FINAL REPORT
A STUDY OF HAZARDOUS WASTE
MATERIALS, HAZARDOUS EFFECTS AND
DISPOSAL METHODS
VOLUME III
For
Environmental Protection Agency
Cincinnati Laboratories
5555 Ridge Avenue
Cincinnati, Ohio 45213
Contract No. 68-03-0032
BAARINC Report No. 9075-003-001
June 30, 1972
.-rl-Xl BOOZ-ALLtN APPLIED RESEARCH INC
WASHINGTON
CHICAGO
LOS ANGELES
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APPENDIX A-6
SIC 29 —PETROLEUM REFINING AND RELATED INDUSTRIES
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VOLUME II
APPENDIX A INDUSTRIAL DESCRIPTIONS
APPENDDCA-1 SIC 10—METAL MINING
SIC 11—ANTHRACITE MINING
SIC 12—BITUMINOUS COAL AND LIGNITE
MINING
APPENDIX A-2 SIC 20—FOOD AND KINDRED PRODUCTS
APPENDDC A-3 SIC 22—TEXTILE MILL PRODUCTS
APPENDIX A-4 SIC 26—PAPER AND ALLIED PRODUCTS
APPENDIX A-5 SIC 28—CHEMICALS AND ALLIED PRODUCTS
INDUSTRIAL ORGANIC CHEMICALS
INDUSTRIAL INORGANIC CHEMICALS
SIC 282—PLASTIC MATERIALS AND SYNTHETIC
RESINS, SYNTHETIC RUBBER,
SYNTHETIC AND OTHER MANMADE
FIBERS, EXCEPT GLASS
SIC 283—DRUGS
SIC 284—SOAP, DETERGENTS, AND
CLEANING PREPARATIONS,
PERFUMES, COSMETICS, AND
OTHER TOILET PREPARATIONS
SIC 285—PAINTS, VARNISHED, LACQUERS,
ENAMELS, AND ALLIED PRODUCTS
SIC 287—AGRICULTURAL CHEMICALS
SIC 2892—EXPLOSIVES
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VOLUME III
APPENDIX A INDUSTRIAL DESCRIPTIONS
APPENDIX A-6
APPENDIX A-7
APPENDIX A-8
APPENDIX A-9
SIC 29—PETROLEUM REFINING AND RELATED
INDUSTRIES
SIC 31—LEATHER AND LEATHER PRODUCTS
SIC 311—LEATHER TANNING AND FINISHING
SIC 32—STONE, CLAY, GLASS, AND
CONCRETE PRODUCTS
SIC 329—ABRASIVE, ASBESTOS, AND
MISCELLANEOUS NONMETALLIC
MINERAL PRODUCTS
SIC 33—PRIMARY METAL INDUSTRIES
SIC 331—BLAST FURNACES, STEEL WORKS,
AND ROLLING AND FINISHING MILLS
SIC 333—PRIMARY SMELTING AND REFINING
OF NONFERROUS METALS
APPENDIX A-10 SIC 34—FABRICATED METAL PRODUCTS,
EXCEPT ORDNANCE, MACHINERY,
AND TRANSPORTATION EQUIPMENT
SIC 347—COATING, ENGRAVING, AND
ALLIED SERVICES
APPENDIX A-ll SIC 80—MEDICAL AND OTHER HEALTH
SERVICES
SIC 806—HOSPITALS
APPENDIX A-12 RADIOACTIVE WASTE (ATOMIC ENERGY
COMMISSION)
APPENDIX A-13 WASTE MANAGEMENT (DEPARTMENT OF
DEFENSE)
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VOLUME III (Continued)
APPENDIX A-14 POWER UTILITIES
APPENDIX B CURRENT LISTINGS OF HAZARDOUS
MATERIALS
APPENDIX C HAZARDOUS MATERIAL RATINGS
(COMPOUNDS FOUND HAZARDOUS BY
RATING SYSTEM)
APPENDIX D SUPPORTING DATA
APPENDIX D-l ACCIDENTS INVOLVING HAZARDOUS
SUBSTANCES
APPENDIX D-2 SIC CODE DISTRIBUTION OF TYPICAL
HAZARDOUS CHEMICALS
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VOLUME III
TABLE OF CONTENTS
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Page
Number
APPENDIX A-6 SIC 29—PETROLEUM AND COAL A-6-1
PRODUCTS
1. ECONOMIC STATISTICS A-6-1
2. WASTE CHARACTERISTICS A-6-5
(1) Refinery Wastes A-6-6
(2) Petrochemical Wastes A-6-9
3. DISPOSAL PRACTICES A-6-16
4. HAZARD EFFECTS OF WASTES A-6-79
APPENDIX A-7 SIC 31—LEATHER AND LEATHER A-7-1
PRODUCTS
SIC 311—LEATHER TANNING AND
FINISHING
1. INDUSTRY DESCRIPTION A-7-1
2. INDUSTRY GROWTH PATTERNS AND A-7-3
PRODUCTION TRENDS
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Number
3. STANDARD PRODUCTION PROCESSES AND A-7-4
WASTE MATERIALS
(1) Typical Processes in the Tanning Industry A-7-5
1. Beamhouse Operation Include A-7-7
Unhairing and Preparation of Hides
for Tanning
2. Tanhouse Processes Convert Hide A-7-8
Fibers Into Leather
3. Retan, Color, Fat Liquor Processes A-7-9
4. Finishing A-7-10
(2) General Processing Trends and A-7-10
Projections
(3) By-Product Utilization, Waste Recovery, A-7-12
and Recycling
(4) Tannery Effluents to Air and Water A-7-15
4. WASTE DISPOSAL PROCESSES AND A-7-15
PRACTICES
(1) Current Waste Treatment Processes in A-7-15
the Tanning Industry
(2) Advanced Treatment Systems for Tannery A-7-17
Wastes
(3) Composition of Waste Streams and A-7-18
Efficiency of Waste Treatment Processes
(4) Extent of Waste Treatment in the Tanning A-7-19
Industry
(5) Estimates of Waste Production A-7-23
1. Net Wasteload Quantities A-7-23
2. Projected Net Wasteload A-7-23
3. Gross Wasteload Projections A-7-24
4. Seasonal Variations A-7-25
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Page
Number
APPENDIX A-8 SIC 32—STONE, CLAY, GLASS, AND A-8-1
CONCRETE PRODUCTS
SIC 329—ABRASIVE, ASBESTOS, AND
MISCELLANEOUS NONMETALLIC
MINERAL PRODUCTS
1. ECONOMIC STATISTICS A-8-1
(1) Location and Number of Establishments A-8-2
with Value Added
(2) Major Raw Materials, Annual Production, A-8-5
and Industry Growth Pattern
2. DESCRIPTION OF PROCESSES AND WASTE A-8-10
SOURCES FOR ASBESTOS PRODUCTS
(1) Mining and Milling A-8-10
(2) Production Processes A-8-14
1. Textiles A-8-14
2. Vinyl Asbestos Tile A-8-16
3. Asbestos Roofing A-8-16
4. Asbestos - Cement Products A-8-16
(3) Waste Summation A-8-18
APPENDIX A-9 SIC 33—PRIMARY METAL INDUSTRIES A-9-1
SIC 331—BLAST FURNACES, STEEL
WORKS, AND ROLLING AND
FINISHING MILLS
1. NUMBER AND SIZE OF ESTABLISHMENTS AND A-9-2
GEOGRAPHICAL LOCATIONS
2. INDUSTRY GROWTH PATTERNS AND A-9-4
PRODUCTION TRENDS
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Page
Number
3. STANDARD PRODUCTION PROCESSES AND A-9-5
WASTE MATERIALS
(1) Typical Manufacturing Processes and A-9-5
Associated Waste Materials in the Steel
Industry
1. Coke Manufacturing A-9-9
2. Iron Manufacturing A-9-10
3. Steel Manufacturing A-9-11
(1) Further Processing of Steel A-9-13
(2) Finishing Operations A-9-13
(2) Production Processing Trends and A-9-15
Projections
1. Effect of Advanced Technology on A-9-15
Volumes of Waste Materials
2. By-Product Utilization, Waste A-9-17
Recovery, and Recycling
(3) Waste Materials From the Steel Industry A-9-18
4. WASTE DISPOSAL PROCESSES AND PRACTICES A-9-19
(1) Current Waste Treatment Processes A-9-19
(2) Advanced Treatment Systems A-9-22
(3) Composition of Waste Streams and A-9-23
Efficiency of Waste Treatment Processes
(4) Current Waste Treatment Practice and A-9-26
Trends
SIC 333—PRIMARY SMELTING AND A-9-33
REFINING OF NONFERROUS
METALS
1. ECONOMIC STATISTICS A-9-33
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Page
Number
2. PRODUCTION PROCESSES AND WASTES A-9-34
(1) Roasting A-9-37
(2) Smelting A-9-38
(3) Hydrometallurgical Processes A-9-39
(4) Specific Applications of General Processes A-9-39
1. Copper A-9-39
2. Lead A-9-44
3. Zinc A-9-45
4. Aluminum A-9-47
5. Rare Earths A-9-48
DISPOSAL PRACTICES A-9-49
(1) Copper A-9-50
(2) Zinc A-9-51
(3) Aluminum A-9-51
APPENDIX A-10 SIC 34—FABRICATED METAL A-10-1
PRODUCTS, EXCEPT ORDNANCE.
MACHINERY, AND TRANSPORTA-
TION EQUIPMENT
SIC 347—COATING, ENGRAVING, AND
ALLIED SERVICES
1. ECONOMIC STATISTICS A-10-1
2. DESCRIPTION OF METAL FINISHING A-10-4
PROCESSES
(1) Primary Finishing Processes A-10-4
1. Anodizing A-10-4
2. Phosphating A-10-5
3. Chromating A-10-5
4. Electroplating A-10-5
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Number
5. Electropolishing A-10-6
6. Oxidizing and Blackening A-10-6
7. Electrogalvanizing A-10-6
(2) Auxiliary Finishing Processes A-10-6
(3) Typical Metal Finishing Operating Sequence A-10-8
3. WASTE CHARACTERISTICS A-10-9
4. DISPOSAL PRACTICES AND TREATMENTS A-10-12
(1) Chemical Methods A-10-14
1. Cyanide Rinse Chemical Treatment A-10-14
2. Chromium Rinse Chemical Treatment A-10-15
(2) Evaporative and Ion Exchange Methods A-10-16
(3) Electrolytical Methods A-10-17
5. IMPACT OF WASTES ON WATER QUALITY A-10-18
(1) Disposal of Waste Into Municipal Sewage A-10-19
Systems
(2) Disposal of Waste Into Streams, Lakes, A-10-22
Etc.
APPENDIX A-ll SIC 80—MEDICAL AND OTHER HEALTH A-ll-1
SERVICES
SIC 806—HOSPITALS
1. ECONOMIC STATISTICS A-ll-1
(1) SIC Classification and Description A-ll-1
(2) Number of Establishments and Relative A-ll-3
Concentration
(3) Bed Capacity A-ll-5
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Page
Number
(4) Hospital Admissions A-ll-5
(5) Services A-ll-8
(6) Hospital Employment A-ll-12
2. WASTE CHARACTERISTICS A-ll-12
(1) Description of Hospital Wastes A-ll-12
(2) Hazardous Materials in Hospital Wastes A-ll-14
3. CURRENT DISPOSAL PRACTICES A-ll-15
4. HAZARDOUS EFFECTS OF WASTES A-ll-20
APPENDIX A-12 RADIOACTIVE WASTE A-12-1
ATOMIC ENERGY COMMISSION
1. INTRODUCTION A-12-1
2. HAZARDOUS EFFECTS RATING A-12-2
3. RADIOACTIVE WASTES FROM NUCLEAR A-12-12
POWER PRODUCTION
(1) Mining and Mill Operations A-12-13
(2) Uranium Conversion A-12-20
(3) Uranium Enrichment A-12-21
(4) Fuel Fabrication A-12-22
1. UO2 Fuel A-12-22
2. PuO2 Fuel A-12-23
(5) Power Reactor Operations A-12-24
(6) Fuel Reprocessing A-12-30
(7) Transportation A-12-47
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Page
Number
RADIOACTIVE WASTES FROM MEDICAL AND
INDUSTRIAL APPLICATIONS
A-12-52
RADIOACTIVE WASTE FROM AEG FACILITIES A-12-53
(1) Radioactive Waste Management Principles A-12-53
and Practices
(2) Description of Available Data A-12-62
RADIOACTIVE WASTE TREATMENT - CURRENT A-12-73
AND FUTURE TRENDS
(1) Current Effluent Treatment Systems A-12-73
1. Gases A-12-73
2. Liquids A-12-74
3. Solids A-12-74
(2) Future Waste Treatment Systems A-12-75
1. Gases A-12-77
2. Liquids A-12-77
3. Solids A-12-77
APPENDIX A-l3
WASTE MANAGEMENT
DEPARTMENT OF DEFENSE
A-13-1
ECONOMIC STATISTICS
A-13-1
WASTE MANAGEMENT
(1) Organization for Control
(2) Base-Post-Station Operations
(3) Production Processes
(4) Maintenance Operations
(5) Supply Operations
(6) Weapon Systems
A-13-2
A-13-3
A-13-4
A-13-8
A-13-10
A-13-10
A-13-11
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Page
Number
CURRENT DISPOSAL OPERATIONS
(1) Chemical Munition Production
(2) Biological Material
(3) Nuclear Material
(4) Excess or Unsafe Munitions
(5) Packaged Hazardous Materials
A-13-12
A-13-12
A-13-15
A-13-15
A-13-17
A-13-19
HAZARDOUS WASTES
A-13-22
APPENDIX A-14 POWER UTILITIES
A-14-1
1. ELECTRIC UTILITIES
A-14-2
2. GAS UTILITIES
A-14-4
POWER RESOURCES
(1) Coal
(2) Petroleum and Natural Gas
(3) Uranium
(4) Hydropower
(5) Geothermal Power
A-14-7
A-14-7
A-14-9
A-14-10
A-14-11
A-14-11
ASSOCIATED ENVIRONMENTAL POLLUTION A-14-11
(1) Air Pollution A-14-13
(2) Water Pollution A-14-14
1. Thermal Pollution A-14-14
(1) Future Outlook for Thermal A-14-14
Pollution
(2) Control of Thermal Pollution A-14-15
2. Radiation Pollution A-14-17
-xiv-
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Number
APPENDIX B
CURRENT LISTINGS
OF HAZARDOUS MATERIALS
APPENDIX C
HAZARDOUS MATERIAL RATINGS
APPENDIX C-l COMPOUNDS FOUND HAZARDOUS BY C-l-1
RATING SYSTEM
APPENDIX C-2 COMPOUNDS FOUND MARGINALLY C-2-1
HAZARDOUS BY RATING SYSTEM
APPENDIX D
SUPPORTING DATA
APPENDIX D-l ACCIDENTS INVOLVING HAZARDOUS D-l-1
SUBSTANCES
APPENDIX D-2 SIC CODE DISTRIBUTION OF TYPICAL D-2-1
HAZARDOUS CHEMICALS
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APPENDIX A-6
SIC 29—PETROLEUM REFINING AND RELATED INDUSTRIES
1. ECONOMIC STATISTICS
According to the American Petroleum Institute (Reference 5),
world petroleum production in 1968 was 14, 000 million barrels. U.S.
consumption was 4, 900 million barrels, broken down as follows:
Million
U. S. Consumption
Transportation
Household & Commercial
Electric Utilities (SIC 4911)
Food & Kindred Products (SIC 20)
Paper & Allied Products (SIC 26)
Chemicals & Allied Products (SIC 28)
Petrol Refine & Related Products
(SIC 29)
Stove Clay Glass & Concrete (SIC 32)
Primary Metal (SIC 33)
All Mineral & Other Mfg. Industries
Miscellaneous
Approximately
Barrels
2, 700
1, 150
188
30
35
302
264
14
59
117
53
(%)
54.6
20.4
3.8
10.3
10.2
4, 900
100%
The principal raw material use of petroleum is as a base input or
feedstock for the production of petrochemicals. The growth rate in
petroleum feed stocks has been approximately 10 percent annually
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APPENDIX A-6-2
between 1964 and 1968. In 1968, approximately 66 percent of the non-
energy petroleum products was consumed in the industrial sector for
making petrochemicals, in aluminum manufacturing (electrodes), as
lubricants and waxes, and other purposes: 29 percent was used in the
commercial sector in the form of asphalt and road oil, and 5 percent
consumed as lubricants in the transportation sector.
Intermediates produced from petroleum (including natural gases)
are used in the synthesis of a wide variety of organic chemicals. Such
intermediates include ethylene, acetylene, propylene, butylene, ethane,
benzene, naptha, toluene, and xylene. Other major petrochemical
products are ammonia, synthetic rubber, plastic, resin, and synthetic
fiber.
The production of petroleum involves the production of brine or
formation water. On the average, two to three barrels of water are
produced for each barrel of oil. These oilfield brines cannot be
discharged into streams without damaging vegetation, fish, and wildlife.
These brines are usually disposed of by returning them to the producing
formation or to a comparable underground brine formation. In some
cases, brines are used to "force out" oil which remains in the for-
mation. The intrusion of brine from such formations into under-
ground fresh water strata must be considered at all times.
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APPENDIX A-6-3
Refineries as well as oilfields process a huge amount of water,
i.e., about 7 gallons of cooling water for each gallon of gasoline
or other product. Such water becomes polluted with oil or by-products
of production and is a pollution hazard if not cooled and treated
(purified). Recirculation of cooling water and treatment improvement
as well as the use of brackish water are becoming common practices
within the industry.
Refinery and petrochemical wastes are a more serious problem,
as most of the various chemicals and wastes produced are toxic to
aquatic life. Progress has been made in controlling wastes and in
improving water quality by use of biological processes, oxidation ponds,
trickling filters, and activated sludge processes. Since refineries
process oils with significant sulfur content, use fluidized catalysts,
and operate various combustion and distillation processes, they emit
air pollutants as well as water pollutants. With technological advances,
new chemicals, new materials, and new fuels will increase the number
of potential pollutants.
At present, industry uses approximately 1,000 million barrels
of petroleum annually. Projections vary widely, from 1, 500 to 5, 000
barrels annually by the year 2000.
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APPENDIX A-6-4
The ratios provided by the 1967 Census of Manufactures , indicates
a relatively high degree of ownership concentration.
Percent Ownership by:
SIC 4 largest 8 largest 20 largest 50 largest
2911 Petroleum re- 33 57 84 96
fining
2951 Paving mixtures 14 22 35 51
and blocks
2952 Asphalt felts 38 65 86 97
and coatings
2992 Lubricating oils— 38 50 68 84
greases
2999 Petroleum and 82 92 99 100
coal products
These concentration ratios are comparable with, but lower than,
those in SIC 28, Chemicals and Allied Products.
Petroleum refining is a major producer of products normally
classified under other SIC codes. For example, in 1967 the petroleum
refining industry produced the following:
Product Value
Class of Products Code ($ Millions)
Cyclic Intermediates and Crudes 2815 60.5
Industrial Organic Chemicals 2818 129.8
Industrial Inorganic Chemicals 2819 39.2
Plastic Materials and Resins 2821 53.7
Surface-Active Agents 2843 15.6
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APPENDIX A-6-5
The geographic distribution of the industry is shown below by
establishments with 20 or more employees.
Petrol. Paving Lube Petrol.
Refining Mixtures Asphalt Oils Prod. Nee.
Division
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Such data indicates an industry which is characterized by a
relatively limited number of establishments which are rather uni-
formly distributed throughout the nation.
2
30
45
22
11
13
102
26
38
11
33
36
6
19
11
13
10
16
6
21
33
9
15
8
26
3
17
3
34
36
15
5
-
5
-
11
7
2
2
2
2.
WASTE CHARACTERISTICS
Hazardous wastes produced within this industry are divided into
two general categories: (1) petroleum refinery wastes, and (2) wastes
resulting from the production of organic chemicals by integrated
refinery-production complexes. The wastes from larger integrated
facilities are a combination of typical refinery wastes plus those
wastes peculiar to the production of organic chemicals.
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APPENDIX A-6-6
(1) Refinery Wastes
The typical production unit in this industry is a larger
plant which processes from 50,000 to 400,000 barrels per day
of crude oil. This basic starting material is augmented, particu-
larly in the case of petrochemical production, by large amounts
of natural gases. Large amounts of sulfuric acid and caustic soda
are also used by all plants, roughly a ton of acid and one-eighth
ton of caustic for each two barrels of crude which is processed.
Typical liquid wastes that are common to almost all
refinery operations can be divided into four categories:
Spent Caustic Solutions—Result from neutralization
of acidic materials in crude oil acidic reaction
products formed during thermal or catalytic cracking
or during chemical treatment processes. These
solutions contain:
Sulfides
Mercaptides
Sulfonate s
Phenolates
Napthenate s
Other similar organic and inorganic compounds.
Spent Sulfuric Acid Products—Result from use of
sulfuric acid as a treating agent and as a catalyst.
These products contain varying compositions of:
Acid sludges
Black acid.
The hydrocarbon content may vary from 2 to 60
percent while the acidity can vary from 20 to 90 per-
cent. A variety of organic materials may be con-
tained in these waste streams.
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APPENDIX A76-7
Foul or Sour Waters—Result from various processing
operations, and contain:
Sulfides, generally hydrogen sulfide
Ammonia
Mercaptans
Phenolic s
Organic acids
Nitrogen bases
Cyanides.
Miscellaneous Wastes—Include a variety of compounds
such as:
Sulfonic acids and sulfonates
Pyridine and quincline
Cyanides (if high nitrogen oils are processed)
Aluminim chloride
Phosphoric acid
Hydroflouric acid
Spent catalysts.
The hazardous material wastes which may be generated
within these plants are dependent on the processes used, the care
exercised in recovering, recycling, eliminating leakage, and
the completeness with which such materials are removed from
effluent streams. Although improvements will be made in
the recycling and recovery of former wastes, the industry
will continue to be faced with difficult disposal problems at the
production sites or, should spills occur, while products are in
transit to consumers.
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APPENDIX A -6 -8
The emissions of hazardous materials from refineries
may be in the form of air contaminants, water pollutants, or
solid wastes. The air contaminants include:
Oxides of sulfur
Hydrocarbons
Carbon monoxide
Oxides of nitrogen
Particulate matter
Odorous (HS and mercaptans).
It is estimated that the loss of hydrocarbons from refineries
as petrochemical plants varies from 0. 1 to 6 percent of the plant
throughput, a substantial amount of which may be air emissions
(Reference 1).
Solid refinery wastes include (1) inert dry solids such
as trash and spent catalysts; (2) combustible solids such as
trash and scrap lumber; (3) sludges containing oil, such as
spent clays; and (4) sludges containing oil, water, and solids,
such as tank bottoms and oil- water separator bottoms.
The disposal of solid wastes is becoming increasingly
difficult. Land disposal of solids by dumping or ponding has
been common in the past. However, adequate land disposal areas
are becoming limited, frequently caused from saturation of available
areas or expansion of production facilities. Increasing emphasis
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APPENDIX A-6-9
on public relations may require elimination of unsightly or
odorous dumps or ponds. Air and water regulations also restrict
dumping or ponding. Ultimately regulations or public relations
may require that wastes discarded in dumps or ponds be removed
or disposed of onsite.
(2) Petrochemical Wastes
The products which can be produced from crude feed stocks,
whether petroleum crude or natural gases, is infinite. The number
of products produced in commercial quantities runs into the
thousands. The wastes that may be produced at any one time
in a particular plant will vary, based on the particular products
being processed and the process used.
Typical waste products which may be produced by various
processes and operations (Reference 2) are shown in Table A-6-1.
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APPENDIX A-6-10
Table A-6-1
Waste Waters from Selected Petrochemical Processes
Process and Operation
Aldehydes and alcohols via
the OXO Process
Hydrogen cyanide from
natural gas and ammonia
Chlorination of methane
and ethylene
Acetylene via cracking of
hydrocarbons
Ethylene and propylene
via thermal cracking'
Polymerization and alkyla-
tion processes
Alcohols from olefins via
sulfates and hydrolysis
Ethylene and propylene
oxide and glycols from
ethylene and ethylene oxide
and propylene
Ketones via dehydrogenation
of alcohols (production of
acetone and methyl ethyl
ketone)
Expected Waste and Effect on Water
Since crude alcohol mixtures are
purified and fractionated by conventional
facilities, still slops probably contain
some soluble hydrocarbons and traces
of aldehydes
Water slops from steam stripping of hydro-
gen cyanide may contain some hydrogen
cyanide and soluble unreacted hydrocarbons
Contaminated wastewater, apparently
containing oil
Probably minor amount of wastewater
containing soluble hydrocarbons
Probably some wastewater containing
soluble hydrocarbons
Wastewater may contain caustic soda,
hydrocarbons including benzene derivatives,
and some catalyst such as phosphoric acid
or aluminum chloride
Probably substantial amounts of waste-
water containing sodium sulfate, poly-
merized hydrocarbons, and alcohols
Possibly substantial amounts of waste-
water containing calcium chloride, spent
lime, polymerized hydrocarbons, ethylene
oxide, thylene dichloride, glycols
Probably distillation slops containing
hydrocarbon polymers, chlorinated
hydrocarbons, glycerol, sodium chloride
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Process and Operation
Aldehydes and alcohols by
hydrocarbon oxidation
Butylenes and butadiene
from butane and butylene
Aromatics via catalytic
reforming
Boiler water treating
and corrosion control
Ammonia production
Conversion of nitrogen via
catalytic processing
Cracking operations
Distillation of intermediate
Specialty processes
Naphtha treating
Acid recovery
Cleaning
APPENDIX A-6-11
Table A-6-1 (Continued)
Expected Waste and Effect on Water
Organic acids, formaldehyde, acetalde-
hyde, acetone, menthanol, higher
alcohols
Amount of waste water probably small,
but containing soluble hydrocarbons
Condensate water may contain catalyst,
aromatic hydrocarbons, hydrogen sulfide
and ammonia
Alkaline waste, lime solids, color
Alkaline wastes
Alkaline wastes
Acidic wastes
Acidic wastes
Usually high in BOD and COD
High toxicity
Color, pH
Color, BOD, toxicity, solids, etc.
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APPENDIX A-6-12
The effluent streams from petrochemical plants may con-
tain varying amounts of raw material, reactants, intermediates,
end products, and non-hydrocarbon pollutants. The liquid
wastes may contain water emulsions, soluble organics, dissolved
inorganics, suspended tars and coke, spent caustic, acids and
acid sludges, spent filter aids, spent catalysts, spent lime,
solvents, and absorbents. Noxious materials such as sulfides
and mercaptans may be in the caustic streams; chromates,
algicides, phosphates, etc.,may be in the process and cooling
water waste streams; furfural, monoethanolamine phenols, etc.,
may be found in the solvent waste streams; and oil and grease
may be in all streams from the quench operations. Unfortunately,
many processes give rise to hot waste streams and generally
the heat is also a pollutant.
A complete listing of all the chemicals in all petrochemical
waste streams would be impossible, but a rough grouping
according to chemical structure indicates the magnitude of the
problem. Table A-6-2 has been prepared by the American
Petroleum Institute as a guide. The groupings are according to
structure and not on relative effect on water use.
Types of waste products which may result from organic
and inorganic compounds (Reference 3) are shown in Figures A-6-1
and A-6-2.
-------
APPENDIX A-6-13
TABLE A-6-2
Classification of Compounds and Waste
Organic Acids Mid Then Salt*
Acetic Acid
Cuprous Ammonium Acetate
Formic Acid
Alcohols
AUyl Alcohol
Ethyl Alcohol
Glycols
Isopiopyl Alcohol
Isobutyl Alcohol
Methanol
Octyl Alcohol
Aldehydes and Ketones
Acetaldehyde
Acetone
Aeiolein
Formaldehyde
Key tones
Octyl Aldehyde
Amines and Amides
Monoethanolamine
Die thy 1 form amide
Esters
Ethylene Diacetate
Methanol Formate
Amyl Acetate
Ethers
Diethyl Ether
Isopropyl Ether
Hydrocarbons
A. Saturated Hydrocarbons
Waste Components of Gasolines
B. Unsaturated Hydrocarbons
Butadiene
Cracked Napthas
Djvmyl Acetylene
Methyl Acetylene
C. Aromatic Hydrocarbons
Aromatic Distillates
Benzene
Cg Aromattcs
Dowtheim
Drphenyl Oxides
Naphthene
Xylene
D. Halogenated Hydrocarbon
Alkyl Chloride
Carbon Tetrachloride
Chlorinated Hydrocarbons
(Long Chain)
Chloroform
Dichloropropane
Ethyl Chloride
Ethylidene Chlonde
Methyl Chloride
Methylene Chloride
Piopylene Dichloride
E. Polymers
Olefinic Polymer
Polychloroethane
Solid Polychloroethane
Polyisobutylene
Rubbers
Phenolic Compounds
Cresol
Phenol
Soaps and Detergents
Detergents
Petroleum Sulfonates
Soaps
Sulfurized Terpenes
Miscellaneous
Dow therm (see Aromatic Hydrocarbons)
Flux Oil
Mercaptaiu
Naphthas
Resins
Soot
Tar
Inorganic
Aluminum Chloride
Ammonia
Ammonium Nitrate
Barium Hydroxide
Calcium Hydroxide
Carbon Bisulfide
Chlorine
Chromates
Chromic Oxide Catalyst
Coke
Copper Chloride
Cyanides
Chromium Oxides
Ferrous Dichloride
Hydrochloric Acid
Hydrogen Cyanide
HyoiogenSulfide
Lime (see Calcium Hydroxide)
Nitric Acid
Phosphoric Acid Catalyst
Potassium Permanganate
Sodium Chloride
Sodium Hydroxide
Sodium Sulfide
Sulfur Dioxide (Sulfurous Acid)
Sulfuric Acid
Sulphates
Waste Caustic Sodas
-------
APPENDIX A-6-14
FIGURE A-6-1
Classification of Organic
Compounds Which May
Occur in Petrochemical
Wastestreams
ton •elublllty
•l|h •eUttlltf
•ot MIT blnte|r«tebU
MluhU thta Mt
bjtrae. bat «*ry nnUvi
Utratinitoo
llc
Organic tut fur
r—rolynon-
Tari •
-rurfaral-
«ad panffu
tT-preteou from ay1tatlea
of olafint
i Ithylaoe
i rroavUni
FroBTlono «l4a
tuted-
htovl ood —
ethyl
chloride
chloro-
fom.
carbon tot.
chlorite.
chlorite
-SynthMl* PIOCMMI
-Subitlcutlon n
-ChlorohydrlBf •
r—Hamthn .
I olaino I—
4— Olitbraol-—I
I •!«
Hiniairtii ——
HjpochlorlMtloo ructloco
"~~1
I— SolvoBU
-Olithanol
achy- —Byloo eanuCacnm
-lltrllai-
-acatoaltillo-
-Solvont for butidlaiu
•atraetlon
:"" «nol» —
••oil —
-,l«nol>-
•pont cauKlci Item primary
— coavaralon, apaclflcally
catalytic aad (luraal
•Sulfonlc aclda-
Hirciptaai-
Scyl rubbar i
lyithyUiu U
rchloroithylaiia '
Doiorgant wnufactura
"Sulfanacloa proc»»i
Spaac cauatlc itrfaaa freai
1 convoratlan
pvtrolew cracking
——rolyaarlullon procaM
_r^Cat«ljr»t tag>nerac Ion
•— High tan?
treating pracaaaa
Solvent axtractlon. n/lon
nanufectura
ln alii
-------
APPENDIX A-6-15
FIGURE A-6-2
Classification of Inorganic
Compounds Which May
Occur in Petrochemical
Wastestreams
HstaUlc
catalysts'
-Al. PC. Hfc. Pi
r. »:. Co. Cu
-Catalytic cracking
-Catalytic reforming
-Dahydrogenatlon Alkylatlon
•Isoaerlxation, Polvnerlut'.on
r-HI tall
——Ant l*eorr«M Ion — — «
Bactericidal
L- — AcctAte »ol'
i
I
n-J
Cu, Cr. In-
Cu-
Inorganic —
I—•an-lferals-
Sodfun
~ COBBWiadl'
Sulfur
-Cooler and boiler water*
Extraction and purification
of butadiene
Removal of carbon Monoxide
from syothaals gas prior
to ammonia synthesis
-Sodli* h]
-Sodluai vulfate
iUB »utfIta ——
-SodlUB aulfIdi
-SodltB eOBbinad with
. Spent cauitlc •cream*
phaael. creeol, xylenol
.Sodlin chloride
-Phenolic apeat cauatlc
a
e^eUCADtmUM
poiypho.9ph.Uct
c«lclua Mitt
sulflde)
ei
c
P
1 3PD;
K
C1
ll
WJ
E Condi
Hydrc
(1
at
C(
a]
tl
Vnci
w
01
pi
— Crude oil deaaltlng
ondenaates and spent
cauatlci from prlawjry
convereloo and refining
proceiie*
ipent cauitlc fraa elkylatlon
solvent In extraction
nt cauatlc froa aromatic
•ultonalIon
:cs tron catalytic
cricking
ii froa coBbuitlon colvenc
In arcoatu extraction
it caustic fron CaOH as
•ashing agent (Chlorlaaclnn)
Condenaatea from catalytic
cracking
Hydrocyanacion reactions
(Nylon aanuf.)
Crude deaalter effluents
and spent cauatlc screams
Corrosion control la
cooling and boiler water
Catalyst In polymerisation,
alkyletlon. end laooerlu-
tlon
Waste sludge from pooling
water treatment
CauseIc wash in refinery
operations
Condenaates Iron retloary
proteins
tic nitration
-------
APPENDIX A-6-16
3. DISPOSAL PRACTICES
Petrochemical and refinery waste disposal practices can be
grouped into> four general methods of treatment:
Reduction of in-process wastes
Physical treatment processes
Chemical treatment processes
Biological treatment processes
Ultimate disposal techniques
Recent legislation requiring the elimination of all waste emissions
into air and water will place increased emphasis on the first category
of treatment methods. The ideal method of controlling wastes is to
eliminate them at the source. The recovery of usable by-products
goes hand-in-hand with the elimination of losses from leaks, spills
or evaporation.
The reduction of in-process wastes includes:
Reduction of raw material losses through elimination of
leaks from storage, transport, and processing facilities
Recovery of usable reaction products through recycling,
conversion, or sale
Process modifications to include new processes and
improved operating 'methods
Water reuse to reduce the quantities of diluted waste
In-plant controls to continuously monitor for leakage or
operational malpractices.
-------
APPENDIX A-6-17
Physical treatment processes include:
Gravity separation
Stripping processes
Solvent extraction
Absorption
Combustion
Filtration
Evaporation
Spraying.
Chemical treatment processes include:
Neutralization and pH adjustment
Coagulation and precipitation
Oxidation
Ion exchange
Reduction.
Biological treatments processes include:
Activated sludge
Trickling filters
Aerated lagoons
Waste stabilization ponds.
Ultimate disposal techniques include:
Incineration
Deep-well injection
Dumping at sea
Approved landfill operations.
-------
APPENDIX A-6-18
Figure A~6-3 illustrates various applications of these tech-
niques in reducing refinery pollutants (Reference 4). A list of in-
plant control and treatment processes for the petroleum refining
industry is presented in Table A-6-3. Another evaluation of the
relative efficiencies of such treatments (Reference 4) are shown
in Table A-6-4.
These tables indicate the variation in possible waste treatment
and give some indication as to the residual contamination
which is to be expected after wastes are treated. Complete elimi-
nation of all contamination from air and water will require sub-
stantial extention of the most advanced techniques throughout the
industry.
The American Petroleum Institute's Manual on Disposal of
Refinery Wastes (Reference 5) contains process summaries for
handling specific wastes.
Present treatment processes do not remove all toxic materials
from the waste streams prior to their discharge into the water or into
the air. If water flows are sufficiently large, or if large bodies of
water are available in which to dilute the effluents, the toxic sub-
stances in the residual waste streams may be sufficiently diluted by
-------
Proceis
Application
Waste
Stre«
General 01
U*
Sour Watei
Spent _
Caul tic
BallHt
Water
Y
m
Pretreatment
S-. Phenol. pH
NH,. RSH
(1)
L
[•
Steam
Stripping
Flue Gas _
Stripping
Oxidation [-
Neutral!- ij
lallon §
Primary Treaunent
Free Oil. SS
(2)
yra
ar
Ilorh
M.
Separator J
Dlscnargi
Enul. Oil. SS.
Colloid. Solids
())
HGas
Flotation
Coagulation
And
Settling
' Sand
Filtration
••
••
s Effluent
Phenols
HCoagul.
and
Settling
01 scnarge
Sec. Treat.
Dissolved
Organ! cs
CO
H Trickling
Filter
f
.Activated1
Sludge
I
Oxidation
I Polishing
1 Panda
_ Aerated I
Lagoon J
-
1
1
Tertiary Treatnent
Dlssolv. Org.
Color. Taste. Odor
(5)
Hfoam
Fractional Ion
f
Activated
Carbon
f
Ozone
Oxidation
Olssolv.
Inorgan.
(o)
J Ion 1
Exchange!
. Electro- .
Dialysis
_J Gat Hydratlon |_j
-j Ultraflltratlon |-
Slop Oil
Sludge Dewaterlng
Sludge Fron
(3) and (It)
(7)
I Sand Beds
Vacuusi
Filtration
§
Thickening
f
Centrifuge
j
J
Sludge Disposal
•I
OcHatered
Sludge
(8)
Incineration
Landfill
Lagoon
Miscellaneous Treat.
Solid. Liquid or
Gaseous Wastei
(9)
J\ Combustion |
U Recovery
SHeatlng.Coagulatlon]
Precoat Filtration
Centrifugal Ion
To Primary or
Secondary Refinery
Treatment Processes.
APPENDIX A-6-
FIGURE A-6-3
Sequence /Sub sti
Diagram of Was
ment Processes
CD
CO
P
-------
APPENDIX A-6-20
Table A-6-3
List of In-plant Control and Treatment Processes
for Petroleum Refining Industry
Types of Wastes
Treatment Processes
Sour Water
Spent Caustic
[Sulfidic)
Ammonia and Hydrogen Sulfide Recovery
Process (by Chevron)(Expected removal:
sulfide, • 99. 9%; ammonia, 99. 9%)
Stripping with Steam (Expected removal:
COD, 40-93%; phenol, 0-30%; sulfide,
70-100%; ammonia, 40-95%)
Stripping with Steam and Acid (Expected
removal: phenol, 0%, sulfide, 85-100%
ammonia, 0%)
Stripping with Flue Gas (Expected
removal: sulfide, 99%; ammonia 8%)
Stripping with Flue Gas and Steam
(Expected removal: phenol, 0-25%;
sulfide, 88-100%; ammonia, 75-90%)
Sulfide Oxidation Tower (with air and
steam) (Expected removal: sulfide,
99-100%; ammonia, 80%)
Sulfide Oxidation Tower (with air and
steam (Expected removal: sulfide, 100%)
Neutralization + Steam Stripping
(Expected removal: sulfide, 100%;
alkalinity, 99-100%)
Direct Sale to Paper Industry
-------
APPENDIX A-6-21
Table A- 6- 3
(Continued)
Types of Wastes
Treatment Processes
Spent Caustics
(Phenolic)
Spent Acid (from
Alkylation Process or
Lube Oil Stock Treating)
Phenol-Bearing Wastes
(process condensate or
steam stripper con-
densate and bottoms)
Ballast Water
(from "clean" ships)
Ballast Water
(from "Black" oil ship)
Neutralization with acid followed by
separation (expected removal:
oil, 99%; phenol, 90-95%, sulfide,
60-70%; alkalinity, 90-100%)
Neutralization with flue gas
(Expected removal: phenol, 90-95%;
sulfide, 60-70%; alkalinity, 99-100%)
Direct sale to chemical plant for
recovery of acid oil (Cresylic Acid)
Treatment for acid recovery
Neutralization with spent caustic or
boiler blowdown
Direct sale to acid manufacturer
Solvent extraction (PHENEX process)
(expected removal: phenol, 75-90%
Reuse at crude desalter (expected)
removal: phenol, 60-90%)
Reuse at cooling tower (expected)'
removal: COD, 70-90%; phenol, 99%)
Separate ballast tank
Separate ballast tank (with steam coil
heating and chemical addition to break
emulsions)
-------
Table A- 6- 3
(Continued )
APPENDIX A-6-22
Types of Wastes
Treatment Processes
Copper and Lead-bearing
Wastes (from Light Oils
Treating Units)
Fluoride-bearing Waste
(from Hydrofluoric
Alkylation Process)
Chromium-bearing Waste
(from Cooling Tower Blow-
down when Chromate is
used)
Spent Aluminurh Chloride
(from Alkylation Process)
Coke Fines (from
hydraulic decoking
of a delayed coker)
Boiler Blowdown
Simple separator at source (spent caustic
in the waste will precipitate copper and
lead)) (expected removal: Cu, greater
than 95%; Pb, greater than 99%)
Chemical precipitation with lime
followed by sedimentation (expected
removal: F, greater than 95%)
Reduction by reducing agent such as
sodium sulfite, sodium bisulfite, sulfur
dioxide (in flue gas), or ferrous
sulfate (in pickle liquor) followed by
precipitation with lime, (expected
removal: Cr, greater than 95%)
Ion exchange (expected removal:
CR, greater than 95%)
Incineration (special)
Burial with crushed limestone
Use as coagulating chemical for
treatment of waste water
Combined with caustic soda to form
aluminum hydroxide
Air wetting of coke fines followed by
sedimentation in a settling pit and
water reuse (expected removal:
suspended solids, greater than 95%)
Separate holding lagoon followed by
neutralization with acid waste
-------
APPENDIX A-6-23
Table A-6-3
(Continued)
Types of Wastes
Treatment Processes
Slop Oil
Sanitary Sewage
Contaminated Storm
Drainage from Padded
Process Areas or
Tank Farms
Separation in slop oil tank with
steam coil heating and chemical
coagulation
Separation by vacuum filter
Separation by centrifuge
Package sewage treatment plant
Discharge to city sewer system
Septic tank with effluent discharged
to general oily sewer
Septic tank followed by tile field
Holding basin followed by controlled
discharge to general oily sewer
-------
Separable Emulsified Phenol Sulfide Sulp. Chloride
Oil Oil S Solids
a Acidity Cyanide pH Tonlclly Top
PNVSICAl TREATMENT
API Separator*
Earthen Separators
Evaporation
Air Flotation
without chemicals
CHEMICAL TREATMENT
Air Flotation
with chcnicals
Chemical Coag. and Precip
BIOLOGICAL TREATMENT
Activated Sludge
Aerat-d Lagoons
Trickling Fillers
Okldation Ponds
TERTIART TREATMENT
Activated Carbon
Oionation
R W
API
Err
API
Err.
API
Err.
API
HI.
API
Err.
API
Eff
API
Err
API
err.
SEC.4
Err
SEC
Err.
f-K'
100
5JB
10-60
10.70
70-95
50-9J
50-90
1.0-do
»-90
K-90
S-$0' 6J-99 N.A Reduced N A. 10-50 N A N A N.A. N A. N.A N A N A
f-liO W-99 N.A Reduced N.A. IO.& N A N.A N.A. N A N A N A 10-90*
100 N.A 100 100 100 100 IUO 100 IUO 10O N A N A N.A
SOD 70-95 10-^0 N.A Reduced JO-liO N.A N.A > N A. N.A. N A N A N A
10-50 75-95 50-90 N.A. Reduced $O-90 N A Reduced N A. N A. N.A. N A N A
IO-50 60-95 50-90 N A. N.A. 50-90 N.A N A. Altered N.A. Altered N A N A
JO-70 N AT. 50-80 65-99 90-99 60.85 N.A y>-95 Altered 65-99 Altered deduced .10-60
25-60 N A 50-80 65-99 90-99 0-10 N.A. 0-li5 Altered 65-99 Altered Reduced 10-90
25-60 N A 50-80 65-99 80-99 ta-K N A 50-95 Altered 65-99 Altered Reduced 10-60
*J-50 N.A. liO-TO 65-99 70-90 20-70 N.A. 10-90 Altered 6'j-99 Altered Reduced 10.90
50-90 N A 50.90 80-99 60-99 N A. N A 10-JO N A *>-99 N A Reduced N A
53-90 N.A. 80-99 80-99 » * «.» '0->0 N A 80-9? N A Reduced N A
BOO and COO fro- separable oil not included.
r Percent of difference between ambient temperature and waste temperature.
' Limited by meteorological conditions
* Chenical or Biological Treatment.
• HPn Noti Probable Process Influent'
recu'ted for efficient ulill'allon
indicates the hind and/or extent of prior treatment
of the specific process under consideration
«O ?. ^ H H >
r— 0) JJ. fj" W *6
r* ^ *^ i n
°- JJ. 0 0> ^
O ff "* L >
1 § «
0> ID ^
3 ° 2
-------
APPENDIX A-6-25
the available waters. As water and air standards tighten, the
release of effluents from production sites will be limited to a greater
degree than now and may even be prohibited.
For these reasons, increased emphasis will be placed on
reducing the volume of waste flows and on means to completely
reduce the residues to an innocuous state. At present the "too hot
to release" wastes may be disposed of in deep wells. However, this
means of disposal may be curtailed much the same as ocean dumping.
Should this occur, little choice remains but to render the wastes
harmless or to place in acceptable land fill sites.
At present the petroleum industry is a leader in the treatment
of waste waters. The 1967 Census of Manufacturing. Water Use in
Manufacturing (Reference 6), provides the wastewater treatment data
given in Table A-6-5.
The petroleum industry ranks high in the treatment of water
prior to its release. For example, all industries discharge approxi-
mately 14. 3 billion gallons annually (1967) and treat only 4. 3 billion
gallons. Such treatment does not, however, ensure that refinery and
petrochemical wastes do not contain materials and suspensions which
may be harmful to water quality.
-------
APPENDIX A-6-.26
Table A-6-5
Petroleum Refinery Disposal Processes
Treatment Method
Coagulation
Primary Settling
Secondary Settling
Trickling Filters
Activated Sludge
Digestion
Ponds or Lagoons
pH Adjustment
Sand Filtration
Chlorination
Flotation
Other
Establishments
19
127
64
12
12
10
103
33
2
7
57
30
Treated Water
Discharges
(Billion Gallons)
19.5
682.8
378.7
7.0
7.3
2.5
363.8
77.3
0.6
420.3
Total establishments surveyed
Total water intake
Total treated water discharges
Total water discharges:
184
1426. 9 billion gallons
917, 1
1217.0 billion gallons
-------
APPENDIX A-6-27
The residual wastes remaining in such effluents were surveyed
and documented by the American Petroleum Institute (Reference 7).
Of a total of 260 operating refineries, 171 responded to the survey.
These plants represent 93 percent of the U. S. capacity and included
all of the petrochemical producers.
Estimated averages for all refineries and the reported charac-
teristics are:
Effluent LbB/Day/1. OOP bbl Crude
BOD 75
COD 250
Oil 30
Phenols 5
Suspended Solids 40
Dissolved Solids 1, 200
Alkalinity 75
Sulphur 5
Phosphate 2
Ammonia Nitrogen 15
The overall net U. S. refinery effluent contaminant loadings following
waste treatment were estimated as follows:
Parameter Pounds Per Day
BOD 800,000
COD 2,500,000
Oil 360,000
Phenol 55,000
Suspended Solids 500.000
4,215,000
-------
APPENDIX A-6-28
The addition of these contaminats to the existing sludge piles, should
water quality standards prohibit their continued release, will sub-
stantially increase the problems concerned with the disposition of
sludge wastes.
Waste treatment processes for petrochemical plants are similar,
in most respects, to those used by refineries. In fact, many modern
refineries are also major producers of petrochemicals.
The actual compound in the waste effluents depends largely
on the products produced in a particular plant and /or the treatment
given the wastes prior to release. Organic pollution is difficult to
define in terms of general factors or in terms of compounds within
the waste streams. Products, by-products, and unconverted fuels are
contained within the same waste streams and may produce, by inter-
action, additional products of unknown composition. Analytical
techniques now available are insufficient to the task of continuously
analyzing and establishing the composition of waste streams.
Although some organic compounds may be more readily removed
in waste treatment, many are resistant to biodegradation, physical or
chemical treatment. If any organic components can be detected in the
wastes it must be assumed that toxic compounds have been released.
-------
APPENDIX A-6-29
To attain a high degree of assurance that no organic compound which
may have latent toxic, carcinogenic, mutagenic, or teratogenic is
released, all organic material must be removed from the wastes.
Tables A- 6-6 and A- 6- 7 show the waste treatment processes
associated with various organic compounds (Reference 8).
An excerpt from The Characteristics and Pollutional Problems
Associated With Petrochemical Wastes (Reference 9) is included after
Tables A-6-6 and A-6-7. This excerpt provides a detailed appraisal
of the current state-of-the-art of waste treatment in the petrochem-
ical industry.
-------
APPENDIX A-6-30
TABLE A-6-6
Waste Treating Process
Being Used for Petro-
chemical Wastes
WARES recu PETROCHEMICAL OitunoNi
Organic.
Acetaldehyde
Acetic acid
Acetone
Acetylene derivatives
Acrolein
Alcohol, general
Alcohols, high boiling
Ally! alcohol
Allyl chloride
Aromatics, Ct
Benzene
Butadiene
Carbonyl products
Carbon tetrachloride
Chlorinated hydrocarbons
Chloroform
Cresols
Cuprous ammonium acetate
Cyanides
Detergents
Dichloropropane
Diethyl ether
Diethyl formamide
Distillate, aromatic
Divmylacetylene
Dodecyl
Dowtherm
Ethyl alcohol
PHYSICAL TIEATMEMT
i
)
_
]
SEPAIATOU (API)
1
1
1
-
1
1
1
18
1
1
1
\
2
4
12
24
4
12
i
.
'X
14
23
23
1
1
'
1
.
CHEMICAL
TREATMENT
5
i
CHEMICAL OXIDATION
•
X
X
23
25
26
I
P
1
BIOLOGICAL
TUATMENT
I'
3
4
5
4
8
4
8
X
4
IS
IS
16
17
X
5
26
IS
17
I
6
3
6
9
3
6
13
X
13
6
,
7
7
10
1
X
ULTIMATE DISPOSAL
|l
38
i
X
1
1
1
X
X
1
27
X
X
X
1
£
20
6
14
28
1
8
I
14
X
19
14
X
§
11
11
X
14
X
11
X
19
21
19
29
1
X
X
X
X
I
1
X
X
22
X
X
X
X
NOTE: Processes being used are indicated by a reference number or an X.
-------
APPENDIX A-6-31
TABLE A-6-6
WASTES FROM PETROCHEMICAL OPERATIONS
Organic
Ethyl benzene
Ethyl chloride
Ethyl ether
Ethylene diacetate
Ethylene dichloride
Ethylene oxide
Ethylidene chloride
Epichlorohydrin
Flux oil
Formaldehyde
Formic acid .
Gasolines
Glycerol
Glycols
Hydrazine
Hydrogen cyanide
Isobutyl alcohol
Ijobutyl and uopropyl alcohol
fjopropyl ether
Kerosine
Ketones
Mercaptans
Methanol
Methyl acetylene
Methyl chloride
Methyl formate
Methylene chloride
Monoethanolamine
PHVSKAL TREATMENT
j
1
i
f
|
. 1
1
"
•
i
1
1
i
! i
•
i ,
i
i
1
! '
|
.
1
i
21
31
32
j
1
I
•
X
36
i
14
X
i
—
i
i
1
CHEMICAL
TREATMENT
1
t
1
1
jj
ii
i
,
•
i
!
xl
•
i
36
|
i
BIOLOGICAL
TREATMENT
BIOLOGICAL FILTERS
M
§
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i being used are indicated by a reference number or an X.
-------
APPENDIX A-6-32
TABLE A-6-6
WASTES FROM PETROCHEMICAL OPERATIONS
Organic.
Naphthas
Naphthene
Octyl alcohol
Octyl aldehyde
Picolmes
Phenolics
Polybutene
Polychloroethane
Polyethylenes, solid
Polyuobutylene
Polymers
Propadiene
Propylene dichlonde
Resins
Rubber
Soaps
Sultanates, petroleum
Tars
Terpenes
Terpenes. sulfurized
Toluene
Urea
Vinyl acetate
Zylene
Inorganic
Aluminum chloride
Ammonia
Ammonium nitrate
PHYSICAL TREATMENT
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FLOTATION
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-------
APPENDIX A-6-33
TABLE A-6-6
WASTES noH PITIOCHEWCAL OWMTIONI
Inorganic.
Barium sludge
Carbon bisulfide
Carbon black
Chlorine
Chromates
Chromic oxide catalyst
Chromium oxide
Copper and compounds
Copper chloride
Ferrous dichlonde
Hydrochloric acid
Hydrogen sulfide
Lime
Nitric acid
Phosphoric acid catalyst
Potassium permanganate
Sodium chloride
Sodium hydroxide
Soot
Sulfur dioxide
SulCunc acid
Sulfates
Sodium sulfide
Waste caustic sodas
PHVIICAL TBEATMENT
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NOTE: Processes being used are indicated by a reference number or an X
-------
APPENDIX A-6-34
TABLE A-6-7
DRW MANUAL—LIQUID WASTES
Summary of Treatment Methods for Petrochemical Wastes Classified by Plant Product
PLANT PRODUCT
General chemicals
Nylon
Nylon chemical intermediates
Organic chemicals
Oxygenated hydrocarbons
Photochemicals
Powders
Resins
Rocket fuels
Rubber, textiles, and plastics
Synthetic rubber
PHYSICAL TREATMENT
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NOTE: Processes being used are indicated by a reference number.
REFERENCES (Tables A-6-6 and A-6-7)
'API Petrochemical Waste Questionnaire (1958) (Private
communication.]
•N V Chalov and L. P. Volskaya, -Decontamination of
Waste Liquors Containing Phenols, Aldehydes and Methanol,"
Zh Pnkl. Khim. 25 1082-8 (1952); Chem. Abstr. 47 3497b
(1953)
• E R Strong and Richard Hatfield, 'Treatment of Petro-
chemical Wastes by Superactivated Sludge Process," Ind Eng.
Chem 46 [2] 308-16 (1954).
' H Heukelekian, et al., "1957 Literature Review," Sewage
Ind. Wastes 30 [6] 717-873 (1958).
*J R Cushman and J. R. Hayes, "Pilot Plant Studies of
Pharmaceutical Wastes at the Upjohn Company," Purdue Univ.
Eng Bull. Ext Ser. 91. 62-72. Lafayette, Ind. (1956).
•R E. McKmney and J. S. Jeris, "Metabolism of Low-
Molecular-Weighl Alcohols by Activated Sludge," Sewage Ind
Wattes 27 [6] 728-35(1955).
'J L Reagan, "Pilot Study of Synthetic Organic Waste
Disposal on Tackling Filters," paper presented at Fourth Ann.
Regional Conf on Indus. Health, 103, Houston (1951)
• H. F Elkm. "Condensates, Quenches and Wash Waters as
Petrochemical Waste Sources," Sewage Ind Wastes 31 [7]
836-40(1959).
• K. L. Schulze and B. N. Raju; "Studies of Sludge Digestion
and Methane Fermentation: II. Methane Fermentation of
Organic Acids," Sewage Ind. Wattes 30 [2] 164-83 (1958)
" D Tarvm and A. M. Buswell, "The Methane Fermentation
of Organic Acids and Carbohydrates," 1. Am. Chem. Soc 56
1751-5 (1934)
UR. V. Green and D. V. Moses, "Destructive Catalytic
Oxidation of Aqueous Waste Materials," Sewage Ind. Wastes
24 [3] 215-21 (1952).
u W. W. Eclcenfelder, Robert Klefferman, and John Walker,
"Some Theoretical Aspects of Solvent Stripping and Aeration
of Industrial Wastes," Purdue Univ. Eng. Bull. Ext. Ser. 91
14-25. Lafayette, Ind. (1956).
"Richard Hatfield, "Biological Oxidation of Some Organic
Compounds," Ind. Eng Chem. 49 [2] 192-6 (1957).
" S J. Paradiso, "Disposal of Fine Chemical Wastes at the
Upjohn Company," Purdue Univ. Eng. Bull. Ext. Ser. 89, 49-60,
Lafayette, Ind. (1955).
"C. B. Lamb and G. F. Jenkins, "B. O. D. of Synthetic
Organic Chemicals," Purdue Univ. Eng. Bull. Em. Ser 79
326-39, Lafayette, Ind. (1952).
"E J Mills, Jr., and V. T. Stack, Jr., "Acclimation of
Microorganisms for the Oxidation of Pure Organic Chemicals,"
Purdue Univ. Eng. Bull. Ext. Ser 87. 449-64, Lafayette, Ind.
(1954)
" E. J Mills, Jr., and V T. Stack, Jr., "Biological Oxidation
of Synthetic Organic Chemicals," Purdue Univ. Eng Bull. Ext.
Ser. 83.492-517. Lafayette, Ind. (1953).
UL. D. Dougan and J. C. Bell, "Waste Disposal at a Syn-
thetic Rubber Plant." Sewage Ind. Wastes 23 [2] 181-7 (1951).
" R. F. Rocheleau. "Incineration of Organic Wastes," Proc.
Air Water Pollution Abatement Conf, 89-98, Mfg Chemists
Assoc. Washington. D C. (1957).
-------
APPENDIX A-6-35
TABLE A-6-7 (Con'O
PETROCHEMICAL WASTE TREATMENT
" D W. Hood. B Stevenson, and L. M Jeffrey. "Deep Sea.
Disposal of Industrial Wastes." Ind. Ens Chem. 50 [6] 885-8
(1958)
11 Isaiah Cellman and H. Heukelekian, "Biological Oxidation
of Formaldehyde," Sewage lad. Wastes 22 [10] 1321-5 (1950).
= H Heukelekian and M. E. Rand, "Biochemical Oxygen
Demand of Pure Organic Compounds," Sewage Ind. Wastes
27 [9] 1041-53 (1955).
"C Taylor, "Chemical Oxidation. Some Laboratory Experi-
ments in the Treatment of Chemical Trade Waste," Water Sen.
Engr 3 [1] 31-3 (1952).
" M. M. Wells, 'The Reactions and Resistance of Fishes in
Their Natural Environment to Salts," J. Expll. Zool. 19 [3]
243-83 (1915).
" N H Kirchgessner, 'Treatment of Phenolic Plastics Manu-
facturing Wastes." Sewage Ind. Wastes 22 [10] 1314-20 (1950).
" F J Ludzack. R B Schaffer, R. N. Bloomhuff, and M B
Etlmger, "Biochemical Oxidation of Some Commercially Im-
portant Organic Cyanides," Sewage Ind. Wastes 31 [1) 33-44
(1959)
57 A. B Cherry. A J. Cabaccia, and H W. Senn, "The
Assimilation Behavior of Certain Toxic Organic Compounds
in Natu-al Water." Sewage Ind Wastes 28 [9] 1137-46 (1956).
" C E Renn. "Biological Properties and Behaviors of Cyano-
gemc Wastes," Sewage Ind. Wastes 27 [3] 297-310 (I95SJ.
"J T. Garrell, "Multipurpose Incineration," Ind. Wastes
2 [5] 111-3 (1957)
"B W. Dickerson, "High-Rate Trickling Filter Operation
on Formaldehyde Wastes," Sewage Ind Wastes 22 [4] 536-45
(1950).
" N H Kirchgessner, "Phenol Recovery by Use of /wpropyl
Ether," Sewage Ind. Wastes 30 [2] 191-8 (1958).
BT Waldmeyer, 'Treatment of Formaldehyde Wastes by
Activated Sludge Methods," Surveyor Municipal County Engr.
111445-7. July 12 (1952).
" B W. Dickerson. "A High-Rate Trickling Filter Pilot Plant
for Certain Chemical Wastes." Sewage Works I. 21 [4] 685-93
(1949)
* "Anaerobic Fermentations." Illinois State Water Surv Bull.
32. 51-3, Urbana, 111 (1939).
KC E. Eden. A M. Freke. and K. V Melbourne, 'Treat-
ment of Waste Waters Containing Hydrogen Peroxide, Hydra-
zir.c. and Methanol," Chem. Ind (London), 1104-6, Dec. IS
(1951)
"I. E Wallen, W C Greer. and R. Lasater, "Toxicily to
Cambusia Affims of Certain Pure Chemicals in Turbid Waters,"
Sewagrlnd Wastes 29 [6] 695-711 (1957)
17 G Gu'.z'il, 'Treatment of Complex Chemicaj Wastes Re-
sulting from Tank Car Cleaning Operations," Srtv'age Works I.
21 [1] 91-9(1949)
"H. O. Henkel. "Surface and Underground Disposal of
Chemical Wastes at Victoria, Texas," Sewage Ind. Wastes 25
[9] 1044-9(1953).
•A. N. Heller, E. W. Clark, and W. M. Reiter, "Some
Factors in the Selection of a Phenol Recovery Process," Purdue
Unlv Eng Bull. Ext. Ser. 94, 103-22, Lafayelle, Ind. (1957).
" D. I. Macht and H. P. Leach, -Pharmacological Studies of
Twenty-three Isomenc Octyl Alcohols," J Pliarmacol Exp
Therap 3971 (1930).
" R. G. Edmonds and G F. Jenkins. "Recovery of Phenolics
from Waste Effluents." Chem Eng Progr 50 [3] 111-5
(1954).
" B. A. Adams, "The Lethal Effect of Vanous Chemicals on
Cyclops and Daphma." Water and Water Eng (London) 29
361-4, Sept. 20(1927)
"IS. Wilson, 'Treatment of Chemical Wastes," Surveyor
Municipal County Engr, 113 315-8, Apr. 17 (1954)
" W. W Malhews, 'Treatment of Ammonia Still Wastes by
the Activated Sludge Process." Sewage Ind. Wastes 24 [2]
164-80(1952).
0 H. W. De Ropp, "Chemical Waste Disposal at the Victoria,
Texas Plant of the Du Pont Company," Sewage Ind Wastes
23 [2] 194-7(1951).
"H H. Black and V. A. Minch, "Industrial Waste Guide.
Wood Naval Stores," Sewage Ind Wastes 25 [4] 462-74
(1953).
" N Federgreen and A J. Weinberger, "Methyl Styrene—A
Case Study in Spent Acid Catalyst Treatment," Ind Eng Chem
49 [1] 46-8 (1957)
" F. Majewski, "The Treatment of Wastes at the Rohm and
Haas Company." Purdue Univ. Eng Bull En Ser. 83, 328-345,
Lafayette. Ind. (1953).
" B. W Dickerson, 'Treatment of Powder Plant Wastes,"
Purdue Univ. Eng Bull. Ext Ser 76, 30-42, Lafayette, Ind.
(1951).
10 D. T. Laurie, "Combustion and Bio-Oxidation Combined
in Waste Plant at Chemstrand Corp ," Power Eng 63 [4] 80-2
(1959).
" S D. Faust and H E. Orford, "Reducing Sludge Volume
with Crystal Seeding in Disposal of Sulfunc Acid Wastes,"
Ind Eng. Chem. 50 [10] 1537-8 (1958).
" A. D. McRae. "Disposal of Alkaline Wastes in the Petro-
chemical Industry." Sewage Ind. Wastes 31 [6] 712-8 (1959).
'•* H D. Lyon, "Disposal of Synthetic Organic Wastes." Chem
Eng Progr. 46 [8] 388-94 (1950).
" "Biological Waste Treatment," Petrochem. Ind 1 [4] 16-9,
Oct. (1958).
a H. W. Eustace and R. J. McVeigh, "Design of a Sedimen-
tation-Type Waste Treatment Plant." Proc Air Water Pollution
Abatement Con/. 99-112, Mfg Chemists Assoc, Washington,
D.C. (1957).
-------
APPENDIX A-6-36
TREATMENT AND CONTROL OF PETROCHEMICAL WASTES
The treatment and control processes discussed herein are cate-
gorized as: (a) reduction of waste strength' by in-process and inplant
control measures, (b) physical treatment processes, (c) chemical
treatment processes, (d) biological treatment processes, and (e) ulti-
mate disposal techniques.
INTERNAL IMPROVEMENTS
The ideal method of controlling petrochemical pollutants is to
eliminate them at the sources. This reduces the cost of waste treat-
ment and in many cases provides valuable economic gains in the form
of reduced losses of expensive petrochemicals and reduced intake of
makeup water.
Reduction of Raw Material Losses - The losses of hydrocarbon
raw materials from storage, transport, and processing facilities are
an important source of water pollution in the petrochemical industry.
Several improvements can be made by trie industry to reduce the mag-
nitude of these losses. The evaporation of light hydrocarbon from
storage tanks can be controlled by floating roof tanks and the use of
tank vents with vapor recovery lines. Purge lines used for process
start-up and shut-down can be connected to vapor recovery systems
The hydrocarbon losses from vacuum jets can be reduced by
installing refrigerated condensers ahead of the jets or by con-
necting the jet exhaust to vapor recovery systems . Pipeline sys-
tems should be used to transfer raw materials whenever feasible in
order to minimize transfer losses. Probably the most important
source of hydrocarbon raw material loss is from malfunctioning equip-
ment, leakages, etc. These losses can be corrected only by careful
in-plant control.
Recovery of Usable Reaction Products - By-products represent a
significant pollutional fraction of petrochemical wastewaters. In many
cases, by-product recovery from the process wastes is justified, not
only in terms of producing a product, but also in reducing the pollu-
tional load to the waste treatment facility. The recovery of sulfur,
-------
APPENDIX A-6-37
for example, from petroleum hydrocarbons minimizes the sulfide and
jmercaptan pollution. The Glaus process and a catalytic combustion
process are currently used to convert hydrogen sulfide to elemental
sulfur, thus, obtaining a reusable product.
Other sources of usable materials found in petrochemical wastes
include catalyst complex metals and the tars from catalytic processes.
Usually, the recovery of materials from the tars does not result in a
direct profit to the petrochemical plant, but it may prove economically
justified by reducing the pollutional discharge. Alkaline wastes from
caustic washes are most significant. Some spent caustic solutions con-
taining sulfides, phenolates, cresolates, and carbonates are marketable.
Spent caustics which contain large amounts of phenols and cresole
can be sold to processors who separate and purify the cresylic acid
fractions for commercial use. Sodium sulfide can be separated
from spent caustics high in sulfides, and marketed. Spent caustics can
also be regenerated for reuse in washing processes by steam hydrolysis,
electrolysis, air regeneration, and the use of slaked lime.
The recovery and recycling of process effluents containing unre-
acted raw materials is common to most petrochemical processes in
which the process reaction is incomplete. Many of the secondary re-
action by-products are also valuable either for use within the petro-
chemical plant or as marketable products. Some of the possible uses
for by-products produced in three common petrochemical processes
are shown in Table 8. The recovery and reuse of oils is very common
in the petrochemical industry. Recoverable oils are reprocessed while
those which are uneconomical to purify are used as fuels. Solvent re-
covery is practiced also, especially when the high costs of solvents are
redeemable.
Process modifications can be classed as: (a) process selection,
(b) prevention of product and chemical losses, and (c) modified operating
conditions. If waste control is considered during process design, it
often can be an important factor in the economics of operation. The
substitution of continuous processes for batch processes tends to elimi-
nate peak discharges of wastes, thus reducing the cost of treatment re-
quired for the waste. The use of downgraded chemicals in processes
which do not require high-quality reactants facilities both process and
waste control. This type of design often utilizes the waste effluents
from one process as reactants in another.
Water reuse is often one of the most effective and economical
means of decreasing the waste discharges from a petrochemical plant.
-------
APPENDIX A-6-38
TABLE 8
USABLE SIDE PRODUCTS FROM SOME
TYPICAL PETROCHEMICAL PROCESSES
(Reference 89)
Primary Product
Side-Products
Use
Butadiene:
Ethylene:
Residue Gas (Hydrogen
methane, ethane, carbon
dioxide)
Propane and Propylene
Butane and Butenes
Aromatic Oils
Residue Gas (Hydrogen,
Methane)
Acetylene
Ethane
Propane and Propylene
Butane and Butyl ene
Aromatic Concentrate
Heavy Oils and Tars
Fuel
Feedstock for Ethylene,
Alkylation
Recycle for Butadiene
Manufacture; Feedstock
for Alkylation
Resin or Plastic Manu-
facture
Fuel
Fuel for Welding Feed-
stock for Several Petro-
chemical Processes
Recycle for Ethylene
Manufacture; Cracking
Feedstock; Fuel
Propane Recycle for
Ethylene Manufacture;
Feedstocks for Several
Petrochemical Processes
(Alcohol, Alkylation,
Polypropylene, etc. )
Feedstock for Synthetic
Rubber Aviation Gas;
Recycle to Cracking
Process
Resin and Plastic Manu-
facture
Refinery Charge Stock Fuel
-------
APPENDIX A-6-39
TABLE 8 (Continued)
USABLE SIDE-PRODUCTS FROM SOME
TYPICAL PETROCHEMICAL PROCESSES
Primary Product
Side-Pro ducts
Use
Ammonia:
Carbon Dioxide
Helium
Argon
Dry Ice, Bottled CO
Fuel
Methanol Manufacture
Lifting Gas
Inert Gas
Inert Gas
-------
APPENDIX A-6-40
In addition to reducing water costs and waste treatment costs, water re-
use increases the flexibility for plant expansion. Small quantities of
concentrated wastes produced by reuse are easier to handle than larger
quantities of dilute wastes, and the plant'benefits by more freedom from
upstream users.
Potential applications of water reuse include the utilization of
poorer quality cooling and boiler water and also the reuse of contami-
nated steams in stripping operations. Water-use systems are
classified as multiple recycle and cascade, but most frequently com-
binations of these schemes are employed.
Steam used for the stripping and quenching of process streams is
an important source of waste. Condensates with high sulfide contents
can be partially oxidized to sulfate and then used to generate low-
quality stripping steam, although oxygen-demanding thiosulfates may
be present. Another condensate reuse scheme has been described in
which phenolic condensate from an olefin unit is washed with the fresh
hydrocarbon feed-stream, thus removing the phenol from the conden-
sate. Other volatile hydrocarbons are then steam-stripped from
the condensate and reused to generate additional steam. A potential'
source of water for reuse in the petrochemical plant is for main boiler
use. Boilers can often tolerate high dissolved solids concentrations,
depending on the type of dissolved solids and the boiler design. Oils
do not seem to deposit in boilers if chelating agents prevent other de-
positions from forming; thus, the oils are steam distilled or leave the
boiler with the blowdown.
In-Plant Control - Operational control is one of the most import-
ant facets of pollution abatement. Inplant operational control includes:
(a) maintenance of pipes, valves, fittings, pump seals, etc., to prevent
leaks; (b) education of all plant personnel as to the effects of accidental
and careless losses of materials; (c) changes in selected operational
procedures; and (d) a highly developed monitoring system to detect the
sources of occurrences of pollutants within the plant. A continuous
monitoring program for important plant sewers can prove invaluable
in locating malfunctioning process units and leaks.
Waste Stream Segregation - Three main segregated collection
systems are normally used in petrochemical plants:
a) Area drains which carry off unpolluted cooling water
and storm runoff from uncontaminated areas;
-------
APPENDIX A-6-41
b) A contaminated water system which contains process
waters, polluted cooling waters, and storm water
runoff from contaminated areas; and
c) A sanitary sewerage system to collect plant domestic
wastes.
Segregation of many process streams may be necessary due to the
incompatibility of certain waste components. Wastes with high solids
concentrations are usually segregated from oily streams since suspended
solids tend to decrease the efficiency of oil separation units. Suspended
solids also can interfere with oil recovery by increasing the solids con-
tents of separator skimmings.
PHYSICAL TREATMENT PROCESSES
The types of physical treatment processes most commonly used in
the treatment of petrochemical wastes include gravity separation, flota-
tion, stripping processes, adsorption, extraction, and combustion. The
waste from a petrochemical plant may require a combination of these
processes if proper treatment is to be provided.
Gravity separation includes the removal of materials less dense
than water such as oils and air- entrained particulates by flotation and
the removal of suspended materials which are more dense than water by
sedimentation. Sedimentation and flotation techniques commonly employ
chemical conditioners to enhance the separation process. Many waste-
waters from petrochemical operations contain significant quantities of
free and emulsified oil which must be removed prior to subsequent treat-
ment. Free oils are much easier to remove if their concentration is
high. Slop oils which are recovered by the separation process can be
cleaned and reused in various processing operations. Probably the most
commonly employed separator design is that presented by the American
Petroleum Institute. Reported efficiencies of some oil separators
operated by the petroleum industry are given in Table 9. Although some
reduction in chemical oxygen demand (COD) can be expected due to re-
moval of oils and tars, little or no biological oxygen demand (BOD) re-
moval will be prevalent.
Oil emulsions present the biggest problem of oil-water separation
because they are not easily separated in gravity separators and other
conventional separation devices. Emulsifying agents prevent the oils
from coalescing and separating from the water phase. These emulsifying
-------
TABLE 9
TYPICAL EFFICIENCIES OF OIL SEPARATION UNITS
Oil
Influent
(mg/1)
Content
Effluent
(mg/1)
7,000-8,000 125
3,200
400-200
220
108
108
90-98
50-100
42
*
API -
10-50
10-40
49
20
50
40-44
20-40
20
Oil
Removed
(%)
98-99+
98-99+
90-95
78
81.5
54
55
60
52
Removed
Type (%)
Circular
Impounding 0
Parallel Plate
API* 45
Circular
Circular 16
API
API
API
Removed Removed
(%) (%) Ref
115
83
59
55 20
111
0 0 20
20
20
20
American Petroleum Institute Standard Design
H
Z
0
i
*»
to
-------
APPENDIX A-6-43
agents are surface-active agents and include catalysts, the sulfonic acids
naphthenic acids, and fatty acids, as well as their sodium and potassium
salts. In an alkaline medium, calcium and magnesium salts form finely
divided suspended solids which stabilize the emulsions. Sources of
oil emulsions within a petrochemical plant include (a) crude oil desalting
water, (b) condensates from distilling operations, (c) v/ash waters which
follow caustic or acid chemical treating operations, (d) cooling waters
from direct-contact condensers, (e) detergent manufacturing processes,
and (f) equipment cleaning operations.
In order to separate the emulsified oils from the wastewater, the
emulsion must be broken. The application of heat and pressure is pro-
bably one of the more effective methods used in de-emulsification of a
waste. Distillation methods, in lieu of the heat requirements, are
also effective in breaking emulsions as are filtration, acidification, and
electrical methods.
Sedimentation processes are utilized in the pre- or primary treat-
ment of petrochemical wastes with high suspended solids concentrations,
in secondary clarification, and for a sludge thickening. Petrochemical
wastewaters high in colloidal material must be chemically treated before
adequate separation by sedimentation can be obtained. The removal of
solids and oils from petrochemical wastewaters and the concentration of
sludges can often be accomplished using the air flotation process. Air is
dissolved under pressures of 30 to 60 psig with the wastewater to be
treated. When the waste is then exposed to the atmosphere, minute air
bubbles are released from solution and carry the suspended materials to
the top of the tank. Gravity oil separators usually precede flotation units
in most industrial applications. One of the big advantages of flotation
over sedimentation is the shorter detention time required to clarify a
waste by flotation, resulting in a unit of considerably smaller size.
Stripping processes are used to remove volatile materials from
liquid streams. These methods are employed, generally, to remove rela-i
tively small quantities of volatile pollutants from large volumes of waste-
water. Stripping is essentially a low-temperature distillation process
whereby reduction of effective vapor pressure by the introduction of the
stripping medium replaces the high temperature requirement. The two
types of stripping agents commonly used are steam and inert gas.
The stripping of hydrogen sulfide and ammonia from sour water is
probably the most common use of stripping employed by the petrochemi-
cal industry for waste treatment. The major stripping agents used to
remove these contaminants are steam, natural gas, and flue gas.
-------
APPENDIX A-6-44
Phenols also can be removed from aqueous waste streams by steam
stripping which is applicable when a wastewater is subject to short vari-
ations in temperature, specific gravity, phenol concentrations, and sus-
pended solids.
Volatile organic compounds can be stripped from aqueous wastes by
using air as the stripping agent. The stripping rate of a volatile organic
compound is a function of temperature, the stripping gas flow rate, and
tank geometry. Laboratory testing has indicated that most of the
BOD removal during the stripping of biodegradable volatile organic com-
pounds was the result of biological action rather than physical stripping.
If an organic compound is non-biodegradable and volatile, air strip-
ping may be a feasible unit process.
Solvent extraction methods utilize the preferential solubility of
materials in a selected solvent as a separation technique. The criteria
for effective use of a solvent in wastewater treatment include (a) low
water solubility, (b) density differential greater than 0. 02 between sol-
vent and wastewater, (c) high distribution coefficient for waste component
being extracted, (d) low volatility and resistance to degradation by heat if
distillation is used for regeneration or low solubility in liquid regener-
ants, and (e) economical to use. Equipment used for extraction of
wastewater include counter current towers, mixer-settler units, centri-
fugal extractors, and miscellaneous equipment of special design.
Solvent extration has been found to effectively remove phenols.
Tricresyl phosphates are excellent solvents for phenol due to their low
solubility in water and their high distribution coefficients for phenol.
However, they are expensive and deteriorate at high temperature. The
electrostatic extractor employed in one phenol recovery process also
recovers usable oil from wastewater which helps to make the process
economical.
Other solvent extraction processes which have been used by the
petrochemical industry include the extraction of thiazole-based chemicals
from a rubber processing effluent with benzene and the extraction of
salicylic and other hydroxy-aromatic acids from a wastewater using
methyl-isobutyl-ketone as the solvent.
Adsorption is the process whereby substances are attached to the
surface of a solid by electrical, physical, or chemical phenomenon. A
carbon media has been the most successful adsorbent in removing cer-
tain refractory chemicals from wastewaters. Phenols, nitriles, and
substituted organics are also adsorbed by carbon when present in low
-------
APPENDIX A-6-45
concentrations. Additionally, benzene hexachloride and other chlorinated
aromatics have been removed from pesticide manufacturing effluents by
carbon adsorption. These chlorinated hydrocarbons can be re-
covered by regeneration with steam or with benzene.
Combustion processes are often feasible for disposal of petrochemi
cal wastes which may be too concentrated, too toxic, or otherwise unsuit-
able for other methods of disposal. Combustion may be either direct or
catalytic, depending on the waste to be oxidized. Incineration and sub-
merged combustion are both direct combustion methods used by the petro-
chemical industry.
Submerged combustion has been used successfully in the total or
partial evaporation of waste streams as well as concentrating dissolved
solids. This method produces an effluent which either has reuse value or
which is easier to dispose of than large volumes of the liquid waste. In-
cineration is the most commonly used combustion process for petro-
chemical wastes. Recently, fluidized bed incinerators have been used
for burning oily sludges. The fluidized-bed incinerator is reported
to provide better controlled combustion with lower requirements for
excess oxygen than conventional incinerators for oily sludges. However,
incineration occasionally converts a water pollution problem into an air
pollution problem. For example, the air pollutants, sulfur dioxide, and
hydrogen sulfide (from incomplete combustion) may be released to the
atmosphere when petrochemical wastes are incinerated.
Filtration processes are used to remove and concentrate solids on
oily materials from a waste stream. A filter can be specifically designed
to remove small quantities of these materials as a final step in waste
treatment, or it may be used to concentrate a waste so that further treat-
ability of wastewater will be enhanced. Sludges produced by chemical
coagulation and clarification of petrochemical wastes are often concen-
trated using centrifugation or vacuum filtration for easier handling and
disposal. If effluent standards imposed on a plant are particularly
stringent, a polishing filter employing sand filtration can be used to re-
move additional suspended material.
Miscellaneous Treatment Methods - Evaporation has been used as
a method for treating some petrochemical wastewaters. Solar evapora-
tion is feasible in areas with low annual rainfall and a relatively warm
climate. Spraying the wastewater into the air will also increase the
evaporation rate.
-------
APPENDIX A-6-46
The separation of surf ace-active agents from wastewater by induced
foaming has been investigated in laboratory and pilot plant studies.
Most of these studies have considered the removal of synthetic detergents
from domestic wastes. It has been demonstrated that the surface-
active agent, naphthylamine, which has little or no foaming ability, could
be removed from solution by adding a foaming agent and inducing froth-
ing.
CHEMICAL TREATMENT
The use of chemical systems for treating specific petrochemical
wastes has been successfully employed. The most common methods for
chemically treating petrochemical wastes include neutralization, preci-
pitation, coagulation, and oxidation.
Neutralization and pH Adjustment - Neutralization of petrochemical
wastes may be desired for several reasons, including:
a) Preparation of a waste for biological treatment,
b) Preparation of a waste for direct discharge,
c) Pretreatment for efficient coagulation,
d) Prevention of attack and corrosion of conveyance or process
equipment, and
e) Prevention of unwanted precipitation of waste components.
Neutralization implies the adjustment of a wastewater pH to values
at or near neutral pH; i. e., pH seven. Types of wastes generally neu-
tralized are (a) dilute acid or alkaline wash waters; (b) spent caustics;
(c) acid sludges from alkylation, sulfonation, sulfation, and acid treat-
ing processes; and (d) spent acid catalysts.
Sulfuric acid is the most common neutralizing agent used to neu-
tralize spent caustic wastes. Acid sludges are normally hydrolyzed
to free acids prior to their use as neutralizing agents. Spent caustic
neutralization with an acid can be designed as a batch or a continuous
system. The carbon dioxide in flue gases can also be used to neutralize
spent caustic solutions. Flue gas neutralization is economically feasible
provided that the gases are available at high enough pressure so that no
compressor is required to inject them into the spent caustic solution.
-------
APPENDIX A-6-47
Spent acid catalyst and sludges have been spread in pits filled with lime,
limestone, or oyster shells for neutralization. It should be noted that pH
adjustment is commonly used to facilitate coagulation and precipitation.
Coagulation - Precipitation - The addition of coagulants under prop-
er conditions causes the formation of a settleable precipitate containing
waste materials which can be removed by conventional sedimentation or
flotation processes. It should be noted that coagulation is always followec
by some type of solids-separation process. The most commonly used
coagulants are hydrated aluminum sulfate (alum), ferrous sulfate, and
ferric salts. The conventional coagulation system utilizes a rapid mix
tank followed by slow agitation of the mixture to promote growth of floe
particles which settle. The sludge-blanket clarifier, which provides
mixing, flocculation, and settling in the same unit, has had many indus-
trial applications because of its compact dimensions.
Coagulant aids are sometimes necessary to promote bridging be-
tween floe particles and render the floe more settleable. The most com-
mon coagulant aids are activated silica, bentonite clays, the organic
polyelectrolytes, and water treatment clarifier sludge. The three types
of polyelectrolytes are categorized by their electrochemical nature,
specifically, cationic, anionic, and nonionic.
A common application of coagulation in the petrochemical industry
is the removal of emulsified oils from waste streams. Suspended solids
and turbidity removals are often as high as 90 percent. However, most
petrochemical wastes contain dissolved organic compounds which are not
easily removed using coagulation methods. Coagulation has been used
also to remove metals such as lead and zinc, water-soluble alkyl-aryl
sulfonates by lime coagulation enhanced with ferrous sulfate, and low
concentrations of sulfide which are precipitated with zinc chloride, ferric
chloride, or copper sulfate.
Provisions must be made for the disposal of the sludges formed by
the settled precipitates from coagulation-precipitation processes. Land-
fills are the most common form of inorganic sludge disposal, while
organic sludges are usually dewatered by some filtration method and sub-
sequently incinerated or buried.
Oxidation processes are used to treat both organic and inorganic
contaminants using oxygen or other chemicals as the oxidizing agents.
The oxidation of sulfides to sulfates using steam and air is an effective
treatment method; however, wastes containing high concentrations of
phenol cannot be treated in this manner because phenols interfere with
-------
APPENDIX A-6-48
sulfide oxidation. If large quantities of mercaptans or mercaptides are
present in the waste, a reoxidizer may be required to ensure complete
oxidation.
Catalytic oxidation is usually applied when the fuel value of a waste
is too low for conventional incineration. The process was originally de-
signed to operate in the vapor phase but has been successfully applied to
aqueous wastes. Laboratory studies have shown that dilute aqueous
organic wastes could be effectively oxidized at temperatures below 600°C,
by using a copper-chromate catalyst. Investigations have demon-
strated that hydrocarbons also could be oxidized by using metal oxide
catalysts. The initial cost of catalytic oxidation units may be 20
to 30 percent greater than that for conventional incinerators, but for
dilute organic wastes the operating costs may be 15 to 20 percent less.
Wastes containing sodium sulfite, which has a very high immediate
oxygen demand, can be oxidized by bubbling air through the system. Iron
catalysts have been employed occasionally to speed the oxidation reaction.
The oxidation of sulfite to sulfate will increase the acidity of the
waste and require subsequent neutralization. Diffused air has also been
used to oxidize metal salts to insoluble hydroxides which were removed
by sedimentation.
Chlorine has been used successfully to oxidize phenol and cyanide
in petrochemical wastes. The oxidation of phenols must be carried to
completion to prevent the release of chlorophenols which cause object-
ionable tastes and odors in drinking water. Cyanides can be oxidized to
carbon dioxide and nitrogen by chlorination if the pH is maintained in
excess of 8. 5 and sufficient chlorine used, thus preventing the release of
toxic cyanogen chloride. Chlorine dioxide has been shown to overcome
these and other disadvantages Of chlorine and hypochlorite oxidation,
although this treatment is very expensive.
Ozone has been proposed as an oxidizing agent for phenols, cya-
nides, and other unsaturated organics because it is a considerably
stronger oxidizing agent than chlorine. The chief disadvantage is the
high initial cost of ozone generation equipment. Ozone has several
advantages, one of which is its ability to react rapidly with phenols and
cyanide.
Oxidation of phenols using hydrogen peroxide and ferrous salts has
been investigated in the laboratory. Treatment of the industrial
wastes in this case produced colored effluents which required additional
treatment with alum.
-------
APPENDIX A-6-49
Miscellaneous Methods - Ion exchange has been used to remove
specific petrochemical pollutants. Quaternary ammonium anion resins
have successfully removed phenols in the laboratory. However, re-
generation of the resin -was difficult and uneconomical. Salicylic acid
recoveries of 80 percent were obtained from aspirin manufacturing efflu-
ents using a caustic- soda regenerated resin. Chemical reduction
has been used in isolated cases to treat constituents of a waste stream.
BIOLOGICAL TREATMENT PROCESSES
Biological treatment of liquid petrochemical wastewaters is usually
the most economical method of reducing its toxicity, organic content,
and objectionable appearance. Extensive pretreatment is often required
before a petrochemical waste stream can be treated biologically.
The applicability of biologically treating a particular waste is a
function of the biological degradability of the dissolved organics present
in the wastewater. When considering the economics of a biological treat-
ment system, the time required to biologically degrade the dissolved
organics is of primary importance. This degradation rate of an organic
compound is a function of the molecular structure of the compound, the
genera and species of microorganisms utilizing it as a food source, and
the time required for the microorganism to develop the enzymes neces-
sary for substrate utilization.
The biodegradability of an organic compound can be classified in
several ways- The BOD parameter establishes a relative degree of
biodegradability provided that acclimated seed is used for the test.
There is much contradictory data relating the molecular structure of a
compound to its biodegradability. However, the amenability or resist-
ance of certain classifications of organic compounds to biological oxida-
tion is well documented as described below.
a) Aliphatic or cyclic aliphatics are usually more susceptible to
biological degradation than aromatics.
b) Unsaturated aliphatics, such as acrylics, vinyl, and carbonyl
compounds are generally biodegradable.
c) Molecular size is significant concerning the biodegradability
of an organic. Polymeric and complex molecular substances
have shown resistance to biological degradation, part of
which is attributed to the inability of the necessary enzymes
-------
APPENDIX A-6-50
to approach and attack susceptible bonds within the compound
structure.
d) Structural isomerisms in organic compounds affect the rela-
tive biodegradability of many compound classes. For
example, primary and secondary alcohols are extremely
degradable while tertiary alcohols are resistant.
e) The addition or removal of a functional group affects the bio-
logical oxidation. A hydroxyl or amino substitution to a
benzene ring renders the compound more degradable than the
parent benzene, while a holgen substitution causes it to be
less biodegradable.
f) Many organic compounds are extremely biodegradable at low
concentrations but are bio-static or bio-toxic at higher con-
centrations.
The relative biodegradability of certain organic compounds is pre-
sented in Table 10.
Nutrients - Effective biological treatment of any organic contami-
nant requires the availability of essential nutrients for the organism.
The mineral nutrients required by bacteria are available in sufficient
amounts in most wastewaters, but nitrogen and phosphorus requirements
are more critical and many petrochemical wastes are deficient in one or
both of these elements. Nitrogen (N) and phosphorus (P) requirements
for biological treatment have been related to the magnitude of the de-
gradable organic content of wastewater as represented by BOD. General-
ly, a BOD:N:P ratio of 100:5:1 will provide sufficient amounts of these
nutrients. Nitrogen is most readily available in its reduced form as
ammonia, ammonium ion, or amino nitrogen. Organic nitrogen,
nitrates, nitrites, and organic compounds containing these forms can
also be used, but a considerable expenditure of energy is required to re-
duce these forms to ammonia nitrogen. Phosphorus is most readily
available to the microorganisms as a phosphate.
Neutralization - Most biological treatment systems operate effi-
ciently at pH values between five and nine, while optimum conditions
usually fall within the pH six to eight range. Therefore, neutralization
or pH adjustment is commonly required in many petrochemical waste-
water treatment systems.
-------
APPENDIX A-6-51
TABLE 10
RELATIVE BIODEGRADABILITY OF CERTAIN ORGANIC COMPOUNDS
(References 72, 73, 81)
Biodegradable Organic Compounds
Compounds Generally
Resistant to Biological
Degradation
Acrylic Acid
Aliphatic Acids
Aliphatic Alcohols (normal, iso,
secondary)
Aliphatic Aldehydes
Aliphatic Esters
Alkyl Benzene Sulfonates w/excep-
tion of propylene-based Benzal-
dehyde
Aromatic Amines
Dichlorophenola
Ethanolamines
Glycols
Ketones
Methacrylic Acid
Methyl Methacrylate
Monochlorophenols
Nitriles
Phenols
Primary Aliphatic Amines
Styrene
Vinyl Acetate
Ethers
Ethylene Chlorohydrin
Isoprene
Methyl Vinyl Ketone
Morpholine
Oil
Polymeric Compounds
Polypropylene Benzene Sulfonates
Selected Hydrocarbons
Aliphatics
Aromatic s
Alkyl-Aryl Groups
Tertiary Aliphatic Alcohols
Tertiary Benzene Sulfonates
Trichlorophenols
Some compounds can be degraded biologically only after extended
periods of seed acclimation.
-------
APPENDIX A-6-52
Equalization - Petrochemical wastes are particularly subject to
wide variations in How and composition; thus, some form of equalization
may be necessary to dampen these fluctuations and minimize transient
effects which may adversely affect the biological process.
Pre- and primary treatment may be required to remove certain
materials which would adversely affect the biological system. Oils are
difficult for the organisms to metabolize due to their low solubility. In-
organic and non- biodegradable organic suspended solids will tend to build
up in a treatment system, decreasing the proportion of active biological
solids, and thus adversely affecting the treatment efficiency. Sulfides
react with dissolved oxygen and reduce the available oxygen to the
organisms. Heavy metals are toxic at defined concentrations and must
be removed or reduced to safe levels. Also, waste streams with poten-
tially toxic organic compounds should be separated and treated prior to
discharge into the biological treatment system.
Temperature - The optimum temperature for most aerobic biologi-
cal treatment systems is approximately 20 to 35 C. High tempera-
tures of waste cause a decrease in oxygen solubility as well as increased
oxygen utilization rates.
The activated sludge process is a continuous system where biologi-
cal growths are mixed with wastewater, aerated, and then undergo bio-
logical sludge separation. A portion of the concentrated sludge is then
recycled and mixed with additional waste. Completely mixed aeration
designs are generally favored over plug flow systems for industrial
waste treatment. These effluents discharged from completely mixed
activated sludge systems generally are of better quality than those ob-
tained from other biological processes in terms of organic and solids
concentrations, but construction and operational costs are usually higher.
Parameters to be considered in the design of an activated sludge
system include the fundamental factors of temperature, pH, and nutrient
availability as well as the following:
a) The organic loading in terms of BOD applied per day per unit
weight of biological solids,
b) The BOD removal kinetics of the specific petrochemical
wastewater,
c) The quantity of biological sludge produced including accumu-
lation of primary sludge.
-------
APPENDIX A-6-53
d) The oxygen requirements of the system, and
e) The settleabilityof the biological sludge and the ease of
gravity solids-liquid separation.
A summary of activated sludge plants treating petrochemical
wastes, including information concerning the petrochemical products,
applied loadings, nutrient requirements, and effluent quality are tabu-
lated in Table 11. It should be recognized that many organic compounds
can be chemically oxidized while remaining resistant to biological degra-
dation, therefore being registered as COD but not BOD. The difference
between the measured COD and BOD values indicates the magnitude of the
organic fraction that is not readily amenable to biological degradation.
Trickling filters are commonly used in industrial waste treatment
as "roughing devices" designed to equalize and reduce organic loads to
activated sludge or aerated lagoon processes. Trickling filters employ
microbial films which are attached to rock or synthetic media to remove
organic materials from the wastewater solution. Most filter processes
employ recirculation to increase the overall filter efficiency and to mini-
mize shock loadings.
Although BOD removals obtained by trickling filters are usually
less than those found in the activated sludge process, toxic effects are
not as pronounced or perpetual. Additionally, filter design and operation
is relatively simple. The recorded treatment of various chemical and
petrochemical wastes using trickling filters is presented in Table 12.
Aerated lagoons are basins six to twelve feet in depth where oxygen
is supplied mechanically. The two general types of aerated lagoons are
the aerobic lagoon and the facultative lagoon. In the aerobic lagoon, all
biological solids are kept in suspension, while sludge settling and conse-
quent anaerobic decomposition are characteristic of the facultative
aerated lagoon. In these lagoons, the solids concentration is allowed to
reach an equilibrium concentration which depends on the organic concen-
tration of the waste, the synthesis sludge rate coefficients, and the
amount of power imparted to the basin liquid. Equilibrium-suspended
solids normally range from 80 mg/1 to 250 mg/1.
High levels of treatment are generally not achieved in the aerated
Lagoons because of the BOD and COD associated with the effluent sus-
pended solids and the relatively small number of active biological solids
in contact with the wastewater. Aerated lagoons are particularly sensi-
tive to transient organic loadings, toxic substances, and temperature
-------
Product
and /or
Process
Refinery,
Natural
Gas Liquids,
Chemical
Specialties,
Sanitary
Sewage
Phthalic
Anhydride,
Phenol,
Salicylic
Acid, Rubber
Chem. ,
Aspirin,
Phenacetin
Refinery,
Detergent
Alkylate
TABLE 11
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
Flow In Out Rem In Out Rem Ib BOD-ftgrents
ftUTfTft fn.-LjT/1\ /i-i-irr/1\ t"! \ (m rr f 1 \ /m rr / 1 ^ 11 \ Tfom/1 T7 nm ±1 -rlr o
wujji ung/i; img/i; \"io) vmg/i; img/i; \/o; ., „„ neqa. nemarKS
4.87 90 20 78 200 90 55 0.1 None Effl.phenol
Effl. oil
0.5mg/l
2.54 45.7 6.1 86.7 0.031 None Brush
Aeration,
treats
trickling
filter em.
55% sludge
return
2. 45 345 50- 71- 855 150- 76. 6- 0. 08 PO4 Phenols in
= 160mg/l
100 85. 5 200 82. 5 Sulfide in
= 150mg/l
Lab scale
Ref
111
110
44
W
Oi
I
-------
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD
Product
and /or Flow In Out
Process (MCD) (mg/1) (mg/1)
Butadiene 2. 0 2, 000 25
Maleic Acid
Butadiene 1.5 1,960 24
Alkylate
Butadiene, 1. 5 1, 960 24
Maleic
Anhydride
Fumaric Acid,
Tetrahydro-
phthalic,
Anhydride,
Butylene
Isomers,
Alkylate
Ethylene 1.44 600 90
Propylene,
Benzene
COD Organic
Loading Nutri-
Rem In Out Rem lbBQD_/d3K ents
("! \ l-mrtl'\\ (rnnl'\\ (1 \ TTrrrf Rrm^i-lre Pi-f
98.8 2,990 480 84 0.24 NH, 34
98.8 2,980 477 98.3 34
98.8 2,980 51 84 0.24 NH_ Surface 84
(MLVSS) aerators
wastes con-
tain: alco-
hols,, maleic
acid, fur
marie acid,
cetic acid,
Cj-C4 alde-
hydes, fur-
fural, water
soluble addi-
tion prod-
ucts
85 700 105 85 None Oilywaters: 92
C^C Qoils
90% pnenol
rpmnval
w
o*
-------
Product
and /or
Process
Naphtha-
lene,
Butadiene,
Phenol,
Acrylo-
nitrile,
Soft De-
tergent
Bases,
Resins,
Other Aro-
matics
Phenol, 2,
4-D Aniline,
Nitro- Ben-
zene, Rub-
ber Chem. ,
Polyester
Resins,
Misc. Chem.
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
Flow In Out Rem In Out Rem JbBCXX/daK ents
ftl/rrrA Imnll} lmall\ ("! \ (rr\ a 1 1 \ tm rr ! 1 \ ("! \ ' TVrri TT om ±1 rlr c T?n<
0.43 500 60 85- 600 90 80- 1.5 NH, Sour waters: 92
90 85 PO4 Oil in = 500
mg/1 Phen-
in = 65 mg/1
pH adjust-
ment, pre-
ceded by
trickling
filter,
phenol re-
moval =
99. 9%
0.97 370 76 76.2 0.4 NH, Accelator 80
PO4 Pilot Plant
Sewage
added in
ratio 1:600
once a wk
w
t>
I
o>
CJT
o>
-------
Product
and /or
Process
Ethylene,
Propylene,
Butadiene,
Benzene,
Polyethylene,
Fuel Oils
Refining
Processes
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
F1
-------
Product
and /or
Process
Nylon
Petroleum
Acrylic
Fibers
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
Flow In Out Rem In Out Rem Ib BDDL/day. ents
Iti/tfTi /mrr/ll fmcr/1^ 11 \ (m a 1 1 \ frn a f "\ \ I"! \ TtrnA Ytftm^r\ra. Tt of
UvlLM img/i; vmg/i; \/o) vnig/i; \rn.g/i> \/ot ., ___ „„ rteqa. riemarKS rtei
0.4 1,540 250 83.8 34
0. 27 440 5 98. 8 500 60 88 Phenol in
= 25 ppm 34
Pheno] out
= 1 ppm
0.2522,260 118- 90- 0.4 Wastes con-105
226 95 tain acrylo-
nitrile, di-
methylamine,
dimethylfor-
mamide, for-
mic acid temp.
3 5-3 7°D re-
turn sludge
10-50%
mechanical
aeration
>
g
R
^
03
1
01
00
-------
Product
and /or
Process
Acetone,
Phenol p-
Cresol,
Ditert. -
Butyl- p-
Cresol,
Dicumyl
Peroxide
Resins-
Formalin,
Aminoplasts,
Phenol- For-
mald. ,
Epoxy Resins
Textile Aux.
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
Flow In Out Rem In Out Rem IbBCDL/dK ents
/h/f/Tft /i-nrr/ll In-t rr t t \ ("] \ (m rt 1 1 \ tmnl'\\ ("! \ Tterr\ Tie- m^i-lre: T7 cf
UVILM \m.gi i) ung/i; \/oi vnig/i; \mg/i> \/o) ., _„ x\eqa. nemarKS xtei
0.2163,560- 1,030- 11- 0.89- Waste 33
4,400 750 83 1.1 phenol 600
ppm Waste
BOD 75, 00-
8, 000 Waste
diluted w/
effl. or
water; pilot
plant
0.2 890 444- 50- 0.8- Diffused- air; 98
266 70 1.2 domestic
waste added;
trickling fil-
ter follows
, 100% recycle
sludge
w
O)
CJT
CO
-------
Product
and /or
Process
Ethylene and
Propylene
Oxides, Gly-
cols, Mor-
pho lines,
Ethylene-
Diamines,
Ethers,
Piperazine
2, 4-D
2,4.5-T
(Acid Wash
Wastes)
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD COD Organic
Loading Nutri-
Flow In Out Rem In Out Rem IbBCCL/dsK ents
rtljTlT* /TI-L JT / 'M fi-nrr/'H I"! \ /mrr/ll Irn a I "\ \ ("f \ TTrnri T7rmTrlrc T7rf
0.15 1,950 20 99 7,970- 5,120- 25- 0.51 None Lab Scale; 43
8,540 5,950 40 extended
aeration;
high non-
biode-
gradable
fraction
followed by
stab, ponds
0.1 1,670 125 92.5 2,500 500 80 0.78 NH 1:1 mixture 42
(MLVSS) PO^ of acid wash
4
streams
diluted 9:1
prior to
treatment
to reduced
chlorides.
toxicity Lab
Scale
W
O5
I
O>
o
-------
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL
WASTES
BOD
Product
and /or Flow In Out
Process (MCD (mg/1) (mg/1)
Cracking, 1, 100 55-
Isomeriza- 110
tion of Butane
and Naphthene,
Alkylation,
Benzene,
Toluene, Alco-
hols, Ketones,
Cresylic Acids
Ethylene, Ace- 20
tylene
Nylon Manuf. -
Adipic Acid
Asidonitricz
Alk. Organics
COD Organic
Loading
Rem In Out Rem Ib HCCL/dap
i"! \ trr\a!\\ fmall} I"! \ '
\/o) vmg/i; vmg/i; \/oi ., _^j „_
90- 0. 5
95
0.23-
0.33
95 85 1.0-
3.0
Nutri-
. ents
• Reqd. Remarks Ref
90-95%
phenol
removed;
Lab Scale
PO4 Effl. phenol
0.1 mg/1
Effl. oil
1 ppm
PO. NH. OHused
4 4
NH_ as nutrient
and neutra-
lizing agent
waste di-
luted 2:1
29
59
30
86
w
§
-------
TABLE 12
TRICKLING FILTER TREATMENT OF PETROCHEMICAL
WASTES
BOD COD Organic
Product Loading
and/or Flow In Out Rem In Out Rem Jb BCDg/dy
rrocess UVILLJ png/i; img/i; \/oi img/i; vmg/i; \/oi - nnn rt,&
I , UUU II
Phenol, Sali- 2. 59 190 58 69.5 40.5
cylic Acid,
Rubber Chem.
Aspirin, 2.59 58 34 41.5 11.8
Phenacetin,
Phthalic An-
hydride
Plastics, 1.061,960 37 98.1 2,660 230 91.5
Amines,
Enzymes
Ethylene, 0.63 170 85 50 400 200 50 89
Propylene,
Butadiene,
Benzene,
Polyethylene,
Fuel Oil
Defi-
cient
. Nutri-
ents Remarks Ref
None Rock Media, 110
recirc. ratio
2.84:1
None Rock Media,
treats effl.
from above
filter, effl.
to act. si.
2 filters, 34
followed
None Plastic 95
filter media
followed by
act. sludge
phenol re-
moval = 95%
influent di-
luted 2:1 w/
cooling water
w
CT5
I
O>
to
-------
TRICKLING FILTER
TABLE 12 (Continued)
TREATMENT OF PETROCHEMICAL WASTES
BOD
Product
and /or Flow In Out
Process QVGGD (mg/1) (mg/1)
Aliphatic 0. 57- 1. 100- 23-
Acids, 0.86 2,300 470
Esters,
Alcohols,
Aroma tics,
Amines,
Inorganic
Salts
Ethylene, 0. 43 1, 300
Propylene,
Butadiene,
Benzene,
Naphthalene,
Phenol, Acry-
lonitrile, Soft,
Detergent
Bases, Resins
COD Organic Defi-
Loading cient
Rem In Out Rem Ib BOD_/dajr Nutri-
(%) (mg/1) (mg/1) (%) ( a J ents
1, 000 ft
57- 42. 1- None
99 82
(Both fil-
ters com-
bined)
1,500 450 60- 140 NH
70 PO^
Remarks Ref
pH adjusted 101
prior to
treatment;
2 filters in
series; Re-
cycle on
1st state
is 14-21:1
Sour 92
Waters,
Rock Media
M
I
0>
CO
-------
TABLE 12 (Continued)
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
BOD
Product
and/or Flow In Out
Process OVIGD) (mg/1) (mg/1)
Pentaery- 0.1185,080- 225-
thritoc Waste 5, 800 232
contains For-
maldehyde,
Sodium For-
mate, Metha-
nol, Pentaer-
thritol
Resins- For- 0.17
maum, Amino-
plasts, Phenol- 0.03
Formal, Epoxy
Resins, Tex-
tile Aus.
Acrylic Fibers 0. 32 13
COD Organic Defi-
Loading cient
Rem In Out RemlbBQD/*y. Nutri-
laf \ fmtr/'n (mall} ("? \ ? rnl-n
v lot \mgiii \mgii) \ lot . 000 ft ents
95- 1st stage 65 NH0
^r O
96 PO.
Yes
82.6 11.7 None
89.3 14.6 None
30- 49 30- 50 NH
70 70 84 PO^
Remarks Ref
2 filters 32
in series
followed by
act. sludge;
recycle 40-1
on prim.
filter, 13-1
second
Both filters 98
treat act.
sludge effl.
Blast fur-
nace slag
media
Waste con-
tains phenol.
formalde-
hyde, methanol
Waste con- 91
tains: acry-
lonitrile and
W
0>
Entire Treatment System
-------
TABLE 12 (Continued)
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
BOD
COD
Product
and/or
Process
Organic
Loading
Defi-
cient
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
In
Out
Rem Jb BDCL/dy. Nutri-
(%) , ^^x> ,.3 ents Remarks
Ref
Synthetic
Resins- Phenol,
Formaldehyde,
Fatty Acids,
Phthalic Acid,
Maleic Acid,
Glycerol,
Pentaery-
thritol,
H. C. Solvents
95-
98
1st stage
85 (as
Phenol)
2nd stage
11.6-L8.2
gpd/ff3
Plastic 27
media, 2-
stage treat-
ment; In-
fluent:
Phenol =
4, 500 mg/1
Formalde-
hyde =
2, 000 mg/1
Fatty acids
= 800 mg/1
Phthalic and
maleic acids
= 1,000 mg/1
Eff. phenol
= 1.5 mg/1
W
a
OJ
0>
en
-------
TABLE 12 (Continued)
-TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product
andlor
Process
BOD
Flor In Out
MOD) (mg/1) (mg/1)
COD
Rem In Out
(%) (mg/1) (mg/1)
Organic Defi-
Loading cient
Rem Jib BCC^/d^ Nutri-
ents
J
1, OOP ft
Remarks Ref
Waste con-
ains Aery-
cetone,
nhibitor oils,
lcohols,
Esters, HJ3O,
Organic Acids
51- None Original
79 None loading was
lower value,
loading in-
creased w/o
any adverse
effects
15,000 Ib
BODe re-
moval
day
23
per
w
en
i
CO
eo
-------
APPENDIX A-e-e?
changes. A summary of reported data on treatment of petrochemical
wastes by aerated lagoons is given in Table 13.
Waste stabilization ponds, which depend on the natural aquatic
processes of bacterial and algal symbiosis, have been used successfully
to treat petrochemical wastes. These ponds are often designed to polish
the effluent from other biological waste treatment processes, but they
have been used in some instances to treat entire plant wastes.
Waste stabilization ponds are categorized as being "aerobic, "
"facultative, " or "anaerobic. " The BOD removal found in these oxida-
tion ponds is comparable to other biological unit processes, but the COD
reduction capacity is often higher. However, highly colored substances
reduce sunlight penetration and cause reduced photosynthesis, often
affecting COD removal capacities. There also are toxic effects of many
compounds on the pond algae which upset the symbiotic algal-bacterial
relationship. Operational data on these ponds in the petrochemical
industry are given in Table 14.
Miscellaneous Biological Treatment Processes - Cooling towers
have been used as biological treatment devices and provide a method for
reuse of water through the means of "free" biological treatment. Pilot
plant investigations using a percolating and filter as a biological treat-
ment process have indicated some promise.
Multiple Biological Treatment Schemes - The complexity of most
biological treatment systems and the associated effluent quality require-
ments often circumvent single-stage biological treatment. Various com-
binations of biological processes, therefore, may be employed to achieve
the desired effluent quality.
A general sequence of biological wastewater treatment process is
demonstrated in Figure 13.
OTHER METHODS OF DISPOSAL
Dilution - This form of disposal is becoming less and less popular
with regulatory authorities. However, certain petrochemical plants are
allowed to discharge their wastes to receiving waters without treatment
providing:
a) Sufficient receiving water is available as a diluent,
-------
AERATED LAGOON
TABLE 13
TREATMENT OF PETROCHEMICAL WASTES
BOD
Product
and /or Flow In Our
Process (MGD) (mg/1) (mg/1)
Refinery 19.1 225 100
Butadiene,
Butyl Rubber
Refinery, 2.45 345 50-
Detergent 100
Alkylate
Cy clohexane, 0.51 100 25
L>-Xylene,
[Benzene, Para-
pnic Naptha,
o-Xylene Gaso-
line Nylon
Fibers
COD Organic
Loading Nutri-
Rem In Out RemlbBCCL/oVv ents
("! \ lrrtftll\ {-mrtll\ f"f\ TTnrrl T7 nm 3 -rlr c: T7of
Acre day
55 610 350 43 4,630 PO4 Followedby 45
stab, pond
temp = 32°C
30% COD is
non- biode-
gradable
Lab Scale
71- 855 150- 77- 6,300 PO4 Influent 44
85 200 83 phenols 160
mg/1 Influ-
ent sulfides
150 mg/1
Lab Scale
75 400 Surface 64
aeration,
waste is
extensively
pretreated.
Followed by
pond
w
S
o>
0>
Q>
-------
Product
and/or
Process
Chemicals
for Lubri-
cating Oils
TABLE 13 (Continued)
AERATED LAGOON TREATMENT OF PETROCHEMICAL WASTES
BOD
COD
Organic
Loading Nutri-
Rem In Out Rem Ib BCCU/dy. ents
(MOD) (mg/1) (mg/1) (%) (mg/1) (mg/1) (%) Acre day Reqd< Remarks
Flow In
Out
0.2
465
180
61 1,050
600
43
Rei
34
W
I
o>
o>
(0
-------
WASTE
STABILIZATION
TABLE 14
POND TREATMENT OF PETROCHEMICAL WASTES
Product
and /or Flow
Process (MCD)
Refinery, 19.1
Butadiene
Butyl Rubber
Resins, 5
Alcohols, 1,
Amines, 5
Esters,
Styrene, 5
Ethylene
Butane, 3.25
Propane,
Nat. Gas,
Ethanol,
Ethyl
Chloride,
Polyethylene,
Ammonia,
H2S04
In
BOD
Out
(mg/1) (mg/1)
100
500-
000
400-
700
25-
50
150
50
400-
700
25-
50
5-
30
7-
15
COD
Rem In Out
(%) (mg/1) (mg/1)
50 350 200
20-
60
88
96
40-
90
90- 260
95
Organic
Loading Nutri-
Rem ,lb BOD-, ents
I"! \ r?rnr1
Acre day M
43 Primary None
pond 91;
Total
ponds 46
96 None
164 None
5 None
75 None
Remarks
Ref
Ponds in ser- 45
ies after
aerated la-
goon Lab
Scale
Anaerobic
Anaerobic
Aerobic
Facultative
13
13
13
113
pond, 18 days
detention
Infl. SO, =
650 mgA
w
§
I
at
i
-------
WASTE
TABLE 14 (Continued)
STABILIZATION POND TREATMENT OF PETROCHEMICAL WASTES
Product
and /or Flow
Process (MCO
Refinery, 2. 45
Detergent
Alky late
Plastics 1.69
Ethylene 0. 15
and Propy-
lene Oxides,
Glycols,
Morpholines,
Ethylene-
diamines,
Ethers,
Piperazine
Mixed
Petrochemi-
cals
BOD COD Organic
~ Loading Nutri-
In Out Rem In Out Rem .lb BOD_. ents
{mrr/ll fmcr/1^ 1"! \ lma!"\\ fmcr/11 I"! \ ' Ttrnrl Pirmar-lra
vmg/i; vnig/i; \/oi vrng/i; vmg/i; \/oj Arrtt A* iteqa. xxemarKS
50- 20- 50- 150- 120 20- 95 None After
100 50 80 200 40 Aerated
Lagoon Or
Act. SI
Lab Scale
686 186 1,681 590 65 Faculta-
tive Ponds
20 5,120- 4,610- 10- 25 None Lab Scale
5,950 4,450 25 Facultative
Ref
44
34
43
Ponds to re-
move some
resid. COD
High non-
biodegrad-
able frac-
tion. After
activated
sludge
95- 75- 100 Faculata-
99 96 live ponds
•
113
w
2
O
i
O)
i
-------
FIGURE 13
VM-MwARiHkMm
^NMt Si*ril»MH LMtf]
IA»«»«->«»II«^I p
1 1»M
,,00
T
s
r
§•
1
»»
en
i
•>»
to
-------
APPENDIX A-6-73
b) There are no toxic or refractory compounds in the waste
stream, and
c) The assimilative and recovery capacity of the receiving
water is adequate.
Joint industrial-municipal treatment has been successful in certain
cases, especially where small petrochemical plants are located near
large metropolitan areas. Usually, some form of pretreatment is neces-
sary befc-re the industry discharges into the municipal sewer. It
generally has been established, however, that individual treatment offers
both economic and political advantages, particularly where large volumes
of petrochemical wastewaters are involved.
Disposal wells used for the subsurface injection of wastewater are
listed in Table 15. Most of the petrochemical wastes noted in Table 15
must be pretreated prior to injection. The more common formations
suitable for injection of wastes include unconsolidated sands, lime-
stones, and dolomites. The dangers of contaminating potable water-
bearing formations can be assessed by studying the overlying and under-
lying strata and locating unplugged wells in the contiguous area.
Ocean Outfall - The direct discharge into the ocean is feasible
when locations permit. Most liquids flow through outfall pipelines, the
distance of discharge from shore depending on the nature of the waste-
water, the ocean currents, and shoreline use. Barge disposal is another
method of conveying wastes to the ocean for disposal.
Submerged combustion is the burning of a gaseous fuel in a spec-
ially designed burner with the burner chamber submerged in the waste-
water. This device has been used successfully in totally or partially
evaporating waste streams, concentrating any dissolved solids, either
which have reuse value or which are easier to dispose of than large
volumes of the liquid waste.
A submerged combustion unit reduced 75 percent of the volume of
a nylon waste stream, the remainder of which was mixed with other
process streams and treated biologically. A polymeric waste
stream containing suspended synthetic rubber particles, organic sol-
vents, inorganic salts, and synthetic detergents was not amenable to
biological treatment and, consequently, treated by submerged combustion.
This waste stream was evaporated to about 10 percent of its
original waste volume with the resulting slurry emptied to a drying bed.
-------
TABLE 15
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
Injection
Flow Depth Pressure
Type Waste (gpm) (ft) (psia) Formation
Acrylonitrile and 650 7, 203 Up to Sat. Brine,
Detergent Manuf. 2, 000 Miocene Sands
Wastes: COD =
17,500 mg/1; pH
= 5.4, SO4 = 10,000
mg/1
10-15% NaCl; Diss. 500- 4 wells: 200 Unconsolidated
Metal Salts; Trace 600
Organics; pH 7. 5- 8. 5 Brine Sands
Refinery and Petro- 500 1, 200 75 Sandstone
chem. Cooling Water
Blow- down Boiler
Blow- down, Process
Waters
Pe trochem. Waste 400 6, 700 400 Sands
Organic Nitrogen
Nitrites
COD p 20, 000 ppm
pH - 12
Uranium 238
Required
Pretreatment
Neutralization; Settling
and Equalization in Pond;
Coagulation pH Adjust-
ment and Clarification;
Gravity Sand Filters
Oil Separation; Settling;
Pressure Leaf Filtra-
tion; Diatomite Filtration
Neutralization, Precipi-
tation - Sedimentation,
Filtration
Ref
92
54
31
48
48
M
OJ
-J
I*.
-------
Type Waste
Phenolic Waste: COD=
12, 000 ppm; 850 ppm
Phenol; 150 ppm Oil;
pH 10.8
Aromatics
Phenols 1,000-2,000
ppm COD 10, 000 ppm
pH 10. 7
0. 3% Acetic Acid
Chlorinated Deriva-
tives
Terephthalic Acid
Manuf.
Cooling and Boiler
Blow- down, Process
Wastes Containing
Organic Acids,
H. C. , inorganics
TABLE 15 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
Injection
Flow Depth Pressure Required
(gpm) (ft) (psia) Formation Pretreatment
300 6,330 1,000 Sat. Brine, Neutralization with
Miocene Sands Efc 804; Clarifier,
Pressure Sand Filter
300 6,100 1,000 Miocene Sands
204 3,700 2,000 Miocene Brine Cool to 150°F. Adjust
Sand pH to 4. 0- 5. 0, Settling
Coal Filter; Cartridge
Filter for Solids 10
150 5,600 Sands Settling, Filtration
Ref
92
48
115
48
W
I
O5
-------
TABLE 15 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
Type Waste
Flow Depth
(gpm) (ft)
Injection
Pressure
(psia) Formation
Required
Pretreatment
Ref
Nylon, Ammonia, Small- 5, 802
Olefins, Polyolefins 96
Refinery, Butadiene,
Sytrene, Synthetic
Rubber 1
800-
1,100
Limestone
Cuprous Ammonium 85
Acetate from Butadiene
Pond; Caustic Waste
from Ethylene Prod.
Caustic and Phenols
from Refinery
4,000
1,500-
2,000
Conventional Waste
Treatment, 0. 3% by
Volume of Acid, Added
Before Injection
Equalization, Settling
Refinery
Cooling & Boiler
Slowdown, Process
Wastes, Brines
Ammonia Prod.
Hydrochloric Acid
50 5,000
600
Sandstone
Settling and Storage
45
40
1,000
1,200
225
14.7
Sandstone
Sandstone
API Separator
None
71
95
48
48
48
W
H
en
I
O>
-------
TABLE 15 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
Type Waste
Flow Depth
(gpm) (ft)
Injection
Pressure
(psia) Formation
Required
Pretreatment
Ref
Detergent Product
32% HC1
Benzene
Chlorinated HC
35 3,400
Miocene Sands
Dilution with Equal
Volume Fresh Water
48
Spent Alkylation 1 5,100
Acid- 90% H2SO4;
7% Oil; 3% H2O
Filtrates and Distil- 1, 400
lates from Chloro-
mycetin Manuf:
BOD 20 = 45,000
ppm; pH 3. 5, Diss.
Solids = 50, 000 ppm
Saturated NaCl, Cone. 3, 000
Ca-Mg, Liquors, Phenols
Chloro-Phenols, Bis-
Phenols, Methocel, Weak
Caustic Washes
55
Saturated
Brine,
Sand
W
Limestone
Suspended Solids
Removed
-------
APPENDIX A-6-78
Volatile organic compounds in the polymeric waste, such as alcohols
and amines, were oxidized or burned so that no odors were detected in
the surrounding area.
Incineration of combustible and partially combustible liquid wastes
is often a feasible method of disposing of concentrated process streams.
The properly designed incineration system considers time, temperature,
and turbulence. Sufficient residence time shoujd be provided to permit
complete oxidation of the organic material, the temperature should be
high enough for the reaction to proceed, and the system should be suffi-
ciently turbulent to ensure that the oxygen in the air is contacted with the
dissolved organic material.
Although incineration is a practical means of handling a wide variety
of effluents, it should be evaluated only in the light of the total pollution
problem, particularly air pollution.
-------
APPENDIX A-6-79
4. HAZARD EFFECTS OF WASTES
Effluent from treatment processes may contain substances that
will cause immediate effects on the environment or may initiate or
perpetuate a chain of events that will ultimately damage the environ-
ment or its inhabitants. The general categories of effluents from
refineries and petrochemical production can be grouped under air,
water, or solid waste contaminants.
Air effluents include all materials that escape to the air from
failure to maintain control (spills, leaks, evaporation, etc.) or from
processes that release contaminants into the air. Air pollution
abatement equipment will reduce, but may not entirely eliminate.the
release of industrial pollutants.
As tighter control is obtained over air pollutants, the materials
formerly released into the air may be captured as liquid or solid
wastes. These wastes may contain compounds that are individually
harmful and may also be capable of degrading the aquatic or land
environment because of the impact of innocuous solid materials.
Some of the debilitating effects that suspended solids may have
on aquatic life include:
Entrapment of small aquatic plants, eggs and animals
Destruction of bottom organisms
-------
APPENDIX A-6-80
Destruction of shell and fish spawning beds
Depletion of oxygen
Change in pH
Gill damage to fish
Reduce or destroy plant photosynthesis.
Solids may also interfere with the irrigation of soils by forming
an impervious blanket that reduces the penetration of air and water,
by fouling recreational areas, by filling river channels or causing
shoals, and by damaging process equipments such as pumps, heat
exchangers, and process lines.
Complete elimination of solids from release into the air by
appropriate treatment will increase the solid wastes to be disposed
of. Increased solid waste may create landfill erosion and water table
pollution problems unless carefully designed and operated.
These effects are in addition to those that may result from the
toxic properties of air, water or solid waste releases. The amounts
of solid materials released into the water environment is both a mea-
sure of the environment damage that may occur solely from the effect
of solids and a measure of the solid waste disposal problem if all
such solids are removed from the water.
-------
APPENDIX A-6-81
REFERENCES
1. "Minimizing Waste in the Petrochemical Industry, " Chemical
Engineering Progress, October 1967, p. 81.
2. "Petrochemical Wastes Effects on Water, " E.F. Gloyna and
J.F. Malina, Jr., Water and Solid Waste, 1963, pp. R-262 to
R-285.
3. Petrochemical Effluents Treatment Practices - Summary,
E.F. Gloyna and D. L. Ford, U.S. Department of Interior,
Federal Water Pollution Control Administration, Pub. PB-192-
310, February 1970.
4. The Cost of Clean Water, Volume III: Industrial Waste Profile
No. 5 - Petroleum Refining, U.S. Department of Interior,
Federal Water Pollution Control Administration, November
1967.
5. "Common Refinery Wastes and Process Summaries - Chapter
15, " Manual on Disposal of Refinery Wastes, American
Petroleum Institute.
6. 1967 Census of Manufactures - Water Use in Manufacturing,
U.S. Department of Commerce, Bureau of the Census, Pub.
MC67(l)-7, April 1971.
7. 1967 Domestic Refiners Effluent Profile, American Petroleum
Institute, September 1968.
8. "Chapter 16, " Manual on Disposal of Refinery Wastes,
American Petroleum Institute.
9. The Characteristics and Pollutional Problems Associated with
Petrochemical Wastes - Summary Report, E.F. Gloyna and
D.L. Ford, Environmental Protection Agency, February 1970.
-------
APPENDIX A-7
SIC 31—LEATHER AND LEATHER PRODUCTS
-------
APPENDIX A-7
SIC 31—LEATHER AND LEATHER PRODUCTS
SIC 311—LEATHER TANNING AND FINISHING
1. INDUSTRY DESCRIPTION
This industry includes establishments engaged in tanning, cur-
rying, and finishing hides and skins into leather. The leather tanning
and finishing industry is characterized by three types of tanneries:
regular tanneries, leather converters, and contract tanneries. The
regular tanneries buy raw materials; tan, curry, and finish the hides
and skins; and sell the finished products. The converters buy the
raw materials, contract with tanneries to convert to finished goods,
and then sell the products. The contract tanneries perform only the
processing function; they do not buy raw materials (hides and skins),
nor do they sell the finished product.
The industry is concentrated in New England and the Mid-Atlantic
States as shown in the accompanying tabulation.
Establishments (1968)
20 or More
Division Total Employees
New England 183 93
Middle Atlantic 176 68
East North Central 74 51
West North Central 13 7
South Atlantic 26 18
East South Central 12 10
West South Central 9 2
West 26 29
519 258
-------
APPENDIX A-7-2
The following table indicates the wide variation in establishment
size (1968 data).
Size of Establishment Total Number
Establishments (No. of Employees) of Employees
146 1-4 300
52 5-9 300
63 10-19 900
98 20-49 3,100
73 50-99 5,300
57 100-299 9,100
25 250-499 8,000
4 500-999
3 700
1 1000-2499 ' '
Although New England and the Middle Atlantic States have 359
of the 518 tanneries (nearly 70 percent), they do less than half of the
total business (approximately 427 million in a total of 870 million).
Fewer but larger tanneries characterize the other areas of the
country.
Employment has remained relatively static over the past ten
years (1958-68) declining slowly from 37,000 in 1958 to 30, 700 in
1968. The value added has varied from year to year within the range
of $740 to $940 million.
Based on an approximation of gallons of water used for each
pound of hide processed and an estimate that approximately 1, 700
million pounds of hides were processed ($847 million value @ 50
-------
APPENDIX A-7-3
per pound), the total effluent in 1968 is estimated at 15,600 million
gallons. The estimate made by the Bureau of the Census, based ona special
water use study, was 15 billion gallons. Of this amount, it is estimated
that 10 billion gallons were treated prior to discharge. Sludge is ap-
proximately 3. 5 percent of the effluent; or 500 million gallons of sludge
must be dumped annually. The content of such sludge is approximately
95 percent water and 5 percent solids. The solids are 55 to 60 per-
cent organic material, the balance being inorganic salts.
Assuming that 10 gallons of the effluent streams' biological
oxygen demand (BOD) content is equivalent to the wastes of one per-
son (Reference 1), the 15 billion gallons discharged annually is equiv-
alent to the wastes of approximately 4 million people.
2. INDUSTRY GROWTH PATTERNS AND PRODUCTION TRENDS
Growth trends in the tanning industry are toward fewer and
larger plants and the application of new technology. The number of
tanneries has decreased constantly over the past 100 years, from a
total of about 7, 500 in 1867, to about 250 as of 1965, as illustrated
below:
No. of
Year Tanneries
1867 7,500
1900 1.000
1952 443
1965 250
-------
APPENDIX A-7-4
In general the industry can be characterized as "old", in terms of plant
age. However, due to modernization programs, most plants employ
relatively new technology.
Overall production trends have remained relatively static over
the past 15 years .with cattle hides delivered fluctuating between about
30 to 35 million per year.
About 89 percent of all leather is used for making shoes. While
the U. S. leather industry has shown no growth during the past 15 years,
the U. S. population has about doubled. Imports of footwear leather
have increased about 500 percent in dollar value, and U. S. exports
have decreased by about 50 percent, as shown below:
Year Leather Footwear All Leather
Imports Exports Imports Exports
($) ($) ($) ($)
1951 24,647,000 19,063,000
1963 80,687,000 8,628,000 143,000,000 17,084,000
1966 128.255,000 8,856,000 243,365,000 24,539,000
3. STANDARD PRODUCTION PROCESSES AND WASTE
MATERIALS
Tanning is the process of converting animal skin into leather.
Generally, it consists of the reaction of collagen fibers with tannin.
chromium, alum, or other tanning agents, to remove the undesirable
-------
APPENDIX A-7-5
protein in the skin. Due to individual preferences as a result of past
experience in leather production, there is a significant variance in
processing techniques of tanners.
(1) Typical Processes in the Tanning Industry
The following paragraphs present a general description of
the manufacturing processes. In order to simplify the descrip-
tions and characterizations of waste loads, the following standard
processes are treated individually: beamhouse and tanhouse; retan,
color, and fat liquor; and finishing. A typical flow diagram of
cattlehide tanning is illustrated in Figure A-7-1. This identifies
the flow of raw materials, process materials, and waste mate-
rials.
Although the processes for cattlehides, pigskins, and
sheepskins differ somewhat, they are combined into a single
general description for the purposes of this report. The major
difference is that in the typical pigskin and sheepskin operation,
the beamhouse processes are largely eliminated, since they are
performed prior to arrival of the skins at the tanning. The trend
in cattlehide processing is also in this direction, with major
beamhouse operations increasingly being performed at the source
of supply.
-------
FLOW
TYPIO
WiTCR 0
^UM H-»
6REE-I SALTED
AND/0) BRINED
HIDtS r
WATER
JHARPCHEM
AIM—ID-*1
DIAGRAM
\L CATTLEHIDE TANNI
.••Nl-NNNNNNNNNNNNNNl JU7U
RECEIVING 1 ~.
STORAGE • ^_
WOE 1 TRIM • itiB P"*1
WASH 1 SOW •
FLESH • -EraE fr
UNHAIR •
'"" ""» IS.DES
V *
' | j_TRINNIKGS
| [ FLESHINGS
| HAIR
•ASIE EFFLUENT
BEAMCUSE
(ALTEWATE)
RECEIVING ENITMES
STORAGE "• ' *
SHE « TRIM _SAH_.
WiSH 1 SDAI _4tlU_l *
„.„ JSBU.H,
(mrnMR) i'lrfit^
^^^^^ BEAMHCUSr
FLESH | TANHOUSE "
| '{TRIMMINGS
(_ FLESHINGS
WASTE EFFLUENT
ER
M
BATI
nci
TAN
SFt
SNA
(1
y
1 j*
I "
« 1 ji
(CHROME) 1 —
•GRAIN SIDES
" 1
j [W.ITS
JSOLID WASTE (SHAVIRGS)
WASTE EFFLUENT
FAMCUSE
tLTEJWTE)
(ATE
HCRLE ^GR»IN SIDES T
TAI( VEGETABLE) W- "'J'*1
SF-LIT
SHAVE
1 JSMTS
[SOLID WASTE (SHAVINGS]
WASTE EFFLUENT
LEGEND
NIOES AND
PROCESS Ml
"ami
LIQUID VAi
flETtN-COLOR-FtTLIOUDR
« » RETAH (CHROME) •
•l -«« FAUIOUOR ^^^^^
I
TERIALS — —
iSL,OS
TES • '
FINISHING
DRTINt 1
COATINS •
STAIINB •
! SOLID WASTE (TRIMMINGS)
WASTE EFFLUENT WASTE EFFLUENT (CLEAN-UP ONLV)
(STAN COLOR FATLIOUCR
(ALTERNATE)
WATER
UNNIN
0 RETAN^ OVE ^
IWR ' OIL
GRAIN SIDES _
FROM TAWOUSE
RETAN (VEGETABLE)
COLOR
FATLIQUDR
WASTE EFFLUENT
Environmental Protection Agency
Flow Diagram —
Typical Cattlehide Tannery
*1
3
d
3 >
M >Tj
^ S
•? 2
As
>
I
-J
I
o>
-------
APPENDIX A-7-7
1. Beamhouse Operation Include Unhairing and
Preparation of Hides for Tanning
The beamhouse operation is the initial step in the
tanning process. Generally it involves washing, to get rid
of excess materials and storage brine, and then various
processes to remove excess hide, flesh, and hair. Beam-
house processes are as follows:
Receiving and storage is the initial beam-
house operation. Typically,this includes the
delivery of cured green salted or brined hides
in bundles of about 3, 200 cubic feet measuring
about 20 by 40 by 4 feet. These bundles are
stored as delivered until processing begins.
Siding and trimming involves unpacking the
hides, trimming off excess material, about
2 to 3 percent of the hide, and siding or cutting
the hide in half along the backbone.
Washing and soaking takes place in vats or
drums where excess dirt, salt, blood, manure,
and nonfibrous proteins are removed.
Green fleshing involves the removal of attached
adipose fatty tissue and meat by processing
hides through a fleshing machine.
Unhairing is the removal of hair by chemical
loosening,followed by machine pulling or
chemical dissolving. Pulling is done if hair
is to be recovered as a by-product. Dissolving,
also referred to as "pulping" or "burning", is
accomplished in a lime slurry with sodium
sulfide or sodium sulfhydrate and does not yield
a recoverable by-product.
Lime splitting involves the slitting of a hide
into two layers. The "split" or the upper
flesh side is sold or discarded while the
"grain" is processed for leather. Normally,
splitting is done only with pigskin hides.
-------
APPENDIX A-7-8
Beamhouse processes are the greatest single source
of tannery wastes. The unhairing process in particular
produces about 50 percent of the tannery total BOD and
about 30 percent of the waste volume. The stock waste
water is high in solids and is 10 to 15 percent of the total
tannery wastewater discharge and 15 to 20 percent of the
BOD. Waste materials from the beamhouse include:
Hide trimmings
Dirt, salt, blood, manure, and nonfibrous
proteins
Fats
Alkalines
Sulfides
Proteins (dissolved)
High BOD
Lime
Sodium sulfide
2. Tanhouse Processes Convert Hide Fibers
into Leather
The tanhouse operations include the basic chemical
processes necessary to convert hide fibers into leather.
These operations include the following:
Bating involves the placing of the hide in a solu-
tion of ammonium salts and enzymes. This
de-limes the hides, reduces swelling, pep-
tizes fibers, and removes protein degrada-
tion products.
Pickling prevents precipitation of chromium
salts in the tanning process and is done by
immersing the hides in a brine and acid solu-
tion.
-------
APPENDIX A-7-9
Tanning involves both vegetable tanning and
chrome tanning. Vegetable tanning is used
for heavy leather such as sole leather, me-
chanical leather, and saddle leather. Hides
are immersed in vats containing a solution of
plant extracts such as vegetable tannins.
Chrome tanning, used for ths majority of light
leathers, consists of immersing hides in drum
baths containing proprietary mixtures of basic
chromium sulfate.
Tanning liquor wastes are second to beamhouse
wastes in concentration of effluents. Spent vegetable
tannins are highly colored and account for 5 to 10 percent
of the total waste flow and 25 to 30 percent of the total
BOD from the tanning process. Batepool waste water is
usually about 40 percent of total tannery waste water flow
and 15 percent of the BOD. These wastes include:
High concentrations of dissolved organic solids
(vegetable tanning)
High concentrations of dissolved inorganic
solids and chromium (chrome tanning)
High coloration
High odors
Total plant BOD (5 percent)
Total plant waste volume (5 percent)
Brine and acid from pickling.
3. Retan. Color, Fat Liquor Processes
As the names imply, these processes involve color-
ing and oiling the hides to produce the desired leather
product. These processes are as follows:
Retanning is used for hides that have not been
fully tanned in the initial tanning processes.
-------
APPENDIX A-7-10
Since vegetable tanning generally produces
leathers which are fuller, plumper and more
easily tooled and embossed, leather tanned
by the chrome method is sometimes retanned
in vegetable tannins.
Coloring is accomplished by placing hides in
a drum with natural or synthetic dyes.
Fat liquoring involves the addition of oils to
replace natural oils lost in the beamhouse and
tanhouse processes and to make the leather
pliable.
Waste materials from the retan, color and fat liquor
processes include:
Dissolved organic solids
Dissolved inorganic solids
Chromium
Dyes.
4. Finishing
Finishing operations include drying, coating, staking,
and plating. These provide only a minor contribution to the
liquid waste.
(2) General Processing Trends and Projections
Technological change has been relatively slow in the tan-
ning industry in comparison to many other industries. Table
A-7-1, giving past, present, and projected trends in the sub-
processes employed by the industry, shows relatively little ex-
pected change over the next 10 years. With respect to the major
sources of waste effluents, the projected increase in lime
-------
APPENDIX A-7-11
Table A-7-1
Subprocessing Trends
Production Process and
Significant Suborocesses
Storage & Trimming
of Cured Hides
Air drying
Salting
Salt & Air Drying
Brine Curing
g & Soaking
Soak or Green Fleshing
Lime Fleshing
Re-Soaking
Hair Saving
Hair Pulping
Bating & Pickling
Tanning
Vegetable
Chrome
Synthetic or Resin
Re tanning
Vegetable
Mineral
Syntan & Resin
No Retan
Coloring
Bleaching
(Hypo, oxalic + syntans)
Fatliquoring
Stuffing (Hot Drum Method)
Filling & Pigment ing in
the Drum
*Envlronmental Protection Agency data.
in the Tanning Industry 1950-1982*
Estimated Percentaee of Plants
Emp levins Process
1950
10
70
20
0
100
70
30
60
40
100
30
70
70
5
15
10
80
45
80
20
70
1963
0
60
20
30
100
90
10
45
55
100
20
80
75
5
20
0
90
35
90
10
80
1967
0
50
20
80
100
90
10
45
55
100
20
80
70
5
25
0
90
35
90
10
85
1972
0
40
20
85
100
80
20
45
55
100
20
80
60
5
35
0
90
35
90
10
85
1932
0
40
20
90
100
40
60
45
55
100
20
30
45
5
50
0
90
35
90
10
95
-------
APPENDIX A-7-12
fleshing would add to the waste streams in the beamhouse op-
eration. Table A-7-2 indicates that little can be gained to re-
duce pollution from implementation of available alternate produc-
tion processes.
(3) By-Product Utilization, Waste Recovery, and Recycling
There are recognized markets for several of the by-
products of the tanning industry. For example, fat is used in
glue manufacturing, hair is used in brushes or upholstering
and rug backing, spent tanbark is used for special purpose
floor coverings for horse shows, circuses, etc. In addition,
there is also a certain amount of recovery and recycling of
wastes such as degreasing liquors and chrome tan liquors.
Often the decision to save a by-product or recover a
waste material for reuse is dependent upon the economics of
the situation. For example, the recent low market price for
hair has not made it profitable for tanneries to save hair in the
beamhouse operations. Consequently, more tanneries use
"pulping" or "burning off" which completely destroys the hair.
In general, recent trends in the tanning industry are toward
less waste recovery and by-product utilization. Table A-7-3
details normal by-product utilization in a tannery.
-------
APPENDIX A-7-13
Table A-7-2
Pollution Reduction Efficiency of Alternate Tanning Subprocesses*
Fundamental
Process and
Alternate Subprocess
Wash & Soak
Long (overnight soak)
Short (short soak)
Unhair
Pulp hair
Save hair
Pollution
Reduction Efficiency.fe)
Vol BOD SS TDS
0
15
0
0
0
17
0
25
0
15
0
30
0
15
0
30
Remarks
Most plants report
no difference in
pollution generated.
Which process used
depends upon demand
for hair.
Bating
Paddle machine
Drum machine
00 00 Most plants report
20 10 10 10 no difference in
pollution generated,
Pickling
Paddle machine
Drum machine
Tanning
Chrome
Vegetable
00 0 0 No significant
10 0 0 10 pollution generated.
00 00 Not really alternate
90 75 50 80 methods since they
produce a different
kind of leather.
Finishing
A tremendous variety
of methods used.
Pollution from fini-
shing generally not
significant.
Note: Pollution reduction efficiencies shown are generally the
highest reported.
*Envlronmental Protection Agency data.
-------
APPENDIX A-7-14
Table A-7-3
By-Product Utilization in the Tanning Industry*
Item
Use
Trimmings - Bellies
Others
Hair
Fleshings
Degreasing Exhaust
Drum Liquors
Spent Lime Liquors
Pickle Solution Wastes
Chrome Tan Liquors
Spent Vegetable Tans
Spent Tanbark
Used for edible purposes.
Oil production after rendering.
Protein feed after rendering.
Gelatin manufacture.
Used in manufacturing, upholstering,
and rug backing.
Glues.
Reuse of solvent in tanning.
Soap.
After settling, the sludge can be
mixed with other plant wastes and
sold as fertilizer.
In the past this solution has been
reused within the tannery for pickling
a number of times. However, tendency
of late has been to omit this reuse
through advent of drum bate, pickling,
and chrome tanning.
Holding and reusing in tannery.
Precipitating the Cr (OH>3t filtering,
redissolvlng chromium with H_no,. Most
tanners consider this economically im-
practical.
Evaporated and sold as boiler compounds.
Used as floor coverings for horse shows,
circuses,« playgrounds • sometimes used
in paperboard manufacturing or In making
white lead.
*Environmental Protection Agency data.
-------
APPENDIX A-7-15
(4) Tannery Effluents to Air and Water
Identifiable wastes in the tanning industry are presented
in Table A-7-4.
4. WASTE DISPOSAL PROCESSES AND PRACTICES
The tanning industry has long been recognized as a major con-
tributor to water pollution because of the high concentrations of or-
ganic and inorganic substances presented in untreated tannery effluents.
A detailed investigation of the U.S. tanning industry in 1965-66,revealed
that,although a number of tanneries were served by various treatment
procedurestno tannery had installed a treatment system that was com-
pletely satisfactory. Subsequent to this investigation, however, a
considerable number of studies and several resulting pilot-scale and
full-scale waste treatment systems have been installed and tested.
(1) Current Waste Treatment Processes in the
Tanning Industry
Current waste treatment processes in the tanning industry
can be grouped into two areas: wastewater treatment processes,
and sludge handling and disposal. In general, tanning industry
wastes originate as wastewater which, after certain treatment,
yields a waste sludge. Both water and sludge processes are
listed in Table A-7-4.
-------
APPENDIX A-7-16
Table A-7-4
Current Waste Treatment Processes in the Tanning Industry
Wastewater Treatment Processes
Screening
Plain Sedimentation
Neutralization (incl. Equalization and pH adjustment)
Coagulation (chemical)
Lagoons (aerobic and anaerobic)
Lagoons (holding)
Activated Sludge
Trickling Filtration
Equalization • beamhouse and tanhouse wastes
Biological Oxidation
Flue Ras and Precipitation with Resins
Polyelectrolyte Treatment and Clarification • lime wastes
from beamhouse
pH Adjustment (sulfuric acid, lime)
Flocculatlon, Double Settling and Equalization Evaporation
of Tan Liquor
Sludge Handling and Disposal
Landfill
Digestion; Liquid Sludge to Land Irrigation
Digestion; Sludge to Lagoons
Digestion; Vacuum Filtration, Flash drying; Landfill
Vacuum Filtration
Incineration
-------
APPENDIX A-7-17
(2) Advanced Treatment Systems for Tannery Wastes
Advanced treatment is concerned with the removal of one
or more specific contaminants to a lower level than afforded by
secondary treatment. Advanced treatment for tannery wastes
should be directed toward the reduction of the following:
Suspended and colloidal solids
Organic materials
Dissolved inorganics
BOD and COD
Color.
The following techniques have been used in other industries
through the application of several physical and/or chemical
processes; however, these processes have not been directly
applied to tannery wastes:
Suspended and Colloidal Solids Removal
Flotation and skimming
Filtration
Micro-straining
Coagulation - flotation.
Dissolved Solids Removal
Activated carbon
Ion exchange
Reverse osmosis.
-------
APPENDIX A-7-18
Certain of these processes may be required when effluent levels,
subsequent to secondary treatment, are unsatisfactory for dis-
charge to streams which have extended low flow periods or
which receive wastes from a highly industrialized area. In this
case, it may be desirable to reduce certain effluent parameters
to the lowest level technically feasible.
(3) Composition of Waste Streams and Efficiency of Waste
Treatment Processes
Some of the more important characteristics of the individual
waste streams are identified in the following table:
Waste Fraction Flov;
(tgpd)*
Wash Water
Soak Water
Lima Water
Rinse Water
Hair Water
Fleshing Water
Bate Water
Spent Tan Liquors
* 1 tgpd - 3785 liters
25
10
10
20
15
5
55
60
per day or
COD Suspended
Solids
1mq/l) (mg/1)
2100
2200
11900
2500
2500
3600
1700
10000
1,000 gal/day
1300
1000
30300
49CO
3100
4900
1000
500
PH
6.8
7.8
12.3
12.3
12.3
12.3
9.0
4.5
As shown above, lime vat, rinse vat, and hair washer
waters contain moderate to high concentrations of COD and
suspended solids (mostly Ca(OH)2),and have a high pH; yet they
-------
APPENDIX A-7-19
make up only 32 percent of the beamhouse wastewater volume.
The wash, soak, and vating waters represent 64 percent of the
waste volume, but are moderate to low in COD and suspended
solids, and near neutral in pH.
There is a significant variation in reported efficiencies
of various treatment processes. With respect to individual
pollutants, some processes inherently contain more effluent
than others. However, treatment efficiencies are also highly
dependent upon the differences in pollutant concentrations arising
from different production subprocesses.
Typically reported treatment removal efficiencies are
presented in Table A-7-5. In actual practice, several individual
treatment processes are combined in most treatment installa-
tions.
(4) Extent of Waste Treatment in the Tanning Industry
Available data waste treatment practices in the tan-
ning industry, indicates that relatively little effective treatment
has been attempted until the past several years. Typically,
tanning wastes are discharged into a municipal sewer system
which provides secondary waste treatment, when available.
-------
APPENDIX A-7-20
Table A-7-5
Waste Treatment Processes and Process Efficiencies*
Normal Pollutant Reduction Efflclencv (TL)
Item
In-Plant Treatment
Screening
Equalization in
Holding Basins
Sedimentation
Chemical Coagula-
tion
Lagoons
Trickling
Filtration
Activated Sludge
BOD
5
0
25-62
41-70
70
65-80
85-95
SS.
5-10
0
69-96
70-97
80
85-90
80-95
Color
0
0
5-10
6-90
25
Est.
15-70
75
Est.
Chromium
0
5-10
5-30
50-80
Est.
10-20
25-75
Est.
75
Est.
SulfidP
0
0
5-20
14-50
Est.
0
75-100
75-100
Sludge treatment by:
Lagoons
Digestion
Vacuum filtration
Incineration
Municipal Treatment
Primary 20-54 14-75 20 20-25 10-15
Est.
Primary and Trickling 85-95 80-95 25-75 25"75 75-100
Filtration Est. Est.
Primary and Activated 75-95 77-95 75 75 75-100
Sludge Est. Est.
Primary and Chemical 50-90 73-96 90 50-90 75-100
Coagulation (lime) Est. Est. Est.
*Environmental Protection Agency data.
-------
APPENDIX A-7-21
Approximately 45 percent of wastes are not treated before dis-
charge into stream, lakes or ocean.
Results of recent waste treatment surveys are presented
in Table A-7-6. The Eye survey of 1967 (Reference 2),repre-
sents about 95 percent of the total industry based upon total
leather production. This survey indicates that screening and
plain sedimentation are the most widely utilized waste treat-
ment practices. Holding lagoons are also fairly common. How-
ever, such processes as neutralization, coagulation, aerobic and
anaerobic lagoons, and activated sludge are utilized by less than
10 percent of the industry.
Current trends in waste treatment indicate that tanneries
are relying increasingly on municipal waste treatment facilities
for effective secondary treatment. This is evident from the
following data on years and percent of tannery discharge into
municipal sewers:
1950 1963 1967 1972
Percent 60 70 75 80 (est. )
-------
APPENDIX A-7-22
Table A-7-6
Waste Treatment Survey*
Stanley
Eye. 1967 Consultants. 1971
j_No. Z_ , No. I
Questionnaires , "
Returned 129 ^ 100 ^3 100
Wastes Discharged to:
Municipal Sewer 82 63 2k 56
Stream or Lake 43 33 6 14
Ocean 32 00
Wastes Currently Are:
Treated Before Discharge 36 28 7 16
Treated with Municipal
Wastes 47 36 5 12
Discharged Untreated 59 45 20 47
Treatment Practices:
Screening 56 43 11 26
Plain Sedimentation 62 48 8 19
Neutralization NA 3 7
Coagulation 12' 9 1 2
Lagoons (Aerobic and
Anaerobic) 1) 9 37
Lagoons (holding) 35 27 11
Activated Sludge None 1 1
NA - Not Available.
*Envlroniflental Protection Agency data.
-------
APPENDIX A-7-23
(5) Estimates of Waste Production
1. Net Wasteload Quantities - 1963
The net waste quantities are equal to the gross
quantities produced,less the pollution removed by industry-
operated and municipally-operated waste treatment fa-
cilities. For the base year, 70 percent of the waste vol-
ume was treated by municipal facilities, with an average
pollution reduction of 80 percent. About 20 percent of the
waste volume was completely treated by industry-operated
facilities, with an average pollution reduction of 62 per-
cent. On this basis, net pollution reaching watercourses,
in 1963,from the tanning industry approximated:
Waste Gross Produced Percent Net Discharged
Item (million Ib) Removed (million Ib)
BOD 150 67. 5 49
SS 425 79.5 87
TDS 650 38. 0 403
2. Projected Net Wasteload
The quantity of pollution load reaching the nation's
watercourses from the tanning industry is expected to de-
crease in the future. This will result from slightly re-
duced gross pollution produced, a larger percentage of
waste treated, and increased removal efficiencies of
waste treatment methods. The net wasteloads are pro-
jected through the year 1982, as follows:
Gross Produced Percent Net Wasteload
Year Waste (million Ib) Reduced (million Ib)
1967 BOD 160 69.0 50
SS 440 81.0 84
TDS 670 38.0 415
1968 BOD 160 69. 5 49
SS 440 81. 5 81
TDS 670 38.0 415
(Continued)
-------
APPENDIX A-7-24
Year Waste
Gross Produced
(million Ib)
Percent Net Wasteload
Reduced (million Ib)
1969 BOD
SS
TDS
160
440
670
70.0
82.0
38.0
48
79
415
1970 BOD 155
SS 430
TDS 660
1971 BOD 155
SS 430
TDS 650
1972 BOD 155
SS 430
TDS 650
1977 BOD 150
SS 420
TDS 640
1982 BOD 145
SS 410
TDS 630
70. 5
82. 5
38.0
71.0
83.0
38.0
71.5
83. 5
38.0
74.0
86.0
40.0
77.0
89.0
45.0
46
75
409
45
73
403
44
71
403
39
59
384
33
45
347
3. Gross Wasteload Projections
Future gross wasteloads are projected below on the
basis of projected growth of the industry and anticipated
improvement in technology.
Volume BOD SS TDS
Year (billion gal) (Million Ib) (Million Ib) (million Ib)
1963
1967
1968
1969
1970
1971
1972
1977
1982
16.0
16.2
16.2
16.2
16.1
16.0
16.0
15.0
14.0
150
160
160
160
155
155
155
150
145
425
440
440
440
430
430
430
420
410
650
670
670
670
660
650
650
640
630
-------
APPENDIX A-7-25
The previous predictions are based on the assumption
that:
The trend toward hair pulping will continue
Beamhouse operations will be slowly trans-
ferred to the slaughterhouse
Water reuse and waste segregation will be
increased
The value added in manufacturing projections
by Federal Water Pollution Control Adminis-
tration are accurate.
4. Seasonal Variations
Based on industry information available, there is
no significant seasonal variation in hides tanned. In the
winter and spring, however, the hides processed tend to
be dirtier and have more hair and fat. This increases:.,
slightly,the pollution load per hide processed.
When industrial wastes are combined with municipal
wastes, waste removal problems include compatibility and
pretreatment. Odors and clogging of sewers,due to pieces
of fat, hair, and precipitated lime,are major nuisances.
Toxicity of chromium and sulfide ions in biological treat-
ment has also been of concern in combined treatment.
High pH values resulting from beamhouse operations may
inhibit biological treatment of combined wastes. Large
quantities of suspended solids overload primary units and
clog secondary units. Excessive grease often creates
problems with skimming devices and small nozzle distri-
bution systems.
It is feasible to treat this industrial waste in an ade-
quately designed and operated municipal wastewater treat-
ment plant. Screening, flotation, and neutralization (under
some situations) are necessary pretreatments.
-------
APPENDIX A-7-26
REFERENCES
1. Industrial Wastes, W. Rudolphs, Library of Engineering
Classics, p. 152.
2. "Survey of Waste Management Practices in the Tanning
Industry, " D.J. Eye, Proceedings of the Fifty-Second Annual
Meeting. Tanners' Council of America, October 1968.
3. Effluent Requirements for the Leather Tanning and Finishing
Industry, Stanley Consultants, Inc., for the Environmental
Protection Agency, Water Quality Office, September 1971.
-------
APPENDIX A-8
SIC 32—STONE, CLAY, GLASS, AND
CONCRETE PRODUCTS
-------
APPENDIX A-8
SIC 32— STONE, CLAY, GLASS, AND CONCRETE PRODUCTS
SIC 329 —ABRASIVE, ASBESTOS, AND MISCELLANEOUS
NONMETALLIC MINERAL PRODUCTS
1. ECONOMIC STATISTICS
Stone, Clay, Glass, and Concrete Products is the title for
Standard Industrial Classification Major Group 32. At the three-digit
SIC code level, the area of this industry which is of primary concern
is SIC code 329, Abrasive, Asbestos, and Miscelleanous Nonmetallic
Mineral Products. Further, at the four-digit level, the following
codes are of concern:
SIC 3292—Asbestos Products
SIC 3293—Gaskets, Packing and Asbestos Insulations.
SIC code 3292 includes those establishments primarily engaged
in manufacturing asbestos textiles, asbestos building materials (except
asbestos paper, included under SIC 2661), and other commodities
composed wholly or chiefly of asbestos, except those covered by SIC 3293
described on the following page.
-------
APPENDIX A-8-2
SIC code 3293 includes those establishments engaged in manu-
facturing packing for steam, water, and other pipe joints; for
engines, air compressors, etc.; for insulating materials for covering
boilers and pipes; and for gaskets. Establishments primarily engaged
in manufacturing leather packing are classified in SIC 3121, rubber
packing in SIC 3069, and meat packing in SIC 3599.
Mining and milling of asbestos are also considerations for the
generation of hazardous waste materials. SIC code 1499 includes those
establishments primarily engaged in mining, quarrying, milling, or
otherwise in preparing nonmetallic minerals not elsewhere classified,
such as asbestos, diatomite, natural gem stones, graphite, greensand.
Iceland spar (optical grade calcite), and vermiculite.
(1) Location and Number of Establishments with Value Added
Table A-8-1 shows the distribution of establishments through-
out the various states included in the SIC codes being considered.
The number of employees and the value added are also
given by state.
Table A-8-2 gives the number of establishments in up to
ten different size groups for the SIC codes under consideration.
The value added is also provided for each size group within each
SIC code.
-------
Table A-8-1
Distribution of Establishments and Employees in SIC 32 Subcategories
(1)
Industry and Geographic Area
SIC 3292 - Abestos Products
United States
New England Division
Middle Atlantic Division
East North Central Division
West North Central Division
South Atlantic Division
East South Central Division
West South Central Division
Pacific Division
SIC 3293 - Gaskets and
Insulations
United States
New England Division
Middle Atlantic Division
East North Central Division
West North Central Division
South Atlantic Division
East South Central Division
West South Central Division
Pacific Division
Establishments
Total
Number
138
14
32
32
6
18
4
12
19
301
16
78
103
17
11
8
28
35
With 20
Employees
Or More
99
11
22
21
4
11
4
10
16
123
8
27
47
5
5
3
14
13
Number
of
Employees
(1000)
21.3
2.8
6.7
4.1
0.5
2.7
0.3
2.1
1.0-2.499
18.5
1.1
4.1
9.1
0.2
0.7
0.3
1.4
1.0-2.499
Value Added
By Manufacture
(million dollars)
308.1
34.6
91.6
62.5
7.8
34.8
5.9
33. 1
(D)T2)
205.5
13.2
54.3
94.7
2.6
5.1
3.4
15.3
H
1
O
00
CO
(1)
(2)
Reference 1.
(D) indicates data has been suppressed to avoid disclosure of individual company information.
-------
APPENDIX A-8-4
Table A-8-2
Distribution of Establishment Size by SIC 32 Subcategories
ITEM
SIC 3292 — Asbestos
Products
Establishments, Total
Establishments with an
average of:
1 to 4 Employees
5 to 9 Employees
10 to 19 Employees
20 to 49 Employees
50 to 99 Employees
100 to 249 Employees
250 to 499 Employees
500 to 999 Employees
1, 000 to 2, 499
Employees
SIC 3293— Gaskets
and Insulations
Establishments, Total
Establishments with an
average of:
1 to 4 Employees
5 to 9 Employees
10 to 19 Employees
20 to 49 Employees
50 to 99 Employees
100 to 249 Employees
250 to 499 Employees
500 to 999 Employees
1,000 to 2,499
Employees
Establishments
(number)
138
20
7
12
14
23
36
18
6
2
301
79
45
54
54
32
21
11
2
3
Number of
Employees
(1000)
21.3
<.05
<.05
0.2
0.4
1.7
5.6
6.1
7.3
(Dr2'
18.5
0.1
0.3
0.8
1.7
2.3
3.2
72)
(D)
4.6
Value Added
By Manufacture
(million dollars)
308.1
0.4
0.5
2.4
5.0
19.4
84.2
98.2
97.9
(D) (2)
205.5
2.0
3.6
9.3
21.4
28.4
36.2
53. 9,.
(D)"'
50.7
(1)
(2)
Reference 1
(D) indicates data has been suppressed to avoid disclosure of
company information.
-------
APPENDIX A-8-5
(2) Major Raw Materials, Annual Production, and
Industry Growth Pattern
The United States is the world's largest consumer of
asbestos, using more than one-fifth of the 3. 5 million short tons
of world's production (in 1968). Approximately 15 percent of the
U. S. asbestos required is obtained from domestic production
and 85 percent from import; Canada provides about 90 percent
of the imported asbestos, and the Republic of South Africa most of
the rest. Domestic demand for asbestos, in the year 2000, has
been forecast in the range of 1.28 to 1. 87 million tons.
Total world production of all grades and varieties, in 1968,
was estimated at 3. 5 million short tons. Of this total,
Canada produced about 46 percent; the U. S. S. R., 25 percent
(estimated); the Republic of South Africa, 7 percent; Southern
Rhodesia, 5 percent; the United States, 3 percent; and Italy,
3 percent. Canada is expected to continue as the leading free-
world producer, but output from other countries should become
increasingly significant. In the United Statesjthe demand for
asbestos fiber requirements is changing, and the substantial
California deposits could reduce the reliance on imports by the
year 2000, provided that products from the relatively short fiber
receive consumer acceptance. A more remote possibility for a
-------
APPENDIX A-8-6
new supply source would be the development of synthetic asbestos
production resulting from research by both government and
industry.
Asbestos is adaptable to more than 2, 000 uses. Because of
its high strength-to-weight ratio and resistance to searing tempera-
tures, it is used in rockets and missiles. Asbestos product plants
are located in 16 states, principally in the East and South.
About 69 percent of the asbestos consumed goes into the
manufacture of asbestos cement products, about 10 percent in
floor tile, 7 percent in asbestos paper, 3 percent into friction
materials and gaskets, 2 percent in asbestos textiles, 2 percent
in paints and caulking, 1 percent in plastics, and 6 percent in
miscellaneous other commodities.
The forecast growth rate for the construction industry for
total new construction is 4. 5 percent. However, the growth
rate for asbestos products used in the construction industry is
not forecasted to be this great. Asbestos cement products will
compete with lumber and other building products, many of which
are increasing rapidly in price. The competitive position of
asbestos cement products, based on price, is offset in part due to
-------
APPENDIX A-8-7
the great dependence on imports to meet demand. Also a
variety of new, alternate ceramic and plastic materials are
becoming available. In the area of paints and caulking, asbestos
also has to compete with an ever-increasing number of new
materials. Use of asbestos in floor tile has been increasing in
recent years, but.because of the many competing mate rials, it
is not expected to grow at an annual rate of 4. 5 percent. Asbestos
paper products used in electrical appliances as well as in con-
struction are expected to grow at an accelerating rate, but the
quantity of asbestos for such uses is relatively small.
Thus, the demand for use of asbestos in the construction
field is forecasted,for the year 2000,at a minimum of 983,000
and a maximum of 1, 475,000 short tons. This repre-
sents a minimum growth rate of 1/3 of the 4. 5 percent,predicted
for the construction industry as a whole, and a maximum growth
rate of 1/2 of the 4. 5.percent forecast base.
Asbestos is an important part of many types of friction
materials used in automobiles, trucks, and other transportation
equipment. In addition to using asbestos in brake linings, today's
automobiles use a super-tough paper containing crocidolite
asbestos to cover metal automatic transmission discs. Although
-------
APPENDIX A-8-8
the quantity of asbestos in each transmission is small, the output
of more than 6 million automatic transmissions annually requires
disc paper production in hundreds of tons.
In 1968,almost 11 million linear feet of woven brake linings
were manufactured containing asbestos yarn, tape, or cloth. Based
on an estimated forecast of the number of motor vehicles produced
in the year 2000, approximately four times 1968 production, and
on the assumption that the use of asbestos per vehicle will decline
to 60 percent of 1968 level, the forecast for asbestos demand in
user-operated vehicles,for the year 2000,is 60, 000 short tons.
Demand for asbestos in textiles is projected to 56,000 short
tons for the year 2000. Asbestos textiles are used in the manu-
facture of yarn and cloth which is used in safety clothing, packings,
brake linings, filters, etc. Carded fibers are 100 percent asbestos,
and are used for the clarification of such liquids as beer, wine,
oils, and chemicals. Asbestos lap is a felted form of carded
asbestos fiber made for the electric wire and cable industry. It is
also used as insulation for heater cords, fixture wires and other
electrical conductors. Asbestos rovings are used by the electric wire
industry as insulation for heater cords, cables, and electrical
heating elements. All maritime specifications and many government.
-------
APPENDIX A-8-9
industrial, and utility specifications require asbestos cloth to
hold insulation in place and to serve as a permanent protection
and fireproof jacket over pipe and boiler insulation. Specially-
processed lint-free asbestos cloths also serve as protective
shields in "clean" areas adjacent to nuclear reactors.
Plastic materials can be reinforced with such different
fibers as asbestos, glass fiber, and cotton. Short asbestos fibers
are used in the manufacture of such items as handles on cooking
utensils, and long asbestos fibers are used in the manufacture of reinforced
plastic rocket nose cones. Asbestos phenolic materials are used
in aerospace applications. Use of asbestos as a reinforcing
material is becoming more significant. The projection for use of
asbestos as a plastics-reinforcing material^for the year 2000,1s
28, 000 short tons. This projection includes the consideration of
more use of asbestos in the bodies of automobiles and in phenolic
materials for aerospace applications.
On the basis of past performance, it is likely that new uses
for asbestos will be forthcoming, and the forecast base of 165, 000
short tons for other uses of asbestos in the year 2000 is made on
the basis of direct correlation with the GNP growth.
-------
APPENDIX A-8-10
2. DESCRIPTION OF PROCESSES AND WASTE SOURCES
FOR ASBESTOS PRODUCTS
Waste sources from asbestos products industries may be
divided into three major categories; mining, products manufacture,
and product use. Production sources include the manufacture of
asbestos textiles, vinyl asbestos tile, asbestos roofing, asbestos-
cement pipe and siding (SIC 3292), as well as asbestos packing and
insulations (SIC 3293). This report is primarily concerned with the mining
and production aspects. The product use, as a source of waste, is widely
distributed and random. Therefore, it is excluded from the subject of
the study.
(1) Mining and Milling
Asbestos is mined both from open pits and large under-
ground mines. Mining methods vary depending on the type of
mine, however, most mines in the United States are the open
pit type, and involve either plowing or shoveling to remove
asbestos ore. In some cases, blasting is necessary to loosen
material. Mined asbestos ore is moved from the mine to
storage areas where it remains until it is transferred to a mill
for processing.
Asbestos milling is a complex operation involving the
separation of chrysotile asbestos from associated massive
fractured serphentine, and classification of the asbestos fiber
-------
APPENDIX A-8-11
by length into a variety of grades. The process consists>
essentially, of coarse crushing, drying, and recrushing in stages,
with fiber being removed by air suction or screening at each
stage.
Pressure packing processes are used in many mills to
pack asbestos fiber under pressure in five-ply paper bags for
shipping.
The main form of pollution from asbestos mining and
milling operations is airborne asbestos, produced during loading,
unloading and moving operations, crushing and mining (especially
where blasting is required). Additional airborne asbestos arises
from wind-blown dumps, storage piles, and roads made from
mine tailings.
No measurements of air pollution from asbestos mines
have been made in the U. S. However, foreign studies of air pol-
lution from asbestos mining have found asbestos dust-fall rates
ranging from 1. 52 grams per 100 square meters per month at a
distance of 4 kilometers, to 34. 6 grams per 100 square meters
per month at a distance of 0. 5 kilometers from mining sites.
Asbestos dust was observed at distances up to 50 kilometers from
sites.
-------
APPENDIX A-8-12
Even though emissions data are not available, an emissions
factor of 93 pounds per ton of asbestos has been estimated for
mining and milling operations, based on the efficiency of typical
emission control systems (see Table A-8-3).
There are no commercial by-products in the production
and milling of asbestos. Asbestos fiber makes up only about 5
to 10 percent of the rock mined, and the waste rock consists
mainly of broken and pulverized serphentine which is of little or no
commercial value. However, practical methods have been devised
for recovery of magnesia from waste rock, and small quantities of
residual crushed stone have been marketed. In addition, mill
waste containing appreciable amounts of asbestos is suitable for
use in vinyl flooring.
Emission control equipment is used to some extent in
virtually all milling factories. Elaborate ventilation systems
have been devised which carry dusty air from emission sources
to a variety of dust collection devices, before discharge to the
atmosphere. These devices include mechanical dust collectors
with or without filter bags, cyclone collectors, bag filters, and
bag houses. None of these systems is capable of collecting all
of the emitted dust, consequently dust abatement is not complete. An
efficiency of 99. 5 percent, as reported in Table A-8-3, is the best
figure attainable with the present state-of-the-art equipment.
-------
APPENDIX A-8-13
Table A-8-3
Asbestos Emissions Factors for Mining and Milling*
Operations
Mining
Loading
Hauling
Unloading
Crushing & Drying
Milling
Tailings
Uncontrolled
X
X
X
X
X
Cyclone
X
X
Baghouse
X
Emission
Factor**
3
2
2
2
10
64
10
93
Based on baghouse efficiency of 99. 5 percent and cyclone
efficiency of 80 percent.
** Pounds per ton of asbestos produced.
-------
APPENDIX A-8-14
Attempts have been made to control dust emissions by covering
trucks and storage bins with tarpaulins. However, these
inevitably become loose resulting in greatly reduced effectiveness.
(2) Production Processes
In the manufacture of asbestos insulation, asbestos fibers
are mixed with magnesium carbonate, wetted, and pressed or
slurried in large volumes of water, and then molded by pumping
the slurry through porous molds. After molding, the products
are cured at high temperatures, then dried, trimmed, and stored.
Wastewater may originate from the slurrying, recycling,
curing, and cooling operations. Effluent is alkaline in nature,
contains appreciable suspended and dissolved solids, and has
relatively low chemical and biological oxygen demands. Treat-
ment of the waste involves sedimentation and neutralization before
discharge. Sludge is removed to landfill areas. Sources of
airborne asbestos are minimal in the process, however, some
may result from grinding the product, and handling the raw fiber.
1. Textiles
During the manufacture of asbestos textiles, raw
asbestos fiber is combined with small amounts of cotton
or organic fiber such as rayon or nylon, to aid in binding
the fiber. After the fibers are thoroughly mixed, they are
-------
APPENDIX A-8-15
combed into a parallel orientation by a succession of
carding rolls, forming a fluffy blanket. The blanket is
then separated into rovings (often with the aid of cotton
or organic yarn^and later spun into yarn. The asbestos
yarn produced is then woven into a variety of forms.
The primary emission from the process is airborne
asbestos resulting from blending, carding, spinning and
weaving processes, and from the handling of raw asbestos
fiber. The largest emissions come from carding and
spinning operations.
Efforts to reduce asbestos emissions include exten-
sive ventilating systems connected to blending, carding,
and weaving machines, and attempts to keep all raw and
finished asbestos material covered with plastic tarpaulin,
and wetting yarn before spinning and weaving.
Emissions to air and water resulting from yarn
treatment are negligible. The fiber may be treated with
aqueous solutions of butadiene or methylmethacrylate to
produce a polymer coating during the spinning process.
Waste produced in the process other than airborne asbestos
encountered in spinning is essentially that resulting from
periodic cleaning of treatment troughs to remove deposits of
polymer. Yarn is generally wet with dilute sodium nitrite
solutions before weaving, but again, waste is minimal.
Finished asbestos cloth for use in fireproofing is treated
by immersion in tanks containing sodium silicate followed
by air or oven drying. Emissions to air and water are
again confined to clean-up operations.
The largest uncontoiled emission of airborne asbestos
probably occurs during textile plant clean-up operations.
Dust collecting on lamps, pipes, walls, and virtually all
surfaces is periodically removed. In some cases, this
involves blowing the surfaces free of dust with high pressure
air hoseSf followed by sweeping after the dust has settled.
Large amounts of asbestos fiber are put into the air, and
since the machines are not running, dust abatement equipment
is also shut down. Carding, spinning, and weaving machines
are also cleaned on a regular basis either by vacuum cleaning
and/or air blasting. Dusts and washing wastes usually show
up in general plant wastes.
-------
APPENDIX A-8-16
2. Vinyl Asbestos Tile
Asbestos is used as a filler and binder in the manu-
facture of vinyl asbestos tile.
Raw materials are blended and pressed into sheets,as
slabs of flooring compound pass through steam heated
colanders. Sheets of tile are then cooled, cut and inspected
prior to packaging and storage.
The chief sources of waste water effluents are con-
dens ate and spent cooling water. Air effluents are primarily
volatalized organic components set free as the flooring com-
pound is heated in colander ing and blending operations.
3. Asbestos Roofing
Asbestos roofing is manufactured by coating asbestos
paper with stone granules using asphalt as a bonding agent
as depicted in Figure A-8-1. There are no water wastes
produced in asbestos roofing manufacture other than cooling
water which may contain stone granules.
4. Asbestos - Cement Products
Asbestos-cement mixtures containing 15 to 20 percent
asbestos and small amounts of other ingredients are used
in the manufacture of asbestos-cement siding and pipes.
Asbestos shingles and siding may be manufactured by
a dry process where a dry mix is spread evenly on a con-
veyor belt before water is added, or a wet process where
water is added before the material is press-formed.
Conduit manufacture involves a fairly complex series
of steps. In one method, a slurry of asbestos-cement
mixture with water is collected on a felt-covered belt, and
the water is removed by suction. The material is then
wound on a rotating metal mandrel to form the pipe. The
pipe wall is built to the desired thickness then steam cured.
High-density asbestos-cement sheets are made by a press
process.
-------
APPENDIX A-8-17
FIGURE A-8-1
A'sbestos Roofing Manufacture
ASBESTOS PAPER STORAGE
HOT LIQUID ASPHALT
FUMES
B
PAPER DIP & SATURATION
STEAM
COOLING WATER
HEAT TREATMENT
UNCOATED ROOFING
• COOLING WATER
D
COATING
COOLING WATER
LI
E
COOLING
SLIGHTLY CONTAMINATED
COO LING WATER
F
CUTTING
ROLLING
PACKAGING
STORAGE
T
CONSUMER
-------
APPENDIX A-8-18
Potential sources of waste waters from the manu-
facture of asbestos-cement products include effluents from
product forming, pressing, finishing, curing, unrecirculated
cooling water, and hydrostatic testing.
Waste treatment procedures of asbestos-cement
products manufacturing wastes include sedimentation and/or
neutralization before discharge or reuse.
5. Gaskets and Packings
Asbestos gaskets and packings are made by treating
asbestos ropes woven from asbestos yarn and by pressing
asbestos fiber with a suitable binder. Emissions from
these processes are minimal, and primarily contained in
the fiber handling and textile production operations.
(3) Waste Summation
Waste water effluents are generally alkaline in nature,
containing a relatively high dissolved and suspended solids content,
and having minimal oxygen demand. Asbestos in water is not
considered to be a significant pollution problem. The main
problems arise from alkalinity, temperature, and solids content.
Table A-8-4 depicts treated effluent quality from five production
sources. The data show that significant volumes of wastewater
with high solids content are produced in the manufacture of
abestos-cement products, and to a lesser extent asbestos insulations.
Wastewater treatment practices include sedimentation, neutraliza-
tion, chemical coagulation.
-------
APPENDIX A-8-19
Table A-8-4
Effluent Quality - Available Levels of
Wastewater Treatment
Asbestos Products
Treatment Operations
ASBESTOS INSULATION:
Sedimentation
Neutralization & Sed'n.
Chen:, coag. & Sed'ti.
VINYL ASBESTOS TILE:
No significant process wastewater
ASBESTOS ROOFING:
No significant process wastewater
ASBESTOS PAPER:
Sedimentation
Neutralization & Sed'n.
Chen. coag. & Sed'n.
ASBESTOS-CEMENT PRODUCTS:
Sedimentation
Neutralization & Sed'n.
Chen. coag. & Sed'n.
PH
6.5-9-0
6.5-9-0
6.5-9.0
6.5-9-0
6.5-9.0
6.5-9.0
Suspended
Solids
Ib/ton
0.5
0.5
0.2
O.fa
O.C
C.3
1.8
1.8
0.8
BOD
Ib/ton
-
0.1Z
0.6
(1)
Reference 2
-------
APPENDIX A-8-20
The main hazardous emission to air in asbestos mining
and processing is asbestos itself. Asbestos is recognized as
being responsible for, and/or associated with,a number of pul-
monary diseases including asbestosis, pleaural calcification and
plagues, cancer of the lung, and mesothelioma of pleaura and
peritoneus, both in asbestos workers and in persons living near
asbestos factories. Workers using asbestos products have also
been reported to have been affected. The main sources of
airborne asbestos are mining, milling, and textile manufacture.
Other manufacturing processes produce minimal amounts of
airborne asbestos.
Present technology used in abatement of asbestos dust
include dust prevention techniques by covering exposed asbestos
fiber and wet spinning and weaving techniques, as well as the use
of elaborate ventilation and dust collection systems. It is
unfortunate that it is not'desirable to wet a large number of
asbestos products.
Dust collection systems consist primarily of suction ventila-
tion systems attached to carding, spinning, blending, etc.
machines. Dust laden air is passed through filter material (bag
houses) where fibers are easily filtered out since the fibers form
-------
APPENDIX A-8-21
a mat which becomes an absolute filter. Cyclone separators
are also used in conjunction with bag houses. Dust laden air is
pumped into the separator where it is made to follow a circular
path, resulting in the sedimentation of the heavier (i. e., larger)
particle. Both large and small particle fractions can be extracted,
however, only the former are worth recycling.
Both scrubbers and electrostatic precipitators offer pos-
sibilities for emission control. Both do not appear to be used
extensively, probably due to the cost factors, and the belief that
bag houses are sufficiently efficient. It should be noted that
attempts to measure concentrations of airborne asbestos in the
vacinity of asbestos plants have generally been proved futile with
present analytical methods.
-------
APPENDIX A-8-22
REFERENCES
1. 1967 Census of Manufactures, U.S. Department of Commerce,
Bureau of Census, 1971.
2. Industrial Waste Study Report, Flat Glass, Cement, Lime,
Gypsum and Asbestos Industries, Sverdrup & Parcel and
Associates, Inc., for the Environmental Protection Agency,
July 1971.
3. Flat Glass Technology. R. Perssons, Butterworths, London,
1969.
-------
APPENDIX A-9
SIC 33—PRIMARY METAL INDUSTRIES
-------
APPENDIX A-9
SIC 33 —PRIMARY METAL INDUSTRIES
SIC 331—BLAST FURNACES. STEELWORKS. AND
ROLLING AND FINISHING MILLS
This industry comprises establishments primarily engaged in
manufacturing hot metal, pig iron, silvery pig iron, and ferroalloys
from iron ore and iron and steel scrap; converting pig iron, scrap iron,
and scrap steel into steel; and in forming hot rolling iron and steel into
basic shapes such as plates, sheets, strips, rods, bars, and tubing.
Merchant blast furnaces and by-product or beehive coke ovens are
also included in this category.
The remaining industries in the SIC 331 classification produce
electrometallurgical products; steel wire drawing and steel nails and
spikes; cold rolled steel sheet, strip, and bars; and steel pipe and
tubes.
Steel industry literature typically classifies steel mills into four
sub industries as follows:
Fully integrated - Coke ovens, blast furnaces, steel fur-
naces, and rolling and finishing mills
Partially integrated (with blast furnaces) - Blast furnaces,
steel furnaces, and rolling and finishing mills
-------
APPENDIX A-9-2
Partially integrated (without blast furnaces) - Steel fur-
naces and either rolling and finishing mills or a forging
department
Nonintegrated - All other establishments, i. e. , beehive
coke ovens, by-product coke ovens operated independently
of blast furnaces and steel departments, merchant blast
furnaces, and establishments with hot rolling and finishing
operations.
1. NUMBER AND SIZE OF ESTABLISHMENTS AND
GEOGRAPHICAL LOCATIONS
Most of the iron and steel industry in the United States is cen-
tered in the integrated facilities of large corporate enterprises. Eight
producers are among the 100 largest industrial corporations in this
country. The comparatively small integrated producer in this industry
represents a very large industrial complex, and even the smallest is,
in actuality,not a small operation.
There were a total of 329 establishments in the steel industry
(SIC 3312) as of 1967. The majority of these are located in the Middle
Atlantic and East North Central geographical divisions (see table on
following page).
-------
Division
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
APPENDIX A-9-3
Establishments'
Total No. With 20 or More Employees
8
116
94
10
24
28
9
3
37
329
6
94
79
6
19
26
4
2
23
259
The overwhelming majority of steel companies are large em-
ployers by general industry standards. In fact, over 90 percent em-
ploy over 1,000 persons and over 80 percent employ better than
2, 500 persons (see table below).
Establishments
39
11
20
26
17
38
40
36
35
67
329
Size (No. of Employees)
1-4
5-9
10-19
20-49
50-99
100-249
250-499
500-999
1,000-2,499
2, 499 or More
Total No. of
Employees
( 50)
100
300
800
1,300
6,300
14,800
26,500
57, 100
425,900
533, 100
-------
2.
APPENDIX A-9-4
INDUSTRY GROWTH PATTERNS AND PRODUCTION TRENDS
The growth pattern in the steel industry has been rather uneven
over the past decade or so. Although there was about a 13 percent
increase in the number of establishments, from 288 in 1963 to 329 in
1967, the percentage growth in employment showed considerable fluc-
tuation and was up only 7 percent as of 1967 (see table below).
Year
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
Establishments
291
NA
NA
NA
NA
288
NA
NA
NA
329
NA
NA
NA
Total No. of
Employees
(1,000)
511.4
507.5
550.0
503.4
502.2
500.5
532.9
565.4
559.4
533. 1
NA
NA
NA
Value
Added
($ Millions)
6,062.2
6,823.4
6,844.4
6, 546. 3
6,620.9
7,506.4
8,479.6
9,379.8
9,643.6
8,910. 1
NA
NA
NA
Total
Tons Prod
(Millions)
85. 3
93.4
99.3
98.0
98.3
109.3
127. 1
131.5
135.0
127.2
131. 5
142.6
134.9
(NA = Not Available)
Industrial production has also shown considerable fluctuation
over the past several years. After steady growth from 85. 3 million
tons in 1958 to 135.0 million tons in 1966, total steel tonnage has fluc-
tuated from 127. 2 million to 142. 6 million. These fluctuations can be
-------
APPENDIX A-9-5
attributed to variations in supply and demand as a result of the national
economy and also vigorous competition from foreign producers.
In summary, it is concluded that the steel industry has entered
a stage of transition and consolidation. In the event of a sustained
improvement in the national economy and stabilization of the world
trade situation, additional growth in steel production is anticipated.
3. STANDARD PRODUCTION PROCESSES AND WASTE
MATERIALS
Pig iron is produced in a blast furnace utilizing iron ore, coke,
and limestone as raw materials. Steel is produced from pig iron by
a variety of processes using the open hearth furnace, basic oxygen
furnace, electric furnace, and Bessemer converter. Modern steel-
making processes utilize a large percentage of steel scrap in addition
to pig iron and various alloying elements.
The following paragraphs describe the basic processes in the
steel industry and identify the waste materials associated with each
process.
(1) Typical Manufacturing Processes and Associated
Waste Materials in the Steel Industry
For the purpose of describing steel manufacturing and iden-
tifying associated waste materials, the steel industry was divided
-------
APPENDIX A-9-6
into five sections, each containing several processes and alter-
nate combinations of processes:
. Coke Manufacturing
Coke
Coal Distillation Products
Coal Chemicals
, Iron Manufacturing
Hot Metal (Liquid Iron)
Pig Iron
Iron Castings
Sinter
Malleable Iron Products
Wrought-Iron Products
Sponge Iron Products
Slag and Slag Products
Steel Manufacturing
Liquid Steel
Slag and Slag Products
Ingots
Steel Castings
. Hot Forming
Slabs
Blooms
Plate
Hot Band
Hot Rolled Sheet
Butt Weld Pipe
Seamless Pipe
Structural Shapes
Hot Rolled Bar
Billets
Hot Rolled Rod
Extruded Steel Shapes
-------
APPENDIX A-9-7
Cold Finishing
Cold Rolled Sheet
Cold Rolled Strip
Tin Plate
Electric Weld Pipe
Cold Drawn Tube
Cold Rolled Bars
Cold Drawn Bars and Shapes
Cold Drawn Wire
Cold Drawn Rod
Nails
(Stainless Steel and Ferro-Alloys Made in Blast Furnaces
are in separate categories.)
A given plant may ship iron or steel at any stage of production
as its final product, thus giving rise to the general classifica-
tion previously described (fully integrated, partially integrated,
etc.). The basic processes in these five areas and the asso-
ciated waste materials are presented in diagrammatic form in
Figure A-9-1.
Although not strictly a steelmaking operation, coke produc-
tion is usually included with the industry. This is because it is
a heavily used raw material and is produced by most steel plants.
Significant waterborne wastes result from almost all steel
mill manufacturing operations. These wastes principally are
suspended solids, oils, heated water, acids, plating solution,
and dissolved organic chemicals. Steel industry wastewaters
-------
RAW MATERIAL
PREPARATION AND
COKE MANUFACTURE
IRON MANUFACTURE
Xv_
STEEL MANUFACTURE
ROLLING
/
N /
SCRAP OR )
PREREDUCEDV-
ORE j
ORE PELLETS
* a \
SINTERING \
\
LIMESTONE -,.-..,..,
/
/
/
COAL COKE /
* OVENS
"
• . AMMONIA STILL
EFFLUENT
• INDIRECT
COOLING WATER
\ BLAST
/ FURNACE
/
r
1
1
1
|
1
1
1
1
1
*
»
CASTING
PIG
IRON
• GAS SCRUBBER
WATER
• SETTLING CHAMBER
SOLIDS
\ /
M
,
r
/
BASIC
OXYGEN
"I
.
i 11
./
\ '"
OPEN
HEARTH
4
1
\ ! II
\ ! '»
\
I
ELECTRIC
FURNACE
'
J
1
\
• GAS SCRUBBER
WATER
• SLAG
FINISHING
COLD-DRAWN
BARS
WIRE
SEAMLESS
PIPE
COLD ROLLED
SHEET ft STRIP
COATINGS ft
PLATINGS
WELDED PIPE ft
TUBING
LIGHT OIL RECOVERY
EFFLUENT
FINAL GAS COOLING
WATER
COKE QUENCHING
WATER
• SLAG COOLING
WATER
• SLAG
CLEANING RINSE
WATER
PICKLING RINSE
WATER
SLUDGE~FROM
PICKLE LIQUOR
NEUTRALIZATION
M
FIGURE A-9-1
Standard Production Processes and
Waste Materials
CO
I
00
-------
APPENDIX A-9-9
are unique among industrial wastes in that the solutions of the
effluent streams are so great.
Typical water usage in an integrated steel mill amounts
to about 40, 000 gallons per ton of steel produced. Water usage
is distributed among the various basic operations as follows:
Manufacturing Operations % of Water Used
Coke 12. 5
Iron 25
Steel 12. 5
Hot forming and rolling 25
Finishing 20
Sanitary, boiler and other 5
1. Coke Manufacturing
Coke is produced by heating coal to a temperature
above which the volatile matter is driven off. In the bee-
hive processor is admitted to the coking chamber in con-
trolled amounts for the purpose of burning the volatile
products distilled from the coal to generate heat for fur-
ther distillation. In the by-product method, air is ex-
cluded from the coking chambers and heat is supplied ex-
ternally. Today the by-product process produces about
99 percent of all metallurgical coke.
Most materials eminate from the coal volatiles col-
lected as a gas and subsequently cooled by spraying with
water. The condensate from the gas and the flushing liquor
consist of a tar high in phenols and an ammonia liquor which
is stored in stills. Some 90 to 95 percent of the phenols in
the ammonia liquor is removed by either the liquid extraction
method or the vapor circulation method. Ammonia in the
coke-oven gas is recovered by either the ammonium sulfate
method or by recovery of anhydrous ammonia. Light oil is
scrubbed from the cooled gas by a high-boiling wash oil.
-------
APPENDIX A-9-10
Significant wastes discharged from coke plants in-
clude the following:
Waste Material
Ammonia still effluent
Indirect cooling water from
coolers and condensers
Light oil recovery effluent
Coke quenching water
(high temperature)
Coke worf drainage
Compounds and
Undesirable Properties
phenol
sulfur
ammonia
chlorides
high temperature
phenol
cyanide
ammonia
oil
cyanogen
Final gas cooler water
phenol
cyanide
solids
solids
color
2.
Iron Manufacturing
Virtually all iron produced in the world today is re-
duced in blast furnaces. Coke is burned to produce carbon
monoxide gas which passes up through the furnace to con-
tact with ore particles (iron oxide). The carbon monoxide
gas combines with the ore to produce carbon dioxide gas
and metallic iron. The heat generated by the burning coke
supplies the heat to make the reaction to proceed and the
heat to melt the metallic iron once it is formed.
The major impurity of most iron ore and coke, silica
(silicon dioxide), is removed from the furnace by the addi-
tion of limestone. At the high temperature in the furnace,
-------
APPENDIX A-9-11
the lime combines with the silica to form a low melting
material called slag. Melted slag is lighter than the
melted iron,thus it can be skimmed off as the iron leaves
the furnace.
Slag is treated either by slow air cooling in dry pits
in the ground from which it is later dug up as a solid mass
or by granulation through rapid cooling from high volume
streams of water.
Gases leaving the top of the furnace are hot, dust
laden and traveling at high velocities. These are treated
by passing through settling chambers, then wet scrubbers
and coolers, and in some instances, electrostatic precip-
itators.
Significant wastes eminating from the iron manufac-
turing processes include:
Waste Material Compound
Gas scrubber waste phenol
nitrogen
cyanide
ammonia
suspended solids
iron oxide
Slag sulfides
Gas settling chamber
Slag cooling water hydrogen sulfide
sulfur dioxide
3. Steel Production
There are three basic methods in use today for the
manufacturing of steel:
Electric Air Furnace
Open Hearth Furnace
Basic Oxygen Furnace
-------
APPENDIX A-9-12
The Bessemer converter which was widely used in the
past is technologically obsolete and today represents a
negligable percent of the steel produced.
All three furnace methods use pure oxygen and/or
air to refine hot metal (iron) and other me tallies into
steel by oxydizing and removing the elements present
such as silicon, phosphorus, manganese and carbon.
Molten steel from any of the three processes is poured
into steel holding ladles and transported either to the
teeming or the continuous casting area. Sometimes fur-
ther processing in the way of further oxidation and alloy-
ing is done in the Vacuum Degassing Process area.
Teeming involves pouring the molten steel from the
holding ladles into ingot molds for cooling, reheating and
then rolling. In the Continuous Casting process,billets,
blooms and slabs are cast in water-cooled open-ended
copper molds directly from the hot steel.
Waste materials from steel production include slag
and various solid and waterborne substances from gas
cleaning operations employed in each of the three methods.
The Basic Oxygen and Open Hearth furnaces both
utilize precipitation and venturi scrubbers, while the
Electric Arc furnace also employs the baghouse. Waste
materials are as follows:
Waste Material Compound
Slag silicon dioxide
manganese oxide
phosphorus pentoxide
sulfur
iron
Gas scrubbing water oxides of iron
sulfur
nitrogen oxide
suspended solids
-------
APPENDIX A-9-13
(1) Further Processing of Steel
In the hot forming and rolling processes,the
steel ingot is generally sent to the blooming or slab-
ing mill. The basic operation involves the gradual
compression of the steel ingot between surfaces of
two rotating rolls to form either blooms, slabs, or
billets of varying square and rectangular shapes.
The basic purpose of the various hot forming
processes is to produce various finished or semi-
finished products. These include pipe, structural
shapes, bars, rods, and extrusions,among other
things.
During most of the hot forming and rolling
processes a considerable amount of waste is gen-
erated in cleaning and cooling the steel.
Cleaning usually involves the removal of scale
and oxides from steel surfaces by pickling in dilute
acid solution. In the reduction, forming, shaping
and rolling from the initial ingot on through all the
hot forming and rolling processes,the wastewater
generated includes the following waste materials:
Waste Material Compound
Cleaning, flushing and suspended solids
pickling rinse water oil
iron scale
Sludge from lime
neutralization of spent
pickle liquor
(2) Finishing Operations
Finishing operations are usually the final ones
in the overall steel manufacturing processes. These
include:
Pickling
Cold rolling
Tin plating
-------
APPENDIX A-9-14
Galvanizing
Chrome plating
Cold shaping
Cold drawing
Coating of all types
Tempering
Polishing
Many of the finishing operations involve special
lubricating, cleaning and cooling operations. Lubri-
cation is typically performed by oil or oil and water
emulsions. Cooling is done by various water sprays
and rinses, and cleaning is usually accomplished by
various pickling solutions.
Finishing operations produce wastewaters and
other waste effluents. These include the following:
Waste Compound or
Waste Material Undesirable Property
Rolling solutions for Oil
lubrication Suspended solids
Cooling water Oil
Submicron solid particles
High temperature
Pickling rinse water Sulfuric acid
Hydrochloric acid
Iron salts
Spent acid baths Sulfuric acid
Hydrochloric acid
Iron salts
Plating and coating Tin
effluent Chromium
Cadmium
Zinc
Nickel
Cyanides
Acids
Alkali
-------
APPENDIX A-9-15
(2) Production Processing Trends and Projections
The general trend in the steel industry is toward the use
of subprocesses which will produce products of lighter unit
weight at increasingly higher speeds with minimum manual op-
erations. Production units generally tend toward the largest
sizes in order to realize the economy of scale.
1. Effect of Advanced Technology on Volumes of
Waste Materials
The application of advanced technology usually pro-
duces increased amounts of waste materials. Levels of
technology in the industry may be described according to
the relative prevalence of certain subprocesses in a par-
ticular plant. New or advanced subprocesses being in-
creasingly employed include:
Basic oxygen furnace
Continuous casting
Vacuum degassing
Hot scarfing
Electrolytic tinplating and galvanizing
Plant sizes vary considerably, however, the ma-
jority of plants produce less than 1 million ingot tons per
year as shown in the following table of 1967 data:
Annual Production
Plant Size % of Plants (Ingot Tons)
Small 53.9 Less than 1,000,000
Medium 15.2 1, 000, 000 to 2, 000, 000
Large 30.9 More than 2,000,000
-------
APPENDIX A-9-16
Generally,the larger plants tend to be the newest and have
a higher percentage of advanced technology as demonstrated
in the following table using 1968 data:
Level of Technology
Old Typical Advanced
Small 31.9 53.8 14.3
Medium 30.0 54.8 15.2
Large 27.8 34.0 38.2
All 30.0 46.0 24.0
Waterborne wasteloads tend to be the greatest with the
newer plants utilizing advanced technology in order to
achieve high-speed high-volume output. This is gen-
erally due to the fact that wastes are generated in pro-
portion to the surface area of steel exposed during the
rolling and finishing operation and in proportion to the
relative gas-liquid interfacial areas in the iron-making
and steel-making operations. The predominance of lighter
products and higher production rates tends to maximize
these areas and thus generate greater unit wasteloads.
Wastewater volume for various levels of technologies is
summarized below:
Gallons Wastewater
Level of Technology per Ingot Ton
Old 9,860
Typical 10,000
Advanced 13,750
The newer installations do, however, generally in-
corporate waste treatment facilities, and actual plant dis-
charges are not necessarily greater in newer plants.
Particularly difficult waste problems arising from
the newer subprocesses includes:
Sub-micron size particles in gas wash water
from ferromanganese furnaces
-------
APPENDIX A-9-17
Very fine suspended particles in wastewaters
from basic oxygen furnaces and hot-strip mills
Soluble oils in effluents from cold mills.
2. By-Product Utilization, Waste Recovery, and
Recycling
Conservation and reuse practices are common in
many areas of the steel industry due to the sheer magni-
tude of the waste materials involved. There are obvious
economic incentives to recover and recycle certain ma-
terials including:
Coke oven gas
Blast furnace gas
Flue dust
Slag
Soluble oils
Mill scale
Coke oven chemicals
Scrap iron and steel
However, much of the industry's wasteload is con-
tained within the large quantities of water used in the
manufacturing process. Except for a few items listed
above, water has not been conceived or reused to a sig-
nificant degree. In most instances,the sheer volume of
wastewater makes recovery and reuse of materials un-
economical. Also contributing to this situation are the
facts that the petrochemical industry is highly competitive
in the product areas in which recovered materials would
fall and also that the industry is geared to heavy high-
volume production with raw materials cheap on a weight
basis and,thereforetusually uneconomical to recover with
expensive processing. Materials which are typically not
reclaimed or reused include:
Pickling acids
Plating solutions
Basic oxygen process dust
Lubricating oils
Coke oven chemicals
Neutralized pickle liquor sludge
-------
APPENDIX A-9-18
(3) Waste Materials from the Steel Industry
A comprehensive list of waste materials from steel mills
is presented below. Since there is a wide variation in the types
of subprocesses employed at any one plant, not all of the wastes
would be found at any one plant.
Waste Materials
Suspended solids
Phenols
Cyanides
Fluorides
Ammonia liquor
Lubricating oils
Sulfuric Acid (H2SO4)
Ferrous Sulphate (FeSO4)
Emulsions
Chromium
Zinc
Tin
Ferric Chloride (FeCl2>
Hydrochloric Acid (HC1)
Kjeldahl nitrogen
Nitrates
Phosphates
Sulfates
Aluminum
Manganese
Sodium
Potassium
Lead
Cadmium
Silicon
Copper
Nickel
Iron
Triocyanates
Heated Water
-------
APPENDIX A-9-19
Waste Materials
Dissolved organic chemicals
Soluble metals
Pickle liquor - sulfuric or hydrochloric acid
Ammonia still waste (contains phenols)
Gas final cooler water (contains cyanogen compounds)
Chlorides
Sulfides
Slag (silica plus limestone) (fluxes)
Plating wastes
Coating effluents
Scaling solutions (contain oil and suspended solids)
Mill scale.
4. WASTE DISPOSAL PROCESSES AND PRACTICES
The characteristically large volumes of wastes in the steel in-
dustry makes for difficult waste control problems. A waste stream
flowing at 10,000 to 25, 000 gallons per minute, presents a very dif-
ficult treatment problem. Nevertheless, there are a large number of
waste treatment processes employed,to varying extents,throughout the
steel industry.
(1) Current Waste Treatment Processes
Table A-9-1 presents a list of the many treatment processes
currently being employed in the steel industry.
-------
APPENDIX A-9-20
Table A-9-1
Waste Treatment Processes and Materials
o
U
o
Waste Treatment Processes
Liquid extraction and distillation
Solvent extraction
Vapor recirculation and stream
distillation
Biological oxidation
Free or Fixed Ammonia Still
Thickening and sintering
Chemical addition
Waste Material
Phenol, Cyanide, BOD
Ammonia
Suspended solids in water
from gas cleaning process
water
0)
o>
•*•»
CO
c
•l-t
s
o1
En
Chemical coagulation
Magnetic agglomeration
Slag processing - iron reclamation
and crushing slag into saleable
product
Chemical Addition
Thickening
Scale Pit (settling chamber)
Oil skimming
Secondary settling
Filtration
Haul out
Deep well
Neutralize
Regenerate (HC1 only)
Gas cleaning wastewater
Slag
{Process waters
Scale
Pickle acid
-------
APPENDIX A-9-21
Table A-9-1 (Continued)
-3
14
0)
c
0)
O
Waste Treatment Process
Stabilization lagoons
Ion-exchange
Dialysis and electrodialysis
Fluid bed regeneration
Pressurized deep bed filtration
(i. e., Pressure Filtration)
Floeculation and clarification
Coagulation (chemical)
Chemical precipitation
Filtration, quartz sand filter
Dissolution, carbon adsorption,
solvent extraction
chemical precipitation
Biological digestion and
sludge activation
Benz ine-NaOH-dephenoliz at ion
Phenosolvan process
Ifazol process
Electrolytic decomposition
Fractionation
Activated sludge
Vaporization by steam
Extn. by steam
Absorption by solids
Deep-well
Pickling, crystallization
and recovery
Liquor regeneration
Waste Material
Pickle liquor
(Scale pit water
\ Plate mill waste
Hot mill waste
Sinters, oil, sediments
Scrubbing water
Waste waters
Nickel, cobalt,
molybdenum
chromium
(super alloy grindings)
Coke sludge
Phenol
Phenol
Phenol
Phenol
Phenol(recovery)
Acid
-------
APPENDIX A-9-22
(2) Advanced Treatment Systems
Just about any known waste treatment process,which is
applicable to the steel industry, can be found in operation in one
place or another. Therefore, rather than looking toward any
vastly new treatment processes on the horizon,the steel industry
is largely attempting to improve the operations and economies
of systems presently in use. Some of the more advanced sys-
tems include the following:
Phenols - A solvent extraction system is reported
to yield 99 percent recovery
Acids - Lime neutralization with solids separation
and recovery of iron oxide is being utilized by some
companies. There are also several proprietary sys-
tems being marketed for acid recovery including:
A sulfuric acid recovery system has been
developed by KSF Chemical Processes Ltd.
Hydrochloric acid recovery systems on the
market include the Turbulator System,
Dr. C. Otto and Co., Bochum, Germany,
and the Fluid Bed Regeneration System, Lurgi
Gesellschatt, Frankfort, Germany.
Oily wastewater treatment systems include equali-
zation, chemical addition with rapid mixing, floccu-
lation, and dissolved air flotation all employed in
sequence.
-------
APPENDIX A-9-23
(3) Composition of Waste Streams and Efficiency of
Waste Treatment Processes
Waste streams from steel plants contain considerable
numbers of types of waste materials. These waste materials
will vary in quantity and type depending upon several factors
such as:
Level of technology employed in each subprocess
Subprocesses used
Types of products being manufactured
Proper operation of facilities
Waste treatment systems employed
Total wasteloads and "wastewater volumes per unit of
product for typical waste materials is presented in Table
A-9-2.
Estimated wasteloads and wastewater volumes for 1968
in terms of millions of pounds and pounds per dollar value added
are given in Table A-9-3.
-------
APPENDIX A-9-24
Table A-9-2
Estimated Waste Loads and Volumes
Wasteload, Pounds Per Ingot Ton Per Day
Wastewater, gals Old Typical Advanced
per ingot ton per day Technology Technology Technology
Suspended Solids 103 125 184
Phenols 0.069 0.064 0. 064
Cyanides 0.029 0.028 0.031
Fluorides 0.033 0.031 0.031
Ammonia 0.082 0.078 0.078
Lube Oils 3.08 2. 72 2. 37
H2SO4 3.03 3. 54 2.83
FeSO4 11.3 13.2 10.5
Emulsions 0.332 0.414 1.17
Chromium - 0.063 0.063
Zinc 0.0025
Tin - 0.016 0.016
FeCl2 - - 2. 10
HC1 - - 0.565
Wastewater volumes on a similar basis are tabulated below:
Wastewater, gals
Technology Level per ingot ton per day
Older 9,860
Typical 10,000
Advanced 13,750
-------
Table A-9-3
Wastewater Loads and Volumes for Typical Waste Materials
Estimated Wasteloads and Wastewater Volumes in 1968
Technology Level Old Typical Advanced Totals Waste Loads and
_ Wastewater Volumes Per
Ingot Tons/Year 41.5x10 63.7x10 33.3x10 138.5x10 Million $ Value Added
Wastewater, Gals./Year 409xl09 637xlQ9 458xl09 I,504xl09
Waste
Suspended Solids
Phenols
Cyanides
Fluorides
Ammonia
Lube Oils
H2S04
FeSO4
Emulsions
Chromium
Zinc
Tin
FeCl2
HC1
Waste Loads in Millions of Pounds Per Year
1.37 x 10
8
4,270
2.86
1.21
1.37
3.40
128
128
469
13.8
-
-
-
-
-
7,960
4.07
1.78
1.97
4.96
173
225
841
26.4
4.01
-
1.02
-
-
6,120 18,
2.13
1.03
1.03
2.61
79.0
94.2
349 1,
38.9
2.11
0.08
0.53
69.9
18.9
350.00
9.06
4.02
4.37
10.97
380. 00
445. 20
659.00
79.10
6.12
0.08
1.55
69.90
18.90
1,668,000*
824*
365*
397*
997*
34. 545*
40,473*
150,818*
7,191*
556*
7.2*
141*
6,354*
1,718*
H
ai
CO
&
en
-------
APPENDIX A-9-26
The normal waste removal efficiency for various waste
treated by a particular waste removal process is presented in
Table A-9-4. Projected net wasteloads for 1970 and 1974
(Table A-9-5) indicates that, in spite of increased percentages
of waste reduction, waste discharge at steel mills will increase.
This is due to the fact that increased steel production by ad-
vanced processes will yield considerably larger wasteloads.
Better waste reduction will not be able to offset the increased
wasteloads.
(4) Current Waste Treatment Practice and Trends
The percentages of steel plants utilizing certain basic
waste removal methods is documented in Table A-9-6. General
trends indicate an increase in the use of various treatment
processes. The more advanced processes including biological
treatment, ion exchange, and regeneration are all expected to
see more widespread usage throughout the industry.
Pickling liquor wastes and pickling rinsewater appear to
be the most troublesome problems plaguing the industry. There
appears to be a general trend toward the use of hydrochloric acid,
which simplifies regeneration processes, to replace sulfuric acid
-------
Table A-9-4
Efficiency of Waste Removal Processes
Removal Method and
Source of Wastes
Plain Sedimentation:
. Blast Furnace & Sinter Pit.
. Hot- Rolling Mills
Coagulation & Sedimentation:
. Plant Furnace & Sinter Pit.
. Hot-Rolling Mills
. Cold Mills
Recirculation and:
. Plain Sedimentation:
- Blast Furnace & Sinter Pit.
- Hot- Rolling Mills
- Cold Mills
. Coagulation & Sedimentation:
- Blast Furnace & Sinter Pit.
- Hot-Rolling Mills
- Cold Mills
. Magnetic Separators
River Water for Coke Quenching:
. Blast Furnace
Still Wastes for Coke Quenching:
. Coke Plant
Normal Removal Efficiency for Indicated Waste
Suspended
Solids
93.8
90.7
98.2
95.4
50.0
98.8
96.9
50.0
99.6
98.4
80.0
80.0
Lube
Oils
20.0
80.0
60.0
90.0
Acids
Soluble
Metals
Emulsions
75.0
95.0
Coke Pit.
Chemicals
90.0
92.7
S
CO
CO
-3
-------
Table A-9-4 (Continued)
Removal Method and
Source of Wastes
Biological Treatment
Deep-Well Disposal
Ion Exchange
Neutralization & Sludge Lagooning
Regeneration Processes
Proper Operation of Facilities
Normal Removal Efficiency for Indicated Waste
Suspended
JSolids
Lube
Oils
Acids
85.0
80.0
80.0
Soluble
Metals
100.0
95.0
Emulsions
Coke Pit.
Chemicals
80.0
100.0
8
2
B
CO
to
CO
-------
APPENDIX A-9-29
Table A-9-5
Projected Net Wasteloads
Waste
Component
o
O)
1-4
£-
£»
O)
1-1
Suspended Solids
Lube Oil
Acids d)
Soluble Metals
Emulsions
Coke Pit. Chemicals
Fluorides
Suspended Solids
Lube Oil
Acids (1)
Soluble Metals
Emulsions
Coke Pit. Chemicals
Fluorides
Gross Waste
Quantity
Generated (Ibs)
20,080 xlO6
401 xlO6
6
2,335 xlO
8.46xl06
6
90.5 xlO
25.62xl06
R
4.65x10
6
27,126 xlO
486 xlO6
2,909 xlO6
11.25xl06
6
138 xlO
6
32 xlO
5.80xl06
Percentage of
Waste Reduction
or Removal
93.9
40.6
76.2
15.5
72. 3
91. 5
0
95.2
52.0
80.7
34.0
73. 5
91.4
0
Net Waste
Quality
Discharged (Ibs!
1,223 xlO6
238.2 xlO6
6
554.7 xlO
7.14xl06
6
25.2 xlO
2.18xl06
6
4.65x10
6
1,317 xlO
233.2 xlO6
560.2 xlO6
7.42xl06
6
36.6 xlO
6
2.75x10
5.80xl06
(1) Free and combined acids.
-------
Table A-9-6
Use of Waste Removal Processes
Removal Method and
Sources of Wastes
Plain Sedimentation:
. Blast Furnace & Sinter Plant
. Hot -Rolling Mills
Coagulation & Sedimentation:
. Blast Furnace & Sinter Plant
. Hot-Rolling Mills
. Cold Mills
Recirculation and:
. Plain Sedimentation:
- Blast Furnace & Sinter Pit.
- Hot -Rolling Mills
- Cold Mills
. Coagulation & Sedimentation:
- Blast Furnace & Sinter Pit.
- Hot -Rolling Mills
- Cold Mills
. Magnetic Separators
River Water for Quenching Coke
. Blast Furnace
Still Wastes for Quenching Coke
. Coke Plants
Estimated Percentage of Plants Employing Method
1950
93
87
0
0
0
5
10
50
2
3
10
5
80
20
1963
85
78
4
1
2
8
15
65
3
6
15
10
50
50
1967
80
68
5
2
4
10
20
70
5
10
20
15
20
80
1972
60
55
15
5
6
15
25
65
10
15
25
20
10
90
1977
40
40
25
10
8
20
30
60
15
20
30
30
10
90
CO
I
CO
o
-------
Table A-9-6 (Continued)
Removal Method and
Sources of Wastes
Biological Treatment
Deep-Well Disposal
Ion Exchange
Neutralization & Sludge Lagooning
Regeneration Processes
Proper Operation of Facilities
Estimated Percentage of Plants Employing Method
1950
0
0
0
10
0
20
1963
5
2
2
50
0
35
1967
10
5
5
80
2
50
1972
15
10
10
85
5
60
1977
20
15
20
75
10
70
M
CO
i
CO
-------
APPENDIX A-9-32
in the pickling processes. However, there is not widespread
agreement among the steel producers as to the best treatment
of waste pickle liquors. Almost every process including neu-
tralization, deep-well disposal, and regeneration, has its
own proponents in the industry.
-------
APPENDIX A-9-3 3
SIC 333—PRIMARY SMELTING AND REFINING
OF NONFERROUS METALS
1. ECONOMIC STATISTICS
Industries in this classification produce primary and secondary
nonferrous metals and alloys from ores and concentrates, or from
scrap. These industries do not include milling or concentrating
operations,since they are located at the mine site and considered mineral
operations, rather than manufacturing activities. Industries which pro-
cess ores to produce chemicals, such as zinc oxide, or which process
ores only, such as alumina from bauxite, are also excluded.
Some overlap with other industries is inevitable. Many of the
smelters and refineries produce considerable quantities of chemicals,
such as sulfuric acid. Others operate their own mines, milling and
concentrate plants, or are fully integrated from mine to refinery.
Relatively few establishments are involved in primary metal
production; most are involved in secondary processing.
Basic statistics related to these industries (Reference 1) are
shown in the following table.
-------
APPENDIX A-9-34
Estab. with
Employees
11,600
2, 700
8,100
23, 800
7,200
17,200
70, 600
20 or more
Employees
32
18
18
24
29
182
303
Value
Added
$ 262,6
48.3
119.5
811.8
139.3
271.2
$1,652.7
3331 Copper
3332 Lead
3333 Zinc
3334 Aluminum
3339 Other Nonferrous
3341 Secondary Smelting
and Refining
Total
The geographic distribution of these industries is given in
Table A-9-7.
The total tonnages involved in this industry are illustrated by
the production data in Table A-9-8.
2. PRODUCTION PROCESSES AND WASTES
There are several typical processes involved in the reduction
of ores. These typical processes are described first, followed by
examples of more specific applications. The wastes associated with
these operations are also noted.
-------
Table A- 9- 7
Geographic Distribution For SIC Code 333
Division
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Totals
Estab V. Ai2
1
6 43.3
3 10.9
2 16.0
1
2 16.3
15
176.1
2
32 262.6
Estab V.A.
£ * i*
4 D
3 D
— — _ —
3 D
3 D
3 D.
18 48.3
Estab V. A.
D D
•• — • -»
D
6 43. C
D D
*
18 119.5
Estab V.A.
2 D
2 D
3
450.9
3
6 253.6
1
228.6
8
25 811.8
Estab V. A.
2
29.1
8
4 9.3
1
2 75.7
6
2
20.3
4
29 139.3
Estab V. A.
9 6.7
47 82.8
60
115.1
9
10 13.1
9 13.8
12 8.3
24 29.5
18fr 269.3
(1)D = Data Withheld
iy.\\T A - 17.0, m AAAoA
APPENDIX A-
CO
CO
en
-------
APPENDIX A-9-3 6
Table A-9-8
Total Production Tonnage
Product
Tonnage
(1000 ST.)
Anode Copper
Unalloyed Copper
Copper Based Alloys
Lead Smelter Products
Refined Unalloyed Lead
Antimonial Lead
Babbitt Metal
Solder
Type Metal
Other Lead and Tin Base Alloys
Refined Zinc
Zinc Residues
Primary Aluminum
Gold
Cadmium
Nickel
Alloys
1030
1430
300
200
400
280
10
100
145
30
1235
265
5360
1530 (ounces)
5.3 (1000 ST.)
0.2
10
These data are approximations only and not sufficiently detailed to identify
the sectors which may produce* hazardous metallic salts.
-------
APPENDIX A-9-37
Roasting and smelting are traditional means for separating metals
from their ores. In recent years, extraction of metal by other processes
(such as leaching or extraction from sea water) have become economically
feasible. The following paragraphs describe these operations.
(1) Roasting
The roasting operation involves heating with a free or con-
trolled access of air, at temperatures too low for fusion. The
objectives may be: the conversion of sulfide ore concentrates to
oxide before reduction (perhaps with the expulsion of volatile
constituents such as arsenic); or reduction, either with a reducing
agent, or to cause a "roast reduction" reaction. Temperature
control is often important, however, the thermal requirements
vary. Self-supporting roast reactions are said to be "autogenous"
(as with zinc sulfide). Control of oxidation-reduction conditions
is also important. Sulfur dioxide must be utilized.
The reaction rates of roasting are limited by the supply
of oxygen to solid-gas interfaces, and by the escape of gaseous
products. Large surface areas, provided by dividing the ore
or by concentrating it in thin layers, are necessary for well
controlled reactions of adequate rate.
-------
APPENDIX A-9-3 8
Flash roasting exploits the observation that: in a multiple-
hearth roaster, a high proportion of the oxidation takes place
when ore falls from one hearth to another. Thus, finely divided
zinc sulfide concentrates, injected by air into a combustion
chamber, are burnt to oxide. As a result, the heat evolved is
adequate to maintain the required temperature.
(2) Smelting
Smelting involves the reduction of an ore (with fusion), at
a high temperature attained by the combustion of fuel or con-
sumption of electricity (electrothermal smelting). The object
is to segregate the metal required in a separate liquid phase. A
flux is added to react with the unwanted material in order to form
a fluid slag. Furnace linings of adequate strength and resistance
to high temperatures and chemical attack are required. Fluxes,
slags and refractories, together form part of the essential chemical
problem in a smelting operation.
Fluxes are classified according to chemical type and are
chosen in relation to the properties desired in slags. The re-
fractories, essential in all pyrometallurgical processes, are
also classified by chemical nature. However, other properties
-------
APPENDIX A- 9- 39
such as resistance to temperature, to temperature changes,
to compression and abrasion, as well as to porosity and volume
change on firing, are also significant.
(3) Hydrometallurgical Processes
The dissolution and precipitation reactions which are the
concern of hydrometallurgy involve handling very large volumes
of solutions and of finely divided solids. To secure sufficient
extraction in a leaching process, the ore or concentrate must be
in a suitable chemical condition for dissolution and must also be
in a state of fine subdivision. Some hydrometallurgy applications
are given in Table A- 9- 9.
(4) Specific Applications of General Processes
The following paragraphs describe extraction operations
related to specific nonferrous metals and alloys.
1. Copper
The blast furnace was suitable only for high-grade
ores and is less adapted to deal with finely divided flotation
concentrates. Thus, the reverberatory furnace (Figure
A-9-2) is presently used for copper smelting.
-------
APPENDIX A-9-40
Table A-9-9
Applications of Hydrometallurgy
Metal
Source
Preliminary
Treatment
Final
Treatment
Copper
Gold
Magnesium
Zinc
Oxide ores,
azurite
(CuCOa Cu(OH)2)
Malachite
(!CuCO3
Cu(OH)2)
etc.
Native
Sea-water
Sphalerite,
etc. (ZnS)
Leaching with dilute
sulfuric acid or ferric
sulfate if su If ides
present
Electrolysis or
"cementation"
(replacement
by iron)
Leaching with dilute
aqueous sodium
cyanide (NaCN)
solution
Precipitation as the
hydroxide and
conversion to
chloride
Oxidizing roast.
leaching with dilute
sulfuric acid
Precipitation by
zinc
Electrolysis
Electrolysis
-------
APPENDIX A-9-41
Waste
hctt
boilers
Slig S
discharge
^Matte tap holes
Charging zone Converter slag spout
Coal-dust
burners
Charge
hoppen
Charge
FIGURE A-9-2
Reverberatory Furnace
Much of the combustion heat is carried away by the waste
gases, which leave the furnace at a very high temperature.
As a result, waste-heat boilers are an integral part of the
furnace.
Converting is the final stage in the smelting process.
This is accomplished by blowing streams of air through the
molten matter, in a refractory-lined converter in order
to oxidize the ferrous sulfide into sulfur dioxide. Thus, the
sulfur as a gas is eliminated. About 2 percent of the copper
escapes during conversion, but it is recovered by means of
a Cottrell precipitator.
-------
APPENDIX A-9-42
The final stage in copper extraction is refining,
because all the impurities are contained in the converter
product. Figure A- 9- 3 is a flow chart for copper refining.
The modern need is for very pure metal (better than 99. 9
percent), for which electrolytic refining is preferable.
This technique has the advantage of removing bismuth,
selenium, tellurium, and nickel and of leading to the
recovery of precious metals. Electrolytic copper refining
cell and electrodes are pictured in Figure A- 9- 4.
H'
j ^ Electrodes
Overfl°"
Electrolyte (
supply pipe
jCL_
Lead-lined
electrolytic tank K
U- ... 1 1 ft ..
n
illjsi
*]
^/Return pipe
mes launder
Copper rod
'-, Anode
*~ — j^ft ,
• f
C
H
~W~¥T
~E K
athode stai tin
sheet
FIGURE A- 9- 4
Electrolytic Copper Refining Cell and Electrodes
The purpose of the "slimes launder" is to collect the
anode slime, which consists of impurities that are not
anodically dissolved and fall to the bottom of the tank.
-------
Blister . Copper
Starting Sheet C
4 1
Anode SI in
Oxidizing
Leachi
Base
Metal
Slag
1 1
le Impure Cathode • — Ca
Electrolyte Starting
Sheets
1
Roast. Fun
Jig
Gold-Silver
Alloy
Parting Cop
Cells 99-S
1
4 4
thodes Slime Impure Anode
Electrolyte X
/ Scrap
/
I /
ace Electrolysis
With Insoluble
Anodes
Copper De-Copperized
Solution
f Nickel Sulfate
>er V
5% Reclaimed Acid
1
APPENDIX A -9 -4
FIGURE A- 9- 3
Copper Refining Flow
Gold
Silver
n
CO
-------
APPENDIX A-9-44
Compositions of the slimes vary greatly, but an average
analysis might be:
Chemical Se Te Cu Ag Au As Sb Pb N SO4
Percent
22.0 3.7 40 10 2.5 0.1 0.2
.04 6.2
Large quantities of solid waste material are generated
in mining, concentrating, and smelting copper ore (see
Appendix A-l for details). Discharge of obnoxious gases
and fumes from smelters is also a problem.
2.
Lead
Lead is recovered from its ores by smelting in
blast furnaces or ore hearths employing carbon fuels. The
sulfur in the concentrates (also containing 70 percent lead
and a small zinc content), are removed by a roasting-sintering
process, usually on a Dwight-Lloyd sintering hearth pictured
below.
ing ore bed.
track of
pallets or cart
FIGURE A- 9- 5
Dwight-Lloyd Sintering Hearth
-------
APPENDIX A-9-45
Lead recoveries at primary lead smelters are usually about
97 to 99 percent of the lead contained in the ore. Precious
metals are recovered in the refining process.
The sequence of processes for softening (the removal
of copper, tin, antimony and arsenic) and desilverizing lead
bullion, and the recovery of by-products, is subject to many
variations. Melting and oxidation characteristics of the
impurities determine the method of removal. The high
corrosion resistance of lead and its alloys permits a high
degree of reclamation.
Lead smelters are equipped with efficient dust and
fume collection systems for a 98 percent recovery factor.
Smoke purification devices collect sulfur fumes and protective
devices prevent lead poisoning. Good ventilation is essential.
3. Zinc
Zinc reduction is accomplished by electrolysis.
The zinc concentrate is roasted to eliminate most of the
sulfur. Recoveries range from 89 to 98 percent.
Secondary zinc is recovered from copper-base
alloys, principally brass. Some scrap is vaporized in a
-------
APPENDIX A-9-46
furnace, while other scrap is processed in a retort. A
flow chart for lead- zinc production processors is shown
in Figure A-9-6.
Lud-zlnc or*
i5T
Iron
concentnta I
concentn
Flub toast
h
-Or-
Slnter
FlnhrnK
>.-—soi—J
lad ilnter .
Zkcilnter
lad
ulllon
Lett
Blutftimoa
Lcadilng
Zinc flan*
Bectrdytfc
Steam "1ofP'1Jte
*|' (eondenied) "xk
Fnctionitlon I
Bectrol/ili
i-h/1
o,—J-,1—o,
-H.S04-*
fT* Buuctn
L J. 1 > » r*7
Pb 81 a A| An Cd Zo
(NH,
HI
H.PO*
liSO. NH,NO. (NH4iHPO<
FIGURE A-9-6
Lead-Zinc Production Processors
Zinc-base alloys are recovered by remelting and
redistillation to be used in commercial zinc products. The
copper-base alloys are remelted and the contained zinc is
used in brass and bronze ingot.
Efficient dust, fume and stack systems permit
collection and utilization of by-products such as lead,
cadmium and sulfur. Zinc contained in metallurgical residues,
-------
APPENDIX A-9-47
at lead and copper smelters,is mostly recovered and
returned to a zinc plant for refining.
4. Aluminum
Most bauxite is refined by the Bayer process. This
process involves a caustic leach of bauxite at elevated
temperature and pressure, followed by separation of the
resulting sodium aluminate solution and selective preci-
pitation of the aluminum as the hydrated aluminum oxide
(ALgOg * 3H2O) alumina. The insoluble tailings (red
mud) are further treated to extract aluminum silicates.
The residuals from this process are known as "brown mud'
and are composed of calcium silicates and iron oxides.
Primary aluminum is produced by the electrolysis of
alumina in a molten bath of cryolite.
Current efficiency ranges from 85 to 90 percent.
Energy losses are principally caused by physical losses of
metal through spillage and evaporation, and reoxidation of
aluminum by carbon dioxide.
To prevent atmospheric pollution, gases are passed
through a collecting and scrubbing system which removes
alumina, carbon, and fluorides.
-------
APPENDIX A-9-48
A second electrolytic cell (the Hoope cell) produces
a superpure aluminum of 99. 95 percent purity. At most
aluminum plants, solid wastes are impounded in large mud
lakes near the plant.
5. Rare Earths
Solvent extraction and ion exchange are the two main
commercial methods of separation. Other methods employ
fractional crystallization by evaporation, and thermal reactions
which include fusion and volatilization.
Technological problems exist in all stages of rare-
earth mineral processing. The separation of individual
rare-earth elements from one another is difficult because
of their chemical similarity. Incomplete reduction and
the difficulty of collecting homogeneous metal modules are
further problems.
Other nonferrous metals have similar smelting and
refining processes as those previously discussed. Specific
procedures, as for gold, must be considered. However,
the waste disposal problems and practices are usually very
similar from one smelting and refining process to another.
-------
APPENDIX A-9-49
3. DISPOSAL PRACTICES
There are many general methods of disposal techniques used in
the smelting and refining of nonferrous metals and alloys. There is a
general scheme for the disposal and treatment of slag, flue gases,
tailings and liquid effluents.
Slag is either trammed to the dump in a molten condition or it
is granulated and sluiced away from the furnace. The slag is then
delivered to decart ponds, where it settles. Water overflow is collected
in settling ponds for the removal of some suspended material. Slag is
removed from the ponds and transported to a disposal area where a
"slinger" distributes it on the dump.
Flue gases are collected to allow settling of dust, after which
they are channeled to a central flue for electrical precipitation and
finally released into the atmosphere. Stack emanations have been
drastically reduced. Dust removed from the flue system is treated again
in the plant. Arsenic and bismuth can be recovered during copper smelting
and refining.
Tailings are disposed of in sites adjacent to the slag disposal
area. Ponds are used for the storage of tailings.
-------
APPENDIX A-9-50
Effluent from plants contain a high concentration of iron which
could pollute streams. Some of the effluent characteristics are:
Flow rate = 3000 to 5000 gpm
pH =3.5 to 4. 0
Fe (iron) content = 2. 5 grains per liter
Effluent water is neutralized with lime (Ca(OH)_) to dissolve the iron
as ferric oxide (Fe(OH)g). After pH is adjusted to about 7.0, the waters
are then released to pond areas.
Dewatering using centrifuges and vacuum filters has been tried
for off- site disposal of precipitated wastes. Synthetic organic poly-
electrolyte coagulant aids are being recognized as valuable in colloid
coagulation. They enhance solid-liquid separation in filtration,
clarification, and thickening processes, and are presently under considera-
tion in industrial waste treatment. BOD removals of over 90 percent
have been achieved in pilot plants by use of synthetic coagulant aids.
(1) Copper
Copper in solution is highly toxic to aquatic life. Therefore,
waste treatment requirements aim for an effluent which contains
less than 0. 5 ppm copper. Large volumes of copper-free water are
used for dilution. Sufficient alkali, preferably lime (Ca(OH).),is
-------
APPENDIX A-9-51
added to raise the pH to near 7. 0. However, lime neutralization
leads to an increase in the hardness values of the water, and
therefore makes it impossible to reuse the water by recirculating
it. As a result, a mixture of sodium hydroxide (NaOH) and sodium
carbonate (Na_CO,) is used to maintain a pH in the range 8 to 9.
£t A
The effluent is crystal clear without the need for settling tanks
or clarifiers.
(2) Zinc
Zinc is removed from waste effluent by chemical precipi-
tation and ion exchange (Reference 2). The latter is being used
more frequently because it offers the possibility of reclaiming
materials for reuse which would otherwise be lost. One of its
limitations, however, is the decreased efficiency of the ion exchange
resins with repeated use. The ion exchange recovery of zinc is
shown in Table A-9-10. In the chemical precipitation,
of lime results in the precipitation of zinc hydroxide. The
efficiency of recovery is dependent upon maintaining an adequate
concentration of lime. This process is shown in Table A-9- 11.
(3) Aluminum
Solvent extraction is used for recovering alumina from waste
solutions. Most of the aluminum is selectively precipitated as
-------
APPENDIX A-9-52
crystalline A1C_ • 6H_O which is thermally decomposed to
o «
produce alumina up to 99. 95 percent pure and to recover HC1
for reuse.
Table A-9-10
Recovery of Zinc by Ion Exchange
Run
#
1
2
3
Total Zn Passed
(Mg)
855
900
1238
Zn Retained
% '
64
68
79
Recovery
" %
99.20
94.10
64.30
Table A-9-11
Recovery of Zinc by Chemical Precipitation
Lime Added
(Mg/1)
300
340
385
425
475
PH
7
8
8,5
9.0
9.5
10.0
Recovery
%
on 4.
£i\l, t
96.5
97.5
97.8
99.5
99.3
Zinc Recovery
mg/mg of Lime
0.868
0.776
0.686
0.632
0.564
-------
APPENDIX A-9-53
REFERENCES
1. 1967 Census of Manufactures. Volume II; Industrial Statistics.
Part II; Major Groups 25-33, U.S. Department of Commerce,
Bureau of Census, January 1971.
2. "Comparative Study of Recovery of Zinc and Nickel by Ion
Exchange Media and Chemical Precipitation, " D. Kantawala,
H.D. Tomlinson, Water and Sewage Works, 1964, pp. R-280
to R-286.
-------
APPENDIX A-10
SIC 34—FABRICATED METAL PRODUCTS, EXCEPT
ORDNANCE, MACHINERY, AND
TRANSPORTATION EQUIPMENT
-------
APPENDIX A-10
SIC 34—FABRICATED METAL PRODUCTS, EXCEPT
ORDNANCE, MACHINERY, AND
TRANSPORTATION EQUIPMENT
SIC 347—COATING, ENGRAVING, AND ALLIED SERVICES
1. ECONOMIC STATISTICS
This section includes establishments engaged in all forms of
electroplating, plating, anodizing, coloring and finishing of metals
(SIC 3471), and those engaged in hot dip galvanizing of mill sheets^
plates and bars, the enameling, lacquering and varnishing of metal
products, and other metal services not elsewhere classified (SIC 3479).
The economic data which is shown covers all those activities. The dis-
cussion of wastes from this industry is largely concerned with those
arising from plating and coating operations.
The two major subsections of the plating and finishing industry
are shown below with data indicating the relative size of establishments
in this industry group.
Size of Establishments
(No. of Employees)
Total 1-4 5-20 20-100 100-500 500-1000
3471 - Plating and Polishing 3241 1237 1149 791 63 1
3479 - Metal Coating 1443 624 470 297 48 3
-------
APPENDIX A-10-2
This data shows that such establishments are primarily shops
with few employees. Only the larger establishments are likely to
have the capability to design their own disposal systems. The re-
maining shops must use disposal methods provided by the equipment
manufacturerSjOr not concern themselves with the problems unless
economic necessity intervenes. Although the census data indicates
less than 5,000 establishments, it is estimated that there are between
15,000 and 20,000 metal finishing facilities in the United States
(Reference 1). This industry is found in every community in the
country and at every sizable military or other Government operational
site.
The value added by this industry,in 1967,was $574.8 million for
plating and polishing,and $289. 6 million for metal coating and allied
services. In 1970,approximately $1 billion was estimated as the annual
value added, or contribution to the GNP, of this industry. This is
approximately 0. 1 percent of the total GNP. While this industry is
relatively small, it should be noted that the value of products shipped
doubled between 1958 and 1967 in each segment, and more than tripled
since 1947.
-------
APPENDIX A-10-3
Value ($) of Primary Products
Shipped
1967 1958 1947
3471 - Plating and Polishing 756.1 349.7 172.5
3479 - Metal Coating 404 184.1 60.8
Although wastes from the plating and coating industry are
small9in comparison with the volume of liquid wastes generated in
other industries, they contain extremely toxic effluents if not properly
treated. These constituents are mainly inorganic acids, metals, and
cyanides. Good treatment methods are available. However, the
statistics on water use within this industry (Reference 2) indicate
that less than one-half of the total water discharged was treated prior
to discharge.
The effect of these waters on fish is significant. A 100-gallon
tank of 50, 000 ppm cyanide solution, although diluted by 50 million
gallons of water, provides enough cyanide to be toxic to fish. One
hundred gallons of chromium plating solution (207,000 ppm Cr),even
though diluted by 200 million gallons of water,will provide enough
chromate to kill most of the fish food (Reference 3).
-------
APPENDIX A-10-4
2. DESCRIPTION OF METAL FINISHING PROCESSES
The plating and coating industry is comprised of a vast number
of metal finishing shops. A variety of metal finishing processes and
techniques are employed, depending on the type of finishes produced
and the specific methods utilized. Several of the metal finishing pri-
mary and auxiliary processes produce wastes, including:
Primary
Anodizing
Phosphating
Chromating
Electroplating
E lectropoli shing
Oxidizing and Blackening
Electrogalvanizing
Auxiliary
Cleaning
Pickling
Finishing
Rock Stripping.
A brief description of each primary and auxiliary process follows.
(1) Primary Finishing Processes
1. Anodizing
Anodizing involves the production of a nonmetallic
oxide coating on metals by means of anode oxidation, i.e.,
the metal article is treated as an anode in a selected
-------
APPENDIX A-10-5
electrolyte. Anodizing baths may contain chromic or
sulfuric acids, or a mixture of acids such as a combina-
tion of sulfuric and oxalic acids. Anodized surfaces may
be finished further by lacquering, staining or other processes.
Anodizing must be followed by water rinsing. Commercial
coatings of this type are produced on a large scale for
aluminum and magnesium, and to a much smaller extent
for zinc, titanium, and other metals.
2. Phosphating
Phosphating involves the production of a primarily
phosphate coating through immersion of metal articles in an
aqueous solution containing metal phosphates. This type
of coating is used particularly in "mass production"
articles such as automobile bodies and refrigerators.
Phosphate coatings can be applied to iron, steel, cadmium,
zinc, aluminum, and various other alloys.
3. Chromating
Production of coatings containing chromium (chro-
mating) is accomplished through immersion in chromates,
chromic acid, or sulfuric acid solutions. Most metals are
chromated in acid solutions; however, aluminum may be
chromated in alkaline solutions as well. Primarily, alum-
inum, magnesium, zinc, cadmium, iron, steel, and nickel
are chromated and,to a lesser extent, tin, copper and
silver. Special additives are used to promote coating
growth, including sulfates, flourides, nitrates, phosphates,
or acetates.
4. Electroplating
After precleaning and/or electropolishing, electro-
plating may be utilized by immersing the article in an
appropriate metal plating bath. The composition of this
bath depends upon the metal and the specific process used
in plating. In general, plating baths contain either alkaline
solutions of cyanides (pHio or above), or acid solutions
which include salts of the metal to be plated. Alkaline con-
ditions must be maintained in cyanide baths to prevent liber-
ation of hydrogen cyanide. In plating processes involving
-------
APPENDIX A-10-6
cyanide baths, cadmium metal and salts and sodium
cyanates and carbonates are used. Cadmium is deposited
principally from cyanide baths, but it may be deposited,
to a lesser extent, from acid baths. For many metals,
both acid and alkaline processes exist for the same metal.
Chromium, zinc, and cadmium are among the most
commonly plated metals.
5. Electropolishing
Electropolishing, known as "brightening," may be
used to provide a final finish or as a treatment prior to
electroplating. This process produces a mirror-like
finish. Electropolishing is performed electrolytically
in baths. These baths may contain sulfuric, orthophos-
phoric, chromic, nitric, etc., acids depending upon the
metal to be polished.
6. Oxidizing and Blackening
Natural protective oxides or hydroxide coatings may
be thickened artifically by oxidizing the metal in salt baths
or aqueous solutions. A blackened oxide coating can be
produced by adding sodium" nitrate or nitrite in an
alkaline bath.
7. Electrogalvanizing
Zinc plating, or electrogalvanizing, may be performed
in acid baths containing zinc sulfate (as a souce of zinc), or
from cyanide baths containing sodium and zinc cyanides
(under alkaline conditions).
(2) Auxiliary Finishing Processes
Prior to any further finishing, stamped and/or machined
items must be cleaned of contaminants. These contaminants
consist of oxide coatings, grease, oils, salt film, and other
-------
APPENDIX A-10-7
foreign materials. Oxide coatings are removed by "pickling,"
the dissolution of the coating by immersion in dilute acid baths
Grease and oil may be removed by immersion in alkaline baths
or by organic degreasing. Waste from these processes include
alkalines, unused acids, and salts of dissolved metals.
To prevent contaimination of the pickling and cleaning
baths, water rinsing is required between and again after these
two stages to prevent contamination of plating and /or finishing
baths. In fact, since the majority of finishing operations are
accomplished through immersion in baths, cold water rinsing
follows every finishing operation. As a consequence, the major
source of effluent is the large volume of rinse water contaminated
with bath solutions. Only after cleaning is the article ready for
a number of different finishing processes (the primary finishing
processes discussed earlier), such as anodizing, electropolish-
ing (brightening), electroplating, phosphating, or chromating.
Sometimes, if defective coatings are produced, they are
stripped and the coating process is repeated. The type of strip-
ping solutions used depends upon the particular coating that must
be stripped. Phosphate coatings are stripped in alkaline solutions
of EDTA (a tetrasodium salt) and phosphoric acid. Chromate
-------
APPENDIX A-10-8
coatings are usually stripped by using solutions of chromic and
phosphoric acids. Racks are used to hold the metal articles
during all finishing operations. These racks build up with
coatings and plating metals and, therefore, must be periodically
stripped.
(3) Typical Metal Finishing Operating Sequence
A specific metal finishing shop may combine any number
of the finishing processes previously mentioned. An example
of a typical operating sequence would be:
Mechanical and thermal treatment (grinding, polish-
ing, abrasive blasting, rolling, pressing, turning,
etc.)
Precleaning with solvents, solvent vapors, alkalai
or other cleaners
Rinsing in cold running water
Pickling in acid solutions or in caustic soda solution
(in the case of aluminum)
Rinsing
-------
APPENDIX A-10-9
Immersion in coating or electropolishing solutions
Rinsing in cold water
Rinsing in hot water with special agents
Air drying
Special after treatment such as coloring, oiling,
greasing, waxing, or lacquering (Reference 1).
3. WASTE CHARACTERISTICS
Primary sources of waste in plating and finishing operations are
as follows:
Rinse waters from plating, cleaning, and other finishing
operations
Concentrated plating and finishing solutions, intentionally
or accidentally discharged
Waste from plant or equipment cleanup
Sludge, filter cakes, etc., produced by naturally occurring
deposition in operating baths, chemical rinsing circuits,
etc.
Regeneration from ion exchange units
Water from vent scrubbers.
-------
APPENDIX A-10-10
Most of the available data on the volume and composition of
electroplating and metal finishing wastes exist for larger plants.
Data demonstrate the wide variation in waste effluent composition
from plant to plant (Reference 1). This variation is dependent upon
local plant conditions, rinsing techniques, and recovery methods.
Little data are available on the volume and composition of
wastes in the smaller finishing shops, especially those that perform
general plating. As a result, it is assumed that waste parameters
are variable. Burford and Masselli (Reference 4) have presented
typical waste concentrations for several different plants, as well as
for the same plant but on different occasions.
These source data indicate that finishing effluents have the
following properties:
pH's ranging from 2 to 11.9
Copper content from 6 to 300 ppm
Iron content from 2 to 21 ppm
Nickel content from 0 to 300 ppm
Zinc content from 0 to 300 ppm
Hexavalent chromium content from 0. 5 to 700 ppm
Cyanide content from 39 to 1,500 ppm.
-------
APPENDIX A-10-11
These data also demonstrate the waste variability from a given source
on different occasions.
In general, total plant waste can range from highly acidic to
highly alkaline depending upon the number of baths used and the
amount of pickling and stripping done. Effluents from most plants
contain high concentrations of toxic cyanide which are used in the
many plating processes. Large concentrations of toxic hexalavent
chromium are also found as a result of metal plating and the extensive
use of chromic acid. A number of other materials such as phosphates,
chromates and plating metal salts can be expected. Some plating
metal salts are particularly toxic,such as hexavalent chromium, lead
and cadmium.
The composition of naturally precipitating metal and processing
reagent sludges are not unlike those of the rinse waters, except that
they are more concentrated. Generally, these sludges are quite toxic
and may be acidic or alkaline as well.
In addition, a number of gaseous and/or airborne pollutants are
produced from the metal plating and finishing operation. These are
primarily dealt with through the use of scrubbers which are connected
to ventilating systems. As a result, those wastes contribute somewhat
-------
APPENDIX A-10-12
to the aqueous waste. Information on gaseous and/or aerosol wastes
is not readily available. Table A-10-1 listing the limitations on air-
borne finishing effluents is presented as an indication of the types of
materials emitted (Reference 5).
4. DISPOSAL PRACTICES AND TREATMENTS
Ultimately, diluted liquid and solid wastes either must be dis-
charged into public waterways and sewer systems or, in the case of
deep well disposal, be hauled away to land fill sites. Reclamation
practices exist for extracting plating metals, acids and process
water. However, employment of these practices is variable.
Usually, rinse water treatment is necessary before disposal.
This is done in order to remove cyanide, hexavalent chromium, oils,
greases, acids, alkalies, and other plating metals. The most widely
used treatment methods involve chemical oxidation and reduction
processes, which remove or convert toxic cyanides and hexavalent
chromium. Other widely used methods are processes including
evaporation, precipitation, filtration, sedimentation, and ion
exchange methods. A variety of more specialized techniques are
available, such as destruction by radiation, dialysis, etc., but are
less commonly used.
-------
APPENDIX A-10-13
Table A-10-1
Maximum Permissible Concentrations of Toxic Gases
and Vapors in Chemical Finishing Processes
Gas or Vapour
Ammonia
Arse nine
Benzene
Hydrogen cyanide
Chlorine
Formaldehyde
Carbon monoxide
Methyl alcohol
Perchloroethylene
Phosgene
Phosphine
Mercury Vapour
Carbon disulphide
Hydrogen sulphide
Sulphur dioxide
Nitrogen dioxide
Carbon tetrachloride
Toluene
Trichloroethylene
Xylene
Sulphuric acid fumes
Hydrogen selenide
Fluorine
Lead dust
Cadmium oxide
Sodium hydroxide fog
Sodium or potassium
Cyanide dust
Chromic acid or
alkali chromate fog
Formula
NH3
AsH3
C6H«
HCN
Cla
H.CHO
CO
CH3.OH
CdjrCCJj
COClj
PH3 Germany-
U.S.A. —
Hg
SOj
H2S
NOj
CO,
f* u r*u
1>(II5 .V,H3
CClj :CHC1
C,H/CH3
HjSO, '
HjSe
F
Pb
CdO
NaOH
NaCN
KCN
NajCrjO?
Western Gcnnuiy
and UJSA.
mg/n,3C) ppmO
70 100
0.2 0.05
80 25
11 10
3 1
6 5
110 100
260 200
1350 200
0.4 0.1
— *. 0.15 0.1
— &> 0.07 0.05
0.1
13 5
60 20
30 20
9 5
160 25
750 200
1050 200
870 200
1
0.2 0.05
0.2 0.1
0.15
0.1
2
0.1
(Cr03)
IU.S.R.
mg/m^*^
20
0.3
100
0.3
1
5
31
50
0.5
0.3
0.01
2
10
10
5(N,05)
100
SO
100
ppm* '
28.5
0.07S
32
0.3
0.3
4
26
39
0.1
0.2
0.8
3.3
7.0
1.0
27
9
23
The following values have been added to supplement Table A-10-1 as they are of special interest
in chemical conversion treatments.
Gas or Vapour
Ethyl alcohol
Ethylene chloride
(dichloioe thane)
Butyl alcohol
Chlorine dioxide
Carbon dioxide
Methylene chloride
Trichloroethane
Vinyl chloride
Formula
CjHs.OH
CHjd.CH2Cl
Qty.OH
ClOj
COj
CHjClj
CH3.ca3
CH,= CH.C1
Maximum permissible
concentration (mg/m3 )•
1880
400
300
0.3
9000
1750
2740
1300
' In air at 20°C and 760 mm Hg pressure, ppm = cc gas vapour per cubic metre air.
-------
APPENDIX A-10-14
(1) Chemical Methods
In general, rinse water is first treated to remove cyanide.
This is followed by treatment to remove hexavalent chromium.
Later, following neutralization, grease and other metals may
be removed by precipitation.
1. Cyanide Rinse Chemical Treatment
Chemical methods for treating cyanide rinses include:
Complete reduction of cyanide by chlorine gas
and/or hypochlorites
Reduction of cyanide to a relatively innocuous
cyanite by chlorine and/or hypochlorites
Conversion of cyanide to ferrus ferrocyanide
by treatment with ferrous sulfates.
These methods involve the addition of oxidizing or other
reagents to either large tanks with constant agitation
(Batch method), or directly to the rinse stream (continu-
ous flow method). Since considerable time is required to
fill one tank and treat the cyanide rinse, two tanks are
usually employed. This way, one tank can be filling while
the treatment process takes place in the other.
In the "destruction of cyanide by chlorine gas"
method, chlorine gas must be added under highly alkaline
conditions in order to prevent the liberation of HCN which
is highly toxic. Since alkaline conditions prevail, the
process is accompanied by metallic hydroxides along with
carbonates and sulfates (depending on the particular
reagents used). If hypochlorites are used, only a suitable
salt (in dry or aqueous form) is added to the rinse water,
thus minimizing sludge formation. This method is more
-------
APPENDIX A-10-15
applicable to smaller plating shops since it requires less
expensive equipment.
In the "cyanide immersion" method, cyanide is
converted to cyanate which is one thousand times less
toxic than cyanide (Reference 6). Conversion processes
require only minutes for complete reaction and may be
carried out, by the addition of chlorine gas under alkaline
conditions or hypochlorites, through either the Batch
method or the continuous flow method. Again, it should
be mentioned that where chlorine gas is used, sludge
formation results.
Cyanides may be precipated as less toxic ferricyan-
ides or ferrocyanides by the synthesis of free cyanide
ions with ferric ions. Unfortunately, this method results
in large volumes of sludge which must be dealt with.
This method is further complicated by the photochemical
regeneration of free cyanide in the presence of light.
2. Chromium Rinse Chemical Treatment
Chemical methods for treating chromium rinses
include the reduction of hexavalent chromium to a less
toxic trivalent chromium using sulfur dioxide of sulfites.
Both large and intermediate plating plants reduce hexa-
valent chromium by using sulfites. The reduction of
hexavalent chromium by use of sulfur dioxide gases is
also utilized in the larger plants.
Recently, sulfur dioxide has been obtained from
waste flue gases in boiler plants. Scrubbers are used for
absorption of sulfur dioxide in the chromium waste solu-
tions. Depending upon the concentration of sulfur dioxide
available, incomplete reduction may result which would
necessitate the use of additional reducing agents.
Reduction,which utilizes agents such as bisulfates,
also requires the use of acids in order to maintain acidic
conditions (pH 2 to 3). It is possible that some savings
may result if sufficient quantities of pickle liquor wastes
are available.
-------
APPENDIX A-10-16
In general, chromium reduction techniques produce
acidic effluent. This effluent contains reduced chromium
and other metals, and requires neutralization. Since
cyanide treatments result in alkaline effluents, neutraliza-
tion of chromium rinse effluents may be achieved by com-
bining the effluents. Generally, neutralization results in
the formation of insoluble carbonates and/or hydroxides
of chromium, nickel, copper and other plating metals.
When ferrous sulfite is used for reduction, iron hydroxide
results. Then solid wastes may be removed by sedimen-
tation, evaporation, filtration, etc. Economic recovery
of precipitated metals, known as the "waste plus waste
method, " has been reported by the U. S. Bureau of
Mines (Reference 7). Alkaline effluents are combined
with stripping solutions to precipitate dissolved metals.
Hexavalent chromium may be precipitated as insol-
uable barium chromate. However, barium is quite toxic
and separation of the precipitate is necessary before dis-
posal.
(2) Evaporative and Ion Exchange Methods
Evaporative and ion exchange methods provide the means for
recovery of cyanides, chromic acid, and other plating metals.
However, these are practical only when the volume of chromic
acid and/or cyanide salts is large enough to be economically
advantageous. Plating operations are generally split into
several kinds of small chromating and cyanide baths, and re-
covery becomes impractical. These techniques are perhaps
best applied to the treatment of rinse waters following plating
operations,so that little or no contamination other than recover-
able metal is present.
-------
APPENDIX A- 10- 17
In ion exchange methods, rinse water is passed through
beds of cationic and anionic exchange resins selected for the
particular application. The beds must be periodically regener-
ated to remove the load of cyanides or metals and this requires the use
of sulfuric acid and/or sodium hydroxide. These solutions are
quite concentrated and generally toxic, and must be treated by disposal
methods previously described, if recovery is not feasible.
Ion exchange has been applied to mixed cyanide and
chromic wastes effluent using a dual-bed process. Mixed wastes
first pass over a cation exchange resin which absorbs metals and
helps break up cyanide complexes, then over anionic exchange
resins to absorb liberated cyanide.
Both alkali cyanide and acidic metallic solutions may
be recovered by evaporative techniques. Rinse waters>contami-
nated by the plating solution, are evaporated to concentrate the
dissolved material and simultaneously produce distilled water.
(3) Electrolytical Methods
Batch wire electrolysis of diluted plating waste has proven
to be cost-prohibitive, since reduction of hexavalent
chromium and oxidation of cyanide is a slow process in
-------
APPENDIX A-10-18
diluted solutions. However, new technology has been designed
(Reference 8) to speed up the processes, making them
efficient and competitive. Such techniques, however, are not
in wide use.
5. IMPACT OF WASTES ON WATER QUALITY
The following paragraphs (Reference 1) summarize the impact
of metal plating wastes on the sewage systems, and the water into
which sewage effluents are released.
Wastewaters from plating and metal finishing plants always end
up in some natural body of water; most of these are surface bodies,
but some are possibly subterranean. However, the routes to these
natural bodies of water are different. A large majority of establish-
ments run their wastes into municipal sanitary sewers. Once in the
sewage system, the industrial wastes are diluted with domestic wastes,
carried along with them to a sewage treatment plant, and then to some
natural body of water. In the sewage system, the toxicity of the plating
waste is decreased by such mechanisms as dilution, mixing, neutrali-
zation, and precipitation, with dilution exerting the greatest effect.
There are many finishing establishments situated in areas where
there is no municipal sewage system. The wastes from these plants
-------
APPENDIX A-10-19
must take a more direct route to natural water bodies. The plants
must provide their own treatment before disposal; the extent of this
treatment will depend on the composition of the waste and on the
levels of pollutants permissible in the stream or lake.
(1) Disposal of Waste into Municipal Sewage Systems
If sufficiently diluted and nearly neutral, plating wastes
are only mildly—if at all—corrosive to sewer structures. But
serious structural damage from corrosion has occurred from
concentrated and acidic wastes not adequately diluted or
neutralized before disposal (Reference 9).
Plating wastes can create toxic conditions directly in
sewers. Sewer workers have been poisoned by cyanide gases
generated from relatively small accumulations of concentrated
plating wastes in sewer systems. Even relatively dilute cyanide
solutions in sewers can be dangerous. Experimentation has shown
that a solution containing as little as 50 ppm of cyanide can
generate lethal concentrations of cyanogen in sewer atmos-
pheres. A maximum of 20 ppm of cyanide in sewer water is
considered a safe level by some, but other investigators state
that 20 ppm of cyanide in small sewers is dangerous and that as
-------
APPENDIX A- 10- 20
low as 10 ppm can be harmful in large sewers where men may
work for long hours (Reference 10).
Plating wastes may also exert indirect toxic effects in
sewers by promoting the anaerobic decomposition of domestic
sewage in sewer lines. Anaerobic decomposition gives rise to
the formation of methane (sewer gas) which has been known to
suffocate sewer workers and which may cause fires or explo-
sions. Fortunately, there are few instances of these phenomena.
Plating wastes also can cause the blockage of sewers by
solids, although this occurs rarely when wastes are sufficiently
dilute.
Plating wastes from plants using secondary treatment
cause the most damage. This is because the chemicals and
metals occurring in these wastes may, if sufficiently concen-
trated, be toxic to the bacterial colonies which make the process
operate. There have been numerous instances where the effici-
ency of secondary treatment plants has been grossly or com-
pletely impaired by slugs of concentrated wastes.
There is another unit operation, practiced by both the pri-
mary and secondary types of plants, in which the metals in
-------
APPENDIX A-10-21
plating wastes are harmful. This is in the so-called "sludge
digestion" step in which primary sludge, either alone or mixed
with secondary sludge, is subjected to treatment by anaerobic
bacteria. In this process the concentrated sludge, still offen-
sive and toxic, is converted to an innocuous, readily disposable
material. Digestion is carried out in the absence of air in
large, closed, heated tanks. The digestion process produces a
mixture of methane, hydrogen, and carbon dioxide which fre-
quently is burned to supply heat for the sewage plant.
The metal components of the plating wastes concentrate
in the settled sludge from primary and secondary treatment and
become even more concentrated in the sludge digestion tanks.
Instances have been reported where sludge digestion processes
were completely halted due to the accumulation of metals (such
as copper) in the digestion tanks. It has been estimated that
when the total concentration of chromium, copper, nickel, zinc,
and cadmium exceeds 400 ppm in digesters, failure can occur.
Such concentrations could be produced by raw sewage containing
1. ^ to 3 ppm of these metals.
Cyanide does not concentrate in sludges and, in fact,
largely decomposes in secondary treatment. However, if the
-------
APPENDIX A-10-22
cyanide content of the raw sewage exceeds certain levels,
enough may be transferred to the digesters to cause trouble.
A steady feed of raw sewage containing 5 ppm of cyanide is
capable of disrupting digester operation.
(2) Disposal of Waste into Streams, Lakes, Etc.
One of the benefits of plating wastes disposal via munici-
pal sewers is that the wastes become highly diluted and mixed
with other wastes; the toxic components are then removed in
the sewage treatment process. This is not true for plants that
dispose of their wastes directly into natural streams and lakes.
Restrictions on the effluents from these plants are significantly
tighter than on effluents destined for municipal sewage systems.
There always is some danger that the components of plating
wastes in streams can be harmful to man. Cases have been
reported where plating wastes were fed to a stream and caused
fatalities to livestock. The major and most frequent danger,
however, is the destruction of aquatic life. This can occur with
extremely low concentrations of cyanides and metal salts.
-------
APPENDIX A-10-23
REFERENCES
1. A State-of-the-Art Review of Metal Finishing Waste Treatment,
Battelle Memorial Institute, for the U.S. Department of Interior,
Federal Water Quality Office, November 1968.
2. 1967 Census of Manufactures, Volume I; Summary and Subject
Statistics, U.S. Department of Commerce, Bureau of the
Census, 1971, pp. 7-21.
3. "industrial Waste: Their Disposal and Treatment, " W. Rudolfs,
ACS Monograph. 1953, p. 288.
4. Theories of Practices of IAD Waste Treatment, Burford and
Masselli.
5. Chemical Hygiene and Accident Prevention, p. 56.
6. "Neutralization of Acid Mine Drainage, " D. W. Hill, Water
Pollution Control Federation Journal, Vol. 41, No. 10,
October 1969, pp. 1702-1715.
7. Mineral Industry Solid Wastes and Our Environment, U.S.
Department of Interior, Bureau of Mines, Staff Report.
8. "Electrolysis Speeds Up Waste Treatment, " Environmental
Science and Technology. Vol. 4, No. 3, March 1970.
9. The Electrolytic and Chemical Polishing of Metals in Research
and Industry, W.J. McGitecart, Pergamon Press, 1959.
10. Symposium on Surface Treatment of Metals, Twenty-Second
Annual Convention of the American Society for Metals,
October 21-25, 1940, Cleveland, Ohio, c.1941.
-------
APPENDIX A-ll
SIC 80 —MEDICAL AND OTHER HEALTH SERVICES
-------
APPENDIX A-11
SIC 80—MEDICAL AND OTHER HEALTH SERVICES
SIC 806—HOSPITALS
1. ECONOMIC STATISTICS
The first hospitals in the United States were established more
than 200 years ago. First attempts at caring for the sick was to pro-
vide shelter, such as almshouses for the poor. The first of these
almshouses was founded in Philadelphia in 1713, followed by others
in other areas. The first bona-fide hospital in the United States
solely for the physically and mentally ill was established in 1751 and
was known as the Pennsylvania Hospital. Other hospitals grew out of
a need to provide a place for clinical practice for medical schools.
The first listing of hospitals in 1873 showed a total of 178 institutions.
By 1909,this count had increased to 4, 359 facilities of all types. In
1914,the number rose to 5, 047, and increased to 6, 852 institutions in
1928, but showed a decline to 6, 166 institutions by 1938. However,
during this period the total bed capacity increased. In 1963 the
number of hospitals increased to almost 8, 200.
(1) SIC Classification and Description
SIC 80—Medical and Other Health Services,includes esta-
blishments primarily engaged in providing medical or other health
-------
APPENDIX A-11-2
services to persons. Associations or groups primarily engaged
in providing medical or other health services to members are
included, but those which limit services to the provision of
insurance against hospitalization or medical costs are excluded.
SIC 806—Hospitals,in eludes establishments primarily engaged
in providing hospital facilities and clinics and dispensaries.
Hospitals are divided into two types: (1) general or short-term,
and (2) specialty or long-term facilities. These are briefly
described as follows:
General Hospitals—General medical and surgical
hospitals are establishments that provide diagnostic
and treatment services for patients who have a
variety of medical conditions both surgical and
non -surgical.
Specialty Hospitals— These are establishments that
usually limit their admissions to patients with
specified illnesses or conditions only. These gen-
erally include: psychiatric, geriatric and chronic,
and tubercular hospitals.
-------
APPENDIX A-11-3
Each state requires that hospitals be licensed in order
to operate. However, requirements and standards for licensure
vary considerably from state to state. State agencies—in most
states, the health department—have the responsibility for the
licensing of these facilities. Accreditation standards, unlike
licensure, do not vary from state to state. Participation in this
program is voluntary on the part of each hospital. Accrediation
is made by the Joint Commission on Accreditation of Hospitals
(JCAH) for one- or two-year periods or may be withheld if the
hospital does not meet specific standards.
(2) Number of Establishments and Relative Concentration
In 1970,there were approximately 6, 574 general hospitals,
and 1,064 specialty hospitals in the United States (see Table
A-11-1). This amounts to a 2 percent decrease in the number
of general hospitals, with the southern region having the
largest concentration. Among the states reporting the greatest
number of general hospitals was California having 582, followed
by Texas with 547. The western region had fewer specialty
hospitals than other parts of the country. Tubercular hospitals
were mostly located in the north central region,with New York
leading, followed by California.
-------
Table A-11-1
Hospitals by Region—1970
Region and Division
United States
Regions:
Northeast
North Central
South
West
Total
Hospitals
7, 638
1, 367
2, 181
2, 649
1,441
General
Medical
and
Surgical
6,574
1,051
1,894
2,353
1,276
Total
1,064
316
287
296
165
Soe<
Psychi-
atric
494
148
157
116
73
:ialtv
Geriatric
and
Chronic
126
63
19
24
20
Tubercular
108
14
46
38
10
Other
336
91
65
118
62
M
-------
APPENDIX A-11-5
(3) Bed Capacity
Table A-11-2 gives a breakdown of both types of hospitals
with respect to size in terms of bed capacity. Hospital bed
capacity data reveal that the United States had a bed capacity
of over 1 million in 1970, approximately 2 percent over that
of 1969, or about 5 beds per 1,000 population. The NorthCentral
region had the highest bed-to-population ratio. The ratios
ranged from 7. 6 in North Dakota to 3. 9 in Maryland. The
specialty hospitals had a capacity of over 500 thousand, about 35
percent of total hospital bed capacity. These were utilized by
the psychiatric hospitals (83 percent), geriatric and chronic
disease hospitals (7 percent), with tubercular and other
hospital services using the remaining 10 percent. The bed-to-
population ratio varied from 5.2 (in Massachusetts), to a low of 0. 6
beds (in Arkansas). Table A-ll-3 shows the number of hospitals,
total hospital beds, and bed-to-population ratio for selected
years between 1963 and 1970.
(4) Hospital Admissions
During 1970,the general hospitals received about 32 million
admissions or about 157 per 1000 population. The southern
-------
Table A-11-2
Bed Size of Hospitals: 1970
Bed size
Total
Less than 25 beds . .
25-49
50-74
75-99
100-199
200-299
300-499
500-999
1, 000 beds or more .
Total
hospitals
7,638
618
1, 658
1,054
758
1, 554
726
695
346
229
General
medical
and
surgical
6,574
508
1 520
944
661
1, 360
644
621
260
5
Total
1,064
110
138
110
97
194
82
74
86
173
Psychi-
tric
494
16
45
35
38
74
33
33
57
163
Specialty
Geriatric
and
chronic
126
6
10
15
10
27
20
15
18
5
Tubercular
108
2
9
14
14
31
13
20
5
Other
336
86
74
46
35
62
16
6
6
5
M
2
0
X
-------
Table A-11-3
Hospitals and Hospital Beds: Selected Years 1963 Through 1970
Year
1970
1969
1968
1967
1963
1970
1969
1968
1967
1963
1970
1969.
1968
1967
1963
Total
Hospitals
7,638
7,845
7,991
8,147
8,183
General
Medical
and
Surgical
4,415
6,715
6,539
6,685
6,710
Total
Specialty
Psychi-
atric
Geriatric
and
Chronic
Tubercu-
lar
Other
Facilities
1,064
1,130
1,452
1,462
1,473
494
506
494
573
581
126
189
291
333
211
108
116
129
169
258
336
319
538
387
423
Beds
1, 534,779
1,656,908
1,564,444
1,631, 101
1,549,952
1,004,415
989,733
934,297
958,729
811,876
530,364
576, 175
630,147
672,372
738,076
437,969
477, 309
503, 042
545,913
614,014
38. 144
40,799
43,291
61,211
38,213
19,836
20, 960
25,381
33,335
50,074
Beds per 1, 000 Population
7.6
7.8
7.9
8.3
8.3
5.0
5.0
4.7
4.9
4.3
2.6
2.9
3.2
3.4
4.0
2.2
2.4
2.5
2.8
3.3
0.2
0.2
0.2
0.3
0.2
0.1
0.1
0.1
0.2
0.3
34,415
37, 116
57,803
31,913
35,658
0.2
0.2
0.3
0.2
0.2
8
>
-------
APPENDIX A-11-8
region accounted for approximately 33 percent of the total, with
California and New York showing 17 percent. Discharges just
about equalled the admissions. The daily average for patients
in the general hospitals,during 1970,numbered 777, 442 patients.
The total admission and discharge for the general hospitals are
given in Table A- 11-4.
The specialty hospitals admitted approximately 1.1 million
persons during 1970, and discharged about the same number. The
northeast region led the nation in number of admissions. Total
admissions approximated a ratio of 2.2 average daily residents per
1000 population, and averaged about 450,000 persons per day.
These figures are shown in Table A- 11-4.
(5) Services
The services provided in the hospitals are varied. The
specialty hospital services,in contrast to those of the general
hospitals, primarily include department of occupational therapy and
social work. Very few of the specialty hospitals reported having
surgical departments. However, 9 percent of these hospitals
reported having a family planning service. Table A- 11-5
shows a detailed breakdown of services for both types of hospitals.
-------
Table A-11-4
Average Daily Patients, Total Admissions,
and Discharges for Hospitals by Region - 1970
Region and Division
United States
« It Regions:
g •£ Northeast
« g North Central
S South
West
United States
S 73 Regions:
•2 -tJ Northeast
o o.
w to North Central
«. o _ lt
co tc South
West
Number
Average
Daily
Patients
777,442
195,303
228,121
237,121
116,897
450,557
171,108
109,107
129,404
40, 938
Admissions
31,632,665
6,848,552
9,097,216
10,249, 186
5,437,711
1,161,726
389, 773
257,361
343, 982
170,610
Discharges
31,634,594
6,854,174
9,092,324
10,243,504
5,444,592
1, 174,534
392,355
261,999
343,987
176,193
Number per 1,000 Population
Average
Daily
Patients
3.9
4.0
4.0
3.8
3.4
2.2
3.5
1.9
2.1
1.2
Admissions
156.9
140.4
161.4
166. 1
159.3
5.8
8.0
4.6
5.6
5.0
Discharges
156.9
140.5
161.3
166.0
159.5
5.8
8.0
4.6
5.6
5.2
M
2
d
R
CO
-------
Table A-11-5
Hospital Services by Type - 1970
Hospital Services
Total
-------
Table A-11-5
(Continued)
Hospital Services
Physical therapy dept.
Postoperative rec. rm.
Premature nursery
Psychiatric services:
Inpatient unit
Outpatient unit
Partial hosp. prog.
Emergency services
Psychiatric foster
and /or home care
Radioisotope facility
Radium therapy
Rehabilitation services:
Inpatient unit
Outpatient unit
Renal analysis:
Inpatient unit
Outpatient unit
Self- care unit
Social work department
X-ray therapy
Hospitals
Reporting
4,176
4,770
2,471
1,419
1,175
739
1,142
242
2, 175
1,583
994
793
649
430
541
2,379
1,997
General
Medical
and
Surgical
3,743
4,507
2,450
947
834
450
913
70
2,132
1,562
622
594
642
424
397
1,678
1,947
Specialty
Total
433
263
21
472
341
289
229
172
43
21
372
199
7
6
144
701
50
Psychi-
atric
184
106
1
432
316
272
224
169
12
5
181
88
1
1
89
412
22
Geriatric
and
Chronic
83
14
-
16
5
3
1
1
3
2
54
18
1
1
16
67
6
Tubercular
19
36
-
4
-
1
-
-
1
-
24
4
-
-
7
69
1
Other
147
107
20
20
20
13
4
2
27
14
113
89
5
4
32
153
21
W
2
D
Source: Unpublished data from the National Center for Health Statistics master facility census.
-------
APPENDIX A-11-12
(6) Hospital Employment
In 1970, nearly 2.5 million persons were employed either
full- or part-time in the general hospitals. Approximately 80
percent of these were full-time employees, averaging out to 2. 9
full-time employees per patient. In the specialty hospitals,more
than 400, 000 persons were employed, of which 379,000 or about
95 percent were full-time personnel. There was less than one
full-time employee per patient. Seventeen states reported more
than one full-time employee per patient.
2. WASTE CHARACTERISTICS
(1) Description of Hospital Wastes
Waste materials generated by hospitals can be divided into
several descriptive types which include the following:
General rubbish—Composed of housekeeping materials
such as newspapers, cardboard and other paperstuff,
flowers, scraps from wastebaskets, disposable gowns,
linens, splints, rubber and cloth.
Food residues—Self explanatory.
-------
APPENDIX A-11-13
Pathological wastes—Comprised of tissue taken at
autopsy or during surgical procedures, animal
carcasses and wastes, microbiological wastes
and cultures, bandaging material, blood and serum.
Radioactive wastes—Self explanatory.
Drug residues and solvents—Includes glass and plastic
containers.
Syringes, needles test tubes and other disposable
surgical items—Self explanatory.
An increasing volume of solid waste generated by hospitals
is due,in large part,to the use of disposable or use-and-discard
items in the hospital environment. As a minimum, approximately
125 such articles are in constant use in the performance of
surgical techniques, laboratory functions, diet preparations,
nursing and general housekeeping services. Two reasons why
plastic and/or other types of disposable items have enjoyed ever-
increasing use arer(l) the role they play in controlling infection,
and (2) economy. In spite of well-designed systems for autoclaving
and maintaining sterility, a greater potential for infection exists
with reusable items than with the use of disposable counterparts.
-------
APPENDIX A-11-14
The economy factor associated with the use of disposables is
not as well documented. Although economies are present in
certain areas, additional expense and demands are present in
others. The increase in bulky shipping cartons alone, adds
considerably to the solid waste volume. Increases in other
elements of hospital waste appear to be related directly to the
patient load of the hospitals.
(2) Hazardous Materials in Hospital Wastes
Accident risk involved in the disposal of needles, syringes,
glass and surgical items, as well as personal and/or environmental
contamination associated with the handling and disposal of patho-
logical materials,appear to be the unique problems associated
with disposal of hospital wastes. The quantities of drug residues,
radioactive wastes or other special chemical wastes do not appear
to present signal hazards. Although radiopharxnaceuticals are
being used in increasing quantity, the half-life of the diagnostic
agents used is quite short and thus, unused materials and other
radioactive wastes decay very quickly to low radiation levels.
The amount of hospital waste has increased from approximately
4 pounds/patient/day, in 1955,to a current figure of approximately
19 pounds /patient /day. The estimated per capita figure for the
-------
APPENDIX A-11-15
United States population is approximately five pounds per day.
One reason for the larger figure estimated for the hospital
patient,is that there are 2. 9 full-time hospital employees per
patient, each contributing substantially to the solid wasteload
of the hospital.
3. CURRENT DISPOSAL PRACTICES
The majority of hospitals dispose of solid waste by incineration,
landfill or a combination of the two processes. Prior to removal to
landfill, many institutions utilize compacting to reduce the volume of
waste that must be disposed of. Liquid wastes are diluted or neutralized
and introduced into the sewage system. Pathological wastes are usually
incinerated. However, prior to incineration, microbiological wastes
may be autoclaved. Radioactive wastes are given to service contracters
or returned to the manufacturer. Unused drug products are flushed
into the sewage system, incinerated or returned to the manufacturer.
Syringes and needles are broken or crushed prior to incineration or
removal to landfill. Several hospitals sterilize food residues and make
them available for animal feed.
To obtain some estimate of waste material quantities and com-
position, inquiries were made at a number of general hospitals repre-
senting a total of 5, 281 beds. At each institution, the hospital
-------
APPENDIX A-11-16
administrator or his designate provided available information. A
summary of waste quantities estimated for each of the hospitals
is presented in the following tabulation:
Estimated Solid Waste
(pounds/day)
32,000
7,200
7,000
3,500
19,000
3,000
2,800
7,650
2,700
Hospital
1
2
3
4
5
6
7
8
9
Total
Number of
Beds
1300
1000
758
600
430
377
350
350
116
5,281
85,200
The estimated average wasteload for these hospitals, as a group, is
16.13 pounds/bed/day and the range 5.8 - 45.0 pounds/bed/day.
Disposal practices employed by some of these hospitals are as
follows:
-------
APPENDIX A-11-17
Hospital No. 1 - The facility disposes of approximately 32,000
pounds of waste per day using incineration, compacting and sanitary
landfill. Approximately 16,000 pounds are incinerated. Pathologic
wastes and all microbiological materials are included in that fraction
that is incinerated. Radioactive wastes are disposed of by service
contract. Unused drugs are returned to the manufacturer or flushed
into the municipal sewage system.
Hospital No. 2 - The waste is divided into several types:
(1) solid wastes including papers, flowers, general trash; (2) food
residues; (3) non-burnables such as plastic and rubber materials;
(4) pathological wastes, including animal carcasses, autopsy and
surgical wastes and microbiological wastes (tubes, cultures, petri
dishes); (5) radioactive wastes; (6) syringes and needles; and (7) return
or low potency drugs.
Solid wastes (7,000 pounds) are incinerated daily at a municipal
incinerator. Food residues (100 pounds per day) are sold to a farmer
who, in turn, sterilizes the material and utilizes it as animal fodder.
Non-burnables (100 pounds/day) are disposed of at a municipal dump.
Hypodermic needles and syringes, included as burnables.are dis-
assembled and broken prior to incineration. Pathological wastes are
incinerated before or after autoclaving. Liquid residues are autoclaved.
-------
APPENDIX A-11-18
diluted and poured into the drain. Radioactive wastes are disposed of
by service contract except for syringes* These are stored in a
lead vehicle until a low-level of radioactivity is reached at which
time they are disposed of by incineration.
Hospital No. 7 - Solid wastes (51000 pounds/day) are disposed
of primarily by a contract service. No information as to the final
disposition (incineration, landfill) was available. Autopsy remains
are either incinerated or buried on the premises. Microbiological
wastes are autoclaved prior to incorporation into the general waste
collection.
The disposal practices described for these hospitals are typical
of those employed by all the hospitals at which inquiries were made.
The following conclusions were derived from the information obtained:
The quantity of solid wastes generated by hospitals is
increasing annually.
The rate of increase in solid waste generation is largely
the result of the broad usage of "use and discard items"
in the medical and surgical environment.
The primary methods of solid waste disposal practiced
by hospitals are incineration and landfill,or a combination
-------
APPENDIX A-11-19
of the two. Pretreatment consists of compacting and in
some instances, sterilization.
Although estimates of total solid wastes are available,
quantitative data for pathological and other potentially
hazardous wastes are limited and unreliable.
Although some information regarding the quantity and composition
of solid hospital waste was obtained from several hospitals, minimal
information describing the quantities of pathological wastes generated
was obtained. One estimate was obtained from a survey of solid waste
practices utilized by the United States Air Force (Reference 1). A.
questionnaire survey of solid waste practices was conducted on all Air
Force installations and data were made available on 98 major installa-
tions. To obtain an idea of the composition of the pathological wastes
generated, the questionnaire requested percentages in the following
categories: tissues, plastics, bandages, paper and "other. " Some items
described in the response to the "other" category included: syringes,
kitchen wastes, serum, cardboard, drugs, glass, blood, splints, vials,
test tubes, petri dishes, cultures, needles, metal, rubber and cloth.
The difficulty in obtaining accurate quantitative composition data is
obvious.
-------
APPENDIX A-11-20
Reported pathological waste generated at medical
treatment facilities varied from 0 to 22, 700 pounds per week. For 77
bases with an in-patient capability, the per capita production of
pathological wastes varied from 0.04 pounds per bed per week to
181.6 pounds per bed per week. There were 21 bases having no beds
or no estimate of the amount of pathological waste. The mean for
those installations having in-patient capability (77) was determined to
be 5. 63 pounds per bed per week (median =1.21 pounds per bed per
week). The majority of the installations dispose of these wastes by
incineration and landfill. Of the bases reporting, 68.0 percent use
incineration only, 13.4 percent use landfill only, 16. 5 percent use a
combination incineration and landfill, and the remaining 2. 1 percent utilize
incineration, landfill and sewage disposal. Approximately 40 percent
of those installations using landfill as the primary disposal technique
autoclave the materials prior to disposal.
4. HAZARDOUS EFFECTS OF WASTES
The danger of disease transmission from hospital wastes is
present to a greater degree than from ordinary domestic refuse.
The cart system of collection, used within the hospital facility, results
in a potential for contamination and accident. Several hospitals use
gravity chutes for collecting waste from the generation source,prior
-------
APPENDIX A-11-21
to removal to disposal sites. Microbiological studies performed on
these installations have suggested a contribution to environmental
contamination.
There does not appear to be any clearly defined solution to the
potential problem of environmental contamination resulting from hospital
wastes. A -wet pulping system is receiving some use as a desirable
means of waste collection. The system reduces the majority of wastes
to a pulp or slurry which is dewatered prior to transport to the ultimate
disposal site. Although the weight of residues is considerably greater
than that of the original material,because of the water residue, an 85
percent reduction in volume is accomplished.
To minimize the accident and contamination risk accompanying
the increased use of disposable items (syringes, needles, blades, etc.),
hospitals are currently destroying such items prior to incineration*
disposal or landfill sites. Another approach currently under investi-
gation is a low-temperature melting process by which such items can
be cast into blocks for ultimate disposal. This process would entrap
infective material within the mass and also permit sterilization of the
exposed surface area.
The possibility of environmental contamination by incinerator
effluents also exists. Although air pollution control regulations usually
-------
APPENDIX A-11-22
require a minimum of effluent contaminants, the control devices
(settling chambers, scrubbers),are not designed to control the
emissions of pathogenic organisms which require high temperature
destruction.
Hazards associated with the disposal of radioactive wastes,
although possible, do not appear to be of great magnitude. The majority
of materials used routinely have relatively short half-lives and decay
to safe levels of emitted radiation is rapid. Chemical toxicity associated
with these substances is small because of the relatively low concentration
of chemical entities in radioactive Pharmaceuticals.
-------
APPENDIX A-ll-23
REFERENCES
1. Solid Waste Practices in the United States Air Force. U.S.
Air Force, Air Force Weapons Laboratory, Kirtland Air
Force Base, New Mexico, Technical Report No. AFWL-TR-
71-119, October 1971.
-------
APPENDIX A-12
RADIOACTIVE WASTE
ATOMIC ENERGY COMMISSION
-------
APPENDIX A-12
RADIOACTIVE WASTE
ATOMIC ENERGY COMMISSION
1. INTRODUCTION
The radioactive waste materials produced in the United States
are from operations of the U. S. Atomic Energy Commission (AEC).
frcm a rapidly growing nuclear power industry, and from medical
and industrial applications. Most of the presently stored and buried
radioactive wastes are from past AEC operations having to do with
our nuclear weapons program. The AEC accumulated wastes are dis-
cussed in Section 5 of this Appendix. In the future, our largest
quantities of radioactive wastes will result from the operations of
nuclear reactors in the power industry and the associated nuclear fuel
cycle. In practice medical and industrial applications do not produce
significant quantities of radiotoxic waste materials. This also holds
true for many of the steps in the nuclear fuel cycle. Mining, milling,
conversion and enrichment operations produce some radioactive wastes
since uranium is in itself radioactive. The wastes from these operations,
however, are small, both quantity-wise and toxicity-wise, compared to those
-------
APPENDIX A-12-2
produced by the fissioning of uranium within the fuel assemblies of a
nuclear power reactor. When the reactor fuel assemblies are spent
they are transferred to a reprocessing plant for recovery of the unused
uranium and the produced plutoniutn, and it is during this operation that
high-level waste is collected. The fuel fabrication operations which
utilize recovered plutonium are also significant producers of radio -
toxic wastes.
2. HAZARDOUS EFFECTS RATING
It is essential to remember during a reading of the following
sections of this appendix that the quantities of radioactive matter
released during the various operations are given in curies but that
the potential hazard is not directly in proportion to the curies released.
The measure of the hazard is the potential radiation dose which may
be received by humans from the release of given curie quantities of
(2)
specific radionuclides. The radiation dose unit is rem .
* A curie (Ci) is a unit denoting an activity of 3. 7 x 10*0 disintegration
per second from a given quantity of radioactive material.
(2)
A rem is a unit of dose equivalent to an imparted energy of 100 ergs/
gram of matter times quality and distribution factors.
-------
APPENDIX A-12-3
In this respect the International Committee on Radiological
Protection (ICRP) and the National Council on Radiation Protection
and Measurements (NCRP) have established limits of exposure for
the general public and have classified the radioisotopes on the basis
of the concentrations that are permissible as soluble or insoluble
material in air and in water media without exceeding the exposure
limits. To illustrate, an examination of the two radionuclides
Na-22 and Tc-99m in an insoluble form would show that a microcurie
_ g
(uCi or 10 Ci) of each would expose the lung of a man to 0. 8 rem
and 0.00053 rem, respectively. That is, Na-22 in this form would
produce a dose 1500 times greater than an equal quantity of Tc-99m.
Accordingly, to assure an equal degree of safety, the maximum
permissible concentrations (MPC) of these radionuclides allowed in
-10 -7
the air for their insoluble forms are 3 x 10 Mc/ml and 5 x 10
/xCi/ml, respectively, or roughly in the inverse ratio to the
radiation exposure dose that equal quantities of each would produce.
In addition to determining MFC's for the radionuclides based
on the exposure they produce per unit quantity of intake, other
effects, such as an ability of a plant or an animal to concentrate
a particular isotope, are taken into consideration when determining
its acceptable concentration. In some cases it is necessary to
restrict the total quantity release of a particular isotope rather than
-------
APPENDIX A-12-4
permit the release of unlimited quantities at low concentration. In
Table A-12-1 a tabulation based on the relative hazard rating of the
radionuclides is given. This specific rating system was developed
in connection with the establishment of the agreed upon international
quantity limitations that have been placed on packages (Type A and
Type B). In addition to quantity limitations each of these types of
packages must meet specific performance requirements before it
is an acceptable package for use in transporting radioactive
materials.
In its regulatory program the U. S. Atomic Energy Commission
has announced a policy of restricting radioactive releases to the
environment to "as low as practicable" and have generally defined
this value for light water power reactors.
At the recent rulemaking hearings of the U.S. AEG the design
objectives were set forth with regard to effluents from light
water reactors. In the case of liquid effluents, the design objectives
were established such that,under the unlikely conditions whereby an
individual received his total drinking water supply and a portion of
his food from the effluent discharge,the exposure would not exceed
5 mrem/year. Briefly, the exposure was limited to this value by
establishing as the design objectives 20 pCi/1 (2 x 10~11Ci/l)
-------
Table A-12-1
Radioisotopes Listed in Order of Relative Hazard
1
XuclioV:
(1) <2)
T>«o
,,Pa:jl
,4Pu=»
t4P"«,C
t4Pn!i:
"A-QlM,
CpiiJ*
rsCf:s"
Cm!1*
..A in141
.jAnv"
Cintis
MCin««
Pu!"
,Jcf;l"
,,Ra»«
Thbrinm-2'JO
Pro(Qcl:nniii!-231 •
Pliitonr'im-JSs)
I'!utonunii-'J40
O.lifornnim-249
P;utominn-242
Actiiiium-227
Ncptunium-237
Cu-iuin-24o
C:ilifo:!!mm-230
Curiuin-246
AmiTicinm-2ll
AnuMifiim-.MS
Cmmm-24.1
Curium-244
Thonum-228
Plutommn-238
CiiliiorzmiMi-252
Kadium-sKO
Iiuolnlilo form
LIIII,; DOKU
{r. -nlvfi
(3)
5.4 v 10
0.1 v 10
•i 0 ' 10
00-10
6.8 X 10
58x 10
2.6 x 10*
5.6 x 10
6.2 x 10
• 10"'*
(i/. 10-"
«x 10-'3
5 A 10-"
6 x 10-"
8 x 10-"
10-"
2 x 10-"
2 x 10-"
S.N 10-"
2.- 10 "
2x 10 "
2x 10-"
3 x 10-"
3 x 10-"
7 x IO-"
2x 10-" .
10-"
Inhalation
doso
(rom/nc)
(6)
2.8 X JO4
9.0 X !«'
7.0 x 10'
7.0 x 10»
7.0 x 10»
6.0 x' 10*
5.0 x 10s
2.8 x 10'
2.S x 10'
2.4 x 10J
2.2 x 10»
2.2 x 10'
2.0 x 10s
1.8 x 10*
1.3 x 10*
l.OxUH
7.0 x 10'
5.>x 10'
3 0 x 10s
Cittical orKan
(7)
Bone
Bono
Bone
Bone
Bone
Bono
Bono
Bone
Bone
Bone
Bono
Bonn
Bono
Bone
Bone
Bone
Bono
Bone
Bone
Wouml doso
(rcm/no)
<8)
•1.1 A 10s
•3.6 \ 104
•3.0 x 104
•3.0 x 104
•2.8 x 104
•2.4 x 104
• 2.0 x 104
•1.2X104
•1.1 x 104
•l.Ox 104
•9.0 x 10*
•9.0 x 10n
•8.0 x 10»
•7.0 x 10»
•5.5 x 10*
•4.0 x 10*.
•2.8 x 10*
•2.2 x 10'
•l.Ox 10'-
Maximum
per-
mmible
botlv
'""el"
(9)
0.05
0.02
0.04
004
0.04
0.05
0.03
0.06
0.04
0.04
0.05
0.03
0.05
0.09
P.1
0.02
0.04
0.01
0.1
Specific
activity
c/g
(10)
1.94 x 10-*
4.52 x 10-'
6.1 x JO-'
2.27 x 10-»
3.05
3.9 x 10-'
7.2 x 10
6.9 x 10-4
1.04 x 10->
1.31 x 10«
3 64 x 10-'
3.24
1.S5 x 10-1
4.21 x 10
8.2 X 10
8.3 x 10'
1 68 x 10
6.5 x 10s
9.8 x 10-'
W
2
a
to
-------
Table A-12-1 (Continued)
Muclido
(1)
pu:n
;iu»*
"rb"'
(.Cmsls
t.Th"'
§,UMJ
jfU18*
»»Sr*°
ttuui
,7Bk*"
t4Posl°
jjU~J
§,Ku52>
8§
t|l*aSM
A ftltB
(jKn11*
..Co1"
Th="t
toTh1M
j]Sm14'
,0Nd141
T Tt3B
\jnat
t,U5JS
1JI»»
(1Bi110
MIU*
t»IIil
8iAt*"
eiEuut
"Pb"-o
Y"
Ru104
,,Sr»
(!)
Plutoniutn-241
Uranium-232
Radium-228
Lcad-210
CuriMm-^42
Thonum-227
Uraim-m-233
Uraimim-z34*
Strontium-90
Uranium-236
Bcrkclium-249
Polonmm-210
Uraniii:n-2:tO
Ilmlmm.2'J:»
Kudi'itn-L'24
Protnctmium-230
Actiniiuh-223
Knropi'im-154
Cerium -144
Natural thorium
Thonum-232
Snnir.rium-147
Ncodymium-144*
Uramum-238
Natural uranium
Urc.nium-235
Iodine- 129
Bismuth-210
Iodine- 126
Iodme-131
Astutinc-211
Eiu opium- 152
(13 \rs)
Lcad-212
Thulium- 170
Yttrium-91
Huthcnium-106
Strontiurn-89
Insoluble form
Lung Uoso
(rom/no)
(3)
5.9 x 10-'
2.3 x 10*
1.7 x 10*
28x 10
43x 10
40x 10
Cox 10
5.4 x 10
1.2
5.3 x 10
5.6 x 10-*
34 x 10
•fi 7 x 10
•3.0 x 10
•1.7y 10
3.7 x 10-'
•2.4
9.6 x 10~l
10
2 8 x 10'
5.2 x 10
2.6 x 10
2.3 x 10
49 x 10
1.1 X 10*
5.1 x 10
9.3 x 10-'
2.0
2 5 x 10-*
3.0 x 10-*
1.1
3.7 x 10-'
•1.7
2.0 X 10-1
2.3 x 10-'
•1.2
2.0 X 10-1
(MFC) a
l«8hr wk
lie/ml
(4)
10-*
9 x 10-'*
10-"
8xlO-»
6 x 10-"
6x10-"
4x 10-"
4 x 10-"
2 x 10-*
4x 10-"
4x 10-'
7 x 10-"
4 x 10-"
8 x 10-"
2 x 10-"
3 x 10-"
6 x 10-*
2xlO-»
2x10-*
10-"
4 x 10-»
7 x 10-"
10""
5x 10 -"
2 x 10-"
4 x 10-"
2 x 10-»
2 x 10-*
10"'
10"'
10~*
Ox 10-»
7 x 10-»
10"*
10"*
2 x 10-*
10-
Soluble form
(MFC) a
108 hr wk
tio/nil
(8)
3 x 10-»
3 x 10-»
2 x 10-"
4 x 10-"
4 x 10-"
lO-io
2 x 10-"
2 x 10 •'•
10-"
2 x 10-"
3x10-"
2 x 10-"
10-"
G x 10-"
2x10-'
6 x 10-"
3 x 10-*
3 x 10-*
6 x 10-"
7 x 10-"
2 x 10-"
3 X 10-"
3 x 10-"
3 x 10-"
2 x 10-:e
6 x 10-"
2 x 10-»
3xR)-*
3 x 10-*
2 x 10-*
4 x 10-*
6 x 10-»
10"*
10~*
3 x 10-*
10-*
Inhalation
iloM
(rom/ue)
(8)
1.3 x 10*
1.1 x 10*
1.2 x 10*
5.5x10
5.0 x 10
2.8 x 10
2.3 x 10
2.3 x 10
3.6 x 10
1.9 x 10
1.2x10
1.2x 10
1.1 x 10
5.5
1.6
6.0
2.0 x 10-1
3.3
1.1
3.6xlO«
3.6 x 10*
2.0 x 10*
2.0 X 10*
8.0 x 10
8.0 x 10
1.9x10
7.0
1.1
1.8
1.6
1.4
4.5xlO-»
4.0 x 10-»
4.0 x 10-'
3.3 x 10-»
3.8 x 10-*
4.0 x 10-'
Critical organ
(7)
Bone
Bone
Bone
Kidnoy
Livor
Bone
Bone
Bone
Bone
Bone
Bone
Spleen
Bono
Bono
Bone
Bone
Bone
Bone
Bono
Bone
Bone
Bone
Bono
Kidnoy
Bono
Bone
Thyroid
Kidney
Thyroid
Thyroid
Thyroid
Kidnoy
Kidney
Bone
Bone
Kidney
Bone
Wound dow
(rara/uo)
(8)
•5.6 x 10*
•4.6 X 10*
•4.0 x 10*
•2.0 X 10*
•2.0 x 10s
•l.lx 10*
•9.0x10
•9.0x10
•9.0 x 10
•7.5x10
•5.0 x 10
•5.0 x 10
4.2 x 10
1.4x10
4.0
•2.6x10
8.0 x 10-1
•1.3x10
•4.5
1.4 x 10'
•1.3 X 10»
•8.0 x 10*
•8.0 x 10*
•3.0 x 10*
•3.0 x 10*
•7.5 x 10
•9.0
•4.0
•2.2
•2.0*
•1.8
•1.8
1.4
•1.5
•1.3
1.6 x 10-»
•1.0
Maximum
per-
miMibl*
hnHv
owijr
burdon
(9)
0.9
0.01
0.06
0.4
0.05
0.02
0.05
0.05
2.0
0.06
0.7
0.03
7 x 10-'
O.C5
0.06
0.07
0.04
6.0
6.0
0.01
0.04
0.1
0.1
5 x 10-*
0.03
0.03
3.0
0.04
1.0
0.7
0.02
20.0
0.02
9.0
6.0
3.0
4.0
Spaeifio
antlvitjr
c/g
(10)
1.14x10*
2.08 x 10
2.34 x 10*
8.8 x 10
3 32 x 10»
3.17 x 10«
9.5 x 10-*
6.2 x 10-*
1.45 x 10*
6.3 x 10-1
1.8 x 10*
4.5 x 10s
2.73 x 10«
5.0 x 10«
1.6 x 10*
3.21 x 10*
2.24 x 10*
1.45 X 10*
3.18x10*
Special
Definition
1.11 x 10-'
1.95 x 10-*
4.97 x 10-«»
3.33 x 10-'
Special
Definition
2.14x10-'
1.62 x 10-«
6.6 x 10-<
7.8 xlO*
1.23 x 10*
2.06 x 10*
1.85 x 10*
1.4 x 10*
6.0 x 10*
2.50 x 10*
3.38 x 10*
2.88 x 10*
M
2!
a
-------
Table A-12-1
(1)
.,NV«
,,Sr"
t,Co»
,,1'm'"
i;Sm'»
i.Th»«
,,r(l""n
Tj'l'a1"
tiHP"
3 x 10-»
10-'
3x10-
3x10-
5x 10-
io-«
10-'
7x 10-
3x10-
3x10-
4x 10-
4x 10-
7x10-
io-T
6x10-
5x 10-
3x10-
3x 10-
8x 10-
7x10-
5x 10-
io-«
7x 10-
3x iO-
10-'
8x 10-
9x 10-
3x10-
7x 10-
0x10-
io-«
10-'
io-«
3xlO-«
0 x 10-»
10-'
io-«
10-'
2x 10-1
5 x 10" •
4x 10-*
(Ml'C).
lOMhr «k
^c/ml
(»)
0 x IO-»
2 x 10-'
10-'
2 x 10-«
2x 10-«
2 x 10-»
10-
10-
10-
7 x 10-«
10-
10-
10-
4x10-
6 x 10-
2> 10-
3x 10-
2x 10-
4x 10-
6x 10-
4x 10-
3x 10
4 x 10-
8/10-
4x 10-
io-T
4x 10-
2x10-
3x 10-
2 x 1'J-
3x 10-
2x 10-
4x 10-
8x 10-
2x 10-
9x 10-
io-7
4 /. 10-
4x 10-
0x10
10-'
lnlikl«tion
doao
(rnn/ite)
(•1
1.8 X 10-«
2.4 X 10-»
8.0 x 10-»
2.0 x 10-
2.0 x 10-
1.8x10-
1.8x 10-
1.8 x 10-
1.6x 10-
8.0 x 10-»
3.6 x 10-
0.0 x 10-
4.0 x 10-
1.3x 10-
4.5 x 10-
8.0 x 10-
1.2x 10-
1.1 x 10-
1.1x10-
2.8x10-
1.0 x 10-
8.0 x 10-
6.0 x 10-
3.6x10-
a x io-
5.5 x 10-
5.0 x 10-
1.8
7.0 x 10-
1.5x10-
H.O x 10-
9.0 x 10-
5.5 x 10-
5.0 x 10-
1.6x10-
2.4 x 10-
1.4x10-
1.3 x 10-
5.5 x 10-
45x 10-
3.6 x 10-
Soluljle form
Critical oigan
<»)
Total Body
Bono
Total Body
Bone
Bono
Bono
Liver
Liver
Spleen
Kidney
Bone
Livor
Thyroid
Bone
Kidney
Liver
Bono
Kidney
Bone
Bone
Bono
Bone
Kidney
Liver
Bone
Total Body
Kidney
Bono
Kidney
Kidney
Kidney
Bono
Bone
Bone
Lung (Sol)
Kidney
Liver
Thyroid
Violate
Kidney
Kidney
Wound dose
(rem/iu)
(8)
2.2 X 10-
8.0 x 10-
2.0 x 10-
•7.0 x 10-
•7.0x10-
•7.0 x 10-
•7.0 x 10-
•7.0 x 10-
•7.0 x 10-
3.0 x 10-
•6.0 x 10-
1.3 x 10-
•6.5 x 10-
•5.0 x 10-
1.6 x 10-
1.1 x !0-
•4.5 x 10-
•4.5 x 10-
•4.5 x 10-
0.0 x lOr
•3.6 x 10-
•3.6 x 10-
2.4 x 10-
1.4 x 10-
•3.0 x 10-
7.0 x 10-
1.6 x 10-
•1.1 x 10-
•2.6 x 10-
3.0 x 10-
2.0 x 10-
•2.4 x 10-
•2.2 x 10-
•2.2 x 10-
6.0 x 10-
1.0 x 10-
5'.0 x 10-
•1.8 x 10-
•1.8x10-
•1.8x 10^ '
1.3xlO-»
Mnximum
pet-
mimblo
body
bimiuu
(uc)
(0)
10
2
10
60
100
4
3
1
4
10
30
20
0.3
100
2
30
70
20
90
10
200
20
6
10
4
80
6
6
0.01
10
3
200
20
90
40
30
20
0.3
.00
1
40
SfWM*ifir
ap^ciuc
activity
»/g
(10)
6.3 x 101
1.26 x 10*
1.14x10*
0.4 xlO*
2.55 x 10
2.32 x 10'
2.64 x 104
6.2 x 10*
1.62 x 10«
4.70 x 10>
1.91 x 10«
1.22 x 10>
1.13x 10«
3.5 x 10-'
2.16x 10*
O.S2 x 10
1.36x10*
2.55 x 10*
1.12x10*
- 1.76x10*
1.05x10*
l.llxlO*
2.29x10*
3.38 x 10*
7.3 xlO*
3.21 x 10-*
0.1 x 10*
2.88 x 10*
1.47 x 10'
4.28 x 10*
2.47 x 10*
45.5
2.12 x 104
3.62 x 10*
1.43 x 10*
5.2 x 10-"
8.3 xlO*
3.48 x 10*
8.2 x 10*
9.0 x 10*
1.01 x 10*
to
-a
-------
Table A-12-1 (Continued)
Nuchdo
I
MTeltJm
09i»»
V"
Snu>
Fe"
"Co"
ioHg20>
,,Pa"s
ioSn121
..Rb**
toSa47
4,Teff
i«Y"
,,Rb»
i.Se"1
47Ag105
Ru!0>
Ni"
l,Sr«»
§,Pr"3
Dy1**
Mn*1
"Rh10*
!!*fb"
ioNdl"
\yi«J
Cu
.J"1
"Teium
ISO"
ioZnitn«
"C8»*m
Cd11'
!!sc«*
''LaM°
Tellurium- 127m
Osmium-185
Vnnadium-48
Tm-113
lron-59
Cobalt-58
Mercury- 203
Protuctinium-233
Tin- 123
Kubidium-86
Calcium-47
Technetium-99
Yttnum-90
Rubidium-87
Cerium- 1 41
Silvcr-'lOS
Rut (ionium- 103
Nickcl-59
Strontium-85
Praseodymium- 143
Dysprosium- 106
Munganese-52
Rhodium- 105
Cnrsium-135
Niobmm-95
Need ymium- 147
Tellurium- 132
Tungsten- 185
Carbon- 14
Iodine- 132
Tungsten- 181
Tcllurium-125m
Sclcnium-75
Zmc-69m
Caesium- 136
Tcchnetium-97m
Cadmium-115
Scandium-48
Lanthanum- 140
Technetium-96
Insoluble form
Lung Do»»
(ram/no)
(3)
•1.7 X 10-
•1.5 X 10-
•1.4 x 10-
•1.4 x 10-
•1.4 x 10-
•1.3x10-
5.8 x 10-
4.2 x 10-
1.1 x 10-
•1.2x 10-
5.7 x 10-
•1.1 x 10-
4.6 x 10-
•1.0 x 10-
4.7 x 10-
•8.8 x 10-
•8.2 x 10-
8.7 x 10-*
6.6 x 10-*
4.6 x 10-'
4.4 x 10-»
•7.7 x 10-*
•7.6 x 10-*
•7.5 x 10-*
•7.2 x 10-*
3.6 x 10-*
•6.4 x 10-*
•6.3 X 10-*
•6.1 x 10-*
5.4 x 10-*
•5.6 x 10-*
•6.6 x 10-*
•5.6 x 10-*
1.1 x 10-*
•4.8 x 10-*
•4.6 x 10-*
2.7 x 10-*
•4.4 x 10-*
•4.4 x 10-*
•4.2 x 10-*
(MFC) a
108 hr wk
lie/ml
10-*
2 x 10-'
2 x 10-*
2 x 10-'
2 x 10-*
2 x 10-*
4 x 10-*
6 x 10-*
3 x 10-'
2 x 10-*
6 x 10-*
2 x 10-*
3 x 10-*
2 x 10-*
5 x 10-*
3 x 10-*
3 x 10-*
3 x 10-'
4 x 10-*
6 x 10-»
7 x 10-*
5 x 10-*
2 x 10-'
4 x 10-'
3 x 10-'
8 x 10-*
4 x 10-*
4 X 10-*
10"*
3 x 10-'
4 x 10-*
4 x 10-'
4 x 10-*
10-'
6 X 10-*
6 x 10-*
6 x 10-*
6 x 10-*
4 x 10-*
8 x 10-*
Soluble form
(MFC) a
168 hr wk
lie/ml
(8)
5 X 10-«
2 X 10-'
6x 10-'
10-'
5 x 10-*
3 x 10-'
2 x 10-*
2 x 10-'
4 x 10-*
10"'
6 x 10-*
7 x 10-'
4 x 10-«
2 X 10-'
2 x 10-'
2 x 10-'
2 x 10-'
2 x 10-'
8 x 10-*
10-'
8 x 10-*
7 x 10-*
3 x 10-'
2 x 10-'
2 x 10-'
10-'
7 x 10-*
3 X 10-'
10"4
8 x 10-*
8 » 10-'
10-'
4 x 10-'
10-'
10-'
8 x 10-'
8 x 10-*
6 x 10-*
6 x 10-*
2 x 10-'
Inhalation
dam
(rem/iio)
(0)
6.0 y 10-*
6.0 X 10-*
2.0 x 10-*
2.8 x 10-*
4.0 x 10-*
2.4 x 10-*
8.0 x 10-
•1.3 x 10-
3.3 x 10-
1.8 x 10-
6.0 x 10-
3.0 x 10-
2.0 x 10-
1.1 x 10-
2.2 x 10-*
2.0xlO-»
4.5 x 10-»
3.0 x 10-*
3.0 x 10-*
2.0 x 10-1
2.0 x 10-*
1.6 x 10-*
7.0 x 10-*
1.5 x 10-*
1.2 x 10-*
1.8 x 10-*
2.4 x 10-*
1.1 x 10-*
2.4 x 10-*
4.6 x 10-*
2.8 x 10-*
1.6 x 10-*
5.0 x 10-*
1.6 x 10-*
8.0 x 10-»
1.5 x 10-*
1.1 x 10-*
1.5 x 10-*
6.0 x 10-*
2.8 x 10-*
Critical organ
(7)
Kidney
Kidney
Kidney
Bone
Spleen
Total Body
Kidney
Bone
Bone
Pancreas
Bone
Kidney
Bone
Pancreas 1
Liver /
Bone
Kidney
Kidney
Bone
Bone
Bone
Bone
Pancreas
Kidney
Liver
Bono
Liver
Kidney
Bone
Bone
Thyroid
Liver
Kidney
Kidney
Prostate
Liver
Kidney
Liver
Bono
Bone
Kidney
Wound dow
(rem/ito)
(8)
1.2x10-
1.5 X 10-
8 xlO-
1.0 x 10-
1.3 x 10-
6.0 x 10-
•1.3 x 10-
5.5 x 10-
•1.2x10-
2.4 x 10-*
1.1 x 10-»
6.0 x 10-*
•1.0 x 10-'
1.4 x 10-*
•9.0 x 10-*
8.0 x 10-*
1.8x10-
•8.0 x 10-
•8.0 x 10-
•8.0 x 10-
•8.0 x 10-
6.0 x 10-
2.2 x 10-*
2.2 x 10-*
5.0 x 10-*
•7.0 x 10-*
6.6 x 10-*
3.8 x 10-*
2.8 x 10-*
•6.0 x 10-*
•9,0x 10-*
3.6 x 10-*
7.0 x 10-*
•6.0 x 10-*
1.2 x 10-*
3.0 x 10-*
•4.5 x 10-*
6.0 x 10-*
2.0 x 10-*
6.5 x 10-*
Maximum
per-
miaible
body
bunion
(nc)
7
8
8
30
20
30
4
40
7
30
5
10
3
200
30
30
20
10*
70
20
5
6
40
200
40
10
3
30
300
0.3
70
20
96
0.7
30
20
3
9
10
10
Bpecifio
activity
(10)
9.8 XlO*
7.3 x 10»
1.7 x 10>
9.7 x 10*
4.92 x 10*%
3.13x10*
1.37 x 10«-
2.08 x 10*
1.05 x 10*
8.1 x 10*
6.9 x 10*
1.71 x 10-*
6.3 x 10>
6.6 x 10-*
2.8 x 10*
3.11x10*
3.19x10*
8.1 x 10-*
2.37 x 10*
6.6 x 10*
2.3 xlO*
4.42 x 10*
8.2 XlO*
8.8 xlO-«
3.93 x 10*
8.0 XlO*
3.06 x 10*
9.7 x 10*
4.69
1.06 x 10'
4.98 x 10*
1.8 x 10*
1.44 x 10*
3.29 x 10*
7.4 x 10*
1.48 x 10*
5.1 xlO*
1.49 x 10*
5.6 xlO*
3.24 x 10*
2!
d
i
t-*
to
-------
Table A-12-1 (Continued)
Nuclido
ID (2)
TILu«"
«.Zr"
,,AC'«
T-»"»
4IAP"1
,»>••'•'»
«M'1W
,,TI<«
,N'i"
,|l'"
„»'•"
,.V"
,,K"
„<>'»
• iS"
.,Ho'«*
HV,o"
,,o«"
,TCo»
,,Sr«
t,Ko»
!!»«"'
•tPr»«
T,Au»*
«Tc"
,,rf"
,,Dyl"
?1Ke«"
7,Rc'»
t|Ir'«
.jPm"*
AH"
,.(>,'«
«Ptl§l
Ir»«
tiKe'"
7oVb'»
7J\V'»
,,1't1"™
«Eii'"
(9 yre)
Lutecium- 177
Zirconiiim-97
Arson ic-70
Tcllurium-lSlm
Silver- 111
Ei-hmm-109
Antimony- 122
Tlmllmm-202
.sodium-24
Io'lme-134
Hromine-82
Yttrium-03
Potnsfiiiim-42
Cerium- 1-4 :t
Siil|>l>nr-35
Holiniiim-186
Mc>lybdt>num-99
(Jnllmm-72
Cobalt-57
Strontium-91
Iron-55
Bunum-131
Praseodymium- H'S
Gol
1.9 xlO*
1.66 x 10*
8.0 x 10>
1.57 x 10*
8.2 xlO«
3.9 x 10s
5.4 x 10*
8.7 x!0«
2.68 x 10'
1.06x10*
3.24 x 10*
6.0 x 10*
6.6 xlO>
4.29 x 104
6.9 x 10*
4.73 x 10*
3.09 x 10*
8.5 x 10*
3.56 x 10*
2.22 x 10*
8.7 x 10*
1.15x10*
2.45
1.42 x 10-«
1.99 x 10*
8.2 xlO*
1.9 x 10»
1.0 x 10*
6.2 x 10«
4.21 x 10*
2.36 x 10*
4.56 x 10*
2.28 x 10*
8.5 x 10*
4.61 x 10*
1.78 xlO»
7.0 x 10*
1.22 x 10'
2.24 x 10*
W
a
CO
-------
Table A-12-1 (Continued)
Niicl:do
(1) (2)
,.0s'»
eo^F1*71"
T,Rc"'
jiSc*7
ai&i "
Y!t
Pd10'
i'SmlIo"
jH1
»iA?'7
;.i\i'<"
elGd»»
Kr171
"Mn".
4 tit1 1
J|xi«
»<>Hnl"
Aii"'
Pt1"
T|too
f|101
"BC'
..Te1"
'\,1H»
loTh"1
,,Cu««
..Co**"
..Si"
4Cr"
..Os1*11"
• •
S°CsIJ1
"ci"
'•F1*
4,In"'">
Osmium- 193
Mercury- 197m
Rhenium- 187
Soimdnim-47
S:rontium-92
Yt.trium-92
Palladium- 103
Sdmornim-153
Ruthenium- 105
Hydrogi-n-3
Ar»-"mc-77
Palladium- 109
O'wlolmium-159
X^ptiinimn-239
Erbium- 171
Miinganese-56
GoldU99
Ruthcnium-97
Nivkcl-65
Mvrcurv-197
Gold- 190
Platinum- 197
Thnllmm-200
Thollinm-201
BcrylIium-7
Tellurium. 127
Lcad-203
Ncodyminm-149
Thonum-231
Coppor-04
Cobalt-58m
Silicon-31
Chromium-51
OHiuium-191m
Zinc-69
Caesium- 131
Chlorine-38
Fluorine-18
Indium- 11 5m
Insoluble form
Lung DOBO
(rom/iie)
O)
•1.4 x 10-
6.6 x 10-
•1.4 x 10-
•1 2x 10-
•1.2x 10-
•1.2 x 10-
1.0 x 10-
•1.1 x 10-
•1.0 x 10-
•I.Ox 10-
•9.0 x 10-
•9.2 x 10-
•9.2 x 10-
7.7x10-'
•8.8 x 10-*
•7 8 x 10->
•1.7 x 10-'
•7.2 x 10-*
•7 1 x 10-*
2.7 x 10-s
46x10-*
•0.7 x 10-'
•6.7 x 10-*
•6.5 x 10-'
•5.9 x 10-*
•4.6 x 10-
4.2 x 10-
•4.6 x 10-
•4.0 x 10-
•4.0 x 10-
•3.8 x 10-
•3.6 x 10-
•3.3 x 10-*
•2.9 x 10-'
7.2 x 10-«
•2.8 x 10-*
•2.7 x 10-*
•2.3 x 10-*
•2.2 x 10-*
(MFC) a
168 hr wk
nc/ml
5.6 x 10*
1.88 x 10'
J2.45 x 10*
' 1.20 x 10*
8.8 x 10*
5.8 x 10*
2.17 x 10*
3.51 x 10*
2.63 X 10*
2.97 x 10*
1.05 x 10'
5.3 x 10*
3.83 x 10*
5.9 x 10*
3.86 x 10'
9.2 x 10*
1.17 x 10*
5.3 xlO'
1.0 x 10*
1.33 x 10*
9.3 xlO'
6.1 x 10*
M
>
i-^
to
o
-------
Table A-12-1 (Continued)
Nuclide
U) (2)
,,PtlMm
"T-l'1,V
4JTc'ein
Go"^
f*ai34ni
\* 9im
Fnn^m
^jTi'9"11
jjSr""™
..Kb'0""
,,RllIM
,.Kr"
i«A41
uXo1"
JOKr'sm
ii^e'"
•iKr«
S4Xo'"m
,,Ar»
Platinum-193m
Te!luriiun-129
Niobium-97
Technctium-96m
Cermanium-71
Caesium- 134m
Yttrium-91ra
Indium- 113m
Technctium-99m
Strontiuin-85in
Rhodium- 103m
Radon-220
K-ypton-37
Ar^on-41
Xenon- 135
Krypton-85m
Xenon- 133
Krypton-85
Xenon-131m
Argon -37
Insoluble form
Lung Dow
(rein/uo)
(3)
•1.9X 10-'
•2 1 x 10-'
•1.8 x 10~*
•1.3x 10-»
•1.2 x 10-»
•1.2 x 10~*
•1.1 x 10-'
•8.4 x 10-«
•5.3 x 10-«
*1.4x 10-«
•1.2 x 10-«
2.6 x 10-'
8.4 x 10-'
7.6 x 10-'
1.2x 10-'
4.4 x 10-'
1.5 x 10-'
2.6 x 10-*
2.1 x 10-'
7.2 x 10-«
(MPC) a
IBSIir wk
uo/ml
(*)
t
2 x 10-«
10"e
2 x 10-«
10"*
2 x 10-«
2 x 10-*
6 x 10-*
2 x 10-*
5 x 10-«
10"*
2 x 10-*
10-'
2 x 10-'
4 x 10-'
10"*
10~*
3xlO-«
3 x 10-«
4 x 10-«
10-'
Soluble form
(MPC) a
lOShr wk
uo/ml
(S)
2 x 10-§
2 x 10-«
2 x 10-«
3 x 10-«
4 x 10"'
10-'
8 x 10-«
3 x 10-«
10"*
10"*
3 x 10-§
Inhalation
doap
(rem/uo)
(1)
5.5 X 10-«
2.8 x 10-«
1.5x IO-«
1.8x 10-»
1.5 x 10-
5.5 x 10-
2.0 x 10-
30x10-
1 Ox 10-
3.3 x 10-
4.0 x 10-
Critical organ
(?)
Kidney
Kidney
Bone
Kidney
Kidney
Liver
Bone
Splcrn \
Kidney /
Total Body
Bone
Spleen |
Kidney j
Wound doie
(rem/ue)
(8)
1.8 x 10-'
6.0 x 10-«
0.0 x 10-«
3.6 x 10-»
5.5 x lO-«
8.0 x 10-»
8.0 x 10-«
0.5 x 10-«
2.0 x 10-»
8.0 x 10-*
1.2xlO-»
Maximum
I..T.
body
burden
(nc)'
(6)
100
5
10
GO
100
100
.•>
30
200
70
200
Specific
activity
c/g
. (10)
1.99 x 10s
1.97 x 10'
2.61 x 10'
3.81 x 10'
1.61 x 10*
7.4 x 10«
4.11 x 10'
1.6 x 10'
5.2 x 10*
3.16x 10'
3.21 x 10'
94 x 10'
2.77 x 10'
4.25 x 10'
2.54 x 10*
8.4 x 10*
1.86 x 10*
3.97 x 10'
8/3 xlO«
1.01 x 10»
Columns I And 2
Columns 3 and 4
Column 3
Column 4
Columns 5, 6. 7
rnd 8
Column 5
Column 6
Column 7
KEY
designate the. niiclido.
refer to the mtclnlc in insoluble form.
is the dose in rein to the lung following the inhalation
of 1 |zc of nucliiic.
is the Maximum PCM mistiihlo Concentration of the
insoluble nuolido in nir in |ic/ml for continuous occu-
pational exposure quoted from 1CKP publication 2 [2].
refer lo tV nuclidc in Holul>li: form.
is the .Viiiximimi Vrnmssiblo Cnnccntrat:on of the
soluble nuclidi.- in air in [ic/inl for l'ic roiitinuoiiti
_orcupr.lionul c.Nposiii^ quoted from 1CKV publieation [2].
is the dose in.rem that will be delivered to the cnticnl
organ lifted in column 6 follouing the inhalation cf
one {ic of the nuclido in soluble form.
IH tho critical organ for columns G and 8.
Column 8 in the dose in rrm that will be delivered to the critical
organ listed in column 6 following the injection of one no
of the soluble nuclido into tho body via a wound.
Column 9 lists the minimum value of the maximum permissible
body burden of the nuclido in \ac quotca in JCRP
publication 2 [2].
Column 10 lists the pppcific activity of the nuclidcs in c/g quoted
in a comprehensive list of nuclides by one of the authors.
NOTE: * Indicates for tho nuclide, which of the do«es. Lung (insoluble
form), Inhalation (soluble form). Wound (soluble form), is tho
greatest.
• Uranium enriched in uranium-235 and containing uramum-234 ia in Group III
(Rcf. Ch. III. 3)
M
I
•• Specific activity leas than 0 002 ue/g, thecunvnt IAUA rrgulations do not requn ma
rial of 0 002 uc/g or luu to be regarded, f 01
U-rial ol
, for purposes of transport, aa radioactive material
-------
APPENDIX A-12-12
for fission and activation products and 5, 000 pCi/1 (5 x 10~9 Ci/1)
for tritium. Most existing reactor facilities operate such that they
fulfill these liquid effluent design objectives.
Similarly with noble gas effluents the design objectives for
light water reactors were set forth as a lOmrem/year exposure
to an individual from all reactors on the site. (It was noted that if
shielding and occupancy were considered,the actual exposure would
be less than 5 mrem/year.) A review of current reactors indicates
that most already comply with this requirement.
Normally an individual receives from natural sources such as
cosmic rays and naturally occurring radioisotopes in food, water,
building materials, etc., an annual radiation exposure of 125 mrem.
In addition medical irradiation can add about another 50 millirem/year
to the accumulated dose of the individual. Since not only reactor opera-
tions but all uses of radioactive materials are regulated to assure the
safety of the public, the effluent releases indicated in the following
sections contribute a relatively small addition to the normal radiation
exposure of the public.
3. RADIOACTIVE WASTES FROM NUCLEAR POWER PRODUCTION
In the U.S. for some years to come the light water reactors
will serve as the heat sources for the production of electrical power.
-------
APPENDIX A-12-13
There are two general types of reactors in use, a boiling water re-
actor and a pressurized water reactor. Both types of reactors use
a similar type of fuel, namely, an enriched uraniurr oxide (UO2) which
is clad with stainless steel or zircalloy. It is in the production, use
and reprocessing of this fuel that most of the future radioactive wastes
will be accumulated, or to a very small extent, released to the en-
vironment.
A preliminary study forecasting the radioactive wastes to be
produced in the nuclear power cycle has been performed by the Pacific
Northwest Laboratory^' and the results were recently published in
Report No. BNWL-B-141 entitled Data for Preliminary Demonstration
Phase of the "Environment Quality Information and Planning System
(EQUIPS) " dated December 1971. Much of the information in this
section was extracted from this report and augmented where necessary
by other published data.
(1) Mining and Mill Operations
Uranium mining operations are predominantly located in
the States of Wyoming, New Mexico, Utah, Colorado and Texas.
The acreage devoted to uranium mining in these and other states
(2)
as of January 1, 1971 is given below.
-------
APPENDIX A-12-15
Table A-12-2
U.S. Acreage Devoted to Uranium Mining
State
Arizona
California
Colorado
Idaho
Montana
Nevada
New Mexico
S & N Dakota
Texas
Utah
Washington
Wyoming
Total
Acres
221,000
436, 000
1, 959,000
21,000
386,000
250,000
4, 717,000
276,000
1, 079,000
3, 640,000
398, 000
11.023,000
24,406,000
A total of about 90, 000, 000 tons of ore have been shipped
to the mills since the beginning of the uranium industry in this
country. In 1970 there were about 2, 800, 000 tons of ore from
open pit mines and 3, 500, 000 tons of ore from underground
production (containing approximately 0. 2 percent UgOg)
shipped to the uranium mills.
-------
APPENDIX A- 12-16
Ores from the mines contain uranium-238 and uranium-235
which are in equilibrium with their long half-life daughter pro-
ducts among which are lead-210, polonium- 210, radium-226 and
thorium-230 and the short half-life gaseous product radon- 2 2 2.
The uranium is leached from the ore and is partially purified
and concentrated in the milling operation. Two types of leaching
processes are used, an acid leach and a carbonate leach. The
amount of ore processed, its uranium content as UgOg. and the
total curies of waste discharge into the different media have
been estimated^) for 1970, 1975, and 1980 and the data are
presented in Table A -12-3.
The expected rates of l^Og recovered in tons which serve
as the basis for determining the radioactive waste discharges
in Table A- 12-2 compare favorably with the forecast data on
commercial requirements from the Grand Junction Office of the
(2)
AEC given in Table A-12-4. The uranium ore processing
mills are tabulated in Table A-12-5.
-------
APPENDIX A-12-17
Table A-12-3
Uranium Mill Operating Quantities and Waste Discharges
1970
1975
1980
Ore Processed (tons)
Acid Leach
Carbonate Leach
Recovered (tons)
Acid Leach
Carbonate Leach
A EC Produced
Radioactive Waste Discharges
(curies)ta)
Acid Leach Process
Air (222Rn)
Land (238u 226Ra230Th
210Pb 210Po)
Water (238u 226Ra 230Th)
Carbonate Leach Process
Air (222Rn)
Land (238U 226Ra 230Th
210pb 210p0)
Water (238U)
3,400,000 8,000,000 14,000,000
1,000,000 2.500,000 4,000.000
6.480
2.000
4.010
15.200
4.800
26,000
8.200
2,000(b) 4,000 7,000
7,000 16,000 30,000
0. 1 0. 2 0. 4
500
2,000
0.5
(b)
1.000
5,000
0.4
2,000
8,000
0.7
(a)Total curies of 238U, 222Rn/ 226Ra< 230Th> 210Pb and 210Po ore
with an average UsOg content of 0. 2% was assumed to contain
515 fiCi of uranium and each of the 5 daughters of interest, for a
total of 3090 /iCi per ton of ore.
The actual distribution of 222Rn in the milling process is not known.
However, in the study it was assumed that all of the 222Rn in secular
equilibrium in the ore is released during crushing and grinding and
is exhausted to the air via the ventilation system. The values
shown do not include radon releases from the decay of radium in the
impounded tailings.
-------
APPENDIX A-12-18
Table A-12-4
Production Forecast through 1985
Year
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
Tons of Us
Annual
6,900
10,200
14,000
16,700
18.400
21.100
24. 400
28, 600
31.700
34. 200
39.300
44. 300
49. 100
53, 900
59, 300
Og in Concentrate
Cumulative
6.900
17.100
31, 100
47, 800
66, 200
87, 300
111. 700
140, 300
172,000
206, 200
245, 500
289, 800
338, 900
392, 800
452, 100
/Q \ o O C
Tails assay of enrichment plant assumed to be 0. 2% U.
(c)
Pu recycle assumed to start in 1974.
Based on assumed fuel processing times and reactor characteris-
tics supplied by reactor manufacturers.
-------
APPENDIX A-12-19
Table A-12-5
Uranium Ore Processing Facilities and Nominal Capacity
Tons/Day
Anaconda Co., Grants, New Mexico 3, 000
Atlas Corp., Moab, Utah 1, SCO
Conoco-Pioneer Nuclear. Falls City. Texas 1. 750
Cotter Corp.. Canon City, Colorado 450
Dawn Mining Co. , Ford, Washington 500
Federal-American Partners, Fremont Co., Wyo. 950
Humble Oil Co., Powder River Basin, Wyoming 2. 000
Kerr-McGee Corp., Grants, New Mexico 7, 000
Mines Development Inc., Edgemont, S. D. 650
Petrotomics Co., Carbon Co. , Wyoming 1, 500
Rio Algom, LaSal, Utah 500
Susquehanna-Western Inc., Falls City, Texas 1, 000
Susquehanna-Western Inc., Three Rivers, Texas 1, 000
Union Carbide Corp., Rifle & Uravan, Colorado 2, 000
Union Carbide Corp., Natrona Co.. Wyoming 1, 000
United Nuclear-Homestake Partners, Grant. N. M. 3, 500
Utah Const. & Mining Co., Fremont Co., Wyoming 1, 200
Utah Const. & Mining Co., Shirley Basin, Wyoming 1, 200
Western Nuclear Corp., Jeffrey Co., Wyo. 1, 200
Total 31,900
-------
APPENDIX A-12-20
(2) Uranium Conversion
The ore concentrates from the mill are reduced from
UsOg with hydrogen (hot cracked ammonia) and converted to
UF4 and finally UFg with anhydrous HF and elemental fluorine,
respectively. The UFg is fractionally distilled to remove im-
purities. The alternate process of purifying the ore concentrate
by solvent extraction prior to denitration to UO2 and subsequent
fluorination does not require a final fractional distillation of the
UFg. Scrap materials are recycled to assure maximum uranium
recovery, but there is some buildup of radioisotopes on the
inert fluid-bed material used in the reduction-fluorination opera-
tions as well as in, the ash from the scrap recycle operation.
The estimates of the waste,' ' most of which is drummed or
impounded in earthen pounds , are given in Table A-12-6.
Table A-12-6
Uranium Conversion-Radioactive Waste Discharges - Curies
Air
Land -
Water
U-238
Ra-226
Th-230
- U-238
1970
—
0.2
0.5
15.2
0.2
1975
-
3.2
1.0
27.3
0.4
1980
-
5.8
1.6
46.0
0.7
Note: Data does not include recycle of uranium from reprocessing
which will still be a small part of the total (10%) through 1980. Re-
cycled uranium will be converted to UFg at reprocessing plants.
-------
APPENDIX A- 12-21
The companies providing conversion services for UsOg to'UFg
are Allied Chemical Corporation, Metropolis. Illinois
(14, 000 tons/year U); and Kerr-McGee Corporation, Sallisaw,
Oklahoma (5,000 tons /year U).
(3) Uranium Enrichment
The enrichment of uranium in 235U content is accomplished
at AEG -owned gaseous diffusion plants where there is very little
waste discharge because of its value. The estimates*1' for 1970
through 1980 are given in Table A -12- 7. All enrichment ser-
vices in the U. S. are provided by U. S. AEC-owned facilities at
Oak Ridge, Tennessee; Paducah, Kentucky; and Portsmouth, Ohio.
Table A -12-7
Uranium Enrichment - Radioactive Waste Discharges
Air
Water
- U-234
U-235
U-236
U-238
- U-234
U-235
U-236
U-238
1970
0.047
0.002
-
0.045
0.366
0.016
0.002
0.035
1975
0.144
0.006
0.005
0.126
1.120
0.047
0.039
0.982
(Curies)
1980
0.269
0.011
0.016
0.228
2.100
0.086
0.125
1.770
-------
APPENDIX A-12-22
(4) Fuel Fabrication
1. UO2 Fuel
The enriched UFs from the gaseous diffusion plant
is converted to UC*2 by vaporization with water, the addi-
tion of NH4OH to form ammonium diuranate and finally
high temperature firing to form large pieces of UO"2. The
UC>2 is pulverized and pelleted. Sintered and ground pel-
lets are encased in stainless steel or zirconium-alloy
tubes which are assembled with spacers, end pieces,
etc. , to form the final fuel assemblies for the power re-
actors. The radioactive waste discharges to environ-
mental media from UC>2 fuel fabrication are provided in
Table A-12-8. The companies providing uranium pro-
cessing and fuel fabrication services are:
General Electric Co., San Jose, Calif., and
Wilmington, N. C.
Westinghouse Electric Corp., Columbia, S. C., and
Cheswick, Penna.
Gulf-United Nuclear Corp., Hematite, Mo., and
New Haven, Conn.
Jersey Nuclear Co., Richland, Wash.
Kerr-McGee Corp., Cimarron, Okla.
Babcock & Wilcox, Lunchburg, Va., and Apollo, Penna.
Nuclear Fuel Services, Inc., Erwin, Tenn.
Combustion Engineering, Inc., Windsor, Conn.
-------
APPENDIX A-12-23
Other companies providing partial services are:
Atomics International, Canoga Park, California
Gulf General Atomic, Inc., San Diego, California
NL Industries, Inc., Albany, New York.
Table A-12-8
UO2 Fuel Fabrication - Radioactive Waste Discharges (Curies)
Air
Land Burial
Water
U-234
U-235
U-238
U-234
U-235
U-238
U-234
U-235
U-238
1970
0.140
0.006
0.033
0.002
-
-
3.300
0.100
0.800
1975
0.441
0.018
0.105
0.007
-
0.002
10. 300
0.400
2.500
1980
0.661
0.027
0.158
0.011
0.009
0.002
15. 500
0.600
3.700
2. PuC«2 Fuel
Plutonium recovered in the reprocessing operation
will be recycled in the mid-70's for fabrication as fuel
assemblies. The waste expected from these operations
is presented in Table A-12-9
The same companies that provide a capability in
uranium processing and fuel fabrication provide the
capability for Pu fuels.
-------
APPENDIX A-12-24
Table A-12-9
PuC>2 Fuel Fabrication - Radioactive Waste Discharges (Curies)
Air
Land Burial*
1970
-
Pu-238
Pu-239
Pu-240
Pu-241
1975
« 70MCi
2,860
579
724
197,500
1980
<630MCi
19, 300
3,850
4,800
1.331,000
* Assuming that waste is not reduced to a homogeneous, non-
oxidizable form before burial.
/0\
Another study* ' predicts that the fuel fabrication
industry will increase its quantity of alpha contaminated
waste for land burial from 26, 000 ft3 with 5. 6 kg of Pu
in 1970 to 2, 700,000 ft3 with 580 kg of Pu in 1990. The
quantity of Pu to land burial in 1980 was estimated to be
175 kg. This is the same order of magnitude as indicated
in the above table which, if converted from curies to
kilograms of Pu, indicates land burial of about 97 kg
just from Pu fuel fabrication.
(5) Power Reactor Operations
Radioactive material during reactor operations is formed
inside of the fuel rods due to fissioning of the contained uranium
-------
APPENDIX A-12-25
and exterior to the fuel rods due to neutron absorption of other
materials including the cladding, the coolant, coolant impurities,
reactor components, and boron poisons. It is primarily the
radionuclides produced by the neutron absorption of these various
materials that are collected by the waste treatment systems at
the power facilities or that are released to the environmental
media. Leakage of fission products through cladding imper-
fections also contributes to the radioactive waste, but the quan-
tities are small. The estimated releases* ' of radioactive waste
materials to environmental media are shown in Tables A-12-10
through A-12-12.
In addition to the amounts of solid waste consisting of spent
resins, solidified liquid wastes and reactor control rods shown
in Table A-12- 11, there will be a significant volume of solid
trash containing relatively small quantities of radioactivity. It
is expected that in 1970, 1975, and 1980, there will be
60, 000 ft3 (30 Ci), 350, 000 ft3 (400 Ci), and 700, 000 ft3
(1, 000 Ci) of this general trash, respectively.
-------
APPENDIX A-12-26
Table A-12-10
Gaseous Effluents from Power Reactors* (Curies)
H-3
N-13
Ar-41
Kr-85 m
Kr-85
Kr-87
Kr-88
Xe-131
Xe-133 m
Xe-133
Xe-135 m
Xe-135
Xe-138
1-131
1-132
1-133
1-135
Total Curies
Atmosphere
Half -Life
12. 4 y
10.0 m
109.0 m
4. 4 h
10. 76 y
76.0 m
2. 8 h
12.0 d
2. 3 d
5.27 d
16. 0 m
9. 2 h
14.0 m
8. 0 d
2.4 h
20.8 h
6. 7h
to the
1970
1
5.0 x 10,
2.8x 10,
4. 6x 10;:
1.6x10*
1.4 x 10*
4. 9 x 10
5.4 x 10.
2
3. 3x 10,
6.0 x 10):
1.7 x 10*
2. 7x 10*
1.1 x 10*
9. 6x 10*
0.4
0.7
0.4
0.6
g
2. 7 x 10°
1975
2
8.0x10
2. 6x 10*
4
4. 2 x 10*
6. 7 x 10*
2. Ox 10
1.5x10°.
l.Bx 10,
3
3. 6x 10?
4
2. 6 x 10*
1.3xl06
8. 3 x 105
3. 2 x 105
2. 9x 106
6.2
2.5
1.3
2.0
g
9. 4 x 10°
1980
„
2.4 x 10.
6.9x10
1.1 x 10°
1.5 x 10,
5. 6x 10g
3.0 x 10
3. 7 x 10
l.Ox 10*
4
6.0 x 10*
3.4 x 10g
1. 7 x 10
6. 4 x 10
5.8 x 10b
18.0
5.0
2.5
3.9
7
2.0 x 10
^Assumes minimum fission gas holdup time of 30 minutes.
-------
Table A-12-11
Solid Waste from Power Reactors to Land Burial (Curies)
Radio-
nuclide
H-3
Mn-54
Fe-55
Fe-59
Co-58
Co -60
Ni-59
Ni-63
Sr-89
Sr-90
Zr-95
Nb-95
Ru-103
Ru-106
Ag-108
Ag-110
Cd-109
Cd-115
In-114
Cs-134
Cs-137
Ce-141
Ce-144
Total Ci
1970
Resin and
Sol. Liquids
1.4x10?
1
2. 7x10^
y
9.7x10
-
1
6.6x10*
4. 6x10
_
2
1.2x10
5.8
2.4
1.7
3.6
6.8x10,
1.6x10
-
-
-
-
_
2.3xl02
8.3xl02
_
7.5
4.4xl03
Tot. cu.ft. 3.0x10
Control
Rods
1.3x103
3
1.8x10*
4
5.6x10
iJ.uxiu
7.0
7.0 ,
3
1.0x10
-
-
-
-
-
3
1.1x10*
3. 9x10*
1.8x10
7.0
2.0
-
_
-
1.0x105
1.2xl02
1975
Resin and
Sol. Liquids
2.3x10?,
2
4.2x10*
4
1.5x10
4.6
X
1.0x10,
6.4x10
_
3
1.8x10*
l.lxiof
4.4xloJ
2.8x107
6.0x10,
1.2x10^
2.8x10
-
-
-
-
_
3.8xl03
1.4xl04
2.0
1.4xl02
7.4xl04
1.7xl05
Control
Rods
7.0xl04
5
1.0x10°
H
3.0x10
1.2X1U
S.SXlOg
3. 5x10^
4
5. 4x10
-
-
-
-
-
4
6.0x10*
2. 1x10^
1.0x10^
4.0x10
1.2xl02
_
-
-
-
5.4x10*1
2.3xlOJ
1ET80
Resin and
Sol. Liquids
6.8x103
3
1.3x10?
4
4. 5x10*
1.4x10,
X
3. 0x10^
1.7x10
4.0X1U
3.0x10^
1.3x10^
s.ixioi
1.7x10,
3.5x10^
iL
7. 9x10
-
-
-
-
-
l.lxlO4
4. IxlO4
6.0
4.0xl02
2.1x10^
3.3x10°
Control
Rods
3.4x10^
5
2. 5x10°
h
8.0x10
2. axiu
8.4x102
8. 4x10,
o
1. 3x10
-
-
-
-
-
5
4.0x10°
1.3x10'
6.0x10,
1.8x10
8. Oxl O2
_
-
-
-
2. 2xl07.
1.35x10*
t
-------
APPENDIX A-12-2a
Table A-12-12
Liquid Waste from Power Reactors to Watercourses (Curies)
Co-58
Co-60
Sr-89
Mo-99
Ru-103
Ru-106
Te-132
1-131
1-132
1-133
1-135
Cs-134
Cs-137
Total curies
H-3
1970
2.1
1.7
0.3
39. 3
29.3
2.7
7.1
11.1
6.5
3.4
1.3
1.9
0.9
excluding Tritium(H-S) 110
1.7xl04
1975
6.1
0.3
0.4
73.7
37.2
3.1
31.6
55.7
41.5
41.2
20. 1
0.8
0.5
339
2. 7xl05
1980
18.3
0.8
1.3
219.2
110.2
9.2
154.5
166.6
124.1
123.5
60.2
2.4
1.5
1010
8. Oxl O5
In recent testimony at rulemaking hearings, the AEC
(4)
staff presented data on the releases of radioactive material
in gaseous and liquid effluents from existing power reactors.
This data for releases in 1970 is summarized in Table A-12-13,
and provides a reasonable crosscheck for the data presented
for 1970 in Tables A-12-10 and A-12-12.
It should be noted that none of the power reactor facilities
listed in Table A-12-13 discharged liquid or gaseous effluents
in excess of the safety limits established by their license, nor
-------
APPENDIX A-12-29
Table A-12-13
Radioactive Waste Discharges from
Operating Nuclear Power Plants
(curies)
Facility
Oyster Creek
Dresden 1
Nine Mile Pt.
Dresden 2
Humboldt Bay
San Onofre
Ginna
Big Rock Pt.
Conn. Yankee
Saxton
Indian Pt. 1
Yankee
LaCrosse
Liquid Effluents
-Fission and
Activation
Products
18.5
8.2
28.0
13.0
2.4
7.6
10.0
4.7
6.7
0.01
7.8
0.03
6.4
Total Releases Ci 113
Tritium
22
5
20
31
-------
APPENDIX A-12-30
A map prepared by the U.S. Atomic Energy Commission
showing the nuclear power plants that are operable, being built,
and ordered but not yet under construction is presented in
Figure A-12-2. Table A-12-14 indicates the features and sig-
nificant milestones related to these reactors.
(6) Fuel Reprocessing
The reprocessing of spent nuclear fuel will be performed
for some years to come by either the Purex process or the
Aquafluor process. Inasmuch as these operations require the
processing of larger quantities of more radiotoxic material
than all other operations of the nuclear power cycle or nuclear
industry in general, a brief description of these processes is
included to identify the sources and the means of handling the
radioactive wastes.
Only one commercial fuel reprocessing plant is in opera-
tion. It is operated by Nuclear Fuel Services, Inc. (NFS) at
West Valley, New York, and it employs the Purex process at a
nominal processing capacity of 300 metric tons of uranium per
year (MTU/yr). General Electric (GE) and Allied-Gulf Nuclear
Services are constructing facilities. The GE facility is in
Morris, Illinois, is designed for the Aquaflor process, and will
-------
n
i—
n
o
0)
»3
sg
l§
° w
» >
ffi
rt- tO
&• i
(K to
0)
CL
en
r-t-
(D
NUCLEAR PLANT CAPACITY
(KILOWATTS)
OPERABLE
BEING BUILT
PLANNED REACTORS ORDERED
TOTAL
10.040.800
45,779.000
51.571,000
107,390,800
TOTAL ELECTRIC UTILITY CAPACITY AS OF
SEPTEMBER 3O. 1971 357.121.607 KILOWATTS
OPERABLE • (23)
BEING BUILT A (54)
PLANNED (Reaclon Ordered) • (52)
U.S. Atomic Energy Commission
December 31. 1971
(See Table A-12-14a, which follows, for description)
CO
-------
APPENDIX A-12-32
Table A-12-14a
Nuclear Power Reactors in the United States
HTI
CAPACITY
UTILITY
MITIAL
M SIGN
•OWE*
OMktam
f feMi tail Unit I
•room tuni Muck* Paw H«it Unit I
Iraom »mt Hock* few FUil Uon 1
Jon» II f ••» Rucka fl«il Uiut I
Mn* • F«k» KMto Ibni UM 1
AftonM Rockv On Unit I
RiicMf On UM I
NondMUl In few tail Uml 1
I* Ouln NiiclHf Gmnino, Sunn Urn I
In Onolro NIKM CMIIWI Slum Uml I
In Drain Nigh* Ginnnit Sum Urn J
0«M> Cnwi Duck* few tail Urn I
OUMi CMIOB Kucta few tail UM 1
I Oil OB
I OH 009
IBS 000
in ooo
in.ooo
noon
1.140000
1.110000
ton.ooo
IJHOOO
mow
i.in.on
unjw
AlkKH few » l«il C>
Alt jnw few > l*il Co
IciU Ga nd Ekcn< Ci
i* Ml Cl > SM D««l G> t El Ci.
to Wil U 1 Soi O.no Ga » El Co
!• bkl El 4 Sv 0«* Gil I EL Ci
»«ilc Gn UK Ekunc Cc
feulc Gil M EUctiic Ci
Mimcwi UMiir Oaa*>
mooo
OlIOO
fewto
nuoo
Oikum few & l^ii Ca
few i l«n Ca
fenlSmon Until
T«UT feM SUMi UMI
Cf«iMKwtan Uml
CIVM «"• tan urn 4
f tan I IM* Ihdv tail U« I
E«w I Hnck IhdUr tail UM I
Aim * VofiH. Jf tan Unit I
Aim * Voilk. Ji tail UM 1
•f t L^n Co.
Fbn* few tap
UMI
**** fe>n Suran UMl
itahv Pow SUM UMJ
Uml
i Strop* UMI
Oiil turn Sumo UMI
i Ci. *>ckK SUM UM 1
i Ci lhck» SUM* UM I
MM 000
1100.000
109.000
Flon* few •>< L*l to.
vto
GwwfewCo
GwfifewCo
•fCo
Ed«m Co
Co«ww«h Ctan Co
M Co
Idi Ednon Co
ElCi-U.-m.GBftEkc.Cl
C«~-. Eo\ Co -li -in Urn ft Eke. Co
Com Ed. Co-li
Cowi Ed Co-In
COOK EdwiCo.
CooMtdwiCo.
Owo AIMH iw« C
C*on CUh INcw few tail UM I
Cdwl CMh •«»• few tail Unit
I Ga ind Ekcn« Co
o G>| OM Ekanc Co.
o Aim* Ekcinc Co
ilowiCo.
•oj Hod POM
M Did fe«i KodM tail
•Until llockof few Sum
(unco FWIK AIOIM few PUnl UM I
Cmo FOTIHI AWK few tail UM i
OmM C Coot tail UM I
OVUM C. Cool tail UM I
i Plm UM I
UMl
•oooudi IhAoi Gwfin>« MM
MOT uu»o Hunm GMIII^ Urn UM I
•MIOMIhcMiGlwIuiinM UMl
>t Mm SUM* UM I
OMtai Edw. Co
OottM E*in Co
|I*OM 1 Mc«w> Ekcinc Co
loduoo » Italiwi Ekcinc Cl
•i Co
• Co.
•OillMfn SlIMI few CO
•JomnSlMifewCo.
•MiMi *ii*kc few Oitn
-------
APPENDIX A-12-33
Table A-12-14a (Continued)
PLANT NAME
CAMCITY
UTIUTV
Of MOM
Feme*
miEIBET
rimllnv
FMMlMT
Oymf Girt *UC>M *IMI Mm UMl
FofkM Hn«t Gcntrtin* SlIfliM UM I
StfMiliKMfGrait'lSUM Until
SMI luck* GnouiiSurai UM|
•MA4I4 HutlM CvfMbiifCuMM UMl
Uii.il
1140 000
unooo
IlltOO)
lafenFiM
SM»
Ia*>
Mntatt
So*
HUTU CMOUiU
UMl
M« font SIM Ui>i]
••» Vik FM Item SWOT UMl
•«• M.* Fnni DuCK« SMWI Unill
I C. C«M IhCHV >OMi H«ll UMl
Skontn IhcM hw Sutw
• 4
u
• A.Fi
UMl
IBM EIKIK Mm umt
*m.t HcbnllKMSUMi UM I
Uitnl
Hjn« Pkm UM 1
termPM Urn 4
•DJOO
I 100 000
420000
111000
IB 000
I.1ISOOO
nijooo
ni ooo
BUBO
1IHOOO
1110 000
tnaa
injoo
tnaa
nun
•Rnc «M C«. * I
»vt Sun Ekra« I Ca C«
ill* 1
IT7I
•11%
itn
NB
IU1
itn
in
tin
itn
itn
III4
« L«n C&
C. ••«•>
liojgoo
UMl
IOIHB Anmc FOOT Sam UMl
Suixm UM 1
toM«f Sura UM I
UDBOOg
unooo
ijnooo
ijonooo
oi urn I
UMi
UMl
iiiirj MM unto Sura UMI
•UTHUmilM
SvnjCrtv
••mbl*
I UMl
• Ckcn Co MTCIt Ha I
• EkcnCa HTGRNa.1
• UMI
UMl
NidwSura UMl
UMl
••nv Sura UM I
• Mm UMI
IfPtaOl UMl
MM UMl
Ml ODD
Ml 000
111 UOO
•1000
IjOSUOO
IMU09
IIVLOOO
1.110.000
Ml 000
ItM
Mm U«i I
Funi UMl
goi »•» UM I
I.III
nn
nn
nit
•nura uteo
Mm DIM
IIHB
i.in.01
-------
APPENDIX A-12-34
Table A-12-14b
Status of Central Station Nuclear Power Reactors
Significant Milestones
P'r-iwl/Lnmiipn
Shippinnnort Atomic
Powrr St. it inn (Pa I
Indian Point Station.
Unit 1 IN V )
P'rvlrn Nurlrni Powrr
Sl.ilion Unit 1 (III )
Yankre Nuclrnt Power
Station (Mass 1
Enrico Fermi Alomic Power
Plant. Unit 1 (Mich )
Pathfinder Alomic Power
Plant IS D I
H.illam Niiclrw Power
Facility (Np|i I
Humholdt Bay Power Plant.
Unit 3 (Calif 1
Elk Rivrr Nuclear
Plant (Minn I
Pp.wh Bottom Atomic Pwr
Sl.ilmn Unit 1 (Pa 1
CiVolmas Virnima Tubs
Reactor IS C )
Piriua Nurlpnr Power
Facility (Ohio)
Biq Rock Pomt Nuclear
Pl.int (Mich 1
Boiling Nuclear Superheater
Powrr Station (P R )
Genoa Nuclear Generating
Station (Wise 1
Ha-Mam Neck Plant
(Conn I
OMfWI
Duqiicwie Light Company
anil AEC
Consolidated Ednon Co
Commonwealth Edison Co
Yankee Atomic
Eire Co
Power Reactor
Development Company
Northern States Power
Company
Consumers Public Power
District and AEC
Pacific Gat & Electric
Company
Rural Cooperative Power
Association and AEC
Philadelphia Electric
Company
Carolina! Virginia Nuclear
Power Associates. Inc
City of Pigua, Ohio
and AEC
Consumers Power Company
of Michigan
Puerto Rico Water Resources
Authority and AEC
Dairy'and Power Cooperative
and AEC
Connecticut Yankee Atomic
Power Company
Cm*
Nit
IMWtl
go
265
700
175
609
585
75
685
22
40
17
11 4
703
165
SO
575
Typ.
PWR
PWR
BWR
PWR
FBR
BWR
SGR
BWR
BWR
HTGR
HWR
OMR
BWR
BWR
BWR
PWR
NSSS/
«
Conrr
Writ
s&w
B&W
O/Vit
GE
Born
West
S&W
PRDC
CA
AC
PSE
Al
Been
GE
Been
AC
S&L
GGA
Been
West
S&W
Al
H&N
GE
Bech
Comb
J&M
AC
S&L
West
S&W
•untie
Annc'd
10/63
2/55
4/55
4/5S
4/55
2/57
4/55
2/58
2/56
11/58
8/57
2/59
12/59
6/58
4/61
12/62
NSSS
Contr
Award
7/53
7/55
7/55
6/56
3/57
5/57
9/57
2/58
6/58
11/58
1/59
6/59
12/59
1/60
6/62
12/62
Conn
Per mil
Applied
NA
3/55
3/55
7/56
I/SB
3/59
2/59
4/59
3/59
7/60
7/59
9/58
1/60
12/59
10/62
9/63
CP/
POL
luiwri
NA
5/56
3/62
5/56
9/59
11/57
7/60
B/56
5/63
5/60
3/64
7/60
8/62
11/60
8/62
12/59
11/62
2/62
1/66
5/60
11/62
1/60
8/62
5/60
fl/62
7/60
4/64
3/63
7/67
5/64
6/67
Inliltl
Crll'
12/7/67
8/2/62
10/16/59
8/19/60
8/23/63
3/24/64
8/25/62
2/16/63
11/19/62
3/3/66
3/30/63
6/10/63
9/27/62
4/13/64
7/11/67
7/24/67
Flril
Eltc
17/18/57
9/16/62
4/15/60
11/10/60
8/5/66
7/25/66
5/29/63
4/18/63
8/24/63
1/27/67
12/18/63
11/4/63
12/8/62
8/14/64
4/26/68
8/7/67
Inilill
0*non
•nwn*
17/57
1/63
6/60
1/61
10/70
9/67
7/63'1
5/63
2/64
5/67
9/65
1/64
3/63
9/65
8/69
12/67
Cnm
mpinal
On> •
NA
10/62
8/60
2/61
i
11/63
8/63
7/64
6/67
3/64d
2/64'1
11 '65
(
2/71
1/68
10
11
12
13
14
15
16
' ' " - 'i ' »inrny rruy r» IOWOT then inn iiithoilnri hv llrtnit InformMlon on Khtovwnmt et tuture mlrmonn band on dlta lurnMMd b* utllliy Actual dim In hnM
I „..»,. ..I. I..I-iltfl In light Imvo*
NA N..I *„.!., .1.1.
fOL P.r,vl..i|.i»l (||».«l.r.g t InnM
• PI.ni M,, ,h,rt ,in.n Orioiw 1967 on •/•/&§ MSP mnounrari phm n InniH •• find boHm toe OBKMton ummw IM
r> Shut (town 9<64
c Pl«nl that down ?/QB
d Shui dawn Jmuw 1967
• Shut dawn tor rtpffn Jtnufr, 1966 opviHnf contract nrmhwnd 12/67
< DJtHkmtoB^LO JiHoninnounoideyei On*, to dhm»nH» tmud tit ln»
but no« eperan h»ueaH»a» 14 1MB
KEY TO «E It
itKl En«lnMil
KEY TO NSSS I (Nuriw S
»rr».,r«n ri»rinr PONK S*rvln Corponttan
C « Conimnnwvallh AwoclvtH
Etvn tl<~ro
G.r*. H,ll Owrurn » Rlctvntfnn
Mplmn md NMOTI
MM J.rk ion •nrl Mraitand
O OwnlH
P^E Plnnnr S«*«tr« and EnglnMrlnf
SAL Suroint Kd Lundy
5SC Smrthwn 5**rw(cn Compiny
SAW Sinn* Mid WMww
UEC Unltx) EnflnMri md Cnnnruclnrl
VII Vllro
AC
Al Alnrnir.i Inmrnillonal
R»lW Bibrork • *Vllca>
Cnmb Combuirlon EnglnM'I
GE Cmtrll Fl«n.l<:
GGA Gulf Gmm Atomic
PROC Pnwn Rwcto>
12/1/71
-------
Table A-12-14b (Continued)
APPENDIX A-12-35
rimOTl'ln utiitn
S.in Onulir Nut Irar Gfl
Station. Unit 1 (CaM 1
N RiMrtci/WPPSS
(Wwh 1 "
Ninr Mile Print Niirlrn
Sl.ilioii. Ihnl 1 IN Y 1
O\«irr C'frk Nuclrar fount
Pl.i.11 Unit 11 N J 1
Prrsclpn Nuclrar Power
SI.MIOO. Unit 3 (III I
Foil St Vram Nuclear
Grnri«linqSta (Colo I
R E Gmna Nuclear
Power Plant. Unit UN V }
Filqnm Station
(Man 1
Millstone Nuclear Power
St.ilion. Unit 1 (Conn I
Indian Point Station
Unit 2 IN V |
Turkey Point Station.
Unit 3 (Fla I
Dresden Nuclear Power
Station. Unit 3 (III )
Paliudn Plant
(Mnh 1
H B Rohmtpn S E
Plant Unit 1 1S C 1
Pnmi Beach Nuclear
Plant Unit 1 (Wise )
Montirrllo Nuclrar
Generating Plant (Minn I
Quad Cin« Station.
Unit 1 III! 1
Browni Ferry Nuclear Pwr
Plant Unit 1 (Ala 1
Browni Feny Nuclear Pwr
Plant Unit 2 (Ala 1
Oronec Nuclear Station.
Unit 1 IS C 1
Oconre Nuclear Station.
Unit 2 IS C 1
Quad Cum Station.
Unit 2 Illl 1
Pparh Bottom Atomic Pwr
SMI ion Unit 2 (Pa )
Penrh Bottom Atomic Pwr
Station Unit 3 (Pa 1
Salrm Nuclear Grrmatlng
Station. Unit 1 IN J I
Own
Southern Call! Erllsonft
Sun Olrqo Gat ft Eloc Co.
Wmhlnqton PuMIc Power
Supply Syitnm and AEC
Nlaqata Mohawk Power
Corporation
Jersey Central Power ft
Lidhl Company
Company
Public Service Company
of Colorado
Rochester Gn ft Electric
Company
Boston Edison Company
The Millstone Point
Company
Consolidated Edison
Company
Florida Power and Light
Company
Common wealth Edison
Company
Consumers Power Company
of Michigan
Carolina Power and Light
Company
Wisconsin Elec Pwr Co and
Wit
(MW.I
430
790
825
650
B09
330
420
ess
652.1
873
693
809
700
700
497
545
809
1065
1065
841
886
809
1065
1065
torn
T»p»
PWR
GR
BWR
BWR
BWR
HTGR
PWR
BWR
BWR
PWR
PWR
BWR
PWR
PWR
PWR
BWR
BWR
BWR
BWR
PWR
PWR
BWR
BWR
BWR
PWR
IfSSS/
AE
Conn
West.
Bech.
Burns
ft Roe
GE
O
GE
BftR
GE
SftL
GGA
S&L
West
Gil
GE
Bech.
GE
Ebdsco
West.
UEC
West
Bech
GE
SftL
Comb
Bech.
West.
Ebasco
West
Bech.
GE
Bech
GE
SftL
GE
0
GE
0
B&W
O
B&W
0
GE
SftL
GE
Bech
GE
Bech.
Weil.
O
Public
Anne'd
4/60
4/62
7/63
5/63
2/66
3/65
6/65
8/65
4/65
11/65
11/65
1/66
1/66
1/68
2/66
4/66
4/66
6/66
6/66
7/66
7/66
7/68
6/66
BAM
BAM
NSBS
Conn
AMtd
1/83
4/83
10/83
12/63
2/65
3/65
6/65
8/66
9/65
11/85
11/65
1/66
1/66
1/68
2/66
4/66
4/66
6/66
6/66
7/68
7/66
7/66
8/68
BA»
SAW
Cnnir
Firml!
AlVlM
2/83
NA
3/64
3/64
4/65
10/68
11/65
6/67
11/65
12/85
3/66
2/66
6/66
7/66
8/66
8/66
5/66
7/68
7/66
11/68
11/66
8/86
2/87
2/B7
12AS8
CF/
POL
Iwmt
3/64
3/67
NA
4/65
8/69
12/64
4/69
1/66
12/69
9/68
4/66
9/69
8/68
5/66
10/70
10/68
10/71
4/67
10/66
1/71
3/67
3/71
4/67
8/70
7/67
10/70
6/67
9/70
2/67
9/71
5/67
5/67
11/67
11/67
2/67
1/B8
1/68
,9A»
Inlllri
cm •
6/14/87
17/31/63
9/5/69
6/3/69
1/7/70
3/72
11/9/69
12/71
10/26/70
2/72
12/71
1/31/71
5/24/71
9/20/70
11/2/70
12/10/70
10/25/71
2/72
2/73
12/71
11/72
12/71
10/72
11/73
2/74
rim
ElK
7/te/e;
4/8/68
11/9/69
9/23/69
4/13/70
12/2/69
11/29/70
7/22/71
9/28/70
11/6/70
3/5/71
Initial
ri'iigfi
r>M»*
o/n;
7/66
1/70
12/69
10/70
7/72
3/70
1/72
12/70
5/72
3/72
11/71
2/71
4/71
6/71
11/71
10/72
10/7T
2/72
1/73
7/72
7/71
3/74
8/74
Cn*n
•"•aw* ifjl
rip. •
1/flfl
12/69
12/69
8/70
1117
7/70
4/72
3/71
6/72
3/72
11/71
3/71
12/70
6/71
17/71
10/72
7/73
.1/72
7/7.T
1/7?
V71
4/74
10/74
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
AfC<
s • Hoe *• oentraetar tar
-------
APPENDIX A-12-36
Table A-12-14b (Continued)
fii^». I 'Lcrminn
Vn ninnt Yankee
(.•irnriMinQ Station (Vl I
Fin t Colhoun Smiion.
lliiil 1 (NrN I
Sii'iy Power Station.
Unit 1 (Va 1
Siiny Power Station,
Unit 2 IVa 1
Diablo Canyon Nuc Power
Pliint. Unit 1 ICahl 1
Thrrr Milr Mand Nuclear
Sl.ilipn Unit 1 (Pa )
Bflilly Cent-rating
Station (Ind 1
Crystal River Plant.
Un.t 3 (Fla 1
Kewaunee Nude* Power
Plant. Unit 1 (Wise I
Maine Yankee Atomic
Power Plant (Maine)
Pnmt Bearh Nuclear
Pliint. Unit 2 (Wuc 1
Prairie Island Nuclear Gen
Planl. Unit 1 (Minn 1
Shoreh.im Nuclear Power
Station IN V 1
Three Mile Wand Nuclear
Station. Unit 2 (Pa 1
Zion Station, Unit 1
(III I
Arkansas Nuclear One.
Unit 1 (Ark I
Cooper Nuclear Station
INebr I
Indian Pomt Station.
Unit 3 IN Y I
Turkey Point Station.
Unit 4 IFIa I
Calvert Clilts Nuclear
Power Plant. Unit 1 (Md )
Calvert CliHs Nuclear
Power Plant Unit 2 (Md 1
Oronee Nuclear Station.
Unit 3 IS C 1
S-tlnm NurlPiir Generating
Still-in Unit 7 IN J 1
Bi-ll Sulinn1
IN Y 1
Brownt Ferry Nuclear Pwr
Plant. Unit 3 (Ala I
Ow-wr
Vermont Yankrn Nuclear
Power Corporation
Omnha PuMIc Power
District
Virginia Electric &
Power Company
Virgmia Electric ft
Power Company
Pacific Gas ft Electric
Company
Metropolitan Editon Co.
Northern Indiana Public
SAcvtco CoiHpsny
Florida Power Corp
Wisconsin Group
(WPSC. WP&LC. MG&EC)
Maine Yankee Atomic
Power Corporation
Wisconsin Elee Pwr Co ft
Wi« Mich Power Co
Northern Statet Power
Company
Long Itland Lighting Co
Jeney Central Power
and Light Company
Commonwealth Editon
Company
Arkaniai Power and Light
Company
Nebraska Public Power
District
Consolidated Edison
Company
Florida Power and Light
Company
Baltimore Gn and
Electric Company
Baltimore Gas and
Electric Company
Ouke Power Company
Public Service Elee & Gas
Co . PEC. ACEC. DP&LC
New York State Electric
and Gas Corp
T ermessfle Valley
Authority
Cup'
Nil
(MW.)
613 B
457.4
788
788
1060
831
680
825
541
790
497
530
BIB
907
1050
820
778
965
693
845
845
888
1115
838
1085
Tvr»
RWR
PWR
PWR
PWR
PWR
PWR
BWR
PWR
PWR
PWR
PWR
PWR
BWR
PWR
PWR
PWR
BWR
PWR
PWR
PWR
PWR
PWR
PWR
BWR
BWR
NSW7
AC
rnntr
r,E
riwvo
Comb
GHDR
West.
SAW
West
saw
West
0
B&W
Gil
GE
S&L
B&W
Gil
West
PSE
Comb
saw
West
Bech
Wein»r-
7//I
•i// t
1,1 If
\7llf
1/74
•V71
R/71
10/72
5/72
12/71
17//7
4/7ri
1/76
7/77
9/73
.1/73
1/74
7/72
1/71
1/74
10/73
1/7'!
4Q/73
f*.om
mat* ill
riow •
1/77
',//!
'.//7
17/77
'i/74
11/71
7/76
9//1
12/72
V7?
1/77
17/77.
V»ri
'./7-i
H/77
q/7i
4/71
3/74
in?
1/71
1'74
11/71
•,'7r-
I'l/H
2/74
Thn unit erioirwllv pKnmd •§ OyfMr Orwk 2. tramlar
InditlntM eDitponemvn annaan
to Tfne Mta MM She amounted bv OPU IXm/eaV
-------
Table A-12-14b (Continued)
APPENDIX A-12-37
1
l"l»'l»i 1 t rt «l*w»
> an IP Ul.inri Nin Irm Gen
n.mt Unit 7 (Minn I
IV'Mltl C CooV Plunl.
Unit 1 (Mirh 1
• poiuM C Cook Plant.
Unn 2 IMich 1
?V PlMVTI
Sl.mon. Unit 1 IP* )
! L'mpitrli Gcnrfiitinq
Station. Unit 1 IP* )
I implied Generating
Station Unit 7 (Pa 1
NoMh Anna Powpr
Station. Unit 1
i/;7
*5/74
tin
5/74
1/74
7/75
7/74
10/77
1/71
I0/7a
tout
1/77
1/78
1/7S
17/74
11/74
r»m
m««'i«l
'lp« '
',//«
Ifl// 1
l//'l
S//1
',in
i?/;i
0/7r)
1/77
r.tlt
t'n
r,/7«
4/74
3/75
1/74
r,/7B
17/n
4/74
I7'74
V77
f,'7B
io ;p
I«HO
'•ITi
7//5
12/74
85
86
87
88
89
90
91
Mi. .
I V VM .VvWMif 9 4 B»JIW»aW MiaVklll ^* !•••••
-------
APPENDIX A-12-38
Table A-12-14b (Continued)
P»il»rl'l.n« «non
lioiiin NiirlrJit Pliint
(Oil-Will
.limn A Fit/r.iliiik Nuc
Pottpr Pl.ml (NY)1
.Uwpph M Fmlpy Nurlrar
Plant Unn 1 (Ala )
Nrnlvld Ul.inrl NIK Gen
Station. Unit HN J 1
Nrwholil Ulanri NIK- Gen
Station Unit 2 IN J 1
Win H Zlmmpr NIIC Power
Station. Unit 1 (Ohio)
William B McGinip Nuclear
Station Unit 1 IN C 1
Willi.im B MrGimr Nuclear
St.itinn. Unit ? IN C I
FprKpd Rivrr Nurlrar Gen
Sl-ilion Unit 1 IN J)'"
North Anna Power
Station. Unit 2 IVa )
&tn Ono're Nuclear Gen
Station Unit 2 (Calif ) n
S.m Onolre Nuclear Gen
Station Unit 3 (Calif 1 n
Edwin 1 Hatch Nuclear
Plant Unit 2 (Ga 1
Aqinrrp Nurlrar Power
Plant (P R 1
Arkansas Nuclear One.
Unit 2 (Ark 1
LaSalle County Nuclear
Station Unit 1 (III )
LaSalle Count* Nuclear
Station. Unit 2 (Ml )
Want Bar Nuclear Plant.
Unit 1 (Tenn )
Wattt Bar Nuclear Plant.
Unit 2 (Tenn )
Wafprford Generating
Station. Unit 3 (La I
Jn\ M F.irl»y Nurlpar
PI ml linn ? (All 1
Mrnrlrx-uin Power Plant.
Unit 1 ICltlf I
Memiorinn Power Plant.
Unit 2 (Calil )
Owner
Pinilanil Gpnrial Elrrtrle
EWftEBnmlPTgiLC
Powft Authority of the
State of New York
Alahama Power Company
Puhlic Service Electric
and Gat Co.
PuHie Service Electric
and Gas Co
Cincinnati Gas ft Elec Co.,
C&SOEC A OP&LC
Duke Power Company
Duke Power Company
Jersey Central Power
and Light Co
Virginia Electric ft
Power Company
Southern Calif Edison and
San Diego Gas & Elec Co
Southern Calif Edison and
San Diego Gas ft Elec Co
Georgia Power Company
Puerto Rico Water
Resources Authority
Arkansas Power and
Light Company
Commonwealth Edison Co
Commonwealth Ednon Co
Tsnnessee Valley Authority
Tennessee Valley Authority
Tennessee Valley Authority
Tennessee Valley Authority
Louisiana Power and
Lioht Company
Alabama Power Company
Pacific Gas &
Flrctr.c Co
Pacific Gas ft
Electric Co
ClO'
N.I
IMWtl
1130
821
829
1088
1088
810
1160
1150
1140
845
1140
1140
786
583
920
1078
1078
1175
1175
1169
1169
1165
829
1128
1128
TVP«
PWR
BWR
PWR
BWR
BWR
BWR
PWR
PWR
PWR
PWR
PWR
PWR
BWR
PWR
PWR
BWR
BWR
PWR
PWR
PWR
PWR
PWR
PWR
BWR
BWR
NSSS/
At
Conlr
Writ
Bird.
GE
SAW
Wnt
SSC/Becti
GE
0
GE
0
GE
S&L
West
0
West
0
Comb
BAR
Wnt
saw
Comb
Bech
Comb
Bech
GESSC
/Bech
WeM
GHDR
Comb
Rerh
GE
SAL
GE
S&L
B&W
B8.W
West
0
Wett
0
Comb
Ehas
West
SSC/
Bech
GE
0
GE
0
Public
Annr ri
2/R7
8/68
6/69
8/89
8/69
3/68
11/69
11/69
12/68
10/67
1/70
1/70
2/70
5/70
5/70
3/70
3/70
8/70
8/70
B/70
8/70
9/70
B/70
2/71
2/71
NSSS
Conlr
A«wtd
11/68
12/68
5/89
8/69
8/69
9/69
11/69
It/69
12/69
1/70
1/70
1/70
2/70
5/70
5/70
5/70
5/70
8/70
8/70
8/70
6/70
9/70
12/70
2/71
2/7 1
Conti
Pnmll
Anplllrl
6/RB
12/08
10/69
2/70
2/70
4/70
B/70
9/70
6/70
3/69
5/70
5/70
7/70
11/70
9/70
11/70
11/70
5/71
5/71
12/70
6/70
8/71
S/71
on
POl
iHIMtf
2/71
5/70
2/71
liiiiiil
Crlt '
7/M
1//I
10//4
0/74
9/76
6/76
7/7S
10//I,
5/76
1/75
7/7S
5/7">
1/77
1/78
•V77
12/77
3/76
12/76
7/76
10/7fi
1/7H
1/79
Flrlt
cue
Inilul
Dvtign
•(MM*
///4
4//J
?//'.
7/1',
1111
9/76
lift
1/77
?/77
6/75
0/75
I0//l>
4/77
4/7B
5/77
2/78
6'76
V77
0/76
?m
1/7H
J//Q
C'i»n
ffMtf III
Op.. •
')//4
'.//I
til',
Ml',
'.III
10/76
11/7'j
•///
H/77
6/T)
1976
1/76
Hi/76
b/77
5'78
7/77
4/78
P/76
S/77
1/77
4/77
T./7H
P/70
»ASNV look ow Niaoar. MohMk oontraei for Emen Plant
JOMV Cixi'il (MI an option for another unit e> iami tut
ScMduta iod.lh.li. pMidlna me
and eanttantd In ttM
nmannl eondlilant
-------
Table A-12-14b (Continued)
APPENDIX A-12-39
f.or. 1 1 Pillion
Viigil C Summn Nurhw
Ji.i Unit 1 IS C 1
WPTSS Nurlm Pion-rt
Mi f (W «h )
Shr.nn Hum Station.
linn 1 INT 1
Shraron Harm Station,
Unn?|NCI
SNp.von H.IIMI Station.
Unn 1INCI
Shr.ii nn Hi* in Sill ion.
Unit 4 |N C )
COMED/WEST 1
Hill
COMED/WEST2
(III!
Nmlh Anru Power
Station llnil3|Vll
North Anna Rower
Station. Unit 4 (V* I
Dvital River Plant.
Unu4|Flal
Alvm W Vonllf Niiclmr
Plum Unit 1 IG» 1
Alvin W Vnollr Nuclear
Plant. Unit 7 1C* 1
Beawr Val'rv Power
Station Unit 1
Nmr Mile Poml Nuclear
Power St»l«'n Unit 7 (NVI
MjiMm Niirlr.ii Plant
Unit 1 ICilil 1
Rom» Pnmt Unil 1 IRII
S**ihrooV Nuclear
Si at. on IN H l"
Bavvrle Gem-rating
Station IN Jl
HoHitlfr Ranch
ICal'l 1
(Ofonol
IVV«h 1
Virgil C Summer Nuclear
Sla Unit 2 IS C 1
Unit I.INJI
Umt 2 IN J )
Unit 1
Unit}
(hm
South Cnolin*
Elvrtric & CM Co
W*KfilnQTon l\iWlr Poww
Sti|'
NM
IMW.I
900
1103
BIS
BIB
BIS
BI6
MOO
1100
900
900
8B7
1100
1100
847
1100
462
950
860
1000
1000
1000
1000
900
1100
1100
1250
12SO
tvn.
pwn
BWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
PWR
BWR
M-KV
AE
r.nnlr
Wmt
Gil
GE
8&R
WPII
Ehai
Wnt
Elm
Wnl
Ehat
Wnl.
Elm
Weil
SM.
Weil
SAL
n&w
SAW
BftW
SAW
Weil
Gil
Weil
SSC/
nocn
Wnt
SSC/
Bech
Wnt
saw
GE
SftW
saw
Public
Aimril
2/71
2/B7
4/71
4/71
4/71
4/71
4/71
4/71
4/71
4/71
8/71
9/71
9/71
9/71
6/71
11/62
4/66
3/67
6/67
6/87
3/68
4/B9
2/71
5/71
5/71
8/71
B/71
•KM
Crmlr
Aw»d
2/71
3/71
4/71
4/71
4/71
4/71
4/71
4/71
4/71
4/71
8/71
B/71
B/71
B/71
B/71
CfMI*
P*ml
8/71
8/71
B/71
9/71
B/71
fl/71
B/71
B/71
11/63
4/69
Cfl
•m.
imiw
on •
llir.
4/77
IO//».
rP//n
fi/70
a mi
ftar
Itiltial
f >...,.
P>««f
Mil
mi
Mil
vm
Q./71
(.-KT,
rjp- •
Mil
•tin
I///
!•(/•<
ri/'i
I'MIJ
10/71)
10/71
IT77
1978
19/8
1978
107-)
10, 7H
in;;
10RO
|f>HO
l«80
1077
1979
IOHI
1178
1980
1970
1080
18
9
ra
21
72
23
124
125
126
127
128
129
130
131
A
B
C
D
E
F
G
M by urtHT on 11/11
-------
APPENDIX A-12-40
Table A-12-14b (Continued)
Pii'lri I ( I'rannn
rrc HIHR i
rtr MiiiR}
Triiy Niirlr.ii Power Plant.
Unit 1 IOH)
Perry Nurlr.v Pown Plant
Unit 2 (PHI
Rome Point. Unit 1 -
N.I
IMW.I
1160
11BO
880
880
BSD
BOO
BOO
BOO
Typi
NSSS/
At
Conn
'iihllr
Annr ft
R/71
0/71
10/71
10/71
1/71
11/71
11/71
11/71
NSSS
Cam>
AMMt
Conn
Cwmll
Appllwl
».P/
P»IU
linint
InllKI
riu •
tlttl
?<••
lr.'.«l
f>"tiO"
r>>n»»-
»«fl>l
'I0» '
I'll 1
rit'i
i'ii"i
rr-.i
rtf,7
rtn
n«o
1979
o
p
a
R
S
T
U
-------
Table A-12-14b
APPENDIX A-12-41
10h AIIIMIIP
57 Aik;invn One No. 1
lOli AikniK.N One No. 2
82 Ainolil Nn 1
48
0 P.iyvtle
72 Braver Valley No. 1
1 30 Braver Valley No. 2
P5 Bell Station
13 Big Rock Pt.
14 BONUS
34 Browns Ferry No. 1
35 Browns Ferry No. 2
66 Browns Ferry No. 3
79 Brunswick No. 1
80 Brunswick No. 2
61 Calvert Cliffs No. 1
62 Calvert Cliffs No. 2
123 COMED/WEST No. 1
124 COM ED/WEST No. 2
68 Cook No. 1
69 Cook No. 2
58 Cooper
49 Crystal River No. 3
127 Crystal River No. 4
11 CVTR
91 Davis Besse
46 Diablo No. 1
89 Diable No 2
3 Dresden No. 1
21 Dresden No. 2
28 Dresden No. 3
9 Elk River
94 Farley No. 1
114 Farley No. 2
5 Fermi No 1
90 Fermi No 2
93 Fitzpatnck
100 Forked River No. 1
43 Fort Calhoun No. 1
22 Ft St Vrain
23 Ginna No. 1
16 Haddam Neck
7 Hal lam
118 Hanford No. 2
119 Harris No 1
120 Harris No. 2
121 Harris No 3
122 Harris No. 4
76 Hatch No. 1
104 Hatch No. 2
E Hollister
Significant Milestones - Index
8 Humlmlclt Nn. 3
77 Hutchlnwn No. 1
2 Inclinn Point No. 1
2G Iralinn Point No. 2
59 Indian Point No. 3
50 Kewaunee No. 1
15 Lacrosse
107 LaSalle No. 1
108 LaSalle No. 2
73 Limerick No. 1
74 Limerick No. 2
51 Maine Yankee
A Malibu No. 1
98 McGuire No. 1
99 McGuire No. 2
115 Mendocino No. 1
116 Mendocino No. 2
85 Midland No. 1
86 Midland No. 2
L Mid South No. 1
M Mid South No. 2
25 Millstone No. 1
78 Millstone No. 2
32 Monticello
18 N Reactor
95 Newbold No. 1
96 Newbold No. 2
19 Nine Mile No. 1
131 Nine Mile No. 2
75 North Anna No. 1
101 North Anna No. 2
125 North Anna No. 3
126 North Anna No. 4
36 Oconee No. 1
37 Oconee No. 2
63 Oconee No. 3
20 Oyster Creek No. 1
F Pacific Power & Light
29 Palisades
6 Pathfinder
10 Peach Bottom No. 1
39 Peach Bottom No. 2
40 Peach Bottom No. 3
N PEC/HTGR No. 1
O PEC/HTGR No. 2
P Perry No. 1
Q Perry No. 2
S Ferryman No. 1
T Perryman No. 2
24 Pilgrim No. 1
12 Piqua
31 Point Beach No. 1
62 Point Beach No. 2
51 Priilrlr Ulanrl No 1
6/ Pr.iinn Mm*! No 2
I PSrG No 1
J PSEG Nn 2
3.1 Quail Cilins No 1
38 Quad Citi« No 2
71 Rancho Sero
U River Bend
30 Robimon No. 2
B Rome Point Unit No. 1
R Rome Point Unit No. 2
41 Salem No 1
64 Salem No. 2
17 San Onofre No. 1
102 San Onofre No. 2
103 San Onofre No 3
C Seabrook
G Seattle/Smohomish
83 Sequoyah No 1
84 Sequoyah No 2
1 Shippingport
54 Shoreham
117 Summer No 1
H Summer No. 2
44 Surry No 1
45 Surry No. 2
87 Susquehanna No. 1
88 Susquehanna No. 2
47 Three Mile No. 1
55 Three Mile No. 2
92 Troian No 1
27 Turkey Point No. 3
60 Turkey Point No. 4
109 TVA/B&W No 1
110 TVA/B&W No. 2
42 Vermont Yankee
81 Verplanck No. 1
128 Vogtle No. 1
129 Vogtle No. 2
113 Waterford No. 3
111 Watts Bar No. 1
112 Watts Bar No. 2
4 Yankee
97 Zimmer No. 1
56 Zion No. 1
70 Zlon No. 2
-------
APPENDIX A-12-42
Table A-12-14c
Nuclear Steam Supply System Contract Awards*
U.S. Central Station Reactors
No. of Units/Net MWE
YEAR
THRU IBM
IOCS
1966
1«i»
19B8
1969
1970
1971
TOTALS
QE
No
5
3
9
R
B
3
3
3
43
MWE
1.613 B
2.110 1
7.7459
7.07BO
7.334 7
2.9860
2.9420
4.459.0
36.273.6
WEST
No.
6
3
6
13
4
3
6
11
60
MWE
1.7870
1.PBGO
4.973 0
10.7770
4.4380
3.1290
4.5950
10.7040
41.8390
RfrW
No.
1
.
3
5
3
2
2
16
MWE
2G60
2.sr.R o
4.242 0
2.1820
2.3500
1.8000
13.397 0
COMB
No.
1
2
6
1
4
13
MWE
IBS
1.1674
4.1080
1.1400
4.3650
10.786 0
OTHER
No.
B
1
8
MWE
1.107 8
3300
1.437.8
TOTAIS
No
M
7
20
31
15
7
14
17
131
MWE
47101
4.417 1
16.1114 3
767030
13.954 7
7.255 0
14.2520 1
16.963 0
103.734 2 ^
1V1/T1
STATUS
Dccornin Isstonoo
Operable1
Buildina'
Contracted
Announcwi
Total
NO.
UNITS
6
23
54
48
20
151
CAPACITY
MWE (Nell
2004
10.0308
45.7790
47.724 0
19.5820
123.3162
1 Achtoed InnW ctlilcriltv. net pwirmntntlv ihutdown
* Conif'UCtiOfi permit
1
Achievement of Commerical Operation Nuclear
Power Reactors Contracted for as of 12/1/71
YEAR
THRU 1970*
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
MWE Net
Annual
3.565 1
12.2178
14.350 1
14.1640
13.6120
4.338 0
16.409 0
12.963 0
4.243 0
1.9670
Cumulative
59052
9.4703
21.688 1
36.038 2
50.2022
63.814 2
68.1522
84.561 2
97.524 2
101.7672
103.734 2
No. of Unlti
An nu •
6
IB
17
IS
14
5
16
13
4
2
Cuimiliave
21
27
45
62
77
91
96
112
125
129
131
a* W3O/71
Informitlo*
IndudH 6 plmtf which KtilMd
HMmi ITS MWM.
PMtlflno^r CM ft MMM.
nd by utHlita.
i prim nan but hew tbiee bom
»lquil1t4MIMil. CVTNIIIMMM.
Elk mm 122 MM.
•ONUS II* B MM.
-------
APPENDIX A-12-43
have a nominal capacity of 300 MTU/yr. The Allied-Gulf
facility is in Barnwell, S. C., is designed for the Purex process,
and will have a nominal capacity of 1500 MTU/yr. The GE
plant is expected to go into operation in late 1972, and the
Allied-Gulf plant in late 1974. The forecast annual require-
ments for spent fuel reprocessing are 1400 MTU in 1975 and
and 2800 MTU in 1980.
In both the Purex and the Aquafluor processes, the spent
fuel, transported in heavily shielded casks from the reactor
facilities to the reprocessing plant, is unloaded underwater and
stored temporarily underwater until there is an elapsed time of
about 150 days from the time of withdrawal from the reactor.
This storage time allows the decay of many short, half-life
fission products in the fuel. After suitable storage, the fuel
assemblies are processed remotely in heavily shielded con-
crete cells.
To start, the fuel assembly (up to 15 ft long) is dismantled
to separate the stainless steel or zircalloy fuel-bearing tubes
from the remainder of the assembly. The stainless and zirc-
alloy tubes are then chopped into small segments to expose the
fuel and these segments are placed in nitric acid which dissolves
-------
APPENDIX A-12-44
the fuel and its fission products and leaves the tubing segment
(hull) intact. This "chop-leach" operation produces contaminated
fuel assembly hardware and hulls as solid waste, and it releases
fission product gases which undergo treatment to remove radio -
iodines and particulates before discharge.
Next, the dissolved fuel is processed by means of solvent
extraction to separate the uranium and plutonium from each
other and from the fission products (high-level wastes). In the
Purex operations, the fission product wastes from solvent ex-
traction are concentrated to recover nitric acid and are stored
in acid-form* in stainless steel tanks for up to five years before
they have to be converted to solids in an acceptable form for
ultimate disposal at a Federal Repository. In the Aquafluor
process, the fission product wastes will not be stored tempo-
rarily as liquids, but will be calcined to a solid form. The cal-
cined solids will be sealed in stainless steel cylinders which will
be stored underwater to remove fission product heat.
Up through the first solvent extraction operation, the
Purex and Aquafluor processes are very similar, and they vary
only in subsequent purification of uranium and plutonium. The
* Initial NFS operations have collected and stored about 500, 000 gallons
of neutralized fission product wastes.
-------
APPENDIX A-12-45
Purex process uses additional solvent extraction operations to
purify both the uranium,and plutonium, and the Aquafluor process
purifies the uranium by fluorination.
Low-level liquid wastes in the reprocessing operation are
primarily the effluent from nitric acid recovery. In the case of
NFS, this and other low-level aqueous waste streams are treated
by scavenging, precipitation, and ion exchange before discharge
to a watercourse. In the design of the GE and Allied-Gulf
facilities, there is no low-level aqueous discharge to the water-
course; instead, there is an internal water recycle with a bleed -
off evaporation step to maintain an equilibrium concentration of
tritium in the recycled water.
The curie quantities of the fission products and the acti-
nides in a metric ton of uranium fuel following different burnups
and after different cooling times are shown in Table A-12-15.
/e n\
The data ' has been listed on the bases of half-lifes of the
fission products and the actinides to show those that are of sig-
nificance for long-term storage, and the radiogases are shown
separately.
-------
APPENDIX A-12-46
Table A-12-15
Curies of Long Half-Life Fission Products and Actinides
per MTU of Fuel for Different Burnups and Cooling Times
Burnup - MWD/MTU
SP. PWR - MW/MTU
CLG. Time - Days
Radionuclide
Sm 151
Cs 137
Sr 90
Eu 154
Sn 121 m
Sb 125
Pm 147
Cs 134
Eu 155
Gd 162
Ru 106
Ce 144
Sn 119 m
Ag 110 m
Radiogases
1-129
H-3
Kr-85
Actinide
Pu-239
Am-243
Pu-240
Am-241
Pu-238
Cm-244
Half -Life
90 y
•/
30 y
28 y
16 y
s y
*/
2. 7y
2. 7y
v
2. 1 y
^
1. 7 y
- >i y
i y
285 d
250 d
249 d
1.6xlO?y
12.4 y
»/
10. 8 y
2 4xl04
-1.0xl04y
6. 58x1 0By
4. 75xl0^y
9. 2xlQly '
1.9xl01y
GE Data
21,900
30
160
l.OxlOJ!
4
7.2x10*
4
5.4x10,
1.3x10^
5.0x101
3
3.8x10;:
1.7x10^
4
3.2x10,
3
1.6x10,
l.OxlOJT
3. 2xlOJ?
7.2x10,
1.0x10,
3.5x10
0.02
_
3
7.4x10
43,800
30
160
1.5xlO|?
5
1.4x10*
4
8. 9x10,
4.0x10,
1.0x10,
3
7. 6x10^
2. 1x10^
4
9. 5x10*
3
4.0x10,
2. 5x1 Og
5. 9x10,.
7. 3x10,
1.0x10,
1.4x10
0.04
_
4
1. 3x10
ORNL Data
33, 000
30
150
1.2x10!?
5
1.1x10*
^
7.7x10,
6.8x10
_
3
8.1x10^
9.9x10*
5
2.1x10,
3
6.4x10,
1.7x10^
4.1x10^
7.7xlOr>
1.0.10
2.6x10
2
6.9x10^
4
1.1x10
3.3x10^
1.7x10,
4.8x10^
2.0x102
2.8x10,
2.5x10
33,000
30
3,652
5. 2x10^
4
8.5x10*
4
6.0x10,
4. 5x10
_
2
6.9x10,
7. 9x10,
3
8. 3x10^
2
1. 6x10
2
5. 5x10^
1.5x10
-
2
4.0x10,
3
6.0x10
-------
APPENDIX A-12-47
(6)
The forecast of the annual generation rate (Ci/yr) and
the total accumulated quantities (Ci) of the significant long half-
life isotopes from fuel reprocessing are shown in Table A-12-16,
including the volumes of these high-level wastes if stored as
liquids or as solids.
(1 6)
The generation rates ' of miscellaneous low-level
solid wastes and of fuel hulls and hardware are given in
Table A-12-17.
(7) Transportation
A good summary of transportation is given in the Nuclear
Industry 1971, WASH-1174-71, by the U. S. AEG. The materials
moved and the types of packages used are given in Table A-12-18
reproduced from that document.
Spent fuel shipments will require a larger tonnage of ship-
ments than any other phase of the nuclear power cycle (i. e.,
until high-level waste shipments to Federal Repository are
necessary) because of the massive shielding that is required
(8)
during shipment. A review of spent fuel shipments indicates
that 73. 5 percent of the known power reactor sites can be served
by rail, 22 percent by truck only, and 4. 5 percent by barge.
-------
Table A-12-16
Forecast of the Generation Rates and the Total Accumulations of
Long-Life Fission Products and Actinides in
High-Level Wastes from Fuel Reprocessing^6)
Isotopes
H-3
Kr-85
1-129
Sr 90
C 137
Pu 238
Pu 239
Pu 240
Am 241
Am 243
Cm 244
/ V
Gals/yr if liq.
Cu ft/yr if sol.
Generation Rate
(curies/year)
1970
4
4.0x10*
6. Oxl O5
2.0
1980
6
2.1x10°
3. 3x10 '
1.1x10
1990
6
6. 2x10°
9. 0x10 '
4.4x10
As High Level Liquid or Solid Wa
6
4.0x10°
g
5. 6x10°
7. Oxl Oj
9.0x10,
2
1.2x10*
9. 0x10^
2.1x10):
1.3x10
4
1.7x10
1.7xl02
8
2.3x10°
8
3.2x10°
4.1x10*
5.0x10,
<
7.0x10;:
5.0x10?
4
1.0x10*
7.4x10
s
9.7x10
9. 7xl03
8
5. 6x10°
8
8.8x10°
2.0x10°
5.0x10*
4
6.0x10*
4.4x10°
1.0x10,
1.8x10
«
2. 7x10
2. 7x10*
Accumulation
(curies)
1970
4
4.0x10*
6.0xlOD
2.0
stes
6
4.0x10°
g
5.6x10°
7.0x10^
9.0x10,
y
1.2x10,
9. 0x10^
2.1x10):
1.3x10
4
1.7x10
1.7xl02
1980
6
7.3x10°
1. 2x10^
4.8x10
8
9. 6x10°
9
1. 2x1 0^
2.0x10*
4
4. 0x10*
2. 3x1 0^
2. 3x1 0_
3.0x10
c
4.4x10
4.4x10*
1990
7
3. 6x10 '
5. 7x10,
2.7x10
9
4.6x10*
9
6. 5x10^
8.3x10°
2.4x10?
4.0x10,
2.3x10^
i.sxio:
1.4x10
7
2.4x10
2.4xl05
(a) Assumes 100 gallons per 10,000 Mwd.
(b) Assumes 1 cu ft per 10, 000 Mwd.
(c) Assumes LWR @ 33, 000 Mwd/MTU, 30 Mw/MTU,
90d. clg;LMFBR @ 80, 000 Mwd/Mtu, 148 Mw/MTU 30d.
(d) Assumes
(e) Assumes
in 1980-
0. 5% of Pu to waste.
introduction of LMFBR
CO
clg.
-------
APPENDIX A-12-49
Table A-12-17
Generation of Miscellaneous Solid Waste and
Hulls and Hardware at Fuel Reprocessing Plants
1970
Pur ex
1975
Miscellaneous
Waste - ft 5. 1x10* 2. 2x10^
- Ci 5.2x10 2.3x10
Cladding - ft3
- Ci
Aquafluor
Miscellaneous
Waste - ft3
- Ci
Cladding - ft3
- Ci
The total accumulation of
by 1980 is estimated to be
2.4xl03
6. 5x10
3. 6x10*
3. 7x10
3. 7x10^
1.0x10°
cladding hulls and
40, 000 cubic feet
1980
6. SxlOJ?
7.8x10
6. 7xl03
1.8x10
4.5x10*
5.6x10
4.8xlOJl
1.3x10
hardware
-------
APPENDIX A-12-50
Table A-12-18
Material Flow in the Nuclear Fuel Cycle
Material
Point to Point
Movement
Packaging
Uranium Ore Cone.
Normal UF
e
b
Enriched
Enriched UC*2
Powder and
Pellets
Fuel Assemblies
Spent Fuel
Uranyl Nitrate
Plutonium Nitrate
Solid Fission Prod.
Waste*
Low-Level Waste
Mill to feed preparation
Feed preparation to
enrichment
Enrichment to material
processing
Material processing
to fuel fabrication
Fuel fabrication to
power reactor
Power reactor to
reprocessor
Reprocessor to fuel
fabrication
Reprocessor to fuel
fabrication
Reprocessor to Federal
Repository
Anyone to waste burial
Drums
Press, cylinders
Press, cylinders and
protective packages
Drums and
birdcages
Protective packages
and birdcages
Shielded casks
Tank trucks and
protective packages
Pu containers and
protective packages
Shielded casks
Drums and pro-
tective packages
* Future shipments.
-------
APPENDIX A-12-51
Accordingly, the 22 percent served by truck only would require
smaller 25-ton casks capable of being transported on load-
limited highways, whereas the other sites could be serviced by
larger 75-ton casks suitable for rail or barge shipments. As-
suming lead-shielded shipping casks with a spent fuel payload
of 0. 25 MTU/ton for the small truck casks, and 0. 045 MTU/ton
for the large rail casks, and round-trip times of 1 week and
3 weeks, respectively, the total tons shipped round-trip and the
number of casks required are shown in Table A-12-19.
Table A-12-19
Spent Fuel Shipments
Year
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
By
Truck Tons
Shipped
1,480
2,670
5.020
8, 180
12,640
17.800
24, 900
32, 000
40, 900
49, 800
58, 700
No. of
25-Ton
Casks
1
2
2
4
5
7
10
13
17
20
23
By
Rail Tons
Shipped
2,940
5,300
9,500
16,300
25. 200
35,400
49, 700
63, 800
81,400
99, 200
116,800
No. of
75-Ton
Casks
2
2
4
7
10
14
19
24
31
38
44
-------
APPENDIX A-12-52
A trend towards uranium-shielded casks could reduce the
above round-trip shipment tonnages, but will not significantly
affect the number of casks required. The number of spent fuel
shipments in 1980 will be about 1, 800.
4. RADIOACTIVE WASTES FROM MEDICAL AND
INDUSTRIAL APPLICATIONS
The medical profession is rapidly developing diagnostic and
therapeutic uses for both reactor-produced and cyclotron-produced
radioisotopes. These uses produce relatively small quantities of
radioactive waste. In diagnostic applications, whereby a patient
ingests radioactive material to permit a direct measurement of an
area of concern, the radioactive material is of short half-life to mini-
mize radiation exposure of the patient. On the other hand, in the case
of therapeutic treatments, radiation energy is utilized so the radio-
isotopes used are of high radiation energy and are long half-life well
encapsulated materials, used to the very maximum before they are
replaced. Replaced encapsulated materials are sometimes reused
for other applications or are of such low activity they are sent to one
of the six land burial sites for disposal which also service nuclear
power facilities. These land burial sites are shown in Table A-12-20.
-------
APPENDIX A-12-53
Table A-12-20
Licensed Low-Level Waste Burial Sites
Site Location
Operation
Area of Site
(acres)
Richland, Wash.
Beatly. Nevada
Sheffield, 111.
Morehead, Ky.
West Valley, N. Y.
Barnwell, S. C.
Nuclear Engineering Co.
Nuclear Engineering Co.
Nuclear Engineering Co.
Nuclear Engineering Co.
Nuclear Fuel Services, Inc.
Chem-Nuclear Services, Inc.
100
80
27
200
10
5.
Table A-12-21 presents some of the radionuclides used
in medical and industrial applications.
RADIOACTIVE WASTE FROM AEC FACILITIES
In this section, all the information provided by the Atomic
Energy Commission for the purpose of inclusion in this study is
presented.
(1) Radioactive Waste Management Principles and Practices
Many things are unique about the production and utilization
of radioactive materials in the United States. One of the most
-------
APPENDIX A-12-54
Table A-12-21
Radionuclides Used in Medical
and Industrial Applications
Radioisotope
Used in Medical Diagnostic Work:
Carbon-11
Nitrogen- 13
Oxygen-15
Fluorine -18
Sulfur -37
Calcium-47
Chromium- 51
Gallium- 68
Selinium-73
Technetium- 99m
Used in Doubly Encapsulated Form
of Therapy Work:
Cobalt-60
Strontium -90
Cesium-137
Plutonium -2 38
Used in Doubly Encapsulated Form
for Industrial Applications:
Cobalt-60
Strontium -90
Cesium-137
Thulium- 170
Iridium-192
Americium- 24 1
Emission
P+
0+
P+
/?+
ft~y
ft*
y
0+Y
/3+Y
P'7
y
P~
y
a
y
8
y
y
y
or
Half -Life
20. 5 m
10.1 m
2. 1 m
1.87 m
5. 0 m
5. 8 d
26.. 0 d
68.0 m
7.0 h
5. 9 h
5.25 y
28.0 y
30.0 y
92.0 y
5.25 y
28.0 y
30. Oy
127.0 y
75.0 d
475.0 y
-------
APPENDIX A-12-55
unusual is the fact that the hazards attending the development
and growth of the pertinent science and technology, which had
been recognized soon after the discovery of radioactivity, were
consciously and explicitly dealt with by means of operating pro-
cedures when large-scale Government activities began in the
early 1940's. The hazards were also recognized by the Congress
when the Atomic Energy Act was passed in 1946, as is illustrated
by Section 5(c)(2) of the Act which stated that "The Commission
shall not distribute any by-product material to any applicant...
who is not equipped to observe or who fails to observe such
safety standards to protect health as may be established by the
Commission.. . " Likewise, Section 12(a)(2) stated that the Com-
mission was authorized to "establish by regulation or order such
standards and instructions to govern the possession and use of
fissionable and by-product materials as the Commission may
deem necessary or desirable to protect health or to minimize
dangers from explosions and other hazards to life or property. "
These statutory provisions were retained when the Act was
thoroughly revised and updated in 1954 and, in addition, a basic
policy statement was added to Chapter 1, Section 2: "d. The
processing and utilization of source, by-product, and special
nuclear material must be regulated in the national interest and
-------
APPENDIX A-12-56
in order to provide for the common defense and security and to
protect the health and safety of the public. " Further, Sections 53,
62, and 81 set up a framework f.or licensing the possession and
use of special nuclear material, source material, and by-product
material. A similar licensing structure was set up for production
and utilization facilities by Chapter 10 of the Act.
Administration of these statutory responsibilities with re-
spect to licensees has been implemented by issuance of Rules
and Regulations, Title 10, Part 20, Standards for Protection
against Radiation. Sections 20. 301 through 20. 305 of Part 20
apply specifically to Waste Disposal. Various other issuances
are also pertinent, such as Part 30 on by-product material,
Part 50 on production and utilization facilities, and Part 71,
Packaging of Radioactive Material for Transport. In addition,
similar requirements are laid on contractors who operate
Government-owned facilities for AEC programmatic purposes.
In these cases, regulations are incorporated in AEC Manual
Chapter 0524, Standards for Radiation Protection.
Central to the CFR and AEC Manual regulations just
referenced is one basic principle that, as mentioned above, has
differentiated the nuclear industry (including the research and
-------
APPENDIX A-12-57
development phases) from other "high technology" activities
that have marked the twentieth century. The environmental
damage that has accompanied such major activities as trans-
portation and electric power generation, where disposal of the
waste products was allowed to follow economic principles that
externalized the costs of pollution by dumping the wastes on the
"commons, " contrasts sharply with nuclear activities where the
basic principle is to contain the wastes rather than to disperse
them. Because of the relative compactness of nuclear wastes,
essentially complete retention is quite practical.
This statement about containment must not be misunder-
stood, for it is not claimed that no radioactivity is released to
the environment. But concentration and retention is the primary
management technique; dilution and dispersal is a secondary tool
used where concentrations are very low and volumes are high.
This concept explains why AEC classifies liquid wastes primarily
on the basis of penetrating radiation as low-activity or high-
activity; the latter class requires retention while the former
either meets appropriate standards for direct discard or can be
treated (by precipitation, ion exchanges, decay-storage, etc.)
to provide a discardable fraction and a fraction that is stored
-------
APPENDIX A-12-58
indefinitely under conditions similar to those required for high-
activity wastes. So-called "intermediate-level" wastes are
treated by the same fractionation techniques used for many low-
level wastes; the major difference is that low-level wastes can
often be discharged directly, after monitoring, whereas inter-
mediate level wastes may require more than one fractionation
to obtain a discardable portion. All solid radioactive wastes,
whether low- or high-level with respect to external radiation
hazard, are retained by storage or land burial.
In addition to the low-high dichotomy, there are other
characterizations of radioactive wastes that are important. A
package of solid wastes, for example, may contain potent gamma-
emitting isotopes of short half-life; special procedures would be
required in handling the package today, but in 10 or 100 years
there may be no residual hazard. On the other hand, a package
containing 10 grams of plutonium would pose no external handling
hazard today, but represents such a serious potential future
danger if mishandled, due to the combination of its long half-
life and high toxicity per unit weight, that it must be stored under
conditions that will keep it out of man's environment for ex-
tremely long periods of time.
-------
APPENDIX A-12-59
While the rules and regulations cited above are quite de-
tailed and the principles they seek to implement may seem quite
simple and clear, it should be realized that this situation has
evolved over a period of about three decades, with considerable
improvement having taken place. Especially in the early days,
there were expedient actions taken that did not result in expos-
ing the public to radiation in excess of standards but which left
the wastes in types of interim storage requiring eventual further
effort for the provision of long-term storage. In particular, the
early storage of relatively dilute and neutralized liquid wastes
from nuclear fuel reprocessing has left a backlog of wastes in
interim storage which cannot be handled by the technology now
available for early conversion to compact solids of the con-
centrated acid wastes from modern reprocessing plants. Con-
sequently, AEC does not claim to have resolved all of the
technical questions on long-term storage of all types of high-
level wastes, but believes the work in progress will resolve
them well within the time provided by safe interim storage.
In order to devote increased management attention to the
resolution of its waste handling problems, the AEC recently
formed a Division of Waste Management and Transportation.
-------
APPENDIX A-12-&)
The staff is currently formalizing and scheduling a number of
objectives, policies, and actions that had long been an informal
part of the AEG waste management responsibility or goals to be
sought. For example, high-level liquid waste storage in tanks
will not henceforth be regarded as an acceptable practice for
long-term storage although it has proven adequate for interim
containment pending the development of policy, technology, and
facilities for long-term management. As a step toward im-
proved interim containment, additional stress is being placed
on solidification for in-tank storage in a form providing reduced
mobility but at the same time not precluding removal to deep
underground storage or transfer to a repository. Whatever
method of long-term storage is finally selected for these high-
level residues, it is intended that there be high assurance of
isolation from man's environment with minimal reliance on per-
petual maintenance and surveillance by man.
Similar principles have been incorporated in the frame of
reference applied to licensee handling of high-level liquid wastes.
Under a recent amendment to AEC regulations, licensed fuel
reprocessing plants are limited in liquid waste inventory to that
processed in the prior five years. The liquid wastes must be
-------
APPENDIX A-12-61
converted to an approved solid form as necessary to comply
with this limit, and be sent within another five years to a Federal
Repository for long-term (that is, indefinite) storage. Technology
to provide a basis for compliance with these regulations has
been provided by AEC development programs, including full-
scale demonstration of the pot, radiant spray, and phosphate
glass processes in the Waste Solidification Engineering Proto-
type pilot plant at Pacific Northwest Laboratories. (See "Status
of the Waste Solidification Demonstration Program, " McElroy,
Blasewitz, and Schneider, Nucl. Technol. , Vol. 12, No. 1,
pp. 69-82, Sept. 1971.)
The Nuclear Fuel Services Facility, West Valley, New
York, is the only licensed fuel reprocessing plant currently in
operation. To date approximately 525, 000 gallons of high-level
radioactive waste have been accumulated at NFS, and these
neutralized liquid waste solutions are contained in underground
storage tanks. The Midwest Fuel Recovery Plant, Morris,
Illinois, scheduled to begin operation about mid-1972, will con-
vert high-level radioactive waste to solid form for interim
storage on site, pending the availability of a Federal Repository
for such wastes. The Barnwell Nuclear Fuel Plant, Barnwell,
South Carolina, is scheduled to begin operations in 1974. It will
-------
APPENDIX A-12-62
store high-level radioactive waste as nonboiling acidic solutions
for an interim period prior to conversion of such wastes to a
solid form for transfer to a Federal Repository.
Commercial land burial facilities are authorized to bury
any waste other than high-level waste generated by fuel repro-
cessing plants. One of the major concerns in authorizing burial
of radioactive wastes has been the possibility of environmental
contamination. In this regard, careful review has been made
of the geological and hydrological aspects of each of the burial
sites to determine whether radioactive material would migrate
from the burial site. Inspection of burial sites has indicated
that there have been no significant problems associated with
the burial of wastes. Results of environmental surveys, con-
ducted by licensees at their burial sites, indicate that there has
been no migration of radioactive material from the burial sites.
(2) Description of Available Data
Having outlined the principles on which control of radio-
active wastes are based, it is appropriate to discuss the infor-
mation that has been assembled. The following paragraphs
describe the kinds of data available and indicate a few limitations
on completeness and usefulness.
-------
APPENDIX A-12-63
Some definition of terms was provided in the earlier
discussion of low-, intermediate-, and high-level radioactivity.
The significance of transuranium content was also discussed,
since the categorization of solid waste packages according to
"high" or "low" level of penetrating radiation may be completely
inadequate as an indication of potential internal hazard. While
a division of solid wastes into transuranic and nontransuranic
classes is philosophically simple and may require important
differences in storage techniques, it is technically and adminis-
tratively difficult. Where solid wastes are transmitted to
another site for burial or long-term storage, there may be un-
certainty on the receiver's side that the shipper has properly
classified each package. The receiver may, therefore, feel it
necessary to open and inspect all packages, an operation of con-
siderable cost and potential hazard.
Another definitional problem posed by any attempts to
tabulate quantities of wastes is possible confusion between
generation and disposition, which could lead to either double
counting or noncounting. The problem comes partly from the
fact that some sites "dispose of" wastes by shipping them to
other sites where they are buried and hence in a sense "disposed
of" again. (Buried wastes are not really "disposed of" in the
-------
APPENDIX A-12-64
sense of sewage plant effluents, since they are physically re-
trievable even though retrieval may never be planned or
necessary.) Equally significant is the rehandling of liquid
wastes during or after interim storage. Several AEG sites
that have large inventories of tanked liquid wastes rehandle
millions of gallons each year as a part of volume reduction and
waste solidification programs. These quantities may greatly
exceed the volumes of new waste generated.
Another category of limitations on the availability of data
stems from the decentralized operational mode of AEC.
General policies and programmatic objectives are established
at Headquarters, with due regard for inputs from the Executive
and Legislative Branches. But the implementation is delegated
to field management which in turn administers the programs
through contractors. In consequence, routine operational data
on activities such as waste disposal are not transmitted to
Headquarters. Collection of such data from the sites would re-
quire considerable effort and take several months.
On the other hand, it is recognized that there are advan-
tages to the maintenance of centralized documentation of the
geographical location of radioactive waste storage facilities and
-------
APPENDIX A-12-65
of the quantities and types of wastes stored in each. It is,
therefore, contemplated that such a system of records be set
up and, in fact, initial contacts have been made at some of the
sites and data collection is underway. A year or more may
elapse before this effort is complete.
Another source of difficulty in assembling the data is the
lack of a single suitable unit of measurement for consolidation
of waste quantities. While gallons or cubic feet are convenient
units, and are used in the appended tables, they have little
meaning for consideration of environmental impact. (They do
indicate real estate requirements and offer some handle on
costs, of course. ) Tabulation of curies or megacuries might
appear more sophisticated, but is not suggested here because
a large fraction of the curie content of solid waste is composed
of relatively short-lived fission products and induced activity
and hence changes rapidly. For a particular storage site and a
particular assumed accident situation, curie content—weighted
by air, water or body burden index values for the major radio-
nuclides present—is a useful parameter, but summation of such
weighted values among sites is of questionable validity. Since
normal conditions at a burial site involve zero release, volume
consumed is the major parameter affecting duration of operations.
-------
APPENDIX A-12-66
The last complication to be cited here is the need to avoid
disclosure of information considered proprietary by the licen-
sees. Since many of the firms involved in the generation,
packaging, transport, and storage of the radioactive wastes are
young and competition for business is keen, the publication of
cubic feet buried per year or gallons stored per ton of fuel pro-
cessed should be avoided. These proprietary aspects are pro-
tected by aggregating data or projections for three or more
licensees; this still allows qualitative indications to be tabulated
for each licensee, which provides at least some geographical
interpretation to be made by or for EPA. (The alternative of
tabulating actual or estimated quantities but concealing the geo-
graphical location would seem less helpful to EPA. )
Table A-12-22 shows the current practices at AEC sites
on a qualitative basis for solid waste and low,-, intermediate-,
and high-level liquids, and indicates whether the solid wastes
contain transuranics. The footnotes to this table on the next
page indicate how the wastes are handled.
Table A-12-23 shows the available quantity data on the
AEC sites with respect to present handling of high-level liquids
and burial or shipment of solids. Five- and ten-year projections
are presented for high-level liquids.
-------
APPENDIX A-12-67
Table A-12-22
Qualitative Indices* to Types of Waste Handled at AEC Sites
Site
HAN
SR
NRTS
LASL
ORNL
FMPC
Y-12
RF
SAN
PANT
NTS
K-25
PAD
PORT
MOUND
BNL
ANL
BMI-C
LRL-B
LRL-L
SNPO
BET
NB
AMES
PIN
LOV
Liquid Wastes
Low
Level
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
(1)
Inter-
mediate
Level
(2)
(2)
(2)
(2)
(2,9)
None
None
(2)
None
None
None
None
None
None
(2)
(2)
(2)
(2)
None
None
None
None
None
None
None
None
High
Level
(3)
(3)
(10)
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
Solid Wastes
Contains
Trans -
uranics
(4)
(4)
(4)
(4)
(4)
None
None
(5)
(4)
(4)
(6)
None
None
None
(8)
None
(8)
None
None
None
None
None
None
None
None
(8)
No
Trans -
uranics
(6)
(6)
(6)
(6)
(6)
(11)
(6)
(7)
(6)
(6)
(6)
(6)
(6)
(6)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(6.8)
(7)
(8)
See next pa
fication of s
for key to index numbers and page A-12(71) for identi-
tes.
-------
APPENDIX A-12-68
Key to Indices of Table A-12-22
(1) Monitored; treated if necessary; after treatment, effluent
released and residue handled as solid waste.
(2) Treated by evaporation, precipitation, ion exchange, decay
storage, etc.; after treatment, effluent released at or below
limits and residue handled as solid waste or high-level
"liquid. "
(3) Concentrated for interim and long-term storage; overheads
treated as intermediate- or low-level waste.
(4) Buried retrievably on site.
(5) Shipped to approved site for retrievable burial.
(6) Buried on site.
(7) Shipped to AEG site for burial.
(8) Shipped to commercial burial ground.
(9) Some ILW has been disposed of by hydrofracturing.
(10) Treated by fluidized bed calcination and stored as dry,
granular solid.
(11) Placed in raffinate pits with sludges from low-level
liquid treatment.
-------
APPENDIX A-12-69
Table A-12-23
Quantities of Wastes Handled per Year at AEG Sites
Site
HAN(1)
SR<1>
NRTS(1>
LASL
ORNL
FMPC
Y-12
RF
SAN
PANT
NTS
K-25
PAD
PORT
MOUND
BNL
ANL
BMI-C
LRL-B
LRL-L
SNPO
BET
NB
AMES
PIN
LOV
Total
High- Level Liquids (million gallons)
Present
8.0
5.0
0.6
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
14(6)
Estimated
1977
0.6
5.0
0.7
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
6
Estimated
1982
0. 1
5.0<5>
0. 7
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
6<5)
Solid Wastes(2)
(thousand cu. ft. )
Present^3)
150
370
400
190
160
30
30
220
<10
-
10-20
<10
10-20
<10
100
<10
30-40
<10
<10
20-30
10-20
20-30
<10
<10
<10
10-20
1700<4>
* See next page for notes and page A-12(7J) for identification of sites.
-------
APPENDIX A-12-70
Key to Indices of Table A-12-23
(1) Liquid waste volume figures are primarily based on the
rehandling of stored inventories since these mask the
smaller volumes from current operations and some of
the latter are classified.
(2) For this column, "handled" means buried or shipped as
indicated in Table A-12-22; excludes solids produced
by concentration of high-level liquids.
(3) Based on data for 1969, 1970, or 1971.
(4) Total burials at AEC sites; excludes quantities shipped
to licensed commercial burial grounds.
(5) Assumes continued operation of production facilities.
(6) Current inventories total about 86 million gallons of
liquids, sludges, and wet salt cake.
-------
APPENDIX A-12-71
Identification of Sites
for Tables A-12-22 and -23
Site Designation
AMES Ames Laboratory
ANL Argonne National Lab.
BET Bettis Atomic Power Lab
BMI-C Battelle Memorial Inst.
BNL Brookhaven Nat. Lab.
FMPC Feed Materials
Production Center
HAN Hanford Facilities
K-25 Oak Ridge Gaseous
Diffusion Plant
LASL Los Alamos Scientific
Laboratory
LOV Lovelace Foundation
LRL-B Lawrence Radiation
Lab, Berkeley
LRL-L Lawrence Radiation
Lab, Livermore
MOUND Mound Laboratory
N. B. New Brunswick Lab
NRTS National Reactor Testing
NTS Nevada Test Site
ORNL Oak Ridge Nat. Lab.
PAD Paducah Gaseous
Diffusion Plant
RF Rocky Flats Plant
SAN Sandia Laboratories
SNPO Space Nuclear Propulsion
Location
Ames, Iowa
Argonne, 111.
Pittsburgh, Pa.
Columbus, O.
Upton, N. Y.
Fernald, O.
Richland, Wash.
Oak Ridge, Tenn.
Contractors
Iowa State Univ.
Univ. of Chicago
Westinghouse
Battelle Mem. Inst.
Asso. Universities
National Lead Co.
of Ohio
Several**'
Union Carbide
Los Alamos, N. M. Univ. of Calif.
Albuquerque,N.M. Lovelace Found.
Berkeley, Calif. Univ. of Calif.
Livermore,Calif. Univ. of Calif.
Miamisburg, O. Monsanto Res.
NewBrunswick.N.J. (AEC)
Idao Falls, Idaho Several(2)
Mercury, Nev.
Oak Ridge,Tenn.
Paducah, Ky.
Reynolds Elec. &
Eng. Co.
Union Carbide
Union Carbide
Rocky Flats, Col. Dow Chemical
Albuquerque,N.M. Sandia Corp.
Jackass Flats,Nev. Westinghouse
-------
APPENDIX A-12-72
Site Designation Location Contractors
SR Savannah River Facil. Aiken, S.C. E.I. du Pont de
Nemours & Co.
Y-12 Y-12 Plant Oak Ridge.Tenn. Union Carbide
Atlantic Richfield Hanford Company; Douglas United Nuclear;
WADCO (subsidiary of Westinghouse); Battelle-Northwest
(Division of Battelle Memorial Institute).
(2)
Argonne National Laboratory; General Electric Company;
Idaho Nuclear Corporation; Westinghouse.
-------
APPENDIX A-12-73
6. RADIOACTIVE WASTE TREATMENT - CURRENT AND FUTURE
Standard chemical waste treatment systems are used to collect,
concentrate and immobilize radioactive waste. A brief description of
the currently used equipment and systems is given in the following
paragraphs followed by a brief discussion of new and improved sys-
tems which will be in use in the near future.
(1) Current Effluent Treatment Systems
1. Gases—Gaseous effluents are generally air which
contains either or both radioactive gases and radioactive
particulates. Gaseous effluent streams with radioactive
particulates are passed through high efficiency filters
capable of a 99. 97 percent removal of particles down to
0. 3 micron in size. An alternate to the high efficiency
filters for very large installations is a sand filter bed
which has a comparable efficiency. Gaseous effluents
with a radioactive gas component are treated in accordance
with the radiotoxicity of the gas. In general, radon gas
of low toxicity from mining and milling operations is
diluted and released; short half-life xenon and krypton
radionuclides from reactor operations are delayed and
decayed before release, and the more toxic radioiodines
-------
APPENDIX A-12-74
released during fuel reprocessing are removed from
other gaseous effluents by means of charcoal absorption,
chemical scrubbing and adsorption in silver reactors.
2. Liquids—Most liquid effluents are water with small
quantities of soluble or insoluble radioactive material.
These low-level radioactive waste effluents undergo a
combination of settling, precipitation, filtration, evapora-
tion, and demineralization operations as appropriate to
remove the radioactive material before the water is
released.
3. Solids — Solid radioactive wastes are generally con-
taminated solid materials such as ion exchange resins
used to remove radioactivity from liquid streams, or
high efficiency filters used to collect particulates in gase-
ous effluents, or rubber gloves, kleenex, and other equip-
ment used in particular operations, or solidified radioactive
waste concentrates from liquid waste treatment systems,
etc. These low-level waste materials are usually shipped
to an authorized waste burial facility (see Table A-12-19)
for final disposal.
-------
APPENDIX A-12-75
The shipment of radioactive material is in authorized,
well-engineered packages which have been designed to meet
rigorous safety requirements. If the material shipped is
more than a very small quantity (millicuries for the more
radiotoxic materials), the package must, in addition to be-
ing capable of withstanding the normal conditions of trans-
port, be capable of meeting a severe hypothetical accident
represented by a 30-foot drop of the package onto an un-
yielding surface, followed by a 40-inch drop onto a 6-inch
diameter steel cylinder, followed by a 30-minute exposure
to a 1475° fire, then finally total immersion for 24 hours
under water. At the completion of this series of tests,
the package must not release more than a very small
quantity of its radioactive contents or it is not authorized.
(2) Future Waste Treatment Systems
Most of the current waste treatment systems are perform-
ing adequately enough to meet the existing license requirements.
Nevertheless, these systems will have to be refined and supple-
mented in the near future in order to comply with the U. S. AEC
announced regulatory policy of maintaining radioactive releases
to the environment at the lowest practicable limits. Most of the
upgrading of waste treatment will be necessitated by a further
-------
APPENDIX A-12-76
restriction on gaseous and liquid releases from the power reac-
tors and the fuel reprocessing plants. New power reactor de-
signs are tending more and more to the so-called "zero" or
"mini" release systems which provide for removal or additional
decay of the several gaseous xenon and krypton radionuclides
and a more complete internal plant recycle of water. Similarly,
the reprocessing plants will be faced with the necessity of de-
signing and providing systems for removing the noble gas Kr-85
and reducing low-level liquid discharges to an absolute minimum.
Current reprocessing designs provide for an in-plant recycle of
water and, therefore, have no liquid discharge.
The reprocessing plants have, in addition to some upgrading
of low-level radwaste treatment systems, a much more complex
problem to solve; namely, that of converting the stored, high-
level fission product and actinide liquid waste, which are the
result of reprocessing, to an acceptably immobile solid waste
form which will permit its ultimate disposal. Another area for
research and development, but to a much lesser degree than
that required for high-level wastes from reprocessing, is to
find an economically feasible system for containing tritium, an
existing effluent from both power reactors and fuel reprocessing
plants. When the new gaseous and liquid treatment systems are
-------
APPENDIX A-12-77
installed and operable, the nuclear industry will have confined
its waste effluents except for tritium which does not pose an
immediate health and safety problem to the public. The pro-
posed new types of waste collection systems are as follows.
1. Gases.—In the case of boiling water reactor, the
proposed systems for radiogases are as follows:
The use of pressurized storage to permit an
extended decay period prior to release,
After minimizing the gaseous volume by
catalytic recombination and dew point reduc-
tion, the ambient temperature absorption of
the noble gas in charcoal beds to extend their
decay period before release, and
A cryogenic distillation of the off-gas to re-
cover the xenon and krypton components for
long-term storage.
2. Liquids—Upgrading of liquid waste treatment sys-
tems will primarily be by the addition of filtration
evaporation and ion exchange systems to permit a more
complete internal plant recycle of water.
3. Solids—It may be necessary in the near future to
isolate contaminated wastes to a greater degree than pre-
viously necessary. In this event, long-term storage
-------
APPENDIX A-12-78
facilities will have to be provided for these materials
pending their ultimate disposal.
The fuel reprocessing plants can use similar systems to
those at nuclear power facilities to reduce their gaseous and
liquid effluents. The high-level waste treatment considerations,
however, are very different. In this regard, the U.S. AEC has
for some time at its Brookhaven, Oak Ridge and Hanford facilities
been developing techniques for concentrating and solidifying the
high-level radioactive wastes from reprocessing into an accepta-
ble form for long-term storage. Recently the work on the per-
formance of three waste solidification techniques ' ' was
completed at Batelle Northwest in Richland, Washington.
These techniques are phosphate glass solidification, spray
solidification, and pot solidification.
The phosphate glass process, originally tested by
Brookhaven National Laboratory, consists of an evaporative
denitration of the high-level waste after the addition of
phosphoric acid, sodium hydroxide, and ferric nitrate. The
bottoms discharge of the denitrator is melted and collected in
a pot for final storage. The overheads from denitration are
condensed and re-evaporated with the bottom, recycled to the
-------
APPENDIX A-12-79
denitrator feed tank, and the overheads fractionated for nitric
acid recovery. The aqueous effluent was decontaminated by a
7 ft c c
factor of 10 to 10 for the non-volatiles, and by 10 to 10 for
the radio-ruthenium. Storage of the phosphate glass product
was adequate; no increase in pressure after the pot cap was
welded in place.
The spray solidification process utilized a spray calciner
to solidify the incoming high-level waste liquor followed by a
fusing of the solids directly in the storage container using a
sodium borosilicate frit as a melt additive. The off-gas from
the calciner is condensed and re-evaporated, and the overheads
are fractionated for HNOQ acid recovery. The bottoms of the
o
evaporator are recycled to the calciner feed tank. The aqueous
g
effluent was decontaminated by a factor of 10 for non-volatiles
e c
and 10 or 10 for radio-ruthenium. The waste containers were
capped and welded and showed no pressure buildup.
The pot solidification process, originally tested at Oak
Ridge National Laboratory, is a direct solidification in the
storage container used for ultimate disposal. The use of
auxiliary evaporator, fractionator, and scrubber equipment
g
provided a 10 decontamination factor for the liquid effluent
-------
APPENDIX A-12-80
g
and greater than 10 for radio-ruthenium. The sealed containers
are still undergoing tests at the Solids Storage Engineering Test
Facility at Hanford.
One of these basic techniques will undoubtedly be utilized
in the near future by both NFS and Allied-Gulf in order to com-
ply with the recent AEC regulation making it mandatory to con-
vert stored high-level waste liquids to a form acceptable for
ultimate disposal. GE has already included spray calcining of
the high-level waste in its design of the Midwest Fuel Recovery
Plant.
Among the remaining problems associated with radio-
active waste materials are the location and type of Federal
Repository required for high-level solidified wastes, the
methods of handling and ultimately disposing of alpha wastes,
and finally, but of much less immediacy, the collection and
retention of tritium.
-------
APPENDIX A-12-81
REFERENCES
(1) Data for Preliminary Demonstration Phase of the "Environmental
Quality Information and Planning System (EQUIPS), " BNWL-B-
141, December 1971.
(2) Statistical Data of the Uranium Industry, January 1, 1971,
Grand Junction Office, U.S. Atomic Energy Commission.
(3) A Survey of Alpha Waste Generation and Disposal as Solids in
the U.S. Nuclear Fuel Industry, BNWL-B-34, December 1970.
(4) Statement on the Sources of Radioactive Material in Effluents
from Light-Water Cooled Nuclear Power Reactors and State of
Technology of Waste Treatment Equipment to Minimize Releases,
H. R. Denton, U.S. AEC, January 10, 1972.
(5) Design and Analysis, Midwest Fuel Recovery Plant, General
Electric Co., filed as Docket 50, U. S. AEC Document Room.
(6) Siting of Fuel Reprocessing Plants and Waste Management
Facilities, ORNL-4451, Oak Ridge National Laboratory,
July 1970.
(7) Safety Series No. 7, Notes on Certain Aspects of the Regulations,
International Atomic Energy Agency, Vienna, 1961.
(8) A Survey of Spent Fuel Shipments in the 1970's, A. E. Aikens, Jr.,
PRS Systems, Inc., January 1970.
(9) Phosphate Glass Solidification Performance during Final Radio-
active Tests in Waste Solidification Engineering Prototypes
(WSEP), J. L. McElroy, et al, January 1971 (BNWL 1541).
(10) Spray Solidification Performance during Final Radioactive Test
in WSEP, W. R. Bond, et al, June 1971 (BNWL 1583).
(11) Pot Solidification Performance during Final Radioactive Tests
in WSEP, J. L. McElroy, et al, January 1972 (BNWL 1628).
(12) Radioactive Waste Handling Information, Letter from Mr. Alex
F. Perge, Assistant Director for Development and Transportation,
Division of Waste Management and Transportation, Atomic Energy
Commission, February 14, 1972.
-------
APPENDIX A-13
WASTE MANAGEMENT
DEPARTMENT OF DEFENSE
-------
APPENDIX A-13
WASTE MANAGEMENT
DEPARTMENT OF DEFENSE
1. ECONOMIC STATISTICS
The Department of Defense (DoD) has the following resources:
An annual budget of $70 - $80 billion
Real property valued at $46 billion
(Total government real property value - $102 billion)
Personal property valued at $143 billion
(Total government real property value - $244 billion)
Forty-three percent of the 3 million federal
employees
Military strengthof approximately 3,000,000 (1971)
Several hundred major bases
Operation of major production, housing, hospital, harbors,
airfield, maintenance, and support facilities at home and
overseas.
Much of the industrial economy is influenced by DoD decisions
and resultant requirements for goods and services. Goods range from
aircraft carriers to paper clips. The feeding and housing of the military
forces involves not only those in military service, but their dependents
-------
APPENDIX A-13-2
as well. Every conceivable human activity is likely to be represented
within its forces.
The magnitude and scope of its operations insure that the
Defense Department is actively involved in all aspects of waste creation,
control, and disposition. Because it operates through a well defined
command structure, it can readily establish controls over its disposal
problems and,to the extent that funds are available,implement advanced
disposal procedures. This capability,to readily apply control measures
as needed?may provide an opportunity to test disposal control procedures
within the Defense environment and establish their feasibility and costs
prior to advocation of their use by the country at large.
2. WASTE MANAGEMENT
The Department of Defense, through its component departments
(Army, Navy, and Air Force), has a long history of effective waste
disposal practices. Safeguarding the health of the military establish-
ment has been a vital mission since the initial forces were gathered to
win freedom for the country. Practices developed within the military
medical departments have been precursors for similar sanitary advances
within the country as a whole.
-------
APPENDIX A-13-3
The manufacture and use of weapons has required the continuous
evaluation of hazards and the development of regulations for their safe
control. Each new weapon or munition development has required the
development of a support system which included its final disposition.
Such support systems frequently prescribe each stop in the acquisition,
storage, use, maintenance, and disposal of such items as procurement
specifications, labeling, packaging, and inspection procedures, as
well as precise direction for its final destruction.
(1) Organization for Control
In addition to the procedures which have been followed
for years, DoD has recently established a monitoring and control
system to ensure that all practical steps are taken to reduce the
release of pollutants to the environment. At the DoD level, the
Assistant Secretary (Health and Environment) ensures that all
directives are adequately prepared and fully implemented. Each
service provides an office at departmental level to monitor and
direct environmental activities. Such directions include moni-
toring programming and budget actions to ensure that funds are
directed toward the priority programs. The actions and programs
within all echelons of the Defense Department are also monitored
by the Environmental Protection Agency (EPA^by their review
-------
APPENDIX A-13-4
of environmental impact statements which must accompany all
new program submissions. Fundamentally, however, control is
exercised through normal command channels. Command priority
is given to ensuring that all measures which can be taken to
reduce hazardous wastes are taken.
The actual waste disposal practices within the service
can be grouped functionally into those concerned with post,
base, or station operations; those related to production opera-
tions; those concerned with supply and maintenance operations;
and those related to weapon systems.
(2) Base-Post-Station Operations
In most respects, waste disposal at the major permanent
operating facilities are comparable to those of a modern city of
the same approximate size which has an active, aggressive waste
management program. A study recently completed by the U. S.
Air Force (USAF) at 98 major installations (Reference 1) shows that
3. 5 pounds per day of household wastes are generated. This
compares closely with the figure of 3. 0 pounds per day estab-
lished by the 1968 National Survey of Civilian Communities.
This study also provides data on pathological wastes from
-------
APPENDIX A-13-5
hospitals, liquid industrial wastes, and pesticides and herbicides
in storage (Tables A-13-1 and A-13-2). This latter category
includes material whose use has been restricted, as well as
materials whose containers have deteriorated and which are
potential hazards while in storage.
Table A-13-1
Typical Base Data
Wastes
Base solid wastes
Family housing solid
wastes
^Wastes
Base solid wastes
Family housing solid
wastes
No. Bases
Reporting
90
90
No. Bases
Reporting
98
98
Total
Tons /Mo.
64,858
21,853
Total
Ft3 /Mo.
20,893,463
6,648,239
Ave. Lbs/
Per s/ Day
5.11
3. 94
Ave.
Lbs /Yd3
172
188
The pathological wastes generated on 77 bases average
42, 371 pounds per week, or 5. 63 pounds per bed per week.
Classified wastes, as reported from 95 bases, were 805 tons
per month. Kelly Air Force Base averages 353 tons per month.
The average base (not including Kelly Air Force Base) produces
327 pounds per day of classified waste (classified documents).
-------
APPENDIX A-13-6
The following data indicates the total volume of industrial
type wastes which are produced monthly. The data is for all
reporting bases.
Table A-13-2
Liquid Industrial Wastes
Waste Material
Engine oil
Hydraulic fluid
Industrial fluids and
petrochemicals
Contaminated fuel
Emergency fuel
destruction
Other wastes
Fire training fuel
TOTAL
Bases
Reporting
86
82
87
91
97
11
98
Average Gal/
Mo. (All Bases)
115,301
12,209
187,736
241,859
9,040
93,889
148,671
808,705
This data indicates that each base will produce between 8,000
and 9, 000 gallons of petroleum product wastes monthly.
The data provided above represents a substantial portion
of the U. S. Air Force. The per capita data shown are probably
-------
APPENDIX A-13-7
comparable to data which would be obtained in similar surveys
in other services.
Typically, the base or post engineer is resppnsibile for
disposal operations at each facility. He is assisted, as needed,
by sanitation engineers who are members of the U.S. Army
Environmental Hygiene Agency, or a similar unit whose opera-
tions are supervised by the Surgeon General of each service.
These specialists continuously inspect all operations to insure
compliance with regulations and to develop solutions to difficult
disposal problems.
The disposal of household wastes on military bases is
comparable to civilian practices. On permanent bases, all
sewage is given a minimum of secondary treatment. In most
cases, additional treatment is given. The disposal of solid
collectible wastes follows conventional practices; over 95
percent is placed on landfill either by contractors or by service
employees. Some incineration takes place and increased funding
will enable more modern incinerators to be built. Pathological
wastes are incinerated to reduce them to disposable ash.
-------
APPENDIX A-13-8
Pharmaceuticals are primarily disposed of by incineration, although
some are still buried in carefully supervised landfills.
Service disposal facilities may be augmented by contract
with civilian communities or agencies. Not infrequently,
service sewage or other disposal facilities may be used by civil-
ian communities. Extensive programs are underway in all
services to modernize their disposal facilities to fully satisfy
environmental standards.
The USAF report provides a detailed picture of current
practices, as well as recommendations for additional progress
towards better disposal practices.
(3) Production Processes
The census data for 1967 credits the Defense Department
with over 4 billion dollars in manufacturing billings; about one-
fourth in research and development, one-fourth in ordnance,
one-fourth in ship building, and the balance scattered among
such activities as aircraft, communications, and miscellaneous
chemical products. This data may understate, somewhat,the
extensive operations of the U.S. Army Ammunition plants which
are government-owned, but contractor-operated.
-------
APPENDIX A-13-9
The munition manufacturing plants were built in World
War II because of the reluctance of civilian industry to invert in
facilities which are frequently inactive. Currently, they are
operating in support of Southeast Asia requirements. They are
the largest group of government production facilities and produce
propellants, explosives, and assemble munitions of many types.
The Naval Shipyards are also part of the historic arsenal
and shipyard system which has provided logistic support to the
combat elements since the country was founded. Although new
shipping and ship repairs may be contracted to private yards,
extensive repair and refitting operations are conducted within
government-operated facilities.
The production operations in these facilities, with the
exception of the munitions plants, generate wastes comparable
to those found in the metal assembly industries. Typical wastes
include solvents, detergents, cutting oils, boiler blowdown
residues, oily wastes, and paints and lacquers. Controls are
exercised over these wastes to insure compliance with both
state and federal requirements.
-------
APPENDIX A-13-10
(4) Maintenance Operations
The military services have an extensive inventory of
hardware which requires continual maintenance. Such activities
scale up from simple motor pool maintenance operations to such
complex facilities as small carriers used exclusively for main-
tenance operations. Minor maintenance facilities are established
in all permanent posts and bases, as well as overseas to support
local needs.
More extensive facilities have been developed to enable
complete overhaul or rebuilding of major items of equipments such
as trucks, tanks, and aircraft. These facilities are comparable
to a manufacturing plant in the scope of operations and in the
wastes generated.
(5) Supply Operations
The support of the defense establishment throughout the
world requires an extensive system of supply depots and the
means to move supplies. Extensive storage, classification,
packing, and movement capabilities are required. Buildings
vary from simple sheds to fully automated warehouses comparable
to those of Sears Roebuck or General Motors. Means of movement
-------
APPENDIX A-13-11
vary from hand trucks to massive C-5A aircraft. Since the supply
system deals with all items (clothing, food, medicines, munitions,
weapons, etc.),the storage problems which arise from deterior-
ating or worn-out material cover a wide spectrum.
Disposal is part of the responsibilities of the supply system.
This operation gathers together worn-out or excess equipment
(supplies for sale to the highest approved bidder or for safe dis-
posal in government disposal facilities). Close control over all
items in the supply system enables the Services to collect, for
recycling operations, items such as mercury switches, batteries,
or lights. Service disposal operations may provide a useful model
for collection and recycling operations in the civilian community.
(6) Weapon Systems
Weapons used in the services range from individual items,
such as pistols and knives, to exotic ship aircraft, missile, and
ground systems which employ a variety of exotic warheads.
Before any weapon system is fielded, plans for its contin-
uous support, maintenance, and safe disposition have been made.
All potential hazards have been investigated and steps taken to
negate or control such hazards. Much as a fire department
-------
APPENDIX A-13-12
continuously trains to overcome civilian accidents, skilled
military personnel train to immediately remedy any failure in
systems safety. Explosive Ordnance Disposal personnel are on
call at all times to take over in the event of accidents. Nuclear,
chemical, and other exotic weapons systems have expert hazards
control personnel available,too.
This brief review of the various functional areas within
the Department of Defense that generate,and are concerned with,
waste disposal provides an overview of the magnitude and diversity
of waste disposal within the Services. The following paragraphs
discuss the type of hazardous wastes which may be produced in
each of these functional areas.
3. CURRENT DISPOSAL OPERATIONS
(1) Chemical Munition Production
The clean-up and decontamination of munitions, facilities,
and land areas used in the manufacture of chemical agents and
munitions pose a special problem. Three major projects con-
cerned with these wastes are now underway.
-------
APPENDIX A-13-13
The first involves the demilitarization of excess and
unserviceable stocks of mustard and nerve gas munitions and
agents at Rocky Mountain Arsenal. The demilitarization process
will produce solid toxic residues which will require further
disposition. The disposal of wastes from the production of these
agents in past years must also be considered. These wastes are
now contained in a sizeable lake. The pollutants which will be
generated in the munitions disposal phase include sodium fluor-
ide, chloride, sulfide, and sulfate and sodium salts from the
reaction of sodium hydroxide and GB. The materials in the lake
include arsenicals from the manufacture of Lewisite in World
War II. There are about 130 million gallons of 7 to 8 percent
dissolved solid waste in the lake, while the program for the
disposal of munitions may develop an additional 25 million
gallons of waste.
Reduction of these wastes to residue solids will be costly.
Special demilitarization process equipment is being assembled.
This equipment will be transportable so that it may be moved
throughout the country to dispose of other munition stocks where
they are now stored.
-------
APPENDIX A-13-14
The cleanup of the lake will be expensive if not prohibi-
tive in cost. Present plans call for evaporation of the lake by
natural processes augmented by spray drying. Once dry the
lake will still contain toxic salts. To fully explore the extent of
soil contamination may involve the taking of thousands of core
samples and their subsequent chemical analyses. An estimated
12 million cubic feet of soil may have to be removed and dis-
posed of elsewhere.
This particular project points up the expense involved if
existing civilian lagoons or sludge piles are to be cleaned up. .
As air and water pollution standards are enforced and more con-
taminants are removed from air and water, the problem of
handling toxic sludge will become greater.
At another location, the manufacture of incendiaries over
many years has resulted in a significant accumulation of "phossy
water" containing phosphorus slag, elemental phosphorus and
oxides of phosphorus. Over 200 million gallons of water will
require treatment.
A third major problem is to clean up sludge deposits from
streams which have accumulated over the years as residues
-------
APPENDIX A-13-15
from the manufacture of pyrotechnics and incendiaries. These
sludges contain dyes, sulfur, magnesium, aluminum and or-
ganic wastes.
These three disposal projects may be the precursors of
similar clean-up operations which may be demanded elsewhere.
The results of these clean-up attempts may be helpful in illumi-
nating the magnitude of ultimate disposal operations and costs,
if all such contaminants are to be safely removed.
(2) Biological Material
Recent presidential decisions, to substantially reduce bio-
logical operationsyhave required that all stockpiles be demili-
tarized. Such operations are now underway at locations having
such stocks. The basic treatment involves sterilization and
subsequent incineration to a harmless residue. These opera-
tions will be performed by the military services under the con-
tinued guidance of state and federal authorities.
(3) Nuclear Material
In general,there are three different categories of nuclear
materials and wastes; those related to weapons, those associated
with sources and radioisotopes, and those related to nuclear
-------
APPENDIX A-13-16
reactors. Because of the classification associated with nuclear
weapons,this area will not be discussed. It will be treated in
general fashion in the discussion of Atomic Energy Commission
(AEC) waste disposal activities.
The use of radioisotopes and sources within the military
structure is comparable to their use and control through the
civilian sector. The Atomic Energy Commission establishes
the basic rules, licenses the holders, and inspects to ensure
that all provisions of their regulations are enforced. The mili-
tary services have a substantial number of officers who are
specially trained in the use and care of nuclear materials. The
safeguards imposed by the AEC are further elaborated by ser-
vice regulations and guides.
All services have a guidance committee to monitor and
approve all actions with respect to reactors. The U. S. Army
Reactor Health and Safety Committee includes one representa-
tive from the Surgeon General's office, two from the Corps of
Engineers, one from the Army Materiel Command, one from the
Transportation Corps, and one from the Army Reactor
Group (an engineer unit at Fort Belvoir). Under AEC guidance
these groups insure that all procedures relating to operation
-------
APPENDIX A-13-17
and waste disposal are carried out. AEC checks on this com-
mittee by annual inspections of all operations involving nuclear
materials.
Nuclear wastes which accumulate at any post, base, or
station are the responsibility of the licensed holder to safeguard
and to release to approved disposal contractors. The latter,
•when notified, pick up the wastes and transport them to final
national disposal sites.
Each of the services operates one or more nuclear re-
actor, with 96 nuclear powered submarines and ships in the
U. S. Navy nuclear ship program. Enclosed as Attachment A-13-I is
a description and the data on the U. S. Naval program for the dis-
posal of radioactive wastes and their environmental monitoring
procedures.
(4) Excess or Unsafe Munitions
In prior years,munitions which were unsafe or in excess of the
need, were disposed of in the most economical manner,
generally by burning, detonation, or dumping at sea. Then, as
now, every effort was made to recover the items of value^if it
could be done safely. When practical, the explosive was
-------
APPENDIX A-13-18
recovered and the metal casings salvaged for eventual melt-
down and reuse. Many thousands of tons of incendiary and toxic
munitions were burned under carefully controlled conditions.
Present regulations sharply restrict disposal methods.
Limitations on atmospheric release which preclude open-pit
burning and restrictions on movement of toxic munitions, have
led to the development of a transportable incineration system to
accomplish the in-place clean-up of toxic munitions at their
present storage sites. Ocean dumping, formerly used as an
ultimate disposal means, has been suspended,while ether dis-
posal alternatives are evaluated.
The magnitude of the munition disposal operation can be
measured by the fact that over 100, 000 tons have been ocean
dumped since 1964. The current estimate is that approximately
80, 000 tons of Navy ammunition now require disposal, and
more will be added to this amount as activity in Southeast Asia
ends. Army munitions disposal requirements will be at least
as large.
Present plans call for extensive use of munition demili-
tarization, i. e., the recycling of most or all of the explosives
-------
APPENDIX A-13-19
and metal parts. Such operations will be keyed to ammunition
renovation programs continuously operated at major storage
areas.
(5) Packaged Hazardous Materials
The services depots contain most products known to man.
Among these products are chemicals, herbicides, pesticides,
industrial gases, and similar products used in housekeeping,
maintenance, production and renovation activities. Such chem-
icals can be hazardous if not properly handled, stored, or
packaged or, if they remain in storage for long periods of time,
deterioration of the packages or contents may create hazardous
or potentially hazardous effects.
Although safety guides, handling instructions, inspection
procedures, and stock rotation and disposal techniques elimi-
nate much of the potential danger, occasionally hazardous con-
ditions can arise. Recently, cans containing wood treatment
material arsenals began to leak and were sold as a lot to a small
plant which treated wood. Because the lot-size was in excess of
his needs, the buyer sold the excess stock. The next purchaser
who wanted only the cans, poured out the contents and, in so doing,
poisoned several local wells. Because events do occur,
-------
APPENDIX A-13-20
procedures governing the disposal of potentially hazardous
materials are continuously reviewed and tightened.
Within the Army, the U. S. Army Environmental Hygiene
Agency (AEHA) acts as advisor to installations who have special
disposal needs. The other services have similar organizations
who make on-site inspections and design special disposal
methods in unique situations. Recently, the AEHA proposed that
all material procurement specifications prescribe safe disposal
practices for all packaged products. Such disposal instructions
would augment present labelling requirements.
The military services have long recognized that extreme
care must be taken to protect people and property from the
hazards. Safety programs in munitions production and handling
have been directed and monitored by the Armed Services
Explosives Safety Board. The U.S. Army Environmental
Hygiene Agency, and its counter-parts in the other services,
supervise all aspects of sanitary, industrial, and environmental
safety.
The prevention of hazardous conditions is emphasized
in the design,construction and use of facilities and equipment.
The care taken,in such matters,is illustrated by the ability of
-------
APPENDIX A-13-21
the services to produce toxics in substantial quantities while
fully containing the toxic products and by-products. While
perfection has not been attained, many of the service design
practices may have useful application in history.
The specific effects of hazardous munitions are well
defined with voluminous effects-data available. The persistency
of such effects is also known (e. g., mustard gas
can remain in the soil for years and still be hazardous). The
effects of more common wastes,such as oils and surfactantsvis
much less well known. The services have not made specific efforts
to define effects on civilian commodities. The military laboratories
which have developed such precise data on military weapons effects
over various geographic areas have the skills to explore the
effects of the more mundane hazards,if so directed. Use of these
skills to assist in establishing hazard potentials of industrial
toxics would appear desirable.
Currently all services have extensive programs to
improve disposal systems so as to fully meet the stringent
requirements of current legislation. This historic concern for
personal and property safety has been broadened to encompass
the total environment.
-------
APPENDIX A-13-22
4. HAZARDOUS WASTES
Since DoD activities are comparable in many respects to the
civilian community, many of the same hazardous materials are pro-
cured, stored and used. While the manufacturing facilities are not
nearly as extensive, the munition and agent production facilities of
the services are extensive.
Typical air and water toxic pollutants involved in conventional
munition production include
Air Water
Acetic Acid Acetic Acid
Acetic Anhydizide Hexamine
Ammonia Ammonia
Butyl Alcohol Sodium Nitrate
Cyclohexanone Sodium Sulfate
Formic Acid Phenols
Iso Butyl Acetate Iso Butyl Acetate
Methylacetate Ammonium Nitrate
Methy Ethylacetone Nitric Acid
Nitric Acid Oils
Oxides of Nitrogen Explosives
Toluene Red Water
Other Organics Sulfuric Acid.
The production of toxic agents results in wastes such as those
previously noted. Other hazardous wastes include typical compounds
involved in the following operations.
-------
APPENDIX A-13-23
Maintenance
Cleaning Solvents
Paints and lacquers
Plating wastes
Oily wastes
Surfactants
Supply
Toxic munitions
Explosive munitions
Propellants
Oxidizing agents
Flammable liquids
Explosives
Pyrotechnics
Pesticides and herbicides
Drugs and medicinals
Corrosive liquids
Nuclear weapon components
Laboratory chemicals
Weapon Systems Support
Hydrazine
Monomethylhydazine
Borane
Analines
Hydrocarbon fuels
Liquid oxygen
Solid propellants
Warheads - nuclear, non-nuclear
Fluorine.
The disposal methods used within the DoD establishments are
comparable^ in all respects,with the best practices found in industry
or municipalities. In some respects, their standards are more
-------
APPENDIX A-13-24
restrictive and their programs for reducing air and water pollution
more comprehensive.
The most significant difference in waste disposal techniques
between the DoD establishment and their civilian counterparts, is
the degree of control which can be exercised over the disposal process.
Implementation of desirable programs is limited only by available
funds. Instruction as to what shall be done and by whom assures imple-
mentation when resources are made available. The salvage programs
operated within the service provide a means to collect^selectively, items
such as mercury containing products, which should be recycled rather
than dumped. The controls which can be exercised over waste disposal
efforts indicate that DoD may provide an ideal test area for
"trying out" elements of any proposed national disposal system.
-------
ATTACHMENT A-13-I
Report NT-71-1
February 1971
ENVIRONMENTAL MONITORING AND
DISPOSAL OF RADIOACTIVE WASTES
FROM U. S. NAVAL NUCLEAR-POWERED SHIPS
AND THEIR SUPPORT FACILITIES
Prepared by
M. E. Miles, J. J. Mangeno, R. D. Burke
Nuclear Power Directorate
Naval Ship Systems Command
Department of the Navy
Approved by
. G. RICKOVER, VADM USN
Deputy Commander
for Nuclear Propulsion
-------
SYNOPSIS
This report summarizes data on disposal of radioactive
wastes from U. S. Naval nuclear-powered ships and their support
facilities and summarizes results of environmental monitoring
performed to confirm adequacy of waste disposal limits and
procedures. The total radioactivity discharged into all ports
and harbors was 0.024 curie in 1970, less than one hundredth
the total annual discharges of the early 1960's. Results of
environmental surveys of harbor water and bottom sediment for
gross radioactivity and for cobalt 60 show that (l) no increase
in radioactivity has been detected in harbor water, (2) dis-
charges of liquid wastes from U. S. Naval nuclear-powered ships
have not caused a measurable increase in the general background
radioactivity of the environment, arid (3) low-level cobalt 60
radioactivity is detectable in localized areas of harbor bottom
pediment around a few piers at operating bases and shipyards
where maintenance and overhaul of Naval nuclear-powered ships
have been conducted over a period of several years; these
levels have decreased in recent years.
This report confirms that procedures used by the Navy to
control discharges of radioactivity from U. S. Naval nuclear-
powered ships and their support facilities are effective in
protecting the health and safety of the general public.
-1-
-------
The radioactivity in wastes discussed in this report originates
in the pressurized water reactors of II. S. Naval nuclear-powered ships.
As of the end of 1970, there were 92 nuclear-powered submarines and 4
nuclear-powered surface ships in operation. Construction, maintenance,
overhaul and refueling of these nuclear propulsion plants involve nine
shipyards, eleven tenders, and two submarine bases. This report first
describes disposal of radioactive liquid wastes, then solid wastes.
The final section discusses monitoring of the environment to determine
the effects of radioactive discharges. This report brings up to date
information in the Navy's 1959 report, reference 1.*
RADIOACTIVE LIQUID WASTE DISPOSAL
In the shipboard reactors, pressurized water circulating through
the reactor core picks up the heat of nuclear reaction. Reactor cool-
ing water circulates through a closed piping system to heat exchangers
which transfer the heat to water in a secondary steam system isolated
from the primary cooling water. The steam is then used as the source
of power for the propulsion plant as well as for auxiliary machinery.
Discharges of radioactivity from ships occur primarily when reactor
coolant water expands as a result of being heated to operating tempera-
ture; this coolant passes through a purification system ion-exchange
resin bed prior to discharge.
Liquid wastes discharged by support facilities result from opera-
tions such as draining shipboard reactor systems, decontaminating radio-
actively contaminated piping systems, and laundering anticontamination
clothing worn by personnel. These facilities are equipped with proces-
sing systems to remove most of the radioactivity from liquid wastes prior
to discharge Into harbors.
The principal source of radioactivity in liquid wastes is from trace
amounts of corrosion and wear products from reactor plant metal Surfaces.
Radionuclides with half-lives greater than one day in these corrosion
and wear products include tungsten 187, chromium 51, hafnium 181, iron
59, iron 55, zirconium 95, tantalum 182, manganese 54, cobalt 58, and
cobalt 60. The predominant and also longest lived of these is cobalt 60,
which has a 5.3 year half-life; cobalt 60 also has the lowest concentra-
tion value for water listed by organizations which set radiological
standards in references 2, 3 and 4. for these corrosion and wear radio-
nuclides. Conservatively therefore, radioactive waste disposal is con-
trolled by assuming that all the long-lived radioactivity is cobalt 60.
* References are listed at end of report.
-2-
-------
The total amounts of long-lived radioactivity discharged into harbors
and seas within twelve miles from shore during the past five years are
listed in Table 1, which updates information in references 5 through 9.
Included are data from U. S. Naval nuclear-powered ships and from support-
ing shipyards, tenders and submarine bases. Locations listed in Table 1
include operating bases and home ports in the U. S. and overseas which
have been visited by Naval nuclear-powered ships. The quantities of radio-
activity listed-in this table are reported as if the entire radioactivity
consisted of cobalt 60, the predominant.long-lived radionuclide.
Although this table shows both gallons and curies discharged, the
curie data are the more important. In 1970 the gallons shown in Ta.ble 1
for most of these organizations are no more than many single U. S. homes
discharge to their sewage systems each year.
The table shows that nearly all the radioactive discharges occur
where shipyards are overhauling nuclear-powered ships. In 1970, for
example, a total of 0.024. curie was discharged into all harbors, includ-
ing those outside the U. S. Essentially all of this came from shipyards
overhauling nuclear-powered ships. Less than one percent of the total
was discharged into all other harbors entered by U. S. Naval nuclear-
powered ships in 1970.
This total radioactivity discharged into harbors is less than the
U. S. Public Health Service (USPHS) in reference 10 reports most individual
electrical power generating nuclear reactors discharge each year. Eval-
uation by USPHS (applicable divisions of which were incorporated in
Environmental Protection Agency late in 1970) of the small radioactive
discharges from electrical power generating reactors shows that these
discharges caused little or no increase in environmental radioactivity.
The 0.024 curie total from the Navy nuclear propulsion program if!
less than the one curie ner year U.S. Atomic Energy Commission (USAEC)
regulations in reference 2 permit a licensee to discharge into a single
sanitary sewage svstem.
Procedures for Liquid Wastes in Harbor
Discharge limits for radioactive liquid wastes from U. S. Naval
nuclear-powered ships and their support facilities are consistent with
applicable recommendations issued by the Federal Radiation Council (in-
corporated in Environmental Protection Agency late in 1970) U. S. Atomic
Energy Commission, National Council on Radiation Protection and Measure-
ments, International Commission on Radiological Protection, International
Atomic Energy Agency, and National Academy of Sciences - National Research
Council (references 2, 3, 4 and 11 through K). In consonance with these
recommendations, the policy of the U. S. Navy is to minimize the amounts
-3-
-------
TABLE 1
RADIOACTIVE LIQUID WASTE DISCHARGED TO HARBORS FROM U. S. NAVAL
NUCLEAR-POWERED SHIPS AND THEIR SUPPORT FACILITIES FOR 1966 THROUGH 1970
1966
Thousand
1967 1968 1969 1970
Thousand Thousand Thousand Thousand
Locations
Portsmouth, New Hampshire
Naval Shipyard
Groton-New London, Conn.
Electric Boat Div., Tender
at State Pier, & Sub Base
Newport News, Virginia
Newport News Shipbuilding
Norfolk, Virginia
Naval Shipyard and Tender
Charleston, South Carolina
Naval Shipyard and Tenders
Pascagoula, Mississippi
IngaJls Nuclear Division
San Dir.fro, California
Tenders at Ballast Point
Long Beach, California
Naval Shipyard and Base
Vallejo, California
Mare Island Naval Shipyard
Brenerton, Washington
Puget Sound Naval Shipyard
Pearl Harbor, Hawaii
Naval Shipyard and Sub Base
Aora H^rl.or. Guam
All other harbors. U.S. & Foreign
Gallons
155
1274
1581
1051
369
< 1 <
18
8 <
270
54 <
654
QQ ^
178
Curies
.011
.025
.055
.023
.034
.001
.001
.001
.187
.001
.031
.001
.013
Gallons
265
606
1533
1784
320
6
28
< 1
140
246'
683
42
<1
Curies
.012
.011
.034
.034
.011
< .001
.001
< .001
.001
.002
.008
.002
< .001
Gallons
171
469
1146
184
227
9 <
< 1 <
< 1 <
391
182
~
886
26
<\ <
Curies
.006
.006
.025
.004
.004
.001
.001
.001
.027
.001
.006
.001
_nm
Gallons
87
615
870
102
131
8 <
< 1 <
2 <
80
152
1279
< 1 <
<1 <
Curies
.002
.006
.022
.005
.001
.001
.001
.001
.001
.001
.008
.001
001
Gallons
68
359
1466
98
Curies
.002
.004
.013
.001
58 < .001
7 <
< 1 <
< 1 <
121
136 <
258
< 1 <
< i <
.001
.001
.001
.002
.001
.002
cOOl
.001
TOTALS 5651 0.381 5653 0.116 3691 0.081 33<' 0.048 2571 0.024
NOTES:
(l) Radioactivity data has been standardized to cobalt 60 and excludes tritium. Volumes? are prior to dilution.
(2) A total of 0.02 curie was discharged into the river at Quincy, Massachusetts from 1961 through March 1969
when all vork on U. S. Naval nuclear-powered ships was discontinued at General Dynamics, Quincy Division.
(3) A total of 0.01 curie was discharged into the river near Camden, New Jersey from I960 through June 1967
wht-n all work on U. S, Naval nuclear-powered ships was discontinued at New York Shipbuilding Corporation.
(4) Sii{-!;t differences in volumes and radioactivity data from past reports result from using more significant figures
in this Tab1.P. Volumes less than 500 gallons are shown as <1 thousand. Curies less than .0005 are shown as < ,001.
-------
of radioactivity discharged within twelve miles from shore including
into harbors. Keeping discharges small minimizes the radioactivity
available to build up in the environment or to concentrate in marine
life. To implement this policy of minimizing discharges, the Navy
has issued standard instructions defining the radioactive waste disposal
limits and procedures to be used by U. S. Naval nuclear-powered ships
and their support facilities. These instructions were reviewed and
concurred in by the U. S. Public Health Service and the U. S. Atomic
Energy Commission.
To achieve low discharges, the waste disposal procedures and limits
used in the Navy nuclear propulsion program are more stringent than in
the preceding references. The following are some of the procedures
required by the Navy in shipyards:
a. Shipyard management at all levels is required to be involved
in control of radioactive liquid waste.
b. Liquids are segregated to minimize volumes required to be proc-
essed as radioactive. Liquids with different chemical contents are
collected separately to ensure the most effective waste treatment is
used. Dilution is not permitted as a means of processing wastes.
c. Several stages of filtration using various pore size filters
are used to remove small size radioactive particles in liquid waste.
Ion exchange resin and activated carbon are normally used to remove
radioactivity from liquid wastes.
d. Each shipyard has a limit specified for the total amount of
radioactivity to be discharged during the year.
e. Samples are collected during processing to ensure liquid wastes
are far be]ow the permissible water discharge limits in reference 2.
Typical limits used by shipyards arc 30 times lower than in reference 2.
f. To ensure against operational error, liquid wastes which have
been completely processed are transferred to a final clean tank and
again sampled prior to discharge. Discharge from this tank ic through
a final filter.
g. Each discharge requires formal approval of a discharge permit
signed by a designated senior radiological control person.
h. An independent organization within the shipyard audits all aspects
of radioactive waste processing. This audit group is separate from the
radiological control organization which monitors the actual waste proc-
essing work.
-5-
-------
i. Audits are also performed by representatives from Naval Reactors
headquarters who are assigned full time at each shipyard.
j. To ensure absolute compliance with even the smallest detail of
operating procedures, each discrepancy found is brought to management
attention for action. Aggressive action on such minor items prevents
incidents from occurring.
Ot- ar Radionuclides
Reactor coolant also contains short-lived radionuclides with half-
li\es of seconds to hours. Their highest concentrations in reactor
coolant are from nitrogen 16 (7 second half-life), nitrogen 13 (10 min-
ute half-life), fluorine 18 (1.8 hour half-life), argon 41 (1.8 hour
half-life), and manganese 56 (2.6 hour half-life). For the longest-
lived of these, about one day after discharge from an operating reactor
the concentration is reduced to one thousandth of the initial concentra-
tion and in about two days the concentration is reduced to one millionth.
Most discharges from ships occur during heating up prior to power opera-
tion of the reactor, when short-lived radionuelides are at low concentra-
tions in coolant. Total short-lived radioactivity in such a discharge
is less than 0.001 curie. Because of their small amounts a.nd rapid decay,
short-lived radionuclides are less important than long lived r-adicnuclides
for waste disposal considerations.
Fission products produced in the reactor are retained metailurgically
bound within the fuel alloy. Ths fission gases krypton end xenon are
also retained within the fuel elements. However, trace quantities of
naturally occurring uranium impurities in reactor structvar-al materials
release small amounts of fission products to reactor coolant. The
concentrations of fission products and the volumes of reactor coolant
discharged are so low, however, that the total radioactivity attributed
to long-lived fission product radionualides strontium 90 and cesium 137
in discharges from U.S. Naval nuclear-powered ships and their support
facilities has been less than 0.001 curie per year for ail harbors
combined. Fallout of these same fission products has often been mere
than this in one rainfall in a single harbor.
Small amounts of -tritium are formed in reactor coolant systems as
a result of neutron interaction with the approximately 0.015 percent
of naturally occurring deuterium present in water, end other nuclear
reactions. Although tritium has a 12 year half-life, the radiation
produced is of such low energy that the radioactivity concentration
guide issued by the International Commission on Radiological Protection,
the USAEC and by other standard-set ting organizations is c-r.e hundred
times higher for tritium than for cobalt 60. This tritium is in the
oxide form and therefore completely soluble in water; it does not
concentrate significantly in marine life or collect on sediment since
it is chemically indistinguishable from water.
-6-
-------
Tritium is naturally present in the environment because it is
generated by cosmic radiation in the upper atmosphere. Reference 15
reports that the production rate from this source is about six million
curies per year, which through rainfall causes a tritium inventory in
the oceans of about one hundred million curies. Because of this naturally
occurring tritium,large discharges of tritium would be required to make a
measurable change in the background tritium concentration.
The total amount of tritium discharged during each of the last 5
}-, ITS from all U. S. Naval nuclear powered ships and their supporting
tenders, bases and shipyards has been less than 200 curies. Most cf
these discharges have been In the ocean greater than twelve miles from
shore. This total tritium discharged from the entire nuclear Navy Is
less than a single typical electrical generating nuclear power station
discharges each year (reference 10). As described above, such discharges
are too small to Increase measurably the tritium concentration in the
environment. Therefore tritium has been excluded from the data In other
sections of this report.
Liquid Waste at Sea
Radioactive liquid wastes are also discharged tt sea under strict
controls. These ocean discharges are consistent with recommendations
the Council on Environmental Quality made in 1970 to the President in
reference 16. Procedures and limits for ocean discharges have been
consistent with recommendations made by the National Academy of
Sciences - National Research Council in reference 12 and by Ine Inter-
national Atomic Energy Agency in reference 13. Ship discharges have
contained much less radioactivity than these reports considered would
be acceptable. Total long-lived radioactivity excluding tritium dis-
charged farther than twelve miles from shore by all U. S. Naval nuclear-
powered ships and their supporting tenders is shown in Table 2 for
recent years.
TABLE 2
Radioactive Liquid Waste Discharged at Sea
by U. S. Naval Nuclear-Powered Ships
and Supporting 'fenders
Thousand Gallons
1966 UOO 1.2
1967 1520 1.3
1968 1630 1.1
1969 1570 1.7
1970 1220 0.8
-7-
-------
Reactor coolant Is purified through an Ion exchange resin bed.
This resin becomes expended and periodically requires replacement.
Expended resin has been discharged at sea, hut this practice was
discontinued during 1970. When discharged at sea, resin sinks and
as It sinks, the radioactive Ions In the resin are rapidly replaced by
ions of the sea water. Some of the small radioactive particles in the
resin bed are dispersed in sea water and the rest sink with the resin
beads. The radioactivity is rapidly dispersed in the ocean due to
motion of ship during discharge and subsequent action of wind, waves
and ocean currents.
Resin discharge at sea was performed in accordance with procedures
recommended in the National Academy of Sciences - National Research
Council Publication 658, "Radioactive Waste Disposal from Nuclear-
Powered Ships" reference 12. Consistent with these recommendations,
Navy procedures for resin discharge at sea required:
(l) the ship be more than 12 miles from any land,
(2) the water depth be greater than 1200 feet,
(3) the ship not be in known fishing areas, and
(4.) other ships not be nearby and will not be in the wake.
Publication 6$8 developed these procedures to assure no adverse impact
on the environment if up to 300 nuclear-powered ships each discharge
4.00 curies of radioactivity every 2 months off the shores of the United
States.
Table 3 summarizes resin discharges at sea during the last five
years. These results show that the total radioactivity discharged in
resin by the entire Navy each year has been less than envisaged in the
National Academy of Sciences report for a single ship. Diluting this
total radioactivity discharged in a year in a volume as small as one
cubic mile of seawater reduces the concentration of radioactivity to
less than occurs naturally in the ocean. Continued effort by the Navy
resulted in improvements in 1970 which have permitted discontinuing
discharge of ion exchange resin at sea. Expended resin is now packaged
for land disposal in USAEC or State licensed burial grounds as solid
radioactive waste.
-S-
-------
TABLE 3
Radioactive Resin Disposal at Sea by
U. S. Naval Nuclear-Powered Ships
Cubic Feet of Resin Curies
1966 119 439
1967 252 259
1968 196 126
1969 406 132
1970 150 60
Two U. S. Navy nuclear powered submarines have been lost at sea in
the Atlantic Ocean. The submarine THRESHER sank 10 April 1963, 100
miles from land in water 8,500 feet deep at latitude 41°45'N and longi-
tude 65°00'W. The submarine SCORPION sank between 21 and 27 May 1968,
4.00 miles southwest of the Azores in more than 10,000 feet of water.
The reactors used in all U. S. Naval submarines and surface ships are
designed to minimize potential hazards to the environment even under
the most severe casualty conditions such as actual sinking of the ship.
First, the reactor core is so designed that it is physically impossible
for it to explode like a bomb. Second, the reactor fuel elements are
made of materials that are extremely corrosion resistant, even in sea
water. The reactor core could remain submerged in sea water for decades
without release of fission products while the radioactivity decays,
since the protective cladding on the fuel elements corrodes only a few
millionths of an inch per year. Thus in the event of a serious accident
where the reactor is completely submerged in sea water, the fuel elements
will remain intact for an indefinite period of time and the radioactive
material contained in these fuel elements should not be released. The
maximum rate of release and dispersal of the raaioactivicy in the ocean,
even if the protective cladding on the fuel were destroyed, would be so
low as to be insignificant.
Radioactive material could be released from this type of reactor only
if the fuel elements were actually to melt and in addition the high-
strength, all-welded reactor system boundary were to rupture. The
reactor's many protective devices and inherent self-regulating features
are designed to prevent any melting of the fuel elements. Flooding of
a reactor with sea water furnishes additional cooling for the fuel elements
and so provides added protection against the release of radioactive
material.
Radiation measurements, water samples, bottom sediment samples and
debris collected from the area where THRESHER sank were analyzed for
radioactivity by various laboratories with highly sensitive equipment.
Similarly, sea water and bottom sediment samples taken near SCORPION'S
hull were analyzed for radioactivity. None of these samples showed
radioactivity above naturally occurring background levels and none showed
evidence of radioactivity released from either THRESHER or SCORPION.
-9-
-------
SOLID RADIOACTIVE WASTE DISPOSAL
During maintenance and overhaul operations, solid low-level radio-
active wastes consisting of contaminated rags, plastic hags, paper,
filters, ion exchange resin and scrap materials are collected by nuclear-
powered ships and their support facilities. High-level radioactive wastes
are associated with expended reactor fuel, all of which Is transferred to
the USAEC for processing. Solid materials from ships are not dumped at
sea. They are packaged in a support facility or transferred to a ship-
yard for packaging. ?or ultimate disposal, the packaged solid radio-
active wastes are shipped to burial sites licensed by the USAEC or a
State under agreement with USAEC since shipyards and shore facilities
are not permitted to dispose of radioactive solid wastes by burial on
their own sites. Table 4 summarizes total radioactivity and volumes of
radioactive solid waste disposal for the last five years.
Because of efforts to minimize solid waste, total volumes have
remained nearly constant in spite of increasing work caused by increas-
ing numbers of ships. The average annual volume 1'or the entire Naval
nuclear propulsion program could be contained in a cube measuring
fifteen yards on a side. The radioactivity does not require excessively
long time care in the licensed burial grounds since the principal radio-
nuclides do not have half-lives longer than five years. In one hundred
years, such radioactivity will have decayed to one millionth the initial
radioactivity. In less than two hundred years, the total of all radio-
activity in Table 4. will have decayed to less than the amount of radio-
activity in a single luminous watch dial.
•
Disposal of solid radioactive wastes at sea is prohibited by the
U. S. Navy. There have been two special exceptions to this policy.
First on 8 April 1959 the radioactive reactor vessel and reactor plant
components removed from the-sodium-cooled nuclear reactor plar/t in the
submarine SEAWOLF were escorted by the U. S. Coast Guard to a disposal
site in the Atlantic Ocean 120 miles off the East Coast of the U. S.
and sunk in 9,000 feet of water at latitude 38°30'N and longitude 72°06'W.
The disposal was conducted at a site approved for sea disposal of radio-
active waste by USAEC. This disposal site was used by other organizations
for a number of years for radioactive waste as noted in reference 16.
The SEAWOLF components containing approximately 33,000 curies of radio-
activity were welded into a steel barge and scuttled. The low corrosion
of this steel container in seawater and the method of packaging were
designed to prevent any release of radioactivity to the surrounding
sea. As of .1970 this radioactivity has decayed to less than 5,000 curies,
essentially all cobalt 60.
-10-
-------
TABLE 4
RADIOACTIVE SOLID WASTE FROM U. S. NAVAL NUCLEAR-POWERED
SHIPS AND THEIR SUPPORT FACILITIES FOR 1966 THROUGH 1970
1966
Thousand
Facility .
Portsmouth, New Hampshire
Naval Shipyard
Groton, New London, Conn.
Electric Boat Div., Tender
at State Pier, & Sub Base
Newport News, Virginia
Newport News Shipbuilding
Norfolk, Virginia
Naval Shipyard and Tender
Charleston, South Carolina
Naval Shipyard and Tenders
Pascagoula, Mississippi
Ingalls Nuclear Division
San Diego, California
Tenders at Ballast Point
Long Beach, California
Naval Shipyard and Base
Vallejo, California
Mare Island Naval Shipyard
Bremerton, Washington
Puget Sound Naval Shipyard
Pearl Harbor, Hawaii
Naval Shiuvard & Sub Base
Cubic
Feet
19
15
7
4
8
0
1
< 1
9
1
1
Curies
10
1093
9
3
6
0
< 1
< 1
367
1
< 1
1967
Thousand
Cubic
Feet
30
5
17
11
15
0
1
< 1
9
14
1
Curies
193
17
702
86
52
0
< 1
< 1
23
193
1
196,"
Thousand
Cubic
Feet
31
4
14
2
14
0
1
< 1
8 -
14
3
Curies
151
21
10
11
110
0
8
< 1
7
48
6
1959
Thousand
Cubic
Feet
8
8
17
6
15
1
< 1
< 1
8
11
4
1970
Thousand
Cubic
Curies
3
328
382
8
'9
< 1
2
< 1
5
42
3
Feet
14
12
28
9
8
0
< 1
< 1
12
18
:5
Curies
16
140
312
146
6
0
1
< 1
2
1327
4
TOTALS
65 1489
103 1272
92 372
78 783
106 195/.
NOTES:
(l) This table includes all radioactive waste from tenders and nuclear-powered ships. This radioactivity is
primarily cobalt 60.
(2) Slight differences from past reports result from using different number of significant figures in this
table. Volumes less than 500 cubic feet are reported <1 thousand and less than 0.5 curie is reported <1.
-------
The second exception was required for radioactive solid wastes from
Pearl Harbor since it was not feasible to establish a burial ground in
the volcanic rocks of Hawaii. Therefore an ocean disposal area 55 miles
from shore was selected with the agreement of the USAEC, the U. S. Public
Health Service, and the Hawaii Department- of Health. The Navy Hydro-
graphic Office determined that normal ocean currents at this location
are away from shore. Low-level radioactive waste packaged primarily in
fifty-five gallon steel drums weighted with concrete were disposed of
by Pearl Harbor Naval Shipyard in 15,000 feet of water at this location,
as shown in Table 5* The radioactivity in this waste was primarily
cobalt 60. In June 1968 use of this ocean disposal area was discontinued
by the Navy and wastes have since been shipped to a USAEC or State
licensed land burial ground in the continental U. S.
TABLE 5
Solid Radioactive Waste Disposal in the Ocean
at Latitude 20°54'N Longitude l6l°06'W
Number of Volume
Disposal Operations cubic feet Curies
1 1647 0.5
1 1275 0.7
1 672 1.4
1 682 0.3
2 1134 1.0
_4 1720 4.5
10 7130 8.4
-12-
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ENVIRONMENTAL MONITORING
Environmental monitoring surveys for radioactivity are periodically
performed in harbors where U. S. Naval nuclear-powered ships are built
or overhauled and where these ships have home ports or operating bases.
These surveys are performed to verify the adequacy of liquid waste dis-
posal procedures and limits. To ensure thoroughness and objectivity
these surveys are made as independent as practicable from waste disposal
operations. Samples from each harbor monitored are also checked at least
annually by a U. S. Atomic Energy Commission (USAEC) laboratory to ensure
analytical procedures are correct and standardized. These USAEC labora-
tory results have been consistent with shipyard results. As a further
independent check of environmental monitoring the U. S. Public Health
Service (USPHS) has conducted detailed surveys of selected harbors
(references 17 and 18). USPHS has monitored the harbors at Charleston,
South Carolina; Pearl Harbor, Hawaii; San Diego, California; Vallejo,
California; New London, Connecticut; Newport News, Virginia; and Norfolk,
Virginia. Navy monitoring results have been consistent with these USPHS
surveys.
The Navy monitoring program initially emphasized analyzing water
because it is used by boats and swimmers and because fish live in this
water. Surveys were conducted in the harbors before any radioactivity
was discharged, to establish base levels of gross beta activity of harbor
water in the vicinity of berths to be used by nuclear-powered ships and
locations where support facilities might discharge processed water.
Results showed that superimposed on the naturally occurring radioactivity
of 0.3 picocurie* of potassium 4.0 per milliliter of harbor waxer vere
large variations of other radioactivity from fallout. Rainwater before
much dilution in harbor water sometimes has measured more than 100 times
higher than this. In addition rates of introduction of naturally radio-
active radium, uranium, thorium and their associated radionuclldes
varied. However, In more than ten years of monitoring seawater for
gross beta activity commencing in 1954 in New London, Connecticut, and
extending to other ports, no increase in water radioactivity was ever
discovered which could be attributed to operation of nuclear-powered ships
or their support facilities.
Although the general background radioactivity measurements previously
used would indicate presence of radioactivity before exceeding concentra-
tions permitted in reference 2, more sensitive measurement techniques
were adopted in 1965. Currently, five water samples are taken in each
harbor once each quarter year in areas where nuclear-powered ships berth
and from upstream and downstream locations. Ihese samples are analyzed
* One picocurie equals 10~^2 curie, or one millionth of one millionth
of a curie.
-13-
-------
for gross gamma radioactivity and for cobalt 60 content. Procedures
for analysis were selected to detect cobalt 60 if its concentration
exceeds 0.1 picocurie per milliliter, which is 300 times lower than
the USAEC limit of reference 2. No cobalt 60 has been detected in
any of the 2560 water samples from 20 harbors monitored.
Harbor bottom sediment contains many of the remnants of water pollu-
tion; the top layer is generally black and has an offensive odor from
decomposing organic waste materials. Silt carried by rivers also deposits
on harbor bottoms, building up in depth from less than one inch per year
to more than three feet per year. In falling to the bottom, this silt
carries radioactivity from the water to the bottom. Therefore sampling
of harbor bottom sediment became part of early Navy environmental
monitoring programs to provide advance indication of radioactivity
buildup in the harbor.
Initially, dried samples of harbor bottom sediment were measured
for gross beta radioactivity. Results varied from 10 picoauries per
gram of sediment to 300 picocuries per gram, and varied widely from sample
to sample and from month to month in a single harbor. However, analysis
of these data showed no harbor had increased its general background
radioactivity from operations associated with U. S. Naval nuclear-
powered ships.
Commencing in 1963 at Navy request, the USPHS made additional
analyses of samples from some harbors to identify radionuclides present
in sediment. These analyses showed cobalt 60 was the predominant
radionuclide added to sediment from nuclear reactor operations. There-
fore Navy monitoring procedures were changed to collect in each harbor
20 to 120 sediment samples once each quarter year. Standard six inch
square samplers modified to collect only the top one-half to one inch
of sediment are used for all sediment collection. The top layer was
selected because it should be more mobile and more accessible to marine
life than deeper layers. The samples are analyzed for gross gamma
radioactivity and for cobalt 60. Results of the 3070 sediment samples
from harbors in the U. S. and possessions for 1970 are summarized in
Table 6. Comparison to previous environmental monitoring dais, in
references 5 through 9 shows that environmental cobalt 60 levels have
been steadily decreasing.
-U-
-------
TABLE 6
SUMMARY OF 1970 SURVEYS FOR COBALT 60 IN BOTTOM SEDIMENT OF U. S. HARBORS WHERE
U. S. NAVAL NUCLEAR-POWERED SHIPS HAVE BEEN REGULARLY BASED, OVERHAULED OR BUILT
Total Bottom Area Estimated Total***
Number of Samples with Cobalt 60 with Cobalt 60 Cobalt 60 in Top
less than between 3 & 30 to 300 over 3 pCi/g*tt Layer of Sediment
3 pCi/g* 30 pCj/g pCi/g # (Square Kilometers) (Curies)
Portsmouth, New Hampshire
Naval Shipyard 176 000 ND
Groton, New London, Conn.
Electric Boat Division, State
Pier, and Submarine Base 377 86 1 0.1 0.02
Newport News, Virginia
Newport News Shipbuilding 152 0 0 0 ND
Norfolk, Virginia
Naval Shipyard and Base 344 000 ND
Charleston, South Carolina
Naval Shipyard and Bases 382 000 ND
Pascagoula, Mississippi
Ingalls Nuclear Division 212 000 ND
San Diego, California
Navy Pier at Ballast Point 157 0 0 0 ND
Long Beach, California
Naval Shipyard and Base 158 0 0 0 ND
Vallejo, California
Mare Island Naval Shipyard 444 000 ND
BremerCon, Washington
Puget Sound Naval Shipyard 141 0 0 0 ND
Pearl Harbor, Hawaii
Naval Shipyard and SubBase 312 0 0 0 ND
Apra Harbor, Guam 128 000 ND
NOTES:
* Minimum detectable radioactivity is approximately 1 pCi/g (picocurie per gram). Results in units of pCi/cm2
lange from two to four times the value of pCi/g.
** One square kilometer is approximately equal to 0.4 square mile. Areas with cobalt 60 over 3 pCi/g were
in immediate vicinity of piers used for berthing nuclear-powered ships.
*** Where total cobalt 60 in the surface sediment layer is less than 0.01 curie, ND is reported. Samples
more than one foot deep from several harbors show that total cobalt 60 present may be two to five times
that measured in the surface layer.
, # No samples from any harbor were greater than 31 pCi/g.
-------
Table 6 shows that some samples taken near liquid waste discharge
points show cobalt 60 radioactivity. However, the affected areas are
small and the total cobalt 60 present is small compared to natural
radioactivity present in harbors.
The first data column in Table 6 includes all samples with less
than three picocuries of cobalt 60 per gram of sediment. These low
levels are difficult to measure because the levels of radioactivity
in sediment from other sources are much higher. The value of 30
picocuries per gram was selected for the top of the second range of
data since it corresponds to the upper limit for exposure in references
2 and 4 even if consumed continuously by members of the general public.
Although sediment can not be consumed by humans, it might serve as a
food source for marine life. Data on uptake of cobalt 60 from sediment
by marine life obtained to date show that in the salt water harbor
bottom environments, no significant buildup of cobalt 60 occurs in
marine life. Therefore the third range of up to 300 picocuries per
gram is selected as a range which would not cause members of the general
public to receive radiation exposure approaching the values set in
references 2, 3, 4 and 14. Concentrations of cobalt 60 up to 300
picocuries per gram are so low that the USAEC does not require those who
might possess them to be licensed. If concentrations higher than 300
picocuries per gram were to persist over substantial areas of a harbor
bottom, further monitoring would be performed to determine if any of
this radioactivity were being taken up by marine life for eventual con-
sumption in food. Because of the low concentrations noted in Table 6,
monitoring of radioactivity in marine life has not been necessary as part
of the routine environmental monitoring programs in these harbors.
References 19 and 20 contain evaluations by USAEC laboratories of
the effects on the environment from the accumulation near points of
discharge of radionuclides from several other nuclear reactors. These
reports conclude for these other reactors that radioactivity levels
much greater than shown in Table 6 have caused no significant exposure
to the general public.
An additional part of the environmental analyses has been to compare
amounts of radioactivity measured in the environment with amounts dis-
charged, as in the following example. If 0.01 curie were discharged each
year for more than ten years into a single harbor, the maximum total
inventory of cobalt 60 in this harbor will be 0.1 curie of cobalt 60,
assuming none of this radioactivity is flushed out with river currents,
tides, or dredging. If all this radioactivity were spread uniformly
over a reasonable area of one square kilometer of the harbor bottom,
the result would be less than ten picocuries of cobalt 60 per square centi-
meter. This cobalt 60 will be distributed deeply through the sediment
-16-
-------
over the years, resulting in an average concentration less than one
picocurie of cobalt 60 per gram of sediment. This is less than the
amount of cobalt 60 which would be detected by present sensitive
environmental monitoring techniques. Results of analyses such as
these help confirm the environmental monitoring data of Table 6 and
confirm that the Navy's waste discharge'limits are satisfactory.
In all monitored harbors, twice per year shoreline areas uncovered
at low tide are- surveyed for radiation levels with sensitive radiation
detectors to determine if any radioactiyity from bottom sediment
washed ashore. All results were the same as background radiation
levels in similar areas, 0.01 to 0.04. millirem per hour. Thus there
is no evidence in these ports that radioactivity from sediment is
washing ashore.
Film badges are continuously posted at locations outside the
boundaries of areas where radioactive work is performed. These films
showed that radiation exposure to the general public outside these
facilities was not above that received from natural background radia-
tion levels.
Naval nuclear reactors and their support facilities are designed
to ensure there are no detectable discharges of airborne radioactivity
to the atmosphere. Filtration equipment is installed in support facilities
to ensure removal of airborne radioactivity without release to the
atmosphere. Exhaust stacks at support facilities which could have
discharged airborne radioactivity have been monitored. There wore
no discharges of airborne radioactivity to the atmosphere measured
above concentrations normally present in the atmosphere.
In addition to the locations listed in Table 6, environmental monitor-
ing is performed by U. S. Navy submarine tenders which serve as operating
bases for U. S. Naval nuclear-powered submarines in Rota, Spain and Holy
Loch, Scotland. Results of the surveys in the harbor at Rota, Spain
have not shown detectable cobalt 60 in harbor bottom sediment samples.
In 1965 in Holy Loch, more cobalt 60 radioactivity than expected was
detected in harbor bottom sediment and on shoreline niud flat areas
uncovered at low tide. However, there had been no increase of harbor
water radioactivity in Holy Loch above normal background levels. Joint
U. S. and British assessments of survey results confirmed that radiation
levels in the vicinity of the Holy Loch anchorage were far below those
which were at all likely to cause an individual to receive radiation
exposure approaching limits for members of the general public. Environ-
mental monitoring during 1970 showed radioactivity levels in Holy Loch
are steadily declining and are now less than half the levels in 1965*
-17-
-------
CONCLUSIONS
1. The total radioactivity discharged into all ports and harbors from
the U. S. Naval nuclear propulsion program was 0.024 curie in 1970.
2. No increase of radioactivity above normal background levels has
been detected in harbor water where U. S. Naval nuclear-powered
ships are based, overhauled, or constructed.
3. Discharges of liquid wastes from U. S. Naval nuclear-powered ships
have not caused a measurable increase in the general background
radioactivity of the environment.
4. Low-level cobalt 60 radioactivity in harbor bottom sediment is
detectable around a few piers at operating bases and shipyards
where nuclear-powered ship maintenance and overhauls have been
conducted over a period of several years. Cobalt 60 is not
detectable above background levels in general harbor bottom
areas away from these piers. Maximum total radioactivity observed
in a U. S. harbor is less than one curie of cobalt 60. Comparison
to previous environmental monitoring data in references 5 through
9 shows that these environmental cobalt 60 levels have been
steadily decreasing.
-18-
-------
REFERENCES
(l) IT. S. Navy Report - Radioactive Waste Disposal from U. S. Naval
Nuclear-Powered Ships, Prepared by T. J. Iltis and M. E. Miles,
January 1959.
(2) Code of Federal Regulations, Title 10 (Atomic Energy Commission),
Part 20, "Standards for Protection Against Radiation."
(3) National Council on Radiation Protection and Measurements, Report
No. 22, "Maximum Permissible Body Burdens and Maximum Permissible
Concentrations of Radionuclides in Air and in Water for Occupational
Exposure" (Published as National Bureau of Standards Handbook 69,
Issued June 1959, superseding Handbook 52).
(4) International Commission on Radiological Protection, Publication
2, "Report of Committee II on Permissible Dose for Internal
Radiation (1959)," with 1962 Supplement Issued in ICRP Publication
6; Publication 9, "Recommendations on Radiation Exposure (l965)"j
and ICRP Publication 7 (1965), amplifying specific recommendations
of Publication 9 concerning environmental monitoring.
(5) U. S. Navy Report - "Disposal of Radioactive Wastes from U. S.
Naval Nuclear-Powered Ships and Their Support Facilities," by
J. W. Vaughnn and M. E. Milesj issued in Radiological Health
Data and Reports, May 1966.
(6) U. S. Navy Report - "Disposal of Radioactive Waste from U. S.
Naval Nuclear-Powered Ships and Their Support Facilities, 1966",
by M. E. Miles and J. J. Mangeno, issued in Radiological Health
Data and Reports, December 1967.
(7) U. S. Navy Report - "Disposal of Radioactive ^/as^es from U. S.
Naval Nuclear-Powered Ships and Their Support Facilities, 1967",
by M. E. Miles and J. J. Mangeno, Issued in Radiological Health
Data and Reports, April 1969.
(8) U. S. Navy Report - "Disposal of Radioactive Wastes from U. S.
Naval Nuclear-Powered Ships and Their Support Facilities, 1968",
by M. E. Miles and J. J. Mangeno, issued in Radiological Health
Data and Reports, September 1969.
(9) U. S. Navy Report - "Disposal of Radioactive Wastes from U. S.
Naval Nuclear-Powered Ships and Their Support Facilities, 1969",
by J. J. Mangeno and M. E. Miles, issued in Radiological Health
Data and Reports, August 1970.
(10) U. S. Public Health Service Report - "Radioactive Waste Discharges
to the Environment From Nuclear Power Facilities" by J. E. Logsdon
and R. I. Chissler, BRH/DER 70-2, Karon 19r"0.
-19-
-------
(ll) Federal Radiation Council Memoranda, approved by President Eisenhower
on May 13, I960, President Kennedy on September 20, 1961, and
President Johnson on July 31, 1964..
(12) National Academy of Sciences - National Research Council, Publica-
tion 658, "Radioactive Waste Disposal from Nuclear-Powered Ships", 1959.
(13) International Atomic Energy Agency, "Radioactive'Waste Disposal into
the Sea," Safety Series No. 5, Vienna 1961.
(14) National Council on Radiation Protection and Measurements, Report
No. 39, "Basic Radiation Protection Criteria", January 1971.
(15) U. S. Atomic Energy Commission Report - "Sources of Tritium and Its
Behavior Upon Release to the Environment" by D. G. Jacobs, TID-24.635,
1968.
(16) Council on Environmental Quality Report to President Nixon - "Ocean
Dumping: A National Policy", October 1970.
(17) U. S. Public Health Service Report - "Radiological Survey of Major
California Nuclear Ports", by D. F. Cahill, D. C. McCurry and W. D.
Breakfield, Clearinghouse for Federal Scientific and Technical
Information No. PH178728, April 1968.
(18) U.S. Public Health Service Report - "Radiological Survey of Hampton
Roads (Norfolk - Newport News), Virginia" by H. D. Harvey, Jr.,
E. D. Toerber and J. A. Gordon, Clearinghouse for Federal Scientific
and Technical Information No. AD683208, January 1968.
(19) Oak Ridge National Laboratory Report - "Clinch River Study" ORNL-4035
April 1967.
(20) Battelle Memorial Institute, Pacific Northwest Laboratory Report -
"Evaluation of Radiological Conditions in the Vicinity of Hanford
for 1969" BHWL-1505 November 1970;. and previous periodic reports
in conjunction with report by J. L. Nelson, R. W. Perkins, J. M.
Nielsen anrt W. L. Haushild, page 139, IAEA Symposium on the
Disposal of Radioactive Wastes into Seas, Oceans and Surface
Waters, Vienna, 16-20 May 1966.
-20-
-------
APPENDIX A-14
POWER UTILITIES
-------
APPENDIX A-14
POWER UTILITIES
These industries are responsible for providing and distributing
energy, essential to the stimulation and support of economic develop-
ment. The United States consumes about 35 percent of the world's
total energy product. In 1970, this amounted to approximately 685 times
15
10 Btu of energy, derived.almost in its entirety from fossil fuels.
Of this energy total,almost one-third is provided in the form of elec-
tricity, 50 percent of which is generated using coal as the energy
source, 20 percent using petroleum, 10 percent using natural gas,
and the remaining 20 percent generated by water power. A small
amount is derived from the use of nuclear fuels (Reference 1).
The industrial consumption pattern for the fossil fuels indicates
that most of the coal is used to generate electricity, while petroleum
and natural gas are used directly for space heating and to provide auto-
motive power for vehicles. This section will discuss two types of
power utilities: electric and natural gas.
-------
APPENDIX A-14-2
1. ELECTRIC UTILITIES
Presently, electric power accounts for about one-third of the
total energy supply. Table A-14-1 summarizes the availability of
electric energy in the United States, as of 1966 (Reference 2). The
availability of power and type of ownership are given for the follow-
ing specific geographic areas:
North East - Maine, New Hampshire, Vermont,
Massachusetts, Rhode Island, and
Connecticut
Middle Atlantic - New York, New Jersey, and
Pennsylvania
East North Central - Ohio, Indiana, Illinois, Michigan,
and Wisconsin
West North Central - Minnesota, Iowa, Missouri, North
Dakota, South Dakota, Nebraska,
and Kansas
South Atlantic - Delaware, Maryland, District of
Columbia, Virginia, West Virginia,
North Carolina, South Carolina,
Georgia, and Florida
East South Central - Kentucky, Tennessee, Alabama,
and Mississippi
West South Central - Arkansas, Louisiana, Oklahoma,
and Texas
Mountain - Montana, Idaho, Wyoming, Colorado,
New Mexico, Arizona, Utah, and
Nevada
Pacific - Washington, Oregon, California,
Alaska, and Hawaii
A-14-2
-------
Table A-14-1
Electric Energy, Power Source and Ownership
Geographical
Area
North East
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Millions of Kilowatt Hours
Electric
Utilities
Fuel
38, 945
143,555
230, 810
57, 294
158,607
100,486
110,266
26,602
80, 030
946,594
Hydro
4,444
23,038
3,654
10,368
12,861
17,099
2,886
24,565
95, 842
194, 756
Total
47,942
166,593
234,464
67,662
171,468
117,584
113,152
54,167
175,872
1, 148,900
Ownership
Private
42, 564
147,363
224, 540
46,317
159,502
35,523
99,060
36,514
89,456
880,837
Public
Municipal
685
831
7,275
6,204
6,290
1,361
7,881
1,220
20, 879
52,627
Other
140
18,399
2,649
15,141
5,676
80, 700
6,211
16,433
65,538
210,886
w
(1)
Reference 2.
00
-------
APPENDIX A-14-4
Table A- 14-2 gives a breakdown in the consumption of fossil fuels,
by the electric industry for 1966 and 1967 (Reference 2). Also shown,
is the amount of fuel that was required per kilowatt-hour of electricity.
The projected growth in demand for electricity in millions of
kilowatt-hours is: for 1975-2,166,000; for 1980- 3,061,000; for
1985 - 4, 238, 000; and for 1990 - 5, 828, 000. The current annual
growth rate for electrical energy is 9 percent. This means that the
capacity must double in the next eight years. The Federal Power
Commission estimates that within 20 years an additional 300 power ;
stations of 3, 000 Mw each, and an additional 7 million acres of new
land for electric transmissions,will be required. Assuming a 10-degree
rise in cooling water for the additional capacity, and without the use
of wet or dry cooling towers, the total water required would approxi-
mate 5 times 1014 gallons per year. This is equivalent to the annual
runoff from 48 contiguous states, and cannot be made available within
the next 20 years (Reference 3).
The use of nuclear fuels compounds this problem, in that those
likely to be used in this time frame are less efficient in converting
heat into electrical power, and hence add more of the energy into the
environmental waters.
2. GAS UTILITIES
The gas utility industry handles various types of gas distributed
as an energy source. Table A- 14-3 shows a breakdown of gas,types
together with the energy content, revenues, and the customer distri-
bution for each commodity (Reference 2).
-------
Table A-14-2
Consumption of Fossil Fuels by Electric Utilities, 1966-1967
Year
1966
1967
Fuel Generated
(mil. kw-hr)
949.594
991,706
Coal (Short Tons)
Anthra.
2,192
2,186
Bit. & Lig.
264,285
271,787
Total
2/J6.477
273,973
Oil
42 Gal bbls.
140, 949
161,275
Gas
Mil- Ft3
2,609,945
2,743,251
Per Kw-hr.
Coal
(lb. )
.869
.870
Oil
(Gal)
.075
.076
Gas
Ft3
10.4
10.4
w
I
Ol
-------
Table A-14-3
Gas Utility Industry Customers, Energy, and Revenue, 1966
Type of Gas
SIC 4922 - Natural
SIC 4925 - Manufactured
- Mixed
- Liquid Petroleum
Total
Customers (1, 000)
Resident.
34,471
91
540
40
35,142
Commercial
2,827
7
31
3
2,868
Industrial
172
1
1
-
174
Total
37,513
99
574
43
38,228
Quantity
(Mil- Therms)
127,525
89
1,297
22
128,932
Revenues
(Mil. Dol. )
7,745
16
111
5
7,878
en
-------
APPENDIX A-14-7
Table A- 14-4 gives a breakdown of the geographical distribution
of the gas utilities in the United States, together with the power consump-
tion and associated revenues (Reference 2).
The future of the gas industry depends largely on technological
advances. The industry, as it is now known (as a direct
fuel for space heating, etc. j^may decline as electric generation grows,
due to better conversion efficiency and environmental acceptability of
coal, petroleum, and nuclear fuels. On the other hand, the demand
for gas may increase,markedly, if gas fuel-cells are used to produce
electrical power efficiently onsite, or where the environmental
problems of coal, petroleum, or nuclear fuels become acute and retard
the growth of the central powers generation concept.
3. POWER RESOURCES
Electric power is generated from the following resources:
Coal
Petroleum and natural gas
Uranium
Hydro power
Geothermal power
(1) Coal
Anthracite - In 1968,the U.S. production was
11, 591 thousand short tons, with a domestic
demand for 10, 160 thousand short tons. Of this
demand,the electric utility industry consumed
2, 203 thousand short tons or about 22 percent. The
projected demand,for the year 2000, is estimated to be
-------
Table A-14-4
Gas Utility Distnoution of Customers, Energy and Revenue, 1966
Geographical
Area
North East
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Customers (1,000)
Resident
1,536
7,387
7, 995
2,858
2,841
1,583
4,003
1,461
5,478
Commercial
98
558
618
273
241
160
383
165
373
Industrial
10
30
37
21
14
6
34
7
14
Total
1,645
7,987
8,657
3,153
3,104
1, 756
4,424
1,673
5,866
Quantity
(Mil- Therms)
1,800
13,597
29, 709
13,970
9,532
8,152
25,174
7,463
19,537
Revenues
(Mil. Dol.)
285
1,406
2,141
729
691
402
815
339
1,071
H
CD
-------
APPENDIX A-14-9
between 1. 0 and 3. 6 million short tons, based on
a continuing decline in coal use. The estimated
domestic anthracite reserves amount to 12,969
million tons, and at a 50 percent recovery,
amount to 6, 485 million tons of this type coal.
Bituminous and Lignite - Production for 1968 was
637, 858 thousand short tons, with a domestic demand
for 498,830 thousand short tons. Of this total,the
electric utility industry consumed 294, 739 thousand
short tons or about 58 percent. The anticipated domestic
demand for the year 2000 lies between 1, 275 to 2, 639
million tons. The proven domestic reserves amount
to 1, 546, 906 million short tons of ore, and at a 50 percent
recovery amount to 773, 453 million short tons of coal.
In additional is believed that additional reserves of
1, 313, 080 million tons of coal may exist. Other
resources include 337,105 million tons that lie at a
depth of 3000 to 6000 feet.
(2) Petroleum and Natural Gas
Petroleum - The 1968 production of petroleum amount-
ed to 6, 008. 1 million (42 gal) barrels, with an industrial
demand of 4, 900. 2 million barrels. The chief consumers
of petroleum are the household and commercial (2, 699. 0
million barrels), and transportation (1, 149.0 million
barrels) sectors. Electric utilities consume only
188.0 million barrels (3.8 percent). The projected domestic
-------
APPENDIX A-14-10
demand for petroleum,in the year 2000,is set between
7. 3 and 16. 4 million barrels. The domestic petroleum
reserves include an estimated 30. 71 billion barrels
of crude oil, 77 percent of which is located in Texas,
California, and Louisiana, and 8. 60 billion barrels
of liquid natural gas, 77. 7 percent of which is located
in Texas and Louisiana.
Natural Gas - In 1968 the domestic supply of dry natural
gas was set at 21, 796, 809 million cubic feet, with a demand
of 18, 957, 124 million cubic feet. Of that total, 3, 143, 858
million cubic feet (33 percent) was consumed by household
and commercial industry, and 6, 250, 997 million cubic feet
(16 percent) being used in the electric utility industry. The
projected requirement for dry natural gas for the year 2000
is set between 34, 800 to 55, 700 billion cubic feet. The dry
natural gas reserves in the United States are currently
estimated at 287. 35 trillion cubic feet.
(3) Uranium
The 1968 total domestic production of uranium amounted to
10, 463 short tons, with a demand of 2, 700 short tons. A total of
2, 658 short tons, or about 99. 9 percent, of the total demand went
into power reactors. For the year 2000, uranium demand is
estimated to be between 72,000 and 81,000 short tons. The amount
of electricity produced,using radioactive fuel,is very small but,
by the year 2000, 40 to 60 percent of electrical power may be
derived from this fuel type.
-------
APPENDIX A-14-11
(4) Hydropower
Around 1960, about 20 percent of the electrical energy was
generated by water power. Water power is restricted by geographical
location, and is not evenly available throughout the year. The Federal
Power Commission estimates that the hydro capacity for the 48
contiguous states is 127 million kilowatts. The projection for
1980 is a total installed capacity of 65 million kilowatts. It is not
anticipated that the domestic hydro capacity will exceed 90 million
kilowatts at any time in the future,because of the increased use
of nuclear power. Exploitation of the theoretical capacity of
127 million kilowatts, would produce only 10 percent of the total
electrical demand in the year 2000 (Reference 4).
(5) Geothermal Power
This is a natural heat source derived primarily from radio-
active decay in the earth. The annual energy flow to the surface of
the earth approximates that provided by 170 billion barrels of
petroleum. Although these natural steam sources have very little
impact on the environment, they are low in atmospheric pollutants
and contain no ash, nitrogen, sulfur oxides, or radiation hazards.
their use as energy sources are severely limited by geographical
location. It is estimated that the worldwide geothermal power
capacity driven by geothermal heat now equals about 700, 000 kilowatts,
and will increase over the next several decades (Reference 5).
4. ASSOCIATED ENVIRONMENTAL POLLUTION
The power utilities contribution to our environmental degradation
is shown in Table A- 14-5.
-------
APPENDIX A-14-12
Table A-14-5
Type of Pollution by Fuels in Electric Utility Industry
Energy
Sources
CO
1— 1
0)
fa
•1-1
CO
CO
o
fa
I 0)
.2 £
TJ •"
&<
f-i .
0) h
•4-1 j>
•rt „
R S
rt P3
Coal
Petroleum
Nat. Gas
Annual Emissions
(Million Tons)
Nuclear
(Uranium)
Hydro
Geothermal
(Steam)
Air
T3 CO
* CO TJ
i *> S 'x m
S *o 2 /^ co
o .^ x» O -S
§ X tn fl rt
C O y CU "3
0 h 0 g> .«
JQ 3 (H 0 S
^ U3 "0 i3 fc
rt 3 >j .PH rt
U m EC 2 PH
X X X X X
X X X X X
X
1 12 1 3 3
Water
Thermal
Radiation
X
X
X
X X
X
Solids
XI CU
03 £
co g rt
^ "S rt 'Q.
fa PQ 03 W
X X
X
24 6 1
X
-------
APPENDIX A-14-13
(1) Air Pollution
The major chemical contributors to air pollution, emitted
by power utilities, are described in the following paragraphs.
Carbon Monoxide- This gas develops due to imperfect
combustion of fossil fuels, and is attributed almost entirely
to man himself. Although large amounts are emitted, it does
not seem to accumulate in the atmosphere. The mechanism for
its removal is not well understood.
Sulfur Oxides - These occur as impurities in fossil
fuels, and are among the most troublesome of the air
pollutants. Sulfur dioxide may form sulfuric acid, or it
may react further to form ammonium sulfate. The life of
sulfur in the atmosphere is about a week, and when it is
removed from the atmosphere by precipitation the acidity
of rain fall results, the increase in acidity shows up as
water pollutants.
Hydrocarbons - These are produced by combustion
of coal, wood, and particularly by the processing and use of
petroleum. The reactions of hydrocarbons with nitrogen
oxides when acted upon by ultra-violet radiation,produce a
photo-chemical smog that is hazardous to health and property.
Oil spills add hydrocarbon pollutants in local concentrations,
which are toxic to many living organisms. These yearly
spills total to about 1 million tons of pollutant,but seem to have
no world wide effects. It appears that bacteria degrade the
oil rapidly.
Nitrogen Oxides- These are produced in the combustion
process, the three most common are nitric oxide, nitrogen dioxide,
and nitrous oxide. Nitrogen dioxide, the worse of the three,
is a strong absorber of ultraviolet radiation, and also involves
photo-chemical reactions causing smog, and when associated
with water can produce nitric acid.
Particulates - Solid particles are injected into the lower
atmosphere from a number of sources, the utilization of
fossil fuels being a major contributer. Pollution technology
now available is adequate for limiting such emission.
-------
APPENDIX A-14-14
(2) Water Pollution
The major contributors to water pollution are thermal and
radiation emissions.
1. Thermal Pollution
This form of pollution is dissipated into the environ-
ment in two ways: through the smoke stacks directly into
the atmosphere, and as heated cooling water.
The world's present energy use-rate is approximately
0. 01 percent of that which the earth absorbs from the sun and
reradiates into outer space to maintain its equilibrium. Present
knowledge indicates a use-rate equal to 1 percent that amount would
cause concern, while a use-rate 10 percent of that amount would
be intolerable. A 3 percent annual increase rate for a period of
150 years would produce the 1 percent rate spoken of earlier,
However, in the nort3eastern United States/ where 40 percent
of the national energy is used, the 1 percent figure has been
reached, with no noticable climatic effect. In the Los
Angeles area, the 1 percent has been exceeded with no noticeable
climatic effects. Thermal pollution is harmful to aquatic and
biological activity. The electric power industry is a chief
contributer, due to its vast requirement for cooling water.
The present trend to move from the use of fossile fuels
to nuclear fuels, for the generation of electrical energy reduces
many pollutants, but adds to the problem of thermal pollution
because about 40 percent more heat is added to the environment
than is the case with fossil fuels (due to conversion efficiency of
the nuclear reactors).
(1) Future Outlook for Thermal Pollution. In 1970,a
total of 5, 596 x 1015 Btu of energy produced 1. 360 x 109
Kwh of electric energy, required about 125 x 109 gallons
of cooling water per day, and released 3. 720 x 10 Btu
to the environment. Predictions for the year 2000 indicate
that 2. 510 x 1014 Btu of energy will produce 6. 100 x 109
Kwh of electricity, requiring 677 x 1014 Btu of energy
to the environment (Reference 6).
-------
APPENDIX A-14-15
The situation,as described,points up the fact that
concerted efforts must be made in the technology associated
with fuel processing, combustion and energy conversion,
and cooling and heat dissipation facilities. An effort must
be made to reduce the consumption of electricity by developing
more applications for by—products of energy production now
wasted. Failure to carry out advances in these areas will
create a large burden for our environmental managers, and
may result in the acceptance of further and more serious
degradation of our environment.
Development of uses for wasted thermal energy is
being pursued in the fields of agriculture (greenhouse,
poultry, and swinehouse heating), aquaculture (heating
water to stimulate growth of certain marine life), and
urban and industrial heating. These uses would require
the proximity of a generating plant.
(2) Control of Thermal Pollution. Thermal pollution
can and should be controlled through an established
environmental control program. Areas to be considered
include:
Reduction of Waste Heat by Improving Thermal
Conversion Efficiency — The efficiency with
which energy fuels are being converted into
electricity have been undergoing improvement
with time. In 1938, it required 16, 500 Btu to
produce 1 Kw of electricity, by 1970 this
amount was reduced to 10,000 Btu's and,by
1980,the Federal Power Commission predicts
the requirement to drop to 8, 500 Btus, however
with these improvements by 1980,60 percent of
all energy used to generate electricity will be
wasted.
Management of Heat Waste in the Environment —
Methods to reduce the degrading effect of heat
waste on the environment must be developed.
These could include efforts to provide turbulence
in receiving waters, injection of heated effluent
into deep portions of the receiving waters,
construction of dams, and even shuting- down power-
plants during certain periods of the year.
-------
APPENDIX A-14-16
Improvement of Heat Disposal Techniques —
Presently heat disposal consists of the once-
through system and closed-cooling cycle.
The Once-Through-System is used where
water is readily available. Water is
brought in from the water source, used for
cooling and discharged back into the water
course. The advantage of this system is
low water consumption, control of tempera-
ture to meet biological objectives, and
dissipation of heat into the atmosphere over
a large area. The Closed Cycle System
includes cooling ponds, spray systems, wet
draft towers, and dry draft towers. Cooling
ponds are used primarily in the southwest
where vast land areas and low humidity pro-
vide good cooling characteristics. Spray
systems are used to increase heat dissipation,
however, water loss from evaporation and
drift are considerable. There are two types
of wet draft towers, natural and mechanical.
In the natural type, cooling is accomplished by
using natural draft or air passing through water
droplets. Cooling is by evaporation,consuming
about 2-1/2 times as much water as the once-
through process, and 3 percent of the total water
must be replaced due to loss. A IpOO Mw
plant requires 30 million gallons daily, which
today is acceptable but may not be in 20 or 30
years. The mechanical cooling systems are
smaller in size than natural tower systems.
Air is forced through the spray by motor driven
fans. Capital costs are lower than natural but
operating costs are higher. There are problems
with fog and ice in humid areas. Dry draft
towers are appreciably larger (350 feet high and
325 feet in diameter) than the wet towers, and
cost three to five times more. This technique
avoids the difficulties of evaporation and water
draft loss, however, warm areas inflict a
severe penalty on thermal efficiencies.
-------
APPENDIX A-14-17
2. Radiation Pollution
Most radioactivity is in the form of fission products
of uranium dioxide fuel. Some are refractory oxides in-
soluble in water, while others are not only soluble but
volatile. These wastes have a very high level of activity
with a heat output of about 10^ Btu/hr/lb of uranium. The
long-term storage of these highly radioactive fission
products are a serious problem. They are determined by
long-lived isotopes, i.e., strontium 90, which has a 28-year
half-life, and cesium 137, which has a 30-year half-life
(Reference 7). The following procedures 'are presently
used in the handling and disposing of these wastes.
Wastes are removed from the reactor in shielded
containers designed to withstand shipping acci-
dents.
Containers are cut open at reprocessing plants;
the contents are dissolved in acid, and uranium
and plutonium recovered. Radioactive fission
products are concentrated and stored in double
walled containers for 5 years.
After 5 years, products are evaporated to dryness,
sealed in steel containers, and shipped to the
national waste repository in central Kansas for
storage at a depth of 1500 feet for a period of a
thousand years.
The shipping and processing techniques have been
developed and proved safe. All nuclear powerplants are
monitored by the United States Public Health Service for
radioactivity, and the disposal of solid wastes follows a
strictly regulated and monitored procedure.
The future of the radioactive waste problem depends
on the advancement of reactor technology. The light-water
reactors used now have two disadvantages: (1) low thermal
efficiency, and (2) requirement for uranium-235 which is
scarse. By 1980, these reactors would require 200,000 tons
of uranium concentrate, and 1. 6 million tons in the year 2000.
-------
APPENDIX A-14-18
This could exhaust our estimate of this low-cost uranium.
The breeder reactor would use the more abundant U-238.
The breeder reactor would require 1. 3 tons uranium per
Mkwh compared to 171 tons for the light-water reactor, and
would increase the conversion efficiency of nuclear power
conversion to that now enjoyed by fossil fuels (Reference 8).
-------
APPENDIX A-14-19
REFERENCES
1. "Human Energy Production as a Process in the Biosphere, "
S.F. Singer, Scientific American, September 1970.
2. Statistical Abstract of the United States, U.S. Department of
Commerce, Bureau of the Census, 1966.
3. "Energy, the Economy and the Environment, "D.C. White,
Technology Review, October/November 1971.
4. Resources in America's Future, Landsbury, Fischman, and
Fisher, The Johns Hopkins Press.
5. "Geothermal-Earth's Primordial Energy, " R.G. Bowan, and
E.A. Groh, Technology Review, October/November 1971.
6. "Must Fossil Fuels Pollute?, " H. Perry and H. Berkson,
Technology Review, December 1971.
7. New Techniques for Energy Conversion, S. N. Levine, Dover
Publications.
8. "Electric Power from Nuclear Fission, " M. Benedict,
Technology Review. October/November 1971.
In addition to this specifically referenced material, much
reliance has been placed on:
Mineral Facts and Problems, U.S. Department of Interior,
Bureau of Mines, Bulletin 650, 1970.
-------
APPENDIX B
CURRENT LISTINGS
OF HAZARDOUS MATERIALS
-------
APPENDIX B
CURRENT LISTINGS
OF HAZARDOUS MATERIALS
The definition of hazardous materials is an elusive quest.
Under certain conditions, distilled water may be hazardous (drowning).
Any listing of hazardous materials is an effort to select and list those
materials of particular impact on the mission of the interested organi-
zation. On the assumption that a comparison of materials on the various
lists would provide insights as to those hazardous materials of most
widespread concern, we have prepared a tabulation which indicates the
materials contained on each list.
The listings identified by the numbers (column headings) are
from:
(1) Designation of Hazardous Substances (draft EPA-WQO
list)
(2) Control of Spillage of Hazardous Polluting Substances -
Battelle
(3) Dangerous Chemicals Code - Los Angeles Fire Department
(4) Manufacturing Chemists Association
-------
APPENDIX B-2
(5) National Institute of Occupational Safety and Health
(6) National Academy of Sceinces
(7) Chemical Safety References - Chemical Section,
National Safety Council.
-------
ABIETIC ACID
ACETALDEHYDE
ACETALDOL
ACETAMIDE
ACETANILIDE
ACETIC ACID
ACETIC ANHYDRIDE
ACETONE
ACETONE CYANHYDRIN
ACETONITRILE
ACETOPHENONE
ACETYL BENZOYL PEROXIDE
ACETYL BROMIDE
ACETYL CHLORIDE
ACETYLENE
ACETYLENE CHLORIDE
ACETYLENE DICHLORIDE
' ACETYL PEROXIDE, WET
SOLID
[ ACRIDINE
L ACROLEIN
, ACRYLIC ACID
ACRYLONITRILE
ADIPIC ACID
. ADIPONITRILE
i A LA NINE
ALKYL ARYL SULFONATE
(1)
X
X
<
X
X
X
X
*
*
X
A
<
<
/
X
X
X
X
(2)
X
K
K
/
K
X
t
*
*
<
A
X
X
X
X
*
X
*
A
X
X
X
<
(3)
X
X
<
X
X
/
*
y
X
y
X
A
<
t
A
<
X
>
(4)
A
<
X
X
X.
K.
y
y
X
X
X
X
>
1
(5)
X
*
*
X
X
X
X
X
(6)
X
X
X
*
<
>*
*
Jlr
A
X
.
(7)
Y
*
X
<
Y
V
Y
X
V
^
V
•a
s
z
D
Cd
co
-------
ALLYL ACETATE
ALLYL ALCOHOL
ALLYL AMINE
ALLYL BROMIDE
ALLYL CHLORIDE
ALLYL CHLOROFORMATE (see allyl)
CHLOROCARBONATE
ALLYL TRICHLORISLIANE
ALLYLDINE DIACETATE
ALUMINUM AMMONIUM SULFATE
ALUMINUM, DUST
ALUMINUM CHLORIDE, ANHYDROUS
ALUMINUM FLUORIDE
ALUMINUM NITRATE
ALUMINUM OXIDE
ALUMINUM SULFATE
ALUMINUM TRIETHYL
AMINOETHYLETHANOLAMINE
4-AMINO-M-TOLUENE
AMMONIA, AQUA
(ammonium hydroxide)
AMMONIUM ACETATE
AMMONIUM ARSENATE
AMMONIUM CARBONATE
AMMONIUM CHLORIDE
. AMMONIUM CHROMATE
AMMONIUM DICHROMATE
AMMONIUM FERRO-CYANIDE
AMMONIUM FLUORIDE
(1)
A
X
<.
X
*
X.
X
X
X
*
><
X
*
<
A
>
<
s.
*
(2)
\
X
•x
X
X
*
X
X
*
X
X
<.
X
X
<
<
X
*
y
X
X
*
<
X
>.
*
(3)
X
X
*>
<
X
X
*
>
X
X
X
X
X
(4)
X
*
X
y
X
V
X
>
x
<
X
*
y
(5)
X
>^
y
(6)
A
*
x
X
(7)
X
Y
*
X
y
.
D
t-*
IX
Cd
-------
AMMONIUM HYDROXIDE
(see Ammonia, aqua)
AMMONIUM MOLYBDATE
AMMONIUM NITRATE
AMMONIUM PERCHLORATE
AMMONIUM PERMANGANATE
AMMONIUM PERSULPHATE
AMMONIUM PICRATE, DRY
AMMONIUM PICRATE, WET
AMMONIUM SULFATE
AMMONIUM SULFIDE
AMMONIUM SULFITE
AMMONIUM THIOCYANATE
AMYL ACETATE (BANANA OIL)
AMYL ALCOHOL (FUSEL OIL)
AMYL ALCOHOL, PRIM. -ISO (Butyl carbinol)
AMYL ALCOHOL, s, -n
AMYL ALCOHOL, s. -iso.
AMYL ALCOHOL, ter.
AMYLAMINE
AMYLAMINE, sec. -mono
AMYLAMINE LAURATE
AMYLAMINE OLEATE
ANYLAMINE STEARATE
AMYL BROMIDE
AMYL MERCAPTAN
AMYL NITRITE (ISOAMYL NITRATE)
AMYL TRICHLOROSILANE PENTANE
(1)
A
*
y
<
X
X
•*
X.
X
X
<
X
X
*
1
1
1
*
<
(2)
X
<
y
X
A
<
*
X
X.
y
y
A
*
<
<
Y
X
X
X.
X
X
! *
A
X
X
V
(3)
*>
X
>
<
X
y
A
X
if
V
X
y
X
X
>
y
; y
! *
X
(4)
<
X
X
X
X.
X
>
X
r
1
•
(5)
*
'
(6)
X
X
1
j
(7)
*
X
y
i
i
t
1
j
i
X
f
>
*ti
S
^
D
X
en
ANILINE, OIL (AMINOBENZENE)
-------
ANILINE HYDROCHLORIDE
ANISOYL CHLORIDE
ANTHRACENE
ANTIMONY PENTACHLORIDE
ANTIMONY PENTAFLUORIDE
ANTIMONY PENTASULFIDE
ANTIMONY POTASSIUM TARTRATE
ANTIMONY, POWDERED
ANTIMONY SULFATE
ANTIMONY SULFIDE
ANTIMONY TRICHLORIDE
ANTIMONY TRIETHYL (TRIETHYLSTIBINE)
ANTIMONY TRIFLUORIDE
ANTIMONY TRIMETHYL (TRIMETHYLSTIBINE)
ANTIMONY TRIOXIDE
ARGON
ARSENIC CHLORIDE
ARSENIC DIETHYL
ARSENIC DIMETHYL
ARSENIC TRICHLORIDE
BARIUM ACETATE
BARIUM CARBIDE
BARIUM CARBONATE
BARIUM CHLORIDE
BARIUM CYANIDE
BARIUM FLUORIDE
BARIUM NITRATE
BARIUM PERCHLORATE
t
(1)
X
*
<
X
<
y
w
*
X.
*
*
*
A
X
X
*
H
X
X
t
^
(2)
X
*
x.
*
<
x
<
<
X
V
/
X-
X
X
<
X
>
<
/s
*
X
1
A
(3)
V
V
/
X
N<:
X
X
V
X
\/
x
X
X
>
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X
X
*
X.
*.
* '
(4)
*
y
X.
^
^<
X
(5)
(6)
(7)
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X
X
*
y
>
X
y
>
*
>
X
X
X
V
X
*
X
X
X
X
X
*
V
•
^
1
r
>
^
t
ts
D
><
tx
i
CT
-------
BARIUM PERMANGANATE
BARIUM PEROXIDE
BARIUM SULFIDE
BENZALDEHYDE
BENZENE IBENZOL)
BENZENE SULFONIC ACID
BENZINE PHOSPHOROUS DICHLORIDE
BENZOIC ACID
BENZONITRILE
BENZOYL CHLORIDE
BENZYL ALCOHOL (PHENYL CARBINOL)
BENZYLAMINE
BENZYL BROMIDE (BROMOTOLUENE)
BENZYL CHLORIDE
BENZYL CHLOROFORMATE
BERYLLIUM, POWDER
BLEACHING POWDER (see calcium hypochlorite)
BORIC ACID
BORON HYDRIDE
BORON TRICHLORIDE, IN CYL.
BORON TRIETHYL
BORON -TRIFLUORIDE
BORON TRIMETHYL
BROMACETONE
BROMINE
BROMINE PENTAFLUORIDE
(1)
>C
<
*
X
*
X.
<
<
H
*
/
X
*
*
X.
X
BROMINE TRIFLUORIDE
(2)
X
!k
X
*
<
<
*
X
X.
X
*
*
X
X
*
*
X
•x
>
*>
<
/
<
*
1
BROMOBENZYL CYANIDE \ X. X
(3)
X.
X
<
X
v
X
<
X
X
><
X
X
*
X
•*
>>
><
A.
>
X.
<
<
X
(4)
X
*
y
X
X
X
y
Y
X
>
X
X
y
X
X
<
y
i
(5)
X
X
X
<
X
X
(6)
X
i
(7)
X
X
X
X
X
*
^
y
X
X
X
>
K
J
i
:
i
i
i
i
f
TJ
Tl
W
z
d
i-^
td
-a
-------
BROMOETHANK (see ethyl bromide)
BROMOMETHANE (see methyl bromide)
BUTADIENE (ERYTHRENE), IN CYL.
IN DRUMS
BUTANE-n (BUTYL HYDRIDE)
BUTANE-iso (2 METHYLPROPANE)
BUTANOL (see butyl alcohol)
BUTENE-1 (ETHYL ETHYLENE)
BUTYL ACETATE-n (BUTYL ETHANOATE)
BUTYL ACETATE-iso
BUTYL ACETATE-sec. (2-BUTANOL ACETATE)
BUTYL ACRYLATE
BUTYL ALCOHOL-n
BUTYL ALCOHOL-iso
BUTYL ALCOHOL-sec
BUTYL ALCOHOL-tert
BUTYL ALDEHYDE-n (BUTYRALDEHYDE)
BUTYLAMINE-n
BUTYLAMINE-sec, mono
BUTYLAMINE-iso
BUTYLAMINE OLEATE-mono
BUTYLENE GLYCOL
BUTYL HYDROPEROXIDE-tert
BUTYL LITHIUM
BUTYL MERCAPTAN
BUt-YL PROPIONATE (BUTYL PROPANOATE)
BUTVRALDEHYDE (BUTYL ALDEHYDE-n)
BUTYRIC ACID-n
(1)
<
*
A
<
*
*
X
X
*
X1
*
(2)
X
*
. X
X.
X
•x
X
*
<
X
X
*
X
X
x
x
v x
A
A
X
x ;
(3)
X
X
X
A
x
X
X
X
X
X
X
*
*
X
X
x
>
x
X
A
(4)
X
^
<
X
I
(5)
*
X
<
*
x
X
X
!
* i i * *
X, ' v
(6)
*
X
X
X
X
A
X
X
A
V
xxx | x
* < x •. v •
(7)
*
X
*
X
X
X
X
AT
X
<
TJ
TJ
n
25
D
i
CO
-------
CADMIUM. POWDERED
CADMIUM BROMATE
CADMIUM CHLORATE
CADMIUM CHLORIDE
CADMIUM NITRATE
CADMIUM OXIDE
CADMIUM PICRATE
CADMIUM SULFATE
CALCIUM
CALCIUM ARSENATE
CALCIUM CARBIDF
CALCIUM CHLORIDE
CALCIUM CYANIDE
CALCIUM FLUORIDE
CALCIUM FLUOROSILICATE
CALCIUM HYDRIDE (HYDROLITH)
CALCIUM HYDROXIDE
CALCIUM HYPOCHLORITE
• CALCIUM HYPOPHOSPHITE
CALCIUM NITRATE
CALCIUM PHOSPHATE
CALCIUM PHOSPHIDE (PHOTOPHOR)
CALCIUM SULFATE
CAMPHOR
CARBON BISULFIDE (OR DISULFIDE)
CARBON DIOXIDE
CARBON MONOXIDE
(1)
x:
<
X
^
*
*
A
•s
<
Nt
<
X.
*
*
X
1
X
*
A
X.
(2)
A
X
<
<
A^
X
X
<
X
X
X
<
X
*
X
X
\
X
x,
(3)
\
*
X.
y
y/
X
X,
X
X
<
y
y
^
/
>
<
X,
X
X
(4)
y
X
*
A
<
x
X
x.
X
Xs
X
X
(5)
X
<
X
X.
X
: A
(6)
X
^
(7)
X
<
y
>
r
X
X
K
X
y
X
X
X
X
/>
•
. — _,
r
1
•1
>
"0
£
2
D
*— <
K^
W
CO
CARBON TETRACHLORIDE
-------
CAUSTIC POTASH (see POTASSIUM HYDROXIDE)
CAUSTIC SODA (see sodium hydroxide)
CETYL ALCOHOL (HEXADECANOL) INSOL
CHARCOAL. ACTIVATED
CHENOPODIUM OIL
CHLORAMINE-t
CHLORINE
CHLORINE TRIFLUORIDE
CHLOROBENZENE (see chlorobenzol)
CHLOROBUTADIENE
CHLOROFORM (TRICHLOROMETHANE)
CHLOROHYDRIN
CHLOROISOCYANURIC ACID
CHLOROMETHANE (see methyl chloride)
CHLOROPHENOL ORTHO, LIQ.
3-CHLOROPROPFNE (see allyl chloride)
CHLOROSULFONIC ACID
CHROMIC ACID, LIQUID
SOLID
CHROMIC ANHYDRIDE
CHROMIUM PICRATE
CHROMIUM TRIOXIDE
CHROMYL CHLORIDE
CITRIC ACID
COBALT CHLORIDE
f— —
COBALT NITRATE
COBALT SULFATE
COBALTOUS NITRATE
(1)
\
X
/•
X
A,
A
A
*
A
/
X.
<
<
X
K
*
^
*
(2)
A
><
*
X
t
X
A
X
*
A
A
A
A
X
A
X
A
X.
X
A
X,
A,
A
(3)
*
A
X
A
X,
X
X
X
A
y
A
X
X
X
A
X
A
(4)
X
X
X
*v
X.
A
X
y
<
X
X,
*
(5)
^
X.
X
X
X
X.
(6)
A
X
X
A
X
X
X
(7)
X
X
X
X
y
<
X
*
>r
>V
A
X
X
>
y
... - >
^
2
w
•z
M
M
W
o
-------
COPPER ACETOARSENITE
COPPER ACETYLENE
COPPER ACETYLIDE
COPPER CHLORATE
COPPER CHLORIDE
COPPER CYANIDE
COPPER NITRATE
COPPER PICRATE
COPPER PROPARGYLATE
COPPER SULFATE
COPPER TETRAZOL
CRESOL (CRESYLIC ACID)
CRESOTIC ACID
CROTONALDEHYDE
CUMENF (ISOPROPYLBENZOL)
CUMENE HYDROPFROXIDE
CUPRIC ACETATECUPRIC CHROME GLUCONATE
CUPRIC OXIDE
CUPRIC SULFATE
CYANOGEN BROMIDE
CYANOGEN CHLORIDE
CYANAMIDE
CYCLOHEXANE (HEXAHYDROBENZENE)
CYCLOHEXANE CARBOXYLIC ACID
CYCLOHEXANOL (HEX A LIN)
CYCLOHEXANONE
CYCLOHEXYLAMINE
DECARBORANE '
(1)
/
X
*
X
X
A"
X
X
A
<
X.
X.
<
X
X
X
X
X
*
X
X
1
>v
(2)
X
>
X
X.
X
X
X
A
X
X
X
<
X
<
X
y.
x !
(3)
*
X
X.
A
X
<
*
X
X
X
A
y
X
*
A
X
<
*
X
(4)
X
X
x.
X
X
X
X
(5)
X.
X
x.
X
X
X
y
(6)
A
A
X
^
X
x:
(7)
X
X
X
X
X
x.
*
*
*
X
y
X
X
-K
>f
Y
X
y
X
•<
'
~1
>
hrt
3
Z
o
>
-------
DEC ALDEHYDE
DECENE
DECYL ALCOHOL
DENATURED ALCOHOL (see methyl alcohol)
DETERGENTS
DIALLYL PHTHALATE
DIAMINOFTHANE
DIAMYLAMINE
DIBORANE
DIBUTYL PEROXIDE
DIBUTYL PHTHALATE-n
DIBUTYL THIOUREA
DICHLORETHYLENE (ETHYLENE DICHLORIDE)
DICHLOROBENZENF-o
DICHLOROBENZFNE-p
2. 3-DICHLOROBUTANE
DICHLRORDIFLUOROMETHANE (FREON 12)
DICHLOROETHYLENE-1,2 (acetylene dichlonde)
DICHLOROETHYLENE-1, 1 (vinylidene chloride)
DICHLRORETHYL ETHER
DICHLRORISOPROPYL FTHER
DICHLOROMETHANE (see(methylene chloride)
DICHLOROPHENOL
2-DICHLOROPROPANE
1, 3-DICHLOROPROPENE
2-DICHLOROPRO
DICHLOROTETRAFLUORETHANE (F-114)
DICYCLOPENTADIENE
(1)
M.
<
j(
<
<
Jk
A
X
X
*v
*
X
(2)
X
*
*
*
<
*
X.
X
^
*
X.
X,
A
>(
A
X
^
V.
X
X
X
*
(3)
y
X
A
X
A.
*
X.
*
A
X
X
X
<
><
X
<
X.
X
>(
(^)
X
X
*
X
X
X
x
X
(5)
X
X
X
*x
X
X
>(
<
K
>
X
*
X
(6)
>-
A
X
A
X
X
V
(7)
X
>-
X
X
V
X
>
X
t
.
1
J
t>
TJ
S
2
d
1— 1
CO
1—
to
-------
DIFMTHVL HYDRAZINF
DIETHANOLAMINE
DIETHVL ALUMINUM CHLORIDE
DIETHYLAMINE
DIETHYL BENZENE
DIETHYLDICHLRORSILANE
DIETHYLENE GLYCOL
DIETHYLENE GLYCOL MONOETHYL ETHER
DIETHYLFNE TRIAMINE
DIETHYL PHTHLATE
DIISOBUTYLENE
DIISOBUTYL KETONE
DIISOPROPANOLAMINE
DIISOPROPYLAMINE
DIISOPROPYL PEROXI DICARBONATE
DIMETHYLAMINE, IN CYL.
25% SOLN.
DIMETHYL DIOXANE
DIMETHYL ETHER (methyl ether) DRUM
DIMETHYL FORMAMIDE (DMF)
DIMETHYL SULFATE (METHYL SULFATE)
DIMFTHYL SULIDE (METHYI SULFIDE)
DIMETHYL SUFORIDE
DINITROANILINE-2. 4
DINITROBENZOL (DINITROBENZENE)
DINITRO CRESOLS
DINITROPHENOL
DINITRGTOLUENE (DINITROTOLUOL)
(1)
•j
<
X
*
X
\
<
x
X
A
X
*
! *
•*
(2)
X.
<
A
>•
*
X
*.
*
*
^
X
X
y.
X
\
X
y
x
*
*
*
*
X
V
<
(3)
*
A
<
X
X
*
X
X
X
X
X
X,
X
y
x.
•<
>
X,
X
X
y
X
(4)
y
*
X
X
y
X
X
X
X.
X
X
(5)
X
X
*
y
X
V
x '
X
/
X
X.
X
(6)
X.
>
X
X
X
X
X
X
X
y
i
(7)
<
X
X
X
X
*
y
K
y
X
X
y
X
V
*
1
: X
/
>
^
^
K
2!
i— i
X
td
CO
1
-------
nroxAVK
DIPFNTENT (CINENE)
DIPHENYLAMINE (phenylanilme)
DIPROPYLENE GLYCOL
DIVINYLBENZENE (Vinylstyrene)
DODECANOL
DODECENE
DODECYL BENZENE, CRUDE
DODECYL MERCAPTAN (see Lauryl mercaptan)
DYES
EPICHLOROHYDRIN
ETHANOLAMINE
ETHERS
ETHOXY TRIGLYCOL
ETHYL ACETATE (ACETIC ETHER)
ETHYL ACRYLATE-MONOMER
ETHYL ALCOHOL (ETHANOL)
ETHYLAMINE (MONOETHYLAMINE)
ETHYL BENZENE (PHENYL ETHANE)
ETHYL CHLORIDE (chloroethane), in cyl.
ETHYLENE (ETHENE)
ETHYLENE CYANOHYDRIN
ETHYLENE DICHLORIDE (DICHLOR ETHYLENE)
ETHYLENE GLYCOL (GLYCOL)
ETHYLENE GLYCOL MONOBUTYL ETHER
ETHYLFNE GLYCOL MONOETHYL ETHER
ETHYLENE GLYCOL MONOETHYL ETHER ACETAT1
ETHYLENE OXIDE, IN CYL.
IN DRUMS
(1)
X,
*.
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(7)
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A
V
X
X
X
X
X
X
V
*
X
:>
^
t
2
HH
X
w
1
*.
-------
ETHYLENIMINE
ETHYLHEXANOL (OCTYL ALCOHOL)
2-ETHYLHEXYL ACRYLATE
ETHYL METHYL KETONE
ETHYL PHTHALATE
2-ETHYL-3 PROPYLACROLEIN
FATTY ACIDS
FERRIC CHLORIDE
FERRIC OXIDE
FERRIC POTASSIUM SULFATE
FERRIC SULFATE
FERROSILICON
FERROUS CHLORIDE
FERROUS OXIDE
FERROUS SULFATE
FERROUS SULFIDE
FERROUS SULFITE
FLUORINE
FLUOSULFONIC ACID
FORMALDEHYDE, 37% solution
FORMIC ACID
FUMARIC ACID
FURFURAL (Furfuraldehyde)
FURFURYL ALCOHOL
GALLIC ACID
GASOLINE
GLYCERINE (GLYCEROL)
GLYCOL DIACETATE (DIACETIN)
(1)
<
X
*
*
X
X
X
X
X
X
X
X
X
*
X
X
*
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*
(2)
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(4)
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,
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(5)
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(6)
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(7)
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s
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X
i
en
-------
GLYOXAL
GUAIACOL
HAFNIUM
HELIUM
n-HEPTANE (Heptyl hydride)
HEPTANOL
1-HEPTENE
HEXAETHYL TETRA PHOSPHATE
HEXAFLUOROPHOSPHORIC ACID
HEXAFLUOROPROPYLENE
HEXAMETHYLENE DIAMINE
HEXANE (Hexyl hydride)
iso-HEXANE
HEXANOL (Hexyl alcohol- n)
HEXYLENE GLYCOL
HEXYL TRICHLOROSILANE
HYDRAZINE (ANHYDROUS DIAMINE)
HYDROCHLORIC ACID (MURIATIC ACID)
HYDROCYANIC ACID
HYDROFLUORIC ACID
HYDROFLUOSILICIC ACID
HYDROGEN
HYDROGEN BROMIDE, ANHYDROUS
HYDROGEN CHLORIDE, ANHYDROUS
HYDROGEN CYANIDE (see hydrocyanic acid)
HYDROGEN PEROXIDE - OVER 52%
HYDROGEN SULFIDE
HYDROQUINONE
(1)
y~
<
<
X,
X
/-
A
X
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(6)
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x,
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(7)
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y
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x
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n
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Cd
i
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en
-------
HYDROXYLAMINE (OXAMMONIUM)
HYPOCHLORITE
HYPOIODITE
IODACETIC ACID
IODINE, TINCTURE OF
IODINE MONOCHLORIDE
ISOBUTENE (2-Methyl propene)
ISOBUTYL ACETATE
ISOBUTYRALDEHYDE (Isobutyl aldehyde)
ISODEC A LDEHY DE
ISODECANOL
ISOOCTANE
ISOOCTENE
ISOOCTYL ALDEHYDE
ISOPENTANE
ISOPHORONE
ISOPRENE
ISOPROPYL ACETATE
ISOPROPYL ALCOHOL (Isopropanol)
ISOPROPYL AMINE
ISOPROPYL ETHER
ISOPROPYL FORMATE
ISOPROPYL MERCAPTAN
LACTIC ACID
LACTONITRILE
LAURYL CHLORIDE (dodecyl chloride)
LEAD ACETATE
i
(1)
* J
A
*
>
*
X
<
X
X
X
(2)
*
X
\
y
>
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A
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x
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(3)
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*
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y.
y
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x
*
x.
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(4)
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(5)
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(6)
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m
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X
>
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y
y
y
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hn
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n
i— i
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ro
i
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-------
LEAD ARSENATE
LEAD ARSFNITE
LEAD CHLORIDE
LEAD CHLORITE
LEAD CYANIDE
LEAD NITRATE
LEAD NITRITE
LEAD PEROXIDE (LEAD OXIDE)
LEAD SULFATE
LEAD SULFOCYANATE
LEAD TETRAMETHYL
LITHIUM CARBONATE
LITHIUM CHLORIDE
LITHIUM FERRO SILLICON
LITHIUM FLUORIDE
LITHIUM HYDROXIDE
LITHIUM HYPOCHLORITE
LITHIUM SULFATE
MAGNESIUM ARSENATE
MAGNESIUM CHLORIDE
MAGNESIUM, DAMP POWDER
Powder, ribbon or chips
MAGNESIUM FLUORIDE
MAGNESIUM NITRATE
MAGNESIUM PERCHLORATE
MAGNESIUM PEROXIDE
MAGNESIUM SILICO- FLUORIDE
MAGNESIUM SULFATE
MAL"C ACID
(1)
*
<
<
*
X
*
X
*
%
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*
^
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(2)
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(5)
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-------
MALEIC ANHYDRIDE
MANGANESE CHLORIDE
MANGANESE NITRATE
MANGANESE SULFATE
MERCAPTANS (DODECYL)
MERCAPTOETHANOL
MERCURIC AMMONIUM CHLORIDE
MERCURIC BENZOATE
MERCURIC BROMIDE
MERCURIC CHLORIDE
MERCURIC CYANIDE
MERCURIC IODINE
MERCURIC NITRATE
MERCURIC OLEATE
y
MERCURIC OXIDE
MERCURIC OXYCYANIDE
MERCURIC POTASSIUM CYANIDE
MERCURIC SALICYLATE
MERCURIC SULFATE AND SUBSULFATE
MERCURIC SULFOCYANATE
MERCUROUS BROMIDE
MERCUROUS CHLORIDE
MERCUROUS GLUCONATE
MERCUROUS IODIDE
MERCUROUS NITRATE
MERCUROUS SULFATE
MERCURY
MERCURY ACETATEMESITYLENE
(1)
X,
*
*•
*
<
*.
*
Y*
X.
(2)
Xs
x<
/.
*
X
X
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X
\
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-------
MESITYL OXIDE
METHANE (MENTHYL HYDRIDE)
METHANOL (see methyl alcohol)
METHYL ACETATE
METHYL ACETYLENE
METHYL ACRYLATE (ACRYLIC ESTERS)
METHYL ALCOHOL (METHANOL)
METHYLAMINE, 30% solution gas
METHYL AMYL ACETATE
METHYL AMYL ALCOHOL
METHYL BROMIDE (BROMOM ETHANE)
METHYL BUTYRALDEHYDE
METHYL CHLORIDE (CHLOROMETHANE)
METHYL CHLOROFORMATE
METHYLENE CHLORIDE (CARRENE)
METHYL DICHLOROSILENE
METHYL ETHER (DIMETHYL ETHER)
METHYL ETHYL ETHER (see ethyl methyl ether)
2-METHYL, 5-ETHYL PYRIDINE
METHYL FORMATE
METHYL HYDRAZINE
METHYL ISOBUTYL CARBINOL
METHYL ISOBUTYL KETONE (HEXONE)
METHYL MERCAPTAN (METHANETHIOL)
METHYL METHACRYLATE MONOMER
METHYLNAPHTHOQUINONF
METHYL SALICYLATE
MINERAL SPIRITS
(1)
A
X,
*
<
*
X.
*
y-
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*
><
X
X,
X
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(2)
X
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x.
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y
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y
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X
X
X
(5)
A
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X,
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(6)
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A
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Y
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A
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(7)
y
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X
ts
to
o
-------
MONOBROMOTRIAUOROMETHANE
MONOBROMO TRICHLOROETHER
MONOCHLOROACETIC ACID
MONOCHLOROACETONE (SEE CHLOROACETONE)
MONOCHLORODIFLUOROMETHANE (FREON 22)
MONOCHLOROFLUOROETHANE
MONOETHANOLAMINE (see ethanolamine)
MONOETHYLAMINE (see ethylamine)
MONOFLUOROPHOSPHORIC ACID, ANHYD.
MONOISOPROPANOLAMINE
MONOMETHYL HYDRAZINE
MORPHOLINE
MOTOR FUEL ANTI-KNOCK COMPOUND
NAPHTHA
NAPHTHALENE (NAPHTHALINE)
NAPHTHALIC ACID
NAPHTHOL-beta
NAPHTHOQUINONE
NAPHTHYLAMINE-beta
NICKEL AMMONIUM SULFATE
NICKEL CARBONYL
NICKEL CHLORIDE
. NICKEL CYANIDE
NICKEL NITRATE
NICKEL SULFATE
NICOTINE HYDROCHLORIDE
NICOTINE SALICYLATE TARTATE AND SULFATE
NITRATING ACID
(1)
X
<
Xs
*s
X,
*
X
X
*
*
X
A
<
*
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X
X
x
(2)
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*
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x
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i
to
*-
-------
NITRIC ACID
NITROANILINE (see mtraniline-meta, para)
NITROBENZENE (NITROBENZOL)
NITROCHLOROBENZENE, meta or para
NITROETHANE
NITROGEN
NITROHYDROCHLORIC ACID (see aqua regia)
NITROMETHANE
NITROPHENOL
1-NITROPROPANE
NITROSYL CHLORIDE (see Nitrogen oxychloride)
p-NITROTOLUOL (nitrotoluene)
NITROUS OXIDE
n-NONANE (Nonyl hydride)
NONTHENE
NONYL ALCOHOL
NONYLPHENOL
OCTODECYL TRICHLOROSILANE
OCTYL ALCOHOL-n (2-Ethylhexyl alcohol)
OCTYL TRICHLOROSILANE
OIL OF VITRIOL (see sulfuric acid)
OLEIC ACID (RED OIL)
OLEUM (Hi- strength sulfuric acid)
ORTHO-NITROANILINE
OXALIC ACID
OXYDIPROPIONITRILE
OXYGEN
OXYGEN DIFLUORIDE
1
(1)
*
*
X
X,
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x
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(2)
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x.
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x
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(4)
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(5)
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(7)
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y
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>
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D
X
Cd
ro
to
-------
PAR A FORMALDEHYDE
PARALDEHYDE (Paracetaldehyde)
' PENTABORANE, in drums
n-PENTANE (AMYL HYDRIDE)
PENTANOL
PENTENE (AMYLENE)
PERACETIC ACID
PERCHLORIC ACID - to 72% strength
PERCHLOROETHYLENE
PERCHLORO-METHYL-MERCAPTAN
PERCHLORYL FLUORIDE
PETROLEUM ETHER (See benzine)
PHENANTHRENE
PHENOL (see carbolic acid)
PHENYCARBYLAMINE CHLORIDE
PHENYLETHANOLAMINE
PHENYLTRICHLOROSILANE
PHOSGENE
PHOSPHINE (phosphoretted hydrogen)
PHOSPHORIC ACID
PHOSPHORIC ANHYDRIDE
PHOSPHORUS, RED
PHOSPHORUS, WHITE OR YELLOW
PHOSPHORUS OXYBROMIDE
PHOSPHORUS OXYCHLORIDE
PHOSPHORUS PENTACHLORIDE
PHOSPHORUS PENTASULFIDE
PHOSPHORUS SESQUISULFIDF
(1)
*.
*
*
*
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1 <
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y
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(4)
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x,
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y
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y
x.
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1
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-------
PHOSPHORUS TRIBROMIDE
PHOSPHORUS TRICHLORIDE
PHTHALIC ANHYDRIDE
PICRIC ACID (TRINITROPHENOL), liquid
POLYPROPYLENE GLYCOL METHYL ETHER
POLYVINYL ALCOHOL
POTASSIUM
POTASSIUM ACETATE
POTASSIUM AMMONIUM NITRATE
POTASSIUM ARSENITE, SOLID
POTASSIUM BIFLUORIDE
POTASSIUM BROMATE
POTASSIUM CARBONATE
POTASSIUM CHLORATE
POTASSIUM CHLORIDE
POTASSIUM CHROMATE
POTASSIUM CUPRIC
POTASSIUM CYANIDE, SOLID
POTASSIUM DICHLOROISOCYANURATE
POTASSIUM DICHROMATE
POTASSIUM FERRICYANIDE
POTASSIUM FERROCYANIDE
POTASSIUM FLUORIDE
POTASSIUM HYDROXIDE, SOLID
POTASSIUM IODIDE
POTASSIUM NITRATE, SOLID
POTASSIUM NITRITE, SOLID
(1)
X.
X,
X
X
X
*
X.
*
X
X.
*
X.
(2)
X
X
*
*
X
X
X
X
K
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A
X
X
X
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X
X.
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X
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X
X
*
X
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X
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X.
y
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. _ .
y
y
(4)
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POTASSIUM PERCHLORATE
-------
POTASSIUM PERMANGANATE
POTASSIUM PEROXIDE
POTASSIUM PERSULFATE
POTASSIUM PHOSPHATE
POTASSIUM SILICOFLUORIDE
POTASSIUM SULFATE
POTASSIUM SULFIDE
POTASSIUM THIOCYANATE
' PROPANE (see also L. P. Gas)
PROPANOLAMINE
PROPIOLACTONE-beta
PROPIONALDEHYDE •
J PROPIONIC ACID
' PROPIONIC ANHYDRIDE
PROPYL ACETATE-n
PROPYL ALCOHOL-n
' PROPYL AMINE, mono-n
PROPYLENE
PROPYLENE BUTYLENE POLYMER
PROPYLENE GLYCOL
PROPYLENE IMINE
PROPYLENE OXIDE
PROPYLENE TETRAMER
PROPYL MERCAPTAN
PROPYL NITRATE-n
PROPYL TRICHLOROSILANE
PYRIDAL MERCURIC ACETATE
PYRIDINE
(1)
>'
X.
<
A
*
*
*
*
A
>c
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x;
X,
Xv
X.
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(2)
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i
tn
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P\ ROCATECHOL
PYROGALLOL
PYRO SULFURYL CHLORIDE
PYROXYLIN, SOLID (see cellulose nitrate)
QUINOLINE
QUINONE
RESIN (ROSIN, COLOPHONY)
RESORCINAL (Dihydroxy benzene-m)
SALIC YLALDEHYDE
SALICYLIC ACID
SAPONINS
SELENIUM, POWDER
SILICON CHLORIDE
SILICON TETRAFLUORIDE
SILVER CHLORIDE
SILVER CYANIDE (see cyanide of silver)
SILVER NITRATE
SODIUM
SODIUM ACETATE
SODIUM ALUMINATE
SODIUM ALUMINUM HYDRIDE
SODIUM AMIDE (SODAMIDE)
SODIUM ARSENATE
SODIUM ARSENITE
SODIUM AZIDE
SODIUM BICARBONATE
SODIUM BIFLUORIbE
SODIUM BISULFATE
(1)
s
*
/
X.
X
A
X
X
X
*
x.
X.
X
*
*
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*
X
X
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A
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A
A
X
X
>
*
X.
X
x^
X,
<
^
y
>
vc
X
>
*
X
y
X
(3)
y
X
X
X
X
x^
X.
X
X.
X.
x:
y
X
X
(4)
y
X
V
y
X
*
y
<
y
X
X
(5)
X
X.
(ff)
(7)
X
y
X
X.
X
JX
*
\
i
1
^
w
D
h-«
M
Dd
to
en
-------
SODIUM BISULFITE
SODIUM BORATE
SODIUM BROMATE
SODIUM BUTYL MERCAPTIDE
SODIUM CARBONATE PEROXIDE
SODIUM CHLORATE
SODIUM CHLORIDE
SODIUM CHLORITE
SODIUM CHROMATE
SODIUM CYANIDE
SODIUM DICHLOROISOCYANURATE
SODIUM DICHROMATE (see sodium bichromate)
SODIUM FERROCYANIDE
SODIUM FLUORIDE
SODIUM FORMATE
SODIUM HYDRIDE, CRYSTALS
SODIUM HYDROSULFIDE
SODIUM HYDROSULFITE
SODIUM HYDROXIDE, SOLID
SODIUM HYPOCHLORITE HYDRATE
SODIUM IODIDE
SODIUM METHYLATE
SODIUM NITRATE, SOLID
' SODIUM NITRITE, SOLID
SODIUM OXALATE
SODIUM PERBORATE
SODIUM PERCHLORATE
SODIUM PERMANGANATE
(1)
X.
X
X
X
*
X
X
X
*
A
<
X.
X
X
X
X
X
A
A
(2)
y
X
X
*
*
X
X
/
X
*
X
X.
>
X.
y
X
X
X
X-
X.
>
X
X.
X
\
y
>>
(3)
X
X
X
X
X
X
X
X
X
X
X
X
X
X.
X
X
X
(4)
<
X
V
X
X
X
>
X
X
y
y
y
(5)
X
(O
(7)
>
• hrl
13
Z
I-*
X
a
to
-------
SODIUM PEROXIDE
SODIUM PHOSPHATES
SODIUM PICRAMATE, DRY
SODIUM-POTASSIUM ALLOY
SODIUM PYROPHOSPHATE PEROXIDE
SODIUM SILICATE
SODIUM STANNATE
SODIUM SULFATE
SODIUM SULFIDE
SODIUM SULFITE
SODIUM THIOCYANATE
SODIUM THIOSULFATE
SODIUM TRIPHOSPHATE
SORBITOL
STRONTIUM ARSENITE
STRONTIUM CHLORATE
STRONTIUM NITRATE
STRONTIUM PEROXIDE
STRYCHNINE
STYRENE (phenyl ethylene)
SUCCINIC ACID PEROXIDE, DRY
SULFOLANE
SULFUR
SULFUR CHLORIDE-mono
SULFUR DIOXIDE
SULFUR HEXAFLUORIDE
SULFURIC ACID
SULFUR TRIOXIDF
i
(1)
X
1
\
X
\
X
X
+
t
x
X.
*
^
<
^
(2)
,<
<
]<
X
X
X
<
X.
X
*
X
>
x
X
«
X
X
*
>(
<
X
X
- * -4
<
X
X
(3)
X
*
/
\
X
X
/
*
X
X
X
<
<
X.
i
*
(4)
<
*
^
X
K
X
X
V
X.
X
X
A
(5)
/*
*
y
X
X
L
(P)
X
X
X
X
I
(7)
X
A
X
Jt
X
>
1
X
X
,
>
TJ
S
i/j
•z
n
l— t
X
n
i
00
-------
SULFURYL CHLORIDE (sulfunc oxychlonde)
SULFURYL FLUORIDE
TANNIC ACID (TANNIN)
TARTARIC ACID (RACEMIC ACID)
TERTIARY BUTYL ISOPROPYL BENZENE
TETRADECANE
1-TETRADECANOL (MYRISTYL ALCOHOL)
TETRAETHYLENE GLYCOL
TETRAETHYLENE PENTAMINE
TETRAETHYL LEAD (all mixes)
TETRAETHYL PYROPHOSPHATE
TETRAFLUORETHYLENE
TETRAHYDROFURAN
TETRAHYDRONAPHTHALENE (tetralin)
TETR A METHYL LEAD
TETRAPROPYLENE
THALLIUM
THIOGLYCOLIC ACID
THIONYL CHLORIDE (sulfur oxychloride)
THIOPHENE
THIOPHENOL
THIOPHOSPHORYL CHLORIDE
THORIUM, POWDER
THORIUM NITRATE
TIN TETRACHLORIDE (stannic chloride)
TITANIUM SULFATE
TITANIUM TETRACHLORIDE
TOLUENE (TOLUOL)
(1)
<
<
<
<
*
<
X.
£
<
<
v.
<
X.
X
X.
X
X
X
(2)
X.
^
<
<
X
X
X
X
*
*
X
X
X
X
X
X
A
X
X
X
*
X
K
\
X
X
(3)
><
X
X
y
X
X
X
*
<
X
X
X
X
*
*
X
X
V
(4)
x.
X.
X
*
X.
*
X.
A
A.
*
X
A
X
X
(5)
X
\
>s
X
y
(6)
X
X
*
X
X
(7)
X
X
*
X
*•
X
V
A
^
-<
X
Jf
K
>
- 3
2!
rt
><
- B
to
CO
-------
TOLUENE DIISOCYANATE
o-TOLUIDINE (2,4-Methyl aniline)
TRIAMYLAMINE
TRIBUTYLAMINE
TRICHLORBENZENE
TRICHLOROETHANE
TRICHLOROETHYLENE
TRICHLOROFLUOROMETHANE (FREON 11)
TR ICHLOROFLUOROSILANE
TRICHLOROISOCYANURIC ACID
TRICHLOROMONOFLUOROMETHANE
(see trichlorofluoromethane)
TRICHLOROPHENOL
TRICHLOROSILANE (SILICON CHLOROFORM)
TRICRESYLPHOSPHATE
TRIDECANOL
TRIETHANOLAMINE
TRIETHYLAMINE
TRIETHYL BENZENE
TRIETHYLENE GLYCOL (dicaproate)
TRIETHYLENE TETRAMINE
TRIMETHYLAMINE
TRIMETHYLCHLOROSILANE
TRINITROBENZENE (TNB)
TRINITROBENZOIC ACID
TRINITRORESORCINOL (styphnic acid)
TRIPROPYLENE
TRITIUM (HYDROGEN 3)
(1)
<
<
X
X
K
><>
X
X
X
X
X,
X
X
X
X
*
(5)
y
X
X
•
X.
(6)
*
>
\
<
X
Xx
<
X
X
(7)
\
X
\
X
A
X
X
X
X
X
X
>
a>
i)
3
2!
i— i
X
ro
i
o
-------
TURBINE OIL (see lubricating oil)
TURPENTINE
UNDECANOL
1-UNDECENE
UNSYMETRICAL DIMETHYL HYDRAZINE
URANYL NITRATE
URFA (PLUS SALTS)
VALERALDEHYE
VANADIUM OXYTRICHLORIDE
VANADIUM PENTOXIDE
VANADIUM TETRACHLORIDE
VANADYL SULFATE
VARNISH
VINYL ACETATE
VINVYL BROMIDE
VINYL CHLORIDE
VINYL ETHER (DIVINYL ETHER)
VINYL FLUORIDE
VINYLIDENE CHLORIDE
VINYL METHYL ETHER, IN CYL.
VINYL TOLUENE
VINYLTRICHLOROSILANE
WAXES
XYLENE (XYLOL)
XYLENOLS
XYLYL BROMIDE
ZINC ACETATE
ZINC AMMONIUM
(1)
\
X
V
*
*
x:
<
X
Xv
*
*
*
X
(2)
*v
X.
X
X
X
<
*
y
X
X
X
*
*
y
*
X
*
X
y
X
X
y
x
X
(3)
X
X.
X
X
X
X.
*
X
X
y
y
x
(4)
X
*
X
*
y
X
A
X
(5)
X.
X
X
((.)
X
X
X
\
y
X
x
(7)
A
X
X
X
y
V
y
y
X"
X
X
•
^
M
n
2!
U
h- 1
X
m
CO
»^
-------
ZINC ARSENATE
ZINC ARSENITE
ZINC CHLORATE
ZINC CHLORIDE
ZINC CYANIDE
ZINC ETHYL
ZINC NITRATE
, ZINC OXIDE
ZINC PERMANGANATE
ZINC PEROXIDE
ZINC SULFATE
t ZIRCONIUM, POWDER
ZIRCONIUM PICRAMATE, DRY
(1)
X
*
X.
*
/
t
*v
^
x>
*
>c
(2)
X
X
*
A
A
A
X
*
X
*
X
*
(3)
X
A
A
X
X
X
X
*
X
X
x,
(4)
Xv
<
/
(5)
A
X
(6)
(7)
X
y
K
X
^
K
s
2:
0
03
i
CO
to
-------
APPENDIX C
HAZARDOUS MATERIAL RATINGS
-------
APPENDIX C-l
COMPOUNDS FOUND HAZARDOUS BY RATING SYSTEM
This appendix contains a selected list of materials whose toxic,
explosive, or flammable properties may create hazardous waste
conditions.
-------
niLi
Acetaldehyde
Acelic Acid
Acetic \nhxilruli
Acetone
Acetone Cyanhydnn
Acetonitnle (Methyl Cyanide)
Acctyl Chloride
Acetylene
Acndine
Acrolem
Acrylic Acid
Acrylonitnle
Aldnn
Allyl Alcohol
Allyl Chloride
Aluminum Fluoride
Aluminum Oxide (Alumina)
Aluminum Sutfate
Ammonia (Aqua- Ammonium Hydroxide)
Ammonium Chloride
Ammonium Chromate
Ammoniuin l>u hrom^lr
Ammonium Fluoride
Ammonium Nitrate
Ammonium Perchlorate
Ammonium Persulfate
Ammonium Pirraii (l)r\)
-o~»*
is:*-
2
2
2
2
3
2
3
1
2
3
3
2
3
2
3
3
2
3
2
1
3
3
3
1
2
1
3
!£S»
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
i
2
3
2
3
sr*
3
1
2
2
2
2
3
1
1
2
2
3
2
3
U
2
1
3
U
2
U
2
2
U
U
1
1
-.„.«»*.
!•_:>
2
2
3
2
3
2
3
1
2
3
3
3
3
2
3
3
1
3
3
1
3
2
3
1
2
1
3
£±T«
I
1
3
1
3
2
2
1
1
U
1
1
U
1
1
U
1
2
1
1
1
1
1
1
1
1 '
1
STt
3
3
2
1
3
2
U
2
3
3
3
3
3
3
1
U
U
2
3
2
2
2
2
2
U
3
U
UWDMTCML
I£3r
2
2
3
1
2
1
3
1
2
2
3
1
2
2
3
2
1
3
2
1
3
3
3
1
2
1
3
il^T.?
2
U
2
2
2
2
2
2
1
2
2
2
2
2
1
2
1
2
2
1
2
2
2
3
3
2
3
"-•/a
2
2
U
U
U
U
U
U
U
U
U
U
U
U
U
3
3
U
U
U
U
U
U
U
U
U
U
low
19
IS
19
13
20
IS
18
11
14
17
19
17
17
17
14
17
12
20
IS
11
16
17
18
11
13
12
17
*
1
1
1
1
1
2
1
1
2
1
1
2
1
2
2
1
1
2
1
2
1
1
2
3
1
2
•"•/I
19
18
22
16
23
18
24
14
17
23
22
20
23
20
20
23
IS
23
21
14
22
20
21
17
22
IS
23
•«•»
/ V
1 S
1 S
1 S
1 S
1 S
1 S
1 0
1 S
1 0
1 0
1 25
1 5
1 0
1 0
1 0
1 S
1 0
1 S
1 S
1 2!
1 2!
1 2S
1 2!
1 5
1 S
1 2!
1 21
,5
0
2S
2S
25
25
25
SO
25
25
25
SO
25
25
25
25
SO
25
SO
25
SO
SO
25
50
25
SO
SO
SO
STTc
1 SO
1 75
1 75
1 75
1 75
1 75
1 SO
1 75
1 25
1 25
1 75
1 75
1 25
1 25
1 25
2 0
1 25
2 0
1 75
1 75
1 75
1 SO
1 75
2 0
2 0
1 75
1 75
*-~//
28
26
33
23
35
26
27
19
17
21
33
30
21
21
17
34
15
40
26
19
28
25
31
22
26
21
30
"•"«
28
31
38
28
40
31
16
24
t\
29
38
35
29
25
2S
41
19
46
37
24
18
30
37
34
44
26
40
S
2!
D
o
I
CO
-------
TITLI
Ammonium I'irratr (Wrt)
Ammonium Sulfide
Amyl Acetate (Banana Oil)
Amyl Alcohol (Fusel Oil)
Aniline
/Vntt|racenes
Antimony
Antimony Pentachlonde
Antimony Pentafluonde
Antimony PenUsulfide
Antimony Potassium Tan rate
Antimony Sulfate
Antimony Sulfide
Antimony Tnethyl (Tnethylstibine)
Antimony Trichloride
Antimony Tnfluoride
Antimony Tnmethyl (Trimethylstibine)
Antimony Triomde
Arsenic
Arsenic Chloride
Arsenic Oiethvl
Arsenic Dimethyl
Arsenic Penttselenide
Arsenic Trichloride
Arsenic Trioxide
Asbestoa Particles
Barium Carbonate
*m IMSMCAL
turn
3
2
2
2
3
u
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
i«i i"
••»•
3
3
2
2
2
2
2
2
2
2
2
2
2
3
2
2
3
2
2
2
3
3
2
3
3
1
1
iCT"
u
3
2
3
1
3
2
2
2
1
1
1
1
U
U
u
u
1
3
3
3
3
3
3
3
U
1
IMTEH MFOEAl
Hd
3
3
2
3
3
3
3
3
3
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
2
inr
i
2
1
1
1
1
1
1
1
2
1
1
2
1
2
1
1
1
1
2
2
I
1
1
1
1
2
IHMII
U
3
3
2
2
U
U
U
U
1
3
U
U
U
3
2
U
3
3
3
3
3
3
3
3
U
1
LAHO DISPOSAL
rc^
3
2
1
2
3
U
2
2
2
1
2
2
2
2
3
2
2
2
2
2
2
2
2
2 '
2
I
1
i in i
HHCMH
2
3
2
2
2
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
2
2
2
2
1
1
111' 1 I
lim
U
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
u
3
3
3
3
3
3
3
U
U
T«u
KHMMI
fHra
«••»
15
21
IS
17
17
10
IS
15
IS
14
17
14
IS
14
18
IS
14
17
22
23
25
23
22
23
23
8
11
•<
UMMMM*
3
1
1
1
1
4
2
2
2
1
1
2
?
3
2
2
3
1
3
1
EINcn
"»•»
24
24
18
20
20
24
21
21
21
17
20
20
21
23
24
21
23
20
22
23
25
23
22
23
23
17
14
•iMMtaii
«••»
1 25
1 S
1 0
1 25
1 5
1 5
1 25
1.0
1.0
1.0
1.0
1.0
1.0
1 0
1.0
1 0
1.0
1.0
1 25
1.0
1 0
1.0
1.0
1.0
1.0
1 5
1 5
•m
25
25
25
25
25
25
25
25
25
5
25
25
5
25
S
25
25
25
S
25
25
25
25
25
25
25
25
IM
^wtiniim
0»»u.
••t
1 5
1 75
1 25
1 5
I 75
1 75
1 5
1 25
1 25
1 S
1 25
1 25
1 5
1 25
1 5
1 25
1 25
1 25
1 75
1 25
1 25
1 25
1 25
1 25
1 25
1 75
1 75
f<«
*>m ii
MM*
**••
22
37
19
25
30
18
22
19
19
17
21
17
22
17
27
19
17
21
38
29
31
29
27
29
29
14
19
MMM
••"»
36
42
22
30
35
42
31
2«
26
21
25
25
31
29
36
25
29
25
38
29
31
29
27
29
29
30
24
B
Z
D
n
-------
IIILI
Barium Chloride
Barium Cyanide
Barium Fluoride
Barium Nitrate
Barium Sulfide
Benzene
Benzene Hexachlonde
Benzene Sulfonic Acid
Benzole Acid
Benzyl Chloride
Beryllium Carbonate
Beryllium Chloride
Beryllium Hydroxide
Beryllium Oxide
Beryllium Powder
Beryllium Selenate
Boron Trichloride
Boron Trifluoride
Bromic Acid
Bromine
Bromine Pentafluonde
Butadiene
Butane
Butanol (Butyl Alcohol)
Butene - 1 (Ethvl Rlhylene)
Butylacetate (Butyl Ethanoate)
Butylacrylate
».HK»U
M0MM
2
3
3
2
2
2
2
3
I
3
3
3
3
3
3
3
2
3
3
3
3
2
2
1
2
1
1
iitr
i
2
2
2
3
2
2
2
1
2
2
2
2
2
2
2
2
1
2
2
2
2
2
2
2
2
2
lfta»
2
U
2
U
U
1
3
|
1
U
3
3
3
3
2
3
2
2
U
U
U
3
1
1
U
1
1
«n.OT»L
Iffcm
3
3
3
2
2
2
3
3
1
3
1
2
2
1
3
3
2
2
3
2
3
2
1
2
1
1
2
££T
2
2
1
1
2
1
1
1
1
2
1
1
1
1
1
1
2
2
1
2
2
U
1
1
1
1
1
1ST"
3
U
1
2
U
3
3
2
2
3
U
U
U
U
3
U
U
U
U
3
U
3
1
3
U
3
2
UMOMFOML
tNH*
1
2
3
1
1
2
2
3
1
3
3
3
3
3
1
3
2
3
3
3
3
1
1
1
I
1
1
innr
i
2
2
2
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17
17
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22
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27
29
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27
26
25
24
27
25
25
29
40
30
35
28
32
31
30
22
S
o
I
I
01
-------
n-Butylamme
Butyl Mercaptan
Butyl Phenol
Butyraldehyde (Butyl Aldehyde - n)
Cacodylic Acid ( Dunethylarsmic Acid)
Cadmium
Cadmium Chloride
Cadmium Cyanide
Cadmium Fluoride
Cadmium Nitrate
Cadmium Oxide
Cadmium Phosphate
Cadmium Potassium Cyanide
Cadmium Sulfate
Calcium Araenate
Calcium Arsenide
Calcium Carbide
Calcium Cyanide
Calcium Fluoride
Calcium Hydride
Calcium Hypochlorite
Calcium Oxide
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Chloride I Phosgene)
Chloral Hydrate
IHKH
2
2
I
I
3
3
3
3
3
3
3
3
3
3
3
3
1
3
1
2
3
3
3
3
3
2
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2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
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2
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2
2
2
2
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3
3
2
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U
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3
3
3
3
3
3
3
3
3
3
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3
1
2
2
3
1
3
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1
1
1
1
1
1
1
2
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1
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9
13
16
15
23
19
16
20
14
15
15
20
19
14
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16
14
10
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13
18
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16
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18
18
18
16
19
21
23
19
22
23
20
21
24
20
22
23
18
22
20
19
21
19
21
18
19
24
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19
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16
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26
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24
20
25
21
19
19
25
24
17
16
28
24
12
26
23
31
26
28
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11
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Mm*
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22
22
22
20
24
37
29
24
27
29
30
26
30
25
27
29
31
38
35
24
37
33
37
31
33
30
19
S
2!
D
»—i
X
n
-------
Chlorine
Chlorine Tnfluonde
ChloroBCCtophenone
Chlorobenzene (Chlorotaenzol)
Chlorodene
Chloroform (Tnehloromethane)
Chloroiulfomc Acid
Chromic Acid
Chromic Fluoride
Chromic Sulfate
Chromium Cyanide
Coal (Particle)
Colbalt Chloride
Cobaltoua Nitrate
Copper Acetoanenite
Copper Cyanide (Cuprous Cyanide)
Capper Nitrate
Copper Sulfale
Creosote
Creiol (Cresylic Acid)
Crotonaldehyde
Cumene (Isopropylbenzol)
Cyanidea
Cyanoacetic Acid
Cycloheane
-------
IIILI
Cyclohexylamine
Demeton
Decyl Alcohol
Oibutyl Phthmlate - n
o - Dichlorobenzene
p - Dichlorobenzene
2. 4 - Dichlorophenoxyacetic Acid<2. 4-L
ODD (Dichloro Diphenyl Dichloro Etheni
DOT (Dichloro DiPhonyl-Trichloroelhon
Diborane (Boron Hydride)
Dichloroethyl Ether
Dichloromethane (Methylene Chloride)
1.2- Dichloropropane
1. 3 - Dichloropropene
Dleldrin
Dieihanolamlne
DlethyUmlne
Diethyl Ether (Ethyl Ether)
Dlethylene Dioxide (1. 4 - Dionne)
Diethylene TrUmine
Dlethylotilbestrol
Dilaobutylene
Dilsobutyl Ketone
DinuUiylunine
Dimethyl Sulfite (Methyl Sulhte)
2.4- Dimtroaniline
Dlnitro - o - Cresoli
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20
21
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14
18
18
18
16
19
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21
20
23
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26
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27
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20
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29
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31
TJ
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58
O
n
00
-------
nru
o - Dinitrobcngol (1.2 - Dimtrobenzenel
2. 4 - Dinitrophenol
2.4- Dinilrotoluene ( Dmitrotoluol)
DiphenyUmme (PhenyUnilme)
Dlpropylene Clycol
Dodecyl Benzene (Crude)
Endrin
Epichloroliydrui
Ethane
Ethanol (Ethyl Alcohol)
Ethanolamlne (Monoethanolamine)
Ethers
Ethyl Aceute (Acetic Ether)
Ethyl AcryUte
Ethylamme (Monoethylamuie)
Ethyl Benzene (Phenyl Ethane)
Ethyl Chloride (Chloroethane)
Ethylene (Ethene)
Ethylene Bromide < Ethylene Dibromide)
Ethylene Cyanohydrin
Ethylene Diamlne
Ethylene Dibromide (Oibromethane)
Ethylene Dichlorlde (1.2- Dichloroetharu
Ethylene Clycol (Clycol)
Ethylene Clycol Monoethyl Ether
Ethylene Qycol Monoethyl Ether Aceut
Ethylene Oxide
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22
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ft
z
o
r-*
X
n
CO
-------
Ethylenimme
2-Ethylhexanol (Octyl Alcohol)
Ethyl MercapUn
Ethyl Methyl Ketone (Uutanone)
Ethyl Phthalate (Diethyl o-Phthalate
2 -Ethyl - 3 Propyl Acrolem
Ferrous Sulfate
Fluorides (e. g . Hydrogen Fluoride, etc
Fluorine (Hydrofluoric Acid)
Formaldehyde - 37% Solution
Formic Acid
Furfural (Furfuraldehyde)
Furfural Alcohol
Cuthion
Heptalchor
Heptane (Heptyl Hydride)
Hexachlorophene (Methylene)
Hexaethyltetraphosphate
Hexamethylene Diamine
Hexane (Hezyl Hydride)
Hydrazine (Anhydrous Diamine)
Hydrobromic Acid
Hydrochloric Acid (Muriatic Acid)
Hydrocyanic Acid (Hydrogen Cyanide)
Hydrofluoric Acid (Hydrogen Fluoride)
Hydrogen Chloride Anhydrous
Hydrogen Peroxide (over 52%)
M
3
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1
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Sodium Iterate
Sodium Caeodylate
Sodium Carbonate
Sodium Carbonate Peroxide
Sodium Chlorate
Sodium Chromate
Sodium Cyanide
Sodium Fluoride
Sodium Formate
Sodium Hydride (Crystals)
Sodium Hydrosulfile
Sodium Hydroxide (Caustic Soda)
Sodium Iodide
Sodium Nitrate (Solid)
Sodium Nitrite (Solid)
Sodium Oxalate
Sodium Oxide
Sodium Perrhlorate
Sodium Peroxide
Sodium Phosphate
Sodium-Potassium Alloy
Sodium Sulfide
Sodium SulTlte
Sodium Thiocyanate (Sodium Sulflcyanide
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Stannous Chloride
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1 rtrarthvl 1 i-ail
Tetrahydrofuran
Tetramethvl Lead
Tetramtromethane
Thallium
Thallium Sulfate
Titanium Tetrachloride
Toluene (Tolyol)
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Trichlorobenzene
Trichloroethane ( • or 0 )
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m - X>lene (Xylox)
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Zinc Ar.ier.ite
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Zinc Chlci .de
Zinc Cjanide
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Zinc Permanganate
Zinc Peroxide
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D
n
00
-------
APPENDIX C-2
COMPOUNDS FOUND MARGINALLY HAZARDOUS BY
RATING SYSTEM
The following compounds were initially considered for inclusion
to the list of Appendix C-l. The ratings received indicated that they
were of lesser probable hazard potential than other compounds. They
have been included in this appendix to illustrate that various cutoff
points may be established to differentiate between potentially hazardous
compounds.
-------
nni
Adipic Acid
Ammoethvlethanolamine
Ilismuth
Hone Acid
Calcium Chloride
Calcium Phosphate
Camphor
Citric Acid
Copper (Dust)
Dichlorodinuoromethane (Freon 12)
Dichlorotetranuoroethane (Freon 114)
Dicyclopentadiene
Diethylene Glvcol
Disopropanolamine
Ethylphenol
Glycerine (dlycerol)
1 - Heptene ( • - Heptylene)
Isobutylene
Isopentane
Manganese Sulfate (Manganous Sulfate)
Nonylphenol
Oleic Acid
Phthallc Anhydride
Polypropylene Glycol Methyl Ether
Polyvlnylchlorlde
Potassium Phosphate
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25
25
25
.25
S
25
.25
25
5
S
S
25
i«*
•»« •
1 75.
1 25
1 25
2 0
1 75
2.0
I.2S
1 75
1 75
1.75
1 S
l.S
1 75
1 25
1 25
1 75
1.75
1 75
1 75
1.7S
1. 5
1 25
1 75
1 25
2 0
2 0
1 75
fatf
•—«
10
9
10
14
14
10
14
16
16
16
12
9
14
4
5
14
9
9
10
12
9
6
10
8
4
12
£r
11
20
21
38
24
4fi
1 7
21
31
2fi
25
11
19
26
27
19
35
40
37
13
31
21
26
44
52
3D
S
2!
U
o
I
10
I
CO
-------
TITLI
Ox\gen
Silica
Sodium Silicate
Sorbitol
Sulfur
Tetrapropvlene
Thiocyaiutes
Trlpropylene (Nonene)
LTea
Zinc Chlorate
Zinc Ethyl (Zinc Diethyl)
UHOttPOUL
M
1
3
1
U
1
1
1
1
1
1
1
IMMM*
•MM*
2
1
1
1
1
1
2
1
1
2
3
!—»•«
llfcm
1
L
-I1
L
1
L
L
j
L'
L
L
MTIM MVCUL
titan
1
1
1
I
1
1
1
1
1
1
1
isr
1
1
I
1
1
1
1
1
1
1
1
iLIHI II
1
1
1
U
1
1
U
1
1
U
L
LMDOtVOIAL
INK*
2
1
1
L
1
1
2
1
1
1
1
'•ST
2
1
1
1
1
1
1
1
1
2
3
1
L— »^»
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1
1
T
t
L'
L
L
L
U
L'
V
1M
tf*cn
12
8
7
t
8
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8
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7
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1
2
6
1
2
3
1
2
3
3
ln*»
•*"•
12
17
13
21
11
13
17
11
13
17
19
PIMWMH
•••»
1 '.
1 0
1 "l
1 S
1 S
i •>
1 0
1 S
1. !i
1 0
1.0
Om MM
•m
i
25
25
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25
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25
5
.25
.25
TM
*•*•«••
*•«•
2 0
1 2S
1 7i
1 7S
2 0
1 75
1 25
1 75
2 0
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Naw*
«••»
24
10
12
i
Mi
12
10
14
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10
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•
ftMM«
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21
-i7
22
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21
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21.
21
44
tt
Z
D
i—i
X
O
(O
i
-------
APPENDIX D
SUPPORTING DATA
-------
APPENDIX D- 1
ACCIDENTS INVOLVING HAZARDOUS SUBSTANCES
A logical approach to the development of an indepth hazardous-
substance accident analysis is to obtain and analyze extensive amounts
of statistical data relating to:
Reporting of accidents (e. g., frequency, apparent causes,
human factors, effects* etc.)
Materials involved in accidents (e. g., weights or'volumes
of hazardous materials, hazardous material properties,
container characteristics, etc. )
Disposal problems (e. g., effects of quantity, characteristics
of the environment such as meteorological conditions and
terrain features including soil, vegetation, and drainage
pattern, details of handling problems such as salvage
possibilities and specific handling instructions, etc.).
It was quickly apparent during this study that data do not exist
in the detail required to determine both direct and indirect accident
causes, to assess fault where human error may be frequently involved,
and to promulgate preventive measures that would be applicable to a
wide-spectrum of environmental conditions. Further search of the
-------
APPENDIX D-1-2
literature revealed that other researchers have approached similar
problems concerning hazardous materials accidents and have reached
the same conclusion with respect to availability of suitable data. For
example, a very recent study by Booz, Allen and Hamilton, Inc.
(Reference 1) examined the problems of hazardous materials handling,
transportation, and disposal. The study and report developed the
nature and magnitude of problems associated with hazardous materials
and examined, quantitatively, the accident experience of the past. The
study concluded that extensive data gaps exist in hazardous materials
statistics which preclude the development and use of a sophisticated
accident analysis and forecasting technique. Data deficiencies were
assessed in the following areas:
Accident reporting
Accident frequency
Accident causes
Accident effects
Materials involved in accidents
Handling quantities
-------
APPENDIX D-l-3
Disposal quantities
Effects of disposal.
The Booz, Allen and Hamilton study and report developed an
initial overview of the hazardous materials situation despite the severe
data limitations. Following is a brief summary of the approach and
findings of the study.. Additional information in the form of tables
and matrices, has been extracted directly from the Booz, Allen and
Hamilton report)and are included as tables at the end of this
appendix.
From many available classification schemes for the systematic
categorization of toxic or hazardous materials, a set of categories was
selected which related closely to the categories and definitions contained
in the Code of Federal Regulations Titles 46 and 49 (See Table D- 1- 1
for categories and definitions).
Trends in the production and transportation of hazardous materials
were developed as were estimates of quantities of hazardous substances
to be handled and transported during the period of the 1970's. (See
Table D-1-2 for Hazardous Material Production Trends 1957-59 to 1968
and Projections to 1980).
-------
APPENDIX D-1-4
A number of cogent observations were presented concerning
production, transportation, and accidents involving hazardous
materials. Details concerning these observations are given in the
report. Several observations most pertinent to the present study are
summarized below:
Total hazardous material quantities transported are
projected to increase by almost 55 percent during the next
ten years (growth rate of hazardous materials production
is estimated at one and one-half times the Gross National
Product growth rate).
Hazardous materials will comprise an increasing pro-
portion of total intercity freight traffic.
The proportion of the total volume of hazardous materials
transported by pipeline is expected to increase relative
to other transport modes.
Historically, accident frequency rates (accidents per unit
of traffic) for hazardous materials have increased for
railroad and water carriers and declined for motor
carriers.
-------
APPENDIX D-l-5
Projections to 1980 of both total accident occurrences and
occurrence of accidents involving hazardous substances
show increases.
There is a distinct possibility of increased severity of
disaster due to trends toward large unit packages of
hazardous materials and large groupings of these packages.
The approach to reduction of disaster from the presence of
hazardous materials in general cargo appears to lie in
action to reduce transportation accidents in general. Also
specific precautionary action could be taken for shipments
composed all, or mostly all, of hazardous materials.
The total environment surrounding operations involving hazardous
substances includes both the natural environment and that created by
specific handling procedures and transportation operations. The Booz,
Allen and Hamilton report discusses a number of stresses that evolve
in the total environment. The natural environmental stresses include
ambient temperature, amount and rates of precipitation, changes in
air pressure, and severe or unusual weather conditions. Each of
these stresses or conditions may have impact on all matter, personnel,
equipment, and hazardous materials in process of handling, movement,
or storage.
-------
APPENDIX D-1-6
Handling and transportation operations include all of the mechani-
cal stresses inherent in the major modes of transportation which involve
handling, loading and unloading, transporting, marshalling, and long-
term storage. Such stresses include shock and vibration, impact,
compression, puncture and pressure, and abrasion.
The Booz, Allen and Hamilton report developed a number of
observations concerning the stresses that are operative in the total
transportation environment and which may contribute to accidents
involving hazardous materials. Detailed discussions of these
observations are presented in the report. Following are summarized
a number of observations of importance to the present study:
Any or all of the natural environmental stresses may
contribute directly or indirectly to the cause of accidents
involving hazardous materials.
Shock and vibration are the dominant factors inherent in
all parts of the loading-transport.-unloading cycle.
The severity of the working environment is greatest in
those areas where personnel discretion is greatest; e. g.,
in handling by hand, forklift, crane, hose, etc. Handling
shock is primarily a result of careless personnel practices and
is therefore difficult to predict.
-------
APPENDIX D-1-7
Transit stresses are more predictable and are primarily a
function of the transportation equipment and the right-of-
way.
Condition of the right-of-way is perhaps the most basic
factor bearing on the accident environment. More important
statistically is maintenance of the vehicle and its safety
equipment.
Marshalling activities, between loading/unloading and
transport, may cause some of the most severe shocks
involved in the transportation cycle (e. g., impacts with
loading docks, railroad car switching, ship docking,
aircraft landings, etc. ).
Inadequate maintenance of rolling equipment is a signifi-
cant contributing factor in accidents. Correction is
complicated by the fact that much is owned, controlled,
and/or loaded/unloaded by the owner of the commodity
rather than the operator of the transport system.
Certain failure modes of currently used containers can
and do,seriously aggravate the scope of the hazard when
an accident occurs.
-------
APPENDIX D-l-8
A survey of 230 spills of hazardous materials to the environ-
ment from a variety of storage, transportation, and industrial
media indicates no specific pattern or causative factors.
(A detailed summary of representative accidents involving
handling and transportation of hazardous materials as
prepared for the Booz, Allen and Hamilton report, is
included in Table D-1- 3.
-------
APPENDIX D-l-9
Table D-l-1
Categories and Definitions of Toxic or Hazardous Materials
Classification/Category
General Nature of Hazard
Flammable Materials
Compressed Gases
Corrosive Materials
Explosives
Oxidizing Agents
Poisons
Etiologic Materials
Cryogenic Materials
Radioactive Materials
Molton Materials
Fire with attendant property damage,
personal injury, or loss of life. Includes
both liquids and compressed flammable
gases.
Nonflammable explosion; possible
property damage, personal injury, or
loss of life.
Severe damage to living tissue, acids,
for example, causing personal burns
and possible loss of life; property damage
mostly to plant life.
Contact hazards of fire or explosion;
property damage; personal injury or
loss of life.
Fire and explosion, depending on material
they come in contact with. Property damage,
personal injury, or loss of life.
Personal sickness and possible death
from both direct and indirect effect
(pesticides); same for animals. Can be
of long-range in effected area.
Infectious disease-producing materials.
Personal sickness and death. Also
possible long range in effected area.
Extremely low temperature. Dangerous to
living tissue; personal injury.
Radioactive emissions both short- and long-
term. Personal sickness and death.
High temperature and heat content; fire
producing. Property damage and personal
injury.
-------
FLAMMABLE MATERIALS
. Total ReH-ied Petroleum Products (Mils of Bob.)
Gwolmc (Mils, of Bbb )
. Paint! and Vamuhn (1957-59 • 100)
. Pai'ici Maienali (195? 59 • 100)
. Cn.de Pet-oleum (Mill, of Bbli)
COMPRESSED CASES
LPlMi (M.'s. of Gallons)
. Induuiul Gaits (1957-59 -lOO)
. Anhydrous Ammonia (Mill of Sht. Tons)
. l>y Natural Gai (Bill of Cu Ft.)
. OUorme (Mih of Sht Tens)
CORROSIVE MATERIALS
. Toul Conouvc Material! fMill of Sht Tom)
Sulfunc Acid (Thoui of Shi Tom)
EXPLOSIVE MATERIALS
Induitnil llicji Explosive Shipment! (Mils of Lbs.)
. Ammunition ard Other (Mill of Lbi )
OXIDIZING AGENTS
. Ammonium Niuaies (Thous of Sht. Ton)
. Qiloram and Bleaches
POISONS
Agricultural Pesticides (Mils, of Lbs.)
. Inorganic Poison snd other Pesticides (Mils, of Lbs)
RADIOACTIVE MATERIALS (Thous. of Shi. Ton)
ETIOLOCICAL AGENTS (Mils, of Shi. Ton)
MOLTEN MATERIALS (Mils of Sht Ton)
CRYOGENIC MATERIALS
LqLiHed Natural Gai (Mils of Gals )
. Liquefied Industrial Gates (Mill, of Tons)
Annual Production
1957-59 Average
3013
1.433
100
100
2.547
7.104
100
4.044
11.252
6
24316
16473
874
1000
2473
270
545
1000
~~
4
5442
3
1968
4044
1.940
130
399
3.329
14.500
249
12093
19.255
12
45052
28.383
1.582
2,400
5.223
700
I013<
1.200
17
8
13
8.390
8
Table D-l-2
Hazardous Material Production Trends,
1957-59 to 1968 and
Projections to 1980
Projected Annual Production
ftfccfit incfcuc
Anninl Growth R«ie
1957-59 Average
3013
1.433
100
100
2.547
7.104
100
4.044
11.252
6
24316
16473
1968
4044
1.940
130
399
3.329
14.500
249
12093
19.255
12
45052
28.383
1970
4.324
2080
138
505
3.560
16.725
329
16000
21391
14
51099
31.591
1975
5.110
2,420
160
911
4070
23.900
662
32.175
27.824
22
70010
41.288
1980
6040
2020
185
1441
4400
24.150
1431
64.700
36.193
31
95*19
53.962
1957-59/1968
34.2%
354
100
2990
30.7
1041
1490
1990
71 1
81 J
702
1968/1980
494*
44.2
424
3IIJ
135.5
434.5
166.1
880
1129
90.1
1957-59/1968
30*
31
24
148
2.7
74
9.5
114
5.5
61
5.5
1968/1980
3.4*
3.1
30
12.5
7.4
150
150
54
6J
5.5
874
1000
2473
270
545
1000
—
4
5442
3
1.582
2400
S.223
700
1.200
17
8
13
8.390
8
1.777
2400
6036
860
1.409
1.380
28
—
15
9400
9
2478
3.200
8465
1440
2.129
1.540
80
—
26
12.500
18
3.183
4000
12.440
2420
3.21 S
1.760
163
—
41
16000
36
810
954
200
2250
48.7
166.7
101.2
138.2
46.7
8S8J
2154
90.7
3500
61
6S
IJf
12.5
40
10J
60
IS
8.6<
20.7
100
ss
136
(I) Bued on 1966 Estinutn.
Source Lxhibiu BI Ihrouih B 9 and wnaortuii data
tt
V
0
I
H-
O
-------
Table D-l-3
Composite and Representative
Hazardous Materials Accident Summary
DATE
HAY U,B«
MAY B »•
JULY 1. BSI
OCCCHBEH I BSS
OCTOBER r. am
AUGUST L Ml
JULY B. ISM
JANUARY U. It*
JARUARV B
JANUARY II
JUHC 13
JULVI
JULY 11
AUGUST a
SEPTEMBER U
SEPT EMBER •
NOVEMBER 11
DECEMBER B
DECEMBER B
FEBRUARY 17. BSI
MARCH U
•AT J
AUGUST B
AUGUST U
AUGUSTS
SEPTEMBER S
OCTOBER 1
OCTOBER 1
OCTOBER D
OCTOBER >l
NOVEMBER X
COMMODITY
ii
u
X
X
X
X
X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
a
.5
JO
•
X
x
II
l\
X
X
M
| EXPLOSIVE
X
X
X
X
X
X
I
2
X
X
X
w
i.
II
o»-
• a
QUANTITY
I
«»
»>
•4
LARGE
1 GALLONS
IOOO.OOC
IS
MODE
X
X
X
X
X
5
X
X
o
s
5
H
£
3
i
X
DEATH
li
B
II
_
1
1
1
1
•
1
_
1
1
J
2
1
S
1
|
1
INJURY
40
>ao
• >
247
_
2
I
~
"
1
1
-
1
-
t
i
14
2
0
1
1
COMMODITY
DAMAGE
I
X
X
X
x
x
X
X
x
X
X
X
X
X
x
X
X
x
X
X
x
x
x
x
x
x
X
I
H
M
^
X
EQUIPMENT
DAMAGE
t*
x
X
X
x
X
X
X
X
X
X
x
"
M
a
M
£
x
X
X
X
X
X
x
x
x
X
x
X
4
x
X
X
X
X
X
PROPERTY
DAMAGE IN
THOUSANDS
OF DOLLARS
130.000
1.000
>B.OOO
>LOOO
10400
ftJBO
109
SI
B
n
n
ISO
s
10
11
EXTENSIVE
11
90
20
12
390
10
B
1
S
41
1
a
1
i
o
5
s
i
u
|
I
o
§
a
.
REMARKS
UNLOADING
EH ROUTE
CHAIN REACTION AT STORAGE FACILITY
LOAOMC'UNLOADINO
PAPXEO ON CITY STREET
1X000 PEOPLE EVALUATED
LOADING
EN ROUTE
LOAOINO
EN ROUTE
EH ROUTE
UNLOADING
CR ROUTE
EH ROUTE
EH ROUTE
LOADING
CRRbJTE
EH ROUTE
EH ROUTE
EH ROUTE
EH ROUTE
UNLOADING
EN ROUTE
EH ROUTE
EH ROUTE
LH ROUTE
EH ROUTE
EN ROUTE
EH ROUTE
LOADING
UNLOADING
25
O
-------
Table D-l-3
(Continued)
DATE
mi
mi
JANUARY i mi
JANUARY II
FEBRUARY »
FCBRtlAIIY 14
•ARCH 17
JULY 19
AUCUIT II
SEPTEMEII 1
OCTOBER 1
OCTOBER »
NOVEWR 1
NOVEIIBER II
NOVEMBER U
OCCWBCRI
OECENBER II
M CUBER II
OCCCIIKRI4
OECUMWNV
ml
M*
INI
COMMODITY
4
3^
I Mi
11
X
X
X
X
X
X
X
X
X
X
X
X
X
a
11
X
X
n»mjiY» i
IAKOHIIO3 1
X
w
3
M
W
K
I
X
X
I
O
X
X
X
?-
5*
Is
X
QUANTITY
I
LARGE
40>
a
•All.
I
u
'».ooo
m
MODE
•.
5
x
JTHUCK
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x
o
o
5
X
X
M
X
J
mi
fc
o
s
X
DEATH
_
.
-
-
.
-
.
_
_
.
-
-
1
1
.
1
1
_
INJURY
• _
.
.
_
I
14
1
-
_
1
-
-
I
1
1
•
_
~
COMMODITY
DAMAGE
i
x
x
X
X
X
X
X
X
X
x
x
X
X
M
M
M
X
X
i
ft.
X
MALI
SMAU
•MALI
EQUIPMENT
DAMAGE
»-
x
EXTENSIVI
X
X
X
X
PARTIAL
X
X
X
X
X
X
X
X
_
X
PROPERTY
DAMAGE IN
THOUSANDS
OF DOLLARS
.
_
EXTDWVE
H
II
a
B
a
-
M
.
M
11
MALL
B
]QD
•
aog
"
£
|
m
5
5
&
§
«
f
1
|
.
j
t
4
B
i
|
1
1
s
1
1
1
REMARKS
1 ACCIDENTS HTM HO ADDITIONAL mFDRMATlON
> ACCIOCNTS *TM NO ADMTtONAL MVOMATlOH
Fine LASTED 1 CATt-FUN KILL EXTENDEDU MILES
PANNED
IN ROUTS
PAHKEOMINOfl CONTAMINATION O* t*f ftSOMNf L
UMLOAOIN6
UHLOAOlllC
^
ENROUTI
nREMD ROT OCCUR
EN ROUTE
EH ROUTE
EH ROUTE
(N ROUTE
CM ROUTE
III ROUTE
~
EN ROUTE
EN ROUTE
I ACCIDENTI anCN.VMG FIRE
If ACaOOTI IMOLVINe FIRE
i AcaouiTi IXVOLVIIIO SFILL«OI EH ROUTE
TJ
H
2
d
i^
x
o
(O
-------
Table D-l-3
(Continued)
DATE
JANUARY 2. BB
JANUARY J
JANUARY 1
JANUARY F
JANUARY 11
JANUARY 14
JANUARY U
JANUARY IF
JANUARY It
JANUARY 8
JANUARY*
FEBRUARY 1
FEBRUARY I
FEBRUARY U
FEBRUARY U
FEBRUARY 8
FEBRUARY U
FEBRUARY a
MARCH 1
MARCH 1
• ARCH 4
MARCH 4
MARCH F
MARCH 14
MARCH »
•ARCH a
•ARCH 9
APRIL 1
APRIL 1
APRIL 1
APRIL'
APRIL'
COMMODITY
•1
4
V
.1 <
u. X
X
X
«
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
o
1
it!
0<
uo
X
X
X
X
X
X
X
X
>3
lot
,4
Ul
.
X
^
i
1
s
!
^ I
5 5
5 2
o o
i I
W W
•v a.
REMARKS
.
LOAOINO
EN mure
.
EN ROUTE
RESIDENTS EVACUATED
EN ROUTE
EN ROUTE
EN ROUTE
EN ROUTE
SINKING
LOADING
EN ROUTE
_
EN ROUTE
COLLISION
_
COLLISION
.
EN ROUTE
EN ROUTE
EN ROUTE
EN ROUTE
VANDALISM
EN ROUTE -NO FIRE
EN ROUTE
UNLOADING
Eh ROUTE
LOAOING'UNLOAOINC
BUSINEII ARIA EVACUATED -
FIRE EXTENDED TO BRIDGE
EN ROUTE - HO FIRE
2!
O
»>-<
X
o
CO
-------
Table D-l-3
(Continued)
DATE
APRIL u. na
APRIL U
APRIL II
APRIL II
APRIL »
APRIL II
APRIL 22
APRIL B
APRIL a
APRIL V
APRILS
APRIL •
MAT i. na
•ATT
•ATI
•ATI
MAY 1
MATH
•AYU
•AYU
•AY 14
•AYU
MATD
MAY a
JUNEI.Ua
JUNE I
JUNE*
JUNES
JUNE'
JUNE*
JWIH
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-------
Table D-l-3
(Continued)
DATE
JUNE ix an
JUNE II
JUNE a
JULY!
JULY*
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JULY IS
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AUGUSTS
AUGUST 14
AUGUST u
AUGUST a
AUGUST 25
SEPTEMBER!
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OCTOBER!
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-------
Table D-l-3
(Continued)
1
DATE
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-------
APPENDIX D-l-17
REFERENCES
1. "An Appraisal of the Problem of Handling, Trans-
portation, and Disposal of Toxic and Other Hazardous
Materials, " Prepared by Booz, Allen and Hamilton,
Inc., Washington, D. C., January 1970.
-------
APPENDIX D-2
-------
Table D-2-1
Typical Hazardous Chemicals Distributed
to Major Industrial Segments by SIC Code
20
Food* Kindred Prod
Acetic Anhydride
Acetic Acid
Aretyl Chloride
Aluminum Fluoride
Aluminum Sulfate
Ammonium Chloride
Ammonium fluoride
Ammonium Per sul fate
Aiml Acetate
Boric And
Carbon Monoxide
Cntric Acid
Crenols
Ethanol
Ethvlamme
Hydrogen Peroxide
Isopentane
Magnesium Oxide
Nitrous Oxide
Potassium Fluoride
Propvlene Di chloride
Sodium Bisulfite
Sodium Nitrite
Sorbitol
Sulfur Dioxide
Zinc Oxide
22
Textile Mill Prod
Acrylic Acid
Acrylonttrile
Ammonium Sulfate
Ammonium Chromate
Ammonium Fluoride
Ammonium Sulfide
Amyl Acetate
Amyl Alcohol
Antimony
Boric Acid
Butyl Acetate
Diethylene Glycol
Ehtanolamines
Ethyl A cry late
Ethylenimine
Formic Acid
Isopropyl Ether
Magnesium Sulfate
Mercuric Chloride
Oxalic Acid
P entac hlorophenol
Pe rchloroet hy le ne
Potassium Dichromate
Sodium A r senates
Sodium Hydro sul fite
Thiocyanates
Tnchloroethane
Tnchlorocthylene
Zinc Oxide
26
Paper A Allied Prod.
Acetic Anhydride
Acrylic Acid
Aluminum Sulfate
Butyl Acetate
Chlorine
Dimethyl Sulfate
Ethyl Acrylate
Ethyl enimine
Hydrogen Peroxide
Magnesium Oxide
Magnesium Sulfate
Mercury
Pentachlorophenol
Potassium Dichromate
Sodium Bisulfite
Sodium Carbonate
Sodium Hydroxide
Sodium Silicate
Sulfur Dioxide
Thiocyanates
29
Petroleum A Coal Prod.
Dimethyl Sulfate
Di nit roc re sol s
Ethanolammes
Ethylene Bromide
Hydrofluoric Acid
Meta-p-Nitroaniline
Methyl Met ha cry late
Nonylphenol
Phosphorus Oxy chloride
Phosphorus Pemasulfide
Potassium Dichromate
Propane
Propylene
Sodium Hydroxide
Strontium
Sulfur Dioxide
Tar Crude
Tetra ethyl Lead
Thiocyanates
Toluene
Tnethylene Glycol
Trl-o-Cresyl Phosphate
31
Leather & Leather Prod
Acrylic Acid
Aluminum Sulfate
Arsenic Tnoxlde
Boric Acid
Ethyl Acrylate
Formic Acid
Lead Acetate
Magnesium Sulfate
Mercuric Chloride
Methyl A cry late
Oxalic Acid
Potassium Dichromate
33
Primary Metal Ind
Acetylene
Aluminum Fluoride
Ammonium Sulfide
Antimony
Arsenic
Barium Carbonate
Boric Arid
Boron Trichloride
Boron Tri fluoride
Calcium Arsenate
Carbon Monoxide
Hydrocyanic Acid
Hydrofluoric Acid
Lead
Lead Cyanide
Mercuric Chloride
Mercuric Sulfate
Nickel
Nickel Cyanide
Nitric Acid
Oxalic Acid
Oxygen
Potassium Cynide
Selenium
Sodium
Sodium Borate
Sodium Nitrite
Sulfur Dioxide
Sulfuric Acid
Tantalum
Thallium
T r ichlora et hane
Zinc Chloride
34
Fabricated Metal Prod.
Acetylene
Ammonium Sul fide
Ammonium Pereulfate
Antimony Trichloride
Boric Acid
Cadmium
Cadmium Salts
Chromic Acid
Cresol
Hexamethylene Diamme
Hydrocyanic Acid
Hydrofluoric Acid
Hydrogen Sulfide
p - Hydroquinone
Isobutyl Acetate
Lead Cyanide
Manganese
Nickel
Nickel Ammonium Sulfate
Nickel Cyanide
Nitric Acid
Oxalic
Potassium Cyanide
Potassium Dichromate
Silver Cyanide
1 Sodium Nitrite
Sulfuric Acid
Thallium
ThlocyanateB
Tnchloroethane
Trichloroethylene
Vinyl Chloride
Zinc Chloride
M
"2
a
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CO
------- |