United States
Environmental Protection
Agency
Hazardous Waste Engineering
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S2-87/068 Feb. 1988
&ERA Project Summary
Manual for Preventing Spills of
Hazardous Substances at
Fixed Facilities
Walter Unterberg, Robert W. Melvold, Kathleen S. Roos, and Patricia A. Scofield
The purpose of this project was to
prepare a manual that provides guidance
on preventing spills of hazardous sub-
stances in fixed facilities that produce
substances from raw or starter mate-
rials, store the substances, or transfer
the substances to and from transporta-
tion terminals. The emphasis is on
smaller-sized chemical manufacturing
facilities.
The manual consists of seven sections
and an Appendix: 1. Introduction; 2.
Manual of Practice; 3. Hazardous Sub-
stances and Their Characteristics; 4.
Fixed Facilities; 5. Facility Spill Preven-
tion Practices; 6. Preventive Engineering
Practices; and 7. Bibliography. The
appendix contains descriptions of fixed
facility chemical processing equipment
components, from which a checklist of
equipment items interacting with
hazardous substances can be derived
for use in preparing a Spill Prevention
Plan.
This Project Summary was developed
by EPA's Hazardous Waste Engineering
Research Laboratory, Cincinnati, OH, to
announce key findings of the research
protect that If fully documented In a
separate report of the same title (see
Project Report ordering Information at
back).
Introduction
The purpose of this project was to
prepare a manual that provides guidance
on preventing spills of hazardous sub-
stances from fixed facilities that produce
hazardous substances from raw or starter
materials as products, byproducts or
waste products; store hazardous sub-
stances; or transport hazardous sub-
stances. The audience to be addressed
includes managerial and supervisory
personnel as well as "hands on" per-
sonnel associated with smaller-sized
chemical manufacturing facilities. The
hazardous substances in question num-
ber almost 700, excluding oil, and are
those designated pursuant to Section 101
(14) of the Comprehensive Environmental
Response, Compensation and Liability Act
of 1980, otherwise known as CERCLA or
Superfund (Public Law 96-510).
The earlier Clean Water Acf (Public
Law 92-500) in Section 311, required
that the President issue regulations
"establishing procedures, methods and
equipment ... to prevent discharges of
oil and hazardous substances from
vessels and from onshore and offshore
facilities..." Under a 1973 executive
order, the U.S. Environmental Protection
Agency (EPA) was to promulgate regula-
tions for preventing nontransportation-
related spills.
In 1973, EPA issued oil pollution pre-
vention regulations (40 CFR Part 112)
that require certain fixed facilities to have
on file a spill prevention, control and
countermeasures plan (SPCC plan). These
regulations have been largely accepted
by industry and have proven to be effective
in preventing oil spills.
In the case of hazardous substances,
no similar federal regulations exist at this
time. In its own interest, a large segment
of the industry producing, storing, and
handling hazardous substances has in-
stituted internal spill prevention plans.
However, many of the smaller affected
facilities may not have generated spill
prevention plans for various reasons.
This manual is designed to assist them in
preparing such plans.
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<*!
Source material for this manual was
derived from government, industry and
commercial publications. Related oil spill
prevention literature included: the Guide
for Inspectors; a report on Prevention
Practices at Small Petroleum Facilities;
state contingency plans, such as the Oil
Spill Contingency Plan of the State of
California; and the extensive Oil Spill
Prevention Control and Countermeasure
Plan Review. Publications dealing with
hazardous substances included cost
analyses for hazardous substance pollu-
tion prevention, Best Management Prac-
tices (BMP) documents, an industrial spill
prevention plan, and a treatise on Safety
and Accident Prevention in Chemical
Operations.
Manual of Practice
Section 2 of the manual presents the
procedure for developing a facility spill
prevention master plan. The procedure is
divided into 10 steps that are expanded
in the remainder of the manual. The
manager selected to oversee the plan,
and constant support of upper level
management, are essential for successful
implementation of the project. Specialists,
as required to perform the various tasks
outlined below, and the involvement of
people from different parts of the facility,
will provide a wide base of support for
the plan and increase its acceptance by
plant personnel who will be its main
beneficiaries. The 10 procedural steps
are as follows:
1. Form a facility spill prevention
organization supervised by a part-
time or full-time manager and backed
by the plant management.
2. Prepare a prevention policy state-
ment approved by management.
3. Define facility boundaries and pre-
pare flowsheets indicating genera-
tion and storage of all substances
within these boundaries, as well as
inflow and outflow of substances
across the boundaries. Hazardous
substances present in raw materials,
products, byproducts, wastes, fuels,
lubes, paints, pesticides, disinfec-
tants, etc., should be identified.
Normal and overload conditions
should be noted.
4. List the substances that are hazard-
ous by reference to Section 3 and
the tables of hazardous substance
characteristics contained therein.
Note the environmental media into
which the substances would be
released, their physical behavior on
release, and the hazards caused by
the release.
5. List all facility areas and equipment
items that interact with hazardous
substances. Include storage vessels
of all kinds (gas, liquid, solid), process
vessels and columns, flow systems
including valves and controls, re-
ceiving and shipping terminals of all
kinds (road, rail, water, air), and
waste treatment and disposal areas.
Use Section 4, Fixed Facilities, to
identify those areas and equipment
that could interact with hazardous
substances.
6. For each area and equipment item
of interest, list possible failure
modes; amount of hazardous sub-
stance involved; hazards caused by
possible release of substance (from
Step 4 above); and specific effects
expected on the rest of the facility
and surroundings, considering
equipment and personnel at various
times and varying weather con-
ditions.
7. For each area and equipment item,
look over Section 5, Facility Spill
Prevention Practices (SPPs), and
extract the applicable Preventive
Engineering Practices.
8. For each area and equipment item,
look over Section 6, Preventive
Engineering Practices (PEPs), and
extract the applicable PEPs.
9. Write a facility spill prevention
master plan under direction of the
manager by combining information
from Steps 3 through 8. The plan
should consider drainage to receiving
waters and facility terrain, and
should include a timetable for carry-
ing out the SPPs and PEPs.
10. Have the plan approved by plant
management and implemented
under direction of the spill prevention
organization, which also should be
responsible for its periodic review
and revision.
Hazardous Substances and
Their Characteristics
Section 3 of the manual contains tables
of information on the almost 700
CERCLA-designated hazardous sub-
stances. Once all the substances within
a plant have been identified, they should
be checked against these tables to deter-
mine which are hazardous. Only those
considered hazardous require further
consideration.
Hazardous substances may be gases,
liquids, or solids; and, they may be re-
leased to the air, water, or ground. The
manual presents four tables: (1) liquids
and solids spilled on water, (2) liquids I
spilled on ground, (3) solids (particulates)
released to air or ground, and (4) gases
released to air (a sample page from each
is provided here as Tables 1 -4, re-
spectively).
Table 1 contains (1) an alphabetical
listing of substances, primarily chemical
compounds; (2) chemical class, some-
times more than one; (3) Chemical
Abstract Service (CAS) number, a stan-
dard in cases where substances are
known by more than one name; (4)
hazards in addition to toxicity; and (5)
behavior in water — sink/float and
soluble/insoluble. The fifth or last column,
"Behavior in Water," is not included in
Tables 2, 3, and 4.
The hazards listed in the fourth column
of each table are defined in 49 CFR 173
(Department of Transportation (DOT)
regulations), the Clean Water Act, and by
the U.S. Department of Health and Human
Services. In the following list, an asterisk
designates definitions developed during
this work.
• Carcinogen — substance identified
as potentially cancer-producing in
humans.
• Combustible — liquid or solid having
a flash point at or above 100°F and
below 300°F; the upper limit was
changed from the DOT value of
200°F to 300°F to realistically in-
clude more substances as com-
bustible.
• Corrosive — substance causing
visible destruction or irreversible
alterations in human skin tissue at
the site of contact.
• Explosive — any chemical compound,
mixture, or device providing sub-
stantial instantaneous release of gas
and heat.
• Flammable — substance as defined
in 49 CFR 173.300 (gas), 49 CFR
173.115 (liquid), and 49 CFR 173.150
(solid).
• Oxidizer — substance that yields
oxygen readily to stimulate the
combustion of organic matter.
• Poison — substance so classed or
labelled in 49 CFR 172.101.
• Polymerizable — substance under-
going a rapid exothermic polymeriza-
tion reaction initiated by exposure tc
heat, light, acids, caustics, or othei
sources.
• Radioactive material — substanct
spontaneously emitting ionizing
radiation.
• Reactive — substance that readily
undergoes violent change withou
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Table 1. Releases in Water
Hazardous Substance
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetic acid
Acetic anhydride
Chemical Class
Aromatics
Aromatics
Aldehydes
Acidic compounds, organic
Acidic compounds, organic
CAS No.
83-32-9
208-96-8
75-07-O
64-19-7
108-24-7
Hazardts). in
Addition to Toxicity
Combustible
Combustible
Flammable
Polymerizable
Combustible
Corrosive
Combustible
Corrosive
Behavior in Water
Insoluble Sinker
Insoluble Floater
Soluble
Soluble
Soluble, decomposes
Acetone
Acetone cyanohydrin
Acetonitrile
Acetophenone
Acetyl bromide
Acetyl chloride
2 -A cetylaminofluorene
1 -Acetyl-2-thiourea
Acrolein
Aery I amide
Ketones
Cyanides and nitrites
Cyanides and nitrites
Ketones
Aliphatics, halogenated
Aliphatics, halogenated
Amines, aryl
Ureas
Aldehydes, Olefins
Amides, anilides, and imides
67-64-1 Flammable
75-86-5 Combustible w/toxic products
Poison
75-05-8 Flammable w/toxic products
98-86-2 Combustible
506-96-7 Flammable w/toxic products
Corrosive
Reactive
75-36-5 Flammable w/toxic products
Corrosive
Reactive
53-96-3 Potential carcinogen
591-08-2
107-02-8 Flammable
Polymerizable
Poison
79-O6-1 Polymerizable
Soluble
Soluble
Soluble
Insoluble Sinker
Decomposes (Sinker)
Decomposes (Sinker)
Insoluble Sinker
Soluble
Soluble
Solubit
detonation in the presence of water
or moist air, or even dry air or oxygen.
• Toxic pollutant — material which
upon exposure, ingestion, inhalation,
or assimilation into any organism,
causes death, disease, behavioral
abnormalities, cancer, genetic muta-
tions, physiological malfunctions, or
physical deformations.
A thorough understanding of the various
hazards is essential for effective selection
of preventive countermeasures. This sec-
tion provides data in the form of four
tables of Hazardous Substance Charac-
teristics for identifying and listing those
substances that are hazardous in ac-
cordance with Step 4 of the procedures
for developing a facility spill prevention
master plan. The first page of each of the
following tables is presented as a sample.
Table #
Release Scenario
1 Releases in Water
2 Liquids Released on Land
3 Paniculate Solids Released on Land
4 Compressed Gases Released Into A ir
Fixed Facilities
The manual can be applied to any fixed
facility. If one excludes the petroleum
refining industry, which is covered by an
existing Oil Pollution Prevention Regula-
tion (40 CFR 112), there are 20 major
industry categories defined in 40 CFR
124, Appendix D, as follows:
No.
Major Industry Category
1 Timber Products Processing
2 Steam Electric Power Plants
3 Leather and Leather Products
4 Iron and Steel Manufacturing
5 Inorganic Chemicals Manufacturing
6 Textile Mills
7 Organic Chemicals Manufacturing
8 Nonferrous Metals Manufacturing
9 Paving and Roofing Materials
10 Paint and Ink Formulation and Printing
11 Soap and Detergent Manufacturing
12 Auto Wash and Other Laundries
13 Plastics and Synthetic Metals
Manufacturing
14 Pulp, Paper and Board Mills, and
Products Manufacturing
15 Rubber Processing
16 Miscellaneous Chemicals
17 Machinery and Mechanical Products
Manufacturing
18 Electroplating
19 Ore Mining and Dressing
20 Coal Mining
Several of these categories fall within
the chemical manufacturing area. Others,
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Table 2. Liquids Released on Land
Hazardous Substance
Acetaldehyde
Acetic acid
Acetic anhydride
Chemical Class
Aldehydes
Acidic compounds, organic
Acidic compounds, organic
CAS No.
75-07-0
64- 1 9-7
108-24-7
Hazardfsj, in
Addition to Toxicity
Flammable
Polymerizable
Combustible
Corrosive
Combustible
Corrosive
Acetone Ketones
Acetone cyanohydrin Cyanides and nitrites
Acetonitrile
Acetophenone
Acety/bromide
Acetyl chloride
Acrolein
Acrylic acid
Acrylonitrile
Ally! alcohol
Cyanides and nitrites
Ketones
t," ;*,•<>, halogenated
Aliphatics, halogenated
Aldehydes,
Olefins
Acidic compounds, organic,
Olefins
Cyanides and nitrites
Alcohols andglycols,
Olefins
67-64-1 Flammable
75-86-5 Combustible w/toxic
products
Poison
75-O5-8 Flammable w/toxic
products
98-86-2 Combustible
506-96-7 Flammable w/toxic
products
Corrosive
Reactive
75-36-5 Flammable w/toxic
products
Corrosive
Reactive
107-02-8 Flammable
Polymerizable
79-10-7 Combustible
Corrosive
Polymerizable
107-13-1 Flammable w/toxic
products
Polymerizable
Potential carcinogen
Poison
107-18-6 Flammable
Poison
such as mining (Nos. 19 and 20), metal
processing in various forms (Nos. 4, 8,
18, and 19), and production of non-
metal lies (Nos. 3, 6, 9, 13, 14, and 15),
also deal with hazardous substances.
Each industry has its own specialized
equipment and facility areas. For the
present purpose, this section lists and
describes the equipment found in chemi-
cal manufacturing plants. For other in-
dustries, this section and the Appendix
would have to be modified.
In accordance with Step 5 of the
procedures for preparing a master plan, a
list of plant component interactions with
hazardous substances is required.
A check list of all facility areas and
components is useful for developing the
final list. Reference to the Chemical
Engineers' Handbook (1973, 5th edition)
led to the identification of major facility
area categories which cover processing,
transportation, storage, waste treatment,
and disposal. A detailed description of
hazardous substance interactive systems
and equipment (including further division
of the major categories) is provided in the
Appendix. A listing of the systems and
equipment is provided here:
1. Transport and storage of fluids
(pumps, pipes, valves, tanks, etc.)
2. Handling of bulk and packaged
solids (conveyors, silos, etc.)
3. Size reduction and enlargement
(mills, compactors, etc.)
4. Heat generation and transport (fired
process equipment, incinerators,
etc.)
5. Heat transfer equipment (heat ex-
changers, condensers, etc.)
6. Evaporative cooling and refrigera-
tion (cooling towers, cryogens, etc.)
7. Distillation columns
8. Gas absorption towers
9. Liquid extraction systems
10. Adsorption and ion exchange
equipment
11. Miscellaneous separation pro-
cesses (crystallization, membranes,
etc.)
12. Liquid-gas systems (contacting,
phase dispersion, phase separation)
13. Liquid-solid systems (contacting,
phase dispersion, phase separation)
14. Gas-solid systems (contacting,
phase dispersion, phase separation)
15. Liquid-liquid systems (contacting,
phase dispersion, phase separation)
16. Solid-solid systems (contacting,
phase dispersion, phase separation)
17. Waste treatment plants (equip-
ment associated with primary,
secondary, and tertiary treatment
and disposal).
Facility Spill Prevention Practices
In general, spill prevention practices
(SPPs) are independent of the exact nature
of the facility, its processes and products.
While most SPPs are based on common
sense and experience and provide few
new revelations, it is useful to have this
compilation of procedures when preparing
a spill prevention master plan.
SPPs have been drawn from govern-
ment and industry reports and publica-
tions. Some, listed here, overlap into
related areas such as response to a spill,
maintenance, and training. If the facility
already has plans and procedures in these
areas, they can be adapted to the present
purpose. A short discussion for each SPF
listed below is given in the manual.
SPILL PREVENTION ORGANIZATIOls
RISK IDENTIFICATION AND
ASSESSMENT
MATERIALS COMPATIBILITY
REPORTING AND RECORDKEEPINC
GOOD HOUSEKEEPING
PREVENTIVE MAINTENANCE
INSPECTION SYSTEMS
SECURITY
EMPLOYEE TRAINING
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Table 3. Paniculate Solids Released on Land
Hazardous Substance Chemical Class
CAS No.
HazardfsJ, in
. Addition to Toxicity
Acenaphthene
Acenaphthylene
2-Acetylaminofluorene
1 -Acetyl-2-thiourea
Aery/amide
Aromatics
Aromatics
Amines, aryl
Ureas
Amides, anilides and
imides
83-32-9
208-96-8
53-96-3
591-08-2
79-06-1
Combustible
Combustible
Potential carcinogen
Polymerizable
Adipic acid
Aldicarb
Aldrin
Aluminum phosphide
Aluminum suit ate
S-fAminomethyll-3-
isoxazolol
Amitrole
Ammonium acetate
Ammonium benzoate
Ammonium bicarbonate
Acidic compounds, organic
Esters
Aromatics, halogenated
Phosphorous and
compounds
Sulfates
Amine, alkyl
Azo compounds
Organic ammonium
compounds
Organic ammonium
compounds
Organic ammonium
compounds
124-04-9
116-O6-3
309-00-2 Combustible w/toxic
products
Potential carcinogen
Poison
20859-73-8 Flammable w/toxic
products
Reactive
10043-01-3
2763-96-4
61-82-5 Potential carcinogen
631-61-8
Ammonium bichromate Chromates
1863-63-4 Combustible w/toxic
products
1066-33-7
7789-O9-5 Corrosive
Oxidizer
Flammable
Preventive Engineering Practices
Preventive engineering practices (PEPs)
may be thought of as SPPs that are
oriented toward equipment rather than
procedures. They are specific to groups
of toxic and hazardous substances and to
the potential sources of spill, that is:
storage areas; loading/unloading areas;
inpfant transfer, process and materials-
handling areas; drainage from plant site
and secondary containment structures;
and waste storage, treatment and disposal
facilities.
PEPs are divided into pre-release and
post-release groups, both designed to
confine release within the facility bound-
aries. The difference between the two is
that pre-release PEPs are of a general
precautionary nature, whereas post-
release PEPs are activated as spill control
devices by a release. Typical pre-release
PEPs include monitoring and alarm sys-
tems, non-destructive testing, labeling all
storage, process and flow equipment, and
proper storage procedures. Typical post-
release PEPs include secondary contain-
ment of liquids and solids by dikes and
berms, flow diversion, vapor control, and
dust control.
The manual discusses the following
subsections (grouped by equipment cate-
gories, emphasizing components found
in chemical manufacturing facilities).
• Bulk Storage
Tank Construction
Tank Support
Tank Placement
Tank Monitoring
Material Storage
Alarms
Fire Protection Systems
Secondary Containment
• Loading and Unloading Areas
Tank Truck Loading/Unloading
Railroad Tank Car
Loading/Unloading
Marine Loading/Unloading
• In-Plant Process and Transfer
Process Materials/Equipment
Instrumentation
Piping
Valving
Venting
Color Coding/Labeling
• Drainage Control
Facility Diking
Road Drainage
Plant Drainage
Drainage Valving
Secondary Containment
• Waste Storage, Treatment and/or
Disposal.
Appendices
The manual includes the following
appendices:
• Fixed Facility Chemical Process
Equipment Components
Transport and Storage of Fluids
Handling of Bulk and Packaged
Solids
Size Reduction/Enlargement
Heat Generation and Transport
Heat Transfer Equipment
Evaporative Cooling and
Refrigeration
Distillation Columns
Gas Absorptive Towers
Liquid Extractive Systems
Adsorption and Ion Exchange
Equipment
Miscellaneous Separation
Processes
Liquid-Gas Systems
Liquid-Solid Systems
Gas-Solid Systems
Liquid-Liquid Systems
Solid-Solid Systems
Waste Treatment Plants
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Tab/* 4. Compressed Gases Released Into Air
Hazardous Substance Chemical Class
Hazardfs), in
CAS No. Addition to Toxicity
Ammonia
Carbon oxyfluoride
Chlorine
Cyanogen
Ammonia
Halides, alkyl
Halogens
Cyanides and nitrites
Dichlorodifluoromethane Halides, alkyl
Dimethylamine Amines, alkyl
Fluorine
Formaldehyde
Hydrogen sulfide
Methyl bromide
Methyl chloride
Methyl mercaptan
Nitric oxide
Phosgene
Halogens
Halides, alkyl
Halides, alkyl
Monomethylamine Amines, alkyl
7664-41-7
353-50-4
7782-50-5
460-19-5
75-71-8
124-40-3
7782-41-4
Aldehydes 50-00-0
Sulfides and mercaptans 7783-06-4
74-83-9
74-87-3
Sulfides and mercaptans 74 -S3 -1
Oxides
Halides, organic
74-89-5
10102-43-9
75-44-5
Corrosive
Reactive
Oxidizer
Poison
Flammable w/toxic
products
Poison
Flammable w/toxic
products
Corrosive
Corrosive
Reactive
Oxidizer
Poison
Flammable
Flammable w/toxic
products
Poison
Combustible w/toxic
products
Poison
Flammable w/toxic
products
Flammable w/toxic
products
Corrosive
Flammable w/toxic
products
Corrosive
Poison
Oxidizer
Combustible w/toxic
products
Poison
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Walter Unterberg. Robert W. Me/volet, Kathleen S. Roos, and Patricia A. Scofield
are with Combustion Engineering, Environmental Monitoring Services. Inc.,
NewburyPark, CA 91320.
Leo T. McCarthy (deceased) was the EPA Project Officer (see below for present
contact).
The complete report, entitled "Manual for Preventing Spills of Hazardous
Substances at Fixed Facilities," (Order No. PB 87-232 815/AS; Cost: $18.95.
subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
John S. Farlow can be contacted at:
Releases Control Branch
Hazardous Waste Engineering Research Laboratory—Cincinnati
U.S. Environmental Protection Agency
Edison, NJ 08837
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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