CONTROL OF OIL AND OTHER
HAZARDOUS MATERIALS
TRAINING MANUAL
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAMS
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U.S. Environmental Protection Agency
OFFICE OF WATER PROGRAMS
MANPOWER DEVELOPMENT STAFF
R. F. Guay, Director
Academic Training Branch
State and Local Operator Training
Programs
Office of Environmental Activities
Direct Technical Training Branch
National Training Center
Cincinnati, OH 45268
REGIONAL MANPOWER OFFICES
REGION I
Manpower Development Branch
Division of Air and Water Programs
424 Trapelo Road
Waltham, MA 02514
REGION II
Manpower Development and Training Office
Air and Water Programs
26 Federal Plaza
New York, NY 10007
REGION III
Manpower Development Office
Air and Water Programs
Curtis Building
6th and Walnut Streets
Philadelphia, PA 19106
REGION IV
Manpower Development Branch
Division of Air and Water Programs
1421 Peachtree Street, NE, Fourth Floor
Atlanta, GA 30309
REGION V
Manpower Development Branch
Office of Air and Water Programs
1 N. Wacker Drive
Chicago, IL 60606
REGION VI
Manpower Development Branch
Air and Water Programs Division
1600 Patterson
Dallas, TX 75201
REGION VII
Manpower Development Branch
Air and Water Programs
1735 Baltimore
Kansas City, MO 64108
REGION VIII
Manpower Development Branch
Air and Water Division
1860 Lincoln Street - 9th Floor
Denver, CO 80203
REGION DC
Manpower Development Branch
Air and Water Division
100 California Street
San Francisco, CA 94111
REGION X
Manpower and Training Branch
Division of Air and Water Programs
1200 Sixth Avenue - Mail Stop 345
Seattle, WA 98101
7.11.72
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CONTROL OF OIL AND OTHER
HAZARDOUS MATERIALS
This course is offered for employees of regulatory
agencies who are assigned direct responsibility for
response to nonrecurring discharges of oil. It is not
intended to dictate arbitrary solutions to technical
problems in spill control but will familiarize students
with alternatives and provide opportunity to practice
response under realistic constraints and measures of
success. In particular, students who complete this
course will be able to function within the guidelines of
Federal, State, or interstate Contingency Plans in
effect in the area where the course is presented.
ENVIRONMENTAL PROTECTION AGENCY
Office of Water Programs
TRAINING PROGRAM
September 1972
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FOREWORD
These manuals are prepared for reference use of students enrolled in
scheduled training courses of the Office of Water Programs, Environmental
Protection Agency.
Due. to the. 1-imite.d a\>a.ila.b-itLty oft the. ma.nu.a.l& ,
-it £& not a.ppfLOpfL.ia.te. to c-ite. the.m cu te.c.hnj.c.0.1
n.e.^e.ie.nc.e.i> -in bibtiogfLCLphie.* on. othe.n. ^o>im& 0(5
to pnodu.c.ti> and ma.nuLda,c.tu.n.e.n.& die.
4.L/iu.t>t>iCiti.on onty; Aac.h fLe.^e.n.e.nc.e.& do not impty
product e.ndorL&e.me.nt by the. 0^-ic.e. ofi Wa.te.1 Pn.ogia.rn*,
hge.nc.ij.
The reference outlines in this manual have been selected and developed with
a goal of providing the student with a fund of the best available current
information pertinent to the subject matter of the course. Individual
instructors may provide additional material to cover special aspects of
their own presentations.
This manual will be useful to anyone who has need for information on the
subjects covered. However, it should be understood that the manual will
have its greatest value as an adjunct to classroom presentations. The
inherent advantages of classroom presentation is in the give-and-take
discussions and exchange of information between and among students and
the instructional staff.
Constructive suggestions for improvement in the coverage, content, and
format of the manual are solicited and will be given full consideration.
Joseph Bahnick
Acting Chief
Direct Technical Training Branch
Division of Manpower and Training
Office of Water Programs
Environmental Protection Agency
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TRAINING PROGRAM
Through the Office of Water Program, Environmental Protection Agency•> conducts
programs of research, 'technical assistance, enforcement, and technical
training for water pollution control.
Training is available at five installations of the Agency. These are: the
National Training Center located at the Robert A. Taft Sanitary Engineering
Center in Cincinnati, Ohio; the Robert S. Kerr Water Research Center, Ada,
Oklahoma; the Southeast Water Laboratory, Athens, Georgia; the Pacific
Northwest Water Laboratory, Corvallis, Oregon; and the Hudson-Delaware
Basins Office, Edison, New Jersey.
The objectives of the Training Program are to provide specialized training in
the field of water pollution control which will lead to rapid application of new
research findings through updating of skills of technical and professional
personnel, and to train new employees recruited from other professional or
technical areas in the special skills required. Increasing attention is being
given to development of special courses providing an overview of the nature,
causes, prevention, and control of water pollution.
Scientists, engineers, and recognized authorities from other Agency programs,
from other government agencies, universities, and industry supplement the
training staff by serving as guest lecturers. Most training is conducted in the
form of short-term courses of one or two weeks' duration. Subject matter
includes selected practical features of plant operation and design, and water
quality evaluation in field and laboratory. Specialized aspects and recent
developments of sanitary engineering, chemistry, aquatic biology, microbiology,
and field and laboratory techniques not generally available elsewhere, are included.
The primary role .and the responsibility of the States in~the training of wastewater
treatment plant operators are recognized. Technical support of operator-training
programs of the States is available through technical consultations in the planning
and development of operator-training courses. Guest appearances of instructors
from the Environmental Protection Agency, and the loan of instructional materials
such as lesson plans and visual training aids, may be available through special
arrangement. These training aids, including reference training manuals, may be
reproduced freely by the states for their own training programs. Special categories
of training for personnel engaged in treatment plant operations may be developed
and made available to the States for their own further production and presentation.
An annual Bulletin of Courses is prepared and distributed by the'^Office of Water '
•Programs. The Bulletin includes descriptions of courses, schedules, application1
blanks, and other appropriate information. Organizations and interested indi-
viduals not on the mailing list should request a copy from one of the training centers
mentioned above.
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CONTENTS
Title or Description Outline Number
HAZARDOUS MATERIALS
General Information on Effects, Causes and Control of Hazardous 1
Material Spills
Personal Safety During Hazardous Material Spill Operations 2
OIL SPILL PROBLEM
Oil Pollution - Report to the President 5
Oil Pollution - Magnitude of the Problem 6
Oil Refinery and Terminal Operation 7
Complex Wastes Associated with Petroleum Refineries 8
Platform Operations - Offshore Oil Production 9
Biological Effects of Oil Pollution 10
OIL CHARACTERISTICS
Chemical and Physical Characteristics of Petroleum 12
Fate and Behavior of Spilled Oil 13
Oil Sampling 14
Analysis of Oil Samples 15
Microbiology of Petroleum 16
OIL SPILL PREVENTION. CONTROL AND TREATMENT
Oil Tanker Operations 17
Treatment of Oil Spills - Dispersants 18
Proposed EPA Tests on Oil Dispersant Toxicity and Effectiveness 19
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CONTENTS
Title or Description Outline Number
Treatment of Oil Spills -
Sinking Agents 20
Burning Agents 21
Gelling Agents 22
Sorbents 23
Control of Oil Spills - Booms 24
Treatment of Oil Spills, Oil Skimming Devices 25
Cleanup of Oil-Polluted Beaches 26
Waste Treatment Methods for Refineries 27
LEGAL RESPONSE
Legislation Affecting Oil 29
National and Regional Contingency Plans 30
Functions, Responsibilities and Role of the On-Scene-Commander 32
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HAZARDOUS MATERIALS
Outline Number
General Information on Effects, Causes 1
and Control of Hazardous Material Spills
Personal Safety During Hazardous Material 2
Spill Operations
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GENERAL INFORMATION ON EFFECTS, CAUSES AND CONTROL
OF HAZARDOUS MATERIAL SPILLS
I INTRODUCTION
More than two billion tons of potentially
hazardous materials were produced and
handled in the United States during 1968-
1969. It is projected that the annual pro-
duction quantities of these materials will
approximate four billion tons in 1980. Over
70 percent of these quantities are transported
by motor truck, railway, water barge and
pipeline. As long as the tonnage of liquid,
solid and gaseous hazardous chemicals
produced, handled, and transported by our
land and waterways continue to follow the
present upward trend, the accidental spillage
of these materials poses a real and growing
threat of pollution to our watercourses.
II EFFECTS
The effects of these materials on watercourses
and the plant and animal life associated with
them may vary, widely. In general, most
chemicals, when present in the environment
above certain critical concentrations, are
toxic to biological life and detrimental to the
environment's aesthetic quality. Although
many substances are obviously hazardous to
aquatic and marine life due to direct acute
toxicity, other substances are equally
detrimental to water ecosystems by virtue
of indirect toxicity resulting from depletion
of the dissolved oxygen supply required to
support various life forms. Still others,
although originally present at less than toxic
or inhibitory levels, may become concentrated
to these levels by residual accumulation through
a succession of food chain transfers. In
addition to direct effects of the spilled haz-
ardous materials, there may be other effects
of the products of reaction between the pollutant
and water or other materials in the watercourse.
Our present knowledge of the adverse effects
of a particular spill on the environment,
especially the persistence of the spilled
material and its immediate and long term
effects, is very limited.
Ill CAUSES
A General
The accidental entrance of a hazardous
material into a watercourse can occur in
a variety of ways. Spills or sudden
discharges can result from mechanical
malfunction, collision, fire or human
error in connection with rail, highway
and water modes of transportation or
with stationary sources such as manu-
facturing or storage facilities. The
most serious type of spill occurs when
a container is violently ruptured and
large quantities of the hazardous material
are spilled almost instantaneously. In
some cases, the material may be dis-
charged directly into a watercourse,
while in others the spilled material may
flow or be washed into sewers, drainage
channels or percolate slowly into ground
water supplies.
B Transportation Sources
A significant portion of the total problem
of hazardous material spills is caused by
transportation accidents. While derail-
ment presents the major potential for
railroad tank car spills, collision and
sinking are obvious sources of barge
spills. Spills may also occur at tank
truck, tank car and barge loading/unloading
facilities due to defective transfer pump
and flange connections, hose failures and
valve packing and seal deficiencies.
C Stationary Sources
1 One of the largest single sources of
pollution incidents in industrial plants
is failure or breakdown of manufacturing
or process equipment. These failures
include broken pipelines in chemical
plants, leaking tanks, malfunction of
refrigeration equipment, overflowing
of chemicals from tanks during
WP.HA. 1.5.71
1-1
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General Information on Effects, Causes and Control of Hazardous Material Spills
manufacture, faulty pressure gauges
and valves, pump breakdown, oper-
ational errors, metal failure due to
corrosion in acid transport pipes,
explosions and fires. These sources
of pollution incidents are compounded
to some degree by the many intentional
discharges of unwanted hazardous
materials into our nation's waters.
Storage facility spills also contribute
to the overall problem. Numerous
fish kills result from leaks from
storage tanks and broken lagoon dikes.
The leaching action of rain water on open
stockpiles of hazardous chemicals stored
in the open at water edge locations has
also greatly added to the contamination
of our waterways.
IV CONTROL
A Prevention
It is generally agreed that the prevention
of hazardous material spills constitutes
the most desirable method for effective
water pollution control. Unfortunately,
previous efforts to provide adequate
safeguards for handling these materials
and for preventing their release into the
aquatic environment have not been very
successful. A recently completed study
initiated by EPA's Office of Oil and
(1)
Hazardous Materials (Water Quality
Office), concluded that there are presently
no uniform industry-wide standards in the
United States for spill prevention and,
consequently, preventive techniques,
equipment and operational procedures
need to be developed to protect the public
health and welfare.
B Countermeasures
1 Although prevention remains the first
and most important line of defense, it
must be recognized that even with the
most comprehensive precautionary
techniques, accidents involving the
uncontrolled release of detrimental
substances to the environment must be
anticipated and appropriate response
measures must be developed to
minimize undesirable ecological effects.
Existing countermeasure techniques
have been developed primarily for
continuous discharge waste treatment
systems under controlled conditions.
However, because of the rapid response
required in the case of spills, the
majority of these available techniques
are not satisfactory for application in
the aquatic environment.
Hazardous materials involved in spills
which enter a watercourse may be
categorized on the basis of their
densities and solubilities in water.
The heavier, insoluble materials such
as ethylene dichloride and sulfur will
sink to the bottom of waterways. The
removal of these contaminants by
physical means, such as suction or
dredge type devices, is a possibility.
Less dense water insoluble chemicals
such as decyl alcohol will tend to float.
The mechanical separation of these
materials by confining the spill to a
small area by booms and removing
the materials by skimming should be
relatively successful. In the case of
water soluble materials such as phenol
and acrylonitrile, mechanical means
of removal are no longer possible
since the spilled material will be in
solution.
2 Priority ranking system
Because water soluble chemicals present
the greatest threat to the water eco-
system from a countermeasure point
of view, a priority ranking system for
estimating the theoretical inherent
hazard of these chemicals was pre-
pared as part of an EPA sponsored
state-of-the-art study '^) on hazardous
material spills. The ranking system
is based on (a) the lowest concentration
range at which a material impairs any
of the beneficial uses of water, (b) the
quantity shipped annually by each mode
of transport and (c) the probability of
an accidental spill to surface waters
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General Information on Effects, Causes and Control of Hazardous Material Spills
for each transport mode. Since a
material's ranking is then representative
of its potential threat to water quality,
it is expected that this system should
provide the guidelines for determining
which chemicals receive the greatest
attention relative to the development
of spill countermeasure techniques.
To illustrate this ranking system, the
top twenty water soluble substances
are arranged in order of decreasing
priority in Table 1.
TABLE 1
PRIORITY RANKING OF SOLUBLE
HAZARDOUS SUBSTANCES
Rank Substance
1 Phenol
2 Methyl Alcohol
3 Cyclic Rodenticides
4 Acrylonitrile
5 Chlorosulfonic Acid
6 Benzene
7 Ammonia
8 Misc. Cyclic Insecticides
9 Phosphorous Pentasulfide
10 Styrene
11 Acetone Cyanohydrin
12 Chlorine
13 Nonyl Phenol
14 DDT
15 Isoprene
16 Xylenes
17 Nitrophenol
18 Aldrin-Toxaphene Group
19 Ammonium Nitrate
20 Aluminum Sulfate
These substances include both organic and
inorganic materials and range from solids
to liquids to gases under standard conditions
of pressure and temperature.
3 Defensive and offensive measures
(2)
The state-of-the-art study also
provides a summary of possible
measures that can be employed in
responding to hazardous material
spills. The countermeasures are
divided into two major classifications:
defensive and offensive. The
defensive measures, which 'do not
counteract the contaminant in the
environment, consist of notifying all
downstream water users of the
occurrence of a spill and physically
removing all bags, barrels and other
containers which may still be leaking
into the watercourse. The offensive
measures include:
a The addition of acidic or basic
solutions to neutralize the spill.
b The addition of specific complexing,
chelating or precipitating agents
for the formation of solids or
compounds less toxic than the
originally spilled contaminant.
c The utilization of large scale equip-
ment to treat contaminated water in
place with powdered activated
carbon, a coagulant such as alum
and a polyelectrolyte so that the
resulting chemical floe precipitates
the carbon together with the adsorbed
contaminants.
d The physical removal of floes, solids
and liquids which have sunk to the
bottom.
e The use of booming and skimming
equipment to remove and contain
light solids or liquids floating on
the surface.
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General Information on Effects, Causes and Control of Hazardous Material Spills
h
Aid natural dilution to reduce con-
centrations of spilled materials to
a level below critical concentrations
by means of mechanical mixers,
such as outboard motors, to augment
flow of the materials.
Contain spilled soluble materials so
as to prevent diffusion throughout
the aquatic environment, since
most countermeasures are more
effective with concentrated pollutants.
Burning of floating volatile materials
where air pollution and safety con-
siderations permit.
4 Critique of countermeasures
In the critique of these countermeasures,
the referenced study '^) points out the
possible dangers that might result in
applying several of these in that the
resulting chemical compounds or
precipitates may be more harmful to
the environment than the original
hazard. Disadvantages of existing
carbon treatment methods are that
granular carbon treatment can be
employed only where some type of
treatment facility already exists, and
in the case of powdered carbon, the
method is listed as speculative. Caution
is advised in the use of the carbon
techniques since there is reason to
believe that the tremendous increase
in the solids load may have undesirable
effects. Removal of products which
sink to the bottom by suction devices
is listed as speculative since this
method might involve the removal of
large quantities of benthos along with
the contaminant. Booming and skimming
techniques, which have been widely used
in the case of oil spills, provide a
possible solution for spills of light
insoluble materials. Mixing techniques
for promoting dilution would be of value
in only a limited number of circumstances.
Containment techniques for soluble
materials are not readily available.
Burning techniques could be applied only
in a very limited number of cases where
the material remains confined in a small
isolated area so as to minimize threats
to safety and air quality.
5 Current status
It is clear from the above that adequate
control, neutralization and treatment
techniques for countering spills of
hazardous materials are practically
nonexistent. These countermeasures
for the most part require technology
not presently available. Nevertheless,
it is considered that new and useful
techniques can be developed by intensive
experimental programs on spill con-
trol and cleanup methods.
Inasmuch as the Water Quality
Improvement Act of 1970 (PL 91224)
requires the designation of appropriate
methods and means of removal of
spilled hazardous materials, EPA's
Division of Applied Science and
Technology (Water Quality Office) has
initiated Request for Proposal WA
71-513 on the development of methods
to treat and control spills of selected
high priority hazardous materials.
The methods to be developed are to
satisfy the following basic criteria:
a Result in no reactivity problems
causing secondary damage to the
environment including generation
of harmful sludges.
b Easily obtainable and transportable
equipment and chemicals.
c Minimum amount of auxiliary
equipment.
d Light in weight.
e Reasonable first costs.
f Rapid application in both congested
and remote areas.
g Safe to handle by untrained
personnel.
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General Information on Effects, Causes and Control of Hazardous Material Spills
Responsive proposals to the RFP are
currently being evaluated and several
contracts are expected to be awarded
by June 1971. These contracts will
cover a wide range of countermeasures
for: containing spills before they reach
surface waters; for containing con-
taminated water after a spill; and for
decontaminating polluted water areas
to return the water to a restored
condition of quality. Specifically,
some of the proposed countermeasures
under consideration include:
a Development of devices to contain
spilled hazardous materials on land
by use of rapidly formed in place
plastic dams or foamed dikes.
b Development of foamed plastic
devices for stopping leaks of
hazardous materials from ruptured
containers both on land and under-
water.
c Development of methods to poly-
merize and remove spilled hazardous
materials on land and to prevent
percolation of the materials into the
ground.
d Development of rapidly deployable
physical barriers which extend
from above the surface of the water
to the bottom of the waterway for the
purpose of containing spilled
hazardous materials in watercourses.
e Development of decontamination
system using floatable mass transfer
media (e.g. ,ion exchange resins and
carbon sorption media modified to
result in specific gravities less than
1) for: subsurface introduction into
waterways; treatment of contaminants;
and collection of spent media at the
water's surface.
Development of a continuous flow
through thin film aerator to which
chemicals can be added to neutralize,
oxidize, precipitate or adsorb
spilled hazardous materials from
watercourses, and to develop a
static sealed centrifuge to remove
gases, precipitates, carbon slurries,
and other solids from the effluent of
the aerator device.
Development of a modular trans-
portable treatment system incor-
porating various unit processes
such as neutralization, flocculation,
precipitation, filtration and carbon
adsorption, for the purpose of on-
site removal and treatment of spilled
hazardous materials in waterways.
REFERENCES
1 Spill Prevention Techniques for Hazardous
Polluting Substances. Arthur D. Little,
Inc. Report No. OHM 7102001,
prepared under Contract 14-12-927
for the Environmental Protection
Agency. February 1971.
2 Control of Spillage of Hazardous Polluting
Substances. Battelle Memorial
Institute, Pacific Northwest Laboratories,
Report No. 15090 FOZ, prepared under
Control 14-12-866 for the Environmental
Protection Agency. November 1970
3 Public Law 91-224, 91st Congress, H.R.
4148. Water Quality Improvement
Act. April 3, 1970.
This outline was prepared by I. Wilder,
Acting Chief, Hazardous Materials Research
Section, Edison Water Quality Laboratory,
OWP, EPA, Edison, NJ 08817.
1-5
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PERSONAL SAFETY DURING HAZARDOUS MATERIAL SPILL OPERATIONS
I INTRODUCTION
Of major concern in the control of hazardous
material spills is the protection of emergency
response personnel from dangers of the spilled
chemicals which are often extremely toxic
and corrosive. The purpose of this outline
is to provide general information on types of
protective devices necessary to insure the
safety of individuals during spill clean-up
operations. Because of the multiplicity of
chemicals that personnel may be exposed to
during spill situations, details of specific
safety equipment for specific hazardous
substances are not possible at this time.
Information contained herein are therefore
only directed towards the reduction of the
hazard potential of dangerous materials in
general.
II TYPES OF EXPOSURE
The accidental release of chemicals to the
environment may be inherently hazardous in
different degrees. Improper protection can
lead to severe personal injury. Injuries
resulting from hazardous material spills are
caused chiefly by chemicals or their fumes
coming in contact with the body (skin and eyes)
or through inhalation.
A Contact with Skin and Eyes
Contact of hazardous materials with the
skin is of primary importance because it
is the most probable type of exposure dur-
ing spills. Many materials in direct con-
tact with the skin will dissolve the fats and
oils in the skin tissue. The most common
result of excessive contact on the skin is
localized itching, dryness,, irritation or
burn. But an appreciable number of
materials are absorbed through the skin
with sufficient rapidity to produce systemic
poisoning. These materials may enter the
body through the skin either as a result of
direct accidental contamination or indirectly
when the material has been spilled on the
clothing. Some quite potent chemicals
such as dimethyl sulfate can cause burns
of disabling extent if but a few drops touch
the clothing.
Contact of chemicals with the eyes is of
particular concern because these organs
are extremely sensitive. Very few sub-
stances are innocuous in contact with the
eyes; most are painful and irritating and
a considerable number are capable of
causing burns and loss of vision.
B Inhalation
When hazardous vapors or gases are in-
haled, they may pass into the general
circulation system and may be distributed
to the heart and central nervous system
with extreme rapidity. Some vapors or
gases act so violently in the upper respi-
ratory system and lungs that they may
cause unconsciousness or even death if
the individual is not promptly removed to
an uncontaminated atmosphere and given
proper medical attention. Other vapors
or gases may first cause mild symptoms
such as headache, dizziness and fatigue,
then nausea, intestinal, visual or mental
disturbances and finally injuries to the
blood, liver, kidneys or other organs.
Ill PROTECTIVE DEVICES
Personnel who may be called upon to work in
atmospheres contaminated with hazardous
substances should have special safety equip-
ment and protective clothing readily avail-
able for emergency use. As a matter of good
operational policy, it is important that all
prospective users of these devices know
where they are stored, how they are used
and what are their limitations. It is also
essential that all personal protective equip-
ment be inspected and cleaned at regular
intervals and always before use by another
'person. A general description of some of
the basic personal protective devices are
given below.
A Respiratory Protection
Self contained air or oxygen respirators
are much safer than the air-purifying
type, since the wearer carries either a
supply of air or an oxygen generating
canister, and this type does not depend on
purification of the contaminated air for
breathing purposes. In emergency situ-
ations, where the concentration of con-
taminants may be high or is unknown, only
self contained respirators should be used.
The supplied air or oxygen (hose type)
respirator will not usually be applicable
SA.HM. 2.5. 71
2-1
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Personal Safety During Hazardous Material Spill Operations
to hazardous material spill situations,
since compressors or other air supplying
devices may not be readily available and
accessible during these emergency con-
ditions. Also, the hose type respirators
limit the wearer's freedom of movement,
whereas the self contained units allow
complete freedom. The pressure demand
compressed air or oxygen respirator is
considered the most fool-proof device
since it provides positive breathing safety
in the most dangerous atmospheres.
Where longer exposure time is required,
the self-generating oxygen respirator is
a good alternative.
The U. S. Bureau of Mines has a testing
section where respiratory devices are
inspected and tested. The Bureau tests
commercial respiratory protective devices
and issues approvals to those which meet
its standards. Maximum safety demands
that only U. S. Bureau of Mines approved
respiratory equipment be used.
Personal respiratory protection should be
used as a primary protective device when
it is necessary to enter a highly contam-
inated area for short periods of time.
Respiratory protective equipment is
basically of two general types:
1 Self contained or supplied air or
oxygen respirators
2 Air-purifying respirators
There are several classifications within
these two types:
1 Self Contained or Supplied Air or
Oxygen Respirators
a Self Contained
These respirators provide the
wearer with respirable air from a
source of supply independent of the
atmosphere where the wearer is
located. They are entirely self
contained and can be used in any
atmosphere. The principal types
of self contained respirators are:
1) Demand Compressed Air or
Oxygen
In this device, compressed air
or oxygen, contained in a cylinder
worn by the user, is supplied
through pressure reducing valves
to a close fitting full face, rubber
face piece only when the wearer
inhales. There is no recirculation
and the exhaled breath is directed
to the atmosphere. These units
are usually rated for 30 minutes
duration and are equipped with
alarm systems which warn the
user when to leave the hazardous
atmosphere because of diminishing
air supply.
2) Pressure Demand Compressed
Air or Oxygen
This respirator is a modification
of the Demand Compressed Air
or Oxygen Respirator. It is
designed to provide an extra mar-
gin of safety for personnel who
must enter atmospheres imme-
diately hostile to life. This unit
also provides air or oxygen on
demand, but in addition, it main-
tains within the face piece a slight
positive pressure above that of
the outside atmosphere. This
positive pressure prevents inward
leaks of dangerous gases, thus
assuring breathing safety in the
most toxic environments.
3) Self-Generating Oxygen
(Recirculating)
In this respirator, the exhaled
breath is directed to a chemical
canister which simultaneously
releases oxygen by the action of
the moisture in the breath on the
chemicals and absorbs carbon
dioxide from the breath. The
breath containing the released
oxygen enters a breathing bag
(which is connected by tubing to
the face piece) for inhalation, and
the exhaled breath repeats the
cycle. The canister for this
respirator, under ordinary usage,
can supply sufficient oxygen for
one hour. Although this respi-
rator is lighter than the pressure
demand type, it is quite bulky,
and once the seal on the canister
is broken, the respirator must
be used or the canister discarded.
b Supplied
These respirators supply air to the
wearer through a hose from an un-
contaminated remote source and are
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Personal Safety During Hazardous Material Spill Operations
therefore independent of the atmos-
phere surrounding the wearer. Ex-
treme care, however, must be ex-
ercised with these respirators in
obtaining a safe air supply. It is
important that blowers or. other air
sources be in an area which is free
from air contaminants. These
respirators provide relatively un-
limited time of use.
2 Air-Purifying Respirators
This type of respirator offers limited
protection, since it depends solely on
gas-absorbing material or mechanical
filtration media to remove specific
contaminants from the air. Since this
device utilizes the air surrounding the
wearer, it is not suitable in an oxygen
deficient atmosphere and must not be
used in environments containing con-
taminants iii concentrations higher than
those for which it was designed. For
example, air-purifying respirators do
not offer protection when oxygen levels
fall below 16% by volume or when con-
centrations of a toxic gas or vapor in
the breathing atmosphere are greater
than 2% by volume (20, 000 parts per
million). Similar to the self-contained
respirators, these units have limited
duration periods (about one hour). The
following are typical air-purifying
respirators:
a Chemical Respirators
In this device, inspired air is drawn
over suitable chemicals in a car-
tridge where gaseous contaminants
are removed. This respirator is
usually designed for a particular
contaminant only, but may also be
designed for combinations of con-
taminants.
b Mechanical Filters
These are similar to the chemical
respirators except that the purifying
chemicals in the cartridge are re-
placed by filters. Filter respirators
are designed to remove either a
specific single particulate contaminant
or several different contaminants.
c Combination Respirators
These are combined respirators, in
one unit, for simultaneous protection
against gases, vapors and partic-
ulates. They consist of chemical
cartridges with mechanical filters
in series, so that inspired air passes
first through the filter and then over
the chemical.
B Eye Protection
Eye protection is of major importance
during spill emergency situations because
of the ever present danger of injurious
vapors or chemical splash. Personnel
exposed to these situations should always
wear suitable safety eye wear. There
are numerous styles and types of safety
glasses available. The following lists
some of the representative types:
1 Plastic-rimmed safety spectacles with
hardened glass or plastic lenses,
available with or without side shields.
2 Plastic chemical splash goggles which
fit the contours of the face and fit
comfortably over all personal and
safety spectacles. Some types of
goggles also protect the nose and fore-
head.
3 Plastic face shields, which cover the
entire face, can also be worn over
personal and safety spectacles.
C Body Protection
Various specially treated protective
garments including coats, suits, over-
alls, aprons, rain wear and similar
clothing should be made available to
personnel to safeguard the body against
exposure to hazardous materials during
spill emergencies. These garments
should be made of solvent-proof plastics,
synthetic rubbers or other suitable pro-
. tective material resistant to corrosive
chemicals.
D Foot Protection
Rubber safety boots with metal reinforced
toe guards are recommended for protection
from heavy objects and other foot hazards.
Boots should be equipped with anti-skid
outsoles to permit the wearer to have a
reasonably secure footing even on oil
covered surfaces.
2-3
-------
Personal Safety During Hazardous Material Spill Operations
E Hand and Head Protection
Many minor injuries to personnel may be
prevented by the proper utilization of
effective hand protection. Heavy butyl
rubber or neoprene molded gloves should
be made available to individuals involved
in spill operations. These gloves are
furnished in different sizes up to elbow
length and are suitable for handling a wide
variety of acids and other corrosives.
Personnel should also be provided with
light weight plastic safety helmets (hard
hats) to guard against head injuries.
F Miscellaneous Protection
Emergency response personnel should
also be equipped with: battery-type lan-
terns for providing emergency illumination;
an explosimeter to determine the explosive
characteristics of an atmosphere; a port-
able oxygen indicator to quickly determine
the oxygen content of a contaminated area;
and portable first aid appliances.
3 Keep victim quiet, warm, lying down
and obtain medical assistance.
C Eye Exposure
1 Continuously wash eyes with clean
water for at least 15 minutes.
2 Obtain medical assistance, preferably
an ophthalmologist with experience in
handling chemical burns of the eye.
V SUMMARY OF GENERAL SAFETY
PRECAUTIONS
Extreme care should be exercised by personnel
involved in hazardous material spills. The
hazardous chemical should not be allowed to
come in contact with the unprotected skin or
eyes, and inhalation of vapors should be
avoided. If necessary to enter a spill area,
PUT ON COMPLETE PROTECTIVE CLOTHING
including goggles, boots, helmet, coveralls,
gloves, etc. and WEAR SELF CONTAINED
BREATHING APPARATUS.
IV FIRST AID
It must be recognized that, despite the most
comprehensive precautionary practices during
spill emergency operations, accidents will
occur and, consequently, injuries to personnel
must be anticipated. For this purpose, the
following general first aid measures are
suggested. For more detailed instructions,
a recognized source, such as the "Textbook
on First Aid" of the American Red Cross,
should be consulted.
A Toxic Vapor Inhalation
1 Remove exposed victim to fresh air at
. once. (Rescuers should be properly
protected).
2 If breathing has stopped, give artificial
respiration.
3 Keep victim quiet, warm, lying down
and obtain medical assistance.
B Skin Exposure
1 Immediately remove all contaminated
clothing from victim. (Those assisting
victim should wear suitable protective
gloves).
2 Thoroughly flush skin with clean water
to remove all traces of hazardous chem-
ical.
2-4
REFERENCES
1 Banme, C. W. , "Fire Protection for
Chemicals", National Fire Protection
Association, Boston, 1961.
2 "Fire Protection Guide on Hazardous
Materials", National Fire Protection
Association, Boston, 1967-1968.
3 "Hazardous Chemicals Data", National
Fire Code No. 49, National Fire Pro-
tection Association, Boston, 1965.
4 Manufacturing Chemists' Association, Inc.,
"Guide for Safety in the Chemical Lab-
oratory", D. Van Nostrand Company, Inc. ,
New York, 1962.
5 Manufacturing Chemists' Association, Inc. ,
"Laboratory Waste Disposal Manual",
1969.
6 Plunkett, E. R. , "Handbook of Industrial
Toxicology", Chemical Publishing
Company, Inc., New York, 1966.
7 Sax, N. I., "Dangerous Properties of
Industrial Materials", Rheinhold Book
Corporation, New York, 1968.
8 Scheflan, L. , Jacobs, M. , "The Handbook
of Solvents", D. Van Nostrand Company,
Inc., New York, 1953
This outline prepared by I. Wilder, Acting
Chief, Hazardous Materials Research Section,
EPA, OWP, Edison Water Quality Laboratory,
Edison, NJ 08817
-------
OIL SPILL PROBLEM
Outline Number
Oil Pollution - Report to the President 5
Oil Pollution - Magnitude of the Problem 6
Oil Refinery and Terminal Operation 7
Complex Wastes Associated with Petroleum 8
Refineries
Platform Operations - Offshore Oil Production 9
Biological Effects of Oil Pollution 10
-------
OIL POLLUTION, REPORT TO THE PRESIDENT*
On May 26, 1967, the President of the United
States directed the Secretary of the Interior
and the Secretary of Transportation to examine
how the resources of the Nation could best be
mobilized against the pollution of water by
spills of oil and other hazardous substances.
Referring to the TORRY CANYON and Cape
Cod incidents earlier this year, the President
considered it "imperative that we take prompt
action to prevent similar catastrophes in the
future and to insure that the Nation is fully
equipped to minimize the threat from such
accidents to health, safety, and our natural
resources. " He asked for a thorough assess-
ment of existing technical and legal resources,
and for recommendations toward an effective
national and international program.
This report responds to the President's
directive. It deals primarily with water
pollution by oil, but where appropriate is
addressed to other hazardous substances as
well. It reflects a conviction that the problem
of oil pollution must be faced and solved as
part of the current general effort to improve
the quality of life in the United States. Just
as the Nation cannot afford to accept the
slow poisoning of its air, or the fouling of its
cities and countryside, it cannot abandon to
pollution the treasure of its waters and
shorelines.
Oil in its many forms — oil in vast quantities --
is one of the necessities of modern industrial
society. Under control, serving its intended
purpose, oil is efficient, versatile, productive.
Out of control, it can be one of the most
devastating substances in the environment.
Spilled into water, it spreads havoc for miles
around.
The destructive characteristics of oil out of
control--and the inadequacy of current
measures for dealing with it--have never
been better illustrated than when the TORREY
CANYON, with 119, 000 tons of crude oil in
her tanks, ran aground and broke up off the
southern coast of England last March. The
desperate efforts of the British and French
to cope with the tragedy captured the attention
and sympathy of people all over the world.
Oil spills, large and small, as well as the
careless or accidental release of other
hazardous materials into the environment,
have long been of concern to pollution control
authorities in this country. Once an area has
been contaminated by oil, the whole character
of the environment is changed. Afloat, even
a relatively small quantity of oil goes where
the water goes. By its nature, oil on water
is a seeker. Once it has encountered something
solid to cling to--whether it be a beach, a rock,
a piling, the feathers of a duck or gull, or a
bather's hair--it does not readily let go.
Cleaning up an oil-contaminated area is
time-consuming, difficult, costly. To the
costs of the cleanup must be added the costs
of the oil invasion itself--the destruction of
fish and other wildlife, damage to property,
contamination of public water supplies and
any number of other material and esthetic
losses. Depending on the quantities and kinds
of oil involved, these losses may extend for
months or years — sometimes for decades—
with correspondingly heavy costs of restoring
the area to its prior condition.
The risks of contamination by oil and other
hazardous substances are as numerous and
varied as the uses made of the many materials
involved and the means of transporting them.
These risks involve terminals, waterside
chemical and other industrial plants, loading
docks, refineries, tankers, freighters, barges,
pipelines, tank cars, trucks, filling stations—
everywhere that oil is used, stored, or moved.
All are subject to mechanical failures com-
pounded by human carelessness and mistakes.
There are countless opportunities for oil to
get out of control.
This country is not fully prepared to deal
effectively with spills of oil or other hazardous
materials—large or small—and much less with
a TORREY CANYON type disaster. Because <
sizable spills are not uncommon, and major
spills are an ever-present danger, effective
steps must be taken to reduce this Nation's
vulnerability.
All preventive measures cost money, and the
actions recommended in this report will be no
exception. The cost of preventive measures
which might be incorporated in ships or
industrial establishments or operating equip-
ment must be weighed against the costs, both
tangible and intangible, that arise from
disastrous spills. Such cost evaluations may
be expected to guide the development of ships
and industrial facilities, with effects on their
future size and operating characteristics. On
the whole, economics and good sense commend
an effort to prevent pollution rather than accept
the costs of its occurring. For this reason,
*This is the introduction from A Report .on Pollution of the Nation's Waters by Oil and Other
Hazardous Substances to the President by the Secretary of the Interior and the Secretary of
Transportation, 2/68.
WP.OI.2.5.71
5-1
-------
Oil Pollution, Report to the President*
the recommendations in this report stress
preventive action.
In spite of preventive efforts there will still
be spills, either due to human carelessness
or to calamities beyond human control. For
those reasons, this report also addresses it-
self to improved cleanup measures. Present
cleanup procedures leave much to be desired
and are often too expensive, too tardy, too
ineffective, and too destructive of the marine
and land environment. There is room for a
great deal of improvement in present techni-
ques, and there is a need for the development
of better ones.
The oil pollution problem has significant
international aspects. First, accidental
or deliberate spills which threaten American
coasts may occur outside the United States
territorial waters. Despite this fact, the
United States must be able to act quickly
against a threat that develops in international
waters so that we may take whatever immediate
Ereventive or remedial steps are necessary.
econdly, vessels which discharge oil may be
outside the registry of an affected coastal
nation and thus not be within the direct and
simple application of the nation's laws. For
this reason, attention has been given for
some years to international cooperation in
control of oil pollution. As an example, the
Subcommittee on Oil Pollution of the Inter-
governmental Maritime Consultative Organiza-
tion (IMCO) has done continuing work in this
field. Through this Subcommittee, IMCO is
presently examining a series of proposals
(parallel at many points with the conclusions
of this report) which might be adopted
internationally to minimize the threat of
future spills. Further efforts to reduce oil
pollution should include seeking expanded use
of international regulation because any other
solution would be incomplete. For these
reasons, this report stresses the need for
rapid international action, as well as urgent
steps to be taken domestically.
5-2
-------
OIL POLLUTION - MAGNITUDE OF THE PROBLEM
I SOURCES AND AMOUNTS
A Broad Picture
Petroleum in its many forms has been on
the move in the United States since 1859
when the first commercially successful oil
well was developed in Pennsylvania.
First transported by wagon and log raft,
oil is now en route from the oil field to
refinery to consumer by pipe, water, rail
and highway. During 1970 more than 4. 5
billion barrels of petroleum moved as
crude oil from the production field through
the refineries and then as refined products
to the consumer. Ocean tankers, barges,
pipelines, railroad tank cars and tank and
trucks are the vital elements of the com-
plex and diversified transportation system
required to move this volume of oil.
Estimated amounts of oil lost as well
as the sources of this form of pollution are
shown in Table 1. It is interesting to note
that the loss of waste or used oil from
vehicles (crankcase oil) may be the largest
single source of oil pollution, larger, in
fact, than the total volume from all sources
lost directly to the oceans.
B Spill Frequency
Obtaining of one barrel of petroleum from
the oil field to the consumer may require
10 to 15 transfers between as many as six
different transport modes. Each mode is
subject to accidents, and at the transfer
points spill frequency is extremely high.
Approximately one barrel of product is
lost for each one million transported.
About 7, 500 oil spills are now occurring
annually with an estimated total loss of
500, 000 barrels (2).Most of the spilled
oil is discharged to water. In addition
to spills, the potential for discharges from
normal vessel operation is in excess of
700, 000 barrels of oil annually.
The number of spills and quantities lost
vary with the type of transport system.
About 217, 000 miles of petroleum pipe-
lines crisscross the United States
transporting 45 percent of the Nation's
annual consumption of petroleum.
Pipeline failures accounted for only
three percent of the product lost in 1969.
A United States fleet of 387 tankers and
2, 900 barges presently operates in the
Nation's waterways. In worldwide oil
traffic. United States vessels make up
only five percent of tanker traffic United
States and foreign flag tankers were
responsible for approximately 80-90
percent of the oil spilled in 1969.
Tank trucks and railroad tank cars
together account for less than one percent
of total product lost. '2'. Tank trucks
are the last leg of the transportation
system, delivering refined products to
the retail consumer. Approximately
158, 000 tank trucks are on the road.
In areas not served by pipelines or
navigable waterways, over 81, 000 rail-
road tank cars take over the transport
of crude and refined petroleum products.
C Why Spills Occur
(4)
Blumer reported that human error
accounted for 88 percent of the total
number of spill incidents. The means
of rectifying this situation is by better
• training and education, improved
engineering, and when all else fails
enforcement by a responsible State or
Federal agency.
WP.OI.3.5.71
6-1
-------
Oil Pollution - Magnitude of the Problem
TABLE 1
ESTIMATES OF OIL INTRODUCED INTO WORLD'S WATERS
AND POTENTIAL LOSSES TO WATERS, 1969
Metric Tons Per Year % of Total
1. Tankers
(normal operations)
Using Control Measures 30, 000
(80%)
Not Using Control Measures 500, OOP
(20%) 530,000 10.7
2. Other Ships
(bilges, etc.) 500,000 10.1
3. Offshore Production
(normal operations) 100,000 2.0
4. Accidental Spills
ships 100,000 2.0
nonships 100, 000 2.0
5. Refineries and
petrochemical 300,000 6.0
SUBTOTAL 1, 630, 000
6. Potential losses to water from
industrial and automotive
(not fuel):
Highway vehicle spent oils 1,800,000 36.6
Industrial plus all other vehicles 1, 500, OOP 30. 6
SUBTOTAL 3,300,000
TOTAL 4, 930, OOP
NOTE: Oil from pleasure craft and natural seeps not included.
6-2
-------
Oil Pollution - Magnitude of the Problem
Another important factor in the cause of
spills by vessels is the stopping ability of
the tankers under crash stop conditions --
vessel in full reverse. It has been reported
thar ' 'the most important factor in
connection with collision and stranding--
the two most dreaded casualties—is the
'crash stop1 ability. Unfortunately, the
ability of tankers to come to a "crash stop1
has decreased as their size has increased.
For the 400, 000 tonner, the straight-line
stopping distance for a 'crash stop1 would
be four to five miles and would take
approximately 30 minutes. During this
period of backing full, the ship's master
is unable to steer her or regulate the speed.
If the engines are not put 'full astern1 but
on 'stop1 it takes up to one hour for the
"Universe Ireland" to come to a stop.
TT.OOOlon.""
5 minute!
I ton. 1/g mile
21 minutes
200,000 tonn 2.5 miles
30 minute*
4.5 miles
1,000,000 lon»
FIGURE 1
H ANALYSIS OF PAST MAJOR SPILLS
Dillingham Corporation under contract to
API, conducted a statistical study to develop
an understanding of the basic characteristics
of major oil spills--defined as a spill of
2, 000 barrels (84, 000 gallons) or more of a
heavy (or persistent) oil which will not
naturally evaporate or disperse rapidly in
the environment--and thus define the nature
and scope of the problem.
Based on an analysis of 38 past spills, which
occurred during the period 1956 to 1969, they
reported that:
A Source
75% were associated with vessels,
principally tankers.
B Composition
90% involved crude or residual oils.
C Volume
70% of the spills were greater than
5, 000 barrels with a median spill volume
of 25, 000 barrels.
D Distance Offshore
80% occurred within 10 miles of shore
and the oil would reach shore within one
day.
E Duration
75% of the spill incidents lasted more than
five days with a median duration of 17 days.
F Extent
80% contaminated less than 20 miles of
coastline with a median extent of four
miles of coast.
G Coastline
85% occurred off shoreline considered to
be recreational.
H Distance from Port
75% occurred within 25 miles of the nearest
port.
Item (D) above is probably one of the most
significant factors revealed by this study.
As shown in Figure 2, fifty percent of the
offshore spills occurred less than one mile
from shore. Since oil appears to drift at
approximately 3% of the wind velocity, and
with an assumed average wind of 15 knots,
the oil slick would drift at approximately
0.5 knots. Thus, with 50% of the spills less
than one mile offshore, an onshore wind
could move oil onto shore in two hours. The
question that now arises is "how does one
mobilize shoreline protection equipment
during this short length of time?"
6-3
-------
Oil Pollution - Magnitude of the Problem
in MAJOR SPILL INCIDENTS 1956-1970
For reference purposes, major spill incidents
along with significant characteristics, are shown
in Table 2(3*5)
REFERENCES
1 Massachusetts Institute of Technology.
1970. Special Study Group.
2 Wyer, R.H., et al. Problems Resulting
from Transportation of Petroleum
Products. Presented WPCF National
Meeting. October 1970.
3 Oliver, E.F., Capt., USN Ret. U.S.
Naval Institute Proceedings. September
1970.
Blumer, Max.
1969.
Personal Communication.
5 Dillingham Corp. 1970. A Review of
Problem - Major Oil Spills.
6 Hess, Richard. Office of Oil and
Hazardous Materials, EPA,
Washington, D. C., Personal
Communication.
7 Gilmore, G.A., et al (1970). Systems
Study of Oil Spill Cleanup Procedures.
Dillingham Environmental Col, La
Joila, California.
This outline was prepared by Richard T.
Dewling, Director, R & D, Edison Water
Quality Laboratory, Office of Water Programs,
EPA, Edison, NJ 08817.
6-4
-------
I00%i
90%-
80%-J
—
'5.
2 60%
c
0>
o
£ 50%
o 40%-
D
E
o 30%-
20%-
10%-
D is fa nee from Shore and Response Time
Available for Shoreline Protection
Data from 25 Incidents
52%
Less Than One Mile
2 Hours
Response Time
(Assuming a 15 knot onshore wind and oil drift a! 3%
of wind velocity)
I Day
H 1—f-
345
10
Miles
H 1 H-
20 30 40 50
10 Days
100
-------
Oil Pollution - Magnitude of the Problem
TABLE 2
MAJOR OIL SPILL INCIDENTS
Name
ALGOL, tanker
ANDRON, tanker
ANNE MILDRED BROVIG, tanker
ARGEA PRIMA, tanker
ARROW, tanker
BENEDICT E, tanker
Bridgeport, Conn., terminal
Chester Creek, pipeline
CHRYSSI P. GOULANDRIS, tanker
Dutch Coast Spill
ES SO ESSEN, tanker
ESSO HAMBURG, tanker
FLORIDA, barge
GENERAL COLOCOTRONIS , tanker
HAMILTON TRADER, tanker
HESS HUSTLER, tank barge
Humboldt Bay, refinery
KENAI PENINSULA, tanker
KEO, tanker
Louisiana, Chevron platform
Louisiana, Shell platform
MARTITA, tanker
Moron, refinery
New. Castle, power station
OCEAN EAGLE, tanker
,R. C. STONER, tanker
Refinery Loading Site
ROBERT L. POLLING, tank barge
Santa Barbara, platform
Schuylkill River, Berks Assoc.
Sewaren, N. J., storage tank
Ship Shoal, drill rig
Staten Island, N.Y., 2 Esso barges
USS SHANGRI-LA (CVA-38) '
YIAMPICO, tanker
TIM, tank barge
TORREY CANYON, tanker
Waikiki Beach
Waterford !5each •
WITWATER, tanker
WORLD GLORY, tanker
• Date
02-09-69
05-05-68
02-20-66
07-17-62
02-04-70
05-31-69
6-15-70
08-08-69
01-13-67
02-16-69
04-29-68
01-29-70
09-16-69
03-07-68
04-30-69
11-12-68
12- -68
11-05-68
11-05-69
04-10-70
12-1-70
09-20-62
03-29-68
1963-65
03-03-68
09-06-67
1962
05-10-69
01-28-69
11-13-70
10-31-69
03-16-69
05-22-70
1965
03- -57
02-18-68
03-18-67
04-21-68
01-18-69.
12-13-68
06-13-68
Cause of spill
Grounding
Sinking
Collision
Grounding
Grounding
Collision
Pumping
Break
Unknown
• Unknown
Grounding-
Grounding
Grounding '
Collision
Grounding
Hose failure
Collision
Hull failure
Fire
Fire
Collision
Pumping
Leak
Grounding
Grounding
Hose failure
Collision
Natural faults
Lagoon failure
Tank failure
Storm shifting
Collision ..
Pumping
Grounding
Sinking
Grounding
Unknown
Unknown
Hull failure
Hull failure
Material
#6 F. 0.
Crude
Crude
Crude
Residual
Crude
#2 F. 0.'
"2 F. 0.
Crude
Residual
CtOide
#2 F. 0.
Crude
. Residual
#6 F. 0.
Diesel
Crude
#4 F. 0.
Crude
Crude
Bunker C
Crude
Residual
Crude
Mixed
Crude
#2 F. 0.
Crude
Volume
(barrels)
4,000
117,000
125,000
28,000
36,000
14,000
20,000
3,500
2,600
1,000
30,000
10,000
4,000
. 30,000
5,000
40
1,400
1,000
210,000
60,000
Unknown as
of this date
4,300
16,000
40-
83,400'
143,300
2,000
4,700
100,000
Waste Crankcase 70,000
Crude
Crude
#6 F. 0.
NSFO
Diesel
#6 F. 0.
Crude
Bunker C
#6 F. 0.
Mixed
Crude
200,000
2,400
10,000
200
60,000
7,000
700,000
15,000
322,000
6-6
-------
OIL REFINERY AND TERMINAL OPERATION
I INTRODUCTION
A petroleum refinery is an organized and
coordinated arrangement of manufacturing
processes designed to provide both physical
and chemical change of crude petroleum into
salable products with the qualities required.
H TYPES OF REFINERIES
Refineries can be classified as simple,
complex, or fully integrated.
A A simple refinery will include crude oil
distillation, catalytic reforming and
treating. Its products will be limited to
LP gas, motor fuels, kerosene, gas oil,
diesel fuel and fuel oil.
B A more complex refinery will make a
greater variety of products and require
the following additional processes:
vacuum distillation, catalytic cracking,
polymerization, alkylation and asphalt
oxidation.
C The fully integrated refinery makes a full
range of products. Additional products
will include lubricating oils, greases, and
waxes. Additional equipment will include
solvent extraction, dewaxing and treating.
A typical refinery flow plan for a fully
integrated refinery is presented as Figure 1.
IH TYPES OF CRUDE OILS
There are over 8, 000 different types of crude
oils in the USA alone and these vary from high
to low sulfur content and from asphaltic to
paraffinic and from heavy to light in specific
gravity.
A The asphalt base crudes cpntain very little
paraffin wax and a residue primarily
asphaltic. These crudes are particularly
suitable for making high quality gasoline
and asphalt.
B Paraffin base crudes contain little asphaltic
material, are good sources of paraffin wax,
quality motor oils, and high grade kerosene.
C Mixed base crudes contain both wax and
asphalt. Virtually all products can be
obtained.
IV TYPES OF PROCESSES
A Atmospheric Distillation
Today's crude distillation occurs in
towers containing a series of horizontal
trays where liquid condenses, collects
and is withdrawn. Since distillation is the
most frequently used unit operation in
refining, a drawing of. a typical distillation
column is presented as Figure 2.
The lighter, more volatile portions of the
crude are withdrawn at the upper part of
the tower and the heavier parts down lower
in the tower. It is in this manner that the
crude oil is first broken into its parts.
Improved separation between products
can be accomplished by installing more
fractionating trays.
B Vacuum Distillation
Normally, it is desired to cut deeper into
the crude oil than would be possible under
atmospheric pressure and reasonable
temperatures. Therefore, vacuum dis-
tillation is performed on the residual from
the atmospheric distillation. This process
is essentially the same as atmospheric
distillation except it is fractionation
performed under a vacuum.
C Catalytic Cracking
The rising needs for producing more
gasoline per volume of crude oil led to the
development of catalytic cracking. Here,
a gas oil, not valuable for any other use,
is fed to the catalytic cracking unit where
-it is cracked in the presence of a catalyst
to gasolines and heating oils.
D Alkylation
Further needs for high octane gasolines
led to the development of another process
called alkylation where several com-
ponents of the refinery gas streams are
combined over a catalyst to make a high
octane component.
IN.PPW.ol.9.5. 71
7-1
-------
Oil Refinery and Terminal Operation
E Polymerization
Here, again, this process was developed
to utilize several components from a
normal refinery gas stream and combine
them into high octane number gasoline
fractions.
F Platforming
This major process development consisted
of the use of a platinum based catalyst to
upgrade the octane number of naphtha
distilled from crude oil to very high levels
for use in aviation and high quality motor
fuels.
G Hydrotreating
This process utilizes the excess hydrogen
produced in the platforming process to
remove sulfur compounds in many refinery
products, motor fuel, lube oil and fuel oil.
H Hydrocracking
The use of hydrogen was extended to the
hydrocracking process which converts
petroleum residues by catalytic hydro-
genation to refined heavy fuel oils or to
high quality catalytic charge stocks.
I Coking
In this process heavy low grade oils are
converted into lighter products and coke
which is sold or burned.
J Treating Process
Many contaminants are present in crude
oils in varying concentrations and include
organic compounds containing sulfur,
nitrogen and oxygen, dissolved metals and
inorganic salts. These contaminants are
removed at some intermediate stage or
just prior to sending the finished product
to storage. Numerous treating chemicals
are used and most fall into one or more of
these classifications:
1 Acid
2 Alkali
3 Solvent
4 Oxidizing agent
5 Absorption agent
V EFFLUENT WATER IMPROVEMENT
PROCESSES
A API Separator
This equipment removes surfaced oil by
skimming and pumping the skimmed oil
to rerunning.
B Equalization Basin
Secondary oil recovery is possible here
because of the large holding time.
C Flocculator-Clarifier
Coagulants are used to break emulsions
and oil is removed by skimming.
D Biological Treatment
The activated sludge uses dispersed air
for mixing and oxygen supply. The water
can also be treated in trickling filters
which are packed with high rate plastic
media.
E Holding Basins
These basins are utilized to permit
checking the quality of the effluent. If
not satisfactory, it can be recycled.
F Ozonator
Here the phenols are reduced by oxidation
and the water is partially sterilized.
G Activated Carbon and Rapid Sand Filtration
Here additional reduction of phenols is
accomplished by mixing the activated
carbon with the waste streams and removing
it in sand filters.
VI TERMINALLING
A Tankers
1 Tankers are loaded or unloaded through
flexible hose connected to shore pipe-
lines or by means of loading booms
made of conventional pipe connected by
swivel joints.
2 Tankers are divided into two groups:
a Dirty or black oil ships which trans-
port crude oilo, fuel oils and diesel
fuels.
7-2
-------
Oil Refinery and Terminal Operation
b Clean or white oil ships which carry
highly refined products.
B Barge
Another form of transport is the barge
usually used on long wide navigable rivers.
Barges usually carry products rather than
crude oil.
C Procedure for Handling Receipts
1 A discussion between the vessel people
and terminal people should be held as
soon as the vessel is properly hooked
up. Sequence of discharging lines to
be used, volume of each product and
permissible pressure must be clearly
understood.
2 Communications
Appropriate signals and means for
transmitting them must be established.
Telephone or walkie-talkies or hand
radios can be utilized.
The vessel deck officer must be notified
whenever a change in receiving tankage
is to made so he can prepare for a
pressure surge.
3 Identification of Lines
All lines and manifolds should be clearly
marked so that the pipelines carrying
each product are identified.
4 Manning
It is prudent operation to maintain one
man on the terminal side of the facil-
ities at all times and one man on the
ship at all times so that in the event of
an emergency the proper steps can be
. taken by each immediately.
5 Vessel Check
Prior to starting the ship's pumps or
notifying the dock crew to begin trans-
fer operations, the senior deck officer
must assure himself that the entire
cargo system is lined up properly.
6 Terminal Check
The terminal superintendent or his
representative should be certain that
all valves controlling flow to and from
tanks involved in the discharge or
loading are in their proper setting and
that valves not involved in the transfer
or loading are closed.
7 Use of Log
The use of a log reading the amount
that the tank has received and comparing
this volume with the amount that the
tanker has discharged every two hours
will quickly inform the terminal personnel
that all material is finding its way into
proper tankage or not.
8 Topping Off and/ or Switching Tanks
Terminal manpower should always be
assigned when the level of oil in a tank
reaches a high point in that tank.
9 Tankage Assignment
Before the cargo arrives, it is impor-
tant that the terminal people in charge
of the receipt check the volume of space
available to receive each product and
conclude whether adequate space is
available. This information should be
entered on the log as the stop-gauge
for the transfer for each specific
product.
This outline was prepared by R. R. Keppler,
R&D Specialist, Office of Water Programs, Boston
Regional Office, Boston, MA 02203
7-3
-------
i
*>.
CRACKING UNIT
dmui • UTUTIK aaama
NATMAL6AS
KM HOOKS AMD WOUSI1T
HIGH OCTANE AVIATION GAS.
AUTOMOTIVE GASOLINE
FINISHED KEROSINE
DOMESTIC HEATING OIL
and DIESEL FUELS
HYDROCARBON GASES
Row Material for
MaWocfivc of:
HIGH OCTANE GASOLINE,
SYNTHETIC DUiBCB.
PLASTICS,
PAINTS AND VAINISHES. .
AICOHOIS AND SOLVENTS.
EXPLOSIVES. AND
MANY OIHEH PIODUCTS
INDUSTRIAL FUEL OIL
FINISHED LUBRICATING OILS
WAX-PARAFFIN
GAS OIL
»COXE
ASPHALT
(0
P
a.
3
(0
a>
'-s
SB
Fig. 1 Simplified Flow Diagram of Refinery
-------
Oil Refinery and Terminal Operation
X \ \ REFLUX LINE
BUBBLE CAPS -
/ , . , A
HEATER
'_ -p r rvmr
III BOTTOM DRA»OFF
Fig. 2 - Bubble Cap-type Fractionating Tower
7-5
-------
COMPLEX WASTES ASSOCIATED WITH PETROLEUM REFINERIES
I INTRODUCTION
Water is used in petroleum refining processes
mainly as a cooling medium, to rinse impurities
out of the oil, and to manufacture steam. In
these uses the water is contaminated with a
complex variety of materials. The nature and
sources of these materials are discussed
below.
II NATURE OF PETROLEUM
Crude oils are mixtures of many substances
from which various oil products, such as
petroleum gas, gasoline, kerosene, jet fuel,
fuel oil, lubricating oil, wax, and asphalt are
manufactured. These substances are mainly
compounds of hydrogen and carbon, and are
therefore called hydrocarbons. The various
oil products may be described in a general
way by their boiling range as shown in the
following table (Table I).
Product
Fuel gases
Propane
Butane
Gasoline
Kerosene and
jet fuel
Furnace and
diesel fuel
Residue (asphalt)
Carbon
Atoms
1-2
3
4
4-12
10-18
11-22
20+
Boiling
Range °F
-259 to - 128
-44
+31
100-400
350-570
355-700
600+
III IMPURITIES IN PETROLEUM
Crude petroleum contains small amounts of
impurities. Among these are:
Brine
Sediment
Sulfur
Nitrogen
Oxygen
Trace elements (copper, nickel, iron,
vanadium, etc.)
As you will see later, some of these same
impurities contribute significantly to the
contamination of water used in the oil refining
processes.
Crude oil, as it is brought up from underground,
is mixed with briny water and sediment. Part
of this is removed in the oil fields, but a
small amount remains emulsified in the oil
and must be removed at the refinery.
Petroleum is the product of decomposition
of animal and vegetable matter, and contains
elements present in the original living
organisms. Among these are sulfur, nitrogen,
and oxygen. Smaller amounts of such elements
as copper, nickel, iron, vanadium, etc., are
also present.
IV REFINERY FLOW DIAGRAM
No crude oil can provide a full range of
finished products in the proportions and
having the properties that the customers
require. The function of a refinery is to
make the required products - both directly
from the crude or by converting the original
material into saleable material. This is
done by the following general steps: separation,
alteration, purification, and blending.
A Distillation
The first step inrefining is to separate,
or distill, crude oil into parts or fractions.
Each fraction has its own typical boiling
range, as was seen in a foregoing table.
Light fractions, such as gasoline and
solvents, boil at low temperatures - while
the heavier fractions, such as fuel oils,
have higher boiling ranges.
Simple distillation can only produce those
products which were in the original crude.
In other words, a particular crude will
yield only so much gasoline and so much
jet fuel. So as the demand for gasoline
increased, refineries brought into use a
process called "cracking".
B Cracking
In cracking, the heavy, high-boiling parts
of the crude oil are broken down by high
temperature into lighter fractions boiling
in the range of gasoline, jet fuel, and diesel
fuel. In the earlier cracking processes -
thermal cracking and coking - high
temperature alone was used to accomplish
cracking. Later catalysts were also used
IN. PPW. ol.7.8. 70
8-1
-------
Complex Wastes Associated With Petroleum Refineries
to improve the yield and quality of the
gasoline produces. The latest cracking
process - hydrocracking - uses not only
high temperature and catalysts, but also
high pressure and an atmosphere of hydrogen.
C Alkylation
Cracking the heavier parts of crude oil to
produce lighter fractions is something like
breaking larger rocks into smaller ones.
In the fracturing process some small
particles are formed. Joining these smaller
molecules together to form material in the
gasoline range is done by cracking-in-
reverse processes called alkylation or
polymerization.
D Catalytic Reforming
Gasoline fractions distilled directly from
crude oil would cause "knock" in your
modern high-compression automobile
engine. In the catalytic reforming process
the chemical structure of the gasoline is
rearranged to improve its anti-knock rating.
E Treating
From the primary refining operations
described in the sections above a wide
range of product streams are obtained. In
most cases the properties of these streams,
either as final products or as feedstocks
for futher processing (for example reforming)
are adversely affected by certain impurities.
These must be removed or converted to
less harmful compounds by further refining
processes called treating". The undesirable
constituents are mainly sulfur, nitrogen,
and oxygen compounds from the original
crude oil and unstable materials formed by
cracking which would later form gummy
residues.
The most modern of the treating processes
is hydrodesulfurization. In this process the
sulfur compounds are converted to hydrogen
sulfide, the nitrogen compounds to ammonia,
and the oxygen compounds to water. The
hydrogen sulfide can be converted to
saleable sulfur by partial combustion with
air.
Older treating processes extract the
undesirable compounds using a variety of
caustic solutions or sulfuric acid. In most
of these processes the solution is
continuously regenerated and the undesirable
extracts are incinerated or recovered for
sale as by-products.
V REFINERY WASTE WATER SOURCES
In a typical refiner, the large-volume sources
of waste water can be grouped in three
categories, as follows:
Table II
Refinery Waste Water Sources
Source
Cooling
Water
Flow, % of Source of
GPM Total Contam-
ination
100-6,000 40-80
Process
leaks, treating
Chemicals and
Concentration
< 10 Treatment and
concentration
20 Direct contact
with oil and
treating chem-
icals
Water 5-300
Softener &
Boiler Blowdown
Refinery ^ 20-1,200
Processes
Crude oil desalting, overhead oily waste from
units such as distillation, cracking, alkylation,
treating, etc.
Although the largest percentage of the water
discharged from a refinery was used for cooling,
purposes, the actual amount varies widely
from one refinery to another. This depends
on whether the cooling system is once -through
or recirculating and to some degree the extent
of use of air coolers.
Cooling water is normally called non-oily.
This is relative, however, since the cooling
water can become oily through leaks in heat
exchangers. These leaks and treatment
chemicals used in the cooling systems are the
main sources of contamination in cooling water.
Pollution in a waste stream from water
softening and boiler blowdown is relatively
minor. Although relatively small volumes of
water are involved, the dissolved solids
content may be high. Chemicals used to treat
the boiler water are the main pollutants.
The greatest sources of pollutants in a refinery
are the so-called process water or oily water
streams. This contamination occurs when the
water is used in direct contact with the
8-2
-------
Complex Wastes Associated With Petroleum Refineries
hydrocarbon process streams. Often this
water was used as steam to strip material
from process streams, such as sulfides or
mercaptans.
The following table lists the pollutants and
approximate concentrations which may be found
in refinery waste water streams.
Table IE
Undesirable Components of Refinery Waste Water
Pollutant Concentration, ppm
Floating and dissolved oil l-> 1, 000
Suspended solids
Dissolved solids 0-5,000
Phenol and other
dissolved organics 0-1, 000
Cyanide 0-20
Chromate 0-60
Organic nitrogen 0-50
Phosphate 0-60
Sulfides and mercaptans 0-100
Caustics and acids 2-11 pH
Color and turbidity
Visible oil on the surface of waste water is
the most common and troublesome pollutant
in refinery waste water. Concentrations can
range from 1 ppm to well over 1, 000 during
accidental spills.
Crude oil entering a refinery usually contains
suspended solids and as much as 1% brine
emulsified in the oil. These impurities are
washed out of the crude using water in a device
called a desalter. Water drained from the
desalter will thus contain suspended dirt and
as much as 5, 000 ppm of dissolved salts. A
relatively high content of dissolved solids can
also be expected in the blowdown from cooling
towers, boilers, and water softeners.
Phenol and cyanide are very important to
water quality criteria. Only very low
concentrations are tolerable in drinking water.
Cyanides are not generally considered as a
major problem to refineries because they are
not often found at significant levels. Phenols,
on the other hand, occur in some crudes and
are formed during cracking, and are a very
common pollution problem in the petroleum
industry. Some process waters contain phenol
concentrations as high as 1, 000 ppm.
Chromium and phosphate compounds are
commonly used as corrosion inhibitors in
cooling water systems. Phosphates are also
sometimes used to treat boiler water.
Ammonia and other nitrogen-containing
compounds are commonly found in the process
waters of cracking units and hydrogenation
units, as the result of decomposition of nitrogen
compounds in the original crude oil.
Mercaptans and sulfides are commonly present
in waste water streams within a refinery.
Special facilities and vigilance are required
to keep them out of the final effluent. These
materials of course are odiferous and can be
detected in very small concentrations.
Caustics and acids are occasionally .used for
treatment of refinery streams, as previously
mentioned. Where these spent treating chemicals
are drained into the effluent water, the presence
of phenols, organic acids, mercaptans, and
sulfides can be expected. Inadvertent spills
of acid or caustic can cause correspondingly
high or low pH in the effluent water. Caustic
or acid extracts also tend to cause a brownish
coloration of the effluent.
This outline was prepared by R. E. Van Ingen,
Coordinator of Design and Development of
New Processes - Shell Oil Company,
New York, NY 10020
8-3
-------
MODERN REFINERY
SIMPLIFIED FLOW DIAGRAM
Crude
Oil
Solvents and Aromatics
'Pitch"
Hrirnon
Glaus
Plant
V
^
I
<
Thermal
Cracking
Or Coking
\
(
I
lk "Cutter" Stock v 1 Residual Fu
"^ \ 'and Asphalt
^ 1
Coke -v
Sulfur
-------
PLATFORM OPERATIONS - OFFSHORE OIL PRODUCTION
I INTRODUCTION
A More than 100 companies are now active
in offshore petroleum, operating off the
coasts of 75 countries. The value of the
work in progress is about $3 billion and
at the end of 1970, the total investment in
the offshore oil industry has amounted to
about $20 billion.
Daily offshore U. S. production is in the
range of 1. 30 million barrels of oil,
representing 14. 5% of the domestic total.
Proved reserves of offshore oil stand at
85 billion barrels, or about 20% of the
estimated world inventory of 425 billion
barrels.
In 1969 approximately 1, 160 wells were
drilled in the offshore U.S. areas. At
the present time there are 2, 564 offshore
platforms, structures and facilities in the
Gulf of Mexico, off the California coast
and in the waters of Alaska. Of this
number, 764 are in navigable (3 miles
from shore) waters. Even though water
is not discharged from all these platforms,
structures and facilities, they do con-
stitute a potential source of pollution due
to blowouts and other accidents.
B Current practice in the offshore oil
industry is to group platforms, structures
and facilities, located in particular fields,
for economy in operation. Thus, for
example, one main platform may serve
as the supporting facility for ten or more
structures. This main platform then
provides living quarters, office space,
treatment facilities and control centers
for the other structures in the group. At
an average bare-bones cost of $8 million,
real estate on these main platforms runs
about $40 per square foot with an average
surface area of 200, 000 square feet. These
surface areas and cost figures play an
important role in the selection of water
treatment equipment.
II TREATMENT OFFSHORE
A The original carboniferous deposits
accumulating within, or at the edge of,
ancient seas constituted the beginning
of petroleum formations. It therefore
follows that some part of those ancient
seas will be produced with the oil and
gas today. This water, which accumu-
lates during the production processing
of oil and gas, is frequently great in
volume sometimes exceeding 20, 000
barrels per day for one field. This
water may constitute from less than 10%
to greater than 50% of the total fluids
produced from a single well.
Depending on several variables, an
offshore operator may decide to:
1 Pump the entire oil/water mixture
to shore for treatment.
2 Pump the oil/water mixture to shore
for treatment following a free-water
knockout process.
3 Treat the oil/water mixture on the
platform and sell the oil to a pipeline
company at the platform.
This last choice requires that the oil
contain a maximum of 2% water and
generally no more than 1% water.
The variables upon which the above
decisions are based include:
1 Distance to shore - 20 to 30 miles is
generally the maximum.
2 The presence and types of solids and
emulsions concerned.
3 The relative specific gravity of the oil
and water.
IN.PPW. 01.13.5.71
9-1
-------
Platform Operations - Offshore Oil Production
4 The chemical characteristics of the
oil - the paraffin content plays an
important role.
5 Economics of treating on shore vs.
on the platform.
6 The percent of water produced with
the oil.
Treatment equipment must take into
account the fact that the above variables
change with time. This requires that
adequate safety factors be included in
design calculations.
There are two basic types of equipment
associated with oil/water separation on
offshore production facilities:
1 Operation equipment
2 Conditioning equipment
Operation Equipment - That equipment
used in the process of separating well
gas from fluids and processing fluids to
remove WATER from the OIL. Depending
upon the throughput volume in operation
equipment, and also upon the presence and
types of solids and emulsions concerned,
the character of the various emulsifying
agents and the relative specific gravity of
oil and water, the oil contamination in the
separated water will frequently be from
200 ppm to 3, 000 ppm or more. As the
water content in the product oil decreases,
the oil content in the effluent water
increases. Therefore, the 2% maximum
(and 1% desired) water content required
by the pipeline company has a direct
bearing on the amount of oil that must be
removed from the discharge, or bleed,
water.
Process units that may be classified as
Operation Equipment include the following:
1 Emulsion treaters
2 Heater treaters
3 Free-water knockouts
4 Phase separators (gas, water and oil)
Prices for this equipment range from
$3, 000 for a 12, 600 gallon free-water
knockout separator (4 hour detention time)
to $52, 000 for a heater treater handling
10, 000 barrels per day.
The free-water knockout and phase
separators are essentially sedimentation
tanks wherein the gas, oil and water
separate by gravity under pressure.
Valves, located at the phase interfaces,
draw off the particular components. The
emulsion and heater treaters make use
of emulsion breakers (either chemical
or heat) to more effectively remove the
water phase.
Conditioning Equipment - That equipment
used downstream from the operational
equipment to treat bleed water prior to
disposal overboard. This equipment
removes OIL from the WATER. Depending
upon the same variables which effect the
operation equipment, the effluent from
the conditioning equipment will contain
from 20 ppm to 200 ppm oil. Close
observation is required in order to
maintain an effluent in the 20 ppm to
50 ppm oil range. This is not always
achieved.
Units which may be classified as
conditioning equipment include:
1 Gravity separators
2 Oil skimmers
3 Clarifiers
4 Gas flotation cells
5 Coalescers
This conditioning equipment can be
installed at a cost of $2 to $3 per barrel
or $20, 000 to $30, 000 for a system
designed to process 10, 000 barrels per
day. This cost is based on the assumption
that the equipment would be customized
and designed to achieve an effluent of
50 ppm oil. This system would occupy
9-2
-------
Platform Operations - Offshore Oil Production
about 300-400 sq ft and would require
3-4 months for delivery. The price
would double if the equipment were
installed after construction of the plat-
form was completed.
Chemical treatment may be used to
provide more consistent results in the
50 ppm oil range. This, however,
generates a large amount of sludge which
is a disposal problem in itself. Operating
data indicate 30 to 500 Ib/day ferric
chloride would be needed to obtain 50 ppm
oil. This would generate 4 cubic feet of
sludge for each pound of chemical used.
Gravity separators, oil skimmers and
clarifiers rely on the gravity separation
of oil from water. Oil is normally skimmed
off the top of these units and water is
drawn from the bottom by way of an out-
side siphon called a "Gun Barrel". These
units are normally used upstream from
other oil removal equipment to eliminate
the bulk of free oil and sedimentation.
Gas flotation units saturate "clean" water
with gas in a pressure tower. This water
is then mixed with the water/oil mixture in
a flotation chamber in which the gas bubbles
expand and carry the oil particles to the
surface where they are skimmed off.
"Clean" water is then drawn off and dis-
charged with a portion being recirculated
to the gasification pressure tower. These
units are capable of removing 90 percent
of the oil from influents ranging as high
as 1000 ppm oil.
In coalescer units the water/oil mixture
enters a settling section where heavier
solids fall out and free oil rises to the
surface. The flow then travels through a
graded filter bed or excelsior section
where oil wetted particles are filtered out
and finely dispersed oil particles are
coalesced to particle size sufficient to
rise out of the water. After filtering, the
water passes to a final settling and surge
section.
New proprietary equipment is being
developed by several companies which,
it is hoped, will reduce the amount of oil
in the bleed water, and at the same time
reduce the equipment space requirements.
To date, this equipment has not been in
service offshore but based on existing
data, it is felt that effluent concentrations
of 10 ppm to 25 ppm oil are achievable.
The space requirements for these units
range from 50 to 80 square feet, with
cost estimates from $20, 000 to $30, 000
installed offshore.
Ill SUMMARY
By 1980 exploratory drilling and possibly
production will be extended to coastal shores
and slopes of about 120 countries. The
estimated value during that year will be
about $ 14 billion and the cumulative value
of offshore operations will be more than
$50 billion.
The offshore oil industry is expanding at a
rapid pace and as the industry grows so does
its associated pollution problems. Present
conditioning equipment is capable of producing
effluent bleed water with oil concentrations
in the 10 to 200 ppm range. If operated
properly, this equipment can discharge
effluents which do not produce oil films,
sheens or discolorations in the receiving
water. The equipment costs about $2 to $3
per barrel per day to install and requires
300-400 square feet of valuable platform
space.
The more efficient equipment which is
currently under development will produce
bleed waters with oil concentrations in a
consistent 10 to 25 ppm range. These new
units are needed so that the offshore industry
can continue to grow without placing additional
loads on an already overburdened environ-
ment.
REFERENCES
1 Van Cleve, H. Office of Oil and Hazardous
Materials, EPA, Washington, D. C.
Personal Communication.
9-3
-------
Platform Operations- Offshore Oil Production
2 Ellis, M.M. and Fisher, P.W.
Clarifying Oil Field and Refinery This outline was prepared by J.S. Dorrler,
Waste Waters by Gas Flotation, Acting Chief, Oil Research and Development
Evangeline Section Regional Meeting, Section, Edison Water Quality Laboratory,
Society of Petroleum Engineers, AIME, Office of Water Programs, Edison, NJ 08817.
Lafayette, LA. November 9-10, 1970.
9-4
-------
BIOLOGICAL EFFECTS OF OIL POLLUTION
I INTRODUCTION
The suffering and mortality caused to birds
by oil pollution, the coating of public and
private property with layers of oil, is ex-
tremely conspicuous and attracts great
public attention and sympathy. We hear con-
flicting statements from competent and re-
spected scientists regarding the biological
effects of these incidents. Why this diver-
gence of opinion? Primarily, because data
upon which to base a sound opinion is either
incomplete, superficial or both.
II EVALUATING EFFECTS OF OIL
It is difficult to evaluate the effects of oil
since it is not a single substance but a
complicated and variable mixture of liter-
ally thousands of chemical compounds. This
fact is clearly demonstrated in Table I which
shows that the toxicity of crude oils alone can
cause mortality in the organism tested from
as high as 89% to a low of 1%. These con-
stituents of oil share many common proper-
ties; however, they also differ considerably
in many properties which influence their
effects on the environment. Among these are:
A Toxicity
Many low boiling aromatic hydrocarbons
are lethal poisons to almost any organism
while some higher boiling paraffin hydro-
carbons are essentially nontoxic to most
forms of life.
B Solubility
Benzene derivatives may be soluble in
water at concentrations around 100 ppm;
naphthalenes at 3C ppm, -virile higher mo-
lecular weight hydrocarbons maybe
essentially insoluble in water. Solubility,
of course, will significantly influence the
toxicity of a component of oil.
C Biodegradability
This varies widely according to such
molecular features as hydrocarbon chain
length and degree of branching. The rate
of degradation, of course, will influence
the persistence of environmental effects.
D Factors such as volatility, density, and
surface- activity which will determine
whether oil components or an oil mixture
will tend to evaporate, sink, or easily
disperse into the water column. Dean
(1968) reports that two thirds of Nigerian
and two fifths of Venezuelean crude oil
will evaporate after a few days.
E Carcinogenicity
Some components of crude, refined, and
waste oils are known to have cancer-
inducing properties. '6'
III EFFECTS OF OIL
A General ^
Oil pollution, whether it be due to the spill
or discharge of a crude oil or a refined
product, may damage the marine environ-
ment many different ways, among which
are:
1 Direct kill of organisms through coating
and asphyxiation.
2 Direct kill through contact poisoning
of organisms.
3 Direct kill through exposure to the
water-soluble toxic components of oil
at some distance in space and time from
the accident.
4 Destruction of the food sources of
higher species.
5 Destruction of the generally more
sensitive juvenile forms of organisms.
6 Incorporation of sublethal amounts of
oil and oil products into organisms
resulting in reduced resistance to in-
fection and other stresses (the principal
cause of death in birds surviving the
immediate exposure to oil).
7 Destruction of food values through'the
incorporation of oil and oil products,
into fisheries resources.
8 Incorporation of carcinogens ini^ the
marine food chain and human food
sources.
WP.OI. 4. 5. 71
10-1
-------
Biological Effects of Oil Pollution
9 Low level effects that may interrupt
any of the numerous events necessary
for the propagation of marine species
and for the survival of those species
which stand higher in the marine food
web.
Because of their low density, relative to
sea water, crude oil and distillates should
float; however, both the experiences of
the "Torrey Canyon" and of the "West
Falmouth" oil spill have shown oil on the
sea floor. Oil in inshore and offshore
sediments is not readily biodegraded; it
can move with the sediments and can
contaminate unpolluted areas long after
an accident.
C Shellfish
(1)
B Waterfowl
(1)
Marine birds, especially diving birds,
appear to be the most vulnerable of the
living resources to the effects of oil
spillage. Harm to the birds from con-
tact with oil is reported to be the result
of a breaking down of the natural insu-
lating oils and waxes shielding the birds
from water and loss of body heat, as well
as due to plumage damage and ingestion
of oil or an oil dispersant mixture. In
addition, birds may be harmed indirectly
through contamination of nesting grounds
or through interruption of their food chain
by destruction of marine life on which the
birds feed.
The possible effects of the spillage on the
bird population will vary with the season.
For example, young birds during the late
nesting season and flightless adults during
the moulting season may be particularly
vulnerable along the shore. Conversely,
various groups of migratory birds may
avoid exposure because of their absence
at the time of the spill. Nonmigratory
birds will be the hardest hit with the pos-
sibility of eliminating an entire colony.
Bird kills in the thousands may result from
a specific spill incident. Efforts to cleanse
or rehabilitate contaminated birds have
generally been unsuccessful with less than
20 percent of the treated birds surviving.
Estimates of the ability of bird groups to
repopulate differ greatly; however, there
is a general concensus that the numbers
of many marine bird types are vastly
reduced from 30 years ago.
Shellfish including mollusks such as clams,
oysters and scallops along with crabs,
lobsters, and shrimp appear to be the
segment of marine life most directly
affected by oil spillage in the coastal zone.
Most of these types will survive contam-
ination by heavy oil alone however the
flavor of the flesh will be tainted. Lighter
petroleum fractions such as diesel or
gasoline appear to be more fatal, and
some species such as clams may exper-
ience significant mortalities. Fortunately,
in most spill incidents, the effects on
shellfish appear to be fairly temporary,
and even in those situations where high
mortalities were observed at the time of
the incident, recovery appears to have
taken place within a period of six months
to two years.
D Fish
(1)
Finfish generally appear to be unaffected
by the presence of spilled oil as their
mobility permits them to avoid areas with-
high oil or chemical concentrations. Dan-
ger to fish is probably limited to possible
harm to eggs, larvae, or juveniles which
seasonally may be found concentrated in
the upper water layers or in shallow areas
nearshore.
E Marine Mammals
(1)
Relatively few observations of any direct
effect of oil spills on larger marine, mam.-
mals such as whales, seals, and sea lions
have been made. These animals appear
to be able to sense and avoid oil on the
surface of the water, and various accounts
of oil-covered animals do not appear to be
substantiated. Possible effects to young
or disabled mammals are viewed as being
comparable to normally occurring mor-
talities, and spilled oil is generally
considered to result in minimal harm to
marine mammals.
F Marshes
"Cowell reports that the short-term effect
of oil on a marsh is that the oil adheres
firmly to the plants and hardly any is
washed off by the tide, except where there
are puddles of oil. Leaves may remain
green under the oil film for a few days,
but eventually they become yellow and die.
Plants recover by producing new shoots,
10-2
-------
TABLE I - Chemical and physical properties of crude oils 1-10 with figures of relative toxicity at different
temperatures. (]_ 4")
Specific Gravity at 16°C/16°C
Sulphur Content %wt.
Asphaltenes Content %wt.
Pour Point °C
| Wax content %wt.
Viscosity at 21°C cSt
Viscosity at 38°C cSt
Total distillate to 149°C %wt.
Total distillate to -232°C %wt.
Total distillate to 343°C %wt.
Total distillate to 371°C %wt.
S.G. at 16°C/16°C of C5 -149°C Cut
S.G. at 16°C/16°C of C5 -371°C Residue
Aromatic content of C5 -149°C Cut %wt .
% Mortality in L. littoral is* at 3°C
% Mortality in L. littoral is at 16°C
1 % Mortality in J.. littoral is at 26°C
*Intertidal Gastropods
1
0.797
0.05
<0.05
27
-
2.34
26.7
42.7
69.7
75.8
0.744
0.842
13.5
45
89
66
2 3
0.843 0.794
0.20 O.I
O.05 NIL
9 13.5
5.1
3.0 1.65
20.1 36.2
37.2 53.2
67.5 75.6
72.5 79.8
0.749 0.731
0.924 0.889
10 i 17
47 24
74 83
47 60
4
0.876
0.96
2.8
7
19.07
8.32
14.6
26.8
48.3
53.6
0.737
.0.961
17
55
63
38
r 5
0.851
1.7
0.5
-26
6
8.2
5.5
17.3
31.5
51.7
56.4
0.705
0.957
8
82
56
56
6
0.869
2.5
1.4
-32
5.5
17.0
9.6
15.3
27.6
44.6
48.7
0.703
0.975
7
71
72
45
7
0.854
1.33
0.7
-21
-J
8.6
5.6
17.9
32.3
52.5
57.4
0.718
0.958
7.5
76
48
62
8
0.89
0.96
0.17
-1
6.5
28.9
13.4
10.7
21.8
43.5
48.4
0.742
0.961
18.5
79
32
53
9
0.851
0.75
0.7
7
11
12.4
6.45
26.3
39.9
60.5
65.1
0.717
0.933
13
7
21
15
10
0.971
2.59
5.8 .
'15
3
3495
739
2.8
7.6
22.7
27.4
0.736
1.013
io
66
1
2
w
5'
h— '
o
H
>-»>
^-*j
a
•>
•ji
o
o
-------
Biological Effects of Oil Pollution
a few of which can usually be seen within
3 weeks of pollution, unless large quan-
tities of oil have soaked into the plant
bases and soil. Seedlings and annuals
rarely recover.
In the long term, recovery from oil spill-
ages has been observed many times (e. g. ,
Buck and Harrison, 1967; Ranwell, 1968;
Stebbings, 1968; Cowell & Baker, 1969).
The cases described cover different salt
marsh communities, different types, vol-
umes and degrees of weathering of oil, and
pollution at different times of year. Veg-
etative recovery from experimental
spraying at different times of year has
been observed (Baker, 1970). The evidence
indicates that marshes recover well from
a single oil spillage, or from successive
oil spillages provided these are separated
by long time intervals. "
G Food Chain
The effects of oil spillage on the marine
food chain or food web (which consists of
plants, bacteria and small marine organisms)
is not well understood because of the wide
fluctuations and cycles that occur naturally
and are totally independent of the effects of
oil. Lower marine plants appear to be
fairly tolerant to contamination by oil and
where destruction has taken place, have
repopulated rapidly although in proportions
varying from original numbers. Some
forms of algae and diatoms, appear to be
stimulated in growth by a certain amount
of oil. Various bacterial organisms will
also feed on available oil and multiply,
thus, providing energy to the protozoan
level of the food chain.
REFERENCES
1 Dillingham Corp. , 1970, "A Review of
the Problem - Characteristics of Major
Oil Spills".
2 Blumer, M., 1970, Personal Correspond-
ence.
3 Murphy, T. , 1970, "Environmental
Effects of Oil Pollution", Presented
at ASCE, July 13, 1970, Boston, Ma.
4 Ottway, S. , 1970, "Comparative Toxicity
of Crude Oils", Field Studies Council,
Oil Pollution Research Unit, Orielton,
U. K.
5 Cowell, E. , et al. , "The Biological
Effects of Oil Pollution and Oil Cleaning
Materials in Littoral Communities,
Including Salt Marshes", FAO Conference,
Rome, 1970.
6 Blumer, M. Oil Contamination in the
Living Resources of the Sea. FAO,
December 1970.
This outline was prepared by R. T. Dewling,
Director, Research & Development, Office of
Water Programs, Edison Water Quality
Laboratory, Edison, NJ 08817.
10-4
-------
OIL CHARACTERISTICS
Outline Number
Chemical and Physical Characteristics of
Petroleum 12
Fate and Behavior of Spilled Oil 13
Oil Sampling 14
Analysis of Oil Samples 15
Microbiology of Petroleum 16
-------
CHEMICAL AND PHYSICAL CHARACTERISTICS OF PETROLEUM
I PHYSICAL CHARACTERISTICS OF -,
PETROLEUM
\(
•f
A Introduction
Crude oil varies in color from black
through various shades of brown and green
to a light yellow. It may be heavy and
viscous such as Bachaquero crude oil
from Venezuela or light and volatile such
as South Louisiana crude oil. The main
physical properties used to characterize
an oil are its specific gravity, API
(American Petroleum Institute) gravity,
viscosity pour point, flash point, cloud
point and ash content.
B Physical Properties
1 Specific gravity is the ratio of the
density of an oil to the density of water
when both are measured at a given
temperature:
s =
do
dw
Where s is the specific gravity, do is
the density (mass per unit volume) of
the oil, and dw is the density of water
(1.000 g/mlat 3.980C).
2 API gravity is defined by the following
equation:
141 s
API gravity = " - 131. 5
Kinematic viscosity is the ratio
of the absolute viscosity to the
specific gravity of the oil at the
temperature at which the viscosity
is measured.
4 Pour point is the lowest temperature
at which the oil will flow,
5 Flash point of an oil is the temperature
at which it gives off sufficient flammable
vapor to ignite. This should not be
confused with the fire point of an oil
which is the temperature at which its
vapors will continue to burn. The
fire point of an oil ranges from IQOto
700 higher than its flash point.
6 Cloud point is the temperature at which
the paraffins of an oil, which are usually
in solution begin to crystallize causing
the oil to become cloudy.
7 Ash content is the amount of non-
combustible material in an oil.
8 Other properties: Many other properties
are also noted for specific types of
petroleum products. For example,
octane number is determined for
gasoline, and viscosity index, an
empirical number indicating the effect
of a change in the temperature on the
viscosity., is determined for lubricating
oils.
where s is the specific gravity of
the oil at 6OOF.
Viscosity is defined as a fluid's
resistance to flow.
a Absolute viscosity is the force required
to move a plane surface area of one
square centimeter over another plane
surface at the rate of one centimeter
per second when the two surfaces are
separated by a layer of liquid one
centimeter in thickness.
II CHEMICAL COMPOSITION OF
PETROLEUM
A Introduction
Another method of classifying a petroleum
product is according to the types of chem-
ical compounds which it contains. For
convenience, a group of definitions is
included.
B Definition of Terms
IN.PPW.ol.!4.5.71
12-1
-------
Chemical and Physical Characteristics of Petroleum
1 Hydrocarbon is a chemical compound
which contains only the elements carbon
and hydrogen.
2 Saturated hydrocarbons are hydro-
carbons which have only single bonds.
3 A single bond is formed when two
valence electrons are shared by two
atoms.
H H
• • • •
H:C:C:H
• • • •
H H
H H
H H
• • • •
H • Ci • • C • H
H H
u
H— C-C—H
u
H H
Figure 2. Carbon-Carbon Double Bond
5 A triple bond is formed when six
valence electrons are shared by two
atoms.
rl • d • • '• C • H
Figure 1. Carbon-Carbon Single Bond
4 A double bond is formed when four
valence electrons are shared by two
atoms.
Figure 3. Carbon-Carbon Triple Bond
6 An unsaturated hydrocarbon is one
which contains one or more double or
triple bonds. The term unsaturated
refers to the fact that hydrogen atoms
are deficient and can be added under
the proper chemical and physical con-
ditions . Thus, ethylene and acetylene
shown in 4 and 5 above, respectively,
are unsaturated hydrocarbons.
12-2
-------
Chemical and Physical Characteristics of Petroleum
An aromatic hydrocarbon is one which
contains at least one 6-membered ring
of carbon atoms and alternate single
and double bonds. Benzene and
napthalene are therefore aromatic.
hydrocarbons.
H H H
Figure 4. Aromatic Compounds,
Top - benzene
Bottom - napthalene
C Chemical Composition of Crude Oils
1 Background
Crude oils vary greatly in composition
but consist mainly of hydrocarbons and
compounds containing oxygen, nitrogen,
sulfur and trace amounts of metals in
addition to carbon and hydrogen.
2 Hydrocarbons are the main class of
compounds present in most crude oils.
The range, however, is a wide one.
Many mid-continent and Gulf of Mexico
crude oils contain 90-95% hydrocarbons
while crude oils of Mexico and California
have only 50% hydrocarbons. The
hydrocarbon compounds in crude oil
consist mainly of paraffins, napthenes,
and aromatic s.
a Paraffins are saturated hydrocarbons
such as propane. A wide range of
paraffins can be found in crude oils.
The light ends, the volatile com-
ponents are mainly low molecular
weight paraffins containing 12 or
less carbons.
1) Straight-chain paraffins are those
in which the carbon atoms are
arranged linearly.
H—C—C—C—H
Figure 5.
propane
H H H
Straight-Chain Paraffin,
2) Branched-chain paraffins are those
which have a linear arrangement of
carbon atoms with other carbon atoms
attached to the carbons of the main
chain.
CH2
I
CH3
PigureG. Branched- Chain Paraffin,
2, 2, dimethylbutane
Napthenes are cyclo-paraffins.
That is, the two ends of an open
chain are joined together, forming
a cyclic structure.
HgC—CHj
HjC—CH.2
Figure 7. A Napthene, Cyclobutane
The cyclo-paraffins of crude oils
consist almost entirely of
cyclopentane and cyclohexane rings
with or without straight or branched-
chain paraffin groups attached to the
ring.
12-3
-------
Chemical and Physical Characteristics of Petroleum
c Aromatics in crude oils are found to
a lesser degree than paraffins or cyclo-
paraffins. They are usually found in
the higher boiling fractions since they
are for the most part of rather high
molecular weight.
d Other hydrocarbons consist of com-
binations of the above three classes.
For example, in the high boiling
fractions napthene rings may be fused
to aromatics with side paraffin
chains attached.
C
I
c c-c-c
c c
•Figure 8. An Alkyl Hydrindene
3 Oxygen- containing compounds in crudes
are almost exclusively acid in nature.
Fatty acids, napthenic acids, and phenols
have been found in very small amounts
in most crudes, but napthenic acids
compose as high as 3% in some Russian
(Baku) and Rumanian crudes. California
crudes have as high as . 5% napthenic
acids in contrast to the trace amounts
found in other USA crudes. Fatty acids
are paraffins with a terminal- -COOH
group.
CH8(CH2)10COOH
Figure 9a. A Fatty Acid, n- dodecanoic acid
4 Napthenic acids are cyclo-paraffins with
a -COOH group attached.
H
« I
COOH
2 \. S 2
H2
Figure 9b. A Napthenic Acid,
Cyclohexanoic Acid
5 Phenols are aromatic compounds with
an OH group attached to the ring.
OH
II
Figure 10, Phenol
c
6 Sulfur-containing compounds
a Crude oils vary in sulfur content
from 0.1% in non-asphaltic
Pennsylvania crudes to as high as
5% in some heavy, asphaltic crudes
of California and Mexico. The
identity of the sulfur compounds in
the high boiling fractions are not
known but those in the low boiling
fractions have been identified as
mercaptans (thiols) and sulfides.
These can be either cyclic, or non-
cyclic or a combination.
1) Mercaptans are paraffins,
napthene, and aromatics with
-S-H groups attached.
12-4
-------
Chemical and Physical Characteristics of Petroleum
C—C—C—C—SH
-C—SH
4 Trace metal compounds are a very
important small component of crude
oils. Vanadium, nickel, and iron
compounds are among the most
prominent. These metals are usually
present as organometallic chelates.
D Classes of Crude Oils are based on the
relative compositions with respect to
paraffinic, napthenic, aromatic, and
asphaltic content. The main types are
shown in. Table 1.
Figure 11. Mercaptans
Top, n-butylmercaptan,
Bottom cyclopentylmercaptan
2) Sulfides are compounds where an
S atom replaces a non-terminal
carbon atom.
c-
-c
TABLE 1
Crude Oil - Classification By Contents
Paraffinic
Napthenic
Paraffinic - Napthenic
Paraffinic - Napthenic - Aromatic
Napthenic - Aromatic
Napthenic - Aromatic - Asphaltic
Aromatic - Asphaltic _ _
Figure 12. Sulfides, Thiophene
Nitrogen-containing compounds are
found in only very small proportions
and consist mainly of quinoline and
pyridine derivatives.
N
Figure 13. Pyridine
E Characteristics of Refined Petroleum
Products
1 Boiling ranges: Petroleum products
are usually classified according to
their boiling ranges. The most common
petroleum products, their boiling
ranges, and approximate molecular
weight ranges are listed in Table 2.
Figure 14. Quinoline
12-5
-------
Chemical and Physical Characteristics of Petroleum
TABLE 2
PRODUCT BP RANGE CARBON ATOMS
LPG
Light Gasoline
Naptha
Kerosene
#1 Fuel Oil
Gas OH
Lube Oils Residuum
#2 Fuel Oil
-450 to
-.50 to
1500 to
1510 to
2100 to
2160 to
2250 to
0.5QC
1500
2100
2700
3306
3430
3600
0 _
4 -
9 -
9 -
12 -
15 -
> 15 -
12 -
4
9
12
16
20
20
20
24
#4 Fuel Oil Heavy straight run or distillate
#5 Fuel Oil Heavy straight run or cracked residual
#6 Fuel Oil Heavier residuum
This outline was prepared by J.P. Lafornara,
Research Chemist, Edison Water Quality
Laboratory, Office of Water Programs, EPA,
Edison, NJ 08817.
12-6
-------
FATE AND BEHAVIOR OF SPILLED OIL
I INTRODUCTION
The tar-asphalt residue of the "weathering"
of oil is a product of a complicated multi-
process phenomenon. The main processes
in roughly the order of occurrence after a
spill are spreading, evaporation, dissolution
and emulsification, auto-oxidation, micro-
biological degradation, sinking and resurfacing
after which the process repeats itself. While
these processes are occurring, the slick may
also be moving.
II MAJOR PROCESSES IN THE DEGRADATION
OF OIL
A Spreading
This process, the first to occur, thins the
slick out to a few millimeters or less and
is dependent on several parameters--among
them, viscosity of the oil, surface tension
of the oil and water, and time.
B Evaporation
Evaporation is the process by which the
low molecular weight compounds of
relatively low boiling point are volatilized
into the atmosphere. The rate of this
process is also governed by many parameters-
among them are viscosity of the oil,
type of oil, and weather conditions, such
as wind and sea state. The major loss due
to evaporation occurs during the first few
days.
C Dissolution
Dissolution is the process by which the low
molecular weight compounds and polar
compounds are lost by the oil to the large
volume of water under and around it. The
rate of this process is also governed by
many parameters including the type of oil,
viscosity of the oil, the amount of oxidation
the oil has undergone before, during and
after the spill and the weather conditions
such as wind, and sea state. Although
this process starts immediately, it is a
long term one and continues throughout
the duration of the total weathering process
since the oxidation and microbiological
degradation processes constantly produce
polar compounds which are finally dissolved
in the water.
D Emulsification
Emulsification is the process by which one
liquid is dispersed into another immiscible
liquid in droplets of optically measurable
size. In the case of oil, the emulsion can
be either an oil-in-water emulsion or a
water-in-oil emulsion.
E Auto- Oxidation
Auto-oxidation is the light catalyzed
reaction by which hydrocarbons react
with atmospheric oxygen to form ketones,
aldehydes, alcohols and carboxylic acids
which are all polar compounds and, there-
fore, can either dissolve in the water or
act as emulsifying agents or detergents.
F Microbiological Degradation
Microbiological degradation is a multi-
faceted process. Certain bacteria,
actinomycetes, filamentous fungi, and
yeasts utilize hydrocarbons and chemically
oxidized hydrocarbons as food sources.
.1 Aerobic microbial oxidation
Most of the microorganisms which
oxidize hydrocarbons require oxygen
in either the free or dissolved form.
When the oxidation of the oil occurs at
the air-water interface there is usually
sufficient oxygen to allow the maximum
biological degradation to occur. How-
ever, areas of activity beneath the
surface in the water column or in
bottom muds are severely limited by
the supply of oxygen.
IN.PPW. 01.12.5.71
13-1
-------
Fate and Behavior of Spilled Oil
2 Anaerobic microbial oxidation
A few organisms are known which
oxidize hydrocarbons when little or
no dissolved or free oxygen is present.
These utilize nitrate or sulfate as their
oxygen source . "Psuedomonas
aeruginosa", for example, utilizes
n-octane or n-hexadecane while reducing
nitrate to nitrite. Many sulfate-reducing
bacteria are known.
Evaporation, dissolution and oxidation of
lighter hydrocarbons may cause the oil to
increase its density. When this happens
to a sufficient degree the oil will sink to
the bottom where anaerobic microbial
oxidation will be the main process of
degradation.
H Resurfacing
If the density of the oil mass is reduced to
a sufficient degree by anaerobic oxidation,
the oil will float again and the processes
above will again occur until the oil has
either completely disappeared or has
reached some land mass.
REFERENCES
1 Fay, James A. The Spread of Oil Slicks
on a Calm Sea, Fluid Mechanics
Laboratory Publication No. 69-G,
Massachusetts Institute of Technology,
Cambridge, Massachusetts. 1969.
2 Blokker, P. C. Spreading and Evaporation
of Petroleum Products on Water, 1964
International Harbor Conference,
Antwerp, Belgium.
3 Smith, J. E. The Torrey Canyon,
Pollution and Marine Life, Cambridge,
University Press. 1968.
4 Scott, G. Atmospheric Oxidation and
Antioxidants, Elsevier, New York. 1965.
5 Davis, J. B. Petroleum Microbiology.
Elsevier, New York. 1967.
6 Holcomb, R.W. Oil in the Ecosystem,
Science, 166,204-206. 1969.
PHYSICAL MOVEMENT OF OIL SLICKS
In the absence of current or debris, an oil
slick will move in the direction of the wind
at a rate about 3-4 percent of the wind velocity.
In the absence of wind or debris, an oil slick
will move in the same direction with the same
speed as the water current. The actual move-
ment will be due to some combination of wind
and current.
This outline was prepared by Dr. J. Lafornara,
Research Chemist, Edison Water Quality
Laboratory, OWP, EPA, Edison, New Jersey
08817.
13-2
-------
OIL SAMPLING
I INTRODUCTION
A A complete oil sampling program is under-
taken for the primary purpose of presenting
legal evidence in a court of law. To pro-
tect the interests of all parties concerned
three basic sampling requirements should
be observed:
1 The sample must represent that oil
which was spilled.
2 The sample must not be physically or
chemically altered by the collection
procedure.
3 Transfer of the sample must be
accomplished using a well defined
chain of custody system.
B The two basic types of oil sample
analysis are:
1 Qualitative - to determine the presence
or absence of oil and to compare the
sample to a suspected source.
2 Quantitative - to determine the amount
of oil present at the spill site.
Collection for qualitative analysis greatly
exceeds collection for other purposes.
For this reason, alternate methods are
under study which will detect the presence
of oil without the requirement for physical
sampling. These methods will use photo-
graphic and electronic sensors and include:
1 Earthbound instrumentation
2 Airborne instrumentation
Earthbound instrumentation would be
deployed in areas of high probability of
spills such as in harbors and near terminals
and refineries. Airborne instrumentation, on
the other hand, would allow occasional
spot checks of other areas and effective
monitoring of cleanup operations.
Ideally, such instrumentation should be
capable of detection, identification and
of providing aerial and thickness measure-
ments .
Methods for tagging oils are also under
study. These methods are grouped into
two categories:
1 Active tagging
2 Passive tagging
Active tagging requires that an inexpensives
coded material be added to oil. This
material must be chemically and physically
stable in both oil and oil slicks. It must
be readily identifiable by available
analytical techniques and it must have
no adverse effect on the oil's subsequent
use.
Passive tagging assumes that oils are so
chemically diverse that their contents
constitute a stable chemical fingerprint
that can be unequivocally disclosed by
laboratory procedures.
Sampling for quantitative analysis is
extremely difficult due to variations in
slick thickness over the spill area. For
this reason experienced, visual obser-
vation will generally provide more
reliable information on the quantity of
oil spilled. Table I is a guide for
estimating the amount of oil on the
water's surface.
II SAMPLE DETERMINATION
A The ideal sampling program is one in
which collections are made BEFORE and
AFTER the spill incident. The very
nature of an oil spill, however, generally
precludes "BEFORE" sampling.
B The types of samples to be collected
depend on the following parameters:
1 Location of the spill
IN. SG. 17.5.71
14-1
-------
Oil Sampling
a Offshore
b Harbor areas
c Inland waters
2 Uses of the area involved:
a Drinking water source
b Shellfish growing area
c Wildlife refuge
d Finfish spawning area
e Recreation
f Commercial fishing
3 Facilities available for analysis:
a Qualitative analysis
b Quantitative analysis
c No analysis
4 Source of spill
a Offshore platform
b Refinery
c Terminal operation
d Storm drain
e Ship - in port
- offshore
TABLE I
Appearance of Slick
Barely discernible
Silvery sheen
Faint colors
Bright bands of color
Dull brown
Dark brown
Amount of Oil
25 gal/sq.mi.
50 gal/sq.mi.
100 gal/sq.mi.
200 gal/sq.mi.
600 gal/sq.mi.
1,300 gal/sq.mi.
C Qualitative analysis is performed to
determine the presence (or absence) of
a particular type of oil. This analysis
may be performed on samples of:
1 Water
2 Fish and shellfish
3 Mud
In addition to direct chemical procedures,
two additional types of qualitative analysis
may also be performed to detect the
presence of oil in water, fish and shell-
fish samples:
1 Taste tests
2 Odor tests
It is emphasized that once a spill has
occurred, qualitative analysis is useless
without a source sample for comparison.
That is, a representative OIL sample
must be collected from the source, such as:
1 The ship - each compartment, bilge
and ballast
14-2
-------
Oil Sampling
2 Offshore platform
3 Terminal - each tank
4 Refinery - various process sources
5 Storm sewer - suspected sources
It may also be desirable to collect benthic,
phytoplankton and zooplankton samples.
However, this should only be done if
BEFORE and AFTER samples can be
obtained and only if a qualified staff or
marine biologists are available for col-
lection, preservation and analysis.
Ill SAMPLE COLLECTION
A Many precautions must be observed when
handling oil samples for analysis since the
character of the sample may be affected
by a number of common conditions
including:
1 Composition of the container--glass
bottles should always be used since
plastic containers, with the exception
of teflon, have been found under certain
conditions to absorb organic materials
from the sample. In some cases, the
reverse is also true in that compounds
have been dissolved from the plastic
containers into the sample itself.
This problem also applies to the bottle
cap liners; therefore, the portion of
the cap that comes in contact with the
sample should be made of glass, teflon,
or lined with aluminum foil.
2 Cleanliness of the container--previously
unused glass bottles are preferred.
If this is impossible, bottles should be
either acid cleaned or washed with a
strong detergent and thoroughly rinsed
and dried.
3 Time lapse between sampling and
analysis--since the chemical charac-
teristics of most oils, especially the
lighter fuel oils, change with time, the
time lapse between sampling and analysis
should be kept to a minimum. If analysis
cannot be completed within 24 hours,
samples can be preserved, depending
upon the volatility of the oil, by
removal of air and exclusion of light.
With heavier type oils, such as No. 4
and residual oils, carbon dioxide may
be used to displace the air. If dry
ice is available, (approximately
0. 5 cu. in.) it may be added to the
sample. As soon as the effervescing
has stopped, the jar should be sealed,
When carbon dioxide or another inert
gas is not available, or in those
instances where volatile components
are present (No. 2 or lighter), the
sample can be preserved by carefully
filling the bottle to the top with water
to displace the air. All samples
should be kept under refrigeration
until analyses are completed.
4 Collection of adequate volume of
sample--it is desirable to obtain as
much of a sample of the oil as possible.
It is suggested that 2 0 mis be con-
sidered as the minimum volume of oil
needed to perform a series of
"identification analyses" on light oils—
No. 2 and below. For heavier oils a
minimum volume of 50 mis is required.
B Oil Sampling Techniques
Sampling of oil presents many difficulties
not immediately obvious. An oil slick
may vary in thickness from several inches
down to a monomolecular layer measured
in microns (10" cm. )„ The quantity of
sample required is therefore important
since such will determine the area of
sweep. For example, 5, 000 gallons of
oil, if assumed to be evenly distributed
over one square mile of water, will
equate to an oil thickness of 0. 0071 mm.
If 200 ml of sample is found necessary,
then all the oil must be recovered from
28 square meters of open water. If
sampling recovery is 50 percent rather
than 100 percent, the sweep area must
be doubled. Table II below describes
theoretical thickness and area, assuming
an even distribution of oil for various
magnitude oil spills.
14-3
-------
Oil Sampling
TABLE II
OIL DISTRIBUTION ON A WATER SURFACE
Spill Area
Gal/Sq. Mile
1, 000, 000
100, 000
10, 000
5,000
1,000
100
Spill Area
ml/Sq. Meter
1430
143
14.30
7.15
1.43
0.143
Area (Sq. Meters)
Req'd to Obtain
200 ml/sample
0.14
1.4
.14
28
140
1400
Oil
Thickness (mm)
1.43
0.143
0.0143
0.0071
0.00143 = 1.43ji
0.000143 = 0.143n
C The ideal oil sampling device should
contain the following characteristics:
1 Be simple to operate
2 Function under diverse conditions
3 Have a few moving parts and not
require electrical power
4 Be inexpensive
5 Collect oil rapidly
6 Not require chemical treatment of
sample
D Current Sampling Procedures
1 Manual Separation
Manual separation is the oldest oil
sampling procedure. The method
involves collection of oil-water mixture
in a container followed by manual
separation of the oil and water phases.
Collection and separation is continued
until about 1 pint of oil has been
collected. The procedure is quan-
titatively inaccurate because of the
crude nature of both the collection and
separation steps.
a Collection devices have included:
1) Simple pail
2) Pail fitted with a bottom tap
3) Sliding plexiglass cylinder whose
fall is controlled by a trigger
4) Dustpan with a stopcock fitted
to the handle
b Separation procedure devices have
included:
1) Manual decantation
2) Separatory funnel
3) Glass filter funnel fitted with a
two-way stopcock
2 Adsorbent materials
Many materials strongly adsorb oil
and other hydrocarbons. Such materials
include teflon shavings, straw,
polypropylene fiber, rope, glass fiber,
paper, and polyurethane foam.
Qualitative sampling requires contact
of the sorbent with the oil followed by
chemical (desorption) or physical
(wringing or compression) recovery
of the sorbed hydrocarbon. Quantitative
sampling requires contact of the sorbent
with a known area of liquid surface;
this application has been impeded by
variable and uncertain adsorption
efficiency.
a French scientists have studied two
applications of textured filter paper.
14-4
-------
Oil Sampling
IV
1) Free floating disks
2) Lined cylindrical containers
At film densities of 650 to 2200 mg/sqm
(2.6 ml/sqm at a density of 0. 85) both
methods sample quantitatively to + 25%
with a single sample.
b Polyurethane foam
Adsorption by polyurethane foam
appears to be a promising procedure.
In practice a 1/4" X 1' sheet is
simply dragged across the surface
until apparent saturation is reached.
The sheet is then passed through a
wringer to recover the adsorbed oil.
When tested with South Louisiana
crude oil this procedure recovered
a sample containing less than 0.1
percent water. Infrared spectro-
graphic analysis revealed no
chemical differences between the
original oil and the sample recovered.
DOCUMENTATION OF EVIDENCE AND
SAMPLES
A Procedures for documentation of evidence
and samples are specified by the National
Oil and Hazardous Materials Pollution
Contingency Plan and its regional deriv-
atives. Collectively these plans guide the
coordinated reaction of Federal, State,
and local government and private agencies
to uncontrolled discharges of hazardous
materials. Documentation procedures
include collection of samples from both
the water course and suspected sources
and preparation of a pollution incident
report (Form FWPCA-209). These
procedures have been established to
document the actual facts of an incident
and to protect the interests of all parties.
B After having been collected as outlined
above each sample should be properly
labeled using the chain of custody record,
Form FWPCA-208 (See Figure 1). The
record should contain the following
information:
1 Sample collection data
This includes name and address of the
agency submitting the sample number,
data and time at which the sample was
taken. A clear description of the source
of the sample and the Jig^atures of the
sample collector and one or more
witnesses. FAILURE TO OBTAIN
THE SIGNATURES OF WITNESSES
MAY RENDER THE SAMPLE LEGALLY
INDEFENSIBLE. Witnesses should
understand that by their signature they
are certifying all information contained
on the custody record, e.g., the date
and time the sample was taken and
description of its source.
2 Shipment certification
This information includes date and
time the sample was submitted for
shipment, the name of individual
from whom it was received, the date
and time it was dispatched, and the
method of shipment, and the name and
address of the consignee. All shipment
information should be certified by an
authorized representative of the common
carrier or a postal official.
3 Certification of sample receipt
The individual receiving the sample
should certify by signature the date
and time of receipt, the name of the
individual from whom the sample wao
received and the proposed disposition.
If the sample is to be shipped to more
than one laboratory, duplicate custody
records bearing the same sample
number should be completed.
In accordance with procedures identified
in the Regional Contingency Plan the on-
scene commander should prepare four
copies of the pollution incident report,
Form FWPCA-209 (See Figure 2), Copies
of the report and additional documents
and attachments should be distributed as
follows:
1 The original and one copy to the
Chairman of the Appropriate Regional
Operations Team.
14=5
-------
Oil Sampling
2 One copy to the Joint Operations Team.
3 One copy to the Headquarters of the
agency supplying the on-scene
commander.
Three areas of the pollution incident report
are especially crucial: Section III
Pollution Data, Section IV Pollution
Sample, and the first endorsement. As
much data, facts, observation and
information as possible should be
included. All statements from persons
directly concerned with the incident
should be signed and witnessed. Although
the on-scene commander may include
other statements and comments, such
information may not be entered as
evidence.
V SUMMARY
Documentation of samples and evidence is
required to adequately protect the interest
of all parties to an incident. The conditions
of collection, shipment and receipt of
samples should be documented with utmost
care to preclude later questions of validity.
REFERENCES
1 Oil Sampling Techniques. Edison Water
Quality Laboratory, Edison, NJ.
December 1969.
2 Oil Tagging System Study. Melpar.
May 1970.
3 Proceedings, Joint Conference on
Prevention and Control of Oil Spills,
API/FWPCA. December 1969.
A full scale oil sampling program is designed
to collect samples, the analysis of which will
be presented as legal evidence in a court of
law. Qualitative and/or quantitative analysis
will be performed on these samples which
may include water, mud, fish and shellfish.
What exactly is sampled depends on several
parameters from the location of the spill to
the analysis equipment available.
Sampling itself is more of an art than a
science. Most methods are based upon
manual collection in a container or adsorp-
tion and subsequent recovery. There is
presently no recognized standard procedure.
This outline was prepared by J.S. Dorrler,
Acting Chief, Oil Research and Development
Section, Edison Water Quality Laboratory,
OWP, EPA, Edison, NJ 08817.
14-6
-------
ANALYSIS OF OIL SAMPLES
I INTRODUCTION
A Oils and oil-water samples are analyzed to
identify the type of spilled petroleum
product or to establish similarity between
samples collected from the environment
and from suspected sources. Common
origin is probable if samples agree in their
. key characteristics.
B Analysis is complicated by effects of
environmental influences and lack of
procedure adapted to oil-water mixtures.
Petroleum analysis is based upon pro-
cedures developed with petroleum products.
C Analysis of environmental samples involves
preliminary cleanup followed by standard
analytical procedures. The complete
analytical sequence shown in Figure 1
involves three levels of activity.
1 Preliminary cleanup intended to
separate the oil from the water and
produce an organic phase amenable to
analysis.
2 Identification of spilled material as a
specific type of petroleum product; e.g.,
gasoline, jet fuel, crude oil, etc.
Identification is accomplished by analysis
according to standard procedure and
comparison of results with prescribed
characteristics of typical petroleum
products. Characteristics of a few
such petroleum products are specified
in Table 1.
3 Further analysis more clearly defines
the relationship between the environ-
mental sample and reference samples
collected from suspected sources.
Results of the analyses are used to
evaluate similarity.
D Both the apparent and suspected nature
of the sample will influence the actual
laboratory procedure. The analyst
himself will normally select the pro-
cedures necessary to accomplish
identification or comparison. The
required level of analysis (e.g.,
identification or identification/comparison)
depends on the nature of the problem.
II CLEANUP
Sample cleanup is commonly accomplished
by one of three basic methods:
A Simple Phase Separation is generally
applicable to distillate fuel oils (Fuel oil
nos. 1,2, and 4, kerosene, gasoline, etc.),
and consists of withdrawing the heavier
aqueous phase from the lighter organic
phase in a separatory funnel. The organic
phase is then dried by passage through
anhydrous CaCl_. The dissolved
petroleum products may be "salted out"
of the aqueous phase by the addition of
Na SO to the water.
B Drying with Centrifugation
When the petroleum product is emulsified
with water (as is the case with some crude
oils and residual fuel oils), it is some-
times possible to break the emulsion by
removal of the water from the matrix with
anhydrous calcium chloride, and then
. centrifuging the sample in a chemical
centrifuge to isolate the oil phase as the
centrifugate.
CH.MET.al.6.5.71
15-1
-------
3
a
ANALYTICAL SCHEME FOR CRUDE OILS
1 1
WBGH
% RESIDUE
KJ II DA HI NITROGEN
ASH WITH
SULFUR 1C ACID
1
INFRARED ANALYSIS
THIN-LA YEI
CH10MAIOOIAPHY
HEXANt-INSOLUUES
INFRARED ANALYSIS
0
-*1
O
w
D
3
^
t
en
* TEMPERATURE PROGRAMING 40-3OO*C
3X SE-10 ON 60/10 CHROMOPORT,
6* » &" COLUMN; SULFUR FLAME PHOTOMETRIC
AND HYDROOIN FLAME IONIZATION DETECTION.
FIGURE 1
-------
Analysis of Oil Samples
TABLE 1
CHARACTERISTICS OF STANDARD PETROLEUM PRODUCTS
PRODUCT API GRAVITY KINEMATIC
(API UNITS) VISCOSITY
(centistokes)
DISTILLATION
RANGE
(I.B.P. - E.P.)
COMMENT
High Gravity
Naphtha
Low Gravity
Naphtha
Gasoline
Jet Fuel
Kerosine
Fuel oil #1
Fuel oil #2
Fuel oil #4
Crude Oil
Fuel Oil #6
45 -
30 -
58 -
40 -
40 -
>35
>26
9 -
13.5 -
-2 -
75
53
62
55
46
36
33.5
18
95°
160°
96°
100°
355°
1.4 - 2.2
<4.3 370°
5.8 - 26.4 420°
- 206° F
- 410° F
- 408° F
- 500° F
- 575° F
- 675° F
(90%)
- 683° F
2.3 - 10.5 40° - >850° F
> 100 > 700° F
Sulfur 0.02%
Contains lead,
halogens
Narrow API
Gravity range
Sulfur exceeds
0.5%
Wide dist.
range
15-3
-------
Analysis of Oil Samples
Phase Separation with Solvent Addition is
accomplished by adding a solvent, such as
chloroform to the oil-water mixture. It is
sometimes possible to obtain a clean
phase separation by solvent addition and
to proceed as in A^ to separate the organic
phase from the aqueous. The organic
phase, after drying with calcium chloride,
is heated to evaporate the solvent.
Ill IDENTIFICATION
A- When cleanup has been completed, the
separated and dried organic phase, is
subjected to analysis. Identification is
normally accomplished by comparison
of sample characteristics to those of
typical petroleum products. Character-
istics of a few typical products are specified
in Table 1.
B The analyses indicated in Figure 1 should
be considered alternatives which the
analyst may select to accomplish identi-
fication. Only a few analyses may be
required in some cases, whereas in other
cases the complete analytical scheme may
be necessary. It is the responsibility of
the analyst to select the combination which
will accomplish the most certain
identification in the time available.
C Analytical Parameters
1 Solubility in organic solvents - Used to
differentiate greases and asphalts from
other petroleum products, and to
distinguish between crude oils and
residual fuel oils from different
locations. Table 2 gives solubility
characteristics for several typical
petroleum products.
2 Specific gravity or API gravity - The
gravity or density is a distinguishing
characteristic of oils. However, since
the loss of volatiles, which occurs in
the early stages of environmental
exposure with volatile distillate fuels
and crude oils results in an increase
of this parameter, it is of limited value.
TABLE 2
SOLUBILITY OF PETROLEUM PRODUCTS
IN ORGANIC SOLVENTS
Solvent
Product
Light Naphtha
Heavy Naphtha
Gasoline
Jet Fuel
Kerosene
Cutting Oil
Motor Oil
Paraffin Wax
White Petroleum
Jelly
Grease
Residual Fuel Oil
Asphalt
VS = very soluble
S = soluble
PS = partly soluble
I = insoluble
Hexane
VS
VS
VS
VS
VS
S
S
S
PS
I
PS
I
Chloroform
vs-
VS
VS
VS
VS
S
S
S
PS
S
S
S
Infrared spectroscopy - Indicates the
relative content of aromatic or carbon-
ring-type compounds. May also indicate
presence of additives such as silicones.
Generally employed to characterize
materials less volatile than #2 fuel oil,
such as #4 and residual fuels.
Average molecular weight - Used to
identify low and high boiling products.
Not commonly employed with other
than pure hydrocarbons.
Distillation range - Defined as the
temperature difference between high
15-4
-------
Analysis of Oil Samples
and low boiling compounds in an oil
observed during distillation. Actual
procedures are specified by ASTM
D 86-56, ASTMD 850, and ASTM D 216.
Reported as the actual temperatures at
which distillation begins and ends:
(l)I.B.P., initial boiling point, and;
(2)E.P., ending boiling point. The
boiling range relates to volatility.
Although potentially valuable, IBP is
useless if the oil has been subjected to
weathering before collection due to
volatilization of lower boiling components.
Typical distillation ranges are presented
in Table 1.
6 Viscosity - -A measure of the resistance
to flow. May be expressed as (a)
Saybolt second units (SSU), the time
required for a standard volume of oil
to pass through a standard orifice, as
specified by ASTM D 445-53T and ASTM
D 446-53; (b) kinematic viscosity at
1000F or 2120F in centistokes (ASTM D
445-65) or in Saybolt Furol units at
1220F. ASTM 2161-63T gives the
relationships between the different
viscosity units.
7 Distillation - As a loss of volatile
components (if present) occurs on
environmental exposure resulting in
an increase of the remaining com-
ponents, these may be put on the same
basis (normalized) by distilling all
samples to a similar degree. This is
accomplished in our laboratory by
distillation in a simple distillation
apparatus to obtain a distillate boiling
point of 275Oc at 40 mm Hg pressure.
The distillate is analyzed by gas
chromatography and the residue for
vanadium, nickel, sulfur, and nitrogen
content and infrared analysis. Column
chromatography may be incorporated
in the analysis.
8 Vanadium is analyzed according to
ASTM D 1548-63.
9 Nickel is analyzed either in the final
solution from the vanadium procedure
by atomic absorption (AAS) or by
dissolving 5g oil in 100 ml of xylene for
determination by AAS.
10 Sulfur is analyzed by the procedure
described in ASTM D 1552-64, using
the Leco induction furnace, or by
ASTM D 129-64, utilizing an oxygen
combustion bomb. In domestic fuel
oils (1967), sulfur values ranged from
0. 001 to 0.45% for # 1 fuel oil; 0. 02 to
1.6% for #2 fuel; 0.2 to 3% for #4 fuel
oil; and 0.4 to 4.25% for #6 fuel oils.
11 Nitrogen is determined by the
Kjeldahl method.
IV SUMMARY
Oil analysis involves three levels of
laboratory activity: sample preparation
and cleanup; basic identification; and final
comparison. Identification as a petroleum
product is accomplished by comparison of
sample characteristics to prescribed
properties of typical products. Further
analysis may be performed to more firmly
establish the similarity between environ-
mental samples and reference samples
collected from potential sources. At all
stages of analysis the judgement of the
analyst is crucial. Typical analyses include
observation of solubility in organic solvents,
infrared spectres copy, API Gravity,
distillation range, gas chromatography,
specific metal determinations, viscosity
measurement, and sulfur determination.
.REFERENCE
1 Kawahara, Fred K., PhD., F.A.I.C.
Laboratory Guide for the Identification
of Petroleum Products, U. S. Department
of the Interior, Federal Water PoUution
Control Administration, Division of
Water Quality Research, Analytical
Quality Control Laboratory, 1014
Broadway, Cincinnati, OH 45202.
2 Kahn, L., Unpublished Data.
This outline was prepared by L. Kahn,
Chief Chemist, Laboratory Branch, Edison
Water Quality Laboratory, Office of Water
Programs, Edison, NJ. 08817.
15-5
-------
MICROBIOLOGY OF PETROLEUM
I INTRODUCTION
While the uses and collection of petroleum
products was known to ancient peoples the
implications of microbial interactions with
these agents has only been explored for about
a century. Concentration of efforts in the
areas of Public Health and characteristics
of individual microorganisms themselves
preceded the study of many areas of value
including the study of petroleum. Since the
1940's, however, increased needs, especially
in the United States, has provided an impetus
to this important field. The relative mag-
nitude of this increase in interest can be
seen from Table 1:
At the present time the number of technologists
directly concerned with petroleum micro-
biology in the world, while difficult to
accurately enumerate, is at least fifty times
greater than 20 years ago.
TABLE 1
SUMMARY OF PUBLICATIONS ON PETROLEUM MICROBIOLOGY
Percent Published Percent Published
Period Total Papers In United States In Europe
1875-1899
1900-1909
1910-1919
1920-1929
1930-1939
1940-1949
12
17
31
65
118
224
8
18.
26
33
50
73
92
82
74
67
50
27
BA.IN.ol.1.5.71 16'1
-------
Microbiology of Petroleum
H THEORIES OF ORIGIN OF PETROLEUM
A Since the 1930's an immense amount of
basic research has taken place regarding
the environment and origin of source
sediments of petroleum. Much of this
research has been under the sponsorship
of the American Petroleum Institute from
privately subscribed funds. An abridge-
ment, for brevity, of the more significant
findings of this outstanding work, designated
as a portion of APIs' "Project 43", is as
follows (with this author's comments):
Finding
1. Biochemically diverse bacteria have
been found in both ancient and recent
marine sediments.
2. Bacteria in abundance have been isolated
from oil well fluids from depths of
several thousand feet.
3. Bacteria are most abundant in ocean
bottom sediments and their numbers
decrease as sediment is sampled in
depth.
4. Laboratory studies have indicated that
certain organic compounds are modified
in the direction of petroleum-like com-
ponents.
5. Certain bacteria are capable of causing
the release of oil from oil-bearing
sedimentary rocks.
Comments
Indicates diverse groups present and
naturally occurring.' These studies
were bacteriological in nature and it
must be emphasized that microorganisms
other than bacteria are capable of
existence and interactions with petroleum.
These effects are still controversial as
to their importance in nature.
This microbial capability has generated
much interest in the areas of oil
prospecting and revitalizing depleted
wells.
16-2
-------
Microbiology of Petroleum
B
IE
At present there is a myriad of theories
regarding the origin of petroleum and its
formation is probably of a complex nature
involving the interactions of many agencies.
It is generally agreed, however, that the
following are true regarding the trans-
formation of organic matter into crude oil:
1 The formation temperatures were low
and probably less than 15QOC.
2 The formation pressures were relatively
low.
3 Formed crude oil is a localized
phenomenon.
4 The marine environment is the primary,
if not the exclusive, forming site.
Since numerous findings have established
that petroleum products can provide a
substrate for microbial activity with
subsequent degradation of the original
material, much controversy has resulted
concerning the relative stability of
petroleum stocks in the earth. Some
possible explanations have been advanced
as follows:
1 Lack or aerobic conditions due to
reducing conditions deep within the
earths' mantle.
2 Preferential breakdown of other com-
•.' pounds within the petroleum mass.
Presence of bacteriostatic substances
(such as metallic ions, hydrogen
sulfide, respiratory products, etc. )
in the sediments, brines, and/or
petroleum.
4 Interactions of these factors.
MICROORGANISMS UTILIZING
PETROLEUM AS A SUBSTRATE
The broad term microorganism is a general
one which is meant to include all of the very
minute living forms such as protozoa, bacteria,
algae, yeasts, molds, etc. Recent compilations
of the microorganisms capable of growing at
the expense of hydrocarbons now total over
100 bacteria, yeasts, actinomycetes and
fungi. Continuing studies of this nature have
brought about the realization that the util-
ization of hydrocarbons is not limited to a
few organisms and that, possibly, they can
serve as routine substrates in taxonomic
classifications.
Numerous genera of bacteria, actinomyces,
and fungi, which are commonly found in soils,
are capable of utilizing the wide range of
hydrocarbons ranging from the paraffin,
kerosene, gasoline, and lubricating and
mineral oils to tars, asphalts, and natural
and synthetic rubbers.
Primary emphasis has been, until recently,
in the areas of investigations relating to the
"problem organisms" and their detrimental
effects upon the industry. Recent concern
regarding treatment practices have ushered
in a wide spectrum of microbiological
investigations.
IV DECOMPOSITION OF HYDROCARBONS
BY MICROORGANISMS
A Substrate Specificity
The utilization of a hydrocarbon or
hydrocarbons by a specific microorganism
does not imply that this substrate is either
the sole source of energy that this orga-
nism is adapted to or one that is
preferentially attacked for metabolism.
In fact, as a rule of thumb, it can be
stated that most hydrocarbon utilizing
microorganisms will oxidize other energy
sources in preference to the hydrocarbon,
•and, in fact, many will show an attenuation
for the original hydrocarbon upon prolonged
exposure to these other sources
(carbohydrates, proteins, fats, etc.) of
energy. Small amounts of these other
energy sources, however, usually speed
up the ability of the microorganism to
oxidize the available hydrocarbon.
As a rule, aliphatic or paraffinic com-
pounds are oxidized more readily than
corresponding aromatic or naphthenic
compounds. Long-chain hydrocarbons
16-3
-------
Microbiology of Petroleum
are more susceptible to oxidation than
those of shorter chain length. Branched
chain, or iso- compounds, are oxidized
more readily than the normal or straight
chained homologs.
B Physical and Chemical Factors
Among a host of factors which control the
rate of petroleum oxidation four can be
singled out as particularly important:
1 Surface area
The magnitude of exposed surface area
to a large degree determines the rate
of oxidation of the petroleum pool.
Since petroleum is relatively insoluble
in water its availability in large surface
area exposures is minimal.
2 Moisture
This universal transport medium is
vital in biological processes and its
relative scarcity in most petroleum
pools severely curtails the decom-
position processes. In such situations
as where water-petroleum interfaces
are available, such as wastewater
discharges, the situation is more
conducive to oxidative processes and
the bulk of microorganism growth and
interactions occur at this interface.
3 Oxygen
This element is vital for the rapid
oxidation of petroleum. In its absence
the decomposition of petroleum can
occur, under anaerobic conditions, at
a much reduced rate.
4 Minerals
The principal requirements here are
for available nitrogen, phosphate,
sulfate, and other trace minerals.
Some of these minerals may be lacking
in the environment and the decomposition
processes may be remarkably slow.
V SELECTED REFERENCES
Since microorganisms do not fit an unchanging
pattern with respect to biochemical inter-
actions, and, to avoid a "cataloging" of
numerous genera of microorganisms, the
following is presented to offer information
on a wide range of interest of scientific
investigation. Each of these individual
study areas must be considered as an
abstracting of a published paper, which
should be consulted for a complete treat-
ment, which is utilized, for purposes of this
outline, to offer an insight to some studies
on the wide spectrum of hydrocarbon products.
2
A Survival of Bacteria in Cutting Oils
The presence of bacteria in cutting oils
is undesirable since they can:
(1) interfere with desired qualities;
(2) form objectional odors; (3) contribute
to dermatitis and infections; (4) contribute
to corrosion; and (5) in certain oils form
objectional discolorations and de-
emulsification tendencies.
In this study thirty different species of
bacteria were tested for their survival
times in nine different cutting oils.
Gram negative bacteria were capable of
surviving for considerable periods of time
while the Gram positive bacteria were
soon killed. Medium straight and emul-
sion type cutting oils permitted survival
of the bacteria for longer periods of time
than the heavy straight type cutting oils.
B Microbiological Sludge in Jet Aircraft
Fuel 3
' This study was undertaken by the author
due to equipment malfunction and diffi-
culties in line aircraft of the U.S. Air
Force. Initial experiments were designed
to follow-up on the guide lines previously
established at the author's laboratory
(Bakamauskas 4, 1948): (1) establish the
presence of microorganisms in the sludge;
(2) isolate the bacteria in pure culture;
(3) establish whether or not the bacteria
16-4
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Microbiology of Petroleum
could cause sludge; (4) determine whether
or not approved corrosion and gum
inhibitors, normally added to the fuel,
were bacteriostatic agents; and (5)
investigate selected water soluble, fuel
insoluble, chemical compounds as
bacteriostatic sludge inhibitors Many
bacteria were isolated in pure culture
from seven types of media. Further
studies were conducted with the cultures
characterized by rapid growth. Some of
these produced very stable emulsions of
the fuel and water; others produced gumlike
residues in the water phase; and some
produced objectionable water-soluble
colorations.
Experiments involving the use of fuel-
soluble inhibitors disclosed that these
were, for the most part, unsatisfactory
since at the usual prescribed concen-
trations they would either prove to be
temporary in effect or totally lacking in
bacteriostatic action to the isolated
cultures. Some success was achieved
with different control agents and con-
tinued research is in progress in this
area.
C Microbial Degradation of Normal Paraffin
Hydrocarbons in Crude Oil °
Fifty active oil degrading cultures were
isolated in enriched seawater containing
crude oil. Oil degradation was measured
with gas chromatography, wet combustion,
and by measurement of surface tension.
Normal paraffin hydrocarbons through C-26
were degraded by two different groups of
microorganisms--those growing in the oil
phase only and those growing in the aqueous
phase. Microbial degradation of 35 to 55
percent of oxidizable crude oil occurred
within 60 hours.
D Reclamation of Soil Contaminated With
Oil6
It is the general opinion that soil is never
permanently sterilized by oil and that
partial reclamation occurred naturally
within about three years. The practice
of aeration, fertilization, and manuring
were definitely beneficial. These opinions
were verified by growth chamber techniques
using a variety of crops. The amount of
oil that plants could tolerate was found to
be species dependent suggesting another
possible way to reclaim contaminated
•soil (previous literature indicates that
small amounts of oil were innocuous and
a conservative estimate of 1 kg oil/sq
mile of surface area being the point where
plant damage begins.)
Use was made of the bacteria Cellulomonas
sp. to seed soil and hasten decomposition
of oil. This method was effective at high
levels of oil contamination using the
criteria of CO_ evolution and seed germi-
nation. Seeding with microorganisms
supplied with nutrients significantly
increased the rate of soil reclamation
over the use of fertilizer alone.
REFERENCE
1 Beerstecher, E. Petroleum Microbiology.
Elsevier, Amsterdam. 1954.
2 Bennett, E.O. and Wheeler, H.O.
Survival of Bacteria in Cutting Oil.
Appl. Microbiol. 2:368-371. 1954.
3 Prince, A.E. Microbiological Sludge in
Jet Aircraft Fuel. Devi, in Ind.
Microbiol. 2:197-203. 1961.
4 Bakamauskas, S. Bacterial Activity in
JP-4 Fuel WADC 58-32. March 1958.
5 Miget, R.J., Oppenheimer, C.H.,
Kator, H.I., and LaRock, P. A.
Microbial Degradation of Normal
Paraffin Hydrocarbons in Crude Oil.
Proc.-Joint Conf. of Prevention and
Control of Oil Spills. API and FWPCA
December 15-17, 1969.
6 Schwendinger, R.B. Reclamation of Soil
Contaminated with Oil. Jour, of the
Inst. of Petrol. 54:182-197. 1968.
This outline was prepared by Rocco
Russomanno, Microbiologist, National
Training Center, OWP, EPA, Cincinnati, OH
45226.
16-5
-------
OIL SPILL PREVENTION, CONTROL AND TREATMENT
Outline Number
Oil Tanker Operations 17
Treatment of Oil Spills - Dispersants 18
Proposed EPA Tests on Oil Dispersant Toxicity 19
and Effectiveness
Treatment of Oil Spills -
Sinking Agents 20
Burning Agents 21
Gelling Agents 22
Sorbents 23
Control of Oil Spills - Booms 24
Treatment of Oil Spills, Oil Skimming Devices 25
Cleanup of Oil-Polluted Beaches 26
Waste Treatment Methods for Refineries 27
-------
OIL TANKER OPERATIONS
I INTRODUCTION
Today's world tank ship fleet amounts to
about 4000 ships with a total dead weight
tonnage of 170 million long tons. Only about
400 ships are American registered.
These tankers range in tonnage from 2000
tons to 312, 000 tons and Japan, the world's
largest shipbuilder, is building a 470, 000
ton tanker.
Supertankers are a recent phenomena. The
first 100, 000 ton tanker went into operation
in late 1959. Today there are over 200
tankers of 100, 000 tons or greater in size
and about 240 under construction. Only
22 percent of these tankers are owned by
oil companies. Another 18 percent are owned
by the governments of the world and the
remainder are privately owned. These
privately owned tankers are contracted for
by the oil companies.
There are two basic trades; the crude oil
trade and the oil products trade. The
supertankers are used almost exclusively
in the crude oil trade. Shifting of ships from
one trade to another are infrequent, however,
when they occur the tanks must be thoroughly
cleaned especially for transfer from the crude
to the products trade.
II SOURCES OF OIL DISCHARGED INTO
SEA FROM TANKER OPERATIONS
A Bilge Oil: Is that oil which collects in the
ship's bottom through seepage or leakage.
B Slop Oil: Is that oil/water emulsion which
is normally collected in an aft center tank
as the residue of tank cleaning operations.
C Overflows: An overflow of oil usually
occurs during the loading or discharge
of cargo and the transfer of cargo from
one tank to another. This is usually
caused by carelessness or inattention.
D Ballast Water: This is normally sea
water taken into empty cargo tanks to
give the vessel stability. The "empty"
cargo tanks usually have a residue of
oil in them.
E Collision or Groundings: Whenever a
loaded tanker vessel is involved in a
collision the result is usually a major
discharge of oil into the surrounding
waters. Groundings are the most
common types of accidents but they do
not usually result in major oil spills.
Ill TANK CLEANING OPERATIONS
A Surface Area: The inner surface of a
cargo tank, if inspected closely, would
be found to be rough, uneven and pock-
marked with thousands of minute pore
openings. The total surface area of the
interior of the cargo tanks of a T-2
tanker is approximately eight and one
half acres.
B Clingage: When a beer glass is filled and
emptied a certain amount of the liquid
adheres to the side of the container. This
is the liquid required to "wet" the surface
of the container. It will vary in amount
as a function of its viscosity, temperature,
volatility and the roughness and con-
figuration of the container.
In the same way, a certain quantity of oil
under fixed conditions is required to wet
the surface of the tanks of a tanker. Under
average conditions based on long experience,
it has been found that this quantity varies
from 0.20% to 0.40% of the cargo. A
median figure might be 0.30%. This
means that if 250, 000 barrels of average
oil cargo were loaded into a tanker and
the tanker immediately pumped out, only
99. 7% of the oil would be recovered in the
shore tanks and 0. 30% or 750 barrels would
remain in the ship. The oil remaining in
the ship would be found to be adhering to
IN.PPW.ol.8.5.71
17-1
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Oil Tanker Operations
the tank surfaces with a very small
portion laying in shallow puddles at the
suction "bell mouths" in the tank and
cargo piping.
C Butterworth System: An operation of
great significance in connection with the
waste oil resulting from tanker operation
is the system used for cleaning or washing
down the tanks. Until the early 193O's,
the cleaning of tankers was accomplished
by long periods of steaming followed by
hand washing with streams from fire hoses.
There was then developed a system for
machine washing of the tanks consisting
of opposed revolving nozzles connected
to a hose lowered to various levels in the
tank to be washed. These nozzles revolve
around both a vertical and horizontal axis
by the action of a water turbin driven by
the washing water at a pressure of about
160 pounds per square inch and a temp-
erature of 170 to 180°F. This is known
as the Butterworth System.
IV LOAD ON TOP PROCEDURES
A Background: Shell introduced the 'load-on-
top' system in 1962. Other major oil
companies soon followed, and today,
encouraged by the oil industry, about 75
percent of the world's crude oil tankers
practice the technique. Refineries of the
major oil companies accepted 'load-on-
top1 residue after an experimental period
in which they proved to themselves that
the residue can be processed through the
refinery unit—if it is less than 1 percent
of the total crude cargo, and if the water
content of the residue is less than 0.15
percent of the total cargo. The main
problem facing the refinery operator is
the removal of salt from the small amount
of sea water discharged with the residue.
The problem of the tanker operator, then,
is to remove as much water as possible
from beneath the oil--without discharging
the oily waste itself.
B Principles of System: What are the
principles of the Load-On-Top system?
This is best described by Kluss :
In the 'load-on-top' system, tanks are
washed in this way during the ballast
passage. The tank washing residues are
accumulated in one tank. Most of the
clean water in this tank is then carefully
drawn off the bottom of the tank and dis -
charged overboard, discharge being halted
whenever oil traces appear in the water
stream. The tank is allowed to settle,
the oil wastes in the tank separate and
float to the surface, and additional water
is repeatedly withdrawn carefully from
the bottom and discharged as before from
beneath the floating layer of oil. Heat
may be applied to hasten the separation
of oil and water. Some companies
occasionally add a demulsifier as well.
When all possible water has been with-
drawn, the next cargo is loaded on top
of the remaining residues in this tank.
Usually, this one compartment is
segregated from the remainder of the
cargo during discharge. Then the
segregated material can be directed,
as the specific situation dictates, to the
fuels processing side of the refinery, to
the refinery slop system for ultimate
recovery, or mixed with the rest of the
cargo being discharged.
C Pitching Ship: In a rolling pitching
vessel, this is no small task. It is
estimated that the oil content of the
water discharged into the vessel's
wake from the 'load-on-top' tank is in
the region of 200 ppm, slowly increasing
to 400 ppm and finally rising momentarily
to 5000 ppm at the shut-off point. A
tanker decanting this residue will not
pollute the sea. Even the momentary
maximum of 5000 ppm is only half of
. one percent. The turbulence in the
moving ship's wake would immediately
dilute any oil to a tiny fraction of its
original concentration. If a vessel
experiences rough weather on its way
to the loading port and the water in the
'load-on-top' is therefore not reduced
to an acceptable level, fresh crude oil
can still be loaded on top. But at the
discharge terminal the mixture at the
bottom of the tank must then be retained
on board to be put through another
'load-on-top1 cycle.
17-2
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Oil Tanker Operations
D PPM of Oil Discharged - "Eyeball
Method": 'load-on-top' is a questionable
first step in the prevention of pollution
of the sea by oil. There are many
questions left unanswered. Members of
the oil shipping industry admit that, at
present, the best method of measuring
the PPM of oil in an oily water discharge
is by the "eyeball" method. This means
that a member of the ship's crew must
constantly watch the overboard discharge
until black oil is seen with the naked eye.
The crew member then signals to the
pump man who in turn starts closing the
discharge line. This may take from
fifteen to thirty seconds. In the mean-
time, a significant amount of oil is lost
overboard. In the 'load-on-top' papsr,
the author admits that at times, the
discharge of oil waste into the sea reaches
a height of 5, 000 PPM.
E Emulsions: The basic problem of the
'load-on-top' system is the question,
"how much oil is contained in the water
being decanted into the sea?"
Emulsions take either one of two forms--
an oil in water emulsion or a water in oil
emulsion. The latter, of which the famous
"chocolate mousse" is formed, is much
more difficult to break than the former.
The oil industry as a whole, has spent
literally millions of dollars trying to
separate oil from their wastewater dis-
charge. This is still a major problem
in the industry today. If the sophisticated
oil/water separators of the major
refineries cannot successfully remove
all of the oil from an effluent discharge,
how can we believe that a simple type
gravity separator on board a rolling ship
can effectively accomplish this?
V TANKER TERMS
A Gross Tonnage: One hundred cubic feet of
permanently enclosed space is equal to
one gross ton-it has nothing whatever to
do with weight. This is usually the
registered tonnage although it may vary
somewhat according to the classifying
authority or nationality.
B Net Tonnage: This is the earning capacity
of a ship. The gross tonnage after
deduction of certain spaces, such as
engine and boiler rooms, crew accommo-
dation, stores, equipment, etc. Port and
harbor dues are paid on Net Tonnage.
C Displacement Tonnage: This is the actual
weight in tons, varying according to
whether a vessel is in a light or loaded
condition. Warships are always spoken
of by this form of measurement.
D Deadweight Tonnage: The actual weight
in tons of cargo, stores, etc. required to
bring the vessel down to her load line,
from the light condition. Cargo dead-
weight is, as the name implies, the actual
weight in tons of the cargo when loaded, as
distinct from stores, ballast, etc.
E Innage: That space occupied in a product
container.
F Outage: Space left in a product container
to allow for expansion during temperature
changes it may undergo during shipment
and use.
G Ullage: That amount which a tank or
vessel lacks of being full.
17-3
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Oil Tanker Operations
VI SINGLE POINT MOORING SYSTEMS
The tankers in the world fleet are growing
bigger each year while the ports serving
these supertankers are still in the World
War T-2 class. The industry, therefore,
advocates the Single Point Mooring System.
A Conventional Mooring System: The
conventional mooring system uses fixed
mooring buoys plus the fore and aft
anchors of the vessel to be moored. The
connecting hose to the underwater pipeline
is connected to a small floating buoy,
which is retrieved when the ship is in a
fixed position. The known objections to
this system are: (1) the vessel cannot
remain in this position in rough weather,
and (2) when the weather turns bad, it
takes too long for the ship to un-moor
and lift anchors.
B "T"-Jetty Mooring System: Some of these
jetties are as long as 6, 000 feet. The
"T" head at the end of the jetty can be
constructed to berth as many as eight
tankers simultaneously. One of the
advantages of this type of installation
is that four pipelines can service six to
eight berths simultaneously. The dis-
advantages of this type of installation are:
1 Extremely expensive to construct.
2 Ships must stop off-loading during
bad weather, and slip moorings.
3 Approach speed to the installation for
large tankers can only be at 1/10 knots.
The problem here is that tankers
personnel cannot sense true speed
during approach and if the vessel strikes
the installation at speeds over 3/10 of
a knot, a large amount of damage can
be expected. A new experimental
radar system is being tried to overcome
this objection.
C Sea Island Mooring System: This system
has the same advantages and disadvantages
as the "T"-Jetty Mooring System. In the
Sea Island System the oil can either be
pumped ashore through underwater pipe-
lines or the oil can be stored on the island
to be later trans-shipped to shore
installations by smaller tankers and
barges.
D Single Point Mooring System: While the
Single Point Mooring is relatively new
in the oil industry (1959), this system is
gaining a widespread acceptance through-
out the industry as a reasonable cost
expense and an effective method to off-
load or on-load a tanker. The Single
Point Mooring System can handle tankers
in much rougher weather than any of the
aforementioned systems. One of the
great advantages of this type of system
is that the wind, high seas and tide forces
straining against the ship is only 1/6 of
the forces received at other mooring
systems. This is due to the fact that the
ship "weathervanes" around the Single
Point Mooring System buoy, bow forward.
At the present time, the industry con-
siders the Single Point Mooring System
as the next best thing to a harbor mooring.
Shell Oil Company and IMODCO of
California are the only two producers of
SPM Systems at the present time.
However, Standard Oil Company (N. J.)
is in the process of patenting and con-
structing an SPM System utilizing a single
anchor mooring which they believe will
be superior to the present system. This
SPM System, considered a third generation
type, will have an underwater swivel
joint. This buoy will have a rigid type
conduit from the sea floor to a swivel
connection approximately 70 feet below
the water surface. When there are
sufficient numbers of SPM buoys through-
out the world, tankers will convert to bow
loading manifolds. The cost of conversion
- to this type of loading will be approximately
$70, 000 per tanker.
VII FUTURE IMPROVEMENTS TO TANKER
OPERATIONS
Because of world concern regarding oil
pollution of the sea, governments of the
world under United Nations sponsorship
are meeting to discuss ways of improving
tanker operations to reduce or eliminate
oil pollution.
17-4
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Oil Tanker Operations
Four of these proposed improvements are:
A Limitation on tank size - this involves
limiting tank sizes on all tankers to
30, 000 cubic meters. It is now in the
process of adoption.
B Compulsory installation of radar and
bridge-to-bridge telephone - both are
designed to reduce the occurrence of
collisions and to improve navigation.
Radar installation is now under discussion
by various U.S. agencies. Congress has
for approval regulations requiring installa-
tion of bridge-to-bridge telephones on all
ships operating in navigable waters of the
United States.
C Establishment of compulsory sealanes -
discussions are now being held at the
international level on adoption of sealanes.
In some restricted waterways (Dover Straits)
sealanes have been established.
D No deballasting at sea - proposed by the
United States at various international
conferences. Earliest adoption cannot
be before 1975 and will likely be later.
This would be the most preferred solution
since deballasting, even with utilizing
Load On Top, is considered the greatest
single source of pollution.
REFERENCES
1 Kluss, W.M. Prevention of Sea Pollution
in Normal Tanker Operations. Institute
of Petroleum Summer Meeting, Brighton
paper No. 6. Mobile Shipping Co. Ltd.
1968.
2 Moss, J. E. Character and Control of
Sea Pollution by Oil. American
Petroleum Institute, Division of
Transportation, Washington, D. C. 1963.
This outline was prepared by H. J. Lamp'l,
Oil Spills Coordinator, Office .of Water Programs,
EPA, Edison Water Quality Laboratory,
Edison, NJ 08817.
17-5
-------
TREATMENT OF OIL SPILLS
DISPERSANTS
I BACKGROUND HISTORY
As far back as the early 1930's water
emulsifiable degreasers were used. These
degreasers were developed to answer the
need for effective methods of cleaning oily
and greasy surfaces. They possessed the
properties of dissolving or dispersing in the
grease or oil, and making the resultant
mixture dispersible in water so that it could
be flushed away with water.
The early products were composed mostly of
soaps and solvents. The demands of the
petroleum shipping industry required products
that could be used effectively aboard ship with
seawater. This led to the use of materials
other than soaps as emulsifying agents because
soap breaks down in seawater. Sulfonated
petroleum oils and later more sophisticated
synthetic detergents made their appearance
in these products.
These emulsifying degreasers were widely
used aboard ship for engine room maintenance,
as well as for the clean-out of petroleum
cargo tanks prior to welding repairs and prior
to upgrading of cargo.
Because of their effectiveness in clean-out
of oil residues it was natural that they should
be tried for treating oil spills. In some cases
they were incorporated in oil slops prior to
dumping overboard to minimize slick formation.
There are presently over 200 commercially
available products which are claimed useful
for dispersing oil from the surface of the
water. These products have been referred to
as "soaps", "detergents", "degreasers",
"complexing agents", "emulsifiers", and
finally "dispersants". This latter term
describes best what this type of product is
intended to accomplish--the dispersion of
oil from the surface into and throughout the
body of water--and therefore is the preferred
terminology.
II COMPOSITION
The primary components of dispersants are
surfactants, solvents and stabilizers.
A Surfactants or Surface Acting Agents (SAA)
This is the major active component in
dispersants.
By their affinity for both oil and water,
surfactants alter the interaction between
oil and water so that the oil tends to
spread and can be more easily dispersed
into small globules--or into what we
commonly call an emulsion.
These agents are often defined according
to their behavior in aqueous solutions.
These solutions will usually wet surfaces
readily, remove dirt, penetrate porous
materials, disperse solid particles,
emulsify oil and grease and produce foam
when shaken. These properties are
interrelated; that is, no surface active
agent possesses only one of them to the
exclusion of the rest.
SAA can be divided into two broad classes
depending on the character of their
colloidal solutions in water. The first
class, ionic, form ions in solution, and
like the soaps are typical colloidal
electrolytes. The second class, the non-
ionic, do not ionize, but owe their
solubility to the combined effect of a
-number of weak solubilizing groups such
as ether linkages or hydroxy groups in the
molecule. A more detailed discussion of
SAS is covered in reference (1).
Commonly used SAA in oil spill dispersants
include soaps, sulfonated organics, phos-
phated esters, carboxylic acid esters of
polyhydroxy compounds, ethoxylated alkyl
phenols and alcohols (APE, LAE), block
polymers and alkanolamides.
IN.PPW.ol.20.5.71
18-1
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Treatment of Oil Spills
B Solvents
Since many of the surface active agents
applicable to oil spill dispersant com-
pounding are viscous or solid materials,
some form of solvent is often necessary
in order to reduce viscosity for ease of
handling. In addition, the solvent may
act to dilute the compound for economic
reasons, to depress the freezing point for
low temperature usage, to enable more
rapid solubility in oil, and to achieve
optimum concentration of surface active
agent for performance reasons. The
presence of a suitable solvent also serves
to thin the oil to be dispersed, reducing
viscosity and making it more easily
emulsifiable. The solvent usually com-
prises the bulk of the dispersant product.
The three general classes of solvents used
in oil spill dispersants are petroleum
hydrocarbons, alcohols or other hydroxy
compounds, and water.
1 Petroleum hydrocarbons
Petroleum fractions with boiling points
above 30QOF are usually used, and these
may produce finished dispersants with
flash points as low as llOop. The
proportion of aromaticity is of concern,
since this effects solubility and emul-
sification properties as well as toxicity.
Wardley Smith, Warren Springs Lab,
UK, in describing the Torrey Canyon
incident, reported that the aromatic
solvents used were 10 times as toxic
to marine life as were the surface
active agents. Some typical fractions
of applicable petroleum solvents include
mineral spirits, kerosene, #2 fuel oil,
and heavy aromatic napthas which con-
tain significant quantities of higher
alkylated benzenes.
2 Alcoholic or hydroxy group of solvents
Includes alcohols, glycols and glycol
ethers. These solvents also lower the
viscosity as well as the freezing points
of finished dispersants. In addition,
they furnish a co-solvent effect, often
needed to mutually dissolve the various
ingredients in a dispersant for stability
of the compound in storage. This group
of solvents may be used in conjunction
with petroleum hydrocarbons as well
as with aqueous solvent systems.
Some of the more frequently encountered
chemicals in this group include ethyl
alcohol, isopropyl alcohol, ethylene
glycol, propylene glycol, ethylene
glycol mono methyl ether, ethylene
glycol mono butyl ether, and diethylene
glycol mono methyl ether. The more
volatile members of the group are quite
flammable.
3 Water
Least toxic, least hazardous and most
economical of the solvents. It lacks
solubility or miscibility with oils.
Where water is used as the solvent,
special problems exist in the choice
of surface active agents and other
additives in order to provide the
necessary miscibility with oils.
Glycols and alcohols are used to aid
in miscibility as well as freezing point
depression when water is used.
C Additives - Stabilizers
Third major component in dispersants,
they may be used to adjust pH, inhibit
corrosion, increase hard water stability,
fix the emulsion once it is formed, and
adjust color and appearance.
Ill DISPERSANT USE
A General
Dispersants theoretically serve to increase
the surface area of an oil slick and disperse
oil globules throughout the larger volume
of water thereby aiding in accelerated
degradation of oils by microbiological
means. The chemical dispersants do not
themselves destroy oil. They vary con-
siderably in toxicity, effectiveness and
ability to stabilize the oil after extended
periods of time. Technology for proper
application of dispersants over large oil
slicks with necessary mixing is currently
18-2
-------
Treatment of Oil Spills
lacking. Use appears far more critical
in harbor and estuary areas and in
proximity to shore. Particular care must
be exercised where water supply might be
affected. The desirability of employing
dispersants in the open sea remains
unresolved although their use here (the
ocean) is potentially more promising
pending additional field data. After wide-
spread dispersant use during major
incidents, reports led to the conclusion
that dispersants or the dispersant-oil
mixture caused more damage to aquatic
life than the oil alone. For beaches, they
actually compounded the problem by adding
to the amount of pollutants present, by
causing the oil to penetrate more deeply
into the sand, and by disturbing the sand's
compactness, so as to increase beach
erosion through tidal and wave action.
B Toxicity
Current information indicates that
dispersants vary considerably in toxicity.
The combination of oil and dispersant may
increase the toxicity of either the oil, the
dispersant chemical or both. The
possibility of this "synergistic" action
must be carefully examined before whole-
sale application of such a product is
permitted. Dispersing of the oil, which
has toxic components, may also compound
the damage.
The toxicity of 40 dispersants, as reported
by the Fisheries Laboratory, Burnham on
Crouch, UK, is shown in Table I. It is
important to point out that the dispersants
used during the Torrey Canyon incident
were mostly solvent based and highly toxic,
killing marine organisms at concentrations
of 10 mg/1. Chemicals available today are
much less toxic.
C Application
(2)
A common method of dispersant application
is by the water eductor method. A con-
trolled amount of dispersant is educted into
a water stream such as a fire hose. This
water jet is an effective vehicle or carrier
for the dispersant and provides good
coverage in treating the slick.
This application procedure however,
while compatible with a water base system,
may be incompatible with a petroleum
base system. This is because a dispersion
of the petroleum solvent-in-water is formed
as soon as the surfactant system is educted
into the water stream. As illustrated in
Figure 1 this accounts for the milky white
appearance of the water after such
applications. In this state, as graphically
shown in Figure 1, it is difficult for the
surfactant to transfer from its termo-
dynamically stable location at the
petroleum solvent-water interface to the
oil spill-sea water interface. Therefore,
for a petroleum base system, neat
application of the chemical directly onto
the oil slick is a more effective application
method.
The prompt application of mixing energy
after the dispersant (solvent or water
base) has been applied is particularly
important. In essence, small oil droplets
must be produced while the immediate
water environment is surfactant-rich.
Water Stream
-./ Water Compatable
Water
Base
Dispersant
p * "" X Surfactant
P o **
Oil Compatable Surfactant
'Tled-Up' In Solvent-
Jn-Water Emulsion
Water
H_
Oil
Base
Dispersant
Solvent \ \~-~yjy " ef&\
Droplets "^V^ ^ \
\ ' \
*T ^ — *~" : ~~
FIGURE 1
18-3
-------
OD
I
TABLE I(3)
Static Bioassays - TL50 48 Hours @ 15°C (ppm)
D
a
8
?
Solvent emulsifiers
Gamlen OSR
Po lye lens
Six ' ' . •
BP 1002
Cleanosol
Essolvene.
'Gamlen D
Gamlen CW
Atlas 1901
Slickgone 1
Slickgone 2
Shamash R1885
Crow Solvent M
DS 4545
DS 4545 in Pink Paraffin
DS 4545 in IPA
DS 4545 in IBA
Aquae lene
Pandalus
montagui
Pink Shrimp
12.5
8.5.
12.1
5. '8
• 32
. 8.6
11.5
. . 14.6
87.2
5.2
4.5
1-3.3
Crangon
crangon
Brown Shrimp
8.8
15.7
..114.5
. 5.8
44 ..
9.6
9.6
120
6.6
3.5
3.3-10
33-100
~- 1000
330-1000
3300-10000
. 330-1000
100-330
Cardium Agonus
edule cataphractus
Armed
Cackle Bull Head
15.8
70
12.7
81
19.2
63
38.8
69.5
48.5
32.4
30.5
330-1000
33-100
Flat Fish Asterias Carcinus
Pleuronectes rubens maenas
limanda(L)
or platessa(P) Star Shore
or f lesus(F) Fish Crab
20.4
23.2
> 300 (15)
10-33 (L) 10-25
102
15-20
> 150
35.0
21.3
Ostrea*
edu lis
Oysters
15- 50
•^ 100
50-100
50-100
*Tests lasted 5 days, not 48 hours.
-------
TABLE I (Continued)
Solvent emulsifiers
(continued)
Esso Solvent FG155
Banner DG01
Banner DG02
Banner DG03
Banner DG04
Basol AD6
Cuprinol 106
Penetone X
Polycomplex A
Craine OSR
Corexit 7664
Mobilsol
Houghto solve
Raynap Sol B
Foilzoil
BP 1100
Ridzlik
Dermol
Corexit 8&66
New Dispersol OS
(Dispersol SD)
New BP 1100 A
New BP 1100 B
Finasol ESK
Finasol SC
Hoe SC 1708
Snowdrift SC 98
Neptune Marine Cleaner
Finasol OSR
BP 1100 A
Sefoil
Pandalus Crangon Cardium Agonus Flat Fish Asterias Carcinus Ostrea
montagui crangon edule cataphractus Pleuronectes rubens maenas edulis
limanda(L)
Armed or platessa(P) Star Shore
Pink Shrimp Brown Shrimp Cockle Bull Head or flesus(F) Fish Crab Oysters
10-33
10-15
8-12
10-15
15-20
10-15
4-8
20-30
100-200 33-100 33-100 (L)
500-750
7500-10000 3300-10000 1000-3300 (L)
10-33
10-33
3.3-10
330-1000 33-100
> 3300 1000-3300 1000-3300
330-1000
148 156 148
> 3300
3300-10000 100-330
> 3300
> 3300
100-330
33-100
330-1000
330-1000
33-100
3300
3300-10000
1000-3300 1000-3300
rt>
n>
3
-h
o
-------
Treatment of Oil Spills
D Cost-Effectiveness
1 Cost
The cost of dispersants ranges from
$2.00 - $5.00 per gallon. Using
manufacturers' recommended doses,
which are usually 1 gallon of dispersant
to 10 gallons of oil, the cost of chemicals
for dispersing a relatively small 500
barrel spill would be about $10, 000.
Based on EPA's actual field experience,
which has indicated that frequently the
necessary dosage is 1 to 1 or 1 to 2, the
cost might run as high as $100, 000 for
this same size spill. Of course, the
amount of chemical required is going
to depend heavily on the type and age
of oil to be treated, type of dispersant
used, and the temperature of the water.
2 Effectiveness
Equally as important as toxicity, is the
effectiveness of a dispersant.
Evaluation of the effectiveness of dis-
persants during accidental spill incidents
is difficult. Lack of adequate methods
for measuring the amount of oil on water
and the rate of natural dispersion make
precise evaluation impossible. Their
effectiveness during the Torrey Canyon
is still being debated. Subsequent
incidents which are claimed to have
demonstrated their effectiveness have
been at remote locations and without
impartial, qualified observers.
Application methods of dispersants and
subsequent agitation, which are critical
for effective performance, have not
always been optimal.
As an initial step in trying to solve this
problem EPA developed a standard test
for measuring emulsion efficiency .
At the present time, four private labs
are "testing the test" to determine its
applicability using a variety of oils and
dispersants. Figure 2, which shows the
results of testing done at the Edison
Water Quality Laboratory adequately
demonstrates the degree of variability
which will occurr when using different
dispersants on the same type of oil and
when using the same dispersant on
different types of oil.
E EPA Policy
The present policy regarding the use of
dispersants is shown on the following pages.
TABLE 2.
APPARENT COMPOSITION OF TEST CHEMICALS
Surfactant Surfactant
Product Ionic Nature1 Basic Composition2 Solvent3
A Nonionic
B Nonionic
C Nonionic
D Nonionic
E Anionic
Ethylene oxide
condensate of
alkyphenol
Ethylene oxide
condensate of
alkylphenol
Polyhydric
alcohol ester
of fatty acid
Alkanolamide
Alkyl aryf
sulfonate
Aromatic, ali-
phatic hydro-
carbon, boiling
point range
similar to that
of number 2
fuel oil
Water, glycol
Water, short-
chained alcohol
Water
Aromatic, ali-
phatic hydro-
carbon, boiling
point range
similar to that
of number 2
fuel oil
1. According to Weatherburn test.1**
2. By infrared spectral analysis of dried (105°C) residue; test was
not definitive, but results consistent with stated, presumed com-
position.
3. By distillation and infrared spectral analysis.
18-6
-------
Treatment of Oil Spills
\
*i run. on SOUTH LOUISIANA
CtUOE
LAOO
CIUDE
BACHAOUERO
CRUDE
SANTA BARBARA BUNKER C
CRUDE
FIGURE 2. OIL DISPERSANT EFFECTIVENESS
18-7
-------
Treatment of Oil Spills
ANNEX X (5)
2000 SCHEDULE OF DISPERSANTS AND OTHER CHEMICALS TO TREAT OIL SPILLS
2001 General
2001.1 This schedule shall apply to the navigable waters of the United States and adjoining
shorelines, and the waters of the contiguous zone as defined in Article 24 of the Convention
on the Territorial Sea and the Contiguous Zone.
2001. 2 This schedule applies to the regulation of any chemical as hereinafter defined that is
applied to an oil spill.
2001.3 This schedule advocates development and utilization of mechanical arid other control
methods that will result in removal of oil from the environment with subsequent proper disposal.
2001.4 Relationship of the Federal Water Quality Administration (FWQA) with other Federal
agencies and State agencies in implementing this schedule: in those States with more stringent
laws, regulations or written policies for regulation of chemical use, such State laws, regulations
or written policies shall govern. This schedule will apply in those States that have not adopted
such laws, regulations or written policies.
2002 Definitions Substances applied to an oil spill are defined as follows:
2002.1 Collecting agents - include chemicals or other agents that can gell, sorb, congeal,
herd, entrap, fix, or make the oil mass more rigid or viscous in order to facilitate surface
removal of oil.
2002.2 Sinking agents - are those chemical or other agents that can physically sink oil below
the water surface.
2002.3 Dispersing agents - are those chemical agents or compounds which emulsify, disperse
or solubilize oil into the water column or act to further the surface spreading of oil slicks in
order to facilitate dispersal of the oil into the water column.
2003 Collecting Agents Collecting agents are considered to be generally acceptable providing
that these materials do not in themselves or in combination with the oil increase the pollution
hazard.
2004 Sinking Agents Sinking agents may be used only in marine waters exceeding 100 meters
in depth where currents are not predominantly onshore, and only if other control methods are
judged by FWQA to be inadequate or not feasible.
2005 Authorities Controlling Use of Dispersants
2005. 1 Regional response team activated: dispersants may be used in any place, at any time,
and in quantities designated by the On-Scene Commander, when their use will
2005.1 - 1 in the judgment of the On-Scene Commander, prevent or
substantially reduce hazard to human life or limb or substantial hazard
of fire to property;
2005. 1 - 2 in the judgment of FWQA, in consultation with appropriate
State agencies, prevent or reduce substantial hazard to a major segment
of the population(s) of vulnerable species of waterfowl; and
18-8
-------
Treatment of Oil Spills
2005. 1 - 3 in the judgment of FWQA, in consultation with appropriate
State agencies, result in the least overall environmental damage, or
interference with the designated uses.
2005.2 Regional response team not activated: provisions of Section 2005.1-1 shall apply.
The use of dispersants in any other situation shall be subject to this schedule except in
States where State laws, regulations, or written policies that govern the prohibition, use,
quantity, or type of dispersant are in effect. In such States, the State laws, regulations
or written policies shall be followed during the cleanup operation.
2006 Interim Restrictions on Use of Dispersants for Pollution Control Purposes Except as
noted in 2005. 1, dispersants shall not be used.
2006.1 on any distillate fuel oil;
2006. 2 on any spill of oil less than 200 barrels in quantity;
2006.3 on any shoreline;
2006.4 in any waters less than 100 feet deep;
2006. 5 in any waters containing major populations, or breeding or passage areas for species
of fish or marine life which may be damaged or rendered commercially less marketable by
exposure to dispersant or dispersed oil;
2006. 6 in any waters where winds and/or currents are of such velocity and direction that
dispersed oil mixtures would likely, in the judgment of FWQA, be carried to shore areas
within 24 hours; or
2006. 7 in any waters where such use may affect surface water supplies.
2007 Dispersant Use Dispersants may be used in accordance with this schedule if other control
methods are judged to be inadequate or infeasible, and if:
2007.1 information has been provided to FWQA, in sufficient time prior to its use for review
by FWQA, on its toxicity, effectiveness and oxygen demand determined by the standard pro-
cedures published by FWQA. (Prior to publication by FWQA of standard procedures, no
dispersant shall be applied, except as noted in Section 2005.1-1 in quantities exceeding 5 ppm
in the upper 3 feet of the water column during any 24-hour period. This amount is equivalent
to 5 gallons per acre per 24 hours.);
2007. 2 applied during any 24-hour period in quantities not exceeding the 96 hour TL,-0 of the
most sensitive species tested as calculated in the top foot of the water column. The maximum
volume of chemical permitted, in gallons per acre per 24 hours, shall be calculated by
multiplying the 96 hour TL value of the most sensitive species tested, in ppm, by 0.33;
except that in no case, except as noted in Section 2005. 1-1, will the daily application rate of
chemical exceed 540 gallons per acre or one-fifth of the total volume spilled, whichever
quantity is smaller.
2007. 3 Dispersant containers are labeled with the following information:
2007.3 - 1 name, brand or trademark, if any, under which the chemical
is sold;
18-9
-------
Treatment of Oil Spills
2007.3 - 2 name and address of the manufacturer, importer or vendor;
2007.3 - 3 flash point;
2007.3 - 4 freezing or pour point;
2007.3 - 5 viscosity;
2007.3 - 6 recommend application procedure(s), concentration(s), and
conditions for use as regards water salinity, water temperature, and
types and ages of oils; and
2007. 3 - 7 date of production and shelf life.
2007.4 Information to be supplied to FWQA on the:
2007.4 - 1 chemical name and percentage of each component;
2007.4 - 2 concentrations of potentially hazardous trace materials;
including, but not necessarily being limited to lead, chromium, zinc,
arsenic, mercury, nickel, copper or chlorinated hydrocarbons;
2007.4 - 3 description of analytical methods used in determining
chemical characteristics outlined in 2007.4-1, 2 above;
2007.4 - 4 methods for analyzing the chemical in fresh and salt
water are provided to FWQA, or reasons why such analytical methods
cannot be provided;
2007.4 - 5 for purposes of research and development, FWQA may
authorize use of dispersants in specified amounts and locations under
controlled conditions irrespective of the provisions of this schedule.
REFERENCES
1 Poliakoff, Melvin, A. Oil Dispersing
Chemicals, 1969. Edison Water Quality
Laboratory, FWPCA, Edison, NJ 08817.
2 Canevari, G.P. General Dispersant
Theory. Proceedings, Joint Conference
on Prevention & Control of Oil Spills,
API-FWPCA, 1969.
3 Portmann, J.E. The Toxicity of 120
Substances to Marine Organisms.
Fisheries Laboratory, Burnham on
Crouch, Essex, United Kingdom.
September 1970.
4 Murphy, T., McCarthy, L. Evaluation of
the Effectiveness of Oil Spill Dispersants.
Proceedings, Joint Conference on
Prevention & Control of Oil Spills,
API-FWPCA, 1969.
5 Federal Register, Volume 35, Number 106,
June 2, 1970.
This outline was prepared by Richard T.
Dewling, Director, R & D, Edison Water
Quality Laboratory, OWP, EPA, Edison,
NJ 08817.
18-10
-------
PROPOSED EPA TESTS ON OIL DISPERSANT
TOXICITY AND EFFECTIVENESS
I INTRODUCTION
Damage to the environment from oil spill
cleanup operations by the indiscriminate use
of chemical dispersants has led to the
establishment of policies regarding the use
of these materials. These are set forth in
the June 1970 National Oil and Hazardous
Materials Pollution Contingency Plan which
was developed pursuant to the provisions of
the Water Quality Improvement Act of 1970.
Among other constraints, it is the policy of
this plan that oil dispersing chemicals, prior
to their use, be tested for relative toxicity
and effectiveness in accordance with
standardized procedures to be established
by the Environmental Protection Agency.
Data on the relative toxicity and effectiveness
of these dispersing chemicals will provide
the basis for the selection of those chemicals
most effective and least toxic to aquatic life,
or for prohibiting their use.
In the faU of 1969, the EPA's National Marine
Water Quality Laboratory at West Kingston,
Rhode Island, provided preliminary methods
for determining the relative toxicity of
dispersants, while EPA's Edison Water
Quality Laboratory at Edison, New Jersey
completed work on tentative procedures for
evaluating dispersant effectiveness. Shortly
thereafter, a joint government/industrial
task force panel reviewed the proposed tests
developed by these laboratories and recom-
mended that an independent evaluation of the
tests be conducted prior to official
promulgation. Accordingly, an intensive
program, sponsored by EPA, is currently
underway by four commerical laboratories
to evaluate the reproducibility of the proposed
tests and to recommend modifications,
improvements and refinements in the testing
procedures. This program is scheduled to
be completed by June 1971.
II PROPOSED EPA DISPERSANT
TOXICITY TESTS
A General Description
These tests involve numerous bioassays
on four aquatic organisms using the
dispersant under investigation and
mixtures of the dispersant with various
oils. The test procedures require
determinations of 96 hour (for fish) and
48 hour (for organisms other than fish)
50% survival values (TL J for both the
raw dispersing chemicaland dilutions
of the dispersant mixed in a 1:10 ratio
with each of two crude oils and two fuel
oils. All test operations are carried out
at 20° C for marine species and 25° C for
fresh water species.
B Standardized Test Conditions
The bioassay methods stipulated in the
tests are based on "Standard Methods
for the Examination of Water and
Wastewaters", 12th Edition, but they
are modified to meet the special problems
arising in the use of fish and of test
organisms other than fish in the bioassay
of dispersants and mixtures of dispersants
with different petroleum products. These
modifications include special bioassay
methods for organisms other than fish
and the standardization of certain aspects
of the bioassays outlined in "Standard
Methods" such as test species, mixing
and agitation, dilution water, aeration,
dissolved oxygen concentrations, temper-
atures, pH and salinity.
The complete testing procedures are
described in reference (4).
BI. BIO. met. 21. 5. 71
19-1
-------
Proposed EPA Tests on Oil Dispersant Toxicity and Effectiveness
C Test Organisms
The four species designated for these
tests are:
1 For marine water determinations
a Mummichog (Fundulus heteroclitus)
Salt Water Fish
b Oyster Larvae (Crassostrea
virginica) - Soft Shell Invertebrate
c Brine Shrimp (Artemia) - Hard
Shell Invertebrate
2 For fresh water determinations
a Fathead Minnow (Pimephales
promelas) - Fresh Water Fish
These four species were selected because
they are widely distributed and, with the
exception of the oyster larvae, can be
secured in many parts of the country.
The three test animals used in the marine
water determinations represent a wide
range of animal classes including: a free
swimming fish; a mollusc (oyster) which
is a bottom dwelling organism which is
stationary at least part of its life; and an
arthropod (shrimp) which represents the
largest class of animal species. The
animals selected for these tests also
provide a wide range of indicators for
relative toxicity. The fresh and marine
water fish are somewhat tolerant animals,
while the brine shrimp and oyster larvae
are sensitive species highly susceptible to
environmental insults.
D Test Oils
The oils used in these tests were selected
on the basis of their availability and their
composition, so as to reflect the varied
range of oils likely to be encountered during
spills. The selected oils are:
1 A refined product (No. 2 fuel oil) per
ASTM Specification D-396-67.
2 A heavy residual fuel oil (No. 6 fuel oil)
per ASTM Specification D-396-67.
3 A heavy, high asphaltic Venezuelan
crude oil (Bachaquero) with the
characteristics shown below.
4 A light, low residual crude (South
Louisiana) with the characteristics
shown below.
APIO
Viscosity, Universal
Pour Point, o p
% Weight Sulfur
% Weight Asphaltenes
Neutralization Number
% Volume Distilled at:
30QC-F
4000 F
7000F
Bachaquero
17
1500
-5
2.2
7.0
2.7
6
17
35
South Louisiana
36.6
41
15
0.20
0.3
0.4
18
43
71
19-2
-------
Proposed EPA Tests on Oil Dispersant Toxicity and Effectiveness
E Discussion
The prime purpose of the EPA Dispersant
Toxicity Tests is to provide data which
will indicate relative, short term (acute)
toxicity of dispersants and oil dispersant
mixtures. These tests do not indicate the
long term toxicity of these chemicals to
aquatic organisms, safe levels for the
aquatic biota or for humans, nor do they
constitute an endorsement of any material
by the EPA.
IE PROPOSED EPA DISPERSANT
EFFECTIVENESS TESTS
A General Description
These tests essentially incorporate the
basic apparatus of the Navy Tank Test
of Specification MIL-S-22864, Solvent -
Emulsifier, Oil Slick with substantial
procedural and equipment modifications
to more closely simulate environmental
conditions. The tests utilize a 24-inch
diameter X 28-inch high cylindrical tank
containing 16-inches of standardized
synthetic sea water with a system for
recirculating the tank contents from the
bottom of the tank to just below the surface
of the water. This simulates the sub-
surface mixing of natural waters. In the
test, 100 ml of oil is poured into a 7. 5
inch diameter stainless steel ring which
is positioned at the water's surface.
The ring is used to contain the oil and
facilitate contact between the oil and the
dispersing chemical. The dispersant to
be investigated is applied (in varying
quantities) in a fine stream to the oil and
a predetermined "contact time" is allowed
for the chemical to contact the oil. The
oil/dispersant mixture is then agitated by
hosing with a pressurized stream of
synthetic sea water under standard con-
ditions until the water level in the tank
reaches 18-inches. At the termination
of hosing, the tank contents are allowed
to recirculate throughout the sampling
period. For determination of "initial
dispersion" the samples are withdrawn
5 minutes after termination of hosing,
which is the shortest time required for
the contents of the tank to stabilize; for
determination of dispersant "stability",
samples are withdrawn at stipulated
intervals for periods of up to 6 hours
after termination of hosing. Oil is
extracted from the samples with an
organic solvent and the quantity of oil
is spectrophotometrically determined.
Results of tests are expressed as percent
of the original 100 ml of oil dispersed--
that is, recovered from the underlying
water.
In these tests, varying quantities of the
dispersant under investigation are mixed
with a constant quantity of oil (100 ml) in
order to establish the minimum quantity
of dispersant required for an "initial
dispersion" of 25%, 50% and 75% of the
total oil sample.
"Stability" determinations are made with
that quantity of dispersant which causes
a 50% "initial dispersion" of the oil.
The "stability" tests measure the relative
persistence of the dispersion for periods
of up to 6 hours of mild agitation and
basically follow the time course in the
decay of the "initial dispersion". It has
been found that the time between addition
of dispersing chemical and agitation
(contact time) may have a profound
influence on dispersant effectiveness, i.e.
longer contact time improves the effective-
ness of some dispersants and reduces that
of others. For this reason, the contact
time in this test is adjusted, to some
extent, to the properties of the dispersing
chemical used. This adjustment is made
by determining initial dispersion values
of the chemical at widely differing contact
times (zero and 10 minutes) and by per-
forming all subsequent tests at that
contact time giving greater dispersion.
Since eduction is frequently suggested by
manufacturers as a method for applying
dispersants, these tests include deter-
minations of dispersant effectiveness when
educted into the agitation hose stream as
compared to effectiveness when applied
undiluted to the oil followed by agitation.
19-3
-------
Proposed EPA Tests on Oil Dispersant'. Toxicity.and Effectiveness
More details of the Proposed EPA
Dispersant Effectiveness Tests are given
in reference (5).
B Test Oils
The oils used in these tests are the same
as those designated for the EPA Dispersant
Toxicity Tests.
C Discussion
The EPA Dispersant Effectiveness Tests,
• which measure both initial dispersion and
stability of dispersion and simulate typical
environmental conditions, have been found
by the Edison Water Quality Laboratory
to produce results which correspond
favorably with field performance. The
tests show promise of providing meaningful
measures of the effectiveness of chemicals
in dispersing oil from the surface of water.
IV SUMMARY
Test procedures have been proposed by the
Environmental Protection Agency for deter-
mining the relative toxicity and effectiveness
of oil dispersing chemicals. The dispersant
toxicity tests include bioassay determinations
on four aquatic organisms using the dispersant
under investigation and mixtures of the
dispersant with two crude oils and two fuel
oils. The dispersant effectiveness tests are
basically modifications and refinements of
the Navy specification for solvent emulsifiers.
These tests measure the relative efficiency
of the dispersant in varying concentrations
with the designated oils.
It is expected that upon completion of the
current evaluations of these proposed tests
by the four commercial laboratories,
meaningful standard procedures will be
finalized which will be reproducible from
day to day and from laboratory to laboratory.
These tests should provide the necessary
tools for the selection of relatively non-toxic,
effective dispersing chemicals for oil cleanup
operations.
REFERENCES
1 National Oil and Hazardous Materials
Pollution Contingency Plan. June 1970.
2 Public Law 91-224, 91st Congress,
H. R. 4148, Water Quality Improvement
Act. April 3, 1970. • .
3 Standard Methods, for the Examination
of Water and Wastewaters, 12th . .
Edition. American Public Health .
Association. New York. 1969.
4 Tarzwell, C.M.- Standard-Methods for
Determination of Relative Toxicity of
Oil Dispersants and Mixtures of
Dispersants and Various Oils to Aquatic
Organisms, Proceedings - Joint
(API/FWPCA) Conference on. Prevention
and Control of Oil Spills. December
1969.. . • ...'-.
5 Murphy, T.A., McCarthy, L. T.
Evaluation of the Effectiveness of Oil-
Dispersing Chemicals, Proceedings -
Joint (API/FWPCA) Conference on
Prevention and Control of Oil Spills.
December 1969.
6 MIL-S-22864 A (Ships), Military
Specification, Solvent-Emulsifier,
Oil-Slick. February 24, 1969.
This outline was prepared by Ira Wilder,
Chemical Engineer, R & D, Edison Water
Quality Laboratory, Office of Water Programs,
EPA, Edison, --NJ,. .
19-4
-------
TREATMENT OF OIL SPILLS - SINKING AGENTS
I DEFINITION - USE POLICY
Sinking agents are oil-attracting and water
repelling sorbent materials designed to sink
oil slicks out of sight rather than agglomer-
ating oil on the water surface. The use of
oil sinkants would seem advantageous in
deeper waters outside heavy fishing zones,
such as off the continental shelf and where
adverse effects upon biological bottom life
may be held at a minimum.'°' Existing
EPA policy on sinking agents restricts their
use to waters exceeding 100 meters in depth.
Oily discharges into inland rivers and coastal
waters do not remain floating forever since
much of the oil will be naturally absorbed
onto clay, silt and other particulate matter
normally suspended in the water, thus causing
eventual sinking of the oil. Sinking by
natural means, for example, is believed to be
one of the primary causes for the disappearance
of oil slicks in the New York Harbor complex.
II TYPES
Various types of natural materials and com-
mercial products are presently available
which are claimed to be effective in sinking
oil slicks. *lj ' Typical agents include sand,
brick dust, fly ash, china clay, volcanic ash,
coal dust, cement, stucco, slaked lime, spent
tannery lime, carbonized-siliconized-waxed
sands, crushed stone, vermiculite, kaolin,
fuller's earth, and calcium carbonate, including
the "Oyma" type chalk used during the TORREY
CANYON.
Sinking agents are believed most efficiently
employed on thick, heavy and weathered oil
slicks in contrast to relatively light and fresh
oils. These agents are granular or fine
particulate solids with a specific gravity
generally between 2. 4 and 3. 0. These agents
must be evenly distributed over the surface of a
a slick and suppled with proper mixing,
agitation and time interaction. The particle-
coated and agglomerated mass eventually
becomes heavier than water and sinks to the
bottom.
Ill PERFORMANCE
The major problem in sinking oils is that the
bonding of the agent with the oil must be
nearly permanent. Experiments in both the
laboratory and field show that many agents
will release entrapped and sunken oils back
to the water environment. Increasing the
application rate two or three times over
prescribed amounts has served to minimize
this release.
Studies conducted by various investigators
(4, 5, 6, 7, 9, 10, 12) indicated that:
A
B
Sulfurized oils may show greater sinking
abilities than desulfurized oils because of
higher potentials for hydrogen bonding.
When sands are used for sinking it may
be expected that the oily mass will be
stable under water when the sands are
closely packed and the interstices are
filled with oil giving an oil content around
40 per cent and a bulk density about 1. 7.
However, when the sands are loosely
packed, the mass will become internally
mobile, so that oil drops will separate and
escape"to the water until equilibrium is
reestablished.
With carbonized sand, it was indicated
that up to three pounds of sand would be
required to sink one pound of oil. Large-
scale applications of amine-coated sands
envision spraying the sand in a slurry
form from a large vessel or hopper dredge.
In ports and harbors it has been mentioned
that turbulence or agitation of the water
body caused by storms or passing vessels
may tend to release oily masses previously
sunk. For siliconized sand, it has also
been suggested that one per cent bone
• flour or an inexpensive fertilizer may be
added to promote bacterial growths and
accelerate
mass.
Tated decomposition of the sunken
' • ' Table 1 summarizes the tyc
types,
application rates and relative costs of
various sinking agents.
IV FIELD EXPERIENCE
The most prominent large-scale application
of sinking agents was that undertaken by the
French to sink large masses of TORREY
CANYON oils in the Bay of Biscay. Some
3, 000 tons of calcium carbonate (blackboard
IN. PPW.ol. 15.5. 71
20-1
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Treatment of Oil Spills - Sinking Agents
chalk from the Champagne area of France)
coated with about one per cent sodium
stearate, was used to treat and sink about
20, 000 tons of floating oils, although this
amount was never precisely defined. The
powdery chalk was sprayed or sprinkled
over the thick, highly viscous and weathered
oil patches and thereafter the water surface
was mixed by vessels criss-crossing the
area. The oil-chalk mixture reportedly
sank in about 60-70 fathoms of water. The
area of sinking was known to partially cover
scamp fishing grounds and thus there was
fear of bottom inundation and oil resurfacing.
Numerous observations, since this incident,
however, have reported no adverse effects
upon fisheries and bottom life, and there
have been no sightings of resurfacing oils
upon the water or adjoining shorelines.
Nevertheless, it was concluded that lack of
knowledge on the precise fate of the oil shows
need for further trials before this method may
be recommended in other situations. "*' * '
Opinion still remains divided on the use of
oil sinkants as to their efficiency, cost,
application, and possible adverse effects.
With sinking agents, the same problems are
encountered in the application and distribu-
tion as was indicated in the lecture on floating
sorbents. However, with sinking agents,
operational logistics become increasingly
more difficult because of the much larger
amounts of material required for treatment.
Although damaging effects have been ascribed
to toxicity and smothering of bottom life by
sunken oils, the sinking approach serves to
localize oil pollution, to prevent its spread
over the water surface, and theoretically
submerge and anchor the oil near the source
of pollution. Considering that the bottom of
harbors and bays near many industrial ports
are grossly polluted and nonproductive,
emergency sinking of oils in these areas may
not increase damage to fisheries. Dilution by
flowing waters in certain areas may also be
sufficient to adequately minimize toxicity to
nearby shellfish grounds. The other impor-
tant point of view is that sinking agents, even
if used in harbor areas because of fire or
explosion danger, can at best be of temporary
benefit. The resurfacing oils, although less
objectionable due to weathering, may require
pick up. Furthermore, sinking may greatly
extend the period over which aquatic fauna and
flora are affected. U,^,8, 1^)
V R & D PROGRESS
(11)
Dutch Shell Laboratories, Holland, ""' was
one of the first groups to really evaluate
sinking agents on a field scale basis. Their
studies, still underway, involve using sand
treated with an amine. One very important
finding from their investigations was that
there was a correlation between clay content
and performance as measured by the per-
centage of oil sunk. The lower the clay
content the more efficient the sinking agent.
The Warren Spring Laboratory, United
Kingdom, ^'impressed by the results of
these studies, conducted similar field
investigations during 1969. Conclusions
reached by the Warren Spring Laboratory
were as follows:
A The sinking was not as effective as first-
hoped and it would appear that the thick-
ness of the oil film is an important factor.
Nevertheless, between 50 and 70 per cent
of the oil put on the sea was sunk.
B The skin divers reported that the oil sank
to the bottom in small particles which
were only slightly more dense than the
sea. Consequently, the tidal current along
the sea bed was sufficient to carry the oil
over the ripples of sand on the bottom.
C Trawling was carried out and although no
actual lumps of oil were collected, suffi-
cient oil was rubbed onto the netting of the
trawl to foul both the catch and the fisher-
men when they were pulling it back into
the vessel.
D The oil which remained afloat was par-
ticularly difficult to dispose of using
either more sand slurry or the normal
solvent emulsifier mixture agitated by
water hoses. Further investigations on
this particular phenomenon are being
carried out both in England and in Holland.
In the United States, the Army Corps of
Engineers, under contract to U. S. Coast
Guard, is evaluating various types of sinking
agents--treated and untreated--as well as
investigating the possibility of using their
hopper dredges, normally used for dredging
harbors, to handle and apply the sinking
agents. Results of these studies should be
available in 1971.
20-2
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Treatment of Oil Spills - Sinking Agents
TABLE I - OIL SINKING AGENTS, APPLICATION RATES AND OTHER OPERATIONAL DATAA
Type Material
Application Ratios
(Weight Sinking Agent: Weight Oil Treated) Comments
Silica, untreated
Carbonized sand
Sands, amine-coated
Sands. 0.5% silicone coated
Fly ash, untreated
Fly ash. 0.5% silicone coated
Released oil easily after sinking
1:1 to 3:1 Higher proportion of sinking agent considered most
appropriate: $27/ton carbonized sand (1948): specific
gravity particles = 2.7
3:2 to 2:1 Large-scale application costs estimated $5 - $10 per
ton of oil treated
More effective on heavier oils
Released oil easily after sinking
2:1 ratio or higher Permanent oil sinking reported; more effective on
lighter oils.
Spent tannery lime
Kaolin clay
Bentonite, montmorillinite
clay, treated and untreated
Calcium carbonate
Fuller's earth 1:1 to 9:1
Calcium carbonate - Champagne
chalk treated with 1% sodium stearate Approx. 1:1
Good oil retention properties after sinking
Released oil easily after sinking
Released oil easily after sinking
1:1 to 3:1 for sulfurized oil; 3:1 to 9:1 fordesulfurized oil.
Used off the coast of France during the Torrey Canyon;
$60 - $80/ton sinking agent. Specific gravity particles - 2.7.
Synthetic silicate
Synthetic plus filler material
4:3 or higher
High efficiency in absorbing fuel and crude oils; some
difficulty in sinking the mass.
Estimated $120/ton sinking agent.
A8ibliography (2.3,4,9, 10,12.13. 14)
20-3
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Treatment of Oil Spills - Sinking Agents
REFERENCES
1 Internal files and laboratory data of the
Oil and Hazardous Material Section,
R&D, WQO, EPA, Edison Water
Quality Laboratory, Edison, NJ.
(Unpublished materials)
2 "Study of Equipment and Methods for
Removing Oil From Harbor Waters, "
Battelle Memorial Institute, Pacific
Northwest Laboratories, Report No.
CR-70-001, prepared under Contract
N62399-69-C-0028 for the Department
of the Navy.
3 Manufacturers' product bulletins and
brochures, and follow-up communica-
tion.
4 "Oil Pollution at Sea, Studies in Con-
nection with the TORREY CANYON
Episode, " Atomic Energy Research
Establishment, Chemistry Division,
Harwell, Berks, Great Britain, Sep-
tember 1967.
5 Struzeski, E. and Dewling, R. , "Chemical
Treatment of Oil Spills, " Proceedings,
Joint Conference on Prevention and
Control of Oil Spills, API and FWPCA.
6 Smith, J. W. , United Kingdom Ministry
of Technology, "Work on Oil Pollution",
Proceedings, Joint Conference on
Prevention and Control of Oil Spills,
API and FWPCA, 1969.
7 "TORREY CANYON Pollution and Marine
Life, " A Report by the Plymouth
Laboratory of the Marine Biological
Association of the United Kingdom,
Cambridge University Press, Great
Britain, 1968.
8 "Chemical Treatment of Oil Slicks, " U. S.
Department of the Interior, FWPCA,
Water Quality Laboratory, Edison, NJ,
March 1969.
9 Hartung, R. and Klinger, G. W. ,
"Sedimentation of Floating Oils, "
Papers of the Michigan Academy of
Science, Arts, and Letters, Vol. LIII,
1968 (1967 Meeting)
10 Correspondence and internal reports
received from Department of the Army,
U. S. Corps of Engineers, Vicksburg,
Miss., and Washington, DC.
11 Meijs, L. J. et al, "New Methods for
Combating Oil Slicks, Proceedings,
Joint Conference on Prevention and
Control of Oil Spills, API and FWPCA,
1969.
12
13
14
15
16
17
Chipman, W. A. and Galtsoff, P. S. ,
Effects of Oil Mixed with Carbonized
Sand on Aquatic Animals, " Special
Scientific Report: Fisheries No. 1,
U. S. Department of the Interior, Fish
and Wildlife Service, Washington, DC,
August 1949.
"The TORREY CANYON, " Presented to
Parliament by the Secretary of State
for the Home Department by Command
of Her Majesty, April 1967. Her
Majesty's Stationery Office, London,
England.
"The TORREY CANYON", Cabinet Office,
Report of the Committee of Scientists
on the Scientific and Technicological
Aspects of the Torrey Canyon Disaster,
Her Majesty's Stationery Office, London,
England. 1967.
"French Explode an Oil Slick Myth, "
article appearing in the MANCHESTER
GUARDIAN, Manchester, England,
July 25, 1968.
Bone, Q. and Holme, N. , "Lessons from
the TORREY CANYON, " New SCIENTIST,
p. 492-493, Septembers, 1968.
Bone, Q. and Holme, N. , "Oil Pollution --
Another Point of View, " NEW SCIENTIST,
37, p. 365, February 15, 1968.
This outline was prepared by R. T. Dewling,
Director, Research & Development, Office of
Water Programs, Edison Water Quality
Laboratory, Edison, NJ 08817.
20-4
-------
TREATMENT OF OIL SPILLS - BURNING AGENTS
I INTRODUCTION
Burning of oil on water or land by special
methods and materials seems to offer an
attractive and perhaps inexpensive means of
eliminating large amounts, providing of course,
the many significant hazards are also recog-
nized. Freshly spilled oils and crudes con-
taining volatile components are relatively
ignitible. If a thick layer of oil on water is
present, the oil will sustain burning until the
volatiles and a portion of the heavier frac-
tions are combusted. Conversely, with fresh
oil spills within a harbor or confined area, a
significant fire danger exists when the level
of hydrocarbon vapors is within the range of
flammability, (e. g. gasoline, aviation fuels,
or light crude oils). (1,2)
Wood, debris or other material caught with-
in an oil slick can serve as a wick to start
or sustain an oil fire. The cooling of a layer
of oil by the water body beneath will greatly
deter burning. However, the wick will with-
draw the oil and insulate the burning oils from
the cooling action of the water, and at the same
time provide a renewal and vaporization
surface for combustion.
II EXPERIENCE ON WATER
A General
Experience by certain investigators has
indicated that floating oils on the sea with
thicknesses less than 3 millimeters (0. 12
inches) will not burn. It is also reported
that layers of kerosene, gas oil, lubri-
cating oil and fuel oil on water will not
burn at all without a wick. In one instance,
attempts were made to ignite fresh Iranian
crude oil five minutes after a spill without
success. Once an oil spillage has spread,
the material quickly loses its volatile
components and ignition is extremely
difficult. Weathered oils are consequently
reported to present almost no fire hazard.
(1,2,3)
B EPA Lab Experiments
In experiments carried out at the Edison
Laboratory, a heavy fuel oil and a light-
weight crude oil were placed atop a layer
of water contained in metal tanks with 24-
square-feet of exposed surface area.
Attempts were made to combust the oils
using different burning agents. It was
concluded from these experiments that
the light crude, freshly applied in a
floating thickness of 2. 5 millimeters (0. 1
inches), required external support with
burning agents and an ignition source to
burn near completion.
When the No. 6 fuel was used for testing,
one of the agents used would not sustain
burning at a thickness of 1/2 to 2/3 inches.
Another agent generously applied over the
surface ot the No. 6 fuel caused sporadic
burning and the minimum required oil
thickness to sustain burning was 1/3 to
1/2 inches. It is important to note that
a thickness of 1/3 to 1/2 inches is equiv-
alent to an oil slick of 7 million gallons/sq.
mile. It was evident after this burning
that appreciable oil was still remaining.
A third agent used performed well with
the No. 6 fuel at a thickness of I/10 to 1/4
inches. The manufacturer producing this
material, however, suggests that in order
to have complete burning of all the oil, the
oil layer must be completely covered with
the material with no broken patches. Re-
quired amounts of this material (very low
bulk density) may be as high as one pound
for each 12-15 square-feet of oil slick.
(3,4)
C EPA Field Tests
Field scale oil slick burning experiments,
with and without special agents have been
undertaken in 1970 by both the U. S. Navy
and the Edison Water Quality Laboratory.
Preliminary data from these experiments
indicate the following:
1 Burning of free floating or uncontained
oil slicks is extremely difficult unless
the thickness of oil is 2mm or greater.
2 Adequate automated seeding methods
for both the powder and nodule-type
burning agents are lacking. Spreading
of the burning agent on the oil slick had
to be accomplished by hand. This con-
clusion was also reached by the Navy,
which conducted burning experiments
in May 1970.
3 Contained South Louisiana crude oil
was successfully burned - 80% to 90%
reduction-without the application of
IN.PPW.ol. 16.5. 71.
21-1
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Treatment of Oil Spills - Burning Agents
burning agents and/or "priming" fuels.
Bunker C could not be ignited under
these same conditions.
4 Bunker C was successfully burned -
80% to 90% reduction - When the slick
was seeded with burning agents and an
appropriate priming fuel. It was
discovered that South Louisiana crude
oil performed better as a priming agent
than did gasoline or lighter fluid.
5 Use of magnesium type flares and
gasoline torches to ignite the burning-
agent-treated slick proved unsuccessful.
Success was achieved, however, using
a blow torch once we learned how to
manipulate the torch in such a manner
that the torch gas pressure did not push
aside the oil and seed material so as to
expose the water surface.
D U. K. Experience
Burning agents were considered when the
TORREY CANYON was in the final stages
of destruction off the British coast in
March of 1967. As a last resort, the
British Government attempted simultaneous
and complete burning of the 15, 000-20, 000
tons of oil remaining in the badly broken
tanker by aerial bombing, incendiaries,
and catalyst-oxidizing devices. The major
objective was to penetrate and lay open
the decks by "explosive surgery, " exposing
the oil in the storage compartments to
large amounts of oxygen required for
burning. High-explosive, 1, 000 pound
bombs filled with aluminum particles,
thousands of gallons of aviation fuel, na-
palm bombs, rockets, and sodium chlo-
rate devices served to produce a massive
fire, if not a sustained fire. The British
concluded that no appreciable amounts of
oil escaped burning, but if any did, it was
lost to the open sea. (5, 6)
E Use Considerations
Controlling the burning oil mass and
ensuing air pollution problems would
appear to preclude intentional burning
except where the oil mass is distant from
the coastline, offshore facilities, vessels,
etc. The safety and welfare of all parties
however remote from the burning site are
of utmost importance. The possible loss
of additional oil, and the loss of a drilling
platform or vessel at the source of the
spill must be recognized. Because of po-
tential merits in controlled burning,
further research is desired on new
methods, techniques and procedures both
in the laboratory and in the field, together
with additional guidelines for burning.
Ill EXPERIENCE ON LAND
J. Wardly Smith, Ministry of the Environ-
ment, United Kingdom, has conducted a
series of research experiments involving
the burning of oil on beaches. The conclu-
sions reached by these studies were:
A The type of heavy oil normally contam-
inating beaches and the foreshore is very
difficult to burn by ordinary means and
combustion ceases when the source of
heat is removed.
B The addition of solid oxidants aids the
combustion of part of the deposit, but a
sticky, tarry residue is left with medium
heat and a residue of dry, black carbon
with prolonged intense heat. About 30
per cent by weight of oxidant has to be
employed to achieve this and when the
deposit occurs on sand, shingle or pebbles
the amount of heat necessary to raise the
whole to ignition temperature is so great
that, in practice, the cost of removal
would probably be excessive.
C The application of an oil-absorbent, com-
bustible material, such as sawdust im-
pregnated with an oxidant, resulted in a
much steadier burning rate and an increased
removal of the deposit. The additive, how-
ever, burns away before the higher-boiling,
tarry fractions begin to burn.
D Although some improvement was obtained
by adding materials which function as a
wick, the same limitation regarding the
amount of heat to be supplied still prevailed.
E A major disadvantage of burning as a
method for the removal of oil deposits on
beaches, especially when dealing with the
large semi-solid lumps, is that, when
heat is applied, the oil becomes mobile
and penetrates deeper into the beach, thus
increasing the contaminated area if it
becomes exposed at a later date.
F On the basis of these small-scale exper-
iments it was considered that, for all
practical purposes, burning beach oil
deposits would be less efficient and more
costly than mechanical or manual removal,
and that further investigation would be
unprofitable.
21-2
-------
Treatment of Oil Spills - Burning Agents
IV COMMERCIAL BURNING AGENTS
Commercial burning aigents are available
for promoting combustion of an oil slick.
However, in most cases it is apparent these
agents are designed for a relatively thick oil
layer which is sufficiently contained. These
agents are intended to serve one or more
functions such as providing increased surface
area exposed to burning; addition of catalysts,
oxidizers and low-boiling volatile components;
absorbence and entrapment of the oil; or
creating a wicking mechanism via surface
diffusion and capillary action by the material
added.
To the best of our knowledge, burning agents
are available from only four sources:
A Eduard Michels GmbH, 43 Essen, Post-
fach 1189, Ruttenscheider Str 1. :
"Kontax", the commercial name for this
agent, ignites spontaneously when it comes
in contact with water. In 1969, the Dutch
conducted field experiments which included
burning of oil on beaches, and in open
waters. Results of this investigation
indicated that the quantity of "agent" re-
quired was dependent upon wind, condition
of sea and continuity and thickness of oil.
Dutch engineers also reported that a
method should be developed to jettison,
hurl or catapult the "agent" from a vessel
in such a way that there is not the slightest
risk of having the "agent" come in contact
with rainwater or spray. Dropping from
an airplane is worth considering provided
special packaging requirements are met.
B Pittsburgh Corning, One Gateway Center,
Pittsburgh, Pa. : Known as "Seabeads",
these cellulated glass nodules are avail-
able in sizes from 1/8" to 1/4" in diameter.
By capillary action, the nodules become
coated with oil. Depending upon the type
and age of the spilled oil, combustion is
accomplished by using an incendiary device
alone, or in combination with a "primer
fluid" such as gasoline. After burning,
SeaBeads still remain, therefore, they
must be collected or left to break up by
abrasion. During the "Arrow" incident in
1970, this burning agent was used, with
varying degrees of success, on small
patches of spilled oil.
C Guardian Chemical Corporation, Long
Island City, NY 11101: Pyraxon, a powder
material, is a catalyst containing small
amounts of oxidizing materials. Pyraxon
liquid is used as the priming agent or
starter fluid, with the powder being
sprayed, blown or dropped onto the oil,
in and around the flame.
D Cabot Corporation, 125 High Street,
Boston, Ma. : Cab-O-Sil ST-2-0 promotes
combustion by acting as a wicking agent.
Produced from fumed silica, this powdery-
like material, is surface treated to render
it hydrophobic. It may be applied directly
to the slick or by spraying in a stream of
water. Combustion is best accomplished
by using an incendiary device in conjunc-
tion with a "primer fluid". Reportedly,
this product was used successfully for
handling a 2, 000 gallon spill at Heard
Pond, Wayland, Ma.
REFERENCES
1 "Study of Equipment and Methods for
Removing Oil from Harbor Waters, "
Battelle Memorial Institute, Pacific
Northwest Laboratories, Report No.
CR-70-001, prepared under Contract
N62399-69-C-0028 for the Department
of the Navy.
2 "Chemical Treatment of Oil Slicks, " U. S.
Department of the Interior, FWPCA,
Water Quality Laboratory, Edison,
NJ. , March 1969.
3 Manufacturers' product bulletins and
brochures, and follow-up commu-
nication.
4 Internal files and laboratory data of the
Oil and Hazardous Material Section,
R&D, EPA, Edison Water Quality
Laboratory, Edison, NJ (Unpub-
lished materials)
5 "The TORREY CANYON, " Presented to
Parliament by the Secretary of State
for the Home Department by Command
of Her Majesty, April 1967, Her
Majesty's Stationery Office, London
England.
21-3
-------
Treatment of Oil Spills - Burning Agents
6 "The TORREY CANYON", Cabinet Office,
Report of the Committee of Scientists
on the Scientific and Technological ™s outline was prepared by R. T Dewling.
AO~«,,*.C. «f <-h~ rr~~~~,r ,-„.,„.,,., Director, Research & Development, Edison
Pter Her MaSfy^s Stationery Water Qualit^ ^oratory. Office of Water
^London England, 196? " Programs, Edison, NJ 08817
21-4
-------
TREATMENT OF OIL SPILLS - GELLING AGENTS
I INTRODUCTION
Gelling agents are applied over the surface
or periphery of a floating oil slick and are
intended to absorb, congeal, entrap, fix, or
make the oil mass more rigid or viscous so
as to facilitate subsequent physical or
mechanical pick up. The gelling concept is
also undergoing extensive study for stabi-
lizing petroleum cargoes aboard a stranded
or heavily-damaged tanker at sea subject to
mass spillage.
II TYPES AND COST
Possible gel agents include molten wax or
soap solutions, lanolin, liquid solutions of
natural fatty acids, soaps of the alkaline
metals, treated colloidal silicas, the amine-
isocyanates, and the polymer systems. One
manufacturer indicates a cost of $3 per
gallon of gel agent, a use ratio of about 1:1,
and the ability to mix the recovered gel mass
with fuel oils serving as replacement bunker
fuel. This gel agent is applied to the surface
of the vrater by a high-pressure spray system
to provide sufficient agitation and mixing of
the gel-oil mass.
Ill R & D FINDINGS
Preliminary research on the gelling of tan-
ker cargoes tends to show that a 3-10 per
cent gel agent will be required at a mater-
ials cost of 13-40 cents per gallon of tan-
ker crude oil gelled. However, total opera-
tional costs, and the ability to salvage and
reuse the gelled cargoes, are not fully known
at this time.
The gelling approach for treating oils on
water, although promising, must provide
greater attention to application and distri-
bution, lower materials and operational costs,
and suitable means of picking up the amorphous
oily masses. Bunker C, heavy crude oils,
and some gel agents by themselves may clog
intakes, pumps and suction lines. The major
difficulty is the ability to harvest the congealed
mixtures isnce gelled oils cannot be easily
collected by mechanical or manual means.
Necessary improvements are needed in the
gelling approach in line with a total opera-
tional cleanup system. (1, 2, 3, 4)
REFERENCES
1 Internal files and laboratory data of the
Oil and Hazardous Material Section,
R&D, EPA, Edison Water Quality
Laboratory, Edison, NJ.
(Unpublished materials)
2 "Study of Equipment and Methods for Re-
moving Oil From Harbor Waters, "
Battelle Memorial Institute, Pacific
Northwest Laboratories, Report No.
CR-70-001, prepared under Contract
N62399-69-C-0028 for the Department
of the Navy.
3 Manufacturers' product bulletins and
brochures, and follow-up communication.
4 "Chemical Treatment of Oil Slicks, " U. S.
Department of the Interior, FWPCA,
Water Quality Laboratory, Edison, NJ.
March 1969.
5 U. S. Patent #3, 198,731, Method of
Treating Oil on the Surface of Water.
6 Northeast Region, R&D Programs,
Federal Water Pollution Control Ad-
ministration. Status Report on Use
of Chemical and Other Materials to
Treat Oil on Water.
This outline was prepared by R. T. Dewling,
Director, Research & Development, Office of
Water Programs, Edison Water Quality
Laboratory, Edison, NJ 08817
IN. PPW.ol. 17.5. 71
22-1
-------
TREATMENT OF OIL SPILLS
Sorbents
I INTRODUCTION
A Sorbents are oil spill scavengers or
cleanup agents which adsorb and/or
absorb oil. Based on origin, sorbents
may be divided into three general classes:
1 Natural products
2 Modified or chemically-treated natural
products
3 Synthetic or man-made products
B Sorbents may be further classified as to
their physical characteristics:
1 Powdery products
2 Granular products
3 Fibrous materials
4 Pre-formed foam slabs or sheets
H TYPES OF SORBENT PRODUCTS
Types of floating sorbent materials presently
available are:
A Natural Origin: Types derived from
vegetative sources comprise straw, hay,
seaweed, kelp, ground bark, sawdust,
reclaimed fibers from paper processing,
and peat moss. Types derived from
mineral sources may include the various
clays, including montmorillinite, kaolin,
fuller's earth, diatamaceous earth, etc.;
vermicultite and the other micas, many
forms of silicates, perlite, pumice, and
asbestos. Sorbents of animal origin
include chrome shavings from leather
processing, wool wastes, feathers, and
textile wastes.
B Modified Natural Products: These
materials comprise most of the sorbent
types mentioned above but are chemically-
treated to produce a more desirable
result. Some of the modified types are
expanded perlite, charcoal, stearate-
coated talc, asbestos treated with
surfactant, and sawdust and vermiculite
coated with silicones.
Synthetic Products: These sorbents
include a vast array broadly categorized
as plastics and rubber, but more
specifically as the ethylenes, styrenes,
resins, polymers and co-polymers.
IE SORBENT CHARACTERISTICS
Desirable Sorbent Characteristics
A Oleophilic - has greater attraction for
oil than water.
B Hydrophobic - repels or rejects water.
C Adsorbtive - oil will adhere to the surface
of the material.
D Absorbtive - oil is assimilated into the
material.
E High oil capacity - the ratio of oil picked
up to material applied (Ib/lb) should be
at least 5:1 but preferably 10:1 or greater.
F Retentive - leaking of oil from material
should be minimal after harvesting.
G Low costs - on a non-reusable product.
High initial costs are acceptable for
reusable products.
H Products should float under all conditions.
Presently, none of the existing products have
all of these desirable qualities.
IN.PPW.ol. 11.5.71
23-1
-------
Treatment of Oil Spills
IV OPERATIONAL ADVANTAGES AND
DISADVANTAGES
A Advantages
1 Aids in removing oil from water surface
and alleviates or precludes undesirable
after effects.
2 Minimizes and decreases spread of oil.
3 Generally, inexpensive and available
in large quantities.
4 Non-toxic.
5 May increase both performance of
booms and skimming techniques.
6 Minimizes shore pollution when
bleached.
B Disadvantages
1 No effective workable system at present.
2 High labor costs associated with
acquisition, transportation, stock-
piling, deployment, distribution on
and working into an oil slick, retrieval
and ultimate disposal.
3 Manual retrieval only practical under
calm conditions.
4 Some products interfere with other
forms of physical removal by clogging
skimming and suction devices.
5 Pollutional problems oil disposal.
6 Some sorbent products ultimately sink.
a As their true density is greater than
water, certain mineral products
sink when air entrained in capillaries
is replaced by oil and/or water or
when products are wetted by water.
b Some natural vegetative products
such as straw, sawdust or waste
pulp fibers become waterlogged upon
prolonged exposure in water and
may sink.
V SORBENT USES
Sorbents may be used for many reasons.
A To agglomerate oil from a massive spill
to minimize spread and potential damage.
The above could be applicable to spills
on large open bodies of water where other
control procedures are ineffective and in
other areas where presently available
control procedures would be effective but
are not readily available.
B To "polish" a slick remaining after other
control procedures such as booming and
skimming have removed most of the oil.
C To sorb free oil from contaminated
surfaces to facilitate cleanup procedures.
D To deploy sorbents onto open waters and
clean beaches in anticipation of the
arrival of an uncontrolled slick.
E Used in conjunction with either fixed or
towed booms.
VI SORBENT EFFECTIVENESS
To define sorbent effectiveness certain basic
questions relating to the environmental use
of sorbents under actual spill conditions must
be considered.
A Why were sorbents used?
B What procedures will be used to harvest
the oil-sorbent mass?
In each of the situations listed in Section V,
the effectiveness must be evaluated differ-
ently because criteria for evaluating
effectiveness must be related to the original
objective for each different use.
For instance, the cost/application ratio
(i.e. product costs/unit of oil sorbed) may
be of primary importance in selecting a
product for agglomerating a massive spill
but would be of a lesser degree of importance
for "polishing" action or for alleviating or
minimizing potential damage.
23-2
-------
Treatment of Oil Spills
VII SORBTION PROCESSES
A The accumulation of oil by sorbent
products is a complex phenomenon
dependent upon several physical
processes. For example, when straw
is used the different processes most
probably occur as follows:
1 Adsorbtion of oil to the straw surface.
2 Absorbtion of oil into the interstitial
fibers and filtration into the hollow
stem.
3 When saturation is reached additional
oil is picked up by oil to oil cohesion.
B Products have different adsorbtive and
absorbtive capacities. For example, for
free flowing oils:
1 A highly pulverized mineral product
manifests primarily adsorbtion. The
pickup capacity is related to the surface
area available.
2 A polymeric foam product manifests
primarily absorbtion because of its
high internal porosity.
3 The extraneous oil pickup of all products
is related to the viscosity of the oil to
be sorbed. The higher the viscosity,
the greater the oil to oil cohesion and
adhesion.
VIE USING SORBENTS EFFECTIVELY
On unconfined oil slicks
A Products should be uniformly applied to the
slick. Most unconfined oil slicks thin out
very readily. Therefore, in order not to
waste product, a thin uniform layer is
preferred.
B The effectiveness of most products is
increased by ultimately mixing the product
into the oil slick. This can be accomplished:
1 By churning up the mass by running
boats through at high speed after broad-
casting of products.
By towing netting stretched between
boats through the mass at slow speed.
By existing environmental energy such
as wind, wave and current action.
If the above is not feasible, a time
period of at least 3-6 hours should
be allowed for the oil and product to
mix. Most spills occur in tidal areas,
and as such, the change of tide produce
a minimum mixing energy. Additionally,
the weight of most sorbent products
will be sufficient to work the product
into the oil if sufficient time is allowed.
A harvesting procedure utilizing
netting or booms which encircles a
given area and concentrates the oil/
sorbent mass by decreasing the area
is also effective.
IX OIL CAPACITY AND COSTS OF SORBENTS
A Presently, there are no standard tests for
evaluating the effectiveness of sorbents.
However, small scale laboratory testing
of many products have been completed
which at least give a measure of the
relative oil capacity of many available
products.
B Table I summarizes the results of bench
scale testing of the oil sorbing capacity
of selected products. The data was
summarized from Edison Water Quality
Laboratory tests, the oil pollution
literature and manufacturers' brochures.
C Table I reflects product costs varying
from $20 to $20, 000 per ton which breaks
down to costs of approximately $0. 02 to
$1. 00 per gallon of oil sorbed. These
costs are product costs only, based on
the reported oil capacity of the products.
They do not reflect the equipment and
labor costs associated with their use in
the environment.
D Compared with other oil spill cleanup
techniques such as booming, skimming,
dispersing and sinking, cleanup with
sorbents is reportedly the most costly
23-3
-------
Treatment of Oil Spills
procedure. The costs vary from $0. 50
to $5. 00 per gallon of oil picked up,
depending on the size of the spill and the
equipment utilized. In the absence of an
effective system for utilizing sorbents
under actual spill conditions, the high
cost are a reflection primarily of the
labor costs of the multi-step process.
X LARGE SCALE SORBENT TESTS
(2)
E.A. Milz of Shell Pipeline Corporation,
Houston, Texas, reported the performance
of 15 floating sorbents tested on a relatively
large scale.
A Summary of test data is presented in
Table II.
B Conclusions from tests.
1 Tests showed that pound for pound
polyurethane and urea formaldehyde
foams are the best oil sorbents. On
a weight basis these materials removed
about 10 times more oil than other
sorbents tested.
2 For long contact times the quantity of
oil sorbed is primarily a function of oil
viscosity and density.
3 In most cases sorbents lose oil after
pickup by drainage and evaporation.
About 80% of oil initially absorbed will
be retained after draining for 24 hours.
a One exception to the above is Kraton
rubber which dissolves oil into the
body of the material and completely
retains it. To facilitate sorbtion,
samples were granulated to a particle
size of 4 mm. Kraton rubber may
also be foamed which should improve
sorbtion.
4 Power mulching machines can effectively
spread up to nine tons of straw or hay
per hour with immediate mixing with
oil. In contrast, when hay was simply
dumped overboard, it remained in large
dry clumps for over half an hour even
in 4-5 foot waves.
5 Power mulchers are satisfactory for
shredding and spreading polyurethane
foams.
6 When sorbents are used with booms the
same problems are encountered as by
containment of oil alone by booms.
Wave action will cause spill-over and
currents above 1 fps will cause under-
sweep.
7 Nets are more effective than booms for
containing relatively small quantities
of stringy material such as hay, bark
and shredded foam. With 1-inch mesh
nets, velocities of 2-3 fps are possible
for small quantities of material without
product loss. For large quantities of
material, velocities of 1-2 fps are
possible without failure (Figure 1).
8 All collection or harvesting processes
for oiled sorbents on open water involve
screening processes. Therefore, the
selection of mesh size for harvesting
devices is critical and is related to the
sorbent particle size.
XI POTENTIAL OF SORBENTS
A Because of the inherent limitations or
regulatory restrictions for such techniques
as booming, skimming, sinking, dispersing,
burning or gelling, the advantages of
sorbent systems for cleaning up oil spills
show great promise.
B Reusable high-oil capacity sorbent products
used in conjunction with self-contained
mechanized systems will be developed
'which will have the following desirable
features:
1 Recovery of oil which decreases prob-
lem of disposal. The recovered oil can
be taken to a separator and incorporated
into refinery feeds rather than buried.
2 Products will be reusable. Certain
poly-foam products have an initially
high-cost which decreases geometrically
for each subsequent re-use. Such
products may be used dozens of times
23-4
-------
Treatment of Oil Spills
D
and potentially hundreds of times by
reinforcement of product with plastic
netting.
3 On open waters under inclement con-
ditions there is no expediency for
harvesting. The products may be
beached and subsequently the oil and
product recovered on the beach or
gathered later under calm conditions
from the water surface.
Costs will decrease as manual labor is
replaced by mechanical equipment
incorporated into continuous self-
contained systems.
Presently the EPA, U. S. Coast Guard
and the API are evaluating proposed
sorbent systems submitted for research
funding.
2 Milz, E.A. Oil Spill Control Equipment
and Techniques. Presented to the
21st Annual Pipe Line Conference,
Dallas, Texas. April 14, 1970.
3 Study of Equipment and Methods for
Removing Oil from Harbor Waters.
Prepared by Battelle Memorial
Institute, Richland, Washington for
U. S. Navy, Civil Engineering Lab-
oratory, Port Hueneme, California.
August 1969.
4 Combating Pollution Created by Oil Spills.
Prepared by A. D. Little, Inc. for
Department of Transportation, U.S.
Coast Guard. June 1969.
REFERENCES
1 Struzeski, E. J. and Dewling, R.T.
Chemical Treatment of Oil Spills.
Published in Proceedings Joint
Conference (API/FWPCA) on
Prevention and Control of Oil Spills,
New York. December 1969.
This outline was prepared by L. T. McCarthy,
Jr., Chemist, Oil Pollution Research
Section, OWP, EPA, Edison Water Quality
Laboratory, Edison, NJ 08817.
23-5
-------
to
CO
TABLE I
COSTS OF SORBENTS
(I)
(Product costs per 1,000 gallon spill. Does not include labor and equipment costs)
Type Material
Ground pine bark, undried
Ground pine bark, dried
Ground pine bark
Sawdust, dried
Industrial sawdust
Reclaimed paper fibers, dried,
surface treated
Fibrous, sawdust and other
Porous peat moss
Ground corncobs
Straw
Chrome leather shavings
Asbestos, treated
Fibrous, perlite, and other
Perlite, treated
Talcs, treated
Vermiculite, dried
Fuller's earth
Polyester plastic shavings
Nylon-polypropylene rayon
Resin type
Polyurethane foam^ '
Polyurethane foam '
Polyurethane
Polyurethane
Polyurethane foam'--''
Pick Up Ratio
Weight Oil Pick Up
Weight Absorbent
0.9
1.3
3
1.2
1.7
3
1.0
5
3-5
10
4
5
2.5
2
2
3.5-5.5
6-15
12
70
15
70
40
80
Unit Cost
Absorbent $
(Ton Absorbent)
6
15
15
56
30
30
30
500
416
230
70-120
25
100
3,100
20,000
4,500
2,260
1,200
$ Cost of Absorbent for
Cleanup of 1,000 Gals.
Oil Spill6
27
47
50
75
21
27
440
290
320
120-210
80
900
1,000
1,050
195
55
*Numbers refer to different types.
-------
TABLE II
LARGE SCALE SOPBENT TESTS(2) .
Test
Sorbent Material
Kraton 1101
Kraton 1107
Urea Formaldehyde
2" x 24" x 60"
Polyurethane" '
Polyurethane'2'
Polyurethane'^'
Ekoperl
Hny <*>
Conditions: Sorbent applied to
Quantity
Used Thickness
(Ibs.) (in.)
25 1/4
25 1/4
1.6 1/4
20 1/4
20 1/4
5 1/4
24 1/4
49 1/4
1. Fine ground polyurethane (ca1. 1/4" diameter).
the polyurethane. There was no trace of oil
oil slick confined to 20
Test Oil
Quantity Viscosity
(Ibs.) (cs.)
700 4
700 4
700 4
556 6
660 6
300 6
300 ' 6
700 6
' x 20' area,
Test
Time
(hrs.)
24
24
24
2
1
5
24
24
For this test there was insufficient
left after removing the polyurethane.
2. Polyurethane in 9-feet long by 2-feet diameter bag. The bag picked up
102 pounds o£ oil.
3. Scraps of polyurethane of 1 and 2-inch thickness in various shapes and
4. Performance of straw and bagasse are similar to hay.
no mixing
Oil Oil to
' Removed Sorbent
(Ibs.) Ratio
23 1.1
ca. 30 1.2
41 26
560 28
100 ' 5
230 46
120 5
210 4
oil present to saturate
over 500 pounds of water and only
sizes up to 1-foot by 4-f eet .
reatment of Oil £
0
E
CD
-------
Treatment of Oil Spills
MAT OF SORBENT FORMS
UPSTREAM FROM SCREEN
O.S TO I FPS,
FIRST FAILURE MODE-
MAT COLLAPSES AGAINST SCREEN
FINAL FAILURE MODE-
SORBENT SWEPT UNDER SCREEN
Fig. 1 - Sorbent Barrier Failure Modes in Current
23-8
-------
CONTROL OF OIL SPILLS
Booms
I INTRODUCTION
In spite of everyone's best efforts at prevention
oil has been, and will continue to be spilled
on the water. What do you do about it once
it's there? From other information presented
in this training manual you know that, if
ignored, it won't go away. It may move away
from the area where it was deposited, but if
left in or on the water, something will be
adversely affected by it. If you are the party
responsible for the loss, it is a violation of
federal law, Section 11 (b) (3), of the Federal
Water Pollution Control Act, as amended
(84 Stat. 92 33 USC 1161) not to report the oil
loss, and after you report it, it will be to your
advantage to do something about it. If you are
a pollution control official or have delegated
responsibilities in this area, you also will
want to do something about it. But what?
The first priority in your control program is
to attempt to limit the spread of the oil mass.
Experience has shown that if left to its own
devices, oil spreads into thinner and thinner
films and breaks apart into smaller patches
covering larger areas. The greater the area
covered the more difficult and costly the clean-
up program becomes. As the oil mass spreads,
resources such as municipal, industrial, and
agricultural water supply sources; waterfowl,
fish and general aquatic flora and fauna;
recreational interests, both public and private,
as beaches, shorefront properties and homes,
marinas, pleasure boats and tourist centers;
and shellfish harvesting, to name a few, may
be affected. To contain an oil spill within a
limited area, oil retention barriers commonly
called "oil booms" have been developed. A
satisfactory boom design has to overcome the
many forces acting upon it.
Forces are exerted by the oil being contained,
and the water in which it is immersed. The
boom may be used to encircle an oil slick to
prevent its spread, to encircle an oil slick and
then compact it so as to decrease the area of
coverage and increase film thickness to make
recovery easier, or to keep the oil away from
sensitive areas. It is an essential tool in any
oil pollution control program and generally
will be the first piece of equipment placed on
scene and the last removed. Considering its
importance, an understanding of the way the
barrier functions, and the limitations of
different designs, is essential.
II CHARACTERISTICS OF OIL ON WATER
In order to understand the forces acting on a
boom being used to contain oil in the water
environment, it is first necessary to under-
stand those forces acting on the oil itself.
When oil is spilled on water, it generally
tends to spread outward on the water surface
forming a thin continuous layer or, depending
on conditions, it may tend to accumulate as
a slick having some particular thickness.
How it will spread depends on the surface
tension of the water, the surface tension of
the oil, and the interfacial tension between
the oil and water. The tendency to spread
is the result of two physical forces: the
force of gravity and the surface tension of
the water on which the oil has been spilled.
The horizontal motion of the oil slick is
caused by outward pressure forces in the oil
which are a direct result of the gravitational
force. Of the forces acting, gravity and
surface tension will tend to increase the
spread of an oil film while inertia and viscous
forces tend to retard it. The spreading •
tendency will be increased by waves, wind, and
tidal currents. In general the spread resulting
from these random motions will be smaller
than those caused by tension and gravity forces.
It must also be recognized that the character
of oil when spilled on water does change with
time, but generally the properties which are
important to spreading, namely, density,
viscosity and the surface and interfacial
tensions, change slowly and, therefore, can
generally be predicted.
IN. PPW. ol.lS.5.71
24-1
-------
Control of Oil Spills
The equations which follow define only what
the diameter of an oil slick would be if it
remained as an integral mass after loss.
The oil mass may be transported to different
locations by wind, tide or current conditions,
while still spreading. If the situation is such,
however, that the slick is broken apart into
many smaller components, these equations
may only be applied to each integral com-
ponent as there is no acceptable way of
accurately predicting the total area which
might be covered by individual oil masses
other than actual field observations.
For the situation in which a quantity of oil is
spilled into the aquatic environment within a
short time frame (not a slow continuous
discharge), the following series of equations
may be used to predict the diameter of the
oil slick (1 in feet) after a specified time
(t in seconds).
The symbols used in the following equations
may be defined as follows:
1 - diameter of the oil slick in ft.
t - time in minutes from entry of oil into
the aquatic environment for which size
is required
v - volume of oil spilled in gallons
g - gravitational constant
32 ft/sec2
v - kinematic viscosity of water
10.7X10"6 ft2/sec
a - net surface tension of oil (typical
order of magnitude)
20. 6 X 10"4 Ibs/ft (30 dynes/cm)
P - difference in mass density between
water and oil (typical order of magnitude
3.12 Ibs/ft3)
Situation 1
The time period within 1 hour after the
spill occurs when gravity and inertia
forces are important:
1 =
(Ag) (v) (0.13) (0(60) 1/4
Substituting typical values for constants -
1 = 11.1 f(v)(t2)] 1/4
Situation 2
The time period from 1 hour to 2 hours
after a minor spill, from 1 hour to 24
hours after amoderate spill, and from
1 hour to 48 hours after a major spill
when gravity and viscous forces dominate:
1 =
(Ag)(v2) (0.13)2 (t
3/2
)(60)
1/2
L!L]
Substituting typical values for constants -
1/6
1 = 6.53[ v2 t 3/2 ]
Situation 3
The final phase when surface tension is
balanced by viscous forces:
1 =
Substituting typical values for constants
1 = 9.66 [ t3] 1/4
Figure 1 illustrates the application of these
3 equations to the special case of a 10, 000
ton oil spill. The 3 situations are clearly
illustrated. It must be remembered that
values calculated are only general
approximations as they are based on order
of magnitude estimates.
24-2
-------
Control of Oil Spills
The thickness in inches (h) of the spill
may be computed at any time by the
equation:
or
I2 (12)
h =•
(0.011)
Situation 2
1 =
"2
Agv (0.13) x
2 3/2~
1/4
L_ v
1/2 7/2
'
Substituting typical values for constants
1/4
1= 3.1
-2
Situation 3
Situation 3 describes a growth pattern
which is independent of the volume v of
the oil spill. This is possible as the
thickness of the slick is no longer of
importance in considering the major
forces involved.
When the oil is being discharged from a
stationary source at a fairly constant
rate, a modification of the above equations
is required to estimate slick width
(I in ft.) at a specific distance (x in ft.)
from the source. These equations may
be used to model discharge patterns from
sunken or grounded tankers and offshore
oil wells.
Additional symbols employed are:
1 - width of slick in feet
v - volume flow rate in gal/sec
x - horizontal distance from stationary
source in feet
M - current in ft/sec
Substituting typical values for constants -
1= 0.449 -
typica
XI
-M -I
It should be noted that in the final phases
of the spill, the spreading is independent
of the volume flow rate.
The force causing the oil to spread may
be calculated from the following equation
(see Figure 2):
F = a - ( o ) (CoS9 ) +(a )
o w o o ow ow'
where
F - force causing the oil to spread in
dyne/cm
The situation description for the following
is the same as for bulk discharge.
a - surface tension of the water,
(typical order of magnitude
1 dyne/cm)
Situation 1
Substituting typical values for constants -
I- i.6irvxV/3
a - surface tension of the oil (typical
order of magnitude 30 dyne/cm)
a - interfacial tension in dyne/cm
9Q - contact angle of oil with water at
water surface in degrees
9 - contact angle of oil/water interface
with water surface in degrees
24-3
-------
10
t (SEC)
Figure I - THE SIZE Jt OF AN OIL SLICK AS A
FUNCTION OF TIME t FOR A 10,000 TON SPILL,
OIL SURFACE TENSION, a.
AIR
WATER SURFACE TENSION, a,
INTERFACE SURFACE TENSION, a,
Figure 2 - FORCES ACTING ON AN OIL DROPLET
ON WATER.
-------
Control of Oil Spills
Although theoretically this force should be
considered in boom design, when compared
with the other forces acting to cause boom
failure in the water environment, it becomes
insignificant as will be seen in Section III.
Another characteristic to be considered is
that a globule or droplet of oil will have a
predictable "rate of rise" as it emerges
from an underwater position and rises to
the water surface. During the "rise" it is
subject to lateral displacement by ocean
currents. Large globules of oil (greater
than 1 inch in diameter) rise at the rate
of approximately 1 foot per second.
Smaller droplets rise at about 1.5 feet
per second. In placing a containment
boom to capture oil either emanating from
a submerged source, or falling from a
substantial height, the "rate of rise"
phenomena has to be considered.
For example:
A tanker has ruptured a line on deck and
residual fuel oil is running out of the
scuppers to the water 20 feet below. The
oil is penetrating into the water to a depth
of 15 feet. It will take 15 seconds to rise
up to the water surface. There is an ebb
tide and the current immediately off of the
anchorage is 1 knot. The oil will return
to the surface approximately 30 feet down
current of the point of entry. A contain-
ment boom placed closer than 30 feet to
the vessel would lose much of the oil being
spilled.
An appreciation of the above concepts is
important in understanding why a boom is
necessary and how it may be used. It can
provide a basis for the spill control officer
to develop his own rules of thumb for pre-
dicting the physical size of the slick he is
going to have to contend with. Coupled
with the rule of thumb that a slick will
move generally in the prevailing wind
direction and at 3% of the wind velocity
and taking into account the effect of tide,
current and sea state, where applicable,
he can begin formulating the plans for his
first line of defense.
Ill FORCES ACTING ON A BOOM
This section will be primarily concerned with
defining the reasons why a boom fails. This
does not mean physical failure of the boom
itself, which is a function of the structural
strength of the materials out of which it is
fabricated, but rather failure of the boom to
contain oil while remaining physically intact.
A boom is supposed to be capable of retaining
oil slicks; concentrating oil slicks so as to
increase thickness; acting as a device to move
oil across the surface of the water from point
to point; and serving as a diversionary or
protection barrier to keep oil out. In almost
all cases there is a regrettable tendency to
overrate these capabilities rather than
underrate them. With present technology,
the most satisfactory way of dealing with an
oil spill is to contain the oil and then physically
remove it as rapidly as possible. The fre-
quent failure of the containment system
greatly complicates the physical removal
effort.
When a barrier is placed in the path of an oil
slick, the spread effect is interfered with and
a pool of oil, generally much deeper than that
which would result from an undisturbed slick,
is formed.
The boom's performance is affected by wind,
waves, and currents. It must be capable of
conforming to the wave profile so as to main-
tain its freeboard and have sufficient structural
strength to withstand the stresses set up by
wave and wind action. Sufficient vertical
stability is required to overcome the roll
effect forces set up by the water current on
the fin and wind on the sail to keep the boom
from being flattened out on the water surface.
Freeboard (sail) must be adequate to prevent
oil from being carried over the top of the
boom by wind action and choppy wave motions.
Although wind and wave action are important
in boom design, water currents are the usual
reason for boom failure. Wind is often the
controlling factor in moving a slick about on
the surface of the water, and wave motion
often contributes to breaking up an integral
slick into many smaller patches. The
24-5
-------
Control of Oil Spills
relative current, the resultant of that
generated by the water current in the area,
be it tidal or river, and the motion of the
boom itself, however, will often be the
controlling factor in boom failure. Boom
failure is defined as a loss of its capability
to retain the oil slick.
The following presents a theory, backed by
experimental and field results concerning
the effects of water currents on oil contain-
ment by booms. This information should
assist the pollution control officer in selecting
the proper depth of skirt and length of boom
required in those cases where mechanical
barriers appear feasible. The thought should
be kept in mind that a mechanical barrier
does not have to remain stationary. The
relative velocity profile can be changed by
allowing the barrier to drift with the oil mass.
The failure mechanism can also be modified
by instituting skimming action as soon as
possible after the slick is boomed. Quite
often, however, the amount of skimming
capability available will not be adequate to
prevent failure without additional action.
The failure characteristics can also be
modified by the use of ad/absorbents which
will change the thickness profile of the oil
in the boom area. An understanding of the
failure mechanism provided by the following
information is intended to provide a basis
for deciding how the boom may best be
implemented (fixed containment, drift con-
tainment, diversionary use, etc.), and how
and when other materials (skimmers, ad/
absorbents) might be implemented.
Experimental work has shown that an oil
slick being contained by a mechanical barrier
will exhibit a shape like that shown in Figure 3.
Initial failure will occur when oil droplets
break away from the lee side of the head wave.
After a critical velocity (u ) is exceeded, oil
droplets will be entrained in the flowing water
stream. Unless the droplets have sufficient
time to rise through the water and rejoin the
slick in Regions I or II, they will be swept under
the barrier.
Region I is the critical area for defining the
limits for oil breakaway. The type of con-
figuration which the oil mass assumes in this
region is similar to a gravity wave. The
thickness of the oil may be found from the
equation:
2
u
h ='
u
Where
h - oil film thickness in feet
u - water current in ft/sec
r
g.- acceleration due to gravity 32 ft/sec^
•w _ 1
p specific gravity of oil
Figure 4 gives the oil thickness for a wide
range of currents and oil types. The depth
of the head wave will be equal to 2.4 h.
To determine the current (u ) at which
droplet formation will start,0 it is necessary
to predict droplet size. The maximum size
possible will be the control.
max
=TT
a £r
1
1/2
Jl~A~p J
Where
d - max. drop size in feet
max
a - oil-water interfacial tension, 30 dynes/cm
gc- 32.2 ft/sec2
2
g. - acceleration due to gravity 32 ft/sec
Ap - waterqdensity minus oil density in
Ibs/ft
The maximum d which can be achieved with
any type of oil is 0.75 inches.
24-6
-------
Control of Oil Spills
Then
1/2
Where
u = critical velocity of which oil droplets
will be torn off
w
density of water, 62.41bs/ft
For critical conditions (max. droplet size)
u will equal 0.62 ft/sec. Below this velocity
n8 droplets will be released from the head
wave. Exceeding this velocity does not
necessarily mean that oil will be lost under
the barrier. It may be redeposited on the
slick in Regions II or III. There will be
circulation and drag phenomena working in
Region II as well as the generation of waves
at the oil-water interface. These will affect
the location of the point of reattachment. In
Region in which runs from the boom to a
point = to approximately 5 times the boom
skirt depth, any oil droplet entering will be
swept under the boom.
The oil droplet, once released from the head
wave, will be affected by the buoyant force,
drag force, gravity force, and to a lesser
extent, by a negative lift force. These will
determine the acceleration of the droplet and
the final velocity or terminal rise velocity
(Vt) achieved. Typical values for this for
No. 2 oil (specific gravity = 0. 8) through No. 6
oil (specific gravity = 0.99) are presented in
Table 2. If the length of the slick in Regions
I and II is longer than
2h
u
the droplet will reenter the oil layer. If the
slick is shorter than this, the droplet will be
carried under the barrier to emerge on the
other side. The slick length in Regions I and
II is going to depend on how the barrier is
deployed and the environmental conditions
existing when it is deployed. In many cases
the maximum possible 1 will be obvious. In
others the use of Figure 4 coupled with an
understanding of the principles discussed in
Section II will be of assistance.
Figures 5 and 6 provide a graphical means
of predicting droplet failure for No. 2 and
No. 6 oil respectively. The region below
the solid horizontal line is completely safe
from droplet failure. In the region above
the sloping lines, droplet failure is certain.
Between the sloping lines and the horizontal
line, failure is uncertain. It is in this area
that environmental factors, other than those
allowed for, may cause problems. The
dashed lines on the graph represent failure
by "draining. " This loss phenomenon occurs
when flow conditions exist where oil can
plunge under or drain past the boom with the
water. Until recently this was felt to be the
primary reason for boom failure. This loss
can be controlled by changing skirt depth as
the loss is essentially independent of the
amount of oil spilled. Graphical information
for determining the appropriate skirt depth
is presented in Figure 7.
The volume of oil per unit breadth of boom
may be calculated based on actual field
conditions, either existing or predicted.
This is the best approach. If this is not
possible, the use of the concepts developed
or referred to previously have been used to
develop Figures 8 and 9. These are for an
oil with a specific gravity approximately
midway between No. 2 and No. 6. Figure 8
provides information which may be fit into
the boom configuration associated with your
particular circumstance. Figure 9 provides
data for an idealized situation. Additional
information may be obtained by consulting
the references noted in the Bibliography,
particularly No. 9 by Dr. Moye Wicks.
Air barriers are beginning to find some
application as protection devices at fixed
installations located in fairly quiescent waters.
Generally the barrier is made from a pipe,
1 inch I. D. or less, with a series of orifices
drilled through the pipe wall 1/16 inch in
diameter or less. Air is supplied by either
an air compressor or blower.
24-7
-------
BEHAVIOR OF AN OIL SLICK CONTAINED BEHIND A BOOM
-------
0.0
I 10
WATER CURRENT, FT/SEC
OIL FILM THICKNESS IN REGION I
FIGURE 4
-------
>*>•
I
n
+
•t
SUMMARY TABLE 1
COMMERCIAL FLOATING BOOMS
Boom
Stage of Development
Cost $/Ft.
Manufacturer
1. Abribat Boom
2. Aqua Fence
3. Boom Kit
Bristol Aircraft Company Boom
5. British Petroleum Company Boom
6. California Oil Company Boom
7. Elo-Boom
8. English China Clay Company Boom
Under Patent
Under Development
In Production
In Production
Under Patent
In Production
In Production
In Production
Unknown Address Unknown
France
Unknown Versatech Corporation
Nesconset, Long Island
New York
Unknown Roberts Plastics Ltd.
England
Unknown Bristol Aircraft Company
England
Unknown British Petroleum Company
Finsburg Circus
London, E. C. 2, England
$2.45 California Oil Company
Perth Amboy, New Jersey 07501
$2.20 Helly J. Hansen A/S
Moss, Norway
Unknown English China Clay Company
England
-------
Boom
Stage of Development
Cost $/Ft.
Manufacturer
9. Flexy Oil Boom
10. Flo-Fence
11. Galvaing Floating Booms
12. Gates Boom Hose
13. Headrick Boom
. Jaton Boom
15. Johns-Manville Spillguard
Booms
16. Kain Filtration Booms
In Production
In Production
In Production
In Production
Under Development
In Production
In Production
In Production
Unknown
Unknown
$16.20-$22.40
$50.00
Expected Price
$25-$35
Unknown
$7.50-$20.00
$18.00-$23.00
Smith-Anderson Company, Ltd.
3181 St. James Street West
Montreal, Quebec
Logan Diving & Salvage Co.
530 Goodwin Street
Jacksonville, Florida 32204
Gamlen Naintre & Cie
92 Clichy, 2,
Rue Huntiziger, France
Gates Rubber Company
6285 East Randolph Street
Los Angeles, California 90022
Headrick Industries, Inc.
4900 Crown Avenue
La Canada, California 91011
Centri Spray Corporation
39001 Schoolcraft Road
Livonia, Michigan 48150
Johns-Manville Company
22 East 40th Street
New York, New York 10016
Bennett International Service
302 A-5645 Topanga Canyon
Boulevard
Woodland Hills, California 91364
O
O
&
s,
9.
-------
CO
I
>-•
to
D
-*-
^
a,
o
Boom
17. Marsan Inflatable Oil
Barrier
18. MP Boom
19. Muehleisen Boom
20. Oscarseal - Hover Platforms
21. Oscarseal - Steel Boom
22. Red Eel
23. • Retainer Seawall
Stage of Development
In Production
In Production
In Production
Patent Pending
Patent Pending
In Production
Patent Pending
Cost $/Ft.
$5.95 -$6.95
$9.75
Submitted Upon
Request
Submitted Upon
Request
$40 - $50
$2.60
$20.00 light duty
$58.60 heavy duty
Manufacturer
Marsan Corporation
Box 83, Route 1
Elgin, Illinois 60120
Metropolitan Petroleum
Company, Inc.
25 Caven Point Road
Jersey City, New Jersey 07305
Muehleisen Manufacturing Co.
1100 North Johnson Avenue
El Cajon, California 92020
The Rath Company
P.O. Box 226
La Jolla, California 92037
Morrison-Knudsen Company, Inc.
Box 7808
Boise, Idaho 83707
Trelleborg Rubber Company, Inc.
P.O. Box 178
225 Main Street
New Rochelle, New York 10802
Environmental Pollution Systems
209 Profit Drive
Victoria, Texas 77901
-------
Boom
Stage of Development
Cost $/Ft.
Manufacturer
2U. Sea Curtain
25. Sea Fence
26. Sealdboom
27. Sea Skirt
28. 6-12 Boom
29. Slickbar Oil Boom
30. SOS Booms.
.In Production
Experimental
In Production
Developmental.
In Production: .
. In. Production.
•,.'•. In Production.
$ 2 -$ k light duty
$10 -$15 heavy duty
Unknown
$12.00
Unknown
,$ 9.75
$3.85-$' 6.80, 4"
$5.25-$12.25,.. 6"
$5.50-$16.50
Kepner Plastics Fabricators, Inc.
4221 Spencer Street
Torrance, California 90503
Aluminum Company of America
4-63 48th Avenue
Long Island City, N.Y.11101
Uniroyal, Inc.
10 Eagle Street
Providence, Rhode Island 02901
Core Laboratories, Inc.
Box 10185
Dallas, Texas 75201
Worthington Corporation*
Pioneer Products Division
P.O. Box 211
Livingston, New Jersey 07039
Neirad Industries
Saugatuck Station
Westport, Connecticut 06880
Surface Separator Systems
103 Mellor Avenue
Baltimore, Maryland 21228
o
o
|
O
i—•
O
t-h
o
Cfl
13
-------
CO
I
>-*
rf^
o
o
>-i
O
H-"
a
o
Boom
31. Transatlantic Plastics Boom
32. T-T Boom
33. Warne Booms
. Water Pollution Controls
Boom
Stage of Development
Unknown
In Production
In Production
Patent Pending
Cost $/Ft.
Unknown
$6.77-$8.08
$15.00-$36.00
Unknown
Manufacturer
Transatlantic Plastics Ltd.
England
East Coast Service, Inc.
34-3 Washington Street
Braintree, Massachusetts 02184
Surface Separator Systems
103 Mellor Avenue
Baltimore, Maryland 21228
Water Pollution Controls, Inc.
2035 Lemoine Avenue
Fort Lee, New Jersey 07024
-------
Ul O^ ^1 OD>O ^*
3.0
DASHED LINE SHOWS THE
CURRENT ABOVE WHICH
FAILURE WILL OCCUR BY
OIL BRAINING PAST THE SKIRT
BOOM(S) SKIRT DEPTH
0.001
0.01 O.I
VOLUME OF OIL PER UNIT
FAILURE DIAGRAM FOR OIL WITH SR
10
BREADTH, BBL /
GR. =0.8. a = 40
FT
DYNES/CM.
-------
DASHED LINE SHOWS THE
CURRENT ABOVE WHICH
FAILURE WILL OCCUR BY
OIL DRAINING PAST THE SKIRT
BOOM(S) SKIRT DEPTH '
IE OF
FAILURE DIAGRAM FOR
PER UNIT BREADTH0 SBL / FT
OIL WITH SR GR. ^0.990c^4O DYNE!
-------
10©
9
0
7
i
9iHi«iBlH;£V1S2BBHMMBMinMlllllllllli5V •••••••• Hill Ifflll Hill Mil
^-I^•»-.«••••• ™.t»I—;-T:— —"""««'_•_• — •«mmmmmmmmmfgrn^B«*_»• ^• •• • •'•••• •'••*•••>«• >
Gal
3 456789 B.O 2 3 456789 10
WATER CURRENT FT/SEC
3UM SKIRT DEPTH TO PREVENT DRAINING
FIGURE 7
-------
DASHED LINE SHOWS THE
CONDITIONS CORRESPONDING
TO 5 BBL/FT OF WIDTH
3 4 567891
•ID
3 4 567891
2 3 4567891 2
DISTANCE, FT
Oil film thickness versus distance for various water current speeds for oil with sp. gr. = 0.90, n = 81 cp.
3 4567891
-------
100
ISO
200 25O
DISTANCE , FT
300
350
4OO
50
c
X
m
. Cumulative oil film volume per unit width it various distances and water velocities for oil with sp. gr. = 0.90. ji= 81 cp.
(0
-------
Control of Oil Spills
As as example of capacities required, a
600 cfm compressor is capable of supplying
adequate air to 100 feet of 1 inch diameter
pipe having 1/16 inch diameter orifices
positioned 40 feet below the water surface.
As the air bubbles exit from the pipe and rise
to the water surface, they impart momentum
to the water. This causes vertical water flow
which becomes horizontal at the water surface.
The surface current generated retains the oil.
Figure 10 illustrates the circulation pattern
developed. In calm waters the maximum
surface current (v ) created is related to
the volume flow rate of air per unit length of
pipe..
max
Q)
Where
max
Q
- maximum generated surface
current ft/sec
- a constant
- acceleration due to gravity
32 ft/sec
- volume flow rate/unit length of
manifold
The surface current reaches a maximum at
a distance from the center line of the barrier
varying between d and d/2 where d is the
distance between the undisturbed water surface
and the location of the manifold (see Figure 10).
It then decreases approximately proportional
j _ -^ _.i_. _ __ ji__ i_ •_ _t__i i • _. j ..
to
where x = the horizontal distance
from the manifold. The effective depth of the
surface current (b) is 2. at x = 1 and increases
linearly for a larger x.
Water currents will cause a distortion in the
plume (see Figure 11). This distortion creates
a flow pattern which will allow some of the oil
to disperse through the bubble screen. The
greater the current, the more severe will be
the problem. As with a mechanical barrier,
oil drops are lost from the bottom of the slick;
in this case, because of the turbulent pattern
produced.
The information presented is intended to
provide the oil pollution control officer with
a basis for making recommendations and with
the hope that it will provide him with an under-
standing of the phenomena with which he is
dealing. It is expected that his experiences
in the field will modify these concepts so that
they best serve the needs of his environ-
mental area.
IV BOOM DESIGNS
The information having now been presented
concerning the factors which should influence
boom design and the mechanisms by which
they are most likely to fail, what types of
barriers are commercially available? What
capabilities should the boom have in addition
to that most important one of oil retention?
One of the more important is transportability.
Cleanup equipment, in general, should be
designed for easy transportation from some
centralized storage point to the site of a
pollution incident. A modular system designed
for air transport would be best. Once the
equipment is on site, ease of deployment is
essential. Regrettably, spills are not in the
habit of occurring in ideal weather conditions.
The equipment should be designed to provide
maximum compatibility with the type of
watercraft that are likely to be used in its
deployment. In particular, weight handling,
towing, and equipment assembly requirements,
should be selected with the capabilities of
available vessels in mind. The barrier
system design should also be as compatible
as possible with the other cleanup equipment
available. Such a simple thing as non-
compatible connecting hitches can destroy a
well laid-out spill control program. Last of
the major points but by no means least, the
containment system should be mutually
supporting to the recovery system. Containing
an oil spill without matching provisions for
optimum physical removal is winning less than
half the battle. Wherever possible, components
within the barrier system should be readily
adaptable for use with the oil removal system.
Oil retained and not removed will end up
being oil lost to the environment.
24-20
-------
MOUND
\ o ° L_. BUBBLE
\ io-»+~Z^
PLUME
MANIFOLD
'max
—Xd— SURFACE
V^ CURRENT
/ S'SS / S S / / /
-CIRCULATION PATTERN AND VELOCITY PROFILES IN
AIR BARRIER
-------
MOUND
STAGNATION LINE
PLUME
CIRCULATION PATTERN UPSTREAM OF
AN AIR BARRIER IN A CURRENT
FIGURE II
-------
Control of Oil Spills
The types of equipment available may be
broadly categorized into three mechanical-
type designs and pneumatic barriers. The
mechanical barriers are:
1 "Curtain booms" which consist of a surface
float acting as a barrier above the surface
and a subsurface curtain suspended from
it. The curtain is flexible along the
vertical axis. It may or may not be
stabilized by weights to provide greater
resistance to distortion by subsurface
currents and have a chain or welded wire
rope to transfer stress along the barrier.
2 &3 Light and heavy "fence booms" have a
vertical fence or panel extending both
above and below the surface of the water
to provide freeboard to counteract wave
carryover and draft below the water
surface. The flotation assembly is
generally bonded to the fence material.
The lower edge of the panel is frequently
stabilized and strengthened by a cable or
chain. The distinction between light and
heavy is generally one of size of components
and weight.
The general characteristics of these designs
are shown in Figure 12.
There are over 50 different commercially-
available booms that would fit into these
three categories available at the present
time. A partial listing is presented in Table 1.
More detailed information for one example
of each type follows. For additional infor-
mation, it is suggested that you consult
Bibliography reference No. 6.
Curtain Boom - Slickbar
The Slickbar boom manufactured by Slickbar,
Inc., Westport, Connecticut, is probably the
most popular and most commonly encountered
of the curtain booms presently available.
All of their present designs consist of a
cylindrical-closed cell, foamed-plastic float
with a flexible plastic curtain extending
approximately half-way into the float. The
curtain is secured to the float by a series of
stainless steel straps which are riveted to
the fin at appropriate intervals depending on
float size. Lead ballast is riveted to the
bottom of the flexible curtain. The amount
and spacing depends upon the environmental
conditions expected at the use site. A
1/4 inch stainless steel cable runs the length
of each boom section immediately below the
plastic float and inside of the stainless steel
strapping (see Figure 13).
The booms are available in 4- and 6-inch
float diameters with curtain (fin) depths
available from 6 to 24 inches. Standard
sections are available in 4- and 9-foot float
lengths with 6 inches of plastic fin extending
beyond each end terminating with stainless
steel connector plates. This extends the
effective length of each boom to 5 and 10 feet
respectively. The sections are connected to
provide a continuous barrier.
Prices for the 6-inch diameter float boom in
10-foot lengths complete with ballast weights,
ranging from 0. 9 to 3.6 pounds per linear
foot and having fin depths available from 6
to 24 inches, range from $6.40 to $9. 85 per
linear foot. These booms are intended for
use in relatively quiescent waters of the type
found in lakes and protected in harbor areas.
A larger and heavier boom with a 12-inch
float and 24-inch skirt is presently under
development by Slickbar for use in estuarine
areas where rougher waters are encountered.
This will cost approximately $12.25 per
linear foot.
Light Fence Boom - "T-T" Boom
The "T-T" boom was developed in Norway :
and is presentlybeing manufactured in the
United States and marketed by Coastal
Services, Inc., a Division of Ocean World.
This boom is becoming increasingly popular
for use in calm and moderate water conditions.
It consists of a vertical section, either 15 or
36 inches deep made of 300 pound per inch
tensile strength PVC plastic-coated nylon
fabric. Aluminum rods are sewn into the
nylon fabric running vertically from top to
bottom at either 2- or 3-foot 4-inch spacing.
Lead weights are permanently fixed to the
fabric at appropriate intervals on the lower
edge of the boom generally beside the vertical
aluminum rods. Increased ballast may be
provided by means of a chain or wire rope
threaded through eyelets on the bottom of the
24-23
-------
Control of Oil Spills
curtain. Plastic floats, either rigid-sealed
polystyrene type or a closed cell foamed
plastic, are attached to the barrier by means
of a sash chain with a toggle bar (cotter pin
type arrangement). These are generally
spaced to fall along the vertical aluminum
rods, and are positioned such that two-thirds
the height of the barrier is below the water
and one-third above. The boom is manu-
factured in standard lengths of 50 meters
(164 feet) which weigh approximately 220
pounds per standard length. One hundred
foot standard lengths are also available.
A -terylene rope running through brass rings
fixed on both top and bottom edges of the
curtain which made it possible to contract the
boom in an accordion-like fashion to reduce
the encircled area of an oil spill, is being
discontinued due to fouling problems in use.
Boom sections are connected by means of a
2-foot overlap of nylon with appropriate hook
and tie lines (see Figure 14).
One of the advantages of the barrier is its
lightweight and removable, easily attachable
floats. Fifty meters of barrier may be stored
in a 3 by 4 foot area and launched by one man
pulling and attaching floats in a short period
of time. When the "T-T" boom is towed in
the water to a site for use or towed in a sweeping
action to compact an oil slick, the ends of the
boom may be equipped with aluminum paravanes
for greatest stability and ease in handling.
A pair of paravanes weighs approximately
220 pounds.
The prices for the 3-foot barrier, having
vertical stiffeners spaced 2 feet on centers
with the polystyrene floats, are $9.50 per
foot. A pair of aluminum paravanes are
$724 per pair and special magnet clamps
designed to attach the boom to vessels and
sheet pilings are $376 per pair.
Heavy Fence Boom - "Headrick Boom"
This boom is manufactured by Headrick
Industries, Inc., LaCanada, California.
It is made up from a series of air inflatable
cylinders in varying configurations designed
for different sea conditions. The boom
cylinders are constructed from high-strength
PVC impregnated into a high-strength nylon
fabric. A series of air-filled flotation
cylinders are positioned above a water-filled
submersible cylinder. The water-filled
cylinder provides ballast and stability to the
total boom assembly. The tubes, as few as
two or as many as four, are interconnected
continuously by a PVC-coated nylon fabric
membrane. A steel cable is permanently
enclosed in a loop of the fabric attached to
and suspended below the water-filled ballast
tube (see Figure 15).
The air tubes are segmented every 50 feet
and the water tube every 20 feet so as to
provide boom integrity when damaged. The
boom is kept stored in a deflated unfilled
condition. When needed, it is either unrolled
or unfolded and each chamber separately
filled with air and water from a surface
vessel. The inflatable tubes are reported
to retain their air supply for several weeks.
If the application situation requires that the
boom remain in the water for long periods
of time without surveillance, the air tubes
may be filled with polyethylene beads,
expanded styrofoam or similar materials.
Once inserted, however, it is not practical
to remove these materials. They also detract
one of the barriers more desirable charac-
teristics, its flexibility.
A boom made up of 3 ten-inch diameter air
tubes and a 10-inch water tube, weighs
approximately 1.8 pounds per foot deflated.
Booms will be available in 10, 13, 16 and
22 inch tube sizes. The 22 inch tube unit
will weigh 3. 6 pounds per foot. The standard
length is 1, 000 feet which is composed of four
250-foot sections complete with the necessary
coupling hardware. These cost $25, 000 to
$35, 000 per standard length.
In addition to the above, some special multi-
purpose mechanical booms are presently
available. Some are designed to provide
ab/adsorbing capability, others integral
skimming capability along with their oil-
retaining function. A partial listing of these
is presented in Table 2.
24-24
-------
CURTAIN BOOM
Freeboard 3"- 6"
Float. Foamed
Plastic or Air
Flexible Curtain.
Canvas or Plastic
Curtain Ballast Weights.
Coble or Cham
LIGHT FENCE BOOM
Freeboard 8" — 12"
Buoyancy Material
Fomed or Molded Plastic
Panel Ballast
Chain or Cable
36
Vertical panel may
be plastic, reinforced
fabric or metal.
HEAVY FENCE BOOM
Buoyancy Float.
Plastic, Drums or
Inflated Chamber.
Tension Cables
Panel may be rigid
or flexible. Wood, plastic,
fabric or metal.
TYPICAL BOOM DESIGNS
FIGURE 12
-------
Control of Oil Spills
AVERAGE WATER LINE STAINLESS-STEEL STRAP STAINLESS-STEEL END PLATES (3)
13 per Float
FOAMED-PLASTIC FLOAT
9 feet long
BRONZE SLEEVE
STAINLESS-STEEL CLIP
STAINLESS-STEEL
NUTS and BOLTS
BRONZE SHACKLI
STAINLESS-STEEL TANC
STAINLESS-STEEL V« " CABLE
ORANGE PLASTIC FIN
STAINLESS-STEEL RIVET HARDENED-LEAD BALLAST, Riveted
Quantity as Required
FIGURE 13
SLICKBAR BOOM
24-26
-------
TEBYIENE UN!
ALUMINUM BAR
STIFFENER
FOAM-PLASTIC FLOAT
PLASTIC SKIRT
LEAD BALLAST
T-T BOOM
Figure 1^.
T-T BOOM
-------
OPEN OCEAN
SEMI.PROTECTED
WATER
>•
*
-
: -
Figure 1 5
HEADRICK BOOM
-------
Control of Oil Spills
TABLE 2 - Calculated Terminal Velocities
Interfaclal Tension -10 Dynes/Cm
Dlam.
In.
o.ooto
0.0020
0.0040
0.0065
0.0100
0.0200
0.0400
0.06SO
0.1000
0.2000
0.4000
0.6500
1 .0000
Oil Specific Gravity
.8
0.003566
0.007133
0.014266
0.023183
0.035668
0.071317
0.141914
0.223815
0.307306
0.369552
0.000000
0.000000
0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.85
.002916
.005832
.01 1664
.018955
.029162
.058317
. 1 1 6273
.185383
.263190
.339260
.000000
.000000
.000000
.9
0.002195
0.004391
0.008782
0.014271
0.021956
0.04391 1
0.087688
0. 141099
0.207284
0.295863
0.000000
0.000000
0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.95
.001351
.002703
.005406
.008785
.013516
.027032
.054041
.087549
. 132S67
.22151 1
.252218
.000000
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000945
.001890
.003781
.006144
.009452
.018906
.037806
.061357
.093750
.170109
.2181 10
.000000
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.98
.00071 1
.001423
.002846
.004626
.0071 17
.014234
.088467
.046231
.070878
.134129
. 190420
. 195046
.000000
.99
0.000438
0.000876
0.001752
0.002847
0.00.4381
0.008762
0.017525
0.028473
0.043759
0.085882
0. 142903
0. 161475
0. 159074
b. Interfacial Tension - 20 Dynes/Cm
Drop
Dlam.
In. .8
.85
Oil Specific Gravity
.9 .95 .97
.98
.99
o.ooio
0.0020
0.0040
0.0065
0.0100
0.0200
0.0400
0.0650
0.1000
0.2000
0.4000
0.6500
1 .0000
0
0
0
0
0
0
0
0
0
0
0
0
0
.003327
.006655
.013310
.021 630
.033278
.066551
.132791
.212642
.306552
.41 1404
.000000
.000000
.000000
0.002720
0.005441
0.010883
0.017685
0.027209
0.05441 6
0.108678
0.! 74993
0.257795
0.371929
0.000000
0.000000
0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.002048
.004096
.008193
.013315
.020485
.040971
.081887
.132451
. 199049
.316105
.342575
.000000
.000000
0.001261
0.002522
0.005044
0.008196
0.012610
0.025221
0.050435
0.081841
0. 124954
0.224870
0.283933
0.000000
0.000000
ooooooooooooo
.000882
.001764
.003527
.005732
.008819
.01 7639
.035277
.057293
.087860
.166831
.239408
.246480
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.000664
.001328
.002656
.00431 6
.006640
.013280
.026561
.043151
.066280
.128913
.203749
.221535
.000000
0.000409
0.00081 7
0.001635
0.002657
0.004087
0-008175
0.01 6351
0.026569
0.040856
0.080979
0.145302
0.177680
0. 182599
Interfacial Tension = 30 Dvnes/Cm
Drop
Olam.
In.
0.0010
0.0020
0.0040
0.0065
0.0100
0.0200
0.0400
0.0650
0.1000
0.2000
0.4000
0.6500
1 .0000
Oil Specific Gravity
0
0
0
0
0
0
0
0
0
0
0
0
0
.8
.003194
.006389
.012778
.020765
.031948
.063894
.127600
.205385
.302108
.433290
.000000
.000000
.000000
.85
0.00261 1
0.005223
0.010447
0.01 6978
0.026121
0.052242
0.104392
0. 1 68641
0.251981
0.387498
0.409167
0.000000
0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.9
.001966
.003933
.007866
.012782
.019666
.039334
.078636
.127405
. 1 9 30 1 1
.323712
.3701 1 1
.000000
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.95
.001210
.002421
.004842
.007868
.0)2106
.024213
.048422
.078617
. 120358
.223538
.301460
.301918
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000846
.001693
.003386
.005503
.008466
.016934
.033868
.055016
.084467
.1 63156
.249643
.265958
.000000
.98
0.000637
0.001275
0.002549
0.004143
0.006374
0.012749
0.025500
0.041431
0.063675
0.135044
0.208851
0.236749
0.233599
.99
0.000392
0.000785
0.001569
0.002550
0.003924
0.007848
0 . 0 1 5 69 7
0.025508
0.039231
0.078010
0. 144561
0.185595
0. 196671
d. Interfaclal Tension - 40 Dynes/Cm
Drop
Diam.
In.
0.0010
0.0020
0.0040
0.0065
0.0100
0.0200
0.0403
0.0650
0.1000
0.2000
0.4000
0.6500
1 .0000
Oil Specific Gravity
.8
0.003104
0.006209
0.012419
0.020181
0.031049
0.062098
0.124065
0.200198
0.297655
0.446685
Q . 463371
0-000000
0.000000
.BJ
0.002538
0.005076
0.010153
0.01 6500
0.025386
0.050773
0.101433
0.164199
0.247139
0.396188
0.432937
0.030303
0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.9
.00191 1
.003822
.007644
.012423
.019113
.038227
.076434
. 123937
. 188509
.326847
.339363
.003000
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.95
.001 1 76
.002353
.004706
.007647
.01 1 765
.023532
.047062
.076427
. 1 1 7 1 60
.221364
.312749
.319623
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000323
.001 645
.003291-
.005348
.003228
.016457
.03291 6
.053475
.082147
. 1 60068
.255406
.279503
.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.98
.033619
.001239
.002473
.034027
.006195
.012391
.024733
.040263
.061935
• 122147
.211015
.246891
.247533
.99
0.000331
0.000763
0.001525
0.032479
1. 033313
0.037627
0.015256
0.024790
0.. 038 132
0.075942
0. 1 43226
0. 190127
0.206333
24-29
-------
Control of Oil Spills
In many cases, a commercial boom is not
available when an oil pollution incident occurs
and maximum use of available materials must
be made to provide at least temporary con-
tainment or diversion capability until better
equipment can be brought to the site. A
partial listing of homemade barrier types is
presented in Table 3. One of the more famous
of these is the Navy boom shown in Figure 16.
The use of air curtains for oil slick contain-
ment was discussed in Section 3 and an
example of one type presented. Submersible
Systems, Inc., Palm Beach, Florida,
manufactures an air barrier system. In
general it is designed for the environmental
conditions existing at the use location. One
unit placed in operation consisted of 20-foot
lengths of 1-inch inside diameter aluminum
pipe with 1/16 inch diameter holes spaced
every 6 inches along its length. The sections
were connected with a semi-flexible com-
pression-type coupling. Air was supplied by
a 600 cfm compressor operating at 45 psi.
The cost for this type of barrier will vary
with the site location.
V EXAMPLE OF USE
The following is a narrative presentation
illustrating one possible use of oil booms
for the control of an oil spill. It does not
specifically represent any singular pollution
incident but rather reflects techniques which
met with at least some degree of success in
actual incidents.
A vessel with a cargo of crude oil struck a
submerged object in the navigation channel
approximately 4 miles from shore. The
forward center and starboard tanks were
holed and approximately 1, 000 barrels of a
fairly heavy crude oil lost before leakage was
controlled. At present the sea is calm and
the current immediately off of the channel
where the oil was lost is approximately 2 knots.
The wind is blowing steadily from the south
at about 9 knots and will move the oil slick
northerly toward a beach area. Making use
of information previously presented, it is
determined that oil will begin reaching the
beach area in about 12 hours. Considering
the time involved, it is likely that at least
part of the slick will reach the shoreface
area and that some procedures will have to
be implemented for its protection. You want
to get equipment out to the site of the slick
as soon as possible to remove as much as
possible before it does reach the beach area.
(See Figure A)
You have two skimmers available one of
400 gpm and one of 200 gpm capacity. Work
boats, fishing boats, various types of
absorbers, and 1, 500 feet of light fence
boom, and 1, 000 feet of pnuematic barrier.
Making use of the information previously
presented in Sections 2 and 3, you determine
that your best defense barrier will not be
capable of holding the oil offshore in a fixed
position while you pump it off the water.
You have also determined, based on the
relative wind velocity, current situation,
and the type of spread to be expected from
this particular grade of oil, that without
some type of containment, you will have a
thin film of oil coming ashore within 12 to
14 hours.
The following is one approach that might be
followed. Put your larger skimmer on a
work boat along with 900 feet of the fence
type barrier and proceed out to the site of
the slick. Set up your equipment as shown
in Figure B. The skimmer should be
positioned so as to work in the pool of oil
collected by the barrier. Note that one end
of the boom is held close alongside the work
boat and skimmer with a small boat out at
the other end. The oil will collect along the
wind side of the boom and then be diverted
along the boom to the skimmer. The
skimmer should be operated at capacity
with the oil-water mix being discharged to I
some type of storage facility for oil-water
separation. Note that -
1 There must be an oil tight connection
between the skimming unit and the boom
at a and the boom and the work boat at b.
2 The position of the upwind end of the boom
and the work boat itself must be changed
quickly as the wind shifts. The flow of the
slick must continue into the area between
the boom and the pump boat.
24-30
-------
3/4" PLYWOOD
1/2" WIRE ROPE
55 GAL. DRUMS
NAVY" BOOM
BALLAST FILLED PLASTIC SKIRT
Figure 16
NAVY BOOM
-------
I
03
to
SUMMARY TABLE2
MULTIPURPOSE BOOMS
O
I
n
o
a
t:
en
Boom
Stage of Development
Cost $/Ft.
Manufacturer
1. ICI Oil Absorbing Boom
2. Roscoff Heavy and Light-
weight Booms
3. Sea Serpent
Skimmer Boom
In Production $6.75 - 7.45
Used at Torrey Canyon Spill Unknown
Under Development Unknown
Patent Pending Unknown
ICI Fibres Ltd.
Harrogate
Yorkshire, England
Marine Biological
Laboratory
Roscoff
North Brittany, France
Johns-Manville Co.
22-East UOth Street
New York, New York 10016
E. P. Hall
FWPCA
Washington, D.C. 20242
-------
Control of Oil Spills
SUMMARY TABLE 3
IMPROVISED BOOMS
Type of Boom
1. Cork-Filled Boom
2. Cork-Float Boom
3. Fire Hose Boom
4. Puerto Rican Boom
5. Rubber Bladder Boom
6. Rubber Tire Boom
7. Steel Pipe Boom
8. U.S. Navy Boom
9. Wooden Float Boom
10. Wooden Timber Boom
11. Wooden V-Boom
Location Where It Was Used
Norfolk, Virginia
Port Hueneme, California
Quiescent Waters
Ocean Eagle Oil Spill
Helford River, Great Britain
Torrey Canyon Oil Spill
Philadelphia, Pennsylvania
Long Beach, California
Chevron Spill, 1970
Pearl Harbor, Hawaii
Quiescent Waters
Peros Gyiroc, France
3 The angle between the wind direction and
the boom should not be greater than 20
degrees. With more angle the boom will
tend to develop a belly in its shape and oil
will be lost under the boom.
4 The work boat and the boat holding the
leading edge of your boom are drifting
at a speed which you have previously
determined will not allow oil to be lost
under the barrier. This s£eed will, of
course, be adjusted based on on-site
conditions.
No comments will be made about the type of
skimmer, oil-water separation system or
storage system. These are obviously a very
important concern and will control the speed
at which the recovery system will move with
the slick to prevent loss. Information con-
cerning these is presented in other parts of
the training manual.
You now have two other problems to contend
with-
1 It is obvious from your calculations that
it will not be possible to remove all of the
oil from the water surface before it gets
into the beach area.
2 The slick is not remaining as one integral
mass and portions of it are breaking away
and being left behind in the bay.
Next, consider handling those portions of the
slick being left behind in the bay. Two small
fishing boats and a contractor's work boat
having flat deck space in the bow, have been
contracted for and the remaining fence boom
and the small skimmer mounted on them.
These can be arranged as shown in Figure C.
The bow string tension line attached to No. 2
boat reduces the sharp bend that would other-
wise exist in the boom and eliminates
24-33
-------
Control of Oil Spills
turbulence and oil loss at the point where the
boom would ordinarily bend when it joins the
work barge as with No. 1 boat. With the boom
system so deployed, this work group begins
chasing those slicks left behind and using the
small skimmer, pumps them to appropriate
storage. The operating speed of this group
is controlled by the structural strength of the
boom in question which has been considerably
increased with the bow string arrangement,
and the thickness of oil being recovered at
any one time. Remember that the wind should
be used to your advantage whenever possible
to assist in diverting the oil down the funnel.
Note that radio communication among the
three boats is essential for proper functioning
of this system.
It is now necessary to consider setting up
some type of protection at the beach area.
As all that is left is the air barrier, this
will have to be implemented. The air barrier
should be placed on the bottom at a distance
from shore that will provide it with a minimum
of 10 feet of water at low tide. The air supply
can come from a diesel powered air com-
pressor mounted on a barge or convenient
headland if available. Taking a look at the
area, the most difficult area to clean is going
to be the rocky section on the northwest side
of the beach. The air barrier should be set
up so as to divert the oil from the rocky section
toward the beach area. A physical absorber
should be placed along the tidal zone of the
beach area to absorb as much of the oil as
possible to prevent penetration into the beach
sand. A float with some type of anchoring
system has been established a short distance
from the end of the air barrier so that the
work barge and skimmer, when they arrive
at this point, will have somewhere to attach
their fence boom. Initially, the oil that has
gotten away from the two skimmers working
in the bay will be diverted toward the beach.
When the main skimming apparatus arrives
on scene, the oil will be diverted along the
air barrier to the fixed mechanical barrier
to the skimmer. (See Figure D)
This is a simplified discussion of boom
placement which does not attempt to take
into account all of the variables which might
be encountered. It is cited as an example
of some of the procedures which could be
implemented making use of the information
presented in Sections I through IV. It must
be emphasized, that getting the boom out
and corralling the mess is only the beginning.
The very difficult task of removing the
material from the environment and its ultimate
disposal has to be as well considered and
planned out as your boom purchasing and
implementation program. There would have
been nothing more useless, for example, than
taking all of the barrier that you had available
in the incident cited above and drawing it
across the beach area and then sitting back
and watching the oil pile up along its face to
finally run under and/or over it to contaminate
the beach area. The best designed equipment,
if not properly used, will not do the job.
24-34
-------
ROCKY
SHOREFACE
SAND-
BEACH AREA
.CURRENT-£KNOT5
N
OIL SLICK
GENERAL POLLUTION SITUATION
FIGURE A
-------
WORK BOAT
(b)
SKIMMER
(a)
/This angle should not
/i exceed 20° :
WIND
— BOAT
FIGURE B. MAIN SLICK RECOVERY
A # I BOAT
#2 BOAT A
Turbulence and
loss of oil at this
sharp bend without
bowstring arrangement.
Bowstring tension
line reduces sharp
bend in boom.
WORK BOAT
TANK
FIGURE C. TOWING A FUNNEL BOOM ARRANGEMENT
-------
N
ROCKY
SHOREFACE
••* -I*--.'
ANCHORO /
FLOAT
SKIMMER BOOM
I SYSTEM WILL BE
I HERE WHEN
! AVAILABLE.
^BARGE MOUNTED
DIESEL
COMPRESSER
REMNANTS OF OIL SLICK
SHOREFACE PROTECTION SCHEME
FIGURE D
-------
Control of Oil Spills
REFERENCES
1 Cross, R.H. and Hoult, D.P. Collection
of Oil Slicks. ASCE National Meeting
on Transportation Engineering, Boston,
Mass. July 1970.
2 Fay, J. A. The Spread of Oil Slicks on a
Calm Sea. Clearinghouse for Federal
Scientific and Technical Information,
No. AD 696876. August 1969.
3 Hoult, D.P. Containment of Oil SpiUs
by Physical and Air Barriers.
Massachusetts Institute of Technology.
Boston 1969.
4 Lehr, W.E. and Schorer, J.O. Design
Requirements for Booms. Joint
FWPCA-API Conference Proceedings.
New York. December 1969.
Milz, E.A. An Evaluation-Oil SpiU
Control Equipment & Techniques.
21st Annual Pipeline Conference.
DaUas. April 1970.
API
Scott, A. L., et al. Removal of Oil from
Harbor Waters. Clearinghouse for
Federal Scientific and Technical
Information, No. AD 834973.
February 1968.
Testing and Evaluation of Oil Spill
Recovery Equipment. Water Pollution
Control Research Series, Grant No.
150-80-DOZ, Federal Water Quality.
1970.
Wicks, M. Fluid Dynamics of Floating
Oil Containment by Mechanical Barriers
in the Presence of Water Currents.
Joint FWPCA-API Conference
Proceedings. New York. December
1969.
6 Oil Spill Containment Systems. Northeast
Region R & D Programs, Federal
Water Quality Administration. 1970.
This outline was prepared by Thomas W.
Devine, Sanitary Engineer, New England
Basins Office, Region I, Environmental
Protection Agency. .-;• . .
24-38
-------
TREATMENT OF OIL SPILLS
Oil Skimming Devices
I INTRODUCTION
A Once an oil spill has occurred, the most
positive approach to protect the environ-
ment is to physically remove the oil from
the water. This may be accomplished, to
a more or less degree, by the use of
• mechanical pickup devices commonly
called "skimmers". The numerous types
of skimmers presently under development
do not permit a presentation on each
particular unit. If the reader desires
information on particular devices, the
Edison Water Quality Laboratory's May
1970 publication titled, "Oil Skimming
Devices", is recommended.
B The ideal oil skimmer should be designed
for:
1 Easy handling
2 Easy operation
3 Low maintenance
4 Ability to withstand rough handling
5 Versatility to operate in various wave
and current situations,
6 Ability to skim oil at a high oil to water
ratio
The present day skimmers are generally
designed to emphasize one or more of the
above characteristics. Before purchasing
a skimmer for use in a particular area,
the buyer should know what he requires
and which characteristics best suit his
needs.
The reports and studies which are ref-
erenced at the end of this outline evaluate
oil skimming devices. Using this information
we will now direct our effort towards
selecting pieces of equipment which will
meet particular needs.
II THE BASIC OIL SKIMMING DEVICES
A Mechanical devices which physically
remove oil from the water's surface
contain three basic components:
1 The pickup head
2 The pump system
3 The oil/water separator
These components may be constructed as
one unit, separate units or any com-
bination of the three. A brief discussion
of each follows.
B The pickup head - Figure 1 shows the
three most popular types of pickup heads
in use today:
1 Weir type
2 Floating suction type
3 Adsorbent surface type
The weir type removes oil from the
water's surface by allowing the oil to
overflow a weir into a collecting device
and holding the water back against the
weir. The efficiency of weir pickup heads
is highly dependent on calm water con-
ditions and an adequate thickness of oil;
however, viscosity of the oil is not too
- important. Even so, a certain amount
of water is drawn over the weir making
it necessary to provide a means for
separating the oil and water. Therefore,
this type of pickup head would be used in
areas where the water conditions are
generally calm and the oil slick thickness
can be maintained at greater than 1/4 inch.
Th-e type of oil is not a major consideration.
The floating suction type operates on the
same principal as the household vacuum
cleaner. The unit is generally small in
IN. PPW. 01.19.5.71
25-1
-------
Treatment of Oil Spills
size and is connected to the oil/water
separation section by either a suction or
a pressure hose. The floating head may
limit the amount of water either by a
system of weirs or by the design of the
intake openings. Water surface conditions
and oil viscosity greatly affect the
efficiency of these devices. The floating
suction heads are well suited for working
in tight areas such as around piers and
ships. Debris and sorbents tend to clog
these units quite readily and therefore
must be considered.
The adsorbent surface type operate on
the principle that a hydrophobic and
oleophilic surface will be preferentially
wetted by oil and not water. As the
adsorbent surface is drawn through the
slick oil will cling to it. This oil is then
removed either by rollers, wringers or
wiper blades. The surfaces are constructed
of aluminum or various oleophilic foams
or fibers.
The problem of additional oil/water
separation is eliminated with these devices.
They have been tested successfully in wave
heights up to 2 feet. Debris interferes
with their efficiency and in some cases may
cause severe damage. These units would
be best suited for open harbor use. The
type of oil to be collected determines the
type of adsorbent surface required. For
example, heavy oils tend to clog foams and
fibers and light oils are not picked up
efficiently on aluminum surfaces.
We have pointed out several parameters which
will effect the selection of a particular
pickup head:
1 Type of oil
2 Sea state - waves and currents
3 Debris - sorbents
4 Physical restrictions - piers, etc.
5 Equipment available to separate oil/
water mixtures
The Pump System - Pumps and other
accessories used with skimmers need
to have the following features incorporated
in their designs:
1 Dependability - carburetors, magnetos,
points and plugs need to be protected
against ocean air and salt spray.
2 Portability - easy to transport.
Equipment must have good balance
and good handles for manual lifting,
and sling attachments for mechanical
lifting.
3 Quick and positive coupling and
uncoupling of hoses and other
connections is essential.
4 Low maintenance costs and easy
cleaning and storage arrangements.
5 Ability to work in gangs to handle
increased volumes.
6 Protection from clogging due to debris
or sorbents.
The selection of the type of pump is very
important. A .centrifugal purnp can handle
large volumes of flow which may be
required to remove very thin slicks.
However, this type of pump imparts
tremendous mixing energy and produces
an oil/water emulsion which may not
separate satisfactorily in the settling
chamber. On the other hand, positive
displacement pumps, such as diaphragm
or piston pumps, while they cannot handle
as large a flow, do not mix or emulsify
the oil/water mixture. The efficiency of
• the settling chamber is thus increased.
Positive displacement pumps also are
very easy to repair, unclog and maintain
and do not require priming.
Here, the choice of a pump depends on the
volume of water flow required, the size
of the oil/water separator available and
the expected amount of maintenance
assistance available; Based on past
experience, the chief cause for an
unsuccessful oil skimming operation has
been due to failure in the pumping system.
25-2
-------
Treatment of Oil Spills
D The Oil/Water Separator - is essentially
a settling chamber where collected oil
separates by gravity from collected water.
A system of weirs and baffles may be
employed to facilitate separation. The
water may either be pumped out or forced
out by gravity. The oil is normally pumped
out when the tank has reached its oil
storage capacity. The separator may be
nothing more than a tank truck or it may
be specially designed to meet particular
needs.
Normally, the weir type and the floating
suction head type pickup units require an
oil/water separator. Likewise, if a
centrifugal pump is used, a separator is
usually required.
IH SUMMARY
A The basic oil skimmer is composed of
three units:
1 Pickup head
2 Pump system
3 Oil/water separator
There are three basic pickup heads in use
today:
1 Weir type
2 Floating suction head type
3 Adsorbent surface type
The pump system usually employs either
of two types of pumps:
1 Centrifugal pump
2 Positive displacement pump
An oil/water separator is required to
separate the large amounts of water
usually picked up with the oil slick.
B Tests and experiences have indicated that
present day skimmers do not operate
efficiently in wave heights greater than 1.5
to 2.0 feet or in currents greater than
1. 0 to 1.5 feet per second.
Prior to purchasing an oil skimmer, the
buyer should determine physical restrictions,
such as piers, shallow water, marshes,
etc., estimate the quantities and types of
oil to be handled, investigate the local
weather conditions and become familiar
with the body of water in which the pro-
posed skimmer is to be used. Using this
information the proper oil skimmer can
then be selected.
REFERENCES
1 Milz, E.A. An Evaluation of Oil Spill
Control Equipment and Techniques,
April 14, 1970, Shell Pipe Line
Corporation, P.O. Box 2648,
Houston, Texas 77001.
2 Proceedings of the Joint Conference on
Prevention and Control of Oil Spills,
December 1969, American Petroleum
Institute, 1271 Avenue of the Americas,
New York, N.Y. 10020.
3 Oil Skimming Devices, Edison Water
Quality Laboratory, May 1970,
Planning and Resources Office, Office
of Research and Development, EPA,
Washington, D. C. 20242.
This outline was prepared by J. S. Dorrler,
Acting Chief, Oil Pollution R & D, Edison
V/ater Quality Laboratory, Office of Water
Programs, Edison, NJ 08817.
25-3
-------
CLEANUP OF OIL-POLLUTED BEACHES
I INTRODUCTION
National and international publicity given to
Torrey Canyon and Santa Barbara incidents
have led to a public outcry to stop the oil
pollution of our national shorelines.
H QUESTIONS ON BEACH CLEANUP
The question is often asked, "How do you
clean an oil polluted beach? " The answer
to this question is relative. What is the
composition of the beach? Is it fine grain
sand; is it coarse sand; is it pebble or
shingle beach? What type of oil pollution
has fouled the beach? Was it a #2 oil,
#6 or a crude oil? How deep is the oil
penetration? What is the temperature and
the season? Where is the beach located?
Does it have access roads? Can it be
reached or traversed by wheeled vehicles
or can it only accomodate tracked vehicles?
Before we can even begin to answer a question
on beach cleanup, we must know as many
background facts as possible.
IE CLEANUP METHODS
A It has often been said that nature is the
best cleaning agent in the world. This is
especially true of rocky shores and stone
beaches. But if anyone reports that
nature removed oil from a sand beach -
dig a little deeper - literally. What
nature cannot remove, it covers up.
Wind blown sand and the seasonal move-
ment of beaches have a tendency to cover
man's mistakes.
B The most elementary method of beach
cleanup is with the use of rakes, shovels
and manpower. If the penetration of oil
into the sand is less than two inches and
the oil is not too fluid, the oil can be raked
into windrows of approximately one foot
and picked up with shovels to be placed
into a front loader or dump truck. If the
oil is not sufficiently weathered to be
viscous, it can be made more workable
through the application of a cold water
spray from a garden hose or a fire hose.
If the pollution damage to the beach is
much more extensive, then mechanical
equipment must be used. Through
research, it has been determined that
a Motorized Elevating Scraper used in
tandem with a motorized scraper, are
the best mechanical equipment to be used
in beach restoration. The combined
uses of these vehicles provide the most
rapid means of beach restoration and in
addition their use results in the removal
of the least amount of excess beach
material. Before allowing mechanical
equipment on the beach, the operators
of these vehicles must be cautioned on
the amount of beach sand to be removed.
IV PREVENTION
A It is much easier to clean up a beach if
the oil is stopped at or near the water
line. An effective method of protecting
a high-use beach from the onslaught of
oil pollution is to throw up a sand berm
approximately three feet high. This can
be accomplished with the use of earth
moving equipment or, if necessary, by
hand labor. The artificial berm should
be placed along the high water mark, to
protect the dry sand above the intertidal
• zone. If the surf is strong or very active,
or if there is an abnormally high tide,
the artificial berm will be destroyed.
Sufficient to say that the artificial berm
will only prove effective in a mild surf
and calm weather.
B Should sufficient time exist between the
notification of an oil spill and its reaching
the shore face, one method of alleviating
the damage to the beach is the extensive
use of straw, either alone, or used in
conjunction with the commercial "sorbents.'
IN. PPW. ol.lQ.5.71
26-1
-------
Cleanup of Oil-Polluted Beaches
Straw, which has a natural absorptive
capacity for oil, will adsorb between four
and ten times its own weight in oil. To
be most effective, the straw should be
laid along the low-water mark and as the
tide and oil move up the beach, the straw
should be worked into the oil, either
through natural wave action or mechanical
methods.
If the oil is still washing ashore a series
of deep pits can be gouged out of the sand
at the water's edge to allow the oil to
build up sufficient thickness to permit
removal by vacuum tank truck.
V CHEMICALS
A We firmly believe that the use of dispersants,
emulsifiers and other chemicals is entirely
unjustified in the cleanup of oil polluted
beaches. In both the Torrey Canyon and
Ocean Eagle incidents, it was noted that
the use of chemicals on sand caused the
sand to become "quick", making it difficult
to walk on and leaving a disagreeable odor
in the treated sand. (However, other
reports cite this same "quicksand" with
oil alone. As the literature on this
subject is very vague, further research
by the government and private industry
seems indicated.)
B In oil penetration tests conducted at
Sandy Hook, N. J., it was concluded that
various types of persistent oil alone
penetrated no more than two inches into
the sand while oil mixed with chemicals
(dispersants, emulsifiers, etc.) caused
penetration of the mixture into the sand
at least three times the depth of the
untreated oil.
C Application of chemicals to an oil soaked
beach and subsequent hosing down of the
mixture with sea water, the sand appeared
cleansed of oil. However, further
investigation revealed that this observation
was deceptive, as the oil and chemical
mixture was found between four and twelve
inches, in irregular bands, below the
surface of the sand.
26-2
VI BURNING
Many attempts have been made to burn oil
on the shore face. Through an extensive
literature search and personal observation
it is concluded that the burning of oil
"in situ" on a contaminated beach is not
very practicable. It has been tried with
commercial burning agents, flame throwers,
"oxygen tiles" and various mixtures of
kerosene and gasoline, but all have met
with no success. Small, "fresh" pools of
neat crudes or light oil can be burned
successfully if their lighter ends have not
evaporated, but this is a patchy operation
at best and is not recommended for cleanup
of massive spills.
VII CLEANUP OF LIGHT OILS
A Sometimes a "high-use" beach becomes
stained with a light oil such as a #2 fuel.
This becomes a problem because of instant
and deep penetration. The only really
effective method of cleansing this type of
pollution is to expose as much of the con-
taminated beach sand to the sunlight and
wind as possible. This can be done
effectively by the use of a harrowing
plow or beach cleaning machines, which
are used to remove trash from beaches.
Number two fuel, in contrast to #6 or
Bunker "C" fuel oil, contains a relative
high amount of light ends. If these light
ends are exposed to evaporation through
wind and weather, they will dissipate
rather rapidly.
B To accelerate, the evaporation and
dissipation of #2 fuel from the beaches,
a mat of straw should be laid on the
beach, at least one inch thick. A disk-
harrow should then be used to work the
straw down into the sand column so the
straw can absorb as much of the oil as
possible. A beach cleaning machine
should then be used to retrieve the oil
soaked straw. The beach should then be
harrowed or mechanically raked to hasten
the dissipation of the remaining oil trapped
in the sub-surface of the sand.
This outline was prepared by H. J. Lamp'l,
Oil Spills Coordinator, Office of Water Programs,
Edison Water Quality Laboratory, Edison, NJ.
-------
WASTE TREATMENT METHODS FOR REFINERIES
I INTRODUCTION
A Requests for information to evaluate water
requirements, wastewater treatments and
possible surface or ground water pollution
by oil refineries requires extensive study.
It is always necessary first to have know-
ledge of size of refinery, type of crude oil,
classification of refinery (topping plant,
topping and cracking plant, topping,
catalytic cracking, plus lubricating proc-
essing or a combination of all processes)
and the products to be produced. Each
refinery is built to satisfy a certain market
for its products. A corporate management
often develops certain processes that are
common only to that organization. There-
fore, it is only possible to supply
generalized information until definite plans,
elevations and location relative to other
industries and developments are available.
B For those who require an understanding of
the problems of crude oil or petroleum
processing, Bland and Davidson is an
excellent text. It furnishes both general
and technical information relating to the
processing of crude oil into useful products.
This book has a limited section on sources
of crude oil and preliminary "crude assays. "
It has extensive sections on processing,
equipment, chemicals and catalysts,
maintenance and construction. There is
also a section on offsite facilities that
includes tankage, blending areas, cooling
systems, refinery sewer systems, waste
treating facilities and utility plants.
3
C The 1968 Refining Process Handbook
describes many of the latest refining
processes.
E WASTEWATER PROCESSING AND QUALITY
CONTROL
4
A Beychok reviews the subject of aqueous
wastes. Following a chapter on "Pollutants
and Effluent Quality Regulations, " he
describes in "Refinery and Petrochemical
Plant Effluents, " three means of
segregating the waste streams of oil
processing plants, then reviews the
various process waste streams. In a
chapter on "Treatment Methods" he
details inplant treatment prior to the use
of API separators with final "Secondary
Treatment. " He also has chapters on
"Miscellaneous Effluents, " "Cost Data, "
an "Appendix, including a Glossary,
description of IOD, BOD and COD Tests, "
and an excellent reference list into the
year 1966. This is the latest and most
complete text on petroleum and petro-
chemical plant wastewater.
B Much has been done by the American
Petroleum Institute, Refining Division,
toward handling of waste streams. **
A copy of the manual should be available
to all involved in the study of refining
waste streams.
The 196.7 Domestic Refinery Effluent
Profile was developed to indicate just
what the sources of waste are and what
the various refineries are doing. This
report divides the various types of
refineries into:
1 Topping plants
2 Topping and cracking plants
3 Topping, cracking and petrochemical
plants
4 Topping, catalytic cracking and
lubricating oil processes
5 Plants, including all processes
The types of wastewater treatments are
also described in general terms by code
number.
C Another series of reprints on waste
treatment is "Waste Treatment and Flare
Stack Design Handbook. " 6 This series of
IN.PPW.ol.6.3. 70
27-1
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Waste Treatment Methods for Refineries
reprints covers the fundamentals of sewer
design through wastewater treatment plans
and the water laws that influence the
petroleum industry.
7
D Chemical Engineering presents a
"Complete Guide to Pollution Control
(Deskbook Issue)" which includes a number
of articles for the control of pollution.
E The National Petroleum Refiners
Association published reprints of papers
presented at their various meetings.
A series of these are attached. ^
F Dr. A. J. Freedman points out that a
normal refinery operation requires 18.3
barrels of water per barrel of crude
processed. Since, as mentioned earlier,
no two refineries are alike, information
presented here cannot be expected to fit
all waste treatment operations. Dr.
Freedman1 s sources and classification
of refinery wastewater are outlined in his
Tables I and II of this paper.
G Stevens and Evans state on page 1,
"Both the process design and operations
groups have generally defined a waste
stream as one from which economic gain
cannot be achieved in the allowable payout
period for capital amortization. " On page 2
there is a complete list of parameters that
should be closely observed. This same
paper states "The techniques available to
the designer of waste control flow sheets
in the refinery are literally all those
available to the designer of the process
flow sheet and, in addition, have the
powerful tool of biological treatment--
a not very common concept in the lexicon
of process flow sheet designers. "
1 Many other ideas and suggestions for
wastewater quality control can be found
in the various NPRA reports.
2 Other references are from the Oil and
Gas Journal.
9a
H Mr. Hickey has an excellent short
article which includes a suggested
wastewater survey, water use and possible
contaminates along with pollution concen-
trations and determinations. Two articles
by Ewing ' review the refinery's use
of activated sludge and lagoons in waste-
water treatment.
To become knowledgeable of the works
of others, the staff of American Oil
Company *0a describes the treatment .„
of oil wastes, and Quigley and Hoffman
describe the flotation of oily wastes.
While the title speaks only of the Petro-
chemical Industry, S.K. Mencher I1
reviews both the refining and petrochemical
industry. This is an extensive report
listing process units, source of pollutants,
pollutants and possible terminal remedy.
Mr. Mencher outlines a schematic dia-
gram of terminal waste disposal facility
for refinery petrochemical complex.
This includes 1) oily water or process
water, 2) sanitary sewers 3) demineralizer
waste and 4) oil free waters. It is stated
that "The bulk of water and in hydrocarbon
processing industries, is used for cooling
purposes and does not ordinarily become
contaminated. However, during process
operations, waste streams are released
from equipment to the sewers at many
points because of leaks, water purging
and line breakage. "
Mr. Mencher indicates that "polluted
water streams are often disgorged in the
following processing operations:
1 Crude oil desalting
2 Steam distillation
3 Steam stripping
4 Water washing of products following
chemical treatment
5 Barometric condensing of steam driven
prime movers
6 Catalyst regeneration
7 Partial pressure reduction with dilution
steam
8 Boiler and cooling tower blowdowris
27-2
-------
Waste Treatment Methods for Refineries
9 Drainage of contaminated areas--
rain water runoff
10 Treatment of water--i. e., nitrate
addition for caustic embrittlement
control
11 Transferring and storing oils
12 Vessel cleaning operations"
The ultimate disposal of any waste stream
leaving process units must be treated by
either of three methods, or a combination:
1 Physical - separating, skimming,
burial, i.e., gravity separators
2 Chemical - neutralization, oxidation,
reduction, i.e., chemical flocculation,
air flotation
3 Biological - bacterial oxidation,
anaerobic processes, i.e., biological
oxidation
in SOURCE WATER AND SHIPPING
CONSIDERATIONS
A As in the case of any steel mill, paper
mill, thermal electric power plant, or
hydrocarbon processing facility that uses
and releases large volumes of water, the
source of water should be known and a
study made of the direction of flow of any
discharge. John Piety 12 describes such
a study in Predicting the Course of an
Effluent Discharge for the south coast of
Long Island, New York. This survey
traced the underwater effluent from a
sewage treatment plant and included the
effect of winds, tides, and coastal currents.
Ross*3 is able to predict pollutant dis-
persion by the mathematics of diffusion.
The equations are derived from "equation
of change" describing mass transport or
from macroscopic balances. His solutions
yield relations desired for correlating
dispersions.
B Any time petroleum—either crude or
refined products--are shipped there are
possible hazards. In the case of tankers
and particularly those carrying 2.5
million barrels, the damage that could
be done in case of an accident is untold.
It is necessary, therefore, to maintain
systems that prevent spillage and if there
are, have safeguards such as extensive
oil booms and enclosures to prevent
release of oil to the water course. All
dockage should be protected. All tankers
necessarily have a certain amount of
ballast water and tank cleaning emulsions
to dispose of. API Manual on Disposal
of Refinery Wastes, Volume 1, Waste -
water Containing Oil, Chapter 5,
"Disposal of Ballast Water and Tank-
cleaning Emulsion from Tankers and
Barges, " and Brummage, et al., "a*
review some of the many problems and
possible solutions. Where both the crude
oil is shipped in as well as products trans-
shipped by water, the hazards are great.
IV REQUIREMENTS
In any proposed refinery, it must be
emphasized that certain information be
available to Federal Water Pollution Control
Administration and/or other agencies having
the safeguard of water as their responsibility.
This includes the name of the company
responsible for the refinery, the source of
crude oil, the methods of receiving and
possible trans-shipment of products, the
docks and protective harbor, type of oper-
ation, whether a topping plant or a more
complete refinery, the names of designing
engineering firm, storage, kind and how
much. These, plus water needs and
wastewater disposal are requirements.
REFERENCES
1 American Petroleum Institute. 1967
Domestic Refinery Effluent Profile.
Crossely, S-D Surveys, Inc.
September 1968.
2 Bland, A.F. and Davidson, R. L.
Petroleum Processing Handbook.
McGraw Hill, New York. 1967.
27-3
-------
Waste Treatment Methods for Refineries
3 Hydrocarbon Processing. The 1968
Refining Processes Handbook.
September 1968.
4 Beychok, M.R. Aqueous Wastes from
Petroleum and Petrochemical Plants.
J. Wiley & Son, New York. 1967.
5 Manual on Disposal of Refinery Wastes,
Volumes I, II, III, IV, and V.
Also Section Biological Factors of
Pollution as Affecting Receiving Waters,
American Petroleum Institute, Division
of Refining, 1271 Ave. of the Americas,
New York.
6 Hydrocarbon Processing. Waste Treat-
ment and Flare Stack Design Handbook.
GulfPubl. Co., Houston, Texas. 1968.
Chemical Engineering.
to Pollution Control.
October 14, 1968.
Complete Guide
Deskbook Issue.
8a Freedman, A. J., et al. The Chemistry
of Refinery and Petrochemical Waste -
water. GL-67-40.
8b Gossom, W. J. Minimized Waste
Abatement Costs Requires Sound Data.
GL-66-43.
8c Stevens, J.I. and Evans, R.R. The Need
for the Process Approach in Pollution
Abatement. GC-66-9.
8d Gossom, W. J. Some Considerations in
Sound Design for Waste Control.
MC-67-49.
8e Johnson, E.E., et al. Waste Disposal
Cost Allocation. MC-68-49.
8f Stevens, J.I. and Evans, R.R. Advanced
Waste Disposal Techniques Presently
Available to the Petroleum Refining
and Petrochemical Industry. GL-66-44.
8g River, C. H., et al. Treatment of
Wastewaters. Shell Chemical,
Houston Plant. MC-68-50.
8h Norwood, B. E. Applications of
Biological Trickling Filter for Treat-
ment of Effluent Water at Shell Oil
Company's Houston Refinery.
NPCEC 68-24.
9a Hickey, J.J. Here's What Refineries
Need for Pollution Measurement.
Oil and Gas Journal. August 12, 1968.
90-94.
9b Ewing, R. C. Refinery Waste Products
Pose Pollution Problem. Oil and
Gas Journal. December 9, 1968.
77-82.
9c Ewing, R.C.
Pollution.
October 12,
Lagoons Help Abate
Oil and Gas Journal.
1968. 92, 96.
lOa American Oil Company. Treating Oily
Wastes. Industrial Water Engineer.
July 1968. 22-24.
lOb Quigley, R.E. and Huffman, E.L.
Flotation of Oily Wastes. A Refinery's
Approach to Wastewater Treatment.
Industrial Water Engineer. June 1967.
22-25.
11 Mencher, S. K. Minimizing Waste in
Petrochemical Industry. Chemical
Engineering Progress. October 1967.
80-88.
12 Piety, John. Predicting the Course of
an Effluent Discharge. Ocean Industry.
August 1968. 56-61.
13 .Ross, L.W. In Air and Water - Predicts
Pollutants Dispersion. Hydrocarbon
Processing, 47:8, 144-150. 1968.
14a Brummage, K. G., Maybourn, R.,
Sawyer, M. F. Keeping Oil out of the
Sea. Ocean Industry. November 1967.
11-16.
14b Brummage, K. G., Maybourn, R.,
Sawyer, M. F. How LOT Affects
Refinery Costs. Hydrocarbon
Processing, 46:7 116-120. 1967.
Phis outline was prepared by L.W. Muir,
former Chemist. National Field Investiga-
tions Center, EPA, Cincinnati, OH 45213.
27-4
-------
LEGAL RESPONSE
Outline Number
Legislation Affecting Oil 29
National and Regional Contingency Plans 30
Functions, Responsibilities and Role 32
of the On-Scene-Commander
-------
LEGISLATION AFFECTING OIL
I INTRODUCTION
On April 3, 1970, the President of the
United States signed into law the "Water
Quality Improvement Act of 1970. " This
is the latest law enacted to fight oil pollution.
It is one of many laws passed to combat oil
spills since the first oil well was drilled in
the United States in Titusville, Pennsylvania
on August 27, 1859.
II PRIOR LAWS
A "Refuse Act"
U.S. Code, Title 33, Section 407 Law
enacted by Congress in March 1899.
Superseded prior act of September 19,
1890. This act not only forbids discharge
of refuse into the navigable waters
(or tributaries of navigable waters, it
also forbids the placing of refuse on the
banks of a navigable water or tributaries
thereof) where such refuse shall be liable
to be washed into the navigable water.
The penalty under this section is covered
by Section 411 and provides for a fine not
exceeding $2, 500 nor less than $500, or
by imprisonment (in the case of a natural
person) for not less than thirty days nor
more than one year, or by both such fine
and imprisonment, in the discretion of the
court, one-half of such fine to be paid to
the person or persons giving information
which shall lead to conviction. (A Federal
Court of Appeals held in 1936 that oil was
refuse matter within the meaning of this
section (La Merced, 84F.2d444). The
U.S. Supreme Court held in 1966 that
gasoline was refuse matter within the
meaning of this section (U. S. v Standard
Oil Co., 384 U.S. 224). The U.S.
Supreme Court has also held in 1960 that
injunctive as well as criminal relief is
available under this section (U.S. v
Republic Steel Corp. 362 U.S. 482).
B U.S. Code Title 33, Section 441 Law
enacted by Congress on June 29, 1888.
Superseded prior act of August 5, 1886.
This act is known as "The Supervisor
of New York Harbor Act", but it also
applies to the harbors of Baltimore,
Maryland and Norfolk, Virginia. This
act provides, upon conviction (for
discharging any matter of any kind into
the harbors that a person shall be
punished by fine or imprisonment, or
both, )such fine to be not less than $250
nor more than $2, 500, and the imprison-
ment to be not less than thirty days nor
more than one year, either or both united,
as the judge before whom conviction is
obtained shall decide, one half of said fine
to be paid to the person or persons giving
information which shall lead to conviction
of this misdemeanor. [A Federal District
Court in 1928 said that waste fuel oil
discharges are prohibited by this section
(The Albania, 30 F.2d 727)].
C Congress enacted the "Oil Pollution Act of
1924" which provided for fines up to
$2, 500 for discharges of oil from vessels
into coastal navigable waters. This Act
was repealed by the Water Quality
Improvement Act of 1970.
D Outer Continental Shelf Lands Act of 1953
U.S. Code Title 43, (sections 1331-1343).
This act authorizes the Secretary of the
Interior to issue on a competitive basis
leases for oil and gas, sulphur and other
• minerals in submerged lands or the
Outer Continental Shelf. Subject to the
supervisory authority of the Secretary and
the Director of the Geological Survey,
drilling and production operations including
pollution prevention are controlled through
the issuance of regulations and orders.
E U. S. Code Title 33, Section 1001 enacted
by Congress in 1961 and amended in 1966.
The Oil Pollution Act of 1961 implemented
WP. POL. oh. 3. 5. 71
29-1
-------
Legislation Affecting Oil
m
the provisions of the International Con-
vention for the Prevention of the Pollution
of the Sea by Oil, 1954. To prevent
discharge or escape of oil or oily mixture
by sea-going vessels, (NOTE: Oily mix-
ture is defined as a mixture with an oil
content of 100 ppm or more). Vessels
required to maintain Oil Record Book.
Prohibited zone: All seas within 50 miles
from nearest land (baseline from which
territorial sea is established) and other
areas as defined in the convention.
Amendments to this law were adopted by
International Convention in 1969 but have
not yet been ratified by U.S.
"Clean Waters Restoration Act of 1966.
This act amended the Oil Pollution Act
of 1924. This was not a strong law
because to obtain a conviction for a
discharge of oil from a vessel you had
to prove "willful spilling" , or gross
negligence. This act was repealed by
the Water Quality Improvement Act of
1970.
WATER QUALITY IMPROVEMENT ACT
OF 1970. PUBLIC LAW 91-224
A Section II Control of Pollution by Oil
1 Quantities of oil which may be
discharged
Title 18, Part 610 of theCode of
Federal Regulations .gives this
definition of oil which may not be
discharged: Include discharge which:
a Violate applicable water quality
standards, or
b Cause a film or sheen upon or dis-
coloration of the water or adjoining
shorelines or causes a sludge or
emulsion to be deposited beneath
the surface of the water or upon
adjoining shorelines.
2 Notification (Penalty)
Title 33, Part 153 of the Code of Federal
Regulations states: Subsection ll(b) (4)
of the Act requires that any person in
charge of a vessel or of an onshore or
offshore facility, as soon as he has
knowledge of any discharge of oil in
harmful quantities from such vessel
or facility into or upon the waters
designated by the Act or the adjoining
shorelines, shall immediately notify
the appropriate agency of the United
States Government of such discharge.
The "appropriate agency" is listed as
follows:
a The Commanding Officer or officer
in charge of any Coast Guard unit
in the vicinity of the discharge;
b The Commander of the Coast Guard
District in which the discharge occurs.
c The Federal official designated in
the Regional Oil and Hazardous
Materials Pollution Contingency
Plan as the On-Scene Commander
(OSC) for spill response purposes.
If the above officials cannot for some
reason be notified, then notification
should be given to:
a The Commandant, U.S. Coast Guard
b Regional Director, EPA Water
Quality Office, for the region in
which the discharge occurs
The penalty for failure to notify one of
the foregoing immediately is up to
$10, 000 or imprisonment for up to one
year.
3 Knowingly discharging oil
Section 11 (b) (5) of the Act provides
$10, 000 fine for knowingly discharging
oil into the navigable waters. This is
a civil penalty and shall be assessed
by the Secretary of the department in
which the Coast Guard is operating.
Each violation is a separate offense.
29-2
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Legislation Affecting Oil
4 Areas affected
The discharge of oil into or upon the
navigable waters of the United States,
adjoining shorelines, or into or upon
the waters of the contiguous zone in
harmful quantities, as determined by
the President, is prohibited, except
(A) in the case of such discharges into
the waters of the contiguous zone,
where permitted under Article IV of
the International Convention for the
Prevention of the Pollution of the Sea
by Oil, 1954, as amended and (B) where
permitted in quantities and at times
and locations or under such circumstances
or conditions as the President may, by
regulation, determine not to be harmful.
Title 33, Part 153 of the Code of
Federal Regulations provides that dis-
charges of oil from properly functioning
vessel engines are not deemed to be
harmful.
5 Removal of oil from water and shoreline
Whenever any oil is discharged, into
or upon the navigable waters of the
United States, adjoining shorelines, or
into or upon the waters of the contiguous
zone, the President is authorized to act
to remove or arrange for the removal
of such oil at any time, unless he deter-
mines such removal will be done properly
by the owner or operator of the vessel,
onshore facility, or offshore facility from
which the discharge occurs.
6 National contingency plan
a Section 11 (c) (2) of the Act calls for
the preparation of a National Con-
tingency Plan. The National Oil and
Hazardous Materials Pollution
Contingency Plan has been estab-
lished and is operative. This Plan
provides for efficient, coordinated,
and effective action to minimize
damage from oil discharges
including containment, disposal
and removal of oil.
b As part of the Plan, Section 11 (c)
(2) (C) of the Act, requires
"establishment or designation of
a strike force consisting of per-
sonnel who shall be trained, prepared,
and available to provide necessary
services to carry out the Plan,
including the establishment at major
ports, to be determined by the
President, of emergency task forces
of trained personnel, adequate oil
pollution control equipment and
material and a detailed oil pollution
prevention and removal plan. "
c Dispersants and other chemicals
As required in section 11 (c) (2) (G)
of the Act, the Plan provides that
dispersants shall not be used:
1) On any distillate fuel
2) On any spill of oil less than 200
barrels in quantity
3) On any shoreline
4) In any waters less than 100 feet
deep
5) In any waters containing major
populations, or breeding or
passage areas for species of fish
or marine life which may be
damaged or rendered commercially
less marketable by exposure to
dispersant or dispersed oil.
6) In any waters where winds and/or
currents are of such velocity and
directions that dispersed oil
mixtures would likely, in the
judgment of EPA, be carried to
shore areas within 24 hours.
7) In any waters where such use may
affect surface water supplies.
29-3
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Legislation Affecting Oil
d Sinking agents
Sinking agents may be used only in
marine waters exceeding 100 meters
in depth where currents are not
predominately on-shore, and only
if other control methods are judged
by EPA to be inadequate or not feasible.
7 Removal or destruction of vessel
When as a result of a marine disaster,
there is a discharge, or an imminent
discharge, or large quantities of oil
from a vessel causing a substantial
threat of danger, the United States may
(a) coordinate and direct all public and
private efforts directed at the removal
or elimination of such threat; and
(b) summarily remove, and, if necessary,
destroy such vessel by whatever means
are available without regard to any
provisions of law governing the employ-
ment of personnel or the expenditure of
appropriated funds.
8 Threat from facilities
When there is an imminent and sub-
stantial threat to the public health or
welfare from an actual or threatened
discharge of oil from an onshore or
offshore facility, judicial relief can be
sought to abate the threat.
9 Cost of cleanup
a Vessel
An owner or operator of a vessel
from which oil is spilled, shall be
liable to the United States Government
in an amount not to exceed $100 per
gross ton of such vessel of
$14, 000, 000, whichever is lesser,
except where it can be proven that
the discharge was caused solely by
(A) an act of God (B) an act of war
(C) negligence on the part of the
U.S. Government or (D) an act or
omission of a third party without
regard to whether such act or
omission was or was not negligent.
Where the United States can show
that such discharge was the result
of negligence or willful misconduct
within the privity and knowledge of
the owner, such owner or operator
shall be liable to the United States
Government for the full amount of
such cost. Such cost shall con-
stitute a maritime lien on such
vessel which may be recovered by
an action in rem in the district
court of the United States for any
district within which any vessel
may be found.
b Offshore facility
The owner or operator of offshore
facility from which oil is spilled,
shall be liable to the United States
Government for the actual cost
incurred for the removal of such
oil by the United States Government
in an amount not to exceed $8, 000, 000,
except where it can be proven that
the discharge was caused solely by
(A) an act of God (B) an act of war
(C) negligence on the part of the
U.S. Government or (D) an act or
omission of a third party without
regard to whether such act or
omission was or was not negligent.
Where the United States can show
that such discharge was the result
of willful negligence or willful
misconduct within the privity and
knowledge of the owner, such owner
or operator shall be liable to the
United States Government for the
full amount of such cost. The
United States Government may
bring an action against the owner
or operator of such a facility in
any court of competent jurisdiction
to recover such cost.
c Onshore facility
The owner or operator from which
oil is spilled shall be liable to the
United States Government for the
actual cost incurred for the removal
of such oil by the United States
Government in an amount not to
exceed $8, 000, 000, except where
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Legislation Affecting Oil
it can be proven that the discharge
was caused by (A) an act of God
(B) an act of war (C) negligence
on the part of the U. S. Government,
or (D) an act or omission of a third
party without regard to whether such
act or omission was or was not
negligent. Where the United States
can show that such discharge was
the result of willful negligence or
willful misconduct within the privity
and knowledge of the owner, such
owner or operator shall be liable to
the United States Government for
the full amount of such cost. The
United States may bring an action
against the owner or operator of
such facility in any court of competent
jurisdiction to recover such cost.
10 Regulations
Consistent with the National Con-
tingency Plan, regulations are to be
issued establishing (A) methods and
procedures for removal of discharged
oil (B) criteria for local and regional
contingency plans (C) procedures,
methods and requirements for equip-
ment to prevent discharges of oil, and
(D) procedures for inspection of vessels
carrying oil. An administrative civil
penalty of up to $5000 can be assessed
for violation of these regulations.
11 Revolving fund
There is authorized to be appropriated
a revolving fund to be established by
the Treasury not to exceed $35, 000, 000
to carry out the provision of cleanup as
stated by the Act. Any other funds
received by the United States under
this Act shall also be deposited in said
fund for such purposes. All sums
appropriated to, or deposited in, said
fund shall remain available until
expended.
12 Evidence of financial responsibility
This section provides that any vessel
over three hundred gross tons, including
any barge of equivalent size, using any
port or place in the United States for
any purpose shall establish and main-
tain under regulations to be prescribed
from time to time by the President,
evidence of financial responsibility of
$100 per gross ton, or $14, 000, 000
whichever is the lesser, to meet the
liability to the United States which
such vessel could be subjected under
this law. In cases where an owner or
operator owns, operates, or charters
more than one such vessel, financial
responsibility need only be established
to meet the maximum liability to which
the largest of such vessels could be
subjected. Financial responsibility
may be established by any one of, or
a combination of, the following methods
acceptable to the President: (A) evidence
of insurance; (B) surety bond; (C) qual-
ification as a self-insurer; or (D) other
evidence of financial responsibility.
Any bond filed shall be issued by a
bonding company authorized to do
business in the United States.
13 This section provides that nothing in
the section shall be construed as
preempting any State or political sub-
division thereof from imposing any
requirement or liability with respect
to the discharge of oil into any waters
within such State.
B Executive Order 11548
This Executive Order, dated July 20, 1970,
assigned the various responsibilities and
authorities for implementing the oil
pollution provisions of Section 11 to EPA,
Department of Transportation (Coast
Guard), Federal Maritime Commission,
and Council on Environmental Quality.
The Coast Guard is responsible for
cleanup and enforcement in coastal and
contiguous zone waters, high seas,
Great Lakes waters. EPA is responsible
for inland waters.
This outline was prepared by J. William
Geise, Jr., Program Advisor (Legal),
Division of Oil & Hazardous Materials,
Washington, D. C. and Howard Lamp'l,
Contingency Plans Officer, Edison Water
Quality Laboratory, EPA, Edison, NJ 08817.
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NATIONAL AND REGIONAL CONTINGENCY PLANS
I INTRODUCTION
The Federal Water Pollution Control Act, as
ammended (P.L. 91-224, 84 Stat. 93, 1970)
directed the preparation of a National
Contingency Plan for Oil and Hazardous
Materials. This plan, published in the
Federal Register on June 2, 1970, super-
seded the National Multiagency Oil and
Hazardous Materials Contingency Plan which
was approved in September, 1968.
II PURPOSE
The Plan provides for a pattern of coordinated
and integrated response to major pollution
incidents by departments and agencies of the
Federal government. It establishes a national
response team and provides guidelines for the
establishment of regional contingency plans
and response teams. The plan promotes the
coordination and direction of Federal, State
and local response systems and encourages
the development of local government and
private capabilities to handle pollution spills.
IE OBJECTIVES
The objectives of the plan are to develop
effective systems for discovering and
reporting the existence of a pollution spill,
promptly instituting measures to restrict
the further spread of the pollutant, to assure
that the public health, welfare and national
resources are provided adequate protection,
application of techniques to cleanup and
dispose of the collected pollutants, and
institution of action to recover cleanup and
effective enforcement of existing Federal
statutes.
IV SCOPE
The plan is effective for all United States
navigable waters including inland rivers,
the Great Lakes, coastal territorial waters,
and the contiguous zone and high seas
beyond this zone where there exists a threat
to United States waters, shoreface or shelf
bottom.
V PARTICIPATING AGENCIES
Each of the primary Federal agencies has
responsibilities established by statute,
Executive Order or Presidential Directive,
which may bear on the Federal response to
a pollution spill. This plan intends to
promote the expeditious and harmonious
discharge of these responsibilities through
the recognition of authority for action by
those agencies having the most appropriate
capability to act in each specific situation.
The primary Federal Agencies are the
Environmental Protection Agency, the
Departments of Transportation, Defense,
Interior, and Health, Education and Welfare,
and the Office of Emergency Preparedness.
VI ORGANIZATION
The plan provides for a National Inter-Agency
Committee (NIC) which is the principal
instrumentality for plans and policies of the
Federal response to pollution emergencies.
At the Washington level, the plan establishes
a National Response Team (NRT) consisting
of representatives from the primary agencies.
This team acts as an emergency response
WP. POL. oh. 1.5. 71
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National and Regional Contingency Plans
team to be activated in the event of a
pollution spill involving oil or hazardous
material which: (a) exceeds the response
capability of the region in which it occurs,
(b) transects regional boundaries, or
(c) involves national security or major
hazard to substantial numbers of persons
or nationally significant amounts of property.
A National Response Center (NRC) in
Washington, D. C. is the headquarters site
for activities relative to pollution spills.
There are established throughout the United
States, Regional Response Teams (RRT) that
perform functions within the regions similar
to that performed by the National Response
Team on the national level. Regional Response
Centers (RRC), similar to the NRC, are
located in each of the pre-designated regions.
The plan further provides that in each region,
there will be established On-Scene-Commanders
(OSC). The On-Scene-Commander is the
single executive agent pre-designated by
regional plan to coordinate and direct such
pollution control activities in each area of the
region. The first responsible Federal
representative to arrive on-scene auto-
matically becomes the on-scene commander
until he is officially relieved by the pre-
designated on-scene commander.
VII DELEGATION OF RESPONSIBILITY
The U.S. Coast Guard is to provide for On-
Scene-Commanders in areas where they have
assigned responsibility, which includes the
high seas, coastal and contiguous zone waters,
coastal and Great Lakes ports and harbors.
The Environmental Protection Agency will
furnish or provide for On-Scene-Commanders
in other areas.
VIE FEDERAL RESPONSE OPERATION
The actions taken to respond to a spill or
pollution incident can be separated into five
relatively distinct classes or phases. For
descriptive purposes, these are:
Phase I. Discovery and Notification
Phase II. Containment and Counter-
measures
Phase HI. Cleanup and Disposal
Phase IV. Restoration
Phase V. Recovery of Damages and
Enforcement
It must be recognized that elements of any
one phase may take place concurrently with
one or more other phases.
K REGIONAL CONTINGENCY PLANS
Separate regional plans are to be developed
by the Environmental Protection Agency
and the United States Coast Guard for the
respective areas of responsibility within
each region. All regional plans are to be
oriented in accordance with the ten (10)
standard Federal administration regions.
All regional contingency plans will contain,
as a minimum the following items:
A A definition of the area covered including
the points of change in jurisdiction between
Environmental Protection Agency and
U. S. Coast Guard.
B A notification and reporting system
beginning with the initial discovery of
a spill.
C Names, addresses and phone numbers of
all pertinent Federal, State, local and
industry personnel involved in the reporting
system.
D A listing of predesignated On-Scene-
Commanders and Regional Response
Centers.
E Listing of resources and equipment
available in the regional area with names,
addresses and phone numbers.
F Categorization of water areas by use to
establish predetermined cleanup priorities.
This outline was prepared by A.W. Bromberg,
Chief, Operations Branch, OWP, EPA,
Edison Water Quality Laboratory, Edison, NJ.
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FUNCTIONS, RESPONSIBILITIES AND ROLE
OF THE ON-SCENE-COMMANDER
I INTRODUCTION
A You may be designated as the On-Scene^
Commander during the next major oil
spill that takes place in your area of
responsibility. Are your prepared?
II BACKGROUND
A What are the qualifications of a good
On-Scene-Commander? He should be a
well trained individual, whose background
includes oil pollution research, experience
with a number of actual spills of different
types of oil, a knowledge of the shipping
•industry and a good background in law and
existing oil pollution legislation.
B Basically, the On-Scene-Commander,is
a decision making "machine", working.at
least twelve hours per day over a long
period of time. To make these decisions
in an intelligent manner, he must have the
basic background to support his decisions.
If a wrong decision is made, the results
could range from embarrassment to the
Federal Government, to injury or death
to substantial numbers of persons.
C A good On-Scene-Commander must have
many attributes. First of all, he must
have good managerial ability. From
utter chaos, he must organize a small
army of men and equipment to remove
the oil from the water and shoreface.
He must be a statistician for he has to
provide and direct great amounts of money,
equipment services and manpower. He
must have a sense of humor, because no
matter how well the cleanup is going,
some elements of the public are going to
cry for instant and dramatic cleanup.
And finally, he must have the ability to
walk a tenuous tightrope, to try to please
as many of the public, who have been
injured by the spill, as possible. For
instance: the sunbathers and swimmers
want the beaches and surf cleaned at once;
the bird lovers want the birds protected
at all cost; the vessel owner wants his
vessel cleaned of all traces of oil pollution;
shore-front property owners want their
homes protected and cleaned; the
commercial and sports fishermen would
rather have the oil come ashore than have
it do any damage to marine life; and finally,
the oil and shipping industry want the
channels kept open at all cost.
Ill ORGANIZATION
A Staff
Every On-Scene-Commander should be
backed up with a fully trained staff. This
staff should include, but is not limited to:
a public information officer, to handle the
countless calls and inquiries from the
news media; a stenographer, to keep a
running account of all business transacted
during any given day; a contracting officer,
to handle the myriad details for the hiring
of and negotiations with various contractors,
purchase request and the recording and
handling of petty cash funds. He should
also have on his staff, technicians to
supervise and "straw-boss" the various
contractors and to do general field work
during the life of the spill. These
technicians should be well versed in oil
pollution work. Finally, the On-Scene-
Commander should have available to him
legal council for consultation when the
need arises; fully trained chemist,
biologist and engineers who have a good
background in oil pollution work.
B Quarters and Equipment
The On-Scene-Commander and his staff
should have a suitable headquarters in
which to work. Ideally, a Coast Guard
Station would provide a suitable head-
quarters if it were near the scene of the
spill. If not, then other quarters must
be found. These quarters could be a
suite of motel or hotel rooms; a house
trailer; a mobile laboratory, as found
WP. POL. oh. 2. 5. 71
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Functions. Responsibilities and Role of the On-Scene-Commander
in the EPA, Water Quality Offices, or a
private beach house.
The operations headquarters should be
equipped with the following items: wall
charts, maps, at least eight telephones,
desks, chairs, writing equipment,
typewriters and if possible, a teletype-
writer. One of the most important items
of equipment in the headquarters, is the
Commander's Log. The Commander's
Log, a permanent bound book, should be
maintained from the inception of the spill
until the case is closed out. In it, there
should be recorded, chronologically, a
reference to all telephone calls received,
meetings held, orders issued, events
taking place, personnel changes, visitors
received, overflights made, etc. This
Log can be an invaluable record of the
spill to be later used in court or congres-
sional hearing.
C Communications
Whenever the On-Scene-Commander and
his staff are housed, the first order of
business upon arrival is to order phones.
At least eight phones should be installed.
One of the eight telephone numbers should
not be given out for general use, but should
be reserved and made known to only a few
selected individuals who may have to
communicate with the On-Scene-Commander
on urgent matters.
It is imperative that the On-Scene-Commander
have communications with the contractors
in the field and with his observers. Small,
portable hand-held radios with sufficient
range would be the ideal answer. If radio
communications are not available, there
is another system which can be found in
most large cities. This system is called
"People Beepers". It is a small, belt-
clip-on radio receiver with a range of
approximately twenty-five miles. To get
a contractor or observer in the field, the
On-Scene-Commander dials a specified
number and asks the operator to have
No. A-16 call headquarters. The
operator in turn activates a "beeper" on
the radio receiver No. A-16 and transmits
the message. The holder of receiver
No. A-16 in turn calls the On-Scene-
Commander by telephone and
communications are established. This
system can be rented for a nominal fee.
Communications between air observers
and headquarters is a necessity and
observation and work vessels should
also be able to contact the field head-
quarters.
IV RELATIONS WITH OTHER ORGANIZATIONS
A Federal
1 Environmental Protection Agency
2 U. S. Coast Guard
3 U.S. Army Corps of Engineers
4 U. S. Health, Education and Welfare
5 Office of Emergency Preparedness
These are the basic Federal Agencies
concerned with a major oil spill.
However, many other Federal Agencies
may be called on to furnish help during
the life of the emergency; they may include,
but are not limited to, the following:
a U. S. Air Force
b U.S. Navy
c U.S. Army
d General Accounting Office
e General Services Administration
B States
Individual states are encouraged to make
commitments to the cleanup of major oil
spills. If the state decides that it wants
to take complete charge of the spill, it is
the policy of the Federal government to
agree and then monitor the situation.
The problem here lies in the fact that
very few states have the funds committed
by legislation to become involved in a
major oil spill cleanup.
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Functions. Responsibilities and Role of the On-Scene-Commander
C Interstate Agencies
Interstate agencies too, are encouraged
to make commitments to the cleanup of
major oil spills. Interstate agencies can
also take complete charge of a major oil
spill, but again, the funding limitations
applies to these agencies as well as to the
individual states.
D Local Government
Local governments will rarely have the
funds to combat a major oil spill.
However, they can be an invaluable
source of manpower and equipment.
E Academic Communities
The academic communities throughout the
country can usually be counted on to
furnish information and advice on the
local environment, during a major spill.
Quite often, you will find that these
institutes have previously made extensive
biological studies of local areas and this
can be of invaluable help in comparison
with post spill biological surveys.
V FINANCING
A All cost of cleanup should be borne by the
polluter. In most cases, the major oil
and shipping companies will shoulder this
responsibility without question. If the
company agrees to finance the cost of
cleanup, they will probably want to take
charge of the operations. This is
agreeable to the Federal Government--
however, the On-Scene-Commander and
his staff should monitor the complete
cleanup operation. Should progress of
the cleanup be not to the satisfaction of
the On-Scene-Commander, he has the
authority to make the company stop its
operations and have the Federal government
proceed with the cleanup. All cost borne
by the Federal government will be
reimbursed by the polluter.
B The individual state government can
assume command of a spill cleanup, if
they so desire. But again, the Federal
government's On-Scene-Commander must
monitor all phases of the cleanup. The
states in turn can recover expended funds
either through the individual state courts
or the monies can be recovered through
the Federal courts.
The Federal government has established
a thirty-five million dollar revolving
fund for the cleanup of oil and other
hazardous materials. This fund is
administered by the U. S. Coast Guard.
All monies expended by the Federal
government in the cleanup process,
will be recovered from the polluter,
either voluntarily or through the Federal
court system.
VI INDEPENDENT CONTRACTORS FOR
CLEANUP
A Prior to the Torrey Canyon incident, it
was very difficult to find a contractor
who had the knowledge of oil spill cleanup
or the desire to cleanup massive spills
of oil. However, since that date, a new
industry has evolved - the so- called
"third party contractor" for the cleanup
of oil spills.
B As mentioned previously, the On-Scene-
Commander should have on his staff a
responsible contracting officer. The
contracting officer should handle all the
details of the contract, payment and the
keeping of complete records pertaining
to all monies expended during the life of
the spill. The On-Scene-Commander
and the contracting officer should keep
in mind that all paper work involved in
cleanup cost will probably end up as
evidence in a federal court.
C Prior to a major spill, a good On-Scene-
Commander should have knowledge of all
"third party" contractors in his area of
responsibility. The On-Scene-Commander
should know the people he is going to be
working with during an emergency. He
should know the amount of equipment the
contractor has on hand, the type of equip-
ment, the conditions of the equipment.
He should know if the contractor has
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Functions. Responsibilities and Role of the On-Scene-Commander
trained personnel or does he recruit from
the streets. All this knowledge is important
to the On-Scene- Commander, for he has
to rely heavily on his working contractors.
D Finally, the On-Scene-Commander should
have available to him trained personnel to
monitor the work of the various contractors
in the field. This is necessary to insure
that the Federal government receives full
value for every dollar spent on the cleanup.
VH REPORTS REQUIRED
A The National Contigency Plan requires that
the On-Scene-Commander submit two
situation reports daily. On at 0800 hours
and one at 2000 hours. These reports are
normally submitted by teletype. If any
event of dramatic importance occurs at
other times of the day, the National
Response Team should be notified by
teletype at once.
B When the emergency is over, and the
Regional Response Team is disbanded,
the On-Scene-Commander should prepare
his "End of Operations" report. This
report should contain as much information
as possible about the entire life of the
spill incident. The Commander's Log
will prove invaluable to the On-Scene-
Commander's preparation of his report.
Once completed, the report should be
forwarded to the National Response Team
through the Regional Response Team.
This outline was prepared by H. J. Lamp'l,
Contigency Plans Officer, Edison Water
Quality Laboratory, Office of Water Programs ,
EPA, Edison, NJ 08817.
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