Edison Water Quality Laboratory
September 1971
 CONTROL OF HAZARDOUS MATERIAL
 SPILLS IN THE WATER ENVIRONMENT:
           AN OVERVIEW
ENVIRONMENTAL PROTECTION AGENCY  WATER QUALITY OFFICE

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                            CONTROL  OF HAZARDOUS MATERIAL
                           SPILLS  IN THE  WATER  ENVIRONMENT:
                                    AN OVERVIEW

                           Ira  Wilder and Joseph Lafornara

                      Hazardous Material  Spills Research Section
                           Environmental  Protection  Agency
                           Edison  Water Quality Laboratory
                                  Edison, New Jersey
                                   I   INTRODUCTION

    More than two billion tons of potentially hazardous materials were produced
and handled in the United States during 1968-1969.  It is projected that the annual
production quantities of these materials will approximate four billion tons in 1980.
Over 70 percent of these quantities are transported by motor truck, railway, water
barge and pipeline.  As long as the tonnage of liquid, solid and gaseous hazardous
chemicals produced, handled, and transported continue to follow the present upward
trend, the accidental spillage of these materials poses a real and growing threat
of pollution to our watercourses.

                                    II EFFECTS

    The effects of these materials on watercourses and the plant and animal life
associated with them may vary widely.  In general, most chemicals, when present in
the environment above certain critical concentrations, are toxic to biological life
and detrimental to the environment's aesthetic quality.  Although many substances
are obviously hazardous to aquatic and marine life due to direct acute toxicity,
other substances are equally detrimental to water ecosystems by virtue of indirect
toxicity resulting from depletion of the dissolved oxygen supply required to support
various life forms.  Still others, although originally present at less than toxic
or inhibitory levels, may become concentrated to these levels by residual accumu-
lation through a succession of food chain transfers.  In addition to direct effects
of the spilled hazardous materials, there may be other effects of the products of
reaction between the pollutant and water or other materials in the watercourse.

                                     Ill  CAUSES

A.  General

    The accidental entrance of a hazardous material into a watercourse can occur
in a variety of ways.  Spills or sudden discharges can result from mechanical mal-
function, collision, fire or human error in connection with rail, highway and
water modes of transportation or with stationary sources such as manufacturing
or storage facilities.  The most serious type of spill occurs when a container is
violently ruptured and large quantities of the hazardous material are spilled al-
most instantaneously.  In some cases, the material may be discharged directly into
a watercourse, while in others' the spilled material may flow or be washed into
sewers, drainage channels or percolate slowly into ground water supplies.

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B.  Transportation Sources

     A  significant portion of the total problem of hazardous material spills is
caused  by transportation accidents.  Wnile derailment presents the major potential
for railroad  tank car spills, collision and sinking are obvious sources of barge
spills.  Spills may also occur at tank truck, tank car and barge loading/unloading
facilities due to defective transfer pump and flange connections, hose failures
and valve packing and seal deficiencies.

C.  Stationary Sources

     1.  One  of the largest single sources of pollution incidents in industrial
plants  is failure or breakdown of manufacturing or process equipment.  These fail-
ures include  broken pipelines in chemical plants, leaking tanks, malfunction of
refrigeration equipment, overflowing of chemicals from tanks during manufacture,
faulty  pressure gauges and valves, pump breakdown, operational errors, metal failure
due to  corrosion in acid transport pipes, explosions and fires.  These sources of
pollution incidents are compounded to some degree by the many intentional discharges
of unwanted hazardous materials into our nation's waters.

     2.  Storage facility spills also contribute to the overall problem.  Numerous
fish kills result from leaks from storage tanks and broken lagoon dikes.  The leach-
ing action of rain water on open stockpiles of hazardous chemicals stored in the
open at water edge locations has also greatly added to the contamination of our
waterways.

                                    IV  CONTROL

A.  Prevention

     It is generally agreed that the prevention of hazardous material spills con-
stitutes the most desirable method for effective water pollution control.  Unfor-
tunately, previous efforts to provide adequate safeguards for handling these
materials and for preventing their release into the aquatic environment have not
been very successful.  A recently completed study^', initiated by the Environmen-
tal Protection Agency's Division of Oil and Hazardous Materials, concluded that
there are presently no uniform industry-wide standards in the United States for
spill prevention and, consequently, preventive techniques, equipment and operational
procedures need to be developed to protect the public health and welfare.

B.  Countermeasures

     1.  General

     Although prevention remains the first and most important line of defense,
it must be recognized that even with the most comprehensive precautionary tech-
niques, accidents involving the uncontrolled release of detrimental substances to
the environment must be anticipated and appropriate response measures must be de-
veloped to minimize undesirable ecological effects.  Existing countermeasure tech-
niques  have been developed primarily for continuous discharge waste treatment
systems under controlled conditions.  However, because of the rapid response re-
quired  in the case of spills,  the majority of these available techniques are not
satisfactory for application in the aquatic environment.

     Hazardous materials involved in spills which enter a watercourse may be cate-
gorized on the basis of their  densities and solubilities in water.  The heavier,
insoluble materials such as ethylene dichloride and sulfur will sink to the bottom
of waterways.  The removal of  these contaminants by physical means, such as suction
or dredge type devices,  is a possibility.   Less dense water insoluble chemicals
such as decyl alcohol will tend to float.   The mechanical separation of these

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materials by  confining  the  spill to a  small area by booms and removing the materials
by  skimming should  be relatively successful.  In the case of water soluble materials
such  as  phenol and  acrylonitrile, mechanical means of removal are not possible since
the spilled material will be  in solution.

      2.  Priority Ranking System

      Because  water  soluble  chemicals present the greatest threat to the water eco-
system from a countermeasure  point of  view, a priority ranking system for estimating
the theoretical  inherent hazard of these chemicals was prepared as part of an EPA
sponsored state-of-the-art  study    on hazardous material spills.  The ranking sys-
tem is based  on  (a)  the lowest concentration range at which a material impairs any
of  the beneficial uses  of water, (b)   the quantity shipped annually by each mode of
transport and (c)   the  probability of  an accidental spill to surface waters for each
transport mode.  Since  a material's ranking is then representative of its potential
threat to water  quality, it is expected that this system should provide the guide-
lines for determining which chemicals  receive the greatest attention relative to the
development of spill countermeasure techniques.

     To  illustrate  this ranking system, the top twenty water soluble substances are
arranged in order of decreasing priority in Table I.

                                     TABLE I

                 PRIORITY RANKING OF SOLUBLE HAZARDOUS SUBSTANCES

                 Rank                         Substance

                  1                    Phenol
                  2                    Methyl Alcohol
                  3                    Cyclic Rodenticides
                  4                    Acrylonitrile
                  5                    Chlorosulfonic Acid
                  6                    Benzene
                  7                    Ammonia
                  8                    Misc. Cyclic Insecticides
                  9                    Phosphorous Pentasulfide
                 10                    Styrene
                 11                    Acetone Cyanohydrin
                 12                    Chlorine
                 13                    Nonyl Phenol
                 14                    DDT
                 15                    Isoprene
                 16                    Xylenes
                 17                    Nitrophenol
                 18                   Aldrin-Toxaphene Group
                 19                   Ammonium Nitrate
                 20                   Aluminum Sulfate

These substances include both organic and inorganic materials and range from solids
to  liquids to gases under standard conditions of pressure and temperature.

     3.   Defensive and Offensive Measures

                               (2)
     The state-of-the-art study    also provides a summary of possible measures
that can be employed in responding to hazardous material  spills.   The counter-
measures are divided into two major classifications:   defensive and offensive.

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 The defensive measures,  which do not counteract the contaminant  in the environment,
 consist of notifying all downstream water users of the occurrence of a spill  and
 physically removing all  bags, barrels and other containers  which may still  be leak-
 ing into the watercourse.  The offensive measures include the following:

      (a)  Physical Containment - These measures are only applicable to insoluble
 hazardous materials which are less dense than water.  In most cases the use of pre-
 sently available "booming" equipment should be successful when environmental  con-
 ditions permit.

      (b)  Physical Removal - This technique offers possibilities for removal  of
 insoluble materials from watercourses.  The use of skimming devices should  be rela-
 tively effective for removal of materials less dense than water, whereas  dredges
 and suction devices are  potential countermeasures for those chemicals more  dense
 than water.

      (c)  Physical Mixing - In the case of  spills of certain soluble hazardous
 materials which  are toxic only at relatively high concentrations,  it may  be possi-
 ble to use agitating devices such as outboard motors to  accelerate natural  dilution,
 and thereby reduce the concentration of the pollutant to a  level far below  critical
 concentrations.   It should be emphasized that this method can only be employed for
 the small number of materials which are toxic only at high  concentration  levels and
 which can be biologically degraded without  detrimental effect to the body of  water
 involved.

      (d)   Chemical  Removal  - For  most  soluble hazardous  materials,  chemical methods
 of  removal  show  the most promise.   There are several  possible chemical  counter-
 measures,  all  of which require further development before they can be operational.
 These include:

           (1)  Addition  of  Chelating,  Complexing,  or  Precipitating Agents - These
 methods  involve  the addition of a  secondary agent  to  react  with  the soluble hazar-
 dous  polluting substance to form  an insoluble product which can  be removed  from the
 watercourse by skimming,  dredging  or suction pumping.  Before these methods can be
 accepted,  studies  must be undertaken to assure  that  the  chelating,  complexing or
 precipitating  agents  and  the resulting compounds  formed  by  reacting these agents
 with  the  spilled  pollutant  are considerably less  harmful  to the  water ecosystem
 than  the  pollutant.

           (2)  Addition  of  Neutralizing Agents  - These methods involve  the addition
 of  acids  or  bases  to  neutralize the spilled  material  and  render  it harmless to  the
 environment.  The  use of  neutralizing  agents  is obviously limited  to only those
 acidic and  basic materials  which are considerably  less toxic  than  the spilled
 chemical  and which, upon  reaction  with the  chemical,  generate no deleterious  secon-
 dary  products.

           (3)  Chemical Removal Using  Chemisorption - Potentially,  this technique
 shows the most promise of any  chemical  removal method.  For several  years, adsorp-
 tion of trace organics on activated carbon has been used  in tertiary sewage or
 potable water treatment.   The  principal  limitation of this method  is  that it  is
 severely dependent  on a  significantly  large,  ready supply of  carbon.  Consequently,
 carbon chemisorption  techniques can not  be readily utilized at the  present time
unless the  spill occurs at a location near to where a treatment facility already
exists.

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     U.  Current Status

     It  is clear from the above that adequate control, neutralization and treatment
 techniques for  countering spills of hazardous materials are practically non-existent,
 These countermeasures for the most part require technology not presently available.
 Nevertheless, it is considered that new and useful techniques can be developed by
 intensive experimental programs on spill control and cleanup methods.

     Inasmuch as the Water Quality Improvement Act of 1970^) requires the designa-
 tion of  appropriate methods and means of removal of spilled hazardous materials,
 the Environmental Protection Agency's Division of Applied Science and Technology
 initiated a number of programs for the development of methods to treat and control
 spills of selected high priority hazardous materials.  These programs cover a wide
 range of countermeasures for:  containing spills before they reach surface waters;
 for containing  contaminated water after a spill; and for decontaminating polluted
 water areas to  return the water to a restored condition of quality.  Specifically,
 some of  the proposed countermeasures under investigation are:

     (a)  development of devices to contain spilled hazardous materials on land
 by use of rapidly formed in place plastic dams or foamed dikes.

     (b)  development of foamed plastic devices for stopping leaks of hazardous
 materials from  ruptured containers both on land and underwater.

     (c)  development of methods to polymerize and remove spilled hazardous mater-
 ials on land and to prevent percolation of the materials into the ground.

     (d)  development of rapidly deployable physical barriers which extend from
 above the surface of the water to the bottom of the waterway for the purpose of
 containing spilled hazardous materials in watercourses.

     (e)  development of a decontamination system using floatable mass transfer
 media (e.g., ion exchange resins and carbon sorption media modified to result in
 specific gravities less than 1) for:  subsurface introduction into waterways;
 treatment of contaminants; and collection of spent media at the water's surface.

     (f)  development of a continuous flow through thin film aerator to which
 chemicals can be added to neutralize, oxidize, precipitate or adsorb spilled
 hazardous materials from watercourses, and to develop a static sealed centrifuge
 to remove gases, precipitates, carbon slurries, and other solids from the effluent
 of the aerator device.

     (g)  development of a modular transportable treatment system incorporating
various unit processes such as neutralization, flocculation, precipitation, filtra-
 tion and carbon adsorption,  for the purpose of on-site removal and treatment of
 spilled hazardous materials  in waterways.

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                                  V  RESEARCH NEEDS

     The Environmental Protection Agency will continue to place substantial emphasis
on research and development programs (in which contracts and grants will be awarded)
to develop new concepts for coping with the hazardous material spill problem.  In
this regard, it is essential that the best available research capabilities be util-
ized to develop the technology required to protect the water ecosystem.  Some of the
EPA's research needs in this area are briefly outlined below.

A.  Prevention

     Because of the chemical and physical nature of hazardous substances and the
inherent difficulty of their removal from watercourses,'. preventive techniques are
viewed as a primary means of mitigating damage to the aquatic environment.  To de-
velop the technology to prevent spills, the need exists to define the critical areas
of maximum spill probability.  For this purpose, potential high frequency spill
sources, such as production sites, terminal and storage facilities and the various
transportation modes, should be explored.

B.  Reporting and Information System

     To insure prompt response to a spill, there is a need for the development of a
spill reporting and information retrieval system.  This system should have the cap-
ability of storing chemical, physical and biological data, past spill information
and control techniques for a continuously expanding library of high priority haz-
ardous materials.  The system would rapidly communicate this information and data
during a spill incident so that the best possible countermeasure devices could be
dispatched to cope with the incident.

C.  Detection, Identification and Monitoring

     The rapid and effective deployment and use of hazardous material spill control
techniques requires the immediate knowledge of the identity and concentration of the
polluting substance, as well as the extent of the spill at any given time.  Accord-
ingly, the need exists for the development of readily available field equipment and
devices to rapidly detect, characterize and monitor spilled contaminants in the
water environment.

D.  Restoration and Damage Assessment

     Severe damages to the aquatic environment may result from spills of hazardous
substances because of failure of preventive techniques or unavailability of ef-
fective, rapid countermeasures.  Consequently, there is a need for the development
of restoration procedures, such as reseeding techniques,  for rebuilding damaged
ecological systems.  To fulfill this need, procedures should also be developed for
assessing the nature and extent of damage to the environment resulting from such
spills.

E.  Fate and Effects

     In order to comprehensively evaluate and assess the ecological damage result-
ing from hazardous chemical spills and to better identify the high priority
materials requiring more detailed prevention methodology, a study is needed to
determine the fate and long term effects of these materials on the environment.
In this respect, information is needed on the persistence of the materials and
their synergistic and antagonistic effects on watercourses.

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F.  Ultimate Disposal

     Methods to contain and/or treat spilled hazardous materials will result in
varying volumes and concentrations of liquids and sludges which must be disposed
of in such a manner as to prevent subsequent hazards to the environment.  Need
exists, therefore, to review and evaluate existing disposal technology that may
be applicable for spill incidents and to develop new, more effective methods where
necessary.

                                  VI  REFERENCES

1.  "Spill Prevention Techniques for Hazardous Polluting Substances", Arthur D.
    Little, Inc., Report No. OHM 7102001, prepared under Contract 14-12-927 for
    the Environmental Protection Agency, February 1971.

2.  "Control of Spillage of Hazardous Polluting Substances", Battelle Memorial
    Institute, Pacific Northwest Laboratories, Report No. 15090 FOZ, prepared
    under Control 14-12-866 for the Federal Water (Duality Administration,
    November 1970.

3.  Public Law 91-224, 91st Congress, H. R. 4148, "Water Quality Improvement Act",
    April 3, 1970.

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