Chapter 14

Spill-Treating Agents
Merv Fingas

Chapter Outline
14.1. Introduction 429 14.5. Recovery Enhancers 431
14.2. Dispersants 429 14.6. Solidifiers 431
14.3. Surface-Washing 430 14.7. Sinking Agents 431
Agents 14.8. Biodegradation Agents 432
14.4. Emulsion Breakers 430
and Inhibitors

14.1. INTRODUCTION
Treating the oil with specially prepared chemicals is another option for dealing
with oil spills. An assortment of chemical spill-treating agents are available to
assist in cleaning up or removing oil. It should be noted, however, that approval
must be obtained from the appropriate authorities before these chemical agents
can be used. In addition, these agents are not always effective, and the treated
oil or the treating chemical may be toxic to aquatic and other wildlife.

14.2. DISPERSANTS
Dispersant is a common term used to label chemical spill-treating agents that
promote the formation of small droplets of oil that “disperse” throughout the
top layer of the water column. Dispersants contain surfactants, chemicals like
those in soaps and detergents, that have molecules with both a water-soluble
and oil-soluble component. Depending on the nature of these components,
surfactants cause oil to behave in different ways in water. Surfactants or
surfactant mixtures used in dispersants have approximately the same solubility
in oil and water, which stabilizes oil droplets in water so that the oil will
temporarily disperse into the water column. Two major issues associated with
the use of dispersantsdtheir effectiveness and the toxicity of the resulting oil
dispersion in the water columndhave generated controversy in the last 40
years. There is an extensive section on dispersants following this introduction.

Oil Spill Science and Technology. DOI: 10.1016/B978-1-85617-943-0.10014-0

Copyright Ó 2011 Elsevier Inc. All rights reserved. 429
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14.3. SURFACE-WASHING AGENTS

Surface-washing agents, or beach cleaners, are different from dispersants.
Surface-washing agents are effective in some situations, but they have not been
widely accepted partially because of this confusion with dispersants. While
toxicity has been a problem with some dispersants in the past, testing has shown
that the better surface-washing agents have very little aquatic toxicity and their
use could prevent damage to shoreline species.
While both products contain surfactants, those in dispersants are equally
soluble in both water and oil, whereas in surface-washing agents, the surfac-
tants are more soluble in water than in oil. Surface-washing agents operate by
a different mechanism than dispersants. This mechanism is known as deter-
gency and is similar to the use of detergents for washing clothes. In fact,
dispersants and surface-washing agents may be quite different. Testing has
shown that a product that is a good surface-washing agent is often a poor
dispersant and vice versa.
Dispersants and surface-washing agents are used for quite different
purposes. Rather than causing the oil to disperse, surface-washing agents are
intended to be applied to shorelines or structures to release the oil from the
surface. During low tide, the oil is sprayed with the surface-washing agent,
which is then left to soak for as long as possible. It is washed off with a low-
pressure water stream in an area that has been isolated using booms and
skimmers. Laboratory- and field-scale tests have shown that these agents
substantially reduce the adhesion of the oil so that as much as 90 to 95% of the
oil can be released from rocks or other surfaces.
There is an extensive section on oil spill surface washing agents in this
chapter.

14.4. EMULSION BREAKERS AND INHIBITORS

Emulsion breakers and inhibitors are agents used to prevent the formation of
water-in-oil emulsions or to cause such emulsions to revert to oil and water.
Several formulations can perform both functions. Water-in-oil emulsions can
seriously complicate a cleanup operation by increasing the amount of material
to be recovered, disposed of, and stored by up to three times. Water-in-oil
emulsions are so viscous that skimmers and pumps often cannot handle them.
There are different types of emulsion breakers and inhibitors, some of
which are best used when little water is present, referred to as a closed system,
and others that are best used on the open water, referred to as an open system.
For example, some contain surfactants that are very soluble in water and are
best used in closed systems so that they are not lost to the water column. Others
contain polymers that have a low water solubility and thus are best used on
open water. The aquatic toxicity of the products also varies widely.
The effectiveness of emulsion breakers and inhibitors is measured as the
minimum dose required to break a stable emulsion or prevent one from
Chapter | 14 Spill-Treating Agents 431

forming. As with dispersants, the use of emulsion breakers or inhibitors is

subject to rules and regulations in most countries. Only a few agents have
passed both the effectiveness and toxicity criteria, and permission is required to
use them. Similar legislation exists in many countries, especially for the use of
these products on open waters. Emulsion breakers are not often used on open
water or in cleanup operations in general.

14.5. RECOVERY ENHANCERS

Recovery enhancers, or viscoelastic agents, are formulations intended to
improve the recovery efficiency of oil spill skimmers or suction devices by
increasing the adhesiveness of oil. These agents can increase the recovery rate
of sorbent surface skimmers for products such as diesel fuel by up to ten times.
These products are not useful, however, with normally adhesive products such
as heavy crude oils and Bunker C. One recovery enhancer consists of a nontoxic
polymer in the form of microsprings, or coiled molecular forms, which increase
the adhesion of one portion of the oil to the other.

14.6. SOLIDIFIERS
Soldifiers are intended to change liquid oil to a solid compound that can be
collected from the water surface with nets or mechanical means. They are
sometimes referred to as gelling agents or collecting agents. Collecting agents
are actually a different category of agent that are the opposite of dispersants and
are not yet fully developed. Solidifiers consist of cross-linking chemicals that
couple two molecules or more, or polymerization catalysts that cause mole-
cules to link to each other. Solidifiers usually consist of powders that rapidly
react with and fuse the oil. Depending on the agent, about 10 to 40% by weight
of the agent is required to solidify the oil, under ideal mixing conditions. An
extensive section on solidifiers follows this introduction.
Solidifiers have not been used in the past for a number of reasons. Most
importantly, if oil is solidified at sea, it makes recovery more difficult as
skimming equipment, pumps, tanks, and separators are built to deal with liquid
or very viscous liquid. Second, such a large amount of agent is required to
solidify oil that it would be impossible to treat even a moderate spill. Third, the
faster solidifiers react with the oil, the less likely the oil is to become solidified
because the oil initially solidified forms a barrier that prevents the agent from
penetrating the remaining oil. Trials at sea have shown that solidifiers often do
not solidify the oil mass even when large amounts of treating agents are used.

14.7. SINKING AGENTS

Sinking agents are any material, usually minerals, that absorbs oil in water
and then sinks to the bottom. The use of sinking agents is banned in almost all
countries, however, due to serious environmental concerns. These agents can
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jeopardize bottom-dwelling aquatic life, and the oil is eventually released to

reenter the water column in the original spill area.

14.8. BIODEGRADATION AGENTS

Biodegradation agents are used to accelerate the biodegradation of oil in the
environment. They are used primarily on shorelines or land. They are not
effective when used at sea because of the high degree of dilution and the rapid
movement of oil.
Many studies have been conducted on biodegradation and the use of these
agents. Hundreds of species of naturally occurring bacteria and fungi have been
found that degrade certain components of oil, particularly the saturate compo-
nent, which contains molecules with 12 to 20 carbon atoms. Some species will
also degrade the lower-molecular-weight aromatic compounds. Hydrocarbon-
degrading organisms are abundant in areas where there is oil, such as near seeps
on land or in water. Studies have shown that many of these native microor-
ganisms, which are already thriving in the local climatic and soil conditions, are
better at degrading oil than introduced species that are not yet acclimatized to
local conditions.
Different types of oil have different potential for biodegradation, based
primarily on their saturate content, which is the most degradable component.
For example, diesel fuel, which is almost 95% saturates, will degrade readily
under the right conditions. However, some types of Bunker C that contain few
saturates will not degrade to any extent under any circumstances. This explains
why asphalt, the asphaltene, and heavy aromatic fraction of oils that does not
degrade is often used in building roads and in roofing shingles.
Biodegradation agents include bioenhancement agents that contain fertil-
izers or other materials to enhance the activity of hydrocarbon-degrading
organisms, bioaugmentation agents that contain microbes to degrade oil, and
combinations of these two.
Studies have shown that adding bioenhancement agents to oil spilled on
land can enhance the removal rate of the saturate and some of the aromatic
fraction of the oil, so that as much as 40% of the oil is degraded in time periods
from one month to a year. It is most important to recognize that one cannot ever
degrade all the oil, especially if it is a heavier type. Much of the oil will remain
undegraded and relatively unaltered, even years later. Furthermore, it may be
difficult to distinguish between oil removed by biodegradation and other
weathering processes.
It has been found that the agents are most effective when added at an oil-
to-nitrogen-to-phosphorus ratio of 100:10:1. Fertilizers that maintain the soil
at a more neutral level are best for degrading oil. Fertilizers that make the
soil acidic usually slow biodegradation. Fertilizers that are more oil-soluble
and less water-soluble are most effective as they are not as likely to be
washed away.
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Bioaugmentation agents are not used as extensively as bioenhancement

agents at oil-contaminated sites. This is because bioaugmentation agents
add new microorganisms, which is not usually as effective as stimulating
existing bacteria. There are strict government regulations about introducing
new, nonindigenous, and possibly pathogenic species to an area. All types of
biodegradation agents are subject to government regulations and approval
before use.
It should be noted that, while biodegradation does remove the saturates and
some aromatic fractions of the oil, it can take weeks or even years to remove the
degradable fraction, even under ideal conditions. Furthermore, the undegrad-
able components of the oil, which constitute the bulk of heavier crudes, remain
at the spill site, usually as a tarry mat often called asphalt pavement. It has been
found that biodegradation is useful for treating oil on grasslands or other land
not used to grow crops where the undegraded asphaltenes, resins, aromatics and
other undegradable components are not likely to pose a problem.