&EPA
United States
Environmental Protection
Agency
Environmental Research
Laboratory
Athens GA 30605
I PA (300 3 /!) ORfi
August 1979
Research and Development
Adsorption of
Energy-Related
Organic Pollutants
A Literature Review
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REPORTING
Research reports of the Office of Research and Development, U.S Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are:
1 Environmental Health Effects Research
2 Environmental Protection Technology
3. Ecological Research
4 Environmental Monitoring
5, Socioeconomic Environmental Studies
6 Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
Th'.--.. document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/3-79-086
August 1979
ADSORPTION OF ENERGY-RELATED ORGANIC
POLLUTANTS: A LITERATURE REVIEW
by
K. A. Reinbold, J. J. Hassett,
J. C. Means, and W. L. Banwart
Institute for Environmental Studies
and
Department of Agronomy
University of Illinois at Urbana-Champaign
Urbana, Illinois 61801
Contract No. 68-03-2555
Project Officer
David S. Brown
Environmental Processes Branch
Environmental Research Laboratory
Athens, Georgia 30605
ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ATHENS, GEORGIA 30605
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DISCLAIMER
This report has been reviewed by the Environmental Research Laboratory, U.S.
Environmental Protection Agency, Athens, GA, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
11
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FOREWORD
Environmental protection efforts are increasingly directed towards
prevention of adverse health and ecological effects associated with specific
compounds of natural or human origin. As part of this Laboratory's research
on the occurrence, movement, transformation, impact, and control of environ-
mental contaminants, the Environmental Processes Branch studies the.-micro-
biological, chemical, and physico-chemical processes that control the trans-
port, transformation, and impact of pollutants in soil and water.
Efforts to achieve our national goal of energy independence will require
increasing use of our country's vast domestic coal reserves. The combustion
of coal or its conversion to a gaseous or liquid fuel, however, can release
numerous organic compounds that are potentially toxic, carcinogenic, or muta-
genic. This report reviews the literature on the adsorption of energy-related
organic pollutants and other compounds on sediments and soils. Information
on the adsorption of these pollutants onto sediments is needed to predict
their movement and fate in aquatic systems so that potential environmental
problems can be anticipated.
David W. Duttweiler
Director
Environmental Research Laboratory
Athens, Georgia
111
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ABSTRACT
This report is a literature review which was completed as the first
phase of a research project on sorption properties of sediments and energy-
related organic pollutants. Adsorption of organic compounds in general is
discussed, and analytical methodology in soil thin-layer chromatography and
chemical analysis as applicable to measurement of sorption properties is
summarized. The literature on the adsorption of energy-related organic
pollutants is reviewed. Reported constants for the adsorption of organic
compounds on several adsorbents are tabulated, and factors which influence
the adsorption are discussed.
This report was submitted in partial fulfillment of Contract No. 68-
03-2555 by the University of Illinois Institute for Environmental Studies
in cooperation with the Department of Agronomy under the sponsorship of the
U.S. Environmental Protection Agency. This report covers the period of
July 1977 to April 1978, and work was completed as of June 1979.
IV
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CONTENTS
FOREWORD iii
ABSTRACT iv
FIGURE vi
TABLES vi
ACKNOWLEDGMENTS vii
1. INTRODUCTION 1
2. SUMMARY AND CONCLUSIONS 8
3. ADSORPTION OF ORGANIC COMPOUNDS 9
The Solid-Solution Interface 9
Adsorptive Forces 9
Adsorption Isotherms 11
4. ANALYTICAL PROCEDURES: SOIL THIN-LAYER CHROMATOGRAPHY 18
5. ANALYTICAL PROCEDURES: CHEMICAL ANALYSIS 22
Recovery of Organic Compounds from Environmental Samples 22
Fractionation, Cleanup, and
Separation of Organic Extract Components 23
Quantitation of Trace Organic Compounds in Solvent Extracts 24
6. REVIEW AND INTERPRETATION OF ADSORPTION DATA 30
Factors Influencing Adsorption 30
Interpretation of Tabulated Data 34
BIBLIOGRAPHY 114
Adsorption of Organic Compounds 114
Analytical Procedures 134
Compound Characteristics 153
Occurrence and Distribution of Energy-related Organic Compounds 158
APPENDIX: FORMULAS OF ORGANIC COMPOUNDS 161
v
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FIGURE
1. Functional Group Model of Bituminous Coal
TABLES
1. Organic Contaminants Present in Coal Tar
from the Synthane Coal Conversion Process 3
2. Contaminants Present in Product Water
from the Gasification of Illinois No. 6 Coal 4
3. Classes of Known or Suspected Carcinogenic or Cocarcinogenic
Compounds Associated with Processing and Utilization of Coal 5
4. Selected Energy-Related Organic Compounds 7
5. Kcw, Calculated Koc, Linear Kp and Measured Koc Values for Sorption of
Pyrene, Dibenzothiophene and Acetophenone by Soils and Sediments 33
6. Adsorption Constants for Organic Compounds 36
7. Average Values of Adsorption Constants for Organic Pesticides 89
8. Relationship between Octanol/Water
Partition and R Values of Pesticides on a Soil 107
9. Leaching of Pesticides from a Soil 108
10. Sorption Dependence on Sorbate Properties 109
VI
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ACKNOWLEDGMENTS
The authors gratefully acknowledge the assistance and coordination
provided by Dr. David Brown, Project Officer, of the EPA Environmental
Research Laboratory in Athens, Georgia. Co-principal investigators for
the project under which this review was done were Dr. John J. Hassett,
associate professor of soils, and Dr. Jay C. Means, assistant research
chemist.
The literature review presented in this report was conducted under the
direction of Dr. Keturah A. Reinbold, associate research biologist, with the
assistance of Ms. Dee Condon and Ms. Carol Wells, research assistants, in
conducting the literature search. Information on soil thin-layer chroma-
tography was summarized by Dr. Wayne L. Banwart, assistant professor of soils.
Appreciation is expressed to Thomas Knecht, publications director of the
Institute for Environmental Studies, and Cindy Bohde, student editorial
assistant, for the technical editing of this report and to Jean Clarke,
Judith Jones, Trace Black, and Sharon Sparling for typing the report.
vn
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1 INTRODUCTION
Fossil fuels are a major source of anthropogenic organic compounds in
the environment. Because supplies of petroleum and natural gas are dwindling,
it will be necessary to utilize increasing amounts of coal to meet our energy
needs in the near future. As Figure 1 illustrates, coal is a complex organic
chemical. Either the combustion of coal or its conversion to a gaseous or
liquid fuel breaks the coal into numerous simpler organic compounds, which
then appear in process waste streams and may be released into the environ-
ment. These coal fragments include a great variety of polycyclic aromatics,
heterocyclic- and carbonyl-polycyclics, and aromatic amines, groups which all
contain known or suspected carcinogens, as well as phenolics and long-chain
aliphatic hydrocarbons (TRW Systems and Energy, 1976; Sharkey et al., 1976).
Coal conversion processes produce large volumes of gaseous and aqueous
effluents (Magee, Bertrand, and Jahnig, 1976). Hundreds of thousands of tons
of gases containing volatile organics, particulates, and combustion gases are
released each day- These emissions may disperse over hundreds of miles, dis-
tributing the effluent materials in both terrestrial and aquatic systems.
With such large volumes of effluents, even trace components are distributed
in significant amounts—up to hundreds of pounds per year. Some of these
materials are potentially toxic, carcinogenic, or mutagenic.
Aqueous effluents may be released at a rate of up to 5 million gallons
each day. Also, large volumes of aqueous leachate from stockpiles of coal or
solid wastes, such as ash and char, are produced. The wastes from the vari-
ous steps of the coal conversion process contain a variety of organic materi-
als.
A number of organic products have been detected in the wastes from
coal conversion pilot plants. Forney et al. (1974) identified some of the
major organic compounds in tars produced by the Synthane coal gasification
process (Table 1), and Schmidt, Sharkey, and Friedel (1974) analyzed the
process water (Table 2). TRW Systems and Energy (1976) listed several or-
ganic compounds which are associated with the processing and utilization of
coal and which are known or suspected carcinogenic or cocarcinogenic com-
pounds (Table 3).
Clearly, large quantities of organic compounds are introduced into
aquatic systems, either directly in aqueous effluents or indirectly from gas-
eous effluents. The behavior of these compounds in aquatic systems depends
largely upon the extent to which they are adsorbed on suspended or settled
sediments.
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\ / \
H H H H
Figure 1. Functional group model of bituminous coal (Wiser).
Source: Wewerka, Williams, and Vanderborgh, 1976.
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TABLE 1. ORGANIC CONTAMINANTS PRESENT IN
COAL TAR FROM THE SYNTHANE COAL CONVERSION PROCESS
Volume (percent)
Illinois
Structural Type No . 6
Benzenes
Indenes
Indanes
Naphthalenes
Fluorenes
Acenaphthenes
3-ring aromatics
Phenyl naphthalenes
4-ring aromatics - peri
4-ring aromatics - cata
Phenols
Naphthols
Indanols
Acenaphthols
Phenanthrols
Diben zo f urans
Dibenzothiophenes
Benzonaphthothiophenes
N-hetero cycles
2.1
8.6
1.9
11.6
9.6
13.5
13.8
9.8
7.2
4.0
2.8
+
0.9
-
2.7
6.3
3.5
1.7
10.8
Lignite
4.1
1.5
3.5
19.0
7.2
12.0
10.5
3.5
3.5
1.4
13.7
9.7
1.7
2.5
-
5.2
1.0
-
3.8
Mon tana
S ubb i turn ino us
3.9
2.6
4.9
15.3
9.7
11.1
9.0
6.4
4.9
3.0
5.5
9.6
1.5
4.6
0.9
5.6
1.5
-
5.3
Pittsburg
Seam
1.9
6.1
2.1
16.5
10.7
15.8
14.8
7.6
7.6
4.1
3.0
+
0.7
2.0
-
4.7
2.4
-
8.8
Source: Forney et al., 1974
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TABLE 2. CONTAMINANTS PRESENT IN PRODUCT WATER
FROM THE GASIFICATION OF ILLINOIS NO. 6 COAL
Compound
Concentration (ppm)
Phenols
Cresols
C -phenols
C -phenols
Dihydric phenols
Benzofuranols
Indanols
Acetophenones
Benzoic Acids
Hydroxybenzaldehyde
Naphthols
Indenols
Benzofurans
Dibenzofurans
Biphenols
Benzothiophenols
Pyridines
Quinolines
Indoles
2,660 to 3,400
2,610 to 2,840
560 to 1,170
70 to 150
60 to 300
70 to 120
60 to 210
40 to 210
110 to 160
90
10 to 30
10
20 to 40
60 to 110
60 to 580
10 to 20
20 to 70
Source: Schmidt, Sharkey, and Friedel, 1974.
OBJECTIVES
To examine the adsorption of energy-related organic compounds in the
environment, a research project was initiated in the Institute for Environ-
mental Studies at the University of Illinois at Urbana-Champaign. The pro-
ject is supported by the U.S. Environmental Protection Agency under contract
number 68-03-2555. This report presents the results of the first phase of
the project, the objective of which was to review published literature on (1)
the adsorption of energy-related organic pollutants on sediments, (2) the
theory of adsorption, and (3) analytical techniques pertinent to^adsorption
measurements. Because the literature survey produced only a limited amount
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of information on the adsorption of energy- related organic compounds, a
variety of organic compounds were included in this review to provide a back-
ground of information.
APPROACH
The literature was searched by a combination of computer and manual
methods. The 1970-77 volumes of Chemical Abstracts were searched using-the
computerized Bibliographic Retrieval Service System. The key words used were
terms such as adsorption, desorption, and sediments accompanied by the names
of compound groups or of specific compounds which may be energy- re la ted or-
ganic pollutants, including all those listed in Table 4. Earlier volumes of
Chemical Abstracts were searched manually, as were pertinent books, series of
Residue Reviews, current journals, and the 1977 Weekly Government Abstracts
from the National Technical Information Service.
The computerized search produced more than 900 citations. Copies of
approximately one-third of these references were obtained for review. With
the addition of those acquired by manual searching, a total of 670 references
were obtained for review. A bibliography is included at the end of this
report.
TABLE 3. CLASSES OF KNOWN OR SUSPECTED CARCINOGENIC
OR COCARCINOGENIC COMPOUNDS ASSOCIATED WITH
PROCESSING AND UTILIZATION OF COAL
Compound Class
Representative Compound
Structure
Polynuclear Aromatic Hydrocarbons
Anthracenes 9- , 10-dimethylanthracene
Chrysenes
Benzanthracenes
Fluoranthenes
Cholanthrenes
chrysene
benzo (a) anthracene
benzo ( j ) f luoranthene
3 -methylcholanthrene
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TABLE 3, continued
Compound Class
Representative Compound
Structure
Benzopyrenes
Dibenzpyrenes
benzo(a)pyrene
dibenzo(a,h)pyrene
Nitrogen-, Sulfur-, and Oxygen-Containing Polycyc'lic Compounds
Mono- and
dibenzacridines
Benzocarbazoles
dibenz(a,h)acridine
7H-benzo (c , g) carbazole
Benzathrones
Aromatic Amines
7H-benz(d,e)anthracen-7-one
Aminoazobenzenes
4-dimethylamincazobenzene
Naphthylamines
a-naphthylamine
Cocarcinogens and Promoting Agents
Phenols/naphthols ot-naphthol
Long-chain aliphatic
hydrocarbons n-dodecane
Source: TRW Systems and Energy, 1976.
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TABLE 4. SELECTED ENERGY-RELATED ORGANIC COMPOUNDS
Polynuclear Aromatics
Anthracene
Phenanthrene
Acenaphthene
Fluorene
Naphthacene
Chrysene
Pyrene
Triphenylene
Perylene
1,2-Benzopyrene
3,4-Benzopyrene
1,2-Benzanthracene
1,2,7,8-Dibenzanthracene
1,2,5,6-Dibenzanthracene
1,2,3,4-Dibenzanthracene
7,12-Dimet±iylbenzanthracene
3-Methylcholanthrene
S-Heterocyclics
2 ,3-Benzothiophene
Dibenzothiophene
N-Heterocyclics
Carbazole
Indole
Acridine
Pyridines
Pyrroles
Benzocarbazole
Dibenzocarbazole
Benzoquinoline
Phenolics
1-Naphthol
2-Naphthol
Acenaphthol
4-Indanol
4-Benzofuranol
4-Hydroxybenzothiophene
2,3,4-Trimethyl Phenol
Miscellaneous
Acetophenone
Anthraquinone
Benzidine
Benzophenone
REFERENCES
Forney, A. J., W. P. Haynes, S. J. Gasior, G. E. Johnson, and J. P. Strakey,
Jr. 1974. Analyses of Tars, Chars, Gases, and Water Found in Effluents
from the Synthane Process. Progress Report 76. Bureau of Mines, U.S.
Department of the Interior.
Magee, E. M., R. R. Bertrand, and C. E. Jahnig. 1976. Environmental impact
and R and D needs in coal conversion. In Symposium Proceedings: Environ-
mental Aspects of Fuel Conversion Technology, III, pp. 395-403. Report No.
EPA-600/2-76-149. Washington, D. C.: Office of Research and Development,
U. S. Environmental Protection Agency.
Schmidt, C. E., A. G. Sharkey, Jr., and R. A. Friedel. 1974. Mass Spectre-
metric Analysis of Product Water from Coal Gasification. Technical
Progress Report 86. Bureau of Mines, U. S. Department of the Interior.
Sharkey, A. G., J. L- Schultz, C. White, and'R. Lett. 1976. Analysis of
Organic Material in Coal, Coal Ash, Fly Ash, and Other Fuel and Emission
Samples. Report No. EPA-600/2-76-075. Washington, D. C.: Office of
Research and Development, U. S. Environmental Protection Agency.
TRW Systems and Energy- 1976.
Processes. Oak Ridge, Tenn
Administration.
Carcinogens Relating to Coal Conversion
: U. S. Energy Research and Development
Wewerka, E. M., J. M. Williams, and N.E. Vanderborgh. 1976. Contaminants in
Coals and Coal Residues. Report No. LA-UR 76-2197- Los Alamos, N. M.:
Los Alamos Scientific Laboratory.
7
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2 SUMMARY AND CONCLUSIONS
We have reviewed the literature on the adsorption of energy-related
organic pollutants and other organic compounds on sediments, soils, and other
selected adsorbents. Adsorption constants reported in the literature for
organic compounds are compiled in Tables 6 and 7, and factors which influence
adsorption are discussed.
Among the many factors which influence adsorption are several molecular
properties of compounds. It has been shown that as chain length, molecular
volume, molecular weight, and carbon number increase, and as polarity de^
creases, adsorption of hydrophobic compounds increases. These properties are
related to water solubility of the compound. The adsorption of hydrophobic
compounds increases with decreasing water solubility, but for more polar
compounds adsorption increases with decreasing water solubility only within
a family of compounds. Soil organic matter content influences adsorption and
has been shown to correlate with the partitioning of nonpolar organic com-
pounds between octanol and water. This relationship makes possible the cal-
culation of Koc and Kp values when Kow is known.
Little of the published information pertains specifically to the adsorp-
tion of energy-related organic pollutants onto sediments or soils. Data are
available on the adsorption of a few such compounds onto carbon, but those
results cannot be directly extrapolated to sediments or soils. Investigation
of adsorption of these compounds on sediments is beginning, as in the lab-
oratory phase of this project. Information on the adsorption of these
pollutants onto sediments is needed to predict their movement and fate in
aquatic systems. To obtain sufficient information, further research is
necessary -
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3 ADSORPTION OF ORGANIC COMPOUNDS
J. J. Hassett
THE SOLID-SOLUTION INTERFACE
The adsorption or concentration of organic materials at the solid-
solution interface is of particular importance in natural waters. Streams,
lakes, and rivers contain a variety of colloidal materials both in their
bottom sediments and dispersed throughout the aqueous phase. These colloids
can actively sorb organic materials, removing them from solution or suspension,
and hence can have a marked effect on the chemical and physiological proper-
ties of the organic pollutants.
The sediments in a natural body of water consist predominantly of
organic colloids (such as clay minerals and metal oxides, hydroxides, and car-
bonates) , of organic colloids, and of living organisms. The metal oxides and
hydroxides and the organic colloids may exist as discrete particles or as
coatings on other colloids such as the clay minerals. A major source of these
inorganic colloids (and, to a certain extent, of the organic colloids) is the
erosion of watershed soils . The properties of the sediments can be quite
similar to those of the soils from which they are derived, or they may be sub-
stantially altered from the original soil, since the sediments may be subject
to physical sorting by the water and often to different chemical environments
(e.g., lower redox potentials).
Adsorption at the solid-liquid interface results when the forces of
attraction between the surface (adsorbent) and the solute (adsorbate) over-
come the forces of attraction between the solvent and the solute. Hence, the
degree of adsorption depends on the relative strengths of the adsorbate-
adsorbent interactions and the solute-solvent interactions. If the adsorbate-
adsorbent interactions dominate due to a strong adsorbate-adsorbent inter-
action or due to a weak solvent-solute interaction, adsorption will take
place and the adsorbing species will be primarily associated with the solid
phase. The net interaction of the surface and the adsorbate may result from
a variety of chemical and electrical interactions (Stumm and Morgan, 1970;
Adamson, 1967).
ABSORPTIVE FORCES
1. Coulomb'ic attraction. This force of attraction results when a
charged surface such as a clay mineral attracts an oppositely charged ion to
maintain electrical neutrality. The force of attraction is given by
Coulomb's law:
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F =
where q-i is the charge density of the surface, q2 is the charge of the adsorb-
ing species, D is the dielectric constant of the solvent and is a measure of
the shielding ofq^ from q2 by the solvent, and X is the distance between the
charges. Sorption of inorganic cations by negatively charged soil colloids in
the process of cation exchange is one example of coulombic attraction. The
sorption of the organic cations paraquat and diquat by montmorillonite and
kaolinite (Weber et al., 1965) is also an example of coulombic attraction.
In the case of paraquat and diquat sorption within the interlayer of montmor-
illonite, other sorptive forces add to the coulombic attraction.
2. London-van der Waals dispersion forces result from the oscillating
electron cloud of one atom rotating in phase with a nonoverlapping oscil-
lating electron cloud of another atom, producing a dipole-like attraction.
The differential heats of adsorption are of the order of 1 to 2 kcal mole
for small molecules and atoms. For large molecules the heats of adsorption
may be much larger. Corkill et at. (1966) gave the heats of adsorption of
methane, ethane, pentane and hexane on carbon black as being 3, 4.3, 9.2 and
11.4 kcal mole"-*-.
3. Orientation energy results from the attraction of a permanent di-
pole for another permanent dipole. The resulting energy of attraction is less
than 2 kcal mole "^.
4. Induction forces result from the attraction of an induced dipole
for the inducing species which can be either a permanent dipole or a charged
site or species. This force often adds to the adsorptive forces present in
cases of coulombic or orientation energy attraction. The energy of attraction
is less than 2 kcal mole .
5. Hydrogen bonding occurs in compounds such as water where electrons
are unequally shared between the more electronegative oxygen and hydrogen.
This arrangement results in a slight negative charge on the oxygen atom and a
slight positive charge on the hydrogen atoms, producing (in the case of water)
a dipole moment of 1.84 Debye units (Douglas and McDaniel, 1965). Hence,
attraction is possible between dissimilarly charged sites of the adsorbate
and the adsorbent. The energy of attraction ranges from 2 to 10 kcal mole .
6. Chemical forces result when the adsorbate-adsorbent bond approaches
an ordinary chemical bond in strength (»10 kcal mole"1) . Chemical forces
extend over only very short ranges and often result in the nature of the ad-
sorbate being significantly different in the adsorbed state. Such adsorption
is often termed chemisorption to distinguish it from the less specific low-
energy physical sorption. It is often difficult to distinguish between chemi-
cal and physical sorption because a chemisorbed layer may have physically
sorbed layers upon it.
For some solutes the attractive force of the adsorbate for the solid
surface can play a subordinate role to the hydrophilic-hydrophobic balance of
the solute with the solvent (Hance, 1967; Stumin and Morgan, 1970) . ThlS type
10
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of adsorption is of particular interest when considering the adsorption of
organic molecules that are concentrated at the solid-solution interface be-
cause of the hydrophobic nature of their hydrocarbon parts. For this type of
adsorption the effect of the adsorbent on the interfacial tension or surface
free energy would appear to be an important consideration in explaining the
observed phenomena. Conversely, some ions that show a strong affinity for the
solvent (for example, ones that are highly hydrated) may stay in solution even
if they are specifically attracted to the adsorbent.
Traube observed a regularity in the lowering of surface tension by
members of three homologous series of esters, alcohols, and fatty acids
(Kipling, 1965) . The rule derived from that study states, in essence, that
the tendency to adsorb organic compounds from aqueous solution increases with
increasing molecular weight for members of a homologous series. Hence, ad-
sorptive energy increases systematically for each additional Ct^ group.
Other general rules (Stumm and Morgan, 1970) concerning the adsorption
of organics state that a polar adsorbent adsorbs the most polar constituent of
a nonpolar solution in preference to the least polar constituent (s) . In con-
trast, a nonpolar surface adsorbs the nonpolar component preferentially from
a polar solution.
ADSORPTION ISOTHERMS
Several mathematical expressions — some with a theoretical basis and
others entirely empirical in nature — have been employed to describe the re-
lationship between the amount adsorbed and the equilibrium solution concen-
tration. Those equations that have a theoretical basis can (if the assump-
tions each is based upon are met) provide valuable information about bonding
or adsorption energies (affinities) , adsorption maxima (capacities) , and in-
terfacial free energies. The empirical equations provide a framework for pre-
dicting the distribution of adsorbate between the solid and aqueous phases.
Langmuir Adsorption Isotherm
The Langmuir equation (1918) , originally developed to describe the ad-
sorption of a gas by a clean solid surface, has been used by numerous inves-
tigators to describe adsorption at the solid-liquid interface. The equation
usually takes the following form (Veith and Sposito, 1977) :
where x/m = amount of adsorbate adsorbed per unit mass of adsorbent
C = the equilibrium concentration of the adsorbate in
solution
K = a constant related to the bonding energy of the
adsorbate to the adsorbent
b = adsorption maximum or capacity factor
Correct use of the equation requires that two assumptions be met:
11
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1. That the adsorbed ions be bound in a monolayer on a homogeneous
surface with localized sites.
2. That the energy of adsorption be the same for each molecule of ad-
sorbate regardless of the degree to which the monolayer is completed.
Veith and Sposito (1977) have shown that it is necessary not only to
meet the basic assumptions of the Langmuir equation but also to have an inde-
pendent means of determining that the only process taking place is adsorption,
since the Langmuir equation will also fit data obtained in situations where
secondary precipitation is taking place. Other investigators (Stumm and
Morgan, 1970; Kipling, 1965) have also cautioned that although a set of data
may fit the equation, that fact is not of itself sufficient evidence that the
assumptions have been met.
The normal application of the Langmuir equation to adsorption data
involves a least-squares fitting of the data to a linear form of equation 2.
At least three linear forms of the Langmuir equation have been used in adsorp-
tion studies:
C/(x/m) = l/Kb=C/b (Eq. 3)
l/(x/m) = 1/b+l/KbC (Eq. 4)
(x/m) = b-(x/m)/KC (Eq. 5)
Equation 3 has been used extensively in adsorption studies involving
soils. A plot of C/(x/m) against C for this equation should yield a straight
line having a slope of 1/b and an intercept at I/Kb. For equation 4 the plot
would be I/(x/m) against 1/C, yielding a slope of I/Kb and an intercept at
1/b. This type of plot is very similar to the double-reciprocal or Lineweaver-
Burk plot used in enzyme studies employing Michaelis-Menten kinetics. For
equation 5 (x/m) is plotted against (x/m)/C, yielding a slope equal to 1/K
and an intercept at b. This plot is of the same form as the Eadie-Hofstee
plot (Hofstee, 1952; 1960) also employed in Michaelis-Menten kinetics.
Dowd and Riggs (1965) compared the statistical fit and the predictabil-
ity of the three linear forms of the Michaelis-Menten equation, which have the
same form as the Langmuir adsorption isotherm and its linear equations:
V C
max s
v =
K + C (Eq. 6)
s
C /v = K /V +C /V (Eq. 7)
s m max s max
1/v = 1/V- +K /V C (Eq- 8)
' ' max m max s
v = V -K v/C
max m s
(Eq. 9)
12
-------
where
v = the initial velocity of the reaction
C = the concentration of the substrate
s
V = the maximum initial velocity
max
K = the Michaelis constant
m
They found that equation 7, which has the same form as equation 3, and
equation 9, which has the same form as equation 5, gave comparable predictions
of the two constants when the error in determining the dependent variable
(i.e., v or x/m) was small, although equation 9 would better show deviations
from linearity. Equation 9 gave the best results when the error associated
with determining the dependent variable was large. These results are sup-
ported by Syers et al. (1973), who in a soil adsorption study compared the
form of the Langmuir equation given in equation 3 with that of equation 5.
Dowd and Riggs (1965) concluded that the Lineweaver-Burk or double reciprocal
plot—equation 8, which has the same form as equation 4--should not be used
even if it fits the data well.
Several nonlinear forms of the Langmuir equation are used in adsorption
studies:
6 = KC/(1+KC) (Eq. 10)
(x/m) = bC/(K'+C) (Eq. 11)
Equation 10 is the same as equation 2 except that adsorption is expressed in
terms of the percentage of the monolayer that is occupied by adsorbate mole-
cules. This results in b, the monolayer capacity, having a value of 1 unit of
adsorption sites and disappearing from the adsorption equation. Equation 11
reduces to equation 2 if K' is replaced with 1/K; hence, K1 = 1/K.
Freundlich Adsorption Isotherm
To describe adsorption from dilute solutions, Freundlich (1922) applied
the adsorption isotherm:
a = ac (Eq. 12)
or in its more commonly used form:
(x/m) = KC1//n (Eq. 13)
where
= the equilibrium concentration in the
solution after adsorption
a or x/m = the adsorption value
13
-------
a, K, and 1/n = constants
In studies of the adsorption of a variety of organic compounds on charcoals
Freundlich found the adsorption exponent 1/n to vary between 0.1 and 0.5.
The Freundlich adsorption equation is normally considered an empirical
equation relating the amount adsorbed to the equilibrium adsorbate concentra-
tion. Kipling (1965) cites a derivation of the Freundlich equation by Henry
(1922) based on combining an expression for the free energy of a surface with
the Gibbs equation. The resulting equation defines the adsorption exponent in
terms of the monolayer capacity and surface free energy:
(x/m) =KC0- (Eq.
hence
1/n = (RT(x/m)m/(a0-0'i) (Eq. 15)
where
(x/m)m = the monolayer capacity
-------
Usually K > K ; that is, a given surface coverage will be in equilibrium with
a greater concentration of the solute for an adsorption process than for the
desorption process.
The Freundlich equation is normally statistically fit to adsorption
data in its linear form:
log(x/m) = logK + 1/n logC (Eq. 19)
A plot of log(x/m) against logC yields a slope of 1/n and an intercept equal
to logK.
In many studies the difference in adsorption of an organic material by
several soils has been correlated with the organic carbon content of the adsor-
bate. When the adsorption constants are put on an organic carbon basis, the
differences in adsorption are often removed.
K = K x -LUU (Eq. 20)
oc %OC
Gibbs Adsorption Equation
The Gibbs equation, originally derived for the adsorption at the liquid-
liquid interface (Kipling, 1965) has been applied to the adsorption of solutes
from dilute solutions by solid surfaces (Stumm and Morgan, 1970):
= 8y (Eq. 21)
is
U LJ •
y . = y .+RTlna. (Eq. 22)
hence,
1-4 _zi
| i RT
(Eq. 23)
T,P. ally's except y.
and y constant
H2°
where
. = the adsorption density of component
ri
Y = the interfacial tension
^2 = the chemical potential
a . = the activity of component i-
^
The Gibbs equation defines adsorption in terms of the effect of a solute in
either increasing or decreasing interfacial tension. The equation illustrates
that solutes which lower the interfacial tension tend to be concentrated at
the interface. Many organic substances tend to lower the interfacial tension
and hence are accumulated at the interface.
15
-------
REFERENCES
Adamson, A. W. 1967. Physical Chemistry of Surfaces. New York: Wiley.
Corkill, J. M., J. F. Goodman, and J. R. Tate. 1966. Adsorption of non-ionic
surface-active agents at the graphon/solution interface. Trans. Far.
Soc. pp. 535-44.
Douglas, B. E., arid D. H. McDaniel. 1965. Concepts and Models of Inorganic
Chemistry. Waltham, Mass.: Blaisdell Publishing Co.
Dowd, J. E., and D. S. Riggs. 1965. A comparison of estimates of
Michaelis-Menten kinetic constants from various linear transformations.
J. Biol. Chem. 240:863-69.
Freundlich, H. 1922. Colloid and Capillary Chemistry. London: Methion
& Co.
Hance, R. J. 1967. Relationship between partition data and the adsorption
of some herbicides by soils. Nature 214:630-31.
Henry, D. C. 1922. A kinetic theory of adsorption. Philos. Mag.
44:689-705.
Hofstee, B. H. J. 1952. On the evaluation of the constants V and K in
enzyme reactions. Science 116:329-31. m m
I
Hofstee, B. H. J. 1960. Nonlogarithmic linear titration curves.
Science 131:39.
Kipling, J. J. 1965. Adsorption from Solutions of Non-electrolytes.
New York: Academic Press.
LaFleur, K. S. 1976. Carbaryl desorption and movement in soil columns.
Soil Sci. 121:212-16.
Langmuir, I. 1918. The adsorption of gases on plane surfaces of glass,
mica and platinum. J. Amer. Chem. Soc. 40:1361-1403.
Stumm, W., and J. J. Morgan. 1970. Aquatic Chemistry. New York:
Wiley Interscience.
Syers, J. K., M. G. Browman, G. W. Smillie, and R. B. Corey. 1973.
Phosphate sorption by soils evaluated by the Langmuir adsorption
equation. Soil Sci. Soc. Amer. Proc. 37:358-63.
Veith, J. A., and G. Sposito. 1977. On the use of the Langmuir equation
in the interpretation of "adsorption" phenomena. So^l Sci. Soc.
Amer. J. 41:697-702.
16
-------
Weber, T. B., P. W. Perry, and R. P. Upchurch. 1965. The influence of
temperature and time on the adsorption of paraquat, diquat, 2,4-D and
prometone by clays, charcoal, and an anion-exchange resin. Soit So'L.
Soc. Am.3 Proc. 29:678-88.
17
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4 ANALYTICAL METHODS: SOIL THIN-LAYER CHROMATOGRAPHY
W. L. Banwart
The principle of thin-layer chromatography (TLC) and evidence of its
widespread use are presented by Stahl (1965). The basis of all chromato-
graphic separations is similar in that a mobile phase passes over a station-
ary phase and thereby transports different substances with varying speeds in
the direction of the flow. Conventional TLC is a form of elution chromato-
graphy in which molecules of the test compounds are exchanged between the
mobile and stationary phase as a solvent carrying the compounds migrates
across a uniform thin layer of stationary phase fixed to a glass plate. The
rate or relative rate of movement of the test compounds is dependent on their
physical properties and on experimental parameters. The solvent employed may
be water, an organic solvent, or a mixture of solvents allowing movement of
the test compounds.
The mobility or migration distances of substances on the TLC chromato-
grams can be expressed in terms of their relative mobility, Rf (Stahl, 1965),
- distance of spot center from .starting point
distance of solvent from starting point.
The use of relative mobilities provides reproducible- data, whereas absolute
mobilities, which are defined simply as the distances of the spot centers from
the starting point, may vary considerably with experimental conditions.
Using TLC to study the mobility of compounds requires a method for doc-
umenting the substances' movement. The final position of the compounds on
the chromatogram can be made visible with dye indicators, fluorescence under
ultraviolet light (Pullan, Howard, and Perry, 1966), a bioassay (Helling,
Kaufman, and Dieter, 1971), a spark-chamber apparatus (Pullan et al, 1966),
a beta camera (Snyder, 1970), and autoradiography using X-ray film (Mangold,
Kammereck, and Malins, 1962). In the last of these methods, chromatograms
are developed using ^c labeled test compounds; X-ray film is then exposed to
the chromatogram for several days before development. The developed films
make it possible to observe visually the movement of the test compounds and
can be used for easy calculations of Rf values. For quantitative measure-
ments, radioactive compounds on TLC plates can be counted directly by commer-
cially available instruments such as strip scanners (Ravenhill and James,
1967) or by zonal analysis where small successive segments of the chromatogram
are scraped from the plate and radio-assayed by liquid scintillation spectro-
metry (Brown and Johnston, 1962). Thin-layer chromatography has been used as
a standard method for separating and identifying many synthetic and natural
organic compounds (Maier and Mangold, 1964; Stahl and Mangold, 1975), includ-
ing polynuclear aromatic hydrocarbons (Zoccolillo and Liberti, 1976; Candeli
et al., 1975).
18
-------
Soil thin-layer chromatography was introduced by Helling and Turner
(1968). In soil TLC a uniform but relatively thin layer (often less than
1 mm) of a soil-water slurry is spread on TLC plates and allowed to dry. The
soil then serves as the stationary phase interacting with compounds carried
by the mobile phase. Soil TLC has provided a much simpler and faster way of
determining compound mobilities in soil than the traditional leaching columns.
Helling and Turner (1968) found that pesticide mobilities determined by soil
TLC correlated well with published data. The mobility of substances on soil
TLC plates have been reported by Helling and Turner (1968) as frontal Rf
values where
_ distance of frontal edge of spot or streak from starting point
distance of solvent edge from starting point
Standard or reference compounds can be spotted on each plate to improve
reproducibility.
Data obtained by soil TLC provide information of a nature somewhat
different from that obtained with sorption isotherms or partition coeffi-
cients. A compound on a soil TLC chromatogram may move as a compact band or
as a diffuse streak. From the type of movement it is possible to draw con-
clusions about the homogeneity of the soil material or of the compound itself.
It is also possible to obtain a relative measure of the distance compounds
might leach in a soil system when finite amounts of water are applied. Rj->
values have been used (Rhodes, Belasco, and Pease, 1970), where
_ distance moved by bottom of spot
k distance traveled by solvent
to measure the relative soil depth through which essentially all of a given
organic compound (pesticide) applied to a soil has leached. Thus, soil TLC
provides some kinds of information that cannot be obtained strictly from
adsorption constants or partition coefficients.
Data recalculated from Rhodes, Belasco, and Pease (1970) showed simple
correlation coefficients of r = 0.95 between Freundlich K and frontal Rf
values for four agricultural chemicals applied to two soils. Helling (1971c)
reported highly significant negative correlation coefficients for soil adsorp-
tion of nonionic herbicides and Rf values of the same or chemically similar
herbicides. As determined by leaching experiments, the mobilities of six
organophosphorus insecticides (McCarty and King, 1966) , three acidic herbi-
cides (Hamaker, Goring and Youngson, 1966) and their five s_-triazine herbi-
cides (Harris, 1966) were inversely related to their adsorption by the soil.
Data by Hance (1967), using two soils and 29 organic compounds, show corre-
lation coefficients ranging from 0.85 to 0.91 for the amount of compound
adsorbed by the soil and the Rf values for TLC using 40% aqueous ethanol as
a solvent. Other workers (Martin and Synge, 1941; Stahl, 1965) have also
discussed the relationship between K and Rf values. If a correlation between
Rf (mobility) and K (adsorption isotherm) values for a given set of organic
compounds can be established, it should be possible to predict K values for
additional test compounds on a particular soil.
The greatest use of soil TLC to date has been the study of pesticide
mobility in soils (Helling 1971a,b,c; Hance, 1967), but applying the tech-
nique to other mobile organic compounds should provide useful data.
19
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REFERENCES
Brown, J. L., and J. M. Johnston. 1962. Radioassay of lipid components
separated by thin-layer chromatography. J. Lipid Res. 3:480-81.
Candeli, A., G. Morozzi, A. Paolacci, and L. Zoccolillo. 1975. Analysis
using thin-layer and gas-liquid chromatography of polycyclic aromatic
hydrocarbons in the exhaust products from a European car running on
fuels containing a range of concentrations of these hydrocarbons.
Atmos. Environ. 9:843-49.
Hamaker, J. W., C. A. I. Goring, and C. R. Youngson. 1966. Sorption and
leaching of 4-amino-3,5,6-trichloropicolinic acid in soils. Advan. Chem
Ser. 60:23-37.
Hance, R. J. 1967. Relationship between partition data and the adsorption
of some herbicides by soils. Nature 214:630-31.
Harris, C. I. 1966. Adsorption, movement, and phytotoxicity of monuron and
s-triazine herbicides in soil. Weeds 14:6-10.
Helling, C. S. 1971a. Pesticide mobility in soils. I: Parameters of
soil thin-layer chromatography. Soil Sci. Soc. Amer. Pros. 35:732-37.
Helling, C. S. 1971b. Pesticide mobility in soils. II: Applications of
soil thin-layer chromatography. Soil Sci. Soc. Amer. Proc. 35:737-43.
Helling, C. S. 1971c. Pesticide mobility in soils. Ill: Influence of
soil properties. Soil Sci. Soo. Amer. Proc. 35:743-48.
Helling, C. S., and B. C. Turner. 1968. Pesticide mobility: Determination
by soil thin-layer chromatography. So-ience 162:562-63.
Helling, C. S., D. D. Kaufman, and C. T. Dieter. 1971. Algae bioassay
detection of pesticide mobility in soils. Weed Sci. 19:685-90.
McCarty, P. L., and P. H. King. 1966. The movement of pesticides in soils.
Purdue Univ. Eng. Bull., Ext. Ser. no. 121:156-71.
Maier, R., and H. K. Mangold. 1964. Thin-layer chromatography. Advan.
Anal. Chem. and Instrum. 3:369-477.
Mangold, H. K. , R. Kammereck, and D. C. Malins. 1962. Thin-layer chroma-
tography as an analytical and preparative tool in lipid radiochemistry.
Micro chemical Journal Symposium Series 2:697-714.
Martin, A. J. P., and R. L. M. Synge. 1941. A new form of chromatography
employing two liquid phases. I: A theory of chromatography. n:
Application to the micro-determination of the higher monoaminoacids in
proteins. Biochem. J. 35:1358-68.
20
-------
Pullan, B. R., R. Howard, and B. J. Perry. 1966. Measuring radionuclide
distribution with crossed-wire spark chambers. Nucleonics 24:72-75.
Ravenhill, J. R., and A. T. James. 1967. A simple sensitive radioactive
scanner for thin-layer chroma tog rams . J. Chromatog. 26:89-100.
Rhodes, R. C., I. J. Belasco, and H. L. Pease. 1970. Determination of
mobility and adsorption of agrichemicals on soils. J- Agri-c. Food
Chem. 18:524-28.
Snyder, R. 1970. Thin-layer radiochromatography and related procedures.
In Progress in Thin-layer Chromatography and Related Methods, ed.
A. Niederwieser and G. Pataki, Vol. 1, pp. 52-73. Ondon: Ann Arbor-
Humphrey Science Publishers.
Stahl. E., ed. 1965. Thin-layer Chromatography. New York: Academic Press.
Stahl, E., and H. K. Mangold. 1975. Techniques of thin-layer chromatog-
raphy- In Chromatography. 3d ed., ed. E. Heftmann, pp. 164-88.
New York: Van Nostrand Reinhold Company.
Zoccolillo, L. , and A. Liberti. 1976. Determination of polycyclic hydro-
carbons by channel thin-layer Chromatography. J. Chromatog. 120:485-88.
21
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5 ANALYTICAL PROCEDURES: CHEMICAL ANALYSIS
J. C. Means
The analysis of trace organic compounds in water or bound to soil and
sediment samples is a complicated task because of a number of factors. First,
the water and soil or sediment may contain a wide variety of organic compounds
of different polarities, molecular weights, and structures. Second, the af-
finities of different types of organic compounds for different soil-sediment
types span a large range. Third, the solubilities of organic compounds in
different solvents vary considerably. Fourth, interactions between soil com-
ponents and many types of organic compounds are poorly understood.
In general, the process of analyzing trace organic components in water
and soil or sediment samples may be divided into these tasks:
1. Quantitative recovery of the organic compound of interest
2. Separation of that compound from other types of organic compounds
3. Quantitation of the organic compound using spectroscopy, chromato-
graphy, and radioactivity or a combination of techniques.
RECOVERY OF ORGANIC COMPOUNDS FROM ENVIRONMENTAL SAMPLES
To accurately determine the amount of a given organic compound in a
water sample or bound to a soil or sediment sample, the compound must be
quantitatively recovered from the gross sample. In the case of a soil or
sediment sample, recovery is routinely accomplished by extracting the compound
from the soil in a Soxhlet apparatus. Depending upon the variety of compounds
which require analysis, a single solvent, a series of solvents, or a mixture
of solvents may be required. For example, a cyclohexane or benzene extraction
(Sawicki, 1964; Hermann, 1974) is typically used to recover aliphatic and
aromatic hydrocarbons 'from sediments, whereas a benzene and methanol mixture
may be used to remove a broad spectrum of nonpolar and polar organics (Giger
and Blumer, 1974; Blumer and Youngblood, 1976). Acetone has been used to
extract polar organics and humic substances.* Regardless of the extraction
procedure used, it is always necessary to perform recovery studies using a
reference compound to verify that the expected extraction efficiencies are
achieved.
Organic compounds may be quantatively recovered from water samples
using one of three techniques. Compounds having low boiling points and low
or intermediate polarities may be stripped from the water by passing a pure
*F. J. Stevenson, 1977: personal communication.
22
-------
inert gas through the sample and collecting it in a trap containing a gas
chromatographic column packing (e.g., Tenax GC) (Bellar and Lichtenberg, 1974;
Kuo et al., 1977) . Soluble organic compounds may be recovered from water by a
series of extractions using single or mixed solvents. In some analytical
schemes, the pH of the water may be altered (i.e., made basic, neutral, and
acidic) to achieve partial separation of compounds having ionizable functional
groups. (U.S. EPA, 1977; Acheson et al., 1976; Chang, 1976; Webb et al.,
1973) . A third technique, one which has been used very successfully, is to
collect organic compounds by sorption on purified activated carbon (Keith et
al., 1976) or on purified sorbant resins (e.g., XAD-2, 4, and 8) (Malcolm,
Thurman, and Aiken, 1977; Junk et. al., 1974; Adams, Menzies, and Levins, 1977).
These techniques have the advantage that the organics contained in a very
large sample volume may be collected on a relatively small amount of resin.
However, the recovery efficiencies for different types of organics adsorbed
from the water and subsequently desorbed from the resin vary significantly.
Therefore, the recovery of each compound of interest should be evaluated.
Another advantage of the resin sorption technique is that both polar and non-
polar organics may be sorbed to the resin and eluted for analysis.
Once an extract has been prepared from either a solid or a water
sample, it is usually necessary to reduce the volume so as to bring the con-
centrations of the extracted components into a detectable (ppm) analytical
range. The best general technique available for this process is the use of a
Kuderna-Danish evaporator (Webb et al., 1973; U.S. EPA, 1977). In some cases
air evaporation or evaporation under a stream of nitrogen may be sufficient,
but several studies have shown that significant losses of extracted organics
may occur (Chiba and Mosley, 1968; Goldberg, Delong, and Sinclair, 1973).
Similarly, rotary vacuum evaporation may be appropriate for certain compounds,
but losses of many extracted components may occur. Extracts are typically
concentrated by a factor of 500 to 10,000, depending upon the origin of the
extract and the sensitivity of the analytical systems being used. Here again,
it is advisable to test the recovery efficiency for the compound of interest
using the concentration .technique being considered.
FRACTIONATION, CLEANUP, AND SEPARATION OF ORGANIC EXTRACT COMPONENTS
Organic extracts of soil or sediments and of water, particularly those
from industrial areas, may contain hundreds of components. These multiple
components tend to complicate the accurate quantitation of individual constit-
uents. Therefore, some steps may be needed to fractionate the extract prior
to analysis. To some extent, fractionation begins with the selection of an
extracting solvent or sorption resin. However, solvent selectivities are
rarely sufficient, especially when concentration factors are high. Solvent-
solvent partitioning of the organics in an extract may be useful in crude
fractionations (e.g., separating polar compounds from nonpolar compounds).
Liquid chromatography and thin-layer chromatography (TLC) provide the
best selectivities in fractionating complex mixtures of organics. For rela-
tively large extracts, separation on liquid chromatographic columns containing
such adsorbents as silica gel, alumina, or Florisil is the method of choice.
Excellent separations of complex mixtures from acidic, basic, and neutral
fractions of coal wastes and cigarette-smoke condensates have been achieved
23
-------
using these three adsorbents (Swain, Cooper, and Stedman, 1969; Bell, Ireland,
and Spears, 1969; Severson et al., 1976).
In the last few years, a number of advances in liquid chromatographic
column packings have provided investigators with a number of gel-permeation
and adsorption materials which can be extremely useful in fractionating and
separating complex mixtures into subsamples which can be analyzed and quanti-
tated.
For relatively small samples, thin-layer chromatography can be used
successfully to fractionate a complex mixture. The same basic substrates men-
tioned above for use in column chromatography are used for TLC separations.
Careful selection of solvents and the use of two-dimensional development can
yield excellent purifications of individual components prior to quantitation.
A large number of investigators have employed TLC to purify compounds for stuiy
or to fractionate extracts prior to quantitative analysis (Treiber, 1976;
Grant and Meiris, 1977; Bender, 1968; White and Howard, 1967; Pierce and Katz,
1975; Stanley, Bender, and Elbert, 1973; additional references are given in
the analytical techniques section of the bibliography at the end of this
report) .
QUANTITATION OF TRACE ORGANIC COMPOUNDS IN SOLVENT EXTRACTS
The quantitation of individual components of a complex mixture after
partial cleanup or fractionation may generally be achieved using the tech-
niques of spectroscopy, gas chromatography, liquid chromatography, or, in
appropriate cases, liquid scintillation counting or combinations of the
above techniques.
Spectroscopic techniques, which are based on some characteristic
absorption wavelength (in the UV, visible, or infrared spectrum) of the com-
pound or a derivative, vary in their selectivity and sensitivity. In cases
where the extracts contain relatively few components, spectroscopic methods
may be successfully used to quantitate a component without additional cleanup
or separation. In most cases, however, the spectroscopic techniques must be
used in combination with compatible separation systems (e.g., liquid chroma-
tography or thin-layer chromatography). A large body of literature exists on
separations and quantitations of organic pollutants using the above techniques.
Representative reports are those of Caton, Matthews, and Walters (1976); Kelly
(1967); Willis (1973); Freudenthal et al. (1975); Jenkins and Baird (1975);
Brocco, Cantuti, and Cartoni (1970); and IUPAC Applied Chemistry Division
(1974) . Additional references are listed in the bibliography.
One spectroscopic technique which offers a relatively high degree of
both selectivity and sensitivity is the use of fluorescence spectra of various
compounds or their fluorescent derivatives (Woo et al ., 1978) . These tech-
niques are particularly useful when combined with liquid chromatography for
the analysis of many coal-derived substances (Stroupe et al., 1977) and pesti-
cides (Mallet, Belliveau, and Frei, 1975). All of these spectroscopic tech-
niques have the advantage that they are not destructive to the sample being
analyzed and that the column packing materials and thin-layer supports used
24
-------
for separations prior to spectral analysis can cover an almost unlimited range
of molecular weights.
Gas chromatography (GC) is perhaps the most widely used technique for
the separation and quantitation of organic compounds. Methods are available
for almost every class of organic pollutant including many energy-related com-
pounds. Column packing materials are available for the separation of com-
pounds representing a broad spectrum of polarities and functional groups. Al-
though fewer liquid phases are readily available, capillary columns have dem-
onstrated increasing utility for the separation of the highly complex mixtures
of organics typically found in environmental extracts.
Gas chromatographic separations in general are better than those
offered by liquid chromatography, but the compounds which can be analyzed by
GC are limited to those having significant vapor pressures at temperatures
below 400 C. In most cases, gas chromatographic analysis is destructive of
the sample. A wide variety of GC detector systems are available. The flame
ionization detector is the most common universal type. A number of other
types of detectors demonstrate selectivities for specific types of compounds
(e.g., the electron capture detector for halogens, the thermionic detector
for nitrogen and phosphorus, and the flame photometric detector for sulfur
and phosphorus). All of these detection systems may be used to quantitate
organic compounds with the use of appropriate internal standardization tech-
niques. The literature contains a large amount of information on this general
topic. Pertinent references are included in the bibliography.
In the last decade, gas chromatography has been combined with mass
spectrometry, providing investigators with a very powerful analytical system
which can be used to both identify and quantitate organic compounds (John
and Nickless, 1977; Janini et al., 1976; Alford, 1977; Oswald, Albro, and
McKinney, 1974; O'Reilly and Murrmann, 1974; Lao, Thomas, and Monkman, 1975;
and McGuire, Alford, and Carter, 1973).
In certain types of experiments, radiolabeled organic compounds may be
used successfully to follow the movement of trace organics in environmental
samples. When labeled compounds are used, many types of samples may be ana-
lyzed directly without the need for extraction, concentration, or cleanup
procedures. Care must be taken, however, to insure that the labeled compound
introduced into the experimental system is not degraded in such a way that the
radioactivity is lost or transferred to other compounds. The sample is typi-
cally separated by (1) thin-layer chromatography followed by radioautography
or liquid scintillation counting or (2) by liquid chromatography followed by
liquid scintillation spectrometry. Carbon -14 or tritium -3 labeled compounds
can be detected in liquid samples by liquid scintillation spectrometry on
aliquots of the samples. If solid samples are to be analyzed, the radiola-
beled compound may be extracted and then analyzed as a liquid sample. Solids
may also be analyzed directly by pyrolytic combustion of the solid and recov-
ery of the radioactivity as 14CO2 or 3H20.
25
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REFERENCES
Acheson, M. A., R. M. Harrison, R. Perry, and R. A. Wellings. 1976. Factors
affecting the extraction and analysis of polynuclear aromatic
hydrocarbons in water. Water Res. 10:207-12.
Adams, J., K. Menzies, and P. Levins. 1977. Selection and Evaluation of
Sorbent Resins for the Collection of Organic Compounds. Report No.
EPA 600/7-77-044. Research Triangle Park, N.C.: Industrial Environ-
mental Research Lab., Office of Research and Development, U.S.
Environmental Protection Agency.
Alford, A. 1977. Environmental applications of mass spectrometry. Bio-
medical Mass Spectrometry 4:1-22.
Bell, J. H., S. Ireland, and A. W. Spears. 1969. Identification of aromatic
ketones in cigarette smoke condensate. Anal. Chem. 41:310-13.
Bellar, T. A. and J. J. Lichtenberg. 1974. Determining volatile organics
at microgram per litre levels by gas chromatography. J. Am. Water Works
ASSOC. 66:739-44.
Bender, D. F. 1968. Thin-layer chromatographic separation and spectro-
photofluorometric identification and estimation of dibenzo[a,e] pyrene.
Environ. Sci. Technol. 2:204-6.
Blumer, M., and W. W. Youngblood. 1976. Poly cyclic. Aromatic Hydrocarbons
in the Environment: Homologous Series in Soils and Recent Marine
Sediments. NTIS No. AD A023637. Office of Naval Research.
Brocco, D., V. Cantuti, and G. P. Cartoni. 1970. Determination of poly-
nuclear hydrocarbons in atmospheric dust by a combination of thin-layer
and gas chromatography.
Caton, R. D. Jr., J. B. Matthews, and E. A. Walters. 1976. Development of
High Pressure Liquid Chromatographic Techniques. NTIS No. AD/A039644.
Tyndall AFB, Fla.: Air Force Civil Engineering Center, Air Force Systems
Command.
Chang, R. C. 1976. Concentration and Determination of Trace Organic
Pollutants in Water. Ph.D. dissertation, Ames Laboratory, Iowa State
University.
Chiba, M. , and H. V. Mosley. 1968. Studies of losses of pesticides during
sample preparation. J. Assoc. Off. Anal. Chem. 51:55-62.
Freudenthal, R. I., A. P. Leber, D. Emmerling, and P. Clarke. 1975. The
use of high pressure liquid chromatography to study chemically induced
alterations in the pattern of benzo[a]pyrene metabolism. Chem. - Biol.
Interact. 11:449-58.
26
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Giger, W.,and M. Blumer. 1974. Polycyclic aromatic hydrocarbons in the
environment: Isolation and characterization by chromatography - visible
ultraviolet, and mass spectrometry. Anal. Chem. 46:1663-71.
Goldberg, M. C., L. Delong, and M. Sinclair. 1973. Extraction and concen-
tration of organic solutes from water. Anal. Chem. 45:89-93.
Grant, D. W., and R. B. Meiris. 1977. Application of thin-layer and high-
performance liquid chromatography to the separation of polycyclic aro-
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Hermann, T. S. 1974. Development of Sampling Procedures for Polycyclic
Organic Matter and Poly chlorinated BiphenyIs. Washington, D.C.: Office
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IUPAC Applied Chemistry Division. 1974. Analytical methods for use in
occupational hygiene: Determination of benzo[a]pyrene and benzo[fe]flu-
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Janini, G. M., G. M. Muschik, and W. L. Zielinski, Jr. 1976. N,N'-Bis[p-
butoxybenzylidene]-a,a'-bi-p-toluidine: thermally stable liquid crystal
for unique gas-liquid chromatography separation of polycyclic aromatic
hydrocarbons. Anal. Chem. 48:809-13.
Jenkins, R. L., and R. B. Baird. 1975. The determination of benzidine in waste
waters. Bull. Environ. Contam. Toxicol. 13:436-42.
John, E. D., and G. Nickless. 1977. Gas chromatographic method for the
analysis of major polynuclear aromatics in particulate matter.
J. Chromatogr. 138:399-412.
Junk, G. A., J. J. Richard, M. D. Grieser, D. Witiak, J. L. Witiak, M. D.
Arguello, R. Vick, H. J. Suec, J. S. Fritz, and G. V. Calder. 1974.
Use of macroreticular resins in the analysis of water for trace organic
contaminants. J. Chromatogr. 99:745-62.
Keith, L. H., A. W. Garrison, F. R. Allen, M. H. Carter, T. L. Floyd, J. D.
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Kelly, J. A. 1967. The Determination of Phenolic-type Compounds in Water
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gas chromatography. Anal. Chem. 49:1023-29.
27
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29
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6 REVIEW AND INTERPRETATION OF ADSORPTION DATA
K. A. Reinbold and J. J. Hassett
A review of the literature revealed relatively few data on the adsorp-
tion of energy-related organic pollutants by sediments or soils. The summary
presented here, therefore, covers literature on a variety of types of organic
compounds, including pesticide data from references not covered by Farmer
(1976).
Some of the published reports included constants for the sorption of
organic compounds on various adsorbents. These constants are tabulated at the
end of this chapter. However, many sources containing sorption data did not
report sorption constants. The latter publications are included in the bibli-
ography .
Except in the case of pesticides, most of the adsorption constants
reported for organics were derived using adsorbents other than sediments,
soils, and clay minerals. The most commonly used adsorbents were activated
carbon or ion exchange resins, which are often used for the removal of organ-
ics in water treatment processes. Nylon and cellulose triacetate have also
been used. The pesticide data, however, do pertain to sorption on sediments,
soils, or clay minerals. The adsorption constants were determined in most
cases by fitting experimentally derived data to various forms of the Freund-
lich or Langmuir adsorption equations.
FACTORS INFLUENCING ADSORPTION
Adsorption is a process in which a solution component is concentrated
at the solid-solution interface. Adsorption results when the forces of at-
traction between the solution component and the surface, that is, the adsor-
bate-adsorbent interaction, overcomes the forces of attraction between the
solution component and the solvent, that is, the solute-solvent interaction.
There are two general cases where the adsorbate-adsorbent interaction is
greater than the solute-solvent interaction and adsorption results.
In the first case there is a strong positive interaction between the
surface and the adsorbate, and this interaction is strong enough to overcome
even a fairly strong solute-solvent interaction. In this case adsorption is
primarily related to the nature of the bonding between the adsorbate and the
adsorbent. The adsorption of organic cations such as paraquat by clay min-
erals or polar organic molecules within the montmorillonitic interlayer are
examples of this type of adsorption (Weber et al.3 1965) . Reviews emphasizing
the effect of adsorbate and adsorbent properties on adsorption have been writ-
ten by MDrtland (1970), Adams(1973), Bailey and White (1970), and Weber (1972).
30
-------
In the second case, adsorption takes place not because of a strong
adsorbate-adsorbent interaction, but rather due to a weak solute-solvent in-
teraction. In this case even a small positive adsorbate-adsorbent interaction
can overcome the solute-solvent interaction and result in adsorption. The
degree of adsorption or partitioning of the adsorbing material between the
solid and aqueous phases is primarily determined by the suitability of the
aqueous phase as a solvent for the material. The poorer the aqueous phase as
a solvent for the adsorbing species, the weaker the solute-solvent interaction
and the greater the adsorption.
The adsorption of nonpolar aromatic hydrocarbons of low water solu-
bility by organic surfaces is an example of this type of adsorption (Karick-
hoff et al., 1979; Means et al., 1979). This type of adsorption has been
called "hydrophobic adsorption" because of the emphasis on the weak solute-
solvent interaction in determining the degree of adsorption in aqueous systems
(Horvath and Melander, 1978)
Hydrophobic or nonpolar adsorption can be considered an example of a
nonpolar organic compound (adsorbate) partitioning between a polar aqueous
phase and a stationary organic phase (adsorbent). In a soil or sediment sys-
tem the aqueous phase would be the soil solution or the interstitial water in
the sediment, while the organic phase would be the naturally occurring humic
materials. Factors which either increase the affinity of the adsorbate for
the humic surfaces or decrease the affinity of the adsorbate (solute) for the
solvent (water) would result in greater adsorption.
Van der Waals forces have been identified as the main source of
adsorbate-adsorbent interactions between nonpolar compounds and nonpolar
organic surfaces (Horvath and Melander, 1978). The differential heats of
adsorption for van der Waals forces are of the order of 1 to 2 kcal mole
for small molecules; these forces may be much greater for larger molecules,
especially with an increase in the number of double and triple bonds (Bailey
and White, 1970) . This 'is illustrated by the adsorption of methane, ethane,
pentane and hexane by carbon black. These hydrocarbons gave differential
heats of adsorption of 3, 4.3, 9.2 and 11.4 kcal mole"1, respectively (Corkill
et at., 1966). The differential heats of adsorption do not increase indef-
initely with increasing molecular size; eventually a point is reached where
increasing molecular size does not increase adsorption and may even decrease
adsorption due to steric hindrance.
Many factors influence the solute-solvent interaction and hence in-
fluence adsorption. Molecular properties such as chain length, molecular
volume, molecular weight, carbon number, and polarity have all been shown to
influence adsorption (Bailey and White, 1970; Gustafson and Paleos, 1971;
Lailach et al., 1968; Cummings et al., 1959; Bartell and Miller, 1924;
Kipling, 1965; Hansen and Craig, 1954; Parkash, 1974). It has been demon-
strated that as chain length, molecular volume, molecular weight, and carbon
number increase, and as polarity decreases, the solute-solvent interaction
weakens and hydrophobic adsorption increases. The effect of all of these
properties on the solute-solvent interaction is integrated into the water
solubility of the compound.
31
-------
The adsorption of hydrophobia compounds has been shown to increase with
decreasing water solubility of the compound (Karickhoff et al . , 1979; Means
et al . , 1979) . The adsorption of more polar compounds has also been shown to
increase with decreasing water solubility, but only within a family of com-
pounds (Bailey and White, 1970) . Aqueous solubilities of organic compounds,
while useful in predicting adsorption, are often difficult to determine. Some
of the difficulties encountered include the approach of the water solubilities
to analytical detection limits, the formation of stable suspensions and the
long equilibration times required to establish equilibrium.
Lambert (1968) discussed the similarity between the role of soil or-
ganic matter in the sorption of organic compounds and the role of an organic
solvent in a liquid-liquid extraction. He observed that the partitioning of
a nonpolar organic compound between the soil solution and soil organic matter
was highly correlated with the partitioning of the compound between water and
an organic solvent. Karickhoff et al . (1979) reported, for sorption placed
on an organic carbon basis (Koc) , a significant correlation between the sorp-
tion of several aromatic hydrocarbons and the partitioning of the compounds
between octanol and water (Kow) .
log Koc = 1.00 log Kow - 0.21 (Eq. 24)
The linear partition coefficients (Kp) for many compounds may be cal-
culated from the following equation:
Kp = Cs/Cw (Eq. 25)
where
Cs = the concentration of the compound in the solid phase at
equilibrium
Cw = equilibrium solution concentration of the compound
When the individual linear partition coefficients for the sorption of a hydro-
phobic organic compound by a variety of different sediments and soils are
divided by the respective sediment or soil organic carbon contents, a unique
constant Koc is produced.
Kp x 100
Koc = ~ — (E(3- 26)
This constant is independent of soil or sediment (adsorbent) properties and
is only dependent on the nature of the adsorbing species (Karickhoff et al . ,
1979; Means et al . , 1979).
The relationship between Koc values and Kow values for hydrophobic
compounds has several distinct merits. First, Kow determinations are more
reliable than water solubility determinations, particularly for the highly
hydrophobic compounds. Second, once a compound's Kow value has been measured
or calculated, its Koc can be determined from equation 24. Third, if the
organic carbon contents of the individual soils or sediments are known, then
their respective Kp values for the adsorption of the compound can be cal-
culated.
32
-------
Table 5 gives an example of linear Kp values, measured Koc values and
Koc values calculated from Kow values for the sorption of three hydrophobic
compounds, pyrene, dibenzothiophene and acetophenone by a variety of sediments.
TABLE 5. Kow, CALCULATED Koc, LINEAR Kp AND MEASURED Koc VALUES FOR SORPTION
OF PYRENE, DIBENZOTHIOPHENE AND ACETOPHENONE BY SOILS AND SEDIMENTS
Koc Sample
Compound Kow
Pyrene 124,000
Dibenzo- 24,000
thiophene
Aceto- 38.6
phenone
(calc'd) No.
76,400 B2
4
5
6
8
9
14
15
18
20
21
22
23
26
14,700 B2
4
5
6
8
9
14
15
18
20
21
22
23
26
23.8 B2
4
5
6
8
9
14
15
18
20
21
22
23
26
%OC
1.21
2.07
2.28
0.72
0.15
0.11
0.48
0.95
0.66
1.30
1.88
1.67
2.38
1.48
1.21
2.07
2.28
0.72
0.15
0.11
0.48
0.95
0.66
1.30
1.88
1.67
2.38
1.48
1.21
2.07
2.28
0.72
0.15
0.11
0.48
0.95
0.66
1.30
1.88
1.67
2.38
1.48
Kp
774
1098
1191
633
125
79
285
783
509
747
1159
811
1130
1023
117.5
180.6
167.1
60.8
9.4
5.8
49.7
179.9
65.1
101.4
276.0
176.3
388.6
134.5
0.44
0.89
0.56
0.68
0.07
0.09
0.12
0.27
0.30
0.29
0.85
0.53
0.68
0.66
Koc
(meas 'd)
63,991
53,019
52,250
87,847
83,333
71,818
59,271
82,453
77,182
57,469
61,628
48,557
47,487
69,108
9711
8725
7329
8444
6267
5273
10,354
18,937
9864
7800
14,681
10,557
16,328
9088
36
43
24
95
48
82
25
28
46
22
45
31
29
45
Average
Koc
63,400
11,230
38.6
33
-------
The range in Kp values for the adsorption of hydrophobia compounds
depends on the compound being adsorbed and the range in organic carbon contents
found in the soils or sediments studied. The upper limit for Koc values de-
pends on the compound, but appears to be around 2,000,000 due to present
analytical chemistry limitations. The lower limit for the validity of the
Koc-Kow relationship has not yet been defined. This limit will be reached
when case 1 adsorption, i.e., a specific strong adsorbate-adsorbent inter-
action, is encountered.
A relationship has been demonstrated for nonlinear Freundlich isotherms
when the data are expressed on a molar basis instead of a mass basis (Osgerby,
1970). Molar Kd values may be calculated from mass Kd values by the following
equation:
Kd(Molar) = Kd(Mass) x Molecular weight (Eq. 27)
Molecular weight
Where Kd(Mass) and 1/n are Freundlich constants and the molecular weight is
that of the adsorbate.
INTERPRETATION OF TABULATED DATA
Various combinations of the influencing factors discussed above are
necessary to explain the adsorption data obtained from the literature and
tabulated at the end of this chapter. For the nonpesticide organics, the ad-
sorbents used in most of the studies reviewed were montmorillonite clay or
carbon rather than natural sediments or soils. Thus, rather than a variety of
adsorbents with a range of characteristics, two distinctly different types are
represented: an inorganic clay mineral and an organic.
The chemical characteristics of the adsorbate account for much of the
variation in adsorption behavior shown in the tabulated data. These effects
were best shown in studies of groups of related compounds. Linner and
Gortner (1935) studied the adsorption of 31 organic acids on carbon; the re-
sults are summarized in Table 6. Traube's rule that adsorption from aqueous
solutions increases with molecular weight for a homologous series was demon-
strated for fatty acids but not for other acids. The branched chain had
little effect on the maximum adsorption of the acids, but the double bond
showed a tendency to decrease adsorption. The introduction of polar groups—
carboxyl, hydroxyl, or keto—caused decreased adsorption. The decrease was
more pronounced as the number of carboxyl groups increased or as a second
hydroxyl group was introduced. The decrease in adsorption caused by the keto
group was dependent on the length of the chain and the position of the polar
group in the chain.
For 52 structurally related N-phenylcarbamates, acetanilides, and
anilines from aqueous 2% ethanol solutions, the inverse relationship between
solubility and adsorption accounted for 60 percent of the total variation in
adsorption, shown by the data in Table 6 (Ward and Upchurch, 1965). All of
the compounds were adsorbed on nylon and cellulose triacetate. Other than
solubility, the principal variable factor affecting adsorption was the diff-
erence in the molecular structures of the compounds. An investigation of
34
-------
compounds having systematic variations in molecular structure shows which
sites in the molecule can be involved in adsorptive processes and how various
substituents may influence the extent of adsorption. For those compounds,
differences in molecular structure caused differences in adsorption as a re-
sult of steric hindrance, tautomerism, chelation, and induction. The results
suggest that the preferred adsorption mechanism of the amido compounds from
aqueous solution is via the adsorbate's imino hydrogen and the adsorbent's
carbonyl oxygen. If neither of these is available, however, alternative
binding sites are utilized.
As a means of establishing a g_uantitative relationship between soil
sorption equilibria and chemical structure, Lambert (1967) proposed the
following relationship between parachor of uncharged organic chemicals for
which no appreciable hydrogen bonding occurs and the soil sorption of those
chemicals :
K = alAu (Eq. 25)
The relationship is based upon extrathermodynamic linear free energy approxi-
mations and uses of parachor as an approximate measure of the molar volume of
the chemical. Distribution equilibria between soil and water for a number of
chemical homologs of two chemical classes, including anilines (see Table 6)
were used to establish the relationship. The relationship emphasizes the im-
portance of using the partition or distribution coefficient, defined with re-
spect to organic matter, as the most representative index of soil sorption
equilibria.
Hance (1969) extended this relationship. A factor given by (parachor-
45N) , where N is the number of sites in a molecule which can participate in
the formation of a hydrogen bond, was correlated with the logarithm of the
Freundlich K value for the adsorption of 29 aromatic herbicides. Again, the
relationship is valid for soils in which organic matter is the dominant adsorb-
ing 'constituent.
In the case of a few compounds, adsorption constants were determined
for more than one adsorbent (Table 6) . Where data were obtained on both a
clay mineral and a sediment, the adsorption was generally greater on the sedi-
ment. Some data on sediments and soils, including those for benz.(a)pyrene,
pyrene, methoxychlor , and carbaryl, show a correlation between adsorption and
organic matter content (Table 6) (Smith, Mabey, Bohonos, Holt, Lee, Chou, MilL
and Bomberger, 1976a; Karickhoff, Brown, and Scott, 1978; La Fleur, 1976a) .
In addition to the adsorption constants for specific compounds and
adsorbents, additional pertinent data are tabulated here. Adsorption con-
stants for a number of pesticides averaged over several soils are shown in
Table 7. Also, Tables 8 and 9 show the inverse relationship between R
values obtained by soil thin-layer chromatographs and adsorption or adsorbate
characteristics .
(Note: the references cited in this chapter are listed beginning on p. 110.)
35
-------
TABLE 6: ADSORPTION CONSTANTS FOR ORGANIC COMPOUNDS
Compound Name
Ref.
en
Acids, Aliphatic
acetic acid
C2H402
Compound properties^
m.w. 60.05
m.p. 16.604°C
b.p. 117.9°C
density 1.0492?°
water sol °°
COMPOUNDS OTHER THAN PESTICIDES
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= ?jj_ -
0.462 0.266 1.736
Adsorption equation: a= aC
1/n
a 1/n
2.46 0.351
Experimental Conditions: 1 gm of adsorbent and
concentrations or reagents varying from 0.01
to 0.25 molar.
Linner
and Gortner.
1935
See notes at end of table
-------
TABLE 6: Continued
Compound Name
Ref.
adipic acid
C6H10°4
Compound properties
m.w. 146.14a
m.p. 151°Ca
b.p. 265°C at 100mma
density 1.360jsa
water sol 1.5
isfc
Adsorbent Adsorption equation: a=—j^—p
nordite
(decolorizing
carbon) °e ° B
2.347 1.886 1.245
Adsorption equation: a=aC
a 1/n
1.79 0.163
Experimental Conditions: same as for acetic acid.
Linner
and Gortner,
1935
butyric acid
C4H8°2
Compound properties0
m.w. 88.12°C
m.p. -4.26°C
b.p. 163.53-C
density 0.95775°
water sol «•
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= ?? c
aB a 8
1.689 0.863 1.957
Adsorption equation: a= oC1'"
a 1/n
2.46 0.177
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref.
butyric acid
C4H8°2
Compound properties0
m.w. 88.12
m.p. -4.26°C
b.p. 163.53°C
density 0.95775°
water sol «°
Adsorbent
activitated
charcoal BIO
Adsorption equation: y= a.x
x - range I
(mmol/dra )
0.08 - 7.18
a b
0.878 0.4
Spahn et al.
1974
CD
n-butyric acid
Adsorbent
XAD-2
(amberlite resin)
Adsorption equation: — = zrr- + ^
(Langmuir)
K(25°C)
b(25°C)
-3
23.7 liter/mole 1.46X10 mole/g
Enthalpy of adsorption:
Gustafson
et al.,
1968
AH°= 2.303
7X10~4 mole
9X10 4 mole
-AH°*
4.1 kcal/mole
2.4 kcal/mole
1.2X10"3 mole 2.1 kcal/mole
*AH decreases with increasing surface coverage, i.e. energetically
preferred sites are utilized first.
-------
TABLE 6: Continued
Compound Name
Ref.
caproic acid
CH3(CH2)4C02H
Compound properties
m.w. 116.16a
m.p. -2 to -1.5°Ca
b.p. 205°Ca
density 0.9274£°a
water sol 0.4 gm/100 ml
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
_
ago 6
8.772 4.636 1.892
Adsorption equation: a= a
a 1/n
3.03 0.175
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
citraconic acid
C5H6°4
Compound properties
m.w. 130.10a
m.p. 91°Cfc
density 1.617a
water sol 238 cold
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= °^_
06 a 3
1.356 1.014 1.337.
Adsorption equation: a=
a 1/n
1.69 0.167
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref.
citric acid
C6H8°7
Compound properties
m.w. 192.14a
m.p. 153°C (anhydrous)"2
b.p. decompa
density 1.542{ab
water sol 133 cold gm/100 ml
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= y^——
aB a 6
1.444 2.757 0.524
Adsorption equation: a= aC1//n
a 1/n
0.73 0.203
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
dibromosuccinic acid
C4H402BT2
Compound properties
m.w. 275.90
m.p. 151-3°C
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= °^
1.397 1.119
1.248
Adsorption equation: a= aC1/"
Linner
and Gortner,
1935
a 1/n
2.58 0.320
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref.
formic acid
HCO H
Compound properties1'
m.w. 46.03
m.p. 8.4°C
b.p. 100.7°C
density 1.220^°
water sol •>
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
agC
1+aC
aB a B
0.273 0.159 1.710
Adsorption equation: a= aC1/"
a 1/n
2.47 0.435
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
fumaric acid
C.H 0.
444
Compound properties
m.w. 116.07fc
m.p. 287°Cb
b.p. 200 subl.fc
165 subl.a
density 1.6355ofc
water sol 0.7025; 9.8looi
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a
08 a B
7.097 5.798 1.224
Adsorption equation: a= aC1//n
a 1/n
2.81 0.248
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref.
glutaric acid
C5H8°4
Compound properties
m.w. 132.lla
m.p. 99°Ca
b.p. 304 decomp.
density 1.424i;5a
water sol 642°a
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
aB a B
3.697 3.104 1.192
Adsorption equation: a= aC
a 1/n
1.96 0.201
1/n
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
glyceric acid
C3H6°4
Compound properties'2
m.w. 106.08
b.p. disintegrates
water sol «
Adsorbent
nordite
(decolorizing
carbon)
a BC
Adsorption equation: a= ,+
06 a B
0.668 0.812 0.823
Adsorption equation: a= aC1'"
a 1/n
1.29 0.267
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref .
glycolic acid
HOCH CO_H
Compound propertiesc
m.w. 76.05
m.p. 80°C
b.p. decomposes
Adsorbent
nordite
(decolorizing
carbon)
n Rf
Adsorption equation: a= ,?
aB a B
0.239 0.249 0.958
Adsorption equation: a= aC-1-/11
a 1/n
1.54 0.390
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
glyoxylic acid
C2H2°3
Compound properties
m.w. 74.04a
m.p. 70-5°Ca
(+l/2w)
98 (anhydrous)
water sol very soluble
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= °
aB a 6
0.508 0.223 2.275
Adsorption equation: a= aC
a 1/n
3.89 0.455
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref -
isobutyric acid
(CH3) 2CHCO2H
Compound properties
nordite
carbon) a (3 a B
Linner
and Gortner,
1935
m.w. 88.lf
m.p. -46.1°Ca
b.p. 153.7°Ca
density 0.96815$°^ .949?°*
water sol 20 20 gm/100 mlb
0.883 0.497 1.776
Adsorption equation: a= aC
a. 1/n
2.36 0.273
,1/n
Experimental Conditions: same as for acetic acid.
isovaleric acid
C5H10°2
Compound properties
m.w. 102.13a
m.p. -29.3°Ca
b.p. 176.7°Ca
density 0.9286$°a
water sol 4.22oi
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
1.630 0.902 1.807
Linner
and Gortner,
1935
Adsorption equation: a= oC
o 1/n
2.51 0.227
,1/n
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref.
itaconic acid
C5H6°4
Compound properties
m.w. 130.10a
m.p. 175°Ca
b.p. decomposes
density 1.632fc
water sol 8.332oi
Adsorbent Adsorption equation: a= y£—
nordite
(decolorizing
carbon) a.& a 0
1.167 0.904 1.291
Adsorption equation: a= ac1//n
a 1/n
1.54 0.148
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
lactic acid (DL)
C3H6°3
Compound properties
m.w. 90.08a
m.p. 18°Ca
b.p. 122°Ca
density 1.249 lsb
water sol •»
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= ° *••
0.437 0.415 1.054
Adsorption equation: a= aC
a 1/n
1.66 0.335
1/n
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref
CTi
levulinic acid
Compound properties
„
m.w. 116.13
m.p. 37.2 °Ca
b.p. 246°C slight decomp.a
density 1.1335?oa? 1.1395j°fc
water sol very sol
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= y^*.,
2.990
a
2.289
8
1.307
Adsorption equation: a=ac n
a
1.83
1/n
0.183
Experimental conditions: same as for acetic acid
Linner
and Gortner,
maleic acid
C4H4°4
Compound properties
m.w. 116.07a
m.p. 139-140°Ca
b.p. 135 decamp-^
density 1.590?oi>a
water sol 78.82S; 392.697-5fc
Adsorbent
nordite
(decolorizing
(carbon)
Adsorption equation : a=
06 a B
1.233 0.884 1.395
Adsorption equation: a=oC
a 1/n
1.90 0.203
Linner
and Gortner,
1935
Experimental conditions: same as for acetic acid
-------
TABLE 6: Continued
Compound Name
Ref
malic acid (I)
C4H6°5
Compound properties
Adsorbent
nordite
(decolorizing
age
rvR n ft
Linner
and Gortner,
1935
m.w. 134.09
m.p. 100°C
b.p. 140°C decomp.
density 1.595
water sol very sol
malonic acid
Compound properties
m.w. 104.06fc
m.p. 135. 6°C subl.£
b.p. decomp. at 140 °C
density 1. 631,,1 sb; 1.619a
water sol 61.1°0gm/100
73.5 gm/100 ml
92.650gm/100 ml
carbon)
0.531 0.574 0.927
Adsorption equation: a=aC
1/n
a 1/n
1.28 0.252
Exoerimental conditions: same as for acetic acid
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
agC
1+aC
aft a 6
1.897 1.540 1.232
Adsorption equation: a=ctC 'n
a 1/n
3.88 0.410
Linner
and Gortner,
1935
Experimental conditions: same as for acetic acid
-------
TABLE 6: Continued
Compound Name
Ref
mesaconic acid
C5H6°4
Compound properties
m.w. 130.10a
m.p. 204.5
b.p. 250°C decomp.
density 1.466$"g/ml^
water sol 2.7 '
118'
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation : a=
ctBC
aB a B
2.706 1.886 1.435
Linner
and Gortner,
1935
Adsorption equation: a=aC
a 1/n
1.80 0.133
1/n
00
Experimental conditions: same as for acetic acid
methylsuccinic acid
C5H8°4
Compound properties
m.w. 132.11
m.p. 111°C
b.p. decomp.
density 1.410g/ml
water sol 66.72 °
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
.
ag a 6
0.664 0.608 1.092
Adsorption equation: a=aC
a 1/n
1.30 0.172
1/n
Linner
and Gortner,
1935
Experimental conditions: same as for acetic acid
-------
TABLE 6: Continued
Compound Name
Ref
monobromosuccinic acid
C4H504Br
Compound properties
fc
m.w. 197.00
m.p. 15
density 2.073
water sol 19
161°C
a
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a=
1+aC
08 a 6
0.934 0.643 1.451
Adsorption equation: a=ccC
a 1/n
1.82 0.195
Experimental conditions: same as for acetic acid
oxalic acid
C2H2°4
Compound properties
m.w. 90.04a
m.p. 189.5°Ca
b.p. 157°C subl.a
density 1.900i7<2
water sol 19.515 gm/lOOml1
Adsorbent
nordite
(decolorizing
carbon)
Adsorotion eauation: a=
Qt6C
1+aC
0.440 0.332 1.325
Adsorption equation: a=oC
1/n
120'° gm/lOOml (hydrated form)
a 1/n
3.62 0.551
Linner
and Gortner,
1935
Linner
and Gortner,
1935
Experimental conditions: same as for acetic acid
-------
TABLE 6: Continued
Compound Name
Ref.
propionic acid
C3H6°2
Compound properties
m.w. 74.08
m.p. -20.8°C
b.p. 140.99'C
density 0.993020
water sol «°
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= ?^
06 a 3
0.925 0.491 1.885
Adsorption equation: a= aC
1/n
a 1/n
2.46 0.236
Linner
and Gortner,
1935
Experimental conditions: same as for acetic acid.
propionic acid
C3H6°2
Compound properties
m.w. 74.08
m.p. -20.8°C
b.p. 140.99'C
density 0.993020
water sol -
Adsorbents
Activated
charcoal BIO
Adsorption equation: y= a-x
Adsorption constants:
x-range I
(mmol/dm )
0.1 - 8.3
a b
0.497 0.4
Spahn
et al.,
1974
-------
TABLE 6: Continued
Compound Name
Compound properties
m.w. 88.06a
m.p. 13.6°Ca
b.p. 165°C slight decomp.
density 1.2272?"
water sol °°
carbon)
a.6 a B
0.979 0.585 1.674
Adsorption equation: a= ctC
a. 1/n
2.44 0.273
,1/n
Ref.
pyruvic acid
C3H4°3
Adsorbent
nordite
r* ft ("*
Adsorption equation: a= ]_+aC
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
succinic acid
C.H,0.
464
Compound properties
m.w. 118.09
m.p. 185°C
b.p. 235°C dissint.
density 1.564 I5 g/ml
water sol 6.8 at 20°C
121 at 100°C
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= °
06 a 6
0.865 0.467 1.854
Adsorption equation: a= aC
1/n
a. 1/n
2.44 0.273
Linner
and Gortner,
1935
Experimental Conditions: same as for acetic acid.
-------
TABLE 6: Continued
Compound Name
Ref
tartaric acid
C.HC0
466
Compound properties
m.w. 150.09^
m.p. 100°C*
density 1.697 ; 1.788a
water sol 20.62ob; 9.23°
Adsorbent
nordite
(decolorizing
carbon)
185101
Adsorption equation: a= "
aB a 6
0.322 0.468 0.687
Adsorotion eauation: a=aC
a 1/n
0.94 0.275
1/n
Linner
and Gortner,
1935
to
Experimental conditions: same as for acetic acid
valeric acid
Compound properties
m.w. 102. 13a
m.p. -33.83°Ca
b.p. 186.05°Ca
density 0.939l5°a; 0.9425°*
water sol 3.7gm/100ml
Adsorbent
nordite
(decolorizing
carbon)
Adsorption equation: a= aC
1/n
a 1/n
2.84 0.182
Adsorption equation: a=
a6 a 6
1.878 0.872 2.154
Linner
and Gortner
1935
Experimental conditions: same as for acetic acid
-------
TABLE 6: Continued
Ui
U)
Compound Name
Acids, Aromatic
benzoic acid
Adsorbents Adsorption equation: —
C..H 0
762 Type BL -
Compound properties activated carbon orption constants:
(Pittsburgh ^
m.w. 122. 13a Chemical Co.)
m.p. 122.4°Ga Surface area Compound pjca
b.p. 249-C* 1000-1100 v /g benzoic acid 4.20
density 1.2659isi
-, n -.n^b -2,4-dichloro 2.76
water. sol 0.18* ,
n 0718°
u • *•• ' i,
2.27sb
-3-amino-2,5- 3.40
dichloro
(amiben)
-3-nitro-2,5- 3.23
dichloro
-2-methoxy-3,6- 1.94
dichloro
(dicamba)
= (TT§C)
pH of
so In.
3
7
11
3
7
11
3
7
11
3
7
11
3
7
11
a*
0.238
0.108
0.081
0.259
0.123
0.108
0.928
0.283
0.025
0.360
0.118
0.035
0.181
0.317
0.068
b
510
124
75
676
159
73
515
131
72
505
130
93
394
154
68
Ref
Ward and
Getzen,
1970
x/m
489
113
67
651
147
69
510
127
51
491
120
72
313
149
59
*0nits: a = liters/y mole
b = v moles/g
c = y moles/liter
— = p moles/g
Experimental conditions: 100 ml aqueous acid solution: lOmg carbon
-------
TABLE 6: Continued
Comoound Name
Ref.
benzole acid
C7H6°2
Compound properties
m.w. 122.13°
m.p. 122.4°ca
b.p. 249°Cb
.,fc
density 1.2659*
ufc
water sol 0.18
0.2718
2.275
Adsorbent
activated
charcoal BIO
Adsorption equation: y= a-x
Adsorption constant:
x-range I
(mmol/dm a
0.1 - 6
3.06 0.181
Spahn
et al.
1974
benzoic acid and
substituted benzoic acids
C7H6°2
Adsorbent
charcoal,
activated,
200 mesh
Adsorption equation:
log x/m = log k + 1/n log c
Hartman,
Kern,
Bobalek,
1946
1/n and log k Values
Acids
Benzoic
o-Chlorobenzoic
o-Aminobenzoic
o-Hydroxybenzoic
o-Toluic
m-Toluic
p-Toluic
log k
1/n
0.3680
0.4060
0.3693
0.3840
0.3879
0.3581
0.3696
20°
0.0613
0.2208
0.3472
0.2700
-0.0215
-0.0092
0.1351
30°
0.0265
0.1834
0.3031
0.2385
-0.0719
-0.0582
0.0762
40°
-0.1091
0.1303
0.2678
0.2091
-0.2510
-0.1791
-0.0324
50°
-0.2551
0.0936
0.2218
0.1844
-0.5232
-0.3732
-0.1886
Adsorption from benzene solutions.
-------
TABLE 6: Continued
Compound Name
phenyl acetic acid
Adsorbent
C6H5CH2C02H Activated
Compound properties" charcoal
m.w. 136.16
m.p. 77°C
b.p. 265. 5°C
density 1.091J7; 1.228"
water sol slightly sol. BIO
LW
Lev 634
BD
Dl
D2
B2
LS- supra
Decaka 9
106/427/1
106/427/5
106/427/3
Adsorption equation:
y= a
b
• x
Ref .
Spahn
et al.,
1974
Adsorption constants:
x-range I
(mmol/dm )
0
0
0
0
0
0
0
0
0
0
0
0
.1 -
.05 -
.1 -
.1 -
.05 -
.1 -
.1 -
.1 -
.1 -
.1 -
1 —
1 —
10
12
8
22
7
8
11
7
8
7
6.5
8
a
2
1
0
1
1
1
1
1
1
1
1
2
.51
.84
.14
.93
.57
.75
.82
.53
.87
.08
b_
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
x-range II
(mmol/dm )
16
165
38
15
162
245
145
18
03
11
144
244
0
0
0
0
0
0
.001 - 0.1
.01 - 0.11
.001 - 0.31
.001 - 0.12
.001 - 0.11
.001 - 0.12
a b
2.6 0.32
1.76 0.56
1.53 0.23
2.05 0.33
1.85 0.3
2.6 0.44
-------
TABLE 6: Continued
Compound Name
Carboxylic acids, aromatic
Phenoxyacetic acid
Adsorbents Adsorption equation:
C H 0
883 Type BL -
Compound properties ^Pittsburgh"60" Adsorption constants:
m.w. 152.14 Chemical Co.)
oqo,-. Surface Area 9 Compound pka
p- 1000-1100 v /g
b.p. 285 °C slight decomp. Phenoxyacetic ^ ^
water sol 1.2 10
-4-chloro- 2.36
Ul
CTv
-2,4-dichloro- 3.31
-2,4,6-
trichloro- 3.35
2,4-dichloro- 3.92
x _ abC
Iff" (1+aC)
pH of
soln.
3
7
11
3
7
11
3
7
11
3
7
11
3
7
11
a*
0.423
0.229
0.209
0.362
0.101
0.115
0.279
0.112
0.070
0.672
0.095
0.073
0.431
0.125
0.100
b
446
105
64
575
198
145
629
223
154
676
239
144
645
235
59
Ref .
Ward and
Getzen,
1970
X
m
436
86
43
560
180
133
607
205
135
666
216
127
630
218
54
Experimental Conditions:
10 mg carbon.
100 ml aqueous acid solution:
Units: a = liters/y mole
b = v moles/g
c = v moles/liter
— = v. moles/g
m
-------
TABLE 6: Continued
Compound Name
Ref.
2,4-dichloro-
phenylacetic acid
*Units: a = liters/y mole
b = y moles/g
c = y moles/liter
— = y moles/g
m
Adsorbents
Type BL -
activated carbon
(Pittsburgh
Chemical Co.)
Surface area
1000-1100 vVg
Adsorption equation: — =/fi~r>
Adsorption constants:
Pjca
3.92
Hard and
Getzen,
1970
pH of
so In.
3
7
11
a*
0.431
0.125
0.100
b
645
235
59
x/m
630
218
54
Experimental conditions: 100 ml aqueous acid solution: 10 mg carbon
-------
TABLE 6: Continued
un
CO
Compound Name
Alcohol
n-butyl alcohol Adsorbent
C4H9OH Graphite
Compound properties Blood Char.
m.w. 74.12G
m.p. -90°CC
b.p. 117-118°CC; 117.71°Cfo
density 0.810?°c
water sol 7.9 gm/100 ml
Ref .
Adsorption equation: — = —(l+N.v./N v ) Bartell,
m m b b a a Thomas,
„ , , . . and Fu,
N = mole fraction
v =
a =
b =
t°C
0
25
45
0
25
45
partial molar volume 1951
solvent
solute
AF°** AH0***
K* kcal/mole kcal/mole
63.3 -2.24 -0.16
61.6 -2.43 -1.47
52.7 -2.50
477 -3.34 -0.94
412 -3.54 -0.52
390 -3.76
*Equilibriuin constant K obtained from the limiting slope of
the adsorption isotherms at zero concentration
**AF° = -RT In K
tT T 1
***AH° = R' 2 1
\m _
(2 X
In K-
_ ~
K,
-------
TABLE 6: Continued
Ul
Compound Name
Amides
acetanilide and derivatives,
adsorption from 2% ethanol
C0H0ON
8 9
Compound properties
m.w. 135.16
ra.p. 114°C
b.p. 305°C
density 1.21JJ
water sol 0.56325,- 3.580
Compound
ff-Ethylacetanilide
4 -Hydroxy acetanilide
Acetanilide
2-Chloroacetanilide
4-Aminoacetanilide
flf-n-Butylacetanilide
2-Nitroacetanilide
2 -Hydroxyacetani 1 ide
tf-Phenylacetanilide
4-Chloroacetanilide
3 , 4-Dichloroacetanilide
4-Nitroacetanilide
4-Bromoacetanilide
2 , 5-Dichloroacetanilide
Adsorption
solubility
(x 10" 4M)
2% ethanol
2320
1580
624
375
352
167
138
32
31
16
12
11
11
10
equation:
V
0.05
0.25
0.21
0.25
0.06
0.23
0.16
0.26
0.26
1.19
6.05
1.02
1.73
0.92
Ref .
(s> = Kcl/n
Ward and
1/n = 1 Upchurch,
1965
V*
0.20
0.13
0.32
0.47
0.05
0.89
0.72
0.15
1.59
2.64
6.83
2.18
3.30
1.59
Method of analysis: UV spectrophotometry with Beckman DO spectrophotometer
* k,, = adsorption on nylon
** k = adsorption on cellulose triacetate
-------
TABLE 6: Continued
(Ti
O
Compound Name
aniline and derivatives,
adsorption from 2% ethanol
C..H NH
D J ^
Compound properties Compound
m.w. 93.13a Aniline
m.p. -6.3°Ca 2-Methylaniline
4-Methylaniline
b.p. 184.13°Ca tf-Methylaniline
density 1.02173?°a 4-Chloroaniline
water sol 3.4^; 6.4^ 2-Chloroaniline
ff-Ethylaniline
2-Nitroaniline
N , ff-Dimethylaniline
2 , 3-Dichloroaniline
3 , 4-Dichloroaniline
2 , 5-Dichloroaniline
4-Nitroaniline
tf-n-Butylaniline
2-Nitro-4-chloroaniline
2 , 4-Dinitroaniline
N- Ben zylani line
N- Phenylanil ine
Adsorption
solubility
(x 104M)
2% ethanol
4450
1670
1240
560
520
450
250
103
95
85
52
49
38
16
9
5
4
3
equation;
V
0.07
0.10
0.05
0.24
0.68
0.55
0.32
0.91
0.52
3.45
4.32
3.78
1.10
1.42
3.70
1.94
3.46
16.50
Ref .
: (-) = KC1/n; Ward and
m Opchurch,
1/n = 1
1965
V*
0.27
0.44
0.50
0.92
3.31
1.94
1.10
2.84
2.12
7.20
10.20
11.20
3.40
6.55
7.80
5.65
19.48
24.00
Method of analysis: UV spectrophotometry with Beckman DU spectrophotometer.
= adsorption on nylon
= adsorption on cellulose triacetate
-------
TABLE 6_J Continued
Compound Name
2
(di-R,) aniline
SD R R
11830 CH3 CH3
12639 C2H5 CH3
11831 C3H7 CH3
13207 C2H5 C2H5
12030 C3H? C2H5
12346 C3Hy C3H?
12400 CH-. iso-C,H.
Adsorption
Ripperdan
1% O.m
125
230
500
320
750
1170
222
Ref .
Lambert ,
equation: In K = aPAU*
1967
K values
soil Sacramento soil
5% O.m
145
193
520
269
702
-
*K = equilibrium constant, estimated from adsorption data
AU
ILL——, P = parachor, P= density of the liquid, y = surface tension, M = molecular weight
P
difference in internal pressures of the solvent phases
-------
TABLE 6: Continued
CT>
Compound Name
crystal violet
(gentian violet)
C25H30C1N3
Compound properties0
m.w. 408.06
water sol soluble
Amino acid
dl-tryptophan, from aqueous
urea solution
C11H12N2°2
Compound properties
m.w. 204.22
m.p. 283-5°C
water sol slightly sol cold
sol hot
Adsorbent
activated
charcoal
Adsorbent
carbon black
Urea
Concentration
H
0
0.11
1.01
3.05
5.03
7.07
Adsorption
BIO
Adsorption
x-range I
(mmol/dm
0.1 - 2
Adsorption
Ref .
Spahn
equation: y= a- x et al.
1974
constants:
a b
0.84 0.09
^_ Nogami, Nagai,
J.TDL
1968
1? AF AH AS fiSt ASS
10 J liter 10 J liter Real Kcal _ „
mole mole
1.63 1.70
1.60 1.70
1.54 1.08
1.28 0.615
1.18 0.472
0.92 0.397
mole mole - - - -
-4.45 0.22 15.4 0 15.4
-4.45 — 15.4 0.05 15.4
-4.18 — 14.5 0.38 14.9
-3.87 — 13.5 1.15 14.7
-3.70 — 12.9 1.68 14.6
-3.57 — 12.5 2.08 14.6
AF = free energy change
AS = entropy change
AS = AS + AS.
s *c
AS. = entropy change of the transfer of tryptophan from
aqueous solution to aqueous urea solution
e.u. = entropy units
-------
TABLE 6: Continued
Compound Name
Ref .
Benzene
benzene - adsorption from
binary mixture
C6H6
Compound properties
m.w. 78.11d
density . 87901fc
m.p. 5.5°Ce
b.p. -80.1°Ce
water sol 820 ppm at 22°C-'
OCT/water part coeff 130s
Solvent
Ethylene dichloride
Cyclohexane
Carbon tetrachloride
Adsorbent
Adsorption equation:
X1X2 = 1
n°AX/m
K
Graphon 18.5
Spheron 6 5
Coconut shell charcoal 19.9
Decolorizing charcoal 16.4
Decolorizing charcoal 16.1
Coconut shell charcoal 18.2
Area of
adsorbent
m2/g
119
57
677
596
374
350
(AH£ - AH°*
cal/g
0. 54
-
12.0
7.1
4 .0
3.8
Zettlemoyer
and Micale,
1971
K = exp-(
AHa
RT
ASa,
-------
TABLE 6: Continued
Compound Name
Carbamates
carbamate derivatives,
adsorption from 2% ethanol
RlNHCOOR2
Adsorption
equation :
x. _
1/n
solubility , t
Compound 2% ethanol ^1
Ethyl-tf-methyl-ff-phenyl
Ethyl-ff-benzyl
Ethyl-ff-phenyl
Ethyl-ff-ethyl-ff-phenyl
Ethyl-ff-(2-nitrophenyl)
ff-Phenylglycine ethyl ester
Phenyl
Isopropyl-ff-phenyl
Ethyl-ff- (4-chlorophenyl)
Ethyl-ff-butyl-ff-phenyl
n-Butyl-ff-phenyl
Ethyl-ff-(4-nitrophenyl)
Ethyl-ff-benzyl-/V-phenyl
Ethyl-ff- ( 2 , 5-dichlorophenyl)
Ethyl -ff- (2 , 3-dichlorophenyl)
Ethyl-ff , ff-diphenyl
Isopropyl-ff- (2-methyl-5-
chlorophenyl)
Methyl-ff- (2 , 4-dichlorophenyl)
Isopropyl-ff- (3-chlorophenyl)
Isopropyl-ff- (3 , 4-dichlorophenyl)
172
121
96
78
71
64
28
16
9.6
8.5
8.5
5.7
2.9
2.6
2.5
1.7
1.6
0.72
0.50
0.32
0.22
0.49
1.03
0.25
0.90
0.16
0.40
1.16
5.70
0.80
2.20
3.65
1.85
4.00
3.65
1.02
3.37
15.10
9.00
23.00
Ref .
Ward and
KC1/" Upchurch,
= 1 1965
V*
1.42
2.03
3.68
1.83
3.25
0.83
0.58
4.95
14.70
6.75
9.62
8.75
12.65
19.40
27.90
9.10
14.00
—
8.45
—
Method of analysis: UV spectrophotometry with Beckman DU spectrophotometer
*kN = (amount adsorbed/weight of nylon) / (C1//n)
**, = (amount adsorbed/weight of cellulose triacetate)/(C /n)
-------
TABLE 6: Continued
Compound Name
Ref.
carbamate derivatives,
adsorption from 2% ethanol
Adsorption equation: ^
KC
(1/n = 1)
Hard and
Upchurch,
1965
Adsorbent
Nylon
(Zytel-101)
(80 mesh)
Compound
Ethyl-ff-phenyl
Isopropyl-JV-phenyl
Ethyl-ff-methyl-JV-phenyl
Ethyl-/»-ethyl-»-benzyl
Ethyl-ff-benzyl-Af-phenyl
Ethyl-ff,»-diphenyl
Isopropy1-ff-(3-chlorophenyl)
Ethyl-ff-(2-nitrophenyl)
Ethyl-JV- (4-nitrophenyl)
Ethyl-ff-(2,3-dichlorophenyl)
10"C
1.03
1.16
0.22
0.25
1.33
0.66
9.00
0.75
3.65
3.70
26.5°C
1.03
1.16
0.22
0.25
1.85
1.02
9.00
0.90
3.70
3.70
50°C
1.03
1.16
0.22
0.25
1.85
1.02
9.00
0.90
3.70
3.70
Method of analysis: UV spectrophotometry with Beckman DU spectrophotometer.
-------
TABLE 6: Continued
Compound Name
Ref.
Carbonyls
acetophenone
C,HCCOCH,
65 3
Compound properties
m.w. 120.16h
m.p. 20.5°Ch
b.p. 202.0°Ch
density 1.0281 at 20°C/4°C?I
water sol 5.6xlO~3M at 25°C1
Adsorbent
activated
charcoal B 10
Adsorption equation: y= a-x
Adsorption constants:
x-range I
(mmol/dm )
0.1 - 4
3.46 0.155
Spahn
et al.,
1974
CTi
N-Heterocyclics
benzo[f]quinoline
C13H9N
Compound properties
m.w. 179.22
m.p. 93.5°C
b.p. 350°C (721 torr)
202-5°C (8 torr)
vapor pressure at 20°C (torr)
water sol ( pg ml"1)
76.112.2
*TOC - total organic carbon
**CEC - cation exchange capacity
Adsorbent
Coyote Creek
sediment
Adsorption equation: S = K S , n=l
TOC*
1.4
CEC*
13.5
13131170
Smith, Mabey,
Bohonos, Holt,
Lee, Chou,
Bomberger, Mill,
1977
-------
TABLE 6: Continued
Compound Name
Ref.
9H-carbazole
C,H.HHC,H.
b 4 64
Compound properties
m.w. 167.21
m.p. 247-248°C
water sol (1.0 pg/ml)
Adsorption equation: Cg = KpCw
Adsorbent
Ca-montmorillonite 3.20±1.06
Coyote creek sediment 175 ±20.9
Smith, Mabey,
Bohonos, Holt,
Lee, Chou,
Mi11, Bomberger,
1977b
7H-dibenzocarbazole (DBC)
C10H6NHC10H6
Compound properties
m.w. 267.31
m.p. 155-159°C
water sol 2.4X10~7M
Adsorbent
Des Moines River
sediment
Coyote Creek
sediment
Searsville Lake
sediment
*TOC = total organic carbon
**CEC = cation exchange capacity
***Based on analysis of the supernatant at equilibrium
Adsorption equation: C = KDCW
TOC*
0.8
1.9
5.0
CEC*
10.5
13.5
34.5
32,600
18,500
27,600
Smi th, Mabey,
Bohonos, Holt,
Lee, Chou,
Mill, Bomberger,
1977a
-------
TABLE 6: Continued
Compound Name
Ref.
pyridine
C5H5N
Compound properties'^
m.w. 79.10
m.p. 42.0°C
b.p. 115.3°C
density .982 at 20°C
water sol -
Adsorbent
activated
charcoal B 10
Adsorption equation: y= a-x
x-range I
|mmol/dm ) a b
0.14 - 7.4 1.22 0.2
Spahn
et al.
1974
CD
pyridine
Adsorption equation:
X = KCen, X = mg/g;
Ce = mg/1
Baker and
Luh,
1971
Temp.
1°
24°
1°
24°
EM
2
2
2
2
K
0.03
0.01
0.12
0.06
n
1.01
1.03
1.04*
1.02
Adsorbent
Na-kaolinite
Na-montmorillonite
Method of analysis: liquid scintillation with Packard Tri-Carb spectrometer
4
Note: clay: pyridine ratio was varied from 12.15 to 6.25x10
for ratio (12.15) effect of pH was studied:
max adsorption for Na-kaolinite was found at pH 5.5; pka pyridine = 5.25
max adsorption for Na-montmorillonite was found at pH 4.0
•discrepancy noted between data given Table 2 p.842 and regression equation p.843, believe
this correct value.
-------
TABLE 6: Continued
Compound Name
Ref.
quinoline
C9H7N
Compound properties
m.w. 129.15
water sol 6.11 yg/ml
pKb - 9.5*
m.p. -14.5°C
b.p. 161.9°C
Adsorption equation:
_
p
adsorbed ,ug in solution
Adsorbent
TOC
0.05
Ca-montmorillonite
Coyote Creek sediment 1.4
CEC
69
13.5
V
7.28+0.52
10.9±0.4
ml
Experimental conditions: quinoline concentrations 4 and 8 p.g/ml
sediment concentrations 1000 to 3000 times that of quinoline.
-1
Smith,
Mabey,Bohonos,
Holt, Lee,
Chou, Mill,
Bomberger,
1976b
Method of analysis: 0V spectrophotometry with Gary Model 11
spectrophotometer.
*Quinoline is calculated to be 97%, 24%, and 0.32% protonated
at pH 3, 5, and 7, respectively.
-------
TABLE 6: Continued
Compound Name
Ref.
-J
O
S-Heterocyclics
ben zo[b]thiophene
C8H6S
Compound properties
m.p. 31.3°C
b.p. 212.9°C
water sol 127.3±2.5 at 20°C
Adsorbent
Coyote Creek sediment
Adsorption equation: S =K S , n=l
TOG CEC £
1.4 13.5 50±5
Experimental conditions: sediment loadings of 2000:1 and
5000:1 sediment: BT by weight
Smi th, Mabey,
Bohonos, Holt,
Lee, Chou,
Mill, Bomberger,
1976c
dibenzothiophene
C12H8S
Compound properties
m.w. 184.27
m.p. 99-100°C
b.p. 332-333°C
water sol 1.11±0.09
Adsorption equation: S =K S , n=l
Adsorbent
Coyote Creek sediment
Toe
1.4
CEC
13.5
1380±130
Smith, Mabey,
Bohonos, Holt,
Lee, Chou,
Bomberger, Mill,
1977
-------
TABLE 6: Continued
Compound Name
Phenols
phenol
C6H5OH
Compound properties
m.w. 9411d
m.p. 40.9°Ce
b.p. 180°C/740mmk
density 1.072 g/ml2*
!•
Ref.
Adsorption equation: y=a- x Spahn
et al.,
Adsorbent
X- range I 1974
activated charcoal (mmol/dm3) a b
D XU
0.1-8 2.16 0.23
X-range II
(mmol/dm ) a b
0.001-0.06 3.6 0.39
water-sol 84.12 mg/ml
Polynuclear aromatics
benz[a]anthracene
C18H12
Compound properties
m.w. 228.28
m.p. 155-7°C
b.p. (at 760 torr)
435°C
water sol at 27°C
Adsorbent
Coyote Creek
sediment
Adsorption equation: s =K S , n=l
s p w
TOC CEC
K
_£_
1.4 13.5 26,200±1700
Smith, Mabey,
Bohonos,
Holt, Lee,
Chou, Bomber-
ger. Mill,
1977
-------
TABLE 6: Continued
Compound Name
benzo[a]pyrene
C20H12
Compound properties
m.w. 252. 32a
m.p. 178°CZ
b.p. ^500°C
311°C at 10 torr
water sol 1.2±0.1 ng/ml
pyrene
C16H10
Compovind properties
m.w. 202 l
m.p. 150°CZ
b.p. 393°CS
density 1.1271a
water sol .135±.005 mg/lm
Oct water part coeff:
KOW=150,000
Ref
Adsorption equation: x=K C Smith, Mabey
P Bohonos ,
K Holt, Lee,
Total organic CEC _•, ^> _4 rhon Mill
Adsorbent carbon {%) meg. lOOg (xlO q) Bobber go r
Ca-montmorillonite 0.06 69.0 1.7+0.5
1976a
Des Moi-nes River 0.6 10.5 3.512.7
Coyote Creek 1.4 13.5 7.6+2.4
Searsville Pond 3.8 34.5 15.0+2.2
Groszek,
Adsorption equation: | = ^ + |^ ^^
q = heat evolved when the [cyclohex] is c
q° = total heat evolved when complete
Equilibrium constants:
Est. from the Est. from heat AF** AH
Adsorbent Langmuir isotherm* of ads. data Kj/mole Kj/mole
graphon 2200
oleophilic graphite 5930
"polar" graphite 2300
1750 18.7 23
4800 21.1 18
2340 18.9 26
Method of analysis: UV spectrophotometry with Onicam SP 500
spectrophotometer.
*at 21°
**AF° = -RTlnK
-------
TABLE 6: Continued
Compound Name
Ref.
pyrene
Compound properties
water sol (mole fractionXlO )=12
Koctanol water=150,000
Adsorbent
Hickory Hill
sand
coarse silt
medium silt
fine silt
clay
Doe Run
sand
coarse silt
medium silt
fine silt
clay
Oconee River
sand
coarse silt
medium silt
fine silt
clay
Adsorption equation:
X=K C;
% O.C.
0.13
3.27
1.98
1.34
1.20
0.086
2.78
2.34
2.89
3.29
0.57
2.92
1.99
2.26
Karickhoff,
Brown, and
Scott,
1979
KOC(X10
5
42
3000
2500
1500
1400
9.4
2100
3000
3600
3800
68
3200
2300
2500
0
0
1
1
1
0
0
1
1
1
0
1
1
1
.32
.92
.3
.1
.2
.11
.76
.3
.2
.2
.12
.1
.2
.1
Experimental conditions: sorbent concentrations 400 mg/ml of suspension
for sand, 20 mg/ml for coarse and medium silt, 10 mg/ml for fine silt
and 1 mg/ml for clay.
Method of analysis: UV spectrophotometry with Perkin Elmer 356
spectrophotometer.
-------
TABLE 6: Continued
Compound Name
Quinone
alizarin
C14H8°4
Compound properties'2
m.w. 240.23
m.p. 289-90°C (cor)
Ref .
Adsorbent
activated Spahn
charcoal Adsorption equation: y= a- x et al.,
B 10
1974
Adsorption constants:
x-range I
(mmol/dm ) a b
0.1 - 8 1.39 0.095
b.p. 430°C (sub)
water sol slightly sol
Sulfonate
sodium naphthalenesulfonate
C 1 C
Adsorbent Adsorption equation: — = zrr- + T-
- CJ JS.D D
Amberlite XAD-2
AH°* AFu0** ASu"***
Kcal/mole Kcal Kcal
25°C 319 4.58X10"5 -4.4 -5.7 +4.4
Method of analysis: UV spectrophotometry
Gustafson
et al.,
1968
*AH° = 2.303 RT,T2 (LogK^-logK')
**fiFu° = RTlnK; K=55.5K; K=e/(l-6)C; e=fractional surface coverage
***ASU° = (AH°-AFu°)/T
-------
TABLE 6: Continued
-J
LH
Compound Name
Carbamates
carbaryl
tf-methyl-1-naphthylcar hamate
C12H11N°2
Compound properties^ Adsorbent
PESTICIDES
Desorption
Adsorption
pH %o.m
m.w. 201 Lakeland s 5.3 0.22
water sol 350 pmol/1 Norfolk Is 6.0 0.57
Norfolk scl 5.4 0.15
Cecil si 6.3 1.77
Cecil c 5.7 0.53
Okenee si 4.65 5.16
Method of analysis: UV spectrophi
Chlorinated hydrocarbons Ad
DDT
1, l'-(2, 2,2-trichloroethylidene)-
bis [4-chlorobenzene]
C14H9C15
Compound properties
Adsorbent
illite 2.
kaolinite 7.
montmorillonite 1-
Ref .
LaFleur,
Equation: K, = P /P
b s w 1976a
Equation : K, = P /P
M f s w
1/0.5 1/1 1/2 1/4 1/1
0.44 0.21 0.16 0.13
1.4 0.36 0.31 0.25
0.72 0.12 0.10 0.08
5.2 1.8 1.6 1.3 0.79
0.88 0.27 0.22 0.19
7.6 3.7 2.6 2.3
atometry .
faorption equation. x/m KL Huang and
Liao,
K 1/n 1970
72xlO~3 3.28
37xlO~6 5.08
10xlO~5 5.97
m.w. 354.49
Method of analysis: GC - electron capture
-------
TABLE 6: Continued
Compound Name
Ref .
dieldrin
1,2,3,4,10,10-hexachloro-
6,7-epoxy-l,4,4a,5,6,7,8,8a-
octahydro-endo-1,4-eio-5 , 8-
dimethanonaphthalene
C12H8C16°
Compound properties
m.w. 380.91
Adsorbent
illite
kaolinite
montmorillonite
Adsorption equation: - = KG1'"
9.45X10
1.46X10
1.05X10
-16
-21
-16
8.82
11.63
9.24
Huang and
Liao,
1970
CTl
Method of analysis: GC-electron capture.
heptachlor
1,4,5,6,7,8,8-heptachloro-
3a,4,7,7a-tetrahydro-4,7-
methano-1S-indene
Adsorption equation: =
Huang and
Liao,
1970
C10H5C17
Adsorbent
illite
kaolinite
montmorillonite
K
1.09X10
5.00X10
1.48X10
-9
-6
-4
1/n
6.07
4.51
3.52
Method of analysis: GC-electron capture.
-------
TABLE 6: Continued
-O
-J
Compound Name
methoxychlor
C16H15C13°2
Compound properties0 Adsorbent
Ref .
Karickhof f ,
Adsorption equation: X = K C; KOC = K /OC Brown, and
p p Scott,
% O.C. Kp KOC(X10"5) 1979
m.w. 345.65 Hickory Hill
m.p. 78-78. 2°C or sand
86-88°C coarse
medium
silt
silt
insol. in water fine silt
clay
Doe Run
sand
coarse
medium
silt
silt
fine silt
clay
0.
3.
1.
1.
1.
0.
2.
2.
2.
3.
13
27
98
34
20
086
78
34
89
29
53
2600
1800
1400
1100
8.3
2200
1700
2300
2400
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
41
80
91
0
92
097
80
73
80
73
Oconee River
sand
coarse
medium
silt
silt
fine sand
clay
0.
2.
1.
2.
-
57
92
99
26
-
95
2500
2000
2100
—
0.
0.
1.
0.
-
17
86
0
93
-
Experimental conditions: sorbent concentrations 400 rag/ml of suspension
for sand, 20 rag/ml for coarse and medium silt, 10 mg/ml for fine silt
and 1 mg/ml for clay.
Method of analysis: UV spectrophotometry with Perkin Elmer 356
spectrophotometer.
-------
TABLE 6: Continued
Compound Name
mirex
C10C112
Compound properties
m.w. 546.0
m.p. 485 (decomp)
Ref
Adsorption equation: S = K S , n=l Smith, Mabey,
s P w Bohonos,
Holt, Lee,
Chou, Bomber'
Adsorbent TOC CEC K ger. Mill,
_E
Coyote Creek 1977
sediment 1.4 13.5 460,000 ± 110,000
vapor pressure
at 50° torr
6 x 10~6
water sol at 22 °C
(pg/ml)
70±20
CD
Organophosphates
aminoparathion
C10H16N°3PS
0,0-diethyl 0-p-aminophenyl
phosphorothioate
Compound properties
m.w. 261.3
water sol 390.0 vg/ml
Adsorbents
Na-montmorillonite*
Ca-montmori1lonite *
Fe-montmorillonite*
Adsorption equation: x/m = KC
1/n
1/n
0.954
1.151
K
46.3
43.3
>99.9%
adsorption
Experimental conditions: 450 mg clay in 30 ml aqueous
insecticide solution
Method of analysis: GC - alkali flame ionization detector
*Prepared from Wyoming bentonite, <2 vm fraction
Bowman and
Sans,
1977
-------
TABLE 6: Continued
Compound Name
Ref.
fenitrothion
0,0-dimethyl 0- (3-methyl-4-
nitrophenyl) phosphorothioate
Adsorption equation:
= KC
"L'n
Bowman
and Sans,
1977
Compound properties
m.w. 277.2
b.p. 118°C
density 1.3227g5
water sol 25.4 ug/ml
Adsorbent 1/n
Na-montmorillonite* 1.163
Ca-montmorillonite* 1.952
Fe-montmorillonite* 1.773
K
71.1
64.0
740.1
Experimental conditions: same as for aminoparathion.
Method of analysis: GC-alkali flame ionization detector.
methyl parathion
0,0-dimethyl 0-p-
nitrophenyl phosphorothioate
Adsorption equation: *- = KCe1//n
Bowman
and Sans,
1977
Compound properties
m.w. 263.2
m.p. 37-38°Cc
density 1.3585°°
water sol 45.0 yg/ml
Adsorbent 1/n
Na-Montmorillonite* 1.032
Ca-Montmorillonite* 1.663
Fe-Montmorillonite* 1.463
K
65.4
56.3
147.3
50 ppm
*Prepared from Wyoming bentonite <2 pm fraction.
Experimental conditions: same as for aminoparathion.
Method of analysis: GC-alkali flame ionization detector.
-------
TABLE 6: Continued
Compound Name
Ref .
CO
O
methyl parathion
0,0-dimethyl 0-p-
nitrophenyl phosphorothioate
Compound properties
m.w. 263.12
Sediment
Ca-montmorillonite
Coyote Creek
Searsville Pond
Navarro River
Des Moines River
Oconee River
Adsorption equation:
K
substate in solution
'n
P
n = 1.0
ml solution
46.1
50.6
55.0
60.3
47.6
41.6
23.6
Smith, Mabey,
Bohonos, Holt,
Lee, Mill,
Bomberger,
1976
95% confidence
limit
±2.2
±4.5
±6.8
±3.5
±3. 2
±2.0
±1.3
Experimental conditions: methyl parathion concentrations at
4 and 8 ug/ml. Sediment concentrations were 1000 to 2000
times as concentrated as methyl parathion at 8 yg/ml and
1000 to 3000 times as concentrated as MP at 4 pg/ml.
-------
TABLE 6: Continued
Compound Name
Ref
parathion
CD
x/m = KC1'/nor
Adsorption equation:
log x/m = log K + 1/n log C
Adsorbent
Soil No.*
10
8
11
13
15
14
El
6.20
6
6
5
3
3
.25
.30
.20
.50
.30
Soil organic
matter, % CEC
0
1
2
5
8
24
.75
.62
.88
.52
.21
.62
18
26
42
19
21
28
.6
.6
.8
.2
.2
.9
Natural
K
7.
12.
38.
125
213
457
67
30
02
.90
.80
.10
Soils
1/n
1.04
1.
1.
1.
1.
1.
05
11
05
03
02
Wahid and
Se th una than,
1978
Oxidized Soils
K 1/n
3.16
10.72
Experimental conditions: 1 g soil in 10 ml aqueous parathion solution
Method of analysis: liquid scintillation
1.33
1.33
amitrole
3-amino-l,2,4-triazole
C2H4N4
pKa =4.14 (3-ATH+=H+ +3-AT)
Compound properties
water sol 28 g/100 ml (23°C)
Adsorbent
H sat. organic matter
Al sat. organic matter
Adsorption equation:
X = X bC/(l+t>C)
m
Nearpass,
1969
63 mM/lOOg
49 mM/lOOg
b**
0.015
0.010
Experimental conditions: 20:1 water to organic matter
Method of analysis: liquid scintillation
*all soils from India
••calculated from figure 2
-------
TABLE 6: Continued
Compound Name Ref.
8-Triazine
cyanazine ^, Majka and
Adsorption equation: — = KC Lavy,
2-[[4-chloro-6-(ethylamino)- m
s-triazin-2-yl]amino]-2- Chromatography thin-layer (soil) 1977
methylpropionitrile
Adsorbents pH % o.m. CEC K 1/n Rf
—
Monona silty clay loam 6.5 2.9 21.2 4.6 0.96 0.39
(Typic Hapludoll)
Valentine loamy fine 6.6 1.4 10.1 3.4 0.86 0.74
sand
(Typic Ustipsamment)
Experimental conditions: 1 g soil with cyanazine added in
0.2 ml methanol: 10 ml water.
Method of analysis: liquid scintillation with Packard 3320
spectrometer.
-------
TABLE 6: Continued
00
Compound Name
prometryne
2 , 4-bis (isoprcpylamino) -
6-methy Ithio- 1,3,5-
triazine
Compound properties
m.w.
water
20°
pKa =
241
sol 200 pM/1 at
C
4.05
Adsorbent
Lakeland s
Norfolk Is
Norfolk scl
Cecil si
Cecil c
Okenee si
5.3
6.0
5.4
6.3
5.7
4.65
%O.M
0.22
0.57
0.15
1.77
0.53
5.16
Desorption
CCC 1/0.5
3.0
6.5
28
15
18
19
1.5
2.1
5.7
7.9
3.7
19
Kb = -
1/1
0.86
1.5
3.4
4.0
2.3
12
Ps
w
1/2
0.74
1.2
2.6
3.2
1.7
9.0
1/4
0.67
1.0
2.3
2.8
1.6
7.0
Ref
LaFleur,
1976b
S?/_ , > K (calcf **
(Kcal/fnol) o
-4.1
-4.1
-3.6
-4.1
-3.3
-4.6
1060
990
420
1110
280
2340
Method of analysis: UV spectrophotometry
*Cation combining capacity - methylene blue adsorption at pH5.
**AG = -RTlnk
sp o
***KQ = Pa/PwPa is PS adjusted to soil weight
-------
TABLE 6= Continued
Compound Name
Ref.
Urea
diuron
3-(3,4-dichlorophenyl)-1,1-
dimethylurea
C9H1()C12N20
Compound properties0
m.w. 233.10
m.p. 158-159°C
water sol 42 ppm at 25°C
Adsorbents
Monona silty clay loam 6.5 2.9
(Typic Hapludoll)
Valentine loamy fine 6.6 1.4
sand
(Typic Ustipsamment)
Adsorption equation: — = KC
Chromatography thin-layer (soil)
pH % p.m. CEC K_ 1/n ^f
21.2 14.3 0.77 0.18
10.1
6.5 0.74 0.39
Majka and
Lavy,
1977
03
Experimental conditions: same as for cyanazine.
Method of analysis: liquid scintillation with Packard 3320
spectrometer.
fluometuron
1,l-dimethyl-3-(o,a,a-
trifluoro-m-tolyl)urea
C10H11F3N2°
Compound properties0
m.w. 232.21
m.p. 163-164°C
water sol 80 ppm at 25°c
Chromatography thin-layer (soil)
Adsorbent
Bethony silt loam
Hector loam
Eufaula sand
Experimental conditions: 10 g soil: 10 ml of 0.01 N CaCl
solution containing 1,2,4, or 8 ppm fluometuron.
Method of analysis: liquid scintillation.
% o.m.
4.4
4.8
0.3
CEC
12.4
9.2
0.6
pH
6.3
6.3
6.7
Kf
0.57
0.65
0.98
Chang and
Stritzke,
1977
-------
TABLE 6: Continued
Compound Name
tebuthiuron
S- [5- (1, l-dimethyl)ethyl] -1,3,4-
thiadiazol-2-yl-ff,A' ' -dimethylurea
Compound properties
Chromatography
Water solvent
water sol 2500 pg/ml Adsorbent
Bethony
Hector
Euf aula
silt loam
loam
sand
%
4
4
0
o.m.
.4
.8
.3
CEC
12.
9.
0.
4
2
6
Ref .
Chang and
Stritzke,
1977
thin-layer (soil)
E3_
6.3
6.
6.
3
7
Rf
0.
0.
0.
58
66
98
Experimental conditions: 10 gm of soil: 10 ml of 0.01 N
CaCl., solutions containing 1,2,4, or 8 ppm tebuthiuron.
Method of analysis: liquid scintillation.
-------
TABLE 6: Continued
00
Compound Name
paraoxon
-------
NOTES, TABLE 6
aWeast, R. C., S. M. Selby, J. W. Long, and I. Sunshine, eds. 1974. CEC
Handbook of Chemistry and Physics. 54th ed. Cleveland, Ohio: Chemical
Rubber Company Press.
Hodgman, C. D., R. C. Weast, R. S. Shankland, and S. M. Selby. 1961.
Handbook of Chemistry and Physios. 43d ed. Cleveland, Ohio: Chemical
Rubber Publishing Co.
o
Windholz, M., S. Budavari, L. Y. Stroumtsos, and M. N. Fertig. 1976.
The Merck Index. 9th ed. Rahway, N. J.: Merck & Co.
Protivova, J., and J. Pospisil. 1974. Antioxidants and stabilizers. XLVII:
Behavior of amine antioxidants and antiozonants and model compounds
in gel permeation chromatography. J. Chromatogr. 88:99-107.
eShults, w. D., ed. 1976. Chemical and Biological Examination of Coal-
derived Materials. Oak Ridge, Tenn.: Oak Ridge National Laboratory.
f
Chiou, C. T., and V. H. Freed. 1977. Partition coefficient and bioaccumu-
lation of selected organic chemicals. Environ. Sci. Technol. 11:475-78.
^Karickhoff, S. W., D. S. Brown, and T. A. Scott. 1979. Sorption of hydro-
phobic pollutants on natural sediments. Water Res. (in press).
h
Dorigan, J., B. Fuller, and R. Duffy. 1976. Chemistry, production and
toxicity of chemicals A-C. Appendix I in Preliminary Scoring of
Selected Organic Air Pollutants. Report No. EPA-450/3-77-008b. Re-
search Triangle Park, N. C. : Strategies and Air Standards Division,
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency-
fj
Fendler, J. H., E. J. Fendler, G. A. Infante, P. Shih, and L, K. Patterson.
1974. Adsorption and proton magnetic resonance spectroscopic investi-
gation of the environment of acetophenone and benzophenone in aqueous
micellar solutions. J. Am. Chem. Soc. 97:89-95.
Dorigan, J., B. Fuller, and R. Duffy. 1976. Chemistry, production and
toxicity of chemicals 0-Z. Appendix IV in Preliminary Scoring of
Selected Organic Air Pollutants. Report No. EPA-450/3-77-008b. Re-
search Triangle Park, N. C.: Strategies and Air Standards Division,
Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency.
^
Hansen, R. S., Y. Fu, and F. E. Bartell. 1949. Multimolecular adsorption
from binary liquid solutions. J. Phys. Colloid Chem. 53:769-85.
87
-------
Hangerbrauck, R. P., D. J. Von Lehmden, and J. E. Meeker. 1964. Emissions
of polynuclear hydrocarbons and other pollutants from heat-generation
and incineration processes. J. Ai-P Pollut. Control Assoc. 14:267-78.
Mackay, D., and W. Y. Shiu. 1977. Aqueous solubility of polynuclear
aromatic hydrocarbons. J. Chem. Eng. Data 22:399-402.
88
-------
TABLE 7: AVERAGE VALUES OF ADSORPTION CONSTANTS FOR ORGANIC PESTICIDES
03
Compound Name
S-triazines
Average* Average* Soils
l/n±S% K±S% (No. )
simazine 0.820±3.48 6
6-chloro-ff, ff'-diethyl-l, 3, 5-
triazine-2, 4-diamine
m.w. 201. 66a
propazine 0.95±1.7 2.68±33.0 4
2-chloro-4,6-bis
Average** Average*** Soils
K,±S% K ±S% ,„ .
d oc (No.)
1.93+6.69 135+6.33 174
16.3±30 159±5.66 2
2.3717.06 160111.6 54
26.719.71 152+3.7 17
( i sopropy lamino ) - a- tr ia zine
m.w. 229. 71a
tHamaker, J. W., and J. M. Thompson. 1972. Adsorption.
In Organic Chemicals in the Soil Environment, Vol. 1,
ed. C. A. I. Goring and J. W. Hamaker, pp. 51-143.
New York: Marcel Dekker, Inc.
C
*K =
1/n
**K, = ^s
***K
; = X/m(pg/g of organic carbon) = d(pg/g of soil)
oc C % organic carbon
Value given is average of K and ]f adjusted for organic carbon
-------
TABLE 7: Continued
Compound Name
atrazine
6-chloro-ff-ethyl-ff ' -
Average* Average*
l/n±S% K±S%
0.772±8.65
0.709±10.7
Soils
(No.)
19
6
Average**
K,±S%
a
2.94±10.8
25.5±20.4
Average***
Koc±S%
17246.42
102+5.80
Soils
(No.)
79
24
(1-methylethyl)-1,3,5-
triazine-2,4-diamine
j.w. 215.69'
prometone
2,4-bis(isopropylamino)-
6-methoxy-a-triazine
C10H19N5°
m.w. 225.30a
0.81+2.1
3.65+26
3.31±16.5
300+19.5
73.8±5.1
49
15
ametryne
ff-ethyl-tf' - (1-methylethyl)
-6- (methylthio) -1,3, 5-triazine-
2, 4-diamine
6.17+11.1
167.4
380+10.0
802
33
1
.w. 227. 33a
prometryne
2,4-bis(isopropylamino)-6
(methylthio)-s-triazine
C10H19N5S
0.855±1.1
1.76
7.83+31
50.3
7.03±8.78
55.8±8.46
513+13.0
311+5.12
53
18
m.w. 241.36C
-------
TABLE 7: Continued
Compound Name
H
6-chloro-ff,ff-diethyl-
S'-(1-methylethyl)-1,3,5-
triazine-2,4-diamine
C10H18C1N5
m.w. 243.74°
hydroxyatrazine
G30026
Norazine
m.w. 201. 66a
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
Average*
K+S%
d
47.7
51.5
0.702
37.4
Average*** Soils
KQCtS% (No.)
2571 1
888
81.8
Ureas and Uracils
Urea
0.717
5.22
14.3
Compound properties
density 1.32,J8
m.w. 60.06
m.p. 132. 7°C
-------
TABLE 7: Continued
Compound Name
fenuron
N , ff-dimethyl-tf' -phenylurea;
l,l-dimethyl-3-phenylurea
m.w. 164. 21a
methylurea
phenylurea
C H N 0
Average*
l/n±S%
0.953±0. 95
1.01±3.20
0.604±2.38
0.832+4.71
0.744+1.34
0.733±2.90
Average*
K±S%
0.554±20.6
6.22±35.3
1.73±26.3
12.5±48.3
1.80±14.8
21.7±52.9
Soils Average**
(No.) Kd±S%
3 0.781±17.0
3 1.01±3.2
3
3
3
3
Average*** Soils
Koc±S% (No.)
0.554+20.6 13
0.622±35.3 1
70.2±7.59
57.6±8.43
76.7±8.83
98.3±12.9
Compound properties
m.w. 136.15
density 1.302
m.p. 147°C
b.p. 238°C
bromacil
0.58, 0.85
0.08, 1.5
19, 123
5-bromo-6- methyl- 3- (1-methylpropyl)-
uracil
Compound properties
m.w. 261.11
m.p. 157.5-160°C
-------
TABLE 7: Continued
Compound Name
U)
terbacil
Average*
l/n±S%
0.50, 0.96
5-chloro-3- (1, 1-dimethylethyl) -
6-methyl-2,4 (lfl,3ff) -
pyrimidinedione
.w. 216. 6T2
monuron
N ' - (4-chlorophenyl) -N ,N-
dimethylurea
Compound properties
m.w. 198.65
m.p. 170. 5-171. 5°C
water sol 230 ppm at 25°C
0.74
0.83
Average*
K±S%
0.15, 1.7
Soils
(No.)
5. 98
23.6
Average*
Kd±S%
2.17±18.9
33.3±22.3
Average***
K ±S%
oc
37, 140
83.1±22.9
163±16.7
Soils
(No.)
31
6
diuron
3- ( 3 , 4-dichlorophenyl) -
1 , 1-dimethylurea
0.818±6.45
0.707±5.10
10 6.29±9.33
3 196±39.2
351±8.95
902±31.9
79
4
Compound properties
m.w. 233.10
water sol 42 ppm at 25°c
-------
TABLE 7: Continued
Compound Name
metobromuron
3-(p-bromophenyl)-1-
methoxy-1-methylurea
C9HllBrN2°2
m.w. 259.lla
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
Average*
Kd±S%
Average*** Soils
(No.).
Koc±S%
60±20
chlorobromuron
217±20
monolinuron
3-(4-chlorophenyl)-1-
methoxy-1-methylurea
C9H11C1N2°2
m.w. 214.650
0.810±0.302
0.832±2.33
9.24±9.75
43.0±48.5
9.24±9.75
43.0±48.5
195±38.9
198±8.67
neburon 0.956+2.51 27.9+53.4
l-butyl-3-(3,4-dichlorophenyl)-
1-methylurea
C12H16C12N2°
m.w. 275.18
linuron 0.75, 0.75 45.2, 67.8
a'- (3,4-dichlorophenyl)-
ff-methoxy-Af-methylurea
787±6.89
18.1±18.7
147±77.2
840±20
653+13.4
26
3
Compound properties
m.w. 249.10
m.p. 93-94°C
water sol 75 ppm
-------
TABLE 7: Continued
Compound Name
Halogenated Hydrocarbons
ethylene dibromide
1 , 2-dibromoe thane
C2H4Br2
Average* Average* Soils Average** Average*** Soils
l/n±S% K±S% (No.) Kd±S% Koc±S% (NO-'
0.967, 0.970 0.408, 0.803 2 0.537±24.8 32.4±23.7 3
1.04 2.16 1 2.13±1.41 14.4±19.4 2
m.w, 187.870
beta-BHC
1,2,3,4,5,6-hexachlorocyclo-
hexane
C6H6C16
m.w. 290.85C
lindane
la,2a,36,4a,5a,66-
hexachlorocyclohexane
C6H6C16
Compound properties
m.w. 290.85
m.p. 112.5°C
insol. in water
0.861
0.950
148
456
0.841,080 45.7, 7.91 2
0.981 331 1
4254
3573
24.7±27.8 1342±15.3 6
321±6.10 1943+20.4 4
-------
TABLE 7; Continued
Compound Name
Ave rage *
l/n±S%
N-serve
2-chloro-6- (trichloromethyl)-
pyridine
Average*
K±S%
Soils
(No.)
Average*
Kd±S%
6.80+30.1
44.5
Average*
Koc±S%
271±11.5
238
Soils
(No.)
9
1
Compound properties"
m.w. 230.93
m.p. 62.5-62.9°C
b.p. 136-137. 5°C
DDT
1.3X105t
LSTXIO*1
1.063X105
1.31X10
3.55X10
2.29X10
Carbamates
chloropropham 1.00
isopropyl-m-chlorocarbanilate 1.00
m.w. 213.67a
propham
isopropyl carbanilate
21
132
9.28±11.8
590±8.35
51
65
m.w. 179.22°
-------
TABLE 7: Continued
ID
Compound Name
Average*
l/n±S%
EPTC
S-ethyl dipropylcarbamothioate
m.w. 189. 32a
cycloate
S-ethyl cyclohexylethyl-
Average* Soils Average**
K±S% (No.) Kd±S%
5.96±24.6
52.6
7.32±25
66.6
Average*** Soils
Koc±S% (NO.)
283±18.9 3
109 1
345±17.4 3
222 1
carbamothioate
C11H21NOS
m.w. 215.36°
pebulate
S-propyl butylethylthio-
carbamate
14.5±20.1
109
719+21.4
363
m.w. 203.:
-------
TABLE 7: Continued
Compound Name
Phosphates
nellite
C H N 0 P
Average* Average* Soils Average**
l/n±S% K±S% (No.) Kd±S%
0.525+72.5
6.30, 6.02
Average***
Koc±S*
30.89±25.9
43.5, 33.2
Soils
(No.)
8
2
m.w. 200.18
00
crotoxyphos
(E)-1-phenylethyl-
3-[(dimethoxyphosphinyl)oxy]•
2-butenoate
6.09+15
173+34
C14H19°6P
m.w. 314.28'
ohorate
0,0-diethyl s-l (ethylthio)
methyl] phosphorodithioate
0.97+2.1
8.76±39
3199+25
m.w. 260. 38
-------
TABLE 7: Continued
Compound Name
disulfoton
0,0-diethyl S-[2-
(ethylthlo)ethyl]
phosphorodithioate
C8H19°2PS3
Compound properties"
m.w. 274.41
b.p. 1D8°C
density 1.144g°
insol. in water
methyl parathion
0,0-dimethyl 0-(4-nitrophenyl)
phosphorothioate
C8H1()N05PS
Compound properties
m.w. 263.23
m.p. 37-38°C
density 1.358J;0
water sol 50 ppm
parathion
0,0-diethyl 0-(4-nitrophenyl)
phosphorothioate
Average*
l/n±S%
0.930±2.38
Average*
K±S%
20.1±18.9
Soils
(No.)
10
Average
Kd±S%
Average*** Soils
(No.)
Koc±S%
2132±25
16
1.04
18.43±20
9799±41
1.03±1.5
2.19±32
10454±38
m.w. 291.26
-------
TABLE 7: Continued
Compound Name
Average* Average* Soils Average** Average*** Soils
l/n+S% K±S% (NO.) Kd±S% Kocf S% (No.)
ethion 0.945±2.5 28.5±15.9 4 15435+39.3
0, 0, 0',0'-tetraethyl 5,5'-
methylenebisphosphorodithioate
C9H22°4P2S4
Compound
properties'
m.w. 384.48
,_, m.p. -12 to -13°C
o
o density 1.220^°
slightly sol in water
carbophenothion 0.940±3.7 74.5+13 4 45368±40.6
5-[ [ ( 4-chlorophenyl ) thio ]met hyl ]
(7,0-dlethyl
Dhosohorodithioate
C11H16C1°2PS3
Compound properties^
m.w. 342.85
b.p. 82°C
density 1.27lgs
insol. in water
-------
TABLE 7: Continued
Compound Name
Amino, Nitrophenyl Sulfones
NO?
R2S02—/QV- N(R,)Z
NO?
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
Average*
Kd±S%
Average*** Soils
Koc±S% (No.)
nitralin
50, 26
500, 520
CH3)
4-(methylsulfonyl)-2,6-dinitro-
ll, N-dipropylbenzenamine
m.w. 345.38
SD11830
12.5, 7.25 125, 145
SD12639
23, 9.65
230, 193
SD13207
C2H5;
32, 13.5 320, 269
SD12030
= C3H7; R2 = C2H5)
75, 35.1
750, 702
SD12346
C3H7; R2
117
1170
SD12400
= CH3; R2 =
22.2
222
-------
TABLE 7: Continued
Compound Name
Carboxylic Acids
dicamba
3,6-dichloro-2-
methoxybenzoic acid
C8H6C12°3
m.w. 221. 04
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
Average*
Kd±S%
0.9
Average*
Koc±S%
Soils
(No.)
O chloramben NH^ salt
chloramben: 3-amino-2,5-
dichlorobenzoic acid
0.320±30.4
4.1
15.4±37
17.4
m.w. 206.03
chloramben methyl ester
MCPA
(4-chloro-2-methylphenoxy)-
acetic acid
3.5±35
0.420±37.4
507+24
m.w. 200.62
-------
TABLE 7: Continued
Compound Name
O
U)
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
picloram
4-amino-3,5,6-trichloro-
2-pyridinecarboxylic acid
C6H3°2C13N2
m.w. 241.46
2,4-D
(2,4-dichlorophenoxy)-
acetic acid
C8H6C12°3
m.w. 221.04a
2,4,5-T
(2,4,5-trichlorophenoxy)-
acetic acid
Average*
Kd±S%
0.453±32.2
Average*
Koc±S%
12.7±21.7
1.59+54.9
1.05+42.3
Soils
(No.)
14
m.w. 255.49'
dichlofcenil
167
4.19+11.4
164±3.57
16
-------
TABLE 7: Continued
Compound Name
Acids
linear alkyl
sulfonates
pentachlorophenol
C,.HC1,0
O D
b
Compound properties
m.w. 266.35
m.p. 190-191°C
b.p. 309-310°C
density 1.97852
water sol. 8 rag/100 ml
methane arsonate
Compound properties b
m.w. 139.96
m.p. 161°C
freely sol. in water
Average*
l/n±S%
Average*
K±S%
Soils
(No.)
Average*
Kd±S%
Average***
Koc±s%
34.2±57.4 1222±10.2
55.3 170
8.96±20.38
12.4±38.9 770±19.1
Soils
(No.)
20(K
Qc)
10
-------
TABLE 7: Continued
Compound Name
Miscellaneous
silvex
2 - ( 2 , 4 , 5-tr ichlorophenoxy )
propionic acid
Average*
l/n±S%
Average*
K±S%
0.639, 0.987 42.1, 34.2
1.05 162
Soils
(No.)
2
1
Average*
Kd±S%
Average1
Koc±S%
2786, 4682
440
Soils
(No.)
Compound properties
m.w. 269.53
m.p. 181. 6°C
0.014% sol. in water at 25°C
chlorthiamid
2 , 6-dichlorobenzene
carbothioamide
0.868±1.28
4.72±8.13
107.2±6.42
chloroneb
1,4-dichloro-2,5-dimethoxy-
benzene
C8H8C12°2
m.w. 207.06a
1.3
20
1159
paraquat
1,1'-dimethyl-4,41-
bipyridinium
C12H14N2
0.566±19.6
0.360±13.3
353±97
5501+16.6
20152±65
m.w. 186.26
-------
NOTES, TABLE 7
a
Wiswesser, W.J., ed. 1976. Pesticide Index. 5th ed. College Park, Mary-
land: The Entomological Society of America.
Windholz, M., S. Budavari, L.Y. Stroumtsos, and M.N. Fertig. 1976. The
Merck Index. 9th ed. Rahway, N.J.: Merck and Co.
106
-------
TABLE 8: RELATIONSHIP BETWEEN OCTANOL/WATER PARTITION COEFFICIENT AND R VALUES OF PESTICIDES
ON A SOIL
Mobility Class
Immobile
Low
Intermediate
Mobile
Very Mobile
0.
0.
0.
0.
0
10
35
65
90
Rf
L.
- 0.09
-0.34
- 0.64
- 0.89
- 1.00
JL.
log P
>3.78
3.78-2.39
2.39-1.36
1.36-0.08
<0.08
Ref
"& 7t '
6
•*• Briggs,
>398 1973
398-74
74-29
29-4.5
<4.5
* P = Octanol/water partition coefficient
** Q = Soil organic matter/water partition coefficient
-------
TABLE 9: LEACHING OF PESTICIDES FROM A SOIL
Compound Name
Ref .
Adsorbent = Hagerstown silty clay loam
%O.M = 2.41, %O.C = %O.M/1.724 = 1.40
Hamaker,
O
00
Pesticide
chloramben
2,4-D
propham
bromacil
monuron
simazine
propazine
dichlobenil
atrazine
chlorpropham
prometone
ametryne
diuron
prometryne
chloroxuron
paraquat
DDT
Rf (soil TLC)
0.96
0.69
0.51
0.69
.48
.45
.41
.22
.47
.18
0.60
0.44
0.24
0.25
0.09
0.00
0.00
Mobility class
5
4
3
4
3
3
3
2
3
2
3
3
2
2
1
1
1
!°£*
12.
32
51
71
83
135
152
164
172
245
300
380
485
513
4,986
20,000
243,000
*K = adsorption coefficient on the basis of organic carbon
-------
TABLE 10: SORPTION DEPENDENCE ON SORBATE PROPERTIES
Compound Name
Compound
pyrene
methoxychlor
naphthalene
2-methylnaphthalene
anthracene
9-methylanthracene
phenanthrene
tetracene
hexachlorobiphenyl
benzene
Water solubility
(mole fraction x
12
6.3
4460
3220
7.57
24.4
130
0.037
0.048
189,000
Compound Properties
-3 *
109 Koc(X1° >
84
80
1.3
8.5
26
65
23
650
1200
0.083
Ref.
, lr)-3. ** Karickhoff, Brown,
ow and Scott,
150 1979
120
2.3
13
35
117
37
800
2200
0.13
*K = partition coefficient based on organic carbon
**K = octanol/water distribution coefficient
ow
-------
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160
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APPENDIX: FORMULAS OF ORGANIC COUMPOUNDS
COMPOUNDS OTHER THAN PESTICIDES
Acids, Aliphatic
acetic acid
CH COOH
adipic acid
butyric acid
CH3CH2CH2COOH
caproic acid
CH CH CH CH CH2COOH
citraconic
CH.CCOOH
3 ii
HCCOOH
citric acid
CH COOH
i ^
HOCCOOH
I
CH2COOH
dibromosuccinic
BrCHCOOH
i
BrCHCOOH
formic acid
HCOOH
fumaric acid
HOOCCH
HCCOOH
glutaric acid
HOOCCH CH CH COOH
£* J-* £•
glyceric acid
OH
i
HOCH2CHCOOH
glycolic acid
HOCH COOH
glyoxylic acid
HCOCOOH
isobutyric acid
CH-,
CH.
;CHCOOH
161
-------
isovaleric acid
CH.,
:CHCH~COOH
CH-
itaconic acid
CH =CCOOH
CH2COOH
lactic acid
COOH
i
CHOH
I
CH0
levulinic acid
CH COCH CH COOH
O £• Z,
maleic acid
HCCOOH
ll
HCCOOH
malic acid
HOCHCOOH
i
CH COOH
malonic acid
HOOCCH2COOH
mesaconic acid
CH.CCOOH
3 ii
HOOCCH
methylsuccinic acid
0
ii
CH OOCCH CH COCH
monobromosuccinic
HOOCCH2CHBrCOOH
oxalic
HOOCCOOH
propionic acid
CH3CH2COOH
pyruvic acid
CH3COCOOH
succinic acid
HOOCCH2CH2COOH
tartaric acid
COOH
i
CHOH
i
CHOH
i
COOH
valeric acid
CH3CH2CH2CH2COOH
Acids, Aromatic
benzoic acid
COOH
phenylacetic acid
phenoxyacetic acid
162
-------
Alcohol
n-butyl alcohol
CH CH CH CH OH
•~J £, £, £
Amines and derivatives
acetanilide
Benzene
Carbamate derivatives
R-LNHCOOR2
Carbonyl compounds
acetophenone
NHCOCH,
aniline
4-(R2 sulfonyl)-2,6-dinitro-N.N.
(di-R-j) aniline
o
N-Heterocyclics
benzo[f]quinoline
9H carbazole
7-H dibenzocarbazole
crystal violet
N(CH3)2C1~
Amino Acid
tryptophan
CH2CH(NH2)COOH
pyridine
quinoline
163
-------
S-Heterocyclics
benzo[b]thiophene
Quinone
dibenzothiophene
Phenols
phenol
alizarin
Sulfonate
sodium napthalenesulfonate
Polynuclear aromatics
ben z[a]anthracene
benz[a]pyrene
pyrene
164
-------
PESTICIDES
Carbamates
carbaryl
O-CO.NH-CH,
CO
cycloate
C,H,-S-CO.N(C1H1)
2,4-D
Cl - >-0-CH,-CO.OH
a
dicamba
CO.OH
3-CH,
dichlobenil
EPTC
CH3CH2
pebulate
CH CH CH
CH2CH2CH3
OCH2CH-
CN
MCPA
O-CH.-CO.OH
CH,
propham
o
NH-CO.O-CH^CH,),
picloram
NH,
ci -^N^\ CO.OH
Carboxylic Acids
chloramben
OH
NH,
2,4,5-T
a-/~Vcwai1-co.oH
cK
165
-------
Halogenated Hydrocarbons
BHC
a a
a a
DDT
c-a,
\=±3S/
dieldrin
a a
ethylene dibromide
heptachlor
a a
a
a
a
lindane
a
Cl
methoxychlor
CH,C
mi rex
ac c
ac
cic-
ca
-c-
a
n-serve
a
a
Organophosphates
carbophenothion
(C,H,-O),-PS.S-CH,-S -d >• Cl
crotoxyphos
CH3°\
CH 0 H i ll i
J 0 CH3 0 C
disulfoton
CH3CH20
ethion
ca,
CH3CH2Ox
oCHoO II HOCH9CH
^ S S 2
166
-------
fenitrothion
(CH,-0),-PS.O-/}>-N01
\i—/
CH,
methyl parathion
(CH,-O)J-PS.O—(7- NO,
S-Triazines
ametryne
C,H,-NH
amitrole
riellite
paraoxon
(QH,-0)]-PO.O
parathion
(QH,),-PS.O
phorate
CH CH 0
CH3CH20
NHCH
SCH CH
Amino, Nitrophenyl Sulfones
Nitralin
NO,
!,-§- /~VN (CH, CH.CH,),
5W
NO,
atrazine
Cl Y^S- NH-CHHCH,),
CaH,-NH
cyanazine
C,H,-NH-(f'NVN
i
Cl
ipazine
NH-CH(CH,),
norazine
prometone
(CH^-CH-hfH-
NH-CH^CHJ,
167
-------
prometryne
(CH,),-CH-NH -^ N*»i -S-CH,
N^N
NH-CH(CH,),
propazine
a
simazine
CI
Ureas & Uracils
bromacil
fluometuron
C F,
linuron
ci
methylurea
H O CH,
H
H
metrobromuron
Br-/~VNH-CO.N-0-CH,
^-=/ CH,
monolinuron
NH-CO.N-CH,(O-CH,)
diuron
a
a
monuron
-NH-CO.N^CH,),
fenuron
CH.
CH
H
3 0
neburon
a
,-a
•JH-CO.N(C.H,)-CH,
168
-------
phenylurea
Miscellaneous
H O H
\
H
chloroneb
a
fSpO-CH,
.O-IS^J
a
tebuthiuron
>-N-CO-NH
CH3 5 CH3 CH3
chlorthiamid
CS.NH,
terbacil
•N-0
paraquat
2CH.-SO,
urea
H O H
\ I /
N—C—N-
silvex
a
a"\/~°"CH(CH)
i>CO.OH
a
169
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-600/3-7 9-086
3. RECIPIENT'S ACCESSIOI^NO.
4. TITLE AND SUBTITLE
Adsorption of Energy-Related Organic Pollutants: A
Literature Review
5. REPORT DATE
August 1979 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
K.A. Reinbold, J.J. Hassett, J.C. Means, and
W.L. Banwart
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Institute for Environmental Studies
University of Illinois at Urbana-Champaign
Urbana, Illinois 61801
10. PROGRAM ELEMENT NO.
1BB770
11. CONTRACT/GRANT NO.
68-03-2555
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Research Laboratory—Athens, Ga,
Office of Research and Development
U.S. Environmental Protection Agency
Athens, Georgia 30605
13 TYPE OF REPORT AND PERIOD COVERED
Final, 7/77 to 4/78
14. SPONSORING AGENCY CODE
EPA/600/01
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report is a literature review on sorption properties of sediments and
energy-related organic pollutants. Adsorption of organic compounds in general is
discussed, and analytical methodology in soil thin-layer chromatography and chemical
analysis as applicable to measurement of sorption properties is summarized. The
literature on the adsorption of energy-related organic pollutants is reviewed.
Reported constants for the adsorption of organic compounds on several adsorbents are
tabulated, and factors that influence adsorption are discussed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Adsorption
Chemical analysis
Coal
Coal gasification
Energy
Organic compounds
Sediments
68C
68D
99A
99D
13. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
178
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
170
•i U S. GOVERNMENT PRINTING OFFICE 1979 -657-060/5411
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