600283115
THREE NEW TECHNIQUES FOR FLOATING POLLUTANT
SPILL CONTROL AND RECOVERY
William W. Bannister and Alfred H. Donate!li
University of Lowell
Lowell, Massachusetts 01854
William A. Curby
Sias Laboratories, Lahey Clinic Foundation
Burlington, Massachusetts 01803
David L. Kan
Massachusetts Maritime Academy
Buzzards Bay, Massachusetts 02532
William J. Dal ton and David A. Porta
Datasonics, Inc.
Cataumet, Massachusetts 02534
Grant Nos. R-806118-01 and R-804628-01
Project Officer
Uwe Frank
Oil and Hazardous Materials Spills Branch
Municipal Environmental Research Laboratory - Cincinnati
Edison, New Jersey 08837
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under Grant Nos. R-806118-01
and R-804628-01 to the University of Lowell. It has been subject to the
Agency's peer and administrative review, and it has been approved for
publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
n
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FORE WORD
The U.S. Environmental Protection Agency was created because of
increasing public and government concern about the dangers of pollution to
the health and welfare of the American people. Noxious air, foul water,
and spoiled land are tragic testimonies to the deterioration of our natural
2nvironment. The complexity of that environment and the interplay of its
:omponents require a concentrated and integrated attack on the problem.
Research and development is that necessary first step in problem
solution; it involves defining the problem, measuring its impact, and
searching for solutions. The Municipal Environmental Research Laboratory
develops new and improved technology and systems to prevent, treat, and
nanage wastewater and solid and hazardous waste pollutant discharges from
municipal and community sources, to preserve and treat public drinking
mater supplies, and to minimize the adverse economic, social, health, and
aesthetic effects of pollution. This publication is one of the products of
that research and provides a most vital communications link between the
researcher and the user community.
This report discusses three new techniques of oil and floating
hazardous material spill control and recovery whereby (1) spills can be
gelled to a solid consistency, (2) cheap, nontoxic and efficient
fluorescent agents can be applied in low concentrations onto spills by
conventional crop-dusting or spray techniques, and (3) underwater sonic
sensing provides excellent synergistic effects with the fluorescence
technique.
Francis T. Mayo, Director
Municipal Environmental Research Laboratory
m
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ABSTRACT
Three new techniques were investigated for controlling and recovering
oil and floating hazardous material spills in water bodies: amine
carbamate gelling agents, fluorescent agents for night-time operations, and
environmental sonic sensing. These methods are aimed at solving the
serious problems posed by the poor visibility that often accompanies spill
situations. Operational capability is nonexistent at night or during other
periods of low visibility. But fast, continuous action is essential to
recovery operations, since cleared areas can be covered again in just a few
hours as the unharvested contaminant drifts back over the cleared track.
Moreover, skimmer operations are most efficient with thicker pollutant
films. Thus the spreading of the material both increases the operational
area and decreases cleanup efficiency.
Amine carbamate gelling agents can be used to gel spills quickly and
completely to a solid consistency. This gel is much more visible than oil,
(for example) does not readily ,rlow or spread, is very easily, quickly, and
completely recovered by nets or sieves, is much less volatile (and thus ,
less hazardous with regard to fire and toxicity), does not permeate sand or
other porous materials, and can be easily regenerated into the original HM
and gelling components.
Cheap, nontoxic, and highly efficient fluorescent agents can be applied
in low (50 ppm) concentrations onto spill areas by conventional crop
dusting or spraying techniques. In open water with no pollutant cover, the
fluorescer is dissipated into the water column; but it is preferentially
retained without extraction into the water wherever there are pollutant
patches. At night, commercial UV (ultraviolet or "black" light) display
lights (or modified ordinary mercury vapor street lights) can be beamed
over the spill area. Vivid fluorescent illumination occurs only from spill
patches, thereby making such areas easily visibile and extending spill
control and recovery operations into night-time hours.
Underwater sonic sensing techniques were shown to be excellent means of
locating near-surface pollutant. In typical spill situations, a large
portion of the pollutant is in a floating globule near the water surface as
a result of surface wave action. This condition is particularly common for
high-density materials. Sonic sensing can also provide much-needed
information on the rate of dissipation of pollutant into the water column.
Sonic sensing and fluorescent techniques also have excellent synergistic
capabilities when used together, though both techniques are excellent alone.
This report was submitted in fulfillment of Grant Nos. R804628-0 and
R806118-01 under the partial sponsorship of the U.S. Environmental
Protection Agency. The report covers the period September 15, 1978, to
September 14, 1979, and work was completed as of May 15, 1982.
iv
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CONTENTS
r or ward ill
Abstract iv
•igures vii
Abbreviations and Symbols x
Conversion Factors xi
Acknowledgements xii
1. Introduction 1
2. Conclusions 5
3. Recommendations 10
4. Results 11
Preliminary U.S. Navy Oil Spill Study 11
OHMSETT Test I: Extrapolation of Amine Carbamate
System to Large-Scale Situation 22
Bay "F" Test I: Carbamation by Liquid/
Gaseous C02 Systems 29
OHMSETT Test II: Design, Construction and Testing of
Prototype Spill Control and Recovery Equipment . 33
Bay "F" Test II: Design, Construction and Testing of
Prototype Portable Spill Control and Recovery
Equipment 34
Field Tests at U.S. Naval Submarine Base,
New London, Connecticut 44
Use of Fluorescent Agents and Acoustic Sensing for
Night-Time Spill Recovery and Control Operations 59
References 73
Appendices
A. Amine Dl™J and its Derivatives, Bulletin OR-132C,
Hercules, Incorporated 75
B. Toxicity of Hercules Amine D to Marine Life 83
C. Toxicology Data Sheets, Uvitex OB and Nopol 94
D. Volatility and Flash Point Studies 99
E. Submissions of Product Listings for Inclusion in Survey
of Equipment for Oil and Floating Hazardous Material
Spill Countermeasures 101
F. Near-Surface Water Column Profiling by Acoustic Sensing as a
Complementary Means to Define Extents of Low-Visibility
Oil and Hazardous Chemical Spills 112
G. Report of Oil Spill Control and Recovery Field Tests at U.S.
Naval Submarine Base, New London, Connecticut 121
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Fluorescent Agents for Night-Time Operations: Results
of Tests Aboard EPA OSV Antelope, 14 September 1981 . . 123
Proposed Oil and Hazardous Chemical Spill Control and
Recovery by Amine Carbamate Gelation 130
Proposed Use of Fluorescent Agents and Acoustic
Sensing for Night-Time Spill Recovery and Control
Operations 137
VI
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FIGURES
Number Page
1 Amine D sprayer 14
2 Application of dry ice 15
3 Gelation occurs quickly 16
4 Harvesting gelled oil 17
5 Detail of gelled oil 18
6 Recovery operation using DIP skimmer craft 19
7 Another view of DIP skimmer 20
8 Herding of gelled oil using Navy piston film 21
9 Pump for delivery of Amine D solution to sprayers 23
10 OHMSETT sprayers in action 24
11 Surface breaker equipment 25
12 Application of powdered dry ice 26
13 Recovery of gelled oil by means of nets 27
14 Sand permeability of gelled versus ungelled oil 28
15 Spraying operation at Bay "F" Test I 30
16 Carbonation at Bay "F" Test I 31
17 Recovery of gelled oil by means of sieve 32
18 "Compass Rose" underway in OHMSETT tank 35
19 Spraying apparatus on "Compass Rose" 36
20 Carbonation from "Compass Rose" 37
21 Gelled oil in OHMSETT tank 38
vii
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FIGURES (continued)
Number Page
22 Gelled oil in OHMSETT tank 39
23 Recovery of gelled oil by net 40
24 Portable hand-operated filter press 41
25 Filter press in operation 42
26 Wave action effects on "Compass Rose" intakes 43
27 Spraying apparatus in operation at Bay "F" Test II 45
28 Carbonation apparatus at Bay "F" Test II 46
29 Gelled oil at Bay "F" Test II 47
30 Herding of gelled oil with screen 48
31 Gelled oil at Bay "F" Test II 49
32 Recovery of gelled oil by net 50
33 Loading rubber raft assembly at New London Sub Base 51
34 Filling Amine D canisters on raft 52
35 Rubber raft equipped at submarine base 53
36 Rubber raft manned, awaiting boom placement . 54
37 Raft "Titanic" in operation at submarine base 55
38 Another view of raft operation 56
39 Trimaran craft at submarine base 57
40 Gelled oil from stern of trimaran raft 58
41 Use of fluorescent agents and acoustic sensing for night-
time oil spill recovery and control operations 60
42 Compatibility of chemicals with fluorescence and
sonic sensing techniques 61
43 Commencement of fluorescence test 63
44 Results of fluorescence test 64
v 1 i 1
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FIGURES (continued)
Number Page
45 EDO Aero 14B airborne spray tank (and auxiliary equipment). . . 65
46 Another view of EDO spray tank . . 66
47 Commencement of fluorescence dusting test 67
48 Dusting with fluorescent powder . 68
49 Results of fluorescence test 69
50 Cropdusting by helicopter 70
51 Breakup of ARGO MERCHANT 71
52 Oil slick from ARGO MERCHANT 71
53 EPA ocean survey vessel ANTELOPE 72
i x
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ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
Amine D
cm
DC
DIP
hp
hr
kg
Ib
m
ml
Nopol
NRL
OHMSETT
Pa
psi
PVC
rpm
UV
Uvitex OB
dehydroabietylamine (or, 1,4a-dimethyl-7-isopropyl
1,2,3,4,4a,9,10,10a-octahydro-l-phenanthrenemethylamine)
centimeter
direct current
dynamic inclined plane
horsepower
hour
kilogram
pounds
meter
mi 11i1iter
6,6-dimethylbi cyclo[3.1.1.]hept-2-ene-2-ethanol
Naval Research Laboratories
Oil and Hazardous Materials Simulated Environmental Testing Tank
Pascal
pounds per square inch
polyvinyl chloride
revolutions per minute
ultraviolet light
trade name (Ciba-Geigy Corp.) for a proprietary stilbene
SYMBOLS
°F
°K
fluorescer
— volts
— degrees Fahrenheit
— degrees Kelvin
— foot
— inch
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CONVERSION FACTORS
Inasmuch as all equipment that was constructed for the current project
and that is proposed for future work has and will be designed in accordance
with English units, all units of measurement in this report will generally be
in English units.
°F
feet
gallons
hp
inches
knots
Ibs
psi
to °K
to meters (m)
.3
to
to
to
to
to
to
m
watts
meters
m/hr
kg
subtract 32, multiply by 0.555, and add 273
multiply by 0.3048
multiply by 3.785 x 10"3
multiply by 746
multiply by 0.0254
multiply by 1,852
multiply by 0.454
Pascals (Pa) multiply by 6.895 x
xi
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ACKNOWLEDGMENTS
Major support for the various phases of the research as discussed in this
report was provided by the U.S. Environmental Protection Agency and the U.S.
Navy. We are also grateful to the Cardox Division of Chemetron, Inc.; the
Ciba-Geigy Corp.; Flexcon Corp.; GTE Laboratories, Inc.; the Hercules Corp.;
Morton Chemical Co.; Norda, Inc.; and the Shell Oil Company for generous dona-
tions of funds, equipment, and technical information in support of the project
work. The University of Lowell Alumni Association provided research fellow-
ships for several of the students working on this project, which was much
appreciated by the group.
Mr. Uwe Frank of the Edison, New Jersey, Municipal Environmental Research
Laboratory of the EPA, and Dr. William Garrett of the Naval Research Labora-
tories were project officers for most of the work reported herein. Their sug-
gestions and technical expertise were vitally important to the success of the
overall project operations.
Grateful acknowledgement is extended to Captain Dwight Paine and the crew
members of the EPA Ocean Survey Vessel ANTELOPE, which was provided to us for
the very successful sea test involving use of fluorescent agents for night-time
spill operations. Mr. Edward S. McLean of the EPA and Mr. Robert Blase and Dr.
Leslie Pierre of the MAR Corporation (operators of the ANTELOPE) were helpful
to us in making the ship available and in providing valuable technical assist-
ance and advice prior to and during these tests.
'The assistance and cooperation provided by the Mason & Hanger - Silas
Mason Company's OHMSETT facility, and by the Commanding Officer and crew of the
Naval Submarine Support Facility at New London, Connecticut, were also invalu-
able to our group in the course of our project work at their facilities.
We also wish to acknowledge the considerable assistance provided to us by
the following individuals: Mr. Cesar Aguilar, President, SEA International;
Mr. Ralph Bianchi, President, JBF Co.; Mr. Robert Castellucci of the Naval
Facilities Engineering Command, and Chief David Miller, USN; Mr. Donald Sounia
of the Cardox Company; Mr. George Duggan, Mr. Robert Edelson, and Mr. Joel
Finkel of GTE Labs/Sylvania Corp.; and Mr. John Farlow and Mr. Leo McCarthy of
the EPA's Edison Laboratories.
Finally, we wish to thank the students (numbering more than 60) of this
group whose ideas, enthusiasm, and industry made all the results of the group
possible. We also wish to dedicate this report to the memory of the late Dr.
Howard Reynolds, Chairman of the Chemical Engineering Department, who helped to
conceive the ideas underlying this project.
x i i
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SECTION 1
INTRODUCTION
In recovery operations for oil and hazardous material* slicks on water
surfaces, a number of devices and techniques have been devised and imple-
mented. Destructive procedures include removal by burning; sorption into
straw or other material to facilitate oil removal for subsequent des-
truction, or into chemically treated sand or other agents that cause the
oil to sink; microbial agents that digest the oil; and dispersion with
surface-active agents that tend to break up the oil slick to facilitate
solution and eventual microbial degradation (1). Nondestructive devices
and techniques include the use of polymeric sorbents that can be spread
over a slick to absorb the oil, with subsequent recovery of the oil by
squeezing from the sorbent; passive restraint systems such as booms, which
prevent further spread of a slick; and active systems such as oil skimmers,
which remove oil by a variety of techniques, from the surface of the water
by mechanical action (2).
Disadvantages of destructive techniques include loss of the oil and the
very serious negative environmental impact on the water and/or atmosphere.
Serious problems are also associated with nondestructive recovery
attempts. Under the most ideal conditions, it is usually not feasible to
recover much more than 90% of a given spill. Recovery efforts are slow and
often frustrating; most oil skimmers, for example, have a maximum opera-
tional speed of 3 knots. Oil slicks usually move back over the previously
cleared track made by a skimmer, so little progress can be made in terms of
actual complete clearing of a given area. Because of the slick's slow
operational speed, the actions of wind, current, and the migrational
tendency of the oil slick can all change the contour and overall area of
the slick at the same time the skimmer is attempting its recovery effort.
Oil slicks are often difficult to distinguish from open water areas,
particularly at low elevations from the surface of the water. Thus the
helmsman of a skimmer craft may find it extremely difficult to follow a
proper track in the recovery of an oil slick. Visibility of oil slicks is
particularly low at dusk or in other periods of poor light.
* The terms "oil and "hazardous material" are frequently used
interchangeably in this report. Gelation, fluorescence, and sonic sensing
techniques are applicable (except where otherwise noted) to all organic
hazardous chemical and oil spills.
1
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Additives have been introduced from time to time to facilitate
collection of oil slicks by gelation or other agglomerative processes
involving the oil. These agents are often expensive, and problems
invariably arise in the addition of the agent to the oil (viscous
interfaces between the oil and the gelling agent tend to prevent complete
and rapid distribution), and frequently in the separation of the oil from
the gel in recovery operations (3).
Recovery work performed by the EPA (4) indicates that the following
observations generally hold for conventional gelling agents or similar
additives:
1. Introduction of congealing agents into hazardous material spills
enables a stable boom to contain the material at a higher current
velocity or tow speed in calm water.
2. To optimize the effect of such agents, time for mixing and absorp-
tion must be allowed, depending on wave condition and turbulence.*
3. Because of splash-over failure, such agents do not enhance
containment in the presence of 0.3-meter harbor chop.
4. Agent acquisition, transportation, distribution, separation, recyc-
ling, and disposal substantially increase the time required for
cleanup efforts.*
5. In some instances, the use of such agents may permit a higher
recovery craft speed than would be the case if such agents were
not used.
6. Vapor concentrations above systems involving sorbents (not gelants)
were sometimes actually higher than when sorbents were not used.*
7. Use of sorbents substantially reduces the extent of emulsification v
of hazardous material into the water column.*?/ /
Our research group became quite active some time ago on processes (5)
whereby hydrocarbon and other organic liquid formulations would be gelled
to a solid consistency quickly, safely, and economically, using readily
available amines. These can be easily admixed with oils to form a complete
solution before gelation occurs, thus completely avoiding any possibility
* As will be noted in appropriate sections of this report, the limitations
noted in items 2, 4, and 6 were not as serious in the observations made in
this investigation of amine carbamate gelling agents. Thus very little or
no mixing time is required; the greatly increased speed and efficiency of
collection greatly offsets the other increased time requirements and there
appears to be a greatly reduced (not increased) vapor concentration over
amine carbamate gelled systems.
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of the formation of viscous interfaces between the oil and the gelling
agent.
This process depends on the action of carbon dioxide on a primary amine
to form a zwitterionic carbamate salt:
+
R-NH2 + C02 - R-NH2C02
(If an aqueous system is present and a desire exists to prevent solution of
the carbamate in the water, a high-molecular-weight primary aliphatic or
alicyclic amine is chosen, with attendant low water solubility.) The amine
is oil soluble, and a thorough solution is easily and quickly attained,
whereupon carbon dioxide can be added for rapid gel formation (usually
within a few minutes). Moreover, oil or other organic formulations can be
separated rather easily and quickly from the gelled mixture by filter
pressing, centrifuging, or a variety of chemical techniques. And in all
such instances the amine gel!ant could be regenerated very economically for
subsequent reuse.
Thus it appears that the principal disadvantages inherent in previously
studied gelling systems do not apply to the amine carbamate system in terms
of potential use in oil spill recovery efforts.
Since 1976, our group has been working on the use of this and related
processes for oil and hazardous material spill recovery and control
operations.
These other developments are largely related to the very serious
problems of poor visibility associated with typical oil and hazardous
chemical spill situations. No operational capability exists at night or in
other periods of low visibility, when operating personnel are unable to
discern spill boundaries. But time is extremely important in spill control
and recovery work; in a few hours, areas cleared of a spill by skimming or
similar operations can be covered again as unharvested oil or chemicals
drift back over the cleared track. Moreover, skimmers are most efficient
with thicker films. Thus spreading the oil not only increases the
operational area, but also decreases film thicknesses with an attendant
decrease in efficiency.
In our earlier work we demonstrated that commercially available,
nontoxic and highly efficient fluorescent agents with both oil and water
compatibility could be applied in very low concentrations to oil spills
with excellent results. At night, when natural light is sufficiently
diminished to permit visibility of fluorescent light, UV light could be
beamed over the spill area to illuminate the resulting fluorescence from
the soil spill patches. The perimeters of such areas would thus be easily
descerned, and operational capabilities would be extended into night-time
hours. This procedure could be particularly important in situations
occurring in winter months in higher latitudes, when night-time conditions
are significantly prolonged.
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At about the same time, information began to become available regarding
new developments in underwater environmental acoustic sensing techniques,
whereby sophisticated sonar gear can be used to detect dispersions of organic
material into near-surface areas of large bodies of water.
Thus, as work progressed in oil and hazardous chemical spill recovery,
it became of increasing interest to investigate the possibilities of syner-
gistic results that might accrue on combination of two or more of the gela-
tion, fluorescence, and sonic sensing processes.
The overall project work to be described in this report will be discussed
in the following order of development:
1. Preliminary investigations (sponsored by the U.S. Navy, 1975-1976).
CH~<.e~ TWt L •-
2. ^Preliminary extrapolation to larger scale situations (EPA,
3. Bay "F" Test I: Carbamation by Liquid/Gaseous CO, Systems (EPA,
early 1978). i
4. OHMSETT Test II: Design, Construction and Testing of Prototype Haz-
ardous Material Spill Control and Recovery Equipment (EPA, 1978).
5. Bay "F" Test II: Design, Construction and Testing of Prototype Port-
able Spill and Recovery Equipment (EPA, 1979).
6. Field tests at U.S. Naval Submarine Base, New London, Connecticut
(U.S. Navy, 1980-1981).
7. Use of Fluorescent Agents and Acoustic Sensing for Night-Time Oil
Spill Recovery and Control Operations (EPA; GTE Laboratories, Inc.,
1981-present).
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SECTION 2
CONCLUSIONS
The following conclusions pertain to the work performed on this project,
and are presented in the order discussed in Section 4 (Results) of the report,
PRELIMINARY U.S. NAVY OIL SPILL STUDY
1. The optimum gelling agent is comprised of a mixture of 70% Amine D,
15% ethyl alcohol, and 15% Nopol, applied in a concentration of
approximately 15% in the oil or hazardous chemical spill.
2. The solubility of Amine D in water is very low—less than 1 part per
million. Only with extreme agitation will any degree of emulsifica-
tion in water occur. For ordinary wave action in open water, there
would probably be no emulsification problem; pounding coastal surf
might cause emulsification, probably of the same order of magnitude
as is the case with oil in such surf.
3. Toxicities of the components of the gelling agent formulation are
low, of the same order of magnitude (or less) than that of hydro-
carbon oil.
4. Film thickness of the oil or hazardous chemical spill does not
appear to be a factor in terms of efficiency of gelation.
5. The optimum carbamating agent has proven to be liquid or gaseous
carbon dioxide.
6. The optimum method of separation of gelled oil or hazardous chemi-
cals into the original ungelled material and the gelling agents is
pressure filtration. Yields of more than 90% of the original oil
can be recovered, with essentially no contamination by either Amine
D or Nopol. The filter cake contains the remaining oil, the amine
carbamate, and the Nopol. The amine carbamate can be heated to
100°C to reverse the carbonation process, affording Amine D and
Nopol which can then be reused for subsequent gelation work.
7. Very significant reductions in rates of volatilization result on
amine carbamate gelation of organic chemicals, by as much as 50%.
Flash points of flammable materials are correspondingly increased,
with resulting decreases in fire hazards; toxicity hazards are also
correspondingly decreased.
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8. Many hazardous chemicals other than hydrocarbons are easily gelled
by this system. Not all organic compounds are easily gelled, how-
ever. Important exceptions include: extremely thick and viscous
materials, in which solution of the amine solution is difficult to
achieve readily; acidic compounds (which react with the basic amine)
do not gel; unsaturated vegetable oils form gels of rather weak
mechanical strength, as is the case of some high-molecular-weight
naphthenic hydrocarbons as are often found in lubricants. The large
majority of organic compounds do form satisfactory gels, however. In
the event the nature of a hazardous material spill is not known, a
simple and quick test can be performed on a small (approximately 25-
ml) sample of the material by adding about 15% of the gelling agent
and treating with carbonated water.
9. Beach-front protection is afforded by gelation of incoming spills;
ungelled materials readily soak into sand, whereas gelled materials
do not, thereby very considerably facilitating beach cleanup efforts.
10. Very significant advantages can be realized in use of amine carba-
mate gelation processes. The gelled oil or hazardous chemical spill
is immobilized and will not readily move back over a cleared track
(as will ungelled spills); the ease and speed of recovery is very
greatly increased, as is the extent of recovery; the gelled spill is
o: much higher visibility than ungelled liquid spills; nets, sieves,
and similar retrieval equipment provide excellent recovery results
(these being totally useless with liquid spills); storage and trans-
port of gelled recovered spills presents no destabilizing free sur-
face effects (i.e., "sloshing") in recovery craft or barges; uncon-
ventional containers such as burlap or plastic bags, cardboard boxes
and the like can be used for short-term storage of gelled recovered
spill material (these being totally unsuitable for ungelled material),
and the ability to use such containers in any available deck space
permits the use of any kind of vessel for such recovery work (where-
as liquid spill recovery vessels must have special liquid cargo
holds or tanks).
OHMSETT TEST I: EXTRAPOLATION OF AMINE CARBAMATE
SYSTEM TO LARGE-SCALE SITUATIONS
1. This series of tests confirmed the feasibility of use of the amine
carbamate gelation system in relatively large situations.
2. The use of solid dry ice as a source of carbon dioxide was shown to
be very infeasible, due to procurement, transportation, storage, and
cost considerations. Also, dry ice is affected adversely by rain or
high humidity.
BAY "F" TESt I: CARBAMATION BY LIQUID/GASEOUS C02 SYSTEMS
1. In this test it was shown that commercially available liquid C02 in
cylinders or tanks delivered in liquid or gas form was an optimam
carbamating agent with none of the drawbacks associated with solid
dry ice.
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2. Improved Amine D sprayer systems were designed and constructed, as
were CCL bubbler systems.
3. It became apparent that a two-pass system (with separate phases in-
volving application of Amine D as a spray, followed by a subsequent
pass with application of CCL) would be infeasible in field operations,
OHMSETT TEST II: DESIGN, CONSTRUCTION, AND TESTING OF PROTOTYPE
HAZARDOUS MATERIAL SPILL CONTROL AND RECOVERY EQUIPMENT
The main objectives of this test series were the design, construction, and
testing of a control and recovery craft that would effect gelation of an oil
spill by simultaneous spraying and carbonation of the slick in a single pass.
It was concluded from this series of tests that:
1. Large spill areas (an acre or more) could be treated and controlled
quickly (within 10 minutes) by use of a craft that could contain rea-
sonable quantities of gelling agents (i.e., 400 gallons of Amine D
solution and 750 pounds of carbon dioxide). Complete recovery of
the resulting gelled oil could be effected in about the same time
interval by means of followup craft equipped with suitable netting
gear.
2. For other than smooth water surfaces (e.g., in harbor chop condi-
tions), further attention needed to be given to design of the
sprayer/carbonator assemblies. Specifically, the interaction of
confused seas with the bow wave of conventional harbor craft tends
to force a large amount of oil in the intended track of the craft to
either side and away from the reach of the sprayer/carbonator assem-
blies mounted on such craft. To avoid this, one solution would be to
mount these assemblies further forward and further outboard of the
craft.
3. Although such a craft would be useful in harbor work, or in similar
areas where storage and maintenance of the craft would present little
problem, a need could exist for a portable spill and recovery craft
that could be easily assembled and disassembled, and that could be
easily stored and transported from central locations to remote spill
areas.
BAY "F" TEST II: DESIGN, CONSTRUCTION, AND TESTING OF PROTOTYPE
PORTABLE. SPILL CONTROL AND RECOVERY EQUIPMENT
In this test a small three-man rubber raft was modified to provide a
small-area spill control and recovery craft that could easily be stored and
transported to remote spill sites. In the small confines of the Bay "F" test
pool, excellent results were obtained, suggesting that the craft would be of
use in possible remote spill situations, particularly in inland waters with
little or no wave action.
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FIELD TESTS AT U.S. NAVAL SUBMARINE BASE, NEW LONDON, CONNECTICUT
Several tests were performed at this activity in late 1980 and early 1981,
in attempts to reduce to practice, in actual oil spill situations, the concepts
and techniques that had been developed in the previous test programs. The fol-
lowing conclusions were derived:
1. The small rubber raft developed in the Bay "F" exercise was found to
be totally unsuitable for open water work, particularly as it was
modified in this work to enable a dual capability for spraying and
carbonating in one pass. The raft was so overladen with equipment
that it presented danger of swamping even in small waves of less than
2 feet in the open water.
2. The raft was considered safe and feasible to use under "mill pond"
conditions as could be encountered in small lakes or other small bod-
ies of water with spill situations. It was considered advisable,
even for these calm condition situations, to have a more sturdy craft
with higher freeboard and greater stability. A further advantage
would also derive from having increased capabilities for larger
spills, in terms of the larger gelling agent loads such a larger
craft could carry.
3. In subsequent tests at the Submarine Base, a trimaran (three-hulled
raft) was utilized, with excellent results. This craft was quite
stable in wave conditions up to 2 feet. It is quite sturdy, and can
easily carry up to 2.5 tons of equipment and supplies, in addition
to a crew of five technicians. It is capable of being powered to
attain working speeds of up to 5 knots, which would enable coverage
of up to an acre of oil slick area to be controlled in approximately
10 minutes, using gelling equipment and supplies that can be car-
ried on the trimaran. By installation of appropriate intake booms
at the bow of the trimaran, bow wave problems (i.e., the tendency
for interaction of the bow wave with confused seas to cause sweeping
of incoming oil to be swept to either side of the craft) should
largely be eliminated.
4. Further work would be desirable to develop a portable trimaran that
could be easily assembled, disassembled, capable of being stored and
transported with all required equipment and supplies in a small van,
and capable of gelling and controlling a large spill area quickly
and completely. The use of nets towed behind the craft could enable
simultaneous control and recovery of such spills.
USE OF FLUORESCENT AGENTS AND ACOUSTIC SENSING FOR NIGHT-TIME
HAZARDOUS CHEMICAL SPILL RECOVERY AND CONTROL OPERATIONS
A number of small tests had been performed, commencing as early as the
preliminary U.S. Navy Oil Spill Studies of this overall series, in which it
was demonstrated that use of fluorescent agents when applied to oil or hazard-
ous chemical spills would provide excellent night-time operational capabili-
ties. Full-scale research efforts in this direction were instituted in mid-
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1981, with extension also to sonic sensing techniques in the Fall. The follow-
ing observations and conclusions pertain to this on-going work.
1. Fluorescent agents can be applied in the form of sprays of liquid
solutions of such agents, or by dusting with powder formulations.
Current tests strongly indicate that the dusting operation is the
more feasible, although both techniques have proven to be extremely
promising.
2. Concentrations of fluorescer in oil spills are quite effective for
excellent night-time visibility, when applied as low as 59 parts per
million in the oil.
3. The best dust formulation appears to be an intimate mixture of the
fluorescer in powdered gypsum (CaSO/j). The optimum spray formulation
appears to be a solution of the fluorescer in di- or tripropylene
glycol monomethyl ether solvents.
4. Uvitex OB(™) (Ciba-Geigy Corp.) and Yellow 131SC(™) Morton
Chemical Co.) have proven to be excellent nontoxic, cheap, and
highly effective fluorescers.
5. The gypsum powder base is entirely nontoxic and with no fire or
other hazardous character associated with use. Glycol ether
solvents have very low fire and toxicity hazards, and in the
concentrations contemplated for use would probably present no
significant hazard.
6. Underwater sonic sensing techniques were shown to have excellent
synergistic effects when used with the fluorescent techniques.
Both techniques would be excellent when used on a stand-alone basis.
Sonic sensing is particularly invaluable in situations in which a
need exists to determine the rate of dissipation of oil into the
water column.
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SECTION 3
RECOMMENDATIONS
In view of the successful results of the research performed in the course
of the EPA, Navy, and similar projects discussed in this report, further work
is proposed to extrapolate these results to full-scale operational situations,
with construction, testing, evaluation, and full utilization of appropriate
equipment and procedures.
The proposed work would have the following objectives:
1. Design, construction, testing, and utilization of a prototype tri-
maran craft for use in hazardous chemical spill recovery and con-
trol operations in inland waters and in harbor situations. The
craft will be portable, easy to assemble and disassemble, capable
of supporting a load of approximately 12,000 pounds for recovery
and control operatiaons over an area of about an acre in about 5
minutes, gelling up to 2,200 gallons of spilled chemicals in a
track up to 17 feet in width and 1/2 mile in length. Equipment for
operations with fluorescent agents under night-time conditions will
be available. The craft, when disassembled, would be stored and
transported in a truck-trailer space of about 8 by 12 by 6 feet,
along with all required chemicals and supplies.
Reference is made to Appendix I of this report for detailed discus-
sions and specifications for the proposed trimaran craft and for
its operation.
2. Performance of full-scale tests with application of fluorescer from
aircraft or from ships onto oil or hazardous chemical spills in wide
open water situations, with subsequent illumination at night by UV
floodlights, to permit full-scale night-time recovery and control
operations. Acoustic sensing gear operated from recovery vessels
will be utilized to permit auxiliary reconnaissance in terms of
locating and tracking such spills, and in ascertaining the course
of recovery and control work.
Reference is made to Appendix J of this report for detailed discus-
sions of the salient features of the proposed tests.
10
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SECTION 4
RESULTS
Results of the work performed on this overall project are discussed in
the chronological order of the undertaking of the major phases of the project:
1. Preliminary U.S. Navy Oil Spill Study
2. OHMSETT Test I: Extrapolation of Amine Carbamate System to Large-
Scale Situations
3. Bay "F" Test I: Carbamation by Liquid/Gaseous CO,, Systems
4. OHMSETT Test II: Design, Construction and Testing of Prototype Haz-
ardous Material Spill Control and Recovery Equipment
5. Bay "F" Test II: Design, Construction and Testing of Prototype Port-
able Spill and Recovery Equipment
6. Field Tests at U.S. Naval Submarine Base, New London, Connecticut
7. Use of Fluorescent Agents and Acoustic Sensing for Night-Time Oil .
Spill Recovery and Control Operations
PRELIMINARY U.S. NAVY OIL SPILL STUDY
In the early part of this phase of the project work, there was undertaken
a study of the physical properties of these gel systems, including the follow-
ing topics:
1. Optimization of gelling agent. Of more than 60 commercially avail-
able, low-toxicity, water-insoluble amines studied, dehydroabietyl-
amine ("Amine D") was by far the most effective as a gelling agent
for oil and hazardous chemical spills on water surfaces. The opti-
mum formulation was found to be comprised of 70% Amine D, 15% ethyl
alcohol, and 15% 6,6-dimethylbicyclo-(3.1.l)-2-heptene-2-ethanol
("Nopol").
2. In determining the solubility of Amine D as the C0£ carbamate salt
in water, both fresh and salt water samples were saturated by shak-
ing with Amine D carbamate for 15 minutes. Using techniques de-
scribed by Ghosh and Whitehouse (7), NBD Chloride (7-chloro-4-
nitrobenzo-2-oxa-l,3-diazole) was used as a fluorigenic reagent with
11
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both aqueous systems and with standard alcohol solutions of Amine D.
By comparison of the fluorescence spectra, it was determined that the
solubility of Amine D in water was less than 1 part per million; work
done at the EPA in Edison, New Jersey, with different fluorogenic
reagents confirmed these findings (8).
3. In determining the emulsification tendency of standard gels formed by
action of Amine D on No. 2 fuel oil in water, no significant emulsi-
fication occurred in test flasks at stirrer speeds up to 250 rpm over
time intervals of 5 minutes. Some emulsification, unstable to the
extent that phase separation occurred within 10 minutes, took place
at stirrer speeds around 1000 rpm. With blender stirrer speeds up to
20,000 rpm, complete emulsification occurred with no phase separation
within 1 day. From results of this work, and from observation of
tests performed at OHMSETT facilities with imposed wave actions up to
1.1 meter harbor chop conditions (in which no observable emulsifica-
tion occurred), it can be concluded that for most sea conditions in
open water, no problem should be anticipated in terms of emulsifica-
tion or other means of dispersion into the water. Dispersion and
emulsification might be a problem in the case of heavy pounding surf.
4. Investigations were undertaken in determining the optimum carbamat-
ing agent. Metal and ammonium carbonates and bicarbonates, and ammon-
ium carbamate all had varying efficiencies as C02 sources, but none
of these were judged to be as effective or desirable from any stand-
point as liquid, solid, or gaseous C02 itself. Unsuccessful attempts
were made to find a solvent cheap enough, water-soluble, and nontoxic
for use with precarbamated amine, which it was hoped could thereby be
sprayed directly into an oil or hazardous chemical spill to afford
gelation without a need for followup with a C02 treatment after
spraying the amine onto the spill.
5. Attempts were made to optimize the capability of separating gelled
oil into the oil and amine carbamate components, the former for imme-
diate availability for use in its intended application, and the car-
bamate for reconversion to the amine for subsequent reuse in spill
control and recovery operations.
Centrifuging represents one such method of separation, but the re-
quirements for adequate separation probably amount to an overall in-
feasibility for real-life field situations. Separations of up to
60% of the original oil were achieved using centrifuge speeds of
4,500 rpm, with centrifuging forces over 2,500 g in a time interval
of 15 minutes.
Extraction of oil from the gel after conversion of the amine to the
hydrogen sulfate (by treatment with dilute sulfuric acid) also proved
infeasible. Even after prolonged water washing of the oil phase
residual levels of the amine salt were still contained in the oil.
Filter pressing proved to be an effective means of separating compo-
nents of the gel. With ordinary vacuum filtration (less than 1 atm
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of pressure on the filter cake) in a Buchner funnel with rubber dam
covering the cake, separations in excess of 80% of the original oil
were readily achieved. Using fluorescence spectroscopy with NBD
Chloride as previously described (7), less than 1 part per million
of Amine D was detected in the oil phase; by gas chromatography, no
Nopol was found in the oil phase. The resulting filter cake con-
tained about 18% of the original oil and essentially all the Amine D
and Nopol. Higher filter pressures should be even more effective.
6. Toxicity levels, with regard to marine life, were conducted in this
phase of the project work; cf. the report of the Lahey Clinic Sias
Laboratories, Appendix B to this report. In summarizing this work.
it was found tht suspensions (not true solutions) of up to 20 ppm of
Amine D in sea water posed no greater toxicity effects to marine life
than would be encountered with similar levels of fuel oil (or simi-
lar hydrocarbon compositions). Inasmuch as Amine D has a solubility
of less than 1 ppm, and since introduction of the amine into the
water column is not an efficient process by emulsification or simi-
lar dispersion mechanism, it would appear that the use of Amine D as
a gelling agent in spill control and recovery operations would pose
no serious threat to marine life, and no-more so than is posed by oil
spills per se. In terms of the facilitation of the recovery and con-
trol of the spill, there is an obvious reduction of toxic effects to
marine life provided by use of this system in such spill control and
recovery efforts.
As is described in Appendices A and B to this report, Amine D is not
only of low toxicity, but also is not a significant skin sensitizer.
Throughout the 7 years in which this compound has been tested in oil
spill control and recovery work by more than 50 members of this
research group, three minor skin rashes were observed by three indi-
viduals. On each of these occasions these individuals had been work-
ing with other compounds or formulations (in one instance, toluene;
on the other two occasions, No. 2 fuel oil), in large quantities of
up to 50 gallons. It is deemed as likely that these rashes (which
disappeared in less than 1 day) were due to other compounds as that
they were due to Amine D. These same individuals were exposed to
Amine D on numerous other occasions with no untoward effects. Al-
though care should be exercised in working with Amine D, as would be
the case with any other chemical agent, this compound appears to be
safe.
Preliminary tests were undertaken in the Summer of 1977 at the JBF Com-
pany at Wilmington, Massachusetts, in small-scale field testing of the amine
carbamate system for use in oil spill control and recovery. Amine solution
sprayers, dry ice spreaders, and recovery nets and sieves as had been devel-
oped were tested, as was the use of DIP (Dynamic Inclined Plane) skimmer
craft, and capabilities for storage of gelled oil in makeshift containers such
as plastic bags and cardboard boxes were investigated. The results of these
tests are shown and discussed in Figures 1 through 8. Extremely efficient
recoveries (more than 99% oil recovery), greatly enhanced visibility of gelled
oil versus ungelled oil, and excellent compatibility of the system with use of
13
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Figure 1. Amine D sprayer.
A 3-gallon garden spray can is being loaded with 2.5
gallons of 70% Amine D/15% Nopol/15% ethyl alcohol.
The sprayer is pressurized by a hand pump that screws
into the top.
14
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Figure 2. Application of dry ice.
Five pounds of crushed dry ice is applied
to oil slick/Amine D solution using siev-
ing technique.
15
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Figure 3. Gelation occurs quickly.
Rapid gelation is essentially com-
pleted before carbonation has been
completed.
16
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Figure 4. Harvesting gelled oil.
A good idea of the firmness of the gel can be
obtained from this picture. It can also be noted
that recovery of the gelled oil is virtually com-
plete, using this technique; there is no residual
sheen. The clarity of the swept water area is
indicated by the vividness of the details on the
bottom of the pool (water depth was 8 feet). The
greatly increased visibility of the gelled oil is
also apparent here (compare with Figure 2).
17
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Figure 5. Detail of gelled oil.
It can be noted here that the thickness of
the oil has more than doubled, due to the
uptake of water into the gel.
18
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Figure 6. Recovery operation using DIP skimmer craft.
In another test at JBF facilities, with oil gelled by
amine carbamate, the following characteristics of the
gelled oil can be observed: (1) the gelled oil is
relatively immobile; there is little if any tendency
for the gelled oil to move away from the recovery craft
or to drift back over previously cleared areas. (2) the
gelled oil is of much greater visibility than the un-
gelled oil, which would considerably facilitate opera-
tions, particularly in conditions of low visibility.
19
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Figure 7. Another view of DIP skimmer.
DIP skimmer in operation on a gelled oil spill
than 99% of the spilled oil was recovered.
More
20
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Figure 8. Herding of gelled oil using Navy piston film.
At the end of this first test in the JBF pool facilities, it
was found that very small amounts of oil, mostly gelled but
with some ungelled oil, had been left behind under boom floats;
ungelled oil had apparently escaped the action of the sprayer.
This residual oil was treated with Navy piston film (similar in
action to Shell "Oil Herder") and then herded by hose action to
one end of the boomed area. Total residual oil amounted to less
than 400 ml in volume, indicating that a 99% recovery had been
effected.
21
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skimmer craft were noted in these tests.
Reference is also made to the following Appendices to this report:
Appendix A: Amine D (Hercules technical report)
Appendix B: Toxicity of Amine D to Marine Life
Appendix C: Toxicology Data Sheet (2), NOPOL
Appendix D: Volatility and Flash Point Studies
OHMSETT TEST I: EXTRAPOLATION OF AMINE CARBAMATE
SYSTEM TO LARGE-SCALE SITUATIONS
For the OHMSETT feasibility tests it was determined that a 12- by 100-
foot lane at the OHMSETT tank would be boomed off for all test runs (in actu-
ality, a 14- by 117-foot lane was provided during the tests). Accordingly,
two 6-foot sprayers, a dry ice crusher-spreader, and a surface breaker for
mixing the oil and amine after spraying were constructed and tested at the
University of Lowell for subsequent reassembly at the OHMSETT site. All Uni-
versity of Lowell tests were performed in a mockup pool 6 feet wide by 20 feet
in length, with a 1-foot depth, which was constructed for these tests. De-
tailed descriptions of these items of equipment, and discussions of the assem-
bly and operation, are provided with photographic illustrations in Figures 9
through 14 of this report.
A series of 10 tests, under calm, 2-foot harbor chop, and 4-foot harbor
chop conditions were originally planned, with both light and heavy CIRCO oils
(which were used as simulants for light and heavy commercial oils); in the
wave tests, two runs were originally scheduled for prolonged wave action of
several hours.
As it transpired, the CIRCO simulants were not optimum choices for the
tests. CIRCO oils (as manufactured by the Sun Oil Company) are alicyclic
(naphthenic) hydrocarbon-based lubricants, which are significantly different •
from conventional commercial oils that are mainly noncyclic aliphatic with
some aromatic components. Both noncyclic and aromatic hydrocarbons have been
found to be readily gelled by amine carbamate gelling agents; low-molecular-
weight naphthenic hydrocarbons also are readily gelled, but it appears that
this is not the case for the higher naphthenic homologs. Thus, the heavy
CIRCO oil was found to be hardly susceptible to gelation, and therefore all
OHMSETT tests with such oil were cancelled. The light CIRCO oil did gel,
using laboratory samples, although the resulting gel was somewhat weaker in
gel strength than is the case with No. 2 fuel oil or similar commercial oils.
The CIRCO oils were dyed red for greater visibility during the test; the red
dye somewhat obscured the very greatly lightened appearance which normally
accompanies the gelation of undyed compositions.
Weather conditions included rain, high humidity, and strong breezes (13
knots the first day, and up to 20 knots the second). Thus, conditions often
to be expected in open water situations were well represented in the tests.
22
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Figure 9. Pump for delivery of Amine D solution to sprayers.
Berghofer 2-hp, 1740-rpm direct-drive gear-tooth pump used to
deliver Amine D solution to sprayers. Intake is shown from 5-
gallon container of amine solution. Rate of delivery for typi-
cal Amine D solution: 7 gallons/minute. Power is supplied from
OHMSETT bridge at 110 volts.
23
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Figure 10. OHMSETT sprayers in action.
Sprayers are two 6-foot sections of 7/8-inch Schedule 40 PVC
tubing with 1/32-inch holes at intervals of 1/2 inch. Sprayers
are on a "T" mount, and are connected to the Berghofer pump by
Tygon tubing.
In this test, under calm water conditions, a boomed-off area of
12 feet by 117 feet was layered with 79 gallons of CIRCO light
oil dyed red for greater visibility, with a mean depth of 2.3 mm.
Thirteen-knot winds tended to blow oil into patches. In the view
above, 14 gallons of Amine D solution (70% amine) is being sprayed
over the area, for an average concentration of about 15%. Good
lateral coverage was obtained, boom to boom. Longitudinal cov-
erage was hampered by too fast an initial spray rate, with heavy
initial does and light final doses, and also due to patchiness of
the slick due to wind action. Despite these problems, very good
gel formation occurred, as can be seen in Figure 13.
After each operation the sprayer was cleaned with isopropyl alco-
hol. Despite this cleaning, spray holes tended to become plugged
due to amine carbamate forming on exposure of the contaminated
tubing to atmospheric C02 over long periods of time. Based on
this observation, in future tests disposable sprayer assemblies
constructed of the cheap PVC tubing with machine drilled spray
holes were used.
24
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Figure 11. Surface breaker equipment.
Mixing of oil and amine solution using surface breaker as suggested
by Dr. William Garrett of NRL and constructed at the University
of Lowell using 3/8-inch Neotex matting stretched onto wooden
2-inch by 4-inch boards, each 4 feet in length. The surface
breaker was obviously too narrow; an attempt was made to provide
complete mixing as much as possible by repeating the passage of
the rig over the other side of the area which had not been effected
in the first pass.
25
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Figure 12. Application of powdered dry ice.
A plywood hopper was mounted on the moving bridge over the OHMSETT
tank. At the bottom of the hopper a motor-driven longitudinal
grinder/spreader was installed which further pulverized the crushed
dry ice and caused it to be distributed over the spill area pre-
viously treated with Amine D solution (see Figures 10 and 11).
Rate of distribution was controlled by the variable-speed motor.
Moisture from rain, spray, and high humidities caused frequent
disruptions due to clumping of the dry ice granules. A large pro-
portion of the crushed dry ice was not retained on the water/oil
surface, but fell through into the water column.
In each run, from two to three 55-pound bags of dry ice were
crushed and distributed through the hopper.
Despite the unevenness of the distribution, excellent results
were obtained, at least in the calm water tests (in harbor chop
tests, poor boom control resulted in excessively uneven boom
widths and concomitant very poor control in administration of
sufficiently even dose rates of amine solution).
26
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Figure 13. Recovery of gelled oil by means of nets.
Conventional, ungelled oil would be impossible to re-
cover using nets or sieves. (Recovery was also shown
to be feasible by means of mechanical suction devices
floating in the middle of the gelled oil.)
Essentially complete recovery of the oil was observed,
with no residual residues of the red dyed oil notice-
able after the completion of the test.
27
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Figure 14. Sand permeability of gelled versus ungelled oil.
A 30- by 12- by 12-inch aquarium was half filled with dry
white beach sand, with a glass plate dividing the two halves
of the tank, resting in the midsection on the surface of the
sand.
100 ml of dyed No. 2 fuel oil was poured in the left portion
of the tank; 100 ml of gelled No. 2 fuel oil was placed in the
right portion.
The gelled oil remained completely on the surface of the sand,
with no permeation. The ungelled oil permeated the sand
(with, as can be seen, some lateral permeation into the area
underlying the gelled oil). (Time: 5 minutes after pouring,
for both samples.)
28
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The following conclusions were derived from these OHMSETT tests:
1. Although the gelled CIRCO oil was of lower mechanical strength than
that of conventional gelled oils, it did not spread on the water,
but remained controlled in rather rigid patches.
2. The gelled oil was easily recovered, using nets—a capability that
would have been impossible for ungelled oils.
3. The gelled oil was not absorbed onto and into the concrete decks of
the OHMSETT facility. In further tests performed after return to
the University of Lowell, the lack of absorption of gelled oil into
sand was noted (see Figure 14). This could be an important consid-
eration in terms of beachfront protection.
4. Using pressure filtration (1 atm as available, in vacuum filtration),
more than 80% recovery of the oil from the gel was achieved. In sub-
sequent higher pressure (approximately 200 ps.i) filtration systems,
more than 90% recoveries were realized. The oil was free of detect-
able concentrations of Amine D and of Nopol; these gel components
were held in the filter cake. The Amine D carbamate was readily re-
converted to the free Amine by boiling in water, thus liberating
the C02 from the carbamate adduct. The recovered Amine D was deter-
mined to be completely effective in subsequent gelation tests.
5. It was obvious that water in the form of rain, spray and high humid-
ity was quite deleterious to the usage of crushed dry ice as a car-
bamating agent. This, coupled with the obvious problems involved in
procurement and storage, made future use of dry ice a highly infea-
sible feature in the gelation process for use in control and recov-
ery of oil slicks. Future work was thus predicated on the feasibil-
ity of using carbon dioxide in liquid/gas form as is available in
commercial ($2 cylinders and tanks.
BAY "F" TEST I: CARBAMATION BY LIQUID/GASEOUS C02 SYSTEMS
Based on the new requirement for a carbonating system that would not
depend on solid dry ice, work was therefore initiated in January 1978 on use
of pressurized COg cylinders or tanks for this purpose. A test pool was con-
structed at the University of Lowell for preliminary studies toward this end,
and gaseous C02 carbonators were constructed for use with the OHMSETT
sprayers.
As a result of these tests, a final field test was performed at the Bay
"F" tank at the EPA's Edison laboratories. Although considerably smaller
than OHMSETT (the Bay "F" tank was 100 feet long, about 12 feet in width, and
4 feet deep), it presented excellent cold-weather test capabilities. Equip-
ment designed and constructed at the University of Lowell was utilized in the
Bay "F" tests. Excellent results were obtained, and these are presented in
Figures 15 through 17. Conclusions drawn from the Bay "F" Test I exercises
are as follows:
29
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Figure 15. Spraying operation at Bay "F" Test I.
The 12- by 100-foot Bay "F" tank was layered to a depth of 2 mm
with 55 gallons of No. 2 fuel oil. Two OHMSETT-type sprayers
(see Figure 10) were mounted on the tank's moving bridge, as
were two C02 underwater bubblers constructed from 6-foot lengths
of 4-inch Schedule 40 PVC pipe drilled with 1/32-inch holes 1/4
inch apart in five lines 1 inch apart. The pipes were plugged
at each end with a 7/8-inch PVC inlet at the centers. Each carbon-
ator was connected to a Size 1A C02 tank holding 60 pounds of C02
at 830 psi. The regulator of each tank was electrically heated
to prevent freeze-up. C02 tanks, Berghofer pump (see Figure 9),
and Amine D drums were carried on the deck of the bridge. 10.5
pounds of Amine D solution was sprayed on the oil to provide a
16% solution (11% in terms of the 70% Amine D concentration in
the solution).
30
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Figure 16. Carbonation at Bay "F" Test I.
After spraying with the Amine D solution, CC>2 was
bubbled from the carbonating pipes; gelation occurred
almost at once. A total of 80 pounds of C02 tanks.
The theoretical weight needed for 10.5 gallons of
Amine D solution (70% Amine D) is 9.4 pounds of C02.
Again, most of the C02 gas lost to the atmosphere.
31
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Figure 17. Recovery of gelled oil by means of sieve.
The gelled oil was recovered manually by means of a
sieve and was collected in a barrel (not shown in this
view). The recovery was complete, with no sheen on the
water surface. (Some residual oil that was on the
water surface from a previous and unrelated test was
also removed from the surface, with the result that the
water surface was cleaner after this test than it was
before adding 55 gallons of No. 2 fuel oil.)
32
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1. Commercially available liquid C02 in cylinders or tanks (in this
test delivered in gas form) is an excellent carbamating agent with
none of the disadvantages observed in the OHMSETT use of dry ice.
2. Improved Amine D sprayer systems were designed and tested.
3. It was apparent that a two-pass system (with separate phases involv-
ing application of Amine D solutions as a spray, followed by a sub-
sequent pass with application of CC>2) would be infeasible in field
operations. Future tests would thus be predicated on a single-pass
requirement in which spraying and carbonation would be conducted
simultaneously.
4. About 10 times the theoretical requirement for C02 was utilized in
the Bay "F" Test I, with much of the C02 being lost to the atmosphere.
Although C02 is a rather cheap commodity, for large-scale operations
it would be highly desirable to have equipment that would permit max-
imum contact of the C02 with the Amine D gelling agent in the oil,
to minimize reagent payload requirements on the control craft.
OHMSETT TEST II: DESIGN, CONSTRUCTION AND TESTING OF PROTOTYPE
SPILL CONTROL AND RECOVERY EQUIPMENT
Based on the requirements for a one-pass (simultaneous amine spraying and
carbonation) capability, and for equipment that would optimize the contact time
for interaction of the C02 and Amine D, work was initiated in the Spring of
1978 in the design and testing of such systems. We also wished to provide a
capability for large area (approximately 1 acre) coverage in a single pass over
a short interval of time (about 15 minutes or less), with a craft that could
be used in open-water harbor conditions presenting wave heights up to 2 feet.
Most of the preliminary test work on this phase was performed at the
Massachusetts Maritime Academy at Buzzards Bay, Massachusetts, using their.
auxiliary small craft, boat shop and other facilities. A 26-foot motor whale
boat ("Compass Rose") was provided for this preliminary work, and also for
final testing at the OHMSETT facility.
Spraying equipment was substantially the same as for the previously de-
scribed exercises, except that the 70% Amine D solution was held in 17-gallon
beer kegs (eight of these stowed in the forward portion of the boat) with air
pressure from a SCUBA tank utilized to force the amine solution through the
sprayers. Sprayers were mounted outboard from the bow of the boat.
Canvass tarpaulins were stretched over port and starboard frames to pro-
vide carbonator chutes, the role of which was to maximize contact time for the
interaction of amine and CO?, thereby minimizing the amount of C02 required
for complete carbonation. £62 was provided from a 1000-pound (empty weight)
transit tank, laden with 750 pounds of liquid C02, which was delivered in
liquid form by pressure hoses leading to the forward ends of the carbonator
chutes, under water.
An improved portable, hand-operated pressure filter apparatus was con-
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structed and shown to be effective in extracting more than 90% of the original
oil, uncontaminated with amine or nopol constituents, from the gelled oil re-
covered in the OHMSETT exercises.
The results of this test are shown in Figures 18 through 26. The summary
conclusions derived from this test series are as follows:
1. Large spill areas (an acre or more) could be treated and controlled
quickly (within 10 minutes) by use of this craft, which can contain
up to 400 gallons of amine solution and 750 pounds of C02- Complete
recovery of the resulting gelled oil could be effected in about the
same time interval by means of followup craft equipped with suitable
netting gear.
2. Excellent results were obtained in smooth water conditions. Sel
time was 2 minutes or less, and there was a high rigidity associated
with the gel. Recovery by nets was exceptionally easy.
3. For other than smooth water conditions, e.g., in harbor chop condi-
tions, further attention needs to be given to design of the sprayer/
carbonator assemblies. Specifically, the interaction of confused
seas with the bow wave of conventional harbor craft tends to force a
large amount of incoming oil in the intended track of the craft to
either side and away from the reach of the sprayer/carbonator assem-
blies. To avoid this, one solution would be to mount these assem-
blies further forward and further outboard of the craft. Another
suggestion would be to mount intake booms, as are situated on most
skimmer craft, to direct incoming oil more directly into the paths
of the sprayer and carbonators.
4. Although such a craft would be useful in harbor or in similar situ-
ations where storage and maintenance of the craft would present
little problem, a need could exist for a portable spill control and
recovery craft that could be easily assembled and disassembled, and
that could be easily stored and transported in a trailer to remote
spill areas from a central location.
BAY "F" TEST II: DESIGN, CONSTRUCTION, AND TESTING OF
PROTOTYPE PORTABLE SPILL CONTROL AND RECOVERY EQUIPMENT
In this test a small, three-man rubber raft was modified to provide a
small-area spill control and recovery craft that could easily be stored and
transported to remote spill sites. In the small confines of the Bay "F" test
pool, very good results were obtained, suggesting that the craft would be of
use in possible remote spill situations, particularly in inland waters with
little or no wave action.
The raft was equipped with right- and left-side fold-up sprayers (which
could be raised and lowered to accommodate maneuvering requirements in ob-
structed areas) and which were fed from canisters of the type used for dis-
pensing soft drink concentrates in soda fountains. The Amine D solution was
directed into the sprayers from the canisters under pressure from a SCUBA
34
-------
Figure 18. "Compass Rose" underway in OHMSETT tank.
Diesel fuel is laid down in front of boat; amine solu-
tion is sprayed directly in front of canvas chutes;
COg (in liquid form) is introduced under the water in
each chute to convert the oil/amine mixture into
gelled oil. Beer kegs in foredeck of boat contain
amine, under pressure; 1700-pound transit tank in rear
of boat delivers C02.
35
-------
Figure 19. Spraying apparatus on "Compass Rose".
36
-------
Figure 20. Carbonation from "Compass Rose".
"Compass Rose" underway in OHMSETT tank at 2 knots.
Diesel fuel (dyed red for greater visibility) is being
laid down in front of the boat; Amine D solution is
being sprayed over the slick as it enters the carbon-
ator chutes on each side of the boat; C02 (in liquid
form) is sprayed from under the water in each carbon-
ator chute to convert the oil/amine mixture into
gelled carbamate.
37
-------
Figure 21. Gelled oil in OHMSETT tank.
The gelled oil as it appeared in the wake of the
"Compass Rose." Gel time was about 2 minutes.
38
-------
Figure 22. Gelled oil in OHMSETT tank.
The gelled oil as it appeared being pushed down the
length of the OHMSETT tank. The gelled oil was in
the form of rigid plates.
39
-------
Figure 23. Recoveryof gelled oil by net.
40
-------
Figure 24. Portable hand-operated filter press,
41
-------
Figure 25. Filter press in operation.
More than 90% of the original oil was extracted from
samples of gelled oil used in this apparatus. The
extracted oil was free from contamination by Amine D
and Nopol gelling agents.
42
-------
Figure 26. Wave action effects on "Compass Rose" intakes.
Test under way at 2.5 knots with a 1-foot harbor chop.
Wave action caused part of the oil to be swept beyond
the chutes on each side of the boat; therefore, only
that portion of the oil entering the chutes was sub-
jected to carbonation, and the remaining oil was ungelled.
Bringing the chutes forward to a position just abaft the
sprayers should substantially rectify this problem.
43
-------
tank carried on the raft. The canisters were carried in racks slung from the
raft on both sides, which- racks also held CO? bottles of the type used in some
fire extinguishing systems and routinely used for dispensing carbonated
beverages.
In the Bay "F" test, separate passes were performed (i.e., an initial
amine spraying run followed by carbonation in a second pass). For actual
spill situations it was intended that spraying and carbonation would be con-
ducted simultaneously, as was demonstrated on a much larger scale in the
OHMSETT II test with the "Compass Rose." The results of this test are shown
in Figures 27 through 32.
FIELD TESTS AT U.S. NAVAL SUBMARINE BASE, NEW LONDON, CONNECTICUT
Several tests were performed at this activity in late 1980 and early 1981
in attempts to reduce to practice, in actual oil spill situations, the con-
cepts and techniques that had been developed in the previous test programs.
Results of these tests are shown in Figures 33 through 40. The following
conclusions were derived:
1. The small rubber raft developed in the Bay "F" exercise was totally
unsuitable for open water work, particularly with the dual capabil-
ity for spraying and carbonating in one pass. The raft w«is so
overladen that it presented danger of swamping even in small waves
of less than 2 feet in open water.
2. The raft might be considered safe and feasible for use in "mill pond"
conditions as may be encountered in small lakes or other small bod-
ies of water. Even for such conditions, however, it was considered
advisable to'have a sturdier craft with higher freeboard and greater
stability. Further advantage would also accrue from having increased
capabilities for larger spills as a result of the larger capacity
for gelling agents which such a larger craft could carry.
3. In subsequent tests at the Submarine Base, a trimaran (three-
hulled raft) was used with excellent results. This craft was quite
stable in wave conditions up to 2 feet. It is quite sturdy, and can
easily carry up to 2.5 tons of equipment and supplies, in addition
to a crew of five technicians. It is capable of attaining working
speeds of up to 5 knots, which would enable coverage of up to an
acre of oil spill area to be controlled by gellation in approxi-
mately 10 minutes, using gelling equipment and supplies that can be
carried on the trimaran. By installation of appropriate intake
booms at the bow of the trimaran, bow wave problems (such as were
encountered with the Compass Rose involving interaction of the bow
wave with confused seas to cause sweeping of incoming oil to be
swept to either side of the craft) should largely be eliminated.
4. Further work would be desirable to develop a portable trimaran that
could be assembled, disassembled, capable of being stored and trans-
ported with all required equipment and supplies in a small van, and
44
-------
Figure 27. Spraying apparatus in operation at Bay "F" Test II.
The Amine D solution is being sprayed into the oil slick (com-
prised of about 40 gallons of diesel fuel) with 11 gallons of
amine solution being applied. As is typically the case, the
oil is barely visible on the water surface, prior to gelation.
45
-------
Figure 28. Carbonation apparatus at Bay "F" Test II.
After spraying with Amine D solution, the spray cans are removed
and replaced with the C02 tanks and the amine solution in the oil
is subjected to reaction with the C02 bubbling up from below the
surface of the water.
46
-------
Figure 29. Gelled oil at Bay "F" Test II.
After 2 minutes the oil is completely gelled and ready for har-
vesting. Note the greatly enhanced visibility of the gelled
oil, and its immobility in the water, both of which factors are
of great importance in recovery efforts.
47
-------
Figure 30. Herding of gelled oil with screen.
The gelled oil is being herded down the tank using
a screen fixed to a board. Ordinary nets and sieves
are equally effective in collecting the gelled oil.
48
-------
Figure 31. Gelled oil at Bay "F" Test II.
49
-------
Figure 32. Recovery of gelled oil by net.
Removal of gelled oil using a sieve, an impossible task in the
case of ungelled oil. Recovery is virtually complete with this
process, versus maximum efficiencies of less than 80% with
other processes. Recovery time is much less with gelled versus
ungelled oil. The water in this tank was demonstrated to be
cleaner after the recovery effort than it was before the oil
was originally laid down.
50
-------
Figure 33. Loading rubber raft assembly at New London Sub Base.
Loading "Titanic" with C02 bottles and Amine D canisters. In this
view the carbonators and sprayers are folded up.
51
-------
Figure 34. Filling Amine D canisters on raft."
(In this view, the carbonators have been lowered into the water)
52
-------
Figure 35. Rubber raft equipped at submarine base.
53
-------
Figure 36. Rubber raft manned, awaiting boom placement.
54
-------
Figure 37. Raft "Titanic" in operation at submarine base.
55
-------
Figure 38. Another view of raft operation.
"Titanic" spraying and carbonating. One
sprayer has been raised to permit maneuver-
ing in boom area.
56
-------
Figure 39. Trimaran craft at submarine base.
Carbonation and amine is being applied at bow. Spaces
between hulls, under the deck, provide ample contact
time for interaction of amine and CO.
57
-------
Figure 40. Gelled oil from stern of trimaran raft.
Gelation occurred within 5 seconds of initiation of sprayer
and carbonator. Most of gelled oil was collected in 1-inch
mesh net (shown at extreme right). Untrapped oil is float-
ing in water behind the net. Combined spraying and carbonat-
ing operations is thus feasible and successful in open water
situations.
58
-------
capable of gelling and controlling a large spill area quickly and
completely. The use of nets towed behind the craft could enable
simultaneous control and recovery of such spills. (See Appendix I
for data constituting plans for such a craft. The following addi-
tional appendices to this report also contain pertinent information
as is indicated):
Appendix E.I: Submission of Product Listing to Canadian Environ-
mental Protection Service regarding Amine Carbamate Gelling Agents
Appendix G: Report of Oil Spill Control and Recovery Field Tests at
U.S. Naval Submarine Base, New London, Connecticut.
USE OF FLUORESCENT AGENTS AND ACOUSTIC SENSING FOR NIGHT-TIME
SPILL RECOVERY AND CONTROL OPERATIONS
Full-scale research efforts in this direction were instituted in mid-1981,
with extension also to sonic sensing techniques in the Fall. In September 1981
a test was performed on the EPA Ocean Survey Vessel ANTELOPE in Cape Cod Bay;
a report of this exercise is provided in Appendix H to this report. The fol-
lowing observations and conclusions pertain to this on-going work.
1. Fluorescent agents can be applied in the form of sprays of liquid
solutions of such agents, or by dusting with powder formulations.
Current tests strongly suggest that the dusting operation is the
more feasible, although both techniques have proven extremely prom-
ising.
2. Very small (about 50 parts per million) concentrations of fluorescer
in oil or hazardous chemical spills are quite effective in providing
excellent night-time visibility.
3. The best dust formulations appear to be intimate mixtures of the
fluorescer in powdered gypsum (CaS04). The optimum spray formula-
tion appears to be a solution of the fluorescer in di- or tri-
propylene glycol monomethyl ether solvents.
4. Uvitex OB (Ciba-Geigy Corp.) and Yellow 131SC (Morton
Chemical Co.) have proven to be excellent nontoxic, cheap, and
highly effective fluorescers. (See Appendix C.I for a description
of the low toxicity of Uvitex OB.)
5. Use of the fluorescence system is not confined to petroleum mate-
rials. Specifically, al_l_ organic chemicals cited in Figure 42 as
being most frequently involved in transportation incidents are com-
patible with the fluorescence system.
6. The gypsum powder base is entirely nontoxic and with no fire or
other hazardous effect. Glycol ether solvents have very low fire
and toxicity effects, and in the concentrations contemplated for use
would probably present no significant hazard. (See Appendices E and
J for additional information regarding features and developments
59
-------
'•>•" •*r~*-~s£j~%-v"-*~*?"? '-•
'^ •- •::.'&&£'**- '-- .,;'•: •:
-••**.-*• '-'*' '"''. " '
- .-'. .- T* >?(IT^'J:,- ;^^^C^^^^ •'"'v ' ' "
.-. ,.?.:..--»- .,-.
7
*
,--_> ^.ife
Figure 41. Use of fluorescent agents and acoustic sensing for
night-time oil spill recovery and control operations.
60
-------
Certain chemicals are most frequently involved in transportation incidents
AHmodo* Wghwor
Commodity
Paints, anamal, lacquar, and stains
Corroslva liquid*
Wat battarias
Flammabla Uould*
Paint ramovar
SuHurlcadd
Hydrochloric acid
Etoctrolyta battary fluid
Plastic and rasui solutions
Flammabla or poisonous Insactlcldas
Ink
Alcohol*
Phosphoric acid
SoOiuRt hydfoxiOvi
Adds*
Anhydrous ammonia
Nitric acid
Solvants*
Corroslva solids*
Comprassad gasas*
Radtoaetiva malarial*
Mathanol
Rust pravantars and ramovars
Acatona
Xywfio
DootM
0
12
0
5
0
2
0
0
0
0
1
0
0
2
1
13
4
0
0
2
0
0
0
0
1
Subtotal 43
All other hazardous material* 168
TOTAL 211
0 Hot tttlorwiM woeHiod. Note (Mo or* lor nponod MeUomt.
tntuit** IncMonl* DoolM kl|urim
28
306
23
211
60
422
104
5
12
28
0
13
32
178
79
404
82
4
56
62
2
10
1 '
4
7
2133
3180
5313
13.304
7.959
5.429
3.076
2.828
2.218
1,760
1.310
1.206
894
829
760
671
635
573
470
437
374
370
512
377
350
266
219
216
47,043
22.988
70,031
0
10
0
5
0
2
0
0
0
0
1
0
0
2
1
12
1
0
0
2
0
0
0
0
1
37
128
165
rwwxn
26
263
20
188
59
212
76
5
11
25
0
8
11
120
35
265
'76
4
28
61
0
7
1
0
3
1504
1740
3244
man
kwMonU
13,075
7.660
5.334
2.763
2.781
1.555
1.502
1.273
1.138
876
819
626
278
451
537
129
395
349
350
465
262
236
265
171
178
43,468
19,790
63.258
Mollwor
DoolM ln|ur.»» Ineidom*
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
3
39
42
0
35
0
19
1
210
28
0
0
3
0
4
21
54
44
139
2
0
0
1
0
3
0
3
0
567
1264
1831
57
235
29
224
17
639
237
17
30
13
3
92
384
173
25
336
31
13
15
28
7
1C6
0
38
29.
2778
2671
5449
22 CAEN Nov. 24, 1980
Figure 42. Compatibility of chemicals with fluorescence
and sonic sensing techniques.
Compatibility of chemicals most frequently involved in trans-
portation incidents with fluorescence and sonic sensing tech-
niques. All organic chemicals cited above are compatible.
61
-------
pertinent to the fluorescence system.)
7. Underwater sonic sensing techniques were shown to have excellent
synergistic effects when used with the fluorescence techniques.
Both techniques would be excellent when used on a stand-alone basis.
Sonic sensing is particularly invaluable in situations in which a
need exists to determine the rate of dissipation of oil into the
water column. (See Appendices F and 0 for additional information
regarding features and developments pertinent to sonic sensing
techniques.)
Figures 43 through 53 discuss developments in sonic sensing and fluores-
cence techniques. Our group believes that these new techniques represent pow-
erful supplements to oil and hazardous chemical spill recovery and control
efforts.
62
-------
Figure 43. Commencement of fluorescence test.
OHMSETT crewman is shown here applying fine spray of Ciba-Geigy
Uvitex OB C\% solution in cellosolve solvent) to diesel oil
slick. Treated oil slick was then allowed to stand for about
5 hours before further observation (see Figures 25 and 26).
63
-------
Figure 44. Results of fluorescence test.
Time: 8:30 PM, August 1, 1979. OHMSETT tank surface illuminated
by longwave (366 nm) UV radiation from a battery of four 4-foot
fluorescent "black light" UV tubes from the OHMSETT bridge, about
4 feet above the water. That portion of fluorescer which encount-
ered oil patches remained in the oil to the extent that night-time
visibility of the oil was readily effected. That portion of the
fluorescer which encountered only open water was distributed into
the water column, to the extent that fluorescence was imparted only
to the oil patches and not to open water areas.
64
-------
Dimensions: 22" diameter (rvtx.)
190" length
660 Ib. empty weight
90 gallon capacity
Bomb Lugs
(30" centers)
AERO I4B AIRBORNE SPRAY TANK
AERO I4'B COMPONENT
CONTAINER
AERO I4B SPRAY TANK
TESTER .
AERO I4B CENTER SECTION
CONTAINER
AERO I4B AIRCRAFT
WIRING TEST BOX
Figure 45. EDO Aero 14B airborne spray tank (and auxiliary equipment)
This military equipment is an ideal apparatus for spraying liquid
agents and would be particularly well adapted for the fluorescent
sprays contemplated for use in this study. It has a capability
for heating the liquids in cold weather situations, and provides
high accuracy.
65
-------
Figure 46. Another view of EDO spray tank.
(The nose cone has been removed for inspection of
spray tank controls.)
66
-------
Figure 47. Commencement of fluorescence dusting test.
80-square-foot test pool immediately after application
of 250 ml of mineral oil. Estimated thickness of patches
of oil produced was about 0.6 mm.
67
-------
Figure 48. Dusting with fluorescent powder.
Dusting with f"luorescer/CaSfty (2%) formulation to provide
estimated 75-ppm concentration of fluorescer in oil.
68
-------
Figure 49. Results of fluorescence test.
Surface of tank, with each patch of oil glowing with
yellow fluorescence induced by UV -illumination. Fluor-
escence was much brighter than is indicated in this
Polaroid photograph.
69
-------
7$f&%^^'T
S^*w?.7">'\ . ; ,-.
&Rg£&vMv yv .-.> •<: .
Figure 50. Cropdusting by helicopter.
Helicopter delivery of a dry-mix agent (in this case,
delivery of fertilizer over Mt. St. Helens area). Similar
delivery patterns are observed in aerial spraying opera-
tions.
70
-------
Figure 51. Breakup of ARGO MERCHANT
December 19, 1976 (NOAA/USCG photo)
Figure 52. Oil slick from ARGO MERCHANT
December 19, 1976. Attempts to keep track of, and to pre-
dict the course of this spill (as has been the case in
many other instances) were severely handicapped by the
inability to observe this slick during the long winter
night hours. (NOAA/USCG photo)
71
-------
Figure 53. EPA ocean survey vessel ANTELOPE.
EPA OSV ANTELOPE, operating from Annapolis, Maryland. OSV
ANTELOPE is utilized by the EPA for environmental research
and surveys on inland, coastal, and open waterways. Fluores-
cence and sonic sensing tests were conducted by this group on
board the ANTELOPE in September 1981; future work of this
nature is contemplated, again on board the ANTELOPE.
72
-------
REFERENCES
1. a. Study of Equipment and Methods for Removing Oil Slicks from Harbor
Waters. Battelle Memorial Institute, Pacific Northwest Laborator- '
ies, Report No. CR-7-001. Prepared under Contract N62399-69-0023
for the Department of the Navy. 1969.
b. Chemical Treatment of Oil Slicks. U.S. Department of Interior,
FWPCA, Water Quality Laboratories, Edison, New Jersey. March 1969.
c. Control of Oil and Other Hazardous Materials. Training Manual,
U.S. Environmental Protection Agency, Office of Water Programs.
September 1972.
d. Chemical and Engineering News. September 7, 1970, p. 48.
e. M.A. Poliakoff. Oil Dispersion Chemicals. Edison Water Quality
Laboratories, FWPCA, Edison, New Jersey. 1969.
f. G.P. Canevari. General Dispersant Theory. Proc. Joint Conference
on Prevention and Control of Oil Spills. API-FWPCA. December 1969.
g. T. Murphy and L. McCarthy. Evaluating the Effectiveness of Oil
Spill Dispersants. ibid. 1969.
2. a. JBF Company. U.S. Patents 3,716,142 (1971) and 3,804,251 (1974).
b. Chemical and Engineering News. May 15, 1972. p. 12.
c. References (1) (a,c).
d. Compressed Air Magazine. June 1974. p. 15.
3. a. Proc. Joint Conference on Prevention and Control of Oil Spills.
pp. 221 ff.
b. Oil Spill Treating Agents - Test Procedures: Status and Recommenda-
tions. BatteHe Memorial Institute, Pacific Northwest Laboratories.
Prepared under Contract 212B00083 for API. May 1, 1970. pp. 20 ff.
c. Proceedings, Industry Government Seminar. Oil Spill Treating
Agents. API/U.S. Department of the Interior. April 8-9, 1970.
pp. 95-97.
73
-------
d. Oil Spill Treating Agents - Selection Based on Environmental Fac-
tors. Battelle Memorial Institute, Pacific Northwest Laboratories.
Prepared by A.D. Little Co. for API. October 1970.
e. Chemical and Engineering News. January 24, 1972. p. 12.
4. M.K. Breslin and M.D. Royer. Use of Selected Sorbents and Aqueous Film
Forming Foam on Floating Hazardous Materials. EPA-600/52-81-211. U.S.
Environmental Protection Agency, Cincinnati, Ohio. October 1981.
5. W.W. Bannister, W.A. Curby, and J.A. Pennace. U.S. Patents 3,684,733
(September 18, 1970), and 3,880,569 (April 29, 1975).
6. W.W.- Bannister. Gelation of Oil Slicks by Amine Carbamates as an Adjunct
to U.S. Navy Oil Spill Recovery Operations. Report prepared under Con-
tract N00014-76-C-0340 for the Office of Naval Research. DDC acquisition
code 202-274-7633.
W.W. Bannister. New Amine Carbamate Gelation Techniques for Use in Oil
Spill Recovery Operations, Report prepared under EPA Project No.
R804628 0.
W.W. Bannister, J.D. Rancourt, W.A. Curby, U. Frank, and C. Aguilar.
Marine Technology. October 1980. pp. 146-149.
7. P.B. Ghosh and M.W. Whitehouse. Biochem. J_^ 108_, 155 (1968).
8. U. Frank. U.S. Environmental Protection Agency, Municipal Environmental
Research Laboratory, Edison, New Jersey. Private communication.
74
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APPENDIX A
AMINE D™ AND ITS DERIVATIVES BULLETIN OR-132C
HERCULES
TECHNICAL
DATA
AMINS D™
AND DERIVATIVES
BULLETIN OR-132C
(Supersedes PC-132B)
AMINE D, AMINE D ACETATE 70%. AND AMINE D ACETATE SOS
AMINE D™ is a mixture of related primary amines derived from a modified
rosin. It can be described chemically as a technical grade of dehydroabietylamine,
the dominant amine comprising it. Amine D readily undergoes the usual chemical
reactions of primary amines. For use in aqueous systems, it can be converted to
the acetic acid salt, which is totally soluble in water. For the convenience of
those who may not have facilities to convert to the acetate form. Hercules
offers AMINE D ACETATE 70% and AMINE D ACETATE SOS, a 70 percent
solids aqueous paste and a 50 percent solids aqueous-alcoholic solution of this
salt, respectively.
This bulletin describes typical uses for Amine D and several of its deriv-
atives, and presents detailed information on their physical and chemical prop-
erties. Toxicity and handling precautions are also included. Indicated appli-
cations include use as surface-active agents, corrosion inhibitors, additives for
asphalt, industrial preservatives, chemical Intel-mediates, and flotation reagents.
A separate bulletin covers the Polyrad® series of ethylene oxide adducts of
Amine D. This family of products is especially effective as inhibitors for acid-
induced corrosion, particulary for hydrochloric acid.
75
-------
OR-132C
TYPICAL USES
Asphalt Additives
Amine D and its acetate salt are useful antistripping agents to improve or pro-
mote adhesion of asphalts to stone aggregates used in road construction or repair.
They are more effective for improving binding of cutback asphalts to siliceous
materials than to basic aggregates such as limestone. Generally, 0.5 to 1.25
percent of the amine or amine derivative is required, depending on type of
asphalt and aggregate to be coated.
Chemical Intermediates
Amine D is a technical grade of the primary amine dehydroabietylamine, and,
as such, is a very reactive chemical. It is used by Hercules and others for man-
ufacture of acetate salts. Many other potentially useful derivatives (see section
Chemical Reactivity under Chemical and Physical Properties of Amine D) can
be made.
Corrosion Inhibitors
Reaction products of Amine D with ethylene oxide (Polyrad products) are
highly effective corrosion inhibitors for hydrochloric acid used in chemical
specialties (bowl cleaners), industrial cleaning, and oil well acidizing. These
water-soluble inhibitors are especially useful in petroleum refinery streams for
reducing corrosion of equipment by hydrogen sulfide, hydrogen chloride, carbon
dioxide, and organic acids. In addition, these materials act as detergents in
loosening and dispersing scale-forming materials present in refinery systems.
Information in greater detail on Polyrad products is available in other Hercules
literature.
Flotation Reagents
The acetate of Amine D is an excellent collector for silica and silicate minerals.
It is used primarily in the beneficiation of nonmetallic ores such as feldspar,
quartz, phosphate rock, and cement rock. It is useful also, alone or in con-
junction with other reagents, for the beneficiation of iron oxide and other
metallic ores. More detailed information on flotation applications of the acetate -
salt is available in another Hercules publication.
Preservatives
The pentachlorophenol salt of Amine D is a very effective ingredient of pre-
servatives used in emulsion paints; wood-treating compounds; and cordage, felt,
fabric, and paper that are not exposed to sunlight. The pentachlorophenate is
neither manufactured nor sold by Hercules, but can be readily made by hot
fusion of the above materials. A description of this derivative follows.
The pentachlorophenol salt of Amine D, which is sometimes referred to as
technical dehydroabietylammonium pentachlorophenoxide, is a dark amber,
brittle, resinous solid. Softening point of a typical sample is 104°C; specific
gravity at 20/20°C is 1.288. Vapor pressure of the pentachlorophenate is
approximately one-tenth that of pentachlorophenol itself. The pentachloro-
phenate of Amine D is readily soluble in polar-type solvents such as pine oil, and
in various aliphatic and aromatic hydrocarbons.
76
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OR-132C
CHEMICAL AND PHYSICAL
PROPERTIES OF AMINE D
Amine D is a mixture of high molecular ., . _u ML1
n3vs >^ .^Un-Nn-
weight primary amines derived from the
resin acid constituents of a modified
rosin. They are mainly stabilized abietyl-
amines, the predominant one being de-
hydroabietylamine whose structural con-
figuration is shown at the right. Typically.
Amine D contains around 92 percent
total amines of which about 3 percent are related secondary amines. It is a clear,
yellow, viscous liquid having a faint ammoniacal ordor. Other physical and
chemical properties are shown below.
Typical Properties of Amine D
Amine D
Color, Gardner
Specific gravity at 25/15.6°C
Refractive index at 20°C
Pounds per gallon at 25°C (kg/I)
Viscosity, poises at 25°C
Flash point, 6F(°C)
Neutralization equivalent
Secondary amine content, %
' Total amine content, %
Solubility - For all practical considerations, Amine D is insoluble in water.
For example, solubility in water is less than 0.5 gram per 100 grams of water
at 100°C. However, it is soluble in common organic solvents, including alcohols,
ethers, hydrocarbons, and chlorinated solvents. For use in water or with aqueous
systems, the amine can be reacted with acetic acid to form a water-soluble salt.
Hercules offers the acetate salt of Amine D as a convenience to users who prefer
to purchase rather than make the salt themselves.
Stability to Heat and Storage - Amine D is quite stable to heat below 100°C.
Above this temperature, gradual decomposition occurs and increases as the
heating time and temperature are increased. This is illustrated by the following
data, on page 4, obtained on a typical sample of Amine D.
77
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OR-132C
Time of Heating
(days)
1
3
7
1
3
7
7.5 hours
Temperature,
°C
100
100
100
150
150
150
203
Weight Loss of Amine D
During Heating, %
1.1
2.2
3.2
10.5
18.0
35.4
14.9
The viscosity of Amine D decreases sharply with increase in temperature.
When cold it is very viscous, but on warming it becomes sufficiently fluid to
pump or otherwise transfer without difficulty.
Most metals are unaffected by Amine D under normal conditions of con-
tact and storage. Laboratory tests showed no effect on black iron, stainless
steel, Monel, copper, nickel, tin, zinc, or aluminum at room temperature. At
300°F (1498C), Amine D caused slight corrosion (approximately 2 mils per
year) of black iron, Monel, nickel, tin, r.nd zinc, but had no effect on stainless
steel, aluminum, or copper.
Surface Activity — Amine D facilitates the wetting of siliceous surfaces, as
illustrated by the contact angle measurement data that follow:
Test Sample
Mineral spirits alone
Mineral spirits + 0.1% Amine D
Mineral spirits + 1.0% Amine D
Mineral spirits + 5.0% Amine D
Contact Angle Against Glass
Immersed in Water (average value)
131°
114°
96°
77°
These tests were made by releasing drops of solution of Amine D in min-
eral spirits beneath glass plates submerged in water, in a horizontal -position,
and measuring the contact angle directly with a microscope. The smaller the
angle, the greater the wetting.
Chemical Reactivity — Amine D offers manufacturing chemists an unusual, high-
purity, high molecular weight amine. As a chemical raw material or intermediate,
it may be considered to be a technical grade of dehydroabietylamine, a con-
densed-ring-structure, partially aromatic primary amine whose structure is shown
on page 3. It undergoes the many and varied reactions commonly associated
with amines of this type. A few examples are its reaction with acids to produce
amine salts, with alkyl halides to produce secondary and tertiary amines and
amides, and with anhydrides to form imides. On the following two pages, in
equation form, are other potential chemical reactions to which Amine D can be
applied.
Particularly valuable derivatives of Amine D are the simple salts formed by
reaction with carboxylic acids and acidic phenols. Examples are the salts of
acetic acid and pentachlorophenol. The commercially available acetates of
Amine D are discussed on page 7.
78
-------
OR-132C
Possible Chemical Reactions of AMINE D (RNH2)
Product:
AMINE SALTS
^SUBSTITUTED AMINtS
(I) Secondary Amines
02) Tertiery AninM
(3) Quaternary Silu
(4) /V-MethylolimiM
(8) Jir.Hvdroxyethyleted
Amines
(6) /V-CarboiyalkyUud
Amines
(7) N-Sul/oelkytated Amines
(8) Ar.Cyanoalkyl«lcd Amine*
ISOCYANATES
Fron RMction of
RNH, With:
>. Mineral Acid.
b. Csrboiylic or
Sulfenk Acid.
c. Stronfly Acidic
Phenols
.. Alky! or Arolkyl
Holides
b. Alkylene Holides
c. OMns
1. Alkyl Holidos
b. Formaldehyde plus
Formic Acid
Alkyl HalidM
Formaldehyde
Ethylono Oxido
>. a/B*o-Chlon> Acid.
b. OMo-PropialoctoM
Hlloalkybulfonic Acid.
Acrylonitrik
PhMfOIW
Accordinf to Thow Equations:
RNH, + HCI -» iRNHspO '
t RNH, •>• H«O, -> IZRNH.I * * |so.]~ ~
RNH, + CH.COOH -» |RNH,|* |CH£OO|"
•cMK.cid Amiat* >otUt*
RNH, + p-CH.C&SOM -» (RNH,n»-CH^:ji^O,r
p-tolucnrwilfonie
•cid
RNH, + CI,CX>H -» |RNH,| *\cucaT
PMIU- Ammo • ptnuchlarophoiiMc
RNH, -r CH,I -* lRNH,CH,rr
methyl moiwomino Mlt
iodide
RNH, * CM,CHf.\ -* |RNH,(CJl^:H,)]*a"
bonxyt moiwomino smlt
chloride
2 RNH, + CICH^HrCl — > !RNH^H<;H,NH,Rp*[2Cl|
ochylcnc dumino oilt
chloride
RNH, + CH.-CHCH, -* RNHCHlCH,),
propene
RNH, » 2 CHJ -» |RNH.CH,),rr + HI
RNH, + 2 HCHO •>• 2 HCOOH — * RNtCH,)t + 2 CO, -r 2 H|O
RNH, + 3 CH,I — «• jRNtCH,),!"!' +. 2 HI
RNH, * HCHO -» RNHCH^DH
RNH,- H.C — CH, -> RNHCHfHAH
t—O — 1 AT-hydrosyethyl Amini •
RNH, 4- 2 H,C CH, -* RNiCH^H-OHl,
1 — O — 1 N. .V-buihydroiyethyl) Amine o
RNH, »nH^r CH, — c RN| CH,CH.O),,.,CH,CH;OH:,
: — O — 1 N, W-baihyrtroxypolyetho. y«thyl 1 Amine •
RNH, - CICH.COOH - 2 N.OH — » RNHCH^COONt - N.C1 - 2 HO
RNH, - CH,CH,C-O — » RNHCHjCH^COOH
1 O ' A^iubitituted Mo-• RNHCH,CH,SO,N. - N.Br + 2 K-J
2'bromoethyl-
•ulfonic acid
RNH: - CH.-CHCN — > RNHCH:CH^N
RNH, .HCI -r COCI, — » KNCO + 3 HCI
•AMINE D.
79
-------
OR-132C
Possible Chemical Reactions of AMINE D(RNH2)
Product:
AMIDES AND IMIDES
N-SUBSnTUTED UREAS
A-SUBSTm-TED
THIOUREAS
CHLORAM1NE
METAL COORDINATION
COMPOUNDS OR AMINES
PHOSPHONIUM
COMPOUNDS
SCHIFF-S BASES
ISONITRILES
From Reaction of
RNH, With:
a. Anhydride! of
(1) Monocarboiylic
Acid.
(!) Diearboiync Acida
b. AcylHalidea
c. Diathyl Oxalate
a. Pounium CyanaU
b. Isocyanatea
c. Urea
Carbon DisuUde
Hypochioroua Acid
Metal Salt*: acetates.
Milfatea. nitrate*, and
chtunde* of Cu. Zn. Ag,
Ni. Mn. Co. H|. Ca. Fe.
AL and Cr
Phoepnoryl Chloride
a. Aldehydes
b. Ketonea
Chloroform
Accordinf to Theee Equations:
RNH, +• (CHCOirO -> CH-CONHR + CH.COOH •
acetic
anhydride
RNH. + O-CCH-CHC.O -» RNHCOCH-CHCOOH
1 O ' t heat
maleic anhydride O - CCH - CMC - O + H,O
1 NR 1
imide
RNH, + 0-CCJi.C-O -> O-CC-H.C..O + H-O
1 — O— 1 -LNRJ
phthaUc imide
anhydride
RNH, -r CH:COCI — » CH.CONHR - HCI
ac«>l
chloride
RNH, + Cm£0,Cl — » C.H30.NHR + HCI
benzene* sulfonamide
aulfonvl
chloride
RNH, » HiCiOOCCOOCSH. — » RNHCOCOOT.H, ^ CsHiOH
\ mnnoomide
RNH, - KCNO +. HCI— > RNlTcONH, , KCI
RNH, - R'NCO — > RNHCONHR'
iR'-alkylocaryl)
RNH, * H:NCONH, — » RNHCONH, * NH,
2 RNH, * H,NCONH, — » RNHCONHR * 2 NH,
2 RNH, - CS, —> iRNH.i '(RXHCSSf
r heat
RNHCSNHR - H-S
tuted thiourea
RNHt - HOCI — » RNHCI - H.O
2 RNH, * .CH.COO :Cu — * |Cu HNHv.hCH.COO.,
2 RNH, -r ZnCI, — » Zn.RNH, ..,,C1,
RNH, -, POCI, -* RNHPOC1: - HCI
RNHPOCI, - RNH, -> (RNH -POC! + HCI
RNH>,POCI -RNH, — »
-------
OR-132C
CHEMICAL AND PHYSICAL PROPERTIES
OF AMINE D ACETATE
The acetic acid salt of Amine D is commercially available from Hercules as
Amine D Acetate. Two concentrations are offered: a 70 percent solids aqueous
paste and a 50 percent solids aqueous-alcoholic solution. Properties of these
products are shown below:
Properties of Amine D Acetate
Amine D Acetate
70% SOS
Solids content, % 70 50
Water content, % 30 39
Isopropyl alcohol content, % — 11
Specific gravity at 25/15.6°C 1.036 1.017
Pounds per gallon at 25°C (kg/I) 8.630 (1.04) 8.460 (1.02)
Viscosity at 25°C, poises solid paste 1.070
Flash point, Tag. open cup, °F (°C) - 140(60)
Freezing point, °F (°C) - 15 (-9)
Solubility — Amine D Acetate is quite soluble in water and lower molecular
weight alcohols. Its solubility in most other organic solvents is not us great.
In very hard waters, the presence of ions such as phosphate, chloride, and sul-
fate causes cloudy solutions. In waters of normal hardness, dilute solutions of
the acetate (0.01 to 1 percent) may frequently be hazy, but higher strength
solutions of from 1 to 50 percent are generally clear. Fifty percent concen-
trations are about the limit of solubility of the acetate in water at room temper-
ature.
NOTE: The 50 percent solids commercial form of this acetate is
readily diluted with water to lower concentrations. The most sat-
isfactory dilution procedure for the 70 percent solids product, which
is a heavy paste, is as follows: (1) add 1 part of water to 1 part of
the paste and stir until mixture is uniform; (2) let stand 24 hours,
after which the fluid paste can be readily diluted to any desired lower
concentration.
Stability to Heat and Storage - The water- and alcohol-free acetate of Amine
D is stable to heat below temperatures of around 90°C. Upon prolonged heating
at higher temperatures, it is converted into the free amine and acetic acid, or
to an N-substituted acetamide when the acetic acid formed cannot readily
escape. For example, in a closed system, when a sample of the acetate of
Amine D (100 percent solids) was heated 65 hours at 65°C, no change in compo-
sition occurred; when heated at 165°C for 1.5 hours, this salt was converted
completely to an acetamide.
81
-------
OR-132C
Stability to Air and Sunlight - A characteristic of high molecular weight pri-
mary amines and their salts is susceptibility to oxidation when thin films on
various substrates are exposed to air in the presence of sunlight. Sunlight cata-
lyzes the oxidation. In the absence of sunlight, oxidation is negligible. The
acetate of Amine D, being a high molecular weight primary amine salt, also
has this characteristic.
Surface Activity - The acetate of Amine D has definite surfactant properties.
It shows marked wetting activity on siliceous surfaces. In aqueous solution,
Amine D Acetate is adsorbed by cellulose fibers, threads, and fabrics, and, after
drying, is not readily removed by subsequent washing. Also, the wetting time
of cotton, as measured by the Draves method, is markedly decreased by the
presence of small amounts of this salt in the water.
The following data illustrate these wetting properties, and show how
surface tension and interfacial tension between water and organic liquids are
decreased by the presence of this acetate:
Amine D Acetate
(concentration in water, %) 0 0.01 0.10 0.15 0.175 0.20 0.50 1.00
Surface tension,
dynes/cm at 25°C 72.1 55.4 37.7 - - 33.4 33.4 -
Interfacial tension
(isooctane-water),
dynes/cm at 25°C 47.5 - 9.2 - - - - 0.9
Wetting speed,
Draves method
(cotton), sec - - 180 50 18 9 - -
TOXICITY AND HANDLING PRECAUTIONS
Like most amines and their salts, Amine D and the acetate, although of rela-
tively low toxicity, should be handled with care. These products may cause skin
irritation. Avoid prolonged or repeated contact with the skin.
Dermatological studies indicate that Amine D and certain of its derivatives
are not skin sensitizers. At concentrations below 0.5 percent, they do not act
as primary irritants even on prolonged exposure to the skin. However, concen-
trated solutions or the undiluted material on prolonged exposure do act as pri-
mary skin irritants, just as do many other amines and their salts.
If accidental contact is made with the skin, wipe off at once. In the case of
Amine D, apply vinegar or a 5 percent solution of acetic acid and follow with
thorough washing, using mild soap and water. The acetate salt form should be
removed promptly by first washing with water followed by thorough washing
with mild soap and water.
Should these products contact the eyes, immediately flush with plenty of
water for at least 15 minutes; get medical attention. If spilled on clothing, re-
move and wash before reuse.
82
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APPENDIX B
TOXICITY OF HERCULES AMINE D TO MARINE LIFE
In an attempt to determine the nature of the toxic substance
or substances in Amine-D and #2 fuel oil mix, several experiments
were conducted. Using the barrier tank apparatus described in
our previous report (see attached), one ml aliquots of #2 fuel
oil with 3% ethanol added were mixed with artificial seawater
to make up one liter final volume. Any one of five Fundulus
heteroclitus taken from the holding tank was checked at random
for normalcy and the other four were placed in the test tank.
At the end of two hours, the fish were sacrificed, and blood
from the caudal artery was analyzed electronically. Standard
slides for microscopic evaluation were also made. Differential
blood counts and photomicrographic images were prepared from
each slide. Figure (A ) shows a photomicrograph taken of a
blood slide from a control sample fish (swimmining in a barrier
tank, in one liter of artificial seawater). Figure (B ) shows
the change in the blood cell population of F. heteroclitus
subjected to 970ppm of #2 fuel oil in artificial seawater for
2 hours. Our previous work showed that F. heteroclitus
specimens were able to withstand 5-10ppm of Hercules Amine-D
(solubilized with 3% ethanol) in artificial seawater for 24
hours without exhibiting any untoward reactions, and that they
83
-------
could withstand the mix of the Amine-D, ethanol and #2 fuel
oil in low concentrations 10-20ppm in artificial seawater for
24 hours. In this latter case, however, the electronic mon-
itoring showed that the blood cells had been altered. In
our final experiments, therefore, we stressed the system and
looked at the acute toxic effects of the Amine-rD/ethanol and
the Amine-D/ethanol plus #2 fuel oil mix in 688ppm concentra-
tion respectively.
Differential blood counts done on all samples showed that
the erythrocyte: lymphocyte: thrombocyte: granulocyte ratios
did not change significantly, The electronic patterns and the
optical microscope observations showed that the erythrocytes
were effected, moreover, fish on both sides of the barrier
which keeps the insoluble chemicals available to only one half
of the fish in the sample were effected similarly, thus indic-
ating that the toxic chemical or chemicals are seawater soluble,
Table 1 summarizes the survival data and the chemical
insults that test populations of F. heteroclitus were subjected
to Amine-D was added directly to the blood of^F. heteroclitus
as a second type of control. Amounts of Amine-D in saline
ranging from 33ppm to full strength were used. All blood
cells were altered regardless of the concentration, however,
the effect was similar to the results seen in Figure ( B),
viz. an elongation of the blood cells with little or no cell
membrane damage.
Acute toxic reaction in fish swimming in artificial sea-
84
-------
water containing ethanol, Amine-D alone or in combination with
#2 fuel oil effected the blood cell membrane in a manner similar
to that seen in chronic copper (II) toxic reactions. The sur-
face of the membrane loses its selective permeability and
spots appear faily evenly distributed over the cell surface. A
difference between the two reactions does exist. In the case
of the Amine-D reaction, the ratios of the formed elements in
the blood do not appear to change. This indicates that the
mechanism of action is different from that seen in F. hetero-
clitus subjected to copper (II) ions. The lethal interval also
is interesting for Amine-D toxicity because it suggests (when
combined with earlier data) that the soluble toxin is in the
Amine-D and may be a contaminant. We have a minimum of infor-
mation sufficient to relate the lethal interval to the Amine-D
concentration regardless of whether the amine is combined in a
gel, in a free mix with #2 fuel oil or solubilized in a small
amount of ethanol follows a relationship which can be pre-
dicted from Graph (1). Amine-D concentrations of less than
20ppm appear to be able to be handled by the fish as easily
as the fuel oil itself and, in fact, cause alterations in the
blood similar to that seen in Figure (B ).
If, as we conclude from the data, it is a soluble con-
taminant in the Amine-D that is causing the observed toxic
response, then further testing will prove the fact. Regard-
less of the toxin, however, in Amine-D concentration levels
of 20ppm or less can be accepted as safe. The concentrations
85
-------
of Amine-D used to incorporate into an oil spill at sea will
be mixed with a volume of water sufficient to lower the con-
centration of the toxin to a safe level at less than 2 feet
below the seawater surface even under the condition of no
mixing.
86
-------
Fig. A. Normal red blood cells show the characteristic eliptical
shape and smooth, rigid membrane. Nuclei in these cells are not
as clearly defined as those in the experimental cells.
Fig. B. Red blood cells from fish exposed to the oil/EtOH
mixture show large deviations in cell width, with most cells
being much narrower than normal.
87
-------
Fig. C. Nuclei appear to project from the cells (A)
shedding of the cytoplasm (B) is evident.
and
Fig. D. Isolated nuclei (A) of red blood cells; some cells show
a loss of cytoplasm exhibited by clearing rings (B) around nuclei,
88
-------
-•• •• • ••• -•-.-
Fig. E. Cytoplasmic membranes show breaks and loss of rigid-
ity (A) in RBC's from the oil/Amine D/EtOH experiments.
Fig. F. Red blood cells from fish exposed to amine-D/EtOH show
a loss of rigidity of the cytoplasmic (A) and nuclear (B)
membranes. Folds and projections of the membrane resemble
psuedopods (C).
89
-------
Fig. G. Cytoplasmic membranes take on a scallop shape as the
projections begin to develop.
Fig. H. Vacuoles or engulfed particles appear (A), possibly
taken in by pseudopodic action.
90
-------
TABLE I
Reference
Figure
1
2
3,
4.
5
6.
7,
8
Lethal
Application
(min.)
--
--
100
30
TEST ENVIRONMENT
Artificial
Seawater
(ml)
1,000
999
999
999
Number 2
Fuel 011
(ml)
--
0.97
0.92
—
Hercules
Amine-D
(ml)
--
--
0.056
0.688
Ethanol
(ml)
-.
0.03
0.024
0.312
RANDOM 300 COUNT OF BLOOD SAMPLES
Erythrocyte
293
292
293
290
Lymphocyte
2
2
3
3
Thrombocyte
5
6
3
7
Granulocyte
„„
--
1
«
-------
vo
N>
\
t
«i
a
I
Graph 1. Lethal Interval for Fuadulus heteroclitua .,,
subjected to acute Insult of Anine D (TH, Hercules, Inc.) '!!:
In sea Mater.
90 100 110 120 130
100 -
0 -
10 20 30
-------
APPENDIX C
TOXICOLOGY DATA SHEETS
TOXICOLOGY DATA SHEET
UVITEX OB™
Classification:
Synthetic organic fluorescent whitening agent.
Animal Toxicology;
Acute:
Oral - rat
LD5Q 10,000 rag/kg
Primary skin irritation - rabbit
Non-irritant (Draize score 0/8)
Eye irritation - rabbit
Non-irritant (score 0/110)
Skin sensitization - guinea pig
Not a sensitizer (O.lJ suspension in saline)
Photosensitization - rabbit
No evidence of photosensitization
(0.1X suspension in saline)
Subacute:
14-week feeding - rat
No evidence of toxicity was observed up to
10,000 ppm in the feed (approximately 5000 mg/
kg/day), the maximum concentration tested.
3-month oral - dog
No effect was observed at 2.5 mg/kg/day (in
gelatin capsules). At 250 and 2500 mg/kg/day
there were no effects other than frequent
loose yellowish stools.
93
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Chronic:
1-year feeding - mouse (including 3-generation
reproductive study)
At 1000 ppm (equivalent to 50 mg/kg/day) in
the diet there were no observed differences from
control animals in any parameters including
tumor incidence. On ultraviolet illumination
of tissue specimens, fluorescent deposits were
seen in adipose tissue.
2-year feeding - rat
At 1000 ppm in the diet, there were no observed
differences from control animals except slight
liver enlargement in male rats, and an increased
incidence of optical lens opacities of trefoil
or Y-shaped configuration. Liver function tests,
and liver histology, were not different from
controls.
Human Toxicology:
Primary Skin Irritation and Sensitization:
No evidence of irritation or sensitization was observed
in.102 subjects who were patched for 48 hours with 0.5
and l£.Uvitex OB in low-melting paraffin, and challenged
with another patch 2 or 3 weeks later.
Symptoms of Poisoning:
No cases of poisoning with Uvitex OB have been reported.
In animal tests, oral administration of large repeated
doses caused diarrhea in dogs.
First Aid and Treatment:
For skin contact: wash with soap and water
For eye contact: flush with water for 15 minutes
For swallowing: since Uvitex OB is of low toxicity,
ingestion of small amounts should
require no treatment other than a
saline laxative. In case of massive
ingestion, if conscious, give water
and induce vomiting or lavage stomach.
Give supporting therapy.
Handling Recommendat ions:
In accord with good industrial practice, handle with due
care and avoid unnecessary personal contact.
94
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TOXICOLOGY DATA SHEET
NOPOL
(NORDA, INC.)
Synonyms: 6.6-Dimethylbicyclo-(3.1.1)-2-heptene-2-ethanol.
Description and physical properties: A colorless liquid.
Preparation: By condensation of beta-pinene with formalde-
hyde under pressure (Arctander, 1969).
Uses: In public use since the 1940s. Use in fragrances in
the USA amounts to approximately 10,000 Ib/yr.
Concentration in final product (%):
Soap Detergent Creams, lotions Perfume
Usual 0.03 0.003 0.015 0.3
Maximum 0.25 0.025 0.08 1.2
Analytical data: Infra-red curve, RIFM No. 76-374.
Status
Nopol is not included in the listings of the FDA, FEMA
(1965), the Council of Europe (1974), or by the Food Chemicals
Codex (1972). CAS Registry Number 128-50-7.
Biological Data
Acute toxicity. The acute oral LD5Q value in rats was
reported as 0.89(0.61-1.29g/kg) and the acute dermal LD50
value in rabbits exceeded 5g/kg (Moreno, 1977). The im LD^Q
for nopol in mice was 0.5 g/kg (Northover & Verghese, 1962).
Irritation. Nopol applied full strength to intact or
95
-------
abraded rabbit skin for 24 hours under occlusion was mod-
erately irritating (Moreno, 1977).
Tested at 8% in petrolatum it produced no irritation
after a 48 hour closed patch test on human subjects (Epstein,
1976).
Sensitization. A maximization test (Kligman, 1966;
Kligman & Epstein, 1975) was carried out on 29 volunteers.
The material (RIFM # 76-374) was tested at a concentration
of 8% in petrolatum and produced no sensitization reactions
(Epstein, 1976).
Pharmacology. In the anesthetized dog, 23 mg/kv iv of
nopol produced a 25% fall in blood pressure. Hypotensive
effects were also noted in the decerebrated and despinal-
ized dog (Northover & Verghese, 1962).
Isolated tissue. Nopol (50 mg), when added to the
perfusate of the isolated hind leg of the anesthetized dog
or isolated rabbit ear, produced vasodilation (Northover &
Verghese, 1962).
96
-------
References
Arctander, S. (1969). Perfume and Flavor Chemicals (Aroma
Chemicals). Vol. II, no 2383. S. Arctander, Montclair,
New Jersey.
CIVO-TNO (1977). Volatile compounds in Food. 4th edition.
Centraal Instituut Voor Voedingsonderzoek ENO. Edited
by S. Van Straten. Zeist, Netherlands.
Council of Europe (1974). Natural Flavouring Substances,
Their Sources, and Added Artificial Flavouring Subst-
ances, Partial Agreement in the Social and Public
Health Field. Strasbourg.
Epstein, W.L. (1976). Report to RIFM, 20 December.
Flavoring Extract Manufacturers' Association (1965). Survey
of flavoring ingredient usage levels. Fd Technol.,
Champaign 19(2), part 2, 155.
Food Chemicals Codex (1972). 2nd ed. Prepared by the Committee
on Specifications, Food Chemicals Codex, of the Comm-
ittee on Food Protection. National Academy of Sciences-
National Research Council Publ. 1406, Washington, D.C.
Kligman, A.M. (1966). The identification of contact aller-
gens by human assay. III. The maximization test. A
procedure for screening and rating contact sensitizers.
97
-------
J. invest. Derm. 47,393.
Kligman, A.M. & Epstein, W. (1975). Updating the maxim-
ization test for identifying contact allergens.
Contact Dermatitis. 1, 231.
Moreno, O.M. (1977). Report to RIFM, 2 February.
Northover, B.J. & Verghese, J. (1962). The pharmacology
of certain terpene alcohols & oxides. J. scient. ind.
Res. 21C, 342.
98
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APPENDIX D
VOLATILITY AND FLASH POINT STUDIES
Static tests were run, on both gelled and ungelled liquids
in closed manometric systems; the results of these tests
strongly bear out that there is no significant effect on the
vapor pressure exerted by the system. Dynamic tests, to be
described, showed very significant advantages for gelled vs.
ungelled systems. Using the apparatus shown below, reductions
in excess of 50% of the rates of evaporation for compounds such
as hexane, ether, and similar vaEatiLle compounds with limited
solubility in water, have been observed for the gelled liquids.
1 Thermos tai
water bat!
Magnetic
stirrers
DYNAMIC VOLATILITY APPARATUS
In practice, the two cups seen through the window in the
wind tunnel are half filled with water, and then layered., in one
cup, with ungelled liquid. The other cup is layered with a 10%
solution of Amine D_solution in the liquid, the entire solution
then being gelled with carbon dioxide in the form of a few
pieces of Dry Ice. The cups are thermostated in a water bath
to a temperature of 25° C., and winds of various velocity
(usually around six knots, wind velocity being measured by the
anemometer) are passed over the cups using the fan indicated
above. Weights of the cups are taken on a periodic basis. In
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-------
the case of the gelled liquids, a crust soon forms on the
evaporation. It is strongly indicated that reductions in fire
hazards for flammable liquids, and in toxicities of poisonous
liquids, would be desirable consequences of this effect.
In an effort to quantify any effects in reduction of fire
hazards, open flash points were determined; the results of these
tests are shown in the following table.
(The same wind tunnel as -was used in the previously
described volatility experiment was utilized to direct a five-
knot wind onto the open cup of a flash point apparatus, in
keeping with the previously described volatility experiment.)
Flash Point,
UNGELLED
Flash Point, °C
GELLED
Literature
Compound
Cyclooctane
1-Dodecene
Ethylbenzene
Ethyl Butyrate
Trial I
52.5
92.5
36.5
39.5
Trial II
53.0
91.5
36.0
38.0
Trial "I
63.5
93 . 0**
49.5
41,5
Trial II
62.0
94 . 0**
54.0
41.5
Value*
23.8
29.4
* Lange's Handbook of Chemistry, 9th ed., edited by W. A. Lange,
Handbook Publishers', Inc., Sandusky, Ohio, 1956; pp. 32-49.
Literature values are significantly lower than ungelled values
in this experiment, inasmuch as in this experiment a five-
knot wind current is being utilized.
** The 1-dodecene gel began to melt at about this temperature.
As can be seen from the above data, significant flash point
elevations were achieved, particularly for the hydrocarbons
which did not melt, upon gelation.
100
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APPENDIX E
SUBMISSIONS OF PRODUCT LISTINGS FOR INCLUSION IN SURVEY
OF EQUIPMENT FOR OIL AND FLOATING HAZARDOUS MATERIAL
SPILL COUNTERMEASURES
Product Listing: AMINE CARBAMATE GELLING AGENTS
1.3 Containment on or in water
- Fluid barriers
1.4 Air containment or vapour suppressor
- Physical
2.2 Recovery from water
- Floating substances
- sorbant surface devices
3.2 Systems for liquids
- Other (immobilization of oil and floating hazardous
liquids by gelatin, thereby reducing spreading rate
over water surfaces)
- Other (use of nets in recovery of gelled oil and
floating hazardous liquids)
4.2 Systems for liquids or solids
- Other (use of plastic bags, cardboard boxes, etc.
for storage of recovered gelled oil and hazardous
liquids)
- Other (reduction of shipboard free surface effects
by gelation of stored recovered oil and hazardous
liquids)
7.3 Treating agents
- Physical converting agents
- gelling agents
- other (increased visibility of oil and hazardous
liquids by conversion to opaque white floating
chunks of gel)
101
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Brief Description
AMINE CARBAMATE GELLING AGENTS
This system is intended to facilitate recovery and control
of oil and hazardous liquids on water surfaces. A trimaran is
equipped with forward mounted sprayers fed by an amine solution
pumped from deck tanks; a liquid C02 transit tank and sparging
system aft of the sprayers; and nets towed behind the craft to
recover the gelled liquid. The gelling reaction has been fully
tested; the trimaran is still under development, one prototype
having been built and successfully tested.
Operating Principle;
The process depends on the reaction of CO_ and an amine, to
form a carbamate salt: A
CO0 —
R-NH2 +
^ ©
R-NH2-CO2
The spill is directed into the path of amine sprayers by
sweeps or booms at the front of the trimaran, and thence between
102
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the pontoon hulls. Liquid CC^ is directed into this mixture,
and the resulting carbamate solidifies the entire liquid system
into white floating chunks of gelled material.
The solidified oil or hazardous liquid is considerably less
mobile and will not readily spread back over the track previously
cleaned by skimmer craft, as would be the case for ungelled
material. Being white and opaque it is much easier to see; due
to its solid consistency it can be recovered by nets towed aft
of the trimaran, and then stored in bags or boxes which would
otherwise be unsuitable for liquid recovered material. The
solid nature of the gelled liquid also prevents spread of un-
gelled liquid areas contiguous to gelled areas. Free surface
("sloshing") effects which tend to destabilize vessels carrying
recovered liquid pollutants are obviated by conversion to the
solid gelled state. Gelled liquids have greatly reduced
evaporation rates and higher flash points, with decreased
toxicity and fire hazards . Should gelled pollutants wash
up on a beach, the solid form will not penetrate the sand or
soil as would ungelled liquids. The pollutant can be recovered
by subjecting the gelled material to pressure filtration, with
recovery also of the carbamate gelling agent which can then be
converted to the starting amine by thermal decarboxylation.
Physical Specification;
Amine Solution A three component solution is used: 70%
(to be applied in A^^ D™ (dehydroabietylamine, manu-
about 15 % concen- J J
tration): factured by Hercules); 15% ethanol; and
15% Nopol (6,6-dimethyl-2-norpinene).
Vessel: Modular trimaran, capable of assembly in
less than two hours; when disassembled
can be stored and transported in a 2.5x3.
7x1.8 meter (8'xl2'x6') truck trailer
with all required equipment and supplies.
Pontoons are perforated polycarbonate
103
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shells clamped around inflatable rubber
bladders. Deck consists of marine ply-
wood panels laid over aluminum bracing.
Overall assembled length (without exten-
ded sweeps), 7.3 meters (24 feet); width,
3.7 meters (12 feet). Draft with full
loading, 0.4 meter (17"); freeboard 0.5
meter (23").
Ancillary Eight 55-gallon (206 liter) drums of
Equipment: Amine D solution; C02 transit tank (320
kg., or 700 Ib capacity) with hose and
sparging system; metering pumps (two)
for Amine D solution; Amine D sprayers
(two); 220-volt electrical generator
(gasoline powered) and GFI (Ground Fault
Interrupter) equipment; forward-mounted
sweeps for increased width of intake
area; two 25-HP marine engines. Life
rafts, life jackets, tool and damage
control locker. Additional drums of
Amine D solution, as may be required,
would be stored and transported sepa-
rately. For situations involving re-
covery and control of more than 5,000
gallons (18,750 liters) of pollutant
liquid spills on water surfaces, a
back-up CO_ transit tank is recommended
also. Liquid CC>2 for filling of transit
tank would be obtained from CO- facility
en route to spill site.
Cost: Trimaran craft and all equipment: $70K
(U.S.).
Supplies: For each 200 kg. drum of
Amine D solution, capable of
104
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application to 1350 liters
(360) gallons of pollutants
$900 (U.S.).
Liquid CO^: Refill of tran-
sit tank: approx. $300.
Operating Vessel designed for operation in inland
Specifications: waters or in situations with less than
0.5 meter (1 1/2-foot harbor chop
situations.
Craft will support a load of five metric
tons of equipment and supplies, at a
fully laden speed of about 3 1/2 kts (6.5
km/hr), and can cover an area of about
0.4 hectare (one acre) in a track five
meters wide by 0.8 km (16 1/2 feet by 0.5
mile), with 8200 liters (2200 gallons
of pollutant spill, in less than 10
minutes. Recovery nets towed by aux-
iliary craft stationed behind the
trimaran could be deployed to recover
the gelled pollutant.
Assembly and loading of the trimaran can
be accomplished at a boat landing, or by
lowering raft and component equipment
from overhead bridges to water surface
by means of a one-ton crane.
Usage: Prototype successfully tested at US
Naval Submarine Base, New London, CT on
17 December 1979, and successfully used
there later on an actual spill.
- No quantitative results.
11 ... successful gellation of an
actual spill on 31 December 1979 at
the Naval Submarine Base New London,
Groton, CT.
105
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. . . The gelation of oil by amine
carbamates would be feasible and
economical under certain conditions.
(Report of Commanding Officer, Naval
Submarine Support Facility, New
London to Commander, Naval Facili-
ties Command, dated 25 Feb 1980.)
Availability Patents: U.S. 3,684,733 and 3,880,569.
Publication: "Amine Carbamate Gelling
Agents for Facilitating Oil Spill
Recovery and Control", Marine
Technology, October 1980, pp. 146-
149.
Manufacturer: University of Lowell
Lowell, MA 01854
Phone: (617)452-5000,
X2509
Contact: W. Bannister
106
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Product Listing; FLUORESCENT AGENTS FOR NIGHT-TIME OPERATIONS
7.3 Treating agents
- Combination or other (fluorescent agents for night-time
oil or hazardous liquid spill recovery and control
operations)
Brief Description;
FLUORESCENT AGENTS FOR NIGHT-TIME OPERATIONS
This system is intended to facilitate recovery and control of
liquid spills on water surfaces. Commercially available, non-
toxic, cheap and highly efficient fluorescing agents with both
oil and water solubility are applied in very low concentrations
to liquid spills with excellent results. In open water the
agent is dissipated into the water column, but is preferen-
tially retained in pollutant patches on the water surface.
At night UV light is beamed over the spill area with illumin-
ation by resulting fluorescence occurring only from patch areas.
Excellent contrast between pollutant patches and open water
areas is thereby obtained, such discernibility enabling night-
time spill recovery and control operations.
Operating Principle;
A solution of the fluorescer is sprayed from aircraft on the
spill area to a concentration of 10 ppm (0.001%) in the pollutant
spill. That portion landing on spill patches is retained; spray
landing on open water is dissipated into the water. At night a
skimmer with longwave (366 nm) UV lights is deployed. Ordinary
visible searchlights are operated intermittently to illuminate
floating debris in the path of the craft. During periods of
searchlight, darkness UV effected fluorescence from the pollutant
patches will provide adequate perception of perimeters of these
patches.
107
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Physical Specification;
Fluorescer
Solution:
Ancillary
Equipment:
Cost:
Operating
Specifications:
Usage:
Availability
and Commercial
Information:
TM
UVITEX OB stilbene fluorescer manu-
factured by Ciba-Geigy, Inc, in a glycol
ether solvent (concentration of solu-
tion about 1%).
Conventional crop-spraying equipment as
used in aerial spraying operations.
UV lights (under development). (In test
operations racks of 1.8 meter, or six
foot 85-Watt UV fluorescent lamps have
been used successfully.)
Suitable helicopter or fixed-wing air-
craft for agent delivery.
For application over 2.5 hectare (25,000
2
m , or ten US acres) it is anticipated
that the fluorescer agent and solvent
would cost about $300 (US).
(See discussion under Operating
Principle.)
Small (10 m2) areas tested at OHMSETT
(August 1979) .
- No quantitative results.
Applications for patent coverage in
progress.
Publication: Marine Technology,
October 1980, pp. 146-149
Manufacturer: University of Lowell
Lowell, MA 01854
Phone: (617) 452-5000,
X2509
Contact: W. Bannister
108
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SUMMARY TABLE A:
Equipment, System or Material Type
•o
o>
*J
c AJ
2 c
e o)
3 a >•>
U Ouot
O T3 O 5
Q 0) rH M
4J Q)Q)
1. Containment £ Jj ^J
1.3 Containment on or in water
- Fluid barriers XXX
1.4 Air containment or vapour suppressor
- Physical XXX
2. Mechanical Recovery
2.2 Recovery from water
- sorbant surface devices XXX
3. Transfer Systems
3.2 Systems for liquids
- Other (immobilization of pollutants
by gelation, thereby reducing
spreading rate over water) XXX
- Other (use of nets in recovery of
gelled pollutant) XXX
4. Temporary Storage
4.2 Systems for liquids or solids
- Other (use of plastic bags, card-
board boxes, etc, for storage of
recovered gelled pollutant) XXX
- Other (reduction of shipboard free
surface effects by gelation of
stored recovered pollutant) XXX
7. Treatment
7.3 Treating agents
- Physical converting agents
- gelling agents XXX
- other (increased visibility of
pollutants by conversion to
opaque white floating chunks of gel) XXX
109
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SUMMARY TABLE A:
CATEGORIZATION BY BEHAVIOUR
AND PROPERTY OF MATERIALS ON THE
EEB PRIORITY LIST OF SUBSTANCES
General applicability:
Liquids: High, medium, or
low flammability
Specific Gravity
less than 1.00
Little reaction or
low miscibility
with water
Group A
Group B_
O
C 0)
-H C
XI O
»-) -M 0)
*0 0) 4J
CJ « (0
E
(DO
c e
,
jd
0)
•O
0» >i
T3 JJ
-H 3
O
C O O O -M
«J rH W 10 OJ
1.3 Containment on or in water
- Fluid barriers
1.4 Air containment or vapour
suppressor
- Physical
2.2 Recovery from water
- sorbant surface devices
3.2 Systems for liquids
- Other
- Other
4.2 Systems for liquids or
solids
- Other
- Other
7.3 Treating agents
- Physical converting agents
- gelling agents
- other
LEGEND:
T = Tested only
P = Possible application to
substance
C JS
0) -P
Q) PQ 0) Q) CO
C C C 0)
Q) rH Q) (1) C
N >1 M
C
Q) 4J -P O
ffl W M E-« !X i-U 0) (V 0) I A3
OQUUWSSS CEHEn
TPT TPPTP T PT
NOTE: All items indicated to the left
apply as indicated above.
Virtually all compounds listed
in Group A and Group B Tables,
and not included in above
listing due to solid state or
density greater than 1.0
characteristics, are gelled by
this system in situations
wherein these are dissolved in
suitable solvents. For
example, solutions of dichlo-
robenzene in hexane are gelled
by amine carbamates.
110
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SUMMARY TABLE A:
Equipment, System or Material Type
7. Treatment
7.3 Treating agents
- Combination or other (fluorescent
agents for night-time hazardous
liquid spill recovery and con-
trol operations
SUMMARY TABLE B:
CATEGORIZATION BY BEHAVIOUR
AND PROPERTY OF MATERIALS ON THE
EEB PRIORITY LIST OF SUBSTANCES
General applicability:
Liquids: High, medium or
low flammability
Specific Gravity
less than 1.00
_.,J_, . .
Little reaction or
1 r>w mi co-i Hilil-v
low misciciiity
with water
7 1 rn_-_4.J _„ -,-^,,4.0
/ . j Treating agents
- Combination or other
§ §
Q)
o
§
S
o)«i
OJHOJOCJS
Q)4J-PO>il
TTTTTT
m
-o
J31
5
•a
i
a. (C
o >
rH M
0)0)
>-o
(DC
a »
Group B
«j
CJ
O
4J 0>
I
-------
APPENDIX F
NEAR-SURFACE WATER COLUMN PROFILING BY ACOUSTIC SENSING
AS A COMPLEMENTARY MEANS TO DEFINE EXTENTS OF LOW-VISIBILITY -
OIL AND HAZARDOUS CHEMICAL SPILLS
Background
(The following remarks, regarding acoustic sensing as a
means of studying oceanic pollution problems, are abstracted
from a paper delivered by J. R. Proni of NOAA, at the 1980
Ocean Acoustic Remote Sensing (OARS) Workshop.
"The use of acoustics in studying oceanic pollution
problems has risen substantially in the last five years.
Since that time numerous uses of acoustics have been
made in studying dumped materials; these materials
include sewage sludge, dredge material, petrochemical
wastes, industrial wastes, pharmaceutical wastes,
sub-surface oil (from the IXTOC-1 oil spill) and,
recently, drilling muds."
"One of the most important characteristics of a
given volume of oceanic water is the rate at which
elution. of a given dump material occurs in that water.
There are various factors which influence the dilution
rate; these include water column stratification,
currents and dispersion (turbulent) characteristics.
Accurate dilution rates are extremely difficult to
oBtain. However, estimates may be made of horizontal
dispersion coefficients, K, which are fundamental in
dilution rate predictions."
(Additional remarks by M. H. Orr of the Woods Hole
Oceanographic Institution, at the OARS Workshop, are abstracted
below.)
"Remote acoustic sensing of atmospheric fluid processes
has developed into an active research discipline. There
are a large number of applied and basic atmospheric
research groups using the acoustic technique in both the
monostatic and bistatic modes of operation. These groups
study both fluid and biological processes. In contrast,
the number of researchers actively using or evaluating
112
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the use of high frequency remove accoustic sensing to
study oceanic fluid processes is quite limited. Although
a few people actively pursued the potential, the
oceanographic community has not adopted the technique
as a tool. This lack of interest may be due to the
discipline's past preoccupation with trying to
understand oceanic circulation on a mesoscale and also
the uncertainty in interpreting the acoustic records
without complementary in situ data."
"The acoustic system developed at the Woods
Hole Oceanographic Institution has been used to
study:
(1) sewage sludge and particulate
distribution in Boston Harbor,
(2) fluid processes such as internal waves,
shear instabilities, air-sea interactions,
shelf-slope frontal zone, interleaving
water masses, and hydraulic jumps across
wills, and
(3) the seasonal dispersion properties of
particulates released or formed during
industrial chemical and sewage sludge
disposal at Deep Water Dumpsite 106
(DWD 106). The research has been conducted
in Boston Harbor, Massachusetts Bay, on
the eastern continental shelf, in Puget
Sound, and in the open ocean."
"Theoretical considerations indicate
that the dominant mechanisms anticipated
for the oceanic environment are:
(1) backscattering from laminae or
isotropic temperature fluctuations which
are developed during turbulent mixing
events,
(2) backscattering from temperature
steps or gradients, and
(3) backscattering from particulate
distributions (either animate or inanimate)
associated with varying water masses. For
example, nearly neutrally buoyant particles,
when falling through the water column,
could have a tendency to collect at density
discontinuities associated with temperature
steps in the water column. Consequently,
113
-------
an acoustic backscattering system would be
able to map the location of the density step
and associated thermal step and the step's
response to internal wave activity and
mixing processes."
Conclusion
"A general overview of the results calls
attention to the potential of using high frequency
acoustic back-scattering systems in the study of:
I. A variety of fluid processes:
A. Internal waves
B. fronts
C. mixing
D. interleaving water masses
II. Particulate distributions:
A. natural in estuary, shelf, and open ocean
environment
B. manmade in estuary, shelf, and open ocean
environment
1. dredge spoils
2. industrial chemical wastes
3- sewage sludge
III. Biology
A. fish stock assessment
B. zooplankton biomass
C. predator-prey interactions
D. Biological avoidance of oceanographic
instrumentation
E. Biological response to fluid processes."
From the foregoing statements it would appear that the
use of a device which can be carried at the surface of a
water column and can give information in real time about the
114
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density of particles at every depth along the water column
has appeal in research at sea. Such a device, acoustic echo
sounding and sensing equipment described above does exist
and its practicability has been demonstrated. Whether the
resolution of particle sizes is shape dependent (as it is in
the case of light scatter as a function of wavelength) remains
to be determined. It is not clear at this time either as to
the contribution to the changes in composition of the echoes
from column that will be changed by other parameters which can
be measured throughout the length of the column. Just as in
the case of light, sound will be scattered in various ways,
depending upon the size and shape of particles, and the
refractive properties of the containing medium. However, the
prediction of the existence of particles having particular
characteristics may be" more difficult than is the case with
light. No doubt, some of the parameters which are monitored
presently as indices of the condition of state and the
quality of water will to some extent alter the propagation of
sound wave fronts. We wish to record several of these
indices at sites which are being simultaneously probed with a
surface carried echo sounder operating from 3 to 300 kHz,
using the Datasonics Model DFS-2100 Environmental Echo
Sounding System; see accompanying information.
High frequency acoustic backscattering techniques have
the potential for becoming a valuable tool in oceanographic
research and monitoring exercises. These will be able to work
in both a complementary and a stand-alone format.
115
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^^^^^^^^^^^^^^^.S^S^^.S^3-f^1^S^SS%fe^S^;:^-*'r-7
• & '. *
*«••••'•«>•* V:"'/.iJ '.!"••:•.•!
SCIENTIFIC ECHO SOUNDING FOR STUDY OF FATE
OF SUSPECTED HYDROCARBON POLLUTANTS
116
-------
Model EPC-3200
Graphic Recorder
•* . f JS '*" %,i
MODEL DFS-2100 DUAL FREQUENCY SCIENTIFIC ECHO SOUNDER
-------
CAPABILITIES
Location, tracking and mapping concentrations of biological
activity.
With a sample taken to ground truth the acoustic record, a
fast, accurate survey can be performed.
The calibrated acoustic system allows calculation of target
strength of individual scatterers, or reverberation level
of scattering layers.
Water column processes including internal waves, interleaving
water masses, shear discontinuties etc. can be detected and
mapped as part of circulation modeling projects as well as
other types of oceanographic research programs.
Tracking dispersions of drilling effluents pumped from offshore
drill rigs.
Location and tracking position of plumes resulting from
sewage sludge, chemical waste and other potentially toxic
material dumped in the ocean.
Survey of dredge spoil dispersion.
Location and tracking position of hydrocarbons in the water
column resulting from spills or natural seepage.
Study of sewage treatment plant outfall effluent dispersion.
Analysis of in water pollutant location, origin, and ultimate
destination.
Port and harbor environmental studies associated with
construction projects.
Component Description Model DFT-210 Transceiver:
The high power, two channel calibrated transceiver generates
two independent transmit signals over a frequency range
between SkHzand 300 kHz. Dual channel low noise, high gain
receivers provide calibrated outputs which incorporate
accurately controlled time varying gain to compensate for
spreading and attenuation losses. Wide system dynamic range
allows processing of large and small scatterers throughout
the water column.
Model TTV-130 Towed Transducer Vehicle;
A light weight tow fish with two transducers installed for
118
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operation at customer specified frequencies between 3 kHz and
300 kHz. Constructed from corrosion resistant stainless steel
and fiberglass, the vehicle can be easily deployed and
recovered by a single person.
Model EPC-3200 Graphic Recorder;
A 19 inch dry paper two channel recorder for simultaneous
display of data at the two selected system operating
frequencies. The recorder has an internal data memory which
allows selective data expansion and display of water column or
sub-bottom sediment data-in the best possible format. Memory
capability allows data display free of interference problems
associated with second bottom multiple echos.
Tow Cable Assembly;
Tow cables are available in different lengths with either
external armoring or a Kevlar braid with urethane jacket to
provide the required breaking strength. A stainless kellums
grip or molded epoxy retention provides a termination at the
tow fish end of the cable. High quality Brantner Sea-Con
connectors are utilized. Internal dedicated coaxial conductors
provide best isolation between channels with lowest possible
noise insetion.
SPECIFICATION FEATURES
Wide Range o_f Operating Frequencies;
Simultaneous dual frequency operation over frequency range from
3 kHz to 300 kHz. Channel 1 frequency adjustable in 10 Hz
steps, Channel 2 in 250 Hz steps.
High Transmitter Output:
4 KW power output each channel, adjustable in 3db steps, open
and short circuit protected.
Selectable Pulse Width and Repetition Rate:
Internal or External control of repetition rate up to 8 pps.
Selectable pulse widths from 100 usec to 2 msec.
Superheterodyne Receiver Utilizes Precise Mechanical Bandpass
filter si
Superheterodyne design allows calibrated control of signal
processing over wide frequency range. Bandwidth selection
1,2,5 or 10 kHz.
119
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Low Noise High Gain Receiver Design;
Use of a very low noise pramphlifier and high overall system
gain capability allows detection of small size particle
scatters and low concentrations of particulate matter. GAIN
control is provided in calibrated 3 db steps.
Accurate Time Varying Gain (TVG) Control and Wide Dynamic
Range;
Allows processing of both large scatterers at close range and
small, more distant scatterers. With greater than 80 db range
and a selectable range reference between 1 meter and 100 meters,
operation is possible in both shallow and deep waters areas.
Accurate Transmission Loss Compensation:
The TVG control provides spreading loss compensation at both
20 Log R and 40 Log R rates with adjustable 2 cc R attention
loss compensation,
Multiple Receiver Outputs;
Calibration;
A calibrated self test signal is available for providing a
field calibration check for proper system operation.
Sub-Bottom Profiling Feature;
Adjustable calibrated sub-bottom TVG with automatic bottom
tracking for optimum high resolution profiling of sediment
structure. Calibrated output 3-llows calculation of relative
reflection strength of successive sub-bottom layers.
Transducer Selection;
Several transducers are available over the frequency range;
including units operating at 3.5 kHz, 7.0kHz, 12kHz, 25kHz,
37 kHz, 50 kHz, 85kHz, 120 kHz, 200 kHz and 300 kHz.
Beamwidths vary with transducer physical dimensions and can be
tailored as required. All units are constructed of piezo-
electric ceramic arrays installed in a pressure compensated
oil filled housing.
120
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APPENDIX G
REPORT OF OIL SPILL CONTROL AND RECOVERY FIELD TESTS AT
US NAVAL SUBMARINE BASE, NEW LONDON, CONN.
NSSF:630:das:DICTA/A
6240
Ser 000244
25 FEE 1980
From: Commanding Officer, Naval Submarine Support Facility
New London,
To: Commander, Naval Facilities Engineering Command
Subj: Gelation of oil by amine carbamates; test and
evaluation of
Ref: (a) COMNAVFACENCCOM Itr 1123C/PCH of 3 Jul 79
(b) CO, NAVSUBSUPPFACKLON Itr Ser 1239 of 30
Jul 79
(c) U.S. Environmental Protection Agency Region I
Itr of 31 Oct 79
(d) State of Connecticut Department of Environ-
mental Protection Itr of 6 Nov 79
Encl: (1) Photographs taken 8 Nov 79 of first attempts
at gelation (7)
(2) Photograph taken 21 Dec 79 and sketch showing
assembly of workable components
(3) Photographs taken 31 Dec 79 showing utilization
in an actual spill situation (4)
1. Reference (a) requested that the Naval Submarine Support
Facility New London perform-a limited oil spill clean-up
test and evaluation of an oil gelling agent; which depends
on the action of carbon dioxide on amine which forms a
sluge like material when combined with oil and forms gel-
lation of the oil it contacts. Once gelled the solution
is to be picked up by mechanical means such as shovel, nets
or large scopes. This method has been developed by the
University of Lowell for the Naval Facilities Engineering
Command. Reference (b) requested authorization for subject
test and evaluation to be conducted by the Naval Submarine
Support Facility New London. References (c) and (d) approved
121
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the use of the gelling agent in the clean-up of a spill of
opportunity.
2. An initial test and demonstration by the University of
Lowell team, with assistance from the Naval Submarine Support
Facilities New London Pollution Control personnel on 8
November 1979, was unsuccessful due to inability to regulate
air pressure within the amine carbamate distribution system.
Enclosure (1) contains photographs of the equipment used.
Enclosure (2) provides a photograph and sketch of a simp-
lified system recommended by the Naval Submarine Support
Facility New London personnel. A successful test using the
modified equipment was conducted on 17 December 1979.-
Enclosure (3) contains photographs of the successful gel-
lation of an actual spill on 31 December 1979 at the Naval
Submarine Base New London, Groton, Connecticut.
3. The gellation of oil by amine carbamates would be
feasible and economical under certain conditions. The fol-
lowing are examples:
a. Inside of drydocks where staging and blocks prevent
the maneuvering of present mechanized equipment (DIF 3001).
b. The boundaries of marsh areas where the gellation
of oil would reduce or prevent further mitigation of oil due
to its adherence to boundary vegetation.
c. For blocking the flow of oil through breakwaters,
canal banks, or quays etc. by accumulation of the gelled
product in the passageways.
T.C. Maloney
Copy to: (w/o enclosures)
University of Lowell, Lowell MA
State of Connecticut Department of Environmental Protection,
Hartford, CT
Seas International, LTD, Needham, MA
COMSUBGRU TWO
COMSUBRON TWO
122
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APPENDIX H
FLUORESCENT AGENTS FOR NIGHT-TIME OPERATIONS:
RESULTS OF TESTS ABOARD EPA OSV ANTELOPE, 14 SEPTEMBER 1981
Time:
Location:
Ship Speed:
Weather
Conditions;
Oil Spill:
Approximately 9:30 - 10:15 PM
Approximately five miles ENE of eastern terminus of
Cape Cod Canal, in Cape Cod Bay, Massachusetts
Approximately four knots
Temperature;
Wind;
Waves;
Visibility;
Approximately 60°F (15°C)
Approximately 5 knots, varying gusts
during squalls
Calm
Full moon, obscured by occasional
cloud cover with intermittent rain
squalls. Overall excellent visi-
bility.
30 gallons of fish oil obtained from Marine Pro-
ducts Company, Boston, Massachusetts, with charac-
teristics as noted below. (Comparative data are
also provided for cyclohexane as a standard, and
#2 Fuel Oil as a typical material frequently en-
countered in oil spills in this area.)
Fish Oil #2 Fuel Oil
Density (g/ml)
Surface Tension
(dynes/cm)
(as received)
0.926
32.0
(as received)
0.74
27.2
Cyclohexane
25.3
Fluorescer:
.TM
UVITEX OB*", manufactured by CIBA-GEIGY Corporation,
Ardsley, NY. Weight used: 8.0 g (providing appro-
ximately 60 ppm concentration in fish oil). The
123
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fluorescer was mixed with the fish oil in a 35-
gallon drum prior to delivery onto water surface.
UV Lamps: Two 400-Watt Sylvania mercury vapor spotlights with
phosphor removed to provide UV illumination, with
about 5% of wattage in the 366 + 5 nm fluorescence
range of the UVITEX OB agent anticipated.
One 565-Watt Hanovia Super-S Alpine sun lamp, manu-
factured in 1948; broad range spectrum with about
2% of wattage available in the 366 + 5 nm fluores-
cence range.
One 100-Watt mercury vapor spotlight with about 5%
of wattage available in the 366 +_ 5 nm fluorescence
range.
Additional
Equipment: Datasonics, Inc. Model DFS-210 Dual Frequence acous-
tic sensing device, tested by Datasonics on this
occasion simultaneously with the fluorescence
system. (Although there is no relationship between
the fluorescence and acoustic systems, these were
demonstrated to be synergistic, as will be des-
cribed in ensuing discussion.)
DISCUSSION OF TEST
The fluorescer was mixed with the fish oil by use of wooden
paddle stirring of the mixture in a 35-gallon drum. Prior to the
test, also, two UV-sensitive fluorescent markers, in the form of
24' x 3' plastic "bubble-cap" sheets, one painted with fluores-
cent red and the other with fluorescent green paint, were made
ready for use to mark the end and beginning of the oil spill.
Intentions were to notify the bridge of both events, in order
that Loran "C" fixes could be obtained to facilitate finding the
oil on a return pass.
An electrically powered gear pump, which we had intended to
use to spray the oil into the water from the stern of the ship,
was found to be inoperable, just prior to the beginning of the
124
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test. Moreover, the two 400-Watt spotlights which we had in-
tended for use as main sources of UV illumination, were dis-
covered to be almost completely deficient in UV, apparently due
to 'incomplete removal of phosphor material from these bulbs.
It was decided, therefore, to lay the oil spill by simply
pouring the oil through a .jury-rigged sieve (made of plastic
buckets with holes punched in the bottoms of these), over the
stern into the wake of the ship. The sole source of illumination
available for fluorescent lighting was the Hanovia 565-Watt sun
lamp, which emitted a very large percentage of its light in the
form of visible white light of rather high intensity; this lamp
was mounted on the fantail, with the light being directed to port
and starboard by swivelling the lamp component in these direc-
tions.
At the commencement of the exercise, the green plastic blan-
ket was thrown as far aft into the wake as possible; unfortunate-
ly, the blanket was caught in eddies of the wake, requiring con-
siderable attention to prevent fouling of the ship's screws. In
the confusion of the moment, no notification was given to the
bridge of the moment when oil spill was initiated, nor at the
completion of the oil spill (although the red fluorescent blan-
ket was successfully deployed shortly thereafter); thus, no Loran
fix was obtained. It was estimated that the duration of the oil
spill was approximately three minutes, for an estimated length
of oil track of about 0.3 mile.
The bridge was notified several minutes after completion of
the spill, and a Williamson turn to port was executed to attempt
a return pass with the oil slick estimated to be to port by
about 25 feet. The UV light was directed to the port beam, and
several minutes later the red fluorescent marker was clearly ob-
served passing to port by about 25 feet. About 100 yards astern
of the marker the oil spill was clearly discernible, as a bright-
ly fluorescent ribbon of about a foot in width, extending for
about 300 feet. Several separated patches of fluorescent oil
were also clearly visible in the contiguous areas of this track,
125
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undoubtedly arising from turbulance effecting separation of the
spill into discrete patches.
At the same time the oil spill ribbon was observed by fluo-
rescence, the operators of the Datasonics acoustic sensing gear
reported sonar signals from globular material near the surface
of the water in the precise vicinity of the oil spill.
After passing the spill area, another Williamson turn was
executed, this time with intention of crossing the oil spill
track (the precise location of the spill was recorded from Loran
fixes during the previous passing maneuver). No fluorescence was
detected,.definitively, although small patches of fluorescence
were reported by separate observers, each such report being un-
confirmed by others, however, during the period of time the ship
was in the vicinity of the previously fixed location of the spill.
Simultaneously, during this period of time, the operators of the
Datasonics acoustic sensing gear reported enhanced sonar signals
from globular material descending from the surface. It appears
that the dense fish oil (density = 0.926, not much less than that
of sea water, or 1.025), of significant water solubility due to
polar carboxy and olefinic character of its components, was mixing
with and falling from the surface of the water. This tended to
be confirmed in a final pass over the area, at which time the
acoustic signals were again strongly detected at significantly
lower depths and with greater dispersion.
Because of the short notice of availability of the ship for
this test, high speed photographic equipment could not be ob-
tained for the test. Conventional photography was attempted, but
illumination from the fluorescent spill area was not sufficient
for this (although the spill area was very easily discernible to
the unassisted eye, and more than enough so to provide adequate
visibility for night-time oil spill control and recovery opera-
tions) .
CONCLUSIONS
In spite of equipment breakdowns, inadequacies and confusion
126
-------
as may be expected in any initial extrapolation of system tes-
ting from small lab bench to full field scale, excellent results
were obtained in this test, indicating that if water dispersible,
oil soluble fluorescing agents can be efficiently distributed in
small concentrations over open water surfaces with floating oil
patches, then sufficient visibility will result from fluorescent
illumination from conventional UV sources to enable night-time
oil spill control and recovery operations. It is even possible
that, with such a system, discernibility of perimeters of oil
patches may be greater than is the case in conventional day-time
operations, in which it is often very difficult to locate such
oil patches.
Very considerable synergistic effect is realized on combina-
tion of this system with environmental underwater acoustic sen-
sing gear, whereby dispersion of the oil into the near surface
can be detected along with surface contaminants.
Future tests should be conducted with emphasis on the
following:
1. Use of more powerful UV illumination (e.g., with con-
ventional high powered UV lamps of 2000 Watts or more
intensity), perhaps on several auxiliary craft stationed
around a given site, to permit considerably larger area
coverage than was attainable in this initial operation
involving a primitive UV lamp which enable illumination
of patches up to 50 to 100 feet away from the ship.
2. Further studies of the combined fluorescence/acoustic
sensing systems, particularly in applications over
wider areas.
3. Delivery of fluorescer from helicopters or fixed wing
aircraft, onto open water areas with floating oil
patches. It is anticipated that such delivery would
occur several hours prior to subsequent night-time oil
spill control or recovery operations, utilizing UV-
induced fluorescent illumination. For such testing pur-
poses, it is suggested that aircraft delivery occur
127
-------
during late afternoon hours, although such delivery could
occur at night as well.
Particularly in terms of the proposed aircraft delivery test
in which a significant time interval will exist between delivery
of the fluorescer onto the oil, and subsequent detection at
night, it is strongly suggested that EPA and Coast Guard per-
mission be obtained for use of hydrocarbon rather fish oil in
formation of the slick. The results of this exercise indicate
that fish oil of high density and significant water solubility
will not persist on a water surface for enough time to permit
surface detection several hours later. It is judged likely that
vegetable oil would behave similarly. Several experienced ob-
servers on board the ship for this test have expressed similar
opinions.
ACKNOWLEDGMENTS
Grateful acknowledgment is extended to Captain Dwight Paine
and the other fine crew members of the EPA Ocean Survey Vessel
ANTELOPE, without whose efforts and assistance this exercise
could not have succeeded; and to the United States Environmental
Protection Agency (represented at this test by Mr. Edward S.
McLean) and the Mar Corporation of Rockville, Maryland (repre-
sented at the test by Dr. Leslie Pierre) who made the ANTELOPE
available for the test, and who provided valuable technical
advice and assistance prior to and during the test.
We are also grateful to the Massachusetts Maritime Academy,
and its Director of Fisheries Programs, Dr. David Kan, for the
cooperation and assistance generously provided for many years to
this group; and to William A. Curby, Director of the Sias Memo-
rial Research Laboratories of the Lahey Clinic of Burlington,
Massachusetts who has materially shared in the development of
the fluorescence process from the concept to implementation
stages.
The contributions by Dave Porta and Bill Dalton of Datasonics,
Inc. in the synchronized utilization of Datasonics acoustic
128
-------
sensing equipment, and in interpretation of acoustic data, were
of obviously great importance in this test. Their innovative
approaches and enthusiastic support is greatly appreciated by
this group.
I wish to acknowledge also the following students without
whose industry, ideas and enthusiasm this project work would not
have been possible, and who have made this work as enjoyable as
it has been: Alberto and Juan Benevides, Brian Daigle, Gene and
Jim DiPoto, Samir Mody, Kingsley Ndi, Stephen Quigley, Manan Shah,
Son Truong, and Ronald Verna. Dr. Albert Donatelli of the
Chemical Engineering Department at the University of Lowell con-
tributed valuable advice and assistance to us, also.
The University of Lowell Alumni Association provided funds
for the support of students working on this project during the
Summer of 1981, during which time this project was brought to its
present successful status, and the students and I are very grate-
ful to the Alumni Association for this generous support.
Finally, I wish to express my thanks to the GTE-Sylvania Corpora-
tion for the donation of equipment, the technical advice and
assistance extensively provided to us, and the encouragement at
all steps expressed to us. Mssrs. George Duggan, Robert Edelson,
Joel Finkel, Charles Morse, and Paul Ulcikus of GTE Laboratories
and GTE-Sylvania were especially helpful to us in this regard.
129
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APPENDIX I
PROPOSED
OIL AND HAZARDOUS CHEMICAL SPILL CONTROL AND RECOVERY
BY AMINE CARBAMATE GELATION
Principal Investigator: William W. Bannister
Department of Chemistry
University of Lowell
Lowell, Massachusetts
ABSTRACT
Hazardous chemical spills on water surfaces pose serious
problems in terms of both water-borne and air toxicity effects,
and, in the case of flammable materials, fire hazards. These
problems are of particular and immediate concern to personnel
involved in spill control and recovery operations, with obvious
requirements for extremely close contacts by these individuals
with the hazardous chemicals.
Our group has had several successful projects with the EPA
and the Navy, in the development of a process whereby oil and
hazardous chemicals on water surfaces can be gelled to a solid
consistency quickly, safely and economically using
dehydroabietylamine (Amine DTM) sprayed in low (ca.16%)
concentrations onto the oil, with subsequent treatment with
carbon dioxide to form the carbamate as a gelling agent. The
gelation process has been shown to reduce volatilities in open
air by 50% or more, with corresponding reductions in toxic and
fire hazards. Moreover, the process is compatible with
fluorescent agents, which our group has demonstrated to thereby
provide considerably extended capabilities into night-time
operational hours. (In this latter process, cheap, non-toxic
and highly efficient fluorescent agents soluble in organic
spills and dispersible into the underlying water column are
applied in extremely low concentrations over the spill area;
in open water with no oil or chemical present the agent is
quickly dissipated into the water, but is retained wherever
oil or chemical spills are present. At night UV light can
then be beamed over the spill area with illumination by
resulting fluorescence from the slick areas permitting easy
discernment of these areas and thus providing excellent
capability for night-time recovery and control work.)
130
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In a recent field test at the US Navy Submarine Base at
New London, CT an actual oil spill was successfully controlled
and recovered quickly and efficiently using a prototype
trimaran craft equipped with a CO^ transit tank, several barrels
of Amine D, and easily constructed disposable spraying
equipment.
It is now proposed that a portable, easy-to-assemble-and-
disassemble trimaran craft for use in oil
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Where launching from a boat ramp will be feasible,casters
on the base of the platform frame will facilitate movement
of the craft. Threaded lugs projecting upward from the
lengthwise and transverse frames will match with pre-drilled
holes in transverse and diagonal frames, and with holes in
4* X 8' marine plywood deck sections, which will then be
secured by lug nuts by means of a pneumatic lug wrench
powered by C02 from the craft's transit tank. Eye bolts
shall be secured in the frame, extending above the deck to
permit crane launching in the event of non-availability of
a boat ramp.
3. Break-away bulkheads (for quick^release in the event of
"emergencies requiring overboarding of heavy items on deck)
shall be located in strategic locations on deck plates to
. provide secure clamping of the transit tank, 55-gallon
Amine D drums, and other items otherwise apt to move
uncontrollably as a result of wave action.
4. Port and starboard booms, hinged at the bow of the trimaran
and held taut by means of adjustable cables under spring
tension. These booms serve to increase the flow of water
(and surface oil) into the spaces between the pontoons, in
which spraying and carbonation to effect gelation take
place. In certain instances involving a moving contaminated
stream of water, these booms could conceivably be extended
from banks of the stream to the moored trimaran gel craft,
to enable treatment of the entire surface area of the
stream.
5. Disposable sprayer heads, constructed of pre-drilled 3% foot
PVC pipes, are located just forward of the channel intakes
between the pontoons.
6. Two variable speed heavy duty metering pumps force Amine "D"
solution from 55-gallon drums located in close proximity to
the pumps and sprayers, through polyethylene tubing (1"
diameter). (Pumps? drums and drum mounts, and feed tubing
are not shown in Figure A. Eight drums can easily be
accomodated on the deck space in the forward end of the gel
craft, providing for treatment of 2,200 gallons of surface
contamination, which would present a spill area of an acre
in the event of a 2 mm slick.
7. A transit tank with a capacity of 700 pounds of liquid CC>2
is located abaft the center of the gel craft, in a position
calculated to provide reasonable average stability. The
transit tank is held in place by a bulkhead with breakaway
sections, to enable immediate overboarding in the event of
imminent capsizing of the craft.
133
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8. Carbonator hoses extend from the transit tank forward to
positions slightly abaft the sprayers, at which points
these connect to spargaing fingers extending to the rear,
under the deck plated and between the pontoons. When
activated,^the tank discharges liquid C02 into the sparging
fingers which expel this into the stream of mixed ammine and
contaminant moving aft between the pontoons.
9. Two 25-HP marine outboard engines are situated at the stern
of the trimaran, providing propulsion and steering for the
craft.
10. For night-time operations, two highyintensity marine
spotlights can be mounted on stanchions at the bow of the
craft, for use with fluorescent agents.
11. Cloth after chutes extend behind the two channels between
the three pontoons. These serve to provide prolonged
contact time between the C02 and amine/oil mixture, to
optimize gelation, and to conduct the gelled oil or
hazardous chemical into nets located at the end of the
chutes.
12. Auxiliary equipment on board will include a gasoline
powered electrical generator, compressed air tanks to
maintain air pressure in inflated pontoons, on as as-needed-
basis, fire extinguishing equipment, a repair locker
equipped with patching supplies and other damage control
equipment, and overhead frames to support transparent
polytheylene tarpaulins in the event of inclement weather
(where wind conditions would permit such use).> GFI
(Ground Fault Interrupter) equipment shall be installed on
the trimaran. When in the water, two three-man life rafts
shall be deployed alongside the trimaran. All crew
personnel shall be equipped with life jackets while on
board, at all times. Sturdy railings shall be installed
on the periphery of the deck.
13. Advice shall be solicited from^qualified US Coast Guard
authorities throughout the design, construction and
testing phases of this project, to ensure that the craft
will be seaworthy and safe to operate. All phases of
construction shall be undertaken in consultation with a
qualified marine engineer and naval architect.
134
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PONTOON DISPLACEMENT, AND LOADING REQUIREMENTS
Assuming 24-foot lengths for each of the pontoons, and 33"
diameters, with half of the pontoon assembly to be available
for freeboard (i.e_., above water elevation), the three
pontoons would "thus displace 13,275 pounds of fresh water, or
13,600 pounds of sea water.
The following estimates are provided by way of suggested
loading requirements:
Pontoon weight (for nine pontoons)
Raft and bracing for raft:
Transit tank and carbonator hoses:
Metering pumps:
Sprayer assemblies:
750 pounds
1,200 "
2,000
600 "
200
8 55-gallon drums of Amine "D" solution4,100
Booms:
2 25-HP marine engines;
Assorted gear:
Generator:
6 Crew personnel:
TOTAL 11,230
1
200
200
500
280
,200
it
it
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Excess displacement
available before
decreasing 16%" free
board requirement:
2,045 pounds (fresh water)
2,370 pounds (Sea water)
135
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PROJECTED MATERIAL AND SUPPLIES REQUIREMENT
*Raft Assembly:
*9 4* X 8' marine plywood
*3 pontoons
*Booms, tension cables
*Steel bracing
^Stanchions, railings
*Frame and tarpaulin
Amine "D" drums, 55gallons; eight
Transit tank rental
Ball valves for tansit tank
2 25* carbonator hoses
COo
a*.
Drum rack and bracing
It is believed that most or all of the following equipment
and supplies requirements can be fulfilled by resources
available to this group:
Pumps: 2 metering, high capacity
Electric generator
Hoisting crane (one ton capacity)
Pnuematic impact wrench
**Crop duster aircraft charges Asterisked items pertain
to fluorescent night-time
**Fluorescer visibility capabilities,
if desired.
**uv illumination equipment
136
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PROPOSED
USE OF FLUORESCENT AGENTS AND ACOUSTIC SENSING FOR NIGHT-TIME HAZARDOUS
MATERIAL SPILL RECOVERY AND CONTROL OPERATIONS
Principal Investigator: William W. Bannister
Department of Chemistry
University of Lowell
Lowell, Massachusetts 01854
ABSTRACT
Oil and hazardous chemical spills pose serious problems in
terms of the very poor visibility often attending such situations.
No operational capability exists at night or in other periods of
low visibility, when operating personnel are unable to discern
spill boundaries. However, time is extremely important in spill
control and recovery work; in the space of a few hours areas cleared
of an oil spill by skimming or similar operations can be covered
again as unharvested oil drifts back over the cleared track.
Moreover, skimmers are most efficient with thicker oil films;
spreading of oil not only increases the operational area, but also
decreases film thicknesses with attendant decrease in efficiency.
of the effort.
We have previously demonstrated that commercially available,
non-toxic and highly efficient fluorescent agents with both oil and
water compatibility can be applied in very low concentrations to
oil spills with excellent results. In open water areas the agent
is dissipated into the water column, but is preferentially retained
in any oil patches on the water surface. At night, when natural
light has sufficiently diminished to permit visibility of fluorescent
light, UV light is beamed over the spill area with illumination by
resulting fluorescence occuring only from the oil spill patches,
thereby enabling easy discernment of the perimeters of such areas
and thus extendj.ng operational capabilities into night-time hours.
This would be particularly important in situations occurring in
winter months in higher lattitudes when night-time conditions are
significantly more prolonged than are daylight conditions.
In our previous work we have demonstrated also that very
considerable synergistic effects are realized on combination of the
fluorescence technique with environmental acoustic sensing gear,
whereby dispersions of oil into the near water surface can be
detected along with surface oil.
We now propose to perform full-scale tests with application
of the fluorescer in a dilute spray delivered either from ships or
from aircraft, over wide open water oil spills, and in other tests
in the form of mixtures fluorescer and finely powdered limestone
delivered as a dust from aircraft. In all cases conventional
skimmer craft equipped with UV flood light, and acoustic sensing
gear operated from such skimmer craft will be utilized to attempt
oil spill reconaissance operations.
137
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SUMMARY OF PROJECT PHASES
PHASE I. FEASIBILITY TESTING
A. Feasibility Testing (June 1^ - September 14. 1981)
This work, culminating in the September 14 ANTELOPE sea
trails, served to demonstrate the feasibility of use of
fluorescent illumination and acoustic sensing as a means
of providing a night-time capability for oil spill
recovery and control operations. Cf. preceding discussion
and Appendices B,C,D and E for details pertaining to this
work.
B. Design and Construction of Spraying Equipment, and
Investigation ot ImprqveH~FTuorescent Formulations
(September 1. 1781 - June 30, 19825
Support for this work has been provided by GTE/Sylvania,
Incorporated. The emphasis of this work is in the design
of shipboard equipment for those situations in which
aerial delivery systems may be inappropriate (e_.£., in
congested harbor situations), and in investigations of
various fluorescers in powdered limestone or other inert
formulations for dusting operations,,
With regard to new fluorescent agent systems we.are
currently investigating fluorescers provided by the Morton
Chemical Co. of Paterson, New Jersey which have significant
solubilities in hydrocarbons and which may be better suited
than stilbene derivatives for this work.
PHASE II. SYSTEM DESIGN AND OPERATIONAL TESTING OF EQUIPMENT
A. Shipboard UV Illumination Systems
No difficulties are anticipated in regard to design and
installation of suitable UV illumination sources for use
on shipboard. We anticipate a requirement for several
tests to determine the number, proper positioning, and
overall intensities .of the lamps to be used in the final
test exercises, and thereafter for routine use. It it
deemed advisable at this early moment to consider the
positioning of such lamps as high in the ship as possible,
to minimize sea-scatter effects and to achieve as wide a
coverage as possible, with lamps to be directed forward
and aft with maneuverability port and starboard.
We intend to consult extensively with the GTE/Sylvania
Corporations' technical personnel with regard to design,
installation, and operational sub-phases.
**• Aerial Devlivery and UV Illumination Systems
Conventional crop dusting techniques and apparatus, as
are available through a variety of firms in this area,
138
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are deemed adequate at this point for delivery of the
fluorescer agents onto spill areas.
The same considerations for UV illumination will apply
in this sub-phase as for the shipboard installations
discussed in the previous section.
C. Near-Surface Water Column Profiling Bv_ Acoustic Sensing
As A Complementary Means of Detecting Extents of Low-
VTsTbility Oil Spills
Datasonics, Inc. will serve in this study to track and
map concentrations of near-surface concentrations of
suspended oil in the water column, as an adjunct means
of detecting otherwise indiscernable (e.g., due to
night-time or other low-visibility conditions) oil
spills. This techniques, moreover, will provide a
gauge as to the rate and extent of dissipation of
surface slicks. The Model DFS-2100 Environmental
Echo Sounding System is a specialized dual frequency
system designed for this application. Operating from
3 to 300 khz, the system makes use of precisely
controlled and measured transmitted and received signal
levels to allow quantitative measurement of echo levels
produced by scatterers throughout the water column.
Use of a stabilized narrow beam transducer provides
extremely good resolution of discrete scatterers
associated with thermal or salinity changes, and other
natural processes which produce a density gradient.
(Reference is made to the last page of Appendix F to
this proposal, which illustrates the type of signal
provided by hydrocarbon suspensions in the water
column in acoustic sensing; the signal is best seen
in the upper left quadrant of this chart.)
Datasonics equipment also includes high resolution
' high powered low frequency, and general purpose
sub-bottom profiling systems with towed vehicle,
"over-the-side" and "in-hull" transducer installations.
D. Description o_f_ Proposed Exercises
It is proposed that an area of about 3,000 feet by 330
feet (about 23 acres) in open water areas of Cape Cod
Bay, or South of Buzzards Bay off the coastline of
Massachusetts, be utilized for both preliminary and
final tests.
The preliminary tests will probably require four
separate days, during which exercises the various sonic
and fluorescent effects and parameters discussed
previously will be studied singly and then jointly,
under various weather and wave conditions, varying
concentrations of fluorescer, and varying intensities
of UV light.
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After preliminary testing has been accomplished, the
overall fluorescent/sonic systems will be tested in
a final two-day exercise, again under varying conditions,
as a means of providing a "real-life" demonstration of
efficacy of the systems. For the final test exercises
the services of the EPA OSV ANTELOPE will be sought,
in view of the excellent research and monitoring
capabilities of this vessel.
Application of fluorescer agents will be tested both
preliminary and final exercises by aircraft dusting
operations. Ship-board systems will be studied, also.
For these purposes the services of a commercial crop
dusting firm are recommended, in view of the equipment
and expertise such a firm would possess for accurate
and even distribution of the agent. For spray purposes,
a volume of about 250 pounds of a fluorescer formulation,
comprised of about 8% of fluorescer suspended in powdered
gypsum or limestone, is recommended for the test,
representing a dose rate of about ten pounds per acre.
Smaller volumes of correspondingly higher concentration
could be utilized, as well. It is anticipated that.
the test area will have light to moderate coverage
(though more extensive spill coverage would be satisfactory,
also) by 2 ma. oil slicks, of any composition (light,medium
or heavy refined, residual or crude stocks) as may be
routinely encountered in the harbor area. Assuming even
distribution of the agent over the test area, oil patches
would then have an applied concentration of the agent in
the oil of about 0.007% (70 ppm). From previous test
results, it is anticipated that fluorescer applied to
open water (lacking oil coverage) would be effectively
dissipated into the water column within one hour after
spraying; for oil patches sprayed with the fluorescer
solution, it has been found that there is very little
extraction of the fluorescer into the water—after three
days, more than 98% of the fluorescer is still retained
in the oil.
An ideal time for application would be about 4PM,
thereby enabling adequate differentiation of oil slick
perimeters shortly after nightfall, some four or five
hours later. Dusting could be accomplished in night-time
operations, however, and this would probably be a
requirement for preliminary tests in which we would
intend to use vegetable or fish oil simulants. For the
final test operations it would be highly desirable to
utilize at least one hydrocarbon type of spill, in view
of the inadequacies (high density and high dispersability
of the simulant oils) which would probably prevent day-time
dusting followed by UV/sonic monitoring several hours
later. For most tests it is suggested that clear weather
(for both day and night phases) and low wind speed (for
the afternoon aerial application) conditions be sought.
Moreover, it would be desirable to choose a date during
which there would be minimal surface movement of the
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sprayed area (£•£•> due to tidal effects) between the
time of application and that of the night-time recovery
effort. Alternatively, use of untethered fluorescent
markers, ded reckoning calculations, or other means
should be employed to provide as much knowledge as
possible regarding movements of the sprayed area.
When deemed sufficiently dark for the recovery phase of
the overall operation, it is then suggested that a DIP
3001 Self-Propelled Harbor Skimmer (or equivalent) be
deployed, especially equipped for this test with two
1000-Watt mercury UV lamps without filters, to operate
continuously during the overall test excercises.
Conventional visible illumination is afforded by these
lamps,' in addition to UV radiation, to afford adequate
navigational capability in the steering of the craft;
at the same time, the enhanced UV-fluoresced visible
light from the oil patches will provide ample means for
full discernment of slicks on the water surface. In
order that wider-range fluorescence can be achieved,
thus providing full capability for overall evaluation
of the recovery effort, it is proposed that a helicopter
equipped with a rack of six 72 85-Watt UV fluorescent
lamps fly overhead to one side of the slick area (to
avoid downdraft effects on the slick area), with radio
communications between the helicopter's observer team
and the skitnmraer craft crew. With this capability the
skimmer could be guided from patch to patch.
At the suggestion of Dr. William Garrett of the Naval
Research Laboratories, it is also proposed at this time
to use a surface collecting agent (e.g., Navy Piston
Film) with a vividly colored fluorescer incorporated
in this agent's formulation, thereby further facilitating
the collection and control effort.
Recording of all events by motion picture and/or by videoj
and still photography would be highly desirable, during
both afternoon and night-time evolutions (the latter
obviously requiring rather sensitive film stock).
ANTICIPATED HAZARDS
TOXICITY: No significant hazards are anticipated. The fluorescent
agents which would be used are widely used additives in
many household detergent formulations, with full approval
by the FDA. The LD 50's for such agents are typically
about 10,000 mg/kg bodyweight for test animals in the
acute dosages, an index of quite low toxicity; in the
terms of chronic exposures (i.e_. , on a continuous basis)
of 1.000 ppm no observable effects are noted in test
animals over one and two year periods. No skin irritations
in human subjects are noted for such agents.
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uv
RADIATION: No hazard is anticipated from UV radiation front the
helicopter rack, in view of the anticipated altitude
(100 feet .or more); speed, motion and typical distance
of the helicopter from the skimmer craft, of 100 yards
or more; and low intensity of radiation. These lamps
are routinely used in outdoor and indoor advertising,
entertainments, and similar applications with no required
eye protection. In as much as these lights will be
projected downward with no upward illumination, aircraft
crew will not be exposed to this radiation at all. The
more powerful 1000 Watt lamps contemplated for use on the
skimmer would present an eye hazard for personnel experiencing
constant radiation within a distance of 100 feet. These
lamps are therefore proposed for mounting on bowsprit
assemblies extending twenty feet in front of the skimmer,
with beams directed forward and downward on the water in
front of the boat out to a distance of 100 feet, and with
complete shielding in back of the lamps to prevent any
radiation onto the skimmer itself.
All personnel working with this project will be issued
goggles to be worn in the event of accidental misalignment
of lamp beams; and all UV sources will be deenergized in
the event of such accidental misalignment.
No serious UV hazards are anticipated.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION>NO.
4. TITLE AND SUBTITLE NEW TECHNIQUES FOR FLOATING POLLUTANT.
SPILL CONTROL AND RECOVERY.
5. REPORT DATE
August 15, 1983
6. PERFORMING ORGANIZATION CODE
7. AUtHOR(S)
W.W. Bannister, W.A. Curby, D.L. Kan, W.J. Dalton,
D.A. Porta, and A.A. Donate!11
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
University of Lowell, Lowell, MA 01854; Sias Labora-
tories, Lahey Clinic Foundation, Burlington, MA 01803
Massachusetts Maritime Academy, Buzzards Bay, MA
02532; Datasonics, Inc., Cataumet, MA 02534
10. PROGRAM ELEMENT NO.
CBRD1A
1. CONTRACT/GRANT NO.
EPA Project Mos. R806118 01
and R804628 01
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory--Cin. ,OH
Office of Research & Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final. 9/15/78-9/14/79
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
Project Officer: Uwe Frank (201) 321-6626
i6.ABSTRACT Hazardous -material (HM) spills pose serious problems in terms of the very
poor visibility often attending such situations. No operational capability exists at
night or other periods of low visibility. However, time is very important in spill
control and recovery work; in a few hours, areas cleared of an HM spill can be cov-
ered again as unharvested HM drifts back over the cleared track. Moreover, skimmer
operations are most efficient with thicker oil films; spreading of oil not only in-
creases the operational area, but also decreases film thicknesses with attendant de-
crease in efficiency of the effort. This report discusses new techniques whereby (1)
HM spills can be gelled quickly and completely to a solid consistency. The gel is of
much greater visibility; does not readily flow or spread; is easily, quickly, and com
pletely recovered by nets; has lower volatility and lower fire and toxicity hazards;
does not permeate into porous materials; and is easily regenerated into the original
HM and gelling components. (2) Cheap, nontoxic and efficient fluorescent agents can
be applied in low (50-ppm) concentrations onto" spills by conventional crop-dusting
or spraying techniques. Where there is open water with no HM cover, the fluorescer is
dissipated into the water, but is preferentially retained wherever there are HM
patches. At night, illumination by UV light (modified mercury vapor street lights)
can be beamed over the spill area. Vivid fluorescent illumination occurs only from
the HM patches, providing night-time control and recovery capability. (3) Underwater
su
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Acoustic Sensing Environmental Techniques;
Amine Carbamates; Amine D; Amine Gelants;
Beach Protection; Fire Hazard Reduction;
Fluorescers; Gelation; Hazardous Material
Spill Control; Hazardous Material Spill Re
covery; Night-Time Operations; Sonic Sens-
ing Environmental Techniques.
8. DISTRIBUTION STATEMENT
Release froj Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (TMtpaft)
Unclassified
22. PRICE
EPA form 2220-1 (»-73)
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