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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