Table 4). In Figure
12, the resulting chromatogram of these analytical standards
is shown. Linear ranges of detection of these compounds

Figure 12. Gas chromatogram showing separation and FPD-S detection of 10
commercially available sulfur-containing standards used in identifying sulfur-
containing products from the reaction of EDB and H2S(aq).

FPD/S RESPONSE
1
2
3
4
5
6
7
8
9
10
TIME (MIN)
BUTANETHIOL
1.2-ETHANEDITHIOL
ETHYL DISULFIDE
CYCLOHEXYLTHIOL
1,4-DITHIANE
BUTYL DISULFIDE
1.3.5-TRITHIANE
1.3-DITHIOLANE-2-THIONE
1.3.5-TRITHIACYCLONONANE
1,4,7,10-TETRATHI ACYC LODODEC A N E
111

112
established under these conditions were from 0.10 nmol to
5.00 nmol (equivalent to 8 to 1100 ng) for each compound
injected.
The sulfur-containing compound, 1,2,5,6-tetrathia-
cyclooctane, not commercially available, was synthesized
following the procedure of Goodrow et al. (1982). After
recrystallization from hexane, most of the product melted
between 90-95°C. Some non-melting solid remained in the
melt up to 300°C. Goodrow et al. (1982) reported similar
observations. With the GC/FPD-S and GC/MS techniques used
in this study, the purity of product after the hexane
recrystallization was adequate for product identification.
Single peaks were present in the GC/FPD-S chromatograms of
both the starting material, 1,2-ethanedithiol, and the
synthesis product (Figure 13). A single product peak was
also obtained in the GC/MS analysis and provided evidence
supporting the fact that the synthesis was successful. This
will be discussed later.
Mass spectra, in both electron impact (El) and chemical
ionization (Cl) modes helped in identifying the EDB
transformation products formed in the solutions with
H2S(aq). The mass spectra of the sulfur-containing
standards introduced earlier (Table 4 and Figure 12) are
presented in Table 13. In the El spectrum of each compound,
the molecular ion (ionized, intact ion M+) was present; it
was the most intense peak (i.e., the base peak, assigned

Figure 13. Gas chromatogram, using FPD-S detection, of solvent blank
(recrystallization solvent, 1,2-ethanedithiol (the precuror for the organic
synthesis), 1,2,5,6-terathiacyclooctane, the product.

FPD/S RESPONSE
1,2-ETHANEDITHIOL
(SYNTHESIS PRECURSOR)
1,2,5,6-TETRAT HIACYC LO-
OCTANE
(SYNTHESIS PRODUCT)
HEXANE
(RECRYSTALLIZATION
SOLVENT)
114

Table 13
Mass spectrometry of sulfur-containing standard compounds.
Chemical Formula/
Compound Formula Weight
S Isotope I’eak Ratio"; Mf2
Fragment Ions, m/z (Relative Intensity)3 Observed Calculated
Electron Impact Modeb Chemical Ionization Modec El, Cl (# of S Atoms)
Adduct
Ions, Cl
l-Butanethiol
C4H10S
90.16
90 (65), 71 (18), 61 (20), 56 (100), 47
(45), 44 (21), 39 (44), 36 (11)
N.A.
N.D.
4.4 (1)
N.D.
1,2-Ethanedithiol
C:H6S,
94.20
% (6), 94 (75), 73 (18), 61 (36), 60
(57), 59 (28), 58 (24), 57 (25), 47
(1001, 45 (40)
N.A.
8.1
8.8 (2)
N.D.
Cyclohexylthiol
c4h12s
116.23
116 (54), 83 (54), 82 (56), 81 (7), 73
(8), 67 (69), 60 (10), 59 (6), 58 (8), 57
(18), 56 (15), 55 (1001, 54 (28), 53
(11)
173 (3), 119 (5), 118 (8), 117
(1001, 116 (15)
3.7, 5.0
4.4 (1)
M + 57
Ethyl disulfide
c4n,«s2
122.25
124 (8), 123 (6), 122 (1001, 94 (59), 68
(7), 66 (89), 64 (10), 61 (8), 60 (11),
59 (14), 58 (10), 57 (17), 56 (11)
N.A.
8.0
8.8 (2)
N.D.
1,4-Dithiane
c4h10s2
120.24
122 (7), 121 (7), 120 (1001, 92 (15), 73
(7), 64 (11), 61 (50), 60 (23), 59 (12),
58 (12), 55 (6)
176 (1), 163 (4), 161 (2), 123
(11), 122 (8), 121 (1001, 120
(8), 117 (2)
7.3, 8.4
8.8 (2)
M + 43
M + 57
l,3-Dithiolane-2-thione
C3H4S3
136.26
138 (11), 137 (5), 136 (1001, 108 (7),
76 (28), 64 (16), 60 (41), 59 (7), 44
(35)
N.A.
10.8
13.2 (3)
N.D.
1,3,5-Trilhiane
138.27
140 (13), 138 (1001, 92 (28), 91 (9), 86
(13), 73 (9), 64 (16), 61 (6), 60 (12),
59 (10), 58 (6), 57 (70), 56 (45), 55
(7)
N.A.
11.5
13.2 (3)
N.D.
Butyldisulfide
c8h18s2
178.36
178 (39), 122 (33), 87 (6), 86 (6), 58
(9), 57 (100), 56 (19), 55 (9)
267 (2), 235 (2), 221 (3), 181
(9), 180 (12), 179 (1001, 178
N.D., 8.5
8.8 (2)
M + 43
M + 57
(16)
(Continued)
115

(Continued) Table 13.
S Isotope Peak Ratio4; M + 2
Chemical Formula/
Fragment Ions, m/z /Relative Intensity/1
Observed
Calculated
Adduct
Compound Formula Weight
Electron Impact Mode2
Chemical Ionization Mode3
El, Cl
(# of S Atoms)
Ions, Cl
1,4,7-Trithiacyclo-
nonane
c6h12s,
180.36
182 (9), 181 (11), 180 Q00), 121 (27),
120 (22), 119 (27), 106 (42), 105 (16),
93 (11), 92 (13), 87 (16), 85 (9), 78
(15), 64 (28), 61 (95), 60 (46), 59 (42),
58 (26), 57 (11), 47 (16)
237 (1), 183 (13), 182(10), 181
(100), 179 (12), 153 (11), 135
(6), 121 (12), 106 (11)
9.1, 12.5
13.2 (3)
M + 57
1,2,5,6-Tetrathiacyclo-
octane
C4H8S4
184.28
186 (18), 184 Q00), 156 (7), 130 (9),
128 (51), 126 (9), 124 (73), 96 (8), 93
(8), 92 (58), 91 (7), 66 (5), 64 (54), 61
(11), 60 (24), 59 (36), 58 (13), 57 (7)
N.A.
18.0
17.6 (4)
1,4,7,10-Tetrathiacyclo-
dodecane
C8lll<>S4
240.47
240 (47), 121 (41), 120 (35), 105 (35),
87 (41), 86 (35), 64 (29), 61 (59), 60
(71), 59 (35), 46 (53), 45 (59), 44 (59),
43 (29), 40 (100/
297 (2), 243 (17), 242 (13), 241
(100/, 240 (15), 213 (17), 195
(7), 153 (9), 135 (5), 121 (8),
106 (12)
N.D., 17.4
17.6 (4)
M + 57
4 Percent of the base ion peak; ions with greater than 5% relative intensity shown for electron impact, greater than 1% shown for chemical ionization.
b Source temperature, ca. 250 °C; 0.2 Torr; electron energy, 70 eV
c Positive ion mode; isobutane ionizing reagent gas; source temperature, ca. 150 °C; electron energy, 70 eV
d S-isotope ratio of molecular ion (M) or pseudo-molecular ion (M + l) peaks shown in El and Cl spectra, respectively; natural abundance 3,S = 4.4%
N.A. Not analyzed in this mode
N.D. Not detected

117
a value of 100%) in 5 of the 11 standards. In the Cl
spectra, pseudo-molecular ions (M+l) were always present as
the base peak. The sulfur isotope ratios observed for the
molecular ions, i.e., M+2/M for the natural occurrence of
34S:32S, 4.4:100, were generally very close to the calculated
values (Table 13). Cl spectra containing M+43 and M+57 were
observed. These are the adduct ions produced by addition of
the isobutane ionization reagent gas. The adduct ions are
useful for confirming molecular weights of the standards and
unknowns. The reconstructed GC/MS chromatogram and the
GC/FPD-S chromatogram of a hexane extract of the reaction
solution (Figure 14), gave peaks with similar retention
times. One (1,4-dithane) of the five sulfur-containing
standard compounds, chromatographed under the same GC/FPD-S
conditions, matched the retention time of a peak in the
extract chromatogram. Mass spectra of well resolved peaks
detected in the extracts of several EDB and H2S(aq)
incubations are compiled in Table 14. In all El mass
spectra, the molecular ion peak (M+, ionized intact com¬
pound) was the most intense ion fragment, i.e., the base
peak assigned a value of 100%, with the exception of the
1,4,7,10-tetrathiacyclododecane (Table 12). In the latter
spectra, the molecular ion was somewhat stable, being 39% of
the m/e 57 ion base ion peak. All El spectra were
representative of each standard with regard to its true
molecular weight. The spectra provided satisfactory

Figure 14. Gas chromatograms of EDB transformation products
from solutions containing H2S(aq) in product studies (top and
middle) and sulfur-containing standards (bottom). The
legend for numbered peaks in the reconstructed ion
chromatogram of positive ion chemical ionization (top) with
assigned identities is as follows: 1=EDB, 4=DT, 5=TTCP,
6=TTCH, 7=TTC0, 8=TTCD.

RELATIVE RESPONSE RELATIVE RESPONSE RELATIVE ION INT ENSIT Y ( x 10)
DEGRADATION PRODUCT IDENTIFICATION
119
1 . 2-ethanedithiol
cyclohexyl mercaptan
1,4-dithiane
butyl disulfide
1 ,4 , 7-trithiacyclononane

Table 14. Mass spectrometry structure elucidation of sulfur-containing products in EDB and
H2S(aq) solutions.
Chemical Formula/
Compound Formula Weight
S Isotope Peak Raliod; M + 2~
Fragment Ions, m/z (Relative IntcnsiivV Observed Calculated
Electron Impact Mode'’ Chemical Ionization Modec El, Cl (# of S Atoms)
Adduct
Ions
1,4-Dithiane
C41110S2
120.24
122 (7), 120 (100), 92 (17), 73 (5), 64
(11), 61 (64), 60 (22), 59 (9), 58 (8),
47 (7), 46 (58), 45 (28)
1,2,3-Trithiacyclopentane
C2H4S3
124.20
126 (11), 124 (100). 96 (26), 64 (10),
60 (40), 59 (26), 45 (16)
l,3-Dithiolane-2-lhione
C3H4S3
136.26
138 (14), 136 (1001, 108 (14), 107 (7),
81 (7), 76 (21), 59 (21), 45 (21), 40
(14)
1,3,5-Trithiane
C3H6S3
138.27
140 (13), 138 (1001, 92 (28), 91 (9), 86
(13), 73 (9), 64 (16), 61 (6), 60 (12),
59 (10), 58 (6), 57 (70), 56 (45), 55
CO
1,2,5-Trithiacycloheptane
C4H8S3
152.22
154 (14), 153 (6), 152(1001, 124 (20),
106 (15), 105 (5), 96 (7), 92 (17), 87
(38), 78 (18), 64 (17), 61 (10), 66 (44),
59 (7), 58 (10), 45 (27)
1,2,3,4-Tetrathiacyclo-
hexane
C3H4S4
156.26
158 (13), 156 (100), 130 (6), 128 (53),
92(10), 64 (32)
1,2,5,6-Tetrathiacyclo-
octane
c4h8s4
184.28
186 (11), 185 (7), 184 (100), 156 (7),
151 (7), 130 (9), 128 (20), 126 (11),
124 (40), 96 (7), 94 (9), 93 (7), 92
(24), 72 (7), 64 (16), 60 (7), 59 (16),
45 (7)
177 (1), 163 (3), 161 (1), 123
(8), 122 (7), 121 (100), 120
(17), 119(3)
6.6, 6.9
8.8 (2)
M + 43
M + 57
137 (3), 127 (13), 125 (100),
124 (33), 105 (5)
11.1, 12.6
13.2 (3)
N.D.
N.A.
14.3
13.2 (3)
N.D.
195 (2), 149 (2), 140 (5), 139
(100), 138 (23), 135 (5), 107
(12)
12.3, 10.3
13.2 (3)
M + 57
209 (1), 195 (2), 155 (14), 154
(9), 153 (100), 152 (18), 151
(1), 125 (2), 124 (1), 119 (2)
13.5, 13.5
13.2 (3)
M + 43
M + 57
N.A.
13.4
17.6 (4)
N.D.
187 (12), 186 (7), 185 (1001,
11.1, 12.3
17.6 (4)
N.D.
184 (17), 135 (2), 133 (3), 125
(3), 124 (4), 107 (2)
(Continued)
120

(Continued) Table 14.
Chemical Formula/
Fragment Ions, m/z /Relative Intensity!
S Isotope Peak Ratio; M + 2
Observed Calculated
Adduct
Compound Formula Weight
Electron Impact Mode
Chemical Ionization Mode
El, Cl
(# of S Atoms)
Ions
1,4,7,10-Tetrathiacyclo- CgH16S4
dodecane 240.47
240 (47), 121 (41), 120 (35), 105 (35),
87 (41), 86 (35), 64 (29), 61 (59), 60
(71), 59 (35), 46 (53), 45 (59), 44 (59),
43 (29), 40 (1001
297 (1), 279 (2), 244 (1), 243
(17), 242 (10), 241 (100), 240
(12), 223 (2), 215 (3), 214 (2),
213 (18), 195 (5), 193 (2), 185
(2), 181 (14), 180 (2), 167 (2),
165 (1), 163 (2), 167 (1), 154
(1), 153 (4), 135 (4), 133 (3),
121 (5), 120 (4), 119 (3), 117
(2), 105 (2), 103 (11), 101 (5)
N.D., 17.0
17.6 (4)
M + 57
* Percent of the base ion peak; ions with greater than 5% relative intensity shown for electron impact, greater than 1% shown for chemical ionization.
b Source temperature, ca. 250 °C; 0.2 Torr; electron energy, 70 eV
c Positive ion mode; isobutane ionizing reagent gas; source temperature, ca. 150 °C; electron energy, 70 eV
d S-isotope ratio of molecular ion (M) or pseudo-molecular ion (M+l) peaks shown in El and Cl spectra, respectively; natural abundance 34S = 4.4%
N.A. Not analyzed in this mode
N.D. Not detected

122
intensity of the M+ ion and informative fragmentation ions
useful for structural confirmation and elucidation of
closely related compounds. The pseudo-molecular ions (MH+
or molecular ion mass + 1, M+l) were present in the positive
Cl mass spectra of all the standards, and were the base ion
peak supporting the molecular weight determined in El mass
spectra. The sulfur-isotope ratio was also used in
elucidating structures. When the M+ ion is strong enough,
the number of sulfur atoms present in a compound can be
determined by the contribution of the 34S isotope (4.4%).
The sulfur-isotope peak ratios (M+2/M+) for the standards
are generally in reasonable agreement with the predicted
(calculated) values for the number of S atoms in the
molecule (Table 13). Lower than expected ratios are
probably due insufficient sensitivity to relatively low
concentrations of M+ present while the spectra were
obtained. Additional evidence for supporting the molecular
weights determinations was provided by reagent gas adduct
ions in positive Cl mass spectra. The C4H9 adduct (M+57)
and the C3H7 adduct (M+43) were present in the spectra of
four standards. The El mass spectra compiled in Tables 13
and 14 are available in Appendix C.
Assignment of molecular weight and structure to sulfur-
containing transformation products in solutions of EDB and
H2S(aq) were made by comparing the mass spectral evidence from
several of the product study incubations to the mass

123
spectral data of the sulfur-containing standards (Table 14).
These data provided direct evidence for identification of
five of the sulfur-containing compounds (DT, DTT, TT, TTCO,
TTCD) present in the extracts of incubations (Table 15).
The mass spectra of these products were essentially
identical to their corresponding analytical standard. The
retention times in GC/MS and GC/FPD-S analyses of these
compounds were identical to standards under the same
chromatographic conditions. Coinjection of incubation
extracts and standards resulted in identical retentions
times (Figure 15). Those peaks not matching a standard
still had very similar retention times to the standards.
The identities of these compounds were based on mass
spectral determination of molecular weight. Structural
rationale for some of the key fragment ions of TTCP, TTCH
and TTCO is presented in Figure 16. Goodrow et al. (1982)
note the presence of an intense m/e 124 fragment as
confirmation of the identity of TTCO. Since no analytical
standards were available for comparison, the identities of
TTCP and TTCH are tentative. Compounds with higher
molecular weights had longer retention times in the
capillary GC analyses. This sequence of elution resembled
chromatographic behavior of a homologous series of compounds
of similar structure. GC retention indices for closely
sulfur-containing compounds have been used for identifying
sulfur vesicants and related compounds elsewhere (D'agostino
et al. 1988) .

Table 15. Chemical and structural formulae of sulfur-containing products from reactions of
EDB and H2S(aq). The identity of these compounds were established by GC/MS and GC retention
times of known standards.
CHEMICAL FORMULA/
STRUCTURAL
COMPOUND
ABBREVIATION
FORMULA WEIGHT
FORMULA
1,2-Ethanedithiol
EDT
C2H6S2
94.20
HSCH2CH2SH
1,4-Dithiane
DT
C4H8S2
120.24
1 1
ch2ch2sch2ch2s
1,2,3-Trithiacyclopentane
TTCP
C2HaS3
124.20
1 1
ch2ch2sss
1,3-Dithiolane-2-thione
DTT
c3h4s3
136.26
1 1
ch2scssch2
1,3,5-Trithiane
TT
C3H6S3
138.27
1 1
ch2sch2sch2s
1,2,5-Trithiacycloheptane
TTCH
C4H8S3
152.22
1 1
ch2ch2sch2ch2ss
1,2,5,6-Tetrathiacyclooctane
TTCO
c4h8s4
184.28
1 ~1
ch2ch2ssch2ch2ss
1,4,7,10-Tetrathiacyclododecane
TTCD
C8H16S4
240.47
1 1
CH2CH2S (CH2) 2S (CH2) 2S (CH2) 2s

Figure 15. Sample GC/FPD-S chromatogram of the sulfur-
containing standards (top) and extracted incubation mixture
of EDB and H2S(aq) (middle) . Coinjection of standards and
incubation extract show superimposing peaks of TT at 12 min
and TTCO and 16 min (bottom).

126

Figure 16. Structural rationale for some key fragment ions
in mass spectrometry electron impact fragmentation of
sulfur-containing transformation products of EDB.

128
/S\
S S
\ /
^ S3 It
S2 It
m/e 64
H2C—CH
m/e 59
-> CH =S +
m /e 45
CH?=S-CH-
m/e 60
S-S
\
It
h2c ch2
I I
H2Cn /CH2
S —S
TTCO
m/e 184
h2c
h2c.
/
H-jC'
,S —S 11
h2c
^S —s
m/e 156
h2c ch2 It
m/e 92
-> S4 It -
m/e 128
-s3T.
m/e 96
s2~I-
m/e 64
m/e 124

129
Ethylene Dibromide in Sulfate Groundwater
Groundwater with a natural potential for producing
H2S(aq) was chosen in an attempt to observe transformation of
EDB by the H2S(aq) alternative degradation route. Groundwater
from four wells in Hendry County and south central Florida
were sampled because of historic data of "high sulfate",
i.e., concentrations in the range of 200-400 mg/L (Appendix
B). The reduction of 200 mg/L of sulfate would produce 71
mg/L (2080 /¿M) H2S(aq). The actual groundwater samples, which
were fortified with EDB and then studied, came from wells
which tapped different depths of the underlying aquifer
(Table 16). With regard to reactants with H2S(aq), one
notable difference between the samples was the presence of
dissolved iron (Fe) and total Fe. The formation of iron
sulfides are common reactions in anaerobic reducing
groundwater.
GC/EC chromatograms of the EDB-fortified water samples
after storage in the dark at 25°C for 9 months are shown in
Figure 17. In the untreated samples, the initial EDB
concentration of 1.0 mg/L had decreased in HE-0057 by 40%,
HE-0058 by 60%, and by 95% in L-02531. The EDB
concentrations in the autoclaved samples had not changed.
The sulfur-containing compounds EDT, TT, and TTCO were
detected in HE-0558 incubations by GC/FPD-S (Figure 18).
This sample was originally fortified, as in the earlier
buffered laboratory water product identification study, to

130
TABLE 16. Florida Ambient Groundwater Monitoring Network sampling
results for the water used in experiments in this study.
Total Well
SITE ID
Sampling
DATE
Temp
£!Q
PH
Units
UMHOS
/CM
so4
Qpg/L)
Fe
(mg/L)
Tot Fe
(me/Ll
Aquifer
Depth
(Feet)
HE-0557
022387
25.1
7.5
4490
357.7
0.01
0.11
Interned.
100
HE-Q558
022387
24.4
7.1
3780
226.0
5.54
7.35
Surficial
014
L-01977
010587
23.4
7.7
1991
226.5
0.05
0.05
Intermed.
185
L-02531
010587
26.7
7.8
3150
385.9
0.05
0.05
Floridian
605

Figure 17. GC chromatograms of extracts of EDB fortifed
groundwater that was incubated for 9 months at 25°C.

He-0558
He-0557
UNTREATED
DEGASSED
MINUTES
AUTOCLAVED

RTA-007
LP-0012P
EDB
UNTREATED
0 3 6 9 12 15 18 21
DEGASSED
_l I I L.
12 15 18 21
AUTOCLAVED
x
0 3 6 9 12 15 18 21
MINUTES

Figure 18. GC chromatograms of extracted groundwater containing naturally occurring
H2S(aq) and incubated anaerobically with EDB at 10 mg/L. Three confirmed sulfur-
containing products are identified.

FPD/S RESPONSE
0 2 4 6 8 10 12 14 16
MINUTES
JUuJ -
I L
0 2
j 1 i i i i i
4 6 8 10 12 14 16
MINUTES
135

136
a resulting concentration of 10 mg/L EDB. After storage of
the extract in a tightly sealed GC sample vial, reanalysis
revealed the EDT peak disappeared and other product peaks
increased. Analysis of the sample by GC/EC on two different
GC columns shows the difficulty experienced using EC
detection for analysis (Figure 19). The chromatograms were
not helpful in product identification. Because EC detection
is especially sensitive to organohalides, peaks in these
chromatograms may be intermediate degradation products
containing bromide.
HE-0558 groundwater EDB-fortified samples incubated for
more than a year contained H2S(aq) concentrations of 73 mg/L
(2060 juM) . In addition, visible guantities of the black
precipitate were present, presumably ferrous sulfide (FeS,
pyrite).

Figure 19. GC chromatograms comparing two chromatographic columns on a gas
chromatograph with an electron capture detector. Upper panels are injections of
sulfur-containing standards; bottom panels are injections of an extract of EDB-
fortified groundwater incubation (same sample in Figure 18).

ECD/25m x 0.20mm COLUMN
ECD/15m x 0.53mm COLUMN
S-STANDARDS
J 1 1-—i 1 1 1 1 1 1 i i i i i
1 1 â–  1 1 1 1 1 1 1 1 i i i i i i
0 4 8 12 16 20 24 28 30
MINUTES
138

DISCUSSION
Analytical Methods
The sensitive analytical methodologies employed in this
study seeked to explore the degradation and transformation
of EDB in aqueous systems and groundwater at EDB
concentrations which might be found at contaminated sites.
The methodology was supported by GC with selective GC
detectors, chemical derivatization, mass spectrometry, and
the liquid scintillation counting of 14C-labeled analyte.
GC/EC analysis of EDB was very sensitive. On the other
hand, GC/EC was not successful for the analysis of sulfur-
containing compounds, but GC/FPD-S was. The value of
monitoring 14C-activity was to (1) detect loss of 14C-analyte
throughout incubations and extractions, and (2) to study to
partitioning of the transformation products from water into
organic extracts. Although not employed in these
experiments, thin layer chromatography of 14C-transformation
products would be useful to isolate individual compounds to
then study their stability and toxicty.
Hydrolysis Reactions
The term "transformation" is commonly used to encompass
any changes in the chemical structure of the compound being
139

140
studied. A chemical contaminant or pesticide in the
environment is transformed by chemical, photochemical and
biochemical routes. The persistence of an organic
contaminant in the saturated zone, i.e., saturated soil or
groundwater, would largely be a function of whether
microogranisms can transform the compound. In contrast,
transformation by chemical hydrolysis alone is much slower.
In my preliminary studies, EDB's disappearence from
groundwater at environmental ambient temperature was
negligible over several months. Similarly, no significant
degradation of EDB was observed in soil at the same time as
the water samples which were obtained from the same regions
of Florida (Weintraub et al., 1985). It might be expected
that the long residence time of EDB in selected Florida
soils would allow adequate time for microbes to metabolize
EDB; however that did not occur. On the other hand,
hydrolytic mechanisms do take place, although at a slower
rate than biochemial degradation catalyzed by microbes.
Hydrolytic reactions of EDB were independent of pH
between 5 and 9. Therefore, the observed degradation rate
constant, kobs, is equivalent to k,, (neutral) in this pH
range. In the general acid/base catalysis expression:
kT = kH[H+] + k* + Iíqh[OH ]
kH, the rate constant for specific-acid catalysis, and koH,
the rate constant for specific-base catalysis are
insignificant. Beyond the environmental pH range, the

141
degradation rate increases, e.g., at pH 14, a 1.0 mg/L
aqueous solution degraded completely in less than 10 days at
23°C. These findings are in agreement with data compiled on
the hydrolysis of the general class of compounds of organic
halides (Maybey et al., 1978; Harris, 1982). For the
purpose of predicting degradation kinetics at environmental
pHs, the pseudo-first rate constant for k^^O], kh is
written for the hydrolysis rate law:
d T EDB1 = kh[EDB]
dt
The temperature dependence of any discrete chemical
process, i.e., no change in mechanism over the temperature
tested, may be expressed by the Arrhenius equation:
k = Ae~Ea/RT
where A is the entropy term, Ea is the activation energy, R
is the gas constant 1.987 cal deg"1 mol’1, and T the absolute
temperature. The Arrhenius plots (In k vs 1/T) for EDB
degradation were linear, supporting the earlier finding of a
single dominant degradation mechanism. A change in the
slope reflects a change in the Ea, which is characteristic
of a change in the reaction taking place. Extrapolating the
experimental rate constants from elevated temperatures in
Arrhenius plots to 22°C, the average temperature of Florida
groundwater, resulted in rate constants ranging from 6.4 x
10 2 to 2.76 x 10 3 d corresponding to half-lives of 772 to
259 days. As pointed out by Mabey and Mill (1978), a random

142
error of 10% in k leads to an Ea accurate only to 100%, or a
factor of 2. The uncertainty in E is magnified when
experimental rate data are extrapolated over 25°C or longer
intervals when making estimates of k under environmental
conditions. Due to inherent error in such determinations,
it is best to regard rate data obtained in this manner as
order-of-magnitude estimates (Harris, 1982).
Reactions with Aqueous Hydrogen Sulfide
The presence of H2S(aq) in solutions increased the
degradation rates of EDB by 3 to 20 fold compared to
hydrolysis reactions. The products are distinctly different
and much more varied as compared to the hydrolysis reaction.
The enhanced reactivity of H2S(aq) over the oxygen analog,
H20, stems from aspects of chemistry of the sulfur atom.
The electrons of sulfur are more numerous and further
removed from the nucleus than those surrounding oxygen;
therefore, sulfur's electrons are more polarizable. When
sulfur acts as a nucleophilic agent, due to its
polarizability, the reactive electron pair is more mobile
and can initiate bonding at a greater distance than can a
pair located on oxygen. Nucleophilicity order for SN2
mechanisms for some common reagents in aprotic solvents in
decreasing order is: SH-, CN-, I-, OH-, N3, Br-, AcO-, C1-,
H20 (March, 1985a). In theory based on mutual perturbation
of molecular orbitals, Klopman (1968) describes the

143
nucleophilic reactions of highly polarizable reagents on a
saturated carbon center as highly favored due to a "soft-
soft" interaction. The larger, more polarizable
nucleophiles (e.g. HS- or H2S) can more easily distort its
electron cloud to bring a greater degree of electron density
to the substrate than the smaller nucleophiles (e.g., OH- or
H20) whose electron clouds are more tigthly held. According
to Swain-Scott's (1953) quantitative relationship for
nucleophilicity, the rate of nucleophilic attack of HS' and
S03'2 on methyl bromide is approximately 1.3 x 105 times
greater than that of water. Hydroxide ion reacts at a rate
approximately 1.6 x 10A times that of water.
The array of sulfur-containing products in the
incubations of EDB and H2S(aq) demonstrates the reactivity of
the initial reactants and of products. The formation of the
thiol and cyclic-alkyl sulfide, disulfide, and trisulfide
compounds that were observed may have resulted from multi-
step pathways which included nucleophilic displacement
reactions by H2S(aq) and thiol functions. The formation of
sulfide linkages as in the di- and tri-sulfide cyclic
compounds are most likely the result of oxidative coupling.
This reaction can be catalyzed by trace metals or oxygen.
The reaction produces a free radical of the alkyl sulfide
which will react with another molecule that had ungone the
same process. This type of process is often called a
disproportionation reaction. Possibly pathways for the

144
formation of the sulfur-containing products are shown in
Figure 20.
Several five-, six, seven- and eight-membered cyclic
disulfides and bis(disulfides) were stable with respect to
polymer of the same molecular size in dilute solutions (ca.
10 mM) of thiol-disulfide interchange studies (Houk et al.,
1989). Similar sized sulfur-containing cyclic products
resulting from EDB and H2S(aq) were stable. Cyclic
trisulfides, like TTCP (found in this study), are not common
in nature. Although larger cyclic trisulfide analogues
could be synthesized, TTCP could not be made (Harpp et al.,
1979). This compound, however was also found in the
hydrolysate of sulfur vesicant chemical warfare agents
(Dagostino et al., 1988).
An attempt was made to establish a common rate term to
fit experimental data from the two EDB degradation
experiments using two different concentrations of H2S(aq).
The second-order rate constants, kH2S and kHS_ were calculated
for the pseudo-first order rate constants with EDB, kobs
(Tables 9 - 12) The rate constant, kHs., specifies that the
rate of EDB degradation will be dependent upon the
concentration of EDB and the concentration of HS~. The
observed produts suggest this may not be true, i.e., EDB
must react with intermediates to form products observed.
The kHS_ calculated for the two concentrations of H2S(aq) are
not in agreement. The description of EDB degradation in the

BrCH,CH,Br + HS' = H,S > BrCH2CH,SH
EDB Hydrogen
sulfide
= BrCH,CH2S' + BrCH,CH,Br
> BrCH2CH2SCH2CH,Br + HS' = H,S > HSCH2CH2SCH2CH2SH
2V'1
+ BrCH2CH2Br
+ HS7H2S
etc....
—> > > disproportionation reactions
cyclic sulfides and cyclic disulfides
Figure 20. Possible pathways of formation of sulfur-containing products observed in this
study.

146
presence of H2S(aq) by kH2s, however, does provide reasonable
agreement among the experimental data.
Another important finding was that there was no
consistent effect of pH on the EDB degradation rate
constants between pH 5 and 9. As ionization of H2S(aq) to HS-
increases with pH (pKa1 = 7.01, 25°C) , it is expected that
the rate of EDB degradation would also increase due to the
higher HS- concentration (HS- being the better nucleophile
of the two). Supporting this idea is the finding that the
rates of EDB degradation at pH 7 at all temperature and both
concentrations of H2S(aq) was 2 to 3 times greater than the
rates at pH 5. In contrast, at pH 9, the rates of EDB
degradation at all temperatures and both concentrations of
H2S(aq> were depressed in most cases compared to the rates of
degradation at pH 7. The effect on the rate of EDB
degradation might be influenced by increases in rates of
concurrent reactions. For instance, H2S(aq) may react less
with EDB and more with other products being formed in the
reaction mixture. The mean (± s.d.) of the second order
rate constant, kH2s, for EDB degradation in buffered
solutions at pH 7 for 25°C was 7.64 ± 1.42 M'1 d"1. At a
neutral pH and an environmental concentration of 10 mg/L
(294 /¿M) H2S(aq) at 25°C, the predicted EDB degradation rate
constant is 2.22 x 10'3 d'1.
The temperature dependence of the rate of EDB
degradation in the presence of H2S(aq) (both 500 and 1000 /¿M

147
experiments) follows Arrhenius kinetics. For solutions
buffered at pH 7, the plots of In k vs. 1/T had correlation
of determination (r2) greater than 0.99. The values of
activation energy (Ea) were between 25.6 and 29.5 Kcal
mol’1. The difference between the rates of degradation of
EDB in the H2S(aq) reaction and the hydrolysis reaction is
borne out in the relative magnitude of the frequency or
entropy factor, A. For degradation in the presence of
H2S(aq), values for A ranged from 5.19 x 1019 to 2.61 x 1022 M’1
d'1, compared to A values between 7.24 x 109 and 1.44 x 1013
M'1d'1 for the hydrolytic degradation.
A simplified rate law which can be used to fit the EDB
degradation experimental data involves terms for hydroylsis
of EDB, transformation by H2S(aq) and other reactive sulfide
species, and for the base-catalyzed reaction, if the pH is
above 10. Under environmental conditions, i.e., pH 6 to 9,
the overall equation to predict the rate of degradation
includes hydrolysis and H2S(aq) transformation terms (Figure
21) . The array of reactions of EDB with H2S(aq) and
intermediate products to form "secondary products"
contribute to the ks term. It follows from this discussion
that a major influence upon the persistence and
transformation products of EDB will be the presence of
H2S(aq) •
Microorganisms play a central role in the cycling of
sulfur species particularly in anaerobic environments

148
EDB + H20
EDB + H2S
EDB + RS'
-d[EDB]
dt
-d[EDB]
dt~
I I
HO OH
Substituted Products
Secondary S-Substituted Products
~ k h
[EDB]
+ kH2S
[EDB]
[H2S]
+ kRS
[EDB]
[RS ]
= kh [EDB] + k s [EDB] [H2S]
Figure 21. EDB transformation kinetics predicted for groundwater.

149
(Pfennig and Widdel, 1982; Bauld, 1986). Under anoxic
conditions H2S(aq) originates primarily from bacterial
reduction of sulfate. Some H2S(aq) may be produced through
the purification of sulfur-containing amino acids. However,
concentrations of H2S(aq) are not commonly reported, perhaps
due to analytical difficulties or highly variable
concentrations in nature. The genera of bacteria,
Desulfovibro and Desulfotomaculum are known to accelerate
the reduction of sulfate to H2S(aq) in natural waters. In
addition to an anaerobic environment, to support the
activities of sulfate-reducing bacteria, a carbon source is
required. Apparently a relatively low level of carbon
source, i.e., less than 1 mg/L of groundwater, is sufficent
to support these bacteria. In one of the few studies
reporting natural concentrations of H2S(aq) Dohnalek et al.
(1983) found H2S(aq) concentration as high as 12 mg/L and
averaged of 5.5 mg/L in deep wells of Elgin, Illinois. Ford
(1971, 1973) provides some indication of the potential
production of H2S(aq) in soils poorly drained soils in
flatwoods areas of central Florida. He studied the H2S
produced in the citrus root environment in these soils and
in the groundwater from the region. Both soil and
groundwater were found to be good sources of sulfides. The
production of H2S(aq) in soils increased to 20 mg/L in 6 days
in laboratory incubation. Over a five month period, the
concentration of total sulfides collected from groundwater

150
in sorptive cells fluctuated between 2 and 16 mg/L. The
stability of H2S(aq) in groundwater or soil is highly
dependent upon environmental factors.
The rate of oxidation of H2S(aq) has been well studied,
mainly due to its offensive taste and odor in drinking
water. Nevertheless, no unified theory on the kinetics and
mechanism of autoxidation of sulfide exists (Millero, 1986).
The oxidation has complex kinetics, not being dependent upon
oxygen concentration, catalysts, or pH in any simple way
(Wilmot et al., 1988; Hoffman et al., 1977). Half-lives for
degradation of H2S(aq) in air-saturated water range from 18 to
50 hours at 25°C and pH 8.0 (Millero et al. , 1987).
If EDB reacts with H2S(aq) in groundwater or the
saturated soil zones and is then transformed to sulfur-
containing compounds, it is of interest to determine their
toxicology relative to EDB. This question was addressed
using a screening assay which is employed in the study of
aquatic pollutants and toxic wastewater. Results are
compiled in Appendix D and suggest slightly increased
toxicity compared to EDB.

SUMMARY AND CONCLUSIONS
The transformations of EDB in aqueous solutions and
groundwater have been studied. The chemical had been used
for numerous agricultural tasks, one of which involved heavy
application to the soil in nematode-infested farmlands in
Florida. The chemical's well-established toxicity in
laboratory studies and in animals made the detection of the
chemical in groundwater, a major source of potable water,
alarming. Little was known about EDB's persistence and fate
in the environment.
In this study, rate constants for the disappearance of
EDB at elevated temperatures were determined in groundwater
samples from regions of Florida known to be contaminated
with the chemical. The extrapolated half-lives ranged from
259 to 772 days at 22°C. The rate of degradation was
independent of pH between 5 and 9. The products of
degradation quantitatively partitioned into the aqueous
phase, while unchanged EDB was extracted into the organic
phase. An assay was developed and used to determine trace
quantities of ethylene glycol in aqueous solution. This
chemical and bromide ion accounted for essentially all of
the conversion products. Vinyl bromide, the reductive
dehalogenation product previously reported as a product in
151

152
aqueous solutions (Vogel and Reinhard, 198), could not be
detected.
In buffered solutions, the rate of disappearance of EDB
was increased by approximately 3 to 20 fold by the presence
of H2S(aq) over that in the absence of H2S(aq). Between pH 7
and 9, the rate of degradation of EDB was first-order in
H2S(aq) and second order overall, dependent upon the
concentration of EDB and H2S(aq). The products of degradation
partitioned into the organic phase after extraction in this
case. The conversion of EDB to sulfur-containing products
included disulfide, cyclic-sulfide, -disulfide, and -tri¬
sulfide compounds with two-carbon unit building blocks.
An evaluation by Microtoxâ„¢ of the relative toxicity of
these sulfur transformation products compared to the
reactants indicates the process may increase toxicity.
These findings suggests that the transformations of
halogenated alkanes and other related anthropogenic
contaminants susceptible to nucleophilic attack by H2S(aq)
or HS- may have significant consequences when certain
environmental conditions exist. More work is required to
ascertain whether compounds formed in these processes
present a health risk. The findings also highlight the
important need to determine the products of an environmental
fate reaction of a chemical contaminant and the implications
they may have on chemical behavior, analysis, and toxicity.
The contamination of groundwater with EDB and other
pesticide residues from previously approved agricultural

153
practices has already had a significant impact on several
major farming states. As evidenced by the large number of
recent research publications, symposia, and media coverage,
the issue of groundwater contamination has begun to receive
widespread attention. Pesticide application practices have
come under greater scrutiny. Problem-solving strategies
include (1) developing groundwater monitoring programs, (2)
educating farmers about recent developments in pesticide
research and the importance of following revised protocols
for pesticide application, and (3) studying the fate and
transport of chemicals in the environment to anticipate
future contamination potential. In the long run,
application of our new knowledge could prevent unexpected
risk to the safety of our critical underground reservoir of
fresh water.

APPENDIX A
ANALYSES OF GROUNDWATER FOR HYDROLYSIS STUDIES

155
'SPEC. 'DIS. ^CONCENTRATION (mg/mL)
'WELL 2EDB 'TEMP. COND. 02
LOCATION (ug/L) 'pH (°C) OiMHQsfcm) (mgL.) Ca Mg Si Na K Cl Fe Al Mn Cu Cr N03 NH4
Richard Groves
Service Well, 7.0, 7.2 6.8, 8.2 27 332 3.10 25 8.7 5 4.3 0.7 5.0 ND ND ND ND NO 0.04 0.15
Burns Avenue
Lake Wales
Polk County
County Maint.
Bldg., Opposite 11.5,10.0 7.0, 8.2 25 225 2.60 20 10.0 10 7.5 1.2 7.0 0.1 ND ND ND ND 0.04 0.30
Agrie. Civic Ctr.,
Highlands County
Private Well off
Hwy. 2E, NE of 4.0,31 6.7,8 0 23 105 6.20 44 0.6 3 Tr 0.1 Tr 0.1 ND ND ND ND 2.30 Tr
Bascom, Jackson
County
Tr = Trace
ND = None Detected
'Sample collection and on-site analysis by DER
"Pesticide Research Laboratory; analysis by project personnel, DER/HRS-EDB monitoring program personnel (n=3, 5%RSD)
3Extension Soil Testing and Analytical Research Laboratory (University of Florida)

APPENDIX B
ANALYSES OF GROUNDWATER FOR HYDROGEN SULFIDE DEGRADATION STUDIES

157
Sample
TEMP
PH
pMHOs
AlCaCI,
NH„
po4
Na
K
Ca
Mg
Cl
so4
SIO,
SITE ID
DATE
ro
UNITS
/cm
(mg/Ll
fmg/Ll
Ima/Ll
(mg/L'i
(mg/1-1
(mg/L)
(mg/L)
(mc/Ll
fmg/l.)
('nm/L'i
IIE-0557
062485
24.6
NA
3942
125.0
0.58
0.015
579.0
18.60
180.5
109.75
1175.0
320.0
21.0
022586
24.6
6.7
4390
125.1
0.01
0.004
582.0
19.20
104.5
110.20
1225.0
362.3
24.0
022387
25.1
7.1
4370
110.5
0.38
0.015
608.0
19.45
172.5
113.70
1157.5
456.9
36.4
022388
25.1
7.5
4490
NA
0.37
0.008
606.5
21.20
175.5
111.00
1241.1
357.7
33.6
HE-0558
062485
24.2
NA
3654
164.0
0.18
0.004
374.0
8.00
269.5
81.30
559.0
212.0
6.3
022586
22.6
5.5
3240
203.1
0.01
0.016
312.5
8.80
188.0
72.20
1100.0
193.1
7.0
022387
24.0
6.8
2550
165.7
0.27
0.078
298.5
8.43
219.0
69.30
789.2
226.0
15.4
022388
21.5
6.9
3100
NA
0.47
0.128
294.0
9.00
220.0
66.45
821.0
165.3
14.5
L-02531
060385
26.8
7.4
2890
102.0
0.34
0.004
446.5
19.75
92.0
84.65
725.0
385.9
10.6
010686
27.4
6.7
3050
119.1
0.36
0.006
405.5
16.15
93.9
80.20
755.0
446.6
9.7
010587
26.7
7.8
3150
106.7
0.35
0.004
461.5
21.35
94.4
90.80
732.8
405.3
17.1
022288
28.3
7.7
3120
NA
0.32
ND
420.8
17.10
100.0
83.95
789.3
382.1
14.5
L-01977
060385
23.8
6.6
3654
117.0
0.51
0.004
518.5
18.00
126.0
92.90
1020.0
226.5
18.0
010686
23.9
6.8
379
132.4
0.59
0.004
465.0
14.40
139.5
86.65
1025.0
324.7
20.3
010587
23.4
7.7
1991
128.9
0.54
0.004
606.0
21.30
136.3
107.00
978.4
311.6
33.3
022288
25.0
7.8
3780
NA
0.47
0.006
466.8
17.10
142.0
86.80
1015.9
302.5
34.2
Sample
TDS
Sr
Fe
TUT Fe
NOj
no2
F
Tor At
TOTCr
TOTCu
TOTMn
TOTPb
TOTZn
SITE ID
DATE
Img/Ll
(me/l-l
(nWU
(ingN/L)
(mg/I.)
(p&O1-
(u«A.)
(tfg/Ll
(Hg/I-I
( (qg/L)
HE-0557
062485
2563
12.92
0.05
0.06
0004
0.004
1.20
1.50
0.95
1.51
4.05
1.40
24
022586
2558
11.17
0.05
0.05
0.004
0.004
1.16
0.60
0.30
0.50
12.85
0.60
45
022387
2589
12.99
0.05
0.14
0.004
0.004
0.99
1.00
0.40
1.69
5.55
0.80
20
022388
2505
12.25
ND
0.11
ND
ND
0.47
ND
ND
ND
4.12
ND
34
HE-0558
062485
2305
17.15
3.11
0.41
0.009
0.009
0.09
5.85
4.13
1.00
12.47
2.80
18
022586
1825
14.38
NA
NA
0.004
0.004
0.54
3.50
0.30
0.50
22.90
3.32
31
022387
1859
14.10
5.54
7.35
0 004
0.004
0.43
6.00
0.51
2.10
28.92
0.80
30
022388
1911
6.75
6.24
8.31
0.006
0.015
0.83
6.29
0.68
7.67
10.67
1.52
49
L-02531
060385
1871
19.21
0.05
0.05
0 004
0004
ND
1.50
0.30
0.40
0.95
040
30
010686
1829
18.19
0.05
0.05
0.004
0.004
1.29
0.70
1.00
0.40
0.60
0.40
15
010587
1842
19.10
1.14
0.02
0.004
0.004
1.37
1.60
030
0.60
0.70
0.30
20
022288
1849
20.05
ND
0.07
ND
ND
0.15
3.34
0.59
1.12
0.90
ND
20
L-01977
060385
2208
18.87
005
0.05
0.004
0.004
1.80
1.50
0.80
0.90
42.80
3.09
30
010686
2060
17.98
0.05
NA
0.004
0.004
1.04
0.70
1.72
1.93
60.30
3.78
25
010587
2115
19.00
0.05
0.12
0.004
0.004
NA
ND
NA
NA
NA
NA
NA
022288
2173
17.50
ND
0.07
ND
ND
0.89
ND
0.51
ND
18.30
0.51
26

APPENDIX C
MASS SPECTRA OF SULFUR-CONTAINING COMPOUNDS IN THIS STUDY
Compiled on the following pages are El mass spectra
obtained from GC/MS analyses of standard sulfur-containing
compounds and sulfur-containing EDB transformation products
found in this study. The spectra of the standards followed
by products are arranged in order of increasing molecular
weight. The results are collected in Tables 13 and 14 in
the results section.
158

100.0-1
50.0 -
MASS SPECTRUM
03/30/89 15:09:00 +
3:20
SAMPLE: STANDARD MIXTURE- 10 ORCANOSULFUR COMPOUNDS
COIOS.: 30M X 0.25MM DB17- 60C->280C 8 12C/M1N, El
ENHANCED (S 15B 2N 0T>
47
DATA: RANDY33089 «400
CALI: CAL032989 »5
BASE M/Z: 47
RIC: 1056.
45
43
42
40
371
M-r
44
IK
94
60
53
57
49
54
-r-i-r
61
73
62 64
iü
.66
f-T-4
34 ^
'in
d*» I
“1 t-i—r-j-r —t-4—,—I—•—r—,—p — ■
tl
Sfi
199.
159

MASS SPECTRUM
03/30/89 15:09:00
3:59
10O.0
SAMPLE: STANOARD MIXTURE- 10 ORCAMOSULFUR COMPOUNDS
COtCS.: 30M X 0.25MM DB17, 60C->280C 0 12C/MIN, El
ENHANCED (S 150 2N 0T)
55
DATA: RANOY33089 «479
CALI: CAL032989 «5
BASE M/2: 55
RIC: 3864.
41
39
37
43
45
47
51
4'J
-I.
67
60
63
II 7
ID
if'
116
86
111. -
, rr" P

100.0-1
r.ñ.ñ
MASS SPECTRUM OATA: RANDY33089 1787
03/30/89 15:09:00 + 6:33 CALI: CAL032989 »5
SAMPLE: STANDARD MIXTURE, 10 ORCANOSULFUR COMPOUNDS
COIIDS.: 30M X 0.25MM DB17, 60C->280C @ 12C/MIN, El
ENHANCED (S 15B 2N 0T)
BASE M/2: 120
RIC: 360.
4b
42
•A
.1
61
sr.
55
T' ” ’■
64
T.. ,’Tr,. ,,
FXi ?iH fll
120
92
105
T-r -r
• • 11'H
I
1 III
82.
161

100.0-1
MASS SPECTRUM DATA: RANDY33089 »458 BASE M/Z: 122
03/30/89 15:09:00 + 3:49 CALI: CAL032989 »5 R1C: 3920.
SAMPLE: STANDARD MIXTURE, 10 ORGANOSULFUR COMPOUNDS
CONOS.: 30M X 0.25MM DB1?, 60C->280C 8 12C/M1H, El
ENHANCED (S 15B 2H 0T)
122
835.
162

100.0-1
Sil. fi
MASS SPECTRUM DATA: RANOY33089 #1537 BASE M/2: 136
03/30/89 15:09:09 + 12:48 CALI: CAL032989 #5 RIC: 467.
SAMPLE: STANDARD MIXTURE, 10 ORGANOSULFUR COMPOUNDS
COHOS.: 30M X 0.25MM DB17, 60C->280C @ 12C/MIN, El
135.9
60.1
44.7
39.8
I
75.9
63.8
107.9
IL
;.o
T ~T'
11» i
11 â– 
148.
163

100.0n
sn.0
MASS SPECTRUM DATA: RAHDY33089 *1296
03/30/89 15:09:00 + 10:48 CALI: CAL032989 *5
SAMPLE: STANDARD MIXTURE, 10 ORGANOSULFUR COMPOUNDS
CONOS.: 30M X 0.25MM DB17, 60C->280C @ 12C/MIN, El
BASE M/Z: 138
RIC: 461.
137.9
45.9
112.
164

100.0-1
r,n. m
I1HSS SPECTRUM DATA: RANOY33089 #994
03/30/89 15:09:00 + 8:17 CALI: CAL032989 #5
SAMPLE: STANDARD MIXTURE, 10 ORCANOSULFUR COMPOUNDS
COIOS.: 30M X 0.25MM D617, 60C->280C 8 12C/MIN, El
57.0
41.0
122.0
r
88.1
1
.10
! AO
"rI
1 n
140
BASE M/H: 57
RIC: 430.
178.0
ISO i;.n
113.
165

100.0-,
so.n
MASS SPECTRUM
03/30/89 15:09:00 ♦ 14:0?
SAMPLE: STA1CAR0 MIXTURE, 10 ORGAHOSULFUR COMPOUNDS
CONOS.: 30M X 0.25MM DB17, 60C->280C 0 12C/HIN, El
DATA: RANOY33089 #1695
CALI: CAL032989 15
44.9
'9.9
60.9
105.9
".9
86.9
92.0
' ' ’ T~r,~' r'Tr_' T *-i
II!
119.0
I
I Ofl
BASE M/Z: 180
R1C: 411.
179.9
! C<
55.
166

100.0 n
so.n
MASS SPECTRUM
04/11/89 16:13:00 + 13:08
SAMPLE: SYNTHETIC 1,2,5.6-TETRATHIACYCLOOCTANE
CONOS.: 30M X 0.25MM DB1, 50C-7300C 0 12C/MIN,
DATA: RANDY489Í *1576 BASE M/Z: 184
ENHANCED < 56-1N-1T) RIC: 14128.
2372.
124
92
64
59
45
1 ll. ,XJ,
86
96
110
119
IP
(00
\~r
I ' ft
17?
T r
110
160 I -fl
167

100.0-1
39.9
MOSS SPECTRUM DOTA:
03/30/89 15:09:00 + 19:14 CALI:
SAMPLE: STAUOARO MIXTURE, 10 ORCANOSULFUR COMPOUNDS
CONOS.: 30M X 0.25MM DB17, 60C->280C 0 12C/MIN, El
60.1
sr.o 121.0
104.9
11ifi (',n
RANOY33089 #2309 BASE M/2: 40
CAL032989 #5 RIC: 130.
240.1
17.
168

ion.o
HASS SPECTRUM DATA: RANDY121566 #1190 BASE !W: 120
12/17/86 10:26:00 + 3:55 CALI: CAL121786 #5 RIC: 636.
SAMPLE: PRODUCT OF 12/15/86, #3, 2 UL GROB INJ.
COHDS.: 3011 X 0.25MI1 DB-5 CAP, 3 MUI @ 50C->300C @ 5C/I1IH, El
EUHAHCED CS 15B 2H 0T)
0.1
t J
r i -i
I MM
It"
120
I."
I 7,
iL,
182.
169

MASS SPECTRUM
02/02/89 18:26:00 + 7:50
SAMPLE: EDB/GROUNOWATER, 1/18/89, HE00558
COtOS.: 30M X 0.25MM 0B17, 60C->288C 0 12C/MIH,
ENHANCED (S 15B 2N 0T)
DATA: RANOY2289A »940
CALI: CAL013089 14
BASE M/2: 124
RIC: 1392.
El
100.0
50.0
124
II 2
100.0
50.O
II 7
12.
512.
170

MASS SPECTRUM
12/17/86 10:26:06 + 19:16
SAMPLE: PRODUCT OF 12/15'86, #3, 2 UL GRÃœB INJ.
COI IDS.: 36M X 0.25MM D6-5 CAP, 3 Mill 0 50C->300C 0 5C MIN, El
ENHANCED (S 15B 211 OT)
DATA: RANDY121586 #2313
CALI: CAL121786 #5
100.0 -i
50.U
BASE M/2: 152
RIC: 3392.
152
60
45
35 331
t r*r*i t
b3
-.1..
64
i Ü
cc 7 3
66 I
4w44
10
8,6 85
124
8J
106
96
to
80
MtJS,
113
106
"rTir
126
146
r 2132.
160
M2
171

100.0-,
50.0-
100.0 -
MASS SPECTRUM DATA: RAN0Y2289A »1302
02/02/89 16:26:00 + 10:51 CALI: CAL013889 #4
SAMPLE: EOB/GROUNOWATER» 1/18/89, HE00558
COK)S.: 30M X 0.25MM 061?, 60C->280C 8 12C/MIN, El
ENHANCED (S 15B 2N 0T)
BASE M/H: 156
RIC: 602.
156
64
105
128
100
T
120
124
r*W
209.
209.
50.0
193 207
?nn
i '
-â– -â– n
-T&-
240
252
rT'r
'PO
^3*
7
'Oft
329
335 349
S.JO :cM
172

BOSE h/Z; 184
RICs 217
MASS SPECTRUM DATA: RANOY2289A 11761
02/02/89 16:26:00 + 14:40 CALI: CAL013089 «4
SAMPLE: EOB/GROUNOWATER, 1/18/89, HE00558
CONDS.: 30M X 0.25*11 DB17, 60C->280C 8 12C/MIN, El
ENHANCED (S 15B 2N 0T)
173

MASS SPECTRUM DATA: RAN0Y2389 11491 BASE M/2
02/03/89 9:54:00 + 12:25 CALI: CAL013089 »4 RIC:
SAMPLE: EDB/GROUNDMATER, 1/23/89, HE0558
CONDS.: 30M X 0.25MM DB1?, 60C->280C 6 12C/M1N, El
ENHAHCED (S 15B 2N 0T)
180.0
50.0 -
45
40
59
76

APPENDIX D
MICROTOXâ„¢ ASSAY EVALUATION OF PRODUCTS
Described by Bulich and coworkers (1979, 1981), the
Microtox assay provides a rapid, reliable estimate of
relative toxicities of aquatic pollutants and toxic
wastewaters, e.g., in complex industrial effluents. This
commercially available test system (Beckman Instruments,
Inc.; San Ramon, CA), which includes a photomultiplier tube,
reagents, and 15°C incubation wells, is recommended by the
U.S. EPA (1984) for water quality assessment.
The assay is based on the sensitivity of Photobacterium
phosphoreum bioluminescence to toxicants. Microtoxâ„¢
typically involves dilution of the test chemical solution to
determine the concentration at which luminescence is
inhibited by 50%, i.e., the effective concentration to
achieve 50% luminescence (EC50) .
Individual solutions of EDB (2,000 mg/L) , H2S(aq) (213
mg/L), 1,2-ethanedithiol (100 mg/L), and 1,4,7-trithia-
cyclooctane (100 mg/L) were prepared in 0.10 M deoxygenated
carbonate (pH 7.0) and 0.001 M Ti (III) citrate redox
buffer. These solutions and acetate, phosphate, and
carbonate buffers each initially containing 10 mg/L EDB and
75 mg/L H2S(aq), and incubated at 25°C until less than 1 mg/L
175

176
remained, and then subjected to the Microtox assay. The
assay was also preformed on EDB-fortified (10 mg/L) HE-0058
after 7 months incubation, and control buffer and
groundwater.
Plots of percent inhibition of luminesence (I) vs.
concentration were constructed using for points. Least-
squares regression analysis established a line equation from
which the EC50 was read.
The EC50 values for EDB, both with and without pH and
redox buffers, ranged from 646 to 1191 mg/L. EDB had the
highest non-control EC50 values, i.e., least toxic effect on
luminescence (Table D-l) . EC50 values for H2S(aq), 9.39-71.28
/xg/mL, were much lower than values for EDB. The greater
luminescence inhibition of the sulfur-containing standards,
EDT and TTCN, indicates the greater toxicity of these
compounds compared to their precursors, EDB or H2S(aq). The
EC50 values of EDT and TTCN ranged from 0.32 to 4.29 mg/L.
EC50 values for the "reaction mixtures" are based upon the
initial EDB concentration of 10 mg/L. They are incubations
from the product study discussed above. Essentially all EDB
in these solutions were transformed to product. The
buffered reaction mixtures had a mean EC50 value of 0.22
(s.d. 0.04) and unbuffered reaction mixtures a mean
EC50value of 0.32 (s.d. 0.18). The HE-0058 groundwater
incubation was also measured as highly toxic (EC50 0.40)
relative to the reactants EDB and H2S(aq).

177
Table D-l. Evaluation of toxicity of solutions sulfur-compond
standards and EDB and H2S(aq) reaction solutions by Microtoxâ„¢
assay.
Test
Data
EC-50
Solution3
Plotb
r2
(mq/L)
STANDARDS
EDB+b
I V.
C
0.9838
742.49
EDB+b
I V.
C
0.9927
909.03
EDB
I V.
C
0.8806
742.49
EDB
Ini \
r. C
0.9756
1191.48
H2S(aq)+b
H2S(aq)+b
H2S(ac)
H2S(aq)
TTCN+b
I V.
InC
0.9985
9.39
I V.
C
0.9844
71.28
I V.
C
0.9956
13.60
I V.
C
0.8485
44.41
I V.
C
0.9048
0.43
TTCN+b
I V.
C
0.9560
2.39
TTCN
I V.
C
0.9565
4.29
EDT+b
I V.
C
0.8888
0.33
EDT+b
I V.
C
0.8200
0.32
EDT
I V.
C
0.8275
0.65
INCUBATIONS
ACE+b
I V.
C
0.9177
0.21
CARB+b
I V.
C
0.8691
0.26
CARB
I V.
C
0.8749
0.47
CARB
I V.
C
0.8129
0.12
PHOS+b
I V.
C
0.9202
0.18
PHOS
I V.
C
0.8920
0.37
HE-0058
CONTROLS
I V.
C
0.9092
0.40
BUFFER
I V.
c
0.9464
18.05
BUFFER
I V.
c
0.9950
22.47
HE-0058
NO I
—
—
a0.01 M buffer (abbreviations in Table 8) and b indicates
0.001 M Ti (III) citrate redox buffer was present
I is inhibition, C is concentration of test chemical
bLinear portion of curve by least-squares regression analysis,
r2 is the coefficient of determination

178
While Microtox is only a screening test, its results
may indicate that the products of the reactions attenuate
the toxicity of EDB and H2S(aq). The following rationale was
the basis for the selection of particular compound for
Micrtox testing. The first was EDT, a non-cyclic compound
is transiently present as a intermediate metabolite in the
reaction of EDB and H2S(aq). The other compound, TTCN is a 9-
membered cyclic compound, containing 3 sulfur atoms is
similar in structure to the stable products of EDB and H2S(aq)
reactions, TTCH, TTCO and TTCD (Table 15). Thus these
compounds represent four of the products that have been
identified.
EC50 of the total reactant mixtures and EDB fortified
HE-0058 were similar in magnitude to the EC50 of EDT and
TTCN individually. These data suggest that no one
metabolite carries a markedly greater toxicologic potential.

REFERENCES
American Public Health Association, American Water Works
Asociation, Water Pollution Control Federation. Standard
Methods for the Examination of Water and Wastewater. 15tn
ed.; American Public Health Association: Washington, DC,
1980.
Amin, T.A.; Narang, R.S. Determination of volatile organics
in sediment at nanogram-per-gram concentrations by gas
chromatography. Anal. Chem. 1985, 57, 648.
Barbero, J.A.; McCurdy, K.G.; Tremaine, P.R. Apparent molal
heat capacities and volumes of aqueous hydrogen sulfide and
sodium hydrogen sulfide near 25°C: the temperature
dependence of H2S ionization. Can. J. Chem. 1982, 60, 1872.
Bauld, J. Transformation of sulfur species by phototrophic
and chemotrophic microbes. In The Importance of Chemical
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BIOGRAPHICAL SKETCH
Randy Alan Weintraub was born in Washington, D.C., in
1958 and later moved to New York State. He graduated from
Hauppauge High School on Long Island in 1976.
Mr. Weintraub received a Bachelor of Science degree
from the College of Agriculture of the University of Florida
in 1980. While enrolled in graduate school at the same
institution, he secured a research assistantship in the
Department of Food Science and Human Nutrition and earned a
Master of Science degree in 1984. His master's thesis was
on the chemical analysis of citrus bioflavanoids and their
major metabolites in humans.
Since his enrollment in 1984 in the Ph.D. program in
the Department of Food Science and Human Nutrition, Mr.
Weintraub worked as a graduate research assistant at the
Pesticide Research Laboratory of the Department. Through
his work and research at the Pesticide Research Laboratory,
he developed a broad working knowledge of modern analytical
instrumentation, government- and corporate-sponsored
pesticide research protocols, and field study of application
practices of pesticides and their movement in soil and
water.
189

190
Mr. Weintraub enjoys swimming and running, having
competed in local and regional biathalons and a national
marathon. He and his wife, Dr. Barbara Ameer, who is an
Associate Professor in the College of Pharmacy of the
University, had their first child in July.

I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosphy.
HuglyAnson Moye, Ch^lr
Professor, Food Science and
Human Nutrition
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosphy.
)7 Willis B. Wheeler
Professor, Food Science and
Human Nutrition
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosphy.
Associate Professor,
and Human Nutrition
Food Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosphy.

I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosphy.
, . /y.j ,
i- / / L
Lori 0. Lim, Assistant Research
Scientist, Food Science
and Human Nutrition
This dissertation was submitted to the Graduate Faculty
of the College of Agriculture and to the Graduate School and
was accepted as partial fulfillment of the requirements for
Dean, Graduate School

UNIVERSITY OF FLORIDA
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