OIL POLLUTION
CONTROL TECHNOLOGY
TRAINING MANUAL
ENVIRONMENTAL PROTECTION AGENCY © EDISON WATER QUALITY LABORATORY
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OIL POLLUTION
CONTROL TECHNOLOGY
This course is offered for employees
of regulatory agencies who are assigned
direct responsiblity for response to
nonrecurring discharges,of oil. It is
not intended to dictate arbitrary solu-
tions to technical problems in spill
control but will familiarize students
with alternatives and provide oppor-
tunity to practice response under rea-
listic constraints and measures of
success. In particular, students who
complete this course will be able to
function within the guidelines of fed-
eral, state, or interstate Contingency
Plans in effect in the area where the
course is presented.
ENVIRONMENTAL PROTECTION AGENCY
EDISON WATER QUALITY LABORATORY
TRAINING PROGRAM
FEBRUARY 1971
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FOREWORD
These manuals are prepared for .reference use of students
enrolled in the Oil Pollution Control Technology Training
Course presented at the Edison Water Quality Laboratory.
Due to the limited production and availability
of the manuals, it is not appropriate to cite
them as technical references in bibliographies
or other forms of publication.
References to products and manufacturers is for
illustration only; such references do not imply
product endorsement by the Environmental Protec-
tion Agency.
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 instruc-
tors may provide additional material to cover special as-
pects of their own presentations.
This manual will be useful to anyone who has need for in-
formation 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.
G. F. McKenna
Regional Training Officer
Edison Water Quality Laboratory
Environmental Protection Agency
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CONTENTS
Title or Description
OIL SPILL PROBLEM
Magnitude of Oil Problem
Refinery and Terminal Operations
Platform Operations
Biological Effects
LEGAL RESPONSE
Legislation Affecting Oil Pollution
National and Regional Contingency Plans
Functions, Responsibilities and Role of On-Scene Commander
OIL CHARACTERISTICS
Chemical and Physical Characteristics
Fate and Behavior
Oil Sampling
Oil Identification
PREVENTION AND CONTROL - TREATMENT
Tanker Operation
CHEMICAL TREATMENT
Dispersants - Policy
EPA Tests
PHYSICAL-METHODS OR TREATMENT
Sinking and Burning Agents
Sorbents
Booms
Skimmers
Beach Cleanup Methods
Outline No.
1
2
3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
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OIL SPILL PROBLEM
Magnitude of Oil Problem
Refinery and Terminal Operations
Platform Operations
Biological Effects
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OIL POLLUTION: MAGNITUDE OF THE PROBLEM
I SOURCES AND AMOUNTS
A Broad Pictu re
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 con-
sumer by pipe, water, rail and
highway. During 1970 more than
4.5 billion barrels of petroleum
moved as crude oil from the pro-
duction field through the refiner-
ies 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 complex and
diversified transportation system
required to move this volume of
oil.
Estimated amounts of oil
as well as the sources of this
form of pollution are shown in
Table I. 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 petrol-
eum from the oil field to the con-
sumer 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 fre-
quency is extremely high. Approx-
imately one barrel of product is
lost for each one million transported.
About 7,500 oil spills^J are now
occurring annually with an estimated
total loss of 500,000 barrels^3).
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 pipelines crisscross the
United States transporting 45 percent
of the Nation's annual consumption of
petroleum. Pipeline failures accounted
for only three percent^3) 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 ^3) of total product lost.
Tank trucks are the last leg of the
transportation system, delivering re-
fined 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 railroad tank cars take over the
transport of crude and refined petroleum
products.
1-1
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TABLE I
ESTIMATES OF OIL INTRODUCED
INTO WORLD'S WATERS AND POTENTIAL LOSSES TO
WATERS, 1969
Metric Tons Per Year
Tankers
(normal operations)
Using Control measures
(80%) 30,000
Not using control measures
(20%) 500,000
% of
Total
530,000 10.7
Other ships
(bilges, etc.) 500,000 10.1
Offshore production
(normal operations) 100,000 2.0
Accidental spills
Ships 100,000 2.0
Nonships 100,000 2.0
Refineries and
petrochemical 300,000 6.0
SUBTOTAL 1,630,000
Potential losses to water
from industrial and auto-
motive (not fuel):
Highway vehicle spent oils 1,800.000 36.6
Industrial plus all other
vehicles 1,500,000 30.6
SUBTOTAL 3,300,000
TOTAL 4,930,000
NOTE: Oil from pleasure craft and natural seeps not included.
1-2
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C Why Spills Occur
II ANALYSIS OF PAST MAJOR SPILLS
Blumer (1969) reported that human
error accounted for 88 percent of
the total number of spill incidents.
The means of rectifying this situa-
tion is by better training and edu-
cation, improved engineering, and
when all else fails enforcement by
a responsible state or federal
agency.
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 that^ ' 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 stop' has decreased as their
size has increased. For the 400,000
tonner, the straight-line stopping
distance for a 'crash stop' 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 astern'
but on 'stop' it takes up to one
hour for the"Universe Ireland"to come
to a stop.
5 minutes
17,000 long
200,000 tonV
400,000 ions
1,000,000
1/5 mile
2.5 miles
30 minutes
Dillingham Corporation (1969), under
contract to API, conducted a statisti-
cal 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 persistant) 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 Sou re e
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.
4.5 miles
E Du rat ion
75% of the spill incidents lasted
more than five days with a median
duration of 17 days.
Figure 1
1-3
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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 consid-
ered to be recreational.
H Distance from Port
75% occurred with 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 II,
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 ques-
tion that now arises is "how does one
mobilize shoreline protection equipment
during this short length of time?"
Ill MAJOR SPILL INCIDENTS 1956-1970
For reference purposes, major spill
incidents along with significant char-
acteristics, are shown in Table II.W)
REFERENCES
Administration, U. S. Dept. of the
Interior.
3 Anon (1968) "Oil Pollution - A
Report to the President", U. S. Dept.
of the Interior and U. S. Dept. of
Transportation.
k Gilmore, G. A., et al (1970), "Sys-
tems Study of Oil Spill Cleanup
Procedures", Dillingham Environmental
Co., La Jolla, California.
5 Oliver. E. F., Capt., USN Ret., U. S.
Naval Institute Proceedings, Septembei
1970.
Massachusetts Institute of Technology,
1970 Special Study Group.
Anon (1970) "Clean Water for the 1970's-
A Status Report", Federal Water Quality
Outline prepared by Richard T. Dewling,
Director, R&D, Edison Water Quality
Laboratory, December 1970.
I-i
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90%-
80%-l
a
en
*_ 70%-
o
o>
CT>
2 60%-
c
o>
50%-
0)
o 40%-
3
e
o 30%H
20%-
10%-
D/stance from Shore and Response Time
Available for Shoreline Protection
Data from 25 Incidents
52%
Less Than One Mile
2 Hours
1
Response Time
(Assuming o 15 knot onshore wind ond oil drift oi 3%
of wind velocity)
I Day
1
H 1f-
345
10
Miles
H 1 rH
20 30 40 50
10 Days
I
100
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TABLE II
MAJOR OIL SPILL INCIDENTS
Name
ALGOL, tanker
ANDRON , tanker
ANNE MILDRED BROVIG, tanker
ARGEA PRIMA, tanker
ARROW , tanker
BENEDICTE, tanker
Bridgeport, Conn., terminal
Chester Creek, pipeline
CHRYSSI P. GOULANDRIS, tanker
Dutch Coast Spill
ESSO 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
Schuylkil 1 River, Berks Assoc.
Sewaren, N. J., storage tank
Ship Shoal, drill rig
Staten Island, N.Y., 2 Esso barges
USS SHANGRI-LA (CVA-38)
VTAMPICO, tanker
TIM, tank barge
TORREY CANYON, tanker
Waikiki Beach
Waterford 3each
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
1 1-12-68
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
Coll ision
Grounding
Grounding
Coll ision
Pumping
Break
Unknown
Unknown
Grounding
Grounding
Grounding
Col 1 ision
Grounding
Hose failure
Col 1 ision
Hull failure
Fire
Fire
Coll ision
Pumping
Leak
Grounding
Grounding
Hose failure
Collision
Natural faults
Lagoon failure
Tank failure
Storm shifting
Col 1 ision
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
Residua 1
Crude
#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
1-6
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REFINERY AND TERMINAL OPERATION
I INTRODUCTION
A A petroleum refinery is an organ-
ized and coordinated arrangement
of manufacturing processes
designed to provide both physical
and chemical change of crude
petroleum into saleable products
with the qualities required.
II TYPES OF REFINERIES
A Refineries can be classified as
simple, complex, or fully inte-
grated.
1 A simple refinery will include
crude oil distillation,
catalytic reforming and treat-
ing. Its products will be
limited to LP gas, motor fuels,
kerosene, gas oil, diesel fuel
and fuel oil.
2 A more complex refinery will
make a greater variety of prod-
ucts and require the following
additional processes: vacuum
distillation, catalytic crack-
ing, polymerization, alkyla-
tion and asphalt oxidation.
3 The fully integrated refinery
makes a full range of products.
Additional products will in-
clude 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.
Ill TYPES OF CRUDE OILS
There are over 8,000 differ-
ent types of crude oils in
the USA alone and these vary
from high to low sulfur con-
tent and from asphaltic to
paraffinic and from heavy to
light in specific gravity.
A The asphalt base crudes
contain very little par-
affin wax and a residue
primarily asphaltic.
These crudes are particu-
larly suitable for making
high quality gasoline and
asphalt.
B Paraffin base crudes con-
tain 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. Vir-
tually 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
2-1
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distillation column is presented
as Figure 2.
The lighter, more volatile por-
tions of the crude are withdrawn
at the upper part of the tower
and the heavier parts down lower
in the tower. Improved separa-
tion between products can be
accomplished by installing more
fractionating trays. It is in
this manner that the crude oil is
first broken into its parts.
B Vacuum Distillation
Normally, it is desired to cut
deeper into the crude oil than
would be possible under atmospher-
ic pressure and reasonable temper-
atures. Therefore, vacuum
distillation is performed on the
residual from the atmospheric
distillation. This process is
essentially the same as-atmospher-
ic 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
components of the refinery
gas streams are combined
over a catalyst to make a
high octane component.
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 frac-
t ions.
F Platforming
This major process develop-
ment 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 Hydrotreat ing
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 petrole-
um residues by catalytic
hydrogenation to refined heavy
fuel oils or to high quality
catalytic charge stocks.
2-2
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I Coking
C Flocculator-Clarifier
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 concentra-
tions and include organic compounds
containing sulfur, nitrogen and
oxygen, dissolved metals and inor-
ganic salts. These contaminants
are removed at some intermediate
stage or ju'st prior 'to sending the
finished product to storage. Num-
erous 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 possi-
ble here because of the large
holding time.
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 recy-
cled.
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 re-
moving it in sand filters.
VI TERMINALLING
A Tankers
1 Tankers are loaded or un-
loaded through flexible
hose connected to shore
2-3
-------
pipelines or by means of load-
ing booms made of conventional
pipe connected by swivel
jo int s.
2 Tankers are divided into two
groups:
a Dirty or black oil ships
which transport crude oils,
fuel oils and diesel fuels.
b Clean or white oil ships
which carry highly refined
products.
B Barge
1 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 dis-
charging lines to be used,
volume of each product and
permissible pressure must be
clearly understood.
2 Commu n ic at ion s
Appropriate signals and means
for transmitting them must be
established. Telephone or
walkie-talkies or hand
radios can be utilized.
The vessel dock officer
must be notified when-
ever a change in receiv-
ing tankage is to. be 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
transfer operations, the
senior deck officer must
assure himself that the en-
tire cargo system is lined
up properly.
2-4
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CHARGE
FROM
HEATER
DRAWOFF
VALVE
I -J- F runr
III BOTTOM DRAWOFF
Fig. 2 - Bubble Cap-type Fractionating Tower
2-7
-------
PLATFORM OPERATIONS
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 off-
shore 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 plat-
forms, structures and facilities,
they do constitute a potential
source of pollution due to blow-
outs and other accidents.
B Current practice in the offshore
oil industry is to group plat-
forms, 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
equ ipment.
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 accumulates 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 consti-
tute from less than 107o to
greater than 50% of the total
fluids produced from a single
well.
Depending on several variables,
an offshore operator may
dec ide t o:
1 Pump the entire oil/water
mixture to shore for treat-
ment .
3-1
-------
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 I7o
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.
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 cal-
culations.
There are two ba~ic types of
equipment associated with
oil/water separation on off-
shore production facilities:
1 Operat ion equ ipment.
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 frequent-
ly be from 200 ppm to 3,000
ppm or more. As the water
content in the product oil de-
creases, the oil content in the
effluent water increases.
Therefore, the 2% maximum (and
1% desired) water content
required by the pipeline com-
pany 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 Equip-
ment include the following:
1 Emulsion treaters.
3-2
-------
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 sedi-
mentation 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 effec-
tively remove the water phase.
Conditioning Equipment That
equipment used downstream from the
operational equipment to treat
bleed water prior to disposal over-
board. 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 sys-
tem designed to process
10,000 barrels per day. This
cost is based on the assump-
tion that the equipment would
be customized and designed to
achieve an effluent of 50 ppm
oil. This system would occupy
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 platform 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 grav-
ity 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 outside siphon
called a "Gun Barrel". These
units are normally used upstream
from other oil removal equipment
3-3
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to eliminate the bulk of free oil
and sedimentation.
Gas flotation units saturate
"clean" water with gas in a pres-
sure 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 recir-
culated to the gasification pres-
sure 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 dis-
persed 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.
C 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 re-
duce the equipment space require-
ments. 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 require-
ments 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 coun-
tries. 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 prob-
lems. Present equipment is
capable of producing effluent
bleed water with oil concentra-
tions in the 50 to 200 ppm
range. This conditioning equip-
ment costs about $2 to $3 per
barrel per day to install and
requires 300-400 square feet of
valuable platform space.
More efficient equipment is
needed so that this industry
can continue to grow without
placing additional loads on an
already overburdened environ-
ment .
Outline prepared by J. S. Dorrler,
Acting Chief, Oil Research and Devel-
opment Section, Edison Water Quality
Laboratory, Edison, New Jersey 08817,
January 1971.
3-4
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BIOLOGICAL EFFECTS OF OIL POLLUTION
I INTRODUCTION
The suffering and mortality caused
to birds by oil pollution, the coat-
ing of public and private property
with layers of oil, is extremely
conspicuous and attracts great public
attention and sympathy. We hear con-
flicting statements from competent
and respected scientists regarding
the biological effects of these in-
cidents. Why this divergence 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 &
single substance but a complicated
and variable mixture of literally
thousands of chemical compounds.
This fact is clearly demonstrated
in Table I (1) 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 constituents of oil
share many common properties; .however
they also differ considerably in many
properties which influence their ef-
fects on the environment. Among these
are:
1. Toxicity - Many low boiling
aromatic hydrocarbons are lethal
poisons to almost any organism while
some higher boiling paraffin hydro-
carbons are essentially non-toxic to
most forms of life.
2. Solubility - Benzene deriva-
tives may be soluble in water at con-
centrations around 100 ppm; naphtha-
lenes at 30 ppm, while higher molecular
weight hydrocarbons may be essentially
insoluble in water. Solubility, of
course, will significantly influence
the toxicity of a component of oil.
3. 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.
4. Factors such as volatility, den-
sity, 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.
5. Carcinogenicity - Some components
of crude, refined, and waste oils are
known to have cancer-inducing properties.
Ill 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
environment many different ways, among
which are:
1) Direct kill of organisms through
coating and asphyxiation.
2) Direct kill through contact poison-
ing 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.
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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 princi-
pal 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 into
the marine food chain and human food
sources.
9) Low level effects that may inter-
rupt 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 Fal-
mouth" oil spill have shown oil on the sea
floor. Oil in inshore and offshore sedi-
ments is not readily biodegraded; it can
move with the sediments and can contami-
nate unpolluted areas long after an
accident.
B Waterfowl
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 re-
sult of a breaking down of the natural
insulating oils and waxes shielding the
birds from water and loss of body heat,
as well as due to plumage damage and in-
gestion of oil or an oil dispersant
mixture. In addition, birds may be
harmed indirectly through contamination
of nesting grounds or through interrup-
tion of their food chain by destruction
of marine life on which the birds feed.
The possible effects of the spill-
age 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. Non-migra-
tory birds will be the hardest hit with
the possibility of eliminating an
entire colony.
Bird kills in the thousands may result
from a specific spill incident. Ef-
forts to cleanse or rehabilitate con-
taminated birds have generally been
unsuccessful with less than 20 percent
of the treated birds surviving. Es-
timates 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.
C Shellfish
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 contamination by heavy
oil alone however the flavor of the
flesh will be tainted. Lighter pe-
troleum fractions such as diesel or
gasoline appear to be more fatal, and
some species such as clams may exper-
ience significant mortalities. For-
tunately, 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 in-
cident, recovery appears to have taken
place within a period of six months to
two years.
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D Fish
Finfish generally appear to be unaf-
fected by the presence of spilled oil
as their mobility permits them to
avoid areas with high oil or chemi-
cal concentrations. Danger 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
Relatively few observations of any
direct effect of oil spills on
larger marine mammals 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 ef-
fects to young or disabled mammals
are viewed as being comparable to
normally occurring mortalities, 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 un-
der the oil film for a few days, but
eventually they become yellow and die.
Plants recover by producing new shoots,
a few of which can usually be seen
within 3 weeks of pollution, unless
large quantities of oil have soaked
into the plant bases and soil. Seed-
lings and annuals rarely recover.
In the long term, recovery from oil
spillages has been observed many times
(e.g., Buck and Harrison,1967;Ranwell,
1968;Stebbings,1968;Cowell & Baker,
1969). The cases described cover dif-
ferent salt marsh communities, different
types, volumes and degrees of weathering
of oil, and pollution at different times
of year. Vegetative recovery from ex-
perimental spraying at different times
of year has been observed (Baker,1970).
The evidence indicates that marshes re-
cover well from a single oil spillage,
or from successive oil spillages provi-
ded 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 under-
stood 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 8
where destruction has taken place, have
repopulated rapidly although in propor-
tions varying from original numbers.
Some forms of algae and diatoms appear
to be stimulated in growth by a certain
amount of oil. Various bacterial organ-
isms will also feed on available oil and
multiply, thus, providing energy to the
protozoan level of the food chain. In
general, based on todays knowledge, oil
spillage does not appear to have lasting
effects on the food elements of the
marine environment.
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References
1. Dillingham Corp., .1970, "A Review
of the Problem - Characteristics
of Major Oil Spills".
2. Blumer, M., 1970, Personal
Correspondence.
3. Murphy, T., 1970, "Environmental
Effects of Oil Pollution", Pre-
sented at ASCE, July 13, 1970,
Boston, Mass.
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 Biolog-
ical Effects of Oil Pollution and
Oil Cleaning Materials in Littoral
Communities, Including Salt Marshes",
FAO Conference, Rome, 1970.
This outline prepared by R. T. Dewling,
Director, Research and Development,
Edison Water Quality Laboratory,
January 1971.
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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 7
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LEGAL RESPONSE
Legislation Affecting Oil Pollution
National and Regional Contingency Plans
Functions, Responsibilities, and Role of On-Scene Commander
-------
LEGISLATION AFFECTING OIL POLLUTION
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, it
also forbids the placing of refuse
on the banks of a navigable water,
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 ex-
ceeding $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 discre-
tion of the court, one-half of
such fine to be paid to the per-
son or persons giving information
which shall lead to conviction.
B U. S. Code Title 33, Section
Law enacted by Congress on June
29, 1888. Superseded
prior to 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 pro-
vides, upon conviction, 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
imprisonment to be not
less than thirty days nor
more than one year, either
or both united, as the
judge before whom convic-
tion 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.
U. S. Code Title 33, Section
433 Law enacted by Congress
on June 7, 1924. This law
was superseded by the Feder-
al Water Pollution Control
Act of 1965-66.
Outer Continental Shelf Land
Act of 1953 U. S. Code Title
43. The Outer Continental
Shelf Land Act of August 7,
1953, among other things,
authorizes the Secretary of
the Interior to issue on a
competitive basis leases for
5-1
-------
Ill
oil and gas, sulphur and other
minerals in submerged lands of
the Outer Continental Shelf, as
defined in section two of the
act. Subject to the supervisory
authority of the Secretary, the
regulations shall be administered
by the Director, Bureau of Land
Management.
E U. S. Code Title 33, Section 1001
enacted by Congress in 1961. Pub-
lic Law 87-167 (International
Convention on Prevention of the
Sea by Oil). To prevent dis-
charge or escape of oily substance
by sea-going vessels (NOTE: Oily
substance is defined as persistent
oil). Vessels required to main-
tain Oil Record Book. Prohibited
zone: All seas within 50 miles
from nearest land (baseline from
which territorial sea is estab-
lished) and other areas as de-
fined in the convention.
F Federal Water Pollution Control
Act of 1965-66. U. S. Code Title
33, Section 466. This act super-
seded the Oil Pollution Act of
1924. This was not a strong law
because to obtain a conviction
under this act you had to prove
"intent", or gross negligence.
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
The Federal Register, Volume
35, #177 dated September 11,
1970, gives this defini-
tion 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 discoloration 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)
The Federal Register, Volume
35, #227 dated November 21,
1970, states: Subsection
1Kb) (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 "appropri-
act agency" is listed as
follows:
a The Commanding Officer
or officer in charge of
any Coast Guard unit in
the vicinity of the dis-
charge;
b The Commander of the
5-2
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Coast Guard District in
which the discharge occurs.
c The Federal official desig-
nated in the Regional Oil
and Hazardous Materials
Pollution Contingency Plan
as the On-Scene Commander
(OSC) for spill response
purposes.
d The Commandant, U. S. Coast
Guard.
e Regional Director, EPA Water
Quality Office, for the
region in which the dis-
charge occurs. The penalty
for failure to notify one
of the foregoing immediately
is $10,000.
\
Knowingly discharging oil
(Penalty)
Section ll(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.
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 Sea by Oil, 1954, as
amended and (B) where
permitted in quantities
and at times and loca-
tions or under such cir-
cumstances or conditions
as the President may, by
regulation, determine
not to be harmful.
5 Removal of oil from water
and shoreline
Whenever any oil is dis-
charged, into or upon the
navigable waters of the
United States, adjoining
shorelines, or into or
upon the waters of the
contiguous zone, the Pres-
ident 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 off-
shore facility from which
the discharge occurs.
6 Strike force
Section ll(c)(2)(c) of the
Act, states, "establish-
ment or designation of a
strike force consisting of
5-3
-------
Personnel who shall be
rained, prepared, and avail-
able 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 person-
nel, adequate oil pollution
control equipment and material
and a detailed oil pollution
prevention and removal plan".
7 Dispersants and other chemicals
Dispersants shall not be used:
a On any distillate fuel.
b On any spill of oil less
than 200 barrels in quantity.
c On any shoreline.
d In any waters less than 100
feet deep.
e In any waters containing
major populations, or breed-
ing 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.
f In any waters where winds
and/or currents are of such
velocity and directions
that dispersed oil mixtures
would likely, in the judg-
ment of EPA, be carried to
shore areas within 24 hours.
g In any waters where such
use may affect surface
water supplies.
8 Sinking agents
Sinking agents may be used
only in waters exceeding 100
meters in depth where cur-
rents are not predominantly
on-shore, and only if other
control methods are judged
by EPA to be inadequate or
not feasible.
9 Removal or destruction of
vessel
Because of a discharge, or
an imminent discharge, of
large quantities of oil from
a vessel, the United States
may (A) coordinate and direct
all public and private
efforts directed at the remov-
al or elimination of such
threat; and (B) summarily
remove, and, if necessary,
destroy such vessel by what-
ever means are available
without regard to any provis-
ions of law governing the
employment of personnel or the
expenditure of appropriated
funds.
10 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
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in an amount not to exceed
$100 per gross ton of such
vessel or $14,000,000,
whichever is lesser, except
that where the United States
can show that such dis-
charge was the result of
negligence or willful mis-
conduct 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 constitute a
maritime lien on such
vessel which may be recover-
ed by an action in rem in
the district court of-the
United States foe any dis-
trict 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 remov-
al of such oil by the United
States Government in an
amount not to exceed
$8,000,000, except that
where the United States can
show that such discharge
was the result of willful
negligence or willful mis-
conduct 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 jurisdic-
tion to recover such
cost.
c Onshore facility
The owner or operator
of an onshore 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 Govern-
ment in an amount not to
exceed $8,000,000, except
that 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.
11 Revolving fund
The provisions of Public Law
91-224 authorizes to be
appropriated a revolving fund
to be established by the
Treasury not to exceed
5-5
-------
$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 appropri-
ated to, or deposited in, said
fund shall remain available
until expended.
12 Evidence of financial responsi-
bility
Public Law 91-224 provides that
any vessel over three hundred
gross tons, including any barge
of equivalent size, using any
port or place in the United
States or the navigable waters
of the United States for any
purpose shall establish and
maintain 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
co the United States which
3uch 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 sub-
jected. Financial responsibil-
ity may be established by any
one of, or a combination of,
the following methods accepta-
ble to the President: (A)
evidence of insurance; (B)
surety bond; (C) qualification
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.
Outline prepared by Howard
Lamp'l, Contingency Plans
Officer, Edison Water Quality
Laboratory, Edison, New Jersey
08817, January 1971.
5-6
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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 prepar-
ation of a National Contingency Plan
for Oil and Hazardous Materials.
This plan was published in the Fed-
eral Register on June 2, 1970. It
superseded the National Multiagency
Oil and Hazardous Materials Con-
tingency Plan which was approved
in September, 1968.
II PURPOSE
tants, and institution of action
to recover clean up 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.
The Plan represents an agreement
among concerned departments and
agencies of the federal government
for a pattern of coordinated and
integrated response to major pol-
lution incidents. It establishes
a national response team and pro-
vided guidelines for the establish-
ment of regional contingency plans
and response teams. The plan pro-
motes the coordination and direc-
tion of federal, state and local
response systems and encourages
the development of local govern-
ment and private capabilities to
handle such pollution incidents.
Ill OBJECTIVES
The objectives of the plan are to
develop effective systems for dis-
covering and reporting the existence
of a pollution incident, 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, appli-
cation of techniques to clean up
and dispose of the collected pollu-
V PARTICIPATING AGENCIES
Each of the primary Federal agencies
has responsibilities established by
statute, Executive Order or Presi-
dential Directive, which may bear
on the Federal response to a pollu-
tion incident. This plan intends
to promote the expeditious and har-
monious discharge of these respon-
sibilities 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 and Health, Education and
Welfare and the Office of Emergency
Preparedness.
VI ORGANIZATION
The plan calls for the establishment
of a National Inter-Agency Committee
(NIC) which is the principal instru-
mentality £or plans and policies of
the federal multi-agency response
to pollution emergencies.
6-1
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At the Washington level, the plan
establishes a National Response
Team (NRT) which consists of repre-
sentatives of the signatory agencies
which shall act as an emergency
response team to be activated in
the event of a pollution incident
involving oil or other 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 (NRG) in Washington, B.C.
is the headquarters site for activ-
ities relative to pollution inci-
dents.
There are established throughout
the United States, Regional Response
Teams (RRT) that perform functions
within the local regions similar
to that performed by the National
Response Team on the national level.
Regional Response Centers(RRC),
similar to the NRG, are located
in each of the pre-designated
regions.
The plan further provides that in
each region, there uill be estab-
lished 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.
VII DELEGATION OF RESPONSIBILITY
The U. S. Coast Guard is to provide
for On-Scene-Commander's in areas
where they have assigned responsi-
bility, 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 Commander's in
other areas.
VIII FEDERAL RESPONSE OPERATION
The actions taken to respond to a
spill or pollution incident can be
separated into five relatively dis-
tinct classes or phases. For
descriptive purposes, these are:
Phase I. Discovery and Notifica-
tion;
Phase II. Containment and Counter-
measures;
Phase III. 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 con-
currently with one or more other
phases.
IX REGIONAL CONTINGENCY PLANS
Separate regional plans are to be
developed by the Environmental Pro-
tection 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:
6-2
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A. A definition of the area covered
including the points of change
in jurisdiction between Environ-
mental Protection Agency and
U. S. Coast Guard.
B. A notification and reporting
system beginning with the ini-
tial discovery of an incident.
C. Names, addresses and phone
numbers of all pertinent fed-
eral, state, local and indus-
try personnel involved in the
reporting system.
D. A listing of predesignated
On-Scene Commander's and
Regional Response Center's.
E. Listing of resources and
equipment available in the
regional area with names,
addresses and phone numbers.
This outline was prepared by A. W.
Bromberg, Chief, Operations Branch
FWQA, Edison Water Quality Laboratory
6-3
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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 respon-
sibility. Are you 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 legisla-
tion.
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 manage-
rial ability. From utter chaos,
he must organize a small army
of men and equipment to remove
. the oil from the water and shore-
face. 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 t he 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 to any damage to
marine life; and finally,
the oil and shipping indus-
try 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
7-1
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contracting officer, to handle
the myriad details for the hir-
ing of and negotiations with
various contractors, purchase
request and the recording and
handling of petty cash funds.
He should also have on his
staff, technicans 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 suit-
able headquarters in which to
work. Ideally, a Coast Guard
Station would provide a suit-
able headquarters is 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
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 tele-
phones; desks; chairs; writing
equipment; typewriters and if
possible, a teletypewriter.
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 congressional hear-
ing.
C Communications
Whenever the On-Scene-Com-
mander 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 com-
munications with the con-
tractors 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
7-2
-------
the field, the On-Scene-
Commander dials a specified
number and asks the operator
to have No. A-16 call head-
quarters. 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 communica-
tions are established. This
system can be rented for a
nominal fee.
Communications between air
observers and headquarters
is a necessity and observa-
tion and work vessels should
also be able to contact the
field headquarters.
IV RELATIONS WITH OTHER ORGANI-
ZATIONS
A Federal
1 Environmental Protection
Agency
2 U. S. Coast Guard
3 U. S. Army Corp of Engineers
4 U. S. Health, Education and
Welfare
5 Office of Emergency Prepar-
edness
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 Admini-
stration
B States
Individual states are
encouraged to make commit-
ments 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 legisla-
tion to become involved in
a major oil spill cleanup.
C Interstate Agencies
Interstate agencies too, are
encouraged to make commit-
ments to the cleanup of major
oil spills. Interstate
agencies can also take com-
plete charge of a major oil
spill, but again, the fund-
ing 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 man-
power and equipment.
7-3
-------
E Academic Communities
The academic communities
throughout the country can
usually be counted on to
furnish information and
advice on the local environ-
ment, 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 compari-
son with post spill biolog-
ical 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 clean-
up 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 govern-
ment proceed with the cleanup.
All cost borne by the federal
government will be reimbursed
by the polluter.
B The individual state govern-
ment can assume command of a
spill cleanup, if they so
desire. But again, the fed-
eral 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.
C 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 fed-
eral government in the clean-
up 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 Caynon
incident, it was very dif-
ficult 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 respon-
sible 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
7-14
-------
end up as evidence in a fed-
eral 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 con-
tractor has on hand, the type
of equipment, the conditions
of the equipment. He should
know if the contractor has
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 contrac-
tors in the field. This is
necessary to insure that the
federal government receives
full value for every dollar
spent on the cleanup.
VII REPORTS REQUIRED
A The National Contigency Plan
requires that the On-Scene-
Commander submit two situa-
tion reports daily. On at
0800 hours and one at 2000
hours. These reports are
normally submitted by tele-
type. If any event of dra-
matic 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 prepara-
tion 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,
FWQA, Edison Water Quality Laboratory
7-5
-------
OIL CHARACTERISTICS
Chemical and Physical Characteristics
Fate and Behavior
Oil Sampling
Oil Identification
-------
PHYSICAL AND CHEMICAL CHARACTERISTICS OF OIL
I PHYSICAL CHARACTERISTICS OF OIL
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) 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 temper-
ature :
do
s = 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/ml at 3.98° C).
2 API gravity is def ined by the
following equation:
1U1.5 -
API gravity = s
131.5
'60°F
where S60° F is the specific
gravity of the oil at 60° F.
3 Viscosity is defined as
the resistance to flow.
a Absolute viscosity is
the force required to
move a plane surface
area of one square cen-
timeter over another
plane surface at the
rate of one centimeter
per second when the
two surfaces are separ-
ated by a layer of
liquid one centimeter
in thickness.
b Kinematic viscosity is
the ratio of the abso-
lute viscosity to the
specific gravity of the
oil at the temperature
at which the viscosity
is measured.
^ 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 con-
fused 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 10° to
70° higher than its flash
point.
6 Cloud Point is the tempera-
8-1
-------
ture 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
noncombustible 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 gaso-
line, and viscosity index, an
empirical number indicating the
effect of a change in the tem-
perature on the viscosity, is
determined for lubricating oils.
II CHEMICAL COMPOSITION OF OIL
A Introduction
Another method of classifying
petroleum products is according
to the types of chemical compounds
which it contains. For convenience,
a group of definitions is included.
B Definition of Terms
1 Hydrocarbon is a chemical com-
pound which contains only the
elements carbon and hydrogen.
2 Saturated Hydrocarbons are
hydrocarbons 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 C C H
A Double Bond is formed when
four valence electrons are
shared by two atoms.
H H
H:C: :C:H
H H
8-2
-------
A Triple Bond is formed when
six valance electrons are
shared by two atoms.
rl *
' H
An Unsaturated Hydrocarbon
is one which contains one or
more double or single bonds.
The term unsaturated refers
to the fact that hydrogen
atoms are defic-ient and can
be added under the proper
chemical and physical condi-
tions. Thus, ethylene and
acetylene shown in 4 and 5
above, respectively, are
unsaturated hydrocarbons.
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.
Chemical Composition of
Crude Oils
1 Background
Crude oils vary greatly
in composition but con-
sist mainly of hydrocar-
bons and compounds
containing oxygen, nitro-
gen, 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 90-957o hydro-
carbons while crude oils
8-3
-------
of Mexico and California have
only 50% hydrocarbons. The
hydrocarbon compounds in
crude oil consist mainly of
paraffins, napthenejs, and
aromatics.
a Paraffins are saturated
hydrocarbons such as ethane.
A wide range of paraffins
can be found in crude oils.
The light ends, the vola-
tile components are mainly
low molecular weight par-
affins containing 12 or
less carbons.
1 Straight-Chain Paraffins
are those in which the
carbon atoms are arranged
linearly.
the carbons of the
main chain.
CH3
C HaC C H 5
CH2
I
CH3
H H H
Napthenes are cyclo-
paraffins. That is, the
two ends of an open chain
are joined together, form-
ing a cyclic structure.
HCCCH
H H H
2 Branched-Chain Paraffins
are those which have a
linear arrangement of
carbon atoms with other
carbon atoms attached to
HaCCH2
H
-------
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.
Arotnatics in crude oils are
found to a lesser degree than
paraffins or eyelo-paraffins.
They are usually found in the
higher boiling fractions
since they are for the most
part of rather high molecu-
lar weight.
Other Hydrocarbons consist
of combinations of the
above three classes. For
example, in the high boiling
fractions napthene rings may
be fused to aromatics with
side paraffin chains attached.
Oxygen-Containing Compounds
in crudes are almost exclu-
sively 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 . 57o
napthenic acids in contrast
to the trace amounts found in
other USA crudes. Fatty
ac ids are paraffins with a
terminal -~COOH group-
CHS(CH2)WCOOH
c
I
c-c-c
Napthenic Acids are eye lo-
paraf fins with a -COOHgroup
attached.
8-5
-------
Phenols are aromatic compounds
with an OH group attached.
been identified as mer-
captans (thiols) and
suIf ides. These can be
either cyclic, or non-
cyclic or a combination.
1 Merc apt ans are paraf-
fins, napthene, and
aromatic s with -S-H
groups attached.
OH
I
C
N:
CCCCSH
CSH
6 Sulfur Containing Compounds
a Crude oils vary in sulfur
content from O.l7o in non-
asphalt ic 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
SuIf ides are compounds
where an S atom
replaces a non-terminal
carbon atom..
8-6
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PRODUCT
LPG
Light Gasoline
Naptha
Kerosene
#1 Fuel Oil
Gas Oil
Lube Oils Residuum
#2 Fuel Oil
TABLE I
CRUDE OIL - CLASSIFICATION BY CONTENTS
Paraf f inic
Napthenic
Paraf f inic - Napthenic
Paraf f inic - Napthenic - Aromatic
Napthenic - Aromatic
Napthenic - Aromatic - Asphaltic
Aromatic - Asphalt ic
TABLE II
BP RANGE
-45° to 0.5° C
-.5° to 150°
150° to 210°
151° to 270°
210° to 330°
216 to 343
CARBON ATOMS
3 -
225° to 360'
9
9
12
15
> 15
12
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
8-7
-------
Nitrogen Containing Compounds
are found in only ver small
proportions and consist mainly
of quincline and pyridine
derivatives.
according to their boiling
ranges. The most common
petroleum products, their
boiling ranges, and approx-
imate molecular weight
ranges are listed in Table
II.
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 pres-
ent as organometallic chelates.
D Classes of Crude Oils are based on
the relative compositions with re-
spect to paraffinic, napthenic,
aromatic, and asphaltic content.
The main types are shown in Table
1.
E Characteristics of Refined Petrole-
um Products
1 Boiling Ranges: Petroleum
products are usually classified
8-8
Outline prepared by J. P.
Lafornara, Research Chemist,
Edison Water^Quality Labora-
tory, Edison, New Jersey
January 1971.
-------
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, eva-
poration, dissolution and emulsi-
fication, 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 milli-
meters or less and is dependent on
several parameters among them,
viscosity of the oil, surface ten-
sion 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 con-
ditions, 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. Al-
though this process starts immedi-
ately, it is a long term one and
continues throughout the duration
of the total weathering process
since the oxidation and microbio-
logical degradation processes con-
stantly 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 drop-
lets of optically measurable size.
In the case of oil, the emulsion
can be either an oil-in-water emul-
sion or a water-in-oil emulsion.
E Auto-Oxidation
Auto-oxidation is the light cata-
lyzed reaction by which hydrocarbons
react with atmospheric oxygen to
form ketones, aldehydes, alcohols
and carboxylic acids which are all
polar compounds which 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, filamen-
tous fungi, and yeasts utilize
hydrocarbons and chemically oxi-
dized hydrocarbons as food sources.
9-1
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1 Aerobic Microblal 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 degra-
dation to occur. However,
areas of activity beneath
the surface in the water
column or in bottom muds
are severely limited by the
supply of oxygen.
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 sul-
fate as their oxygen source.
"Psuedomonas aeruginosa", for
example, utilizes n-octane or
n-hexadecane while reducing
nitrate to nitrite. Many sul-
fate-reducing bacteria are
known.
G Sinking
Evaporation, dissolution and
oxidation of lighter hydrocar-
bons may cause the oil to in-
crease its density. When this
happens to a sufficient extent
the oil will sink to the bottom
where anaerobic microbial oxida-
tion 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
reaches some land mass.
Ill PHYSICAL MOVEMENT OF OIL SLICKS
In the absence of current or debris,
an oil slick will move in the direc-
tion 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.
REFERENCES
1 Fay, James A., The Spread of
Oil Slicks on a Calm Sea,
Fluid Mechanics Laboratory
Publication No. 69-G, Massa-
chusetts Institute of Tech-
nology, Cambridge, Massa-
chusetts. 1969.
2 Blokker, P. C., Spreading and
Evaporation of Petroleum
Products on Water, 1964
International Harbor Con-
ference, Antwerp, Belgium.
3 Smith, J. E., The Torrey Can-
yon, Pollution and Marine
Life, Cambridge, University
Press. 1968.
4 Scott, G., Atmospheric Oxida-
tion and Antioxidants, Else-
vier, New York. 1965.
5 Davis, J. B., Petroleum Micro-
biology, Elsevier, New York.
1967.
6 Holcomb, R. W., Oil in the Eco-
system, Science, 166, 204-206.
1969.
9-2
This outline was prepared by Dr. J.
Lafornara, Research Chemist, Edison
Water Quality Laboratory, Edison, NJ
January 1971.
-------
OIL SAMPLING PROGRAM
I INTRODUCTION
A complete oil sampling program is
undertaken for the primary purpose
of presenting legal evidence in a
court of law. To protect the inter-
ests 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 physi-
cally or chemically altered by
the collection procedure.
3 Transfer of the sample must be
accomplished using a well de-
fined chain of custody system.
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 sus-
pected source.
2 Quantitative - to determine the
amount of oil present at the
spill site.
Collection for qualitative analy-
sis 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 photographic and elec-
tronic 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 instrumen-
tation, on the other hand, would
allow occasional spot checks of
other areas and effective monitor-
ing of cleanup operations.
Ideally, such instrumentation
should be capable of detection,
identification and of providing
aerial and thickness measurements.
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
inexpensive, coded material be
added to oil. This material must
be chemically and physically
stable in both oil and oil
slicks. It must be readily iden-
tifiable by available analytical
techniques and it must have no
adverse effect on the oil's sub-
sequent use.
Passive tagging assumes that oils
are so chemically diverse that
their contents constitute a stable
chemical fingerprint that can be
unequivocally disclosed by labora-
tory procedures.
10-1
-------
Sampling for quantitative analysis
is extremely difficult due to varir
ations in slick thickness over the
spill area. For this reason
experienced, visual observation
will generally provide more relia-
ble 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.
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
TABLE I
Appearance of Slick
Barely discernible
Silvery sheen
Faint colors
Amount of Oil
25 gal/sq. mi.
50 gal/sq. mi.
100 gal/sq. mi.
Bright bands of color 200 gal/sq. mi.
Dull brown 600 gal/sq. mi.
Dark brown 1,300 gal/sq. mi.
10-2
-------
4 Source of spill
a Offshore platform
b Refinery
c Terminal operation
d Storm drain
e Ship - in port
- offshore
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 pro-
cedures, two additional types of
qualitative analysis may also be
performed to detect the presence of
oil in water, fish and shellfish
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 repre-
sentative OIL sample must be collected
from the source, such as:
1 The ship - each compartment, bilge
and ballast
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. How-
ever, this should only be done
if BEFORE and AFTER samples can
be obtained and only if a quali-
fied staff of marine biologists
are available for collection,
preservation and analysis.
Ill SAMPLE COLLECTION
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 it-
self. 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
10-3
-------
glass, teflonj 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
characteristics 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 pre-
served, depending upon the volatil-
ity 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, (approxi-
mately 0«5 cuo 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 compon-
ents are present (No. 2 or lighter),
the sample can be preserved by
carefully filling the bottle to the
top with water to displace the air0
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 20 mis be considered 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 obvi-
ous. An oil slick may vary in
thickness from several inches down
to a monomolecular layer measured
in microns (10 cm.). The quanti-
ty 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 recov-
ery is 50 percent rather than 100
percent, the sweep, area must be
doubled. Table nbelow describes
theoretical thickness and area,
assuming an even distribution of
oil for various magnitude oil
spills.
10-4
-------
TABLE II
OIL DISTRIBUTION ON A WATER SURFACE
Spill Area
Gal/Sq. Mile
Spill Area
ml/Sq. Meter
Area (Sq. Meters)
Req'd. to Obtain
200 ml/sample
1,000,000
100,000
10,000
5,000
1,000
100
1430
143
14
7
1
0
.30
.15
.43
.143
0
1
14
28
140
1400
.14
.4
Oil
Thickness (mm)
1.43
0.143
0.0143
0.0071
0.00143 = 1.43(1
0.000143= 0.143U,
C The ideal oil sampling device should
contain the following characteris-
tics:
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. Collec-
tion and separation is continued
until about 1 pint of oil has been
collected. The procedure is
quantitatively 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
10-5
-------
4 Dustpan with a stopcock fitted
to the handle
b Separation procedure devices have
included:
1 Manual dec ant at ion
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 materi-
als include teflon shavings, straw,
polypropylene fiber, rope, glass
fiber, paper, and polyurethane foam.
Qualitative sampling requires con-
tact 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.
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 quantita-
tively to * 25% with a single sample.
b Polyurethane foam
Adsorption by polyure-
thane 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 spectrographic
analysis revealed no chem-
ical differences between
the original oil and the
sample recovered.
IV DOCUMENTATION OF EVIDENCE AND SAMPLES
A Procedures for documentation of
evidence and samples are speci-
fied by the National Oil and
Hazardous Materials Pollution
Contingency Plan and its regional
derivatives. Collectively these
plans guide the coordinated reac-
tion of Federal, State, and local
government and private agencies
to uncontrolled discharges of
hazardous materials. Documenta-
tion procedures include collection
of samples from both the water
course and suspected sources and
preparation of a pollution inci-
dent report (Form FWPCA-209).
These procedures have been
10-6
-------
established to document the actual
facts of an incident and to protect
the interests of all parties.
After having been collected as out-
lined above each sample should be
properly labeled using the chain of
custody record, Form FWPCA-208 (See
Figure 1). The record should con-
tain 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 signatures
of the sample collector and one
or more witnesses. FAILURE TO
OBTAIN THE SIGNATURES OF WIT-
NESSES MAY RENDER THE SAMPLE
IEGALLY 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 sub-
mitted for shipment, the name of
individual from whom it was re-
ceived, 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 repre-
sentative 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 was re-
ceived and the proposed
disposition. If the sample
is to be shipped to more
than one laboratory, dupli-
cate custody records bear-
ing 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 inci-
dent report, Form FWPCA-209
(See Figure 2). Copies of
the report and additional doc-
uments and attachments should
be distributed as follows:
1 The original and one copy
to the Chairman of the
Appropriate Regional Opera-
tions Team.
2 One copy to the Joint Opera-
tions 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
10-7
-------
endorsement. As much data,
facts, observation and in-
formation as possible should
be included. A1-1 statements
from persons directly con-
cerned 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.
References;
1 "Oil Sampling Techniques", Edison
Water Quality Laboratory, Edison,
New Jersey (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).
V SUMMARY
A full scale oil sampling program
is designed to collect samples,
the 'analysis of which will be pre-
sented 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 sam-
pled 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 adsorption and subse-
quent recovery. There is pres-
ently no recognized standard
procedure.
Documentation of samples and evi-
dence is required to adequately pro-
tect the interest of all parties
to an incident. The conditions of
collection, shipment and receipt of Outline prepared by J. S. Dorrler,
samples should be documented with Acting Chief, Oil Research and
utmost care to preclude later ques- Development Section, Edison Water
tioris of validity. Quality Laboratory, Edison, New
Jersey 08817, January 1971.
10-8
-------
FEDERAL WATER POLLUTION CONTROL C|U|M Qf CUJTO()y RE<-OR(>
A U Ml.* IJ T K ATION
NAME OF UNIT AND ADDRESS
3AMPUK NO.
TIME T A K E N (hour») DATE TAKEN
PLE
ri N*~ME~~6F~~PE~R3ON TAKING SAMPLE (Firtt, Inltimi, Lm»t N»at
< WIT N ESSIES) TO T A K INC S AMPU ^ (Firtt, Inittml, Lmtt N*tti9)
U
1 hereby certify that I received this sample and disposed of it as
noted below.
'* RECEIVED FROM DATE RECEIVED TIME RECEIVED
U* DtSPOSITlON OF SAMPLE SIGNATURE
(C
1 hereby certify that 1 obtained this sample and dispatched it aa
s~"\ \ tu shown below.
z
<
I*.
o
z
u
SENT TO SIGNATURE
Figure 1
10-9
-------
o
I
U. 5. DEPARTMENT OF THE INTERIOR
POLLUTION INCIDENT REPORT
SECTION I - VESSEL DATA
4. NAME OF VESSEL
12. OWNER(S) OF VESSEL (name & address)
3. .OFFICIAL NUMBER
13. LOCAL AGENTS (name & address)
SECTION II SHORE FACILITY DATA
SECTION III - POLLUTION DATA
(name and address H available)
a EQUIPMENT | 1 PERSONNEL
FAILURE L_J FAILURE
ZQ
K >
< z
a: ~
hi -i
a. in
n z
N a
UJ
a.
NAME
geodrophic coordinates)
23. TIME
24. DATE
A TTACHED
DUTY
LICENSE NL
JMBER (it applicable)
SIGNED STATEMENT
ATTACHED
YES
NO
SECTION IV - POLLUTION SAMPLES
FWPCA 209 f7.6B1
TIME TAKEN
WITNESS
CO
ra
'O
i
o
m,
1-1
Figure 2
-------
SECTION IV (Continued)
31. REMARKS (Civo full description of incident, including attitudes ol personnel and cooperation received. It necessary, continue on blank paper and attach.)
o
H-
ra
r-)
o
FIRST ENDORSEMENT
34. FROM
3S. TO
30. SIGNA TURE
37. DATE
33A. DATE SIGNED
SECOND ENDORSEMENT
38. FROM
3». TO
40. SIGNA TURE
41 . DATE
FWPCA 209 (7-68) (Ro.er..)
Figure 3
-------
ANALYSIS OF OIL SAMPLES
I INTRODUCTION
A Oils and oil-water samples are ana-
lyzed to identify the type of spilled
petroleum product or to establish
similarity between samples collected
from the environment and from suspect-
ed sources. Common origin is probable
if samples agree in their key charac-
teristics .
B Analysis is complicated by effects of
environmental influences and lack of
procedure adapted to oil-water mix-
tures. Petroleum analysis is based
upon procedures developed with petro-
leum products.
C Analysis of environmental samples
involves preliminary clean-up fol-
lowed by standard analytical proce-
dures. The complete analytical se-
quence shown in Figure 1 involves
three levels of activity.
1 Preliminary clean-up intended to
separate the oil from the water
and produce an organic phase amen-
able 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 compari-
son of results with prescribed
characteristics of typical petro-
leum products. Characteristics
of a few such petroleum products
are specified in Table 1.
3 Further analysis to more clearly
define the relationship between
the environmental sample and
reference samples collected from
suspected sources. Results of
the analyses are used to evaluate
similarity.
D Both the apparent and suspec-
ted nature of the sample will
influence the actual labora-
tory procedure. The analyst
himself will normally select
the procedures necessary to
accomplish identification or
comparison. The required
level of analysis (e.g., iden-
tification or identification/
comparison) depends on the
nature of the problem.
II CLEAN-UP
Sample clean-up is commonly accom-
plished by one of three basic me-
thods:
A Simple Phase Separation is
generally applicable to dis-
tillate fuel oils (Fuel oil
nos. 1, 2, and U, kerosine,
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 CaCl2- The dissolved
petroleum products may be "salted
out" of the aqueous phase by the
addition of Na2$0^ to the water.
B Drying with Centrifugation
When the petroleum product,as
is the case with some crude
oils and residual fuel oils,
is emulsified with water and/
or solid matter, it is some-
times possible to break the
emulsion by removal of the
water from the matrix with an-
hydrous calcium chloride, and
then centrifuging the sample
in a chemical centrifuge to
isolate the oil phase as the
centrifugate.
11-1
-------
Analysis of Oil Samples
C Phase Separation with Solvent Addi-
tion is accomplished by adding a sol-
vent, such as chloroform to the oil-
water mixture. It is sometimes poss-
ible to obtain a clean phase separa-
tion by solvent addition and to pro-
ceed as in A to separate the organic
phase from the aqueous. The organic
phase, after drying with calcium chlo-
ride, is heated to evaporate the sol-
vent.
Ill IDENTIFICATION
A When clean-up 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 identification. 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 combina-
tion 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 petro-
leum products, and to distin-
guish between crude oils and
residual fuel oils from differ-
ent locations. Table 2 gives
solubility characteristics for
several typical petroleum pro-
ducts .
2 Specific or API Gravity - The
gravity or density is a distin-
guishing characteristic of oils.
However, as the loss of volatiles,
which occurs in the early stages
11-2
of environmental exposure
with volatile distillate
fuels and crude oils, re-
sults in an increase of
this parameter, it is of
limited value.
Infrared Spectroscopy -
Indicates the relative con-
tent of aromatic or carbon-
ring-type compounds. May
also indicate presence of
additives such as silicones.
Generally employed to char-
acterize materials less vola-
tile than #2 fuel oil, such
as tfk and residual fuels.
Average Molecular Weight -
Used to identify low and high
boiling products. Not com-
monly employed with other
than pure hydrocarbons.
Distillation Range - Defined
as the temperature difference
between high and low boiling
compounds in an oil observed
during distillation. Actual
procedures are specified by
ASTM D 86-56, ASTM D 850, and
ASTM D 216. Reported as the
actual temperatures at which
distillation begins and ends:
(1) I.E.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 vola-
tilization of lower boiling
components. Typical distilla-
tion ranges are presented in
Table 1.
Viscosity - A measure of the
resistance to flow. May be
expressed as (a) Saybolt se-
cond units (SSU), the time
required for a standard volume
of oil to pass through a stan-
dard orifice, as specified by
-------
Analysis of Oil Samples
ASTM D 445-53T and ASTM D 446-53;
(b) kinematic viscosity at 100°F
or 212°F in centistokes (ASTM D
445-65) or in Saybolt Furol units
at 122°F. ASTM 2161-63T gives
the relationships between the
different viscosity units.
7 Distillation - As a loss of vola-
tile 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 distill-
ing all samples to a similar degree.
This is accomplished in our labora-
tory by distillation in a simple
distillation apparatus to obtain a
distillate boiling point of 275°C
at 40 mm Hg pressure. The distill-
ate is analyzed by gas chromato-
graphy 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 oil; 0.2
to 3% for #4 fuel oil; and 0.4 to
4.25% for #6 fuel oils.
11 Nitrogen is determined by the Kjel-
dahl method.
IV SUMMARY
Oil analysis involves three levels
of laboratory activity: sample pre-
paration and clean-up; basic iden-
tification; and final comparison.
Identification as a petroleum pro-
duct is accomplished by comparison
of sample characteristics to pre-
scribed properties of typical pro-
ducts. Further analysis may be
performed to more firmly establish
the similarity between environmental
samples and reference samples col-
lected from potential sources. At
all stages of analysis the judge-
ment of the analyst is crucial.
Typical analyses include observa-
tion of solubility in organic sol-
vents, infrared spectroscopy, API
Gravity, distillation range, gas
chromatography, specific metal deter-
minations, viscosity measurement,
and sulfur determination.
REFERENCE
Kawahara, Fred K., Ph D., F.A.I.C.
Laboratory Guide for the Identi-
fication of Petroleum Products,
U.S. Department of the Interior,
Federal Water Pollution Control
Administration, Division of
Water Quality Research, Analy-
tical Quality Control Laboratory,
1014 Broadway, Cincinnati, OH
45202. January 1969
Kahn, L., Unpublished data
This outline was prepared by L.
Kahn, Chief Chemist, Laboratory
Branch, Environmental Protection
Agency, Edison Water Quality Labo-
ratory, Edison, N.J. 08817, Jan-
uary 1971
11-3
-------
ANALYTICAL SCHEME FOk tkUuc GILa
DISCARD AQUEOUS PHASE
OIL + WATER SAMPLE
PHASE SEPARATION
AND DRYING OF OIL
INFRARED ANALYSIS
VISCOSITY AT 37.8-C
DENSITY AT 2O-2S°C
DISTILLATION
TO 275°C AT 40 TORR
WEIGH
% RESIDUE
KJELDAHL NITROGEN
ASH WITH
SULFURIC ACID
INFRARED ANALYSIS
THIN-LAYER
CHROMATOGRAPHY
HEXANE-INSOLUBLES
INFRARED ANALYSIS
*GAS
CHROMATOGRAPHY
VANADIUM BY
ATOMIC ABSORPTION
NICKEL BY
ATOMIC ABSORPTION
TEMPERATURE PROGRAMING 40-300°C
3* SE-30 ON 60/60 CHROMOPORT,
6' x V," COLUMN; SULFUR FLAME PHOTOMETRIC
AND HYDROGEN FLAME IONIZATION DETECTION.
-------
Analysis of Oil Samples
TABLE 1
CHARACTERISTICS OF STANDARD PETROLEUM PRODUCTS
PRODUCT
API GRAVITY KINEMATIC
(API UNITS) VISCOSITY
(centistokes)
DISTILLATION
RANGE
(I.E.P. - E.P.)
COMMENT
High Gravity
Naphtha
Low Gravity
Naphtha
Gasoline
Jet Fuel
Kerosine
Fuel oil ftl
Fuel oil ff2
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°
2.3 - 10.5 40°
> 100 >
- 206° F
- 410° F
- 408° F
- 500° F
- 575° F
- 675° F
(90%)
- 683° F
- >850° F
700° F
Sulfur 0.02%
Contains lead,
halogens
Narrow API
Gravity range
Sulfur exceeds
0.5%
Wide dist.
range
11-5
-------
Analysis of Oil Samples
SOLUBILITY
PRODUCT
LIGHT NAPHTHA
HEAVY NAPHTHA
GASOLINE
JET FUEL
KEROSINE
CUTTING OIL
MOTOR OIL
PARAFFIN WAX
WHITE PETROLEUM JELLY
GREASE
RESIDUAL FUEL OIL
ASPHALT
VS = very soluble
S = soluble
PS = partly soluble
I = insoluble
TABLE 2
OF PETROLEUM PRODUCTS IN ORGANIC SOLVENTS
SOLVENT
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
11-6
-------
PREVENTION AND CONTROL - TREATMENT
Tanker Operation
-------
TANKER OPERATIONS
I INTRODUCTION
Various government and oil industry
sources estimate that anywhere from
33,000 barrels of oil per day, up to
ten million tons of oil per year
foul the world's oceans and seas.
This may be a conservative estimate.
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 col-
lected in an aft center tank
as the residue of tank cleaning
operat ions.
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 inatten-
tion.
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: Whenever a loaded
tanker vessel is involved in a
collision the results is usually
a major discharge of oil into
the surrounding waters.
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 pockmarked
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, tem-
perature, volatility and the
roughness and configuration of
the container.
In the same way, a certain
quantity of oil vunder fixed con-
ditions 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
12-1
-------
would be found to be adhering
to 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 opera-
tion of great significance in
connection with the waste oil
resulting from tanker opera-
tion is the system used for
cleaning or washing down the
tanks. Until the early 1930'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 tempera-
ture 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
per cent of the world's crude
oil tankers practice the tech-
nique. Refineries of the major
oil companies accepted 'load-
on-top' residue after an experi-
mental period in which they
proved to themselves that the
residue can be processed
through the refinery units
if it is less than 1 per cent
of the total crude cargo, and
if the water content of the
residue is less than O."l5 per
cent 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 opera-
tor, then, is to remove as much
water as possible from beneath
the oil without discharging
the oily waste itself.
B. Principals 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 discharged
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 withdrawn,
the next cargo is loaded on top
of the remaining residues in this
tank. Usually, this one compart-
ment 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.
12-2
-------
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 decant-
ing this residue will not pollute
the sea. Even the momentary
maximum of 5000 ppm is only half
of one per cent. 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-top' cycle.
D. PPM of Oil Discharged - "Eye-
ball Method": "Load-On-Top"
is a questionable first step
in the prevention of pollution
of the sea by oil. There are
too many questions left unan-
swered. 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 than 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" paper, the author
admits that at times, the dis-
charge of oily 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 formsan oil in water emul-
sion 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 indus-
try as a whole, has spent liter-
ally millions of dollars trying
to separate oil from their waste-
water discharge. This is still
a major problem in the industry
today. If the sophisticated
oil/water separators of the
major refineries cannot success-
fully 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 earn-
ing capacity of a ship. The
gross tonnage after deduction
of certain spaces, such as engine
12-3
-------
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, vary-
ing 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
deadweight is, as the name implies,
the actual weight in tons of the
cargo when loaded, as distinct
from stores, bassast, 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.
VI SINGIE 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
vessle to be moored. The con-
necting hose to the underwater
pipeline., is connected to a small
floating buoy, which is retrieved
when the ship is in a fixed posi-
tion. The known objections to
this system are: (1) the vessel
cannot remain in this position
in rough weather, and (2) when
whe 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 advan-
tages of this type of installation
is that four pipelines can service
six to eight berths simultaneously.
The disadvantages of this type
of installation are:
(1) Extremely expensive to
construct.
(2) Ships must stop off-load-
ing 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 per-
sonnel 1 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 experi-
mental 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 pipelines o.r the oil
12-4
-------
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 accep-
tance throughout 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
considers the Single Point
Mooring System as the next
best thing to a harbor moor-
ing. Shell Oil Company and
IMDDCO 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 constructing 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 approxi-
mately 70 feet below the water
surface. When there are suf-
ficient numbers of SPM buoys
throughout the world, tankers
will convert to bow loading
manifolds. The cost of conver-
sion to this type of loading
will be approximately $70,000
per tanker.
REFERENCES
1 Kluss, W. M. Prevention of Sea
Pollution in Normal Tanker
Operations. Institute of
Petroleum Summer Meeting,
Brighton 1918, paper No. 6.
Mobile Shipping Co. Ltd.
2 Moss, J. E. Character and
Control of Sea Pollution by
Oil. American Petroleum
Institute, Division of Trans-
portation, Washington, D.C.
1963
This outline was prepared by H.J.
Lamp'l, Oil Spills Coordinator, FWQA,
Edison Water Quality Laboratory
12-5
-------
CHEMICAL TREATMENT
Dispersants - Policy
EPA Tests
-------
DISPERSANTS
I BACKGROUND HISTORY
As far back as the early 1930's
water emuIsiftable 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 dis-
persing in the grease or oil, and
making the resultant mixture dis-
persible 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 ship-
ping 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 sea-
water. Sulfonated petroleum oils
and later more sophisticated syn-
thetic detergents made their
appearance in these products.
These emulsifying degreasers were
widely used aboard ship for en-
gine room maintenance, as well as
for the clean-out of petroleum
cargo tanks prior to welding re-
pairs 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 over-
board to minimize slick formation.
There are presently over 200
commercially available products
which are claimed useful for dis-
persing oil from the surface of
the water. These products have
been referred to as "soaps", "de-
tergents", "degreasers", "complex-
ing agents", "emulsifiers", and
finally "dispersants". This latter
term describes best what this type
of product is intended to accom-
plish 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 dis-
persants are surfactants, solvents
and stabilizers.
A Surfactants or Surface Acting
Agents (SAA)
This is the major active compon-
ent 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 what we commonly call an
emulsion.
These agents are often defined
according to their behavior in
aqueous solutions. These solu-
tions will usually wet surfaces
readily, remove dirt, penetrate
porous materials, disperse solid
13-1
-------
particles, emulsify oil and
grease and produce foam when
shaken. These properties are
interrelated; that is, no sur-
face active agent possesses
only one of them to the exclu-
sion 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 solu-
tion, and like the soaps are
typical colloidal electrolytes.
The second class, the non-ionic,
do not ionize, but owe their
solubility to the combined ef-
fect of a number of weak solu-
bilizing groups such as ether
linkages or hydroxy groups in
the molecule. A more detailed
discussion of SAS is covered
in reference (l).
Commonly used SAA in oil spill
dispersants include soaps, sul-
fonated organics, phosphated
esters, carboxylic acid esters
of polyhydroxy compounds,
ethoxylated alkyl phenols and
alcohols (APE, LAE),block
polymers and alkanolamides.
B Solvent s
Since many of the surface active
agents applicable to oil spill
dispersant compounding are
viscous or solid materials, some
form of solvent is often neces-
sary in order to reduce viscos-
ity 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 eas-
ily emulsifiable. The solvent
usually comprises the bulk of the
dispersant product.
The three general classes of sol-
vents used in oil spill dispersants
are petroleum hydrocarbons, alco-
hols or other hydroxy compounds,
and water.
1 Petroleum Hydrocarbons
Petroleum fractions with boil-
ing points above 300°F are
usually used, and these may
produce finished dispersants
with flash points as low as
110°F. The proportion of aro-
maticity is of concern, since
this effects solubility and
emu1sification properties as
well as toxicity. Wardley Smith,
Warren Springs Lab, UK, in des-
cribing the Torrey Canyon inci-
dent, 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 contain signifi-
cant quantities of higher
alkylated benzenes.
13-2
-------
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 vari-
ous ingredients in a dis- III
persant 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 en-
countered 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 sol-
vents. It lacks solubility or
raiseibility 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 neces-
sary raise ibility with oils.
Glycols and alcohols are used
to aid in raiseibility as well
as freezing point depression
when water is used.
C Additives - Stabilizers
Third major component in dis-
persants, 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.
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
considerably in toxicity, effec-
tiveness and ability to stabilize
the oil after extended periods of
time. Technology for proper appli-
cation of dispersants over large
oil slicks with necessary mixing
is currently 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 con-
clusion that dispersants or the
dispersant-oil mixture caused more
13-3
-------
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 deep-
ly into the sand, and by dis-
turbing the sand's compactness,
so as to increase beach erosion
through tidal and wave action.
B Toxic ity
Current information indicates
that dispersants vary consider-
ably in toxic ity. The combina-
tion of oil and dispersant may
increase the toxic ity 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 toxic ity 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
A common method of dispersant
application is by the water
eductor method. A controlled
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 diffi-
cult for the surfactant to trans-
fer from its thermodynamically
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 appli-
cation 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.
Eductor
Water Stream
, . 1 .. ^
Water
Water
Base
Dispersant
J \ ^ r^.
\ %<>-
H >
""--Oil
Water Compatable
4 Surfactant
- ~M i _ .J ^
Eductor
Oil Compilable Surfactant
'Tied-Up1 In Solvcnt-
In-Water Emulsion
Figure 1-
-------
TABLE I(3)
Static Bioassays - TL$Q 48 Hours @ 15°C (ppm)
Solvent emulsifiers
Gamlen OSR
Polyc lens
Six
BP 1002
Cleanosol
Essolvene
Gamlen D
Gamlen CW
Atlas 1901
Slickgone 1
SI ic kg one 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
?r 1000
330-1000
3300-10000
. 330-1000
100-330
Cardium Agonus
edule cataphractus
Armed
Cockle 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 flesus(F) Fish Crab
20.4
23.2
> 300 (15)
10-33 (L) 10-25
102
15-20
> 150
35.0
21.3
Ostrea*
edulis
Oysters
15- 50
^ 100
50-100
50-100
*Tests lasted 5 days, not 48 hours.
CO
i
-------
10
1
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 8666
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
-------
D Cost-Effectiveness
1 Cost
The cost of dispersants ranges
from $2.00 - $5.00 per gallon.
Using manufacturers' recommend-
ed doses, which are usually 1
gallon of dispersant to 10
gallons of oil, the cost of
chemicals for dispersing a rel-
atively small 500 barrel spill
would be about $10,000.
Based on EPA's actual field ex-
perience, 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 toxici-
ty, is the effectiveness of a
dispersant.
Evaluation of the effectiveness
of dispersants 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 evalua-
tion impossible. Their effec-
tiveness 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 disper-
sants and subsequent agitation,
which are critical fbr 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 deter-
mine its applicability using -a
variety of oils and dispersants.
Figure 2, which shows the results
of testing done at the Edison Water
Quality Lab adequately demonstrates
the degree of variability which
will occur 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 follow-
ing pages.
13-7
-------
10
nooueto.
B? FUEl OH IOUIH LOUISIANA IAOO
CRUDE CBUDE
BACMAOUERO
CRUDE
SANTA BARBARA BUNKER C
CRUDE
TABLE 2.
APPARENT COMPOSITION OF TEST CHEMICALS
Surfactant Surfactant
Product Ionic Nature1 Basic Composition2 Solvent3
Nonionic
Fig. 2: Oil Dispersant Effectiveness
13-8
o
E
Nonionic
Nonionic
Nonionic
Anionic
Ethylene oxide
condensate of
alkyphenol
Ethylene oxide
condensate of
alkylphenol
Polyhydric
alcohol ester
of fatty acid
Alkanolamide
Alkyl aryl
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.19
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.
-------
ANNEX
2000 SCHEDULE OF DISPER5ANTS 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 con-
tiguous zone as defined in Article 2k 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 mechan-
ical and 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, regu-
lations or written policies shall govern. This schedule will apply in
those States that have not adopted such laws, regulations or written
polic ies.
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 dis-
persal of the oil into the water column.
2003 Collecting Agents Collecting agents are considered to be gener-
ally acceptable providing that these materials do not in themselves or in
combination with the oil increase the pollution hazard.
13-9
-------
2004 Sinking Agents Sinking agents may be used only in marine waters
exceeding 100 meters in depth where currents are not predominantly on-
shore, 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 sub-
stantial hazard to a major segment of the population(s)
of vulnerable species of waterfowl; and
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
13-10
-------
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 veloc-
ity 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 procedures 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 TL5Q of the most sensitive species tested as calculated in
the top foot of the water column. The maximum volume of chemical per-
mitted, in gallons per acre per 24 hours, shall be calculated by multi-
plying the 96 hour TLso 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;
2007.3 - 2 name and address of the manufacturer, im-
porter or vendor;
2007.3 - 3 flash point;
2007.3 - 4 freezing or pour point;
2007.3 - 5 viscosity;
13-11
-------
2007.3 - 6 recommend application procedure (s), concen-
tration(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 hazard-
ous trace materials; including, but not necessarily
being limited to lead, chromium, zinc, arsenic, mer-
cury, 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.
13-12
-------
REFERENCES
Poliakoff, Melvin, A., "Oil
Dispersing Chemicals", 1969,
Edison Water Quality Laboratory,
FWPCA, Edison, New Jersey 08817.
Canevari, G. P., "General Dis-
persant Theory", Proceedings,
Joint Conference on Prevention
& Control of Oil Spills, API-
FWPCA, 1969.
Portmann, J. E., "The Toxicity
of 120 Substances to Marine
Organisms", Fisheries Laboratory,
Burnham on Crouch, Essex, United
Kingdom, September 1970.
Murphy, T., McCarthy, L., "Evalu-
ation of the Effectiveness of Oil
Spill Dispersants", Proceedings,
Joint Conference on Prevention
& Control of Oil Spills, API-
FWPCA, 1969.
Federal Register, Volume 35, Num-
ber 106, June 2, 1970.
Outline prepared by Richard T. Dewling,
Director, R&D, Edison Water Quality
Laboratory, December 1970.
13-13
-------
PROPOSED EPA TESTS ON OIL DISPERSANT
TOXICITY AND EFFECTIVENESS
I INTRODUCTION
Damage to the environment from oil
spill clean-up operations by the
indiscriminant use of chemical dis-
persant s has led to the establishment
of very restrictive policies regarding
the use of these materials. These
restrictions are set forth in the June
1970 National Oil and Hazardous Materi-
als Pollution Contingency Plan which
was developed pursuant to the provisions
of the Water Quality Improvement Act of
1970. Among other constraints, it is II
the policy of this plan that oil dis-
persing chemicals, prior to their use,
be tested for relative toxicity and
effectiveness in accordance with
standardized procedures to be estab-
lished by the Federal Water Quality
Administration. "Data on the relative
toxic ity and effectiveness of these
dispersing chemicals will provide the
basis for the selection of those chem-
icals most effective and least toxic to
aquatic life and for recommending or
prohibiting their use.
In the fall of 1969, the Federal Water
Quality Administration's National
Marine Water Quality Laboratory at
West Kingston, Rhode Island, provided
preliminary methods for determining the
relative toxicity of dispersants, while'
FWQA's Edison Water Quality Laboratory
at Edison, New Jersey completed work on
tentative procedures for evaluating
dispersant effectiveness. Shortly
thereafter, a joint government/indus-
trial task force panel reviewed the
proposed tests developed by these labor-
atories and recommended that an
independent evaluation of the tests
be conducted prior to official
promulgation. Accordingly, ah inten-
sive program, sponsored by FWQA, is
currently underway by four commercial
laboratories to evaluate the reproduc_
bility of the proposed tests and to
recommend modifications, improvements
and refinements in the testing pro-
cedures. This program is scheduled to
be completed by June 1971.
PROPOSED FWQA DISPERSANT TOXICITY TESio1
A General Description
These tests involve numerous bio-
. assays on four aquatic organisms
using the dispersant under investi
gation and mixtures of the dis-
persant with various oils. The
test procedures require determina-
tions of 96 hour (for fish) and 48
hour (for organisms other than fish)
50% survival values O^Q) for bot
the raw dispersing chemical and
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 Edi-
tion, but they are modified to mee\.
-------
the special problems arising in the
use of fish and of test organisms
other than fish in the bioassay of
dispersants and mixtures of dis-
persants with different petroleum
products. These modifications in-
clude 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, dilu-
tion water, aeration, dissolved
oxygen concentrations, temperatures,
pH and salinity.
The complete testing procedures are
described in reference (4).
C Test Organisms
The four species designated for these
tests are:
I 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 most any
portion of the country. The three
test animals used in the marine
water determinations represent a
wide range of animal classes includ-
ing: a free swimming fish; a mollusc
(oyster) which is a bottom dwelling
organism and is stationary at least
part of its life; and ah anthropod
(shrimp) which represents the largest
class of animal species. The animals
selected for these tests also provide
a wide range of indicators for rela-
tive 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 avail-
ability 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.
114-2
-------
Bachaquero
South Louisiana
API0
Viscosity, Universal 100°F
Pour Point, °F
% Weight Sulfur
% Weight Asphaltenes
Neutralization Number
% Volume Distilled at:
300°F
400°F
700 °F
17
1500
-5
2.2
7.0
2.7
6
17
35
36.6
41
15
0.20
0.3
0.4
18
43
71
III
E Discussion
The prime purpose of the FWQA
Dispersant Toxic ity 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
toxic ity of these chemicals to
aquatic organisms, safe levels for
the aquatic biota or for humans,
nor do they constitute an endorse-
ment of any material by the FWQA.
PROPOSED FWQA DISPERSANT EFFECTIVENESS
TESTS
A General Description
These tests essentially incorporate
the basic apparatus of the Navy
Tank Test of Specification MIL-S-
22864, Solvent-Emu Is ifier, Oil Slick
with substantial procedural and
equipment modifications to more close-
ly simulate environmental conditions.
The tests utilize a 24-inch diameter
x 28-inch high cylindrical tank con-
taining 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 subsurface 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 vary-
ing 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 pressur-
ized stream of synthetic sea water under
standard conditions 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
14-3
-------
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 spectro-
photometrically determined. Results
of tests are expressed as percent
of the original 100 ml of oil dis-
persed that is, recovered from
the underlying water.
In these tests, varying quantities
of the dispersant under investiga-
tion 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 be-
tween addition of dispersing chemi-
cal and agitation (contact time)
may have a profound influence on
dispersant effectiveness, i.e. long-
er contact time improves the effec-
tiveness 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 dispers-
ion values of the chemical at
widely differing contact times
(zero and 10 minutes) and by
performing all subsequent tests
at that contact time giving
greater dispersion.
Since eduction is frequently, sug-
gested by manufacturers as a
method for applying dispersants,
these tests include determinations
of dispersant effectiveness when
educted into the agitation hose
stream as compared to effective-
ness when applied undiluted to the
oil followed by agitation.
More details of the Proposed FWQA
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 FWQA Dispersant Toxicity Tests.
C Discussion
The FWQA Dispersant Effectiveness
Tests, which measure both initial
dispersion and stability of dis-
persion and simulate typical envir-
onmental conditions, have been
found by the Edison Water Quality
Laboratory to produce results which
correspond favorably with field
performance. The tests show prom-
ise 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 Federal Water Quality Administra-
tion for determining the relative
toxicity and effectiveness of oil dis-
persing chemicals. The dispersant
toxic ity tests include bioassay
determinations on four aquatic organ-
isms using the dispersant under inves-
tigation 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 pro-
posed tests by the four commercial
laboratories, meaningful standard pro-
cedures 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
Toxicity of Oil Dispersants and
Mixtures of Dispersants and Various
Oils to Aquatic Organisms", Pro-
ceedings - Joint (API/FWPCA) Confer-
ence on Prevention and Control of
Oil Spills, December 1969.
Murphy, T. A., McCarthy, L. T., "Evalu-
ation of the Effectiveness of Oil-
Dispersing Chemicals", Proceedings -
Joint (API/FWPCA) Conference on
Prevention and Control of Oil Spills,
December 1969.
MIL-S-22864 A (Ships), Military
Spec ificat ion, So1vent-Emu Is ifier,
Oil-Slick, February 24, 1969.
1 National Oil and Hazardous Materi-
als Pollution Contingency Plan,
June 1970.
2 Public Law 91-224, 91st Congress,
H.R. 4148, "Water Quality Improve-
ment Act", April 3, 1970.
3 "Standard Methods for the Examina-
tion of Water and Wastewaters", 12th
Edition, American Public Health
Association, New York, 1969.
4 Tarzwell, C. M., "Standard Methods
for Determination of Relative
Outline prepared by Ira Wilder, Chemical
Engineer, R&D, Edison Water Quality
Laboratory, December 1970.
14-5
-------
PHYSICAL METHODS OR TREATMENT
Sinking and Burning Agents
Sorbents
Booms
Skimmers
Beach Cleanup Methods
-------
SINKING AGENTS
I DEFINITION - USE POLICY
Sinking agents are oil-attracting and wa-
ter repelling sorbent materials designed
to sink oil slicks out of sight rather than
agglomerating oil on the water surface.
The use of oil sinkants would seem advan-
tageous in deeper waters outside heavy
fishing zones, such as off the continental
shelf and where adverse effects upon bio-
logical bottom life may be held at a mini-
mum. (**) Existing EPA policy on sinking
agents restricts their use to waters ex-
ceeding 100 meters in depth.
Oily discharges into inland rivers and
coastal waters do not remain floating for-
ever since much of the oil will be naturally
absorbed onto clay, silt and other particu-
late matter normally suspended in the wa-
ter , 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
commercial products are presently avail-
able which are claimed to be effective in
sinking oil slicks.( ' ) Typical agents in-
clude 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 be-
tween 2.4 and 3.0. These agents
must be evenly distributed over the
surface of a slick and supplied with
proper mixing, agitation and time
interaction. The particle-coated
and agglomerated mass eventually be-
comes 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. Ex-
periments in both the laboratory and
field show that many agents will re-
lease entrapped and sunken oils back
to the water environment. Increas-
ing the application rate two or three
times over prescribed amounts has
served to minimize this release.
Studies conducted by various investi-
gators (4,5,6,7,9,10,12) indicated
that:
1 Sulfurized oils may show greater
sinking abilities than desulf urized
oils because of higher potentials
for hydrogen bonding.
2 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. How-
ever , when the sands are loosely
15-1
-------
packed, the mass will become inter-
nally mobile so that oil drops will
separate and escape to the water un-
til equilibrium is re-established.
3 With carbonized sand, it was indica-
ted that up to three pounds of sand
would be required to sink one pound
of oil. Large-scale applications of
amine-coated sands envision spray-
ing the sand in a slurry form from a
large vessel or hopper dredge.
In ports and harbors it has been men-
tioned 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 fer-
tilizer may be added to promote bacterial
growths and accelerated decomposition of
the sunken mass.' ' > Table I summari-
zes the types, application rates and rela-
tive costs of various sinking agents.
IV FIELD EXPERIENCE
The most prominent large-scale applica-
tion of sinking agents was that underta-
ken by the French to sink large masses of
TORREY CANYON oils in the Bay of Bis-
cay. Some 3,000 tons of calcium carbon-
ate (blackboard 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 fa-
thoms of water. The area of sinking was
known to partially cover scamp fish-
ing grounds and thus there was fear
of bottom inundation and oil resur-
facing. 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 shore-
lines. 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 re-
commended in other situations.' ''
14,15,16,17)
Opinion still remains divided on the
use of oil sinkants as to their effi-
ciency, cost, application, and pos-
sible adverse effects. With sinking
agents, the same problems are en-
countered in the application and dis-
tribution as was indicated in the lec-
ture on floating sorbents. However,
with sinking agents, operational lo-
gistics become increasingly more dif-
ficult 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 pollu-
tion , to prevent its spread over the
water surface, and theoretically sub-
merge and anchor the oil near the
source of pollution. Considering that
the bottom of harbors and bays near
many industrial ports are grossly pol-
luted and nonproductive , emergency
sinking of oils in these areas may not
increase damage to fisheries. Dilu-
tion by flowing waters in certain areas
may also be sufficient to adequately
15-2
-------
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; S27/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 for desulfurized 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 S120/ton sinking agent.
ABibliography (2,3,4,9, 10, 12, 13, 14)
15-3
-------
minimize toxicity to nearby shellfish
grounds. The other important point of
view is that sinking agents, even i£ used
in harbor areas because of fire or explo-
sion 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. (^,8 ,12)
V R & D PROGRESS
Dutch Shell Laboratories, Holland,
was one of the first groups to really eval-
uate sinking agents on a field scale basis.
Their studies, still underway, involve us-
ing 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 percentage of oil sunk. The lower
the clay content the more efficient the
sinking agent. The Warren Spring Labora-
tory, United Kingdom, ^ impressed by the
results of these studies, conducted simi-
lar field investigations during 1969. Con-
clusions reached by the Warren Spring
Laboratory were as follows:
1 The sinking was not as effective as
first hoped and it would appear that
the thickness of the oil film is an
important factor. Nevertheless, be-
tween 50 and 70 per cent of the oil
put on the sea was sunk.
2 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 ti-
dal current along the sea bed was suf-
ficient to carry the oil over the rip-
ples of sand on the bottom.
3 Trawling was carried out and al-
though no actual lumps of oil were
collected, sufficient oil was
rubbed onto the netting of the
trawl to foul both the catch and
the fishermen when they were pul-
ling it back into the vessel.
4 The oil which remained afloat was
particularly difficult to dispose
of using either more sand slurry
or the normal solvent emulsif ier
mixture agitated by water hoses.
Further investigations on this par-
ticular phenomenon are being
carried out both in England and in
Holland.
In the United States, the Army Corps
of Engineers, under contract to the
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
1970.
REFERENCES
1 Internal files and laboratory data
of the Oil and Hazardous Material
Section, R&D, EPA, Edison Water
Quality Laboratory, Edison, N. J.
(Unpublished materials)
2 "Study of Equipment and Methods
for Removing Oil From Harbor Wa-
ters," Battelle Memorial Insti-
tute , Pacific Northwest Labora-
tories, Report No. CR-70-001,
prepared under Contract N62399-
69-C-0028 for the Department of
the Navy.
15-4
-------
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 Pre-
vention and Control of Oil Spills, API
and FWPCA
6 Smith, J. W. , United Kingdom Minis-
try of Technology, "Work on Oil Pol-
lution" , Proceedings, Joint Conference
on Prevention and Control of Oil
Spills, API and FWPCA, 1969
7 "TORREY CANYON Pollution and Ma-
rine 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, N. J. , 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,
D. C.
11 Meijs, L. J. et al, "New Methods
for Combatting Oil Slicks , Pro-
ceedings , Joint Conference on Pre-
vention and Control of Oil Spills,
API and FWPCA, 1969
12 Chipman, W. A. and Galtsoff, P.S. ,
"Effects of Oil Mixed with Carbon-
ized Sand on Aquatic Animals,"
Special Scientific Report: Fisher-
ies No. 1, U. S. Department of the
Interior , Fish and Wildlife Service ,
Washington, D. C. , August 1949
13 "The TORREY CANYON," Presen-
ted to Parliament by the Secretary
of State for the Home Department
by Command of Her Majesty, April
1967, Her Majesty's Stationery Of-
fice, London, England
14 "The TORREY CANYON" , Cabinet
Office , Report of the Committee
of Scientists on the Scientific and
Technicological Aspects of the
Torrey Canyon Disaster, Her Ma-
jesty's Stationery Of f ice, London,
England, 1967
15 "French Explode an Oil Slick Myth,"
article appearing in the MANCHES-
TER GUARDIAN, Manchester, Eng-
land, July 25, 1968
16 Bone, Q. and Holme, N. , "Lessons
from the TORREY CANYON," New
SCIENTIST, p. 492-493, September
5, 1968
17 Bone, Q. and Holme, N. , "Oil Pol-
lution -- Another Point of View,"
NEW SCIENTIST, 37, p. 365., Feb-
ruary 15, 1968
15-5
-------
BURNING AGENTS
I INTRODUCTION
Burning of oil on water or land by spe-
cial methods and materials seems to of-
fer an attractive and perhaps inexpensive
means of eliminating large amounts, pro-
viding of course, the many significant
hazards are also recognized. Freshly-
spilled oils and crudes containing volatile
components are relatively ignitible. If a
thick layer of oil on water is present,
the oil will sustain burning until the vola-
tiles and a portion of the heavier frac-
tions are combusted. Conversely, with
fresh oil spills within a harbor or con-
fined area, a significant fire danger ex-
ists when the level of hydrocarbon vapors
is within the range of flammability, (e. g.
gasoline, aviation fuels, or light crude
oils) (2 , 8, 19 - see references in "Sink-
ing A gents" lecture).
Wood, debris or other material caught
within 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 be-
neath will greatly deter burning. How-
ever, the wick will withdraw 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 mil-
limeters (0.12 inches) will not burn.
It is also reported that layers of
kerosene, gas oil, lubricating
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 ma-
terial quickly loses its volatile
components and ignition is ex-
tremely difficult. Weathered
oils are consequently reported
to present almost no fire ha-
zard. (2, 3, 8, 19 - see refer-
ences in "Sinking Agents" lec-
ture)
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 experi-
ments that the light crude, fresh-
ly 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 of the No. 6
15-6
-------
fuel caused sporadic burning and the
minimum required oil thickness to sus-
tain burning was 1/3 to 1/2 inches. It
is important to note that a thickness
of 1/3 to 1/2 inches is equivalent 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 1/10
to 1/4 inches. The manufacturer
producing this material, however, sug-
gests 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. (1,3- see references in
"Sinking Agents" lecture)
C EPA Field Tests
Field scale oil slick burning experi-
ments , with and without special
agents have been undertaken in 1970 by
both the U. S. Navy and the Edison
Water Quality Laboratory. Prelimin-
ary data from these experiments in-
dicate the following:
1 Burning of free floating or un-
contained oil slicks is extremely
difficult unless the thickness of
oil is 2 mm or greater.
2 Adequate automated seeding me-
thods for both the powder and
nodule-type burning agents are
lacking. Spreading of the burn-
ing agent on the oil slick had to
be accomplished by hand. This
conclusion was also reached by
the Navy, which conducted burn-
ing experiments in May 1970.
3 Contained South Louisiana
crude oil was successfully
burned - 80% to 90% reduc-
tion - without the applica-
tion of 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% reduc-
tion - when the slick was
seeded with burning agents
and an appropriate priming
fuel. It was discovered that
South Louisiana crude oil per-
formed 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 destruc-
tion off the British coast in
March of 1967. As a last resort,
the British Government attemp-
ted simultaneous and complete
burning of the 15,000-20,000 tons
15-7
-------
of oil remaining in the badly broken
tanker by aerial bombing, incendi-
aries, and catalyst-oxidizing devi-
ces. 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, napalm bombs, roc-
kets, and sodium chlorate devices
served to produce a massire fire,
if not a sustained fire. The Brit-
ish concluded that no appreciable
amounts of oil escaped burning, but
if any did, it was lost to the open
sea. (13, 14, 18 - see references
in "Sinking Agents" lecture)
E Use Considerations
Controlling the burning oil mass
and ensuing air pollution problems
would appear to preclude intention-
al burning except where the oil mass
is distant from the coastline , off-
shore 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 Envi-
ronment, United Kingdom, has con-
ducted a series of research experi-
ments involving the burning of oil
on beaches. The conclusions reached
by these studies were:
1 The type of heavy oil normally
contaminating beaches and the
foreshore is very difficult to
burn by ordinary means and com-
bustion ceases when the source of
heat is removed.
2 The addition of solid oxidants aids
the combustion of part of the de-
posit, but a sticky, tarry residue
is left with medium heat and a re-
sidue 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 re-
moval would probably be excessive.
3 The application of an oil-absorbent,
combustible material, such as saw-
dust impregnated with an oxidant,
resulted in a much steadier burning
rate and an increased removal of
the deposit. The additive, however,
burns away before the higher-
boiling, tarry fractions begin to
burn.
4 Although some improvement was
obtained by adding materials which
function as a wick, the same limi-
tation regarding the amount of heat
to be supplied still operated.
5 A major disadvantage of burning as
a method for the removal of oil
15-8
-------
deposits on beaches, especially when
dealing with the large semi-solid
lumps , is that, when heat is applied,
the oil becomes mobile and penetra-
tes deeper into the beach, thus in-
creasing the contaminated area if it
becomes exposed at a later date.
6 On the basis of these small-scale ex-
periments 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 in-
vestigation would be unprofitable.
IV COMMERCIAL BURNING AGENTS
Commercial burning agents 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 con-
tained. These agents are intended to
serve one or more functions such as pro-
viding increased surface area exposed to
burning; addition of catalysts, oxidizers
and low-boiling volatile components; ab-
sorbence 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:
1 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 experi-
ments which included burning of oil on
beaches, and in open waters. Results
of this investigation indicated that
the quantity of "agent" required
was dependent upon wind, con-
dition 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 pac-
kaging requirements are met.
Pittsburgh Corning, One Gateway
Center, Pittsburgh, Pa.: Known
as "SeaBeads" , these cellulated
glass nodules are available in sizes
from 1/8" to 1/4" in diameter. By
capillary action, the nodules be-
come 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 "pri-
mer 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.
Guardian Chemical Corporation,
Long Island City, N. Y. 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.
15-9
-------
Cabot Corporation, 125 High Street,
Boston, Mass. : 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 hydro-
phobic. It may be applied directly to
the slick or by spraying in a stream
of water. Combustion is best accom-
plished by using an incendiary device
in conjunction with a "primer fluid".
Reportedly, this product was used
successfully for handling a 2 ,000 gal-
lon spill at Heard Pond, Wayland,
Mass.
This outline was prepared by R. T.
Dewling, Director, Research & Develop-
ment, Edison Water Quality Laboratory,
Edison, N. J. December 1970.
15-10
-------
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 sta-
bilizing petroleum cargoes aboard a stran-
ded or heavily-damaged tanker at sea sub-
ject 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 ami-
neisocyanatates, 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 replace-
ment bunker fuel. This gel agent is ap-
plied to the surface of the water by a high-
pressure spray system to provide suffi-
cient 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 appli-
cation and distribution, lower
materials and operational costs,
and suitable means of picking up
the amorphous oily masses. Bun-
ker 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
since gelled oils cannot be easily
collected by mechanical or manu-
al means- Necessary improve-
ments are needed in the gelling ap-
proach in line with a total opera-
tional systems cleanup. (1, 2, 3,
8 - see lecture on "Sinking Agents"
for these references)
REFERENCES
1 U. S. Patent #3, 198,731,
Method of Treating Oil
on the Surface of Water.
2 Northeast Region, R & D Pro-
grams , Federal Water Pol-
lution Control Administra-
tion. Status Report on Use
of Chemical and Other Ma-
terials to Treat Oil on
Water.
This outline was prepared by R. T.
Dewling, Director, Research & De-
velopment, Edison Water Quality
Laboratory, Edison, N. J. Decem-
ber 1970.
15-11
-------
SORBENTS
I INTRODUCTION
A. Sorbents are oil spill scav-
engers or clean-up 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 classi-
fied as to their physical char-
acteristic s:
1. Powdery products.
2. Granular products.
3. Fibrous materials.
4. Pre-formed foam slabs or
sheets.
II TYPES OF SORBENT PRODUCTS
A. Types of floating sorbent
materials presently available
arei:
1. Natural Origin: Types
derived from vegetative
sources comprise straw,
hay, seaweed, kelp, ground
bark, sawdust, reclaimed
fibers from paper process-
ing, and peat moss. Types
derived from mineral sources
may include the various
clays, including montmoril-
linite, kaolin, fuller's
earth, diatamaceous earth,
etc.; vermicultite and the
other micas; many forms
of silicates; perlite;
pumice; and asbestos. Sor-
bents of animal origin
include chrome shavings
from leather processing,
wool wastes, feathers, and
textile wastes.
2. Modified Natural Products:
These materials comprise
most of the sorbent types
mentioned above but are
chemically-treated to pro-
duce a more desirable
result. Some of the modi-
fied types are expanded
perlite, charcoal, stearate-
coated talc, asbestos treated
with surfactant, and saw-
dust and vermiculite coated
with silicones.
3. 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.
Ill SORBENT CHARACTERISTICS
A. Desirable Sorbent Character-
istics
1. Oleophilic - has greater
attraction for oil than
water.
2. Hydrophobic - repels or
rejects water.
3. Adsorbtive - oil will ad-
here to the surface of the
material.
16-1
-------
IV
4. Absorbtive - oil is assimi-
lated into the material.
5. 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.
6. Retentive - leaking of oil
from material should be min-
imal after harvesting.
7. Low costs - on a non-reusable
product. High initial costs
are acceptable for reusable
products.
8. Products should float under
all conditions.
Presently, non of the existing
products have all of these de-
sirable qualities.
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 quanti-
ties.
4. Non-toxic.
5. May increase both perfor-
mance of booms and skimm-
ing techniques.
6. Minimizes shore pollution
when beached.
B. Disadvantages
1. No effective workable
system at present.
2. High labor costs assocaited
with acquisition, trans-
portation, stockpiling,
deployment, distribution
on and working into an
oil slick, retrieval and
ultimate disposal.
3. Manual retrieval only
practical under calm con-
ditions.
4. Some products interfere
with other forms of phys-
ical removal by clogging
skimming and suction
devices.
5. Pollutional problems on
disposal.
6. Some sorbent products
ultimately sink.
a. As their true density
is greater than water,
certain mineral pro-
ducts sink when air
entrained in capil-
laries is replaced
by oil and/or water
or when products are
wetted by water.
b. Some natural vegeta-
tive products such
as straw, sawdust or
waste pulp fibers
become waterlogged
upon prolonged expo-
sure in water and
may sink.
V SORBENT USES
A. Sorbents may be used for
many reasons
16-2
-------
1 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 inef-
fective and in other areas
where presently available
control procedures would
be effective but are not
readily available.
2 To "polish" a slick remain-
ing after other control pro-
cedures such as booming and
skimming have removed most
of the oil.
3 To sorb free oil from con-
taminated surfaces to facil-
itate cleanup procedures.
To deploy sorbents onto
open waters and clean
beaches in anticipation
of the arrival of an un-
controlled slick.
sorbent mass?
In each of the situations
listed in Section VI, the
effectiveness must be
evaluated differently be-
cause criteria for evalu-
ating effectiveness must
be related to the original
objective for each differ-
ent 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.
VII SORBTION PROCESSES
5 Used in conjunction with
either fixed or towed booms.
VI SORBENT EFFECTIVENESS
A To define sorbent effective-
ness certain basic questions
relating to the environmental
use of sorbents under actual
spill conditions must be con-
sidered.
1 Why were sorbents used?
2 What procedures will be
used to harvest the oil-
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
must 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
16-3
-------
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 mani-
fests primarily absorbtion be-
cause 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 viscos-
ity, the greater the oil to oil
cohesion and adhesion.
VIII USING SORBENTS EFFECTIVELY
A On unconfined oil slicks
1 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.
2 The effectiveness of most prod-
ucts is increased by ultimately
mixing the product into the oil
slick. This can be accom-
plished:
a By churning up the mass by
running boats through at
high speed after broadcasting
of products.
b By towing netting
stretched between boats
through the mass at slow
speed.
c By existing environmental
energy such as wind, wave
and current action.
d If the above is not feas-
ible, 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.
e A harvesting procedure
utilizing netting or
booms which encircles a
given area and concen-
trates 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 labora-
tory 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
16-4
-------
of bench scale testing of the oil
sorbing capacity of selected
products. The data was summarized
from Edison Water Quality Labora-
tory 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 reported-
ly the most costly 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
E. A. Milz(2) 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 re-
moved 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-
hour s.
a One exception to the
above is Kraton rubber
which dissolves oil
into the body of the
material and completely
retains it. To facili-
tate sorbtion, samples
were granulated to a
particle size of 4 mm.
Kraton rubber may also
be foamed which should
improve sorbtion.
k Power mulching machines
can effectively spread up
to nine tons of straw or
hay per hour with immedi-
ate mixing with oil. In
contrast, when hay was
simply dumped overboard,
16-5
-------
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 en-
countered 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, veloci-
ties 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 har-
vesting devices is critical and
is related to the sorbent
particle size.
XI POTENTIAL OF SORBENTS
A Because of the inherent limita-
tions 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 con-
junction with self-contained
mechanized systems will be
developed which will have the
following desirable features:
1 Recovei of oil which de-
creases problem 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 geometri-
cally for each subsequent
re-use. Such products may
be used dozens of times and
potentially hundreds of
times by reinforcement of
product with plastic netting.
3 On open waters under incle-
ment conditions 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.
C Costs will decrease as manual
labor is replaced by mechanical
equipment incorporated into
continuous self-contained
systems.
D Presently the FWQA, U. S. Coast
Guard and the A.P.I, are evalu-
ating proposed sorbent systems
submitted for research funding.
16-6
-------
TABLE I
COSTS OF SORBENTS
(1)
(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
*-1-'
CT>
i
Polyester plastic shavings
Nylon-polypropylene rayon
Resin type
Polyurethane foam*
Polyurethane ^ '
Polyurethane
Polyurethane
Polyurethane
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
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 Spill8
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 SORBENT TESTS(2)
_, Test Conditions: Sorbent applied to oil slick confined to 20' x 20' area
CTi
1
00
Sorbent Material
Kraton 1101
Kraton 1107
Urea Formaldehyde
2" x 24" x 60"
Polyurethane^)
( 2")
Polyurethanev '
Polyurethane^3)
Ekoperl
Hay(i°
Quantity
Used
(Ibs.)
25
25
1.6
20
20
5
24
49
Thickness
(in.)
1A
1/4
1/4
1A
1/4
1A
1/4
1A
Test Oil
Quantity
(Ibs.)
700
700
700
556
660
300
300
700
Viscosity
(cs.)
4
4
4
6
6
6
6
6
Test
Time
(hrs.)
24
24
24
2
1
5
24
24
, no mixing
Oil
Removed
(Ibs.)
28
ca. 30
41
560
100
230
120
210
Oil to
Sorbent
Ratio
1.1
1.2
26
28
5
46
5
4
1. Fine ground polyurethane (ca. 1/4" diameter). For this test there was insufficient oil present to saturate
the polyurethane. There was no trace of oil left after removing the polyurethane.
2. Polyurethane in 9-feet long by 2-feet diameter bag. The bag picked up over 500 pounds of water and only
102 pounds of oil.
3. Scraps of polyurethane of 1 and 2-inch thickness in various shapes and sizes up to 1-foot by 4-feet.
4. Performance of straw and bagasse are similar to hay.
-------
MAT OF SORBENT FORMS
UPSTREAM FROM SCREEN
FIRST FAILURE MODE-
MAT COLLAPSES AGAINST SCREEN
FINAL FAILURE MODE-
SORBENT SWEPT UNDER SCREEN
Fig. 1 - Sorbent Barrier Failure Modes in Current
16-9
-------
References
1 Struzeski, E. J. and Dewling, R. T.,
Chemical Treatment of Oil Spills.
Published in Proceedings Joint Con-
ference (API/FWPCA) on Prevention
and Control of Oil Spills, New York,
December 1969.
2 Milz, E. A., Oil Spill Control Equip-
ment and Techniques. Presented to
the 2lst 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 Insti-
tute, Richland, Washington for U. S.
Navy, Civil Engineering Laboratory,
Port Hueneme, California, August
1969.
4 Combating Pollution Created by Oil
Spills. Prepared by A. D. Little,
Inc. for Department of Transporta-
tion, U. S. Coast Guard, June 1969.
Outline prepared by L. T. McCarthy, Jr.,
Chemist, Oil Pollution Research Section,
Edison Water Quality Laboratory, Edison,
New Jersey, January 1971
16-10
-------
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 (8^ Stat. 92
33 USC Il6l) 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 pro-
gram 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 cleanup 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 over-
come 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 understand 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.
17-1
-------
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.
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 trans-
ported 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 component 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 (l 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
-y - kinematic viscosity of water
10.7x10'^ ft2/sec
-------
Substituting typical values for constants
1 =9.66 [t3j u
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.
The thickness in inches (h) of the spill
may be computed at any time by the
equation:
or
h =
h =
v (0.13)
1* (12)
(0.011)
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 (T 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
« - current in ft/sec
The situation description for the
following is the same as for bulk
discharge.
Situation 1
i - kg v(3.i:
Substituting typical values for constants
/.
1 = 1.61 TV i
Situation 2
Substituting typical values for constants -
T = 3.6
Situation 3
Substituting typical values for constants
T = O.U9 x!
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):
Where
FQ - force causing the oil to spread
in dyne/cm
0^^- surface tension of the water,
(typical order of magnitude
1 dyne/cm)
o<,0 - surface tension of the oil (typical
order of magnitude 30 dyne/cm)
17-3
-------
10'
10=
to
UJ
LJ
0 I04
HR
DAY WEEK MONTH
ll I I I
10s
I04 10°
t (SEC)
I0e I07
Figure I - THE SIZE JL 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, ac
Figure 2 - FORCES ACTING ON AN OIL DROPLET
ON WATER.
-------
o(j>rt - interfacial tension in dyne/cm
Q0 - contact angle of oil with water
at water surface in degrees
Oovl/ - contact angle of oil/water
interface with water surface in
degrees
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.
characteristic to be considered
a globule or droplet of oil will
Another
is that
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 dis-
placement by ocean currents. Large
globules cf 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
containment 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 predicting 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 formulat-
ing 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 frequent 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 inter-
fered with and a pool of oil, generally
much deeper than that which would result
from an undisturbed slick, is formed.
17-5
-------
The boom's performance is affected by wind,
waves, and currents. It must be capable
of conforming to the wave profile so as
to maintain its freeboard and have
sufficient structural strength to with-
stand 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
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 containment 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 containment,
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 by Figure 3- Initial failure
will occur when oil droplets break away
from the lee side of the head wave.
After a critical velocity (uc) 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 Region I, II, or III, they will be
swept under the barrier.
Region I is the critical area for
defining the limits for oil breakaway.
The type of configuration 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:
u<.
2*1
/,,
Where
h - oil film thickness in feet
u - water current in ft/sec
g, - acceleration due to gravity
32 ft/sec2
17-6
-------
x=o
REGION I
OIL-
FtOW
&ROPUT BREAKAWAY
O
C
IE
m
OJ
BEHAVIOR OF AN OIL SLICK CONTA.NED BEH,ND A BOOM
-------
1
fo
specific gravity of oil
#2 oil - 1-
0.3 #6 - 1
.99
.
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.U h.
To determine the current (uc) at which
droplet formation will start, it is
necessary to predict droplet size. The
maximum size possible will be the control.
_.... = If
Where
dmRX - max. drop size in feet
& - oil-water interfacial tension,
30 dynes/cm
gc - 32.2 ft/sec2
g, - acceleration due to gravity
32 ft/sec2
AP - water density minus oil density
in Ibs/ft3
The maximum d which can be achieved with
any type of oil is 0.75 inches.
Then
'/*
Where
u = critical velocity of which oil
droplets will be torn off
J>w = density of water, 62.h Ibs/ft^
For critical conditions (max. droplet size)
uc will equal 0.62 ft/sec. Below this
velocity no 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 reattachraent. In Region III
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(V&)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 -H
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 h 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
17-8
-------
100
LU
X
o
UJ
o:
CO
en
UJ
o
0.01.
WATER CURRENT, FT/SEC
OIL FILM THICKNESS IN REGION I
17-9
FIGURE 4
-------
TABLE 2 - Calculated Terminal Velocities
Interfacial Tension = 10 Dynes/Cm
17_10
Diam.
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
Diam.
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
Drop
Diam.
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
Drop
Diam.
In.
0 .0010
0.0020
0.0040
0.0065
0 .0 100
0.0200
0 .0403
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.
b.
8
003566
007133
014266
023183
035668
071317
141914
22381 5
307306
369552
000000
000000
000000
0.
o.
0.
o.
0.
o.
0.
0.
o.
o.
o.
o.
o.
85
00291 6
005832
01 1 664
018955
0291 62
05831 7
1 1 6273
185383
263190
339260
000000
000000
000000
.9 .95
0.002195 0.001351
0.004391 0.002703
0.008782 0.005406
0-014271 0.008785
0.021956 0.01 351 6
0.043911 0.027032
0.087688 0.054041
0. 141099 0.087549
0.207284 0. 132567
0.295863 0.221 51 1
0.000000 0.252218
0.000000 0.000000
0.000000 0-000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000945
.00 1890
.003781
.0061 44
.009452
.018906
.037806
.061357
.093750
. 1 70109
.2181 10
.000000
.000000
0.
0.
0.
0.
0.
0.
o.
o.
0.
0.
0.
o.
o.
98
00071 1
001423
002846
004626
0071 1 7
01 4234
028467
046231
070878
1 34129
1 90420
195046
000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.99
.000438
.000876
.001 752
.002847
.00.4381
.008762
.01 7525
.023473
.043759
.085882
. 1 42903
. 1 61 475
. 1 59074
Interfacial Tension = 20 Dynes/Cm
Oil Specific Gravity
>
0.
0 .
0.
0.
0.
0.
0 .
0.
0.
0.
0.
0.
0.
c .
8
003327
006655
01 3310
021 630
033278
066551
132791
212642
306552
41 1404
000000
000000
000000
.
o.
o.
o.
o.
o.
0.
o.
o.
o.
o.
o.
o.
o.
85
002720
005441
010883
01 7685
027209
05441 6
103678
1 74993
257795
371929
000000
000000
000000
.9 .95
0.002048 0.001261
0 .004096 0-002522
0.008193 0.005044
0.01331 5 0.008196
0.020485 0.012610
0.040971 0.025221
0.081887 0.050435
0. 1 32451 0.081841
0. 1 99049 0 . 124954
0.316105 0 .224870
0.342575 0.283933
0.000000 0-000000
0.000000 0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000882
.001 764
.003527
.005732
.008819
.01 7639
.035277
.057293
.087860
. 1 66831
.239408
.246480
.000000
0.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
98
000664
001 323
002656
00431 6
006640
01 3280
026561
0431 51
066280
12891 3
203749
221 535
000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.99
.000409
.00081 7
.00 1 635
.002657
.004087
.0081 75
.01 6351
.026569
.040856
.080979
. 1 45302
. 1 77630
. 132599
Interfacial Tension = 30 Dvnes/Cm
Oil Specific Gravity
0.
0.
0.
3
003194
006389
012778
0.020765
0.
0.
0.
0.
0.
0.
0.
0.
0.
d.
031 948
063894
127600
205385
302108
433290
000000
000000
000000
.
o.
o.
o.
o.
o.
o.
o.
o.
0.
0.
0 .
0.
0.
85
00261 1
005223
010447
01 6978
026121
052242
104392
1 68641
251981
387498
4091 67
000000
000000
.9 .95
0.00 19660 .00 1210
0.003933 0.002421
0.007866 0 .004842
0-012782 0.007368
0.019666 0.012106
0.039334 0.024213
0.078636 0 .048422
0. 127405 0.07861 7
0.193011 0.120353
0.323712 0.223538
0 .3701 1 1 0.30 1460
0.000000 0.301918
0.000000 0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000846
.001 693
.003386
.005503
.008466
.01 6934
.033863
.05501 6
.084467
. 1 631 56
.249643
.265958
-000000
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
98
000637
001275
002549
0041 43
006374
0 1 2749
025500
041 431
063675
125044
208851
236749
233599
0
0
0
0
0
0
0
0
0
0
0
0
0
.99
.000392
.000735
.00 1 569
.002550
.003924
.007843
.0 1 5697
.025503
.039231
.078010
. 1 44561
. 185595
. 1 96671
Interfacial Tension - 40 Dvnes/Cm
Oil Specific Gravity
0.
0.
0.
0.
0 .
0.
0.
0.
0.
0.
Q
6.
0.
3
003104
006209
012419
020181
031049
062098
124065
200198
297655
446685
463371
000000
000000
.
0.
o.
o.
0.
o.
o.
0.
0.
0.
o.
o.
o.
o.
3j
002538
035076
010153
01 6530
025386
050773
101 433
1 64199
247139
396183
432937
030303
000000
.9 .95
0.00191 1 0.001 1 76
0.003322 0.002353
0.007644 0.004706
0.0124?3 0.007647
0.019113 0.011765
0.038227 0.023532
0.076434 0.047062
0. 123937 0 .076427
0 . 188509 0 1 1 71 60
0.326847 0.221 364
0.339363 0.312749
0.000000 0.319623
0.000000 0.000000
0
0
0
0
0
0
0
0
0
0
0
0
0
.97
.000323
.001 645
.033291
.005348
.003223
-0 1 6457
.03291 6
.053475
.0821 47
. 1 60068
.255406
.279503
.030000
0-
0.
o.
o.
o.
o.
o.
0.
o.
o.
o.
o.
o.
93
303619
001239
032473
334027
0061 95
0 1 239 1
024733
040263
061935
122147
21 1015
246891
247533
0
3
3
0
3
0
0
0
0
0
,3
0
0
.99
-033331
.003763
.031 525
.03247-)
.00331 3
.037627
.0 1 5256
.324790
0331 32
075942
. 1 43226
.190127
.206333
-------
u> o -g a>~o
3.0
DASHED LINE SHOWS THE
CURRENT ABOVE WHICH
FAILURE WILL OCCUR BY
OIL BRAINING PAST THE SKIRT
BOOM(S) SKIRT DEPTH
0.01 O.I
VOLUME OF OIL PER UNIT
FAILURE DIAGRAM FOR OIL WITH SP.
10
BRE
GR.
ADTH, BBL/
= 0.8, a = 40
FT
DYNES/CM.
-------
-o
I
DASHED LINE SHOWS THE
CURRENT ABOVE WHICH
FAILURE WILL OCCUR BY
OIL DRAINING PAST THE SKIRT
BOOM(S) SKIRT DEPTH "
O.OI O.I 1.0
VOLUME OF OIL PER UNIT BREADTH, BBL/FT
FAILURE DIAGRAM FOR OIL WITH SR GR. =0.99, a =40 DYNES/CM.
-------
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.
As an 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 psoitioned ko 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 verticle 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
(vmax) created is related to the volume
flow rate of air per unit length of
pipe.
Where
vmax ~ maximum generated surface
current ft/sec
k - a constant
g - acceleration due to gravity
32 ft/sec2
Q - 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 to -^~ where x = the horizontal
distance from the manifold. The
effective depth of the surface current
(b) is-^- at x = 1 and increases linearly
for a larger x.
Water currents will cause a distortion
in the plume (see Figure ll). This
17-13
-------
17-]
456789 1.0 2 3 456789 10
WATER CURRENT FT/SEC
MINIMUM SKIRT DEPTH TO PREVENT DRAINING
FIGURE 7
-------
4tiltiliHrtlllttt?-i1llM- M $ M i: 'llliMta-'li.'iHIHtltHlllitHitWiilillaM t f tt
DASHED LINE SHOWS THE
CONDITIONS CORRESPONDING
TO 5 BBL/FT OF WIDTH
.10
1000
4 567891
4567891 2 34567891 2 3
DISTANCE, FT.
Oil film thickness versus distance for various water current speeds for oil with sp. gr. = 0.90, n = 81 cp.
2 3 4567891
-------
CD
50
100
ISO
200 250
DISTANCE , FT
300
35O
4OO
450
50
CD
C
;0
m
. Cumulative oil film volume per unit width at various distances and water velocities for oil with sp. gr. = 0.90, /n = 81 cp.
-------
-CIRCULATION PATTERN AND VELOCITY PROFILES IN
AIR BARRIER
-------
MOUND
STAGNATION LINE
-z^_BUBBLE
PLUME
CIRCULATION PATTERN UPSTREAM OF
AN AIR BARRIER IN A CURRENT
17-18
FIGURE II
-------
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 understanding
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 environmental 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 transport-
ability. Cleanup equipment, in general,
should be designed for easy transporta-
tion 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.
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
17-19
-------
17-20
CURTAIN BOOM
Float. Foamed
Plastic or Air
Flexible Curtain.
Canvas or Plastic
Curtain Ballast Weights.
Cable 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
Freeboard 24
Buoyancy Float.
/*"^v S" ^S£ Plastic, Drums or
/ ^ ( \ Inflated Chamber.
Tension Cables
Panel may be rigid
or flexible. Wood, plastic,
fabric or metal.
TYPICAL BOOM DESIGNS
FIGURE 12
-------
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
Unknown
Unknown
Unknown
Unknown
$2.45
$2.20
Unknown
Address Unknown
France
Versatech Corporation
Nesconset, Long Island
New York
Roberts Plastics Ltd.
England
Bristol Aircraft Company
England
British Petroleum Company
Finsburg Circus
London, E. C. 2, England
California Oil Company
Perth Amboy, New Jersey 07501
Helly J. Hansen A/S
Moss, Norway
English China Clay Company
England
ru
-------
ro
r\j
Boom
Stage of Development
Cost $/Ft.
Manufacturer
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 Product ion
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
Garnien 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
-------
Boom
Stage of Development
Cost $/Ft.
Manufacturer
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
In Production
In Production
In Production
Patent Pending
Patent Pending
In Production
Patent Pending
$5.95 -$6.95
$9.75
Submitted Upon
Request
Submitted Upon
Request
$40 - $50
$2.60
$20.00 light duty
$58.60 heavy duty
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
ru
-------
rv
Boom
24. Sea Curtain
25. Sea Fence
26. Sealdboom
27. Sea Skirt
28. 6-12 Boom
29. Slickbar Oil Boom
30. SOS Booms
Stage of Development
In Production
Experimental
In Production
Developmental
In Production
Cost $/Ft.
Manufacturer
In Production
In Production
$ 2 -$ 4 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
463 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
-------
Boom
Stage of Development
Cost $/Ft.
Manufacturer
31. Transatlantic Plastics Boom
32. T-T Boom
33. Warne Booms
34. Water Pollution Controls
Boom
Unknown
In Production
In Production
Patent Pending
Unknown
$6.77-$8.08
$15.00-$36.00
Unknown
Transatlantic Plastics Ltd.
England
East Coast Service, Inc.
343 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
I
ro
VJ1
-------
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 information, 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 £-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 k- and 6-inch
float diameters with curtain (fin)
depths available from 6 to 2k inches.
Standard sections are available in k-
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 2k inches,
range from $6.UO 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 2U-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 presently being 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 U-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 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 arrange-
ment) . 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
17-26
-------
water and one-third above. The boom is
manufactured in standard lengths of 50
meters (l6k 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
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 U 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,
was $9.50 per foot. A pair of aluminum
paravanes are $72U 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 poly-
ethylene 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
characteristics, 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
17-2?
-------
AVERAGE WATER LINE STAINLESS-STEEL STRAP STAINLESS-STEEL END PLATES (3)
13 per Float
FOAMED-PLASTIC FLOAT
9 feet long
STAINLESS-STEEL
NUTS and BOLTS
BRONZE SHACKLI
STAINLESS-STEEL V* " CABLE
STAINLESS-STEEL TANG
STAINLESS-STEEL CLIP
ORANGE PLASTIC FIN
STAINLESS-STEEL RIVET HARDENED-LEAD BALLAST, Riveted
Quantity as Required
Fig. 13 SLICKBAR Boom
17-28
-------
ALUMINUM BAR
STIFFENER
FOAM-PLASTIC FLOAT
TERYLENE LINE
PLASTIC SKIRT
LEAD BALLAST
T-T BOOM
SSBCS*-^*
Figure 14.
T-T BOOM
17-29
-------
OPEN OCEAN SEMI.PROTECTED
WATER
SHELTERED
WATER
17-30
Figure 1 5
HEADRICK BOOM
-------
SUMMARY TABLE 2
MULTIPURPOSE BOOMS
Boom
Stage of Development
Cost $/Ft.
Manufacturer
1. ICI Oil Absorbing Boom
Roscoff Heavy and Light-
weight Booms
3. Sea Serpent
4. Skimmer Boom
In Production
Used at Torrey Canyon Spill
Under Development
Patent Pending
$6.75 - 7.45
Unknown
Unknown
Unknown
ICI Fibres Ltd.
Harrogate
Yorkshire, England
Marine Biological
Laboratory
Roscoff
North Brittany, France
Johns-Manville Co.
22 East 40th Street
New York, New York 10016
E. P. Hall
FWPCA
Washington, D.C. 20242
-------
SUMMARY TABLE 3
IMPROVISED BOOMS
Type of Boom
Location Where it was Used
1. Cork-Filled Boom
Norfolk, Virginia
2. Cork-Float Boom
Port Hueneme, California
3. Fire Hose Boom
Quiescent Waters
Puerto Rican Boom
Ocean Eagle Oil Spill
5. Rubber Bladder Boom
Helford River, Great Britain
6. Rubber Tire Boom
Torrey Canyon Oil Spill
7. Steel Pipe Boom
Philadelphia, Pennsylvania
8. U.S. Navy Boom
Long Beach, California;
Chevron Spill, 1970
9. Wooden Float Boom
Pearl Harbor, Hawaii
10. Wooden Timber Boom
Quiescent Waters
11. Wooden V-Boom
Peros Gyiroc, France
17-32
-------
3/4" PLYWOOD
1/2" WIRE ROPE
BALLAST FILLED PLASTIC SKIRT
NAVY BOOM
Figure 16
NAVY BOOM
17-33
-------
presently available. Some are designed
to provide ah/adsorbing capability,
others integral skimming capability along
with their oil-retaining function. A
partial listing of these is presented
in Table 2.
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 containment 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
containment 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 compression-type coupling. Air
was supplied by a 600 cfm compressor
operating at ^5 psi. The cost for this
type of barrier will vary with the site
location.
V EXAMPLE OF USE
The following is a narrative presenta-
tion 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 h
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.
You have two skimmers available having
a combined capacity of about 600
gallons per minute (water-oil). 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 of 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 Ik
hours.(See figure A)
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
-------
ROCKY
SHOREFACE
SAND-
BEACH AREA
.CURRENT-2KNOTS
N
OIL SLICK
GENERAL POLLUTION SITUATION
17-35
FIGURE A
-------
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 some type of
storage facility for oil-water separa-
tion. 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.
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.
k 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 speed 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
concerning 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 otherwise exist in the boom and
eliminates 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 arrange-
ment, 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
17-36
-------
WORK BOAT
(b)
SKIMMER
(a)
/This angle should not
X exceed 20°
WIND
~BOAT
FIGURE B. MAIN SLICK RECOVERY
/\ # I BOAT
#2 BOATA
Turbulence and
loss of oil at this
sharp bend without
bowstring arrangement.
Bowstring tension
line reduces sharp
bend in boom.
WORK BOAT
FIGURE C . TOWING A FUNNEL BOOM ARRANGEMENT
17-37
-------
17-38
N
ROCKY
SHOREFACE
ANCHORD /
FLOAT
SKIMMER BOOM
j SYSTEM WILL BE
I HERE WHEN
_J AVAILABLE.
'BARGE MOUNTED
DIESEL
COMPRESSER
\
REMNANTS OF OIL SLICK
SHOREFACE PROTECTION SCHEME
FIGURE D
-------
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 compressor
mounted on a barge or convenient head-
land 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.(3P^ firuro 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.
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
Spills by Physical and Air Barriers,"
Massachusetts Institute of Technology,
Boston, 1969.
k Lehr, W. E. and Schorer, J. 0., "Design
Requirements for Booms," Joint FWPCA-API
Conference Proceedings, New York,
December 1969.
5 Milz, E. A., "An Evaluation-Oil Spill
Control Equipment & Techniques," API
21st Annual Pipeline Conference,
Dallas, April 1970.
6 Oil Spill Containment Systems,
Northeast Region R&D Programs, Federal
Water Quality Administration, 1970.
7 Scott, A. L., et al "Removal of Oil
from Harbor Waters," Clearinghouse
for Federal Scientific and Technical
Information, No. AD 83U973, February
1968.
17-39
-------
8 Testing and Evaluation of Oil Spill
Recovery Equipment, Water Pollution
Control Research Series, Grant No.
150-80-DOZ, Federal Water Qualitj»1970.
9 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.
This outline was prepared by Thomas W.
Devine, Sanitary Engineer, New England
Basins Office, Region I, Water Quality
Office, Environmental Protection Agency.
17-40
-------
OIL SKIMMING DEVICES
I INTRODUCTION
Once an oil spill has occurred,
the most positive approach to
protect the environment is to
physically remove the oil from
the water. This may be accom-
plished, 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 publica-
tion titled, "Oil Skimming
Devices", is recommended.
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
situat ions.
6 Ability to skim oil at a high
oil to water ratio.
The present day skimmers are gen-
erally designed to emphasize one
or more of the above characteris-
tics. 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 referenced 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 con-
structed as one unit, separate
units or any combination 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.
18-1
-------
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 conditions and an
adequate thickness of oil; how-
ever, viscosity of the oil is
not too important. Even so, a
certain amount of water is drawn
over the weir making it neces-
sary 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. The
type of oil is not a major con-
s ide rat ion.
The .floating suction type operates
on the same principal as the
household vacuum cleaner. The
unit is generally small in 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 effect 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 sur-
faces are constructed of
aluminum or various oleo-
philic 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 dam-
age. 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 particu-
lar pickup head:
1 Type of oil.
2 Sea state - waves and
currents.
3 Debris - sorbents.
18-2
-------
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 arrange-
ments.
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
pump can handle large volumes of
flow which may be required to re-
move very thin slicks. However,
this type of pump imparts tremen-
dous mixing energy and produces
an oil/water emulsion which may
not separate satisfactorily in the
settling chamber. On the
other hand, positive dis-
placement 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 dis-
placement 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 mainte-
nance assistance available.
Based on past experience,
the chief cause for an
unsuccessful oil skimming
operation has been due to
failure in the pumping sys-
tem.
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.
18-3
-------
Three types of skimmers
1. Weir type
To suet ion .
pump
WATER
2. Floating suction type
Roller or wiper for squeezing or
wiping oil into pon
Collection pon
WATER
3. Absorbent surface type
Figure 1
BOOM
Figure 2 Absorbent Belt for Oil Skimmer
18-4
-------
Normally, the weir type and the
floating suction head type pick-
up units require an oil/water
separator. Likewise, if a
centrifugal pump is used, a
separator is usually required.
Ill SUMMARY
B
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.
Tests and experiences have indi-
cated 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.
C 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
proposed skimmer is to be
used. Using this informa-
tion the proper oil skimmer
can then be selected.
REFERENCES
1 Milz, E. A. , "An Evaluation
of Oil Spill Control Equip-
ment and Techniques", April
14, 1970, Shell Pipe Line
Corporation, P. 0. 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, New York 10020.
3 "Oil Skimming Devices",
Edison Water Quality Labora-
tory, May 1970, Planning and
Resources Office, Office of
Research and Development,
EPA, Washington, D. C. 202U2.
Outline prepared by J. S. Dorrler,
Acting Chief, Oil Pollution R&D,
Edison Water Quality Laboratory,
Edison, New Jersey 08817, January
1971.
18-5
-------
BEACH CLEANUP
I
INTRODUCTION
National and international publicity
given to the Torrey Canyon and Santa
Barbara incidents have led to a
public outcry to stop the oil pol-
lution of our national shorelines.
II -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.
Ill 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 movement 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 approxi-
mately 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.
C If the pollution damage to the beach
is much more extensive, then mechanical
equipment must be used. Through re-
search, 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 com-
bined uses of these vehicles provide
the most rapid means of beach restor-
ation 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 iritertidal 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.
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B Should sufficient time exist be-
tween 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". Straw.
which has a natural absorptive cap-
acity 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.
C 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 re-
moval by vacuum tank truck.
V CHEMICALS
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 "quick-
sand" with oil alone. As the lit-
erature 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 con-
cluded that various types of per-
sistant oil alone penetrated no
more than two inches into the sand
while oil mixed with chemicals (dis-
persants, 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 re-
vealed 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.
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
Sometimes a "high-use" beach becomes
stained with a light oil such as a
#2 fuel. This becomes a problem be-
cause of instant and deep penetration.
The only really effective method of
cleansing this type of pollution is
to expose as much of the contaminated
beach sand to the sunlight and wind
as possible. This can be done effec-
tively by the use of a harrowing plow
or beach cleaning machines, which
are used to remove trash from beaches.
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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.
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.
Outline prepared by Howard J. Lamp'I,
Oil Spills Coordinator, Edison Water
Quality Laboratory, Edison. New
Jersey 08817, January 1971'.
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