&EPA
United States
Environmental Protection
Agency
Off ice of Water 1982
Regulations and Standards (WH-553) Final Report
Washington DC 20460
Water
AQUATIC FATE
PROCESS DATA FOR
ORGANIC PRIORITY
POLLUTANTS
Final Report
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DISCLAIMER
This report has been reviewed by the Office of Water Regulations and
Standards, U.S. Environmental Protection Agency, and approved for publica-
tion. Approval does not signify that the contents necessarily reflect
the views and policies of the U.S. Environmental Protection Agency, nor
does mention of trade names or commercial products constitute endorsement
or recommendation for use.
ii
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FOREWORD
Effective regulatory action for toxic chemicals requires an under-
standing of the human and environmental risks associated with the manu-
facture, use, and disposal of a chemical. The assessment of risk requires
the best scientific judgment about the probability of harm to the environment
resulting from known or potential environmental concentrations. Environ-
mental concentrations are a function of (1) the amount and form of the
chemical released per unit time into the environment, (2) the geographic
area, (3) prior accumulation, (4) time of measurement after release, and
(5) the behavior of the chemical in the environment. The behavior, or
fate and transport characteristics, of toxic pollutants in the environment
depends on a variety of chemical, physical, and biological processes
(e.g., photolysis, hydrolysis, oxidation, volatilization, sorption, bio-
degradation, biotransformation). These processes were placed into perspective
and summarized for 129 chemical substances in a two-volume report entitled
"Water-related Environmental Fate of 129 Priority Pollutants" (EPA-440/
4-79-029a&b). Although this review contained literature data on some of
the processes, data were incomplete for many of the processes affecting the
114 organic compounds.
This report takes data and information from the "129 report" as well
as from other sources and puts it in a form for use in modeling the fate
of the 114 organic priority pollutants.
Michael W. Slimak, Chief
Exposure Assessment Section
Water Quality Analysis Branch
Monitoring and Data Support Division (WH-553)
Office of Water Regulations and Standards
Note: This report was revised in late 1982 after review within EPA.
Some values have been changed as a result of reexamination of
information available.
iii
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ABSTRACT
Equilibrium and kinetic constants for evaluating the transformation
and transport in aquatic systems for 114 organic chemicals on EPA's
priority pollutant list have been obtained from the literature and from
theoretical or empirical calculation methods. Constants for selected
physical properties and for partitioning, volatilization, photolysis,
oxidation, hydrolysis, and biotransformation are listed for each chemical
along with the source of the data. Values are reported in units suitable
for use in a current aquatic fate model. A discussion of the empirical
relationships between water solubility, octanol-water partition coefficients,
and partition coefficients for sediment and biota is presented. The
calculation of volatilization rates for organic chemicals in aqueous
systems also is discussed.
iv
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CONTENTS
FOREWORD iii
ABSTRACT iv
LIST OF ILLUSTRATIONS vii
LIST OF TABLES vlii
ACKNOWLEDGMENTS
1. INTRODUCTION 1
1.1 Purpose 1
1.2 Background 1
1.3 References 5
2. ASSESSMENT OF CONCENTRATIONS AND HALF-LIVES OF CHEMICALS IN
AQUATIC ENVIRONMENTS 6
2.1 The Process Modeling Approach 6
2.2 Applications of the Process Modeling Approach 13
2.3 Definitions of Processes and Sources of Data 16
2.3.1 Bases for Derivation of Process Data 16
2.3.2 Chemical Name and Molecular Weight 18
2.3.3 Melting and Boiling Point 18
2.3.4 lonization Constants 19
2.3.5 Partitioning Constants 20
2.3.6 Volatilization Constants 22
2.3.7 Photolysis Data 24
2.3.8 Oxidation Rate Constants 27
2.3.9 Hydrolysis Rate Constants 30
2.3.10 Biotransformation Rate Constants 32
2.4 References 35
3. PROCESS DATA FOR TRANSPORT AND TRANSFORMATION OF CHEMICALS IN
AQUEOUS SOLUTION 38
3.1 Organization of Data Sheets and Sources of Data ••• 38
3.2 Pesticides 51
3.3 PCBs and 2-Chloronaphthalene 113
3.4 Halogenated Aliphatic Chemicals 131
3.5 Halogenated Ethers 191
3.6 Monocyclic Aromatic Chemicals 213
3.7 Phthalate Esters 279
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3.8 Polycyclic Aromatic Hydrocarbons 297
3.9 Nitrosamines and Other Nitrogen-containing Chemicals. 355
4. CALCULATION OF PARTITION COEFFICIENTS OF ORGANIC CHEMICALS IN
AQUATIC ENVIRONMENTS 373
4.1 Background 373
4.2 Calculation Methods 374
4.2.1 Correlation Equations 375
4.2.2 Units and Conversion Factors 376
4.3 Calculation of K andS from K 378
OC , W , .OW 070
4.3.1 Partitioning Thermodynamics J/o
4.3.2 Comparison of Reported Correlations 388
4.4 Calculation of K Value from Structural Parameters • 404
ow
4.5 References 408
5. CALCULATION OF RATES OF VOLATILIZATION OF ORGANIC CHEMICALS
FROM NATURAL WATER BODIES 409
5.1 Introduction 409
5.2 Calculation Methods 409
5.2.1 Outline of General Procedure 409
5.2.2 Calculation of the Henry's Constant 411
5.2.3 Calculation of Diffusion Coefficients 414
5.2.4 Other Parameters 415
5.2.5 Sample Calculation 415
5.3 Calculation of the Volatilization Rates of the Priority
Pollutants 419
5.4 Theoretical Considerations 423
5.4.1 Two-film Theory 423
5.4.2 Choice of Parameters in Table 5.1 428
5.4.3 Selection of Volatilization Rate Input
Data for the EXAMS Model 430
5.5 References 432
VI
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ILLUSTRATIONS
Figure Page
2.1 Transport and Transformation Processes in Aquatic Environ- 8
ments
4.1 Lattice Model of a Solute (S) Partitioning Between Octanol 379
(o) and Water (w) Phases.
4.2 Lattice Model of a Higher Mole Fraction of Solute (S) Par-
titioning Between Octanol (o) and Water (w) Phases. 379
4.3 Enthalpy of Fusion Correction Factor for Aqueous Solubil-
ity at 25°C as a Function of Melting Temperature 387
4.4 Comparison of Solubility-K Equations for Liquid Solutes 394
4.5 Solubilities of Hexachlorocyclohexanes (a,3,6,Y-BHC) 398
4.6 Comparison of Solubility-K Equations for Solid Solutes 399
5.1 Estimated Half-Lives versus Henry's Constant for the
Priority Pollutants in Rivers 421
5.2 Estimated Half-Lives versus Henry's Constant for the
Priority Pollutants in Lakes or Ponds 422
vii
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TABLES
Table Page
2.1 Percent Chemical Remaining as a Function of Half-Lives 12
2.2 Estimated Rate Constants for Biotransformation of Chemicals
by Bacteria in Water Body Solution Phase 34
4.1 Conversion Factors for Composition Units 377
4.2 Effect of Melting Point Concentration on Water Solubility 386
Rates
4.3 Reported Correlations of K , K , and S 389
ow oc w
4.4 Data Bases for K -K Correlations 392
oc ow
4.5 Calculated versus Measured Solubilities for Chlorinated
Methanes and Ethanes 395
4.6 Calculated versus Measured Solubilities for Low Melting
Point Aromatics 397
4.7 Calculated versus Measured Solubilities for Selected
Pesticides
4.8 Aqueous Solubilities of High Melting Point Chemicals 402
4.9 Correlation of Measured and Calculated Values of K 406
ow
5.1 Summary of Constants and Values for Substitution into
Equation (5.2) 416
5.2 Oxygen Reaeration Rates in Representative Water Bodies 429
5.3 Water Evaporation Rates for Lakes 428
viii
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ACKNOWLEDGMENTS
This work was conducted by SRI International under EPA Contract
68-01-3867. The support and comments of the Project Officer, Mr. Michael
Slimak, are gratefully acknowledged; the comments and assistance of
Mr. Mark Sonnenschein of EPA's Office of Water Regulations and Standards
are also appreciated. Discussions with Dr. L. A. Burns of the Environ-
mental Systems Branch of EPA's Environmental Research Laboratory, Athens,
GA., were invaluable in preparing data for use in modeling for this
report. Unpublished information from and discussions with Mr. G. L.
Baughman, Ms. D. F. Paris, and Drs. S. Karickhoff, N. L. Wolfe, and R. G.
Zepp of the Environmental Processes Branch, EPA-ERL, Athens, GA., also
are gratefully acknowledged. We also gratefully acknowledge the assistance
and support of Drs. L. A. Mulkey and K. F. Redden, Technology Development
and Applications Branch, EPA-ERL, Athens, GA., in the revision and publication
of this report.
The assistance of the following SRI staff in preparing this report
is also acknowledged:
M. Comas, J. Etherton, D. Haynes, H. Schaeffer.
ix
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SECTION 1
INTRODUCTION
1.1 PURPOSE
The purpose of this report is to provide data for selected chemical,
physical, and biological processes that occur in aquatic environments for
organic chemicals on the EPA's list of priority pollutants. These data
can be used with appropriate environmental parameters (e.g., pH, sediment
loadings, bacterial populations, sunlight intensity) to calculate half-
lives of chemicals in aquatic systems. The concentration of a chemical
as a function of time or distance in a particular aquatic system may also
be calculated from these data using computer models that include the hydro-
logical properties of a water body. Some of the data in this report have
been calculated or estimated using empirical or theoretical methods and
are intended primarily for use by EPA's Office of Water Regulations and
Standards (EPA-OWRS) in its assessment program. EPA-OWRS will use data
from this report to obtain preliminary estimates of chemical concentrations
in aquatic systems using aquatic fate models that incorporate the process
modeling approach (see Section 2.2). As the needs for better process data
are identified, laboratory or other studies will be conducted.
This report is published in recognition that these data are of interest
to other environmental programs; users of these data must be responsible
for how the definition, sources, limitations, and reliability of these data
may be significant or inapplicable in the context of their own assessment
programs. Users of the data in this report are encouraged always to seek
more current data to confirm or supplant the data presented.
1.2 BACKGROUND
The Office of Water Regulations and Standards, U.S. EPA, is conduct-
ing a program to evaluate the environmental fates of 129 chemicals in
aquatic systems; these chemicals are commonly referred to as priority
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pollutants. A brief history of EPA's overall efforts on priority pollutants
has been described by Keith and Telliard (1979). As part of the EPA program,
EPA-OWRS has recently published a comprehensive literature review on the
physico-chemical properties and the transformation and transport processes
of priority pollutant chemicals for use in environmental exposure assess-
ments (Callahan et al., 1979). Although the review contains literature
data on some processes, the data were incomplete for most chemicals and
often information was qualitative, of suspect reliability, or did not exist.
However, some of these process data can be calculated or estimated by
theoretical or empirical methods so that the significant transport and
transformation processes can be identified, and provisional calculations
of chemical concentrations in aquatic systems can be made for rough exposure
assessments. These results can then be used to decide what process data
must be upgraded in the context of the particular assessment.
This report takes data and information from the 1979 EPA-OWRS literature
review (Callahan et al., 1979) as well as from other sources to provide data
for use in modeling the fate of the individual organic priority pollutants.
The data presented in this report are in units used in one particular aquatic
fate model (known as EXAMS, the Exposure Analysis Modeling System, see Sec-
tion 2.2), but may also be used in other fate assessments.
This report has five sections. The first three sections provide the
data intended for use in aquatic fate modeling and include brief discussions
of the processes or data for which values are given. These sections also
describe the basic theory (including equations) related to the process and
use of the data along with the estimation or calculation methods or sources
of data. Sections 4 and 5 describe in detail the calculation methods for
evaluating sorption and volatilization data, respectively.
The organic priority pollutant chemicals for which data are provided
in this report are listed below according to the classes or groups of
chemicals as listed in the 1979 EPA-OWRS report, "Water Related Environ-
mental Fate of 129 Priority Pollutants," by Callahan et al. 1979.
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Pesticides
1. Acrolein
2. Aldrin
3. Chlordane (cis and trans isomers)
4. DDD
5. DDE
6. DDT
7. Dieldrin
8. Endosulfan (a and g isomers)
9. Endosulfan sulfate
10. Endrin
11. Endrin aldehyde
12. Heptachlor
13. Heptachlor epoxide
14. a-Hexachlorocyclohexane
15. $-Hexachlorocyclohexane
16. 6-Hexachlorocyclohexane
17. Y~Hexachlorocyclohexane (lindane)
18. Isophorone
19. TCDD
20. Toxaphene
PCBs and 2-Chloronapht.halene
21. Aroclor 1016
22. Aroclor 1221
23. Aroclor 1232
24. Aroclor 1242
25. Aroclor 1248
26. Aroclor 1254
27. Aroclor 1260
28. 2-Chloronaphthalene
Halogenated Aliphatic Hydrocarbon
29. Chloromethane (methyl chloride)
30. Dichloromethane (methylene chloride)
31. Trichloromethane (chloroform)
32. Tetrachloromethane (carbon tetrachloride)
33. Chloroethane (ethyl chloride)
34. 1,1-Dichloroethane (ethylidine chloride)
35. 1,2-Dichloroethane (ethylene dichloride)
36. 1,1,1-Trichloroethane (methyl chloroform)
37. 1,1,2-Trichloroethane
38. 1,1,2,2-Tetrachloroethane
39. Hexachloroethane
40. Chloroethene (vinyl chloride)
41. 1,1-Dichloroethene (vinylidine chloride)
42. 1,2-trans-Dichloroethene
43. Trichloroethene
44. Tetrachloroethene (perchloroethylene)
45. 1,2-Dichloropropane
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46. 1,3-Dichloropropene
47. Hexachlorobutadiene
48. Hexachlorocyclopentadiene
49. Bromomethane (methyl bromide)
50. Bromodichloromethane
51. Dibromochloromethane
52. Tribromomethane (bromoform)
53. Dlchlorodlfluoromethane
54. Trichlorofluoromethane
Halogenated Ethers
55. Bis(chloromethyl)ether
56. Bis(2-chloroethyl)ether
57. Bis(2-chloroisopropyl)ether
58. 2-Chloroethyl vinyl ether
59. 4-Chlorophenyl phenyl ether
60. 4-Bromophenyl phenyl ether
61. Bis(2-chloroethoxy)methane
Monocyclic Aromatics
62. Benzene
63. Chlorobenzene
64. 1,2-Dichlorobenzene (^o_-dichlorobenzene)
65. 1,3-Dichlorobenzene (m-dichlorobenzene)
66. 1,4-Dichlorobenzene (j^-dichlorobenzene)
67. 1,2,4-Trichlorobenzene
68. Hexachlorobenzene
69. Ethylbenzene
70. Nitrobenzene
71. Toluene
72. 2,4-Dinitrotoluene
73. 2,6-Dinitrotoluene
74. Phenol
75. 2-Chlorophenol
76. 2,4-Dichlorophenol
77. 2,4,6-Trichlorophenol
78. Pentachlorophenol
79. 2-Nitrophenol
80. 4-Nitrophenol
81. 2,4-Dinitrophenol
82. 2,4-Dimethyl phenol
83. £-Chloro-m-cresol
84. 4,6-Dinitro-o-cresol
Phthalate Esters
85. Dimethyl phthalate
86. Diethyl phthalate
87- Di-n-butyl phthalate
88. Di-n-octyl phthalate
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89. Bis(2-ethylhexyl)phthalate
90. Butyl benzyl phthalate
Polycyclic Aromatic Hydrocarbons
91. Acenaphthene
92. Acenaphthylene
93. Anthracene
94. Benzo(a)anthracene
95. Benzo(b)fluoranthene
96. Benzo(k)fluoranthene
97. Benzo(ghi)perylene
98. Benzo(a)pyrene
99. Chrysene
100. Dibenzo(a,h)anthracene
101. Fluoranthene
102. Fluorene
103. Indeno(l,2,3-cd)pyrene
104. Naphthalene
105. Phenanthrene
106. Pyrene
Nitrosamines and Other Nitrogen-containing Chemicals
107. Dimethyl nitrosamine
108. Diphenyl nitrosamine
109. Di-n-propyl nitrosamine
110. Benzidine
111. 3,3'-Dichlorobenzidine
112. 1,2-Diphenylhydrazine (hydrazobenzene)
113. Acrylonitrile
1.3. REFERENCES
Callahan, M. A., M. W. Slimak, N. W. Gabel, I. P. May, C. F. Fowler,
J. R. Freed, P. Jennings, R. L. Durfee, F. C. Whitmore, B. Maestri,
W. R. Mabey, B. R. Holt, and C. Gould, 1979. Water-Related Environ-
mental Fate of 129 Priority Pollutants. U.S. EPA, Washington, D.C.
VoL I, EPA-440/4-79-029a; Vol. II, EPA-440/4-790029b.
Keith, L. H., and W. A. Telliard. 1979. Priority Pollutants. I. A Per-
spective View. Environ. Sci. Technol. 13(4):416-423.
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SECTION 2
ASSESSMENT OF CONCENTRATIONS AND HALF-LIVES OF
CHEMICALS IN AQUATIC ENVIRONMENTS
2.1 THE PROCESS MODELING APPROACH
A reliable and documented estimate of the concentration of a chemical
in the environment is required for most chemical hazard evaluation programs.
To predict such chemical concentrations, the fate of the chemical in the
environment can be evaluated in terms of transport and transformation pro-
cesses. The emphasis is then on the effects of the environment on the chemical,
rather than the effects of the chemical on the environment as in ecological
stuides (Baughman and Lassiter, 1978). Once the concentration of the
chemical is estimated for the environments of concern, species population,
toxicological data and other factors can be included to complete the hazard
assessment.
One method for predicting the concentrations of chemicals in the
environment is the process modeling approach in which it is assumed that
the total rate of loss of the chemical is determined by the sum of rates
of the individual chemical and biological transformation and physical trans-
port processes that occur for the chemical in an environment (Baughman and
Burns, 1980; Baughman and Lassiter, 1978, Mill, 1978; Smith et al. 1977,
1978). Data for the individual processes may be obtained in laboratory
stuides, by structure-activity relationships for a class of chemicals, or
from empirical correlations that apply to the chemical of concern. Combined
with data for the appropriate environmental conditions (such as pH, sunlight
flux, organism population) the process data can be used to calculate rates
for the process in the particular environment. The rates for the processes
in an environment may then be summed to estimate an overall rate for loss
of chemical in the environment.
In this report, process data are defined as data relating to rate
constants, equilibrium constants, or properties that describe the intrinsic
processes the chemicals may undergo independent of environmental influences.
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The term environmental parameter as used in this report refers to properties
or data that describe (or are a function of) the environment.
The process modeling approach to predicting environmental concentra-
tions of chemicals has several advantages over approaches such as field
studies or, on a smaller scale, microcosms. Although both approaches have
been considered representative of an environmental situation, the latter
fails to identify which process or processes are important for transforming
or transporting the chemical in the environment. Lack of such information
may then make the observed loss rate unreliable and undocumentable as to
whether the chemical generally may be expected to behave in a similar manner
in the same or in different environments. The field study approach also
has a drawback in that a hazard may actually be created in performing the
experiment. The microcosm experiment has problems in extrapolating the
data obtained to the real environment.
Although the process modeling approach should be verified by actual
experience in aquatic systems, it does offer a flexible and documentable
method for predicting environmental concentrations of a chemical. An in-
direct benefit of the process modeling approach is that attempts to verify
the models will advance the understanding of how the individual processes
operate in the environment and therefore guide efforts in research on these
processes and suggest what new processes should be included in future modeling
efforts.
The processes that can be important for transforming or transporting
a chemical in an aquatic environment are shown in Figure 2.1. The follow-
ing discussion summarizes the mathematical basis for the process modeling
approach applied to such aquatic systems in three, steps: (1) the evaluation
of rates of loss of chemical due to transformations and volatilization
processes, (2) the influence of sorption processes on the rates of loss
of chemical, and (3) the prediction of concentration and half-life of
chemical in the aquatic environment including terms for input of chemical,
dilution, and finally flow out of the environment. This discussion assumes
that return of the chemical from the atmosphere to the aquatic system is
included in the term for the inflow of the chemical and that sorption to
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particulates in the environment is not kinetically controlled (i.e.,
sorption equilibrium is attained instantaneously).
Inflow of
Chemical
Outflow of
Chemical
Volatilization
i]
Organic Chemical
in Aquatic
Environment
n
Sorption/Desorption
to Particulates,
II
Chemical Transformations
Photochemistry
Hydrolysis
Oxidation
Biotransformations
Hydrolysis
Oxidation
Reduction, etc.
Sedimentation
FIGURE 2.1 TRANSPORT AND TRANSFORMATION PROCESSES IN
AQUATIC ENVIRONMENTS
Evaluation of Chemical Loss Rates. The. rate of loss of a chemical due
to the above transformation processes plus volatilization, R , is given
by the sum of the rates of the individual processes, R., according to the
equation
RT =
• f\v 1 rri
W1 J
(2.1)
where k. is the rate constant for the i-th process, [E ] is an environ-
mental parameter that is kinetically important for the i-th process, and
[C] is the concentration of the chemical. The calculations of R. for
i
individual processes from environmental parameter and process data are
discussed in Sections 2.3.6 through 2.3.10 and in Sections 4 and 5 and
therefore will not be discussed here. The important environmental parameters
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for each process have been reviewed and the use of the parameters in the
calculations of environmental transformation rates has been discussed in
detail by Baughman and Burns (1980), Mill (1978), and Smith et al. (1977).
The above expression for R assumes that the loss of chemical is first
order in the chemical concentration, as certainly must be the case at the
highly dilute concentrations expected in the environment. Equation (2.1)
also requires that the rate of loss of chemical due to any one process R.,
is first order in the environmental parameter term E.; R. is then considered
as following overall second-order kinetic behavior. If it is assumed that
the low concentration of chemical in the environment has no significant
effect on the environment (i.e., does not change pH, biomass, dissolved
oxygen, etc.) and that the environmental parameter, E., is constant over
/ -1
a specific region and time period, the term k. [E.] can be expressed as a
simple pseudo-first-order rate constant, k., and then
or
RT = [Zk^fC]- kT[C] (2.2)
= Ik. (2.3)
where k_ is the overall pseudo-first-order rate constant for loss of chemical
due to transformation and volatilization. The half-life for loss of chemical
due to these processes is then given by
t^ = £n2/kT (2.4)
Influence of Sorption. In addition to losses of chemicals due to
these transformation and volatilization processes, sorption to particulates
can also reduce the concentrations of chemicals in aquatic systems. These
particulates may be either suspended sediments or biotic in origin, and
may eventually be deposited into benthic sediments. The suspended or benthic
sediment may later serve as a source of chemical from sorption-desorption
equilibrium as the chemical in solution is lost due to volatilization or
undergoes transformation in the water column. If biotransf ormation does
not occur .in biota (such as bacteria, algae, fish), the chemical may be
released back into solution when the organism dies and decomposes. The
understanding of chemical transformation when sorbed onto particulates is
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inadequate to predict or measure the rates of such reactions for use in
modeling efforts. Therefore, the following discussion assumes that no
transformations occur on participates and that sorption is completely
reversible and rapid in comparison with transformations that occur in
solution.
The partitioning of a chemical between particulates (sediment or biota)
and water at the low concentrations of chemicals usually found in the environ-
ment can be expressed as a partition coefficient K
KP - r (2-5)
r w
where C and C are the equilibrium concentrations of chemical on sediment
s w A
and in water, respectively (Raughman and Lassiter, 1978; Smith and Bomberger,
1980). For a chemical in aqueous solution containing particulates, the chemical
is equilibrated between the water and particulate (P) according to the equation
C + P —^ (C-P)
and the partition coefficient can be rewritten as
KP=T?TW (2-6)
where [C-P] is the mass of sorbed chemical per unit solution volume and
[P] is the mass of sorbing particulate per unit solution volume. The mass
balance of chemical in the solution-sediment system is given by
[CJ = [C-P] + [C ] (2.7)
i w
where [C ] is the total mass of chemical in a unit solution volume of
water containing [P] grams of particulate. Combination of equations (2.6)
By convention, Kp is unitless when Cs is in units that are equivalent to
Cw (i.e., Cs is in yg chemical per g particulate and Cw is in yg chemical
per g water). In this discussion, [C^,] will be defined in these weight
units and [C] will be defined in molecular units (moles liter"1); since
1 g water is approximately 1 ml, it follows that [Cj = 103[Cw][MW]"1 where
MW is the molecular weight of chemical. Note that [C] and [CWJ can be
used interchangeably in expressions such as equation (2.2) since first-
order rate constants are concentration independent, but the rate of loss
term, R, is of course defined in units corresponding to [Cw] or [C].
10
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and (2.7) then gives the fraction of the total chemical dissolved in solution:
[cw] i
w l - (2.8)
[CT] Kp[P] + 1
Baughman and Lassiter (1978) have pointed out that, given the relationship
shown in equation (2.8), the fraction of chemical in solution may be quite
high inspite of a large K value because the sediment or biota loading,
[P] , is often low in aquatic systems (i.e., K [P]<1).
The concentration of chemical in solution [C ] in the presence of
w
a particulate-water system is then given by
[CJ
(2'9)
Substitution of equation (2.9) into equation (2.2) for the rate of loss
of chemical then gives
k C
R =
T [P]K + 1
P
This relationship shows that, unless transformation on particulate is as
rapid (or faster) than in solution, the net effect of sorption will be to
reduce the overall rate of loss of chemical from the aquatic system. From
equation (2.10), it also follows that the half-life of the chemical is
given by
!Hn2
- <2-u)
Steady-state Concentrations. These equations describe the fate of a
chemical in a water body with no inflow or outflow. In a real aquatic
system, there is of course a rate of introduction of the chemical into
the water body, RT . The rate of loss of chemical in the environment R^
is the sum of R_ (as defined above) and the rates of dilution, and flow out
of the system (R and R , respectively). In a given segment of the water
body, a steady-state concentration of chemical is attained when R equals
R (Mill, 1978),
RI =RL=RT+RD+R0
11
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R
R
i
(2.13)
The steady-state concentration of chemical is then
[RX - RQ - RD](KP[P] + i)
<2'U)
The preceding discussion shows that along with the rate constant k_,
other factors such as initial concentrations, sorption, and dilution will
determine the final concentration of chemical in an aquatic environment.
The persistence of the chemical, however, is often described In terms of
a half-life where tj = In2/k . The half-life is simply the time
^ l
at which one-half of the initial concentration remains (or is lost), and
is not concentration dependent for the first-order processes assumed in
most calculations or environmental models. Table 2,1 shows the relation-
ship between the percentage of a chemical remaining as a function of time
in terms of ha If -lives. From these data it is clear that a short half-life
of a chemical may not be a sufficient argument for the safe discharge of
the chemical if the initial concentration must be substantially reduced by
environmental processes.
Table 2.1
PERCENT CHEMICAL REMAINING AS A FUNCTION
OF HALF-LIVES
% Chemical Number of Half-Lives
Remaining _ Elapsed _
75 0.42
50 1.0
25 2.0
10 3.3
5 4.3
1 6.6
0.1 10
0.01 13
12
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From the above discussion and equations, it is obvious that although
the half-lives and concentrations of chemicals in aquatic environments can
be predicted by manual calculations, the time required and the chances for
calculational errors may be overwhelming in some assessments. Therefore,
a computer program for executing these calculations is useful. The use
of process data and environmental parameters in calciilating half-lives
and concentrations of chemicals for different types of assessments using
manual computations and several existing computer programs is discussed
in Section 2.2.
2.2 APPLICATIONS OF PROCESS MODELING
The process modeling approach for predicting the persistence and con-
centrations of chemicals in an aquatic environment can be applied to many
types of assessments. According to the scope of an assessment, each evaluation
can be performed within limitations of time, cost, and the availability
(or reliability) of data. The process approach is the only economical way
in which sensitivity analyses can be performed to determine the relative
importance of environmental parameter and process data variables for chemicals
in aquatic environments.
"Worst case" or other scenarios can also be easily evaluated using a
process modeling approach; the worst case situation may be defined in
terms of environmental conditions least likely to transform a chemical or
in terms of the availability (or reliability) of process data where in--
complete data do not permit all processes to be included in the assessment.
The purpose of such assessments may range from simply establishing priorities
for future research to actually predicting environmental concentrations of
chemicals for regulatory/control strategy decisions.
Although the process modeling approach should be verified by actual
experience in the environment, it is explicit as to what processes and
environmental conditions are (and are not) used in any assessment and
therefore has potential for rational modifications and additions of new
processes. Three examples of the application of the process approach are
described below to demonstrate the utility of the process data and the
flexibility of the approach.
13
-------
The simplest level of application of the process modeling approach
is the manual calculation of rate or partitioning constants for a specific
environment. Thus, if the hydrolysis rate constant of a chemical is very
rapid within the time concern of an assessment, no other work need he con-
ducted even if other reactions are, in fact, faster hut the data are less
reliable or not available. If several processes appear to be equally
important, the overall first-order rate constant, k^> for loss of chemical
is given by the sum of individual constants
kT = Ek. (2.3)
and the half-life is then
£n2 ,r
Partitioning data may be used to calculate manually the fraction of chemical
in water or in biota and sediments for assessments. The K value may be
P
also used in equation (2.11) for the half-life of the chemical to include
the influence of partitioning of the chemical to aquatic parf.iculates.
Manual calculations may then be used for a number of simple aquatic fate
assessments in a cost-effective manner that does not require computer
facilities or personnel.
A higher level of sophistication for the process model approach is
an application in which manual calculations of the first-order rate constants
k. and of partition coefficients are integrated using a computer model that
allows for transformations and transport in and among several compartments
of a water body. The computer calculates solutions of the differential
equation for loss of chemical to obtain the concentration of chemical as
a function of time. Application of such a model has been used by Smith
et al. (1978) in estimating concentrations of chemicals in several types
of aquatic environments. Such an aquatic fate assessment requires the
participation of persons knowledgeable in the evaluation and use of the
individual process data and environmental parameters and yet is relatively
inexpensive in terms of the computer time required.
A more sophisticated level of application of the process approach
currently in use is a computer model that uses process data and environmental
14
-------
parameters to calculate the concentrations and half-lives of chemicals
in aquatic environments. One multicompartment model, known as the
Exposure Analysis Modeling System (EXAMS), has been applied to evaluate
the transport and transformation of phthalate esters in aquatic systems
(Wolfe et al., 1980).
The EXAMS model can calculate rate and partitioning constants as a
function of temperature if suitable temperature-dependence data are avail-
able. EXAMS can also include transformation processes in sediment and
biota if such process data are available. EXAMS requires less chemical
and biological expertise for manual calculations than the model described
by Smith et al. (1978), but is more expensive in terms of computer time.
Data presented in Section 3 of this report are in the units used in the
EXAMS model. Since EXAMS is a steady state model, it is limited to
applications of constant pollutant input, and more dynamic models
would closely simulate environmental situations.
In summary, the process modeling approach is a flexible procedure
that can be tailored to the needs of an individual assessment. Computer
manipulation of data is easily applied to these assessments, but manual
calculations are also practical if persons with suitable expertise are
available. It is certain that the iterative process involving the use,
verification, and subsequent modification of the process modeling approach
will allow better process models to evolve and contribute to an overall
better understanding of the environmental fate of chemicals.
15
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2.3 DEFINITIONS OF PROCESSES AND SOURCES OF DATA
2.3.1 Basis for Derivation of Data
The data on organic priority pollutants given in this report were
obtained from the literature and from calculations based on theory, structure-
activity relationships (SAR), or empirical calculations. In general, the
physical properties of a chemical are functions of the molecular structure
as an entity; that is, the elemental composition, spatial relationships
and size, molecular weight, and functional groups of the molecule all may
contribute to the property of the chemical. By contrast, the chemical or
biological reactivity of a molecule is usually due to selected functional
groups in the molecular structure, and the functional group may undergo
transformation with sometimes only minor changes in the total structure of
the molecule. The toxicity of a chemical may also be due, in part, to
functional groups on a chemical structure, although physical properties
will certainly be important in the transport, accumulation, and excretion
of the chemical in an organism.
Although many of the data on toxicity and concentration of chemicals
in the environment are expressed in terms of weight units (i.e., ppm), the
toxic impact and dynamic aspects of transport and transformations of the
chemical actually occur on a molecular level. Therefore, kinetic/equilibrium
units and concentrations are better expressed as molecular units (i.e., moles
liter or M), especially when relative reactivities or properties of chemicals
are compared to provide estimates or calculations of fate data.
The individual processes that chemicals may undergo can then be
classified and evaluated either according to specific physical properties
or according to the reactive functional groups that these chemicals may
have in common. The basis for the empirical correlations between K , K ,
ow oc
S , and K, are discussed in Section 4 and will not be discussed here except
to point out that all these constants describe equilibrium processes for the
chemical, between water and a second (organic) phase. Similarly, the volatil-
ization of a chemical can be evaluated in terms of Henry's constants, which
are functions of vapor pressure and water solubility (see Section 5)-
16
-------
The reactivity of a chemical may be classified according to select
functional groups in the molecular structure. For evaluations of hydrolysis
reactions, chemicals are classified as carboxylic acid esters (-C02R),
carboxylic acid amides (-CONH2), alkyl halides (R-X), phosphoric acid esters
((RO)3PO), to name only a few. Data for hydrolysis of a chemical can often
be estimated by analogy to another chemical with a similar functional group
or calculated by more formal procedures using linear-free energy relation-
ships such as the Taft equations, Hammett equation, or other such cor-
relations (Mill, 1979; Wolfe et al., 1978 and 1980).
Chemical oxidation rate constants can be calculated by evaluating
the reaction of an oxidant at a particular type of carbon-hydrogen bond
(i.e., hydrogen abstraction process) or at an olefinic bond (see Section
2.3.8).
No structure-activity relationship (SAR) or correlation method is now
available for predicting a direct photolysis rate constant except by analogy
to other chemicals, which is often unreliable because of the complex chem-
istry of photoexcited states. When absorption spectral data are available,
a maximum rate constant (ie., fastest' reaction possible) may be calculated
if a reaction quantum yield of unity is assumed. The maximum rate constant
is useful for comparison with other rate constants to determine whether
photolysis may be an important process, but probably will overestimate the
photolysis rate because the reaction quantum yield is usually less than
unity. The use of SAR and correlation procedures in environmental assess-
ments has been discussed by Mill (1979), by Wolfe et al. (1980). and in
Sections 4 and 5 of this report.
In using the theoretical equations, SARs, and empirical correlations,
it is important to remember that the scientific basis for understanding
these relationships is still being developed and verified. The situation
of the several empirical correlations between S and K is a good example
of such problems, in that different groups of chemicals have been used to
establish empirical correlations that, not surprisingly, give different
equations. Recognition of the influence of sediment particle size on K
oc
measurements has also redefined the K data base, which changed the cor-
relation equations (see Section 4 and Karickhoff et al., 1979). Thus
17
-------
the existence of several SARs or empirical correlations for individual
properties, reactivities, or processes should not be considered a problem
or contradiction, but rather a reflection of the developing understanding
and increased data base available for such data prediction methods.
For this report, data obtained from calculations involving theory,
SARs, or empirical correlations have been clearly identified so that the
user can recognize the source of such data and can recalculate data using
more current or improved procedures as they become available.
The following sections contain descriptions of environmental processes
and the process data important in aquatic fate assessments. The process
data are discussed in the order that they appear on the data sheets in
Section 3. The sources of the process data are also discussed.
2.3.2 Chemical Name and Molecular Weight
The names of the chemicals used on the data sheets in Section 3 are
those used by Callahan et al. (1979); alternative names are also given in
*
that report. The Toxic Substances List (TSL) number is given in that
report to provide an unambiguous reference to toxicological data.
The molecular weight is not used for environmental assessments in
itself, but is required for conversion of units from ppm to molar units
(M). The molecular weight has also been used to calculate the oxygen re-
aeration rate ratio (see Section 5.)
2.3.3 Melting and Boiling Point
These data are not used directly in aquatic fate assessments, but
they show in which phase (gas, liquid, solid) the pure chemical is found
under environmental conditions. If the heat of vaporization, AH , of a
^ vap
chemical is not available, it may be estimated from Trouton's rule
AHvaP - 21TBP (2'16)
where the boiling point, T , is given in degrees Kelvin (= °C + 273);
Trouton's Rule is discussed in most physical chemistry textbooks. A value
of AH can then be used to calculate vapor pressure values at any
*
Registry of Toxic Effects of Chemical Substances, published yearly by the
National Institute of Occupational Safety and Health.
18
-------
temperature using the Clausius-Clapeyron equation, which is also found in
chemistry textbooks. The melting point should be used in the calculation
of water solubility from K data for compounds that are solids above 25°C
ow
(see Section 4) .
Most melting point and boiling point data were taken from Callahan
et al. (1979) and are reliable within several degrees. Boiling point data
are usually cited for 760 torr (or 1 atmosphere) unless otherwise noted.
2.3.4 lonization Constants
The pH values found in most aquatic systems range from approximately
pH 4 to 9, with extreme values down to pH 2 and up to pH 11. If a chemical
is ionized under environmental conditions, the physical properties as well
as the chemical reactivity will change with pH (for instance, the solubility
of an ionic form of an organic chemical will likely be greater than for the
neutral species) . The ionization of a neutral organic chemical HA possess-
ing acidic properties can be written as
HA ^^ H+ + A~
and the ionization constant K. defined as
A
_
K ~
A ~ [HA]
The constant K is often expressed logarithmically as the pK , where
A A
PKA = -log KA (2.18)
For basic compounds, the equilibrium between the neutral basic species,
B, and water is written as
B + H20 ^— ^ BH+ + OH~
and the ionization constant K is defined as
D
= [BH+][OH~]
KB [B] U'19)
where the water concentration (55.5 M) is taken as constant and included
in the K value. The negative logarithm of K is defined as the pK .
19
-------
For some chemicals, several pK or pK values may exist for different
moieties or stages of ionization. Although no such chemicals are among
the organic priority pollutants, data on multifunctional ionization constants
may be required for other chemicals. Note that K and K are also temperature-
A. D
dependent; the temperature dependence of K or K is generally not available
A. -D
for organic compounds. In this report K or KB is given for 25°C unless
otherwise noted.
Data for pK or pKn are reported as available. Where ionization or
A B
ionic forms do not occur in the aquatic environment, the code pK-NER
(for pK not environmentally relevant) is entered for the data value. When
several forms (ionic or netural) of the chemical may exist in the environment,
process data are given for each form if data are available. Additional
comments on such data are included in footnotes on the data sheets.
2.3.5 Partitioning Constants
Chemicals in aquatic environments may be sorbed to sediments, biota,
or suspended particulates. If not degraded, the sorbed chemical may be
transported on the particulates or enter the food chain and may later be
desorbed from the particulates back into solution in the water column.
The importance of sorption of a chemical in determining the concentration
and half-life of a chemical in aquatic systems is discussed in Section 2.1;
other aspects of the sorption/solubility phenomena and calculation of partitioning
constants from empirical correlations are detailed in Section 4. The follow-
ing discussion briefly defines each partition constant (including water
solubility) and the units of data presented in this report. The sources
of data and the codes used on the data sheets are also explained.
Water Solubility, S (ppm, or mg liter *). Water solubility data
are required for calculating Henry's constant (see Section 2.3.6) and for
calculating other partition coefficients using the correlation equations
discussed in Section 4.
Octanol/Water Partition Coefficient. K (unitless). This constant
_ .—_ ow——• — —•
has been used in medical and environmental science as a measure of the
hydrophobicity/hydrophilicity of chemicals (Hansch and Leo, 1979; Kenaga
and Goring, 1978). The K values in this report were used to calculate
ow
20
-------
S , K , and K data as discussed in Section 4.2. The calculation of K
itself from structural features of the molecule is discussed in Section 4.3.
Sediment Partition Coefficient, Normalized for Organic Carbon Fraction,
K (unitless). The product of K and the environmental parameter value
—oc oc
for the fraction of organic carbon in sediment, f , gives the coefficient
for partitioning onto that particular sediment, K . This K is only for
P P
sorption due to the hydrophobicity/hydrophilicity of a chemical and does
not include ionic or other phenomena that may additionally contribute to
sorption of a chemical to sediments.
Microorganisms/Water Partition Coefficient, K^ [(yg/g)(mg/liter) ].
. — _—. .____ y
This value is used to evaluate the partitioning of a chemical between
microorganisms and water in the water column. Since there are many com-
plicating factors in the partitioning into biota, this value of K should
be used with caution. The values of 1C, listed in this report were calculated
B
from the correlation equation discussed in Section 4.
As discussed in Section 4, values of K , S , K , and K_ are also
ow w oc B
useful for calculating their complementary partitioning coefficients either
for direct use in assessments or for verifying the accuracy of a literature
or laboratory-measured value. Many of the K data in this report were
calculated using the octanol/water partition coefficient calculation com-
puter program developed at SRI using the procedures and data base of Hansch
and Leo (1979) (see Section 4). Values of K and K were generally cal-
culated from values of K using the correlation equations described in
ow
Section 4. S data were calculated from K values using the correlation
w ow
equations given in Section 4 when literature data were either unavailable
or considered unreliable. Values of K,,, K , and S calculated from K
B oc w ow
values are coded in the form C-KB f Kow, C-Koc f Kow, and C-Sw f Kow respectively.
When literature data were available for K or S , these values were
oc w
compared with the values calculated from K , and the best value was chosen
r ow
based on a critical review of the original literature and an evaluation of
the strengths and weaknesses of the database used for the K calculation.
ow
Some comparisons of data are discussed in Section 4. In a few cases, the
calculated K values were clearly inaccurate (by over an order of magnitude),
21
-------
and therefore K values were "back-calculated" from the K -S correlation
ow ow w
equations given in Section 5; such cases are discussed in footnotes to the
data sheets in Section 3.
2.3.6 Volatilization Constants
Volatilization is an important loss process for some chemicals in
aquatic systems, and current research is rapidly increasing the understand-
ing of the process and improving methods for predicting volatilization rates
for use in environmental assessments. The theory and procedures for cal-
culating the rate constants and half-lives for volatilization of chemicals
from aquatic systems are discussed in detail in Section 5. This section
describes the use of the data on the data sheets in Section 3 and discusses
the source of the data.
Vapor Pressure, P (torr). The vapor pressure of an organic chemical
is, in itself, a qualitative or relative measure of the volatility of the
chemical in its pure state and can be used to calculate the Henry's constant
used in volatilization rate constant calculations. Most vapor pressure data
in this report were taken directly from Callahan et al. (1979). It is not
clear in that report if the vapor pressures for solids that were extrapolated
to 20°C from literature vapor pressure data obtained above the melting point
have been corrected for the phase change (see Section 5.3.) If the
correction was not made, the calculated vapor pressure and H will be too
c
high.
Henry's Constant, H (atm m3 mole"1). The calculation and use of
Henry's constants for calculating volatilization rate constants and half-
lives are discussed in Section 5. Most H values in this report were
calculated from vapor pressure and water solubility data, which are also
listed on the data sheets. In some cases where P and S were available
v w
only at slightly different temperatures (i.e., differences less than 10°C),
H was calculated without any correction for temperature. If a better
value for H^ is required, the user may interpolate or extrapolate the P
or Sw data as necessary to recalculate another H value; this recalculation
was not done for this report to minimize confusion and maintain the integrity
of the individual Sw or P values as referenced. The values of H calculated
22
-------
in such a manner are coded as C-VP25°/S30° on the data sheets, indicating
a value Calculated from vapor pressure data at 25°C and water jsplubility
data at 30°C. The H values calculated from P and S data at the same
- c v w
temperature are coded C-VP/S-300, for example, indicating that both values
were given for 30°C.
C 0
Reaeration Rate Ratio, k /k (unitless) . This value is ratio of
the first-order rate constant for loss of chemical from aqueous solution
divided by the rate constant for oxygen uptake by the same solution. It
may be measured in the laboratory (Smith and Bomberger, 1980) or obtained
by calculation procedures (see Section 5) . The use of this ratio is
applicable only to high volatility chemicals or to chemicals with Henry's
constants (H ) greater than 3500 torr M"1 (or 4.6 x 10~3 m3 atm mole"1).
° CO
For chemicals with smaller H values, the use of k /k will overestimate
c v v
the importance of volatilization.
C 0
Most of the k /k data in this report were calculated using the equation
v
k° =
V
which is developed and discussed in Section 5 (equation 5.39). The source
code for such values is C-DC.7, indicating a Calculated value using diffusion
Coefficients with an exponent of 0. 7. When the Henry's constant is so low
that the use of rate ratio will overestimate the volatilization rate, as
discussed in Section 5, the code NAV is entered for the value indicating
that the reaeration rate ratio is not applicable for volatilization cal-
culations. In general, NAV is entered for chemicals with H < 2 x 10
c
atm m mol
23
-------
2.3.7 Photolysis Data
Photolysis of chemicals in aquatic systems occurs when sunlight of
irradiating wavelengths above 290 nm is absorbed by the chemical. Strato-
spheric ozone filters out the lower, more energetic wavelengths of sunlight.
Photolysis of a chemical may be considered to result from two types of
processes. One process, in which the chemical absorbs light and then under-
goes reaction, is referred to as direct photolysis. The rate of direct
photolysis of a chemical in a dilute solution in pure water, R , is given by
the equation
R = bcj>Ie,I, [C] (2.20)
p A A
where b is a constant to provide appropriate units, is the reaction quantum
yield, and F and I are light absorption coefficients and light fluxes,
A A
respectively, at wavelength intervals, A. Details on calculations of direct
photolysis rates in aquatic systems have been described by Zepp and Cline
(1977), Zepp (1979), and Mabey et al. (1980).
For direct photolysis of a chemical, the first-order photolysis rate
constant, k , is then given by
k = bZe,I. (2.21)
p A A
In sunlit aquatic environments, the rate constant k will vary because
the distribution and intensity (or photon flux) of sunlight vary with
time of day, season, and latitude. Thus a photolysis rate constant must
be referenced to a specific time period (e.g., averaged over a 24-hour
day, averaged over several hours at midday, instantaneous rate constant
at noon), specific season, and latitude.
Photochemical transformations of a chemical in natural waters may
also occur due to processes involving an initial light absorption by
natural substances present in the water, which then causes reaction of
the chemical. Since the chemical itself does not absorb the incident
light, these processes have generally been referred to as indirect photo-
lyses.
One type of indirect photolysis is a photosensitized process in which
the excited state energy of the natural substances (probably humic or fulvic
materials) is transferred to the chemical, which then undergoes reaction.
24
-------
At present there are a few examples of such reactions occurring in natural
waters, and these reactions are the subject of current research (Zepp et al.,
1980; Spanggord et al., 1980).
Other types of indirect photolyses are oxidation processes in which
irradiation of natural materials produces free radical or singlet oxygen
intermediates, which then react with a chemical to produce transformation
products. Because the free radical or singlet oxygen intermediates react
with the chemical in its ground state, it is usually convenient to consider
such reactions as oxidation processes (see Section 2.3.8). In the evaluation
of literature information or laboratory experiments, it is important to
recognize that these oxidation processes, as well as direct photolysis or
sensitized photolyses, may lead to oxidation and thereby complicate identifi-
cation of the particular process for use in a generalized environmental
assessment.
The rate of loss of a chemical due to an indirect process may be
written in the general form
R' = k '[C] (2.22)
P P
where k is a first-order rate constant for the particular photoreaction.
P t
For a photosensitized process, k would be a composite of terms, including
the quantum yield for energy transfer from the natural substance excited
state species to the chemical, the concentration of natural substance and
the sunlight intensity. For the free radical or singlet oxygen reactions
discussed in Section 2.3.8, the rate constant k nominally would be equal
to k [OX]. As in direct photolysis, the value of k must be referenced
to a particular time period because the irradiating sunlight intensity and
distribution responsible for these reactions will vary with time of day,
season, and latitude.
Present knowledge of environmental photochemistry allows prediction
of only the direct photolysis rate constant using equation (2.21). Although
indirect photolyses can be faster than direct photolyses for some chemicals,
incomplete knowledge of photosensitized reactions in the environment does
not permit reliable predictions of k values based on process data and
p
25
-------
environmental parameters. Where literature information shows that indirect
photolyses of a chemical in natural waters do occur, this information and
the rate constant data are listed as a footnote on the data sheets in
Section 3. Such data may be used at the option of the user. Process data
for calculating the rate constants for direct photolysis of chemicals in
aquatic environments are described below.
Absorption Spectrum Coefficients, E (in M cm ). The absorption
coefficients of the chemical are determined from the uv-visible spectrum
of the chemical and are used with sunlight photon flux data, I , to calculate
the direct photolysis rate constant, k . The value of k may be calculated
by computer (Zepp and Cline, 1977) or by manual calculation (Mabey et al.,
1980). The e values are given at the wavelengths required for the k
A P
calculation computer program of Zepp and Cline (1977).
The absorption spectrum coefficients, e,, for organic chemicals in
A
this report are given as follows on the data sheets in Section 3:
(1) If the chemical has no significant absorptions above 290 nm,
the code PNES (photolysis riot environmental ^significant) is
entered on the data sheet along with the source of this conclusion.
(2) If no spectra are available, the space is left blank.
Chemicals in this category are known or suspected to
have significant absorptions above 290 nm by analogy to
similar chemicals structures and will require laboratory
measurements to obtain data.
(3) When e data are available, DATA-ATT is entered in the
value space to signify data attached, and the data are
given in a footnote. If a published absorption spectrum
is available but not suitable for accurate calculation
of e, values, SPEC-ATT is entered in the value space to
signify that the spectrum is attached, and the spectrum
is located by a footnote. Although some of these spectra
were obtained in nonaqueous solvents, they are useful
for a qualitative assessment of the possible importance
of photolysis.
Reaction Quantum Yield, 4>, (unitless). The reaction quantum yield
is the efficiency with which light absorbed by a chemical results in
transformation of the chemical and is defined as the ratio of the number
of moles of chemical transformed to the number of einsteins (a light flux
quantity) absorbed by the chemical. The reaction quantum yield is used
26
-------
with e data and light flux data (an environmental parameter) to calculate
A
the rate constant for direct photolysis, k . Values of are given on the
data sheets along with the source of the value; when PNES is entered for the
absorption spectrum coefficients, PNER is entered for the $ value, indicating
that the reaction quantum yield is riot environmentally _relevant.
Photolysis Rate Constant, k (hr"1). Some literature data are avail-
p
able for photolysis experiments conducted in sunlight, but without any
measurements of e or . The rate constants for these experiments are
A
entered as k values and with appropriate information (such as season,
latitude) as may be available or surmised from the literature reference.
In most cases, additional comments are also provided as footnotes.
Where data are available for e and , a value of k is calculated
A P
for a particular stated time interval to assist the reader who does not
have access to I data for calculating k . The source of such calculated
A p
values is usually the computer program SOLAR of Zepp and Cline (1977), and
is designated CC-SOLAR, meaning Computer Calculated using the SOLAR program.
2.. 3.8 Oxidation Rate Constants
Chemical oxidation of organic chemicals in aquatic environments
may occur due to several different oxidants, among which are singlet oxygen
(102), alkyl peroxyl radical (R02»), alkoxy radical (R0»), or hydroxyl
radical («OH). As discussed in Section 2.3.7, the source of these oxidants
is primarily photochemical, but since the oxidants react with chemicals in
their ground state, and oxidation therefore does not involve the photo-
chemistry of the chemical itself, oxidations are reasonably considered as
discrete processes apart from photochemistry.
Each oxidant has a unique reactivity toward organic moieties, and the
relative as well as absolute concentrations of these oxidants will probably
vary with environmental parameters such as concentrations , origin of
humic-fulvic materials, and sunlight intensity. Therefore, the application
of an "average oxidant concentration" concept to predict a total oxidation
rate is not recommended.
Literature information has reported data on oxidation of organic
27
-------
chemicals by oxy radicals such as R02- and 102 . The laboratory study
conducted by Mill et al . (1980) using natural waters indicates that R02-
— 9
radical concentrations of a. 1 x 10 M may be present in the surface waters
of sunlit water bodies. Oxidation reactions initiated by R02- include the
following:
R02-
R02-
R02»
R02-
1
+ -C-H
i
\ ,-
+ r=r
+ /u u\
+ ArOH
+ ArNH2
>
*"
— ^
+
RO
RO
RO
RO
2H
+
1 1
1
-C»
1
2-c-c«
1 1
2H
2H
4-
ArO
•
+ ArNH
Of these reactions, the last two are quite rapid in aquatic environments
(tj < several days), whereas the others are slower and usually will not
-3
be important for most chemicals.
_ i 2
Zepp et al. (1978) have shown that 102 can be formed at w 1 x 10 M
concentrations in sunlit natural waters. The most important reactions for
102 with organic chemicals are those involving reaction with olefinic
moieties (Ranby and Rabek, 1978) .
CHa- |
* -C-C
t
N
02 + .C=C - * -C-C=CH
OOH
x XCH2-
- > C-C - > Products
"I r
0-0
Some rate constants for 102 and R02« are listed in a review by Mill (1980).
The rate of loss of organic chemicals R by oxidation is
U/C
ROX = kR02.[R°2*] [C] + kl02[1°2]C + kox[OX][C] (2'23)
where k and [OX] are the rate constants and concentration values for
other unspecified oxidants . Only data for second-order rate constants
k_-. and ki have been estimated for this report. When two rate constants
KU 2 * u 2
are given on the data sheets, the second-order rate constants should be
multiplied by their respective oxidant concentrations to determine which
of the first-order rate constant values is larger, and that rate constant
should be used for an assessment.
28
-------
Apart from a direct measurement of a rate constant at a specific
temperature (which is rare), most rate constants in this report were obtained
either from extrapolation of a rate constant for the organic chemical mea-
sured at another temperature or from a correlation of structure with re-
activity as discussed below.
Rate Constant for Oxidation by Peroxyl Radical, R02», k (M hr )
— 1 j. '- ox •—
Because many chemicals in the priority pollutant list have several kinds
of reactive centers for oxidation by R02-, the overall rate constant k _
KU 2
was obtained by first calculating the individual rate constants for each
reactive site and then summing these rate constants. For example, acrolein
has two reactive sites: (1) addition to the double bond and (2) H-atom
transfer from the carbonyl
')
R02- + CH2=CHCHO———»• CH2=CHCO + R02H (2.25)
R02- + CH2=CHCHO ———*• R02C-C-CHO (2.24)
k2
V - ki + k*
For aldrin, there are two kinds of double bonds and three kinds of CH bonds.
Each rate constant was estimated, but since only the addition to the un-
substituted bond was very fast, the other reactions were ignored. When
there were more than one -CH bond of a given kind, the rate constant was
multiplied by the number of similar -CH bonds to give the correct total
rate constant for oxidation of that CH bond.
Two kinds of procedures were used to calculate individual k values
OX
for R02» reactions. In the first, when a structure was analogous to another
chemical structure with a measured rate constant at a similar temperature,
the measured rate constant was used directly (Hendry et al., 1974). (The
-CHO bond in acrolein is an example.) The second procedure, used most often,
is based on structure-reactivity relations established by Howard and coworkers
for H-atom transfer (Korchek et al., 1972) and addition to double bonds
(Howard, 1972), as shown here.
For the hydrogen atom transfer reaction
log k = 18.96-0.2[D(R-H)] (2.26)
KU2
where D(R-H) is the bond dissociation energy of the CH bond.
29
-------
For the R02 addition to double bonds
log k = [16.54-0.2D(xCR2-H)]/0.75 (2.27)
RO 2
where D(XCR2-H) is the bond dissociation energy of a species that gives
the radical formed by R02 addition and where R02 is assumed to have the same
effect as Me on D(C-H). Thus for oxidation of vinyl chloride
i-cr
R02- + C=C > R02
' N II
the closest analog would be MeCH2CHCl, and the value of D(MeCH2CHCl-H)
would be used in equation (2.27). Bond dissociation energies were taken
from Furuyama et al. (1969).
Rate Constant for Oxidation by Singlet Oxygen, 102, k (M hr ) .
OX
Only a few of the chemicals discussed in this report are reactive toward ^O,,;
these include some polycyclic aromatic and a few olefinic double bond or
diene systems. When no reactive center was recognized, chemicals were
assigned kj < 3600 or < 360 M h . All reactive chemicals were assigned
rate constants by analogy with similar structures having shown rate constants
for reaction with singlet oxygen. For cyclic olefins, the values of Matsuuro
et al. (1973) were used. For alicyclic olefins and other structures, the
rate data summarized by Gollnick (1978) were used.
Since all oxidation rate constants given in Section 3 were calculated
by the above methods, the data source code C-OX (calculated-oxidation) is
entered for all values.
2.3.9 Hydrolysis Rate Constants
Hydrolysis refers to reaction of a chemical with water, usually
resulting in the introduction of a hydroxyl function into a molecule and
loss of a leaving group -X
R-X + H20 * ROH 4- HX
The hydrolyses of some classes of compounds are catalyzed by acid or base,
and therefore the hydrolysis rates of these chemicals in the environment
can be pH dependent. The subject of hydrolysis in aquatic systems has
30
-------
been reviewed in detail by Mill et al. (1980), and an extensive compilation
of hydrolysis data was published in a review by Mabey and Mill (1978).
The rate of hydrolysis of a compound at a specific pH value is given
by the equation
Kg = kh[C] = (kA[H+] + kjj + kB[OH~])[C] (2.28)
where k_ is the first-order rate constant for hydrolysis at the pH, k
A
and kg are second-order rate constants for acid- and base-promoted hydro-
lyses, and k^ is the first-order rate constant for the pH-independent,
neutral hydrolysis process. Using the autoprotolysis equilibrium expression
[H+] [OH~] = K , (2.29)
w
equation (2.28) can be rewritten as
kh = kA[H ] + \ + kBKw (2.30)
Equation (2.30) shows that k, will be dependent on the pH of the aquatic
system and on the relative values of k , k , and lc^. There is at present
no reliable information to show that hydrolysis rates in aquatic environ-
ments will be catalyzed by species other than [H ] or [OH ].
The hydrolysis rate constants k,, k,-, and k.T used to calculate k. as
A B N h
a function of pH are described below along with the source codes for cal-
culating or estimating the values of the rate constants.
Acid-Promoted Rate Constant, k, (M hr ). This rate constant is
for the acid-promoted hydrolysis of a chemical. In regions where only k
+ - 'A
contributes to hydrolysis (i.e., k [H ] » k^ + kg [OH ]), k will decrease
by a factor of 10 for each 1-unit increase in pH.
Base-Promoted Hydrolysis Rate Constant, k,, (M hr ) . This rate
,— is
constant is for the base, (OH ), promoted hydrolysis of a chemical. In
regions where only k contributes to hydrolysis, Ic will increase by a
factor of 10 for each 1-unit increase in pH.
Neutral-Hydrolysis Rate Constant, k^ ( hr ). This rate constant is
for the pH-independent hydrolysis of a chemical.
31
-------
Data or sources pertaining to the hydrolysis of the organic chemicals
have been entered in the data sheets in several ways. When a chemical
structure had rio Jiydrolyzable functional groups, NHFG is entered. When
chemical hydrolysis occurs only at extreme pH values or temperatures or
with catalysts not available in aquatic environments, HNES is entered
(hydrolysis nx>t environmentally significant). The terms NACM (or NBCM)
are used to indicate that no a.cid (or _base) Catalyzed mechanism involving
H (or OH ) species is known. For all such cases, zero is entered for the
value of the process data to clearly eliminate the particular process from
further consideration. For alkyl halides, Mabey and Mill (1978) have shown
that the acid- and base-catalyzed terms in equation (2.28) are not important
compared with the neutral hydrolysis term, and therefore HPHI (hydrolysis
pH-independent) is entered. Since k and k are not zero, but are insigni-
ficant for environmental assessment purposes, a hyphen has been entered
for the process data value. Other data for hydrolysis are referenced, or
the rationale is explained in footnotes to the data sheet.
2.3.10 Biotransformation Rate Constants
Biotransformations are undoubtedly important processes for degrada-
tion of chemicals in aquatic environments, resulting in hydrolysis, oxidation,
and reduction of the chemical structure to ultimately produce carbon dioxide
and water. The complex factors influencing the biotransformation of a
chemical include pH, temperature, dissolved oxygen, available nutrients,
th,e presence of other organic chemicals (synthetic or naturally occurring)
that may serve as cometabolites or alternative energy sources, and the
populations and types of organisms capable of transforming the chemical.
For most assessments, the initial biotransformation step is of prime
importance (i.e., removal of the specific chemical from the environment).
However, the biotransformation process is still too complex to reliably
predict a biotransformation rate constant using theoretical approaches
such as those available for chemical and physical processes.
Maki et al. (1980) recently reviewed some of the aspects of the measure-
ment of biotransformation rates and the use of such data. The rates of
biotransformation are complex functions of chemical concentration and
32
-------
microbial biomass. However, at the concentrations of a chemical in the
environment (
-------
Table 2.2
ESTIMATED RATE CONSTANTS (ml cell hr ) FOR BIOTRANSFORMATION
OF CHEMICALS BY BACTERIA IN WATSR BODY SOLUTION PHASE
Category I
3 x 10~6
Phenol
Category II
1 x 10~7
4-Cl-phenyl phenyl ether
Benzene
Toluene
2-C1 phenol
Category III
3 x 10 '
Acrolein
Aid r in
Isophorone
Endosulfan
Category IV
1 x lO'10
ODD
Endrin
Endosulfan sulfate
Hexa-Cl-cyc lohexane
Category
3 x 10"1
Chlordane
DDE
DDT
Dieldrin
V
2
CO
2,4-Di-Cl phenol
4-Nitro phenol
2,4-Dimethyl phenol
4-Nitro phenol
2,4-Dimethyl phenol
Diethyl phthalate
Naphthalene
Endrin aldehyde
2-Cl-naphthalene
Bis(2-Cl-ethyl)ether
4-Br-ohenvl phenvl ether
Cl-benzene
Ethyl benzene
Nitrobenzene
2,4,6-Tri-Cl phenol
Penta-Cl phenol
2-Nitro phenol
2,4-Dinitro phenol
£—Cl—m-cresol
4,6-Dinitro—o^cresol
Butyl benzyl phthalate
Acenaph thene
Acenaphthylene
Anthracene
Acrylonitrile
Fluorene
Lindane
TCDD
Tetra-Cl-methane
1,2-Di-Cl-ethane
Tri-Cl-ethene
Tetra-Cl-ethene
1,2-Di-Cl-propane
1,3-Di-Cl>-pr opane
Hexa^Cl-ethane
Hexa-Cl-butadiene
Hexa-Cl-cyclo pentadiene
Br-di-Cl-methane
Di-Br-Cl-methane
Tri-Br-methane
Bis(2-Cl-isopropyl)ethyl
2-Cl-ethyl vinyl ether
1,2-Di-Cl-benzene
1,3-Di-Cl-benzene
1,4-Di-Cl-benzene
1,2,4-Tri-Cl-benzene
2,6-Dinitrotoluene
Benzo[a]anthracene
Chrysene
Fluoranthene
Pyrene
Heptachlor epoxide
Toxaphene
_is(2-Cl-ethoxy) methane
Hexa-Cl-benz ene
Benzo(b)fluorantbene
Benzo(k)-fluoranthene
Benzo[ghi]perylene
Benzo[a]pyrene
uibenzo[ah]anthracene
Indeno [1,2,3~c.d] pyr ene
Dimethyl nitrosamine
3,3'-Di-Cl-benzidine
Di-n-propyl nitrosamine
1,1,2-Tri-Cl-ethane
1,1,2,2-Tetra-Cl-ethane
(Category IV cont.)
Diphenyl nitrosamine
Benzidine
1,2-Diphenylhydrazine
-------
2.4 REFERENCES
Baughman, G. L., and L. A. Burns. 1980. Transport and Transformation of
Chemicals: A Perspective. In: The Handbook of Environmental Chemistry,
Vol. 2, Part A. 0. Hutzinger, Ed. Springer-Verlag, New York.
Baughman, G. L., and R. R. Lassiter. 1978. Prediction of Environmental
Pollutant Concentration. In: Estimating the Hazard of Chemical Sub-
stances to Aquatic Life, ASTM STP 657 John Cairns Jr., K. L. Dickson,
and A. W. Maki, Eds., pp. 35-54. American Society for Testing and
Materials, Philadephia, PA.
Baughman, G. L., D. L. Paris, and W. C. Steen. 1980. Quantitative Expression
of Biotransformation Rate. In: Biotransformation and Fate of Chemicals
in Aquatic Environment. A. W. Maki, K. L. Dickson, and J. Cairns, Jr.,
Eds. American Society for Microbiology, Washington DC.
Callahan, M. A., M. W. Slimak, N. W. Gabel, I. P. May, C. F. Fowler, J. R. wreed,
P. Jennings, R. L. Durfee, F. C. Whitmore, B. Maestri, W. R. Mabey,
B. R. Holt, and C. Gould. 1979. Water-Related Environmental Fate of 129
Priority Pollutants. U.S. EPA, Washington D.C. Vol. I, EPA-440/4-79-029a;
Vol. II, EPA-440/4-79-029b.
Furuyama, S., D. M. Golden, and S. W. Benson. 1969. Kinetic Study of the
Reaction CH3I + HI «* CH2I2: A Summary of Thermochemical Properties
of Halomethanes and Halomethyl Radicals. J. Amer. Chem. Soc. 91:7564-7569.
Gollnick, K. 1978. In: Singlet Oxygen, B. Ranby and J. F. Rabek, Eds.
John Wiley and Sons, New York.
Hansch, C., and A. Leo. 1979. Substituent Constants for Correlation
Analysis in Chemistry and Biology. Wiley-Interscience, New York.
Hendry. D. G., T. Mill, L. Piszkiewicz, J. A. Howard, and H. K. Eigenmann.
1974. A Critical Review of H-Atom Transfer in the Liquid Phase. J.
Phys. and Chem. Ref. Data 3:937-978.
Howard, J. A. 1972. Absolute Rate Constants for Reactions of Oxyl Radicals
Adv. Free Radical Chem. 4:49-174.
Karickhoff, S. W., D. S. Brown, and J. A. Scott. 1979. Sorption of
Hydrophobic Pollutants on Natural Sediments. Water Research 13, 241.
Kenaga, E. E., and C.A.I. Goring. 1978. Relationship Between Water
Solubility, Soil-Sorption, Octanol-Water Partitioning, and Bioconcen-
tration of Chemicals in Biota. In: Aquatic Toxicology, ASTM STP 707,
J. G. Eaton, P. R. Parrish, and A. C. Hendricks, Eds. American Society
for Testing and Materials, Philadephia, PA.
Korcek, S., J. H. B. Chenier, J. A. Howard, and K. V. Ingold. 1972. Absolute
Rate Constants for Hydrocarbon Oxidation. Can. J. Chem. 50:2285-2297.
Mabey, W. R., and T. Mill. 1978. Critical Review of Hydrolysis of Organic
Compounds in Water Under Environmental Conditions. J. Phys. Chem. Ref.
Data 7:383-415.
35
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Mabey, W. R., T. Mill, and D. G. Hendry. 1980. Photolysis in Water.
In: Laboratory Protocols for Evaluating the Fate of Organic Chemicals
in Air and Water. EPA Report (Draft). EPA Contract 68-03-2227.
Maki, A. W., K. L. Dickson, and J. Cairns, Jr., Eds. 1980. Biotransfor-
mation and Fate of Chemicals in Aquatic Environments. American Society
for Microbiology, Washington DC.
Matsuura, T., A. Horinaka, and R. Nakashima. 1973. Photoinduced Reactions.
LXXII. Reactivity of Singlet Oxygen Toward Cyclic Olefins. Chem.
Letters, 887-890.
Mill, T. 1978. Data Needed to Predict Environmental Fate of Organic Com-
pounds. Symposium on Environmental Fate held at meeting of American
Chemical Society, Miami, FL, September 1978.
Mill, T. 1979. Structure Reactivity Correlations for Environmental Re-
actions. Washington, D.C. EPA Report. EPA-560/11-79-012.
Mill, T. 1980. Photooxidation in the Environment. In: Handbook of
Environmental Chemical, 0. Hutzinger, Ed., Vol. 2, Part A. Springer-
Verlag, Herdelberg. Contract No. DAMD17-78-C-8081.
Mill, T., D. G. Hendry, and H. Richardson. 1980. Free Radical Oxidants
in Natural Waters. Science 207:886-887.
Mill, T., W. R. Mabey, and D. G. Hendry. 1980. Hydrolysis in Water.
In: Laboratory Protocols for Evaluating the Fate of Organic Chemicals
in Air and Water. EPA Report (Draft). EPA Contract 68-03-2227.
Ranby, B., and J. F. Rabek, Eds. 1978. Singlet Oxygen. John Wiley and
Sons, New York.
Smith, J. H., and D. C. Bomberger. 1980. Volatilization from Water.
In: Laboratory Protocols for Evaluating the Fate of Organic Chemicals
in Air and Water. EPA (Draft). EPA Contract 68-03-2227.
Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T.-W. Chou,
D. C. Bomberger, and T. Mill. 1977. Environmental Pathways of Selected
Chemicals in Freshwater Systems. Part I. Background and Experimental
Procedures. U.S. EPA Athens, GA. EPA-600/7-77-113.
Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T.-W. Chou,
D. C. Bomberger, and T. Mill. 1978. Environmental Pathways of
Selected Chemicals in Freshwater Systems. Part II. Laboratory
Studies. U.S. EPA Athens, GA. EPA-600/7-78-074.
Spanggord, R. J., T. Mill, T.-W Chou, W. R. Mabey, J. H. Smith, and S.
Lee. 1980. Environmental Fate Studies on Certain Munition Waste-
water Constituents. Phase II Laboratory Studies. Final Report,
Contract No. DAMD17-78-C-8081, U.S. Army Medical Research and Develop-
ment Command. Fort Detrick, MD.
36
-------
Wolfe, N. L., L. A. Burns, and W. C. Steen. 1980. Use of Linear Free
Energy Relationships and an Evaluative Model to Assess the Fate and
Transport of Phthalate Esters in the Aquatic Environment. Chemosphere
9:393-402.
Wolfe, N. Lee, R. G. Zepp, and D. F. Paris. 1978. Use of Structure-Re-
activity Relationships to Estimate Hydrolytic Persistence of Carbamate
Pesticides. Water Res. 12:561-563.
Zepp, R. G. 1979. Quantum Yields for Reaction of Pollutants in Dilute
Aqueous Solution. Environ. Sci. Technol. 12(3):327-329.
Zepp, R. G., and D. M. Cline. 1977. Rate of Direct Photolysis in Aquatic
Environment. Environ. Sci. Technol. 11(4):359-366.
Zepp, R. G., G. L. Baughman, and P. F. Schlotzhauer. 1980. Photosentization
of Pesticide Reactions by Humic Substances. Abstract, 180th Meeting of
American Chemical Society, San Francisco, August 25-29. PEST 6.
Zepp, R. G., N. L. Wolfe, G. L. Baughman, and R. C. Hollis. 1977. Singlet
Oxygen in Natural Water. Nature 267:421-423.
37
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SECTION 3
PROCESS DATA FOR TRANSFORMATION AND TRANSPORT OF
CHEMICALS IN AQUEOUS SOLUTION
3.1 ORGANIZATION OF DATA SHEETS AND SOURCES OF DATA
Process data for organic priority pollutant chemicals are given
for the following properties or processes:
• Physical properties and transport processes
Molecular weight
Melting point
Boiling point
lonization constant
Partition constants
Volatilization constants
• Transformation processes
Photolysis data
Oxidation rate constants
Hydrolysis rate constants
Biotransformation rate constant.
For each property or process, the property, rate constant, or parti-
tioning constant is defined in Sections 2.3.2 through 2.3.10. These
sections also give the units of the values reported and discuss the sig-
nificance and use of each value in terms of the particular process and
how it is used in calculating rate or equilibrium constants for environ-
mental assessments. The sources of the individual process data are also
discussed in these sections. The units for each value are also listed on
the data sheets for the individual chemicals.
The data in this report were estimated for the use of EPA-OWRS in
modeling the aquatic fate of the organic priority pollutants. For most
chemicals in this report, the process data are useful for a general,
38
-------
nonsite-specif±c evaluation of the persistence of the chemical. In model-
ing such situations, any uncertainties in the data are likely to be equalled
or surpassed by the unknowns or variabilities in the environmental para-
meters. The process data also are generally useful for identifying processes
that will be most important under general or specific aquatic conditions.
When such processes are identified, the user of the data should review the
sources and reliability of the data to determine what limitations, un-
certainties, or weaknesses exist and therefore whether the data need improve-
ment in the context of a particular use. This report represents information
available as of mid-1980; the user is encouraged to seek more recent data
to augment this information.
Data for the processes that occur in aquatic environments have been
obtained by several methods. Some methods for calculating data based on
structure reactivity relationships or empirical correlations were developed
for use in environmental assessments. Other methods were developed in other
basic and applied research activities in physical and life sciences. Data
presented in this report were obtained by three methods; review of the
literature, calculation, and estimation, as discussed below.
Environmental literature and other chemical and biological literature
were the sources of most data. In many cases data were taken directly
from the 1979 EPA report "Water-Related Environmental Fate of 129 Priority
Pollutants" by Callahan et al. For some chemicals, the original paper
cited in the Callahan report was critically reviewed to determine the
source or reliability of the data. Other data were obtained from recent
literature, from colleagues in the environmental research field, or from
research under way at SRI.
Other data in this report were obtained from calculations based on
empirical correlations or on structure reactivity relationships. The
rate constants for oxidation of chemicals by singlet oxygen and alkyl-
peroxyl radical were calculated using structure reactivity relationships
developed, in part, at SRI (see Section 2.3.9; Mill, 1979). Most of
the partitioning data (K , K , S , and K, ) were obtained using the K
r ow oc w b ow
calculations and correlation equations described in Section 4. Data for
volatilization rate constant calculations were calculated using the theory
39
-------
and methods described in Section 5.
When reliable data suitable for use in aquatic fate assessments were
not available, the data were estimated. Estimated data should be clearly
differentiated from calculated data in that the latter has a defined
mathematical basis, whereas estimations, although based on the expertise
and judgment of a person experienced in research on a particular process,
have not been documented by experimental work. Estimated data are preceded
by the notation (E) on the data sheets. These data should be used only
to establish what processes may be important for a chemical in an aquatic
environment. If process data preceded by (E) are found to be important,
the value should be measured in laboratory studies or calculated using
structure reactivity correlations, if available. If process data preceded
by (E) are found to be unimportant, the value may be calculated or measured
if a more reliable and complete data base is desired.
For some processes or properties, conflicting data required that SRI
staff choose a "best" value for inclusion in this report. The choice of
the value was made based on the experience and judgment of the SRI staff
member. Whenever available, the reliability of the data is given as a standard
deviation; when no statistics were available, the value is given to the
appropriate number of significant figures as judged appropriate by the
author responsible for the evaluation.
The basis for the choice of any datum has not been detailed in this
report since such efforts would require extensive discussion. Users of
the data are, of course, encouraged to compare these data with other
values in current literature to determine the reliability of the data or
the range of values that have been reported. The persons responsible for
evaluations of the several kinds of process data are as follows:
Partitioning constants: T. Podoll, J. Gates, and J\ Jaber
Volatilization constants: J. Smith, D. Haynes , and H. Jaber
Photolysis data: W. Mabey
Oxidation rate constants: T. Mill
Hydrolysis rate constants: W. Mabey
Biotransformation rate constants: T.-W. Chou
40
-------
In the preparation of the data sheets, an effort has been made to
enter information for each process on every chemical. The value and data
source spaces have been left blank only when nothing is known about the
process/property for a particular chemical. In these cases, data should
be obtained from laboratory studies because sufficient information is not
available for any theoretical or empirical estimates.
When no specific data are available, but evidence clearly shows that
no reaction can occur in aquatic environments, this information has been
indicated (i.e., no hydrolyzable functional groups and therefore no hydrolysis
will occur).
The sources of data on the following data sheets are described in one
of three ways:
(1) References are given by authors and year of referenced
paper. Citation of a reference means that this publication was
critically reviewed and that data were taken directly from the
reference. References are given at the end of the section.
(2) A code is given in many cases to describe the basis
for calculating or estimating the data. Thus CC-Kow entered as
a source for K values indicates that the octanol-water partition
ow — —
coefficient, K , was Computer Calculated using the computer
program described in Section 4. Similarly, C-Koc f Kbw signifies
that K „ was calculated from Kn.r value using a K -K correlation
—-OC — — —-*JW ° OC OW
equatimr (see Section 4). An aTphabetical list of the codes is
given on the following pages. Where possible, each code
r'efers to a section where the particular source is discussed
more completely.
Data from the CRC Handbook or from the two-volume report
"Water-Related Environmental Fate of 129 Priority Pollutants"
by Callahan et al. (1979) have also been listed in code
(CRC and WREF, respectively). Data cited by WREF were taken
directly from the EPA report; the original paper was not re-
viewed.
(3) A footnote is used to describe a source of data that
is not common enough to justify a code. The footnotes are
noted in brackets and listed at the bottom of the second page
of the data sheets.
As a convenience to the user, the chemicals are listed by formula
and data sheet number following the List of Source Codes.
41
-------
LIST OF SOURCE CODES
CC-Kow
Value of K was obtained by computer calculation,
ow
using FRAGMENT calculation procedure (See Section 4.3)
CC-SOLAR
Direct photolysis rate constant was calculated using
the SOLAR computer program (Zepp and Cline, 1977).
C-CT/CRC
Vapor pressure value was calculated from data in
critical tables. Weast, R. C., ed., 1973. Handbook
of Chemistry and Physics, 54th ed. CRC Press,
Cleveland, Ohio. D-162.
C-DC.7
Reaeration rate ratio was calculated from D./D to
0.7 power (See Section 5.)
C-kB
Base catalyzed rate constant kB was calculated from
is.
information in Callahan et al. (1979).
C-KBASE
Acid-catalyzed rate constant was calculated fifom > ;
assumption is made that acid and base catalyzed
hydrolysis rate constants are equal at pH 5.0 (Mabey
and Mill, 1978). As a result,
10~S k. = 10~9 kn
A B
or
kA-10~*kB
The value of k. is probably good within a factor of 10.
C-KB f Kow
The value of K_ was calculated from the K -K correlation
B B ow
of Baughman and Paris (1981) discussied in Section 4.2.3.
log K = 0.907 log K - 0.21
D OW
42
-------
C-Koc f Kow The value of K was calculated from the K value
oc ow
using the equation K = 0.48K . Subsequent to the
oc ow
writing of Section 4, where several K -K correlations
oc ow
are discussed, Hassettet al. (1980) have reported the
following correlation equation for sorption of poly-
nuclear aromatic chemicals onto whole sediments (i.e.,
unfractionated sediments):
log K = log K - 0.317
oc ow
Another similar correlation equation for sorption of
some 40 chemicals to whole sediments has been found by
Karickhoff (1980):
log K = 0.987 log K - 0.336
& oc & ow
The equation used to calculate K values in this
M oc
report is the nonlogarithmic form of the equation of
Hasset et al. (1980) (see Section 4).
C-OX Oxidation rate constants are calculated, using functional
group reactivity toward peroxyl radical (R02) and singlet
oxygen (102) (see Section 2.3.8).
CRC Weast, R.D., ed., 1975. Handbook of Chemistry and
Physics, 56th ed. CRC Press, Cleveland, Ohio.
C-Sw f Kow The value of S was calculated from the K value using
w ow
the equation of Yalkowsky and Valvani (1980); the cal-
culation of S values is discussed in Section 4.2.3.
w
C-VP—°/S—° Henry's constant, H , was calculated from vapor pressure
and water solubilities at the temperatures given (°C),
respectively. When the temperatures were the same,
only one temperature is given (see Section 2.3.6).
DATA-ATT UV-visible absorption coefficients are listed in
footnotes (data attached).
43
-------
E-AC-H
Rate constant was estimated by analogy to chloroform.
Mabey and Mill (1978) have calculated that the rate of
the base catalyzed process for chloroform is equal to
the neutral hydrolysis process at pH 6, or k [OH] =
when [OH~] = 10
8
If the assumption is made that the same expression holds
for all trihalomethanes , then k^ = 10 k .
E-APAH
This estimated value is the average of reaction quantum
yields for several polycyclic aromatic hydrocarbons
measured by Zepp and Schlotzhauer (1980).
E-KB
Estimate of biotransformation rate constant, k, is based
on relative rates of transformation reported in literature
or on structure—reactivity analogies as judged by reviewer.
E-H
Estimate of hydrolysis rate constant is based on analogy
to reactivity of other similar chemicals and judgment
of reviewer.
E-P
HF-NBD
This estimate .of photolysis rate constant for environ-
mental significance of photolysis is based on analogy
to reactivity of other chemicals and judgment of reviewer,
Hydrolysis is too fast for biotransformation studies
to be conducted. No biotransformation data are there-
fore available.
HNES
Hydrolysis is not environmentally significant. Chemical
hydrolysis occurs only at extreme pHs or temperatures
or with catalysts not avilable in aquatic environments.
HPHI
Hydrolysis is pH-independent; this assignment is based
on finding of Mabey and Mill (1978) that alkyl halides
are, in general, hydrolyzed by the neutral hydrolysis
process in the pH region from pH 3 to approximately 10,
and without any evidence of base or acid catalyzed
mechanisms.
NACM
No acid catalyzed mechanism.
.44
-------
NAV
Reaeration rate ratio is not applicable for calculating
the rate constant for volatilization (see 2.3.6).
NHFG
pK-NER
PNER
No hydrolyzable functional groups in molecule.
pK or pK^ is not environmentally relevant for fate of
chemical.
Photolysis is not environmentally relevant.
PNES
Photolysis is not environmentally significant.
SPEC-ATI
UV-visible absorption spectrum is shown in footnotes
(spectrum attached).
UV-ATLAS
UV-visible spectrum is found in UV Atlas (Perkampus,
et al., 1966).
VF-NBD
Volatilization is too fast for biotransformation studies
to be conducted, and no biological data are available.
WREF
Water-related environmental fate of 129 priority
pollutants by Callahan et al. (1979). U.S. Environmental
Protection Agency, Office of Water Planning and Standards.
EPA-440/4-79-029.
45
-------
FORMULA INDEX TO DATA SHEET
DATA SHEET
FORMULA NUMBER CHEMICAL NAME
HCl. 32 Tetrachloromethane
1 4
C Cl F 53 Dichlorodifluoromethane
C Cl F 54 Trichlorofluoromethane
C-H ^r Cl 50 Bromodichloromethane
C1H1Br_Cl1 51 Dibromochloromethane
C.-H.-Br 52 Tribromomethane
C H Cl 31 Trichloromethane
C H Cl 30 Dichloromethane
C-H -Br.. 49 Bromomethane
C H Cl 29 Chlorome thane
C^Cl. 44 Tetrachloroethene
2 4
C0C1- 39 Hexachloroethane
2 b
C H Cl 43 Trichloroethene
C0H Cl 42 1,2-trans-Dichloroethene
2. 2. 2.
C2H2C12 41 1,1-Dichloroethene
C2H2C14 38 1,1,2,2-Tetrachloroethane
C H Cl 40 Chloroethene
36 1,1,1-Trichloroethane
37 1,1,2-Trichloroeth
34 1,1-Dlchloroethane
C H Cl 37 1,1,2-Trichloroethane
C H C12 35 1,2-Dichloroethane
C^R C12Q^ 55 Bis (2-chloromethyl) ether
C2H5C11 33 Chloroethane
C2H6N201 107 Dimethylnitrosamine
C3H3N1 113 Acrylonitrile
C H^C12 46 1,3-Dichloropropene
C H.O.!^ 1 Acrolein
C3H6C12 45 1,2-Dichloropropane
C.Clg 47 Hexachlorobutadiene
C4H7C1101 58 2-Chloroethyl vinyl ether
CHCl 56 Bis (2-chloroethyl) ether
46
-------
FORMULA NUMBER CHEMICAL NAME
C^Clg 48 Hexachlorocyclopentadiene
C5H10<^"'~202 ^ Bis(2-chloroethoxy)methane
CgClg 68 Hexachlorobenzene
CgH^Cl^O^ 78 Pentachlorophenol
CgH^Cl^ 67 1,2,4-Trichlorobenzene
C6H3C13°1 77 2,4,6-Trichlorophenol
CgH,Cl2 64 1,2-Dichlorobenzene
C6H4C1"2 65 1,3-Dichlorobenzene
CgH,Cl2 66 1,4-Dichlorobenzene
C6H4C12°1 76 2,4-Dichlorophenol
C6H4N205 81 2,4-Dinitrophenol
C,HCC1.. 63 Chlorobenzene
65 1
C,HcClnO- 75 2-Chlorophenol
o _> -LI
C6H5N102 70 Nitrobenzene
C HL^O 79 2-Nitrophenol
C,HCN10. 80 4-Nitrophenol
D _) 1 J
C,H, 62 Benzene
D D
C,H,Cl, 14 a-Hexachlorocyclohexane
ob o
C,H.,Cl, 15 g-Hexachlorocyclohexane
DO D
C,H,Cl, 16 6-Hexachlorocyclohexane
DO o
C,H,C1, 17 Lindane
o o o
C,H,.01 74 Phenol
o o 1
C,H.0C1_01 57 Bis(2-chloroisopropyl)ether
O L2. / 1
C-HT.NTO, 109 Di-n-propylnitrosamine
o 14 ^ 1
C-,H,N00. 72 2,4-Dinitrotoluene
/ O / 4
C^H,N00. 73 2,6-Dinitrotoluene
70/4
C^H.,0,. 84 4,6-Dinitro-o-cresol
7 o 5
C?H Cl-O 83 _p_~chloro~H~creso1
C^H0 71 Toluene
7 o
C_Hn n 69 Ethylbenzene
o 1U
C.H nO^ 82 2,4-Dimethylphenol
8 10 1
CnH,Cl,00S1 8 a,0-Endosulfan
9 o o J 1
C^H^Cl^O.S, 9 Endosulfan sulfate
96 641
C..H . O, 18 Isophorone
9 14 1
CHC1 12 Heptachlor
47
-------
FORMULA NUMBER CHEMICAL NAME
C H Cl 0 13 Heptachlor epoxide
C10H,C10 3 Chlordane
1U b o
C QH Cl 28 2-Chloronaphthalene
C, nHQ 104 Naphthalene
_LU o
C10H10C18 2° Toxaphene
CIQH 0 85 Dimethyl phthalate
C12H4C1402 19 TCDD
Cn 0H0 92 Acenaphthylene
I/ o
C10HQC1, 2 Aldrin
I/ O O
CnoHQCl,01 7 Dieldrin
12 O D 1
C10HQC1,01 10 Endrin
Li. O D 1
C10H.C1,0- 11 Endrin aldehyde
1Z O D 1
C19H Cl 21-27 PCBs; x + y = 10 and 2 < y < 10
12 x y ' J - J -
C1-HgBr 0 60 4-Bromophenyl phenyl ether
C12H Cl 0 59 4-Chlorophenyl phenyl ether
C 2H 91 Acenaphthene
C H Cl N 111 3,3'-Dichlorobenzidine
C 2H 0N20 108 Diphenylnitrosamine
GI?H1?N? 112 1,2-Diphenylhydrazine
C12H12N2 110 Benzidine
C12H14°4 86 Diethyl phthalate
C13H1Q 102 Fluorene
C14H8C14 5 DDE
C14H9C15 6 DDT
C14H10 105 Phenanthrene
C-4H-_ 93 Anthracene
C14H10C14 4 DDD
C16H1Q 101 Fluroanthene
C16H1Q 106 Pyrene
C16H22°4 87 Di-n-butyl phthalate
C18H12 99 Chrysene
C-nH, 94 Benzo[a]anthracene
48
-------
FORMULA NUMBER CHEMICAL NAME
C19H20°4 90 Butyl benzyl phthalate
^20^12 9^ Benzo[b]fluoranthene
^20^12 9^ Benzo[k]fluoranthene
^20^12 98 Benzo[a]pyrene
^22^12 ^ Benzo[ghi]perylene
C22E12 103 Indeno[l,2,3-cd]pyrene
^22^14 ^®® Benzo[a,h]anthracene
C24H38°4 89 Bis(2-ethylhexyl)phthalate
C24H38°4 88 Di-n-octyl phthalate
49
-------
References for 3.1
Baughman, G. L. , and D. F. Paris. 1981. Microbial Bioconcentration of
Organic Pollutants for Aquatic Systems - A Critical Review. Critical
Reviews in Microbiology. January.
Callahan, M. A., M. W. Slimak, N. W. Gabel, I. P. May, C. F. Fowler,
J. R. Free, P. Jennings, R. L. Durfee, F. C. Whitmore, B. Maestri,
W. R. Mabey. B. R. Holt and C. Gould, 1979. Water-Related Environ-
mental Fate of 129 Priority Pollutants. U.S. EPA, Washington B.C.
Vol. I, EPA~440/4-79-029a; Vol. II, EPA-440/4-79-029b.
CRC Handbook. 1973. Handbook of Chemistry and Physics, 54th edition.
R. C. Weast, editor. CRC Press, Cleveland, OH.
Hassett, J. J., J. C. Means, W. L. Banwart, and S. G. Wood. 1980. Sorp-
tion Properties of Sediments and Energy Related Pollutants. U.S. EPA,
Washington D.C. EPA-600/3-80-041, April.
Karickhoff, S. 1980. Private communication.
Mabey, W. R., and T. Mill. 1978. Critical Review of Hydrolysis of Or-
ganic Compounds in Water Under Environmental Conditions. J. Phys.
Chem. Ref. Data 7:383-415.
UV Atlas. 1971. UV Atlas of Organic Compounds. Vol. I-V. Plenum Press,
New York.
Yalkowsky, S. H., and S. C. Valvani. 1980. Solubility and Partitioning.
I: Solubility of Nonelectrolytes in Water. J. Pharm. Sci. 69(8):
912-922.
Zepp, R. G., and D. M. Cline. 1977- Rate of Direct Photolysis in Aquatic
Environment. Environ. Sci. Technol. 11(4):359-366.
Zepp, R. G., G. L. Baughman, and P. F. Schlotzhauer. 1980. Photosenti-
zation of Pesticide Reactions by Humic Substances. Abstract, 180th
Meeting of American Chemical Society, San Francisco, August 25-29.
PEST 6.
50
-------
SECTION 3.2. PESTICIDES
1. Acrolein
2. Aldrin
3. Chlordane (cis and trans isomers)
4. ODD
5. DDE
6. DDT
7. Dieldrin
8. Endosulfan (a and 6 isomers)
9. Endosulfan sulfate
10. Endrin
11. Endrin aldehyde
12. Heptachlor
13. Heptachlor epoxide
14. a-Hexachlorocyclohexane
15. 3-Hexachlorocyclohexane
16. 6-Hexachlorocyclohexane
17. Y-Hexachlorocyclohexane (lindane)
18. Isophorone
19. TCDD
20. Toxaphene
51
-------
CHC
1. ACROLEIN
CAS No. 107-02-8
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
56.06
-87.7
52.5
pK-NER
Data Source
WREF
WREF
Partition constants: [1-1]
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.1 x 10 (20°C)
1.02
0.49
0.44
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants: [1-1]
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
5.66 x 10
-5
220 (20°C)
NAV
C-VP/S-20C
WREF
53
-------
1. ACROLEIN
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
SPEC-ATT [1-2]
Direct photolysis rate
constant, k (hr )
P
at latitude [1-2]
Oxidation constants at 25°C: [1-1]
For 1C>2 (singlet oxygen),
ox
For R02 (peroxy radical) ,
kox (M"1 hr"1}
Hydrolysis rate constants:
For base-promoted process,
1 -1
1 x 10'
3.4 x
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1) (E) 3 x 10
-9
Data Source
UV-ATLAS
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[1-1] The values of KOW, K^, K^, kc/k°, P and oxidation rate constants
are calculated or given for tKe unhycfrated acrolein species;
hydration of acrolein may be extensive in aquatic environments,
and the above properties will therefore be different than listed.
54
-------
1. ACROLEIN
[1-2] UV spectrum of acrolein in hexane solvent is shown below
(UV Atlas, 1966). Acrolein undergoes rapid hydration
(tjj < 1 day) to 3-hydroxypropionaldehyde. This hydration
destroys the chromophores that absorb light above 290 nm
and therefore the UV-spectrum of acrolein in water may be
insignificant above 290 nm (WREF).
X (nm)
55
-------
Cl
2. ALDRIN
CAS No. 309002
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
365
104-105
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(Ug/g)(mg/£)-1\
0.180 (25°C) F2-11
2.0 x 105
9.6 x 104
2.8 x 10
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm
1
mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.6 x 10
-5
6 x 10 6 (25°C)
NAV
C-VP/S-25'
WREF
57
-------
2. ALDRIN
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25 °C:
For 102 (singlet oxygen) ,
kox (M-l hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB (M"1 hr"1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
k, (hr"1)
Biotransf ormation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
PNES
PNER
latitude PNER
<36QQ
5 x 10"
(E) 3 x 10
-9
E-P
C-OX
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[2-1] Several water solubility values, ranging from 0.017-0.18 ppm,
have been reported (WREF.)
58
-------
Cl
Cl
3. CHLORDANE
CAS No. [3-1]
trans isomer [3-2]
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
409.8
[3-3]
175 (2mm)
pK-NER
Data Source
WREF
WREF [3-41
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/g)(mg/£)-1\
0.056 (25°C) [3-5] WREF
3 x 105 CC-Kow
1.4 x 10'
4.0 x 10
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
9.4 x 10
-5
x 10~5 (25°C)
NAV
C-VP/S-25'
WREF
59
-------
3. CHLORDANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, 4>,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr"1)
For acid-promoted process,
kA (NT1 hr-1)
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
latitude PNER
<3600
^30
(E)3 x 10
-12
E-P
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[3-1] Chemical Abstracts numbers are 5103-71-9 for trans isomer,
5103-74-2 for cis isomer.
60
-------
3. CHLORDANE
[3-2]
Cl
cis isomer
[3-3]' Melting point 103.0 - 105.0 for trans isomer and 107.0 - 10S.8 for
cis isomer.
[3-4] Boiling point reported for a mixture of the isomers.
[3-5] Two solubility values, 0.056 ppm and 1.85 ppm were given
in WREF. Solubility data are for a mixture of the isomers.
61
-------
CHCI,
4.
DDD
CAS No. 72548
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
320
112
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
[4-1]
1.6 x 10
7.7 x 10'
1.8 x 10"
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.2 x 10
-8
[4-2]
NAV
C-VP30°/S25C
WREF
63
-------
4. ODD
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox (>rl hr"1}
For R02 (peroxy radical) ,
V (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
k (M-1 hr~!)
ji
For acid-promoted process,
k
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr-1)
<5 x 10
-7
<3600
<1600
5.0 (27°C)
4 x 10 7 (27°C)
(E)1 x 1Q~10
[4-3]
C-OX
C-OX
WREF [4-4]
HNES
WREF [4-51
E-KB
E: Estimated value; see List of Source Codes.
[4-1] Two water solubility values have been reported for the pp'
isomer at 25°C: 0.02 ppm and 0.09 ppm. A value of 0.10 ppm
has been reported for the op' isomer (WREF).
[4-2] Vapor pressures at 30°C have been reported as 10.2 x 10~7
torr for the pp' isomer and 18.9 x 10"7 torr for the op' isomer.
64
-------
4. DDD
[4-3] Several papers report that the direct photolysis of DDD is
slower than that of DDT (WREF). Since the half-life of DDT
is greater than 150 years, the photolysis rate constant of DDD
should be much slower than 5 x 10~7 hr"1.
[4-4] The hydrolysis half-life of DDD has been calculated using
structure-reactivity relationships and literature data (WREF).
The base promoted hydrolysis at 27°C was calculated to be
5.0 M-1 hr~!.
[4-5] A half-life has been reported (WREF) of 190 years for DDD at
pH 5 and 27°C. This corresponds to a rate constant of
4.2 x 10~7 hr"1, which is assumed to be due to the neutral
rate process, k .
65
-------
DDE
CAS No. 72559
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
318
82
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.04 (20°C)
9.1 x 106
4.4 x 106
8.9 x 10"
WREF [5-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
6.8 x 10
,-5
[5-2]
NAV
C-VP/S-20C
WREF
67
-------
5. DDE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 313 _ nm
Direct photolysis rate
constant, k (hr )
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox (M~! hr~1}
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k CM"1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
0.3
<3600
1.2 x 1(T
<6.6 x 10 (27°C)
(E) 3 x 10
-12
WREF
C-OX
C-OX
HNES
HNES
[5-3]
E-KB
E: Estimated value; see List of Source Codes.
[5-1] Several water solubility values have been reported for the
pp' isomer at various temperatures (WREF). Water solubilities
have been reported ranging from 0.014 ppm to 0.12 for the
pp' isomer and 0.140 ppm for the op' isomer (WREF).
[5-2] Vapor pressures reported are 6.5 x 10"6 torr for pp' isomer and
6.2 x 10~5 torr for op' isomer at 20°C (WREF).
68
-------
5. DDE
[5-3] A hydrolysis half-life for DDE of more than 120 years at
pH 7 and 25°C has been reported (WREF). This corresponds to
a rate constant of 6.6 x 10~7 hr"1; it is assumed that at
this pH only the neutral process is occurring.
69
-------
6. DDT
CCI
CAS No. [6-1]
pp1 isomer [6-2]
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
354.5
108.5-109.0 [6-3]
185
pK-NER
Data Source
WREF
WREF [6-A]
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
5.5 x 10 3 (25°C) WREF [6-5]
8.1 x 10
3.9 x 10
8.0 x 10
CC-Kow [ 6-61
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
3 1C
(atm m^ mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.58 x 10
-5
1.9 x 10 7 (25°C)
NAV
C-VP/S-250 [6-7]
WREF
71
-------
6. DDT
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25°C:
For C>2 (singlet oxygen) ,
kox (M-1 hr~1}
For R02 (peroxy radical) ,
kox (M-1 hr~!)
Hydrolysis rate constants:
For base-promoted process,
k (M-l hr'1)
D
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell""1 hr-1)
PNES
PNER
<5 x 10
-7
<3600
3600
36 (27°C)
6.8 x 10 6 (27°C)
(E)3 x 10
-12
WREF [6-8]
C-OX
C-OX
WREF [6-9]
HNES
WREF [6-10]
E-KB
E: Estimated value; see List of Source Codes.
[6-1] Chemical Abstracts numbers are 502-93 for pp' isomer and
789-02-6 for op' isomer. Constants are calculated for the
pp1 isomer only.
72
-------
6. DDT
[6-2]
[6-10]
CCI
op' isomer
[6-3] The melting point given above is for the pp' isomer; the
melting point of the op' isomer is 74-74.5°C.
[6-4] No boiling point is reported for the op' isomer (WREF).
[6-5] Several values for the water solubility of both isomers
have been reported: a range of 1.2 x 10"3 - 2.5 x 10~2 ppm
for the pp' isomer and 2.6 x 10~2 and 8.5 x 10~2 ppm for the
op' isomer. See WREF for all values reported. The water
solubility has also been calculated using the octanol-water
partition coefficient to be 9.2 x 10" 3 ppm.
[6-6] See WREF for other calculated and measured Kow values.
[6-7] Calculation of Henry's Law constant was based on data from
the pp' isomer at 25°C, i.e., solubility - 5.5 x 10~3 pp' and
vapor pressure - 1.9 x 10 7
PP1
[6-8] A photolysis half-life of greater than 150 years has been
reported for DDT (WREF). This corresponds to a rate constant
of 5 x 10~7 hr"1.
[6-9] The base-promoted hydrolysis rate constant for DDT has been
measured (WREF) to be k = 9.9 x 10" d M"1 sec"1, which
corresponds to a base-catalyzed process of 36 M"1 hr"1.
A hydrolysis rate constant of 6.8 x 10~6 hr"1 has been
reported for DDT at pH 3-5 and 27°C (WREF). It is assumed
that at these pHs, only a neutral process is occurring.
73
-------
Cl
7.
DIELDRIN
CAS No. 60-57-1
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
381
175-176
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
•„
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.195 (25°C)
3.5 x 103
1.7 x 103
710
WREF [7-11
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm m mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
4.57 x 10
-10
1.78 x 10 7 (20°C)
NAV
C-VP20°/S25'
WREF
75
-------
DIELDRIN
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, 4>,
at nm
Direct photolysis rate
constant, k (hr )
P
at 40° latitude
Oxidation constants at 25°C:
For 02 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k (M-1 hr-1)
A.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, lo (ml cell-1 hr"1)
Value
4.8 x 10
-4
<3600
30
(E) 3 x 10
-12
Data Source
T7-21
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[7-1] Several values, ranging from 0.186 ppm to 0.200 ppm, have
been reported for the water solubility.
[7-2] The half-life for direct photolysis of dieldrin has been
reported to be 2.1 to 1.8 months in sunlight (WREF). If
the average half-life is used, a rate constant of 4.8 x
10-4 hr-1 is obtained.
76
-------
8. a-ENDOSULFAN
CAS No. 115-29-7
Cl Cl
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
406.9
108-110
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.530 (25°C)
0.02
9.6 x 10
-3
0.012
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
q _ 1 Q
(atm m mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.0 x 10
-5
1 x 10 5 (25°C)
NAV
C-VP/S-25'
WREF
77
-------
a-ENDOSULFAN
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, $ ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25° C:
For 10£ (singlet oxygen) ,
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
1 -1
For acid-promoted process,
k
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
Value
<3600
>3.6 x 10
8.3 x 10 (20°C)
1.6 x 10 4 (20°C)
(E) 3 x 10
-9
E: Estimated value; see List of Source Codes.
Data Source
C-OX
C-OX
[8-1]
[8-2]
E-KB
[8-1] The hydrolysis rate constants for a-endosulfan have been
measured at two pHs (WREF): pH 7 is 2.0 x 10~2 days-1
and pH 5.5 is 4.6 x 10"3 days"1. Based on the assumption
that only the base promoted process is responsible for
hydrolysis at pH 7, k = k-[OH] or 2.0 x 10~2 days"1 =
kB[10~7]; kB then equals 2.0 x 105 days'1, or 8.3 x 10+3 hr-1.
78
-------
8. ct-ENDOSULFAN
[8-2] The neutral rate constant for a-endosulfan can be calculated
using the base-promoted rate constant and the overall rate
constant at pH 5.5, It = k [OH] + k or k = k^ - kgfOH].
The assumption is that at pH 5.5 there is no acid-promoted
contribution to the overall hydrolysis rate process.
79
-------
3- ENDOSULFAN
CAS No. 115-29-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
406.9
207-209
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/g)(mg/£)-1\
0.280 (25°C)
0.02
9.6 x 10
_0
0.012
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.91 x 10
-5
1 x 10 5 (25°C)
NAV
C-VP/S-25'
WREF
81
-------
8. g-ENDOSULFAN
TRANSFORMATION DATA
Property or Process Value Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
For acid-promoted process,
k (M-1 hr-1)
kQX (l^T hr-) <3600 _ C-OX
For R02 (peroxy radical),
k (M-1 hr'1) >3.6 x 1Q4 C-OX
Hydrolysis rate constants:
For base-promoted process, ~
k_ (M-* hr-1) 8.3 x 10 (20°C) [8-3]
D
For neutral process,
k (hr-1) 1.3 x 10~4 (200C) [8-4]
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell-1 hr"1) (E) 3 x 10E-KB
E: Estimated value; see List of Source Codes.
[8-3] See [8-1] for a discussion on calculation of k . The rate
constants at pH 7 and pH 5.5 are 1.9 x 10~2 days and
3.7 x 10"3 days, respectively.
[8-4] See [8-2] for calculation of k from k and pH 5.5 hydrolysis
rate constant.
82
-------
Cl
9. ENDOSULFAN SULFATE
Cl
CAS No. 1031-07-8
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
422.9
198-201
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w (ppm)
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(ug/g)(mg/£)-1\
0.22 [9-1]
0.05
0.024
0.029
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
3 1 C
(atm nr mol x)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.6 x 10
-5
1 x 10 5 (25°C)
NAV
C-VP/S-250 [9-2]
19-2]
83
-------
9. ENDOSULFAN SULFATE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 02 (singlet oxygen) ,
For
Hydrolysis rate constants:
For base-promoted process,
hr'1)
(peroxy radical) ,
hr-1)
For acid-promoted process,
k (M"1 hr~:)
f\
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, 1<_ (ml cell""1 hr"1)
<3600
20
5.3 x 10 (20°C)
1.3 x 10 (20°C)
(E) 1 x 10
-10
C-OX
C-OX
[9-3]
[9-4]
E-KB
E: Estimated value; see List of Source Codes.
[9-1] No temperature was reported with the water solubility.
[9-2] Vapor pressure value was assigned by analogy to endosulfan.
Henry's constant was calculated using vapor pressure value for
endosulfan.
84
-------
9. ENDOSULFAN SULFATE
[9-3] See [8-1]. The assumption is made that rate constants for
3-endosulfan are the same for endosulfan sulfate.
[9-4] See [8-2] for the calculation of
V
85
-------
Cl ci
.—ci
Cl
10. ENDRIN
CAS No. 72-20-8
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
381
235
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w (ppm)
(unitless)
Sediment-water. K (unitless)
oc
Microorganisms-water,
KB /(yg/g)(mg/£)-1\
0.25 (25°C)
3.5 x 103
1.7 x 103
710
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
4.0 x 10
-7
2 x 10 7 (25°C)
NAV
C-VP/S-25'
WREF
87
-------
10. ENDRIN
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield,
-------
11. ENDRIN ALDEHYDE
CAS No. 7421-93-4
Cl
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
381
145-149
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
50 (25°C)
1.4 x 10"
670
310
C-Sw f Kow
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration .rate ratio,
kc/k°
v v
2 x 10
-9
2.0 x 10 7 (25°C)
C-VP/S-250 [11-1]
[11-1]
NAV
89
-------
11. ENDRIN ALDEHYDE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, (J> ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (trl hr"1}
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr"1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
<3600
3100
(E) 3 X 10
-9
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[11-1] Vapor pressure was assigned by analogy to endrin; this is the
value used in the calculation of Henry's constant.
90
-------
12.
HEPTACHLOR
CAS No. 76-44-8
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
373.5
95-96
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
0.18 (25°C) [12-1]
2.6 x 104
1.2 x 104
4.4 x 10'
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4.0 x 10
-3
3.0 x 10 4 (25°C)
0.355
C-VP/S-25C
WREF
C-DC.7
91
-------
12. HEPTACHLOR
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1(>2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
kox (trl hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (IT1 hr'1)
For acid-promoted process,
k (M"1 hr~!)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr-1)
3 x 10
10
2500
3.00 x 10 2 (30°C)
C-OX
C-OX
[12-2]
[12-2]
WREF
HF-NBD
E: Estimated value; see List of Source Codes.
[12-1] Another solubility value has been reported as 0.056 ppm at
25-29°C (WREF).
[12-2] Hydrolysis rate is likely to be pH independent by analogy to allyl
chloride (Mabey and Mill, 1978).
92
-------
Cl Cl
13. HEPTACHLOR EPOXIDE
Cl
CAS No. 1024-57-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
389.2
157-160
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.350 (25°C)
450
2.2 x 102
1.1 x 10
WREF [13-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
o 1 C
(atm m mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.9 x 10
-4
3 x 10 4 (25°C)
NAV
C-VP/S-250 [13-21
[13-2]
93
-------
13. HEPTACHLOR EPOXIDE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
at
latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
k (M"1 hr-1)
OX
For R02 (peroxy radical),
kox (M~! hr"1}
Hydrolysis rate constants:
For base-promoted process,
Promote
hr-1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
Value
<3600
20
(E)3 x 10
-12
Data Source
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[13-1] Several water solubility values, ranging from 0.20 to 0.35 ppm,
were reported (WREF).
[13-2] Vapor pressure value is assigned by analogy to heptachlor.
This vapor pressure is used in the calculation of Henry's
constant.
94
-------
14. a-HEXACHLOROCYCLOHEXANE
Orientation of
Cl atoms on ring
AAEEEE
EEEEEE
AAAEEE
AEEEEE
AEEAEE
CAS No. 319-84-6
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
291
157-158
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow '
Sediment-water, K (unitless)
Microorganisms-water
(yg/g)(mg/i)
-\\
1.63 (25°C)
7.8 x 1Q3
3.8 x 103
1.5 x 10-
WREF [14-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
6.0 x 10
-6
2.5 x 10 5 (20°C)
NAV
C-VP20°/S25'
WREF
95
-------
14. a-HEXACHLOROCYCLOHEXANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr )
at latitude
Oxidation constants at 25°C:
For 02 (singlet oxygen),
k (M"1 hr"1)
For R02 (peroxy radical),
k (M"1 hr"1)
OX
Hydrolysis rate constants:
For base-promoted process,
kB (M-l hr-1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
PNES
PNER
PNER
<3600
(E) 1 x 10
E-P
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[14-1] Several water solubility values, ranging from 1.21 ppm to
2.03 ppm,have been reported (WREF).
96
-------
15. e-HEXACHLOROCYCLOHEXANE
CAS No. 319-85-7
See a-Chlorocyclohexane for structure
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
291
309
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
' oc
Microorganisms-water,
0.24 (25°C)
7.8 x 103
3.8 x 103
1.5 x 10"
WREF [15-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q "I C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
4.5 x 10
-7
2.8 x 10 7 (20°C)
NAV
C-VP20°/S25'
WREF
97
-------
15. 3-HEXACHLOROCYCLOHEXANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <|> ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For Q£ (singlet oxygen) ,
kox (M-1 hr-1)
For ROj (peroxy radical),
kox (>rl hr"1}
Hydrolysis rate constants:
For base-promoted process,
k£ (M-1 hr"1)
For acid-promoted process,
1 -1
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
<3600
(E) 1 x 10
-10
E-P
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[15-1] Several water solubility values, ranging from 0.13 ppm to
0.70 ppm, have been reported (WREF).
98
-------
16. 6-HEXACHLOROCYCLOHEXANE
CAS No. 319-86-8
See a-Chlorocyclohexane for structure
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
291
138-139
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
31.4 (25°C)
1.4 x 104
6.6 x 103
3.5 x 10'
WREF [16-1]
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.07 x 10
-7
C-VP20°/S25'
1.7 x 10 (20°C) WREF
NAV
99
-------
16. (S-HEXACHLOROCYCLOHEXANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox (M"1 hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
Value
PNES
PNER
latitude PNER
<3600
(E) 1 x 10
-10
Data Source
E-P
C-OX
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[16-1] Several water solubility values, ranging from 8.64 ppm to
31.4 ppm, have been reported (WREF).
100
-------
Cl
17. LINDANE
CAS No. 58-89-9
•Cl
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
291
112.9
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
7.8 (25°C)
7.8 x 103
3.8 x 103
1.5 x 10-
WREF [17-1]
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
7.8 x 10
-6
1.6 x 10 (20°C)
NAV
C-VP/S-25'
WREF
101
-------
17- LINDANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kfi (M-l hr'1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr-1)
PNES
PNER
PNER
<3600
(E)l x 10
-10
E-P
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[17-1] Several solubility values, ranging from 0.04 ppm to 12 ppm,
have been reported (WREF).
102
-------
18. ISOPHORONE
CAS No. 78591
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
138.2
-8
215
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
„
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.2 x 10 [18-1]
180
_87
48
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
5.75 x 10
-6
0.38 (20°C)
NAV
C-VP20°/S-[18-1]
WREF
103
-------
18. ISOPHORONE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, <|> ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
at
latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
Value
SPEC-ATT [18-2]
x 10
225
(E)3 x 10
-9
Data Source
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[18-1] No temperature is reported for water solubility ; This
value was used in the calculation of Henry's constant.
104
-------
18. ISOPHORONE
[18-2] UV spectrum of isophorone in ethanol solvent is shown
below (UV Atlas, 1966).
A (nm)
105
-------
19. TCDD
CAS No. 1746-01-6
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
322
303-305
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/gXmg/t)-1)
2 x 10
-4
6.9 x 10
6
3.3 x 10
6
6.9 x 10'
WREF [19-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.1 x 10
-3
1 x 10
-6
0.373
C-VP/S [19-21
[19-3]
C-DC.7
107
-------
19.
TCDD
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr~l)
P
_ at __ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
k^ (M-I hr"1)
D
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
<360
<1
(E) 1 x 10
-10
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[19-1] No temperature is reported for the water solubility.
[19-2] Vapor pressure and the water solubility given above are used in the
calculation of Henry's constant.
[19-3] Vapor pressure calculated from structure using methods described
by Lyman et al. (1982). Calculation conducted by R. T. Podoll,
SRI International.
108
-------
20. TOXAPHENE
CAS No. 8001-35-2
TOXAPHENE (AVERAGE FORMULA
CHj
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
414
pK-NER
Data Source
[20-1]
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.50 (25°C)
2.00 x 103
964
429
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.21
0.2-0.4 (25°C)
0.330
C-VP/S-25'
WREF
C-DC.7
109
-------
20. TOXAPHENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <(>,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
k (M"1 hr"1)
OX
For R02 (peroxy radical),
Hydrolysis rate constants:
For base-promoted process,
-1 hr-1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
<3600
(E) 3 x 10
-12
E-P
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[20-1] Toxaphene is a chlorinated camphene mixture containing 67-69%
chlorine. Value reported here is an average molecular weight
for the mixture.
110
-------
References for 3.2
Lyman, W. J., W. F. Rechl and D. H. Rosenblatt. 1982. Handbook of
Chemical Property Estimation Methods. McGraw-Hill, New York.
Mabey, W. R., and T. Mill. 1978. Critical Review of Hydrolysis of
Organic Compounds in Water Under Environmental Conditions. J. Phys.
Chem. Ref. Data 7:383.
Pomona College Medicinal Data Base, June 1982.
UV Atlas. 1971. UV Atlas of Organic Compounds. Vol. I-V. Plenum
Press, New York.
Ill
-------
SECTION 3.3. PCBS AND 2-CHLORONAPHTHALEHE
21. Aroclor 1016
22. Aroclor 1221
23. Aroclor 1232
24. Aroclor 1242
25. Aroclor 1248
26. Aroclor 1254
27. Aroclor 1260
28. 2-Chloronaphthalene
See footnotes for Aroclor 1016 (data sheet number 21) for comments
on data for PCB mixtures that constitute Aroclors
113
-------
5' 6
21. AROCLOR 1016
CAS No.
Numbering sequence for polychlorinated
biphenyl
PHYSICAL AND TRANSPORT DATA [21-1]
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
257.9
pK-NER
Data Source
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.42 (25°C)
3.8 x 105
1.8 x 105
5.0 x 10
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
3.3 x 10
4 x 10 (25°C)
NAV
C-VP/S-25°C
WREF
115
-------
21. AROCLOR 1016
TRANSFORMATION DATA [21-2]
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
kox
-------
22. AROCLOR 1221
CAS No. 11-042-82
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
200.7
pK-NER
Data Source
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
40.0 (25°C)
1.2 x 104
5.8 x 103
2.2 x 10"
C-Sw f Row
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.7 x 10
-4
6.7 x 10 3 (25°C)
NAV
C-VP/S-25'
WREF
117
-------
22. AROCLOR 1221
TRANSFORMATION DATA (see [21-2])
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (M-l hr-1)
For R02 (peroxy radical) ,
ox
Hydrolysis rate constants:
For base-promoted process,
kR (M-1 hr"1)
ri
For acid-promoted process,
k (M~! hr-1)
A
For neutral process ,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
«360
C-OX
C-OX
HNES
HNES
HNES
(E) 3 x 10 9^3 x 10 12 E-KB
E: Estimated value; see List of Source Codes.
118
-------
23. AROCLOR 1232
CAS No. 111-411-65
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process Value Data Source
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
232.2
pK-NER
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
407 (25°C)
1.6 x 103
771
351
C-Sw f Kow
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm
T
mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.13 x 10
-5
C-VP/S-25'
4.06 x 10 (25°C) WREF
NAV
119
-------
23. AROCLOR 1232
TRANSFORMATION DATA (see [21-2])
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For ^Og (singlet oxygen) ,
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
«360
«1
C-OX
C-OX
HNES
HNES
HNES
(E) 3 x 10 9V3 x 10 12 E-KB
E: Estimated value; see List of Source Codes.
120
-------
24. AROCLOR 1242
CAS No. 534-692-19
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process Value Data Source
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
266.5
pK-NER
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
0.23 (25°C)
1.3 x 1Q4
6.3 x 103
2.3 x 10-
WREF F24-21
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
1
(atm nr mol"1)
Vapor pressure, P
(torr)
Reaeration rate ratio,
kc/k°
v v
1.98 x 10
-3
1.3 x 10 (25°C)
0.382
C-VP/S-25'
C-DC.7
121
-------
24. AROCLOR 1242
TRANSFORMATION DATA (see [21-2])
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, 4>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen) ,
kox (M"1 hr~1}
For R02 (peroxy radical) ,
kox (lrl hr~1}
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k (M-1 hr"1)
f\.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, lo (ml cell"1 hr"1)
«360
<1
C-OX
C-OX
HNES
HNES
HNES
JE) 3 x 10 9^3 x 10 12 E-KB
E: Estimated value; see List of Source Codes.
122
-------
25. AROCLOR 1248
CAS No. 126-722-96
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process Value Data Source
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
299.5
pK-NER
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.054 (25°C)
5.75 x 1Q5
2.77 x 105
7.29 x 10
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
3.6 x 10
-3
4.94 x 10 (25°C)
0.370
C-VP/S-2S0
WREF
C-DC.7
123
-------
25. AROCLOR 1248
TRANSFORMATION DATA (see [21-2])
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25° C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
ox
Hydrolysis rate constants:
For base-promoted process,
k- (W1 hr'1)
D
For acid-promoted process,
k
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
«360
«1
c-ox
c-ox
HNES
HNES
HNES
(E) 3 x 10 9V3 x 10 12 E-KB
E: Estimated value; see List of Source Codes.
124
-------
26. AROCLOR 1254
CAS No. 110-976-91
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process Value Data Source
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
328.4
pK-NER
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water
0.031 (25°C)
1.1 x 106
5.3 x 105
1.3 x 10"
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.6 x 10
-3
0.359
WREF
7.71 x 10 (25°C) WREF
C-DC.7
125
-------
26. AROCLOR 1254
TRANSFORMATION DATA (see [21-2])
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
hr-1)
For R0£ (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB Or1 hr'1)
For acid-promoted process,
kA (M"1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
Value
«360
«1
Data Source
C-OX
C-OX
HNES
HNES
HNES
(E) 3 x 10 9^3 x 10 12 E-KB
E: Estimated value; see List of Source Codes.
126
-------
27. AROCLOR 1260
CAS No. 110-968-25
PHYSICAL AND TRANSPORT DATA (see [21-1])
Property or Process Value Data Source
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
375.7
pK-NER
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/gMmg/Jl)-1)
2.7 x 10 3 (25°C)
1.4 x 107
6.7 x 106
1.3 x 10
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.74
0.346
C-VP/S-25'
4.05 x 10 5 (25°C) WREF
C-DC.7
127
-------
27. AROCLOR 1260
TRANSFORMATION DATA (see [21-1])
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, 4>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
at
latitude
Oxidation constants at 25°C:
For 02 (singlet oxygen) ,
hr'1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
«360
«1
C-OX
C-OX
HNES
HNES
HNES
(E) 3 x 10 9V3 x 10 12 E-KE
E: Estimated value; see List of Source Codes.
128
-------
28. 2-CHLORONAPHTHALENE
CAS No. 91-58-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
162.62
61
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
6.74 (25°C)
1.0 x 104
4.8 x 103
1.8 x 10"
WREF
WREF
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
0 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
5.4 x 10
-4
0.017 (20°C)
NAV
C-VP20°/S25l
WREF
129
-------
28. 2-CHLORONAPHTHALENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For C>2 (singlet oxygen) ,
ox
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr'1)
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
«360
«1
(E) 3 x 10
-9
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
130
-------
SECTION 3.4. HALOGENATED ALIPHATIC CHEMICALS
29. Chloromethane (methyl chloride)
30. Dichloromethane (methylene chloride)
31. Trichloromethane (chloroform)
32. Tetrachloromethane (carbon tetrachloride)
33. Chloroethane (ethyl chloride)
34. 1,1-Dichloroethane (ethylidine chloride)
35. 1,2-Dichloroethane (ethylene dichloride)
36. l,l,l-Trichlorod:hane (methyl chloroform)
37. 1,1,2-Trichloroethane
38.' 1,1,2,2-Tetrachloroethane
39. Hexachloroethane
40. Chloroethene'(vinyl chloride)
41. 1,1-Dichloroethane (vinylidine chloride)
42. 1,2-trans-Dichloroethene
43. Trichloroethene
44. Tetrachloroethene (perchloroethylene)
45. 1,2-Dichloropropane
46. 1,3-Dichloropropene
47. Hexachlorobutadiene
48. Hexachlorocyclopentadiene
49. Bromomethane (methyl bromide)
50. Bromodichloromethane
51. Dibromochloromethane
52. Tribromomethane (bromoform)
53. Dichlorodifluoromethane
54. Trichlorofluoromethane
131
-------
29. CHLOROMETHANE
H
CAS No. 74-87-3
a— c —H
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
50.49
-97.73
-24.2
pK-NER
Data Source
CRC
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
6.45 x 10J (20°C)
8.9
4.3
3.2
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
0.04
3.76 x IP"1 (20°C)
0.752
C-VP/S-20C
WREF
C-DC.7
133
-------
29. CHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <)>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25° C:
For 102 (singlet oxygen),
kox (M-l hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1>
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr"1)
For acid-promoted process,
k (M-l hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
«360
0.05
6.8 x 10 5 (25°C)
E-P
C-OX
C-OX
HPHI
NACM
WREF
VF-NBD
E: Estimated value; see List of Source Codes.
134
-------
30. DICHLOROMETHANE
CAS No. 75-09-2
Cl
Cl C H
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
84.94
39.75
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.0 x 10 (20°C)
18.2
8.8
6.0
WREF [30-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.03 x 10
-3
362.4 (20°C)
0.650
C-VP20°/S25'
WREF
C-DC.7
135
-------
30. DICHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr )
P
_ at _ latitude
Oxidation constants at 25° C:
For ^2 (singlet oxygen),
kox OT1 hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
1 -1
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
kN (hr-1)
Biotransf ormation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
Value
PNES
PNER
PNER
«360
0.2
1.15 x 10 ' (25°C)
Data Source
UV-ATLAS
C-OX
C-OX
HPHI
NACM
WREF
VF-NBD
E: Estimated value; see List of Source Codes.
[30-1] Several values, ranging from (1.32 - 2.00) x 10^ ppm, have been
reported (WREF).
136
-------
31. TRICHLOROMETHANE
CAS No. 67-66-3
a-
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
119.38
-63.5
61.7
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
8.2 x 10 (20°C)
44
26
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.88 x 10
-3
150.5 (20°C)
0.583
C-VP/S-20C
WREF
C-DC.7
137
-------
31. TRICHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
ox
hr"1}
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr"1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
PNES
PNER
latitude PNER
«360
0.7
0.23 (25°C)
2.5 x 10 9 (25°C)
Data Source
UV-ATLAS
c-ox
c-ox
Mabey & Mill, 1978
NACM
Mabey & Mill, 1978
VF-NBD
E: Estimated value; see List of Source Codes.
138
-------
3 2. TETRACHLOROMETHANE
CAS No. 56-23-5
a—c—a
I
a
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
153.82
-22.99
76.54
pK-NER
Data Source
CRC
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microoranisms-water,
785 (20°C)
912
439
211
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.023
90 (20°C)
0.536
C-VP/S-2Q0
WREF
C-DC.7
139
-------
32. TETRACHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25 °C:
For Q£ (singlet oxygen) ,
kox ^ hr~1}
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell'1 hr"1)
Value
PNES
PNER
latitude PNER
«360
«1
[32-1]
(E) 1 x 10
-10
Data Source
UV-ATLAS
c-ox
c-ox
HPHI
NACM
E-KB
E: Estimated value; see List of Source Codes.
[32-1] The kinetics of hydrolysis of CCl^ has been reported as
being second order in CCl^ concentration, although no
explanation for this behavior is available. At 1 ppm
concentrations, the calculated half-life is 7000 years at
pH 7 and 25°C (Mabey and Mill, 1978).
140
-------
33. CHLOROETHANE
CAS No. 75-00-3
H H
H
C - Cl
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
64.52
-136.4
12.27
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/g) (ing/A)-1)
5.74 x 10 (20°C)
30.9
14.9
9.8
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
0.148
1.0 x 10 (20°C)
0.645
C-VP/S-20C
WREF
C-DC.7
141
-------
33. CHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
ox
hr"!)
For ROj (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water,
PNES
PNER
PNER
«360
«1
7.2 x 10 4 (25°C)
(ml cell'1 hr'1) -
E-P
C-OX
C-OX
HPHI
NACM
WREF
VF-NBD
E: Estimated value; see List of Source Codes.
142
-------
34. 1,1-DICHLOROETHANE
Cl H
CAS No. 75-34-3
C H
Cl H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
98.96
-96.98
57.28
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
5.5 x 10 (20°C)
_63
30
19
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4.26 x 10
-3
180 (20°C)
0.580
C-VP/S-20C
Verschueren, 1977
C-DC.7
143
-------
34. 1,1-DICHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For C>2 (singlet oxygen) ,
ox
hr-1>
For R02 (peroxy radical) ,
kox (N~l ^
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr-1)
PNES
PNER
PNER
«360
1.15 x 10 7 (25°C)
E-P
c-ox
c-ox
NACM
[34-1]
VF-NBD
E: Estimated value; see List of Source Codes.
[34-1] Hydrolysis neutral rate constant has been assigned by
analogy to dichloromethane.
144
-------
o a
H-
H
35. 1,2-DICHLOROETHANE
CAS No. 107-06-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
98.98
-35.36
83.47
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
8.69 x 10'
_30
14
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
9.14 x 10
-4
61 (20°C)
NAV
C-VP/S-200
WREF
145
-------
35. 1,2-DICHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
kQX (M-1 hr"1)
For R02 (peroxy radical),
k (M-1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
-1 v,,.—1\
For acid-promoted process,
k OF1 hr-1)
A.
For neutral process ,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
PNES
PNER
PNER
<360
<1
1.8 x 10 9 (25°C)
(E) 1 x 10
-10
E-P
c-ox
c-ox
NACM
WREF
E-KB
E: Estimated value; see List of Source Codes.
146
-------
a H
a-
c —H
a H
36. 1,1,1-TRICHLOROETHANE
CAS No. 71-55-6
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
133.41
-30.41
74.1
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
/'(yg/gHmg/Jl)-1
720 (25°C)
152
81
Pilling, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
0.03
123 (25°C)
0.533
C-VP/S-25C
Billing, 1977
C-DC.7
147
-------
36. 1,1,1-TRICHLOROETHANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, <(>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (M-1 hr-1>
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
l
k£
hr'1)
For acid-promoted process,
hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr-1)
Value
PNES
PNER
PNER
«360
0
1.7 x 10 4 (25°C)
E: Estimated value; see List of Source Codes.
Data Source
WREF
C-OX
C-OX
NACM
WREF
VF-NBD
148
-------
a a
a
H H
37. 1,1,2-TRICHLOROETHANE
CAS No. 79-00-5
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
133.41
-36.5
113.77
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
4.5 x
117
56
33
(20°C)
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
"3 1 C
(atm m^ moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
7.42 x 10
-4
19 (20°C)
NAV
C-VP/S-20C
WREF
149
-------
37. 1,1,2-TRICHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, »
at _ nm
Direct photolysis rate
constant, k (hr-1)
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen) ,
For R02 (peroxy radical) ,
ox
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k, (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, It (ml cell"1 hr"1)
PNES
PNER
PNER
«360
1.2 x 10 7 (25°C)
(E) 3 x 10 12
WREF
c-ox
c-ox
NACM
E-H [37-1]
E-KB
E: Estimated value; see List of Source Codes.
[37-1] Neutral hydrolysis rate constant was assigned by analogy
to dichloromethane.
150
-------
I T
H-
38. 1,1,2,2-TETRACHLOROETHANE
CAS No. 79-34-5
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
167.85
-36
146.2
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.9 x 10 (20°C)
245
118
91
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
o 1 C
(atm m3 mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.8 x 10
-4
5 (20°C)
NAV
C-VP/S-20'
WREF
-------
38. 1,1,2,2-TETRACHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, t|>,
at _ nm
Direct photolysis rate
constant, k (hr-1)
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr'1)
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, le (ml cell"1 hr"1)
PNES
PNER
PNER
«360
1.2 x 10 (25°C)
(E) 3 x 10
-12
WREF
C-OX
C-OX
NACM
E-H [38-1]
E-KB
E: Estimated value; see List of Source Codes.
[38-1] Hydrolysis neutral rate constant is assigned by analogy to
dichloromethane.
152
-------
39. HEXACHLOROETHANE
CAS No. 67-72-1
a a
a— c — c
I I
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
236.74
186.8-187.4
186 (777mm)
pK-NER
Data Source
CRC [39-1]
WREF [39-1]
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
50 (22°C)
4.2 x 10
2.0 x 104
6.75 x 10-
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
O 1 C
(atm m^ mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.49 x 10
-3
0.4 (20°C)
0.443
C-VP20°/S22C
WREF
C-DC.7
153
-------
39. HEXACHLOROETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
kR (M-1 hr'1)
D
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
(E) 1 x 10
-10
WREF
c-ox
c-ox
HNES
NACM
HNES
E-KB
E: Estimated value; see List of Source Codes.
[39-1] Hexachloroethane sublimes on heating.
154
-------
40. CHLOROETHENE
CAS No. 75-01-4
Cl
\
\
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
62.5
-153.8
-13.37
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.7 x 10 (25°C)
8.2
5.7
Pilling, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
8.14 x 10
-2
2.66 x 10 (25°C)
0.675
C-VP/S-25'
WREF
C-DC.7
155
-------
40. CHLOROETHENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <|>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (>rl hr"!)
For R02 (peroxy radical) ,
kox (trl hr~1}
Hydrolysis rate constants:
For base-promoted process,
kfi (IT1 hr-1)
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
PNES
PNER
PNER
WREF
c-ox
c-ox
HNES
HNES
HNES
VF-NBD
E: Estimated value; see List of Source Codes.
156
-------
a
\
/
\
H
41. 1,1-DICHLOROETHENE
CAS No. 75-35-4
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
96.94
-122.1
37
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
M
400 (20°C)
135
65
53
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.190
591 (25°C)
0.601
C-VP25°/S20£
WREF
C-DC.7
157
-------
41. 1,1-DICHLOROETHENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, t}> ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
kox (trl hr"1}
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
k.. (M-l hr-1)
D
For acid-promoted process,
k (M~l hr-1)
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
WREF
C-OX
C-OX
HNES
HNES
HNES
VF-NBD
E: Estimated value; see List of Source Codes.
158
-------
42.
1,2-TRANS-DICHLOROETHENE
CAS No. 540-59-0
\
./'
a
\
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
96.94
47.5 [42-1]
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
600 (20°C)
123
59
48
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.067
326 (20°C)
0.601
C-VP/S-20C
Billing, 1977
C-DC.7
159
-------
42. 1,2-TRANS-DICHLOROETHENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25°C:
For •'•02 (singlet oxygen) ,
ox
hr"1}
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
Data Source
UV-ATLAS
c-ox
c-ox
HNES
HNES
HNES
VF-NBD
E: Estimated value; see List of Source Codes.
[42-1] No pressure is reported for the boiling point.
160
-------
43.
TRICHLOROETHENE
Ct
\
CAS No. 79-01-6
\
Cl
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
131.39
-73
87
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water
1.1 x 10 (20°C)
263 _
126
97
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
9.1 x 10
-3
57.9 (20°C)
0.548
C-VP/S-20°C
WREF
C-DC.7
161
-------
43.
TRICHLOROETHENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kQX (M"1 hr"1)
For R02 (peroxy radical),
k (M-1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
k (M"1 hr" )
For acid-promoted process,
k. (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
Value
PNES
PNER
PNER
]CE) 1 x 10
-10
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
162
-------
44. TETRACHLOROETHENE
\
a
CAS No.
127-18-4
a
./
\
a
PHYSICAL AND TRANSPORT DATA
Property or Process .Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
165.83
-22.7
121
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
200 (20°C)
759
364
252
WREF [44-1]
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.0153
14 (20°C)
0.509
C-VP/S-20C
WREF
C-DC.7
163
-------
44. TETRACHLOROETHENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, (J>,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
kox (H-l hr-1)
For R02 (pero^xy radical),
Hydrolysis rate constants:
For base-promoted process,
kfi (M-1 hr"1)
For acid-promoted process,
k. (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
Value
PNES
PNER
PNER
«100
(El 1 v IP
-10
Data Source
UV-ATLAS
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[44-1] A range of solubility values, from 150 ppm to 200 ppm,
has been reported (WREF).
164
-------
H a
H
a— c — c — c —H
I I l
H H H
45. 1,2-DICHLOROPROPANE
CAS No. 78-87-5
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
112.99
-100
96.8
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water,
2.7 x 10 (20°C)
105
30
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.31 x 10
-3
42 (20°C)
0.530
C-VP/S-20C
WREF
C-DC.7
165
-------
45. 1,2-DICHLOROPROPANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
(singlet oxygen) ,
For
ox
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr-1)
For acid-promoted process,
k (M-1 hr-1)
£\
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
Value
PNES
PNER
PNER
«360
7.2 x 10 (25°C)
(E) 1 x 10~10
Data Source
WREF
c-ox
c-ox
NACM
[45-1]
E-KB
E: Estimated value; see List of Source Codes.
[45-1] Hydrolysis neutral rate constant is assigned by analogy to
chloroethane.
166
-------
°
\
\
\
Cl
46. 1,3-DICHLOROPROPENE
CAS No. 542-75-6
(TRANS ISOMER) [46-1]
PHYSICAL AND TRANSPORT DATA
Property or Process
Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
110.98
104.3, 112
pK-NER
Data Source
WREF [46-2]
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
, ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.7 x 10
2.8 x 10
3 (25°C)
100
48
40
WREF [46-3]
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.33 x 10
-3
25 (20°C)
NAV
C-VP20°/S25°[46-33]
WREF
167
-------
46. 1,3-DICHLOROPROPENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
k (M"1 hr"1)
OX
For R02 (peroxy radical),
k (M"1 hr"1)
OX
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr-1)
For acid-promoted process,
k (M"1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
44
4.2 x 10 (25°C)
E-P
_(E) 1 x 10
-10
c-ox
C-OX [46-4]
HPHI
NACM
[46-5]
E-KB
E: Estimated value; see List of Source Codes.
a
[46-1] Cl H
C
H c = G' (CIS ISOMER)
/ \
H H
168
-------
46. 1,3-DICHLOROPROPENE
[46-2] Boiling points of 104.3°C for the cis isomer and 112°C for the
trans isomer were reported.
[46-3] Water solubilities of 2700 ppm for the cis isomer and
2800 ppm for the trans isomer were reported. The
solubility of the cis isomer is used in the calculation
of Henry's constant.
[46-4] 44 M"1 hr"1 is the minimum oxidation rate constant for
oxidation by peroxy radical.
[46-5] The hydrolysis rate constant for 1,3-dichloropropene which
is reported in WREF does not reflect the hydrolytic
reactivity characteristic of allylic halides. For example,
allyl chloride has a rate constant of 4.16 x 10-l* hr
at 25°C and is pH independent (Mabey and Mill, 1978).
Because of its similar structure compared with allyl
chloride, a hydrolysis rate constant of 4.2 x 10-Lf hr"1
has been assigned to 1,3-dichloropropene.
169
-------
4 7. HEXACHLORO-1,3-BUTADIENE
\
a
Cl
/
\
CAS No. 87-68-3
a
cr
/
\
a
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
260.76
-21
215
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.0 (20°C)
6.0 x 104
2.9 x 104
1.3 x 10
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
0.0256
0.15 (20°C)
0.415
C-VP/S-20C
WREF
C-DC.7
171
-------
47. HEXACHLOROBUTADIENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <)>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M~! hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
PNES
PNER
PNER
(E) 1 x 10
-10
WREF
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
172
-------
48. HEXACHLOROCYCLOPENTADIENE
Cl
\
CAS No. 77-47-4
\
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
272.77
-9.9
239 (753mm)
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.8 (25°C)
1.0 x 104
4.8 x 103
1.8 x 10-
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
0.016
0.081 (25°C)
0.413
C-VP/S-25'
WREF
C-DC.7
173
-------
48. HEXACHLOROCYCLOPENTADIENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, $ ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
kQX (M-1 hr'1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
Value
DATA-ATT [48-1]
3.9
<1CT
12
2.0 x 10 3 (25°C)
(E) 1 x 10
-10
Data Source
Zepp, 1980
WREF
C-OX
C-OX
HPHI
NACM
WREF
E-KB
E: Estimated value; see List of Source Codes.
174
-------
48. HEXACHLOROCYCLOPENTADIENE
[48-1] Table of absorption coefficients and the corresponding
wavelengths is given below (Zepp, 1980).
WAVELENGTH EPSILON
(nm) (M"1 cm"1)
297.50 0.1120E+04
300.00 0.1140E+04
302.50 0.1150E+04
305.00 0.1240E+04
307.50 0.1300E+04
310.00 0.1360E+04
312.50 0.1420E+04
315.00 0.1460E+04
317.50 0.1500E+04
320.00 0.1510E+04
323.10 0.1520E+04
330.00 0.1410E+04
340.00 0.1170E+04
350.00 0.8000E+03
360.00 0.4480E+03
370.00 0.2120E+03
380.00 0.8200E+02
390.00 0.2000E+02
175
-------
49. BROMOMETHANE
H
CAS No. 74-83-9
H C Br
I
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
94.94
-93.6
3.56
pK-NER
Data Source
CRC
CRC
Partition constants:
Water solubility, S
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
900 (2Q°C)
12.3
5.9
4.2
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
3 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.197
1.42 x 103 (20°C)
0.737
C-VP/S-20C
WREF
C-DC.7
177
-------
49. BROMOMETHANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, <)>,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kQX (IT1 hr"1)
For R02 (peroxy radical),
kQX (M-1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
Value
PNES
PNER
PNER
«360
0.1
1.44 x 10 3 (25°C)
Data Source
WREF
c-ox
c-ox
HPHI
NACM
WREF
VF-NBD
E: Estimated value; see List of Source Codes.
178
-------
50. BROMODICHLOROMETHANE
Br
I
a— c —a
H
CAS No. 75-27-4
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
163.83
-57.1
90
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
4.5 x 10"
126
61
35
C-Sw f Row
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
v
Reaeration rate ratio,
kc/k°
v v
2.41 x 10
-3
50 (20°C)
0.655
C-VP20°/S22'
WREF
C-DC.7
179
-------
50. BROMODICHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25° C:
(singlet oxygen),
For
ox
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kR (M-l hr'1)
D
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr-1)
PNES
PNER
PNER
«360
0.2
5.76
5.76 x 10 (25°C)
(E) 1 x 10
-10
E-P
C-OX
C-OX
WREF
NACM
E-AC-H
E-KB
E: Estimated value; see List of Source Codes.
[50-1] Solubility value was obtained from unpublished work done
at SRI International.
180
-------
51. DIBROMOCHLOROMETHANE
CAS No. 124-48-1
Br
I
O C Br
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
208.29
<-20
119-120 (748mm)
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
4.0 x 10-
174
84
47
C-Sw f Kow
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
o 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
9. 9 x 10
-4
76 (20°C)
NAV
C-VP20°/S22° [51-2]
[51-2]
181
-------
51. DIBROMOCHLOROMETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
ox
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k, (ml cell""1 hr-1)
PNES
PNER
PNER
«360
0.5
2.88 (25°C)
2.88 x 10 8 (25°C)
(E) 1 x 10
-10
E-P
C-OX
C-OX
WREF
NACM
E-AC-H
E-KB
E: Estimated value; see List of Source Codes.
[51-1] Water solubility data obtained from unpublished results
at SRI International.
[51-2] Vapor pressure value at 20°C is obtained from the value
at 10.5°C and the Clausius Clapeyron equation.
182
-------
52.
TRIBROMOMETHANE
Br
CAS No. 75-25-2
Br C Br
I
H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
252.75
8.3
149.5
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w (ppm)
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.01 x 10 (20°C)
240
116
63
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm mj mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
5.6 x 10
-4
5 (20°C)
NAV
C-VP/S-20C
Jordan, 1954
183
-------
5 2. TRIBROMOMETHANE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox (M"1 hirl>
For R02 (peroxy radical),
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
kR (M-1 hr'1)
D
For acid-promoted process,
k. (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
«360
0.5
1.15 (25°C)
2.5 x 10 (25°C)
(E) 1 x 10
-10
Data Source
UV-ATLAS
C-OX
C-OX
WREF [52-1]
HNES
[52-2]
E-KB
E: Estimated value; see List of Source Codes.
[52-1] This hydrolysis rate constant at pH 7 and 25°C reported in
WREF is assumed to be due to the base promoted process.
[52-2] The neutral hydrolysis rate constant, K^, has been assigned by
analogy to trichloromethane.
184
-------
5 3. DICHLORODIFLUOROMETHANE
CAS No. 75-71-8
a
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
120.91
-158
-29.8
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
280 (25°C)
120
58
33
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.98
0.615
C-VP/S-25'
4.87 x 10 (25°C) Jordan, 1954
C-DC.7
185
-------
53. DICHLORODIFLUOROMETHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <|>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
kox (M~l hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
promote
l hr"1)
For acid-promoted process,
k (M-1 hr-1)
J\
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
PNES
PNER
PNER
E-P
C-OX
C-OX
HNES
HNES
HNES
VF-NBD
E: Estimated value; see List of Source Codes.
186
-------
54. TRICHLOROFLUOROMETHANE
CAS No. 75-69-4
• a
a
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
137.4
-111
23.8
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
1.1 x 10 (20°C)
331
159
84
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
0.11
667.4 (20°C)
0.571
C-VP/S-20C
WREF
C-DC.7
187
-------
54. TRICHLOROFLUOROMETHANE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"-'- hr~*)
Value
PNES
PNER
PNER
Data Source
WREF
c-ox
c-ox
HNES
HNES
HNES
VF-NBD
E: Estimated value; see List of Source Codes.
188
-------
References for 3.4
Billing, W. L. 1977. Interphase Transfer Processes. II. Evaporation
Rates of Chloromethanes, Ethanes, Ethylenes, Propanes, and Propy-
lenes from Dilute Aqueous Solutions. Comparisons with Theoretical
Predictions. Environ. Sci. Technol. 11:405-409.
Jordan, T. E. 1954. Vapor Pressure of Organic Compounds. Interscience
Publishers, Inc., New York. 266 pp.
Mabey, W. R., and T. Mill. 1978. Critical Review of Hydrolysis of Or-
ganic Compounds in Water Under Environmental Conditions. J. Phys.
Chem. Ref. Data 7:383.
UV Atlas. 1971. UV Atlas of Organic Compounds. Vol. I-V. Plenum Press,
New York.
Verschueren, K. 1977. Handbook of Environmental Data on Organic Chemicals,
Van Nostrand/Reinhold Press, New York. 659 pp.
Zepp, R. G. 1980. Private communication.
Pomona College Medicinal Data Base, June 1982.
189
-------
SECTION 3.5. HALOGENATED ETHERS
55. Bis(chloromethyl)ether
56. Bis(2-chloroethyl)ether
57. Bis(2-chloroisopropyl)ether
58. 2-Chloroethyl vinyl ether
59. 4-Chlorophenyl phenyl ether
60. 4-Bromophenyl phenyl ether
61. Bis(2-chloroethoxy)methane
191
-------
55. BIS(CHLOROMETHYL)ETHER
CAS No. 542-88-1
Cl
H
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
115
-41.5
104
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.2 x 10 (25°C)
2.4
1.2
WREF
1.0
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
n 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.1 x 10
-4
30 (22°C)
NAV
C-VP22°/S25C
WREF
193
-------
55. BIS(CHLOROMETHYL)ETHER
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen) ,
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr'1)
For acid-promoted process,
k (JT1 hr-1)
A.
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
«360
65 (20°C)
WREF
c-ox
c-ox
HPHI
HPHI
WREF
HF-NBD
E: Estimated value; see List of Source Codes.
194
-------
56.
BIS(2-CHLOROETHYL)ETHER
CAS No. 111-44-4
a — c — c — o — c — c
II II
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
143
-24.5
178
pK-NER
Data Source
CRC
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water.
1.02 x 1(T [56-11
13.9
9.2
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.3 x 10
-5
0.71 (20°C)
NAV
C-VP20°/S-[56-11
WREF
195
-------
56. BIS(2-CHLOROETHYL)ETHER
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen) ,
kox (M"T ^
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr'1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr )
PNES
PNER
PNER
«360
24
4 x 10 6 (25°C)
(E) 3 x 10
-9
WREF
C-OX
C-OX
HPHI
HPHI
[56-2]
E-KB
E: Estimated value; see List of Source Codes.
[56-1] No temperature reported for the water solubility; data generated
at room temperature* This value is used in the calculation
of Henry's constant.
196
-------
56. BIS(2-CHLOROETHYL)ETHER
[56-2] A hydrolysis rate constant of 1.5 x 10~5 min"1 has been
reported for bis(2-chloroethyl)ether in aqueous dioxane
at 100°C (WREF). This rate constant corresponds to a half-
life of 32 days. Allowing for a factor of two decrease
in rate,constant for each 10°C decrement, the half-life
is calculated as 22 years (or 256 times slower) at 20°C.
This rate constant is much slower than expected based on
a simple analogy to ethyl chloride where a half-life of
38 days is predicted at pH 7 and 25°C (Mabey & Mill, 1978).
The relatively slow hydrolysis rate of bis(2-chloroethyl)
ether compared with ethyl chloride is due to the effect on the
adjacent carbon of the -OCt^CI^Cl group. Data have been
obtained which show that aqueous solvolysis of 2-methoxy-
ethyl iodide at 60°C is 6.4 x 10~3 times the rate of ethyl
iodide under the same reaction conditions (Streitwieser,
1962). Assuming that this 6.4 x 10~3 factor holds for
the chloroaliphatic compounds as well as for the iodo
compounds, the 38 day half-life of ethyl chloride can be
used to obtain a half-life of 16 years for bis(2-chloro-
ethyl) ether. This estimate of the half-life is in fair
agreement with the 22 year half-life calculated from the
aqueous dioxane solvent data cited in WREF. For this
assessment, an estimated half-life of 20 years is used to
obtain a neutral rate process, k , of 4 x 10~6 hr"1.
The hydrolysis of bis(2-chloromethyl)ether should be
independent of pH by analogy to other aliphatic halocarbons.
197
-------
57. BIS(2-CHLOROISOPROPYL)ETHER
CAS No. 108-60-1
c — c — o
H CH,
C C
CH3 H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
171.1
189
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow '
Sediment-water, K (unitless)
Microorganisms-water,
1.7 x 10 [57-1]
126
35
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.1 x 10
-4
0.85 (20°C)
NAV
C-VP20°/S-[57-11
WREF
199
-------
57. BIS(2-CHLOROISOPROPYL)ETHER
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen).
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
kN (hr-1)
Biotransformation rate constant:
For bacterial transformation
"1
PNES
PNER
PNER
«360
4 x 10 6 (25°)
in water, k (ml cell"1 hr l) (E) 1 x 10
-10
WREF
C-OX
C-OX
HPHI
HPHI
[57-2]
E-KB
E: Estimated value; see List of Source Codes.
[57-1] Experimental water solubility data was generated at room
temperature; no specific temperature was reported.
This value was used in the calculation of Henry's constant.
200
-------
57. BIS(2-CHLOROISOPROPYL)ETHER
[57-2] Rate constant assigned by analogy to bis(2-chloroethyl)ether
(see footnote [56-3])
201
-------
58. 2-CHLOROETHYL VINYL ETHER
CAS No. 110-75-8
OH H H
II II
H C C 0 C = C
\ I
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
106.6
108
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water
1.5 x 10 (25°C)
13.8
6.6
4.7
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
*3 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.50 x 10
-7
26.75 (20°C)
NAV
C-VP20°/S25'
WREF
203
-------
58. 2-CHLOROETHYL VINYL ETHER
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
For
Hydrolysis rate constants:
For base-promoted process,
kB CM-1 hr'1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process ,
Biotransf ormation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
(peroxy radical) ,
PNES
PNER
PNER
1 x 10
10
34
WREF
4 x 10 6 (25°C)
C-OX
C-OX
HPHI
HPHI
[58-1]
(E) 1 x 10
-10
E-KB
E: Estimated value; see List of Source Codes.
[58-1] The chloride group in 2-chloroethyl vinyl ether will be
hydrolyzed at a rate similar to that of bis(2-chloroethyl)ether.
The assigned hydrolysis rate constant, k , is 4 x 10"6 hr"1
as for bis(2-chloroethyl)ether. No data are available to
assess the possible effect of the vinyl ether functional
group on the rate of hydrolysis. Hydrolysis of the chloride
group is expected to be independent of pH by analogy to
other halogenated aliphatics.
204
-------
59. 4-CHLOROPHENYL PHENYL ETHER
CAS No. 7005-72-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
204.66
-8
293
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.3 (25°C)
1.2 x 105
5.8 x 104
1.8 x 10
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm nr mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.19 x 10
-4
2.7 x 10
-3
NAV
C-VP/S-25'
WREF
205
-------
59. 4-CHLOROPHENYL PHENYL ETHER
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr )
_ at _ latitude
Oxidation constants at 25° C:
For 102 (singlet oxygen) ,
kox (M-1 hr-1)
For R02 (peroxy radical) ,
For acid-promoted process,
k
Hydrolysis rate constants:
For base-promoted process,
hr~!)
p
1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
«360
«1
(E) 1 x 10
-7
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
206
-------
60. 4-BROMOPHENYL PHENYL ETHER
CAS No. 101-55-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
249.11
18.72
310.14
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water,
4.8 (25°C)
8.7 x 104
4.2 x 104
1.3 x 10
C-Sw f Kow
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
Q 1 C
(atm md mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.0 x 10
-4
1.5 x 10 3 (20°C)
NAV
C-VP20°/S25'
WREF
207
-------
60. 4-BROMOPHENYL PHENYL ETHER
TRANSFORMATION DATA
JProperty or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kR (M-l hr'1)
D
For acid-promoted process,
hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
Value
«360
«1
(E) 3 x 10
-9
Data Source
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
208
-------
61. BIS(2-CHLORQETHOXY)METHANE
CAS No. 111-91-1
H
C
H
H
C 0
H
H H
I I
C C
I I
H H
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
173.1
218.1
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
8.1 x 10 (25°C)
10.7
5.2
3.7
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.8 x 10
-7
(20°C)
NAV
C-VP20°/S25'
WREF
209
-------
61. BIS(2-CHLOROETHOXY)METHANE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen) ,
For R02 (peroxy radical),
Hydrolysis rate constants:
For base-promoted process,
hr"1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
«360
52
4 x 10 6 (25°C)
(E) 3 x 10
-12
WREF
C-OX
C-OX
HPHI
HPHI
[61-1]
E-KB
E: Estimated value; see List of Source Codes.
210
-------
61. BIS(2-CHLOROETHOXY)METHANE
[61-1] A neutral hydrolysis rate constant, lc , of 4 x 10~8 hr"1
for the loss of chloride from the ethane group is assigned
to 2-chloroethoxy methane by analogy to bis(2-chloroethyl)ether.
Hydrolysis with loss of chloride is independent of pH by
analogy to other alkyl halides (Mabey & Mill, 1978).
The carbon-oxygen bonds of the acetal linkage are also
suspectible to hydrolysis. The acid-catalyzed hydrolysis
rate constant, k , for this process has been measured at
2.53 x 1CT6 M"1 sec"1 (WREF). At pH 3, this rate constant
corresponds to a half-life of 8.7 years. Since the acid-
promoted hydrolysis will decrease by a factor of ten for
each pH unit increase, hydrolysis of the compound at
the chlorinated position will dominate over the acetal
hydrolysis at environmental pHs.
211
-------
References for 3.5
Mabey, W. R., and T. Mill. 1978. Critical Review of Hydrolysis of Or-
ganic Compounds in Water Under Environmental Conditions. J. Phys.
Chem. Ref. Data 7:383.
Streitwieser, A., Jr. 1962. Solvolytic Displacement Reactions. McGraw-
Hill, New York.
212
-------
SECTION 3.6. MONOCYCLIC AROMATIC CHEMICALS
62. Benzene
63. Chlorobenzene
64. 1,2-Dichlorobenzene (o-dichlorobenzene)
65. 1,3-Dichlorobenzene (m-dichlorobenzene)
66. 1,4-Dichlorobenzene (p-dichlorobenzene)
67- 1,2,4-Trichlorobenzene
68. Hexachlorobenzene
69. Ethylbenzene
70. Nitrobenzene
71. Toluene
72. 2,4-Dinitrotoluene
73. 2,6-Dinitrotoluene
74. Phenol
75. 2-Chlorophenol
76. 2,4-Dichlorophenol
77. 2,4,6-Trichlorophenol
78. Pentachlorophenol
79. 2-Nitrophenol
80. 4-Nitrophenol
81. 2,4-Dinitrophenol
82. 2,4-Dimethyl phenol
83. j3-Chloro-m-cresol
84. 4,6-Dinitro-o-cresol
213
-------
62. BENZENE
CAS No. 71-43-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
78.12
5.5
80.1
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
„
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water
1.78 x 10 (25°C)
135
_65
37
WREF [62-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
5.5 x 10
-3
95.2 (25°C)
0.574
C-VP/S-25'
WREF
C-DC.7
215
-------
62. BENZENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, <(>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For ^02 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M"1 hr-1)
A.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr""1)
PNES
PNER
PNER
«360
«1
(E) 1 x 10
-7
Data Source
UV-ATLAS
C-OX
c-ox
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[62-1] Several water solubilities, ranging from 820 ppm to 1800 ppm,
have been reported.
216
-------
63. CHLOROBENZENE
CAS No. 108-90-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
112.56
-45
132
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
„ (ppm)
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
488 (25°C)
690
330
164
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.58 x 10
-3
11.7 (20°C)
0.528
C-VP20°/S250
WREF [63-1]
C-DC.7
217
-------
63. CHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (M-1 hr~!)
For R02 (peroxy radical) ,
kox (M-1 hr~1}
Hydrolysis rate constants:
For base-promoted process,
kB CM-1 hr'1)
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
«360
«1
(E) 3 x 10
-9
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[63-1] Two values for vapor pressure - 11.7 torr and 8.8 torr - have
been reported. The 11.7 torr value was obtained from the
table of vapor pressures, critical temperatures and critical
pressures in CRC Handbook, while the 8.8 torr value is
reported in Verschueren, 1977.
218
-------
64. 1,2-DICHLOROBENZENE
CAS No. 95-50-1
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
147.01
-17.0
180.5
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
100 (20°C)
3.6 x 103
1.7 x 103
730
Verschueren, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.93 x 10
-3
1.0 (20°C)
0.495
C-VP/S-20'
Verschueren, 1977
C-DC.7
219
-------
64. 1,2-DICHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
» _ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox <*~l hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
PNES
PNER
PNER
«360
«1
(E) 1 x 10
-10
E-P
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
220
-------
65. 1.3-DICHLOROBENZENE
CAS No. 541-73-1
a
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
147.01
-24.7
173
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
123 (25°C)
3.6 x 103
1.7 x 103
730
Verschueren, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
3.61 x 10
-3
2.28 (25°C)
0.495
C-VP/S-25'
WREF
C-DC.7
221
-------
65. 1,3-DICHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
at
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell""1 hr"1)
PNES
PNER
latitude PNER
«360
«1
(E) 1 x 10
-10
E-P
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
222
-------
66. 1,4-DICHLOROBENZENE
CAS No. 106-46-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
147.01
53.1
174
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
79 (25°C)
3.6 x 10"
1.7 x 10'
730
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.1 x 10
-3
1.18 (25°C)
0.495
C-VP/S-25'
WREF
C-DC.7
223
-------
66. 1,4-DICHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
k (M-l hr'1)
D
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, It (ml cell"1 hr-1)
PNES
PNER
PNER
«360
«1
(E) 1 x 10
-10
E-P
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
224
-------
67. 1,2,4-TRICHLOROBENZENE
CAS No. 120-82-1
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
181.45
16.95
213.5
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
30 (25°C)
1.9 x 10
9.2 x 10-
3.3 x 10-
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2 . 3 x 10
-3
0.29 (25°C)
0.465
C-VP/S-25'
Dreisbach, 1955
C-DC.7
225
-------
67. 1,2,4-TRICHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
kR (M-1 hr'1)
JO
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
DATA-ATT [67-1]
«360
«1
(E) 1 x 10
-10
Data Source
Zepp, 1980
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
226
-------
67. 1,2,4-TRICHLOROBENZENE
[67-1] The absorption coefficients and the corresponding
wavelengths are as follows (Zepp, 1980):
WAVELENGTH EPSILON
(nm) (M"1 cm"1)
297.50 0.4000E+01
300.00 0.1400E+01
302.50 0.6100E+00
305.00 0.3600E+00
307.50 0.2600E+00
310.00 0.2200E+00
312.50 0.2000E+00
315.00 0.1800E+00
317.50 0.1600E+00
320.00 0.1500E+00
323.10 0.1000E+00
330.00 0.5300E-01
340.00 0.1300E-01
227
-------
68. HEXACHLOROBENZENE
CAS No. 118-74-1
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
284.79
230
322 [68-1]
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
6 x 10 3 (25°C)
2.6 x 106
1.2 x 106
2.9 x 10"
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6 . 8 x 10
-4
1.09 x 10 5 (20°C)
NAV
C-VP20°/S25C
WREF
229
-------
68. HEXACHLOROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-l hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
b
«360
«1
(E) 3 x 10
-12
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[68-1] No pressure is reported with the boiling point.
230
-------
69. ETHYLBENZENE
CAS No. 100-41-4
CH3CH2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
106.16
-94.9
136.2
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
152 (20°C)
2.2 x 103
1.1 x 103
470
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6 . 6 x 10
-3
7 (20°C)
0.489
C-VP/S-20'
WREF
C-DC.7
231
-------
69.
ETHYLBENZENE
TRANSFORMATION DATA
JProperty or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, 4>,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
kQX (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
kA (M-1 hr'1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
b
PNES
PNER
PNER
«360
720
(E) 3 x 10
-9
E-P
c-ox
c-ox
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
232
-------
70. NITROBENZENE
CAS No.
98-95-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
123.11
5.6
211
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.9 x 10 (20°C)
_74
22
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.31 x 10
-5
0.15 (20°C)
NAV
C-VP/S-200
WREF
233
-------
70. NITROBENZENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, cf>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (M"1 hr-1)
For R02 (peroxy radical) .
kox OT1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
fi
hr"1)
For acid-promoted process,
k (M~! hr-1)
ci.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
SPEC-ATT [70-1]
«360
«1
(E) 3 x 10
-9
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
234
-------
70. NITROBENZENE
[70-1] UV spectrum in light petroleum solvent (b.p. 100-120°C)
is shown below (UV Atlas, 1966).
u
X (nm)
235
-------
71. TOLUENE
CAS No. 108-88-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
92.13
110.6
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
534.8 (25°C)
620
300
148
Verschueren, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6.66 x 10 J
28.7 (20°C)
0.526
C^VP2Q°/S25°
Verschueren, 1977
C-DC.7
237
-------
71. TOLUENE
TRANSFORMATION DATA
JPrgperty or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, cf>,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen),
PNES
PNER
PNER
«360
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, le (ml cell"1 hr"1)
Data Source
UV-ATLAS
UA
For R02 (peroxy radical) ,
k (M"1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr-1)
For acid-promoted process,
k (M-1 hr-1)
144
0
0
(E) 1 x 10
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
238
-------
72. 2,4-DINITROTOLUENE
CAS No. 121-14-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
182.14
70
300
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow '
Sediment-water, K (unitless)
oc
Microorganisms-water
270 (22°C)
95
45
39
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
4.5 x 10
-6
C-VP20°/S22°
5.1 x 10~3 (20°C) Maksimov, 1968
NAV
239
-------
72. 2,4-DINITROTOLUENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, $,
at 313 nm
Direct photolysis rate
constant, k (hr-1)
P
summer at 40° latitude
Oxidation constants at 25°C:
For Q£ (singlet oxygen),
hr"1)
For R02 (peroxy radical) ,
kox (>rl hr-1>
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr-1)
Value
DATA-ATT
7.5 x 10
-4
1.6 x 10
-2
«360
144
1 x 10
-7
Data Source
[72-1]
[72-1]
[72-1]
C-OX
C-OX
HNES
HNES
HNES
[72-1]
E: Estimated value; see List of Source Codes.
240
-------
72. 2,4-DINITROTOLUENE
[72-1] Photolysis and biotransformation data are reported in Spanggord
et al. (1980). The measured sunlight photolysis half-life of
2,4 DNT in pure water is approximately 42 hours; however, the
sunlight photolysis half-lives in three natural waters ranged
from 3 hrs to 10 hrs, showing that humic substances can promote
the photolysis.
It also should be noted that an acclimated system capable of
biotransforming 2,4 DNT was obtained in only one natural water
sample, and k was measured using that mixed culture system.
The absorption coefficients for 2,4 DNT reported in Spanggord
et al. (1980) are listed below.
WAVELENGTH
(nm)
297.50
300.00
302.50
305.00
307.50
310.00
312.50
315.00
317.50
320.00
323.10
330.00
340.00
350.00
360.00
370.00
380.00
390.00
400.00
410.00
EPSILON
CM-1 cm"1)
0.4104E+04
0.3747E+04
0.3390E+04
0.3033E+04
0.2677E+04
0.2320E+04
0.1963E+04
0.1784E+04
0.1606E+04
0.1338E+04
0.1249E+04
0.1071E+04
0.7140E+03
0.5350E+03
0.3570E+03
0.2680E+03
0.1780E+03
0.8900E+02
0.3600E+02
O.OOOOE+00
241
-------
73. 2,6-DINITROTOLUENE
CAS No. 606-20-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
182.14
65
285
pK-NER
Data Source
WREF
WREF [73-1]
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
180 (20°C)
190
92
51
[73-2]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
7.9 x 10
-6
0.018 (20°C)
NAV
C-VP/S-200 [73-31
Maksimov, 1968
243
-------
73. 2,6-DINITROTOLUENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, cf> ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
Value
«360
144
(E) 1 x 10
-10
Data Source
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[73-1] No pressure value is reported for the boiling point.
[73-2] The water solubility value has been estimated from the
water solubility of 2,4-dinitrotoluene.
244
-------
73. 2,6-DINITROTOLUENE
[73-3] The Henry's Law constant was obtained by extrapolating the
data beyond the melting point and adjusting by
exp
i- -Ml
TM " T/J
where T is the melting point in °C and T is the temperature
at which H is being estimated.
245
-------
74.
PHENOL
CAS No. 108-95-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
94.11
43
181.75
9.89 (20°C)
Data Source
CRC
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc '
Microorganisms-water,
9.3 x 10 (25°C)
14.2
9.4
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4.54 x 10
-7
0.341 (25°C)
NAV
C-VP/S-25'
Biddiscombe &
Martin. 1958
247
-------
74. PHENOL
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
<7 x 10"
1 x 10
(E) 3 x 10
-6
E-P
c-ox
c-ox
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
248
-------
75. 2-CHLOROPHENOL
CAS No. 95-57-8
PHYSICAL AND TRANSPORT DATA
Property or Process [75-11
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
128.56
175.6
8.85 (25°C)
Data Source
CRC
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.85 x 10 (20°C)
151
_73
41
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.03 x 10
-5
1.77 (20°C)
NAV
C-VP/S-20"
C-CT/CRC
249
-------
75. 2-CHLOROPHENOL
TRANSFORMATION DATA
Property or Process [75-1] Value
Photolysis data:
Absorption spectrum PNES
Reaction quantum yield, 4>,
at nm PNER
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
k^ (M-1 hr-1)
15
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process ,
Biotransformation rate constant:
For bacterial transformation
Direct photolysis rate
constant, k (hr"1)
at latitude PNER
<7 x 10"
1 x 10
in water, k (ml cell"1 hr"1) (E) 1 x 10
-7
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[75-1] All data are calculated for the neutral form unless
otherwise stated.
250
-------
76. 2,4-DICHLOROPHENOL
CAS No. 120-83-2
PHYSICAL AND TRANSPORT DATA
Property or Process [76-11
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
163.0
45
210
7.85 [76-2]
Data Source
WREF
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB '
4.6 x 10 (20°C)
790
380
186
Verschueren 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.8 x 10
-6
0.059 (20°C)
NAV
C-VP/S-200 [76-31
C-CT/CRC
251
-------
76. 2,4-DICHLOROPHENOL
TRANSFORMATION DATA
_ Property or Process [76-1] _ Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, <|>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude [76-4]
Oxidation constants at 25°C:
For 102 (singlet oxygen) ,
hr"1) <7 x 105
Data Source
For R02 (peroxy radical) ,
k^v (M-1 hr"1)
UA
Hydrolysis rate constants:
For base-promoted process,
hr"1)
1 x 107
For acid-promoted process,
kA (M"1 hr"1) 0
A
For neutral process,
kN (hr"1) _0
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell-1 hr"1) (E) 1 x 10
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[76-1] All data are calculated for the neutral form unless otherwise
stated.
[76-2] No temperature is reported for the ionization constant.
252
-------
76. 2,4-DICHLOROPHENOL
[76-3] The Henry's Law constant was obtained by extrapolating the
data beyond the melting point and adjusting by
exp
where T is the melting point in °C and T is the temperature
M
at which H is being estimated.
[76-4] Conflicting literature information has been reported for
the photolysis of 2,4-dichlorophenol (WREF). One paper
reports that, after 10 days exposure to sunlight, no starting
chemical could be detected in solution; the other reference
indicated that at wavelengths greater than 280nm, irradiation
induced negligible photolysis.
253
-------
OH
77. 2,4,6-TRICHLOROPHENOL
CAS No. 88-06-2
PHYSICAL AND TRANSPORT DATA
Property or Process [77-1]
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
197.5
68
244.5
5.99 [77-2]
Data Source
WREF
WREF
Verschueren, 1977
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, R (unitless)
ow
Sediment-water, R (unitless)
oc
Microorganisms-water,
800 (25°C)
4.1 x 103
2.0 x 103
824
Verschueren, 1977
CC-Kow
C-Koc f Row
C-KB f Row
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4 x 10
-6
0.012 (25°C)
NAV
C-VP/S-250 T77-31
C-CT/CRC
255
-------
77. 2,4,6-TRICHLOROPHENOL
TRANSFORMATION DATA
_ Property or Process [77-1]
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
hr-1)
Value
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
1 -1
For acid-promoted process,
k (M"1 hr-1)
£\.
For neutral process,
<7 x 10
1 x 10
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell-1 hr"1) (E) 3 x IP"
Data Source
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[77-1] All data are calculated for the neutral form unless otherwise
stated.
[77-2] No temperature is reported for the ionization constant.
256
-------
77. 2,4,6-TRICHLOROPHENOL
[77-3] The Henry's Law constant was obtained by extrapolating the
data beyond the melting point and adjusting by
r AHf ,
where T is the melting point in °C and T is the temperature
M
at which H is being estimated.
c
257
-------
7 8. PENTACHLOROPHENOL
CAS No. 87-86-5
PHYSICAL AND TRANSPORT DATA
Property or Process [78-1] Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
266.4
190
310
4.74 [78-2]
Data Source
WREF
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
14 (20°C)
1.1 x 10-
5.3 x 10
1.6 x 10
Verschueren, 1977
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.8 x 10
-6
C-VP/S-20C
1.1 x 10 (20°C) WREF
NAV
259
-------
7 8. PENTACHLOROPHENOL
TRANSFORMATION DATA
Property or Process [78-1] Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, cf>,
at nm
Direct photolysis rate
constant, k (hr-1)
P
at latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen), o
hr'1) <7 x 10
Data Source
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB CM-1 hr'1)
D
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
1 x IO-
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell'1 hr"1) (E) 3 x 10"
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[78-1] All data are calculated for the neutral form unless
otherwise stated.
[78-2] No temperature was reported for the ionization constant,
260
-------
79. 2-NITROPHENOL
CAS No. 88-75-5
PHYSICAL AND TRANSPORT DATA
Property or Process f79-H
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
139.1
45.3
216
8.28 (25°C)
Data Source
WREF
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.1 x 10 (20°C)
_56
_27
17
Verschueren, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
7.56 x 10
-6
0.151 (20°C)
NAV
C-VP-/S200 F79-21
C-CT/CRC [79-31
261
-------
79. 2-NITROPHENOL
TRANSFORMATION DATA
Property or Process [79-1] Value
Photolysis data:
Absorption spectrum SPEC-ATT [79-4]
Reaction quantum yield, <|>,
at _ nm
Direct photolysis rate
constant, k (hr )
P
_ at _ latitude
Oxidation constants at 25 °C:
For C>2 (singlet oxygen) ,
For R02 (peroxy radical) ,
kox (M": hr"'>
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
^
For neutral process,
<2 x 10"
2 x 10
Biotransformation rate constant:
For bacterial transformation
in water, 1 (ml cell"1 hr"1) (E) 3 x 10
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[79-1] All data are calculated for the neutral form unless
otherwise stated.
262
-------
79. 2-NITROPHENOL
[79-2] The Henry's Law constant was obtained by extrapolating the
data beyond the melting point and adjusting by
AH,
exp
R
M
where T is the melting point in °C and T is the temperature
at which H is being estimated.
[79-3] No temperature is reported for the vapor pressure.
[79-4] UV spectrum of 2-nitrophenol in water is shown below
(UV Atlas, 1966).
X (nm)
263
-------
80. 4-NITROPHENOL
CAS No. 1QQ-07-7
PHYSICAL AND TRANSPORT DATA
Property or Process [80-1]
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
139.1
114.9
279
7.15 (25°C)
Data Source
WREF
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.6 x 10 (25°C)
_93
45
27
Verschueren, 1977
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.5 x 10
-5
2.2 (146°C)
NAV
C-VP146°/S25<
WREF
265
-------
80. 4-NITROPHENOL
TRANSFORMATION DATA
Property or Process [80-1]
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Value
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25°C:
For ^2 (singlet oxygen) ,
For R02 (peroxy radical) ,
kQX (M-1 hr'1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
For neutral process ,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell
-l
SPEC-ATT [80-2]
latitude [80-3]
<2 x 10"
2 x 10
) (E) 1 x 10
-7
Data Source
UV-ATLAS
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[80-1] All data are calculated for the neutral form unless
otherwise stated.
266
-------
80. 4-NITROPHENOL
[80-2] UV spectrum of 4-nitrophenol in water is given below
(UV Atlas, 1966).
182
Kf-
\
200
*?-
250
mp.-
300
I
400
soc
\
ISO
300
I
400
I
sa
X (nm)
[80-3] 4-Nitrophenol at concentrations of 200 ppm in aqueous solutions
has been reported to be degraded after 1-2 months in
sunlight. Given the high concentration of chemical and
uncertain pH of the solution, this information should be
considered only as a qualitative observation that 4-nitrophenol
can be photolyzed in sunlight.
267
-------
81. 2,4-DINITROPHENOL
CAS No. 51-28-5
PHYSICAL AND TRANSPORT DATA
Property or Process [81-1] Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
184.1
114
3.96 (15°C)
Data Source
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
Kg /(yg/gMmg/fc)-1
5.6 x 10 (18°C)
34>7
16.6
15.4
Verschueren, 1977
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm
1
mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v
6.45 x 10
-10
-5
C-VP/S-18'
1.49 x 10 (18°C) Hoyer & Peperle, 1958
NAV
269
-------
81. 2,4-DINITROPHENOL
TRANSFORMATION DATA
Property or Process [81-1]
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
hr'1)
Value
Data Source
For R02 (peroxy radical),
hr-1)
Hydrolysis rate constants:
For base-promoted process,
kB (M-l hr-1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
3 x 10
5 x
in water, kfe (ml cell
-l
) (E) 3 x 10
-9
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
270
-------
82. 2,4-DIMETHYLPHENOL
CAS No. 105-67-9
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
122.2
27-28
210.9
10.60 [82-1]
Data Source
CRC
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
Microorganisms-water
590 (25°C)
200
96.
75
C-Sw f Row
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.7 x 10
-5
0.062 (20°C)
NAV
C-VP20°/S25'
WREF [82-2]
271
-------
82. 2.4-DIMETHYLPHENOL
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
<4 x 10
1.1 x 10
(E)1 x 10
-7
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[82-1] No temperature is reported for the ionization constant.
[82-2] This value of the vapor pressure is for the supercooled
liquid.
272
-------
83. p-CHLORO-m-CRESOL
CAS No. 59-50-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
142.6
66
235
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.85 x 10 (20°C)
125S _
604
400
Verschueren. 1977
Pomona
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.5 x 10
-6
0.05 (20°C)
NAV
C-VP/S-2Q0
[83-11
273
-------
83. p-CHLORO-m-CRESOL
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen) ,
k^ (M~ hr )
OX '
For R02 (peroxy radical),
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
<7 x 10"
1 x 10
(E) 3 x 10
-9
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[83-1] Vapor pressure value is assigned by analogy; no data are
available.
274
-------
84. 4.6-DINITRO-o-CRESOL
CAS No. 534-52-1
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
198.1
85.8
4.35 [84-1]
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
290 (25°C)
500
240
122
C-Sw f Row
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol'1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4 x 10
-5
5 x 10~2 (20°C)
NAV
C-VP20°/S2V
[84-21
275
-------
84. 4,6-DINITRO-o-CRESOL
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen),
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
-1 u
i, (M-I VIT--M
KB ( nr '
For acid-promoted process,
k (M"1 hr"1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in
Value
3 x 10
5 x 10'
water, \a (ml cell'1 hr L) (E) 3 x 10
-9
Data Source
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[84-1] No temperature is reported with the ionization constant.
[84-2] Vapor pressure value assigned by analogy; no data were
available.
276
-------
References for 3.6
Biddiscombe, D. P., and J. F. Martin. 1958. Vapor Pressures of Phenol
and the Cresols. Trans. Faraday Soc. 54:1316-1322.
Dreisbach, R. R. 1955. Physical Properties of Chemical Compounds.
Advances in Chemistry Series No. 15. American Chemical Soceity,
Washington, DC. 536 pp.
Hoyer, H., and W. Peperle. 1958. Dampfdruckmessungen an Organischen
Substanzen und Ihre Sublimationswarmen. Z. Elektrochem. 62:61-65.
Maksimov, Y. Y. 1968. Vapour Pressures of Arotmatic Nitro-compounds
at Various Temperatures. Russ. J. Phys. Chem. 42:1550-1552.
Spanggord, R. J., T. Mill, T.-W. Chou, W. R. Mabey, J. H. Smith, and S.
Lee. 1980. Environmental Fate Studies on Certain Munition Waste-
water Constituents. Phase II Laboratory Studies. Final Report
submitted, U.S. Army Medical Research and Development Command.
Fort Detrick, MD.
UV Atlas. 1971. UV Atlas of Organic Compounds. Vol. I-V. Plenum Press,
New York.
Verschueren, K. 1977. Handbook of Environmental Data on Organic Chemicals
Van Nostrand/Reinhold Press, New York. 659 pp.
Zepp, R. G. 1980. Private communication.
Pomona College Medicinal Data Base, June 1982.
277
-------
SECTION 3.7. PHTHALATE ESTERS
85. Dimethyl phthalate
86. Diethyl phthalate
87. Di-n-butyl phthalate
88. Di-n-octyl phthalate
89. Bis(2-ethylhexyl)phthalate
90. Butyl benzyl phthalate
279
-------
85. DIMETHYL PHTHALATE
0
II
c
c
I!
0
CAS No. 131-11-3
o
o
CH,
•CH,
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
194.2
0
282
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
•w
(unitless)
Sediment-water, K (unitless)
Microorganisms-water,
5.00 x 10 (20°C)
36.3
17.4
16.0
Verschueren, 1977
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
2.15 x 10
-6
,-3
C-VP/S-20C
4.19 x 10 (20°C) C-CT/CRC
NAV
281
-------
85. DIMETHYL PHTHALATE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, <}>,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For ^02 (singlet oxygen),
ox
hr"1}
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kfi
For acid-promoted process,
kA (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k^ (ml cell"1 hr-1)
DATA-ATT [85-1]
PNER
PNER
«360
0.05
248 (30°C)
0.025 (30°C)
Data Source
Zepp, 1980
5.2 x 10
-6
C-OX
C-OX
WREF
C-KBASE
HNES
Wolfe et al.. 1980
E: Estimated value; see List of Source Codes.
282
-------
85. DIMETHYL PHTHALATE
[85-1] Table of absorption coefficients and the corresponding
wavelengths for dimethyl phthalate is given below (Zepp, 1980)
WAVELENGTH EPSILON
(nm) (M"1 cm-1)
297.50 0.8000E+01
300.00 0.2800E+01
302.50 0.1000E+01
305.00 0.3700E+00
307.50 0.1600E+00
310.00 0.8000E-01
312.50 0.6000E-01
315.00 0.4000E-01
317.50 0.4000E-01
320.00 0.3000E-01
323.10 0.3000E-01
330.00 0.2000E-01
340.00 0.1000E-01
283
-------
86. DIETHYL PHTHALATE
0
II
c
II
o
CAS No. 84-66-2
0 —C2H5
O —C2H5
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
222.2
-40.5
298
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
896 (25°C)
295
142
107
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.2 x 10
-6
3.5 x 10 3 (25°C)
NAV
C-VP/S-25'
C-CT/CRC
285
-------
86. DIETHYL PHTHALATE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, $,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
kox (M"1 hr~T)
For R02 (peroxy radical) ,
kox (M"1 hr"J)
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr-1)
For acid-promoted process,
k (M-1 hr-1)
r\.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
PNES
PNER
PNER
«360
1.4
43.2 (30°C)
4.32 x 10 3 (30°C)
(E) 1 x 10
-7
WREF
C-OX
C-OX
WREF
C-KBASE
HNES
E-KB
E: Estimated value; see List of Source Codes.
286
-------
87, DI-n-BUTYL PHTHALATE
0
II
c
c
II
0
CAS No. 84-74-2
o
o
'C4H9
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
278.3
340
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow '
Sediment-water, K (unitless)
Microorganisms-water.
13 (25°C)
3.6 x 10"
1.7 x 10f
4.7 x 10
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.8 x 10
-7
^-VP/S-250
1.0 x 1Q~ (25°C) Jaber, 1982
NAV
287
-------
87. DI-n-BUTYL PHTHALATE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
k CM"1 hr'1)
D
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr""1)
Value
PNES
PNER
latitude PNER
«360
1.4
79.2 (30°C)
7.92 x 10 3 (30°C)
(1.9-4.4) x 10"
E: Estimated value; see List of Source Codes.
Data Source
WREF
c-ox
c-ox
WREF
C-KBASE
HNES
Steen et al., 1979
288
-------
88. DI-n-OCTYL PHTHALATE
CAS No. 117-84-0
C 0 Cj,H17
C
II
o
C8H17
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
391
-25
220 (4mm)
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.0 (25°C)
7.4 x 109
•3 .ft x 109
3 . 9 x 10
8
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol'1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.7 x 10
-5
1.4 x 10 4 (25°C)
NAV
C-VP/S-25'
[88-1]
289
-------
88. DI-n-OCTYL PHTHALATE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr""1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
For neutral process,
\ (hr-1)
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
Value
PNES
PNER
PNER
«360
1.4
79.2 (30°C)
7.92 x 10 3 (30°C)
3.1 x 10
-10
Data Source
WREF
c-ox
c-ox
[88-2]
[88-2]
HNES
Wolfe et al., 1980
E: Estimated value; see List of Source Codes.
[88-1] Vapor pressure value assigned by analogy. This value is
used in the calculation of Henry's constant.
[88-2] Hydrolysis rate constant is assigned by analogy to
di-n-butyl phthalate.
290
-------
89. BIS(2-ETHYLHEXYL)PHTHALATE
CAS No. 117-81-7
O
II
c
c
II
O
O CH2CH(C2H5)C4Hg
0 CH2CH(C2Hg)C4H9
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
391
-50
386.9 (5mm)
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
0.4 (25°C)
4 . 1 x 109
2 . 0 x 109
2 . 3 x 10
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
3 x 10
-7
2 x 10 7 (20°C)
NAV
C-vp20°/s250
C-CT/CRC
291
-------
89. BIS(2-ETHYLHEXYL)PHTHALATE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 02 (singlet oxygen),
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
k£ (M-1 hr'1)
For acid-promoted process,
k (M-1 hr-1)
n.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
PNES
PNER
PNER
«360
7.2
0.4 (30°C)
4.0 x 10 5 (30°C)
4.2 x 10
-12
WREF
C-OX
C-OX
WREF
C-KBASE
HNES
Wolfe et al., 1980
E: Estimated value; see List of Source Codes.
292
-------
90. BUTYL BENZYL PHTHALATE
O
II
c
c
II
O
CAS No. 85-68-7
O
O
-C4H9
-CH- -
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
312
-35
377
pK-NER
Data Source
WREF
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
2.9
3 . 6 x IP"
1 . 7 x 1(T
4 . 7 x 10H
WREF [90-1]
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
8.3 x 10
-6
6 x 10
-5
NAV
C-VP/S [90-2]
[90-3]
293
-------
90. BUTYL BENZYL PHTHALATE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For
(singlet oxygen),
OF1 hr-1)
(peroxy radical) ,
For
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in
Value
PNES
PNER
PNER
«360
280
79.2 (30°C)
7.92 x 10 (30°C)
water, K (ml cell"1 hr"1) (E) 3 x 10
Data Source
WREF
C-OX
C-OX
[90-4]
[90-4]
HNES
E-KB
E: Estimated value; see List of Source Codes.
[90-1] No temperature is reported with the water solubility.
[90-2] Henry's constant calculated using solubility and vapor
pressure values at unknown temperatures.
294
-------
90. BUTYL BENZYL PHTHALATE
[90-3] The vapor pressure was calculated using Trouton's Rule.
No specific temperature is given.
[90-4] Hydrolysis rate constant is assigned by analogy to di-n-butyl
phthalate.
295
-------
References for 3.7
Jaber, H. 1982. SRI International, unpublished analysis.
Pomona College Medicinal Data Base, June 1982.
Steen, W. C., D. F. Paris and G. L. Baughman. 1979. 177th National
Meeting of American Chemical Society, Honolulu, Hawaii. April.
(ENVR 43)
Verschueren, K. 1977. Handbook of Environmental Data on Organic Chemicals.
Van Norstrand/Reinhold Press, New York. 659 pp.
Wolfe, N. L., D. F. Paris, W. C. Steen, and G. L. Baughman. 1980. Correla-
tion of Microbial Degradation Rates with Chemical Structure. Environ-
mental Sci. Technol. 14:1143-4.
Zepp, R. G. 1980. Private communication.
296
-------
SECTION 3.8 POLYCYCLIC AROMATIC HYDROCARBONS
91. Acenaphthene
92. Acenaphthylene
93. Anthracene
94. Benzo(a)anthracene
95. Benzo(b)fluoranthene
96. Benzo(k)fluoranthene
97. Benzo(ghi)perylene
98. Benzo(a)pyrene
99. Chrysene
100. Dibenzo(a,h)anthracene
101. Fluoranthene
102. Fluorene
103. Indeno(l,2,3-cd)pyrene
104. Naphthalene
105. Phenanthrene
106. Pyrene
297
-------
91. ACENAPHTHENE
CAS No. 83-32-9
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
154.2
96
279
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.42 (25°C)
9.6 x 103
4.6 x 103
1.8 x 10-
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atin m^ mol )
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
9.1 x 10
-5
C-VP/S-25'
1.55 x 10 (25°C) Hoyer & Peperle, 1958
NAV
299
-------
91. ACENAPHTHENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
_ at _ latitude
Oxidation constants at 25°C:
For 62 (singlet oxygen) ,
kox (M-l hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB (M-l hr"1)
For acid-promoted process,
kA (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr-1)
SPEC-ATT [91-1]
(E)5 x 10
-3
< 3600
8 x 10"
(E) 3 x 10
-9
Data Source
UV-ATLAS
E-APAH
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
300
-------
91. ACENAPHTHENE
[91-1] UV spectrum of acenaphthene in heptane solvent is shown
below (UV Atlas, 1966).
1 ' I I
400 500
X (nm)
301
-------
92. ACENAPHTHYLENE
CAS No. 208-96-8
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
152.2
92
265-275
pK-NER
Data Source
WREF
CRC [92-1]
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.93 (25°C)
5.3 x 103
2.5 x 103
1.0 x 10"
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.45 x 10
-3
0.029 (20°C)
NAV
C-VP20°/S25t
WREF
303
-------
92. ACENAPHTHYLENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For Q£ (singlet oxygen),
kQX (M"1 hr'1)
For R02 (peroxy radical),
kQX (M-1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
hr-1)
For acid-promoted process,
kA (M-1 hr-1)
For neutral process,
k, (hr-1)
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
SPEC-ATT [92-2]
(E)5 x 10
-3
x 10
5 x 10"
(E) 3 x 10
-9
Data Source
UV ATLAS
E-APAH
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[92-1] No pressure is reported for the boiling point.
304
-------
92. ACENAPHTHYLENE
[92-2] UV spectrum of acenaphthylene in hexane solvent is
shown below (UV Atlas, 1966).
A (nm)
305
-------
93. ANTHRACENE
CAS No. 120-12-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
178.2
216
226.5 (53mm)
pK-NER
Data Source
WREF
CRC [93-1]
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.045 (25°C)
2.8 x 104
1.4 x 104
4.7 x 10~
May et al, 1978
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
8.6 x 10
-5
C-VP/S-25'
1.7 x 10 (25°C) Jaber, 1982
NAV
307
-------
93. ANTHRACENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
P
winter at 35° latitude 0.15
Oxidation constants at 25° C:
For 102 (singlet oxygen),
ox
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr'1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
DATA-ATT [93-2]
5 x 10
2.2 x 10"
(E) 3 x 10
-9
Data Source
Zepp, 1980
WREF
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[93-1] Compound sublimes at 226.5°C and 53 mm pressure.
308
-------
93. ANTHRACENE
[93-2] Table of absorption coefficients and the corresponding
wavelengths for anthracene is given below (Zepp, 1980).
WAVELENGTH EPSILON
(nm) (M"1 cm"1)
279.50 0.6700E+03
300.00 0.7200E+03
302.50 0.8500E+03
305.00 0.3000E+03
307.50 0.5000E+03
310.00 0.6700E+03
312.50 0.7900E+03
315.00 0.1100E+04
317.50 0.1100E+04
320.00 0.1700E+04
323.10 0.2300E+04
330.00 0.2030E+04
340.00 0.3300E+04
350.00 0.3430E+04
360.00 0.4430E+04
370.00 0.2840E+04
380.00 0.2640E+04
390.00 0.7500E+02
309
-------
94. BENZO[a]ANTHRACENE
CAS No. 56-55-3
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
228.3
155-157
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
5.7 x 10 3
(20°C)
4.1 x 105
2.0 x 105
5.3 x 10
Smith et al, 1978
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1 x 10
-6
C-VP/S-20C
2.2 x 10 (20"C) Hoyer & Peperle, 1958
NAV
311
-------
94. BENZO[a]ANTHRACENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 313 nm
Direct photolysis rate
constant, k (hr"1)
midday P
summer at 4Q° latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
ox
hr~1>
For R02 (peroxy radical) ,
kox Or1 hr"1)
Hydrolysis rate constants:
For base-promoted process,
k.. (M-1 hr'1)
D
For acid-promoted process,
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
DATA-ATT [94-1]
3.3 x 10
-3
1.39
5 x 10
2 x 10
(E)1 x 10
-10
Data Source
Smith et al, 1978
Smith et al, 1978
Smith et al, 1978
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
3i.fi
-------
94. BENZO[a]ANTHRACENE
[94-1] Absorption coefficients and the corresponding wavelengths
for benzo[a]anthracene obtained from work done at SRI
are listed below.
WAVELENGTH
(nm)
297.50
300.00
302.50
305 . 00
307.50
310.00
312.50
315.00
317.50
320.00
323.10
330.00
340.00
350.00
360.00
370.00
380.00
390.00
400.00
410.00
420.00
430.00
440.00
450.00
460.00
470.00
480.00
490.00
500.00
EPSILON
(M-1 cm-1)
0.7930E+04
0.7070E+04
0.5880E+04
0.3790E+04
0.3200E+04
0.3480E+04
0.3900E+04
0.4200E+04
0.4170E+04
0.4120E+04
0.4800E+04
0.5450E+04
0.5390E+04
0.4850E+04
0.3350E+04
0.1560E+04
0.6620E+03
0.4170E+03
0.1720E+02
0.1810E+02
0.1810E+02
0.1360E+02
0.3360E+02
0.1540E+02
0.1180E+02
0.3630E+02
0.8200E+01
0.1800E+01
O.OOOOE+00
313
-------
95. BENZO[b]FLUORANTHENE
CAS No. 205-99-2
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
252.3
167-168
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
0.014 (25°C)
1.15 x 106
5.5 x 105
1.4 x 10"
C-Sw f Row
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
1.22 x 10
-5
5 x 10 7 (20°C)
NAV
C-VP20°/S25'
WREF
315
-------
95. BENZO[b]FLUORANTHENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, <(>,
at nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen),
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB Or1 hr'1)
For acid-promoted process,
k (M-1 hr-1)
A.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, le (ml cell"1 hr"1)
Value
4 x 10
5 x 10"
(E) 3 x 10
-12
Data Source
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
316
-------
96. BENZO[k]FLUORANTHENE
CAS No. 207-08-9
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
252.3
217
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow '
Sediment-water, K (unitless)
oc
Microorganisms-water,
4.3 x 10 3 (25°C) C-Sw f Kow
1.15 x 10
5.5 x 10-
1.4 x 10-
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.87 x 10
-5
5 x 10 7 (20°C)
0.374
C-VP20°/S25t
WREF
C-DC.7
317
-------
96. BENZO[k]FLUORANTHENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, <(>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr~l)
For acid-promoted process,
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell~l hr"1)
4 x 10'
5 x 10-
(E) 3 x 10
-12
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
318
-------
97. BENZO[ghi]PERYLENE
CAS No. 191-24-2
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
276
222
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
„
(unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water,
2.6 x 10 4 (25°C)
3.2 x 106
1.6 x 106
3.5 x 10'
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.44 x 10
-7
,-10
C-VP/S-250
1.03 x 10 (25°C) Murray et al. 1974
NAV
319
-------
97. BENZO[ghi]PERYLENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, (f>,
at _ nm
Direct photolysis rate
constant, k (hr-1)
at
latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
kox (M-l hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k CM"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, le (ml cell"1 hr"1)
Value
<360
<36
(E)3 x 10
-12
Data Source
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
320
-------
98. BENZO[a]PYRENE
CAS No. 50-32-8
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
252
179
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
3.8 x 10 3 (25°C)
1.15 x 106
5.5 x 106
1.4 x 10"
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4.9 x 10
-7
-9
C-VP/S-25'
5.6 x 10 (25°C) Murray et al, 1974
NAV
321
-------
98. BENZO[a]PYRENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, <)>,
at 313 nm
Direct photolysis rate
constant, k (hr"1)
winter, at 40° latitude
midday
Oxidation constants at 25°C:
For 102 (singlet oxygen),
kox (M-1 hr-1)
For R02 (peroxy radical),
kox (>rl hr-1)
Hydrolysis rate constants:
For base-promoted process,
k^ (M-1 hr"1)
D
For acid-promoted process,
k (M-1 hr-1)
A.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr-1)
Value
DATA-ATT [98-1]
!.9 x 10
-4
0.58 [98-2]
5 x 10
2 x 10
(E)3 x 10
-12
Data Source
Smith et al, 1978
Smith et al, 1978
Smith et al, 1978
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
322
-------
98. BENZO[a]PYRENE
[98-1] Absorption coefficients and the corresponding wavelengths
for benzo[a]pyrene were'obtained from work done at SRI
(Smith et al, 1978).
WAVELENGTH EPSILON
(nm) (M"1 cm"1)
297.50 0.4660E+05
300.00 0.2770E+05
302.50 0.1390E+05
305.00 0.6670E+04
307.50 0.4840E+04
310.00 0.3970E+04
312.50 0.3890E+04
315.00 0.3650E+04
317.50 0.3730E+04
320.00 0.3570E+04
323.10 0.3650E+04
330.00 0.5400E+04
340.00 0.8330E+04
350.00 0.1230E+05
360.00 0.1810E+05
370.00 0.1968E4-05
380.00 0.2191E+05
390.00 0.1516E+05
400.00 0.2100E+04
410.00 0.1100E+04
420.00 O.OOOOE+00
[98-2] Photolysis rate constant calculated using SOLAR (see Section
2.3.7).
323
-------
99. CHRYSENE
CAS No. 218-01-9
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
228.3
256
448
pK-NER
Data Source
WREF
CRC [99-1]
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water
1.8 x 10 3 (25°C)
4.1 x 105
2.0 x 105
5.3 x 10
May. 1978
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) °
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
1.05 x 10
-6
C-VP/S-25'
6.3 x 10 (25°C) Hoyer & Peperle. 1958
NAV
325
-------
99. CHRYSENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen),
V Or' hr-1)
For R02 (peroxy radical) ,
kox (M-l hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k. (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
DATA-ATI [99-2]
2.8 x 10
-3
x 10
1 x 10'
Data Source
Zepp, 1980
Zepp &
Schlotzhauer,1979
(E) 1 x 10
-10
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[99-1] No pressure is reported for the boiling point.
326
-------
99. CHRYSENE
[99-2] Table of absorption coefficients and the corresponding
wavelengths of chrysene is given below (Zepp, 1980).
WAVELENGTH EPSILON
(nm) _ (M-1 cm"1)
297.50 0.6160E+04
300.00 0.6080E+04
302.50 0.6900E+04
305.00 0.7720E+04
307.50 0.6960E+04
310.00 0.5160E+04
312.50 0.4760E+04
315.00 0.5810E+04
317.50 0.7100E+04
320.00 0.7000E+04
323.10 0.3600E+04
330.00 0.8740E+03
340.00 0.3230E+03
350.00 0.1960E+03
360.00 0.1940E+03
370.00 0.2400E+02
380.00 0.1300E4-02
327
-------
100. DIBENZO[a.h]ANTHRACENE
CAS No. 53-70-3
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
278.4
270
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
w
(unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
5 x 10 4 (25°C)
6.9 x 10
6
3.3 x 10
6.9 x 10"
WREF
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
7.3 x 10
-8
1 x 10 10 (20°C)
NAV
C-VP20°/S25t
WREF
329
-------
100. DIBENZO[a,h]ANTHRACENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, (J> ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen),
For ROj (peroxy radical) ,
kox (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr"1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"1 hr"1)
SPEC-ATT [100-1]
5 x 10
1.5 x 10
(E) 3 x 10
-12
Data Source
UV-ATLAS
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
330
-------
100. DIBENZO[a,h]ANTHRACENE
[100-1] UV spectrum of dibenzo[a,h]anthracene in heptane solvent
is shown below (UV Atlas, 1966).
X (nm)
331
-------
101. FLUORANTHENE
CAS No. 206-44-0
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
202.3
111
217 (30mm)
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
0.26 (25°C)
7.9 x 1Q4
3.8 x 104
1.2 x 10
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6.5 x 10'
-6
,-6
C-VP/S-25"
5.0 x 10 (25°C) Hoyer & Peperle. 1958
NAV
333
-------
101. FLUORANTHENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 313 _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
kox Or1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
kA (M-1 hr'1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
SPEC-ATT [101-1]
1.2 x 10~4 [101-2]
<3600
<360
(E) 1 x 10
-10
Data Source
UV-ATLAS
Zepp &
Schlotzhauer, 1979
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
334
-------
101. FLUORANTHENE
[101-1] UV spectrum of fluoranthene in methanol solvent is
shown below (UV Atlas, 1966).
X (nm)
[101-2] At 366 nm, the quantum yield is 2 x 10 6.
335
-------
102. FLUORENE
CAS No. 86-73-7
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
116.2
116-117
293-295
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.69 (25°C)
1.5 x 1Q4
7.3 x 103
3.8 x 1(T
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
6.4 x 10
-5
7.1 x 10
-4
NAV
C-VP/S-25'
Irwin, 1982
337
-------
102. FLUORENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, (j>,
at _ nm
Direct photolysis rate
constant, k (hr"1)
at
latitude
Oxidation constants at 25 °C:
For 62 (singlet oxygen) ,
For R02 (peroxy radical) ,
V (M-1 hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, le (ml cell"1 hr"1)
Value
SPEC-ATT [102-1]
<360
3 x 10"
(E) 3 x 10
-9
Data Source
UV-ATLAS
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
338
-------
102. FLUORENE
[102-1] UV spectrum of fluorene in heptane solvent is shown
below (UV Atlas, 1966).
X (nm)
339
-------
103. INDENO[l,2,3-cdlPYRENE
CAS No.
193-39-5
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
276.3
164
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
•„
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
5.3 x 10 4 (25°C)
3.2 x 106
1.6 x 10
6
3.5 x 10'
C-Sw f Kow
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6.95 x 10
-8
1.0 x 10 10 (20°C)
NAV
C-VP20°/S25t
WREF
341
-------
103. INDENO[1.2,3-cd]PYRENE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, $ ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
P
_ at _ latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
k^ (M-1 hr'1)
D
For acid-promoted process,
k (M~! hr-1)
A
For neutral process ,
Biotransformation rate constant:
For bacterial transformation
in water, lo (ml cell"1 hr"1)
5 x 10
2 x 10
(E) 3 x 10
-12
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
342
-------
104. NAPHTHALENE
CAS No. 91-2,0-3
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
128.2
80
218
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
„
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
31.7 (25°C)
1.95 x 103
940
420
May et al, 1978
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 moI"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
4.6 x 10
-4
0.087 (25°C)
NAV
C-VP/S-25'
C-CT/CRC
343
-------
104. NAPHTHALENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 313 nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For 02 (singlet oxygen),
k (M"1 hr"1)
For R02 (peroxy radical),
kQX (M-1 hr'1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k OT1 hr-1)
f\.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k, (ml cell"! hr~^)
DATA-ATT [104-1]
1.5 x 10
-2
<360
<1
(E)l x 10
-7
Data Source
Zepp, 1980
Zepp &
Schlotzhauer, 1979
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
344
-------
104. NAPHTHALENE
[104-1] Table of absorption coefficients and the corresponding
wavelengths for naphthalene is given below (Zepp, 1980)
WAVELENGTH EPSILON
(nm) (M"1 cm"1)
297.50 0.3160E+03
302.50 0.2400E+03
305.00 0.2140E+03
307.50 0.1660E+03
310.00 0.1990E+03
312.50 0.1120E+03
315.00 0.7200E+02
317.50 0.2800E+02
320.00 0.2400E+02
323.10 0.1200E+02
330.00 0.2000E+01
345
-------
105. PHENANTHRENE
CAS No. 85-0108
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
178.2
101
210-215 (12mm)
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water,
1.00 (25°C)
2.8 x 104
1.4
10
4.7 x 10-
May et al, 1978
CC-Kow
C-Koc £ Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
2.26 x 10
-4
C-VP/S-25e
9.6 x 10 (25°C) C-CT/CRC
NAV
347
-------
105. PHENANTHRENE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 3i3 nm
Direct photolysis rate
constant, k (hr"1)
P
at latitude
Oxidation constants at 25°C:
For ^2 (singlet oxygen) ,
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M"1 hr-1)
A
For neutral process,
Biotransf ormation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
Value
DATA-ATT [105-1]
0.01
<360
<36
1.6 x 10
-7
Data Source
Zepp, 1980
Zepp &
Schlotzhauer, 1979
C-OX
C-OX
NHFG
NHFG
NHFG
Paris et al., 1980
E: Estimated value; see List of Source Codes.
348
-------
105. PHENANTHRENE
[105-1] Table of absorption coefficients and the corresponding
wavelengths for phenanthrene is given below (Zepp, 1980)
WAVELENGTH EPSILON
(nm) (ET1 cm"1)
297.50 0.1590E+04
300.00 0.5090E+03
302.50 0.2860E+03
305.00 0.2050E+03
307.50 0.2000E+03
310.00 0.1860E+03
312.50 0.2010E+03
315.00 0.2390E+03
317.50 0.1780E+03
320.00 0.1780E+03
323.10 0.2600E+03
330.00 0.2040E+03
340.00 0.1640E+03
350.00 0.8220E+02
360.00 0.1290E+02
349
-------
106. PYRENE
CAS No. 129-00-0
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
202.3
150
393
pK-NER
Data Source
WREF
CRC
Partition constants:
Water solubility, S
w
(ppm)
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
0.13 (25°C)
8.0 x 104
3.8 x 104
1.2 x 10
May et al. 1978
CC-Kow
C-Koc f Row
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
5.1 x 10
-6
2.5 x 10 6 (25°C)
NAV
C-VP/S-250
Hoyer & Peperle 1958
351
-------
106. PYRENE
TRANSFORMATION DATA
Property or Process
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at 313 _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For ^2 (singlet oxygen) ,
hr-1)
For R0£ (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kfi (tr1 hr-1)
For acid-promoted process,
hr'1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, It (ml cell"1 hr-1)
DATA-ATT [106-1]
2.1 x 10"3 [106-2]
5 x 10
2.2 x 10
(E) 1 x 10
-10
Data Source
Zepp, 1980
Zepp &
Schlotzhauer, 1979
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
352
-------
106. PYRENE
[106-1] Table of absorption coefficients and the corresponding
wavelengths for pyrene is given below (Zepp, 1980).
WAVELENGTH EPSILON
(nm) (M"1 cm-1)
297.50 0.3500E+04
300.00 0.3900E+04
302.50 0.6030E+04
305.00 0.7810E+04
307.50 0.7850E+04
310.00 0.7140E+04
312.50 0.8480E+04
315.00 0.1170E+05
317.50 0.1800E+05
320.00 0.1960E+05
323.10 0.1250E+05
330.00 0.1810E+05
340.00 0.1060E+05
350.00 0.5370E+03
360.00 0.2850E+03
370.00 0.1400E+03
380.00 0.1500E+02
[106-2] At 366 nm, the quantum yield is 2.1 x 10"
353
-------
References for 3.8
Hoyer, H., and W. Peperle. 1958. Dampfdruckmessungen an Organischen
Substanzen and Ihre Sublimationswarmen. Z. Elektrochem. 62:61-66.
Irwin, K. C. 1982. SRI International, Unpublished analysis.
Jaber, H. M. 1982. SRI International, Unpublished analysis.
May, W. E., S. P. Wasik, and D. H. Freeman. 1978. Determination of the
Solubility Behavior of Some Polycyclic Aromatic Hydrocarbons in
Water. Anal. Chem. 50(7):997-1000.
Murray, J. M., R. F. Pottie, and C. Pupp. 1974. The Vapor Pressures
and Enthalpies of Sublimation of Five Polycyclic Aromatic Hydro-
carbons. Can. J. Chem. 52:557-563.
Paris, D. F., W. C. Steen, J. T. Barnett and E. H. Bates. 1980. Kinetics
of Degradation of Xenobiotics by Microorganisms. Paper ENVR-21,
180th National Meeting, American Chemical Society, San Francisco.
August.
Pomona College Medicinal Data Base, June, 1982.
Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T.-W. Chou,
D. C. Bomberger, and T. Mill. 1978. Environmental Pathways of
Selected Chemicals in Freshwater Systems: Part II. Laboratory
Studies. U. S. Environ. Prot. Agency, Environ. Res. Lab. U.S. NTIS,
PB Rep., PB 288 511/AS. 406 pp.
UV Atlas. 1971. UV Atlas of Organic Compounds. Vol. I-V. Plenum Press,
New York.
Zepp, R. G., and P. F. Schlotzhauer. 1979. Photoreactivity of Selected
Aromatic Hydrocarbons in Water. In: Polynuclear Aromatic Hydro-
carbons, P. W. Jones and P. Leber, editors. Ann Arbor Publishers,
Inc., Ann Arbor, MI.
Zepp, R. G. 1980. Private communication.
354
-------
SECTION 3.9. NITROSAMINES AND OTHER NITROGEN-CONTAINING CHEMICALS
107. Dimethyl nitrosamine
108. Diphenyl nitrosamine
109. Di-n-propyl nitrosamine
110. Benzidine
111. 3,3'-Dichlorobenzidine
112. 1,2-Diphenylhydrazine (hydrazobenzene)
113. Acrylonitrile
355
-------
107- DIMETHYL NITROSAMINE
H
H
O
II
N
N
CAS No. 62-75-9
H
H
H
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
74.1
154
pK-NER
Data Source
CRC
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water.
miscible
0.21
0.10
0.11
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) c
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3.3 x 10
-5
8.1 (25°C)
4SIAV
C-VP/S-250 riQ7-11
Chang (1976)
357
-------
107. DIMETHYL NITROSAMINE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, cj>,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 02 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
k (M-1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k~ (ml cell""1 hr"1)
Value
[107-2]
<3600
<3600
(E) 3 x 10
-12
Data Source
WREF
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[107-1] A water solubility value of 6.3 x ID4 ppm, calculated from
Kenaga and Goring's equation, is used in the calculation
of Henry's constant (see Section 4).
[107-2] Although nitrosamines are reported to be unstable to sunlight,
no environmentally relevant and reliable data are available
to estimate photolysis rate constants.
358
-------
108. DIPHENYL NITROSAMINE
CAS No. 86-30-6
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
198.2
67
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water
40 (25°C)
1349
648
426
C-Sw f Kow
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
6.6 x 10
-4
0.1 (25°C)
NAV
C-VP/S-250 [108-11
[108-1]
359
-------
108. DIPHENYL NITROSAMINE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, $ ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25 °C:
For 62 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
kB (M-1 hr'1)
For acid-promoted process,
k (M-1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, K (ml cell"1 hr"1)
see [107-2]
<3600
<3600
(E) 1 x 10
-10
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[108-1] Vapor pressure value was assigned by analogy; no data were
available. This value is used in the calculation of
Henry's constant.
360
-------
CH3 CH2 CH2
109. DI-n-PROPYL NITROSAMINE
CAS No. 621-64-7
O
II
N
N
CH2CH2CH3
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
130.2
205
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
oc
Microorganisms-water
9900 (25°C)
15
9.8
WREF
CC-Kow
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
6.3 x 10
-6
0.4 (37°C)
NAV
C-VP37°/S25° riQ9-l]
[109-1]
361
-------
109. DI-n-PROPYL NITROSAMINE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr"1)
at
Oxidation constants at 25°C:
For 1C>2 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
hr-1)
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k CM"1 hr-1)
A
For neutral process ,
For bacterial transformation
in water, k (ml cell"1 1
Value
latitude see [107-2]
<3600
<3600
Biotransformation rate constant:
i
[) (E) 3 x 10
-12
Data Source
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[109-1] Vapor pressure was calculated using Trouton's rule; this
value was used in the calculation of Henry's constant.
362
-------
110. BENZIDINE
CAS No. 92-87-5
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Data Source
184.2
129
402
4.66. 3.57 [110-1]
WREF
WREF
CRC
Partition constants:
Water solubility, S (ppm)
w
Octanol-water, K (unitless)
ow
Sediment-water, K (unitless)
Microorganisms-water,
400 (12°C)
21.9
10.5
10.1
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
3 x 10
-7
5 x 10
-4
NAV
C-VP-/S120 rilO-21
[110-2]
363
-------
110. BENZIDINE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25°C:
For C>2 (singlet oxygen) ,
kox Of-' hr-1)
For R0£ (peroxy radical) ,
kox (>rl hr"1}
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
kA CM"1 hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr"1)
<4 x 10
1.1 x 10
(E) 1 x 10
-10
C-OX
C-OX
NHFG
NHFG
NHFG
E-KB
E: Estimated value; see List of Source Codes.
[110-1] The two ionization constants are pKal = 4.66 and
pKa2 = 3.57 at 30°C.
[110-2] Vapor pressure was calculated using Trouton's rule; no
temperature was specified. This value was used in the
calculation of Henry's constant.
364
-------
111. 3,3'-DICHLOROBENZIDINE
CAS No. 91-94-1
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
253.1
132
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
4.0 (22°C)
3.236 x IP"
1553
941
WREF
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
v v
8 x 10
-7
1 x 10 5 (22°C)
NAV
C-VP/S-220 [111-11
[111-1]
365
-------
111. 3,3'-DICHLOROBENZIDINE
TRANSFORMATION DATA
Property or Process
Oxidation constants at 25 °C:
For 102 (singlet oxygen) ,
hr-1)
For R02 (peroxy radical) ,
kox (>rl hr"1}
Hydrolysis rate constants:
For base-promoted process,
lc (M-l hr'1)
D
For acid-promoted process,
k (If1 hr-1)
A
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k_ (ml cell"1 hr-1)
Value
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at nm
Direct photolysis rate
constant, k (hr-1)
P
summer at 40° latitude 2.1 x 10
-6
<4 x 10
4 x 10
(E) 3 x 10
-12
Data Source
WREF
c-ox
c-ox
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
[111-1] Vapor pressure value was assigned by analogy; no data were
available. This value was used in the calculation of Henry's
constant.
366
-------
112. 1.2-DIPHENYLHYDRAZINE
CAS No. 122-66-7
PHYSICAL AND TRANSPORT DATA
Property or Process Value
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
184.2
131
pK-NER
Data Source
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
KB /(yg/g)(mg/£)-1\
1.84 x 10'
871
418
286
C-Sw f Row
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1)
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
3.4 x 1Q"9 (25°C)
2.6 x 10~5 (25°C)
NAV
C-VP/S
Jaber, 1981
387
-------
112. 1,2-DIPHENYLHYDRAZINE
TRANSFORMATION DATA
Property or Process
Value
Data Source
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr"1)
_ at _ latitude
Oxidation constants at 25°C:
For 102 (singlet oxygen),
For R02 (peroxy radical) ,
Hydrolysis rate constants:
For base-promoted process,
hr'1)
For acid-promoted process,
hr-1)
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, k (ml cell"1 hr"1)
<4 x 10
1 x 10'
)l x 10
-10
C-OX
C-OX
HNES
HNES
HNES
E-KB
E: Estimated value; see List of Source Codes.
368
-------
113. ACRYLONITRILE
CAS No. 107-13-1
H\
H/
C = C
H
N
PHYSICAL AND TRANSPORT DATA
Property or Process
Molecular weight
Melting point, °C
Boiling point, °C
lonization constant
Value
53.1
-83.5
78.5
pK-NER
Data Source
CRC
WREF
Partition constants:
Water solubility, S
Octanol-water, K
ow
w (ppm)
(unitless)
Sediment-water, K (unitless)
oc
Microorganisms-water,
7.9 x'lO (25°C)
1.78
0.85
1.04
Klein et al, 1957
Pomona
C-Koc f Kow
C-KB f Kow
Volatilization constants:
Henry's constant, H
(atm m3 mol"1) C
Vapor pressure, P (torr)
Reaeration rate ratio,
kc/k°
8.8 x 10
-5
100 (22.8°C)
NAV
C-VP22.8°/S25t
WREF
369
-------
113. ACRYLONITRILE
TRANSFORMATION DATA
Property or Process
Photolysis data:
Absorption spectrum
Reaction quantum yield, ,
at _ nm
Direct photolysis rate
constant, k (hr-1)
P
_ at _ latitude
Oxidation constants at 25 °C:
For 1C>2 (singlet oxygen) ,
ox
hr~1}
For R02 (peroxy radical) ,
kox (M-1 hr"1}
Hydrolysis rate constants:
For base-promoted process,
For acid-promoted process,
k (M-1 hr-1)
J\.
For neutral process,
Biotransformation rate constant:
For bacterial transformation
in water, Ic (ml cell"1 hr"1)
Value
PNES
PNER
PNER
x 10
36
(E) 3 x 10
-9
E: Estimated value; see List of Source Codes.
Data Source
WREF
C-OX
C-OX
HNES
HNES
HNES
E-KB
370
-------
References for 3.9
Chang, E. T. 1976. Vapor Pressure of N-Nitrosodimethylamine. NTIS
AD-A021 064/1ST Space and Missile Systems Organization, Zir Force
Systems Command. Los Angeles, CA.
Jaber, H. M. 1981. Unpublished work at SRI.
Klein, E., J. W. Weaver, and B. G. Webre. 1957. Solubility of Acryloni-
trile in Aqueous Bases and Alkali Salts. Chem. Eng. Data Ser. 2:72-75.
Pomona College Medicinal Data Base, June 1982.
371
-------
Section 4
CALCULATION OF PARTITION COEFFICIENTS OF
ORGANIC CHEMICALS IN AQUATIC ENVIRONMENTS
4.1 BACKGROUND
The partitioning of a chemical between water and sediment and between
water and biota will affect the concentration of the chemical in water
and the rate of loss of the chemical from aquatic systems (See Section 2.1).
Solubility data, on the other hand, are required for calculation of Henry's
constants, which are needed to calculate volatilization rates of chemicals
in aquatic systems (see Section 5.2.2).
This section discusses the relationships between water solubility,
the partition coefficients for a chemical between sediment and biota, and
the partition coefficient for a chemical between octanol and water.
Moreover, the theoretical basis for such relationships is explained, and
some of the published correlations for these data are discussed. This
section also briefly discusses the calculation of the octanol-water
partition coefficient data used to calculate many of the other partitioning
constants. The data for the four partitioning constants (including water
solubility) are given for 114 individual organic chemicals in Section 3.
As discussed in Section 2.2, the partioning of a chemical is given
by the equation
KP = CP/Cw (A.D
where C and C are the concentrations on a particulate material (sediment
p w
or biota) and in water, respectively, and K is the partitioning constant
(or coefficient) whose units are determined by those of C and C (see.
Section 2.2). In practice, C is usually defined as the amount of chemical
per dry weight of sediment (.or organisms) to correct for the variability
of the particulate water content. The partition coefficient between
373
-------
microorganism and water, K , given for individual organic chemicals in
Section 3, is in units of micrograms of chemical per gram of microorganism
divided by grams of chemical per liter of water. Because the amount of
organic chemical sorbed to sediments has been found to depend on the
amount of organic carbon in the sediment, it is useful to normalize a
measured sediment partition coefficient (K ) for organic carbon content:
K = K /f (4.2)
oc p oc
where f is the fraction of organic carbon and K is the normalized
(for organic carbon content) partition coefficient. Karickhoff et al.
(1979) have also shown that, because f varies with sediment particle
size, the distribution of sediment particle Size will markedly affect
measured K values.
oc
The octanol-water partion coefficient K has commonly been used
ow
as a measure of the hydrophobicity of a chemical in medical and toxico-
logical applications as well as in environmental chemistry (Hansch and
Leo, 1979; Kenaga and Goring, 1978). A large number of K values is
ow
therefore available as a result of the number of uses of such data. Most
significantly; K values can be calculated from molecular structure (.see
Section 4.4). The K data in Section 3 are given to allow calculations
of other properties (partitioning coefficients for biota as well as toxi-
cological data) for use in environmental assessments of the organic
priority pollutants.
4.2 CALCULATION METHODS
Several correlation equations have been proposed to calculate the
water solubility (S ), K , and 1C from K values and to calculate K
values from water solubility. The more widely used of these equations
are discussed and analyzed in Section 4.3. Although we recognize that
better equations are evolving as more experimental data are obtained,
the following equations are recommended for use in environmental fate
assessments.
374
-------
4.2.1 Correlation Equations
In the following equations, all partition coefficients (K , K and
Vare unitless, and water solubility (S ) is in units of parts per million
* w
(ppm). As discussed in Section 4.2.2, however, the solubility units of
molarity (moles per liter) or mole fraction are preferred.
K and K are correlated by the following equation (Karickhoff, 1979):
log K =1.00 log K - 0.21 C4 3)
6 oc 6 ow \t-JJ
Correlation of S and K was reported by Yalkowsky and Valvani (1980)-
For organic pollutants that are liquid in their pure state at 25°C:
log S = -1.08 log K + 3.70 + log MW (4.4)
w ow
where MW is the molecular weight of the pollutant (g mole ). For organic
pollutants that are solid in their pure state at 25°C:
/ASF
$.70 + log MW-VY^
log Sw = -1.08 log KQW + 3.70 + log MW-l^pj^ (mp-25) (4.5)
where mp is the melting point of the pollutant (°C) and ASf is the entropy
of fusion of the pollutant (cal mol deg ). If ASf is not known, it
may be approximated by (Yalkowsky and Valvani, 1980):
ASf ~ 13.6 + 2.5 (n - 5) (4-6)
where n is the number flexible atoms (i.e., atoms not involved in double
bonds, triple bonds, or part of a ring structure) in the pollutant molecule,
other than hydrogen. If n is less than 5, (n - 5) is set equal to zero.
The original equations in the literature are different if they were
reported in different solubility units. Refer to Section 4.2.2 for
the appropriate solubility units conversion factors.
375
-------
Correlation of K and S is provided by (Kenaga and Goring, 1978):
oc w
log K = -0.55 log S + 3.64 (4.7)
oc w
can be correlated with K by
ow
K_ = 0.16 K (4.8)
B ow
4.2.2 Units and Conversion Factors
Three commonly used units of aqueous solubility are defined below:
(.1) Mole fraction, x, the unitless ratio of the number of moles of
solute to the total number of moles of solute plus water. In
symbols, for a binary solution of n moles of solute in n moles
of water
x = n/ (n + n )
w
~- n/n for n » n (4.9)
w w
(2) Molarity, S, expressed in moles of solute per liter of solution
(M):
S(M) = n(mol) /liter of solution (4.10)
(.3) Weight fraction, expressed in milligrams of solute per liter of
water, or parts per million, ppm
S (ppm) • n
-------
or
s =
/ N
(1 - x)
^ 55.5 x for x < 10
2
(4.13)
To convert from molarity to ppm is straightforward by substituting
Equation (4.10) into equation (4.11)
ppm - S(MW) (1000) for S < 1 M
(4.14)
Thus to convert from mole fractions to ppm follows from equations
(4.11) and (4.13)
ppm = ,?5'5..*, (MW) (1000)
(1 - x )
~55.5(x) (MW) (1000) for x < 10
These conversion factors are summarized in Table 4.1.
-2
(.4-15)
Table 4.1
CONVERSION FACTORS FOR COMPOSITION UNITS
FROM
ppm
(mole fraction)
M
(Molarity)
TO
ppm
(mole fraction)
M
(Molarity)
5.55 x 104(MW)
(MW) (103)
1.80 x 10 5
MW
—
1
55.5
10~3
MW
55.5
377
-------
Concentration in aqueous solution is preferably given in mole fraction
or molarity units since these units are measures of the amount of solute
per amount of solution. The weight fraction or ppm, on the other hand,
expresses the weight of solute per weight of solution and is thus a
function of the molecular weight of the molecule, which is not relevant
to environmental or toxicological effects.
4.3 CALCULATION OF K and S FROM K
OC W OW
The sediment partition coefficient, normalized for organic carbon
content (K ), and aqueous solubility (S ) of an organic pollutant are
critical to its environmental fate. Because K and S values may be
oc w J
unmeasured or unreliable, it is important to be able to correlate these
environmental parameters with other experimental quantitites, namely, to
predict unmeasured values and appraise the reliability of measured values.
It is useful to correlate these parameters with octanol/water
partition coefficients (K ) for practical as well as theoretical reasons.
Practically, K values are easier to measure and, where K measurements
have not been made, calculated values may be used with confidence. The
theoretical basis for expecting correlations of K and S with K is
oc w ow
described below. The correlation of K with other partitioning constants
is not discussed in this section since a recent review of the subject is
available.
4.3.1 Partitioning Thermodynamics
This discussion first considers the partitioning of a chemical
between octanol and water, with octanol being a representative organic
phase. If a small amount of a chemical is added to a closed vessel
containing n-octanol and water, the vessel is shaken, and the octanol
and water are allowed to separate, the chemical will partition between
the two phases (see Figure 4.1). By convention, the small amount of
chemical in each phase is called the solute. The partitioning of the
solute molecules between the two phases can be understood in terms of a
simple lattice model. If we assume that every molecule (water, octanol,
378
-------
CO
-a
co
O
w w w w w w w
w w w w s w w
w w w w w w w
w w w w w w w
SA-6729-8
FIGURE 4.1 LATTICE MODEL OF A SOLUTE (S)
PARTITIONING BETWEEN OCTANOL
(0) AND WATER (W) PHASES
Kow =
= 2
s
0
0
w
w
w
w
0 0
0 0
S 0
WWW
w s w
WWW
WWW
s o
0 0
0 S
WWW
WWW
WWW
w s . w
SA-6729-9
FIGURE 4.2 LATTICE MODEL OF A HIGHER MOLE
FRACTION OF SOLUTE (S) PARTITIONING
BETWEEN OCTANOL (O) AND WATER
(W) PHASES
Because the environment of each solute mole-
cule is the same, KQ
Figure 4.1.
Co/Cw = 2 as in
-------
and solute) in both phases occupies a particular site on a three-dimensional
lattice, with uniform spacing between sites, then the fraction of sites
in each phase occupied by the chemical is the mole fraction x. A two-
dimensional cross section of this lattice is shown in Figures 4.1 and
4.2.
The tendency for a solute molecule to leave either phase is propor-
tional to the solute mole fraction in that phase and to the forces acting
on the solute in that phase. The forces acting on a solute molecule will
depend on which molecules occupy neighboring sites on the lattice.
Figures 4.1 and 4.2 show that, over the mole fraction range of x = 1/28
to x = 1/14, solute molecules in the water phase are surrounded by water
w
molecules. Thus, the forces acting on the solute in the water phase are
independent of the solute mole fraction. Consequently, the tendency (f)
of a solute molecule to leave the water phase is directly proportional
to its mole fraction:
f = Hx (4.16)
where H is a constant representing the forces exerted on the solute by
the solvent. At higher solute mole fractions, where solute-solute inter-
actions become important (that is, where the solute is concentrated
enough that solute molecules occupy neighboring lattice sites), H becomes
a function [H(x)] of the solute mole fraction, and thus f is no longer
directly proportional to x:
f = H(x) x (4.17)
The partitioning of the chemical between the octanol and water phases
depends on this relative tendency of the chemical to leave each phase (f),
which is conveniently viewed as a force per unit area. In thermodynamics,
*
f is called the fugacity and, as explained above, is proportional to the
relative amount of the solute in the phase, x, and the forces acting on
the solute within each phase; explicitly.
See, for example, G. L. Lewis and M. Randall, Thermodynamics, revised
by K. S. Pitzer and L. Brewer (McGraw-Hill, NY, 1961).
380
-------
fw - (fV Xw <
fo = (f\) xo (4.19)
where subscripts w and o refer, respectively, to the water and octanol
n
phases, and f and y. are, respectively, the reference fugacity and
activity coefficient, which together represent the forces acting on the
solute in the i phase. At equilibrium
fw=fo
so that
.R
f Y Y
W W
In general, at constant pressure, f depends only on the temperature and
y. depends on the composition as well as the temperature of the i phase.
In sufficiently dilute solutions, however, the forces acting on a solute
molecule will be independent of x. because, as explained above, the
•p
environment of a solute molecule will remain constant. Thus (f Y.) will
be a function only of temperature
(fRYl) = H± (4.22)
where H. is the Henry's constant for a very dilute solution of the solute
in phase i. Thus
xo/Xw=Hw/Ho <
is a function only of temperature. However, if x or x is large enough
that Y or Y is not constant, then K will also no longer be constant.
381
-------
Because composition is commonly measured in moles liter (M), it
is convenient to define:
K = C /C = r (x /x ) = r (H /H ) (4.25)
ow o w wo o w wo wo
where r is a constant equal to.the ratio of the molar volume of water
wo n
r = v /v (= 0.115) (4.26)
wo wo
to that of octanol. (In terms of the lattice mode, r is equal to the
wo ^
ratio of the number of sites per unit volume of octanol to that of water.)
Numerous workers have correlated the partitioning of chemicals be-
tween sediment and water and between biota and water with octanol/water
partition coefficients. Before discussing these specific correlations
in detail, it is useful to understand the conditions that must be met
for these correlations to be successful.
Partitioning of a solute between water and any other water immiscible
phase p (i.e., biota, sediment) may be described by
K = r (H /H ) (4.27)
pw wp w p '
From equation (4.25) for partitioning between octanol and water
H = K H /r (4.28)
w ow o wo
thus
K = (r /r )(H /H )K = r (H /H )K (4.29)
pw wp wo op ow op o p ow
where r is the ratio of the molar volume of octanol to that of phase
op
p. Thus, taking the logarithm of both sides of equation (.4.29)
382
-------
log K = log K + log (r H /H ) (4.30)
6 pw 6 ow B op o p
Thus, for the second term on the right-hand side of equation (4.30) to
remain constant for a set of chemicals partitioning between water-octanol
and water-phase p, phase p must be chemically similar to octanol and both
K and K must be measured at low enough solute concentrations that
ow pw &
solute-solute interactions are absent.
The success of K -K correlations (to be discussed in detail below),
ow oc
for example, may thus be understood. First, by normalizing adsorption
for organic carbon content, we ensure the chemical similarity of phase p
(.that is, the organic content) and octanol. Second, the partitioning of
the chemical between the water and sediment phases is usually measured
at very low surface coverage (in the linear region of the adsorption
isotherm) where adsorbate-adsorbate interactions are minimal.
Octanol/water partition coefficients have been used not only to
correlate other partitioning data, but also to predict aqueous solubili-
ties. The assumptions implicit in these predictions become apparent
on close examination of the octanol/water partition experiment.
If it is assumed that the ratio of the number of solute molecules
in each phase remains constant up to the limit of solubility, then
Kow = (Co/Cw) dilute = ^Wsaturated (.4.31)
From equation (4.21), this means that the ratio of activity coefficients
y /Y remains constant up to saturation. As explained above, however,
wo ^
the ratio y /Y will depend on solute concentration, particularly if
X O
C (saturated) is large enough that solute-solute interactions become
w
*Because of the chemical similarity of a neutral organic solute with
n-octanol, it is expected that y will not vary significantly with
383
-------
important. Furthermore, if we assume that the solubility of the chemical
in pure water equals its solubility in the octanol-saturated water phase
of the partition measurement, then
K = S /S (4.32)
ow o w v '
where S and S are solubilities in moles liter (M) in pure octanol and
o w
pure water, respectively.
To correlate aqueous solubility with K , many authors have proposed
an equation of the form:
log S = -(I/a) log K + c (4.33)
w ' ow
where a and c are constants. Equation (4.33) may be derived by modifying
equation (4.32) to account for deviations of real systems from model be-
havior:
K = (S /S )a (4.34)
ow o w
This equation is clearly identical to equation (4.32) for a = 1. Taking
the logarithm of both sides of equation (4.34) and rearranging terms:
log S = - (I/a) log K + (I/a) log S (4.35)
w ow o
If S is assumed constant for a set of solutes in octanol, equation
o
(4.35)becomes
log S = - (I/a) log KQW + c (4.36)
and the correlation coefficients a and c may be calculated from a plot
of known values of log S versus known values of log K for the given
w ow
384
-------
set of solutes. Clearly, if the assumptions implicit in equation (.4.32)
are reasonable, the calculated value of a. should be close to one.
The variability of S for a set of solutes is difficult to quantify
except by comparing liquid and solid solutes. If two solutes are identi-
cal except that one is a liquid and the other is a solid in its pure state
at temperature T, the solid will be less soluble than the liquid because
of the additional energy required to remove solute molecules from the
solid phase. Thus, if we assume that all liquid solutes have the same
solubilities in n-octanol, and we use this pure liquid solute as the ref^-
erence state, calculated solid solubilities must be corrected for the
energy necessary to transform the solid to the liquid state. This energy
is called the enthalpy of fusion, and from simple thermodynamic argu-
ments, we can modify equation (.4.35) for solid solutes:
&Ef Tf- T
log Sw = - (I/a) log KQW f c - (I/a) -^ (4.37)
where AH is the enthalpy of fusion, R is the gas constant, and T is
the melting temperature of the solute. At the melting point,
AHf - Tf ASf (A.38)
Therefore at 25°C, equation (.4.38) becomes
AS
log S = - (I/a) log K + c - nmfim Cmp-25) (.4.39)
where mp is the melting point (in °C) and AS is the entropy of fusion
-1 -1
(in cal deg mole ). This correction is zero for solutes that are
liquid at 25°C, but substantial for solutes with high melting points.
Assuming that the theory is approximately correct and the correlation
coefficient a. is approximately equal to one, Table 4.2 and Figure 4.3
illustrate the magnitude of this correction as a function of melting
point for a hypothetical solute with an uncorrected solubility of 100 ppm
and a typical entropy of fusion of 13.6 entropy units (cal deg mol ).
385
-------
Table 4.2
EFFECT OF MELTING POINT CORRECTION
ON WATER SOLUBILITY VALUES
Solubility . . Solubility*
(uncorrected) Melting Point (corrected)
(ppm) (°C) (ppm)
100 25 100
100 50 56
100 100 18
100 200 2
100 300 0.2
log S (.corrected) = log S Cuncorrected) - 0.01 (mp-25) at 25°C,
where AS = 13.6 and a = 1 are assumed in equation (4.39) and S
f w
is the water solubility in ppm.
386
-------
f 0.6 -
f = S... (corrected )/Sw( unconnected)
w
w'
f = lo-(0.01)(mp-25)
-50
50 100 150 200 250
MELTING TEMPERATURE (°C)
300 350
SA-6729-10
FIGURE 4.3 ENTHALPY OF FUSION CORRECTION FACTOR FOR AQUEOUS SOLUBILITY
AT 25°C AS A FUNCTION OF MELTING TEMPERATURE
387
-------
4.3.2 Comparison of Reported Correlations
Table 4.3 lists a representative sample of recently published
correlations among K , K , S . This section examines these correla-
ow oc w
tions in detail.
K -K . As discussed earlier, the sorption constant K is the
oc ow f oc
amount of chemical adsorbed per unit weight of organic carbon in the
sediment divided by the equilibrium concentration of the chemical in
the water phase. This constant is useful because, once K has been
^ oc
determined for a chemical, the sorption partition coefficient may be
calculated if the fraction organic content (f ) is known:
oc
K = K (f , = C /C (4.40)
p oc oc) s w
where
K = Sorption partition coefficient
P
K = Sorption partition coefficient normalized for organic carbon
oc
content
f = Fraction of organic content in the sediment (0 < OC <1)
oc
C = Concentration of the adsorbed chemical
s
C = Equilibrium solution concentration.
w
Furthermore, it is useful to be able to predict K values from
oc
the more easily measured K values. The theoretical basis for expect-
ow
ing good K -K correlations has been discussed above. Two recent
oc ow
K -K correlations that have appeared in the literature are listed in
oc ow
Table 4.3. The significantly different correlation equations of Kenaga
and Goring (1978) and Karickhoff et al. (1979) probably reflect the
different data bases used to correlate K with K
oc ow
388
-------
Table 4.3
REPORTED CORRELATIONS OF K , K AND S
ow oc w
Correlation
K - K
oc ow
W
00
K - K
oc ow
S - K
w ow
Equation
log K = 0.54A log K + 1.377
° oc B ow
log K = 1.00 log K - 0.21
oc ow
- 0.922 log K +4.184
ow
S in ppm
w
Data Base
Authors
(4.41) Pollutants
(4.3)
Aromatic hydrocarbons (8)
Carboxylic acids and esters (5)
Phosphorus containing insecticides (5)
Ureas and uracils (7)
Symmetrical triazines (6)
Miscellaneous (14)
Adsorbents
Variety of soils
Pollutants
Polycyclic aromatics (8)
Chlorinated hydrocarbons (2)
(4.42) Substituted benzenes and halobenzenes (12)
Halogenated biphenyls and diphenyl oxides (11)
Aromatic hydrocarbons (9)
Phosphorus containing insecticides (16)
Carboxylic acids and esters (9)
Ureas and uracils (7)
Miscellaneous (24)
Kenaga and Goring (1978)
Karickhoff et al. (1979)
Kenaga and Goring (1978)
S - K
w ow
log x = - 1.08 log K - 1.04
(mp - 25)
1360
x is the mole fraction solubility at 25 C
s
AS is the entropy of fusion in cal deg mol
mp is the melting point in °C (if mp < 25
then the term in brackets is zero)
(4.43) Simple aliphatics and aromatics
in the following groups (n = 114)
Alcohols
Halogens
Amines
Carboxylic acids and esters
Aldehydes and ketones
Ethers
Nitro compounds
Yalkowsky (1980)
Number in parentheses refer to the number of pollutants in the data base.
-------
in ppm
Table A.3 (continued)
REPORTED CORRELATIONS OF K , K AND S
ow oc w
Correlation
K - S
oc w
Equation
log K = - 0.55 log S + 3.64
oc w
Eg.
Data Base
(4.7) Similar to data base for equation (4.41)
Authors
Kenaga and Goring (1978)
K - S log K = - 0.56 log S + 0.70
oc w om w
log K = - 0.56 log S + 0.93
(4.45)
O)
(4.44) Pollutants
Polychlorinated biphenyls (3)
Pesticides (4)
Halogenated ethanes and propanes (6)
Tetrachloroethene
1 , 2-Dichlorobenzene
Adsorbents
Willamette silt loam
Miscellaneous other soils
Chiou et al. (1979)
K - S log K = - 0.54 log x + 0.44
OC W OC S
(4.46) Similar to data base for equation (4.3)
Karickhoff (1979)
x in the mole fraction solubility
s
K is the sorption partition coefficient normalized for organic matter reported by
Chiou et al. (1979). Assuming K = 1.7 K , equation (4.45) is derived.
a om
-------
The theoretical equation of Table 4.4,
log K = 1.00 log K + constant (.4.47)
follows from assuming that the second term on the right-hand side of
equation (4.30) is constant; the data base required for a good fit with
equation (4.47) follows from the assumptions used in the derivation of
equation (4.30). It is clear from Table 4.4 that the data base and
correlation equation of Karickhoff et al. (1979) closely conform with
the theoretical model; however, the data base and correlation equation
of Kenaga and Goring (1978) do not.
The advantages and disadvantages of using these alternative equa-
tions are not as well defined, however. Although the equation of
Karickhoff et al. (.1979) conforms to a simple model and accurately pre-
dicts sorption coefficients from K data for a limited class of organic
ow
chemicals, it has not been widely tested and may be highly inaccurate
for a more universal set of pollutants and soil/sediments. The equation
of Kenaga and Goring (1978), however, is strictly empirical and only
roughly predicts K values from K data, but it is applicable to a
o c ow
more universal set of pollutant/adsorbent systems because of the data
base used. When more precise K and K data are available, it will
oc ow
be of interest to assess the predictive value of both of these correla-
tions for both the universal set and individual classes of pollutant/
adsorbent systems. It may become apparent that several correlation
equations may be required to adequately predict K values from K
values for the variety of systems of interest.
S - K •. Several comparisons of the equations of Kenaga and Goring
w ow
(1978) and Yalkowsky (1980) can be made. For reasons discussed earlier,
the mole fraction units of solubility used by Yalkowsky are to be pre-
ferred to the ppm units used by Kenaga and Goring. In fact, to compare
equation (4.42) of Kenaga and Goring with equation (4.43) of Yalkowsky,
we must assume an average molecular weight for the chemicals in the data
391
-------
Table 4.4
DATA BASES FOR K -K CORRELATIONS
oc ow
Kenaga and Goring (1978)
Karickhoff et al. (1979)
Theoretical
log K
oc
K
ow
0.54 log K + 1.38
& ow
Measured and calculated
values compiled from
literature
1.00 log K - 0.21
ow
Measured by Karickhoff
et al.
1.00 log K + constant
0 ow
Measured for very
dilute solution
CO
CO
to
K
oc
Calculated average values
for each chemical from
adsorption coefficients
for widely differing soils
Measured values for the
silt (high organic content)
fractions of two natural
sediments
Uniform organic content
of soil/sediment. Mea-
sured for adsorption
from very dilute solutions
Chemicals
Very wide range of
organic classes
Nonpolar or slightly
polar organics
Nonpolar organics
-------
base of Kenaga and Goring. Converting equation (4.42) from ppm to mole
fractions units
log x = - 0.922 log K - 0.56 - log MW (4.48)
S OW
where x is the mole fraction solubility and MW is the average molecular
S
weight.
The variation of equation (4.48) with MW is shown in Figure 4.4
and compared with Yalkowsky's equation for liquid solutes. Two observa-
tions can be made about Figure 4.4. First, the molecular weight depen-
dence of equation (4.48) is not very great for chemicals in the molecular
weight range of 100-400. Second, because the average molecular weight
of chemicals in the data base used to determine equation (4.48) is in
the range of 100-400, it is clear that solubilities predicted by equation
(4.48) will be approximately an order of magnitude lower than those
predicted by equation (4.43).
A comparison of measured solubilities (in molarity units, M) with
those predicted by the equations of Kenaga and Goring and of Yalkowsky
is shown in Table 4.5 for a series of chlorinated methanes and ethanes.
Note that all the chemicals listed in Table 4.5 (except hexachloroethane,
which sublimes) are liquid at 25 C. Furthermore, is is clear from
Table 4.5 that equation (4.43) of Yalkowsky predicts the aqueous solu-
bility of chlorinated methanes and ethanes very accurately, whereas the
corresponding prediction of equation (4.42) is an order of magnitude
lower. Table 4.6, which compares calculated and measured solubilities
for some low melting point aromatics, further supports these conclusions.
The cause of this discrepancy becomes clear when we examine the con-
trasting methods and data bases used by Kenaga and Goring and by Yalkowsky
to develop their correlations. Kenaga and Goring empirically correlated
K with the solubility of a set of chemicals, most of which are solid
ow J
at 25°C. In other words, Kenaga and Goring implicitly used a solid
solute reference state; consequently, their correlation equation cannot
accurately predict the solubility of a chemical that is liquid at 25 C.
393
-------
-2
-3
-5
-7
-8
Kenaga and Goring
(log xs = -0.922 log Kow -0.56 - log MW)
Yalkowsky
(log xs =-1.08 log Kow -1.04}
xs = Mole Fraction Solubility
MW = Molecular Weight
MW = 10
MW = 100
MW = 200
MW = 400
I
1
log K
ow
SA-6729-11
FIGURE 4.4 COMPARISON OF SOLUBILITY Kow EQUATIONS FOR LIQUID SOLUTES
394
-------
Table 4.5
CALCULATED VERSUS MEASURED SOLUBILITIES FOR CHLORINATED METHANES AND ETHANES
log S
to
01
Chloromethane
Dichloromethane
Chloroethane
1,1-Dichloroethane
Trichloromethane
1,1.2-Trichloroethane
1,1,1-Trichloroethane
1,1,2,2-Tetrachloroethane
Tetrachloromethane
Hexachloroethane
mp
w
-LUti JN.
OW
0.95
1.26
1.49
1.80
1.96
2.07
2.50
2.66
2.96
4.62
(uc)
-98
-95
-136
-97
-64
-37
-30
-36
-23
Sublimes
Kenaga and Goring
-1.4
-1.87
-2.03
-2.45
-2.67
-2.84
-3.25
-3.48
-3.70
-5.45
Yalkowsky
-0.32
-0.66
-0.91
-1.24
-1.41
-1.53
-2.00
-2.17
-2.49
-4.29
Measured
-0.89
-0.80
-1.05
-1.25
-1.16
-1.47
-2.27
-1.76
-2.29
-3.68
Sources for these measured values are given on the data sheet for each chemical
(see Section 3).
-------
Yalkowsky, on the other hand, explicitly used a liquid solute reference
state. To calculate the solubilities of chemicals that are solid at
25 C, Yalkowsky included an entropy of melting correction term. Thus
the equation of Yalkowsky, assuming accurate known values of the entropy
of fusion (AS,) and melting point (T ), is equally valid for liquid
and solid solutes.
As discussed earlier, if two solutes are identical except that one
is a liquid and the other is a solid in its pure state at 25 C, then the
solid will be less soluble than the liquid by a factor of
exp [-2.303CAS /1360)(mp-25)] (4.49)
where AS is the entropy of fusion and mp is the melting point ( C).
If AS is constant, then it is clear from equation (4.46) that solu-
bility decreases as the melting point increases. Assuming ASf = 13.6
entropy units and converting mole fraction solubilities to molarity
units, Figure 4.5 illustrates that equation (4.43) of Yalkowsky, in
contrast with equation (.4.42) of Kenaga and Goring, successfully predicts
the decrease in solubility with increase in melting point for a-, g-,
&-, and y-BHC.
Figure 4.5 also indicates that implicit in equation (4.42) of
Kenaga and Goring is an empirical average of the solid solute correction
term. Because the solubilities of liquid solutes predicted by equation
C4.42) are approximately an order of magnitude lower than measured values,
we can assume that this average correction term is approximately equal
to 0.10, which is the dashed line in Figure 4.3. Thus, the predicted
solubilities of equation C4.42) should approximate those of Yalkowsky
and measured values for solutes with melting points in the 100 to 200 C
temperature range. Figure 4.6 illustrates, in fact, that for solutes
with an approximate molecular weight of 150, an entropy of fusion of
13.6 and a melting point of 125 C, the correlation equations of Yalkowsky
and of Kenaga and Goring are similar. Moreover, Table 4.7 illustrates
396
-------
Table 4.6
CALCULATED VERSUS MEASURED SOLUBILITIES FOR LOW MELTING POINT AROMATICS
w
CO
mp
log S
w
Nitrobenzene
Benzene
Toluene
Chlorobenzene
Ethylbenzene
1 , 2-Dichlorobenzene
-Log *•
6 ow
1.87
2.13
2.79
2.84
3.34
3.56
( c)
5.6
5.5
-95
-45
-94.9
-17
Kenaga and Goring
-2.63
-2.63
-3.35
-3.48
-3.92
-4.26
Yalkowsky
-1.32
-1.60
-2.31
-2.37
-2.90
-3.14
Measured'
-1.82
-1.64
-2.24
-2.37
-2.85
-3.00
Sources for measured values are given on data sheet for each chemical
(see Section 3)
-------
-2.0
-3.0
~ -4.0
en
5 -5.0
-6.0
-7.0
0
Yalkowsky
Kenaga and Goring
Measured
5 - BHC
7 - BHC
0-BHC -
I I
I
50 100 150 200 250
MELTING TEMPERATURE (°C)
300 350
SA-6729-12
FIGURE 4.5 SOLUBILITIES OF HEXACHLOROCYCLOHEXANES (a-, 0-, 6-, 7-BHC)
AS A FUNCTION OF MELTING TEMPERATURE
398
-------
-3
-4 -
-5
en
O
-7
> Kenaga and Goring
- log xs = -0.922 log Kow -0.56 - log MW
MW = 150
Yalkowsky
log xs = -1.08 log Kow -1.04 -[(mp - 25)ASf/1360]
ASf = 13.6 mp = 125°C
I I I I I
1
3
log Kow
6
SA-6729-13
FIGURE 4.6 COMPARISON OF SOLUBILITY - KQW EQUATIONS FOR SOLID SOLUTES
399
-------
o
o
Table 4.7
CALCULATED VERSUS MEASURED SOLUBILITIES FOR SELECTED PESTICIDES
log K
ow
Lindane
Aldrin
Chlordane
ODD
DDT
3.
5.
5.
6.
6.
89
30
48
20
91
MP
(°C) I
113
104
108
112
109
log Sw (M)
Cenaga and Goring
-4.
-6.
-6.
-7.
-7.
85
24
46
04
74
Yalkowsky
-4.
-5.
-6.
-6.
-7.
38
80
04
85
59
Measured
-4
-6
-5
-6
-6
.40
.30
.30
.5
.6
to
to
to
to
to
Sources of measured values are given on the data sheets for each chemical
(_see Section 3).
-------
that for selected pesticides with melting points around 110 C the cor-
relations of Yalkowsky and of Kenaga and Goring compare equally well
with measured values.
Figure 4.5 also suggests that solubilities predicted from equation
(.4.42) of Kenaga and Goring will become progressively higher relative
to measured values as the melting temperature increases above 200 C.
Table 4.8 indicates that, indeed, measured solubilities of chemicals
with melting points above 200 C systematically fall below those pre-
dicted by Kenaga and Goring.
In summary, equation (.4.42) of Kenaga and Goring should be re-
stricted to chemicals with melting points in the 100 to 200 C range,
but equation (4.43) of Yalkowsky, because it includes a melting point
correction factor is not limited by melting point restrictions.
K - S . To compare equation (4.7) with equations (4.45) and
(4.46), it is again necessary to assume an average molecular weight
for the correlation equation of Kenaga and Goring. If an average
molecular weight of 200 is assumed, converting equations (4.7) and
(4.45) to mole fraction solubility units gives
log K = - 0.55 log x - 0.23 (Kenaga and Goring, 1978) (4.50)
QC- S
log K = - 0.56 log x - 0.04 (Chiou et al. , 1979) (4.51)
oc s
log K = - 0.54 log x + 0.44 (Karickhoff et al., 1979) (4.46)
oc s
Several observations can be made about these equations. First,
the similarity of equations (4.50) and (4.51) is remarkable, consider-
ing the contrasting data bases used by Kenaga and Goring and by Chiou
et al. to determine their correlation coefficients. In fact, equations
C4.50), (4.51), and (.4.46) may all be written in the form
, «, -0.55(±0.01) (4.52)
K = (constant) x v
oc s
401
-------
Table 4.8
AQUEOUS SOLUBILITIES OF HIGH MELTING POINT CHEMICALS
Chemical Name
Benzo[k]fluoranthene
Anthracene
Benzo[g,h,i]perylene
Chrysene
Dibenz[a,h]anthracene
TCDD
B-BHC
Melting Point
217
219
222
258
270
303
309
Solubilities
(ppm)
Measured
5.6 x 10
0.045
2.6 x 10
1.8 x 10
5 x 10~4
2 x 10~4
0.24
-4
-4
-3
Predicted by
Equation (4.42)'
0.04
1.2
0.015
0.1
9 x 10
-3
7.5 x 10
4.0
-3
Kenaga and Goring (1978)
402
-------
It is not clear why the solubility coefficient of -0.55(±0.01) should
appear in each of these correlations. If as expected from the above
discussions [see equations (4.3), (4.42), and (4.43)],
log K = a log K + constant (4.53)
oc ° ow
and
log K = - a log x + constant (4.54)
where a — 1, then by substituting equation (.4.54) into equation (4.53)
2
log K = - a log x + constant //,
OC S \
•*• - 1.0 log x + constant
S
It is also apparent that none of these three equations accounts for
the variation in solubility and hence variation in K value with the
J oc
melting point of the adsorbed chemical. The difference in adsorption
behavior between solid and liquid solutes, in general, has been well
documented in the literature (see, for example, Kipling, 1965). In fact,
Roe (1975) has accounted for this difference in terms of the solid solute
correction factor discussed earlier in this report. Karickhoff et al.
(1979), in discussing their relatively poor correlation of K with x
(.compared with their excellent correlation of K with K ) , mention
that a correction term is probably needed in equation (4.40) to account
for the enthalpy of fusion of the chemicals they studied.
K., - K . The partitioning of organic chemicals has recently been
o ow
reviewed by Baughman and Paris (1981), who noted the paucity of reliable
data available for correlating K_ with other partitioning parameters.
For the chemicals in Section 3, the following equation was used to cal-
culate K,,
D
KB = °'16 Kow C4'8)
403
-------
which is the simplified version of the equation given by Baughman and
Paris (1981),
log K = 0.907 log KQW - 0.21 (4.56)
The reader is referred to the above review for an excellent exposition
on the problems of reliably measuring K and the use of correlation
equations to calculate K from S or from K or K data.
B w oc ow
4.4 CALCULATION OF K FROM STRUCTURAL PARAMETERS
ow
The thermodynamics of partitioning of a chemical solution between
octanol and water phases was discussed in 4.3.1, and the use of the
octanol/water partition coefficient, K , for calculating S , K and
K ow 6 w' oc
1C was described in Section 4.3.2. Although K is the symbol used by
a ow
many scientists for this partition coefficient, earlier literature and
some current medical toxicology literature has commonly referred to the
logarithm value of K as "log P" (Hansch and Leo, 1979). For discussion
ow
in this section only, the log P nomenclature will be used instead of
log K , although the K term will be used.
& ow ow
The K data on the data sheets in Section 3 were calculated using
ow &
a computer program developed at SRI; it uses the FRAGMENT method for
calculating log P values (flansch and Leo, 1979). The theory and pro-
cedures for these calculations are discussed in detail in that reference.
Briefly, the method assumes that select groups of atoms in a molecule
can be considered fragments, each of which contributes to the total log
P value in an additive manner
log P = Z a f (4.57)
^ n n x
where a is the number of occurrences of fragment f of structural type n.
Values of f have been empirically derived from the vast body of log P
data available in the literature. Since the calculation of log P values
404
-------
for complex molecules can be time-consuming and subject to numerous cal-
culation errors, the FRAGMENT calculation method and the data base for
fragment values have been incorporated into a computer program using the
*
PROPHET computer network. The log P data are generated by first enter-
ing the structure on a graphic tablet. The log P program then uses an
ordered substructure search routine to obtain fragment values for frag-
ments of the molecular structure. Fragments are used, rather than atoms,
because atomic contributions to log P vary with certain structural en-
vironments. The program then adds the fragment values to obtain log P
values. It also identifies where the log P calculation may be incomplete
because of the absence of values for particular fragments or because
polar interactions must be accommodated by manual calculations. The log
P program is under continuing development and evaluation at SRI and
other laboratories .
The manual calculation of log P values using the FRAGMENT method
is already established as a valid method for obtaining these data (Hansch
and Leo, 1979). The calculations are, of course, subject to errors
arising from subtle structural differences that are not recognized or
cannot be accounted for when obtaining empirical values for the molecular
fragments. In fact, the primary source of error is the original data
on which the fragment values are based. The lack of reliable data is
also a dilemma for verification of calculated log P values.
As an indicator of the accuracy of the log P calculation program
Table 4.9 compares the K values recently published by Hassett et al.
r ow
(1980) with the K values calculated by the log P program. Although
ow
the chemicals are not among the organic priority pollutants, they do
represent some of the best K data currently available. The calculated
r ow
and measured K values agree within the factor of two for 8 of the 14
ow
*PROPHET is a NIH resource available to biological and chemical i
scientists on a time-share basis. Information on the log P/PROPHET
system can be obtained from Dr. Howard L. Johnson at SRI.
405
-------
Table 4.9
CORRELATION OF MEASURED AND CALCULATED VALUES OF K
ow
Computer-Calculated
n , Measured K ± S.D.a K b
Compound ow ow r
Pyrene 124,000 + 11,000 79,400 1.6
7,12-Dimethylbenz[a]anthracene 953,000 ± 59,000 871,000 1.1
Dibenz[a,h]anthracene 3,170,000 + 883,000 5,890,000 0.54
3-Methylcholanthrene 2,632,000 ± 701,000 9,330,000 0.28
Dibenzothiophene 24,000 ± 2,200 33,900 0.71
° Acridine 4,200 ± 940 2,570 1.6
13H-Dibenzo[a,i]carbazole 2,514,000 ± 761,000 692,000 3.6
Acetophenone 38.6 ± 1.2 38.9 0.99
1-Napthol 700 ± 62 417 1.7
Benzidine 46.0±2.2 35.5 1.3
2-Aminoanthracene 13,400 ± 930 1,660 8.1
6-Aminochrysene 96,600 ± 4,200 24,000 4.0
Anthracene-9-carboxylic acid 1,300 ± 130 15,500 0.08
a Hassett et al. (1980).
b Ratio of measured K to calculated K
ow ow
-------
compounds listed and agree within a factor of five for 12 of the 14
compounds. It is also significant to note that the last three compounds
in Table 4.9 show the most disagreement between calculated and measured
K values, and these compounds are large molecules containing groups
that may participate in H^bonding interactions.
In general, the accuracy of log P calculations by this method
closely approaches the accuracy of experimental determinations performed
over the last ten or twenty years because the fragment values were
derived largely from those experimental data (by regression analysis)
and incorporate the same experimental errors. It is not uncommon for
measured log P values for a given compound in the literature to vary
by 1 to 2 units; this corresponds to a factor of 10 to 100 in measured
K variation.
ow
407
-------
4.5 REFERENCES
Baughman, G. L. , and D. F. Paris. 1981. Microbial Bioconcentration
of Organic Pollutants from Aquatic Systems - A Critical Review.
Critical Reviews in Microbiology, January 1981.
Chiou, C. T., L. J. Peters, and V. H. Freed. 1979. A Physical Concept
Of Soil-Water Equilibria for Nonionic Organic Compounds. Science, 206,
831.
Hansch, C. , and A. Leo. 1979. Substituent Constants for Correlation
Analysis in Chemistry and Biology (Wiley- Interscience, New York)
Karickhoff, S. W. , D. S. Brown, and J. A. Scott. 1979. Sorption of
Hydrophobic Pollutants on Natural Sediments. Water Research 13, 241.
Kenaga, E. E. , and C. A. I. Goring. 1978. Relationship Between Water
Solubility. Soil-Sorption, Octanol-Water Partitioning and Bioconcen-
tration of Chemicals in Biota. ASTM, Third Aquatic Toxicology Symposium,
October 17-18, New Orleans, LA
Kipling, J. J. 1965. "Adsorption From Solutions of Non-Electrolytes",
(Academic Press, London).
Lewis, G. L. , and M. Randall. 1961. "Thermodynamics", revised by K. S.
Pitzer and L. Brewer, (McGraw-Hill, New York).
Roe, R. J. 1975. Adsorption of Solid Solutes from Solution: Application
of the Multilayer Theory of Adsorption. J. Colloid Interface Sci.,
50, 64.
Yalkowsky, S. H. and S. C. Valvani. 1980. Solubility and Partitioning I:
Solubility of Nonelectrolytes in Water. J. Pharm. Sci.,jS9_, 912.
408
-------
SECTION 5
CALCULATION OF THE RATES OF VOLATILIZATION
OF ORGANIC CHEMICALS FROM NATURAL WATER BODIES
5.1 INTRODUCTION
This section describes the procedures and theory used to calculate
the rates of volatilization of organic chemicals from aquatic systems.
The data needed for these calculations include the Henry's constant and
oxygen reaeration rate ratio, which are used to calculate volatilization
data in many aquatic fate models, plus the vapor pressure. The calcula-
tion methods are outlined in Section 5.2. The results are summarized
under the respective organic chemical in Section 5.3. Since the rate
constants and half-lives for volatilization of chemicals depend on
environmental parameters as well as process data, the rate constants
have not been included in Section 5.3. Section 5.4 describes the theo-
retical basis of estimation methods and presents a plot of volatilization
half-lives as a function of Henry's constant for the organic priority
pollutants for two representative aquatic systems.
5.2 CALCULATION METHODS
5.2.1 Outline of the General Procedure
The general procedure to be used is based on the two-film theory
first proposed by Whitman (1923). The detailed theory will be described
in Section 5.4. In this section, only the calculation procedure will be
described.
Volatilization of an organic chemical from water is a first-order
rate process. Therefore, the volatilization rate, RV, is written as
d[Cw3
409
-------
where [C ] is the concentration of the chemical in moles liter (M) in
water and k is the volatilization rate constant in units of time
(usually hr or day ). The full expression for estimating the volatili-
zation rate constant of the chemical from a natural water body is
-1
kc-i
kv L
1 . RT
+
8 S
(5.2)
where
L = mixing depth of the water body (cm)
k = liquid phase mass transport coefficient of oxygen in the water
body (cm hr )
D = liquid phase diffusion coefficient of the chemical (C) or
oxygen (0) in water (cm ~
m = 0.5 to 1.0, depending on the liquid phase turbulence
R = gas constant, 62.4 torr deg M or 8.205 x 10 m atm deg
mol'1
T = temperature (K)
H = Henry's constant (torr M or m atm mol )
k = gas phase mass transport coefficient for water (cm hr )
o
D = gas phase diffusion coefficient for the chemical (C) or water
S (W) in air (cm2 sec~l)
n = 0.5 to 1.0, depending on the gas phase turbulence
Equation (5.2) takes into account mass transport resistance in both the
gas and liquid phases. The derivation of equation (5.2) is given in
Section 5.4.1.
In the following subsections, we will show how to estimate each of
C
the parameters in equation (5.2) and how to calculate k for various
Q V
water bodies. The value of k obtained by using this procedure depends
on the accuracy of the value of the Henry's constant and the choice of
k and k for the specific water body.
SL g
410
-------
5.2.2 Calculation of the Henry's Constant
Henry's law states that, for ideal gases and solutions, the partial
pressure of chemical above a solution, P., is proportional to its concen-
tration in the solution, [C ]. Mathematically, it can be written
Pi = Hc [Cwi] <5-3>
Henry's constant, H , is the proportionality constant. In other words,
the magnitude of H is a measure of the tendency of a chemical to parti-
tion between the gas and liquid phases at equilibrium.
Several different units for Henry's constant are reported in the
rature. Units <
following equation:
-1 3 -1
literature. Units of torr M can be converted to atm m mole by the
_ M ) _6 _!
(atm m mole ) = Q x 1QO() = 1.32 x 10 ° HC (torr M ^ (5.4)
Henry's constant is also reported as the ratio of concentrations in the
gas and solution phase. This conversion factor depends on temperature
and, at 20°C, is:
H (torr M"1) _1
H (unitless) = C RT - = 5.47 x 10 H^torr M ) (5.5)
If a measured value of Henry's constant H is not available, the
following physical property data for a chemical must be obtained or
measured before H can be calculated:
c
o
• Melting point (T , C and K)
-1 -1
• Solubility in water at 20°C (S , g liter and mole liter )
• Vapor pressure at 20°C (P , torr)
• Heat of fusion, AH,-, is required if the chemical is a solid at
at 20°C and if the vapor pressure used to calculate Hc is for
the liquid. If a measured value of AHf is not available, an
estimation method can be used.
411
-------
Mackay and Wolkoff (1973) showed that the value of H is equal to
the vapor pressure of the chemical, P, divided by the solubility at S
Hc = P/Sw (5.6)
This equation is correct only if the vapor pressure and the solu-
bility data are for the pure material at the same temperature and the
same phase (solid or liquid). The equation is also true for gases. The
major difficulty in calculating H is often the estimation of P and the
lack of reliable solubility data for many chemicals with solubility
below 1 ppm.
If the chemical is a liquid over the temperature range of interest,
the vapor pressure data can be calculated using the Clausius-Clapeyron
equation
= P
exp
AH
v
R
Vi ~ 4
(5.7)
P« is the vapor pressure of the liquid at temperature T~, which is the
ambient temperature and P is the vapor pressure of the liquid at tempera-
-L JG
ture T , which is a higher temperature for which vapor pressure data are
available. Vapor pressure data are also often reported in the form
Iog10 P2£ = (- 0.2185 A/T2) + B (5.8)
where A and B are constants; data in the CRC handbook are given in this
form. Since the vapor pressure versus temperature equation is given in
various forms in the literature, the vapor pressure at 20°C should be
calculated for each chemical using the equation available.
If the chemical is a solid at 20°C and the vapor pressure data were
obtained above the melting point of the chemical, extrapolation of the
vapor pressure data at 20°C will give the vapor pressure of the super-
cooled liquid (P2 .). Thus, equation (5.7) becomes
412
-------
- P
AH
~R~
(5.9)
However, to calculate H , it Is necessary to obtain the vapor pressure for
the solid phase at the same temperature as the solubility data, because
the vapor pressure P in equation (5.6) must be for the stable pure form
of the chemical at the same temperature as the solubility data (e.g.,
ambient temperature). Prausnitz (1979) has shown that the extrapolated
vapor pressure for the solid phase (P ) can be estimated from the extra-
polated vapor pressure of the supercooled liquid phase (P_ ) by
*- s jc
p = P
2s r2s£
R
m
(5.10)
where AHf is the heat of fusion for the chemical (cal mol ), R is the
-1-1
gas constant (1.987 cal K mol ), and T is the melting point in Kelvin.
If solubility data are not available, the solubility can be estimated
using equation (4.4), in Section 4.2.1 of this report.
Therefore, the following expressions should be used to calculate the
vapor pressure and Henry's constants. For chemicals that are liquids at
the ambient temperature T :
P = P
*2£ *]
AH
exp
v
1.987 IT
(5.11)
or
log P2 = (- 0.2185 A/T2) + B
Hc - P2£/Sw
(5.8)
(5.12)
For solids, at 20°C, when a value for AH- is available:
P = P
2s *
I" AHv /I 1 ^
eXP I QP7 IT T~
[ 1'987 \T1 T2^
Hc = P2s/SW
AHr
lexpl~987
/i - J,\"
\Tm T2/
(5.13)
(5.14)
413
-------
The value of !„ is chosen as 20°C = 293 K, or equal to the same tempera-
ture as reported for the solubility data.
Yalkowski and Valvani (1979) have suggested that AH- be calculated
from the melting temperature and entropy of fusion, AS,-, using equation
(5.15)
AH,, = T AS,,
f m f
(5.15)
where AS- = 13.5 entropy units and is nearly constant for rigid molecules.
If the value of AH is not available, equation (5.16) is used to calculate
P0 for solids.
2s
p = p
2s 1£
AH
exp
V
1.987 IT
AS,
exp
1.987
1 -
m
(5.16)
5.2.3 Calculation of Diffusion Coefficients
As shown in Section 5.4, the gas and liquid phase diffusion coeffi-
cients are used in Equation (5.2). The liquid phase diffusion coefficients
D should be estimated using the Haydeck and Laudie modification of the
Othmer and Thakar relation (Reid et al., 1977, p. 573)
13.26 x 10
1.4
w
T0.589
u
b
(5.17)
where r\ is the viscosity of water (centipoise) and V, is the molar volume
at the normal, boiling point (cm mol ). The ratio of liquid diffusion
C 0
constants for the chemical and oxygen in water, D /D becomes
0.589
(5.18)
The molar volume is estimated using the molar volume increments proposed
by LeBas (Reid et al., 1977, p. 58) and the molar volume of oxygen, 25.6
3 -1
cm mol , which was calculated from diffusion coefficient data (Reid et
al., 1977, p. 58).
414
-------
S-\ r -T
The ratio of the gas phase diffusion coefficients D /D should be
& 5
calculated using the Fuller, Schettler, and Giddings method (Reid et al.,
1977, p. 554). The gas phase diffusion coefficients are
0.001 T1'75 (l/^ + 1/M2)1/2
where M is the molecular weight and Zv is the atomic diffusion volume.
The subscripts 1 and 2 refer to the chemical or water and to air, respec-
tively. The value of Zv is 12.7 for water and can be calculated for
other chemicals using the volume increments recommended in Reid et al.
(1977, p. 554). The ratio, DC/DW, reduces to
o o
_ TT (1/M + 0.0347)1/2
DL/DW = 85 T ^rp: -^ (5.20)
g g CV,^ I/3 4-9 79 2
-,-
.72J
where M and (£v) are the molecular weights and the diffusion volume
c c
of the chemical, respectively.
5.2.4 Other Parameters
The values entered into equation (5.2) for calculation of the vola-
Q
tilization rate constant, k , are summarized in Table 5.1. The rationales
for these choices are given in the Section 5.4.2. The half-life of the
chemical is
t^ (hr) = (ln2Vk^ (5.21)
0 "W
The rationales for the choices of k., m, k , and n are also discussed in
^ g
Section 5.4.2.
5.2.5 Sample Calculation
As an example, the calculation of the volatilization rate constant
for 2,6-dinitrotoluene (2,6-DNT) is shown in this section. The necessary
physical properties are:
415
-------
Table 5.1
SUMMARY OF CONSTANTS AND VALUES FOR SUBSTITUTION INTO EQUATION (5.2)
Constant/value
Rivers
Lakes
L (cm)
k (cm hr )
m
T (K)
RT (torr M"1)
RT (m3 atm mol"1)
kW (cm hr'1)
g
n
200
8
0.7
293
18,283
2.40 x 10~2
2100
0.7
200
1.8
1.0
293
18,283
2.40 x 10~2
2100
0.7
416
-------
Molecular weight: 182.14
Solubility: No data. Estimated to be equal to the solubility of .
2,4-DNT, which is 180 mg liter at 20°C or 9.88 x 10 M.
Melting Point: 65°C.
Sample Calculation of H for 2,6-DNT. The vapor pressure data used
here are from Maksimov (1968), who reported 11 measurements between 150°
and 260°C. Since all the data are above the melting point, extrapolation
of the vapor pressure data to 20°C will give the vapor pressure of the
supercooled liquid. The vapor pressure data for 2,6-DNT are not reported
in a form that fits equation (5.5). However, Maksimov reports that
~1 °
AH = 13.55 kcal mol and that the boiling point is 285 C (where the
vapor pressure must equal 760 torr) . The heat of fusion, AH^, is not
available, but the melting point, T , is 65°C. Therefore, equation (5.16)
m
is used to calculate the vapor pressure of the solid phase of 2,6-DNT at
20°C.
•7£n f 13,550 / 1 1 \"| f 13.5
760 [exp -T-gg7 (285 + 273 - ^3)] [exp 3-
65 + 273
= 4.2 x 10~3 torr
This value can be compared with the data of Pella (1977), who measured
the vapor pressure of solid 2,6-DNT at 20° C and obtained 3.5 x 10 torr.
The agreement is reasonable, considering the range of extrapolation of
the vapor pressure data and that a value for AIL. is not available. Using
Fella's vapor pressure data, Henry's constant is
H = P0 /S
c 2s w
= 3.5 x 10~4/9.88 x 10~4 = 0.35 torr M"1 (5.14)
-1 3 -1
To convert H in torr M to atm m mol ,
c
Hc(.t.
= 1.32 x 10~6 H (torr
417
-------
For 2,6-DNT,
H = 0.35 x 1.32 x 10~6 = 4.6 x 10~ atm m3 mol~
c
Calculation of the Diffusion Constant Ratios for 2,6-DNT. The
liquid phase diffusion constant for 2,6-DNT was calculated from equation
(5.18),
The molar volumes, V, , were calculated from the molar volume increments
proposed by LeBas (Reid et al., 1977, p. 58). For 2,6-DNT, there are
7 carbons, 6 hydrogens, 4 oxygens jointed to nitrogen, 2 nitrogens, and
1 six-membered ring. Therefore,
V^ = (7 x 14.8) + (6 x 3.7) + (4 x 8.3) + (2 x 15.6) - 15.0 = 175.2 cm3mol
b
3 -1
The recommended value of V, for On is 25.6 cm mol . Then
b Z
0.589 „ ,„„ 3 _-L
= (25.6/175.2)°'589 = 0.322 cm mol"
Similarly,
|l/2
C. W (l/Mc + 0.0347J
The diffusion volume of 2,6-DNT, using the molecular increments of LaBas,
is
(Zv)1/3 = [(7 x 16.5) + (6 x 1.98) + (4 x 5.48) + (2 x 5.69) - 20.2]1/3
= 140.481/3 =5.20 cm3 mol"1
Then,
1 /?
CW = (1/182 + 0.0347)J-/Z
S 8 [5.20 + 2.72]2
= 85 x (0.200/62.7) = 0.271
418
-------
To calculate k , the appropriate constants and values in Table 5.1
the c
For lakes ,
,
plus the constants calculated above are substituted into equation (5.2)
kC = _1_ r 1 ^ 62.4 x 293 n 1
V 2°° '_1.8 x (0.322)1'0 0.35 x 2100 x (0.
(1.72 + 62.O)"1 = 7.84 x 10~5 hr"1
3 "I
.271)°'7J
200
t^ = (In 2)/7.84x 10~5 = 8.84 x 103 hr = 368 days
For rivers,
-1
kC =
v
= 1 [" 1 + 62_. 4 x 293 "I
200 [8 x (0.322)0'7 0.35 x 2100 x (0.271)°'7J
1 (0.276 + 62.0) 1 = 8.02 x 10 5 hr
200
tj = (In 2)/8.02 x 10~5 = 8.64 x 103 hr = 360 days
•
5.3 CALCULATION OF THE VOLATILIZATION RATES OF THE PRIORITY POLLUTANTS
The volatilization rate constants of the priority pollutants were
estimated using the methods described in Section 5.2. The Henry's
constant, H , is the critical parameter in these estimates. If a
measured value of H was not available, the literature values of the
vapor pressures and solubilities were used.
In many cases, the vapor pressure at 20° C was obtained from the
report of Callahan et al. (1979); however, because it was not clear in
that report how the vapor pressure for solids was calculated, we do not
know if their vapor pressure data were extrapolated from data obtained
above the melting point of the chemical or from the solid phase. In
other cases, the vapor pressures reported were obtained from Verschueren
(.1977), but the source of those data is not cited in the reference.
Therefore, we do not know the reliability of many of the values of H
for solids. We mention this in detail because, if the reported vapor
419
-------
pressure at 20°C was calculated from data obtained above melting point
and not corrected for the phase change, using equation (5.13), H could
be as much as an order of magnitude too high.
Values of D /D and D /D were calculated using equations (5.18)
a £ g s r w
and (.5.20). The values for DC/D° ranged from 0.21 to 0.66, and D^/D
ranged from 0.18 to 0.52. Figures 5.1 and 5.2 are plots of H versus
Q
the calculated half-lives, tj , and k for the priority pollutants in
•^ v
example rivers (Figure 5.1) and lakes or ponds (Figure 5.2). The striking
conclusion from these calculations is that the value of H determines
k and t, for volatilization, while the size of the molecule, which
v % c
affects the diffusion coefficients, causes only a range in tt or k of a
-2 v
factor of less than two for a given value' of H . Also, volatilization
may be a significant process (tj > 10 days) in lakes and ponds if H is
-1 ^ -53-1 °
greater than about 50 torr M (= 6.6 x 10 atm m mol ), when liquid
phase mass transport resistance controls about 80% of the volatilization
rate for lakes or ponds and 14% for rivers.
Aroclors. The seven aroclors consist of various proportions of
chlorinated biphenyls, which include components with chlorine substitution
C 0
ranging from zero to nine. The diffusion coefficient ratios D /D and
C W ^
D /D for each component of the mixtures (e.g., the C19 component) were
So £-
first calculated. Overall diffusion coefficient ratios for each of the
seven mixtures were then determined by
and
„ „ 9
f.(DC/DW).
i g g i
where f. is the fraction of the i component of the mixture and (D /D ) .
and (D /D ). are the diffusion coefficient ratios of the i components.
O O
The Henry's constants for the aroclors were calculated from solubility
and vapor pressure data of the complete mixture.
420
-------
(O
iu~
105
"«
ta
co 104
cc
LLJ
2 103
—
UJ
U.
i io2
LL.
_J
X
10
I I I I I I I I I I _
Half- Life = t1/2 = In 2/kJ
1 —
lcc 1 [ 1 ^ RT I
V 1 I i 1
L 1 i^O (n^/D^ )n H k^' (D^/D^ i111 J
Vxx c g g g
_ * ,
.^ —
•"
•
••• —
^k»
*/«0
_ *»*•
• —
*""*•».••• «J • .•
i i i i i i ***r**H»v* i>»*. • •! . i •
io-6 -T
c7=
1Q-5 ^
2
^
in-4 ^
1 U 2
o
LU
TO'3 <
or
o
io-2 P
<
N
d
io-1 5
-J
o
>
10"4 10
~3
10
-2
10
-1
1.0
10 102 103 104 105 106
HENRY'S LAW CONSTANT (torr liter mole"1)
SA-6729-4B
FIGURE 5.1 ESTIMATED HALF-LIVES VERSUS HENRY'S CONSTANT FOR THE PRIORITY
POLLUTANTS IN RIVERS
(Values used: L = 200 cm, k°= 8.0 cm hr"1, kw = 2100 cm hr"1, n = m = 0.7)
-------
w
10"
'en
CO
2 105
CO
LU
^
-1 104
Q
"Z.
<
CO o
Q 1Q3
"Z.
o
CL
S 102
LU
LL
Ij
1
i 10
x
I
Half- Life =
1
—
_
—
—
•
*
I
•t.
t
\,
K
9
.•.-,.
. zv
* I
c _ '
L
: .
•".
I
= t1/2 = '" 2/kC
I
r™»~r
_kc Dc DK )
, m
* "*•••• *»*i* %* •
• •
I
c g
^t •
g g J
<
I
—
—
» —
10'6 T_
o =
10~5 ^
<
10-4 1
0
o
LU
10'3 <
oc
_
10"2 P
N
_l
0
~4 "3
10~ 10" 10" 10
,-2 m-1
1.0
10 102 103 104 105 10
~1
HENRY'S LAW CONSTANT (torr liter mole
FIGURE 5.2 ESTIMATED HALF-LIVES VERSUS HENRY'S CONSTANT FOR THE PRIORITY
POLLUTANTS IN LAKES OR PONDS
SA-6729-3B
(Values used: L = 200 cm, k°= 1.8 cm hr"1, kw = 2100 cm hr~1 , n = 1; m = 0.7.)
-------
Toxaphene. Toxaphene is mainly a mixture of polychlorinated camphenes.
The average formula is C.. ..H- _C1,,, which was used to calculate an "average"
diffusion coefficient ratio. A Henry's constant was determined from
solubility and vapor pressure data for the complete mixture.
Chlordane. The two major isomers of chlordane were considered in
these calculations. Diffusion coefficient ratios were calculated for
these isomers and were found to be equal because they have the same
molecular formula and very similar structures. The Henry's constant for
clordane was determined from solubility and vapor pressure data for the
complete mixture.
5.4 THEORETICAL CONSIDERATIONS
In this section, we will derive equation (5.2) and discuss the
selection of environmental parameters recommended in Table (5.1). The
reader is referred to the references for the theoretical discussion of
the calculation of vapor pressures (any general physical chemistry textbook
plus Reid et al. 1977), Henry's constant (Mackay and Wolkoff, 1973), and
the diffusion constants (Reid et al., 1977).
5.4.1 Two-Film Theory
The approach we have used is based on the two-film theory developed
by Whitman (1923), which was recently described by Liss and Slater (1974),
by Mackay and Leinonen (1975), and Smith and Bomberger (1980). The
general expression for the volatilization rate of a chemical is
d[Cw]
R = - . W = k [C ] (5.1)
v dt v w
L
(5.22)
where
R = volatilization rate of a chemical, C
v (moles liter"1 hr"1)
423
-------
C = concentration of C in water
k = volatilization rate constant (hr )
L = depth (cm)
k = liquid phase mass transport coefficient
(cm hr"1)
H = Henry's law constant (torr M )
k = gas phase mass transport coefficient
8 (cm hr"1)
The derivation of equation (5.22) is given in Liss and Slater (1974) and
Mackay and Leinonen (1975). It is based on the assumption that the fluxes
of a chemical through the liquid and gas phase boundary layers and the
air-water interface are equal. The equation suggests that volatilization
is inversely proportional to the solution depth and directly proportional
to the turbulence in either or both the liquid and gas phases.
The volatilization rate of a chemical may depend on liquid phase or
gas phase resistance or both, depending on the relative magnitude of k
and H k . Liss and Slater (1974) estimated values of k for CO,-,
(20 cm hr~ ) and of k for water (1000 to 3000 cm hr" ). These values
O
were assumed to be typical and substituted into equation (5.22). Then,
the ratio of the first term to to the sum of the two terms is set equal
to the fraction of gas or liquid phase control, and the equation is
solved for H . The calculation shows that mass transfer in the liquid
phase controls about 95% of the volatilization rate constant when the
-i -3 3 -1
value of H is greater than about 3500 torr M L (4.6 x 10 atm m mol ).
We have called chemicals that meet this requirement high volatility
compounds. A similar calculation shows that if H is less than 10 torr
-1 -53-1 °
M (1-3 x 10 atm m mol ), mass transfer in the gas phase is rate
controlling. These are low volatility compounds. If H is between about
10 and 3500 torr M , then both terms in equation (5.22) are significant.
A similar procedure has been described by Billing (1977).
If H > 3500 torr M , R is determined by the value of k and is
limited by diffusion through the liquid phase boundary layer since
kv = k£/L (5.23)
424
-------
For low volatility compounds, where H < 10 torr M , only the second
term in equation (5.22) is significant. Then
H k
and the volatilization rate is limited by gas phase mass transport resis-
tance. For intermediate volatility compounds, where 3500 < H < 10 torr
_^ c
M , both terms in equation (5.22) are significant. The method we
Q
recommend for calculating k takes into account the fact that either or
both terms in equation (5.22) may be important, depending on the magnitude
of H .
c
In both the gas and liquid phase
kg = Dg/6g (5.26)
where D is the diffusion coefficient and 6 is the boundary layer thickness,
These equations suggest that the liquid and gas phase mass transport
C C
coefficients of the chemical, k and k , are proportional to the gas and
§ p
liquid phase diffusion coefficients, D^ and D , respectively. The diffu-
A/ §
sion constants depend on the temperature and viscosity of the fluid phase,
but are independent of the turbulence. Therefore, numerous authors have
proposed that the ratio of mass transport coefficients for two chemicals
in the same solution should be independent of the turbulence level (Hill
et al., 1976; Tsivoglou et al., 1965; Paris et al., 1978; Smith et al.,
1977 a,b: Smith and Bomberger, 1978 and 1980; Smith et al., 1980).
> (5-27)
D*) (5.28)
In the liquid phase, oxygen is a convenient choice for a reference
chemical since HC for oxygen is 1.2 x 10 torr M at 25°C and liquid
phase mass transport controls the transport of oxygen from air to water.
425
-------
If liquid phase mass transport resistance controls the volatilization
rate, then equation (5.29) is correct for a wide range of chemicals and
kj/k° = k^/k° = f (D^ = constant (5.29)
laboratory conditions (see Smith et al. 1980 and references therein).
Smith et al. (1980) have shown that
(5.30)
where m = 0.61 for their, laboratory conditions. The exponent arises because
the classical two-film theory is not the correct mathematical formulation
of the mass transport theories. The theoretical reasons may be found
elsewhere (Trebal, 1968; Smith and Bomberger, 1980; Smith et al., 1980).
C 0
Since the ratio k /k is a constant over a wide range of environmental
v v &
conditions, equation (5.22) should be applicable over a wide range of
environmental conditions, provided H is greater than about 3500 torr
M = 4.6 x 10 atm m mol
(kC) = (k^k0), , (k°) (5.31)
v env v v lab v env
C —1
where k is the volatilization rate constant for the chemical (hr ) and
k is the oxygen reaeration rate constant (hr ) in the laboratory or
v CO
the environment. The ratio k /k for benzene is independent of turbu-
lence, salt concentration (seawater) , temperature (4°-50°C) , or the
presence of a surface-active compound (Smith et al., 1980). Also the
value of (kC/k°)n . can be predicted using
v v lab
0.61
(5.32)
where D. is the liquid phase diffusion coefficient. This equation was
COG
also tested using laboratory measurements of k /k and estimates of D
for 13 compounds (Smith et al., 1980).
;
426
-------
For chemicals where gas phase mass transport resistance determines
the volatilization rate, the ratio of the gas phase mass transport coef-
ficients for two chemicals measured simultaneously will be constant.
Thus, from equation (5.28)
kA/kB = f(DA/DB/) = a constant (5.33)
g g g g
which means that the ratio of mass transport coefficients should be
independent of the gas phase turbulence. Then, for the chemical and
for water evaporation
(kC/kW) = (kC/kW). , = f(DC/DW) = a constant (5.34)
g' g'env g g lab g g
If classical two-film theory were a valid description of the mass trans-
port, equation (5.33) would become
kC/kW = f (DC/DW) = (DC/DW)m = a constant (5.35)
g g g g g g
where m = 1. However, for theoretical reasons beyond the scope of this
discussion, m is probably less than 1 (see Tamir and Merchuk, 1978).
Rearranging equations (5.30) and (5.35) gives
kC = kW (DC/DW)n (5.37)
g g g g
0 W
If we know or can estimate k , k , the diffusion constant ratios, and
C *• 8
H , then k can be calculated by substituting equations (5.36) and (5.37)
into equation (5.22).
r i r i T?T I""-'-
(5.22)
C _ 1 [i + _RT_T1
V L kC HCkC
L £, c gj
•I i TI m -L
L
RT
H kW(DC/DV (5>2)
c g g g
This equation was used to estimate the volatilization rate constants of
the priority pollutants.
427
-------
5.4.2 Choice of Parameters in Table 5.1
The values of L and T for the environment are arbitrary and could
Q
be adjusted to fit specific situations. The value of k is not strongly
dependent on temperature, especially if liquid phase mass transport
resistance is significant (the chemical is a high or intermediate vola-
tility chemical).
The values of k „ were calculated from literature estimates of k ,
I v
which are summarized in Table 5.2.
Table 5.2
OXYGEN REAERATION RATES IN REPRESENTATIVE WATER BODIES
Values used in
Q
Smith et al.
0
<.
v
Literature values
(day'1)
-1 -1
(day ) (hr ) (cm)
Corresponding
value of k.
(cm hr"1)
Pond
River
Lake
0.11 - 0.23b
r A
0.2, 0.1 - 9.3
0.10 - 0.30b
0.19
0.96
0.24
0.008
0.04
0.01
200
300
500
1.6
12
5
Smith et al. (1977).
Metcalf and Eddy (1972).
°Grenney et al. (1976).
Langbein and Durum (1967); taken from Table 2 for rivers such as the
Allegheny, Kansas, Rio Grande, Tennessee, and Wabash. Values for other
rivers as well as a method for calculating k^ in rivers are given in
this reference.
428
-------
One way to calculate an appropriate value of the gas phase mass
W
transport coefficient for water, k , is to use the water evaporation rate
W
or flux, N , since
(5.38)
e \ J^-J- /
W W
where P and P are the saturated and actual partial pressure of water
s
vapor at temperature T. The field data that we have found for water
evaporation rates from lakes are summarized in Table 5.3. We have not
been able to locate equivalent data for streams or rivers. Assuming an
W
average relative humidity of 50%, the average value of k for the fresh-
-1 -1 ^
water lakes would be 0.59 cm sec = 2100 cm hr . An alternative method
is described in the next section (Section 5.4.3).
Table 5.3
WATER EVAPORATION RATES FOR LAKES
T . Average Evaporation Rate _ _
Location , Li T nf>\ Reference
(cm sec x x 10")
Lake Hefner, Oklahoma 4.8 Marciano and Harbeck (1952)
Lake Mead, Nevada and Arizona 6.8 Harbeck et al. (1958)
Pretty Lake, Indiana 3.8 Ficke (.1972)
Average 5.1
429
-------
The values of the exponents m and n in equation (5.2) are based on
laboratory work carried out at SRI International. Smith et al. (1980)
found that, for the volatilization rates of 13 high volatility compounds
measured in the laboratory, m = 0.62. The data for four chemicals suggest
that n is about 0.8 or 0.9 under their laboratory conditions. Both m
and n should vary from 0.5 to 1.0, depending on the turbulence; the values
approach 1.0 as the turbulence level decreases. However, systematic
studies to estimate the values of m and n in environmental situations
have not been made. Therefore, the choices recommended in Table 5.1 are
reasonable, but somewhat arbitrary.
5.4.3 Selection of Volatilization Rate Input Data for the EXAMS Model
The EXAMS model was described in Section 2.2. If no other volatili-
zation rate data are available, EXAMS uses the Henry's constant to cal-
culate the volatilization rate constant, using a modified version of
equation (5.2). The value of Henry's constant is calculated by EXAMS using
equation (5.7), the Clausius-Clapeyron equation. If the chemical is a
solid, equation (5.13) should be used to calculate H , since EXAMS does
not make the vapor pressure correction for the heat of fusion.
If a value for kC/k° (variable KVOG in EXAMS) is not entered, the
environmental mass transport coefficients for k. (variable K02 in EXAMS
W
and k (variable WAT in EXAMS) are estimated from the inverse ratio of
g
the square roots of the molecular weight of oxygen or water and the
chemical. This assumption gives values that are within about +20% of
the experimental values, (Smith et al., 1980). In EXAMS, estimation
C 0
procedure can be overidden by entering a value of k /k (variable KVOG).
0 0
Therefore, for high volatility compounds, the measured value of k /k is
reported in Section 3. If an experimental value is not available, the
value calculated from equation (5.39) for streams and rivers is reported.
kX = kX = Kv°G= (DX)0'7 <5-39>
£
The calculation procedure for k cannot be overridden in the current
B C W
version of EXAMS, so estimates of D /D have not been included in Section 3.
o 6
430
-------
In EXAMS, the value of k is calculated from the wind speed, which
W ^
used to calculate k from
g
WAT(kW) = 0.1857 + 11.36 WINDG (5.40)
o
where WINDG is the wind speed 10 cm above the water surface. The default
-1 W -1
value of WINDG is 2 m sec , which gives a value of k = 2290 cm hr ,
-1 ^
in good agreement with the value of 2100 cm hr that was estimated from
the field data for water evaporation summarized in Table 5.3.
431
-------
5.5 REFERENCES
Callahan, M. A., M. W. Slimak, N. W. Gabel, I. P. May, C. F. Fowler,
J. R. Freed, P. Jennings, R. L. Durfee, F. C. Whitmore, B. Maestri,
W. R. Mabey, B. R. Holt and C. Gould. 1979. Water-Related Environ-
mental Fate of 129 Priority Pollutants. U.S. EPA, Washington, B.C.,
Vol. I, EPA-440/4-79-029a; Vol. II, EPA-440/4-79-029b.
Billing, W. L. 1977. Interphase Transfer Processes: II Evaporation
Rates of Chloro Methanes, Ethanes, Ethylenes, Propanes, and
Propylenes from Dilute Aqueous Solutions. Comparisons with Theor-
etical Predictions. Environ. Sci. Tech., 11: 405-409.
Ficke, J. F. 1972. Comparison of Evaporation Computation Methods,
Pretty Lake, Lagrange County, Northeastern Indiana. USGS Profes-
sional Paper 686-A.
Grenney, W. B., B. B. Porcella, and M. L. Cleave. 1976. Water Quality
Relationships to Flow Streams and Estuaries, in Methodologies for
the Determination of Stream Resource Flow Requirements: An Assess-
ment, C. B. Stalmaker and J. L. Arnette, Eds. Utah State University,
Logan, Utah.
Harbeck, G. E., Jr., M. A. Kohler, G. E. Koberg, et al. 1958. Water
Loss Investigations: Lake Mead Studies. USGS Professional Paper
298.
Hill, J., IV; H. P. Kollig, B. F. Paris, N. L. Wolfe, R. G. Zepp,
"Bynamic Behavior of Vinyl Chloride in Aquatic Ecosystems";
U.S. Environmental Protection Agency, EPA-600/3-76-001, Jan 1976.
Hill, J. IV, et al. 1976. Dynamic Behavior of Vinyl Chloride in Aquatic
Ecosystems, in U.S. Environmental Protection Agency, EPA-600/13-76-001,
January.
Langbein, W. B., and W. H. Durum. 1967. The Aeration Capacity of Streams,
in Geological Survey Circular 542.
Liss, P- S., and P. G. Slater. 1974. Flux of Gases Across the Air-Sea
Interface. Nature, 247:181-184.
Mackay, B., and P. J. Leinonen. 1975. Rate of Evaporation of Low-
Solubility Contaminants from Water Bodies to Atmosphere. Environ.
Sci. Tech. 9(13):1178-1180.
Mackay, B., and A. W. Wolkholf. 1973. Environ. Sci. and Tech.
7:611-614.
Maksimov, Yu. Ya. 1968 Vapor Pressures of Aromatic Nitrocompounds at
Various Temperatures. Russian J. Phys. Chem., 42(11):1550-1552.
432
-------
Marciana, J. J., and G. E. Harbeck, Jr. 1952. Mass-transfer Studies,
in Water-Loss Investigations: Lake Hefner Studies. USGS Profes-
sional Paper 269, pp. 46-70
Metcalf and Eddy, Inc. 1972. Wastewater Engineering: Collection,
Treatment, Disposal. McGraw-Hill, New York, New York.
Paris, D. F., W. C. Steen, G. L. Baughman. 1978. Role of Physio-
Chemical Properties of Aroclors 1016 and 1242 in Determining
their Fate and Transport in Aquatic Environments. Chemosphere,
4:319-325.
Pella, P. A. 1977. Measurement of the Vapor Pressures of TNT, 2,4-DNT,
2,6-DNT, and EGDN. J. Chem. Thermo. 9:301-305.
Prausnitz, J. M. 1969. Molecular Thermodynamics of Fluid-Phase
Equilibria. Prentice-Hall, Inc., Englewood Clifts, New Jersey.
Reid, R. C., J. M. Prausnitz, and T. K. Sherwood. 1977. The Properties
of Gases and Liquids, 3rd ed., McGraw-Hill Book Company, New York.
Smith, J. H., et al. 1977. Environmental Pathways of Selected Chemicals
in Freshwater Systems, Part I: Background and Experimental Procedures.
U.S. Environmental Protection Agency, Athens, GA. [EPA Report No.
EPA-600/7-77-113, October 1977; Part II: Laboratory Studies, EPA
Report No. EPA-600/7-78-074, May 1978.]
Smith J. H., and D. C. Bomberger. 1978. Prediction of Volatilization
Rates of Chemicals in Water, presented at the AIChE 85th National
Meeting, Philadelphia, June 4-8, 1978. Published in Water, 1978.
Smith, J. H., and D. C. Bomberger. 1980. Volatilization From Water.
Chapter 7, in T. Mill et al., Laboratory Protocols for Evaluating
the Fate of Organic Chemicals in Air and Water. Submitted to the
U.S. Environmental Protection Agency, Athens, GA in partial ful-
fillment of EPA Contract No. 68-03-2227
Smith, J. H., D. C. Bomberger, and D. L. Haynes. 1980. Prediction of
the Volatilization Rates of High Volatility Chemicals from Natural
Water Bodies. Environ. Sci. Tech. 14(11):1332.
Tamir, A., and J. C. Merchuk. 1978. Effect of Diffusivity on Gas-Side
Mass Transfer Coefficient, in Chem. Eng. Sci. 33:1371-1374.
Treybal, R. E. 1968. Mass-Transfer Operations, Second edition McGraw
Hill Book Co., New York.
Tsivoglou, E. C., R. L. O'Connel, C. M. Walter, P. J. Godsil, G. S.
Logsdon, Water Pollut. Control Fed. 1965, 37, 1343.
433
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Verschveren, K. 1977- Handbook of Environmental Data on Organic Chemicals,
Van Nostrand.
Whitman, W. G. 1923. Preliminary Experimental Confirmation of the
Two-Film Theory of Gas Absorption. Chem. Metall. Eng. 29:146-
148; CA17:3118.
Yalkowski, S. H., and S. C. Valvani. 1979. Solubilities and Partition-
ing 2. Relationships between Aqueous Solubilities, Partition
Coefficients, and Molecular Surface Areas of Rigid Aromatic
Hydrocarbons. J. Chem. Eng. Data, 24(2):127-129.
434
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
2.
3. RECIPIENT'S ACCESSION>NO.
TITLE AND SUBTITLE
5. REPORT DATE
Aquatic Fate Process Data for Organic Priority
Pollutants: Final Draft Report
1QS1
6. PERFORMING ORGANIZATION CODE
AUTHOR(S)
W.R. Mabey, J.H. Smith, R.T. Podoll, H. L. Johnson
T. Mill, T.-W. Chou, J. Gates, I. Waight Partridge, anc
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORGANIZATION NAME AND ADDRESS D. Vandenberg
SRI International
333 Ravenswood Ave.
Menlo Park, Calif. 94025
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-3867
EPA 68-03-2981
12. SPONSORING AGENCY NAME AND ADDRESS
United States Environmental Protection Agency
Monitoring and Data Support Division (WH-553)
401 M Street, SW
Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Equilibrium and kinetic constants for evaluating the transformation and
transport in aquatic systems for 114 organic chemicals on EPA's priority
pollutant list have been obtained from the literature and from theoretical
or empirical calculation methods. Constants for selected physical properties
and for partitioning, volatilization, photolysis, oxidation, hydrolysis, and
biotransformation are listed for each chemical along with the source of the
data. Values are reported in units suitable for use in a current aquatic fate
model. A discussion of the empirical relationships between water solubility,
octanol-water partition coefficients, and partition coefficients for sediment
and biota is presented. The calculation of volatilization rates for organic
chemicals in aqueous systems also is discussed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. cos AT I Field/Group
Partition coefficients
Sorption
Henry's Constant
Volatilization
Photolysis
Hydrolysis
Oxidation
Biotransformatio
Transport
Transformat ion
Priority Pollutants
Environmental Fate
Aquatic Fate
18. DISTRIBUTION STATEMENT
Distribution Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
446
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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