EPA-600/2-81-205
September 1981
GUIDELINES FOR THE USE OF CHEMICALS IN
REMOVING HAZARDOUS SUBSTANCE DISCHARGES
by
C.K. Akers, R.J. Pilie, J.G. Michalovic
Calspan Corporation
Buffalo, New York 14221
Contract No. 68-03-2093
Project Officer
Joseph P. Lafornara
Oil & Hazardous Materials Spills Branch
Municipal Environmental Research Laboratory - Cincinnati
Edison, New Jersey 08837
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Oil & Hazardous Materials Spills
Branch, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the American people. Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem solution
and it involves defining the problem, measuring its impact, and searching for
solutions. The Municipal Environmental Research Laboratory (MERL) develops
new and improved technology and systems for the prevention, treatment, and
management of wastewater and solid and hazardous waste pollutant discharges
from municipal and community sources, for the preservation and treatment of
public drinking water supplies, and to minimize the adverse economic, social,
health, and aesthetic effects of pollution. This publication is one of the
products of that research; a most vital communications link between the
researcher and the user community.
The detrimental impact on the environment due to discharges of chemical
pollutants is often compounded by the potential toxic side effects caused
by misuse of chemical and biological agents during mitigation of the spilled
pollutant. The MERL Office of Research and Development recognized the impor-
tance of this potential hazard and directed this successful study to develop
guidelines on the use of various agents to mitigate discharges of hazardous
materials.
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ABSTRACT'
This project was undertaken to develop guidelines on the use of various
chemical and biological agents to mitigate discharges of hazardous substances.
Eight categories of mitigative agents and their potential uses in remov-
ing hazardous substances discharged on land and in waterways are discussed.
The agents are classified as follows: (1) Mass Transfer Media, (2) Absorbents;
(3) Thickening and Gelling Agents, (4) Biological Treatment Agents, (5) Dis-
persing Agents, (6) Precipitating Agents, (7) Neutralizing Agents, and
(8) Oxidizing Agents.
The classification of each agent is developed in terms of:
(a) Characteristic properties of the mitigative agent
(b) Potential spi-ll situations in which the agent could be used
(c) The effects on the environment caused by use of the agent
(d) Possible toxic side effects caused by byproduct formation
(e) Recommendations for use of the agent
A counter-measure matrix that references various classes of mitigative
agents recommended for treatment of hazardous substances involved in spills
near or into a watercourse has been developed and includes a listing of haz-
ardous chemicals, the corresponding EPA toxicity classification, and the
physical properties of the chemical.
This report was submitted in fulfillment of Contract No. 68-03-2093 by
Claspan Corporation under the sponsorship of the U.S. Environmental Protection
Agency.
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CONTENTS"
Foreword iii
Abstract iv
Figures vi
Tables vi
1. Introduction 1
Objective 1
Scope , 1
2. Summary and Conclusions 3
3. Recommendations 8
4. Spill Mitigation Measures 12
Mass Transfer Media 12
Absorbents 25
Thickening and Gelling Agents 30
Biological Treatment Agents 32
Dispersing Agents 37
Precipitation Agents 40
Neutralizing Agents 43
Oxidizing Agents 49
5. Hazardous Substance - Counter-measure Matrix 51
6. Mitigation and Selection Parameters 53
Physical-Chemical Parameter 54
Watercourse Parameter 55
Monitoring 56
Toxicity Parameters 57
References 59
Appendices
A. Hazardous Substance/Countermeasure Matrix 62
B. Hazardous Chemicals Classified According to P/C/D Category ... 72
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FIGURES -
Number Page
1 Bacterial growth phases 33
2 Treatment of strong acid with base 46
3 Treatment of a weak acid with base 47
TABLES
1 Mitigation Categories 4
2 Amenability of Typical Organic Compounds to Activated
Carbon Adsorption 16
3 Reported Organic Compounds Readily Removed from
Aquatic Environment / 20
4 Reported Organic Compounds Removed from Aquatic
Environment with Acclimated Microorganisms 21
5 Liquids Tested with Multipurpose Gelling Agent 31
6 Biological Oxidation 35
7 Biological Oxidation 36
8 Reported Organic Compounds Resistant to Removal
from Aquatic Environment 38
9 Metal Ions Subject to Sulfide Precipitation 41
10 Commonly Spilled Acids and Bases 43
11 Sulfuric and Hydrochloric Acid Neutralization 45
12 Toxicity of Different Reaction Products Formed in
Neutralization of NH40H 45
13 Acids and Bases Suitable for Spill Neutralization 46
14 EPA Toxicity Category 51
15 Relative Potential Environmental Damage of Hazardous Substances 55
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SECTION V
INTRODUCTION
OBJECTIVE
The objective of this program, sponsored under EPA Contract 68-03-2093,
Exhibit 8, was to conduct a research and development project to determine
guidelines for the use of chemicals to remove hazardous substance discharges
from the environment. These guidelines are to be used by the EPA in the
future to expand and revise Annex X of the National Oil and Hazardous Sub-
stance Pollution Contingency Plan CFR40, Chapter V, Part 1510, to include
specific reference to chemical use for spills of hazardous substances. The
guidelines develop the rationale to determine under what circumstances the
use of chemicals or other additives is harmful to the environment.
SCOPE
Guidelines are established for the use of various chemicals and other
additives to mitigate and remove spills of hazardous substances. These chem-
icals and other additives are currently addressed only in general terms by the
statement of intent in Annex X, paragraph 2001,4: "no harmful quantities of
any substances be applied to the waters to remove or mitigate the effect of
oil and hazardous substances discharges."
Specific tasks were undertaken to address eight classes of mitigation
agents. These are summarized below:
1. Mass Transfer Media: Determine under what circumstances it is per-
missible to add mass transfer media to a water column with no pro-
vision for removing the spent media and the ecological consequences
of applying the media to a stream at the incorrect place such that
the spill plume is missed completely.
2. Absorbents: Since absorbents are used routinely in oil spill miti-
gation, and may be chemically attacked by some hazardous substances,
guidelines for their use shall be established.
3. Thickening and Gelling Agents: Determine under what circumstances
these agents may be used in spill mitigation. The effects of unre-
trieved agents upon the environment shall be considered.
4. Biological Treatment Agents: Determine under what circumstances bio-
logical treatment agents may be appropriate for treating hazardous
spilled materials.
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5. Dispersing Agents: Determine under what conditions dispersing agents
may be used as a mitigating agent.
6. Precipitating Agents: Determine whether or not precipitate or pre-
cipitated ion, redissolved by chemical or microbiological means, are
threats to the food chains.
7. Neutralizing Agents: Determine the circumstances that would dictate
the use of neutralizing agents to decontaminate a spill of an acid
or base and their effective use under the constraint of minimal en-
vironmental stress. The byproducts of neutralization and the poten-
tial biological damage that may be caused by overtreatment, under-
treatment, or no treatment at all.
8. Oxidizing Agents: Determine under what circumstances oxidizing
agents may be used for treating spills in a watercourse. Recogniz-
ing that these agents do not oxidize substances to C02 and ^0, oxi-
dizing agents that only result in innocuous byproducts should be
considered.
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SECTION 2-
SUMMARY AND CONCLUSIONS
The use of chemicals to mitigate hazardous substance spills can be justi-
fied only with proper controls and understanding of the secondary harmful
effects they have on the environment. It is highly recommended that the haz-
ardous spilled material be removed, if possible, from the environment by me-
chanical means. This mechanism of mitigation does not introduce any material
to the environment that may have harmful effects. However, before any chemi-
cal is added to a watercourse as a mitigation procedure, the effects of the
chemical on the environment, as well as the byproducts produced, must be
understood.
Many of the chemicals that can be used in a mitigation procedure are
harmful to the environment. Also, the byproducts of a mitigating chemical
agent and the spilled hazardous material can present an undesirable long-term
harmful effect on the environment. Generally, these byproducts are not re-
moved from the ground or watercourse and data are not available to determine
the environmental consequences of these byproducts. The environmental harm
caused by the spill must be weighed against that of the mitigation agent and
byproducts.
In order to minimize the harmful effects of a chemical mitigation agent,
there must be adequate analytical monitoring during the entire mitigation pro-
cedure. Only with analytical monitoring can the on-scene coordinator (OSC)
know where the hazardous material has spread with respect to the spill site
and its concentration profile. This information is required in order that the
OSC can determine which, if any, countermeasure should be used, where to
counteract the spill, how much agent should be added to the watercourse, and
when to cease mitigation procedures. Monitoring is an essential requirement
in all mitigation procedures that must be accomplished with trained personnel
using up-to-date equipment and analytical procedures at the spill scene.
Chemicals used in the mitigation of spills react differently with hazard-
ous substances. Therefore, agents have been divided into eight categories
(see Table 1). Chemicals and other additives were evaluated in each agent
category. Emphasis was placed on the harmful effect that the mitigation
agents would have if they were not retrieved and left in the environment.
Mass Transfer Media: Within this category, activated carbon and ion ex-
change resins were evaluated. The use of activated carbon for purification of
potable water and food industries indicates that it is nontoxic to the human
environment. The bioassay indicated that activated carbon is nontoxic unless
it is used in massive quantities. In this situation, the activated carbon
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TABLE 1. MITIGATION CATEGORIES
1. Mass transfer media
2. Absorbing agents
3. Gelling and thickening agents
4. Biological treatment agents
5. Dispersing agents
6. Precipitating agents
7. Neutralizing agents
8. Oxidizing agents
physically interferes with the respiratory function of the gills, causing a
harmful effect. Inadequate data exist for evaluation of irretrievable acti-
vated carbon on benthic organisms.
The mechanism of the interaction between hazardous material and activated
carbon is not clearly understood. The efficiency of activated carbon is in-
creased with either high concentrations of pollutant or with compounds with low
solubility. Organic material in general does not readily desorb. However,
acid herbicides (i.e., 2,4-0 and 2,4,5-T) and phenylurea herbicides (i.e.,
Diuros) readily desorb. The persistence of contaminated activated carbon left
in the watercourse is not known even though the contaminated agent will act as
a substrate for biodegradation. Data on the long-term toxicity of the hazardous-
material-activated carbon are not available in the literature. The toxic mate-
rial may be released at sub-toxic concentrations. Activated carbon is manu-
factured in many forms. The spill situation (hazardous chemical and water-
course parameters) will dictate which form of activated carbon is most
efficient.
Ion exchange resins are used routinely in the food industry and in water
purification. Some resins are ingested directly to reduce salt (Na+) intake.
No evidence is available to indicate that exchange resins are toxic to the
environment. The toxicity of exchange groups is generally low. All available
evidence suggests that uncontaminated ion exchange resins would not produce
toxicity problems if left in the environment. The mechanism of ion exchange
resins is a one-to-one exchange of ionic species. The condition to regenerate
the resin is by treating the resin with caustic or strong acid. These condi-
tions will not readily occur in the environment. The desorption rate of haz-
ardous material is not known. Therefore, the persistence of a toxic effect
cannot be adequately addressed.
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Because the desorption rates of many hazardous chemicals from mass
transfer media in natural surface water is not known, it is not possible to
evaluate the chronic toxicity problems that may be associated with the use of
irretrievable agents. It may be safely recommended that irretrievable mass
transfer agents be used to relieve the acute toxicity problems of spills of
materials that degrade rapidly to nontoxic forms in natural surface water. It
is also safe to recommend that such agents be used to mitigate acute effects
of spills of other materials when it can be shown that the dispersed rate is
such as to reduce total concentration (free + bound concentration) to nontoxic
levels before desorption can occur. More research is required on desorption
rates and dispersal rates to adequately define when the latter conditions
exist.
Absorbing Agents: The available data on the use of absorbing agents per-
tain to oil and petroleum products. Natural absorbing products (i.e., straw,
sawdust) are routinely used in oil mitigation. However, the spilled material
readily desorbs and must be removed from the environment. There are several
synthetic materials available for mitigating hydrophobic chemicals. These
agents are nontoxic themselves and do not present a hazard to the environment
in the uncontaminated state. However, desorption is significant since the
agents can be regenerated by squeezing or wringing out the spent agent to be
used again. There are some synthetic materials that can be used for mitigat-
ing hydrophillic chemicals. However, the desorption rate is again very high.
It may be concluded that absorbent materials are acceptable agents for
spill treatment only under those circumstances in which the contaminated sor-
bent can be removed. Thus their use in water spills is limited to treatment
of those materials that are insoluble and float. They are applicable in land
spills of any materials that are effectively absorbed.
Thickening and Gelling Agents: Thickening and gelling agents are really
special cases of absorbing agents. Their purpose in spill treatment is to
immobilize the spilled material to prevent further spread into the environ-
ment and to condition the spill for mechanical removal. Like other absorbents,
effective thickening and gelling agents are appropriate for use on all land
spills and on water spills of organic liquids that float.
Manufacturers usually claim that these agents are nontoxic to the envi-
ronment, but supporting data are not always presented.
Biological Treatment Agents: Biological treatment agents have previously
been used in treating oil and oil-derived products. The method of mitigation
is feasible on several other classes of organic materials. However, there are
limitations to the technique as a general mitigation procedure. The time in-
volved for biological degradation requires that the spilled hazardous material
be contained and isolated from the environment for treatment. Otherwise,
treatment is uncontrollable. The microbes that are added to the spilled mate-
rial must be supplied with the essential nutrients to allow adequate growth.
This implies that a culture maintenance program must be initiated. A third
consideration is whether the ecological system will be maintained in balance.
Microbes should not be introduced into the environment that will cause any sig-
nificant change to the ecological balance. Data on the long-term effects of
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biodegradation (i.e., the toxicity of byproducts and bioamplification) are not
available in the literature.
The use of biological treatment agents for mitigation of hazardous spills
is generally not appropriate except when the contaminated environment can be
contained for sufficient time to permit detoxification. In general, it is
recommended that other spill treatment agents be used whenever possible.
Dispersing Agents: Dispersing agents can be used to increase the rate of
biodegradation of spilled material, to avoid damage to fowl by removal
of oil and other organic materials from the water surface, to minimize fire
hazard, and prevent contamination of beaches and solid objects.
Some dispersants are themselves toxic. Others are not. Some pollutants
are more toxic after disposal than before disposal. It is necessary in each
case to determine that the treatment does not increase toxicity of the spill
before deciding upon its use.
Precipitating Agents: Precipitation is a valid mitigation technique for
removing metal ions from solutions. Many metal ions can be precipitated with
hydroxide ions at high pH. However, these salts will re-enter the water col-
umn when the pH returns to neutral, thereby causing a long-term hazard to the
environment.
Sodium sulfide, wlren introduced as a solution into a spill, will precipi-
tate heavy metal ions. At toxic concentration of heavy metal ions, an insol-
uble metal sulfide will form and reduce toxicity rapidly.
The sulfide ion and the hydrogen sulfide toxicity require that the sodium
sulfide contain a strong base such as NaOH to raise the pH to inhibit H2S for-
mation. After treatment, the water column should be aerated if possible to
remove residual hydrogen sulfide byproducts. The metal sulfide is sufficiently
insoluble to reduce to a nontoxic level any reentry of metal ions into the
environment.
Neutralizing Agents: Neutralization is an acceptable treatment for all
spills of acids or bases provided some method for monitoring pH is available.
Whenever possible, neutralization should be accomplished on land spills before
the spilled material enters aquifers or surface water. After the spilled mate-
rial has entered surface waters the toxicity associated with the change in pH
from natural conditions is usually most critical. Neutralization of spills of
large quantities of material is usually appropriate regardless of the neutral-
ization agent available. However, when a choice of agents is available, it is
extremely important to select the agent that produces the least toxic reaction
products in returning the pH to normal. In some cases, post-treatment for
toxic metallic ions may be necessary. All other considerations being equal,
some advantage can be obtained by selecting weak agents as opposed to strong
agents. Depending on the nature of the spilled material, some advantages can
be obtained by selection of neutralization agents with optimum physical char-
acteristics, but it is usually advisable to avoid use of solid agents when
possible.
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Temperature changes associated with exothermic neutralization reactions
can produce secondary thermal pollution but this problem appears to be of sec-
ondary importance. Caution should be observed to avoid personnel injury due
to sputtering or bubbling caused by exothermic reactions.
When the monitoring system is not sufficiently accurate to assure treat-
ment to exactly the desired pH, it is usually better to undertreat than to
risk overtreatment. pH values between 6 and 9 are acceptable.
Oxidizing Agents: Oxidizing agents are toxic to most organisms at
low concentrations. Oxidation reactions are extremely difficult to control and
seldom go to completion. Toxic intermediate reaction products are often left
in the environment unless excess oxidizing agent is available. The agents are
nonspecific and react with most organic materials.
The potential hazards in use of oxidizing agents for spill mitigation are
so great that they are recommended only as a last resort and then only on land
spills and water spills that are completely contained.
Mitigation Countermeasure Matrix: A mitigation countermeasure-hazardous
substance matrix has been prepared to summarize the counter-measures that are
effective on the EPA-proposed hazardous substances. This counter-measure matrix
(see Section 5) is based on the chemical and biological literature. Where
data are available, the secondary environmental effects were considered.
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SECTION 3-
RECOMMENDATIONS
The available literature contains little information on the effectiveness
of mitigation agents in treating hazardous substance discharges. Many miti-
gating agents (i.e., oxidizers, neutralizes, precipitators) are themselves
toxic if used in excess. Because of the variety of spill scenarios that
exist, the potential toxic effect of excess agent cannot be properly addressed.
The effectiveness of a mitigating agent depends heavily on the specific
spill situation. The amount of agent needed to counteract a hazardous sub-
stance discharge can be determined only for the academic situation of a labor-
atory evaluation. The spill conditions will vary in a real-life encounter.
The size of the watercourse can range from a small pond to a large lake,such
as the Great Lakes, to the ocean along the seacoast.
The conditions of'flow can also vary from a slow-moving, low-flow creek
during summer to a high-volume, turbulent river during spring.
The possible number of varied conditions of a watercourse dictate that a
classification system must be formulated and agreed upon. A mitigation pro-
cedure that is applicable for one spill scenario could be totally inappropri-
ate for another. For example, biological treatment agents may be effective
for a spill in an isolated small pond, but would not be suitable in a turbu-
lent river.
Only after this has been achieved can the effectiveness of a mitigation
procedure and the long-term toxic effects of irretrievable contaminated agents
and byproducts be adequately determined. It is recommended that a research
program be initiated to formulate a classification system of spill scenarios.
The persistence of toxic material in the environment,either treated or un-
treated, will be a factor in the selection of a counter-measure when the miti-
gating agent is not retrievable. The treatment will reduce the acute toxic
effect of the hazardous substance discharge. The long-term toxic effect of the
hazardous substance/mitigating agent complex may present an undesirable situa-
tion. The available literature indicates a lack of data to determine this po-
tential hazard to the environment. It is recommended that a research program
be initiated to determine the long-term toxic effect of irretrievable mitigat-
ing agents that have been contaminated with hazardous materials. This program
should address itself to the reentry of the hazardous material into the eco-
system and the toxicity of the contaminated mitigation agent.
The rationale for the use of chemicals and other additives to counteract
a discharge of a hazardous substance has been made based upon the available
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chemical and biological literature. The literature contains information that
can be applied to the mitigation process only in the ideal laboratory situa-
tions. There is little available information on the application of the miti-
gating agents to spills. It is recommended that a research program be initi-
ated to determine the limitations of chemical mitigating agents under differ-
ent field conditions.
Based on the available chemical and biological literature, recommendations
for the use of chemicals and other additives are made. The following recommen-
dations are made with respect to the classes of mitigating agents (mass trans-
fer media, absorbing, thickening and gelling, biological treatment, dispers-
ing, precipitating, oxidizing, and neutralizing).
Mass Transfer Media: Available evidence indicates that activated carbon
or ion exchange resins introduced in moderate amounts to the aquatic environ-
ment will not in themselves be toxic. Confirmatory bioassay testing is recom-
mended to more precisely determine concentrations which various fish and ben-
thic organisms may tolerate.
Potential persistence of toxic organic compounds in the aquatic environ-
ment, both in solution and bound to mass transfer media, must be a factor in
decisions relative to the use of irretrievable mass transfer agents for spill
treatment. It may be safely assumed that:
1. Those toxic substances that are readily removed from the solution by
biological processes in natural surface water are also readily re-
moved by these processes when bound to mass transfer media.
2. The total toxic effect of those biodegradable materials can be re-
duced if acute toxicity is minimized by use of irretrievable mass
transfer media,and natural biological processes are relied upon to
prevent chronic toxicity that would otherwise occur as a result of
desorption processes that are expected in natural surface waters.
Therefore, it is recommended that the use of irretrievable mass transfer
media be considered acceptable for treatment of that class of materials that
are biodegradable under all conditions.
Those materials that are not quickly degraded to nontoxic products in the
natural environment cannot be expected to degrade more rapidly in the bound
condition. Even though acute toxicity of a spill of such materials can be re-
duced by use of irretrievable mass transfer media, a serious chronic problem
could result with desorption. Under special circumstances in which it can be
shown that dispersion would reduce total contaminant concentration (i.e., in
solution and bound to mass transfer media) to nontoxic levels before desorp-
tion could occur, the use of mass transfer media to alleviate the acute tox-
icity problem would still be appropriate. Additional research on dispersion
rates, toxicity levels, and desorption rates would be required to permit the
on-scene coordinator to establish when those circumstances exist. We recom-
mend that such research be performed. Until the results of that research are
available, we recommend that irretrievable mass transfer media be considered
appropriate for treatment of spills of such materials only as a last resort.
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Absorbing Agents: It is recommended that the use of absorbents, both
natural and synthetic, be authorized for treatment of spills only in those
situations in which the sorbent can be removed from the environment. For
water spills, utility is therefore limited to organic liquids that are insol-
uble and float. For land spills, natural sorbents are useful for all liquids,
and synthetics for all organics that are absorbed.
Thickening and Gelling Agents: It is recommended that thickening and
gelling agents, either as specific compounds or as blended agents, be consid-
ered appropriate for use in treatment of land spills of all liquid materials
on which they are effective. Individual agents should be considered appropri-
ate for treatment of water spills of insoluble organics that float.
Thickening and gelling agents should not be used on water spills of mate-
rials that sink or mix into the water column.
More research is required to determine the effectiveness and behavior of
blended gelling agents in water before general recommendations can be made
relative to application to water spills.
Biological Treatment Agents: It is recommended that biological agents be
considered appropriate for mitigating spills of those materials that are bio-
degradable, but only for those cases in which the contaminated medium can be
contained. Because of the difficulty in controlling biological processes and
variables that affect them, it is recommended that other mitigation agents be
used for spill treatment whenever possible.
Dispersing Agents: The advantages of using dispersants to treat spills
are: (1) the rate of biodegradation is increased, (2) damage to marine fowl
is avoided since oil or other hazardous material is removed from the water
surface, (3) the fire hazard from the spill is reduced by dispersion of the
hazardous material several feet into the water column, (4) the spill is pre-
vented from wetting solid surfaces such as beach sand and shore property, and
(5) natural dilution is enhanced.
Dispersants are recommended as desirable additions to enhance the bio-
logical degradation of spilled material. However, they must be chosen with
care and the quantity used carefully controlled to avoid unnecessary harm to
aquatic life. Prior to the use of dispersants on a specific spilled substance,
it should be established through research that no increase in toxicity will
result from the dispersed substance or the degradation product of the added
dispersant.
Precipitating Agents: It is recommended that a solution of sodium sulfide
stabilized with sodium hydroxide be used as a precipitating agent for heavy
metal ions. The reentry of heavy metal sulfide precipitate into the water-
course will be sufficiently small to minimize any secondary toxic effects un-
less the heavy metal sulfide is converted to an organo metallic salt (e.g.,
mercury salts). Further study is required to determine the chronic effect of
metal salts in the water system.
Neutralizing Agents: It is recommended that neutralization be used as
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the primary treatment for all spills of acids and bases that are sufficiently
large as to create an environmental problem. Adequate monitoring is necessary
for all spill treatment. Treatment should be accomplished on land whenever
possible (i.e., before the spilled material flows into surface water).
In most spills of acids or bases, the principal toxic problem is caused
by the change in pH. In general, the return of pH to normal values reduces
toxicity regardless of neutralization agent used. It is recommended, however,
that care be taken when possible to select a neutralization agent that pro-
duces the least toxic byproducts in the neutralization reaction. It is fur-
ther recommended that other considerations being equal, weak acids and weak
bases be selected in preference to strong acids and bases as treatment agents.
By so doing, potential for overtreatment can be minimized.
Oxidizing Agents: Because of a variety of potential problems with the
use of oxidizing agents in spill control, it is recommended that their use be
limited to land spills and water spills that are completely contained. Oxi-
dants should be used on land and in surface waters only when no other spill
mitigation measure is available and only when the spilled material can be
contained for sufficient time to permit accurate control and monitoring of the
treatment.
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SECTION 4 "
SPILL MITIGATION MEASURES
This section discusses some of the parameters that enter into the
decision-making process used by the on-scene coordinator and what specific
counter-measures are effective for particular hazardous substance discharges.
The mitigation process has been divided into classes. The biological and
chemical literature was reviewed to evaluate various counter-measures. The
possible toxic effect of countermeasure agents was evaluated to determine the
acute toxicity of the agent and the long-term toxicity and persistence of the
nonretrieved agent contaminated with hazardous substances.
MASS TRANSFER MEDIA
This category of counter-measures involves use of those agents that will
remove the hazardous substance from the watercourse either by adsorption (e.g.,
activated carbon) or by mass transfer (e.g., ion exchange resins).
There is no doubt that the acute toxicity of many spills can be substan-
tially reduced by treatment with mass transfer media. When irretrievable mass
transfer media are used, a potential exists for desorption of the spilled mate-
rials to proceed at such a rate as to create a chronic toxicity problem. Some
of these materials have been identified, but others probably exist. Current
literature is inadequate. Therefore, it is recommended that the general use
of mass transfer media for spill treatment be limited to those spill materials
that degrade naturally to nontoxic products in uncontaminated surface water.
The effectiveness of treatment therefore is limited to the mitigation of the
acute toxicity problem.
In special cases, such as in large, fast-flowing streams where it can be
accurately determined that dispersion produces total contaminant concentra-
tion (i.e., free + bound) to nontoxic levels before desorption can occur, the
use of mass transfer media would also be applicable. Additional research on
desorption rates, toxicity levels, and dispersion rates would be required to
establish those conditions that constitute special cases.
Activated carbon is produced from organic materials by heating in the ab-
sence of air to drive off volatiles followed by steam or sometimes chemical
treatment to increase porosity. The most common raw materials used for acti-
vated carbon production are coal and lignin.
There is much evidence indicating the relative nontoxicity of activated
carbon to man. Carbon for water purification has been used over the ages. In
1817, Thomas Thompson (1) stated, "when putrid water at sea is mixed with about
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1/9th its weight with charcoal powder, it is rendered quite fresh." Activated
carbon is still routinely used to remove tastes and odors from potable water
supplied either by filtration through carbon beds or direct introduction of
carbon slurries to water supply reservoirs.
The direct introduction of powdered carbon into water supply reservoirs
has been used for algae control as well as taste and odor control. Dosages
for algae purposes are small, in the order of one to a few parts per million.
However, dosages are repeated, sometimes on a daily basis, until the algae
problem is eliminated. Activated carbon is not considered toxic per se to
algae; rather, it reduces the penetration of light, thus reducing algal growth.
The literature does not contain references related to effects on fish or ben-
thic organisms when activated carbon is used for reservoir treatment. If sig-
nificant fish kills occurred, one would expect documentation in the literature.
In a bioassay study on the toxicity of powdered activated carbon on fish
(2) it was found that fathead minnows could survive short contact times in a
10% carbon slurry. The 24-hour LDso (i.e., that water concentration at which
half the test organisms survived over a 24-hour period) for fathead minnows in
carbon-treated water was 30,000 ppm.
In water bodies, carbon will either settle to the bottom (with the excep-
tion of special floatable carbon such as AQUA NUCHAR C-190) in the immediate
vicinity of the spill treatment, or be carried near or far downstream before
settling.
In either case, the concentration of activated carbon should decrease
rapidly after a single application since it behaves physically like silt in
the water column.
Based on available evidence, the application of activated carbon alone to
water bodies will not constitute a threat to human or aquatic life unless ap-
plied in massive quantities. Further bioassay testing, especially on the ef-
fects of activated carbon on benthic organisms, is recommended to confirm the
concentration of carbon which the aquatic environment is able to assimilate
without significant stress. Thus, with reservations pending results of those
tests on benthic organisms, it is concluded that a single application of irre-
trievable activated carbon at the incorrect location (i.e., missing the spill
plume) is not expected to present a serious ecological effect other than the
temporary aesthetic problem.
Ion exchange resins consist of insoluble high-molecular-weight organic
polymers containing charged functional groups that are able to exchange with
either positive or negative ions in aqueous solution. Resins that exchange
cations from functional groups for cations in solution are cation exchange
resins. Resins that exchange anions from functional groups for anions in sol-
ution are anion exchange resins. In strong acid ion exchange resins, the func-
tional group is normally a sulfonic group and weak acid ion exchange resins
usually contain a carboxylic or phenolic group. The functional groups in
strong base anion exchange resins are generally quarternary ammonium compounds
and weak base anion exchangers employ an amino or imino functional group.
13
-------
Commercially available ion exchange resins employ H and Na as the pre-
dominant exchangeable cations while Cl" and OH~ appear as the predominant ex-
changeable anions. The toxicity of the above ions is relatively low.
In a spill situation, depending on what material is spilled and what
type of resin is used, there will be exchange of the spilled substance for
one of the above. As an example, for a spill of a heavy metal salt of mercury
using a strong acid ion exchange resin, the following occurs:
2RS03H + Hg+2 -» (RS03)2Hg + 2H*
where
R = Resin matrix
S03H = Functional group
It is of importance to note that exchange is stoichiometric, resulting in
weight equivalent exchange.
The question arises as to whether or not the organic matrix or the func-
tional groups of exchange resins are toxic to humans, fish or other aquatic
organisms.
The relative human nontoxicity of ion exchange resins prepared according
to specifications is supported by their use in the food and pharmaceutical in-
dustries. Ion exchange resins are used to purify water used in food prepara-
tion, purify water for use in manufacture of distilled alcoholic beverages,
purification of Pharmaceuticals, and color and other impurity removal from
sugars. Resins are also ingested directly to reduce salt (Na"1") intake.
Ion exchange resins used in food and pharmaceutical preparation are sub-
ject to Food and Drug Administration (FDA) regulations. The regulations list
the types of resins that can be used in the preparation of food based on com-
position of the resin matrix. There are 16 listed types of resin matrices
including the more common ones identified in the regulations. The exchange-
able cations or anions normally employed in exchange resins (i.e., H"1", Na ,
Cl", OH-) are approved for use under proper conditions.
The regulations stipulate the procedures for use of ion exchange resins
in food preparation, and testing and labeling requirements for ion exchange
resins to be used in the treatment of food. It is of importance to note the
very low solubility requirements in various solvents (no more than 1 ppm or-
ganic extractives in distilled water, alcohol, and acetic acid).
The differences between food and pharmaceutical and normal ion exchange
production is the high degree of quality control and purification for the for-
mer. The use of approved food or pharmaceutical-grade ion exchange resins for
spill treatment is not expected to pose any hazard to water for human consump-
tion. These resins would also not be expected to be toxic to fish or aquatic
organisms. However, direct evidence of nontoxicity to fish or aquatic life is
not available. Confirmatory bioassay tests are recommended.
14
-------
It is also quite probable that ion exchange resins not having food or
pharmaceutical approval would still not pose a threat to aquatic life or
drinking water when used to treat spills. Recall that the differences in man-
ufacture are mainly differences in quality control. If irretrievable ion ex-
change resins are introduced at the incorrect location, there will be some ex-
change with natural ionic material that occur in trace amounts in surface
water. This may cause a temporary depletion of desirable ionic species but it
is not expected to produce any significant problems.
Hazardous Pollutant Removal by Mass Transfer Media
In addition to selecting a nontoxic agent for hazardous spill treatment,
it is highly desirable to select a treatment agent that gives the highest pro-
bability of effective spill treatment. The agent selected for treatment should
be that which most effectively adsorbs or exchanges the spilled hazardous pol-
lutant from solution, thereby rendering it less hazardous to the aquatic envi-
ronment. The effectiveness of activated carbon and ion exchange resins for
'removal of specific organic and inorganic compounds from water (under ideal
conditions of contact) were investigated.
The mechanisms of carbon adsorption and ion exchange have been examined
with respect to prediction of the degree to which these media will remove or-
ganic and inorganic compounds from solution.
The mechanisms ofcarbon adsorption are not well understood, but empiri-
cal observation of adsorption phenomena have resulted in a number of general-
izations that are of value in predicting adsorbability. It has been well dem-
onstrated that both the rate and degree of carbon adsorption increase with the
concentration of pollutant in water. The strategy of fast response to spills
before extensive dilution is extremely important.
In general, it is found that carbon adsorption is more effective for com-
pounds of low solubility (Lundelius1 rule). Since solubility of organic com-
pounds generally decreases with increasing chain length, it has been observed
that adsorption from aqueous solution increases as a homologous series is as-
cended (Traube's rule). However, the rate of adsorption generally decreases
with increasing molecular weight.
For organic compounds that are structurally simple, carbon adsorption is
at a minimum for the charged species in water and at a maximum for neutral
species. As compounds become more complex, effects of ionization become of
decreasing importance.
The amenability of organic compounds to activated carbon was studied by
Guisti et al. (3) with activated carbon dosages that were five times the pol-
lutant concentration. Table 2 provides their data on the percent reduction of
pollutant. This information can provide valuable assistance relative to the
applicability of mass transfer agents for spills of specific substances, but
cannot predict the degree of success for specific spill scenarios. The time
to respond, water current, turbulence, and volume of water affected are other
determinants of spill treatment effectiveness, as well as choice of treatment
agent.
15
-------
TABLE 2. AMENABILITY OF TYPICAL ORGANIC COMPOUNDS
TO ACTIVATED CARBON ADSORPTION
Compound
Alcohols
Methanol
Etnanol
Propanol
Butanol
n-Amyl alcohol
n-Hexanol
Isopropanol
Allyl alcohol
Isobutanol
t-Butanol
2-£thyl butanol
2-Ethyl hexanol
A1 dehydes
Formaldehyde
Acetaldehyde
Propionaldehyde
Butyaldehyde
Acrolein
Crotonaldehyde
Benzaldehyde
Paraldehyde
Amines
Di-N-PropyTamine
Butyl ami ne
Oi-N-Butylamine
Allylamine
Ethyl enedi ami ne
Diethylenetriamine
Monethanolamine
Oiethanolamine
Triethanolamine
Monoisopropanolamine
Oiisopropanolamine
Pyridines & Morpholines
Pyridine
2-Methyl 5-Ethyl pyridine
N-Methyl morpholine
N-Ethyl morpholine
Aromatics
Benzene
Toluene
Ethyl benzene
Phenol
Hydroquinone
Aniline
Styrene
Nitrobenzene
Esters
Methyl acetate
Ethyl acetate
Molecular
Weight
32.0
46.1
60.1
74.1
88.2
102.2
60.1
58.1
74.1
74.1
102.2
130.2
30.0
44.1
58.1
72.1
56.1
70.1
106.1
T32.2
101.2
73.1
129.3
57.1
60.1
103.2
61.1
105.1
149.1
75.1
133.2
79.1
121.2
101.2
115.2
78.1
92.1
106.2
94.0
110.1
93.1
104.2
123.1
74.1
88.1
Aqueous
Solubility
(%)
CO
CD
CO
7.7
1.7
0.58
CO
CO
8.5 -
CO
0.43
0.07
oo
00
22.0
7.1
20.6
15.5
0.33
10.5
CO
CO
00
CO
CO
CO
CO
95.4
CO
CO
87.0
00
si. sol.
CO
CO
0.07
0.047
0.02
6.7
6.0
3.4
0.03
0.19
31.9
8.7
Concentration (mq/1 )
Initial (CQ) Final (Cf)
1000
1000
1000
1000
1000
1000
1000
1010
1000
1000
1000
700
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1012
996
1000
1000
1000
1000
. 1000
1000
1000
416
317
115
1000
1000
1000
180
1023
1030
1000
964
901
811
466
282
45
874
789
581
705
145
10
908
381
723
472
694
544
60
261
198
480
130
686
893
706
939
722
670
800
543
527
107
575
467
21
66
18
194
167
251
18
44
760
495
Adsorbabi 1 i ty *
g Compound/
g Carbon
0.007
0.020
0.038
0.107
0.155
0.191
0.025
0.024
0.084
0.059
0.170
0.138
0.018
0.022
0.057
0.106
0.061
0.092
0.188
0.148
0.174
0.103
0.174
0.063
0.021
0.062
0.015
0.057
0.067
0.040
0.091
0.095
0.179
0.085
0.107
0.080
0.050
0.019
0.161
0.167
0.150
0.028
0.196
0.054
0.100
Percent
Reduction
3.6
10.0
18.9
53.4
71.8
95.5
12.6
21.9
41.9
29.5
85.5
98.5
9.2
11.9
27.7
52.8
30.6
45.6
94.0
73.9
80.2
52.0
87.0
31.4
10.7
29.4
7.2
27.5
33.0
20.0
45.7
47.3
89.3
42.5
53.3
95.0
79.2
84.3
80.6
83.3
74.9
88.8
95.6
26.2
50.5
Dosage: 5 g Carbon C/1 of solution.
(continued)
16
-------
TABLE 2 (CONTINUED)
Compound
Esters
Propyl acetate
Butyl acetate
Primary amyl acetate
Isopropyl acetate
Isobutyl acetate
Vinyl acetate
Ethylene glycol monoethyl
ether acetate
Ethyl acrylate
Butyl acrylate
Ethers
Isopropyl ether
Butyl ether
Dichloroisopropyl ether
Clycols & Glycol Ethers
Ethylene glycol
Diethylene glycol
Triethylene glycol
Tetraethylene glycol
Propylene glycol
Dipropylene glycol
Hexylene glycol
Glycol s & Glycol Ethers
Ethylene glycol
monomethyl ether
Ethylene glycol
monoethyl ether
Ethylene glycol
monobutyl ether
Ethylene glycol
monohexyl ether
Diethylene glycol
monoethyl ether
Diethylene glycol
monobutyl ether
Ethoxytriglycol
Halogenated
Ethylene dichloride
Propylene dichloride
Ketones
Acetone
Methyl ethyl ketone
Methyl propyl ketone
Methyl butyl ketone
Methyl isobutyl ketone
Methyl isoamyl ketone
Di isobutyl ketone
Cyclohexanone
Acetophenone
Isophorone
Molecular
Weight
102.1
116.2
130.2
102.1
116.2
86.1
132.2
100.1
128.2
102.2
130.2
171.1
62.1
106.1
150.2
194.2
76.1
134.2
118.2
76.1
90.1
118.2
146.2
134.2
162.2
178.2
99.0
113.0
58.1
72.1
86.1
100.2
100.2
114.2
142.2
98.2
120.1
138.2
Aqueous
Solubility
2.0
0.68
0.2
2.9
0.63
2.8
22.9
2.0
0.2
1.2
0.03
0.17
00
00
00
00
CO
CD
00
00
00
00
0.99
00
00
00
0.81
0.30
CO
26.8
4.3
V. Si. SOl .
1.9
0.54
0.05
2.5
0.55
1.2
Concentration (mg/1)
Initial (CQ)
~
1000
1000
985
1000
1000
1000
1000
1015
1000
1023
197
1008
1000
1000
1000
1000
1000
1000
1000
1024
1022
1000
975
1010
1000
1000
1000
1000
1000
1000
1000
983
1000
986
300
1000
1000
1000
Final TCf)
248
154
119
319
180
357
342
226
43
203
nil
nil
932
738
477
419
884
835
386
886
705
441
126
570
173
303
189
71
782
532
305
191
152
146
nil
332
28
34
Adsorbability*
g Compound/
/g Carbon
0.149
0.169
0.175
0.137
0.164
0.129
0.132
0.157
0.193
0.162
0.039
0.200
0.0136
0.053
0.105
0.116
0.024
0.033
0.122
0.028
0.063
0.112
0.170
0.087
0.166
0.139
0.163
0.183
0.043
0.094
0.139
0.159
0.169
0.169
0.060
0.134
0.194
0.193
Percent
Reduction
75.2
84.6
88.0
68.1
82.0
64.3
65.8
77.7
95.9
80.0
100.0
100.0
6.3
26.2
52.3
58.1
11.6
16.5
61.4
13.5
31.0
55.9
87.1
43.6
82.7
69.7
81.1
92.9
21.8
46.8
69.5
80.7
84.8
85.2
100.0
66.8
97.2
96.6
* Dosage: 5 g Carbon C/l of solution.
(continued)
17
-------
TABLE 2 (CONTINUED)
Compound
Organic Acids
Formic acid
Acetic acid
Propionic acid
Butyric acid
Valeric acid
Caproic acid
Acrylic acid
Benzoic acid
Oxides
Propylene oxide
Styrene oxide
Molecular
Weight
46.0
60.1
74.1
88.1
102.1
116.2
72.1
122.1
58.1
120.2
Aqueous
Solubility
00
00
00
00
2.4
1.1
00
0.29
40.5
0.3
Concentration (mg/1)
Initial (CQ)
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
Final (Cf)
765
760
674
405
203
30
355
89
739
47
Adsorbability*
g Compound/
g/ Carbon
0.047
0.048
0.065
0.119
0.159
0.194
0.129
0.183
0.052
0.190
Percent
Reduction
23.5
24.0
32.6
59.5
79.7
97.0
64.5
91.1
26.1
95.3
* Dosage: 5 g Carbon C/l of solution.
The adsorption and desorption. from ion exchange resins depend upon the
exchange resin matrix and the chemical pollutant. The primary consideration
is whether or not "strong" versus "weak" ion exchange resins are to be recom-
mended for spill treatment. In strong acid ion exchange resins, the functional
group is normally a sulfonic group such as -S03H or -SOsNa. A weak acid ion
exchange resin usually.-contains a carboxylic (-COOH) or phenolic group (-OH).
Weak acid cation exchangers normally exchange only the cations associated with
weak acid salts such as bicarbonate, carbonates, and acetates. They generally
do not react with cations of strong acid salts such as chlorides, sulfates,
and nitrates. Therefore, strong acid cation exchange resins are preferable
for general use for spilled substances amenable to cation exchange treatment.
The functional groups in strong-base anion exchange resins are generally
quarternary ammonium compounds, while weak-base anion exchangers employ an
amino or imino functional group. Weak-base anion exchangers usually do not
exchange the anions associated with the salts of weak acids, whereas strong-
base anion exchange resins exchange anions of both weak and strong acids and
their salts. It is also pointed out in manufacturers' specifications for anion
resins that weak-base anion exchange resins are effective only in the pH range
0 to 7, whereas strong-base anion exchange resins are effective in the entire
pH range of 0 to 14. Thus, strong-base anion exchange resins have greater
utility in spill treatment.
Desorption and Persistence of Hazardous
Pollutants From Mass Transfer Media
Given that a hazardous substance is removed from surface water by acti-
vated carbon or an ion exchange resin, it is of importance to ascertain the
extent to which desorption may occur and the biological consequences of this
desorption. In addition, it is of importance to ascertain if toxic substances
(captured) on carbon or ion exchange resins persist, or are chemically or bio-
logically degraded to a less, or possibly more, toxic product.
18
-------
Information from manufacturers and the literature indicates that desorp-
tion from activated carbon or ion exchange resins should not easily occur in
natural waters. Normally, to strip carbon of the adsorbed organics or to re-
move exchanged ions from exchange resins, drastic changes of ambient condi-
tions such as pH adjustment, solvent extraction, or heating at 1600°F to 1800°F
and ion exchange resins are often regenerated by treatment with caustic or
acid. Such extreme changes in ambient conditions would not be expected in
natural water bodies.
Desorption from activated carbon by water alone has, however, been ob-
served for some pesticides (4). Moderate amounts of acidic herbicides (2,4-0
or 2,4,5-T) have been found to be readily desorbed from activated carbon by
water. The phenylurea herbicides (Diuron and Monuron) have been found to be
adsorbed on activated carbon in large amounts only to be readily desorbed in
uncontaminated water.
The question posed with regard to the use of carbon or ion exchange res-
ins on substances that may later exhibit desorption is whether desorption pro-
duces a greater toxicologic problem than if the agent were not used. The
question of persistence in adsorbed or nonadsorbed states must be considered
in overall evaluations.
There are no studies in the literature on the release of hazardous sub-
stances from ion exchange resins and resultant influence on fish or other
aquatic organisms. It'is apparent that further study is needed to more clearly
establish the desorptive behavior of hazardous pollutants from activated car-
bon and ion exchange resins in the aquatic environment and subsequent influ-
ence on fish and benthic organisms.
As discussed previously, the degree to which organic pollutants persist
in the aquatic environment in either adsorbed or unadsorbed states enters into
decisions to treat hazardous substances with irretrievable mass transfer media.
Ideally, treatment of a spilled hazardous organic substance with carbon or ion
exchange resin will substantially reduce acute toxicity, followed by chemical
and/or biological decomposition of the adsorbed organic to a nonhazardous sub-
stance. Persistence in the adsorbed state accompanied by chronic poisoning of
the aquatic habitat is undesirable.
Washington University researchers compiled, organized, and interpreted a
mass of data on the persistence of organic chemicals in dilute aquatic systems
such as might be present in a quiescent lake (5). They reported degradation of
organic compounds as a percent of the theoretical oxidation under various con-
ditions including "as-is" river water, sewage seed, and acclimated activated
sludge seed. The Washington State researchers then categorized the various
organics into one of three groups:
1. Organic compounds readily removed from aquatic environment (Table 3),
2. Organic compounds removed from aquatic environment with acclimated
microorganisms (Table 4), and
3. Organic compounds resistant to removal from aquatic environment.
19
-------
TABLE 3. REPORTED ORGANIC COMPOUNDS READILY REMOVED FROM AQUATIC ENVIRONMENT
Compound
Alcohols
Ally! alcohol
Ethanol
Glycerol
Glycol
n-Hexadecanol
p-Hydroxy benzole acid
Methanol
1 ,5-Pentanediol
Phenols
o-Cresol
m-Cresol
p-Cresol
1-Naphthol
Phenol
Aldehydes, Acids and Salts
Furfural
Acetic acid
Citric acid
Formic acid
Lactic acid
Mandolic acid
Oxalic acid
Quinic acid
Tartaric acid
Ammonium acetate
Calcium formate
Calcium gluconate
Ethyl formate
Phenyl acetate
Nitrogen Compounds
Alanine
Glutamic acid
Glycine
Miscellaneous
2-Ethyl 3-propyl acrolein
Dextrin
Glucose
Starch
Styrene
Xylose
AS - Activated sludge seed
Resp. - Respirometer
RW - River water
CA - Chemical analysis
B - Bacterial culture
Technique
-
BOD AS
Resp. AS
Resp. AS
Resp. AS
RW CA-C02
Resp. B
Resp. AS
BOO AS
RW CA
RW CA
RW CA
RW CA
RW CA
RW CA
Resp. AS
Resp. AS
Resp. AS
Resp. AS
Resp. B
Resp. AS
Resp. B
Resp. AS
Resp. AS
BOD AS
Resp. AS
BOD AS
Resp. B
Resp. AS
Resp. AS
Resp. AS
BOD RW
Resp. AS
Resp. AS
Resp. AS
CA-C02
Resp. AS
Ref.
375
366
429
429
319
507
366
375
159
159
159
159
159
157
429
429
429
429
507
429
507
429
429
375
429
375
507
429
429
429
499
429
429
429
411
429
20
-------
TABLE 4. REPORTED ORGANIC COMPOUNDS REMOVED FROM AQUATIC
ENVIRONMENT WITH ACCLIMATED MICROORGANISMS
Compound
Hydrocarbons
n-Butyl benzene
Ethyl benzene
n-Propyl benzene
Alcohols
n-Amyl alcohol
sec-Amy! alcohol
Benzyl alcohol
n-Butanol
sec-Butanol
tert-Butanol
n-Dodecanol
n-Hexanol
Isoamyl alcohol
Isobutanol
Isopropanol
Methanol
4-Pentanol
n-Propanol
Phenols
o-Chlorophenol
p-Chlorophenol
Aldehydes, Ketones , Acids, Salts,
Acetaldehyde
Benzaldehyde
Cinnamaldehyde
Crotonoldehyde
Formaldehyde
2,4-Hexadienal
Methacrolein
Resp. - Respirometer
AS - Activated sludge seed
RW - River water
CA - Chemical analysis
BOD - Biological oxygen demand
Technique
Resp. AS
Resp. AS
Resp. AS
BOD AS
BOD AS
Resp. AS
Resp. AS
Resp. AS
Resp. AS
Resp. AS
BOO AS
BOD AS
Resp. AS
Resp. AS
Resp. AS
BOD RW
Resp. AS
CA RW
CA RW
and Ethers
Resp. AS
BOD AS
BOD RW
BOD RW
Resp. AS
BOD RW
BOD RW
* Uli^fc. * ..,. ...
" ' - " ~~- ""'*' -._- T_ i -. -, ... _ii. / '
(
Ref.
59
59
59
219
219
366
366
366
366
59
375
219
366
366
137
499
366
158
158
429
375
499
499
429
499
499
'continued
21
-------
TABLE 4 (CONTINUED)
Compound
Aldehydes, Ketones, Acids, Salts,
Propionaldehyde
Acetone
Di ethyl ketone
Methyl n-amyl ketone
Methyl isobutyl ketone
Methyl phenyl ketone
Methyl isopropyl ketone
Acrylic acid
Ben zoic acid
Caproic acid
Formic acid
Heptanoic acid
Methacrylic acid
Valeric acid
Diethylene glycol monoethyl
ether acetate
Di glycol di acetate
Ethyl ene di chloride
Propene oxide
Methylmethacryl ate
2 Methoxy ethyl acetate
Sodium formate
Sodium oleate
Sodium stearate
Vinyl acetate
Dimethoxy methane
2-Ethoxy ethanol
2-Methoxy ethanol
Methyl phenyl ether
Tri ethyl ene glycol
Nitrogen Compounds
Acetanilide
Acetonitrile
Acetyl ethanol ami ne
Res p. - Respirometer
AS - Activated sludge seed
RW - River water
CA - Chemical analysis
BOD - Biological oxygen demand
Technique
and Ethers (continued)
BOD AS
COD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD RW
CA-C02
BOD AS
BOD AS
BOD AS
BOD AS
CA-C02
BOD AS
BOD AS
BOD AS
BOD AS
COD AS
CA-COz
BOD AS
Resp. AS
BOD AS
BOD AS
CA-C02
COD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD RW
CA-N2
BOD AS
90
Ref.
219
219
375
375
375
375
499
411
153
153
153
153
411
153
375
375
375
219
411
375
137
59
59
411
219
59
375
375
375
374
331
375
(continued)
-------
TABLE 4 (CONTINUED)
Compound
Nitrogen Compounds (continued)
Acrolein
Ac ryl amide
Acrylonitrile
Adiponitrile
Anthranallic acid
Arginine
Benzonitrile
Diaminoethane
Diethanolamine
lactonitrile
Leucine
Methionine
Monoethanolamine
Morpholine
Oxydipropionitrile
Phenylalanine
3-Picol ine
Pyridine
Threonine
Tryptophane
Tyros ine
Valine
Sulfur Compounds
n-Butyl benzene sulfonate
sec-Butyl benzene solfonate
n-Dodecyl sodium sulfonate
Ethyl benzene sulfonate
Lauryl sulfate
Methyl benzene sulfonate
n-Octyl benzene sulfonate
sec-Octyl sulfonate
n-Propyl benzene sulfonate
sec-Propyl benzene sulfonate
Sodium benzene sulfonate
Resp. - Respirometer
AS - Activated sludge seed
RW - River water
CA - Chemical analysis
BOD - Biological oxygen demand
Technique
-
BOD RW
COD RW
CA-N2
CA-N2
Resp. AS
BOD AS
CA-N2
BOD RW
BOD AS
CA-RW-N2
BOD AS
BOD AS
BOO AS
BOD AS
CA RW-N2
BOD AS
CA RW
CA RW
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
BOD AS
Ref.
499
104
331
331
369
153
331
374
375
331
153
153
375
375
331
153
156
156
153
153
153
153
457
457
464
457
464
457
457
457
457
457
59
23
-------
It appears reasonable to believe that organic compounds that readily de-
grade in water will also degrade in an aqueous system when adsorbed on carbon
or are attached to ion exchange resins.
The mass transfer media should provide a good substrate for bacteria and
other organisms to consume the adsorbed pollutant. Adsorption to reduce acute
toxicity, followed by microbial degradation^ appear to be a reasonable treat-
ment sequence if degradation is reasonably fast and degradation products are
not themselves significantly toxic. Bioassay tests to ascertain the degree to
which adsorbed or ion exchanged hazardous substances degrade, and attendant
toxicity phenomenon accompanying this degradation, are recommended.
It has been found in soil studies that, generally, adsorption of pesti-
cides on soil and organic matter reduces toxicity. Concurrently, however, a
number of pesticides, especially chlorinated hydrocarbons, have been found to
persist for longer periods of time when adsorbed on soil or organic matter.
Similar behavior appears reasonable when adsorption is on carbon or ion ex-
change resins. Studies of the persistence and toxicity of pesticides (and
other hazardous pollutants) when adsorbed on activated carbon or ion exchange
resins are recommended.
Conclusions and Recommendations
Available evidence indicated that activated carbon or ion exchange resins
introduced in moderate-amounts to the aquatic environment will not in them-
selves be toxic. Confirmatory bioassay testing is recommended to more pre-
cisely determine concentrations which various fish and benthic organisms may
tolerate.
Potential persistence of toxic organic compounds in the aquatic environ-
ment, both in solution and bound to mass transfer media, must be a factor in
decisions relative to the use of irretrievable mass transfer agents for spill
treatment. It may be safely assumed that
1. Those toxic substances that are readily removed from the solution by
biological processes in natural surface water are also readily re-
moved by these processes when bound to mass transfer media, and
2. The total toxic effect of those biodegradable materials can be re-
duced if acute toxicity is minimized by use of irretrievable mass
transfer media and natural biological processes are relied upon to
prevent chronic toxicity that would otherwise occur as a result of
desorption processes that are expected in natural surface waters.
Therefore, it is recommended that the use of irretrievable mass transfer
media be considered acceptable under all conditions for treatment of that class
of materials which are biodegradable. Specific materials that are known to be
in this class are indicated in the countermeasure matrix presented in Section 5.
Those materials that are not quickly degraded to nontoxic products in the
natural environment cannot be expected to degrade more rapidly in the bound
condition. Even though acute toxicity of a spill of such materials can be
24
-------
reduced by use of irretrievable mass transfer media, a serious chronic problem
could result with desorption. Under special circumstances in which it can be
shown that dispersion would reduce total contaminant concentration (i.e., in
solution and bound to mass transfer media) to nontoxic levels before desorp-
tion could occur, the use of mass transfer media to alleviate the acute tox-
icity problem would still be appropriate. Additional research on dispersion
rates, toxicity levels and desorption rates~would be required to permit the
on-scene coordinator to establish when those circumstances exist. We recom-
mend that such research be performed. Until the results of that research are
available, we recommend that irretrievable mass transfer media be considered
appropriate for treatment of spills of such materials only as a last resort.
Activated carbon is sold in many forms from a fine powder to large gran-
ules. Multipurpose activated carbon that may be used in spill mitigation may
be obtained from these companies:
American Novit Company
Calgon Corporation
ICI America, Ltd.
Westvaco Chemical Division
Union Carbide Corporation
Barneby-Cheney Company
Ion exchange resins are also sold in many forms by several manufacturers.
Dow Chemical Company and Rohm and Haas Company manufacture and market a large
variety of ion exchange resins that are appropriate for spill mitigation. We
recommend that company representatives be contacted at the time of a spill to
determine which available ion exchange resin is most appropriate for use on
the specific material involved in the spill.
ABSORBENTS
The use of absorbents for treatment of spills of hazardous substances
other than oil has not been practiced or even studied to a great extent.
Available information indicates that absorbents would be of value for treat-
ment of all land spills and of water spills of some organic materials. Use of
absorbents for treatment of water spills will probably be limited to those sub-
stances that are insoluble and float on the water surface (i.e., that behave
much like oil).
Absorbents can be divided into two general types: natural and synthetic.
Natural absorbents include natural products such as vegetation residues includ-
ing corn plant stalks and straw, and wood residues including sawdust and lig-
nin. These natural materials have been used for years in mitigating oil
spills. However, specific data are not available on their effectiveness for
absorbing other organic liquids.
Absorbent materials derived from natural materials including straw, corn-
based absorbents, and wood-based and others are presumed to be nontoxic though
confirmatory data are not available. A large amount of these materials intro-
duced into a water body could produce a high biological oxygen demand (BOO)
upon degradation by microorganisms. Slowly degradable substances such as
25
-------
lignin-based materials, or sawdust, would not be expected to impose as rapid
biological oxygen demands as straw or other highly biodegradable organics.
Synthetic products have been made from various organic polymers including
polypropylene, alklystyrene and polyurethane. They are specifically manufac-
tured to absorb hydrophobic organic liquids while repelling hydrophillic
liquid such as water. A review of commercial synthetic products shows that
a variety of different polymers are used. Three commercial products that rep-
resent different types of organic polymers will be discussed:
1. 3M "Oil Absorbent" - polypropylene
2. Dow "Imbiber Beads" - cross-linked co-polymer
3. SSC "Absorbents" - polyurethane
3M Company "Oil Absorbent" is a white, fibrous polymer made from polypro-
pylene, has a density of 0.91 and remains buoyant after saturation with oil and
most other organic liquids. It is insoluble in water and resistant to all com-
mon solvents.
Dow imbiber beads are made from a number of lightly cross-linked polymers
including alkylstyrene polymers or tertiary butyl polymers. The exact compo-
sition is unknown. The density of the imbiber heads varies from 0.95 to
slightly over 1.0. A special property of Dow imbiber beads is their tendency
to swell up to three diameter sizes upon imbibition of organics, including aro-
matic hydrocarbons, benzene, toluene, styrene and chlorohydrocarbons without
dissolution of the polymer matrix. Imbiber beads are insoluble in water,
methanol, or acetone.
SSC absorbents are prepared from specially treated polyurethanes. The
nature of the "special" treatment is not given in product literature. SSC
absorbents are also buoyant before and after oil adsorption.
Some information on toxicological properties of these commercial absor-
bents mentioned previously have been provided by the manufacturers. The "oil
absorbent" which is 100% polypropylene is claimed as nonirritating to the skin
and the eyes according to information provided to the U.S. Department of Labor
by the 3M Company (6). However, protective gloves are advised for continuous
handling. Communication with 3M Company (7) reveals that this material has FDA
approval for use in removing oils from household foodstuffs such as gravy. It
can be considered, therefore, as nontoxic to humans. Bioassay test data with
fish and other aquatic organisms is not available, although it may be reason-
ably assumed that polypropylene is nontoxic to fish.
Communications with Dow Chemical (8) reveal that some of the imbiber
bead products have undergone bioassay tests and have been approved for use as
absorbents by the State of California, State Water Resources Control Board.
As such, they have been ascertained to be nontoxic to fish.
The Sorbent Sciences Corporation (SSC) has shown that their polyurethane
absorbent material is nontoxic to brine shrimp and California killfish in
26
-------
concentrations ranging from 0.5 gm/1 to 10.0 gm/1. Bioassay tests were con-
ducted over 72-hour periods according to Standard Methods for the Examination
of Water and Wastewater. The SSC absorbent material has also been approved
for use as a collecting agent by the State of California, State Water Re-
sources Control Board, based on results of bioassay testing.
In addition to bioassay tests, SSC tested degradation of polyurethane
absorbents in sea water. There was no weight loss over a 20-day period, indi-
cating that biodegradation or chemical degradation of the product does not
occur in sea water.
Treatment Effectiveness
There are no data indicating the extent to which natural materials such
as straw, ground corn cobs, sawdust, etc. will absorb organic liquids other
than oil. Various companies have provided some data on synthetic product
absorption of specific organic liquids or classes of organic liquids. Most
data that have been provided concerns absorption of pure organic liquids.
This information can be reasonably extrapolated to ascertain the effectiveness
of the agents for land spills. In cases where spills occur in water, estimates
of removal effectiveness cannot be directly inferred from the data on absorp-
tion of pure liquids. Extrapolation is reasonable for highly insoluble organ-
ic liquids that float on the water surface.
The 3M Company provided data on the absorption capacity of its polypropy-
lene absorbent for a number of pure organic liquids, as given below:
Absorption Capacity,
Chemical g Chemical/g Sorbent
Hexane 7.4
Benzene 10.0
Naphtha 8.5
Kerosene 8.2
Freon 133 15.8
Chloroform 17.8
Ethyl ether 8.1
Ethyl acetate 10.7
Butyraldehyde 8.8
Methyl ethyl ketone 11.9
n-Amyl alcohol 10.9
Polyethylene glycol 400 MW 4.2
Methanol 12.1
Dimethyl formamide 15.4
These data pertain to pure organic liquids and are therefore applicable
for land spills. Beginning with ethyl ether and proceeding downward, the named
substances are highly soluble or miscible with water. Absorption of these sub-
.stances from water is therefore expected to be poor according to 3M (9).
27
-------
Dow imbiber beads can be custom-made to absorb specific substances. They
are generally made of alkylstyrene tertiary butyl copolymers. The copolymers
are claimed to be capable of absorbing a number of organic liquids including
the following (10):
Linear aliphatics such as hexane and gasoline
No. 1,2 and 3 fuel oils
Chlorinated solvents such as methyl chloroform and trichlorobenzene
Aromatic solvents such as benzene, styrene, and methyl naphthalene
Some polar materials including methylisobutylketone, ether, and
tetrahydrofuron
A partial listing of specific substances that are said to be imbibed by
one type of Dow cross-linked swellable polymer (Imbiber Bead "S") includes the
following:
cumene
divinyl benzene
ethyl benzene
benzene
pyridine
toluene
Chlorobenzene
dichlorobenzene
benzyl chloride
methyl bromide
xylenes
epichlorohydrin
dibromochloropropane
styrene
trichlorofluoromethane
chloroform
chloromethane
dichlorodifluoromethane
perch!oroethylene
trichloroethylene
halogenated hydrocarbons
ethylene dichloride
trichlorobenzene/PCB mixtures
In addition to imbibition of hydrocarbons floating on the surface of the
water, imbiber beads have been shown to remove kerosene, toluene, and benzene
that were dissolved in water up to saturation. Removal by agitated contact
with cross-linked alkylstyrene polymers was 74% for dissolved kerosene, 95.9%
28
-------
for dissolved toluene, and 96.5% for dissolved benzene (11).
The SSC specially treated polyurethane foam is claimed to pick up low-
and high-viscosity oil, paint, petrochemicals, tar, vegetable oils, and many
other organic materials from water surfaces. Storage capacity of 40 to 60
times the weight of the absorbent is claimed.
Of the two categories of absorbents (natural and synthetic), there are
little data available to estimate the absorption of organic liquids other than
oil by natural absorbents. The limited data given in previous sections of this
report give some guidance, but perhaps not all that is needed for complete tab-
ulation of organic liquid treatment using synthetic absorbents. As a general
rule, it appears that polar substances with appreciable solubility or misci-
bility with water must be rated as poorly removed by synthetic absorbents. In
addition, dense organic liquids that sink in the water column cannot be effec-
tively removed by absorbents. The problem is relating the degree of organic
liquid solubility to a treatment rating for synthetic absorbents in terms of
"good," "fair," and "poor" 'removability from water. There is little data to
provide guidance in rating the many substances under consideration on the pro-
posed "hazardous substance list."
The synthetic absorbent material has been designed for organic material
based on chemical theory. Therefore, they are not expected to be efficient in
the absorption of inorganic liquids.
Desorption and Persistence of Hazardous Pollutants from Absorbents
Natural absorbents such as straw and corn will absorb oil and perhaps sim-
ilar organics only from surfaces having thick floating deposits. Desorption
from these materials is known to be significant. Removal of oil-soaked or
other organic-soaked straw and other natural absorbents is imperative for ef-
fective spill treatment. In a similar manner, most synthetic absorbents only
loosely absorb oil and other organic liquids. Wringing or squeezing the ab-
sorbed organics from the synthetic absorbents for reuse is claimed to be logis-
tically advantageous as well as cost effective.
A notable exception to the above types of absorbents are the swell able
imbiber beads as represented by the Dow Chemical alkylstyrene tertiary butyl-
copolymers. It is claimed to be impossible to squeeze imbibed organic liquids
from the Dow imbiber bead products (12). In this case, the pollutant would
either not be released back to the aquatic environment, or be released at only
a slow rate. Retrieval of the pollutant-saturated imbiber beads from the spill
environment does not appear to be as critical for this type of absorbent. Bio-
degradation of absorbed pollutants and residual toxicity of pollutant-laden
imbiber beads must be ascertained through bioassay testing, however, before a
recommendation can be made for their use as irretrievable agents.
Recommendations
It is recommended that the use of absorbents, both natural and synthetic,
be authorized for treatment of spills only in those situations in which the
absorbent can be removed from the environment. For water spills, utility is
29
-------
therefore limited to organic liquids that are insoluble and float. For land
spills, natural absorbents are useful for all liquids, and synthetics for all
organics that are absorbed.
Absorbents that are applicable for organic liquids may be obtained from
several manufacturers:
BASF Wyandotte Corporation
B.F. Goodrich Company
Mine Safety Appliances
Dow Chemical Company
Rohm and Haas
Phillips Petroleum Company
Union Carbide
Sorbent Sciences Corporation
3M Company
THICKENING AND GELLING AGENTS
Thickening and gelling agents are really a subclass of absorbent. Their
purpose in spill treatment is to immobilize the spilled material to prevent
further spread into the environment and to condition the spill for mechanical
removal. Like other absorbents, effective thickening and gelling agents are
appropriate for use on all land spills and in some cases they may be appropri-
ate for water spills of organic liquids that float.
Under previous contracts (EPA 68-01-0110 and 68-03-2093) Calspan evalu-
ated a wide variety of thickeners and gelling agents for spill treatment.
Most commercially available materials were found to require vigorous mixing of
the agents with the spilled material and/or temperature control of the mixture
to promote thickening. None was effective on all classes of liquid chemicals.
However, materials were found to be specifically effective for thickening four
general classes of potential spill materials.
Natural proteinaceous compounds (i.e., gelatine) can be used for gelling
hazardous aqueous solutions, but water-soluble polyelectrolyte polymers such
as Gelgard M (Dow Chemical) and Kelzan (Kelco) were found to be most effective
for thickening most water-soluble liquids.
Imbiber beads (the Dow Chemical product discussed previously) were found
to be most effective for gelling nonpolar organic liquids.
Three polymers, Hycar 1422 (a polyacrylonitrile-butadine copolymer pro-
duced by B.F. Goodrich), Soloid (a Kelco, Inc. derivative of xanthan gum), and
Klucel (a hydroxypropyl cellulose polymer by Hercules Corp.) were shown effec-
tive on polar and chlorinated organic liquids.
Alcohols were effectively gelled by Carbopol 934 (B.F. Goodrich), a poly-
acrylate polymer, and Klucel (mentioned above for polar organics).
The agents described above can be used independently to congeal ground
spills of the materials of the chemical classes with which they are associated
30
-------
above. As indicated earlier, imbiber beads can also be used on water spills
of insoluble materials that float on water. In an effort to produce a single
agent that would be effective for congealing all liquid spills, Calspan (under
EPA sponsorship) blended four of the agents described above to produce a
multipurpose gelling agent according to the following recipe:
Gelgard M 5%
Imbiber beads 30%
Carbopol 934 25%
Hycar 1422 30%
Cabosil 10%
Cabosil is a fluidizing agent produced by Cabot Corporation, and was in-
corporated to promote ease of application. With this recipe the multipurpose
gelling agent was found to be effective for congealing all liquids tested with
a dosage of approximately 1 pound of agent to 1 gallon of spilled liquid.
Table 5 lists the test liquids used in evaluating the multipurpose gelling
agent.
Toxicity of Gelling Agents
There is very little toxicity data available on synthetic polymers used
as thickeners or gelling agents. The manufacturers state without presenting
supporting data that their products are nontoxic. The toxicity of irretriev-
able agents that have gelled hazardous substance is not known. There is also
no data on the rate of desorption from the gelled mass.
TABLE 5. LIQUIDS TESTED WITH MULTIPURPOSE GELLING AGENT
Acetone Formaldehyde
Acetone cyanohydrin Gasoline
Acrylonitrile Isoprene
Ammonium hydroxide Isopropanol
Analine Kerosene
Benzaldehyde Methanol
Benzene Methyl ethyl ketone
Butanol Octane
Carbon disulfide 0-dichlorobenzene
Carbon tetrachloride Petroleum ether
Chlorine water (saturated) Phenol (89%)
Chloroform Pyridine
Cyclohexane Sulfuric acid
Ethanol Trichloroethylene
Ethyl acetate Water
Ethylene Dichloride Zylene
Ethylene Glycol
31
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Further research must be performed to determine the secondary toxic ef-
fects of irretrievable gelling agents with and without the absorbed hazardous
material.
Recommendations
It is recommended that thickening and gelling agents, either as specific
compounds or as blended agents, be considered appropriate for use in treatment
of land spills of all liquid materials on which they are effective. Individual
agents should be considered appropriate for treatment of water spills of in-
soluble organics that float. Thickening and gelling agents should not be used
on water spills of materials that sink or mix into the water column.
More research is required to determine the effectiveness and behavior of
blended gelling agents in water before recommendations can be made relative to
application to water spills.
BIOLOGICAL TREATMENT AGENTS
The use of biological agents has been restricted, for the most part, to
treatment of oil and oil derivatives or components, and is still not a common
practice in emergency spill treatment. In principle, microbial degradation may
be effective for a variety of hydrocarbons. Although there are many limita-
tions on the use of biological degradation, the advantage of this method of
dealing with spills is that it is a natural means of removal through biochemi-
cal breakdown. The spill may be attacked in situ, in areas inaccessible to
other methods of treatment, at a minimum of cost and effort if conditions are
appropriate. In addition, biological treatment may be utilized as a supple-
mental tool to other methods of spill treatment.
Biological agents for the mitigation of organic liquids is recommended
only if (1) the spill is contained (i.e., as in a pond or stream that may be
dammed), (2) sufficient time is available for biodegradation, and (3) the in-
troduction of the microbes will not be detrimental to the existing environ-
ment. The spilled material must be contained to allow sufficient time for bac-
terial population growth.
The actual growth of bacteria applied to a spilled material will be influ-
enced by many factors: the culture viability, length of lag phase, acclima-
tion, growth requirements, temperature, oxygen availability, type of substrate,
surface availability, and contact time.
As a general rule, the life cycle of a bacteria population includes four
reasonably distinct phases. Upon innoculation into a new medium, the cycle
begins with a lag phase, which is not a quiescent stage, but one of synthesis
of new kinds of enzymes and adjustment to the chemical and physical environment
(Figure 1). The length of the lag phase is dependent upon the physiological
condition of the bacteria, the innoculum dosage, acclimation and other effects.
Addition of essential nutrients, such as nitrogen and phosphorus, to the spil-
led material may speed or enhance growth and shorten the length of the lag
period. These nutrients may be added in the form of ammonium chloride
phosphoric acid (H^PO*), or sodium hexametaphosphate
32
-------
Log of the
number of
bacteria
Lag
Phase
Log
Phase
Stationary
Phase
Decline
Phase
Figure 1. Bacterial growth phases.
A period of rapid growth, known as the log or experimental phase, charac-
teristically follows the lag phase when conditions are satisfactory for growth.
The third phase, termed stationary, is characterized by a constancy due to
either complete cessation of cell division or to the balancing of reproduction
rate by the death rate.. Finally, a death phase ensues in which the death rate
exceeds the reproduction rate. It is often possible to prolong the log and
stationary phases by the re-addition of nutrients essential to growth, unless
a buildup of inhibitory products of degradation prevents new growth.
The length of the lag time is critical to the effectiveness of using
microbial degradation to combat spills. In some spi.ll situations, the rapid
dispersion of spilled material may make such a counter-measure completely im-
practical. The most practical step that might be taken to minimize this prob-
lem is containment of the spill. Use of cultures that are acclimated to the
chemicals being treated can be of significant advantage, but would not neces-
sarily solve the problem. For example, in one experiment bacteria in activated
sludge acclimated to aniline required 192 hours to oxidize 34% of the phenol
added. Bacteria acclimated to phenol required only 12 hours to oxidize 39% of
the same material (13). In another case, acclimated bacteria removed 95% of
phenol in 24 hours while unacclimated bacteria of the same culture removed only
24% in 23 hours (14). There are significant reductions in lag time, but it
would not be sufficient under many spill conditions unless the spilled material
is contained.
The effectiveness of biological treatment of toxic materials is dependent
upon several variables that cannot be fully controlled in spill situations.
Oxygen is essential for aerobic degradation. In most situations where the
spill is contained, natural aeration is probably inadequate for rapid detoxifi-
cation, and some method for forced aeration will be required. Agitators, com-
pressed air-bubble systems, or spray systems could be used where equipment is
available.
33
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Temperature affects the acclimation of bacteria, rate of bacteria growth,
and overall effectiveness of treatment. In most cases temperature cannot be
controlled. Where it could be controlled, elevated temperatures would usually
increase the rate of bacterial growth and thus treatment rate, but may result
in increased toxicity of spilled material, degradation products or additives
used as part of the treatment.
The nature of the spilled material is, of course, an uncontrollable vari-
able that severely limits the utility of biological treatment. Tables 6 and 7
summarize the findings in the literature relative to potential effectiveness
of treatment for different materials.
It is apparent from considerations of the life cycle of bacterial popula-
tions applied to a new medium and the lack of control of important variables on
which treatment effectiveness depends, that the use of biological agents for
mitigation of spills is not appropriate except where the spilled material can
be contained for substantial periods of time. The potential for sufficient
containment exists for land spills, for spills in small lakes and farm ponds,
and probably in small streams that can be temporarily dammed. Perhaps the
greatest potential exists at industrial installations that are already equip-
ped with aeration lagoons or settling ponds where cultures of acclimated bac-
teria may already be present or deliberately maintained.
Bacteria useful in oxidation of hazardous materials include natural cul-
tures in soil and surface waters, sewage sludge, acclimated sewage sludge and
special strains being developed commercially.
The problem of producing and storing a large quantity of bacteria species
specific for various kinds of hazardous materials is a serious constraint to
the use of biological countermeasures. It is desirable, therefore, to find a
species of bacteria that is effective for oxidation of a broad spectrum of
toxic materials and is relatively easy to produce in large volumes. The
pseudomonads have been found to be versatile in this respect. Pseudomonas
fluoresceus, for example, will grow on sugars, ami no acids, organic acids,
aromatic compounds, and other cyclic organic compounds.
A new hybrid bacteria was developed by researchers at General Electric
(14) that consumes crude oil at a rate several times greater than other oil
degradation bacteria. This bacteria, a Pseudomonas species, was developed
when scientists transmitted plasmids containing ONA from oil-consuming bacteria
to a single strain. The microorganism has the genetic information to produce
digestive enzymes for a variety of hydrocarbon molecules. The implication of
this to the future of microbial degradation is that, while at one time mixtures
of bacterial strains were applied to the spill, one strain could now be util-
ized. This eliminated competition for nutrients by the strains, increased ef-
ficiency for the treatment, and led to the possibility of developing other
single organisms with the ability to degrade a variety of hazardous substances.
For effective utilization of biological media as a spill treatment agent,
adequate supplies of microorganisms must be maintained at suitable locations
for innoculation of contaminated environment. Activated sludge from sewage
treatment plants provide the only readily available source of highly
34
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TABLE 6. BIOLOGICAL OXIDATION
(Quiescent Conditions)
Chemi cal
%
Oxidation
Seed Source
BOD
Duration
Benzene
Benzene
Ethyl benzene
n-Propanol
Acetaldehyde
Acrolein
Furfural
Benzoic acid
Formic acid
Cresols
Phenol
Acrylonitrile
Adiponitrile
Benzonitrile
Potassium cyanide
1.9
8.0
2.7
94
93
33
Formaldehyde (500 mg/1) 47
Formaldehyde (333 mg/1). 94
100
46
40
95-100
42-100
0-67
40
40
0
Sewage sludge 5 days
Acclimated activated 5 days
sludge
Sewage and acclimated 5 days
activated sludge
Activated sludge seed 5 days
Acclimated activated 5 days
sludge
Acclimated trickling 10 days
filter seed
Acclimated activated 5 days
sludge
Acclimated activated 5 days
sludge
Acclimated activated 2 days
sludge
Sewage seed 10 days
Activated sludge seed 5 days
Sewage seed 2-7 days
Sewage seed 2-10 days
Sewage seed 5-10 days
Sewage seed 5 days
Sewage seed 5 days
Activated sludge seed 7 days
Ref: Ryckman, et al., 1966.
concentrated cultures normally available throughout the country. Armstrong,
et al. (15) reported that most of the 20 top-ranked hazardous materials were
amenable to oxidation by bacteria from this source. Problems of acclimation
still exist, however. Some hydrocarbons (i.e., short chained alkanes) are
known to be toxic to microorganisms. Regardless of source or organisms used,
the potential success of the specific organism for the treatment of the speci-
fic spill in the required time must be established before application to the
contaminated region.
35
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TABLE 7. BIOLOGICAL OXIDATION
(Biological Treatment Plant Conditions)
Chemical
Benzene
Chlorobenzene
Ethyl benzene
Styrene
Toluene
Xylenes
Propanol
Acetaldehyde
Formaldehyde
Butanoic acid
Cresol
Phenol
Phenol
% Oxidation
3.5-13.0*
17.1
8.2-25.2*
18
34.8*
0-35.8*
55
49**
99
32.2
28.4-36.6*
'34*
35***
Seed. Technique
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Activated sludge
Respirometer
Test Duration
6-192 hours
192 hours
6-192 hours
10 hours
192 hours
192 hours
24 hours
23 hours
5 days
24 hours
192 hours
192 hours
12 hours
* Acclimated to aniline
** Acclimated to ethanol
*** Acclimated to phenol
Ref: Ryckman, et al., 1966.
There are a number of special cultures now marketed and approved for use
in treatment of oil discharges (16). The need for acclimation remains a prob-
lem for general utilization on hazardous spills.
Bacteria may be stored for long periods of time in the dormant state, in
a frozen or lyophilized powder form, which can be reconstituted when needed.
Storage in liquid form is also possible and may be desirable because they are
ready for immediate application. Storage in the lyophilized form is desirable
since bacteria may be left at room temperature, but reconstitution of the pow-
dered culture requires a few hours of preparation time.
Ecological Imbalance and Toxicity
Further limiting to the use of microbial degradation is the introduction
of undesirable bacteria to the ecosystem. Toxic effects of these organisms or
their competition with normal flora and fauna of the area may lead to an im-
balance in the ecology. Other toxicity considerations include the toxicity to
36
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aquatic life of the degradation products and of additives that increase the
rate of degradation. The resulting metabolic products of the treated spill
may be more toxic and have a greater solubility (17). For example, the con-
version of butyl benzene to 3-phenylpropionic acid by a Pseudomonas species
resulted in a solubility increase of more than 100 times (60 mg/1 to 6000
mg/1).
Ideally, microorganisms used for spill treatment should be uniformly dis-
tributed throughout a contaminated liquid medium or over a land surface.
Spray application seems most appropriate from a mitigation viewpoint, but harm-
ful effects to human lungs exposed to the spray can be serious. Toxicity of
microbes to human and other animal life must be ascertained before treatment.
Toxic effects of applied organisms and their competition with natural flora
and fauna of the area may lead to imbalance in the ecology.
In addition to the toxicity of the organisms, the toxicity of the degra-
dation products of the spilled material must be considered. The metabolic
products of a treated spill can be more toxic and have greater solubility than
the original contaminant.
Recommendations
Many materials are amenable to treatment by biological .degradation.
Table 3 lists substances found to be readily removed from the environment.
Many of these appear on the hazardous substance list, i.e., cresol , phenol,
and furfural.
Other materials found to be removed by biological degradation with ac-
climated microorganisms are summarized in Table 4. Those materials not com-
patible with biological treatment are listed in Table 8. These should not be
considered for mitigation by means of degradation.
It is recommended that biological agents be considered appropriate for
mitigation of spills of those materials listed in Tables 3 and 4, but only for
those cases in which the contaminated medium can be contained. Because of the
difficulty in controlling biological processes and variables that affect them,
it is recommended that other mitigation agents be used for spill treatment
whenever possible.
DISPERSING AGENTS
The use of chemicals to facilitate the action of biological degradation
may be considered for hazardous spill treatment, as they have been for oil
spills. Dispersants may be added to the spill to increase the surface area
available to the organisms for degradation.
Dispersants, which promote the formation of hydrocarbon-in-water suspen-
sions, contain surfactants, solvents, and stabilizers. The surfactants reduce
the surface tension of organic material and provide the chemical species neces-
sary to form a molecular layer.
37
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TABLE 8. REPORTED ORGANIC COMPOUNDS RESISTANT TO
REMOVAL FROM AQUATIC ENVIRONMENT
Compound Technique
Hydrocarbons
Benzene BOD AS
tert-Butyl benzene BOO AS
Ethylene chloro-hydrin BOD AS
n-Dodecane BOD AS*
Alcohols
tert-Amylalcohol BOD AS
2-Hydroxybutanol ' BOD AS
Pentaerythritol Resp. AS
2,2'-Oxydiethanol BOD AS
Polyethylene glycol 400 BOD AS
Tetraethylene glycol BOD AS
Aldehydes, Ketones, Acids, Salts, and Ethers
Croton aldehyde BOD AS
Methyl vinyl ketone BOO TF
Thioglycolic acid Resp. AS
Dioxane - BOD AS
di-Ethyl ether BOD AS
bis-2-Ethoxy ethyl ether BOD AS
Ethyleneglycol diethyl ether BOD AS
Polyethylene glycolacetate 400 BOD AS
Nitrogen Compounds
Acetylmorphine BOD AS
Cystine Resp. AS
Thioacetamide Resp. AS
Triethanolamine BOD AS
Sulfur Compounds
sec-Amy! benzene sulfonate BOD AS
tert-Amyl benzene sulfonate BOD AS
tert-Butyl benzene sulfonate BOD AS
tert-Dipropane benzene sulfonate BOD AS
tert-Pentapropane benzene sulfonate BOD AS
tert-Tripropane benzene sulfonate BOD AS
tert-Tetrapropane benzene sulfonate BOD AS
AS -
TF -
Ref:
Activated
Trickling
Ryckman ,
sludge
filter
et al.
seed
, 1966.
AS* -
Resp. -
BOD -
Acclimated activated sludge
Respirometer
Biological oxygen demand
seed
38
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The purpose of dispersing agents is primarily to promote biological de-
gradation either with natural biota present or in conjunction with biological
treatment agents. Chemical enhancement of the biodegradation of crude oil has
been reported by many (18-20). When the watercourse conditions (fast-moving,
large-volume river) exist such that containment and removal of hazardous spill
is not possible, dispersants may be used to aid in diluting the spilled mate-
rial to a concentration below its toxic level. The dispersing agent must also
be carefully selected in order that additional environmental damage will be
minimized.
Many investigations of spill situations have reported that the dispers-
ants used to fight the spill were more toxic than the spilled oil (21, 22).
Comparisons of the toxicities of dispersants used to clean the Torrey Canyon
oil spill with dispersants developed since the incident revealed that toxic
concentrations are many orders of magnitude greater for more recent formula-
tions (22). Research since 1968 has produced formulations containing water or
saturated hydrocarbons as solvents.
In addition, consideration must be given to the possibility of creating
an oxygen deficit in the water system that may cause indirect biological dam-
age. The addition of chemical dispersants to oil spills was found to produce
high values for biological oxygen demand (23). It was estimated that a spill
of 75,000 barrels of oil in the Delaware River which was treated with dispers-
ant chemicals would produce an oxygen deficit of 3.4 mg/1 Q£ by the third day.
No biological stress would be expected unless the percent saturation decreased
to 50% (4.6 mg/1).
It may be concluded that properly selected chemical dispersants are com-
patible with the environment.
Recommendations
The advantage of using dispersants to treat spills are (1) the rate of
biodegradation is increased, (2) damage to marine fowl is avoided since oil or
other hazardous material is removed from the water surface, (3) the fire haz-
ard from the spill is reduced by dispersion of the hazardous material several
feet into the water column, (4) spill is prevented from wetting solid surfaces
such as beach sand and shore property.
Dispersants are recommended as desirable additions to enhance the biologi-
cal degradation of spilled material. However, they must be chosen with care
and the amount carefully controlled, to avoid unnecessary harm to aquatic life.
Prior to the use of dispersant on a specific spilled substance, it should be
established through research that no increase in toxicity will result from the
dispersed substance or the degradation product of the added dispersant.
A compendium of information available on dispersing agents was prepared by
Battelle (18). As a single source of information, it was intended as an aid in
logistic planning and as a reference in an emergency for selection of agents
for oil spills. However, it is applicable to other hazardous spills. The com-
pendium summarizes the composition, shelf life, storage requirements, type of
oil substrates, and conditions for use of these agents.
39
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PRECIPITATION AGENTS
Many pollutants are ultimately converted in the environment to environ-
mentally acceptable chemicals. Both chemical and biological processes ulti-
mately oxidize most organics to carbon dioxide and water. Metal ions differ
from organics in that metal ion spills continue to be an indefinite threat
unless they are rendered insoluble by some precipitation or complex reaction.
Precipitation has been shown to be effective in reducing the concentration
of metal ions in solution by both hydroxide and sulfide precipitation. Both
processes should be considered acceptable for treatment of spills of heavy
metal compounds.
Many metallic hydroxides are insoluble in water only at elevated pH. As
a water body returns to normal after spill treatment, many hydroxide precipi-
tates will redissolve. Hydroxide precipitation therefore should be limited
for spill treatment to those situations in which the precipitate can be mech-
anically removed from the environment. Thus, utility is limited to land spills
or water spills 'in small ponds.
Sulfide precipitates are usually the least soluble salts of toxic metals.
It is therefore permissible to use hydroxide precipitation under some situa-
tions in which the precipitate cannot be removed from the watercourse. The
limitation is associated primarily with the toxicity of the sulfide ion and
the difficulty of controlling application rates to stoichiometric proportions
in large spills. It is recommended, therefore, that sulfide precipitation be
considered acceptable for use even with the crude controls described herein on
small spills of metallic compounds and that its use be limited on large spills
only to those situations in which adequate monitoring of the reaction is
available.
It is well known that the most insoluble salts of many metals are the
sulfides. This is true for most of the metals listed in Table 9. In most
cases, sulfides are extremely difficult to solubilize except in extremely
acidic media.
Treatment using sulfide ion (S) can be affected by using such materials
as hydrogen sulfide gas or aqueous sodium sulfide as the treatment agent:
M+* + S" -» MS4-
At concentrations of heavy metal ions that present a toxic hazard, forma-
tion of the insoluble metal sulfide proceeds rapidly, and acute toxicity can
be reduced within seconds. Sodium sulfide solutions used for treatment are
usually stabilized with sodium hydroxide to prevent evolution of toxic hydro-
gen sulfide fumes. Since the reaction proceeds most rapidly in high-pH media,
this stabilization usually promotes even more rapid and efficient reaction.
A wide range of heavy metal compounds can be treated by this sulfide pre-
cipitation method. Almost all soluble compounds of the metals listed in Table
9 are subject to sulfide treatment because the sulfide is their least soluble
compound whenever excess sulfide ions are available. Sulfide precipitation,
40
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TABLE 9. METAL IONS SUBJECT TO SULFIDE PRECIPITATION
Vanadiam Tantalum
Manganese - Osmium
Iron I rich" urn
Cobalt Platinum
Nickel Gold
Copper Mercury
Zinc Thallium
Gallium Lead
Zirconium Bismuth
Molybdenum Polonium
Ruthenium Cerium
Palladium Arsenic
Silver Praseodymium
Cadmium Neodymium
Indium Thorium
Antimony Uranium
however, is not effective for treatment of spills of all metal ions, particu-
larly those that are organically complexed or those that are anionic species.
Compounds of chromium, molybdenum, and manganese as the ionic species are
difficult to precipitate unless changed into other chemical forms. For ex-
ample, chromate chrome (CR+°), if first chemically reduced to chromium (Cr+3)
with a suitable reducing agent such as sodium thiosulfate, can then be precip-
itated as the Cr^S^ insoluble salt.
Due to the toxicity of the sulfide ion and of any generated hydrogen sul-
fide gas, the use of sulfide precipitation may require both pre- and post-
treatment of the spill and careful control of reagent additions. Pre-treatment
would require raising the pH to a point at which sulfide treatment is effec-
tive. Alternating use of a solution of sodium sulfide containing a strong base
such as caustic soda (NaOH) accomplishes the same purpose. Post-treatment may
be necessary to oxidize any unreacted sulfide to the sulfate. Aeration, which
occurs naturally in fast-flowing streams, is effective for this purpose.
In the case of small spills (typical of heavy metal discharges), treatment
can be monitored on the basis of a simple test : when a small amount of sodium
sulfide is injected at the spill site and a visible precipitate forms, addi-
tional concentrated sodium sulfide is added until no more precipitate is
41
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formed. This will generally produce a slight excess of sodium sulfide. For
large spills, more elaborate monitoring requirements are necessary to prevent
inadequate or excessive treatment.
To use sulfide as a mode of spill control, the toxicity of the spilled
heavy metal must be compared with the toxicity of the sodium sulfide treatment.
When one considers a wide range of metals and their potential toxicity on the
basis of volume of water affected, sodium sulfide treatment is approximately
l/20th as toxic as the original metal spilled. Detailed discussion of toxic-^
ity considerations associated with sulfide precipitation is presented by Pilie,
et al. (2).
The recommended treatment material is a solution of sodium sulfide in
water. The solution should be as concentrated as practically possible to con-
serve space and weight. An aqueous solution of sodium sulfide at 0°C contains
0.85 Ibs of sulfide per gallon of water containing 0.04 Ibs of sodium hydrox-
ide. The hydroxide is present to retard formation of hydrogen sulfide. Two
gallons of this solution are sufficient for the treatment of spills 2 to 10
gallons in size, depending on the heavy metal.
There are some metals that have a tendency to form oxides more readily
than the sulfides. These materials are generally easily hydrolyzable and can
be treated just with water to render them immobile. Titanium compounds are
typical of this group of chemicals. Some hydroxides form at pH below 7.
Others, such as nickel (II), iron (II) and manganese (II) require pH values
above 9 to be effectively formed. Solubility constants of the hydroxides, how-
ever, may be more readily available than large concentrations of sodium sul-
fide.
Although hydroxide precipitation is not to be considered to be a primary
mode of removal of toxic heavy metal ions from large or flowing water bodies,
it can be used to immobilize soluble heavy metals in liquid spills upon the
land or in a small water body (e.g., farm pond) where the precipitate can be
removed. Such treatment could remove the threat of the metal being transported
to a water system. Since it is desirable that the pH will revert to neutral
conditions under which the metal precipitate will redissolve, removal of the
hydroxide precipitate is necessary.
Precipitating agents are effective in decreasing the overall toxicity of
a heavy metal spill. However, the precipitated material on the bottom of a
lake or stream could exert a toxic effect on the bottom-dwelling organisms.
Insoluble mercuric salts can be converted to an organo-mercuric compound by
bacterial action. These compounds are more soluble than the inorganic form
and do not enter into the food chain. Some heavy metals (i.e., thallium) do
not enter into the food chain and are not bioamplified (24). Wilber (25)
states that there is not enough data available to determine if precipitated
metal salts will re-enter into the environment to be bioamplified. Of the 1300
references in an annotated bibliography on the biological effects of metals in
aquatic environment (26), there were no references to the possible chronic
effect of insoluble inorganic metal salts.
When the metal salt is not converted to a more toxic organic form and is
42
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sufficiently insoluble, the re-entry of the metal ion would be reduced below
a toxic level by dilution in a stream or river. However, in a closed system
such as a lake or a pond it is recommended that the precipitated metal salt
be removed from the watercourse until the chronic toxic effect of insoluble
metal salts is known by further research.
NEUTRALIZING AGENTS
In any spill of an acid or base, regardless of the specific chemicals in-
volved, the potential exists for creating toxic conditions as a result of a
pH change. A prime consideration therefore is to adjust the pH in the spill
to the environmentally acceptable condition of the natural waterway. Neutral-
izing agents are those materials that can be used to adjust the pH of a spill
plume to the desired environmental value, i.e., to a value between pH 6 and
pH 9. Bases may be used to neutralize acidic plumes in which pH less than 7
and acids may be used to neutralize basic plumes in which pH is greater than 7.
Consideration should be given to the treatment of any spill in which the
pH is changed markedly from the ambient state. Volume of the spill and the
dilution rate of the body of water in which the spill occurred must be consid-
ered. Based on fish toxicity studies, spills where the pH has been altered to
below pH 6 or above pH 9 must be considered for treatment. A list of common
spill acids and bases is included in Table 10.
When to Neutralize
The acids and bases that would be used as neutralizing agents would pro-
duce toxic pH conditions if applied to a region that is not affected by the
spill or if applied in excess quantities to the spill. In order to avoid
treating the wrong portion of a waterway (i.e., missing the spill) or over-
treating a spill, it is essential that some method be available to the On-Scene
Coordinator (OSC) for measuring pH of the water and monitoring pH changes as
treatment progresses.
TABLE 10. COMMONLY SPILLED ACIDS AND BASES
Acetic Acid Phosphoric Acid
Fatty Acids Sulfuric Acid
Chiorosulfuric Acid Sodium Hydroxide
Chromic Acid Potassium Hydroxide
Formic Acid Sodium Carbonate
Hydrochloric Acid Sodium Bicarbonate
Nitric Acid Calcium Oxide
Perchloric Acid Calcium Hydroxide
43
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Ground spills must, if possible, be immediately contained. Contained
spills on the land can then be removed by physical methods such as shoveling,
suction, etc. If physical removal is not possible, neutralization to mitigate
ground percolation to the nearest water system must be performed.
It is generally advantageous to neutralize all large spills of acids or
bases which occur in water. Neutralization^ spills in water should not be
attempted, however, unless adequate pH monitoring equipment is available. If
only a small quantity of acidic or basic material is spilled in a waterway
that provides for rapid dilution to nontoxic pH levels, it may be more appro-
priate to avoid neutralization, depending on the quality of the system avail-
able for monitoring the progress of treatment.
Selection of Neutralization Agents
In general, the chemical reaction involved in neutralization may be writ-
ten as follows:
Acid + Base * Salt + Water
While it is usually the case that the salt ions produced by the reaction are
less toxic than the treated spill, options may exist for the OSC to select a
neutralizing agent that results in reaction products at minimum toxicity when
applied to the spilled material. The reduction in toxicity of a spill plume
that can be achieved by'neutralization is illustrated in Table 11. In each
case shown, the salt produced by the neutralization reaction is substantially
less toxic than either the spilled material or the treatment agent. Since the
salts are themselves toxic, an important consideration, when a choice of neu-
tralization agent is available, is the selection of the agent that results in
the least toxic reaction product. Table 12 illustrates this point. Obviously
a substantial toxicity advantage will result if ammonium hydroxide is treated
with sulfuric acid rather than the other agents listed. However, it is better
to treat with less than ideal agents than not to treat at all. The list of
potential neutralization agents presented in Table 13 would generally result in
reaction products that are less toxic than the acute pH change produced by
spills of concentrate materials against which they may be used.
A final caution is necessary in considering toxicity of reaction products
of neutralization. In some cases, such as with a spill of arsenic acid, the
salt produced by neutralization will contain a toxic metallic ion. This can-
not be avoided in neutralization regardless of agent used. If the pH produced
by such a spill is at toxic levels it would be necessary to treat first with a
neutralizing agent to eliminate the pH problem and to post-treat with a pre-
cipitating agent to remove the metallic ion.
The decision to treat with a neutralization agent is made, therefore, to
eliminate toxicity due to pH. Where a choice of neutralization agents is avail-
able, it is most important to select the agent that results in the least toxic
reaction products. Assuming that several available agents are equally appro-
priate in this respect, further selection may be based on minimizing the poten-
tial for over-treatment and ease of application. These topics are discussed in
the following subsections.
44
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TABLE 13. ACIDS AND BASES SUITABLE FOR SPILL NEUTRALIZATION
Acids
1. Acidic acid
2. Sulfuric acid
3. Hydrochloric acid
Bases
1\ Calcium hydroxide
2. Sodium hydroxide
3. Sodium carbonate
4. Sodium bicarbonate
Strong vs Weak Neutralizing Agents--
To examine the potential for overtreatment of an acid or base spill, it
is useful to consider some illustrative titration curves. Such curves illus-
trate how pH would change as increasing amounts of the neutralizing agent is
added. Figure 2 compares typical titration curves that may be expected from
treatment of a spill of strong acid with a strong base and with a weak base.
It is apparent that during the early stages of treatment there is little or no
advantage in using a weak or strong base as treatment material. When approach-
ing the amount of neutralizing agent required for neutralization, the slope of
the titration curve increases very rapidly. A small addition of neutralizing
agent at this point causes a large change in pH. If a strong base is used for
neutralization, the high slope persists until highly toxic values of pH are
achieved. If a weak base is being used, the rate of change of pH with addi-
tional treatment material begins to decrease when neutrality is reached. The
danger of serious overtreatment is thereby reduced. Furthermore, the ultimate
pH achieved by massive overdosage of a weak treatment agent, while frequently
toxic, is substantially smaller than that achieved by a similar overdose of a
strong base. Similar comparisons can be made for treatment of the spill of a
strong base with strong or weak acids.
14-
12-
10-
8 -
6~
4~
2-
Treatment with
strong base
Treatment with
weak base
Volume of base
Figure 2. Treatment of strong acid with base,
46
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Figure 3 presents a comparison of illustrative titration curves that are
typical of treatment of a weak acid spill with a strong base and a weak base.
As with the treatment of a strong acid, the titration curves for treatment of
a weak acid with a strong or weak base are not substantially different during
the early stages of treatment.
Once neutrality is achieved, a small addition of a strong base causes a
sharp rise in pH to toxic values. The slope of the titration curve for treat-
ment with a weak base begins to decrease shortly after neutrality is achieved.
Therefore, the potential for serious overtreatment is substantially reduced.
Similar comparisons can be made for treatment of a weak base with strong and
weak acids.
Two conclusions can be drawn. First, it is easier to control the treat-
ment operation to avoid overtreatment if weak acids and bases are selected as
treatment materials than if strong acids or bases are selected. This does not
mean that strong acids or bases should not be used for neutralization when
available. It does mean that more careful monitoring is required if the strong
materials are used.
A secondary conclusion is that for those occasions when two or more mate-
rials are required (because of supply, for example) to neutralize a spill, it
is better to use the stronger acid or base during the early stages of treat-
ment and retain the weaker agent to use when neutrality is approached.
Table 13 presents lists of acids and bases that are acceptable neutraliz-
ing agents and that are arranged in order of increasing strength. Materials at
the top of the lists offer greater ease of operational control and minimum
potential for pH overshoot with overtreatment.
Physical Properties of Neutralizing Agents and Reaction Products--
Some of the acids and bases that may be used for spill neutralization are
available in both solid and liquid form. In general, much greater control of
14-
12-
10-
8-
6-
4-
2-
0-
Treatment with
strong base
Treatment with
weak base
Volume of base
Figure 3. Treatment of a weak acid with base.
47
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the spill can be obtained through use of liquid phases. In some cases, such
as with the use of lime, the solubility of the agent may be so low that opera-
tional problems would result from the amount of water that would have to be
handled. Under such conditions, a slurry might be used but only with caution.
Reaction rates will be retarded and the potential for overtreatment signifi-
cantly increased.
A wide variety of concentrations of neutralizing agents may be used in
spill treatment. In general, the lower the concentration the greater will be
the degree of control and uniformity of treatment. In some spills, it may be
desirable to use concentrated solutions. For example, if a dense acid such as
concentrated sulfuric acid is spilled, it will tend to remain near the bottom
of the waterway. Treatment with a concentrated solution of sodium hydroxide
would provide similar physical characteristics and increase the probability of
mixing of the spilled and neutralizing agent. .At substantial downstream dis-
tances, the acid may be well mixed in the stream and the use of dilute solu-
tions may be more desirable.
Substantial temperature changes will result from exothermic neutraliza-
tion when treating highly concentrated spill plumes with concentrated solu-
tions or slurries of neutralizing agents. Treatment should be applied in a
controlled manner to avoid sputtering and the danger of serious burns. Mini-
mization of temperature changes will also minimize mixing in the waterbody
which, in turn, would minimize plume spread. Use of dilute solutions for
treatment will in general minimize these problems but the quantity of treat-
ment material that must be handled becomes extremely large. To avoid, or at
least account for, ecological damage due to heating, temperature should be
monitored prior to, during, and following neutralization.
Depending on the nature of the spilled and neutralizing agent, some gas-
eous reaction products may be evolved. Carbon dioxide is usually released
when carbonates are involved in the reaction. Deleterious effects of gaseous
release may include increased mixing and plume spread, possible frothing, bub-
bling or sputtering that could cause equipment damage or personnel injury.
When to Stop Treating
Since shock produced by even small pH changes can cause significant eco-
logical damage, it would be ideal to adjust the pH of the spill plume to the
value of the unaffected water. Considering the degree of control available in
a large-scale field operation, however, and the high slope of the titration
curves in near-neutral conditions, the probability of achieving the exact pH
desired is small. Since it is desirable to minimize the amount of foreign
material in water (either the treatment material or the reaction products), it
is generally more desirable to undertreat than to overtreat. Exactly how
close the ideal pH should be approached depends on the monitoring network
available and the nature of treatment material being used. It is acceptable
to stop treatment when the pH of the treated waters is between 6 and 9.
48
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Recommendations
Neutralization should be considered an acceptable treatment for all spills
of acids or bases, provided some method for monitoring pH is available. When-
ever possible, neutralization should be accomplished on land spills before the
spilled material enters aquiferous or surface water. After the spilled mate-
rial has entered surface waters, the toxicity associated with the change in pH
from natural conditions is usually most critical. Neutralization of spills of
large quantities of material is usually appropriate regardless of the neutrali-
zation agent available. However, when a choice of agents is available, it is
extremely important to select the agent that produces the least toxic reaction
products in returning the pH to normal. In some cases, post-treatment for
toxic metallic ions may be necessary. All other considerations being equal,
some advantage can be obtained by selecting weak agents as opposed to strong
agents. Depending on the nature of the spilled material, some advantages can
be obtained by selection of neutralization agents with optimum physical char-
acteristics, but it is usually advisable to avoid use of solid agents when
possible.
Temperature changes associated with exothermic neutralization reactions
can produce secondary thermal pollution, but this problem appears to be of sec-
ondary importance. Caution should be observed to avoid personnel injury due
to sputtering or bubbling caused by exothermic reactions.
When the monitoring system is not sufficiently accurate to assure treat-
ment to the desired pH, it is usually better to undertreat than to risk over-
treatment. pH values between 6 and 9 are acceptable.
OXIDIZING AGENTS
Because of a variety of potential problems with the use of oxidizing
agents in spill control, it is recommended that their use be limited to land
spills and water spills that are completely contained.
In dilute solutions, oxidation reactions are generally slow. Except in
closed systems, they will seldom go to completion. The ultimate products of
oxidation of hydrocarbons are C02 and 1^0. With complex organic materials,
however, the reactions involve several intermediate steps and intermediate re-
action products which very probably remain in the environment in open systems
and are frequently toxic. To control the reaction and assure that it goes to
completion, it is necessary to overtreat to such an extent that severe toxic
conditions are produced by the treatment agent.
Oxidation reactions can never be limited to reactions of the agent with
the spilled material. Oxidation of natural organic material in the environ-
ment, including living organisms, will always accompany oxidation of the
spilled pollutant. Thus, valuable organic material is destroyed and the eco-
logical balance is invariably upset.
Because of the utilization of some fraction of the oxidizing agent in re-
actions with natural organic material, and the inability to drive the reaction
with the pollutant to completion, it is impossible to determine the quantity
49
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of agent required for spill treatment on the basis of stoichiometric relation-
ships. The potential for overtreatment or undertreatment is therefore high.
Since the oxidizing agents themselves are highly toxic to most living organ-
isms, residual agent aftertreatment in open systems can cause significant tox-
icity problems.
Oxidizing agents have not been used extensively for detoxification of haz-
ardous materials except in aeration lagoons and in other closed systems where
reactions can be completely controlled. There is little experience, there-
fore, in their use against spills. We believe that this practice should be
continued. Oxidants should be used on land and in surface waters only when no
other spill mitigation measure is available and only when the spilled material
can be contained for sufficient time to permit accurate control and monitoring
of the treatment.
50
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SECTION 5
HAZARDOUS SUBSTANCE - COUNTERMEASURE MATRIX
A counter-measure matrix has been generated to reference which classes of
mitigation agents are recommended for treating hazardous substances involved
in spills near or into a watercourse (Appendix A). The chemicals are listed
in alphabetical order in the first column. In the second column, the EPA tox-
icity classification is listed. The LCcg toxic concentration for each cate-
gory is given in Table 14. The third and fourth column list the density of
the hazardous substance and the physical form of the pure hazardous substance,
respectively.
The fifth column is the P/C/D category. The P/C/D category takes into
consideration the solubility, density, volatility and the ability to disperse
in water of each hazardous substance. The eight P/C/D categories are:
1. IVF (insoluble volatile floaters)
2. INF (insoluble nonvolatile floaters)
3. IS (insoluble sinkers)
4. SM (soluble mixers)
5. P (precipitator)
6. SS (soluble sinker)
TABLE 14. EPA TOXICITY CATEGORY
Category
A
B
C
D
Toxicity Range
1
10
100
ppm <
ppm <
ppm <
LC
LC
LC
LC
50
50
50
50
<_ 1 ppm
I10
<_ 100
<_ 500
ppm
ppm
ppm
51
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7. SF (soluble floater)
8. M (miscible)
A complete definition of each category and the hazardous substances with-
in each category is listed in Appendix B.
The remainder of the matrix specifies which categories of counter-measures
are effective for controlling hazardous substances discharged on ground or into
the watercourse.
The Coast Guard has issued a report that discusses various mitigation
agents and methods for hazardous spill control (27). This report classifies
the hazardous chemicals on the Coast Guard CHRIS list into categories and dis-
cusses methods of mitigation for each class of chemical.
52
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SECTION 6
MITIGATION AND SELECTION PARAMETERS
The 1972 Federal Water Pollution Control Act amendment of PL 92-500 states
that the EPA shall develop and revise the regulation, of hazardous substances
to include chemicals when discharge into the environment presents a danger to
the public welfare. It is recognized that every chemical substance has a
potential of being hazardous to the public welfare. However, a set of criteria
was derived to determine what chemicals should be designated as hazardous
substances.
Two criteria were proposed to determine if a chemical should be desig-
nated as a hazardous substance: the toxicity of the chemical, and the poten-
tial for it to be spilled.
The tentative toxicological criteria were stated in the Federal Register
on August 22, 1974. The advance notice states: "Any element or compound pro-
duced in excess of research quantities possesses sufficient danger potential
to be considered as a candidate hazardous substance if it is lethal to: (a)
one-half of a test population of aquatic animals in 96 hours or less at a c
centration of 500 milligrams per liter (mg/1) or less; or (b) one-half of a
test population of animals in 14 days or less when administered as a single
oral dose equal to or less than 50 milligrams per kilogram (mg/kg) of body
weight; or (c) one-half of a test population of animals in 14 days or less
when dermally exposed to an amount equal to or less than 200 mg/kg body wei
for 24 hours; or (d) one-half of a test population of animals in 14 days or
less when exposed to a vapor concentration equal to or less than 200 cubic
centimeters per cubic meter (volume/volume) in air for one hour; or (e) aquatic
flora as measured by a 50% decrease in cell count, biomass, or photosynthetic
ability in 14 days or less at concentrations equal to or less than 100 mg/1."
The second criterion is the probability that a material will be spilled
based on the annual amount produced, methods of transporting, handling and
storage of the material, past history of spills, and physical-chemical proper-
ties. Some chemicals that were classified hazardous substances because of the
toxicity criteria were finally excluded from the hazardous substance classifi-
cation for the following reasons:
1. No past history of a spill,
2. Low annual production,
3. Limited commercial use or distribution, and
53
con-
ght
-------
4. High dollar value to the product.
The EPA has proposed to define a hazardous substance as any material that
met the above criteria if the material is discharged into navigable water, ad-
joining shoreline, into the waters of the contiguous zone from vessels, and
onshore or offshore facilities. The proposed list of hazardous substances was
published in the Federal Register (Vol. 40, No. 250) on December 30, 1975 (see
Appendix A).
The hazardous substance list is subdivided with respect to aquatic toxi-
city (LCso values for 96-hour exposure) into four categories -- A, B, C, and
D, respectively -- as having LC5Q values of less than 1 ppm, 1 to 10 ppm, 10
to 100 ppm, and 100 to 500 ppm. Pesticides are the most toxic group of chemi-
cals, with over 75% being in Category A, having a toxicity less than 1 ppm.
Polar and chlorinated organic compounds have LCso values ranging from less than
1 ppm (e.g., PCB, Acrolin) to greater than 100 ppm (e.g., amines, organic hal-
ides). Nonpolar organic chemicals generally have LCso values greater than 10
ppm. Also, inorganic salts are within this same range except for salts of Cd,
Mg, As, Cu, and CN.
The 1972 Water Pollution Control Act Amendment gives the EPA the respon-
sibility of removing from the environment the spilled hazardous substance.
This responsibility raises many questions on how to effectively remove dis-
charged hazardous substances. The general mitigation procedure consists of
three parts: first, to contain the spilled material; second, to counteract
the hazardous material either by physical removal or by chemical action, which
produces a less toxic substance; and third, cleaning up the spill site after
treatment by removing any hazardous byproducts and restoring the area to an
environmentally sound state.
There are various parameters involved in each of these steps which enter
into the decision-making process on how to counteract a hazardous substance
spill, and which countermeasure, if any, should be used.
PHYSICAL-CHEMICAL PARAMETER
The physical-chemical properties of the chemical discharged is a factor
in deciding what countermeasure action should be taken. The location of the
discharge in the environment and the physical state of the discharge will de-
termine the complexity of the mitigation process. When a solid chemical is
spilled on land, the spill is the easiest to mitigate. The spilled material
is essentially contained at the spill site,with removal being accomplished by
placing the chemical spill into containers for proper disposal or recycling.
When the spilled chemical is in a liquid state, the mitigation process is
more complicated. The discharge first must be contained to minimize the envi-
ronmental contamination. The liquid discharge must not be allowed to spread
into the environment either by surface runoff or ground percolation. Once the
spill is contained, it may be treated by the appropriate countermeasure. In
some cases, such as the use of precipitating agents, the countermeasure will
help to contain the hazardous material. If the spill gets into a watercourse,
either directly or indirectly from a land discharge site, containment and
treatment is more complicated.
54
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The physical-chemical properties of the chemical discharges must be con-
sidered in estimating the environmental harm of the discharge. The EPA has
proposed to rank spills in waterways into eight P/C/D categories that depict
the potential harm the discharge may have on the environment. The eight P/C/D
categories are based on solubility, density, volatility, and the ability to
disperse in water. The definition of category and chemicals included in each
are presented in Appendix A. The eight material classifications are ranked in
increasing order of relative damage potential. This P/C/D factor has a value
from 0 to 1 which correlates the potential harm of the eight material classes
to the environment.
When the P/C/D factor is combined with the four toxic categories, the
potential environmental damage of a given unit of a hazardous substance can be
compared. For example, one pound of a chemical that is miscible (P/C/D cate-
gory M) and in a toxic category A is potentially 5000 times as damaging to the
environment as one pound of a chemical that is an insoluble, volatile floater
(P/C/D category IVF).and in a toxic category D. Physical, chemical, and dis-
persal properties and the toxicity of hazardous substances will determine to
what extent the material must be removed from the environment (Table 15).
WATERCOURSE PARAMETER
Watercourses can be divided into four general classifications based upon
the difficulty of containment and treatment.
1. Small lake or pond
2. Large lake
3. Small stream
4. River
In a pond or small lake, the discharged hazardous material is essentially con-
tained within the boundaries of the body of water. This minimizes the
TABLE 15. RELATIVE POTENTIAL ENVIRONMENTAL DAMAGE OF HAZARDOUS SUBSTANCES
Toxic
Category
A
B
C
D
P/C/D Category
IVG
500
50
5
1
INF
1150
115
11.5
2.3
IS
1800
180
18
3.6
SM
2450
245
24.5
4.9
P
3100
310
31
6
SS
3750
375
37.5
7.5
SF
4400
440
44
9
M
5000
500
50
10
55
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potential for environmental damage. Mitigation and removal of the spilled
material can then proceed.
When the hazardous material is discharged into a large lake, the environ-
mental damage is ultimately contained to the boundaries of the lake. Treating
the enormous volume of water within the lake is not possible. Therefore, the
spill must be contained in as small a volume as possible. If the spill is at
the shoreline, then the contaminated area will consist of the shoreline and
the water in the lake. If a lake spill is away from the shoreline, the con-
taminated volume of water will expand in an elliptical manner, moving in the
direction of the flow of water.
When the hazardous material is discharged into a river or stream, the vol-
ume of water contaminated will depend on the geometry of the waterway, the
rate and volume of water flow. The geometry of the waterway (straight or wind-
ing stream, bottom characteristics, etc.) will have an effect on the mixing of
the spilled material with the water. This will influence what, if any, con-
tainment procedure can be effectively used. For example, a mitigation proce-
dure for floating substances may not be as effective on a turbulent stream com-
pared with a nonturbulent stream.
Containment of a low-volume waterway may be accomplished by damming or
diverting the stream, but this is not feasible for a large river. If the
stream and river characteristics forbid containment, then mitigation procedures
must be initiated as soon as possible. The decision may be made that no coun-
termeasure treatment should be initiated. This decision would be based on the
ability of a waterway (large, turbulent river) to dilute the hazardous sub-
stance below its toxic level.
MONITORING
In order to determine the extent that the hazardous substance has affected
the environment, there must be adequate monitoring of the spilled material.
The use of a computer model (i.e, CHRIS) via telephone communications would
give a first-order approximation on the extent that the waterway was affected
by the spill.
The input to the model would be the physical-chemical, dispersant and
toxic characteristics of the spilled material, the watercourse parameter (flow,
direction of flow, width, depth, type of watercourse, etc.) and the elapsed
time since the discharge occurred. The computer output would consist of con-
centration contours that would indicate where the spilled material was, with
respect to the discharge site.
The computer model will indicate where chemical monitoring of the spill
must take place. Only through an adequate monitoring program can the extent
that the watercourse is contaminated, and the hazardous material concentration
profile downstream of the spill site, be determined. This information would
(1) determine where to initiate containment and mitigation procedures, (2) be
a guide in determining the potential environmental harm (i.e., to warn down-
stream water users), and (3) to update the computer model to determine the ef-
fectiveness of treatment and containment procedures.
56
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The monitoring program must be continued throughout the entire mitigation
procedure. The decision to increase or decrease the amount of mitigating agent
being used can only be based on the results from a monitoring program. If the
location and the concentration of the hazardous material is not known, then
the decision on where to treat the spill or how much mitigating agent should
be used cannot be made. Thus the effectiveness of a countermeasure can only
be determined with proper analytical monitoring.
Spilled hazardous material classified into five groups (inorganic salts,
inorganic acids and bases, polar and chlorinated organics, nonpolar organics,
and pesticides) have different monitoring requirements. Some of these hazard-
ous materials, such as inorganic acids and bases, can be monitored easily with
pH. Heavy metal inorganic salts can be monitored directly with precipitating
agents. The nonprecipitating inorganic salts must be monitored by an analyti-
cal chemical procedure. This analytical procedure should be a wet analytical
or colorimetric procedure.
The monitoring of organic hazardous .materials, including pesticides, must
use analytical instrumentation. An indirect procedure such as Total Organic
Carbon could be used, but is nonspecific. Gas chromatography is preferred as
a field monitoring procedure.
TOXICITY PARAMETERS
When a hazardous substance discharge is treated with a countermeasure, one
of three situations will occur: (1) you will overtreat the spill, (2) treat
the spill enough to render it nontoxic to the environment, or (3) undertreat
the spill. The toxic effect of each treatment situation must be considered in
the decision to use a specific countermeasure. When the spill is overtreated,
the toxicity of the byproducts of the countermeasure, as well as the counter-
measure agent, must be considered. When the spill is treated .properly, then
only the toxicity of the byproducts of the mitigation need be considered.
When the spill is undertreated, then the byproducts of the countermeasure and
the residual untreated toxic material must be taken into consideration.
When a particular countermeasure is considered to mitigate a spilled haz-
ardous material, the potential that the byproducts of the mitigating agent has
upon the environment is an important factor in the decision-making process.
In most cases the countermeasure does not physically remove the hazardous mate-
rial from the environment, but chemically transforms it into a less toxic state.
The persistence and degradation of a byproduct may cause long-term harm
to the environment. The degradation may be caused by biological decay, de-
sorption, or solubilization. Biological decay may transform the toxic material
into a harmless substance that will not cause further damage to the environ-
ment. However, if the toxic byproduct enters into the food chain of aquatic
plants and animals, and is bio-amplified, then a serious long-term environ-
mental effect may result. But a byproduct of a countermeasure (e.g., heavy
metal which is adsorbed to a mass transfer agent or is an insoluble salt) may
be slowly released back into the water and be diluted to such a degree that no
long-term toxic effect will be seen. In some cases, the mitigating agent it-
self is a toxic substance and restraints must imposed on its use. For example.
57
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if sodium hydroxide is being used to counteract a sulfuric acid spill and the
counter-measure is added to the stream in the wrong place, then two hazardous
substance spills exist instead of one.
Therefore, the primary and secondary effects of a countermeasure upon the
environment must be carefully considered in the decision as to whether to use a
specific mitigating agent or not.
58
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REFERENCES
1. Thompson, T. A System of Chemistry. Baldwin, Cradock and Joy, London,
1817. p. 230.
2. Pilie, R., R. Baier, R. Ziegler, R. Leonard, J. Michalovic, S. Pek, and
0. Bock. Methods to Treat, Control and Monitor Spilled Hazardous Mate-
rials. Environmental Protection Agency, Cincinnati, Ohio. Publication
Number 660/2-75-042. June 1975.
3. Guisti, 0. Activated Carbon Adsorption of Petrochemicals. J. Water Poll,
Control Fed. 46:947-965. May 1974.
4. Whitehouse, J. A Study of the Removal of Pesticides From Water. Ken-
tucky Water Resources Institute for United States Public Health Service.
1967.
5. Behavior of Organic Chemicals in the Aquatic Environment: A Literature
Critique. Washington University, St. Louis, for Manufacturing Chemists
Assoc. 1966.
6. United States Department of Labor, Safety and Health Regulations for Ship
Repairing, Shipbuilding and Shipbreaking. 29CFR 1915, 1916, 1917.
7. Telecon between R. Leonard, Calspan Corp., and Or. David Puchek, 3M Com-
pany. 13 February 1976.
8. Telecon between R. Leonard, Calspan Corp., and Richard H. Hall, Dow Chem-
ical Company. 13 February 1976.
9. Communication from Dr. David J. Buchek, 3M Company, to Richard Leonard,
Calspan Corp. 16 January 1976.
10. Hall, R. and D. Haigh. Imbiber Polymer Beads That Soak Up Oil Spills.
Dow Chemical Company. Updated report. 1976.
11. Haigh, D., and R. Hall. Expansive Imbibition for Practical Pollution
Particulation,or Separating Things From Stuff. Presented at SAE Mid-
Michigan and American Chemical Society Midland Section, Midland, Michigan.
October 1970.
12. Telecon between R. Leonard, Calspan Corp., and M.F. Gray, Vice President,
Spill Control Company. 16 February 1976.
59
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13. Ryckmon, D., A.U.S. Prabhabora Rov, and J.C. Buzzell, Jr. Behavior of
Organic Chemicals in the Aquatic Environment: A Literature Critique.
Manufacturing Chemists Association. 1966.
"14. Pearce, A.S., and S.E. Punt. Biological Treatment of Liquid Toxic Wastes.
Effluent and Water Treatment Journal. 1975.
15. Armstrong, N., 0. Wyso, E. Glozna, and V. Behn. Biological Counter-measures
for the Mitigation of Hazardous Material Spills. In: Control of Hazardous
Material Spills, Proceedings of the 1974 National Conference, San Francis-
co, California. 1974.
16. Battelle Pacific Northwest Laboratories. Oil Spill Treating Agents: A
Compendium for the American Petroleum Institute. Publication Number 4150.
1972.
17. Cobert, A., H. Guard, and H. Chatigry. Considerations in Application of
Microorganisms to the Environment for Degradation of Petroleum Products.
In: The Microbial Degradation of Oil Pollutants. Center for Wetland
Resources. LSU-SG-73-01. 1973.
18. Robichaux, T., and H. Myrick. Chemical Enforcement of the Biodegradation
of Crude Oil Pollutants. J. of Petroleum Technology. 1972.
19. Blacklaw, J., J. Strand, and P. Walkup. Assessment of Oil Spills Treat-
ing Agent Test Methods. In: Prevention and Control of Oil Spills.
American Petroleum Institute, Washington, DC. 1971. p. 253.
20. Canevari, G.P. Soil Spill Dispersants - Current Status and Future Outlook.
In: Prevention and Control of Oil Spills. American Petroleum Institute,
Washington, DC. 1971. p. 263.
21. Smith, J. Torrey Canyon Pollution and Marine Life. Cambridge University
Press. 1968.
22. Cerame-Vivoo, M. The Ocean Eagle Spill. Dept. of Marine Science, Uni-
versity of Puerto Rico. 1968.
23. Dewling, R., J. Dorrler, and G. Pence, Jr. Dispersant Use vs Water Qual-
ity. In: Prevention and Control of Oil Spills. American Petroleum
Institute, Washington, DC. 1971. p. 271.
24. Unpublished Calspan report.
25. Wilber, C. The Biological Aspects of Water Pollution. Charles C. Thomas,
Springfield, Illinois. 1969. Chapter 5.
26. Eisler, R., et al. Annotated Bibliography on Biological Effects of
Metals in Aquatic Environment. EPA Report Number 600/3-75-008. October
1975. p. 406.
60
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27. Bauer, W., D. Barton, J. Bulloff. Agents, Methods and Devices for Amelio-
ration of Discharges of Hazardous Chemicals in Water. Department of
Transportation, U.S. Coast Guard. Report Number CG-D-38-76. August
1975. p. 181.
61
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APPENDIX B
HAZARDOUS CHEMICALS CLASSIFIED ACCORDING TO P/C/D CATEGORY
Category IVF: Insoluble volatile floater - material lighter than water
with a vapor pressure greater than 20 mmHg and a solubility of less than 1000
ppm, or materials with vapor pressure greater than 100 ppm and solubility less
than 10,000 ppm.
Ally! chloride
Benzene
Cyclohexane
Isoorene
Methyl mercaptan
Methyl methacrylate
Styrene
Toluene
Category INF: Insoluble nonvolatile floater - material lighter than
water with vapor pressure less than 10 mmHg and solubility less than 1000 ppm.
Amy! acetate
Category IS:
ity less than 1000
Xylene
Insoluble sinker
ppm.
Aldrin
Arsenic disulfide
Benzyl chloride
Calcium arsenate
Chlorobenzene
Chloroform
Chromous chloride
Cupric acetoarsenite
Cupric oxalate
Cupric tartrate
Cuprous bromide
2,4-0 acid
2,4-D esters
Diazinon
EDTA
Guthion
Heptachlor
Kelthane
Lead arsenate
Lead fluroide
Lead iodide
Lead sulfate
Ethyl benzene
- material heavier than water and solubil-
Lead thiosulfate
Lead tungstate
Methoxychlor
Methyl parathion
Naled
Naphthalene
Nickel hydroxide
Parathion
Pentachlorophenal
Phosphorus
Polychlorinated biphenyls
Strontium chromate
Strychnine
2,4,5-T acid
2,4,5-T esters
TDE
Tetraethyl lead
Toxaphene
Trichlorophenol
Uranium peroxide
Zinc carbonate
Zinc cyanide
72
-------
Lead sulfide
Lead thiocyanate
Zinc phosphide
Zinc potassium chromate
Category SM:
greater than 1000
Soluble mixers - solid substances that have a solubility
grams per liter of water.
Ammonium acetate
Ammonium sulfamate
Ammonium thiocyanate
Ammonium thiosulfate
Calcium hypochloride
Calcium oxide
Chromic acid
Lithium bichromate
Lithium chromate
Potassium hydroxide
Sodium bichromate
Sodium hypochlorite
Sodium phosphate, dibasic
Category P: Precipitator -.salts that dissociate or hydrolyze in water
with subsequent precipitation of a toxic ion.
Aluminum fluoride
Aluminum sulfate
Antimony pentachloride
Antimony pentafluoride
Antimony potassium
tartrate
Antimony tribromide
Antimony trichloride
Antimony trifluoride
Antimony trioxide
Arsenic acid
Arsenic pentoxide
Arsenic trichloride
Arsenic trioxide
Beryllium chloride
Beryl!ium fluoride
Beryl!ium nitrate
Cadmium bromide
Cadmium fluoride
Calcium carbide
Cobaltous bromide
Cobaltous fluoride
Cobaltous formate
Cobaltous sulfamate
Cupric acetate
Cupric chloride
Cupric formate
Cupric glycinate
Cupric lactate
Cupric nitrate
Cupric subacetate
Cupric sulfate
Cupric sulfate
ammoniated
Ferric ammonium citrate
Ferric ammonium oxalate
Ferric chloride
Ferric fluoride
Ferric nitrate
Ferric sulfate
Ferrous ammonium
sulfate
Ferrous chloride
Ferrous sulfate
Lead acetate
Lead chloride
Lead fluoborate
Lead nitrate
Lead stearate
Lead tetracetate
Mercuric acetate
Mercuric cyanide
Mercuric nitrate
Mercuric sulfate
Mercurous nitrate
Nickel ammonium sulfate
Nickel chloride
Nickel
Nickel
formate
nitrate
Nickel sulfate
Potassium arsenate
Potassium arsenite
Uranyl acetate
Uranyl nitrate
Urany! sulfate
Vanadium pentoxide
Vanadium sulfate
Zinc acetate
Zinc ammonium chloride
Zinc bichromate
Zinc borate
Zinc bromide
Zinc chloride
Zinc fluoride
Zinc formate
Zinc hydrosulfide
Zinc nitrate
Zinc phenolsulfonate
Zinc silicofluoride
Zinc sulfate
Zinc su!fate, mono-
hydrate
Zirconium acetate
Zirconium nitrate
Zirconium oxychloride
Zirconium potassium
fluoride
Zirconium sulfate
Zirconium tetrachloride
73
-------
Category SF: Soluble floaters
ubility greater than 1000 ppm.
Acetic anhydride
Acetone cyanohydrin
Acrolein
Acrylonitrile
Adiponitrile
Ammonia
Butyl acetate
Chlorine
- material lighter than water and of a sol-
Diethyl amine
Dimethyl amine
Ethylenediamine
Ma-leic anhydride
Monoethylamine
Trimethylamine
Vinyl acetate
Category M:
proportion.
Miscible - liquids that are free to mix with water in any
Acetaldehyde
Acetic acid
Ally! alcohol
Ammonium hydroxide
Butyl amine
Butyric acid
Formaldehyde
Formic acid
Hydrofluoric acid
Hydrogen cyanide
Mevinphos
Monoethylamine
Nitric acid
Nitrogen dioxide
Phosphoric acid
Proprionic acid
Proprionic anhydride
Propyl alcohol
Sulfuric acid
Tetraethyl pyrophosphate
Category SS: Soluble sinkers - materials heavier than water and of solu-
bility greater than 1000 ppm.
Acetyl
Acetyl
bromide
chloride
Ammonium
Ammonium
Ammonium
Ammonium
Ammon iurn
Ammonium
Ammonium
benzoate
bicarbonate
bichromate
bifluoride
bisulfite
bromide
carbamate
Ammon i urn
Ammonium
Ammonium
Ammonium
Ammonium
Ammon i urn
Ammonium
Ammon i urn
Ammonium
Ammonium
Ammon i urn
Ammonium
Aniline
Barium cyanide
Benzoic acid
Benzonitrile
chloride
chromate
citrate
fluoborate
hypophosphate
oxalate
pentaborate
persulfate
silicofluoride
sulfide
sulfite
tartrate
Dodecylbenzenesulfonic acid
Duraban
Endosulfan
Ethion
Fumaric acid
Furfural
Hydrochloric acid
Hydroxylamine
Isopropanolamine dodecylbenzene-
sulfonate
Lindane
Malath ion
Maleic acid
Naphtheric acid
Nitrogenzene
Nitrophenol
Paraformaldehyde
Phenol
Phosgene
Phosphorous oxychloride
Phosphorous pentrasulfide
Phosphorous trichloride
Potassium bichromate
Potassium chromate
Potassium cyanide
Potassium permanganate
74
-------
Benzoyl chloride
Cadmium acetate
Cadmium arsenite
Calcium chromate
Calcium cyanide
Calcium codocylbenzenesulfonate
Calcium hydroxide
Captan
Carbonyl
Carbon disulfide
Chlorosulfonic acid
Chromic acid
Chromic sulfate
Chromyl chloride
Coumaphas
Cresol
Cyanogen chloride
Dalapon
Dicamba
Dichlobenil
Dichlone
Oichlonous
Dieldrin
Dinitrobenzene
Dinitrophenol
Diquat
Disulfoton
Diuron
Pyrethins
Quinoline
Resorcinol
Selenium oxide
Sodium
Sodium arsenate
Sodium arsenite
Sodium bifluoride
Sodium bisulfite
Sodium chromate
Sodium cyanide
Sodium dodecylbenzenesulfonate
Sodium fluoride
Sodium hydrosulfide
Sodium hydroxide
Sodium methyl ate
Sodium nitrite
Sodium phosphate, monobasic
Sodium phosphate, tribasic
Sodium selenite
Sodium sulfide
Stannous fluoride
Sulfur monochloride
Trichlorfon
Triethanolamine dodecyl-
benzenesulfonate
Xylenol
Zectran
75
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-81-205
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Guidelines for the Use of Chemicals in
Removing Hazardous Substance Discharges
5. REPORT DATE
September 1981
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
C.K. Akers, J.G. Michalovic, R.J. Pilie
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Calspan Corporation
Buffalo, New York 14221
AZB1B
11. CONTRACT/GRANT NO.
EPA 68-03-2093
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory - Cin.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
OH
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Contact: John E. Brugger (201) 321-6634
16. ABSTRACT
This report was undertaken to develop guidelines on the use of various chemical and
biological agents to mitigate discharge of hazardous substances. Eight categories
of mitigative agents and their potential uses in removing hazardous substances dis-
charged on land and in waterways are* discussed. . The agents are classified as follows:
(1) Mass Transfer Media; (2) Absorbents; (3) Thickening and Gelling Agents; (4) Bio-
logical Treatment Agents; (5) Dispersing Agents; (6) Precipitating Agents; (7) Neu-
tralizing Agents; and (8) Oxidizing Agents.
The classification of each agent is developed in terms of: (a) Characteristic proper-
ties of the mitigative-agent; (b) Potential spill situations on which the agent could
be used; (c) The effects on the environment caused by use of the agent; (d) Possible
toxic side effects caused by byproduct formation; and (e) Recommendations for use of
the agent.
A counter-measure matrix that references various classes of mitigative agents recom-
mended for treatment of hazardous substances involved in spills near or into a water-
course has been developed and includes a lis.ting of hazardous chemicals, the corre-
sponding EPA toxicity classification, and the physical properties of the chemical.
This report was submitted in fulfillment of Contract No. 68-03-2093 by Calspan Cor-
poration under the sponsorship of the U.S. Environmental Protection Agency.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS.
b. IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Water Pollution, Water Treatment, Hazard-
ous Materials, Activated Charcoal, Ion
Exchange, Dispersants, Neutralizing,
Thickening, Gelling Agents, Oxidizers,
Sedimentation Precipitation (Chemistry),
Microorganism Control, Absorbers
Mitigation of Hazardous
Substance Discharge,
Countermeasure Matrix
13/02
07/01
11/07
07/04
8. DISTRIBUTION STATEMENT
Release to public
19. SECURITY CLASS /This Report)
Unclassified
21. NO. OF PAGES
82
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (FUv. 4-77)
76
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