national enforcement investigations center
denver federal center bldg 51 b()xJS227 denver, LO 8022S
SUMMARY
PRETREATMENT CRITERIA
Taken from Pretreatment Standards
for Existing and New Sources
and from Various EPA Limitations-Guidelines
Development Documents
[Current as of March 1977]
EPA-330/1-77-010
us. environmental protection agency
office of enforcement
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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/1-77-010
SUMMARY
PRETREATMENT CRITERIA
Taken from Pretreatment Standards
for Existing and-New Sources
and from Various EPA Limitations-Guidelines
Development Documents
[Current as of March 1977]
July 1977
National Enforcement Investigations Center
Denver, Colorado
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CONTENTS
Port
405 D.AIRY PRODUCTS INDUSTRY 1
406 GRAIN MILLING INDUSTRY . 5
407 CANNED AND PRESERVED FRUITS AND VEGETABLES INDUSTRY. ... 9
408 CANNED AND PRESERVED SEAFOOD PROCESSING INDUSTRY 12
409 BEET SUGAR PROCESSING 16
409 CANE SUGAR REFINING 17
409 RAW CANE PROCESSING 19
410 TEXTILES MANUFACTURING 21
411 CEMENT MANUFACTURING INDUSTRY 25
412 FEEDLOTS INDUSTRY 27
413 ELECTROPLATING AND METAL FINISHING INDUSTRY 29
414 ORGANIC CHEMICALS MANUFACTURING INDUSTRY 39
415 INORGANIC CHEMICALS MANUFACTURING INDUSTRY 48
416 PLASTICS AND SYNTHETICS MATERIALS MANUFACTURING
INDUSTRY . . . '. 66
417 SOAP AND DETERGENT MANUFACTURING 72
418 FERTILIZER MANUFACTURING INDUSTRY 78
419 PETROLEUM REFINING INDUSTRY 87
420 IRON AND STEEL MAKING SEGMENT OF IRON AND STEEL
INDUSTRY 91
420 HOT FORMING, COLD FINISHING AND SPECIALTY STEEL
SEGMENT OF IRON AND STEEL INDUSTRY 97
421 ALUMINUM, COPPER, LEAD AND ZINC SEGMENT OF THE
NON-FERROUS METALS MANUFACTURING INDUSTRY 106
422 PHOSPHATE MANUFACTURING INDUSTRY 118
423 STEAM ELECTRIC POWER GENERATING INDUSTRY 126
424 FERROALLOYS MANUFACTURING INDUSTRY 133
425 LEATHER TANNING AND FINISHING INDUSTRY 140
426 (INSULATION) FIBERGLASS MANUFACTURING 146
426 FLAT GLASS, PRESSED GLASS AND BLOWN GLASS MANUFACTURING. . 148
427 ASBESTOS PRODUCTS MANUFACTURING INDUSTRY 153
428 RUBBER PROCESSING INDUSTRY 157
429 TIMBER PRODUCTS INDUSTRY 163
430 UNBLEACHED KRAFT AND SEMICHEMICAL PULP/PAPER MILLS .... 171
430 BLEACHED KRAFT, GROUNDWOOD, SULFITE, SODA, DEINK AND
NON-INTEGRATED PULP/PAPER MILLS 174
431 BUILDING PAPER AND ROOFING FELT MANUFACTURING 179
432 RED MEAT SEGMENT OF THE MEAT PRODUCTS INDUSTRY 181
432 PROCESSOR SEGMENT OF MEAT PRODUCTS INDUSTRY 184
432 RENDERING SEGMENT OF THE MEAT PRODUCTS INDUSTRY 187
432 POULTRY SEGMENT OF THE MEAT PRODUCTS INDUSTRY 189
434 COAL MINING INDUSTRY 192
435 OFFSHORE AND ONSHORE OIL AND GAS EXTRACTION INDUSTRY ... 194
436 MINERAL MINING AND PROCESSING INDUSTRY 199
439 PHARMACEUTICAL MANUFACTURING - 203
440 ORE MINING AND DRESSING INDUSTRY 205
443 PAVING AND ROOFING (TARS AND ASPHALT) MATERIALS
INDUSTRY . 208
446 PAINT FORMULATING 210
447 INK FORMULATING 212
454 GUM AND WOOD CHEMICALS MANUFACTURING 214
455 PESTICIDE CHEMICALS MANUFACTURING 216
457 EXPLOSIVES MANUFACTURING 219
458 CARBON BLACK MANUFACTURING 221
459 PHOTOGRAPHIC PROCESSING 223
460 HOSPITALS 226
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FOREWORD
Pretreatment standards and criteria are expected to undergo considerable
change in the future and those who deal with pretreatment issues should
strive to keep informed of all updatings.
This Pretreatment Report has been prepared to satisfy, at least in part,
a pressing need for information on pretreatment of industrial wastes --
that is, treatment before these wastes are properly received into
municipal collection and disposal systems. This information has been
widely requested. In connection with ongoing technical support activities
on pretreatment, the Environmental Protection Agency (EPA) National
Enforcement Investigations Center (NEIC), Denver, Colorado has compiled
and summarized available data on pretreatment principally as found in
the Code of Federal Regulations, Title 40 - Protection of the Environment,
Subchapter N - Effluent Guidelines and Standards, Parts 405-460. This,
in turn, was supplemented by various available USEPA Effluent Limitations
Guidelines Development Documents prepared from 1973 through the present.
This Pretreatment Report covers 42 different industries, which are
represented by 50 sections. Each section is divided into various
subparts consisting of: Subcategorization and Description of the
Industry; Nature of the Problem; Waste Parameters of Concern; Preliminary
*
Limitations for Discharge to POTW's ; and Prescribed Pretreatment Measures.
Detailed industry description is provided for two reasons: 1) to
summarize this information in a single EPA report; and 2) since NEIC in
June 1977 published another document summarizing Limitations Guidelines
for Existing Sources and New Sources across the same industry classifications,
a thorough industry description will enable easier and more complete use
of the June 1977 publication.
Publicly Owned Treatment Works
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In the Federal Register of February 2, 1977, the USEPA gave notice of
intentions to issue regulations setting up mechanisms and procedures for
controlling the introduction of industrial wastes into POTW's. The
preamble to these general pretreatment regulations would set forth EPA's
overall policy for the establishment and enforcement of pretreatment
regulations. Four options were proposed giving various approaches to
establishing and enforcing pretreatment requirements. These options
differed mainly in terms of the degree to which industrial users of
POTW's would be controlled by Federally promulgated technology-based
standards vs. locally developed and applied pretreatment limits. The
options also vary in terms of the particular government body (i.e.
Federal, State or local) charged with primary responsibility for en-
forcement of applicable requirements. These options are very briefly
delineated below. It is intended that one of these options will be
selected in the near future as part of a National Pretreatment Strategy.
Option I - Local enforcement, monitoring and reporting would be
heavily emphasized. Local agencies would be expected
to require compliance with Federal technology-based
standards or alternative standards where variances are
approved.
Option II - Local enforcement of technology standards integrated with
locally-derived water quality based pretreatment limits
in lieu of Federal standards.
Option III - Local enforcement but with Federal technology-based
standards for the more hazardous pollutants and the more
significant industries discharging these pollutants.
Local standards would apply in all other cases.
Option IV - The regulatory program would rely heavily upon the
USEPA and the NPDES States, and Federal technology-based
pretreatment standards would be issued.
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In connection with the above notice, the USEPA in January 1977 released
a three-volume document titled "Federal Guidelines and State and Local
Pretreatment Programs," EPA Report MCD-43. The report provides introduction
to the pretreatment problems and information on management of a control
program, legal aspects of a control program, monitoring, pollutants
which interfere with POTW's, and removal and pass-through of pollutants
in POTW's. Volumes II and III comprise a series of useful technical
appendices.
This report is a compilation of draft, interim, interim final, and final
regulations, and information from the various Development Documents and
other sources, current through March 1977. Where pretreatment regulations
have been superseded, remanded or revoked, these changes are indicated.
However, all changes in the Code of Federal Regulations may not have
been incorporated in this report; therefore, such accuracy is not
claimed. Much of the information contained herein is of guidance nature
only. It is recommended this Report be used as a summary, or desk
reference. The Federal Register should be consulted for official
application of pretreatment limitations.
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DAIRY PRODUCTS INDUSTRY
(40, 41, 42)
[Part 405]
SUBCATEGORIZATION OF THE INDUSTRY
The Dairy Products Industry is divided into twelve Subcategories as
defined below:
A - Receiving Stations
B - Fluid Products
C - Cultured Products
D - Butter
E - Cottage Cheese and Cultured Cream Cheese
F - Natural and Processed Cheese
G --Fluid Mix for Ice Cream and Other Frozen Desserts
H - Ice Cream, Frozen Desserts, Novelties and Other Dairy Desserts
I - Condensed Milk
J - Dry Milk
K - Condensed Whey
L - Dry Whey
Subcategory A, Receiving Stations. Establishments engaged in the as-
sembly and reshipment of bulk milk for the use of manufacturing or pro-
cessing plants. Receiving stations have been further subdivided into
establishments receiving more than 150,000 Ib. milk daily vs. those re-
ceiving less than 150,000 Ib. milk daily.
Subcategory B, Fluid Products. Manufacture of market milk, flavored
milk (chocolate and others), and cream (of various fat concentrations,
plain and whipped). Fluid product plants have been further subdivided
into establishments receiving more than - and less than - 250,000 Ib.
milk equivalent daily.
Subcategory C, Cultured Products. Manufacture of cultured products,
including cultured skim milk, yogurt, sour cream, and dips of various
types, including cultured cream cheese dip. Cultured product plants
have been further subdivided into establishments receiving more than -
and less than - 60,000 Ib. milk equivalent daily.
Subcategory D, Butter. Manufacture of butter, either by the churning
or continuous process. Butter plants have been further subdivided into
establishments processing more than - and less than - 175,000 Ib milk
equivalent daily.
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Subcategory E. Cottage Cheese and Cultured Cream Cheese. Manufacture
of cottage cheese curd and cultured cream cheese (soft), as opposed
to rennet curd natural and processed cheese. Cottage cheese plants have
been subdivided into establishments processing more than - and less
than - 25,000 Ib. milk equivalent daily.
Subcategory F, Natural and Processed Cheese. Manufacture of natural
cheese (hard curd) and processed cheese.These plants have been sub-
divided into establishments processing more than - and less than -
100,000 Ib. milk equivalent daily.
Subcategory G, Fluid Mix For Ice Cream and Other Frozen Desserts. These
products are manufactured for later freezing in other plants. The fluid
mix plants have been subdivided into establishments receiving more than -
and less than - 85,000 Ib. milk equivalent daily.
Subcategory H, Ice Cream, Frozen Desserts, etc. Manufacture of ice
cream, ice milk, sherbet, water ices, stick confections, frozen novelties
products, frozen desserts, melonne, puddings and other dairy product-base
desserts. Ice cream and associated plants have been subdivided into es-
tablishments receiving more than - and less than - 85,000 Ib. milk equiva-
lent daily,
Subcategory I, Condensed Milk. Manufacture of condensed whole milk, con-
densed skim milk, sweetened condensed milk and condensed buttermilk.
Condensed milk plants have been subdivided into establishments condensing
more than - and less than - 100,000 Ib milk equivalent daily. For the
smaller size plants, the limitations documents indicate that once-through
barometric condenser waters may be discharged untreated if the composite
NET entrainment is less than 15 mg/1 BOD,- for any single day, and less
than 10 mg/1 BODj- as an average for 30 consecutive days.
Subcategory J, Dry Milk. Manufacture of dry whole milk, dry skim milk,
and dry buttermilk. Milk drying plants have been subdivided into es-
tablishments receiving more than - and less than - 145,000 Ib. milk
equivalent daily.
Subcategory K, Condensed Whey. Manufacture of condensed whey and con-
densed acid whey. Whey condensing plants have been subdivided into
establishments receiving more than - and less than - 300,000 Ib. fluid
raw whey daily. For the smaller size plants the limitations documents
indicate that once-through barometric condenser waters may be discharged
untreated if the composite NET entrainment is less than 15 mg/1 B005 for
any single day, and less than 10 mg/1 BODj- as an average for 30 consecutive
days. b
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Subcategory L, Dry Whey. Manufacture of dry sweet whey and dry acid
whey. Whey drying plants have been subdivided into establishments re-
ceiving more than - and less than - 57,000 Ib of 40 percent dry solids
daily.
NATURE OF PROBLEM
In 1970, there were approximately 5,500 dairy plants in the United
States. Many are multi-product facilities. Pollutants in wastewaters
from dairy product plants represent materials lost through processing
of raw materials into finished products, and materials lost from an-
cillary operations. The former consists of milk, milk products and
non-dairy ingredients such as sugar, fruit, nuts, etc. The latter con-
sists of cleaners and sanitizers, lubricants, sanitary wastes, etc.
Dairy plant wastes with the possible exception of certain lubricants,
cleaners, sanitizers and concentrated wheys are relatively degradable
in biological waste treatment systems. Refractive materials are generally
present in fairly low concentrations.
PARAMETERS OF CONCERN
BOD Phosphorus
COD Nitrogen
TSS Chlorides
pH Temperature
The majority of phosphorous is contributed by wasted detergents. Some
cleaning solutions may be recycled. Quaternary ammonium compounds used
for sanitizing and certain detergents can be a source of nitrogen in
dairy wastewaters. Principal sources of chloride include brine leaked
from refrigerator systems and chlorine-based sanitizers.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
PRETREATMENT MEASURES
Np_ specific pretreatment limitations have been developed for Existing
and/or New dairy product establishments. It has been determined that
dairy plant discharges are treatable and can be handled by biological
treatment provided that suitable design and capacity have been incor-
porated into the POTW. Equalization of dairy wastes may be necessary
in some cases. Difficulties may be experienced in attaining normal
treatment efficiencies when the BOD load attributable to whey exceed
10 percent of the total POTW load received. This is especially true
without proper wastes equalization. Consequently, under given situa-
tions, whey may not be a compatible pollutant at the POTW.
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The best approach by dairy plants to reduce excessive surcharges and
waste load to the POTW is to practice good in-plant controls and re-
cycling of cooling waters. If the local authority requires pretreat-
ment, this may take the form of anaerobic digestion, high-rate bio-
logical systems, stabilization ponds, aerated ponds, or chemical treat-
ment. Anaerobic digestion may be applicable to small plants discharg-
ing low volume wastes. If dairy wastes comprise a significant portion
of the total load to the POTW, it may be necessary to completely sep-
arate the whey to avoid upset of the treatment works.
Grease, fats and oils in dairy wastes generally do not pose a large
problem to the municipality. Large quantities of floating fats and
grease from dairy effluents could, however, adhere or cling to sewer
lines and in some cases, clog sewerage systems.
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GRAIN MILLING INDUSTRY
(96, 97, 98, 99, 100, 101, 102, 103)
[Part 406]
SUBCATEGORIZATION OF THE INDUSTRY
The Grain Milling Industry is divided into 10 Subcategories. Six Sub-
categories are devoted to!grain processing including corn, wheat and
rice. The remaining four;subcategories cover the production of animal
feeds, breakfast cereals,.and wheat starch. These subcategories are
described in further detail below.
A - Corn Wet Milling!
B - Corn Dry Milling:
C - Normal Wheat Flour Milling
D - Bulgur Wheat Flour Milling
E - Normal Rice Milling
F - Parboiled Rice Processing
G - Animal Feeds
H - Hot (Breakfast) Cereals
I - Ready-to-eat (Breakfast) Cereals
J - Wheat Starch and .Gluten
Subcategory A, Corn Wet Milling. Processing includes the dry cleaning
of the shelled corn, followed by softening of the kernels in the steep-
ing operations, followed by wet milling. The latter serves to separate
the germ, starch, gluten and hulls. Further wet processing can;be used
to produce corn oil, regular modified starches, corn syrup, dextrose
and animal feed.
Subcategory B. Corn Dry Milling. Differs substantially from corn wet
milling. After the corn is washed, only dry processing is used ;to pro-
duce corn meal, grits, flour, oil and animal feed.
Subcategory C, Normal Wheat Flour Milling. Preparation of wheat into
ground:flour or granular product is fundamentally a dry milling process,
which distinguishes it from the production of bulgar flour. After clean-
ing with water or air, moisture is added in a tempering process with no
water discharged, followed by dry milling. Dry milling in this case
separates the germ and bran from the flour.
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Subcategory D, Bui gar Wheat Flour Milling. Differs from normal wheat
flour milling in that the wheat is parboiled, and then dried before
milling.
Subcategory E, Normal Rice Milling. In contrast to corn and wheat, the
product of rice processing is the whole grain rather than the flour or
meal. Rough rice is cleaned and then milled to remove hulls, bran and
germ. The latter may be sold separately or combined into animal mill
feed. The polished rice is eventually enriched with vitamins and min-
erals before packaging.
Subcategory F, Parboiled Rice Processing. Parboiling differs from normal
rice processing only in the soaking and cooking operations known as par-
boiling.
Subcategory G, Animal Feeds. Animal feeds (formula feed concentrate)
are manufactured primarily using grain and grain by-products, which may
be supplemented by proteins, Pharmaceuticals, vitamins or mineral
additives.
Subcategory H, Hot Cereals. The production of various breakfast cereals
from grains, principally wheat and oats, and requiring cooking prior to
normal human consumption.
Subcategory I. Ready-To-Eat Cereal. The processing of various grains
and other materials (whole grain wheat, rice, corn grits, oat flour,
sugar and minor ingredients) to produce various breakfast cereals nor-
mally available for human consumption without cooking.
Subcategory J, Wheat Starch and Gluten. Wheat flour is used as a raw
material for production of wheat starch and gluten (protein) components
through conventional processes of physical separation and subsequent
refinement.
NATURE OF PROBLEM
The industry incorporates the three main grains of corn, wheat and rice.
Finished products from the milling of the different grains are quite
distinct. Corn milling products range from corn meal and grits to starch
and syrup. Wheat milling principally produces flour for baking and
other purposes, and the specialty product of bulgar wheat. Rice milling
yields ordinary and parboiled rice for human consumption.
The animal feed, breakfast cereal, and wheat starch industries all uti-
lize products from basic grain processing mills for raw materials.
Grain and grain milling by-products are the chief ingredients in animal
feed. The manufacture of breakfast cereals utilize both milled and whole
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grain, particularly corn, wheat, oats and rice. Wheat starch manufac-
turing employs wheat flour as its raw material. Of all cereal grain
produced in the U.S., only about 15% is used as food for human consump-
tion. The vast majority of the grain harvested is used to feed poultry
and livestock. "Complete feeds" have been replaced by "feed concen-
trates." The farmer mixes his own grain with the feed concentrates.
Also, many manufacturers of drugs and feed ingredients have developed
combinations of drugs and vitamins known as "premixes" to which protein
and grain are added.
Corn wet milling uses more water and generates more waste water than
any other grain milling process. Major waste streams include: con-
densates from steep water evaporation, cooling water from once-through
barometric condensers, waste water from modified starch production,
and waste water from activated carbon and ion exchange units and evapor-
ation of syrup in the syrup refining operations. Raw waste waters from
wet corn milling plants may range from 1 to 30 MGD. The BODg of these
wastes averages 415 lbs/1,000 Standard Bushels. The term Standard
Bushel means a bushel of shelled corn weighing 56 Ibs.
A large percentage of grain mills discharge to POTW's. Regarding
starch and gluten mills in particular, these effluents may require
.special pretreatment in order to reduce waste strength prior to entering
the municipal system.
PARAMETERS OF IMPORTANCE
BOD TDS
COD Phosphorous
TSS Total Nitrogen
pH Temperature
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
Except for excessive peak discharges of Corn Wet Milling wastes into
POTW's, which may need to be closely controlled, the Federal Regulations
and accompanying EPA Development Documents for Grain Mills describe
these wastes as compatible with POTW's. Np_ pretreatment limitations
have been placed upon Existing mills within Subcategories A through F,
and both Existing and New mills within Subcategories G through J.
Pretreatment limitations for New Sources within Subcategories A through
F are not completely defined. However, they would likely approximate
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limitations given for Existing Sources in these same Subcategories,
which means the absence of any limitations. The one possible exception
is given as follows.
For Subcategory A, Corn Wet Milling. New Sources, redefined in response
to the Federal Court remand of May 5, 1975.
"Process waste water shall not be discharged to a POTW at a flow
rate or pollutant mass laoding rate which is excessive over any
time period during the peak load at a POTW. Excessive (peak)
discharges are defined as those in which the flow of BODr or TSS
exceed the respective values of P from the following formula,
which is based upon dry weather conditions:
P = K (Q + R) - S
Where:
P = Maximum allowable Peak waste load for the New Corn Wet Milling
Source to be discharged to the POTW (gallons per hour for flow,
and Ibs per day for BODr and TSS)
Q = Average existing waste load to POTW
R = Average waste load for the New Corn Wet Milling Source to be
discharged to the POTW
S = Existing peak load of POTW
K = 2, except when ratio of S/Q >1.5 in which case K = 3
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CANNED AND PRESERVED FRUITS AND VEGETABLES INDUSTRY
(10, 30, 132, 133, 134, 135)
[Part 407]
SUBCATEGORIZATION OF THE INDUSTRY
The industry has been divided into eight subcategories but some of the
subcategories comprise a great number of commodities as described below:
A - Apple Juice
. B - Apple Products
C - Citrus Products
D - Frozen Potato Products
E - Dehydrated Potato Products
F - Canned and Preserved Fruits, in turn including:
Apricots Grape Juice-Canning Pineapple
Caneberries Grape Juice-Pressing Plums
Cherries-Sweet Olives Raisins
Cherries-Sour Peaches Strawberries
Cherries-Brined Pears Tomatoes
Cranberries Pickles-Fresh Pack
Dried Fruit Pickles-Process Pack
Pickles-Salt Stations
G - Canned and Preserved Vegetables, in turn including:
Beets Dehydrated Vegetables Sauerkraut-Canning
Broccoli Dry Beans Sauerkraut-Cutting
Carrots Lima Beans Snap Beans
Corn-Canned Mushrooms Spinach
Corn-Frozen Onions-Creamed Squash
Dehydrated Onion' Peas Potatoes
and Garlic
H - Canned and Miscellaneous Specialties, in turn including:
Added Ingredients Ethnic Foods
Baby Food Jams and Jellies
Chips-Corn Mayonnaise and Dressings
Chips-Potato Soups
Chips-Tortilla Tomato-Starch-Cheese Canned Specialties
NATURE OF PROBLEM
In 1971, 164 apple processing plants were identified and located among
28 States. Citrus is the largest fruit crop in the U.S. Some 97 citrus
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10
plants were identified in 14 States, primarily Florida, Californa, Texas
and Arizona. In 1972, there were 112 canned and frozen potato processing
plants in 31 States. Of all potatoes processed, frozen french fries
account for 45 percent, dehydrated potatoes about 20 percent, potato
chips 30 percent, and canned potatoes the remaining 5 percent.
Excluding apples, citrus and potatoes, the industry operated more than
2,000 plants in 1967. Approximately 30 million tons of fruits and
vegetables are processed annually. It is estimated around 55 percent
of the processing plants discharge their liquid wastes to municipal
sewers, 33 percent have land disposal, and 12 percent discharge to
navigable waterways.
Although effluents from this industry are generally considered compatible
with well designed and operated biological POTW's, judgement must be
made as to the type and degree of pretreatment necessary to protect
the POTW. Citrus wastes containing citrus oil may be biologically
treated but only with difficulty. The oil also creates sludges that
are difficult to dewater. Fruit and vegetable wastes have the poten-
ial to adversely affect POTW's in many ways:
Flow Volume: The industry is frequently characterized by high volumes
of waste discharged seasonally, also having high hourly fluctuation
in flow. Flow equalization may be necessary. Installation of cool-
ing towers may serve to reduce high-volume cooling water discharges.
Organic Strength: Wastes are oftentimes high in BOD but are
compatible to POTW's provided that the municipal system has
sufficient capacity to handle the combined municipal and industrial
waste loads. In troublesome cases, pretreatment may be necessary
by the industrial plant to reduce organic loads.
Oil and Grease: Certain sectors of the industry discharge high
concentrations of oil and grease. Regulation may be required to
protect the collection system from stoppages and to safeguard the
treatment works.
Dissolved Solids: Appreciable concentration of chlorides and
other inorganic solids may be experienced by the POTW receiving
certain subcategory wastes. These constituents will pass through
the POTW and this condition may determine whether the municipality
should accept the subject wastes.
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11
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity COD
BOD Nitrogen, including Ammonia N
TSS Phosphorous
Oil/Grease IDS
Fecal Coliforms Temperature
Chlorides Peticides
pH: Low pH levels can be experienced during slicing, grinding and
macerating operations. Wastewater from steam-peeled carrots and
blanched prunes is acidic enough in some cases to require lime
treatment before final release. Conversely lye peeling waste may re-
quire neutralization with acid prior to final discharge.
IDS. Chlorides: High chlorides in wastewaters from pickle,
sauerkraut, olive and other brine processing plants may be of
significance when biological treatment is utilized. Although
aerobic biological systems may possibly adapt to high chlorides,
concentrations should be constrained to a fairly narrow range,
either by in-plant control of brine wastes or by flow equaliza-
tion. Shock loads to the biological system, can substantially
reduce treatment efficiency.
Other Pollutants: Agricultural chemicals and pesticides are
found in wastewaters from fruit and vegetables processing plants
primarily in the initial washings of raw commodities. However,
they should not constitute significant pollutants.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
No specific limitations have been prescribed to date.
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
No across-the-board unit operations are defined, although screening,
flow equalization, grease removal, and possible pH control, may be
implied for a number of fruit and vegetable processing plants.
Especially with citrus and potato wastewaters, three streams have been
found detrimental to POTW's having secondary treatment including:
spent caustic solutions from peeling operations; d'limonene from citrus
peel processing operations; and oils from frying operations. Adequate
control methods should be used to minimize effects of these particular wastes
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CANNED AND PRESERVED SEAFOOD PROCESSING INDUSTRY
(30, 104, 105, 106, 107)
[Part 408]
SUBC'ATEGORIZATION OF THE INDUSTRY
The Canned and Preserved Seafood Industry has been divided into 33 Sub-
categories. The various subcategories cover processing of catfish,
crab, shrimp, tana, fish meal, salmon, bottom fish, clam, oyster, sar-
dine, scallop, herring fillet and abalone commodities. These 33 sub-
categories are tabulated and described below.
A - Farm-Raised Catfish
B - Conventional Blue Crab Processing
C - Mechanized Blue Crab Processing
D - Non-Remote Alaskan Crab Meat Processing
E - Remote Alaskan Crab Meat Processing
F - Non-Remote Alaskan Whole Crab and Crab Section Processing
G - Remote Alaskan Whole Crab and Crab Section Processing
H - Dungeness and Tanner Crab Processing in the Continguous States
I - Non-Remote Alaskan Shrimp Processing
J - Remote Alaskan Shrimp Processing
K - Northern Shrimp Processing in the Continguous States
L - Southern Non-Breaded Shrimp Processing in the Continguous States
M - Breaded Shrimp Processing in the Continguous States
N - Tuna Processing
0 - Fish Meal Processing
P - Alaskan Hand-Butchered Salmon Processing
Q - Alaskan Mechanized Salmon Processing
R - West Coast Hand-Butchered Salmon Processing
S - West Coast Mechanized Salmon Processing
T - Alaskan Bottom Fish Processing
U - Non-Alaskan Conventional Bottom Fish Processing
V - Non-Alaskan Mechanized Bottom Fish Processing
W - Hand-Shucked Clam Processing
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X - Mechanized Clam Processing
Y - Pacific Coast Hand-Shucked Oyster Processing
Z - Atlantic and Gulf Coast Hand-Shucked Oyster Processing
AA - Steamed and Canned Oyster Processing
AB - Sardine Processing
AC - Alaskan Scallop Processing
AD - Non-Alaskan Scallop Processing
AE - Alaskan Herring Fillet Processing
AF - Non-Alaskan Herring Fillet Processing
AG - Abalone Processing
Subcategory A, Farm-Raised Catfish. Applicable to facilities processing
more than 3,000 Ibs raw material/day on any day during the calendar
year, and all New sources.
Subcategory B, Conventional Blue Crab. Manual picking or separation
of crab meat from the shell. Applicable to facilities processing more
than 3,000 Ib raw material/day on any day during the calendar year, and
all New sources.
Subcategory C, Mechanized Blue Crab. Processing of blue crab in which
mechanical picking or separation of crab meat from the shell is utilized.
Subcategories D and E, Non-Remote and Remote Alaskan Crab Meat. The pro-
cessing of dungeness, tanner and King crab meat both in Subcategories
D and E. Non-remote refers to population or processing centers in
Alaska including but not limited to Anchorage, Cordova, Juneau,
Ketchikan, Kodiak and Petersburg.
Subcategories F and G, Non-Remote and Remote Alaskan Whole Crab Sections.
The processing of dungeness, tanner and King whole crab and crab sections
both in Subcategories F and G.
Subcategories I and J, Non-Remote and Remote Alaskan Shrimp Processing.
Self explanatory.
Subcategory K, Northern Shrimp Processing in Continguous States.
Applicable to the States of Washington, Oregon, California, Maine, New
Hampshire and Massachusetts and to plants processing more than 2,000 Ib
raw material/day on any day during a calendar year, and all New sources.
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14
Subcategory L, Southern Non-breaded Shrimp Processing in Contlnguous
States. Applicable to States of North and South Carolina, Georgia,
Florida, Alabama, Mississippi, Louisiana and Texas, and to plants
processing more than 2,000 Ib raw material/day on any day during a
calendar year, and all New sources.
Subcategory M, Breaded Shrimp Processing in Continguous States. Appli-
cable to plants processing more than 2,000 Ib raw material/day on any
day during a calendar year, and all New sources.
Subcategory 0, Fish Meal Processing. Processing of menhaden on the Gulf
and Atlantic coasts and processing of anchovy on the West Coast into
fish meal, oil, and solubles.
Subcategory U, Non-Alaskan Conventional Bottom Fish Processing. Appli-
cable to processing of bottom fish outside of Alaska in which unit
operations are carried out predominately through manual methods.
However, the use of scaling machines and/or skinning machines are con-
sidered normal in this Subcategory. Commercially.processed species of
bottom fish include flounder, ocean perch, haddock, cod, sea catfish,
sole, halibut and rockfish. Subcategory U applies to plants proces-
sing more than 4,000 Ib raw material/day on any day during the calendar
year, and all New sources.
Subcategory V, Non-Alaskan Mechanized Bottom Fish Processing. Refers
to processing of bottom fish such as whiting and croaker.
Subcategory W, Hand-Shucked Clam Processing. Applies to plants proces-
sing more than 4,000 Ib raw material/day on any day during the calendar
year, and all New sources.
Subcategory Y, Pacific Coast Hand-Shucked Oyster Processing. Applicable
to plants processing more than 1,000 Ib of product (oyster meat after
shucking)/day on any day during the calendar year, and all New sources.
Subcategory Z, and Gulf Coast Hand-Shucked Oyster Processing. Same size
plant as defined for Subcategory Y.
Subcategory AA, Steamed and Canned Oyster Processing. Applies to plants
processing mechanically shucked oysters.
Subcategory AB, Sardine Processing. Applies to canning of sardines or
sea herring for sardines but the Subcategory does not cover the relatively
new steaking operations in which cutting machines are used for preparing
fish steaks.
Definitions of Subcategories not specifically cited above, are thought
to be self-explanatory.
self-
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15
NATURE OF THE PROBLEM
Quantities of waste discharged from seafood processing plants can range
from 30 to 80% or more of the weight of raw material. In many cases,
there is little or no pretreatment of seafood processing wastes, before
final discharge. Generally, major waste sources in a seafood processing
plant include: receiving, pre-processing, evisceration, pre-cooling,
picking and cleaning, shucking, preserving, canning, freezing, plant
cleanup and byproduct operations.
PARAMETERS OF IMPORTANCE
BOD
COD
Settleable Solids
TSS
Oil/Grease
pH
TKN, Ammonia and Nitrate N
Phosphorous
Coliform Bacteria
Chlorides
Temperature
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
No constituents in the waste discharges from seafood processing plants
have been found in the concentrations measured, to interfere with, pass
through, or otherwise be incompatible with well-designed and well-operated
biological POTW's. It is however, suggested that these effluents should
be passed through primary treatment in order to remove settleable solids
and excessive oils and greases. Sodium chloride levels may also be suf-
ficiently high to warrant dilution.
The Federal Regulations for Seafood Processing have determined that
Existing Sources within all 33 Subcategories be allowed entry into
municipal POTW's without pretreatment limitations. Similar definition
is given for New Sources within Subcategories 0 through AG. Pretreat-
ment for New Sources in Subcategories A through N appears to be the
same as for Existing Sources in these same Subcategories, which is
determined to be "None" although primary treatment is preferred.
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16
BEET SUGAR PROCESSING
(30, 59, 60)
[Part 409]
SUBCATEGORIZATION OF THE INDUSTRY
The Beet Sugar Processing Industry is defined as a single Subpart, i.e.
Subcategory A of the overall sugar processing industry. However, this
Subcategory has been divided into different BPT and BAT effluent limi-
tations based upon the size of plant, availability of land for waste
disposal and other criteria. Beet sugar processing plants convert raw
sugar beets into refined crystalline and liquid refined sugar.
NATURE OF THE PROBLEM
Fifty-three beet sugar processing factories were identified during the
EPA Guidelines study of the early 1970's. Twelve of these plants were
reported to be achieving zero waste discharge. Major waste streams
include flume water, lime mud slurry, diffuser water, cleaning wastes
and barometric condenser waters. Only a few sugar beet mills are
connected to municipal sewers and waste treatment systems.
PARAMETERS OF CONCERN
BOD COD
TSS Total and Fecal Coliforms
pH IDS
Temperature Nitrogen, especially Ammonia
Phosphorous
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTVJ AND PRESCRIBED TREATMENT
MEASURES
The Federal Register documents appropriate to Existing and New sugar
beet mills have described resulting effluents as essentially compatible
to receiving POTW's. No limitations have been given. It has been
determined that pretreatment is not necessary and beet sugar process
wastes may thereupon be discharged directly to a POTW.
However it is noted in the 1960's, cases of municipal plant failures or
at least significant deterioration were recorded when relatively large
quantities of beet sugar wastes were received into the municipal
system. The POTW must be both properly designed and operated to handle
large BOD and TSS loads from the sugar mill, especially heavy overloads.
Pretreatment would seem highly desirable when the sugar mill is large
in comparison to the municipal STP.
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17
CANE SUGAR REFINING
(56, 57, 58)
[Part 409]
SUBCATEGORIZATION OF THE INDUSTRY
The Cane Sugar Refining segment of the overall sugar processing industry
is divided into two Subcategories as shown below:
Subcategory B - Crystalline Cane Sugar Refining, converting
raw cane sugar into crystalline refined sugar.
Subcategory C - Liquid Cane Sugar Refining, converting raw
cane sugar into liquid refined sugar.
NATURE OF THE PROBLEM
Twenty nine domestic sugar cane refineries were identified including
plants on the mainland United States, in Hawaii and Puerto Rico. EPA
studies in the early 1970's indicated that three refineries at that
time were achieving zero discharge of pollutants to navigable waters
by means of land retention; two refineries were discharging all process
wastes to municipal treatment systems; and 10 additional refineries were
releasing all wastes except barometric condenser waters to municipal
systems. The remaining 14 plants partially treat their waste waters.
Principal water streams from cane sugar refineries include barometric
condenser cooling waters, filter cake slurry, char wash water, floor
wash waters, carbon slurries, truck and car washes, and ion exchange
regeneration water. The filter cake stream may be handled separately
in either a dry or slurry form. Both the removal of solid materials
from the incoming raw cane sugar and the biological treatment of sugar
cane refining wastes generate appreciable quantities of solid wastes
which must be disposed of at the plant site or to landfill.
PARAMETERS OF CONCERN
BOD COD
TSS Total and Fecal Coliforms
pH IDS
Temperature Nitrogen, especially Ammonia
Phosphorous
-------
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
Regulations contained in the Federal Register of March 20, 1974 have
described crystalline and liquid cane sugar refineries as discharging
compatible pollutants to POTW's. It is cautioned, however that the
filter cake slurry waste stream with its extremely high concentrations
of BOD and TSS could in some cases interfere with the operation of
publicly-owned treatment works. These situations should be controlled
by the operator of the POTW. If necessary, such highly-concentrated
wastes may be dry-handled and disposed of as solid waste. Process
wastes from Subcategory B and C plants have been determined to be
more or less amenable to treatment when directly released to a POTW.
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19
RAW CANE SUGAR PROCESSING
(54, 55)
[Part 409]
SUBCATEGORIZATION OF THE INDUSTRY
The raw cane sugar processing segment of the sugar processing industry
has been divided into five Subcategories as follows:
Subcategory D - Louisiana raw cane plants which convert sugar
cane into a raw cane sugar.
Subcategory E - Florida and Texas raw cane sugar processing plants.
Subcategory F - Hilo-Hamakua Coast raw cane plants on the Island
of Hawaii.
Subcategory G - Hawaiian raw cane plants not included in Sub-
category F.
Subcategory H - Puerto Rico raw cane plants.
NATURE OF THE PROBLEM
Raw sugar cane is grown in four states of the U. S. including Florida,
Louisiana, Texas and Hawaii, and also in the Commonwealth of Puerto
Rico. There were a total of 70 to 75 raw sugar cane factories operating
in the above areas in 1973-1974.
Waste water streams from raw cane sugar processing factories include
barometric condenser waters, filter cake slurry, ash slurries, floor
washes, excess condensates, chemical cleaning and wash waters from
evaporators and vacuum pans, and cane wash waters. Contact and non-
contact cooling waters represent additional waste streams together
with boiler blowdowns. Pollutants which enter into the effluent streams
comprise: 1) dissolved matter including sugar from the washing of sugar
cane, entrainment of sugar into the vapors of the evaporators and
vacuum pans which are condensed into the barometric waters, and spills
which are integrated into floor washings; 2) solid materials arising
from trash and extraneous matter brought into the factory with the raw
cane. Solids enter into the cane wash water stream during the washing
of the cane; into the filter cake slurry during clarification and
filtration of the juice; and into the ash slurry stream if bagasse is
burned and wet scrubbing is employed.
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20
PARAMETERS OF CONCERN
BOD COD
TSS Total and Fecal Coliforms
pH TDS
Temperature Nitrogen, especially Ammonia
Phosphorous
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTM AND PRESCRIBED TREATMENT
MEASURES
The EPA Development Document of February 1975 for the Raw Cane Sugar
Industry claims that effluents from cane sugar factories contain no
constituents that are known to be incompatible with a well-designed
and well-operated municipal waste water treatment plant, nor any
pollutants that would pass through a POTW. In general, however,
municipal treatment plants are not available to the raw cane industry
because the latter are predominately located in highly rural areas.
Quantity of solids in the waste waters discharged by a cane sugar
factory could be substantial. A judgment may be necessary as to the
amount of solids allowed to enter a municipal treatment system.
Existing municipal load and total design capacity of the POTW must be
considered. If it is determined that pretreatment for solids removal
is necessary, primary settling should be provided at the cane sugar
factory.
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21
TEXTILES MANUFACTURING
(27, 28, 136)
[Part 410]
SUBCATEGORIZATION OF THE INDUSTRY
The textiles industry is divided into seven main subcategories described
below together with additional waste load allowances for simple and complex
manufacturing operations that may be applicable for certain plants in
Subcategories D, E, and F. Further load allowances are given for "com-
mission finishing." Commission finishing refers to the finishing of
textile materials, 50% or more of which are owned by others, in mills
that are 51% or more independent. These mills must generally process
20% or more of their commissioned production through batch, non-con-
tinuous processing in contrast to the usual continuous processing.
A - Wool Scouring
B - Wool Finishing
C - Dry Processing, includes greige mills, coated fabrics,
laminated fabrics, tire cord fabric felts, carpet
tufting and carpet backing.
D - Woven Fabric Finishing
E - Knit Fabric Finishing
F - Carpet Mills
G - Stock and Yarn Dyeing and Finishing
NATURE OF PROBLEM
Of approximately 7,100 mills, knitting mills are the largest group num-
bering about 2,700, but there are also about 1,000 weaving mills of
various types, and over 1,000 plants which process miscellaneous textile
goods. "Wet" process plants probably account for less than 700 mills in
the industry.
PARAMETERS OF CONCERN
BOD TDS
TSS Ammonia and total nitrogen
COD Phosphates
Oil and grease Color
pH, acidity, Temperature
alkalinity Heavy metals including
Fecal Coliforms copper, zinc, mercury
Chromium Toxic organic chemicals
Qnl-Firla Dkian/O e-
Sulfide Phenols
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22
Color is found throughout the textile industry. Some colors are water
soluble but others are not, such as those caused by dispersed dyes. Bio-
degradability is variable. Many hues are used in dyeing and these appear
in the wastewaters. A common waste color is gray or black.
Chromium is widely used as an oxidant in the form of sodium dichromate in
vat and sulfur dyes and as an oxidant for wool dyes. Substitutes are
available but chromium is still widely used. Chromium is the most signi-
ficant heavy metal in the industry. Others are employed selectively.
Other Heavy Metals include copper salts used in some dyeing operations,
which can be harmful to biological treatment systems. Zinc nitrate is
used as a catalyst for durable press goods. Mercury may be present
but generally in relatively small quantities.
Phenols are widely used as carriers in dyeing polyesters;>and:.blerids.
Some natural materials such as lignins removed in scouring and some dye
compositions may analyze as phenols.
Sulfides originate from sodium sulfide incorporated in one or more
types of dye, and from other sulfur-containing chemicals.
Toxic Organics may be present. One such compound was Dieldrin, a
moth proofing agent used in carpets but reported as no longer employed.
Some carriers, particularly the chlorinated benzenes are considered
toxic, and should not be used in textile manufacturing.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
The Federal Register, Part 410 specifies that Pretreatment Standards for
New Sources shall for incompatible pollutants be equivalent to the
standards of performance for New Sources (numerical limits same as
BPT). Additionally, Pretreatment for Existing Sources shall, for in-
compatible pollutants, be equivalent to BPT limitations.
The Development Document of January 1974 for Textiles cites as follows
"The constituents of the wastewater from plants within the textile
industry have been found which would interfere with, pass through, or
otherwise be incompatible with a well designed and operated publicly
owned activated sludge or trickling filter wastewater treatment plant.
Wastewater constituents include grease from wool scouring operations,
latex from carpet mills and heavy metals such as chromium used in dyes.
Adequate control methods can and should be used to keep significant
quantities of these materials out of the wastewater. Dye substitutes
are available for many dyes containing heavy metals."
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23
Based upon the above, 40 CFR, Part 410 stipulates that COD, total
chromium, phenol, sulfide and oil and grease are waste pollutants which
would interfere with the operation of POTW's, pass through such works
untreated or inadequately treated or otherwise be incompatible with such
treatment works. After careful consideration, it was the opinion of the
EPA for existing sources that pretreatment should reduce COD, total
chromium, phenol, sulfide and oil and grease to the levels required by
BPCTCA.
For Subcategory A, Existing and New Sources:
Parameter
Avg. 30 Days Max. Day
(lb/1,000 Ib product)1 (lb/1,000 Ib product)1
Oil /Grease
Total Chromium
Phenol
Sulfide
COD
• 3.6
0.05
0.05
0.10
69.0
7.2
0.10
0.10
0.20
138.0
For Subcategory B, Existing and New Sources:
Total Chromium
Phenol
Sulfide
COD
0.07
0.07
0.14
81.5
0.14
0.14
0.28
163.0
For Subcategory C, Existing and New Sources:
Parameter
Avg. 30 Days Max. Day
(lb/1,000 Ib product)2 (lb/1,000 Ib product)2
COD
1.4
2.8
For Subcategory D, Existing and New Sources:
Total Chromium
Phenol
Sulfide
COD
0.05
0.05
0.10
30.0
0.10
0.10
0.20
60.0
But if "simple" manufacturing operations are employed (desizing,
fiber preparation and dyeing), COD limitations shall be incrementally
1 Ibs. product received into mill
2 Ibs. final product
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24
increased by 10 and 20 lb/1,000 Ib for 30 consecutive day and max..day
conditions, and if "complex" manufacturing operations are employed
(simple operations plus printing, waterproofing or applying stain
resistant or other fabric finishes), the above COD limitations shall be
increased by 20 and 40 lb/1,000 Ib, respectively.
For Subcategory F, Existing and New Sources:
Avg. 30 Days Max. Day
Parameter (lb/1,000 Ib product)2 (lb/1,000 Ib product)2
Total Chromium 0.02 0.04
Phenol 0.02 0.04
Sulfide 0.04 0.08
COD , 35.1 70.2
But if "complex" manufacturing operations are employed at the carpet
mill, COD limitations shall be increased by 10 and 20 lb/1,000 Ib
for 30 consecutive day and max. day conditions respectively over
the above COD levels.
For Subcategory G, Existing and New Sources:
Total Chromium 0.06 0.12
Phenol 0.06 0.12
Sulfide 0.12 0.24
COD 42.3 84.6
PRESCRIBED TREATMENT FOR DISCHARGE TO POTW
No specific treatment practices have been cited, although pretreatment
for incompatibles for existing sources is "equivalent" to BPCTA, which
in turn generally consists of screening, primary treatment and secondary
biological treatment. In-plant controls and recovery would partially
substitute for treatment. Pretreatment limitations for New Sources on
incompatibles approximates that for Existing Sources.
*Lbs final product.
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25
CEMENT MANUFACTURING INDUSTRY
(77, 78, 79)
[Part 411]
SUBCATEGORIZATION OF THE INDUSTRY
The Cement Manufacturing Industry is divided into three Subcategories.
Two of the Subcategories involve manufacturing, and the third Subcate-
gory is for plant area runoff. These are described below:
A - Nonlcaching Subcategory
B - Leaching Subcategory
C - Materials Storage Piles Runoff Subcategory
Subcategory A, Nonleaching Activities. Process in which several
mineral ingredients (limestone or other natural sources of calcium
carbonate, silica, alumina, iron and gypsum) are used in the
manufacturing of cement. Plants in this Subcategory do not contact
kiln dust with water in the process, and water is not used in wet
scrubbers to control kiln stack emissions.
Subcategory B, Leaching Activities. Processes in which several
mineral ingredients are used in the manufacture of cement. Plants
in this Subcategory contact kiln dust with water as an integral
part of the process and/or water is used in wet scrubbers to con-
trol kiln stack emissions.
Subcategory B, Materials Storage Piles Runoff. Discharges result-
ing from runoff over materials storage piles. Stored materials
include raw products, intermediate products, finished products and
waste materials associated with the manufacture of cement under
either Subcategory A or B.
NATURE OF THE PROBLEM
The cement manufacturing industry produces various types of Portland
cement to meet given specifications. In the early 1970's, there were 51
companies with 166 cement plants in operation in the U.S. and Puerto
Rico. Cement is manufactured by the continuous process, normally
interrupted only to reline the kilns. Three major steps in the produc-
tion process include: 1) the grinding and blending of raw materials;
2) clinker production; and 3) finish grinding.
Normal ingredients for cement include lime (calcium oxide), silica,
alumina, and iron. Lime is usually the largest single ingredient.
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26
Materials such as sand, clay, shale, iron ore and blast furnace slag
are subsequently added. At "wet" cement plants, materials are ground
with water and fed to the kiln in a slurry. At "dry" cement plants,
raw materials are dried, ground, and fed to the kiln in a dry state.
The ground raw materials fed to the kiln are heated to around 1600°C
to form "clinker." The clinker along with added gypsum are ground to
a fine powder representing the final product ready for shipment or use.
Dust collection is achieved by means of cyclones, electrostatic preci-
pitators, bag filters and/or wet scrubbers.
PARAMETERS OF CONCERN
pH, alkalinity Turbidity
TSS Aluminum
TDS Iron
Potassium Calcium
Sulfate Magnesium
Temperature Sodium
Chlorides
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES'
The Development Document of August 1973 indicates in general that POTW's
are not available to cement plants due to a lack of sewerage facilities.
If municipal connection is possible, the major troublesome pollutant
would most likely be high TDS in the waste waters. It may be necessary
to determine the maximum allowable load of dissolved solids to a particular
POTW.
The Federal Register of February 20, 1974 indicates existing cement
manufacturing plants do not require specific pretreatment, nor removal
of particular pollutants before entering a POTW.
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27
FEEDLOTS INDUSTRY
(52, 53)
[Part 412]
SUBCATEGORIZATION OF THE INDUSTRY
The Feedlots Industry is divided into two main subcategories, as
described below:
Subcategory A. All Feedlots Except Ducks. This subpart applies to
the following types of feedlots: beef cattle-open lots; beef
cattle-housed lots; dairy cattle-stall barn (with milk room);
dairy-free stall barn (with milking center); dairy cowyards (with
milking center); swine-open dirt or pasture lots; swine-housed,
slotted floor; swine-solid concrete floor, open or housed lot;
sheep-open lots; sheep-housed lots; horses-stables (race tracks);
chickens-broilers housed; chickens-layers (egg production),
housed; chickens-layer breeding or replacement stock, housed;
turkeys-open lots; turkeys-housed. Furthermore, limitations shall
apply only to feedlot operations equal to or larger than the
capacities presented below:
1,000 slaughter steers and heifers; 700 mature dairy
cattle; 2,500 swine weighing over 55 pounds; 10,000
sheep; 55,000 turkeys; 100,000 laying hens or broilers
when facility has unlimited continuous flow watering
systems; 30,000 laying hens or broilers when facility
has liquid manure handling system; 500 horses; and
1,000 animal units from a combination of slaughter
steers and heifers, mature dairy cattle, swine over
55 pounds and sheep.
Subcategory B, Ducks. This subpart applies to duck feedlots
equal to or larger than 5,000 ducks and covers both dry lot
and wet lot operations.
Excluded from these limitations guidelines are facilities used to
aise pets, small game and wild game.
PARAMETERS OF CONCERN
BOD Total Solids
TSS Color
pH Turbidity
TDS Odor
Temperature Nitrogen, especially Ammonia N
Fecal Coliforms Phosphorous
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28
PRELIMINARY LIMITATIONS FOR DISCHARGE TO PQTVI AND PRESCRIBED TREATMENT
MEASURES
The Federal Register of February 14, 1974 describes Subcategory A feed-
lots as generating waste materials characterized by solids, organic
materials, andnutrients. In rare cases these feedlots may have a storm
water discharge or overflows from a livestock watering system to a
POTW. Such effluents could contain high concentrations of pollutants
,in runoff. Watering system releases would have low waste concentra-
tions. Suitable capacity can be provided in the municipal treatment
works to satisfactorily handle intermittent, concentrated storm dis-
charges or continuous, low concentration livestock drinking water
overflows.
Wastes from Subcategory B establishments also contain considerable
solids, organic materials and nutrients. However, the concentration
of these pollutants is generally low and the discharge considerably
diluted.
It has been determined that wastes from Subcategory A and B feed-
lots are amenable to treatment in POTW's and may be discharged to such
works without need for pretreatment. Consequently np_ pretreatment
limitations have been developed for this industry.
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29
ELECTROPLATING AND METAL FINISHING INDUSTRY
(18, 19, 20, 21, 129)
[Part 413]
SUBCATEGORIZATION OF THE INDUSTRY
The Electroplating and Metal Finishing Industry consists of six subcate-
gories. Subcategories A, B, C include plants having essentially
electroplating operations in contrast to Subcategories D, E, F plants
conducting metal finishing operations.
A) Electroplating of Common Metals Subcategory. Electroplating
of ferrous, non-ferrous and plastic base materials by copper,
nickel, chromium, zinc, cadmium, tin, lead, aluminum and iron.
B) ' Electroplating of Precious Metals Subcategory. Electroplating
of ferrous or non-ferrous base materials by gold, silver, indiums
palladium, platinum, rhodium, ruthenium.
C) Electroplating of Specialty Metals Subcategory (Reserved).
Intended to apply to electroplating by beryllium, magnesium,
calcium, tellurium, rhenium, cobalt and mercury.
D) Amodizing Subcategory. A protective film is deposited onto
ferrous or non-ferrous objects, usually aluminum, the latter
acting as an anode.
E) Coatings Subcategory. A protective coating is applied to
ferrous or non-ferrous objects by chromating, phosphating or
immersion plating.
F) Chemical Etching and Milling Subcategory. Ferrous or non-
ferrous materials receive etching or chemical milling, and in this
process some portion of the base material is dissolved or removed.
NATURE OF PROBLEM
Metallic coatings are applied to surfaces by electrodeposition by both
independent (job) platers and captive operations associated with product
fabrication and assembly. Approximately 20,000 Companies are engaged
in metal finishing. Approximately 3,500 of these shops provide only
plating services. (Subcategories A, B, C).
An electroplating process includes cleaning, electroplating, rinsing,
and drying. Cleaning generally consists of two or more steps required
for removing grease, oil, soil and oxide films from the base metal surface
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30
and providing good electroplate adhesion. Cleaning will usually involve
a minimum of alkaline solution treatment followed by acid solution treat-
ment, and then rinsing. In electroplating, metal ions in either acid,
alkaline or neutral solutions are reduced onto cathode surfaces, which
are the work pieces being plated. Hundreds of different electroplating
solutions have been developed commercially, but only two or three types
are utilized widely for copper, zinc and cadmium. Cyanide solutions are
common for copper, zinc and cadmium. However non-cyanide alkaline solu-
tions containing pyrophosphate or other chelating agents have been
developed for zinc and copper. Acid sulfate solutions are also used
for zinc, copper and a number of other metals. Rack plating is utilized
for perhaps 90% of the surface area processed commercially.
Metal Finishing Operations (Subcategortes D, E, F) are conducted by both
independent (job) platers and captive operations associated with product
metal finishing;. Of the 15,000 to 20,000 companies involved in metal
finishing, about 1,000 of these conduct processes covered by regulations
for Subcategories D, E, and F.
PARAMETERS OF CONCERN
For Subcategp.ry A, Electroplating With Common Metals.:
Coipper Tin
Nickel Iron
Chromium, hexavalent and total IDS
Zinc COD
Cyanide, amenable to chlorine BOD
oxidation Oil/Grease
Cyanide, total Turbidity
TSS CosTor
pH, acidity, alkalinity Temperature
F T u o n d'e A1 um.t n urn
Phosphate Nitrate and: Ammonia N
Cadmium
Lead
For Subcategory B,. Electroplating. With Precious Metals:
Silver Paladium
Gold Platinum
Indium Rhodium
Osmium Ruthenium'
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31
Subcategories C through F. Parameters same as above.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
I). For Subcategory A, Electroplating With Common Metals, the limita-
tions for Existing Sources are more or less the same as BPT; and for
New Sources, they are equivalent to BAT.
a) For Existing Sources -
Avq. 30 DayMax. Day
Parameter (mg/nr/operation) (mg/m2/operation)
Copper
Nickel
Chromium, total
Chromium, hexavalent
Zinc
Cyanide, total
Cyanide, amenable to
oxidation
Fluoride
Cadmium
Lead
Iron
Tin
Phosphorous
TSS
PH
80
80
80
8
80
80
8
3200
48
80
160
160
160
3200
6.0 to 9.5
160
160
160
16
160
160
16
6400
96
160
320
320
320
6400
b) But for Small Existing Sources, defined as having less than
11 employees with a discharge less than 2,061 gals/hour, and a
production rate less than 4.9 m2/hr/employee, the following limi-
tations shall apply in lieu of the above limitations -
Cyanide, amenable
to oxidation 8 16
Cyanide, total 80 160
pH 6.0 to 9.0
c) Definitions for Existing and New Sources -
The term "m2", shall mean the area acted upon by the
coating process expressed in square meters.
The term, "operation," shall mean any step in the coating
process which is followed by a rinse, and in which a
protective film is deposited on the basic material.
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32
Additional definitions of "Operation," for Existing and New Sources
are as follows:
. • The post plating steps of chromating, if followed by a
rinse, phosphating and coloring, may be included under
the term "operation" for the purpose of calculating
effluent discharges, provided that such steps are an
integral part of the plating line.
Stripping, where followed by a rinse and conducted in
conjunction with electroplating for the purpose of
salvaging improperly plated parts, may be included
under the term "operation" for the purpose of calculat-
ing effluent discharges.
Electroless plating on non-metallic materials for the
purpose of providing a conductive surface on the base
material, preceding the actual electroplating step,
forming an integral step in the plating line and followed
by a rinse may be included under the term "operation"
for the purpose of calculating effluent discharges.
d) For New Sources -
Avg. 30 DayMax. Day
Parameter (mg/m2/operation) (mg/m2 operation)
Copper 40 80
Nickel 40 80
Chromium, total 40 80
Chromium, hexavent 4 8
Zinc 40 80
Cyanide, total 40 80
Cyanide, amenable
to oxidation 4 8
Fluoride 1,600 3,200
Cadmium 24 48
Lead 40 80
Iron 80 160
Tin 80 160
Phosphorous 80 160
TSS 1,600 3,200
pH 6.0 to 9.5
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33
II). For Subcategory B, Electroplating With Precious Metals, the
limitations for Existing Sources are more or less the same as BPT; and
for New Sources, they are equivalent to BAT.
a) 'For Existing Sources -
Avg. 30 DayMax. Day
Parameter . (mg/nr/operation) (mg/m2/operation)
Silver
Gold
Cyanide, amenable
to oxidation
Cyanide, total
Chromium, total
Chromium, hexavalent
Iridium
Osm'ium
Palladium
Platinum
Rhodium
Ruthenium
Phosphorous
TSS
PH
8
8
8
80
80
8
8
8
8
8
8
8
160
3,200
6.0 to 9.5
16
16
16
160
160
16
16
16
16
16
16
16
320
6,400
b) Additional definitions of "Operation" for Existing and New
Sources are as follows:
Stripping (see definition under Subcategory A).
Electroless plating (see definition under Subcategory A)
c) For New Sources -
Silver 4 8
Gold 4 8
Cyanide, amenable
to oxidation 4 8
Cyanide, total 40 80
Chromium, total 40 80
Chromium, haxavalent 4 8
Iridium 4 8
Osmium 4 8
Palladium 4 8.
Platinum 4 8
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34
Rhodium 4 8
Ruthenium 4 8
Phosphorous 80 160
TSS 1,600 3,200
pH 6.0 to 9.5
III). For Subcategory D, Anodizing, the limitations for Existing
Sources are more or less the same as BPT; and for New Sources, they
are equivalent to BAT.
a) For Existing Sources -
Avq. 30 DayMax. Day
Parameter (mg/m2operation) (mg/m2/operation)
Copper 45 90
Nickel 45 90
Chromium, total 45 90
Chromium, haxavalent 4.5 9
Zinc 45 90
Cyanide, total 45 90
Cyanide, amenable
to oxidation 4.5 9
Fluoride 1,800 3,600
Cadmium 27 54
Iron 90 180
Tin 90 180
Phosphorous 90 180
TSS 1,800 3,600
pH 6.0 to 9.5
b) But for Small Existing Sources, defined as having less than
11 employees with a discharge less than 2,061 gals/hour, and a
production rate less than 4.9 m2/hr/employee, the following limi-
tations shall apply in lieu of the above limitations -
Cyanide, amenable
to oxidation 4.5 9
Cyanide, total 45 90
pH 6.0 to 9.0
c) Additional definitions of Operations for Existing and New
Sources are as follows:
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35
Post plating steps (see definition under Subcategory A)
Stripping (see definition under Subcategory A).
Electroless plating (see definition under Subcategory A).
d) For New Sources -
Avg. 30 DayMax. Day
Parameter (mg/m2/operation) (rng/m2/operation)
Copper 23 45
Nickel 23 45
Chromium, total ' 23 45
Chromium, hexavalent 2.3 4.5
Zinc 23 45
Cyanide, total 23 45
Cyanide, amenable to
oxidation 2.3 45.
Fluoride 900 1,800
Cadmium 14 27
Iron 45 90
Tin 45 90
Phosphorous 45 • 90
TSS 900 1,800
pH 6.0 to 9.5
IV). For Subcategory E, Coatings, the limitations for Existing Sources
are more or less the same as BPT; and for New Sources, they are equiva-
lent to BAT.
a) For Existing Sources -
Copper 40 80
Nickel 40 80
Chromium, total 40 80
Chromium, hexavalent 4 8
Zinc 40 80
Cyanide, total 40 80
Cyanide, amenable to
oxidation 4 8
Fluoride 1,800 3,600
Cadmium 24 48
Iron 80 160
Tin 80 160
Phosphorous 80 160
TSS 1,800 3,600
pH 6.0 to 9.5
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36
b) But for Small Existing Sources, defined as having less than
11 employees with a discharge less than 2,061 gals/hour, and a
production rate less than 4.9 m2/hr/employee, the following limi-
tations shall apply in lieu of the above limitations -
Avg. 30 Day:Max. Day
Parameter (mg/rrr/aperation) (mg/m2/operation)
Cyanide, amenable
to oxidation 4 8
Cyanide, total 40 80
pH 6.0 to 9.0
c) Additional definitions of "Operation" for Existing and New
Sources are as follows:
Post plating steps (see definition under Subcategory A).
Stripping (see definition under Subcategory A).
Electroless plating (see definition under Subcategory A).
d) For New Sources -
Copper 20 40
Nickel 20 40
Chromium, total 20 40
Chromium, hexavalent 2 4
Zinc 20 40
Cyanide, total 20 40
Cyanide, amenable to
oxidation 2 4
Fluoride 900 1,800
Cadmium 12 24
Iron 40 80
Tin 40 80
Phosphorous 40 80
TSS 900 1,800
pH 6.0 to 9.5
V). For Subcategory F, Chemical Etching and Milling, the limitations
for Existing Sources are more or less the same as BPT; and for New
Sources they are equivalent to BAT.
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37
a) For Existing Sources -
Avg. 30 Day Max. Day
Parameter (mg/m2/operation) (mg/m2/operation)
Copper 60 120
Nickel 60 120
Chromium, total 60 120
Chromium, hexavalent 6 12
Zinc 60 120
Cyanide, total 60 120
Cyanide, amenable
to oxidation 9 18
Fluoride 2,400 4,800
Cadmium 36 72
Iron 120 240
Tin 120 240
Phosphorous 120 240
TSS 2,400 4.800
pH 6.0 to 9.5
b) But for Small Existing Sources, defined as having less than
11 employees with a discharge less than 2,061 gals/hour, and a
production rate less than 4.9 m2/hr/employee, the following limi-
tations shall apply in lieu of the above limitations -
Cyanide, amenable
to oxidation 4.5 9
Cyanide, total 45 90
pH 6.0 to 9.0
c) Additional definitions of "Operation" for Existing and New
Sources are as follows:
Post plating steps (see definition under Subcategory A)
Stripping (see definition under Subcategory A).
Electrolysis plating on non-metallic materials for the
purpose of providing a conductive surface on the base mate-
rial, preceeding the actual electroplating step, forming an
integral step in the plating line and followed by a rinse
may be included under the term "operation" for the purpose
of calculating effluent discharges.
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38
d) For New Sources -
Avg. 30 Day Max. Day
Parameter (mg/mVoperation) (mg/m2/operation)
Copper 30 60
Nickel 30 60
Chromium, total 30 60
Chromium, hexavalent 3 6
Zinc 30 60
Cyanide, total 30 60
Cyanide, amenable
to chlorination 5 9
Fluoride 1,200 2,400
Cadmium 18 36
Iron 60 120
Tin 60 120
Phosphorous 60 120
TSS 1,200 2,400
pH 6.0 to 9.5
PRESCRIBED TREATMENT FOR DISCHARGE TO POTW
BPT and Pretreatment for Existing Sources emphasize both end-of-line
chemical waste treatment and in-process controls. Chemical treatment
includes segregation of the acid and alkali waste streams, the chromium
stream, and the cyanide stream; cyanide destruction by oxidation; reduc-
tion of haxavalent chromium to the trivalent form; neutralization; and
co-precipitation of metals as hydroxides or hydrated oxides together
with settling to remove TSS prior to final discharge. In plant controls
include reduction of dragout of concentrated solutions, use of reclaim
tanks, still rinses, overall water conservation, and other feasible
recovery techniques.
BAT and Pretreatment for New Sources emphasize end-of-line chemical
waste treatment coupled with Best in-process controls, especially to
conserve rinse waters.
SUSPENSION AND REVOCATION OF ELECTROPLATING EFFLUENT REGULATIONS AND
GUIDELINES
On December 3, 1976, the Federal Register announced that certain effluent
guidelines and standards for the Electroplating and Metal Finishing
Industry previously published on March 28, 1974 and April 24, 1975,
merited reconsideration. Thereby, certain sections of 40 CFR Part
413 were temporarily suspended or revoked. It appears most if not
all of the pretreatment limitations may be in suspended status pending
promulgation of new pretreatment regulations expected around mid-1977.
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39
ORGANIC CHEMICALS MANUFACTURING INDUSTRY
(61, 62, 63, 64, 65 66)
[Part 414]
SUBCATEGORIZATION OF THE INDUSTRY
The Organic Chemicals Manufacturing Industry has been divided into four
main Subcategories described below as containing a total of 67 product/
process segments. Each of these Subcategories contains Phase I and
Phase II organic chemicals, the compounds varying considerably in
pollution consequence.
Subcategory A - Nonaqueous processes.
Subcategory B - Processes with process water contact only as steam
diluent quench or vent gas absorbent.
Subcategory C - Aqueous liquid phase reaction systems.
Subcategory D - Batch and semicontinuous processes.
Subcategory A, Nonaqueous Processes. These processes have minimum con-
tact between water and reactants or products. Water is not required as
a reactant or diluent, and is not formed as a reaction product.
Subcategory A, Phase I, Major Products and Processes:
Product Process
Cyclohexane Hydrogenation of benzene
Vinyl Chloride Addition of hydrochloric acid
to acetylene
BTX Aromatics Hydrotreatment of pyrolysis gasoline
BTX Aromatics Solvent extraction from reformate
Subcategory A, Phase II, Major Products and Processes:
BTX Fractional distillation
Cumene Alkylation of benzene with propylene
p-xylene Isomerization, crystallization and
filtration of mixed xylenes
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40
Subcategory B, Processes with Process Mater Contact as Steam Diluent
or Absorbent. Process water usage is in the form of dilution steam,
direct contact quench, or as an absorbent for reactor effluent gases.
Reactions are all vapor phase and carried out over solid catalysts.
Most processes have an absorber coupled with steam stripping of chemi-
cals for purification and recycle.
Subcategory B, Phase I, Major Products and Processes.
Product Process
Ethylene and Propylene
Butadiene
Butadiene
Butadiene
Methanol
Acetone
Acetaldehyde
Vinyl Acetate
Acetylene
Ethylene Oxide
Formaldehyde
Ethylene Dichloride
Vinyl Chloride
Styrene
Methyl Amines
Ethyl Benzene
Pyrolysis of naptha or liquid
petroleum gas
Co-product of ethylene
Oxidative dehydrogenation of butylene
Dehydrogenation of n-butane
Steam reforming of natural gas
Dehydrogenation of isopropanol
Oxidation dehydrogenation of ethanol
Synthesis of ethylene and acetic atid
Partial oxidation of methane
Catalytic oxidation of ethylene
Oxidation of methanol
Direct chlorination of ethylene
Cracking of ethylene dichloride
Dehydrogenation of ethyl benzene
Addition of ammonia to methanol
Alkylation of benzene with ethylene
For purposes of effluent limitations, Subcategory B, Phase I, has been
further subdivided into two classes of products i.e., B 1, with lower
allowable waste loads, and B 2 products with higher allowable waste
loads. The B 1 products include Ethylene and Propylene; Butadiene
(as a co-product of ethylene); Acetone; Ethyl Benzene; Ethylene
Dichloride; Ethylene Oxide; Formaldehyde; Methanol; Methyl Amines;
Vinyl Acetate; and Vinyl Chloride. The B 2 products include: Acetalde-
hyde; Acetylene; Butadiene (by the dehydrogenation and oxidative -
dehydrogenation of butylene); and Styrene.
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41
Subcategory B, Phase II, Major Products and Processes.
Product Process
• Adiponitrile Chlorination of butadiene
Benzole Acid and Catalytic oxidation of toluene
Benzaldehyde with air
Chloromethanes Chlorination of methyl chloride and
methane mixture
Diphenylamine Deamination of aniline
Hexamethylenediamine Hydrogenation of adiponitrile
Hexamethylenediamine Ammonolysis of 1,6-hexanediol
Maleic Anhydride Oxidation of benzene with hydro-
chloric acid
Methyl Ethyl Ketone Dehydrogenation of sec-butyl alcohol
Phthalic Anhydride Oxidation of o-xylene
Subcategory C, Aqueous Liquid Phase Reaction Systems. These systems
comprise liquid phase reactions where the catalyst is generally in
aqueous media such as dissolved or emulsified mineral salt, or acid
and caustic solutions. Continuous regeneration of catalyst systems
requires extensive water use. Substantial removal of spent inorganic
salt by-products may also be necessary.
Subcategory C, Phase I, Major Products and Processes.
Product Process
Phenol and Acetone Cumene oxidation and cleavage
Oxo Chemicals Carbonylation and condensation
Acetaldehyde Oxidation of ethylene with air
and/or oxygen
Acetic Acid Oxidation of acetaldehyde
Methyl Methacrylate Acetone cyanohydrin process
Ethylene Glycol Hydration of ethylene oxide
Acrylic Acid Synthesis with carbon monoxide
and acetylene
Acrylates Esterification of acrylic.acid
Terephthalic Acid (TPA) Nitric acid oxidation of p-xylene
(Catalytic)
Terephthalic Acid (TPA) Catalytic oxidation of p-xylene
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42
Product
Process
Polymer Grade TPA
Dimethyl Terephthalate
p-Cresol
Aniline
BisphenoT A
Caprolactam
Tetraethyl Lead
Coal Tar Products
Coal Tar Products
Purification of crude terephthalic
acid
Esterification of terephthalic acid
Sulfonation of toluene
Hydrogenation of nitrobenzene
Condensation of phenol and acetone
Oxidation of cyclohexanone
Addition of ethyl chloride to
lead amalgam
Coal tar distillation
Pitch forming
For purposes of effluent limitations, Subcategory C, Phase I was further
subdivided into four classes of products, i.e., Cl through C4, with in-
creasing allowable waste loads when progressing from C 1 through C 4. The
C 1 products include Acetic Acid; Acrylic Acid; Coal Tar Products (dis-
tillation); Ethylene Glycol; Terephthalic Acid (oxidation of p-xylene);
and Polymer Grade Terephthalic Acid. The C 2 products include:
Acetaldehyde (oxidation of ethylene with oxygen); Caprolactam; Coal Tar
(pitch forming); Phenol and Acetone; and Oxo Chemicals. The C 3 Products
include Acetaldehyde (oxidation of ethylene with air); Aniline; Bis-
phenol A; and Dimethyl terephthalate. The C 4 Products include:
Acrylates; p-Cresol; Methyl Methacrylate; Terephthalic acid (nitric acid
process); and Tetraethyl lead.
Subcategory C, Phase II, Major Products and Processes.
Product Process
Ethyl acetate
Acrylonitrile
p-AminophenoT
Calcium stearate
Hydrazine solutions
Isobutylene
Isopropanol
Sec-butyl alcohol
Esterification of ethyl alcohol
with acetic acid
Ammoxidation of propylene
Catalytic reduction of nitrobenzene
Neutralization of stearic acid
The Raschig process
Extraction from a mixture of
C 4 hydrocarbons
Hydrolysis of propylene carbohydrates
Sulfonation and hydrolysis of
mixed butylenes
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43
Subcategory D, Batch and Semi-Continuous Processes. Processes are
carried out in reaction kettles equipped with agitators, scrapers,
reflux condensers, etc., depending upon the nature of the operation.
Many reactions are liquid phase with aqueous catalyst systems. Re-
actants are transferred to batch reactors by gravity flow, pumping or
pressurization with air or inert gas. Much of the material handling
is manual, and there is limited use of automatic process control.
Filter presses and centrifuges are commonly used to separate solid
products from liquid. Where drying is required, air or vacuum ovens
are used. Cleaning of noncontinuous production equipment constitutes
a major source of process waste water.
Subcategory D, Phase II, Major Products and Processes.
Product Process
Citronellol and Gernaiol Citronella oil distillation
lonone and Methylionone Condensation and cyclization of citral
Methyl Salicylate Esterification of salicylic acid with
methanol
o-Nitroaniline Ammonolysis of o-nitrochlorobenzene
p-Nitroaniline Ammonolysis of p-nitrochlorobenzene
Plasticizers Condensation of phthalic anhydride
Tannic Acid Extraction of natural vegetable
matter
NATURE OF PROBLEM
The Organic Chemicals Industry is a highly complex and integrated in-
dustry in which there are approximately 454 Companies and 665 plants
manufacturing several thousand products. Synthetic organic chemicals
are derivative products of petroleum, natural gas and coal, which have
undergone at least one chemical conversion. The organic chemicals
industry was initially dependent upon coal as the sole source of raw
materials. However, over the last two decades the industry has moved
rapidly from coal to petroleum-based feedstocks. In recognition of the
change in raw materials, the term "petrochemical" has come into common
usage. This term commonly refers to all organic chemical products
derived from petroleum fractions and byproducts, or materials derived .
from natural gas constituents.
The organic chemicals manufacturing category consists of approximately
260 product commodities listed under SIC Code 2865 - Cyclic Inter-
mediates, Dyes, Organic Pigments and Coal Tar Crudes; and under SIC
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44
Code 2869 - Industrial Organic Chemicals not elsewhere identified.
From this list, 40 major product/process segments were selected and
incorporated into Phase I. The Phase I product/process segments re-
present approximately 75% of the production capacity in the organic
chemicals industry. Subsequently, data were developed on 27 additional
product/process segments which became known as the Phase II Study.
Guideline limitations on other product/process segments will be de-
veloped in the future.
In the Phase II Organic Chemicals area, high concentrations of Cyanide
which could be inhibitory to biological systems were observed particu-
larly in the waste streams from the manufacture of hexamethylenediamine,
adiponitrile and acryonitrile. Heavy metals in significant concentra-
tions were found in the waste streams from the following Phase II
product-process segments:
Adiponitrile Cu, Fe, Cr
Chloromethanes Fe, Cr
Hexamethylenediamine Zn
Maleic Anhydride Cd
Hydrazine Cd
Plasticizers Cu
These metals could interfere with biological treatment systems when
present in significant concentrations.
PARAMETERS OF CONCERN
BOD Iron
COD, TOC TDS
TSS ' Sulfate
Oil/grease Sulfides
Phenols Chlorides
pH, acidity, alkalinity Hardness
Cyanide Phosphorous
Ammonia N Calcium
Total Kjeldahl N Magnesium
Heavy Metals including Color
Zinc, Copper, Lead,
Chromium, Cadmium, Chlorinated hydrocarbons
Cobalt, Nickel,
Vanadium Toxicity
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45
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTM AND PRESCRIBED
TREATMENT MEASURES
The USEPA published regulations on Organic Chemicals Guidelines Limi-
tations, especially those covering the Phase II chemicals describe
effluents from these manufacturing plants as containing many hazardous
substances over and above the organic byproducts specifically cited in
the regulations. As more data becomes available on the severity of risk
resulting from exposure to the pollutants in organic plant chemical
.waste streams, additional substances and product lines will be covered
by effluent limitations guidelines.
Cyanide and copper were considered to be among the more deleterious sub-
stances referred to in the published Federal Register regulations of
January 5, 1976. Besides toxicity of individual pollutants, the waste
streams from organic chemical plants contain substances that create
multiple stress on fish and other aquatic life. These wastes also in-
troduce combinations of metals and chemicals into raw water supplies
used for drinking water, the synergistic effects of which have received
relatively little attention. The hazards which attach to organic chemi-
cal effluents are increased by the clustering of these plants on major
rivers and waterways used as drinking water sources as well as major
recreational areas.
The prevelance of organic chemicals as products, byproducts, inter-
mediate chemicals and raw materials in the nation's waters, is con-
sidered by many to be a significant threat to human health. Certain
organic chemicals, covered both by Phase I and II regulations, if
present in significant quantity are acutely toxic to people and to
aquatic life, cause cancer in test animals and man, bring about first-
generation birth deformities, or alter genetic patterns. A majority
of these organic compounds are also listed in the DHEW's Toxic Substances
List of 1974.
Many synthetic organic chemicals found in drinking water supplies of the
U.S. have resulted in concern that the organic problem may have in-
itially been grossly underestimated. The House of Representatives
Committee on Interstate and Foreign Commerce recently declared that
"more than 12,000 chemical compounds are now being used commercially,
not counting additional variants and fractions. About 500 new chemi-
cals are added each year. Many of these will find their way into the
Nation's drinking water supplies."
EPA has conducted recent surveys of contamination of drinking water by
organic chemicals. At least 187 organic compounds have been found
present in one or more randomly selected water supplies. Many of these
compounds are suspect carcinogens. This list will undoubtedly grow as
work continues in the analysis of drinking water and as analytical
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46
techniques are improved for the concentration, separation, identifi-
cation and measurement of organic compounds in drinking water. With few
exceptions, all the organic compounds found in drinking water have
also been found in the effluents of organic chemical plants under Phases
I and II regulations. Many synthetic organics have their origin only
in the discharges of organic chemical plants.
Examples are given below of products incorporated into Phase II guide-
lines limitations which have troublesome public health implications:
Cumene, p-Xylene and Adiponitrile - contained in DHEW Toxic Substances
List of 1974.
Benzoic Acid - also on the TSL, and besides having high acute toxicity,
causes skin effects.
Maleic Anhydride - cited as a carcinogen.
Phthalic Anhydride and Acrylonitrile - on the TSL; occupational exposure
standards have been established.
Hydrazine - causes neoplastic effects, i.e., growth of different or ab-
normal tissues or a tumor.
Isopropanol, Butyl Alcohol, Citronellol, lonone, Methyl Salicylate and
Nitroaniline - are all toxic and on the TSL.
Tannic Acid - has neoplastic properties.
The EPA Development Documents on Organic Chemicals published in December
1973 and November 1975 made a significant distinction between manufac-
turing plants in Subcategories A and B vs. those in Subcategories C and
D. The former group are considered likely to contain appreciable am-
ounts of free and emulsified oils of petroleum origin in the waste-
waters, whereas wastes of the latter grouping more probably will contain
significant quantities of heavy metals. Fatty acid wastewaters from the
manufacture of products in Subcategory D may contain free and emulsified
oils primarily of animal and vegetable origin.
The manufacture of acrylonitrile (included in Subcategory C) produces a
highly toxic wastewater which is very difficult to treat biologically
unless pretreatment is provided for cyanide. Cyanide levels have been
reported in the range of 500 to 1,800 mg/1. These wastes are usually
segregated from other process effluents and disposed of by incineration
or other acceptable means. They are generally not discharged to muni-
cipal collection systems. Recommended pretreatment schemes given below
assume the exclusion of acrylonitrile wastes from the POTW.
Oil separation may be required when the oil content (petroleum-based),
of a wastewater exceeds 100 mg/1. Animal and vegetable oils in fatty
acid wastewaters should also be segregated in order to minimize solids
separation problems at the municipal works.
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47
Heavy metals, if present in harmful quantities in organic chemicals
manufacturing wastes, may require pretreatment via chemical precipi-
tation to remove and/or lower these toxic materials.
Pretreatment unit operations will generally consist of a minimum of
equalization, neutralization, oil separation, and possibly phenols
and/or metals reduction.
With Suspended Growth With Fixed Growth Physical-Chemical
Biological System Biological System System
For Subcategory A and B Plants Discharging to POTW
Oil Separation and Oil Separation and Oil Separation and
Equalization Equalization Equalization
+ Neutralization and + Neutralization and + Neutralization and
Chemical Precipitation Chemical Precipitation Chemical Precipitation
For Subcategory C and D Plants Discharging to POTW
Equalization + Neutral- Equalization + Equalization +
ization + Chemical Neutralization Neutralization
Precipitation
The Federal Register of April 25, 1974 established that wastewaters from
Subcategory A, B and C industries may be discharged to POTW's pending
the above statements, except for the Subcategory C plants manufacturing
Phenol and Acetone via the Cumene process, Bisphenol A, and p-Cresol
manufacturing. Phenols are determined to be detrimental to POTW's if
these systems are not acclimated to phenolic loads. Pretreatment for
existing sources are defined as more or less equivalent to BPCTCA levels
and that for New Sources equivalent to NSPS levels as shown below:
Pretreatment for Existing and New Sources:
Avg. 30 Day Max. Day
Parameter (lb/1,000 Ib final product) (lb/1,000 Ib final product)
Phenol 0.020 0.045
REMAND/REVOCATION OF EFFLUENT GUIDELINES LIMITATIONS
In accordance with a decision of the U.S. Court of Appeals for the
Fourth District arrived at on February 10, 1976, the USEPA has revoked
all of 40 CFR, Part 414 promulgated on April 25, 1974 (i.e. Phase I)
except that portion of butadiene; and also all of 40 CFR, Part 414 pro-
mulgated and proposed on January 5, 1976 (i.e. Phase II). The Agency
intends to repromulgate the Regulations as soon as possible, using a
more adequate base. Regardless of the revocation, the discussion given
above on pretreatment should continue to be largely applicable.
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48
INORGANIC CHEMICALS MANUFACTURING INDUSTRY
(46, 47, 48, 49, 50, 51, 130)
[Part 415]
SUBCATEGORIZATION OF THE INDUSTRY
The Inorganic Chemicals Manufacturing Industry as defined to date by
the USEPA consists of 63 Subcategories covering 74 different inorganic
chemical products. These are described below:
A - Aluminum Chloride.Production
B - Aluminum Sulfate
C - Calcium Carbide
D - Calcium Chloride
E - Calcium Oxide and Calcium Hydroxide
F - Chlorine and Sodium or Potassium Hydroxide
G - Hydrochloric Acid
H - Hydrofluoric Acid
I - Hydrogen Peroxide
J - Nitric Acid
K - Potassium Metal Production
L - Potassium Dichromate
M - Potassium Sulfate
N - Sodium Bicarbonate
0 - Sodium Carbonate
P - Sodium Chloride
Q - Sodium Dichromate and Sodium Sulfate
R - Sodium Metal
S - Sodium Silicate
T - Sodium Sulfite
U - Sulfuric Acid
V - Titanium Dioxide
W - Aluminum Fluoride
X - Ammonium Chloride
Y - Ammonium Hydroxide (reserved)
Z - Barium Carbonate (reserved)
AA - Borax Production
AB - Boric Acid
AC - Bromine
AD - Calcium Carbonate
AE - Calcium Hydroxide
AF - Carbon Dioxide Production (reserved)
AG - Carbon Monoxide and Byproduct Hydrogen
AH - Chrome Pigments
AI - Chromic Acid
AJ - Copper Sulfate
AK - Cuprous Oxide (reserved)
AL - Ferric Chloride
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49
AM - Ferrous Sulfate (reserved)
AN - Fluoride Production
AO - Hydrogen
• AP - Hydrogen Cyanide
AQ - Iodine
AR - Lead Monoxide
AS - Lithium Carbonate
AT - Manganese Sulfate (reserved)
AU - Nickel Sulfate
AV - Strong Nitric Acid (reserved)
AW - Oxygen and Nitrogen production
AX - Potassium Chloride
AY -. Potassium Iodide
AZ - Potassium Permanganate (reserved)
BA - Silver Nitrate
BB - Sodium Bisulfite (reserved)
BC - Sodium Fluoride
BD - Sodium Hydrosulfide (reserved)
BE - Sodium Hydrosulfite (reserved)
BF - Sodium Silicofluoride
BG-_ Sodium Thiosulfate (reserved)
BH - Stannic Oxide
BI - Sulfur Dioxide Production (reserved)
BJ - Zinc Oxide (reserved)
BK - Zinc Sulfate
Subcategory A, Aluminum Chloride. Formed by reaction of gaseous
chlorine with molten aluminum.
Subcategory B, Aluminum Sulfate. Formed by reaction of bauxite ore
with sulfuric acid.
Subcategory C, Calcium Carbide. Reaction of calcium oxide with carbon
in uncovered high-temperature furnaces.
Subcategory D, Calcium Chloride. Produced by the brine extraction
process.
Subcategory E, Calcium Oxide and Calcium Hydroxide. Made from calcin-
ing various types of limestone in continuous vertical or rotating kilns,
Subcategory F, Chlorine and Sodium or Potassium Hydroxide. Chlorine
is produced by the electrolysis of sodium or potassium brines. Sodium
hydroxide and potassium hydroxides are byproducts. Chlorine is formed
by one of two methods: the mercury cell process and the diaphram cell
process.
Subcategory G. Hydrochloric Acid. Manufacturing utilizes the direct
reaction of chlorine with hydrogen, or hydrochloric acid is obtained
as a byproduct of organic chlorination reactions.
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50
Subcategory H, Hydrofluoric Acid. Hydrofluoric acid is produced by the
reaction of fluorospar with sulfuric acid in a furnace.
Subcategory I, Hydrogen Peroxide. Manufactured by three processes:
1) the electrolytic process; 2) oxidation of alkyl hydroanthraquinones;
and 3) as a byproduct in making acetone from isopropyl alcohol.
Limitations guidelines are applicable only for the first two processes.
Subcategory J, Nitric Acid. Produced by the catalytic oxidation of
ammonia to nitrogen dioxide which in turn is reacted with water vapor
under pressure to obtain nitric acid.
Subcategory K, Potassium Metal. Results from the reaction of potassium
chloride with sodium vapors.
Subcategory L, Potassium Pi chromate. Results from the reaction of
sodium dichromate dihydrate solution with potassium chloride.
Subcategory M. Potassium Sulfate. A naturally-occurring potassium
magnesium sulfate ore is reacted with potassium chloride to yield
potassium sulfate.
Subcategory N, Sodium Bicarbonate. Sodium carbonate is reacted with
water and carbon dioxide under pressure to yield sodium bicarbonate.
Subcategory 0, Sodium Carbonate (Soda Ash). Produced by the Solvay
process, or by the mining of trona (sodium sesquicarbonate). The
Solvay process reacts ammonia and carbon dioxide in a brine solution
to yield sodium bicarbonate. Heating converts the bicarbonate to
carbonate. Ammonia can be recovered by adding slaked lime to the
used liquor.
Subcategory P, Sodium Chloride. Produced by solution brine mining;
by solar evaporation of sea water; or by conventional mining of rock
salt. Effluent limitations apply only to the first two processes.
Subcategory Q, Sodium Dichromate and Sodium Sulfate. These chemicals
are prepared by calcining chrome ore, sodium carbonate and lime, which
is followed by leaching with water.
Subcategory R, Sodium Metal. The metal is generated during the
electrolysis of fused sodium chloride, i.e. the Downs cell process.
Subcategory S, Sodium Silicate. Soda ash or anhydrous sodium hydroxide
is reacted with silica to yield sodium silicate.
Subcategory T, Sodium Sulfite. The reaction of sulfur dioxide with
soda ash.
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51
Subcategory U, Sulfuric Acid. The sulfur burning contact process is
used in both single and'double adsorption plants. The effluent limi-
tations are not applicable to plants burning sulfides, or recovering
sulfuric acid from waste streams of other processes such as oil refining
or metallurgical operations.
Subcategory V, Titanium Dioxide. Produced by the sulfate process and
by the chloride process. The effluent limitations are not applicable
to processes in which benefication of raw ilmenite ore and chlorination
are inseparably combined in the same process step.
Subcategory W, Aluminum Fluoride. Formed by the reaction of hydrated
alumina with hydrogen fluoride.
Subcategory X, Alumimum Chloride. Guidelines cover the formation of
aluminum chloride by reacting anhydrous ammonia with hydrogen chloride
gas; or by extracting aluminum chloride from waste mother liquors using
the Solvay process in producing sodium carbonate.
Subcategory AA, Borax. Produced by mining and extraction from borax
ore, and also by the Trona process.
Subcategory AB, Boric Acid. Made by reacting borax and sulfuric acid.
Boric acid is also produced by the Trona process utilizing liquid-
liquid solvent extraction-evaporative crystallization operations.
Subcategory AC, Bromine. May be produced by the Trona process, or by
extraction from well brines.
Subcategory AD, Calcium Carbonate. Produced by various processes.
One process involves reaction of slaked lime with carbon dioxide.
Other methods react selected waste streams from the Solvay process
used to manufacture sodium carbonate.
Subcategory AE, Calcium Hydroxide. Reaction of calcium oxide with
water.
Subcategory AG, Carbon Monoxide and Byproduct Hydrogen. Methane, air
and water are catalytically reacted to form a mixture of carbon monox-
ide, carbon dioxide, and hydrogen. The carbon monoxide and hydrogen
are separated and purified.
Subcategory AH, Chrome Pigments and Iron Blues. A number of pigments
are included in the chrome pigments Subcategory. Iron blues are
formed by reaction of ferrous sulfate with sodium ferrocyanide in the
presence of ammonium sulfate. Chrome pigment wastewaters usually con-
tain chromium, lead, zinc, iron, cyanide, dissolved sodium salts and
acetates.
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52
Subcategory AI, Chromic Acid. Waste liquors from sodium dichromate
manufacturing are reacted with sulfuric acid to yield chromic acid.
Subcategory AJ, Copper Sulfate. Copper sulfate can be produced from
a pure copper raw material or from impure copper sources. A pure
copper raw material is reacted with sulfuric acid, air and water. A
waste stream from a copper refinery may also be fed to an oxidizer
tank and reacted with copper shot, steam and air to yield copper sul-
• fate.
Subcategory AL, Ferric Chloride. Produced from waste pickle liquor
by reacting with iron, chlorine and sometimes hydrochloric acid.
Subcategory AN, Fluoride. Formed from the electrolysis of hydrogen
fluoride. The reaction either involves direct electrolysis of liquid
hydrofluoric acid, or an electrolysis of fused salts containing potas-
sium acid fluoride.
Subcategory AO. Hydrogen. Generally obtained from the refining and
purification of crude hydrogen obtained as refinery byproduct gas.
Subcategory AP, Hydrogen Cyanide. Manufactured by the Andrussow
process and also derived as a byproduct of acrylonitrile manufacturing.
Hydrogen cyanide receives refining and purification in both processes.
Subcategory AQ, Iodine. Obtained from brine solutions containing
iodide.
Subcategory AR. Lead Monoxide. Produced by the thermal oxidation of
lead.
Subcategory AS, Lithium Carbonate. Manufactured by the Trona process
and/or from spodumene ore.The latter involves reacting the ore with
sulfuric acid. In the Trona process, a solid residue is reclaimed
from potassium chloride and bromine production. This residue is with-
drawn as dilithium sodium phosphate which in turn is reacted with
sulfuric acid yielding lithium sulfate. Lithium sulfate is reacted
with sodium carbonate to give the desired end product.
Subcategory All, Nickel Sulfate. Produced from pure nickel, from nickel
oxide and from impure nickel substances. The pure metal or pure oxide
is digested in sulfuric acid. When impure nickel is used, the sulfuric
acid reaction solution must be treated with oxidizers to remove impuri-
ties.
Subcategory AW. Oxygen and Nitrogen. Process involves distillation of
liquefied air. Air is compressed, cooled and then separated into nitro-
gen and oxygen by distillation.
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53
Subcategory AX, Potassium Chloride. Produced by the Trona process and/
or by extraction from sylvite ore which is a potassium chloride-sodium
chloride mineral. In the Trona process, a brine solution is concentrated
and potassium chloride recovered. When sylvite ore is used, it is ground and
converted into a brine solution from which potassium chloride is reclaimed.
Subcategory AY, Potassium Iodide. Potassium hydroxide is reacted with
iodine.
Subcategory BA, Silver Nitrate. Silver is dissolved in nitric acid.
Subcategory BC, Sodium Fluoride. Two processes are used. Anhydrous
hydrofluoric acid is reacted with sodium carbonate and sodium fluoride
eventually recovered. Also, sodium silicofluoride can be reacted with
sodium hydroxide and sodium fluoride separated and purified.
Subcategory BF, Sodium Silicofluoride. Fluorosilicic acid is reacted
with sodium chloride. Sodium silicofluoride is alternately manufactured
by reacting impure phosphoric acid containing fluorides with sodium
carbonate.
Subcategory BH, Stannic Oxide. Two processes are available. In a dry
process, metallic tin is thermally reacted with oxygen. In the second
process, tin is recovered from scrap materials and subsequently oxidized.
Subcategory BK. Zinc Sulfate. Sulfuric acid is reacted with crude zinc-
containing materials.
NATURE OF THE PROBLEM
In many inorganic chemical manufacturing processes, wet scrubbers are
used to control air pollution. The scrubbing solution is generally
treated and may be reused. Operations for treating process wastewater
in the inorganic chemicals manufacturing industry include settling,
filtration, chemical coagulation, ion exchange, carbon adsorption and
evaporation. Some treatment processes may generate large volumes of
sludge in turn creating a substantial solid waste problem. Landfill
or lagoon sites of adequate size and good design may be essential.
PARAMETERS OF CONCERN
Primary Parameters include:
• pH, Acidity, Alkalinity Cadmium
COO, TOC Iron
TSS Lead
Chromium Mercury
Arsenic Cyanide
Fluoride
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54
Parameters of slightly less importance:
Oil/Grease
Boron
IDS
Ammonia N
Nitrate and Nitrite N
Fluoride
Chloride
Sulfate
Sulfite
Phosphate
Phenols
Silicates
Barium
Chlorinated Hydrocarbons
Cyclic Hydrocarbons
Temperature
Aluminum
Selenium
Copper
Manganese
Molybdenum
Nickel
Tin
Titanium
Vanadium
Zinc
Silver
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
For Subcategories A through U, Pretreatment for Existing Sources has
been established equivalent to BPCTCA limitations and Pretreatment for
New Sources has been made equivalent to New Source Performance Standards,
It is further indicated where the effluent limitation guidelines based
on BPCTCA are not defined for incompatible pollutants (such as TDS), no
pretreatment will be required for such incompatible pollutant unless
persuant to 40 CFR 128, the wastes interfere with the operation or per-
formance of the POTW, or pretreatment is required by local or
law. As best as can be determined, pretreatment criteria are those
shown below:
For Subcategory A, Existing and New Sources of Aluminum Chloride
Production
No discharge allowed.
For Subcategory B, Existing and New Sources of Aluminum Sulfate
Production.
Essentially no discharge except for low frequency runoff. No limita-
tions are given for incompatibles.
For Subcategory C. Existing and New Sources of Calcium Carbide
Production.
No discharge.
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55
For Subcategory D, Existing Sources of Calcium Chloride Production.
Discharge allowed. No limitations given for incompatible pollutants.
For Subcategory D, New Sources of Calcium Chlorj'de Production.
No discharge.
For Subcategory E, Existing and New Sources of Calcium Oxide and
Calcium Hydroxide Production.
See explanation under Subcategory B.
e
For Subcategory F, Existing Chlorine Production Source, Mercury Cell
Process.
Avg. 30 DayMax Day
Parameter (1b/1000 1b final product)(1b/1 OOP 1b final product)
Mercury .00014 .00028
For Subcategory F, Existing Chlorine Production Source, Diaphram
Process.
Lead .0025 .005
For Subcategory F, New Chlorine Production Source, Mercury Cell Process.
Mercury .00007 .00014
For Subcategory F, New Chlorine Production Source, Diaphram Process.
Lead .00004 .00008
For Subcategory G. Existing and New Sources of Hydrochloric Acid
Production.
No discharge.
For Subcategory H, Existing Sources of Hydrofluoric Acid Production.
Fluoride .18 and up to .36 (and up
30 mg/1) to 60 mg/1)
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56
For Subcategory H, New Sources of Hydrofluoric Acid Production.
Avg. 30 Day Max Day
Parameter . (lb/1000 Ib final product)(lb/1000 Ib final product)
Fluoride 0.12 and up to 0.24 (and up
25 nig/1) to 50 mg/1)
For Subcategory I, Existing Sources of Hydrogen Peroxide Production by
Oxidation of Alkyl Hydroanthraquinones.
TOC 0.22 0.44
For Subcategory I, Existing Sources of Hydrogen Peroxide Production by
Electrolytic Process.
Cyanide, amenable .0002 .0004
to chlorine
oxidation
For Subcategory I, New Sources of Hydrogen Peroxide Production by
Oxidation of Alkyl Hydroanthraquinones.
No discharge.
For Subcategory I, New Sources of Hydrogen Peroxide Production by
Electrolytic Process.
See explanation under Subcategory B.
For Subcategory J, Existing and New Sources of Nitric Acid Production.
No discharge.
For Subcategory K, Existing and New Sources of Potassium Metal
Production.
No discharge.
For Subcategory L, Existing and New Sources of Potassium Dichromate
Production.
No discharge.'
For Subcategory M, Existing and New Sources of Potassium Sulfate
Production.
See explanation under Subcategory B.
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57
For Subcategory N, Existing and New Sources of Sodium Bicarbonate
Production..
No discharge.
For Subcategory 0, Existing Sources of Sodium Carbonate Production.
Discharge allowed. No limitations given for incompatibles.
For Subcategory 0. New Sources of Sodium Carbonate Production.
No discharge.
For Subcategory P, Existing Sources of Sodium Chloride Production.
Discharge allowed. No limitations given for incompatibles.
For Subcategory P. New Sources of Sodium Chloride Production.
No discharge.
For Subcategory Q, Existing and New Sources of Sodium Dichromate and
Sodium Sulfate Production.
Avg. 30 DayMax Day
Parameter (lb/1000 Ib final product) (lb/1000 Ib final product)
Chromium, hexavalent .0005 .009
chromium, total .0044 .0088
For Subcategory R, Existing Sources of Sodium Metal Production.
Discharge allowed. No limitations given for incompatibles.
For Subcategory R, New Sources of Sodium Metal Production.
See explanation under Subcategory B.
For Subcategory S. Existing Sources of Sodium Silicate Production.
Discharge allowed. No limitations given for incompatibles.
For Subcategory S, New Sources of Sodium Silicate Production.
See explanation under Subcategory B.
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58
For Subcategory T, Existing Sources of Sodium Sulfite Production.
Avg. 30 DayMax Day
Parameter (lb/1000 Ib final product)(lb/1000 Ib final product)
COD 1.7 3.4
For Subcategory T, New Sources of Sodium Sulfite Production.
No discharge.
For Subcategory U, Existing and New Sources of Sufuric Acid Production.
No discharge.
For Subcategory V. Existing Sources of Titanium Dioxide Production by
the Chloride Process.
Iron 0.36 0.72
For Subcategory V, Existing Sources of Titanium Dioxide Production by
the Sulfate Process.
Iron 1.7 3.4
For Subcategory V, New Sources of Titanium Dioxide Production by the
Chloride Process.
Iron 0.18 0.36
For Subcategory V, New Sources of Titanium Dioxide Production by the
Sulfate Process.
Iron 0.42 0.84
For Subcategory W, Existing Sources of Aluminum Fluoride.
Aluminum 0.17 0.34
Fluoride 0.34 0.68
For Subcategory W. New Sources of Aluminum Fluoride.
Aluminum 0.017 0.034
Fluoride 0.034 0.068
For Subcategory X, Existing and New Sources of Ammonium Chloride.
Ammonia N 0.5 1.0
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59
For Subcategory AA, Existing and New Sources of Borax Production.
Parameter Pretreatment Standard
Boron as B 1 mg/1
Arsenic as As 1 mg/1
Residual brine and depleted liquors may be returned to the body of
water from which the process brines were originally withdrawn.
For Subcategory AB, Existing and New Sources of Boric Acid Production
by Trona Process.
Arsenic as As 0.5 mg/1
Boron as B 1.0 mg/1
Residual brine and depleted liquors may be returned to the body of
water from which the process brines were originally withdrawn.
For Subcategory AB, Existing and New Sources of Boric Acid Production
From Ore Mined Borax.
Avg. 30 Day Max. Day
Parameter (IbjflOOO Ib. final product) (lb/1000 Ib final product)
Arsenic .0014 .0028
For Subcategory AC, Existing and New Sources of Bromine Production.
Parameter Pretreatment Standard
Free Bromine (molecular) 0.1 mg/1
Residual brine and depleted liquors may be returned to the body of
of water from which the process brines were originally withdrawn.
For Subcategory AD, Existing and New Sources of Calcium Carbonate
Production.
No Limitations.
For Subcategory AE, Existing and New Sources of Calcium Hydroxide.
No Limitations.
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60
For Subcategory AG, Existing Sources of Carbon Monoxide and Byproduct
Hydrogen Production.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib final product)(lb/1000 Ib final product)
COD 0.25 0.5
For Subcategory AG, New Sources of Carbon Monoxide and Byproduct
Hydrogen Production
COD 0.125 0.25
For Subcategory AH, Existing Sources of Chrome Pigments Production.
Chromium, total 0.034 0.10
Chromium, hexavalent 0.0034 0.01
Lead 0.14 0.42
Zinc At 0.27 0.72
Cyanide Att 0.0034 0.01
Cyanide 0.034 0.10
Iron 0.27 0.72
For Subcategory AH. New Sources of Chrome Pigments Production.
Chromium, total 0.017 0.051
Chromium, hexavalent 0.0017 0.0051
Lead 0.033 0.099
Zinc At • 0.67 0.20
Cyanide Att 0.0017 0.0051
Cyanide 0.017 0.051
Iron 0.067 0.20
For Subcategory AI, Existing and New Sources of Chromic Acid Production,
Pretreatment
Parameter Standard
Total Chromium 0.5 mg/1
t Zinc limitatation is based on production of Zinc yellow.
tt Cyanides amenable to chlorination.
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61
For Subcategory AJ, Existing and New Sources of Copper Sulfate Produc-
tion Using Pure Copper Raw Material
Avg. 30 Day Max. Day
Parameter (lb/1000 1b. final product)(lb/1000 Ib. final product)
Copper 0.0002 0.0006
For Subcategory AJ, Existing Sources of Copper Sulfate Production
from Impure Copper.
Copper 0.001 0.003
Nickel 0.002 0.006
Selenium 0.0005 0.0015
For Subcategory AJ, New Sources of Copper Sulfate Production from
Impure Copper.
Copper 0.00046 0.0014
Nickel 0.00046 0.0014
Selenium 0.00023 0.00069
For Subcategory AK, Existing and New Sources of Ferric Chloride
Production.
Pretreatment
Parameter Standard
Iron 4 mg/1
For Subcategory AN, Existing and New Sources of Fluorine Production,
Fluoride 20 mg/1
For Subcategory AO, Existing and New Sources of Hydrogen Production.
Oil/Grease 100 mg/1
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62
For Subcategory AP, Existing Sources of Hydrogen Cyanide Production
by Andrussow Process.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Cyanide 0.025 0.05
Cyanide, amenable to 0.0025 0.005
chlorine oxidation
Ammonia as N 0.18 0.36
For Subcategory AP, Existing Sources of Hydrogen Cyanide Production
from Acrylonitrile Wastes.
Parameter Pretreatment
Standard
Cyanide 0.5 mg/1
Cyanide, amenable to 0.05 mg/1
chlorine oxidation
For Subcategory AP, New Sources of Hydrogen Cyanide Production by
Andrussow Process.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Cyanide 0.0023 0.0046
Cyanide, amenable to 0.00023 0.00046
chlorine oxidation
Ammonia as N 0.016 0.032
For Subcategory AP, New Sources of Hydrogen Cyanide Production from
Acrylonitrile Wastes.
Pretreatment
Parameter Standard
Cyanide 0.5 mg/1
Cyanide, amenable to 0.05 mg/1
chlorine oxidation
Ammonia as N 30.0 mg/1
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63
For Subcategory AQ, Existing and New Sources of Iodine Production.
No Limitations.
For Subcategory AR, Existing and New Sources of Lead Monoxide Production.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Lead 0.015 0.030
For Subcategory AS, Existing and New Sources of Lithium Carbonate
Production.
No Limitations.
For Subcategory AU, Existing and New Sources of Nickel Sulfate Produc-
tion from Pure Materials.
Pretreatment
Parameter Standard
Nickel 2 mg/1
For Subcategory AU, Existing and New Sources of Nickel Sulfate Produc-
tion from Impure Raw Materials.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Nickel 0.002 0.006
For Subcategory AW, Existing and New Sources of Oxygen and Nitrogen
Production.
Pretreatment
Parameter Standard
Oil/Grease 100 mg/1
For Subcategory AX, Existing and New Sources of Potassium Chloride
Production.
No Limitations.
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64
For Subcategory AY, Existing Sources of Potassium Iodide Production.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Sulfide 0.005 0.015
Iron 0.005 0.015
Barium 0.003 0.009
For Subcategory AY, New Sources of Potassium Iodide Production.
Sulfide 0.0036 0.0069
Iron 0.0036 0.0069
Barium 0.0023 0.011
For Subcategory BA, Existing Sources of Silver Nitrate Production.
Silver 0.003 0.009
For Subcategory BA, New Sources of Silver Nitrate Production.
Silver 0.0015 0.0045
For Subcategory BC, Existing and New Sources of Sodium Fluoride
Production.
Pretreatment
Parameter Standard
Fluoride 20/mg/l
For Subcategory BF. Existing and New Sources of Silicofluoride
Production.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib. final product)(lb/1000 Ib. final product)
Fluoride 0.25 0.50
For Subcategory BG, Existing and New Sources of Stannic Oxide Production.
No Liimttatiions.
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65
For Subcategory BK, Existing and New Sources of Zinc Sulfate Production.
Pretreatment
Parameter Standard
Cadmium 1.0 mg/1
REMAND AND REVOCATION OF INORGANIC CHEMICALS MANUFACTURING EFFLUENT
REGULATIONS AND GUIDELINES
n November 23, 1976, the Federal Register announced that certain
effluent guidelines and standards for the Inorganic Chemicals Produc-
tion Industry merited reconsideration and/or change. Thereby, certain
sections of 40 CFR Part 415 were withdrawn or temporarily suspended.
Regarding pretreatment standards, the following revisions were made
effective by the USEPA.
A. Pretreatment Standards for Existing Sources.
Subcategories W - Aluminum Fluoride; AH-Chrome Pigments; AP-
Hydrogen Cyanide; and BF-Sodium Silicofluoride have been withdrawn,
B. Pretreatment Standards for New Sources.
Subcategories G-Hydrochloric Acid; H-Hydrofluoric Acid; I-Hydrogen
Peroxide; J-Nitric Acid; 0-Sodium Carbonate; R-Sodium Metal; S-
Sodium Silicate; U-Sulfuric Acid; V-Titanium Dioxide; W-Aluminum
Fluoride; AH-Chrome Pigments; AP-Hydrogen Cyanide; and BF-Sodium
Silicofluoride have either been remanded and/or revoked.
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66
PLASTICS AND SYNTHETICS MATERIALS MANUFACTURING INDUSTRY
(156, 157, 158, 159, 160, 161, 162)
[Part 416]
SUBCATEGORIZATION OF THE INDUSTRY
The Plastics and Synthetics Manufacturing Industry involves a diverse
series of processing and products as described below. Twenty-one
subcategories have been established to date by the USEPA with additional
subcategories scheduled for adoption in the future. The 21 subcategories
are described below:
A - Polyvinyl Chloride Manufacturing
B - Polyvinyl Acetate
C - Polystyrene
D - Polypropylene
E - Polyethylene
F - Cellophane
G - Rayon
H - Acrylonitrile - Butadiene - Styrene (ABS) and Styrene -
Acrylonitrile (SAN) Resin Copolymers
I - Polyester
0 - Nylon 66
K - Nylon 6
L - Cellulose Acetate
M - Acrylics
N - Ethylene - Vinyl Acetate Copolymers
0 - Polytetrafluoroethylene
P - Polypropylene Fiber
Q - Alkyds and Unsaturated Polyester Resins
R - Cellulose Nitrate
S - Polyamide (Nylon 6/12)
T - Polyester Resins (Thermoplastic)
U - Silicones
Subcategory A, Polyvinyl Chloride. Includes plants employing poly-
merization reaction of vinyl chloride by bulk polymerization, suspension
polymerization, or emulsion polymerization.
Subcategory B. Polyvinyl Acetate. Polymerization of polyvinyl acetate
and associated processes.
Subcategory C, Polystyrene. Refers to plants utilizing the polymeriza-
tion reaction of Styrene by suspension polymerization or by bulk poly-
merization, and the processing associated with polystyrene manufacturing.
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67
Subcategory D, Polypropylene. Applies to the polymerization reaction
of polypropylene and processes associated with the manufacture of poly-
propylene.
Subcategory E, Polyethylene. Includes plants producing low-density
polyethylene by the polymerization of ethylene; and the manufacture
of high-density polyethylene by the polymerization of ethylene by the
solvent process or by the polyform process.
Subcategory F, Cellophane. The processing of wood pulp to produce
cellophane together with associated manufacturing.
Subcategory G, Rayon. The processing of wood pulp to produce rayon and
associated manufacturing.
Subcategory H, Acrylonitrile-Butadiene-Styrene (ABS) and Styrene-
Acrylonitrile (SAN) Resin Copo1ymers"i Includes plants utilizing
polymerization of acrylonitrite, butadiene and styrene, together
with the various associated processing to make ABS and SAN resins.
Subcategory I, Polyesters. Refers to plants utilizing polymerization
of dihydric alcohol and terephthalic acid or dimethyl terephthalate,
and subsequent processing for the manufacture of polyester fibers.
Subcategory J, Nylon 66. Polymerization of hexamethylene diamine
and adipic acid together with associated processing for the manufacture
of nylon 66 resin and/or the fiber.
Subcategory K, Nylon 6. Refers to the polymerization of caprolactum
and the various associated processing used to make nylon 6 resin
and/or the fiber.
Subcategory L, Cellulose Acetate. Processing of wood pulp with acetic
acid and acetic anhydride, together with the various associated process-
ing for the manufacture of cellulose acetate fibers and/or the resins.
Subcategory M, Acrylics. Polymerization of acrylonitrile and the
copolymerization of acrylonitrile and vinylidene chloride and/or
vinyl chloride to make acrylic resins and fibers.
Subcategory N, Ethylene-Vinyl Acetate. Reaction of vinyl acetate and
ethylene monomers by polymerization in order to produce ethylene vinyl
acetate copolymers.
Subcategory 0, Polytetrafluoroethylene. The manufacture of granular
and fine powder grades of polytetrafluoroethylene together with the
production of the monomer from the precursor, chlorodifluoromethane.
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68
Subcategory P, Polypropylene Fibers. Applies to plants manufacturing
polypropylene fibers from polypropylene.
Subcategory Q. Alkyds and Unsaturated Polyester Resins. Involves
complex polymerization processing.
Subcategory R, Cellulose Nitrated Fibrous cellulose is reacted with a
mixture of sulfuric and nitric acids to manufacture cellulose nitrate.
Subcategory S, Polyamide (Nylon 6/12). Production of Nylon 6/12.
Subcategory T. Polyester Resins (Thermoplastic). The manufacturing of
saturated polyester polymers based on poly (ethylene terephthalate) and
poly (butylene terephthalate), together with associated processing.
Subcategory U, Silicones. Applicable to plants manufacturing silicone
fluids, greases, emulsions, rubber and resins.
NATURE OF PROBLEM
The plastics and synthetics industry is more or less comprised of
three segments: manufacture of raw materials or monomers; conversion
of monomers into resin or plastic material; and the conversion of this
plastic material into plastic items such as toys, synthetic fibers,
packaging film, adhesives, paints, etc. The effluent guidelines for
the plastics and synthetics industry mainly cover the manufacturing
of the plastic or synthetic resins. However, they also include the
production of synthetic fibers such as nylon, polyester, and acrylic
fibers; and man-made cellulosic fibers including rayon and cellulose
film, namely cellophane. The synthetic fibers have been growing in
importance whereas the cellulosic fibers are declining in use.
In the plastics and synthetics industry, the major oil companies and
others have integrated from oil and monomer raw material production
into resin manufacture. A number of chemical companies have also
integrated back to raw materials and forward into end products. In
many cases, a given facility will produce monomer, polymers and the
end products. The large volume commodity resins, generally comprise
part of a petrochemical complex which may include production of the
monomer (such as ethylene), and the production of end products (such
as film). Because of dependency on petroleum and gas feedstocks,
many petrochemical plants are located on the Gulf coast. The petro-
chemical complexes may ship their intermediate products to resin and
plastic manufacturers located closer to the market areas.
Polymerization in very simplistic terms, involves the splitting of a
double carbon bond hydrocarbon monomer and rearrangement to form a
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69
long-chain polymer compound with normal carbon bond linking. Catalysts
and modifiers are employed to initiate and control the polymerization
reaction. Upon leaving the reactor, the polymer contains unreacted
monomer and various contaminants and byproducts. The latter are vacuum
distilled, condensed, recovered and/or sent to the sewer. Processes
for removal and/or recovery of catalyst may generate significant process
wastes.
Subcategories A Through M. Cellophane involves viscose preparation
from wood pulp and alkali cellulose., film casting and coating. In
rayon manufacturing, the processes basically comprise viscose prepara-
tion from wood pulp and fiber spinning. Polyester fiber is made from
the molten fiber passed through a spinerette and then cooled, and
formed into staples or coils. Nylon fibers are manufactured in the
form of staple bales, continuous yarn or textile filaments. Acrylic
fibers are made through both wet and dry spinning methods and shipped
in staple form.
Subcategories N Through U. Ethylene-vinyl acetate copolymers are often
made in facilities manufacturing polyethylene. In the final process
step, the EVA pellets are remelted9 combined with additives and
repelletized. Many of the uses of the EVA final product involve
direct contact with food. Polytetrafluoroethylene is the most important
of the fluorocarbon polymers,, and is polymerized from the monomer,
tetrafluoroethylene. The monomer is generated via a continuous process
based on pyrolysis of chlorodifluoromethene. In polypropylene fiber
manufacture, polypropylene flake is colored, melted and extruded as
pellets. The pellets are passed through a spinerette, cooled and
drawn and converted into monofilaments, fibers or film. Polypropylene
fiber is employed in carpets and for various textile needs. The
alkyd and unsaturated polyester resins differ principally in that for
the alkyds the acid component is supplied by long chain unsaturated
acids vs. phtholic and maleic anhydrides used in the unsaturated poly-
esters. Alkyd resins are mainly used in paint formulations and molding
compounds. The unsaturated polyester resins are mainly used in the
manufacture of plastic reinforced with glass and metallic fibers, etc.
Cellulose nitrate or nitrocellulose generates wastewater containing
acids and alcohols lost from processing. Nylon 6/12 (DuPont) resins
are produced in somewhat similar fashion as Nylon 66 above except that
sebacic acid is used rather than adipic acid. The Thermoplastic
saturated polyester resins mostly used for molding materials, are
formed from polymerization using ethylene glycol and either dimethyl
terephthalate (DMT) or terephthalic acid (TPA). Silicones encompass
a wide variety of products with complex processing. Typical opera-
tions at a single silicone plant may include production of methyl
chloride, varied methyl chlorosilanes and other chlorosilanes, the
hydrolysis of dimethyl dlchlorosilane, a range of silicone resins,
elastomer products, and specialties comprising surfactants, coupling
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70
agents, fluorosilicones, etc. Solvents, acids, heavy metals, and
fluorides may be generated in silicone manufacturing wastewaters.
Available data show that treated effluents from plastics and synthetics
manufacturing plants generally have relatively high COD/BOD ratios
denoting large amounts of refractory residual remaining after conven-
tional treatment. This seems to be especially true of acrylic plants
and treatment of waste from this type of manufacturing represents one
of the most difficult situations in the industry. Waste equalization
appears to be a prerequisite for satisfactory treatment of plastics
and synthetics manufacturing effluents.
PARAMETERS OF CONCERN
Primary parameters include:
BOD Zinc
COD Phenolic compounds
TSS Chromium
pH, Alkalinity, Acidity
Other important parameters comprise:
Iron Nitrogenous compounds
Aluminum IDS
Nickel Oil/Grease
Vanadium Color
Titanium Turbidity
Molybdenum Phosphates
Cobalt Sulfides
Copper Magnesium
Cadmium Antimony
Cyanide Temperature
Mercury Manganese
Fluorides Polychlorinated organics
Lead Toxic compounds
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTV1
For Subcategories A Through F. i.e. Polyvinyl Chloride, Polyvinyl
Acetate, Polystyrene, Polypropylene, Polyethylene and Cellophane
Manufacturing, Existing Sources. No limitations presently prescribed
for process wastes to POTW's.
For Subcategories G Through M, i.e. Rayon, ABS and SAN Resin Copolymers,
Polyester, Nylon 66, Nylon 6. Cellulose Acetate and Acrylics, Existing
Sources.'Limitations not yet established for these Subcategories.
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71
For Subcategon'es N and 0, i.e. EVA Copolymers and Polytetrafluoroethy-
lene, Existing Sources.No limitations presently prescribed for process
wastes to POTW's.
For Subcategory P, Polypropylene Fibers, Existing Sources. No limita-
tions prescribed except for oil and grease with a Pretreatment Standard
of 100 mg/1.
For Subcategory Q Through T, i.e. Alkyds and Unsaturated Polyester
Resins, Cellulose Nitrate, Nylon 6/12 and Polyester (Thermoplastic)
Resins, Existing Sources. No limitations presently prescribed for
process wastes to POTW's.
For Subcategory U, Silicones, Existing Sources. No limitations
prescribed except for Copper with a Pretreatment Standard of 1 mg/1.
For Subcategon'es A Through U, i.e. All Subcategdries. New Sources.
Limitations not yet established.
REVOCATION AND SUSPENSION OF REGULATIONS FOR THE PLASTICS AND SYNTHETIC
MANUFACTURING INDUSTRY
The 40 CFR Part 416, Federal Resister publication of May 19, 1975
suspended the entire Acrylics Subcategory (Subcategory M) together
with applicable limitations. On March 10, 1976, the U.S. Court of
Appeals for the 4th Circuit further remanded Subcategories A through
M and the effluent limitations guidelines and the new source performance
standards to the EPA for reconsideration. Doubt was also cast on
Subcategories N through U, and their associated effluent limitations
guidelines and new source performance standards. Proposed pretreatment
standards for existing sources in alj_ established Subcategories were
similarly determined to be rescinded.
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72
SOAP AND DETERGENT MANUFACTURING
(29, 30, 31, 32)
[Part 417]
SUBCATEGORIZATION OF THE INDUSTRY
The Soap and Detergent Manufacturing Industry is divided into 19 Sub-
categories. Subcategories A - H are essentially soap and soap product
manufacture, and Subcategories I through S are detergent product man-
ufacture.
A - Soap Manufacturing by Batch Kettle
B - Fatty Acid Manufacturing by Fat Splitting
C - Soap Manufacturing by Fatty Acid Neutralization
D - Glycerine Concentration
E - Glycerine Distillation
F - Manufacture of Soap Flakes and Powders
G - Manufacture of Bar Soaps
H - Manufacture of Liquid Soaps
I - Oleum Sulfonation and Sulfation
J - Air/S03 Sulfation and Sulfonation
K - SO., Solvent and Vacuum Sulfonation
L - Sulfamic Acid Sulfation
M - Chlorosulfonic Acid Sulfation
N - Neutralization of Sulfuric Acid Esters and Sulfonic Acids
0 - Manufacture of Spray Dried Detergents
P - Manufacture of Liquid Detergents
Q - Manufacturing of Detergents by Dry Blending
R - Manufacturing of Drum Dried Detergents
S - Manufacture of Detergent Bars and Cakes
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73
PARAMETERS OF CONCERN
BOD IDS
COD Nitrogen
TSS Phosphorous
Surfactants (NBAS) Boron
Oil/Grease Sodium Salts
pH, Acidity, Alkalinity Sulfate
Zinc Barium
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
In early guidelines documents, COD, oil and grease and surfacants were
described as incompatible pollutants to POTW's. This was subsequently
changed with oil and grease and surfactants said to be removed through
adequately designed and operated POTW's. COD pretreatment limitations
were deleted for some subcategories and retained for others. Whereas
surfactants and other compounds expressed as COD in most subcategories
were determined to be relatively biodegradable, concern was especially
raised over wastes from the production of industrial and institutional
detergents. The latter materials are highly refractive and may thusly
adversely affect POTW's through bacteriostatic or bacteriocidal effects,
or pass through POTW's without significant reduction. Consequently,
COD pretreatment limitations were retained for spray dried and liquid
detergent, and dry blending and drum-dried detergent manufacturing.
For Subcategories A through N and Subcategory S, Existing and New
Sources:
Wastewaters are considered to contain no incompatibles and therefore may
be discharged to POTW's without pretreatment. No pretreatment limi-
tations are given.
For Subcategory 0, Spray Dried Detergents, Existing Sources:
COD - Where more than 25 percent of the annual production is represented
by final products having a COD: BODr ratio greater than 4, the
allowable COD discharge shall be restricted to 2.5 lb/1,000 Ib
anhydrous product for that portion of the production representing
final products with a COD: BODr ratio equal to or greater than 4.
For that portion of the production representing final products
with a COD: BODr ratio less than 4, the incremental COD discharge
shall be restricted to 8.0 lb/1,000 Ib anhydrous product.
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74
For Subcategory 0, Spray Dried Detergents, New Sources:
COD - Where waste streams have a COD: BOD7 ratio of 10 or less, or the
streams have a COD content of 2.4 lb/1,000 Ib anhydrous product
or less, no pretreatment limitations are given.
Where waste streams have a COD: BOD7 ratio greater than 10 and a
COD content of more than 2.4 lb/1,000 Ib anhydrous product, COD
pretreatment limits are:
1) With normal operation of spray drying towers:
Avg. 30 Day
(lb/1,000 Ib
anhydrous product)
Max. Day
(lb/1,000 Ib
anhydrous product)
0.04
0.08
2)
For air quality restricted operation of spray drying tower,
but only when high rate of wet scrubbing is necessary which
produces more waste than can be recycled to process :
0.25
0.50
3)
For fast turnaround operation of a spray tower when the number
of turnarounds over any 30 day period exceeds 6, the maximum
daily allowable waste load shall be sum of 1) or 2) directly
above plus the appropriate value of 0.07 lb/1,000 Ib anhydrous
product. Also, the avg. 30 day allowable load shall be the
number of turnarounds in excess of 6 multiplied by 0.07
lb/1,000 Ib anhydrous product and prorated to 30 days plus
the value contained in either 1) or 2) above.
For Subcategory P. Manufacture of Liquid Detergents. Existing Sources:
COD - Where more than 25 percent of the annual production is represented
by final products having a COD: BOD5 ratio greater than 4, the
allowable COD discharge shall be restricted to 1.0 lb/1,000 Ib
anhydrous product for that portion of the production representing
final product with a COD: BOD,- ratio equal to or greater than 4.
For that portion of the production representing final products
with a COD: BODg ratio less than 4, the incremental COD discharge
shall be restricted to 4.0 lb/1,000 Ib anhydrous product.
For Subcategory P, Manufacture of Liquid Detergents, New Sources:
COD - Where waste streams have a COD: BODy ratio of 10 or less or
the streams have a COD content of 1.1 lb/1,000 Ib anhydrous pro-
duct or less, no pretreatment limitations are given.
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75
COD - Where waste streams have a COD: BOD ratio greater than 10 and a
COD content of more than 1.1 lb/1,000 Ib anhydrous product, COD
pretreatment limits are:
1) With normal liquid detergent operations:
Avg 30 Day Max. Day
(lb/1,000 Ib (lb/1,000 Ib
anhydrous product) anhydrous product)
0.22 0.44
2) For fast turnaround operation of automated fill lines, when
the number of turnarounds exceeds 8 over any 30 day period, the
maximum daily allowable waste loads shall be the sum of 1)
directly above plus the appropriate value of 0.07 lb/1,000 Ib
anhydrous product. Also, the avg. 30 day allowable load shall
be the number of turnarounds in excess of 8 multiplied by
0.07 lb/1,000 Ib anhydrous products and prorated to 30 days plus
the value contained in 1) above.
For Subcategory Q, Manufacture of Detergents by Dry Blending, Existing
Sources:
COD - Where more than 25 percent of the annual production is represented
by final products having a COD: BOD,- ratio greater than 4, the
allowable COD discharge shall be restricted to 0.25 lb/1,000 Ib
anhydrous product for that portion of the production representing
final products with a COD: BODr ratio equal to or greater than 4.
For that portion of the production representing final products
with a COD: BODr ratio less than 4, the incremental COD discharge
shall be restricted to 0.50 lb/1,000 Ib anhydrous product.
For Subcategory Q, Manufacture of Detergents by Dry Blending, New Sources:
COD - Where waste streams have a COD: BOD7 ratio of 10 or less or the
streams have a COD content of 0.26 lb/1,000 Ib anhydrous product
or less, no pretreatment limitations are given.
Where waste streams have a COD: BOD-, ratio of 10 or more and a
COD content of more than 0.26 lb/1,000 Ib anhydrous product, COD
pretreatment limits are:
Avg 30 Day Max. Day
(lb/1,000 Ib (lb/1,000 Ib
anhydrous product) anhydrous product)
0.07 0.14
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76
For Subcategory R, Manufacture of Drum Dried Detergents, Existing Sources:
COD - Where more than 25 percent of the annual production is represented
by final products having a COD: BOD5 ratio greater than 4, the
allowable COD discharge shall be restricted to 0.15 lb/1,000 Ib
anhydrous product for that portion of the production representing
final products with a COD: BOD,- ratio equal to or greater than 4.
For that portion of the production representing final products with
a COD: BOD5 ratio less than 4, the incremental COD discharge shall
be restricted to 0.30 lb/1,000 Ib anhydrous product.
For Subcategory R, Manufacture of Drum Dried Detergents, New Sources:
COD - Where waste streams have a COD: BOD^ ratio of 10 or less or the
streams have a COD content of 0.20 lb/1,000 Ib anhydrous product
or less, no pretreatment limitations are given.
Where waste streams have a COD: BOD^ ratio of 10 or more and a
COD content of more than 0.20 Ib/I500o Ib anhydrous product, COD
pretreatment limits are:
Avg. 30 Day Max. Day
(Tb/1,000 Ib (lb/1,000 Ib
anhydrous product) anhydrous product)
0.05 0.10
PRESCRIBED TREATMENT FOR DISCHARGE TO POTW
No specific pretreatment systems have been defined for soap and detergent
plants discharging to municipal sewers. However, the EPA Development
Document on Soap and Detergent Manufacturing emphasizes caution with
respect to fats and oils from both soap and detergent plants. Other
areas of caution include the manufacture of industrial cleaners and po-
tentially high zinc levels in wastes throughout the industry.
Fats and oils in wastes from soap plants, if excessive, should be passed
through gravity-type separators or well-designed fat traps. This type of
pretreatment should remove at least 9Q% of the free oils which are re-
ported as the main source of problems in both municipal sewers and
treatment plants. Fats and oils from detergent plants behave more like
hydrocarbons encountered in the organic chemical industry rather than
the natural fats. Detergent-type fats are consequently less biodegradable.
Zinc concentrations greater than 5 mg/1 can exert adverse effect upon
biological POTW's. Should zinc problems arise, alkaline precipitation
pretreatment may be employed. Certain industrial cleaners contain
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phosphoric acid, hydrofluoric acid and certain organics such as the
chlorinated benzenes. Release of phosphates and fluorides may possibly
be controlled by in-house measures. Chlorinated organics should be
restricted and/or controlled to a very close degree because of toxicity
to man and deleterious effects to waste treatment plants and receiving
waters.
The Federal Register of February 20, 1975 discusses pretreatment to
reduce COD loads from New Sources in the Soap and Detergent Industry.
Such measures may include installation of on-site storage to eventually
facilitate recycling of wastewater and materials back into the process.
Reasonable use of in-plant controls, especially when formulations con-
tain large amounts of refractory organic materials, will further reduce
COD loads to prescribed levels.
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FERTILIZER MANUFACTURING INDUSTRY
(182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 196)
[Part 418]
SUBCATEGORIZATION OF THE INDUSTRY
The fertilizer industry has been divided into seven distinctly different
subcategories which have different pollutants, waste treatment tech-
nologies and waste management problems. These subcategories are described
below:
A - Phosphate Subcategory. Applicable to plants manufacturing sulfuric
acid by sulfur burning, and the manufacture of wet process phosphoric
acid, normal superphosphate, triple superphosphate and ammonium phos-
phate. The manufacture of phosphoric acid includes phosphate rock
grinding, acid attack of phosphate rock, phosphoric acid concentration, .
and phosphoric acid clarification. All of these operations usually
occur in a single complex separate from nitrogen fertilizer products.
B - Ammonia Subcategory. Applicable to plants manufacturing (anhydrous)
ammonia. Ammonia is manufactured by high temperature - high pressure
gaseous reactions. Adequate treatment of the primary waste constituent,
ammonia, can only be accomplished by treatment separate from other
operations in a nitrogen fertilizer complex, i.e. ammonia stripping, and
hence these activities are classed in a single Subcategory.
C - Urea Subcategory. Applicable to plants manufacturing urea. The
synthesis of urea is characterized by high pressure gaseous reactions.
D - Ammonium Nitrate Subcategory. Applicable to plants manufacturing
(anhydrous) ammonium nitrate!Liquid ammonia and nitric acid are mixed
in a low pressure vessel and subsequently water is removed by flash
vaporization.
E - Nitric Acid Subcateqory. Applicable to plants producing nitric acid
used as an intermediate for the manufacture of fertilizer or for other
intermediates. Nitric acid is essentially produced via the oxidation of
ammonia at elevated temperatures.
F - Ammonium Sulfate Subcategory. Applicable to plants producing ammo-
nium sulfate by the "Synthetic" process and by coke oven byproduct re-
covery. This Subcategory does not^apply to ammonium sulfate as a by-
product of caprolactum manufacturing. In the synthetic process, virgin
ammonia and sulfuric acid are directly combined. Coke oven ammonium
sulfate is produced from ammonia reclaimed from the coking of coal by
absorption with sulfuric acid.
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79
G - Mixed and Blend Fertilizer Production Subcategory. Applicable to
plants producing mixed fertilizer and blend fertilizer. "Mixed fer-
tilizer" manufacturing refers to a process which mixes wet and/or dry
straight fertilizer materials, mixed fertilizer materials, fillers and
additives progressing through chemical reactions to give a certain
formulation. "Blend fertilizer" manufacturing refers to a process which
mixes dry, straight and mixed fertilizer materials to a given N-P-K
formulation.
NATURE OF PROBLEM
The Fertilizer Industry manufactures three types of nutrient products:
1) the nitrogen fertilizers including ammonia, urea, ammonium nitrate
and ammonium sulfate; 2) the phosphate fertilizers including phosphoric
acid, normal superphosphate and triplephosphate; and 3) combination
fertilizer comprising the ammonium phosphates, "Mixed" fertilizers, and
"Blend" fertilizers.
In the Phosphate Subcategory, processing requires large amounts of
cooling waters. Leaks in heat exchange equipment cause escape of sul-
furic acid. Waste pollutants from phosphates and sulfuric acid manu-
facturing include low pH, phosphorous, fluorides, cadmium, arsenic,
vanadium and uranium. Cadmium is a major pollutant found in raw waste-
waters from phosphate Subcategory plants. Phosphoric acid used for
fertilizers is produced by adding a strong acid, usually sulfuric, to
phosphate ores. The ore is not pure and abundant fluorides and trace
amounts of cadmium, arsenic, vanadium and uranium will be leached out by
the acid. Fluorine is volatized in processing and collected via water
scrubbers. Large amounts of byproduct gypsum formed in the reaction are
sluiced to gypsum ponds. The wastewaters from the scrubbers are usually
sent to this same pond. When phosphoric acid is concentrated, impurities
will be volatilized and collected within the barometric condenser waters.
Escaping gases from the production of superphosphates and ammonium
phosphates are treated by wet scrubbers. Phosphorous and fluorides are
present in these waters. Ammonia is found in ammonium phosphate scrubber
waters.
In the Ammonia Subcateqory, nitrogen waste will be present as ammonia.
Highly varying pH levels and oil and grease are important pollutants.
The principal process wastewater results from the condensation of excess
steam used in the primary reformer. Ammonia in the condensate origi-
nates from recycle of purge gas, from feed air containing ammonia, and
from ammonia inadvertantly formed in the shift converter. Because
cryogenic equipment is used, condensate about the pipes, etc., can
absorb ammonia from leaks in seals. Ammonia also emanates from absorp-
tion in cooling towers of various ammonia emissions. Oil and grease are
mainly derived as drippings from pumps and high-pressure compressors.
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in the Urea Subcategory, nitrogen waste is characterized by ammonia and
organic nitrogen mixed with urea. Highly varying pH levels are also
experienced. Following high-pressure gaseous reactions, the pressure is
reduced and ammonia, carbon dioxide and ammonium carbamate are flashed
from the ur.ea product. These flashed gases receive water scrubbing.
This scrub liquor together with condensates from the urea concentration
step, result in a waste containing urea, ammonium carbamate, ammonia and
carbon dioxide. Prill tower operations are responsible for increased
loads of ammonia and urea. Fine dust from prill towers and/or urea pan
.granulators will enter the liquid waste collection systems via rain
water and wash waters.
In the Ammonium Nitrate Subcategory, nitrogen waste is characterized by
ammonia and nitrates. Flash vaporization of water from the dilute
nitric acid is a major process wastewater. The nitric acid-ammonia
reaction is highly exothermic, and large quantities of water with am-
monia, nitric acid, nitrates and nitrogen dioxide are evaporated. Air
scrubbing transfers these pollutants to the water phase. As for urea,
prilling of ammonium nitrate causes a fine dust which can enter the
liquid waste collection systems via wash waters and rain waters.
In the Nitric Acid Subcategory. nitrogen waste is characterized mainly
by nitrates. The oxidation of ammonia at elevated temperatures gen-
erates little or no process wastewaters. Leaks and spills are reported
as the only sources of pollution from nitric acid manufacturing.
In the Ammonium Sulfate Subcategory, major waste sources include con-
taminated water, closed loop tower waters, crystal wash waters, pro-
cess condensates, spills and leaks, and miscellaneous. Contaminated
waters mostly refer to barometric condenser waters coming off the sa-
turator-crystallizers and excess waters withdrawn from the plant re-
circulated water system(s).
Mixed and Blend Fertilizer processing is represented by a significantly
large number of establishments in the U.S. Waste streams can include
contaminated water, process waters, spills and leaks, and miscellaneous.
Contaminated water in most cases will encompass liquors from the wet
scrubbing of drier and/or ammoniator exhaust gases. Contaminated water
is usually bled out of the closed loop recirculation system serving the
scrubbers.
In summary, principal wastewaters in fertilizer production are from
manufacturing operations including product washdown and purification,
closed loop tower blowdowns, process condensates, wet scrubbing ef-
fluents, spills and leaks, and various runoff.
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PARAMETERS OF CONCERN
pH, Acidity, Alkalinity IDS
Ammonia Nitrogen Phosphorous, phosphates
Organic Nitrogen Sulfates
Nitrates, Nitrites Cadmium
Fluorides Arsenic
COD Vanadium
TSS Uranium
Hardness Radium-226
Oil and Grease Temperature
Phenols
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
For Subcategory A, Phosphate Production. Existing Sources
Pretreatment limitations have been equated to BPT limitations which are
described below.
I. Process wastewaters are prohibited from discharge. However for
(process) wastewaters from a calcium sulfate storage pile runoff fa-
cility operated separately or in combination with a water recirculation
system, there shall be no discharge except when there is an excess over
and above a surge capacity equal to the runoff from a 10-year, 24-hour
rainfall event; or_ when extremely unusual precipitation events cause the
water level to rise into the surge capacity in which case the wastewater
must be treated and discharged whenever the water level equals or exceeds
the mid-point of the surge capacity.
The following concentrations shall be adhered to for excess storage
pond waters:
Pollutant
Total Phosphorus
Fluoride
TSS
PH
Avg. 30 Day
mg/1
as P 35
25
50
6.0 to 9.5
Max. Daily
mg/1
105
75
150
But the above TSS limits may be waived when process waters are chem-
ically treated and then settled in order to meet the other pollutant
limits.
II. "Contaminated non-process wastewaters" are defined as: "any water
including precipitation runoff which, during manufacturing or process-
ing, comes into incidental contact with any raw material, intermediate
product, finished product, byproduct or waste product by means of: 1)
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precipitation runoff; 2) accidental spills; 3) accidental leaks caused
by the failure of process equipment and which are repaired or the dis-
charge of pollutants therefrom contained or terminated within the short-
est reasonable time which shall not exceed 24 hours after discovery or
when discovery should reasonably have been made, whichever is earliest;
and 4) discharges from safety showers and related personal safety
equipment, and from equipment washings for the purpose of safe entry,
inspection and maintenance; provided that all reasonable measures have
been taken to prevent, reduce, eliminate and control to the maximum
extent feasible such contact, and provided further that all reasonable
measures have been taken that will mitigate the effects of such contact
once it has occurred." For these contaminated non-process waters, the
following concentrations shall be adhered to:
Pollutant
Total Phosphorus as P
Fluoride
PH
Avg. 30 Day
mg/1
30
25
6.0 to 9.5
Max. Daily
mg/1
105
75
For Subcategory A, Phosphate Production, New Sources
There shall be no discharge of process wastewater pollutants.
For Subcategory B, Ammonia Production, Existing Sources
Pretreatment limitations have been equated to BPT limitations which are
described below.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib anh. ammonia 1b/l,000 Ib anh. ammonia
Ammonia as N 0.0625 0.1875
pH 6.0 to 9.0
For Subcategory B, Ammonia Production, New Sources
Pretreatment limitations have not yet been specified.
For Subcategory C, Urea Production, Existing Sources
Pretreatment limitations have been equated to BPT limitations which are
described below. Limitations are applicable to the manufacture of urea.
Discharge from shipping losses and precipitation runoff are excluded.
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I. Manufacturing operations in which urea is "prilled" or granulated.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib urea product lb/1,000 Ib urea product
Ammonia as N 0.46 0.92
Organic nitrogen as N 0.55 1.03
pH 6.0 to 9.0
II. Manufacturing operations in which urea is produced as a solution
product.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib urea product lb/1,000 Ib urea product
Ammonia as N 0.43 0.85
Organic nitrogen as N 0.27 0.50
6.0 to 9.0
For Subcategory C. Urea Production, New Sources
Pretreatment limitations have not yet been specified.
For Subcategory D, Ammonium Nitrate Production, Existing Sources
Pretreatment limitations have been equated to BPT limitations which are
described below. Limitations are applicable to the manufacture of
ammonium nitrate. Discharges from shipping losses and precipitation
runoff are excluded.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib ammomium nitrate lb/1,000 Ib ammonium nitrate
Ammonia as N 0.35 0.66
Nitrate as N 0.36 0.66
pH 6.0 to 9.0
For Subcategory D, Ammonium Nitrate Production. New Sources
Pretreatment limitations have not yet been specified.
For Subcategory E, Nitric Acid, Existing Sources
Pretreatment limitations have been equated to BPT limitations which
are described below. Limitations are applicable to the manufacture
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of nitric acid in concentrations up to 68%. Discharge from shipping
losses are excluded. In the regulations, certain terms are defined.
"Shipping losses" refer to the discharges from loading tank cars or
tank trucks; discharges from cleaning tank cars or tank trucks; and
discharges from air pollution control scrubbers designed to control
emissions from loading or cleaning tank cars or tank trucks. The
term "shipped liquid ammonia" refers to liquid ammonia commercially
shipped for which the Department of Transportation requires 0.2%
minimum water content. The term "non-contact cooling water" shall
mean water which is used in a cooling system designed so as to main-
tain constant separation of the cooling medium from all contact with
process chemicals but which may on the occasion of corrosion, cooling
system leakage or similar cooling system failure contain small amounts
of process chemicals,...."
I. Nitric acid production in which all raw material ammonia is in
the gaseous form.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib nitric acid on lb/1,000 Ib nitric acid on
the basis of 100% HN00 the basis of 100% HNO-
Ammonia as N
Nitrite as N
PH
0.0007
0.044
6.0 to 9.0
0.007
0.33
II. Nitric Acid production in which all raw material ammonia is in the
shipped liquid form.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib nitric acid on lb/1,000 Ib nitric acid on
the basis of 100% HN00 the basis of 100% HNO-
Ammonia as N
Nitrate as N
PH
0.0008
0.044
6.0 to 9.0
0.08
0.33
III. Non-Contact Cooling Water Limitations.
Parameter Limitation
pH 6.0 to 9.0
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85
For Subcateqory E, Nitric Acid, New Sources.
Limitations are applicable to the manufacture of nitric acid in con-
centrations, up to 68%. Discharges from shipping losses are excluded.
I. Nitric Acid production in which all raw material ammonia is in the
gaseous form.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib nitric acid on lb/1,000 Ib nitric acid on
the basis of 100% HN03 the basis of 100% HN03
Ammonia as N 0.00045 0.0045
Nitrate as N 0.023 - 0.17
II. Nitric acid production in which all raw material ammonia is in the
shipped liquid form.
Avg. 30 Day Max. Daily
Pollutant lb/1,000 Ib nitric acid on lb/1,000 Ib nitric acid on
the basis of 100% HN03 the basis of 100% HN03
Ammonia as N 0.008 0.08
Nitrate as N 0.023 0.17
III. Non-contact cooling water limitations.
Parameter Limitation
pH 6.0 to 9.0
For Subcategory F, Ammonium Sulfate Manufacturing, Existing and New Sources
Pollutant Pretreatment Standard
Ammonia as N 30 mg/1
pH, BOD, TSS No limitations
For Subcategory G, Mixed and Blend Fertilizer Production, Existing and
New Sources
Pollutant Pretreatment Standard
Ammonia as N 30 mg/1
Total Phosphorous as P 35 mg/1
pH, BOD, TSS, Nitrates No limitations
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86
In summary, the waste waters from fertilizer plants, if passed to con-
ventional secondary treatment municipal plants may not be amenable to
reduction of wastwater pollutants, and furthermore, could cause severe
adverse impact on proper functioning of the POTW. Accordingly, pre-
treatment criteria especially for ammonia nitrogen, should be relatively
stringent.
SUSPENSION AND REVOCATION OF CERTAIN FERTILIZER EFFLUENT REGULATIONS
AND GUIDELINES
On June 23, 1975, the Federal Register effectively suspended the whole
of Subcategory D (Ammonium Nitrate) effluent limitations and regulations
including pretreatment stipulations.
The Federal Register publication of March 25, 1977 made subsequent
changes on pretreatment limitations for the Fertilizer Industry. Spe-
cifically, for Subcategories A and E, respectively, the Phosphate and
Nitric Acid Subcategories, pH limits were revoked for Existing and for
New Sources. It was determined that maintaining pH levels in the 6-9
range from the subject plants was not completely reasonable.
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PETROLEUM REFINING INDUSTRY
(197, 198, 199, 200)
[Part 419]
SUBCATEGORIZATION OF THE INDUSTRY
The Petroleum Refining Industry has been divided into six major sub-
categories described as follows:
A - Topping Subcategory. Applies to facilities which produce petroleum
products by topping and catalytic reforming whether or not the facility
includes other processes in addition to topping and catalytic reforming.
This subcategory is not applicable to facilities having thermal pro-
cesses such as coking, visbreaking, and catalytic cracking operations.
Specialized definitions are given for "runoff", "ballast", "feedstock",
"once-through cooling water", and units of measurement shown below.
These definitions are important in terms of additional waste load allo-
cations permitted under BPT, BAT and New Source regulations.
Runoff - refers to the flow of storm water.
Ballast - refers to the flow of wastes from a ship, which are treated
at the refinery.
Feedstock - refers to the crude oil and natural gas liquids fed to the
topping units.
Once-through Cooling Waters - refers to discharges that are used for the
purpose of heat removal and that do not come into direct contact with
any raw material, intermediate, or finished product.
M gal. - shall mean one thousand gallons; M bbl. shall mean one thousand
barrels. One barrel is equivalent to 42 gallons.
B - Cracking Subcategory. Applies to facilities which produce petroleum
products by topping and cracking, whether or not the facility includes
any other processes in addition to topping and cracking. This sub-
category is not applicable to facilities having processes specified
under Subcategories C, D or E.
Specified definitions are the same as for Subcategory A plants.
C - Petrochemical Subcategory. Applies to facilities which produce
petroleum products by topping, cracking and petrochemical operations,
whether or not the facility includes any processes in addition to
topping, cracking and petrochemical operations. This subcategory is not
applicable to facilities having processes specified under Subcategories D
and E. Specialized definitions are the same as for Subcategory A plants
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88
to which is added the term "petrochemical operations." Petrochemical
operations are defined as the production of second generation petro-
chemicals, i.e., alcohols, ketones, cumene, styrene, etc., or first
generation petrochemicals and isomerization products, i.e. BTX, olefins,
cyclohexane, etc., when 15 percent or more of refinery production com-
prises first generation petrochemicals and isomerization products.
D - Lube Subcategory. Applies to facilities which produce petroleum
products by topping, cracking and lube oil manufacturing processes,
whether or not the facility includes any processes in addition to top-
ping, cracking and lube oil manufacturing. This subcategory is not
applicable to facilities having processes specified under Subcategories
C and D. Specialized definitions are the same as for Subcategory A
plants.
E - Integrated Subcategory. Applies to facilities which produce petro-
leum products by topping, cracking and lube oil manufacturing processes,
and petrochemical operations, whether or not the facility includes any
process in addition to topping, cracking, lube oil manufacturing pro-
cesses and petrochemical operations. Specialized definitions are the
same as for Subcategory C plants.
In terms of providing general understanding of petroleum refining pro-
cessing, the following description of processes may be helpful:
Distillation - separates hydrocarbon molecules by differences in their
physical properties, i.e., boiling points.
Cracking - the breaking down of high molecular weight hydrocarbons to
lower weight hydrocarbons.
Polymerization and Alkylation - the rebuilding of hydrocarbon molecules.
Isomerization and Reforming - the rearranging of molecular structures.
Solvent Refining - the separation of hydrocarbon molecules by differences
in solubility in other compounds.
Desalting and Hydrotreating - the removal of impurities occurring in
the feedstocks.
Miscellaneous Operations - these include the removal of impurities from
finished products by various treating and
finishing processes, et. al.
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NATURE OF PROBLEM
As of January 1973, a total of 247 operating petroleum refineries were
reported in the United States having a combined crude oil processing
capacity of 14 million barrels/day. Individual plants ranged in capacity
from 200 to 434,000 barrels/day. Because of crude supply limitations,
most new refinery capacity is being designed to handle higher sulfur
crudes. This trend leads to increased sour water stripping, desalting,
more sour heavy bottoms, and greater efforts to reduce sour gas emis-
sions and general problems of corrosion through the refinery.
Ammonia, sulfide and phenol at a refinery originate from sour water
waste streams. Sour waters are produced when steam is used as a strip-
ping medium in the various cracking processes at a refinery.
Oil and grease may be generated by a wide variety of operations at a
refinery, including pad washings, tank bottom washings, and contaminated
storm runoff.
Chromium is primarily associated with cooling tower blowdown when chro-
mium compounds are employed as corrosion inhibitors in the refinery
cooling water systems.
PARAMETERS OF CONCERN
BOD Zinc
COD IDS
Oil/Grease TSS
Sulfides TOC
Ammonia N Temperature
pH, Acidity, Alkalinity Chlorides
Phenols Fluorides
Chromium, total and Phosphates
hexavent ».. ,, . ,
Other Metals
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PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
Pretreatment Standards for Existing Plants Within Subcategories A
Through E~(That for New Sources have not yet been clearly defined).
Parameter Daily Max. Value
Ammonia as N 100 mg/1
Oil/Grease 100 mg/1
pH Shall not be lower than 5.0 in order
to minimize corrosive structural damage,
unless the POTW is specifically designed
to accommodate the given conditions.
It is recognized at relatively low concentrations in biological treat-
ment, ammonia may serve usefully as a nutrient. At excessively high
levels however, ammonia will inhibit the biological process and pass
through the POTW untreated.
Phenolic compounds are said to be biodegradable by acclimated biota.
Many POTW's can accept phenol-containing industrial wastes without
upset. In cases where a POTW cannot handle phenolic wastes of a spe-
cific refinery, a maximum daily phenol limitation of 0.35 mg/1 has been
developed as guidance.
Chromium pretreatment limits have not been established. However, when
chromium is' judged to cause detrimental effect upon POTW's a daily max-
imum total chromium limit of 1.0 mg/1 can be attained and is cited as
guidance. It is suggested that cooling tower blowdown be segregated,
and hexavalent chromium be reduced to trivalent chromium using sulfur
dioxide, followed by waste settling.
SuIfides in refinery wastewaters can interfere with successful operation
of POTW's and cause corrosion in concrete waste conveyance pipelines.
When sulfides are judged to cause significant detrimental effect upon
POTW's, a daily maximum sulfide limit of 3.0 mg/1 can be attained and is
cited as guidance to POTW's.
It is reported that pretreatment limitations for the Petroleum Refining
Industry will generally require implementation of control and pretreat-
ment technology similar to that practiced by direct dischargers in the
industry. This includes sour water strippers for removing ammonia from
sour water waste streams; and dissolved air flotation (DAF) units or
equivalent methods, in addition to API separators, for removing oil and
grease content. Also, sufficient waste equalization should be strongly
considered in all pretreatment systems.
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IRON AND STEEL MAKING SEGMENT OF IRON AND STEEL INDUSTRY
(12, 208, 209, 210)
[Part 420]
SUBCATEGORIZATION OF THE INDUSTRY
Twelve Subcategories described as Subcategories A through L have been
defined for the Iron and Steel Making Segment of the Iron and Steel
Industry. Fourteen other Subcategories are included under the Hot
Forming and Cold Finishing Segment of the Iron and Steel Industry which
are described in another section of this report. It is noted that
Subcategories G, K and L and their accompanying pretreatment limita-
tions below encompass alloy and stainless steel in addition to customary
carbon steel.
A) Byproduct Coke subcategory
B) Beehive Coke subcategory
C) Sintering subcategory
D) Blast Furnace (Iron) subcategory
E) Blast Furnace (Ferromanganese) subcategory
F) Basic Oxygen Furnace (semi-wet air pollution controls)
subcategory
G) Basic oxygen Furnace (wet air pollution controls) subcategory
H) Open Hearth Furnace subcategory
I) Electric Arc Furnace (semi-wet air pollution controls)
subcategory
J) Electric Arc Furnace (wet air pollution controls) subcategory
K) Vacuum Degassing subcategory
L) Continuous Casting and Pressure Slab Molding subcategory
Subcategory A. Byproduct Coke - Coke making operations conducted
by the heating of coal in slot-type ovens in the absence of air
to produce coke.
Subcategory B, Beehive Coke - Coke making operations conducted
by the heating of coal with the admission of air in controlled
amounts. Beehive coking operations do not have accompanying
byproduct plants.
Subcategory C. Sintering - A sinter plant conducts heating of
iron bearing wastes (mill scale and dust from blast and steel
making furnaces) together with fine iron ore, limestone and coke-
fines in an ignition furnace in order to produce a special
agglomerate or sinter. This latter is charged into the blast
furnace.
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Subcategory D, Blast Furnace (Iron) - Comprises the making of iron
in which iron ore is reduced to molten iron within a blast furnace.
Subcategory E, Blast Furnace (Ferromanganese) - Iron/manganese
ores are reduced to molten ferromanganese in a blast furnace.
Ferromanganese differs from Subcategory D (Iron blast furnace)
in requiring higher operating temperatures in the blast furnace,
which in turn is said to produce higher concentration of pollutant
parameters, notably cyanides, in the gas washing waters.
Subcategory F. Basic Oxygen Furnace (with semi-wet air pollution
controls) - Carbon steel is manufactured in a basic oxygen furnace
equipped with a semi-wet dust collection system. With the semi-
wet system a spark box or a spray chamber using slightly more
water than can be evaporated is used to condition the gases for
further cleaning, producing a highly contaminated but relatively
small volume of waste water.
Subcategory G, Basic Oxygen Furnace (with wet air pollution con-
trols) - Carbon steel is manufactured in a basic oxygen furnace
equipped with a wet dust collection system. With the wet system
high energy scrubbers or wet gas washers are used to cool and to
condition furnace gases, producing much larger volumes of
moderately-contaminated waste waters than are found for the
semi-wet systems.
Subcategory H, Open Hearth Furnace - Carbon steel is manufactured
in an open hearth furnace equipped with wet dust collection systems.
Subcategory I, Electric Arc Furnace (with semi-wet air pollution
controls) - Carbon steel is manufactured in electric arc furnaces
equipped with semi-wet dust collection systems. With the semi-wet
system, a spark box or a spray chamber using slightly more water
than can be evaporated is used to condition the gases for further
cleaning in a precipitator or baghouse. A relatively small
volume of contaminated waste water may be produced, depending
upon the degree of excess spray water employed.
Subcategory J, Electric Arc Furnace (with wet air pollution controls
Carbon steel is manufactured in electric arc furnaces equipped with
wet furnace off-gas dust collection. With the wet system, high
energy scrubbers or wet gas washers are used to cool and to condi-
tion furnace gases, producing much larger volumes of moderately-
contaminated waste waters than are found for the semi-wet systems.
Subcategory K. Vacuum Degassing - Degassing operations comprise
application of a vacuum to molten steel to further refine the
steel product. Degassing removes hydrogen, carbon and oxygen and
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any other volatile alloys from the steel, along with minute
particles of iron oxide. These gases together with exhaust
steam, are condensed by direct contact with cooling water,
producing a contaminated waste water.
Subcategory L, Continuous Casting and Pressure Slab Molding -
The continuous formation of a primary steel shape (such as a
slab, billet or bloom) from molten steel by casting through a
water cooled mold. Most of the water serving the continous
casting operations is used for mold and machine cooling. The
latter represent noncontact systems on closed recycle with no
contamination. Dirty process waters originate from open spray
methods. Pressure slab molding is the casting of a slab in a
mold by a bottom pouring method.
NATURE OF PROBLEM
Approximately 92 percent of the 1972 total U.S. annual steel ingot
production was produced by 15 major steel corporations. This also
represented 22.5 percent of the world total of 625 million ingot tons
of steel produced in 1972. Steel production in 1969 was a record
141 million ingot tons. In 1972, approximately 65 million tons of
coke, 83 million tons of iron, and 134 million tons of steel, were
manufactured.
Three series of operations are involved in the production of steel.
Coal is first converted to pure carbon, coke. Secondly, coke is
combined with iron ore and limestone in a blast furnace to produce
iron. Thirdly, iron is purified into steel in either an open hearth,
basic oxygen, or electric arc furnace. Further refinements include
degassing, etc. Steel not cast into ingot molds can be cast in a
process called continuous casting. The sintering plant as part of
the present day integrated steel mill has the main function of agglo-
merating and recycling (waste) fines back to the blast furnace.
Characteristics of wastes from the various Subcategories and the
identified sources of pollutants are described as follows:
A) By Product Coking - Major pollutants include ammonia, BOD,
cyanides, phenols, oils and grease, sulfides, TSS (and varying pH).
Major waste sources comprise excess ammonia liquor resulting from
the condensation of moisture originally present in the raw coal
before coking; wastes from the light oil recovery system; overflows
from the final cooler recycle system; condensates from desulfurizers;
effluents from baro-meter condensers; and indirect cooling waters.
Additional waste sources may include coke wharf drainage, quench
water overflow, and coal pile runoffs. Beyond conventional waste
treatments, additional technology for reducing waste at by-product
coke plants includes steam stripping of ammonia liquor, depheno-
lization, and desulfurization.
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94
B) Beehive Coke - Important pollutant parameters are ammonia,
BOD, cyanides, phenols, TSS and heat. In comparison to byproduct
coking, wastewater quantities from beehive coking are considerably
lower since the bulk of the volatile waste components (unfortu-
nately) are allowed to escape to the atmosphere. Process water
contacts the coke materials during the quenching operation carry-
ing along fine particles of coke and dissolving various residues
from the product.
c) Sintering - Significant pollutants include TSS, oil and grease,
sulfides and fluorides. Sinter plants built in the 1950's are
more likely to have wet scrubbers vs. plants constructed more
recently. Main pollutants associated with a wet system are TSS
washed out of the process gases; oils and greases from mill scale
which are vaporized during sintering then scrubbed out; sulfides
from coke fines; and fluorides from fluorspar and limestone
found in flue dusts from the steelmaking processes. The pollu-
tants will vary depending upon the various blends of iron bearing
dust and mill scale, coke fines and limestone constituting a
typical sinter burden.
D) Blast Furnace (Iron) - Major pollutants are TSS, cyanides,
phenols, ammonia, sulfides (and varying pH). Main waste sources
include the waters used for contact tooling of blast furnace gases
and the scrub waters used to wash blast furnace gases free of fine
particulates so as to permit their use as a fuel. TSS, in the waste
waters originate with these fines from the gases. Cyanides, phenols
and ammonia originate with the coke material charged to the blast
furnace especially if the coke had been quenched with contaminated
waters. Sulfides are produced as hydrogen sulfide gas caused by
the reducing atmosphere in the blast furnace. Fluorides occur in
the gas streams from the decomposition of raw materials charged to
the furnace which are easily transferred to the gas washer waters.
E) Blast Furnace (Ferromanganese) - Pollutants include TSS,
cyanides^ phenols, ammonia, sulfides, manganese (and varying pH).
The two main waste sources are the waters used for cooling the
blast furnace gases, and the waters for scrubbing the gases free
of fine particulates to permit their use as fuel. TSS in the
waste waters originate with these particulates which are relatively
high in manganese. Cyanides, phenols and ammonia originate from
the coke material charged to the furnace. Sulfides are produced
as hydrogen sulfide gas caused by the reducing atmosphere in the
blast furnace.
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F) Basic Oxygen Furnace (semi-wet air pollution controls)
Pollutant parameters principally comprise TSS and fluorides,
both of which are scrubbed out of the BOF gas streams during
water contact. Varying pH may also constitute a problem.
G) Basic Oxygen Furnace (wet air pollution controls) - Pollutants
and waste sources are the same as described above for Subcategory F.
H) Open Hearth Furnace - Known pollutants include TSS, fluorides,
zinc, nitrates, and varying pH. These contaminants are scrubbed
out of the furnace gas streams during water contact.
I) Electric Arc Furnace (semi-wet air pollution controls)
Important pollutants are TSS, zinc and fluorides, all of which
are scrubbed out of the furnace gas streams during water contact.
J) Electric Arc Furnace (wet air pollution controls) - Pollu-
tants and waste sources are the same as described above for
Subcategory I.
K) Vacuum Degassing - Known significant constituents in the
waste waters comprise TSS, zinc, manganese, lead, nitrates (and
varying pH). These contaminants originate from the water scrub-
bing of the gases under vacuum.
L) Continuous Casting and Pressure Slab Molding - Major
pollutants include TSS, oil and grease (and varying pH). These
contaminants are derived from the contact cooling of the cast
materials and the washing and cleaning of the molds.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity* TDS
Ammonia* Turbidity
BOD* Beryllium
Cyanide, total* Chlorides
Oil/Grease* COD
Phenols* Color
Sulfides* Heat
TSS* Mercury
Manganese* TKN
Fluorides* Sulfates
Zinc* Thiocyanates
Nitrates* TOC
Lead* Sodium
Aluminum Potassium
Hardness Phosphorous
Most significant pollutants.
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PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
For Subcategories A through L, Existing and New Sources.
No specific limitations have been prescribed to date for Existing and
New sources in the Iron and Steel Industry connected to POTW's. How-
ever, the Federal regulations and the EPA Development Document for the
Iron and Steel Making Segment of the Iron and Steel Industry describe
wastewaters from Subcategories A through L as containing high concen-
trate of ammonia, oil/grease, cyanide, sulfides, phenols, fluorides,
nitrates, lead, zinc and manganese all of which could interfere with
the successful operation of POTW's, pass through such works untreated
or inadequately treated, or otherwise be incompatible with the POTW.
Therefore, such process waste waters should receive special considera-
tion by the operator of the POTW, and are subject to future regulation.
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HOT FORMING, COLD FINISHING AND SPECIALTY STEEL
SEGMENT OF IRON AND STEEL INDUSTRY
(11, 12, 206, 207)
[Part 420]
SUBCATEGORIZATION OF THE INDUSTRY
Fourteen Subcategories described as Subcategories M through Z have
been defined for the Hot Forming and Cold Finishing Segment of the
Iron and Steel Industry. The first twelve Subcategories, i.e. Sub-
categories A through L have been previously incorporated under the
Steel Making Segment of the Iron and Steel Industry. Pretreatment
limitations for the Steelmaking Segment are given in another section
of this report. The Subcategories and limitations below cover both
carbon steel and specialty steel hot forming and cold finishing
operations.
M) Hot Forming, Primary
N) Hot Forming, Section
0) Hot Forming, Flat
P) Pipes and Tubes
Q) Pickling, Sulfuric Acid, Batch and Continuous
R) Pickling, Hydrochloric Acid, Batch and Continuous
S) Cold Rolling
T) Hot Coating, Galvanizing
U) Hot Coating, Terne
V) Miscellaneous Runoffs
W) Combination Acid Pickling, Batch and Continuous
X) Scale Removal, Kolene and Hydride
Y) Wire Pickling and Coating
Z) Continuous Alkaline Cleaning
Subcategory M, Hot Forming, Primary - Operations involving reduction
of hot steel ingots into slabs and blooms by rolling and associated
processes.
Subcategory N, Hot Forming, Section - Operations involving reduction
of hot steel blooms into various shapes and sizes of products including
billets, bars, rods and sections.
Subcategory 0, Hot Forming, Flat - Operations involving the reduction
of hot steel slabs into plates, strips and sheet steel or skelp.
Subcategory P, Pipes and Tubes - Operations producing welded or seam-
less pipe or tube, either by welding hot or cold skelp, or by piercing
hot blooms.
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Subcategory Q, Pickling, Sulfuric Acid Batch and Continuous - Operations
involving the immersion of rods, wire, strip or similar steel products
in a sulfuric acid bath and subsequent rinsing.
Subcategory R, Pickling, Hydrochloric Acid Batch and Continuous -
Operations involving the immersion of rods, wires, strip or similar
steel products in a hydrochloric acid bath with rinsing and associated
absorber vent and fume hood scrubbers.
Subcategory S, Cold Rolling - Operations involving the size reduction
and improvement in surface or mechanical properties of unheated steel
with associated rolling and cooling oils and solutions.
Subcategory T,. Hot Coat, Galvanizing - Operations involving the immer-
sion of steel strip or pipe in a bath of molten zinc; and associated
processes.
Subcategory U, Hot Coat, Terne - Operations involving the immersion of
steel in a bath of molten lead and tin, and associated processes.
Subcategory V, Miscellanous Runoffs - Runoff from coal, limestone, and
ore storage piles and discharges from castings and slagging operations.
Subcategory W, Combination Acid Pickling, Batch and Continuous -
The pickling of specialy steel in a nitric acid and hydrofluoric acid
bath, with or without a sulfuric acid or hydrochloric acid bath used
in-line with the nitric-hydrofluoric acid bath. After immersion in
the acid bath(s), the steel is rinsed.
Subeategory X, Scale Removal, Kolene and Hydride - The removal of
scale from alloy or stainless steel by immersion in a bath of a molten
salt such as kolene or hydride.
Subcategory Y, Wire Pickling and Coating - The pickling of alloy or
stainless steel wire and the coating of the wire (with copper or
another metal) to assist in further drawing of the wire.
Subcategory Z. Continuous Alkaline Cleaning - The removal of rolling
oil or other material from alloy or stainless steel in a continuous
process involving the electrolysis of the steel in an alkaline solution.
NATURE OF PROBLEM
Hot steel working differs considerably from cold finishing operations.
Essentially hot working of steel involves the deformation of steel at
elevated temperatures of 2150°F to 2450°F whereas cold finishing
processes are carried out at far lower temperatures, i.e. less than
1000°F. Hot forming operations rquire relatively large pieces of
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machinery and auxiliary equipment. Generally cold finishing processes
deal with much small steel sizes and do not utilize relatively large
equipment. Cold finishing processes are used to impart certain surface
characteristics to the steel products. Similarly, pickling and coating
are surface preparation procedures and do not involve any of the princi-
pal forming or shaping operations.
Pickling processes clean the metal surface by chemical means, i.e. with
acids. Coating operations serve to cover the surface of the steel with
another metal in order to impart special surface characteristics such
as corrosion resistance. Pickling and coating processes may be either
batch or continuous type. The principal coating materials include tin,
chromium, copper, lead and zinc.
Principal wastewater characteristics include oil and grease and TSS
from hot forming and cold rolling processes; and tin, lead, chromium,
copper and zinc from coating operations. Certain operations particularly
steelmaking, pickling and hot coating processes require the use of
wet gas cleaning equipment which create unique liquid scrubbing effluents.
Characteristics of wastes from the various subcategories and the iden-
tified sources of pollutants are described as follows:
M) Hot Forming, Primary - TSS, oil and grease are derived from
washing scale from the surface of the steel with water. Water
is also used to transport scale through the flumes below the mill
lines. The oils and greases principally originate from hydraulic
and lubricating systems. Additional wastewaters are generated
from scarfing operations which include the flush water to remove
the hot scale from the product generated by the scarfer; sprays
to protect against heat and flying scale particles; and wet
scrubbing effluents for removal of fume and smoke generated by
scarfing.
N) Hot Forming, Section - TSS, oil and grease principally coming
from washing scale off the surface of steel with water, and other
water used to transport scale through the flumes beneath the mill
lines.
0) Hot Forming, Flat - TSS, oil and grease principally coming
from washing scale off the surface of steel with water, water
used to transport scale through the flumes beneath the mill lines,
and other water for cooling the strip on the runout table.
P) Pipes and Tubes - TSS, oil and grease contained in roll spray
cooling waters, cooling bed and spray quench waters.
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Q) Pickling, Sulfuric Acid, Batch and Continuous - TSS, dissolved
iron and low pH's associated with spent, concentrated waste pickle
liquor and dilute solutions from the dunk and spray rinsing of
pickled.products. Wastewaters are also generated by fume scrubbers,
R) Pickling, Hydrochloric Acid, Batch and Continuous - TSS,
dissolved iron and low pH's associated with the same type of pick-
ling operations as for Subcategory Q. The operations of hydro-
chloric acid regeneration plants represents an additional potential
waste source.
S) Cold Rolling - TSS, oil and grease caused by the dumping of
spent rolling solutions used to provide cooling and lubrication
to the rolls and the products. These wastes contain oil and
grease in the form of water soluble oils as well as tramp oils
from mill equipment lubricating systems.
T) Hot Coatings, Galvanizing - TSS, oil and grease, zinc,
chromium and varying pH in wastes from cleaning, chemical
treatment and acid, alkaline or neutral rinses applied to
the products before and after coating together with spent
baths and other solutions from the coating operations. Wet
fume hood scrubbers may also be present generating a waste
scrubbing effluent.
U) Hot Coatings, Terne - TSS, oil and grease, lead, tin and
varying pH levels resulting from various cleaning or coating
rinses utilized on the products before and after coating.
Wet fume hood scrubbers may also be present generating addi-
tional waterborne waste.
V) Miscellaneous Runoffs, Storage Piles, Casting and Slagging -
TSS is reported as the main pollutant.
W) Combination Acid Pickling, Batch and Continous - TSS,
chromium, iron, fluorides and nickel associated with spent
concentrated waste pickle liquors and dilute solutions from
the dunk and spray rinsing of pickled products. Wastewaters
are also generated by fume scrubbers.
X) Scale Removal, Kolene and Hydride - TSS, chromium, iron,
cyanide (and possible pH problems) resulting from the removal
of scale by molten salt baths and ensuing dunk or spray
rinsing.
Y) Wire Pickling and Coating - TSS, chromium, iron, cyanide,
fluorides, nickel, copper, and low pH's resulting from pickling
and coating operations. Wastewaters may consist of spent con-
centrated solutions and dilute rinses.
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Z) Continuous Alkaline Cleaning - TSS, chromium, iron, nickel
and high pH's resulting from the cleaning of alloy or stainless
steel strip for the removal of oils and greases. Wastes may consist
of spent concentrated solutions and dilute rinses.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity
Alumi num
Ammonia N
Beryllium
BOD
Cadmium
Calcium
Chlorides
Chromium, hexavalent
and total
Cobalt
Color
COD
Copper
Cyanide, free and
total
Flow
Fluoride
Hardness
Iron, dissolved, ferrous
and total
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Nitrogen
Odor
Oil and Grease
Phenols
Phosphates
Selenium
Sulfates
Sulfide
Sulfite
IDS
Temperature
Thiosulfate
Tin
Titanium
TOC
TSS
Tungsten
Turbidity
Zinc
Zirconium
PRELIMINARY LIMITATIONS AND PRESCRIBED PRETREATMENT FOR DISCHARGE TO
POTW
In the EPA Development Document for the Hot Rolling and Cold Finishing
Segment of the Iron and Steel Industry, it is reported that pickle
liquor generally can be discharged to public sewers but only in limited
quantities. Furthermore these liquors should be at least partially
neutralized with soda ash, caustic soda or ammonia prior to release.
In certain cases, such discharges could impose unnecessarily excessive
loads upon the municipal system. Recovery of byproducts is possible
by the industry.
Proposed pretreatment regulations for existing and new sources in the
iron and steel industry are given in the Federal Register, 40 CFR,
dated March 29, 1976 as follows:
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102
M) Hot Forming, Primary Subcategory
For Existing and New Sources: Oil/Grease - 100 mg/1.
N) Hot Forming, Section Subcategory
For Existing and New Sources: Oil/Grease - 100 mg/1.
0) Hot Forming, Flat Subcategory
For Existing and New Sources: Oil/Grease - 100 mg/1.
P) Pipe and Tube Subcategory
For Existing and New Sources: Oil/Grease - 100 mg/1.
Q) Pickling, Sulfuric Acid Subcategory
For Existing and New Sources: Dissolved iron - 50 mg/1.
Oil/Grease - 100 mg/1
R) Pickling, Hydrochloric Acid Subcategory
For Existing and New Sources: Dissolved iron - 50 mg/1.
Oil/Grease - 100 mg/1
S) Cold' Rolling Subcategory
For Existing and New Sources: Dissolved iron - 50 mg/1.
Oil/Grease - 1.00 mg/1.
T) Hot Coating, Galvanizing Subcategory
For Existing Sources:
Avg. Max. Day
Pollutant tlb/1000 Ib. final product) (lb/1000 Ib. final product
Zinc .0125 .0375
Chromium. .0075 .0225
Oil/Grease 100 mg/1 100 mg/1
For plants with wet fume hood scrubbing, add the following
limitations to existing sources:
Zinc .0125 .0375
Chromium .0075 .0225
For New Sources:
Zinc .0050 .0150
Chromium .0005 .0015
Oil/Grease 100 mg/1 100 mg/1
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103
For plants with wet fume hood scrubbing, add the following
limitations to new sources.
Avg. 30 Day Max. Day
Pollutant (lb/1000 Ib. final product) (lb/1000 Ib. final product)
Zinc
Chromium
.0050
.0005
.0150
.0015
U) Hot Coating, Terne Subcategory
For Existing Sources:
Tin .01250 .03750
Lead .00125 .00375
Oil/Grease 100 mg/1 100 mg/1
For Plants with wet fume hood scrubbing as part of the coating
operation, add the following limitations to existing sources.
Tin .01250 .03750
Lead .00125 .00375
For New Sources:
Tin .00500 .01500
Lead .00063 .00189
Oil/Grease 100 mg/1 100 mg/1
For Plants with wet fume hood scrubbing as part of the coating
operation, add the following limitations to new sources.
Tin .00500 .01500
Lead .00063 .00189
V) Miscellaneous Runoffs Subcategory
For Existing and New Sources: Oil/Grease - 100 mg/1
W) Combination Acid Pickling, Batch and Continuous Subcategory.
For Continuous Operations, Existing and New Sources:
Diss. Chromium .0021 .0063
Diss. Nickel .0010 .0030
Diss. Iron 50 mg/1 50 mg/1
Oil/Grease 100 mg/1 100 mg/1
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104
For Batch Pipe and Tube Operations, Existing- and New Sources:
Avg. 30 Day Max. Day
Pollutant (lb/1000 Ib. final product) (lb/1000 Ib. final product)
Diss. Chromium
Diss. Nickel
Diss. Iron
Oil /Grease
.0015
.0007
50 mg/1
100 mg/1
.0045
.0021
50 mg/1
100 mg/1
For Other Batch Operations, Existing and New Sources:
Diss. Chromium .0004 .0012
Diss. Nickel .0002 .0006
Diss. Iron 50 mg/1 50 mg/1
Oil/Grease TOO mg/1 100 mg/1-
For Subcategory W the term "product" refers to the steel material that
is pickled in a combination of nitric and hydrofluoric acid.
X) Scale Removal, Kolene and Hydride Subcategory For Ketone,
Existing and New Sources:
Cyanide .0005 .0015
Diss. Chromium .0010 .0030
Diss. Iron 50 mg/1 50 mg/1
Oil/Grease 100 mg/1 100 mg/1
For Hydride, Existing and New Sources:
Cyanide .0013 .0039
Diss. Chromium .0025 .0075 .
Diss. Iron 50 mg/1 50 mg/1
Oil/Grease 10D mg/1 100 mg/1
Y) Wire Pickling and Coating Subcategory
For Existing and New Sources:
Diss. Nickel .0010 .0030
Diss. Copper .0010 .0030
Diss. Chromium .0021 .0063
Cyanide .0010 .0030
Diss. Iron 50 mg/1 50 mg/1.
Oil/Grease 100 mg/1 100 mg/1
Z) Continuous Alkaline Cleaning. Subcategory
-------
For Existing and New Sources:
105
Avg. 30 Day
Pollutant (lb/1000 Ib. final product)
Max. Day
(lb/1000 Ib. final product)
Diss. Chromium
Diss. Nickel
Diss. Iron
Oil /Grease
.00010
.00005
50 mg/1
100 mg/1
.00030
.00015
50 mg/1
100 mg/1
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106
ALUMINUM, COPPER, LEAD AND ZINC SEGMENT OF THE
NON-FERROUS METALS MANUFACTURING INDUSTRY
(145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155)
[Part 421]
SUBCATEGORIZATION OF THE INDUSTRY
The Aluminum, Copper, Lead and Zinc Segment of the Non-Ferrous Metals
Manufacturing Industry has been divided into 8 Subcategories as
described below:
A) Bauxite (Aluminum) Refining Subcategory
B) Primary Aluminum Smelting Subcategory
C) Secondary Aluminum Smelting Subcategory
D) Primary Copper Smelting Subcategory
E) Primary Copper Refining Subcategory
F) Secondary Copper Subcategory
G) Primary Lead Subcategory
H) Primary Zinc Subcategory
Subcategory A, Bauxite Refining. Bauxite refining is the process of
extracting alumina from aluminum ore (bauxite) by the Bayer process
or by combination processes. The Bayer process dissolves the alumina
in a caustic solution to form sodium aluminate. The sodium aluminate
is precipitated as aluminum hydroxide. The precipitate is filtered and
dried and becomes purified "alumina," the raw material for the produc-
tion of aluminum metal.
Subcategory B, Primary Aluminum Smelting. Primary aluminum smelting
involves the electrolytic reduction of purified "alumina" to produce
aluminum metal utilizing the Hall-Heroult process. Alumina is dissolved
in a solution or bath of molten cryolite and other fluoride salts.
The bath is kept molten in a carbon crucible. The crucible further
serves as the cathode and a carbon block (or blocks) inserted into the
bath serves as the anode. Electrolysis decomposes the alumina into
aluminum and oxygen. The aluminum sinks to the bottom of the crucible
and is captured. A primary aluminum facility typically consists of a
reduction cell operation, an anode formation plant, and an aluminum
casting house.
Subcategory C, Secondary Aluminum Smelting. Secondary aluminum smelting
is the process of remelting, purifying and recovering aluminum-bearing
scrap to produce an aluminum alloy of marketable specifications. A
variety of products are manufactured. Secondary aluminum smelters
recycle a moderately priced metal which otherwise would become a solid
waste. Secondary aluminum smelters receive two types of scrap raw
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107
material: 1) solids and 2) residues. The first of these includes metal
borings and turnings, new clippings and forgings5 old castings and sheet
and aluminum containing iron. Residues comprise two subtypes: dross
and skimmings from melting operations at foundries9 fabricators and the
primary aluminum industry; and secondly, slags formed during secondary
smelting operations. "Demagging," which is the removal of excess mag-
nesium from the melt, represents an important operation in secondary
aluminum smelters. Demagging is accomplished by passing chlorine
through the melt with the formation of magnesium chloride, or by mixing
aluminum fluoride with the melt resulting in the formation of magnesium
fluoride. Heavy fuming occurs with demagging, and extensive air scrub-
bing operations are generally available.
Subcategory D, Primary Copper Smelting. Includes all primary copper
smelting facilities and accompanying copper refineries, if such opera-
tions may exist on-site. The basic process used by the primary copper
industry, is pyrometallurgical. The primary smelter receives the
copper concentrates and subjects the concentrates to roasting, smelting,
and converting. Blister copper is produced. Blister copper is normally
purified by fire-refining, a pyrometallurgical operation. If additional
purification is necessary, an electrolytic process is used. The final
product is cathode copper. Byproducts consisting of gold, silver, etc.
which are actually contaminents of blister copper, are collected as
"slimes" during electrolytic refining and subsequently recovered.
Roasting serves to reduce sulfur and other impurities in the feed.
Smelting is carried out in a reverberatory furnace or an electric fur-
nace. The smelter provides for collection of a molten copper-iron-
sulfide material called "matte," suitable for subsequent treatment in
converters. In this process, slag is separated and discarded. Matte
is converted to blister copper with air blowing in large, horizontal,
cylindrical furnaces. Converter slag is removed and the crude copper
containing varying amounts of heavy metals, arsenic and sulfur is
ready for refining.
Subcategory E, Primary Copper Refining. Includes all primary copper
refineries which are not operated on-site with a primary copper smelter.
The blister copper described above is further refined into either fire-
refined copper or anode copper. Impurities are removed, more slag
produced and cuprous oxide formed. Deoxidation is accomplished by
coke addition and other means. This is usually followed by electrolytic
refining. In the latter process, copper is separated from its impuri-
ties by electrolytic dissolution at the anode, and deposition as the
pure metal, at the cathode. Non-copper values accumulated in the
"slimes" and in the solution electrolyte, are eventually recovered.
Subcategory F, Secondary Copper Facilities. Covers plants primarily
engaged in the recovery of copper from new and used scrap and from
residues gathered from melting operations. These residues comprise
spills, slags, skimmings, etc. This Subcategory includes establishments
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108
melting and refining copper alloys obtained from secondary brass and/or
secondary bronze scrap sources. Also included are establishments melting
and refining copper-bearing scrap to recover principally pure (unalloyed)
copper. "Primary" copper may occasionally be processed. Major operations
comprise presmelting, melting, smelting, refining and alloying. Products
consist of blister copper, brass or bronze ingots, fire-refined copper
ingots, and electrolytically refined and cast high-grade copper commo-
dities.
Subcategory G, Primary Lead Facilities. Includes plants primarily engaged
in smelting lead from ores, and refining lead by any process. Primary
lead in the U.S. is recovered entirely from sulfide ores, which are
associated with other metals chiefly zinc, copper and silver. The
primary lead facility receives the ore concentrate which is blended with
flux and other materials, and then provides sintering, blast furnace
smelting and refining operations to remove (and in some cases to recover)
metallic impurities. Sintering serves to reduce the sulfur oxide content
of the charge, to eliminate other undesirable impurities, and to produce
an even size feed for the blast furnace. The furnace separates consti-
tuents into the desirable molten metal and slag. Dressing is usually
the first step in the refining of the lead bullion as received from the
blast furnace. Dressing is performed in heated kettles and promotes
removal-of copper. The bullion then passes through "softening" accom-
plished by oxidative slagging or oxidation in a reverberatory furnace.
Generally two stages of slag are obtained. Softened lead is further
subject to desilverizing and dibismuthizing. The Parke process uses
zinc metal for purposes of combining with gold and silver, which are
recovered. Zinc is sequentially removed by vacuum dezincing. Debis-
muthizing consists of adding calcium and magnesium to form a calcium-
magnesium-bismuth crust which is later processed and recovered. Final
refining involves addition of sodium hydroxide and/or sodium nitrate
to the lead to effect removal of residual zinc, antimony and arsenic.
Subcategory H, Primary Zinc Facilities. Includes plants primarily
engaged in smelting zinc from ores, and/or refining zinc by any process.
The primary zinc industry in the U.S. includes both electrolytic and
pyrometallurgical retort plants. Zinc smelters receive sulfide con-
centrates which are blended and roasted. Roasting serves to remove
sulfur, and also eliminates some of the other impurities from the zinc
concentrates including lead, mercury and cadmium. Roaster off-gases
are passed to sulfuric acid manufacturing. For purposes of a uniform
feed, the roasting product is sintered, with off-gases treated for
particulate control. Large amounts of lead and cadmium are eliminated
in sintering, and the dust is recylced or recovered for cadmium and lead
values. In pyrolytic reduction, the zinc oxide content is reduced in
the furnace and all gases exhausted. These gases contain metallic zinc
vapor and carbon monoxide. The zinc vapor is specially condensed and
recovered. Residues are recycled and/or recovered for zinc or other
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109
metal values. In electrolytic zinc production, the zinc concentrate is
acid washed to remove unwanted magnesium sulfate and the roasted product
is finely ground. This material is then leached with a sulfuric acid
solution serving as an electrolyte. The purpose is to dissolve as
much zinc as possible and precipitate iron and accompanying impurities.
The pregnant solution is purified largely by addition of zinc dust
which precipitates copper, cadmium, cobalt, nickel, etc. by replacement.
All residuals are recovered. The electrolytic room receives the zinc
laden electrolyte. Zinc is deposited onto aluminum cathodes and eventually
stripped off. The final zinc products include various grades of slab zinc,
zinc oxide, and zinc dust. : .
NATURE OF PROBLEM
Major waste sources from the aluminum, copper, lead, and zinc subcate-
gories of the Non-Ferrous Metals manufacturing industry are described
as follows:
Bauxite Refining. Bauxite refining produces about equal amounts
of alumina and red mud waste and the latter represents an important
solid waste disposal problem. Other wastes comprise spent liquor,
condensates, barometric condenser and miscellaneous cooling waters.
Primary Aluminum Smelting. The majority of waste from primary
aluminum smelting originates from wet scrubbing devices for con-
trolling air emissions. Resulting scrub liquors contain acids,
hydrocarbon tars and oils, sulfur oxides, alumina, chlorides and
fluorides. Other wastes include cooling waters from casting,
rectifiers, and fabrication.
Secondary Aluminum Smelting. Waste waters are generated princi-
pally from the cooling of molten aluminum alloy, the wet scrub-
bing of fumes during magnesium removal, and the wet milling of
residues such as dross and slag. High TDS and TSS content of the
waste are generally attributable to the wet milling of residues.
Primary Copper Smelting. Smelting furnace slag represents a major
solid waste disposal problem at copper smelters. Sulfur oxide
emissions are treated by air pollution control devices which in
turn produce significant liquid waste. Air particulate control
and treatment are also important at primary copper smelters.
Other wastes originate from slag granulation, acid plant blowdown,
and from fire-refined copper.
Primary Copper Refining. Many of the same types of waste originate
from primary copper refining as found in primary copper smelting,
but in lesser degree. Specific waste sources include disposal of
spent electrolyte, electrolytic refinery washing, and slimes recovery,
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no
Secondary Copper. Waste waster is generated principally from six
operations: cooling of molten unalloyed or alloyed copper, slag
quenching and granulation, slag milling and classification, fur-
nace exhaust scrubbing, electrolytic refining, and equipment cooling.
Primary Lead Smelting and Refining. Major waste waters from pri-
mary lead establishments include waterborne effluent from a variety
of air cleaning/scrubbing devices, spent streams from blast furnace
slag and slag granulation circuits, acid plant blowdowns, and
various cooling waters.
Primary Zinc Smelting and Refining. Process wastes from zinc
establishments include scrub waters from the cleaning of roaster
off-gases, acid plant blowdowns, bleed streams from reduction
furnace gas cleaning operations, metal casting cooling, excess
liquors from cadmium recovery, preleaching of zinc concentrates,
electrolytic purification washwater and spills, boiler blowdowns,
scrub waters from auxiliary wet air pollution devices, and a
variety of "non-contact" cooling waters.
The non-ferrous metals manufacturing industry is characterized by
comparatively large plants but relatively limited in number. As of the
early 1970's, the following plants were identified for the domestic
industry: 9 bauxite refineries; 31 aluminum reduction plants; 85 plants
producing secondary aluminum metal; 22 plants or properties engaged in
primary smelting and refining of copper; 50 plants classified as secondary
copper smelters; 7 plants or properties engaged in lead smelting and/ or
refining; and 6 primary zinc establishments. In the zinc sector the
pyrometallurgical plants because of significant air pollution problems
and high corrective costs, are considered more vulnerable to future
shutdown.
PARAMETERS OF CONCERN
Bauxite Refining: pH, Alkalinity COD
IDS Oil/Grease
TSS Color
Temperature Turbidity
Sulfates Trace Metals
Primary Aluminum pH COD
Smelting: Fluorides Chlorides
TSS Sulfates
Oil/Grease Temperature
Cyanide Trace Metals (includes
TDS zinc, copper and nickel)
-------
in
Secondary Aluminum pH IDS
Smelting: TSS Chlorides
Oil/Grease Magnesium
COD Cyanide
Fluorides Nickel
Ammonia nitrogen Zinc
Aluminum Cadmium
Copper Lead
Sodium
pH: Raw wastewater from demagging fume scrubbers is very
acidic, with a pH range of 1.0 to 2.5. Metal cooling waters
are less acidic with a pH range of 4.5-6.5. Residue milling
wastewaters in contrast generally have a pH of 8.0-9.5.
Oil/Grease: Significantly exceed 100 mg/1 in some metal
cooling waters.
TSS: High levels of TSS are found in some wastewaters from
metal cooling and especially, residue milling. Excessive
TSS may cause blockage of sewer lines.
Aluminum: May be present in very high levels up to 200 mg/1
or more, in raw demagging fume scrub wastewaters and residue
milling wastewaters. Aluminum is present primarily in parti-
culate form, and therefore relatively settleable.
Ammonia: May be present in certain residue milling waste
waters in concentrations of several hundred mg/1. Ammonia
was determined to be "generally" amenable to biological
treatment by the POTW, if present in "limited" quantities.
Copper: Found in residue milling wastewaters. Studies
show about 75% of the incoming copper may be removed by a
POTW and eventually concentrated in treatment plant
sludges.
Primary Copper pH, Acidity, Sulfates
Smelting and Alkalinity Chlorides
Refining: TSS COD
Oil/Grease Cyanide
Arsenic Temperature
Cadmium Nickel
Copper Silver
Lead Cobalt
Selenium Iron
Zinc Antimony
TDS Tin
Aluminum Mercury
Chromium
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112
Secondary Copper: pH Cadmium
TSS Nickel
Oil/Grease Selenium
Ammonia nitrogen Silver
Copper Tin
Zinc Cobalt
Aluminum Magnesium
Iron Antimony
Lead Boron
COD Fluorides
Chromium
Copper; Most heavy metals including copper, are reported
as generally not susceptible to treatment by biological
means at POTW's. Past studies show approximately half of
the incoming copper will pass through the POTW, and the
other half is concentrated in treatment plant sludges. Copper
•is reported capable of causing toxic interference with
biological treatment with consequent reduction in waste
removal efficiencies. Copper in sludges may restrict reuse
and disposal of these sludges.
Zinc: Dissolved zinc is generally considered as not being
susceptible to biological treatment by POTW's. In slug
doses and in the presence of copper, zinc can be toxic to
biological treatment with consequent reduction in waste
removal efficiency. Zinc accumulating in treatment plant
sludges does not seem to restrict the reuse and/or disposal
of these sludges.
Lead: This metal is considered as generally not susceptible
to biological treatment by POTW's. Significant quantities
of lead are said to pass through the POTW while the remainder
of the lead is carried down with the sludges. Lead toxicity
can lower removal efficiencies of the biological treatment
plant. Lead accumulation in sludges may serve to restrict
the reuse and/or normal disposal of these sludges.
Cadmium; Represents a dangerous cumulative toxicant to
animals and humans, with possible mutagenic or tetratogenic
properties, and with marked acute and chronic effects. Cad-
mium acts synergistically with other metals including copper
and zinc. Cadmium is reported as generally not susceptible
to biological treatment by POTW's. Significant quantities
of cadmium may pass through the POTW, and the remainder
concentrates in treatment plant sludges. Cadmium toxicity
can significantly reduce biological treatment plant waste
removal efficiencies. Cadmium accumulation in sludges can
restrict the reuse and disposal of these sludges.
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113
Primary Lead Smelting
and Refining:
Primary Zinc Manu-
facture:
pH Various metals including
TSS aluminum, antimony, cobalt
Cadmium copper, chromium, iron,
Lead magnesium, nickel, silver,
Zinc selenium and tin.
Mercury
IDS Other possible pollutants
Sulfates of concern include arsenic,
cyanide, fluorides, bismuth,
oil/grease, chlorides,
temperature and phosphates
pH IDS
TSS Sulfates
Arsenic Chlorides
Cadmium Phosphates
Mercury
Selenium Various metals including
Zinc aluminum, magnesium,
Lead antimony, chromium,
Copper cobalt, iron, nickel,
silver and tin.
Other including cyanide,
temperature, etc.
PRETREATMENT LIMITATIONS FOR PI CHARGE TO POTVI
The Federal Register publications and supporting Development Documents
for the Non-Ferrous Metals Manufacturing industry indicate the follow-
ing pretreatment limitations:
Bauxite Refining, Subcategory A, Existing Sources (New Sources not
yet clearly defined).
N£ discharge of process wastes to POTW except for possible over-
flow from impoundment ponds during months of excess precipitation.
Primary Aluminum Refining, Subcategory B, Existing Sources (New
Sources not yet clearly defined).
Process waste water shall conform to the following values:
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114
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib product)t (lb/1000 Ib product)t
Fluorides 1.0 2.0
TSS 1.5 3.0
pH Allowable range of 6.0 to 9.0
Secondary Aluminum Smelting, Subcategory C, Existing Sources (New
Sources not yet clearly defined)!
For Metal Cooling Waste water:
Parameter Avg. 30 Day Max. Day
Oil/Grease - 100 mg/1
pH Not less than 5.0
For Fume Scrubbing Waste Water from Demagging operations:
Parameter
PH Allowable range of 5.0 to 10.0
For Residue Milling Waste Water:
Parameter Avg. 30 Day Max. Day
Ammonia 50 mg/1 100 mg/1
pH Not less than 5.0
Primary Copper Smelting, Subcategory D, Existing and New Sources.
Parameter Pretreatment Standard
Arsenic 10.0 mg/1
Copper 0.25 mg/1
Lead 0.5 mg/1
Cadmium 0.5 mg/1
Selenium 5.0 mg/1
Zinc 5.0 mg/1
Hoi aliarn-num metal produced.
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115
Primary Copper Refining, Subcategory E, Existing and New Sources.
Parameter
Oil /Grease
Arsenic
Zinc
Selenium
Copper
Secondary CojDper
Sources not yet
Avg. 30 Day
(lb/1000 Ib product)tt
0.02
0.02
0.01
0.01
0.0005
Manufacturing, Subcategory F,
clearly defined) .
Max. Day
(lb/1000 Ib p»
0.04
0.04
0.02
0.02
0.001
Existing Sources
*oduct)t
(New
The limitations below apply to all process wastes from secondary copper
mills:
Parameter Avg. 30 Day Max. Day
Copper 0.5 mg/1 1.0 mg/1
Cadmium 0.2 mg/1 0.4 mg/1
Oil/Grease - 100 mg/1
pH Not less than 5.0
Primary Lead Facilities, Subcategory G, Existing and New Sources.
Avg. 30 Day Max. Day
Parameter (lb/1000 Ib product)ttt (lb/1000 Ib product)ttt
Cadmium 0.0004 0.0008
Lead 0.0004 0.0008
Zinc 0.004 0.008
tt Electrolytically refined copper.
ttt Lead bullion.
-------
VT6
Primary Zinc Facilities, Subcategory H. Existing and New Sources.
• Avg. 30 Day Max. Day
Parameter Ob/1000 lb product)ttft (lb/1000 lb product)ttt
Arsenic
Cadmium
Selenium
Zinc
8.0 x 10 - 4
0.004
0.04
0.04
1.6 x 10
0.008
0.08
0.08
_3
PRESCRIBED TREATMENT MEASURES OR EQUIVALENT
Specifically for Secondary Aluminum, Subcategory C Facilities:
Metal Cooling Haste Waters: Treatment is required to remove
excessive oil and grease and TSS before release to a POTW.
Grease traps and specialized skimming equipment are identi-
fi cable technology for reduction of oil and grease. Adjust-
ment of pH may be necessary.
Demagging Fume Scrubber Waste Water: Aluminum is the prime
parameter of concern in these spent waters. Identified pre-
treatment technology for these effluents include pH adjustment
and/or neutralization,, floceulation and settling prior to release
to the POTW'.. In lieu of POTW discharge, complete recycle of
this wastewater is considered feasible and may be less, expensive.
Residue Milling Waste Water. Identified pretreatment technology
for the spent waters is settling, although pH adjustment and
floccolation may also be necessary.
Specifically for Secondary Copper, Subeategory F Facilities:
Overall Pretreatment: Identified technology is chemical treat-
ment consisting of controlled precipitation followed by settling.
Skimming is advocated where necessary to control oil and grease
levels. Mercury-laden wastes are subject to treatment with
sodium sulfide, the pollutant; removed by precipitation and
filtering. Neutralization with lime to a pH of 8 to 11; will
reduce concentrations of most metals and with proper settling,
will also reduce TSS. Each metal has an optimum pH for chemical
tttf Zina metal...
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117
precipitation. Metals such as lead, cadmium and mercury may show
lesser degrees of removal when the pH is above pH 7. Treatment
will likely require pH adjustment representing a compromise
between .the maximum removal of copper and zinc, and that suited
for maximum removal of cadmium, lead, antimony, tin, etc. Recycle
and reuse of process waste water streams should be carefully
considered.
Metal Cooling Waste Haters: Neutralization may not be necessary
for these waters. Pretreatment if needed will involve adjustment
of pH to between 8 and 10, followed by settling. Sludge removal
is probable when charcoal cover is employed in the metal cooling
and quenching process. Waste discharges to the POTW can be
reduced or eliminated by recycling process waters.
Slag Quenching/Granulation Waste Haters and Furnace Exhaust
Scrub Waters: Pretreatment comprises pH adjustment and/or
neutralization, followed by waste settling. Waste streams may
be treated separately or combined.
Electrolytic Refining Operations Waste Water. Identified
technology consists of removal or copper by cementation with
iron, followed by lime neutralization and solids settling
prior to release to the POTW. Special treatment for mercury
may be additionally required.
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1:18
PHOSPHATE MANUFACTURING INDUSTRY
(176, 177, T78, 179, 180, 1:81)
[Part 422]
SUBCATEGORIZATION OF THE INDUSTRY
The Phosphate Manufacturing Industry has been divided into six major
subcategories. It is defined separate from the Fertilizer Industry
although intermediate products are transferred between the two
industries. The first three subcategories are based upon use of phosphate
ores and "dry process" phosphoric acid whereas the last three subcate-
gories are based upon phosphate ores and/or "wet process" phosphoric
acid. The six subcategories are:
A) Phosphorous Production
B) Phosphorous Consuming
C) Phosphate Manufacturing
D) Defluorinated Phosphate Rock
E) Defluorinated Phosphoric Acid
F) Sodium Phosphates
Subcategory A. Phosphorous Production. Refers to the smelting and
reduction of phosphate ore to produce phosphorous and ferrophosphorous.
Copious amounts of water are used for cooling and granulating slag, and
for condensing phosphorous vapors from the furnace.
Subcategory B. Phosphorous Consuming. Elemental phosphorous is used
for the manufacture of various phosphorous compounds by the "dry
process". Products include phosphoric acid, phosphorous pentoxide,
phosphorous pentasulfide, phosphorous trichloride and phosphorous
oxychloride. Liquid phosphorous is burned, and the ?2^5 vapors are
quenched and hydrolyzed. Phosphoric acid mist is collected.
Subcategory C. Phosphate Production. Phospates including sodium,
tripolyphosphate, animal feed grade calcium phosphate, and human food
grade calcium phosphate are manufactured from dry process phosphoric
acid. For sodium tripolyphosphate, the acid is neutralized with
caustic soda and soda ash producing a mixture of mono and di-sodium
phosphates. The mixture is dried and calcined to yield the tripoly-
phosphate. The calcium phosphates are similarly made by the neutrali-
zation of phosphoric acid with lime giving mono, di-, or tricalcium
phosphate.
Subcategory D. Defluorinated Phosphate Rock. Applies to plants
practicing defluorination of phosphate rock by high temperature treat-
ment together with wet process phosphoric acid, silica and other reagents.
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Subcategory D, E and F plants use phosphate rock and importantly "wet
process" phosphoric acid as starting raw materials. The distinction
between "dry" and "wet" processes is provided under Nature of Problem
in this report.
Phosphate rock can be processed to provide animal feed supplements,
mainly the essential of calcium and phosphorous incorporated into
animal foodstuffs. However the 3-4 percent fluorine content in this
rock is too high for animal usage. Accordingly various proprietory
processes were developed to defluorinate phosphate rock, as incorporated
into Subcategory D plants.
Subcategory E. Defluorinated Phosphoric Acid. Two processes are
available. The first of these involves the concentration of "wet
process" phosphoric acid from a 52-54% P205 level up to a 68-72% P205
strength, i.e. superphosphoric acid. When water is evaporated from
the acid, fluorine is removed generally to a sufficient degree to
permit its use in the manufacture of animal feed supplements. The
second method of acid defluorination relies upon an additive incor-
porated into the acid which facilitates fluorine removal by aeration.
Defluorinated phosphoric acid may be mixed with limestone to produce
dicalcium phosphate for animal feed supplement use. Otherwise, it is
used for liquid fertilizer production. Superphosphoric acid is also
an intermediate used in the production of dry mixed fertilizer.
Subcategory F. Sodium Phosphates. These high quality salts usually
employ "wet process" phosphoric acid as a starting material, which
has been derived from calcined phosphate rock. A series of operations .
are employed for the removal of flurosilicates, arsenic, sulfates, iron,
aluminum and residual fluorine from the acid. The acid is eventually
converted to a salt laden, neutralized solution. Precipitated
impurities can be recovered for incorporation into fertilizer. The
solution is subjected to evaporation which serves to crystallize out
monosodium phosphate. Other end products include sodium meta phosphate,
disodium phosphate and tri-sodium phosphate.
NATURE OF PROBLEM
Background.
The Phosphate Manufacturing Industry may be descriptively defined as
the non-fertilizer phosphorous industry. The industry is almost
entirely based upon the production of elemental phosphorous from mined
phosphate rock. Phosphate rock in the U.S. is situated in the Tennessee,
Idaho-Montana and Florida areas. The first line product derived from
phosphate rock is elemental phosphorous with ferrophosphorous as a by-
product. (Subcategory A plants). A large portion of the elemental
phosphorous is used to manufacture high-grade phosphoric acid by the
"dry" process (as opposed to the "wet" process which converts phosphate
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rock directly into phosphoric acid; this lower grade wet process acid
is largely used in the fertilizer industry). The remainder of elemental
phosphorous is either marketed directly or converted to chemicals such
as phosphorous pentoxide, phosphorous pentasulfide, phosphorous trich-
loride and phosphorous oxychloride (Subcategory B plants). The latter
are used chiefly for synthesis in the organic chemicals industry.
Phosphoric acid is directly marketed to the food industry or to the
fertilizer industry, or otherwise is used for the manufacture of two
classes of phosphates: 1) the water soluble phosphates for detergents
and water treatment such as sodium tripolyphosphate; and 2) the water
soluble calcium phosphates used for addition to animal feeds and human
foods (Subcategory C plants).
Plants in Subcategories D, E and F, i.e., Defluorinated Phosphate Rock,
Defluorinated Phosphoric Acid, and high-quality Sodium Phosphates use
phosphate rock and "wet process" phosphoric acid as starting raw mate-
rials. These products find their way into animal feeds as nutritive
supplements, are used as fertilizer intermediates and for other needs.
Water Sources and Pollutional Characteristics.
In Phosphorous Production plants a grossly impure raw material is
employed.Consequently the wastes and byproducts generated are far
greater in quantity than the primary products recovered. The remainder
of the industry starts with relatively pure materials and generates
less unit wastes.
Electrostatic precipitators collect a dust that contains about 50 percent
phosphorous pentoxide, with other solids. The calciner and wet furnace
fume scrubber produce a highly acidic "phossy" liquid effluent containing
sulfur dioxide, iron oxides and phosphates, sulfates and fluorides. A
sludge originates in the phosphorous condenser sump. This is a mixture
of dispersed phosphorous and other solids that are scrubbed from the
air. This colloidal type waste is extremely harmful to aquatic organisms.
A slag quenching liquor stream is also present containing high TSS and
TDS, mainly sulfates and fluorides.
In Phosphorous Consumption plants, air pollution abatement systems
serving casting of phosphorous pentasulfide, product purification resi-
dues, tail gas seals, vessel cleaning, and leaks and spills represent
major waste sources. Chlorination is employed in production of
phosphorous trichloride and phosphorous oxychloride which leads to the
formation of hydrochloric acid and a difficult waste water problem.
In Phosphate Production plants, effluents are derived from wet scrubbers,
spray and dust deposits, clarified waste water from centrifuges and
filtrate fractions. A defluorination process in food grade phosphate
production contributes large amount of TSS. The raw wastes from phos-
phate production contain fluoride, calcium and sodium compounds, arsenic
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121
compounds, phosphorous, phosphoric acid, sulfurous acid, sulfuric acid,
hydrochloric acid, TSS, chromates, IDS and ammonia. Large amounts of
cooling waters are used by these plants, and heat is a general problem
in the discharges. Some western ores contain considerable cadmium.
This element does not normally appear in the phosphate manufacturing
discharges. Vanadium and radium occur in some ores and are potential
pollutants.
In Defluorinated Phosphate Rock production, serious waste water prob-
lems result from wet phosphoric acid production which is the same case
for the production of defluorinated phosphoric acid and sodium phosphate
salts i.e. Subcategories E and F. These wastes include large amounts
of sulfuric acid derived from stack or tail gas scrubbing, filtration,
solids washing and acid manufacturing. Also included are large quan-
tities of solid wastes from various manufacturing together with signi-
ficant amounts of gypsum and phosphate rock debris. The major wastes
from plants processing defluorinated phosphate rock are the scrub effluents
from cleaning gaseous effluents.
In Defluorinated Phosphoric Acid production, major wastes are the scrub
effluents from wet air pollution control devices and the condensates
from the acid concentration process. Other waste sources include
spills, pump seal leaks, etc. The condensates contain phosphoric acid,
fluorides, etc.
In Sodium Phosphates production, wastes result from various salting out
processes and the solids removed via precipitation means. Phosphoric
acid by the "wet process" produces a type of waste already described
above. Other waste sources include pump and seal leaks, spills, etc.
Solid wastes control is very important in the phosphate industry.
The waste waters and the treatment processes generate considerable
volumes of hydrated fluorsilicaceous and silicaceous materials.
These hydrated solid wastes form relatively unstable landfill deposits.
In order to ensure long term protection of the environment from what-
ever hazardous and harmful constituents may be present, special pre-
cautions must be exercized over waste disposal sites. The landfills
should be selected and designed to prevent horizontal and vertical
migration of these critical constituents to ground and surface waters.
Also, the location of solid hazardous materials disposal sites should
be permanently and legally recorded.
PARAMETERS OF CONCERN
pH, Alkalinity, Acidity
TSS
TDS
Phosphates, phosphites
Sulfates, sulfites
Fluorides, fluorosilicates
Arsenic
Vanadium
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PHr.0s4Jho.rQ.u5 „ e^emejiitad; phosphorous; Rad!i;ujn^22j5;
Chlorides Uranium;
Cadmium liron
Aluminum: Ca.lcium.
Temperature COD
Radium-226 is one of the most hazardous radioisotopes of the uranium
decay series, when present in. water. The human body preferentially
utilizes radium, over? calcium when present in food or drink. Plants
and animals concentrate radium,, leading to a multiplier effect upon
the food chain.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
For Subcategory A. Phosphorous Production:, Existing Sources.
Limitations have been* equated to BPT limits; which are:
Avg. 30 Day Max. Day
Pollutant (lb/1.000 Ib. product}(lb/l.QOO Ib Ib product)
TSS 0.5 1.0s
Total Phosphorous 0.15 0.30
Fluorides 0.05 0.10
Elemental Phosphorous No detectable quantity
6.0 to 9.0
For Subcategory A, Phosphorous Production, New Sources.
Limitations have not yet been defined.
For Subcategory B, Phosphorous Consuming, Phosphoric Acid, Phosphorous
Pentoxide and Phosphorous Pentasulfide Manufacturing, Existing Sources.
No discharge of process waste water pollutants is allowed.
For Subcategory B, Phosphorous Consuming. Phosphorous Trichloride
Manufacturing, Existing Sources.
Have been equated to BPT limitations which are:
TSS 0.7 1.4
Total Phosphorous 0.8 1.6
Arsenic 0.00005 0.0001
Elemental Phosphorous No detectable quantity
pH 6.0 to 9.0
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For Subcategory B, Phosphorous Consuming, Phosphorous Oxychloride
Manufacturing, Existing Sources.
Have been equaled to BPT limits, which are:
TSS 0.15 0.30
Total Phosphorous 0.17 0.34
pH 6.0 to 9.0
For Subcategory B, Phosphorous Consuming. All New Sources.
Limitations have not yet been defined.
For Subcategory C, Phosphate Manufacturing, Existing Sources.
Have been equated to BPT limits, which are:
TSS 0.06 0.12
Total Phosphorous 0.03 0.06
pH 6.0 to 9.0
For Subcategory C, Phosphate Manufacturing, New Sources.
Limitations have not yet been defined.
For Subcategory D, Defluorinated Phosphate Rock, Existing Sources.
Avg. 30 Day Max. Day
Pollutant mg/1 mg/1
BOD, TSS, pH No limitations No limitations
Total Phosphorous 35 70
Fluorides 15 30
Volume restrictions are implied on wastewaters to be released to a POTW
but these limitations are not clearly defined. Previously this limita-
tion was described as an excess flow from an impoundment capable of
holding a 10 year, 24 hour rainfall event or the difference between
precipitation into the impoundment and evaporation from the pond water
surface area. However the latter definition has since been changed.
For Subcategory D, Defluorinated Phosphate Rock, New Sources.
BOD, TSS, pH No limitations No limitations
Total Phosphorous 35 70
Fluorides 15 30
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The volume of allowable process waste water is defined in the same
manner as given above for existing sources of Defluorinated Phosphate
Rock.
For Subcategory E, Defluorinated Phosphoric Acid, Existing Sources.
Avg. 30 Day Max. Day
Pollutant (mg/1) (mg/1)
BOD, TSS, pH No limitations No limitations
Total Phosphorous 35 70
Fluorides 15 30
The volume of allowable process waste water is defined in the same
manner as given above for existing sources of Defluorinated Phosphate
Rock.
For Subcategory E, Defluorinated Phosphoric Acid, New Sources.
.BOD, TSS, pH No limitations No limitations
Total Phosphorous 35 70
Fluorides 15 30
The volume of allowable process waste water is defined in the same
manner as given above for existing sources of Defluorinated Phosphate
Rock.
For Subcategory F, Sodium Phosphates, Existing Sources.
Avg. 30 Day Max. Day
Pollutant (lb/1,000 Ib. product)(lb.1,000 Ib product)
BOD, TSS, pH No limitations No limitations
Total Phosphorous 0.40 0.80
Fluorides 0.15 0.30
For Subcategory F, Sodium Phosphates, New Sources.
BOD, TSS, PH No limitations No limitations
Total Phosphorous 0.40 0.80
Fluorides 0.15 0.30
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
With regard to f 1ow rate to a POTW, it has been recommeded that each
plant in the phosphate industry be required to determine impact of its
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flow upon the hydraulic capacity of the POTW collection and treatment
system should the POTW be used by the industry. This analysis should
include effects of a time-varying flowrate.
With respect to TSS, high concentrations of inorganic solids could
overload primary sludge collectors, the primary sludge pumps, the
sludge thickeners, dewatering operations, and the sludge disposal
system. Furthermore these solids would provide no food for the micro-
flora in secondary treatment and also reduce the activity of the biomass.
It is recommended that the maximum concentration of suspended inorganic
solids be held to 250 mg/1.
For Metals, it is noted that elemental phosphorous in phossy waters
and enriched arsenic compounds are potential substances discharged
to POTW's. There is special need to pretreat waste waters for removal
of these materials. It is recommended that pretreatment standards
provide for zero discharge of metals or harmful materials to POTW's.
Dissolved Phosphates would affect sludge operations in POTW's. Gravity
thickened sludges are generally conditioned with various chemicals.
However, phosphates would react with these chemicals and be precipitated,
detracting from the efficiency of these agents in properly conditioning
the sludges. In the case of tertiary treatment at a POTW, phosphates
are generally removed by using lime, ferric chloride or alum. Phosphate
industry discharges would cause greatly increased chemical dosages and
seriously impact upon the sludge handling capacity of the POTW. It is
recommended that the maximum permissable phosphate concentration (as
P04) to a POTW be held to 30 mg/1.
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STEAM ELECTRIC POWER GENERATING INDUSTRY
(201, 202, 203, 204, 205)
[Part 423]
SUBCATEGORIZATION OF THE INDUSTRY
The Steam Electric Power Generating Industry has been divided into
four main subcategories as described in the following paragraphs.
A) Generating Unit Subcategory.
A generating unit operated by an establishment primarily engaged
in generating electricity for distribution and sale which results
primarily from a process utilizing fossil-type fuel (coal, oil or
gas) or nuclear fuel in conjunction with a thermal cycle employ-
ing the steam water system as the thermodynamic medium. The
term "generating unit" however shall not include those units
defined below as either "small" or "old."
Small Unit shall mean any generating unit (except one defined
as being old) having less than 25 megawatts rated net generat-
ing capacity or any unit which is part of an electric utilities
system with a total net generating capacity of less than 150
megawatts.
Old Unit shall mean any generating unit of greater, than 500
megawatts rated net generating capacity place in service on
or before January 1, 1970, or any generating unit of less
than 500 megawatts rated net generating capacity placed in
service on or before January 1, 1974.
B) Small Unit Subcategory
A small unit operated by an establishment primarily engaged in
generating electricity for distribution and sale which results
primarily from a process utilizing fossil-type fuel (coal, oil
or gas) or nuclear fuel in conjunction with a thermal cycle
employing the steam water system as the thermodynamic medium.
For further definition of Small Unit see Subcategory A directly
above.
C) Old Unit Subcategory
An old unit operated by an establishment primarily engaged in
generating electricity for distribution and sale which generally
results primarily from a process utilizing fossil-type fuel (coal,
oil or gas) or nuclear fuel in conjunction with a thermal cycle
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employing the steam water system as the thermodynamic medium.
For further definition of Old Unit see Subcategory A above.
D) Area Runoff Subcategory
This Subcategory applies to discharges from material storage
runoff and construction runoff which are used in or are derived
from generating units covered under Subcategories A, B and C.
Special definitions for this Subcategory are given below.
Material storage runoff shall mean the rainfall runoff from
or through any coal, ash or other material storage pile.
Construction runoff shall mean the rainfall runoff from any
construction activity and any earth surface disturbed by such
activity from the start of construction until the completion
of construction and the disturbed earth is returned to a
vegetative or other cover state commensurate with the intended
land use.
Other definitions appropriate to all subcategories are included below:
Slowdown shall mean the minimum discharge of recirculating
water for the purpose of getting rid of materials contained
in these waters, the further buildup of which would cause
concentrations in amounts exceeding limits established by
best engineering practices.
Sufficient land shall mean 1,100 square feet or more of
land per megawatt of nameplate generating capacity.
Low Volume Waste Sources shall mean wastewater from diverse
sources except those for which specific limitations have
been otherwise established. Low volume waste sources include
but are not limited to waters from wet scrubber air pollution
control systems, ion exchange water treatment systems, water
treatment evaporator blowdown, laboratory and sampling
streams, floor drainage, cooling tower basin cleaning wastes,
and blowdown from recirculating house service water systems.
Ash transport water shall mean water employed in hydraulic
transport of either fly ash or bottom ash.
Metal cleaning wastes shall mean any cleaning compounds, rinse
waters, or any other waterborne residues derived from cleaning
any metal process equipment including, but not limited to
boiler tube cleaning, boiler fireside cleaning and air preheater
cleaning.
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Once-through cool ing water shall mean water passed through
the main cooling condensers in one or two passes for the
purpose of removing waste heat from the generating unit.
Recirculated cooling water shall mean water passed through
the main condensers for the purpose of removing waste heat
from the generating unit, passed through a cooling device,
other than a cooling pond or a cooling lake, for the purpose
of removing such heat from the water and then passed again,
except for blowdown, through the main condenser.
Cooling pond shall mean any man-made water impoundment which
does not impede the flow of a navigable stream and which is
used to remove waste heat from heated condenser water prior
to returning the recirculated cooling water to the main
condenser.
Cooling lake shall mean any man-made water impoundment which
impedes the flow of a navigable stream and which is used to
remove waste heat from heated condenser water prior to recir-
culating the water to the main condenser.
NATURE OF PROBLEM
Steam-electric power plants burn fuel to produce heat to generate
steam, which in turn drives turbine generators for the production
of electrical energy. The spent, expanded steam is condensed to water
by transferring the unusable waste heat to a cooling water circuit(s).
The condensed steam becomes high quality water which is returned to the
powerplant boiler ready for reuse. The rejected heat is wasted to the
environment.
Steam electric powerplant (.stations) consist of one or more generating
units. Typically, a generating unit consists of a discrete boiler,
turbine-generator, and a condenser system. However some units employ
multiple boilers associated with multiple turbine-generators. Fuel
storage and handling, water treatment facitilies, and miscellaneous
components may be part of a discrete generating unit, or may service
more than one generating unit.
Generally, the newer, larger, more efficient generating units are
assigned base-load service; and the older, smaller, less efficient
generating units are used for meeting peak demands. The type of
service (whether base load, etc) and the remaining service life
characteristics of the unit are important factors affecting ability
in meeting effluent reductions relative to the quantities of heat
generated.
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The Federal Power Commission describes base-load, intermediate,
and peaking units as follows. Base-load units are designed to run more
or less continuously near full capacity except for periodic maintenance
shutdowns. Peaking generating units are designed to provide electricity
principally during periods of maximum system demand and operate only a
few hours a day. Units employed for intermediate service range between
the extremes of base-load and peaking service and are designed to respond
readily to swings in system demand, or cycling. Net generation at
any unit is less than the gross generation because electricity is
used by the power plant itself.
Nuclear power generation units are almost always used for base-load
service in spite of the significantly larger quantities of waste
heat discarded to cooling water compared to otherwise similar fossil-
fuel base-load units.
Base-load units represent approximately 70 percent of the total U.S.
installed capacity of steam-electric powerplants; cycling about 25
percent;.and peaking units about 5 percent. However when viewed in
terms of the total U.S. steam electric energy actually produced, the
base-load units account for approximatly 90 percent of the real
energy (and spent heat) generated; cycling units about 10 percent;
and peaking units less than 1 percent.
Steam electric powerplants discharge around 50 trillion gallons of
waste water per year, which amounts to about 15% of the total flow
of waters in U. S. rivers and streams. Almost all of these waters
contain heat and in come cases, chemicals added by the powerplants.
The general types of wastewater streams from powerplants include: 1)
cooling system waste waters; 2) metal cleaning wastes; 3) boiler
blowdowns; 4) ash transport waters; and 5) various low volume wastes.
These are described below:
Condenser cooling systems at power plants are classified either as
once-through or recirculating. In once-through cooling systems,
biocides such as chlorine or hypochlorites are generally added to
the system to minimize biological growth within the condenser(s) and
are therefore likely discharged. In recirculating cooling systems
the waters will contain: a) chemical additives to control growth of
organisms (chlorine, hypochlorites, organic chromates, etc); chemical
additives to inhibit corrosion (organic phosphates, chromates, zinc
salts, etc); and materials present in the intake waters (but at much
higher concentration due to evaporative losses).
Metal cleaning wastes are derived from the cleaning of metal process
equipment. Such equipment includes boiler tubes, boiler fireside
and air preheaters. Pollutants in these wastes include oil and grease,
iror. copper, nickel, zinc, TSS, and chromium.
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130
Boiler blowd'own wastes usually demonstrate high pWi and high IDS.
Phosphates used for the precipitation of calcium and magnesium salts
are generally found in boiler blowdown.
When coal and oil are burned, ash residues are created. These ashes may
be transported by water to a settling pond or basin. Some or all of the
water from the pond or basin may be dis-charged. Ash handling wastes
derived from coal-fired plants may contain TSS, iron, aluminum, mercury,
and oil and grease. Oil-fired plants can additionaly produce vanadium.
Low volume wastes include ion exchange water treatment, water treat-
ment evaporative blowdown, laboratory and sampling streams, floor
drainage, cooling tower basin cleaning, ash pollution device effluent,
and other aqueous power plant wastes not previously cited. These
wastes contain primarily TSS and oil and grease.
Area runoff can contain TSS and oil and grease. Runoff from coal
piles may also contain iron, high or low pH. values, copper, zinc and
manganese.
The Steam Electric Power Industry is comprised of approximately 1,300
plants throughout the continguous U.S. Some 98 plants or 7.7 percent,
are said to discharge wastewaters to POTW's. Steam Electric plants
tied into POTW's are smaller on the average than plants discharging
to surface streams. These plants averaged 150 MW vs. about 400 MW for
the entire Stream Electric Industry. Plants connected to POTW's are
also older than plants discharging to surface streams. No nuclear
powered plants are believed to be connected to POTW's.
PARAMETERS OF CONCERN,
pH, Acidity, Alkalinity*
Algicides
Aluminum
Ammonia W
BOD
Boron
Bromide
COD
Chlorides
Copper*
Debris
Fecal Coliforms
Fluorides
Chlorine-free available and
total, residual*
Heat*
TDS
Magnesium
Manganese
Mercury
Nitrate N:
Oil/Grease*
Phenols
Selenium
Sulfates
Sulfites
Surfactants
Total chromium*
Hardness
Phosphorous
TSS*
Turbidity
* Most significant pollutant parameters.
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Iron Vanadium
Lead Zinc*
Nickel*
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
The USEPA Draft Supplement for Pretreatment to the Development Docu-
ment for the Steam Electric Power Generating Industry tentatively
concluded that power plants discharging to POTW's are capable of pre-
treating effluents equivalent to BPCTCA. However, a survey of current
industry practices indicated that most plants provide little pretreat-
ment of their chemical-type wastewaters.
The USEPA has determined that control of copper, nickel and zinc
associated with metal cleaning wastes at a power plant are required.
Additionally, control of oil and grease from the plant's combined dis-
charge to the POTW is required. The metals were found incompatible
because they can interfere with proper operation of the POTW; they
may not be adequately treated; and threats are posed both to the
receiving waters and to vegetation and crops grown on soil treated
with sludges from the POTW. A pretreatment standard of 1 mg/1 copper
was established because this level can be attained by BPT technology
(lime precipitation). Limits for nickel and zinc were not imposed
because they are indirectly controlled through the regulation of
copper. When copper may not be present in significant quantity but
nickel and zinc are found in high levels, it may be necessary for the
POTW to regulate the latter metals to concentrations achievable by
lime precipitation. Discharge of oil/grease of petroleum origin
exceeding 100 mg/1 from a power plant could interfere with the POTW
or be inadequately treated. Power plants can comply with the oil/
grease standard of 100 mg/1 by using good housekeeping procedures
and by other methods.
Pretreatment Standards for Existing Sources Within Subcategories A, B,
and C (New Source Limitations not yet clearly defined).
Parameter Limitation
Copper in metal cleaning wastes 1 mg/1 Quantity of copper
allowed = flow of metal
cleaning wastes x 1 mg/1.
Oil/Grease in combined discharge 100 mg/1; Quantity of oil/
grease allowed to POTW =
combined flow x 100 mg/1
PCB's Prohibited
pH pH shall not be less than
5.0, unless the POTW is
designed to accomodate
this condition.
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Pretreatment Standards for Existing Sources Mi thin Subcategory D.
(New Source Limitations not yet clearly defined).
Parameter Limitation
pH pH shall not be less than 5.0
unless the POTW is designed
to accomodate this condition
Treatment can lower the oil/grease content to 20 mg/1 or below by
using properly-designed oil skimmers. The pretreatment standard of
100 mg/1 for oil and grease should be easily attainable by good
housekeeping practices. Treatment of metal cleaning wastes to achieve
the pretreatment standard of 1.0 mg/1 copper would consist of oil and
grease skimming, waste equalization, lime addition to attain a pH
level of about 9, followed by settling. This treatment sequence
should also significantly reduce nickel, zinc and choromate pollutant
loads. Disposal of chemical sludges from the treatment works must be
conducted so as to ensure long-term protection of the environment
especially adjacent surface and ground waters. The recommended pre-
treatment technology for power facilities further includes in-plant
measures to recycle and reuse waste waters at the industrial site.
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FERROALLOYS MANUFACTURING INDUSTRY
(165, 166, 167, 168, 169, 170)
[Part 424]
SUBCATEGORIZATION OF THE INDUSTRY
The Ferroalloy Industry is divided into seven subcategories predicated
upon type of melting furnace used, air pollution control devices
available, and specific ferroalloy or metal produced. These are:
A - Open Electric Furnaces with wet air pollution control
devices subcategory
B - Covered Electric Furnaces and other smelting operations
with wet air pollution control devices subcategory
C - Slag Processing subcategory
D - Covered Calcium Carbide Furnaces with wet air pollution
control devices subcategory
E - Other Calcium Carbide Furnaces subcategory
F - Electrolytic Manganese Products subcategory
G - Electrolytic Chromium subcategory
Further description of major processing operations within each sub-
category is provided below:
Subcategory A. Applies to the smelting of ferroalloys in open electric
furnaces with wet air pollution control devices. Includes electric
furnaces of such construction or configuration that the furnace off-gases
are burned above the furnace charge level by air drawn into the system.
After combustion, the gases are cleaned via a wet air pollution control
device, such as a scrubber, an ESP with water, or other aqueous sprays,
etc. This subcategory does not include electric furnaces which are
covered, closed, sealed or semi-covered, or where the off-gases are not
burned prior to collection.
Subcategory B. Applies to covered electric furnaces or other smelting
operations not defined elsewhere under the ferroalloy industry, and
having wet air pollution control devices. Included are those furnaces
of such construction or configuration and known as covered, closed,
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sealed, semi-covered or semi-closed, and in which the furnace off-gases
are not combusted prior to collection and cleaning. The off-gases after
collection are cleaned in a wet scrubber, wet baghouse etc. This
subcategory includes non-electric furnace smelting operations such as
exothermic, smelting, ferromangenese, etc., equipped with wet air pollu-
tion control devices. Furnaces which utilize dry dust collection
techniques are not included.
Subcategory C. In slag conversion, either the "concentration" or the
"shotting" process is used. In the first process, the slag floats to
the surface of the water, and the metal particles which are eventually
recovered, sink to the bottom. The concentration process is generally
employed on ferrochromium slags. The shotting practice involves the
granulation of molten slag in water and is usually employed with ferro-
manganese slags.
Subcategory D. Applies to the production of calcium carbide in covered
electric furnaces which employ wet air pollution control devices. In-
cludes electric furnaces of such construction or configuration and known
as covered, closed, sealed, semi-covered or semi-closed, and in which
the furnace off-gases are not combusted prior to collection and cleaning.
The off-gases once collected are cleaned in a wet scrubber, wet baghouse,
etc. This subcategory excludes furnaces which utilize dry dust col-
lection techniques such as dry baghouses, etc.
Subcategory E. Applies to the production of calcium carbide in covered
furnaces which do not utilize wet air pollution controls. Covered
calcium carbide furnaces with wet air pollution controls are regulated
under Subcategory D above. Open or uncovered calcium carbide furnaces
are regulated under 40 CFR, Part 415, the Inorganic Chemicals Industry.
Subcategory F. Applies to the manufacture of electrolytic manganese
products such as electrolytic manganese metal or electrolytic manganese
dioxide. The processing involves leaching the metal from the ores,
purification of the leach solution, plating of the product and final
product preparation. Ammonia is used in the production of both electro-
lytic manganese and chromium, but not manganese dioxide.
Subcategory G. Applies to the manufacture of chromium metal by the el-
ectrolytic process. However, this subcategory is not applicable to the
manufacture of chromium metal by aluminothermic or other methods.
NATURE OF THE PROBLEM
Farroalloys are used for deoxidation, alloying and graphitization of
steel and cast iron. In the nonferrous metal industry, silicon is used
primarily as an alloying agent for copper, aluminum, magnesium and
nickel. Manganese is the most widely used element in ferroalloys
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135
followed by silicon and chromium. Other elements include molybdenum,
tungsten, titanium, zirconium, vanadium, boron and columbium. The U.S.
is almost entirely dependent upon commercial sources of manganese,
chromium and other ores from outside the country. Ores are crushed
prior to entry into the melt furnaces.
There are four major methods used to produce ferroalloy and high-purity
metallic additives for steel making which are: 1) the blast furnace;
2) the electric furnace; 3) the alumino or silicothermic process; and
4) electrolytic deposition. Electric smelting furnaces produce most
of the ferroalloy tonnage. The major ferroalloys produced are silicon
alloys e.g. ferrosilicon; chromium alloys e.g. high carbon ferro-
chromium; and manganese alloys, e.g. standard ferromanganese. Air pol-
lution control devices are in widespread use in the industry including
baghouses, wet scrubbers, and electrostatic precipitators. Accordingly,
the largest source of water-borne pollutants other than thermal in the
industry is the use of wet methods for air pollution control. There are
some 40 plants in the U.S. which produce ferroalloys, chromium, manga-
nese and other additive metals.
Calcium carbide is manufactured by thermal reduction of lime and coke
in an electric furnace. Emissions from calcium carbide furnaces have
a major impact upon water pollution in plants using wet air pollution
controls. Manganese metal and chromium metal are manufactured electro-
lytically from ores, ferroalloy slag or ferroalloys.
Major waste sources and pollutants within the seven subcategories of
the Ferroalloy Manufacturing Industry are summarized as follows:
Subcategory A. Open Electric Furnaces with wet air pollution control
devices. Wet air cleaning collects particulates from furnace gases
either by gas scrubbing, or by water sprays prior to electrostatic pre-
cipitators. The particulates are generally oxides of the material
being smelted. With this type of furnace, most cyanide and phenol
is destroyed in the combustion of the off-gases. The wastewaters con-
tain large amounts of TSS and smaller amounts of manganese and chromium.
Yet smaller quantities of phenol and oil are generally found in these
effluents.
Subcategory B. Covered Electric Furnaces and other smelting operations
with wet air pollution control devices. Wastes are similar to those
for Subcategory A but since in covered smelting furnaces the off-gases
are not combusted, this results in cyanide and phenol being present in
rather significant quantities in the scrubber wastewaters.
Subcategory C. Slag Processing. The most important pollutant may be TSS
with manganese and chromium present in lesser amounts.
Subcategory D. Covered Calcium Carbide Furnaces with wet air pollution
control devices. The off-gases from covered calcium carbide furnaces
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136
usually contain about 70% carbon monoxide and lesser amounts of cyanides.
Calcium carbide manufacturing and scrubbing wastes contain predominately
TSS with cyanides also present. These wastes usually are of high pH.
Subcategory .E. Other Calcium Carbide Furnaces. Air pollution control
by plants in this subcategory may be by baghouses in conjunction with
evaporative cooling, or is non-existent. Therefore, little water pol-
lution potential is usually present.
Subcategory F. Electrolytic Manganese. The main pollutants in waste-
waters from the manufacture of electrolytic ferroalloys are TSS and
ammonia. Manganese is found to some extent in the spent waters from
all electrolytic products. Electrolytic manganese plants appear to
have two main waste streams. The first is a highly concentrated effluent
referred to as strong electrolytic manganese waste derived from the hy-
draulic transport of filter residues to tailings ponds and which also
carries small quantities of electrolyte solution (spilled or dumped).
These wastes may contain several thousand mg/1 TSS, manganese and
ammonia, and may also have low pH. The second stream is referred to
as the weak electrolytic manganese waste derived from product washing
and other. This waste may contain a few hundred mg/1 of TSS, manganese
and ammonia.
Subcategory G. Electrolytic Chromium. Resulting wastes may contain
several thousand mg/1 of chromium, TSS and ammonia and have a low pH.
Manganese can also be present in appreciable quantities.
PARAMETERS OF CONCERN
pH, alkalinity, acidity Oil and Grease
Temperature Phenols
TSS Phosphates
Total Chromium Iron
Hexavalent Chromium Zinc
Cyanides Aluminum
Manganese Lead
TDS Color
Ammonia-N Calcium, Sodium,
Turbidity Potassium, Silica
LIMITATIONS FOR DISCHARGE TO POTW
Pretreatment limitations for existing and new sources in the
Ferroalloy Manufacturing Industry have been proposed as follows:
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137
For Subcategory A, Open Electric Furnaces With Wet Air Cleaning,
Existing Sources
Have been equated to BPT limits which are:
Avg. 30 Days Max. Day
Pollutant (Ib/Megawatt hrs. energy (Ib/Megawatt hrs. energy
consumed in furnace) consumed in furnace)
TSS
Chromium, total
Chromium, hexavalent
Manganese, total
PH
0.352
0.007
0.0007
0.070
6.0 to 9.0
0.703
0.014
0.0014
0.141
For Subcategory A. Open Electric Furnaces With Met Air Cleaning, New Sources
Limitations have not yet been defined.
For Subcategory B, Covered Electric Furnaces and Other Smelting With
Wet Air Cleaning, Existing Sources
Have been equated to BPT limits which are:
TSS 0.461 0.922
Chromium, total 0.009 0.018
Chromium, hexavalent 0.0009 0.0018
Manganese, total 0.092 0.184
Cyanide, total 0.005 0.009
Phenols 0.009 0.013
pH 6.0 to 9.0
Provided however, that for non-electric furnace smelting operations, the
permitted limits shall read as Ib/ton of products rather than Ib/Mwh, and
the limits except for pH, shall be three times the numerical values given
in the above table.
For Subcategory B, Covered Electric Furnaces and Other Smelting With Met
Air Cleaning, New Sources.
Limitations have not yet been defined.
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138
For Subcategory C, Slag Processing, Existing Sources.
Have been equated to BPT limits which are:
Avg. 30 Days Max. Day
Pollutant (lb/ton processed) (lb/ton processed)
TSS 2.659 5.319
Chromium, total 0.053 0.106
Manganese, total 0.532 1.064
pH 6.0 to 9.0
For Subcategory C, Slag Processing, New Sources.
Limitations have not yet been defined.
For Subcategory D, Covered Calcium Carbide Furnaces With Wet Air Cleaning,
Existing and New Sources.
Pretreatment
Pollutant Standard
TSS, pH No limitations
Cyanide 0.5 mg/1
For Subcategory E, Other Calcium Furnaces, Existing and New Sources.
No limitations.
For Subcategory F, Electrolytic Manganese Products, specifically the
production of manganese. Existing and New Sources^
Avg. 30 Days Max. Day
Pollutant (lb/1,000 lb product) (lb/1,000 Ib product)
Manganese 1.356 2.711
Ammonia-N 20.334 40.667
TSS, pH No limitations No limitations
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139
For Subcategory F, Electrolytic Manganese Products, specifically the
production of manganese dioxide, Existing and New Sources.
Avg. 30 Days Max. Day
Pollutant (lb/1000 Ib. product) (lb/1000 Ib. product)
Manganese 0.352 0.705
Ammonia-N 5.287 10.574
TSS, pH No limitations No limitations
For Subcategory G, Electrolytic Chromium, Existing and New Sources.
Avg. 30 Days Max. Day
Pollutant (lb/1000 Ib. product) (lb/1000 Ib. product)
Manganese
Chromium
Ammonia-N
TSS, pH
1.055
0.053
5.276
No limitations
2.111
0.106
10.553
No limitations
PRESCRIBED TREATMENT MEASURES OR EQUIVALENT
Although np_ pretreatment schemes have been described or formulated, it
is noted that certain BPT methods may be applicable for ferroalloy com-
panies discharging to POTW's. The latter may include neutralization,
physical-chemical treatment for removal of metals and TSS, settling,
sand or multi-media filtration, cyanide destruction by alkaline chlori-
nation or other oxidation, breakpoint chlorination for phenols reduction,
overall biologial treatment, and possible ammonia treatment by steam
stripping or breakpoint chlorination.
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LEATHER TANNING AND FINISHING INDUSTRY
(25, 26, 211, 212)
[Part 425]
SUBCATEGQRIZATION OF THE INDUSTRY
The'Leather Tanning and Finishing Industry has been divided into seven
Subcategories described below:
A - Hair - pulp - chrome tan
B - Hair - save - chrome tan
C - Hair - save - nonchrome tan
D - Retan only
E - No beamhouse tannery
F - Thru-the-blue
G - Shearlings tannery
Specialized definitions used in subcategorization are provided as
follows:
Hide shall mean any animal pelt or skin received by a tannery as raw
material.
Finish means the final steps performed on a tanned hide including but not
limited to retan, bleach, color and fatliquor.
Hair Pulp shall mean the removal of bair by means of chemical dissolution.
Hair Save shall mean the physical or mechanical removal of hair which
has not been chemically dissolved.
Chrome Tan means the process of converting hide into leather using a
chromium agent.
Vegetable Tan means the process of converting hide into leather using
chemicals either derived from vegetable matter or equivalent synthesized
chemicals.
Split means the nongrain part of a hide which results from a cut parallel
to its surface.
Beamhouse is that portion of the tannery where the hides are washed,
limed, fleshed, and unhaired when necessary, preparatory to the tanning
process.
Tanyard or Tanhoiise is that portion of the tannery in which bating,
pickling, and tanning are performed on the hides or skins.
Fatliquoring is a process by which oils and related fatty substances
replace natural oils lost in the beamhouse and tanyard processes. Fat-
liquoring regulates the softness and pliability of the leather.'
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141
Further description of plants within the various Subcategories is given
as follows:
Subcategory A, Hair - pulp - chrome. Include tanneries that primarily
process raw or cured cattle or other hides into finished leather, chemi-
cally dissolving the hide hair, and using chrome tanning and usually
wet and dry finishing.
Subcategory B, Hair - save - chrome. Includes tanneries that primarily
process raw or cured cattle or other hides into finished leather,
loosening and removing at least a portion of the hide hair as a solid,
and using chrome tanning and usually wet and dry finishing.
Subcategory C, Hair - save - nonchrome. Includes tanneries that pri-
marily process raw or cured cattle or other hides into finished leather
usually hair save, using less than 20% chrome tanning, using instead
vegetable, alum, syntans, oils or other methods for tanning, and usually
wet and dry finishing.
Subcategory D, Retan only. Includes tanneries that primarily process
previously tanned hides and/or skins (including splits) into finished
leather, the major wet process consisting of retanning, coloring and
fatliquoring.
Subcategory E, No beamhouse. Includes tanneries that primarily process
hides and/or skins, with the hair previously removed, into finished
leather using either chrome or nonchrome tanning methods. Materials
primarily include pickled sheepskin and cattlehides and pigskins.
Subcategory F, Thru-the-blue. Includes tanneries that primarily process
raw or cured cattle or other hides through-the-blue tanned state only,
with no retanning or finishing operations, using chrome tanning.
Subcategory G, Shearling. Includes tanneries that primarily process
raw or cured sheep or sheep-like skins, with the wool or hair retained
on the hides, into finished leather using chrome or nonchrome tanning;
or a wool pullery, a plant which processes hair-on raw or cured sheep or
sheep-like skin by first removing the wool and then pickling the skin
for use by a sheepskin tannery (i.e. Subcategory E).
NATURE OF PROBLEM
There are approximately 200 to 210 tanneries (wet process) in operation
at present time across the U.S. Another 225 to 260 firms are engaged
in finishing operations (mostly dry operations) for the leather tanned
at some other location. Cattle hides represent about 20 percent of the
total estimated pounds of hides tanned in this country. Other types of
hides include sheep, lamb, pigskin, horse, goat, etc. Currently, waste
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142
from around 90 percent of the tanneries, constituting about 80% of the
production, is discharged to municipal sewers. Tannery wastes can ex-
hibit high strength, i.e. 2,000 to 3,000 mg/1 TSS, up to 850 mg/1 oil
and grease, and sulfides up to 250 mg/1.
Leather tanning and finishing wastewaters contain hair, hide scraps,
pieces of flesh, blood, manure, dirt, lime, surface active agents,
tannins, dyes, solvents, etc. These wastes are generally characterized
as having appreciable amounts of TSS, TDS, BOD, COD, oil and grease,
total chromium, sulfides, total kjeldahl nitrogen, ammonia nitrogen,
chlorides, alkalinity, heat, fecal coliforms, and possible pH problems.
Major wastewater sources in a leather tanning and finishing plant in-
clude: washing and soaking, degreasing, unhairing, bating, pickling,
tanning, retanning, coloring, fatliquoring, drying, and finishing opera-
tions. Finishing may generate various wastewaters such as wet scrubbing
of buffing dust and spray booth washdowns.
Washing and soaking create spent waste streams containing dirt, manure,
salts and other foreign materials. Degreasing (usually only for sheep-
skins and pigskins) contributes animal fats and associated waste ma-
terials from the skins, plus spent detergents or solvents. With solvent
degreasing, most plants utilize a solvent recovery system. Detergents
used will be dependent upon the type of hide or skin to be degreased.
Unhairing is performed by either the "hair save" or the "hair pulp"
method. Hair save refers to mechanical removal of chemically-loosened
hair. This hair is mostly disposed of to landfill although some may
enter the plant sewer. In the hair pulp method, the hair is dissolved
completely. The latter method is the most important waste source of
proteinaceous organic and inorganic lime-type pollutants, characterized
by wastewaters of high pH and containing substantial amounts of BOD,
TSS, sulfides, alkalinity and nitrogen. Beamhouse processes whicb_in-
clude washing through unhairing operations, typically generate u'p to
75 percent of the waste load expected at a complete tannery.
Bating produces inorganic calcium salts, proteinaceous hair and waste
hide substances together with large amounts of ammonia nitrogen.
Pickling operations are responsible for low pH wastes which also contain
large amounts of salts.
Tanning is accomplished primarily using trivalent chromium salts or
tannins in extracts derived from special forms of tree bark. Spent
chrome tanning liquors will contain high concentrations of trivalent
chromium in low pH waters together with BOD, TSS and heat. Slowdown
associated with vegetable tanning is highly colored and contains sub-
stantial amounts of BOD, COD and TDS.
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143
Retarding, coloring, and fatliquoring contribute additional trivalent
chromium, vegetable tannins, synthetic tannins, natural and synthetic
oils and spent acid dyes found in relatively large wastewater volumes.
These wastes have moderate-to-low amounts of BOD and TSS, moderate
levels of COD, and may contain significant color and heat.
Drying and the various finishing operations (such as pasting, frame
washing, rewet conditioning, vacuum dryer cooling, wet scrubbing of
buffing dust, spray booth washdowns, etc.) generally cause relatively
small volumes of low strength wastewaters.
It is reported in POTW's properly designed to handle leather tanning and
finishing wastewaters that BOD, TSS, sulfides, oil/grease and chromium
loads from the tanning industry should be compatible pollutants.
Almost all POTW's receiving major amounts of leather tanning and fin-
ishing wastes where sulfide problems could become severe, have imple-
mented special measures primarily to control pH fluctuations. Sulfides
are thought to be readily ozidized in secondary-type POTW's. Various
municipal sewer ordinances include provisions to limit sulfide inputs to
the sewer. However, where sulfide problems have occurred, they have
been quite severe. Documentation is available regarding sewer crown
corrosion, odors, asphyxiation and death of municipal workers, and el-
ectrical and mechanical equipment corrosion both within sewer collection
systems and treatment works. High surges of oxygen demand are caused
by rapid oxidation of sulfides in the system. Ammom'a nitrogen is also
a problem associated with leather tanning wastes. Treatment alternatives
for reducing ammonia include beamhouse stream segregation and precipi-
tation of proteins (from pulped hair) after the sulfides have been oxi-
dized, and the possible substitution of ammonia in the bating process.
Specific effects upon POTW'S include the large pieces of scrap hide,
leather trimmings, hair and other screenable solids which can clog
pipes, pumps and equipment. Industrial batch processes can produce
wide fluctuation in hydraulic, organic and pH loadings to the POTW.
Unhairing wastewaters containing sulfides can cause odor, corrosion
and hazardous gases. Disposal of POTW sludges containing undue amounts
of chromium may be of special concern. Ammonia nitrogen may pass through
a POTW. Pretreatment of leather tanning wastes for sulfides, chromium
and/or ammonia may well be indicated in specific cases.
PARAMETERS OF CONCERN
BOD
Total Chromium
Oil/grease
TSS
Sulfide
Chlorides
pH, Acidity and
Alkalinity
COD
Kjeldahl and Total Nitrogen
Ammonia Nitrogen
Fecal Coliforms
Color
Phenols pH, Acidity and
TDS
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144
Total Chromium. Most leather in the U.S. is tanned with chromium salts,
Evidence indicates that chromium in both the trivalent and hexavalent
forms is harmful, and thusly total chromium is measured.
Sulfide. Sulfide compounds are used extensively in the beamhouse for
the unhairing process and consequently are commonly found in tannery
effluents. A significant portion of the alkaline sulfides contained in
tannery wastewaters can be converted to hydrogen sulfide at pH's below
8.5 to 9.0, resulting in release of this gas. The gas is not only
Odorous but is also oxidized to sulfuric acid, causing sewer "crown"
corrosion. At high concentrations, this gas can be lethal, and is a
significant hazard in sewer maintenance.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTU
For Subcategory A, Hair Pulp, Chrome Tan, limitations for existing
plants; (limits for New plants have not yet been clearly defined).
Parameter Pretreatment Standard
pH Acceptable range of 7 to 10
For Subcategory B, Hair Save, Chrome Tan, limitations for Existing
plants; (limits for New plants have not yet been clearly defined).
pH Acceptable range of 7 to 10
For Subcategory C, Hair Save, Non-chrome Tan, limitations for Existing
plants; (limits for New plants have not yet been clearly defined).
pH Acceptable range of 7 to 10
For Subcategory D, Retan, limitations for Existing plants; (limits for
New plants have not yet been clearly defined).
pH Acceptable range of 6 to 10
For Subcategory E, No Beamhouse, Subcategory, limitations for Existing
plants; (limits for New plants have not yet been clearly defined).
pH Acceptable range of 6 to 10
For Subcategory F, Through-The-Blue, Subcategory, limitations for Ex-
isting plants; (limits for New plants have not yet been clearly defined)
pH Acceptable range of 7 to 10
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145
For Subcategory G, Shearling Subcategory, limitations for Existing
plants; (limits for New plants have not yet been clearly defined).
Parameter Pretreatment Standard
pH Acceptable range of 6 to 10
PRESCRIBED TREATMENT FOR DISCHARGE TO POTW
Undue amounts of sulfide and chromium may be responsible for serious
problems at POTW's but adequate POTW control methods are reported
available to minimize effects. Non-contact cooling waters can be
recycled. Spent unhairing, chrome tanning and vegetable tanning
liquors can be recovered and reused as makeup. Other cases involve
protein recovery from beamhouse wastewaters, and chromium recovery
from tanyard wastewaters. Substitution for ammonia in the bating
process can significantly reduce the amount of dissolved ammonia in
tannery wastewaters.
Chromium removal may be necessary by the tannery prior to the municipal
system where stringent water quality limits have been imposed on the
POTW or where the POTW utilizes a sludge destruction process such as
incineration, pyrolysis or wet oxidation which most likely generate
hexavalent chromium which in turn cannot be properly disposed of be-
cause of lack of appropriately controlled landfill sites. Sulfide
removal may be necessary by the tannery prior to the municipal system
when there may be appreciable HLS gas evolution in the sewers, or
when the municipality has experienced a history of severe odor and
corrosion problems in spite of various control procedures. The Federal
regulations of March 23, 1977 indicate where important operational
or sludge disposal problems occur or stringent water quality standards
are prevailing, the local authority should be invoked to require pre-
treatment.
Basic pretreatment at leather tanning facilities may include waste
equalization, effective fine screening and close pH control. Tanneries
employ waste holding, carbonation, screening, settling, lagoons, etc.
One study has recommended pretreatment consisting of waste equalization,
carbonation with flue gas, followed by settling with removal of settle-
able solids. Chemical treatment includes use of alum, lime, iron salts
or polymers, pH adjustment followed by necessary sludge handling and
disposal.
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(INSULATION) FIBERGLASS MANUFACTURING
(94, 95)
[Part 426]
SUBCATEGORIZATION OF THE INDUSTRY
Fiberglass Manufacturing has been defined as Subcategory A of the overall
Glass Manufacturing Industry. The process is one in which glass is made
either directly or indirectly, continuously fiberized, and chemically
bonded with phenolic resins into a wool-like final product. Insulation
fiberglass or thermal insulation fiberglass includes but is not limited
to noise insulation products, air filters, and bulk wool products. These
operations are referred to as a primary process as contrasted to secondary.
processes e.g. where waste textile fiberglass is processed into an insula-
tion product. The term insluation fiberglass is synonymous to the descrip-
tions-glass wool, fibrous glass, and construction fiberglass.
NATURE OF PROBLEM
Insulation fiberglass is manufactured by only three companies in the
U.S. A total of 19 plants has been identified. One waste stream of
particular concern is cullet cooling water. Cullet water is necessary
in order to solidify molten glass from a furnace whenever the glass
spinning portion of the operation is interrupted or discontinued.
Cullet water can contain high levels of TSS ranging from a few hundred
mg/1 to tens of thousands of mg/1 even after settling.
PARAMETERS OF CONCERN
BOD Ammonia
COD Color
Phenols Turbidity
TSS Oil/Grease
TDS Temperature
pH Dyes
Toxicity
Phenols. Basic constituents of the binder in fiberglass are phenol,
formaldehyde, urea and ammonia which react to form various mono and
poly methylol phenols. Free phenols will occur in any water having
contact with uncured resin. Phenols levels range from 4 mg/1 in once-
through process waters to several hundered mg/1 in recycled waters.
COD. Fiberglass manufacturing raw waste streams may contain COD's
ranging from 3,300 to 44,000 mg/1.
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147
Dissolved Solids. IDS concentrations can be increased significantly
from chain washing and wet scrubbing of air streams. Net increases
of 200 mg/1 IDS are reported. Gross concentrations of up to 40,000
mg/1 IDS have also been observed.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
The Development Document for Fiberglass Manufacturing indicates process
waste waters can contain high concentrations of phenols, formaldehyde
and other hazardous materials which interfere with the operation of
POTW's, pass through these works untreated or inadequately treated, or
otherwise are incompatible with the treatment works. Accordingly, it
has been determined that fiberglass process waste waters from existing
sources shall receive pretreatment to the level required by BPCTCA, and
new sources shall receive pretreatment to the level required by New
Source Performance Standards. However, both BPCTCA and NSPS call for
np_ discharge of process wastes. Two exceptions to the above pretreat-
ment requirements are cullet waters from both existing and new sources;
and wastewaters resulting from "advanced air emission control devices"
at existing plants, when such waters cannot be consumed in the process.
Under BPCTCA limitations for advanced air emission control devices, the
following allowances are specified:
Avg. 30 Day Max Day
Parameter (lb/1000 Ib final product)(lb/1000 Ib. final product)
Phenol
COD
BOD*
TSS*
pH*
0.0003
0.165
0.012
0.015
Range of 6 to 9
0.0006
0.330
0.024
0.030
0.030
Cullet water is defined as water necessary to solidify molten glass
coming off the furnace when the glass spinning portion of the operation
may be discontinued for some reason. Cullet waters may contain large
quantities of finely divided silica particles in suspension together
with heat, but this waste has been determined to be amenable for
acceptance into POTW's.
Are likely considered compatible pollutants for POTW purposes.
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FLAT GLASS, PRESSED GLASS AND BLOWN GLASS MANUFACTURING
(88, 89, 90, 91, 92 and 93)
[Part 426]
SUBCATEGORATION OF THE INDUSTRY
The Glass Manufacturing Industry is divided into 13 subcategories.
Fiberglass manufacturing, which is Subcategory A of the glass industry,
has been given elsewhere in this report. The remaining 12 Subcategories
are discussed below. Subcategories B through E deal with primary glass
manufacturing. Subcategories F and G deal with automobile window glass
fabrication. Subcategories H through M cover a wide range of pressed
and blown glass prbducts.
B - Sheet Glass Manufacturing
C - Rolled Glass Manufacturing
D - Plate Glass Manufacturing
E - Float Glass Manufacturing
F - Automotive Glass Tempering
G - Automotive Glass Laminating
H - Glass Container Manufacturing
I - Machine Pressed and Blown Glass Manufacturing (Reserved)
J - Glass Tubing (Danner) Manufacturing
K - Television Picture Tube Envelope Manufacturing
L - Incandescent Lamp Envelope Manufacturing
M - Hand Pressed and Blown Glass Manufacturing
Subcategory B, Sheet Glass. Manufactured from sand, soda ash, limestone,
dolomite, cullet, etc., these raw materials being mixed and melted in a
furnace. The material is drawn vertically from a melting tank to form
sheet glass.
Subcategory C, Rolled Glass. The same raw materials as used in Sub-
category B are mixed, melted in a furnace and cooled by rollers to form
rolled glass.
Subcategory D, Plate Glass. The same raw materials as used in Sub-
category B are mixed, melted in a furnace, pressed between rollers, and
subsequently ground and polished to form plate glass.
Subcategory E, Float Glass. Equivalent to plate glass manufacture except
a molten tin bath is used after the melting furnace and no grinding or
polishing is required.
Subcategory F. Automotive Glass Tempering. Mostly float glass is used,
which is cut, ground, polished, bended and tempered to produce front and
back windows for automobiles.
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149
Subcategory G, Automobile Glass Lamination. Deals with the fabrication
of auto windshields. Fabrication consists of inserting a vinyl plastic
sheet between two layers of glass, immersing in an oil bath, and washing,
cutting and seaming.
Subcategory H, Glass Containers. Includes plants which melt raw materials
at their facility and mechanically process the resulting glass into glass
containers.
Subcategory I, Machine Pressed and Blown Glass. Includes plants which
melt raw materials at their facility and mechanically process the result-
ing glass into pressed or blown glass products.
Subcategory J, Glass Tubing (Danner). Includes plants which melt raw
materials at their facility and produce glass tubing as the final product.
Subcategory K, Television Picture Tube Envelopes. Includes plants which
melt raw materials at their facility and produce TV tube envelopes as
the final product.
Subcategory L, Incandescent Lamp Envelopes. Includes plants which melt
raw materials at their facility and produce incandescent lamp envelopes.
Also includes plants which frost the envelopes by etching with hydro-
fluoric acid.
Subcategory M, Hand Pressed and Blown Glass. Includes plants which melt
raw materials at their facility and hand process the resulting glass into
pressed or blown glass products.
NATURE OF THE PROBLEM
Flat Glass (Subcategories B through G)
There are a total of 36 plants owned by 11 Companies which manufacture
flat glass and fabricate automobile window glass in the U.S. (Sub-
categories B through G). Major operations in primary glass manufacturing
consist of batching raw materials, melting, forming, annealing, grinding
and polishing, washing and cooling. Major operations in automobile win-
dow glass fabrication include windshield laminating and solid tempering.
Pressed and Blown Glass (Subcategories H through M).
Various plants identified by the USEPA for the manufacture of Pressed
and Blown Glass in the U.S. and Puerto Rico include as follows:
Glass Container plants - 30 Companies having 140 plants; Machine Pressed
and Blown Glassware - 50 plants; Glass Tubing - 30 plants; TV Picture
Tube Envelope plants - 10 establishments; Incandescent Lamp Envelope
facilities - 18; Hand Pressed and Blown Glassware - approximately 50
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plants. Major operations in the pressed and blown glass industry in-
clude: weighing an.d< mixing of raw, materials, melting, of raw materials,
forming of moltet glass, annealing of formed glass products, and special
ftm string operations.
PARAMETERS OF CONCERN
BOD* Lead
COD Ammonia
TSS IDS
Oil/grease Phosphorus
pH", acidity, Temperature
a1ka1i n i ty Turbi d i ty
Fluoride
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTVI AND PRESCRIBED TREATMENT
MEASURES
Flat Glass (Subcategories B through G)
The Federal regulations indicate for Existing Sources in the Flat Glass
Subcategories, that the wastewaters generally contain pollutants com-
patible with POTW's. The one exception is Subcategory G, i.e., Automo-
tive Glass Lamination, which generates a wastewater high in oil. Raw
wastes from the laminating process typically contain 1,000 to 2,000 mg/1
of oil. The proposed regulations of February 14, 1974, require that
BPCTCA limitations for oil/grease be attained as shown below. This is
necessary because of the known detrimental effect of high concentration
of oil on biological treatment systems, and the inability of POTW's to
adequately remove oil.
For Subcategory G, Automotive Glass Lamination:
Avg. 30 Day Max. Day
Parameter (lb/1,000 ft2 final product) (Ib 1,000 ft? final product)
Oil/Grease 0.36 0.36
Pressed and Blown Glass (Subcategories H through M)
The Federal regulations for Existing Sources in the Pressed and Blown
Glass Subcategories have established limitations for mineral-type oils
and fluoride in certain Subcategories, and also indicate concern over
lead and ammonia loads.
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151
Animal and vegetable oils were reported as adequately removed by POTW's,
whereas mineral oils are much more persistent and may pass through POTW's
untreated. Consequently, only mineral-type oils have been limited.
The criteria have been developed in terms of mg/1 and also on the basis
of Ibs. of "furnace pull" which means the amount of molten glass drawn
from the molten furnace(s).
For Subcategory H, Glass Container Manufacturing, Existing Sources:
Parameter Daily Max.
Oil (Mineral) 100 mg/1
For Subcategory H, Glass Container Manufacturing, New Sources:
Avg. 30 Day Max. Day
Parameter (lb/1,000 Ib furnace pull) (lb/1,000 Ib furnace pull)
Oil (mineral) 0.03 0.06
For Subcategories I and J - No limitations.
For Subcategory K, TV Picture Tube Envelope Manufacturing, Existing Sources
Fluoride 0.07 0.14
Oil(mineral) - 100 mg/1
For Subcategory K, TV Picture Tube Envelope Manufacturing, New Sources:
Oil (mineral) 0.13 0.26
Fluoride 0.06 0.12
For Subcategory L, Incandescent Lamp Envelope Manufacturing, Forming
Operations, Existing Sources:
Parameter Daily Max.
Oil (mineral) 100 mg/1
For Subcategory L, Incandescent Lamp Envelope Manufacturing, Forming
Operations, New Sources:
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152
Avg. 30- Day Max.. Day
Parameter (lb/1,000 Ib furnace pull)' (lb/T',000 Ib furnace pull)
Oil (mineral); 0.115 0.230
For Subcategory L, Incandescent Lamp Envelope Manufacturing, Finishing
Operations, Existing Sources:
Avg. 30 Day Max., Day
Parameter (lb/1.,000 Ib product frosted)(lb/l ,000 Ib. product, frosted)
Fluorfde 0.115 0.230
Oil (mineral) - 100 mg/1
For Subcategory L, Incandescent Lamp Envelope Manufacturing, Finishing
Operations, New Sources:
Fluorfde 0.052 0.104
Oil (mineral), - TOO mg/1
For Subcategory M, Hand. Pressed and; Blown: Glass Manufacturing, Existing
Sources:
No Limitations
For Subcategory M, Hand Pressed and Blown Glass Manufacturing; produces
hand pressed or blown leaded glassware and employs HF acid finishing,
New Sources:
Avg. 30 Day Max. Day
Parameter mg/T mg/1
Fluoride 13.0 26.0
For Subcategory M, Hand Pressed and Blown Glass Manufacturing; produces
non-leaded hand pressed or blown glassware and employs HF acid finishing,
New Sources:
Fluoride - 13.0 26.0
For Subcategory M, Hand Pressed and Blown Glass Manufacturing; produces
leaded or non-leaded pressed or blown glassware and does not use HF acid
finishing, New Sources:
No Limitations..
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153
ASBESTOS PRODUCTS
MANUFACTURING INDUSTRY
(83, 84, 85, 86, 87)
[Part 427]
SUBCATEGORIZATION OF THE INDUSTRY
The Asbestos Manufacturing Industry has been divided into eleven Subcat-
egories. The first seven Subcategories represent industrial activities
under the Building, Construction and Paper Segment of the Industry, and
the last four Subcategories represent processes incorporated under the
Textile, Friction Materials and Sealing Devices Segment of the Asbestos
Industry. These Subcategories are described below:
A - Asbestos Cement Pipe
B - Asbestos Cement Sheet
C - Asbestos Paper (Starch Binder)
D - Asbestos Paper (Elastomeric Binder)
E - Asbestos Millboard
F - Asbestos Roofing
G - Asbestos Floor Tile
H - Coating or Finishing of Asbestos Textiles
I - Solvent Recovery
J - Vapor Absorption
K - Wet Dust Collection
Subcategory A, Asbestos-Cement Pipe. Asbestos, Portland cement, silica
and other ingredients are mixed and blended for the fabrication of as-
bestos-cement pipe.
Subcategory B, Asbestos - Cement Sheet. Asbestos, Portland cement,
silica and other ingredients are mixed and blended in the manufacture
of asbestos-cement sheets. Asbestos-Cement sheet laboratory tops are
excluded from this Subcategory.
Subcategory C, Asbestos Paper, Starch Binder. Asbestos, starch binders
and other materials are used in the manufacture of starch binder type-
asbestos paper.
Subcategory D. Asbestos Paper, Elastomeric Binder. Asbestos, elasto-
meric binders, and other materials are used in the manufacture of elasto-
meric binder type-asbestos paper.
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1,54.
Subcategflry E, Asbestos Millboard. Asbestos in combination, with; other
materials such as cement, starch, clay, lime and mineral wool are
used to produce asbestos millboard.
Subcategory F, Asbestos Roofing. Asbestos paper is saturated with as-
phalt or coal tar followed by various surface treatments in order to
manufacture asbestos roofing products.
Subcategory 6. Asbestos Floor Tile. Asbestos, polyvinyl chloride resin,
chemical stabilizers, limestone and other fillers are mixed for the
manufacture of asbestos floor tile.
Subcategory H, Coating or Finishiing of Asbestos Textiles. The process
of coating or impregnating asbestos textiles with selected materials
to obtain desired finished products or to eliminate the problem of air-
borne particles in the further handling, of the textiles.
Subcate.gory I, Solve.nt Recovery,. In some textiles coating and friction
materials; operatiioris,, the solvents driven1 off in drying! ovens are. cap-
tured by adsorption onto activated carbon. The solvents are then steam-
stripped; off the carbon and recovered by decanting or further distilling.
Subcatej.ory J, Vapor Absorption. In some textiles drying operations, the
so 1 vent I dr i ven of fa re removed from the exhaust, gases by absorption in
wet scrubbers. Solvents are not recovered and they are discharged with
the s,c rubber waters.
Subcategory K, Wet Dust Collection. Finishing; operations associated with
friction, materials., e.gj;,, grinding and, drilling, can generate excess
airborne.' parti culates;. Wet scrubbing: results in additional raw waste
loads.
NATURE OF THE PROBLEM
Building. Construction and Paper Segment of Asbestos Manufacturing
In the 1970's, this portion of the Asbestos Manufacturing, industry was
identified as consisting of 51 plant operations under 12 different com-
panies. Asbestos is normally combined with other materials to yield
manufactured products, and consequently loses its identity. Asbestos
is actually a group name that refers to several serpentine minerals
having different chemical composition, but similar characteristics.
The most widely used variety is chrysotile. Asbestos fibers are graded
on the basis of length, with the longest grade priced 10 to 20 times
higher than the shorter grades. The shorter grades are normally used
in the products described herein. Overall, asbestos^eement products
and. pipes consume about 70% of all asbestos mined.
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155
At many asbestos product plants, there is considerable manufacture of
non-asbestos products. For example, organic cellulose fiber paper
is commonly made at asbestos plants. Organic cellulose manufacturing
effluents often have high waste strength and may be more difficult to
treat than asbestos-type wastes.
Increased concern with the health effects of asbestos fibers in the air
has brought about changes that have in turn impacted upon water pollu-
tion. For example, dry processes have been converted over to wet pro-
cesses, and there is increased use of water sprays to minimize dust from
mining operations and slag piles. Much research has been carried out on
the health effects of asbestos fibers in air. Conversely, there has
been little study on the effects of fibers in water until the recent
findings of asbestos-like material in the drinking water supply of the
city of Duluth, Minnesota.
Textile, Friction Materials and Sealing Devices Segment of Asbestos
Manufacturing.
This portion of the asbestos industry essentially deals with the manu-
facture of asbestos textile products including yarn, cord, rope, thread,
tape, wicks and various fabrics; friction materials including brake
linings, clutch facings, etc.; and asbestos-containing gaskets, pack-
ings, seals, washers, etc. In many plants producing the above products,
little or no water is used in manufacturing, and liquid wastes are not
generated. Wastewaters from Coating, Solvent Recovery and Vapor Absorp-
tion type plants contain a variety of synthetic organic resins, elasto-
mers and/or solvents. The wastes from wet dust collectors are char-
acterized by high levels of suspended solids.
PARAMETERS OF CONCERN
BOD Oil and Grease
COD, TOC Nitrogen
TSS Phosphorous
pH, alkalinity Color
acidity
Temperature Heavy Metals including: Cadmium,
Chromium, Copper, Mercury, Zinc,
Phenols Nickel, Barium
Solvents Asbestos
Toxicity
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156
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
The various Federal documents on effluent limitations/guidelines have
not developed specific pretreatment limitations to date on asbestos
manufacturing effluents. Although these effluents may contain complex
organics together with appreciable amounts of suspended solids and
asbestos, the streams are reported as compatible with municipal systems
and many industrial plants are discharging to POTW's with little or no
pretreatment.
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157
RUBBER PROCESSING INDUSTRY
(108, 109, 110, 111, 112, 113)
[Part 428]
SUBCATEGORIZATION OF THE INDUSTRY
The Rubber Industry has been divided into 11 Subcategories. Subcate-
gories B, C, D include the (primary) synthetic rubber production
plants. Subcategories E, F and G comprise molded, extruded and fabri-
cated rubber plants; Subcategories H and I - reclaimed rubber plants;
and Subcategories J and K - latex rubber operations. The various sub-
categories are described below:
A - Tire and Inner Tube Plants
B - Emulsion Crumb Rubber
C - Solution Crumb Rubber
D - Latex Rubber
E - Small-Sized General Molded, Extruded, and Fabricated
Rubber Plants
F - Medium-Sized General Molded, Extruded, and Fabricated
Rubber Plants
G - Large-Sized General Molded, Extruded, and Fabricated
Rubber Plants
H - Wet Digestion Reclaimed Rubber
I - Pan, Dry Digestion, and Mechanical Reclaimed Rubber
J - Latex - Dipped, Latex Extruded, and Latex Molded Rubber
K - Latex Foam
Subcategory A, Tire and Inner Tube Plants. Production of pneumatic tires
and inner tubes.
Subcategory B, Emulsion Crumb Rubber. The manufacture of emulsion crumb
rubber* other than acrylonitrile butadiene rubber. Emulsion polymeri-
zation is the traditional process for the production of synthetic rubber
crumb. To an aqueous medium are added the ingredients of the reaction,
emulsifiers, catalysts, activators, etc. The emulsified product is then
coagulated with a combination of electrolyte and acid to form the
rubber crumb.
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158
Sutxcategpry C., 'Solution Cnumfa Rubber. Solution pol;ymeTi,zation Is ;a
nona'queous process for "the .production of synthet-tc 'rubber crumb.
Poljmerization (occurs in an organic solvent 'and the crumb rubber sub-
sequently coagulates by the addition of hot water and agitation.
Subcategory D, Latex Rubber. Similar to emulsion crumb rubber produc-
tion with the exception .of the coagulation, crumb rinsing, and dewater-
ing steps. Unlike crumb rubber production, short production runs are
.common.
Subcategory E, Small-Sized General 'Molded, Extruded, and Fabricated
Rubber Plants. Refers to the production of molded, extruded and
fabricated rubber items, foam rubber .backing, rubber cement-dipped
goods and retreaded'ttres in plants processing less than 8,200 Ib/day
raw materials,.
Subcategory F., Medium-Sized General Molded, Extruded, and Fabricated
Rubber Plants. Production of similar products as described for Sub-
category E in plants processing -between 8,200 :and 23,000 Ib/day raw
materials.
Subcategory G, Large-Sized General Molded, Extruded, and Fabricated
Rubber Plants. Production of similar products as described for Sub-
category E, i:n plants processing greater than 23,000 l:b/:day raw materials,
Subcategory H-, Wet Digestion Reclaimed Rubber. Rubber scrap is broken
down into small particles for defibering in .a digestor. Defibering
agents and plasticizing oils are added to facilitate chemical degra-
dation of the fibers.
Subcategory I, Pan., !Dry Digestion, and Mechanical Reclaimed Rubber.
Mechanical means of defibering are used in place of chemical defibering
employed by Subcategory H plants, thus avoiding defibering chemicals
and dissolved fibers in the waste waters.
Subcategory J, Latex-.Dipped, Latex Extruded and Latex Molded Rubber.
Latex is used as a raw material in the production of latex thread, and
latex-dipped or molded items.
Subcategory K, Latex Foam. The production of latex foam.
NATURE OF PROBLEM
Major waste sources from tire and tube plants (Subcategory A) include
tire .and inner tube production materials which come into contact with
process-waters and raw materials storage areas coming in contact with
storm water. Major waste waters from synthetic rubber plants (Sub-
categories B, C, D) originate from reaction vessel cleaning in the
emulsion processes, crumb washing and dewatering, and plant washdown.
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159
Major waste sources from general molded, extruded and fabricated rubber
plants (Subcategories E, F, G) include waste process solutions, wash-
downs, runoff from outdoor storage sites, spills/leaks of organic sol-
vents and lubricating oils, and vulcanizer condensates. Excess lead
can originate from lead-sheathing operations and excess COD from cloth-
wrapped curing.
Major waste waters from reclaimed rubber operations (Subcategories H and
I) include waste process solutions, washdowns, outdoor runoff, spills
and leaks, discharge from air pollution control devices, and dewatering
liquor from the wet digestion process.
Waste waters from latex rubber operations (Subcategories J and K) ori-
ginate as product wash and rinse waters, spills, leakage, washdown and
runoff. Chromium is present in spent waters from latex-dipped and
latex-molded rubber facilities. Zinc is contributed by latex foam
facilities.
PARAMETERS OF IMPORTANCE
BOD Lead
COD Chromium
TSS Zinc
Oil and Grease Other Metals
Surfactants IDS
pH, acidity, alkalinity Temperature
Color
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
The Federal Regulations have determined for Subcategory A Rubber
Processing Plants, that process waste waters are amenable for discharge
to POTW's without any pretreatment. Waste waters from Subcategory B
through K Plants are reported compatible to POTW's, with exceptions
in pretreatment criteria as defined below:
For Subcategory A, Tire and Inner Tube Plants, Existing and New Sources.
No Limitations
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160
For Subcategory B, Emulsion Crumb Rubber, Applicable to Existing Sources,
and apparently also to New Sources.
Avg. 30 Day Max. Day
Parameter • (lb/1,000 Ib final product) (lb/1.,000 Ib final product)
COD 8.0 12.0
For Subcategory C, Solution Crumb Rubber, Applicable to Existing Sources
and apparently also to New Sources.
COD 3.94 5.91
For Subcategory D, Latex Rubber, Applicable to Existing Sources, and
apparently also to New Sources.
COD 6.85 10.27
For Subcategories E, F and G, i.e. General Molded, Extruded, and Fab-
ricated Rubber Plants, Applicable to Existing and New Sources.
Avg. 30 Day Max. Day
Parameter (lb/1,000 Ib raw materials) (lb/1,000 Ib raw materials)
Oil/Grease - 100 mg/1
Lead* 0.0007 0.0017
For Subcategory H, Wet Digestion Reclaimed Rubber, Existing and New
Sources.
Avg. 30 Day Max. Day
Parameter (lb/1,000 Ib final product) (lb/1,000 Ib final product)
Oil/Grease ' - 100 mg/1
COD 6.11 14.70
For Subcategory I, Pan, Dry Digestion, and Mechanical Reclaimed Rubber,
Existing and New Sources.
Oil/Grease - 100 mg/1
COD 2,8 6.7 -
* Attributable to lead-*sheathed hose production, wastes from which
are discharged to a POTW.
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161
For Subcategory J, Latex-Dipped, Latex-Extruded, and Latex-Molded
Rubber, Existing and New Sources.
Avg. 30 Day Max. Day
Parameter ' (lb/1,000 Ib raw materials) (lb/1,000 Ib raw materials)
Oil /Grease
*
Chromium
0.0036
100 mg/1
0.0086
For Subcategory K, Latex Foam, Existing and New Sources.
Zinc 0.024 0.058
The EPA Development Documents on the Rubber Processing Industry indicate
the following pretreatment measures are desired for rubber processing
waste waters before release to a POTM:
Tire and Inner Tube Plants (Subcategory A). Process wastes should re-
ceive separation of oils and solids in an API gravity separator together
with flow equalization in order to prevent shock loads of oil, TSS, or
batch dumps of dipping solutions from upsetting the POTW.
Synthetic Rubber Plants (Subcategories B, C, D). Emulsion crumb and
solution crumb slurry overflow waste waters should be passed through
crumb pits to remove floatable rubber crumb. Few POTW's have primary
settling equipment adequate to handle large quantities of agglomerated
rubber crumb solids. Waste waters from emulsion crumb and latex pro-
duction facilities are invariably laden with uncoagulated latex solids.
Since POTW's generally do not have coagulation capabilities, these
waste waters should be at least chemically coagulated with a "sinking
agent" and clarified. The following pretreatment measures apply res-
pectively to Subcategory B, C and D rubber plants.
Emulsion Crumb Plants. Gravity separation of crumb fines in crumb pits,
chemical coagulation and clarification of latex-laden waste waters, and
neutralization or equalization of utility wastes.
Solution Crumb Plants. Gravity separation of crumb fines in crumb
pits, and neutralization or equalization of utility wastes.
Latex Plants. Chemical coagulation of latex-laden waste waters, and
neutralization or equalization of utility wastes.
Attributable to plants employing the chromic acid form-cleaning
operation, the wastes from which are discharged to a POTW.
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162
General Molded, Extruded and Fabricated Rubber Products (Subcategories
E, F, G). Process wastes should be passed through an API Separator for
separation of. oils and solids, together with an equalization basin to
prevent shock loads of oil, TSS or batch dumps of dipping solutions,
etc., from upsetting the POTW. In addition, waste waters containing
excess lead must be treated prior to release to the POTW.
Met Digestion Reclaimed Rubber (Subcategory H). Process wastes should
be treated for separation of oils and solids followed by use of equali-
zation. An API separator is appropriate for oil removal if the waters
do not contain digested fibrous materials. If the fiber is digested
along with the rubber scrap, an abundance of fibrous material will be
present, which is difficult to settle. An oversize settling lagoon may
be adequate prior to discharge to a POTW.
Pan, Mechanical and Dry Digestion Operations (Subcategory I). Oil and
solids removal together with flow equalization.
Latex Products (Subcategories J and K). Coagulation and clarification
of solids-laden wastes followed by chemical precipitation for Chromium
and Zinc, if found necessary.
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163
TIMBER PRODUCTS INDUSTRY
(2, 114, 115, 116, 117, 118, 119, 120, 121, 122, 127)
[Part 429]
SUBCATEGORIZATION OF THE INDUSTRY
The Timber Products Industry has been divided into 19 subcategories.
Subcategories A through H comprise the Plywood, Hardboard and Wood
Preserving Segment of the industry; Subcategories I through 0 - the Wet
Storage, Sawmills, Particleboard and Insulation Board aspects of the
industry; and Subcategories P through S include furniture and fixture
manufacturing operations and plants. These subcategories are further
described below.
A - Barking Operations
B - Veneer Manufacture
C - Plywood
D - Hardwood - Dry Processing
E - Hardwood - Wet Processing
F - Wood Preserving
G - Wood Preserving - Steam
H - Wood Preserving - Boultonizing
I - Wet Storage
J - Log Washing
K - Sawmills and Planing Mills
L - Finishing
M - Particleboard Manufacturing
N - Insulation Board Manufacturing
0 - Insulation Board Manufacturing with Steaming
or Hardboard Production
P - Wood Furniture and Fixture Production without Wash
Spray Booth(s) or Laundry Facilities
Q - Wood Furniture and Fixture Production without Wash
Spray Booth(s) but with Laundry Facilities
R - Wood Furniture and Fixture Production with Water
Wash Spray Booth(s) but without Laundry Facilities
S - Wood Furniture and Fixture Production with Water Wash
Spray Booth(s) and with Laundry Facilities
Subcategory A, Barking. Operations for removal of bark from logs. Bark-
ing is accomplished by mechanical abrasion or by hydraulic force. Ma-
terial removed by barking is generally used as a feed material to other
plants in the Timber Processing Industry.
Subcategory B, Veneer. Operations converting barked logs or heavy tim-
ber into thinner sections of wood known as veneer.
Subcategory C. Plywood. Layers of veneer are laminated to produce fin-
ished plywood. Plywood manufacturing is mostly "dry" except that water
is used in cleaning the glue application equipment.
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164
Subcategory D. Hardwood Dry Processing. Manufacturing operations assoc-
iated with finished hardboard made from chips, dust, logs, etc., using
the dry_ matting process in forming the board mat.
Subcategory E, Hardwood Wet Processing. Manufacturing operations asso-
ciated with finished hardboard made from chips, dust, logs, etc., using
the wet matting process in forming the board mat. Fibers are diluted
from 40 percent to less than 1.5 percent prior to mat formation.
Subcategory F, Wood Preserving. Wood preserving plants in which steam-
ing or boultonizing is not the predominant method of conditioning,
waterborne salts are used in pressure and non-pressure processes, and
preserving methods are of the non-pressure type.
Subcategory G, Mood Preserving-Steam. Processes that use direct steam
impingment on the wood as the predominant method of conditioning.
Subcategory H, Wood Preserving-Boultonizing. Wood preserving methods
utilizing the Boulton process for conditioning stock.
Subcategory I, Wet Storage. Includes: 1) the holding of unprocessed
wood, i.e., logs or roundwood with bark; 2) the holding of barked logs
in self-contained bodies of water (mill ponds or log ponds); or 3)
land storage of logs with water being sprayed on the wood (wet decking).
Subcategory J, Log Washing. Logs are passed through pressure sprays,
the water serving to remove foreign material from the surface of the log
before further processing.
Subcategory K, Sawmills and Planing Mills. Includes one or more of
the following operations: log washing, bark removal other than hy-
draulic barking, sawing, resawing, edging, trimming, planing, and/or
machining.
Subcategory L, Finishing. Consist of operations following edging and
trimming, which include drying, planing, dipping, staining and coating,
moisture proofing, fabrication, and by-product utilization.
Subcategory M, Particleboard Manufacturing. Particleboard refers to
board products that are composed of distinct particles of wood or other
lignocellulosic materials not reduced to fibers which are subsequently
bonded together with an organic or inorganic binder.
Subcategory N, Insulation Bond Manufacturing. Production of insulation
board where the wood material is not subject to a pressure created by the
steam. Excluded is the manufacture of insulation board from bagasse.
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165
Subcategory 0, Insulation Board Manufacturing Hith Steaming or Hardboard
Production. Production of insulation board at facilities which either
steam condition the raw material before refining, or produce hardboard
at the same facility. Excluded is the manufacture of insulation board
from bagasse.
Subcategory P, Hood Furniture and Fixture Production Without Water Hash
Spray Booth(s) or Laundry Facilities. Applies to manufacture of wood fur-
niture and fixtures at establishments that: 1) do not utilize wash spray
booths to collect and contain the overspray from spray applications of
finishing materials; and 2) do not maintain on-site laundry facilities
for the fabrics utilized in various finishing operations.
Subcategory Q, Wood Furniture and Fixture Production Without Water Hash
Spray Booth(s) but Hith Laundry Facilities.Applies to manufacture of
wood furniture and fixtures at establishments that: 1) do not utilize
wash spray booths to collect the overspray from spray applications of
finishing materials; but 2) maintain on-site laundry facilities for the
fabrics utilized in various finishing operations.
Subcategory R, Hood Furniture and Fixture Production Hith Water Hash
Spray Booth(s) but Hithout Laundry Facilities.Applies to manufacture
of wood furniture and fixtures at establishments that: 1) utilize water
wash spray booths to collect and contain overspray from spray applica-
tions of finishing materials; but 2) do not maintain on-site laundry fa-
cilities for the fabrics utilized in various finishing operations.
Subcategory S, Hood Furniture and Fixture Production Hith Hater Hash
Spray Booth(s) and Hith Laundry Facilities.Applies to manufacture of
wood furniture and fixtures at establishments that: 1) utilize water
wash spray booths to collect and contain overspray from spray application
of finishing materials; and 2) maintain on-site laundry facilities for
the fabrics utilized in various finishing operations.
NATURE OF PROBLEM
Plywood, Hardboard and Hood Preserving Subcategories (A through H).
Comprise establishments thought to be the most significant sources of
water pollution problems across the timber products industry. As of
around 1970, there were 340 plywood plants in the U.S. and about 160
veneer plants. In 1973, there were 27 known hardwood manufacturing
facilities of which 17 represented variations of the dry process and
10 utilized variations of the wet process. Het or dry refers to the
formation or felting of fibers to form a mat which is eventually formed
into sheets or boards. The main difference is essentially that dry
process fibers are suspended in air rather than in water. Hood preser-
ving subjects round and saw cut wood products to a chemical injection
process which imports fungistatic, insecticidal, and fire-resistance
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166
properties to the wood. In 1971, a total of 390 wood preserving plants
were recorded. Common preservatives are creosote, pentachloro-phenol
and special formulations of water soluble inorganic chemicals including
copper, chromium and arsenic. Fire retardants are generally formulations
of borates, phosphates and ammonium compounds. In veneer and plywood
mills, major waste sources are log conditioning, cleaning of veneer
dryers, washing of glue appertanances and cooling needs. Major waste
sources from hardwood mills comprise log washing, chip washing, fiber
preparation, mat formation and pressing, resin system, caul washing,
housekeeping and humidification. Wood preserving effluents typically
have high phenolics, COD and oils including the emulsified form together
with low pH.
Wet Storage, Sawmill, Particleboard and Insulation Board Subcategories
(I through 0).Represent a diverse group of establishments.Subcate-
gories I and J include the handling and storage of logs. Sawmills and
planing mills (Subcategory K) produce lumber products from logs. Additional
operations falling under Subcategory K comprise fabrication using adhesives
to join wood members, machining, etc. Finishing operations covered
under Subcategory L include drying, dipping, staining and coating, and
by-product conversion. Particleboard made by Subcategory M plants, is
divided into low, medium and high density particleboard. Insulation
board made by Subcategory N and 0 plants, principally include building
board, insulating roof deck, roof insulation, ceiling tile, lay-in-
panels, sheathings and sound deadening insulation board. In 1967, a
total of 10,270 sawmills and planing mills in the U.S. was estimated.
It was also reported that there were 76 particleboard plants and 18
large-sized insulation board plants in the U.S.
Wood Furniture and Fixture Subcategories (P through S). Consist of
approximately 7,000 establishments which are highly diversified. More
than 90 percent of these plants have less than 100 employees and are
primarily located in North Carolina, the middle Atlantic, southern
Atlantic, the east northcentral States, and California. Raw materials
include lumber, veneer, plywood, hardwood and particle-board. Wood is
dried, machined and bent to desired shape. Parts are assembled generally
using glue. Finishing operations include bleaching, staining, filling,
sealing, topcoating, wood graining etc. Wood finishing materials are
applied by brush or roller, but most often are sprayed onto the wood
utilizing dry booths or water wash spray booths. In the dry booth, air
is withdrawn and passed through one or more filters or paint arresters.
Especially in larger furniture factories, laundry facilities for the
rags used in various finishing operations, are common. Major sources of
wastewater include the water wash spray booths, laundry facilities and
glue applicators which may require cleaning. Miscellaneous sources
comprise bleaching, bending operations, and air pollution control devices.
Generally, wastewaters from wood finishing plants are high in pH because
alkaline surfactant agents are used to disperse the finishing materials.
Strong detergents emanate from laundry facilities. These wastes may
demonstrate relatively low biodegradability.
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PARAMETERS OF CONCERN
BOD Temperature
COD TDS
Phenols Phosphorous
Oil/Grease Ammonia Nitrogen
pH Fluorides
TSS Boron
Zinc Arsenic
Copper Pentachlorophenol
Chromium Color
Mercury
Specifically for the Wood Preserving Segment of the Timber Products
Industry (Subcategories F, G, H) the following parameters are of
special importance:
pH: The pH level of wood preserving waste waters from creosote
and pentachlorophenol treatments generally varies from 4 to 6
but may be lower than 4.0.
Phenols: Phenolics in waste waters originate from contact with
creosote, pentachlorophenol-petroleum solutions, and from products
treated with these preservatives. Principal phenolics present in
the waste waters include para-, meta- and ortho-creosols, and
various derivatives of these compounds. Phenolics concentrations
in the waste waters range from 1 mg/1 up to 600 mg/1 or higher.
Phenolics are "presumed" to be readily degraded by acclimated
bacteria in biological POTW's.
Pentachlorophenol: PCP is soluble in water up to around 15-20
mg/1, but frequently exceeds these levels in wood preserving
wastes. The fate of pentachlorophenol in POTW's has not yet
been precisely determined.
Oil/Grease: Prevalent in both creosote and pentachlorophenol-
petroleum solutions. May occur either in free or emulsified form
in associated wastewaters. Oil/grease concentrations may range
from less than 100 mg/1 to much in excess of 1,000 mg/1 after
primary oil separation.
Copper, Chromium, Arsenic and Zinc: Constitute active ingredients
in wood preserving fire retardant formulations. In addition,
chromium and zinc are incorporated into fire retardant formu-
lations.
Boron: Boric acid and sodium tetraborate constitute ingredients
in commercial fire retardant mixtures used by the wood preserving
industry.
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Fluorides: Occur as sodium or potassium fluoride, the latter an
active constituent in one type of wood preserving solution. After
lime treatment, fluorides in wastewater may still be present in
the range of 10 to 20 mg/1.
Nitrogen and Phosphates: Both ammonium compounds and phosphates
are ingredients in fire retardants. Ammonia N and phosphates have
been measured in concentrations up to 25 mg/1 in the waste waters
originating from wood preserving plants employing fire retardants.
PRELIMINARY PRETREATMENT LIMITATIONS FOR DISCHARGE TO POTW
Subcategories A through E Including Barking, Veneer. Plywood and
Hardwood Processing. (New Source limitations are not yet clearly
defined).For Existing Sources, the Federal Regulations have determined
that waste waters from plants in the above subcategories are compatible
and may be introduced into POTW's without the need for pretreatment.
However, the pH of waste entering POTW's shall not be less than 5.0
unless the POTW is specifically designed to accomodate these pollutants.
Subcategories F. G, H, the Wood Preserving Subcategories. Proposed
Federal Regulations of April 18, 1974 indicate that wastewaters from
wood preserving plants may contain pollutants such as heavy metals,
phenols and/or oil and grease that could interfere with the operation of
POTW's, pass through such works untreated or inadequately treated, or
otherwise be incompatible with such works. Accordingly, for Subcategory
F, i.e. Wood Preserving, it was specified that there shall be np_ dis-
charge or process waste pollutants. For Subcategories G and H, the
following limitations are given and the pH of wastes to the POTW, is
to be controlled at 5.0 or above.
Subcategory G, Wood Preserving - Steam, Existing Sources.
Parameter
Oil /Grease
Copper
Chromium
Arsenic
Max. Day
(mg/1)
100
5
4
4
Max. Day
(grams/m3 production)
20.5
0.62
0.41
0.41
Subcategory H, Wood Preserving - Boultonizing, Existing Sources.
Oil/Grease
Copper
Chromium
Arsenic
100
5
4
4
20.5
0.62
0.41
0.41
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A Draft Report on Pretreatment for the Timber Products Industry
prepared by the EPA in August 1976 did not prescribe specific limi-
tations but indicated that pollutant levels after recommended pre-
treatment should conform to the following values:
For Wood Preserving Subcategory Plants. Oil separation in
combination with flocculation-filtration or decantation should
provide:
Concn. Limit, mg/1 Mass Limit, g/cu.m. Product
Oil/Grease 80 14.43
Pentachlorophenol 10 1.80
Copper 2.2 0.40
Chromium 2.6 0.43
Arsenic 4.1 0.74
Zinc 4.4 0.79
Boron 0.9 " 0.17
For Hood Preserving - Steam Subcategory Plants. Oil separation
followed by a flocculation-filtration system should provide:
Oil/Grease - less than 80 mg/1, and possibly 10 mg/1.
Pentachlorophenol - apparently 10 to 20 mg/1.
Copper - apparently 2.2 mg/1
Chromium - 2.6 mg/1
Arsenic - 4.1 mg/1
For Wood Preserving - Boultonizing Subcategory Plants. Oil separa- .
tion in combination with flocculation-filtration or decantation,
shall provide concentration and mass limits similar to those above
for Wood Preserving Subcategory Plants.
Subcategories I through 0, Wet Storage, Log Hashing, Sawmills and Planing
Mills, Finishing, Particleboard Manufacturing, Insulation Board
Manufacturing (New Source limitations are not yet clearly defined).
For Existing Sources, the Federal Regulations have determined that waste
waters from plants in Subcategories I through 0 are compatible for
acceptance into POTW's, and therefore no pretreatment limitations have
been specified. However the pH of wastes entering the POTW shall not be
less than 5.0 unless the POTW is designed to accomodate such pollutants.
Subcategories P through S, Wood Furniture and Fixture Production. (New
Source limitations are not yet clearly defined). For Existing Sources,
the Federal Regulations have determined that waste waters from Sub-
categories P through S are compatible for acceptance into POTW's, and
therefore no pretreatment limitations have been specified. However, the
pH of wastes entering POTW's shall not be less than 5.0 unless the POTW
is specifically designed to accomodate these pollutants.
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PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
Specifically for the Wood Preserving Segment of the Timber Products
Industry (i.e. Subcategories F, G, H), all or a portion of the follow-
ing treatment and control technologies and procedures have been tenta-
tively recommended by the EPA:
Oil separation and the use of flocculation-filtration.
Segregation of waste streams, water conservation measures,
elimination of leaks, flow equalization and recovery
systems when applicable.
Biological treatment has been identified but is unlikely as
pretreatment.
Importantly, it is noted that the Wood Preserving Subcategory
i.e. Subcategory F, was described as capable of achieving np_
discharge of process waste water to a POTW.
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UNBLEACHED KRAFT AND SEMICHEMICAL PULP/PAPER MILLS
(30, 142, 143, 144)
[Part 430]
SUBCATEGORIZATION OF THE INDUSTRY
Five Subcategories have been established for the Unbleached Kraft and
Semi chemical Mill Segment of the Pulp, Paper arid Paperboard Industry as
follows:
A - Unbleached Kraft Mills
B - Sodium-Based Neutral Sulfite Semi-Chemical Mills
C - Ammonia-Base Neutral Sulfite Semi-Chemical Mills
D - Unbleached Kraft, Neutral Sulfite Semi-Chemical
(Cross Recovery) Mills.
E - Paperboard From Waste Paper Mills
Further description of processes employed within Subcategories A
through E is provided below:
A) Unbleached Kraft Subcategory. Includes mills producing pulp
and paper by the unbleached kraft process. Wood, the fiber raw
material of unbleached Kraft pulp, enters the pulp mill as
logs or chips. Bark is removed from the logs either by a
wet or dry process. The chips are carried to a digester, a
large steel pressure vessel heated by steam to approximately
150°C. The chips are cooked in either a batch or continuous
operation to dissolve lignin and separate the cellulose fibers.
The cooking liquor is a mixture of sodium hydroxide and
sodium sulfite, which because of high costs, makes necessary
a chemical recovery system. The pulp with spent cooking
liquor is transferred to a brown-stock chest and then to
vacuum drum washers or continuous diffusers which separate
the pulp from the spent cook liquors. Paper is made by
depositing from a dilute water suspension of pulp, a layer
of fiber onto a fine screen which permits the water to drain
through but which retains the fiber layer. This layer is
removed from the wire, pressed and dried. Unbleached kraft
pulp is principally used for the manufacture of linerboard
and grocery sacks.
B) Sodium-Based Neutral Sulfite Semi-Chemical Subcategory.
Includes the production of pulp and paper by a neutral sul-
fite cooking liquor having a sodium base. NSSC mills may
purchase their cook chemicals, but more commonly they pre-
pare the cook liquors on the premises by burning sulfur and
absorbing it in soda ash or ammonia. Chemical recovery in
the sodium-base NSSC process is considerably more difficult
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than for the Kraft process. Most mills simply evaporate and
burn the spent cook liquor without recovery, but a few large
sodium-base NSSC mills do have chemical recovery systems. No
successful system has been developed for chemical recovery in
the ammonia-based NSSC mills (Subcategory C below), and the
spent liquors may be incinerated. The principal product from
Subcategory B mills is corrugated paperboard.
C) Ammonia-Base Neutral Sulfite Semi-Chemical Subcategory.
Includes the production of pulp and paper by a neutral sul-
fite cooking liquor having an ammonia base.
D) Unbleached Kraft. Neutral Sulfite Semi-Chemical (Cross
Recovery) Subcategory.Includes the production of pulp and
paper in combined unbleached Kraft and neutral sulfite semi-
chemical (NSSC) mills and where the sodium-based NSSC spent
liquors can be disposed of to the Kraft chemical recovery
system.
E) Paperboard From Waste Paper Subcategor.y. Paperboard products
such as corrugated boxes, box board, newspapers, etc. can be
manufactured from a wide variety of waste paper. In these
mills, waste paper represents 80 percent or more of the
fibrous materials incoming to the facility. Waste paper is
converted to secondary fiber waste paper by adding sufficient
water to dilute the materials to about 4-6 percent solids
and charging with chemicals to permit a controlled feed rate
to the pulper along with steam. The paper is ripped, shredded
and finally defibered. The stock is then passed through
centrifugal cleaners and a thickener. Reject material is
dewatered for disposal, and the stock sent to the refiners
which serve the paper machines.
NATURE OF PROBLEM
Major waste producing sectors include wood preparation, the pulping
processes, and the paper machines. Waste sources comprise wet barking,
pulp washing waters, various condensate streams in cooling and pulping,
chemical recovery operations and paper production waters.
In the pulp and paper industry, the dewatering and disposal of sludges
represents a major problem with high attendant costs. These sludges in
past decades were primarily placed into holding basins from which free
water was decanted. When a basin was full, it was simply abandoned, or
if sufficient drying occurred, the cake was excavated and deposited onto
marginal land. More advanced practices for better handling paper and
pulp mill sludges are now employed extensively through the industry.
Hopefully, these excess sludges will not enter into POTW's.
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PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTM AND PRESCRIBED TREATMENT
MEASURES
The subject of pretreatment, for both Existing and New Sources of
unbleached Kraft and semichemical pulp and paper mills has been
addressed in the Federal Register publications of January 15, 1974
and May 29, 1974. However up through the present no specific limita-
tions nor recommended pretreatment methods have been advanced for pulp
and paper mill wastes in the unbleached and semichemical segment of
the industry. Process waste water may be introduced into publicly-
owned treatment works pending future recommendations on pretreatment.
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BLEACHED KRAFT, GROUNDWOOD, SULFITE, SODA, DEINK AND
NON-INTEGRATED PULP/PAPER MILLS
(13, 14, 131, 141)
[Part 430]
SUBCATEGORIZATION OF THE INDUSTRY
Sixteen subcategories have been established for the Bleached Kraft,
Groundwood, Sulfite, Soda, Deink and Non-Integrated Mill Segment of the
Pulp, Paper and Paperboard Industry as follows:
F) Bleached Kraft Dissolving Pulp
G) Bleached Kraft Market Pulp
H) Bleached Kraft, Paperboard, Coarse and Tissue Papers (BCT)
I) Bleached Kraft, Fine Paper
J) Papergrade Sulfite (Blow Pit Wash)
K) Dissolving Sulfite Pulp
L) Groundwoodv Chemi-Mechanical (Fine Papers, Newsprint and
Molded Fiber Products)
M) Groundwood, Thermo-Mechanical (Fine Papers, Newsprint and
Tissue Papers)
N) Groundwood, Coarse, Molded Fiber and Newsprint (CMN)
0) Groundwood, Fine Papers
P) Soda Mills
Q) Deink Mills
R) Non-Integrated Fine Papers
S) Non-Integrated Tissue Papers
T) Non-Integrated Tissue Papers From Waste Paper
U) Papergrade Sulfite (Drum Wash)
Further description of mills within the various subcategories is pro-
vided below:
F) Bleached Kraft Dissolving Pulp Subcategory. Includes mills
which make a bleached pulp by a "full cook" process using a strong
alkaline sodium hydroxide and sodium sulfide cooking liquor. A "pre-
cook" operation termed pre-hydrolysis is employed. The principal pro-
duct is a highly-bleached and purified dissolving pulp destined for
rayon manufacture or for other needs requiring a high alpha cellulose
content.
G) Bleached Kraft, Market Pulp Subcategory. Includes mills which
make a bleached pulp by a "full cook" process using a strong alkaline
sodium hydroxide and sodium sulfite cooking liquor. Final product is
a papergrade market pulp.
H) BCT Bleached Kraft Subcategory. Includes the integrated pro-
duction of bleached kraft pulp and paper. Bleached kraft is made in
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175
a "full cook" process with a strong alkaline sodium hydroxide and
sodium sulfide cooking liquor.
I) Bleached Kraft, Fine Papers Subcategory. The integrated pro-
duction of bleached kraft pulp and fine paper. Bleached kraft is made in
a "full cook" process with a strong alkaline sodium hydroxide and sodium
sulfide cooking liquor. Fine papers comprise business, writing and printing
papers.
J) Papergrade Sulfite (Blow Pit Wash) Subcategory. The integrated
production of sulfite pulp and paper. Sulfite pulp is made in a "full
cook" process using an acidic cook liquor of sulfites of calcium, mag-
nesium, ammonia, or sodium. Following cooking, the spent cooking liquor
is separated from the pulp in blow pits. Principal products are tissue
papers, newspaper, fine papers, and market pulp.
K) Dissolving Sulfite Pulp Subcategory. Includes mills making a
highly bleached and purified pulp from softwoods by a "full cook" pro-
cess involving strong solutions of sulfites of calcium, magnesium,
ammonia, or sodium. These pulps are used principally for the manufacture
of rayon and other products requiring the virtual absence of lignin.
L) Groundwood, Chemi-Mechanical Subcategory. The integrated pro-
duction of chemical-mechanical groundwood pulp and paper. A chemical
cooking liquor is employed in a partial cook of the wood followed by
mechanical defibration. Principal products are fine papers, newsprint
and molded fiber items.
M) Groundwood, Thermo-Mechanical Subcategory. The production of
thermo-mechanical groundwood pulp and paper. Groundwood is made by a
brief cook utilizing steam with or without cooking chemicals such as
sodium sulfite, which is followed by mechanical defibration. Principal
products are market pulp, fine papers, newsprint, and tissue papers.
N) Groundwood, CMN Papers Subcategory. The integrated production
of groundwood pulp and paper. The pulp is made utilizing only mechani-
cal defibration. Principal products are coarse papers, molded fiber
items, and newsprint.
0) Groundwood, Fine Papers Subcategory. The integrated production
of groundwood pulp and fine papers. The pulp is made utilizing only
mechanical defibration. Principal products are fine papers comprising
business, writing and printing papers.
P) Soda Subcategory. The integrated production of bleached soda
pulp and paper. The pulp is made by a "full cook" process with a
strong alkaline sodium hydroxide cooking liquor. Principal products
are fine papers comprising printing, writing and business papers,
together with market pulp.
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176
Q) Deink Subcategory. The integrated production of deinked pulp
and paper. Deinked pulp is generally made from waste papers using an
alkaline treatment procedure to remove contaminants such as ink and
coating pigments. Principal products besides pulp are printing,
writing and business papers, tissue papers, and newsprint.
R) Non-Integrated Fine Papers Subcategory. Includes mills which
produce fine papers from wood pulp or deinked pulp prepared off-site.
Principal products are printing, writing, business and technical papers.
S) Non-Integrated Tissue Papers Subcategory. Includes mills which
produce tissue papers from wood pulp or deinked pulp prepared off-site.
Principal products are facial and toilet papers, glassine, paper dia-
pers, and paper towels.
T) Non-Integrated Tissue Papers From Waste Paper Subcategory.
Includes mills which produce tissue papers from waste papers without de-
inking. Principal products are facial and toilet papers, glassine,
paper diapers and paper towels.
U) Papergrade Sulfite (Drum) Hash) Subcategory. Integrated pro-
duction of sulfite pulp and paper. The sulfite pulp is made in a
"full cook" process employing an acidic cooking liquor of sulfites of
calcium, magnesium, ammonia or sodium. The spent cooking liquor is
then washed from the pulp on vacuum or pressure drums. Also included
are belt extraction systems for pulp washing. Principal products are
tissue papers, fine papers and newspapers, together with market pulp.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity Settleable Solids
BOD Turbidity
TSS • COD
Color Resin Acids
Ammonia N Polychlorinated Biphenyls
Zinc Coliform Organisms
Temperature Mercury
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
Proposed pretreatment regulations for existing and new sources' in the
pulp, paper and paperboard industry, Subcategories F through U, were
published in the Federal Register of February 19, 1976 and subsequently
modified in a recent publication of January 6, 1977.
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Subcategory F - Bleached Kraft, Dissolving Pulp.
For existing and new Sources: No limitations.
Subcategory G - Bleached Kraft Market Pulp.
For existing and new Sources: No limitations.
Subcategory H - Bleached Kraft, Paperboard, Coarse, Tissue Paper.
For existing and new Sources: No limitations.
Subcategory I - Bleached Kraft, fine Papers.
For existing and new Sources: No limitations.
Subcategory J - Papergrade Sulfite.
For existing and new Sources: Limitations not yet established. -
Subcategory K - Dissolving Sulfite Pulp.
For existing and new Sources: No limitations.
Subcategory L - Groundwood, Chemi-Mechanical.
For existing Sources where Zinc Hydroxide used as bleaching agent:
Zinc, lb/1,000 Ib product
Avg. 30 Day - .06
Max. Day - .12
For new Sources where Zinc Hydroxide used as bleaching agent:
Avg. 30 Day - .048
Max. Day - .095
Subcategory M - Groundwood, Thermo-Mechanical.
For existing Sources, where Zinc Hydroxide used as bleaching agent:
Zinc, lb/1,000 Ib. product
Avg. 30 Day - .05
Max. Day - .105
For new Sources, where Zinc Hydroxide used as bleaching agent:
Avg. 30 Day - .0455
Max. Day - .090
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Subcategory N - Groundwood, Coarse, Molded Fiber, Newsprint.
For existing Sources, where Zinc Hydroxide used as bleaching agent:
Zinc, 1b/1.000 Ib. product
Avg. 30 Day - .05
Max. Day - .105
For new Sources, where Zinc Hydroxide used as bleaching agent:
Avg. 30 Day - .0455
Max Day - .090
Subcategory 0 - Groundwood, Fine Papers.
For existing Sources, where Zinc Hydroxide used as bleaching agent:
Zinc, lb/1,000 Ib. product
Avg. 30 Day - .048
Max. Day - .095
For new Sources, where Zinc Hydroxide used as bleaching agent:
Zinc, lb/1.000 Ib. product
Avg. 30 Day - .044
Max. Day .090
Subcategory P - Soda Mills.
For existing and new Sources: No Limitations.
Subcategory Q - Deink Mills.
For existing and new Sources: No Limitations.
Subcategory R - Non-Integrated Fine Papers.
For existing and new Sources: No Limitations.
Subcategory S - Non-Integrated Tissue Papers.
For existing and new Sources: No Limitations.
Subcategory T - Non-Integrated Tissue Papers from Waste Paper.
For existing and new Sources: No Limitations.
Subcategory U - Papergrade Sulfite (Drum Wash).
For existing and new Sources: Limitations not yet established.
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BUILDING PAPER AND ROOFING FELT MANUFACTURING
(80, 81, 82)
[Part 431]
SUBCATEGORIZATION OF THE INDUSTRY
Building Paper and Roofing Felt Manufacturing is considered to be part
of the overall Building Paper and Buiilders Board Industry. To date,
only Subcategory A has been defined by the EPA guidelines limitations,
also known as the Builders Paper and Roofing Felt Subcategory.
NATURE OF PROBLEM
Builders Paper and Roofing Felt mills produce the heavy papers used in
the construction industry made from cellulose fibers in turn derived
from waste paper, wood flour and sawdust, wood chips and rags. Bleaching
and chemical pulping are not employed by these mills.
Builders papers are generally characterized as saturating papers, floor-
ing paper, and deadening papers used by the construction and automotive
industries. They differ from the roofing felts in thickness and possible
chemical additives to the builders papers.
Dry roofing felt is a strong, highly absorbent material used as backing
and support for subsequent bituminous coating. These coatings serve to
waterproof the final product.
Waste loads from Builders Paper and Roofing Felt mills originate princi-
pally from the stock preparation and board manufacturing processes. Loss
of fiber and miscellaneous materials occur from both the "white water"
and stock cleaning rejects which are continuously discharged. Cleaning
losses are also encountered. Additional waste sources may include cool-
ing and quenching the coatings on roofing felts. Mica, talc or similar
solids can be lost to the waste streams.
Fifty-six mills which produce saturated papers and/or coating or
dry roofing felt were identified in the industry. The majority of the
mills are located in or near metropolitan areas. It was found that up
to 75 percent of the mills have access to municipal sewers and POTW's.
PARAMETERS OF CONCERN
BOD Turbidity TSS
TSS Color
pH Nitrogen and Phosphorous
Settleable Solids Polychlorinated Biphenyls
Oil/Grease
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PQLYCHLORINATED BIPHENYJ.S (PCB's) are chemically and thermally-stable
compounds contained in waste papers, Recycled office papers appear to
be a main source of PCB's although recycled paperboard also shows evi-
dence of PCB's.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTVI AND PRESCRIBED TREATMENT
MEASURES.- No specific limitations have been developed to date in the
Federal regulations for the discharge of builders paper and roofing
felt wastewaters to municipal collection and treatment systems. The
pollutants in these waste waters are considered to be chiefly organic
materials and solids, and generally compatable to municipal treatment.
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RED MEAT SEGMENT OF THE MEAT .PRODUCTS INDUSTRY
(171, 172, 173, 174, 175)
[Part 432]
SUBCATEGORIZATION OF THE INDUSTRY
The overall Meat Products Industry has been divided into 15 subcate-
gories including subcategories A through D covering the Red Meat
Segment of the industry; subcategories E through I described as the
Processor Segment of the industry; subcategory J representing the
Rendering Segment; and subcategories K through 0 the Poultry Processing
Segment of the industry. These are tabulated as follows:
A) Simple Slaughterhouse
B) Complex Slaughterhouse
C) Low Processing Packinghouse
D) High Processing Packinghouse
E) Small Processor
F) Meat Cutter
G) Sausage and Luncheon Meats Processor
H) Ham Processor
I) Canned Meats Processor
J) Renderer
K) Chicken Processor
L) Turkey Processor
M) Fowl Processor
N) Duck Processor
0) Further Processing Subcategory
The Red Meat Segment of the industry consisting of four distinct sub-
categories is described below:
Subcategory A, Simple Slaughterhouses. A slaughterhouse is
defined as a plant that slaughters animals and has as its main
product fresh meat in whole, half, or quarter carcasses or
smaller cut meats. A "simple slaughterhouse" refers to a
slaughterhouse which accomplishes very limited by-product
processing, if any, such as rendering, paunch and viscera
handling, blood, hide or hair processing.
Subcategory B, Complex Slaughterhouses. A slaughterhouse that
performs extensive byproduct processing, generally including
at least three operations such as rendering, paunch and viscera
handling, blood, hide or hair processing.
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182
Subcategory C, Low-Processing Packinghouses. A packinghouse is
defined as a plant that both slaughters animals and subsequently
processes carcasses into cured, smoked, canned or other prepared
meat products. A "low processing" packinghouse refers to a
packinghouse that processes no more than the total animals killed
at that particular plant, and normally processes less than the
total kill.
Subcategory D. High-Processing Packinghouses. A packinghouse
which processes both animals slaughtered at the site and addi-
tional carcasses from outside sources.
NATURE OF PROBLEM
Plants in the meat products industry range from establishments that
carry out only one operation, such as slaughtering, to full-line
plants that not only slaughter, but also conduct processing to vary-
ing levels, i.e. conversion of meat products into sausages, cured
hams, smoked products, etc. Slaughtered animal types include cattle,
calves, hogs and sheep. As of March 1973, 5990 meat slaughtering
plants were recorded in the U.S. Fifteen percent of the plants in
the industry account for 90 percent or more of the total production.
In 1966, about 70 percent of all waste water in the meat packing
industry was discharged to municipal sewers. Waste waters from meat
slaughtering, packinghouses and associated facilities such as stock-
yards, rendering and feed manufacturing plants contain organic matter,
grease, TSS and inorganic materials such as phosphates and salts.
These materials enter sewers and streams as manure, curing and pickling
solutions, caustic or alkaline detergents, et. al.
PARAMETERS OF CONCERN
pH Ammonia N
BOD TKN
COD Nitrates, nitrites
TSS Phosphorous
TDS Chlorides
TVS Temperature
Oil and Grease
Total and Fecal Coliforms
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PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
The 40 CFR Part 432 Federal Regulations for both existing and new
sources in the meat products industry have not formulated pretreatment
limitations, and thusly, these wastes may be discharged to POTW's.
PRESCRIBED PRETREATMENT FOR DISCHARGE TO POTW
The Development Document of October 1973 on the Meat Products Industry
together with the Federal Register publications on meat industry wastes
describe the subject effluents as containing no constituents which
would interfere with, pass through, or otherwise be incompatible with
well-designed and operated POTW's. However, suggestions have been
made that these effluents before reaching the POTW should receive in-
plant recovery for the removal of grease and gross solids. Grease can
be a valuable by-product when collected and sent to rendering. Greases
are collected via catch basins, grease traps or dissolved air flotation
units. Solids are removed by settling or via screens-static, vibrating
or rotating and generally self-cleaning types. Waste equalization
is desirable. In-plant controls should emphasize the following practices:
Prevent waste materials from interfacing with water streams.
Covering and dry cleaning of livestock holding pens, careful
control over drinking water troughs, and separate disposal
of pen manure etc. to agricultural fields.
Separate collection and recovery of blood wastes.
Separate handling and disposal of paunch materials.
Precluding viscera wastes from entering plant sewers.
Installation of troughs under the killing room to keep blood,
trimmings, bone dust and miscellaneous off the floors.
Wastewater from rendering should be condensed and/or evaporated
for sale or disposal as "stickwater." Tankwater, greases
and cracklings should receive high priority for recovery.
Overflows from hide curring vats or raceways should receive
close control.
Hog scald tanks contain strong wastes which should be
collected, treated, and if possible, reused.
Consideration should be given to special handling of spent
pickling and curing liquors which contain high levels of
salt and in many cases, also have high sugar content.
Many possibilities of water reuse and water reduction inside
the meat processing plant have been demonstrated and warrant
serious attention for implementation.
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PROCESSOR SEGMENT OF MEAT PRODUCTS INDUSTRY
(16, 17)
[Part 432]
SUBCATEGORIZATION OF THE INDUSTRY
The Meat Products Industry consists of 15 Subcategories. The Processor
Segment described herein includes five Subcategories, i.e. E through I.
The slaughtering of animals, rendering and poultry processing are
covered elsewhere in this report.
Meat processing plants included in this segment of the industry are
plants which manufacture prepared meats and meat products from purchased
carcasses, meat cuts and other materials, and perform np_ slaughtering
at the same plant site. Processing plants that produce 6,000 Ibs. or
less of finished product per day are categorized as Small Processors.
Remaining plants are described as large processors and are further
divided into four Subcategories, i.e. F through I. Canned pet foods
are not included in the meat processing industry.
Subcategory E. Small Processors. Refers to the production of
finished meat products such as fresh meat cuts, smoked products,
canned products, hams, sausages, luncheon meats or similar products
by a small processor. A small processor is further defined as an
operation that produces 6,000 Ib/day or less of finished products.
Subcategory F. Meat Cutters. Refers to the fabrication or manu-
facture of fresh meat cuts such as steaks, roasts, chops, etc. by
a meat cutter. A meat cutter is further defined as an operation
which fabricates, cuts or otherwise produces fresh meat cuts and
other finished products from livestock carcasses, at rates greater
than 6,000 Ib/day.
Subcategory 6, Sausage and Luncheon Meat Processors. Applies to
the manufacture of fresh meat cuts, sausage, bologna and other
luncheon meats by a sausage and luncheon meat processor. A
sausage and luncheon meat processor is defined as an operation
which cuts fresh meats, grinds, mixes, seasons, smokes or other-
wise produces finished products as sausage, bologna, and luncheon
meats at rates greater than 6,000 Ib/day.
Subcategory H. Ham Processors. Applies to the manufacture of hams
alone or in combination with other finished products by a.ham
processor. A ham processor is defined as an operation which manu-
facturers finished products at rates greater than 6,000 Ib/day.
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185
Subcategory I. Canned Meat Processor. Applies to the manufacture of
canned meats alone or in combination with other finished products by a
canned meats processor. A canned meat processor is defined as an opera-
tion manufacturing canned meats such as stew, sandwich spreads or other
finished products at rates greater than 6,000 Ib/day.
NATURE OF PROBLEM
A total of 1374 meat processing plants were included in the 1967 Census
of Manufacturers in the U. S. An additional 168 meat processing plants
were reported under Federal inspection up through June 30, 1973. The
small processing plant handling less than 6,000 Ibs finished product
per day, is estimated to account for 85 to 90 percent of the total
number of plants, but only produces 10 to 15% of total meat processed
across this Segment of the industry. In 1967, it was estimated about
70% of all meat packing and processing wastewaters found their way into
municipal sewers. By 1972, 80% or more of the meat processing plants
were said to be discharging to municipal sewers.
Typical operations and major water sources inside a meat processing
installation include: meat materials preparation, pickling, product
cooking and cooling, and canning.
PARAMETERS OF CONCERN
pH, acidity, alkalinity
BOD
COD
TSS
TDS
TVS
Oil and Grease
Nitrogen including Ammonia N,
TKN, nitrates and nitrites
Phosphorous
Chlorides
Temperature
Fecal coliforms
Ammonia Nitrogen is but one of many forms of nitrogen-type pollutants
present in meat processing wastewaters. Anaerobic decomposition of
protein, which is essentially organic nitrogen, leads to the formation
of ammonia. Thusly, anaerobic waste treatment lagoons or digesters can
produce high levels of ammonia. Septic or anaerobic conditions in
traps, holding chambers, etc. also leads to ammonia formation in waste-
water. Another source of ammonia is leakage from ammonia refrigeration
systems, thought to be fairly common in meat processing plants.
Nitrates and nitrites are the result of the oxidation of ammonia and
organic nitrogen. Nitrates and nitrites are also ingredients in curing
and pickling solutions and in processed meat formulations.
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186
Chlorides originate from meat processing plants as salt from animal
tissues, pickling and curing solutions, cleaning chemicals, blowdown
waters and the salt sprinkled on processing plant floors to prevent
slipping.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
The 40 CFR, Part 432 Regulations of January 3, 1975 give no specific
limitations for existing and new meat processing installations dis-
charging wastes to municipal sewers.
PRESCRIBED TREATMENT FOR DISCHARGE TO POTVJ
The Development Document of August 1974 on Meat Processor Plant waste-
waters describes these effluents as containing no constituents which
would interfere with, pass through, or otherwise be incompatible with
well-designed and operated POTW's. It is however reported that this
wastewater should pass through materials recovery operations in order
to remove settleable solids and a majority of the grease. Materials
recovery is accomplished by in-plant control measures and primary treat-
ment. It is possible that grease remaining in the partially-treated
effluent to a POTW can cause difficulties at the POTW. A concentration
of 100 mg/1 oil and grease is usually cited as the upper limit to the
POTW. An air flotation system may be required in addition to catch
basins. If the BOD strength of wastes going to the POTW must be
reduced further, anaerobic contact, aerated lagoons and other methods,
may be considered for pretreatment.
In-Plant Control methods at Meat Processor Plants generally include
collection of spent pickling and curing solutions, various water
conservation practices and modification of plant cleanup procedures
including dry squeegeeing or scraping of affected surfaces, proper
use of drain basins, minimization of water and detergents, and automa-
tion of conveyors, piping and other equipment. Primary treatment
consists of one or more operations of waste flow equalization,
screening, catch basins, and dissolved air flotation.
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RENDERING SEGMENT OF THE MEAT PRODUCTS INDUSTRY
(15, 16, 171)
[Part 432]
SUBCATEGORIZATION OF THE INDUSTRY
Rendering has been defined as Subcategory J of the overall Meat Products
Industry. This segment of the industry considers only independent
rendering plants which collect animal byproducts such as bone, offal,
fat and dead animals from slaughterhouses, processing plants, butcher
shops, restaurants, feed lots, ranches, and process these materials
into end products such as fats, oils, and solid proteinaceous meal.
Heat melts the fat out of tissues, coagulates all proteins and evaporates
material moisture. The end products may be either edible or inedible.
Plants processing fish byproducts are not included in this study.
An independent rendering plant may also cure hides as an ancillary
operation.
The term "renderer" is specifically defined as an independent or off-
site rendering operation, conducted separately from a slaughterhouse,
packinghouse, or poultry processing plant, which manufactures at rates
greater than 75,000 pounds of raw material per day. Raw material
includes meat meal, tankage, animal oils, grease and tallow, but excludes
marine oils, fish meal and fish oils. The term "tankage" shall mean
dried animal by-product residues used in feedstuffs. The term "tallow"
shall mean a material made from beef cattle or sheep fat that has a
melting point of 40°C or higher.
NATURE OF PROBLEM
Of about 450 renderers encompassed by this study, approximately one-half
discharge to municipal sewers; one-quarter achieve zero discharge of
pollutants; and one-quarter directly discharge to surface waterways.
PARAMETERS OF CONCERN
pH. Acidity, Alkalinity Ammonia N
BOD - TKN
COD Nitrates, Nitrites
TSS Phosphorous
TDS Chlorides
TVS Total and fecal coliforms
Oil and Grease Temperature
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Oil and Grease is a major pollutant in waste streams from rendering
plants. Sources of grease are primarily the spillage of processed
tallow and associated materials and the cleanup of equipment, floors,
barrels and trucks. Grease forms unsightly films on water, interferes
with aquatic life, clogs sewers, disturbs biological treatment processes,
and can become a fire hazard. Levels of grease in raw waste will
average around 1600-1700 mg/1.
Ammonia and Kjeldahl Nitrogen pollution loads are highly affected by
.blood losses from raw material drainage and blood and feather opera-
tions, and the degree of liquid entrainment in the cooking vapors.
Typical raw waste TKN concentrations will range from 50 to 800 mg/1.
Chlorides in rendering plant wastes originate as salts from animal
tissues, hide curing operations and blood. Chlorides are much higher
in plants processing hides and sewering the blood wastes.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
The 40 CFR, Part 432 Regulations of January 3, 1975 provide np_ specific
limitations for existing and new rendering sources which discharge wastes
to municipal sewers.
PRESCRIBED PRETREATMENT FOR DISCHARGE TO POTW
The Development Document of August 1974 on Rendering Plant wastewaters
describes those effluents as containing no constituents which would
interfere with, pass through, or otherwise be incompatible with well-
designed and operated POTW's. It is however reported that this waste-
water should pass through materials recovery in order to remove
settleable solids and a majority of the grease. Materials recovery is
accomplished by in-plant measures and primary treatment. It is possible
that grease remaining in the partially-treated effluent to the POTW
can cause difficulty at the POTW. Trickling filters appear to be
particularly sensitive. A concentration of 100 mg/1 oil and grease is
usually cited as the upper limit to the POTW. An air flotation system
may be required of the renderer in addition to catch basins. If the
BOD strength of wastes going to the POTW must be reduced, anaerobic
contact, aerated lagoons and other methods, may be considered for pre-
treatment.
In-Plant Control methods at rendering plants include special handling
of condensables and high-strength liquid wastes, truck and barrel
washings, odor control and plant cleanup and spills. Primary treatment
would consist of one or more methods of waste flow equalization,
screening, use of catch basins and dissolved air flotation.
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POULTRY SEGMENT OF THE MEAT PRODUCTS INDUSTRY
(22, 23)
[Part 432]
SUBCATEGORIZATION OF THE INDUSTRY
For the Poultry Industry, five sub-classes are proposed:
Subcategory K. Chicken Processor. A chicken dressing plant that
primarily slaughters broilers. The plant may also cut up, further
process and/or render at the same plant site.
Subcategory L. Turker Processor. A turkey dressing plant that
primarily slaughters turkeys. The plant may also cut up and
further process concurrently or seasonally and/or render at the
same plant site.
Subcategory M. Fowl Processor. A fowl dressing plant that
primarily slaughters light or heavy fowl, i.e. mature chickens.
The plant may also cut up, further process and/or render at the
same plant site. Geese and capon dressing plants are included
in this Subcategory.
Subcategory N. Duck Processor. A duck processing plant that
primarily slaughters ducks. The plant may also cut up, further
process and render at the same plant site.
Subcategory 0. Further Processing. A poultry plant that conducts
only "further processing" with any type of bird, but has no onsite
slaughtering. Cooking is involved in all "further processing"
plants. Various ingredients are mixed with the poultry meat and
the numerous products .are formed, cooked (into cut, ground, chopped
breaded, etc.), packaged, and usually frozen. Plants that process
eggs or manufacture such products as canned soups and TV dinners
are excluded from the above subcategories.
NATURE OF PROBLEM
Principal waste sources within poultry processing are killing, breeding,
scalding, defeathering, evisceration, chilling, further processing,
rendering, and various condenser operations.
Wastewaters from poultry processing plants contain organic matter,
grease, TSS, inorganics such as phosphates, nitrates and nitrites, and
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190
coliform bacteria. Waste materials consist of meat and fatty tissue,
offal, feathers, body fluids from the birds, blood, loss of materials
from processing, preservatives, lost product ingredients and caustic or
alkaline detergents.
The end products of slaughtering and eviscerating operations are ice
packed or chilled ready-to-cook broilers and chickens, fresh or frozen
fowl, turkeys, etc. Small game are also processed by the industry.
"Further processing" leads to a variety of cooked, canned and processed
poultry meat items such as pre-cooked breaded parts, roasts, rolls,
patties, meat slices in gravy, canned boned chicken and various sausages,
In 1973, there were 248 Federally-inspected poultry plants that only
conducted slaughtering, 288 that processed only, and 144 plants that
both slaughtered and processed.
PARAMETERS OF CONCERN
BOD Ammonia N
COD TKN
TSS Nitrates, nitrites
IDS Phosphorous
TVS Chlorides
Oil and Grease pH
Total and Fecal Coliforms Temperature
Grease is a major pollutant in raw wastes from poultry processing
establishments. Grease forms unsightly films and layers on water,
interfers with aquatic life, clogs sewers, disturbs biological processes
in POTW's, and can also become a fire hazard. The concentration of
grease in poultry processing raw waste waters ranges from 100 to 400
mg/1. Grease can foul municipal treatment facilities especially trick-
ling filters, and seriously reduce their effectiveness. Thus, grease
may be of great concern to municipal treatment plants.
Phosphorous in raw poultry wastewaters originates from bone meal in
cutting, detergents used in cleanup, food additives, and from boiler
water additives.
LIMITATIONS FOR DISCHARGE TO POTVJ
No specific limitations have been prescribed up to this time. Main
pollutant parameters that were considered for limitation include BOD,
TSS, Oil and Grease, Fecal Coliforms and pH.
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PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
No constituents have been found in poultry processing wastewaters
which would interfere with, pass through, or otherwise be incompatible
with a well-designed and operated biological-type POTW's. The poultry
processing effluent before reaching the municipal sewer, should how-
ever be passed through byproduct recovery and in-plant primary treat-
ment at the poultry plant in order to remove settleable solids and the
majority of the grease. It is possible that greases remaining in the
poultry plant effluent can cause difficulty at the POTVJ. Trickling
fitters appear especially sensitive. A concentration of 100 mg/1 oil
and grease is usually cited as the upper limitation for acceptance
by a POTW. Achieving this level may require an effective air flotation
system in addition to catch basins. If the waste strength measured as
BODg must be further reduced, biological unit operations including
anairobic contact, trickling filtration or aerated lagoons, can be
used for pretreatment.
In-Plant Controls and byproduct recovery include one or more of the
following practices.
Control and minimize water usage throughout the plant.
Stun birds during killing so as to reduce carcass movement
during bleeding.
Confine bleeding, provide sufficient bleed time and recover
all collectable blood.
Consider reuse of chiller water for makeup to the scalder.
Consider dry offal handling in lieu of waste fluming.
Closely monitor screening systems used for offal and feathers,
and deploy backup screens if at all possible.
Separate and treat offal truck drainage before sewering.
Use dry cleanup prior to floor and equipment washdown. This
is particularly important in bleeding and cutting areas.
Minimize chemicals and detergents used in cleaning.
All spent raw materials should be routed to rendering rather
than to plant sewers.
Segregate all overflows from the cooking sector for grease
and solids recovery and/or treatment.
Offal and feathers in respective flow-away systems to be
properly screened, collected and taken to rendering.
In-Plant primary treatment and byproduct recovery should consist of
the following: flow equalization, effective screening, use of catch
basins and if necessary, dissolved air flotation and electrocoagulation.
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COAL MINING INDUSTRY
(73, 74, 75, 76)
[Part 434]
SUBCATEGORIZATION OF THE INDUSTRY
The Coal Mining Industry is divided into coal production and coal prep-
aration. Mining creates both acid and alkaline drainage. Preparation
involves preparation plant waste water and area wastewater around the
plant. The industry has been divided into four subcategories as shown
below:
A - Coal preparation plant
B - Coal storage, refuse storage and coal preparation plant
ancillary area
C - Acid or ferruginous mine drainage
D - Alkaline mine drainage
NATURE OF THE PROBLEM
The Federal Regulations contained in the Federal Register, Part 434 are
applicable to discharges resulting from the cleaning or beneficiation
of coal of any rank including but not limited to bituminous, lignite and
anthracite.
In coal preparation plants process methods generally require an alkaline
media for efficient and economical operation. Therefore, process water
does not dissolve significant quantities of constituents found in raw
coal. Coal preparation plants generate TSS as a principal pollutant.
Coal storage, refuse storage and coal preparation ancillary areas have
wastes generally similar to drainage at the mine served by the prepara-
tion plant. Coal mining produces drainage which may vary in character
from grossly polluted to drinking water quality. Two main types of mine
drainage are found: 1) acid or ferruginous-high in acid and iron and
with varying concentrations of aluminum, manganese, nickel and zinc,
and usually requiring neutralization and settling; and 2) alkaline -
possibly requiring settling. Water enters mines via precipitation,
ground water infiltration and runoff, where it may become polluted by
contact with materials in the coal, the overburden material, or the
mine bottom.
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193
PARAMETERS OF CONCERN
pH, acidity, alkalinity IDS
Iron, dissolved and total Sulfate
Manganese Fluoride
Aluminum Strontium
Nickel Ammonia N
Zinc TSS
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
Wastewaters from the Coal Mining Industry are not characteristic of
wastes considered amenable to treatment by biological means. Coal
mining wastes are generally not compatible with sanitary sewage because
of their potential acidic nature, metals content, and large volume
rates. However, certain metallic salts such as aluminum sulfate and
ferrous salts may be considered beneficial and are used in wastewater
treatment as coagulants. It has been shown under controlled conditions
that acid mine drainage and municipal wastes may be handled by joint
treatment.
The Federal Regulations on Existing Sources of Coal Mining indicates
these wastewaters, if necessary, may possibly be accepted into POTW's.
However, the operator of a POTW is cautioned that certain constituents
in coal mining wastewaters may interfere with the treatment works or
can pass through the treatment works inadequately treated. Therefore,
these waste waters should receive special consideration by the operator
of the POTW and the wastes may be subject to further regulations.
For New Sources of Coal Mining, special pretreatment limitations have
been prescribed for Subcategory A, coal preparation plants, and for
Subcategory B, coal storage, refuse storage and coal preparation plant
ancillary areas as shown below:
Subcategory A - Max. daily of 50 mg/1 dissolved iron
Subcategory B - Max. daily of 50 mg/1 dissolved iron
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OFFSHORE AND ONSHORE OIL AND GAS EXTRACTION INDUSTRY
(137, 138, 139, 140)
[Part 435]
SUBCATEGORIZATION OF THE INDUSTRY
The Oil and Gas Extraction Industry has been divided into six subcate-
gories, the first two relating to Offshore installations and other four
to Onshore installations. Major pollutants are derived from the pro-
duction of crude petroleum and natural gas, drilling of oil and gas
wells, and oil and gas field exploration services. The six subcate-
gories comprise:
A - Near Offshore Subcategory
B - Far Offshore Subcategory
C - Onshore Subcategory
D - Coastal Subcategory
E - Beneficial Use Subcategory
F - Stripper Subcategory
Subcategory A - Near Offshore Facilities. Includes offshore structures
within State waters engaged in the production, field exploration, drill-
ing, well completion and well treatment of oil and gas.
Subcategory B - Far Offshore Facilities. Includes offshore structures
within Federal waters engaged in the production, field exploration,
drilling, well completion and well treatment of oil and gas.
Subcategory C - Onshore Facilities. Includes onshore structures engaged
in the production, field exploration, drilling, well completion and well
treatment of oil and gas, but is not applicable to those onshore facili-
ties defined in Subcategories D, E and F. "Onshore" means all land and
water areas landward from the inner boundary of the territorial seas,
including the Great Lakes.
Subcategory D - Coastal Works. Includes coastal facilities engaged in
the production, field exploration, drilling, well completion and well
treatment of oil and gas. The term "coastal" is interpreted as com-
prising all land and water areas landward from the inner boundary of
the territorial seas, and bounded on the inland side by a line defined
by the inner boundary of the territorial seas as defined above eastward
of the point defined by 89° 45' W. Longitude and 29° 46' N Latitude and
continuing as follows west of that point:
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195
Direction to West Longitude Direction to North Latitude
West, 89° 48' North, 29° 50'
West, 90° 12' North, 30° 06'
West, 90° 20' South, 29° 35'
West, 90° 35' South, 29° 30'
West, 90° 43' South, 29° 25'
West, 90° 57' North, 29° 32'
West, 91° 02' North, 29° 40'
West, 91° 14' South, 29° 32'
West, 91° 27' North, 29° 37'
West, 91° 33' North, 29° 46'
West, 91° 46' North, 29° 50'
West, 91° 50' North, 29° 55'
West, 91° 56' South, 29° 50'
West, 92° 10' South, 29° 44'
West, 92° 55' North, 29° 46'
West, 93° 15' North, 30° 14'
West, 93° 49' South, 30° 07'
West, 94° 03' South, 30° 03'
West, 94° 10' South, 30° 00'
West, 94° 20' South, 29° 53'
West, 95° 00' South, 29° 35'
West, 95° 13' South, 29° 28'
East, 95° 08' South, 29° 15'
West, 95° 11' South, 29° 08'
West, 95° 22' South, 29° 56'
West, 95° 30' South, 28° 55'
West, 95° 33' South, 28° 49'
West, 95° 40' South, 28° 47'
West, 96° 42' South, 28° 41'
East, 96° 40' South, 28° 28'
West, 96° 54' South, 28° 20'
West, 97° 03' South, 28° 13'
West, 97° 15' South, 27° 58'
West, 97° 40' South, 27° 45'
West, 97° 46' South, 27° 28'
West, 97° 51' South, 27° 22'
East, 97° 46' South, 27° 14'
East, 97° 30' South, 26° 30'
East, .97° 26' South, 26° IT
East to 97° 19' W. Longitude and Southward to the U.S.-Mexican border.
Along all boundaries of the territorial seas except the Gulf of Mexico,
the term "coastal" is not defined.
Subcategory E - Beneficial Use. This subcategory is applicable to
onshore facilities for which produced water has a beneficial use when
discharged to navigable waters. These facilities are engaged in the
production, drilling, well completion and well treatment of oil and gas.
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196
Subcategory F - Stripper Works. This subcategory is applicable to
onshore facilities which produce less than 10 barrels per calendar
day of crude oil and one operating at the maximum feasible rate of
production in accordance with recognized conservation practices.
These facilities are engaged in the production and well treatment of
oil and gas.
NATURE OF PROBLEM .
There are some half million producing oil wells onshore generating
produced water in excess of 10 BGD. Approximately 17,000 wells have
been drilled offshore in U.S. waters and there are around 11,000
operations producing both oil and gas. Offshore leasing, exploration
and development will expand rapidly over the future, and offshore
production will constitute an increasing proportion of the domestically-
produced supplies of gas and oil.
Wastes associated with offshore and onshore oil and gas extraction
facilities result from the discharge of produced water, deck drainage,
drilling muds, drill cuttings, well treatment, sanitary and domestic
needs and produced sands. Produced waters are those wastes generated
when the natural oil-water or gas-water interfaces within the oil-gas
bearing formations are disrupted. Deck drainage includes waste from
platform washings, deck washings, and runoff from curbs, gutters, and
drains including drip pans and work areas. Drilling muds are materials
used to maintain hydrostatic pressure in the well, lubricate the drill-
ing bit, remove drill cuttings from the well, or to stabilize the walls
of the well during drilling and workover. Drill cuttings contain metals
and mineral particles from drilling into subsurface geologic formations.
Drill cuttings are brought to the surface of the well with drilling
muds and are then separated from the muds. Well treatment wastes arise
from acidizing and hydraulic facturing to improve oil recovery. Sani-
tary and domestic wastes originate from toilets, showers, etc. Produced
sands consist of slurried particles from hydraulic fracturing and the
accumulated formation sands generated during production.
PARAMETERS OF CONCERN
Oil/Grease
Fecal Coliforms
Floating solids
Chlorine residual
BOD
TOC
Heavy metals (arsenic,
chromium, copper, lead
nickel, silver and zinc)
TDS
Chlorides
Oxygen demand
Phenolics
Toxicants
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197
Major pollutants expected in oil and gas extraction industry wastewaters
include oil and grease, residual chlorine, and floating solids. Water
insoluble hydrocarbons and free floating and emulsified oils in the
wastewaters can affect aquatic flora and fauna by interfering with
oxygen transfer, coating bottom life and food, damaging the plumage of
water fowl and animals, and causing taste and toxicity problems. Resi-
dual chlorine is important in controlling fecal coliform bacteria in
sanitary wastes from offshore and onshore facilities. Floating solids
derive in most part from domestic and sanitary wastes. Pollutants
may settle or float, and can lead to objectionable odors.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
For Subcategories A and B, Offshore Facilities. Oil and gas extraction
facilities in the offshore subcategories have the option of piping
their wastes to onshore treatment facilities. This method could be
preferra-ble to treatment at the offshore works.
Subcategories A and B, Offshore Facilities, Both Existing and New
Sources:
Oil /Grease
Waste Source
Produced water
Deck drainage
Drilling muds
Drill cuttings
Well treatment
Produced sand
Sanitary wastes*
Domestic wastes*
Avg. 30 Day
(mg/1)
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No limitations
No limitations
Max. Day
(mg/1)
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No waste
discharge
No limita-
tions
No limita-
tions
Residual Chlorine
Max. Day
(mg/1)
No waste discharge
No waste discharge
No waste discharge
No waste discharge
No waste discharge
No waste discharge
No limitations
No limitations
* There shall be no float-ing solids as a result of discharge of these
wastes.
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For Subcategories C, D, E, F, Onshore Facilities. Limitations have
been proposed only for New Sources as shown below:
BOD - No limitations
TSS - No limitations
pH - No limitations
Oil/Grease 100 mg/1
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199
MINERAL MINING AND PROCESSING INDUSTRY
(67, 68, 69, 70, 71, 72)
[Part 436]
SUBCATEGORIZATION OF THE INDUSTRY
The Mineral Mining and Processing Industry has been divied into 38
discrete Subcategories which are described below. Differences in raw
materials, processing, and the use of wet air pollution control devices
have largely determined subcategorization. Effluent limitations have
been developed to date for 21 of the 38 Subcategories.
A - Dimension Stone (Reserved)
B - Crushed Stone
C - Construction Sand and Gravel
D - Industrial Sand
E - Gypsum
F - Asphaltic Minerals
G - Asbestos and Wollastonite
H - Lightweight Aggregates (Reserved)
I - Mica and Sericite (Reserved)
J - Barite
K - Fluorospar
L - Salines from Brine Lakes
M - Borax
N - Potash
0 - Sodium Sulfate
P - Trona (Reserved)
Q - Rock Salt (Reserved)
R - Phosphate Rock
S - Frasch Sulfur
T - Mineral Pigments (Reserved)
U - Lithium (Reserved)
V - Bentonite
W - Magnesite
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X - Datqmite
Y - Jade
Z - Novaculite
AA - Fire Clay (Reserved)
AB - Attapulgite and Montmorillonite (Reserved)
AC - Kyanite (Reserved)
AD - Shale and Common Clay (Reserved)
AE - Aplite (Reserved)
AF - Tripoli
AG - Kaolin (Reserved)
AH - Ball Clay (Reserved)
AI - Feldspar (Reserved)
AJ - Talc, Steatite, Soapstone and Pyrophyllite (Reserved)
AK - Garnet (Reserved)
AL - Graphite
NATURE OF THE PROBLEM
More than 11,000 establishments have been identified as included within
the Mineral Mining and Process Industry in the U.S. The large majority
of these plants are contained within the Crushed Stone and Construction
Sand and Gravel Subcategories (i.e., Subcategories B and C).
At the mine, sources of waste pollutants include surface runoff of rain-
water into the mine and mine water treatment systems, ground water seep-
age and infiltration into the mine, and water used to transport the ore
to the processing plant.
At the process plant, sources of waste include transport water, ore and
product wash water, dust suppression water, classification water, heavy
media separation water, flotation water, solution water, air emissions
control equipment water, and equipment and floor washdown water.
BPCTCA regulations for many of the mineral mining and process subcat-
egories specify that no discharge conditions are to be achieved at
least for the process water originating from the process plant. Ex-
emptions could be allowed during times of extreme runoff.
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PARAMETERS OF CONCERN
pH, acidity, alkalinity Asbestos
TSS BOD
Iron Oil and Grease
IDS Phosphates
Sulfide Ra-226 (Phosphate Rock Subcategory)
Turbidity Chlorides
Sulfate Possibility of trace constituents
(including antimony, arsenic, barium,
Fluoride boron, cadmium, chromium, copper, cyanide,
mercury, nickel, manganese, lead, selenium,
Temperature tin and zinc)
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
For Pretreatment of Existing Sources in the Mineral Mining and Processing
Industry and subsequent waste discharge to POTW's, the Federal Register
has declared that these process wastes are generally amenable to munici-
pal treatment and there is little or no requirement for pretreatment.
However, the operator of a POTW is cautioned that some of the consti-
tuents of the process waste waters may interfere with the treatment
works or pass through the treatment works inadequately treated. These
process wastes may warrant special consideration by the POTW and could
be the subject of future regulations.
For Pretreatment of New Sources in the Mineral Mining and Processing
Industry and subsequent discharge to POTW's, regulations are the same
as for existing sources above with apparent change only in Subcategory D,
Industrial Sand, and in Subcategory AL, Graphite as shown below.
Limitations for Subcategory D, Industrial Sand Production:
Avg. 30 Day Max. Day
Parameter (lb/1,000 Ib product) (lb/1,000 Ib product)
Total fluoride 0.003 0.006
Limitations for Subcategory AL, Graphite Production:
Parameter Pretreatment Standard
Dissolved Iron 50 mg/1
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The EPA Development Documents of October 1975 and June 1976 for the
Mineral Mining and Processing Industry recommend the following pretreat-
ment measures:
1) No pretreatment necessary for compatible pollutants.
2) Pollutants such as COD, TOC, phosphorous and phosphorous compounds,
nitrogen and nitrogen compounds, and oils and greases do not re-
quire removal provided the POTW is designed to remove these pollu-
tants and will accept them. Otherwise, pretreatment for Existing
Sources should be set at the BPCTCA levels, and pretreatment for
New Sources should be established at New Source Performance
Standards levels. Incompatible pollutants and suspended materials
laden with hazardous pollutants are subject to these same limi-
tations.
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PHARMACEUTICAL MANUFACTURING
(1, 126, 163)
[Part 439]
SUBCATEGORIZATION OF THE INDUSTRY
The Pharmaceuticals Manufacturing Industry has been divided into five
subcategories as shown below:
A - Manufacture of Fermentation Products
B - Biological and Natural Extraction Products C - Chemical
Synthesis Products D - Mixing/Compounding and Formulating E
Research Activities
NATURE OF PROBLEM
Available reports indicate that pollutants of special significance in
the pharmaceutical industry, in addition to BOD, COD, TOC and TSS
include mercury, cyanide, ammonia nitrogen, organic nitrogen and total
phosphorous.
Mercury salts are used to produce medicinal products and disinfectants.
Cyanides are primarily used as catalysts in chemical synthesis processes.
Mercury and cyanide can exert toxic impact upon biological treatment
works. High concentrations of organic and inorganic nitrogen have been
observed in raw waste waters of the pharmaceutical industry. High
total phosphorous concentrations are apparent in the raw wastes from
some fermentation and chemical synthesis product plants.
Waste waters from some chemical synthesis and fermentation operations
contain metals such as copper, nickel, mercury, cyanides, etc. together
with anti-bacterial constituents, which can seriously affect biological
treatment processes. A biological treatment works can be deactivated if
these pollutants are present in significant quantities. Equalization of
pretreated process wastes is likely necessary before release to a POTW.
PARAMETERS OF CONCERN
BOD TSS
COD pH
TOC Cyanides
Metals (Fe, Cu, Ni, Hg, Phenolics
Ag and others) Oil and Grease
Ammonia N Chlorinated hydrocarbons
Organia N TDS
Phosphates Bioassay (testing)
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LIMITATIONS FOR DISCHARGE
No specific limitations established! at, tins time.
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
Equalization is generally required for pharmaceutical process wastes.
Excess solvents in waste waters may be (partly) removed by gravity
separation and skimming. Neutralization may be required for waste
waters from specific pharmaceutical manufacturing. Odor controls are
also possible.
For Fermentation and Chemical Synthesis-Type Plants. Pretreatment
processes could consist of equalization, neutralization, solvent
separation, chemical precipatation for metals removal, and possible
cyanide oxidation.
For Extraction Product, Pharmaceutical Formulation and Research.-Type
Installations. Pretreatment could consist of waste equalization and
neutralization.
It is further noted for purposes of calculating Raw Waste Loads appli-
cable to NPDES discharges to receiving streams - the regulations specify
that separable mycelia and solvents shall be excluded from these raw
waste Toads. Removal, disposal and reuse practices include physical
separation and removal of separable mycelia, recovery of solvents from
waste streams, incineration of concentrated solvent waste streams
(including tar still bottoms), and fermentation broth concentrated and
disposed of in some acceptable manner other than to the treatment system.
Whereas these regulations do not preclude discharge of the above wastes
to a POTW, they do strongly suggest the described practices are the most
effective means of significantly reducing raw wastes whether to a POTW
or to an industrial treatment works.
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ORE MINING AND DRESSING INDUSTRY
(33, 34)
[Part 440]
SUBCATEGORIZATION OF THE INDUSTRY
The Ore Mining and Dressing Industry is divided into seven major sub-
categories based upon the particular metal ore produced or processed.
These seven subcategories have been further arrayed into 22 subdivi-
sions. The seven subcategories are described as follows:
A - Iron Ore Subcategory
B - Base and Precious Metals Subcategory
C - Bauxite Ore Subcategory
D - Ferroalloy Ores Subcategory
E - Uranium, Radium and Vanadium Subcategory
F - Mercury Ore Subcategory
G - Titanium Ore Subcategory
Subcategory A, Iron Ore. Includes: 1) mines producing iron ore re-
gardless of the type of or mode of occurrence; 2) mills beneficiating
iron ores by physical and chemical separation or by physical means only;
and 3) mills beneficiating iron ores by magnetic and physical separation.
Subcategory B, Base and Precious Metals. Includes: 1) mines producing
copper bearing ores, lead ores, zinc ores, gold ores or silver bearing
ores; 2) mills which employ the froth-flotation process for treating
the above ores; 3) mines/mills which employ dump, heap, in-situ leach
or vat-leach processing for extracting copper from ores; 4) mills which
extract gold or copper by the cyanide process only; 5) mills which
extract gold or silver by the amalgamation process alone; and 6) mines/
mills beneficiating gold, silver, tin or platinum ores by gravity sep-
aration.
Subcategory C, Bauxite Ore. Applies to mines producing bauxite/aluminum
ores.
Subcategory D, Ferroalloy Ores. Includes: 1) mines producing at least
5,000 metric tons of ferroalloy ores annually; 2) mines/mills producing
less than 5,000 metric tons of ferroalloy ores yearly by methods other
than ore leaching; 3) mills producing at least 5,000 metric tons of
ferroalloy ores yearly by purely physical means; 4) mills producing at
least 5,000 metric tons of ferroalloy ores yearly by froth flotation;
and 5) mills processing ferroalloy ores by leaching and associated
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chemical beneficiation. Ferroalloy metals include: chromium, cobalt,
columbium, tantalum, manganese, molybdenum, nickel, tungsten and va-
nadium.
Subcategory E, Uranium, Radium Vanadium. Includes: 1) mines producing
uranium, radium and vanadium ores; and 2) mills using acid, alkaline
or combination leach processing for the extraction of uranium, radium
and vanadium values.
Subcategory F, Mercury Ores. Includes: 1) mines producing mercury ores;
and 2) mills beneficiating mercury ores by gravity separtion or froth-
flotation methods.
Subcategory G, Titanium Ores. Includes: 1) mines producing titanium
ores from lode deposits; 2) mills beneficiating titanium ores by elec-
trostatic methods, magnetic and physical methods, or flotation methods;
and 3) mines engaged in dredge mining of deposits containing rutile,
ilemite, leucoxene, monazite, zircon, and other heavy metals, together
with the milling procedures employed in conjunction with dredge mining.
NATURE OF PROBLEM
Major pollutants of ore mine drainage and mill process wastewaters
comprise a variety of common and heavy metals in the solubilized
form, suspended and dissolved solids, radionuclides, organic and in-
organic matter, and reagents used in the milling process.
Process wastes from ore mining and milling include ore transport waters,
ore and product washes, dust suppression waters, grinding and classifi-
cation wastes, heavy media separation waters, and equipment and floor
washes. Additional streams consist of boiler blowdown and contact and
non-contact cooling waters. Raw waste loadings from ore mining and
milling are unrelated, or only indirectly related to production quanti-
ties, and consequently, effluent limitations are expressed in terms of
concentration rather than units of production.
PARAMETERS OF CONCERN
pH, Acidity,
TSS
Oil/Grease
COD
Cyanide
Ammonia N
Aluminum
Antimony
Alkalinity
Iron
Lead
Manganese
Mercury
Molybdenum
Nickel
Vanadium
Zinc
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Arsenic Radionuclides, especially Ra-226
Beryllium Uranium
Cadmium Asbestos
Chromium Flotation reagents having
Copper potential toxicity
Fluorides
Other potential or probable parameters include:
Barium Carbonates
Boron Nitrate, Nitrite
Calcium Selenium
Magnesium Silicate
Potassium Tin
Strontium Zirconium
Sodium IDS
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED
TREATMENT MEASURES
The EPA Development Document of October 1975 and effluent limitations
guidelines consider TSS as an incompatible pollutant to a POTW when pre-
sent in high concentrations. Most wastewaters in this industry require
settling in order to reduce the TSS to a level of around 500 mg/1 where
they may be normally accepted by a POTW. Phosphorous and nitrogen com-
pounds and fats and greases are thought to be compatible with properly
designed and operated POTW's. Otherwise, these pollutants should be
pretreated to equivalent BPCTCA discharge levels. Hazardous pollutants
such as cyanides, chromates, heavy metals etc. which may interfere with
biological unit operations at POTW's would require pretreatment to
equivalent BPCTCA levels. Waste equalization was recommended by the
Development Document. Chemical treatment, settling and pH control might
also constitute required pretreatment ahead of the POTW.
The Federal Register of November 6, 1975 on Ore Mining and Dressing
wastes, although providing JTO_ specific limitations for Existing and
New plants in the industry, nevertheless indicated that certain pol-
lutants in process waste discharges may interfere with the POTW or
pass through the treatment works inadequately treated. Therefore,
these process waters should receive special consideration by the POTW,
and may be the subject of further regulations.
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PAVING AND ROOFING (TARS AND ASPHALT) MATERIALS INDUSTRY
(43, 44, .45)
[Part 443]
SUBCATEGORiZATION OF THE INDUSTRY
The Paving and Roofing Materials Industry is divided into four Sub-
categories which are described below:
A - Asphalt Emulsions
B - Asphalt Concrete
C - Asphalt Roofing
D - Linoleum and Printed Asphalt Felt
Subcategory A includes plants engaged in production of oxidized
asphalt for use in both roofing and paving material. Oxidizing
consists of blowing hot air through asphalt. The oxidized asphalt
is stored as paving asphalt or as roofing and paving emulsions.
Subcategory B includes plants producing asphalt concrete which is
asphalt mixed with crushed rock or gravel, and used for paving such
as blacktop.
Subcategory C includes plants producing roofing felts, impregnated
roofing felts, shingles, tar papers, impregnated siding* canal liners,
expansion joints, roofing cements, etc. The process consists of
saturating and coating an organic felt with asphalt. The coated felt
may be subsequently covered with crushed rock.
Subcategory D includes plants producing linoleum and printed asphalt
felt floor coverings. The process consists of painting or embossing
a design on a saturated felt backing.
NATURE OF THE PROBLEM
Approximately 5,100 plants have been identified in the paving and
roofing materials industry, most of which are contained in Subcategory
B, i.e. Asphalt Concrete.
Major Waste sources from paving and roofing materials plants include
various codling waters both contact and non-contact; plant area
runoff; concentrated slurries from air pollution control equipment;
product cooling waters which may contain the majority of pollutant
loads; dried paints and inks; and cleaning waters resulting from the
washdown of floor, equipment and work areas. Typical waste streams
from this industry contain organic and inorganic solids (predominately
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the latter), suspended and settleable matter, oils and greases principally
petroleum-derived, and some potentially harmful solvents. Suggestions
have been made that the potentially harmful nature of industry waste-
waters resulting from contact with asphalt, tars and similar materials
should possibly lead to zero discharge limitations across the industry.
PARAMETERS OF CONCERN
BOD IDS
COD or TOC Nitrogen
TSS Phosphorous
Oil/Grease Phenols
pH ' Heavy Metals
Temperature Turbidity
Suspended solids in paving and roofing plant wastewaters were found to
range from less than 10 mg/1 up to 35,000 mg/1. Generally, when carbon-
ate rocks are used as raw material by the plant, a higher level of TSS
occurs. A lower level occurs with igneous rock. Paving and roofing
plants have reported trace amounts of one or more of the following
metals in their effluents: cadmium, chromium, copper, iron, lead,
nickel, zinc and aluminum. Arsenic and cyanide can originate from
stone or rock used by the plants, or from other sources.
PRELIMINARY LIMITATIONS FOR DISCHARGE TO PQTW AND PRESCRIBED PRETREATMENT
MEASURES
The Development Document for Paving and Roofing indicates that waste-
water from asphalt concrete plants may contain large amounts of suspended
sand and gravel which can cause or contribute to sewer line obstruction.
The Federal Register regulations have established a maximum limit of
100 mg/1 oil/grease in the discharge from both existing and new paving
and roofing establishments entering municipal sewer systems. This
limitation is applicable to plants in all four subcategories of the
industry. No other pretreatment limitations have been developed to
date.
Depending upon specific pretreatment needs dictated mostly by Regional
and local authorities, paving and roofing materials plants should strongly
consider good in-plant controls and water recycle augmented by oil
skimming, primary settling, filtration and sludge handling and disposal.
Other pretreatment may also be necessary.
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PAINT FORMULATING
(35, 36, 37)
[Part 446]
SUBCATEGORIZATION OF THE INDUSTRY
The Paint Formulating Industry was described by the EPA Development
Document of February 1975 on Paints and Inks and by the Federal
Register of February 26, 1975 as consisting of two subcategories
including: A) Oil-Based Paints and B) Water-Based Paints. This was
subsequently modified by the Federal Register of July 28, 1975 which
gave Final Limitations for only a single Subcategory titled "Oil Base
Solvent Wash Paint." Solvent wash paints represent a subpart of the
original Oil-Base Paints Subcategory.
The industry produces paints, varnishes and lacquers, which consist of
film-forming binders (resins or drying oils) dissolved in volatile
solvents or dispersed in water. In addition, all paint and most lacquers
contain pigments and extenders (calcium carbonate, clays and silicates).
The industry also produces side products such as putty, caulking com-
pounds, sealants, paint and varnish removers and thinners. Al-based
paints include all of the above items that use oil as the major carrier.
Water-based paints include all of the above items that use water as the
major carrier vehicle.
NATURE OF PROBLEM
Approximately 1,630 plants are represented in the paint formulating
industry of which less than 200 are reported to be discharging to sur-
face receiving waters. The remainder either discharge to municipal
sewers or have no waste discharge. Sources of wastes are principally
cleaning and milling equipment, cleanup of product and raw material
spills and leaks from product transfer equipment. Treatment of paint
manufacturing wastes leads to accumulation of solid wastes and liquid
concentrates. Some of these concentrated materials may be hazardous
and require special handling and disposal. Landfill sites receiving
these hazardous wastes should be selected and maintained so as to prevent
horizontal and vertical migration of contaminants into ground water.
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PARAMETERS OF CONCERN
pH, acidity, alkalinity Chromium
BOD Boron
COD Cadmium
TSS Iron
Oil/Grease Titanium
Mercury Bactericides, fungicides
Lead Special additives
Copper Solvents
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTH AND PRESCRIBED PRETREATMENT
MEASURES
The Development Document of February 1975 reported that wastewater from
the manufacture of oil-base paints entering most municipal sewer systems
are fairly well controlled. The wastes from water-base paint formulators
have generally been accepted by municipalities and a majority of paint
plants are connected to municipal sewers. Metals in paint wastes
generally become part of the suspended solids. The organics in water-
base paint wastes are said to be relatively biodegradable.
Many paint plants discharging to municipal systems employ waste settling
as pretreatment. Physical-chemical methods may be used by other plants
to meet state and local pretreatment limitations. These methods may
consist of holding, chemical coagulation and settling.
The Federal Register of February 26, 1975 proposed zero discharge of
process wastes from new paint installations to the POTW unless the
municipality can guarantee removal of incompatible pollutants. The
Federal Register of July 28, 1975 gave Final limitations for only the
specialized oil-base solvent wash paint plants. It indicated for both
existing and new sources that there shall be np_ discharge of process
water pollutants to the POTW. Final pretreatment limitations for other
types of paint plants await future publication.
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INK FORMULATING
(35, 38, 39)
[Part 447]
SUBCATEGORIZATION OF THE INDUSTRY
The Ink Formulating Industry is divided into Oil-Base and Water-Base
inks as described in the EPA Development Document of February 1975.
Accordingly, the Federal Register of February 26, 1975 divided the
industry into two proposed subcategories of A) Oil-Based Inks; and
B) Water-Based Inks. This was subsequently modified by the Federal
Register of July 28, 1975 which gave Final Limitations for a single
subcategory titled "Oil Base Solvent Wash Ink." Solvent wash plants
represent a subpart of the original Oil-Base Inks Subcategory.
The industry produces oil and water-base printing inks. The major
components include drying oils, resins, varnish, pigments and many
specialty additives. Oil-base inks use oil or solvent as the major
carrier. Water-base inks use water as the major carrier vehicle.
NATURE OF PROBLEM
Less than 50 ink formulating plants discharge wastewater to surface
receiving streams. The number of ink plants discharging to POTW's
are thought to be far greater. A significant number of establishments
are believed to approach zero discharge of process wastes. Sources
of wastes are principally cleaning and milling equipment, cleanup of
product and raw material spills, and leaks from product transfer equip-
ment. Treatment of paint manufacturing wastes leads to accumulation
of solid wastes and liquid concentrates. Some of these concentrated
materials may be hazardous and require special handling and disposal.
Landfill sites receiving these hazardous wastes should be selected
and maintained in such a manner as to prevent horizontal and vertical
migration of contaminants into ground water.
PARAMETERS OF CONCERN
pH, acidity, alkalinity Chromium
BOD Boron
COD Cadmium
TSS Iron
Oil/Grease Titanium
Mercury Bactericides, fungicides
Lead Special additives
Copper Solvents
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PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW AND PRESCRIBED TREATMENT
MEASURES
The Development Document of February 1975 reported that wastewater from
the manufacture of oil-base inks entering most municipal sewer systems
are controlled in reasonable degree. The wastes from water-base ink
formulators have generally been accepted by municipalities and the
large majority of ink plants are connected to municipal sewers. Metals
in ink wastes generally become part of the suspended solids. The
organics in water-base ink wastes are said to be relatively biodegradable.
Many ink plants discharging to municipal systems employ waste settling
as pretreatment. Physical-chemical methods may be used by other plants
to meet state and local pretreatment limitations. These methods may
consist of holding, chemical coagulation and settling.
The Federal Register of February 26, 1975 proposed zero discharge of
process wastes from new ink formulating plants to the POTW unless the
municipality can guarantee removal of incompatible pollutants. The
Federal Register of July 28, 1975 gave Final Limitations for only the
specialized oil base solvent wash ink plants. It indicated for both
existing and new sources that there shall be ru3 discharge of process
waste pollutants to the POTW. Final pretreatment limitations for other
types of ink plants await future publication.
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GUM AND WOOD CHEMICALS MANUFACTURING
(6, 193)
[Part 454]
SUBCATEGORIZATION OF THE INDUSTRY
Six types of manufacturing plants have been defined as shown below:
A - Char and charcoal briquets
B - Gum rosin and turpentine
C - Wood rosin, turpentine and pine oil
D - Tall oil rosin, pitch and fatty acids
E - Essential oils
F - Rosin based derivatives
NATURE OF PROBLEM
Waste sources in the gum and wood chemicals manufacturing industry
include watery wastes from reactors, filtration systems, decanting
systems, distillation vacuum exhaust scrubbers, caustic scrubbers,
process equipment cleaning, production area washdowns, refinery area
washdowns, formulation equipment cleanups, and washdowns of spills.
Gum and wood chemicals wastewaters may be characterized as having
high concentrations of soluble oxygen-demanding materials, are generally
acidic and deficient in nitrogen and phosphorous. Significant levels of
zinc are noted in the effluents of plants within Subcategories B and F.
Appreciable oil and grease are seen in the discharges of plants in
Subcategories B, D and F. Separable oils should be removed from these
process streams by skimming prior to being received into municipal
sewers. Phenol is a significant waste parameter for installations in
Subcategory F and possibly those in Subcategory D.
Certain substances may be present in gum and wood chemical wastewaters
exerting inhibitory effects upon subsequent biological treatment. Because
of high soluble oxygen demand, gum and wood chemical wastes may require
increased oxygen transfer, solids handling and disposal capacity at the
POTW. Otherwise, the industrial plant may need to provide biological
pretreatment to supplement the POTW. In all cases the manufacturer
should provide sufficient waste equalization and neutraliza-tion to
minimize adverse impacts upon the POTW.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity Temperature
BOD Nitrogen compounds
COD ~ Phosphorous
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TOC Zinc
TSS Sulfates
IDS Phenols
Oil/Grease Pesticides
Toxicity
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW.
No specific limitations given to date.
PRECRIBED PRETREATMENT MEASURES OR EQUIVALENT
Pretreatment unit operations which may be necessary by gum and wood
chemicals manufacturing plants prior to discharge to a POTW include:
For Subcategory B, D, F Plants - Oil separation plus equalization
plus neutralization plus chemical precipitation (depending upon
metal content)
For Subcategory C, E Plants - Equalization plus neutralization.
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PESTICIDE CHEMICALS MANUFACTURING
(8, 123, 124, 125)
[Part 455]
SUBCATEGORIZATION OF THE INDUSTRY
Five types of pesticides manufacturing establishments have been defined
as shown below, Subcategory A-D Plants are involved in the direct manu-
facture of the active ingredient. Subcategory E comprises plants that
formulate, blend, and package pesticides.
A - Alogenated organics pesticides
B - Organo - phosphorous pesticides
C - Organo - nitrogen pesticides
D - Metallo - organic pesticides
E - Pesticide formulators and packagers
NATURE OF PROBLEM
Pesticides can affect the aquatic environment and water quality in many
ways. A number of pesticides will degrade very slowly and consequently,
are extremely persistent. Other pesticides will degrade rapidly, some
into products that are more toxic than the parent compound, and some to
harmless products. A significant number of pesticides have high poten-
tial for bioaccumulation and biomagnification in the food chain, thereby
posing a serious threat to many organisms, including man.
The chlorinated organic pesticides represent a large group of chemicals
having wide use, stability in the environment, toxicity to wildlife and
nontarget organisms, and adverse physiological effects upon humans.
This group of pesticides readily accumulates in aquatic organisms and
man. They are stored in fatty tissues and not readily metabolized.
The organo-phosphorous pesticides will more rapidly hydrolyze or break
down into less toxic compounds as compared to the halogenated compounds.
This group exhibits a wide range of toxicity, some having high mammilian
toxicity. Accumulation of these pesticides results in a dysfunction of
the cholinesterase of the nervous system when ingested in small amounts
over a long period of time.
The organo-nitrogen pesticides are generally less persistent in the
environment than the halogenated organic pesticides. This group has
a wide range of toxicity. The carbamates are especially toxic-to
mammals by acting on the nervous system in the same manner as the
organo-chlorine pesticides.
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Metallo-organic pesticides include the arsenicals, mercury compounds,
and those containing zinc, manganese, tin, cadmium, lead and other
metals. Toxicity of these compounds is highly variable. Arsenic is
notorious for its toxicity to humans. Mercuro-organic compounds are
significantly toxic and demonstrate biomagnification.
The organic pesticides cited above are notquately measured by the
conventional waste parameters of BOD, COD, TOC, etc. Pesticides are
frequently toxic to organisms utilized in the BOD analysis. Their
reponse to the COD and TOC tests is not well known. Levels of critical
pesticide pollution may in certain cases be below the detection limit
of available analytical methods.
PARAMETERS OF CONCERN
pH, Acidity,
Alkalinity Ammonia N
BOD TKN
COD Total phosphates
TOC/TOD Cyanide
TSS Sulfide
TDS Metals including Zinc, Copper,
Oil and Grease Arsenic, Manganese, Tin
Chlorides Cadmium, Chromium, Lead,
Phenols Mercury, Nickel
Pesticides*
Typical halogenated organic pesticides include: PCNB, Terrazole
Toxaphene, DCPA, Chlorothalonil, Chlorobenzilate, 2-4D, 2-4D-5T,
POP, Endrin, Heptachlor, MCPA, DDT. Typical organo-phosphorous
pesticides include: Coumaphos, Disolfoton, Azinphosmethyl,
Mathamidophos, Fensulfothion, Fenthio, Demeton, Methyl Dementon,
Monitor, Diazinon, Methyl Parathion, Ethyl Parathion, Dursban,
Crufornate, Eonnels Aspon, Rabon} Vapona.
Typical organo-nitrogen pesticides include: Benefin, Trifluralin,
Isopropalin, Oryzalin, Pipron, Tebuthurion, Atrazine, Metribuzin,
Benzazimide, Simazine, Propazine, Ametrynes Prometryne, Sinutryne,
Sumitol, Terbetryne, Prometone, Cybnazine, Dinoseb, Alachlor,
Propochlor, Bromacil, Diuron, Aldicarb.
Typical metallo-organic pesticides include: DSMA, MSMA, PMAS Copper
8 Quinolate, CMP, Zineb, Tricyclohexyltin Hydroxide, Triphenyltin
Hydroxide, Tributyltin Oxide, Maneb.
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The BOD test is reported as sensitive to toxic materials. Therefore,
if toxic materials are present in a pesticides manufacturing waste-
water, the BOD value could be erroneous. This situation can be remedied
by conducting a microorganism toxicity test, i.e., serially diluting the
wastewater sample until the BOD value attains a plateau indicating that
the waste is at a low enough concentration to no longer inhibit biologi-
cal activity.
LIMITATIONS FOR DISCHARGE TO POTVJ
No specific limitations established at this time.
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
Even though the EPA Effluent Guidelines Division study cites many
pesticide plants discharging to POTW's, no description is given in the
August 1976 Draft Development Document of pretreatment limitations
and controls before release of pesticide wastes to a POTW. Such
technology will presumably be delineated in future publications.
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EXPLOSIVES MANUFACTURING
(7, 194)
[Part 457]
SUBCATEGORIZATION OF THE INDUSTRY
Four types of explosives manufacturing plants have been identified as
shown below. It must be recognized however that the Federal Register,
Part 457, has so far only recognized plants in Subcategories A and C.
A - Production of explosives, e.g., dynamite, nitroglycerin, RDX,
HMX, TNT.
B - Production of propel 1 ants
C - Load, assemble and pack operations
D - Production of initiating compounds
NATURE OF PROBLEM
Of special significance is the problem of trace amounts of the explo-
sive products themselves. Explosives such as nitroglycerin, TNT, RDX
and HMX have high potential hazard, toxicity or inhibitory impact upon
biological life. Some investigators have shown nitroglycerin to be
amenable to biological treatment whereas others have had little success
with biological treatment.
Process wastewaters from explosives manufacturing contains high levels
of soluble oxygen-demanding materials, TSS, nitrates, sulfates, organic
nitrogen, carbon, trace metals and trace quantities of explosives.
Metals such as lead and mercury can be discharged in significant amounts
as to disrupt biological activity. Lead concentrations of 200 mg/1 have
been found in explosive wastes, which would require physical/chemical
precipitation as a pretreatment measure.
Trace explosives present in wastewaters being discharged to a POTW can
lead to serious problems for the POTW because of the toxicity and
hazardous nature of the industrial waste.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity Nitrogen compounds including
BOD TKN, ammonia, nitrates
COD Sulfates
TOC Lead
TSS Mercury
TDS Other metals
Oil/Grease Trace explosives
Color Toxicity
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220
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW.
Since oil/grease in high concentrations can be disruptive to POTW's
under certain circumstances, a pretreatment limit of 100 mg/1 oil and
grease has been established for both existing and new installations in
the explosives industry.
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
It is recommended that explosives manufacturing wastewaters be treated
on site. If municipal treatment is employed, pretreatment must remove
potentially hazardous explosives wastes.
Discharge of explosives manufacturing wastes to POTW's is not common.
High sulfates can disrupt a biological secondary treatment system
thereby requiring calcination as necessary pretreatment. Wastes high
in TNT may require activated carbon absorption prior to municipal sew-
erage to remove the dissolved explosives and its isomers together with
associated toxicity. High concentration of nitrocellulose suspended
solids are disruptive to biological systems, but can be economically
removed by centrifuging. Heavy metals concentrations potentially toxic
to microorganisms and the activated sludge process can be reduced by
physical/chemical pretreatment. Oil and grease can be reduced to 100
mg/1 or lower by skimming or equivalent means.
Pretreatment for minimizing toxicity and safety hazards with explosives
wastes, may consist of a minimum of waste equalization, chemical preci-
pitation of metallics, and neutralization.
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221
CARBON' BLACK MANUFACTURING
(213)
[Part 458]
SUBCATEGORIZATION OF THE INDUSTRY
The Carbon Black Industry has been divided into four subcategories which
are described below:
A - Carbon black furnace process.
B - Carbon black thermal process.
C - Carbon black channel process.
D - Carbon black lamp process.
NATURE OF THE PROBLEM
Wastewater sources from carbon black manufacturing include scrubber
waters, process equipment cleanouts, production area washdowns, spill
washdowns, and laundry operations.
Under best practicable control technology, carbon black furnace and
thermal process plants (Subcategories A and B) are reported capable of
achieving no discharge of process wastewater pollutants by virtue of
recycling these wastes to the quench step. Channel and lamp black
process plants (Subcategories C and D) are reported to be dry opera-
tions also resulting in no discharge of process wastewater pollutants.
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity Iron
TSS Copper
TDS , Manganese
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTH AND PRESCRIBED
TREATMENT MEASURES
For Subcategory A, furnace process, New sources (Limitations for Existing
sources not yet defined).
Parameter Pretreatment Standards
BOD5, TSS No limitations
Oil/grease 100 mg/1
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222
For Subcategory B, thermal process, New sources (limitations for Existing
sources not yet defined).
Parameter Pretreatment Standard
BOD5, TSS No limitations
Oil/grease 100 mg/1
For Subcategory C, channel process, New sources (limitations for Existing
sources not yet defined).
BOD5, TSS No limitations
Oil/grease 100 mg/1
For Subcategory D, lamp process, New sources (limitations for Existing
sources not yet defined).
BOD5, TSS No limitations
Oil/grease 100 mg/1
In-process controls are important for minimizing waste loads from the
carbon black industry. Good practices include minimizing and containing
spills and leaks, segregating waste streams, water conservation and reuse,
wastewater equalization and good housekeeping, and process operation and
equipment maintenance.
New carbon black plants can minimize future waste abatement costs by
including:
1. dikes, emergency holding ponds, catch basins and other contain-
ment for leaks, spills and washdowns.
2. piping, trenches, sewers, sumps and other isolation facilities
to keep leaks, spills and process waters separated from cooling
and sanitary waters.
3. non-contact condensers for cooling waters.
4. efficient reuse, recycling and recovery of all possible raw
materials and byproducts.
5. closed cycle water utilization whenever possible.
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223
PHOTOGRAPHIC PROCESSING
(9, 164)
[PART 459]
SUBCATEGORIZATION OF THE INDUSTRY
The photographic processing industry was not subcategorized because the
pollutant loads per unit of production were found to fall in a relative-
ly narrow range. The photographic industry as presently defined by the
EPA does not include the manufacture of photographic film, photographic
plates and photographic paper.
NATURE OF PROBLEM
There are around 12,500 photographic processing plants in the U. S., of
which about 3,000 are amateur operations; 3,000 are "captive" labs
serving business and industrial firms; 650 are major labs specializing
in work for professional and industrial photographers; and the remaining
plants are portrait and commercial studios. Major sources of waste-
water in the photographic processing industry are photoprocessing
solution overflows and wash waters. It is estimated that 95 percent
of all photographic processing establishments after varying degrees of
in-plant pollution abatement discharge their effluents to municipal
sewarage. Certain pollutants such as silver and cyanide, which can
exert toxic effects upon POTW's together with non-biodegradable materials
may be contained in these releases. Therefore, in-plant measures or
pretreatment to reduce these contaminants to levels acceptable to local
authorities must be practiced. The yearly discharge of cyanide salts
from photographic sources has been estimated at over 5 million pounds.
Silver and ferrocyanide represent the prevalent incompatible pollutants.
The developer solutions, couplers and fixers become a problem if dumped
in a slug to the POTW. Discharge of these materials mostly occurs
during emergencies, periodic shutdowns, contamination, or exhaustion of
solutions. The most practical pretreatment of incompatible pollutants
involves regeneration and reuse of processing solutions. Both silver
and ferrocyanide can be recovered and reused. To prevent shock loads
to the municipal system, waste equalization and/or holding is advised.
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224
PARAMETERS OF CONCERN
pH, Acidity, Alkalinity Boron
BOD/COD/TOC Cadmium
TSS Chromium
Phenols Cyanide
IDS Ferrocyanide
Phosphorous , Silver
Nitrogen Compounds Thiosulfate
Sulfates Temperature
Wastewaters generated by the photographic processing industry are
characterized as containing high concentrations of BOD, COD, TOC,
silver and cyani.de in various forms.
The Ferrocyanide ion in the photographic industry originates from the
bleach used in some color processes, i.e., ferrocyanide bleach. Ferro-
cyanide is one of the most objectionable pollutants from photographic
processing. The complexed ion is potentially harmful because it is
converted to free, highly-toxic CN in the presence of sunlight. It
degrades only slowly in POTW's. The ferro and ferrocyanide complexes
impose a distinct threat to the environment. Fortunately, methods to
recover or minimize these compounds are currently being employed by
the industry.
Silver is a prevalent heavy metal in photographic processing
wastewaters. It is mostly derived from either the fix or bleach-fix
bath overflow. At this stage, silver is usually in a soluble complex
form, e.g., silver thiosulfate, which is somewhat less toxic than ionic
silver. While silver itself is not considered to be toxic, many of its
salts are poisonous. Toxicity of silver to POTW's seems to be dependent
upon the free filver ion concentration.
PRELIMINARY LIMITATIONS FOR DICHARGE TO POTW
Existing sewer ordinances generally specify that cyanide discharges be
maintained in the range of 0.0 to 10.1 mg/1. Pretreatment standards for
New sources within the photographic processing industry are given below:
Pollutant 30 Day Avg. Limit Max. Day Limit
(lb/1000 ft2, product) (Ib/IQOO ft2 product)
Silver .00034 .00067
Total Cyanide .00170 .00340
pH 6 to 9
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225
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
Besides in-plant controls, pretreatment for New sources would include
cyanide destruction, dual-media filtration and ion exchange.
General pretreatment unit operations which may be necessary by
photographic processing plants prior to discharge to a suspended growth
biological system, a fixed growth biological system, or to a physical -
chemical system of a municipal POTW would consist of equalization, .
physical methods and chemical precipitation plus solids separation.
The following in-plant controls are recommended:
1) Silver can be recovered by any of four available methods:
metallic replacement, electrolytic plating, ion exchange
and chemical precipitation.
2) Regeneration of ferrocyanide bleach can be accomplished by
oxidation with persulfate or ozone.
3) Developer solutions can be cleaned for reuse by ion exchange,
or precipitation and extraction.
4) Physical wastewater carryover between the process steps can
be reduced by mechanical means of using squeegees.
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226
HOSPITALS
(5, 195)
[Part 460]
NATURE OF PROBLEM
Approximately 92 percent of the more than 7,000 hospitals in the U.S.
discharge their effluents to municipal sewerage.
Sanitary wastes usually comprise a significant portion of total hospital
discharges. Major sources of wastes include patient rooms, laundries,
cafeterias, surgical suites, laboratories and X-ray departments. Be-
sides the usual waste parameters, hospital effluents may contain mercury,
silver, barium, beryllium, boron, and a wide range of solvents. Various
anti-bacterial constituents, e.g., disinfectants, may exert toxic im-
pacts upon subsequent biological waste treatment works. Radionuclides
can be released within patient excrement. One radioisotope having wide-
spread use is Iodine-131. The above-cited waste pollutants should be
recovered by in-house techniques in order to eliminate them from the
raw waste load. Radioactive wastes should be temporarily stored until
certified safe release to the environment is possible. Hospitals dis-
charging to municipal sewer facilities may expect additional pretreat-
ment standards in the future.
PARAMETERS OF CONCERN
Compatible Pollutants
BOD, TSS, pH and fecal coliform bacteria are defined as compatible
pollutants along with other pollutants which POTW's are designed to
remove.
Incompatible Pollutants
Silver, mercury and boron together with other parameters are considered
incompatible pollutants in hospital wastes and are subject to removal
by in-process modification or end-of-pipe treatment methods.
PH, Acidity, Alkalinity Ammonia N
BOD Barium
COD Beryllium
TOC Mercury
TSS Silver
TDS Radioactivity
Oil/grease Fecal Col iforms
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227
PRELIMINARY LIMITATIONS FOR DISCHARGE TO POTW
Pretreatment standards for New Sources specify a limit of 100 mg/1 oil
and grease in the discharges to a POTW.
IN-PLANT CONTROLS
The following in-plant controls are recommended methods of dealing with
hospital wastes:
1) X-ray units should utilize the boron-free fixer.
2) Stand-by controls should be installed on X-ray processing units
to decrease water consumption by the processer. Water flows should
be reduced to the maximum practicable extent consistent with obtain-
ing a good final radiograph.
3) Silver discharge from X-ray processing should be controlled by a
silver recovery system or return of the spent developer to the
manufacturer.
4) Hospital personnel should be acutely aware of mercury pollution
and disposal problems.
5) All radioactive waste should be contained and held pending safe
disposal.
PRESCRIBED PRETREATMENT MEASURES OR EQUIVALENT
Pretreatment unit operations which may be necessary by hospitals prior
to waste discharge to a suspended growth biological system, or fixed
growth biological system, or to a physical-chemical system of a muni-
cipal POTW are outlined below:
Suspended Growth Biological System: Chemical precipitation (for metals)
plus solids separation.
Fixed Growth Biological System: Chemical precipitation (for metals)
plus solids separation.
Physical-Chemical System: Chemical precipitation (for metals) plus
solids separation and oil and grease skimming.
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REFERENCES
1. "Development Document for Interim Final Effluent Limitations
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4. "Supplemental for Pretreatment to the Development Document for the
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-------
10. "Development Document for Interim Final and Proposed Effluent
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-------
21. 40 CFR Part 413, 40 FR 18130-18148, Apr. 24, 1975.
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-------
38. 40 CFR Part 447, Proposed Rules, 40 FR 8307, Feb. 26, 1975.
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48. 40 CFR Part 415, Proposed Rules, 36 FR 28174-28194, Oct. 11, 1973.
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51. 40 CFR Part 415, Proposed Rules, 40 FR 22402-22445, May 22, 1975.
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-------
55. 40 CFR Part 409, Interim Final and Proposed Rules, 40 FR 8498-85:11,
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63. 40 CFR Part 414, Proposed Rules, 38 FR 34706-34716, Dec. 17, 1973.
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69. "Development Document for Interim Final Effluent Limitations Guide-
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84. "Development Document for Proposed Effluent Limitations Guidelines
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85. 40 CFR Part 427, 39 FR 7526-7535, Feb. 26, 1974.
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99. 40 CFR Part 406, Proposed Rules, 38 FR 33438-33445, Dec. 4, 1973.
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105. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed New Source Performance Standards for the Fish
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and Abalone Segment of the Canned and Preserved Seafood Processing
Point Source Category," Effluent Guidelines Division, USEPA, January
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106. 40 CFR Part 408, 39 FR 23134-23156, June 26, 1974.
107. 40 CFR Part 408, 40 FR 55770-55801, Dec. 1, 1975.
108. "Development Document for Proposed Effluent Limitations Guidelines
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109. "Development Document for Proposed Effluent Limitations Guidelines
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Rubber Segment of the Rubber Processing Point Source Category,"
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110. 40 CFR Part 428, Proposed Rules, FR 28219-28228, Oct. 11, 1973.
111. 40 CFR Part 428, 39 FR 6660-6667, Feb. 21, 1974.
112. 40 CFR Part 428, 39 FR 30632-30645, Aug. 23, 1974.
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Jan. 10, 1975.
114. "Development Document for Proposed Effluent Limitations Guidelines
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and Wood Preserving Segment of the Timber Products Processing Point
Source Category," Effluent Guidelines Division, USEPA, December,
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115. "Development Document for Proposed Effluent Limitations Guidelines
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Particleboard, and Insulation Board Segment of the Timber Products
Processing Point Source Category," Effluent Guidelines Division,
USEPA, August 1974.
116. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Wood Furniture and
Fixture Manufacturing Segment of the Timber Products Processing
Point Source Category," Effluent Guidelines Division, USEPA, November
1974.
117. 40 CFR Part 429, Proposed Rules, 39 FR 938-949, Jan. 3, 1974.
118. 40 CFR Part 429, 39 FR 13942-13954, April 18, 1974.
119. 40 CFR Part'429, Proposed Rules, FR 30892-30903, Aug. 26, 1974.
120. 40 CFR Part 429, 40 FR 2804-2810, Jan. 16, 1975.
121. 40 CFR Part 429, Proposed Rules, 39 FR 40236-40242, Nov. 14, 1974.
122. 40 CFR Part 429, 40 FR 23824-23830, June 2, 1975.
123. "Development Document for Interim Final Effluent Limitations Guide-
lines for the Pesticides Chemicals Manufacturing Point Source
Category," Effluent Guidelines Division, USEPA, November 1976.
124. 40 CFR Part 455, 41 FR 48088-48096, Nov. 1, 1976.
125. 40 CFR Part 455, 41 FR 54181, Dec. 13, 1976.
126. 40 CFR Part 439, 41 FR 50676-50686, Nov. 17, 1976.
127. 40 CFR Part 429, 41 FR 53930-53938, Dec. 9, 1976.
128. 40 CFR Part 421, 41 FR 54850-54854, Dec. 15, 1976.
129. 40 CFR Part 413, 41 FR 53018-53019 and 53070, Dec. 3, 1976.
130. 40 CFR Part 415, 41 FR 51598-51603 and 51621, Nov. 23, 1976.
131. 40 CFR Part 430, 42 FR 1398-1426, Jan. 6, 1977.
132. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Citrus, Apple and
Potato Segment of the Canned and Preserved Fruits and Vegetables
Processing Point Source Category," USEPA, Effluent Guidelines
Division, Washington, D.C., November 1973.
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133. 40 CFR Part 407, 39 FR 10862-10870, March 21, 1974.
134. 40 CFR Part 407, Interim Final and Proposed Rules, 40 FR 40222-49265,
October 21, 1975.
135. 40 CFR Part 407, 41 FR 16272-16286, April 16, 1976.
136. 40 CFR Part 410, 39 FR 30134-30135, August 21, 1974.
137. "Development Document for Interim Final Effluent Limitations Guide-
lines and New Source Performance Standards for the Offshore Segment
of the Oil and Gas Extraction Point Source Category," USEPA,
Effluent Guidelines Division, September, 1975.
138. 40 CFR Part 435, 40 FR 42543-42551 and 42572-42577, Sept. 15, 1975.
139. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed New Source Performance Standards for the Oil and
Gas Extraction Point Source Category," USEPA, Effluent Guidelines
Division, September 1976.
140. 40 CFR Part 435, Interim Final and Proposed Rules, 41 FR 44942-44952.
141. 40 CFR Part 430, 41 FR 27741-27744, July 6, 1976.
142. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Unbleached Kraft and
Semi-Chemical Pulp Segment of the Pulp, Paper, and Paperboard Mills
Point Source Category," USEPA, Effluent Guidelines Division, January
1974.
143. 40 CFR Part 430, Proposed Rules, 39 FR 1908-1916, Jan. 15, 1974.
144. 40 CFR Part 430, Proposed Rules, 39 FR 18742-18754, May 29, 1974.
145. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Bauxite Refining
Subcategory of the Aluminum Segment of the Non-Ferrous Metals
Manufacturing Point Source Category," USEPA, Effluent Guidelines
Division, October 1973.
146. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Primary Aluminum
Smelting Subcategory of the Aluminum Segment of the Non-Ferrous
Metals Manufacturing Point Source Category," USEPA, Effluent Guide-
lines Division, October 1973.
147. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Secondary Aluminum
Smelting Subcategory of the Aluminum Segment of the Non-Ferrous
Metals Manufacturing Point Source Category," USEPA, Effluent Guide-
lines Division, October 1973.
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148. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed New Source Performance Standards for the Primary
Copper Smelting Subcategory and the Primary Copper Refining Sub-
category of the Copper Segment of the Non-Ferrous Metals Manufactur-
ing Point Source Category," USEPA, Effluent Guidelines Division,
February 1975.
149. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed New Source Performance Standards for the Secondary
Copper Subcategory of the Copper Segment of the Non-Ferrous Metals
Manufacturing Point Source Category," USEPA, Effluent Guidelines
Division, February 1975.
150. "Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for the
Lead Segment of the Non-Ferrous Metals Manufacturing Point Source
Category," USEPA, Effluent Guidelines Division, February 1975.
151. "Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for the
Zinc Segment of the Non-Ferrous Metals Manufacturing Point Source
Category, USEPA, Effluent Guidelines Division, February 1975.
152. 40 CFR Part 421, Proposed Rules, 38 FR 33170-33183, Nov. 30, 1973.
153. 40 CFR Part 421, 39 FR 12822-12830, April 8, 1974.
154. 40 CFR Part 421, 40 FR 8514-8535, Feb. 27, 1975.
155. 40 CFR Part 421, 40 FR 24539-24540, June 9, 1975.
156. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Synthetic Resins
Segment of the Plastics and Synthetic Materials Manufacturing Point
Source Category," USEPA, Effluent Guidelines Division, August 1973.
157. "Addendum to Development Document for Proposed Effluent Limitations
Guidelines and Mew Source Performance Standards for the Synthetic
Resins Segment of the Plastics and Synthetics Materials Manufactur-
ing Point Source Category," USEPA, Effluent Guidelines Division,
September 1974.
158. "Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Synthetic Polymers Segment of
the Plastics and Synthetic Materials Manufacturing Point Source
Category," USEPA, Effluent Guidelines Division, January 1975.
159. 40 CFR Part 416, 39 FR 12502-12525, April 5, 1974.
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160. 40 CFR Part 416, Final and Proposed Rules, 40 FR 3718-3732, Jan. 23,
1975.
161. 40 CFR Part 416, Final and Proposed Rules 40 FR 21731-21732 and
1740-21741, May 19, 1975.
162. 40 CFR Part 416, 41 FR 32587-32589 and 32613, Aug. 4, 1976.
163. 40 CFR Part 439, 42 FR 6813-6814, FEb. 4, 1977.
164. 40 CFR Part 459, 41 FR 29078-29082, July 14, 1976.
165. 40 CFR Part 424, Proposed Rules, 38 FR 29008-29018, Oct. 18, 1973.
166. 40 CFR Part 424, 39 FR 6806-6814, Feb. 22, 1974.
167. 40 CFR Part 424, Interim Final and Proposed Rules 40 FR 8030-8041,
Feb. 4, 1975..
168. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Smelting and Slag
Processing Segment of the Ferroalloy Manufacturing Point Source
Category," USEPA, Effluent Guidelines Division, August 1973.
169. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed New Source Performance Standards for the Calcium
Carbide Segment of the Ferroalloy Manufacturing Point Source Category,"
USEPA, Effluent Guidelines Division, February 1975.
170. "Development Document for Interim Final Effluent Limitations Guide-
lines and Proposed Mew Source Performance Standards for the Electro-
lytic Ferroalloys Segment of the Ferroalloy Manufacturing Point
Source Category," USEPA, Effluent Guidelines Division, February
1975.
171. 40 CFR Part 432, Proposed Rules 39 FR 31486-31497, Aug. 28, 1974.
172. 40 CFR Part 432, Proposed Rules 38 FR 29858-29868, Oct. 29, 1973.
173. 40 CFR Part 432, 39 FR 7894-7908, Feb. 28, 1974.
174. 40 CFR Part 432, Proposed Rules 40 FR 902-914, Jan. 3, 1975.
175. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Red Meat Processing
Segment of the Meat Product and Rendering Processing Point Source
Category," USEPA, Effluent Guidelines Division, October 1973.
176. 40 CFR Part 422, Proposed Rules, 39 FR 24470-24476, Sept. 7, 1973,
177. 40 CFR Part 422, 39 FR 6580-6588, FEb. 20, 1974.
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178. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Phosphorous Derived
Chemicals Segment of the Phosphate Manufacturing Point Source
Category," USEPA, Effluent Guidelines Division, August 1973.
179. 40 CFR, Part 422, Interim Final and Proposed Rules, 40 FR 4102-4113,
Jan. 27, .1975.
180. 40 CFR Part 422, 41 FR 25974-25979, June 23, 1976.
181. "Development Document for Interim Final Effluent Limitations Guide-
. lines and Proposed New Source Performance Standards for the Other
Non-Fertilizer Phosphate Chemicals Segment of the Phosphate Manufactur-
ing Point Source Category," USEPA, Effluent Guidelines Division,
January 1975.
182. 40 CFR Part 418, 39 FR 12832-12844, April 8, 1974.
183. 40 CFR Part 418, 40 FR 2650-2655, Jan. 14, 1975.
184. 40 CFR Part 418, 40 FR 26275, June 23, 1975.
185. 40 CFR Part 418, Proposed Rules, 40 FR 33052-33054, Aug. 6, 1975.
186. 40 CFR Part 418, 41 FR 20582-20585, May 19, 1976.
187. 40 CFR Part 418, 40 FR 36337-36339, Aug. 20, 1975.
188. 40 CFR Part 418, Proposed Rules, 41 FR 29429-29432, July 16, 1976.
189. 40 CFR Part 418, 41 FR 2386-2388, Jan. 16, 1976.
190. 40 CFR Part 418, Proposed Rules, FR 33852-33860, Dec. 7, 1973.
191. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Formulated Fertilizer
Segment of the Fertilizer Manufacturing Point Source Category,"
USEPA, Effluent Guidelines Division, September 1974.
192. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Basic Fertilizer
Chemicals Segment of the Fertilizer Manufacturing Point Source
Category," USEPA, Effluent Guidelines Division.
193. 40 CFR Part 454, 41 FR 20506-20519, May 18, 1976.
194. 40 CFR Part 457, 41 FR 10180-10188, March 9, 1976.
195. 40 CFR Part 460, 41 FR 18779-18780, May 6, 1976.
196. 40 CFR Part 418, 42 FR 16140-16141, March 25, 1977.
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197. 40 CFR Part 419, 42 FR 15684-15690, March 23, 1977.
198. 40 CFR Part 419, 40 FR 21939-21954, May 20, 1975.
199. 40 CFR Part 419, 39 FR 16560-16575, May 9, 1975.
200. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Petroleum Refining
Point Source Category," USEPA, Effluent Guidelines Division,
Washington, D.C., December 1973.
201. 40 CFR Part 423, 39 FR 36186-36211, Oct. 8, 1974.
202. 40 CFR Part 423, Proposed Rules, 39 FR 8294-8307, March 4, 1974.
203. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Steam Electric Power
Generating Point Source Category," USEPA, Effluent Guidelines
Division, March 1974.
204. "Supplement for Pretreatment to the Development Document for the
Steam Electric Power Generating Point Source Category," USEPA,
Effluent Guidelines Division, November 1976.
205. 40 CFR Part 423, 42 FR 15690-15696, March 23, 1977.
206. 40 CFR Part 420, 41 FR 12990-13030, March 29, 1976.
207. 40 CFR Part 420, Interim Final and Proposed Rules, 41 FR 2218-
32219 and 32242, Aug. 2, 1976.
208. 40 CFR Part 420, 39 FR 24114-24133, June 28, 1974.
209. 40 CFR Part 420, 39 FR 6484-6505, Feb. 19, 1974.
210. "Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Steel Making Segment
of the Iron and Steel Manufacturing Point Source Category," USEPA,
Effluent Guidelines Division, February 1974.
211. 40 CFR Part 425, 42 FR 15696-15704, March-23,- 1977.
212. "Supplement for Pretreatment to the Development Document for the
Leather Tanning and Finishing Point Source .Category," USEPA, Effluent
Guidelines Division, November 1976.
213. 40 CFR Part 458, 41 FR 20496-20504, May 18, 1976.
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