EPA-600/8-80-042b
TREATABILITY MANUAL
VOLUME II. Industrial Descriptions
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
a^tora
60804
July 1980
-all' l)\ th<> .Sll[»'I!lltl"l'!( lit lit Pi.I ll!!i"'..» < .. i 11,11 ".I I'llll'll .
\V;islilni.'tiMi, 1> (' :^U4()^
-------
PREFACE
In January, 1979, EPA's Office of Enforcement and Office of
Water and Waste Management requested help from the Office of
Research and Development in compiling wastwater treatment per-
formance data into a "Treatability Manual". This Manual was to
be used in developing NPDES permit limitations for facilities
which, at the time of permit issuance, were not fully covered
by promulgated, industry-specific effluent guidelines authorized
under Sections 301, 304, 306, 307, and 501 of the CWA.
A planning group was set up to manage the treatability program
under the chairmanship of William Cawley, Deputy Director,
Industrial Environmental Research Laboratory - Cincinnati. The
group includes participants from: 1) the Industrial Environmen-
tal Research Laboratory - Cincinnati, 2) Effluent Guidelines
Division, Office of Water and Waste Management; 3) Permits
Division, Office of Enforcement; 4) Municipal Environmental
Research Laboratory - Cincinnati; 5) R. S. Kerr, Environmental
Research Laboratory - Ada; 6) Industrial Environmental Research
Laboratory - Research Triangle Park; 7) Monsanto Research Corpo-
ration; and 8) Aerospace Corporation.
The objectives of the treatability program are:
• To provide readily accessible data and information on
treatability of industrial and municipal waste streams
for use by NPDES permit writers, enforcement personnel,
and by industrial or municipal permit holders;
• To provide a basis for research planning by identifying
gaps in knowledge of the treatability of certain pollut-
ants and wastestreams;
• To set up a system allowing rapid response to program
office requirements for generation of treatability data.
The primary output from this program is a five-volume Treat-
ability Manual. The individual volumes are named as follows:
Volume I
Volume II
Volume III
Volume IV
Volume V
Treatability Data
Industrial Descriptions
Technologies
Cost Estimating
Summary
6/23/so
11
-------
ACKNOWLEDGEMENT
The sheer size and comprehensiveness of this document should make it
obvious that this had to be the effort of a large number of people. It
is the collection of contributions from throughout the Environmental
Protection Agency, particularly from the Office of Enforcement, Office of
Water and Hazardous Materials and the Office of Research and Development.
Equally important to its success were the efforts of the employees of the
Aerospace Corporation, MATHTECH, INC., and the Monsanto Research Corporation
who participated in this operation.
No list of the names of everyone who took part in the effort would in
any way adequately acknowledge the effort which those involved in preparing
this Manual made toward its development. Equally difficult would be an
attempt to name the people who have made the most significant contributions
both because there have been too many and because it would be impossible to
adequately define the term "significant." This document exists because of
major contributions by the contractor's staff and by members of the following:
Effluent Guidelines Division
Office of Water and Waste Management
Permits Division
Office of Water Enforcement
National Enforcement Investigation Center
Office of Enforcement
Center for Environmental Research Information
Municipal Environmental Research Laboratory
Robert S. Kerr Environmental Research Laboratory
Industrial Environmental Research Laboratory
Research Triangle Park, NC
Industrial Environmental Research Laboratory
Cincinnati, OH
Office of Research and Development
The purpose of this acknowledgement is to express my thanks as Committee
Chairman and the thanks of the Agency to the Committee Members and others who
contributed to the success of this effort.
William A. CSwley, Deputy Director, IERi-Ci
Chairman, Treatability Coordination Committee
iii
-------
TABLE OF CONTENTS
Page
II.I Introduction II.1-1
11.2 Auto and Other Laundries 11.2-1
11.2.1 Industry Description 11.2-1
11.2.1.1 General Description 11.2-1
II.2.1.2 Subcategory Descriptions II.2-4
II.2.2 Wastewater Characterization II.2-8
11.2.3 Plant Specific Description 11.2-20
11.2.4 Pollutant Removability 11.2-26
11.3 Coal Mining 11.3-1
11.3.1 Industry Description 11.3-1
11.3.1.1 General Description 11.3-1
II.3.1.2 Subcategory Descriptions II.3-3
II.3.2 Wastewater Characterization II.3-6
11.3.3 Plant Specific Description 11.3-8
11.3.4 Pollutant Removability 11.3-8
II.4 Electroplating II.4-1
11.4.1 Industry Description 11.4-1
11.4.1.1 General Description 11.4-1
II.4.1.2 Subcategory Descriptions II.4-2
II.4.2 Wastewater Characterization II.4-20
11.4.3 Plant Specific Description 11.4-24
11.4.4 Pollutant Removability 11.4-24
11.5 Inorganic Chemicals Manufacturing 11.5.1-1
11.5.1 Industry Description 11.5.1-1
11. 5.1.1 General Description 11.5.1-1
II.5.1.2 Subcategory Descriptions II.5.1-1
II.5.2 Wastewater Characterization II.5.2-1
11. 5. 3 Plant Specific Description 11. 5.3-1
11.5.4 Pollutant Removability 11. 5.4-1
II.6 Iron and Steel Manufacturing II.6.1-1
11. 6.1 Industry Description 11.6.1-1
11.6.1.1 General Description 11.6.1-1
11.6.1.2 Subcategory Descriptions 11.6.1-2
II.6.2 Wastewater Characterization II.6.1-18
11.6.3 Plant Specific Description 11.6.1-62
II.6.4 Pollutant Removability II.6.1-106
Date: 6/23/80 V
-------
II.7 Leather Tanning and Finishing
11.7.1 Industry Description 11.7-1
11.7.1.1 General Description 11.7-1
II.7.1.2 Subcategory Descriptions II.7-2
II.7.2 Wastewater Characterization II.7-8
11.7.3 Plant Specific Description 11.7-17
II.7.4 Pollutant Removability II.7-17
II.8 Machinery and Mechanical Products
II.8.1 Aluminum Forming
II.8.1.1 Industry Description
11.8.1.1.1 General Description
11.8.1.1.2 Subcategory Descriptions
II.8.1.2 Wastewater Characterization
11.8.1.3 Plant Specific Description
II.8.1.4 Pollutant Removability
II.8.2 Battery Manufacturing
II.8.2.1 Industry Description
II.8.2.1.1 General Description
11.8.2.1.2 Subcategory Descriptions
II.8.2.2 Wastewater Characterization
II.8.2.3 Plant Specific Description
II.8.2.4 Pollutant Removability
II.8.3 Coil Coating II.8.3-1
II.8.3.1 Industry Description II.8.3-1
11.8.3.1.1 General Description 11.8.3-1
II.8.3.1.2 Subcategory Descriptions . . II.8.3-8
II.8.3.2 Wastewater Characterization II.8.3-10
II.8.3.3 Plant Specific Description . .'. . . II.8.3-20
II.8.3.4 Pollutant Removability II.8.3-22
II.8.4 Copper Forming
II.8.4.1 Industry Description
II.8.4.1.1 General Description
II.8.4.1.2 Subcategory Descriptions
II.8.4.2 Wastewater Characterization
II.8.4.3 Plant Specific Description
II.8.4.4 Pollutant Removability
II.8.5 Electrical and Electronic Components
II.8.5.1 Industry Description
II.8.5.1.1 General Description
11.8.5.1.2 Subcategory Descriptions
II.8.5.2 Wastewater Characterization
II.8.5.3 Plant Specific Description
II.8.5.4 Pollutant Removability
Date: 6/23/80 vi
-------
II.8.6 Foundries II.8.6-1
II.8.6.1 Industry Description II.8.6-1
II.8.6.1.1 General Description II.8.6-1
II.8.6.1.2 Subcategory Descriptions . . II.8.6.1-2
11.8.6.2 Wastewater Characterization 11.8.6-5
11.8.6.3 Plant Specific Description 11.8.6-20
II.8.6.4 Pollutant Removability II.8.6-34
II.8.7 Mechanical Products
II.8.7.1 Industry Description
II.8.7.1.1 General Description
II.8.7.1.2 Subcategory Descriptions
II.8.7.2 Wastewater Characterization
II.8.7.3 Plant Specific Description
II.8.7.4 Pollutant Removability
II.8.8 Photographic Equipment and Supplies
II.8.8.1 Industry Description
II.8.8.1.1 General Description
II.8.8.1.2 Subcategory Descriptions
II.8.8.2 Wastewater Characterization
II.8.8.3 Plant Specific Description
II.8.8.4 Pollutant Removability
II.8.9 Plastics Processing
II.8.9.1 Industry Description
II.8.9.1.1 General Description
II.8.9.1.2 Subcategory Descriptions
II.8.9.2 Wastewater Characterization
II.8.9.3 Plant Specific Description
11.8.9,4 Pollutant Removability
11.8.10 Porcelain Enameling 11.8.10-j.
11.8.10.1 Industry Description 11.8.10-1
11.8.10.1.1 General Description 11.8.10-1
II.8.10.1.2 Subcategory Descriptions . . II.8.10-3
II.8.10.2 Wastewater Characterization .... II.8.10-6
II.8.10.3 Plant Specific Description II.8.10-17
11.8.10.4 Pollutant Removability 11.8.10-19
II.9 Miscellaneous
II.9.1 Adhesives and Sealants
II.9.1.1 Industry Description
II.9.1.1.1 General Description
II.9.1.1.2 Subcategory Descriptions
II.9.1.2 Wastewater Characterization
II.9.1.3 Plant Specific Description
II.9.1.4 Pollutant Removability
Date: 6/23/80 vii
-------
Page
11.9.2 Explosives Manufacture 11.9.2-1
II.9.2.1 Industry Description II.9.2-1
11.9.2.1.1 General Description 11.9.2-1
II.9.2.1.2 Subcategory Descriptions . . II.9.2-3
11.9.2.2 Wastewater Characterization 11.9.2-8
II.9.2.3 Plant Specific Description II.9.2-11
II.9.2.4 Pollutant Removability II.9.2-11
II.9.3 Gum and Wood Chemicals
II.9.3.1 Industry Description
II.9.3.1.1 General Description
II.9.3.1.2 Subcategory Descriptions
II.9.3.2 Wastewater Characterization
11.9.3.3 Plant Specific Description
II.9.3.4 Pollutant Removability
II.9.4 Pesticide Manufacturing
II.9.4.1 Industry Description
II.9.4.1.1 General Description
II.9.4.1.2 Subcategory Descriptions
II.9.4.2 Wastewater Characterization
II.9.4.3 Plant Specific Description
II.9.4.4 Pollutant Removability
11.9.5 Pharmaceutical Manufacturing 11. 9.5-1
I I. 9. 5.1 Industry Description
I I. 9. 5. 1.1 General Description . . .
I I. 9. 5. 1.2 Subcategory Descriptions
I I. 9. 5. 2 Wastewater Characterization. . .
I I. 9. 5. 3 Plant Specific Description . . .
I I. 9. 5. 4 Pollutant Removability
11.10 Nonferrous Metals Manufacturing
I I. 10.1 Industry Description
I I. 10. 1.1 General Description. . . .
I I. 10. 1.2 Subcategory Descriptions .
1 1. 10. 2 Wastewater Characterization
I I. 10. 3 Plant Specific Description
I I. 10. 4 Pollutant Removability
11.11 Ore Mining and Dressing
I I. 11.1 Industry Description
I I. 11. 1.1 General Description. . . .
I I. 11. 1.2 Subcategory Descriptions .
I I. 11. 2 Wastewater Characterization
I I. 11. 3 Plant Specific Description
I I. 11. 4 Pollutant Removability
. . II. 9. 5-1
. . II. 9. 5-1
. . II. 9. 5-3
. . II. 9. 5-7
. . II. 9. 5-16
II. 9. 5-17
. . II. 10-1
. . II. 10-1
. . II. 10-1
. . II. 10-2
. . II. 10-7
. . 11.10-24
11.10-36
. . II. 11-1
. . II. 11-1
. . II. 11-1
. . II. 11-6
. . II. 11-7
. . 11.11-13
. . 11.11-13
Date: 6/23/80
-------
11.12 Organic Chemicals Manufacturing
II.12.1 Industry Description
II.12.1.1 General Description
II.12.1.2 Subcategory Descriptions
II.12.2 Wastewater Characterization
II.12.3 Plant Specific Description
II.12.4 Pollutant Removability
11.13 Paint and Ink Formulation 11.13-1
11.13.1 Industry Description 11.13-1
11.13.1.1 General Description 11.13-1
II.13.1.2 Subcategory Descriptions . . II.13-4
11.13.2 Wastewater Characterization 11.13-6
II.13.3 Plant Specific Description 11.13-15
11.13.4 Pollutant Removability 11.13-25
11.14 Petroleum Refining II.14-1
11.14.1 Industry Description 11.14-1
II.14.1.1 General Description II.14-1
11.14.1.2 Subcategory Descriptions . . 11.14-1
II.14.2 Wastewater Characterization II.14-4
11.14.3 Plant Specific Description 11.14-15
11.14.4 Pollutant Removability 11.14-19
11.15 Plastic and Synthetic Materials Manufacturing
II.15.1 Industry Description
II.15.1.1 General Description
11.15.1.2 Subcategory Descriptions
II.15.2 Wastewater Characterization
II.15.3 Plant Specific Description
II.15.4 Pollutant Removability
11.16 Pulp and Paperboard Mills and Converted
Products 11.16-1
11.16.1 Industry Description 11.16-1
11.16.1.1 General Description 11.16-1
11.16. ..2 Subcategory Descriptions . . . 11.16-2
11.16.2 Wastew iter Characterization 11.16-8
II.16.3 Plant •",>ecific Description 11.16-13
11.16.4 Pollutanc Removability 11.16-13
11.17 Rubber Processing II.17-1
II.17.1 Industry Description II.17-1
11.17.1.1 General Description 11.17-1
II.17.1.2 Subcategory Descriptions . . . II.17-3
II.17.2 Wastewater Characterization 11.17-10
II.17.3 Plant Specific Description 11.17-27
II.17.4 Pollutant Removability 11.17-31
Date: 6/23/80 ix
-------
11.18 Soap and Detergent Manufacturing 11.18-1
II.18.1 Industry Description II.18-1
11.18.1.1 General Description 11.18-1
II.18.1.2 Subcategory Descriptions . . . II.18-2
II.18.2 Wastewater Characterization 11.18-11
II.18.3 Plant Specific Description 11.18-16
II.18.4 Pollutant Removability 11.18-25
11.19 Steam Electric Power Plants II.19-1
II.19.1 Industry Description II.19-1
11.19.1.1 General Description 11.19-1
II.19.1.2 Subcategory Descriptions . . . II.19-2
II.19.2 Wastewater Characterization II.19-7
II.19.3 Plant Specific Description 11.19-26
II. 19.4 Pollutant Removability 11.19-38
11.20 Textile Mills II.20-1
11.20.1 Industry Description 11.20-1
11.20.1.1 General Description 11.20-1
11.20.1.2 Subcategory Descriptions . . . 11.20-2
II.20.2 Wastewater Characterization 11.20-10
II.20.3 Plant Specific Description 11.20-12
II.20.4 Pollutant Removability 11.20-28
11.21 Timber Products Processing 11.21-1
11.21.1 Industry Description 11.21-1
11.21.1.1 General Description 11.21-1
11.21.1.2 Subcategory Descriptions . . . 11.21-1
II.21.2 Wastewater Characterization II.21-7
II.21.3 Plant Specific Description 11.21-13
II.21.4 Pollutant Removability 11.21-16
11.22 Publicly Owned Treatment Works (POTW'S) II.22-1
11.22.1 Industry Description 11.22-1
II.22.1.1 General Description II.22-1
II.22.1.2 Subcategory Description. . . . 11.22-1
II. 22.2 Wastewater Characterization 11.22-1
11.22.3 Plant-Specific Descriptions 11.22-2
II.22.4 Pollutant Removability II.22-9
Date: 6/23/80
-------
GLOSSARY
AAP: Army Ammunitions Plant.
AN: Ammonium Nitrate.
ANFO: Ammonium Nitrate/Fuel Oil.
BATEA: Best Available Technology Economically Achievable.
BAT: Best Applicable Technology.
BDL: Below Detection Limit.
BEJ: Best Engineering Judgement.
,BOD: Biochemical Oxygen Demand.
clarification: Process by which a suspension is clarified to give
a "clear" supernatant.
cryolite: A mineral consisting of sodium-aluminum fluoride.
CWA: Clean Water Act.
cyanidation process: Gold and/or silver are extracted from finely
crushed ores, concentrates, tailings, and low-grade mine-run
rock in dilute, weakly alkaline solutions of potassium or
sodium cyanide.
comminutor: Mechanical devices that cut up material normally
removed in the screening process.
effluent: A waste product discharged from a process.
EGD: Effluent Guidelines Division.
elutriation: The process of washing and separating suspended
particles by decantation.
extraction: The process of separating the active constituents of
drugs by suitable methods.
fermentation: A chemical change of organic matter brought about
by the action of an enzyme or ferment.
6/23/80
XI
-------
flocculation: The coalescence of a finely-divided precipitate.
fumigant: A gaseous or readily volatilizable chemical used as a
disinfectant or pesticide.
GAC: Granular Activated Carbon.
gravity concentration: A process which uses the differences in
density to separate ore minerals from gangue.
gravity separation/settling: A process which removes suspended
solids by natural gravitational forces.
grit removal: Preliminary treatment that removes large objects,
in order to prevent damage to subsequent treatment and
process equipment.
influent: A process stream entering the treatment system.
intake: Water, such as tap or well water, that is used as makeup
water in the process.
lagoon: A shallow artificial pond for the natural oxidation of
sewage or ultimate drying of the sludge.
LAP: Loading Assembly and Packing operations.
MGD: Million Gallons per Day.
MHF: Multiple Hearth Furnace.
NA: Not Analyzed.
ND: Not Detected.
neutralization: The process of adjusting either an acidic or a
basic wastestream to a pH near seven.
NPDES: National Pollutant Discharge Elimination System.
NRDC: National Resources Defense Council.
NSPS: New Source Performance Standards.
photolysis: Chemical decomposition or dissociation by the action
of radiant energy.
PCB: PolyChlorinated Biphenyl.
POTW: Publicly Owned Treatment VJorks.
6/23/80
y i
-------
PSES: Pretreatment Standards for Existing Sources.
purged: Removed by a process of cleaning; take off or out.
screening process: A process used to remove coarse and/or gross
solids from untreated wastewater before subsequent treatment.
SIC: Standard Industrial Classification.
SS: Suspended Solids.
SRT: Solids Retention Time.
starved air combustion: Used for the volumetric and organic re-
duction of sludge solids.
terpene: Any of a class of isomeric hydrocarbons.
thermal drying: Process in which the moisture in sludge is re-
duced by evaporation using hot air, without the solids being
combusted.
TKN: Total Kjeldahl Nitrogen.
TOC: Total Organic Carbon.
trickling filter: Process in which wastes are sprayed through
the air to absorb oxygen and allowed to trickle through a
bed of rock or synthetic media coated with a slime of micro-
bial growth to removed dissolved and collodial biodegradable
organics.
TSS: Total Suspended Solids.
vacuum filtration: Process employed to dewater sludges so that a
is produced having the physical handling characteristics
and contents required for processing.
VSS: Volatile Suspended Solids.
WQC: Water Quality Criterion.
6/23/80
xiii
-------
II.1 INTRODUCTION
Volume II of the Treatability Manual provides generic process
descriptions for the industrial categories listed in Table 1-1.
This table also presents those categories currently included _
and those categories with additional data added. The categories
not currently included will be added as sufficient information
becomes available.
The objective of this volume is to characterize the wastewaters
discharged from the above categories on a facility by facility
basis, prior to treatment and after treatment. The pollution
control methods used with the treated final effluent pollutant
concentrations are also provided.
Each industrial category is defined according to the Standard
Industrial Classification (SIC) Codes of the U.S. Department
of Commerce and by the general industrial descriptions found in
current contractor draft development documents and published
development documents on each industry. The categories are
generally divided into subcategories which are described when
sufficient data are available. The total number of facilities
in each category discharging an aqueous effluent either directly
to a receiving stream or indirectly to a publicly owned treat-
ment works (POTW) is given in an industrial summary table.
Wastewater characteristics are provided for each category/
subcategory when sufficient information is available. Subcate-
gory wastewater characteristics are broken into separate pro-
cesses when sufficient data are available. These descriptions
include the complete pollutant analyses available in the refer-
ences. These analyses generally consist of conventional pollutants,
the 129 toxic pollutants, and other miscellaneous pollutants found
in the wastewater. The data presented should be assumed screening
quality unless specifically labeled verification quality.
Plant specific descriptions are also presented in this volume.
These descriptions generally include a treatment system descrip-
tion, plant production, and wastewater flow. Conventional
and toxic pollutant concentration data, as well as treatment sys-
tem removal efficiency are presented in site-specific tables.
6/23/80 II.1-1
-------
TABLE 1-1. INDUSTRY CATEGORIES FOUND IN VOLUME II
Section
II. 2
II. 3
II. 4
II. 5
II. 6
II. 7
II. 8
II. 8.1
II. 8. 2
II. 8. 3
II. 8. 4
II. 8. 5
II. 8. 6
II. 8. 7
II. 8. 8
II. 8. 9
II. 8. 10
II. 9
II. 9.1
II. 9. 2
II. 9. 3
II. 9. 4
II. 9. 5
11.10
11.11
11.12
11.13
11.14
11.15
11.16
11.17
11.18
11.19
11.20
11.21
11.22
Category
Auto and Other Laundries
Coal Mining
Electroplating
Inorganic Chemicals
Manufacturing
Iron and Steel Manufacturing
Leather Tanning and Finishing
Machinery and Mechanical
Products
Aluminum Forming
Battery Manufacturing
Coil Coating
Copper Forming
Electrical and Electronic
Components
Foundries
Mechanical Products
Photographic Equipment
and Supplies
Plastics Processing
Porcelain Enameling
Miscellaneous
Adhesives and Selants
Explosives Manufacture
Gum and Wood Chemicals
Pesticide Manufacturing
Pharmaceutical Manufacturing
Nonferrous Metals Manufacturing
Ore Mining and Dressing
Organic Chemicals Manufacturing
Paint and Ink Formulation
Petroleum Refining
Plastic and Synthetic Materials
Manufacturing
Pulp and Paperboard Mills and
Converted Products
Rubber Processing
Soap and Detergent Manufacturing
Steam Electric Power Plants
Textile Mills
Timber Products Processing
Publicly Owned Treatment Works
(POTW)
Included
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Revised
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
6/23/80
II.1-2
-------
Pollutant removability achievable by currently used treatment
systems is presented in the final section of each category.
Currently used treatment methods are described and the removal
efficiencies are reported. Potential treatment technologies
suggested in the reference documents are also presented. Com-
plete wastewater treatment alternative descriptions are given
in Volume III of this manual.
This volume is a general reference to be used in the decision
making process for NPDES permit applications. It should be noted
that no industrial description provided here takes into account
every plant within that industry; rather this volume presents a
general overview. Plant specific descriptions are not exemplary
plants within an industry but have been selected based on the
completeness of the available data. Treatment technologies
presented may not be the only control methods currently in use.
References are located on the final page of each report. Data
from these references are reported unchanged except reduced to
reasonable significant figures. Average pollutant removability
has often been calculated to provide a complete efficiency
table. If it is necessary to review these documents contact
lERL-Cincinnati which is retaining copies of each document.
6/23/80 II.1-3
-------
II.2 AUTO AND OTHER LAUNDRIES
II.2.1 INDUSTRY DESCRIPTION [1, 2]
II.2.1.1 General Description
The Auto and Other Laundries Industry in the United States is a
nonhomogeneous industrial group whose members are linked by the
fact that they provide cleaning services for their clients. Some
portions of the industry additionally provide the garments, rags,
rugs, or other products they clean to their customers instead of
cleaning customer-owned items. Because of this heterogeneity the
industry is covered by the standard industrial classification
(SIC) codes found in Table 2-1.
TABLE 2-1. SIC CATEGORIES OF THE LAUNDRY INDUSTRY [1, 2]
SICApproximate number
Category title code number of establishments
Power laundries, family
and commercial
Linen supply
Diaper service
Coin-operated laundries
and dry cleaning
Dry cleaning plants,
except rug cleaning
Carpet and upholstery
cleaning
Industrial laundries
Laundry and garment services,
not elsewhere classified
Car wash establishments
7211
7213
7214
7215
7216
7217
7218
7219
7542
3,100
1,300
300
32,000
28,400
2,700
1,000
2,700
40,000
There are four basic process divisions in this industry: water
wash (laundering), dry cleaning, dual-phase processing, and
carpet-upholstery cleaning. Brief descriptions of these
Date: 6/23/80 II.2-1
-------
processes and the car wash variation of the water wash process
are provided below.
Water Wash
In this portion of the industry, the primary cleaning is ac-
complished by a water wash. Soiled materials are first sorted
according to the processing required. If necessary, stains which
may set during washing must be removed. This can involve a
simple cold water soak or the use of acids, bleaches, and/or
multiple organic solvents. Once laundry is loaded into a machine
it undergoes a series of cleaning steps. These steps vary
according to the different types of desired final product and
range from wetting, sudsing, and rinsing the fabric, to souring
(reducing pH to about 5 to remove yellowing sodium bicarbonate),
blueing, bleaching, and finishing.
Dry Cleaning
In this group of processes the primary cleaning is accomplished
by an organic-based solvent rather than an aqueous-based deter-
gent solution. There are three different processes in the dry
cleaning industry. The first uses a controlled amount of water
and detergent throughout the cleaning cycle, in addition to the
solvent, to dissolve the water-soluble solids. The second is
similar but adds detergent only at the beginning of the cycle.
The third uses only solvent. This process requires prespotting
to remove water-soluble spots.
Solvents are generally filtered and recovered for further use.
Distillation purifies the solvent and removes odor-causing con-
taminants. Less expensive solvents are vented to the atmosphere
in some cases.
Dual-Phase Processing
In dual-phase or dual-stage processing the water/detergent wash
is preceded or followed by a separate solvent wash. This is used
almost exclusively by industrial laundries to clean items that
contain large amounts of both water-soluble soils and oil and
grease, such as work shirts and wiping rags.
Carpet and Upholstery Cleaning
Carpet and upholstery cleaning may be done on location or in a
plant. On-location cleaning is done by the powder, dry foam,
rotary brush, or hot water extraction method. In all of these
on-location methods, the carpet or upholstered item is vacuumed
and prespotted to remove stains before any other cleaning is
attempted.
Date: 6/23/80 II.2-2
-------
These on-location methods are similar processes that involve
working a medium into the soiled item, followed by vacuum extrac-
tion. They each use a different amount of water. The hot water
extraction process differs in that hot detergent solution is
injected and immediately wet vacuumed out.
In-plant carpet cleaning is done on a rug cleaning machine or on
a special cleaning floor, depending on carpet size. The rug is
mechanically beaten or vacuumed to remove loose soil, and stains
are.removed by prespotting with various solvents. This is fol-
lowed by a prewash in which a detergent solution is worked into
the pile. The carpet is then scrubbed, rinsed, and moved to a
drying room.
In a few plants dry cleaning machines are used for very delicate
and dye-sensitive rugs and tapestries. In these the only waste-
waters are cooling water from the solvent distillation unit and
the moisture removed from the carpet with the solvent.
Car Washes
Car washes are considered a variation of the water wash process.
The variation comprises facilities designed for the automatic or
self-service washing of vehicles. There are three main types of
car washes; tunnels, rollovers, and wands. The tunnel wash, the
largest of the three, is usually housed in a long building. The
vehicle is pulled by conveyor or driven through the length of the
building, passing through the separate washing, waxing, rinsing,
and drying areas. A trench, usually running the length of the
building, collects the wastewaters. Installation of a dam in the
trench permits separation of rinse wastewaters, facilitating
their treatment and reuse.
At a rollover wash, the vehicle remains stationary while the
equipment passes over it. Similar in design are the exterior
pressure washes which utilize high-pressure streams of water in
lieu of brushes. At both types, all the wastewater is collected
in a single trench, usually situated beneath the car.
The car also remains stationary at a wand wash, but here the
customer washes his own car with a high-pressure stream of water
from a hand-held wand. As at a rollover, both the wash and rinse
waters are collected in a single trench or sump. Because many
self-service washes are unmanned, the customer is able to wash
both vehicles and other objects. These can include engines and
undercarriages, motorcycles, farm equipment, animals; anything
that can be brought into the bay. Furthermore, it is possible
to change oil in the bay and to pour the used oil into the sump.
The waste load at such a facility can therefore vary tremendously.
Since the laundry and dry cleaning industries are almost exclu-
sively confined to the urban and suburban areas where their
Date: 6/23/80 II.2-3
-------
customers are located, more than 99% of all plants discharge to
publicly owned treatment works (POTW's). Table 2-2 lists the
number of subcategories and the type and number of dischargers
found in the Auto and Other Laundries Industry.
TABLE 2-2. INDUSTRY SUMMARY [3]
Industry: Auto and Other Laundries
Total Number of Subcategories: 9
Number of Subcategories Studied: 8
Number of Dischargers in Industry:
• Direct: 350
• Indirect: 90,000
• Zero: 20,000
II.2.1.2 Subcategory Descriptions
The modern Auto and Other Laundries Industry is grouped into the
following subcategories:
(1) Power Laundries, Family and Commercial
(2) Linen Supply
(3) Diaper Service
(4) Coin-Op Laundries and Dry Cleaning
(5) Dry Cleaning Plants Except Rug Cleaning
(6) Carpet and Upholstery Cleaning
(7) Industrial Laundries
(8) Car Washes
(9) Laundry and Garment Services, Not Elsewhere Classified
Seven of the nine subcategories have been submitted for exclusion
under Paragraph 8 of the NRDC Consent Decree. These subcategor-
ies are Power Laundries, Diaper Service, Coin-Op Laundries and
Dry Cleaning, Dry Cleaning Plants, Carpet and Upholstery Clean-
ing, Car Washes, and Laundry and Garment Services, not elsewhere
classified.
II.2.1.2.1 Power Laundries, Family and Commercial [1]
Power laundries are defined as establishments primarily engaged
in operating mechanical laundries with steam or other power. Ex-
cluded are laundries using small power equipment of the household
type as well as establishments that have power laundries but are
primarily engaged in specialty work such as diaper services,
linen supplies, or industrial laundries.
Date: 6/23/80 II.2-4
-------
Currently, 75% of power laundry receipts are from traditional
family and bachelor-type work, but almost 18% is derived from dry
cleaning.
II.2.1.2.2 Linen Supply [I]
Linen suppliers are defined as establishments engaged primarily
in supplying, on a rental basis, laundered items such as bed
linens, towels, table covers, napkins, aprons, and uniforms.
These establishments may operate their own power laundry facili-
ties or they may contract the actual laundering of the items they
own.
Because linen supply laundries are more efficient in water,
chemical, and energy usage than are on-premise laundries, sales
in the linen supply business have been increasing at a moderate
(14.6%) rate over the 1963-1974 period. One avenue of growth
being tapped by the linen supply subcategory is the light-to-
medium industrial laundry market. Currently, 80% of the dollar
value of the work done fits in the linen supply category, while
12% of the work is of the type usually handled by industrial
laundries.
This subcategory is being considered for possible exclusion under
Paragraph 8 of the NRDC Consent Decree.
II.2.1.2.3 Diaper Service [1]
Diaper service establishments are those primarily engaged in
supplying diapers (including disposables) and other baby linens
to homes, usually on a rental basis. Diaper services may or may
not operate their own power laundry facilities. There are ap-
proximately 300 such firms in the United States, which account
for about 0.6% of total laundry receipts.
The diaper service industry has not diversified as have many of
the other laundry categories. Traditionally, diaper services
have rented diapers and other baby linens to household users.
This role has remained essentially unchanged except that dispos-
able diapers are now also supplied to customers. Approximately
95% of the receipts are derived from the traditional sources.
The number of establishments and receipts for this industry have
been declining due to the falling birth rate and the increasing
popularity of disposable diapers.
This subcategory is being considered for possible exclusion under
Paragraph 8 of the NRDC Consent Decree.
II.2.1.2.4 Coin-Operated Laundries and Dry Cleaning [1]
The coin-op category is made up of establishments primarily en-
gaged in providing coin-operated laundry and/or dry cleaning
Date: 6/23/80 II.2-5
-------
equipment on their own premises. Included are establishments
that install and operate coin-operated laundry machines in apart-
ment houses, motels, etc.
In 1967 this subcategory encompassed 28% of all laundry estab-
lishments and accounted for almost 9% of total laundry revenues.
Over the past decade coin-op receipts have increased by 10% per
year, and it is expected that future growth will continue at a
moderate rate.
This subcategory is being considered for possible exclusion under
Paragraph 8 of the NRDC Consent Decree.
II.2.1.2.5 Dry Cleaning Plants Except Rug Cleaning [1]
Establishments belonging to this subcategory are those primarily
engaged in dry cleaning or dyeing apparel and household fabrics,
other than rugs, for the general public. There are about 28,000
such establishments, most of them relatively small. Dry cleaning
plants accounted for 54% of all laundry establishments and about
41% of all laundry receipts in 1967.
The number of dry cleaning establishments and real receipts in
this segment of the industry have both declined by 29% from 1963
to 1974. This is largely due to the new clothing fabrics
developed over the past 20 years. Many of these fabrics do not
require dry cleaning, or they shed soil more easily and hence re-
quire it less often than the old fabrics. Dry cleaners have
diversified into related fields such as shirt cleaning and
laundering in order to provide customers with one-stop cleaning
services. Relatively recent developments are drapery, rug, and
furniture cleaning and the sale and/or rental of working apparel.
This subcategory is being considered for possible exclusion under
Paragraph 8 of the NRDC Consent Decree.
II.2.1.2.6 Carpet and Upholstery Cleaning [1]
Carpet and upholstery cleaners are defined as establishments
primarily engaged in cleaning carpets and upholstered furniture
at a plant or on a customer's premises. It is estimated that 25%
of these businesses operate in-plant cleaning facilities. The
number of in-plant operations has declined significantly over the
last 10 years with a corresponding growth in the on-location type
cleaners. This is a result of the increase in the use of wall-
to-wall carpeting.
Firms in this category are not very diversified. Their basic
services include carpet and rug cleaning, repairing, and dyeing,
and upholstered furniture cleaning. Approximately 85% of the
receipts are from these activities. A small number of these
Date: 6/23/80 II.2-6
-------
firms offer in-plant dry cleaning services for specialty items
such as Orientals, Aubussons, Savonneries, and tapestries.
This subcategory is being considered for possible exclusion under
Paragraph 8 of the NRDC Consent Decree.
II.2.1.2.7 Industrial Laundries [1]
Industrial laundries are establishments primarily engaged in
supplying laundered or dry cleaned work uniforms; wiping towels;
safety equipment (gloves, flame-resistant clothing, etc.); dust
control items such as treated mats or rugs, mops, tool dust
covers and cloths; and similar items to industrial or commercial
users. These items may belong to the industrial launderers and
be supplied to users on a rental basis, or they may be the custo-
mers' own goods. Establishments included in this SIC category
may or may not operate their own laundry and dry cleaning
services.
Most industrial launderers offer their customers a variety of
textile maintenance services, but approximately 88% of the re-
ceipts are derived from the activities defined above. Although
there is some overlap in the work done by industrial launderers
and linen suppliers, industrial launderers can generally be dis-
tinguished because they rent personalized garments fitted and
labeled for the individual, while linen suppliers provide rental
garments by size.
II.2.1.2.8 Car Washes [1, 2]
Car wash trade associations have estimated that the total number
of car washes is about 40,000. Approximately 40% of these are
rollovers, 40% are wands, and 20% are tunnels. The industry
continues to grow at a rate of 3% to 4% a year, although the dif-
ferent types are growing at different rates. The number of new
tunnel facilities built each year is fairly constant. Rollovers
are primarily found at service stations where oil companies have
often used them as promotional devices. Sales are therefore de-
pendent on such things as the availability of gas.
The largest increases in sales have been for the self-service
wand-type car washes. The resurgence in sales is partly due to a
general upgrading of merchandise and facilities. Furthermore,
wand washes offer the best return for the least investment. The
number of bays sold for a location is generally tuned to what the
market requires, and the tendency is to begin with four bays.
This subcategory is listed for possible consideration for exclu-
sion under Paragraph 8 of the NRDC Consent Decree.
Date: 6/23/80 11.2-7
-------
II.2.1.2.9 Laundry and Garment Services Not
Elsewhere Classified [1]
This subcategory, Laundry and Garment Services NEC, is defined as
those establishments primarily engaged in furnishing other laundry
services, including both repairing, altering, and storing clothes
for individuals and the operation of hand laundries. Additional
services provided by these firms include fur garment cleaning, re-
pairing, and storage; glove mending; hosiery repair; pillow clean-
ing, and renovating; and tailoring. There are approximately 2,700
establishments in this category, most of which are very small.
This subcategory is being considered for a Paragraph 8 exclusion.
No data on discharges are available because this subcategory was
not studied, and it will not be considered further.
II.2.1.3 Wastewater Flow Characterization [1, 2]
The volume of wastewater produced by plants in this industry
range from 0.9 to 1,400 m3/d (24° to 360,000 gpd). This excludes
two subcategories: (1) Carpet and Upholstery Cleaning, for which
figures are not available, and (2) Dry Cleaning, which uses a
negligible amount of water (20 to 200 cm3 [0.023 to 1.0 gal] of
water per pound cleaned). Table 2-3 indicates water discharge
rates of those subcategories for which data are available.
TABLE 2-3. PROCESS WASTEWATER DISCHARGE RATES, BY SUBCATEGORY
mVkq (gal/lb)
Subcategory
Industrial laundries
Linen supplies
Power laundries
Diaper services
Coin-operated laundries
Car washes
Minimum3
0.008
(0.9)
0.014
(1.7)
0.018
(2.2)
0.006
(0.7)
0.007
(0.8)
(35)b
Maximum3
0.080
(9.6)
0.086
(10.3)
0.043
(5.1)
0.045
(5.4)
0.093
(11.2)
(80)b
Average
0.038
(4.6)
0.030
(3.6)
0.029
(3.5)
0.029
(3.4)
0.032
(3.8)
<->b
Minimum3
32
(8,600)
14
(3,600)
6.8
(1,800)
12
(3,100)
0.9
(240)
1.2
(300)
mj/day (gpd]
Maximum3
1,100
(290,000)
1,400
(360,000)
1,100
(290,000)
680
(180,000)
77
(20,000)
185
(48,000)
1
Average
260
(68,000)
410
(110,000)
230
(61,000)
160
(41,000)
14
(3,600)
Minimum and maximum values apply only to the laundries surveyed and do not necessarily
reflect absolute minima and maxima for the industry as a whole.
Gallons per car ( ).
Note: Blanks indicate data not available.
11.2.2 WASTEWATER CHARACTERIZATION
The physical and chemical characteristics of laundry wastewaters
are influenced by three primary factors: the general type of
cleansing process employed (i.e., water versus solvent wash), the
Date: 6/23/80
II.2-8
-------
types and quantity of soil present on the textiles being laun-
dered, and the composition of the various chemical additives used
in the process. Water wash effluents contain all of the soil and
lint removed from the textiles, as well as the laundry chemicals
employed in the process. On the other hand, wastewaters from dry
cleaning processes tend to contain water-soluble materials; lint,
grit, and insoluble organic and inorganic compounds are largely
removed by the solvent filter or confined to the still bottoms.
However, dry cleaning effluents also contain appreciable quan-
tities of solvent, which are not normally present in water-wash
effluents.
Tables 2-4 and 2-5 present subcategory wastewater descriptions
for conventional and toxic pollutants found in this industry.
II.2.2.1 Industrial Laundries
In comparison to domestic sewage, industrial laundry wastewaters
typically contain high loadings of BOD5, COD, TOC, suspended
solids, and oil and grease. BOD5 concentrations as low as
91 mg/L and as high as 7,800 mg/L were observed, which attests
to the extreme variability in industrial laundry wastewater
strength. The median TSS concentration in 69 wastewater ef-
fluents was 700 mg/L. Suspended solids loadings were also quite
variable, however, ranging from 68 mg/L to 6,100 mg/L. Oil and
grease concentrations ranged from 17 mg/L to 7,900 mg/L in 66
industrial laundry effluents, with a median value of 730 mg/L.
The high concentrations of oil and grease, suspended solids, and
biodegradable organics in industrial laundry wastewaters are pri-
marily attributable to the nature of the workload handled by
industrial laundries. Heavily soiled uniforms, shop towels, and
gloves used in the chemical and manufacturing industries often
comprise a substantial portion of the business handled by these
establishments. Pollutant loadings vary extremely from plant to
plant because of differences in equipment and in customers
served. This variability is at least partially attributable to
the soil loading on the articles being water washed. The highest
pollutant loadings are found in wastewaters from plants process-
ing a high percentage of wiping towels used in print shops,
machine shops, automotive repair shops, chemical plants, and
other heavy industrial operations. Much lower pollutant concen-
trations are found in the wastewaters from plants handling a high
percentage of uniforms and dust control items used in light
manufacturing concerns.
Factors such as water usage per pound of material washed and the
application of dual-phase or dry cleaning processes also affect
the concentrations at which various pollutants are found in in-
dustrial laundry wastewaters. For example, oil, grease, and many
other organic substances are more soluble in organic solvents
than in water, and, thus, they are not present to a large extent
Date: 6/23/80 II.2-9
-------
TABLE 2-4. WASTEWATER CHARACTERIZATION OF
AUTO AND OTHER LAUNDRIES [1, 2]
Number
Pollutant analyzed Maximum
BODs , mg/L
COD , mg/L
TOC, mg/L
TSS, mg/L
Total phosphorus, mg/L
Total phenols, mg/L
Oil and grease, mg/L
pH, pH units
51
60
24
69
12
19
66
62
Median
Mean
Number
analyzed Maximum Median
Industrial laundries
7,800
7,000
6,800
6,100
41.6
1.5
7,900
11.9
920
3,800
1,200
700
9.1
0.18
730
10.5
1,300
5,000
1,400
1,000
12.2
0.32
1,100
10.4
50
26
2B
59
5
7
52
58
Power laundries
BOD5, mg/L
COD, mg/L
TOC, mg/L
TSS, mg/L
Total phosphorus, mg/L
Total phenols, mg/L
Oil and grease, mg/L
pH, pH units
BOD5 , mg/L
COD , mg/L
TOC, mg/L
TSS, mg/L
Total phosphorus, mg/L
Total phenols, mg/L
Oil and grease, mg/L
pH, pH units
8
11
4
11
6
5
9
14
31
18
1
28
2
3
13
29
940
1,400
240
410
23.5
0.97
370
11.1
Coin-operated
500
930
68
630
18.0
0.30
74
9.2
210
580
160
230
4.0
0.073
52
9.6
laundries
120
270
-
85
9.8
<0.002
23
8.0
340
660
150
220
7.3
0.31
110
9.4
5
8
2
8
2
3
7
9
Mean
Linen laundries
1,500
4,000
1,200
1,200
48.5
0.26
910
12.3
610
1,500
300
360
14.5
0.12
300
10.2
620
1,600
400
400
18.7
0.12
330
10.1
Diaper laundries
560
1,100
400
280
30.0
0.080
330
11.0
240
520
390
130
22.8
0.036
85
10.4
320
580
390
150
22.8
0.040
120
9.9
Carpet cleaning plant
140
340
-
140
9.8
0.10
26
7.9
1
1
1
1
1
1
1
Dry cleaning plants
BODS , mg/L
COD, mg/L
TOC, mg/L
TSS, mg/L
Total phosphorus, mg/L
Total phenols, mg/L
Oil and grease, mg/L
pH, pH units
1
1
1
1
1
2
1
1
<2
8
2
3
0.2
<0.005
<2
7.2
_
-
-
-
-
<0.003
-
-
_
-
-
-
-
<0.003
-
-
45
NA
NA
45
NA
6
45
7
99
280
46
100
29.0
19
7.1
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Car washes
220
-
-
2,970
-
0.024
655
8.4
42
-
-
121
-
<0.002
68
7.2
58
-
-
270
-
<0.006
26
7.1
Date: 6/23/80
II.2-10
-------
TABLE 2-5. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATER FROM AUTO AND OTHER LAUNDRIES [1, 2]
(M9/L)
Laundry feedwater
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Sliver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitrosodiphenylamine
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dinitrophenol
2 , 4-Dimethylphenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene .
Dichlorobenzenes
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Anthracene/phenanthrene
Benz anthracene
Benzopyrene ^
Benzofluoranthene
2 -Chloronaphthalene
Fluoranthene
Naphthalene
Pyrene
Halogenated aliphatics
Carbon tetrachloride
Chlorodlbromomethane
Chloroform
Dlchlorobromomethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1,2-rrans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1 , 1 , 1-Trichloroethane
1, 1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
Pesticides and metabolities
Chlordane
4,4' -DDE
4,4' -DDT
Heptachlor
Isophorone
Number8
7/29
4/29
9/31
18/31
23/31
12/31
10/31
6/31
2/28
3/31
2/28
22/31
25/36
3/36
20/36
7/36
3/36
3/36
1/36
2/36
5/36
1/36
4/33
1/33
2/36
2/33
13/33
1/36
2/36
8/33
22/33
15/33
4/33
1/33
16/33
15/33
5/33
4/33
2/33
1/36
Maximum
27
11
20
80
300
100
e
60
4
30
6
300
1,200
S10
14
S10
S10
S10
S10
S10
S10
S10
40
2
S10
5
140
$10
410
20
140
88
£10
49
14,700
420
140
S10
130
S10
Median
<10
<1
<2
10
30
<20
<0.7
<5
<1
<5
<5
94
S10
BDL
S10
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
12
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Mean
<10
<1
<2
16
48
<20
<0.4
<6
<1
<5
<5
72
S50
S8
S5
S2
£0.8
BDL
SO. 3
SO. 6
SI
SO. 3
52
BDL
SO. 6
0.3
S8
SO. 3
SO. 6
S2
S25
9
BDL
BDL
S600
S16
S5
<0.7
5
SO. 3
Number3
20/22
14/24
1/14
32/36
32/35
36/36
19/28
35/36
22/24
31/36
2/16
11/26
36/36
16/19
3/19
8/19
1/19
4/19
1/19
2/19
6/19
1/19
11/18
1/19
8/18
17/18
4/19
1/19
10/19
2/18
14/18
2/18
7/18
13/18
5/18
8/18
1/18
1/19
Industrial
Maximum
1,800
1,600
5
520
8,800
11,000
1,000
22,000
19
2,400
120
130
9,000
17,500
1,500
820
S10
410
1,800
460
840
S10
23,400
1,100
17,500
50,900
470
17
4,800
1,700
34,600
20
540
93,200
6,600
800
3
190
. laundry
Median
140
17
<1
66
440
1,200
26
3,200
1
160
<1
5
2,400
560
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
12
BDL
BDL
1,000
BDL
BDL
23
BDL
15
BDL
BDL
84
BDL
BDL
BDL
BDL
Mean
240
77
<1
88
880
1,700
140
4,500
2
290
8
26
3,000
3,100
96
100
SO. 5
35
95
25
89
SO . 5
2,500
58
1,100
5,200
47
0.9
790
95
3,300
0.2
46
9,100
370
120
BDL
10
(CONTINUED)
Date: 6/23/80
II.2-11
-------
TABLE 2-5 (continued)
Power laundries
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Fhthalates
Bis(2-ethylhexyl> phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitrosodiphenylamine
Phenols
2 -Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dini trophenol
2,4-Dimethylphenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene b
Dichlorobenzenes
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Anthracene/phenanthrene
Benz anthracene
Benzopyrene ,
Benzofluoranthene
2 -Chloronaphthalene
Fluoranthene
Naphthalene
Pyrene
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromome thane
Chloroform
Dichlorobromome thane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1,2- TTans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Trichloroethylene
Trichlorofluorome thane
Pesticides and metabolities
Chlordane
4,4' -DDE
4,4' -DDT
Heptachlor
Isophorone
Number
5/6
2/6
3/5
6/7
7/7
1/5
6/7
5/8
4/7
2/7
6/6
4/4
4/4
4/4
1/4
3/4
2/4
1/4
2/4
2/4
3/4
1/4
1/4
2/4
1/4
2/4
1/4
3/4
1/4
3/4
1/4
2/4
1/4
1/4
1/4
1/4
Maximum
570
20
46
360
370
28
430
3
50
8
540
300
78
22
S5
75
1
1
55
9
2
S5
3
S10
0.3
£10
0.3
41
72
310
2
12
S3
S3
S3
S3
Hedi an
16
<15
3
25
110
<28
60
0.6
19
<7
430
100
16
18
BDL
46
BDL
BDL
BDL
BDL
1
BDL
BDL
BDL
BDL
BDL
BDL
27
BDL
15
BDL
BDL
BDL
BDL
BDL
BDL
Mean
160
<15
11
76
160
<28
110
0.7
14
<7
430
150
28
15
SI
42
0.7
0.2
14
3
1
SI
0.8
S3
0.08
S3
0.08
24
18
85
BDL
4
BDL
BDL
BDL
BDL
Number3
5/7
4/7
5/36
24/36
15/15
5/7
27/36
12/36
19/36
1/7
4/7
1/7
36/37
4/5
2/5
3/5
1/5
1/5
1/5
2/5
4/5
1/5
4/5
3/5
1/5
4/5
2/5
2/5
1/5
Linen laundries
Maximum
37
26
120
980
3,300
77
3,000
51
500
3
47
6
2,800
9,000
S10
26
S5
S5
£5
S10
30
11
99
16
1,200
180
92
S10
S10
Median
7
6
<2
46
210
35
240
0.2
28
2
2
5
700
160
BDL
S10
BDL
BDL
BDL
BDL
S10
BDL
25
S10
BDL
20
BDL
BDL
BDL
Mean
10
7
9
100
520
33
460
3
61
2
8
5
900
1,900
S3
S9
SI
SI
SI
S3
S15
2
S43
S7
240
63
25
S3
S2
(CONTINUED)
Date: 6/23/80
II.2-12
-------
TABLE 2-5 (continued)
Coin-operated laundries Dry cleaning plants
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Number3
2/3
1/3
1/3
1/3
3/3
2/3
2/3
Maximum
16
11
23
5
70
72
2
Median
13
<10
<2
<5
70
36
2
Mean Number3 Maximum Median
10
<10
8
<5
67 1/2 50 25
36 1/2 40 20
1
Mean
25
20
Nickel
Selenium
Sliver
Thallium
Zinc 3/3
Phthalates
Bis(2-ethylhexyl) phthalate 2/2
Butyl benzyl phthalate
Di-n-butyl phthalate 1/2
Diethyl phthalate 1/2
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitrosodiphenylamine
Phenols
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4-DimethyIphenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Tnchlorophenol
p-Chloro-oi-cresol
Aromatics
Benzene 1/3
Chlorobenzene .
Dichlorobenzenes
Ethylbenzene
Toluene 1/3
Polycyclic aromatic hydrocarbons
Anthracene/phecanthrene
Benzanthracene
Benzopyrene
Benzofluoranthene
2-Chloronaphthalene
Fluoranthene
Naphthalene
Pyrene
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromomethane 1/3
Chloroform 2/3
Dichlorobromomethane 1/3
1,2-Dichloroethane
1,1-Dichloroethylene 1/3
1,2-rrans-dichloroethylene 1/3
Methylene chloride 1/3
Tetrachloroethylene 1/3
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
Pesticides and metabolities
Chlordane
4,4'-DDE
4,4'-DDT
Heptachlor
Isophorone
670
840
55
25
160
800
28
12
310
800
28
12
1/2
1/2
1/2
14
BDL
BDL
1/2
1/2
1/2
0.3
12
70
19
3
5
6
25
BDL
20
BDL
BDL
BDL
BDL
BDL
4
30
6
BDL
BDL
2
8
1/2
1/2
1/2
1/2
1/2
1/2
1/2
1/2
2/2
1/2
1/2
1/2
S10
£10
S10
S5
<5
S5
S5
£5
S10
25
12
12
6
S5
12
6
= 10
4
2,300
3
500
23
460
30
58,600
2,500
3,000
440
2
1,200
1.5
250
12
230
15
29,400
1,200
1,500
220
2
1,200
1.5
250
12
230
15
29,400
1,200
1,500
220
(CONTINUED)
Date: 6/23/80
II.2-13
-------
TABLE 2-5 (continued)
Diacer laundries
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Number9
2/4
1/5
4/4
1/2
2/4
1/3
2/4
5/5
Maximum
40
22
100
60
35
0.9
100
10,000
Median
<6
<10
80
<50
<24
<0.9
<35
4,000
Mean
11
<10
79
<50
<24
<0.9
<35
5,700
Number*
7/7
7/7
7/7
7/7
7/7
7/7
45C
7/7
7/7
7/7
7/7
7/7
45C
4/5
2/5
1/5
Car washes
Maximum
17
1,560
<15
26
64
860
4,200
26
690
<5
<10
<5
2,420
1,000
31
15
Median
5.2
<10
<5
20
30
140
510
4
120
<5
<5
<1
590
56
22
15
Mean
7.9
230
<5
17
34
340
890
<1
260
<5
<5
• <2
750
280
22
15
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitrosodiphenylamine
Phenols
2-Chlprophenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4-Dimethylphenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
p-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene .
Dichlorobenzenes
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Anthracene/phenanthrene
Benzanthracene
Benzopyrene b
Benzofluoranthene
2-Chloronaphthalene
Fluoranthene
Naphthalene
Pyrene
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromomethane
Chloroform
Dichlorobromomethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-JTans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
Pesticides and metabolities
Chlordane
4,4'-DDE
4,4'-DDT
Heptachlor
Isophorone
2/5
1/5
3/5
1/1
38
NA
NA
1/1
72
NA
NA
1/5
1/5
1/5
1/5
1/5
1/5
1/5
1/5
3/5
1/5
4/5
1/5
1/5
16
19
15
34
12
12
12
14
170
11
12
83
33
640
13
120
16
19
14
34
12
12
12
14
170
11
12
37
33
240
13
120
16
19
13
34
12
12
12
14
170
11
12
47
33
280
13
120
Tlumber of times detected/number of analyses performed.
cNumber of times detected; no indication of number of analyses.
Reference reported compound in this form.
Note: Blanks indicate pollutant not detected.
Date: 6/23/80
II.2-14
-------
in the wastewaters from solvent cleaning and some dual-phase
cleaning processes.
In addition to plant-to-plant variability, wastewater strength
at any given industrial laundry may be quite variable from day to
day and from hour to hour. This is caused by the changing nature
of the workload and, on an instantaneous basis, by the particular
wash cycle effluents that are being discharged. For example, the
initial rinse, break, and wash waters contain much higher pollut-
ant- loadings than the final rinse waters.
Table 2-6 presents pH, BOD5, TSS, and oil and grease data for the
wastewater from one industrial laundry sampled on 30 separate
days over a several-year period. These data clearly illustrate
the fluctuating characteristics of industrial laundry wastes.
TABLE 2-6.
VARIABILITY OF CONVENTIONAL POLLUT-
ANT LOADINGS IN WASTEWATER FROM ONE
INDUSTRIAL LAUNDRY [1]
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Minimum
Maximum
Mean
PH
11.9
12.0
12.6
11.6
12.2
11.8
11.8
10.0
11.5
11.6
11.7
11.4
11.6
10.7
10.8
10.9
10.7
10.1
10.4
10.2
11.0
12.0
11.9
9.4
10.2
9.4
12.6
11.2
Pollutant, mg/L
BOD 5
1,700
2,500
710
650
1,300
690
940
680
930
1,400
1,600
2,200
3,700
650
3,700
1,500
TSS
2,300
2,100
2,400
1,900
1,900
2,100
5,000
2,800
3,600
4,000
3,800
2,700
2,300
810
650
3,500
1,700
1,800
2,600
4,400
3,800
5,300
1,300
2,400
2,000
2,000
2,600
650
5,300
2,700
Oil and grease
490
1,800
2,200
240
5,300
2,100
2,800
2,600
3,400
3,400
3,800
400
510
1,600
970
720
1,200
1,200
2,600
3,500
3,900
1,500
1,400
2,400
2,300
2,400
1,300
2,400
240
5,300
2,100
Note: Blanks indicate data not available.
Date: 6/23/80
II.2-15
-------
Ten toxic pollutant metals were found in more than 50% of the
industrial laundry effluents. Lead, zinc, and copper were
detected in virtually all of the samples and were present at
higher concentrations than any of the other metals. Chromium,
nickel, antimony, cadmium, arsenic, silver, and mercury were also
detected in the majority of the plant wastewaters, but generally
at much lower concentrations.
A total of 25 toxic organic pollutants were detected in one or
more of the 19 industrial laundry effluents analyzed for these
substances. Six toxic organic pollutants were detected in more
than 50% of the wastewater samples: toluene, bis(2-ethylhexyl)
phthalate, tetrachloroethylene, naphthalene, chloroform, and
benzene; however, only toluene and bis(2-ethylhexyl) phthalate
were consistently present at concentrations greater than 0.1 mg/L
in the wastewaters.
Ethylbenzene, 1,1,1-trichloroethane, methylene chloride, phenol,
di-n-butyl phthalate, di-n-octyl phthalate, anthracene, and tri-
chloroethylene were also found in 20% to 50% of the plant
effluents.
II.2.2.2 Linen Supply
Linen supply wastewaters typically contain higher concentrations
of BOD5, COD, TOC, suspended solids, and oil and grease than does
domestic sewage, but much lower concentrations of these pollut-
ants than do industrial laundry wastewaters. This is attributed
to the lighter soil loading on items such as bed sheets, pillow-
cases, towels, napkins, tablecloths, and uniforms, which comprise
the majority of the linen supply business. Phosphorus and pH
were found at similar levels in industrial laundry and linen
supply effluents, which reflects the fact that these pollutants
are introduced to the wastewater by process additives rather than
by soil on the articles being laundered.
Many linen supplies service industrial-type garments and flatwork
articles as well as the more traditional linen supply items.
Plant-to-plant differences in the amount of "industrial laundry"
work performed is a major cause for variable pollutant concentra-
tions. However, BOD5, TSS, and oil and grease loadings are also
influenced by the particular types of "linen supply work" per-
formed. For example, the wastewaters from laundries washing a
high percentage of aprons, tablecloths, napkins, etc., used in
restaurants contain higher levels of oil and grease than do
wastewaters from laundries washing a high percentage of sheets
or towels used in hotels.
Laundering chemicals are not considered a major source of BOD5,
TSS, or oil and grease in industrial laundry wastewaters. How-
ever, detergents, soaps, starches, and other organic process
chemicals contribute BOD to the wastewater; soap is also a source
Date: 6/23/80 II.2-16
-------
of oil and grease. These pollutant sources are considerably more
significant in comparison to soil loading in the linen supply
subcategory than in the industrial laundry subcategory. Variable
oil and grease concentrations in linen laundry wastewaters are at
least partially attributable to the fact that some establishments
use soap while others use synthetic detergents. Seven toxic pol-^
lutant metals were detected in 50% or more of the wastewater
samples analyzed for these substances. However, only zinc, lead,
and copper were found at average concentrations greater than
100-pg/L.
Sixteen toxic organic pollutants were detected in at least one of
five linen laundry effluents analyzed for these compounds. With
few exceptions, these were the same compounds found in the in-
dustrial laundry wastewaters. Much lower concentrations were
observed in the linen supply effluents, however; only bis(2-
ethylhexyl) phthalate, naphthalene, and chloroform were found in
any of the effluents at concentrations greater than 100 \jg/L.
II.2.2.3 Power Laundries, Family and Commercial
Power laundry wastewaters typically contain lower concentrations
of BOD5, COD, TOC, suspended solids, and oil and grease than
either industrial laundry or linen supply wastewaters. Much
narrower ranges in concentration are also indicated.
Both of these observations are related to the types of customers
serviced by power laundries. Family wash has been traditionally
the largest source of business for these establishments, but many
power laundries now service commercial businesses and service
organizations. However, very little industrial-type work is per-
formed; hence, the soil loadings on garments washed in these
laundries tend to be light.
The median and mean concentrations of BOD5, COD, TOC, TSS, oil
and grease, and phosphorus are comparable to the levels at which
these pollutants are found in domestic sewage. However, power
laundry wastewaters tend to be more alkaline than does domestic
sewage due to the use of alkali in the washing process.
Only five toxic pollutant metals (antimony, zinc, lead, copper
and chromium) were present in any of the effluent samples at con-
centrations greater than 100 (jg/L. Except for zinc and copper,
median concentrations of these metals were all much less than
100 M9/L, in the range of detection limits.
Twenty-five toxic organic pollutants were present in one or more
of the four wastewaters analyzed for these compounds, but only
bis(2-ethylhexyl) phthalate and tetrachloroethylene were found
in any of the samples at concentrations greater than 100 pg/L.
Date: 6/23/80 II.2-17
-------
II.2.2.4 Diaper Services
In terms of BOD5, COD, and oil and grease, these wastewaters
appear to be roughly equivalent to the wastewater discharged by
power laundries. Higher concentrations of TOC and phosphorus,
and lower concentrations of suspended solids were present in the
diaper service effluents, but these observations are based on
limited data and may not represent the entire industry.
Median and mean concentrations of all conventional pollutants,
excluding pH, are roughly comparable to the levels at which these
pollutants are present in domestic wastewaters.
Seven toxic pollutant metals were detected in at least one
sample, but only zinc was present at more than 100 ug/L in any of
the samples. No other toxic pollutants were found at significant
levels, which is understandable in light of the types of soil
present on diapers.
II.2.2.5 Coin-Operated Laundries
Coin-op wastewaters are less heavily polluted than are the waste-
waters from any of the four commercial laundry subcategories
previously discussed, and they are comparable to low-strength
domestic wastewaters. Lightly soiled family wash accounts for
nearly all of the business at these establishments.
Eight toxic pollutant metals and 12 toxic organic pollutants were
detected in at least one of these effluent samples, but only
zinc, total phenol, and bis(2-ethylhexyl) phthalate were present
at concentrations greater than 100 pg/L in any of the samples.
II.2.2.6 Carpet and Upholstery Cleaners
Except for phosphorus, all pollutant concentrations in this sub-
category are comparable to or less than the median and mean
pollutant loadings shown for coin-operated laundry wastewaters.
Zinc, copper, lead, and tetrachloroethylene were the only toxic
pollutants found at a concentration greater than 100 |jg/L.
II.2.2.7 Dry Cleaning Plants
Conventional and toxic pollutant data from tne dry cleaning
industry were obtained from two plants that use perchloroethylene
(tetrachloroethylene) solvent. All pollutant concentrations are
extremely low—in the range of or below analytical detection
limits. The source of process wastewater at these plants was
condensate from the steam regeneration of carbon columns used for
solvent vapor emission control.
Date: 6/23/80 II.2-18
-------
Eighteen toxic organic pollutants were detected in one of the
wastewater samples, but none was found in both effluents except,
as expected, tetrachloroethylene.
Chlorinated ethanes, ethylenes, and chloroform were the only
toxic pollutants, other than tetrachloroethylene, found at con-
centrations greater than 50 M9/L-
II.2.2.8 Car Washes
The primary wastes present in car wash wastewater are suspended
and dissolved solids, oil and grease, BOD5, lead, and zinc.
Other priority metals are sometimes encountered (especially in
wand wash effluents) in small amounts.
The sources of solids are road grit, dust or mud, salt, snow, and
ice, as well as plant and animal materials. Solids may also be
picked up from suspended particles in the air.
Oil and grease may enter the wastewater either from the vehicle
wash equipment and operation, or the vehicle itself. Much of the
equipment used for car washing at tunnel and rollover facilities
is hydraulically operated and may leak hydraulic fluid into the
drain trench. Surfactants and waxes used in the washing opera-
tions may account for a portion of the measured oil and grease.
Leaky crankcases and the washing of undercarriages and engines
will account for much of the oil and grease measured in car wash
effluents. The dumping of oil down the drains at unsupervised
wand washes may also occur.
The main sources of BOD5 are the detergents and waxes used for
cleaning purposes, although it may also result from organic plant
and animal materials carried into the wash on car bodies and
tires.
The presence of lead in the wastewater results from the use of
lead additives in gasoline. Significant lead levels accumulate
in crankcase oil and the exhaust fumes of automobiles, and lead
may be introduced into the carwash via these sources. Gasoline
deposits on the body of the car and on tire treads may also act
as sources of lead.
Zinc may be used in the manufacture of automobile tires which may
then act as a source of this metal.
Other trace metals such as arsenic, cadmium, chromium, copper,
mercury, and nickel are often detected in car wash effluents.
However, the concentrations found are generally quite low.
The variations encountered in waste loads are great and may be
seasonal as well as regional. Winter conditions will increase
the suspended solids load due to ice, grit, and mud accumulations
Date: 6/23/80 11.2-19
-------
Lead may also increase as a result of the use of fly ash as part
of the road sanding material. Fly ash analysis usually shows a
high lead content. Dusty soils will be turned into hard-to-
remove mud during rainy seasons. Geographical differences will
be due to soil types, type and extent of industry, road condi-
tions, etc. Variations in waste loads will also be found among
the different types and locations of car washes. Wand washes
tend to produce the heaviest loads, as vehicles other than cars
(four-wheel drive vehicles, trucks, RV's, motorcycles), parts of
the-car other than the body (engines, undercarriages), and a wide
variety of other objects, may be washed. At unattended sites
customers may perform oil changes in the bay, and may dump the
oil down the drain. Rollovers tend to exhibit a lighter waste
load than either tunnels or wands. Many rollovers are situated
at rental agencies and car dealerships where cars are washed with
more than average frequency.
11. 2. 3 PLANT SPECIFIC DESCRIPTIONS
II.2.3.1 Car Washes
The sampling done at these plants was completed over a 4-hour
period when road conditions were dry.
Plant IB is a total recycle tunnel facility at which 75 cars were
processed during the study. In this plant suspended solids and
oil and grease concentrations were low compared to domestic sew-
age. Metal concentrations were generally low, with seven metals
at less than 10 ug/L. Of the remaining six metals only zinc,
nickel, and lead concentrations exceeded 100 ug/L. In this plant
no analyses were performed to measure the toxic organics.
Wash water and rinse water are treated by different methods at
this plant. The wash water is processed solely by settling in
settling tanks. The rinse water is processed by settling fol-
lowed by filtration through turbidity filters. Plant IB plant
specific data are presented in Tables 2-7 and 2-8.
Plant 2A is a total recycle wand facility where 57 cars were
processed during sampling. The sampling results at this plant
showed high suspended solids concentrations and low oil and
grease concentrations compared to domestic sewage. Metal con-
centrations were generally low, with four metals at less than
10 ug/L and six metals at less than 100 ug/L. Only copper, lead,
and zinc were present at high concentrations ranging from 860 to
1,230 ug/L. Several groups of toxic organics appeared in the
waste, but no organic was at a higher concentration than 100 ug/L.
The groups concerned were the phthalates, phenols, ethers,
nitrogen compounds, polycyclic aromatics, and halogenated
aliphatics.
Date: 6/23/80 II.2-20
-------
TABLE 2-7.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR AUTO LAUNDRY IB [1]
Concentration, mg/L
Pollutant
BOD 5
TSS '
IDS
Total phenols
Oil and grease
pH
Raw
wash
42
56
690
<0.002
21
7.3
Treated
wash
42
24
700
<0.002
20
7.4
Percent
removal
0
57,
_b
-
5
™
Concentration, mg/L
Raw
rinse
42
64
600
<0.002
24
7.3
Treated
rinse
42
9.3
650
<0.002
4.7
7.2
Percent
removal
0
85,
_b
-
80
""
Except pH values, which are given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
TABLE 2-8.
PLANT SPECIFIC TOXIC METALS
FOR AUTO LAUNDRY IB [2]
Concentration, [jg/L
Raw
Toxic pollutant wash
Treated
wash
Concentration, pg/L
Percent Raw Treated
removal rinse rinse
Percent
removal
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
5
5
<0
25
64
85
<0
470
<1
690
<1
<1
<1
720
.2
.0
.1
.3
.3
.2
.002
4.4
10
<0 . 1
30.8
86.2
114
<0.002
910
<1
331
<1
<1
< j
1,000
15 3
-a 5
-,
-------
TABLE 2-9. PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR AUTO LAUNDRY 2 A [2]
Concentration, mg/La
Pollutant
BOD 5
TSS
TDS
Total phenols
Oil and grease
pH
Raw
wastewater
120
520
1,300
<0.002
20.5
7.2
Treated
wastewater
35
36
880
<0.002
18
7.2
Percent
removal
71
93
30
-
12
•.
aExcept pH values, which are given in pH units.
TABLE 2-10. PLANT SPECIFIC TOXIC POLLUTANT
DATA FOR AUTO LAUNDRY 2A [2]
Concentration, M9/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Ethers
Bis ( 2-chloroethoxy )methane
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Nitrogen compounds
1 , 2-Diphenylhydrazine
Phenols
2 , 4-Dinitrophenol
4-Nitrophenol
Polycyclic aromatic hydrocarbons
Anthracene
Benz ( a ) anthracene
Benzo(a)pyrene
Benz o ( k ) f 1 uor anthene
Fluoranthene
Phenanthrene
Pyrene
Halogenated aliphatics
Chlorodlbromomethane
Chloroform
Dlchlorobromome thane
Methylene chloride
Trichloroethylene
Raw
wastewater
11
28
-------
concentrations were generally low with nine metals at less than
10 pg/L. Only copper, lead, nickel, and zinc concentrations ex-
ceeded 100 (jg/L. Only a very small number of toxic organic
compounds were found in the wastewater and, with the exception of
methylene chloride, at concentrations less than 100 pg/L. The
only toxic groups found were the phthalates, phenols, and halo-
genated aliphatics.
Wastewater treatment in this plant consists of the following
sequence of steps: settling, centrifugal separation, and
turbidity filtration. At this point the stream is split, and
one portion is used as wash water. The other portion is filtered
through activated charcoal and iodinated before it is used as
rinse water. Plant specific information for this facility is
shown in Tables 2-11 and 2-12.
II.2.3.2 Other Laundries
Plant B is an industrial laundry without wastewater recycle. COD,
suspended solids, and oil and grease concentrations found during
sampling were high compared to domestic sewage. Concentrations
of three metals (copper, lead, and zinc) were high, ranging from
1,600 to 9,400 pg/L. Of the other metals analyzed for, four were
found in concentrations of less than 100 pg/L and four were not
detected. Toxic organic compounds were not present in a wide
variety, but those found tended to high concentrations, with 10
of 11 at greater than 100 pg/L. Two of these, N-nitrosodiphenyl-
amine and naphthalene, were present at 1,600 pg/L and 4,000 pg/L,
respectively. At least one representative of each organic group
except ethers, cresols, and polychlorinated biphenyls was
detected.
The wastewater treatment used by this plant consists of calcium
chloride coagulation of the solids with polymer addition, fol-
lowed by dissolved air flotation. The floe from the flotation
step is then skimmed from the surface and transferred to a sludge
pit. Plant specific information for this plant is presented in
Tables 2-13 and 2-14.
Plant G is a linen supply laundry with wastewater recycle. The
wastewater from this plant exhibited very high levels of BOD,
COD, TOC, and TSS concentrations as compared to domestic sewage.
On the same basis, the phosphorus level was low and the oil and
grease level was in the medium range. Metal concentrations
tended to be high, although concentrations of six metals were
below 100 pg/L and two metals were not detected. Copper,
mercury, and zinc were present at concentrations from 2,000 to
5,800 pg/L. Only five toxic organics were detected, three of
them at concentrations of less than 100 pg/L. Only one,
naphthalene, had a concentration greater than 1,000 pg/L. The
compound classes detected were phthalates, phenols, and poly-
cyclic aromatics.
Date: 6/23/80 II.2-23
-------
TABLE 2-11.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR AUTO LAUNDRY 3A [2]
Pollutant
BOD5
TSS
TDS
Total phenols
Oil and grease
pH
Concentration ,
Raw
wastewater
8
210
510
Sample broken
6.0
6.2
mg/La
Treated
wastewater
<3
7.0
450
<0.002
30
5.8
Percent
removal
62
97
12
~h
^
Except pH values, which are given in pH units.
^Treated effluent concentration exceeds raw
wastewater concentration.
TABLE 2-12.
PLANT SPECIFIC TOXIC POLLUTANT
DATA FOR AUTO LAUNDRY 3A [2]
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Phenols
Pentachlorophenol
Halogenated aliphatics
Methylene chloride
Trichlorofluoromethane
Raw
wastewater
2.5
<10
<5
2
10
140
< 0.004
460
<1
160
<5
<5
<2
340
31
16
ND
470
ND
Treated
wastewater
1
<10
<5
<1
<5
130
<0.004
11
<1
40
<5
<5
<2
140
ND
ND
58
1,200
150
Percent
removal
60
-
-
50
50
7
-
98
-
75
-
_
-
59
100
100
_a
_a
a
Treated effluent concentration exceeds raw wastewater concentration
Date: 6/23/80
II.2-24
-------
TABLE 2-13.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR INDUSTRIAL LAUNDRY B [1]
Pollutant
COD
TSS
Total phenols
Oil and grease
pH
Concentration
Raw
., mg/La
Treated
wastewater wastewater
3,800
700
0.016
440
11.6
1,300
48
<0.001
190
7.0
Percent
removal
66
93
94
57
M.
Except pH values, which are given in pH units.
TABLE 2-14.
PLANT SPECIFIC TOXIC POLLUTANT
DATA FOR INDUSTRIAL LAUNDRY B [1]
Concentration, \ig/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Thallium
Zinc
Phthalates
Di-n-butyl phthalate
Nitrogen compounds
N-ni trosodiphenyl amine
Phenols
Phenol
Aromatics
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites
Isophorone
Raw
wastewater
41
12
170
270
1,600
9,400
2
150
<5
4,500
ND
1,800
600
260
750
4,000
10
540
880
210
190
Treated
wastewater
<20
<10
23
<130
"330
230
<0.2
<50
<5
200
290
620
120
110
790
790
e
500
1,000
30
ND
Percent
removal
51
17
86
52
79
98
90
67
-
96
_a
66
80
58a
a
80
20
7.
a
86
100
3Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80
II.2-25
-------
Wastewater treatment in this plant consists of polyelectrolyte
coagulation and dissolved air flotation (with skimmers pushing
the solids into a sludge hopper). All or part of this clarified
water is passed through a multimedia filter and recycled. When
100% recycle is not employed the excess is discharged. Plant
specific information is presented for plant G in Tables 2-15 and
2-16.
Plant J is a power laundry utilizing wastewater recycle. During
sampling wastewater from this plant had low to medium concentra-
tions of all the classical pollutants compared to domestic sewage.
Metal concentrations also tended to be low with only the zinc
concentration above 100 |jg/L. There were 19 toxic organics from
4 toxic pollutant categories present, but none at a higher con-
centration than 100 [jg/L, and most at less than 10 (jg/L. The
four categories of organics are phthalates, phenols, polycylic
aromatics, and halogenated aliphatics.
The wastewater treatment used in this facility is polyelectrolyte
coagulation followed by dissolved air flotation equipped with
skimmers. All or part of this clarified water may be filtered
via a multimedia filter and recycled. Plant specific information
for this facility is presented in Tables 2-17 and 2-18.
Plant N is a service laundry with no wastewater recycle. The
concentrations of classical pollutants observed were all in the
low range compared to domestic sewage. Metal concentrations also
tended to be low, with six metals not detected and concentrations
of only two (copper and zinc) greater than 100 yg/L. A small
number of toxic organics was present with only one above 10 ng/L.
The classes of organics detected were phthalates, phenols, mono-
cyclic aromatics, and halogenated aliphatics.
The wastewater treatment process used in this plant is: alum
coagulation and clarification by settling, and treatment of the
clarified effluent by carbon adsorption, filtration, and
chlorination/dechlorination. Plant specific information for
Plant N is shown in Tables 2-19 and 2-20.
II.2.4 POLLUTANT REMOVABILITY [1, 2]
Treatment technology for this industry falls into two distinct
groups, methods employed at car washes and methods employed at
other laundries. Because of the large difference in the treat-
ment methods, they are described separately below.
II.2.4.1 Car Washes [1, 2]
Settling is used by a large majority of car washes before recycle
or discharge. New tunnel facilities are almost always equipped
for recycle of their wash water after treatment by settling. The
solids and oil and grease are removed from the settling tank
Date: 6/23/80 II.2-26
-------
TABLE 2-15.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR LINEN SUPPLY FACILITY G [1]
Concentration, mg/La
Pollutant
BOD 5
COD
TOC
TSS
Total phosphorus
Total phenols
Oil and grease
Raw
wastewater
2,000
2,600
1,100
1,300
5.7
0.082
130
Treated
wastewater
1,100
1,800
530
210
3.7
0.21
240
Percent
removal
45
31
52
84
35a
a
Treated effluent concentration exceeds raw waste-
water concentration (3-day composite).
TABLE 2-16.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR LINEN SUPPLY FACILITY G [1]
Concentration, pg/L
Toxic pollutant
Raw
wastewater
Treated
wastewater
Percent
removal
Metals and inorganics
Antimony 45
Arsenic 33
Cadmium 240
Chromium 670
Copper 2,000
Cyanide 63
Lead 4,000
Mercury 5
Nickel 880
Selenium 2
Silver 10
Zinc 5,800
Phthalates
Bis(2-ethylhexyl) phthalate 280
Di-n-butyl phthalate 26
Phenols
Phenol 24
Polycyclic aromatic hydrocarbons
Anthracene/phenanthrene 16
Naphthalene 1,200
4
15
<2
170
200
88
720
1
50
7
<1
580
96
11
24
12
520
91
55
99
75
82
80
90
90
66
58
25
57
aTreated effluent concentration exceeds raw wastewater concentration.
Reference reported compound in this form.
Date: 6/23/80
II.2-27
-------
TABLE 2-17. PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR POWER LAUNDRY FACILITY J [1]
Concentration, mg/L
Pollutant
BOD 5
COD
TOC
TSS
Total phosphorus
Total phenols
Oil and grease
Raw
wastewater
113
497
135
50
0.8
0.432
39
Treated
wastewater
118
378
94
40
0.7
0.264
16
Percent
removal
_a
24
30
20
12
39
59
aTreated effluent concentration exceeds raw
wastewater concentration.
TABLE 2-18. PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR POWER LAUNDRY FACILITY J [1]
Concentration, ug/L
RawTreatedPercent
Toxic pollutant wastewater wastewater removal
Metals and inorganics
Antimony <10 <10
Cadmium <2 <2
Chromium 26 16 38
Copper 55 52 5
Cyanide 29 11 62
Lead <22 <22
Nickel <36 <36
Silver <5 <5
Zinc 290 105 64
Phthalates
Bis(2-ethylhexyl) phthalate 82 54 34
Butyl benzyl phthalate 17 8 53
Di-n-butyl phthalate 2 0.9 55
Di-n-octyl phthalate 28 4 86
Phenols
2-Chlorophenol 3 2 33
2,4-Dichlorophenol 12-
2,4-Dimethylphenol 2 29 -
Pentachlorophenol 3 10 -
Phenol 2 7 -a
Polycyclic aromatic hydrocarbons
Anthracene/phenanthrene 0.9 2 -
Fluoranthene 0.3 0.4 -a
Naphthalene 0.9 0.9 0
Pyrene 0.3 0.3 0
Halogenated aliphatics
Chloroform 41 12 71
Methylene chloride 5.7 52 -a
1,1,2,2-Tetrachloroethane ND 9 -a
Tetrachloroethylene 220
1,1,1-Trichloroethane 2 ND 100
Trichlorofluoromethane ND 5 -a
aTreated effluent concentration exceeds raw wastewater concentration.
Reference reported compound in this form.
Date: 6/23/80 II.2-28
-------
TABLE 2-19.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR SERVICE LAUNDRY N [1]
Concentration, mg/L
Pollutant
BOD 5
COD
TOC
TSS
Total phosphorus
Total phenols
Oil and grease
Raw
wastewater
163
240
63
40
7.0
0.038
15
Treated
wastewater
23
59
21
37
0.9
0.013
0.75
Percent
removal
86
75
67
8
87
66
95
TABLE 2-20.
PLANT SPECIFIC TOXIC POLLUTANT
DATA FOR SERVICE LAUNDRY N [1]
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Phenols
Phenol
Aromatics
Toluene
Halogenated aliphatics
Chi orodibromome thane
Chloroform
Dichlorobromomethane
1,1,2, 2 -Tetrachloroe thane
Tetrachloroethylene
Trichloroethylene
Raw
wastewater
51
39
138
<2
71
55
14
609
ND
ND
ND
ND
1.8
5
0.6
ND
ND
ND
2
0.5
Treated
wastewater
14
25
32
<2
31
37
7
244
16
4
3
2
ND
6
ND
9.5
1.0
0.7
31
3.0
Percent
removal
73
36
77
-
56
33
50
60
_a
Si
100
_a
100
_a
a
_a
a
a
Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80
II.2-29
-------
periodically for disposal. Hydrocyclones are gaining popularity
and have been used quite sucessfully at some installations. Sand
and multimedia turbidity filters may also be used to remove
finely divided suspended solids, almost always in conjunction
with settling. It is estimated that 5% to 10% of all car washes
use this technology.
Activated charcoal filters are used to remove detergents and
other organics from water to be used for rinsing purposes, but
they are installed less frequently than turbidity filters. Foam
fractionators are used in some car washes to remove surfactants
from the wastewaters. Pollutant removal efficiencies for systems
incorporating these technologies are included in Section II.2.3.1.
II.2.4.2 Other Laundries [1]
Table 2-21 indicates the technologies being used in the other
laundries segment and the estimated percentage of plants
utilizing each. Tables 2-22 through 2-24 provide removability
data for the three most common systems.
Bar screens are used in a small percentage at industrial and
linen supply laundries to remove large solids (6.3 mm to 19 mm).
Lint screens are used in the majority of industrial, linen supply,
and power laundries and by more than a third of diaper service
laundries to remove lint and particles such as sand and grit (in
the range of 3.2 mm to 9.5 mm). Catch basins are used in ap-
proximately the same proportions in the industry to provide for
settling of solids, with retention times of 15 to 40 minutes
being typical. The only other technology in common use (approxi-
mately the same proportions) is countercurrent heat exchange
between the wastewater and the incoming feedwater; this serves
to reduce both fuel consumption for water heating and the
temperature of the final effluent.
The following technologies are used by very small numbers of
plants but provide greater reductions in pollutant concentrations
than the common technologies. Equalization tanks having reten-
tion times of 2 to 4 hours smooth the discharge flow and remove
solids and grease from the wastewater stream. These tanks are
used in a small percentage of industrial, linen supply, and power
laundries, as is pH adjustment. Dissolved air flotation (DAF)
with chemical addition is used in a small percentage of indus-
trial, linen supply, and power laundries to destabilize and
remove the colloidal suspensions which contain most of the
pollutants that result from plant operations in this industry
segment. In the small proportion of the industry utilizing
wastewater recycle, multimedia filters are used for removal of
fine particulates remaining after dissolved air flotation. Re-
movability data for systems containing these components are
Date: 6/23/80 II.2-30
-------
TABLE 2-21.
ESTIMATED PERCENT OF LAUNDRIES (BASED ON TECHNICAL
SURVEY DATA) HAVING CONTROL TECHNOLOGY [1]
Industrial Linen supply
Control technology laundries laundries
Pretreatment technology
(Number of responses)
Bar screens
Lint screens
Catch basins
Heat reclaimers
Oil skimmers
Equalization tanks
pH adjustment
Physical-chemical systems
Other1
(74)
2.7
70
72
70
15 v,
1.2b
4.1b
1.3b
8.1
(59)
5.1
81
78
81
0 _
2.1C
5.1
0.38C
3.4
Power Coin-op Diaper
laundries laundries service
(20) (1)
0
65
55
25
0 .
0.033a
15 H
0.033a
0
3 (75)
0
36
20
32
0
0
0
0
4.0
Treatment technology for discharge other than to municipal treatment systems
(Number of responses) (0) (0) (2)a (33)
Physical-chemical systems 6.3g 0
Biological 42
-...n
Other1
None
27
31
(0)
Note: Blanks indicate data not available.
aNumber of responses not sufficient to provide valid estimate.
Estimate based on 12 physical-chemical system with equalization tanks operating at
the 1,013 industrial laundry indirect dischargers.
cEstimate based on 5 physical-chemical systems with equalization operating at the
1,308 linen supply indirect dischargers, plus the 1.7% of linen supplies that have
equalization tanks based on survey responses.
Estimate based on 1 physical-chemical system with equalization operating at the 3,078
power laundry indirect dischargers.
eMajor unit operations consist of chemical addition and floe- removal.
Other includes filtration, separators, oil hold back devices, and miscellaneous
operations.
^Estimate based on 1 physical-chemical system operating at the 16 power laundry direct
dischargers.
Other includes filtration, settling, chlorination, and miscellaneous operations.
TABLE 2-22. RESULTS OF CONVENTIONAL TREATMENT - SYSTEM I
a,b
[1]
Pollutant
parameter
Oil and grease, mg/L
BOD 5 , mg/L
TSS, mg/L
Copper, |jg/L
Lead, |jg/L
Zinc, pg/L
Number
of data
points
9
9
9
8
9
5
Concentration
Washroom discharge
Median
620
310
500
120
520
450
Range
190 -
170 -
210 -
30 -
220 -
380 -
1,350
660
1,300
690
2,400
860
Sewer discharge
Median
480
300
480
100
270
420
Range
140
190
270
10
50
5
- 1,360
- 970
- 1,600
- 420
- 1,300
- 830
Percent removal
Median
19
6
0
28
32
0
Range
0
0
0
0
0
0
- 65
- 18
- 20
- 66
- 91
- 99
based on sampling results from three laundries.
System uses a bar screen, lint screen, catch basin, and heat reclaimer.
Date: 6/23/80
II.2-31
-------
TABLE 2-23. RESULTS OF CONVENTIONAL TREATMENT - SYSTEM IIa'b [1]
Pollutant
parameter
Oil and grease, mg/L
BOD5 , mg/L
TSS, mg/L
Copper, pg/L
Lead, pg/L
Zinc, M9/L
Number
of data
points
3
3
3
2
3
3
Concentration
Washroom discharge
Median Range
760
310
420
310
700
750
420
150
230
220
100
430
- 850
- 540
- 470
- 400
- 1,100
- 890
Sewer discharge
Median
460
240
390
270
450
570
Range
420
230
280
220
350
370
- 550
- 500
- 630
- 320
- 600
- 610
Percent removal
Median
51
7
17
9
40
14
Range
0
0
0
0
0
0
- 72
- 23
- 33
- 18
- 50
- 29
aData based on sampling results from one laundry.
System uses a bar screen, lint screen, catch basins, oil skimmer, and heat reclaimer.
TABLE 2-24. RESULTS OF CONVENTIONAL TREATMENT - SYSTEM IIIa/b [1]
Pollutant
parameter
Oil and grease, mg/L
BOD s , mg/L
TSS, mg/L
Copper, M9/L
Lead, pg/L
Zinc, pg/L
Number
of data
points
3
3
3
3
3
3
Concentration
Washroom discharge
Median
770
610
280
300
310
960
Range
890
450
220
260
250
780
- 1,260
- 650
- 340
- 350
- 43,000
- 2,000
Sewer discharge
Median
740
710
340
340
450
1,500
Range
340
690
240
320
350
920
- 1,070
- 730
- 1,450
- 920
- 600
- 1,700
Percent removal
Median
41
0
0
0
0
4
Range
0
0
0
0
- 42
0
- 14
- 9
0
- 15
Data based on sampling results from one laundry.
System uses a lint screen, catch basins, equalization tank, and heat reclaimer.
found in Section II.2.3 and listed in Tables 2-25 through 2-31.
These systems are the most efficient currently in use.
In addition, three other technologies are potentially applicable
to this segment of the industry: ultrafiltration, diatomaceous
earth filtration, and electrocoagulation.
Both bench- and pilot-scale tests have shown that ultra-
filtration (UF) using tubular modules is feasible, but it is not
technically or economically feasible to use spirally wound mem-
branes. From a technical standpoint UF systems with tubular
modules have advantages over physical-chemical systems utilizing
chemical addition and DAF. UF does not incorporate coagulation;
thus it does not require chemical additives. Since laundry
wastewater is highly variable, it can be difficult to provide an
effluent of consistent quality based on a specific coagulant or
Date: 6/23/80 11.2-32
-------
TABLE 2-25. RESULTS OF LAUNDRY WASTEWATER.TREATMENT
WITH ALUM COAGULATION AND DAFa [1]
Pollutant
parameter
Oil and grease, mg/L
BODS, mg/L
TSS, mg/L
Phosphorus , mg/L
Copper, vg/L
Lead,* pg/L
Zinc, pg/L
PH*
Number
of dat<
points
3
3
3
2
3
3
3
5
Concentration
i Equalization tank
Range
ISO
180
51
23
620
100
1,000
9.9
- 260
- 352
- 510
- 25
- 1,000
- 1,300
- 3,300
-11.0
Median
175
340
487
24
620
800
1,800
10.6
Mean
195
290
349
24
660
730
2,000
_c
Effluent
Range
11
63
16
1.5
360
10
500
4.6
- 50
- 120
- 118
- 2.6
- 130
- 300
- 1,300
-7.2.
Median
43
65
24
2.1
340
60
1,000
7.0
Percent removal
Mean
35
83
53
2.1
280
120
930
-c
Range
72 -
65 -
69 -
80 -
45 -
77 -
45 -
-
94
81
95
93
66
92
61
Median
81
66
77
87
64
90
50
Mean
82
71
80
87
SB
86
52
'Results based on sampling and analysis of laundry effluent from one industrial laundry.
Given in pH units.
°Not reported.
TABLE 2-26.
RESULTS OF LAUNDRY WASTEWATER TREATMENT WITH
CALCIUM CHLORIDE COAGULATION AND DAFa [1]
Pollutant
parameter
Oil and grease, mg/L
BODS, mg/L
TSS, mg/L
Phosphorus , mg/L
Copper, Mg/L
Lead, M9/L
2inc pg/L
PH"
Number
of data
points
13
^
10
2
5
10
10
5
Concentration
Equalization tank
Rl
212
460
390
13
1,000
2,600
1,000
11.0
inge
- 1,600
- 2,400
- 950
- 42
- 1,700
- 9,400
- 4,500
- 11.6
Median
477
657
835
27
1,500
4,800
3,200
11.4
Mean
647
1,212
741
27
1,200
5,400
3,000
_C
1
9
130
18
1.7
200
50
10
6.5
Effluent
lange
- 230
- 1,000
- 240
- 23
- 500
- 700
- 780
- 7.5
Median
116
345
69
12
340
170
150
7.0
Percent removal
Mean
116
447
104
12
300
210
210
_c
Rl
57
6
71
0
67
89
76
inge
- 99
- 78
- 98
- 96
- 80
- 99
- 99
-
Median
77
68
88
48
78
98
94
-
Mean
79
59
85
48
73
96
93
-
aData from sampling of six industrial laundries.
Given in pH units.
cNot reported.
TABLE 2-27. RESULTS OF LAUNDRY WASTEWATER TREATMENT
WITH FERRIC SULFATE AND DAFa [1]
Pollutant
parameter
Oil and grease, mg/L
BODS, mg/L
TSS, mg/L
Phosphorus , mg/L
Copper, pg/L
Lead, M9/L
Zinc, pg/L
PH*
Number
Concentration
of data
points
8
8
8
3
3
6
8
5
Equalization tank
Range
160
485
300
12
200
200
420
- 580
- 2,000
- 840
- 23
- 300
- 600
- 1,100
_c
Median
375
1,550
535
22
200
350
600
c
Mean
412
1,420
536
19
230
330
670
_c
Effluent
Range
13
100
22
0.05
300
20
500
5.8
- 428
- 2,400
- 770
- 0.49
- 500
- 200
- 1,100
- 7.0
Median
24
235
64
0.35
400
750
1,100
6.1
Mean
100
187
61
0.30
110
90
910
_c
Percent removal
Range
0 -
0 -
0 -
97 -
0
66 -
0
-
97
87
96
99
90
Median
91
80
89
98
0
70
0
•
Mean
76
87
89
98
0
73
0
-
aResults arc obtained from sampling and analysis of one linen supply laundry.
Given in pH units.
Not reported.
Date: 6/23/80
II.2-33
-------
TABLE 2-28. RESULTS OF LAUNDRY WASTEWATER TREATMENT WITH
FERROUS SULFATE COAGULATION AND DAFa [1]
Pollutant
parameter
Oil and grease, mg/L
BODS, mg/L
TSS, mg/L
Phosphorus , mg/L
Copper, Mg/L
Lead, -pg/L
Zinc, Mg/
PH"
Number
Concentration
of data
points
8
e
8
3
3
8
8
5
Socialization tank
Range
347
757
260
17
800
3,000
940
10.6
- 2,600
- 1,900
- 1,405
- 27
- 8,000
- 13,000
- 3,400
- 11.7
Median
735
1,235
635
21
2,000
6,700
2,600
11.3
Mean
915
1,312
710
21
3,600
7,200
2,500
_c
Effluent
Range
12
85
34
0.05
30
20
70
6.6
- 41
- 370
- 190
- 0.33
- 100
- 300
- 300
- 7.7
Median
27
215
75
0.05
90
100
110
7.0
Percent removal
Mean
28
209
86
0.14
730
130
130
_c
Range
93 -
77 -
58 -
99
87 -
90 -
85 -
99
91
93
99
99
90
Median
97
87
90
99
96
99
95
Mean
97
84
88
99
80
98
95
Results obtained from sampling and analysis at one industrial laundry.
Given in pH units.
GNot reported.
TABLE 2-29.
RESULTS OF LAUNDRY WASTEWATER TREATMENT
WITH POLYELECTROLYTE AND DAFa [1]
Pollutant
parameter
Oil and grease, mg/L
BOD5, mg/L
TSS, rog/L
Phosphorus , mg/L
Copper, M9/L
Lead, pg/L
Zinc, Mg/L
PH*
Number
of data
points
5
10
9
3
5
5
10
5
Concentration
Equalization tank
Range
400
725
390
1.1
90
40
170
8.6
- 560
- 2,600
- 3,000
- 6.6
- 2,000
- 2,000
- 2,000
- 10.1
Median
420
1,185
615
3.6
580
950
590
9.7
Mean
418
1,385
904
3.8
740
810
900
_C
Effluent
Range
68
545
110
0.05
70
50
70
7.5
- 216
- 1,500
- 670
-0.49
- 480
- 950
- 1,000
-10.0
Median
150
931
410
0.35
180
210
390
8.5
Mean
193
944
387
2.3
200
320
410
_c
Percent removal
Range
50
0
0
97
0
0
0
- 88
- 62
- 96
- 99
- 96
- 84
- 80
Median
64
25
32
98
35
51
45
Mean
54
32
57
39
73
60
54
*Results obtained from sampling and analysis of three linen supply laundries.
Given in pH units.
cNot reported.
Date: 6/23/80
II.2-34
-------
TABLE 2-30.
to
I
U)
en
CONCENTRATIONS OF SELECTED ORGANICS IN LAUNDRY WASTEV/ATER BEFORE
AND AFTER TREATMENT, BY TYPE OF CHEMICAL ADDITION [1]
(lJg/L)
Organic pollutant
Anthracene/phenanthrenef
Bis(2-ethylhexyl) phthalato
Butyl benzyl phthalate
Chrysene
Carbon tetrachloride
Pentachlorophenol
Chloroform
2-Chloronaphthalene
Dichlorobenzenes
Chlorobenzene
Di-n-butyl phthalate
1 , 1-Dichloroethylene
Di-n-octyl phthalate
Dichlorobromoethane
2 , 4-Dimethylphenol
1 , 2-Dichloropropane
Ethylbenzene
1 , 2-rrans-dichloroethylene
Isophorone
Methylene chloride
Naphthalene
N-nitrosodiphenylamine
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Toluene
Phenol
Benzene
Pyrene
System A System
Influent Effluent Influent
20
120g 1009 4,700g
1,700 30
20g 20g 20
300g 2709 30
10g
2209
40 1,200
iog
6,600 100
20g
20g 20g 20
BC
Effluent
10
450g
10
10
30g
2,600g
520
30g
80g
20
System
Influent
380
l,900g
310
20
1,100
50g
150
460
1,0009
190^
320g
4,000g
1,800
190g
20
210
l,600g
100g
90
Cd
Effluent
70
610g
30
260
150g
30
80g
3,300g
7909
630
650g
10
30
840g
100g
160
System Ee
Influent Effluent
470 10
5,100 110
1,500 40
200
40
10
20
60
660 20
1,000
410
290
930
50
410 100
80
190
120
20
Blanks indicate concentrations were below 10 |jg/L or compound was not detected. Values represent one data
point only.
Physical-chemical treatment with alum coagulation and DAF for floe removal.
Physical-chemical treatment with polyelectrolyte coagulation and DAF for floe removal.
Physical-chemical treatment with calcium chloride coagulation and DAF for floe removal.
ePhysical-chemical treatment with ferrous sulfate coagulation and DAF for floe removal.
Reference reported compound in this form.
gValues are median concentrations for two or more data points.
-------
TABLE 2-31. SUMMARY OF LAUNDRY WASTEWATER TREATMENT FOR REMOVAL OF
ORGANIC CONTAMINANTS WITH PHYSICAL CHEMICAL SYSTEMS9 [1]
to
I
Concentration ,
Organic pollutant
An thracene/phenanthrene
Benzene
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Carbon tetrachloride
Chloroform
2-Chloronaphthalene
Dichlorobenzene
Di-n-butyl phthalate
Di-n-octyl phthalate
2 , 4-Dimethylphenol
Ethylbenzene
Isophorone
Methylene chloride
Naphthalene
N-nitrosodiphenylamine
Phenol
Tetrachloroethylene
1, 1,1-Trichloroethane
Trichloroethylene
Toluene
Equalization tank
Range
160 - 470
130
820 - 9,000
170 - 1,500
1,700
180
14 - 20
1,100
660
28 - 410
46
17,500
D
10 - 540
4,800
1,800
600
880
18 -.6,600
D
19 - 2,600
Median
380
65
740
310
850
20
17
55
160
150
230
25
190
57
810
900
28
30
3,300
210
250
Mean
290
65
2,300
610
850
38
17
550
230
200
230
2,700
190
120
1,700
900
110
190
3,300
210
720
pg/L
Effluent
Range
10
120
35
30
15
18
11
6,
84
16
1,
14
14
- 66
- 200
- 1,000
42
- 36
28
- 19
- 260
- 350
33
29
970
_D
000
840
- 620
- 190
000
-1.100
_b
- 8,300
Median
12
160
140
33
12
17
140
100
15
44
220
500
350
45
57
57
30
380
Mean
29
160
310
17
33
15
17
140
150
12
15
250
1,400
450
350
70
350
57
30
1,400
Percent removal
Range
25
0
53
0
0
0
0
0
78
0
0
0
0
0
0
0
22
0
- 98
0
- 98
- 99
- 88
- 76
- 5
- 76
- 97
- 99
- 99
- 99
- 91
- 99
- 66
- 80
- 94
-.98
_b
- 65
Median
83
0
68
97
49
41
2
38
55
86
50
3
99
0
78
33
0
0
60
86
0
Mean
69
0
63
83
49
41
2
38
48
88
50
37
99
19
66
33
19
13
60
86
19
Blanks indicate concentration was below 10 pg/L.
Medians and means represent one data point.
-------
based on a set coagulant dosage rate. UF systems also require
less space than comparable physical-chemical systems with DAF.
Removability data for the tubular ultrafiltration module is given
in Table 2-32.
TABLE 2-32.
RESULTS OF LAUNDRY WASTEWATER TREATMENT USING
A TUBULAR ULTRAFILTRATION MODULE [1]
Pollutant
parameter
Oil and grease
BOD 5
TSS
Average
concentration,
mg/L
Influent Effluent
2,100 86
3,500 310
1,500 5
Average
percent solids
of sludge
concentration ,
mg/L
1.9
4.5
—
Average
percent
removal
96
91
99
aResults obtained from laboratory bench-scale unit.
, Not applicable.
Diatomaceous earth (DE) filters applied to treatment of laundry
wastewater were found to be generally capable of excellent
removal of suspended solids but not of colloidal matter. Waste-
water at a linen supply laundry with an average flowrate of
530 m3/day (140,000 gpd) was treated by DE filtration. Effluent
from an equalization tank was injected with DE and a proprietary
oil adsorbent, then pumped through precoated pressure filters.
Capabilities of this system, in terms of removing pollutants, are
given in Table 2-33. The system was in full-scale operation;
however, it has since been replaced by a treatment system using
calcium chloride coagulation and DAF.
TABLE 2-33.
RESULTS OF LAUNDRY WASTEWATER TREATMENT
USING DIATOMACEOUS EARTH FILTRATION [1]
Oil
BODS
TSS,
Lead
Zinc
Pollutant
parameter
and grease, mg/L
, mg/L
mg/L
- M9/L
. M9/L
Number
of data
points
5
5
5
4
5
Concentration
Equalization tank
Median Range
390
610
460
300
570
250
460
330
200
430
- 430
- 680
- 680
- 600
- 1,100
Effluent
Median
210
460
200
200
430
Range
180
350
140
50
340
- 350
- 340
- 210
- 300
- 500
Percent
Median
43
32
65
45
35
removal
Range
0
0
39
0
0
- 53
- 43
- 75
- 99
- 55
obtained from 1 laundry; system is no longer in operation.
Date: 6/23/80
II.2-37
-------
Electrocoagulation (EC) systems are designed to treat laundry
wastewater through two mechanisms. With the first, electrolysis
includes coagulation by neutralizing or imparting a positive
charge to negatively charged colloidal material. With the second,
microbubbles formed as a result of electrolysis float the re-
sulting floe to the surface of the contained effluent where it
can be skimmed off.
In EC pilot tests chemical addition was required prior to elec-
trolysis to achieve removal of pollutants. Alum, sulfuric acid,
and polymer were added to the laundry effluent. Test results of
laundry wastewater treatment using chemical addition and elec-
trolysis are given in Table 2-34.
TABLE 2-34. RESULTS OF LAUNDRY WASTEWATER TREATMENT
USING A PILOT ELECTROCOAGULATION SYSTEM [1]
Pollutant
parameter
Oil and grease, mg/L
BOD 5 , mg/L
TSS, mg/L
Copper, (jg/L
Lead, pg/L
Zinc, \ig/L
Number
of data
points
4
4
4
4
1
4
Concentration
Influent
Median
530
770
290
200
1,100
640
Range
380
660
250
200
460
- 690
- 960
- 330
- 300
-
- 760
Effluent
Median
79
270
140
100
20
350
Range
74
140
120
100
300
- 146
- 600
- 170
- 200
-
- 440
Percent removal
Median
80
70
53
50
98
40
Range
75 -
9 -
48 -
33 -
-
35 -
89
82
51
50
53
aSystem incorporates chemical addition with alum, sulfuric acid, and polymer at
average dosage rates of 1,100 mg/L, 850 mg/L, and 4 mg/L, respectively.
Other technologies have been tested on laundry wastewaters with
varying degrees of success. In general, these techniques are not
applicable to the pollutants present or are not considered eco-
nomically competitive. They include reverse osmosis, foam
separation, distillation and carbon adsorption.
11.2 . 3 REFERENCES
1. Technical Support Document for Auto and Other Laundries
Industry (draft contractor's report). Contract 68-03-2550,
U.S. Environmental Protection Agency, Washington, D.C.,
August 1979.
2. Status Report on the Treatment and Recycle of Wastewaters
from the Car Wash Industry (draft contractor's report).
Contract 68-01-5767, U.S. Environmental Protection Agency,
Washington, D.C., July 1979.
3. NRDC Consent Decree Industry Summary - Auto and Other
Laundries.
Date: 6/23/80 11.2-38
-------
II.3 COAL MINING
II.3.1 INDUSTRY DESCRIPTION [1, 2]
II.3.1.1 General Description
Coals are classified into several ranks or types related to
chemical composition and physical characteristics. The standard
classes are anthracite, bituminous, subbituminous, and lignite.
All ranks of coal are mined by the coal industry, which can be
divided into the following two segments: (1) the production of
anthracite, and (2) the production of bituminous coal, subbitumi-
nous coal, and lignite. The industry can also be divided by
production processes into coal mining and coal services (coal
cleaning and coal preparation), as indicated by the major SIC
categories for this industry:
SIC 1111 Anthracite Mining
SIC 1112 Anthracite Mining Services
SIC 1211 Bituminous Coal and Lignite Mining
SIC 1213 Bituminous Coal and Lignite Mining Services
Once historically significant in the economic and industrial
growth of the United States, the importance of anthracite coal as
an energy source in this nation has been declining in recent
years. Consequently, the anthracite industry is currently under
consideration by the EPA for exemption from BATEA regulations.
The mining of bituminous coal and lignite constitutes the major
portion of the coal mining industry. U.S. Geological Survey
estimates indicate that bituminous coal and lignite currently
comprise over 99% of the nation's total coal reserves.
According to the Bureau of Mines there were 6,168 active bitumi-
nous coal and lignite mines in the industry in 1975. The
majority of the mines were small operations, with individual
production of less than 90,700 Mg (100,000 tons) per year.
Although these small mines comprised over 80% of the active
facilities in 1975, they accounted for less than 20% of the
bituminous coal production. Large mines producing greater than
90,700 Mg per year represented less than 20% of the facilities,
but produced almost 81% of the coal. The recent trend has been
toward larger mines and consolidation of mining companies.
Date: 6/23/80 II.3-1
-------
The coal mining industry currently operates in 25 states located
in Appalachia, the Midwest, and the Mountain and Pacific regions.
The six leading coal producing states in 1975 were, in order of
output, Kentucky, West Virginia, Pennsylvania, Illinois, Ohio,
and Virginia. Production in these states accounted for 74% of
the total U.S. output.
Table 3-1 presents industry summary data for the Coal Mining
point source category in terms of the number of subcategories,
number of dischargers, pollutants and toxics found in significant
quantities, total number of toxic pollutants detected, and
candidate treatment and control technologies [1, 3].
TABLE 3-1. INDUSTRY SUMMARY [I, 3]
Industry: Coal Mining
Total Number of Subcategories: 3
Number of Subcategories Studied: 3
Number of Dischargers in Industry:
• Direct: 6,000
• Indirect: 0
• Zero: Not available
Pollutants and Toxics Found in Significant Quantities
Methylene chloride 2,6-Dinitrotoluene
Chloroform Chlorobenzene
Bis(2-ethylhexyl) phthalate Suspended solids
Benzene Iron
Toluene Manganese
1,1,2,2-Tetrachloroethylene Antimony
1,2-Trans-dichloroethylene Arsenic
Di-n-butyl phthalate Chromium
1,1,1-Trichloroethane Copper
Trichlorofluoromethane Lead
Ethylbenzene Mercury
1,2-Dichloroethane Nickel
Anthracene/Phenanthrene Thallium
Zinc
Number of Toxic Pollutants Found in:
Raw Treated
wastewater effluent
Acid or ferruginous mines 15 16
Alkaline mines 29 48
Preparation plants 54 28
Candidate Treatment and Control Technologies:
Aeration Carbon adsorption
Neutralization Filtration
Sedimentation Flocculation
Ozonation Ion exchange
Reverse osmosis Starch xanthate
Date: 6/23/80 II.3-2
-------
II.3.1.2 Subcategory Descriptions
Based on similarities in raw materials, final products, manu-
facturing processes, and waste characteristics, the following
subcategories of the coal mining industry were established [1]:
1. Acid or Ferruginous Mines
2. Alkaline Mines
3. Coal Preparation Plants and Associated Areas
Since wastewater characteristics within each of the subcategories
are similar, these three subcategories are adequate to character-
ize the coal mining and preparation industries for the purpose of
establishing effluent guidelines for the best available technol-
ogy economically achievable (BATEA).
Subcategory 1 - Acid or Ferruginous Mines
Characterizing the industry according to the quality of mine
drainage is difficult because of the lack of readily available
information on a mine-by-mine basis. However, the 1976 Develop-
ment Document for the Coal Mining point source category generally
categorizes mines in Maryland, Ohio, Pennsylvania, and northern
West Virginia as being potentially acid or ferruginous [1]. Ac-
cording to the Bureau of Mines, there are an estimated 2,605
mines located in acid areas. Mines that are potentially acid
make up a large portion of the bituminous surface mining facil-
ities. Almost 50% of the surface mines reported by the Bureau
of Mines in 1975 could be classified as potentially acid or
ferruginous. Acid drainage, however, does not appear to be as
much of a problem among deep mines in the bituminous industry.
Approximately 70% of these mines can be categorized as having
alkaline drainage.
Acid mine drainage is generated under natural conditions when
pyritic coal seams are mined. The pyrites or iron sulfides
contained in the coal and associated strata are exposed to the
atmosphere during the mining process. In the presence of oxygen,
water, and certain species of oxidizing bacteria (Thiobacillus
ferroxidans and Ferrobacillus fevroxidans) , these sulfides
oxidize to ferrous sulfate, forming an acidic, ferruginous
leachate.
Subcategory 2 - Alkaline Mines
Most bituminous and lignite coal mines are located in areas
where the potential for the formation of acid mine drainage does
not exist. According to estimates made by the Bureau of Mines,
there are 3,563 bituminous coal and lignite mines which can be
classified as having alkaline drainage (50% of the surface mines
and 70% of the underground mines).
Date: 6/23/80 II.3-3
-------
Alkaline mine drainage can be generated under natural conditions
similar to those found in mines with acid drainage. Iron sul-
fides, however, are transformed into ferrous bicarbonates, and an
alkaline iron-bearing water is produced. Additionally, there are
large areas of coal reserves where the naturally occurring
associated groundwaters are alkaline. The coal in these areas is
usually lower in pyritic sulfur, and the resulting mine drainages
do not develop the low pH characteristic of acid mine drainage.
Subcategory 3 - Coal Preparation Plants and Associated Areas
The physical coal cleaning processes used today are oriented
toward product standardization and reduction of ash, with in-
creasing attention being placed on sulfur reduction. Coal pre-
paration in commercial practice is currently limited to physical
processes. In a modern coal cleaning plant, the coal is typi-
cally subjected to: (1) size reduction and screening, (2) grav-
ity separation of coal from its impurities, and (3) dewatering
and drying.
The commercial practice of coal cleaning is currently limited to
separation of the impurities based on differences in the specific
gravity of coal constituents (i.e., gravity separation process)
and on the differences in surface properties of the coal and its
mineral matter (i.e., froth flotation).
Coal preparation can be classified into five general levels.
Levels 1 to 3 are generally used in the preparation of steam coal.
Level 4 is used for metallurgical grade coal, and Level 5 has not
yet been commercially demonstrated in this country. The five
general levels of coal preparation are described below.
Level 1 - Crushing and Drying. Level 1 plants use rotary
breaker crushers and screens for top size control and for the
removal of coarse refuse. No washing is done and the entire
process is dry. Since most removal of pyritic sulfur is accom-
plished by hydraulic separation, this level of cleaning is
inefficient for reducing sulfur levels.
Level 2 - Coarse Size Coal Beneficiation. Level 2 cleaning
plants^in addition to crushing and screening raw coal, also
perform wet beneficiation of the coarse material with a jig or
dense medium vessel. The fine material is mixed with the coarse
product without washing. A finer sizing of the coal is accom-
plished than in Level 1. This system provides removal of only
coarse pyritic sulfur material and is therefore recommended for
a moderate pyritic sulfur content coal.
Level 3 - Coarse and Medium Size Coal Beneficiation. Level
3 cleaning is basically an extension of Level 2. Coal is crushed
and separated into three size fractions by wet screening. The
coarse material is cleaned in a coarse coal circuit. Medium
Date: 6/23/80 JX 3_4
-------
fractions are beneficiated by hydrocyclones, concentrating
tables, or dense medium cyclones. Fine coal is dewatered and
shipped with the clean coal or discarded as refuse. However, the
level of beneficiation is not substantially greater than that of
Level 2 with respect to sulfur removal and this system is
recommended for use on low and medium sulfur coals which are
relatively easy to wash. This process provides rejection of
free pyrite and ash, as well as enhancement of energy content.
Level 4 - Coarse, Medium, and Fine Size Coal Beneficiation.
In Level 4 preparation, coal is crushed and separated into three
or more size fractions by wet screening. All size fractions are
beneficiated. Heavy media processes are used for cleaning coarse
and medium size fractions. Froth flotation processes or hydro-
cyclone processes are used for cleaning fine particles. Level 4
coal preparation systems provide high efficiency cleaning of
coarse and fine coal fractions with lower efficiency cleaning of
the ultrafines. This method accomplishes free pyrite rejection
and improvement of Btu content.
Level 5 - "Deep Cleaning" Coal Beneficiation. Level 5
cleaning is basically Level 4 preparation in which one size frac-
tion is rigorously cleaned to meet a low sulfur-low ash product
specification. Two or three coal products are produced to
various market specifications. This level also uses a fine coal
recovery circuit to increase total plant recovery. Coal prepara-
tion processes are discussed in greater detail in the open
literature.
There were 388 preparation plants processing bituminous coal and
lignite in 1975 according to the Bureau of Mines [1]. Ninety-five
percent of the preparation plants listed in the 1976 Keystone
Coal Industry Manual used wet processing methods [1]. Only 21
plants were found to use dry processes. The majority of the wet
processing plants use either heavy media separation or froth
flotation, or both.
Wastewater from coal preparation emanates from two different
sources: (1) process-generated wastewater, and (2) wastewater
from associated areas which include coal preparation plant yards,
immediate access roads, slurry ponds, drainage ponds, coal refuse
piles, and coal storage piles and facilities.
The liquid discharges from coal preparation plants are often
combined with discharges of the associated storage piles, refuse
areas, and plant areas prior to final effluent treatment. The
wastewater from these areas is characterized as being similar to
the raw mine drainage at the mine being served by the preparation
plant. Consequently, some refuse piles produce an acid leachate
and others produce an alkaline leachate. The origin of the acid
leachate is the same as that for acid mine drainage, and its
prevention is the same; i.e., keep water away from the pyrites.
Date: 6/23/80 TT.3-5
-------
II.3.2 WASTEWATER CHARACTERIZATION [1]
This section describes the sources and characteristics of waste-
water from the coal mining industry. No wastewater is purposely
generated in the extractive portion of coal mining because water
is almost always a hindrance and an extra expense to pump and
treat. A minor exception is the use of water for dust suppres-
sion and equipment cooling. Water enters coal mines via precipi-
tation, groundwater infiltration, and surface runoff, and it can
become polluted by contact with materials in the coal, overbur-
den, or mine bottom. Most water entering underground mines
passes through the mine roof from overlying strata (rock units).
These rock units generally have well developed joint systems,
which tend to cause vertical flow. Chemicals used in mining and
repair of mining machinery may also be wastewater pollutants.
Mine water is therefore considered a wastewater for the mining
segment of the coal industry. It is discharged as mine drainage
which may require treatment before it can enter into surface
waters.
Based on these considerations and the industry categorization, it
is possible to characterize wastewater from the coal mining
industry in the following way.
I. Mining of Anthracite, Bituminous Coal, and Lignite
A. Acid or Ferruginous Mines
1. Raw Mine Drainage (untreated mine drainage
definitely requiring neutralization and
sedimentation treatment)
2. Treated Mine Drainage
B. Alkaline Mines
1. Raw Mine Drainage
2. Discharge Effluent (untreated mine drainage
of generally acceptable quality; i.e., not
requiring neutralization or sedimentation)
3. Sediment-Bearing Effluent (mine drainage
which has passed through settling ponds
or basins without a neutralization treatment)
II. Mining Services for Anthracite, Bituminous Coal,
and Lignite
A. Coal Preparation Plant Wastewater
B. Coal Storage, Refuse Storage, and Coal Preparation
Plant Ancillary Wastewater
Date: 6/23/80 II.3-6
-------
II.3.2.1 Subcategory 1 - Acid or Ferruginous Mines
Drainage from acid mines presents the most serious threat to the
environment from the coal mining category. Acidity is delete-
rious to a variety of forms of life including fish and benthic
organisms. The ferruginous components (ferric ion and ferrous
ion), though not highly toxic in themselves, do contribute to the
formation of insoluble hydroxides which coat benthic organisms,
cover other aquatic food sources, and block fish gills. The
acidic nature of this wastewater creates a strong solvent for
many metals and minerals, and the data base confirms the elevated
levels of many classical pollutants and heavy metals derived
from both the coal seams and the associated strata.
All operations studied dewater their mines either on an inter-
mittent or continual basis. The amount of wastewater discharged
from these facilities varies considerably, ranging from
approximately 3,800 to 265,000 m3/d (1 to 7 Mgal/d).
II.3.2.2 Subcategory 2 - Alkaline Mines
The data base for this study shows that heavy metals and other
toxic pollutants are seldom present in elevated concentrations in
alkaline mine drainage, but alkaline wastewaters may be high in
suspended "solids and require settling.
Over 50% of the facilities studied in this subcategory dewater
their mines on a continual basis. Of the rest, dewatering occurs
only infrequently or not at all. The amount of wastewater dis-
charged from these facilities ranges from 0 to 9,500 m3/d (0 to
2.5 Mgal/d).
II.3.2.3 Subcategory 3 - Coal Preparation Plants and
Associated Areas
Since cleaning techniques generally require an alkaline medium
for efficient and economic operation, process water does not
dissolve appreciable quantities of the metallic minerals present
in raw coal. On the other hand, some minerals and salts such as
chlorides and sulfates of the alkalies and the alkaline earth
metals found in raw coal dissolve easily in water. The principal
pollutant present in preparation plant process water, however, is
suspended solids. Process water from plants using froth flota-
tion (Level 4 preparation plants) typically contains less sus-
pended solids than such water from plants that do not recover
coal fines.
All preparation plants studied use water in their cleaning proc-
esses, and 17 of 18 recycle at least 50% of their process water.
The total process water circulated varied from 830 to 12,700 L/Mg
Date: 6/23/80 II.3-7
-------
(240 to 3,700 gal/ton) of coal processed, and process water dis-
charges to surface waters ranged from no discharge to 1,630 L/Mg
of coal produced (475 gal/ton).
Tables 3-2 through 3-4 present the toxic pollutants detected for
raw wastewater and secondary effluents, by subcategory. Tables
3-5 through 3-7 present conventional and classical pollutant raw
wastewater and treated effluent concentrations, by subcategory.
Values are generated from plant specific verification data pre-
sented in Section II.3.3.
II.3.3 PLANT SPECIFIC DESCRIPTION [1]
Reference 1 cites verification data for approximately 18 sample
locations representative of 7 plants. Nine of the 18 sample
locations (representative of 7 plants) had data for both
untreated and treated wastewater, and 9 (representative of 3
plants) had data for treated wastewater only. Tables 3-8 through
3-18 present toxic pollutant and classical pollutant data for
these 18 sample locations on a plant specific basis, by
subcategory.
Verification data were not available to describe "associated
areas," which is consequently defined based on screening data
alone. Table 3-19 presents plant specific data for "associated
areas."
Unless otherwise noted, all values are averages based upon a
3-day sampling period. Whenever a less-than value was encoun-
tered, its limit value was used to compute the given average.
Unless present in all of the initial values, the less-than
symbol (<) was dropped from the final average.
II.3.4 POLLUTANT REMOVABILITY
Full-scale treatment methods that have been cited in the litera-
ture, but for which no data were presented, include: neutraliza-
tion sometimes followed by aeration and oxidation of Fe (II) to
Fe (III) , reverse osmosis, ion exchange, settling, ozonation,
mixed media filtration, and engineering design (planning) to
prevent acid formation (entailing oxygen, water, and contact
time exclusion).
II.3.5 REFERENCES
1. Technical Assistance in the Implementation of the BAT Review
of the Coal Mining Industry Point Source Category (draft
contractor's report). Contracts 68-01-3273, 68-01-4762, and
68-02-2618, U.S. Environmental Protection Agency, Washington,
D.C., March 1979.
Date: 6/23/80 II.3-8
-------
2. Development Document for Interim Final Effluent Limitations
Guidelines and New Source Performance Standards for the Coal
Mining Point Source Category. EPA 440/1-75/057 Group II,
U.S. Environmental Protection Agency, Washington, D.C.,
October 1975.
3. NRDC Consent Decree Industry Summary - Coal Mining.
Date: 6/23/80 II.3-9
-------
ft
(D
NJ
tJ
CO
o
TABLE 3-2.
00
I
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN ACID OR FERRUGINOUS MINE WASTEWATER [1]
Toxic pollutants
Raw wastewater
Number of
sample
locations
Range Median
Treated effluent
Number of
sample
locations Range Median
Metals and inorganics* mg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalatesr pg/L
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
1
1
NA
1
1
1
1
1
1
_a
1
1
1
1
1
1
1
0.034
0.028
NA
0.009
0.010
0.080
0.043
<0.005
0.100
_a
1.000
0.002
0.003
0.008
2.00
<10
<10
0.034
0.028
NA
0.009
0.010
0.080
0.043
<0.005
0.100
_a
1.000
0.002
0.003
0.008
2.00
<10
<10
1
1
NA
1
1
1
1
1
1
_a
1
1
1
1
1
1
1
1
0.016
0.027
NA
<0.001
<0.002
0.020
<0.006
<0.006
<0.020
_a
<0.005
0.003
0.003
<0.005
<0.060
<6.7
<10
<10
0.016
0.027
NA
<0.001
<0.002
0.020
<0.006
<0.006
<0.020
_a
<0.005
0.003
0.003
<0.005
<0.060
<6.7
<10
<10
Analysis not received.
-------
a
0)
rt
(D
CTi
U)
CO
o
TABLE 3-3. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN ALKALINE MINE WASTEWATER [I]
H
10
I
Raw wastewater
Toxic pollutants
Metals and inorganics , mg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates , pg/L
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl pthalate
Diethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds, pg/L
3-3 ' -Dichlorobenzidine
1 , 2-Diphenylhydrazine
N-nitrosodiphenylamine
Phenols, pg/L
2 , 4-Dinitrophenol
Pentachlorophenol
Phenol
Number of
sample
locations Range
5
1
NA
1
1
1
1
5
1
~
1
5
5
5
1
4
4
4
4
4
<0.002
<0
<0
0
0
<0
<0
<0
<0
<0.002
<0.005
<0
<0
ND
ND
ND
ND
- 0.006
.002
NA
.001
.002
.100
.006
.005
.020a
.005
- <0.005
- 0.01
.005
.060
- <10
— <10
-------
D
ft
fl)
•«
o^
\
to
u>
\
00
o
TABLE 3-3 (continued)
U)
i
M
NJ
Raw wastewater
Toxic pollutants
Monocyclic aromatics, ug/L
Benzene
1 / 2-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic
hydrocarbons , vg/L
Anthracene
Benz (a) anthracene
Benzo (ghi) perylene
Dibenz (ah) anthracene
Fluoranthene
Indeno (1,2, 3-cd ) pyrene
Naphthalene
Pyrene
Halogenated aliphatics, ug/L
Carbon tetrachloride
Chloroform
1 , 2-bichloroethane
1 , 1-Dichloroethylene
Hexachloroe thane
Methylene chloride
1,1, 1-Trichloroe thane
1,1, 2-Tr ichloroe thane
Trichloroethylene
Pesticides and metabolites, gg/L
Aldrin
o-BHC
6-BHC
Y-BHC
Heptachlor
Heptachlor epoxide
Number of
sample
locations
4
4
4
4
4
4
4
4
4
4
3
Range Median
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 ND
ND - <10 <1.7
ND - <10 ND
ND - <10 ND
Treated effluent
Number of
sample
locations
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
9
9
9
9
9
9
Ranqe
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
<6.7
<10
<10
<6.7
<6.7
<10
<10
<3.3
8
<6.7
6.3
<10
<3.3
<6.7
<10
<3.3
<10
<6.7
21
<10
<3.3
<3.3
<3.3
0.02
0.05
<10
<3.3
<6.7
Median
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
ND
ND
0.003
ND
ND
ND
ND
ND
Analysis not received.
-------
a
fa
rt
(D
u>
00
o
TABLE 3-4. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN PREPARATION PLANT WASTEWATER [1]
to
I
!-•
U)
Raw wastewater
Number of
sample
Toxic pollutants locations Range
Metals and inorganics, mg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
3
3
NA
3
3
3
3
3
3
_a
3
3
3
3
3
0.002 - 0.034
0.051 - 0.253
NA
<0.010 - 0.057
<0.020
0.233 - 0.530
0.233 - 1.33
<0.005
0.400 - 0.967
_a
0.217 - 1.23
<0.003 - 0.034
<0.002 - <0.005
<0.005 - 0.015
<0.600 - 5.33
Treated effluent
Number of
sample
Median locations Range
<0.005
0.18
NA
<0.01
<0.020
0.367
0.687
<0.005
0.467
_a
0.30
<0.005
<0.005
0.006
<0.600
3
3
NA
3
3
3
3
3
3
_a
3
3
3
3
3
<0.005 - 0.007
0.002 - 0.035
NA
<0.001
<0.002 - 0.003
0.013 - 0.043
0.006 - 0.009
<0.005
<0.020 - 0.053
3
0.003 - 0.100
0.003 * 0.006
<0.002 - <0.005
<0.005
<0.060 - 0.06
Median
0.006
<0.005
NA
<0.001
<0.002
0.013
0.008
<0.005
0.023
_a
0.01
0.003
<0.005
<0.005
<0.060
Ethers, pg/L
Bis(2-chloroethoxy) methane
4-Chlorophenyl phenyl ether
Phthalates, vg/i
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds, ug/L
1,2-Diphenylhydrazine
N-nitrosodiphenylamine
Phenols, yg/L
2-Chlorophenol
2,4-Dimethylphenol
2-Nitrophenol
Phenol
Cresols, yg/L
4,6-Dinitro-o-cresol
ND - 3.3
- 50
<3.3 -
<3.3 -
<3.3 -
ND - <3.3
ND - <3.3
ND - <3.3
ND - 30
ND - 36
ND - 22
ND - 19
ND - <1C
ND - 194
ND
<6.7
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
ND - <3.3
<3.3 - <6.7
ND - <3.3
<3.3 - <10
<3.3 -
ND - <6.7
ND
<6.7
ND
<3.3
<3.3
<3.3
(continued)
-------
D
tu
ft
n>
(Ti
U)
CD
O
I
M
.to.
TABLE 3-4 (continued)
Raw wastowater
Toxic pollutants
Monocyclic aromatics, ug/L
Benzene
2 , 4-Dinitrotoluene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic
hydrocarbons, pg/L
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Benzo(a) pyrene
Benzo (ghi) perylene
Benzo (k) f luoranthene
Chrysene
Dibenz (ah) anthracene
Fluoranthene
Fluorene
Indeno (1,2, 3-cd) pyrene
Naphthalene
Pyrene
Polychlorinated biphenyls
and related compounds, yg/L
2-Chloronaphthalene
Halogenated aliphatics, ug/L
Chloroform
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroe thane
Trichloroethylene
Pesticides and metabolites, pg/L
a-Endosulfan
6-Endosulfan
Isophorone
Number of
sample
locations
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Range
ND -
ND -
ND -
ND -
ND -
ND -
ND -
<10 -
6 -
<10 -
<3.3 -
<3.3 -
ND -
ND -
<6.7 -
<6.7 -
ND -
<10 -
<3.3 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
15
6
<6.7
7
8
'
<10
8
132
10.3
12
12
12
29
<3.3
16
42
<6.7
402
19
<3.3
<6.7
82
7.67
<10
<6.7
<6.7
307
Treated effluent
Number of
sample
Median locations
<3.3
ND
ND 3
ND
ND 3
<3.3
ND
33 3
<10
<10
<10
<10
ND
ND
<10
<10
ND
43.5
<10
ND
ND 3
ND 3
3
3
ND 3
ND 3
ND
ND
ND
Range Median
ND - <3. 3 ND
ND - 7.3 ND
ND-<3.3 <3.3
ND - <6.7 ND
ND - 19 <3.3
ND - <3.3 ND
ND - <3.3 ND
ND - <3. 3 ND
ND - <10 <10
Analysis not received.
-------
TABLE 3-5. WASTEWATER CHARACTERIZATION,
ACID OR FERRUGINOUS MINES[1]
Influent flowrate, gpd: 5,970,000
Characteristics
COD,
TOC,
pH
mg/L
mg/L
Raw
Number of
sample
locations
1
1
1
wastewater
Range
62.
8.
4.
7
0
4
Median
62
8
4
.7
.0
.4
Treated effluent
Number of
sample
locations
1
1
1
Range
4
3
8
.6
.9
.2
Median
4
3
8
.6
.9
.2
TABLE 3-6. WASTEWATER CHARACTERIZATION, ALKALINE MINES [1]
Influent flowrate, gpd: 53,000 median (2,880 to 710,000 range at
5 sample locations)
Raw wastewater
Number of
sample
Characteristics locations Range
COD,
TOC,
mg/L
mg/L
Total phenols, mg/L
PH
5
5
5
5
14.3
7.2
<0.010
6.6
- 90
- 57
- <0
- 8.
.7
.0
.020
2
Treated effluent
Number of
sample
Median locations
24.0
23.3
<0.010
7.6
14
14
14
14
13
2
Range ,
.7 -
.9 -
<0.010 -
6
.3 -
136
65.3
<0.020
8.5
Median
22.5
7.8
<0.010
7.8
Date: 6/21/79
TABLE 3-7. WASTEWATER CHARACTERIZATION, PREPARATION PLANTS [1]
Influent flowrate, gpd: 9,976,000 median (274,000 to 12,432,960 range at
3 sample locations)
Raw wastewater
Number of
sample
Characteristics locations Range
COD, mg/L
TOC, mg/L
Total phenols, mg/L
pH
3
3
3
3
20,724 -
1,492 -
<0.010 -
6.6 -
46,792
8,447
<0.020
7.3
Median
36,300
2,063
<0.010
6,37
Treated effluent
Number of
sample
locations Range
3
3
3
3
19.2
6.8
<0.010
6.8
- 118.7
- 96.8
- <0.020
- 7.4
Median
20.3
19.1
<0.010
6.9
Date: 6/23/80
II.3-15
-------
TABLE 3-8. WASTEWATER CHARACTERIZATION, MINE NC-20 [1]
Category: Coal Mining
Subcategory: Acid or Ferruginous Mines
Raw vastevater flowrate, gpd: 5,790,000
Hastewater
characterization
Pollutant
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
pH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Toxic pollutants, ug/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachlor oe thane
1 , 2-Dichloroe thane
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
1,1,2, 2-Tetrachloroe thane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
Raw wastewater ,
characterization
134.4
391.3
1.4
62.7
8'°d
4.4
<0.010
46.7
0.034
0.028°
<0.005
0.009
0.333
0.010
367
0.080
0.367
0.043
167
0.100
100
"•
0.083
1.000
0.002
0.003
403
0.008
0.093
<0.020
0.040
0.167
2.00
<0.005
e
_e
e
e
ND
e
e
_e
~e
ND
e
ND
Treated effluent
concentration
47
90
<0.1
4.6
3'9d
8.2
<0.010
0.133
0.016
0.027
<0.005
<0.001
0.267
<0.002
570
0.020
<0.005
<0.006
0.233
<0.020
57.3
0.833e
-
<0.005
<0.005
0.003
0.003
427
<0.005
0.020
<0.020
<0.010
<0.020
<0.060
<0.005
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
Date: 6/23/80
II.3-16
-------
TABLE 3-8 (continued)
Pollutant
Toxic pollutants, gg/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3' -Dichlorobenzidine
1,1-Dichloroethylene
2,4-Dimethylphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy) me thane
Methylene chloride
Bromoform
Trichlorfluorone thane
Isophorone
Naphtha.lene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
Bis (2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz(a) anthracene/chrysene
Benzo(a)pyrene
Benzo (b) f luoranthene/
benzo(k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi ) pery lene
Fluorene
Dibenz (ah) anthracene
Indenod , 2 , 3-cd)pyrene «
Pyrene
Tetrachloroa thy lene
Toluene
Trichloroe thy lene
Aldrin
a-Endosulfan
6-Endoaulfan
Endrin
Heptachlor
Heptachlor epoxide
o-BHC
t-BHC
S-BHC
Wastewater
characterization
Raw wastewater . Treated effluent
b c
characterization concentration
ND
ND
ND
e
ND
ND
ND
-
ND
ND
ND
£
C
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-C
„
e
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
<10
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
aAll data based on 3-day sampling, except as noted.
b
Raw mine water.
CTreated effluent.
d
Data based on 2 days.
Analysis not available.
Date: 6/23/80 II.3-17
-------
o
PJ
TABLE 3-9. WASTEWATER CHARACTERIZATION, MINE NC-8 [1]
to
U)
CO
O
u>
I
M
00
Category: Coal Mining
Subcategory: Alkaline Mines
Raw wastewater flowrate, gpd: 12,432,960
Raw wastewater
Pollutant Influent to pond 003
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
pH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin'
Titanium
Vanadium
Yttrium
Zinc
Cyanide
7.9
207
<0.1
24
23.3
6.6°
<0.020
0.97
<0.002
<0.002
0.013
<0.001
0.43
0.002
243
0.100
<0.005
<0.006
0.630
<0.020
100
4.000
d
<0.005
<0.005
<0.005
<0.005
313
<0.005
0.030
<0.020
<0.010
<0.020
<0.060
<0.005
Treated effluent
Nondischarging Nondischarging Active pond 004 Active pond 005
active pond 002 active pond 003 treated effluent treated effluent
16.4
197
0.1
13.9
2.9
8.3
<0.020
0.700
0.002
0.002
0.009
<0.001
0.300
<0.002
110
0.037
-------
D
0)
rt
(D
TABLE 3-9 (continued)
co
00
O
H
•
CO
I
Treated effluent
Raw wastewater Nondischarging Nondischarging Active pond 004 Active pond 005 Nondischarging
Pollutant influent to pond 003 active pond 002 active pond 003 treated effluent3 treated effluent* active pond 006
Toxic pollutants, gg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroe thane
1 , 2-Dichloroe thane
1,1, 1-Trichloroe thane
1,1, 2-Tr ichloroethane
1 , 1 , 2, 2-Tetrachloroe thane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3' -Dichlorobenzidine
1 , 1-Dichloroethy lene
2 , 4-Dimethy Iphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis ( 2-chloroethoxy ) methane
Methylene chloride
Bromoform
Tr i chlor of luor one thane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C
<10
<10r
C
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
c
c
ND
<10C
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NLJ
ND
ND
ND
ND
Mn
wu
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
f
~ f
<6.7f
~f
-f
-
NDf
ND
<6.7
<6.7
<6.7f
ND
ND
NDf
<6.7
ND
NDf
~t
_f
ND
ND
ND
ND
ND
ND
f
"f
~f
~{
~{
~f
~f
~f
~f
NDf
""
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
< 1Q
-------
a
OJ
rt
(D
U)
00
O
TABLE 3-9 (continued)
H
U)
I
, —
Raw wastewater Nondisr-harging Nondisr-harqinq
Pollutant influent to pond 003 active pond 002 active pond 003 t
Toxic pollutants, ug/L (cont'd)
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a ) anthracene/chrysene
Benzo (a )py rene
Benzo (b) f luoranthene/
benzo ( k ) f luor an thane
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi)perylene
Fluorene
Dibenzo(ah) anthracene
Indeno (1,2, 3-cd ) py rene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
o-Endosulfan
B-Endosulfan
Endrin
Heptachlor
Heptaclor epoxide
a-BHC
T-BHC
(5-BHC
2,4-Dinitrophenol
Pentachlorophenol
<10
<10
<10
ND
ND
c
c
c
c
ND
<10
<10
ND
<10
<10
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
'10
'10
'10
ND
'10
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
<10
'10
'10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
Treated effluent
Active pond 004 Active pond OO5 Nondischarqi ng
reatrd effluent treated effluent active pond 006
'10
'10
ND
<10
ND
<3.3
ND
ND
ND
<3.3
<3.3
ND
8
6.3
<3.3,
f
f
"f
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
'10
'10
'6.7
ND
ND
ND
ND
ND
'3.3
ND
ND
ND
ND
ND
ND
ND
_
t
f
f
f
~f
~f
~f
<3.3
<3.3
'10
'10
'10
'10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
Data for toxic pollutants based on 2-day sampling, except as noted.
All data for classical parameters and metals based on 3-day sampling, except as noted.
CData based on 2-day sampling.
Analysis not available.
eData for toxic pollutants are based on 1-day sampling, except as noted.
Data based on 1-day sampling.
-------
o
0)
ft
(D
TABLE 3-10. WASTEWATER CHARACTERIZATION, MINE V-8 [11
\ Category: Coal Mining
w Subcategory: Alkaline Mines
oo
o
U)
I
Raw wastewater flowrate, gpd: 53,000
Wastewater
characterization
Raw wastewater ,
Pollutant characterization
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
PH
Phenol, mg/L
Metals, mg/L
Antimony
Arsenic
Selenium
Silver
Thallium
Cyanide
102.7
243.3
0.13
90.7
57.0
7.6
<0.010
0.006
0.004
0.002
<0.005
<0.005
<0.005
Treated effluent
concentration0
28.5
365.3
0.10
76.0
57.8
8.1
<0.010
0.011
<0.002
0.002
<0.005
<0.005
<0.005
aAll data based on 3-day sampling, except as noted.
Pond #4 influent.
CPond #4 effluent.
-------
TABLE 3-11. WASTEWATER CHARACTERIZATION, MINE V-8 [1]
Category: Coal Mining
Subcategory: Alkaline Mining
Raw wastewater flowrate, gpd:
2,880
Wastewater
characterization
Pollutant
Raw wastewater .
characterization
Treated effluent
concentration0
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
PH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Toxic pollutants, pg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
44.8
168.0
80'.0
54.3
7.9
<0.010
0.027
0.006
0.002
<0.005
<0.005
<0.005
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
28.9
123.1
38,
21,
8,
<0.010
0.015
0.005
<0.002
<0.005
<0.005
<0.005
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
<6.7
ND
(continued)
Date: 6/23/80
II.3-22
-------
TABLE 3-11 (continued)
Pollutant
Toxic pollutants, pg/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3' -Dichlorobenzidine
1 , 1-Dichloroethylene
2 , 4-Dimethylphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy) methane
Methylene chloride
Bromoform
Trichlorf luoromethane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodi phenyl ami ne
Phenol
Bis (2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a ) anthracene/chrysene
Benzo (a) pyrene
Benzo (b) f luoranthene/
benzo (k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi ) perylene
Fluorene
Dibenz (ah) anthracene
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulf an
6-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Wastewater
characterization3
Raw wastewater . Treated
effluent
characterization concentration0
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
<10
ND
ND
ND
<3.3
ND
ND
ND
13.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
<3.3
<3.3
ND
ND
ND
<3.3
<6.7
ND
<10
ND
Note: Blanks indicate data not received.
aAll data based on 1-day sampling,
Pond No. 6 influent.
cPond No. 6 effluent.
Date: 6/23/80
II.3-23
-------
TABLE 3-12. WASTEWATER CHARACTERIZATION, MINE V-8 [1]
Category: Coal Mining
Subcategory: Alkaline Mines
Wastewater
characterization
Raw wastewater . Treated effluent
Pollutant characterization concentration
Classical parameters
TSS, mg/L 61.9
Total volatile solids, mg/L 418
Settleable solids, mL/L <0.1
COD, mg/L 136
TOC, mg/L 65.3
pH 8.1
Phenol, mg/L <0.010
Metals, mg/L
Aluminum
Antimony 0.010
Arsenic 0.005
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium 0.003
Silver <0.005
Sodium
Thallium 0.006
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide <0.005
Toxic pollutants, yg/L
Acenaphthene ND
Benzene <6.7
Carbon tetrachloride ND
Chlcrobenzene ND
Hexachloroethane ND
1,2-Dichloroethane ND
1,1,1-Trichloroethane <10
1,1,2-Trichloroethane ND
1,1,2,2-Tetrachloroethane ND
2-Chloronaphthalene ND
Chloroform ND
2-Chlorophenol ND
(continued)
Date: 6/23/80 II.3-24
-------
TABLE 3-12 (continued)
Wastewater
characterization
Raw wastewater . Treated effluent
Pollutant characterization concentration
Toxic pollutants, pg/L (cont'd)
1,2-Dichlorobenzene ND
1,4-Dichlorobenzene ND
3,3'-Dichlorobenzidine ND
1,1-Dichloroethylene <10
2,4-Dimethylphenol ND
2,4-Dinitrotoluene ND
1,2-Diphenylhydrazine ND
Ethylbenzene ND
Fluoranthene ND
4-Chlorophenyl phenyl ether ND
Bis (2-chloroethoxy(methane ND
Methylene chloride 12.7
Brorooform ND
Trichlorfluoromethane ND
Isophorone ND
Naphthalene ND
Nitrobenzene ND
2-Nitrophenol ND
4,6-Dinitro-o-cresol ND
N-nitrosodiphenylamine ND
Phenol ND
Bis<2-ethylhexyl) phthalate ND
Butyl benzyl phthalate <3.3
Di-n-butyl phthalate <3.3
Di-n-octyl phthalate ND
Diethyl phthalate ND
Dimethyl phthalate ND
Benz (a)anthracene/chrysene ND
Benzo (a)pyrene ND
Benzo(b)fluoranthene/
benzo(k)fluoranthene ND
Acenaphthylene ND
Anthracene/phenanthrene ND
Benzo(ghi)perylene ND
Fluorene ND
Dibenz(ah)anthracene ND
Indeno(1,2,3-cd)pyrene ND
Pyrene ND
Tetrachloroethylene ND
Toluene <6.7
Trichloroethylene <3.3
Aldrin ND
a-Endosulfan ND
B-Endosulfan ND
Endrin ND
Heptachlor <6.7
Heptachlor epoxide ND
a-BHC ND
Y-BHC <3.3
6-BHC ND
Note:Blanks indicate data not received.
aAll data based on 3-day sampling.
Raw wastewater data not available.
cGrab composite from three ponds.
Date: 6/23/80 II.3-25
-------
TABLE 3-13. WASTEWATER CHARACTERIZATION, MINE V-9 [1]
Category: Coal Mining
Subcategory: Alkaline Mines
Raw wastewater flowrate, gpd:
710,000
Wastewater
characterization
Pollutant
Classical parameters
TSS, rog/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
pH
Phenol , mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Raw wastewater .
characterization
61.0
99.0
0.11
16.3
10.8
8.2
<0.010
<0.002
0.002
<0.002
0.01
<0.005
<0.005
Treated effluent
concentration0
78'6d
52 -5d
<0.1d
13.7
9.6
7.7
<0.010
<0.002
<0.002
<0.002
<0.01
<0.005
<0.005
Toxic pollutants, yg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
(continued)
Date: 6/23/80
II.3-26
-------
TABLE 3-13 (continued)
Pollutant
Toxic pollutants, pg/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3" -Dichlorobenzidine
1 , 1-Dichloroethylene
2 , 4-Dimethylphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy)methane
Methylene chloride
Bromof orro
Trichlorf luororaethane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a ) anthracene/chrysene
Benzo (a) pyrene
Benzo (b1) f luoranthene/
benzo (k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi ) perylene
Fluorene
Dibenz (ah) anthracene
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulfan
g-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Wastewater
characterization
Raw wastewater . Treated effluent
characterization concentration
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
<10.0
ND
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Note: Blanks indicate data not received.
aAll data from 3-day sampling, except as noted.
Pollack pond raw water.
cPollack pond settling pond effluent.
Data from 2 days.
Date: 6/23/80
II.3-27
-------
TABLE 3-14. WASTEWATER CHARACTERIZATION, MINE V-9 [1]
Category: Coal Mining
Subcategory: Alkaline Mines
Raw wastewater flowrate, gpd:
41,000
Wastewater
characterization
Pollutant
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
PH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
yttrium
Zinc
Cyanide
Raw wastewater .
characterization
110.6
122
0.33
14.3
7.2
7.6
<0.010
<0.002
<0.002
0.003
0.01
<0.005
<0.005
Treated effluent
concentration
46.1
75
0.17
18.3
14.6
7.5
<0.011
<0.002
<0.002
<0.002
<0.01
<0.005
<0.005
Toxic pollutants, pg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
Date: 6/23/80
II.3-28
-------
TABLE 3-14 (continued)
Pollutant
Toxic pollutants, yg/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenrene
3,3' -Dichlorobenzidine
1 , 1-Dichloroethylene
2 , 4-Dimethylphenol
2 ,4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy)methane
Methylene chloride
Bromoform
Trichlorfluorome thane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a)anthracene/chrysene
Benzo (a) pyrene
Benzo (b) f luoranthene/
benzo(k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi)perylene
Fluorene
Dibenz (ah) anthracene
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulfan
6-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Wastewater
characterization
Raw wastewater . Treated effluent
characterization concentration
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
O.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
<6. 7
ND
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Note: Blanks indicate data not received.
°All data from 3-day sampling.
Dugout pond raw water.
cDugout pond settling pond effluent.
Date: 6/23/80
II.3-29
-------
TABLE 3-15. WASTEWATER CHARACTERIZATION, MINE NC-22 [1]
Category: Coal Mining
Subcategory: Alkaline Mines
CO
o
H
•
U)
I
Pollutant
Classical parameters
TSS , mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD , mg/L
TOC, mg/L
PH
Phenol , mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Nondischarging
active pond
Raw wastewater P 1371 AD-002
19.6
217.7
NA
17.6
8.3
7.4
<0.010
<0.050
0.016
<0.005
0.037
<0.001
0.093
<0.002
250
0.060
<0.005
<0.006
<0.200
0.020
91
0.197
<0.001
0.017
<0.005
0.003
<0.005
59
<0.005
0.008
<0.020
<0.010
<0.020
<0.060
<0.005
Nondischarging
inactive pond
P 485-001
20.7
86
NA
21.1
7.5
6.3
<0.010
0.130
0.010
<0.005
0.060
<0.001
0.067
0.004
58
0.020
0.006
0.008
0.833
0.083
23
0.233
<0.001
0.020
0.027
0.003
<0.005
<15
<0.005
0.030
-------
D
fa
rt
(D
TABLE 3-15 (continued)
to
00
O
U)
I
U>
Pollutant
Raw wastewatera
Nondischarging
active pond •
P 1371 AD-002
Nond i scha rg i ng
inactive pond
P 485-001
Nond i scha rg i ng
active pond
P 0063 AD-001
Nond i scha r'.} ing
inactive pond
P 0063 AD-002
Toxic pollutants, ug/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroe thane
1 , 2-Dichloroethane
1,1, 1-Tr ichloroe thane
1,1, 2-Tr ichloroethane
1,1, 2, 2-Tetrachloroethane
2-Ch loronaph tha lene
Chloroform
2-Chlorophenol
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3* -Dichlorobenzidine
1 , 1-Dichloroe thy lene
2 , 4-Dimethy Iphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
F luoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy) me thane
Methylene chloride
Br OHIO form
Trichlorf luorome thane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
ND
<3.3
ND
ND
ND
<3.3
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
21
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
<10
ND
ND
<3.3
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
<10
ND
ND
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
<3.3
ND
<10
ND
ND
<3.3
ND
ND
ND
ND
'3.3
<3.3
ND
ND
<6.7
ND
ND
ND
ND
<3.3
ND
ND
ND
<3.3
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
<10
ND
(continued)
-------
rt
fD
CTl
\
KJ
U)
\
00
o
H
CO
I
co
NJ
TABLE 3-15 (continued)
Pollutant
Toxic pollutants, gg/L (cont'd)
Diethyl phthalate
Dimethyl phthalate
Benz (a) anthracene/chrysene
Benzo(a) pyrene
Benzo(b) f luoranthene/
benzo(k) f luoranthene
Acenaph thy lene
Anthracene/phenanthrene
Benzo (ghi) pery lene
Fluorene
Dibenz (ah) anthracene
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroe thy lene
Toluene
Trichloroe thy lene
Aldrin
a-Endosulfan
$-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Nondischarging
active pond
Raw wastewater3 P 1371 AD-002
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3. j
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Nondischarging
inactive pond
P 485-001
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Nondischarging
active pond
P 0063 AD-001
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.007
ND
ND
ND
ND
ND
ND
ND
0.007
Nondischarging
inactive pond
P 0063 AD-002
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
0.003
ND
ND
ND
ND
ND
0.02
ND
0.05
Raw wastewater data not available.
-------
TABLE 3-16. WASTEWATER CHARACTERIZATION, PLANT NC-8 [I]
Category: Coal Mining
Subcategory: Preparation Plant6
Raw wastewater flowrate, gpd: 12,432,960
Wastewater
characterization
Pollutant
Classical parameters0
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
PH
Phenol, mg/L
Metals, mg/L
Aluminum
Ar. timony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Toxic pollutants, pgYLe
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachl or oe thane
1 , 2-Dichloroe thane
1,1, 1-Tr ichloroe thane
1,1, 2 -Tr ichloroe thane
1,1,2, 2-Tetrachloroe thane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
Raw wastewater
characterization
34,400
18,131
247
36,300
1,492
7.3
<0.020
200
0.002
0.253
5.67
0.057
3.00
<0.020
493
0.530
0.500
1.33
1,000
0.967
87
8.0
NA
0.600
1.23
<0.005
<0.005
293
0.006
0.200
3.67
0.833
0.333
5.33
<0.005
<10
15
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated effluent
concentration''
8.9
163.3
<0.1
19.2
96.8
7.4fl
<0.020
<0.050
0.006
0.002
0.050
<0.001
0.767
<0.002
77
0.013
<0.005
0.006
0.267
<0.020
25
0.050
NA
0.040
<0.005
0.006
<0.005
283
<0.005
<0.005
<0.020
<0.010
<0.020
<0.060
<0.005
~d
~3
~ j
u
~d
~d
~j
Q
~d
ND,
Q
~ J
U
(continued)
Date: 6/23/80
II.3-33
-------
TABLE 3-16 (continued)
pollutant
Toxic pollutants, rog/L (cont'd)
1 2-Dichlorobenzene
1 4-Dichlorobenzene
3 3'-Dichlorobenzidine
1 1-Dichloroethylene
2 4-Dimethylphenol
2 4-Dinitrotoluene
1 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-chlorophenyl phenyl ether
Bis (2-chloroethoxy)methane
Methylene chloride
Bromoform
Trich lor fluorome thane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylan\ine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a) anthracene/chrysene
Benzo(a)pyrene
Benzo (b) f luoranthene/
benzo (k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi) perylene
Fluorene
Dibenz (ah) anthracene
Indeno(l,2 ,3-cd)pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulfan
6-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Wastewater
characterization
Raw wastewater Treate
characterization conce
KD
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
<10
<10
<10
<10
ND
<10
ND
<10
<10
<10
ND
<10
<10
<10
ND
ND
<10
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
d effluent
ntrationc
d
~d
~d
~d
~d
ND
NDd
ND
ND
ND
<3.3d
~d
ND
ND
NDd
~d
ND
<5.0
<3.3
<3.3
<3.3
ND
<3.3d
~ A
u
"" H
u
ND
ND
ND
ND
ND
ND
ND,
Q
d~
~ d
ND
ND
ND
ND
ND
ND
ND
ND
ND
Slurry pond influent.
Slurry pond decant.
CA11 data for classical parameters and'metals representative of 3-day
sampling, except as noted.
Data from 2-day sampling.
eData for toxic pollutants are for 1-day sampling, except as noted.
Date: 6/23/80
II.3-34
-------
TABLE 3-17. WASTEWATER CHARACTERIZATION, PLANT NC-20 [1]
Category: Coal Mining
Subeategory: Preparation Plants
Raw wastewater flowrate, gpd: 9,976,000
Wastftwater
characterization
Pollutant
Classical parameters
TSS, mg/L
Total volatile solids, mg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
PH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Toxic pollutants, yg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroe thane
1 , 2-Dichloroe thane
1,1, 1-Tr ichloroethane
1,1, 2-Tr ichloroethane
1,1,2, 2-Tetrachloroe thane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
Raw wastewater .
characterization
9,131
7,567
56.3
20,724
2,868
6.87
<0.010
35
0.034
0.051
0.353
<0.010
0.600
<0.020
453
0.367
<0.050
0.687
70
0.400
58
2.67
NA
0.100
0.217
<0.003
<0.002
480
<0.005
<0.060
0.767
0.200
<0.200
<0.600
<0.005
<3.3
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated effluent
concentration0
62.9
254
0.2
118.7
19. ld
6.8d
<0.010
0.100
0.007
0.035
0.167
<0.001
0.300
<0.002
440
0.013
0.023
0.009
3.333
0.023
40
2.00
NA
0.008
0.100
0.003
<0.002
397
<0.005
<0.005
<0.005
<0.010
<0.020
0.060
<0.005
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
Date: 6/23/80
II.3-35
-------
TABLE 3-17 (continued)
Pollutant
Toxic pollutants, vg/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3' -Dichlorobenzidine
1 , 1-Dichloroethylene
2,4-Dimethylphenol
2 ,4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis (2-chloroethoxy)methane
Methylene chloride
Bromof orm
Trichlorfluorome thane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylaroine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a) anthracene/chrysene
Benzo(a)pyrene
Benzo (b) f luoranthene/
benzo (k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi) perylene
Fluorene
Dibenz (ah) anthracene.
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulfan
B-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
o-BHC
Y-BHC
6-BHC
Wastewater
characterization
Raw wastewater . Treated effluent
characterization concentration
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
ND
ND
ND
ND
ND
43.5
ND
ND
ND
ND
ND
50
<3.3
<6.7
ND
<3.3
ND
10.3
<10
<3.3
ND
33
<6.7
<6.7
ND
ND
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
ND
<10
ND
<10
ND
ND
ND
ND
ND
<3.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
aAll data based on 3-day sampling, except as noted.
bSlurry.
°Recycled preparation plant water.
Data from 2-day sampling.
Date: 6/23/80
II.3-36
-------
TABLE 3-18. WASTEWATER CHARACTERIZATION, PLANT NC-22 [1]
Category: Coal Mining
Subcategory: Preparation Plants
Raw wastewater flowrate, gpd: 274,000
Wastewater
characterization*
Pollutant
Classical parameters
TSS, mg/L
Total volatile solids, reg/L
Settleable solids, mL/L
COD, mg/L
TOC, mg/L
pH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
Yttrium
Zinc
Cyanide
Toxic pollutants, pg/L
Acenaphthene
Benzene
Carbon tetrachloride
Chlorobenzene
Hexachloroethane
1 , 2-Dichloroethane
1,1, 1-Tr ichloroethane
1,1, 2-Trichloroethane
1,1,2, 2-Tetrachloroethane
2-Chloronaphthalene
Chloroform
2-Chlorophenol
Raw wastewater .
characterization
13,876
17,908
202
48,792
8,447
6.6
<0.010
57
<0.005
0.18
2.0
-------
TABLE 3-18 (continued)
Pollutant
Toxic pollutants, ug/L (cont'd)
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
3,3' -Dichlorobenzidine
1 , 1-Dichloroethylene
2 , 4-Dimethylphenol
2 , 4-Dinitrotoluene
1 , 2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
4-Chlorophenyl phenyl ether
Bis ( 2-chloroethoxy ) methane
Methylene chloride
Bromoform
Trichlorf luoromethane
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4 , 6-Dinitro-o-cresol
N-nitrosodiphenylamine
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Benz (a) anthracene/chrysene
Benzo (a) pyrene
Benzo (b) f luoranthene/
benzo(k) f luoranthene
Acenaphthylene
Anthracene/phenanthrene
Benzo (ghi) perylene
Fluorene
Dibenz (ah) anthracene
Indeno (1,2, 3-cd) pyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Aldrin
a-Endosulfan
B-Endosulfan
Endrin
Heptachlor
Heptachlor epoxide
a-BHC
Y-BHC
6-BHC
Wastewater
characterization
Raw wastewater . Treated effluent
characterization concentration
ND
ND
ND
ND
22
6
<3.3
<6.7
16
<3.3
ND
82
ND
ND
307
402
7
19
194
30
<10
<10
<3.3
<3.3
<3.3
<3.3
<3.3
6/29
12
12
8
132
12
47
<3.3
<6.7
19
ND
8
<10
ND
<6.7
<6.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<3.3
ND
ND
<3.3
19
ND
ND
ND
ND
ND
ND
ND
ND
<6.7
<6.7
ND
<3.3
ND
<3.3
ND
ND
ND
ND
ND
<3.3
ND
ND
ND
ND
ND
<3.3
7.3
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
nAll data based on 3-day sampling, except as noted.
bSlurry.
cSlurry effluent.
Data based on 2-day sampling.
Date: 6/23/80
II.3-38
-------
TABLE 3-19. WASTEWATER CHARACTERIZATION, PLANT NC-15 [I]
Category: Coal Mining
Subcategory: Associated Areas (screening data)
Wastewater
characterization
Pollutant
Classical parameters
Total solids, mg/L
TSS, mg/L
Total volatile solids, mg/L
Volatile suspended solids, mg/L
COD, mg/L
TOC, mg/L
pH
Phenol, mg/L
Metals, mg/L
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Vanadium
yttrium
Zinc
Cyanide
Toxic pollutants, ug/L
Benzene
Chlorobenzene
1 , 2-Dichloroe thane
1,1, 1-Tr ichloroethane
1,1,2, 2-Tetrachloroe thane
Chloroform
1 , 2-trans-Dichloroethylene
2, 6-Dinitrotoluene
Ethylbenzene
Methylene chloride
Trichlorfluorome thane
Toluene
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Anthracene/phenanthrene
Raw wastewater .
characterization
410
11.4
34
2.2
15.5
3.6
4.0
<0.02
1.47
0.002
0.003
0.127
<0.002
0.024
<0.02
26.5
<0.024
0.038
0.006
0.509
<0.06
15.5
2.09
0.0048
<0.01
<0.05
0.003
<0.025
38.8
<0.001
<0.099
0.014
<0.099
<0.01
0.168
<0.005
48
KD
ND
ND
NO
45
ND
ND
ND
460
ND
14
ND
ND
ND
ND
Treated effluent
concentration0
260
62
36
19.6
29.1
5.5
9.7
<0.035
<0.99
0.002
0.004
0.17
<0.02
0.11
<0.2
8.0
<0.24
<0.1
<0.04
1.0
<0.6
3.0
<0.2
0.0043
<0.1
<0.5
0.004
<0.250
65.0
<0.001
<0.99
<0.1
<0.99
<0.1
<0.25
<0.005
6.3
ND
ND
1.7
1.2
19
1.7
ND
ND
66,000
22
2.0
6,100
210
ND
ND
aAll data based on 1-day sampling.
Refuse pile raw water.
cRefuse pile treated effluent.
Date: 6/23/80 II.3-39
-------
II.4 ELECTROPLATING
II.4.1 INDUSTRY DESCRIPTION
II.4.1.1 General Description [1]
The Electroplating Industry includes those facilities that apply
a metallic surface coating to a second material typically by
electrodeposition to provide corrosion protection, wear or
erosion maintenance, antifrictional characteristics, or for
decorative purposes. Approximately 13,000 companies are engaged
in some phase or type of metal plating in the United States. Of
these, 74% are captive shops (i.e., facilities plating products
made in shop), while the remaining companies are independent
(job) platers.
Electroplating facilities vary greatly in size and character
from one plant to another. A single facility for plating
individual parts formed by stamping, casting, and machining may
employ plating or processing solutions (excluding water rinses)
ranging in volume from less than 0.4 m3 (100 gal) to more than
20 m3 (5,300 gal). The area of the products being plated in
these facilities varies as much as three orders of magnitude,
from less than 10 to more than 1,000 m2/d (100 to 10,000 ft2/d).
The power consumed by a single facility varies from a few kWh/
day to as much as 20,000 kWh/day. Products being plated vary in
size from less than 6.5 cm2 (1 in.2) to more than 1m2 (10 ft2)
and in weight from less than 30 g (1 oz) to more than 9,000 kg
(10 tons). Continuous strip and wire are plated in some plants
on a 24-hr/d basis. Some companies have capabilities for electro-
plating 10 or 12 different metals and alloys, but others special-
ize in just 1 or 2. Because of differences in character, size,
and processes, facilities are custom tailored to the specific
needs of each individual plant.
Table 4-1 presents an industry summary for the Electroplating
Industry including the total number of subcategories, number of
subcategories studied, and the types of dischargers.
The industry dischargers in the table do not add up to the 13,000
initially estimated. This may be due to an overestimation by the
first reference or to exclusion of some of the plants from the
second reference.
Date: 6/23/80 II.4-1
-------
TABLE 4-1. INDUSTRY SUMMARY
Industry: Electroplating
Total Number of Subcategories: 10
Number of Subcategories Studied: 10
Number of Dischargers in Industry:
• Direct: 2,932
Indirect: 6,586
Zero: 200
II.4.1.2 Subcategory Descriptions [1]
The industry summary (Table 4-1) notes that this industry has 10
Subcategories. However, the primary reference used for this
industry report (written in August 1979) lists only seven
Subcategories. The three missing Subcategories may have been
absorbed into other Subcategories or may have been eliminated
because of their insignificance in the industry. This report
will be limited to the seven Subcategories for which descriptions
are available:
(1) Common Metals Plating
(2) Precious Metals Plating
(3) Anodizing
(4) Coating
(5) Chemical Milling and Etching
(6) Electroless Plating
(7) Printed Circuit Board Manufacturing
Although the Subcategories are not mutually exclusive subdivi-
sions of this industry, the categorization is based on the fact
that distinctly different production processes are performed
in each of the Subcategories. The subcategory descriptions
that follow provide an overview of the industry in the area of
production processes and product descriptions.
Surface preparation, plating, and posttreatment are process steps
common to nearly all the Subcategories. To avoid repetition
these three steps will be briefly described before the subcate-
gory descriptions are presented.
Surface Preparation
The surface of the basic material must be cleaned or descaled
prior to plating. Cleaning removes from the surface the oil,
grease, and dirt that interefere with the plating step. Any of
several cleaning methods may be used, including solvent, alkaline,
acid, emulsion, and ultrasonic cleaning. Associated with each
Date: 6/23/80 II.4-2
-------
method are advantages and disadvantages that affect the cleaning
potential, polluting potential, and type of metal to be plated.
Solvent cleaning of metals is classified as either hot cleaning,
such as vapor degreasing, or cold cleaning, in which the solvent
is used at room temperature. Hot cleaning is effective in remov-
ing lubricants high in nonsaponifiable oils or sulfurized or
chlorinated components. Cold cleaning solvents are selected
based on the type of soil to be eliminated.
Alkaline cleaning is used to remove oily soils or solid soil from
workpieces. The detergent nature of the solution provides the
majority of the cleaning action, with agitation of the solution
being secondary. Pieces may be sprayed, soaked, or cleaned
electrolytically. Electrolytic cleaning produces the cleanest
surfaces available from conventional methods of alkaline cleaning
as a result of solution agitation by the gas evolution and the
oxidation-reduction reactions that occur.
Emulsion cleaners consist of common organic solvents dispersed
in an aqueous medium by emulsifying agents. Emulsion cleaning is
conducted in the same manner as solvent cleaning.
Ultrasonic energy is finding increased use for the agitation of
cleaning solutions and may represent substantial savings in time
and labor. Ultrasonic cleaning is used to remove difficult
inorganic and organic soils from intricate parts.
Acid cleaning is used to remove oxides that are formed on the
metal surfaces prior to plating. The removal involves the dis-
solution of the oxide in an acid. Sulfuric, hydrochloric, and
phosphoric acids are most commonly used.
Each of the above cleaning processes potentially generates waste-
water pollutants in the form of the soils on the materials and
the cleaning solutions used. Normally several of the above
processes are used to ensure that the surface is thoroughly
cleaned.
Salt bath descaling uses as molten salt bath - water quench -
acid dip sequence to clean hard-to-remove oxides from stainless
steels and other corrosion-resistant alloys. The work is immersed
in the molten salt (temperature range from 400°C to 540°C), water
quenched, and then acid dipped. Oxidizing, reducing, and electro-
lytic baths are available; the oxide to be removed governs the
choice of bath.
Plating
The electroplating processes apply a surface coating for func-
tional or decorative purposes. In electroplating, metal ions in
Date: 6/23/80 II.4-3
-------
either acid, alkaline, or neutral solutions are reduced on
cathodic surfaces (the surfaces of the workpiece being plated).
The metal ions in solution are usually replenished by the
dissolution of metal from anodes or small pieces contained in
inert wire or expanded metal baskets. Replenishment with
metal salts is also practiced, especially for chromium plating.
In this case, an inert material must be selected for the anodes.
Hundreds of different electroplating solutions have been adopted
commercially, but only two or three types are utilized widely for
any particular metal or alloy. Cyanide solutions are popular
for copper, zinc, brass, and cadmium, for example, yet noncyanide
alkaline solutions containing pyrophosphate or another agent have
come into use in recent years for zinc and copper. Zinc, copper,
tin, and nickel are plated with acid sulfate solutions, especially
pieces with relatively simple shapes. Cadmium and zinc are
sometimes electroplated from neutral or slightly acid chloride
solutions.
The electroplating process is basically an oxidation-reduction
reaction. Typically, the part to be plated is the cathode, and
the plating metal is the anode. Thus, to plate copper on zinc
parts, the zinc parts are the cathodes, and the anode is a copper
bar. On the application of electric power, the copper bar anode
will be oxidized, dissolving it in the electrolyte (which could
be copper sulfate):
Cu = Cu+2 + 2e~
The resulting copper ions are reduced at the cathode (the zinc
part) to form a copper plate:
Cu+2 + 2e~ = Cu
With some exceptions, notably chromium plating, all metals are
usually electroplated in a similar manner. In chromium plating,
the typical anode material is lead, and the chromium is supplied
to the plating baths as chromic acid.
Parts are most commonly plated either in barrels or on racks.
Barrel plating is used for small parts that tumble freely in
rotating barrels. Direct current loads up to several hundred
amperes are distributed to the parts being plated. For rack
plating, parts may be attached to plastic-coated copper frames
designed to carry current equally to a few hundred small parts,
several medium-size shapes, or just a few large products through
springlike rack tips affixed to the rack splines. Racks fabri-
cated for manual transfer from cleaning, plating, and rinsing
tanks usually hold workpieces totaling 0.5 to 1 m2 (5 to 10 ft2)
in area. Larger racks for heavier parts are constructed for
use with mechanical hoist and transfer systems.
Date: 6/23/80 II.4-4
-------
Posttreatment
After deposition of a metallic coating by either electro or elec-
troless techniques, an additional coating is sometimes applied to
prepare the metal surface for painting or the application of a
colored finish or to improve lubricity or corrosion protection.
These posttreatments are the chromating, phosphating, and metal
coloring processes of chemical conversion coating which are dis-
cussed later in the coating subcategory description.
Subcategory 1 - Common Metals Plating
This subcategory covers the electroplating of the following
common metals, or any combination of them, onto a surface:
aluminum, cadmium, chromium, copper, iron, lead, nickel, or tin.
The paragraphs below describe some of the individual characteris-
tics of the different types of plating done in this subcategory.
Aluminum Electroplating. Application of aluminum on a
commercial basis is limited. It has been used for coating
uranium and steel strip and electroforming. Because it is more
reactive than hydrogen, aluminum cannot be plated from aqueous
solutions or any solution containing acidic hydrogen. Only
plating from a hydride bath with the basic ingredients of diethyl
ether, aluminum chloride, and lithium aluminum hydride has had
any commercial applications.
Cadmium Electroplating. Cadmium electroplating provides a
corrosion protection coating over the basis material. Iron and
steel are the most commonly used basis materials. Since cadmium
is relatively high priced, only thin coatings are applied. It is
sometimes used as an undercoating for zinc. Cadmium plating is
often used on parts consisting of two or more metals to minimize
galvanic corrosion. Cadmium cyanide baths are by far the most
popular because they cover completely and give a dense, fine-
grained deposit which can be made very lustrous by the use of
stable brighteners.
Chromium Electroplating. Chromium electroplating solutions
contain chromic acid and silicate or fluoride ions. Three basis
materials account for the bulk of the chromium plate work:
steel, nickel-electroplated steel, and nickel-electroplated zinc.
Solutions containing 150 to 400 g/L of chromic acid are the
common baths for electroplating 0.0002 mm to 0.10 mm (0.000008 to
0.00040 in.) of decorative chromium or hard chromium (for resist-
ing wear) on steel and aluminum. Unlike the copper and nickel
plating processes, which utilize soluble copper or nickel anodes
to replenish the metal deposited on the workpieces, chromium
electroplating processes always use insoluble lead alloy anodes.
Thus, some portion of the chromic acid added regularly for main-
tenance is consumed by reduction to chromium metal at cathode
surfaces.
Date: 6/23/80 II.4-5
-------
Copper Electroplating. Copper is electroplated from several
types of baths, among them alkaline cyanide, acid sulfate, pyro-
phosphate, and fluoborate, which are prepared with the corre-
sponding copper salt. The cyanide solutions contain sodium
carbonate and may also contain sodium hydroxide or sodium potas-
sium tartrate. All four types may also contain a small amount of
an organic chemical for refining the grain or brightening the
plate. Cyanide solutions are used extensively for copper electro-
plating, but acid copper solutions have been adopted for plating
large numbers of steel, plastic, and zinc alloy products. Steel
and zinc are customarily plated first in a cyanide strike bath to
insure good electroplate adhesion.
Alloyed forms of copper also find use in electroplating, the most
common being brass and bronze. Brass, a combination of copper
and zinc, is often used as a decorative plate on furniture hard-
ware. Several types of bronze solutions including copper-tin,
copper-cadmium, and copper-zinc are utilized primarily as
decorative finishes.
Iron Electroplating. The electroplating of iron is used for
certain specialized purposes such as electroforming and buildup
of worn parts. Iron does not alloy with solder, which has led to
iron plating of soldering tips. While there are several difficul-
ties in the maintenance of an iron electroplating line, the iron
electroplating solutions are comparatively stable and simple to
operate. Special noncorrosive equipment is needed to heat and
agitate the plating bath. Also, care must be taken that the
plating bath does not oxidize. However, these disadvantages may
be offset by the great abundance of low cost iron. Iron may be
deposited as a hard and brittle or soft and ductile coat. Almost
all iron is plated from solutions of ferrous salts at low pH's.
The most common baths contain sulfate, chloride, fluoborate, and
sulfamate.
Lead Electroplating. Lead is most resistant to hydrofluoric
and sulfuric acids and is used for protective linings as well as
coatings on nuts and bolts, storage battery parts, and bearings.
Lead is often an undercoat for indium plating. Lead-tin and
lead-antimony alloys are used. Solder plating is a 40/60 lead-
tin alloy which is widely used in the electronics field.
Fluosilicate and fluoborate baths are the most widely used. The
fluoborate bath is more expensive, but it gives finer grained,
denser deposites, adheres better to steel, and will not decompose
as readily.
Nickel Electroplating. Nickel is electroplated from several
baths; among these are Watts (sulfate-chloride-boric acid),
sulfamate, all chloride, and fluoborate baths. Each type of
solution is prepared with the corresponding nickel salt, a buffer
Date: 6/23/80 II.4-6
-------
such as boric acid, and a small concentration of a wetting agent.
A small amount of another organic chemical may be added to
brighten the deposits or control other properties. Nickel is
extensively electroplated in a three-metal composite coating of
copper, nickel, and chromium. Nickel is also electrodeposited
on steel for decorative-protective finishes and on other
materials for electroforming. In these applications, nickel
electroplating is preceded by cleaning and activating operations
in a sequence selected for a specific basis material.
Organic agents that refine the grain size of the deposit and
brighten the plate are added to all nickel plating baths adopted
for sequential nickel-chromium plating. Proprietary agents are
supplied by metal finishing supply companies that have developed
stable, effective chemicals for insuring mirrorlike, corrosion-
protection deposits requiring no buffing;
Tin Electroplating. In terms of tonnage of product produced,
continuous tin electroplating of coil steel represents the
largest application of electroplating in the world. Resistant to
corrosion and tarnish, tin is also solderable, soft, and ductile.
These properties of tin make it excellent for food handling equip-
ment, electronic components, and bearing surfaces where lubricity
to prevent seizing and scoring is desired.
Tin electroplate can provide a mat or bright deposit. The common
baths of alkaline stannate and acid fluoborate produce a mat
finish while the acid sulfate process can result in either type
of deposit. Commonly, mat finishes are brightened by a post-
plating operation of melting the deposit. This method is called
"reflowing."
Zinc Electroplating. Zinc is electroplated in (a) cyanide
solutions containing sodium cyanide, zinc oxides, or cyanide and
sodium hydroxide; (b) noncyanide alkaline solutions prepared with
zinc pyrophosphate or another chelating agent such as tetrasodium
pyrophosphate, sodium citrate, or the sodium salt of ethylene-
diamine tetraacetic acid; (c) acid or neutral chloride baths
prepared with zinc chloride and a buffer salt such as ammonium
chloride; or (d) acid sulfate solutions containing zinc sulfate
and a buffer salt such as aluminum chloride or sulfate. A small
concentration of an organic compound such as glucose, licorice,
or glycerin may be added to the chloride or sulfate baths for
brightening purposes.
Subcategory 2 - Precious Metals Plating
This subcategory is very similar to subcategory 1 in that it uses
the same surface preparation, plating, and posttreatment proc-
esses. The difference lies in the type of metals to be plated
onto the surfaces, of which there are six in this subcategory:
Date: 6/23/80 II.4-7
-------
gold, indium, palladium, platinum, rhodium, and silver. Since
the processes are very similar to those described above, no
repetitive description is presented here. Individual char-
acteristics of the plating metals and their processes are
briefly described below.
Gold Electroplating. Gold electroplating provides not only
decorative finishes and corrosion protection; it is also import-
ant in providing electrical contact surfaces, bonding surfaces,
and electroformed conductors. Plating baths have been developed
for each of these uses. Four types of gold baths are used.
Three of these are cyanide baths - unbuffered alkaline with a
pH range of 8.5 to 13, acid buffered with a pH range of 3 to 6,
and a neutral buffer with a pH range of 6 to 8.5. The fourth is
noncyanide.
Indium Electroplating. Indium electroplating is used in the
manufacture of aircraft engine bearings. Corrosion of the
originally plated cadmium-silver-copper bearings is reduced by
an indium overlayer and heat treating. Indium is often alloy
plated with copper, tin, lead, cadmium, nickel, bismuth, or
rhodium.
Initially, indium baths were composed of cyanide and sugar.
Today the sulfate bath is the most widely used, along with alka-
line, fluoborate, sulfamate, chloride, perchlorate, and tartrate
baths.
Platinum Metals Electroplating. Of the six metals in the
platinum group only platinum, rhodium, and palladium are electro-
plated to any extent. Of these, rhodium is most often deposited.
Decorative coatings for silverware, jewelry, and watches are very
thin (0.1 pm) and are used to prevent tarnish and excessive wear
of silver and to enhance the color of gold and gold-filled
products. When the basis metal is not a silver or a gold alloy
an undercoat of nickel is generally used. Coatings 25 um (0.001
in.) thick are used for wear and corrosion resistance in the
electronics industry and provide a surface of high optical
reflectivity.
Platinum is electroplated on titanium and similar metals which
are used as insoluble anodes in other plating operations (e.g.,
rhodium and gold). Electroplated platinum is used as an under-
coat for rhodium plate. Ruthenium electroplating is used on
high intensity electrodes to improve electrical contact.
Commercial electroplating of osmium and iridium are believed
to be nonexistent.
Rhodium electroplating baths are supplied as phosphate or sulfate
concentrates. The only additions made to the diluted concen-
trate are phosphoric and/or sulfuric acids at concentrations of
Date: 6/23/80 II.4-8
-------
25 to 75 mL per liter of plating bath. A rhodium concentration
of 2.0 g/L is used for decorative coatings. Concentration is
increased to 10 to 20 g/L for achieving thicker deposits.
The pallaidum content in plating solutions ranges from 2.5 to
10 g/L in the form of an amino nitrite complex. Other constitu-
ents are 11 g/L sodium nitrite and 40 mL/L of concentrated
ammonium hydroxide. Palladium deposition has been accomplished
from chloride or bromide solutions and from a molten cyanide
bath.
Silver Electroplating. The use of silver electroplating is
expanding in both the engineering and the decorative fields.
Silver is typically electroplated in two types of baths, a con-
ventional low metal bath and the high speed bath with a much
higher silver content. Most baths are now based on potassium
formulations because they provide high plating speeds, better
conductivity, increased tolerance to carbonates, and smoother
deposits.
Subcategory 3 - Anodizing
Anodizing is an electrolytic oxidation process which converts
the surface of the metal to an insoluble oxide. These oxide
coatings provide corrosion protection, decorative surfaces, a
base for painting and other coating processes, and special
electrical and engineering properties. Aluminum is the most
frequently anodized material, while some magnesium and limited
amounts of zinc and titanium are also anodized.
Surface preparation for anodizing can be minor or extensive
depending on the alloying elements in the basis material and the
amount of oil, grease, or oxide present on the part. Generally,
the surface is prepared by four sequential cleaning steps, each
(except degreasing) followed by rinsing. The vapor degreasing
step is required only if an excessive amount of oil and grease
is present. The principal cleaning step, inhibited soak
cleaning, follows the degreasing step. Acidic cleaning and an
optional etching step complete the surface preparation. The
etching step may form a smutlike surface when an alkaline etch
is used on an alloying metal which is cleaned by a nitric acid
bath. After a final rinse the piece is ready for anodizing.
For aluminum parts, the formation of the oxide occurs when the
parts are made anodic in dilute sulfuric acid or dilute chromic
acid solutions. The oxide layer begins formation at the extreme
outer surface, and as the reaction proceeds, the oxide grows into
the metal. The last formed oxide, known as the boundary layer,
is located at the interface between the base metal and the oxide.
The boundary is extremely thin and nonporous. The sulfuric
acid process is typically used for all parts fabricated from
Date: 6/23/80 II.4-9
-------
aluminum alloys except for parts subject to stress or containing
recesses in which the sulfuric acid solution may be retained and
attack the aluminum.
Chromic acid anodic coatings are more protective than sulfuric
acid anodic coatings. This is partly due to the retention of
chromic acid in the coating and its relatively thick boundary
layer. For these reasons, a chromic acid bath is used if a
complete rinsing of the part cannot be achieved.
Subcategory 4 - Coating
This section deals with chemical conversion coating by chromating,
phosphating, metal coloring, and immersion plating. These coatings
are applied to previously deposited metal or basis materials for
increased corrosion protection, lubricity, preparation of the sur-
face for additional coatings, or formulation of a special surface
appearance.
In addition to the surface preparation steps described earlier,
polishing is often used in coating operations to obtain the de-
sired surface prior to coloring. Mechanical polishing, electro-
poloshing, and chemical polishing are used to obtain specific
surface finishes.
Anodic coatings once applied are usually improved by a sealing
process, usually involving an acid mixture, that modifies the
surface to give better corrosion protection and improved paint
adhesion. Unsealed anodic coatings may be colored by immersion
in inorganic or organic dyes followed by a sealing process.
Other posttreatment processes include applying special surface
characteristics and drying.
Chromating. Chromate conversion coatings are protective
films formed on the metal surfaces. During the process of chro-
mating, a portion of the base metal is converted to one of the
components of the film by reaction with aqueous solutions con-
taining hexavalent chromium and active organic or inorganic com-
pounds. Chromating solutions are generally acidic and contain
chromic acid or its sodium or potassium salts, plus organic or
inorganic compounds such as activators, accelerators, or catalysts.
Although chromate conversion coatings can be applied by chemical "
or electrochemical action, the bulk of the coatings are usually
applied by a chemical immersion, spray, or brush treatment. Most
chromate treatments used in industry employ proprietary solutions.
Additional coloring of the coatings can be achieved by dipping
the organic dye baths to impart red, green, blue, and other
colors. Besides their use as protective or decorative films,
chromate conversion coatings are extensively employed to provide
an excellent base for paint and other organic finishes which do
not adhere well to untreated metal surfaces.
Date: 6/23/80 II.4-10
-------
Phosphating. Phosphate conversion coatings produce a mildly
protective layer of insoluble crystalline phosphate on the surface
of a metal. Phosphate coatings are used to (a) provide a good
base for paints and other organic coatings, (b) condition the sur-
faces for cold forming operations by providing a base for drawing
compounds and lubricants, and (c) impart corrosion resistance to
the metal surface by the coating itself or by providing a suitable
base for rust-preventive oils or waxes. Phosphate conversion
coatings are formed by the immersion of iron, steel, or zinc-
plated steel in a dilute solution of phosphoric acid plus other
reagents.
The method of applying the phosphate coating is dependent upon
the size and shape of the part to be coated. Small parts are
coated in barrels immersed in the phosphating solution. Large
parts, such as steel sheet and strip, are spray coated or con-
tinuously passed through the phosphating solution. Supplemental
oil or wax coatings are usually applied after phosphating unless
the part is to be painted.
Coloring. Metal coloring by chemical conversion methods
produces a large group of decorative finishes. This section covers
only chemical methods of coloring in which the metal surface is
converted into an oxide or other insoluble metal compound. The
most common colored finishes are used on copper, steel, zinc, and
cadmium.
Application of the color to the cleaned basis metal involves only
a brief immersion in a dilute aqueous solution. The colored films
produced on the metal surface are extremely thin and delicate.
Consequently, they lack resistance to handling and the atomsphere.
A clear lacquer is often used to protect the colored metal surface.
Immersion Plating. Immersion plating is a chemical plating
process in which a thin metal deposit is obtained by chemical dis-
placement of the basis metal. In immersion plating, a metal will
displace from solution any other metal that is below it in the
electromotive series of elements.
The lower (more noble) metal will be deposited from solution while
the more active metal (higher in the series) will be dissolved.
A common example of immersion plating is the deposition of copper
on steel from an acid copper solution.
The thickness of immersion deposits is usually of the order of
0.25 pm (0.00001 in.) although a few processes produce deposits
as thick as 2.5 pm to 5 pm (0.001 in. to 0.0002 in.). This thin-
ness limits the usefulness of immersion deposits as to applica-
tions other than corrosion protection such as decoration or
preparation for further processing such as painting or rubber
bonding. The most widely used immersion plating processes are
(a) tin on brass, copper, steel, or aluminum, (b) copper on
Date: 6/23/80 II.4-11
-------
steel, (c) gold on copper or brass, (d) nickel on steel, and
(e) zinc on aluminum.
Subcategory 5 - Chemical Milling and Etching
Chemical milling and etching processes are used to produce spe-
cific design configuration and tolerances on metal parts by con-
trolled dissolution with chemical reagents or etchants. Included
in this general classification are the specific processes of
chemical milling, chemical etching, bright dipping, electropolish-
ing, and electrochemical machining.
In addition to the normal surface preparation processes, masks
are applied by dip, spray, brush, roll or flow coating, silk-
screen techniques, or photosensitive resists to prevent metal
removal where it is not desired. Typically photographic tech-
niques are used for the blanking of small, intricately shaped
parts or for the production of nameplates, dials, and fine-mesh
screen. After masking, parts may be dipped in acid to activate
the surface prior to chemical milling or etching.
Chemical Milling. Chemical milling is similar to the etch-
ing procedure used for decades by photoengravers, except that the
rates and depths of metal removal are usually much greater.
Chemical milling is especially suited for removing metal from
shallow depths on formed complex shaped parts (e.g., forgings,
castings, extrusions) from thin sections and from large areas.
The amount of metal removed or the depth of removal is controlled
by the immersion time in the milling solutions. The metal can be
removed from an entire part or restricted to selected areas by
masking.
Typical solutions for chemical milling include ferric chloride,
nitric acid, ammonium persulfate, chromic acid, cupric chloride,
hydrochloric acid, and combinations of these reagents. Aluminum
is milled in ferric chloride or hydrochloric acid or sodium
hydroxide solutions. Copper is milled in ferric chloride,
cupric chloride, chromic acid, or ammonium persulfate solutions.
Etching. Chemical etching is the same process as chemical
milling, except that relatively small amounts (1-5 mils) of metal
are removed. Bright dipping, a specialized example of the etch-
ing process, is used to remove oxide and tarnish from ferrous
and nonferrous materials. Bright dipping can produce a range of
surface appearances from bright clean to brilliant depending on
the surface smoothness desired in the finished part. A smoother
surface results in a more brillant appearance.
Bright dipping solutions usually involve mixtures of two or more
of sulfuric, chromic, phosphoric, nitric, and hydrochloric acids.
The rate of attack on the metal is controlled by the addition of
Date: 6/23/80 II.4-12
-------
inhibiting materials. The quantity of these materials is depend-
ent upon the metals that are to be dipped. The type and quantity
of the parts to be bright dipped greatly influence the composi-
tion of the bath. For parts with simple shapes which can be
easily removed from the dipping solution and quickly rinsed,
fast-acting dips are used. Slow-acting dips are used for bulk
loads of parts and parts with complex shapes.
Subcategory 6 - Electroless Plating
Electroless plating is a chemical reduction process which depends
upon the catalytic reduction of a metallic ion in an aqueous solu-
tion containing a reducing agent and the subsequent deposition of
metal without the use of external electrical energy. It has found
widespread use in industry due to its several unique advantages
over conventional electroplating. Electroless plating provides a
uniform plating thickness on all areas of a part regardless of
the part's configuration or geometry. This makes it possible to
plate deep recesses and niches that electroplating cannot effec-
tively reach due to current distribution problems. An electroless
plate on a properly prepared surface is dense and virtually non-
porous. Furthermore, certain types of electroless platings pro-
vide better hardness and corrosion protection than their electro-
plated counterparts. Copper and nickel electroless plating are
the most common. Others found on a smaller scale are iron,
cobalt, gold, palladium, and arsenic.
The basic ingredients in an electroless plating solution are:
A source of metal, usually a salt.
A reducer to reduce the metal to its base state.
A chelating agent to hold the metal in solution (so the
metal will not plate out indiscriminately).
Various buffers and other chemicals designed to maintain
bath stability and increase bath life.
Of particular interest among the constituents of electroless
plating baths are the chelating agents. Chelation is an equilib-
rium reacton between a metal ion and a complexing agent character-
ized by the formation of more than one bond between the metal and
a molecule of the complexing agent. This results in the formation
of a ring structure incorporating the metal ion and thus holding
it in solution. Chelating agents control metal ions by blocking
their reactive sites, thus preventing them from carrying out
their normal (and in many cases undesirable) reactions.
In the electroless plating processes, the purpose of the chelat-
ing agent is to hold the metal in solution, to keep it from plating
out indiscriminately. Thus, the chelate can only be replaced by
Date: 6/23/80 II.4-13
-------
some material capable of forming an even more stable complex;
that is, the part to be plated.
One of the drawbacks in the use of chelating agents is the diffi-
culty in precipitating chelated metals out of wastewater during
treatment. Quite often, plants which are engaged in plating
activities that make use of chelating agents have treatment sys-
tems based on the precipitation and the settling out of heavy
metals. Unfortunately, in the treatment system, the chelating
agents continue to hold the metal in solution, and cause the
chelated metal to pass through the treatment system without pre-
cipitation and settling. In some situations, particularly with
the stronger chelates, special treatment is necessary to remove
the bound metals.
Electroless plating is performed on two different types of sur-
faces, metal and plastic. For electroless metal plating, prep-
aration consists of the conventional electroplating cleaning
steps for metals with active surfaces. In addition, the smoother
the surface, the better the resulting plating finish. Therefore,
the parts usually undergo mechanical preparation, such as honing,
and chemical treatment, such as acid dipping or alkaline cleaning.
Some metals require an activation step which involves a flash
deposit of a catalyst on the metal surface.
Surface preparation for electroless plastic plating, different
from that for metal plating, involves roughening or etching and
catalyst application. Roughnening is accomplished either by
mechanical means such as tumbling or by chemical means such as
etching. Following this step a catalyst is applied to allow
metal deposition to occur. All plastics require this catalytic
preparation prior to plating.
Two different catalyst application methods have been employed and
both are based on the interaction of stannous and palladium
salts. One method involves adsorbing stannous tin on the surface,
then immersing the part in palladium chloride. This reduces the
palladium to the metal form and oxidizes the tin from stannous to
stannic. A molecular layer of palladium metal is deposited on
the surface of the part and the tin remains in the solution.
The other process used for catalyst application involves the
application of a mixture of stannous and palladous compounds on
the part. This activator is adsorbed on the part, and a reaction
takes place when the part is exposed to a solution that dissolves
tin on the surface. After the catalyst is applied, the part is
immersed in the electroless bath and the desired metal plates
out on the palladium. After the initial layer of metal is
applied it becomes the catalyst for the remainder of the plating
process.
Plating is completed by immersing the activated piece in a plat-
ing tank long enough for the desired thickness to accumulate.
Date: 6/23/80 II.4-14
-------
Advantages of electroless plating over electroplating on metals
include greater hardness values and greater resistance to wear
and abrasion. Plastic electroless plating is done on nearly
every type of plastic and allows for low cost pieces.
The most common operation carried out after electroless plating
is electroplating. Virtually all of the electroless plating done
on plastics is followed by some form of electroplating operation.
Although an electroless plate has superior hardness and corrosion
protection characteristics, it may be covered by some coating
such as a lacquer.
Subcategory 7 - Printed Circuit Board Manufacturing
Printed boards are fabricated from nonconductive board materials
such as plastic or glass on which a circuit pattern of conductive
metal, usually copper, has been formed. The board not only pro-
vides a surface for the application of a conductive wiring path
but also gives support and protection to the components it con-
nects. As a means of packing and interconnecting electronic
devices, printed boards find widespread use in business machines,
computers, and communications and home entertainment equipment.
Printing Methods. The printed board industry is limited to
three main production methods: subtractive, additive, and
semiadditive.
The subtractive process derives its name from the large amount of
material that is removed to make the circuit. The simplest of
the subtractive techniques is the print and etch process which
begins with a board of nonconductive materials, such as glass or
plastic, which is clad with a copper foil. The circuit pattern
is printed onto this foil in oil, cellulose, asphalt, vinyl, or
resin based ink and then the board goes through an etching opera-
tion in which the area of the foil not covered by the ink is
removed. Next, the ink is stripped from the foil, leaving only
the desired circuit of copper on the board.
At this point, the board can be handled in one of two ways. If
it is to be panel plated, the whole board is electroplated with
copper. Then a plating resist is applied in such a form that
only the desired circuit is left exposed (not covered by resist).
This exposed area is then electroplated (by immersing the entire
board in the plating solution) with an etch resist, usually
solder. If it is to be pattern plated, the plating resist is
applied directly after the electroless copper step, so only the
circuit is copper electroplated and likewise solder plated.
Following the application of the solder plate by either method
the plating resist is stripped off, exposing the copper in areas
where the circuit is not required. This copper is then etched
off, leaving only the desired circuit which was etch protected by
Date: 6/23/80 II.4-15
-------
solder plate. The tabs or fingers at the edges of the boards are
now stripped of their solder in preparation for subsequent plating.
These tabs are electroplated according to the specifications of
the customer (in most cases with gold or nickel and gold). The
solder plate in the circuit pattern is now reflowed to completely
seal the copper circuitry and act as a corrosion preventive. The
last steps are blanking and cutting of boards to size and final
inspection.
The additive process involves deposition of plating material on
the board in the pattern dictated by the circuit, rather than
removal of metal already deposited (as in the subtractive proc-
ess). There have been several "additive" methods for producing
printed boards. The original method consisted of depositing a
thin layer of electroless copper on a bare unclad board and fol-
lowing this up with conventional subtractive processing.
The additive process presently employed by some manufacturers is
more totally additive than the original method. The process
begins with a bare board which may or may not be impregnated with
a catalyst. Holes are then formed by drilling or punching. An
adhesion promotion operation (in which the surface is roughened
or etched) is next, followed by the plating resist, describing
the required circuit pattern, which is applied to the board in the
noncircuit areas. The accelerator step necessary for electroless
plating is then carried out, and the board goes into the electro-
less copper bath. Since the board does not initially have any
copper in noncircuit areas and a resist is applied to these areas
prior to electroless plating, a copper etching step is not neces-
sary. Following copper deposition, the tabs are plated in the
same manner as in the subtractive process. At this point, differ-
ent finishing steps may be applied, such as application of a pro-
tective coating to the board.
A recently developed additive method involves sensitizing the
entire board and then selectively activating the catalyst in the
pattern of the circuit by means of ultraviolet light.
A semiadditive production process is a compromise between the
additive and subtractive methods. The process sequence begins
with an unclad board which undergoes hole fabrication (drilling
or punching). An adhesion promotion operation is performed on
the board just as in the additive process, the board being etched
to obtain a microporous surface. At this point, the sequence
follows the subtractive process. The entire board is catalyzed
and activated, and electroless copper is applied to the entire
board including the inside surfaces of the holes. The circuit
pattern is then applied by conventional methods (screening or
photoimaging). Copper electroplate is deposited to build up the
circuit to the desired thickness. The solder plate for etch
masking is then applied, and the plating mask is stripped from the
noncircuit areas. The subsequent etching operation is a quick
Date: 6/23/80 II.4-16
-------
etch (as compared with the subtractive process etch) because only
the electroless copper flash has to be removed. In the subtractive
process, the copper foil on the board and the electroless copper
have to be etched away, but this is not required for the semiaddi-
tive process. Thus its advantage over the subtractive process is
a reduction in copper waste. After the etch operation, the solder
stripping, tab plating, and any final fabrication processes are
performed as in the conventional subtractive process.
Production Processes. Printed board production for all the
above board types can be broken down into the following operations:
cleaning and surface preparation, catalyst application and electro-
less plating, pattern printing and masking, electroplating, and
etching. Brief descriptions of these processes are presented
below.
Cleaning and surface preparation is a crucial step in printed
board production. For a board to be plated correctly without
flaws, it must be cleaned and properly treated. In many cases,
the boards go through a mechanical scrubbing before they reach
the plating lines. In the case of multilayer boards, after they
are bonded or laminated they go through an acid hole-cleaning
operation to remove any bonding epoxy which spilled over the holes.
Once on the plating line, all types of boards are alkaline cleaned
to remove any soil, fingerprints, smears, or other substances
which cause plating flaws. A mild etch step is then performed
with ammonium or sodium persulfate to prepare the copper foil
surface (for copper clad boards) for subsequent plating. The
copper clad boards are then acid treated to roughen the exposed
plastic surfaces (inside areas of holes) so they will readily
accept the catalyst.
Electroless copper deposits quite readily on a copper clad board,
but for a deposit to form on the exposed plastic or on a bare
board (as in the additive process or in through-hole plating), a
catalyst must be involved for the copper plate on the nonmetal.
The application and activation of the catalyst is a two-step
process. The catalyst application consists of the deposition of
a thin layer of palladium on the surface of the part.
Three different catalyst application methods have been employed,
and all are based on the interaction of stannous and palladium
salts. One method involves adsorbing stannous tin on the surface,
then immersing the part in palladium chloride. This reduces the
palladium to the metal form and oxidizes the tin from stannous to
stannic. A molecular layer of palladium metal is deposited on
the surface of the part and the tin remains in the solution.
Another process used for catalyst application involves the appli-
cation of a mixture of stannous and palladous compounds on the
part. This activator is adsorbed on the part, and a reaction
Date: 6/23/80 II.4-17
-------
takes place when the part is exposed to a solution that dissolves
tin, leaving only palladium on the surface. This step is commonly
referred to as "acceleration."
In a recently developed method, specifically for printed boards,
a catalyst is applied only to the area to be occupied by the
circuit. Stannous chloride is adsorbed on the entire part's sur-
face. Then the surface is exposed to ultraviolet light shone
through a stencil. The light oxidizes the stannous tin to stannic
in the area not to be plated. This area, when exposed to palla-
dium chloride, undergoes no reaction, and no palladium is de-
posited. Only the unexposed area receives a palladium deposit.
Once the catalyst is applied, the metal in the electroless bath
plates out on the palladium. After the initial layer of metal is
applied, it becomes the catalyst for the remainder of the plating
process.
After the boards have been catalyzed, they go into the electro-
less copper solution and are panel plated in the subtractive and
semiadditive processes or pattern plated in the additive process.
The electroless copper bath contains copper salts (copper sulfate
being most prevalent), formaldehyde as a reducer, chelating agents
to hold the copper in solution (in most cases either a tartrate
or an ethylenediaminetetraacetic acid compound), sodium hydroxide
as a pH buffer, and various polymers and amines which serve as
brighteners and bath stabilizers. These chemicals vary according
to each bath supplier and his own "proprietary" formulas.
Another key step in the manufacture of printed circuit boards is
the pattern printing. The precision of this artwork is crucial
since the quality of the final board can be no better than the
image printed on it. There are three principal methods in which
the image or pattern is applied to the board: screening, photo-
sensitive resist techniques, and offset printing. All of the
methods apply a resist material to the board.
Screening consists of selectively applying resist material
through a stencil or screen. The screen material is placed over
the work, and the ink or resist material is squeegeed through the
screen. The screening method is highly acceptable for simple
low density circuits because its low cost allows for high volume
production.
Photosensitive resist is a light sensitive polymer which, after
curing, has a significant chemical resistance. After the board
has been cleaned and prepared, the polymer is applied by dipping
or rolling. A light source (usually ultraviolet) is applied
through a pattern onto the resist. The light sensitive material
hardens, and the unexposed resist is then removed by one of
several methods; usually a trichloroethylene degreaser is used.
This is followed by a baking or curing step after which the resist
Date: 6/23/80 II.4-18
-------
is able to withstand plating solutions. This type of precision
masking has made possible the production of high density and in-
tricate circuits.
Offset printing is a high volume production technique similar to
the operation of a printing press. An etched plate (the print-
ing plate) serves as a master pattern. Ink is transferred from
an ink roller to the plate on a rubber cylinder. The ink image
is then deposited on the copper-covered board. Enough ink can be
built up on the board in several passes to form a plating or
etching resist.
Whether an additive, semiadditive, or subtractive process is
used, masking is applied when the tabs are being plated. The
simplest and most commonly used mask for such applications is a
water repellent tape which can be easily applied to or removed
from the board.
Electroplating is performed at several junctures in the produc-
tion of printed boards. It is employed in the actual buildup of
the circuit (in the subtractive and semiadditive processes); it
applies the etch resist and anticorrosion layer to the circuit;
and it covers the tabs or fingers of all boards.
To build up the desired circuit in the subtractive and semiaddi-
tive processes, copper electroplating is followed by solder
electroplating. The copper bath itself is usually one of four
types: cyanide copper, fluoborate copper, pyrophosphate copper,
or sulfate copper. The solder electroplate serves a dual purpose:
it acts as a mask during the etching process, and it protects the
copper circuit from corrosion after final fabrication. This
solder plate usually consists of 60-40 tin-lead, although tin-
nickel and gold are used in some instances.
The tabs or fingers of the printed circuit boards are electro-
plated for most applications (additive, semiadditive or subtrac-
tive). In the subtractive and semiadditive processes, a solder
strip operation precedes plating to ensure better adhesion; this
step is unnecessary in the additive process. In most cases,
nickel and gold or simply gold is used.
Etching is that process by which all the unwanted copper (i.e.,
any copper other than in the circuit) is removed from the board.
This step follows, in sequence, the pattern print and pattern
plate. Most companies make use of mechanical etchers which spray
solutions from various tanks (containing etch solutions, solder
brighteners or activators, and rinse waters) onto horizontally
traveling boards.
Date: 6/23/80 II.4-19
-------
The etch solutions include:
Ferric chloride base - This provides good uniform etching
but removal of the residual acid from the work is difficult.
Cupric chloride - This is suitable for any resist and has
the advantage of continued regeneration through addition
of chemicals.
Chromic acid base - This is the most expensive etchant
listed here and requires special attention in waste treat-
ment for chromium reduction. It is also very effective.
Ammonium persulfate - This is clean and easy to handle,
but the solution can be somewhat unstable.
Etching is always used in the subtractive production method,
while an abbreviated etch is employed in the semiadditive process.
The etching operation is not a part of the additive process.
After etching, the boards are ready for solder stripping and the
electroplating of the tabs.
Table 4-2 presents best practicable control technology effluent
limitations for several subcategories in the electroplating
industry.
II.4.2 WASTEWATER CHARACTERIZATION [1]
Electroplating process wastewater is generated by (1) alkaline
cleaning operations, (2) acid cleaning operations, (3) catalyst
application and acceleration processes, (4) plating operations
and posttreatment, and (5) auxiliary operations.
Wastewater constituents from the above sources include the basis
material being finished as well as the components in the proces-
ing solutions. Predominant wastewater constituents for the
industry include copper, nickel, chromium, zinc, lead, tin, cad-
mium, gold, silver, and platinum, as well as ions such as phos-
phates, chlorides, and various complexing agents.
The following paragraphs describe the major waste sources for
normal plating operations.
II.4.2.1 Alkaline Cleaners
Cleaning solutions usually contain one or more of the following
chemicals: sodium hydroxide, sodium carbonate, sodium metasili-
cate, sodium phosphate (di- or trisodium), sodium silicate,
sodium tetraphosphate, and a wetting agent. The specific content
of cleaners varies with the type of soil being removed. Waste
waters from cleaning operations contain not only the chemicals
Date: 6/23/80 II.4-20
-------
rt
n>
NJ
to
00
o
I
KJ
TABLE 4-2. BPT EFFLUENT LIMITATIONS FOR THE ELECTROPLATING INDUSTRY [3]
TABLE 4-2. BPT EFFLUENT LIMITATIONS FOR THE ELECTROPLATING INDUSTRY
Concentration. mg/m2 (Ib/M ft2) per operationb
Parameter
Cadmium
Chromium, total
Chromium, VI
Copper
Cyanide, total
Cyanide, A
Fluoride
Gold
Iridium
Iron
Lead
Nickel
Osmiun
Palladium
Phosphorus
Platinum
Rhodium
Ruthenium
Silver
Tin
Zinc
TSS
PH
Common metals
Daily
maximum
96(19.2)
160(32.7)
16(3.3)
160(32.7)
160(32.7)
16(3.3)
6,400(1,310) 3
320(65.4)
160(32.7)
160(32.7)
320(65.4)
320(65.4)
160(32.7)
6,400(1,310) 3
6-9
plating
30-day
average
48(9.6)
80(16.4)
8(1.6)
80(16.4)
80(16.4)
8(1.6)
,200(654)
160(32.7)
80(16.4)
80(16.4)
160(32.7)
160(32.7)
80(16.4)
,200(654)
.5
Precious metals plating
Daily 30-day
maximum average
160(32.7)
16(3.3)
160(32.7)
16(3.3)
16(3.3)
16(3.3)
16(3.3)
16(3.3)
320(65.4)
16(3.3)
16(3.3)
16(3.3)
16(3.3)
6,400(1,310) 3,
6-9.
80(16.4)
8(1.6)
80(16.4)
8(1.6)
8(1.6)
8(1.6)
8(1.6)
8(1.6)
160(32.7)
8(1.6)
8(1.6)
8(1.6)
8(1.6)
200(654)
5
Anodizing
Daily
maximum
54(8.8)
90(18.4)
9(1.8)
90(18.4)
90(18.4)
9(1.8)
3,600(738)
180(36.8)
90(18.4)
180(36.8)
180(36.8)
90(18.4)
3,600(738)
30-day
average
27(4.4)
45(9.2)
4.5(0.9)
45(9.2)
45(9.2)
4.5(0.9)
1,800(369)
90(18.4)
45(9.2)
90(18.4)
90(18.4)
45(9.2)
1,800(369)
6-9.5
Coating
Daily
maximum
48(9.8)
80(16.4)
8(1.6)
80(16.4)
80(16.4)
8(1.6)
3,600(738)
160(32.8)
80(16.4)
160(32.8)
160(32.8)
80(16.4)
3,600(738)
30-day
average
24(4.9)
40(8.2)
4(0.8)
40(8.2)
40(8.2)
4(0.8)
1,800(369)
80(16.4)
40(8.2)
80(16.4)
80(16.4)
40(8.2)
1,800(369)
6-9.5
Chemical milling
and etching
Daily
maximum
72(14.8)
120(24.6)
12(2.4)
120(24.6)
120(24.6)
18(3.8)
4,800(984)
240(49.2)
120(24.6)
240(49.2)
240(49.2)
120(24.6)
4,800(984)
30-day
average
36(7.4)
60(12.3)
6(1.2)
60(12.3)
60(12.3)
9(1.9)
2,400(492)
120(24.6)
60(12.3)
120(24.6)
120(24.6)
60(12.3)
2,400(492)
6-9.5
Note: Blanks indicate data not available.
For the electroless plating and printed circuit board subcategories, only pretreatment standards have been promulgated. Other subcategories are not
mentioned in the Federal Register at this tine.
Except pH values (given in pH units).
-------
found in the alkaline cleaners but also soaps from the saponifi-
cation of greases left on the surface by polishing and buffing
operations. Some oils and greases are not saponified but are,
nevertheless, emulsified.
The raw wastes from cleaning process solutions and dissolution
of basis metals show up in the rinse waters, spills, dumps of
concentrated solutions, wash waters from air-exhaust ducts, and
leaking heating or cooling coils and heat exchangers. The con-
centrations of dissolved basis metal in rinses following alkaline
cleaning are usually small relative to acid dip rinses.
II.4.2.2 Acid Cleaners
Solutions for pickling or acid cleaning usually contain one or
more of the following: hydrochloric acid (most common), sulfuric
acid, nitric acid, chromic acid, fluoboric acid, and phosphoric
acid. The solution compositions vary according to the nature of
the basis metals and the type of tarnish or scale to be removed.
These acid solutions accumulate appreciable amounts of metal as a
result of dissolution of metal from workpieces or uncoated areas
of plating racks that are recycled repeatedly through cleaning,
acid treating, and electroplating baths. As a result, the baths
usually have a relatively short life, and when they are dumped
and replaced, large amounts of chemicals must be treated or re-
claimed. These chemicals also enter the waste stream by way of
dragout from the acid solutions into rinse waters.
II.4.2.3 Catalyst Application and Acceleration
In electroless plating on plastics, a catalyst must be applied
to the plastic to initiate the plating process. The catalyst
consists of tin and palladium, and in the acceleration process
the tin is removed. A chromic acid surface preparation of the
plastic usually precedes the catalyst application.
II.4.2.4 Plating Operations and Posttreatment
Plating and posttreatment baths contain metal salts, acids,
alkalies, and various compounds used for bath control. Common
plating metals include copper, nickel, chromium, zinc, cadmium,
lead, iron, and tin. Precious plating metals include silver,
gold, palladium, platinum, and rhodium. In addition to these
metals, ammonia, sodium, and potassium are common cationic con-
stituents of plating baths. Anions most likely to be present
in plating and posttreatment baths are borate, cyanide, carbonate,
fluoride, fluoborate, phosphates, chloride, nitrate, sulfate,
sulfide, sulfamate, and tartrate.
Many plating solutions contain metallic, metallo-organic, and
organic additives to induce grain refining, leveling of the plat-
ing surface, and deposit brightening. Arsenic, cobalt, molybdenum,
and selenium are used in this way, as are saccharin and various
Date: 6/23/80 II.4-22
-------
aldehydes. These additives are generally present in a bath at
concentrations of less than 1% by volume or weight.
Complexing and chelating agents are important constituents of
some plating baths, especially electroless plating solutions.
Most electroless plating baths in commercial use are proprietary
and identification of complexing agents present is difficult.
From a wastewater standpoint, the prime importance of the agents
lies in the difficulties they present for effective metal removal
since they hinder precipitation of metal ions.
Chromium, aluminum, and manganese are the metal constituents
most common in anodizing baths; ammonia, sulfate, fluoride, phos-
phate, and various bases are the most important nonmetal constit-
uents. Basis metal, usually aluminum, will also be present in
the bath. Posttreatment for anodized surfaces often consists
only of hot water rinsing. Occasionally, anodized parts are
sealed with a chromium salt solution or colored with organic or
inorganic dyes.
Chromating baths are nearly all proprietary and little informa-
tion about their formulation is available. However, all baths
have chromate and a suitable activator (an organic or inorganic
radical) usually in an acid solution. Chromate conversions can
be produced on zinc, cadmium, aluminum, magnesium, copper, and
brass, and these metals will dissolve into the chromating baths.
Posttreatment of chromate conversion coatings may include dipping
in organic dips or sealing in a hot water rinse.
The phosphates of zinc, iron, manganese, and calcium are most
often used for phosphate coatings. Strontium and cadmium phos-
phates are used in some baths, and the elements aluminum, chro-
mium, fluorine, boron, and silicon are also common bath constit-
uents. Phosphoric acid is used as the solvent in phosphating
solutions. Phosphated parts may be colored in a posttreatment
step, or conditioned in very dilute chromic or phosphoric acid.
Solutions for chemical milling, etching, and associated opera-
tions contain dissolved or particulate basis metals and either
chemical agents for metal oxidation or electrolytes for elec-
trical metal removal (as in electrochemical machining). Bath
constituents for chemical removal of basis metals include mineral
acids, acid chlorides, alkaline ammonium solutions, nitro-organic
compounds, and such compounds as ammonium peroxysulfate. Common
electrolytes are sodium and ammonium chloride, sodium and ammo-
nium nitrate, and sodium cyanide. Posttreatment baths for chemical
milling or etching would not contain constituents significantly
different from those listed above.
Immersion plating baths usually are simple formulations of metal
salts, alkalies, and complexing agents. The complexing agents are
typically cyanide or ammonia and are used to raise the deposition
Date: 6/23/80 II.4-23
-------
potential of the plating metal. Parts plated by immersion are
seldom posttreated except in the case of zinc immersion plating
of aluminum. This process is used to form a base for subsequent
electroplating, usually copper.
II.4.2.5 Auxiliary Operations
Auxiliary operations such as rack stripping, although essential
to plant operation, are often neglected in considering overall
pollutant reduction. Stripping solutions using a cyanide base
can form compounds which are difficult to treat. One such com-
pound is nickel cyanide, in which the cyanide is not readily
amenable to chlorination. Frequent cleaning of stripping baths
and use of alternative chemicals can significantly reduce the
pollutants evolving from this type of source.
Water is used in the Electroplating Industry for rinsing work-
pieces; for plant washdown, air scrubbing, and auxiliary opera-
tion rinsing; and in preparing solutions. Approximately 90% of
the water used is for rinsing, which removes the process solution
film from the workpiece surface and from the racks used in rack
stripping. The water becomes contaminated with the constituents
of the process solutions and is not directly reusable.
Plant cleanup operations create dilute wastewater that is the
result of spills and air scrubbing operations. This wastewater
is usually added to acid/alkali wastestream prior to treatment.
Most wastewaters emanating from this industry are contaminated
with the particular constituents of the solutions used at the
individual plant sites. The ranges of wastewater concentrations
for the subcategories studied are presented in Table 4-3. No
additional information is available at this time.
II.4.3 PLANT SPECIFIC DESCRIPTION
No plant specific information is available at this time for the
Electroplating Industry.
II.4.4 POLLUTANT REMOVABILITY [1]
This section reviews the technology currently available and used
to remove or recover pollutants from the wastewater generated
from 196 plants in the electroplating data base. The technology
available includes both in-plant recovery and reuse of water
and final wastewater treatment.
II.4.4.1 In-Plant Technology
The intent of in-plant technology for the overall electroplating
point source category is to reduce or eliminate the waste load
requiring end-of-pipe treatment and thereby improve the efficiency
Date: 6/23/80 II.4-24
-------
Concentration range
Pollutant
parameter
Conventional
pollutants , mg/L
TSS
Toxic inorganic
pollutants , pg/L
Cadmium
Chromium, total
Chromium, VI
Copper
Cyanide , total
Cyanide, A
Lead
Nickel
Silver
Zinc
Nontoxic
pollutants , (jg/L
Fluoride
Gold
Iron
Palladium
Phosphorus
Platinum
Rhodium
Tin
Common
metals
plating
0.1 -
7 -
88 -
5 -
32 -
5 -
3 -
660 -
19 -
110 -
22 -
250 -
20 -
60 -
10,000
21,600
530,000
330,000
270,000
150,000
130,000
25,000
3,000,000
250,000
140,000
1,500,000
140,000
100,000
Precious
metals
plating Electroless
0.1 - 10,000 0.1 - 39.0
2 - 48,000
5 - 10,000 5 - 12,000
3 - 8,400 5 - 1,000
28 - 47,000
50 - 180,000
110 - 18,000
13 - 25,000
27 - 630
20 - 140,000 30 - 109,000
110 - 6,500
34
60 - 90,000
Anodizing Coating
36.0 - 920 19.0
270 - 79,000 190
5 - 5,000 5
5 - 78,000 5
4 - 68,000 4
140
410
180 - 33,000 60
100
- 5,300
- 79,000
- 5,000
- 130,000
- 68,000
- 200
- 170,000
- 53,000
- 6,600
Chemical
milling and
etching
0.1 -
88 -
5 -
210 -
5 -
5 -
110 -
22 -
75 -
60 -
340 -
4,300
530,000
330,000
270,000
130,000
100,000
200,000
140,000
260,000
140,000
6,600
Printed
circuit
boards
1.0
5
5
200
5
5
10
27
1
280
6
5
51
60
- 610
- 48,000
- 4,400
- 540,000
- 11,000
- 9,400
- 10,000
- 13,000
- 480
- 680,000
- 110
- 230
- 54,000
- 54,000
Note: Blanks indicate data not available.
aOnly one plant had a measurable level of this pollutant
-------
of waste treatment. In-plant technology involves the selection
of rinse techniques (with the emphasis on closed loop rinsing),
plating bath conservation, recovery and/or reuse of plating and
etch solutions, process modification, and integrated waste
treatment.
Rinse Techniques
Reductions in the amount of water used in electroplating can be
realized through installation and use of efficient rinse tech-
niques. Cost savings associated with this water use reduction
manifest themselves in reduced operating costs in terms of lower
cost for rinse water and reduced chemical costs for wastewater
treatment. An added benefit is that the waste treatment effi-
ciency is also improved. It is estimated that rinse steps consume
over 90% of the water used by a typical plating facility. Conse-
quently, the greatest water use reductions can be anticipated
to come from modifications of rinse techniques.
Several different methods of rinsing are available, with each
method having a particular use, efficiency, and water usage rate.
Methods may be combined to produce cleaner pieces. Other factors
may also affect the choice and efficiency of a rinsing method.
Recirculation of the rinse water is a possibility.
Plating Bath Conservation
If the overflow water from a rinse tank can be reused, it does
not have to be treated, and additional water does not have to be
purchased. One approach currently in use is to replace the
evaporative losses from the plating bath with overflow from the
rinse station. This way a large percentage of plating solution
normally lost by dragout can be returned and reused. The useful-
ness of this method depends on the rate of evaporation from the
plating bath and the overflow rate from the rinse tank. The
evaporation from a bath is a function of its temperature, surface
area, and ventilation rate, while the overflow rate is dependent
on the dilution ratio, the geometry of the part, and the dragout
rates.
Chemical Recovery
A number of techniques are utilized to recover and/or reuse
plating solutions or etchants. The incentive to recover or
reuse may be primarily economical, but the ecological impact of
not having to treat these concentrated solutions for discharge
should also be considered. The solutions can be reclaimed using
any one of a number of techniques such as reverse osmosis, ion
exchange, and evaporation.
Date: 6/23/80 II.4-26
-------
Process Modification
Process modifications can reduce the amount of water required for
rinsing and, thus, reduce the overall load on a waste treatment
facility. As an example, for electroless plating, a rinse step
can be eliminated by using a combined sensitization and activa-
tion solution followed by a rinse instead of a process sequence
of sensitization-rinse, activation-rinse. Another potential
process modification would be to change from a high concentration
plating bath to one with a lower concentration. Parts immersed
in the lower concentration bath require less rinsing (a dilution
operation), which decreases water usage relative to high concen-
tration baths. The use of noncyanide plating baths and phosphate-
free and biodegradable cleaners, where possible, reduces the
waste load on an end-of-pipe treatment system.
Integrated Waste Treatment
Waste treatment iself can be accomplished on a small scale in the
plating room with constant recycling of the effluent. This proc-
ess is generally known as integrated waste treatment. Integrated
treatment uses a treatment rinse tank in the process line
immediately following a process tank (plating, chromating, etc.).
Treatment solution (usually caustic soda in excess) circulating
through the rinse tank reacts with the dragout to form a
precipitate and removes it to a clarifier. This clarifier is a
small reservoir usually designed to fit near the treatment rinse
tank and be an integral part of water use in the production
process. Further treatment may take place in the clarifier
(cyanide oxidation, chrome reduction), or settling alone may
be used to separate the solids. Sludge is removed near the
spillover plate on the effluent side of the clarifier, and the
effluent is returned to the treatment rinse tank. Consequently,
no pollutants are directly discharged by the waste treatment
process. Although further rinsing of the parts is required to
remove treatment chemicals, this rinse will not contain pollut-
ants from the original process tank, and no further treatment
is needed.
II.4.4.2 Individual Treatment Technologies
Table 4-4 summarizes the individual treatment technologies that
are used by the plants in the electroplating data base. Some
of them are described below.
Chemical Reduction of Hexavalent Chromium
Reduction of hexavalent chromium has proven effectiveness in the
industry with up to 99.7% reduction efficiency possible. This
technique is highly reliable because it can e controlled auto-
matically and it operates at ambient conditions. Limitations
Date: 6/23/80 II.4-27
-------
TABLE 4-4. INDIVIDUAL TREATMENT TECHNOLOGIES51 [1]
Number of
plants in
Technology data base
Chemical reduction of hexavalent chromium 120
pH adjustment 158
Clarification 151
Diatomaceous earth filtration 5
Flotation 6
Chemical oxidation (chlorine) 90
Ion exchange 11
Evaporation 12
Reverse osmosis 7
Ultrafiltration 2
Membrane filtration 1
Electrodialysis 1
Filter press 8
Sludge drying beds 3
Vacuum filtration 21
Centrifugation 12
Electrolyte oxidation 3
aSome plants use more than one treatment technology.
include possible chemical interference by other wastes, and the
necessity for precise pH control.
pH Control
The control of pH is standard in most industries to provide
controlled effluent acidity/alkalinity. Because of its extensive
use the technology is well developed. A possible problem with
this technique is the disposal of a substantial quantity of
sludge.
Clarification
Clarification is also a well defined treatment technology.
Capable of handling large amounts of wastewater, it is the most
common technology used in this industry.
Diatomaceous Earth Filtration
Diatomaceous earth filtration, combined with pH adjustment and
precipitation, is an alternative to settling for suspended solids
removal. This technique, used to remove metal hydroxides and
other solids from the wastewater, releases high quality effluent.
Table 4-5 presents the information available for this technique.
Date: 6/23/80 II.4-28
-------
TABLE 4-5. DIATOMACEOUS EARTH FILTER [1]
Concentration,
mg/L
TSS
Zinc
Trivalent chromium
Iron
Copper
Nickel
Raw
waste
524
13.4
12.2
5.81
7.53
2.57
Effluent
10
0.139
0.611
0.248
0.444
0.044
Percent
removal
98
99
95
96
94
98
Flotation
Flotation units are commonly used to remove emulsified oils and
greases as well as dissolved solids with a specific gravity
close to that of water. The performance of the unit depends on
production of sufficient air bubbles to float the suspended
solids. Only limited application of this method has been
demonstrated in this industry.
Chemical Oxidation
Chlorine is used in treating industrial waste to oxidize cyanide.
Advantages of this process include low cost, availability of
automatic control, and operation at ambient temperatures. Dis-
advantages may include the release of toxic volatile components
from intermediate reactions, chemical interference, and the
potential hazard in using chlorine gas. Table 4-6 presents the
available information from the Electroplating Industry on this
treatment method.
TABLE 4-6. CHEMICAL OXIDATION (CHLORINE) [1]
Parameter
Cyanide
Phenol
Color
Turbidity
Odor
Percent
reduction
99.6
100
99
99.4
85
Date: 6/23/80 II.4-29
-------
Ion Exchange
Ion exchange is used extensively for water and wastewater treat-
ment to allow for recovery of valuable waste materials or by-
products, particularly ionic forms of precious metals such as
silver, gold, and uranium. This compact, relatively inexpensive
technique can often be installed with minimal production inter-
ruption. However, many materials may clog or foul the resin
capacity, reducing efficiency. When operated properly, this
method is highly efficient and generates a high quality effluent.
Table 4-7 is an example of the effluent characteristics from an
ion exchange column.
TABLE 4-7. ION EXCHANGE [1]
Pollutant
Aluminum
Cadmium
Chromium
Copper
Iron
Nickel
Silver
Tin
Cyanide
Sulfate
Phosphate
Concentration
, mg/L
Raw Treated
wastewater wastewater
5.60
1.05
7.60
4.45
3.70
6.20
1.50
0.50
0.80
21.0
3.75
0.24
0.00
0.06
0.09
0.10
0.00
0.00
0.00
0.20
2.0
0.80
Percent
reduction
96
100
99
98
97
100
100
100
75
90
79
Evaporation
Evaporation is advantageous because it permits recovery of a wide
variety of plating and other process chemicals; the water
recovered is of high purity, allowing for recycle; and it con-
centrates waste effluent, which is difficult by other means.
However, this process is energy intensive and heating
efficiency decreases as the heating plates scale up.
Others
Several other techniques, noted on Table 4-4, are available for
treating wastewater from this industry. These techniques are
currently being developed and at present are only being used
in a few of the electroplating plants. Descriptions of these
technologies are available in Volume III of this manual.
Date: 6/23/80 II.4-30
-------
II.4.5 REFERENCES
1. Final Development Document for Existing Source Pretreatment
Standards for the Electroplating Point Source Category. EPA
440/1-79/003, U.S. Environmental Protection Agency,
Washington, D.C., August 1979. 526 pp.
2. NRDC Consent Decree Industry Summary - Electroplating.
3. Environmental Protection Agency Effluent Guidelines and
Standards for Electroplating. Environment Reporter,
135:0341-0351, as of 5 May 1980.
Date: 6/23/80 II.4-31
-------
II.5 INORGANIC CHEMICALS MANUFACTURING
II.5.1 INDUSTRY DESCRIPTION [1]
II.5.1.1 General Description
In terms of Standard Industrial Classification (SIC) code numbers,
the major industries included for application of effluent limita-
tions, new source performance standards, and pretreatment stand-
ards within the Inorganic Chemicals Manufacturing Point Source
Category are:
SIC 2812 - Alkalies and chlorine
SIC 2813 - Industrial gases
SIC 2816 - Inorganic pigments
SIC 2819 - Industrial inorganic chemicals,
not elsewhere classified
Table 5-1 presents industry summary data for the Inorganic Chemi-
cals point source category in terms of the number of subcategor-
ies defined for study by Effluent Guidelines Division (EGD), the
number studied by EGD, and the number of dischargers in the in-
dustry.
TABLE 5-1 INDUSTRY SUMMARY [2]
Industry: Inorganic Chemicals
Total Number of Phase I Subcategories: 55
Number of Subcategories Studied: 11
Number of Dischargers in Industry:
• Direct: 630
• Indirect: 120
• Zero: 0
II.5.1.2 Subcategory Descriptions
Based on results of toxic pollutant screening and verification
sampling and on evaluation of applicable technologies for dis-
charge control and treatment, it has been recommended that
Date: 6/23/80 II.5.1-1
-------
effluent limitation guidelines, new source performance standards,
and pretreatment standards for new and existing sources be pro-
posed for 11 inorganic chemical manufacturing subcategories.
These subcategories, described herein, include [1]:
Aluminum fluoride Nickel sulfate
Chlor-alkali Sodium bisulfite
Chrome pigments Sodium dichromate
Copper sulfate Sodium hydrosulfite
Hydrofluoric acid Titanium dioxide
Hydrogen cyanide
Additionally, 3 of the 11 subcategories may be further subdivided
based on process subdivisions as follows:
Subcategory Process subdivisions
Chlor-alkali Mercury cell
Diaphragm cell
Titanium dioxide Sulfate
Chloride-rutile
Chloride-ilmenite
Hydrogen cyanide Andrussow process
Acrylonitrile byproduct
In addition to the 11 subcategories to be discussed in depth, 44
subcategories have been recognized and recommended as candidates
for exclusion either under Paragraph 8 of the NRDC consent decree
or for other reasons. The 44 additional subcategories are:
Aluminum sulfate Lithium carbonate
Ammonium chloride Manganese sulfate
Ammonium hydroxide Nitric acid
Barium carbonate Nitric acid (strong)
Borax Oxygen and nitrogen
Boric acid Potassium chloride
Bromine Potassium dichromate
Calcium Potassium iodide
Calcium carbide Potassium metal
Calcium carbonate Potassium permanganate
Carbon dioxide Sodium bicarbonate
Carbon monoxide Sodium carbonate
Chromic acid Sodium fluoride
Cuprous oxide Sodium hydrosulfide
Ferric chloride Sodium metal
Ferrous sulfate Sodium silicate
Fluorine Sodium thiosulfate
Hydrochloric acid Stannic oxide
Hydrogen Sulfur dioxide
Hydrogen peroxide Sulfuric acid
Iodine Zinc oxide
Lead monoxide Zinc sulfate
Date: 6/23/80 II.5.1-2
-------
Table 5-2 (next page) presents subcategory profile data for the
55 subcategories of the inorganic chemicals industry. Table 5-3
presents best practicable control technology (BPT), parameters
suggested for each subcategory and lists available data.
II.5.1.2.1 Aluminum Fluoride
Aluminum fluoride is used as a raw material in the production of
cryolite (which is used in the production of aluminum), as a
metallurgical flux (for welding rod coatings), as a ceramic flux
(for glazes and enamels), and as a brazing flux (for aluminum
fabrication).
Partially dehydrated alumina hydrate is reacted with hydrofluoric
acid gas in the dry process for the manufacture of aluminum' flu-
oride. The product, aluminum fluoride, is formed as a solid and
is cooled with noncontact cooling water before being sent for
milling and shipping. The gases from the reactor are scrubbed
with water to remove unreacted hydrofluoric acid before being
vented to the atmosphere.
Wastewater flows emanating from different streams generated from
the production of aluminum fluoride are summarized in Table 5-4.
Data were generated from prior development documents, industry
visits, and 308 questionnaires.
TABLE 5-4. WASTEWATER FLOWS FROM ALUMINUM
FLUORIDE MANUFACTURING PLANTS [1]
(ro3/Mg of aluminum fluoride)
Wastewater
source
Scrubber water
Maintenance, equipment cleaning,
and work area washdown
Other (storm water)
Plant code
605
20.0
1.61
705
9.1
2.39
837
3.44
1.13
7.55
Note: Blanks indicate data not available.
II.5.1.2.2 Chlor-Alkali Industry
Chlorine, hydrogen, and caustic soda (NaOH) or caustic potash
(KOH) are produced together by electrolysis of brine. Chlorine
is used in the pulp and paper industry and the plastics industry,
for water treatment, and as an input in the manufacture of vinyl
chloride, chlorinated ethers, and other inorganic and organic
chemicals. About two-thirds of the production is for captive
use.
Date: 6/23/80 II.5.1-3
-------
ft-
(D
cn
to
u>
CO
o
M
•
Ul
TABLE 5-2. INORGANIC CHEMICALS SUBCATEGORY PROFILE DATA SUMMARY [1-3]
308 Data on file
Subcategory
Aluminum fluoride
Chlor-alkai
Diaphragm cell
Mercury cell
Chrome pigments
Copper sulfate
Hydrofluoric acid
Hydrogen cyanide
Nickel sulfate
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxJde
Chloride process
Sulfate process
Aluminum sulfate
Ammonium chloride
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
Bromine
Calcium
Calcium carbide
Calcium carbonate
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Total subcategory Total subcategory Total
production production per number of
capacity, Mg/yr yaar, Mg/yr plants
8,270,000 6,430,
3,540,000 2,750,
63,000 64,
37,
363,000 262,
289,000 166,
140,000 137,
40,300 39,
610,000 389,
401,000 259,
1,100,
123,
567,
130,
12,200,000 1,820,
277,
138,
000
000
500
000
000
000
000
900
000
000
000 (1974)
h
91 (1973)
000
K
000 (1971)
OOO
000
000
h
000 (1974)
7
45
32
11
18
14
11
12
9
5
2
8
5
84
6
6
7
3
4
105
5
0
21
Number
of
plants
on file
6
19
15
4
10
8
3
6
2
3
1
5
3
5
2
3
12
5
Production
14
19
3
7
8
4
20
16
31
4
30
1
Range,
Mg/yr
38-45,600
,700-1,500,000
,100-198,000
,500-8,800
45-9,100
,300-62,000
,500-64,600
62-8,250
,700-23,600
,700-66,800
20,400
,900-42,500
,000-74,500
,600-13,400
206-9,500
158-26,200
,200-63,700
555-49,800
,600-155,000
47-63,000
Average ,
Mg/yr
24,
221,
77,
6,
2,
22,
57,
2,
17,
37,
28,
49,
300
000
900
300
020
100
800
100
800
300
400
000
Percent of
Median, subcategory
Mg/yr production
35,500
103,000
70,400
6,400
510
15,800
57,800
1,600
16,900
24,800
25,600
43,000
143,000a
66
40
30
78
68
82
a
17,700
28,300a
82
51
37
95
a
29,800
17.0003
48,7003
77
56
31
40
Wastewater,
flow range ,
mVd
539-2,200
1,100-7,100
4-2,100
360-800
0-28
0-4,700
1,150-7,310
<1-200
3-100
455-720
273
1,140-4,770
35,000-125,000
(continued)
-------
D
JD
ft
n>
CTi
U)
CD
O
TABLE 5-2 (continued)
I
cn
Total subcategory
production
Subcategory capacity, Mg/yr
Hydrochloric acid
Hydrogen
Hydrogen peroxide
Iodine
Lead monoxide
Lithium carbonate
Manganese sulfate
Nitric acid 9,180,000
Nitric acid (strong)
Oxygen and nitrogen 31,200,000
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanganate
Sodium bicarbonate
Sodium carbonate 8,650,000
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate 814,000
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid 42,100,000
Zinc oxide
Zinc sulfate
Total subcategory
production per
year, Mg/yr
2,270,000
85,700
7,170,000
4,000
123,000
100 (1972)
250,000 (1973)
6,460
679,000
30,500,000
Total
number of
plants
83
7
17
0
87
171
1
9
3
10
4
12
5
30
6
15
151
Number
of
plants Range,
on file Mg/yr
20
3 5,560-28,700
11
5 5,300-60,200
9 2,400-378,000
4 79-634
8
3 3,800-36,500
2
7 12,400-57,300
5 4,400-27,000
5 27,800-170,000
47 5,300-47,700
308 Data on file
Production
Percent of Wastewater,
Average, Median, subcategory flow range,
Mg/yr Mg/yr production m3/d
25
66
11
121,000a
1,470,0003
10
2,830,000a
44,7003
300,0003
37
70,3003
364,000a
21
Note: Blanks indicate data not available.
Production per year (Mg/yr) of 308 data file plants. Total subcategory production rate not available.
Indicates the year data taken.
-------
TABLE 5-3.
BPT PARAMETERS FOR INORGANIC
CHEMICAL SUBCATEGORIES [1,5]
Pollutant, kg/Mg of Product (mg/L)
Aluminum
Subcategory
Chromium (total)
Daily maximum 30-Day average Daily MX!mum 30-Day average Daily maximum 30-Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0.34(20.0)
0.17(10.0)
0.10(1.5)
0.034(0.5)
Ho discharge of process wastewater pollutants to navigable waters.
No discharge of process wagtewater pollutants to navigable waters.
Reserved
Reserved
0.0044
No discharge of process wastewater pollutants to navigable waters except rainwater discharge
allowance for total suspended solids.
Ho discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater
Reserved
No discharge of process wastewater
Reserved
No discharge of process wastewater
No discharge of process wastewater
No discharge of process wastewater
pollutants to navigable waters.
pollutants to navigable waters.
pollutants to navigable waters.
pollutants to navigable waters.
pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor nay be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
0.009(7.5) 0.003(2.5)
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to r*"'gable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-6
-------
TABLE 5-3 (continued)
Pollutant, kg/Mg of Product (mg/L)
Chromium (+6)
Subcategory
Copper
Cyanide
Daily^naximum jO-Day^tverage Daily maximum 30-Day average Daily maximum 30-Day averag
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
fjrunoniujn chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
1 Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic aci
-------
TABLE 5-3 (continued)
Pollutant, kg/Mg of Product (mg/L)
Subcatpgory
Cyanide (A)
Fluoride
maximum ^ JO-Day average Daily maximum 30-Pay average Daily maximum^ 30-Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials]
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfitfe
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0.68(40.0)
0.34(20.0)
0.10(0.2)
0.034(0.10)
0.27(4.0)
15(30)
0.005(0.1) 0.0025(0.05)
No discharge of process wastewater pollutants to navigable waters.
Re served
Reserved
0.72
1.7(8.1}
0.36
0.84(4.0)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Re served
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
0.0004 0.0002
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor may be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters,
0.015(12.5) 0.005(4.2)
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-8
-------
TABLE 5-3 (continued)
Pollutant, kg/Mg of Product [rog/L)
Subcategory
Mercury
Nickel
Daily maximum 30-Day average Daily maximum 30-Day average Daily maximum 30-Day average
Aluminum fluoride
Chlor-«lkali
Diaphrahm cell
Mercury cell
Chrome pigment!
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andru**ow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichrornate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichrornate
Potassium iodide
Potassium metal
Potassium pernanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0.0025(0.005)
0.42(6.3) 0.14(2.1)
0.00014(0.00028)
0.006(6.5)
0.002(2.2)
No discharge of process wastewater pollutants to navigable waters.
0.006(5.1) 0.002(1.7)
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor may be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastevater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-9
-------
TABLE 5-3 (continued)
Pollutant, kg/M£__of _froduct (mg/U
Subcategory
Selenium Sulfide Zing
Pa_jly _aia_ximum 30-Day average Da»^n>*'tiinum 30-Day average Daily maximum 30-Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process?
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
{Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0.72(10.6) 0.27(4.0)
0.0015(1.6) 0.0005(0.5)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor may be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
0.015(12.5) 0.005(4.2)
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastawater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-10
-------
TABLE 5-3 (continued)
BQDS
_Ppllutant, kg/Mg^ of Product (mg/L)
TOC
TSS
Subeategory
Daily maximum 30-Day average Daily maximum 30-Day average Daily maximum 30-Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichrornate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process}
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(SoIvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium caroonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
ITrona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Pot&ssium iodide
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0.86(50.6)
0.43(25.3)
0.32(0,64)
0.32(0.64)
5.1(76,1) 1.7(25.4)
3.6(72.0) 1.6(36.0)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
0.069(74.2)
25(50)
2.4(48.0)
0.096(82.1)
0.44
4.6
21.0(100)
(50)
0.023(24.7)
1.2(24.0)
0.032(27.4)
0.22
2.3
10.5(50.0)
(25)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
0,14 0.07
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
0.56(50.0)
1.16(49.6)
0.12(19.5)
0.28(25.0)
0.58(24.8)
0.44
0.22
0.8
0.005
0.4
0.0025
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
2.7 0.9
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor may be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
0.09(75) 0.03(25}
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
0.20(222) 0.10(111)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved 0.46 0.23
Reserved 0.01 0.005
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-11
-------
TABLE 5-3 (continued)
Pollutant, kq/Mg of Product (rog/L)
Subca tegory
Daily maximum 30-Day average Daily maximum 30-Day average Daily maximum 30~Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
Ammonium chloride
(Anhydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Milk of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Feme chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process)
Iodine
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric acid
Zinc oxide
Zinc sulfate
0,36(7.2) 0.18(3.6)
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
8.8 4.4
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
0.0028 0.0014
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
0.002(51.3) 0.001(25.6)
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor may be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
NO discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
(continued)
Date: 6/23/80
II.5.1-12
-------
TABLE 5-3 (continued)
Subcategory
Pollutant, kg/Mg of Product (mq/L)
COD
Daily maximum 30-Day average
Aluminum fluoride
Chlor-alkali
Diaphrahm cell
Mercury cell
Chrome pigments
Copper sulfate
(Recovery process)
(Pure raw materials process)
Hydrofluoric acid
Hydrogen cyanide (Andrussow process)
Nickel sulfate
(Pure raw materials)
(Impure raw materials)
Sodium bisulfite
Sodium dichromate
Sodium hydrosulfite
Titanium dioxide
(Chloride process)
(Sulfate process)
Aluminum sulfate
Ammonium chloride
(Annydrous)
(Solvay byproduct)
Ammonium hydroxide
Barium carbonate
Borax
Boric acid
(Ore mined)
(Trona)
Bromine
Calcium
Calcium carbide
Calcium carbonate
(Mil* of lime)
(Solvay process)
Carbon dioxide
Carbon monoxide
Chromic acid
Cuprous oxide
Ferric chloride
Ferrous sulfate
Fluorine
Hydrochloric acid
Hydrogen
Hydrogen peroxide
(Organic process)
(Electrolytic process) •
Iodine \
Lead monoxide
Lithium carbonate
(Spodumene ore)
(Trona process)
Manganese sulfate
Nitric acid
Nitric acid (strong)
Oxygen and nitrogen
Potassium chloride
Potassium dichromate
Potassium iodide
Potassium metal
Potassium permanaganate
Sodium bicarbonate
Sodium carbonate
Sodium fluoride
Sodium hydrosulfide
Sodium metal
Sodium silicate
Sodium thiosulfate
Stannic oxide
Sulfur dioxide
Sulfuric at _d
Zinc oxide
Zinc sulfate
6.0-9.0
6.0-9.0
No discharge of process wastewater pollutants to navigable waters.
6.0-9.0
Reserved
Reserved
6.0-9.0
Wo discharge of process wastewater pollutants to navigable waters.
6.0-9.0
Reserved
Reserved
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
6.0-9.0
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
No discharge of process wastewater pollutants except that residual brine and depleted liquor may
be returned to original body of water.
Re served
Reserved
0.5(81.3) 0.25(40.7) 6.0-9.0
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
6.0-9.0
6.0-9.0
No discharge of process wastewater pollutants to navigable waters.
NO discharge of process wastewater pollutants to navigable waters.
€.0-9.0
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
6.0-9.0
No discharge of process wastewater pollutants to navigable water except that residual brine and
depleted liquor nay be returned to the original body of water.
No discharge of process wastewater pollutants to navigable waters.
6.0-9.0
No discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
No discharge of process wastewater pollutants to navigable waters.
Reserved
Reserved
Reserved
Reserved
No discharge of process wastewater pollutants to navigable waters.
Reserved
Vto discharge of process wastewater pollutants to navigable waters.
Reserved
No discharge of process wastewater pollutants to navigable waters.
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.1-13
-------
Two types of cells are currently used for the production of chlo-
rine and caustic: mercury and diaphragm cells. Mercury cells
account for approximately 30% of the production while the dia-
phragm cell accounts for 65%. The Downs cell is another electro-
lytic process for producing chlorine and sodium (or potassium)
from fused salt. However, the amount of chlorine produced by
this process is relatively small. Since the predominant method
of making chlorine and byproduct caustic is by the use of mercury
and diaphragm cells, this study of the chlor-alkali subcategory
is restricted to these two processes. In the processes described
below, sodium chloride is used as the starting material. The
same descriptions hold true, however, when potassium chloride is
used, but with one difference—the byproduct in the latter case
is caustic potash (KOH) instead of caustic soda (NaOH).
Mercury Cell Process. The sodium chloride (NaCl) solution
(brine or salt dissolved in water) is purified before it is sent
to the mercury cell for chlorine, caustic, and hydrogen produc-
tion. This is done by the addition of soda ash (Na2C03) and
small amounts of caustic soda until the pH increases to 10 or
11. The calcium and iron present in the brine and trace amounts
of other metals are precipitated as hydroxides or carbonates,
and the brine is sent to a clarifier for solids separation. The
underflow from the clarifier, known as brine mud, is sent to a
lagoon or is filtered. The overflow from the clarifier, which
is brine, is heated and brought to saturation by the addition of
salt recovered from the caustic evaporation. Its pH is then
lowered to 3-4 by addition of HC1 before it is introduced to the
mercury cell.
The mercury cell, in general, consists of two sections: the
electrolyzer and the decomposer or denuder. The electrolyzer is
an elongated steel trough that is inclined slightly from the
horizontal so that the mercury flows in a thin layer at the
bottom. This forms the cathode of the cell, and the brine flows
concurrently on top of the mercury. Parallel graphite or metal
anode plates are suspended from the cover of the cell. Electric
current flowing through the cell decomposes the brine, liberating
chlorine at the anode and sodium metal at the cathode. The me-
tallic sodium forms an amalgam with mercury:
2 NaCl (aq) + Hg±^Cl2 (aq) + 2 Na (Hg)
The amalgam from the electrolyzer flows to the denuder. The
spent brine (reduced to 22% saturation) is recycled to the brine
purification process where it is acidified to pH 3, blown with
steam for dechlorination, and saturated by the addition of salt
for reuse. In the denuder, the amalgam becomes an anode to a
short-circuited iron or graphite cathode. Deionized water added
to the denuder reacts with the amalgam to form hydrogen and
caustic. The mercury is returned to the electrolyzer. The
caustic formed has a concentration of 50% NaOH and is either sent
Date: 6/23/80 II.5.1-14
-------
to the storage tank or evaporated (if higher concentrations are
needed). The hydrogen gas is cooled by refrigeration to remove
water vapor and mercury. The chlorine gas process is similar to
that practiced for diaphragm cells.
Diaphragm Cell Process. As in the mercury cell process,
the brine is purified by the addition of caustic soda to elimi-
nate or reduce the calcium, magnesium, and iron impurities. The
resulting brine mud is similar to that produced from the mercury
cell except that it lacks the small amounts of ionic and metallic
mercury present in the recycled brine. The final pH of the
purified brine solution i"s adjusted to 6 by the addition of HCl,
and the brine is then fed to the diaphragm cells.
The saturated salt solution (26% concentration) is electrolyzed
in the diaphragm cell to form chlorine, hydrogen, and sodium hy-
droxide according to the reaction:
2 NaCl + 2 H2O±^:ci2 + 2 NaOH + H2
In one pass through the cell the salt solution is decomposed to
approximately half of its original concentration. The diaphragm
cell contains a porous asbestos diaphragm separating the anode
from the cathode. Chlorine is liberated at the anode, and the
hydrogen and caustic are produced at the cathode. In the past,
the predominant anode material was graphite with lead used to
provide an electrical contact and support. In recent years,
however, the majority of graphite anodes have been changed to
stabilized metal anodes. The use of metal anodes tends to re-
duce or eliminate the chlorinated organics and lead impurities
in the wastewaters.
The hydrogen from the top of the cathode is cooled to remove wa-
ter and other impurities, and it is either sold, vented to the
atmosphere, or burned to produce steam. The caustic leaving the
cathode has a concentration of 11% to 12% NaOH, which may be in-
creased to 50% through multiple-effect evaporation. If the
vapor evolved from the last effect of the evaporator is air
condensed in direct contact with water using barometric condens-
ors, the amount of wastewater produced may be quite large.
During evaporation, salt crystallizes and is removed from all of
the evaporators. The concentrated caustic is then settled and
stored. The chlorine from the cell is cooled to remove water
and other impurities. The condensates are either discharged
without treatment or recycled to the brine purifier after steam
stripping for chlorine recovery. The chlorine gas, after cool-
ing, is scrubbed with concentrated sulfuric acid to remove
water, the acid being used until a constant dilution is reached.
Wastewater Flows. Wastewater flows emanating from different
streams generated from the production of chlorine, hydrogen, and
caustic soda by mercury-cell manufacturing plants are summarized
Date: 6/23/80 II.5.1-15
-------
in Table 5-5. Data were generated from prior development docu-
ments, plant visits, and 308 questionnaires.
TABLE 5-5. WASTEWATER FLOWS FROM CHLORINE/CAUSTIC
MANUFACTURING PLANTS (MERCURY CELL) [1]
(m3/Mg of C12)
Wastewater Plant code
source 167 299 317 343 385 589 674 747 907
Brine mud 0.67 0.54 0.65 0.87
Tail gas
scrubber 2.25 0.11 0.05 3.39 0.58 0.02
Mercury-contaminated
wastewater 0.53 1.57 0.36
Note: Blanks indicate no data available.
The wastewater flows from chlorine/caustic manufacturing plants
using diaphragm cells are summarized in Table 5-6. Data were
collected from a prior development document, plant visits, and
308 questionnaires.
TABLE 5-6. WASTEWATER FLOWS FROM CHLORINE/CAUSTIC
MANUFACTURING PLANTS (DIAPHRAGM CELL) [1]
(m3/Mg of da)
Wastewater
source
Brine mud
Cell wash
Tail gas
scrubber effluent
Plant code
261 277 589 736 858
0.83 0.02 1.68 0.42
0.38 0.02 0.05 0.017 0.084
0.17
0
0
0
967a
.28
.18
.29/0.11
Note: Blanks indicate no data available.
a
Graphite anode plant.
II.5.1.2.3 Chrome Pigments
Chrome pigments are primarily sold in the merchant market; conse-
quently, captive use is minor. They are extensively used in
paints, printing ink, floor covering products, and paper, as well
as in ceramics, cement, and asphalt roofing.
Chrome pigments (a family of inorganic compounds containing chro-
mium, lead, iron, molybdenum, and zinc) include chrome yellow,
chrome orange, molybdate chrome orange, anhydrous and hydrous
Date: 6/23/80 II.5.1-16
-------
chromium oxide, zinc yellow and iron blues. At some manufactur-
ing plants, compounds are made in the same facility either
simultaneously or sequentially, depending on sales and market
requirements.
Chromium Oxide. Chromium oxide consists of two compounds,
anhydrous and hydrated chrome oxide (Guignet's green). Anhydrous
oxide is prepared by calcination of sodium dichromate with sulfur
or carbon. The use of sulfur as the reducing agent eliminates
C02, CO, and S02 emissions, but increases the sulfate raw waste.
In the manufacturing process using sulfur, raw materials consist-
ing of sodium dichromate and sulfur are mixed with water and the
resultant solution is fed to a kiln. The material is heated, and
reacted materials from the kiln are slurried with water, fil-
tered, washed, dried, ground, screened, and packaged. The efflu-
ent gases from the kiln containing sulfur dioxide and sulfur
trioxide are wet scrubbed before venting to the atmosphere.
Hydrated chromium oxide, also known as chromium hydrate and
Guignet's green, is made by reacting sodium dichromate with boric
acid. The raw materials are blended in a mixer, heated in an
oven, slurried with water, and filtered. The filtered solids are
washed with water, dried, ground, screened, and packaged. The
filtrate and wash water are treated with sulfuric acid to recover
boric acid. A waste stream containing some boric acid and sodium
sulfate leaves the boric acid unit.
Chrome Yellow and Chrome Orange. Chrome yellow is one of
the most important synthetic pigments. The chrome yellows con-
sist primarily of lead chromate and are made by reacting sodium
dichromate, caustic soda, and lead nitrate. Lead chromate is
formed as a precipitate during the reaction and is filtered and
treated with chemicals to develop the desired pigment properties.
The product is then dried, milled, and packaged. The filtrate
from the filtration operation is sent to the wastewater treatment
facility.
Molybdenum Orange. Molybdenum orange is made by the copre-
cipitation of lead chromate (PbCrOn) and lead molybdate (PbMoOi*).
The process consists of dissolving molybdic oxide in aqueous so-
dium hydroxide and adding sodium chromate. The solution is mixed
and reacted with a solution of lead nitrate. The precipitate
from the reaction is filtered, washed, dried, milled, and pack-
aged. The filtrate is sent to the treatment facility.
Chrome Green. Chrome greens are a coprecipitate of chrome
yellow and iron blues. Iron blues are manufactured by reaction
of aqueous solution of iron sulfate and ammonium sulfate with
sodium hexacyanoferrate. The precipitate formed is separated and
oxidized with sodium chlorate or sodium chromate to form iron
blues (Fe [NHi*] [Fe{CN}6] ) • Chrome green is produced by mechani-
cally mixing chrome yellow and iron blue pigments in water.
Date: 6/23/80 II.5.1-17
-------
Zinc Yellow. Zinc yellow, also called zinc chromate, is a
complex compound of zinc, potassium, and chromium made by the
reaction of zinc oxide, hydrochloric acid, sodium dichromate, and
potassium chloride. Zinc yellow is formed as a precipitate and
is filtered, washed, dried, milled, and packaged for sale.
Wastewater Flows. Process wastewater flows generated from
the production of chrome pigments are summarized in Table 5-7.
Data were generated from prior development documents, industry
visits, and 308 questionnaires.
TABLE 5-7. PROCESS WASTEWATER FLOWS FROM CHROME
PIGMENT MANUFACTURING PLANTS [1]
(m3/Mg of product)
WastewaterPlant code
source 002 257 409 894
Chrome yellow and chrome orange
Molybdate chrome orange
Zinc yellow
Chrome green
Chrome oxide
35
31
20
44
40
19
29
120
110
48
31
Note: Blanks indicate data not available or not
applicable.
II.5.1.2.4 Copper Sulfate
Most of the copper sulfate produced is sold in the merchant mar-
ket, and captive use is very small. Copper sulfate is used in
agriculture as an insecticide, an algicide, and as an addition to
copper-deficient soils. It is also used in electroplating, in
petroleum refining, and as a preservative for wood.
Copper sulfate is produced by reacting copper shot (blister cop-
per) with sulfuric acid, air, and water. Some plants do not
start with copper metal but use a waste stream from a copper re-
finery, which consists of copper, sulfuric acid, and a small
amount of nickel.
The resulting copper sulfate solution is either sold or fed to
crystallizers producing copper sulfate crystals. These are cen-
trifuged, dried, screened, and then packaged dry for sale.
Wastewater flows emanating from different streams generated from
the production of copper sulfate are summarized in Table 5-8.
Data were generated from prior development documents, plant vis-
its, and 308 questionnaires.
Date: 6/23/80 II.5.1-18
-------
TABLE 5-8. WASTEWATER FLOWS FROM COPPER
SULFATE MANUFACTURING PLANTS [1]
(m3/Mg of CuS04)
Wastewater
source Plant 034
CuSOi* waste
Effluent from lime treatment
Stream condensate
2.23
2.23
0.371
II.5.1.2.5 Hydrofluoric Acid
Produced as both anhydrous and aqueous products, hydrofluoric
acid (hydrogen fluoride) is used in the manufacture of fluorocar-
bons, which are used as refrigerating fluids, as plastics for
pressurized packing, and as dispersants in aerosol sprays. It is
also used in the production of aluminum, in the refining and en-
riching of uranium fuel, in the pickling of stainless steel, in
petroleum alkylation, and for the manufacture of fluoride salts.
With respect to volume of production, hydrofluoric acid (HF) is
the most important manufactured compound in the fluorine family.
The raw materials used for the manufacture of HF are fluorspar
(mainly CaF2) and sulfuric acid. The reaction between fluorspar
and sulfuric acid is endothermic. Reaction kinetics and product
yield depend on the purity and fineness of the fluorspar. The
sulfuric acid concentration, temperature of the reaction, and the
ratio of sulfuric acid to fluorspar are the most important reac-
tion variables.
Hydrogen fluoride generators are primarily externally fired rota-
ry kilns with acid and fluorspar continuously fed through a screw
conveyor at the forward end, and calcium sulfate (gypsum) removed
from the other end through an air lock. The product also leaves
this end, at the top, as a gas. The hydrogen fluoride gas leav-
ing the reactor is cooled in a precooler to condense high boiling
compounds, known as drip acid. These condensables consist pri-
marily of fluorosulfonic acid and unreacted sulfuric acid. Most
plants return the drip acid to the reactor, and the remaining
plants send it to wastewater treatment. The HF gas from the pre-
cooler is further cooled and condensed in a cooler/refrigeration
unit. The uncondensed gas containing the HF is scrubbed with
sulfuric acid and refrigerated to recover the product. The
scrubbed acid liquor is returned to the kiln, and residual vent
gases are further scrubbed with water to remove HF and other
fluoride compounds before they are vented to the atmosphere.
Crude hydrofluoric acid is then distilled to remove the residual
impurities, and the concentrate (anhydrous hydrofluoric acid) is
Date: 6/23/80 II.5.1-19
-------
stored in tanks. If aqueous hydrofluoric acid is desired, this
is then diluted with water to form a 70% HF solution as the final
product.
Wastewater flows emanating from different streams generated from
the production of hydrofluoric acid are summarized in Table 5-9.
Data were generated from prior development documents, 308 ques-
tionnaires, and industry visits.
TABLE 5-9. WASTEWATER FLOWS FROM HYDROFLUORIC
ACID MANUFACTURING PLANTS [1]
(m3/Mg of hydrofluoric acid)
Wastewater
source
Gypsum slurry
Drip acid
Scrubber wastewater
Other
Plant code
251
64.0
0.049
14.4
0.53
987
a
—
8.3
0.53
753
b
~d
2.3
8.4
426
a
~d
~b
120
~d
0.624
5.55
722
c
~d
-
167
41^6
40
5.2
705
c
0.018
11.2
22.5
837
6.5J
—
1.12
Dry disposal.
Not available.
Q
Total recycle.
Not applicable.
II.5.1.2.6 Hydrogen Cyanide
Over 50% of the hydrogen cyanide manufactured in the United
States is produced'by the Andrussow process, while about 40% is a
byproduct from acrylonitrile manufacture. A major portion of
the production is used in the manufacture of methyl methacrylate
for Lucite, Plexiglas molding and extrusion powders, and surface
coating resins. It is also used as a fumigant for orchards and
tree crops.
The hydrogen cyanide subcategory in this study is confined to the
Andrussow process, in which air, ammonia, and methane are reacted
to produce hydrogen cyanide. The raw materials are reacted at
elevated temperatures over a platinum catalyst. In addition to
hydrogen cyanide, the reacted gases contain ammonia, nitrogen,
carbon monoxide, carbon dioxide, hydrogen, and small amounts of
oxygen. The reactor gases are cooled and then scrubbed in one of
two processes that are used to remove the unreacted ammonia. In
one process the gases are scrubbed with phosphate liquor, the re-
sulting solution is decomposed, and the phosphate solution is re-
circulated. The recovered ammonia is recycled to the reactor.
In the second process sulfuric acid is used to absorb ammonia
from the reactor gases.
Date: 6/23/80 II.5.1-20
-------
The hydrogen cyanide is recovered from the ammonia scrubber ef-
fluent gases by absorption in cold water, and the waste gases are
vented to the atmosphere. The absorbed solution containing hy-
drogen cyanide, water, and other contaminants is distilled to
produce HCN gas of over 99% purity.
The water produced during the initial reaction for the formation
of hydrogen cyanide is purged with the distillation bottom stream
and is either recycled or discharged to the treatment facility.
Wastewater flows emanating from different streams generated from
the production of hydrogen cyanide are summarized in Table 5-10.
Data were generated from prior development documents, industry
visits, and 308 questionnaires.
TABLE 5-10. WASTEWATER FLOWS FROM HYDROGEN
CYANIDE MANUFACTURING PLANTS [1]
(m3/Mg of hydrogen cyanide)
Wastewater Plant code
source 765 782
Recovery and purification 6.3
Pump seal quenches 0.58
Flare stack flushes 0.09
Sample hoods 0.02
NH3 stripper caustic 0.24
Steam condensate from NH3 stripper 0.90
Freeze protection 0.06
Washdowns and cleanup 0.25
Boiler blowdown and condensate 1.48
Total 57 9.9
Note:Blanks indicate data not available.
II.5.1.2.7 Nickel Sulfate
The majority of the nickel sulfate produced in the United States
is sold in the merchant market. The major use of nickel sulfate
is in the metal plating industry, although it is also used in
dyeing and printing fabrics and for producing a patina on zinc
and brass.
Pure nickel or nickel oxide powder, spent nickel catalysts, and
nickel plating solutions or residues may be used to produce
nickel sulfate. The nickel sulfate produced when pure raw mate-
rials are used is filtered and sold or processed further using a
crystallizer to produce a solid nickel sulfate product.
The use of impure raw materials produces a nickel sulfate solu-
tion that must be treated in sequence with oxidizers, lime, and
Date: 6/23/80 II.5.1-21
-------
sulfides to precipitate impurities which are then removed by
filtration. The nickel sulfate solution can be sold or the prod-
uct may be crystallized, classified, dried, and screened to pro-
duce solid nickel sulfate for sale.
Wastewater flows emanating from different streams generated from
the production of nickel sulfate are summarized in Table 5-11.
Data were generated from prior development documents, plant vis-
its, and 308 questionnaires.
TABLE 5-11. WASTEWATER FLOWS FROM NICKEL SULFATE
MANUFACTURING PLANTS [I]
(m3/Mg of nickel sulfate)
Wastewater Plant code
source 369 572 120
Untreated wastewater 0.417
Treated wastewater 0.417
Scrubber wastewater 3.15
NiSOif wastewater 0.722
All nickel wastes 7.54
Treated effluent 7.54
Note: Blanks indicate data not applicable.
II.5.1.2.8 Sodium Bisulfite
Manufactured in both liquid and powdered form, sodium bisulfite
is used in the production of photographic chemicals, organic
chemicals, textiles, and in food processing. It is also used
in the tanning industry and in the sulfite process for the manu-
facturing of paper products.
Sodium bisulfite is produced by reacting sodium carbonate (soda
ash) with sulfur dioxide and water. This reaction produces a
slurry of sodium bisulfite crystals which can be sold, but which
is usually processed to form anhydrous sodium metabisulfite.
This requires thickening, centrifuging, drying, and packaging
operations.
Wastewater flows emanating from different streams generated from
the production of sodium bisulfite are summarized in Table 5-12.
Data were generated from prior development documents, plant vis-
its, and 308 questionnaires.
Date: 6/23/80 II.5.1-22
-------
TABLE 5-12. WASTEWATER FLOWS FROM SODIUM BISULFITE
MANUFACTURING PLANTS [1]
(m3/Mg of sodium bisulfite)
WastewaterPlant code
source 282 586 987
Untreated waste 2.67
Treated waste 2.67
MBS sump #1
MBS sump #2
Amine oxidation pond
Zinc sulfate pond effluent
Lime treatment influent
Truck washdown
S02 wastewater
No. 1 filter wash
Floor wash, spills, etc.
No. 2 filter wash
54-hour aeration
188
9.
9.
2.
78.
110
0.
85.
68
68
77
5
134
9
0.102
0.133
0.051
0.0123
0.0386
0.133
Note: Blanks indicate data not applicable.
II.5.1.2.9 Sodium Bichromate
Most of the sodium dichromate produced in the United States is
used in the chromic acid and pigment industries. It is used for
leather tanning and metal treatment, and as a corrosion inhibitor.
The starting materials for the preparation of sodium dichromate
are chromite ore, limestone, and soda ash. Their reaction forms
sodium chromate, which is reacted with sulfuric acid to produce
sodium dichromate.
Chromite ore is a chromium iron oxide containing ferrous chromite
(FeCr2Oi+ or FeOCr2O3) as well as small amounts of aluminum,
silica, and magnesia. At the plant site, the ore is ground to a
fine powder, mixed with soda ash, and calcined in rotary kilns.
The reacted product is leached with hot water and filtered. The
solid filter cake is dried in rotary kilns. The aluminum present
in the thickener overflow is hydrolyzed and removed from the chro-
mate solution as precipitated aluminum hydrate in slurry form.
The solution is centrifuged and the centrate is evaporated, to
give a concentrated solution of sodium chromate; the latter is
reacted with sulfuric acid to give sodium dichromate and sodium
sulfate. Sodium sulfate crystallizes as anhydrous sodium sulfate
from the boiling solution, and the crystals are removed by filtra-
tion. The filtrate is concentrated in multiple-effect evapora-
tors and fed to a water-cooled crystallizer. Sodium dichromate
crystallizes out and is centrifuged, dried, and packaged for sale
or future use.
Date: 6/23/80 II.5.1-23
-------
Wastewater flows emanating from different streams generated from
the production of sodium dichromate are summarized in Table 5-13.
Data were generated from prior development documents, 308 ques-
tionnaires responses, and industry visits.
TABLE 5-13. WASTEWATER FLOWS FROM SODIUM DICHROMATE
MANUFACTURING PLANTS [1]
(m3/Mg of sodium dichromate)
Wastewater Plant
source 493
Raw wastewater 4.95
Residue slurry 2.13
Mud slurry waste
Primary pond effluent
Treated effluent 28.9
Surface runoff
Noncontact cooling water
code
376 398
7
7
4
4
.68
.68
.16
-16 a
277a
Note: Blanks indicate data not
a2 streams.
appl
icable .
II.5.1.2.10 Sodium Hydrosulfite
Most of the sodium hydrosulfite produced in the United States is
sold in the merchant market. Sodium hydrosulfite is extensively
used in dyeing (cotton) and in the printing industry. It is a
powerful reducing agent and is used in the wood pulp bleaching,
reducing, and stripping operations of the food, vegetable oil,
and soap industries.
In the formate process, sodium hydrosulfite is produced by react-
ing sodium formate solution, sodium hydroxide solution, and
liquid sulfur dioxide in the presence of a recycled stream of
methanol solvent. Sodium hydrosulfite precipitates and forms a
slurry in the reactor. The coproduct, sodium sulfite is also
formed, as are sodium bicarbonate and carbon monoxide gas.
Methyl formate, a minor side product, is produced as the result
of a side reaction between sodium formate and methanol. This
side reaction product remains in the recycling methanol during
the entire process. As a result, some of the methanol must be
periodically purged from the recycle system to avoid excessive
buildup of this impurity.
The resulting slurry of sodium hydrosulfite in the solution of
methanol, methyl formate, and coproducts is sent to a pressurized
filter operation which recovers the crystals of sodium hydrosul-
fite. The crystals are dried in a steam-heated rotary drier,
then recovered and packaged. Filtrate and backwash liquors from
Date: 6/23/80 II.5.1-24
-------
the filter operation are sent to the solvent recovery system as
is the vaporized methanol from the drying operation. Excess heat
is avoided in the drying process as sodium hydrosulfite is heat
sensitive and tends to decompose to sulfite.
Wastewater flow emanating from plant 672, the only plant sampled,
totaled approximately 53 m3/d (14,000 gal/d). The three streams
making up this wastewater production were a coproduct stream pro-
ducing 0.91 m3/Mg of product, a raw waste stream yielding 1.87
m3/Mg of product, and a treated effluent stream producing 4.68
m3/Mg of product. The higher flow of the treated effluent stream
is due to the addition of sanitary waste and dilution water to
the aeration basin plus cooling tower and boiler blowdown to the
chlorine contact tank. Data were generated by prior development
documents, plant visits, and 308 questionnaires.
II.5.1.2.11 Titanium Dioxide
Titanium dioxide (Ti02) is manufactured by both a chloride and a
sulfate process. Ranking within the first 50 chemicals of all
United States chemical production, over 50% of this high volume
chemical is used in paints, varnishes, and lacquers. Approxi-
mately one-third is used in the paper and plastic industries.
Other uses are found in ceramics, ink, and rubber manufacturing.
Chloride Process. The chloride process uses rutile or up-
graded ilmenite ores as raw material, because the process re-
quires relatively pure materials with a high titanium and low
iron content. A beneficiation process, used to upgrade the ilmen-
ite ore, removes a part or all of the iron from the low quality
titanium ore. It is assumed that the wastes from the chloride
process using beneficiation differ from wastes of the process us-
ing pure high grade titanium ore. Therefore, the titanium di-
oxide subcategory has been further subdivided into three separate
categories: sulfate process using ilmenite ore, chloride process
using rutile or upgraded titanium ore, and chloride process using
ilmenite ore. This section is restricted to the chloride process
using rutile ore.
In the chloride process, ore and coke are dried and then reacted
with chlorine to form titanium tetrachloride. The titanium tetra-
chloride is then reacted with oxygen or air to form titanium di-
oxide and chlorine, the latter being recycled to the process.
The reaction generally takes place in a fluidized bed reactor and
the product gases leaving the reactor are cooled to remove the
impurities, although in some cases purification is accomplished
by washing the gases with liquefied titanium dioxide. Residual
uncondensed gases are treated to remove acidic materials before
being vented to the atmosphere.
The liquefied titanium tetrachloride contains impurities which
are removed by distillation. The distillate is the purified
Date: 6/23/80 II.5.1-25
-------
titanium tetrachloride and the impurities remain as a residual
which becomes waste. The tail gases from the distillation column
are scrubbed to remove acidic materials. The titanium tetrachlo-
ride product is then reacted with oxygen, as air, to form titani-
um dioxide and chlorine.
After the oxygenation reaction, the titanium dioxide forms a
solid and is separated from the gases. Residual chlorine is re-
frigerated and liquefied. Tail gases are scrubbed with caustic
soda to remove chlorine before being vented to the atmosphere.
The titanium dioxide is then sent to the finishing operation
where it is vacuum degassed and then treated with alkali, using
a minimum amount of water to remove traces of absorbed chlorine
and hydrochloric acid. The pigment is then milled, surface
treated for end-use application, dried, and packaged for sale.
Wastewater flows emanating from different streams generated from
the production of titanium dioxide by the chloride process are
summarized in Table 5-14. Data were generated by prior develop-
ment documents, industry visits, and 308 questionnaires.
TABLE 5-14. WASTEWATER FLOWS FROM TITANIUM DIOXIDE
MANUFACTURING PLANTS (CHLORIDE PROCESS) [1]
(m3/Mg of titanium dioxide)
Wastewater
source
Pit solids and distillation bottom waste
Settling pond overflow
Ti02 scrubber and other product wastewater
Inlet to wastewater treatment pond
Plant code
102 172 559
13.9
13.9
90
28.9 35.8 95.7
Note: Blanks indicate data not applicable or not available.
Sulfate Process. Ilmenite ore and slag from iron production
generally comprise the raw materials used for preparation of ti-
tanium dioxide by the sulfate process. Large amounts of water
and sulfuric acid are used in this process, and the majority of
plants are colocated with sulfuric acid plants. The preparation
of TiO2 by the sulfate process utilizes three important steps:
digestion, precipitation, and calcination.
The ore is dried, ground, and then reacted with sulfuric acid.
After the reduction, the product is dissolved in water and clari-
fied with the aid of flocculation agents to remove insoluble im-
purities such as silicon, zirconium, and unreacted ore. The con-
centrated solution is diluted with water and heated to form
titanium dioxide hydrate which precipitates out. The suspension
is filtered and the filtrate (known as strong acid) is separated
and either discharged or recycled. Filter residue is slurried
Date: 6/23/80 II.5.1-26
-------
with water, and conditioning agents (including potassium, zinc,
antimony, calcium compounds, and phosphate salts) are added to
control particle size, color, dispersibility, and photochemical
stability. This solution is then filtered. Residual acid and
iron originally present in the precipitate are removed with the
water of hydration by calcination. The resulting Ti02 pigment
is sent to finishing operations, which vary according to the
end-product requirement and application. Wet finishing opera-
tions may include some, or all, of the following steps:
repulping, milling, surface treatment, washing, and drying.
Alternative dry finishing operations may include one or more
milling steps followed by packaging.
Wastewater flows from the production of titanium dioxide by the
sulfate process are summarized in Table 5-15. Data were genera-
ted by prior development documents, industry visits, and 308
questionnaires.
TABLE 5-15. WASTEWATER FLOWS FROM TITANIUM DIOXIDE
MANUFACTURING PLANTS (SULFATE PROCESS) [1]
(m3/Mg of titanium dioxide)
WastewaterPlant code
source 555 559 605
Strong acid wastewater
Weak acid wastewater
Other process wastewater
8.49
78.2
362
7.4
85
7.8
93
597
II.5.1.2.12 Candidate Subcategories for Paragraph 8 and
Other Exclusions
The following paragraphs briefly describe the remaining 44 sub-
categories, which are candidates for exclusion under Paragraph 8
or for other reasons. No further consideration of these sub-
categories with respect to wastewater characteristics will be
presented in the remainder of this report due to this candidacy
and the absence of data.
Aluminum Sulfate. Aluminum sulfate is produced by the reac-
tion of concentrated sulfuric acid with bauxite, clay, and other
compounds containing aluminum oxide. The resultant solution is
purified to yield a product which can be sold or dehydrated to
form crystals. The primary use for aluminum sulfate is as a
flocculant in water treatment. Another use is in the papermaking
industry where iron-free aluminum sulfate is required for sizing
paper.
Date: 6/23/80 II.5.1-27
-------
Due to the small quantity of wastewater discharged by this indus-
try, this subcategory has been recommended as an exclusion candi-
date under Paragraph 8.
Ammonium Chloride. Most ammonium chloride is produced as a
byproduct in the manufacture of sodium carbonate (soda ash) by
the Solvay process. It is used in the manufacture of dry cell
batteries, explosives, dyes, as a washing powder, a soldering
flux, a chemical reagent, and a medicinal additive to livestock
feed. It is also used in pharmaceutical preparations and freez-
ing mixtures.
No significant concentrations of toxic pollutants were found in
the waste during screening of ammonium chloride plant 736. Am-
monium was found to be the only pollutant of significance. Since
ammonia is not a toxic pollutant, this subcategory has been recom-
mended as an exclusion candidate under Paragraph 8.
Ammonium Hydroxide. Ammonium hydroxide is predominantly
used as a chemical intermediary and reagent. It is also used in
the dyeing and bleaching of fabrics, the production of ammonium
salts and aniline dyes, and the extraction of alkaloids from
plants.
No plants with a discharge were found in this subcategory. There-
fore, this industry has been recommended as a Paragraph 8 exclu-
sion candidate.
Barium Carbonate. Barium carbonate is used in glass manu-
facturing, as a flux in ceramics and enameling, as an intermedi-
ate in the production of barium oxide and hydroxide, and as a
coating for photographic paper. It is also used in the synthetic
dyestuff industry and for the removal of soluble sulfate in brick
manufacturing.
No toxic pollutants were found at significant levels in the waste
during screening of barium carbonate plant 360. On the basis of
these findings, this subcategory has been recommended as an exclu-
sion candidate under Paragraph 8.
Borax. No descriptive information is available in Refer-
ences 1 through 4.
Boric Acid. Boric acid is used in the manufacture of chro-
mic oxide, glazes, enamels, textile fiberglass, and heat resist-
ant glass. It is also used medicinally as a mild antiseptic and
in atomic power plants as a nuclear moderator.
This subcategory has only three plants, and the total waste water
discharge is not high. Because of the nature of this industry,
it has been recommended that this subcategory be further studied.
Date: 6/23/80 II.5.1-28
-------
Bromine. No descriptive information is available in Refer-
ence s~T~~thro"ugh 4 .
Calcium. No descriptive information is available in Refer-
ences 1 through 4.
Calcium Carbide. Calcium carbide is produced by the reac-
tion of calcium oxide and coke. Calcium carbide is used to pro-
duce acetylene by reaction with water. Because the process for
calcium carbide production is dry, little wastewater is generated.
This subcategory has limited water effluent from the production
plants and has been recommended as an exclusion candidate under
Paragraph 8.
Calcium Carbonate. Calcium carbonate is manufactured both
in pure and impure form and it is extensively used in many indus-
tries. In the pure form, it is used in the rubber, paint, cement,
paper, and pharmaceutical industries.
No toxic pollutants were found at significant levels in the raw
waste during screening of calcium carbonate plant 883. On the
basis of these findings, this subcategory has been recommended as
an exclusion candidate under Paragraph 8.
Carbon Dioxide. Carbon dioxide is produced in gaseous, liq-
uid, or solid form. A major portion of the production is used
captively for the production of urea and for the secondary recov-
ery of oil and natural gas. It is also used for refrigeration,
in the food industry, for the carbonation of beverages, in fire
extinguishing equipment, and for oil well stimulation.
The only toxic pollutant found at a significant concentration in
the raw waste during screening at plant 241 was zinc at a concen-
tration of 910 yg/L. When the data were reviewed with plant per-
sonnel, it was discovered that the high zinc level was due to
zinc corrosion inhibitors; it was not process related. Therefore,
this subcategory has been recommended as an exclusion candidate
under Paragraph 8.
Carbon Monoxide and Byproduct Hydrogen. In the production
of hydrogen by refining natural gas, carbon monoxide is also pro-
duced. Carbon monoxide is recovered from several gas sources in-
cluding, partial combustion of oil or natural gas, coke oven gas,
blast furnace gas, water gas, and methane reformer gas.
Carbon monoxide and byproduct hydrogen form the building blocks
for other chemicals such as ammonia and methanol. The major use
of carbon monoxide is for the manufacture of methanol. It is al-
so used as a gaseous fuel for reducing oxides for special steels,
in nickel refining, and in the manufacture of ammonia, acetic
acid, and zinc white pigments.
Date: 6/23/80 II.5.1-29
-------
The only pollutants of significance, in terms of waste loads, in
this subcategory are chrome and zinc. However, this is the re-
sult of the use of corrosion-inhibiting additives in cooling
water; it is not process related. Therefore this subcategory has
been recommended as a Paragraph 8 exclusion candidate.
Chromic Acid. No descriptive information is available in
References 1 through 4.
Cuprous Oxide. Copper oxide is used in the manufacturing of
glass, ceramics, marine paints, and photoelectric cells. It is
also used in agriculture as a seed fungicide, and as an antisep-
tic and catalyst.
Only one plant was found to be producing this product at the time
of screening. Because this is now a single-plant industry, this
subcategory has been recommended for exclusion under Paragraph 8.
Ferric Chloride. Commercial solutions of ferric chloride
are produced from iron and steel pickling liquors which contain
ferrous chloride and hydrochloric acid. The steel pickling liq-
uors are preheated with steam and then reacted with iron, chlo-
rine, additional hydrochloric acid, and water to produce the
desired solution. These solutions are used as copper etchant in
photoengraving, in textile dyes, for the chlorination of copper
and silver ores, in pharmaceutical production, as an oxidizing
agent in chemical synthesis, and for water purification.
This subcategory has been recommended for exclusion under
Paragraph 8.
Ferrous Sulfate. No descriptive information is available in
References 1 through 4.
Fluorine. No descriptive information is available in Refer-
ences 1 through 4.
Hydrochloric Acid. Most hydrochloric acid is produced as a
byproduct in the manufacture of chlorinated organic compounds.
It is used in oil well activation, pickling of steel, metal clean-
ing, monosodium glutamate manufacture, and starch hydrolysis. It
is also used as an acid reagent in several chemical manufacturing
processes.
On the basis of the low toxic pollutant findings, this subcatego-
ry has been recommended as an exclusion candidate under Paragraph
8.
Hydrogen. No descriptive information is available in Refer-
ences 1 through 4.
Date: 6/23/80 II.5.1-30
-------
Hydrogen Peroxide. The organic process is the most commonly
employed method in the manufacture of hydrogen peroxide. Hydro-
gen peroxide is used as a bleaching agent in the textile and the
pulp and paper industries. It is also used in chemical manufac-
ture (e.g., plasticizers and glycerine) and wastewater treatment,
and as a rocket propellant.
During verification sampling of plant 765 it was discovered that
the presence of the organics listed in Table 5-16 (Section II. 5.2)
was not process related; it was caused by a weed killer used at
the plant site. Therefore, this subcategory has been recommended
for exclusion under Paragraph 8.
Iodine. No descriptive information is available in Refer-
ences 1 through 4.
Lead Monoxide. Lead monoxide is generally produced by the
air oxidation of metallic lead, followed by rapid cooling of the
product, then milling. Most plants in this subcategory do not
use water in the manufacturing process. Its major uses are for
noncontact cooling water and dust washdown. Thus, only plants
with a significant dust problem will have a significant quantity
of wastewater. This subcategory has been recommended for exclu-
sion under Paragraph 8 for this reason.
Lithium Carbonate. No descriptive information is available
in References 1 through 4.
Manganese Sulfate. Manganese sulfate is normally sold as
a mixture of tetra- and penta-hydrates. It is used in oils for
the manufacture of varnishes, in dyeing, and in the manufacture
of porcelain. It is also used in the fertilizer industry.
Only one plant in this subcategory was found to be in production
at the time of screening. Out of the eight plants contacted,
four no longer produced it, two were fertilizer manufacturers,
and one manufactured reagent-grade manganese sulfate. Because
this is now a single-plant industry, this subcategory has been
recommended for exclusion under Paragraph 8.
Nitric Acid. Most of the nitric acid produced is used in
the manufacture of ammonium nitrate and other nitrogen fertiliz-
ers. On-site captive use is extensively practiced. It is also
used in the manufacture of explosives, plastics, and other organ-
ic products, and as an acidic and pickling agent.
2,4-Dinitrophenol was found in the raw wastewater during screen-
ing at two plants and it is presumed to be from contamination by
the organic products manufactured at the plants, not process re-
lated. The chromium and zinc found are due to cooling water con-
ditioners present in the blowdown which is mixed with process
streams.
Date: 6/23/80 II.5.1-31
-------
It has been recommended that this subcategory be included in the
fertilizer industry guidelines.
Nitric Acid (Strong). Strong or concentrated nitric acid is
used in the manufacture of organic compounds where nitric acid is
required to act as an oxidizing agent rather than as an acid. It
is also used in the manufacture of dye intermediates and
explosives.
In a followup to the sampling discussed in the section entitled
Nitric Acid, it was found that the chromium and zinc are used as
corrosion inhibitors in the cooling water, and are not process
related. The other values are below significant levels. Verifi-
cation sampling at plant 623 confirmed this. On the basis of
these findings, this subcategory has been recommended for exclu-
sion under Paragraph 8.
Oxygen and Nitrogen. Oxygen, along with nitrogen, is pro-
duced from air by distillation of liquefied air. Oxygen is used
in the production of steel; in gas welding, medicine, jet fuel,
and sewage treatment plants; and in the manufacture of ethylene
and acetylene. In rocket propulsion, liquid oxygen is often used
as a cryogenic liquid oxidizer in the main stage boosters used
for space exploration.
The largest use of nitrogen is in the manufacture of ammonia by
the Haber process. It is also used in cryosurgery. As an inert
gas, it is used to prevent oxidation by air. In the liquid form,
it is used for low temperature refrigeration.
Only one toxic pollutant, copper, was found at a significant
level in the raw waste during screening of oxygen and nitrogen
plant 993.
Due to the small quantity of wastewater discharged by the indus-
try and the resulting low waste load generated, this subcategory
has been recommended as an exclusion candidate under Paragraph 8.
Potassium Chloride. No descriptive information is available
in References 1 through 4.
Potassium Dichromate. Only one United States plant current-
ly manufactures potassium dichromate. The production process in-
volves the reaction of a sodium dichromate dihydrate solution
with potassium chloride. The product is then crystallized by
vacuum cooling. Potassium dichromate is used as an oxidizing
agent and in brass pickling operations, electroplating, pyrotech-
nics, explosives, textiles, dyeing, printing, chrome products,
and Pharmaceuticals, and in many other processes.
This subcategory has been recommended for exclusion under Para-
graph 8 on the basis of being a one-plant industry.
Date: 6/23/80 II.5.1-32
-------
Potassium Iodide. Potassium iodide is used in photographic
emulsions, animal and poultry feeds, table salts, and analytical
chemistry. It also has a number of medical uses.
Due to the small quantity of wastewater discharged by the indus-
try, and the resulting low waste loads generated, this subcatego-
ry has been recommended as an exclusion candidate under Paragraph
8.
Potassium Metal. For the production of potassium metal,
potassium chloride is melted in a gas-fired melt pot and fed to
an exchange column. In the column the molten potassium chloride
contacts ascending sodium vapors, and sodium chloride and potas-
sium metal are formed. Major uses of potassium metal include
manufacture of organo-potassium compounds and production of sodi-
um potassium alloys used in lard modification and nuclear reactor
coolant.
Because the industry has only one primary plant, this subcategory
has been recommended as a candidate for a Paragraph 8 exclusion.
Potassium Permanganate. No descriptive information is avail-
able in References 1 through 4.
Sodium Bicarbonate. Sodium bicarbonate is made by the reac-
tion of sodium carbonate with water and carbon dioxide under
pressure and is typically a minor byproduct of soda ash manufac-
turers. Major uses include food processing, chemical processes,
Pharmaceuticals, synthetic rubber processes, and leather, paper
and textile production.
This subcategory has been recommended for exclusion under Para-
graph 8 due to the low quantities of toxic pollutants.
Sodium Carbonate. On-site captive production of sodium car-
bonate (soda ash) is a dominant practice. Sodium carbonate is
used in the manufacture of sodium bicarbonate, ammonium chloride,
and calcium chloride. Because of the nature of this industry, it
has been recommended that this subcategory be further studied.
Sodium Fluoride. Sodium fluoride is produced by three
plants in the United States with each plant using a different
process. Sodium fluoride is used to fluoridate water, to heat
treat salts, for pickling stainless steel, and as a wood preserva-
tive, an adhesive, an insecticide, and an antiseptic.
This subcategory has been recommended for exclusion under Para-
graph 8 due to the small number of plants.
Sodium Hydrosulfide. Sodium hydrosulfide is used in the
manufacture of sodium sulfide and other chemicals and paper
Date: 6/23/80 II.5.1-33
-------
(kraft). It is also used in dehairing of hides and industrial
wastewater treatment.
Due to the very small flows and waste loads generated by this in-
dustry, this subcategory has been recommended as a Paragraph 8
exclusion candidate.
Sodium Metal. Sodium metal is manufactured with chlorine by
electrolysis of fused salt. It is used in the production of tet-
raethyl lead gasoline additives, sodium cyanide, sodium peroxide,
and titanium and zirconium metals. In liquid form, it is used as
a nuclear reactor coolant; it is also used as a light, thermally
conductive solid in various applications.
No toxic pollutants were found at significant concentrations dur-
ing screening of sodium metal plant 339. On the basis of these
findings, this subcategory has been recommended as an exclusion
candidate under Paragraph 8.
Sodium Silicate. Sodium silicate is manufactured both in
liquid and anhydrous powdered form. It has many industrial
uses, such as additives in adhesives, flocculants, and cleaning
agents. It is also used in the production of soap and household
detergents.
Due to the low waste loads generated by this industry, this sub-
category has been recommended as an exclusion candidate under
Paragraph 8.
Sodium Thiosulfate. Sodium thiosulfate is extensively used
in the development of negatives and prints in the photographic
industry. It is also used in medicine, in the paper and dyeing
industries, and as a bleaching agent for natural products.
No toxic pollutants were found at significant levels in the raw
waste during screening of sodium thiosulfate plant 987.
On the basis of these findings, this subcategory has been recom-
mended as an exclusion candidate under Paragraph 8.
Stannic Oxide. No descriptive information is available in
References 1 through 4.
Sulfur Dioxide. Most sulfur dioxide is produced in the gas-
eous form, although a small percentage is also produced in liquid
form. In the gaseous form, it is predominantly used in on-site
manufacture of sulfuric acid. It is also used in the paper and
petroleum industries, as well as for fermentation control in the
wine industry, for bleaching in the textile and food industries,
and in the production of other chemicals.
Date: 6/23/80 II.5.1-34
-------
No toxic pollutants were found at significant levels in the waste
during screening of sulfur dioxide plant 363. On the basis of
these findings, this subcategory has been recommended as an exclu-
sion candidate under Paragraph 8.
Sulfuric Acid. Sulfuric acid is one of the most extensively
used of all manufactured chemicals. The major industrial use is
in the fertilizer industry, with on-site captive use of the prod-
uct as a dominant practice. It is also used in the manufacturing
of plastics, explosives, detergents, hydrofluoric acid, nuclear
fuel, and several other organic and inorganic products.
No toxic pollutants were found at significant concentrations in
the raw waste during screening of sulfuric acid plant 363. On
the basis of these findings, this subcategory has been recommend-
ed as an exclusion candidate under Paragraph 8.
Zinc Oxide. No descriptive information is available in
References 1 through 4.
Zinc Sulfate. No descriptive information is available in
References I through 4.
Date: 6/23/80 II.5.1-35
-------
11.5 . 2 WASTEWATER CHARACTERIZATION
Wastewaters in the Inorganic Chemicals industry vary considerably
between subcategories. Toxic pollutants are generally metals ex-
cept in cases where organic products are also produced at the
same plant. Concentrations and effluent flows range from insig-
nificant to considerable amounts. The following descriptions
provide detailed wastewater characterization information for the
11 inorganic subcategories not proposed for exclusion either
under Paragraph 8 of the NRDC consent decree or for other reasons,
Table 5-16 presents the maximum concentration of each toxic pol-
lutant found in each subcategory within the industry.
II.5.2.1 Aluminum Fluoride Industry
Water Use
Water is used in noncontact cooling of the product, for seals on
vacuum pumps, and for scrubbing the reacted gases before they are
vented to the atmosphere. Water is also used for leak and spill
cleanup and equipment washdown.
Wastewater Sources
Noncontact Cooling Water. Noncontact cooling water is used
to cool the product coming out of the reactor. In some cases it
is recirculated and the blowdc w>-> treated separately from other
process contact wastewater or discharged without treatment. The
water can be monitored for fluoride and if process contamination
occurs it can be diverted to the wastewater treatment facility
for fluoride removal.
Floor and Equipment Washings. The quantity and quality of
wastewater generated from these operations is variable and de-
pends largely on the housekeeping practices at the individual
plants.
Scrubber Wastewater. This is the major source of wastewater
requiring treatment before discharge or recycle back to the
scrubber. It is contaminated with hydrofluoric acid, aluminum
fluoride, and aluminum oxide, and, in some cases, the presence
of sulfuric acid and silicotetrafluoride has been detected.
These originate as impurities in the hydrofluoric acid used in
the process.
Wastewater Characteristics
A summary of daily and unit product raw waste loads found in
screening and verification sampling is shown in Table 5-17.
Date: 6/23/80 II.5.2-1
-------
D
0>
rt
(D
(Ti
M
U)
00
o
TABLE 5-16.
Ln
•
NJ
I
NJ
MAXIMUM RAW WASTEWATER CONCENTRATIONS OF TOXIC POLLUTANTS
FOUND AT SAMPLED INORGANIC CHEMICAL PLANTS3 [1]
(yg/L)
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Organics
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
Hexachloroe thane
Chloroform
Dichlorobromomethane
Bis(2-ethylhexyl) phthalate
Tetrachloroethylene
Phenol
Pentachlorophenol
Naphthalene
2 , 4 -Dinitrophenol
1,1, 1-Trichloroethane
C
Aluminum Fluoride Mercury cell
Verification Verification
Screening (2 plants) Screening (5 plants)
200 475 <200 9SO
<10 400
0.85 33 0.4 787
77 1,140 7.7 235
120 235 350 1,480
1 1,900
2 11 150 27,600
150 285 <100 2,450
110 97
0.6 1,460
<250 650
230 34,800
:hlor-Alkali
Diaphragm eel;
Metal anode
Verification
Screening (4 plants)
20 43b
10 660
2 62
940 18,800
525 16,600
255 2,000
9 347
54,400 22,100
<9 93
14
24 4,290
L
Graphite
anode
1,910
680
46
300
7,450
1,630,000
74
640
<2
3,200
15
197
621
90
691
309
120
196
Chrome Pigments
Verification
7,700 1,480
79 1,250
55,000 349,000
7,500 4,700
360 8,200
36,000 69,000
160 740
<10 28
7 20
4,100 273,000
-------
o
rr
• •
a\
to
\ TABLE 5-16 (continued)
CO
o
H
•
in
•
ro
I
U)
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
zinc
Copper
Screening
307
3,500
870
1,850,000
175
112,000
11,000
sulfate
Verification
(1 plant)
330
3,500
870
1,850,000
180
112,000
11,100
Hydrofluoric acid
Screening
70
10
2
73
770
5,190
2
150
25
5.5
8,120
Verification
(3 plants)
2,805
158
20
1,180
595
199
43
2,005
234
63
11,313
Hydrogen cyanide Nickel
Verl f icatlon
Screening (2 plants) Screening
9
1,300
73.3OO
166 186
55
4
175,500
<235
25 21
sulfate
Verification
(2 plants)
160
110
355
120
10
1,115,000
141
<3
Organio
Benzene
Carbon tetrachloride
1,2-Dichloroethane
Hexachloroethane
Chloroform
Dichlorobromomethane
Bis(2-ethylhexyl) phthalate
Tetrachloroethylene
Phenol
Pentachlorophenol
Naphthalene
2,4-Dinitrophenol
1,1,1-Trichloroethane 244
(continued)
-------
rr
0)
cr\
to
U)
00
o
Ul
K>
I
TABLE 5-16 (continued)
Titanium dioxide
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thalliua
Zinc
Sodium
Screening
30
6
17
375
8
3
250
2
2,480
bisul fate
Ver i f ication
(2 plants)
650
41
3,360
926
1,050
16.7
455
<30
3,600
Sodium
Screening
252,000
35
12,500
<5
<0.5
544
dichromat"
Verif icati on
(2 plants)
312,000
240
1,260.
22
228b
1,230
Sodium
hydro'.ulf ite
43
9,300
1,450
101
1,290
28
1,660
34
128
27,400
Chlondp Sul fate-
Verl f icat ion
(2 plants) Screening
20
11
338
15,200 124,000
1,480
5,150 3,730
6,230 6,370
64
19
3,110 3,840
Verif icat ion
(2 plants)
1,400
340
11.7
30,600
1,000
5,190
1,300
<15
41
16,600
Organics
Benzene
Carbon tetrachloride
1,2-Dichloroethane
Hexachloroethane
Chloroform
Dichlorobronomethane
Bis(2-ethylhexyl) phtnalate
Tetrachloroethylene
Phenol
Pentachlorophenol
Naphthalene
2,4-Dinitrophenol
1,1,1-Trichloroethane
160
373
(continued)
-------
o
»
rt
(D
(Ti
U)
oo
o
cn
TABLE 5-16 (continued)
Toxic pollutant
Metals and Inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Carbon Carbon
Boric acid dioxide monoxide
Screening Screening Screening
2,590
340
1.6 1.2
1.4
140
1,190 910 820
Hydrochloric
acid
Screening
3.5
2.0
5.5
Hydrogen Nitric
peroxide Screening
Screening (2 plants)
1109
<0.04
29
0.47
170
0.5
1209
acid
Verification
(1 plant)
1009
<0.02
<10
4.5
85
<15
7919
Nitric acid
Screening
(2 plants)
<2
40.0009
0.02
70
8.6
<5
0.69
9009
(strong)
Verification
(1 plant)
<2
<509
<0.02
<10
1.2
<50
<15
1159
Organice
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
Hexachloroe thane
Chloroform
DichlofpbronoMthane
Bls(2-ethylhexyl) phthalate
Tetrachloroethylene
Phenol
Pentachlorophenol
Naphthalene
2 , 4 -Dinltrophenol
1,1,1 -Tr ichloroethane
530
29f
4,850
215
(continued)
-------
o> TABLE 5-16 (continued)
rt
(D —
Oxygen
and Potassium Sodium carbonate Sodium Sodium
nitrogen iodide (Solvay process) hydro »ul fide silicate
O> Toxic pollutant screening Screening Screening Screening Screening
\
NJ Metals and inorganics
W Antimony 430
\ Arsenic
00 Asbestos
° Beryllium 230
Cadmium
Chromium
Copper 590 1,900
Cyanide
Lead 2,700
Mercury 1.3
Mickel 121
Selenium
Silver 35 <57 1.3
Thallium 28. 200
Zinc 930 750
Organic!
" Carbon tetrachlorida
H 1,2-Oichloroethane
Bexachloroethane
01 Chloroform
* Dichlorobromomethane
BisU-«thylnexyl) phthalata
Tstrachlorosthylene
Phenol 76
Pentachlorophenol
Naphthalene 90
2,4-Dinitrophenol
1,1,1-Trichloroethane
*No toxic pollutants were found in the following subcategories> ammonium chloride, barium
carbonate, calcium carbonate, sodium metal, sodium thiosulfata, sulfur dioxide, and su If uric
acid. Samples were taken but no data were given for the following suboategories: annonium
hydroxide, cuprous oxide, and manganese sulfate. No data were available for the following
subcategories: aluminum aulfate, borax, bromine, calcium, calcium carbide, chromic acid,
ferric chloride, ferrous sulfate, fluorine, hydrogen, iodine, lead monoxide, lithium
carbonate, potassium chloride, potassium dichronate, potassium metal, potassium permanganate,
sodium bicarbonate, sodium fluoride, stannic oxide, zinc oxide, and zino sulfate.
Found at one plant only.
jFrom organic pigment process.
Due to contaminated groundwater.
"includes other cyanide process wastes.
Organics due to organic weed killer - not process related.
jjchromium and zinc concentrations due to anticorrosion additives.
.Zinc concentration due to water source.
Presumed to be from contamination by the organic products manufactured at the plant - not
process related.
Note: Blanks indicate no data available.
-------
D
QJ
ft
(D
fo
U)
en
o
H
Ul
K>
I
TABLE 5-17,
SUMMARY OF RAW WASTE LOADINGS FOUND IN SCREENING AND
VERIFICATION SAMPLING - ALUMINUM FLUORIDE SUBCATEGORY [1]
Raw waste loadings
Pollutant
Toxic pollutants
Arsenic
Cadmium
Chromium
Copper
Nickel
Mercury
Selenium
Conventional pollutants
TSS
Fluorine
Aluminum
Minimum,
kg/d
0.071
0.072
0.02
0.025
0.0013
0.051
751
493
98.4
Average ,
kg/d
0.078
0.010
0.16
0.16
0.13
0.0041
0.11
2,920
727
220
Maximum ,
kg/d
0.086
0.25
0.33
0.26
0.0095
0.17
5,510
986
352
Minimum ,
kg/Mg
0.0007
0.0016
0.0002
0.00025
0.000027
0.001
16.3
9.71
0.97
Average,
kg/Mg
0.0016
0.0002
0.0035
0.0033
0.003
0.00005
0.0015
53.7
11.9
4.40
Maximum,
kg/Mg
0.002
0.0054
0.0071
0.0056
0.00009
0.002
No. of
plants
averaged
3
1
2
3
3
3
2
Note: Blanks indicate data not available.
-------
II.5.2.2 Chlor-Alkali Industry
Water Use
The water uses common to both mercury and diaphragm cells include
noncontact cooling, cell washings, tail gas scrubbing, equipment
maintenance, and area washdown. Noncontact cooling water is used
in cooling brine, caustic, chlorine, rectifiers, and compressors.
Large amounts of water are also introduced into the process
through the salt solution.
One water application unique to the mercury cell process is in
the decomposition of mercury-sodium amalgam to form caustic in
the denuder. In mercury cell plants, the quantity of water usage
was found to range from 7.6 to 204 cubic meters per metric ton of
chlorine produced, with noncontact cooling comprising approximate-
ly 70% of the total.
In the diaphragm cell process a large quantity of water is used
in the barometric condensers if the vapors from the caustic
evaporators are contact cooled. For plants practicing contact
cooling through barometric condensers, the average amount of
water usage is twice that of the mercury cell plant per metric
tons of chlorine produced (15 to 492 m3/Mg). Of the total water
usage in diaphragm cell plants, approximately 50% is used for
noncontact cooling. In addition, the amount of water used for
cleaning diaphragm cells is higher than that required for mercury
cells.
Waste Sources
Some of the waste sources produced during the manufacture of chlo-
rine and caustic by diaphragm and mercury cells are similar with
the notable exception of the presence of mercury in the waste-
waters from mercury cells and asbestos fibers in the wastewater
from the diaphragm cell plants. Following are descriptions of
the common wastewater streams, followed by descriptions of the
individual streams specific to mercury and diaphragm cells.
Common Wastes (Mercury Cell and Diaphragm Cell).
Brine mud - Brine mud is the major portion of the waste
solids produced from the two processes. The solids content of
the stream varies from 2% to 20% and ranges in volume from 0.04
to 1.5 cubic meters per ton of chlorine produced. The waste is
either sent to a pond or filtered. The overflow from the pond
(filtrate) is recycled to the process as makeup water for the
brine. In the mercury cell process, only 16% of the NaCl solution
is decomposed in the cell, and the unconverted brine is recycled
to the purification unit after dechlorination. This recycled
brine is contaminated with mercury and, therefore, the resulting
brine mud contains small amounts of mercury.
Date: 6/23/80 11.5.2-8
-------
Cell room wastes - The major components of this stream
include leaks, spills, and cell wash waters. The amount of cell
room waste generated per metric ton of chloride is generally
higher for diaphragm cell plants, and the wastewater from the
washing and rebuilding of the cathode contains asbestos fibers,
dissolved chlorine, and brine solution. In mercury cell plants,
the cell room wastes contain mercury, dissolved hydrogen, chlo-
rine, and some sodium chloride.
Cell room waste constitutes one of the major streams that has
to be treated for mercury. If graphite anodes are used in either
the mercury or diaphragm cells, the cell room wastes contain lead
and chlorinated organic compounds in addition to the normal
pollutants.
Chlorine condensate - Condensation from the cell gas is
contaminated with chlorine. At some plants, the condensates are
recycled to the process after chlorine recovery. Both contact
and noncontact water is used for chlorine cooling and for removal
of water vapor, so the amount of wastewater varies from plant to
plant. When graphite anodes are used, chlorinated hydrocarbons,
lead, and other impurities carried with the chlorine condense in
the first-stage cooler. The chlorinated organic compounds that
have been detected when graphite anodes are used are: chloroform,
methylene chloride, hexachlorobenzene, hexachloroethane, and
hexachlorobutadiene.
Spent sulfuric acid - Concentrated sulfuric acid is
used to remove the residual water from the C12 gas after the
first stage of cooling. In most cases, sulfuric acid is used
until a constant concentration of 50% to 70% is reached. The
spent acid might contain mercury, asbestos fibers, or chlorinated
hydrocarbons (depending on the type of cell) in addition to
chlorine. The volume of waste acid is typically of the order of
0.01 cubic meter per metric ton of chlorine.
Tail gas scrubber liquid - The uncondensed chlorine gas
from the liquefaction stage, containing some air and other gases,
is scrubbed with sodium/calcium hydroxide to form sodium/calcium
hypochlorite. When the equipment is purged for maintenance, the
"sniff" gas, or tail gas, is absorbed in calcium or sodium hy-
droxide, producing the corresponding hypochlorites. The amount
of tail gas scrubber water varies from 0.04 to 0.58 cubic meter
per metric ton of chloride for both diaphragm and mercury cell
plants.
Caustic filter washdown - The 50% caustic produced from
both mercury and diaphragm cells is treated with chemicals and
filtered to remove salt and other impurities. The filters are
backwashed periodically as needed; the wastewater volume is vari-
able and usually contains small amounts of mercury or asbestos
fibers in addition to the salt.
Date: 6/23/80 II.5.2-9
-------
Process Specific Wastes.
Condenser drainage - In mercury cells, the hydrogen pro-
duced is cooled in surface condensers to remove mercury and water
that is carried over with the gas. The wastewater is sent either
to the wastewater treatment facility or to the mercury recovery
facility. After mercury recovery, the water may be discharged to
the treatment facility or returned to the denuder after deioniza-
tion. Information on the volume of this waste stream is not
available.
Barometric condenser water - The wastewater specific to
the diaphragm cell process is the barometric condenser water. A
significant amount of water is used in contact cooling the vapors
from the evaporators used to concentrate the caustic. In the
mercury cells, the caustic comes out at a concentration of 50%
and does not require evaporators unless a caustic of high concen-
tration (e.g., 73%) is required. The barometric condenser waste-
water ranges from 89 to 191 cubic meters per metric ton of chlo-
rine. The barometric condenser wastewater is either discharged
without treatment or recycled, and a bleed is discharged with or
without pH adjustment.
Discharges from the barometric condensers contain some salt and
caustic as' a result of the carryover from the caustic solution.
When graphite anodes are used, the barometric condenser waste-
water contains lead.
Sulfate purge wastewater - During the concentration of
the caustic by evaporation, sodium chloride precipitates out.
The salt is removed and is washed with water to remove sodium
sulfate. A portion of wash water is recycled and the rest is
purged to waste in order to stop the buildup of sulfates. The
stream is one of the major sources of wastewater from chlorine/
caustic plants using diaphragm cells.
A summary of daily and unit product raw waste loads for all
plants sampled in the chlor-alkali/mercury cell subcategory is
shown in Table 5-18. Similar data for diaphragm cell plants are
presented in Table 5-19.
II.5.2.3 Chrome Pigment Industry
Water Use
In the chrome pigment industry water is used for noncontact cool-
ing, for washing the precipitated product, and as boiler feed for
steam generation. In some cases water is introduced into the
reactor along with the raw materials. In anhydrous and hydrated
chrome oxide manufacture, water is used for slurrying of the
reaction product and in scrubbing the reactor vent gases.
Date: 6/23/80 II.5.2-10
-------
TABLE 5-18. SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING
(MERCURY CELL PROCESS [1]
Pollutant
Toxic pollutants:
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Conventional pollutants:
TSS
Minimum,
Xg/d
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
6.
0059
00045
00032
0014
029
034
086
018
00036
0027
11
76
Average ,
kg/A
0.15
0.086
0.0091
0.028
0.11
0.068
2.84
0.046
0.058
0.071
0.42
307
Raw
waste loadings
Maximum,
kg/d
0.
0.
0.
0.
0.
0.
6.
0.
0.
0.
1.
1,200
29
27
025
094
020
13
71
072
22
14
10
Minimum,
kg/Mg
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
00001
000001
0000008
000004
0001
000089
0002
00003
00001
00002
0003
018
Average ,
kg/Mg
0.00045
0.0003
0.00005
0.00009
0.00033
0.00032
0.016
0.00026
0.00022
0.0003
0.0023
2.19
Maximum,
kg/Mg
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
10.
00074
01
0002
0004
0006
0007
063
0007
0008
001
01
8
No. Of
plants
averaged
3
5
5
6
6
5
6
4
4
4
6
Note: Blanks indicate data not available.
TABLE 5-19.
SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING
(DIAPHRAGM CELL PROCESS) [1]
Raw waste loadings
Pollutant
Toxic pollutants:
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
Mercury
Selenium
Antimony
Thallium
Conventional pollutants:
TSS
Minimum,
kg/d
0.000028
0.00034
0.0036
0.0037
0.00086
0.013
0.017
0.00018
0.00023
7.39
Average,
kg/d
0.0021
0.0015
0.58
0.12
0.021
0.28
0.08
0.00053
0.0016
0.00064
0.000045
23.8
Maximum,
kg/d
0.0033
0.0029
2.81
0.27
0.064
0.88
0.17
0.00082
0.003
53.9
Minimum,
kg/Mg
0.00000015
0.000001
0.000015
0.000011
0.0000037
0.00004
0.000057
0.0000003
0.000003
0.026
Average,
kg/Mg
0.0000056
0.0000033
0.00095
0.00041
0.000042
0.00064
0.00024
0.0000013
0.000004
0.000003
0.0000002
0.069
No. of
Maximum, plants
kg/Mg averaged
0.000014
0.000006
0.0046
0.0012
0.000095
0.0014
0.0007
0.0000025
0.000005
0.18
5
5
5
5
5
5
4
3
2
1
1
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.2-11
-------
Waste Sources
Some plants produce different pigment products sequentially in
the same process. At a few plants the different pigment products
are manufactured concurrently and the wastewaters combined and
treated at a single facility. The wastewater sources are similar
for all pigment products except that at chrome oxide plants an
additional scrubber waste is produced. The quantity of waste-
water and the pollutants vary for the different pigment products
since the pollutants are dependent on the raw materials used.
All the wastewaters generated in the chrome pigments subcategory
contain dissolved chromium and pigment particulates.
Additional pollutants that can be present are given below for
each major pigment group.
Chrome yellow and chrome orange: The raw wastewaters contain
sodium acetate, sodium chloride, sodium nitrate, sodium sulfate,
and lead salts.
Chrome oxide: The aqueous process effluent contains sodium sul-
fate. If boric acid is used in the preparation of hydrated
chromic oxide, the wastewater will contain sodium borate and
boric acid.
Chrome yellow and chrome orange: Additional pollutants present
in the raw wastewater from chrome yellow and chrome orange manu-
facture include sodium acetate, sodium chloride, sodium nitrate,
sodium sulfate, and lead salts.
Molybdenum orange: Process waste effluents from the manufacture
of molybdenum orange contain sodium chloride, sodium nitrate,
sodium sulfate, chromium hydroxide, lead salts, and silica.
Chrome green: The raw wastewater contains sodium nitrate. If
iron blue is manufactured on site as part of the process for
chrome green manufacture, the wastewater also contains sodium
chloride, ammonium sulfate, ferrous sulfate, sulfuric acid, and
iron blue pigment particulates.
Zinc yellow: The raw wastes contain hydrochloric acid, sodium
chloride, potassium chloride, and soluble zinc salts.
Because various plants make several chrome pigments sequentially
or concurrently, the unit hydraulic load going to the treatment
facility will be an average of all the waste loads from the dif-
ferent processes. The raw waste from a complex plant may contain
nearly all of the following substances: sodium acetate; sodium
chloride; sodium nitrate; sodium sulfate; potassium chloride;
lead, iron, and zinc salts; soluble chromium; and pigment
particulates.
Date: 6/23/80 II.5.2-12
-------
Wastewater Characteristics
A summary of daily and unit product raw waste loadings for all
plants sampled is shown in Table 5-20.
TABLE 5-20.
SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
CHROME PIGMENTS SUBCATEGORY [I]
Raw waste
Pollutant
Toxic pollutants
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
Cyanide
Organics
Phenols
Phenolics
Minimum,
kg/d
5.
90
0.87
698
6.
237
1.
52.
3.
06
38
2
11
Average,
kg/d
51.
5.
1,020
50.
347
1.
361
24.
0.
8.
,7
,44
.8
,71
4
93
80
Maximum,
kg/d
98.
10.
1,330
95.
458
2.
712
45.
0
0
2
03
8
loadings
Minimum,
kg/Mg
0.14
0.02
11.5
0.14
5.46
0.032
0.86
0.072
Average ,
kg/Mg
0
0
21
0
6
0
8
0
0
0
.87
.16 .
.5
.86
.49
.0325
.63
.41
.015
.14
Maximum,
kg/Mg
1.61
0.09
30.8
1.58
7.62
0.033
16.4
0.75
No. of
plants
averaged
2
2
2
2
2
2
2
2
1
1
Conventional pollutants
TSS
3,050
70.4
Note: Blanks indicate data not available.
11. 5 . 2 . 4 Copper Sulfate Indus t; ry_
Water Use
Water is used in the process as a reaction component which be-
comes a part of the dry product as its water of crystallization.
Water is also used for noncontact cooling, pump seals, and
washdowns.
Waste Sources
Noncontact Cooling Water. Noncontact cooling water is used
in the crystallizers and constitutes one of the main wastes.
This waste is treated before final discharge.
Contact Water. Washdowns, spills, and leaks are sources of
contact wastewater, but the flows are relatively small and inter-
mittent, and do not represent a major waste source.
Steam Condensate. A few plants use evaporators, and steam
condensate is an additional noncontact waste formed in the
process.
Solid Waste. Solid waste is produced by some plants. The
copper metal used in the process contains copper sulfides, which
are filtered out of the liquor and disposed of in a landfill.
Date: 6/23/80
II.5.2-13
-------
Plants that produce copper sulfate in the liquid form have no
contact waste streams from the process. The copper metal, acid,
and water are reacted together to form the copper sulfate solu-
tion product with no generation of liquid wastes.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for plant
034 is presented in Table 5-21.
TABLE 5-21.
SUMMARY OF RAW WASTE LOADINGS FOUND AT
COPPER SULFATE PLANT 034 [1]
Pollutant
Raw waste loadings
Average, Average,
kg/d kg/.Mg
Toxic pollutants
Antimony 0.014 0.00069
Arsenic 0.16 0.0078
Cadmium 0.039 0.0019
Copper 83.9 4.11
Lead 0.0079 0.00039
Nickel 5.08 0.25
Zinc 0.50 0.024
Conventional pollutants
TSS 1.78 0.087
II.5.2.5 Hydrofluoric Acid Industry
Water Use
Water is used in hydrofluoric acid production in noncontact
cooling, air pollution control, product dilution, seals on pumps
and kilns, and for equipment and area washdown. Although non-
contact cooling constitutes the major use of water, water is
also used, in a majority of cases, in the transport of gypsum
as a slurry to the wastewater treatment facility. The water for
gypsum transport is provided either by recycling the water from
the treatment facility or by using once-through cooling water.
Waste Sources
Drip Acid. Drip acid is formed in the first stage of cool-
ing of the gases emitted from the kiln. The drip acid primarily
contains high boiling compounds consisting of complex fluorides
and small amounts of hydrofluoric acid, sulfuric acid, and water,
Date: 6/23/80
II.5.2-14
-------
Nine out of eleven plants producing HF recycle the drip acid back
to the reactor.
Noncontact Cooling Water. Noncontact cooling water is used
for precooling the product gases emitted from the kiln. This
stream is relatively unpolluted, and the possibility of product
or other process compounds leaking into it is small. In some
plants, the cooling water is used to transport the waste gypsum.
Scrubber Wastewater. Scrubber wastewater constitutes the
predominant and major source of wastewater in plants which prac-
tice dry disposal of gypsum. The water contains fluoride, sul-
fate, and acidity. The fluoride is present as hydrogen fluoride,
silicon tetrafluoride, and hexafluosilicic acid. Scrubber water
consequently needs treatment for fluoride before discharge.
Distillation Wastes. Distillation wastes generally contain
HF and water. In some cases, vent gases from the distillation
column are scrubbed before they are emitted to the atmosphere,
resulting in scrubber water.
Gypsum Solids. Additionally, gypsum solids are generated as
a byproduct. Seven out of eleven plants producing hydrofluoric
acid slurry the gypsum with water and send it to a wastewater
treatment facility. Three of the plants transport the gypsum as
a dry solid.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for all plants
sampled in this subcategory is shown in Table 5-22.
TABLE 5-22. SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
HYDROFLUORIC ACID SUBCATEGORY [1]
Raw waste
Pollutant
Toxic pollutants
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Conventional pollutants
TSS
Fluorine
Minimum,
Kg/a
0
0
0
0
0
0
0
0
0
0
0
13,600
497
.015
.012
.0036
.14
.60
.10
.0027
.14
.016
.0054
.49
Average ,
kg/d
1
0
0
1
1
1
0
3
0
0
21
133,000
2,970
.63
.46
.011
.73
.42
.74
.056
.90
.066
.084
.1
Maximum ,
kg/a
6
1
0
5
2
S
0
13
0
0
72
247,000
7,890
.44
.12
.017
.49
.80
.62
.20
.0
.12
.16
.1
loadings
Minimum,
kg/Mg
0
0
0
0
0
0
0
0
0
0
0
170
14
.0003
.003
.0001
.0043
.015
.003
.00008
.0004
.0005
.00016
.014
.6
Average ,
kg/Mg
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
2,710
45.
03
0056
00027
024
028
046
00065
051
001
0021
41
4
Maximum,
kg/Mg
0
0
0
0
0
0
0
0
0
0
1
5,700
86
.12
.012
.00031
.06
.051
.165
.002
.14
.002
.003
.33
.9
No. Of
plants
averaged
4
3
3
4
4
4
4
4
3
2
4
Note: Blanks indicate data not available -
Date: 6/23/80
II.5.2-15
-------
II.5.2.6 Hydrogen Cyanide Industry
Water Use
Water is used in noncontact cooling in the absorber, pump seal
quenches, flare stack flushes, for washdown and cleanup of tank
cars, and for washing equipment and cleaning up leaks and spills.
Waste Sources
The following are the sources of wastewater produced from the
manufacture of hydrogen cyanide by the Andrussow process.
Distillation Bottoms. The wastewater contains ammonia,
hydrogen cyanide, and small amounts of organic nitriles. The
water consists of the water produced by the reaction plus scrub-
ber water used for the absorption of HCN. The absorption water
distillation bottoms are either recycled to the ammonia absorber
or discharged to the treatment facility. Even if the distilla-
tion bottom stream is recycled to the absorber, a portion of it
is discharged to stop the buildup of impurities.
Scrubber Streams. If the scrubber liquid is recycled, a
portion of it has to be purged to control the accumulation of
impurities. The bleed contains the acid used for scrubbing and
minor amounts of organic nitriles. The scrubber solution can
also be used for the manufacture of other products in which case
nothing is discharged from the scrubber operation.
Other Wastewater. This includes leaks and spills, equipment
and tank car washings, noncontact cooling water blowdown, and
rainfall runoff.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for all
plants sampled in this subcategory is presented in Table 5-23.
TABLE 5-23. SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
HYDROGEN CYANIDE SUBCATEGORY [1]
Raw waste loadings
Pollutant
Toxic pollutants
Total cyanide
Free cyanide
Conventional pollutants
TSS
NH3~N
BOD5
Minimum/
kg/d
173
106
152
3,880
24.5
Average ,
kg/d
205
113
383
5,790
4,320
Maximum,
kg/d
237
120
614
7,700
8,620
Minimum,
kg/Mg
0.81
0.49
1.02
26.2
0.16
Average ,
kg/Mg
1.20
0.65
1.94
31.1
20.2
Maximum,
kg/Mg
1.60
0.81
2.87
36.0
40.3
No. of
plants
averaged
2
2
Note: Blanks indicate data not available.
Date: 6/23/80 II.5.2-16
-------
II.5.2.7 Nickel Sulfate Industry
Water Use
Noncontact cooling water is used for nickel sulfate production in
the reactor and in crystallizers. Water is used for direct pro-
cess contact in the reactor. Small amounts of water are used for
maintenance, washdowns, cleanup, etc.
Waste Sources
Noncontact Cooling Water. Noncontact cooling water is the
main source of wastewater, but it is usually not treated before
discharge.
Contact Water. Direct process contact water constitutes
the major portion of treated waste. The water comes from the
preliminary preparation of spent plating solutions used in the
process. Plants which use impure nickel raw materials generate
a filter backwash waste stream with high impurity levels. This
stream must be sent through the treatment system.
Washdowns, spills, pump leaks, and maintenance uses account for
the remaining wastes produced by nickel sulfate plants.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for all
plants sampled is presented in Table 5-24.
TABLE 5-24.
SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
NICKEL SULFATE SUBCATEGORY [1]
Raw waste loadings
Pollutant
Toxic pollutants
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Minimum,
kg/d
0.000014
0.00023
0.0011
0.000082
0.27
0.00027
Average ,
kg/d
0.0015
0.00091
0.039
0.0014
0.000027
10.8
0.00059
0.000032
Maximum,
kg/d
0.0045
0.0018
0.11
0.0028
31.5
0.00091
Minimum,
kg/Mg
0.000002
0.00001
0.0001
0.00002
0.035
0.00003
Average,
kg/Mg
0.00017
0.00025
0.01
0.0001
0.00003
1.20
0.000035
0.000009
Maximum ,
kg/Mg
0.0005
0.0005
• 0.03
0.0003
3.45
0.00004
No. of
plants
averaged
3
2
3
3
1
3
2
1
Conventional pollutants
TSS
0.34
31.2
92.5
0.031
10.1
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.2-17
-------
II.5.2.8 Sodium Bisulfite Industry
Water Use
Direct process contact water is used to slurry the sodium carbon-
ate for the reaction. Noncontact cooling water is another water
use at one plant. Water is also used for pump seals, maintenance,
and washdowns.
Waste Sources
Noncontact Cooling Water. Noncontact cooling water from the
centrifuge is asource of waste at one plant.
Contact Water. Direct process contact water is the main
source of wastewater which must be treated, together with miscel-
laneous wastes such as water used for maintenance purposes, wash-
downs, and spill cleanup.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for all
plants sampled in this subcategory is shown in Table 5-25.
TABLE 5-25. SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
SODIUM BISULFITE SUBCATEGORY [1]
Raw waste loadings
Pollutant
Toxic pollutants
Antimony
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Conventional pollutants
TSS
COD
Minimum,
kg/d
0.00045
O.OQ023
0.018
0.005
0.000091
0.000091
0.0032
0.016
3.20
54.4
Average ,
kg/d
0.0018
0.0003
0.54
0.011
0.0045
0.00021
0.0068
0.18
12.9
117
Maximum/
kg/d
0.0041
0.00041
1.05
0.015
0.0095
0.00045
0.0091
0.42
25.4
234
Minimum!
kg/Mg
0.000007
0.000004
0.0003
0.00007
0.000007
0.000001
0.00005
0.0002
0.21
1.33
Average,
kg/Mg
0.000052
0.00001
0.011
0.00046
0.000092
0.000006
0.00031
0.0053
0.27
2.94
Maximum ,
kg/Mg
0.00008
0.000017
0.022
0.001
0.0002
0.00001
0.0007
0.0088
0.38
4.04
No. Of
plants
averaged
2
3
2
2
3
2
3
3
Note: Blanks indicate data not available.
II.5.2.9 Sodium Dichromate Industry
Water Use
Water is used for noncontact cooling, in leaching, for scrubbing
vent gases, and for process steam for heating.
Date: 6/23/80
II.5.2-18
-------
Water Sources
Spent Ore. The unreacted ore is removed from the process
as a sludge. The solids contain chromium and other impurities
originally present in the ore. The waste is disposed as a solid
waste in a landfill or is slurried with water and sent to the
treatment facility.
Noncontact Cooling Water and Cooling Tower Breakdown. The
noncontact cooling water is either used on a once-through basis
and discharged or is recycled and the blowdown discharged to the
treatment facility. In addition to dissolved sulfate and chlo-
ride, it may contain chromates.
Boiler Blowdown. The steam used for heating is recovered
as condensate, while the boiler blowdown is discharged to the
treatment facility. It may become contaminated with chromium
escaping from the process area and hence should be sent to the
wastewater treatment facility for treatment.
The majority of aqueous streams resulting from the manufacture
of sodium dichromate are recycled. Streams recycled include
condensates from product evaporation and drying; product recovery
filtrates; air pollution control scrubber effluents from product
drying, leaching, and roasting kilns; filter wash waters; and
equipment and process area washdowns. At two plants the waste-
water, consisting of boiler and noncontact cooling tower, is used
to slurry the spent ore residue to the wastewater treatment facil-
ity. At one plant, the only wastewater resulting from process
operations is the noncontact cooling water, which is used on a
once-through basis.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for all
plants sampled in this subcategory is presented in Table 5-26.
TABLE 5-26. SUMMARY OF RAW WASTE LOADINGS FOUND IN
SCREENING AND VERIFICATION SAMPLING -
SODIUM DICHROMATE SUBCATEGORY [1]
Pollutant
Toxic pollutants
Chromium
Hex . chromium
Copper
Nickel
Silver
Zinc
Selenium
Arsenic
Minimum,
kg/d
82
27.
0.
0.
o
.1
,5
.0091
.27
.067
Average,
kg/a
132
1,210
0,
4.
0.
0.
0.
0.
.32
.26
.058
.22
.23
.005
Raw waste
Maximum,
kg/a
181
3,105
0.92
8.98
3.91
loadings
Minimum,
kg/Mg
0.
0.
0.
0.
0.
.95
.466
.00005
.006
.0009
Average,
ka/Mg
1.
15.
0.
17
7
0046
0.034
0.
0.
0.
0.
0009
002
003
00008
Maximum,
kg/Mg
1.39
43.9
0.013
0.049
0.003
No. of
plants
averaged
2
3
3
3
1
3
1
1
Conventional pollutants
TSS 26,600 131,000 236,000 140 2,070 4,000
Note. Blanks indicate data not available.
Date: 6/23/80 II.5.2-19
-------
II.5.2.10 Sodium Hydrosulfite Industry
Water Use
Water is used in the process as makeup for the reaction solutions
and for steam generation in the rotary dryers. Water is also
used for noncontact cooling in the reactor gas vent scrubbers and
dryers, as well as pump seals and washdowns.
Water Sources
Distillation Column Residue. The strongest process waste is
the aqueous residue from the distillation column bottoms (solvent
recovery system). This waste contains concentrated reaction co-
products and is purged from the system at a rate of approximately
53 m3/d (14,000 gal/d). At one plant (672) this waste is sent to
a coproduct pond where it is held and either sold to the pulp and
paper industry or bled into the treatment system.
Dilute Wastes. The dilute wastes from process are contrib-
uted from leaks, spills, washdowns, and tank car washing. At one
plant (672) this is collected in a sump and then sent to the bio-
logical treatment system.
Blowdown. Cooling tower and boiler blowdown constitutes a
noncontaminated wastewater source. This is sent to the final
compartment of the chlorine contact tank without treatment for
discharge with the combined effluent of the treatment plant.
Scrubber Wastewater. The vent gas scrubbers create a waste-
water source which is sent to the methanol recovery distillers
for recycle. This waste eventually goes to the coproduct pond
with the distilling column bottoms.
Wastewater Characteristics
A summary of daily and unit product raw waste loads for the plant
sampled (672) is presented in Table 5-27.
II.5.2.11 Titanium Dioxide Industry
II.5.2.11.1 Chloride Process
Water Use. Water is used in noncontact cooling, for scrub-
ing tail gases from the purification and oxidation reactor to
remove contaminants, and in some cases, in the finishing opera-
tion of the product. The total amount of water usage varies from
45.3 m3/Mg to 383 m3/Mg of Ti02 produced. Cooling water consti-
tutes the major use of water and varies from 10.7 m3/Mg to 280
m3/Mg of Ti02 produced.
Date: 6/23/80 II.5.2-20
-------
TABLE 5-27.
SUMMARY OF RAW WASTE LOADINGS FOUND AT SODIUM
HYDROSULFITE PLANT 672 (FORMATE PROCESS) [1]
Pollutant
Raw waste loadings
Average, Average,
kg/d kg/Mg
Toxic pollutants
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Pentachlorophenol
Phenol
Conventional pollutants
TSS
COD
0.0041
0.81
0.11
0.041
0.16
0.0045
0.63
0.04
0.017
91.6
1,690
0.00007
0.14
0.0019
0.0007
0.0027
0.00008
0.011
0.0007
0.0003
1.57
28.9
Waste Sources.
Wastes from cooling chlorinator gas - These wastes
consist of solid particles of unreacted ore, coke, iron, and
small amounts of vanadium, zirconium, chromium and other heavy
metal chlorides, which are either dissolved in water and sent to
the wastewater treatment plant, or disposed in a landfill as
solid waste.
Chlorinator process tail gas scrubber waste - The un-
condensed gases, after the liquefaction of titanium tetrachlo-
ride, are wet scrubbed to remove hydrogen chloride, chlorine,
phosgene, and titanium tetrachloride and chlorine in the first
stage. In the second stage, they are scrubbed with caustic soda
to remove chlorine as hypochlorite.
Distillation bottom wastes - These contain copper,
sulfide, and organic complexing agents added during purification
in addition to aluminum, silicon, and zirconium chlorides. These
are removed as waterborne wastes, and reaction with water con-
verts silicon and anhydrous aluminum chlorides to their respec-
tive oxides.
Oxidation tail gas scrubber wastes - The gases from the
oxidation unit are cooled by refrigeration to liquefy and recover
chlorine. The uncondensed off-gases are scrubbed with water or
caustic soda to remove residual chlorine. When caustic soda is
used as the scrubbing solution, the resulting solution of sodium
Date: 6/23/80
II.5.2-21
-------
hypochlorite is either sold, decomposed, sent to the wastewater
treatment facility, or discharged without treatment. The scrub-
ber waste stream also contains titanium dioxide particulates.
Finishing operations waste - The liquid wastes from the
finishing operation contain titanium dioxide as a suspended solid
and dissolved sodium chloride formed by the neutralization of
residual hydrochloric acid with caustic soda.
Wastewater Characteristics. A summary of daily and unit
product raw waste loads found in screening and verification
sampling is shown in Table 5-28.
TABLE 5-28.
SUMMARY OF RAW WASTE LOADINGS FOUND IN SCREENING
AND VERIFICATION SAMPLING - TITANIUM DIOXIDE
SUBCATEGORY (CHLORIDE PROCESS) [1]
Raw waste loadings
Pollutant
Toxic pollutants
Chromium
Lead
Nickel
Zinc
Conventional pollutants
TSS
Iron
Minimum,
Kg/d
1.76
0.0032
0.14
0.75
442
7.57
Average ,
kg/d
64.4
2.0
2.04
1.47
4,140
768
Maximum,
kg/d
127
4.0
3.93
2.19
7,830
1,530
Minimum,
kg/Mg
0.024
0.0004
0.002
0.01
6.06
0.10
Average ,
kg/Mg
0.79
0.024
0.025
0.019
51.0
9.40
Maximum,
kg/Mg
1.55
0.049
0.048
0.027
95.9
18.7
•No. Of
plants
averaged
2
2
2
2
II.5.2.11.2 Sulfate Process
Water Use. Water is used in the preparation of titanium
dioxide by the sulfate process for noncontact cooling, air
emission control, and process reactions. In the process, water
is used to leach the soluble sulfate salts from the reaction
mass and to convert the titanyl sulfate to titanium dioxide hy-
drate. Water is also used to wash the titanium dioxide hydrate
precipitate free from residual acid and iron. Water is used for
air emission control during the drying of ore, on digester units,
and for the cleaning of the kiln gases before they are vented to
the atmosphere. In the digester unit, water seals are used to
maintain a vacuum. Large amounts of water are also used in the
finishing operations.
Waste Sources.
Strong acid waste - The concentration of sulfuric
acid in strong acid waste varies from 15% to 30% as H2S04. In
addition to sulfuric acid, the waste stream contains ferrous
Date: 6/23/80
II.5.2-22
-------
sulfate, titania, antimony, and other heavy metal salts. A
part of the acid is returned to the process and the rest is sent
to the treatment facility.
Weak acid waste - The waste generated from washing the
titanium dioxide hydrate precipitate is known as weak acid. The
concentration of sulfuric acid in this waste varies from 2% to
4% as HaSOit and contains various impurities, including iron sul-
fate, titania, antimony, and other heavy metal salts. It also
includes, in some cases, the conditioning agents added to the
precipitate prior to washing, to control and improve the quality
of the final product. The weak acid may also include kiln ex-
haust gas scrubber waste.
Scrubber wastes - Scrubber wastewater results from the
scrubbing of vapors emitted during the drying of the ore, during
digestion, and during kiln drying. The amount of wastewater
generated depends on the amount of water used and type of emis-
sion controls practices. The scrubber water contains titanium
dioxide particulates, acid mist, sulfur trioxide, and sulfur
dioxide. Of all the waste produced by the titanium dioxide-
sulfate process manufacture subcategory, the scrubber wastewater
constitutes the major portion.
Wet milling waste - These wastes are generated during
wet finishing of the titanium dioxide pigment. Wet milling is
used to produce pigment particles of the desired size and surface
character and requires steam and water for repulping the pigment.
Caustic soda is also used to remove any residual acidity from the
titanium dioxide pigment during the finishing operation. The
wastewater from wet finishing operations, therefore, contains
titania, sodium sulfate, and other agents added to improve or
achieve desired properties in the final product.
Digester sludge - After the digestion of the ore in
sulfuric acid, the resulting sulfates are dissolved in water and
the insoluble impurities are removed in a clarifier or filter.
These include silica, alumina, sulfuric acid, and unreacted iron.
The quality of this waste varies and depends on the type and
quality of ore used. Data on the quantity of this waste indicate
that approximately 210 kg/Mg is produced.
Copperas - The recovered ferrous sulfate is marketed
or disposed of as a solid waste. The amount of copperas gener-
ated is about 950 kg/Mg of Ti02. The copperas generally contains
small amounts of adsorbed sulfuric acid.
Wastewater Characteristics. A summary of daily and unit
product raw waste loads found in screening and verification
sampling is shown in Table 5-29.
Date: 6/23/80 II.5.2-23
-------
TABLE 5-29.
SUMMARY OF RAW WASTE LOADINGS FOUND IN SCREENING
AND VERIFICATION SAMPLING - TITANIUM DIOXIDE
SUBCATEGORY (SULFATE PROCESS) [1]
Raw waste loadings
Pollutant
Toxic pollutants
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Zinc
Organics
Phenol
Conventional pollutants
TSS
Iron
Minimum,
kg/d
7.66
0.091
132
8.30
3.28
8.30
53.4
0.20
Average, Maximum,
kg/d kg/d
18,
1,
2.
200
11,
8,
11,
0,
55,
20,500
58,500
. 0 28.3
.31
.40 6.85
327
.6 15.1
.56 12.4
.5 14.7
.76
.3 57.1
Minimum, Average,
kg/Mg kg/Mg
0.08 0.
0.
0.0009 0.
1.36 2.
0.094 0.
0.037 0.
0.086 0.
0.
0.55 0.
0.
211
602
21
014
027
11
12
089
12
0078
57
002
Maximum,
kg/Mg
0.32
0.078
3.37
0.16
0.13
0.15
0.59
No. of
plants
averaged
2
1
3
3
3
3
2
1
2
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.2-24
-------
II.5.3 PLANT SPECIFIC DESCRIPTIONS
The following paragraphs, tables, and figures describe, in as
much detail as possible, specific plants for 11 of the inorganic
chemical subcategories. Descriptions are limited to plants
chosen from the available data because they have the lowest con-
centrations of toxic pollutants in their final effluent streams
and/or are described in sufficient detail in Reference 1.
II.5.3.1 Aluminum Fluoride
Two plants were selected for more detailed description from avail-
able data on the aluminum fluoride industry based on the lowest
concentration of toxic pollutants in the final effluent stream.
Plant 705
Screening and verification data are provided for plant 705, which
produces both hydrofluoric acid and aluminum fluoride. Waste-
waters from both processes are mixed and sent to the treatment
facility. The combined wastewater is neutralized with lime and
sent to a series of settling ponds. Effluent from the last pond
is given a final pH adjustment before a portion is discharged and
the remainder recycled to the process. Plant 705 does not treat
noncontact cooling water.
Figure 5-1 (next page) shows a simplified block diagram of the
process including the wastewater treatment facility and sampling
locations. Table 5-30 summarizes the flow data of the sample
streams and the emission characteristics for important classical
pollutant parameters for screening and verification data. Table
5-31 provides toxic pollutant raw waste loads.
TABLE 5-30. FLOW AND POLLUTANT CONCENTRATION DATA OF
THE SAMPLED WASTESTREAMS FOR PLANT 705
PRODUCING ALUMINUM FLUORIDE [1]
Sampling
phase
Screening
Verification
Wastestream
description
AlF3 scrubber
Surface drains3
cooling tower,
blowdown, etc.
Treated waste
A1F3 scrubber
Surface drains,3
cooling tower,
blowdown, etc.
Treated waste
Flow,
m3/Mg
A1F3
8.9
17.8
24
8.9
17.8
24
SS
117
3.5
1.98
12.8
3.57
0.048
kg/Mg A1F3
Fluoride
4.67
6.14
1.63
12.3
3.01
0.55
Aluminum
6.94
0.76
0.168
4.08
0.475
0.012
Contribution from both HF and A1F3 plants.
Date: 6/23/80 II.5.3-1
-------
M
a£3
u u <
t=Z =
\
1
i
j
5
I
i
5
1
j
i
k
!
1
C
'•
\
i
1
i
1-
1
s
a
J
«
a
t
s
3
i
|
?
I
M
i I
fr
S
t
E!
V *
2i
b
a
3
&.
M
9
i
f
•4
lik
t
i
t
3
B
1
I
|
t
\
-*
§
— ••
U
i
L»
r*
P
«
i
s
1
f
j
i
I
i
i
\
\
***
_j^
-%§
K
i
i
ft
§
1
«
i
1
f
s
J
•
B
i
5
Sg
i^
ii
s
®,
1
«— »•
1
a
e
\
i
i
c
c
i
S
I
(
!
i
i
i
I
4
I Ik U
;s;
i
&*
i
5
!
?
j
H
S
;
2
i
I
1
i
1
i
(
»-
K
e
rj
ASTE STREAMS !
icturing
] -
» 'U 1—
* 4-) L_,
X) §„
•^ (0 .p
g c
•H
tn o
£a
i i fi
e -U
l-i -H
rt j
P! e
4J tQ
m
r- ^
e ^
(T5 4J
tT* hn
fO c
•H -H
'O ^
o
O in
W -H
en ^
QJ o
3
O r-H
M 4-4
M i
ro C
1-1 -H
aj e
C 3
QJ rH
O to
r— |
1
in
3
•H
Date: 6/23/80
II.5.3-2
-------
TABLE 5-31.
Plant 605
TOXIC POLLUTANT LOADS IN RAW WASTE
ALUMINUM FLUORIDE AT PLANT 705 [1]
(kg/Mg product)
Pollutant
Arsenic
Selenium
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Cadmium
Screening
phase
0.002
0.001
0.0016
0.0027
0.0004
0.000036
0.003
0.008
Veri-
fication
phase
0.002
0.0054
0.0071
0.001
0.000027
0.0056
0.0047
0.0002
Screening and verification
data shown in table were not
completely identified in
Reference 1; reported data
were assumed by MRC to corre-
spond to the screening and
verification phases as noted
in the table.
Note: Blanks indicate data not
available.
Verification data are provided for plant 605, which produces
hydrofluoric acid and aluminum fluoride. Wastewaters from the
two processes are combined and sent to gypsum ponds for suspended
solids removal. The overflow is treated with an effluent stream
from another plant product for pH control and neutralization
prior to discharge.
Figure 5-2 is a simplified flow diagram showing the sampling
points for plant 605. Table 5-32 summarizes the verification
data for the wastestream flows and the emissions of selected
classifical pollutants. Table 5-33 presents data for water usage,
wastewater flow, and solids generated for plants 705 and 605.
Date: 6/23/80
II.5.3-3
-------
ft
fD
Ul
00
o
<_n
U>
I
J „ ' K
H * . I**1"
in* en* wren
«ir rum
II
11
«
imM4iMtai
WASTE STREAMS SAMPLED
13"
Mti «CID not onm
Figure 5-2. General process flow diagram at plant 605 manufacturing
aluminum fluoride, showing the sampling points [1] .
-------
TABLE 5-32. FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
605 PRODUCING ALUMINUM FLUORIDE [1]
Stream
4
6
2
3
Wastestream
description
A1F3 scrubber water
S02 scrubber water
Gypsum pond influent
Gypsum pond effluent
Flow,
m3/Mg
A1F3
11.9
12.2
24.9
24.8
kg/Mg
SS
14.7
2.6
0.232
A1F3
Fluoride
5.53
19.3
16.4
8.00
TABLE 5-33. WATER USAGE, WASTEWATER FLOW, AND
SOLIDS GENERATION FOR ALUMINUM
FLUORIDE PLANTS 705 and 506 [1]
(m3/Mg A1F3)
PlantPlant
Description 705 605
Water usage
Noncontact cooling
Indirect process contact 1.15
(pumps, seals, leaks, spills)
Maintenance 2.4 1.6
(cleaning and work area
washdown)
Scrubber 9.52 20.0
Wastewater flow
Scrubber water 9.1 20.0
Maintenance (equipment cleanup 2.39 1.61
and work area washdown)
Other
Solids generated 54 69
Note.Blanks indicate data not available.
Date: 6/23/80 II.5.3-5
-------
II.5.3.2 Chlor-Alkali
II.5.3.2.1 Chlor-Alkali Mercury Cell
Two plants (plants 747 and 317) were selected for detailed de-
scription from available data on the chlor-alkali (mercury cell)
industry. One other plant (plant 167) is described because of
the variety of treatments used in processing the final effluent;
however, no final effluent data are available for that plant.
Plant 747. Verification data are provided for plant 747.
At that plant, the brine dechlorination system has been converted
from barometric condensers to a steam ejector system. The con-
version resulted in increased chlorine recovery and reduced con-
tact wastewater. By providing settling and secondary filter
facilities, the brine filter backwash has been eliminated. The
tail gas scrubber liquid is offered for sale; if not marketed,
it is decomposed. The mercury-bearing wastewaters are collected
and treated with Na2S. The reacted solution is filtered, and the
filtered solids are retorted for mercury recovery. The filtrate
is mixed with the other process wastewaters, and the pH is ad-
justed before discharge.
The flow diagram of the manufacturing process, including the
wastewater treatment facility, is given in Figure 5-3 (next page),
Table 5-34 provides the flow data for the sampled streams. The
residual chlorine effluent loading at Plant 747, after treatment,
ranged from 0.0 to 0.006 kg/Mg. Table 5-35 presents residual
mercury loadings, and Table 5-36 shows final effluent loadings of
toxic pollutants.
TABLE 5-34.
FLOW AND POLLUTANT CONCENTRATION DATA OF THE SAMPLED
WASTESTREAMS FOR PLANTS 747, 317, AND 167 PRODUCING
CHLORINE BY USING MERCURY CELLS [I]
Haeteatreaa
Plant Str«a»
Cell waate
Treated *»*t*
Input da drying
tower
(XitpMt Cla drying
Cower
Dechloro ayKeai
Cla condensete
Tail gat-hypo
0.23
0.23
0.15
0.43
0 00*7
0.022
O.O00073
0.000017
0.00041
Cell waat* 0.29
Brirv* *ud filtrate 0.54
Tank car wash 0.11
Collection tank 0.41
tHa+31
Treated effluent 0.41
Daioniver effluent 0.29
Honcontact US
cooling water
Tinal affluent 136
Ul chlorine 3.35
waste*
Cell M»h O.OO93
•rin« proceia 1.78
water
Created chlorine 5.SB
wait*
flr in* leud 0 fc;
0.16
0.014
O.OOOO043
0.00000087
0. 000031
0.00398
0.000063
0.000011
0.000066
0.0000038
0.0014
0.0032
O.OO024
0.0000026
O.OOO01B
0.00065
0.00696
0.0037
0.000027
0.013
0.26
0.00196
8.67
0.044
0.0052
2.16
2.45
1.89
0.00057
O.O071
0.013
3.99
0.0043
0.000023
0.0000035
0.000015
0.0000018
0.0000008
0.000014
0.019
0.0000036
0.00056
0.000043
0.00000029
0 00014
0.00036
0.013
0.0000067
0.000009
o ooi e
.000087
•tote llankB indicate data not available
Date: 6/23/80
II.5.3-6
-------
o
pj
ft
CD
CTl
fO
U>
00
O
H
UJ
I
-J
T
-»^-Q BUM
je MM
t- GVHTIN
*-| tOffXMIDCT *J
L WJ
ncnno.
°°" «
T
» 10*1
> f-
r
1
IS
s
MLT1
cn
£
t
ojmc
uj
An
^ H
man
MO
OU.II
a2
^~
»«9
-•/>,
Miai
J
c
14
ai
cno.
"j
n»ir.
t
t
•f
WASTE STREAMS SAMPLED
II
I U
nun ID
UMTIU.
FWOCT
Figure 5-3. General process flow diagram at plant 47, manufacturing chlorine
caustic (mercury cell), showing the sampling points [1].
-------
TABLE 5-35. EFFLUENT LOADINGS FROM SELECTED CHLOR-ALKALI
PLANTS USING MERCURY CELLS [1]
Mercury waste load, kg/Mg
Plant Average
Maximum daily
Max imum
30-day average
747
747d
317d
0.000055
0.000055
0.000006
0.00008
0.000083
0.000048
0.000067
0.000065
0.00001
From plant long-term monitoring data.
TABLE 5-36.
EFFLUENT TOXIC POLLUTANT LOADS
FOLLOWING MERCURY TREATMENT AT
CHLORO-ALKALI PLANTS3' [1]
(kg/Mg product)
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
Plant 747
<0.059
<0.002
0.03C
<0.011
<0.006
0.016
<0.011
<0.0035
<0.01
<0.006
Plant 317
<0.10
<0.008
<0.001
<0.02
<0.012
0.07
<0.028
<0.006
<0.1
<0.21
Flow = 0.23 m3/Mg at Plant 747,
and 0.41 m3 at Plant 317.
""Results of 3-day verification
sampling.
i
'Indicates effluent load higher
than influent load.
Plant 317. Verification data are provided for plant 317.
At that plant, the brine purification mud is mixed with spent
sulfuric acid and sodium hypochlorite solution. The treatment
removes mercury from the mud and transfers it to the solution.
The solution is filtered, and the solids are landfilled. The
filtrate is mixed with other mercury-contaminated wastewater,
which includes the brine purge, cellroom liquid wastes, and plant
Date: 6/23/80
II.5.3-8
-------
area washwater. This is then reacted with sodium hydrosulfide to
precipitate the mercury as mercury sulfide and then filtered.
The solids are sent to a mercury recovery unit; the filtrate is
sent to a holding tank. The effluent from the holding tank is
mixed with deionizer waste and noncontact cooling water before
discharge.
The process flow diagram, given in Figure 5-4 (next page), shows
the waste streams sampled. Table 5-34 summarizes the flow data
and pollutant emissions for the sampled streams. Table 5-35
presents residual mercury loadings for plant 317; Table 5-36
shows final effluent loadings of toxic pollutants. Table 5-37
provides the unit flow data from the different wastestreams for
plants 317 and 167.
TABLE 5-37. WASTE FLOW DATA FOR CHLOR-ALKALI
PLANTS USING MERCURY CELLS [1]
Wastestream description
Brine mud
Tail gas scrubber
(hypochlorite solution)
Mercury-contaminated
wastewaters
Plant
317
167
317
167
317
167
Flow,
m3/Mg C12
0.54
0.67
0.046
2.25
0.529
Note. Blanks indicate data not available.
Plant 167. Verification data are provided for plant 167.
At that plant, the wastewater streams, consisting of filter back-
wash, cell-room wash, rainwater runoff, and leaks and spills, are
combined and treated for mercury removal. The water is sent to
a holding lagoon; the overflow is reduced by reaction with fer-
rous chloride, which precipitates mercury. The reacted solution
is sent to a clarifier. The clarifier underflow is disposed of
in a landfill. The overflow is filtered, and the filtrate is
passed through activated carbon and an ion exchange column prior
to discharge to a lagoon. Effluent from the lagoon, after pH
adjustment, is discharged.
Figure 5-5 shows the simplified process flow diagram for plant
167, including the sampling locations. Table 5-34 gives the
flow data and pollutant emissions for the sampled streams. Table
5-38 presents toxic pollutant loadings for raw waste from three
plants.
Date: 6/23/80 II.5.3-9
-------
ft
to
(Ti
NJ
CO
CO
O
Ln
•
OJ
I
SMT
or GAS
e
WASTE STREAMS SAMPLED
DC-IONIZED Nnrcoriracr
WV5TK COOLING
Figure 5-4. General process flow diagram at plant 317, manufacturing chlorine
caustic (mercury cell), showing the sampling points [1].
-------
D
0)
rt
(Ti
U>
CD
O
U1
•
U)
I
mrucN^D
V
TO mare * up tun
a_ J-t
fiMUmUN
so.
10 C
1
JUS
UM>
1
•auMii
r
wtm
riLiu ^. cam
i
kK:
MO M
«Mt9l
FOB
«i
1C'
MOM9H -rlj.
H-0 •cms*
"/* H/J
mi«
SffMT MM L
MDH ttnmtn.
^. OtXlJH
'•» t
nncLK '"
COX HIM "f
ro SIUNICX^
COL IUM
wau»H9
MO SPIUS
1
«
1
>
•n
«2
PMMI
00. 10 I
•""* 1
*f°
"l
H
I
!»<
artrasa*
«H)
oum
ajDuai
*S "/* |0»BM««TirM
» 1 f
OXXA
"j
- "T
•-c up n
i K>»^ ^
' 'OCNJCMBKI* 1 '
•UM
men
B mm
LB
R
mua
NONTa
M»U
/"V^l
^
±>
It
J
"».
9RKTI
mcr
-».nm,iN
• »fot
at
l «»»9im
uam
Clj TMU clj
- t
M
c'j
TWI.S
1
L* , T tDiK wacl
-MXWmL-T TO'*9"
C MtlBI H n
V
(D
WASTE STREAM SAW
1O M< MXU9T- •*
WHT HO rilM.
DISQIMCK
LMXCM
<(^
«li>-
II
KM
OCIWIZ
DCnVKIEO
CMOOI
c
D
IT
SMOHIAD
Figure 5-5. General process flow diagram at plant 167, manufacturing chlorine
caustic (mercury cell), showing the sampling points [1].
-------
TABLE 5-38.
TOXIC POLLUTANT LOADS IN RAW WASTE
AT CHLOR-ALKALI PLANTS 747, 317,
AND 167 [1]
(kg/Mg product)
Pollutant Plant 747C
Plant 317
Plant 167C
Mercury
Chromium
Thallium
Arsenic
Nickel
Cadmium
Copper
Lead
Zinc
Antimony
Silver
0.0044
0.00004
0.000001
0.00003
0.00001
0.0002
0.0001
0.0005
0.00001
0.00002
0.063
0.000048
0.00014
0.0003
0.0007
0.0002
0.0006
0.0007
0.010
0.00005
0.013
0.0004
0.0001
0.001
0.0001
0.0001
0.0002
0.0006
Does not include brine muds.
Note. Blanks indicate data not available.
II.5.3.2.2 Chlor-Alkali Diaphragm Cell
One plant employing a metal anode was selected for detailed de-
scription from the available data on the chlor-alkali (metal
anode) diaphragm cell industry based on the lowest concentration
of toxic pollutants in the final effluent stream.
Plant 736. Verification data are provided for plant 736,
which has demisters installed to control the vapors evolved from
the last stage of the evaporator during the concentration of
caustic. In this treatment, the steam evolved from the concen-
tration of cell liquors passes through metal-wool filters to
reduce entrained solids. Cell room washings are sent to a set-
tling chamber, and settled asbestos is sent to a landfill. Other
waste waters, consisting of caustic evaporator washings and
wastes from salt separation, brine purification operations, and
caustic filtration backwash waters, are combined and sent to one
of two settling ponds. Skimming devices on the settling ponds
remove any oil that separates; the settled solids in the ponds
are dredged and diposed of in an abandoned brine well.
Figure 5-6 shows the process flow diagram and sampling points.
Table 5-39 provides the pollutant loadings of the streams sampled,
Table 5-40 presents the toxic pollutant raw waste load for the
plant.
Date: 6/23/80
II.5.3-12
-------
rt
CD
CTi
to
U)
CD
O
M
U)
I
. T
—?"t\ Dicsoum
?
I mow
ooouta Man
ruurutncM
acMicuB
>T
UUFIBI Wrura }*• cm. •
-i—^—I—' I ™ .h
1 I WT
£*i ., m.TOI BKBMH f
^y " TO tar wu. cm.
_ _._ _ DI3TOSM. KXM
BUM NJOTO
tor «J.
DisneM.
MIUMJUUf TO MHJHIWMt
OK CMTIVStn
» 7
owner
MOTH TO SGUD
TO MVDI MI9K
DI90CM.
I.IOIID
atouiB
TO nawx
oamcT waai
TO UVBI
r*l^
HUT
BJMDMOI
•9-
comer wna
OWSTHUJIDC
KVKPomicn
cnnKcr
I"*!™
K-t
THOU •0'
I
Cmmrn L
arooua |
.J—*—I-
-*^ nm««na« |
oo»ot-r t«n«
WASTE STREAMS SAMPLED
EUOTH
10 DOT tax
oisrasa.
comer wam
10 GETTUMI ran
OUBTIC
^J-cgSSgo. [*— T
1 (S^ JL
f I (7ot o«
(7ot o«jsna
10 anruic roo
Figure 5-6. General process flow diagram at plant 736, manufacturing chlorine
caustic (diaphragm cell), showing the sampling points [1].
-------
TABLE 5-39.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
736 PRODUCING CHLORINE USING METAL
ANODE DIAPHRAGM CELLS [1]
Wastestream
Stream description
Flow,
m3/Mg kg/Mg C12
C12 SS Lead
Asbestos
1 Cell wash 0.652 0.06
2 Cell room drain 0.0163 0.00462
3 Brine mud 1.63 32.6
4 50% Barometric (32 mg/L)c
condenser
5 70% Barometric (20 mg/L)c
condenser
6 95% Barometric (90 mg/L)c
condenser
7 Chlorine 0.163 0.00039
condenser
0.00000091
0.00000275
0.000031
<0.01 mg/L)c
«0.01 mg/L)c
0.000000085
(0.0001 mg/L)'
(0.001 mg/L);
(0.01 mg/L)3 (4 x 10~11 mg/L)3
0.00000163
Flow rate of sampled stream is not available; hence pollutant concentration
is given in mg/L.
Note. Blanks indicate data not available.
TABLE 5-40.
PRIORITY POLLUTANT LOADS IN RAW WASTE
AT CHLOR-ALKALI PLANTS 736 and 967a [1]
Pollutant
Plant 736 Plant 967
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Antimony
Arsenic
Cadmium
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
Hexachloroethane
Chloroform
Dichlorobromomethane
Hexachlorobutadiene
Bis(2-ethylhexyl) phthalate
Tetrachloroethylene
0.000044
0.0012
0.0000037
0.0000025
0.000056
ND
ND
0.0007
0.000003
0.000014
0.000006
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.00026
0.0019
0.273
0.000022
0.00054
ND
ND
0.00054
0.00026
0.0028
0.000004
0.000004
0.0003
0.001
0.00014
0.0011
0.00046
0.00005
0.00001
0.00046
Does not include brine ifluds.
DUses graphite anodes
Date: 6/23/80
II.5.3-14
-------
One plant (plant 967) employing a graphite anode was selected for
detailed description from the available data on the chlor-alkali
(graphite anode) diaphragm cell industry.
Plant 967. Verification data are provided for plant 967.
Plant cell washings are sent to an asbestos pond that has a con-
tinuous cover of water. Periodically, the settled solids are
removed, sealed in drums, and disposed of in a landfill. The
overflow from the pond is treated with soda ash to precipitate
lead, treated with sulfuric acid to bring the pH down to 6-9,
and finally settled.
Table 5-41 shows the wastestreams sampled and waste loadings for
plant 967. Figure 5-7 (next page) shows a general process flow
diagram, and Table 5-42 shows toxic pollutant removal at the lead
treatment facility for the plant. Toxic pollutant raw waste
loadings are presented in Table 5-40.
TABLE 5-41.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
967 PRODUCING CHLORINE USING GRAPHITE
ANODE DIAPRAGM CELLS [1]
Wastestream
Stream description
1
2
3
4
5
6
Cell building
wastes
Lead pond
effluent
Caustic plant
effluent
Brine filter
back wash
Cell wash
Condensate and
spent H2SO«
Plow,
mVMg
C13
0.
0.
5.
0.
0.
0.
18
55
38
45
18
79
kg/Mg C12
SS
0.
0.
0.
5.
0.
0.
187
03
841
75
05
85
0
0
0
0
0
0
Lead
.1
.016
.014
.0002
.0086
.00073
Asbestos
0.
0.
0.
0.
0.
0.
000075
0000156
00076
0000018
00066
0000098
TABLE 5-42. TOXIC POLLUTANT REMOVAL IN LEAD TREATMENT
FACILITY AT CHLOR-ALKALI PLANT 967a [1]
Pollutant
kg/M<
Pollutant
Antimony
Arsenic
Chromium
Copper
Mercury
Nickel
Zinc
Lead
Thallium
Influent
average
0
0
0
0
0
0
0
0
<0
.00078
.00032
.00016
.0049
.000026
.00069
.0016
.733
.00004
loads,
3
Effluent
average
0
0,
0
0
0,
<0.
<0.
0
0,
.00005
.00037
.00005
.00003
.00005
.00005
.0001
.029
.00015
Percent
removal
93.6
68.7
99,4
>92.8
>93.8
96.0
Flow - 1.0 mVMg.
Negative removal.
Date: 6/23/80
II.5.3-15
-------
o
D)
rt
0>
oo
o
ID NUUCBfT
Figure 5-7. General process flow diagram at plant 967, manufacturing chlorine
caustic (diaphragm cell), showing the sampling points [1].
-------
Waste flow data from the various sampling points at plants 736
and 967 are contained in Table 5-43. Table 5-44 presents the
results of asbestos sampling at the two plants.
TABLE 5-43. WASTE FLOW DATA FOR CHLOR-ALKALI
PLANTS USING DIAPHRAGM CELLS [1]
Wastestream description
Brine mud
Cell wash
Tail gas scrubber effluent
Flow, m3
Plant 967
0.277
0.29; 0.105
/Mg C12
Plant 736
1.68
0.0168
Note: Blanks indicate data not available.
TABLE 5-44.
RESULTS OF ASBESTOS SAMPLING AT CHLOR-ALKALI
PLANTS USING DIAPHRAGM CELLS [1]
Million fibers/liter
Plant
736
a
967
Wastestream description
Supply
Cell wash
Barometric condenser
Barometric condenser
Barometric condenser
Supply
Cell waste
Pond effluent
Caustic wash
Brine filter backwash
Cathode wash waste
Condensate and spent
acid
Neutralizer waste
Total asbestos
fibers
0.7
20,000,000
1.8
5.3
140
970
24,000
2,400
7,800
800
320,000
270
2,100
Chrisotile
0.7
20,000,000
0
5.3
140
970
24,000
2,400
7,800
620
320,000
180
2,100
Amphibole
0
0
1.8
0
0
BDL
800
BDL
BDL
180
BDL
89
BDL
Uses graphite anode.
II.5.3.3 Chrome Pigments
Two plants were selected for detailed description from the avail-
able data on the chrome pigment industry based on the lowest con-
centration of toxic pollutants in the final effluent stream.
Date: 6/23/80
II.5.3-17
-------
Plant 894
Screening data are provided for plant 894, which produces over
100 products including organic pigments such as copper phthalo-
cyanine. All wastes are combined and treated together. Treat-
ment consists of chromium VI reduction, equalization, and
neutralization, followed by clarification and filtration. Sulfur
dioxide is added to reduce the hexavalent chromium to the tri-
valent state at a low pH prior to hydroxide precipitation. The
backwash from the sand filters is recycled to the equalization
tank. Sludge from the clarifiers is passed through filter
presses and then hauled to a landfill, which has a bottom com-
posed of two clay layers with gravel in between to allow the col-
lection of leachate drainage. Water from the sludge is trapped
in the gravel layer, then pumped out and returned to the plant
for retreatment.
Figure 5-8 (next page) shows the treatment system flow diagram
and the sampling points. Table 5-45 provides waste flows and
pollutant loadings. Table 5-46 presents influent and effluent
verification data as well as monitoring data for the treated
effluent.
TABLE 5-45. FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANTS
PRODUCING CHROME PIGMENTS [1]
Flow,
Wastestream m3/Mg
kg/Mg product
Plant
894
(Verification
phase)
002
(Verification
phase)
description
Treatment
influent
Treatment
effluent
Leachate
Sand filter
feed
Untreated
waste
Unfiltered
treated
waste
Filtered
treated
waste
product TSS Chromium
100 78.1 7.93
100 0.393 0.032
0.258
100 1.1 0.060
85.6 59.8 26.2
85.6 11.1
85.6 82.9 29.9
Iron
4.9
0.03
0.39
0.10
4.64
0.128
4.25
Lead
1.52
0.011
0.164
0.068
13.9
10.0
14.3
Copper
0.356
0.004
0.008
0.0005
Note. Blanks indicate no data analyzed.
Date: 6/23/80
II.5.3-18
-------
o
[1J
ft
tD
U)
00
o
<_n
I
M
VO
ii
* «
t 1
^1 nauiNnai I r
1 ^ 1
sr" I—^*^r I—
».»-«.» I I 1
•O-
IS
niM.
» uvn
•auma
SAMPU POINTS
Figure 5-8. General wastewater treatment process flow diagram at plant 894,
manufacturing chrome pigment, showing the sampling points [1].
-------
TABLE 5-46.
MONITORING AND VERIFICATION SAMPLING OF
CHROME PIGMENTS PLANT 894 [1]
Verification sampling'
Influent
Effluent
Pollutant
TSS
Chromium
Chromium VI
Iron
Lead
Zinc
Total cyanide
Free cyanide
Antimony
Cadmium
Copper
Nickel
yg/L
780,000
78,000
<10
49,000
15,200
4,200
5,100
<940
740
900
3,560
17
kg/Mg
78
7.8
<0.001
4.9
1.52
0.42
0.51
<0.094
0.074
0.090
0.36
0.0017
yg/L
3,900
320
<30
300
110
58
<66
<11
300
8.4
40
<24
kg/Mg
0.39
0.032
<0.003
0.03
0.011
0.0058
<0.0066
<0.0011
0.030
0.00084
0.004
<0.0024
Monitoring Data - Treated Effluent
Concentration, yg/L Waste load
Pollutant
TSS
Chromium VI
Chromium
Copper
Lead
Zinc
Free cyanide
Total cyanide
Arsenic
Cadmium
Mercury
Av
11,200
110
440
130
410
44
<12
120
80
80
<1
30-day av
23,500
300
730
250
870
75
44
310
160
120
1.7
(av) , kg/Mg
1.92
0.018
0.074
0.023
0.069
0.0072
0.0019
0.019
0.0125
0.013
0.00007
Average flow = 153 m3/Mg.
Plant 002
Verification data are provided for plant 002, which normally
produces over 100 products. However, at the time of sampling,
zinc chromate was being produced by a continuous production unit,
All process contact wastes are treated continuously. The waste
is pumped to a treatment tank where sulfur dioxide is added to
convert hexavalent chromium to trivalent. The pH is adjusted
to 8.5 and the waste is then passed through precoated filters
and discharged to a sewer.
Date: 6/23/80
II.5.3-20
-------
Figure 5-9 (next page) shows the waste treatment flow diagram and
sampling points. Table 5-45 shows the waste flows and pollutant
loadings. At sample point 2, half of the sample was filtered
through a glass filter on a Buechner funnel to simulate the
filtration process that was bypassed at the time of sampling.
Table 5-47 presents toxic pollutant raw waste loads for both
plants. Table 5-48 shows water usage and aqueous process waste
effluents.
TABLE 5-47.
TOXIC POLLUTANT LOAD IN RAW WASTE
AT CHROME PIGMENT PLANTS [1]
(kg/Mg product)
Pollutant Plant 894 Plant 002
Cyanide
Chromium
Cadmium
Copper
Lead
Zinc
Antimony
Nickel
Phenols
Phenolics
0.754
11.5
0.165
1.58
7.52
0.855
1.612
0.0334
0.0152
0.145
0.072
0.020
30.8
0.140
5.46
16.4
0.136
0.032
Note: Blanks indicate data not
available.
TABLE 5-48
WATER USAGE AND AQUEOUS PROCESS WASTE
EFFLUENTS FROM CHROME PIGMENT PLANTS [1]
(m3/Mg product)
Description
Water usage
Noncontact cooling
Consumed in product
boiler feed
Chrome
yellow
and
chrome
orange
3.3
Plant
Molybdate
chrome
orange
0
3.5
894
Chrome
oxide
4.7
2.0
Chrome
yellow
and
Chrome chrome
green orange
3.1
1.0
Plant 002
^
Molybdate
chrome
orange
5.0
1.3
Zinc
yellow
0
1.0
Process waste effluent
120
110
31
48
35
31
20
Note. Blanks indicate data not available.
Date: 6/23/80
II.5.3-21
-------
HAH WSTE 9) ACID
f' M
CJSOe THEKBVirf
INK
p»l 3.0
(FILTFI6 M7T WOKKUT. 90
ICHE UB1HU BYTASSED,
TllIS UUULU BE 'HIE FLCM
IF
SAMPLING POINTS
1U SttfR
Figure 5-9.
General wastewater treatment process flow
diagram at plant 002, manufacturing chrome
pigment, showing the sampling points [1].
Date: 6/23/80
II.5.3-22
-------
II.5.3.4 Copper Sulfate
One plant was selected for detailed description from the avail-
able data on the copper sulfate industry based on the lowest
effluent concentration of toxic pollutants in the final effluent
stream.
Plant 034
Verification data are provided for plant 034. Waste from the
plant drains into a sump from which it is pumped to two neutral-
ization tanks where lime is added. The waste is then passed
through a filter press, and filter residue is hauled to a land-
fill disposal site. The filtrate is mixed with noncontact cool-
ing water and steam condensate in a collection tank. Wastes are
then passed through a cloth filter for final polishing and dis-
charged to a sewer.
Figure 5-10 (next page) shows the process flow and sampling
points for this plant. Table 5-49 provides data on waste flows
and classical pollutant emissions. Table 5-50 presents a summary
of the raw waste loadings at this plant, and Table 5-51 gives
treated and 30-day monitoring data.
TABLE 5-49.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR
PLANT 034 PRODUCING COPPER SULFATE [I]
Wastestream
description
CuSO» wastea
Effluent from
lime treatment
Steam condensate
Flow,
inVMg
product
2.23
2.23
0.371
TSS
0.0862
0.0769
0.00133
kg/Mg
Phenol
0.00004
0.000027
"
product
Copper
4.11
0.0101
0.00167
Nickel
0.248
-
"
Infiltration of groundwater into the collection sump was
suspected at the time of sampling.
TABLE 5-50.
SUMMARY OF RAW WASTE LOADINGS FOUND
AT COPPER SULFATE PLANT 034 [1]
Loadings
Pollutant
Average Average
kg/day Icg/Mg
Priority pollutants:
Antimony
Arsenic
Cadmium
Copper
Lead
Nickel
Zinc
0.014
0.16
0.039
83.9
0.0079
5.08
0.50
0.00069
0.0078
0.0019
4.11
0.00039
0.25
0.024
Conventional pollutants:
TSS
1.78
0.087
Date: 6/23/80
II.5.3-23
-------
o
0)
ft
0>
oo
o
aor •
IM
M W1»
T
8nnM OGMXNEMTI
o
SAMPLING POINTS
Loam
-
gern/i
CAM
in
-n»
> rtimt*
, ,
.nr-nr.
3*m«
1
1
ion
»»
«
i
m
^
•c
LI
Ll«
mm
»« ,
CBfnu
im
on
!
CUB
ruz
m
I
1
4
_
'
*L
Mill tn»
Tl i
f T
"izr 1
^ 1
wm» riL-n» I
H*S8 1
M"
^ _ ^ CDUJTTIGN ODTJJM:
t TM«
1
oxmt
»' run*
PIHCINUK
K>
EfM*
Figure 5-10. General process flow diagram at plant 034, manufacturing
copper sulfate, showing the sampling points [1].
-------
TABLE 5-51.
VERIFICATION SAMPLING AT
COPPER SULFATE PLANT 034 [1]
Pollutant
Raw waste
Treated effluent
yg/L
kg/Mg
yg/L
kg/Mg
TSS
Copper
Nickel
Antimony
Arsenic
Cadmium
Chromium
Lead
Selenium
Zinc
Verification Sampling
39,200
1,850,000
112,000
330
3,500
870
142
180
11,100
0.087
4.1
0.248
0.0007
0.0078
0.0019
0.00038
0.00039
0.000024
0.025
35,000
4,650
240
36
<20
1
5
5
100
16
0.078
0.010
0.0005
0.000079
0.000044
0.000002
0.00001
0.00001
0.00022
0.000035
Monitoring Data - Treated Effluent
Concentration, yg/L Waste load
Pollutant
TSS
Copper
Nickel
Zinc
Arsenic
Selenium
Av
26,000
4,300
340
120
12
7
30-day avg
62,400
6,900
750
290
41
43
(av) , kg/Mg
0.096
0.016
0.0013
0.00044
0.000044
0.00003
Raw waste flow =2.23 m3/Mg.
Before combining with noncontact cooling and steam
condensate streams.
cTreated effluent flow - 3.7 m3/Mg.
II.5.3.5 Hydrofluoric Acid
One plant was selected for detailed description from the avail-
able data on the hydrofluoric acid industry based on the lowest
concentration of toxic pollutants in the final effluent stream.
Information on an additional plant is also presented due to the
significant amount of available data.
Date: 6/23/80
II.5.3-25
-------
Plant 705
Screening and verification data are provided for plant 705, which
produces hydrofluoric acid and aluminum fluoride. The drip acid
is sent to the wastewater treatment facility, and the gypsum
produced from the reaction is slurried with water and also sent
to the treatment facility. Wastewaters from the HF production
facility are combined with the aluminum fluoride plant waste-
waters. The combined raw wastewater is treated with lime and
sent to settling ponds before discharge.
Figure 5-11 (next page) shows the general process and the loca-
tions of the sampling points. Table 5-52 provides the screening
and verification flow data and TSS and fluoride emissions. Table
5-53 shows pollutant removability data for plant 705.
TABLE 5-52
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS OF PLANTS
PRODUCING HYDROFLUORIC ACID [1]
Plant
705
(Screening
phase)
Stream
1
2
Wastestream
description
Kiln slurry
Scrubber waste
Flow,
m3/Mg
HF
26.6
10
kg/Mg
Fluoride
14.6
9.6
HF
SS
1,360
0.07
water
Surface drains
cooling tower
blowdown
20
6.9
3.92
705
(Verification
phase)
251
(Verification
phase)
4
1
2
4
5
5
6
2
3
Treated effluent
Kiln slurry
Scrubber waste
water
Surface drains
cooling tower
blowdown
Treated effluent
AHF plant
hosedown
SC>2 scrubber
waste
Gypsum pond
inlet
Gypsum pond
outlet
23.3
26.6
10
20
23.3
1.2
14.4
82.3
82.3
1
3
1
3
0
1
0
54
26
.58
.8
.52
.38
.54
.9
.31
.5
1.
4,730
0.
4.
0.
0.
0.
1,530
0.
91
023
02
04
26
1
8
Date: 6/23/80
II.5.3-26
-------
o
D)
rt
(D
NJ
CO
CO
o
en
CO
I
ISJ
WASTE STREAMS SAMPLED
Figure 5-11. General process flow diagram at plant 705, manufacturing
hydrofluoric acid, showing the sampling points [1].
-------
TABLE 5-53. TOXIC POLLUTANT REMOVAL AT
HYDROFLUORIC ACID PLANT 705
(kg/Mg)
a,b
[1]
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Influent
0.00065
0.0025
0.0006
0.024
0.018
0.0031
0.00036
0.035
0.00016
0.015
Effluent
0.00012
<0.0006
0.0001
0.0029
0.0012
0.0014
0.00003
<0.0006
0.0003
0.00007
0.0033
Flow = 62.1 m3/Mg; value for
total raw waste from HF only.
Values are for combined wastes
from HF and A1F3.
Note: Blanks indicate data not
available.
Plant 251
Verification data are provided for plant 251, in which the final
effluent stream was not sampled. The drip acid at this facility
is sent to the waste treatment plant, and the hydrofluoric acid
wastewaters are combined with aluminum fluoride plant waste for
treatment. In addition to drip acid, the plant wastewater con-
sists of scrubber water, gypsum slurry, and plant area hose down.
The treatment consists of gypsum ponds in which the suspended
solids are removed. Overflow from the last gypsum pond is
neutralized, and the pH is adjusted with wastes from other
product lines.
Figure 5-12 provides a block diagram of the process showing the
sampling locations. Table 5-52 gives a summary of the waste flow
verification data and the concentration and loads of important
classical pollutants. Table 5-54 give raw waste toxic pollutant
loads for the above two plants. Water usage, wastewater flow,
and solids generation data are presented in Table 5-55.
Date: 6/23/80
II.5.3-28
-------
ft
CD
NJ
OJ
"X
O
BUM *
H
Ul
U)
| MOG> DOWt
|^j WTCK
VI
ou
UGUB
SH
MW
»
nr
[
3T
TUM
Ml
DC
IMOJ
£OQ
L
•— *•
AM
H3
H
MM
i
^
IN
c
'
Riff)
ndtiF
T
I I r
i
Mr} ruwr *
HACVQH WJ fc'i1
i r
| 1 Air PKXUCT ^-^
I11 Mr J
1
. _ Mr nvnrr AI^
•HT V
11 £ A «*• HUM WTDI
^LT Mr ruwr
^A ^ crmM ran ^^ *> wunwjumai ^ »ru««r
12 11 ..
'WASTE STREAMS SAMPUO
MJUU.UB
itcio not ontu
Figure 5-12. General process flow diagram at plant 251, manufacturing
hydrofluoric acid, showing the sampling points [1].
-------
TABLE 5-54.
TOXIC POLLUTANT LOAD IN RAW WASTE
AT HYDROFLUORIC ACID PLANTS [1]
(kg/Mg product)
Pollutant
Arsenic
Copper
Lead
Nickel
Selenium
Zinc
Cadmium
Chromium
Mercury
Antimony
Thallium
Plant 705
0.003
0.027
0.003
0.004
0.0005
0.269
0.0001
0.0043
0.00008
0.0016
Plant 705
0.018
0.0075
0.032
0.014
0.0004
0.018
0.0004
0.0004
Plant 251
0.012
0.015
0.0098
0.143
0.0013
0.031
0.06
0.002
0.0003
Note: Blanks indicate data not available.
TABLE 5-55.
WATER USAGE, WASTEWATER FLOW, AND
SOLIDS GENERATION FOR HYDROFLUORIC
ACID PLANT 251 AND PLANT 7-5 [I]
(m3/Mg HF)
Description
Water usage
Noncontact cooling
Gypsum slurry transport
Maintenance, equipment,
and area washdown
Air pollution control
Wastewater flow
Gypsum slurry
Drip acid
Scrubber wastewater
Other
Solids generation
Gypsum solids going to
treatment facility
Total solids produced
Kiln residue produced
Total wastewater influent
to treatment facility
Plant 705
30
30
16.9
11.2
Total recycle
0.018
11.2
22.5
3,300
3,380
a
58.2
Plant 251
154
0
7.9
64.0
0.049
14.4
0.53
1,530
1,650
4.0a
82.4
Residue is slurried with water.
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.3-30
-------
II.5.3.6 Hydrogen Cyanide
Two plants were selected for detailed description from the avail-
able data on the hydrogen cyanide industry based on the lowest
concentration of toxic pollutants in the final effluent stream.
Plant 765
Screening and verification data are provided for plant 765. The
combined wastes for the plant consist of distillation bottoms,
ammonia recovery purge liquor, tank car washings, leaks, spills,
and equipment cleanout, purge from the noncontact cooling water
system, and stormwater runoff. These combined wastes are com-
mingled with the other cyanide production wastewaters and sent to
the alkaline chlorination treatment facility, which consists of a
trench, where the pH is adjusted to 10 with dilute caustic,
followed by two ponds. Sodium hypochlorite is added at the pond
inlets. The effluents from the ponds are discharged to a third
pond where sufficient chlorine and caustic are added to reach the
required effluent quality; namely, an oxidizable free-cyanide
residual of 0.1 ppm and a residual chlorine of about 15 to 20
ppm. The third pond is operated in a continuous-flow mode and is
baffled to control circulation. Agitation is provided in the
flow channel, and the outlet is equipped with a control device to
stop the flow when the effluent cyanide concentration exceeds the
desired level.
Figure 5-13 (next page) is a flow diagram of the treatment proc-
ess indicating the sampling locations used during the screening
program. Table 5-56 provides the flow and pollutant data for the
sampled streams. A comparison of the raw and treated effluent
data in the table indicates that the plant achieves a cyanide
reduction of 99%. Table 5-57 gives treated effluent and daily
monitoring data for plant 765.
TABLE 5-56. FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
765 PRODUCING HYDROGEN CYANIDE [1]
Wastestream description
Raw HCN waste
Influent to the pond
Treated effluent from
the final pond
Flow,
m3/Mg
HCN
57
"?
57b,c
kg/Mg HCN
Ammonia
SS nitrogen
1.08 27.2
55.8° 11. lb.
1.9b 7.05b
Cyanide
0.82
0.388
<0. 000114
b
Stream is a commingled wastewater? flow given is the amount
contributed by the HCN process.
Pollutant load was calculated by apportioning the mass
emitted between the two wastestreams on the basis of
measured flows; this is clearly a very approximate process,
and the results must be used with caution.
Addition or loss of water from rainfall, addition of chemi-
cals, and evaporation has not been estimated.
Date: 6/23/80 II.5.3-31
-------
tftuccot CYANIDE
MlfffE tMTER
CYANIDE PRODUCT
man
WASTE STREAMS SAMPLED
Figure 5-13. General wastewater treatment process flow
diagram at plant 765, manufacturing hydrogen
cyanide, showing the sampling points [1].
Date: 6/23/80
II.5.3-32
-------
TABLE 5-57.
VERIFICATION SAMPLING AT HYDROGEN
CYANIDE PLANT 765 [1]
Verification sampling
Influent
Pollutant
b
TSS
Total cyanide
Free cyanide
BOD
Ammonia
mg/L
71
28.4
6.81
6.3
194
kg/Mg
6.52
2.61
0.626
0.580
17.8
Effluent
quality,
mg/L
19
<0.0026
<0.002
<33
124
Monitoring Data - Treated Effluent
Concentration, mg/L
Waste load, kg/Mg
Parameter
Total cyanide
Oxidizable cyanide
Ammonia nitrogen
(NH3-N)
COD
TOC
TSS
Minimum
0.78
0.01
3.86
54.2
15.7
5.0
Average
3.8
0.2
72
320
166
35
Maximum
9.2
3.27
204
904
512
267
Minimum
0.039
0.0005
0.193
2.71
0.78
0.25
Average
0.192
0.01
3.63
15.9
8.3
1.75
Maximum
0.46
0.16
10.2
45.2
25.6
13.4
Flow = 57 m3/Mg.
Average for 2 days only.
"Results of a 28-day comprehensive test.
Plant 782
Verification data are provided for plant 782, which combines the
plant wastewater with other production wastewater and treats the
combined flow in a complex biological treatment system. A part
of the commingled wastewater is sent to an ammonia stripper from
which the aqueous effluent is mixed with the rest of the waste-
water and sent to the treatment facility. The primary treatment
facility consists of oil skimmers, grit removal, and pH adjust-
ment. Effluent from the primary treatment goes through an API
separator and into an aerated lagoon. Effluent from the lagoon
is flocculated and sent to a clarifier. Overflow from the
clarifier is sent to a final settling basin before discharge.
Surface drainage from the hydrogen cyanide and other process
areas is collected separately. It is treated chemically and
passed through a trickling filter from which a portion of the
Date: 6/23/80
II.5.3-33
-------
A general flow diagram of the treatment process including the
streams sampled is shown in Figure 5-14 (next page). Table 5-58
provides the flow data and concentrations of the important pollut-
ants. Because of the intermixing of the various product waste-
waters, unit pollution loads are uncertain and not given. The
total wastewater generated from HCN manufacture and the amount
going to the treatment facility was verified during the plant
visit and was confirmed in the 308 Questionnaire response pro-
vided by the industry. Based on that flow and the concentrations
determined by analysis, the raw waste load is that shown below:
Effluent from
combined plant
waste treatment
Flow,
m3/Mg
9.9
Total
cyanide,
kg/Mg HCN
0.02
Ammonia
nitrogen,
kg/Mg HCN
0.05
TSS,
kg/Mg HCN
0.74
The load values assigned to the HCN process were estimated by
proportioning the total loads in relation to the respective flow
rates. The result is, therefore, approximate and must be used
with caution. In calculating the pollutant loads, the loss or
gain of water to the treatment system due to factors such as
evaporation, loss through filtered solids, precipitation, and the
water introduced by treatment chemicals, has been neglected.
TABLE 5-58.
FLOW AND POLLUTANT CONCENTRATION DATA OF
OF THE SAMPLED WASTESTREAMS FOR PLANT 782
PRODUCING HYDROGEN CYANIDE [1]
Stream
Wastestream description
Plow,
m3/day
Total
cyanide
mg/L
Ammonia
nitrogen
TSS
1 Distillation bottom purge
2 Ammonia stripper influent
3 Ammonia stripper effluent
4 Influent to primary treatment
facility
5 Final treated effluent
11.3
1,140
1,140
5,560
70
167
51.3
31
2.2
887
410
41
1,380
24
76
162
110
5.16 74.3
Note. Blanks indicate data not available.
Date: 6/23/80
II.5.3-34
-------
own* PJCCCXTT
ORIOK
e
SAMPLING POINTS
DISCSXJCE
Figure 5-14.
General wastewater treatment process flow
diagram at plant 782, manufacturing hydrogen
cyanide, showing the sampling points [1].
Date: 6/23/80
II.5.3-35
-------
The final concentrations of cyanide and ammonia in the treated
effluent shown in Table 5-58 indicate that the treatment system
is efficient in the removal of these pollutants with cyanide
destruction exceeding 99 percent. Table 5-59 gives treated
effluent and daily monitoring data for plant 782.
TABLE 5-59.
VERIFICATION SAMPLING AT HYDROGEN
CYANIDE PLANT 782 [1]
Verification samplingc
Influent
Pollutant
mg/L
kg/Mg
Effluent
quality,
mg/L
TSS
Total cyanide
Free cyanide
BOD
Ammonia
110
31
19.0
1,550
1,380
2.87
0.808
0.495
40.3
36.0
74
2.2
1.73
376
5.04
Daily Monitoring Data - Treated Effluent
Concentration, mg/L
Waste load, kg/Mg
Parameter
BOD
Oxidizable cyanide
Total cyanide
Ammonia
TSS
Minimum
9.0
0.021
0.38
2.0
5.0
Average
39.7
0.112
2.33
27.1
103
Maximum
125
0.18
8.83
281
585
Minimum
0.041
0.0014
0.0025
0.023
0.0088
Average
2.38
0.0072
0.14
1.7
6.5
Maximum
10.2
0.013
1.0
24.1
50.6
Flow =6.25 m3/Mg.
Water usage and wastewater flow data are presented in Table 5-60
for plants 765 and 782. The large variation in flow is the re-
sult of plant 765 not recycling the water used to absorb the
hydrogen cyanide from the reactor gases. This procedure is used
because the plant is located where sufficient cold water is
readily available at low cost, and once-through use is cost
effective. Table 5-61 gives toxic pollutant raw waste loads for
the plants.
Date: 6/23/80
II.5.3-36
-------
TABLE 5-60. WATER USAGE AND WASTEWATER FLOW DATA FOR
HYDROGEN CYANIDE PLANTS 765 AND 782 [1]
(m3/Mg)
Description Plant 765 Plant 782
Water usage
Noncontact cooling 29.5 18.93
Total consumption 58.3 8
Wastewater flow 57 9.9
TABLE 5-61. TOXIC POLLUTANT LOADS IN RAW WASTE
AT HYDROGEN CYANIDE PLANTS [1]
(kg/Mg product)
Pollutant
Total cyanide
Free cyanide
Thallium
Plant 765
5.9
0.0014
Plant 782a
0.808
0.49
Plant 765a
1.6
0.807
Verification data.
Note: Blanks indicate data not available.
II.5.3.7 Nickel, Sulfate
Two plants were selected for detailed description from the avail-
able data on the nickel sulfate industry based on the lowest con-
centration of toxic pollutants in the effluent stream.
Plant 120
Verification data are provided for plant 120. Treatment of pro-
cess wastes at the plant consists of pH adjustment to precipitate
nickel and other trace metals, followed by sand filtration. The
wastes are mixed with other plant wastes and discharged through
a single outfall. Solid wastes from the plant are disposed of or
used as landfill.
Figure 5-15 provides the general process flow diagram. Figure
5-16 presents the wastewater treatment process flow diagram in-
cluding sampling points. Table 5-62 gives flow and concentration
data for the sampled wastestreams. Table 5-63 presents the
treated effluent and daily monitoring data for plant 120.
Date: 6/23/80 II.5.3-37
-------
wen a
01 Of
•OIUTWN
MOBUCT
**J DKSESTOR
m
LIOI
_.-,,__. ^ **"T »W"io tOkunoN
OIGESTOR
*• - *
p-j FILTER ^— | |— — | FILTER j 1
0fNT NICKU.
-------
COD Hll.'KU.
TO N190.
^SAMPLING POINTS
Figure 5-16
General wastewater treatment process flow
diagram at plant 120, manufacturing nickel
sulfate, showing the sampling points [1].
Date: 6/23/80
II.5.3-39
-------
TABLE 5-62.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR
PLANTS PRODUCING NICKEL SULFATE [1]
Plant
120
369
Waste stream
description
NiSOi* waste
All nickel wastes
Treated effluent
Untreated waste
Treated waste
Flow,
m3/Mg
product
0.722
7.54
7.54
0.417
0.417
TSS
0.031
0.521
0.032
kg/Mg
Nickel
0.0355
0.094
0.0015
0.073
0.00058
product
Copper
0'. 00015
0.0002
0.031
0.0075
Lead
0.00004
0.0005
0.0002
Note. Blanks indicate data not available.
TABLE 5-63.
WASTE CHARACTERISTICS OF
NICKEL SULFATE PLANT 120 [1]
Verification sampling
Raw waste
yg/L
Pollutant
TSS
Nickel
Average
43,000
49,200
Maximum
64,000
75,800
kg/Mg
Average
0.842
0.962
Maximum
1.25
1.48
Treated effluent
quality, yg/L
Average
4,330
200
Maximum
8,000
340
Effluent Monitoring - Daily Data
Concentration, yig/L Waste load, kg/Mg
Pollutant Minimum Average Maximum Minimum Average Maximum
Nickel 80 1,830 8,330 0.043 0.35 1.89
Flow =0.72 m3/Mg.
Plant 369
Screening data are provided for plant 369. Treatment at this
plant consists of adjusting the pH to between 9 and 10 to pre-
cipitate metal hydroxides, which are removed by settling prior
to final discharge. Table 5-62 gives flow and concentration
data for the sampled waste streams. No flow diagram is available
for plant 369.
Date: 6/23/80
II.5.3-40
-------
Table 5-64 presents raw waste load data for plants 120 and 369,
Table 5-65 presents water usage information for the two plants
TABLE 5-64.
TOXIC POLLUTANT LOADS IN RAW WASTE
AT NICKEL SULFATE PLANTS [1]
(kg/Mg product)
Pollutant Plant 369 Plant 120
Nickel
Copper
Chromium
Lead
Zinc
Mercury
Cadmium
Selenium
Thallium
0.073
0.030
0.0005
0.00002
0.00011
0.000004
0.000009
0.035
0.0002
0.00001
0.00006
0.00004
0.000002
0.00004
Note: Blanks indicate data not
available.
TABLE 5-65. WATER USAGE FOR NICKEL SULFATE
PLANTS 120 AND 369 [1]
(mVMg)
Description
Plant 120'
Plant 369
Noncontact cooling 13.6
Direct process contact 4.01
Miscellaneous 0
(main, pump seals, etc.)
0.417
0.783
0.094
Includes uses for other process.
II.5.3.8 Sodium Bisulfite
Two plants were selected for detailed description from the avail-
able verification data on the sodium bisulfite industry based on
the lowest concentration of toxic pollutants in the effluent
stream.
Plant 987
The filter wash is the main process waste at plant 987. This
waste is neutralized with 50% caustic soda to a pH of 9 to 10 in
Date: 6/23/80
II.5.3-41
-------
an oxidation tank while mechanically agitating to convert the
bisulfite waste to sulfite. The sulfite is then oxidized to
sulfate with air. The treated waste, including solids, is dis-
charged to a river after a 17-hour retention period.
Figure 5-17 (next page) provides a process flow diagram of plant
987 including sampling points. Table 5-66 provides flow and
pollutant concentration data on the sampling points.
TABLE 5-66. FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANTS
PRODUCING SODIUM BISULFITE [1]
Plant
987
586
Wastestream description
Filter wash 1
Floor wash, spills, etc.
Filter wash 2
Treatment influent
(1+2+3)
54-hour aeration
Treated effluent
MBS sump 1
MBS sump 2
Amine oxidation pond
ZnSO« pond effluent
Lime treatment influent
Truck washdown
S02 wastes
Final treated effluent
Flow,
m3/Mg
product
0.051
0.0123
0.0386
0.102
0.133
0.133
9.68
9.68
2.77
78.5
110
0.134
85.9
188
kg/Mg product
TSS
0.113
0.0457
0.0052
0.315
0.375
0.0031
0.191
0.051
2.43
11.8
10.8
0.0117
1.97
4.27
COD
1.42
0.299
0.908
3.46
1.19
1.02
1.12
0.455
2.33
0.759
28.6
0.0975
52.5
21.7
Zinc
0.000071
0.000044
0.000039
0.00024
0.00024
0.000000799
0.0067
0.0025
0.0031
1.38
0.00517
Copper
0.000018
0.0000111
0.0000357
0.000075
0.000075
0.000036
0.011
0.00031
0.00028
0.0022
0.0040
0.00000269
Note: Blanks indicate data not available.
Plant 586
The sodium bisulfite wastes at plant 586 are combined with
process wastes from an amine plant, a zinc sulfate plant, and
truck wash waste. Lime is added to the wastes, which are then
passed through an aeration tank with an 8-hour retention time.
Treated waste goes through primary and secondary settling before
final discharge.
Figure 5-18 (page II.5.3-44) is a general flow diagram of plant
586 showing the sampling point locations. Table 5-66 provides
flow and pollutant concentration data for the sampled streams.
Table 5-67 gives final treated effluent concentrations for TSS,
COD and zinc.
Date: 6/23/80
II.5.3-42
-------
D
OJ
rt
(D
to
CO
oo
o
CO
I
U)
TO ATMTSIlll-BE
Ftl.TtV MVll
WKAJ.INE SUHWY
(J) WASTE STREAMS SAMPLED
DRAINS, DRIPS.
SPIIJS.
12
14
OXIDATION 1MK
AND
(XHTAIi TO RIVER
15 AJU 16
AIR
Figure 5-17. General process flow diagram at plant 987, manufacturing
sodium bisulfite, showing the sampling points [1].
-------
o
OJ
ft
CD
oo
o
M
CO
I
SWUM
AM) 12
ntm
ITUfC
I.IHE
AIR
H..
-o-
17
AEHATIfW TANK
WASTE STREAMS SAMPLED
•o-
14
sern.iK?
'A IXIA1HS
^ m I riiry i«vsm>i4 I
16 ' '
[ 7na>4
CLAHr
srni.fNG ru«i
TTNNK
IB
Figure 5-18. General flow diagram at plant 586, manufacturing
sodium bisulfite, showing the sampling points [1]
-------
TABLE 5-67. TREATMENT PRACTICES AND VERIFICATION SAMPLING
AT SODIUM BISULFITE PLANT 586 [1]
Treated effluent
TSS
COD
Zinc
Treatment
Flow,
mg/L kg/Mg mg/L kg/Mg yg/L kg/Mg m3/Mg
Lime pH adjustment aera-
tion, and settling
22.7 0.386
115
1.96
59
0.001
17
Combined treatment with other process wastes.
Note: Blanks indicate data not available.
Table 5-68 provides water usage data for plants 586 and 987.
Table 5-69 gives raw waste toxic pollutant loads for the selected
plants.
TABLE 5-68. WATER USAGE AT SODIUM
BISULFITE PLANTS [1]
(m3/Mg)
Description
Direct contact process
Noncontact cooling
Maintenance, washdowns, etc.
Plant 986
1.
0
0.
15
397
TABLE 5-69.
TOXIC POLLUTANT LOADS IN RAW WASTE
AT SODIUM BILSULFITE PLANTS [1]
(kg/Mg product)
Pollutant Plant 987'
Plant 586'
Copper
Zinc
Cadmium
Chromium
Lead
Mercury
Nickel
Antimony
0.00007
0.0002
0.000004
0.0003
0.00007
0.000001
0.00005
0.000007
0.0002
0.0088
0.00001
0.022
0.0002
0.00001
0.00017
0.00008
Verification data.
Date: 6/23/80
II.5.3-45
-------
II.5.3.9 Sodium Bichromate
Two plants were selected for detailed description from the avail-
able data on the sodium dichromate industry based on the lowest
concentration of toxic pollutants in the final effluent stream.
Screening data are provided for plant 493, and verification data
are given for plant 376.
Plant 493
At plant 493, the wastewater going to the treatment facility
includes the boiler and cooling tower blowdown and a small volume
of effluent from a scrubber on a by-product sodium sulfate opera-
tion. The total waste includes the spent ore residue, which is
also sent to the treatment facility. At the treatment facility,
the alkaline wastewaters are reacted with imported acidic indus-
trial waste at an elevated temperature in a reactor. The chro-
mium is precipitated during the reaction. The reacted waste is
sent to clarifiers via holding tanks. In the clarifiers, large
quantities of water are used to wash the precipitated solids in
a countercurrent fashion. The final clarifier overflow, which
is the the treated effluent, is filtered and discharged, and the
clarifier underflow is disposed of in a quarry.
Figure 5-19 (next page) provides a block diagram of the treatment
process and indicates the streams sampled. Table 5-70 gives the
flow data and pollutant emissions of the streams sampled.
Treated effluent data are given in Table 5-71 and Table 5-72.
TABLE 5-70.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANTS
PRODUCING SODIUM DICHROMATE [1]
Plant
493
(Screening
phase)
Stream
1
2
Wastestream
description
Raw wastewater
Treated
effluent
Flow,
m3/Mg
product
4.95
28.9
kg/Mg product
TSS
183
0.018
Hexavalent
chromium
3.5
0.00004
Chromium
1.25
0.022
376
(Verification
phase)
3 Residue slurry 2.13
1 Mud slurry 7.68
waste
2 Primary pond 7.68
effluent
185
3,990
0.0004
0.407
0.591
3.93
1.04
0.808
3
4
Surface runoff
Effluent
4.16
4.16
0.621 0.057
7.94
0.55
0.77
Note. Blanks indicate no data available.
Date: 6/23/80
II.5.3-46
-------
BD1IW SUSIE*
•e-
i)
ft"
TKKTTD OTUtJIT
WASTE STREAMS SAMPLED
Figure 5-20. General wastewater treatment process flow
diagram at plant 376, manufacturing sodium
chromate, showing the sampling points [1],
TABLE 5-73. TOXIC POLLUTANT RAW WASTE LOADS
AT SODIUM DICHROMATE PLANTS [1]
(kg/Mg product)
Pollutant
Chromium
Copper
Lead
Nickel
Zinc
Selenium
Arsenic
Plant 493a
0.
0.
0.
0.
95
00005
047
002
Plant 376
1.
0.
0.
0.
0.
0.
39
0008
0002
006
003
0008
Screening data.
Note: Blanks indicate no data
available.
Date: 6/23/80
II.5.3-49
-------
TABLE 5-74. WATER USAGE IN SODIUM DICHROMATE SUBCATEGORY [1]
(m3/Mg)
Water usage
Description Plant 376 Plant 493
Noncontact cooling 11.4 5.7
Direct process contact 2.85
Indirect process contact 0.2
(pumps, seals, leaks and
spills)
Maintenance (e.g., clean- 0.2
ing and work area
washdown)
Air pollution control 1.0
Noncontact ancillary uses 3.12
Note:Blanks indicate data not available.
II.5.3.10 Sodium Hydrosulfite
One plant was selected for detailed description from data avail-
able on the sodium hydrosulfite industry based on the lowest con-
centration of toxic pollutants in the final effluent stream.
Plant 672
Screening data are provided for plant 672; two different streams
at the plant were analyzed. Because of the nature of the two
wastestreams, each one is handled differently. The dilute waste
is first sent to a holding pond, where the flow is equalized and
the waste is mechanically aerated. This pond also contains
approximately 5.7 m3/d (1,500 gpd) of waste from a sodium bisul-
fite process. The pH of the pond effluent is adjusted with
sulfuric acid, and the effluent is then sent to an aeration
basin. A nitrogen-phosphate fertilizer and urea are added as
nutrients. Approximately 13 m3/d (3,500 gal/d) of sanitary waste
and up to 98 m3/d (25,900 gal/d) of clean dilution water are also
added to the aeration basin. This basin formerly had mechanical
aerators, but now has air diffusers that allow better temperature
control for biological oxidation. Effluent from aeration goes to
a clarifier. Approximately 53 m3/d (14,000 gal/d) of the settled
sludge is returned to the aeration basin and 9 m3/d (2,400 gal/d)
is sent to drying piles on site. More dilution water is added to
the clarifier when needed for TDS control. Overflow from the
clarifier goes to a chlorine contact tank because of the sanitary
waste. Blowdown water from the cooling tower and boilers is
added to the final chamber of the chlorine contact tank. Efflu-
ent from this unit is sent to a final polishing pond for settling
and equalization before discharge.
Date: 6/23/80 II.5.3-50
-------
The coproduct waste from the distilling column bottoms is sent to
a lined coproduct pond at a rate of 53 m3/d (14,000 gal/d) and
held for one of two possible disposal methods. When there is a
market for the coproducts, the waste is concentrated and sold to
the pulp and paper industry. When this is not possible and the
pond reaches near capacity, the waste is bled into the treatment
system described above through the dilute waste holding pond.
A general flow diagram of the biological treatment system is
included in Figure 5-21 (next page). Table 5-75 shows the indi-
vidual wastestreams, the total combined input to the treatment
system, the treated effluent quality, and the efficiency of the
system.
TABLE 5-75. FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
672 PRODUCING SODIUM HYDROSULFITE
tl]
Stream
1
2
3
4
Wastestream
description
Coproduct
Dilute waste
Raw influent
Treated effluent
Flow,
m3/Mg
0.91
1.87
1.87
4.68C
COD
mg/L
77,922
14,628
15,487
740
kg/Mg
70.9
27.4
29.0
3.46
TSS
mg/L
61
263
843
25
kg/Mg
0.056
0.49
1.58
0.12
Zinc
U9/L
24,000
770
5,850
122
k.g/Mg
0.022
0.0014
0.011
0.00057
Percent removal
95-2
Only dilute wastewater being treated at sampling time.
b
All values are an average of 3 days of sampling.
Higher flow due to the addition of sanitary waste and dilution water to the aeration basin plus
cooling tower and boiler blowdown to the chlorine contact tank.
Table 5-76 presents final treated effluent concentrations and
loadings; raw waste pollutant loadings are presented in Table
5-77.
TABLE 5-76.
SCREENING RESULTS
HYDROSULFITE
FROM SODIUM
PLANT 672a [1]
Pollutant
COD
TSS
Zinc
Chromium
Copper
Lead
Nickel
Cadmium
Phenol
Pentachlorophenol
Raw waste
ug/L
15,500,000
840,000
5,800
7,400
1,000
830
1,400
37
150
370
influent
kg/Mg
29.0
1.58
0.011
0.014
0.0019
0.0015
0.0027
0.000069
0.0003
0.0007
Treated
ug/L
740,000
25,000
120
<43
28
70
160
29
<10
<10
effluent
kg/Mg
3.46
0.12
0.00057
<0.0002
0.00013
0.00013
0.00075
0.00014
<0. 00005
<0. 00005
Flow of raw waste influent = 1.87 mVMg; flow of treated
effluent =4.68 mVMg. The higher flow in the treated efflu-
ent is due to the addition of sanitary wastes and dilution
water to the aeration basin, plus cooling tower and boiler
blowdown to the chlorine contact tank.
Date: 6/23/80
II.5.3-51
-------
o
DJ
ft
0)
CTl
00
CO
o
Ul
*
OJ
I
tn
to
SGDIIM irvwwcice soumoN
Figure 5-21. General process flow diagram at plant 672, manufacturing
sodium hydrosulfite [1].
-------
TABLE 5-77.
SUMMARY OF RAW WASTE LOADINGS FOUND
AT A SODIUM HYDROSULFITE PLANT
(FORMATE PROCESS) 672 [1]
Loadings
Pollutant
Average
kg/day
Average
kg/Mg
Priority
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Pentachlorophenol
Phenol
Conventional
TSS
COD
0.0041
0.81
0.11
0.041
0.16
0.0045
0.63
0.04
0.017
91.6
1,690
0.00007
0.14
0.0019
0.0007
0.0027
0.00008
0.011
0.0007
0.0003
1.57
28.9
II.5.2.11 Titanium Dioxide
II.5.3.11.1 Chloride Process
Two plants were selected for detailed description from the avail-
able data on the titanium dioxide chloride process industry based
on the lowest concentration of toxic pollutants in the final
effluent stream.
Plant 559
Screening and verification data are provided for plant 559 which
uses the conventional chloride process to produce titanium di-
oxide. The solids, hereinafter called pit solids and consisting
mainly of unreacted ore, coke, iron, and trace metal chlorides,
including TiCla, separated from the first stage cooling of the
chlorinated gases, are slurried with water and sent to the waste-
water treatment facility. The wastewater from the chloride
process is mixed with other product wastewater and treated in
combination. A flow diagram of the treatment facility, including
the sampling locations, is shown in Figure 5-22. Slurried pit
solids and the distillation column bottom residue are sent to
a large settling pond where they are mixed with the other process
wastewater. Overflow from the settling pond is neutralized with
ground calcium carbonate in a reactor. The scrubber and other
wastewater from the chloride process is mixed with other product
Date: 6/23/80
II.5.3-53
-------
D
QJ
rt
(D
(Ti
00
o
I
Ul
OIUBR WOOUCT
oncM PWMJCT
Benuioiao
PIT aouos
•&
-M men*
seriUNC ran
HFTUWfT
kil
— OISIIUATICH 8OITCM
e
sciuum
SAMPLING POINTS
nearr
WSTER
Figure 5-22. General flow diagram at plant 559, manufacturing titanium dioxide
(chlorine process), showing the sampling points [1].
-------
wastewater and combined with the settling pond effluent. The
combined solutions are neutralized with lime in a second reactor
and then sent to a settling pond before discharge. Because the
chloride process wastewaters are mixed with other product waste-
water prior to treatment, the sampling results represent the
total input mixture rather than only the Ti02 process raw wastes.
Problems were encountered during the sampling of the pit solids
and distillation bottoms. The pipes carrying the wastes from the
process discharged at the bottom of the settling pond, and it was
not possible to take the samples right at the outlet of the pipe.
The combined sample of the two streams was taken at the surface
of the discharge. It is probable that some solids settled before
the stream reached the surface.
Table 5-78 provides the waste flows and pollutant loadings for
the streams sampled at plant 559. Treated effluent pollutant
concentrations are given in Table 5-79.
TABLE 5-78.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
559 PRODUCING TITANIUM DIOXIDE USING
THE CHLORIDE PROCESS fl]
Stream
Wastestream
description
Flow,
m3/Mg
Ti02
kg/Mg Ti02
SS Iron Chromium
2
3
Pit solids and distillation 13.9 95.7 18.7
bottom waste
Settling pond overflow 13.9a 0.22
TiOa (Cl process) scrubber 90 28.2 38.
and other product
wastewater
Final effluent 1043 2.33 0.45^
?a,b
,a
1.55
0.36
0.0096C
0.0026
Pollutant load was calculated by apportioning the mass emitted between the
two wastestreams on the basis of measured flows; this is clearly a very
approximate process and results must be used with caution.
Effluent value is higher than influent because of the introduction of
other product wastewater in the pond contributing to higher load.
Date: 6/23/80
II.5.3-55
-------
TABLE 5-79.
RAW WASTE AND TREATED EFFLUENT
QUALITY AT TITANIUM DIOXIDE PLANT
USING CHLORIDE PROCESS [1]
Verification sampling
Plant 559
a,b
Pollutant
TSS
Iron
Chromium
Lead
Nickel
Zinc
Raw waste,
kg/Mg
6.06
0.104
0.024
0.00004
0.002
0.010
Plant 172
Treated
yg/L
6,670
327
17
<2.3
<10
90
effluent
kg/Mg
0.245
0.012
0.00062
<0. 000084
<0. 00037
0.0033
Raw waste,
kg/Mg
95.9
18.7
1.55
0.049
0.048
0.027
Treated
effluent,
yg/L
23,000
4,400
25
<2.3
5
61.7
Monitoring Data - Plant 172 Treated Effluent
Pollutant (average) yg/L kg/day kg/Mg
TSS
Chromium
Copper
Zinc
3,140
4
10
12
8.34
0.013
0.027
0.028
0.114
0.00018
0.00037
0.00038
Loads in effluent not included because it includes other process
wastes.
"'Average raw waste flow = 13.9 m3/Mg.
'Average flow of treated effluent = 35.9 m3/Mg.
Plant 172
Screening and verification data are provided for the chloride
process wastewater in plant 172. The wastewater from the process,
mainly the scrubber water, is collected in trenches and sent to
a central reactor basin. Other discharges, including a part of
the total rain runoff, are also collected in ditches and sent
to the reactor basin. In the reactor basin, sodium hyroxide is
used for neutralization, and the resulting effluent is mixed with
the remaining rainwater runoff and sent to the first of two re-
tention basins arranged in series. Overflow from the second
retention is adjusted for pH using sulfuric acid before discharge.
A simplified diagram of the treatment system including the sam-
pling points is shown in Figure 5-23. Table 5-80 provides the
Date: 6/23/80
II.5.3-56
-------
FKXSSSVKSIS WOO
MUD RN3T
MUM xiorr
SAMPLING POMS
pB ADJOSTBCUT
13
Figure 5-23,
General flow diagram at plant 172,
manufacturing titanium dioxide
(chloride process) showing the
sampling points [1].
Date: 6/23/80
II.5.3-57
-------
TABLE 5-80.
FLOW AND POLLUTANT CONCENTRATION DATA OF THE
SAMPLED WASTESTREAMS FOR PLANT 172 PRODUCING
TITANIUM DIOXIDE USING CHLORIDE PROCESS [1]
Stream
2
3
Wastestream
description
Inlet to wastewater
treatment pond
Wastewater treatment
effluent
Flow,
m3/Mg
Ti02
35.8
35.8
kg/Mg Ti02
pH TSS Zinc Chromium Iron Nickel
7.9 7.97 0.0096 0.0223 0.107 <0.0008
7.6 0.238 0.003 0.0006 0.011 <0. 00036
waste flow and pollutant loadings for the streams sampled. Table
5-79 presents treated effluent and monitoring data, and Table
5-81 presents water usage.
TABLE 5-81.
WATER USAGE AT TITANIUM DIOXIDE PLANT
172 USING CHLORIDE PROCESS [1]
(m3/Mg Ti02)
Descript/ion
Water usage
Noncontact cooling 10.7
Direct process contact 15.3
Indirect process contact 0.72
Maintenance, equipment 0.52
cleaning and work area
washdown
Air pollution control 7.14
Noncontact ancillary uses 10.4
Sanitary and potable water 0.31
Total 45.3
Table 5-82 gives the raw wastewater toxic pollutant loadings for
exemplary plant 559.
Date: 6/23/80
II.5.3-58
-------
TABLE 5-82. TOXIC POLLUTANT LOADS IN RAW WASTE
AT TITANIUM DIOXIDE PLANT 559
USING THE CHLORIDE PROCESS [1]
(kg/Mg product)
Pollutant
Chromium
Lead
Nickel
Zinc
Raw waste
load
1.55
0.049
0.048
0.027
II.5.3.11.2 Sulfate Process
One plant was selected for detailed description from the avail-
able data on the titanium dioxide-sulfate process industry based
on the lowest concentration of toxic pollutants in the final ef-
fluent stream.
Plant 559
Verification and screening data are provided for plant 559 which
uses the sulfate process to produce titanium dioxide. At this
plant, the strong acid is sent to a lined holding pond for equal-
ization. Effluent from the pond is neutralized with ground
calcium carbonate in a reactor; a sufficient amount is added to
raise the pH to a level such that calcium sulfate, but not fer-
rous hydroxide, is precipitated. The CO2 formed during the
reaction is vented to the atmosphere, and the calcium sulfate
slurry goes to a clarifier. Underflow from the clarifier is
filtered to produce pure gypsum crystals at a concentration of 70
to 80%.
The weak acid is sent to a settling pond, where it is combined
with a small quantity of other wastes. Effluent from the weak
acid pond is mixed with the calcium sulfate clarifier overflow
and neutralized with ground calcium carbonate in a three-stage
reactor. Pebble and slaked lime are also added to raise the pH
and precipitate more calcium sulfate. Air is also introduced to
convert the ferrous iron to ferric. Effluent from the reactor
goes to another clarifier, and the clarifier underflow is fil-
tered to concentrate the solids to 70%. Overflow from the second
clarifier is mixed with the other process wastewaters, which
include the scrubber finishing, and cooling wastewaters. The
combined water is neutralized with slaked lime before it is sent
to a final settling pond, the effluent from which is discharged.
Date: 6/23/80 II.5.3-59
-------
Figure 5-24 (next page) represents the flow diagram of the treat-
ment process and shows the sampling locations for both screening
and verification. Table 5-83 provides the flow data for the
waste streams and Table 5-84 presents pollutant data for the
effluent; Table 5-85 presents daily monitoring data of the efflu-
ent. Table 5-86 presents raw waste toxic pollutant loading for
both sampling phases.
TABLE 5-83.
FLOW AND POLLUTANT CONCENTRATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANT
559 PRODUCING TITANIUM DIOXIDE USING
THE SULFATE PROCESS [1]
Stream
4
3
5
6
Flow,
Waste stream m3/Mg
description TiOz
Weak acid pond 107
overflow
Strong acid pond 9.7
overflow
Scrubber and 583
other product
wastewater
Final treatment 7003'
effluent
kg/Mg Ti02
SS Iron Chromium
1.75* 3053 2.813
1.94 87.6 0.18
183a 83. 6a 0.0623
16,1 3.08 0.017
Pollutant load was calculated by multiplying the flow con-
tributed by the sulfate process stream times the concentra-
tion of pollutant. Pollutant load = (total stream flow) x
(fraction contributed by sulfate process waste) x (stream
pollutant concentrated),
While calculating the unit flow, the contributions to the
treatment process from precipitation, the water in the
treatment chemicals, and the losses from evaporation and
from solids leaving the process have not been considered.
TABLE 5-84.
VERIFICATION RESULTS OF RAW WASTE AND
TREATED EFFLUENT FOR TITANIUM DIOXIDE
PLANT 559a [1]
Treated effluent
Pollutant
TSS
Total iron
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Zinc
Raw waste
Average
310
670
0.015
0.008
5.0
0.13
0.16
0.19
0.004
0.72
, kg/Mg
Maximum
330
770
0.020
0.001
5.6
0.14
0.17
0.22
0.008
0.76
yg/L
Average
23,000
4,400
<15
<10
0.1
25
<5
2
<5
<5
61
Maximum
38,000
7,900
<15
<10
0.2
30
<5
3
<5
<5
65
kg/Mg
Average
19.5
3.7
0.01
<0.008
0.0001
0.02
<0.004
0.002
0.004
0.002
0.05
Flow = 616 m3/Mg; includes cooling water and a small part of
chloride process waste.
Note: Blanks indicate data not available.
Date: 6/23/80
II.5.3-60
-------
o
0)
rt-
(D
O1
\
to
I
CTi
am* naurr
MunKWrm
MEM wrto
MtSIE SimiM
•e-
SIWMS JC1IT—*
»J lonun I—M riun» I »
J loewre j-»J rural I—T—I
m.iue ID
simmer/
IfHflll.
ora* rwucr
w\sn wvrtu
H\STE HUTU
I WASTE STREAMS SAMPLED
Figure 5-24.
General flow diagram at plant 559, manufacturing titanium dioxide
(sulfate process), showing the sampling points [1] .
-------
TABLE 5-85.
SUMMARY OF DAILY EFFLUENT MONITORING DATA
FOR COMBINED WASTEWATER TREATMENT DISCHARGE
AT TITANIUM DIOXIDE PLANT 559 USING SULFATE
PROCESS [1]
Waste load
Concentration,
Parameter
Chromium
Cadmium
Total iron
Dissolved iron
Lead
Nickel
Zinc
TSS
Minimum
10
1
400
80
2
10
10
Average
21
9
3,250
279
17
29
27
35,800
yg/L
Maximum
119
20
19,100
4,980
50
80
300
kg/Mg
Minimum
0.00049
0.00004
0.29
0.04
0.00008
0.00057
0.00049
lbs/1,000 Ibs
Average
0.0014
0.00062
2.14
0.194
0.0012
0.0019
0.0019
23.9
Maximum
0.0045
0.0012
12.99
4.0
0.003
0.0046
0.022
Note. Blanks indicate data not available.
TABLE 5-86.
TOXIC POLLUTANT RAW WASTE LOADS AT
TITANIUM DIOXIDE PLANT 559 USING
THE SULFATE PROCESS [1]
(kg/Mg)
Pollutant
Cadmium
Chromium
Copper
Arsenic
Lead
Nickel
Zinc
Antimony
Phenol
Thallium
Screening
phase
0.0009
3.37
0.118
0.0135
0.103
0.151
0.55
0.08
0.0078
Verification3
phase
0.003
1.36
0.155
0.128
0.086
0.589
0.002
Screening and verification data shown
in table were not completely identi-
fied in Reference 1; reported data
were assumed by MRC to correspond to
screening and verification phases as
noted in table.
Note: Blanks indicate not detected in
measurable quantities.
Date: 6/23/80
II.5.3-62
-------
II.5.4 POLLUTANT REMOVABILITY
The inorganic chemicals industry discharges a variety of toxic
pollutants into plant wastewater streams due to the large number
of products manufactured by the different subcategories of this
industry. Each subcategory has specific major pollutants, and in
some subcategories a specific treatment method is used to control
pollutant discharge. Generally, these major pollutants are toxic
metals. Table 5-87 (next page) lists the toxic metals and the
treatment methods normally used to reduce their concentrations.
The treated waste concentrations and removal efficiencies are
assumed to represent the best performance characteristics obtain-
able under the specified operating conditions. The operating
conditions are assigned as optimal conditions.
II.5.4.1 Aluminum Fluoride Industry
The toxic pollutants found in actual aluminum fluoride plant
wastewaters include copper, arsenic, chromium, and selenium. In
the case of selenium, it is apparent that the source was largely
the raw water supply. Therefore, selenium is not regarded as a
process related pollutant, but its control in the treated efflu-
ent may be required.
Copper and'chromium trace impurities may be present in the hydro-
fluoric acid used to react with bauxite to form aluminum fluoride.
Arsenic may originate as an impurity in the bauxite ore. Waste
treatment processes should be designed to control fluoride, cop-
per, arsenic, and chromium.
Toxic pollutants are generally reduced in the wastewater from
this industry by neutralization and settling. Lime, soda ash,
and alum are the common chemicals used to precipitate the pollut-
ants. Fluoride is also precipitated as calcium fluoride using
this technology.
No effluent data are available at this time.
Potential treatment technologies include the exchange of copper
and chromium for hydrogen or sodium ions by ion exchange from
clarified solutions. Copper and chromium at low levels may also
be controlled by xanthate precipitation, although the process is
not widely used. Sulfide precipitation will reduce copper to
very low levels but does not control chromium or arsenic. A
combination of lime and ferric sulfate coagulation is probably
the most effective proposed method for reducing arsenic
concentrations.
Date: 6/23/80 II.5.4-1
-------
D
0)
rt
(D
oo
o
TABLE 5-87. WASTEWATER TREATMENT OPTIONS AND PERFORMANCE
DATA SUMMARY FOR TOXIC METALS [1]
Antimony
Arsenic
Treatment technology
Activated alumina
Activated carbon
Initial Final removal pH Initial
400-1,000*
400-1,000
Final
<400
<4,000
Percent
remova 1
96-99+
63-97
PH
6.8
3.1-3.6
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter 600 200 62 6.4
Bisulfite reduction
l~l Caustic soda/filter
*~* Chlorine precipitation
' (alkaline chlorination
^" in presence of cyanide)
* Ferric chloride 300 50 98
, Ferric chloride/filter 500 200 65 6.2
J, Ferric sulfate 5,000 50O 90 6.0
Ferric sulfate/filter
Ferrite coprecipitation
Ferrite coprecipitation/ftlter
Ferrous sulfate/filter
Ferrous sulfide (Sulfex) cd cdcd cd
Lime 5,000, 5,000 1,000, 1,400 80, 72 10.0, 11.5
Lime softening 200 30 85
Lime/ferric chloride/filter 3,000 50 98 10.3
Lime/filter 600 400 28 11.5
Lime/sulfide
Reduction/1irae
Sodium carbonate/filter
Sodium hydroxide
Sodium hydroxide/filter
Sulfide
Sulfide precipitation
Sulfide/filter 50 6~7
Sulfur dioxide reduction
(continued)
-------
o
(a
ft
w TABLE 5-87 (continued)
00
o
Be ry 111 um
Concentration, pg/L Percent Concentration, ng/I. Percent
Treatment technology Initial Final removal pH Initial Final removal pH
Activated alumina
Activated carbon
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Al in/filter
Bisulfite reduction
Caustic soda/filter
•t Chlorine precipitation
ii (alkaline chlorinatlon
, in presence of cyanide)
^jl Ferric chloride
. Ferric chloride/filter
•C* Ferric sulfate
I Ferric 3ulfate/filter
CO Ferrite coprecipitation
Ferrite coprecipitation/filter 240,000 8 >99 Neutral
Ferrous sulfate/filter
Ferrous sulfide (Sulfex) 4.000 10 >99 8.5-9.0
Line
Lime softening 440-1,000 8 92-98 5-6.5
Lime/ferric chloride/filter cd cdcd cd
Lime/filter 100 6 99.4 11.5 5,000, 5,000 250, 100° 95, 98 10.0, 11,5
Line/sulfide 300-1,000 6 >98 8.5-11.3
Reduction/lime
Sodium carbonate/filter
Sodiun hydroxide
Sodium hydroxide/filter
Sulflde
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction
(continued)
-------
o
JU
ft
(D
\ TABLE 5-87 (continued)
00 —
O Copper
Concentration, pg/L Percent
Treatnent technology Initial Final removal pj)
Activated alunina
Activated carbon
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum 3,000 200 93 6.5-7.0
Alum/filter
Bisulfite reduction
Caustic soda/filter
M Chlorine precipitation
H (alkaline chlorination
* in presence of cyanide)
U1 Ferric chloride
* Ferric chloride/filter
, Ferric sulfate
^ Ferric sulfate/fllter 5.000 300 95 6.0
Ferrite coprecipitation
Ferrite coprecipitation/fllter 10 >99
Ferrous sulfate/filter
Ferrous sulfide (Sulfex) 3,200, 4,000 20, 10 99, >99 8.5-9.0
Lime 1,000-2,000, 3,000 1,OOO-2,OOO, 200 90, 93 >8.5, 9.5
Lime softening
Lime/ferric chloride/filter . . .
Lime/filter 3,200, 5,000, 5.OOO 7O.40O, 500 98, 92, 91 8.5-9.0, 10, 11,5
Lime/sulfide 50,000-130,000 <500 5.0-6.5
Reduction/lime
Sodium carbonate/filter
Sodium hydroxide
Sodium hydroxide/filter
Sulfide
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction
(continued)
-------
ft
fD
oo
o
TABLE 5-87 (continued)
Treatment technology
Activated alumina
Activated carbon
Activated carbon
(granular)
Activated carbon
Chromium IIT Chromium VI
Concentration, v^/L Percent Concentration, ug/L Percent
Initial Final removal pH Initial Final removal pH
3,000 500 98 6.0
10,000, 10,000 1,500, 400 85, 96 3.0, 2.0
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter
Bisulfite reduction 50-1,000
Caustic soda/filter
Chlorine precipitation
1—4 (alkaline chlorination
HI in presence of cyanide)
• Ferric chloride
<•" Ferric chloride/filter
* Ferric sulfate >98 6.5-9.3
I Ferric sul£ate/fliter 5,000 50 99
' Ferrite coprecipitation 50O BDL
Ferrite coprecipitation/filter 10,000 <10
Ferrous sulfate/filter
Ferrous sulfide (Sulfex)
Lime 15,000, 3,200 100, <100 9.5
Lime softening 150 >98 10.6-11.3
Lime/ferric chloride/filter
Lime/filter 5,000,C, 5,000 100,C 100, 50 98,c 98 10,c 11.5, 7-9
Lime/sulfide
Reduction/lime 140,000, 1,300,000 1,000, 60 7-8
Sodium carbonate/filter
Sodium hydroxide
Sodium hydroxide/filter
Sulfide
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction 5O-1,000
(continued)
-------
ox
TABLE 5-87 (continued)
00 I£i|d
O Concentration, Mg/L Percent
Treatment technology Initial Final removal p_H
Activated alumina
Activated carbon
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter
Bisulfite reduction
Caustic soda/filter
Chlorine precipitation
M (alkaline chlorination
^ in presence of cyanide)
* Ferric chloride
1/1 Ferric chloride/filter
" Ferric sulfate
I Ferric sulfate/filter
-L Ferrite coprecipitation
Ferrite coprecipitation/fliter 475,000 10 99.9
Ferrous sulfate/filter 5,000 75 98.5 6.0
Ferrous sulfide (Sulfex) 189,000 100 99.9 8.5-9.0
Lime
Lime softening
Lime/ferric chloride/filter . r d cd cd
Lime/filter 189,000, 5,000, 5,000 100, 75, 100 99.9, 98.5, 98.0 8.5-9.0, 10, 11.5
Lime/sulfide
Reduction/lime
Sodium carbonate/filter 1,260,000, 5,000 600, 10-30 >99, >99 10.1, 9.0-9.5
Sodium hydroxide
Sodium hydroxide/filter 1,700,000 600 >99 10.5
Sulfide
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction
(continued)
-------
rt
(D
TABLE 5-S1 (continued)
Mercury II
00 Concentration, pg/L Pprcfnt
O Treatment technology Initial Final removal j>H
Activated alumina
Activated carbon 10-50, 60-90 <0.5-60
Activated carbon
(granular)
Activated carbon --
(pulverized, Pittsburgh type RC) """
Activated carbon/alum 20-30 9
Alum
Alum/filter
Bisulfite reduction
Caustic soda/filter
Chlorine precipitation
(alkaline chlorination
tH in presence of cyanide)
H Ferric chloride
Ferric chloride/filter
^ Ferric aulfate
* Ferric sulfate/filter
, Ferrite coprecipitation 6,000-7.400 1-5 99.9
^j Ferrite coprecipitation/filter
Ferroue sulfate/filter
Ferrous sulfide (Sulfex)
Lime
Line softening
Line/ferric chloride/filter
Lime/filter
Line/sulfide
Reduction/line
Sodim carbonate/filter
Sodiun hydroxide
Sodium hydroxide/filter
Sulfide 300-50,000, 10,000 10-120, 1,800 -,s, 96.4 10.0
Sulfide precipitation
Sulfide/filter 16,000, 36,000, 300-6,000 40, 60, 10-125 99, 99.8, 87-99.2 5.5, 4.0, 5.8-8.0
Sulfur dioxide reduction
(continued)
-------
o
p»
rt
w TABLE 5-87 (continued)
CO
o
Nickel Silver
Concentration, ug/L Percent Concentration, ug/L Percent
Treatment technology Initial Final removal p_H Initial Final removal pH
Activated alumina
Activated carbon
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter
Bisulfite reduction
Caustic soda/filter 300 11.0
H Chlorine precipitation 105,000-250,000 1,000-3,500 >97
H " (alkaline chlorination
• in presence of cyanide)
(Jl Ferric chloride
• Ferric chloride/filter 500 40 98.2 6.2
*> Ferric sulfate 150 30-40 72-83 6-9
I Ferric sulfate/fliter
C° Ferrite coprecipttation
Ferrite coprecipitation/filter
Ferrous sulfate/filter
Ferrous sulfide (Sulfex) 75,000 <50 99.9 8.5-9.0
Lime 75,000 1,500 98 8.5-9.0
Lime softening 150 10-30 80-93 9.0-11.5
Lime/ferric chloride/filter . . , -
Lime/filter 5,000, 5,000 300, 150 94, 97 10.0, 11.5
Lime/sulfide
Reduction/lime
Sodium carbonate/filter
Sodium hydroxide 54,000 15,000 72 9.0
Sodium hydroxide/filter
Sulfide
Sulfide precipitation verV hi9h 5-11
Sulfide/filter
Sulfur dioxide reduction (continued)
-------
ft
(D
to
w TABLE 5-87 (continued)
00
O Selenium Thallium
Concentration, l)g/L Percent Concentration, ug/L Percent
Treatment technology Initial Final removal gH Initial Final remova 1 pH
Activated alumina
Activated carbon
Activated carbon
(granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter 500 260 48 6.4 600 400 31 6.4
Bisulfite reduction
caustic soda/filter
Chlorln* precipitation
(alkaline chlorination
In presence of cyanide)
Perrlc chloride
Ferric chloride/filter 100, 50 30, 10 75-80 6.2, 6.2 600 400 30 6.2
Ferric sulfate 100, 100 2O, 30 82, 75 5.5, 7.0
Ferric sulfate/filter
Ferrlte coprecipitation
Ferrite coprecipitation/filter
Ferrous sulfate/filter
Ferrous sulfide (Sulfex)
Lime
Line softening
Line/ferric chloride/filter
Lime/filter 500, 60 30O-4O 35, 38 11.5, 11.5 500 2OO 6O 11.5
Lime/sulfide
Reduction/lime
Sodium carbonate/filter
Sodium hydroxide
Sodium hydroxide/filter
Sulfide
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction .
(continued)
-------
o
(1)
ro TABLE 5-87 (continued)
_ Concentration. uq/L _ __ ___ Percent
Treatment technology _ Initial _ Final _ removal _ pH
(_nj Activated alumina
^\ Activated carbon
OO Activated carbon
O (granular)
Activated carbon
(pulverized, Pittsburgh type RC)
Activated carbon/alum
Alum
Alum/filter
Bisulfite reduction
Caustic soda/filter
Chlorine precipitation
(alkaline chlorination
in presence of cyanide)
Fe
M Fe
ric chloride
ric chloride/filter
ric sulfate
ric imitate/filter
rite coprecipitation 18,000 20 >99
H Ferrite coprecipitation/filter
9 Ferroua sulfate/filter
<-n Ferrous sulfide (Sulfex) 3,600 10-20 >99 8 5-9.0
• Lime
i Lime softening
' Lime/ferric chloride/filter
Q Lime/filter 3,600, 16,000, 5,000,c 5,000 250, 20-230, 800,c 1.200 93, -, 84,c 77 8.5-9.0, -, 10.0,c 11.5
Lime/sulfide
Reduction/line
Sodium carbonate/filter
Sodium hydroxide 33,000 1,000 97 9.0
Sodium hydroxide/filter
Sulfide 42,000 1,200 97
Sulfide precipitation
Sulfide/filter
Sulfur dioxide reduction
'Activated alumina (2 g/L).
Activated carbon (3 mg/LI.
cLime (260 mg/L).
dLime (600 mg/L).
Concentration as chromium VI.
Concentration as chromium III.
^Percent removal unavailable due to form of data.
Note: Blanks indicate no data available.
Multiple tests are reported, if available, with values separated by commas.
-------
II.5.4.2 Chlor-Alkali Industry
Mercury Cells
Existing chlorine plants using mercury cells are already control-
ling mercury in their wastewaters in response to current regula-
tions which call for a discharge of less than 0.00014 kg/Mg of
product as a 30-day average. Potential candidates for further
control are the common heavy metals: chromium, nickel, zinc,
copper, lead, and antimony, as well as arsenic, thallium, and
asbestos, most of which respond to the sulfide process for
mercury precipitation. Some of these metals represent corrosion
products from reaction between chlorine and the plant materials
of construction.
With the phasing out of graphite anodes, chlorinated organics are
not common constituents of mercury cell wastewaters, although
some may originate by the contact of chlorine with rubber linings
and other organic structural components. Traces of certain toxic
organics were found but none in significant concentrations.
Air pollutant emissions, generally called tail gas emissions, are
a result of noncondensable gas emissions and often have high
chlorine concentrations. These emissions are normally scrubbed
with caustic soda or lime solution to produce hypochlorite which
may be sold, decomposed to chloride, sent to the water treatment
plant, or discharged without treatment. Other scrubbing proces-
ses often used include steam and vacuum stripping, and chlorine
absorption columns.
There are many water treatment practices used to reduce the
pollutant concentrations in chlor-alkali wastewater. Most of the
toxic pollutants can be essentially removed by sulfide precipi-
tation followed by settling or filtration. However, chromium and
asbestos are not affected by such treatment. Alkaline precipi-
tation controls all of the heavy metals with varying degrees of
removability at a given pH. Mercury levels are generally control-
led by mercury sulfide precipitation as a result of treatment
with hydrochloric acid and sodium bisulfide. Other technologies
currently being practiced on a limited scale include ferrous
chloride reduction, activated carbon absorption, ion exchange,
and chemical treatment with sodium bisulfite, sodium hydrosul-
fide, sodium sulfide, and sodium borohydride.
Tables 5-88 and 5-89 show the effluent loadings for treated ef-
fluent emanating from mercury cell chlor-alkali manufacturing
facilities.
Date: 6/23/80 II.5.4-11
-------
TABLE 5-88.
EFFLUENT LOADINGS FROM SELECTED
CHLOR-ALKALI MERCURY CELL PLANTS
(kg/Mg)
[1]
Mercury waste load
Plant
343
907
898
195
106
747
589
299
747a
317a
1953
324a
Average
0.000025
0.00002
0.00006
0.00004
0.000065
0.000055
0.000055
0.00004
0.000055
0.000006
0.000022
0.00086
Maximum
daily
0.00094
0.00026
0.0025
0.00073
0.00022
0.00008
0.00086
0.00019
0.000083
0.000048
0.00066
0.0022
Maximum
30-day average
0.00029
0.00003
0.00043
0.00015
0.000096
0.000067
0.00049
0.000056
0.000065
0.00001
0.0001
0.0018
From plant long-term monitoring data.
TABLE 5-89.
Flow, m3/Mg:
EFFLUENT TOXIC POLLUTANT LOADS
FOLLOWING MERCURY TREATMENT [1]
(kg/Mg)
0.23, plant 747; 2.8, plant 106;
0.41, plant 317; 1.5, plant 299
Plant
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
747
<0.059
<0.002
0.036
<0.011
<0.006
0.016
<0.011
<0.0035
<0.01
<0.006
106
1.6
<0.015
<0.039
<0.028
0.15
1.05°
0.40
0.72
0.71
<0.23
317
<0.10
<0.008
<0.01
<0.02
<0.012
0.07
<0.028
<0.006
<0.1
0.21
299
0.22
0.092
0.11
0.09
0.055
<0.074
<0.074
0.022
0.3
0.15
Results of 3-day verification sampling.
3Effluent load higher than influent load.
Date: 6/23/80
II.5.4-12
-------
Diaphragm Cells
Existing regulations in diaphragm cell-graphite anode chlorine
plants call for lead discharge to be less than 0.0025 kg/Mg as a
30-day average. Other toxic pollutants to be controlled include
asbestos, antimony, arsenic, chromium, copper, nickel, and chlo-
rinated organics.
The use of graphite anodes, in either mercury cell or diaphragm
cell plants, results in the generation of a variety of simple
chlorinated hydrocarbons as a result of the attack of the product
chlorine on the anodes. These organic pollutants are sometimes
produced by the reaction of the chlorine with process exposed
rubber.
Toxic heavy metals are normally controlled by sulfide or carbon-
ate precipitation. Asbestos is trapped in a chemical flocculant
or may be settled or filtered to remove the toxic fibers. Chlo-
rinated organics are normally controlled by a reboiler on the
chlorine purifier or by a vacuum stripper. Carbon absorption and
steam stripping are also used for this purpose.
Alternate metal removal methods include ion exchange and xanthate
precipitation. Hydrocarbons may be removed by waste incinera-
tion. Membrane separation for metal control has not proven to be
a viable alternative.
Table 5-90 gives a subcategory profile of treatment processes
used at reported plants for the diaphragm cell subdivision of the
chlor-alkali industry. Table 5-91 shows the lead wasteload and
the removal efficiency of a lead treatment facility associated
with graphite anode-diaphragm cell plant 967.
TABLE 5-90.
EFFLUENT LOADINGS - CHLOR-ALKALI
DIAPHRAGM CELL PLANTS [1]
(kg/Mg)
Suspended solids
Lead waste load waste load
Plant Average Maximum Average Maximum
589a
738a
261a
014a
967
0
0
0
0
0
.002
.001
.0025
.006
.0085
0
0
0
0
.030
.015
.019
2.81
.024
Plant uses metal anodes.
Date: 6/23/80
II.5.4-13
-------
TABLE 5-91.
TOXIC POLLUTANT REMOVAL AT LEAD TREATMENT
FACILITY, PLANT 967 [1]
Flow: 1.0 m3/Mg
Pollutant load,
kg/Mg
Pollutant
Antimony
Arsenic
Chromium
Copper
Mercury
Nickel
Zinc
Lead
Thallium
Influent
average
0.00078
0.00032
0.00016
0.0049
0.000026
0.00069
0.0016
0.733
<0. 00004
Effluent
average
0.00005
0.00037
0.00005
0.00003
0.00005
<0. 00005
<0.0001
0.029
0.00015
Removal,
percent
93.6
-
68.7
99.4
>92.8
>93.8
96. g
Negative removal.
II.5.4.3 Chrome Pigments Industry
The toxic pollutants found within the chrome pigments industry in
significant amounts are the heavy metals often found in chromium
ore, including chromium, antimony, copper, cadmium, nickel, lead,
and zinc. In some raw wastes, ferro- and ferricyanide are found,
presumably from metal complexing steps in the ore processing and
the manufacture of iron blues. These complex cyanides may pass
through the treatment processes and could slowly revert to simple
cyanide ions.
All of the common heavy metals (except hexavalent chromium) found
in chrome pigment wastes are normally treated by alkaline pre-
cipitation with substances such as lime or caustic soda, although
the optimum pH may differ from each metal. Reaction with sulfide
compounds such as sodium bisulfide precipitates the same metals,
but in a less pH-dependent manner and, with the exception of
chromium, to lower concentrations. Chromium in its hexavalent
form is reduced to its trivalent form by S02 reduction and then
precipitated as chromium hydroxide at a pH above 10. Ion ex-
change, biological oxidation, filtration, and settling are other
treatment methods used for pollutant reduction within this
industry.
Table 5-92 shows treated effluent verification data for plant 894
of this subcategory.
Date: 6/23/80
II.5.4-14
-------
TABLE 5-92. VERIFICATION SAMPLING OF CHROME
PIGMENTS PLANT 894 [1]
Average flow: 153 m3/Mg
Influent
Pollutant
TSS
Chromium
Chromium VI
Iron
Lead
Zinc
Cyanide
Cyanide (free)
Antimony
Cadmium
Copper
Nickel
yg/L
780,000
78,000
<10
49,000
15,200
4,200
5,100
<940
740
900
3,560
17
kg/Mg
119
11.9
<0.0015
7.5
2.3
0.64
0.78
0.14
0.11
0.14
0.54
0.003
Effluent
yg/L
3, 900
320
<30
300
110
58
<66
<11
300
8.4
40
<24
kg/Mg
0.60
0.05
0.005
0.046
0.017
0.009
0.010
<0.0017
0.046
0.0013
0.006
<0.0037
Percent
removal
99.5
99. 6a
-
99.4
99.3
98.6
98.7
98.8
59.5
99.1
98.9
"
Negative removal.
II.5.4.4 Copper Sulfate Industry
The toxic pollutants found in copper sulfate plant wastewaters
are closely related to the purity of the copper and acid sources.
The heavy metals (cadmium, nickel, and zinc) which were found
during field sampling may originate as trace impurities in copper
scrap. Arsenic was found at one plant in wastewater containing
floor washings and infiltrated groundwater. A possible source of
arsenic, and other copper ore trace metals, is the use of sulfur-
ic acid made from sulfur dioxide produced in the roasting of
copper sulfide ore. In any event, it appears that copper,
arsenic, cadmium, nickel, and zinc are typical toxic pollutants
encountered in copper sulfate wastewaters.
Copper, nickel, cadmium, and zinc can be separated from solution
by alkaline precipitation at pH values from 7.2 (copper) to 9.7
(cadmium). Arsenic levels are also reduced by this treatment at
high pH levels. Other technologies currently employed include
aeration, clarification, gravity separation, centrifugation, and
filtration.
Metal removal from plant wastewaters could also be accomplished
by sulfide precipitation, ion exchange from clarified solutions,
or the xanthate process. Arsenic removal can also be achieved
by the addition of ferric chloride during alkaline or sulfide
precipitation.
Date: 6/23/80
II.5.4-15
-------
Table 5-93 shows verification data for the raw waste, treated
effluent, and removal efficiencies for plant 034.
TABLE 5-93. VERIFICATION SAMPLING OF COPPER
SULFATE PLANT 034 [1]
Flow: 2.23 m3/Mg
Raw waste
Pollutant
TSS
Copper
Nickel
Antimony
Arsenic
Cadmium
Chromium
Lead
Selenium
Zinc
yg/L
39,200
1,850,000
112,000
330
3,500
870
142
180
<11
11,100
kg/Mg
0.087
4.1 '
0.248
0.0007
0.0078
0.0019
0.00038
0.00039
0.000024
0.025
Treated
yg/L
35,000
4,650
240
36
<20
1
5
5
100
16
effluent3
kg/Mg
0.078
0.010
0.0005
0.000079
0.000044
0.000002
0.00001
0.00001
0.00022
0.000035
Percent
removal
10.7
99.7
99.8
89.1
>99.4
99.9
96.5
97.2
99.8
Before combining with noncontact cooling and steam condensate
streams.
Negative removal.
II.5.4.5 Hydrofluoric Acid Industry
Toxic pollutants in raw wastewaters and slurries typical of the
hydrogen fluoride industry include the heavy metals zinc, lead,
nickel, mercury, chromium, arsenic, copper, and selenium, which
are often found as impurities in fluorspar. Raw wastewaters
from plants practicing dry disposal of kiln wastes may include
some of the heavy metals in scrubber and area washdown wastes,
but in considerably smaller amounts, since the spent ore is
hauled as a solid waste and bypasses the wastewater treatment
facilities. Although a fluoro-sulfonate complex is found in
hydrofluoric acid wastes containing drip acid, organic compounds
are not anticipated in wastewaters from this industry.
Raw wastewater from this industry is presently being treated by
alkaline precipitation, settling, filtration, clarification, and
complete recycle of wastewater.
Treatment methods currently under study or feasible due to other
industry applications include sulfide precipitation, xanthate
process, and ion exchange from clarified solutions. Sulfide
precipitation from cleared solutions will control zinc, lead,
nickel, copper, and, to a lesser extent, antimony.
Date: 6/23/80
II.5.4-16
-------
Tables 5-94 and 5-95 present treated effluent and waste influent-
treated effluent comparisons for several hydrofluoric acid
manufacturing plants.
TABLE 5-94.
Flow,
TOXIC POLLUTANT REMOVAL AT
HYDROFLUORIC ACID PLANTS3 [1]
(kg/Mg)
m3/Mg:
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
62.1,
Plant
Influent
0.00065
0.0025
0.0006
0.024
0.018
0.0031
0.00036
0.035
-
0.00016
0.015
plant
70S
Effluent
0.00012
<0.0006
0.0001
0.0029
0.0012
0.0014
0.00003
<0.0006
0.0003
0.00007
0.0033
705; 127, pi
Plant
Influent
0.0058
0.019
-
0.060
0.015
0.011
0.0034
0.14
0.008
-
0.031
167
Effluent
<0.026C
<0.003
<0.0003
0.032
0.010
0.0047
<0. 00015
0.077_
0.011
0.0010
0.023
Values are for combined wastes from HF and A1F3.
Values are for total raw waste from HF only.
Negative removal.
TABLE 5-95.
SUMMARY OF EFFLUENT QUALITY ATTAINED AND
VARIABILITY OBSERVED AT FOUR REPRESENTA-
TIVE HYDROFLUORIC ACID PLANTS [1]
Parameter
Plant 664
Daily average
Daily maximum
Monthly average
Monthly maximum
Plant 753
Daily average
Daily maximum
Monthly average
Monthly maximum
Plant 722
Daily average
Daily maximum
Monthly average
Monthly maximum
Plant 705
Dally average
Dally maximum
Monthly average
Monthly maximum
Treated waste load
Fluoride,
pH kg/Mg
6.8 0.10
2.9 - 7.7 0.34
6.8 0.10
5.0 - 7.5 0.16
0.72
2.0
0.64
0.76
9.0 0.81
2.8 - 12.2 2.6
0.49
0.8
TSS,
kg/Mg
0.29
1.1
0.27
0.63
0.38
0.54
1.2
0.84
1.53
Flow, m3/Mg
(gal/short ton)
5.6
16
5.6
10.5
11
10.2
24
26.8
139
(1,340)
(3,760)
(1,340)
(2,500)
(2,650)
(2,450)
(5,760)
(6,430)
(33,400)
Note: Blanks indicate no data available.
Date: 6/23/80
II.5.4-17
-------
II.5.4.6 Hydrogen Cyanide Industry
The only toxic pollutant found during field sampling within the
hydrogen cyanide industry was cyanide, both oxidizable and in the
form of metallic complexes such as ferro- and ferricyanides.
Ammonia, which is present as a nonconventional pollutant, exerts
a demand for the chlorine used to oxidize cyanide and should be
removed by steam stripping.
Cyanide is decomposed readily by oxidation at high pH levels,
forming cyanate as an intermediate product. Further decomposi-
tion into carbon dioxide and nitrogen is possible with complete
oxidation. Alkaline chlorination is widely used in the electro-
plating industry to break down metallic cyanide complexes. Al-
though oxidation agents such as hydrogen peroxide might be used,
their operating costs are generally not favorable. If ammonia
is present, it increases the cost of chlorination since it also
reacts with the chlorine. If ammonia is not to be controlled,
ozonation may prove to be a more cost effective oxidant.
Due to excess chlorine usage, the discharge from cyanide destruc-
tion is high in chlorine, and dechlorination is generally needed.
Biological treatments such as aeration and trickling filtration
are used to reduce the chlorine concentration in the raw waste-
water. Other technologies often used include sodium hypochlorite
treatment, API separators, and caustic adjustment.
Ozonation to oxidize the chlorine in the wastewater is currently
under study for use as a treatment method within this industry.
Sulfur dioxide is also a potential treatment technology.
Table 5-96 shows raw waste and treated effluent verification data
and removal efficiencies for plants 765 and 782.
TABLE 5-96.
VERIFICATION SAMPLING OF
HYDROGEN CYANIDE PLANTS [1]
Flow, m3/Mg: 57, plant 765; 6.25, plant 782
Plant
code Pollutant
765 TSSa
Cyanide
Cyanide
BOD
Ammonia
782 TSS
Cyanide
Cyanide
BOD
Ammonia
(total)
(free)
(total)
(free)
Influent
mg/L
71
28.4
6.81
6.3
194
110
31
19.0
1,550
1,380
kg/Mg
6
2
0
0
17
2
0
0
40
36
.52
.61
.626
.580
.8
.87
.808
.495
.3
.0
Effluent,
mg/L
19
<0
<0
<33
124
74
2
1
376
5
.0026
.002
.2
.73
.04
Percent
removal
73.
>99.
>99.
36.
32.
92.
90.
75.
99.
2
9
9,
1
7
9
9
7
6
Average for 2 days only.
Negative removal.
Date: 6/23/80
II.5.4-1!
-------
II.5.4.7 Nickel Sulfate Industry
The toxic pollutants present in a specific process operation de-
pend upon the sources and nature of the raw materials being used,
which presumably could vary from time to time. If impure raw
materials include spent plating solutions, most of the heavy
metals will be rejected from the process as sludges by the
purification of the plating solutions prior to nickel sulfate
production. The sludge produced may be handled as a solid or
slurry waste, with the former being safely landfilled and the
latter being treated and settled in treatment facilities. The
only significant toxic pollutant found in the sampling program
was nickel.
Alkaline precipitation will remove nickel and most other heavy
metals from solution, allowing them to be settled and filtered
in successive steps. Nickel and the common heavy metals, except
chromium, can also be precipitated as metallic sulfide, for later
separation by settling and filtration.
Table 5-97 shows raw waste and treated effluent characteristics
and removal efficiency for plant 120.
TABLE" 5-97. VERIFICATION SAMPLING OF WASTE CHARACTER-
ISTICS AND TREATED EFFLUENT QUALITY OF
NICKEL, SULFATE PLANT 120 [1]
Flow: 0.72 m3/Mg
Raw
pg/L
Pollutant
TSS
Nickel
Average
43,000
49,200
Maximum
64,000
75,800
waste
kg/Mg
Average
0.842
0.96
Maximum
1.25
1.48
Treated
quality
Average
4,330
200
effluent
, yg/L
Maximum
8,000
340
Percent
removal
89.9
99.6
Based on raw waste and treated effluent average values.
II.5.4.8 Sodium Bisulfite Industry
Toxic pollutants should not normally be present in wastes origi-
nating solely from the manufacture of sodium bisulfite from
sodium carbonate and sulfur dioxide. However, it is reported
that some sources of sodium carbonate contain zinc and other
trace metals in measurable amounts. Dissolved zinc was found in
some sodium bisulfite wastewaters during the sampling program.
It may be assumed that zinc enters the wastestream by corrosion
Date: 6/23/80 II.5.4-19
-------
of galvanized metals from coproduct operations, or from non-
process zinc compounds used by the industry.
Raw wastewater from this industry is generally treated by alka-
line precipitation to remove the toxic metal pollutants. Lime,
sodium carbonate, and caustic soda are normally used for this
treatment, which is usually followed by a settling basin. Sodium
hypochlorite may also be used as a treatment chemical.
Three other treatment methods may also be feasible for this indus-
try: sulfide precipitation, which readily precipitates zinc from
solution; ion exchange from clarified solutions; and the xanthate
process.
Table 5-98 shows treated effluent verification data for plants
282 and 586.
TABLE 5-98. TREATMENT PRACTICES AND VERIFICATION SAMPLING
AT SODIUM BISULFITE PLANTS [1]
Flow, m3/Mg: 2.67, plant 282; 17, plant 586
Treated effluent
Plant
282
Treatment
Caustic neutraliza-
TSS
mg/L kg/Mg
159 0.424
COD
mg/L kg/Mg
979 2.61
Zinc
yg/L kg/Mg
2,540 0.0068
tion, sodium
hypochlorite
oxidation
586a Lime pH adjustment, 22.7 115 59
aeration, and
settling
"Combined treatment with other process wastes.
Note: Blanks indicate data not available.
II.5.4.9 Sodium Dichromate Industry
Toxic pollutants found within the sodium dichromate industry in
significant amounts are the primary pollutant, hexavalent chro-
mium, and the common heavy metals often present as impurities in
the chromium ore, notably zinc and nickel. By controlling chro-
mium, the incidental removal of other trace heavy metals will
also be achieved.
Alkaline precipitation and reaction with sulfite are two methods
used to separate nickel and zinc from solution. Hexavalent chro-
mium must be reduced to its trivalent form by reacting with
Date: 6/23/80 II.5.4-20
-------
sodium bisulfide before it can be precipitated by alkaline sub-
stances. Clarification, filtration, and settling are also used
as control technologies.
Although ion exchange or xanthates can remove metals from clari-
fied solutions, they are inappropriate for treating raw waste
slurries from this industry.
Table 5-99 shows chromium and suspended solids effluent waste
loadings and a brief description of the waste treatment practices,
Table 5-100 shows verification toxic pollutant data for treated
effluent from plants 398 and 493.
TABLE 5-99. EFFLUENT CONTROL AND TREATMENT PRACTICES
AND ACHIEVEMENTS AT SODIUM DICHROMATE
PLANTS [1 ]
Effluent waste load, kg/Mg
Control and Chromium Chromium VI
Plant Treatment practice p_H Average Maximum Average Maximum Average Maximum
398 Once-through cooling 6.6 tO 8.5 0.0079 0.034
water, dispose of
ore residue as
solid, no treatment
of cooling water
discharge.
493 Recirculate cooling 6.3 to 8.3 0.00038 0.0049 0.00018 0.1 0.3
water, slurry ore
residue, treat all
wastes with pickle
liquor, counter-
current solids
wash, clarify and
filter effluent.
376 Recirculate cooling 0.00058 0.0017 0.00058 0.047 0.69
water, slurry or
residue, treat all
wastewater with
sodium sulfide,
remove solids in
settling ponds.
TABLE 5-100. VERIFICATION SAMPLING OF
SODIUM DICHROMATE PLANTS [1]
Flow, m3/Mg: 584, plant 398; 3.8, plant 493
Plant 398a
treated efflue
Pollutant kg/Mg
TSS
Chromium VI
Chromium
Nickel
Zinc
Copper
2.05
43.9
0.049
0.0009
0.013
Plant 493
nt, Raw waste,
kg/Mg
140
2.64
0.95
0.047
0.002
0.00005
Treated
yg/L
2,000
4
2,500
90
110
16
effluent
kg/Mg
0.0075
0.000016
0.0094
0.00034
0.00041
0.00006
No treatment, only cooling water outfalls.
Less than supply water of 495 ng/L.
Date: 6/23/80 II.5.4-21
-------
II.5.4.10 Sodium Hydrosulfite Industry
Although sodium hydrosulfite is being manufactured by both the
zinc process and the formate process, the trend is away from the
zinc process for environmental reasons. This discussion con-
cerns only the formate process, using a sodium formate feedstock
from a source which appears to contain significant heavy metal
impurities (chromium, zinc, nickel, lead, and copper), as well as
trace amounts of cyanide. A predominant characteristic of sodium
hydrosulfite wastes is their high chemical oxygen demand result-
ing from various forms of sulfite, from methyl formate, and from
residual methanol after a solvent recovery process. Low levels
of phenolic compounds are also found in the raw wastes.
The significant heavy metals appear largely in a coproduct waste-
stream which is often sold for use in the pulp and paper industry.
When no market exists, these wastes are bled into the product
wastes.
Practical technologies for controlling COD include various forms
of mechanical and biological oxidation. For the relatively
simple chemical oxidation of sulfite to sulfate, intimate con-
tact with atmospheric oxygen is effective, using submerged air
diffusers, induced air in a circulating system, or mechanical
surface aeration. For biochemical oxidation of resistant organ-
ics such as formates, phenols, chlorinated hydrocarbons, and
methanol, trickling filtration, rotating biological discs, or
variations of the activated sludge process can provide intimate
contact between organic pollutants and the microbiological
organisms which use them as food.
Technologies for controlling heavy metals include alkaline pre-
cipitation, which is effective for the common heavy metals, and
sulfide treatment, which precipitates nickel, zinc, and copper,
but does not control chromium without a subsequent pH increase.
In this subcategory an exception is made to the assumed exclusion
of sanitary sewage from the wastestream. To utilize the nutri-
ents and bacteria present in sewage as support for a biological
oxidation system to control organics and COD, the plant sanitary
wastes are included in the biological treatment.
Vent scrubber water containing methanol is also treated by the
above processes.
Table 5-101 shows concentrations, loadings, and the removal ef-
ficiency for conventional and toxic pollutants for plant 672.
Date: 6/23/80 II.5.4-22
-------
TABLE 5-101.
SCREENING RESULTS FROM SODIUM
HYDROSULFITE PLANT 672 [1]
Flow, m3/Mg: 1.87, influent; 4.68, effluent'
Pollutant
COD
TSS
Zinc
Chromium
Copper
Lead
Nickel
Cadmium
Phenol
Pentachlorophenol
Raw waste
yg/L
15,500,000
840,000
5,800
7,400
1,000
830
1,400
37
150
37
influent
kg/Mg
29.0
1.58
0.011
0.014
0.0019
0.0015
0.0027
0.000069
0.0003
0.0007
Treated
yg/L
740,000
25,000
120
<43
28
70
160
29
<10
<10
effluent
kg/Mg
3.46
0.12
0.00057
<0.0002
0.00013
0.00013
0.00075
0.00014
<0. 00005
<0. 00005
Percent
removal
95.2
97.0
97.9
>99.4
97.2
91.6
88.6
11.7
>93.4
>97.3
Higher flow due to the addition of sanitary wastes and dilution water
to the aeration basin, plus cooling tower and boiler blowdown to the
chlorine contact tank.
II.5.4.11 Titanium Dioxide Industry
Toxic pollutants to be controlled in this industry are the common
heavy metals found in the ore (i.e., chromium, lead, nickel, and
zinc). Although coke and certain proprietary organic complexing
agents are used in the chloride process, the amount of chlori-
nated organic toxic pollutants produced is insignificant and
pollutants are found in all ores, nor are they found in all
plants utilizing the same process.
Alkaline substances and sulfide compounds are used to control the
heavy metals by precipitation as metallic hydroxides, carbonates,
or sulfides. Lime neutralization also reduces the concentration
of arsenic in the wastewater, although the removal mechanism is
not known. Dissolved air flotation, settling, filtration, and
centrifuging are a few of the physical methods used for pollutant
control.
Among potential treatment technologies, ion exchange can remove
metals from clarified solutions, but it is seldom specific enough
to remove only the trace metals and is not effective in solutions
saturated with calcium. Lime treatment combined with ferric iron
may be the most effective means of controlling arsenic
concentrations.
Date: 6/23/80
II.5.4-23
-------
Table 5-102 and Table 5-103 show verification effluent data for
the chloride process and sulfate process, respectively.
TABLE 5-102.
FLOW AND POLLUTANT CONCENTRATION VERIFICATION DATA
OF THE SAMPLED WASTESTREAMS FOR PLANTS PRODUCING
TITANIUM DIOXIDE (CHLORIDE PROCESSES) [1]
Average flow, m3/Mg: 35.9, plant 172; 13.9, plant 559
Pollutant
TSS
Iron
Chromium
Lead
Nickel
Zinc
Raw waste,
kg/Mg
6.
0.
0.
0.
0.
0.
06
104
024
00004
002
010
Plant 172
Treated
yg/L
6,670
327
17
<2.3
<10
90
Plant 559a
effluent
0
0
0
<0
<0
0
kg/Mg
.245
.012
.00062
.000084
.00037
.0033
Raw waste ,
kg/Mg
95.
18.
1.
0.
0.
0.
9
7
55
049
048
027
Treated effluent,
pg/L
23,000
4,400
25
<2.
5
61.
3
7
Loads in effluent not included because it includes other process water.
TABLE 5-103.
SUMMARY OF DAILY EFFLUENT MONITORING
VERIFICATION DATA FOR COMBINED WASTE
WATER TREATMENT DISCHARGE AT TITANIUM
DIOXIDE PLANT 559 (SULFATE PROCESS) [1]
Flow: 616 m3/Mga
Raw waste,
kg/Mg
Pollutant
TSS
Total, iron
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Thallium
Zinc
Average
310
670
0
0
5
0
0
0
0
0
.015
.008
.0
.13
.16
.19
.004
.72
Max imum
330
770
0.
0.
5.
0.
0.
0.
0.
0.
020
001
6
14
17
22
008
76
Treated effluent
lag/L
Average
23,000
4,400
<15
<10
0.1
25
<5
2
<5
<5
61
Maximum
38,000
7,900
<15
<10
0.2
30
<5
3
<5
<5
65
Average ,
kg/Mg
19.
3.
<0.
<0.
0.
0.
<0.
0.
0.
0.
0.
5
7
01
008
0001
02
004
002
004
002
05
Includes cooling water and a small part of chloride process
waste.
Note: Blanks indicate no data available.
Date: 6/23/80
II.5.4-24
-------
11.5.5 REFERENCES
1. Draft Development Document for Inorganic Chemicals Manufac-
turing Point Source Category - BATEA, NSPS, and Pretreatment
Standards (draft contractor's report). Contract 68-01-4492,
U.S. Environmental Protection Agency, Effluent Guidelines
Division, Washington, D.C., April 1979.
2. NRDC Consent Decree Industry Summary - Inorganic Chemicals
Industry.
3. Supplement for Pretreatment to the Development Document for
the Inorganic Chemicals Manufacturing Point Source Category.
EPA-440/1-77/087A, U.S. Environmental Protection Agency,
Washington, D.C., July 1977.
4. Development Document for Effluent Limitations Guidelines
and NSPS for the Major Inorganic Products Point Source
Category. EPA-440/l-74-007-a, U.S. Environmental Protection
Agency, Washington, D.C., March 1974.
5. Environmental Protection Agency Effluent Guidelines and
Standards for Inorganic Chemicals (40CFR415; 39FR9612,
March 12, 1974; amended as shown in Code of Federal Regu-
lations, Vol. 40, revised as of July 1, 1976; 41FR51599
and 51601, November 23, 1976; 42FR17443, April 1, 1977,
42FR10681, February 23, 1977; 42FR37294, July 20, 1977).
Date: 6/23/80 II.5.4-25
-------
II.6 IRON AND STEEL MANUFACTURING
II.6.1 INDUSTRY DESCRIPTION [1-9]
II.6.1.1 General Description
The Iron and Steel Manufacturing Industry encompasses all opera-
tions under SIC codes 3312, 3315, 3316, and 3317. Within these
classifications are establishments involved in the production of
iron, steel, and those ferrous products which do not require
machining (rolling and drawing are not considered machining oper-
ations for these classifications). It also includes ancillary
processes necessary to the primary functions of the plants.
Therefore, coke production, scale removal, pickling, and alkaline
cleaning are all included in this industry. Excluded are those
operations engaged in the manufacture of iron and steel castings,
which are classified under group 332 of the SIC code.
There are 1,863 plants in this industry, but far fewer plant
sites. Because of the interrelationships of these plants, there
are frequently a large number of plants on a single site with the
product of one plant serving as the feedstock for another through
a series of operations that produce one or more final products
(usually several). Depending on the suricategory, about 40% to
80% of the plants in this industry are located in Pennsylvania
and Ohio. Approximately 75% to 85% of all plants are located in
the states of Pennsylvania, Ohio, West Virginia, Kentucky,
Indiana, Illinois, Michigan and Wisconsin. These plants are
grouped around the coal and iron mining regions, where shipping
distance of the needed raw materials is short and shipment is
inexpensive. The remaining plants tend to be found in coastal
portation costs also tend to be moderate (especially Alabama,
California, Texas, and Georgia). Furthermore, all the states
mentioned have sizable contiguous bodies of water available for
use. There are a few plants in the arid region of the Southwest,
but they must necessarily be among the portion of the industry
with low or zero discharge rates.
Discharge rates in the industry vary from 0 to over 384 m3/Mg
(23,000 gal/ton) with a mean discharge of 30.5 m3/Mg (1,827 gal/
ton). Additional industry data are found in Table 6-1.
Date: 6/23/80 II.6.1-1
-------
TABLE 6-1. INDUSTRY SUMMARY [10]
Industry: Iron and Steel Manufacturing
Total Number of Subcategories: 25
Number of Subcategories Studied: 24
Number of Dischargers in Industry:
• Direct: 1,405
Indirect: 238
Zero: 220
II.6.1.2 Subcategory Descriptions [1-10]
The following paragraphs briefly describe the 24 Subcategories of
this industry that were studied. Process descriptions, number of
facilities, subdivisions, production capacity and wastewater dis-
charge flow rates are included in this general description. The
wire pickling and coating subcategory is not described in this
section due to a lack of information. However, some categories
address related subjects and may be referred to if information
is needed.
Table 6-2 presents best practicable control technology pollutant
data for each subcategory within this industry.
Cokemaking [2]
The production of metallurgical coke is an essential part of the
iron and steel industry, since coke is one of the basic raw mate-
rials necessary for the operation of ironmaking blast furnaces.
Cokemaking has been divided into the byproduct recovery cokemak-
ing subcategory and the beehive cokemaking subcategory. Of the
two traditional processes for the manufacture of coke, byproduct
recovery has virtually eclipsed beehive oven in commercial appli-
cation. Less than 1% of the metallurgical coke produced in 1977
was made in beehive ovens (four small plants in three states).
The remaining 99% of coke production comes from coke plants
practicing varying degrees of byproduct recovery (61 locations,
some with 2 or 3 plants per location, in 17 different states).
Byproduct Recovery Coke. The byproduct recovery process, as
the name implies, places emphasis not only on the production of
high-quality coke for use as blast furnace or foundry fuels and
carbon sources, but also provides a means for recovery of valuable
byproducts of the distillation reaction. Air is deliberately
excluded from the coking chambers, while heat for the distilla-
tion process is supplied from external combustion of fuel gases
in flues located within dividing walls separating adjacent ovens.
Date: 6/23/80 11.6.1-2
-------
Oi
rt
(D
TABLE 6-2. BPT LIMITATIONS FOR IRON AND STEEL MANUFACTURING [11]
to
LO
00
o
H
I
UJ
Subcategory
Byproduct coke
Beehive cokec
Sintering
Blast furnace (iron)
Blast furnace (ferromanganese)
Basic oxygen furnace (senijnwet
air pollution control)
Basic oxygen furnace (wet air
pollution control)
Open hearth furnace
Electric arc furnace (semiwet
air pollution control)
Electric arc furnace (wet air
pollution control)
Vacuum degassing
Continuous casting and pressure
slab molding
Hot forming-primary
Hot forming-section
Hot forming-flat
Pipe and tube
Pickling-sulfuric acid, batch
and continuous
Pickling-hydrochloric acid,
batch and continuous
Cold rolling
Hot coating-galvanizing
Hot coating-terne
Combination acid pickling
(batch and continuous)
Scale removal (kolene and
hydride
Wire pickling and coating
Continuous alkaline cleaning
Oil and grease,
kg/Mq
0.0327/0 0109
0.0063/0.0021
0.0234/0.0078
0.0684/0.0288
0.328S/0.1095
0.5004/0.1668
0.1254/0.0418
0.00312/0.00104
0.0039/0.0013
0.00312/0.00104
0.1125/0.0315
0.1125/0.0375
0.1251/0.0417
0.1251/0.0417
Pollutant parameter
Ammonia, Cyanide, Dissolved iron,
TSS, kq/Mq kg/Mg kg/Mg Phenol, kg/Mq kg/Mg Zinc, kq/Mg
0.1095/0.0365 0 2736/0.0912 0 0657/0.0219 0.0045/0.0015
0.0312/0.0104
0.0780/0 0260 0.1953/0.0651 0.0234/0 0078 0.0063/0 0021
0.3129/0.1043 1 5636/0.5212 0.4689/0.1563 0 0624/0.0208
0.0312/0.0104
0.0312/0.0104
0.0312/0.0104
0.0156/0.0052
0.0780/0.0260
0.1113/0.0371
0.7260/0.2420
0.5004/0.1668
0.4254/0.1418
0.0156/0.0052 0.00033/0.00011
0.0189/0.0063 0.00039/0.00013
0.0078/0.0026 0.00030/0.00011
0.3750/0.1250 0.0375/0.0125
0.3750/0.1250
0.3129/0.1043 0.0126/0.0042
0.1563/0.0521 0.0015/0.0005 0.0063/0.0021
0.3129/0.1043 0.0030/0.0010 0.0126/0.0042
0.0156/0.0052 0.0006/0.0002
(continued)
-------
o
&>
ft
(D
OJ
00
o
TABLE 6-2 (continued)
CTl
Dissolved
. chronium,
fuucategory kg/Kg
Byproduct coke
Beehive coke
Sintering
Blast furnace (iron)
Blast furnace (ferromanganese)
Basic oxygen furnace (seninwet
air pollution control)0
Basic oxygen furnace (wet air
pollution control)
Open hearth furnace
Electric arc furnace (seaiwet
air pollution control)
Electric arc furnace (wet air
pollution control)
Vacuum degassing
Continuous casting and pressure
slab molding
Hot forning-prinary
Hot forming-section
Hot forming- flat
Pipe and tube
Pickling-sulfuric acid, batch
and continuous
Pickling-hydrochloric acid,
batch and continuous
Cold rolling
Hot coating-galvanizing 0.0225/0.0075
Hot coating- terne
Combination acid pickling
(batch and continuous) 0.0063/0.0021
Scale removal (kolene and
hydride 0.0030/0.0010
Wire pickling and coating 0.0063/0.0021
Continuous alkaline cleaning 0.0003/0.0001
Pollutant parameter
Hexavalent Dissolved Dissolved
chromium. Fluorine, nickel copper,
kq/Mq Lead, kg/Mq Tin, kq/Mq kq/Mg kq/Mg kg/Mq pH
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
0.00015/0.00005 6 to 9
0.00375/0.00125 0.0375/0.0125 6 to 9
0.1878/0.0626 0.0030/0.0010 6 to 9
0.0003/0.0001 6 to 9
0.1878/0.0626 0.0030/0.0010 0.0030/0.0010 6 to 9
0 00015/0.00005 6 to 9
Note: Blanks indicate no data available.
values are daily maxiinum/30-day average Imitations.
Although not a subcategory, Miscellaneous runoffs from casting and slagging have the following BPT limitation: there shall be no discharge of process
wastewater pollutants from casting and slagging to navigable waters (but the limitation does not apply to any operation in Mahoning Valley).
There shall be no discharge of process wastewater pollutants to navigable waters
-------
Volatile components are recovered and processed in a variety of
ways to produce tars, light oils, phenolates, ammonium compounds,
naphthalene, and other materials, including coke oven gas. A
complete list of coal chemicals produced by byproducts coke
plants appears in Table 6-3.
TABLE 6-3. COAL CHEMICALS PRODUCED BY U.S. BYPRODUCTS
RECOVERY COKEMAKING PLANTS [2]
Crude coal tar
Crude light oils
Ammonium sulfate
Sodium phenolate or sodium carbolate
Toluene, all grades
Xylene, all grades
Intermediate light oils
Naphthalene, solidifying at <74°C
Naphthalene, solidifying at between 74°C and 79°C
Benzene, specification grades
Benzene, all other industrial grades
Solvent naphtha, all grades
Pitch-of-tar, soft (S.P. <43.3°C)
Pitch-of-tar, hard (S.P. >71.1°C)
Creosote oils, straight distillate
Creosote oils, in coal tar solutions
Enriched ammonia liquor (high NH3 content)
Crude chemical oil (tar acid oils)
Mono- and diammonium phosphate
Phenol, industrial grades
Phenol, all other grades
Cresols
Cresylic acid
Picolines
Anhydrous ammonia
Elemental sulfur
Production capacities of the 59 byproduct recovery cokemaking
plants range from 520 Mg/d (580 tons/d) to 21,000 Mg/d (23,000
tons/d), with a total annual capacity of 69,000,000 Mg
(77,000,000 tons). The average raw wastewater flow for the by-
product recovery cokemaking subcategory is 0.38 m3/Mg (92 gal/
ton) of product.
Beehive Coke. The beehive process utilizes ovens in which
carefully controlled quantities of air are admitted to the coking
chambers so that the volatile products which distill from the
coal are immediately burned, thus generating additional heat for
further coking of the coal. No attempt is made to recover gases
or other byproducts of this distillation process. The average
Date: 6/23/80 II.6.1-5
-------
raw wastewater flow for the beehive cokemaking subcategory is
1.5 m3/Mg (370 gal/ton) of product.
This subcategory has been recommended as a Paragraph 8 exclusion
under the NRDC Consent Decree.
Sintering [3]
The 35 sintering steel mills in the United States have an annual
production capacity of 48,000,000 Mg (53,000,000 tons). Fourteen
of these mills operate dry dust collecting systems and do not
discharge wastewater; therefore they are not included in the data
base for this report. Production capacity at the 21 wet sinter-
ing mills ranges from a minimum of 450 Mg/d (500 tons/d) to a
maximum of 11,000 Mg/d (12,000 tons/d).
Sintering is an agglomeration process in which iron-bearing
material, generally fines from various sources, is taken and
mixed with finely divided fuel such as coke breeze. The mixture
is placed on a traveling grate, the bed of raw feed mix is
ignited on the surface, and, as the mixture moves along on the
traveling grate, air is pulled down through the mixture (wind
boxes) to enhance combustion and to sinter the fine ore particles
into lumps. The combusted sinter drops off the traveling grate
at the end of the machine and is then cooled, crushed, and
screened before the proper size sinter is sent to the blast
furnace. Improper size sinter is returned to the head of the
sinter process.
Wastewater flow rates for this subcategory range from 0.11 m3/Mg
(26 gal/ton) to 39 ms/Mg (9,300 gal/ton). Process water varies
from 0.50 m3/Mg (120 gal/ton) to 39 m3/Mg (9,300 gal/ton).
Blast Furnaces [3]
Blast furnace operations produce both pig iron and ferromanganese
iron. Therefore, there are two blast furnace subcategories,
blast furnace-iron and blast furnace-ferromanganese. Only one
furnace was found producing ferromanganese on a regular basis.
The following description of blast furnace operations applies to
both pig iron and ferromanganese furnaces, with the exception
that ferromanganese ore is used in the latter.
Blast furnaces are large, cylindrical steel structures approxi-
mately 100 feet high. Iron is produced by combusting a mixture
of iron ore, coke, and limestone which is fed periodically
through the top of the furnace. Combustion is promoted by blow-
ing heated air into the lower part of the furnace. As the raw
materials melt and decrease in volume, the entire mass of the
charge descends. Additional raw materials are added to keep the
mass within the furnace at a constant level.
Date: 6/23/80 II.6.1-6
-------
Cleaning of top gases produced in the furnace can be accomplished
using a variety of wet or dry processes. One method uses one wet
scrubber (primary), a second type uses two wet scrubbers (primary
and secondary), and a third uses one wet scrubber and one dry air
pollution control device.
There are 55 plants with blast furnace operations in the United
States, most having more than one blast furnace, for a total of
174 blast furnaces. The annual capacity of the 55 plants is
109,000,000 Mg (120,000,000 tons). Productions range from 720
Mg/d (800 tons/d) to 20,000 Mg/d (22,000 tons/d).
Basic Oxygen Furnaces [4]
Basic oxygen furnace (EOF) steelmaking operations are divided
into two subcategories: basic oxygen furnace-semiwet air pollu-
tion control, and basic oxygen furnace-wet air pollution control.
The latter is further subdivided into open combustion and sup-
pressed combustion.
All EOF furnace methods use pure oxygen to refine the hot metal
(iron) and other metallics into steel by oxidizing and removing
the elements present such as silicon, phosphorus, etc.
The basic oxygen furnace top blown steelmaking process is a
method of producing steel in a pearshaped, refractory-lined,
open-mouth furnace with a mixture of hot metal, scrap, and fluxes.
Pure oxygen is injected at supersonic velocities through a water-
cooled copper-tipped steel lance for approximately 25 minutes.
As this process is exothermic, (heat generating), a definite per-
centage of steel scrap can be melted without use of external
fuel. The general ratio is about 70% hot metal and 30% scrap.
The waste products from the basic oxygen process are heat, air-
borne fluxes, slag, carbon monoxide and dioxide gases, and oxides
of iron (FeO, Fe203, Fe3O4) emitted as submicrometer dust.
The basic oxygen furnace is always equipped with some type of
gas-cleaning system for containing and cooling the huge amounts
of hot gases and collecting the submicrometer particulates
produced. Water is always used to quench the offgases to temper-
atures where the gas-cleaning equipment can effectively handle
them. Two main process types of gas-cleaning systems are used
for the basic oxygen furnace, precipitators and venturi scrubbers,
although a bag filter type installation is presently being
installed for a EOF specialty steel producer.
There are 10 semiwet EOF steelmaking operations in the United
States producing approximately 19,000,000 Mg (21,000,000 tons)
annually; there are 13 wet-open combustion plants producing
nearly 44,000,000 Mg (48,000,000 tons) annually; and there are
6 wet-suppressed combustion plants producing 15,000,000 Mg
Date: 6/23/80 II.6.1-7
-------
(16,000,000 tons) annually. In 1976, the basic oxygen process
accounted for about 63% of steel production.
Open Hearth Furnace [4]
The open hearth subcategory is subdivided into plants using semir-
wet air pollution control methods (APCM) and wet APCMs. There
are five open hearth facilities in the United States with only
one facility using a semiwet APCM. Production capacity at these
five plants ranges from 3,500 Mg/d (3,800 tons/d) to 9,100 Mg/d
(11,000 tons/d).
The open hearth furnace steelmaking process is an old method of
steel production. A shallow rectangular refractory basin or
hearth enclosed by refractory-lined walls and roof is used. The
front wall has water-cooled doors for charging raw materials.
These raw materials may be all scrap, but the most common charge
is a 50-50 mixture of hot metal and scrap steel. A tap hole is
provided to drain the molten metal from the furnace.
Open hearth furnaces are normally equipped with some type of gas-
cleaning system for cooling and scrubbing the hot gases emitted
from the furnace. Dry, semiwet, and wet APCMs may be used.
Semiwet systems generally consist of a spark box or spray chamber
that cools the gas by water spray to approximately 280°C (550°F).
The wet scrubber systems quench the gases emanating from the
furnace by evaporation. If waste heat boiler tubes are used less
heat is required to be removed. Scrubbers may be independently
mounted or manifolded into a central system. Effluent from
these process is discharged for treatment.
The applied flow rate is 5 m3/Mg (1,200 gal/ton) at the semiwet
APCM facility; it ranges from 3.4 m3/Mg (900 gal/ton) to 16.7
ms/Mg (4,400 gal/ton) at the wet APCM plants. The discharge flow
rate is 0.26 m3/Mg (69 gal/ton) at the semiwet APCM facility, and
it ranges from 0.40 ms/Mg (105 gal/ton) to 2.2 m3/Mg (580 gal/ton)
at the wet APCM plants.
Electric Arc Furnaces [5]
The electric arc furnace (EAF) steelmaking process is a method of
producing high-quality and alloy steels in refractory-lined
cylindrical furnaces utilizing a cold steel scrap charge and
fluxes. The heat for melting the scrap charge, fluxes, etc., is
furnished by passing an electric current (arcing) through the
scrap or steel bath by means of three triangularly spaced
cylindrical carbon electrodes inserted through the furnace roof.
Electric arc furnace steelmaking operations are divided into two
subcategories by the type of air pollution control system used:
electric arc furnace-semiwet APCM, and electric arc furnace-wet
APCM. These air pollution control methods have been briefly
described in previous subcategories. The majority of electric
Date: 6/23/80 II.6.1-8
-------
arc furnace operations in the United States are dry operations
with no discharge and are therefore not considered a subcategory.
There are four semiwet electric arc furnace plants in the United
States with an annual production capacity of 3,800,000 Mg
(4,200,000 tons). The eight wet electric arc furnace plants have
an annual production capacity of 4,700,000 Mg (5,100,000 tons).
There is one specialty steel wet electric arc furnace operation
which has an annual production capacity of 830,000 Mg (910,000
tons).
Applied flow rates for process wastewater for semiwet electric
arc furnace plants range from 1.13 m3/Mg (270 gal/ton) to
2.67 m3/Mg (640 gal/ton). For wet electric arc furnace plants
the range is 3.46 m3/Mg (830 gal/ton) to 14.6 m3/Mg (3,500
gal/ton). The discharge flow ranges from 0 m3/Mg (0 gal/ton) to
1.13 m3/Mg (270 gal/ton) for semiwet operations and from 0 m3/Mg
(0 gal/ton) to 14.6 m3/Mg (3,500 gal/ton) for wet operations.
Vacuum Degassing [5]
The vacuum degassing subcategory is subdivided into specialty
steel and carbon steel vacuum degassers. There are a total of
35 vacuum degassers in the United States, with 7 producing carbon
steel and the remainder producing specialty steels. Annual pro-
duction capacity of the carbon steel facilities is approximately
6,100,000 Mg (6,700,000 tons); for specialty steels it is
6,900,000 Mg (7,700,000 tons).
The vacuum degassing operation serves as an intermediary step in
steelmaking. After the hot metal has been refined to steel in
EOF, EAF, or open hearth furnaces, the heat of steel is trans-
ferred to the vacuum degasser for further refining. Degassing is
performed only if steel order specifications require it.
Vacuum degassing is the process whereby molten steel is subjected
to low pressures in order to eliminate gases absorbed by the
steel that may reduce its quality. Gases such as hydrogen,
oxygen, and nitrogen can impact detrimental qualities to the
finished product if not removed from the steel while it is in
its molten state. Hydrogen, in particular, can cause flaking
and embrittlement of steel. Oxygen and nitrogen when in combina-
tion with other elements can remain in the steel as weakening
impurities.
Hydrogen and oxygen are removed from the molten steel by decreas-
ing the partial pressure of each above the molten bath. Oxygen
is removed as carbon monoxide or by complexing with strong
deoxidizers such as aluminum, titanium, or silicon. After
degassing the steel is sent to final product processing. Vacuum
degassing is used primarly for specialty steels. Only 7 of the
35 degassing plants refine more carbon steel than specialty steel,
Date: 6/23/80 II.6.1-9
-------
Continuous Casting [5]
Continuous casting plants in the United States are identified as
carbon steel or specialty steel casters. There are 54 continuous
casting facilities in the United States with a total annual
production of 24,849,000 Mg (27,392,000 tons) of cast steel.
Five of these plants are specialty steel facilities and the
remainder produce carbon steel.
In the continuous casting process the hot molten steel is poured
from the ladle into a refractory-lined tundish that maintains a
constant head of molten metal. This constant head is essential
to a controlled rate, and in multiple-strand operations it
distributes the molten metal to the casting networks. The molten
metal is poured into oscillating water-cooled copper molds where
partial solidification occurs. These molds oscillate to prevent
the steel from sticking to them. As the metal solidifies, the
product is removed continuously to a series of cooling zones.
The rough product is then sent to finishing.
Flow rates for applied process water in this subcategory vary
from 0.09 ms/Mg (22 gal/ton) to 67 m3/Mg (16,000 gal/ton) and
average 19.6 m5/Mg (4,700 gal/ton). Discharge flow rates range
from 0 m3/Mg (0 gal/ton) to 23 m3/Mg (5,300 gal/ton) and average
1.7 m3/Mg (400 gal/ton).
Hot Forming-Primary [6]
The hot forming-primary mill is the first step toward making a
finished product from steel ingots. Primary mills produce either
blooms, slabs, or billets. Blooming mills can be coupled with
billet mills so that the semifinished bloom can immediately be
rolled in the billet mill while it is still hot. There are,
however, many variations of primary mills depending upon the
plants' needs.
The hot forming-primary subcategory is subdivided into carbon
steel and specialty steels. The 86 hot forming-primary carbon
steel mills in the United States have an annual production
capacity of 192,000,000 Mg (212,000,000 tons). The 14 hot
forming-primary specialty mills have an annual production
capacity 12,400,000 Mg (13,700,000 tons).
Typical primary mill operations begin when an ingot buggy trans-
fers a heated ingot from the soaking pits where the ingot is main-
tained at approximately 1200°C, to an ingot-receiving table
which, in turn, delivers the ingot to the mill-approach tables.
The latter tables transport the ingot to the front table or
roller table in preparation for rolling.
Depending upon the type of primary mill, (reversing, tandem,
etc.), the hot ingot is passed between the mill rollers and
Date: 6/23/80 II.6.1-10
-------
reduced in cross-sectional size. After the ingot is rolled to
the desired size, the end of the bloom, slab, or billet is cut
off or "cropped." The crop shear removes a sufficient length
of stock to meet chemical and metallurgical specifications.
Blooms from the primary mill are processed into rails and joint
bars, structural and other sections, and billets. Billets are
further processed into tube rounds, bar and rod, wire, and
special products.
Average flow rates of the eight sampled carbon primary mills are
2.8 m^/Mg (670 gal/ton) applied flow and 1.4 ms/Mg (320 gal/ton)
discharge flow. Average flow rates at the nine sampled specialty
steel mills are 12 m3/Mg (2,800 gal/ton) applied flow and 7.0 m3/
Mg (1,700 gal/ton) discharge flow.
Hot Forming-Section [6]
Section rolling mills take the semifinished product from blooming
mills and hot roll either an intermediate finished product
called a billet (which is further reduced in other finishing
mills) or roll the bloom directly to a finished product. Most
billets are rolled directly from the blooming mill without
reheating furnaces, but some steel plants do provide furnaces
between the blooming and billet mills.
The intermediate and finished products from a section mill
include rails, joint bars, I-beams, channels, angles, wide
flanged beams, H-beams, sheet piling, and billets (which are
further processed into tube rounds, bar and rod, wire, and
numerous special sections).
The hot forming-section steel mills are of two types: carbon
steel and specialty steel mills. The 235 hot forming-section
carbon steel mills in the United States have an annual production
capacity of 130,000,000 Mg (140,000,000 tons), and the 37 special
steel section mills have an-annual production capcity of
15,000,000 Mg (16,000,000 tons). Daily production at hot forming-
section steel mills ranges from 8.1 Mg (9 tons) to 9,700 Mg
(11,000 tons). Average applied and discharge flow rates for the
hot forming-section mills sampled are 19 m3/Mg (4,500 gal/ton)
applied flow and 6.9 m3/Mg (1,660 gal/ton) discharge flow.
Hot Forming-Flat [6]
The hot forming-flat subcategory is subdivided into plate mills
and hot strip and sheet mills. In the United States there are a
total of 68 facilities in this subcategory. The 26 plate mills
annually produce 2.2 x 107 Mg. The 42 flat-hot strip and sheet
mills annually produce 9.4 x 107 Mg. Some mills are capable of
producing both types of product.
Date: 6/23/80 II.6.1-11
-------
The basic operation of a plate mill is the reduction of a heated
slab to the weight and dimensional limitations defining plates
(more than 8 inches wide and at least 0.23 inch thick or over
48 inches wide and 0.18 inch thick). This is accomplished by
heating the slab descaling, rolling, leveling or flattening,
cooling, and shearing to desired size.
Hot strip mills are often continuous. These mills use slabs
that are reheated to rolling temperature by reheating furnaces.
The basic operation of a hot strip mill is the reduction of
slabs to flat strip steel in thicknesses of 0.04 inch to 1.25
inches, widths of 24 inches to 96 inches and lengths up to 2,000
feet. The product may be sold as produced, further processed in
cold reduction mills, or used for plated or coated products.
Pipe and Tube [7]
The pipe and tube subcategory is subdivided into hot forming
and cold forming operations. In the United States there are
55 hot forming pipe and tube mills (with an annual production
capacity of 17,000,000 Mg [19,000,000 tons]) and 108 cold form-
ing pipe and tube mills (with an annual production capacity of
8,794,000 Mg [9,696,000 tons]).
Within the pipe and tube subcategory, the processes employed and
the equipment used vary between hot forming and cold forming
operations. The basic differences between the two arise in the
process water usage rates and the wastewater characteristics.
A hot forming pipe and tube mill takes hot steel and processes it
into products such as seamless pipe and tube. Relatively high
water rates are required for the various contact and noncontact
cooling systems. On the other hand, the cold forming process
takes a cold semifinished product and manufactures cold drawn
or welded pipe and tube. Water requirements are lower and the
presence of soluble oil distinguishes the wastewater.
Daily production capacity of the hot forming pipe and tube mills
ranges from 44 Mg (48 tons) to 3,100 Mg (3,400 tons). Daily
production capacity of the cold forming pipe and tube mills
ranges from 0.73 Mg (0.8 tons) to 3,100 Mg (3,400 tons). Average
applied flow rate for all 55 hot forming pipe and tube mills is
25.8 m3/Mg (6,200 gal/ton) and the average discharge rate is 17.7
m3/Mg (4,250 gal/ton). The average applied flow rate for the 108
cold forming pipe and tube mills is 11 m3/Mg (2,700 gal/ton) and
the average discharge rate is 7.1 m3/Mg (1,700 gal/ton).
Sulfuric Acid Pickling [8]
The sulfuric acid pickling subcategory is subdivided into con-
tinuous pickling and batch pickling, each further subdivided into
carbon steel and specialty steel. The 44 continuous sulfuric
Date: 6/23/80 II.6.1-12
-------
acid pickling operations in the United States have an estimated
annual production capacity of 14,500,000 Mg (16,000,000 tons);
the 105 batch sulfuric acid operations have an estimated annual
production capacity of 8,200,000 Mg (19,000,000 tons).
Annual production at batch H2S04 pickling-carbon steel mills
ranges from 180 Mg (200 tons) to 840,000 Mg (920,000 tons). At
batch H2S04 pickling-specialty steel mills the range is 3,800 Mg
(4,200 tons) to 280,000 Mg (300,000 tons); at continuous H2SO4
pickling-carbon steel mills it is 1,000 Mg (1,100 tons) to
2,500,000 Mg (2,800,000 tons); and at continuous H2S04 pickling-
specialty steel mills it is 17,200 Mg (19,000 tons) to 261,000 Mg
(288,000 tons).
The traditional method of scale removal is "pickling," the
chemical removal of surface oxides from metal by immersion in a
heated solution. Carbon steel pickling is almost universally
accomplished in either hydrochloric or sulfuric acid, and
stainless is pickled in hydrofluoric or nitric acid. Acid
type used, bath temperature, use of inhibitors, and source of
agitation depend on the type of material to be pickled.
Various organic chemicals are used in pickling to inhibit acid
attachment on the base metal, while permitting preferential
attachment to the oxider. Wetting agents are used to improve
the effective contact of the acid solution with the metal
surface. Pickling may be done on a batch or a continuous basis
depending on the product being pickled. A rinse step normally
follows the operation to reduce acid carryover.
The major wastewater flows arise from rinsing and fume-scrubbing
operations. Rinse water flows are somewhat dependent on product
retirements and process line configuration. As process lines
become more complex, an occasional opportunity arises to reduce
flows via recirculation of a portion of the rinse water. For
example, final rinse water can be reused for initial spray rins-
ing and for makeup to fume scrubber, thus reducing the total
process wastewater.
Discharge flow rates of wastewater vary throughout this subcate-
gory. Continuous pickling generaly discharges slightly more
water than does batch pickling. Continuous processes consisting
of rinses, fume hood scrubbers, acid recovery systems, and spent
pickle liquor condensates release averages of 2.3, 0.42, 0.32,
and 0.086 m3/Mg of product, respectively. Batch processes use
the same general processes and release 2.0, 0.55, 0.012, and
0.075 m3/Mg of product, respectively.
Date: 6/23/80 II.6.1-13
-------
Hydrochloric Acid Pickling [8]
The hydrochloric acid pickling subcategory includes continuous
strip pickling and batch pickling operations. There are 43
hydrochloric acid pickling steel mills with an annual production
capacity of 23,000,000 Mg. Pickling is accomplished by one of
two general processes dependent upon the type of material to be
pickled. Pickling lines for hot-rolled strip operate continuo-
usly on long coils. The steel passes through the pickler counter-
currently to the flow of the acid solution. Most pickling opera-
tions are followed by several rinsing steps which remove the
excess acid and oxides that may cling to the surface. The water
for the rinse can be reused in subsequent rinsing operations.
Continuous operations have several wastewater sources including
acid regeneration, neutral rinse, and specialty, carbon steel,
and wire product rinses. Average flow from the various continu-
ous operations are:
Acid regeneration 1.0 m3/Mg
Neutral rinse 1.7 m3/Mg
Specialty steel pickling 2.7 m3/Mg
Carbon steel pickling 1.8 m3/Mg
Wire pickling 6.8 m3/Mg
Batch operations normally use much more water. Average flows
for this pickling process are:
Neutral rinse 5.5 ms/Mg
Carbon steel pickling 3.8 m3/Mg
Wire pickling 7.9 m3/Mg
Cold Rolling [7]
Cold rolling is an operation in which unheated metal is passed
through a pair of rolls to reduce its thickness, generally by a
relatively small amount; to produced a smooth, dense surface;
and/or to develop controlled mechanical properties in the metal.
A typical modern cold rolling shop would contain a continuous
pickling operation (sulfuric or hydrochloric acid) for the
removal of scale and rust from the hot rolled breakdown coil.
Oil applied to the strip as it leaves the pickler prevents
rusting and acts as a lubricant in the cold rolling mill. The
coil is then fed into a continuous cold rolling reducing mill
that can contain up to six rolling stands in series.
During rolling the steel becomes quite hard and unsuitable for
most uses. As a result, the strip must usually undergo an
annealing operation to return its ductility and to effect other
required changes in mechanical properties. This is done in
either a batch or continuous annealing operation.
Date: 6/23/80 II.6.1-14
-------
The cold rolling subcategory is divided into three subsections:
recirculating mills, direct application mills, and combination
mills. There are 170 recirculating cold rolling mills in the
United States with an annual production capacity of 27,000,000 Mg
(30,000,000 tons). The 79 direct application cold rolling mills
have an annual production capacity of 17,000,000 Mg (19,000,000
tons). Annual production capacity at the 20 combination cold
rolling mills is 13,000,000 Mg (15,000,000 tons).
Hot Coating [9]
Hot coating operations are divided into two subcategories, hot
coating-galvanizing and hot coating-terne plating. Hot coating
processes in the iron and steel industry involve the immersion of
clean steel into baths of molten metal for the purpose of attach-
ing a thin layer of this metal onto the steel surfaces. Such
coatings serve to provide certain desired qualities, such as
resistance to corrosion, safety from contamination, or a decora-
tive bright appearance. Finished products retain the strength of
steel while gaining the improved surface quality of the coated
metal for a fraction of the cost of products made entirely of
that metal alone.
The principal metallic coating operations practiced in the iron
and steel industry can be divided into two major classes; hot
coating and cold coating. Zinc, terne, and aluminum coatings
are most often applied hot, while tin and chromium are usually
applied electrolytically from plating solutions maintained at
20°C to 90°C (68-194°F), not actually "cold," but relatively so
when compared with molten metal temperatures encountered in the
hot dip processes. This cold coating process is not considered
within this industry description due to its inclusion in the
electroplating industry.
Continuous hot dip-galvanizing is the most common method used for
hot coating steel with zinc. The process starts with annealed
and tempered strip which receives a light muriatic acid (HC1)
pickle and rinse, then proceeds directly through a layer of
fluxing agent to the molten zinc bath. The coated strip is
dried and recoiled, or cut to size for shipment.
Terne (from a French word meaning "dull") is an inexpensive,
corrosion-resistant, hot dip coating consisting of tin and lead
in a ratio typically near five or six parts lead to one part tin.
A major portion of all terne-coated material is used in the auto
industry to manufacture gas tanks, with lesser amounts going into
the production of automotive mufflers, oil pans, air cleaners,
and radiator parts.
Date: 6/23/80 II.6.1-15
-------
The third major metallic coating applied using the hot dip tech-
nique is aluminum. Products made of aluminum-finished steel
include bright and matte finished sheets and strip used as build-
ing materials in marine, industrial, or other environments where
high degrees of resistance to corrosion are required.
There are 94 hot coating plants in the United States, of which 68
responded to basic DCP's. The annual production capacity of
those 68 plants (representing 173 production lines) is 7,700,000
Mg (8,500,000 tons).
Daily production at the nine sampled hot coating-galvanizing
plants ranges from 5 Mg/d (6 tons/d) to 1,585 Mg/d (1,750
tons/d). At the three sampled hot coating-terne plating plants
daily production ranges from 475 Mg/d (525 tons/d) to 510 Mg/d
(560 tons/d).
Combination Acid Pickling [8]
Pickling is the process of chemically removing oxides and scale
from the surface of a metal by the action of water solutions of
inorganic acids. While pickling is only one of several methods
of removing surface oxides, it is widely used in the manufacture
of various steel products because of its comparatively low
operating costs and ease of operation. Considerable variation
in the types of pickling solutions, operations, and equipment is
found in the industry.
In combination acid pickling, a minimum of two different acid
solutions act on the product being processed. These two acids
can be in different tanks or can be mixed together, as is done
in some cases with nitric and hydrofluoric acids. Depending on
the type of material to be pickled, combination acid pickling
(CAP) is carried out by one of two general processes, the sub-
divisions of this subcategory: CAP-batch type and CAP-continuous
type.
Batch Type Pickling. Large, open tanks of a wide range of
sizes are used for batch type pickling, principally for rods,
bars, billets, sheet, strip, wire and tubing. The tanks,
generally rubber lined and brick sheathed, hold a large volume
of heated acid solution. After reaching a certain iron buildup
due to scale removal, the acid solution is considered spent and
dumped as a batch.
Continuous Pickling. Continuous pickling is done on a small
number of steel products, including, strip, sheet, and wire. In
this process, there are at least two acid tanks, each usually
divided into 4 or 5 compartments. The fresh acid solution is
added to the last tank section and cascades through the tank to
an overflow located in the first section. Acid flow is opposite
to the direction of product travel.
Date: 6/23/80 II.6.1-16
-------
After pickling, the product is rinsed before moving on to the
next sequence in the process. The rinse step may vary from a
one-step dunk to more sophisticated multistage rinsing.
In the United States there are 57 plants with 152 combination
acid pickling mills. Of these mills, 78 are batch type and 74
are continuous type operations. The annual production capacity
of the 78 batch type operations is 3,000,000 Mg (2,700,000 tons);
that of the 74 continuous type operations is 3,100,000 Mg
(3,400,000 tons).
Wastewater discharge at combination acid facilities varies with
the process type used. Batch type processes discharge 2.1 m3
of water per Mg of product (500 gal/ton) while continuous type
processes discharge nearly 11 m3 of water per Mg of product
(2,500 gal/ton). Other sources of wastewater include fume hood
scrubber water (6.3 m3/Mg [1,500 gal/ton]) and spent pickle
liquor (0.063 ms/Mg [15 gal/ton]).
Scale Removal, Kolene and Hydride [9]
The scale removal subcategory is subdivided into kolene scale
removal and hydride scale removal. Kolene scale removal opera-
tions are further subdivided into continuous and batch type
operations. In the United States there are 11 continuous type
kolene scale removal mills, which have an annual production
capacity of 120,000 Mg (130,000 tons). There are 10 batch type
kolene scale removal mills with an annual production capacity of
260,000 Mg (280,000 tons). The eight hydride scale removal mills
in the United States have an annual production capacity of
92,000 Mg (100,000 tons).
The kolene process utilizes highly oxidizing salt baths at 370°C
to 480°C (700-900°F), which react far more aggressively with
scale than with the base metal. This results in a smoother
surface than is obtainable with acid pickling.
Sodium hydride descaling depends on the strong reducing proper-
ties of a 1.5% to 2% by weight concentration of sodium hydride
in a fused caustic soda bath at 370°C (700°F). Most scale-
forming oxides are reduced to the base metal; oxides of metals
that form acid radicals are partially reduced. Hydride and
kolene descaling operations are operated only as an integral
part of the pickling process.
The average discharge flow rates for kolene scale removal mills
are 6.20 m3/Mg (1,500 gal/ton) for batch type operations and 1.8
m3/Mg (420 gal/ton) for continuous type operations. The average
discharge flow rate for hydride scale removal mills is 2.6 m3/Mg
(610 gal/ton).
Date: 6/23/80 II.6.1-17
-------
Continuous Alkaline Cleaning [9]
Alkaline cleaners are used where mineral and animal fats and oils
must be removed. Mere dipping in solutions of various composi-
tions, concentrations, and temperatures is often satisfactory.
The use of electrolytic cleaning may be advisable for large-scale
production, or where this method yields a cleaner product.
Caustic soda, soda ash, alkaline silicates, and phosphates are
common alkaline cleaning agents. Sometimes the addition of
wetting agents to the cleaning bath will facilitate cleaning.
Alkaline cleaning may be carried out by two different methods.
Continuous cleaning is used at 70% of the mills that responded to
questionnaires, and the balance use batch cleaning. Continuous
cleaning mills use approximately 1.8 m3 of water per Mg of
product (434 gal/ton) to clean sheet, strip, or wire. Batch
cleaning transfers the product from the wash to the rinse
manually and uses approximately 1.3 m3 of water per Mg of product
(307 gal/ton).
Alkaline cleaning lines are usually operated as a part of a
larger, more complex line such as an annealing, galvanizing, or
pickling line. Water flow rates range from 0.002 m3/Mg (0.059
gal/ton) of product to 1.25 ms/Mg (300 gal/ton) of product.
Products from this process vary considerably, ranging from
sheet and strip to chain link fence.
II.6.2 WASTEWATER CHARACTERIZATION [1-9]
The following paragraphs and tables describe the wastewater gener-
ated from each subcategory. These descriptions normally include
a general statement on the potential sources of wastewater, aver-
age wastewater flow, and the common pollutants found in the
wastewater. Tables present median, maximum, and average conven-
tional and toxic pollutant concentrations for the raw and treated
wastewater when sufficient data are available. The tables were
generated from the sampling data found in the reference documents.
Also reported is the average percent removal determined by the
reduction in the average treated effluent concentration compared
with the average raw wastewater concentration.
II.6.2.1 Subcategory 1 - Byproduct Cokemaking [2]
Raw waste loads from byproduct cokemaking operations differ
widely based on the type of coal used, variations in recovery
processes, water use system configurations, oven carbonizing
temperatures, and duration of the cycle. The major liquid
wastes generated during cokemaking and byproduct recovery opera-
tions include excess ammonia liquor, final cooler wastewater,
light oil recovery wastes from the benzol plant, barometric
condenser wastes, desulfurizer wastes, and contaminated waters
Date: 6/23/80 II.6.1-18
-------
from air pollution emission scrubbers. Some additional waste-
water may result from coke wharf drainage, quench pump overflows,
and coal pile runoff. Table 6-4 shows the ranges of volumes for
these sources.
TABLE 6-4.
WASTEWATER FLOWS FROM SOURCES IN THE
BYPRODUCT COKEMAKING SUBCATEGORY [2]
Wastewater stream
Average,
mVMg
Excess ammonia liquor 0.17
Final cooler wastewater 0.14
Benzol plant wastes 0.25
Barometric condenser 0.16
Desulfurizer 0.081
Air pollution emission scrubbers 1.7
Steam condensates 0.040
Miscellaneous wastes 0.15
Conventional pollutants often found in the raw wastewater include
significant concentrations of total suspended solids, ammonia,
sulfide, and oil and grease. Subcategory data are presented in
Table 6-5. Toxic pollutants found in the wastewater generally
consist of metals, phenols, and aromatics. Table 6-6 lists
information on these pollutants.
TABLE 6-5.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANT FOR THE BYPRODUCT RECOVERY
COKEMAKING SUBCATEGORY [2]
Raw wastewater
Number
Parameter detected
Ammonia
Thiocyanate
Oil and grease
Phenol
Sulfide
TSS
PH
7
7
7
7
7
7
7
Concentration,
Median Maximum
2,400
593
83
630
440
59
8.6
8,300
1,250
180
1,700
1,800
97
9.7
mg/La
Number
Average detected
2,900
530
140
740
630
67
8.3
9
9
B
7
8
8
9
Treated effluent
. — i
Concentration, mg/L I
Median
220
29
11
5.1
91
41
8.5
Maximum Average 1
4,900
1,050
40
220
1,800
540
11.8
900
29
16
26
320
120
8.9
Average
>ercent
removal
69
95
90
96
49
_b
*Except pH values, given in pH units.
Negative removal.
Date: 6/23/80
II.6.1-19
-------
D
QJ
rt
(0
CTi
N)
OJ
00
O
TABLE 6-6. WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOR THE BYPRODUCT RECOVERY COKEMAKING SUBCATEGORY [2]
I
N5
O
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cyanide
Selenium
Silver
Zinc
Nitrogen compounds
Acrylonitrile
Phenols
2 , 4-Dimethylphenol
2 -Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
4, 6-Dinitro-o-cresol
Aromatics
Benzene
2,4-Dinitrotoluene
2, 6-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic aromatics
Acenaphthylene
Benzo ( a ) anthracene
Benzo ( a jpyrene
Chrysene
Fluor anthene
Fluorene
Naphthalene
Pyrene
Halogenated aliphatics
Chloroform
1, 1-Dichloroethylene
Pesticides and metabolites
Isophorone
Number
detected
3
3
7
4
6
5
5
3
2
1
7
1
2
2
7
1
1
5
5
7
3
4
S
7
7
7
6
5
2
2
Raw
wastewater
Treated effluent
Concentration, M9/L
Median
33
660
26,000
410
25
130
2,700
5,000
770
395
120,000
400
2,200
530
27,000
1,900
240
300
5,700
3,200
150
360
320
950
370
27,500
760
120
2,000
Maximum
335
170,000
190,000
2,600
670
470
4,700
84,000
1,500
670,000
4,300
970
86,000
640
17,000
6,400
1,200
1,100
1,500
3,100
2,500
39,000
2,600
1,400
3
4,000
Average
120
57,000
47,000
860
130
200
2,700
23,000
770
240,000
2,200
530
29,000
340
6,700
3,000
490
480
550
1,200
700
25,000
910
400
3
2,000
Number
detected
3
2
5
3
4
3
2
0
1
1
5
0
2
1
5
1
1
4
5
5
3
3
0
5
5
4
5
3
1
Concentration ,
Median
41
210
2,500
640
17
130
1,600
<5
49
48
33
<5
260
510
140
27
73
7
5
13
8
10
700
8
200
170
Maximum
130
400
22,000
650
25
220
3,000
53,000
64
140,000
6,600
11,000
1,600
260
13
500
190
5,900
280
280
Mg/L
Average
60
210
8,800
430
17
110
1,600
11,000
33
30,000
1,700
2,600
330
88
9
110
47
1,800
64
180
0
Average
percent
removal
50
99
81
50
87
45
40
99
88
95
94
99
a
78
42
a
61
89
82
98
91
87
95
55
92
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
Treated effluent concentration exceeds raw wastewater concentration.
-------
II.6.2.2 Subcategory 2 - Beehive Cokemaking [2]
This subcategory provides sufficient oxygen to burn volatile by-
products during the cokemaking process. As a result of this
complete burning and the lack of byproduct recovery, relatively
simple wastewater is generated, solely from the quenching opera-
tion. Total suspended solids is the only pollutant requiring
control in this subcategory. Table 6-7 shows conventional pollu-
tant data for the beehive cokemaking process.
TABLE 6-7. WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLU-
TANTS FOR THE BEEHIVE COKEMAKING SUBCATEGORY [2]
Raw wastewater
Parameter
Ammonia
Cyanide , total
Oil and grease
Phenol
TSS
PH
Number
detected
3
3
3
3
3
3
Concentration,
Median
0
0
<5
0
170
7.3
Maximum
0.33
0.002
<5
0.011
720
7.3
mg/L
Average
0.11
0.0007
<5
0.004
310
7.2
Number
detected
3
3
3
3
3
1
Treated effluent
Concentration
Median
0
0
0
0
0
Maximum
0.24
0.004
<5
0.014
36
,mg/La
Average
0.08
0.001
<1.6
0.005
12
7.1
Percent
removal
27
_b
68
-b
96
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
Effluent flow rates range from 0 to 2.04 m3/Mg. Total recycle
is often used because of the low pollutant loadings.
II.6.2.3 Subcategory 3 - Sintering [3]
Process wastewaters emanating from the sintering subcategory ex-
hibit common quality characteristics. Suspended solids, oil and
grease, sulfide, and fluoride are normally present in some con-
centrations. However, the quantities of these regulated param-
eters exhibit considerable variability depending on the number
of sources generating wastewater. Tables 6-8 and 6-9 present
conventional and toxic pollutant data for this subcategory.
TABLE 6-8. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR SINTERING SUBCATEGORY [3]
Average rav wastewater flow. 2 0 m3/Mq (485 gal/ton)
Average treated effluent flow 0.55 m5/Mg (132 gal/ton)
Raw wastewater
Parameter
Fluoride
TSS
0x1 and grease
Sulfide
PH
Number
detected
4
5
5
5
5
Concentration^
Median
4.7
4,300
200
5.8
11.4
Maximum
18 0
20,000
500
190
12.7
tog/I."
Average
t 9
6,000
240
52
10.4
Treated
effluent
Number Concentration^
detected Median
4 20
4 420
3 180
4 4.1
4 8.9
Maximum
180
15,000
1,100
11
12.8
mg/L*
Average
55
3,900
430
5.0
9.4
Percent
removal
_b
36
_b
91
Except pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80 II.6.1-21
-------
O
DJ
rt
(D
K>
UJ
OO
O
I
to
to
TABLE 6-9. WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOR SINTERING SUBCATEGORY [3]
Raw wastewater
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Phenols
2,4-Dinitrophenol
Phenol
Polycyclic aromatics
Benzo ( a ) anthracene
Benz o ( a ) pyrene
Chrysene
Fluoranthene
Pyrene
Number
detected
2
3
3
4
2
2
2
3
3
3
3
1
3
2
2
2
2
3
Concentration,
Median
690
98
520
260
5,600
110
12
940
85
120
20
14
56
260
220
160
130
7
Maximum
1,300
620
600
15,000
5,900
200
13
8,700
290
250
370
1,000
516
430
320
254
320
pg/L
Number
Average detected
690
250
400
3,900
5,600
110
12
3,400
130
130
130
380
260
220
160
130
110
2
2
3
3
3
2
2
3
3
3
3
1
3
3
3
3
3
3
Treated effluent
Average
Concentration, M3/L percent
Median
420
50
270
160
800
74
10
940
580
170
350
140
630
150
190
53
310
300
Maximum Average removal
770
90
550
1,100
5,500
130
10
5,000
990
420
490
990
260
240
410
860
1,100
420
50
410
430
3,200
70
10
1,900
520
200
280
370
140
140
160
390
470
39
80
a
89
43
36
17
44
a
a
a
a
2
46
36
_
a
a
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater concentrations.
-------
Wastewater is generated from several areas. Sinter machine and
pretreatroent areas produce an average wastewater flow of 6.06
m3/Mg of product (1,442 gal/ton). If a large discharger is
eliminated from the data set, the average flow reduces to 1.34
m3/Mg (319 gal/ton). The final product treatment area produces
an average wastewater flow of 2.03 m3/Mg of product (4999 gal/ton)
Other areas generating smaller quantities of wastewater include
storage areas, sinter cooling, and crushing/screening operations.
II.6.2.4 Subcategories 4 and 5 - Blast Furnace-Iron and
Ferromanganese [3]
Blast furnace process wastewater is water which comes into inti-
mate contact with the process or its products, thus becoming con-
taminated with various pollutants associated with the process.
This wastewater may be a combination of several wastestreams, but
it is primarily associated with the scrubber wash water from the
wet scrubbing of blast furnace top gases. Other miscellaneous
waters may include floor drains, drip legs, and dekishing opera-
tions .
Top gases contain large amounts of particulates, carbon dioxide,
carbon monoxide, and organic substances. Large particulates are
removed by dry processing, and the gas is then wet scrubbed to
remove other contaminants. Thus, the wastewater entering the
treatment system contains quantities of suspended solids and
organic substances. Wastewater flow entering treatment ranges
from 2.52 m3/Mg product to 37.7 m3/Mg. Treated discharge ranges
from 0 m3/Mg (water recycle) to 27.9 m3/Mg.
Tables 6-10, 6-11, and 6-12 present conventional and toxic pollu-
tant data on a subcategory basis. Data come from sampled plants.
No toxic pollutant data are available for the ferromanganese
subcategory.
TABLE 6-10.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR BLAST FURNACE-IRON
SUBCATEGORY [3]
Raw wastewater
Parameter
Ammonia-N
Cyanide
Fluoride
Phenol
TSS
Sulfide
PH
Number
detected
4
4
4
4
4
4
4
Concentration, mg/La
Median Maximum
39
6.2
13
2.8
1,600
7
9.7
64
85
160
5.4
7,100
68
10.2
Number
Average detected
40
24
48
2.8
2,700
21
9.1
4
4
4
4
4
3
4
treated effluent
*
Concentration, mg/La r
Median Maximum Average i
30
0.66
12
2.4
54
0.4
9.8
45
33
147
6.7
168
0.5
10.9
30
8.6
44
2.9
78
0.4
9.5
iverage
>ercent
removal
75
64
8
_b
97
98
Except pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80
II.6.1-23
-------
TABLE 6-11.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOUND IN BLAST FURNACE-IRON
SUBCATEGORY [3]
Toxic pollutant
Metala and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Silver
Zinc
Phthalatee
BiB(2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
DietHyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenole
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Phenol
Aronatics
Hexachlorobenzene
Polycyclic aromatics
Benzo(a)pyrene
Chryeene
Fluoranthene
Fluorene
Naphthalene
Pyrene
Halogenated aliphatics
Chloroform
1
1
4
4
4
2
3
1
3
4
4
4
4
2
1
4
1
3
3
1
3
3
3
2
3
3
4
Raw wast
37
46
100
300
240
21,000
230
63
57
25,000
100
95
320
10
47
82
240
3
640
103
7
15
82
15
14
53
12
200
630
1,200
43,000
1,200
73
90,000
3,200
340
9,800
16
12,000
53
2,800
9,500
310
11,000
21
19
10, 000
48
yg/L
100
330
420
18,000
480
47
36,000
860
130
2,600
10
3,000
18
1,200
3,200
110
3,600
15
14
3,400
20
1
1
3
3
4
4
3
1
3
3
4
4
4
2
3
3
2
2
4
0
2
3
4
4
3
3
4
Treated effluent
15
6
10
23
28
81
60
4
10
1,200
320
8
94
86
3
36
30
83
590
5
7
15
8
3
12
31
""l""""
11
54
170
3,100
94
26
32,000
11,000
350
190
170
120
86
44
163
1,800
8
74
230
29
15
41
54
Average
10
29
60
830
54
14
8,500
2,900
94
73
86
30
32
30
83
770
5
28
65
12
5
20
34
59
87
90
91
85
95
89
94
-
76
a
28
98
-
36
99
88a
38
>99
99
75
98
20
64
99
Mote- Blanks indicate no data available
Dashes indicate negligible removal.
^Treated effluent concentration exceeds raw wastewater concentration
TABLE 6-12.
WASTEWATER CHARACTERIZATION OF
CONVENTIONAL POLLUTANTS FOR THE
BLAST FURNACE-FERROMANGANESE
SUBCATEGORY [3]
Raw wastewater
Treated effluent
Parameter
Number Number Percent
detected Concentration, mg/La detected Concentration, mg/L removal
Ammonia-N
cyanide
Manganese
Phenol
Sulfide
TSS
PH
1
1
1
1
1
1
1
710 1
690 1
500 1
64 1
130
4,200 1
8.8 - 11.1 1
680
710
53
6.3
410
8.8 - 11.1
4
_b
89
3
90
Note: Blanks indicate no data available.
Except pH values, given in pH units.
Treated effluent concentration exceeds raw concentration.
Date: 6/23/80
II.6.1-24
-------
II.6.2.5 Subcategories 6 and 7 - Basic Oxygen Furnace-Semiwet
and -Wet Air Pollution Control [4]
Wastewater results from the steelmaking process when wet gas
collection systems are used on furnaces. Spray water cooling and
quenching or the use of wet washers result in wastewaters con-
taining particulates from the gas stream. The basic oxygen fur-
nace has four main water systems:
1. Oxygen lance cooling water system,
2. Furnace trunnion ring and nose cone cooling water
system,
3. Hood cooling water system, and
4. Fume collection scrubber and gas cooling system.
The first three can be either "once-through" systems or closed
recirculating systems. Fume collection systems can vary from a
completely dry precipitator to a semiwet precipitator to a wet,
high energy venturi scrubber. Water use and characterization
varies with each system. The raw wastewater flow rate as deter-
mined by EPA field sampling varies from plant to plant, depending
on the gas-cleaning system used. The flow rates are presented
in Table 6-13.
TABLE 6-13. DISCHARGE FLOW RATES FOR BASIC OXYGEN
FURNACE PLANTS SAMPLED [4]
Gas treatment
Semiwet
Wet-open combustion
Wet-suppressed combustion
Plant
code
0432A
0396D
0112A
0584F
0020B
0856B
0868A
0112D
0060
0384A
0856N
0684F
Discharge flow
ma/Mg
0
0.12
1.83
0.27
2.7
2.0
0.54
0.42
0.31
0.33
0.37
0.04
gal/ton
0
29
440
65
640
470
130
100
75
80
89
10
The raw effluent discharges from the semiwet, wet-open and wet-
suppressed combustion gas-cleaning systems are similar in waste
characterization of the regulated parameters of suspended solids,
fluoride, and pH. However, the quantity of solids may vary
depending on the gas-cleaning system installed. Semiwet systems
discharge less solids than wet systems, and open combustion
Date: 6/23/80 II.6.1-25
-------
systems discharge more than suppressed systems. Fluoride concen-
trations vary with the amount of raw material, fluorspar, which
is used as a fluxing compound. EOF raw and effluent waste loads
for semiwet, wet-open combustion, and wet-suppressed combustion
are shown in Table 6-14.
TABLE 6-14. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE BASIC OXYGEN FURNACE
SUBCATEGORIES [4]
Raw
^ Ayerage fIpw^j^/Mg wastcwater
Semiwet 0.98
Wet-open combustion 3.0
Wet-suppressed combustion 4.1
Raw wastewater
Subcategory
Semiwet APCM
Wet-open combustion
TSS
Fluoride
pH
TSS
Fluoride
PH
Number
detected
2
1
2
4
1
4
Concentration^
Median
420
11.8
7,800
11.7
Maximum
330
3.1
11.5
3,500
8.5
9.8
mg/La
Average
300
11.5
4,000
9.8
Number
detected
1
1
2
6
2
6
Treated e
ffluent
Concentration ,
Median
125
11.9
1,200
9
11.9
Maximum
81
3.8
11.6
50
6.7
10.1
ma/La
Average
81
3.8
11.6
340
6.7
10
percent
removal
75K
92
21
Wet-suppressed combustion TSS 3 1,500 380 840 3 55 47 38 95
pH 3 11.3 9.4 10 3 10 8.8 8.9
*Except pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
A total of 68 different toxic pollutants were detected at the
nine wet-open and wet-suppressed combustion basic oxygen furnace
plants sampled. Semiwet plants were not sampled because these
technologies are recommended by BPT and BAT limitations as zero
discharges. The toxic pollutant data for raw waste loads and
gross treated effluent wastewater are shown in Table 6-15.
II.6.2.6 Subcategory 8 - Open Hearth Furnace [4]
The open hearth furnace process has two separate water systems.
The furnace cooling system normally includes a checker reversal
valve system and is generally limited to cooling the furnace
doors and the valve system. Because it is usually a once-through
system, the only parameter of concern is temperature.
The fume collection water system conditions the flue gas from the
furnace for final release. Pollutants captured by this system
are dependent on the type of fuel used in the furnace, and the
system's wastewater may contain nitrous and sulfur oxides. The
aqueous discharge from the high venturi scrubbers are scrubbing
waters from primary quenching operations. Wet and semiwet air
pollution control methods divide the open hearth furnace sub-
category into two subdivisions. The raw effluent discharges
from the semiwet and wet gas-cleaning systems are similar in
Date: 6/23/80 II.6.1-26
-------
o
0)
rl-
CTl
U>
00
O
H
H
to
TABLE 6-15,
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR
THE BASIC OXYGEN FURNACE-WET SUBCATEGORY [4]
Wet-open combustion
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Aromatics
Benzene
Number
detected
1
2
3
3
4
4
3
3
2
2
2
4
2
2
Raw
wastewater
Concentration, ug/L
Median
17
60
174
360
825
370
33
47
16
27
11
3,400
1.
Maximum
70
260
17,000
1,200
12,000
34
675
28
43
15
48,500
120
.5 3
Average
0.01
60
150
5,800
600
3,300
16.8
244
16
27
11
14,300
60
1.5
Number
detected
2
3
4
4
4
4
4
2
2
2
4
4
Treated
effluent
Concentration, ug/L
Median
12
10
540
217
455
0.05
530
20
175
70
706
72
Maximum
17
488
30,100
476
942
0.30
2,020
31
339
80
2,140
317
Average
12
170
7,800
230
517
0.15
773
20
175
70
970
118
Average
percent
removal
80=,
a
a
62
84
"a
a
a
a
93
a
Polycyclic aromatics
Chrysene
Fluoranthene
Pyrene
Halogenated aliphatics
Chloroform
13
34
32
23
13
56
122
62
(continued)
-------
D
0)
rt
(D
• *
CT\
ro
LO
X.
\
oo
o
M
M
cn
*
I-1
1
00
TABLE
6-15 (continued)
Wet-suppressed combustion
Raw wastewater
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Phenols
Phenol
Aromatics
Toluene
Polycyclic aromatics
Pyrene
Number
detected
1
1
2
3
1
3
1
2
1
2
1
2
1
2
1
2
1
Concentration, pg/L
Median
4
62
603
63
1
700
0.2
174
3
12
8.3
447
9
8
2
5
Maximum
91
1,050
310
27,000
327
19
868
11
3
Average
0.01
62
603
3
13,850
174
12
447
7
2
Number
detected
2
3
2
2
3
2
3
3
2
Treated
effluent
Average
Concentration, pg/L percent
Median
9
12
10
645
10
12.5
227
29
10
Maximum
10
13
100
822
691
15
281
298
10
Average removal
9 85
11.6 98
60
645 95
237 -a
12.5 4.2
203 -a
112 75
10 -a
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
Treated effluent concentration exceeds raw wastewater concentration.
-------
waste characterization as regards the regulated parameter of
suspended solids, fluoride, pH, etc. However, the quantity of
solids is variable according to the gas-cleaning systems
installed. Semiwet gas-cleaning systems discharge less solids
than wet systems. Fluoride concentrations are variable depend-
ing on fluorspan usage. Wastewater characterization for conven-
tional pollutants for sampled wet system open hearth plants is
presented in Table 6-16. Toxic pollutant data are found later
in the plant specific section of this subcategory, because only
one semiwet and one wet air pollution control plant have been
sampled. See Tables 6-70 and 6-71.
TABLE 6-16. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE OPEN HEARTH FURNACE
SUBCATEGORY, WET APCM SUBDIVISION [4]
Average raw wastewater flow: 2.2 m3/Mg (510 gal/ton)
Average treated effluent flow: 1.5 a>3/Mg (360 gal/ton)
Raw wastewater Treated effluent
" . Percent
TSS
Fluoride
Nitrate
PH
1
1
1
1
1,500
100
640
6.7
1
1
1
1
15
27
450
9.1
99
63
30
aExcept pH values, given in pH units.
''Treated effluent concentration exceeds raw concentration.
II.6.2.7 Subcategories 9 and 10 - Electric Arc Furnace-Semiwet
and -Wet Air Pollution Control [5]
The electric arc furnace (EAF) subcategory has two main plant
water systems. A once-through cooling system that maintains
the door and electrode rings generates heated water that may
be recirculated or released. Pollutant levels in this stream
are small. A fume collection cooling scrubbing system may be
a dry, semiwet, or wet system. Dry systems do not produce
any aqueous discharges. The semiwet system employs a spark box
or spray chamber to condition the hot gases for a precipitator
or baghouse. Aqueous discharges from such systems are general-
ly treated with other, similar wastes. The wet high energy
venturi scrubber systems extract gases from the furnace and
condition and cool them. The discharge is similar to that of
a basic oxygen furnace.
The raw effluent discharges from semiwet and wet gas-cleaning
systems are similar in waste characterization of the regulated
parameter of suspended solids, fluoride, zinc, and pH. However,
the quantity of solids is variable according to the gas-cleaning
systems installed. Semiwet gas-cleaning systems discharge less
solids than wet systems. pH is generally in the range of 7.0
to 9.0 for all gas-cleaning systems. Fluoride concentrations
are variable, but. this is due to the amount of raw material,
Date: 6/23/80 II. 6.1-29
-------
fluorspan (a fluxing compound), rather than the type of gas-
cleaning system used. Zinc concentrations are likewise
variable; they are highly dependent upon the amount of galva-
nized scrap charged to the furnace.
Only one plant (059B) was sampled for toxic pollutants in the
electric arc furnace-semiwet subcategory. Data for this plant
are presented in the plant specific section in Tables 6-74 and
6-75.
Conventional pollutant data for the semiwet subcategory are
presented in Table 6-17.
TABLE 6-17. WASTEWATER CHARACTERIZATION FOR CONVENTIONAL
POLLUTANTS FOR ELECTRIC ARC FURNACE-SEMIWET
SUBCATEGORY [5]
Average raw wastewater flow: 0.4 m3/Mg (975 gal/ton)
Average treated effluent flow: 0 m3/Mg (0 gal/ton)
Raw wastewater Treated effluent
Parameter
TSS
Fluoride
PH
Number
detected
1
1
1
Number
Concentration, mg/L detected Concentration, mg/L
2,200 1 530
30 1 28
7.8 1 6.7
Percent
removal
76
7
Note: Blanks indicate no data available.
Except pH values, given in pH units.
Conventional pollutants are characterized in Table 6-18 for wet
operations. Wastewater characterization of toxic pollutants for
the electric arc furnace-wet subcategory is presented in Table
6-19.
TABLE 6-18. WASTEWATER CHARACTERIZATION FOR CONVENTIONAL
POLLUTANTS FOR ELECTRIC ARC FURNACE-WET
SUBCATEGORY [5]
Average raw wastewater flow: 2.4 m3/Kg (578 gal/ton)
Average treated effluent flow: 1.3 m3/Mg (309 gal/ton)
Parameter
TSS
Fluoride
PH
Raw wastewater
Number Concentration,
detected Median Maximum
3 2,800 6,300
2 39 49
3 7.1 9.0
Treated effluent
mg/La
Average
3,400
39
7.9
Number Concentration,
detected Median
3 38
2 30
3 7.6
Maximum
86
34
7.8
mg/La
Average
44
30
7.6
Average
percent
removal
99
Date: 6/23/80 II.6.1-30
-------
ft
(D
N)
OJ
oo
o
TABLE 6-19.
H
I
U)
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR
ELECTRIC ARC FURNACE-WET SUBCATEGORY [5]
Raw wastewater
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Phthalates
Bis (2 -ethylhexy 1 ) phthal ate
Butyl benzyl phthal ate
Di-n-butyl phthal ate
Phenols
4-Nitrophenol
Pentachlorophenol
Number
detected
1
1
1
1
1
1
1
1
3
3
3
3
2
2
Concentration ,
Median
670
120
3,300
4,300
1,300
9
43
63
100,000
160
57
17
19
22
Maximum
190,000
170
150
65
31
40
pg/L
Average
97,000
110
70
30
19
22
Number
detected
1
1
1
1
1
1
1
1
2
3
2
3
0
1
Treated effluent
Concentration, jjg/L
Median Maximum Average
10
11
1,500
550
80
1,500
10
10
29,000 38,000 29,000
110 330 150
51 95 51
11 21 12
14
Average
percent
removal
99
91
55
87
94a
77
84
70
3
27
60
>99
36
Aromatics
Benzene
Polycyclic aromatics
Fluoranthene
Pyrene
10
30
28
25
58
53
14
30
28
12
7
72
28
10
150
15
7
72
77
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater concentration.
-------
II.6.2.8 Subcategory 11 - Vacuum Degassing [5]
The effluent discharges from the vacuum degassing process are
characteristically low in concentrations of the following
regulated parameters: suspended solids, lead, manganese,
nitrate, zinc, and pH. Typical concentrations of these param-
eters in degasser effluent waters are:
Suspended solids
Lead
Manganese
Nitrate
Zinc
PH
30 mg/L
1 mg/L
10 mg/L
25 mg/L
mg/L
- 9.0
5
6.0
The appearance of lead, manganese, and zinc in degasser efflu-
ents is due to the use of these metals in specialty steels.
The gases emitted from the molten steel contain these consti-
tuents, which come into contact with barometric condenser
cooling water during degassing. Nitrates occur in the effluent
as a result of the reaction of nitrogen gas with oxygen in the
high-temperature environment. Nitrogen gas is used to blanket
the molten steel bath to enhance degassing, and it is there-
fore available for conversion to nitrate form. Wastewater
characterization data for conventional and toxic pollutants
emitted from sampled carbon steel vacuum degassing plants are
presented in Tables 6-20 and 6-21. Refer to Tables 6-79 and 6-80
of the plant specific section for wastewater characterization for
toxic pollutants for the sampled specialty steel vacuum degassing
plant.
TABLE 6-20.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUTANTS
FOR THE VACUUM DEGASSING SUBCATEGORY [5]
Average raw wastewater flow: 1.3 m3/Mg (303 gal/ton)
Average treated effluent flow: 1.2 m3/Mg (280 gal/ton)
Parameter
TSS
Nitrate
Manganese
pH
Number
detected
4
3
3
2
Raw wastewater
Concentration,
Median Maximum
30 81
2.8 27
4.0 9.0
8.1 8.6
Treated effluent
mg/L*
Average
47
10
5.0
7.9
Number
detected ^
3
2
3
3
Concentration ,
ledian
29
14
0.27
7.9
Maximum
39
27
9
7.9
I
mg/La i
Average i
28
14
3.1
7.0
iverage
>ercent
removal
40
_b
36
aExcept pH values, given in pH units.
bAverage treated effluent concentration exceeds average raw wastewater concentration.
Date: 6/23/80
II.6.1-32
-------
ft
(D
NJ
U)
00
o
TABLE 6-21.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR THE VACUUM
DEGASSING SUBCATEGORY, CARBON STEEL SUBDIVISION [7]
Toxic pollutant
Raw wastewater
Treated effluent
Number
Concentration, pg/L
Number
Concentration, pg/L
Average
percent
detected Median Maximum Average detected Median Maximum Average removal
I
U>
OJ
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
130 3,000 1,100 3
90 440 190 3
300 2,000 830 3
32 40 32 2
2,000 30,000 10,800 3
Note: Blanks indicate no data available.
a,
'Treated effluent concentration exceeds raw waste water concentration.
26 3,000 1,000 10.
210 440 230 -c
90 2,000 720 13
22 30 22 31
330 30,000 10,000 8
Phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
2
2
34
31
57
43
34 •
31
2
2
28
260
53
500
28
260
18a
-------
II.6.2.9 Subcategory 12 - Continuous Casting [5]
The continuous casting steelmaking process produces mill scale
and oils and greases from the secondary spray cooling process.
Withdrawal and guide rolls guide the cast product through
the solidification stage. Since the cast product is hot, the
surface oxidizes and the resulting scale washes out with the
spray cooling water. Additional mill scale flakes off when
the cast product discharges onto caster runout tables. Caster
equipment employs hydraulic and lubrication systems which add
oils and greases to the wastewater. A typical analysis of the
regulated parameters is as follows:
Suspended solids 50 mg/L.
Oil and grease 25 mg/L
pH 6-9
The appearance of heavy metal constituents, such as chromium,
lead, and zinc, in caster wastewaters is due to the use of
these metals in steelmaking and alloying. Concentrations of
heavy metals in the wastewater, however, are generally low and
have little impact upon the treatment of caster wastes. Also,
relatively few organic pollutants are found in wastewater
samples.
Wastewater characterization for conventional pollutants for
sampled continuous casting carbon steel plants is presented in
Table 6-22. Major toxic pollutants for this subcategory are
listed in Table 6-23.
II.6.2.10 Subcategory 13 - Hot Forming-Primary [6]
The hot forming process produces scale and oil and grease as the
waste products from the primary rolling mill operation. As the
hot ingot is being rolled in the mill stands, the steel surface
oxidizes and is continuously scaling and chipping off. These
scale particles range in size, with approximately 6% being less
than 100 mesh, and consist primarily of iron oxides. Oils are
found in rolling mill wastewaters as a result of oil spills,
line breaks, and excessive dripping of lubricants as well as
wash down oils. Another wastestream that contributes to the
pollutant loading is the emission gas scrubber, which collects
particulates and other pollutants. The raw effluent discharges
from the primary carbon and specialty rolling mills have simi-
lar waste characterization for the regulated parameters of sus-
pended solids, oil and grease, and pH. However, the quantities
of solids vary between carbon and specialty rolling mills. The
carbon rolling operation results in higher scale quantities, and
specialty scale is much finer. Applied water rates are general-
ly higher for specialty steel rolling mills.
Date: 6/23/80 II.6.1-34
-------
TABLE 6-22.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE CONTINUOUS SUBCATEGORY [5]
Average raw wastewater flow: 12 m3/Kg (2,852 gal/ton)
Average treated effluent flow: 0.28 m3/Mg (67.5 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
pH
4
4
4
Concentration, rag/La
Treated effluent
Number
Median Maximum Average detected
25
22
7.4
48
39
8.3
26
23
7.2
4
4
4
Concentration, mg/La i
Average
>ercent
Median Maximum Average removal
15
2
7.8
37
35
9.4
15
15
8.0
_b
35
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
TABLE 6-23.
WASTEWATER CHARACTERIZATION FOR TOXIC POLLUTANTS
FOR CONTINUOUS CASTING SUBCATEGORY [5]
Raw wastewater
Toxic pollutant
Me tale and inorganics
Copper
Nickel
Selenium
Zinc
Phenols
p-Chloro-B-cresol
Phthalates
Di-n-butyl phthalate
Di-n-octyl phthalate
Aromatics
Toluene
Number
detected
4
4
3
4
3
3
4
4
Concentration, pg/L
Treated effluent
Number
Median Maximum Average detected
54
11
10
250
16
12
19
7
160
100
220
740
110
84
180
26
72
32
80
360
45
34
57
12
4
3
3
4
2
3
3
4
Average
Concentration, Pff/L percent
Median Maximum Average removal
120
27
8
290
7
45
11
6
210
90
10
970
11
50
710
10
120
47
8
430
7
43
180
6
75
90,
84
50
aTreated effluent concentration exceeds raw wastewater concentration.
The appearance of heavy metal constituents such as chromium,
lead, and zinc in hot forming wastewaters is due to the use
of these metals in steelmaking and alloying. Concentrations of
heavy metals in the wastewater, however, are generally low and
have little impact upon the treatment of the wastewater. Also,
relatively few organic toxic pollutants were detected in the
water of plants sampled.
Wastewater characterization data for conventional pollutant
parameters for sampled hot forming-primary mills are presented in
Table 6-24. Toxic pollutant concentrations for all sampled hot
forming-primary (carbon and specialty) steel mills are presented
in Table 6-25.
Date: 6/23/80
II.6.1-35
-------
TABLE 6-24. WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUTANTS
FOR THE HOT FORMING-PRIMARY SUBCATEGORY [6]
Average raw wastewater flow: 2.8 m3/Mg (678 gal/ton)
Average treated effluent flow-. 1.3 m3/Mg (323 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
PH
5
5
9
Concentration, mg/La
Number
Median Maximum Average detected
54
35
7.9
240
170
8.9
87
60
7.9
5
5
8
Treated effluent
Concentration, mq/L s
Median Maximum Average i
2
10
7.8
18
12
8.1
6
9
7.6
Average
>ercent
removal
93
85
aExcept pH values, given in pH units.
II.6.2.11 Subcategory 14 - Hot Forming-Section [6]
The hot forming process produces scale and oil and grease as
the waste products from the section rolling mill operation.
Wastewater sources and loadings are very similar to those of the
hot forming-primary subcategory and include scale pit effluent,
rolling mill wastewater, oil spill wastes, high pressure water
sprays, and wet precipitation or scrubber for cleaning gaseous
emissions. Rolling mill wastewaters generally contain 100 to
200 mg/L of suspended solids and 50 to 100 mg/L of oil and
grease. The pH of these wastewaters rarely deviates from the
6.0 to 9.0 range. The appearance of heavy metal constitutuents
such as chromium, lead, and zinc in hot forming wastewaters is
due to the use of these metals in steelmaking and alloying.
Concentrations of heavy metals in the wastewaters, however, are
generally low and have little impact upon treatment of the
wastewater. Also, relatively few organic toxic pollutants were
detected in the waters of the plants sampled. Conventional
pollutant concentrations for hot forming-sections mills are pre-
sented in Table 6-26. Toxic pollutant concentrations for hot form-
ing-section mills are presented in Table 6-27.
II.6.2.12 Subcategory 15 - Hot Forming-Flat [6]
The raw effluent discharges from plate mills in the hot forming-
flat subcategory are similar in character to the wastewaters
of other hot forming mills. Plate mill wastewaters generally
contain 100 to 200 mg/L of suspended solids and 50 to 100 mg/L
of oil and grease. The pH range of these wastewaters rarely
deviates from the 6.0 to 9.0 range. Wastewater sources are
also similar to those of the previously described hot forming
subcategories. Major sources include rolling mill wastewater,
oil and grease spills, and wet scrubbing of gaseous emissions.
Wastewater characterization for flat plate mills is presented
Date: 6/23/80 II.6.1-36
-------
a
CU
ft
CD
to
CJ
CD
O
TABLE 6-25,
WASTEWATER CHARACTERIZATION FOR TOXIC POLLUTANTS FOR
HOT FORMING-PRIMARY SUBCATEGORY [6]
I
u>
Raw wastewater
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Halogenated aliphatics
Chloroform
Methylene chloride
Trichloroethylene
Number
detected
5
5
5
2
5
5
5
5
3
2
3
6
2
3
Treated effluent Average
Concentration, |jg/L Number
Median Maximum Average detected
<10
50
300
2
300
220
20
100
18
6
7
<10
2
100
<10
130
970
2
810
570
20
140
149
10
7
13
2
270
<10
80 5
440 5
2
330 5
310 5
20
90 5
71
6
6
<10
2
63
Concentration, ug/L percent
Median Maximum Average removal
40 130 62 22
40 760 180 59
50 320 10 97
20 480 120 61
30 100 48 47
Note: Blanks indicate no data available.
-------
TABLE 6-26.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HOT FORMING-SECTION
SUBCATEGORY, [6]
Average raw wastewater flow: 18 m3/Mg (4,400 gal/ton)
Average treated effluent flow: 3 m3/Mg (720 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
PH
10
10
10
Concentration, mg/La
Treated effluent
Number
Median Maximum Average detected
44
32
7.6
260
250
8.1
66
47
7.6
10
10
10
Concentration, mg/La j
iverage
jercent
Median Maximum Average removal
10
9
7.8
87
30
9.5
26
11
7.9
60
77
Except pH values, given in pH units.
TABLE 6-27.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR THE HOT FORMING-SECTION
SUBCATEGORY [6]
Raw wastewater
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Dimethyl phthalate
Number
detected
1
10
10
10
10
10
5
1
3
Treated effluent
Concentration, tig/L Number
Median Maximum Average detected
10
30
60
50
55
80
ISO
14
5
240
600
790
830
1,230
1,300
11
67
70
140
230
270
190
7
10
10
9
9
10
Average
Concentration, (jg/L percent
Median
36
38
50
22
47
Maximum Average removal
130
760
320
490
2,200
59
130
85
170
280
12=,
39
26
Phenols
2,4-Dinitrophenol
Polycyclic aromatice
13
19
12
Naphthalene
Pyrene
Ralogenated aliphatice
Methylene chloride
3
2
4
10
160
10
5
190
7
5
44
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
"Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80
II.6.1-38
-------
in Tables 6-28 and 6-29. Tables 6-30 and 6-31 present conven-
tional and toxic wastewater characteristics for the hot forming-
flat hot strip and sheet mills.
TABLE 6-28. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HOT FORMING-FLAT SUB-
CATEGORY, PLATE MILL SUBDIVISION [6]
Average raw wastewater flow: 10 m3/Mg (2,500 gal/ton)
Average treated effluent flow: 5.0 ms/Mg (1,200 gal/ton)
Raw wastewaterTreated effluentT"~~
-_Average
Number Concentration, mg/L Number Concentration, ag/L percent
Parameter detected
TSS
Oil and grease
PH
7
7
7
Median Maximum Average detected
35
18
7.7
110
72
8.9
49 7
30
7.8 10
Median Maximum Average removal
1
10
7.4
7
13
7.9
2.5
10
7.5
45
59
*Except pH values, given in pH units.
II.6.2.13 Subcategory 16 - Pipe and Tube [6, 7]
Wastewater results from the hot forming operation because of the
large amount of direct contact cooling and descaling waters
required between the hot steel and the piercing, plug, and
reeler mill equipment. Seamless pipe and tube operations and
butt weld mills emit wastewater from the cleaning of the dies
and the rolling operations respectively. Roll cooling sprays
used in butt welded pipe mills are generally once-through
water systems where the scale- and oil-bearing waters are
discharged to scale pits. Seamless tube mills have similar
roll cooling wastewaters, plus a once-through spray quench
water system. The cold forming process produces wastewater as
a result of continuous flushing of rolls and welders with
soluble oil coolant solutions. The raw effluent discharges
from pipe and tube mills are similar in character to other hot
forming mill wastewaters. Pipe and tube mill wastewaters gen-
erally contain 100 to 200 mg/L of suspended solids and 50 to 100
mg/L of oil and grease. The pH of these wastewaters rarely
deviates from the 6.0 to 9.0 range. Oils are found in hot mill
wastewaters as a result of oil spills, line breakers, and ex-
cessive dripping of lubricants; appreciable quantities of spent
oils and greases are added when equipment is washed down. The
appearance of heavy metal constituents such as chromium, lead,
and zinc in hot forming wastewaters is due to the use of these
metals in steelmaking and alloying. Concentrations of heavy
metals in the wastewater, however, are generally low and have
little impact upon treatment of the wastewater. The scale
formed in the cold worked mills is primarily a very fine ferric
oxide (Fe203) which occurs as a result of surface oxidation of
the steel.
Date: 6/23/80 II.6.1-39
-------
D
0)
rt
(D
CTl
U>
oo
o
TABLE 6-29.
Toxic pollutant
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR THE HOT
FORMING-FLAT SUBCATEGORY, PLATE MILL SUBDIVISION [6]
mZ^ZHHAverage
percent
Raw wastewater
Treated effluent
Number
Concentration,
Number
Concentration, pg/L
detected Median Maximum Average detected Median Maximum Average removal
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
7
7
7
7
7
40
210
60
150
90
120
330
470
980
110
50
190
140
270
80
7
7
7
7
7
640
40
50
40
30
1,000
50
50
40
70
460
40
46
34
34
A
79
67
87
57
I
*.
o
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols
2,4-Dimethylphenol
P entachloropheno1
Halogenated aliphatics
Methylene chloride
430
32
14
820
14
12
120
350
44
< 0.01
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater concentration.
-------
TABLE 6-30.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HOT FORMING-FLAT SUB-
CATEGORY, HOT STRIP AND SHEET MILL
SUBDIVISION [6]
Average raw wastewater flow: 22 m3/Mg (5,300 gal/ton)
Average treated effluent flow: 22 m3/Mg (5,300 gal/ton)
Raw wastewater
Treated effluent
Number
Concentration, mq/L
Number
Concentration, mg/L
Average
percent
Parameter detected Median Maximum Average detected Median Maximum Average removal
TSS
Oil and grease
PH
2
2
2
52
e
7.8
57
10
8.1
52
e
7.8
2
2
2
21
3
7.8
38
4
7.9
21
3
7.8
60
67
aExcept pH values, given in pH units.
Water soluble and emulsified oils, which are essential to the
operation of the cold forming mill, are found in appreciable
quantities in the wastewater. Suspended solids concentrations
are generally in the range of 100 to 200 mg/L. The pH is some-
times slightly acidic, but it is generally in the range of 6.0
to 9.0.
As is true for hot forming operations, wastewaters are generally
low in heavy metals and organic toxic pollutants.
Wastewater characterization for conventional and toxic pollu-
tants for two sampled hot forming pipe and tube mills is present-
ed in Tables 6-32 and 6-33. Heavy metal toxic pollutants originate
in the raw materials used in steel making. These metals find their
way into the process wastewaters when the product scale contami-
nates the wastewater. Copper was the only toxic metal found in
the data reviewed. No toxic organics were detected at levels
greater than 10 (jg/L and are not reported due to this. Refer to
Table 6-96 in the plant specific section for wastewater character-
ization for conventional pollutants for the sampled cold forming
pipe and tube plant.
II.6.2.14 Subcategory 17 - Sulfuric Acid Pickling [8]
There are three main sources of wastewater in sulfuric acid
pickling operations: spent pickle liquor (acid concentrates),
rinse waters, and acid vapors and mists. Typical spent sulfuric
pickle liquor averages about 8% free acid and 8% dissolved iron.
On this basis, each ton of steel pickled (at 1% loss) would gen-
erate about 25 gal of spent pickle liquor.
After pickling, the material is subjected to a water rinse to
remove the acid/iron solution from the surface. Typical rinse
water flow rates range from 1 to 50 L/S (15 to 80 gal/min).
Date: 6/23/80
LI.6.1-41
-------
D
O
rt
U)
CO
o
CTt
•
M
I
to
TABLE 6-31.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR THE HOT FORMING-
FLAT SUBCATEGORY, HOT STRIP AND SHEET MILL SUBDIVISION [11]
Toxic pollutant
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols
2 , 4-Dinitrophenol
Halogenated aliphatics
Chloroform
Number
detected
2
2
1
1
2
1
2
1
1
Raw wastewater
Treated effluent Average
Concentration, pg/L Number Concentration, pg/L percent
Median Maximum Average detected Median Maximum Average removal
86 170
35 45
50
20
112 200
279
23
28
18
86 2 88 174 88 -a
35 2 16 31 16 54
1 50 0
1 20 0
112 2 105 206 105 6
12
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater concentration.
-------
TABLE 6-32.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE PIPE AND TUBE SUBCATEGORY,
HOT FORMING SUBDIVISION [6]
Average raw wastewater flow: 31 m3/Mg (7,500 gal/ton)
Average treated effluent flow: 34 m3/Wg (8,100 gal/ton)
Parameter
TSS
Oil and grease
pH
Number
detected
2
2
2
Raw wastewater
Concentration,
Median Maximum
51 66
6.5 7.9
7.6 7.8
mg/La
Average
51
6.5
7.6
Number
detected
4
4
4
Treated effluent
Concentration,
Median Maximum
20 38
4 4
7.6 7.8
mg/La
Average
20
4
7.6
Average
percent
removal
61
38
Except pH values, given in pH units.
TABLE 6-33.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR THE PIPE AND TUBE SUB-
CATEGORY, HOT FORMING SUBDIVISION [6]
Raw wastewater
Toxic pollutant
Metals and inorganics
Beryllium
Cadmium
Ci~,r om i urn
Copper
Lead
Nickel
Zinc
Number
detected
1
1
2
?
7
2
2
Concentration, pg/L
Number
Median Maximum Average detected
10
<10
140
73
430
300
160
240
80
800
500
250
140
73
430
300
160
2
2
1
1
1
Treated effluent
Average
Concentration, pg/L percent
Median Maximum Average removal
37
26
50
20
120
43
31
210
37
26
120
74
64
88
93
25
Note. Blanks indicate no data available.
Many pickling facilities are equipped to include a scrubbing
device which uses water to collect the acid mist. Others use
condensing "demisters" to trap acid vapors for return to the
pickling tanks. Most large continuous H2S04 picklers utilize
wet scrubber systems with recycle of frame scrubber wastewaters.
Efficient operations achieve less than 3% blowdown from their
scrubbers.
Date: 6/23/80
II.6.1-43
-------
Another source of acid vapors and mists is the absorber vent
scrubber associated with an acid recovery mist. Other recovery
units tend to use demister type or dry vent controls for pre-
venting pollution from this source. In most cases condensates
are returned to the pickling tank.
Wastewater characterization for conventional pollutants is pre-
sented in Table 6-34 for sulfuric acid batch pickling opera-
tions and in Table 6-35 for sulfuric acid continuous pickling
operations. Toxic pollutant data for batch pickling opera-
tions are presented in Table 6-36. Two continuous pickling
operations were sampled for toxic pollutants, and data for both
plants (094 and 097) are presented in Tables 6-97 and Table
6-98 in the plant specific section.
TABLE 6-34. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE SULFURIC ACID PICKLING
SUBCATEGORY, BATCH SUBDIVISION [8]
Average raw wastewater flow: rinse water - 0.68 m3/Mg (271 gal/ton)
Gross raw wastewater Gross process effluent
Number Concentration, rog/La Number concentration, rog/La
Parameter detected Median Maximum Average detected Median Maximum Average
TSS 5 32 360 180 0.6 1.3 0.7
Oil and grease 5 18 48 24 4 8.8 11 4.9
pH 5 1.8 6.9 3.3 8.4 9.0 8.3
Note: Blanks indicate no data available.
'Except pH values, given in pH units.
TABLE 6-35. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE SULFURIC ACID PICKLING
SUBCATEGORY, CONTINUOUS SUBDIVISION [8]
Average raw wastewater flow: spent concentrate - 0.083 m3/Mg (19.8 gal/ton)
rinse water - 0.69 m3/Mg (164 gal/ton)
fume hood scrubber - 0 037 m3/Mg (8.9 gal/ton)
: — • •
Number Concentration, irg/L* Number
Parameter detected Median Maximum Average detected
TSS 7 200 17,000 2,600 13
Oil and grease 6 10 46 18 3
PH 7 <1 2
Rinse water Fume hood scrubber
Concentration, mq/La Number Concentration, mg/L*
38 500 192 3 7.5 200 69
14 33 19 3 2.5 9 4.5
4 5.7 43 1.7 1.9 1.7
Note: Blanks indicate no data available
Except pH values, given in pH units
Date: 6/23/80 II.6.1-44
-------
D
0)
rt
(0
N)
U>
00
O
TABLE 6-36.
I
>b>
ui
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR THE
SULFURIC ACID PICKLING SUBCATEGORY, BATCH SUBDIVISION [8]
Spent concentrate
Concentration, M9/L
Toxic pollutant
Metals and inorganics
Arsenic
Cadmium
Hexavalent chromium
Chromium, Total
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phenols
2,4, 6-Trichlorophenol
Aromatics
Benzene
Toluene
Number
detected
1
2
2
2
2
2
2
2
2
2
1
1
Median
170
270
4
232,000
3,600
13
800
25,000
51
74,000
41
<10
Maximum
280
260,000
4,700
17
1,600
27,000
600
133,000
Average
270
232,000
3,600
13
800
25,000
51
74,000
Rinse
water
Concentration, pg/L
Number
detected
3
3
3
3
2
3
3
3
1
Median
<10
<10
50
140
11
40
60
90
<10
Maximum
173
302
2,000
2,400
11
1,000
13,800
1,800
Average
64
107
680
860
11
360
4,600
640
Polycyclic aromatics
Acenaphthylene
Naphthalene
Pyrene
Halogenated aliphatics
Chloroform
Methylene chloride
Trichloroethylene
Aromatics
Benzene
Polycyclic aromatics
Fluoranthene
Naphthalene
Halogenated aliphatics
Chloroform
Methylene chloride
1 <10
2 <10 <10 <10
1 20 2 <10 <10 <10
2 33 52 33 3 43 165 73
1 <10
Treated wastewater
Concentration, M9/L
Number
detected Median Maximum Average
2 <10 <10 <10
1 <10
2 <10 <10 <10
5 20 25 22
5 154 230 140
Note: Blanks indicate no data available.
-------
II.6.2.15 Subcategory 18 - Hydrochloric Acid Pickling [8]
The process wastewater generated during pickling operations
include spent acid concentrations, rinse water, fume hood
scrubber wastewater, and absorber vent scrubber wastewater. A
typical discharge flow rate for an acid concentrate is 0.084
m2/Mg (20 gal/ton). The spent pickling solution may contain
free acid, ferrous salts, and relatively small amounts of
other metal sulfates, chlorides, lubricants, inhibitors, and
hydrocarbons. Rinse water is used to flush the pickled metal
and thus appears as dilute spent liquor. Continuous facili-
ties use 6 to 65 L/S (100 to 1,000 gpm) and batch facilities
use 1.5 to 20 L/S (25 to 300 gpm). Fume hood scrubbers and
absorber vent scrubbers collect acid mists to prevent air
contamination; as a result their discharges must be treated to
neutralize the captured acid.
Most chemical characteristics show significant variation,
reflecting pickling line configuration and applied flows. Note
that the major constituents of the wastewater are dissolved
iron and suspended solids. The concentrations of other con-
stituents are generally less than 1 mg/L except in the con-
centrates where chromium, copper, nickel, and zinc concentra-
tions were generally greater than 10 mg/L. Tables 6-37 through
6-40 present conventional and metal concentrations for raw
wastewater and gross treated effluent for continuous line acid
concentrates, rinse water, fume hood scrubbers, and absorber
vent scrubbers. Table 6-41 presents toxic pollutant concentra-
tion data for the continuous line raw wastewater. Additional
data on the hydrochloric acid pickling subcategory appear in
the plant specific section. Also found in the plant specific
section is information on batch-type hydrochloric acid pickling.
TABLE 6-37. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS AND METALS FOR THE HYDROCHLORIC
ACID PICKLING SUBCATEGORY, CONTINUOUS SUB-
DIVISION (CONCENTRATES) [8]
Average raw waste flow: 0.08 m3/Mg (19.5 gal/ton)
Average gross effluent flow: 0.17 n3/Kg (41.4 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
PH
Antimony
Arsenic
Cadmium
Total chromium
Copper
Lead
Nickel
Zinc
6
1
3
2
2
2
3
3
1
3
3
Concentration, i
Median Maximum 1
97
<1
8.7
11
13
4.2
320
<1
3.7
0.4
0.31
18
28
13
4.6
Gross effluent jMri-i-im-
a a Average
«g/L Number Concentration, raq/L percent
tverage detected Median
120 1
5.1 1
<1 1
1.9
0.21
0.3
9.4
14
2.1
9.5
3.6
Maximum Average removal
36 30
<1 80
8.4
Note: Blanks indicate no data available.
TExcept pH values, given in pH units.
Date: 6/23/80 II.6.1-46
-------
TABLE 6-38.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUTANTS
AMD TOXIC METALS FOR THE HYDROCHLORIC ACID PICKLING
SUBCATEGORY, CONTINUOUS SUBDIVISION (RINSES) [8]
Average raw waste flow: 0.5 ro3/Mg (120 gal/ton)
Average gross effluent flow: 0.64 m3/Mg (152 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
pH
Antimony
Arsenic
Cadmium
Total chromium
Copper
Lead
Nickel
Zinc
9
6
11
2
2
1
3
5
2
4
5
Concentration, mg/La
Number
Median Maximum Average detected
15
28
1.6
0.57
0.67
0.73
0.38
210
150
4.2
0.19
0.24
0.79
1.6
0.43
1.3
1.4
34
40
2.4
0.19
0.23
0.01
0.57
0.72
0.29
0.78
0.49
5
5
5
2
2
1
2
1
2
2
Gross effluent
Concentration,
Median Maximum
2 36
1 6
9.0
0.044
0.25
0.44
0.066
f
mg/La t
Average
>ercent
Average removal
12
3.5
8.0
0.031
0.011
0.22
0.14
0.032
0.25
0.045
65
91
86b
61
81
89
68
91
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
Gross effluent concentration exceeds raw waste concentration.
TABLE 6-39. WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUTANTS
AND TOXIC METALS FOR THE HYDROCHLORIC ACID PICKLING
SUBCATEGORY, CONTINUOUS SUBDIVISION (FUME HOOD
SCRUBBERS) [8]
Average raw waste flow: 0.11 m3/Mg (25 gal/ton)
Average gross effluent flow: 0.078 m3/Mg (18.6 gal/ton)
Raw wastewater
Parameter
TSS
Oil and grease
PH
Antimony
Arsenic
Cadmium
Total chromium
Copper
Lead
Nickel
Zinc
Number
detected
4
4
6
2
2
3
4
1
3
4
Concentration,
Median
7.5
29
1.4
0.10
0.055
0.15
0.19
0.35
0.1
0.13
Maximum
2,100
330
3.3
0.11
0.07
0.24
0.76
0.2
1.5
mg/La
Average
530
95
1.6
0.10
0.055b
0.16
0.31
0.13
0.45
Number
detected
2
2
2
2
1
1
2
1
2
1
Gross effluent
Concentration^
Median
0.008
0.011
0.075
0.17
0.025
0.13
0.027
Maximum
11
1.9
9.0
0.013
0.28
0.19
mg/La
Average
7.0
1.4
8.0
0.008
0.17
0.13
Average
percent
removal
98
99
99
53
55
93
23
94
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
Detected but not quantified.
Date: 6/23/80
II.6.1-47
-------
TABLE 6-40. WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUTANTS
AND TOXIC METALS FOR THE HYDROCHLORIC ACID PICKLING
SUBCATEGORY, CONTINUOUS SUBDIVISION (ABSORBER VENT
SCRUBBERS) [8]
Average raw waste flow: 0.86 m3/Mg (205 gal/ton)
Average gross effluent flow: 0.71 m3/Mg (170 gal/ton)
Number
Parameter detected
TSS
Oil and grease
pH
Antimony
Arsenic
Cadmium
Total chromium
Copper
Lead
Nickel
Zinc
6
2
6
1
1
1
2
1
2
2
Raw wastewater
Concentration ,
Median Maximum
85 150
2.2
5.6 7.1
1.3
0.79
1.1
mg/La
Number
Average detected
80
2.0
4.2
0.21
0.017
_c
0.98
0.87
0.1
0.72
0.9
1
1
1
1
1
1
Gross effluent A-unr*™
Concentration, mg/L percent
Median Maximum Average removal
9.7
0.47 75
0.002 0.002 -
o.oiib b
0.024b b 98
0.059. K 92
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
Detected but not quantified.
Gross effluent concentration exceeds raw waste concentration.
II.6.2.16 Subcategory 19 - Cold Rolling [7]
The major water use on cold rolling mills is for cooling the rolls
and the material being rolled. This is accomplished by using a
flooded lubrication system to supply both lubrication and cooling.
A water-oil emulsion is sprayed directly on the material and rolls
as the material enters the rolls. Each stand has its own sprayer
and, where recycle is used, its own recycle system.
The water used in cold rolling mill must be of fairly good
quality, free of suspended matter. High quality rolling oils
are added to form the emulsion. Recirculating mills recircle
the oil emulsion. The material being rolled is clean and free
from rust, and because no scale is generated during the rolling,
oil and temperature are the basic pollutants in the discharge
when the emulsion is not recirculated.
Direct application mills constantly add fresh rolling solutions on
a once-through basis. Normally these plants install treatment
systems to recover the oils for potential reuse. This process is
normally used only when a high quality product is desired.
A third type of cold rolling mill is a combination mill which
combines the recirculation and direct application of the
rolling emulsion. The discharge rate at such a mill is
substantially less than that at a direct application mill due
to the partial recirculation. Wastewater characterization
for conventional pollutants for the three subdivisions of the
Date: 6/23/80 II.6.1-48
-------
ft
(D
TABLE 6-41.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR THE
THE HYDROCHLORIC ACID PICKLING SUBCATEGORY, CONTINUOUS
SUBDIVISION [14]
to
CO
oo
o
M
•
CTl
Absorber vent scrubber
raw wastewater Fume hood scrubber
raw wastewater
Concentration, pg/L Concentration, pg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols
Pentachlorophenol
Aromatics
Benzene
Chlorobenzene
Number
detected
1
1
1
1
2
2
2
1
1
2
1
1
1
2
Number
Maximum Average detected
<210
<23
<20
<20
<200
1,600
18
<600
32
790
<35
<250
<70
1,300
2
3
1
4
<140 3
850 4
10 4
3
1
420 3
3
4
1
670 4
1
Rinse wastewater
Concentration, pg/L
Number
Median Maximum Average detected
175
66
<20
<12
150
120
6
<100
2
150
<10
<20
<50
87
26
26
200
75
<200
<330
390
12
<600
<500
<10
<250
270
43
170
50
59
190
180
6
260
230
7
75
120
26
3
3
1
6
6
5
6
6
6
3
6
6
Median
<100
233
<20
<15
390
690
8
260
690
<10
21
380
12
Maximum Average
190
290
<200
840
1,500
75
6,200
1,300
200
<250
1,500
14
110
190
a
45
300
770
20
1,250
700
70
58
520
12
Polycyclic aromatics
Fluoranthene
Pyrene
Halogenated aliphatics
Chlorodibromomethane
Chloroform
1,1-Dichloroethylene
1,2-Trans-dichloroethylene
Methylene chloride
Tetrachloroethylene
Trichloroethylene
26
23
1,100
14
13
<10
12
550
16
82
12
34 6
3
2
11
22
37
65
75
37
3,600
40
65
19
22
16
690
24
37
(continued)
-------
O
fl>
ft
(D
TABLE 6-41 (continued)
NJ
00
O
CFi
i
U1
O
Spent pickle liquor
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Aromatics
Benzene
Polycyclic aromatics
Fluoranthene
Pyrene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
Trichloroethylene
Number
detected Median
2
2
4
5
5
5
4
5
4
4
1
5
5
4
5
5
3
2,100
35
140
6,700
11,000
8
1,700
13,000
<10
290
180
4,200
<10
<10
<10
14
31
Maximum
4,100
45
280
37,000
22,000
11
1,500,000
22,000
170
390
61,000
65
75
100
3,500
40
Discharge wastewater
Concentration, ug/L
Number
Average detected
2,100
35
150
13,000
11,000
8
390,000
10,000
50
250
15,000
21
26
28
720
27
2
3
1
5
5
5
5
5
1
5
4
5
1
5
2
5
5
5
5
2
2
Median
100
230
<20
<20
440
680
14
420
<2
640
6
23
<50
600
12
<10
<10
<10
15
29
50
Maximum
190
260
240
2,300
900
74
33,000
860
20
250
290,000
14
56
65
36
3,600
37
90
Average
100
170
96
770
620
23
7,000
540
9
70
58,000
12
20
22
15
740
29
50
Note: Blanks indicate no data available.
a.
Detected but not quantified.
-------
cold rolling subcategory is presented in Table 6-42 through
Table 6-44. Wastewater characterization for the cold rolling
subcategory for toxic pollutants is presented in Table 6-45.
TABLE 6-42. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE COLD ROLLING SUBCATEGORY,
RECIRCULATING MILL SUBDIVISION [7]
Average raw waste flow: 27.7 m3/Mg (6,602 gal/ton)
Average gross effluent flow: 0.2 m3/Mg (50.3 gal/ton)
Raw wastewater
Parameter
TSS
Oil and grease
PH
Number
detected
3
3
3
Concentration,
Median
2,200
37,000
6.5
Maximum
5,000
82,000
6.7
mg/La
Average
2,600
40,000
6.3
Number
detected
2
2
8
Gross effluent
Concentrati on ,
Median
110
71
6.1
Maximum
200
140
8.2
mg/La
Average
110
71
6.1
Average
percent
removal
96
99
aExcept pH values, given in pH units.
TABLE 6-43. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE COLD ROLLING SUBCATEGORY,
DIRECT APPLICATION MILL SUBDIVISION [7]
Average raw waste flow: 2.7 m3/Mg (659 gal/ton)
Average gross effluent flow: 2.7 m3/Mg (659 gal/ton)
Parameter
TSS
Oil and grease
pH
Number
detected
1
1
1
Raw wastewater
Concentration, mg/L
Median Maximum Average
290
1,900
7.2
Number
detected
1
1
1
Gross effluent
Concentration, mg/La
Median Maximum Average
300
1,400
3.3
Average
percent
removal
_b
26
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
TABLE 6-44. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE COLD ROLLING SUBCATEGORY,
COMBINATION MILL SUBDIVISION [7]
Average raw waste flow: 1.4 m3/Mg (339 gal/ton)
Average gross effluent flow: 1.4 m3/Mg (339 gal/ton)
Raw wastewater
Number
Parameter detected
TSS
Oil and grease
PH
2
3
3
Concentration,
Median
630
1,000
6.2
Maximum
990
1,400
7.1
mg/La
Number
Average detected
630
1,000
6.2
2
2
2
Gross effluent
Concentration, mg/La :
Median Maximum Averaae i
11
5
7.9
16
6
8.2
11
5
7.9
Average
jercent
removal
98
99
Note: Blanks indicate no data available.
a_
Except pH values, given in pH units.
Date: 6/23/80 II.6.1-51
-------
o
D)
rt
CD
(Ti
NJ
U>
00
o
I
cn
TABLE 6-45.
WASTEWATER CHARACTERIZATION OF POLLUTANTS
FOR COLD ROLLING SUBCATEGORY [7]
Raw wastewater
Toxic pollutant
Metals and inorganics
Antimony
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
2-Nitrophenol
Pentachlorophenol
Phenol
4, 6-Dinitro-o-cresol
Aromatics
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1, 1,2,2-Tetrachloroe-thane
Tetrachloroethylene
1,1, 1-Trichloroethane
Pesticides and metabolites
Xylene
Note: Blanks indicate no data
a_ . , ,.,.-
Number
detected
1
2
2
3
2
3
2
3
2
2
2
1
2
1
1
2
1
3
1
2
2
1
available.
Concentration,
Median
580
45
380
2,260
23
1,550
740
680
17,760
12,530
35,030
43
160
94
390
87
110
80
815
217
4,300
Maximum
45
6,500
7,450
34
2,500
1,250
1,750
35,500-
25,000
70,000
110
540
1,150
415
Mg/L
Average
45
2,300
3,470
23
1,420
740
870
17,760
12,530
35,030
250
87
210
0.005
815
217
Number
detected
2
1
3
2
2
1
1
3
1
1
2
1
Treated effluent Average
Concentration, \ig/L percent
Median
200
20
600
43
70
35
21
288
10
60
34
16
Maximum Average removal
300 200 66
56
1,170 600 74
65 43 99
90 70 95
95
>99
536 288 -a
98
31
43 34 83
98
-------
II.6.2.17 Subcategories 20 and 21 - Hot Coating-Galvanizing and
-Terne Plating [9]
The major wastewater flows generated during hot coating opera-
tions in the iron and steel industry fall into several distinct
groupings such as:
1. Continuously running dilute wastewater from rinsing and
scrubbing operations following alkaline or acid cleaning steps,
rinses following chemical treatment or surface passivation
steps and final product rinses after hot dripping. These
waters carry suspended and dissolved matter, chlorides,
sulfates, phosphates, silicates, oily matter, and varying
amounts of dissolved metals (iron, zinc, chromium, lead, tin,
aluminum, cadmium) depending on which coating metal is used.
2. More concentrated intermittent discharges, including spent
alkaline and acid cleaning solutions, fluxes, chemical treat-
ment solutions, and regenerant solutions from in-line ion
exchange systems. These discharges contain higher concentra-
tions of the parameters listed above as being present in rinse
water.
3. Terne scrubber wastewaters, produced by continuously scrub-
bing vapors and mists collected from the coating liner cleaning
and coating steps. Scrubbers may be once-through a recirculat-
ing, and the wastewaters from scrubbing can be used as process
rinses, since only volatile components are scrubbed out of the
air. Less than one-third of the hot coating lines have wet
fume scrubbers.
4. Noncontact cooling waters, used to control temperatures of
the furnaces and molten metal bath pots associated with coating
operations. Except for an increase in temperature, these
waters do not pick up any pollutants during their passage
through the coating lines; thus, they require no treatment
if they are kept separate from contaminated process waters.
Wastewater characterization of conventional and toxic pollu-
tants for the nine sampled plants in the hot coating-galviniz-
ing subcategory is presented in Tables 6-46 and 6-47. Waste-
water characterization of conventional pollutants for three
plants sampled in the hot coating-terne plating subcategory
is presented in Table 6-48. Toxic pollutant data on the terne
plating subcategory are currently limited to one plant and may
be found in the plant specific section of this report.
Date: 6/23/80 II.6.1-53
-------
TABLE 6-46.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HOT COATING-GALVANIZING
SUBCATEGORY [9]
Raw wastewater flow: 4.3 m3/Mg (1,025 gal/ton)
Treated effluent flow: 4.3 m3/Mg (1,026 gal/ton)
Parameter <
Hexavalent
chromium
Oil and grease
TSS
PH
Raw wastewater
Number Concentration,
letected Median Maximum
8 0.005 7
10 20 210
10 84 330
10 6.1 11.2
Treated effluent
mg/La
Average
0.88
45
100
5.8
Number Concentration,
detected Median
5 0.006
6 6
6 9
6 8.1
Maximum
0.077
11
43
9.0
- — Average
mg/L percent
Average removal
0.020 77
6 87
17 83
8.2
II.6.2.18 Subcategory 22 - Combination Acid Pickling [8]
The wastewater from continuous acid pickling operations can
originate from three sources depending on the wastewater dis-
posal practices at the mill and the type of equipment installed.
The first source of wastewater is the rinse tank(s) used to
rinse the-acid solution from the product after it is pickled.
This wastewater source has the highest flow and contains solids,
oils and greases, and dissolved metals, and it normally has a
very low pH.
If fume hood scrubbers are installed, wastewater characteris-
tics similar to those found in the rinse waters are generated.
Fume hood scrubbers represent the second source of wastewater
from continuous and pickling operations. The flow rates
through the scrubbers vary considerably throughout this sub-
category, but the discharge flow rate from this source can be
reduced to below 0.42 m3/Mg (100 gal/ton) of steel processed if
recycle is practiced.
The third source of wastewater from continuous acid pickling
operations is the spent pickle liquor bath, which has lower
flow rates but higher contamination levels than the other two
sources. Because of the small volume and high pollutant levels
in this source, the waste is handled off site in more than 60%
of the mills. Typical levels in the three sources are summa-
rized in Table 6-49.
Wastewater characterization data for pickle rinse water for the
combination acid pickling-batch type is shown in Tables 6-50
and 6-51. Wastewater characterization data of conventional
pollutants for pickle rinse water in the combination acid
pickling-continuous type is shown in Table 6-52. No toxic
pollutant data are currently available for the continuous
combination acid process.
Date: 6/23/80
II.6.1-54
-------
D
PJ
ti-
ro
CTv
\
to
00
O
TABLE 6-47.
I
U1
cn
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR
THE HOT COATING-GALVANIZING SUBCATEGORY [9]
Raw wastewater
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Selenium
Sliver
Thallium
Zinc
Phenols
2-Cnlorophenol
2 , 4-Dichlorophenol
2 , 4-Dinitrophenol
2-Nitrophenol
Pentaehlorophenol
Phenol
2 , 4, 6-Trichlorophenol
4 , 6-Dinitro-o-cresol
Aromatics
Benzene
1 , 3-Dichlorobenzene
Toluene
Polycyclic aromatics
Acenaphthene
Acenaphthylene
Anthracene
Benzo( a ) anthracene
Benzo ( a ) pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrftne
Pyrene
2-chloronaphthalene
Halogenated aliphatics
Chloroform
Dichlorobromome thane
1, 2-rra/is-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
Trichloroethylene
Numbei
detected
1
3
1
6
6
6
6
6
3
6
1
6
2
3
1
3
1
2
3
1
2
1
1
1
4
3
1
5
6
1
1
5
5
2
1
Concentration,
Med i an
3
14
<20
20
15
90
12
310
10
20
50
9, 100
7
5
5
5
5
8
5
144
8
5
10
5
7
5
5
5
13
10
5
16
10
39
46
Maximum
40
200
10,200
2,500
19
25,000
10
2,500
88,900
10
5
22
10
11
10
24
10
21
106
12
17
67
ug/L
Average
21
45
2,113
487
12
4,390
8.4
65
26,760
7
5
ND
10
8
ND
11
8
ND
ND
11
10
ND
12
37
134
10
39
Number
detected
1
3
6
6
6
6
6
3
6
1
6
2
1
1
2
3
2
1
2
4
3
S
5
1
1
4
1
6
4
2
1
5
2
6
5
2
2
2
Treated
effluent
Concentration,
Median
3
10
<20
20
35
30
10
145
10
20
50
130
4
10
5
5
5
a
5
10
6
10
5
5
7
S
S
5
9
S
10
7
7
4
12
13
8
19
7
Maximum
10
20
200
170
21
600
12
250
770
5
5
5
10
20
10
10
5
10
10
10
10
10
10
5
48
230
8
32
10
, Mq/L
Average
9
'0.
17
77
52
9.
270
11
70
1,390
4
5
4
a
10
7
ND
8
5
7
6
7
6
10
7
4
18
ND
ND
60
8
19
7
Average
percent
removal
-
51
.02
62
96
90
8 18
94.
_
95
43
_
60h
38.
36
>99.
_
30h
b
36
14.
42b
51
>99
>99
20
51
85
Note:
Blanks indicate no data available.
Dashes indicate negligible removal.
Indicates water quality of central treatment effluent.
Treated effluent concentration exceeds raw wastewater concentration.
-------
TABLE 6-48.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HOT COATING-TERNE PLATING
SUBCATEGORY [9]
Average raw waste flow: 5.2 m3/Mg (1,239 Ib/ton)
Average gross effluent flow: 5.2 ms/Mg (1,239 Ib/ton)
Parameter
Oil and grease
TSS
pH
Number
detected
1
1
1
Raw wastewater
Concentration, mg/La
Median Maximum Average
4
11
6.5
Number
detected
1
1
1
Gross effluent
Concentration, mg/La
Median Maximum Average
4
11
6.5
Average
percent
removal
-
-
Note: Dashes indicate negligible removal.
^Except pH values, given in pH units.
TABLE 6-49.
TYPICAL CONTAMINANT LEVELS IN THE THREE
WASTEWATER SOURCES IN COMBINATION ACID
PICKLING OPERATIONS [8]
Flow/parameter
Flow
- normal, m2/Mg
- after recycle, m'/Hg
Parameter concentration, mg/L*
TSS
Oil and grease
Dissolved iron
Fluoride
Dissolved chromium
Dissolved nickel
Nitrateec
Copper
PH
Pickle rinse water,
batch type
2.1
1,300
12.5
300
230
75
45
150
1.7
2.5
continuous type
10.5
200
3.3
80
75
20
15
0.21
4.0
Fume hood
scrubber water
6.3
0.42
50
5
190
2,000
40
20
2.S
Spent pickle
liijuor
0.063
150
2.0
20,000
5,000
3,500
4,800
5,000
ieo
1.2
Note: Blanks indicate data not available.
*Except pH values, given in pH units.
Fluorides are present in significant quantities only when hydrofluoric acids are used in the
combination acid pickling process.
cNitrates are present in significant quantities only when nitric acids are used in the
combination acid pickling process.
TABLE 6-50. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE COMBINATION ACID PICKLING
SUBCATEGORY, BATCH-TYPE SUBDIVISION [8]
Avenge raw waste flew. 1.2 ma/Mg
Average gross effluent flow: 1.2 ma/Mg
Number
Parameter detected
TSS
Oil and grease
Fluoride
pH
4
4
3
4
Concentration, mg/La Number
80 460
6 10.5
37 52
3.1 9
124 4
7.1 4
36 3
4.5 4
Gross effluent
— Average
Concentration, mg/L oercent
40 530
6.6 24
19 95
9 9 11.9
159
11
41
9.9
Note: Blanks indicate no data available.
"Except pH values, given in pB units.
Treated effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80
II.6.1-56
-------
ft
(D
LO
oo
o
TABLE 6-51. WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS FOR
THE COMBINATION ACID-BATCH-TYPE SUBDIVISION [8]
Raw wastewater flow: 5.2 m3/Mg (1,239 Ib/ton)
Treated effluent flow: 5.2 m3/Mg (1,239 Ib/ton)
Raw wastewater
Number
Concentration, mg/L
Parameter detected Median
H
^H Total iron
Total lead
I—1
^ Oil and grease
TSS
Total tin
PH
3
3
3
3
3
3
19
<0.06
3
11
<2
3.6 - 5.2
Maximum
110
0.2
10
48
<2
5.2 - 6.1
Average
45
0.1
4.3
22
<2
4.5
Number
Treated effluent
Concentration, mg/La
detected Median
3
3
3
3
3
3
19
<0.06
4.3
11
<2
3.6 - 5.2
Maximum
110
0.25
13
51
<2
5.2 - 6.1
Average
46
0.12
7.1
24
<2
4.5
Average
percent
removal
_b
-b
_b
-b
-
-
Note: Dashes indicate negligible removal.
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw wastewater concentration.
-------
TABLE 6-52.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR COMBINATION ACID PICKLING-
CONTINUOUS-TYPE SUBDIVISION [8]
Average raw wastewater flow: 6.6 m'/Mg
Average treated effluent flow: 6.64 »3
/Kg
Number
Parameter detected
TSS
Oil and grease
Fluoride
Nitrate
pH
1
1
1
1
1
Raw waBtewater
Concentration, «q/L* Number
Median Maximum Average detected
14
6.3
180
0.35
7.5
1
1
1
1
Treated effluent
Concentration, mg,/La Percent
Median Maximum Average removal
e
4.3
9.5
7.9
43
32
94
Note: Blanks indicate data not available.
*Except pH values, given in pH units.
II.6.2.19 Subcategory 23 - Scale Removal [9]
The major source of wastewater in the kolene operation is the
discharge from the quench water tank and/or the rinse steps
that follow the scale removal operation. The wastewaters
generated in these steps contain significant levels of solids,
and total and hexavalent chromium, and they are at elevated pH
and temperature levels. The quality of the rinse water may
vary greatly depending on the age of the salt solution in the
kolene bath and the amount of carry-over into the rinse tanks.
Wastewater characterization data of conventional and toxic
pollutants for kolene scale removal mills is represented in
Tables 6-53 and 6-54, respectively.
TABLE 6-53.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR KOLENE SCALE REMOVAL
SUBDIVISION3 [9]
Average raw wastewater flow: 1.31 »3/Mg
Average treated effluent flow: 1.31 na/Mg
Raw wastewater
Parameter
TSS
Hexavalent
chromium
pH
Number
detected
4
3
4
Concentration,
Median
440
120
12.5
Maximum
1.200
260
13
ma/Lb
Average
J40
160
12.4
Treated e
ffluent
Number Concentration,
detected Median
4 71
3 1
4 8.5
Maximum
190
80
11.7
«g/Lb I
Average i
88
27
10.8
'ercent
removal
74
83
Note: Blanks indicate data not available.
* includes batch and cintinuous processes.
Except pB values, given in pH units.
Date: 6/23/80
II.6.1-58
-------
TABLE 6-54,
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR KOLENE SCALE REMOVAL
SUBDIVISION [9]
Toxic pollutant
Metals and xnorganics
Antimony
Cadmium
Total chromium
Copper
Nickel
Selenium
Zinc
Halogenated aliphatics
Chloroform
Number
detected
3
2
3
3
3
1
3
1
Raw uast
Concentration,
Median
100
80
365,000
133
835
27
80
41
Maximum
450
140
367,000
4,750
37,500
179
M9/L
Average
190
80
278,000
1,645
13,034
93
Number
detected
1
1
3
3
3
3
1
Treated effluent
Concentration ,
Median Maximum
203
20
15,000 102,000
50 61
835 1,350
34 40
141
, M9/L
Average
39,060
53.7
820
31.3
Average
percent
removal
-a
75
85
98
94
66
Note: Blanks indicate data not available.
Dashes indicate negligible removal,
aTreated effluent concentration exceeds raw waetewater concentration.
Because different salt solutions are used in the hydride scale
removal process, the flow and wastewater characteristics from
that process are significantly different than those from the
kolene operations. The flow rate averages approximately
2.52 ms/Mg (600 gal/ton) of product. Generally, the same
pollutants are found, but in different quantities, in the
waste streams from both processes. In addition, cyanide is
sometimes generated in the hydride process but not in the
kolene process. Wastewater characterization data for conven-
tional and toxic pollutants for the hydride process are pre-
sented in Tables 6-55 and 6-56, respectively.
TABLE 6-55.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HYDRIDE SCALE REMOVAL
SUBDIVISION [9]
Average raw waste flow: 5.3 m3/Mg
Average gross effluent flow: 5.3 m3/Mg
Raw wastewater
Number Concentration,
Parameter
TSS
Dissolved iron
PH
detected Median
2 440
2 18
3 11.9
Maximum
490
37
12.4
mg/La
Average
440
18
11.9
Grose effluent
Number Concentration,
detected Median
2 43
2 0.53
3 7.9
Maximum
69
0.83
8.2
mg/La
Average
43
0.53
7.9
Percent
removal
91
97
Note: Blanks indicate no data available.
Except pH values, given in pH units.
Date: 6/23/80
II.6.1-59
-------
TABLE 6-56.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR HYDRIDE SCALE REMOVAL
SUBDIVISION [9]
Raw wastewater
Metals and inorganics
Antimony
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Silver
Zinc
Number
detected
2
1
2
2
0
2
2
1
1
2
Concentration,
475
12
0,400
593
675
4,510
35
115
138
750
15,300
670
1,100
8,700
75
Treated effluent
pg/L Number Concentration,
475
8,400
593
675
4,510
138
1
1
2
2
2
2
2
0
2
2
250
10
24,000
50
203
50
780
20
32.5
47,800
50
369
50
1,350
20
40
vq/L |
24,000
SO
203
50
780
20
32.5
Average
percent
47
35,
93
83
82
76
Note: Blanks indicate data not available.
*Treated effluent concentration exceeds raw waetevater concentration.
II.6.2.20 Subcategory 24-Continuous Alkaline Cleaning [9]
In the alkaline cleaning process, wastewaters are generated in
the cleaning solution tanks and in the subsequent rinsing steps.
The first potential source, the bath itself, contains a caustic
solution that usually has a high level of sodium compounds and
other constituents, depending on the type of solutions being
used. Some mills have demonstrated the ability to reuse the
same cleaning solution continuously, and they add fresh solu-
tion only to make up for evaporation losses. However, due to
the buildup of contamination in the baths, most mills discharge
the contents of the bath on a weekly or monthly basis, or as
soon as the cleaning ability of the solution is impaired by the
buildup of dissolved solids and oils.
Depending on the type of cleaning solutions used, the constituents
in the wastewater from this process may vary considerably. The
usual pollutant materials present in the waste streams from the
process are suspended and dissolved solids, oils and greases
that are sometimes in emulsions, and lesser amounts of
dissolved metals. These pollutants are generated by the mills
using the standard cleaning solution prepared with a caustic
such as sodium hydroxide. However, some mills use solutions
containing phosphates or permanganates that may contribute
additional pollutants to the waste stream. Because of the
nutrient potential of the phosphates, in some forms, the
impact of this parameter on receiving bodies may be
significant.
Because most alkaline cleaning baths are used to process a
large amount of product, contamination can build up in the tank
Date: 6/23/80
II.6.1-60
-------
to extremely high levels. Average levels of pollutants found in
alkaline cleaning baths are shown below:
Parameter Typical value
Alkalinity 1,000 mg/L
Iron (total) 100 mg/L
Oil and grease 1,500 mg/L
pH 12-13
TDS 25,000 mg/L
TSS 1,000 mg/L
Temperature 70°F - 200°F
The rinse step(s) following the cleaning operation represent
the second source of wastes from the alkaline cleaning process.
After immersion of the product into the cleaning bath, rinsing
is required to remove residual cleaning solution from the
product and to cool the product if the cleaning bath was
heated. Rinsing is usually performed in drip tanks or spray
chambers, using either one tank or several depending on the
degree of rinsing required. Although some mills use standing
(or bath) rinse tanks (i.e., no continuous flow through the
tanks), many mills use rinse tanks that have continuous water
feed and overflows. This is done to keep the rinse water
relatively free from contamination and at a low temperature,
so that the product may be cooled if necessary. The quality
of the wastewater being discharged from the rinse tanks can
vary considerably depending on such factors as the type of
rinsing used (i.e., whether rinsing is done on a batch or
flow-through basis), the age of the solution in the cleaning
tanks, and the amounts of cleaning solution carried over from
the cleaning step.
Tables 6-57 and 6-58 present conventional and toxic pollutant
data, respectively, for the alkaline cleaning subcategory.
TABLE 6-57. WASTEWATER CHARACTERIZATION OF CLASSICAL POLLUTANTS
FOR THE ALKALINE CLEANING SUBCATEGORY [9]
Average raw waste flow: 1.49 m3/Mg
Average gross effluent flow 1.49 m3/Mg
Raw wastewaterGross effluent"
-- - -- -— • — Average
Number Concentration, mg/L Number Concentration, mg/L percent
Parameter detected
TSS
Oil and grease
Dissolved iron
pH
3
3
3
3
Median Maximum Average detected
11
9
0.34
9
17
21
0.70
10.8
7.2
13
0.38
9.2
3
3
3
3
Median Maximum Average removal
16
4
0.83
7.5
92
4.5
18
7.6
36
4.1
6.3
7.1
_c
66
_c
*Includes batch and continuous cleaning.
Except pH values, given in pH units.
°Effluent concentration exceeds raw wastewater concentration.
Date: 6/23/80 II.6.1-61
-------
TABLE 6-58.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOUND IN THE CONTINUOUS
ALKALINE CLEANING SUBCATEGORY [9]
Raw wastewater
Treated effluent
Toxic pollutant
Metals and inorganics
Nickel
Phenols
Phenol
Aromatics
2,6-Dinitrotoluene
Fluoranthene
Pyrene
Halogenated aliphatics
Chloroform
Tetrachloroethylene
Number
Concentration, pg/L
Number
Concentration, gg/L
Average
percent
detected Median Maximum Average detected Median Maximum Average removal
20
24
47
24
32
48. 5
37
4,175
7,000
4,175
52
49
48.5
37
64.5
52
65
64.5
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
*Treated effluent concentration exceeds raw wastewater concentration.
II. 6.3 PLANT SPECIFIC DESCRIPTION [2-9]
The following paragraphs describe conventional and toxic pollut-
ant data, and treatment methods at selected plants within each
subcategory of the iron and steel industry. Plants were select-
ed on the basis of completeness of sampling data and description
of control methods. Only conventional data are presented for
some subcategories due to the lack of toxic pollutant analyses.
One plant was selected for presentation for each subcategory and
subdivision. Selection was based on the availability of data
and description of the treatment method used. Additional plant
specific data are available in the draft contractor reports
(See references).
II.6.3.1 Subcategory 1 - Byproduct Coke [2]
Plant 009
This plant uses a physical/chemical treatment system. Excess
ammonia liquor from two coke plants is mixed and then passed
through a .gas flotation unit, a mixed media filtration unit,
an activated carbon adsorption unit, and free and fixed ammonia
strippers. Benzol plant wastewaters for both plants are mixed
and passed through the gas flotation, mixed media filtration,
and activated carbon adsorption units prior to disposal in coke
quenching. Table 6-59 and Table 6-60 present plant specific
conventional and toxic pollutant data, respectively, for Plant
009 in the byproduct coke subcategory.
Date: 6/23/80
II.6.1-62
-------
TABLE 6-59. PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR THE BYPRODUCT COKE SUB-
CATEGORY (PLANT 009) [2]
Raw wastewater flow: 0.20 m3/Mg (47 gal/ton)
Treated effluent flow: 0.40 m3/Mg (97 gal/ton)
Concentration, mg/La
Parameter
Ammonia
Oil and grease
Total phenols
Sulfide
TSS
PH
Raw
wastewater
8,300
83
1,700
980
97
8.6
Treated
effluent
220
9
1
550
31
9
Percent
removal
97
89
99
68
aExcept pH values, given in pH units.
II.6.3.2 Subcategory 2 - Beehive Coke [2]
Plant E
Coke quench runoffs from this plant are treated in simple settl-
ing ponds with no provision for recycle. Table 6-61 presents
conventional pollutant data for this plant.
II.6.3.3 Subcategory 3 - Sintering [3]
Plant 019
Sinter plant wastewaters are treated by mixing them with lime
to aid floe formation. The floe is settled in a Lamella
thickener. Overflow is mixed with makeup water and recycled
to scrubbers. Underflow is discharged to a blast furnace
clarifier for further treatment.
Table 6-62 and Table 6-63 present plant specific conventional
and toxic pollutant data, respectively, for Plant 019 in the
sintering subcategory.
II. 6.3.4 Subcategory 4 - Blast Furnace-Iron [3]
Plant 028
Blast furnace gas cleaning system wastewaters are treated by
aeration, neutralization with lime, chlorination, coagulation
Date: 6/23/80 II.6.1-63
-------
o
C"
rt
(D
oo
o
TABLE 6-60.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR THE BYPRODUCT
COKE SUBCATEGORY (PLANT 009) [2]
H
H
Average raw wastewater flow: 1.49 m3/Mg
Average treated effluent flow: 1.49 m3/Mg
Raw wastewater
Parameter
TSS
Oil and grease
Dissolved iron
PH
Number
detected
4
3
3
4
Concentration,
Median
18
5
0.10
8.3
Maximum
550
21
0.30
12
mg/L
Average
150
10
14
10
Number
detected
4
4
4
4
Treated
effluent
Concentration^
Median
54
4
9.4
6.9
Maximum
130
5
24
7.5
mg/L
Average
60
3.6
11
6.9
Average
percent
removal
60
64
21
aExcept pH values, given in pH units.
-------
TABLE 6-61. PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR PLANT E, BEEHIVE COKE
SUBCATEGORY [2]
Raw wastewater flow: 2.05 m3/Mg
Treated effluent flow: 2.05 m3/Mg
Concentration, mg/La
Parameter
Ammonia
Oil and grease
Total phenols
Sulfide
TSS
PH
Raw
wastewater
0.33
<5
0.011
<0.02
170
7.3
Treated
effluent
0.24
<5
0.014
<0.02
36
7.1
Percent
removal
27
_b
-
78
Note: Dashes indicate negligible removal.
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
TABLE 6-62. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 019, SINTERING SUBCATEGORY [3]
Raw wastewater flow: 1.25 m3/Mg
Treated effluent flow: 0.11 ms/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Total phenols
Raw
wastewater
810
210
5.9
2,200
Treated
effluent
15,000
1,100
8.6
2,100
Percent
removal
_b
_b
5
Treated effluent concentration exceeds raw
wastewater concentration.
Date: 6/23/80
II.6.1-65
-------
TABLE 6-63.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT, 019 FOR THE SINTERING
SUBCATEGORY [3]
Toxic pollutant
Concentration, pg/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Phenols
Phenol
2,4-Dinitrophenol
1,300
20
600
260
5,300
200
13
8,700
85
124
20
1,000
ND
770
10
270
160
800
130
10
5,000
990
420
490
990
ND
41
50
55
38
85
35
23
43
a
a
Polycylic aromatic hydrocarbons
Benz ( a ) anthracene
Benzo(a)pyrene
Chrysene
Fluoranthene
Pyrene
ND
ND
ND
ND
7
260
190
53
860
1,100
_a
"a
"a
~a
~a
Note: Blanks indicate no data available
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration.
with polymer, thickening, cooling and recycle. A portion of
the recycle water is blown down and discharged to a municipal
sanitary sewer.
Date: 6/23/80
II.6.1-66
-------
Tables 6-64 and 6-65 present plant specific classical and toxic
pollutant data, respectively, for Plant 028 in the iron blast
furnace subcategory.
TABLE 6-64. PLANT SPECIFIC CLASSICAL POLLUTANT DATA FOR
PLANT 028, IRON BLAST FURNACE SUBCATEGORY [3]
Raw wastewater flow: 9.5 m3/Mg (2,300)
Treated effluent flow: 0.78 mVMg (190)
Concentration, mg/La
Parameter
Ammonia-N
Fluoride
Total phenols
TSS
Sulfide
PH
Raw
wastewater
25
9
2.5
1,600
2.5
10.2
Treated
effluent
16
7.9
2.0
44
0.5
8.8
Percent
removal
36
14
80
97
80
aExcept pH values, given in pH units.
II.6.3.5 Subcategory 5 - BlastFurnace-Ferromanganese [3]
Plant 025
Venturi scrubber wastewaters at this plant are treated via
thickening and complete recycle to the scrubbers. Gas cooler
wastewaters are treated in a similar manner. As a result, this
plant achieves zero discharge.
Tables 6-66 and 6-67 presents plant specific classical and toxic
pollutant data, respectively, for Plant 025 in the ferromanganese
blast furnace subcategory.
II. 6.3.6 Subcategory 6 - Basic Oxygen Furnace - Semiwet Air
Pollution Control [4]
Plant U
Table 6-68 presents plant specific conventional pollutant data
for Plant U in the basic oxygen furnace-semiwet air pollution
control subcategory.
Date: 6/23/80 II.6.1-67
-------
TABLE 6-65.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT 028, THE IRON BLAST FURNACE
SUBCATEGORY [3]
Concentration , p g/L
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Phenol
Raw
wastewater
150
630
1,200
23,000
1,200
73
30,000
3,200
340
540
ND
ND
130
240
3
250
Treated
effluent
10
9
30
83
60
5
330
11,000
9
180
ND
3
90
44
ND
560
Percent
removal
93
99
98
99
95
93
99
_a
97
67
_
a
31
82
>99
a
Aromatics
Hexachlorobenzene
ND
ND
Polycylic aromatic
Benzo(a)pyrene
Fluoranthene
Flourene
Chrysene
Naphthalene
Pyrene
Halogenated aliphatics
Chloroform
ND
ND
ND
ND
8
ND
10
190
23
10
ND
15
12
32
_a
_a
~a
_
_a
_a
_a
Note: Blanks indicate no data available
Dashes indicate negligible removal.
Treated effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-68
-------
TABLE 6-66.
PLANT SPECIFIC CLASSICAL POLLUTANT DATA FOR
PLANT 025, FERROMANGANESE BLAST FURNACE
SUBCATEGORY [3]
Raw wastewater flow: 48.1 m3/Mg (11,500 gal/ton)
Treated effluent flow: 48.3 m3/Mg (11,600 gal/ton)
Concentration, mg/La
Parameter
Ammonia-N
Manganese
Total phenols
Sulfide
TSS
PH
Raw
wastewater
710
500
6.5
130
4,200
11.3
Treated
effluent
680
53
6.3
410
Percent
removal
4
89
3
90
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
TABLE 6-67.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 025, FERROMANGANESE BLAST FURNACE
SUBCATEGORY [3]
Concentration, vg/L
Toxic pollutant
Metals and inorganics
Cyanide
Zinc
Aromatics
Benzene
Toluene
Raw
wastewater
690,000
30,000
21
17
Treated
effluent
710,000
26,000
10
4
Percent
removal
_a
13
52
76
Polycylic aromatic
Napthalene
Halogenated aliphatics
Chloroform
Tetrachloroethylene
39
160
64
24
140
9
38
13
86
aTreated effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-69
-------
TABLE 6-68. PLANT SPECIFIC POLLUTANT DATA FOR PLANT U,
BASIC OXYGEN FURNACE - SEMIWET AIR
POLLUTION CONTROL SUBCATEGORY [4]
Raw wastewater flow: 3.0 m3/Mg (730 gal/ton)
Treated effluent flow: 3.0 m3/Mg (730 gal/ton)
Concentration, mg/L
Parameter
TSS
Fluoride
PH
Copper
Lead
Mercury
Zinc
Raw
wastewater
420
3.1
11.8
0.03
1.0
0.001
1.1
Treated
effluent
38
3.8
11.9
1.0
0.0027
1.6
Percent
removal
91
_b
_
_b
_b
Note: Blanks indicate data not available.
Dashes indicate negligible removal.
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
This plant utilizes chemical coagulation, thickening, and recy-
cle of all wastewaters generated by its gas cleaning system.
Thirteen percent of the recycle is reused for slag processing.
System equipment is comprised of thickener and vacuum filters
for solids dewatering.
II. 6.3.7 Subcategory 7 - Basic Oxygen Furnace- Wet Air
Pollution Control [4]
Open Combustion
Plant 036. This plant uses primary solids separation
(cyclones and classifiers). Classifier overflow is discharged
to a thickener. Thickener overflow is recycled with 53% blow-
down. Makeup water is added to the recycle. Slowdown is dis-
charged to sewers. Thickener underflow is discharged to
centrifuges for final dewatering.
Suppressed Combustion
Plant 032. This plant uses primary solids separation
(hydroclones and classifiers). Overflow from primary solids
Date: 6/23/80 II.6.1-70
-------
separation is discharged to thickeners. Thickener overflow is
recycled after pH adjustment with 6.1% blowdown. Slowdown is
discharged to a clarifier, and this overflow is discharged to a
central wastewater treatment system. Thickener and clarifier
underflows are discharged to settling lagoons. The EOF system
has a secondary ventilation scrubber system that also dis-
charges effluents to the thickeners.
Table 6-69 and Table 6-70 present plant specific conventional
and toxic pollutant data, respectively, for both Plant 036 and
Plant 032 in the open combustion and suppressed combustion
subdivisions of the basic oxygen furnace - wet air pollution
control subcategory.
TABLE 6-69. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA FOR
PLANTS 036 and 032, BASIC OXYGEN FURNACE - WET
AIR POLLUTION CONTROL SUBCATEGORY, OPEN COMBUSTION
AND SUPPRESSED COMBUSTION SUBDIVISIONS [4]
Plant 036 Plant 032
(Open (Suppressed
combustion) combustion)
Raw wastewater flow, m3/Mg:
Treated effluent flow, m3/Mg:
Plant 036
Concentration, mg/La
Raw Treated
Parameter wastewater effluent
TSS 7,100 1,200
pH 11.3 12
1.91 6.16
1.02 0.41
Plant 032
Concentration, mg/La
Percent Raw Treated
removal wastewater effluent
82 1,500 55
9.2 8.8
Percent
removal
96
aExcept pH values, given in pH values.
II.6.3.8 Subcategory 8 - Open Hearth Furnace [4]
Semiwet Air Pollution Control
Plant 043. The gas cleaning system used at this plant is a
semiwet unit whereby gases are temperature conditioned for pre-
cipitation cleaning. Each furnace has its own spray chamber
and is manifolded to a central precipitator gas cleaning
system. A common water treatment system services all of the
spray chambers.
The water treatment system consists of a thickener for sedimen-
tation. Thickener overflow is recycled with a 0.3% blowdown
Date: 6/23/80 II.6.1-71
-------
TABLE 6-70.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
(PLANTS 036 AND 032), THE BASIC OXYGEN
FURNACE - WET AIR POLLUTION CONTROL
SUBCATEGORY, THE OPEN COMBUSTION AND
SUPPRESSED COMBUSTION SUBDIVISIONS [4]
Plant 036
(Open combustion)
Concentration, mg/L
Toxic Pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Raw
wastewater
170
370'
330
370
34
47
43
2,000
10
Treated
effluent
10
40
360
160
0.1
10
340
710
110
Percent
removal
94
43«
57
99
79«
65
_a
Plant 032
(Suppressed combustion
Concentration, mq/L
Raw
wastewater
98
1,100
320
27,000
340
30
8,400
60
7
Treated
effluent
e
13
9
470
10
15
230
29
10
Percent
removal
92
99
97
98
97
50
97
52.
Balogenated aliphatics
Chloroform
53
120
0.04
Mote: Blanks indicate no data available.
Dashes indicate negligible removal.
Treated effluent concentration exceeds raw wastewater concentration.
discharged to a final polishing lagoon. Thickener underflow is
conveyed to a settling lagoon. The dry precipitation dust
is slurried and evacuated from precipitation hoppers by
pneumatic conveyors with water jet ejectors. The effluent
is discharged to another thickener. The thickener overflow is
recycled to the water jet ejectors, and the underflow is dis-
charged to the same settling lagoons as are the spark box
effluents.
Table 6-71 and Table 6-72 present plant specific conventional
and toxic pollutant data, respectively, for Plant 043 in the
semiwet air pollution control subdivision of the open hearth
furnace subcategory.
Wet Air Pollution Control
Plant 042. This plant uses a manifolded, wet hydroscrub-
ber, gas cleaning system by which all furnaces are exhausted
through a common ductwork to three gas cleaning systems. Three
central ducters of hydroscrubbers serve as the gas cleaning
Date: 6/23/80
II.6.1-72
-------
TABLE 6-71.
PLANT SPECIFIC CLASSICAL POLLUTANT DATA PLANT 043,
OPEN HEARTH FURNACE SUBCATEGORY, SEMIWET AIR
POLLUTION CONTROL SUBDIVISION [4]
Raw wastewater flow: 4.9 m3/Mg (1,160 gal/ton)
Treated effluent flow: 0.02 mVMg (3.7 gal/ton)
Concentration, mg/La
Parameter
TSS
Fluoride
Nitrate
PH
Raw
wastewater
510
260
10
2.7
Treated
effluent
30
32
9.1
10.8
Percent
removal
94
88
9
Except pH values, given in pH units.
TABLE 6-72.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 043, THE OPEN HEARTH FURNACE
SUBCATEGORY, THE SEMIWET AIR POLLUTION
CONTROL SUBDIVISION [4]
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Nickel
Zinc
Raw
wastewater
80
83
39
53
600
Treated
effluent
10
13
6
9
40
Percent
removal
78
84
85
83
93
Phthalates
Di-n-butyl phthalate
21
10
52
Note: Blanks indicate data not available.
Dashes indicate negligible removal.
system, with each cluster capable of serving a number of
furnaces through the manifolded ductwork. The hydroscrubber
uses steam or air and a water jet ejector to pump and clean
open hearth off gases. Waste heat boilers furnish the
steam.
Date: 6/23/80
II.6.1-73
-------
The joint water treatment system serves both the electric arc
furnace shop and the open hearth shop. The effluent discharge
waters are neutralized, flocculated with polymers, and then
discharged to clarifiers for sedimentation. Clarifier overflow
is recycled with a 71% blowdown that is discharged to final
polishing lagoons. Clarifier underflow is dewatered in vacuum
filters.
Table 6-73 presents plant specific classical pollutant data for
Plant 042 in the wet air pollution control subdivision of the open
hearth furnace subcategory.
TABLE 6-73. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 042,
OPEN HEARTH FURNACE SUBCATEGORY, WET AIR
POLLUTION CONTROL SUBDIVISION [4]
Raw wastewater flow: 2.1 ms/Mg (510 gal/ton)
Treated effluent flow: 1.5 m3/Mg (360 gal/ton)
Concentration, mg/La
Parameter
TSS
Fluoride
Nitrate
PH
Zinc
Raw
wastewater
1,500
100
640
6.7
390
Treated
effluent
15
27
450
9.1
4
Percent
removal
99
73
30
99
Except pH values, given in pH units.
II.6.3.9 Subcategory 9 - Electric Arc Furnace Semiwet Air
Pollution Control [5]
Plant 059B The treatment system at this plant consists
of a clarifier for sedimentation. Clarifier overflow is dis-
charged, and the underflow is dewatered using vacuum filters.
Table 6-74 and Table 6-75 present plant specific conventional
and toxic pollutant data, respectively, for Plant 059B in the
electric arc furnace - toxic pollutant data, respectively,
for Plant 059B in the electric arc furnace - semiwet air
pollution control subcategory.
Date: 6/23/80 II.6.1-74
-------
II.6.3.10 Subcategory 10 - Electric Arc Furnace-Wet Air
Pollution Control [5]
Plant 052
Plant 052 uses neutralization, flocculation, and clarification
to treat the wastewaters from the electric arc furnace (EAF)
shop. The water treatment system also treats open-hearth shop
wastewaters. The wastewaters from the steam hydroscrubber
systems of the EAF and open-hearth shops discharge to a pump
station and are pumped to a flocculation and neutralization tank
which is followed by a clarifier. Thirty percent of the
clarifier overflow is recycled to the gas cleaning system.
Vacuum filters dewater the clarifier underflow. Slowdown is
discharged to mill settling ponds.
Tables 6-76 and 6-77 present conventional and toxic pollutant
data for plant 052 in this subcategory.
II.6.3.11 Subcategory 11 - Vacuum Degassing [5]
Carbon Steel
Plant 062. This plant utilizes a combination treatment
system for its vacuum degasser and continuous caster. Vacuum
degasser wastewater is discharged to a hot well from which a
sidestream is treated through a belt filter. The filter
effluent and the remaining degasser wastewater is then discharged
to a main hot well. From the hot well, the combined degasser
and caster wastewaters are treated through a scale pit, sand
filters, and cooling tower. A recycle is taken from the cooling
tower back to the degasser. This system has zero discharge
since the plant recirculates its water through a 7.6 x 10* m3
(20 M gal) reservoir.
Tables 6-78 and 6-79 present conventional and toxic pollutant
data for carbon steel vacuum degasser plant 065.
Specialty Steel
Plant 068. Vacuum degasser wastewater discharges to a hot
well and is then treated via the mill central treatment facility.
Treatment includes deep bed filters and clarifiers. A recycle
is taken from the central treatment facility to the vacuum
degasser.
Tables 6-80 and 6-81 present conventional and toxic pollutant
data for specialty steel vacuum degasser plant 068.
Date: 6/23/80 II.6.1-15
-------
TABLE 6-74.
PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 059B, ELECTRIC ARC FURNACE -
SEMIWET AIR POLLUTION CONTROL SUBCATEGORY [5]
Raw wastewater flow: 0.33 m3/Mg
Treated effluent flow: 0.33 m3/Mg
Concentration, mg/L
Raw , Treated
Parameter
wastewater
effluent
TSS
Fluoride
pH
120
64
8.1
Except pH values, given in pH units.
DA representative raw wastewater sample
could not be obtained.
TABLE 6-75.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 059B, ELECTRIC ARC FURNACE -
SEMIWET AIR POLLUTION CONTROL SUBCATEGORY
[5]
Toxic pollutant
Concentration, pg/L
Raw Treated
wastewater effluent
Metals and inorganics
Cyanide (EPA)
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
Phenol
Halogenated aliphatics
Chloroform
1,2-trans-Dichloroethane
3
450
31
21
7
51
ND
57
ND
66
14
Note: Blanks indicate data not available.
aA raw wastewater sample could not be obtained.
Date: 6/23/80 II.6.1-76
-------
TABLE 6-76. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 052, ELECTRIC ARC FURNACE-
WET SUBCATEGORY [5]
Raw wastewater flow: 4.96 m3/Mg
Treated effluent flow: 3.5 m3/Mg
Concentration, mg/La
Parameter
TSS
Fluoride
PH
Raw
wastewater
890
30
9.0
Treated
effluent
7
27
7.8
Percent
removal
99
10
aExcept pH values, given in pH units.
TABLE 6-77. PLANT SPECIFIC DATA FOR PLANT 052, THE ELECTRIC ARC
FURNACE-WET AIR POLLUTION CONTROL SUBCATEGORY [5]
Concentration,
Raw Treated Percent
_ Toxic pollutant _ wastewater effluent removal
Metals and inorganics
Zinc 2,000
Ph thai ate s
Bis(2-ethylhexyl) phthalate 160 330 -a
Butyl benzyl phthalate 7 95 -a
Di-n-butyl phthalate 7 11 35
Phenols
4-Nitrophenol ND ND
Pentachlorophenol ND ND -
Aromatics
Benzene 7 5 29
Polycyclic aromatic hydrocarbons
Fluoranthene ND ND -
Pyrene ND ND -
Note: Blanks indicate data not available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration .
Date: 6/23/80 II. 6. 1-77
-------
TABLE 6-78.
PLANT SPECIFIC POLLUTANT DATA FOR PLANT 062,
VACUUM DEGASSER SUBCATEGORY, CARBON STEEL
SUBDIVISION [5]
Raw wastewater flow: 0.73 m3/Mg (175 gal/ton)
Treated effluent flow: 0.66 m3/Mg (159 gal/ton)
Concentration, mg/L
Parameter
TSS
Nitrate
Manganese
PH
Raw
wastewater
30
2.8
2.0
8.6
Treated
effluent
16
0.27
7.9
Percent
removal
47
87
aExcept pH values, given in pH units
TABLE 6-79.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 062, VACUUM DEGASSER SUBCATEGORY,
THE CARBON STEEL SUBDIVISION [5]
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
Raw
wastewater
130
90
300
23
2,000
57
43
Treated
effluent
26
207
60
13
330
3
7
Percent
removal
80
80
43
84
95
84
Note: Blanks indicate data not
available.
Dashes indicate negligible removal.
aTreated effluent concentration
concentration .
exceeds raw
wastewater
Date: 6/23/80
II.6.1-78
-------
TABLE 6-80.
PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 068, VACUUM DEGASSER SUBCATEGORY,
SPECIALTY STEEL SUBDIVISION [5]
Raw wastewater flow: 2.8 m3/Mg
Treated effluent flow: 2.8 m3/Mg
Concentration, mg/L
Parameter
TSS
Nitrate
Manganese
pH
Raw
wastewater
81
0.7
4,000
8.1
Treated
effluent
39
0.7
0.13
7.9
Percent
removal
52
-
99
Note: Dashes indicate negligible removal.
aExcept pH values, given in pH units.
TABLE 6-81.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 068, VACUUM DEGASSER SUBCATEGORY,
THE SPECIALTY STEEL SUBDIVISION [5]
Concentration, Mg/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
Raw
wastewater
50
47
200
40
500
ND
ND
Treated
effluent
19
23
90
30
300
53
500
Percent
removal
62
51
55
75
40
a
a
Note: Blanks indicate data not available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-79
-------
II.6.3.12 Subcategory 12 - Continuous Casting [5]
Carbon Steel
Plant AF. The continuous caster at this plant is on a
combination treatment system with a vacuum degasser. The treat-
ment consists of a scale pit, high-flow-rate pressure filters, a
cooling tower, and a recycle pump system. Slowdown is less than
2%.
Table 6-82 presents pollutant data for plant AF.
TABLE 6-82. PLANT SPECIFIC POLLUTANT DATA FOR PLANT AF,
CONTINUOUS CASTING SUBCATEGORY, CARBON STEEL
SUBDIVISION [5]
Raw wastewater flow: 6.2 ms/Mg (1,500 gal/ton)
Treated effluent flow: 3.9 m3/Mg (930 gal/ton)
Concentration, mg/La
Parameter
TSS
Oil and grease
pH
Copper
Zinc
Raw
wastewater
89
3
6.6
37
2.6
Treated
effluent
22
<0.5
6.8
0.25
1.6
Percent
removal
80
98
99
38
aExcept pH values, given in pH units.
II.6.3.13 Subcategory 13 - Hot Forming-Primary [6]
Carbon Steel
Plant 083. The wastewater treatment system at plant 083
serves several hot forming mills and steelmaking facilities
(BOF, electric arc furnace, etc.). The hot forming mills in-
clude primary, section, and plate rolling mills, (blooming mill,
structural mill, plate mill, and rod mill). The blooming mill
wastewaters are discharged to a main pump station after passing
through primary scale pits with oil collection equipment. The
rod mill has its own treatment equipment and discharges only a
blowdown to the central treatment system. Other mill wastewaters
discharge to the main pump station as well. The combined waste
stream is then treated by flocculating clarifiers and is recycled
through a cooling tower to the mills. Tables 6-83 and 6-84
present conventional and toxic pollutant data for this plant.
Date: 6/23/80 II.6.1-80
-------
TABLE 6-83.
PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 083 (53 IN.), HOT FORMING-PRIMARY
SUBCATEGORY, CARBON SUBDIVISION [6]
Raw wastewater flow: 1.3 m3/Mg
Treated effluent flow: 0.05 mVMg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Raw
wastewater
240
35
7.1
Treated
effluent
9
10
7.6
Percent
removal
96
71
Except pH values, given in pH units.
TABLE 6-84.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 083 (53 IN.) FOR HOT FORMING-PRIMARY
SUBCATEGORY, CARBON STEEL SUBDIVISION [6]
Toxic pollutant
Concentration, pg/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
120
530
70
9
100
130
40
50
20
70
92
29
30
Note: Blanks indicate no data available
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration.
Specialty Steel
Plant 082. The wastewater treatment system at plant 082
serves a combination of hot forming mills consisting of primary
and flat rolling mills (two slab mills, two plate mills) for
carbon and specialty steel production. The wastewaters from
the specialty, primary, and flat rolling mills are discharged
to the waste treatment plant main collection sump after passing
Date: 6/23/80
II.6.1-81
-------
through primary and combination secondary scale pits. The waste-
waters from the main collection sump are discharged to settling
basins which, in turn, discharge to filters. Filtered water is
then discharged to the river. No recycle is employed.
Tables 6-85 and 6-86 present conventional and toxic pollutant
data for this plant.
TABLE 6-85.
PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 082 (140 IN) HOT FORMING-
PRIMARY-SPECIALTY STEEL [6]
Raw wastewater flow: 0.71 m3/Mg (170 gal/ton)
Treated effluent flow: 0.71 m3/Mg (170 gal/ton)
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Raw
wastewater
83
75
7.8
Treated
effluent
1
12
7.5
Percent
removal
99
84
Except pH values, given in pH units.
TABLE 6-86.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 082 (140 IN), FOR HOT FORMING-
PRIMARY SUBCATEGORY, SPECIALTY STEEL
SUBDIVISION [6]
Toxic pollutant
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Concentration,
(jg/L
Raw Treated
wastewater effluent
50
190
400
570
80
30
40
50
50
30
Percent
removal
40
79
88
91
63
Date: 6/23/80
II.6.1-82
-------
II.6.3.14 Subcategory 14 - Hot Forming-Section [6]
Carbon Steel
Plant 088. Bar mill wastewaters at plant 088 are first
treated by two sets of scale pits. One set receives wastewaters
from the hot saws, shears, stands, pull rods and bar rotators
and then recycles them to the process. The second set of pits
accepts bar mill stands effluent and skip cooling water. A
partial recycle is taken from the scale pits back to the process,
The remainder of the scale pit effluent is sent to a mix tank
and then to a clarifier. Clarifier overflow is recycled to the
bar mill. Three percent of the overflow is blowdown to the
sewer. Clarifier underflow is discharged to an underflow pond.
Tables 6-87 and 6-88 present conventional and toxic pollutant
data for hot forming-section-carbon steel plant 088.
TABLE 6-87. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 088 (14 IN. BAR MILL), HOT FORMING-
SECTION SUBCATEGORY, CARBON SUBDIVISION [6]
Raw wastewater flow: 29 m3/Mg
Treated effluent flow: 0.58 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Raw
wastewater
80
68
7.5
Treated
effluent
87
15
7.5
Percent
removal
_b
79
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
Specialty Steel
Plant 081. The wastewater treatment system for plant 081
serves a combination of hot forming mills consisting of primary
and section rolling. The wastewaters are discharged to a Lamella
separator after passing through primary scale pits. The overflow
from the Lamella is recycled to the primary and section rolling
mills. A 7.1% blowdown from the Lamella is discharged to a
central wastewater treatment system which also treats the waste-
water from combination acid pickling, alkaline cleaning, kolene
Date: 6/23/80 II. 6.1-83
-------
TABLE 6-88.
PLANT SPECIFIC TOX POLLUTANT DATA FOR
PLANT 088, (14 IN. BAR MILL) FOR THE HOT
FORMING-SECTION SUBCATEGORY, CARBON STEEL
SUBDIVISION [6]
Toxic pollutant
Concentration, pg/L
RawTreatedPercent
wastewater effluent removal
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
30
75
66
180
1,200
120
270
95
470
2,200
_a
-a
a
"a
—
Note: Blanks indicate no data available
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration.
and hydride descaling, continuous alkaline cleaning, and one-
section rolling mill. Makeup water is added to the Lamella
separator and section mills as required.
Tables 6-89 and 6-90 present conventional and toxic pollutant
data for hot forming-section-specialty steel plant 081.
TABLE 6-89.
PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR PLANT 081 (NO. 4 HOT MILL),
HOT FORMING-SECTION SUBCATEGORY,
SPECIALTY STEEL SUBDIVISION [6]
Raw wastewater flow: 34 m3/Mg (8,200 gal/ton)
': 1.4 m5/Mg (340 gal/ton
Treated effluent flow:
Parameter
Concentration, mg/L
Raw Treated Percent
wastewater effluent removal
TSS
Oil and grease
PH
84
250
7.3
23
8
7.9
73
97
Except pH values, given in pH units.
Date: 6/23/80
II.6.1-84
-------
TABLE 6-90.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 081 (NO. 4 HOT MILL), HOT FORMING-
SECTION SUBCATEGORY, SPECIALTY STEEL
SUBDIVISION [6]
Toxic pollutant
Concentration, pg/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
90
130
50
830
85
70
75
50
490
45
22
42
-
41
47
Note: Blanks indicate no data available
Dashes indicate negligible removal.
II.6.3.15 Subcategory 15 - Hot Forming-Flat [6]
Plate Mills
Plant 082. Wastewaters from the 3.56 m (140-inch) mill go
to primary scale pits and then to a combined secondary scale pit.
Overflow from the secondary scale pits is discharged to three
common settling basins set in parallel. The effluent from the
settling basin is then passed through media filters. Filtered
water is then discharged to a receiving stream. Filter backwash
is taken to a backwash settling basin which discharges to the
three parallel settling basins.
Tables 6-91 and 6-92 present conventional and toxic pollutant
data for plant 082 of this subdivision.
Hot Strip and Sheet Mills
Plant 087. Plant 087 is a central treatment system serving
a merchant mill, butt weld pipe mill, blooming mill, hot scarfer
and a 1.12 m (44-inch) hot strip mill. Wastewaters from the
various sources pass first through their individual scale pits
equipped with baffler and oil removal equipment and are then
pumped to clarifiers. Coagulant aids are added at the clarifier
inlet to assist in settling. Clarifier overflow is discharged
to a receiving stream as the underflow is processed by vacuum
filters.
Table 6-93 presents conventional and toxic pollutant data for
plant 087 of this subdivision.
Date: 6/23/80
II.6.1-85
-------
TABLE 6-91. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 082 (140 IN. MILL), HOT FORMING-
FLAT SUBCATEGORY, PLATE MILL SUBDIVISION [6]
Raw wastewater flow: 0.50 ms/Mg
Treated effluent flow: 0.50 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
pH
Raw
wastewater
67
46
8.9
Treated
effluent
1
10
7.4
Percent
removal
99
78
Except pH values, given in pH units.
TABLE 6-92. PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 082 (140 IN. MILL) HOT FORMING-
FLAT SUBCATEGORY, PLATE MILL SUBDIVISION [6]
Concentration, jjg/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Raw
wastewater
60
160
260
37
80
Effluent3
1,000
40
40
40
30
Percent
removal
h
75
h
63
Note: Blanks indicate no data available
Dashes indicate negligible removal.
aEffluent from primary scale pit.
Treated effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-86
-------
TABLE 6-93. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 087
(44 IN. HOT STRIP), HOT FORMING-FLAT SUB-
CATEGORY, HOT STRIP AND SHEET SUBDIVISION [6]
Raw wastewater flow: 20.1 m3/Mg
Treated effluent flow: 20.1 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Chromium
Copper
Zinc
Raw
wastewater
57
6
7.6
170
45
200
Treated
effluent
38
4
7.6
170
35
210
Percent
removal
33
33
-
22
_b
Note: Blanks indicate not determined.
Dashes indicate negligible removal.
aExcept pH values, given in pH units.
T.
Treated effluent concentration exceeds raw
wastewater concentration.
II.6.3.16 Subcategory 16 - Pipe and Tube [6, 7]
Hot Forming
Weld Mill (Plant 087). This mill practices once-through
treatment and utilizes a primary scale pit that discharges to a
central clarification water treatment facility. The primary
scale pit overflow waters are mixed with other wastewater from
a merchant mill, hot strip mill, and blooming mill hot scarfer
before treatment in the clarifier. Lime and polymer are added
as coagulant aids. Clarifier overflow is discharged to a
receiving stream, while the clarifier underflow is dewater
through vacuum filters.
Table 6-94 presents conventional and toxic pollutant data respec-
tively, for plant 087.
Date: 6/23/80 II.6.1-87
-------
TABLE 6-94. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 087
(WELD MILL), TUBE AND PIPE SUBCATEGORY, HOT
FORMING SUBDIVISION [6]
Raw wastewater flow: 34 ms/Mg
Treated effluent flow: 34 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Chromium
Copper
Lead
Nickel
Zinc
Raw
wastewater
66
5
7.4
240
65
800
500
250
Treated
effluent
38
4
7.5
43
31
21
Percent
removal
42
20
82
52
92
aExcept pH values, given in pH units.
Cold Forming
Plant HH-2. Tubing mill wastewaters discharge to a settling
and cooling basin which receives wastes from other mill opera-
tions such as open hearths and rolling mills. Overflow from
this settling basin flows to a similar basin and then to oil-
skimming facilities. The effluent is then pumped to a large
main reservoir from which all of the water is recycled. However,
if the reservoir is full, the treated effluent, after oil
skimming, is discharged to a receiving stream.
Table 6-95 presents conventional pollutant data for cold-forming
plant HH-2. No toxic pollutant data are currently available for
this subdivision.
II.6.3.17 Subcategory 17 - Sulfuric Acid Pickling [8]
Continuous Pickling
Plant 094. Spent concentrates from this plant are hauled
off-site.Rinses are combined with all other finishing mill
wastewaters, equalized, skimmed, treated with lime and polymers,
and clarified with thickening and centrifugation of underflows.
These treated effluents are discharged.
Date: 6/23/80 II.6.1-88
-------
TABLE 6-95. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT HH-2, PIPE AND TUBE SUBCATEGORY,
COLD FORMING SUBDIVISION [7]
Raw wastewater flow: 24.2 m3/Mg
Treated effluent flow: 0 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Raw
wastewater
23
63
5.8
Treated
effluent
4.3
2
6.2
Percent
removal
81
33
Note: Blanks indicate no data available.
aExcept pH values, given in pH units.
Tables 6-96 and 6-97 present conventional and toxic pollutant
data for continuous sulfuric acid pickling plant 094.
TABLE 6-96. PLANT SPECIFIC CLASSICAL POLLUTANT DATA FOR
PLANT 094, SULFURIC ACID PICKLING SUBCATEGORY,
CONTINUOUS PICKLING SUBDIVISION [8]
Rinsewater flow: 1.5 m3/Mg
Carbon treated wastewater: 1.5 m3/Mg
Concentration, mg/La
Pollutant
TSS
Oil and grease
Dissolved iron
PH
Rinsewater
38
9
40
5.7
Carbon-
treated
wastewater
6
6
0.05
7.8
Percent
removal
84
33
99
aExcept pH values, given in pH units.
Batch Pickling
Plant 092. Treatment at this facility includes contract
hauling of major portions of the spent concentrates, blending
Date: 6/23/80 II.6.1-89
-------
TABLE 6-97.
PLANT SPECIFIC TOXIC POLLUTANTS FOR PLANT 094,
FOUND IN THE SULFURIC ACID PICKLING SUBCATEGORY,
CONTINUOUS PICKLING SUBDIVISION [8]
Concentration,
Toxic pollutant
Sheet
pickling
Strip
pickling
Treated
wastewater
Metals and inorganics
Arsenic <10
Cadmium <10
Chromium <10
Copper 55
Cyanide 11
Lead 40
Nickel 60
Silver <10
Zinc 40
Phthalates
Bis(2-ethylhexyl) phthalate <10
Butyl benzyl phthalate ND
Di-n-butyl phthalate <10
Diethyl phthalate ND
Dimethyl phthalate ND
Aromatics
Benzene <10
Polycyclic aromatics
Acenaphthylene ND
Fluoranthene ND
Naphthalene ND
Pyrene <10
Halogenated aliphatics
Chloroform <10
Methylene chloride 170
50
140
11
11
10
90
34
ND
ND
20
10
8
10
40
10
70
62
ND
10
19
230
Note: Blanks indicate no data available.
and equalization of some concentrates and all rinses, and
treatment via a central facility, which includes chromium
reduction, neutralization with lime, coagulation with polymer,
sedimentation with a clarifier, thickening and vacuum filtra-
tion of underflows, and oil skimming.
Tables 6-98 and 6-99 present conventional and toxic pollutant
data for batch-type sulfuric acid pickling plant 092.
Date: 6/23/80
II.6.1-90
-------
TABLE 6-98. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 092, SULFURIC ACID PICKLING
SUBCATEGORY, BATCH PICKLING SUBDIVISION [8]
Concentrate flow: 0.061 m3/Mg
Rinsewater flow: 1.4 m3/Mg
Concentration, mg/La
Pollutant
TSS
Oil and grease
PH
Dissolved iron
Spent
concentrate
310
17
<1
39,000
Rinsewater
360
43
6.9
52
Rinse
process
effluent
29
9
8.3
0.45
aExcept pH values, given in pH units.
II.6.3.18 Subcategory 18 - Hydrochloric Acid Pickling [8]
Continuous Strip Pickling
Plant 091. This plant pickles wire in a continuous mode.
Spent pickle liquor and rinses are neutralized with lime,
oxidized, clarified, and filtered through pressure sand filters
prior to discharge to a receiving stream. Clarifier sludge is
dewatered by vacuum filtration prior to disposal.
Tables 6-100 and 6-101 present conbentional and toxic pollutant
data respectively, for this plant.
Batch Pickling
Plant U-2. The waste pickle liquors and rinse waters from
the batch pickling operations are neutralized in a batch treat-
ment tank by sodium carbonate prior to sanitary sewer discharge.
Table 6-102 presents conventional pollutant data for the above
batch hydrochloric acid pickling plant.
II.6.3.19 Subcategory 19 - Cold Rolling [7]
Recirculating Mills
Plant 101. The cold mill wastes at this plant originate
at twelve different cold mill operations. All wastes are
collected in a holding tank and are treated in an ultrafiltratlon
Date: 6/23/80 II.6.1-91
-------
TABLE 6-99.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT, 092, FOUND IN THE SULFURIC
ACID PICKLING SUBCATEGORY, BATCH
SUBDIVISION [8]
Concentration, pg/L
Toxic pollutant
Metals and inorganics
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2 , 4-Dichlorophenol
2 , 4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
4, 6-Dinitro-o-cresol
Polycyclic aromatics
Acenapthene
Acenaphthy 1 ene
Benzo(a)pyrene
Chrysene
Fluoranthene
Fluorene
Pyrene
Halogenated aliphatics
Chloroform
Dichlorobromomethane
Methylene chloride
Tetrachloroethylene
Tr i chl or oethy 1 ene
Raw rinse
wastewater
39
4,000
16,300
740
38
ND
1,400
ND
3,900
1,100
<10
54
ND
ND
ND
26
ND
39
ND
11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
27
ND
ND
Process
effluent
10
10
360
40
39
<10
330
<10
12
26
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
10
ND
11
ND
ND
Percent
removal
74
99
99
95
_a
a
76
-
99
97
99
99
_
-
99
-
99
99
-
-
—
-
-
.
—
_
-
_a
99
59
_
—
Process effluent concentration exceeds rinse water concentration,
Date: 6/23/80 II.6.1-92
-------
TABLE 6-100.
PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 091, HYDROCHLORIC ACID PICKLING
SUBCATEGORY, CONTINUOUS WIRE PICKLING
SUBDIVISION [8]
Concentrate
Rinses
Raw wastewater flow, n3/Mg:
Treated effluent flow, m'/Mg:
0.076
0.076
Concentrate
Parameter
Dissolved iron
TSS
Oil and grease
pH
Concentration, mg/L
Raw
wastewater Effluent
56,000
2,900
1
<1
21,000
9.8
1.7
8.3-8.5
Percent
removal
63
>99
_d
NA
1.3
1.3
Rinses
Concentration, ag/L*
Raw
wastewater Effluent
-b 0.3
24,000 0.83
-b 0.51
8.3-8.5
Percent
removal
_c
>99
_c
a£xcept pH values, given in pR values.
Blanking results in negative concentration.
cUnable to perform calculation
d,
Gross effluent exceeds raw waste concentrate.
TABLE 6-101.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT 091, THE HYDROCHLORIC ACID
PICKLING SUBCATEGORY, CONTINUOUS
STRIP PICKLING SUBDIVISION [8]
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phenols
2,4-Dichlorophenol
4,6-Dinitrophenol
2,4-Dimethylphenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
4,6-Dinitro-o-cresol
280
37,000
22,000
8
1,600,000
22,000
61,000
5
5
S
5
ND
5
ND
30
1,700
610
58
24,000
610
290,000
5
ND
5
ND
10
ND
70
20
40
30
21
190
30
130
10
ND
ND
5
ND
ND
ND
Aromatics
Benzene
Polycyclic aromatica
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)pyrene
chryiene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
Trichloroethylene
ND
5
5
ND
5
5
10
ND
ND
ND
5
10
10
5
ND
ND
5
5
5
5
5
11
5
5
5
12
8
15
8
65
5
5
5
ND
10
ND
10
ND
ND
ND
10
5
21
ND
10
Note: Blanks indicate no data available.
Date: 6/23/80
II.6.1-93
-------
TABLE 6-102. PLANT SPECIFIC POLLUTANT DATA FOR PLANT U-2,
HYDROCHLORIC ACID PICKLING SUBCATEGORY, BATCH
PICKLING SUBDIVISION [8]
Concentrate Rinses
Raw wastewater flow, m3/Mg: 0.027
Treated effluent flow, m3/Mg:
Parameter
Dissolved iron
TSS
Oil and grease
PH
Concentrate
Concentration,
mg/La
Raw
wastewater
77,000
400
<1
Rinses
Concentration, mq/L
Raw Treated .
wastewater effluent
190
0
3
i.e
0.5
390
5
8.5
0.39
0.39
Percent
removal
99
_c
_c
Note: Blanks indicates data not available.
'Except pH values, given in pH units.
Effluent is contractor hauled.
cEffluent concentration exceeds raw influent concentration.
unit on a batch basis. The discharge from this treatment goes to
a POTW. There is no other discharge from this plant.
Tables 6-103 and 6-104 present conventional and toxic pollutant
data for the raw and treated wastewater stream at this plant.
TABLE 6-103. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 101, COLD ROLLING SUBCATEGORY,
RECIRCULATING MILL SUBDIVISION [7]
Raw wastewater flow: 0.078 m3/Mg
Treated effluent flow: 0.078 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
Dissolved iron
PH
Raw
wastewater
2,200
82,000
34
6.5
Treated
effluent
200
140
810
4.1
Percent
removal
91
99
_b
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
Date: 6/23/80 II.6.1-94
-------
TABLE 6-104.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT 101, COLD ROLLING SUBCATE-
GORY, RECIRCULATING MILL SUBDIVISION [7]
Toxic pollutant
Concentration, p g/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Antimony
Cadmium
Chromium
Copper
Cyanide
Lead
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-Chlorophenol
2,4-Dimethylphenol
2-Nitrophenol
Pentachlorophenol
Phenol
4,6-Dinitro-o-cresol
Aromatics
Ethylbenzene
Toluene
150
45
6,500
7,500
11
1,600
1,800
36,000
25,000
70,000
ND
540
ND
390
110
300
20
1,200
65
90
ND
23
22
ND
ND
210
540
ND
10
60
Note: Dashes indicate negligible removal.
Blanks indicate no data available.
aTreated effluent concentration exceeds raw wastewater
concentration.
56
66
99
94
>99
>99
>9
97
45
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Methyl chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
110
80
1,200
420
ND
43
<10
16
<10
>99
46
>99
>99
Date: 6/23/80
II.6.1-95
-------
Direct Application Mills
Plant 105. This mill uses waste oil handling tanks and oil
skimming. Discharge from this process goes to central treat-
ment lagoons where additional oil and solids are removed.
Tables 6-105 and 6-106 present pollutant data for this facility.
TABLE 6-105. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 105,
COLD ROLLING SUBCATEGORY, DIRECT APPLICATION
MILL SUBDIVISION [7]
Raw wastewater flow: 0.49 m3/Mg
Treated effluent flow: 0.49 m3/Mg
Concentration, mg/La
Parameter
TSS
Oil and grease
PH
Dissolved iron
Raw
wastewater
290
1,900
7.2
23
Treated
effluent
300
1,400
3.3
170
Percent
removal
_b
26
_b
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
Combination Mills
Plant YY-Z. This facility uses primary settling, oil
skimming, chemical treatment, and final settling in a clarifier.
Other wastes are combined with cold mill wastes before being
treated in a central treatment system.
Conventional pollutant data are given in Table 6-107. No toxic
pollutant data are currently available on these mills.
II.6.3.20 Subcategory 20 - Hot Coating - Galvanizing [16]
Plant 111. In this plant wiper waters are collected and
recycled via hot rolling mills, with a small continuous bleed-
off to the treatment system. Pickling rinses and spent HC1
concentrations are combined with wastes from nail and fence
galvanizing, treated with lime, aerated, clarified and pressure-
sand filtered prior to discharge.
Date: 6/23/80 II.6.1-96
-------
TABLE 6-106.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR PLANT 105,
THE COLD ROLLING SUBCATEGORY DIRECT APPLICATION
MILL SUBDIVISION [7]
Toxic pollutant
Concentration, pg/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Silver
Zinc
Phenols
Phenols
Aromatics
1,2-Dichlorobenzene
1,3-Dichlorobenzene
16
30
140
170
240
15
420
350
26
180
200
53
11
17
290
31
200
240
450
13
600
500
76
250
680
54
ND
ND
a
'a.
'a
"a
•
a
13.
>99
>99
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 1-Dichloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
33
39
14
82
140
43
67
93
71
190
13
Note: Blanks indicate no data available.
aTreated effluent concentration exceeds raw wastewater
concentration.
Treatment influent and effluent pollutant concentrations are
given in Tables 6-108 and 6-109.
II.6.3.21 Subcategory 21 - Hot Coating-Terne Plating [9]
Plant 113
Wastewaters from this continuous terne plating line are currently
discharged without treatment. A combined chemical treatment
plant is currently under construction.
Date: 6/23/80
II.6.1-97
-------
TABLE 6-107. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT YY-2, COLD ROLLING SUBCATEGORY,
COMBINATION MILL SUBDIVISION [7]
Raw wastewater flow: 0.58 m3/Mg
Treated effluent flow: 0.58 m3/Mg
3
Concentration, mg/L
Parameter
TSS
Oil and grease
pH
Raw
wastewater
260
620
7.1
Treated
effluent
16
6
8.2
Percent
removal
94
99
aExcept pH values, given in pH units.
TABLE 6-108. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA
FOR PLANT 111, HOT COATING-GALVANIZING
SUBCATEGORY [9]
Raw wastewater flow: 5.9 m3/Mg
Treated effluent flow: 5.9 m3/Mg
Concentration, mg/La
Parameter
Oil and grease
pH
TSS
Hexavalent
chromium
Raw
wastewater
20
7.4
67
0.002
Treated
effluent
4
8.4
11
0.006
Percent
removal
80
84
_b
aExcept pH values, given in pH units.
Effluent concentration exceeds raw wastewater
concentration.
Raw wastewater concentrations are given in Table 6-110 and
6-111.
Date: 6/23/80 II.6.1-9!
-------
TABLE 6-109.
PLANT SPECIFIC TOXIC POLLUTANT DATA
FOR PLANT 111, HOT COATING-GALVANIZING
SUBCATEGORY [9]
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Die thy 1 phthalate
Dimethyl phthalate
Concentration, pg/L
Raw Treated
wastewater effluent
140
60
7
200
30
<20
3,200
86
ND
ND
ND
5
5
40
30
21
180
20
20
120
130
ND
18
ND
10
5
Percent
removal
71
50
_a
10
33
96
_a
_
_a
M
_a
—
Phenols
Pentachlorophenol
Aromatics
Benzene
1,3-Dichlorobenzene
Polycyclic aromatics
Fluoranthene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
1,1,1-Trichloroethane
Trichloroethylene
ND
ND
ND
ND
15
120
13
67
46
5
ND
10
5
21
ND
ND
10
a
a
67
83
>99
>99
78
Note: Blanks indicate no data available.
Dashes indicate negligible removal.
aTreated effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-99
-------
TABLE 6-110. PLANT SPECIFIC CONVENTIONAL POLLUTANT
DATA FOR PLANT 113, HOT COATING-TERNE
PLATING SUBCATEGORY [9]
Raw wastewater flow: 4.2 m3/Mg
Treated effluent flow: 4.2 m3/Mg
Concentration, mg/La
Parameter
Oil and grease
PH
TSS
Raw
wastewater
0
6.5
11
Treated
effluent
4
6.5
11
Percent
removal
_b
0
Hexavalent
chromium 0.002
aExcept pH values, given in pH units.
Treated effluent concentration exceeds raw
wastewater concentration.
II.6.3.22 Subcategory 22 - Combination Acid Pickling [8]
Batch Type
Plant 122-2. The pickling wastes from this plant are com-
bined with wastes from approximately 20 other sources and then
undergo equalization and neutralization, flocculation with
polymers, and clarification with oil skimming. Sludge formed in
the treatment process is dewatered in mechanical centrifuges.
The discharge from this system goes to a receiving stream.
Tables 6-112 and 6-113 present conventional and toxic pollutant
data for this facility.
Plant I. Plant I utilizes lime neutralization of spent
pickling solutions, mixing with acid rinses, and sedimentation
in a lagoon to treat wastewater generated by the strip pickling
process.
Conventional data for this plant are given in Table 6-114. No
toxic pollutant data were available for this plant.
Date: 6/23/80 II.6.1-100
-------
TABLE 6-111.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR PLANT
113, HOT COATING-TERN PLATING SUBCATEGORY [9]
Toxic pollutant
Concentration, pg/L
RawTreatedPercent
wastewater effluent removal
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver-
Thallium
Zinc
Phenols
2,4-Dichlorophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
p-Chloro-m-cresol
Aromatics
Benzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic aromatics
Acenaphthene
Anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Chrysene
Fluoranthene
Fluorene
Phenanthrene
Pyrene
<6
<2
<8
<80
700
40
3
670
0.7
230
2
25
50
93
3
7
11
3
3
7
0.003
3
3
7
3
7
3
3
3
7
7
3
7
7
8
700
40
3
670
0.1
590
25
93
85
(continued)
Date: 6/23/80
II.6.1-101
-------
TABLE 6-111 (continued)
Concentration, pg/L
RawTreatedPercent
Toxic pollutant wastewater effluent removal
Halogenated aliphatics
Chloroform 53
1,1-Dichloroethylene 3
1,2-rrans-dichlproethylene 9
Methylene chloride 830
Tetrachloroethylene 14
1,1,1-Trichloroethane 3
Pesticides and metabolites
Isophorone 3
Note: Blanks indicate no data available.
aNo organic sampling conducted.
Concentration level needs further evaluation.
TABLE 6-112. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 122-2,
COMBINATION ACID PICKLING SUBCATEGORY, BATCH-
TYPE SUBDIVISION [8]
Raw wastewater flow: 0.84 m3/Mg
Treated effluent flow: 1.30 m3/Mg
Concentration, mg/La
Parameter
TSS
Dissolved iron
Oil and grease
Fluoride
pH
Raw
wastewater
460
360
7
37
9
Treated
effluent
17
0.83
4.5
19
7.6
Percent
removal
96
99
35
49
aExcept pH values, given in pH units.
Date: 6/23/80 II.6.1-102
-------
TABLE 6-113.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 122-2, COMBINATION ACID PICKLING
SUBCATEGORY, BATCH-TYPE SUBDIVISION [8]
Toxic pollutant
Concentration, pg/L
Raw Treated Percent
wastewater effluent removal
Metals and inorganics
Arsenic
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
10
60,000
1,700
71
600
37,000
300
ND
180
50
35
50
,400
40
>99
99
97
51
92
96
87
Halogenated aliphatics
Chloroform
Tetrachloroethylene
20
24
<10 50
ND >99
Note: Blanks indicate no data available.
TABLE 6-114.
PLANT SPECIFIC POLLUTANT DATA FOR PLANT I,
COMBINATION ACID PICKLING SUBCATEGORY,
CONTINUOUS TYPE SUBDIVISION [8]
Raw wastewater flow: 7.6 m3/Mg
Treated effluent flow: 7.6 ms/Mg
Concentration, mg/La
Parameter
TSS
Fluoride
Nitrate
Oil and grease
Dissolved iron
PH
Copper
Chromium
Nickel
Zinc
Raw
wastewater
560
33
26
0.7
62
6.5
0.15
17.1
6.0
0.75
Treated
effluent
130
9.1
32
1.5
24
6.2
ND
1.8
5.2
0.24
Percent
removal
76
72b
~b
61
>99
89
13
68
^Except pH values, given in pH units.
Affluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-103
-------
II.6.3.23 Subcategory 23 - Scale Removal [9]
Kolene Scale Removal
Plant 131. Treatment at this plant consists of chromium
reduction, neutralization with lime and other wastes, settling in
a classifier, and final settling in a polishing lagoon. Sludges
generated are dewatered by vacuum filters.
Tables 6-115 and 6-116 give raw and treated wastewater pollutant
concentrations.
TABLE 6-115. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA FOR
PLANT 131, SCALE REMOVAL SUBCATEGORY, KOLENE
SCALE REMOVAL SUBDIVISION [9]
Raw wastewater flow: 0.75 m3/Mg
Treated effluent flow: 0.75 m3/Mg
Concentration, mg/La
Parameter
TSS
Hexavalent
chromium
pH
Raw
wastewater
120
120
12.6
Process
effluent
50
1
9.4
Percent
removal
58
99
Except pH values, given in pH units.
Hydride Scale Removal
Plant 132. This facility treats its wastewater by neutral-
ization, flocculation with polymers, and clarification with oil
skimming. The sludges are dewatered in cyclones.
Tables 6-117 and 6-118 present pollutant concentrations at this
facility.
II.6.3.24 Subcategory 24 - Continuous Alkaline Cleaning [9]
Mill 156
This mill utilizes a complex central treatment system. The
wastes from the alkaline cleaning line comprising less than 1%
of the total flow to the central treatment system. The alkaline
cleaning solutions and rinses are combined with wastes from
other sources and then undergo eguilization, neutralization, and
Date: 6/23/80 II.6.1-104
-------
TABLE 6-116.
PLANT SPECIFIC TOXIC POLLUTANT DATA FOR
PLANT 131, THE SCALE REMOVAL SUBCATEGORY,
KOLENE SCALE REMOVAL SUBDIVISION [9]
Concentration, gg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Nickel
Selenium
Thallium
Zinc
Raw
wastewater
21
30
140
370,000
130
770
27
65
180
Treated
effluent
200
<10
20
15,000
61
280
ND
50
34
Percent
removal
67
85
96
53
63
>99
23
81
Halogenated aliphatics
Chloroform
ND
140
aTreated effluent concentration exceeds raw wastewater
concentration.
TABLE 6-117. PLANT SPECIFIC CONVENTIONAL POLLUTANT DATA FOR
PLANT 132, SCALE REMOVAL SUBCATEGORY, HYDRIDE
SCALE REMOVAL SUBDIVISION [9]
Raw wastewater flow: 0.24 m3/Mg
Treated effluent flow: 0.24 m3/Mg
Concentration, mg/L
Parameter
TSS
Dissolved iron
PH
Raw
wastewater
490
0.45
12.4
Treated
effluent
17
0.83
7.6
Percent
removal
>99
_b
aExcept pH values, given in pH units.
Effluent concentration exceeds raw wastewater
concentration.
Date: 6/23/80
II.6.1-105
-------
TABLE 6-118.
PLANT SPECIFIC TOXIC METAL CONCENTRATION DATA
FOR PLANT 132, THE SCALE REMOVAL SUBCATEGORY,
HYDRIDE SCALE REMOVAL SUBDIVISION [9]
Toxic pollutant
Concentration, pg/L
RawTreatedPercent
wastewater effluent removal
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
<10
15,000
670
ND
25
8,700
20
75
<10
180 99
50 93a
35 "a
50 -a
1,400 84
20
40 47
Note: Blanks indicate not sampled
Dashes indicate negligible
.
removal .
aTreated effluent concentration exceeds raw
concentration .
wastewater
primary clarification in a thickener. From the clarifier the
wastes enter a high-density-sludge (HDS) unit where the solids
and metals are settled out. The overflow from the HDS unit is
then filtered. The filtrate is discharged to a final polishing
lagoon where additional settling and temperature equalization is
carried out prior to discharge to a receiving stream.
Pollutant concentrations for the raw and treated wastewater are
presented in Table 6-119.
II.6.4 Pollutant Removability [1-9]
The iron and steel industry generates a wide variety of waste-
waters from its subcategories. Pollutant concentrations and
waste loads differ significantly not only within the industry
but also within subcategories, creating problems in the selec-
tion of the treatment technology to be used. Central treatment
facilities often combine waste streams from several subcatego-
ries, increasing the selection dilemma. This stream combining
is a direct result of many subcategories being represented on a
single plant site.
Wastewater from this industry is generally low in organic con-
centrations due to the limited use of organic materials. Con-
centrations of these organics are generally less than 0.1 mg/L
and are often less than 0.01 mg/L. Only the byproduct recovery
cokemaking subcategory has concentrations that are usually
Date: 6/23/80
II.6.1-106
-------
TABLE 6-119. PLANT SPECIFIC POLLUTANT DATA FOR PLANT 156,
CONTINUOUS ALKALINE CLEANING SUBCATEGORY [9]
Raw wastewater flow: 0.28 m3/Mg
Treated effluent flow: 0.28 m3/Mg
Concentration,
Raw Etrluent
Parameter waste waste
TSS 11 1
Oil and grease 9.0 4.0
Dissolved iron 0.34 0.045
pH 7.7 7.5
Chromium 0.055 0.03
Lead 0.075 0.075
Zinc 0.30 0.13
Pentachlorophenol 0.029
aExcept pH values, given in pH units.
greater than this. This is the direct result of the recovery
of the organic byproducts. Biological treatment methods are
often used to reduce these toxic organic concentrations.
Metal concentrations in this industry vary considerably. Indi-
vidual subcategories may release significant concentrations of
particular metals used within their processes. An example of
this is the hot coating subcategories, which may release large
concentrations of lead, chromium, and zinc. Metal cocentrations
are generally reduced by settling, chemical addition, neutrali-
zation, or filtration.
Treatment technologies used in the iron and steel industry vary
between subcategories. However, several methods are more preva-
lent than others. Scale pits and settling ponds are used in
17 of the subcategories. This treatment is used at most facili-
ties because of the high concentration of solids normally
present in the wastewater. Clarification and sludge thickening
are also used to reduce the solids concentration and volure.
Chemical addition is used both as a pH adjustment and as ;-.
flocculant aid. Common chemicals used include lime, polymers,
alum, and ferric sufate. Dissolved metals may be precipitated
with this treatment method, reducing the metal concentration in
the final effluent.
Filtration is also a common treatment method that may be used as
a solids removal mechanism or as a sludge thickening process.
Several filtration methods are currently in use including pres-
sure, sand, deep bed, and vacuum filters.
Date: 6/23/80 II.6.1-107
-------
Recycling of treated water is a very common practice in this
industry. Twenty-three of twenty-four subcategories studied
used this technology to reduce effluent volume and control cost.
Nine subcategories have facilities practicing 100% recycle, and
several other subcategories recycle over 80% of their fume
scrubber and rinsewater streams. Wastewater is generally treat-
ed in some manner before recycling.
Generally, more than one technology is used at each facility.
Settling is normally a preliminary step to another treatment
method and may also be present more than once in a treatment
scheme. Chemical addition and filtration treatments are often
used in conjunction with other treatment technologies.
Table 6-120 presents treatment technologies currently used in
this industry, by subcategory. The data are based on available
information from 308 questionnaires and from plant sampling
visits in each subcategory.
Removal efficiency data may be found in the wastewater charac-
terization section (II.6.2) and in the plant specific section
(II.6.3) of this industry description.
Date: 6/23/80 II.6.1-108
-------
o
ft)
ft
(D
TABLE 6-120.
TREATMENT TECHNOLOGIES CURRENTLY IN USE IN THE
IRON AND STEEL INDUSTRY [1-9]
Subcategory number
O
-------
II.7 LEATHER TANNING AND FINISHING INDUSTRY
II.7.1 INDUSTRY DESCRIPTION
II.7.1.1 General Description [1]
The leather tanning and finishing industry in the United States
is included within the U.S. Department of Commerce, Bureau of
Census Standard Industrial Classification (SIC) Code 3100,
Leather and Leather Products. The part of the industry discussed
in this report is identified as SIC 3111, Leather Tanning and
Finishing.
Leather tanning is a general term encompassing the numerous
processing steps included in converting animal skins or hides
into leather. There are three primary hide or skin types used
to manufacture leather, namely, cattle hides, sheepskins, and
pigskins. Other skins utilized in smaller quantities include
goatskin, horse hide, deerskin, and elkskin.
There are approximately 188 tanneries producing leather products
in the United States. These tanneries are located in four
general regions: the New England states, the Mid-Atlantic
states, the Midwest, and the Pacific Coast. Of these, about
75% are privately owned.
Table 7-1 summarizes pertinent information regarding the total
number of subcategories, the number of subcategories studied by
the Effluent Guidelines Division, and the number and type of
dischargers in the leather tanning and finishing industry.
TABLE 7-1. INDUSTRY SUMMARY [1, 2]
Industry: Leather Tanning and Finishing
Total Number of Subcategories: 9
Number of Subcategories Studied: 7
Number of Dischargers in Industry:
Direct: 18
Indirect: 170
Zero: 1
Date: 6/23/80 II.7-1
-------
Best practicable technology (BPT) limitations for the seven
categories are listed in Table 7-2.
TABLE 7-2. BPT LIMITATIONS FOR THE LEATHER TANNING
AND FINISHING INDUSTRY [1]
(kg/Mg)
Subcategory
Daily
maximum
30-day
average
Daily
maximum
30-day
average
BODS
TSS
Hair pulp/chrome tan/retan-wet finish
Hair save/chrome tan/retan-wet finish
Hair save/nonchrome tan/retan-wet finish
Retan-wet finish
No beamhouse
Through-the-blue
Shearling
7.
8.
6.
2.
5.
4.
20.
0
2
0
6
0
0
8
3
4
3
1
2
2
10
.5
.1
.0
.3
.5
.0
.4
11.
13.
9.
4.
8.
6.
33.
2
4
6
2
0
6
6
5
6
4
2
4
3
16
.6
.7
.8
.1
.0
.3
.8
Total chromium
Oil and grease
pH
Hair pulp/chrome tan/retan-wet finish
Hair save/chrome tan/retan-wet finish
Hair save/nonchrome tan/retan-wet finish
Retan-wet finish
No beamhouse
Through- the-blue
Shearling
0
0
0
0
0
0
0
.24
.28
.20
.086
.17
.14
.70
0
0
0
0
0
0
0
.12
.14
.10
.043
.083
.07
.35
2.
2.
1.
0.
1.
1.
5.
0
2
7
70
4
1
8
1
1
0
0
0
0
2
.0
.1
.83
.35
.69
.56
.9
6
6
6
6
6
6
6
.0
.0
.0
.0
.0
.0
.0
- 9.0
- 9.0
- 9.0
- 9.0
- 9.0
- 9.0
- 9.0
In pH units.
11.7.1,2 Subcategory Description
The primary criteria for subcategorizing the leather tanning and
finishing industry are (1) the type or condition of animal hide
processed, (2) the method of hair removal, (3) the type of tan-
ning agent used, and (4) the extent of finishing performed. Also
taken into consideration are plant size, age, location, waste-
water characteristics, and water usage.
The seven subcategories that were derived, based on the above
criteria, are defined as follows:
1. Hair pulp/chrome tan/retan-wet finish - facilities that
primarily process raw or cured cattle or cattle-like hides into
finished leather by chemically dissolving the hair (hair pulp);
tanning with chrome; and retanning and wet finishing.
2. Hair save/chrome tan/retan-wet finish - facilities that
primarily process raw or cured cattle or cattle-like hides into
finished leather by chemically loosening and mechanically remov-
ing the hair; tanning with chrome; and retanning and wet
finishing.
Date: 6/23/80
II.7-2
-------
3. Hair save/nonchrome tan/retan-wet finish - facilities that
process raw or cured cattle or cattle-like hides into finished
leather by chemically loosening and mechanically removing the
hair; tanning, primarily with vegetable tannins, alum, syntans,
oils, or other chemicals; and retanning and wet finishing.
4. Retan-wet finish - facilities that process previously
unhaired and tanned hides or splits into finished leather through
retanning and wet finishing processes including coloring, fat-
liquoring, and mechanical conditioning.
5. No beamhouse - facilities that process previously unhaired
and pickled cattle hides, sheepskins or pigskins into finished
leather by tanning with chrome or other agents, followed by
retanning and wet finishing.
6. Through-the-blue - facilities that process raw or cured
cattle or cattle-like hides into the blue-tanned state only, by
chemically dissolving or loosening the hair and tanning with
chrome, with no retanning or wet finishing.
7. Shearling - facilities that process raw or cured sheep or
sheep-like skins into finished leather by retaining the hair on
the skin; tanning with chrome or other agents; and retanning
and wet finishing.
The following paragraphs discuss the subcategory processes in
detail.
Hair Pulp/Chrome Tan/Retan-Wet Finish
Tanneries in this subcategory primarily process brine-cured or
green salted cattle hides into finished leather. Various amounts
of water are used in performing the three wet processing opera-
tions, namely, beamhouse, tanyard, and retan-wet finish. Water
use for individual subprocesses typically employed is described
in the following paragraphs.
Soak and Wash. The purpose of this operation is to remove
salt, restore the moisture content of the hides, and remove any
foreign material such as dirt and manure. Brine-cured hides are
soaked and washed simply to remove salt, while green salted hides
require the removal of manure and dirt as well as salt. The
quantity of manure and dirt varies with the season of the year
and the origin of the hide. Industry data estimate the waste-
water volume from this subprocess to be about 20% of the total
wastewater flow.
Date: 6/23/80 II.7-3
-------
Fleshing. Fleshing follows the soak and wash operation if
this was not done previously. Fleshings are isolated as a solid
waste and, when handled properly, do not make a significant
contribution to the total waste loads of a cattle hide tannery.
Unhairing. Pulping to remove hair involves the addition of
lime and sharpeners (e.g., sodium sulfhydrate) in relatively
high concentrations. The process dissolves the proteinaceous
hair enough to dissipate it in the unhairing solution. As
reported by various tanneries, this segment of beamhouse opera-
tions generates between 20 and 38% of the total tannery flow, an
average of 32% for those facilities reporting such information.
Bating and Pickling. The bating subprocess delimes, reduces
swelling, peptizes the fibers, and removes protein degradation
products. Major chemical additions are ammonium sulfate to
reduce pH to an acceptable level and enzyme to condition the
protein matter.
Following the bating process, hides are prepared for tanning by
pickling. Pickling solutions contain primarily sulfuric acid and
salt, although small amounts of wetting agent and biocide are
sometimes added. Since protein degradation products, lime, and
other waste material are removed through bating, the quantities
of BOD5, suspended solids, and nitrogen are relatively low.
Principal waste constituents are the acid and salt. Bate and
pickle wastewater volumes, reported as a combined total by
several tanneries, range from 9 to 50% of the plant flow and
average 26% for the combined process flow.
Tanning. Chrome tanning employs a chromium sulfate or a
chrome tanning solution as the tanning agent. Other chemical
additives include sodium formate and soda ash. The chromium
must be in the trivalent form and must be dissolved in an acidic
medium to accomplish desired results.
For those plants reporting data, the median and average flows
associated with the tanning process were found to be 4.4 and
6.6% of total plant water use.
Retanning, Coloring and Fatliquoring. The chrome-tanned
hides normally remain in the same drums for these three subproc-
esses. Retanning increases the penetration of tanning solution
into the hides after splitting and uses either chrome, vegetable,
or synthetic tanning agents. Because retanning uses lower con-
centrations of chemicals, the wastewater strength is not high and
does not represent a significant portion of the total waste flow.
Date: 6/23/80 II.7-4
-------
The most variable process in the tannery is coloring. There are
hundreds of different kinds of dyes, both synthetic and vegetable
based. Synthetic dyes are the most widely used in the industry
and usually require the addition of acid to facilitate dye up-
take in the leather. The fatliquoring operation can be performed
either before or after coloring. Ultimate use of the leather
product dictates the type and amount of oil required for this
subprocess.
Drying by the pasting method requires a small amount of water,
first to prepare the mixture and then to wash it off. Even
though the volume is very small, pollutants associated with the
starch can be present in relatively high concentrations. Several
tanneries report the reuse of paste mixtures, which minimizes the
amount of material entering the waste stream.
Process effluent from wet finishing (retan, color, and fatliquor-
ing) is considered high-volume, low-strength wastewater, compared
to the waste streams associated with beamhouse and tanyard opera-
tions. Because wet finishing imparts color to the process water,
recycling is not normally practiced. The wastewater volumes from
the combined subprocesses, reported as a percentage of total
tannery flow, are highly variable, ranging from 12 to 30%.
Finishing. Because leather finishing operations are
basically dry, they contribute the lowest wastewater flow of any
tannery process. There is some wet processing, such as wetting
the hides to facilitate handling in the staking or tacking opera-
tions, but most leather finishers do not have a contaminated
discharge resulting from their processing activities.
Hair Save/Chrome Tan/Retan-Wet Finish
In the hair save unhairing operation, the hair is loosened for
subsequent machine removal. The depilatory chemicals utilized
are the same as those characteristic of hair pulping, but are
present in lower concentrations.
The second step in the hair save operation is machine removal of
hair from the hide. Removed hairs require washing only if they
are to be baled and sold; otherwise they are handled as solid
wastes.
The average water consumption of hair save operations is
approximately 20% greater than for hair pulp tanneries. The
higher water use is associated with machine removal and washing
of the hair.
Hair Save/Nonchrome Tan/Retan-Wet Finish
The principal difference between this subcategory and the pre-
vious one is the tanning operation. Cattle hides leaving the
Date: 6/23/80 II.7-5
-------
beamhouse are bated and pickled in a similar manner but are
tanned with such agents as alum, zirconium, and other metal
salts, as well as syntans, gluteraldehyde, and formaldehyde.
Vegetable tannings accomplish the major portion of nonchrome
tanning.
Spent solutions from the vegetable tanning process are quite
different from chrome solutions. The reaction rate of vegetable
tannings with the hides is much slower than that associated with
chrome. Because of the longer contact time, the process nor-
mally proceeds in vats with some type of gentle agitation. Proc-
ess solution conservation is prevalent due to the cost of these
tanning agents.
Retan-Wet Finish
These tanneries receive previously tanned hides or splits for
retanning and finishing. Either chrome, vegetable, or synthetic
tanning agents can be used for retanning. Wastewater sources
for the wet finishing steps are coloring, fatliquoring, and
drying. Without the beamhouse and tanyard operations, flow and
waste loads per unit of production decrease. The average flow
for a retan-wet finish facility is less than one-half of the
volume characteristic of tanneries with beamhouse and tanyard
processes.
No Beamhouse
These tanneries primarily include plants that tan unhaired pig-
skins and pickled sheepskins. They may also receive pickled and
unhaired cattle hides, which are subjected to tanyard and retan-
wet finish processes.
Unhaired, pickled sheepskins require fleshing if this has not
previously been done. Previously fleshed skins usually require
refleshing after tanning. Pigskins are not subjected to this
operation.
Grease removal is necessary for both sheepskins and pigskins and
follows the soak and wash step. Utilizing the same drums,
degreasing proceeds by one of two methods: (1) hot water with
detergent, or (2) solvent addition. In either case, the grease
is separated and recovered as a by-product having some commercial
value. For pigskins, the total amount of grease removed from the
skin can approach 10% of the skin weight. The quantity entering
the waste stream is usually a small part of the total. In
solvent degreasing, the solvent is recovered for reuse. BOD5,
COD, and suspended solids are other constituents in waste streams
generated by this operation.
Date: 6/23/80 11.7-6
-------
Prior to tanning pigskins, the tanneries must remove the embedded
portion of the hair from the skins. The pickling step follows to
prepare the skins for tanning.
Sheepskins and pigskins may be tanned with chrome or vegetable
tannins, although the majority of tanneries utilize the chrome
tanning method. The conventional practice is to tan pigskins
completely, thus eliminating the need for a retan operation.
Tanned sheepskins are retanned in a manner similar to cattle
hides. The wet finishing operations for both types of skins are
equivalent to those previously described.
Elimination of the beamhouse results in lower average flow and
waste loads per unit of production than is typical; however, the
no-beamhouse segment generates higher flows and waste loads than
tanneries which only retan and wet finish.
Through-the blue
Facilities in this segment process raw or cured cattle hides
through the blue-tanned state only. The remaining steps to
produce finished leather are performed by other tanneries.
Unhairing of the hides may use either the hair pulp or the hair
save method. Hair pulping results in the higher waste loads,
while hair save uses more water. Following bating and pickling,
the unhaired hides are chrome tanned to the blue stage.
Average wastewater flows for through-the-blue tanneries are
lower than those for no-beamhouse tanneries, but greater than for
facilities that only retan and wet finish.
Shearling
Tanneries in this subcategory process raw or cured sheepskins
into finished leather with the hair (wool) intact. The major
processing operations include tanyard and retan-wet finish.
Prior to the tanning operation, the skins are soaked and washed
to cleanse them of foreign matter. This step requires a sub-
stantial amount of water for shearlings. The shearling hides
are fleshed after washing. Degreasing follows, using either of
the two methods described in the no-beamhouse subcategory; how-
ever, grease recovery is not normally practiced by shearling
tanneries.
Unlike unhaired sheepskins, shearling hides are pickled in the
manner characteristic of cattle hide processing, i.e., prior to
tanning. They do not, however, require liming and bating. Tan-
ning may be accomplished with chrome or vegetable tannins,
Date: 6/23/80 II.7-7
-------
although the chrome method is generally preferred. The retanning
and wet finishing steps for shearlings follow.
Because shearling hides are processed with the hair intact, aver-
age water consumption is more than four times the volume per unit
of production observed for the no-beamhouse process, which
essentially employs the same processing steps.
II.7.1.3 Wastewater Flow Characterization
The volume of water utilized in the leather tanning and finish-
ing industry fluctuates. Processing techniques within each
subcategory of the industry may differ from tannery to tannery.
Most tanneries have combined processes that fall under several
different subcategories, and all process wastewater is generally
discharged to a common sewer. Wastewater flows are tabulated in
Table 7-3.
TABLE 7-3. SUMMARY OF SUBCATEGORY FLOWS [1]
Subcategory
Hair pulp/chrome tan/retan-
wet finish
Hair save/chrome tan/retan-
wet finish
Hair save/nonchrome tan/
retan-wet finish
Retan-wet finish
No beamhouse
Through- the-blue
Shearling
Total number
of plants
reporting flow
31
12
16
8
14
2
3
Total number
Average operating below
flow, L/kg average flow
38
46
33
14
28
23
116
16
6
8
4
7
1
2
II.7.2 WASTEWATER CHARACTERIZATION [1]
Water is used extensively in the leather tanning and finishing
industry. Some of its purposes for use are listed below:
(1) for soaking and washing unprocessed hides.
(2) as a medium which allows chemicals to react with
hides/skins.
(3) as a carrier for dyes and pigments which impart the
desired color to the final product.
(4) for cleaning processing areas and equipment.
II.7.2.1 Hair Pulp/Chrome Tan/Retan-Wet Finish
The primary constituents of the soak and wash waste stream are
BOD5, COD, suspended solids, and dissolved solids. For a cattle
hide tannery with this operation preceding hair pulping and
chrome tanning, typical ranges for BOD5 and suspended solids
range from 7 to 22 and 8 to 43 kg/Mg of hide (lb/1,000 Ib of
Date: 6/23/80 II.7-8
-------
hide), respectively. Because the incoming hides are generally
either brine-cured or green-salted, the salt must be removed
in preparation for unhairing. This removal results in relatively
high total solids values, ranging from 143 to 267 kg/Mg of hide
(lb/1,000 Ib of hide).
The liming and unhairing process is one of the principal contrib-
utors to the plant effluent. Spent unhairing liquors contain
very high concentrations of proteinaceous organic matter, dis-
solved and suspended inorganic solids, and sulfides (mostly in
the dissolved form) in a highly alkaline solution. Most sul-
fides found in tannery wastewater come from spent unhairing
liquors, although some potentially significant amounts, depend-
ing upon the specific processes and formulations, carry over
into spent tanning and retanning liquors. The BOD5 content of
the waste from this operation may range from 53 to 67 kg/Mg of
cattle hide processes. Concurrently, the estimated total nitro-
gen levels range from 11 to 15 kg/Mg (lb/1,000 Ib) of raw
material.
In the bating of unhaired hides, lime reacts with ammonium sul-
fate to produce calcium sulfate, which enters the plant effluent.
The total nitrogen content of the waste stream varies from 5 to
8 kg/Mg of hide, with ammonia constituting two-thirds. The
pickling step which follows generates relatively low levels of
pollutant including BOD5, suspended solids, and nitrogen.
The chrome-tanning operation generates signficant wastes because
it is the major source of chromium in the total plant effluent;
however, the organic content of the spent tanning solution,
including BOD5 and suspended solids, is generally low.
The wet finishing operations, which include retanning, coloring
and fatliquoring, generate high-volume, low-strength wastewaters
compared to the effluents from beamhouse and tanyard processes.
The temperature of the retan, color, and fatliquor waste streams
is high, typically exceeding 37.7°C (100°F). Use of high temper-
atures in retanning ensures maximum chromium uptake, thereby
reducing its discharge to the total waste stream.
Since this subcategory represents the largest portion of the
leather tanning industry, considerable data are available for
characterizing its wastewaters, particularly for classical param-
eters. Table 7-4 summarizes the classical parameters which were
employed to characterize the raw loads associated with this
industry segment. The values for the selected wastewater
constituents represent subcategory averages. Table 7-5 summa-
rizes the toxic pollutant present. Constituents are character-
ize by pollutant type, times found, and concentration.
Date: 6/23/80 II.7-9
-------
TABLE 7-4. WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HAIR PULP/CHROME TAN/
RETAN-WET FINISH SUBCATEGORY [1]
Pollutant
Number of
data points
Concentration, mg/L
Range of
individual
data points Mean
BOD 5
COD
TSS
TKN
Total phenols
Sulfides
Oil and grease
Total chromium
Ammonia
205
170
210
58
15
170
75
180
168
210
180
25
90.0
0.140
0.800
15
3.00
17.0
- 4,300
- 27,000
- 36,000
- 630
- 110
- 200
- 10,000
- 350
- 380
1,600
4,600
2,400
330
1.0
64
400
76
100
II.7.2.2 Hair Save/Chrome Tan/Retan-Wet Finish
The principal difference between this subcategory and the pre-
vious one is the method of removing hair from cattle hides.
Although water use is greater for machine removal and washing of
hair, the waste loads associated with the hair save process are
substantially less than those for hair pulp operations. The
proteinaceous hair does not dissolve totally in the unhairing
solution for the hair save process. This results in a lower
BOD5 content in the waste stream, ranging from 17 to 58 kg/Mg
of raw material. The total nitrogen and sulfide content also
decrease correspondingly. The remaining tannery operations
essentially are the same as for subcategory one, thereby
contributing similar waste loads.
Tables 7-6 and 7-7 summarize the raw wastewater characteristics
for this subcategory in terms of classical parameters and toxic
pollutants. Classical pollutants have been normalized based on
production and are presented as subcategory averages.
II.7.2.3 Hair Pulp/Nonchrome Tan/Retan-Wet Finish
The tanning of cattle hides by nonchrome methods distinguishes
this segment from the previous one. The most significant
difference between the raw waste loads of the two subcategories
occurs in the total chromium content. The use of nonchrome
tanning agents reduces the average chromium level. The small
amount of chromium present in the effluent from nonchrome
tanneries, generally originates in the retanning operations
which may require chromium salts.
Date: 6/23/80
II.7-10
-------
TABLE 7-5. WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR THE HAIR PULP/CHROME
TAN/RETAN-WET FINISH SUBCATEGORY [1]
Toxic pollutants
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Ethers
Bis(2-chloroisopropyl ) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 , 2-Diphenylhydrazine
N-nitrosodiphenylaroine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Peiitachlorophenol
Phenol
2,4, 6-Ti ichlorophenol
Aromat ics
Benzene
ChLorobenzene
1 , 2-Dichlorobenzene
1 . 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitiobenzene
Toluene
1 , 2 , 4-Trichlorobenzene
Number
of
samples
3
3
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Number
detected
3
3
2
3
3
3
1
1
1
1
3
2
3
1
1
2
1
3
Concentration, ug/L
Range Mean
43,000 - 160,000 80,000
50 - 380 173
20 - 60 40
1, 100 - 2,400 1,700
20 - 60 40
200 - 580 430
ND
51
ND
ND
ND
120
27
ND
ND
ND
ND
Present
ND
3,000 - 4,000 3, 700
880 - 5,900 3,400
10 - 20 15
ND
260
ND
54
88 88
ND
430
150 - 400 280
ND
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated aliphatics
Chi orodibromome thane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1 , 2-Dichloroethane
1 , 2-frans-dichloroethylene
1,1,2,2 -Tetr achloroethane
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Tnchlorof luoromethane
Pesticides and metabolites
Chlordane
Isophorone
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
1
2
1
1
3
1
1
1
1
1
32
16
ND
ND
ND
24 - 67 46
94
ND
ND
20
10 10
20
ND
30
10
Present
10
ND
ND
ND
Note: ND = not detected.
Date: 6/23/80
II.7-11
-------
TABLE 7-6.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE HAIR SAVE/CHROME TAN/
RETAN-WET FINISH SUBCATEGORY fl]
Pollutant
BOD.
COD
TSS
TKN
Total phenols
Suif:deE
Oil and grease
Total chromium
Ammonia
Number of
data points
101
30
62
56
24
70
30
56
31
Concentration,
Range of
individual
data points Me
140 - 2,800
700 - 5,700 2
94.0 - 8,600 • 1
63 0 - 3,600
0 440 - 6.80
0.030 - 300
49.0 - 620
0 006 - 390
0 400 - 660
S57T-
an
980
,600
,900
140
2 2
20
240
3 I
90
TABLE 7-7.
WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR THE HAIR SAVE/CHROME
TAN/RETAN-WET FINISH SUBCATEGORY [1]
NUBbef
of
Toxic pollutants Banples
Metals and inorganics
Chromiua
Cyanide
Lead
Nickel
Zinc
Ethers
Bis(2-chloroisopropyl) ether
Phthalatec
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 , 2-Dlphenylhydrazine
N-nitrosodlphenylaaune
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
2 ,4,6-Trichlorophenol
Aromatics
Benzene
Chlorobenzene
1 , 2-Dlchlorobenzene
1 , 3-Dlchlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1,2, 4-Tnchlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated aliphatics
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1, 2-Dlchloroethane
1,1,2, 2-Tetrachloroe thane
1,1, 1-Trichloroethane
1 , 1,2-Tnchloroe thane
Trichlorof luorome thane
Pesticides and metabolites
Chlordane
Isophorone
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Number
detected
2
2
2
2
2
1
1
1
2
1
1
1
1
2
1
1
1
1
2
1
Concentration, ug/L
Range Mean
31,000 - 150,000 90,500
20 - 50 35
100 - 1,300 700
5-40 22
240 - 400 315
ND
32
ND
ND
ND
ND
ND
ND
ND
ND
114
ND
6,200
252 - 5,500 2,900
4,800
10
10
ND
ND
ND
150
ND
ND
10 - 150 BO
ND
ND
ND
ND
2
ND
49
56
1
10 - 41 26
ND
ND
ND
ND
10
ND
ND
ND
ND
ND = not detected.
Date: 6/23/80
II.7-12
-------
Lesser variations occur for the classical parameters, such as
BOD5 and suspended solids. Table 7-8 presents these values
along with the waste loads for chromium and phenols. Table 7-9
summarizes the presence of other toxic pollutants and their
respective levels for hair pulp/nonchrome tan/retan-wet finish
tanneries.
TABLE 7-8.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE NONCHROME TAN/RETAN-WET
FINISH SUBCATEGORY [1]
Concentration, mg/L
Number of
Range of
individual
Pollutant data points data points
BOD5
COD
TSS
TKN
Total phenols
Sulf ides
Oil and grease
Total chromium
Ammonia
48
40
55
21
16
29
32
30
20
1.00
1,100
28.0
130
0.280
0.100
2.00
0.250
23
- 7,800
- 75,000
- 8,200
- 1,200
- 100
- 330
- 1,300
- 110
- 680
Mean
1,200
5,100
1,700
200
1.2
68
340
11
90
Tables 7-10 and 7-11 characterize the tannery wastewaters for
conventional and toxic pollutants, respectively.
II.7.2.4 Retan-Wet Finish
The tanneries in this industry segment limit their operations to
retan and wet finish hides or splits that have been unhaired and
tanned. The absence of the beamhouse process results in lower
organic and sulfide loadings for this subcategory.
II.7.2.5 No Beamhouse
These tanneries consist only of tanyard and retan-wet finish
operations with no beamhouse. Since unhairing operations are
absent from these tanneries, the raw waste loads, including
BOD5, suspended solids and sulfide, are lower. Tanyard opera-
tions increase conventional pollutant levels beyond those typical
for strictly retan-wet finish facilities. Tables 7-12 and 7-13
present the average values for conventional and toxic pollutants
in no-beamhouse tanneries.
II.7.2.6 Through-the-Blue
Hair removal and chrome tanning of cattle hides are the basic
operations of the through-the-blue tanneries. Relatively high
organic loads, as well as the nitrogen and sulfide contents,
reflect beamhouse operations; total chromium levels result from
Date: 6/23/80
II.7-13
-------
TABLE 7-9. WASTEWATER CHARACTERIZATION OF TOXIC
POLLUTANTS FOR THE NONCHROME TAN/
RETAN-WET FINISH SUBCATEGORY [1]
Toxic pollutants
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Ethers
Bis(2-chloroisopropyl ) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 , 2-Dipheny Ihydrazine
N-nitrosodiphenylamine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
Aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1,2, 4-Tr ichlorobenzene
Number
of
samples
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated aliphatics
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1, 2-Dichloroe thane
1 , 2-rrans-dichloroethylene
1,1,2 , 2-Tetrachloroe thane
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1, 2-Tr ichloroethane
Trichloroethylene
Trichlorofluorome thane
Pesticides and metabolites
a-BHC ,
p-BHC !
Chlordane
Isophorone
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
Number Concentration, pg/L
detected Range Mean
4 430 - 10,000 5,100
4 100 - 740 380
2 60 - 100 80
4 100 - 200 140
4 40-95 61
4 300 - 700 490
ND
ND
ND
1 Present
1 Present
ND
ND
ND
ND
ND
ND
ND
2 10 - 2,900 1,500
4 51 - 25,000 9,000
3 10-10 10
ND
3 49 - 200 126
ND
3 19-20 20
3 10 - 120 58
ND
ND
4 10-15 12
ND
ND
ND
ND
ND
ND
3 6-59 32
1 8
ND
1 24
1 10
ND
ND
ND
1 10
1 23
ND
ND
ND
ND
ND
ND
ND
Note: ND = not detected.
Date: 6/23/80
II.7-14
-------
TABLE 7-10.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUT-
ANTS FOR THE RETAN-WET FINISH SUBCATEGORY [1]
TABLE 7-11.
Number of
Pollutant data points
BOD5 30
COD 9
TKN 9
Total phenols 8
Sul fides 7
Oil and grease 29
Total chromium 24
Ammonia 9
Concentration
Range of
individual
data points
200 - 1,600
1,200 - 4,800
110 - 480
0.230 - 17.0
0.160 - 2.40
58 - 850
1.60 - 380
58.0 - 160
WASTEWATER CHARACTERIZATION OF
FOR THE RETAN-WET
Number
of
Toxic pollutant! samcles
Metals and inorganics
ChroBiua 3
Copper 3
Cyanide 2
Lead 3
Nickel 3
Zinc 3
Ethers
Bis(2-chloroisopropyl ) ether 3
Phthalatee
Bi>(2-ethylhexyl) phthalate 3
Butyl benzyl phthalate 3
Di-n-butyl phthalate 3
Olethyl phthalate 3
Dimethyl phthalate 3
Nitrogen compounds
Benzidine 3
3, 3 '-Dichlorobenzidine 3
1,2-Diphenylhydrazine 3
N-nitrosodlphenylamine 3
Phenol!
2, 4-Dichlorophenol 3
2,4-Dinethylphenol 3
Pentachlorophenol 3
Phenol 3
2 .4, 6-Tnchlorophenol 3
Aromatic*
Benzene 3
Chlorobenzene 3
1 , 2-Dichlorobenzene 3
1 , 3-Oichlorobenzene 3
1 , 4-Dichlorobenzene 3
Ethylbenzene 3
Hexachlorobenzene 3
Nitrobenzene 3
Toluene 3
1. 2,4-Trichlorobenzene 3
Polycyclic aromatic hydrocarbon!
Acenaphthene 3
Acenaphthylene 3
Chrysene 3
Fluoranthene 3
Fluorene 3
Naphthalene 3
Fhenanthrene/anthracene 3
Pyrene 3
Haloaenated aliphatic!
chloroform 3
Dichlorobromomethane 3
1, 1-Dichloroe thane 3
1,2-Dichloroethane 3
1.2-rrans-dichloroethylene 3
1, 1,2,2-Tetrachloroethane 3
Tetrachloroethylene 3
1, 1, 1-Trichloroethane 3
1,1.2-Trichloroethane 3
Trichloroethylene 3
Tnchlorofluoromethane 3
Peiticidea and metabolites
o-BHC ,
S-BHC ' 3
chlordane 3
Isophorone 3
TCDD 3
, mq/L
Mean
780
3,100
210
3.9
1.1
270
53
110
TOXIC POLLUTANTS
FINISH SUBCATEGORY [1]
Number Concentration, uo/L
detected Ranae M«ar*
3 16.000 - 130,
3 160 - 330
1
000 89,000
250
in
3 100 - 3,500 1.300
3 6-100
3 150 - 280
1
1
1
2 3,200
2 570
2
3 10 - 150
3 10 - IX
1
1
2 110 - 140
2 10-10
1
45
198
ND
ND
ND
Present
Present.
ND
ND
ND
ND
250
ND
ND
ND
3 , 200
570
10
ND
ND
ND
ND
80
ND
ND
10
ND
Present
ND
ND
ND
ND
120
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Note- ND = not detected.
Date: 6/23/80
II.7-15
-------
TABLE 7-12.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUT-
ANTS FOR THE NO BEAMHOUSE SUBCATEGORY [1]
Concentration, mq/L
Pollutant
BOD 5
COD
TSS
TKN
Total phenols
Sulfides
Oil and grease
Total chromium
Ammonia
Number of
data points
130
64
124
12
20
13
32
66
22
Range of
individual
data points
20 - 20,000
140 - 38,000
120 - 37,000
22.0 - 160
0.112 - 9.90
0.090 - 6.40
85.0 - 1,200
2.80 - 1,900
6.20 - 99.0
Mean
1,000
1,700
632
168
1.2
3.2
340
68
36
TABLE 7-13.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOR THE NO BEAMHOUSE SUBCATEGORY [1]
Toxic pollutants
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Number
of
samples
3
3
3
3
3
3
Number
detected
3
3
3
3
3
Concentration,
Range
16.000 - 170,000
140 - 260
60 - 1,600
6-30
96 - 2,600
U9/L
Mean
74.000
190
ND
790
15
1,000
Ethers
Bis(2-chloroi«opropyl) ether
Phthalates
BiE(2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Dl-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 . 2-Diphenylhydrazine
N-mtrosodiphenylaaine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Penatchlorophenol
Phenol
2,4, 6-Tnchlorophenol
Aromatics
Benzene
Chlorobenzne
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzenc
Hexachlorobenzene
Ni trobenzene
Toluene
1,2, 4-Tnchlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluor an thene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated allphatics
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1 , 2-Dichloroethane
1 , 2-7"rans-dichloroethylene
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Tnchloroethane
1,1. 2-Tnchloroe thane
Tnchloroethylene
Trichlorof luorome thane
Pesticides and metabolites
o-BHC ,
B-BHC '
Chlordane
Isophorone
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2 3,400 - 3,700 3,600
1 6,200
3 2,400 - 4,200 3,300
2 10 - 150 80
ND
1 36
ND
1 13
2 10 - 150 80
ND
ND
2 10 - 150 80
ND
ND
ND
ND
ND
ND
2 5-49 27
2 111 - 130 120
ND
3 2-16 10
1 10
ND
ND
ND
ND
1 40
ND
ND
1 10
ND
ND
ND
ND
not dct ected
Date: 6/23/80
II.7-16
-------
chrome tanning procedures. Average raw waste loads for the major
parameters are presented in Table 7-14. Table 7-15 identifies
the toxic pollutants and their respective concentrations.
TABLE 7-14. WASTEWATER CHARACTERIZATION OF
CONVENTIONAL POLLUTANTS FOR THE
THROUGH-THE-BLUE SUBCATEGORY [1]
Pollutant
BOD5
COD
TSS
TKN
Total phenols
Sulfides
Oil and grease
Total chromium
Ammonia
Number of
data points
8
5
8
5
1
4
9
4
4
Concentr ati onj
Range of
individual
data points
1,300 - 11,000
10,500 - 33,000
1,200 - 14,000
960 - 1,800
9.60
137 - 680
67.0 - 6,200
230 - 400
400 - 610
, mg/L
Mean
2,500
6,400
3,900
118
560
100
dMean reported in reference was outside range of data.
II.7.2.7 Shearling
Tanneries in this subcategory tan and wet finish sheepskins with
wool intact. Subprocessing operations eliminate the need for a
beamhouse; however, the amount of foreign matter which must be
removed from the wool creates higher organic waste loads than
those of no-beamhouse tanneries. The absence of grease recovery
during the degreasing step is responsible for the higher oil and
grease loads. Chrome tanning is prevalent for shearling proc-
essing and results in significant levels of total chromium in
the untreated wastewater. Tables 7-16 and 7-17 summarize the
conventional and toxic pollutants found at shearling tanneries.
II.7.3 PLANT SPECIFIC DESCRIPTION [1]
Tables 7-18 through 7-27 present toxic pollutant and conventional
pollutant data for leather tanning and finishing process plants.
The data presented are based on information from six plants in
five subcategories. An end-of-pipe treatment system was used
for each tannery. The treatment system used by each site is
listed on each table. No additional information is currently
available on an individual plant basis.
II.7.4 POLLUTANT REMOVABILITY
II.7.4.1 Industry Application
The leather tanning and finishing industry utilizes two general
systems to minimize the quantity of pollutants discharged by
tanneries. They are (1) in-plant process control and (2) end-of-
pipe effluent treatment systems. End-of-pipe treatment
approaches include preliminary treatment and primary treatment,
Date: 6/23/80 II.7-17
-------
TABLE 7-15
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOR THE THROUGH-THE-BLUE SUBCATEGORY [1]
Number
of
Toxic pollutants samples
Metals and inorganics
Chromium
Copper
Lead
Nickel
Zinc
Ethers
Bis(2-chloroisopropyl ) ether
Phthalates
Bis(2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 , 2-Diphenylhydrazine
N-nitrosodiphenylamine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
2,4, 6-Tr ichlorophenol
Aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated aliphatics
Chloroform \
Dichl or obromome thane
1 , 1-Dichloroe'thane
1 , 2-Dichloroe thane
1 , 2-rrans-dichloroethylene
1,1,2 , 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Tnchloroe thane
Trichloroethylene
Trichlorofluorome thane
Pesticides and metabolites
n-BHC ,
p-BHC '
Chlordane
Isophorone
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Number
detected
1
1
1
1
1
1
1
1
1 .
1
1
1
1
1
1
1
1
1
Concentration, pg/L
Range Mean
550,000
100
28
160
980
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Present
ND
Present
Present
ND
ND
ND
Present
Present
Present
ND
ND
Present
ND
ND
Present
ND
ND
Present
Present
Present
ND
Present
ND
ND
ND
ND
ND
ND
Present
ND
ND
ND
ND
Present
ND
Note: ND = not detected.
Date: 6/23/80
II.7-18
-------
TABLE 7-16.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL POLLUT-
ANTS FOR THE SHEARLING SUBCATEGORY [1]
Pollutant
BOD,
COD
TSS
TKN
Sul fides
Oil and greaae
Total chroMiua
Asnoma
Number of
data point*
24
19
25
7
10
12
16
7
Concentration,
Rang* of
individual
data point*
100 - 3. tOO
170 - ll.SOO
120 - 7,600
39.0 - 7SO
0.0*0 - 68.0
$6.0 - 1,200
0.020 - 140
9.70 - 35.0
•a/I.
Mean
3 so
900
390
S3
0.2
ISO
13
13
TABLE 7-17.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOR THE SHEARLING SUBCATEGORY [1]
Number
of
Toxic pollutants *a«>i««
Metals and inorganics
chromium
Copper
Cyanide
Lead
Nickel
Zinc
Ethers
Bis(2-chlorolsopropyl ) ether
Phthalates
Bls(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Dl-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Benzidine
3,3' -Dichlorobenzidine
1 , 2 -Diphenylhydraz me
N-nitrosodlphenylamine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dlmethylphenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Aromatlcs
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dlchlorobenzene
1 . 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1.2, 4-Triehlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene/anthracene
Pyrene
Halogenated aliphatics
Chloroform
Dlchlorobromome thane
1 . 1-Dichloroe thane
1 , 2-Dichloroethane
1 . 2-rrans-dichloroethylene
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
1.1, 2-Trichloroe thane
Trichloroethylene
Trichlorofluorome thane
Pesticides and metabolites
a -BHC
B-BHC '
Chlordane
Isophorone
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Number Concentration. ua/L
detected Range Mean
2 2,000 - 53,000 36,500
2 35 - 120 78
2 10 10
2 75
2 20-27 24
2 190 - 500 340
ND
1 93
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1 400
1 91
ND
2 5-10 8
ND
1 61
ND
2 19-20 20
ND
ND
ND
2 9-10 10
ND
ND
ND
ND
ND
ND
2 26
1 36
ND
2 12-20 16
ND
ND
ND
ND
1 18
ND
ND
ND
ND
ND
ND
ND
ND
Note: ND « not detected.
Date: 6/23/80
II.7-19
-------
TABLE 7-18
CONCENTRATIONS OF CONVENTIONAL
POLLUTANTS FOUND IN THE HAIR
PULP/CHROME TAN/RETAN-WET FINISH
SUBCATEGORY FOR PLANT 47 [1]
Treatment type: Activated sludge
Concentration, mq/La Percent
Pollutant
BOD 5
COD
TSS
TKN
Sul fides
Oil and grease
pH
Ammonia
Influent
1,500
6,000
6,400
750
19
250
8.6
440
Effluent
49
560
230
280
17
35
7.6
240
removal
97
91
96
63
9
86
46
Except pH, given in pH units.
TABLE 7-19. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
THE HAIR SAVE/NONCHROME TAN/RETAN-WET FINISH
SUBCATEGORY FOR PLANT 47 [1]
Treatment type: Activated sludge
Pollutant
Concentration, pg/L
InfluentEffluent
Percent
removal
Metals and inorganics
Chromium 6,400 170 97
Copper 200 25 88
Cyanide 100 400 -
Lead 100 50 50
Nickel 60 30 50
Zinc 460 59 87
Phthalates
Bis(2-ethylhexyl) phthalate ND 26 -a
Phenols
Pentachlorophenol 2,900 200 93
Phenol 850 ND >99
2,4,6-Trichlorophenol 1,700 38 98
Aromatics .
Benzene <10 <10
1,2-Dichlorobenzene 49 ND >99
1,4-Dichlorobenzene 19 ND >99
Ethylbenzene 43 <10 98.
Toluene <10 <10
Polycyclic aromatic
hydrocarbons
Naphthalene 19 ND >99
Phenanthrene/anthracene 7.6 ND >99
Halogenated aliphatics .
Chloroform ND ND -
1,1,2,2-Tetrachloroethane <10 ND >99
Pesticides and metabolites
"-BHC _l
p-BHC j ND ND -
Note: ND = not detected.
Negative removal.
Negligible removal.
Date: 6/23/80
II.7-20
-------
TABLE 7-20.
CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND IN THE HAIR SAVE/CHROME TAN/RETAN-WET
FINISH SUBCATEGORY FOR PLANTS 248 and 320 [1]
Treatment type: Extended aeration,
activated aludge
Concentration. ao/L*
Pollutant
BOD,
COD
TSS
TKN
Sulfldes
Oil and grease
pH
Ammonia
BOD.,
COD
TSS
TKN
Sulfldes
Oil and grease
PH
Ammonia
Influent
1,200
2,600
1.100
250
50
170
11.0
98
2,000
4,000
2.250
290
16
550
8.4
150
Effluent
Plant 248
920
1,800
560
190
30
91
10.5
60
Plant 320
300
890
130
160
6
17
7.6
123
Percent
removal
26
31
49
26
40
47
39
86
87
94
43
63
97
18
TABLE 7-21.
Except pH, given in pB units.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE HAIR
SAVE/CHROME TAN/RETAN-WET FINISH SUBCATEGORY FOR
PLANTS 248 and 320 [1]
Treatment type Extended aeration, activated sludge
Plant 248
Concentration. VQ/L
Pollutant
Metals and inorganics
Chroniun
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexylJ phthalate
Phenols
Pentachlorophenol
Phenol
2 4 6-Tnchlorophenol
Aromat ics
Benzene
1 , 2-Dichlorobenzene
1.4-Dichl robenzene
Ethylbenz ne
Toluene
Polycyclic romatic hydrocarbons
Naphthale f
Phenanthr ne/anthracene
Halogenated aliphatic*
Bromoform
1.1,2.2-Tetrachloroethane
Influent
31,000
57
20
100
5
230
ND
9.500
480
10,500
HD
215
99
KD
<10
49
56
41
ND
Effluent
20 . 000
37
40
30
34
140
ND
3,100
435
4,300
ND
69
21
ND
<10
15
<10
<10
HD
Percent
removal
35
35,
70
a
39
a
67
9
59
b
68
79
D
-
69
98
98,
b
Plant 320
Concentration, pq/L
Influent
170,000
220
50
3,100
75
2.100
32
HD
5,500
ND
'10
HD
HD
>100
>100
ND
2 9
<10
ND
Effluent
1,700
8
40
60
30
170
6
12
1,400
12
<10
< 10
<10
<10
< 10
2 3
1 4
ND
HD
Percent
rmoval
99
96
20
98
60
92
83
a
75
a
_b
a
a
99
99
a
52
>99
b
Pesticides and metabolites
a-BHC
P-BHC '
Note HD = not detected
'Negative removal
Negligible removal
Date: 6/23/80
II.7-21
-------
TABLE 7-22. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND
IN THE SHEARLING SUBCATEGORY FOR PLANT 253 [1]
Treatment type: Activated sludge
Pollutant
BODS
COD
TSS
TKN
Sulfides
Oil and grease
pH
Ammonia
Concentration ,
mq/La
Influent Effluent
1,000
2,400
770
49
0.16
410
5.2
11
27
490
110
27
0.13
25
7.7
17
Percent
removal
97
79
86
45
17
94
V,
aExcept pH, given in pH units.
Negative removal.
TABLE 7-23. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
THE SHEARLING SUBCATEGORY FOR PLANT 253 [1]
Treatment type: Activated sludge
Concentration, pg/LPercent
Pollutant Influent Effluent removal
Metals and inorganics
Chromium 53,000 2,200 96
Copper 120 7 94
Cyanide 10 <10 >0
Lead 80 30 63
Nickel 27 19 30
Zinc 500 68 86
Phthalates
Bis(2-ethylhexyl) phthalate 93 34 63
Phenols
Pentachlorophenol 400 130 68
Phenol 91 ND >99
2,4,6-Trichlorophenol ND ND ND
Aromatics
Benzene 5 ND >99a
1,2-Dichlorobenzene ND ND -
1,4-Dichlorobenzene 20 ND >99a
Ethylbenzene ND ND -
Toluene 9 ND >99
Polycyclic aromatic hydrocarbons
Naphthalene 35 ND >99
Phenanthrene/anthracene 36 6 83
Halogenated aliphatics
Chloroform 12 10 16
1,1,2,2-Tetrachloroethane 18 ND >99
Pesticides and metabolites
or-BHC , „_. »— a
P-BHC } ND ND -
Note: ND = not detected.
Negligible removal.
Date: 6/23/80 II.7-22
-------
TABLE 7-24,
. CONCENTRATIONS OF CONVENTIONAL
POLLUTANTS FOUND IN THE HAIR
PULP/CHROME TAN/RETAN-WET FINISH
SUBCATEGORY FOR PLANT 184 [1]
Treatment type: Aerated lagoons
Concentration, mg/La
Pollutant
BOD 5
COD
TSS
TKN
Sulfides
Oil and grease
PH
Ammonia
Influent
1,900
5,500
2,900
500
200
720
8.4
260
Effluent
20
220
160
100
0.4
17
6.8
64
Percent
removal
99
96
95
79
99
98
76
TABLE 7-25.
aExcept pH, given in pH units.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
HAIR PULP/CHROME TAN/RETAN-WET FINISH SUBCATEGORY
FOR PLANT 184 [1]
Treatment type: Aerated lagoon
Pollutant
Concentration, pg/L Percent
Influent Effluent removal
Metals and inorganics
Chromium 160,000 1,100 99
Copper 50 5 90
Cyanide 60 150
Lead 1,100 80 93
Nickel 60 30 50
Zinc 500 49 90
Phthalates
Bis(2-ethylhexyl) phthalate 51 2 96
Phenols
Pentachlorophenol ND ND
Phenol 4,400 ND >99
2,4,6-Trichlorophenol 880 ND >99
Aromatics
Benzene <10 <10
1,2-Dichlorobenzene 260 ND >99
1,4-Dichlorobenzene 54 ND >99
Ethylbenzene 88 ND >99
Toluene >100 <10 99
Polycyclic aromatic hydrocarbons
Naphthalene 24 ND >99.
Phenanthrene/anthracene ND ND -*
Halogenated aliphatics
Chloroform ND ND
1,1,2,2-Tetrachloroethane ND ND
Pesticides and metabolites
l-BHC } N13 m
Note: ND = not detected.
Negligible removal.
_a
"a
Date: 6/23/80
II.7-23
-------
TABLE 7-26. CONCENTRATIONS OF CONVENTIONAL
POLLUTANTS FOUND IN THE RETAN-WET
SUBCATEGORY FOR PLANT 247 [1]
Treatment type: Physical/chemical
Concentration, mg/La
Pollutant
BODS
COD
TSS
TKN
Sulfides
Oil and grease
pH
Ammonia
Influent
620
1,900
520
180
0.5
160
4.3
110
Effluent
6.7
2B
7.7
4.4
0.3
15
4.4
1.5
Percent
removal
99
99
98
98
40
91
-
99
aExcept pH, given in pH units.
TABLE 7-27. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
RETAN-WET FINISH SUBCATEGORY FOR PLANT 247 [1]
Treatment type: Physical/chemical
Pollutant
Concentration, pg/L Percent
Influent Effluent removal
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Phenols
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Aromatics
Benzene
1,2-Dichlorobenzene
1,4-Dichlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Phenanthrene/anthracene
Halogenated aliphatics
Chloroform
1,1,2,2-Tetrachloroethane
Pesticides and metabolites
a-BHC ,
6-BHC '
16,000
260
300
6
150
ND
ND
3,200
570
ND
ND
>100
11
ND
130
ND
ND
<20
<8
8
4
61
ND
ND
60
ND
ND
12
8.5
7.3
ND
ND
>99
97.
97
33
61
98
99
_a
_a
"a
92
99
95
Note : ND = not detected .
Negligible removal.
Date: 6/23/80
II. 7-24
-------
secondary treatment, and advanced waste treatment. Preliminary
treatment includes in-plant controls, preliminary treatment of
segregated streams, and primary treatment of combined streams by
coagulation-sedimentation. Secondary treatment is intended for
use to remove biodegradable organic material. Advanced waste
treatment includes technologies that remove certain pollutants
and produce an effluent of high clarity and extremely low content
of conventional, nonconventional, and toxic pollutants.
Current treatment employed in the tanning industry ranges from no
treatment to several types of secondary treatment. Twelve
percent of the industry dischargers have no pretreatment; yet,
all the direct dischargers have at least primary treatment and
some form of secondary treatment. Eighteen plants discharge
their wastewaters directly to surface waters. One-hundred
and seventy indirect dischargers discharge to municipal treat-
ment plants.
II.7.4.2 Treatment Methods
In-Plant Control
Process Changes. Process changes are difficult to make
because of the numerous tanning methods employed. Substitution
of effluents from one process for make-up water in another is
generally feasible at some points within a tannery. Before
tanneries can make this change, however, they must establish the
quantity and pollutant content of water required for each
operation.
Substitution of Process Ingredients. Chemical ingredients
of low pollution potential can often be substituted for problem
pollutants. A number of process chemical substitution oppor-
tunities exist.
Water Conservation and Reuse. Conscientious use of water
helps to reduce both the volume of wastes and the amount of water
used. One plant in the industry currently employs a comprehen-
sive water conservation program. Through implementation of this
program, the total use of water has decreased nearly
Water may also be conserved by reusing it in another process.
The water, however, must be filtered or treated. Batch washing
reduces water consumption by approximately one-fifth.
Automatic Monitoring Devices. Automatic monitoring equip-
ment for detecting abnormal levels of selected constituents
guards against the failure of established precautionary measures.
In addition to indicating loss of materials, automatic sensing
devices also can operate recovery equipment.
Date: 6/23/80 II.7-25
-------
Recovery and Reuse of Process Chemicals. The most efficient
method of eliminating pollutants from tannery wastes and of
reducing the volume of effluent is through reuse of water and
chemical agents and through recovery of materials that are
normally used. Four plants in the industry are currently using
this approach. These facilities use recycle systems to reduce
the amounts of tanning liquor discharged into the waste streams.
Preliminary Treatment
Screening. The principal function of screening is to
remove objectionable material that has a potential for damaging
plant equipment and clogging pumps or sewers. Much of the
screening employed in this industry has been ineffective due to
poorly operated screens, or screens with openings that are too
large, or both.
Carbonation of Beamhouse Waste Stream. Carbonation is
effective in the treatment of alkaline wastes. Four tanneries
in the United States have operated flue gas or carbon dioxide
Carbonation systems. Carbonation is attractive for tannery pre-
treatment facilities. The effectiveness of flue gas Carbonation
of beamhouse waste streams is optimal when the pH is lowered to
the isoelectric point. The introduction of only flue gas can
limit the degree of treatment possible.
Secondary Treatment
Activated Sludge Systems. The activated sludge process is
one of the most controllable and flexible of all secondary treat-
ment systems. It is applicable to almost all treatment situa-
tions and plays a very important role in this industry for treat-
ment of toxic pollutants. With proper design and operation, high
organic removals are possible. Designs based on solids retention
time (SRT) afford optimum residence time for solids with minimal
hydraulic retention. However, pilot studies are required to
establish appropriate design parameters defining the relative
rate of biological growth and decay with a given wastewater.
Activated sludge systems, including various modifications, have
been and can be effective in organic reductions to low BOD5 con-
centrations even under low temperature conditions. Removals of
suspended solids prior to final effluent discharge and mainte-
nance of a large quantity of active biomass in the aeration basin,
especially during winter months to compensate for lower rates of
organism activity, appear to depend on conservative design and
diligent operation of the final clarifier.
Physical-Chemical Processes
Chappel Process. The Chappel process is a patented
physical-chemical process for treating wastewater streams. The
Date: 6/23/80 11.7-26
-------
basis for this process is the assumption that all waste streams
contain components that flocculate or settle in the proper
environment.
Activated Carbon. The use of activated carbon in treating
industrial wastewaters has been generally successful depending on
the application, the soundness of engineering, the degree of
proper operation and maintenance, and the performance criteria
established for the system. A relatively new application of
powdered activated carbon (PAC) is being tested and evaluated
in combined carbon-biological systems because of the ability of
activated carbon to improve the performance of biological
systems. This concept is now undergoing extensive testing, using
powdered carbon material in activated sludge systems. The carbon
is metered into the system with the influent at a concentration
normally less than 100 mg/L. It is recirculated and purged
along with the biological solids at a rate that maintain an
equilibrium concentration of 1,000 to 2,000 mg/L. Since the
powdered carbon is added directly to the activated sludge proc-
ess, this eliminates the need for carbon-adsorption beds or
columns.
Other treatment technologies may also be in current use in the
leather tanning and finishing industry.
II.7.5 REFERENCES
1. Development Document for Proposed Effluent Limitations
Guidelines, New Source Performance Standards, and Pretreat-
ment Standards for the Leather Tanning and Finishing Point
Source Category. U.S. Environmental Protection Agency,
Effluent Guidelines Division, Washington, D.C., July 1979.
2. Effluent Guidelines and Standards for Leather Tanning and
Finishing. U.S. Environmental Protection Agency, 40 CFR 425;
39FR 12958, April 9, 1974.
3. NRDC Consent Decree Industry Summary. Leather Tanning and
Finishing Industry.
Date: 6/23/80 II.7-27
-------
II.8.3 COIL COATING
II.8.3.1 Industry Description
II.8.3.1.1 General Description [I]
The coil coating industry consists of approximately 70 plants
processing approximately 4 billion square meters of painted coil
each year. Facilities vary in size and corporate structure,
ranging from independent shops to captive operations. Indepen-
dent shops obtain untreated coil, conversion coating chemicals,
and paints, and produce a wide variety of coated coil. Typical-
ly, the annual production at these plants is low compared to that
from the captive coating operations. The captive coil coating
operation is usually an integral part of a large corporation
engaged in many other kinds of metal production and finishing.
The coil coating sequence, regardless of basis material or con-
version coating process used, consists of three functional
steps: cleaning, conversion coating, and painting. Basically,
there are three types of cleaning operations used in coil coat-
ing, and they can be used alone or in combinations. These are:
mild alkaline cleaning, strong alkaline cleaning, and acid
cleaning. There are four basic types of conversion coating
operations, and the use of one precludes the use of the others
on the same coil. These are: chromating, phosphating, use of
complex oxides, and no-rinse conversion coating. Some of these
conversion coating operations are designed for use on specific
basis materials. The painting operation is performed by roll
coating and is independent of the basis material and conversion
coating. Some specialized coatings are supplied without conver-
sion-coating the basis material. For example, Zincrometal is a
specialized coating consisting of two coats of special paints
that do not require conversion coating. In this process, coils
are cleaned and dryed, and then receive two coats of the special
paints.
The selection of basis material, conversion coating, and paint
formulation is an art based upon experience. The variables that
are typically involved in the selection are appearance, color,
gloss, corrosion resistance, abrasion resistance, process line
capability, availability of raw materials, customer preference,
and cost. Some basis materials inherently work better with cer-
tain conversion coatings, and some conversion coatings work
better with certain paint formulations. On the whole, however,
the choice of which combination to use on a basis material is
limited only by plant and customer preferences.
The following subsections describe the coil coating processes
in more detail.
Date: 6/23/80 II.8.3-1
-------
Cleaning. Coil coating requires that the basis material be
cleanlA thoroughly clean coil assures efficient conversion
coating and a resulting uniform surface for painting. The soils,
oils, and oxide coatings found on a typical coil originate from
rolling mill operations and storage conditions prior to coil
coating. Such substances can stop the conversion coating reac-
tion, cause a coating void on part of the basis material, and
cause the production of a nonuniform coating. Cleaning opera-
tions must chemically and physically remove these interfering
substances without degrading the surface of the basis material.
Excessive cleaning can roughen a basically smooth surface to a
point where a paint film will not provide optimum protective
properties.
Aluminum and galvanized steel are prone to develop an oxide coat-
ing that acts as a barrier to chemical conversion coatings.
However, these oxide films are easier to remove than rust and
therefore require a less vigorous cleaning process. A mild alka-
line cleaner is usually applied with power spray equipment to
remove the oxide coating and other interfering substances. The
cleaning solutions normally used consist of combinations of sodi-
um carbonates, phosphates, silicates, and hydroxides. These com-
pounds give the solution its alkaline character and emulsify the
removed soils. Soap and detergents may be added to the solution
to lower the surface and interfacial tension. A good cleaning
solution also rinses easily. Solutions may be made stronger with
the addition of more sodium hydroxide.
Steel, unless adequately protected with a film of oil subsequent
to rolling mill operations, has a tendency to form surface rust
rather quickly. This rust on the surface of the metal prevents
proper conversion coating. A traditional method of removing rust
is an acid applied by power spray equipment. The spraying action
cleans both by physical impingement and the etching action of the
acid. The power spray action is followed by a brush scrub which
further removes soil loosened by the acid. The brush scrub is
followed by a strong alkaline spray wash which removes all traces
of the acid and neutralizes the surface.
A spray rinse follows the alkaline cleaning step. Spray rinsing
is conducive to the fast line speeds which make coil coating an
economical coating procedure. The spray rinse physically removes
alkaline cleaning residues and soil by both the physical impinge-
ment of the water and the diluting action of the water. The
rinse water is usually maintained at approximately 66°C (150°F)
to keep the coil warm for the subsequent conversion coating
reactions and to help the rinsing action. The rinsing action
prevents contamination of the conversion coating bath with clean-
ing residues which are dragged out on the strip and that could be
subsequently deposited in the conversion coating solutions. The
Date: 6/23/80 II.8.3-2
-------
rinsing step also keeps the surface of the metal wet and active,
which permits faster conversion coating film formation.
The no-rinse conversion coating and the Zincrometal processes
require a coil that is clean, warm, and dry. For these proces-
ses, a squeegee roll and forced air drying are used to assure a
clean, dry coil following alkaline cleaning and rinsing.
Conversion Coatings. The basic objective of the conversion
coating process is to provide a corrosion-resistant film that is
integrally bonded chemically and physically to the base metal and
that provides a smooth and chemically inert surface for subse-
quent application of a variety of paint films. The conversion
coating processes effectively render the surface of the basis
material electrically neutral and immune to galvanic corrosion.
Conversion coating on basis material coils does not involve the
use of applied electric current to coat the basis material. The
coating mechanisms are chemical reactions that occur between
solution and basis material.
Four types of conversion coatings are normally used in coil
coating:
• Chromate conversion coatings
• Phosphate conversion coating
• Complex oxides conversion coatings
• No-rinse conversion coatings
Chromate conversion coatings, phosphate conversion coatings, and
complex oxide conversion coatings are applied in basically the
same manner. No-rinse conversion coatings are roll applied and
use quite different chemical solutions than phosphating, chromat-
ing, or complex oxides solutions. However, the dried film is
used as basis for paint application similar to phosphating,
chromating, and complex oxide conversion coatings films.
Chromate conversion coatings can be applied to both aluminum and
galvanized surfaces but are generally applied only to aluminum
surfaces. These coatings produce an amorphous layer of chromium
Chromate complexes and aluminum ions. The coatings offer unusu-
ally good corrosion-inhibiting properties but are not as abrasion
resistant as phosphate coatings. Scratched or abraded films
retain a great deal of protective value because the hexavalent
chromium content of the film is slowly leached by moisture, pro-
viding a self-healing effect. Under limited applications, these
coatings can serve as the finished surface without being painted.
If further finishing is required, it is necessary to select an
organic finishing system that has good adhesive properties.
Chromate conversion coatings are extremely smooth, electrically
neutral, and quite resistant to chemical attack.
to chemical attack.
Date: 6/23/80 II. 8.3-3
-------
Chromate conversion coatings for aluminum are carried out in
acidic solutions. These solutions usually contain one chromium
salt, such as sodium chromate, or chromic acid and a strong oxi-
dizing agent such as hydrofluoric acid or nitric acid. The final
film usually contains both products and reactants and water of
hydration. Chromate films are formed by the chemical reaction of
hexavalent chromium with a metal surface in the presence of
"accelerators", such as cyanides, acetates, formates, sulfate,
chlorides, fluorides, nitrates, phosphates, and sulfamates.
Chromate conversion coating requires that the basis material be
alkaline-cleaned and spray-rinsed with warm water. The cleaning
and rinsing assures a clean, warm, wet surface on which the con-
version coating process takes place. Once the film is formed, it
is rinsed with water followed by a chromic acid sealing rinse.
This latter rinse seals the free pore area of the coating by
forming a chromium chromate gel. Also, the sealing rinse more
thoroughly removes precipitated deposits that may have been form-
ed by hard water in previous operations. The coil is then sub-
jected to a forced air drying step to assure a uniformly dry
surface for the following painting operation.
Phosphate conversion coatings provide a highly crystalline, elec-
trically neutral bond between a base metal and paint film. The
most widespread use of phosphate coatings is to prolong the useful
life of paint finishes. Phosphate coatings are primarily used on
steel and galvanized surfaces but also can be applied to aluminum.
Basically, there are three types of phosphate coatings: iron,
zinc, and manganese. Manganese coatings are not used in coil
coating operations because they are relatively slow in forming
and, as such, are not amenable to the high production speeds of
coil coaters.
The remaining two phosphate coatings are applied by spraying or
immersing the coil, with the major difference between them being
the weight and thickness of the dried coating. Iron phosphate •
coatings are the thinnest and lightest and generally the cheap-
est. Iron phosphate solutions are applied chiefly as a base for
paint films. Spray application of iron phosphating solutions is
most commonly used. The coating weights range from 0.22 to
0.86 g/m2.
Zinc phosphate coatings are quite versatile and can be used as a
base for paint or oil, as an aid to cold forming, to increase
wear resistance, and to provide rustproofing. Zinc phosphate
coatings can be applied by spray or immersion with applied coat-
ing weights ranging from 1.08 to 10.8 g/m2 for spray coating and
from 1.61 to 43.1 g/m2 for immersion coating.
Date: 6/23/80 II.8.3-4
-------
Phosphate coatings are formed in the metal surface, incorporating
metal ions dissolved from the surface. This creates a coating
that is integrally bonded to the base metal. In this respect,
phosphate coatings differ from electrodeposited coatings, which
are superimposed on the metal. Most metal phosphates are insol-
uble in water but soluble in mineral acids. Phosphating solu-
tions consist of metal phosphates dissolved in carefully balanced
solutions of phosphoric acid. As long as the acid concentration
of the bath remains above a critical point, the metal ions remain
in solution. Accelerators speed up film formation and prevent
the polarization effect of hydrogen on the surface of the metal.
Accelerators commonly used include nitrites, nitrates, chlorates,
and peroxides. Cobalt and nickel nitrite accelerators are the
most widely used and develop a coarse crystalline structure. The
peroxides are relatively unstable and difficult to control, while
chlorate accelerators generate a fine sludge that may cause dusty
or powdery deposits.
After phosphating, the coil is passed through a recirculating hot
water spray rinse. The rinsing action removes excess acid and
unreacted products, thereby stopping the conversion coating reac-
tion. Insufficient rinsing could cause blistering under the sub-
sequent paint film from the galvanic action of the residual acid
and metal salts.
The basis material is then passed through an acid sealing rinse
comprised of up to 0.1% by volume of phosphoric acid, chromic
acid, and various metallic conditioning agents, notably zinc.
This solution seals the free pore area of the coating by forming
a chromium chromate gel. Also, this acidic sealing rinse more
thoroughly removes precipitated deposits formed by hard water in
the previous rinses. Modified chromic acid rinses have found
extensive use in the industry. These rinses are prepared by
reducing chromic acid with an organic reductant to form a mixture
of trivalent chromium and hexavalent chromium in the form of a
complex chromium chromate.
Complex oxide conversion coatings can be applied to aluminum and
galvanized surfaces but are generally applied to only galvanized
surfaces. The nature of the film and the chemical and physical
reactions of its formation are a function and a reinforcement of
the naturally occurring protective oxide coating that is found
on galvanized surfaces. The physical properties of the complex
oxide conversion coating film are comparable to those of chromate
conversion coating films and phosphate conversion coating films.
Complex oxide film is formed in a basic solution while the films
described earlier are formed in an acidic solution. Complex
oxide conversion coating reactions do not contain either hexa-
valent or trivalent chromium ions. However, the sealing rinse
Date: 6/23/80 II.8.3-5
-------
contains much greater quantities of hexavalent and trivalent
chromium ions than do the sealing rinses associated with phos-
phate conversion coatings and chromate conversion coatings.
Recent developments in chromate conversion coating solutions have
resulted in a solution that can be applied to cold rolled steel,
galavanized steel, or aluminum without the need for any rinsing
after the coating has formed on the basis material. The basis
material must first be alkaline cleaned, thoroughly rinsed, and
forced-air dried prior to conversion coating. The conversion
coating solution is applied with a roll mechanism used in roll
coating paint. Once the solution is roll coated onto the basis
material, the coil is forced-air dried at approximately 66°C.
The no-rinse solutions are formulated in such a way that once a
film is formed and dried, there are no residual or detrimental
products left on the coating that could interfere with normal
coil coating paint formulations.
Although no-rinse conversion coatings currently represent a small
proportion of the conversion coating techniques that are used,
they offer several advantages, including fewer process steps in a
physically smaller process line, higher line speeds, application
of a very uniform thickness by roll coating rather than spray or
dip coating, and reduction of waste treatment requirements
because of the reduced use of chromium compounds. Disadvantages
include roll coating mechanism wear possibly reducing quality,
the closer coordination of entire line that is needed, difficulty
in adaptation, and the hazardous organic acids content of the
no-rinse conversion coating chemicals.
Painting. Roll coating of paint is the final process in a
coil coating line. Roll coating is an economical method to paint
large areas of metal with a variety of finishes and produces a
uniform and high quality coating. The reverse roll procedure for
coils is used by the coil coating industry, and allows both sides
of the coil to be painted simultaneously.
The paint formulations used in the coil coating industry have
high pigmentation levels (providing hiding power), adhesion, and
flexibility. Most coatings of this type are thermosetting and
are based on vinyl, acrylic, and epoxy functional aromatic poly-
ethers, and some reactive monomer or other resin with reactive
functions, such as melamine formaldehyde resins. Also, a variety
of copolymers of butadiene with styrene or maleic anhydride are
used in coating formulations. These coatings are cured by oxida-
tion mechanisms during baking similar to those that harden drying
oils.
Date: 6/23/80 II.8.3-6
-------
After paint application, all coils are cured in an oven. Curing
temperatures depend upon basis material, conversion coating,
paint formulation, and line speed. Typical temperatures range
from about 93°C to a maximum of about 371°C. Upon leaving the
oven, the coils are quenched with water to induce rapid cooling
prior to rewinding.
The quench is necessary for all basis materials, conversion coat-
ings, and paint formulations. A coil that is rewound when too
warm will develop internal and external stresses, causing a pos-
sible degradation of the appearance of the paint film and of the
forming properties of the coil. The volume of water used in the
quench often has the largest flow rate of all of the coil-coating
processes. However, the water is often circulated to a cooling
tower for heat dissipation and reuse.
The finished coils are used in a variety of industries. The
building products industry utilizes prefinished coils to fabri-
cate exterior siding, window and door frames, storm windows and
storm gutters, and various other trim and accessory building
products. The food and beverage industries utilize various types
of coils and finishes to safely and economically package and ship
a wide variety of food and beverage products. Until recently,
the automotive and appliance industries have made limited use of
prefinished coils. These industries have relied on post assembly
finishing of their products. Recently, the automotive industry
has begun using a cold rolled steel coil coated on one side with
a finish called Zincrometal. This coating is applied to the
under surfaces of the exterior automobile sheet metal to protect
them from corrosion. The appliance industry uses prefinished
coils in constructing certain models of refrigerator exteriors to
provide a finished product that minimizes the costly and labor-
intensive painting operation after forming.
Coil coating operations are located throughout the country,
usually in well established industrial centers. Compared to some
other industries, coil coating operations are not physically
large. Coil coating operations use large quantities of water and
are often a significant contributor to municipal waste treatment
systems or surface waters. In addition, the curing ovens from
coil coating operations are a source of air pollution in the form
of reactive hydrocarbons.
Table 8.3-1 presents an industry summary of the coil coating
industry.
Date: 6/23/80 II.8.3-7
-------
TABLE 8.3-1. INDUSTRY SUMMARY [1, 2]
Industry: Coil Coating
Total number of subcategories: 3
Number of subcategories studied: 3
Number of Dischargers in industry:
• Direct: 36
• Indirect: 54
• Zero dischargers: 0
II.8.3.1.2 Subcategory Description
The primary purpose of subcategorization is to establish group-
ings within the coil coating industry such that each group has a
uniform set of effluent limitations. While subcategorization is
based on wastewater characteristics, a review of the other sub-
categorization factors reveals that the basis material used and
the processes performed on these basis materials are the princi-
pal factors affecting the wastewater characteristics of plants in
the coil coating industry. The coil coating industry is there-
fore divided into the following three subcategories:
Coil Coating on steel
Coil coating on zinc coated steel (galvanized)
Coil coating on aluminum or aluminized steel
The following subsections describe the above subcategories.
Subcategory 1 - Coil Coating on Steel. The coil coating on
steel subcategory consists of approximately 31 plants, of which
eight facilities coat steel alone. The remaining plants coat a
combination of steel coils and coil from the other subcategories.
Approximately 470 x 106 m2 of coated steel are produced each
year. Operations used at these facilities include acid cleaning,
strong alkaline cleaning, phosphating, no-rinse conversion coat-
ing, roll coating, and Zincrometal coating. Table 8.3-2 presents
water usage data for the general operations at steel coating
facilities.
Date: 6/23/80 II.8.3-1
-------
TABLE 8.3-2,
SUMMARY OF WATER USAGE RATES FOR THE
COIL COATING INDUSTRY BY SUBCATEGORY [1]
Operation
Number
of points
Water use, L/m2
Range
Mean
Median
steel
Cleaning
Conversion coating
Paintinga
All operations
9
8
20
13
0.30 -
0.041 -
0.29 -
0.37 -
7.3
0.76
5.1
13
2.3
0.43
2.1
4.5
1.5
0.41
2.1
4.7
galvanized
Cleaning
Conversion coating
All operations
10
10
12
0.17 -
0.025 -
0.65 -
4.4
0.84
8.4
1.1
0.40
3.7
0.83
0.50
2.0
aluminum
Cleaning
Conversion coating
All operations
12
12
15
0.21 -
0.18 -
0.39 -
2.0
1.8
6.3
0.97
0.56
2.9
0.97
0.47
2.4
Painting water usage listed under steel is for all basis
materials.
Subcategory 2 - Coil Coating on Zinc Coated Steel
(Galvanized). The coil coating on galvanized steel sub-
category consists of 15 plants with an annual production of
approximately 600 x 106 m2. Only three facilities produce coated
galvanized steel alone. Five plants also coat steel coils, and
seven facilities coat steel and aluminum along with galvanized
steel. Operations used at the galvanized coating facilities
include mild alkaline cleaning, phosphating, chromating, complex
oxide treatment, no-rinse conversion coating, roll coating, and
Zincrometal coating. Table 8.3-2 above also presents water usage
data for the general operations at galvanized coating facilities.
Subcategory 3 - Coil Coating on Aluminum. This subcategory
consists of 32 facilities producing 470 x 106 m2 of product
annually. Fifteen facilities coat only aluminum coils, eleven
coat steel coils with the aluminum, and seven coat all three
types of basis metal. The aluminum coating facilities use mild
alkaline cleaning, phosphating, chromating, complex oxide treat-
ment, no-rinse conversion coating, and roll coating. Table 8.3-2
above also gives water usage information for the general pro-
cesses in this industry.
Date: 6/23/80
II.8.3-9
-------
II.8.3.2 Wastewater Characterization [I]
Water is used in virtually all coil coating operations. It pro-
vides the mechanism for removing undesirable compounds from the
basis material, is the medium for the chemical reactions that
occur on the basis material, and cools the basis material follow-
ing baking. Water is the medium that permits the high degree of
automation associated with coil coating and the high quality of
the finished product. The nature of coil coating operations, the
larg-e amount basis material processed, and the quantity and type
of chemicals used produces a large volume of wastewater that
requires treatment before discharge.
Wastewater generation occurs for each basis material (steel, gal-
vanized and aluminum) and for each functional operation (clean-
ing, conversion coating, and painting). The wastewater generated
by the three functional operations may (1) flow directly to a
municipal sewage treatment system or surface water, (2) flow
directly to an on-site waste treatment system and then to a muni-
cipal sewage treatment system or surface water, (3) be reused
directly or following intermediate treatment, or (4) undergo a
combination of the above processes.
Coil coating operations that produce wastewater are characterized
by the pollutant constituents associated with respective basis
materials. The constituents in the raw wastewaters include ions
of the basis material, oil and grease found on the basis mate-
rial, components of the cleaning and conversion coating solu-
tions, and the paints and solvents used in roll coating the basis
materials. The following tables present wastewater characteri-
zation data for each subcategory. These data are the result of
verification sampling at a number of plants in each subcategory.
Screening samples were generally first analyzed to determine what
compounds should be analyzed. The pollutants that have been
chosen were found in a concentration greater than 0.010 mg/L.
Tables 8.3-3 through 8.3-10 present raw wastewater characteriza-
tion data for each general process in each subcategory and for
the wastewater in each subcategory when combined into a single
representative stream as a whole. Table 8.3-11 presents raw
wastewater flow data for each subcategory.
Date: 6/23/80 II'. 8.3-10
-------
TABLE 8.3-3.
CONVENTIONAL AND NONTOXIC POLLUTANT CONCEN-
TRATIONS FOR THE RAW WASTEWATER IN THE COIL
COATING INDUSTRY, BY SUBCATEGORY [1]
Pollutant
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Nontoxic inorganic
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Fluorides
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Nontoxic inorganic
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Strontium
Tin
Titanium
Vanadium
yttrium
Fluorides
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Nontoxic inorganic
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Fluorides
Number
of points
13
6
8
12
12
13
2
2
2
2
13
2
13
2
2
1
2
2
2
2
12
3
5
11
12
12
11
12
12
15
3
5
15
15
15
15
15
1
1
1
1
15
Number Concentration, mg/L
detected hange Mean Median
13
6
8
12
12
12
1
1
2
1
13
2
13
2
2
1
1
1
1
1
12
3
5
9
12
11
11
12
12*
15
3
5
11
14
15
15
15
1
1
1
1
15
steel
17 - 2,900
700 - 15,000
5.8 - 120
<0.010 - 0.21
2.1 - 1,400
0.020 - 1.9
0.53
0.25
16 - 70
0.31
0.78 - 21
4.4 - 21
0.25 - 1.3
<0.010 - 0.066
310 - 500
0.33
0.33
0.042
0.031
0.021
galvanized
35 - 570
170 - 1,600
8.7 - 56
<0.010 - 0.071
2.3 - 870
0.29 - 5.3
0.40 - 17
<0.010 - 0.81
0.21 - 9.4
aluminum
3.4 - 880
910 - 1,300
1.7 - 12
<0.010 - 0.071
1.3 - 730
4.3 - 680
9.0
0.18 - 10
20
0.050
170
0.060
2.4 - 240
490
5,700
52
0.047
510
0.66
0.53
0.25
43
0.31
10
13
0.60
0.038
400
0.33
0.33
0.042
0.031
0.021
190
740
26
0.026
200
2.2
4.6
0.17
3.7
240
1,100
6.7
0.028
130
190
9.0
3.6
20
0.050
170
0.060
67
150
1,700
43
0.020
340
0.61
0.53
0.25
43
0.31
10
13
0.53
0.038
400
0.33
0.33
0.042
0.031
0.021
110
430
15
<0.010
53
1.7
2.8
0.12
2.1
85
1,100
7.0
0.026
58
110
9.0
3.4
20
0.050
170
0.060
21
Note: Blanks indicate no data available.
Date: 6/23/80
II.8.3-11
-------
D
0)
rt
(D
cr>
NJ
U>
CD
O
TABLE 8.3-4
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW WASTEWATER
FOR THE COIL COATING INDUSTRY, BY SUBCATEGORY [1]
H
CO
U)
I
Number
of
Metals and inorganics
Antinony
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
BisU-ethylhexyl) rhthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Dlethyl phthalate
Dlaethyl phthalate
Di-n-octyl phthalate
Phenol!
2.4-Dimethylphenol
Phenol
Aromatic*
Benzene
Bthylbenzan*
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benc (a ) anthracene
Benzo (a ) pyrene
Benzo (b) f luoranthane
Benzo (ghi ) pery lene
Benzo fluoranthene
Chrysene
Dlbenz (ah) anthracene
Fluoranthene
Indeno (1,2, 3-cd ) pyrene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
1 , 1-Dichloroethane
1 , 1-Dlchloroethylene
1 , 2-rptms-dichloroethylene
Methylene chloride
Tetrachloroe thy lene
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
1
2
13
13
13
12
13
2
13
2
13
12
12
12
12
12
5
S
1
1
5
13
12
12
12
12
12
12
12
12
12
12
12
7
1
1
8
8
12
Number
detected
1
1
7
13
13
7
10
2
9
1
13
11
2
10
10
4
1
1
1
1
1
1
11
5
1
1
1
5
6
4
6
11
4
1
1
6
6
'
Numbet
Concentration, ug/L of Number
Range Mean Median points detected
steel
i.noo
75 '5
-10 - 39 -10
40 - 330,000 62.000
11 - 140 52
<10 - 55 21
11 - 1,500 TOO
•10 10
<10 - 2.100 620
20 20
1,500 - 340,000 40,000
<10 - 620 98
<10 - 300 150
<10 - 600 140
<10 - 180 59
21 21
16 16
<10
<10
<10 <10
<10 - 1,400 340
<10 - 160 69
<10 <10
35 35
35 35
<10 - 160 59
<10 - 130 45
<10 - 300 90
<10 - 25 <10
<10 - 1,400 340
<10 - 50 21
18 18
< 10
<10 <10
600 600
1,000
< 10
6. -100
SI
12
140
390
7,600
35
150
56
29
21
16
<10
<10
<10
64
56
<10
35
35
23
40
30
64
16
18
<10
600
1 ^
11
12
12
12
12
11
11
11
11
11
11
2
4
4
11
11
11
11
11
11
11
11
11
11
11
11
11
9
U
11
u
H
11
12
7
12
6
12
11
4
8
11
1
0
0
0
6
6
2
1
0
6
4
6
0
6
3
6
5
3
Number
Range Mean Median points
gaiv,
<10
49
<10
<10
<10
'10
2,300
<10
<10
<10
<10
<10
<10
<10
<10
•10
<10
<10
<10
in i zed
- 200 55 45
- 130,000 46 000 5B.OOO
- 60 21 '10
160 89 82
- 2,100 680 420
- 3,200 760 400
- 150,000 51,000 25,000
- 1,100 250 180
- 32 <10 <10
- 160 29 <10
- 390 85 48
- 390 <10 <10
10 <10 <10
- 250 49 <10
- 25 <10 <10
clO <10 <10
tlO <10 <10
(10 *10 <10
- 78 24 <10
- 71 18 <10
<10 <10 <10
240 85 15
- 1,300 260
- 1,300 310 <10
15
1'
15
15
15
14
14
14
14
2
14
14
14
Number Concentration, pg/L
detected Range Mean Median
15
13
12
n
15
13
6
11
4
1
4
1
6
a] uninum
'IP <10 <10
1,800 27,000 71.000 43.000
<10 - 180 80 43
<10 - 18,000 4,800 570
54 - 200 120 120
12 - 15,000 2,200 200
<10
-------
TABLE 8.3-5.
CONVENTIONAL AND NONTOXIC INORGANIC POLLUTANT
CONCENTRATIONS IN THE RAW WASTEWATER FOR
CLEANING OPERATIONS IN THE COIL COATING
INDUSTRY, BY SUBCATEGORY [1]
Number
Number
Concentration, mq/La
Pollutant of points detected Range
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
Conventional
TSS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
Note: Blanks indicate
a , . ,
9
4
7
8
9
9
9
9
9
9
9
10
1
3
9
10
10
10
10
10
10
10
12
9
12
12
12
12
12
12
12
12
no data
9
4
7
5
9
9
9
9
7
9
9
10
1
9
7
10
10
10
10
9
10
9
12
6
11
9
12
12
9
12
12
9
available.
steel
52 -
1,100 -
11 -
0.019 -
9.8 -
6.8 -
7.4 -
0.18 -
0.27 -
0.93 -
0.26 -
galvanized
19 -
200
9.4 -
0.010 -
10 -
2.2 -
7.4 -
0.16 -
0.41 -
0.19 -
0.012 -
aluminum
6 -
0.69 -
0.010 -
1.0 -
7.1 -
8.4 -
0.43 -
8.6 -
0.077 -
0.021 -
440
17,000
78
0.27
1,700
10.9
11.9
3.4
0.85
80
1.7
630
56
0.079
970
9.4
11.9
16
4.9
18
0.73
970
100
0.16
2,800
11.0
11.9
9.5
940
0.69
15
Mean
220
9,200
46
0.11
520
8.7
10.0
1.3
0.45
25
0.80
250
200
33
0.037
260
6.4
10.2
2.5
2.4
4.8
0.19
180
63
0.047
530
9.4
10.6
2.0
400
0.35
5.0
Median
260
9,300
42
0.020
260
8.5
10.6
0.98
0.34
5.2
0.63
160
200
33
0.021
110
7.6
10.6
1.1
1.3
1.0
0.16
49
90
0.020
75
10.0
11.2
0.8
250
0.28
1.3
Date: 6/23/3-
II.8.3-13
-------
o
tu
rt
n>
NJ
00
o
TABLE 8.3-6.
CO
•
LO
I
CONCENTRATONS OF TOXIC POLLUTANTS FOUND IN THE RAW WASTEWATER FOR
CLEANING OPERATIONS IN THE COIL COATING INDUSTRY, BY SUBCATEGORY [1
Toxic pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Polycyclic aromatic hydrocarbons
Arenaphthylene
Anthracene
Benz (a) anthracene
Benzo (a) pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
Number
of
points
9
9
9
8
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
6
6
9
Number
Number
Concentration, yg/L of
detected Range
Mean Median points
steel
2
8
9
5
3
5
9
7
1
5
6
3
1
7
2
2
1
1
2
7
5
4
1
3
28
21
9
180
3
220
5
5
5
2
1
1
5
2
2
1
- 6
- 620
- 180
- 120
- 1,100
- 210
- 42,000
- 150
360
- 30
- 210
5
5
- 280
- 30
- 30
68
1
- 20
- 280
- 4
- 22
18
4
240
70
44
540
69
10,000
45
360
12
72
5
5
69
16
16
68
1
12
69
3
7
18
4
180
59
24
460
39
3,200
20
360
5
32
5
5
10
16
16
68
1
12
10
2
3
18
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
Number
Number
Concentration, yg/L of
detected
Range
Mean
Median points
Number
Concentration, UQ/L
detected Ran-je
galvanized
2
9
9
4
9
1
10
9
1
7
8
1
3
4
4
3
4
2
3
3
4
2
1
6
59
9
12
180
690
14
2
5
10
5
5
5
5
10
1
1
- 120
- 610
- 57
- 43
- 2,600
150
- 120,000
- 340
13
- 170
- 420
5
- 250
- 27
- 27
5
- 85
- 38
- 47
5
- 6
- 2
47
45
310
30
22
1,600
150
63,000
120
13
44
140
5
93
15
15
5
35
21
26
5
4
1
47
40
270
20
17
2,000
150
85,000
74
13
25
86
5
20
14
14
5
26
21
20
5
4
1
47
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
3
9
9
9
5
10
10
2
7
2
2
3
1
3
2
aluminum
3-21
2R - 6,000
9 - 210
5 - 260
60 - 220
13 - 14,000
1 - 450
5-12
20 - 450
2-5
5
1-2
5
2-5
5
9
1,300
84
40
140
1,600
130
8
170
3
5
2
5
3
5
3
180
75
10
no
210
15
e
80
3
5
2
5
2
5
Note: Blanks indicate no data available.
-------
TABLE 8.3-7.
CONVENTIONAL AND NONTOXIC INORGANIC POLLUTANT
CONCENTRATIONS IN THE RAW WASTEWATER FOR THE
CONVERSION COATING OPERATION IN THE COIL
COATING INDUSTRY, BY SUBCATEGORY [1]
Number
Pollutant of points
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
8
3
6
7
7
8
8
8
8
8
8
Number
detected
8
3
6
4
6
8
8
8
5
8
8
Concentration, mg/la
Range
steel
27 -
3,300 -
9.7 -
0.001 -
2 -
3.3 -
5.1 -
1.1 -
0.20 -
3.3 -
0.11 -
250
3,500
71
0.23
18
11.4
11.5
74
10.6
77
1.5
Mean
130
3,400
41
0.067
7.6
5.8
7.7
31
3.0
19
0.61
Median
130
3,400
43
0.018
6.6
4.3
7.5
27
1.2
9.2
0.49
galvanized
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
10
1
7
10
10
10
10
10
10
10
10
10
1
7
7
10
10
10
9
10
10
68 -
450
2,500
3.8 -
0.005 -
1.3 -
2.4 -
3.3 -
1.5 -
1.3 -
0.84 -
0.035 -
66
0.067
110
11.1
12.0
71
10.6
21
1.3
250
2,500
33
0.021
19
4.5
8.2
16
3.6
6.6
0.25
190
2,500
25
0.020
11
3.4
8.6
11
2.3
5.1
0.12
aluminum
Conventional
TSS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
12
2
12
12
12
12
12
12
12
12
12
2
8
9
12
12
12
12
12
12
4.2 -
13 -
0.004 -
0.20 -
1.6 -
3.7 -
18 -
11 -
0.83 -
0.049 -
1,200
16
0.14
60
5.4
6.7
510
410
87
12
160
15
0.029
9.4
3.0
5.2
210
160
21
1.4
55
15
0.011
2.0
2.5
5.1
31
110
7.8
0.34
Note: Blanks indicate
no data
available.
.
Date: 6/23/80
II.8.3-15
-------
o
D)
n-
tt>
TABLE 8.3-8.
to
CO
o
CO
•
U)
I
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
RAW WASTEWATER OF CONVERSION COATING OPERATIONS
IN THE COIL COATING INDUSTRY, BY SUBCATEGORY [1]
Number
of
Toxic pollutant points
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
Bls(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Polycyclic aromatic hydrocarbons
Aeenaphthylana
Anthracene
Benz (a) anthracene
Benzo(a)pyrene
Chrysana
Fluoran thane
Fluorene
Naphthalene
Phenanthrene
Pyrene
Kalogenated aliphatic.
1 , 1-Dlchloroethane
1 , 1-Dichloroethylene
1 , 2-Tmna-dichloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
8
8
8
7
8
8
a
7
7
7
7
7
7
7
7
7
7
7
8
8
Number
dct« ctcj Ranyu
3
8
6
1
3
4
a
5
3
6
1
1
3
1
2
4
3
1
3
3
steel
1-73
280 - 920, OOO
29 - 160
92
10 - 3.600
120 - 19,000
530 - 140,000
S - 110
4-14
10 - 180
760
5
5
5
5
5
5
77
0.1-41
1-88
t ion . tig/
Mean
Number
1. of
•fc-d i an ]
loint1.
Number
Number
Concentration, IJQ/I. of
detect,1') Range
M.-ar
Median l-o
Inti
Number
Concentration, lig/L
detected Range
Mean
Median
qalvanized alumin'jn
27
320.000
54
92
1.400
3,100
54.0OO
11
a
120
760
S
5
5
S
5
S
77
IS
15
6
71,000
32
92
480
6,800
51.000
14
5
130
760
5
5
5
5
5
5
77
1
14
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
5
10
8
5
10
6
10
9
3
3
9
1
3
1
1
1
1
S
3
1
4
1
2
2
1
8
3.400
4
120
5
13
33.000
10
5
IS
5
S
S
16
1
29
- 110
- 790,000
- 140
- 470
- 1.300
- 31.000
- 710,000
- 1,200
5
- 20
- 300
1
- 290
5
5
21
5
- 15
- 290
11
- 140
2
- 15
- 110
516
42
290,000
31
290
560
7.600
220,000
240
5
10
86
«
1
99
5
S
21
5
7
9»
11
2
8
71
516
10
120.000
1R
200
500
4,400
75,000
41
5
5
51
3
5
5
S
23
5
5
5
11
2
8
71
516
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
1
12
10
9
2
4
12
9
2
9
1
1
4
2
1
4
3-19
15,000 - 970,000
11 - 9SO
17 - 7,500
170 - 400
18 - 260
16 - 43,000
2 - 300
5
110
2-5
2-3
2-5
2-5
10
270. OOO
190
J.200
290
120
8,800
52
4
8
120,000
52
2,600
290
110
540
20
4
Mote: Blanks indicate no data available.
-------
ft
(D
NJ
00
o
M
H
U)
I
TABLE 8.3-9,
CONVENTIONAL AND NONTOXIC INORGANIC POLLUTANT
CONCENTRATIONS IN THE RAW WASTEWATER FOR PAINT-
ING OPERATIONS FOR THE COIL COATING INDUSTRY [I]
Total industry
Pollutant
Conventional
TSS
TDS
Total phosphorus
Total phenols
Oil and grease
Minimum pH
Maximum pH
Fluorides
Nontoxic inorganic
Aluminum
Iron
Manganese
Number
of points
20
3
18
20
20
20
20
20
20
20
20
Number
detected
18
3
11
15
15
20
20
20
8
20
15
Concentration
, mg/L
Range Mean
0.010
99
0.25
0.003
1.0
4.9
7.2
0.15
0.46
0.018
0.002
- 24
- 1,100
- 15
- 0.040 0.
- 26
- 8.0
- 9.0
- 11
- 1.4 0
- 1.6 0
- 0.78 0
6.9
440
3.2
016
7.1
6.8
7.9
1.6
.96
.37
.18
a
Median
5.0
130
0.78
0.015
5.0
6.8
7.7
0.85
1.0
0.14
0.021
Except pH, which is given in pH units.
-------
D
0)
rt
(D
CPi
K)
UJ
00
o
TABLE 8.3-10.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE RAW WASTEWATER
FOR PAINTING OPERATIONS IN THE COIL COATING INDUSTRY [1]
oo
U)
I
Total industry
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Polycyclic aromatic hydrocarbons
Anthracene
Benzo (a) pyrene
Benzo (b) f luoranthene
Benzo (ghi) perylene
Benzo (k) f luoranthene
Fluoranthene
Naphthalene
Phenanthrene
Halogenated aliphatics
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Number
of points
20
20
20
20
20
20
20
18
18
18
18
18
18
16
18
18
18
18
18
18
18
6
6
9
9
Number
detected
37
15
7
17
2
11
20
14
2
16
15
2
1
2
1
1
1
1
1
3
2
1
1
4
5
Concentration, yg/L
8
4
4
5
32
14
3
5
2
10
2
2
1
0.1
Range
- 270
- 440
- 17
- 200
- 64
190
- 5,000
- 880
- 15
- 20
- 330
- 4
5
5
5
5
5
5
5
- 5
5
36
43
- 3,100
- 3,100
Mean
97
57
8
39
48
190
610
94
10
6
78
3
5
5
5
5
5
5
5
4
5
36
43
900
730
Median
14
13
6
21
48
190
150
17
10
5
50
3
5
5
5
5
5
5
5
5
5
36
43
250
5
Note: Blanks indicate no data available.
-------
TABLE 8.3-11. WASTEWATER FLOW FOR THE
COIL COATING INDUSTRY [1]
Operation
Cleaning
Conversion coating
All operations
Number
of points
9
8
13
Range
7.7
14
9
steel
- 650
- 75
- 890
m3/day
Mean
170
38
440
Median
130
44
500
Cleaning
Conversion coating
Cleaning
Conversion coating
Painting
20
galvanized
10
10
15
1.8
- 330
- 75
105
36
98
45
aluminum
12
12
11
15
- 160
- 60
83
39
85
45
total industry
36 - 1,100
320
250
Wastewaters from the coil coating on steel subcategory generally
have higher levels of phosphorus than that from the other sub-
categories because of the use of concentrated phosphate alkaline
cleaners. Oil and grease in this subcategory are also found in
larger concentrations than the other basis materials wastewater
because of the increased raw material protection needed to inhib-
it rust. This can often cause an increase in the number of
hydrocarbons found in this wastewater. Suspended solids may be
greater because of the adhering dirts in the oil.
Coil coating on galvanized steel generally produces significant
suspended solids concentrations in wastewater. Another pollutant
problem is the high concentration of dissolved zinc and iron in
the wastewater as a result of the dissolved metals from the
cleaning operation. Significant concentrations of hexavalent
chromium are generally expected in all three subcategory
wastewaters.
Wastewaters from the coil coating on aluminum subcategory contain
higher levels of cyanide and fluorides than the other subcate-
gories as a result of chromating solutions containing cyanide
ions and hydrofluoric acid. Aluminum wastewater is also more
acidic and contains more dissolved aluminum. This is due to the
acidic nature of the chromating solutions that dissolve more
aluminum than the phosphating solutions.
Date: 6/23/80
II.8.3-19
-------
Painting wastewater generally consists of quench water. Waste-
water from this operation is generally less toxic than wastewater
from the other general operations; normally only the following
pollutants are expected to exceed 0.010 mg/L: oil and grease,
fluorides, TSS, iron, zinc, bis(2-ethylhexyl) phthalate, and
diethyl phthalate.
II.8.3.3 Plant Specific Information
A limited amount of individual plant specific data for the coil
coating industry is available. Data available in the reference
documents on the influent and effluent streams from the sedimen-
tation treatment system for the plants discussed in the follow-
ing subsections are summarized in Table 8.3-12. These data are
assumed to be screening data because of the lack of definition in
the reference document. All three subcategories are represented
by these facilities.
II.8.3.3.1 Plant 11055
This site uses the chromating and phosphating processes to coat
cold rolled steel, galvanized steel, and aluminum. The data pre-
sented is the analysis of the clarifier influent and effluent at
the site.
II.8.3.3.2 Plant 15436
This facility coats only aluminum basis material by a chromating
process. Approximately 1.6 x 107 m2 of aluminum material is
cleaned and coated and 2.6 x 107 m2 is painted. The plant uses
water at 0.48 L/m2 of product. Treatment consists of clarifica-
tion followed by discharge to surface waters.
II.8.3.3.3 Plant 36058
This plant produces coil-coated metal from all three subcate-
gories. Chromating and phosphating processes are used to clean
and coat 2.0 x 10U m2 of aluminum, 4.7 x 106 m2 of galvanized
steel, and 1.9 x 107 m2 of steel. Water usage at the site is
approximately 19.5 L/m2 for each subcategory. Treatment consists
of clarification, chemical reduction, pH adjustment, and skim-
ming prior to surface discharge, although the treatment sequence
is not indicated.
II.8.3.3.4 Plant 01057
This aluminum coil coating facility uses a chromating process.
Treatment consists of lagooning and sedimentation.
Date: 6/23/80 II.8.3-20
-------
TABLE 8.3-12.
PLANT SPECIFIC INFORMATION ON COIL
COATING PLANTS USING SEDIMENTATION [1J
Concentration
Parameter
Oil and grease, mg/L
TSS, mg/L
Aluminum, yg/L
Chromium, total, yg/L
Copper, yg/L
Iron, yg/L
Lead, yg/L
Nickel, yg/L
Zinc, yg/L
Oil and grease, mg/L
TSS, mg/L
Aluminum, yg/L
Chromium, total yg/L
Copper, yg/L
Iron, yg/L
Lead, yg/L
Nickel, yg/L
Zinc, yg/L
Oil and grease, mg/L
TSS, mg/L
Aluminum, yg/L
Chromium, total, yg/L
Copper, yg/L
Iron, yg/L
Lead, yg/L
Nickel, yg/L
Zinc, yg/L
Oil and grease, mg/L
TSS, mg/L
Aluminum, yg/L
Chromium, total, yg/L
Copper, yg/L
Iron, yg/L
Lead, yg/L
Nickel, yg/L
Zinc, yg/L
Raw
Plant
210
1,100
1,900
35,000
6
15,000
1,500
150
340,000
Plant
170
710
130,000
50,000
14
5,000
150
ND
120
Plant
710
250
71,000
95
110
14,000
130
ND
7,600
Plant
3.8
7.1
4,300
1,800
ND
250
ND
ND
210
Treated
11055
6.4
31
ND
180
15
ND
110
120
500
15436
2.000
52
11,000
2,800
17
900
40
ND
210
36058
ND
120
130
120
15
2,400
ND
ND
720
01057
3.6
2.7
3,300
3
ND
130
ND
ND
34
Percent
removal
97
97
>99
>99
_a
>99
93
20
>99
99
93
92
94
_a
82
73
a
>99
52
82
_a
77
83
>99
96
5
62
23
>99
48
84
Note: ND means not detected.
aNegative removal.
Date: 6/23/80
II.8.3-21
-------
II.8.3.4 Pollutant Removability [1]
This section describes the treatment techniques currently in use
to recover or remove wastewater pollutants normally found at coil
coating facilities. The treatment processes can be divided into
six categories: recovery techniques, oil removal, dissolved
inorganics removal, cyanide destruction, trace organics removal,
and solids removal.
Recovery of process chemicals in coil coating plants is applica-
ble to chromating baths and sealing rinses. Recovery techniques
currently in use include ion exchange and election-chemical chro-
mium regeneration.
Other possible recovery processes that are not currently in use
include evaporation and insoluble starch xanthate. Ion exchange
columns are used at four facilities within the coil coating
industry. The wastewater stream is filtered to remove solids and
then flows through a column of ion exchange resin which retains
copper, iron, and trivalent chromium. The stream then passes
through an anion exchanger which retains hexavalent chromium.
Several columns may be necessary to achieve the desired levels.
By regenerating the exchange resin the life expectancy of the
column is extended. In some regeneration procedures, hexavalent
chromium is removed by conversion to sodium dichromate with
sodium hydroxide. The sodium dichromate is then passed through
a cation exchanger which converts it to chromic acid for reuse.
The cation exchanger can be regenerated with sulfuric acid.
Electrochemical chromium regeneration oxidizes trivalent chro-
mium to hexavalent chromium by electro oxidation. This system
can be used with the wastewater or the drag-out sludge from a
settling basin. One coil coating operation presently uses this
technique for chromic acid regeneration. This system offers
relatively low energy consumption, operation at normal bath tem-
peratures, elimination of metallic sludges, and regeneration of
chromic acid.
Oils occuring in wastewaters from the coil coating industry gen-
erally come from cutting fluids, lubricants, and preservative
coatings used in metal fabrication operations. Oil skimming is
the only current method used in this industry to remove this oil.
Oil flotation has been suggested for this industry to achieve low
oil concentrations or to remove emulsified oils but is not in
current practice.
Oil skimming as a pretreatment method is effective in removing
naturally floating waste material. It can also improve the per-
formance of subsequent downstream treatments. Many coil coating
plants employ this treatment process.
Date: 6/23/80 II.8.3-22
-------
The dissolved inorganic pollutants for the coil coating category
are hexavalent chromium, chromium (total), copper, lead, nickel,
zinc, cadmium, iron, and phosphorus. Removal of these inorganics
is often a major step toward detoxifying wastewater. Chromium
reduction, which can be carried out chemically or electrochemi-
cally, is frequently a preliminary step. The next major step in
the classic treatment system is chemical precipitation, which is
often accomplished by the addition of lime, sodium sulfide, sodi-
um hydroxide, sodium carbonate, or ammonia. These additives
resu.lt in the precipitation of metal hydroxides.
Cyanide destruction in coil coating facilities is necessary to
reduce the cyanide concentration in wastewater from the plating
and cleaning baths. Cyanide is generally destroyed by oxidation.
Alkaline chloririation is the standard technique used in the coil
coating industry, but oxidation by ozone, hydrogen peroxide, or
electrochemically have been suggested for use. These alternate
techniques, however, have not been demonstrated at this time.
Plant sampling data show that organic compounds tend to be
removed in standard wastewater treatment equipment. Oil separa-
tion not only removes oil but also removes organics that are more
soluble in the oil than in water. Clarification also removes
organic solids by adsorption on inorganic solids. Carbon adsorp-
tion to remove organics has been demonstrated in the electro-
plating industry but is not presently used in the coil coating
industry.
Sedimentation by means of clarification is the most common tech-
nique used for the removal of precipitates. The major advantage
of sedimentation is the simplicity of the process. Sedimentation
is used in 55 coil coating plants in various forms, including
ponds, lagoons, slant tube clarifiers, and Lamella clarifiers.
Granular bed filters are used in 10 coil coating plants to remove
residual solids from the clarifier effluent. Chemicals may be
added upstream to enhance the solids removal. Pressure filtra-
tion is also used in this industry to reduce the solids concen-
tration in clarifier effluent and to remove excess water from the
clarifier sludge. Other sludge dewatering technologies used
include vacuum filtration, centrifugation, and sludge bed drying.
Table 8.3-12, presented in section II.8.3.3 of this report, gives
the available pollutant removability data.
Date: 6/23/80 II.8.3-23
-------
II.8.3.5 References
1. Development Document for Effluent Limitations Guidelines and
Standards for the Coil Coating Point Source Category.
EPA 440/l-79/071a, U.S. Environmental Protection Agency,
Effluent Guidelines Division, Washington, DC, August 1979.
2. NRDC Consent Decree Industry Summary - Coil Coating Industry,
Date: 6/23/80 II.8.3-24
-------
II.8.6 FOUNDRIES
II.8.6.1 Industry Description
II.8.6.1.1 General Description [1]
The foundry industry comprises facilities that pour or inject
molten metal into a mold to produce intricate metal shapes that
cannot be readily formed by other methods.
The foundry industry in the United States employs over 400,000
workers in 4,400 foundries that produce over 17,230 Mg (19
million tons) of product annually. This production includes cast
pieces made of iron, steel, aluminum, brass, and copper, as well
as other metals. Included in this industry are Standard
Industrial Classification (SIC) Codes 3321, 3322, 3324, 3325,
3361, 3362, and 3369.
The basic foundry process is essentially the same regardless of
the method of melting, molding, or finishing. A raw material
charge is melted in a furnace, from which the molten metal is
withdrawn as needed. The mold for the product is a sand cast or
a set of metal die blocks which are locked together to make a
complete cavity. The molten metal is ladled into the mold, and
then the mold is cooled until the metal solidifies into the de-
sired shape. The rough product is further processed by removing
excess metal, quenching, cleaning and chemical treatment.
Table 8.6-1 presents industry summary data for the foundry indus-
try including the number of subcategories and the number and type
of wastewater dischargers.
TABLE 8.6-1. INDUSTRY SUMMARY [2]
Industry: Foundries
Total number of subcategories: 9
Number of subcategories studied: 6
Number of dischargers in industry:
Direct: 1,050
Indirect: 498
Zero: 450
No BPT limitations are currently listed for this industry by the
EPA in the available references.
Date: 6/23/80 11.8.6-1
-------
II.8.6.1.2 Subcategory Description [1]
The foundry industry includes a number of foundry types as well
as processes within these foundry types. Plants are capable of
casting one or more metals on a site and each site may utilize
one or more processes that can generate wastewater.
The following subcategories have been selected to describe the
foundry industry based on the type of metal cast, the type of
process, plant size, geographical location, age, wastewater
characteristics and treatability, process water usage, and method
of effluent disposal.
(1) Iron and steel foundries
(2) Aluminum casting
(3) Zinc casting
(4) Copper casting
(5) Magnesium casting
(6) Lead casting
(7) Tin casting
(8) Titanium casting
(9) Nickel casting
Iron and Steel Foundries. Iron is the world's most widely
used metal.When alloyed with carbon, it has a wide range of
useful engineering properties. Four general classes of iron are
produced in foundries: gray, ductile, malleable, and steel.
The same general processes are used with all four classes of
metal in the production of products ranging from cooking utensils
and pipe fittings to steel railroad car wheels.
Aluminum Casting. Aluminum is a light metal with good
tensile strength. It is easily cast, extruded, or pressed, and
it weighs half as much as a similar product made from steel.
Establishments that are engaged in producing castings and die
castings of aluminum and its alloys produce household and hospi-
tal utensils, and machinery castings.
Zinc Casting. Zinc, with a lower melting point than most
metals, is generally die cast, making its process different from
other foundry subcategories. Because it is not as strong as most
metals, it is usually alloyed with metals such as copper, alumi-
num, or magnesium. Common products from this subcategory are
zinc castings.
Copper Casting. Copper is second only to aluminum in impor-
tance among the nonferrous metals. It is often alloyed with tin,
lead, and zinc to produce brass and bronze. Copper castings are
Date: 6/23/80 II.8.6-2
-------
produced by several methods which include centrifugal molds,
green sand molds, and die casting. Products include bushings and
bearings, propellers, and other cast products.
Magnesium Casting. Most magnesium is generally cast in sand
molds. This is to prevent metal-mold reactions, which may occur
because of the reactive nature of molten magnesium. Inhibitors
such as sulfur, boric acid, or ammonium fluorosilicate are often
mixed with the sand to prevent these reactions.
Lead Casting. Lead foundries produce lead castings such as
lead wheel balancing weights and sash balances, as well as white
metal castings.
Other Subcategories. The remaining three subcategories, Tin
Casting, Titanium Casting, and Nickel Casting, have been recom-
mended for Paragraph 8 exclusion under the NRDC Consent Decree.
This recommendation is based on the low number of plants and low
production by these subcategories.
II.8.6.1.3 Subcategory Operations
Several of the above subcategories may be divided into separate
operation types. These operations are presented below with a
brief description of each.
Aluminum Casting. The aluminum foundry industry can be
subdivided into five operations which represent different proc-
esses within the foundry. These include investment casting,
melting furnace scrubbers, casting quench operations, die casting
operations, and die lube operations. Investment (also known as
precision or lost wax) casting operations use molds that are
produced by surrounding an expendable pattern with a ceramic
slurry that hardens at room temperature. The pattern, normally a
wax, is then melted or burned out of the hard mold. These molds
provide very close tolerances. After the molten metal is poured
into the mold and solidifies, the mold is broken away. Thus, a
new mold is needed for each casting. Process wastewaters include
those resulting from mold backup, hydroblast (of castings), and
dust collection (used in conjunction with hydroblasting and the
handling of the investment material and castings).
A second operation inherent to the aluminum foundry industry
involves the use of wet scrubbers to remove noxious materials
from melting furnace gases. The wastewater sources resulting
from this process are either the discharges from wastewater
scrubber equipment packages or the discharge from treatment
systems separate from the scrubber system.
Date: 6/23/80 II.8.6-3
-------
The third operation type, cast quenching, is practiced more
frequently in nonferrous than in ferrous foundries. Ordinarily,
it is used to promote the rapid cooling and solidification of
casting material or to produce certain metal grain structures
that are obtainable only through sudden thermal changes. In
these cases, the casting is quenched in a water bath which may be
plain water or may contain an additive to promote some special
condition. The only wastewaters considered in association with
this operation are those which are discharged from the casting
quench tanks.
Theoretically, the fourth operation type, die casting, does not
produce a process wastewater. However, in most die casting
operations major sources of wastewater include contact mold
cooling water, die surface cooling sprays, casting machine
hydraulic systems using water, and leakage from various noncontact
cooling systems which are subsequently contaminated by dirt, oil,
and grease.
Die lube operations involve the application of lubricants to die
casting molds to prevent the casting from sticking to the die.
The lubricants used are dependent on the temperature of the
metal, the operating temperature of the die, and the alloy to be
cast. The lubricants, generally organic compounds, may enter the
waste stream through leaks in mold machinery.
Copper and Copper Alloy Casting. The copper and copper
alloy foundry industry can be subdivided into three operation
types which represent various processes within the plant: dust
collection, mold cooling and casting quench, and continuous
casting. Mold cooling is commonly used in casting operations
which employ permanent molds. In such an operation, it is often
necessary to force cool the mold with water which subsequently
becomes contaminated with materials picked up from the mold
surface.
Continuous casting is used in operations where a slab or billet
is "worked" to produce a final product. Such slabs are continu-
ously cast by pouring molten metal into a water-cooled mold at a
controlled rate and withdrawing a solid piece from the bottom of
the mold. This piece is then cut into lengths for further
processing. Wastewaters result from the cooling of the molds and
castings used in and produced from continuous casting equipment.
Dust collection and casting quench operations are similar to
those used in aluminum foundries.
Ferrous Foundries. Ferrous (iron and steel) foundries have
five operations that can produce wastewater in some form. These
include dust collection, melting furnace scrubber, slag quench-
ing, casting quench and mold cooling, and sand washing operations.
Slag quenching is commonly used to rapidly cool and fragmentize
Date: 6/23/80
-------
slag (a mixture of nonmetallic fluxes introduced with the "charge"
to remove impurities from the molten metal) to an easily handled
bulk material. The quench water is a waste product that must be
handled.
The reclamation and reuse of sand is a major operation in found-
ries which use sand as a molding media. In this operation, water
is used to "wash" impurities, primarily "spent" binders and sand,
from the casting sand prior to its reuse in the molding opera-
tions. The sand and binders become "spent" as a result of the
heat present in the casting process. Additionally, sand can be
"washed" using a number of dry and thermal methods. These latter
methods have the advantage of not producing a wastewater stream.
Dust collection, melting furnace scrubber, casting quench and
mold cooling operations are similar to those described for
aluminum and copper/copper alloy foundries.
Magnesium Casting. Magnesium foundries generate wastewater
in grinding scrubber and dust collection operations. Because of
the violent reaction of fine magnesium particles with air, wet
scrubbers are used to control the dust from the grinding
operations.
Zinc Casting. Zinc foundry operations include casting
quench operations and melting furnace scrubber operations
similar to those described above.
II.8.6.1.4 Wastewater Flow Characterization [1]
Table 8.6-2 presents wastewater flow characterization for the
foundry industry by subcategory. Also presented in this table
is the degree of process water recycle, and the number of plants
surveyed with central wastewater treatment facilities for all of
the processes at that plant. The discharge flow represents all
processes within the subcategory.
II.8.6.2 Wastewater Characterization [1]
Each type of operation in the foundry industry can produce dif-
ferent types of pollutants in the wastewater stream. Also
because each subcategory operation often involves different
processes, subcategory pollutant concentrations may vary. The
character of wastewater for each subcategory is given in Tables
8.6-3 through 8.6-12. Operations within each subcategory have
been combined to give an overall view of the subcategory. More
detailed information on each operation is provided in the section
of this report dealing with each specific plant.
Date: 6/23/80 II.8.6-5
-------
Date: 6/23/80
n
CD
1
CT>
TABLE
Subcategory
Iron and steel foundries
Aluminum casting
Zinc casting
Copper casting
Magnesium casting
Lead casting
8.6-2. WASTEWATER FLOW CHARACTERIZATION BY SUBCATEGORY [1]
Amount bF
Respondents, Discharge flow, mj/d recycle.
no. of plants Range Average Median %
283 0 - 100
30 0.15 - 2.0 x 10* 170 7.3 0 - 100
14 10.3 - 280 99 11.4 0 - 100
21 1.2 - 6.7 x 10* 1,800 420 0 - 100
2 0.01 - 3.2 1.6 1.6 0 - 100
0
Central treatment Operation
facilities, treatment facility.
no. of plants no. of plants
82 178
7 18
6 8
7 14
0 2
Notei Blanks indicate no information currently available.
-------
TABLE 8.6-3.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR THE IRON AND STEEL
FOUNDRIES [1]
Pollutant
TSS
Total phenols
Sulfides
Oil and grease
pH
Number of times Concentration, mg/La
Sampled Detected Maximum Average Median
23 23 8,900 2,700 1,100
20 19 31 2.9 0.59
9 9 10 2.1 1.0
18 16 200 29 10
21 21 11 7.7 7.5
aExcept pH values
TABLE 8.6-4.
, which are given in pH units.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR ALUMINUM CASTING [1]
Pollutant
TSS
Total phenols
Oil and grease
PH
Number of times Concentration, mg/L
Sampled Detected Maximum Average Median
8 8 1,700 540 100
4 4 66 17 0.07
8 8 8,500 1,200 20
8 8 8.6 7.3 7.2
aExcept pH values
TABLE 8.6-5.
, which are given in pH units.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR ZINC CASTING [1]
Pollutant
TSS
Total phenols
Oil and grease
pH
Number of times Concentration, mg/La
Sampled Detected Maximum Average Median
3 3 3,800 1,300 92
3 3 1.4 0.52 0.11
3 3 17,000 5,700 70
3 3 7.4 6.8 7.4
aExcept pH values, which are given in pH units.
Date: 6/23/80
II.8.6-7
-------
TABLE 8.6-6.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR COPPER CASTING [1]
Number of times
Pollutant
TSS
Oil and grease
PH
Sampled
2
3
3
Detected
2
2
3
Concentration, mg/La
Maximum
610
38
8.3
Average
230
23
7.7
Median
230
30
7.8
Except pH values, which are given in pH units.
TABLE 8.6-7.
WASTEWATER CHARACTERIZATION OF CONVENTIONAL
POLLUTANTS FOR MAGNESIUM CASTING [1]
Number of times Concentration, mg/La
Pollutant
TSS
Total phenols
Oil and grease
pH
Sampled
1
1
1
2
Detected Maximum Average
1
1
1
2 9.8 8.7
Median
8.3
1.1
6
8.7
Except pH values, which are given in pH units.
Date: 6/23/80
II.8.6-8
-------
TABLE 8.6-8.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOUND IN IRON AND STEEL FOUNDRIES [1]
Number of times
Toxic pollutant Sampled
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Ethers
Bis(2-chloroethyl) ether
Bis (2-chloroethoxy )me thane
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Benzidine
N-nitrosodiphenylamine
N-nitroso-di-n-propylamine
8
8
16
10
10
17
22
17
21
17
10
4
4
17
3
3
10
8
10
9
9
2
1
6
1
Detected Range, |Jg/L Median, pg/L
5
4
9
3
8
15
12
14
13
13
1
2
2
11
1
2
7
6
6
5
4
2
0
5
1
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
BDL -
ND -
900
160
BDL
740
700
4,400
370
140,000
3.6
910
BDL
30
BDL
170,000
BDL
20
1,200
200
200
39
2,200
41
1,400
50
2
BDL
ND
35
300
6
320
0.1
40
ND
NDa
NDa
590
ND
BDL
5.5
16
a
6
1
ND
a
41
ND
12
BDL
(continued)
Date: 6/23/80
II.8.6-9
-------
TABLE 8.6-8 (continued).
Toxic pollutant
Phenols
2-Chlorophenol
2 ,4-Dichlorophenol
2 ,4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
£-Chloro-m-cresol
4,6-Dinitro-o-cresol
Aromatics
Benzene
Chlorobenzene
2 ,4-Dinitrotoluene
2,6-Dinitrotoluene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1,2,4-Trichlorobenzene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo(a)pyrene
Benzo (b ) f luoranthene
Benzo ( k ) f luoranthene
Chrysene
Flucranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Number
Sampled
7
7
9
6
4
6
9
7
6
6
10
2
3
4
5
1
2
8
3
9
9
9
7
4
3
2
9
10
8
10
9
10
of times
Detected
4
5
6
4
3
4
6
3
4
4
5
2
3
4
4
1
2
5
2
6
6
7
5
4
3
2
4
7
6
5
7
6
Range
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
, ^g/L
200
2,200
1,100
40
40
130
20,000
80
ND 170
ND -
ND -
BDL
BDL -
BDL -
ND -
<3 -
ND -
ND -
ND -
ND -
ND -
ND -
BDL -
BDL -
BDL -
ND -
ND -
ND -
ND -
ND -
ND -
38
100
<50
<50
BDL
<280
40
7
36
40
<410
21
<30
<36
6
21
<390
<620
93
<410
<1,100
Median, pg/L
BDL
20
11
ioa
13a
21a
100
ND
BDL
14a
ND3
BDL
<7
<7a
BDL
BDL
<140
I3
BDL
BDL
BDL
<3
9
BDL
6
6a
ND
I3
44
ND3
<3
6a
(continued)
Date: 6/23/80
II.8.6-10
-------
TABLE 8.6-8 (continued).
Toxic pollutant
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232
1248, 1260
Aroclor 1221, 1254, 1424
Halogenated aliphatics
Carbon tetrachloride
Cloroform
Dichlorobromome thane
1 , 2-Trans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
B-BHC
6-BHC
Y-BHC
Chlordane
4, 4 '-DDE
4,4'-DDD
4, 4 '-DDT
Dieldrin
a-Endosulfan
p-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
Number
Sampled
10
10
8
10
3
1
10
10
10
3
7
6
7
7
8
6
5
5
5
9
7
5
5
4
5
5
7
6
6
of times
Detected
4
3
6
3
1
1
6
4
6
2
3
3
0
2
1
3
0
2
1
3
6
4
2
2
4
2
2
0
1
Range
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
. nq/L
270
330
20
80
37
470
370
60
20
180
BDL
30
20
20
20
BDL
20
20
BDL
BDL
BDL
9
20
20
BDL
Median, pg/L
ND
ND
BDL
ND
ND
<11
BDL
ND
BDL
BDL
ND
ND3
ND
ND
ND
ND3
ND
ND
ND
ND
BDL
BDL
ND
NDa
BDL
ND
ND
ND
ND
Determination of median concentration involved averaging of given value
and BDL.
Date: 6/23/80
II.8.6-11
-------
TABLE 8.6-9.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOUND IN ALUMINUM CASTING FOUNDRIES [1]
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Ethers
Bis(2-chloroethyl) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitroso-di-n-prppylamine
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
2-Nitrophenol
Pentachlorophenol
Phenol
2 , 4 , 6-Trichloro.phenol
4 , 6-Dinitrophenol
p_-Chloro-m-cresol
4,6-Dinitro-o-cresol
Number
Sampled
8
1
9
9
9
9
9
9
X
9
3
9
7
4
3
2
3
7
7
5
3
6
8
4
&
5
of times
Detected
4
1
7
4
5
4
2
9
1
7
3
9
6
3
3
2
3
7
7
5
3
5
7
2
5
5
Range
ND -
ND -
ND -
ND -
ND -
ND -
90 -
ND -
BDL -
BDL -
ND -
ND -
BDL -
34 -
BDL -
BDL -
BDL "
BDL -
B*DL -
ND -
ND -
ND -
ND -
BDL -
, pg/L
<100
14
2,000
0.9
300
<40
8,800
820,000
690
5,400
730
35
4
210
53
5,700
91
330
1,600
26,000
380
140
280
70
Median, (JQ/L
NDa
450
5
50
BDL
ND
ND
810
9
680
BDL
74
91*
29a
BDL
120
53
22
41
29
BDL
570
250
ND
71
61
(continued)
Date: 6/23/80
11,9.6-12
-------
TABLE 8.6-9 (continued)
Number of times
Toxic pollutant Sampled Detected Range, ua/L Median, ug/L
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo(a)pyrene
Chrysene
Fluor anthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254, 1424
Halogenated aliphatics
Bromofonn
Carbon tetrachloride
Chlorodibronone thane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1 , 2-Dichloroethane
9
1
4
8
5
7
4
3
4
4
7
7
5
4
7
8
8
1
6
1
9
6
1
3
9
1
3
7
3
3
4
2
3
3
6
5
4
4
7
8
8
1
6
1
5
4
1
3
BDL -
ND -
ND -
ND -
ND -
BDL -
ND -
ND -
ND -
ND •
ND -
ND -
BDL •
BDL -
BDL -
BDL -
BDL -
ND -
ND -
BDL •
84
78
540
200
47
<470
< 13, 000
53
43,000
320
800
160
<470
250
830
1,400
480
450
2
170
BDL
250
BDL
.BDL
BDL
ND»
-------
TABLE 8.6-9 (continued)
Number of times
Toxic pollutant Sampled Detected Range. pg/L Median. pq/L
Halogenated aliphatics
(continued)
1,2-Trans-dichloroethylene 20 ND
Hethylene chloride 9 4 ND • 2.400 ND
1,1,2,2-Tetrachloroethane 2 2 BDL - 18 18
Tetrachloroethylene 8 3 ND - 160 ND
1,1,1-Trichloroethane 3 2 ND • 16,000 140
1,1,2-Trichloroethane 1 1 BDL
Trichloroethylene 8 7 ND • 280 BDL
Pesticides and metabolites
Aldrin
o-BHC
^-BHC
6-BHC
Y-BHC
Chlordane
4, 4' -DDE
4 ,4 '-ODD
4, 4 '-DDT
Dieldrin
a-Endosulfan
0-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
2
7
5
8
2
5
6
2
8
3
3
3
2
3
2
4
2
2
6
4
8
2
4
5
2
7
3
3
2
2
2
2
3
1
BDL
ND • 26
ND - 70
BDL - 2
BDL
ND - 38
ND • 10
BDL
ND - BDL
BDL
BDL
ND - BDL
BDL
ND - BDL
BDL
ND - BDL
ND - BDL
BDL
BDL
BDL
BDL
BDL
BDL
10*
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
ND
'Determination of median concentration involved averaging of given value
and BDL.
Date: 6/23/80 „ „
II.8.6-14
-------
TABLE 8.6-10.
WASTEWATER CHARACTERIZATION OP TOXIC POLLUTANTS
FOUND IN ZINC CASTING [1]
Number of times
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
4-Nitrophenol
4 , 6-Dinitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p_-Chloro-m-cresol
Aromatics
Benzene
Toluene
2 ,4-Dinitrotoluene
2 , 6-Dinitrotoluene
Ethylbenzene
Nitrobenzene
1,2, 4-Trichlorobenzene
Polyacrylic aromatic
hydrocarbons
Acenaphthene
Acenaphthlyene
Benzo(a) anthracene
Chrysene
Samples
3
3
4
4
3
3
3
4
4
3
4
3
2
1
2
3
4
1
2
1
4
3
3
2
2
1
1
1
1
1
3
2
1
1
Detected
3
1
3
4
2
2
0
4
4
3
4
2
2
1
2
3
4
1
2
1
4
3
3
2
2
1
1
i
i
i
2
2
1
1
Range ,
MQ/L
<10
ND-150
ND-19
<10
ND-0.3
ND-3
3,700-350,000
67-5,500
<10-80
<10-217
ND-110
<10-80
19-210
<10-1,300
32-12,000
<10-900
<10-30,000
51-1,400
14-73
<10-150
<10-27
ND-37
<10-43
Median,
- --M9/L
<10
ND
9
<10
0.3
ND
ND
41,000
2,100
<10
14
<10
45
2,800
120
25
75
1,600
460
<10
260
65
30
80
19
<37
<37
<10
60
1,000
<10
27
<10
<10
Date: 6/23/80
II. 8. 6-15
-------
TABLE 8.6-10 (continued)
Toxic pollutant
Number of times
Samples Detected
Range,
Median,
Polyacrylic aromatic hydro-
carbons (continued)
Anthracene
Fluorene
Phenanthrene
Fluoranthene
Naphthalene
Pyrene
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254, 1424
1
2
1
3
4
3
1
2
1
3
4
3
<10-46
<10-3,300
<5-54
<5-43
<86
28
<86
12
30
<5
<5
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 2-Trans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Bromoform
Dichlorobromome thane
Pesticides and metabolites
Aldrin
d-BHC
6-BHC
6-BHC
Y-BHC
Chlordane
4, 4 '-DDE
4, 4 '-ODD
4,4'-DDT
a-Endosulfan
B-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
2
4
1
4
3
1
2
1
1
1
2
1
4
1
2
4
2
4
2
2
1
1
2
1
2
2
2
1
2
1
1
2
1
1
1
2
1
4
1
2
4
2
4
2
2
1
1
2
1
2
<10-29
ND-57
ND-290
ND-132
<10-230
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
15
<5
43
6
ND
144
120
<10
<10
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
Date: 6/23/80
II.8.6-16
-------
TABLE 8.6-11.
WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOUND IN MAGNESIUM CASTING [1]
Toxic Pollutant
Metals and inorganics
Copper
Cyanide
Lead
Mercury
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-Chlorophenol
2-Nitrophenol
Pentachlorophenol
Phenol
2, 4-Dimethylphenol
Aromatics
Benzene
1, 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1, 4-Dichlorobenzene
Hexachlorobenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Benzo (a)pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254, 1424
Halogenated aliphatics
Chloroform
Dichlorobromoraethane
Hexachloroe thane
Methylene chloride
Tetrachloroethylene
pesticides and metabolites
o-BHC
Y-BHC
4, 4 '-ODD
4,4' -DDT
Dieldrin
a-Endosulfan
Endrin aldehyde
Heptachlor epoxide
Number
Sampled
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
1
2
2
2
1
2
1
1
2
2
1
1
1
2
1
1
2
1
of times
Detected
2
0
2
0
0
1
0
1
1
0
0
1
1
1
0
1
1
1
1
1
1
1
1
2
0
0
1
0
2
1
2
2
2
1
0
0
1
1
0
1
1
1
2
1
1
2
0
Range (ug/L) Median (ug/L)
20-60
30-80
ND-1,200
ND-10
ND-40
ND-32
BDL-<30
ND-10
BDL- 3
BDL-<30
BDL-<7
BDL
ND-44
BDL
BDL
40
ND
55
ND
ND
600
ND
5
20
ND
ND
BDL
11
6
ND
BDL
BDL
BDL
BDL
BDL
18
11
16a
<30a
ND
ND
5
ND
33
BDL
<3§a
<7a
BDL
BDL
ND
ND
BDL
22
ND
BDL
BDL
BDL
BDL
BDL
BDL
BDL
ND
Determination of median concentration involved averaging of given value and BDL.
Date: 6/23/80
II.8.6-17
-------
TABLE 8.6-12. WASTEWATER CHARACTERIZATION OF TOXIC POLLUTANTS
FOUND IN COPPER AND COPPER ALLOY CASTING [1]
Number of times
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
1 , 2-Diphenylhydrazine
Phenols
2 , 4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
4 , 6-Dinitrophenol
4,6-Dinitro-o-cresol
Aromatics
Benzene
2 , 6-Dinitrotoluene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Benzo(a)pyrene
Samples
3
1
3
3
3
3
3
3
3
3
3
3
2
2
2
1
2
1
1
2
2
1
1
2
1
2
1
2
2
3
1
1
2
Detected
2
0
2
1
2
1
1
0
3
1
2
1
2
2
2
1
2
1
1
2
2
1
1
1
1
1
1
1
2
2
1
1
2
Range ,
pg/L
ND-100
ND-110,000
ND-490
ND-28,000
ND-0.1
ND-720
2,000-130,000
ND-11
ND-180
ND-1
BDL-6
15-38
BDL
BDL-36
11-17
BDL-25
ND-BDL
ND-BDL
ND-BDL
BDL- 5
ND-6
BDL-6
Median,
pg/L
100
ND
350
ND
70
ND
ND
ND
2,700
ND
6
ND
6a
27
BDL
BDL
36a
BDL
BDL
14
25a
BDL
BDL
ND3
BDL
ND3
4
ND3
5a
BDL
<21
<29
6a
Date: 6/23/80 II.8.6-18
-------
TABLE 8.6-12 (continued)
Toxic pollutant
Number of times
Samples Detected
Range,
Median,
Polycyclic aromatic hydro-
carbons (continued)
Benzo(k)fluoranthene
Benzo(b)fluoranthene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254, 1424
1
1
2
3
2
1
1
3
1
1
2
2
2
1
1
3
3
3
0
0
BDL-57
ND-4
BDL
BDL-12
<7
<7
57
BDL
BDL
11
a
ND
ND
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chloroform
Hexachlorocyclopentadiene
Methylene chloride
Tetrachloroethylene
Trichloroethylene
1 , 1 , 1-Trichloroe thane
Pesticides and metabolites
Aldrin
a-BHC
P-BHC
6-BHC
Y-BHC
Chlordane
4, 4 '-DDE
4,4'-DDT
Dieldrin
Endosulfan sulfate
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
1
1
3
1
3
2
I
1
2
3
3
3
2
2
3
2
1
3
2
3
2
1
1
1
0
1
0
1
1
1
1
0
1
2
1
1
3
0
0
1
2
1
2
1
ND-80
ND-BDL
ND-BDL
ND-BDL
ND-BDL
ND-BDL
BDL
ND-BDL
BDL-4
ND-BDL
BDL
BDL
11
ND
BDL
ND
40
56
37
a
ND
ND
ND
BDL
A
NDa
NDa
BDL
ND
ND
ND
4a
ND
BDL
BDL
Determination of median concentration involved averaging of given value and
BDL.
Date: 6/23/80
II.8.6-19
-------
II.8.6.3 Plant Specific Descriptions [1]
The following plants have been selected to present plant-specific
information on each subcategory and, when possible, each process
within the subcategory. Plants were selected on the basis of the
completeness of the available information. A brief description
is given of each plant, its treatment system, and the toxic and
conventional pollutants emitted.
II.8.6.3.1 Iron and Steel Foundries
Plant 291C. This large foundry has a separate treatment
system for melting scrubbing waters. This consists of chemical
additions, clarification, and vacuum filtration of the settled
materials. Clarifier overflow is recycled with makeup from non-
contact cooling water.
Dust collection scrubber water, slag quench water, and sand wash-
ing wastewaters are settled and recycled with makeup from noncon-
tact cooling water. Excess water is discharged to a Publicly
Owned Treatment Works (POTW).
Plant 417A. This plant employs a heat-treated casting
quench operation involving the complete recycle of all process
wastewaters. The treatment system utilizes a settling channel,
from which solids are removed infrequently, and a cooling tower
to provide for quench water cooling.
Tables 8.6-13 and 8.6-14 present plant-specific information for
each process within the iron and steel foundry industry.
II.8.6.3.2 Aluminum Foundries
Plant 4704. Wastewaters from mold backup, hydroblast cast-
ing cleaning, and dust collection are co-treated. Polymer is
added to aid settling in a Lamella inclined-plate separator. The
Lamella unit sludge is filtered through a paper filter, and the
filtrate is returned to the head of the treatment system. The
treated effluent is discharged to the river.
Plant 715C. This plant provides for the complete recycle of
all die lubricating operation solutions. The die lubrication
solutions are collected both by gravity drains connected to a
holding tank and by drip pans beneath each casting machine.
Wheeled tanks are used to collect and transport the die lubricant
solutions collected in these pans to the die lubricant storage
tanks.
A skimmer located on the holding tank provides for tramp oil
removal. The die lubricant solutions are pumped from the holding
tank, through a cyclonic separator, and then to a storage tank
Date: 6/23/80 n. 8.6-20
-------
Date: 6/23/80
TABLE 8.6-13. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN THE IRON
AND STEEL SUBCATEGORY, PLANT 291C AND PLANT 417A [1]
Plant 291C Plant 417A
Melting furnace Slag Sand Casting
scrubber operations Dust collectors quenching operations washing operations quench operations
H
H
CO
1
to
Concentration ,
mg/La
Flow/pollutant Raw Treated
Flow, m3/Mg 2.1 2.1
Pollutant
TSS 1,100 71
Total phenols 3 12
Sulfides
Oil and grease 70 21
pH 6.9 6.9
Concentration,
Percent mg/La
removal Raw Treated
0.40 0.40
94 410 41
-b 0.23
1 0.2
70 3 2.7
7.2 7.3
Concentration, Concentration, Concentration,
Percent mg/La Percent mg/La Percent mg/La Percent
removal Raw Treated removal Raw Treated removal Raw Treated removal
0.42 0.42 0.84 1.05 21 21
90 630 170 73 90 62 31
2.1 1.7 19 0.01 0.022 -b
80 10 2 80
10 200 39 81 4 ND 9 -b
7.0 6.2 8.6 8.6
Note: Blanks indicate no information available.
Except flow, which is given in m3/Mg, and pH values, which are given in pH units.
b
Negative removal.
-------
o
ft)
ri-
ft)
TABLE 8.6-14.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE IRON AND
STEEL SUBCATEGORY, PLANT 291C AND PLANT 417A [I]
oo
cr>
i
ho
to
Melting furnace
scrubber operations
Concentration,
pg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
800
160
ND
740
430
3,400
47
100,000
1.1
110
ND
30
BDL
150,000
Treated
400
30
BDL
840
BDL
220
180
8,500
1.1
130
BDL
BDL
BDL
190,000
Percent
removal
50
W,
94v,
92
Plant
Dust collectors
Concentration ,
Raw
70
ND
ND
ND
7
90
7
30
ND
ND
ND
ND
W9/L
Treated
BDL
BDL
BDL
BDL
BDL
BDL
74
10
1
20
BDL
370
Percent
removal
67K
291C
Plant 417A
Slag
quenching operations
Concentration,
Mg/L Percent
Raw
200
700
350
ND
6,100
2.1
40
ND
25,000
Treated removal
BDL -a
BDL -a
BDL -a
ND
590 90
2 5
39 2
BDL -a
8,000 68
Sand
washing operations
Concentration,
ug/L
Raw
300
3
ND
ND
ND
ND
5
100
0.1
BDL
ND
ND
Treated
BDL
BDL
BDL
BDL
BDL
70
25
80
1.3
BDL
BDL
12,000
Percent
removal
_
_
_
_
_
b
_b
20
b
a
a
b
Casting
quench operations
Concentrations,
Raw
ND
ND
ND
ND
ND
20
3
ND
ND
ND
ND
ND
ND
ND
Ug/L
Treated
BDL
BDL
BDL
BDL
BDL
50
2
60
0.8
BDL
BDL
BDL
BDL
140
Percent
removal
_
_
_
_
_
33
a
b
Ethers
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl)
ether
Phthalates
Bis(2-ethylhexyl) phthalates
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Acrylonitrile
Benzidine
1,2-Diphenylhydrazine
N-nitrosodiphenylamine
Phenols
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2 ,4 ,6-Tnchlorophenol
p-Chloro-w-cresol
4,6-Dinitro-o-cresol
90
74
ND
ND
660
84
41
190
30
320
73
9
ND
ND
3
ND
BDL
2
BDL
8
BDL
44
70
ND
ND
ND
ND
39
ND
ND
40
130
80
ND
ND
ND
23
BDL
BDL
190
85
40
400
30
20
140
2,600
72
63
88
ND BDL
ND BDL
ND BDL
ND BDL
ND 12
ND 3
ND 2
ND
ND 7
1,200
20
110
39
ND
1,400
20
20
60
40
21
100
80
120
20
90
27
70
20
180
36
99
87
ND
ND
ND
11
BDL
BDL
BDL
10
BDL SDL
ND BDL
40
ND >99
40 33
40
27
88
51
17
36
BDL
BDL
BDL
ND
ND
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL BDL
BDL ND
(continued)
-------
tu
rt
en
NJ
00
\
00
o
TABLE 8.6-14 (continued)
oo
ro
U)
Plant 291C Plant 4!
Melting furnace
scrubber operations
Concentration ,
ug/L
Toxic pollutant
Aromatics
Benzene
Chlorobenzene
2 , 4-Dinitrotoluene
2 , 6-Dinitrotoluene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1 , 2 , 4-Trichlorobenzene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Benzo (a) pyrene
Chrysene
Fluoranthrene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Raw
16
BDL
BDL
BDL
<280
3
ND
ND
ND
78
9
4
390
620
ND
78
1,100
Treated
17
300
300
BDL
BDL
BDL
570
BDL
16
32
BDL
BDL
97
9
270
32
47
Percent
removal
-a
~b
a
59
a
75
"a
53
96
Dust collectors
Conce
Raw
ND
<7
<7
<3
ND
7
ND
ND
3
ND
BDL
ND
ND
ND
ND
3
ND
nt rat ion,
lig/L
Treated
BDL
BDL
10
10
51
BDL
13
6
5
BDL
51
19
Percent
removal
-
-
b
~b
~b
-
b
b
-b
~b
7 A
Slag Sand Casting
quenching operations washing operations quench operations
Concentration, Concentration, Concentrations,
tiq/L Percent ug/L Percent jg/L
Raw Treated removal Raw Treated removal Raw Treated
100 60 40 BDL ND BDL
BDL
40 40 -C
20 27 - ND BDL -3
40 57 - ND BDL -
ND ND <4 -
20 60 - BDL BDL
BDL
ND ND BDL -3 ND BDL
51 72 -** ND BDL -3 ND BDL
53 68 -c
20 20 - ND BDL - ND BDL
ND ND <4
ND ND BDL -a ND BDL
Percent
removal
-
a
a
Polychlorinated biphenyls
and related compounds
Arochlor 1016, 1232,
1248, 1260
Aroclor 1221, 1254,
1424
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Dichlorobromomethane
1,2-Dichloroethane
270
330
ND
ND
46
55
BDL
26
83
83
BDL BDL
ND BDL
ND 18
20
20
20
80
37
20
20
210
23
b
38
ND
ND
<20
ND
BDL
BDL
ND BDL
ND BDL
BDL BDL
ND BDL
(continued)
-------
D
0)
TABLE
(continued)
rr
(D
Plant 291C
•* Melting furnace
scrubber operations
Concentration,
CTl ug/L
\
K)
O.'
^
00
o
h- <
f-H
•
CD
•
CTi
1
NJ
Toxic pollutant
Halogenated aliphatics
(continued)
Methylene chloride
Tetrachloroethylene
1,1, 1-Tr ichloroethane
1,1,2 -Tr ichloroethane
Tnchloroethylene
Pesticides and metabolites
Aldriri
a-BHC
B-BHC
6-BHC
Y-BHC
Chlordane
4, 4 '-DDE
4,4' -DDD
4,4' -DDT
Dieldrin
a-Endosul fan
B-Endosul fan
Endosul fan sulfate
Endr in
Endrin aldehyde
Heptachlor
Heptachlor epoxide
I sophorone
Note: Blanks indicate no
Raw
20
ND
ND
ND
ND
BDL
ND
BDL
BDL
ND
BDI,
BDL
ND
9
ND
Treated
36
4S
0
BDL
30
BDI,
R
BDL
BDL
BDL
BDL
BDL
BDL
BDI,
BDL
Percent
removal
b
b
"b
a
~b
a
b
a
a
a
b
b
a
a
Dust collectors
Concentration,
pg/L Percent
Raw Treated removal
ND 5 b
ND 1 "b
ND BDL a
BDL BDL a
BDL
ND BDL a
ND BDL a
BDL
ND BDL a
BDL
ND BDL a
RDL
ND
Slag Sand
quenching operations washing operations
Concentration, Concentration,
pg/L Percent pg/L
Raw
470
370
60
20
180
ND
20
20
20
20
20
20
20
20
Treated removal Raw
230 51 ND
72 SI BDL
40 33 ND
20 89
BDL a
ND
ND
20 c ND
20 c ND
ND
ND
BDL
20 c ND
ND
ND
BDL
BDL
20 c ND
ND
ND
Treated
10
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Percent
removal
b
a
a
a
a
~a
a
a
a
a
a
a
a
a
Plant 417A
Casting
quench operations
Concentrations ,
Raw
ND
ND
BDL
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ug/L Percent
Treated removal
BDL a
BDL a
BDL "b
BDL a
BDL
BDL a
BDL "a
BDL a
BDL ~a
BDL
BDL a
BDL a
BDL
BDL a
BDL a
BDL a
BDL ~a
information currently available.
Negative removal.
Indicates negligible removal.
-------
for reuse. A paper filter is used to remove solids from the
cyclone concentrate; the filtrate goes into the storage tanks.
The die lubricants collected in the pans are filtered using a
paper filter prior to discharge to the storage tanks. In the
storage tanks the solutions are "freshened" with makeup water or
new lubricants as needed. The wheeled tanks mentioned above are
then used to transport the die lubricants back to the machines.
An extensive maintenance program is followed to minimize leakage
of various fluids at the die casting machines which would result
in contamination of the die lubricant solutions.
Plant 574C. Aluminum and zinc die casting waters are
co-treated. After collection in a receiving tank where oil is
skimmed, they are batch treated by emulsion breaking, floccula-
tion, and settling before discharge. The released oil is
returned to the receiving tank for skimming, and the settled
wastes are vacuum filtered and dried before being landfilled.
Filtrate water is returned to the receiving tank.
Tables 8.6-15 and 8.6-16 present plant-specific information on
conventional and toxic pollutants for the above facilities.
II.8.6.3.3 Copper Foundries
Plant 6809. Mold cooling and casting wastewaters are
recycled through a cooling tower in this system; a portion of the
process wastewater flow is "blowndown" for treatment with other
nonfoundry wastewaters. The mold cooling and casting quench
system blowdown represents 3% of the combined wastewater flow.
These combined wastewaters are settled and skimmed in a lagoon
and are then discharged.
Plant 9979. This plant is a continuous casting operation
producing both copper and aluminum products. This 100% recycle
operation uses a cooling tower to reduce the wastewater system
heat load.
Plant 9094. This plant has requested confidentiality. No
treatment technology description is available.
Tables 8.6-17 and 8.6-18 present conventional and toxic pollutant
data for the above copper foundry facilities.
II.8.6.3.4 Magnesium Foundries
Plant 8146. This foundry uses dust collectors and magnesium
grind! ig scrubbers from which the wastewater flow is discharged
untreated. No treatment description or treated wastewater con-
centrations are available. Tables 8.6-19 and 8.6-20 present
conventional and toxic pollutant data for this facility.
Date: 6/23/80 II.8.6-25
-------
D
Pi
rt
(D
TABLE 8.6-15.
CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN THE ALUMINUM
CASTING SUBCATEGORY, PLANT 4704, PLANT 574C, AND PLANT 715C [1]
to
CD
O
CD
•
cr>
I
Plant 4704
Investment
casting operations
Concentration ,
mg/La Percent
Flow/pollutant Raw Treated removal
Flow, m3/Mg 21 21
Pollutant
TSS 930 83 91
Total phenols
Sulf ides
Oil and grease 18 10 44
pH 7 7.1
Plant 574C Plant 715C
Die Die
casting operations lube operations
Concentration, Concentration,
mg/La Percent mg/La
Raw Treated removal Raw Treated
5.5 5.5
530 9.9 98 1,700 1,600
66 64
3.3 <0.2
20 12 40 8,500 9,900
7.2 9.1 6.9 7.1
Percent
removal
6
3
94
_b
Note: Blanks indicate no information currently available
aExcept' pH values, which are given in pll units.
Negative removal.
-------
TABLE 8.6-16.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
ALUMINUM CASTING SUBCATEGORY, PLANT 4704,
PLANT 574C, AND PLANT 715C [1]
Toxic pollutant
Plant 4704
Investment
casting operations
Concentration,
ycj/L Percent
Raw Treated removal
'Plant 574C
Die
casting operations
Concentration,
ug_/L Percent
Raw Treated removal
Plant 715C
Die
lube operations
Concentration,
pq/L Percent
Raw Treated removal
Polychlorinated biphenyls and
related compounds
Aroclor 1016, 1232,
1248, 1260 10 BDL 50
Aroclor 1221, 1254 .
1424 3 BDL
Halogenated aliphatics
Carbon tetrachloride 26 10 62 BDL BDL
Chloroform ND 20 47
Dichlorobromomethane BDL
1,1-Dichloroethane k
1,2-Dichloroethane 5 BDL
1,2-r7-a>is-dichloroethylene ND ND BDL
Methylene chloride 40 34 15 2 39
1,1,2,2-Tetrachloroethane BDL
Tetrachloroethylene 10 94 - ND 30
1,1,1-Tnchloroethane 140 46 67, ND 51
1,1,2-Tnchloroethane BDL BDL
Trichloroethylene 69 78 - ND 21
Pesticides and metabolites
Aldrin
a-BHC
e-BHC
J-BHC
Y-BHC
Chlordane
4, 4 '-DDE
4, 4 '-ODD
4, 4 '-DDT
Dieldrin
a-Endosulfan
^-Endosulf an
Endosulfan sulfate
Endrin
Heptachlor
Heptacnlor epoxide
ND
ND
BDL
ND
ND
ND
BDL
BDL
ND
BDL
ND
ND
ND
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
,
BDL
,
~h BDL
~h BDL
BDL
BDL
BDL
BDL
"b BDL
BDL
BDL
BDt
570
810
480
450
55
2,400
160
16,000
280
BDL
26
70
BDL
7
38
BDL
BDL
BDL
BDL
480
650
55
500
2,500
18
210
2,200
7
140
BDL
6
55
BDL
<5
24
BDL
BDL
BDL
BDL
16
20
89
83
50
77
29
Note: Blanks indicate no information currently available.
Negative removal.
Indeterminate removal.
Date: 6/23/80
II.8.6-27
-------
TABLE 8.6-16 (continued)
Plant 4704
Investment
casting operations
Concentration,
ug/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Ethers
Bis(2-chloroethyl) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
N-nitroso-di-n-propylamine
Phenols
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
2-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
4 , 6-Dinitro-o-cresol
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Ben zo ( a ) pyrene
Chrysene
Fluoranthrene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Raw
20
450
ND
50
0.2
5
ND
490
ND
BDL
6
BDL
ND
4
BDL
5
BDL
BDL
ND
ND
BDL
BDL
BDL
ND
2
BDL
ND
ND
ND
BDL
ND
BDL
24
Treated
30
83
7
BDL
BDL
BDL
BDL
100
12
BDL
BDL
13
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
10
12
BDL
BDL
BDL
Percent
removal
a
82a
60b
""jj
~k
80
a
~k
"""^
-
_
_b
_
__
A
_a
b
"V
_D
17
Plant 574C
Die
casting operations
Concentration ,
yg/L
Raw
<100
5
200
BDL
<90
<40
1,300
9
5,500
690
74
730
BDL
34
BDL
41
16
110
BDL
ND
200
<10
ND
53
780
370
800
160
<10
80
Treated
<150
23
150
BDL
<40
BDL
40
32
BDL
1
BDL
BDL
BDL
BDL
62
BDL
ND
BDL
BDL
BDL
BDL
BDL
10
BDL
BDL
3
BDL
BDL
Percent
r emova 1
a
a
25b
56
50
97
b
96
97
99
97
50
jj
44
_b
j-j
90
~ V
O
62
99
96
98
98h
__D
75
Plant 715C
Die
lube operations
Concentration ,
ug/L
Raw
BDL
8
2,000
BDL
BDL
BDL
1,600
820,000
5,400
600
29
207
5,700
1,600
26,000
350
84
250
540
18
470
32
470
Treated
BDL
10
2,100
BDL
BDL
BDL
1,500
16,000
9,300
10,500
34,000
69
50
470
180
500
3,200
7,300
93
10,000
3,200
3,200
Percent
removal
b
Q
~b
""]-}
~t)
6
98
jj
-
80
4t>
_a
67
&
_a
8i
(continued)
Date: 6/23/80
II.8.6-28
-------
0
CD
TABLE 8.6-17. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND IN THE COPPER FOUNDRIES SUBCATEGORY
6/23/80
hH
M
00
cr>
to
PLANT 9979
Plant 9979
Continuous
casting operations
Concentration ,
mg/La Percent
Flow/pollutant Raw Treated removal
Flow, m3/Mg 8.8 8.8
Pollutant
TSS 18 11 39
Total phenols
Oil and grease ND 11
pH 7.8 7.9
— i * • i « • f . •
, PLANT 6809, AND PLANT
Plant 6809
Molding cooling and
casting quench operations
Concentration ,
mg/La Percent
Raw Treated removal
0.76 0.76
52 20 62
30 6.2 79
8.3 7.9
.
9094 [1]
Plant 9094
Dust
collection systems
Concentration ,
mg/La
Raw Treated
610 2
2.1 0.01
8 0.4
7.1 7.7
Percent
remova 1
>99
>99
95
Note: Blanks indicate no information currently available.
aExcept flow, which is given in m3/Mg and pH values, which is given in pH units.
Negative removal.
-------
TABLE 8.6-18.
CONCENTRTIONS OF TOXIC POLLUTANTS FOUND IN THE
COPPER FOUNDRIES SUBCATEGORY, PLANT 9979,
PLANT 6809, AND PLANT 9094 [1]
Plant 9979
Continuous
cas t jjg^ o£grat ions
Concentration,
uJL Percent
Toxic pollutant
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Raw
ND
ND
ND
70
ND
ND
ND
2,700
ND
6
ND
Treated rein
10
2,400
1
130
BDL
BDL
BDL
4,400 ~
320
30
Nitrogen compounds
Benzidine
1,2-Diphenylhydrazine
Phenols
2,4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
p-Chloro-m-cresol
4,6-Dinitro-o-cresol
Aromatics
Benzene
2,6-Dinitrotoluene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Chrysene
Fluoranthrene
Fluorene
Naphthalene
Phenanthrene
Pyrene
17
BDL
BDL
ND
BDL
BDL
BDL
BDL
BDL
Plant 6809
Molding cooling and
casting quench operations
Concentration,
ug/L Percent
Raw
100
350
ND
ND
0.3
ND
ND
2,000
BDL
20
ND
BDL
15
BDL
ND
ND
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Treated removal
40 60
110 69
2 a
BDL "b
0.9 "a
60 "a
BDL "b
1,400 30
170 a
20 "c
19 "a
14 "a
93 ~b
BDL _b
19 _a
BDL _b
19 a
BDL "b
BDL _b
Plant 9094
Dust
collection systems
Concentration ,
M9/L
Raw
100
ND
110,000
49
28,000
ND
720
ND
130,000
11
180
1
6
38
BDL
BDL
BDL
36
BDL
BDL
11
25
BDL
BDL
BDL
4
BDL
5
6
<21
<29
6
<7
<7
57
4
BDL
11
<21
6
Treatet
BDL
BDL
160
1
81
0.5
BDL
BDL
450
17
BDL
11
BDL
11
6
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
12
Percent
i removal
b
"b
>99
98
>99
a
"b
"b
>99
_a
~b
a
"b
71
_a
_b
_b
b
'b
~b
_b
b
"b
~b
b
~a
(continued)
Date: 6/23/80
II.8.6-30
-------
TABLE 8.6-18 (continued)
Plant 9979
Continuous
casting operations
Toxic pollutant
Concentration,
yg/L
Raw Treated
Percent
removal
Plant 6809
Molding cooling and
casting quench operations
Concentration,
ug/L Percent
removal
Plant 9094
Raw
Treated
Dust
collection systems
Concentration,
ug/L
Percent
Treated removal
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254
1424
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chloroform
Hexachlorocyclopentadlene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
6-BHC
4-BHC
Y-BHC
Chlordane
4,4' -DDE
4,4' -DDT
Dieldrin
B-Endosulfan
Endosulfan sulfate
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
ND
ND
ND
ND
BDL
ND
ND
BDL
BDL
ND
<5
ND
ND
ND
BDL
BDL
BDL
15
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
_b
_b
_b
a
b
~b
_b
_b
_b
_b
ND
ND
BDL
11
ND 230 _a
ND 30 _a
80 93 a
37 44 "a
50 56 ~a
ND
ND
BDL
BDL
BDL
ND
BDL
BDL
BDL
BDL
BDL BDL _b
ND
ND
ND
BDL
ND
ND
ND
ND
ND
ND
ND
BDL
ND
ND
4
ND
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
_b
_b
_b
_b
_b
b
~b
"b
"b
~b
_b
_b
Note: Blanks indicate no information currently available.
aNegative removal.
Indeterminate removal.
clndicates negligible removal.
Date: 6/23/80
II.8.6-31
-------
o
0>
ft
(D
N;
to
CO
o
c»
o>
i
w
ts>
TABLE 8.6-19. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND N THE MAGNESIUM FOUNDRIES
SUBCATEGORY, PLANT 8146 [1]
Grinding
scrubber operations
Concentration, mg/La
Pollutant Raw Treated
Dust
collection systems
Concentration, mg/La
Raw Treated
TSS
Oil and grease
PH
9.8
8.3
6
7.6
Note: Blanks indicate no information currently available.
aExcept pH, which is given in pH units.
No treatment at this facility.
-------
TABLE 8.6-20.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
MAGNESIUM FOUNDRIES SUBCATEGORY, PLANT 8146 [1]
Grinding
scrubber operations
Concentration ,
Toxic pollutant
Raw Treated8
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-Chlorophenol
2,4-Dimethylphenol
2-Nitrophenol
Pentachlorophenol
Phenol
Aromatics
Benzene
1,200
51
ND
ND
ND
ND
Dust
collection systems
Concentration,
ug/L
Raw
Treated
Metals and inorganics
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
60
ND
80
ND
ND
20
ND
30
ND
ND
ND
14
ND
10
40
ND
ND
ND
<20
11
6
BDL
1 , 2-Dichlorobenzene
Hexachlorobenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Benzo (a) pyrene
Chrysene
Fluoranthrene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphonyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254
1424
Halogenated aliphatics
Chloroform
Dlchlorobromomethane
Hexachloroethane
Methylene chloride
Tetrachloroethylene
Pesticides and metabolites
a-BHC
>-BHC
4, 4 '-DDE
4,4' -DDT
Dieldrin
Endrin aldehyde
Heptachlor epoxide
BDL
BDL
ND
BDL
ND
ND
ND
ND
BDL
BDL
BDL
BDL
BDL
ND
ND
BDL
44
ND
BDL
BDL
BDL
BDL
BDL
ND
18
11
32
<30
ND
ND
10
ND
3
BDL
<30
7
ND
SD
ND
BDL
BDL
BDL
Note: Blanks indicate no information currently available,
aNo treatment at this facility.
Date: 6/23/80
II.8.6-33
-------
II.8.6.3.5 Zinc Foundries
Plant 436-E. Zinc die casting quench wastes, aluminum die
casting quench wastes, cutting and machining collants, and impreg-
nating wastes are co-treated in a batch-type system. The zinc
casting quench waste is actually the effluent from a system that
recycles the quench tank contents through a settling and skimming
operation and back to the quench tanks. The zinc casting quench
wastes represent approximately 25% of the total treatment volume.
After undergoing a sulfuric acid-and-alum emulsion break, neu-
tralization, flocculation, and solids separation, the treated
effluent is discharged to a land-locked swamp.
Plant 462-G. This plant has requested confidentiality. No
treatment technology description is available. However, raw and
treated data are presented.
Tables 8.6-21 and 8.6-22 present conventional and toxic pollutant
data for the two zinc foundries described.
II.8.6.3.6 LeadFoundries
There are no plant-specific data in the available source docu-
ments concerning the lead foundry subcategory.
II.8.6.4 Pollutant Removability [1]
Two conventional pollutants represent the major wastewater pollu-
tant concerns in the foundry industry. Suspended solids are
present in high concentrations in nearly every wastewater source
emanating from the foundry processes. oil and grease are also
present in many of these sources. Primary treatment technologies
are generally used to reduce the amounts of these pollutants
emitted. Metals may also be present in the wastewater streams
and can be removed by chemical precipitation.
The most common treatment method used to reduce the high solids
content in the wastewater is sedimentation. Wastewaters from
foundry processes are treated by lagooning, clarification with
chemical addition, cyclone separation, dragout chambers, and
Lamella inclined-plate separators.
Chemicals used for clarification include polymers, lime and alum.
Sulfuric acid and alum are also used as emulsion breakers.
Settled sludges are dewatered by filtration or other techniques
and are generally hauled away by waste disposal contractors.
Ultrafiltration is used at a few plants to trap high molecular
weight organics prior to discharge to a POTW.
Date: 6/23/80 n. 8.6-34
-------
D
fti
ft
U)
\
00
o
h-l
00
•
en
CO
en
TABLE 8.6-21. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN THE ZINC
FOUNDRIES SUBCATEGORY, PLANT 462G AND PLANT 436E [1]
Plant
Melting
furnace scrubbers
Pollutant
TSS
Total phenols
Oil and grease
PH
Concentration ,
mg/La
Raw Treated
430 310
91 14
760 860
4.7
Percent
removal
28
85
-b
462G
Plant 436E
Casting
quench operations
Concentration ,
mg/La
Raw Treated
40
0.048 0.
22
7.4
32
009
29
Percent
removal
20
81
-b
Casting
quench operations
Concentration ,
mg/La
Raw Treated
92 8.0
0.11 0.38
70 4.2
5.7 9.1
Percent
removal
91
b
94
Note: Blanks indicate no information currently available.
aExcept pH values, which are given in pH units.
Negative removal.
-------
TABLE 8.6-22.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE ZINC
FOUNDRIES SUBCATEGORY, PLANT 462G AND PLANT 436E [1]
rt
(D
CO
\
oo
o
00
cr«
u
en
Plant
Melting
furnace scrubbers
Concentration ,
Ug/L
Toxic pollutant
Metals and inorganics
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
f-Chloro-m-cresol
Aromatics
Benzene
2, 4-Dinitro toluene
2 ,6-Dinltrotoluene
Ethylbenzene
Nitrobenzene
Toluene
1,2,< Trichlorobenzene
Polycyclic aromatic
Hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz (a) anthracene
Chrysene
Fluoranthene
Fluorene
Naphthalene
f henanthrene
Py rene
Raw
BDL
ND
8
BDL
0.3
ND
ND
19,000
5,500
80
<10
110
80
1,300
12,000
30,000
1,400
<10
<37
<37
<10
60
<1 0
1,000
37
43
<86
<10
<10
12
46
3,300
<86
<10
Treated
5.7
7.3
BDL
0.5
BDL
9.9
11,000
5,500
49
70
180
130
220
490
2, 300
600
<10
<17
<17
<10
39
<10
26
<10
17
Percent
removal
b
"9
a
~b
"b
"b
42
_c
39
b
b
_b
77
96
92
57
c
54
54
_c
b
77
_b
>99
_b
462G
Casting
quench operations
Concentration ,
Raw
BDL
ND
9
BDL
0.3
ND
ND
3,700
170
<10
17
<10
<10
<10
42
<10
53
65
<10
14
<10
<10
Treated
BDL
79
79
BDL
0.8
BDL
9.5
2,300
180
<10
110
<10
< 10
<10
<10
<10
27
<10
33
<10
20
Percent
removal
a
b
"b
a
_b
~a
"b
38
b
~c
"b
_c
c
c
76
81
58
c
b
-
b
Plant 436E
Cast inq
quench operations
Concentration ,
l,q/L Percent
Raw Treated removal
BDL BDL a
150 50 67
ND 4 _b
BDL BDL _a
ND 0.3 _b
30 120 "b
ND BDL a
350,000 36,000 90
47 15 68
-------
Qi
TABLE 8.6-22 (continued)
00
o
00
i
u>
Toxic pollutant
Polychlorinated biphenyls
and related compounds
Aroclor 1016, 1232,
1248, 1260
Aroclor 1221, 1254
1424
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Methylene chloride
Tetrachloroethylene
Tr ichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
B-BHC
6-BHC
y-BHC
Chlordane
4,4' -DDE
4,4' -ODD
4, 4 '-DDT
o-Endosulfan
B-Endosulfan
Endrin
Endrin aldehyde
Heptachlor •
Heptachlor epoxide
Plant <
Melting
furnace scrubbers
Concentration ,
ug/L Percent
Raw Treated removal
<5
<5
<20
ND <10 b
ND <10 "b
ND <10 ~b
<10 <10 ~c
<5 <5 _c
<5 <5 c
<5 <5 "c
<5 <5 ~c
<5
Casting
quench operations
Concentration,
Ug/L Percent
Raw Treated removal
<5
<5
ND
ND
ND
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5 _c
<10 b
<10 "b
31 >
<5 _c
<5 _c
<5 _c
Plant 436E
Casting
guench operations
Concentration,
pg/L
Raw Treated
<10
11 800
<5
<5 <5
<5 <5
<5 <5
<5
<5
<5 <5
<5
<5
Percent
removal
_b
-
-c
-
_c
Note: Blanks indicate no information currently available.
"indeterminate removal.
Negative removal.
clndicates negligible removal.
-------
Oil skimming is also used at foundry facilities to remove the oil
and grease that results from housekeeping and from machinery
leaks.
Another common control method used extensively in the foundry
industry is the recycling of wastewater. Most processes have
facilities that recycle 100% of the wastewater and can be
classified as zero dischargers. Processes can also recycle
less than 100% of the wastewater; these normally treat the non-
recycled wastewater before discharge.
Tables 8.6-13 through 8.6-20 (Sections II.8.6.3.1 through
II.8.6.3.5) present pollutant removability data for each foundry
subcategory. This information is the result of a screening
program. No data are currently available concerning the
treatability of wastewater emanating from the magnesium or lead
foundry subcategories.
II.8.6.5 REFERENCES
1. Foundry Industry (Contractor's Draft Report). Contract
68-01-4379, U.S. Environmental Protection Agency, Washington,
D.C., May 1979.
2. NRDC Consent Decree Industry Summary - Foundries.
Date: 6/23/80 n.,.8-38
-------
11.8.10 PORCELAIN ENAMELING
II.8.10.1 Industry Description
II.8.10.1.1 General Description [1, 2]
The porcelain enameling industry consists of approximately 130
plants enameling approximately 200 million square meters of
steel, iron, aluminum, and copper each year (each coat of multi-
ple, coats is considered in this total). Porcelain enameling is
the application of glass-like coatings to the metals mentioned
above. The purpose of the coating is to improve resistance to
chemicals, abrasion, and water, and to improve thermal stability,
electrical resistance, and appearance. The coating applied to
the metal, called a "slip," is composed of one of many combina-
tions of frits (glassy raw materials), clays, coloring oxides,
water, and special additives such as suspending agents. These
vitreous inorganic coatings are applied to the metal by a variety
of methods such as spraying, drying, and flow coating and are
bonded to the metal at temperatures over 500°C.
Several processes are used in the porcelain enameling industry
regardless of the metal being coated. These processes, discussed
below, include preparation of the enamel slip, surface prepara-
tion of the base material, and enamel application and firing to
fuse the coating to the metal.
Enamel Sliff Preparation. The preparation of the enamel slip
includes ball milling the frit and raw materials to the appropri-
ate consistency. Frit is the glassy raw material that makes up
the backbone of porcelain enameling. Most frit is manufactured
outside the operation but some plants do include captive opera-
tions. Other raw materials, such as clay, gums, or opacifiers,
are mixed into the frit by the ball mill, which then releases
this mixture to the coating operation.
Base Material Surface Preparation. In order for the porce-
lain enamel to form a good bond with the workpiece, the base
metal to be coated must be properly prepared. Depending on the
type of metal being finished, one or more preparation processes
are performed. Solvent cleaning removes oil, greases, and fin-
gerprints from the metal by exposing it to nonflammable solvents
such as trichloroethylene or 1,1,2-trichloroethane at their boil-
ing points. This process may also be combined with water to
provide a two-phase cleaning system for solvent-soluble and
water-soluble contaminants.
Alkaline cleaning removes oils and soils from the workpieces by
the detergent nature of the solution. Soaking, spraying, and
electrolytic alkaline cleaning are the common methods used, with
the electrolytic process providing the cleanest surface. If
Date: 6/23/80 II.8.10-1
-------
aluminum is the metal being coated, a stronger alkaline solution
is often used as a mild etch that removes the surface oxides.
Acid treatment is used to remove rust, scale, and oxides from the
base and may be carried out in the form of acid cleaning, pick-
ling, or etching. Each option involves a slightly stronger acid
solution. Generally, sulfuric acid is used for this treatment,
although other acids may be employed.
Nickel deposition is a common step when enameling steel in order
to improve the bonding of the enamel to the metal. Nickel is
normally deposited after the part has been acid treated and
rinsed. Neutralization normally follows acid pickling and nickel
deposition to remove the last traces of acid left on the metal.
Chromate cleaning and grit blasting may also be used to prepare
the base metal prior to the coating process. When used, grit
blasting is normally the sole preparation step because it cleans
the metal and roughens the surface, providing a good base for
bonding.
Enamel Application and Firing. Once the workpiece has
undergone the proper base metal preparation and the enamel slip
has been prepared, the next step is the actual application of the
porcelain enamel. Included among the application methods are air
spraying, electrostatic spraying, dip coating, flow coating, pow-
der coating, and silk screening. After each coating is applied
the part is fired in a furnace to achieve a fusion between the
enamel coating and the base metal or substrate.
Air spraying is the most widely used method for enamel applica-
tion. In this process the enamel is atomized and propelled by
air onto the base metal to form an enamel coating. Overspraying
is a common problem with this technique since the atomized
particles may not adhere to the part. Spray booths to collect
this oversprayed enamel are necessary. A modification of this
technique is the electrostatic spray coating method where the
atomized particles are charged at 70,000 to 100,000 volts and
directed toward the grounded part. This charge increases the
adhering efficiency but does not eliminate the need for the spray
booth collectors. Other advantages such as edging and the coat-
ing of both sides at once are also seen.
Dip coating consists simply of dipping the workpiece in an enamel
bath and allowing it to drain. Flow coating floods the piece
with enamel and then recycles the unused, recovered enamel. Pow-
der coating is the dusting of a red hot cast iron workpiece with
porcelain enamel in the form of a dry powder. The glass powder
melts as it strikes the hot surface. Silk screening is used to
apply a decorative pattern on a porcelain enameled piece.
Date: 6/23/80 11.8.10-2
-------
Porcelain enameling plants are located primarily in the states of
Wisconsin, Illinois, Indiana, Michigan, Ohio, Pennsylvania,
Kentucky, and Tennessee. Seventy-seven percent of the facilities
discharge to POTW's, 21% to streams or rivers, and 2% to both.
Approximately 10% of the plants recycle, with an average recycle
of 9.6 m3/hr, which represents 46% of the average process water
usage rate of 20.8 m3/hr. Average plant production is approxi-
mately 1.5 x 106 m2/yr.
Table 8.10-1 presents an industry summary of the number of sub-
categories and the number and type of dischargers for this
industry.
TABLE 8.10-1. INDUSTRY SUMMARY [2]
Industry: Porcelain Enameling
Total Number of Subcategories: 4
Number of Subcategories Studied: 4
Number of Dischargers in Industry:
• Direct: 30
Indirect: 100
Zero: 0
II.8.10.1.2 Subcategory Descriptions [1]
The porcelain enameling industry consists of four Subcategories,
porcelain enameling on: steel, iron, aluminum, and copper. This
subcategorization was chosen on the basis of the base metals
used. Other possible Subcategories (dependent on wastewater
characterization, manufacturing processes, products, water use,
etc.) were considered, but all were found to be directly related
to the base metal used. In addition to the four Subcategories
selected, steel and aluminum base metals may be further divided
into two segments, sheet and strip, to account for the signifi-
cant water saving potential of continuous operations relative to
individual sheet processing. However, because only two porcelain
enameling facilities treat strip, no separate division is neces-
sary at this time.
In general, only 10% of the porcelain enameling facilities enamel
more than one type of base metal. Over 70% of the plants enamel
solely on steel, 10% on aluminum, and 8% on iron. Less than 1%
of the plants enamel copper, strip steel, or strip aluminum
separately.
Subcategory 1 - Porcelain Enameling on Steel. Steel is by
far the most widely used base metal for porcelain enameling with
Date: 6/23/80 II. 8.10-3
-------
an average yearly production usage of 1.9 x 108 m2 (2.1 x 109
ft2) for 1976. This figure represents the area of enamel applied.
For multiple coats, the area for each coat is considered. Among
the products which use porcelain enameled steel are the following:
cooking and heating equipment such as ranges, home laundry equip-
ment (washers and dryers), refrigerators, freezers, dishwashers,
water heaters, process vessels, architectural panels, plumbing
fixtures, and various appliance parts.
Several processes are used when enameling on steel. The parts to
be coated are first alkaline cleaned and rinsed to remove soils.
An acid treatment step and rinse follow in which sulfuric acid,
ferric sulfate in conjunction with sulfuric acid, or muriatic
acid are used for oxide removal. A nickel deposition step and
rinse ensues, followed by a neutralization operation which
removes any remaining traces of acid.
Following surface preparation and drying, the part is ready for
the enamel application. Steel parts are either sprayed, dipped,
or flow coated. The enamel slip can be applied in a single coat-
ing operation (referred to as direct-on), or a ground coat and a
cover coat may be applied separately. For the direct-on process,
corners and edges are usually reinforced (precoated) to ensure
coverage. For either case, each coat is fired at a temperature
of approximately 820°C (1,500°F). Total thickness of sheet steel
enamels involving a ground coat and cover coat is in the range of
0.13 to 0.20 mm (5 to 9 mils).
When the direct-on process is utilized, surface preparation
requirements are more critical to ensure effective enamel
adhesion. The acid etch is often deeper and the nickel deposi-
tion is always thicker. Typically, the nickel coating is 0.10 to
0.20 g/ft2 for direct-on coating as compared to 0.03 to 0.07
g/ft2 for two-coat applications. A few porcelain enamelers
prefer to omit the nickel deposition step. While the nickel
enhances the enamel bonding, product quality requirements may not
require nickel deposition. The omission of the nickel step
necessitates the utilization of a heavy acid etch to ensure a
clean, properly conditioned surface for enamel bonding.
Subcategory 2 - Porcelain Enameling on Cast Iron. Cast iron
is porcelain enameled primarily for plumbing fixtures for the
sanitary products industry. It is also used for cookware and for
various appliance parts such as grates for gas ranges. The aver-
age yearly production for 1976 is estimated at 1.0 x 107 m2 (1.1
x 10s ft2). This figure represents the areas of enamel applied.
For multiple coats, the area for each coat is considered.
The porcelain enameling of cast iron is a process in which water
is not generally used for metal preparation but is sometimes used
for coating application. The casting to be coated is blasted
Date: 6/23/80 II.8.10-4
-------
with sand or a combination of grit and sand to produce a smooth,
velvety surface. The parts are then brushed off and any rough
edges are removed by grinding.
The ground coat is then applied by spraying, dipping, or flow
coating. If only one coat is required, a heavy ground coat is
applied. If there is to be a ground coat and a top coat, a thin
layer of enamel is used for the ground coat. The ground coat is
then fired. The firing period is longer than for sheet steel
because of the greater mass of the enameled body, and firing
temperature is reduced to avoid excessive baking. When the cast
is removed from the furnace and still red hot, the top coat is
applied by powder coating. The enamel in powder form is dusted
on the hot part and fuses to the surface. Total thickness of dry
process coatings is approximately 0.50 mm (20 mils).
Subcategory 3 - Porcelain Enameling on Aluminum. Porcelain
enameling on aluminum finds use in the cookware and housewares
industry. It is also used for panels and signs. The estimated
yearly production for 1976 is 4.7 x 106 m2 (5.0 x 107 ft2). This
figure represents the area of enamel applied. For multiple
coats, the area for each coat is considered.
Although all aluminum parts can be coated in a similar fashion,
the surface preparation can vary from company to company. The
choice of surface preparation methodology is based upon the alloy
type of the base metal and the cleanliness requirements involved.
Pure aluminum requires only a cleaning step. A heat treatable
alloy may require a pickling step in addition to cleaning.
Porcelain enameling on a high magnesium alloy could necessitate a
chromate cleaning process. This chromate coating retards the
oxidation of the magnesium in this high strength alloy.
Nearly all aluminum parts are first treated in an alkaline solu-
tion. In some cases this is only a cleaner for removing grease
and soils; sometimes it is a mild etchant to remove a layer of
metal and its oxides. Frequently, this is all the surface prep-
aration that is necessary. Any further preparation steps are to
remove residual oxides (example: chemical deoxidizing with
nitric acid) or to impart a thin protective layer on the metal
(alkaline chromate treatment). The users of such processes were
limited in the plants studied [1].
Aluminum does not require a ground coat. Enamel is generally
applied by spraying, with firing accomplished by heating to 450°C
to 550°C (850°F to 1,040°F) for 2 to 10 minutes.
Subcategory 4 - Porcelain Enameling on Copper. Porcelain
enameling on copper represents a very small part of the porcelain
enameling category. It is not practiced by many firms and the
ones involved with it do it on a small scale. Enameled copper is
Date: 6/23/80 II.8.10-5
-------
used mostly for ornamental purposes, such as jewelry, decorative
ware, and metal sculpture.
Since it is essential to remove all the oil and grease on the
copper before coating, the part is first alkaline cleaned,
degreased, or annealed. After cleaning, the part is then typi-
cally pickled for oxide removal.
The enamel application involves two processes: a ground coat or
backing coat, and a cover coat to prevent the copper base from
being taken into solution with the enamel and causing discolora-
tion. This ground coat is applied by either spraying or dipping.
The cover coat can be applied by powder coating or with silk
screening to achieve patterns.
Other Subdivisions - In addition to the above subcategories,
porcelain enameling on continuous strip is a subdivision within
this industry. However, because there are only two plants in the
United States producing this product, a separate subcategory is
not necessary. These plants start with coils of steel, aluminum,
or aluminized steel, porcelain enamel them, and either recoil
them for sale to metal fabricators or shear them into pieces for
use as architectural panels or chalkboards. The estimated pro-
duction for 1976 is 2.0 x 106 m2 (2.2 x 107 ft2). This figure
represents the area of enamel applied. For multiple coats, the
area for each coat is considered.
The surface preparation operations for strip are dependent upon
whether the basis material is steel or aluminum. The surface
preparation steps for steel strip are minimal in comparison to
porcelain enameling on steel sheets since precleaned strip steel
is used. Steel strip is nickel immersion plated prior to the
enameling step. Surface preparation for aluminum involves only
cleaning. The enamel for either basis material is applied by
means of spray guns which are aimed at the surface of the moving
strip. Two coats are normally applied, the strip being fired
after each coat.
II.8.10.2 Wastewater Characterization [1]
This section presents water uses and discharges, and waste con-
stituents emanating from the porcelain enameling category. Pub-
lished literature, data collection portfolio (dcp) responses, and
sampling data have been used to obtain the relevant information.
The majority of the waste constituent data result from a sampling
program in which plants were sampled downstream of the porcelain
enameling process but prior to any treatment for a 3-day sampling
period.
Table 8.10-2 presents wastewater flow data on a subcategory and
stream basis for the porcelain enameling industry.
Date: 6/23/80 II.8.10-6
-------
TABLE 8.10-2.
WASTEWATER FLOWS FROM THE PORCELAIN
ENAMELING INDUSTRY [I]
Stream
Number
of
points
Wastewater flow, m3/day
Range Median Mean
P/E on steel
Alkaline cleaning
Acid treatment
Nickel deposition
Neutralization
Coating
Total raw waste
P/E on iron
Coating
P/E on aluminum
Alkaline cleaning
Coating
Total raw waste
15
15
9
5
15
15
9.4
5.7
19
1.0
1.9
20
120
44
30
15
300
410
30
20
24
15
4.0
180
45
20
23
11
70
150
0.64 - 7.2
1.2
2.9
8
8
8
19
4.8
68
220
55
220
170
30
200
130
29
160
P/E on copper
Acid pickling
Coating
Total raw waste
2
3
3
7.3
0.64
1.3
- 1
- 7
.3
.9
0
7
.64
.9
7
0
5
.3
.85
.7
Note: Blanks indicate insufficient data available.
Subcategory 1 - Porcelain Enameling on Steel. Wastewater
from porcelain enameling on steel is generated by base metal sur-
face preparation, enamel application, ball milling, and related
operations. The constituents in the wastewater include the base
material being coated (iron), as well as the components of the
surface treatment solutions and enamels being applied.
Water rinses are used in surface preparation operations such as
acid pickling, alkaline cleaning, and nickel deposition to remove
any process solution film left from the previous bath. A water
rinse may also follow the neutralization step. Another common
water use is in the ball milling process, which uses water as the
vehicle for the enamel ingredients, as a cooling medium, and for
cleaning up the equipment. Coating application processes nor-
mally employ wet spray booths to capture oversprayed enamel
particles. Water wash spray booths use a water curtain into
which the enamel particles are blown and captured.
The major sources of waste generated by this subcategory are the
process solutions used in basis material preparation, the base
metal being coated, and the enamel being prepared. Alkaline
cleaning solution varies with the type of soil being removed.
Wastewaters from this operation contain constituents of the
Date: 6/23/80
II.8.10-7
-------
cleaning solution as well as oil and greases. Wastewater also
contain iron but in lesser concentrations than those from the
acid pickling process. Alkaline cleaning wastes enter the waste-
stream in three ways: during the rinse step, from the cleaning
bath overflow, and in the batch dump of the spent alkaline bath.
Acid treatment is typically sulfuric acid with lesser amounts of
hydrochloric, phosphoric, and nitric acids being used. Acid
solutions develop a high metallic content due to the dissolution
of the steel itself during the pickling operation. As a result,
the baths are frequently dumped, putting large amounts of iron
into the wastestream. Also present in significant concentrations
are phosphorus and manganese. The stream has a low pH as well.
Nickel deposition can place large amounts of nickel and iron into
the wastestream by batch dumping and dragout. The neutralization
step eases the pH burden and adds little additional loading of
any pollutant.
The introduction of enamel into the wastestream results in an
increase in the concentration of metals, but these metals (anti-
mony, titanium, zirconium, tin, cobalt, and manganese) are in
solid form while the metals generated by surface preparation are
normally in dissolved form. These solid metals increase the sus-
pended solids concentration of the stream. Other metals that may
be found in the enamel preparation and application wastestream in
significant amounts include aluminum, copper, iron, lead, nickel,
and zinc. Table 8.10-3 presents pollutant sampling data for the
processes used in the porcelain enameling on steel industry. The
not detected values have been excluded from the calculation of
the ranges, medians, and averages throughout this section.
Subcategory 2 - Porcelain Enameling on Iron
There are two different types of cast iron porcelain enameling:
wet process and dry process. The dry process uses no water and
does not produce wastewater. Wet process enameling of cast iron
employs water for ball milling and enamel application. These
processes are very similar to the ones described for the steel
subcategory. Surface preparation involves sand or grit blasting
and uses water only in an air scrubber operation. Ball milling
uses water as a vehicle for the enamel slip ingredients, as cool-
ing water, and for equipment cleanup. Coating application uses
water as a trap for the excess enamel particles during the spray
step. Wastewater constituents in significant concentrations in
the streams emanating from this subcategory include suspended
solids, aluminum, iron, copper, lead, manganese, nickel, titanium,
zinc, and cobalt. All of these metals are the result of the
enamel carryover via spray booth blowdown or ball mill washdown.
Table 8.10-4 presents wastewater characterization data for the
streams in this subcategory.
Date: 6/23/80 11.8.10-8
-------
O
QJ
rt
CD
CTi
NJ
U)
oo
o
TABLE 8.10-3.
WASTEWATER CHARACTERIZATION OF THE PORCELAIN
ENAMELING ON STEEL SUBCATEGORY [I]
CO
o
I
Pollutant
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
AntijMHiy
Arsenic
Berylliua
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Seleniuai
Zinc
Organic*
Toluene
1 , 2-Dichlorobenzene
Chloroform
Dichlorobromome thane
1,1.2,2-Tetrachloroethane
Tetrachloroethylene
Nontozic inorganics
AlUBUilUB
Iron
Hanganese
Titanitai
Cobalt
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
pH
Fluorides
Toxic pollutants
Hetals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Number
of
samples
14
13
13
5
14
IS
IS
15
IS
15
14
IS
s
IS
13
IS
14
3
IS
12
13
15
15
7
6
6
4
8
9
9
9
9
9
9
9
4
9
9
9
9
Number
not
Median,
detected Range, ing/L"
0
1
1
0
0
0
IS
15
15
12
10
2
5
IS
9
14
2
3
3
0
3
15
14
0
0
1
0
0
0
0
9
0
Alkaline cleaning.
6 2 - 650
1 1 - 27
0.006 - 0 69
12 - 63
2 -11
0.26 - 1.8
0.005 - O.OM
0.004 - 0.01
0.002 - 0.22
0.014 - 0.063
0.013 - 0.81
0.081 - 0.92
0.10 - 8.3
0.066 - 0.36
Nickel deposition
2-77
1.1 - 8.3
0.008 - 0.042
1-18
2.0 - 6.2
0.27 - 0.80
0 019 - 0 13
0 008 - 0 079
2 9 - 280
0 036 - 0 27
»g/L"
44
7 1
0 018
16
8.3S
0 94
0 018
0.006
0 071
0.021
0.003
0.029
0.1S
1.6
0.16
0.001
Average
»q/L
147
4 3
0 081
32
7 6
0.91
0
0
0
0.036
0.006
0.040
0
0
0.030
0.003
0.10
0
0.23
2.9
0.19
0
0.001
Number
of
samples
13
6
9
4
14
15
15
15
15
15
15
15
8
15
15
15
15
3
IS
15
15
15
15
Nimber
not
detected
0
0
4
0
0
0
15
15
15
15
0
0
4
11
3
15
0
3
5
0
0
15
0
Range
Acid
1 9
7 1
0 015
2
2
0 14
0.011
0.006
0.05
0.60
0.017
O.OS4
180
0.57
0.017
.»q/La
treatment
- 140
- 12
- 0 043
- 17
- 3 4
- 1 1
- 3.1
- 0.38
- 0.1
- 11
- 0.25
- 0.52
- 10.000
- 53
- 0.38
Median,
mg/LJ
10
a 9
0 027
4 2
2 3
0 72
0.32
0.064
0 072
2.4
0 091
0.22
1.300
3 4
0.036
Average.
•g/L1
18
9 4
0.028
6 8
2.4
0 61
0
0
0
0
0 79
0 092
0
0.074
4.2
0
0 11
0
0.23
2,600
11
0
0.121
Neutralisation
4
4.4
0.029
4.9
2.7
0 50
0 044
0 019
8 7
0 073
20
4.5
0.028
7 2
3.3
0.51
0
0
0
0
0 060
0 032
0
0
73
0
0 10
3
4
3
3
4
4
4
4
4
4
4
4
3
4
4
4
4
0
1
0
0
0
0
4
4
4
4
2
3
3
4
0
4
0
8.0
0.04
0.004
3
8.4
0.32
0.012
0.075
0 OU
- 9.0
- 7 S
- 0 024
- 3.8
- 9.0
- 1.1
- 0.032
- 9 4
- 0 025
9 0
0.38
0 004
3 3
9 0
0 42
0 014
o n
0 012
8.7
2.6
0 Oil
3.4
6.9
0.55
0
0
0
0
0.022
0 014
0
0
2 S
0
0 015
(continued)
-------
a
&
rt
fD
fO
OJ
TABLE 8.10-3 (continued)
M
M
O
I
Number
Pollutant samples
Numbei
not
detected
Range m
Number Number
Hedlan Aveiage of not Median
q/L3 mg/L raq/L samples detected Range, mq/L* «g/L
Nickrl deposition
Toxic pollutants
Organics
Toluene
1 . 2-Dichlorobenzene
chloroform
Dichlorobromome thane
1 1 2 2-Tetrachioroethane
letrachloroefhylene
Nontoxic inorganic!.
Aluminum
1 t on
Manganese
Titanium
Cobel t
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
pH
Fluorides
Toxic pollutants
Hetali and inorganics
Ant lawny
Arsenic
Beryllium
CadBium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Organics
Toluene
1 . 2-Dlchlorobcnzene
Chloroform
Di chlorobromone thane
1, 1,2,2-Tetrachloroetha.ne
Te t rachloroe thylene
Nontoxic inorganics
Manganese
Cobalt
9
9
9
t
-------
TABLE 8.10-4.
WASTEWATER CHARACTERIZATION OF THE PORCELAIN
ENAMELING ON CAST IRON SUBCATEGORY [1]
]
Pollutant !
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Nontoxic inorganics
Aluminum
Barium
Boron
Iron
Magnesium
Manganese
Molybdenum
Tin
Titanium
Gold
Sodium
Calcium
Cobalt
Coating
lumber
of
samples
7
7
6
3
7
7
7
7
7
7
7
7
3
7
1
7
7
1
1
7
7
1
1
6
1
7
1
1
7
1
1
1
7
Number
not
detected Range, mg/La
0
1
0
0
0
0
6
4
3
3
0
0
2
0
0
3
0
1
1
1
0
1
0
1
0
0
0
0
3
1
1
1
0
6,600
0.49
0.008
1.0
7.9
2.0
1.9
0.002
0.014
0.0
0.001
0.49
0.25
0.43
0.68
0.38
18
0.003
0.022
0.044
- 81,000
- 2.1
- 0.038
- 9.5
- 11.4
- 115
- 2.8
-0.12
- 9.6
- 1.1
- 8.8
- 880
- 67
- 160
- 650
- 1,200
- 150
- 65
- 100
- 95
Median,
mg/L
19,000
0.93
0.017
3.7
9.4
23
6.0
2.4
0.036
0.59
0.21
0.42
0.009
7.6
0.001
33
9.3
9.0
240
0.157
38
3.1
2.2
0.037
0.033
37
8.9
Average,
mg/L*
27,000
1.1
0.020
4.7
9.4
41
6.0
2.4
0.049
2.7
0.43
2.6
0.009
170
0.001
33
29
0
0
127
340
0
0.157
56
3.1
15
0.037
0.033
44
0
0
0
24
Note: Blanks indicate insufficient data available.
aExcept pH values, given in pH units.
Date: 6/23/80
II.8.10-11
-------
Subcategory 3 - Porcelain Enameling on Aluminum
Wastewaters from this subcategory come from surface preparation,
enamel application, ball milling, and related operations. Con-
stituents of this wastewater include aluminum and components of
the surface preparation solutions and the enamels being applied.
Water is used in this subcategory as solution makeup and for
rinsing in the surface preparation process, as the vehicle for
the- coating in the application process (normally done by spray
coating), and for cooling and cleanup in the ball milling operation.
The surface preparation process contributes pollutants to the
wastewater by the continuous overflow of the cleaning bath (if a
continuous process), by the batch dumping of spent solutions, and
by the rinsing steps directly following the process. Generally,
significant quantities of dirt and grease are removed during this
cleaning process. Also entering the wastestream is a consider-
able amount of aluminum. When an alkaline cleaning process is
used the wastewater contains significant concentrations of sus-
pended solids, phosphorus, and aluminum. Acids used to deoxidize
the surface normally remove a larger amount of aluminum than
alkaline treatments and therefore increase the dissolved aluminum
concentration. The enamel preparation and application steps con-
tribute significant amounts of suspended solids and metals, par-
ticularly cadmium, lead, titanium, zinc, aluminum, barium, iron,
selenium, and antimony due to use of these metals in the enamel
itself. There are also high levels of fluorides and phosphorus.
Table 8.10-5 presents conventional and toxic pollutant concentra-
tions for the porcelain enameling on aluminum subcategory.
Subcategory 4 - Porcelain Enameling on Copper
Wastewater from this subcategory is generated as in the previous
subcategories; by surface preparation, enamel application, ball
milling, and related operations. Wastewater constituents gener-
ally consist of copper and the components used to form the enamel.
Water is used to rinse the workpieces after various operations,
as a constituent of the enamel slip, in spray booths, and in
cleaning, cooling and air scrubbing. Pollutants such as dirt and
greases enter the wastestream from the surface preparation and
rinsing steps. Acid pickling adds dissolved copper to the waste-
stream. Enamel preparation and application may add high concen-
trations of aluminum, titanium, manganese, nickel, zinc, and
cobalt, as well as fluorides, antimony, copper, lead, and iron.
Table 8.10-6 gives conventional and toxic pollutant concentra-
tions for the porcelain enameling on copper subcategory on a
stream basis.
Date: 6/23/80 II.8.10-12
-------
TABLE 8.10-5.
WASTEWATER CHARACTERIZATION OF THE PORCELAIN
ENAMELING ON ALUMINUM SUBCATEGORY [1]
Pollutant
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Organics
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Toluene
Nontoxic inorganics
Aluminum
Barium
Iron
Manganese
Titanium
Cobalt
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Number
of
samples
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
3
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
Number
not
detected
0
0
1
4
0
0
8
8
8
7
6
6
6
6
8
8
1
8
8
3
1
8
0
5
8
8
0
0
3
5
0
0
6
8
8
1
0
2
7
0
8
4
0
Range, mg/L
Alkaline cleaning
1.0 - 180
0.41 - 24
0.005 - 0.016
3 - 11
6.3 - 10.4
0.72 - 0.98
0.007 - 0.018
0.021 - 0.056
0.015 - 0.18
0.040 - 4.3
0.019 - 0.54
0.68 - 26
0.013 - 0.33
0.019 - 0.18
Coating
55 - 650
0.38 - 65
0.005 - 0.018
2.3 - 4.7
7.0 - 10
0.92 - 1.9
0.21 - 0.36
0.29 - 54
0.008 - 0.039
0.005 - 0.18
3.5 - 38
0.53 - 7.1
0.15 - 2.0
Median,
mq/La
17
9.4
0.007
6.7
8.8
0.91
0.003
0.17
4.5
0.059
0.14
320
1.3
0.008
3.3
9.0
0.94
5.0
0.027
0.030
0.002
9.1
0.65
0.66
Average ,
mg/L
40
8.5
0.008
6.9
8.7
0.88
0
0
0
0.003
0.012
0.038
0.095
2.2
0
0
0.21
0
0
0
6.6
0
0.097
0.11
0
0
330
9.8
0.010
3.4
8.9
1.2
0.29
0
0
11
0.024
0.057
0.002
15
0
2.2
0.74
(continued)
Date: 6/23/80
II. 8.10-13
-------
TABLE 8.10-5 (continued)
Pollutant
Number
of
samples
Number
not
detected
Range ,
mq/La
Median,
mq/La
Average,
mq/L8
Coating
Toxic pollutants (continued)
Organics
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Toluene
Nontoxic inorganics
Aluminum
Barium
Iron
Manganese
Titanium
Cobalt
8
8
3
8
8
8
8
8
8
8
8
3
0
0
0
6
0
7
0.25
0.11
0.11
0.003
3.1
- 2.1
- 1.4
- 0.94
- 0.011
- 30
0.36
0.36
0.19
6.0
0.029
0
0
0
0.62
0.59
0.33
0.007
10
0.029
Total raw waste
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Organics
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Toluene
Nontoxic inorganics
Aluminum
Barium
Iron
Manganese
Titanium
Cobalt
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
3
8
8
8
8
8
8
0
0
0
3
0
0
6
8
8
1
0
2
6
0
8
4
0
8
8
3
0
0
0
3
0
1
12
0.88
0.0
1.7
6.3
0.74
0.15
0.007
0.001
0.0
0.005
0.15
0.11
0.12
0.077
0.010
0.017
0.002
0.093
0.
- 190
- 24
- 0.015
- 11
- 10.4
- 0.98
- 0.26
- 5.2
- 0.013
- 0.13
-0.14
- 12
- 0.63
- 0.53
- 10
- 0.24
- 0.71
- 0.13
- 6.1
.006
93
9.5
0.007
4.5
8.8
0.92
2.3
0.006
0.046
3.1
0.44
0.33
2.7
0.039
0.17
0.018
2.1
0.006
105
9.3
0.007
5.8
8.7
0.89
0.21
0
0
2.2
0.006
0.048
0.073
3.9
0
0.40
0.30
0
0
0
3.8
0.10
0.24
0.046
2.6
0.006
Note: Blanks indicate insufficient data available.
"Except pH values, given in pH units.
Date: 6/23/80
II.8.10-14
-------
TABLE 8.10-6.
WASTEWATER CHARACTERIZATION OF THE PORCELAIN
ENAMELING ON COPPER SUBCATEGORY [1]
Pollutant
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Organics
1 , 2-Dichlorobenzene
Toluene
Chloroform
Dichlorobromome thane
1 , 1 ,2 ,2-Tetrachloroethane
Tetrachloroethylene
Nontoxic inorganics
Aluminum
Iron
Manganese
Titanium
Cobalt
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
pH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Number
of
samples
2
2
2
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Number
not
detected
0
1
1
0
0
0
2
2
2
2
0
0
2
2
2
2
0
2
2
2
2
2
0
0
0
2
2
0
0
3
0
0
0
0
2
1
0
0
0
2
0
0
0
0
Range, mg/La
Acid pickling
14 - 24
6.2 - 6.6
0.11 - 0.12
0.008 - 0.009
9.7 - 12
0.049 - 0.22
0.050 - 0.17
0.15 - 51
0.010 - 0.019
Coating
14,000 - 94,000
2.0 - 98
7.6 - 10.1
46 - 66
1.6 - 3.5
0.035 - 0.059
0.097 - 0.26
0.20 - 0.63
4.7 - 7.1
2.3 - 4.8
38 - 49
0.51 - 0.81
58 - 200
Median , Average ,
mg/L mg/L
19
0.52 0.52
0.006 0.006
200 200
6.45
0.12
0
0
0
0
0.008
11
0
0
0
0
0.13
0
0
0
0
0
0.11
26
0.014
0
0
31,000 46,000
1.0 1.0
0
10 37
8.7 8.8
56 56
2.4 2.5
0.42 0.42
0.047
0.22 0.19
0.30 0.38
5.9 5.9
0.055 0.055
4.8 4.0
40 42
0.77 0.70
82 110
(continued)
Date: 6/23/80
II.8.10-15
-------
TABLE 8.10-6 (continued)
Pollutant
Toxic pollutants (continued)
Organics
1 , 2-Dichlorobenzene
Toluene
Chloroform
Dichlorobromome thane
1,1,2, 2-Tetrachloroe thane
Tetrachloroethylene
Nontoxic inorganics
Aluminum
Iron
Manganese
Titanium
Cobalt
Conventional parameters
TSS
Total phosphorus
Total phenols
Oil and grease
PH
Fluorides
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Organics
1 , 2-Dichlorobenzene
Toluene
Chloroform
Dichlorobromome thane
1,1,2 , 2-Tetrachloroe thane
Te trachloroethylene
Nontoxic inorganics
Aluminum
Iron
Manganese
Titanium
Cobalt
Number
of
samples
1
3
3
3
3
3
3
3
3
3
3
3
1
3
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
3
3
3
3
3
3
Number
not
detected
1
3
0
1
1
1
0
0
0
0
0
0
0
2
0
0
0
0
2
1
0
0
0
2
0
0
0
0
3
0
0
0
1
0
0
0
0
0
Range , mg/L
Coating
0.00
0.00
0.00
100 - 200
15 - 29
64 - 120
120 - 560
48 - 64
Total raw waste
1,100 - 94,000
2 - 190
6.2 - 10.1
3.8 - 56
0.13 - 2.4
0.005 - 0.035
0.008 - 0.22
0.023 - 0.63
7.1 - 12
0.19 - 4.8
3.1 - 49
0.041 - 0.81
4.8 - 200
0.00
0.00
0.00
0.00
8.1 - 200
1.4 - 48
5.2 - 120
9.7 - 560
3.9 - 64
Median,
mg/La
0.00
180
16
85
220
51
2,500
0.080
0.006
8.1
5.4
0.28
0.42
0.021
0.032
9.3
0.004
0.38
3.2
0.062
6.6
0.00
0.00
15
29
6.9
18
4.1
Average,
mg/La
0
0
0.00
0.00
0.00
0
160
20
89
300
54
33,000
0.080
0.006
95
7.8
22
0.92
0.42
0.020
0.083
0.23
9.3
0.004
1.8
18
0.30
69
0
0.00
0.00
0.00
0.00
73
26
43
190
24
Note: Blanks, when not associated with a number of samples, indicate no data avilable.
Except pH values, given in pH units.
Date: 6/23/80
II.8.10-16
-------
II.8.10.3 Plant Specific Description [1]
Only a limited amount of information is available on specific
plants within this industry. This section describes the treat-
ment practice and wastewater composition at five plants: three
that enamel on steel, one on aluminum, and one on strip steel.
The major treatment operation employed is a settling technique.
Treatment operations are not necessarily listed in this narrative
in the same order that they are used at the plants. Wastewater
composition data were obtained from verification sampling.
Porcelain Enameling on Steel
Plant 33617. This facility produces approximately 1.56 x
107 iti'Vyr of porcelain enameled steel and uses 0.009 m3 of water/
m2 of product for this production. Average process water flow
rate is 23 m3 of water/hr. The mixed wastestream (combined with
other process wastes) is treated by several treatment methods
including settling, pH adjustment by lime and/or acid, equaliza-
tion, inorganic coagulation, clarification, sedimentation lagoon-
ing, ultrafiltration, and contract removal of the oil sludge.
Discharged water is released to a surface stream.
Plant 40063. This plant produces 370 m2/hr of porcelain
enameled steel and uses 0.031 m3 of water/in2 of product in the
process. Average process water flow rate is 11.7 m3 of water/hr.
The treatment facility treats only the process wastewater and
consists of equalization, pH adjustment with lime, polyelectro-
lyte coagulation, clarification, vacuum filtration, and sludge
landfill. Discharge is to a surface waterway.
Plant 47033. This plant produces 1.4 x 106 m2/yr of porce-
lain enameled steel and minor amounts of other products. Process
water used per square meter of product is 0.06 m3, and the flow
rate is 44.7 m3/hr. The unmixed wastestream is discharged to a
municipal treatment works after undergoing equalization, settling,
pH adjustment with caustic, and contract removal of the sludge.
Table 8.10-7 gives the water use for each process in the produc-
tion of porcelain enameled steel for the above plants. Pollutant
concentrations for the raw and treated effluents are presented in
Table 8.10-8.
Porcelain Enameling on Aluminum
Plant 33077. This facility produces 4.5 m2/yr of porcelain
enameled aluminum and uses 0.11 m3 of process water/m2 of prod-
uct. The mixed wastewater stream is treated by equalization,
settling, pH adjustment with lime and/or acid, polyelectrolyte
coagulation, clarification, and contractor removal of the result-
ing sludge prior to discharge to a surface stream. Water use for
Date: 6/23/80 II.8.10-17
-------
TABLE 8.10-7. WATER USE IN THE PORCELAIN
ENAMELING ON STEEL SUBCATEGORY [1]
(m3 of water/m2 product)
Plant identification
Process
33617
40063
47033
Alkaline cleaning
Acid treatment
Nickel deposition
Neutralization
Ball milling
Coating
0.00094
0.00014
0.00033
0.00011
0.00004
0.00066
0.0032
0.0026
0.0027
0.0016
0.0173
0.0112
0.103
0.0376
0.0208
0.0056
0^00102
Use of dip coating and spray coating in a dry
booth.
TABLE 8.10-8. CONCENTRATIONS OF POLLUTANTS FOUND IN PORCELAIN
ENAMELING ON STEEL FACILITIES3 [1]
Raw
wastewater,
Pollutant mg/L
Treated
effluent,
mg/L
Raw
Percent wastewater,
removal mg/L
Plant 33617
Conventional parameters
TSS
Total phosphorus
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
Nontoxic inorganics
Aluminum
Cobalt
Iron
Manganese
Titanium
1,660
14
ND
0.062
0.005
0.570
0.560
0.28
10.80
ND
2.78
24
4.1
150
6.0
2.0
16
1.5
ND
ND
ND
ND
0.009
ND
1.04
ND
0.032
ND
0.08
0.85
0.35
ND
99
89
100
100
100
98
100
90
99
100
98
99
94
100
Treated
effluent,
mg/L
Raw Treated
Percent wastewater, effluent. Percent
removal mg/L mg/L removal
Plant 40063
3,600
12
10
6.9
ND
ND
0.63
ND
5.5
30
16
28
4.7
110
210
125
13
1.0
ND
ND
ND
ND
0.003
ND
ND
ND
0.044
0.35
ND
0.57
0.012
ND
99+
92
100
100
99+
100
100
99+
99
100
99
99+
100
Plant 47033
190
3.4
31
ND
0.35
0.028
0.15
ND
1.0
ND
1.4
4.9
2.1
29
3.3
3.3
90
2.2
3.3
ND
0.12
0.019
0.031
NO
0.77
ND
0.23
0.55
0.26
9.7
0.43
0.22
53
35
89
66
32
79
23
84
89
88
67
87
93
Note: Blanks indicate insufficient data available.
"Treatment involves sedimentation.
this production consists of 0.14, 0.014, and 0.014 m3 of water/m2
of product for surface preparation, ball milling, and coating,
respectively. Table 8.10-9 presents pollutant concentrations for
the raw and treated effluents.
Date: 6/23/80
II.8.10-18
-------
Porcelain Enameling on Strip Steel
Plant 36077. This plant produces 9.7 x 10s m2/yr of strip
steel and uses 0.006 m3 of process water/m2 of product. The
unmixed wastewater stream is settled before discharging to a
surface stream. Amounts of water used for the production process
are 0.0021, 0.0021, and 0.0018 m3/m2 for ball milling, coating
application, and cooling, respectively. Rinse from the nickel
deposition step is recycled. Table 8.10-9 presents pollutant
concentrations for the raw and treated wastewater at this plant.
TABLE 8.10-9.
CONCENTRATIONS OF POLLUTANTS FOUND IN PORCELAIN
ENAMELING ON ALUMINUM AND STRIP STEELa [1]
Raw Treated
wastewater, effluent, Percent
Pollutant mg/L mg/L removal
Conventional parameters
TSS
Total phosphorus
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
Nontoxic inorganics
Aluminum
Cobalt
Iron
Manganese
Titanium
Aluminum
66
80
ND
ND
20
0.06
0.020
30
ND
3.8
0.70
1.0
0.30
0.008
20
plant 33077
5
3.6
ND
ND
0.9
0.006
ND
0.5
ND
0.084
0.070
0.20
ND
ND
0.4
92
96
96
90
100
98
98
90
80
100
100
98
Raw Treated
wastewater, effluent,
mg/L mg/L
Strip steel
22,000
17
ND
8.0
ND
3.0
40
30
0.72
400
200
30
20
5.0
100
plant
340
ND
ND
2.0
ND
0.20
3.0
1.0
ND
5.0
10
0.3
2.0
0.3
10
Percent
removal
36077
98
100
75
93
93
97
100
99
95
99
90
94
90
Note: Blanks indicate insufficient data available.
Treatment involves sedimentation.
II.8.10.4 Pollutant Removability [1]
Treatment technologies used in the porcelain enameling industry
are generally chosen to remove the major wastewater components:
suspended solids and toxic metals. Table 8.10-10 presents a
summary of the treatment and disposal techniques used by this
industry. Usually more than one treatment method is used at each
facility.
Some type of settling technique is used in a large portion of the
plants, with a settling tank the most common technique. pH
adjustment by chemical addition is another common treatment that
is used to neutralize the alkaline or acid wastes. Coagulants
are sometimes used to aid settling. Once the settling nears
Date: 6/23/80
II.8.10-19
-------
TABLE 8.10-10.
TREATMENT METHODS IN CURRENT USE IN
THE PORCELAIN ENAMELING INDUSTRY [1]
Number of plants using
the method, by subcategory Total
Treatment method
Skimming
Settling tank
Clarifier
Sedimentation lagoon
Tube/plate settler
Equalization
pH adjustment-lime
pH adjustment-caustic
pH adjustment-acid
pH adjustment-carbonate
pH adjustment- final
Coagulant-polyelectrolyte
Coagulant-inorganic
Chromium reduction
Emulsion breaking
Chlorination
Ultrafiltration
Pressure filtration
Vacuum filtration
Filtration
Aeration
Trickling filter
Centrifugation sludge
Material recovery
Air pollution control
Process reuse-oil
Contract removal-oil
Contract removal-sludge
Landfill-oil
Landfill-sludge
Sludge drying bed
Sludge thickening
Steel
2
35
16
11
3
24
15
7
6
1
6
10
3
2
1
1
2
5
5
3
2
1
1
1
1
1
7
8
2
17
3
1
Iron
8
2
1
1
1
1
2
2
1
Aluminum
6
2
2
2
1
1
1
1
1
1
Copper plants
2
1 50
18
11
3
28
18
7
7
2
6
12
4
3
1
1
2
5
5
3
2
2
1
3
1
1
7
9
3
19
4
1
completion, filtration techniques are used to concentrate the
sludge, which is then landfilled or contractor hauled. Oils may
be treated in a similar manner. Table 8.10-11 presents data
collection portfolio (dcp) effluent characterization data from
the plants within this industry. Tables 8.10-8 and 8.10-9 in the
plant specific section give raw wastewater concentrations, treated
effluent concentrations, and percent removal of the pollutants.
Brief descriptions of the common treatment practices and the
water reuse and recycle techniques follow.
Equalization/Neutralization
Raw waste waters are commonly collected in equalization basins to
even out the flow and the pollutant contaminant load. This permits
uniform and controlled operation of subsequent treatment facilities
Date: 6/23/80
II.8.10-20
-------
o
n>
CPl
\
U>
\
CO
o
TABLE 8.10-11. EFFLUENT CHARACTERIZATION FOR THE PORCELAIN ENAMELING INDUSTRYa
00
o
I
[1]
Number
of
Pollutant samples
Range, mg/Lb
Mediag,
Average ,
mg/L
P/E on steel
Conventional parameters
TSS
Total phosphorus
Oil and grease
PH
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Chromium, hexavalent
Copper
Lead
Nickel
Selenium
Zinc
Nontoxic inorganics
Iron
Conventional parameters
TSS
Total phosphorus
Oil and grease
pH
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Chromium , hexavalent
Copper
Lead
Nickel
Selenium
Zinc
Nontoxic inorganics
Iron
37
15
26
10
3
4
17
31
5
27
29
39
2
38
32
0
1
0
0
0
0
1
0
0
1
1
1
1
1
1 -
0.13 -
0.4 -
4.9 -
0.001 -
0.001 -
0 -
0.01 -
0 -
0 -
0 -
0.02 -
0.001 -
0 -
0.17 -
P/H
1,400
2,100
250
8.7
0.014
0.15
0.75
124
0.044
6.7
18
900
0.020
6.9
200
96
7.3
7.1
7.0
0.001
0.024
0.008
0.15
0.005
0.09
0.20
0.50
0.20
9.3
390
150
24
7.2
0.005
0.050
0.060
4.4
0.017
0.40
1.2
26
0.94
23
Number
of
samples
15
2
13
6
0
0
0
8
0
7
8
9
7
8
on copper
0.125
0.010
0.010
0.010
1.0
0.010
14
0.125
0.010
0.010
0.010
1.0
0.010
14
49
20
36
16
3
4
19
36
5
31
34
45
2
41
33
Range
9.8
0.12
0.4
4.8
0.01
0.03
0.06
0.12
0.15
0.17
, -g/Lb
Median,
mg/L15
P/E on iron
- 1,100
- 5.4
- 58
- 7.0
- 124
- 0.10
- 0.48
- 22
- 2.3
- 150
40
5.2
7.0
0.015
0.08
0.25
1.6
0.20
1.7
Average,
mg/E"
210
2.8
17
6.4
16
1.02
0.24
4.1
0.50
37
Number
of . Median, Average,
samples Range, mg/L mg/L mg/L
5
3
4
0
0
0
2
4
0
4
4
4
2
0
P/E on aluminum
20 - 390 230 200
9.2 - 16 14 13
1-44 7.5 15
0.13 - 0.53 0.33
0.01 - 1.45 0.37 0.60
0.01 - 0.10 0.06 0.060
0.13 - 3.6 0.36 1.4
0.01 - 0.36 0.13 0.16
0.43 - 0.77 0.60
P/E industry
1
0.12
0.4
4.8
0.001
0.001
0
0.01
0
0
0
0.01
0.001
0
0.013
- 1,400
- 2,100
- 250
- 8.7
- 0.014
- 0.15
- 0.75
- 124
- 0.044
- 6.7
- 18.4
- 900
- 0.020
- 6.9
- 200
124
8.3
8.0
7.0
0.001
0
0.009
0.15
0.005
0.08
0.17
0.71
0.20
6.5
370
110
22
6.9
0.005
0.050
0.09
3.9
0.017
1.1
22.6
0.01
0.91
23
Note: Blanks indicate insufficient data available.
aBased on historical data from the plant dcp responses.
Except pH values, given in pH units.
-------
Wastes in this industry generally require pH adjustment which can
be performed in mixed equalization basins or in separate neutrali-
zation reactor basins following equalization.
Sedimentation/Settling
Sedimentation by means of clarification or simple settling is the
most common technique for removal of precipitates. It is often
preceded by chemical precipitation, which converts dissolved
pollutants to solid form, and by coagulation, which enhances
settling by coagulating suspended solids into larger, faster-
settling particles. Sedimentation preceded by chemical addition
is often referred to as clarification. Simple sedimentation
normally requires a long retention time to adequately reduce the
solids content. When clarification is used retention times are
reduced and removal efficiency is increased. A properly operated
sedimentation system is capable of efficient removal of suspended
solids, metal hydroxides, and other wastewater impurities.
Chemical Addition/Precipitation
Chemical precipitation is used in porcelain enameling to precipi-
tate dissolved metals and phosphates. Chemical precipitation can
be utilized to permit removal of metal ions such as iron, lead,
tin, copper, zinc, cadmium, aluminum, mercury, manganese, cobalt,
antimony, arsenic, beryllium, molybdenum, and trivalent chromium.
Removal efficiency can approach 100% for the reduction of heavy
metal ions. Porcelain enameling plants commonly use lime, caus-
tic, and carbonate for chemical precipitation and pH adjustment.
Granular Bed Filtration
Granular bed filters are used in procelain enameling wastewater
treatment to remove residual solids from clarifier effluent.
Filtration polishes the effluent and reduces suspended solids and
insoluable precipitated metals to very low levels. Fine sand and
coal are media commonly utilized in granular bed filtration. The
filter is backwashed after becoming loaded with solids, and the
backwash is returned to the treatment plant influent for removal
of solids in the clarification step.
Sludge Concentration and Dewatering
Sludges from clarifiers can be thickened in gravity thickeners or
mechanically thickened by centrifuges. Thickened sludges can be
further dewatered on one of a number of dewatering operations
including vacuum filters, pressure filters, and belt filter
presses. Dewatered sludges are disposed generally to landfills
which must be properly constructed to conform with provisions of
the Resource Conservation and Recovery Act and regulations govern-
ing disposal of hazardous wastes.
Date: 6/23/80 II.8.10-22
-------
In-Plant Technology
Many facilities in this industry use in-plant technology to
reduce or eliminate the waste load requiring end-of-pipe treat-
ment and thereby improve the quality of the effluent discharge
and reduce treatment costs. In-plant technology involves water
reuse, process material conservation, reclamation of waste enamel,
process modifications, material substitutions, improved rinse
techniques, and good housekeeping practices.
Water reuse is practiced at several plants in this industry.
Water that may be reused for such purposes as rinse water, makeup
water, and cleanup water includes air conditioning water, acid
treatment rinse water, and noncontact cooling water. Reuse of
acid rinse water in alkaline rinses has been demonstrated at many
electroplating plants.
Process material conservation is practiced by the recovery,
reuse, or purification of the materials used in the processes.
In the nickel deposition process the nickel solution is filtered
to reduce its iron content, giving a longer life to the solution.
Because the bath is dumped less often, the pollutant load is
reduced.
The use of dry spray booths can also reduce the wastewater volume
from the plant as well as increasing excess enamel recovery and
reuse. Overspray is captured on filter screens and then swept up
and reused in the enamel slip. Several plants use this and
other, similar processes to recover the enamel raw material.
Process modifications, material substitutions, improve rinsing
techniques, and good housekeeping procedures may also signifi-
cantly reduce the amount and loading of the wastewater released.
II.8.10.5 References
1. Development Document for Effluent Limitations Guidelines and
Standards for the Porcelain Enameling Point Source Category.
EPA-440/l-79/072a, U.S. Environmental Protection Agency,
Washington, D.C., August 1979.
2. NRDC Consent Decree Industry Summary - Porcelain Enameling
Industry.
Date: 6/23/80 11.8.10-23
-------
II.9.2 EXPLOSIVES MANUFACTURE
II.9.2.1 Industry Description [1]
II.9.2.1.1 General Description
The Explosives Manufacture point source category is covered by
Standard Industrial Classification (SIC) Code 2892. This category
includes the following operations:
(I) Manufacturing operations that produce
(a) explosives
(b) blasting agents
(c) solid propellants
(d) pyrotechnics
(e) initiating explosive compounds.
(2) Packaging or assembling operations in which the products
listed above are converted into end-use products. These
operations include the loading, assembling, and packing of
ammunition and military ordnance.
(3) Operations used to demilitarize or dispose of obsolete, off-
grade, contaminated, or unsafe explosives and propellants.
The Explosives Manufacturing Industry may generally be divided
into the commercial (private) sector and the military sector. On
a production basis the military sector, consisting of 24 plants,
has operations that are for the most part distinctly different
from those used by the commercial sector, which consists of
280 plants. Operations common to both apply in only a few areas.
The major products manufactured by the commercial sector of the
industry are blasting agents and dynamites. Other products
manufactured in limited quantities include double-base propellants,
nitroglycerin, nitroglycerin/ethylene glycol dinitrate mixtures,
special grained ammonium nitrate for use in dynamites, pyrotech-
nics, and initiating explosives.
Production processes consist primarily of mixing, blending, and
loading, assembling, and packing (LAP) operations.
The military sector manufactures explosives and propellants at
separate installations. The products are then shipped to munitions
loading plants for assembly into finished items. Munitions load-
ing plants are designated LAP operations.
Most military explosives manufacturing facilities are government
owned, contractor operated. Of the 24 plants, only 10 Army
Ammunition Plants (AAP) were scheduled to operate in 1978, and
Date: 6/23/80 II.9.2-1
-------
the level of production ranges from 10% to 70% of total plant
capacity. The common explosives produced by the military include
trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), cyclo-
tetramethylenetetranitramine (HMX), nitrocelluose, and nitro-
glycerin. Nitroguanidine is often used by the military but is
normally purchased from commercial sources. Pyrotechnics supple-
mental to those manufactured by the military are also purchased
from commercial sources.
Water usage is minimal in the explosives industry, the major uses
being equipment and facility cleanup and safety. Reuse is limited,
however, due to the possibility of introduction of foreign mate-
rials that could sensitize an explosion in the processing
equipment.
In 1977, over 1,686 Gg (3.7 billion pounds) of industrial explo-
sives, blasting agents, and unprocessed explosive-grade ammonium
nitrate were sold for consumption in the United States. Approx-
imately 85% of this total was processed blasting agents and
unprocessed ammonium nitrate.
Table 9.2.1 summarizes information pertinent to the commercial
sector of the explosives manufacture point source category in
terms of the number of subcategories and the number and type of
dischargers in the industry [2], Only the commercial sector of
the Explosives Manufacturing Industry is discussed herein,
because the military sector operates a limited number of plants,
produces very few products in the primary subcategory for consid-
eration, and products are manufactured for use within the military.
TABLE 9.2-1. INDUSTRY SUMMARY [2]
Industry: Explosives Manufacture
Total Number of Subcategories: 5
Number of Subcategories Studied by Effluent Guidelines Division: 1
Number of Dischargers in Industry:
• Direct: 180
• Indirect: 0
• Zero: 100
Best practicable control technology parameters are not currently
available for the five subcategories as defined in Section
II.9.2.1.2. BPT regulations previously published in the Federal
Register are [3]:
Date: 6/23/80 II.9.2-2
-------
Manufacture of explosives: 1-day 30-day
maximum average
COD, kg/Mg 7.77 2.50
BOD5, kg/Mg 0.72 0.24
TSS, kg/Mg 0.25 0.084
pH 6-9
LAP operations:
Oil and grease, kg/Mg 0.11 0.035
TSS, kg/Mg 0.26 0.088
pH 6-9
II.9.2.1.2 Subcategpry Descriptions [1]
Five subcategories, based on the variety of production processes,
product types, and wastewater characteristics, have been selected
for the explosives industry. Factors such as plant location,
size, age, solid-waste generation, air pollution control techno-
logy, and energy consumption do not have a significant impact on
waste characteristics; they therefore are not included in the
subcategorization criteria. The five subcategories are:
Subcategory 1 - Manufacture of Explosives
Subcategory 2 - Manufacture of Propellants
Subcategory 3 - LAP of Explosives
Subcategory 4 - Manufacture and LAP of Initiating Compounds
Subcategory 5 - Formulation and Packaging of Blasting Agents,
Dynamite, and Pyrotechnics
The annual production estimate for the Explosives Manufacture
Industry is presented in Table 9.2-2. Also presented is the
precentage of total industry production contributed by each sub-
category in 1977. As indicated by the table, 95.3% of the total
industry output is represented by Subcategory 5, Formulation and
Packing of Blasting Agents, Dynamite and Pyrotechnics. Due to
the dominance of this Subcategory in the industry, this report
primarily addresses the Formulation and Packaging of Blasting
Agents, Dynamite, and Pyrotechnics in terms of wastewater charac-
teristics. Since this Subcategory does not include military
explosives products, only data regarding the commercial sector
are reported.
Subcategory 1 - Manufacture of Explosives. The manufacture
of explosives includes operations that produce explosive compounds
by the mixed acid nitration of organic material. Raw materials
used in this process include nitric acid or ammonium nitrate as
the nitrate source and either sulfuric or acetic acid as a de-
hydrating agent. Examples of the organic molecules used are
glycerin, ethylene glycol, toluene, resorcinol, hexamine, and
Date: 6/23/80 II.9.2-3
-------
TABLE 9.2-2. ESTIMATE OF ANNUAL INDUSTRY
PRODUCTION BY SUBCATEGORY [1]
Production13, Percent of total
Subcategory Subcategory title Gg industry output
1 Manufacture of Explosives 23 2
2 Manufacture of Propellants 10 1
3 Load, Assemble, and Pack
(LAP) Explosives 16 1.4
4 Manufacture and LAP of Ini-
titiating Compounds 4 0.3
5 Formulation and Packaging of
Blasting Agents, Dyanmite,
and Pyrotechnics 1,090 95.3
1,143 100.0
a
Based on 1977 industry production.
b
Production excludes explosive-grade ammonium nitrate.
cellulose. Upon nitration, these organic molecules form, in the
order presented above, the following products: trinitroglycerin
(TNG) and dinitroglycerin (DNG), ethylene glycol dinitrate (EGDN),
trinitrotoluene (TNT), and dinitrotoluene (DNT), trinitroresorcinol
(TNR), cyclotrimethylenetrinitramine (RDX), and nitrocellulose
(NC). Nitration may be accomplished on either a batch or a con-
tinuous basis. Initiating compounds, dynamite, and black powder
are not included in the Subcategory due to differences in process
and wastewater characteristics.
Production in this Subcategory creates relatively large volumes
of wastewater from neutralization and washing of the final product.
Wastewaters are generally low in suspended solids, contain soluble
nitrate and sulfate salts, and have organic concentrations that
are proportional to the solubility of the products and byproducts.
Subcategory 2 - Manufacture of Propellants. This Subcategory
includes the manufacture of nitrocellulose-based propellants and
gas generators. Propellants are similar to explosive products in
that they are mixtures of oxidant and fuel held together in a
polymeric matrix. They differ in the rate at which the reaction
proceeds. Explosives detonate in a chain reaction that occurs
extremely rapidly while propellants simply burn, evolving large
volumes of gas in a definite and controllable manner. The most
Date: 6/23/80 II.9.2-4
-------
commonly produced commercial propellants are called smokeless
powders and are designated as either single-base, double-base,
or triple-base propellants. Single-base propellants are basically
nitrocellulose, double-base propellants are chiefly nitrocellulose,
and nitroglycerin, and triple-base propellants primarily contain
nitrocellulose, nitroglycerin, and nitroguanidine. These pro-
pellants find principal use as the propelling charge in munitions,
but they are also used in gas generators and rocket propulsion.
Another type of propellant is the composite propellant, an
intimate mixture of a fuel, usually aluminum powder, and an
oxidizer, usually ammonium perchlorate, held together by a poly-
meric binder. Composite propellants are used principally for
rocket propulsion.
Relatively large volumes of wastewater are generated as the result
of water used to transport propellant between unit operations,
to remove solvents from the final product, to cool and lubricate
in the cutting and machining of the final product, and to clean
and wash down process equipment. The presence of organic solvents
often makes organic loading higher than in Subcategory 1, and
the suspended solids present are generally propellant fines from
the cutting and machining operations.
Subcategory 3 - LAP of Explosives. This subcategory includes
facilities that obtain the necessary explosives and propellants
from outside sources, then mix and pack these materials into a
final product. Included in the commercial sector of this subcate-
gory are the loading and assembly of small- to intermediate-caliber
ammunition, and the manufacturers of explosive devices. The mili-
tary sector of this subcategory produces large-caliber shells,
bombs, grenades, and other munitions that are filled with blends of
TNT and other ingredients. Propellants and small explosive devices
are usually loaded dry, while explosives are normally melted down
in kettles and molded as liquids. The small volumes of wastewater
produced reflect the characteristics of the materials being
handled and generally result from plant cleanup operations.
Subcategory 4 - Manufacture and LAP of Initiating Compounds.
This subcategory includes plants that manufacture "sensitive"
explosive compounds, such as trinitroresorcinol, nitromannite,
isosorbide dinitrate, tetryl, tetracene, lead azide, lead
styphnate, and mercury fulminate. Initiating compounds, which
are produced by the mixed acid nitration of organics, are extremely
sensitive materials that can be made to explode by the application
of heat or a slight shock. They are very dangerous to handle and
are used in comparatively small quantities to initiate the detona-
tion of larger quantities of less sensitive explosives. Plant
facilities often include a LAP operation on site to reduce the
bulk shipping of these hazardous compounds. Final products
include primers, detonators, detonating cords, percussion caps,
and electric blasting caps. The LAP operation differs from
Subcategory 3 by the small amounts of explosives used.
Date: 6/23/80 II.9.2-5
-------
Wastewater from this subcategory is generated by neutralization
and purification of the compounds, safety practices, and plant
and equipment cleanup. Wastewater volume is generally higher
per unit production than in other subcategories due to safety
procedures. Pollutant loads result from the production processes
and from chemical treatment of catch basins and sumps to desensi-
tize released initiating compounds.
Subcategory 5 - Formulation and Packaging of Blasting Agents,
Dynamite, and Pyrotechnics. Subcategory 5 includes operations
that manufacture blasting agents, dynamite, black powder, and
pyrotechnics. Processes that produce pyrophoric materials, which
ignite spontaneously if not covered with water, are excluded
because of the liberal use of water necessary to prevent sponta-
neous ignition.
Blasting agents—Blasting agents include ANFO and
slurries (water gels). ANFO (ammonium nitrate/fuel oil) blasting
agent compositions, also known as nitrocarbonitrates, are easily
prepared and inexpensive, and they dominate the explosives market
today. They are generally used in mining operations, with the
major portion produced being used for bulk loading into dry bore
holes. If water is present, the ANFO compositions may be placed
in water-resistant containers and used.
The raw materials used to manufacture ANFO mixtures include fuel
oil, explosive-grade ammonium nitrate (AN), aluminum granules,
ferrophosphorus, and dinitrotoluene. The AN used is normally
produced under special prilling conditions that give the prills
high porosity for better absorption of the oil. Small amounts
of anticaking agents are also used.
Fuel oil is received in bulk and is stored in large tanks. When
needed it is pumped to the use site. The AN is received in bulk
railroad hopper cars and may be transferred to a storage area or
used from the hopper car. The remaining ingredients are normally
received in bags or steel drums.
ANFO may be produced by dry mechanical mixing, injection of the
fuel oil into the AN as it is transferred to the packaging area,
or injection of the fuel oil into the AN as it is transferred
into the bore hole at the use site. Packaging, when used, consists
of cylindrical plastic tubes, plastic-lined bags, or metal
cannisters.
Approximately 75 plants produce ANFO. Their wastewater is limited
to periodic cleanup of the plant area and rainfall runoff from
the unloading areas. Dry cleanup is used when possible, but AN
is very hydroscopic and tends to become pasty and hard to clean
in humid conditions. Heated floors are sometimes used to reduce
hydroscopic effects and thereby aid in the cleanup process.
Date: 6/23/80 II.9.2-6
-------
Slurries (water gels) are water-resistant, high energy blasting
agents used for wet bore holes and applications requiring greater
energy than that supplied by ANFO. Slurry products usually
require a high explosive primer for detonation. Slurry formulation
is an art and can produce a desired energy release as well as the
desired explosive properties. Sensitivity relies on the type
and characteristics of the raw materials used and the method of
mixing. Water resistance and gel consistency are achieved by
addition of cross-linking soluble gums. There are approximately
21 slurry manufacturing plants in the United States.
Raw materials are received in the same way as at ANFO plants, with
sodium nitrate, aluminum granules, and organic liquid extenders
also being received in bulk.
Slurries may be prepared on site or at the plant. For packaged
slurries the entire formulation is prepared by premixing the
liquid ingredients into a paste, then adding the solids and
packaging the product. On-site production may be carried out in
two ways. In one method the slurry is prepared as above but the
gum crosslink agent is not added until the slurry is pumped into
the bore hole. In the second method the paste is prepared, all
the dry ingredients are added at the use site, and the mixture
is pumped into the bore hole.
Wastewater from slurry production comes from automatic packaging
machinery, periodic equipment cleanup, dust control scrubbers,
and rainfall runoff.
Dynamites—Seven plants produce high explosive dynamite
compositions that are used in underground mines and for blasting
small-diameter bore holes. Dynamite consists of nitroglycerin
or ethylene glycol dinitrate, porous filler material, and oxidiz-
ing salts such as AN. The grained AN used in dynamite is produced
by controlled evaporation of high concentration AN solutions fol-
lowed by crystallization in open-top agitated vessels (kettles).
Production occurs in three general steps. First, all ingredients
except the nitroglycerin or ethylene glycol dinitrate are mixed
in batch blenders in a building known as a dope house. The dope
mixes are then transferred to the mix house where the nitro-
glycerin or ethylene glycol dinitrate is added in batch blenders.
The mix is then sent to the packaging house and loaded into
cardboard tubes by wooden tamping machines.
Plant and equipment cleanup and dust control wet scrubbers are
the major sources of wastewater.
Pyrotechnics--The 45 commercial pyrotechnic plants in
the United States are divided into 2 general types. The fireworks
industry consists of 13 major and 25 minor plants. The flare
Date: 6/23/80 II.9.2-7
-------
industry, which produces illuminating flares, distress flares,
and smoke generators, consists of seven plants.
Fireworks consist primarily of black powder and metal salts, which
produce the colors. The mixture is held together by a water
soluble binder such as sugar or gum. The ingredients are combined
in dry batches and water is added. The wet mixture is then molded
and air dried. Black powder is also used for the fuse and pro-
pelling charge of the assembled device. Flares are produced
similarly but may use an organic binder instead of a water soluble
one. If so, an organic solvent may be necessary to clean the
equipment. Fireworks production equipment is generally dry clean-
ed with brushes.
Ammonium Nitrate (AN). Explosive-grade ammonium nitrate
plants, although they do not fall directly under this SIC code,
are related to the industries of Subcategory 5 because of the
extensive use of AN as a raw material in their products. Approx-
imately 16% of all the AN produced in the United States in 1976
was used in explosives products. Ammonium nitrate is produced
by several processes including the Stengel, prilling, and grain-
ing processes. The general procedure is evaporation of the water
from a solution of AN by a physical process.
Wastewater from the production of AN generally is limited to
plant housekeeping, air pollution control, and fugitive discharges,
although some wastewater may result from the evaporation steps
in the process. AN is the major pollutant in the wastewater,
which allows the wastewater to be recycled, if not too contaminat-
ed, or sold as dilute fertilizer solution.
Table 9.2-3 presents a list of the common ingredients for the
products described above.
II.9.2.2 Wastewater Characterization [I]
The general nature of the wastewater sources within the explosives
industry results in a wide variance of wastewater volumes. The
volume of wastewater generated depends on operating methods, equip-
ment type and condition, housekeeping practices, safety practices,
product mix, and package type. Table 9.2-4 presents wastewater
flowrate data for each type of production in Subcategory 5.
Wastewater does not originate from direct contact within the
process with the ingredients used to produce the products; there-
fore, only cleanup operations normally have the potential to
contribute pollutants to the wastewater stream. The materials
that may possibly enter the wastewater stream include the ingred-
ients of each type of explosive found in Table 9.2-3. Ammonium
nitrate, which is used extensively in this industry, is generally
found in all wastewater from Subcategory 5 facilities and con-
tributes to the TKN, NH3-N, N03-N, and TDS levels. Inorganic
Date: 6/23/80 II.9.2-8
-------
TABLE 9.2-3
COMMON EXPLOSIVE INGREDIENTS
Product
Ingredients
Dynamite
Black powder
Ammonium nitrate/fuel
oil mixtures
Slurries (water gels)
Propellants
Pyrotechnics
Initiating compounds
Nitroglycerin, barium sulfate, ammonium
nitrate, ammonium chloride, sodium ni-
trate, sodium chloride, calcium carbonate,
calcium stearate, sulfur, nitrocellulose,
phenolic resin or glass beads, bagasse,
sawdust or wood flour, coal, cornmeal and
cornstarch, inorganic salts, grain and
seed hulls and flour
Charcoal, sulfur, potassium nitrate
Ammonium nitrate, ferrophosphorus, calcium
silicate, dinitrotoluene, fuel oil,
aluminum, coal, mineral oil
Ammonium nitrate, sodium nitrate, guar
gum, water, crosslinking agents for gum,
ethylene glycol, aluminum granules,
flakes, or powders, glass microspheres,
fuel oil, smokeless powder, trinitro-
toluene, carbon fuel, organic amines,
ferrophosphorus, silicon
Nitrocellulose, plasticizers, density
modifiers, burning rate modifiers, nitro-
glycerin, nitroguanidine, aluminum powder,
oxidizers (e.g., ammonium perchlorate),
polymeric binders
Black powder, potassium nitrate, copper
salts, barium nitrate, strontium nitrate,
strontium carbonate, aluminum metal,
magnesium metal, potassium chlorate,
potassium perchlorate, antimony sulfide,
red phosphorus, ammonium perchlorate,
boron, manganese oxide, lead oxide, copper
oxide, sugar, linseed oil
Pentaerythritol tetranitrate (PETN) ,2 , 4 , 6-
trinitroresorcinol (styphnic acid), nitro-
mannite (HNM), isosorbide dinitrate,
trinitrophenylmethylnitramine (tetryl),
tetracene, lead azide, lead styphnate,
mercury fulminate
Date: 6/23/80
II.9.2-9
-------
o
to
rt
(D
M
CO
\
CD
O
TABLE 9.2-4. SUMMARY OF WASTEWATER FLOWRATE DATA FOR SUBCATEGORY 5 [1]
v£>
»
N)
Wastewater volume
m3/d (gal/d)
Product type
ANFO
Slurry
Dynamite
Pyrotechnics
Average3
0.3 (79.3)
5.2 (1,374)
72 (19,022)
b
Minimum
0
0
0
0
Maximum
3.8 (1,004)
31 (8,190)
348 (91,942)
0.76 (201)
m3/Mg of
Average3
0.009 (0.001)
0.20 (0.024)
0.11 (0.013)
b
product (gal/lb)
Minimum
0
0
0
0
Maximum
0.04 (0.005)
0.81 (0.097)
2.8 (0.336)
0.13 (0.016)
Average is based on plants reporting data only.
Average value is not presented since only a fraction of pyrotechnics plants generate
wastewater.
-------
salts and metals are used in most Subcategory 5 product types and
contribute to TDS, TSS, and nitrate levels, and to heavy metal
concentrations. Small concentrations of organic materials may
also be found in some industry wastewaters.
Tables 9.2-5 and 9.2-6 summarize the available verification data
on toxic pollutants and on conventional and classical pollutants,
respectively, for the Explosives Manufacture Industry. Since
most plants have several production processes on site, the data
have been collated into these processes representing wastewater
production processes rather than an average plant.
II.9.2.3 Plant Specific Description [1]
Based on the products manufactured and the quantity of information
available, the four plants described below were selected for
presentation of plant specific data. Final treated effluent data
are not currently available for any of these sampled plants.
• Plant 03 - Plant 03 produces ANFO products, slurry products,
and explosive-grade ammonium nitrate. Raw wastewater from the
plant is sent to an evaporative/percolative pond where the water
is lagooned. The lagoon has no effluent reported.
• Plant 27 - Plant 27 produces only ANFO products. Raw waste-
water is collected in a clay-lined pond, then periodically applied
to vegetation-covered land adjacent to the plant.
* Plant 30 - Plant 30 produces dynamite, ANFO products, and
NCN products. Treatment consists of an evaporative/percolative
pond that has no reported effluent.
* Plant 63 - Plant 63 produces solely pyrotechnic products.
Very little wastewater is produced. An evaporative/percolative
pond is used to hold the wastewater produced by the process. No
effluent flow was reported.
Table 9.2-7 presents toxic and conventional pollutant concentration
data for the selected plants. Data are from the verification
sampling phase except as noted. Each plant is divided into
product lines and is usually presented as an entire plant.
Treated effluent data were not available. Pollutant loading data
for each plant subdivision are presented in Table 9.2-8.
II.9.2.4 Pollutant Removability [1]
Treatment practices are limited in number in the explosives in-
dustry due to the small volumes of wastewater produced and the
typical characteristics of the wastewaters from the plants.
Effluent data are very limited, since most plants do not recognize
any effluent discharge from plant property. No plant specific
treatment data are available at this time.
Date: 6/23/80 II.9.2-11
-------
D
DJ
ri-
ft
TABLE 9.2-5.
00
o
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATER FROM THE FORMULATION AND PACKAGING OF
BLASTING AGENTS, DYNAMITE, AND PYROTECHNICS [1]
Toxic pollutant
Metals and inorganics
Antimony
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Phenol
Phenol
Pesticides and metabolites
Isophorone
Metals and inorganics
Antimony
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Phenol
Phenol
Pesticides and metabolites
Isophorone
ANFO
Number
of times Concentration,
Ana- De- yg/L
lyzed tected Av Med Max
20 ND
2 2 470 470 940
1 1 14 14 14
4 2 30 5 110
1 1 100 100 100
20 ND
4 3 730 730 1,400
2 2a 68 68 70
Ammonium nitrate
10 ND
1 1 30 30 30
2 1 10 10 20
11 222
2 2 70 70 116
Slurry
Number
of
Ana-
lyzed
1
1
2
2
2
1
1
1
1
1
1
1
1
1
1
times Concentration,
De- ug/L
tected Av Med Kax
I 350 350 350
1 10 10 10
2 1,300 1,300 2,600
2 50 50 80
2 510 510 980
0 ND
Pyrotechnics
0 ND
1 37 37 37
1 150 150 150
1 ND
0 ND
1 45 45 45
1 72 72 72
0 ND
1 15 15 15
Dynamite
Number
of times Concentration,
Ana- De- Ug/L
lyzed tected Av Med Max
11 10 10 10
11 10 10 10
1 1 1,400 1,400 1,400
11 20 20 20
NOTE: Blanks indicate not analyzed or not reported.
Both below minimum detection.
-------
Date: 6/23/80
n
I—I
vD
N>
1
H
CO
TABLE y.2-b. CONCtNTKAl iUWb Ur UUJNVtJNi J.UINAL. ruuiji
WASTEWATER FROM THE FORMULATION AND
AGENTS, DYNAMITE, AND PYROTECHNICS
Number
of times
Pollutant
BOD5
COD
TSS
TKN
Oil and grease
TDS
NH3-N
NO3-N
BODs
COD
TSS
TKN
Oil and grease
TDS
NH3-N
NO3-N
Ana-
lyzed
1
1
1
1
1
1
1
1
2
2
1
2
1
2
2
De-
tected
1
1
1
1
1
1
1
1
2
2
1
2
1
2
2
ANFO
JJ.rtJ.NJ.£> rUUINU ilN JVttVK
PACKAGING OF BLASTING
[1]
Slurry
Number
Concentration, of times Concentration,
mg/L
Av
3,120
2,760
1,130
13,500
1,300
80,100
12,000
19,600
Dynamite
6
18
8
41
320
33
25
Med
3,120
2,760
1,130
13,500
1,300
80,100
12,000
19,600
6
18
8
41
320
33
25
Ana-
Max lyzed
3,120 2
2,760 3
1,130 3
13,500 3
1,300
80,100 3
12,000 3
19,600 3
8 1
20 3
8
45 3
320
33 3
27 3
De- mg/L
tected Av Med Max
2 6,060 6,060 9,870
3 5,880 4,020 13,600
3 935 820 1,980
3 4,690 5,770 8,240
3 18,900 18,000 38,000
3 3,520 4,940 5,580
3 5,860 7,780 9,160
Ammonium nitrate
1 90 90 90
3 69 27 168
3 248 97 582
3 165 83 350
3 478 104 1,250
NOTE: Blanks indicate not analyzed or not reported.
-------
o
(u
rt
TABLE 9.2-7. WASTEWATER CHARACTERIZATION FOR EXEMPLARY PLANTS
IN THE FORMULATION AND PACKAGING OF BLASTING AGENTS,
DYNAMITE, AND PYROTECHNICS INDUSTRY [1]
00
o
V£>
Pollutant
Metals and inorganics, ug/L
Antimony
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
Organics, ug/L
Benzene
1 , 2-Dichloroethylene
1,2-Trana-dichloroethylene
Trichlorof luoromethylene
Bis(2~ethylhexyl) phthalate
Isophorone
2-Nitrophenol
Di-n-octyl phthalate
Pher.ol
Toluene
Conventional, rag/L
BOD
COD
TKN
NHj-N
NOa-N
TDS
TSS
Oil and grease
Influent flowrate, raVd
Plant 03
ANFOa Slurry AN
ND 350 ND
ND 80 20
ND 980 116
2,260
4,020 12
5,770 64
5,580 61
7,780 104
38,000
1,980
0.19 2.4 340
Plant 27
Plant ANFO
38b
K 94°
26b 14
110
100
ND
1,330
W
30b
13b
65
69 3,120
371 2,760
245 13,500
215 12,000
934 19,600
80,100
1,130
1,300
371 0.24
Plant 30
Dynamite ANFO NCN Plant
3 OK
10 ND 20 80
1,450 136 2,740 l,070b
L
36b
«h
90b
96b
9c 9
15C 130
45C 155
33 118
27-j 317
320°
8C
347 0.6 0.6 385
Plant
Pyrotechnics
ND
37
154
ND
ND
45
72
ND
15
1.0
63
Plantb
30
41
30
23
105
111
130
1.0
NOTE: Blanks Indicate data not available.
"slurry prepared by mixing 200 mg of ANFO or NCN product per liter of distilled deionized water.
Screening data.
CMix house and dope house effluents only; no washdown.
-------
TABLE 9.2-8. WASTEWATER TOXIC AND CONVENTIONAL POLLUTANT LOADINGS FOR
ft
(D
C,At,nrL,AKX fUftJNTb J.W THtt tUKMULiA
BLASTING AGENTS, DYNAMITE, AND
T1UN AND PACKAGING OF
PYROTECHNICS INDUSTRY [1]
Cj*
\
[^ Pollutant
Plant 03
ANFO Slurry AN
Plant 273
ANFO
Plant 30 Plant 63
Dynamite ANFO NCN Pyrotechnics
\
°P Metals and inorganics, g/d
Antimony
Chromium
Copper
Cyanide
Lead
Nickel
Silver
Zinc
»-i Organics, g/d
t— 1
'yj Phenol
i Conventional, kg/d
171 BOD
COD
TKN
NH3-N
N03-N
TDS
TSS
Oil and grease
<0.01 0.84 <3.4
<0.01 0.19 6.8
<0.01 2.4 39.4
5.4
9.6
13.8
13.3
18.6
90.8
4.7
36.9
0.38
0.75
0.67
3.2
2.9
4.7
19.2
0.27
<0.01
0.04
0.15
3.5 <0.03 0.06 <0.01
503 0.4 8.2 0.05
0.01
2.8
5.2
15.5
11.4
8.3
110
NOTE: Blanks indicate data not available.
Quantities calculated based on product concentration in wastewater of 1%. Screening data.
-------
Control and treatment practices in use today can be divided into
in-plant source control and end-of-pipe treatment.
II.9.2.4.1 In-Plant Wastewater Source Control
Control practices within the plant can consist of wastewater
reduction, recycle, or isolation. Reduction of wastewater volume
is accomplished by use of dry cleaning practices and cleanup water
recycle. Dry cleanup consists of dry sweeping floor areas and
shovel collection of waste, equipment cleanup with brushes, and
use of wet vacuum systems. The material collected can be reused
if not overly contaminated with foreign material.
Cleanup water recycle deals with the dust control wet scrubber
system. Because dust must be controlled for safety and industrial
hygiene reasons, the pollutant load in the raw wastewater from
the dust control system cannot be reduced. However, the volume
of the wastewater can be reduced significantly by recirculation
of the wet scrubber water. This recirculation increases the
ammonium nitrate loading and can make it feasible to recycle the
wastewater to an AN plant. Alternative dust collectors, such as
cyclone-type collectors, can reduce or eliminate this source of
wastewater and must also be considered.
Direct recycle of wastewater into the product is not applicable
in this industry. However, a few plants practice concentration
by evaporation and reuse the concentrated wastewater in ammonium
nitrate production. Care must be taken to prevent contamination
of this recycle for safety reasons. Isolation or containment of
wastewater is practiced by enclosing loading and unloading areas,
diking or trenching storage areas, and collecting runoff in
lagoons.
II.9.2.4.2 End-of-Pipe Treatment
Treatment methods being used by the explosives manufacturing
industry to control pollutant levels in raw wastewater streams
include ponding, land application, biological oxidation in con-
junction with other raw waste loads, and solids removal by filtra-
tion, settling ponds, or air flotation. Only a few of the treat-
ment systems used have any effluent discharge and most treat a
combination of wastewater sources. Table 9.2-9 shows a summary
of the treatment systems used by some Subcategory 5 plants.
Ponding. Ponding is the most common form of treatment for
Subcategory 5 plants. Generally, the ponds are not lined and
natural percolation could be occurring. Long winter seasons
create some problems for ponding because of the large inventory
storage with negligible percolation or evaporation. Evaporation
ponds are very effective where the natural evaporation rate from
stagnant water exceeds rainfall. This would generally include
states west of the Mississippi. Increased evaporation by
Date: 6/23/80 II.9.2-16
-------
Q>
K>
W
\ TABLE 9.2-9. SUMMARY OF INDUSTRY CONTROLS FOR SUBCATEGORY 5 [1]
o
I
H>
~J
Control data
Total number of plants estimated
Number of plants studied
Plants reporting no process-related wastewater
Plants reporting wastewater discharge without
treatment
Plants using evaporative/percolative ponds
Plants using land application
Plants using solids separation only
Plants discharging to a combined wastewater
treatment system
ANFO
75
64
11
46
6
3
0
1
Slurry
23a
23
2C
4
8
4
4
1
Dynamite
7
6
1
0
1
1
2
1
Pyrotechnics Total
45b
7b
2b
0
1
0
0
2e
150
100
16
50
16
8
6
5
Includes one plant which is reported to be inactive; includes two plants at one plant site.
38 plants produce fireworks only and are considered dry operations without wastewater discharge;
7 plants produce flares, distress signals, etc.
f*
Includes one plant which concentrates and recirculates process wastewater.
Includes filtration, settling ponds or tanks, and air flotation. Settling sumps may be used at
other plants prior to ponding or discharge to treatment plants.
elncludes one plant that has collected wastewater hauled by disposal firm.
-------
mechanical methods, such as sprayers or cooling towers, may also
be effective for other areas but is not in current use.
Slow-Rate Land Treatment. Land application of wastewater
using spray irrigation is the second most often practiced method.
Wastewater is collected in a pond and is applied to plant-covered
land areas during the growing season. Mobile or stationary
sprayers may be used. The amount of water applied per acre varies
at each site according to the amount of wastewater produced and
land area available. No negative effects have been observed on
green plants in the treatment areas. Dilution may be necessary
for wastewaters with very high nitrogen content.
Biological Treatment. Biological treatment is used at one
plant to handle wastewater from several sources. Slurry plant
wastewater is combined with explosives manufacturing plant waste-
water for a combined flow of approximately 150 m3/day (40,000 gpd),
The water is treated in a diffused-air, extended aeration, activat-
ed sludge treatment system. Based on verification data from this
plant, cyanide and ammonia nitrogen levels were reduced more than
90% and nitrate nitrogen increased from 900 mg/L to 1,400 mg/L.
Other combined wastewater treatment systems include septic tanks,
equalization and neutralization ponds a facultative ponds, and
activated sludge treatment.
Solids Separation. Suspended solids are found at various
levels in wastewater from slurry and dynamite plants. Dynamite
wastewater has very small particles which originate from the
airborne dust collected by the wet scrubbers. Slurry wastewater
generally contains larger particles, such as granular aluminum
or glass microspheres. Small settling ponds, air flotation, and
continuous paper belt filler are three methods used to remove
these solids from the wastewater. Another method uses caustic
to dissolve the aluminum present, then neutralizes the treated
wastewater to convert the paint grade aluminum in the raw waste-
water to a settleable sludge. The sludge is then recovered and
reused.
Alternative Technologies. Several potential technologies
for treating industrial wastewater containing high levels of
ammonium and nitrate nitrogen have been studied. These technolog-
ies include biological processes involving a variety of process
configurations, and physical/chemical unit processes, such as
reverse osmosis, ammonia stripping, and ion exchange. Break
point chlorination and electrodialysis have also been suggested.
II.9.2.5 References
1. Technical Review of the BAT Analysis of the Explosives Indus-
try (draft contractor's report). U.S. Environmental Protec-
tion Agency, Washington, D.C., April 1979.
Date: 6/23/80 II.9.2-18
-------
2. NRDC Consent Decree Industry Summary - Explosive Manufacturing,
3. Environmental Protection Agency Effluent Guidelines and Stand-
ards for Explosives Manufacturing. 40 CFR 457; 41 FR 10180,
March 9, 1976.
Date: 6/23/80 II.9.2-19
-------
II.9.3 GUM AND WOOD CHEMICALS
II.9.3.1 Industry Description
II.9.3.1.1 General Description [1]
The Gum and Wood Chemicals Industry in the United States is cov-
ered by Standard Industrial Classification (SIC) Code 2861. With-
in this classification are establishments primarily engaged in
manufacturing hardwood and softwood distillation products, wood
and gum naval stores, charcoal, natural dyestuffs, and natural
tanning materials. SIC 2861 does not include establishments
primarily engaged in manufacturing synthetic tanning materials
and synthetic organic chemicals, or those engaged in the produc-
tion of synthetic organic dyes; rather, these establishments are
included within SIC Codes 2869 and 2865, respectively.
Some materials produced under SIC 2861, such as rosins, may be
further processed into materials classified under different SIC
codes. Those cases in which materials change classifications
within the same plant are included in this description. Excluded
are those cases where materials are purchased from one SIC 2861
plant for further processing in a different plant into a product
with a different SIC code.
Table 9.3-1 summarizes pertinent information regarding the number
of subcategories, the number of subcategories studied by Effluent
Guidelines Division, and the number and type of dischargers in
the Gum and Wood Chemicals Industry.
TABLE 9.3-1. INDUSTRY SUMMARY [1, 2]
Industry: Gum and Wood Chemicals
Total Number of Subcategories: 7
Number of Subcategories Studied: 4
Number of Dischargers in Industry:
Direct: 14
Indirect: 6
Zero: 3
Best Practicable Technology (BPT) limitations currently promul-
gated for each subcategory are presented in Table 9.3-2. No
information regarding limitations on the sulfate turpentine sub-
category is available.
Date: 6/23/80 11.9.3-1
-------
D
(a
ft
(B
OJ
00
O
VD
U>
I
NJ
TABLE 9.3-2.
BPT LIMITATIONS FOR THE GUM AND WOOD
CHEMICALS MANUFACTURING INDUSTRY [3]
Concentration, kg/Mg
BOD5 TSS
Subcategory
Char and charcoal briquets
Gum rosin and turpentine
Wood rosin, turpentine, and pine oil
Tall oil rosin, pitch, and fatty acids
Essential oils
Rosin-based derivatives
Sulfate turpentine
Daily "30-day Daily
maximum average maximum
30-day
average pH
No discharge of process wastewater
to navigable waters
1.42 0.755 0.077
2.08 1.10 1.38
0.99 0.53 0.705
22.7 12.0 9.01
1.41 0.748 0.045
0.026
0.475
0.243
3.11
0.015
pollutants
6.0-9.0
6.0-9.0
6.0-9.0
6.0-9.0
6.0-9.0
No specific limitations for this subcategory are available; however, other subcategory
limitations may address portions of this subcategory.
-------
II.9.3.1.2 Subcategory Descriptions
The modern Gum and Wood Chemicals Industry is grouped into the
following major areas:
(1) Char and charcoal briquets
(2) Gum rosin and turpentine
(3) Wood rosin, turpentine, and pine oil
(4) Tall oil rosin, fatty acids, and pitch
(5) Essential oils
(6) Rosin derivatives
(7) Sulfate turpentine
Three of the seven Gum and Wood Chemicals subcategories (char and
charcoal briquets, gum rosin and turpentine, and essential oils)
have been submitted for exclusion under Paragraph 8 of the NRDC
Consent Decree. These subcategories are described herein; how-
ever, no wastewater characterizations are presented.
Char and Charcoal Briquets. The char and charcoal industry
in the United States is comprised of some 80 plants primarily
concentrated in the eastern section of the country. Char is pro-
duced from the destructive distillations of softwood and hardwood
(primarily the latter). Char, in turn, may be processed into
charcoal briquets or activated carbon. Charcoal, in itself, is
one of the more economically important products of the Gum and
Wood Chemicals Industry with its wide use in the chemical and
metallurgical industries (although largely replaced therein by
coke) and in other areas, including use as a filter for gaseous
and liquid streams.
Exclusion of revised BAT and NSPS limitations has been recom-
mended for all specific pollutants on the basis of Paragraph 8 of
the NRDC Consent Decree since the existing BAT and NSPS require
no discharge of process wastewater. The only discharge of water
to surface water occurs from runoff which is regulated by BPT.
Gum Rosin and Turpentine. Currently, there are only seven
plants identified in the gum rosin and turpentine subcategory,
all of which are located in Georgia. The two largest plants have
diversified and are now producing rosin-based derivatives in
conjunction with gum rosin and turpentine. In terms of product
value, gum rosin and turpentine products are a minor portion of
the Gum and Wood Chemicals Industry.
Date: 6/23/80 II.9.3-3
-------
Exclusion of BAT, NSPS, and pretreatment standards has been recom-
mended for all specific toxic pollutants on the basis of Para-
graph 8. Of seven plants in the industry, one is an indirect
discharger, and the remaining six are self-contained dischargers.
These six plants operate on a seasonal basis between May and
September (approximately 180 days per year). Flows of process
wastewaters in this subcategory are quite low (averaging about
5.3 m3/day per plant).
The only toxic pollutants found during screening analysis of the
indirect discharger were benzene, toluene, 6-BHC, and metals.
However, this plant is also a rosin-based derivatives producer
which is covered under the rosin derivatives subcategory of the
Gum and Wood Chemicals Industry. Exclusion of the NSPS limita-
tions is recommended since no new sources exist and most existing
plants are expected to close within the next 10 years for eco-
nomic reasons. Exclusion of pretreatment is recommended since
only one indirect discharger exists, and the effluent from this
plant will be regulated under the rosin derivatives subcategory.
Wood Rosin, Turpentine, and Pine Oil. The wood rosin, tur-
pentine and pine oil industry consists of five plants in the
United States. In a typical process, pine stumps are brought
into the plant, conveyed, and washed. The water and sediment
flows to a settling pond from which water is recycled back to the
washing operation. Pine stumps are reduced to chips; the chips
undergo an extraction process that enables them to be used as
fuel (the solvent used during the extraction process is removed
from the chips by steaming); and spent chips are removed from the
retort and sent to the boilers as fuel. The solvent is recycled
for use in the retorts.
The extract liquor is sent to a distillation column to separate
the solvent from the products. The bottom stream from the first
distillation column enters a second distillation column. The
bottom stream from the second column is the finished wood rosin
product.
The crude terpene, which has been removed in the second distilla-
tion column, is stored until a sufficient quantity has been ac-
cumulated for processing in a batch distillation column. The
distillation column is charged with the crude terpene material,
and the condensed material enters a separator. The terpene and
pine oil products are removed from the separator.
Tall Oil Rosin, Fatty Acids, and Pitch. Twelve tall oil
distillation plants, primarily located in the Southeastern United
States, are currently in operation. Two additional plants are
not in operation but could be made operational if economic con-
ditions so dictated.
Date: 6/23/80 11.9.3-4
-------
Crude tall oil is particularly attractive as a raw material be-
cause of its availability as a "waste" product of the kraft pulp
and paper industry.
The crude tall oil is treated with dilute sulfuric acid to remove
some residual lignins as well as mercaptans, disulfides, and
color materials. Acid wash water is discharged to the process
sewer. The stock then proceeds to the fractionation process,
where the pitch is removed from the bottoms of the first column
and is either sold, saponified for production of paper size, or
burned in boilers as fuel. The remaining fraction of the tall
oil (rosin and fatty acid) proceeds to the pale plant, where the
quality of the raw materials is improved. The second column
separates low-boiling-point fatty acid material, and the third
column completes the separation of fatty and rosin acids.
The wastewater generated in this subcategory results from pulling
a vacuum on the distillation towers. This water is generally
recycled, but excess water is discharged to the plant sewer.
Essential Oils. The only essential oil being produced in
this subcategory is cedarwood oil. Cedarwood oil is produced by
steaming cedarwood sawdust in pressure retorts to remove the oil
from the wood particles.
Exclusion of BAT, NSPS, and pretreatment standards has been recom-
mended for all specific toxic pollutants on the basis of Para-
graph 8. The subcategory includes seven plants, none of which is
a direct discharger; one is an indirect discharger and the re-
maining six have no discharge. Flows of process wastewater in
this subcategory are low (a maximum flow of 57 m3/d from the
indirect discharger under full-scale production). The only toxic
pollutants detected during screening of the indirect discharger
were benzene and metals, and all were at low levels.
Rosin Derivatives. Rosin derivatives are not included in
SIC 2861, Gum and Wood Chemicals, but in SIC 2821, Plastics and
Synthetic Materials. Derivatives production is a natural exten-
sion of processing in gum and wood chemicals plants since the
rosin is available in the plants. This industry description is
applicable only to those derivative operations which are located
within and in conjunction with gum and wood chemicals facilities.
Another derivatives operation that occurs in gum and wood chemi-
cals plants is terpene derivatives. Derivative products include
ink resins, paint additives, paper size, oil additives, adhe-
sives, wetting agents, chewing gum base, and chemical-resistant
resins.
Sixteen gum and wood chemicals plants currently are producing
rosin or terpene derivatives. These plants are located within
all four types of rosin-producing plants.
Date: 6/23/80 II.9.3-5
-------
Process operating conditions in the reaction kettle are dependent
on product specifications, raw materials, and other variables. A
simple ester is produced under high temperature vacuum conditions.
A steam sparge is used to remove excess water of esterification,
and the condensable impurities are condensed in a noncontact
condenser on the vacuum leg and stored in a receiver. Noncon-
densables escape to the atmosphere through the reflux vent and
steam vacuum jets.
Wastewater is developed from the chemical reaction and separation
of product.
Sulfate Turpentine. Sulfate turpentine was originally con-
sidered to be a waste product in the kraft pulp and paper proc-
ess. However, modern technology allows it to be profitably re-
covered by a distillation process to such an extent that sulfate
turpentine is the major source of turpentines in the Gum and Wood
Chemicals Industry.
During the distillation of sulfate turpentine, the first tower is
usually used to strip odor-causing mercaptans from the turpentine.
Subsequent fractionation breaks the turpentine into its major
components: a-pinene, p-pinene, dipentene, and sulfated pine
oil.
The distillation of sulfate turpentine is an intermediate produc-
tion step. The operations are usually batch reactions that take
place in reaction kettles in the presence of some organic solvent
and metal catalyst. The catalyst and solvent used depend on the
type of products required. There are approximately 200 products
produced in this area.
Wastewater usually is generated from the condensation in the
distillation tower and from washdown of reactors.
II.9.3.1.3 Wastewater Flow Characterization
The volume of wastewater produced by the plants in the Gum and
Wood Chemicals Industry ranges from 0 to 7,570 ms/d. Discharge
flow rates for each subcategory are difficult to quantify because
most plants have combined processes that fall under several dif-
ferent subcategories, and all process wastewater typically is
discharged to a common sewer. Although total plant flow can be
determined from this discharge pipe, a breakdown into components
from each process is not possible. Wastewater flows have been
tabulated in Table 9.3-3 (next page) for each plant, and grouped
according to the processes within the plant.
II.9.3.2 Wastewater Characterization [1]
Wastewater characteristics for the Gum and Wood Chemicals Indus-
try demonstrate that organic solvents are generally the most
Date: 6/23/80 II.9.3-6
-------
TABLE 9.3-3. TABULATED WASTEWATER FLOWS BY PLANT [1]
Subcate-
gories
G
G,F
G,C,F
G,D,F
B,F
C
C,F
D,F
D
Plant
No.
009
885
159
571
222
743
993
485
934
242
334
244
714
660
454
040
049
759
436
590
Discharge
type
Indirect
Indirect
Direct
Indirect
Indirect
Direct
-b
Indirect
Direct
Direct
Direct
Direct
Indirect
Indirect
-b
-b
-b
Direct
Direct
-b
Production,
kg/d
57,700
86,400
45,300
218,000
465,000
209,000
467,000
45,400
48,200
336,000
199,000
139,000
192,000
69,200
306,800
227,000
270,000
164,000
152,000
193,000
Wastewater
flow, m3/d
273
1,230
4,470
2,200
1,750
681
1,360
19
587
7,310
636
2,020
186
447
3,410
1,330
158
2,270
984
aB = gum rosin and turpentine; C = wood rosin, turpen-
tine, and pine oil; D = tall oil rosin, pitch, and
fatty acid; F = rosin- and terpene-based derivatives;
G = sulfate turpentine.
Plant discharges into the waste treatment system of
another plant.
prevalent pollutants. These solvents are used in the extraction
processes across all subcategories. Some heavy metals have been
listed as natural components of the raw materials (e.g., tree
stumps) that are utilized in this industry.
Due to the nature of the Gum and Wood Chemicals Industry there is
a great deal of overlap among the various subcategories. Al-
though the subcategories were defined according to the principal
product(s) peculiar to a set group, most of the plants within a
subcategory secondarily produce products which are primary to
another subcategory. The resulting overlap makes separation of
available data relative to specific pollutants difficult to
achieve.
Date: 6/23/80
II.9.3-7
-------
II.9.3.2.1 Wood Rosin, Turpentine, and Pine Oil
Principal toxic pollutants observed were some organic solvents
(particularly toluene), chromium, and zinc. Conventional pollut-
ants included COD and BOD. Levels of methylene chloride and
benzene in the groundwater are unusually high and probably indi-,
cate contamination.
Of the five plants that process wood stumps for their extractable
components, only one has segregated wood rosin wastestreams (the
remaining plants have multiprocess wastestreams). The multi-
process streams could not be used to characterize the'wastewater
from this subcategory; thus, Tables 9.3-4 and 9.3-5 present con-
centrations of toxic pollutants and conventional and classical
pollutants for the wood rosin, turpentine, and pine oil subcate-
gory based on sampling conducted at one plant.
TABLE 9.3-4. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
WOOD ROSIN, TURPENTINE, AND PINE OIL SUB-
CATEGORY WASTEWATER [1]
(pg/L)
Raw7Treated
Toxic pollutant Intake wastewater effluent
Metals and inorganics ,
Arsenic <10 <10 <15
Chromium <10 1,500 110
Copper <10 33 <12
Lead <10 15 <10r?
Zinc <10 160e 37
Monocyclic aromatics
Ethylbenzene <10 50f '~*n
Toluene <10
Halogenated aliphatics
Chloroform 20 <10 17
Methylene chloride 910 190 340
aProcess makeup water-well water.
Influent to equalization basin.
Q
From aerated and settlinglagoon; average of three samples
Blank adjusted value is <10.
Blank adjusted value is 130.
Indeterminate because of high organic compound loading.
Date: 6/23/80 II.9.3-8
-------
TABLE 9.3-5. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND IN WOOD ROSIN, TURPENTINE, AND PINE
OIL SUBCATEGORY WASTEWATER [1]
(mg/L)
Raw Treated
a |~\ /-<
Pollutant Intake wastewater effluent
BODs <10 1,500 22
COD" 11 1,200 230
Suspended solids <10 240 55
Total phenols 0.12 0.46 <0.06
Oil and grease
Process makeup water-well water.
Influent to equalization basin.
c
From aerated and settling lagoon; average of three
samples.
II.9.3.2.2 Tall Oil Rosin, Fatty Acids, and Pitch
Principal toxic pollutants observed were methylene chloride,
benzene, copper, and chromium. Conventional pollutants included
total phenols, COD, and oil and grease. Unusually high levels of
methylene chloride, toluene, and benzene are probably due to
contamination.
Three tall oil distillation plants currently in the industry
perform only tall oil distillation and some rosin size opera-
tions. As indicated in Tables 9.3-6 and 9.3-7 (next page), one
plant in this subcategory was sampled. The other tall oil distil-
lation plants have combined processes, making their wastestreams
unsuitable for characterization.
II.9.3.2.3 Rosin Derivatives
Principal toxic pollutants observed were ethylbenzene, toluene,
methylene chloride, and zinc. Conventional pollutants included
COD, BOD, and oil and grease.
In one plant the rosin derivatives process wastewater was sepa-
rated from that of other processes. The results of the verifica-
tion analyses are shown in Tables 9.3-8 and 9.3-9 for three sam-
pling locations.
Date: 6/23/80 II.9.3-9
-------
TABLE 9.3-6. CONCENTRATIONS OF TOXIC POLLUTANTS
FOUND IN TALL OIL ROSIN, PITCH, AND
FATTY ACIDS SUBCATEGORY WASTEWATER [1]
Toxic pollutants Intake '
Metals and inorganics
Chromium 110
Copper <10
Lead <10
Nickel 13
Selenium <10
Zinc <10
Monocyclic aromatics
Benzene 120
Ethylbenzene <10
Toluene 20
Halogenated aliphatics
Chloroform 10
Methylene chloride 740
Raw
a
wastewater
83
150
14
19
11
50
120
20
20
10
710
Treated
effluent3
88
220
43
<10
44
120
20
10
85
Values not blank adjusted. See Plant 949 in Section
II.9.3.3 for identification of blank values.
Process makeup water-well water.
TABLE 9.3-7. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND IN TALL OIL ROSIN, PITCH, AND FATTY
ACIDS SUBCATEGORY WASTEWATER [1]
(mg/L)
Pollutant
BOD5
COD"
Suspended solids
Total phenols
Oil and grease
Raw
Intake wastewater
<10 42
<10 1,100
<10 44
<0.01 0.55
<10 48
Treated
effluent
<10
130
19
0.029
13
Note: Blanks indicate data not available.
Date: 6/23/80 II.9.3-10
-------
TABLE 9.3-8.
CONCENTRATIONS OF TOXIC POLLUTANTS
FOUND IN ROSIN DERIVATIVES SUB-
CATEGORY RAW WASTEWATER [1]
Toxic pollutant
Raw wastewater sample'
706 730 737
Metals and inorganics
Arsenic 53
Cadmium 120
Chromium 62
Copper 180
Lead 72
Nickel 34
Zinc 38,000
Phenols
Phenol
Monocyclic aromatics
Benzene 170
Ethylbenzene 2,200
Toluene 5,300
Halogenated aliphatics
Chloroethane <10
Methylene chloride 7,300
1,1,1-Trichloroethane 830
41
95
48
300
54
100
12,000
17,000
2,700
100
34
190
49
35
38,000 38,000
14,000 >10,600 23,000
710
28,000
>4,000
520
6,700
Sample locations presented in Reference 1 in
coded form; all location codes are for raw
wastewater samples.
TABLE 9.3-9.
CONCENTRATIONS OF CONVENTIONAL POLLUTANTS
FOUND IN ROSIN DERIVATIVES SUBCATEGORY
RAW WASTEWATER [1]
(mg/L)
Raw wastewater sample'
Pollutant
BOD 5
COD"
Suspended solids
Total phenols
Oil and grease
706
450
40,000
87
46
146
730
1,260
31,000
71
41
92
737
<10
38,000
70
53
62
Sample locations presented in Reference 1
in coded form; all location codes are for
raw wastewater samples.
Note: Blanks indicate data not available.
Date: 6/23/80
II.9.3-11
-------
effluents from other processing areas. Median concentrations of
the three plants' wastewaters were used to determine the values
in Tables 9.3-10 and 9.3-11 (next page), since the wastestream
from one plant is very different from those of the other two.
Wastestreams differ based on the types of end products manufac-
tured by the various plants. The varying product lines of the
sulfate turpentine fractionators make this subcategory very dif-
ficult to characterize.
II.9.3.3 Plant Specific Description [1]
Tables 9.3-12 through 9.3-15 present toxic pollutant and conven-
tional pollutant data for gum and wood chemical process plants.
The data in this section are based on the most current represen-
tative information available from four of the plants contacted.
Verification sampling data are used to supplement historical data
obtained from the plants for the conventional pollutants, and in
most cases are the sole source of quantitative information for
toxic pollutant raw waste loads.
II.9.3.4 Pollutant Removability [1]
II.9.3.4.1 Industry Application
A matrix of the current in-place treatment technology in the Gum
and Wood Chemicals Industry is shown in Table 9.3-16. Many of
the direct dischargers have primary treatment in place at this
time. Pretreatment processes used by indirect dischargers depend
on the requirements of the receiving treatment works. Six in-
direct dischargers discharge their wastewater to POTW's. Six
plants discharge their wastewater to the wastestreams of other
industries such as pulp and paper mills. The plants that dis-
charge to POTW's have treatment equipment to meet POTW require-
ments. The plants that discharge to the wastestreams of other
industries pretreat by skimming the surface oil and settling
solids.
II.9.3.4.2 Treatment Methods
Oil Separation
Free oil removal - Oily products such as turpentine and
fatty acids are a major factor in this industry. Gravity oil-
water separation is used throughout the industry to recover oil
for use as a fuel supplement or, in some cases, for recycle to
the plant process. Oil-water separation, of course, reduces the
toxicity and the oxygen demand of the wastewater by removing the
oil.
A baffle separator at the effluent end of an equalization basin
is the most common system used in the industry. The oil can be
skimmed from the basin either manually or continously depending
Date: 6/23/80 II.9.3-12
-------
D
fa
ft
to
10
GO
o
TABLE 9.3-10.
CONCENTRATIONS OF TOXIC POLLUTANT?
TURPENTINE SUBCATEGORY WASTEWATERC
(M9/L)
FOUND IN SULFATE
[1]
H
H
ȣ>
U)
t-1
OJ
Toxic pollutants
Arsenic
Chromium
topper
Lead
Nickel
Selenium
Zinc
Bis(2-ethylhexyl) phthalate
Phenol
Benzene
Toluene
Chloroform
Methylene chloride
Number
of
samples
1
2
2
2
2
1
2
1
1
2
2
1
2
Intake
Range
<10-120
<10-250
<10
<10-36
<10
<10-74
<10
400-560
Median
<10
65h
130b
<10b
23b
<10
<10
<10
<10b
42b
<10,
480
Number
of
samples
3
6
6
6
6
3
6
3
3
6
6
3
6
Raw wastewater
Range
<10-110
49-1,300
1,600-6,000
<10-21
140-4,100
<10
170-530
<10
<10-760
<10-140
<10-2,200
980-1,400
<10-16,000
Median
<10
545
2,250
11.5
370
<10
265
<10
130
<10
960
1,000
695
Number
of
samples
3
6
6
6
6
3
6
3
3
6
6
3
6
Treated effluent
Range
<10
94-880
1,800-4,700
<10-19
46-1,100
<10-14
99-450
<10-1,900
<10-850
<10-240
<10-2,000
900-1,400
490-2,400
Median
<10
365
2,500
13.5
325
<10
320
<10
<10
165
635
1,000
1,800
Values not blank adjusted.
Value averaged from two samples.
-------
o
P)
ft
(D
N)
CO
00
O
TABLE 9.3-11.
OJ
I
CONCENTRATIONS OF CONVENTIONAL AND CLASSICL POLLUTANTS FOUND
IN SULFATE TURPENTINE SUBCATEGORY WASTEWATER [1]
(mg/L)
Toxic pollutants
BOD 5
COD
TSS
Total phenols
Oil and grease
Number
of
samples
2
2
2
2
2
Intake
Range Median
-------
ti-
ro
TABLE 9.3-12. WASTEWATER CHARACTERIZATION, PLANT 464 [I]
OO
O
u>
I
(-•
Ul
Category: Gum and Wood Chemicals
Subcategory-. Wood rosin, turpentine, and pine oil
Wastewater Treatment Description: Biological treatment by aerated lagoon or settling basin.
Unique pretreatment procedure includes mixing boiler wood
ash with equalized wastewater.
Concentration
Process makeup
Pollutant and well water
Methylene chloride, ug/L 910
Chloroform, ug/L 20
Ethylbenzene,ug/L <10
Toluene, ug/L <10
Arsenic, \ig/L <10
Copper, pg/L <10
Chromium, Mg/L <10
Lead, ug/L <10
Zinc, ug/L <10
Total phenols, pg/L 120
Suspended solids, mg/L <10
COD, mg/L 11
BOD, mg/L <10
Oil and grease, mg/L <10
Equalization
basin influent
190
<10
50
<10
33
1,500
15
160
460
240
1,200
1,500
<10
Equalization
basin effluent
560
10
10
>400
<10
<10
980
17
89
980
220
1,100
650
<10
Ash settling
Blank basin effluent
NA 260
NA 30
NA <10
NA >400
15 14
<10 <10
<10 620
<10 13
<10 150
<10 10
<10 160
<10 730
<10 270
<10 18
Blank
NA
NA
NA
NA
17
<10
-------
o
D>
rt
(D
N)
00
O
VO
•
u>
I
TABLE 9.3-13. WASTEWATER CHARACTERIZATION, PLANT 949 [1]
Category: Gum and Wood Chemicals
Subcategory: Tall oil rosin, pitch, and fatty acids
Wastewater Treatment Description: Primary treatment supplemented by use of alum
coagulation to enhance settling of emulsified
oils. Biological treatment by aerated lagoons.
Concentration
Process makeup
Pollutant and well water
Methylene chloride, pg/L 740
Chloroform, pg/L 10
Benzene , pg/L 120
Ethylbenzene , pg/L <10
Toluene, pg/L 20
Phenol, pg/L <10
Copper, pg/L <10
Chromium , pg/L 110
Lead, pg/L <10
Nickel, pg/L 13
Selenium, pg/L <10
Zinc, pg/L <10
Total phenols, pg/L <10
Suspended solids, mg/L <10
COD, mg/L <-10
BOD, mg/L <10
Oil and grease, mg/L <10
Raw Init ial settling
wastewater Blank effluent
710 30
10 <10
120 <10
20 <10
20 <10
<10 <10
150 16
83 35
14 <10
19 20
11 <10
50 70
550 <10
44 <10
1,100 <10
42 <10
48 <10
780
10
110
10
50
<10
230
9'/
<10
24
<10
27
100
15
160
12
<10
Barametric condenser Treated
closed system effluent
210
<-10
30
<10
70
7,500
300
280
26
66
<10
80
1,700
170
8,400
176
167
85
10
110
<10
20
<10
220
88
<10
43
<10
44
29
19
130
<10
13
Note: Values not blank adjusted.
-------
o
* TABLE 9.3-14. WASTEWATER CHARACTERIZATION, PLANT 097 [1]
(D
Category: Gum and Wood Chemicals
c^ Subcategory: Rosin Derivatives
00
O
H
H
Concentration
Pollutant
Chloroe thane, pg/L
Methylene Chloride, pg/L
1, 1, 1-Trichloroethane, pg/L
Benzene, pg/L
E the Ibenz ene , p g/L
Toluene, pg/L
Phenol, pg/L
Arsenic, pg/L
Cadmium, pg/L
Copper, pg/L
Chromium, pg/L
Lead, pg/L
Nickel, pg/L
Zinc, pg/L
Total phenols, pg/L
Suspended solids, mg/L
COD , mg/L
BOD , mg/L
Oil and grease, mg/L
Sample 730
<10
2,700
<10
<10
12,000
17,000
>10,600
41
95
300
48
54
100
38,000
41,000
71
31,000
1,260
92
Sample 706
<10
7,300
830
170
2,200
5,300
14,000
53
120
180
62
72
34
38,000
46,000
87
40,000
450
146
Sample 737 Blank
520 <10
6,700 630
<10 <10
710 <10
28,000 <10
>4,000 <10
23,000 <10
ND <10
100 <10
190 <10
34 <10
49 <10
35 <10
38,000 <10
53,000 <10
70 <10
38,000 <10
<10 <10
62 <10
Note: Values not blank adjusted.
-------
o
01
ft
(D
U)
oo
o
UD
•
U)
I
M
CD
TABLE 9.3-15. WASTEWATER CHARACTERIZATION, PLANT 610 [1]
Category: Gum and Wood Chemicals
Subcategory: Sulfate Turpentine
Concentr a ti on
Pollutant
Methylene chloride, pg/L
Benzene, pg/L
Toluene, pg/L
Bis(2-ethylhexyl) phthalate, pg/L
Arsenic, pg/L
Copper, pg/L
Chromium, pg/L
Lead, pg/L
Nickel, pg/L
Selenium, pg/L
Zinc, pg/L
Total phenols, pg/L
Suspended solids, mg/L
COD , mg/L
BOD , mg/L
Oil and grease, mg/L
Plant
influent
560
<10
<10
<10
<10
250
120
<10
36
<10
<10
18
<10
16
<10
<10
Raw
wastewater
6,620
<53
<1,000
<10
<43
2,000
200
<11
170
<10
240
6,330
240
10,000
1,500
290
Blank
NA
NA
NA
<10
<10
190
36
<10
13
<10
30
<10
<10
<10
<10
<10
Treated
effluent
2,000
<77
<63
<640
<10
2,970
150
16
230
<13
360
5,900
420
4,700
440
140
Blank
300
<10
<10
<10
<10
220
16
<10
16
<10
30
<10
<10
<10
<10
<10
Note: Values not blank adjusted.
aAverage of three samples.
-------
o
D)
rt
CO
CTi
KJ
LO
OO
O
H
U>
I
TABLE 9.3-16. SUMMARY OF IN-PLACE TREATMENT TECHNOLOGY
Description
Type of discharger
Oil separation
Equalization
Air flotation
Neutralization
Nutrient addition
Aerated lagoon
Chrome reduction
Metals removal
Clarificat ion
Filtration
Granular carbon adsorption
Chemical coagulation
Settling
Mixing carbonaceous fly
Nonae rated pond
Activated sludge
778 476
D 0
X X
X
X
X
X
X
X X
976 068 291 649 017
D I I 0 I
X XXX
X X
X X
X X
X X
X
X X X X X
X
Plant code
110 687A 687B 974 474 573 877 286
I D I 0 0 D D
XX X X X X X
XX X
X
X
X XX
XXX
X
X X
xx xxx
X
102
D
X
X
X
X
X
X
X
X
140 479
O I
X X
X
X
X
X
X X
864 943
V 0
x x
X
X
X
X X
X
X
767
D
X
X
X
X
X
A
X
1) - direct, 0 - plant discharges into the wastestream of another plant, 1 - indirect.
-------
on the wastewater flow and the quantity of oil products produced
at the plant. In this study, free oil removal was not considered
part of the treatment system, and wastewater characteristics
across oil-water separators were not considered.
Chemical flocculatipn - Wastewater from the industry
typically has high concentrations of emulsified oil, the quantity
of which varies from plant to plant depending on the efficiency
of the oil-water separator and the pH of the wastestream. At a
pH less than 3, the emulsion problem is greatly reduced; however,
the pH of the wastestreams in the industry typically ranges from
3 to 9.
Two plants in the industry are currently using chemical coagula-
tion. One plant fractionates tall oil, and the other plant has
major production in the wood rosin and turpene area. These
plants reduce oil and grease by 65% to 85% using coagulation and
settling equipment with a polymer as a flocculation aid. The
flocculated effluent generally contains from 7 to 16 mg/L of oil
and grease.
Equalization. Equalization is used in the treatment system
to smooth out surges in both flow and pollutant concentration.
Some type of equalization will be required by the industry in
general.
Air Flotation. Air flotation devices are used by plants 778
and 767. A study conducted by plant 778 reported that air flota-
tion removed 204 kg/day (450 Ib/day) of BOD, 181 kg/day (400 lb/
day) oil and grease, and 236 kg/day (521 Ibs/day) of COD. Plant
767 is in the process of installing the flotation equipment, and
pollutant removal rates are not available at this time.
Plant 102 is using a dissolved air flotation process. A study
conducted by the plant showed a reduction of TOC across the flo-
tation unit of 2,860 kg/day (6,300 Ib/day). Oils recovered from
the flotation unit are used as a fuel supplement.
Neutralization. Gum and wood chemicals industrial waste-
streams vary in pH from 3 to 9. Neutralization is required to
adjust the pH of the stream to levels necessary for the various
treatment steps. Oil emulsion breaking requires a pH of less
than 3; metals precipitation requires a pH of approximately 9;
and biological treatment requires a pH of approximately 7. The
pH adjustment can be made with the addition of either alkalies or
acids, depending on what pH is required. Alkalies commonly used
are lime, caustic, or soda ash. The acid used in neutralization
is usually sulfuric acid.
Carbon Adsorption. Presently, there is one facility using
activated carbon adsorption. Plant 102 has oil-water separation,
neutralization, dissolved air flotation, filtration, and finally
Date: 6/23/80 II.9.3-20
-------
granular activated carbon (GAC). Before installing the GAC,
carbon isotherm and pilot plant studies were performed.
Adsorption isotherms were developed by three separate labora-
tories using the parameter COD. The results were carbon loadings
of between 0.85 and 1.2 kg COD/kg carbon (0.85 Ib COD/1.2 Ib
carbon). The pilot plant studies revealed that the optimal con-
ditions were flow rates of 176 to 293 m3/m2/day (3 to 5 gpm/ft2)
and a contact time of 45 to 50 minutes. At these conditions, COD
removals were 75% to 85%. The pilot plant results confirmed the
isotherm results by yielding a carbon loading of approximately
1.0 kg COD/kg carbon (Ib COD/lb carbon).
The GAC system was designed and is operating at a carbon loading
of approximately 1.2 kg COD/kg carbon (1.2 Ib COD/lb carbon) and
0.44 kg TOC/kg carbon (Ib TOC/lb carbon). Pollutant reductions
were approximately 84% COD and 79% TOC. Representative perfor-
mance data for the GAC system are shown in Table 9.3-17 (next
page). The performance of the entire treatment system was better
than 95% removal of COD and TOC. Typical performance data for
the total treatment system are shown in Table 9.3-18.
Very little data are available on adsorption of toxic pollutants
in gum and wood chemicals wastewater. Carbon adsorption is not
effective for removing most metals. The organics commonly identi-
fied during screening and verification were benzene, toluene,
ethylbenzene, and phenol.
As indicated in Table 9.3-19, the toxic pollutants found at plant
102 were benzene, toluene, phenol, and bis(2-ethylhexyl) phthalate.
The bis(2-ethylhexyl) phthalate was found only in the effluent of
the carbon adsorption unit.
Evaporation. Due to the significant volumes of plant waste-
water generated, evaporation is not a feasible or widely used
technology in the Gum and Wood Chemicals Industry for achieving
no-discharge status. However, it may be applicable for disposal
of specific, high strength, low volume, process wastestreams.
II.9.3.5 References
1. Technical Review of the Best Available Technology, Best
Demonstrated Technology, and Pretreatment Technology for the
Gum and Wood Chemicals Point Source Category (draft
contractor's report). Environmental Science and Engineering,
Inc.
2. NRDC Consent Decree Industry Summary - Gum and Wood Chemicals
Industry.
3. Environmental Protection Agency - Effluent Guidelines and
Standards for Gum and Wood Chemicals Manufacturing. 40 CFR
454; 41FR 20506, May 18, 1976.
Date: 6/23/80 II.9.3-21
-------
TABLE 9.3-17 SECONDARY TREATMENT FEED AND EFFLUENT ANALYSIS
AND PERFORMANCE DATA FOR PLANT 102 GRANULAR
ACTIVATED CARBON SYSTEM [I]
Item
Design
12,260 m3/day (3.24 MGD/d)
COD, mg/L
TOC, mg/L
BOD, mg/L
Startup period
9,810 ms/day (2.59 MGD/d)
COD, mg/L
TOC, mg/L
Typical operation
9,810 m3/day (2.59 MGD/d)
COD, mg/L
TOC, mg/L
Selected samples
9,810 m3/day (2.592 MGD)
BOD, mg/L
Phenols, mg/L
Ni, mg/L
Zn, mg/L
Cd, mg/L
Cu, mg/L
Cr, mg/L
TS, mg/L
SS , mg/L
DS, mg/L
Chlorides, mg/L
N02, mg/L
Oil and grease, mg/L
Influent
600
160
250
975
222
752
203
300
4.66
1.02
1.11
0.91
1.29
1.12
1,210
81
1,130
1.82
5.16
28.1
Effluent
125
30
50
152
46
160
42
82
0.58
0.33
0.29
0.22
0.36
0.26
965
13
952
0.84
4.28
2.2
Percent
reduction
79
81
80
84
79
79
79
73
88
68
74
76
72
77
20
84
16
48
17
92
Removal,
kg/ day
5,810
1,590
2,450
8,070
1,590
5,810
1,590
2,130
40
6.8
8.2
6.8
9.1
8.6
2,400
680
1,720
8.6
8.6
254
Date: 6/23/80 II.9.3-22
-------
TABLE 9.3-18.
TYPICAL TOTAL TREATMENT SYSTEM PERFORMANCE
DATA [1]
Parameter
COD
TOC
BOD
TSS
Oil and grease
Raw Waste-
water
mg/L
3,200
1,200
1,600
320
500
Primary
Treated
effluent,
mg/L
670
198
267
72
25
Secondary
Treated
effluent,
mg/L
143
37
73
12
2
Overall
reduction,
°/
/o
95.5
96.9
95.4
96.3
99.6
Oil-water separation, neutralization, dissolved air flotation,
filtration, and granular activated carbon at 9,810 m3/d
(2.592 MGD).
TABLE 9.3-19.
REMOVAL OF ORGANIC PRIORITY POLLUTANTS FOR
PLANT 102 ACROSS ACTIVATED CARBON COLUMN [1]
Pollutant
Sample prior to
carbon column
Sample after carbon column
Day 1 Day 2 Day 3
Benzene
Toluene
Phenol
Bis(2-ethylhexyl)
phthalate
590
2,500
120
ND
131
180
ND
400
200
400
ND
260
300
1,300
49
ND
Date: 6/23/80
II.9.3-23
-------
II.9.5 PHARMACEUTICAL MANUFACTURING
II.9.5.1 INDUSTRY DESCRIPTION
II.9.5.1.1 General Description [1,2]
The pharmaceutical manufacturing industry produces hundreds of
medicinal chemicals by means of many complex manufacturing tech-
nologies. The Pharmaceutical Manufacturing Point Source Category
may be subdivided to cover the following products, processes, or
activities [1]:
• Biological products covered by SIC Code 2831.
• Medicinal chemicals and botanical products covered by
SIC Code 2833.
• Pharmaceutical products covered by SIC Code 2834.
• All fermentation, biological and natural extraction, chemical
synthesis, and formulation products, which are considered
to be pharmaceutical active ingredients by the Food and Drug
Administration but are not covered by SIC Codes 2831, 2833,
or 2834.
• Cosmetic preparations covered by SIC Code 2844 which function
as skin treatments, excluding products which serve to enhance
appearance or provide a pleasing odor.
• The portion of a product with multiple end uses which is
attributable to the pharmaceutical manufacturing industry.
• Pharmaceutical research which includes biological, micro-
biological, and chemical research; product development;
clinical, and pilot-plant activities.
Information on 436 pharmaceutical manufacturing plants is presently
included in the EPA data base, representing the feedback from more
than 900 308 Portfolios distributed. Most pharmaceutical manufac-
turing firms are located in New York, New Jersey, Pennsylvania,
Indiana, Michigan, Missouri, Ohio, and California with production
concentrated in the industrial areas of the east and midwest. Of
the 436 plants identified in the EPA data base, approximately 80%
are located in the eastern part of the United States.
Table 9.5-1 summarizes pertinent information regarding the total
number of subcategories, the number of subcategories studied by
EGD, and the number and type of discharges in the industry. Only
11% of the surveyed pharmaceutical plants have direct discharges,
whereas the majority of the plants in the industry discharge their
wastewaters to POTW's. Current Best Practicable Control Technology
Currently Available (BPT) regulations pertaining to the pharma-
ceutical manufacturing industry are presented in Table 9.5-2.
Date: 6/23/80 II.9.5-1
-------
TABLE 9.5-1. INDUSTRY SUMMARY [1,3]
Industry: Pharmaceutical Manufacturing
Total Number of Subcategories: 5
Number of Subcategories Studied: 5
Number of Dischargers in Industry:
• Direct: 50
• Indirect: 245
• Combined Direct and Indirect: 7
• Zero: 134a
aNo process wastewater is disposed of
at 104 plants; five plants use land
application, four use subsurface dis-
posal, five use a septic system, two
use ocean disposal, seven use contract
disposal, and seven use evaporation to
achieve zero discharge.
TABLE 9.5-2. PHARMACEUTICAL MANUFACTURING BPT REGULATIONS [4]
Parameter Subcategories Current BPT regulation
BODs A,B,C,D,E The allowable effluent discharge limitation for the daily
average mass of BODs in any calendar month shall be ex-
pressed in mass per unit time and shall specifically re-
flect not less than 90% reduction in the long-term daily
average raw waste content of BODs multiplied by a vari-
ability factor of 3.0.
COD3 A,B,C,D,E The allowable effluent discharge limitation for the daily
average mass of COD in any calendar month shall be ex-
pressed in mass per unit time and shall specifically re-
flect not less than 74% reduction in the long-term daily
average raw waste content of COD multiplied by a vari-
ability factor of 2.2.
TSS B,D,E The average of daily TSS values for any calendar month
shall not exceed 52 mg/L.
pH A,B,C,D,E The pH shall be within the range of 6.0 to 9.0 standard
units.
aTo assure equity in regulating discharges from the point sources covered by this
subpart of the point source category, calculation of raw waste loads of BODs and COD
for the purpose of determining NPDES permit limitations (i.e., the base numbers to
which the percent reductions are applied) shall exclude any waste load associated
with solvents in those raw waste loads; Provided, that residual amounts of solvents
remaining after the practice of recovery and/or separate disposal or reuse may be
included in calculation of raw waste loads. These practices of removal, disposal or
reuse include recovery of solvents from waste streams and incineration of concen-
trated solvent waste streams (including tar still bottoms). This regulation does
not prohibit inclusion of such wastes in the raw waste loads in fact, nor does it
mandate any specific practice, but rather describes the rationale for determining
the permit conditions. These limits may be achieved by any one of several or a com-
bination thereof of programs and practices.
Date: 6/23/80 II.9.5-2
-------
II.9.5.1.2 Subcategory Descriptions [1,2]
Under the regulation established for BPT, the Pharmaceutical Man-
ufacturing Point Source Category was grouped into the five product
or activity areas shown below. This subcategorization was based •
on distinct differences in manufacturing processes, raw materials,
products, and wastewater characteristics and treatability.
Subcategory A - Fermentation Products
Subcategory B - Biological and Natural Extraction Products
Subcategory C - Chemical Synthesis Products
Subcategory D - Formulation Products
Subcategory E - Pharmaceutical Research
• The EPA has decided to deemphasize pharmaceutical research
(Subcategory E) because this activity does not fall within
SIC Codes 2831, 2833, and 2834, which were identified in the
Consent Decree.
• Many plants within the industry are involved in activities
associated with more than one subcategory. Table 9.5-3 in-
dicates that 78.9% of the plants in the EPA data base are
involved in formulation (Subcategory D) activities. Table
9.5-4 presents a breakdown of the industry by manufacturing
subcategory, listing the number of plants and the percent of
total plants for each subcategory combination. Formulation
(Subcategory D) is by far the most common manufacturing op-
eration in this industry. Many plants having either Sub-
category A or C operations also have Subcategory D activities.
• Table 9.5-5 gives the number of batch, continuous, and semi-
continuous operations for each subcategory and for the total
industry. Batch-type operations are by far the most prevalant
form of pharmaceutical production activities.
Subcategory A - Fermentation Products
Fermentation, the basic method used for producing most antibiotics
and steroids, involves three basic processing steps: inoculum and
seed preparation, fermentation, and product recovery.
Production of a fermentation pharmaceutical begins with spores from
the plant master stock. The spores are activated with water, nut-
rients, and heat. The cultures are then propagated under labor-
atory conditions to produce sufficient mass for transfer to the
seed tank.
Fermentation is a-batch process, although most large operations
are highly automated. In each batch cycle, the broth is discharged
from the previous cycle, and then the fermenter is washed down with
water and sterilized with live steam. Sterilized raw materials
are then charged into the vessel. After optimum conditions are
achieved, the microorganisms in the seed tank are drained into the
fermenter, and fermentation begins.
Date: 6/23/80 II.9.5-3
-------
TABLE 9.5-3. PLANTS ASSOCIATED WITH OVERALL MANUFACTURING
SUBCATEGORIES [3]
Overall manufacturing
subcategorya
A
B
C
D
Number
of plants
30
64
113
344
Percent of
total plants
6.9
14.7
25.9
78.9
Excludes subcategory E.
TABLE 9.5-4. PLANTS ASSOCIATED WITH MANUFACTURING
SUBCATEGORY COMBINATIONS [3]
Manufacturing subcategory
combination3
A
B
C
D
AC
AD
BC
BD
CD
ABC
ABD
BCD
ABCD
Number
of plants
3
20
40
255
3
6
7
20
41
1
3
6
7
Percent of
total plants
0.7
4.6
9.2
58.5
0.7
1.4
1.6
4.6
9.4
0.2
0.7
1.4
1.6
aExcludes subcategory E.
Date: 6/23/80 II.9.5-4
-------
TABLE 9.5-5. PHARMACEUTICAL INDUSTRY SUBCATEGORY AND
PRODUCTION OPERATION BREAKDOWN [3]
Number of operations
Subcategory
Parameter
Type of operation
Batch
Continuous
Semi continuous
Number of operations
Percent of total operations
A
25
3
9
37
6.1
B
60
0
9
69
11.4
C
109
14
18
141
23.2
D
327
16
17
360
59.3
Total
521
33
53
607
100.
0
After a period of 12 hours to one week, depending on the fermen-
tation process, the broth is ready for product recovery. The
four common methods of product recovery are solvent extraction,
direct precipitation, ion exchange, and carbon adsorption. In
solvent extraction, an organic solvent is used to remove the
pharmaceutical product from the aqueous broth to form a more con-
centrated, smaller volume solution. Direct precipitation consists
of first precipitating the product from the aqueous broth, filter-
ing the broth, and then extracting the product from the solid
residues. Ion exchange and carbon adsorption involve removal of
the product from the broth using a solid material (i.e., ion ex-
change resin or activated carbon). The product is then removed
from the solid phase using an elutriant or a solvent and sub-
sequently recovered.
Subcategory B - Biological and Natural Extraction
Many materials used as Pharmaceuticals are derived by extraction
from natural sources, which include roots and leaves of plants,
animal glands, and parasitic fungi. All extractive Pharmaceuticals
are too complex to synthesize commercially. In addition, syn-
thesis represents an expensive manufacturing process because ex-
traction requires the collection and processing of very large
volumes of specialized plant or animal matter to produce very small
quantities of product.
The extraction process consists of a series of operating steps in
which, following almost every step, there is a significant reduc-
tion in the volume of material being handled. In some processes,
the volume reductions may be in orders of magnitude, and the com-
plex final purification operations may be conducted on quantities
of materials that are only a few thousandths of the amount handled
in earlier steps. Therefore, neither continuous processing
Date: 6/23/80 II.9.5-5
-------
methods nor conventional batch methods are suitable for extraction
processing. Instead, a unique processing method has been developed
which can be described as assembly-line small-scale batch. In
this method, material is transported in portable containers through
the plant in batches of approximately 19.8 L to 26.4 L. A con-
tinuous line of such containers is sent past a series of operating
stations. At each station, operators perform specific tasks on
each batch in turn. As the volume of material being handled de-
creases, individual batches are successively combined to maintain
reasonable operating volumes, and the line moves more slowly.
When the volume is reduced to a very small quantity, the containers
being used also become smaller, with laboratory-size equipment
used in many cases.
An extractive plant may produce one product for a few weeks, and
then, by simply changing the logistical movement of pots and re-
definjng the tasks to be conducted at each station, it can con-
vert almost overnight to the manufacture of a different product.
Subcategory C - Chemical Synthesis Products
Most of the compounds used today as drugs are prepared by chemical
synthesis generally using a batch process. The basic equipment
consists of a conventional batch reaction vessel, which is one of
the most standardized equipment designs in industry. Synthetic
pharmaceutical manufacture includes the use of one or several of
these vessels to perform, in a step-by-step fashion, the various
operations necessary to make the product. Following a definite
recipe, the operator (or a programmed computer) adds reagents, in-
creases or decreases the flow rate of cooling water, chilled water,
or steam, and starts and stops pumps to withdraw the reactor con-
tents into another similar vessel. At the appropriate steps of
the process, solutions are pumped through filters or centrifuges,
or pumped into solvent recovery headers or waste sewers.
Each pharmaceutical is usually manufactured in a "campaign" in
which one or more process units are employed for a few weeks or
months to manufacture enough compound to satisfy the projected
sales demand. At the end of the campaign, another is scheduled,
and the same equipment and operating personnel are used to make
a completely different product, utilizing different raw materials,
executing a different recipe, and generating different wastes.
Subcategory D - Formulation Products
Although pharmaceutical active ingredients are produced in bulk
form, they must be prepared in dosage form for use by the con-
sumer. Pharmaceutical compounds can be formulated into tablets
capsules, liquids or ointments, as described below
Date: 6/23/80 II.9.5-6
-------
Tablets are formed by blending the active ingredient, filler, and
binder. The mixture is placed in a tablet press machine and some-
times coated by tumbling with a coating material and drying. The
filler (usually starch or sugar) is required to dilute the active
medicinal to the proper concentration; binder (such as corn syrup
or starch) is necessary to bind the tablet particles together. A
lubricant (such as magnesium stearate) may be added for proper
tablet machine operation. After the tablets have been coated and
dried, they are bottled and packaged.
Capsules are produced by first forming the hard gelatin shell.
These shells are produced by machines that dip rows of rounded
metal dowels into a molten gelatine solution and strip the cap-
sules from the dowels after the capsules have cooled and solidi-
fied. The active ingredient and any filler are mixed and poured
into the empty gelatin capsules by a machine operation. The
filled capsules are bottled and packaged.
Liquid preparations can be formulated for use by injection or oral
consumption. In either case, the liquid is weighed and then dis-
solved in water. Injectable solutions are packaged in bottles and
heated or bulk sterilized by sterile filtration and poured into
sterile bottles. Oral liquid preparations are bottled directly
without subsequent sterilization.
Subcategory E - Pharmaceutical Research
Because of the high cost of a new drug and the general importance
to the public health, companies are mainly interested in cures
for the more common ailments. Nevertheless, many remedies for
rare diseases and diagnostic agents have come from the laboratories
of the pharmaceutical industry. The three areas of research in
the pharmaceutical industry are chemical, microbiological, and
biological.
Laboratory animals are used extensively at pharmaceutical research
facilities. The types of animals used include dogs, cats, monkeys,
rabbits, guinea pigs, rats, and mice. The animal colonies where
the test animals are housed can be major wastewater sources. The
animal cages are usually dry-cleaned and the residue washed into
the plant sewer system. Collected feces and any animal carcasses
are incinerated or landfilled if the waste matter is not infected.
Exhaust gases from the incinerators pass through wet scrubbers,
and the scrubber blowdown in subsequently discharged to the plant
sewer system.
II.9.5.2 WASTEWATER CHARACTERIZATION [1,2]
Plants in the pharmaceutical manufacturing point source category
operate continuously throughout the year. Their processes are
largely characterized by batch operations, which have significant
Date: 6/23/80 II.9.5-7
-------
variations in pollution characteristics during any typical oper-
ating period. However, some continuous unit operations are used
in the fermentation and chemical synthesis subcategories [2].
Plants in Subcategory A (Fermentation products) and Subcategory C
(Chemical synthesis products) generate wastewaters with the highest
pollutant concentrations. In Subcategory A, these high levels are
primarily due to the spent solvents used in extraction processes
and sewered fermentation beers. In Subcategory C, a myriad of
organic chemicals are used as intermediates in the production of
fine chemicals, and they contribute significant pollutant loads
to plant wastewater effluents [2] .
The major sources of process wastewaters in the pharmaceutical man-
ufacturing point source category include product washings, product
purification and separation, fermentation processes, concentration
and drying procedures, equipment washdowns, barometric condensers,
and pump-seal waters. Wastewaters from this point source category
can be characterized as having high concentrations of BOD5, COD,
TSS, and volatile organics. Wastewaters from some wet chemical
syntheses may contain heavy metals (iron, copper, nickel, and
silver) or cyanide and may have antibacterial constituents, which
can exert a toxic effect on biological waste treatment processes.
Considerations significant to the design of treatment works are
the highly variable BOD5 loadings, high chlorine demand, presence
of surface-active agents, the possibility of nutrient deficiency,
and the possibility of potentially toxic substances [2],
Table 9.5-6 presents available wastewater characterization data
by overall manufacturing Subcategory in terms of median pollutant
loadings and concentrations. As previously shown in Table 9.5-4,
nearly 30% of the pharmaceutical manufacturing plants have proc-
esses associated with more than one of the four major subcategories.
For this reason, the screening data shown in Table 9.5-7 are pre-
sented in terms of pollutant concentrations by manufacturing sub-
category combinations.
II.9.5.2.1 Subcategory A - Fermentation Products
The sources of wastewater from fermentation operations are (1) spent
fermentation beers; (2) floor and equipment wash waters; (3) chem-
ical wastes, such as spent solvents from the extraction processes;
and (4) barometric condenser water. Of these, spent fermentation
beer is by far the most significant waste discharge [1]. Spent
beer contains residual food materials such as sugars, starches,
and vegetable oils not consumed in the fermentation process. Spent
beer contains a large amount of organic material, protein, and
other nutrients; frequently, it also contains large amounts of
nitrogen, phosphate, and other growth factors as well as salts,
such as sodium chloride and sodium sulfate [2].
Date: 6/23/80 II.9.5-1
-------
a
rt-
CD
to
U)
00
o
U1
I
TABLE 9.5-6. MEDIAN POLLUTANT LOADINGS AND CONCENTRATIONS
BY OVERALL MANUFACTURING SUBCATEGORY [2]
Subcategory
Flow, m3/d
Pollutants
Toxic pollutant metals
and inorganics:
Arsenic
Chromium
Copper
Cyanide
Lead
Mercury
Selenium
Zinc
Other metals:
Aluminum
Calcium
Iron
Magnesium
Manganese
Potassium
Sodium
Classical and conventional:
BOD
COD
TSS
TDS
TKN
N03-N
Phosphorous (total)
Phenol (total)
Hardness
Oil and grease
Sulfate
Sulfide
Chloride
A
1,500
Median value
kg/d
•
0.30
0.09
ND=
0.015
ND*
ND3
0.133
ND»
ND8
140
ND8
9.5
0.009
67
240
4,500
9,300
4,400
520
0.0015
61
0.30
500
530
210
NA
92
mg/L
a
0.15
0.06
ND8
0.009
ND8
ND3
0.0633
ND8
ND8
150
ND8
3'1 a
0.0044
39
190
2,500
5,800
840
3,300
280
NO
43
0.18
330
390
130
NA
66
B
400
Median
kg/d
NA
NA
o ioa
0.023
0.13a
ND3
NA
0.27"
0.043
71a
0.503
NA
NA
NA
50a
17
41
250 1
2.9
ND
2.2
O.OO6a
NA
0.31
42
NA
410
C
value
mg/L
NA
NA
o.iia
0.23
0.15a
ND3
NA
0.313
0.453
81a
0.578
NA
NA
NA
560*
150
300
32
,000
8.3
ND
3.7
0.013*
NA
2.1
64
NA
470a
2,
Median
kg/d
a
14
0.20
NA
0.028
NA
NA
NA
NA
NA
280
17a
64a
NAa
150*
4,900
2,500
7,200
6,900
240
0.085
131
2.5
700a
200
2,600
NA
1,600
300
value
mg/L
gl
12a
0.16
NA a
0.016
NA
NA
NA
NA
NA
120
2.4"
52a
HAa
120a
810
1,900
3,500
280
6,700
800
0.13
44
1.2
570a
86
1,700
NA
550
D
280
Median value
kg/d
NA
NA
0.13
0.038
0.085
0.0005
NA
0.55
NA
14
0.15
NA
NA
NA
5.6a
210
350
360
5.5
0.15
1.6
NAa
180
21
22
0.0213
31
mg/L
NA
NA
0.12
0.020
0.093
0.0003
NA
0.49
NA
73
0.64
NA
NA
HA.
3,600
380
670
49
660
25
0.13
10
NA
120a
15
39 a
0.014
28
E
180
Median
kg/d
NA
NA
0.19a
NA
A
0.040
0.002
NA
0.52a
NA
22
0.20
NA
NA
HA
2.5a
20
43
100
5.0
0.02
0.95
a
0.053
NA
j*
3.1
32
NA
19
value
mg/L
NA
NA
0.233
NA
0.048a
0.0024
NA
0.62
NA
62
0.38
NA
NA
m a
3.9*
200
400
50
480
2.7
0.031
10 a
0.29
NAa
17
72
NA
47
Based upon single reported value.
-------
a
rt
to
NJ
Ul
00
o
TABLE
U1
I
9.5-7. POLLUTANT CONCENTRATIONS BY MANUFACTURING SUBCATEGORY COMBINATIONS
(ug/L)
[1]
a a
A D
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Mercury
Selenium
Zinc
Ethers
Bis(2-chloroethyl) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Nitrogen compounds
1 , 2-Diphenylhydrazine
Phenols
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Tr ichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methyl bromide
Methyl chloride
Methylene chloride
Tetrachloroethylene
1 , 1 , 1-Trichloroethane
1,1, 2-Trichloroethane
Trichlorofluoromethane
Raw
wastewater
28
31
ND
ND
29
ND
ND
60
89
ND
ND
ND
ND
ND
1,600
ND
70
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated
effluent
50
47
ND
17
48
ND
6.4
150
120
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
70
ND
ND
ND
ND
Raw
wastewater
ND
ND
ND
30
50
ND
ND
ND
300
ND
170
20
ND
ND
ND
62
ND
ND
79
11
900
ND
300
19
ND
ND
ND
470
36
ND
ND
ND
Treated
effluent
ND
ND
ND
10
30
ND
ND
ND
200
ND
30
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14
ND
ND
ND
ND
12
ND
ND
ND
ND
AD
Effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
390
ND
53
300
1,400
ND
ND
ND
ND
200,000
ND
1,300
ND
ND
CD3 CEa
Raw
wastewater
NA
NA
ND
NA
NA
ND
ND
NA
NA
ND
ND
ND
ND
13,000
3,500
ND
17,000
ND
ND
ND
ND
ND
ND
ND
30
ND
ND
ND
ND
ND
1,300
ND
Treated
effluent
90
7,000
ND
9
35
ND
ND
310
70
ND
ND
ND
ND
4,100
1,100
ND
17,000
ND
ND
ND
ND
ND
ND
20
370
ND
ND
ND
ND
ND
890
ND
Raw
wastewater
ND
ND
6
6
21
1,000
ND
ND
60
5
6
ND
10
ND
ND
ND
32
7
20
71
17,000
6,000
1,600
74
95
15
1,500
20,000
ND
ND
ND
ND
Treated
effluent
ND
ND
ND
7
ND
32
ND
ND
36
10
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
700
ND
ND
ND
ND
ND
ND
100
ND
ND
ND
ND
(continued)
-------
o
n-
• •
cr>
\
NJ
U)
\
oo
o
VD
•
Ul
I
TABLE 9.5-7 (continued)
Toxic pollutant
Conventional, mg/L
BOD
COD
TSS
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Ethers
Bis(2-chloroisopropyl) ether
Phthalates
Bis ( 2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Tr ichlorophenol
Raw
wastewater
NA
NA
NA
Raw
wastewater
ND
ND
ND
30
80
ND
ND
ND
ND
ND
ND
ND
ND
50
ND
20
ND
ND
ND
ND
ND
ND
ND
A3
Treated
effluent
140
300
97
DE3
Treated
effluent
ND
ND
ND
10
20
ND
ND
ND
ND
ND
ND
ND
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
D3
Raw
wastewater
260
490
150
Treated
effluent
19
54
15
ACD3
Raw
wastewater
24
120
32
14
27
ND
46
ND
89
ND
ND
250
ND
39
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
56
ND
ND
16
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
AD
CD3
Raw
Effluent wastewater
c
c
c
ACEa
Raw
wastewater
ND
ND
ND
145
145
840
10
0.8
200
ND
ND
250
ND
100
ND
90
22
5
60
ND
ND
220
7
NA
NA
NA
Treated
effluent
ND
ND
ND
15
10
400
ND
ND
100
ND
ND
50
ND
200
ND
12
55
4
3.5
ND
ND
24
6
Treated
CE"
Raw
effluent wastewater
NA 1
NA 3
NA
ADE
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
,500
,500
84
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5
ND
ND
ND
ND
ND
ND
ND
11
ND
Treated
effluent
120
750
210
BDE3
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
30
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
-------
a
P
rt
CD
TABLE 9.5-7 (continued)
to
00
00
o
U1
I
Toxic pollutant
Aroma tics
Benzene
Chlorobenzene
1 , 4-Di Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Naphthalene
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chloroform
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
1 , 3-Dichloropropene
Methylene chloride
1,1,2 , 2-Tetrachloroe thane
Te trach loroethy lene
1,1, 1-Trichloroe thane
1,1,2-Trichloroe thane
Trichloroe thy lene
Trichlorofluorome thane
Pesticides and metabolites
Isophorone
Classical
BOD
COD
TSS
DE
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
130
15
ND
ND
800
ND
ND
ND
17
ND
ND
ND
NA
NA
NA
a
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
250
ND
ND
ND
ND
ND
ND
ND
NA
850
350
ACD
Raw
wastewater
820
ND
ND
ND
ND
10,000
ND
ND
ND
ND
1,200
ND
ND
ND
20
ND
ND
ND
ND
ND
ND
ND
990
3.000
400
a
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
72
940
200
ACE3
Raw
wastewater
2,100
600
5
86
ND
25
ND
14
ND
ND
210
ND
ND
ND
5,900
10
ND
ND
ND
11
ND
ND
2,000
4,800
NA
Treated
effluent
8
200
1
3
ND
ND
ND
7
ND
ND
ND
ND
ND
ND
210
ND
ND
ND
ND
ND
ND
ND
70
200
56
ADE
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3,100
ND
ND
ND
ND
ND
ND
ND
1,900
2,500
4103
Treated
effluent
ND
ND
ND
11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
88
ND
ND
5
ND
ND
ND
ND
13
200
82a
BDE
Raw
wastewater
40
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
130
ND
ND
ND
ND
ND
ND
ND
7,500
12,000
4,900
a
Treated
effluent
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
210
ND
ND
ND
ND
ND
ND
ND
4,600
7,400
4,000
(continued)
-------
D
D)
ft
n>
LO
CD
o
H
U1
I
TABLE 9.5-7 (continued)
CDE3
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Ethers
Bis(2-chloroethyl) ether
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl bentyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Nitrogen compounds
N-nitrosodiphenylatnine
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
Cresols
4 , 6-Dinitro-o-cresol
Aroma tics
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 4-Dinitrotoluene
Ethylbenzene
Toluene
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
169
ND
360
10
31
ND
ND
ND
ND
ND
ND
10
ND
37
6
ND
ND
49
41
370
Treated
effluent
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
114
ND
ND
ND
ND
ND
ND
8
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
9
160
ACDE3
Raw
wastewater
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
NA
BCDE
Treated Raw
effluent wastewater
14
ND
ND
10
65
0.02
5
ND
11
10
ND
265
ND
380
ND
ND
ND
ND
ND
ND
ND
ND
ND
7,100
ND
250
ND
ND
ND
ND
ND
350
28
<20
ND
16
22
120
ND
ND
ND
16
ND
150
ND
130
ND
ND
ND
12
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Treated
effluent
ND
ND
ND
16
41
ND
ND
ND
ND
ND
ND
250
ND
28
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ABCDE
Raw Treated
wastewater effluent
10
ND
ND
94
180
580
7.5
1.3
28
ND
24
500
ND
12
ND
ND
ND
ND
ND
ND
ND
ND
ND
230
ND
ND
ND
ND
ND
ND
7
190
ND
10
ND
23
47
180
10
0.65
110
ND
ND
195
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
12
ND
ND
ND
ND
ND
>100
(continued)
-------
o
0)
ft
CTl
\
K>
CD
O
H
H
VD
Ul
I
M
.£>.
TABLE 9.5-7 (continued)
CDE3
Toxic pollutant
Polycyclic aromatic compounds
Acenapthene
Anthracene
Fluor ene
Phenanthrene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 1-Dichloroe thane
1 , 2-Dichloroe thane
1 , 1-Dichloroethy lene
1 , 2-trons-dichloroe thy lene
Methylene chloride
Tetrachloroe thy lene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Trichloroethylene
Trich lorof luorome thane
Pesticides and metabolites
Isophorone
Conventional , mg/L
BOD
COD
TSS
Raw
wastewater
104
7
14
7
ND
13
ND
ND
ND
ND
320
13
131
10
62
ND
500
600
1,200
20
Treated
effluent
ND
ND
ND
ND
ND
9
ND
ND
ND
ND
60
ND
6
ND
7
ND
ND
29
180
30
ACDEd
Raw
wastewater
ND
ND
ND
ND
ND
NA
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
Treated
effluent
ND
ND
ND
ND
ND
450
28
7,000
10
550
850,000
ND
360,000
ND
ND
ND
ND
NA
NA
NA
BCDE
Raw
wastewater
ND
ND
ND
ND
ND
51
ND
ND
ND
ND
63
ND
ND
ND
ND
ND
ND
a
4 , 100
16,000a
2503
Treated
effluent
ND
ND
ND
ND
ND
130
ND
ND
ND
ND
32
ND
ND
ND
ND
ND
ND
a
600
NA3
i,oooa
ABCDE
Raw
wastewater
ND
ND
ND
ND
ND
130
ND
14
ND
ND
2,400
ND
ND
ND
ND
ND
ND
5,900
39,000
2,000a
Treated
effluent
ND
ND
ND
ND
ND
58
ND
33
ND
ND
214
ND
ND
ND
ND
ND
ND
140
7,500
390a
Medians derived from less than three plants.
Wastewater undergoes no treatment prior to discharge.
Not applicable.
-------
Disinfectants can contribute to the pollutant load from fermenta-
tion processes. Although steam is used to sterilize most equip-
ment, many instruments cannot withstand high temperatures.
Although there is no published information indicating which dis-
infecting agents are used, a number of toxic pollutants in-
cluding phenol, can be used for that purpose. The fermentation
process occasionally creates massive discharges of contaminated
wastewater, which occur whenever a plant becomes infested with a
phage [1].
Wastewaters from fermentation processes are generally character-
ized by high BOD, COD, and TSS concentrations; large flows; and
a pH range of about 4.0 to 8.0 [1].
II.9.5.2.2 Subcategory B - Biological and Natural Extraction
Products
The principal sources of wastewater from biological/natural extrac-
tion operations are (1) spent raw materials, such as waste plasma
fractions, spent eggs, spent media broth, plant residues, etc.;
(2) floor and equipment wash waters; (3) chemical wastes, such as
spent solvents; and (4) spills [1]. Whenever possible, bad batches
are recycled; if this is not feasible, the bad batches are dis-
charged to the plant process sewer system [2].
Wastewaters from biological/natural extraction processes are gen-
erally characterized by low BOD, COD, and TSS concentrations;
small flows; and a pH range of about 6.0 to 8.0 [1].
II.9.5.2.3 SubcategoryC - Chemical Synthesis Products
Primary sources of wastewater from chemical synthesis operations
are (1) process wastes, such as spent solvents, filtrates, cen-
trates, etc.; (2) floor and equipment wash waters; (3) pump seal
waters; (4) wet scrubber spent waters; and (5) spills [1].
Wastewaters from chemical synthesis operations are generally char-
acterized as having high BOD, COD, and TSS concentrations; large
flows; and an extremely variable pH ranging from 1.0 to 11.0 [1].
II.9.5.2.4 Subcategory D - Formulation Products
Sources of wastewater from mixing/compounding/formulation oper-
ations are (1) floor and equipment wash waters, (2) wet scrubbers,
(3) spills, and (4) laboratory wastes. The use of water to clean
out mixing tanks can flush materials of unusual quantity and con-
centration into the plant sewer system. The washouts from recipe
kettles, which are used to prepare the master batches of the phar-
maceutical compounds, may contain inorganic salts, sugars, syrup,
etc. Dust fumes and scrubbers used in connection with building
Date: 6/23/80 II.9.5-15
-------
ventilation systems or, more directly, on dust and fume generating
equipment, can be another source of wastewater depending on the
characteristics of the material being removed from the air
stream [1].
Wastewaters from mixing/compounding/formulations processes are
generally characterized as having low BOD, COD, and TSS concen-
trations; relatively small flows; and a pH range of about 6.0 to
8.0 [1].
II.9.5.2.5 Subcategory E - Pharmaceutical Research
Generally, quantities of materials being discharged by research
operations are relatively small compared with the volumes gener-
ated by production facilities. Research operations are frequently
erratic with regard to quantity, quality, and time schedule when
wastewater discharging occurs. Flammable solvents, especially
volatile solvents such as ethyl ether, that can cause explosions
and fires are the most common problem. The major sources of
wastewater are vessel and equipment washings, animal cage wash
water, and laboratory-scale production units. The wastewaters
are generally characterized as having BOD5 and COD concentrations
similar to those in domestic sewage; pH values are between 6.0
and 8.0 [2].
II.9.5.3 PLANT SPECIFIC DESCRIPTIONS
Tables 9.5-8 through 9.5-21 present plant specific information for
each of the subcategory combinations as follows:
A
D
A,D
C,D
D,E
A,C,D
B,D,E
C,E
A,C,E
A,D,E
C,D,E
A,C,D,E
B,C,D,E
A,B,C,D,E
In cases where sampling data were available for more than one
plant in a particular subcategory combination, one plant was
selected for inclusion in the plant specific description section
based on consideration of effluent concentrations, percent removal,
and amount of available data. For each of the following 14 plants,
four types of information are presented: a summary of screening
data, a description of the wastewater treatment plant, when avail-
able, performance results of the treatment system, and a flow
diagram of the wastewater treatment plant.
Except for BOD and COD, all reported pollutant levels were ob-
tained as a result of the screening program. The BOD and COD
values were derived from data in the 308 portfolios.
Date: 6/23/80 II.9.5-16
-------
It should be noted that all analysis of toxic pollutants was con-
ducted on each sample from each plant. The screening summaries
reported on Tables 9.5-8 through 9.5-21 present only those com-
pounds which were detected. Only the influent and effluent levels
are reported for each plant. Data from other locations within
the plant, which may have been sampled, were omitted in order to
highlight the effects of BPT-type treatment on the removal of
toxic pollutants.
II.9.5.4 POLLUTANT REMOVABILITY
Wastewaters from pharmaceutical manufacturing activities vary in
quantity and quality depending upon the type of operations em-
ployed. However, in general, the wastes are readily treatable.
Table 9.5-22 presents a summary of the wastewater treatment tech-
nologies identified by the industry survey and the number of
plants found to be using each particular process. End-of-pipe
systems in the pharmaceutical manufacturing industry rely heavily
upon the use of biological treatment methods, particularly the
activated sludge process. A majority of the plants that are con-
sidered to have BPT treatment in-place use activated sludge sys-
tems. One facility has installed a pure oxygen system? another
plant reported using powdered activated carbon in its activated
sludge unit. Other biological methods identified in the survey
include trickling filters, aerated lagoons, and waste stabiliza-
tion ponds. Primary treatment includes equalization to minimize
shock loads to downstream units at many of the plants. This
finding is consistent with the fact that most pharmaceutical man-
ufacturing operations produce wastewaters on an intermittent
basis. Neutralization is required at almost two-thirds of the
plants to neutralize acidic or alkaline wastes generated from the
production of specific products.
Primary separation methods to remove solids were shown by the
survey to be widely practiced. Physical/chemical systems also are
being utilized to achieve higher levels of wastewater treatment.
Thermal oxidation of strong chemical waste streams has proven
successful at two pharmaceutical facilities. Another three sites
reported using evaporation methods to reduce wastewater flows.
Effluent polishing including polishing ponds, chemical floccula-
tion/clarification, sand and multimedia filtration, and chlorin-
ation were identified at 22 pharmaceutical facilities.
Table 9.5-23 presents conventional pollutant removability and
respective treatment for 20 plants identified in the Pharmaceutical
Manufacturing Development Document [2] grouped according to man-
ufacturing subcategory combinations. These data were from an in-
itial verification survey for the conventional pollutants. Table
9.5-24 presents a key to the coded treatment operations listed in
Table 9.5-23 and in all other tables in Section II.9.5.3.
Date: 6/23/80 II.9.5-17
-------
Table 9.5-25 presents conventional pollutant removability and
respective treatment for 27 plants identified in Reference 1 grouped
according to manufacturing subcategory. These data were obtained
from the 308 portfolios. Table 9.5-26 presents similar information
for toxic pollutants; in this case the data was obtained from a
toxic pollutant screening survey.
Date: 6/23/80 II.9.5-18
-------
o -------
OJ
rt
CD
CTl
\
NJ
\ TABLE 9.5-8. SUMMARY OF SCREENING PROGRAM AT PLANT C [3]
g SUBCATEGORY A
H
H
O1
I
Summary
of screening data
Concentration, yg/L
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Chromium
Copper
Mercury
Selenium
Zinc
Phenols
4-Nitrophenol
Phenol
Halogenated aliphatics
Methylene chloride
Raw wastewater
283
3ia
ND
293
ND
60a
89a
1,600
70
ND
Treated effluent
50
47
17
48
6.4
150
120
ND
ND
70
Wastewater Treatment
Wastewater treatment plant description
Type of treatment: Biological
Unit operations: Activated sludge, aerated lagoon,
sludge stabilization
Wastewater quantity, m3/d = 1,140 (0.30 MGD)
Performance of treatment system
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
BODb -° 143
CODb -C 297
TSS -° 97
Plant Flow Diagram
Percent
removal
d
"d
"d
Not available.
Highest value chosen.
BOD and COD values were obtained from data in the 308 portfolios.
Confidential.
Intermediate.
-------
TABLE 9.5-9.
SUMMARY OF SCREENING PROGRAM AT PLANT L [3]
SUBCATEGORY D
SujTBnary of screening data Wastewater treatment plant description
Concentration, ug/L
Toxic pollutants Raw wastewater
Metals and inorganics
Chronivm 30
Copper 50
2ir,'c 300
Pnthalates
BisC-ethylhexyl)
Fhthalate 170
Di-n-butyl phthalate 20
Phenols
Pentachlorophenol 62
Aromatics
Benzene 79
Ethylbenzene 11
Toluene 900
Halogenated aliphatics
Chloroform 300
1, 2-Eichloroethane 19
Methylene chloride 470
Tetrachloroethylene 36
INDUSTRIAL »
WASTEWATER
340 m3id PR"'MAR~
CLARIflE
SANITARV
WASTEWATER , i-
97 tqlO 600,
in K^C COD
J7k4/a Iss
2C in^L BOC,
IX mga COD
HC "V. TSS
CARBON FEED
Treated effluent Type of treatment: Biological
Unit operations: Eq
ac
10 si
30 la
200 Wastewater quantity,
30
ND
ND
ND
ND Performa
jalization, primary sedimentation,
livated sludge, other polishing,
idfill
m3/d * 300 (0.08 MGD)
nee of treatment system
ND Concentration, rog/L Percent
Pollutant Raw Wastewater Treated effluent removal
14
ND BODS 259
12 COD3 489
ND TSS 146
Wastewater Treatment Plant Flow Diagram
SUPERNATNANT
r~l i
— *• -»n ] |-*-
., EQUALIZATION U9'I TS^ 'r. ._..... JT^iiij/iic
i rJ FINAL j«nkg/rtT
/ R' FT^i? CIAR'F'ER jlmg/LBO
r — ^r--- — i L—J*^ i51 "s"- c
1 98m/d SLUDGt PUMPS jl5mg(LT!
19 92.7
54 89
15 89.7
SLUDGE TO
»- CONTRACT
1C THICKENER DISPOSAL
TER
CI2 FEED
EFFLUENT
390 m3/d
OD5 CHT??iN£ 20 kg/d COD 5
>S ftOkgldTSS
D5 13 mg/L BOD^
DO 51 mg/L COD
S 15 mg/L TSS
POLYMER FEED J^VsS , , BS~
MANUAL AS ECQA ««
7500 mg/L TSS
NOTE: All ROM RATES ARE DESIGN
AVERAGES
SAMPLING PROGRAM
Cajnple location
1. Influent to treatment facilities -
"Raw Wastewater".
2. Discharge from clarifier - "treated
effluent".
B0r< and COD values were obtained from data in the 308 portfolios.
Date: 6/23/80
II.9.5-20
-------
D
0)
rt-
ro
• •
CTi
\
NJ
CO
\
00
o
TABLE 9.5-10. SUMMARY OF SCREENING PROGRAM AT PLANT X [3]
SUBCATEGORIES A,D
vo
01
I
Summary
of screening data
Wastewater treatment plant description
Concentration, ug/L
Toxic pollutants
Aromatic s
Benzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Methylene chloride
1,1, 1-Trichloroethane
Raw wastewater
390
53
300
1,400
200,000
1,300
Treated effluent
MA
NA
NA
NA
NA
NA
Wastewater Treatment
Type of treatment: None
Unit operations: Neutralization
Wastewater quantity, m3/d = 530 (0.14 MGD)
Performance of treatment system
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
Not applicable.
Plant Flow Diagram
Percent
remova 1
Not applicable.
-------
rt
CD
to
to
00
o
TABLE 9.5-11.
SUMMARY OF SCREENING PROGRAM AT PLANT W [3]
SUBCATEGORIES C,D
H
VD
•
Ul
I
to
Summary of screening data
Toxic pollutants
Concentration, pg/L
Raw wastewater Treated effluent
Metals and inorganics
Antimony NA
Arsenic NA
Chromium NA
Copper NA
Selenium NA
Zinc NA
Phenols
2-Nitrophenol 13,000a
4-Nitrophenol 3,500
Phenol 17,000a
Halogenated aliphatics
1,2-Dichlorethane ND
1,1-Dichlorethylene 30
1,1,2-Trichloroethane 1,300
Trichlorofluoromethane ND
90
7,2003
35
3103
703
4,100
1,100
17,000
20
370
890
80
Wastewater treatment plant description
Type of treatment: Chemical precipitation and
clarifier
Unit operations: Equalization, neutralization,
chemical precipitation, clarifier
Wastewater quantity, m3/d = 1,700 (0.45 MGD)
Performance of treatment system
Concentration, mg/L
Percent
Pollutant Raw wastewater Treated effluent removal
Not available.
Wastewater Treatment Plant Flow Diagram
Not available.
Highest value chosen.
-------
D
rt
• •
(T>
\
M
U)
\
00
o
H
H
VO
I
NJ
(W —
r*
ts> r»
a o
-II
»
rt I-* vfl K"
I- O 0» 3
A H« rt n
3 O A
tt> JJ QJ
n f»
o *o
5 g-
Q. rt
o
m
!-• O
K) O
ro o O
O O O
Z Z Z
DO O
H O to
WOO
01 V.
to
CD 00 -J
1C *» -J
rji ** KJ
i_n (T> ip
O 00 K>
00 Co -J
S
to o
% i
y n
it> in
CO
KJ
O
Z
O
S
o
M
M
d
rt
to
3
rt
1
8
O
n
3
M
p
rt
H-
O
3
lO
t-»
n n>
g n
< A
pi 3
M rt
5
tUrttsiZfOOO5>'>
M3'^HAO3'D'H5
3- 1 rt f-- M P- p H- O
ft" A TO C § f) 3
!-• rt U) 3 •<
» 3-
rt *<
A M
K
""*
ta i-1
. 0.0.^. «0»
Z MWZZZZZZ
z _
U) H-
rt rt
1 5
A 2
rt
*0 "§ O
A 0* 3
>1 3 »
O M-
M r*
3 « «a a. rt c
O 3 W - H- ft f»
(B u O 3 »-• i-
\ W » S » H-
o a o» 3 3 in M
"* it • • * t^ rt
H U) O H- O
A ^J IT O W 3
Pi CD f" 3 O •»
rt o o - >-
3 K- 3
A — & Pi O> A
3 MM- OWC
rf • »O rt " rt
O A H- »1
U) O U < H D>
< rt o a K-
w 2C H- rt 3 •*
rt O O AON
A D 3 0. < »
3 " &• rt
W K1 M-
« »-• « O
M C 3
C & TJ -
O> it) *•(
iD f» H- O
A -3O
V flt
i K: w
I A
g
C*
rt
rt
(0
g
C
&
m
rt
?
Cu
rt
A
M
*?
n>
rt
s.
A
Hi
I-*
C
A
3
rt
^
0
ft
s
rt
3
rt
H-
O
o
a)
a
M
§
o
A
3
rt
rt
M-
o
3
-r
•"*
w
3
g
3
o
Mt
Id
O
HI
n
3
H
3
a
a
a«
§
w
ViO
•
U1
1
M
UJ
C/3 W
G G
W 2
O 2
•-3 »
W Kj
O 0
I 1
W en
en o
> M
- W
0 3
•* i i
•* (— )
D 2
O
*T^
W
0
Q
3
2
jjq
IT1
K
i— >
OJ
-------
TABLE 9.5-12.
SUMMARY OF SCREENING PROGRAM AT PLANT S [3]
SUBCATEGORIES D,E
Summary of screening data
Concentration , vq/L
Toxic pollutants
Raw wastewater Treated effluent
Metal* and inorganics
Chromium
Copper
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Halogenated aliphatics
Chloroform
1,2-Dichloroethane
Methylene chloride
1,1,2-Trichloroethane
30
80
ND
50
20
130
15
800
17
10
20
100
10
ND
ND
ND
250
ND
Wastewater treatment plant description
Type of treatment: Biological
Unit operations: Activated sludge, mechanical thicken-
ing, centrifugation, landfill
Wastfwater quantity, m3/d - 610 (0.16 MGD)
Performance of treatment system
Concentration, mg/L Percent
Pollutant Raw wastewater Treated effluent removal
COD
TSS
847
349
Wastewater Treatment Plant Flow Diagram
AERATION .
TANK
(1,290m3 gal)
1 1 '
AERATION _
j TANK
(1,290m3 gal)
f
—r
. AERATION
TA
(1.290
l
i
. AERA
TA
(1,290
NK
m gal)
1
1 1
TION
NK
m ga
EFailENT
)
AIR
COMPRESSOR
\
AIR
EQUALIZI
(300 m3/g<
S
y PUMPS CD
JO
II
1 STREAM 1
1 STREAM 2
STREAM 3
STREAM 4
— — ^— CTnDIM U/4TTD
RECYCLE VALVE
©
SAMPLING PROGRAM
Sample location
1. Influent to WWTP
2. Effluent from WKT
COD value was obtained from data in the 308 portfolios.
Unknown.
Indeterminate.
Date: 6/23/80
II.9.5-23
-------
TABLE 9.5-14.
SUMMARY OF SCREENING PROGRAM AT PLANT H [3]
SUBCATEGORIES B,D,E
Summary of icraenina data
Concentration, uq/L
Toxic pollutants
Raw wattewater Treated effluent
Phthalates
Bi8(2-ethylhexyl)
phthalate
Aromatics
Benzene
Toluene
Halogenated aliphatlcs
Methylene chloride
30
40
140
130
ND
10
ND
210
wagtewater treatment plant description
Typ» of treatment: Biological
Unit operations: Activated sludge, chemical con-
ditioning, eentrifugation, dewater-
ing, landfill
Wastewater quantity, m'/d - 640 (0.17 MGD)
Performance of treatment system
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
BOD 7,520
COD* 12,032
TSS 4,923
Wastewater Treatment Plant Flow Diagram
4,636
7,418
4,048
Percent
removal
38.4
38.3
17.8
SLUDGE OfWATtRING BUILDING
_r ,. MFT
|
C
c
3x«48x
TIME- (~
SLUDGE A(
Z.MOppmBOD.
l,820k9lllBOD.
l.OtBppmfSS
6Wko/ilTSS
25«a
AERATION POND
5,000 pom TSS
>.720kgTSS
3,HOppmVSS
6, lOOkgVSS
76m3CLARlF!ER
SLUDGE THROUGH
OVERFLOW
-i—
-------
TABLE 9.5-15.
SUMMARY OF SCREENING PROGRAM AT PLANT P [3]
SUBCATEGORIES C,E
Summary
Toxic pollutants
Metals and inorganics
Cadir.iuir,
Ck.ramiuir.
Coyyer
C>anide
Zinc
Pntnalates
Bis(2-ethylhexyl)
Fhthalate
P.'.enols
Phenol
2,4, 6-Trichlorophenol
Aromatics
Etr.ylbenzene
Toluene
Halogenated allphatics
Carbor. tetrachloride
Cnloroform
1 , 2-Dichloroethane
of screening data
Concentration, jjg
Rav wastewater Treated
11
11
41
2 , 000
120
11
64
13
130
470
11,000
3,200
17
'L
effluent
ND
14
ND
63
11
15
ND
ND
ND
ND
ND
ND
NC
Wastewater treatment plant description
Type of treatment: Biological
Unit operations: Equalization, neutralization,
vated sludge, Berated lagoon,
acti-
polishing pond, anaerobic digestion
Wastewater quantity, ma/d - 300 (0.08 MGD)
Performance of Treatment System
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
BODa 1,865 93
COD3 4,240 946
TSS 84 326
Percent
removal
95.0
77.7
b
Wastewater Treatment Plant Flow Diagram
TOTAL WASTE
PLANT AREA
PROCESS & SANITARY
20DAY RETENTIONS 348Umm
AERATION POND NOMINAL 20-DAY
RETENTION 8 174 Umm FEED
3 37 x 103 WATT AERATORS
AERATION POND NOMINAL 20-DAY
RETENTION » IT L/mm FEED
37 x 103 WATT AERATORS'
©
I
Pa ISH ING POND
5-DAY RETENTION
ADDED JULY 1,1977
-COOLING WATERS
OUTFALL 002
SAMPLING PROGRAM
Sample location
1. Influent to neutralization building
2. Discharge from treatment plant
BOD and COD values were obtained from data in the 308 portfolios.
^.Negative removal.
Date: 6/23/80
II.9.5-26
-------
TABLE 9.5-16.
SUMMARY OF SCREENING PROGRAM AT PLANT 0 [3]
SUBCATEGORIES A,C,E
Summary
Tcxic pollutants
Metals and inoraanics
C'-romiur
Oo, per
C\ ar.ide
P.-,..'10lS
O-.Ni tr^L henol
Aromatic s
Benzene
Etvvlbenzene
Toluene
nalocenated aliDhatics
Cr.lorofcrrT!
1 , i-Z'icr.lo roe thane
M-t^siene -"Icridc
Tricrloroefi) lene
of screening data
Concentration,
ug/L
Raw wastewater Treated effluent
200
200
1 , 500
120
4, 000
13C
50
370
12
11, TOO
20
ND
ND
400
ND
ND
ND
ND
ND
KL
24'J
ND
Wastewater treatment plant description
Type of treatment : Three-stage biological
Unit operations: Equalization, neutralization, coarse
settleable solids removal, primary
sedimentation, primary chemical
flocculation/clarification, activated
sludge, trickling filter, waste
stabilization ponds, flotation
thickening, centrifugation , centri-
fugatlon dewatering, incineration,
landfill
Wastewater quantity, m3/d = 3780 fl.OO MGD)
Concentration, mg/L Percent
Pollutant Rau vvastewater Treated effluent removal
BOD3 2,330 29 98.8
COD3 4,800 203 95.8
TES -b 29 -c
Wastewater Treatment Plant Flou Diagram
SANITAR-i WASTE
PROCESS WASTES
CLARIFIER
AND DIGESTER CHLORIN4TION
BASIN
SANITARY FLOTftTION AND
SEDIMENTATION SLUDGES
OARIFIER *-i*jJ*_2j*_3j
SLUDGE SLUDGE AERATION
910m3
.OVERFLOW |—. f \SOLIDS,
|ni »-r/2l—--{SCREEN^——t-inl-
»_FINAL TRICKLING
FILTERS
OR
SEDIMENTATION
BASIN
SAMPLING PROGRAM
Sample location
1. Sedimentation basin effluent - "Raw wastewater"
2. Final clarifier effluents DAF skimminos
Date: 6/23/80
II.9.5-27
-------
TABLE 9.5-17.
SUMMARY OF SCREENING PROGRAM AT PLANT Q [3]
SUBCATEGORIES A,D,E
Summary of screening data
Concentration,
Toxic pollutants
wastewater Treated effluent
Metals and inorganics
Chroauum
Copper
Mercury
Selenium
Tnalllum
Zinc
Fntnalates
Bls(2-ethylhexyl)
phthalate
Phenols
Fnenol
Aromatics
Benzene
Toluene
Kalogenated aliphatics
Carbor. tetracnlorlde
Chloroform
1,1-Dlcnloroetnylene
Methylene chloride
Tetrachloroethylene
1,1,1-Trichloroetnane
Trichloroethylene
Tnchlorofluorome thane
16
73
1.7
280
18
250
180
260
310
16
180
230
,200
14
22
24
970
10
ND
ND
30
11
100
68
80
ND
ND
ND
ND
ND
ND
NC
ND
ND
ND
Wastewater treatment plant description
Type of treatment: Multiple-stage biological
Unit operations: Activated sludge, trickling filter,
aerated lagoon, waste stabilization
pond, polishing pond, sludge sta-
bilization, cropland use
Wastewater quantity, m3/d « 4,500 (1.2 MGD)
Performance of treatment system
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
Percent
removal
BOD
COD3
TSS
1,340
2,520
705
13
197
44
99.1
92.1
93.8
Wastewater Treatment Plant Flow Diagram
AGRICULTURAL
RESEARCH
(?) 1 RAW
^ f WASTE
BOD-5.M0kg/d
COD • 9. 500 kgld
S.S.-2,MO»g
-------
TABLE 9.5-18. SUMMARY OF SCREENING PROGRAM AT PLANT R [3]
SUBCATEGORIES C,D,E
Summary of screening data
Wastewater treatment plant description
Concentration, ug/L
Toxic pollutants
Ethers
Bis (2-chloroisopropyl)
ether
Phthalates
Butyl-benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
2,4-Dunethyl phenol
Aromatics
Benzene
Chlorobenzene
2 1 4-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic organic
compounds
Acenapthene
Anthracene
Fluorene
Phenanthrene
Halogenated allphatics
Chloroform
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Trichloroethylene
Pesticides and
metabolites
Isophorone
Raw wastewater
300
720
19
61
ND
73
12
65
82
790
92
14
27
14
26
640
26
260
19
120
1,000
Treated effluent
180
ND
ND
ND
15
ND
ND
ND
17
320
ND
ND
ND
ND
IB
120
ND
12
ND
14
Type of treatment: Biological
Unit operations: Equalization, neutralization, primary
sedimentation, activated sludge,
aerated lagoon, landfill
Wastewater quantity, mVd - 38 (0.01 MGD)
Performance of treatment system
Concentration, mg/L Percent
Pollutant P\aw wastewater Treated effluent removal
BODa 600 30 95.0
COD3 1,200 60 95.0
TSS 20 30 -b
Wastewater Treatment Plant Flow Diagram
Raw waste >• Neutralization *• Primary sedimentation *• Aeration units
(activated sludge) >• Lagooning.
Design considerations
Detention time of aerators: 2 hr
Detention time of lagoons: 60 d
Treatment plant capacity: 110 m3/d
Solvent wastes >• Recovery
SAMPLING PROGRAM
Sample location
Industrial stream influent
Secondary clarifier effluent
BOD and COD values were obtained from data in the 308 portfolios.
Negative removal.
Date: 6/23/80 II.9.5-29
-------
o
Cu
it
(D
UJ
oo
o
TABLE 9.5-19.
Ul
I
OJ
o
SUMMARY OF SCREENING PROGRAM AT PLANT T [3]
SUBCATEGORIES A,C,D,E
Summary
of screening data
Wastewater treatment plant description
Concentration, ug/L
Toxic pollutants
Metals and inorganics
Antimony
Chromium
Copper
Cyanide
Lead
Nickel
Selenium
Zinc
Phthalates
Bis (2-ethylhexyl)
phthalate
Phenols
Phenol
Aromatics
Toluene
Halogenated aliphatic s
Chloroform
1 , 1-Dichloroethane
Paw wastewater
21
20
130
0.04
10
22
20
530
760
14,000
2.0
1.5
1.7
Treated effluent Type of treatment: None
Unit operations: No treatment provided
Wastewater quantity, m3/d = 4,010 (1.06 MGD)
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
Performance of treatment system
NA Concentration, mg/L Percent
Pollutant Raw wastewater Treated effluent removal
NA
NA (Not applicable)
Wastewater Treatment Plant Flow Diagram
(Not applicable)
-------
TABLE 9.5-20.
SUMMARY OF SCREENING PROGRAM AT PLANT E [3]
SUBCATEGORIES B,C,D,E
Summary of screening data
Toxic pollutants
Concentration, ug/L
Metals and inorganics
Antimony
Arsenic
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Nitrogen compounds
N-nitroso-
diphenylamined
Aromatics
Toluene
Halogenated aliphatic s
Chloroform
Methylene chloride
68
32
16
35
590
80
ND
20
30
ND
150
38
34
290
860
1,100
Raw wastewater Treated effluent
Nn
ND
16
26
52
ND
1.6
40
ND
58
99
28
ND
ND
1,000
32
Wastewater treatment plant description
Type of treatment: Biological
Unit operations: Equalization, neutralization, aerated
lagoon, incineration
Wastewater quantity, mVo" = 1,320 (0.35 MGD)
Performance of treatment system
Concentration, mg/L
Pollutant Raw wastewater Treated effluent
Percent
removal
SOD
COD3
TSS
7,100
15,700
369
869,
1,790
87.8
Wastewater Treatment Plant Flow Diagram
PHOSPHORIC ACIO
STORAGE 'AW
CAL'STIC
FtED
FACILITIES
1
1
1
Q ApH.RC
UNTREATEC T 1 T
PROCESS WASTES •*• — f"5~ »• j
D!D ~J
6 ^M -.,--. ...
.. s .. ,
FUD PUMPS
FIRC
rn ,
rL L
j ' .«
•v^-- ^4n—
" tASIN EQUALIZATION , !
(FJClSTINCi TAWCIWISTINGI -,,\ \ "• '
SPRAV WATIR FOR
150 ™3 WASnWATER
LIFT PUMPS
i
1 /*%
I
| \ \ : p"
: | j ;, A^X """I**1 Q /—v^™™*
• ij i j ' " T ' j ill/
D D ^ D D L-j , ^JJ A X ©
^^ EFFLUENT PRETREATED EFFLUENT
° D Cl O 5UWP TO ACCESS PIT
' S3 SPARGE ' "r3 THENTOSTP
1 RING 1 ' — , -*^«
AEBATIOf. TANK «... 5
W ™3 UGEW, 950m3
A ALARM
C CONTROlifR
F FLOW
1 ItiOICATOR
UFI" LL LIQUID LEVEL
• — OPI 5, pHR£SSUIi£
R RECORDER
1C TOTAL CARBON
IOC rOJAt OUGAMC CABBC*1
SAMPLING PROGRAM
Sample location
1. Influent to pretreatment system
2. Effluent from pretreatment system
BOD and COD values were obtained from data in the 308 portfolios.
Unknown.
Indeterminate.
Negative removal.
Date: 6/23/80
II.9.5-31
-------
TABLE 9.5-21.
SUMMARY OF SCREENING PROGRAM AT PLANT K [3]
SUBCATEGORIES A,B,C,D,E
ftetals and inorganic*
ChroiM\iP
Copper
Cyanide
Hercurj
Thill lufli
Fhthalatet
i)
phthalatt
Phtnoit
Pentachlorophenol
Phenol
AlOmatJCi
Benzene
i , «-Dichlerobenzene
1 , 4-Cichlcrobernene
Ethylbennne
TclutM
Halogenated aliphatici
Carbon tetracMondt
Chloroforrr
1 ,2-Dichloroethan*
1 , l-DiChioro«thyi«n*
Mtthyltn* chloride
T^icrJ.oro•t^Jlene
Trichiorofiuorometh»ne
160
3,100
860
»-
230
390
LI
3,100
360
29C
10
1,600
560
SO
i30
2, 000
19C
4,800
2,100
63
300
TO
NP
NC
NO
16C
HD
56
Typ» of trtiimtntt
Unxt op«ritioni,
• F«nn«nt«tion wtitt tr«tfl«nt Byittm - *qu*lii«tior,,
neutralization, cotnt •*ttl«»bl« tolidt r»ircvtl,
primary Mdinwntation, »ctiv*ttd tludqe, anaerobic
digait ion, c«ntrifugation dtwattring, landfill
• Chemical vatti treatment lyiteir - equalization,
neutralisation, coatae Mttleablt tolid* removal,
primary •edimentation, primary chemical floccula-
tlon/clarificatien, aerated'lagoon, anaerobic
gifettion, eentrifuflation dewatering landfill
• Secondary thermal oxidation lyicem - equalixetion,
neutralitation, priaary ••paration. thermal
oxidation
• Waetetfftter pretreatment •y§te» - phyiicil/charrucal
treatment, h«*t conditioning
WastvMter quantity, m'/di 1,780 (1.00 MGD)
_?trfenutnce of treiat»j«nt_yyiteiq_.
Treat** Percent Raw Treated Percent
^ treatment By_Kterr
12,4:, 244 96 24,000
Fermentation
1,740
24C.OOO
1,450
4.4TC
S2,000
4.48C
d
457
d
355,000 20 99.9
Wastewater Treatment Plant _FlQw _Diagrair
93.2
96.6
SANITARY WASTES
ID1UJTI MlOCiSS WASTES
AND HUMAN W*$Tl FROM
ION SECTOR >
SCRLJIBER WAUOS
STORM SEWtRS tCiNTft
EAST SIDE OF PlAtfTl
'COOLING WATER
SAMPLING PRQGRA^
sample locat
1. 001 Discharge
2 Combined effluent frotr limestone bed and
hillside storm se*er
ver, high
8CC and COD values wer>
^Negative removal.
obtained froir data in the 308 portfoln
Date: 6/23/80
II.9.5-32
-------
TABLE 9.5-22. SUMMARY OF TREATMENT OPERATIONS
UTILIZED IN THE PHARMACEUTICAL
MANUFACTURING INDUSTRY3 [3]
Treatment operations Number of plants
Equalization 55
Neutralization 72
Coarse settleable solids removal 39
Primary sedimentation 33
Primary chemical flocculation/clarification 11
Dissolved air flotation 2
Activated sludge 45
pure oxygen 1
powdered activated carbon 1
Trickling filter 8
Aerated lagoon 19
Waste stabilization pond 8
Intermittent sand filtration 4
Physical/chemical treatment 15
thermal oxidation 2
evaporation 4
Polishing pond 9
Multimedia filtration 7
Activated carbon filtration 2
Other polishing such as chemical 13
flocculation/clarification, sand filtration,
chlorination
aFrom 308 data.
Date: 6/23/80 II.9.5-33
-------
o
0)
rt
(D
NJ
U>
CO
O
H
VD
I
U)
TABLE 9.5-23. CONVENTIONAL POLLUTANT REMOVABILITY AT 20 PHARMACEUTICAL PLANTS [2]
BOD
Concentration, my/L
Suhcategory
A
B
C
D
E
AC
BD
DE
BDE
ABCDE
Plant
09
20
1)8
12
10
11
15
ia
05
14
01
04
21
22
25
03
Or)
24
n
21
26
Haw
wastewater
3,200
1,400
19
25
1,200
2, 200
10,000
750
310
100
-
1 , 300
1, 300
2,400
800
178
360
90
520
11
1,200
Treated
effluent
26
ao
5.8
-b
47
200
2,000
59
0.22
13
-C
160
66
14
280b
3.5
8b
2
48
Percent
removal
99
93
70
9(>
91
80
92
99
87
99
88
95
99
65
99
91
82
96
COb
Concentration, m
-------
TABLE 9.5-24. KEY TO CODED TREATMENT OPERATIONS [2]
Wastewater conditioning
Cl Equalization
C2 Neutralization
Primary wastewater treatment
PI Surface skimming
P2 Coarse settleable solids removal
P3 Primary sedimentation (clarification)
P4 Primary chemical flocculation/clarification (chemical precipitation)
P5 Primary separation
P6 Gas flotation with chemical addition
P7 Multimedia filtration
Secondary wastewater treatment
Si Activated sludge
S2 Activated sludge with pure oxygen
S3 Trickling filter
S4 Aerated lagoon
S5 Waste stabilization pond
S6 Polishing pond
S7 Other polishing
Tertiary wastewater treatment
Tl Activated sludge with powdered activated carbon
T2 Multiple effect evaporation
Sludge treatment
Wl Sludge stabilization
W2 Flotation thickening
W3 Mechanical thickening
W4 Centrifugal thickening
W5 Aerobic digestion
W6 Anaerobic digestion
W7 Chemical conditioning
W8 Chemical stabilization
W9 Thermal conditioning
WlO Vacuum filtration
Wll Dewatering
W12 Centrifugal dewatering
Disposal
Dl Incineration
D2 Thermal oxidation
D3 Landfill
D4 Cropland use
Date: 6/23/80 II.9.5-35
-------
TABLE 9.5-25.
CONVENTIONAL POLLUTANT REMOVABILITY AT 27
PHARMACEUTICAL PLANTS3 [1]
BOO
Concentration, mg/L
Sub-
category Plant
A C
D L
AD X
CD M
CE N
P
DE S
ACD G
ACE K
0
ADE A
J
C
U
BDE H
CDE R
2
E
ACDE T
Y
AA
BCDE D
E
F
ABCDE B
I
K,
Kf
Kq
Xh
K1
K3
°From 308 data.
Indeterminate.
.Not applicable.
Raw
wastewater
NA
260
-C
HA
1,000
1,900
NA
990
1,600
2,300
2,500
NA
1,300
-c
7,500
600
NA
C
NA
C
1,200
7,100
NA
3,000
1,200
12,000
5,700
NA
NA
37,000
Treated
effluent
140
19
-C
NA
150
93
NA
72
110
29
200
7
13
-C
4,600
30
28
C
NA
C
330
870
NA
120
150
240
1,100
NA
1
60
ODD
Concentration , »g/L
Percent Raw
renoval waetewater
-b
93 490
b
- NA
86 2,700
95 4,200
-b NA
93 3,000
93 NA
99 4,800
92 HA
-" HA
99 2,500
-c
39 12,000
95 1,200
b
- NA
C
-" HA
_c
73 NA
88 16,000
- NA
96 NA
88 2.600
98 24,000
81 1,700
-b 240,000
36,000
99 HA
Treated Percent
effluent r«K>val
300 -b
54 89
b
HA -
550 80
950 77
850 -b
940 69
HA -b
200 96
w
600 -b
40 -b
200 92
-c
7,400 38
60 95
b
290 -
c
SA -b
C
HA -b
%
NA -°
NA -b
410 84
1 , 500 94
d
4,500
52,000 78
20 99^
280 -b
TSS
Concentration , mg/L
Raw
va\*tewater
HA
150
-c
NA
HA
84
NA
400
NA
NA
100
NA
710
-c
4,900
20
NA
c
NA
c
120
370
NA
950
2,000
4,500
4,500
NA
NA
HA
Treated
effluent
97
15
-c
NA
90
330
350
200
83
29
50
70
44
-c
4,000
30
29
c
NA
C
250
1,800
NA
500
320
310
460
NA
10
NA
Percent
removal
_b
90
b
_b
d
b
50
b
b
50
_b
11
d
b
_b
d
_d
~b
47
84
93
90
_b
b
b
Flow
L/S
13
3.5
t.l
20
39
3.5
7.0
44
57
44
21
22
53
1,300
74
0.44
4.4
46
66
IS
11
15
0.40
21
53
44
(«GD)
( 0.30)
( 0.08)
( 0.14)
( 0.45)
( 0.90)
( O.OB)
( 0.16)
( 1.00)
( 1.30)
( 1.00)
( 0.50)
( 0.05)
( 1.20)
(30.00)
( 0.17)
( 0.01)
( 0.10)
( 1 06)
( 1.50)
( 0.40)
( 0.26)
( 0.35)
( 0.01)
( 0.50)
( 1.20)
( 1.00)
Treatment
S1,S4,W1
C1,P3,S1,S7,
W1,W11,D3
C2
C1,C2,P3,P4
C1,C2,P3,S1,
K2,W8,W10,
D3
C1,C2,S1,S4,
S6.W6
S1,«3,W4,D3
M1,C1,C2,P2,
P3,P7,S1,
W2,W6,Dfc
C1,C2,P2,P3,
S1,S3,W3,
W7 ,W10,D1,
D3
C1,C2,P2,P3,
P4,S1,S3,
S5,W2,W4,
W12.D1.D3
C1,C2,P2,P3,
S4.S5.W6,
D3
C1,C2,P2,P3,
S1,W6,D6
S1,S3,S4,S5,
S6.W1.D4
C2
S1,W7,W12,D3
C1,C2,P3,S1,
S4.D3
C1,C2,H1,S7,
w7,we,wio,
D3
P2,K1,S7,T1,
W8.W10.D3
P2,P3,M1,W10,
D3
No data avail
C2,S1,S4,W3,
D6
C1,C2,S4,D1
54
C1,C2,S1,U4,
D4
C2,P2,P4,S2,
H3,D5,W7,
W10.D6
C1,C2,P2,P3,
S1,M6,K12,
D3
C1,C2,P2,P3,
P4,S4,W8,
W12.D3
M1.W9
C1,C2,P5
P2,P3,K1,W10,
D3
Negative removal.
-Floor wash treatment.
Fermentation waste treatment system.
^Chemical waste treatment system.
VWastewater pretreatment system.
Secondary thermal oxidation.
^Direct discharge treatment aysteff.
Date: 6/23/80
II.9.5-36
-------
TABLE 9-5.26.
TOXIC POLLUTANT REMOVABILITY FOR SUBCATEGORIES
AND SUBCATEGORY COMBINATIONS3 [1]
Treatment operations:
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Chromium
Copper
Mercury
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Phenols
2-Nitrophenol
4-Nitrophenoi
Pentachlorophenol
Phenol
Aromatics
Benzene
Ethylbenzene
Toluene
Haloqenated aliphatics
Carbon tetrachlonde
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methylene chloride
Tetrachloroethylene
1 , 1 ,1-Tnchloroethane
1,1, 2-Trichloroethane
Trlchlorofluorome thane
Treatment operations: cl
Toxic pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Cyanide
zinc
Ethers
BisU-chloroethyl) ether
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Nitrogen compounds
1, 2-Diphenylhydrazine
Phenols
Phenol
2,4, 6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methyl oromide
Methyl chloride
Methylene chloride
1,1, 2-Trichloroe thane
A
Plant C
S1.S4.W1
Concentration, U9/L
Raw Treated
wastewater effluent
w
28W 50
31b 47
ND 17
29 48
ND 6 . 4
60^ 150
89 120
ND ND
NO ND
ND ND
1 , 600 ND
ND ND
70 ND
ND NO
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND 70
ND ND
ND ND
ND ND
ND ND
Plant N
,C2,P3,S1,W2,W8,W10,D3
Concentration, ug/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
ND ND
ND ND
10 20
ND ND
ND ND
20 ND
ND ND
ND ND
40 ND
12 ND
33,000 1,400
ND ND
16 ND
130 ND
190 ND
30 ND
3,000 ND
40,000 200
ND ND
D
Plant L
C1,P3,S1,S7,W1,W11,D3
Concentration, pg/L
Raw Treated
wastewater effluent
ND ND
ND ND
30 10
50 30
ND ND
ND ND
300 200
170 30
20 ND
-------
Treatment operations:
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalates
Di-n-butyl phthalates
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2-Nitrophenol
Phenol
2,4, 6-Trichlorophenol
Aromatics
Benzene
Chlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Toluene
Polycyclic aromoatic
hydrocarbons
Naphthalene
Halogenated
Chloroform
1 , 2-Dichloroethane
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tr ichloroethy lene
Treatment operations:
Toxic pollutants
Metals and inorganics
Chromium
Copper
Mercury
Selenium
Thallium
Zinc
Ethers
Bis (2-chloroisopropyl)
ether
Phthalates
Bis(2-ethylhexyl)
phthalate
Butyl benzyl phthalate
Phenols
2-Chlorophenol
4-Nitropnenol
Pentachlorophenol
Phenol
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
TABLE 9.
ACD
Plant G
K1,C1,C2,P2,P3,P7,S1,
W2,W6,06
Concentration, yg/L
Raw Treated
wastewater effluent
24 ND
120 ND
32 ND
14 ND
27 ND
ND ND
46 ND
ND ND
89 56
250 16
39 ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
820 ND
ND ND
ND ND
ND ND
10,000 ND
ND ND
1,200 ND
ND ND
20 ND
ND ND
ND ND
Plant A
Cl , C2 , P2 , P3 , S4 , S 5 , rf6 , D3
Concentration, pg/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
NO ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
5-26 (continued)
ACE
Plant M
C1,C2,P2,P3,S1,S3,W3
W7,W10,D1,D3
Concentration, yg/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
90 30
90 20
170 400
20 ND
1.6 ND
400 200
500 100
200 400
180 24
*
43 110
9 7
ND 7
430 48
14 12
160 16
1,200 400
10 2
42 6
ND ND
28 14
70 ND
9,000 400
750 180
ND ND
21 ND
Plant J
C1,C2,P2,P3,S1,W6,D6
Concentration, yg/L
Raw Treated
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
450 ND
ND ND
18 ND
ND ND
ND 15
42 ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
Plant O
, C1,C2,P2,P3,P4,S1,S3,
W2,W4,W12,D1,D3
Concentration, ug/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
200 ND
200 ND
1,500 400
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
20 ND
ND HL
ND ND
4 , 000 ND
ND ND
ND ND
130 ND
50 ND
ND ND
370 ND
12 ND
11,000 240
20 ND
ND ND
ADE
Plant 2 Plant U
S1,S3,S4,S5,S6,W1,D4 C2
Concentration, pg/L Concentration, pg/L
Raw Treated Raw Treated
16 10 ND ND
73 ND ND ND
1.7 ND ND ND
280 30 ND ND
18 11 ND ND
250 100 ND ND
ND ND NA 300
180 68 NA 10
ND ND ND ND
ND ND NA 31
ND ND ND ND
ND ND ND ND
ND 80 NA 21
260 ND ND ND
ND ND NA 11
18 ND NA 21
ND ND ND 22
310 ND ND ND
Date: 6/23/80
II.9.5-38
(continued^
-------
TABLE 9.5-26 (continued)
ADE
Treatment operations: Cl
Toxic pollutants
Polycyclic aromatics
hydrocarbons
Acenapthene
Halogenated aliphaticb
Bromo form
Carbon tetrachloride
Chloroform
1 , 1-Dichloroethylene
1 , 3-Dichloropropene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Trlchlorofluoromethane
Pesticides and metabolites
Isophorone
Treatment operations
Toxic pollutants
Ethers
Bis (2-Chloroetnyl) ether
Phthalates
Bis(2-etnyinexyl) phthalate
Butyl benzyl pnthalate
Di-n-butyl phtnalate
Diethyl phthalate
Phenols
2, 4-DimetnylL nenol
4-Nitrophenoi
Phenc ,
Aromatics
Benzene
Chlorobenzere
? , 4-Dinitrotoluene
Etnyl benzene
Toiuene
Acenaphthene
Anthracene
Fluorene
Phenanturene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
." . 1 , 1-Tnchloroethane
! , 1 , 2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Iscphorone
Plant A
,C2,P2,P3,S4,S5,W6,D3
Concentration « ug/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
NA 72
ND ND
ND ND
ND ND
ND ND
ND ND
BDE
Plant H
S1,W7,W12,D3
Concentration, g/L
Raw Treated
wastewater effluent
ND ND
30 ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
40 10
ND ND
ND ND
ND ND
140 ND
ND ND
ND ND
ND ND
ND ND
ND ND
130 210
ND ND
ND ND
ND ND
ND ND
ND ND
Plant J
C1,C2,P2,P3,S1,W6,D6
Concentration, yg/L
Raw Treated
wastewater effluent
2 ND .
ND ND
ND ND
ND ND
ND ND
100 ND
77 350
ND ND
ND 10
ND ND
ND ND
11 ND
Plant R
C1,C2,P3,S1,S4,D3
Concentration, g/L
Raw Treated
wastewater effluent
300 180
ND ND
720 ND
19 ND
61 ND
ND 15
ND ND
ND ND
73 ND
12 ND
65 ND
82 17
790 320
92 ND
14 ND
27 ND
14 ND
26 18
640 120
26 ND
260 12
19 ND
120 14
1 , 000 ND
Plant Q_
S1,S3,S4,S5,S6,W1,D4
Concentration, ug/L
Paw Treated
wastewater effluent
ND ND
NC ND
18 ND
180 ND
230 ND
ND ND
6,200 ND
14 ND
22 ND
24 I-'D
970 ND
ND NP
CDE
Plant Z
Chemical waste treat -
ment system: Cl ,
C2,M1,S7,W7,W8,W10,
D3
Floor wash treatment
system: P2,M1,S7
T1,W8,W10,D3
Concentration, g/L
Raw Treated
wastewater effluent
36 48
ND ND
ND ND
ND ND
ND ND
ND ND
ND 19
19 ND
ND NL
ND ND
32 ND
ND ND
ND ND
135 ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
Plant U
C2
Concentration, ug/L
Raw Treated
wastewater effluent
ND ND
NA 12
NA 490
NA 700
ND ND
»:D ND
NA 99
ND ND
NA 380
ND ND
ND ND
ND ND
(continued)
Date: 6/23/80
II.9.5-39
-------
TABLE 9.5-26 (continued)
Treatment operations:
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Nitrogen compounds
N-nitrosodiphenylamine
Phenols
Phenol
Cresols
4 , 6-Dinitro-o-cresol
Aroma tics
Benzene
1 , 2-Dichlorobenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroform
1 , 1-Dichloroethane
1,2-Dichloroethane
1 ,1-Dichloroethylene
1,2-trvms-Dichloroethylene
Methylene chloride
1,1, 1-Trichloroethane
ACDEC
Plant Y
P3,P3,M1,W10,D3
Concentration, ug/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
NA 280
ND ND
NA 500
ND ND
NA 700
ND ND
NA 900
NA 54
NA 14 , 000
NA 20
NA 1,100
NA 1,700,000
NA 720,000
Plant D
C2,S1,S4,W3,D6
Concentration, ug/L
taw Treated
waatewater effluent
28 ND
<20 30
140 170
22 41
ND ND
ND ND
0.9 0.5
NA ND
16 30
ND ND
190 250
13% 44
12 ND
45 ND
ND 15
ND ND
12 ND
ND ND
ND ND
51 ND
ND ND
ND ND
ND ND
ND ND
35 31
ND ND
BCDE
Plant E
C1,C2,S4,D1
Concentration, ug/L
Raw Treated
wastewater effluent
68 ND
32 ND
16 16
35 26
590 52
80 ND
ND 1.6
20 40
30 ND
ND 58
150 99
38 28
34 ND
ND ND
ND ND
ND ND
ND ND
290 ND
ND ND
860 1 , 000
ND ND
ND ND
ND ND
ND ND
1,100 32
ND ND
Plant F
S4
Concentration, ug/L
Raw Treated
wastewater effluent
ND ND
ND ND
ND 12
60 110
120 ND
ND 13
ND ND
ND ND
ND ND
ND ND,
140 510
160 15
ND ND
ND ND
ND ND
ND 10
ND ND
ND ND
ND 61
ND 130
ND ND
ND ND
ND ND
ND ND
63 130
ND ND
ABCDE
Treatment operations:
Plant B
C1,C2.S1,W4,D4
Plant I
C2,P2,P4,S2,W3,D5,W7,
Plant K
Fermentation waste
Plant V
P2,P3,M1,W10,D3
W10.D6
system: C1,C2,P2,
P3,S1,W6,W12,D3
Chemical waste
treatment system:
C1,C2,P2,P3,P4,S4,
H6,H12,D3
Wastewater pre-
treatment system:
M1.W9
Secondary thermal
oxidation system:
C1,C2,P5,D2
Concentration, ug/L
Toxic pollutants
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Raw
wastewatez
b
22b
70b
NDK
680b
180b
580^
15°
NDb
630
ND.
47b
540b
24
Treated
effluent
ND
20
ND
190
31
7,700
24
ND
190
ND
29
160
33
Concentration, pg/L
Raw
wastewater
20
ND
ND
23
88
ND
63
1.3
28
ND
ND
500
ND
Treated
effluent
ND
ND
ND
19
16
ND
20
1.3
37
ND
ND
300
25
Concentration, ug/L
Raw
wastewater
ND
ND
ND
160
3,100
860
ND
9.6
ND
ND
230
390
52
Treated
effluent
ND
ND
ND
26
63
300
ND
ND
ND
ND
ND
63
ND
Concentration, ug/L
Raw
wastewater
ND
NA
NA
ND
NA
NA
ND
NA
NA
NA
ND
NA
ND
Treated
effluent
ND
20
40
ND
100
60
ND
400
300
26
ND
230
ND
Date: 6/23/80
II.9.5-40
(continued)
-------
Treatment operations:
TABLE 9.5-26 (continued)
ABCOE
Plant B
C1.C2,SI.114,04
Plant I
Plant K
C2,P2,P4,S2,W,D5,W7,
W10.D6
Fermentation waste
system: C1,C2,P2,
P3,S1,W6,W12,D3
Chemical waste
treatment system:
C1,C2,P2,P3,P4,S4,
W6,W12,D3
Kasteweter pre-
treatnent system:
M1,W9
Secondary thermal
oxidation system:
C1,C2,P5,D2
P2,P3,M1,W10,D3
Toxic pollutants
Phenols
2-Chlorophenoi
2 , 4-Dimethylph»no-
2-Nitrophenol
Pentachlorophenol
Phenol
Aromatics
Benzene
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachlorlde
Chloroform
1,2-Dichloroethane
1 , 1-Dichloroethylene
Methylene chloride
1 t 1 , 1-Trichloroethane
Trichloroethylene
Tnchlorofluoromethane
Concentration, yg/i
Raw Treated
wastewater effluent
240b
NDb
31
NDb
230b
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
290
ND
67
ND
ND
ND
Concentration, ua/L
taw Treated
wastewater effluent
ND
62
ND
ND
38
ND
ND
ND
14
190
ND
150
28
ND
1,400
27
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
90
ND
ND
ND
33
ND
ND
Concentration , pg/L
taw Treated
wastewater effluent
ND
ND
ND
11
3,100
380
290
10
1,600
560
50
130
3,000
190
4,800
ND
2,100
620
ND
ND
ND
ND
ND
44
ND
ND
160f
ND
56
65
90f
ND
ND
280
Concentration, ug/L
Raw Treated
wastewater effluent
ND
ND
ND
ND
NA
NA
ND
ND
ND
NA
NA
NA
ND
ND
ND
100
>100
24
ND
ND
ND
>200
6P
360
No percent removal data is presented here due to the nature of the data.
Highest value chosen.
CNo data available for plant AA.
Date: 6/23/80
II.9.5-41
-------
II.9.5.5 REFERENCES
1. Effluent Limitations Guidelines for the Pharmaceutical Manufac-
Industry. (draft contractors report). U.S. Environmental
Protection Agency, Washington, D.C., May 1979.
2. Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for
the Pharmaceutical Manufacturing Point Source Category.
EPA 440/1-75/060. U.S. Environmental Protection Agency, Wash-
ington, D.C., December 1976. 344 pp.
3. Supplement to the Draft Contractor's Engineering Report for
the Development of Effluent Limitations Guidelines for the
Pharmaceutical Industry (BATEA, NSPS, BCT, BMP, Pretreatment).
U.S. Environmental Protection Agency, Washington, D.C., July
1979.
4. Environmental Protection Agency Effluent Guidelines and Stan-
dards for Pharmaceutical Manufacturing. 40 CFR 439; 41 FR
50676, November 17, 1976; Amended by 42 FR 6813, February,
1977.
Date: 6/23/80 II.9.5-42
-------
11.10 NONFERROUS METALS MANUFACTURING
II.10.1 INDUSTRY DESCRIPTION
II.10.1.1 General Description [1]
The nonferrous metals industry encompasses the primary smelting
and refining of nonferrous metals [Standard Industrial Classifi-
cation (SIC) Number 333] and the secondary smelting and refining
of nonferrous metals (SIC Number 334). The industry does not
include the mining and beneficiation of metal ores; rolling,
drawing, or extruding metals; or scrap metal collection and
preliminary grading.
Primary smelting and refining includes the final recovery of pure
or usable metal from a metal ore. Some metals, such as aluminum,
are produced by essentially one process, while others, e.g.,
copper and zinc, may be produced either pyrometallurgically or
electrometallurgically. Byproducts and coproducts can often be
produced as a result of the smelting or refining of the base
metals.
Secondary recovery refers to processors of scrap. This scrap is
generally collected from scrap dealers or industrial plants.
Scrap often has a high level of impurities and generally needs
classification to separate recoverable metal from nonmetallic
material. Scrap metal can then be treated in a similar manner
as in primary metal recovery or can be refined by other, more
efficient recovery methods.
There are an estimated 800 plants in the United States involved
in the primary or secondary recovery of nonferrous metals. These
plants represent 61 subcategories. However, many of these sub-
categories are small, represented by only one or two plants, or
do not discharge any wastewater. This report focuses on 296
facilities that produce the major nonferrous metals (aluminum,
columbium (niobium), tantalum, copper, lead, silver, tungsten,
and zinc). In 1973 these facilities produced 8,100,000 Mg
(8,900,000 tons) of the listed nonferrous metals.
Nonferrous metal facilities are distributed throughout the United
States. Most sites are located near ore production facilities,
near adequate transportation facilities, or near adequate power
supplies.
Date: 6/23/80 II.10-1
-------
Table 10-1 presents an industry summary for the nonferrous metals
industry indicating the number of subcategories and the number
and type of dischargers.
TABLE 10-1. INDUSTRY SUMMARY [1, 2]
Industry: Nonferrous Metals
Total Number of Subcategories: 61
• Phase I Coverage: 26
• Phase II Coverage: 35
Number of subcategories studied: 12
Number of dischargers in industry:
• Direct: 129
• Indirect: 79
• Zero dischargers: 215
Table 10-2 presents best practicable technology limitations that
have been promulgated and reported in the Federal Register.
TABLE 10-2. BPT LIMITATIONS FDR THE NONFERROUS
METALS INDUSTRY3' [3]
Secondary aluaunun
melting
Primary Chlorine
aluminum demagging.
smelting, kg/Mg of
kg/MG of magnesium
Parameter product recovered
COD 6 5
TSS 3 0 175
Oil and grease
Ammonia
(as nitrogen)
pH 6 0-9 0 7 5-9 0
Fluoride 2 0
Aluminum
Arsenic
Cadgtium
Copper
Lead
Selenium
Zinc
Wet
processing,
kg/Hg of
product
1 0
1 5
0 01
7 S-9 0
0 4
1.0
0.3
Primary
copper
saelting.
•Q/L
SO
6 0-9 0
20
1.0
0 5
1 0
10
10
Primary
copper
refining.
•g/L
50
20
6 0-9 0
20
0.5
10
10
Pruiary
copperd
refining
kg/Hg of
product
0.10
0.04
6.0-9.0
0 04
0.001
0.02
0.02
Primary
Secondary Primary lead,
copper, lead, kg/Kg of
»q/L mq/L product
50 50 0 042
20
6 0-9.0 6 0-9 0 6 0-9 0
0 0008
1 0
0 5
1.0 0.0008
10 10 0 008
Primary
zinc ,
kg/Mg of
product
0 42
6 0-9 0
0 0016
0 008
0 08
0 08
Note- Blanks indicate parameter not regulated for BPT in this subcategory.
Maximum daily discharge, 30 day average Bay not exceed one half reported aaounts.
b
pH is reported in pH units
Zero discharge except for excess of monthly rainfall over Monthly evaporation
Located in a historic area of net precipitation
II.10.1.2 Subcategory Description [1]
The nonferrous metals industry is divided into 61 subcategories
by the type and source of the metal to be smelted and/or refined
and by similar wastewater sources. Twelve of these subcategories
Date: 6/23/80
II.10-2
-------
have been chosen for detailed study. The remainder of the sub-
categories lack sufficient data to be reported, and either have
been deferred to Phase II of the nonferrous metals study or are
Paragraph 8 exclusion subcategories. Table 10-3 lists the subcate-
gories studied, deferred, and excluded for this report. The follow-
ing subparagraphs describe the 12 subcategories chosen for detailed
study.
TABLE 10-3.
SUBCATEGORIES WITHIN THE NONFERROUS
METALS INDUSTRY [1, 2]
Subcategories and SIC codes chosen for detailed study:
Primary aluminum (3334) Primary lead (3332)
Secondary aluminum (3341) Secondary lead (3341)
Primary columbium (3339) Secondary silver (3341)
Primary tantalum (3339) Primary tungsten (3339)
Primary copper (3331) Primary zinc (3333) ,
Secondary copper (3341) Primary cadmium (3339)
Subcategories and SIC codes lacking sufficient data for study:
Primary beryllium Primary tellurium
Primary selenium Primary silver
Subcategories to be deferred to phase II:
Primary boron
Secondary boron
Primary cesium
Primary cobalt
Secondary cobalt
Secondary columbium
Primary gallium
Primary germanium
Primary gold
Secondary precious metals
Primary hafnium
Indium
Primary lithium
Primary magnesium
Secondary magnesium
Primary mercury
Secondary mercury
Primary molybdenum
Paragraph 8 exclusion subcategories and SIC codes:
Primary arsenic (3339) Secondary cadmium (3341)
Primary antimony (3339) Primary calcium (3339)
Primary barium (3339) Secondary tantalum (3341)
Secondary beryllium (3341) Primary tin (3339)
Primary bismuth (3339) Secondary babbitt (3341)
Primary columbium and primary tantalum are studied together
because of similar processes and wastewaters.
Primary zinc and cadmium are studied together because
simultaneous recovery is common.
Primary nickel
Secondary nickel
Secondary plutonium
Primary rare earths
Primary rhenium
Secondary rhenium
Primary rubidium
Primary platinum group
Secondary tin
Primary titanium
Secondary titanium
Secondary tungsten
Primary uranium
Secondary uranium
Secondary zinc
Primary zirconium
Bauxite
Primary Aluminum
Aluminum metal is produced from alumina in electrolytic pots by
the Hall-Heroult process. The pots are made of cast iron lined
with carbon and contain an electrolytic solution composed of
cryolite, calcium fluoride, and aluminum fluoride. Alumina is
Date: 6/23/80
II.10-3
-------
added to the pots periodically and electrical current causes the
reduction of alumina to aluminum metal.' Molten aluminum is re-
moved from the bottom of the pot.
The carbon-lined pot and the molten aluminum which collects in
the pot serve as the cathode. The anode is a carbon rod prepared
from petroleum coke and pitch. During the reduction process that
produces the aluminum the anodes are oxidized, producing carbon
monoxide and carbon dioxide.
The'molten aluminum is tapped and conveyed to holding furnaces
for subsequent degassing and alloying. Degassing with chlorine
(and sometimes nitrogen and carbon dioxide) serves to remove
hydrogen and to mix the aluminum to ensure a uniform alloy. At
most plants the final step is casting the finished metal.
Secondary Aluminum
In this subcategory the use of varied raw materials requires two
operations: presmelting and smelting.
Presmelting varies with the raw material being recovered. With
relatively pure feedstocks only sorting and perhaps oil removal
by drying may be required. However, crushing, screening, and
iron removal frequently are necessary.
Smelting of the cleaned, purified aluminum involves charging the
furnace with scrap and flux, addition of any necessary alloying
agents, "demagging" to remove magnesium, and skimming to remove
waste slag.
Primary Columbium and Tantalum
Columbium (also known as niobium) and tantalum metals are pro-
duced from purified salts which are prepared from ore concen-
trates and slags resulting from foreign tin production. The
concentrates and slags are leached with hydrofluoric acid to
dissolve the metal salts. Solvent extraction or ion exchange is
used to purify the columbium and tantalum. The salts of these
metals are then reduced via one of several techniques, which
include aluminothermic reduction, sodium reduction, carbon re-
duction, and electrolysis. Owing to the reactivity of these
metals, special techniques are used to purify and work the metal
produced.
Primary Copper
Smelters producing copper metal from ores use smelting and con-
verting processes plus an optional roasting step. Roasting is
used to reduce the content of sulfur and other impurities prior
to smelting. Smelting converts the ore to a molten copper/iron
sulfide material (matte) which is sent to a converter. In the
Date: 6/23/80 II.10-4
-------
converter, air is introduced and the iron sulfide is oxidized to
sulfur dioxide and iron oxide. The resulting product, called
blister copper, is cast into anodes and purified by electrolytic
refining.
In the copper refining process blister copper purchased from a
nonassociated smelter or transferred from an associated smelter
is cast into anodes and electrolytically deposited on the cathode.
All impurities become concentrated in the electrolytic solution
and in insoluble slimes. The slimes are processed for byproduct
rec&very of copper, lead, selenium, tellurium, gold and other
precious metals.
Secondary Copper
In secondary copper operations, scrap containing copper is
processed to recover the copper. Low-grade copper waste such as
slag is added in small amounts to copper alloy melts or is melted
to produce black copper. Intermediate grade scrap is used to
produce brass and bronze alloys after removal of some associated
impurities. High grade scrap is dried and baled or sawed, then
used to produce blister or refined copper.
Primary Lead
Lead is produced in a two-step process involving refining and
smelting. Typically, both operations are carried out at the same
site, but there are also nonintegrated smelters and refiners.
In the smelting process ore concentrates are blended with recycle
products and fluxes, pelletized, and sintered. The sinter is fed
with flux, coke and wastes (such as slag and dust) to a blast
furnace from which lead bullion is drawn for refining. Slag and
matte are frequently withdrawn and processed to recover any
other metals present.
In the refining process the first step is dross decopperizing.
In this step lead is maintained slightly above its melting point
and copper slag is skimmed off the top. Additional slagging
steps are carried out to remove antimony, tin, arsenic, gold,
silver, and bismuth before the lead refining process is complete.
Secondary Lead
Scrap lead from batteries and other lead-base materials is
charged to furnaces to produce soft or hard (antimonial) lead.
The soft lead may be refined or oxidized to make battery paste.
The hard lead may be used in the manufacture of battery plates
or processed to make lead alloy.
Date: 6/23/80 II.10-5
-------
Secondary Silver
Wastes containing silver include materials from photography, the
arts, electrical components, industry, and miscellaneous sources.
These wastes are processed by a wide variety of techniques to
recover the silver. Because the process is highly specific for
the type of waste, no attempt to discuss the various processes
will be made in this document.
Primary Tungsten
There are several variations in the processes of this industry
depending on the ore. In each process one of the intermediate
products is tungstic acid. The tungstic acid is converted to
ammonium tungstate, which is dried and heated to form ammonium
paratungstate. This intermediate is converted to oxides in a
nitrogen-hydrogen atmosphere. Finally, the oxides are reduced
to tungsten metal powder at high temperature in a hydrogen
atmosphere.
Primary Zinc - Primary Cadmium
In this industry, the concentrates are roasted to remove sulfur
and other volatile impurities. The product, called calcine, is
processed either pyrolytically or electrolytically to recover the
zinc. All of these plants also recover cadmium and send their
wastes to other processers for recovery of other metals.
Primary Beryllium
Primary beryllium production occurs at two plants within the
United States; one of these plants discharges its wastewater to
the environment. Because of the limited number of facilities,
beryllium production will not be discussed in this document.
Primary Selenium
Primary selenium recovery occurs at a single site which does not
discharge to the environment. Consequently, this subcategory is
not discussed further in this document.
Primary Tellurium
No information is currently available for this nonferrous metal.
Primary Silver
There are four primary silver production facilities in the United
States. Of these, two discharge wastewaters. No further infor-
mation on this subcategory is currently available.
Date: 6/23/80 II.10-6
-------
II.10.1.3 Wastewater Flow Characterization [1]
The volume of wastewater discharged in this industry varies from
0 to 540 m3/Mg (0-160,000 gal/ton) of metal is produced. In the
sampled plants, daily flows varied from 0.45 to 61,000 m3/d (120
to 16 MGD).
11.10.2 WASTEWATER CHARACTERIZATION [1]
Each metal subcategory uses different processes and emits differ-
ent pollutant concentrations and types in the process wastewater.
The following subparagraphs and tables present information on the
wastewater streams for each of the 12 subcategories studied.
II.10.2.1 Primary Aluminum
Process wastewater sources for this subcategory are primarily
related to air pollution control. Wet air pollution controls
on anode bake furnaces generate wastewater in plants utilizing
prebaked anodes. Suspended solids, oil and grease, sulfur com-
pounds, and fuel combustion products characterize this stream.
Some organics may also be present due to coal tar products
released by anode baking. Degassing with chlorine requires wet
air pollution control methods and results in a wastewater stream.
Cryolite recovery also produces a wastewater stream that has
significant amounts of fluoride, suspended solids, and TOC.
Other waste streams may also be produced by cooling water,
cathode making, and storm water runoff.
Tables 10-4 and 10-5 present conventional and toxic verification
data for the primary aluminum subcategory.
TABLE 10-4.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS
IN PRIMARY ALUMINUM RAW WASTEWATER [1]
Number of
Pollutant
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Fluoride
Analyses
2
2
2
3
2
1
3
Times
detected
2
2
2
3
2
1
3
Concentr
Range
3.4
150
2,300
0.11
4.2
2.4
- 5,700
- 440
- 11,400
- 0.27
- 5.5
- 13,000
ation,
Median
0.13
120
190
mg/L
Mean
2,900
295
6,850
0.17
4.85
120
4,400
Some numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not
having concentration values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow
and then subtracting the concentration present in the intake; refer to
Table v-6, Reference 1.
Date: 6/23/80
II.10-7
-------
ft
0>
cr»
CO
\
00
o
TABLE 10-5
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN PRIMARY ALUMINUM RAW WASTEWATER [1]
o
i
o>
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Die thy 1 phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
Phenol
Aromatics
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo(a)pyrene
Benzo(b) f luoranthene
Analyses
3
3
1
3
3
3
3
3
3
3
3
3
3
3
3
7
7
7
7
7
7
6
8
8
8
7
7
7
7
7
7
Times
detected
2
2
1
2
3
2
3
2
3
2
3
2
2
1
2
5
2
1
1
0
0
1
1
0
1
1
1
4
3
3
1
Concentral
Range
ND
ND
ND
2.3
ND
13
< 0.004
0.58
<0.1
500
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 770
- 260
- 76
- 200
- 2,200
- 140
- 29
- 780
- 1.3
- 770
- 450
- <250
- <50
- 540
- 40
- 86
- 120
- 2.5
- 70
- 6.0
- 1.0
- 50
- 30
- 150
- 180
- 570
- 260
:ion, pg/L '
Median
99
130
2.2 x 10»°c
33
24
86
77
0.022
650
0.40
660
0.20
0.40
ND
25
12
0.8
0.2
8.4
7.6
8.6
Mean
290
130
36
75
760
77
9.7
480
0.60
640
150
83
<17
188
82
22
19
0.4
12
0.8
0.2
8.4
5.6
40
38
95
37
(continued)
-------
o
0)
ft
(5
TABLE 10-5 (continued)
00
o
Toxic pollutant
Polycyclic aromatic hydrocarbons (continued)
Benzo ( k ) f luoranthene
Chrysene
Dibenz ( ah ) anthracene
Fluoranthene
Fluorene
Indeno (1,2, 3-cd )pyrene
Naphthalene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites
Aldrin
6-BHC
Y-BHC
Chlordane
4,4' -DDT
Dieldrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
Note: Blanks indicate insufficient data.
Except asbestos, which is given in Fibers/L.
Number
Analyses
of
Times
detected
Concentration, pg/La<
Ranqe Median
* • • • ' -* ~_
7
7
7
7
7
7
7
7
7
7
8
8
8
9
8
8
8
7
7
7
7
7
7
7
7
7
7
2
2
1
4
1
2
1
4
0
0
1
0
0
1
0
0
0
0
0
1
0
0
0
0
0
0
1
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
210
230
110
320 49
50
350
20
219
6.0
15
0.01
1.5
b
Mean
?Q
j ^
40
1 fi
J. U
95
7 4
/ • ^
53
3 .0
70
0.8
3.0
0.2
All concentrations except those for asbestos were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and then subtracting the concentra-
tion present in the intake; refer to Table V-5, Reference 1.
"Maximum value.
-------
II.10.2.2 Secondary Aluminum
Sources of process wastewater in the secondary aluminum industry
include demagging air pollution control, wet nulling of residues,
and contact cooling water. Removal of magnesium (demagging) in-
volves passage of chlorine or aluminum fluoride through the melt,
causing the release of magnesium in heavy fuming. The waste-
streams from the air pollution control devices contain significant
levels of suspended solids and chlorides or flourides as well as
moderate amounts of heavy metals. Milling streams also contain
suspended solids, and contact cooling water contains oil and
grease, chlorides, and suspended solids. Tables 10-6 and 10-7
present conventional and toxic pollutant concentrations found in
the wastewater streams of this subcategory.
TABLE 10-6.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS
IN THE RAW WASTEWATER OF THE SECONDARY
ALUMINUM SUBCATEGORY [1]
Number of
Pollutant
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Fluoride
Chloride
Analyses
4
4
4
4
4
2
1
3
Times
detected
4
3
4
4
4
2
1
3
Concen
Range
9 -
ND -
63 -
0.003 -
3.1 -
<0.10 -
400 -
580
140
20,000
0.025
98
140
6,000
tration, mg/L
Median
35
4
150
0.010
13
400
3,400
Mean
160
36
5,100
0.012
32
70
400
3,300
Some numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not having
concentration values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and
then subtracting the concentration present in the intake; refer to
Table v-11, Reference 1.
II.10.2.3 Primary Columbium - Primary Tantalum
The production of columbium and tantalum involves the processing
of ore concentrates and slags to obtain columbium and tantalum
salts, and the subsequent reduction of those salts to the respec-
tive metals. The ore concentrates are dissolved by hydrofluoric
acid, and the insoluble gangue is removed by filtration. Waste
gangue is generally settled in holding ponds. Overflow from this
pond is extremely acidic and contains metals, fluorides, and sus-
pended solids. After filtration, the digested solution is
extracted with an organic solvent and the raffinate is discharged
as a wastestream with high concentrations of organics, fluorides,
metals, and suspended solids. The organic stream is then
stripped with water to yield aqueous solutions of columbium and
Date: 6/23/80
11.10-10
-------
D
fu
rt
fD
CTi
\
t-O
GO
\
00
o
TABLE 10-7.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW WASTE-
WATERS OF THE SECONDARY ALUMINUM SUBCATEGORY [1}
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) ph thai ate
Butyl benzyl phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
3,3' -Dichlorobenzidine
Aromatics
Benzene
Chlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benzo ( a )pyrene
Benzo ( b ) f 1 uor anthene
Benzo (ghi )perylene
Benzo ( k ) f luoranthene
Chrysene
Fluoranthene
Naphthalene
Analyses
4
4
1
4
4
4
4
3
4
6
6
6
6
6
6
10
10
6
10
6
6
6
6
6
6
6
6
6
6
Times
detected
2
3
1
4
4
4
4
4
3
3
3
1
2
1
4
4
2
3
1
1
1
1
0
1
0
0
1
1
1
0
0
0
1
2
1
Concentration. gcr/La'b
Range
ND -
ND -
<7.0 -
<35 -
<5 -
<70 -
<0.001 -
ND -
ND -
ND -
ND -
ND -
ND -
<2.000 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
950
4,000
310
2,000
1,200
6,100
0.008
5,600
6.4
620
200
30
540
5,900
2,000
98
44
56
25
2.0
94
26
17
4.0
12
190
12
1.0
Median
150
32
7.5 x 10"
97
240
380
575
0.004
1,000
0.38
28
0
<12
ND
2,200
46
9.5
4.2
0.3
Mean
31
1,000
130
630
490
1,800
0.004
1,900
1.8
170
50
14
180
3,000
380
19
16
9.5
4.2
0.3
9.4
4.3
2.8
0.7
2.0
32
0.2
(continued)
-------
rt
CD
u>
\
00
o
TABLE 10-7 (continued)
o
I
Number of
Toxic pollutant
Polycyclic aromatic hydrocarbons (continued)
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chlorodibromome thane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroethane
1 , 2-Dachloroethane
1 , 2-rra/is-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Tr ichloroe thane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
3-BHC
y-BHC
Chlordane
4,4' -DDE
4,4' -ODD
4,4' -DDT
Dieldrin
a-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Note: Blanks indicate insufficient data.
aExcept asbestos in fibers/L.
A 1 1 r^r\r»/-'«nt-»*a+-irt«e? a*rr*ar\+- 4~H^e?^ fi-\ r* rar>ViAr*+-A*« I.*&*-A
Analyses
6
6
6
6
10
10
10
10
10
10
10
10
10
10
10
10
10
10
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Times
detected
1
1
1
1
0
1
0
6
1
0
0
5
1
0
1
0
0
5
0
1
1
1
1
1
0
1
1
0
1
1
1
1
Concentration, pq/La
Range
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
10
24
0.3
0.9
10
34
19
57
93
310
530
0.1
0.4
0.1
0.3
0.01
0.02
0.2
0.01
0.4
0.4
0.2
Median Mean
1.7
4.5
0.1
0.4
1.0
3.4
1 .9
19
9.3
32
61
0.1
0.1 0.1
All concentrations except those for asbestos were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and then subtracting the conentration
present in the intake; refer to Table V-10, Reference 1.
-------
tantalum. Precipitation of the salts is accomplished by ammonia
addition and is followed by filtration. The filtrate typically
contains high concentrations of ammonia as well as significant
levels of fluoride, various metals, and suspended solids. Con-
version of the salts to metals produces wastewater from air
pollution control scrubbers and reduction leachates. These
streams contain high levels of dissolved solids and significant
concentration of fluoride.
Tables 10-8 and 10-9 present conventional and toxic pollutant
concentration data for this subcategory.
TABLE 10-8.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS
IN THE RAW WASTEWATER OF THE PRIMARY COLUMBIUM
AND PRIMARY TANTALUM SUBCATEGORIES [1]
Number of
Pollutant Analyses
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Fluoride
Chloride
3
3
3
3
3
3
3
1
Times
detected
3
3
3
3
3
3
3
1
Concem
Range
140
45
570
0.016
5.3
64
2,200
- 6,700
- 1,000
- 8,700
- 0.10
- 16
- 2,400
- 13,000
bration, mg/L
Median
400
120
3,900
0.018
7.3
380
3,500
120
Mean
2,400
390
4,400
0.
9.
948
9,350
120
045
5
Some numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not having
concentration values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and
then subtracting the concentration present in the intake; refer to
Table V-19, Reference 1.
II.10.2.4 Primary Copper
Both smelting and refining are practiced by the primary copper
industry. Some plants engage in smelting only, others practice
only refining, and some facilities practice both operations.
Significant differences in wastewater characteristics associated
with smelting and refining are found.
Smelting process wastewater sources include acid plant blowdown,
contact cooling, and slag granulation. Acid plant blowdown
results from the recovery of sulfur from the smelting operation.
Contact casting cooling water used by primary copper smelters is
normally recycled after cooling in towers or ponds. Furnace slag
is disposed of by either dumping or granulation. Molten slag is
granulated by using high pressure water jets. The wastewater
from this granulation is typically high in suspended and dis-
solved solids and contains some toxic metals.
Date: 6/23/80
11.10-13
-------
D
&>
ft
(D
CO
00
O
TABLE 10-9.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW WASTEWATERS OF
THE PRIMARY COLUMBIUM AND PRIMARY TANTALUM SUBCATEGORIES [1]
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
Pentachlorophenol
Aroraatics
Benzene
Chlorobenzene
2,4-Dinitrotoluene
2 , 6-Dinitro toluene
Ethylbenzene
Hi trobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo ( a )pyr ene
Benzo ( b ) f luoranthene
Benzo (ghi Jperylene
Benzo ( k ) f luoranthene
2-Chloronaphthalene
Chrysene
Dlbenz ( ah (anthracene
Analyses
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
IS
15
15
15
15
IS
8
22
22
15
15
22
15
22
15
15
15
15
15
15
15
15
15
15
15
15
Times
detected
2
3
1
3
3
3
3
3
3
3
3
2
3
3
3
12
2
5
1
2
1
1
2
0
1
1
0
2
0
2
1
1
1
1
1
0
1
0
1
1
1
Concentration, yg/
Range Median
ND - 11,000 10
180 - 14,000 380
1.4 X 1010
20 - 190 89
8.0 - 19,000 48
3,000 - 520,000 3,000
400 - 260,000 500
0.002 - 0.012 0.004
3,000 - 2.7 x 10' 3,000
< 0.1 - 36 6.0
600 - 2,600 2,000
ND - 24,000 <10
<20 - 610 60
ND - <100 24
540 - 700,000 6,000
ND - 1,100 22
ND - 47
ND - 60
ND - 17
ND - 39
ND - 95
ND - 17
ND - 44
ND - 16
ND - 16
ND - 163
ND - 260
ND - 17
ND - 2.0
ND - 2.0
ND - 1.0
ND - 1.0
ND - 2.0
ND - 3.0
ND - 45
ND - 4 .0
La,b
Mean
3,700
4,900
100
6,400
180,000
87,000
0.006
9.0 X 10*
14
1.700
8,000
230
41
240,000
ISO
6.3
12
1.7
4.1
6.6
2.1
4.4
1.7
1.7
18
22
1.1
0.2
0.3
0.1
0.1
0.2
0.3
3.1
0.3
(continued)
-------
o
Q>
ft
fD
CT.
UJ
00
o
o
I
TABLE 10-9 (continued)
Number of
Toxic pollutant
Polycyclic aromatic hydrocarbons (continued)
Fluoranthene
Fluorene
I ndeno( 1 , 2 , 3-cd )pyrene
Naphthalene
Fhenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chlorodibronome thane
Chloroform
Dichlorobromome thane
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Rexachloroe thane
Hethylene chloride
1,1,2, 2-Tetrachloroe thane
Tetrachloroethylene
1,1, 1-Tr ichloroe thane
1,1, 2 -Tr ichloroe thane
Trichloroethylene
Pesticides and metabolites
Aldrin
a -BBC
ft -BBC
6 -BBC
y-BHC
Chlordane
4, 4' -DDE
4,4'-DDT
Dieldrin
or-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
I sophorone
Toxaphene
Analyses
15
15
15
15
15
15
15
15
22
22
22
22
22
22
22
22
IS
22
15
22
22
22
22
15
15
15
15
15
15
15
15
15
15
IS
15
15
15
15
15
IS
Times
detected
1
2
1
1
1
1
1
1
1
2
3
7
1
6
1
6
1
1
1
1
2
2
3
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Concentration, pq/La
Range Median
ND - 7.2
KD - 2.0
ND - 4.0
ND - 84
ND - 2.0
ND - 3.0
ND - 32
ND - 52
ND - 21
ND - 74
ND - 81
ND - 140
ND - 13
ND - ISO
ND - 22
ND - 480
ND - 23
ND - 88,000
ND - 6.0
ND - 65
ND - 40
ND - 29
ND - 230
ND - 4.0
ND - 0.04
ND - 4.5
ND - 4.0
ND - 0.03
ND - 0.8
ND - 0.4
ND - 1.0
ND - 0.1
ND - 0.01
ND - 0.03
ND - 5.4
ND - 0.2
ND - 0.5
ND - 0.1
ND - 29
ND - 0.1
Mean
1.1
1.3
0. 3
6.1
0.3
0.5
2.6
4.1
1.2
5.1
5.2
7.8
4K6
13
1.4
49
1.5
4,000
0.5
3.6
2.5
2.1
21
0.3
0.4
0.3
0.1
0.1
0.4
2.1
Note: Blanks indicate insufficient data.
aExcept asbestos, which is given in fibers/1..
Concentrations were calculated by multiplying the concentrations of the various wastestreams by the normalized
percentage of the total flow and then subtracting the concentration present in the intake; refer to Table V-18,
Reference 1.
-------
Refining operations have two principal wastestreams, waste elec-
trolyte and cathode and anode wash water. Spent electrolyte is
normally recycled. A bleed stream is treated to reduce copper
and impurity concentration. Varying degrees of treatment are
necessary because of the differences in the anode copper. Anode
impurities, including nickel, arsenic, and traces of antimony and
bismuth, may be present in the effluent if the spent electrolyte
bleed stream is discharged.
Table 10-10 and Table 10-11 present conventional and toxic
pollutant data for raw wastewater in this subcategory.
10-10. CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS IN RAW
WASTEWATER FROM THE PRIMARY COPPER SUBCATEGORY [1]
Number of
Pollutant Analyses
COD
TOC
TSS
Total phenol
Oil and grease
3
3
3
2
1
Times
detected
3
3
3
2
1
Concenti
Range
<2.0
3.5
5.3
0.005
- 730
- 7.0
- 4,400
- 0.033
ration, mg/L
Median
24
4.9
18
6.0
Mean
252
5.
1,500
0.
6.
.1
.019
,0
Some numbers in this table do not represent the concentration of the combined
total wastewater from the plant but instead represent only one or several
wastestreams. This is due to one or more of the streams not having concentra-
tion values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and then
subtracting the concentration present in the intake; refer to Table V-24,
Reference 1.
II.10.2.5 Secondary Copper
Wastewater is generated by several processes in this subcategory.
Slag milling and classification generates wastewater that is high
in suspended solids, copper, lead, and zinc. Air pollution con-
trol at the site generates acidic wastewater that contains sig-
nificant levels of copper. Other wastewater sources may include
contact cooling, electrolyte disposal, and slag granulation.
Tables 10-12 and 10-13 present conventional and toxic pollutant
data for the secondary copper recovery subcategory.
II.10.2.6 Primary Lead
Primary lead facilities have two major processes associated with
wastewater generation. The smelting process generates a major
wastestream from the sintering operation. These wastewaters are
typically high in dissolved solids and metals such as cadmium,
lead, and zinc. Acid plant blowdown, slag granulation, and air
pollution control methods are also associated with smelting
operations. Refining operations also generate wastewater from
air pollution equipment and from noncontact cooling water.
Date: 6/23/80
11.10-16
-------
TABLE 10-11.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW WASTE-
WATER FROM THE PRIMARY COPPER SUBCATEGORY [1]
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Fhthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Phenols
2 , 4-Dimethylphenol
Aromatics
Benzene
Chlorobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Chrysene
Fluoranthene
Fluorene
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromome thane
Chloroform
Dichlorobromomethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methylene chloride
1, 1,2,2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
P-BHC
Y-BHC
Chlordane
4,4' -DDT
4,4' -DDT
Dieldrin
or-Endosulfan
p-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
Number
Analyses
3
3
3
3
3
3
2
3
3
3
3
3
3
3
11
11
11
11
2
11
11
11
11
11
11
11
11
11
11
11
9
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
of
Times
detected
3
3
3
3
3
3
2
3
3
3
3
3
3
3
5
1
2
1
1
1
1
1
1
4
1
0
1
1
4
1
1
1
4
2
4
2
1
0
1
4
5
0
1
1
1
1
1
1
1
1
0
1
0
1
1
1
1
1
Concentration,9 ug/L
Range Median
<50 - 3,300 100
<2.0 - 310,000 9,300
<2 - 7.7 6.0
<5 - 9,600 7.0
<10 - 73 51
1,600 - 450,000 2,300
<0.001 - <0.02
<20 - 170,000 470
<0.5 - 48 4.6
<20 - 1,100 340
6.0 - 310 15
20 - 480 54
21 - <100 <100
30 - 150,000 400
ND - 78
ND - 1.0
ND - 75 0.7
ND - 3.0
NO - 14
ND - 3.0
ND - 40
ND - 1.0
ND - 3.0
ND - 21
ND - 1.0
ND - 1.0
ND - 1.0
ND - 21 7.0
ND - 1.0
ND - 0.6
ND - 0.7
ND - 40
ND - 13
ND - 93 5.0
ND - 14
ND - 7.0
ND - 6.8
ND - 12
ND - 15 4.0
ND - 2.0
ND - 9.0
ND - 0.01
ND - 0.04
ND - 0.2
ND - 0.01
ND - 0.02
ND - 0.02
ND - 0.01
ND - 0.1
ND - 0.4
ND - 0.01
ND - 0.01
ND - 3.0
Mean
1,200
110,000
5.2
3,200
45
150,000
0.01
56,000
18
490
110
185
74
50,000
17
0 . 1
7.6
0.3
7.0
0.7
8.4
0.2
0.3
6 . 1
0.1
0 . 3
0.1
7.1
0.4
0.1
0.1
8.4
1.2
16
1.3
0.6
0.6
1.9
5.4
0.2
1.5
0.1
0.01
0.3
Note: Blanks indicate insufficient data.
Concentrations were calculated by multiplying the concentrations of the various wastestreams by the normalized
percentage of the total flow and then subtracting the concentration present in the intake; refer to Table v-23,
Reference 1.
Date: 6/23/80
11.10-17
-------
TABLE 10-12. CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS IN THE RAW
WASTEWATER OF THE SECONDARY COPPER SUBCATEGORY3 [1]
Number of
Pollutant Analyses
COD
TOC
TSS
Total phenol
Oil -and grease
Fluoride
5
5
5
4
4
1
Times
detected
5
5
5
4
4
1
Concentration, mg/L
Range
9.7
6.0
4.0
0.0063
1.7
- 900
- 99
- 11,000
-0.22
- 30
Median
75
30
65
0.045
4.2
0.29
Mean
230
40
2,700
0.
10
0.
079
29
Some numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not having
concentration values reported; refer to Table V-29, Reference 1.
Tables 10-14 and 10-15 present conventional and toxic pollutant
data of the raw wastewater generated in this subcategory.
II.10.2.7 Secondary Lead
The principal raw material for the secondary lead industry is
scrap batteries. Wastewater is generated from battery acid
streams, wash down streams, and saw cooling for cracking the
batteries. These streams contain significant levels of suspended
solids, antimony, arsenic, cadmium, lead, and zinc. Smelting
operations for this subcategory generate wastewater from air pol-
lution control devices and contact cooling streams.
Tables 10-16 and 10-17 present conventional and toxic pollutant
data for the raw wastewater in this subcategory.
II.10.2.8 Secondary Silver
Secondary silver is recovered from photographic and nonphoto-
graphic sources. Wastewater sources from photographic wastes
include leaching and stripping, precipitation and filtration of
silver, electrolysis, and pollution control. Nonphotographic
scrap wastewater is generated by similar processes. These waste-
water streams contain significant concentrations of chromium,
copper, lead, and zinc as well as some organic priority
pollutants.
Tables 10-18 and 10-19 present pollutant data for this subcategory,
II.10.2.9 Primary Tugsten
Tungsten production involves processing ore concentrates to
obtain the salt, ammonium paratungstate (APT), and subsequent
reduction of APT to metallic tungsten. Wastewater is generated
Date: 6/23/80
11.10-18
-------
O
O
ft
tt>
cn
N)
Co
\
Co
o
o
I
TABLE 10-13. CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATERS FROM THE SECONDARY COPPER SUBCATEGORY [1]
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Aromatics
Benzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzo ( a ) pyrene
Benzo (b ) f luor anthene
Benzo ( k ) f luor anthene
Chrysene
Dibenz ( ah ) anthracene
Fluoranthene
Fluorene
I ndeno ( 1 , 2 , 3 -cd ) pyrene
Analyses
5
5
2
5
5
5
5
4
5
5
5
5
5
5
S
12
12
12
12
12
12
10
10
12
12
10
12
12
12
12
12
12
12
12
12
12
12
Times
detected
2
3
2
4
5
5
5
4
5
5
5
2
3
2
5
10
2
6
3
0
2
2
1
1
0
1
3
4
3
1
0
0
3
0
4
4
0
Concentrat:
Range
ND
ND
3.3 x 107
ND
5.0
5.0
620
<0.001
450
ND
7.0
ND
ND
ND
1,400
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 11,000
- 4,200
- 1.0 x 10' '
- 160
- 1,200
- 2,100
- 2.1 x 106
- 0.026
- 53,000
- 0.6
- 3.1 x 10s
- 270
- 1,600
- 53
- 1.5 x 106
- 7,000
- 56
- 390
- 83
- 67
- 13
- 4.0
- 5,000
- 10
- 36
- 120
- 3,000
- 1.0
- 10,000
- 3,000
- 94
ion, pg/L
Median
ND
100
30
50
<240
40,000
0.006
10,000
0.53
3,000
ND
<10
ND
40,000
53
9.5
5.8
1.0
Mean
2,200
940
5.0 x 1010
58
390
640
450,000
0.010
17,000
0.35
620,000
98
370
21
330,000
1,100
5.3
56
11
1.3
0.4
420
1.7
4.6
23
260
0.1
840
280
14
(continued)
-------
O
CU
rt
CO
00
O
o
i
N)
O
TABLE 10-13 (continued)
Number of
Toxic pollutant
Polycyclic aromatic hydrocarbons (continued)
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Dichlorobromome thane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
p-BHC
6-BHC
Y-BHC
Chlordane
4,4'-DDE
4, 4' -ODD
4,4' -DDT
Dieldrin
or-Endosulfan
p-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
Analyses
12
12
12
14
14
10
10
10
10
10
10
10
10
10
10
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
Times
detected
4
4
4
1
1
2
6
0
1
3
1
3
1
3
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
1
Concentratj
Range
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
5,000
3,000
7,000
2.0
3.0
120
1,000
32
530
5.0
510
4.0
72
70
0.2
0.2
0.02
0.2
0.04
0.7
0.02
0.1
0.03
0.03
0.3
0.3
0.4
0.3
0.02
0.4
Lon, pg/Lb
Median Mean
550
260
610
0.5
0.5
12
7.0 130
3.2
57
0.5
80
0.4
8.8
7.1
0.1
Note: Blanks indicate insufficient data.
Some numbers in this table do not represent
represent only one or several wastestreams.
reported.
DExcept asbestos, which is given in fibers/L.
of the combined total wastewater from the plant but instead
This is due to one or more of the streams not having concentration values
-------
TABLE 10-14.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS
IN THE PRIMARY LEAD SUBCATEGORY [1]
Number of
Pollutant
COD
TOC
TSS
Total phenol
Ammonia
Analyses
3
1
1
2
2
Timei
detect<
2
1
1
2
2
s Concentration, ma/L
;d Range
ND -
0.012 -
0.43 -
170
0.050
3.8
Median
3.7
3.3
26
Mean
58
3
26
0
2
.3
.031
.1
Some numbers in this table do not represent the concentration of the
of the combined total wastewater from the plant but instead repre-
sent only one or several wastestreams. This is due to one or more
of the streams not having concentration values reported.
TABLE 10-15.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND I*
WASTEWATER OF THE PRIMARY LEAD SUBCATEGORY0
RAW
[1]
Number of
Toxic pollutant Analyses
Metals and inorganics
Antimony 3
Arsenic 3
Beryllium 3
Cadmium 3
Chromium 3
Copper 3
Cyanide 2
Lead 3
Mercury 3
Nickel 3
Selenium 3
Sliver 3
Thallium 3
Zinc 3
Polycyclic aromatic hydrocarbons
Pyrene 3
Halogenated allphatlcs
Methylene chloride 4
Times
Concent
detected Range
2 ND
3 58
1 ND
3 690
3 9.1
3 100
2 <0.02
3 7,900
3 0.29
3 SO
3 3.1
2 ND
2 ND
3 2,700
1 ND
2 ND
- <330
- 96
- 6.7
- 2,700
- 30
- 5,300
- 0.13
- 24,000
- 7.5
- 150
- <13
- <20
- <100
- 20,000
- 7.0
- 25
iration, pg/L
Hedi an
3 *
93
ND
1,300
14
610
10,000
0.68
130
5.4
7.0
15
5.300
3.0
Mean
110
82
2.
1,600
18
2,000
0.
14,000
2.
110
7
9
38
9,300
2
7
.2
.08
.8
.2
.0
.3
8
Note. Blanks indicate insufficient data.
Some numbers in this table do not represent the concentration of the combined total wastewater
from the plant but instead represent only one or several wastestreams. This is due to one or
more of the streams not having concentration values reported.
Concentrations were calculated by multiplying the concentrations of the various wastestreams
by the normalized percentage of the total flow and then subtracting the concentration in the
intake; refer to Table V-32, Reference 1.
TABLE 10-16.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS
IN THE SECONDARY LEAD SUBCATEGORY [1]
Number of
Pollutant Analyses
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Chloride
3
3
4
4
3
1
1
Times
detected
3
3
4
4
3
1
1
Concenl
Range
65
4.0
0.06
< 0.004
6.4
- 220
- 130
- 3,700
- 0.012
- 40
:ration, mg/L
Median
ISO
70
760
0.010
35
12
79
Mean
145
68
1,300
0.009
27
12
79
Some numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not
having concentration values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and
then subtracting the concentration in the intake; refer to Table V-38,
Reference 1.
Date: 6/23/80
11.10-21
-------
o
D>
sr
TABLE 10-17.
00
o
o
i
to
to
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATER OF THE SECONDARY LEAD SUBCATEGORY [1]
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
2inc
Phthalates
Bis ( 2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Benzidine
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benzo ( a ) pyrene
Benzo(b)fluoranthene
Benzo (ghi)perylene
Benzo ( k ) f luor anthene
Chrysene
Fluor anthene
Fluorene
Analyses
4
3
1
3
4
4
4
4
4
4
4
3
3
3
4
5
5
5
5
5
5
10
10
10
5
10
5
5
5
5
5
5
5
5
5
Times
detected
4
3
1
3
4
4
4
4
4
4
4
1
3
3
4
5
2
4
3
3
1
1
1
1
2
0
2
2
2
1
0
1
3
3
1
Concent]
Range
1,700 -
3,000 -
1.0 -
220 -
110 -
220 -
0.002 -
7,000 -
0.6 -
210 -
ND -
90 -
50 -
790 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
80,000
13,000
30
1,900
1,000
8,200
<0.01
1.8 x 106
12
2,000
<2.0
250
620
15,000
580
85
27
13
27
6.0
2.0
5.0
1.2
16
35
20
10
5.3
5.3
540
27
2.0
ration, pg/La'
Median
38,000
7,000
1.3 x 101J
3.2
800
480
3,200
0.006
22,000
0.78
960
ND
100
350
3,600
30
13
2.0
3.0
40
1.0
b
Mean
39,000
7,700
11
930
520
3,700
0.006
460,000
3.5
1,000
0.67
150
340
5,700
180
17
12
2.6
9.0
1.2
0.2
0.5
0.3
3.2
8.6
4.0
2.0
1.6
1.6
140
7.6
0.4
(continued)
-------
o
&
rt
to
LO
00
O
o
i
TABLE 10-17 (continued)
Number of
Toxic pollutant
Polycyclic aromatic hydrocarbons (continued)
Indeno( 1 , 2 , 3-cd )pyrene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1246
Aroclor 1254
Halogenated aliphatics
Bromoform
Chloroform
1, 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-rra/is-dichloroethylene
1,1,2, 2-Tetrachl oroe thane
Tetrachloroethylene
1, 1,2-Trichloroe thane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
P-BHC
Y-BHC
Chlordane
4,4' -DDE
4, 4 '-DDT
Dieldrin
cr-Endosulfan
p-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
Note: Blanks indicate insufficient data.
aExcept asbestos, which is given in fibers/L.
t> - .
Analyses
5
5
5
5
5
5
10
10
10
10
10
10
10
10
10
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Times
detected
1
1
2
3
1
1
2
4
2
2
0
1
1
0
1
1
1
1
1
1
1
1
1
1
0
1
1
1
1
1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
ND
ND
ND
a h
Concentration, pg/L '
Range Median
- 1.0
- 4.0
- 20
-38 1.0
- 3.1 1.3
- 2.6 1.8
- 49
- 31 3.0
- 10 4.0
- 10 2.0
- 4.0
- 5.0
- 6.0
- 0.1
- 0.2
- 0.3 0.1
- 0.1
- 0.2 0.2
- 0.2
- 0.1
- 0.2
- 0.2
- 4.0
.6
- 0.3 0.1
- 0.2 0.1
- 2.7
Mean
0.2
0.8
4.6
10
1.4
1.3
5.7
6.9
4.0
3.7
1.0
1.1
0.8
0.1
0.2
1.0
0.1
0.1
0.1
1.8
streams by the normalized percentage of the total flow and then subtracting the concentration present in the intake;
refer to Table V-37, Reference 1.
-------
TABLE 10-18. CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS IN THE RAW
WASTEWATER OF THE SECONDARY SILVER SUBCATEGORY3 [1]
Number of
Pollutant Analyses
COD
TOC
TSS
Total phenol
Oil -and grease
Ammonia
Fluoride
Chloride
3
3
3
3
3
2
1
1
Times
detected
3
3
3
3
3
2
1
1
Concenl
Range
220
24
110
0.02
8.0
12.0
- 12,000
- 9,200
- 1,100
- 28
- 110
- 1,500
:ration, mg/L
Median
3,000
440
110
0.04
17
1.2
32,000
Mean
5,100
3,200
440
9
45
760
1
32,000
.4
.2
aSome numbers in this table do not represent the concentration of the com-
bined total wastewater from the plant but instead represent only one or
several wastestreams. This is due to one or more of the streams not
having concentration values reported.
Concentrations were calculated by multiplying the concentrations of the
various wastestreams by the normalized percentage of the total flow and
then subtracting the concentration in the intake; refer to Table V-43,
Reference 1.
during all three processes and results from the precipitation
and filtration of the salt, the leaching to convert to tungstic
acid, and the air pollution control methods associated with the
processes. Wastewaters may be acidic and contain significant
concentration of chlorides, arsenic, lead, zinc, and ammonia.
Tables 10-20 and 10-21 present pollutant data for the primary
tungsten subcategory.
II.10.2.10 Primary Zinc - Primary Cadmium
Wastewater is generated in the primary zinc and primary cadmium
recovery subcategories by acid plant blowdown, which results from
sulfuric acid recovery, air pollution control, leaching, anode/
cathode washing, and contact cooling. The streams may contain
significant concentrations of lead, arsenic, cadmium, and zinc.
Tables 10-22 and 10-23 present pollutant data for the primary
zinc-primary cadmium subcategories.
II. 10.3 PLANT SPECIFIC DESCRIPTION [1]
Tables 10-24 through 10-32 provide plant specific data for the
conventional and toxic metal pollutant concentrations found in
the untreated and treated wastewaters for plants in the non-
ferrous metals industry. Data for toxic organic pollutants are
not available on an individual plant basis. The available data
cover 17 plants in 10 of the 12 subcategories studied. Primary
copper and primary cadmium are not reported owing to lack of
Date: 6/23/80
II .10-24
-------
TABLE 10-19.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW WASTE-
WATERS OF THE SECONDARY SILVER CATEGORY [1]
— ~~~ Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Si 1 ver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Di-n-octyl phthalate
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Anthracene
Fluoranthene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromof orm
Carbon tetrachloride
Chlorodlbromome thane
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Tnchloroethane
Tnchloroethylene
Pesticides and metabolites
Aldnn
a-BHC
p-BHC
6-BHC
y-BHC
Chlordane
4,4' -DDE
4,4' -ODD
4,4' -DDT
Dieldrin
Endnn
Endnn aldehyde
Heptachlor
Analyses
3
3
1
3
3
3
3
3
3
3
3
3
3
3
3
5
S
5
5
5
6
6
6
6
5
5
5
5
S
5
3
3
6
6
6
6
6
6
6
6
4
6
6
6
3
3
3
3
3
3
3
3
3
3
3
3
3
Times
detected
1
3
1
2
3
3
3
3
3
1
3
1
3
1
3
5
2
5
2
4
6
1
4
6
2
2
0
1
2
1
1
1
1
2
2
1
4
3
0
4
2
6
3
6
1
0
1
1
0
1
1
1
1
1
1
0
1
Concentration , u q/La '
Range
ND - 25,000
40 - 900
5.8 x 10"
ND - <20
1,000 - 80,000
2,000 - 27,000
7,400 - 70,000
0.001 - 2.1
4,000 - 50,000
ND - 5.5
1,100 - 800,000
ND - 590
<250 - 4,700
ND - 510
8,400 - 2.0 X 10"
7.0 - 34
ND - 53
ND - 300
ND - 38
ND - 58
3.0 - 160
ND - 9.0
ND - 21
3.0 - 55
ND - 10
ND - 4.0
ND - 1.0
ND - 4.0
ND - 2,100
ND - 0.5
ND - 0.7
ND - 65
ND - 2,300
ND - 64
ND - 890
ND - 560
ND - 6,100
ND - 3,100
ND - 32
ND - 109
ND - 22
ND - 900
ND - 1.1
ND - 0.02
ND - 1.1
ND - 0.1
ND - 0.01
ND - 0.1
ND - 0.01
ND - 0.01
ND - 2.0
ND - 0.02
Median
ND
40
19
3.200
20,000
60,000
0.05
4,200
ND
30,000
ND
410
ND
20,000
11
IS
33
66
0.5
18
8.5
21
170
36
230
Mean
8,300
330
13
28,000
16,000
46,000
0.72
19,000
1.8
280,000
200
1,800
170
680,000
16
11
75
7.6
30
75
2.8
9.2
21
2.0
0.8
0.2
0.8
430
0.2
0 .2
11
380
11
160
120
1,100
1,000
8.0
43
7.3
360
0 .4
0.4
0.7
Note: Blanks indicate insufficient data.
a£xcept asbestos, which is given in fibers/L.
^Concentrations were calculated by multiplying the concentrations of the various wastestreams by the normalized per-
centage of the total flow and then subtracting the concentration in the intake; refer to Table V-42, Reference 1.
Date: 6/23/80
11.10-25
-------
TABLE 10-20.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS IN THE
WASTEWATER OF THE PRIMARY TUNGSTEN SUBCATEGORY3 [1]
Number of
Concentration, tng/L
Pollutant Analyses Times detected Range
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Chloride
3
3
3
3
3
3
2
3
3
3
3
3
3
2
120
6.0
42
0.038
6.3
3.9
850
- 880
- 270
- 6,700
- 0.089
- 17
- 1,600
- 26,000
Median
320
27
210
0.039
6.8
900
Mean
440
100
2,300
0.
10
830
13,000
055
Some numbers in this table do not represent the concentration of the combined total
wastewater from the plant but instead represent only one or several wastestreams.
This is due to one or more of the streams not having concentration values reported.
Concentrations were calculated by multiplying the concentrations of the various
wastestreams by the normalized percentage of the total flow and then subtracting
the concentration present in the intake; refer to Table V-48, Reference 1.
sufficient data. When data on several plants were available,
reported plants were selected based on the completeness of the
data and on the overall pollutant removal efficiency.
The following subparagraphs briefly describe the selected plants.
11.10.31 Primary Aluminum
Plant B generates wastewater by contact cooling (830 m3/d) and
by cryolite recovery (220 m3/d). Wastewater is treated by alka-
line chlorination and neutralization.
Plant D generates wastewater from air pollution control equipment
(4,900 m3/d), paste plant waste (570 m3/d) and anode cooling and
baking. Treatment consists of settling.
II.10.3.2 Secondary Aluminum
Plant B in this subcategory generates wastewater by processes
involving dross milling (140 m3/d) and demagging air pollution
control (95 m3/d). Treatment consists of sodium hydroxide
neutralization and settling prior to discharge.
Plant E generates wastewater by demagging air pollution control
(90 m3/d). Treatment consists of neutralization with soda ash.
II.10.3.3 Primary Columbium - Primary Tantalum
Plant B in this subcategory emits wastewater from leaching wastes
and powder wash (310 m3/d), gangue slurry pond overflow (53 m3/d),
and ammonia stripper supernatant (76 m3/d). Treatment consists
of lime addition followed by settling.
Date: 6/23/80
II .10-26
-------
0)
r+
TABLE 10-21.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATER OF THE PRIMARY TUNGSTEN SUBCATEGORY [1]
cr>
\
CD
O
N)
-J
Number of
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzo ( a )pyrene
Chrysene
Fluoranthene
Fluorene
Concentration, pg/L
Analyses Times detected Range
3
3
1
3
3
3
3
3
3
3
3
3
3
3
3
5
5
5
5
5
9
9
9
S
9
5
5
5
5
5
5
5
5
1
3
1
3
3
3
3
3
3
3
3
2
3
2
3
5
3
0
0
2
1
0
1
0
3
0
2
2
2
1
2
1
2
ND -
10 -
6.0 x
<2.0 -
19 -
44 -
95 -
0.002 -
<200 -
0.20 -
<50 -
ND -
76 -
ND -
250 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
700
7,200
109
29
190
2,000
5,000
0.14
20,000
3.00
1,000
1,000
270
600
1,900
860
23
1.0
3.0
11
45
100
110
150
1.0
240
1.0
55
Median
ND
210
<10
<20
48
120
0.013
240
1.0
92
20
86
200
520
10.0
3.0
,c
Mean
230
2,500
14
76
700
1,700
0.052
6,800
1.4
380
340
140
270
890
180
0.2
0.7
2.2
11
21
23
30
0.2
48
0.2
11
(continued)
-------
rt
fD
ro
u>
\
oo
o
TABLE 10-21 (continued)
o
i
K)
00
Number of
Toxic pollutant
Analyses Times detected
Polycyclic aromatic hydrocarbons (continued)
Naphthalene 5
Phenanthrene 5
Pyrene 5
2
0
0
Concentration, jg/L '
Range Median
ND -
1,100
c
Mean
220
Polychlorinated biphenyls and related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Chlorodibromome thane
Chloroform
Dichl or obromome thane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
1,1,2, 2-Tetrachloroe thane
Tetrachloroethylene
1,1, 1-Tnchloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
p-BHC
Y-BHC
Chlordane
4,4' -ODD
4,4' -DDT
Dieldrin
a-Endosulfan
3-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
5
5
9
9
9
9
9
9
9
9
9
9
9
5
5
5
5
5
5
5
5
5
5
5
5
5
5
9
1
1
3
2
3
0
1
3
1
2
6
2
3
1
1
1
1
1
1
1
1
2
2
1
1
1
1
0
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
0
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
1.0 0.2
5.4 0.4
48
38
1,800
8.0
19
2.0
35
69
10
19
7.0
0.6
0.1
0.2
1.2
0.1
0.1
15 0.1
15
0.8
0.9 0.2
0.2
0.2
0
1
9
4
.3
.4
.3
.2
210
2
4
0
5
1
2
1
0
0
0
0
3
3
0
0
0
0
.1
.3
.2
.2
20
.1
.9
.4
.1
.1
.2
.1
.2
.1
.2
.3
.1
.1
Note: Blanks indicate insufficient data.
aSome numbers in this table do not represent the concentration of the combined total wastewater from the plant but
instead represent only one or several wastestreams. This is due to one or more of the streams not having con-
centration values reported.
Except asbestos, which is given in Fibers/L.
CA11 concentrations except those for cyanide and asbestos were calculated by multiplying the concentrations of
the various wastestreams by the normalized percentage of the total flow and then subtracting the concentration
in the intake; refer to Table V-47, Reference 1.
-------
o
flJ
ft
CO
CD
O
TABLE 10-22. CONVENTIONAL AND NONCONVENTIONAL POLLUTANTS FOUND IN THE
RAW WASTEWATER OF THE PRIMARY ZINC SUBCATEGORY [1]
Number of
Concentration. mq/L
Pollutant Analyses Tiaes detected Range Median Mean
COD
TOC
TSS
Total phenol
Oil and grease
2
2
2
4
2
2
2
2
4
2
20 -
7.3 -
13 -
< 0.002 -
10 -
59
9.3
15
0.025 0.007
14
40
8.
14
0.
12
.3
010
Some numbers in this table do not represent the concentration of the com-
bined total wastewater fro* the plant but instead represent only one or
several waatestreans. This is due to one or store of the streams not
having concentration values reported.
TABLE 10-23.
o
i
N)
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN RAW
WASTEWATERS OF THE PRIMARY ZINC SUBCATEGORY Ml
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
3,3' -Dichlorobenzidine
Phenols
Pentachlorophenol
Aroma tics
Benzene
Ethylbenzene
Hexachlorobenzene
Toluene
1,2, 4-Tnchlorobenzene
Analyse)
4
4
2
4
4
4
2
4
9
9
9
9
9
9
9
9
9
9
9
9
9
Number of
i Times detect
4
4
2
4
4
4
4
4
4
4
4
4
4
2
4
7
2
2
2
2
0
0
1
2
1
2
2
0
Concentration, pg/L '
d Range
<2.0
3.0
3 2 X 10'
<2.0
350
'24
37
0.002
280
2.9
<50
24
<2S
•20
8,700
ND
ND
ND
ND
ND
- 2,100
- 3,000
- 4.3 x 10'
- '20
- 44.000
- 610
- 26,000
-0.38
- 18,000
- 52
- 4,300
- 1,200
- 740
- 360
- 1.7 x 10"
- 98
- 30
- 26
- 18
- 22
Median
58
150
7 5
3,400
64
1,200
0.007
4,400
5.4
590
360
58
160,000
15
5.0
Mean
550
820
3.8 x 10'
9.3
13,000
190
1 , 100
0.099
6,700
16
1,400
490
220
190
630,000
28
3.3
3.6
2.7
2.4
ND - 8.0
ND - 24
ND - 2.0
ND - 100
ND - 54
7.0
0.9
2.7
0.2
11
7.5
(continued)
-------
o
JU
ft
TABLE 10-23 (continued)
CO
\
CD
O
o
i
Number of
Toxic pollutant Analyses Tines detected
Polycyclic aromatic hydrocarbons
Acenaphthylene 9 2
Anthracene 1
Chrysene 2
Fluoranthene 2
Fluorene 2
Naphthalene o
Phenanthrene 0
Pyrene
Polychlorinated biphenyls and related compound*
Aroclor 1248 0
Aroclor 1254 0
Balogenated aliphatic*
Bromoform 9 0
Chloroform 9 3
1 . l-Dichloeoethane
1 , 2-Dichloroe thane
1, 1-Dichloroethylene
Methylene chloride
Tetrachloroethylene
Trichloroethylene
Trichloro fluorome thane
Pesticides and metabolites
Aldrin
o-BHC
P-BHC
Chlordane
4,4' -ODE
4, 4' -DDT
Dieldrin
Heptachlor
2
2
2
5
1
2
2
0
0
0
0
0
0
0
Heptachlor epoxide 9 0
Isophorone 9 2
Concentration. ii
-------
TABLE 10-24.
CONCENTRATION OF POLLUTANTS IN THE RAW AND TREATED
WASTEWATERS OF PLANTS IN THE PRIMARY ALUMINUM
SUBCATEGORY [1]
Parameter
Conventional,4 mg/L
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
Fluoride
Toxic inorganic, Mg/LC
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Sliver
Thallium
Zinc
Raw
5,700
440
11,400
0.11
4.2
120
2,600
130
76
24
86
140
29
780
1.3
660
ND
Plant B
Treated
18
16
220
0.0063
4.0
31
68
ND
ND
ND
ND
10
0.022
ND
ND
ND
540
Plant D
Percent
removal
99
96
98
94
5
74
98
>99
>99
>99
>99
93
>99
>99
>99
>99
h
Raw
3.8
150
2,300
0.13
5.5
190
770
260
2.2 x 10'°
33
200
2,200
77
7.5
650
<0.1
500
450
<250
<50
ND
Treated
120
44
80
0.0061
10
2.4
370
35
<8.0
<80
<100
24
0.0043
<260
0.2
200
23
<100
99
60b
60
95
699
63
96
97
99
50
62
65
92
>99
>99
91
Raw
48
3.0
89
0.025
98
<0.10
6,000
300
4,000
7.5 X 10*
310
2,000
97
210
<0.001
2,000
6.4
<50
200
<25
2,000
Plant E
Treated
40
120
2,000
0.011
7.3
<0.10
4,100
60
<2.0
170
1,000
76
200
<0.001
<180
3.5
<200
20
<25
10,000
Percent
removal
17.
_b
«~
56
93
_c
32
80
>99
45
50
22
_b
91
_b
90
_c
_b
Note: Blanks indicate no data currently available.
All conventional pollutant concentration* are corrected for blanks and concentra-
tions found in the water supply.
Negative removal,
Negligible removal.
Except asbestos, which is given in fibers/L.
Date: 6/23/80
11.10-31
-------
TABLE 10-26.
CONCENTRATION OF POLLUTANTS FOUND IN
THE RAW AND TREATED WASTEWATERS OF THE
COLUMBIUM AND TANTALUM SUBCATEGORIES [1]
Parameter
Conventional , a mg/L
COD
TOC
TSS
Total phenol
oil and grease
Ammonia
Fluoride
Toxic inorganic, M9/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
400
120
3,900
0.018
5.3
380
3,500
ND
380
89
48
3,000
400
0.004
3,000
6.0
2,000
ND
60
ND
540
Plant B
Treated
44
9
36
0.012
3.5
240
16
ND
ND
ND
2
3
4
0.0017
50
ND
55
ND
ND
ND
ND
Percent
removal
89
93
99
33
34
37
>99
>99
>99
96
>99
99
58
98
>99
97C
>99C
>99
Raw
6,700
1,000
8,700
0.016
16
64
13,000
11,000
14,000
190
19,000
520,000
260,000
0.012
2.7 X 10'
36
2,600
24,000
610
24
700,000
Plant D
,, Treated
150
27
89
0.030
4.0
27
6.0
200
450
20
<200
<240
110
0.007
5,000
0.8
500
4.5
<250
50
6,000
Percent
removal
98
97
"b
>5
58
>99
98
97
89
99
>99
*99
42
>99
98
81
>99
"b
99
Note: Blanks indicate no data currently available.
*A11 conventional pollutant concentrations are corrected for blanks and concentrations
found in the water supply.
Negative removal.
Negligible remova 1.
TABLE 10-27.
CONCENTRATION OF POLLUTANTS FOUND IN RAW AND
TREATED WASTEWATERS OF PLANTS IN THE
SECONDARY COPPER SUBCATEGORY [1]
Plant A
.Plant E
Parameter
Raw
Treated
Percent
removal
Raw
Treated
Percent
removal
Conventional, mg/L
COD 36 20 44
TOC 43 21 51
TSS 4.0 3.3 16
Total phenol 0.0063 0.006 5
Oil and grease 4.7 3.7 21
Fluoride
75
30
65
0.080
3.7
1,300
21
200
0.11
4.3
0.43
Note: Blanks indicate no data currently available.
*A11 conventional pollutant concentration* are corrected for blanks and
concentrations found in the water supply.
Effluent concentration exceeds influent concentration.
cExcept asbestos, which is given in fibers/L.
Negligible removal.
30,
Toxic inorganic, wq/L
Antimony
Arsenic
Asbestos
Beryllium
cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Sliver
Thallium
Zinc
ND
ND
0.3
6.0
140
15,000
0.026
450
0.07
7,000
ND
<10
~ND
1,400
ND
ND
ND
ND
ND
ND
0.015
ND
ND
5.0
ND
ND
ND
3
~ A
Q
>99
>99
>99
>99
42
>99
>99
>99d
_a
>99^
_d
>99
11,000
4,200
3.3 x 107
30
1,200
2,100
2.1 X 10«
0.004
20,000
0.53
3.1 X 10«
220
1,600
53
97,000
4,000
2,000
30
2,300
2,200
27,000
0.0027
26,000
0.23
310,000
2,300
250
60
100,000
64
52
d
"V
D
~b
99
33
D
57
90h
D
84>,
b
~b
Date: 6/23/80
11.10-32
-------
TABLE 10-28.
CONCENTRATIONS OF POLLUTANTS FOUND IN THE
RAW AND TREATED WASTEWATERS OF PLANT B OF
THE PRIMARY LEAD SUBCATEGORY [1]
Parameter
Conventional , mg/L
COD
Total phenol
Ammonia
Toxic inorganic, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
ND
0.012
0.43
3.1
96
ND
2,700
9.1
5,300
10,000
0.29
150
3.1
7.0
15
2,700
Treated
ND
0.009
0.25
ND
19
ND
110
6.0
50
<0.001
1,400
0.02
20
2.7
ND
7.4
970
Percent
removal
b
25
42
>99
80fa
96
34
99
86
93
87
13
>99
51
64
Note: Blanks indicate no data currently available.
aAll conventional pollutant concentrations are corrected
for blanks and concentrations found in the water supply.
Negligible removal.
TABLE 10-29.
CONCENTRATION OF POLLUTANTS IN RAW AND
TREATED WASTEWATERS OF PLANTS IN THE
SECONDARY LEAD SUBCATEGORY [1]
Parameter
Conventional , a mg/L
COD
TOC
Total phenol
Oil and grease
Chloride
Toxic inorganic, Mg/Lc
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Sliver
Thallium
Zinc
Haw
220
130
3,700
0.010
35
56
60,000
7,000
1.0
900
320
3,300
0.008
29,000
0.81
920
ND
100
350
4,200
Plant A
Treated
32
19
350
0.009
15
110
2,000
2,900
<9
370
200
1,000
0.002
6,000
12
580
ND
ND
100
2,900
Percent
removal
85
85
91
10
57.
_b
97
59
b
59
38
70
75
37d
>99
71
31
Raw
150
70
1,100
0.012
6 4
80,000
13,000
1.3 x lO'l
3 2
1,900
1,000
8,200
0.005
1.8 X 10s
0 3
2,000
ND
90
620
15,000
Plant C
Treated
59
34
68
0.005
52
1.3 x 1011
11
55
25
0.001
200
12
<20
100
100
Percent
removal
61
51
58
>99
>99,
_d
99
95
>99
80
>99
"b
78
84
99
Note: Blanks indicate no data currently available
aAll conventional pollutant concentrations are corrected for blanks and concentrations
found in the water supply.
Negative removal.
Except asbestos, which is given in fibers/ L.
TJegligible removal.
Date: 6/23/80
11.10-33
-------
TABLE 10-30.
CONCENTRATION OF POLLUTANTS IN THE RAW AND
TREATED WASTEWATERS OF PLANTS IN THE
SECONDARY SILVER SUBCATEGORY [1]
Parameter
Conventional , a mg/L
COD
TOC
TSS
Total phenol
Oil and greaae
Ammonia
Fluoride
Chloride
Toxic inorganic, pg/Lc
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
230
24
110
0.04
8.0
12
3,200
ND
40
ND
1.000
2,000
70,000
0.05
4,000
ND
30,000
KD
410
ND
20,000
Plant B
Treated
5.0
1.0
10
0.01
10
0.6
670
1,500
1,300
<9
2,000
8,000
300,000
0.05
20,000
0.1
60,000
ND
7,000
ND
30,000
Percent
removal
92
96
91
75b
95
79
W
"* h
fa
-Jj
~fo
b
"j
"*jj
"*|j
— v
-£
"k
**d
™j-
_D
Raw
12,000
9,200
1,100
28
110
25,000
900
5.8 X 10*
<20
3,200
27,000
7,400
2.1
4,200
5.5
1,100
590
<2SO
510
8,400
Plant C
Percent
Treated removal
30,000
14,000
120
25
67
450
700
<20
3,000
8,000
1,000
1.5
3,000
1.6
4,000
400
<250
640
5,000
K
~Jj
89
11
39
98
22
4
6
70
86
29
29
71b
32d
-),
40
Note: Blanks indicate no data currently available.
aAll conventional pollutant concentrations are corrected for blanks and
concentrations found in the water supply.
Negative removal.
cExcept asbestos, which is given in fibers/L.
Negligible removal.
TABLE 10-31.
CONCENTRATION OF POLLUTANTS FOUND IN RAW
AND TREATED WASTEWATERS OF PLANT B IN
THE PRIMARY TUNGSTEN SUBCATEORY [1]
Parameter
Conventional a rog, L
COD
TOC
TSS
Total phenol
Oil and grease
Ammonia
chloride
Toxic inorganic, pg/L
Ajitimony
Arsenic
Be t y 1 1 1 urn
Cadnuuun
Chromiujn
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Si Iver
Thai lium
Z me
Raw
0
26
7
2
5
0
20
1
1
320
6.0
210
.089
6.3
3.9
,000
ND
,200
29
190
,000
,000
013
,000
1.0
,000
20
270
600
.900
Treated
53
10
ISO
0.91
4.6
5.2
19,000
ND
70
<10
72
<50
60
0.0037
<200
95
KD
10
eoo
520
Percent
removal
"b
29b
2\
27
c
99
66
62
98
99
72
99
91
>99
96b
73
dAll conventional pollutant concentrations are corrected
for blanks and concentrations found in the water supply.
Negative removal
cNegligible removal
Date: 6/23/80
11.10-34
-------
TABLE 10-32.
CONCENTRATION OF POLLUTANTS FOUND IN RAW
AND TREATED WASTEWATERS FROM PLANTS IN
THE PRIMARY ZINC SUBCATEGORY [1]
Parameter
Conventional , a mg/L
COD
TOC
TSS
To'tal phenol
Oil and grease
Toxic inorganic, ng/Lc
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
59
9.3
15
0.004
14
67
12
4.3 x 107
7.0
5,000
610
560
0.003
3,000
6.9
4,300
270
<25
100,000
Plant C
Treated
17
8.3
9.3
0.009
1.3
51
10
3.0
36
160
53
0.007
250
2.0
620
40
16
<50
1,200
Percent
removal
71
11
38,
D
91
24
17
57
99
74
91b
U
92
71
86
85
36
99
Raw
20
7.3
13
0.025
10
<2.0
3
3.2 x 107
<2.0
350
<24
37
0.38
280
2.9
<50
24
<25
8,700
Plant E
Treated
17
8.3
<1.0
0.009
7.3
2.7
2.3
<2.0
630
<24
18
0.008
<60
0.5
<50
27
<25
7,700
Percent
removal
15.
_b
92
64
27
K
U
23
d
~b
~(j
51
98
79
83d
u
b
~ j
u
11
Note: Blanks indicate no data currently available.
All conventional pollutant concentrations are corrected for blanks and concentrations
found in the water supply.
Negative removal.
cExcept asbestos, which is given in fibers/L.
Negligible removal.
Plant D generates wastewater from extraction raffinate (870 m3/d)
and digester air pollution control (870 m3/d). Treatment con-
sists of ammonia stripping, lime addition, and settling.
II.10.3.4 Secondary Copper
Plant A has a sole source of raw wastewater from the furnace
scrubbers in the acid plant (380 m3/d). This wastewater is
treated by lime and sodium hydroxide neutralization, and polymer
addition followed by settling.
Plant E generates wastewater by the disposal of waste electrolyte
and area cleaning water (110 ms/d). This wastewater is treated
by settling.
Date: 6/23/80
11.10-35
-------
II.10.3.5 Primary Lead
Plant B generates wastewater from several sources. The acid
plant sump combines blast furnace blowdown, and slag and material
granulation (4,500 m3/d) into one stream. Other undefined proc-
ess wastes (1,100 m3/d) are also treated. Treatment consists of
simple settling.
II.10.3.6 Secondary Lead
Plant A of the secondary lead subcategory generates wastewater
from the battery electrolyte process (8 m3/d) and from saw
cooling during battery cracking (16 m3/d). Treatment consists
of ammoniation, lime neutralization, and settling.
Plant C of this subcategory releases wastewater from the saw
wash down (11 m3/d) and battery electrolyte processes (11 m3/d).
Treatment consists of lime addition and settling.
II.10.3.7 Secondary Silver
Plant B treats spent plant liquor, contact cooling, and air pol-
lution control wastewater (10 m3/d) by lime neutralization, fer-
rous chloride addition, and aluminum chloride addition followed
by settling.
Plant C uses neutralization, polymer addition, settling, and
filtration to treat slurry supernatants (3 m3/d), film waste
effluent (8 m3/d), and sludge tank effluent (3 m3/d).
II.10.3.8 Primary Tungsten
Plant B in this subcategory treats tungstic acid precipitant
rinsewater (130 m3/d) by lime addition followed by settling.
II.10.5.9 Primary Zinc
Plant C generates wastewater from air pollution control equip-
ment, boiler blowdown, and preleaching filtrate (1,600 m3/d).
Treatment consists of lime addition followed by settling.
Plant E in this subcategory uses settling to control roaster
and reduction wastewater, cooling water, and scrubber wastewater
(1,600 m3/d).
II.10.4 POLLUTANT REMOVABILITY [1]
There are several methods for pollutant removal currently used
in this industry. Some are used industry-wide; others are used
only in specific applications.
Date: 6/23/80 11.10-36
-------
Those used industry-wide include: physical-chemical methods
(precipitation, coagulation and flocculation, pH adjustment, and
ammonia stripping) and physical separation methods (filtration,
sedimentation and centrifugation) . Lime, caustic, soda ash, and
calcium chloride are used as precipitants in the industry, espe-
cially for removal of the soluble metals. In the coagulation-
flocculation system polymer, lime, and iron or aluminum salts
are mixed into the waste stream to facilitate breakdown of
colloidal suspensions. Air and steam stripping are widely
practiced techniques for the reduction of volatile compounds
such as ammonia, hydrogen sulfide, and organics.
The physical separation methods find wide application in this
industry because of the nature of the wastes. Centrifugation may
be feasible in some applications but is not suitable for abrasive
or very fine particles (less than 5
There are several potential treatment technologies that may be
applicable, but are more expensive, than the methods currently
used. These potential treatments are: sulfide precipitation,
ultrafiltration, reverse osmosis, deep-well disposal activated
carbon or activated alumina absorption, solidification, or ion
exchange .
Pollutant removal data for toxic organic pollutants in subcate-
gories studied are presented in Tables 10-33 through 10-42. The
average removal percentage was determined by comparing the
average raw wastewater concentrations found in the Wastewater
Characterization section with the average treated wastewater
concentrations presented in these tables. In some instances in-
sufficient data were available to determine accurately an average
concentration. Removal data for toxic metals and conventional
pollutant data are presented on an individual facility basis in
the plant specific section.
Date: 6/23/80 11.10-37
-------
TABLE 10-33.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM
RAW WASTEWATER IN THE PRIMARY ALUMINUM
SUBCATEGORY [1]
Number of
Toxic pollutant Samples
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-in-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
Phenol
Aromatics
Benzene
2 , 4-Dinitrotoluene
2 , 6-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo(a)pyrene
Benzo ( b ) f luoranthene
Benzo ( ghi )perylene
Benzo ( k ) f luoranthene
Chrysene
Dibenz ( ah ) anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Chloroform
1 , 2-Dichloroethane
1, 1-Dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites
Aldrin
6-BHC
Y-BHC
Chlordane
4,4' -DDT
Dieldrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
9
9
9
9
9
9
4
14
9
9
14
14
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
14
14
14
14
14
14
14
8
8
8
8
8
8
8
8
8
9
Times
Treated effluent
concentration, pg/L
detected Range Median
3
1
4
0
1
2
0
3
1
1
2
1
5
1
3
1
2
1
1
1
1
0
4
1
1
1
3
4
3
2
2
7
1
2
2
1
1
1
1
1
I
1
1
1
0
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
120
75
30
5.0
13
33
7.0
1.0
12
6.8
13
7.0
11 2.6
6.0
8.0
6.0
11
6.0
140
79 11
1.0
1.0
1.0
11
80 9.0
320
5.5
4,000
4,200
1.0
61
120
0.1
0.1
0.01
0.1
0.01
0.1
0.2
0.2
0.2
Mean
17
9.6
5.0
1.0
1.8
4.0
0.9
0.1
0.8
0.5
5.0
1.9
4.7
0.7
2.1
0.7
0.1
1.1
17
22
0.2
0.1
0. 1
0. 1
20
23
0.4
360
0 . 1
44
8 . 5
Average
percent
removal
79
56
74
>99a
£
>99
-
-
-
-
••
40
66
88
98
98
98
>99
97
58
100
77
97
>99
97
12
71
_a
a
a
~a
a
a
"a
a
~a
a
"a
a
"a
"a
a
~a
-> QQ
' y y
Note: Blanks indicate insufficient data.
aNegative removal.
Date: 6/23/80
II .10-38
-------
0
01
rt
CT>
\
NJ
CO
\
00
o
TABLE 10-34.
REMOVAL OF TOXIC ORGANIC POLLUTANTS FROM RAW WASTE-
WATER IN THE SECONDARY ALUMINUM SUBCATEGORY [1]
o
CA)
Number of
Toxic pollutant Samples
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
3,3' -Dichlorobenzidine
Arotnatics
Benzene
Chlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthyl ene
Benzo ( a ) pyrene
Benzo ( b ) f luoranthene
Benzo ( k ) f luoranthene
Chrysene
Fluoranthene
Naphthalene
Pyrene
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chi orodibromome thane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroethane
1, 2-Dichloroethane
1 , 2-rrans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Pesticides and metabolites
Isophorone
Note: Blanks indicate insufficient
a
7
7
7
7
7
7
11
11
7
11
7
7
7
7
7
7
7
7
7
11
11
11
11
11
11
11
11
11
11
11
7
data.
Times
Treated
effluent
concentration, pg/L
detected Range
7
1
4
1
2
0
1
1
0
1
1
0
1
1
1
1
0
1
1
2
1
3
7
4
1
2
3
2
1
1
2
0
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
1,200
2.0
50
3.0
100
5.0
7.0
6.0
2.0
1.0
2.0
2.0
2.5
1.0
1.0
4.7
6.0
29
170
18
7.0
20
75
200
1.0
5.0
8.5
Median Mean
5.3 290
0.
13
0.
15
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
4.
32
3.
0.
2.
1.0 9.
18
0.
0.
2.
6
6
7
5
5
3
1
3
3
4
1
1
0
5
9
0
6
3
2
1
5
3
Average
percent
removal
24
97
19
94a
>99
93a
a
1
a
^j
>99
95a
£
99
>99
50
3
50
a
a
a
a
52a
^
a
a
>99
-------
o
0)
rt-
(D
co
oo
o
TABLE 10-35.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW WASTEWATER IN
THE PRIMARY COLUMBIUM AND PRIMARY TANTALUM SUBCATEGORIES [1J
o
i
Number of
Toxic pollutant
Times
Samples detected
Treated effluent
concentration, yg/L
Range
Median Mean
Phthalates
Bis(2-ethylhexyl) phthalate 4
Butyl benzyl phthalate 4
Di-n-butyl phthalate 4
Diethyl phthalate 4
Dimethyl phthalate 4
Di-n-octyl phthalate 4
Phenols
Pentachlorophenol 2
Aromatics
Benzene 7
Chlorobenzene 7
2,4-Dinitrotoluene 4
2,6-Dinitrotoluene 4
Ethylbenzene 7
Nitrobenzene 4
Toluene 7
1,2,4-Trichlorobenzene 4
Polycyclic aromatic hydrocarbons
Acenaphthene 4
Acenaphthylene 4
Anthracene 4
Benz(a)anthracene 4
Benzo(a)pyrene 4
Benzo(b)fluoranthene 4
Benzo(ghi)perylene 4
Benzo(k)fluoranthene 4
2-Chloronaphthalene 4
Chrysene 4
Dibenz(ah)anthracene 4
Fluoranthene 4
Fluorene 4
Indeno(l,2,3-cd)pyrene 4
Naphthalene 4
Phenanthrene 4
Pyrene 4
3
0
1
1
2
1
2
1
0
0
2
0
3
3
3
1
1
0
0
1
1
1
0
0
0
0
1
0
0
1
1
ND - 9.5
ND
ND
ND
ND
- 9.0
- 2.0
- 20
- 2.0
ND - 40
ND - 65
ND - 49
ND - 17
ND - 16
ND - 2.8
ND - 12
ND - 2.0
ND - 1.0
ND - 2.0
ND - 69
ND - 12
ND - 4.9
2.8
7.5
6.9
0.9
1.5
1.5
0.4
3.8
2.2
0.5
5.0
0.5
6.9
13
7.0
8.9
7.4
1.2
3.8
0.5
0.2
0.5
17
3.8
1.4
Average
percent
removal
97
>99
82
71.
92
>99
_a
"a
>99
>99.
64
a
"a
>99
>99
C
0.
>99
>99
>99
>99
C
>99
>99
(continued)
-------
o
0)
ft
TABLE 10-35 (continued)
CO
\
00
o
o
i
Toxic pollutant
Polychlorinated biphenyls and
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chlorodibromomethane
Chloroform
Dichlorobromome thane
1 , 2-Dichloroethane
1, 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Hexachloroethane
Methylene chloride
1,1,2, 2-Tetrachloroe thane
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
P-BHC
6-BHC
Y-BHC
Chlordane
4,4' -DDE
4,4' -DDT
Dieldrin
a-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
I sophorone
Toxaphene
Number of
Times
Samples detected
related
3
3
7
7
7
7
7
7
7
7
4
7
7
7
7
7
7
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
3
compounds
0
0
0
3
1
4
2
3
3
0
0
2
2
5
0
1
3
1
1
1
1
0
1
0
0
1
0
0
1
0
1
0
1
0
Treated
effluent
concentration, M9/L
Range
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 110
- 5.0
- 47
- 16
- 18
- 140
- 600
- 190
- 190
- 5.0
- 190
- 0.5
- 0.01
- 0.3
- 0.5
- 1.0
- 0.01
- 0.01
- 0.3
Median Mean
21
0.7
9.0
2.3
3.0 5.9
21
85
10 54
10 54
32
0.2
0.1 0.1
0.2
0.1
Average
percent
removal
>99
>99
>99
a
87
a
>99
55
a
>99
>99
98a
a
>99
a
33
75
33
_a
>99
90
>99
3
>99
Note: Blanks indicate insufficient data.
a
-------
TABLE 10-36.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATERS IN THE PRIMARY COPPER SUBCATEGORY [1]
Number of
Toxic pollutant
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Samples
5
5
5
5
Times
detected
5
2
3
2
Treated effluent
concentration, pg/L
Range
ND -
ND -
ND -
ND -
480
48
73
190
Median Mean
17 110
9.6
25
38
Average
percent
removal
a
Phenols
2,4-Dimethylphenol
Aromatics
>99
Benzene
Chlorobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Chrysene
Fluoranthene
Fluorene
Phenanthrene
Pyrene
Polychlonnated biphenyls and
related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Carbon tetrachloride
Chi or odlbromome thane
Chloroform
Dichlorobromome thane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
p-BHC
y-BHC
Chlordane
4,4' -DDE
4,4' -DDT
Dieldrin
or-Endosulfan
p-Endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
0
0
0
0
4
0
1
1
1
1
0
1
1
0
0
0
0
0
2
0
1
1
2
0
1
1
1
1
1
1
0
1
0
1
1
1
1
1
0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 1.
- 6.
- 17
- 2.
- 2.
- 14
- 17
- 1.
- 1.
- 10
- 9.
- 3.
- 10
- 3.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
- 0.
0
0
0
0
0
5
0
0
0
2
01
9
1
1
04
2
1
4
2
1
0
1
6
0
0
2
3
1.0 0
0
3
3
1
3
0
0
0
.4
.2
.2
.4
.4
.8
.4
.8
.5
.8
.2
.0
.4
.6
.2
.1
43
a
>99
>99
0
>99
a
a
~a
52
>99
a
a
>99
>99
>99
>99
>99
a
>99
a
81
a
>99
60
a
£»
a
0
>99
>99
Note: Blanks indicate insufficient data.
Negative removal.
Date: 6/23/80
11.10-42
-------
TABLE 10-37.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATER IN THE SECONDARY COPPER SUBCATEGORY [1]
Number of
Times
Treated
effluent
concentration, yg/L
Toxic pollutant Samples detected Range
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
. Di-n-octyl phthalate
Aromatics
Benzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzol a Jpyrene
Benzo(b) fluoranthene
Benzo( k ) fluoranthene
Chrysene
Dibenz ( ah ) anthracene
Fluoranthene
Fluorene
Indeno( 1,2, 3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and
related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Dichl or obromome thane
1 , 2-Dichloroethane
1, 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites
Aldrin
o-BHC
P-BHC
6-BHC
Y-BHC
Chlordane
4,4' -DDE
4,4' -ODD
4,4' -DDT
Dieldrin
o-Endosulfan
p-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
Note: Blanks indicate insufficient
aNegative removal .
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
13
data.
2
3
2
2
2
2
1
1
1
0
2
1
0
5
1
1
1
2
0
2
3
1
1
5
4
1
1
2
5
1
1
0
0
0
2
2
1
0
1
1
1
0
1
1
1
1
1
1
1
1
1
1
1
0
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
590
23
110
82
1.3E3
170
36
2.0
220
1.0
69
36
36
140
9.0
12
12
8.0
8.0
17
100
8.0
930
140
38
260
320
7.0
1.0
14
12
2.0
0.2
0.2
0.01
0.1
0.5
0.1
0.04
0.1
0.2
0.6
0.1
0.1
0.4
0.2
0.1
Median Mean
34.0 84
3.3
16.0 32
15
1.0 210
15
2.8
0.2
30
5.6
2.8
2.8
5.0 19
1.5
0.8
0 . 6
2.0 3.9
23
0.6
87
5.0 19
3.0 7.8
20
43
0.5
2£
. b
1.7
0.2
0.1
0.1
0.1
0.1
0.1
Average
percent
removal
92
38
*!•
"a
"a
85
50
'!•
a
39
>99
"a
>99a
~
99a
8?a
99
99
f n
60
60
_a
6?>
>99
v QQ
> yy
•> QQ
>99a
"
81
97
0
Date: 6/23/80
11.10-43
-------
rt
fD
CTi
to
CD
O
o
i
TABLE 10-38. REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATER IN THE PRIMARY LEAD SUBCATEGORY [1]
Toxic pollutant
Polycyclic aromatic hydrocarbons
Pyrene
Halogenated aliphatics
Methylene chloride
Number of
Times
Samples detected
1 0
1 1
Treated effluent Average
concentration, pg/L percent
Range Median Mean removal
>99
54 54 -a
Note: Blanks indicate insufficient data; not calculable.
aNegative removal.
-------
TABLE 10-41.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATERS IN THE PRIMARY TUNGSTEN SUBCATEGORY [1]
Number of
Toxic pollutant Samples
Phthalates
Bis ( 2-ethylhexyl ) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
-Di-n-octyl phthalate
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
1,2, 4-Tnchlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzol a (pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and
related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Chi or odlbromome thane
Chloroform
Dichl or obromome thane
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
P-BHC
y-BHC
Chlordane
4,4' -ODD
4. 4 '-DDT
Dieldrin
o-Endosulfan
p-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
2
2
2
2
2
4
4
4
2
4
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
4
4
4
4
4
4
4
4
4
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Times
Treated effluent
concentration, pq/L
detected Range
2
2
2
2
2
2
1
1
1
1
1
0
0
1
1
0
1
0
2
1
2
1
1
0
0
3
2
3
3
1
1
2
0
4
0
0
0
1
1
1
0
0
1
1
0
0
0
0
1
32 -
22 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
4.0 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
3.0 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
730
66
16
230
43
17
1.0
1.0
5.5
1.0
55
B.O
1.0
1.0
32
e.o
15
2.4
1.9
870
12
29
29
2.0
9.0
20
68
0.1
0.5
0.2
0.6
0.2
6.0
Median Mean
380
44
8.0
120
22
7.5 8.0
0.3
2 .8
0.3
4.8
4 .0
0.5
0.5
16
4.0
7.5
1.2
1.0
29 230
6.0 6.0
7.5 11
10 12
0.5
5.3 5.0
7.0 9.3
41
0.3
0.1
0.3
0.1
3.0
Average
percent
removal
a
"a
"a
"a
"a
a
"•
9!«
>99
>99
87a
>99a
-
>99
"•
Q
a
a
>99
Q
3
3
3
a
4
54
>99a
—
>99
>99
>99
>99a
-
-
>99
91
97
>99
>99
>99
>99
Note: Blanks indicate insufficient data.
Negative removal.
Date: 6/23/80
11.10-47
-------
TABLE 10-42.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATER IN THE PRIMARY ZINC SUBCATEGORY [1]
Number of
Toxic pollutant
Samples
Times
detected
Treated effluent
concentration, |jg/L
Range
Average
percent
Median Mean removal
Phthalates
Bis(2-ethylhexyl) phthalate 11
Butyl benzyl phthalate 11
Di-n-butyl phthalate 11
Diethyl phthalate 11
Dimethyl phthalate 11
Di-n-octyl phthalate 11
Nitrogen compounds
3,3'-Dichlorobenzidine 11
Phenols
Pentachlorophenol 11
ND - 170
ND - 0.1
ND - 12
ND - 0.9
ND - 1.0
ND - 2.0
14
4.0
Note: Blanks indicate insufficient data.
aNegative removal.
22
1.6
0.1
0.1
0.2
21
56
96
96
>99
Aromatics
Benzene
Ethylbenzene
Hexachlorobenzene
Toluene
1,2, 4 -Tri chlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and
related compounds
Aroclor 1246
Aroclor 1254
Halogenated aliphatics
Bromoform
Chloroform
1 , 1-Dichloroethane
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
Methylene chloride
Tetrachloroethylene
Tri chloroethylene
Trichlorofluorome thane
Pesticides and metabolites
or-BHC
P-BHC
Chlordane
4, 4 '-DDE
4, 4' -DDT
Dieldrin
Heptachlor
Heptachlor epoxide
I sophorone
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
1
1
0
1
2
1
1
1
0
1
1
1
1
1
2
2
2
0
0
0
1
2
2
0
1
1
1
1
1
1
1
1
0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 3.0
- 6.0
- 5.3
- 47
- 8.0
- 9.0
- 0.7
- 3.0
- 6.0
- 9.0
- 8.0
- 9.8
- 7.0
- 44
- 54
- 7.0
- 22
- 19
- 0.7
-0.03
- 1.6
- 0.2
- 0.4
-0.03
- 0.7
- 0.7
0.4
3.0 0.8
4.3
0.7
7.0 1.6
0.3
0.5
1.4
0.9
0.9
0.6
4.0
5.4
0.8
2.6
2.0
0.1
0.2
0.01
0.03
0.1
0.1
85a
>99
89a
a
65
>99
81a
3
72
6a
a
3
66
>99
>99
>99
>99g
—
89
>99
£
3
£|
3
3
a
>99
Date: 6/23/80
11.10-48
-------
TABLE 10-39.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATERS IN THE SECONDARY LEAD SUBCATEGORY [I]
Number of
Toxic pollutant Samples
Phthalates
Bis(2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Benzidine
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Benzo( a (pyrene
Benzo(b ) f luoranthene
Benzo(ghi )perylene
Benzof k ) f luoranthene
Chrysene
Fluoranthene
Fluorene
Indeno(l,2 3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and
related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-7'ra/is-dichloroethylene
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 2-Trichloroe thane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
P-BHC
Y-BHC
Chlordane
4,4' -DDE
4,4' -DDT
Dieldrin
o-Endosulfan
p-Endosulfan
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Isophorone
Note: Blanks indicate insufficient
a.
4
7
7
7
4
7
4
4
4
4
4
4
7
7
7
7
7
7
7
7
7
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
data.
Times
Treated effluent
concentration.
detected Range Median
4
1
2
0
1
0
1
0
1
0
1
0
1
0
0
1
0
1
0
0
0
1
1
0
1
1
0
4
1
2
2
0
1
1
2
0
1
1
1
1
1
1
1
0
1
0
0
1
1
0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-22 9.5
- 4.0
-35 1.5
- 2.0
- 7.0
- 4.0
- 1.0
- 2.0
- 1.0
- 2.0
- 3.0
- 2.0
- 1.9 1.3
- 1.6 1.0
- 32
- 2.0
- 17
- 22
- 3.0
- 7.2
- 28
-0.04
- 0.3
- 0.02
- 31 9.0
- 0.02
- 0.1
- 0.4 0.2
- 0.1
- 0.3
- 0.1
pg/L
Mean
5.5
1.0
9.5
0.5
1.0
0.6
0.3
0.5
0.3
0.5
0.8
0.5
1.1
0.9
4.6
0.3
2.4
3.1
0.6
1.0
4.7
0.1
4.6
0.1
0.1
Average
percent
removal
97
94
21
>99
78
>99
£
>99a
-
>99fl
-
>99
88
>99
>99a
-
>99
99
>99
>99
>99
0
89
>99
36
15
>99
-
93a
3
>99
45a
-
0
a
>99
>99
0
>99
>99
Date: 6/23/80
11.10-45
-------
TABLE 10-40.
REMOVABILITY OF TOXIC ORGANIC POLLUTANTS FROM RAW
WASTEWATER IN THE SECONDARY SILVER SUBCATEGORY [1]
Number of
Toxic pollutant Samples
Phthalates
Bis ( 2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Di-n-octyl phthalate
Aromatics
Benzene
Chlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthene
Anthracene
Fluoranthene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and
related compounds
Aroclor 1248
Aroclor 1254
Halogenated aliphatics
Bromoform
Carbon tetrachloride
Chlorodibromomethane
Chloroform
Dichlorobromomethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
a-BHC
^-BHC
6-BHC
Y-BHC
Chlordane
4,4' -DDE
4,4' -ODD
4,4' -DDT
Dieldrin
Endrin
Endrin aldehyde
Heptachlor
5
5
5
5
5
9
9
9
9
5
5
5
5
5
5
2
2
9
9
9
9
9
9
9
9
8
9
9
9
2
2
2
2
2
2
2
2
2
2
2
2
2
Times
detect*
5
3
2
0
3
5
1
3
2
0
0
2
0
0
2
1
1
2
6
1
6
4
4
2
3
3
6
1
4
1
1
1
1
0
1
1
1
1
1
1
1
1
Treated
effluent
concentration, pg/L
id Range
3.4 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
0.2 -
0.3 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
0.01 -
ND -
ND -
ND -
ND -
0.02 -
ND -
ND -
ND -
0.01 -
120
52
79
69
59
4.0
14
19
200
180
2.6
1.9
13
1,700
2,800
2,900
240
3,400
44
790
25
35
5.0
330
0.1
0.04
0.03
0.1
0.01
0.01
0.03
0.1
0.2
0.5
0.04
Median Mean
17 37
1.0 18
7.0 19
16
14
0
3
2
40
36
1
1
1
19 310
750
130 440
2.0 48
390
4
160
5
8
0
51
0
0
0
.4
.9
.7
.4
.1
.4
.9
.9
.3
.6
.1
.1
.2
Average
percent
removal
_a
_a
75
>99
47
81
86
58
87
>99
>99
a
>99
>99
92
a
_a
87
26,
_a
~a
4
60
65
-
84
26
81
92
86
>99
>99
86
-
Note: Blanks indicate insufficient data.
Negative removal.
Date: 6/23/80
11.10-46
-------
II.10.5 References
1. Draft Development Document for Effluent Limitations Guide-
lines and Standards for the Nonferrous Metals Manufacturing
Point Source Category, Effluent Guidelines Division, Office
of Water and Waste Management, U.S. Environmental Protection
Agency, September, 1979.
2. NRDC Consent Decree Industry Summary - Nonferrous Metals
Manufacturing Industry.
3. Environmental Protection Agency - Effluent Guidelines and
Standards for Nonferrous Metals. 40 CFR 421; 39 FR 12822,
April 8, 1974; Amended by 40 FR 8514, February 27, 1975;
40 FR 48348, October 15, 1975; 41 FR 54850, December 15,
1976.
Date: 6/23/80 11.10-49
-------
11.11 ORE MINING AND DRESSING
II.11.1 INDUSTRY DESCRIPTION [1]
II.11.1.1 General Description
Subgroups of the metal mining industries are identified as major
group 10 in the Standard Industrial Classification (SIC) Manual,
which includes establishments engaged in mining ores for the
production of metals, and includes all ore dressing and benefici-
ating operations, whether performed at mills operating in con-
junction with the mines served or at mills operated separately.
These include mills which crush, grind, wash, dry, sinter, or
leach ore, or perform gravity separation or flotation operations.
As mined, most ores contain the valuable metals whose recovery
is sought, disseminated in a matrix of less valuable rock called
gangue. The purpose of ore beneficiation is the separation of
the metal-bearing minerals from the gangue to yield a product
that is higher in metal content. To accomplish this, the ore
must generally be crushed and/or ground small enough for each
particle to contain either the mineral to be recovered or mostly
gangue. Separation of the particles on the basis of some dif-
ference between the ore mineral and the gangue can then yield a
concentrate high in metal value, as well as waste rock (tailings)
containing very little metal. The separation is never perfect,
and the degree of success attained is generally described by two
parameters: (1) percent recovery, and (2) grade of the concen-
trate. Widely varying results are obtained in beneficiating
different ores; recoveries may range from 60% or less to greater
than 95%. Similarly, concentrates may contain less than 60% or
more than 95% of the primary ore mineral. In general, for a
given ore and process, concentrate grade and recovery are inverse-
ly related. (Higher recovery is achieved only by including more
gangue, yielding a lower grade concentrate.)
Many properties are used as the basis for separating valuable
minerals from gangue, including specific gravity, conductivity,
magnetic permeability, affinity for certain chemicals, solubility,
and the tendency to form chemical complexes. Separation pro-
cesses in general use are gravity concentration, magnetic separ-
aration, electrostatic separation, flotation, and leaching.
Amalgamation and cyanidation, which are variants of leaching,
deserve special mention. Solvent extraction and ion exchange are
Date: 6/23/80 II.11-1
-------
widely applied techniques for concentrating metals from leaching
solutions, and for separating them from dissolved contaminants.
All of these processes are discussed in general terms in the
paragraphs that follow. This discussion is not meant to be all-
inclusive; rather, its purpose is to discuss the primary process-
es in current use in the ore mining and milling industry.
Gravity-concentration processes utilize the differences in dens-
ity to separate valuable ore minerals (values) from gangue.
Several techniques (e.g., jigging, tabling, spirals, and sink/
float separation) are used to achieve the separation. Each is
effective over a somewhat limited range of particle sizes, the
upper bound of which is set by the size of the apparatus and the
need to transport ore within it, and the lower bound by the point
at which viscosity forces predominate over gravity and render the
separation ineffective. Selection of a particular gravity-based
process for a given ore will be strongly influenced by the size
to which the ore must be crushed or ground to separate values
from gangue, as well as by the density difference and other
factors.
Ores can be leached by dissolving away either gangue or values
in aqueous acids or bases, liquid metals, or other special
solutions. The examples below illustrate various leaching
possibilities.
(1) Water-soluble compounds of sodium, potassium, and boron
can be mined, concentrated, and separated by leaching
with water and recrystallizing the resulting brines.
(2) Vanadium and some other metals form anionic species
that occur as insoluble ores. Roasting of such insolu-
ble ores with sodium compounds converts the values to
soluble sodium salts. After cooling, the water-soluble
sodium salts are removed from the gangue by leaching
in water.
(3) Uranium ores are only mildly soluble in water, but they
dissolve quickly in acid or alkaline solutions.
(4) Native, finely divided gold is soluble in mercury and
can be extracted by amalgamation (i.e., leaching with a
liquid metal). One process for nickel concentration in-
volves reduction of the nickel using ferrosilicon at a
high temperature and extraction of the nickel metal
into molten iron. This process, called skip-lading, is
related to liquid-metal leaching.
(5) Certain solution (e.g., potassium cyanide) dissolve
specific metals (e.g., gold) or their compounds, and
leaching with such solutions immediately concentrates
the values.
Date: 6/23/80 II.11-2
-------
In the amalgamation process, mercury is alloyed with some other
metal to produce an amalgam. The process is applicable to free
milling precious-metal ores, those in which the gold is free,
relatively coarse, and has clean surfaces. Lode or placer gold/
silver that is partly or completely filmed with iron oxides,
greases, tellurium, or sulfide minerals cannot be effectively
amalgamated. Hence, prior to amalgamation auriferrous ore is
typically washed and ground to remove any films on the precious-
metal particles. Although the amalgamation process has been used
in the past extensively for the extraction of gold and silver
from pulverized ores, it has largely been superseded in recent
years by the cyanidation process owing to environmental
considerations.
In the cyanidation process, gold and/or silver are extracted
from finely crushed ores, concentrates, tailings, and low-grade
mine-run rock in dilute, weakly alakaline solutions of potassium
or sodium cyanide. The gold is dissolved by the solution and
subsequently sorbed onto activated carbon ("carbon-in-pulp"
process) or precipitated with metallic zinc. The gold particles
are recovered by filtering, and the filtrate is returned to the
leaching operation.
Ion exchange and solvent extraction processes are used on preg-
nant leach solutions to concentration values and to separate the
from impurities. Ion exchange and solvent extraction are based
on the same principle: polar organic molecules tend to exchange
a mobile ion in their structure [typically, Cl~, N05, HSOs, or
COa (anions) or H-f or Na+ (cations) ] for an ion with a greater
charge or a smaller ionic radius.
Table 11-1 presents industry summary data for the Ore Mining and
Dressing point source category in terms of the total number of
subcategories, the number of subcategories studies by EGD, and
the number and types of dischargers [1-3].
TABLE 11-1. INDUSTRY SUMMARY [1-3]
Industry: Ore Mining and Dressing
Total Number of Subcategories: 7
Number of Subcategories Studied: 7
Number of Dischargers in Industry: Undefined
• Direct: 750
• Indirect: 0
• Zero: No definition for this industry
Table 11-2 presents current BPT limitations for each subcategory
in the Ore Mining and Dressing Industry.
Date: 6/23/80 II.11-3
-------
TABLE 11-2.
BPT LIMITATION REGULATIONS FOR THE
ORE MINING AND DRESSING INDUSTRY [4]
Subcategory
Iron ore
Mines and mine drainage
Physical/chemical benef iciation
Magnetic/physical benef iciation
Aluminum ore
Base and precious metals
Open pit and underground mines
Froth flotation process
Amalgamation process
Gravity separation
Uranium
Mine drainage
Mills using acid leach, alkaline
leach, combined leaching, in-
cluding mill-mine in-eitu
leaching
TSS
Fe
TSS
Fe
PH
TSS
Fe
Al
pH
TSS
Cu
Zn
Pb
Hg
pH
TSS
Cu
Zn
Pb
Hg
Cd
pH
TSS
Cu
Zn
Hg
PH
TSS
COD
Ra
Ra
U
Zn
pH
TSS
COD
A5
Ra
Ra
NH3
Parameter
(dissolved)
(dissolved)
(= 6 to 9)
No
(= 6 to 9)
(= 6 to 9)
(= 6 to 9)
(= 6 to 9)
226 (dissolved)
226 (total)
(= 6 to 9)
226 (dissolved)
226 (total)
Maximum
for 1 day,
mg/L
30
2.0
30
2.0
discharge3
30
1.0
2.0
30
0.30
1.5
0.6
0.002
30
0.3
1.1
0.6
0.002
0.1
30
0.3
1.0
0.002
30
200
10r
30C
4
1.0
30
1.0
IOC
30C
30-Day
average ,
mg/L
20
1.0
20
1.0
20
0.5
1.0
20
0.15
0.75
0.3
0.001
20
0.15
0.5
0.3
0.001
0.005
20
0.15
0.5
0.001
20
100
3C
2
2
0.5
20
500
p
3C
10C
100
pH (=6 to 9)
(continued)
Date: 6/23/80
II.11-4
-------
TABLE 11-2 (continued)
Subcategory
Parameter
Maximum
for 1 day,
mg/L
30-Day
average,
mg/L
Ferralloy
Mine drainage from mines producing
5,000 metric ton/yr
Drainage from mines producing
less than 5,000 metric tons/yr
and mills processing less than
5,000 metric ton/yr
Drainage from mills processing
greater than 5,000 metric/ton yr
using froth flotation
Mercury
Mine drainage
Mills - gravity separation
Mills - froth separation
Metal ore not elsewhere classified
Titanium
TSS
Cd
Cu
Zn
Pb
As
pH (= 6 to 9)
TSS
pH (= 6 to 9)
TSS
Cd
Cu
Zn
As
CN
pH {= 6 to 9)
TSS
Hg
Ni
pH (= 6 to 9)
30
0.
0.
1.0
0.6
1.0
50
30
0.1
0.3
0.2
30
0.002
0.2
20
0.005
0.015
0,
0.
0.
30
20
0.05
0.15
0.5
0.05
0.1
20
0.001
0.1
Mine drainage
Mill benef iciating using
electrostatic, magnetic,
physical, or flotation
methods
Mine drainage from dredge
mining
TSS
Fe
pH (= 6 to 9)
TSS
Zn
Ni
pH (= 6 to 9)
TSS
Fe
pH (- 6 to 9)
30
2
30
1.0
0.2
30
2
20
1
20
0
0
20
1
.5
.1
No discharge from mines and mills that employ dump, heap, in-situ leach, or vat
leach process to extract copper or ore waste. No discharge from gold or silver
mills that use the cyanidation process. Discharge is allowed if rainfall exceeds
evaporation in the discharge area. Volume of discharge allowed is equal to the
amount needed to equalize rainfall and evaporation.
No BPT regulations promulgated for this process.
"Picocuries/L.
Discharge is allowed, if rainfall exceeds evaporation in the discharge area.
Volume of discharge allowed is equal to the amout needed to equalize rainfall
and evaporation.
Date: 6/23/80
II.11-5
-------
II.11.1.2 Subcategory Descriptions
Based on similarities in types of processing, technology,
wastewater, end products, and other factors, the following
subcategories of the Ore Mining and Dressing Industry were
established [1,2]:
• Iron Ore (SIC Code 1011)
• Aluminum (SIC Code 1051)
• Base and Precious Metals (SIC Codes 1021, 1031, 1041, and
1044)
• Uranium (SIC Code 1094)
• Ferroalloy (SIC Code 1061)
• Mercury (SIC Code 1092)
• Metal Ore Not Elsewhere Classified (SIC Code 1099)
Subcategory 1 - Iron Ore
This subcategory covers mining and/or milling operations involved
in the excavation and extraction of iron ore.
Subcategory 2 - Aluminum (Bauxite)
The bauxite mining industry is classified as SIC 1051, which in-
cludes establishments engaged in mining and milling bauxite and
other aluminum ores. However, no other aluminum ores are being
commercially exploited on a full-scale basis at present, and the
bauxite mining industry serves as the sole representative of SIC
1051.
Subcategory 3 - Base and Precious Metals
This subcategory encompasses the mining and milling of copper,
zinc, lead, gold, and silver, falling under SIC Codes 1021, 1031,
1041, and 1044.
Subcategory 4 - Uranium
The factors evaluated in consideration of subcategorization of
the uranium, radium, and vanadium mining and ore dressing indus-
try are: end product, type of processing, ore mineralogy, waste
characteristics, treatability of wastewater, climate, rainfall,
and location. Based upon an intensive literature search, plant
inspections, NPDES permits, and communications with the industry,
this category is categorized by milling process and mineralogy
(and, thus, product). The milling processes of this industry in-
volve complex hydrometallurgy. Such point discharges as might
occur in milling processes (i.e., the production of concentrate)
are expected to contain a variety of pollutants that need to be
limited. Mining for the ores is expected to lead to a smaller
set of contaminants. While mining or milling of ores for uranium
Date: 6/23/80 II.11-6
-------
or radium produces particularly noxious radioactive pollutants,
these are largely absent in an operation recovering vanadium only.
Subcategory 5 - Ferroalloy
A tentative subcategorization of the industry was developed after
collection and review of initial data, based primarily on end
product (e.g., tungsten, molybdenum, manganese, etc.), with fur-
ther division on the basis of process, in some cases. Further
data, particularly chemical data on effluents and more complete
process data for past operations, indicated th.at process was the
dominant factor influencing wastestream character and treatment
effectiveness. Examination of the industry additionally showed
that size of operation could also be of great importance. Other
factors, except as they are reflected in or derived from the
above, are not believed to warrant industry subcategorization.
Subcategory 6 - Mercury
The mercury industry in the United States currently is at a re-
duced level of activity due to depressed market prices. Two
facilities were found to be operating at present, although it is
thought that activity will increase with increasing demand and
rising market prices. The decreased use of mercury due to strin-
gent air and water pollution regulations in the industrial sector
may be offset in the future by increased demand in dental, elec-
trical, and other uses. Historically, little beneficiating of
mercury ores has been known in the industry. Common practice for
most producers (since relatively low production characterizes rrvosi
operators) has been to feed the cinnabar-rich ore directly to a
kiln or furnace without beneficiation. Water use in most of the
operations is at a minimum.
Subcategory 7 - Metal Ore Not Elsewhere Classified
This group of metal ores was considered on a metal-by-metal basis
because of the wide diversity of mineralogies, processes of ex-
traction, etc. Most of the metal ores in this group do not have
high production figures and represent relatively few operations.
For this entire group, ore mineralogies and type of process
formed the basis of subcategorization. The metals ores examined
under this category are ores of antimony, beryllium, platinum,
tin, titanium, rare earths (including monazite), and zirconium.
II. II.2 WASTEWATER CHARACTERIZATION [1]
The wastewater situation evident in the mining segment of the
ore mining and dressing industry is unlike that encountered in
most other industries. Usually, industries (such as the milling
segment of this industry) utilize water in the specific processes
they employ. This water frequently becomes contaminated in the
process and must be treated prior to discharge. In the mining
segment, process water is not normally utilized in the actual
Date: 6/23/80 II.11-7
-------
mining of ores, except where it is used in placer mining opera-
tions (hydraulic mining and dredging) and in dust control.
Water is a natural feature that interferes with mining activities.
It enters mines by groundwater infiltration and surface runoff
and comes into contact with materials in the host rock, ore, and
overburden. An additional source of water in deep underground
mines is the water that results from the backfilling of slopes
with the coarse fraction of the mill tailings. Transportation of
these sands underground is typically accomplished by sluicing.
Mill wastewater is usually the source of the sluice water. The
mine water then requires treatment depending on its quality
before it can be safely discharged into the surface drainage
network. Generally, mining operations control surface runoff
through the use of diversion ditching and grading to prevent, as
much as possible, excess water from entering the working area.
The quantity of water from an ore mine thus is unrelated, or only
indirectly related, to production quantities.
Water is used in the ore mining and dressing industry for several
principal uses under three major categories:
(1) Noncontact cooling water
(2) Process water: wash water
transport water
scrubber water
process and product consumed water
(3) Miscellaneous water: dust control
domestic/sanitary uses
washing and cleaning
drilling fluids
Noncontact cooling water is defined as cooling water that does
not come into direct contact with any raw material, intermediate
product, by-product, or product used in or resulting from the
process. Process water is defined as that water which, during
the beneficiation process, comes into direct contact with any
raw material, intermediate product, by-product, or product used
in or resulting from the process.
Wastewater characteristics for the Ore Mining and Dressing Indus-
try in general reflect the diversity of the mining and milling
operations associated with the various ores mined and processed.
Each ore exhibits its own particular set of waste characteristics,
as shown in Table 11-3. The peculiarities were, in part, criteria
used to determine the various subcategories.
Table 11-3 presents available data, by subcategory, for raw waste-
water pollutant concentrations for subcategories 1, 3, 4, 5, and
6 [1]. Data for subcategory 2, aluminum, have been excluded
because they are extremely limited. Subcategory 7, Metal Ore Not
Elsewhere Classified, has been excluded because of the small size
Date: 6/23/80 II.11-8
-------
TABLE 11-3.
RAW WASTWATER POLLUTANT CONCENTRATIONS
BY SUBCATEGORY [1]
Parameter
Conventional , mg/L
PH8
COD
TSS
TDS
Inorganics, yg/L
Fe, total
Fe, dissolved
Manganese
Number
of
mines Range
8
e
8
B
e
8
8
7.2
1.0
<1
120
<20
<20
<20
-
-
-
-
-
-
-
Median
Number
of
mills
Range
Median
Subcategory 1 - Iron Ore
8.4
48
48
1,300
4,500
80
3,200
7"5b
17h
13b
500
9°°K
30h
400b
6
7
7
7
7
7
7
Subcategory 3 - Base and Precious Metal
Conventional, mg/L
PH3
COD
TOC
TSS
TDS
Oil and grease
Toxic inorganics, yg/L
Antimony
Arsenic
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Other inorganics, yg/L
Aluminum
Boron
Cobalt
Gold
Iron
Manganese
Molybdenum
Strontium
7
7
7
7
7
7
7
7
7
7
7
7
6
7
7
7
7
7
7
7
3.5
4
2.3
2
450
<1.0
<20
<10
500
<50
<0.1
<50
<3
<50
10
<50
<400
<50
<200
90
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
9.6
39
31
40
29,000
17
<500
<70
92 , 000
<500
78
240
96
170,000
2,200
1,900
2,000,000
100,000
<500
120,000
Subcategory 3 - Base
Conventional, mg/L
PH3
COD
TOC
TSS
TDS
Oil and grease
Toxic inorganics, yg/L
Cadmium
Chromium
Copper
Lead
Mercury
Zinc
Other inorganics, yg/L
Iron
Manganese
8
8
8
8
8
8
8
8
8
8
4
8
8
8
3.0
<10
<1
<2
260
0
<2
<20
<20
100
<0.1
30
<20
<20
-
-
-
-
-
-
-
-
-
-
-
-
-
-
8.1
630
11
1,000
1,700
29
80
420
2,100
4,900
0.1
38,000
22,000
57,000
7.0
<10
10
8
2,200
1
<500
<70
5,300
<100
0.5
<100
25
2,800
100
60
6,000
1,400
<500
830
4
4
4
4
1
2
4
4
4
4
1
1
1
4
1
1
1
4
1
1
1
and Precious Metals,
5
3
3
3
3
3
3
3 2
3
7.3 -
<1.0 -
12 -
200 -
400 -
<20 -
32 -
9.5
23
55
2,400
1,200,000
160
330,000
8.2C
12
28
b
b
670b
210,000
60
110,000
b
b
b
s , Copper
110
8.1 -
,000 -
400 -
<0.05 -
150
4
550
<20 -
,000 -
<10 -
<10 -
0.6 -
,800 -
,000 -
10
470,000
4,300
1
<70
910,000
170
21,000
6.0
310,000
19,000,000
8.9
350,100
2,700
<0.6
<500
<50
270,000
10
1,400
2.0
2,800
<3.0
<100
8,100
<500
1,680
<50
7,700,000
31,000
29,000
1,200
Lead/Zincd'e
21
1
9
4
76
160
,900
300
7.9 -
,000 -
,200 -
,800 -
,800 -
,000 -
,000 -
,000 -
,000 -
11
270,000
16,000
40,000
500,000
560,000
3,000,000
35,000,000
570,000
(continued)
Date: 6/23/80
II.11-9
-------
TABLE 11-3 (continued)
Parameter
Convention, mg/L
PH4
COD
TOC
TSS
TDS
Oil and grease
Toxic inorganics , pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Other inorganics , ug/L
Aluminum
Barium
Boron
Calcium
Iron (total)
Magnesium
Manganese
Molybdenum
Potassium
Sodium
Strontium
Tellurium
Titanium
Vanadium
Orgamcs , pg/L
Phenol
Conventional , mg/L
pH3
COD
TOC
TSS
TDS
Oil and grease
TKN
Toxic inorganics, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Number
mines
Subcategory
2
3
1
3
3
3
1
2
1
3
1
3
3
2
1
2
1
1
3
2
1
1
1
3 1
1
2
1
1
1
1
1
1
1
1
Subcategory 3
1
2
2
2
2
2
1
2
2
2
2
2
2
2
2
2
Number
Range
Median mills
3 - Base and Precious Metals
3.3 - 6.2
27 - 3,800
5-81
530 - 4,700
<0.1 - 1.0
30 - 80
<20 - 40
<20 - 1,700
<10 - 440
<100 - 820
60 - 100
<10 - 7,300
140 - <200
,200 - 210,000
140 - 12,000
4.8
35
12
14
1,200
1
<100
60
<2.0
25
<20
56
<10
450
<0.1
80
20
50
2,300
170
<500
180
87,000
25,000
80,000
6,700
<200
44,000
80,000
780
100
<500
0
<10
- Base and Precious Metals,
12 - 20
16 - 17
<2
500 - 620
2-4
<200
<70
<2.0
<20
<100
<20
'10
<100 - 180
0.4 - 2.0
8.0
16
17
<2
560
3
<0.2
<200
<70
<2.0
<20
<100
<20
<10
140
1.2
, Gold
4
4
4
4
3
4
4
4
4
3
4
4
Silver
4
4
4
4
3
4
4
4
4
4
Range
11
12
2
460
50
<10
30
<10
60
1.1
130
<500
f
16
12
2
470
<200
<70
<10
30
<100
0.8
- 220
- 97
- 550,000
- 4,500
- 3,700
- 100
- 200
- 81,000
- <100
- 4.2
- 3,100
- 77,000
- 220
- 29
- 550,000
- 1,200
- 1,850
- 3,500
- 20
- 780
- 560
- 130
Median
110
42
490,000
1,100
<70
<20
480
2,600
<10
4.0
760
1,200
41
23
150,000
770
<200
<70
<20
240
<100
3.0
(continued)
Date: 6/23/80
11.11-10
-------
TABLE 11-3 (continued)
Parameter
Toxic inorganics, ug/L
Nickel
Selenium
Silver
Thallium
Zinc
Toxic organics, ug/L
Phenol
Other inorganics, pg/L
Aluminum
Barium
Boron
Calcium
Iron (total)
Magnesium
Manganese
Molybdenum
Potassium
Sodium
Strontium
Tellurium
Titanium
Vanadium
Parameter
Conventional, mg/L
COD
TOC
TSS
Toxic inorganics, yg/L
Arsenic
Copper
Lead
Nickel
Zinc
Other inorganics, vig/L
Aluminum
Calcium
Iron
Magnesium
Manganese
Molybdenum
Radium
Thorium
Titanium
Uranium
Vanadium
Number
of
mines
(continued)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Number
of
mines
2
2
1
2
2
2
2
2
1
2
2
Range Median
60 - 90
6.8 - 126
<20
<100
<20 - <30
<10
<20
<500 - <600
80 - 110
45,000 - 46,000
330 - 2,100
28,000 - 32,000
430 - 6,300
<200
8,000 - 15,000
7,000 - 12,000
150 - 210
<300
<500
<200
Subcategory 4 -
Range
240 - 600
16 - 25
300
93,000 - 120,000
230 - 470
36,000 - 45,000
500 - 530
2,700,000 - 3,200,000
<100
12,000
500 - 1,000
Number
of
mills
4
2
3
3
4
3
f
Uranium
Range Median
50 - 140 100
140 - 150 150
<20 <20
20 - 370 170
50 - 540 <200
<300 <300
Alkaline process
Number
of
mills
2
2
2
2
2
2
1
1
1
1
2
1
2
2
2
1
1
2
2
Range
28 - 56
<1 - 450
110,000 - 290,000
330 - 1,400
<500 - 1,100
<5 - 690
520
<500
18,000
32,000,000
920 - 1,600
190,000
<200 - 38,000
<300
110,000 - 19,000,000
<100
400
3,900 - 44,000
500 - 17,000
Number
of
mills
1
2
2
2
2
2
1
2
1
1
1
2
2
2
1
2
2
Acid process
Range
64 - 630
6-24
250,000 - 530,000
130 - 2,300
680 - 1,700
840 - 2,100
1,400
<500
740,000 - 1,600,000
220,000
330,000
550,000
110,000 - 210,000
300 - 16,000
230,000 - 690,000
3,000
31,000 - 170,000
120,000 - 130,000
(continued)
Date: 6/23/80
11.11-11
-------
TABLE 11-3 (continued)
Parameter
Conventional, mg/L
pHa
COD
TSS
TDS
Oil and grease
Ammonia
Toxic inorganics, yg/L
Arsenic
Cadmium
Chromium
Copper
Cyanide (total)
Lead
Zinc
Other inorganics, yg/L
Calcium
Iron
Manganese
Molybdenum
Vanadium
Number
of
mines
4
3
2
4
4
4
3
4
4
4
3
Range
4.5 - 7.3
1.0 - 14
0.12 - 0.15
<10 - <70
<5 - 70
<20 - 3,800
60 - 190
50 - 7,000
210 - 6,800
<100 - 500
<500
Subcategory 6
Median
6.8
2.0
0.14
<40
<10
<40
140
90
5,400
' <100
<500
- Mercury '
Number
of
mills
2
4
3
5
5
2
5
5
2
5
4
5
4
1
4
5
5
2
3.5
24
2.30
210
1
0.16
10
<5
20
30
<10
<20
<20
440
190
500
Range
- 8.6
- 170
- 500,000
- 2,600
- 15
- 1.4
- 100
- 740
- 30
- 51,000
- 450
- 9,800
- 27
- 1,500,000
- 57,000
- 18,000
<500
Median
6.1
40
150,000
2,300
3.4
0.78
<70
30
520
<10
<100
50
206,000
24,000
50,000
2,200
<500
Conventional, mg/L
6.5 - 8.2
7.4
Toxic organics, yg/L
Antimony
Arsenic
Cadmium
Copper
Lead
Mercury
Zinc
Other inorganics, yg/L
Iron
Manganese
Tellurium
2
2
1
1
1
1
1
2
2
1
<500 - 3,800 2,200
20 20
420
1,300
580
28,000
140 - 1,000 620
<500 - 2,900,000 1,500,000
7,000 - 50,000 29,000
<80
Values in pH units.
Average value.
Flow range for seven copper mines was 1.08 x 10s to 1.1 x 107 gpd with a median of
8.65 x 10s gpd; flow range for four copper mills was 5.10 x 106 to 7.35 x 107 gpd
with a median of 2.73 x 107 gpd.
The mines concerned use seepage and seepage plus drill cooling water combined.
The form of the data did not permit determination of median values.
Median values not presented for silver mines, uranium mines and mills, and mercury
mills due to insufficient data.
n
Values in picocuries/L.
Water not used; surface and groundwater, if encountered, are not discharged.
Date: 6/23/80
11.11-12
-------
of operations involved, the diversity of this subcategory, and
the lack of specific reference material pertinent to this
classification.
II.11.3 PLANT SPECIFIC DESCRIPTION [1, 2]
Tables 11-4 through 11-13 present pollutant concentrations ob-
served at several mines, mills, and mine/mill complexes through-
out the industry. All subcategories are encompassed. Some data
are screening sampling values, and other data are verification
sampling values. Footnotes with each table indicate the type of
data reported. The tables do not list influent flowrates because
they are not clearly defined for this industry.
Plants were selected by the amount of information available,
treatment process, number of streams, and removal efficiency.
Some plants combine mine and mill wastewaters; this combination
often depends on the location and water reuse rate of the plant.
II.11. 4 POLLUTANT REMOVABILITY
Pollutants in the Ore Mining and Dressing industry originate from
two distinct sources: particles from raw ores, and beneficiation
(dressing) reagents. Pollutants from various ores generally con-
sist of heavy metals contained in the ore. These pollutants are
normally in a natural state as dissolved or suspended particles
resulting from contact with rainwater and seepage water. The
beneficiation or dressing process generally contributes cyanide
or phenols and may result in high volumes of waste loads when
combined with the natural pollutants.
In-process recycle of wastestreams after thickening or filtering
is used at several plants within the industry. Water also may be
recovered by dewatering tailings prior to final discharge. The
recovered water may be reused as makeup or as a process control
measure for additional metal recovery. In-process recycle may
reduce the volume of wastewater discharged by 5% to 17%; when
tailing wastewater is recovered, the wastewater volume may be
reduced by up to 50%. This reduction allows for a smaller waste-
water treatment system. Mine drainage also has been used as mill
makeup water, which has a similar effect on the treatment system.
Several treatment methods are currently being used by the Ore
Mining and Dressing industry. Settling, chemical treatment, and
filtration, are techniques commonly employed. Other methods for
wastewater treatment also are used but on a smaller basis.
Chemical treatment involves the addition of a chemical compound,
usually lime or alum, to precipitate dissolved metals. Prelimi-
nary settling may be used to remove larger particles prior to
chemical treatment, which is generally followed by sedimentation.
Date: 6/23/80 11.11-13
-------
TABLE 11-4. WASTEWATER CHARACTERIZATION, MINE 1108 [1,2]
Category: Ore Mining and Dressing
Subcategory: Iron Ore
Wastewater treatment description: Settling pond
Discharge method: To surface
Effluent flowrate: 15.8 x 103 m3/d (4.17 x 106 gpd)
Mine water and
wastewater
characterization
Pollutant
Classical pollutants
pH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC , mg/L
Toxic pollutants, yg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Benzene
Diethyl phthalate
Settling pond
influent
7.65
110,000
80
96
22
<100
<10
<20
<5
500
130
80
<0.5
2,700
20
20
<100
500
2.3 x 1011
3.8 x 1010
<0.04
<0.004
6.2
55
Settling pond
effluent
7.25
<1
<1
4
11
<50
<2
<20
<5
10
100
<20
<0.5
<20
<5
<10
<100
30
4.3 x 107
4.1 x 106
<0.02
0.006
4.2
ND
Data based on screening sampling.
Date: 6/23/80
11.11-14
-------
TABLE 11-5. WASTEWATER CHARACTERIZATION, MINE 51023 [1,2]
Category: Ore Mining and Dressing
Subcategory: Aluminum
Wastewater treatment description: Lime neutralization,
settling pond
Discharge method: To surface
Effluent flowrate: 4.16 x 10" m3/d (1.1 x 107 gpd)
Mine water and
wastewater
characterization
Pollutant
Classical pollutants
PH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC , mg/L
Toxic pollutants, ug/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Phenol
Bis (2-ethylhexyl)
phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Treatment pond
influent
3.05
2.8
1.6
<2
2
<50
<2
<20
<5
30
60
<20
37
60
<5
<10
<100
570
3.5 x 107
5.5 x 106
<0.02
<0.002
ND
ND
ND
ND
ND
ND
Treatment pond
effluent
8.60
6
5
<2
4
<50
<2
<2
<5
25
50
<20
84
<20
<5
<10
<100
<20
1.4 x 109
2.0 x 10s
<0.02
<0.002
210
50
66
140
1.9
3.1
Data based on screening sampling.
Date: 6/23/80 11.11-15
-------
D
0)
ft
n>
CT\
to
OJ
CO
o
TABLE 11-6. WASTEWATER CHARACTERIZATION, MINE/MILL 2120 [1,2]
Category: Ore Mining and Dressing
Subcategory: Base and Precious Metals, Copper
Wastewater treatment description: Lime precipitation, settling, pH adjustment,
partial recycle to mill
Discharge method: To surface .
Effluent flowrate: 2.596 x 10* m3/d (9.50 x 10° gpd)D
Plant water and wastewater characterization
Pollutant
Classical pollutants
PH
TSS , mg/L
VSS, mg/L
COD, mg/L
TOC , mg/L
Toxic pollutants, pg/L
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Tailings
pond
influent
12.00
164,000
NA
3,210
12
<100
3,600
30
120
800
370,000
18,000
22
1,500
1,000
1,700
<100
27,000
1.3 x 1013
1.7 x 1012
<0.02
0.014
Tailings
pond
recycle
9.90
13
NA
10
10
<100
<2
<5
<5
<20
<20
<20
<1
<20
<5
<10
<100
<20
7.8 x 107
1.2 x 107
<0.02
0.024
Combined treatment
pond effluent and
surge pond overflow
11.20
3
NA
14
17
<100
20
<5
<5
400
120
<20
<1
150
<5
40
<100
50
8.6 x 106
1.3 x 106
<0.02
0.012
Treatment
pond influent
11.75
14
NA
10
19
<100
40
<5
<5
<20
500
40
<1
<20
<5
<10
<100
160
2.3 x 108
9.1 x 106
<0.02
0.018
Treatment
pond effluent
3.45
4
NA
18
12
<100
30
<5
<5
<20
80
40
1
30
<5
<10
<100
<20
2.7 x 107
1.7 x 106
<0.02
0.012
Data based on verification sampling.
^
Combined mine/mill operation.
-------
TABLE 11-7. WASTEWATER CHARACTERIZATION, MINE/MILL/
SMELTER/REFINERY 3107 [1,2]
Category: Ore Mining and Dressing
Subcategory: Base and Precious Metals, L«*<3 and Zinc
stopes backfilled with sand tails, settling pond
Discharge method t To
Effluent flowrate: 1.
surface
36 x 10" mVd
(3.59 x 10« gpd)
Plant water and
Pollutant
Classical pollutants
pH
TSS. mg/L
VSS, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, ug/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fiber e/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Benzene
Methylene chloride
Toluene
Chloroform
Trichlorof luoromethane
Carbon tetrachloride
Other pollutants, ug/L
Iron
Classical pollutants
pH
TSS, mg/L
VES, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, ug/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Bls(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Benzene
Methylene chloride
Toluene
Chloroform
Trichlorof luoromethane
Carbon tetrachloride
Other pollutants, ug/L
Iron
drainageb
4.92
3,600
170
138
1
'100
2,750
<5
145
70
1,015
10,500
18
380
28
45
'100
85,000
1.7 x 10'°
3.93 x 10'
0.33
0.007
NA
NA
4
163
< 1
3
<1
NA
NA
2.15
109
19
210
2
'100
400
<5
7,500
105
1,800
24,200
9
205
12.5
140
'100
545,000
3.3 x 10e
6.8 x 107C
<0.02
<0.002
NA
NA
NA
201
NA
NA
NA
NA
NA
8.88
101,950
4,300
3,150
7
<525
1,500
<5
620
935
14,750
154,500
30
3,700
100
450
<265
222,500
1.8 x 10"
4.1 x 10><>c
3.0
0.011
NA
NA
3
425
< i
<1
<1
NA
NA
2.7
12.5
NA
11
1
<500
28
<5
3,050
75
705
2,750
30
275
<5
<20
NA
86,000
NA
NA
0.175
0.02
NA
NA
NA
NA
NA
NA
NA
NA
58,000
ation
10.08
18.5
4.5
5
4.5
<100
60
<5
660
35
70
5,350
6.5
<20
17.5
20
'100
3,500
6.3 x 1C7
1.1 x 107
<0. 02
0.072
NA
NA
<; 1
6C
NA
4
NA
<1
NA
6.7
19
NA
3
2
'500
4
<5
220
25
60
215
1.7
75
<5
'20
NA
5,500
NA
NA
0.035
0.032
"c
°'3c
NA
NA
NA
NA
NA
2,350
aData based on verification sampling.
Average of two values.
One sample c>nly.
Date: 6/23/80
11.11-17
-------
TABLE 11-8. WASTEWATER CHARACTERIZATION, MINE/MILL 4401a [1,2]
Category: Ore Mining and Dressing
Subcategory: Base and Precious Metals, Silver
Wastewater treatment description: Multiple pond settling
Discharge method: Decant to surface; recycle
Effluent flowrate: 2.93 x 103 m3/d (7.21 x 105 gpd)
Plant water and wastewater characterization
Pollutant
Classical pollutants
pH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, pg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Benzene
Methylene chloride
Bis (2-ethylhexyl)
phthalate
Tetrachloroethylene
Toluene
Di-n-butyl phthalate
Diethyl phthalate
Butyl benzyl phthalate
Carbon tetrachloride
Raw
mine
water
7.40
23
6
19
16
<50
20
<2
<5
<10
160
<20
0.5
40
<5
20
<100
50
3.8 x 107
1.1 x 107
<0.02
0.004
0.26
5.0
0.1
11
ND
ND
ND
ND
ND
Treated mine
water to recycle
or discharge
7.70
3
3
4
1
<50
10
<2
<5
<10
100
20
<0.5
40
<5
30
<100
30
5.7 x 107
1.1 x 106
<0.02
<0.002
ND
ND
0.02
ND
0.64
ND
ND
ND
ND
Tailings
pond
influent
7.40
397,000
62,800
15,100
25
18,000
800
<20
<10
380
15,000
27,000
7.2
390
<40
2,200
<100
4,600
7.1 x 1011
1.1 x 1011
<0.02
<0.01
ND
ND
15
ND
0.83
27
51
ND
1.0
Supernatant
from decant
tower
7.80
13
3
18
11
200
20
<2
<5
15
620
30
<0.5
50
<5
<10
<100
20
2.1 x 109
1.8 x 108
<0.02
<0.002
ND
ND
8.6
ND
2.1
ND
ND
32
ND
Data based on screening sampling.
Date: 6/23/80
11.11-18
-------
TABLE 11-9. WASTEWATER CHARACTERIZATION, MINE/MILL 4105 [1,2]
Category: Ore Mining and Dressing
Subcategory: Base and Precious Metals, Gold
Wastewater treatment description: Not available
Discharge method: Mill makeup
Effluent flowrate: 3.79 x 103 m3/d (1.37 x 106 gpd)
Plant water and
wastewater characterization
Pollutant
Classical pollutants
PH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC , mg/L
Toxic pollutants, ng/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Tetrachloroethylene
Raw mine
water
7.95
26
3.2
8
14
<50
40
<2
<5
45
50
<20
6.3
<20
<5
<10
<100
50
V,
TNTC
5.5 x 106
<0.02
0.01
ND
Sand plant
thickener
overflow
9.00
97
8
8
5
100
5
<20
<5
50
280
20
540
<20
5
<10
<100
420
5.5 x 108
4.4 x 107
0.90
<0.002
ND
Tails and
city sewage
to creek
8.65
60,200
1,290
700
18
<100
200,000
30
<5
1,600
2,600
370
Ib
<500
150
100
<100
3,900
1.1 x 1011
2.7 x 109
6.8
<0.002
3,560
*Data based on screening sampling.
3Total fibers too numerous to count.
Date: 6/23/80
11.11-19
-------
TABLE 11-10. WASTEWATER CHARACTERIZATION, MINE/MILL 9411 [1,2]
Category: Ore Mining and Dressing
Subcategory: Uranium
Wastewater treatment description: BaCl2 coprecipitation,
settling
Discharge method: To surface
Effluent flowrate: 1.36 x 10" m3/d (3.59 x 106 gpd)
Plant water and
wastewater
characterization
Pollutant
Classical pollutants
PH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, pg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Bis(2-ethylhexyl) phthalate
Other pollutants, pCi/L
Total radium 226
Dissolved radium 226
Raw
mine
water
8.05
280
28
37
8
50
3
<20
<5
50
40
40
3.8
<20
5
<10
<100
60
2.3 x 109
1.1 x 108
<0.02
<0.002
47
56. 9C
60.2
Treated
mine
water
8.15
7
1
17
<1
<50
<2
<2
<5
25
<20
50
<0.5
<20
10
<10
<100
30
5.7 x 108
2.7 x 107
<0.02
<0.002
2.4
<2^
_d
Data based on screening sampling.
°Picocuries/L.
'Within sensitivity limits; most Ra 226 is dissolved.
Analysis unreliable.
Date: 6/23/80
11.11-20
-------
TABLE 11-11. WASTEWATER CHARACTERIZATION, MINE/MILL 6102 [1, 2]
Category: Ore Mining and Dressing
Subcategory: Ferroalloy
Wastewater treatment description: Tailings pond, recycle,
chlorination, electrocoagulation, flotation
Effluent discharge: Mine to mill treatment: 3.8 x 10s m'/d
(1.0 x 10' gpd)
Mill treatment discharge: 1.1 x 10" nr/d
(2.91 x 10' gpd)
Plant water and
wastewater characterization
Pollutant
Classical pollutants
pH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, pg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
1,1, 1-Trichloroe thane
Chloroform
Methylene chloride
6-BHC
Diethyl phthalate
Aldrin
•y-BHC
a-BHC
Trichlorofluorome thane
Toluene
Dichlorobromome thane
Butyl benzyl phthalate
Other pollutants, yg/L
Molybdenum
Mine water
6.4
550
35
33
3.5
<200
1.5
13.5
27.5
65
740
65
<1
100
4.5
<50
<100
1,680
6.05 x 109
9.56 x 108
<0.02
0.009
0.99
0.065
2>9b
<10P
0.007*
d""
ND
ND
ND
ND
ND
9,150
Mill tailings
10. B
426,000
6,930
38
14
<200
75.5
37.5
140
2,150
9,350
5,550
45
1,800
75
450
<100
18,750
1.45 x 1012
3.7 x 10s
0.32
<0.004.
0.352J
0.035D
2.10
ND
0.058°
ND
ND
<10£
0.061D
0.226
ND
ND
14.5
Treated
effluent
6.45
1
1.5
5
3
<200
<1
<5
10
25
<20
60
<1
75
<5
<50
<100
25
4.2 x 106
1.5 x 105
0. 048
<0.002
0.63
4.6
2.5
ND
ND
<10
ND
ND
ND
NDfa
0.02
0.418
5.5
aData based on screening sampling (average of two values except
where noted).
One sample only.
cUnconfirmed.
Detected as <10 yg/L in one sample but not confirmed.
Date: 6/23/80
11.11-21
-------
TABLE 11-12. WASTEWATER CHARACTERIZATION, MINE 9202 [1,2]
Category: Ore Mining and Dressing
Subcategory: Mercury
Wastewater treatment description: Total recycle
Discharge method: None
Effluent flowrate: 0 m3/d
Pollutant
Mine water and
wastewater characterization
Decant water
Tailings pond from
influent recycle sump
Classical pollutant
PH
TSS, mg/L
VSS, mg/L
COD, mg/L
TOC, mg/L
Toxic pollutants, yg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
2 , 4-Dimethylphenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Ethylbenzene
Dimethyl phthalate
8.00
139,000
4,300
60
<1
53,000
1,100
90
560
460
850
1,000
230,000
1,600
<10
10
200
2,400
1.3 x 1012
1.5 x 1011
<0.05
0.92
140
76
9.2
56
66
ND
ND
8.30
1.6
<1
22
13
200
110
<20
6
15
50
<20
50
<20
<5
<10
<100
40
7.7 x 108
5.7 x 107
<0.02
0.22
270
66
15
40
9.6
8.8
9.5
Data based on screening sampling.
Date: 6/23/80 11.11-22
-------
TABLE 11-13. WASTEWATER CHARACTERIZATION, MINE/MILL 990 53 [1,2]
Category: Ore Mining and Dressing
Subcategory: Metal Ore Not Elsewhere Classified
Wastewater treatment description: Settling, partial recycle
Discharge method: To surface
Effluent flowrate: 2.65 x 103 m3/d (7.01 x 10s gpd);
varies with precipitation
Plant water and
wastewater characterization
Pollutant
Classical pollutants
pH
TSS , mg/L
VSS, mg/L
COD, mg/L
TOC , mg/L
Toxic pollutants, vg/L,
except as noted
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Asbestos, fibers/L,
Total
Chrysotile
Total cyanides, mg/L
Total phenols, mg/L
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Chloroform
Methylene chloride
Toluene
Ethylbenzene
Mine pit
effluent
7.95
<1
<1
2
8
<50
<2
<2
<5
<10
20
20
<0.5
<20
<5
<10
<100
20
1.9 x 106
1.4 x 105
<0.02
0.03
12
6.3
ND
ND
ND
ND
Raw
mill
water
7.50
57,900
<1
47
3
200
<10
<2
<5
740
880
50
<0.5
630
15
<10
<100
3,500
7.1 x 109
1.1 x 10»
<0.02
0.01
ND
ND
ND
ND
ND
7.2
Treated
mill water
to recycle
7.65
<1
<1
4
5
100
<2
<2
<5
<10
100
40
<0.5
40
<5
<10
<100
20
1.5 x 108
1.3 x 106
<0.02
0.01
7.4
ND
1.1
8
0.44
ND
Data based on screening sampling.
Date: 6/23/80
11.11-23
-------
Land quantities of sludge may be produced that may be disposed of
in an abandoned mine.
Settling is used at mine/mill 1108, where the tailing-pond ef-
fluent is treated with alum, followed by polymer addition and
secondary settling to reduce suspended solids from approximately
200 mg/L to an average of 6 mg/L. At mine/mill 3121, initiation
of the practice of polymer addition to the tailings has greatly
improved the treatment system capabilities. Mean concentrations
of total suspended solids, lead, and zinc in the tailing-pond
effluent were reduced by 64%, 43%, and 17%, respectively, over
those previously attained as shown in Table 11-14.
TABLE 11-14.
IMPROVEMENT IN TREATMENT SYSTEM CAPABILITY
RESULTING FROM POLYMER ADDITION TO EFFLUENT
AT MINE/MILL 3121
Effluent levels
attained prior to
use of polymer, mg/L
Effluent levels
attained subsequent
to use of polymer, mg/L
Parameter Mean
TSS
Pb .
Zn
0
0
39
.51
.46
Range
15 -
0.24 -
0.23 -
80
0.80
0.86
Mean
0.
0.
14
29
38
Range
4
0.14
0.06
- 34
- 0.
- 0.
67
69
Similarly, the use of a polymer at mine 3130 reduced mean concen-
trations of total suspended solids, lead and zinc in treated ef-
fluent by 89%, 76%, and 41%, respectively, over those attained
prior to use of polymer as shown in Table 11-15.
TABLE 11-15.
IMPROVEMENT IN TREATMENT SYSTEM CAPABILITY
RESULTING FROM POLYMER ADDITION TO EFFLUENT
AT MINE 3130
Effluent levels
attained prior to use
of polymer and secondary
settling ponda, mg/L
Effluent levels
attained subsequent to
use of polymer and
secondary settling ponda, mg/L
Parameter Mean
TSS
Pb
Zn
0
0
19
.34
.45
Range
4
0.11
0.23
- 67
- 1.1
- 1.1
Mean
0
0
2
.08
.32
Range
0.2
<0.05
0.18
- 6.
- 0.
- 0.
2
10
57
Secondary settling pond with 0.5-hour retention time.
Date: 6/23/80
11.11-24
-------
Filtration is used as a polishing or pretreatment step to primary
treatment methods. Microscreens or granular-media filtration are
used to remove solids from wastewater. Both full-scale and
pilot-scale operations are currently being studied by this indus-
try. A full-scale multimedia filtration unit is currently in
operation at molybdenum mine/mill 6102. The filtration system
consists of four individual filters, each composed of a mixture
of anthracite, garnet and pea gravel. This system functions as
a polishing step following settling, ion exchange, lime precipi-
tation, electrocoagulation, and alkaline chlorination. Since its
startup in July 1978, the filtration unit has been operating at
a flow of 63 L/s (1,000 gpm) and four months of monitoring data
have demonstrated significant reductions in TSS, iron, and zinc.
Suspended-solids concentrations have been reduced by approximate-
ly 92%, from an average 62 mg/L to less than or equal to 5 mg/L.
Zinc removals from 0.08 mg/L (influent) to 0.06 mg/L (effluent)
and iron removals of 0.50 mg/L (influent) to 0.38 mg/L (effluent)
have also been achieved.
Cyanide is often used in the beneficiation process for several
ores and is normally present in the wastewater. Because of its
toxicity, treatment methods are needed to reduce cyanide concen-
tration. Alkaline chlorination and ozonation are two methods
being used to achieve cyanide destruction.
A full-scale system has been implemented at mill 6102 for cyanide
reduction. The unit is an integral part of a total treatment
system employing lime precipitation, electrocoagulation-flotation,
alkaline chlorination, and multimedia filtration, followed by
final pH adjustment. The alkaline-chlorination system involves
on-site generation of sodium hypochlorite by electrolysis of
sodium chloride. The hypochlorite is injected into the waste-
water following the elctrocoagulation-flotation process and
immediately preceding the filtration unit. At this point in the
system, some cyanide removal has already been realized incidental
to the lime precipitation-electrocoagulation treatment. Opera-
ting data from the first four months show the concentration of
cyanide at 0.09 mg/L prior to the electrocoagulation unit. Con-
centrations of cyanide progressively decrease from 0.04 mg/L
(electrocoagulation effluent) to less than or equal to 0.01 mg/L
after filtration and less than 0.01 mg/L after the final retention
pond. Mill personnel expect this removal efficiency to continue
throughout the optimization period of the system. The problem of
chlorine residuals elevated levels has not yet been resolved.
Ozonation tests in the laboratory showed substantial destruction
of cyanide. Although the target level of less than 0.025 mg/L of
cyanide was not achieved and the tests under pilot-plant condi-
tions showed less favorable results, ozonation did result in sub-
stantial removal of manganese as well as cyanide.
Date: 6/23/80 11.11-25
-------
Phenolic compounds are also used to dress the raw ores. The
low-concentration, high-volume phenolic wastes generated lend
themselves most readily to treatment by chemical oxidation or
aeration. Aeration is the only treatment currently in use
although phenols may be incidentally reduced by treatment of
traditional parameters such as TSS. No individual plant data on
the treatment systems used are currently available.
Radium 226, a product of the radioactive decay of uranium, occurs
in both dissolved and insoluble forms and is found in wastewater
resulting from uranium mining and milling. Coprecipitation of
radium with a barium salt is typically used for wastestream re-
moval of radium. Dosages vary from 10 mg/L to 300 mg/L depending
on the characteristics of the wastestream.
At uranium mine/mill 9452, a unique mine-water treatment system
exists that employs radium 226 ion exchange in addition to floc-
culation, barium chloride coprecipitation, settling, and uranium
ion exchange. The mine water to be treated is pumped from an
underground mine to a mixing tank where flocculant is added. The
water is then settled in two ponds, in series, before barium
chloride is added. After barium chloride addition, the water is
mixed and flows to two additional settling ponds (also in series),
The decant from the final pond is acidified before it proceeds to
the uranium ion-exchange system. The effluent from the uranium
ion exchange column is pumped to the radium 226 system. After
treatment for removal of radium 226, the final effluent is pumped
to a holding tank for either recycle to the mill or discharge.
The unique feature of this treatment approach is the radium 226
ion exchange system, which consists of two up-flow ion exchange
columns operated in parallel. Each column is constructed of
fiber-reinforced plastic (FRP) and contains approximately 11.3 m3
(400 ft3) of resin, supported on a FRP distribution plate. Min-
ing personnel have estimated that the theoretical life of the
resin at the present loading is 50,000 years. The total treat-
ment system at mine/mill 9452 is capable of reducing radium 226
from levels of 955 picocuries/L (total) and 93.4 picocuries/L
(dissolved) to 7.18 picocuries/L (total) and less than 1
picocurie/L (dissolved). This performance represents 99.2%
removal of total radium 226 and greater than 98.9% removal of
dissolved radium 226.
Asbestos is often found in the ores from this industry. Although
several bench-scale and pilot-scale plants have been proposed,
only settling ponds are currently in use. For mill treatment
systems consisting primarily of tailing ponds and settling or
polishing ponds, some facilities have demonstrated reductions
of 10U and 105 fibers/L. Examination of these treatment systems
indicates several factors in common: high initial suspended-
solids loading, effective removal of suspended solids, large
systems or systems with long residence times, and/or the presence
of additional settling or polishing ponds.
Date: 6/23/80 11.11-26
-------
Other methods, which are used to a lesser extent and normally in
the pilot-plant stage, include: flocculation, centrifugation,
oxidation, adsorption, and solvent extraction.
II.11.5 REFERENCES
1. Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Ore Mining and
Dressing Point Source Category, Volumes I and II. U.S.
Environmental Protection Agency, Washington, DC, July 1978.
2. Development Document for BAT Effluent Limitations Guidelines
and New Source Performance Standards for the Ore Mining and
Dressing Industry (draft contractor's report). Contract No.
68-01-4845, U.S. Environmental Protection Agency, Washington,
DC, 25 September 1979.
3. NRDC Consent Decree. Industry Summary - Ore Mining and
Dressing.
4. Environment Reporter, EPA Effluent Guidelines and Standards
for Ore Mining and Dressing, (40CRF440, November 6, 1975;
41FR21191, May 24, 1976; 42FR3165, January 17, 1977,
43FR29771, July 11, 1978; 44FR7953, February 8, 1979;
44FR11546, March 1, 1979), pg 135:0881.
Date: 6/23/80 11.11-27
-------
11.13 PAINT AND INK FORMULATION
11.13.1 INDUSTRY DESCRIPTION [I, 2]
The Paint and Ink Formulation Industry can be divided into two
general categories: paint manufacturing and ink formulation.
Each of these categories is described below. Table 13-1 summarizes
information pertaining to the paint and ink formulation industry
in terms of the number of subcategories and the number and types
of dischargers in the industry [3].
TABLE 13-1. INDUSTRY SUMMARY [1-3]
Industry: Paint and Ink
Total Number of Subcategories: 4
Number of Subcategories Studied: 2
Number of Dischargers in Industry:
Direct: 4
Indirect: 1,211
• Zero: 845
The following limitations establish the quantity and quality of
pollutants or pollutant properties which may be discharged by a
point source resulting from the production of oil-base paint or
oil-base ink (where the tank washing system uses solvents) after
application of the best practicable control technology currently
available: There shall be no discharge of process waste water
pollutants to navigable waters [4, 5]. Appropriate BPT effluent
limitations for water and/or caustic wash and solvent wash
indirect dischargers are yet to be established.
II.13.1.1 General Description of the Paint Industry [I]
Overall, the paint industry consists of an estimated 1,400 to
1,600 manufacturing sites operated by 1,150 to 1,300 companies.
The two major products of the paint industry (SIC 2851) are trade
sales paints, which are primarily off-the-shelf exterior and
interior paints for buildings and other structures, and industrial
Date: 6/23/80 II.13-1
-------
finishes, also called chemical coatings, which are sold to manu-
facturers for factory application to diverse products such as
automobiles, aircraft, furniture, and machinery.
In addition to paints, the industry also produces varnishes and
lacquers, which consist of film-forming binders (resins or drying
oils) dissolved in volatile solvents or dispersed in water. All
paints and most lacquers contain pigments and extenders such as
calcium carbonate, clays, and silicates. Other common allied
products produced by the paint industry are plasticols, epoxy
compounds, asphaltic coatings, adhesives, sealants, paint removers
and stains.
Paint manufacturers can also be classified by the percent of water
base (also called latex-base) paints and the percent of solvent-
base (or solvent-thinned) paints produced. Thirty-three percent
of the paint plants produce 90 percent or more solvent-base paints
but only 8 percent of the plants produce a like percentage of
water-base paints. The "average" plant produces approximately
60 percent solvent-base paint and only 35 percent water-base
paints. Generally, plants making primarily solvent-base paint
produce mostly industrial coatings, while the plants dedicated to
water-base products manufacture primarily trade sales products,
with a high proportion of white or tint-base paints.
There is little difference in the production processes used to
produce either solvent-base or water-base paints. The major
production difference is the carrying agent; solvent-base paints
are dispersed in an oil mixture, while water-base paints are dis-
persed in water with a biodegradable surfactant as the dispersing
agent. The cleanup procedure also differs for each production
process. Because the water-base paints contain surfactants, formu'
lating tanks can be easily cleaned with water. Tanks used to make
solvent-base paint are generally cleaned with an organic solvent,
but cleaning with a strong caustic solution is also common
practice.
The principal raw materials used in paint manufacture, in terms
of pounds consumed, are oils, resins, pigments, and solvents.
Drying oils, such as linseed oil, are used as the film-forming
binder in some solvent-base paints. Semidrying oils are used in
the manufacture of water-base (latex) paints.
The paint industry is a large consumer of solvents, which are
used as the volatile vehicles in coatings and certain specialty
products. Mineral spirits, toluene, xylene, naphtha, ketones,
esters, alcohols, and glycols are the major solvents used. In
addition, the industry consumes a wide variety of other additives
and chemical specialties such as dryers, bactericides and fungi-
cides, defearners, dispersants, and thickeners.
Date: 6/23/80 II.13-2
-------
All paints are generally made in batches. Batch size is an indica-
tor of paint plant size. A small paint plant will produce batches
of 400 to 1,900 liters (100 to 500 gallons), while a large plant
will manufacture batches up to 23,000 liters (6,000 gallons).
Because of the large number of color formulations generally pro-
duced, a continuous process is not feasible.
Solvent-Base Paint Production
The three major steps involved in the solvent-base paint manufac-
turing process are (1) mixing and grinding of raw materials,
(2) tinting and thinning, and (3) filling operations.
At most plants, the mixing and grinding of raw materials for
solvent-base paints are accomplished in one production step. For
high-gloss paints, the pigments and a portion of the binder and
vehicle are mixed into a paste of specified consistency. The
paste is fed to a grinder or mill, which disperses the pigments
by breaking down particle aggregates rather than reducing the
particle size. For other paints, raw materials are mixed and
dispersed in a mixer.
Following the mixing and grinding of raw materials, the paint is
transferred to tinting and thinning tanks in which the remaining
binder and liquid, as well as various additives and tinting colors,
are incorporated. The paint is then analyzed, and the composition
is adjusted as necessary to obtain the correct formulation for
the type of paint being produced. The finished product is then
transferred to a filling operation for filtering, packaging, and
labeling.
Water-Base Paint Production
The pigments and extending agents for water-base paints are usually
received in proper particle size, and the dispersion of the pig-
ment, surfactant, and binder into the vehicle is accomplished
with a saw-toothed high-speed dispenser. In small plants, the
paint is thinned and tinted in the same tank; in larger plants,
the paint is transferred to special tanks for final thinning
and tinting. Once the formulation is correct, the paint is trans-
ferred to a filling operation for filtering, packaging, and
labeling.
Other Manufacturing Operations
Some of the large paint plants manufacture their own synthetic
resins such as the usual alkyd resin, a water-soluble alkyd resin,
or an acrylic resin. For the purposes of this manual, the waste-
water resulting from the manufacture of such resins is not asso-
ciated with the paint industry; hence, it is not further discussed
herein.
Date: 6/23/80 II.13-3
-------
Following the production of either solvent- or water-base paints,
considerable waste or "clingage" remains affixed to the sides of
the preparation tanks. Three specific methods of tank cleaning
are used in the paint industry: (1) solvent wash, (2) caustic
wash, and (3) water wash. Solvent wash is used exclusively for
cleaning tanks used for solvent-base paint formulation. When
solvent washing is used in solvent-base operations, essentially
no wastewater is discharged. Caustic-wash techniques may be used
to clean both solvent-base and water-base paint manufacturing
tanks. Water-wash techniques are also used in both the solvent-
base and water-base segments of the industry. For solvent-base
operations, water washing is usually used only to follow the
caustic washing of solvent-base tanks. For water-base operations,
water washes often constitute the only tank cleaning operation.
However, periodic caustic cleaning of water-base paint is also
a common practice.
Because the paint industry has simple technology and low capital
investment, it includes many small companies. About 41 percent
of the companies have less than 10 employees and account for less
than 5 percent of industry sales. According to the Kline Guide,
the four largest companies (Sherwin Williams, Du Pont, PPG Indus-
tries, and SCM-Glidden) accounted for over 30 percent of industry
sales in 1974. Total paint production in 1974 was valued at
$3.67 billion ($1.87 billion from trade sales and $1.80 billion
from industrial finishes).
Geographically, paint plants tend to be clustered around popula-
tion centers, due to the expense of transporting paint long
distances. Approximately 46 percent of all paint plant sites are
contained in five states (California, New Jersey, New York,
Illinois, and Ohio) and 87 percent in twenty states.
II.13.1.2 General Description of the Ink Industry [2]
The printing ink industry (SIC 2893) includes establishments
primarily engaged in the manufacture of printing ink; it does not
include captive ink establishments that produce ink only for use
within the parent plant. Captive plants are considered to be
contained in SIC 27, which includes printed items manufactured as
final products.
The printing ink industry consists of an estimated 460 to 500
manufacturing sites operated by approximately 200 companies. The
plant sites are dispersed throughout the nation with higher con-
centrations in the North Central and Coastal Areas. Five states
(California, Illinois, New Jersey, New York, and Ohio) contain
42 percent of the plants and ten states include 65 percent.
Plants are located near population centers due to transportation
costs and the need to be near customers. A large majority (71
percent) of the ink manufacturing facilities are small and employ
less than 20 personnel.
Date: 6/23/80 II.13-4
-------
Ink Production
Ink production involves three major ingredients: the vehicle,
pigment, and drying agent. The vehicle, normally water or solvent,
is used to transport the pigment, which may be either an inorganic
or organic compound. The drying agent may be a separate compound
or the vehicle for the ink. The drying agent aids in the prelim-
inary fixing of the ink on the surface and functions by oxidation,
absorption, or evaporation.
In the ink industry, the primary plant operation is the blending
of the ingredients to produce various sized batches of ink.
Blending is accomplished with the use of high-speed mixers and/or
a wide variety of mixing mills. The blending occurs in a series
of steps, normally one or two; the number of steps depends on the
dispersion characteristics of the ingredients. Ink is often
custom manufactured and may be continuously produced, as in news-
paper inks, or batch produced in quantities as small as five
pounds.
After the ink product has been removed, the formulation tub is
normally cleaned. A solvent-base solvent wash is often used to
clean solvent-base ink from a tub. A caustic wash, followed by
a water rinse, is also commonly used for solvent-base inks. This
technique is also used for water-base inks, although a water-only
wash is more common. This water can be reused or treated and
released.
Major Types of Ink
There are four major types of ink; each type has its own ingredi-
ents and characteristics. Letterpress inks are viscous tacky
pastes that use an oil or varnish base and dry by oxidation of
the vehicle. Lithographic inks are similar to letterpress inks
but have a higher concentration of pigment to offset the thinner
film used in printing this type of ink. Flexographic inks are
liquids that may be solvent or water-based and dry by evaporation,
absorption, or decomposition. Gravure ink is a liquid that dries
by solvent evaporation and used for a variety of purposes.
Varnish, an allied product of the industry, is produced by
20 percent of the ink formulation plants.
Product Mix
Approximately half of the plants in the ink industry specialize
primarily in either paste or liquid ink. The remaining half
produce both types of ink, with a wide variety of fractional mix.
An "average" plant, based on all plants, produces 65 percent paste
ink and 35 percent liquid ink. Ink manufacturers may also be
classified by the percentage of water-base ink and solvent- or
oil-base ink produced. Thirty-seven percent of the plants produce
Date: 6/23/80 II.13-5
-------
100 percent solvent- or oil-base ink, and only 3 percent produce
100 percent water-base ink.
Using this type of classification, the "average" plant would pro-
duce 60 percent oil-base ink, 25 percent solvent-base ink, and
15 percent water-base ink. Plants that manufacture primarily
solvent- and oil-base ink also produce primarily paste inks; plants
that manufacture primarily water-base ink produce primarily liquid
inks.
II.13.1.3 Subcategory Description
The paint and ink formulation industry is divided into the follow-
ing two subcategories based on the tank cleaning techniques used:
(1) water-wash and/or caustic-wash, and (2) solvent-wash (solvent-
base solvent-wash).
Water-Wash and/or Caustic-Wash Subcategory
This subcategory encompasses those facilities using either water-
wash or caustic-wash operations to clean their formulation tanks.
Rinse waters generated following caustic wash are sometimes less
concentrated than wastewaters generated exclusively from water
rinse, although the pollutants contained in these two types of
wastewater are similar. Consequently, the methods of treatment
and disposal are essentially the same.
Solvent-Wash (Solvent-Base Solvent-Wash) Subcategory
This subcategory encompasses those facilities using solvent-wash
operations to clean their formulation tanks. Effluent Limitations
Guidelines for the solvent-base solvent-wash have already been
promulgated except for existing indirect dischargers (EPA 440/1-75,
050a). Hence, solvent-base wash operations will not be considered
II.13.2 WASTEWATER CHARACTERIZATION
The paint industry, in total, generates approximately 5.7 million
liters (1.5 million gallons) of process wastewater daily. About
half of this water is actually discharged; the other half is
reused by paint plants, evaporated, or drummed for disposal as a
solid waste. The ink industry, on the other hand, generates
about 150,000 liters (40,000 gallons) of wastewater daily, of
which 75 percent is actually discharged. For the purposes of this
manual, process water is defined as only that wastewater which
has an opportunity to contact paint solids, such as tank or fillin<
equipment wash water, caustic-wash rinse water, and floor wash
water. Other wastewaters, such as sanitary or noncontact cooling
water, are not considered to be part of the process wastewater
stream.
Date: 6/23/80 II.13-6
-------
The percentage of solvent-base and water-base paints or inks pro-
duced is the most important factor that affects the volume of pro-
cess wastewater generated and discharged at both paint and ink
plants. Due to their greater use of water-wash, plants producing
90 percent or more water-base paint (or ink) discharge more waste-
water than plants producing 90 percent or more solvent-base paint
(or ink). Additional factors influencing the amount of wastewater
produced include the pressure of the rinse water and the existence
or absence of floor drains. Where no troughs or floor drains
exist, equipment is often cleaned by hand with rags; when wastewater
drains are present, there is a greater tendency to use hoses.
11.13.2.1 Water-Wash and/or Caustic-Wash Subcategory
Batch mixing tanks for water-base paint (or ink) that are rinsed
with water generate considerable quantities of wastewater. The
spent tank and equipment rinse water is usually handled in one
of four ways: (1) reuse in the next compatible batch of paint
(or ink) as part of the formulation, (2) reuse either with or
without treatment, to clean tanks and equipment until spent (if
sludge settles out, it is disposed of as a solid waste), (3) dis-
charge with or without treatment as wastewater, and (4) disposal
as a solid waste.
Plants that use caustic-rinse systems usually rinse the residue
with water, although a few plants allow the caustic to evaporate
from the tanks. Evaporation of caustic solution, however, can
leave a residue that will interfere with some types of paint
formulas. There are two major types of caustic systems commonly
used by the paint and ink industries. In one type of system,
caustic is maintained in a holding tank (usually heated) and
is pumped into the tank to be cleaned. The caustic drains to a
floor drain or sump where it is returned to the holding tank. In
the second type of system, a caustic solution is prepared in the
tank to be cleaned, and the tank is soaked until clean. Most
plants using caustic reuse the solution until it loses some of
its cleaning ability. At that time, the caustic is disposed of
either as a solid waste or wastewater, with or without treatment.
The water rinse following a caustic wash is rarely reused in a
subsequent batch of paints (or ink). Generally, any generated
wastewater is combined with the regular clean-up water, and
disposed of by one of the same methods.
II.13.2.2 Solvent-Wash (Solvent-Base Solvent-Wash) Subcategory
Batches of solvent-base paint or ink that are rinsed with solvent
ordinarily generate no wastewater. The used solvent is generally
(1) used in the next compatible batch of paint (or ink) as part
of the formulation, or (2) collected and redistilled, either by
the plant or by an outside company, for subsequent reuse or
resale, or (3) reused with or without settling to clean tanks and
Date: 6/23/80 II.13-7
-------
equipment until spent, and then drummed for disposal. If sludge
settles out, it is also drummed for disposal as a solid waste.
In addition to process wastewater generated as a result of tank
and equipment cleaning, there are other sources of pollutants
within the typical paint or ink plant and these include: (1) bad
or spoiled batches that are not reused in other products or
discharged as a solid waste, and (2) residue from spills that is
discharged to the sewer or combined with other wastewater.
Tables 13-2 and 13-3 present information on the toxic and classi-
cal pollutants found in detectable concentrations for the plant
water supply, raw wastewater, and treated effluents for the
"water-wash and/or caustic-wash" subcategory of the paint indus-
try. Similar data are presented in Tables 13-4 and 13-5 for the
ink industry. Values for both the paint and ink industries were
generated from verification and field sampling results repre-
senting 22 paint plants and 6 ink plants.
Not included in Table 13-2 are 19 toxic pollutants of concentratio
less than 10 mg/L that were detected in one or more samples of
the untreated wastewater. They are acrolein, 2-chloronapthalene,
3,3'-di-chlorobenzidine, 2,4-dichlorophenol, fluoranthene, bis(2-
chloroethoxy) methane, 4,6-dinitro-o-cresol, diethyl phthalate,
benzo(a)pyrene, anthracene, aldrin, dieldrin, 4,4'-DDE,
b-endosulfan, heptachlor epoxide, a-BHC, b-BHC, q-BHC, and w-BHC.
Also not included in Table 13-2 are eight toxic pollutants found
in one or more treated effluent samples above the detectable limit
and eleven toxic pollutants detected once or twice at less than
10 mg/L. The pollutants found in one or more treated effluent
samples above the detectable limits are arsenic, selenium, 1,2-
dichloropropylene, bis(2-chloroethoxy) ether, 2,4-dinitrophenol,
di-n-octyl phthalate, butyl benzyl phthalate, and dimethyl
phthalate. The pollutants detected once or twice at less than
10 mg/L are chlorobenzene, chloroethane, 1,2-diphenylhydrazine,
diethyl phthalate, acenaphthylene, anthracene, phenanthrene,
4,4'-DDD, b-endosulfan, endrin aldehyde, and b-BHC.
Eighteen additional toxic pollutants not reported in Table 13-2
were found in one or more tap water samples. They are chloro-
benzene, arsenic, selenium, 2,4,6-trichlorophenol, 3,3'-dichloro-
benzidene, 2,4-dichlorophenol, 2,4-dinitrotoluene, fluoranthene,
brornoform, butyl benzyl phthalate, diethyl phthalate, benzo(b)-
fluoranthene, benzo(k)fluoranthene, anthracene, endrin aldehyde,
a-BHC, b-BHC, and q-BHC. Quantitative values were not available.
Not included in Table 13-4 (for the ink industry) are 21 toxic
pollutants that were detected in one or two samples of untreated
wastewaters at concentrations less than 10 mg/L. They are
acenaphthene, 1,2,4-trichlorobenzene, 2,4,6-trichlorophenol,
p-chloro-m-cresol, 1,2-dichlorobenzene, 1,4-dichlorobenzene,
Date: 6/23/80 II.13-8
-------
rt
(D
hJ
U)
00
o
TABLE 13-2.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
PAINT PLANT WASTEWATER AND INTAKE [1]
CO
VO
Number of
Samples
Toxic pollutant analyzed
Metals and inorganics
Antxroony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols
Pentachlorophenol
Phenol
Uromatica
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromomethane
Chloroform
Dichlorobromorae thane
1 , 1-Dichloroethane
1, 2-Dichloroethan«
1 , 1-Dichloroethylene
1, Z-Trcma-dichloroe thy lene
1 , 2-Dichloropropz-ne
Methylene chloric'e
Tetrachloroethylene
1,1, 1-Trich loroethane
1,1, 2-Trichloroethane
Trichloroethylene
Pesticides and met-ibolites
Isophorone
49
41
51
51
51
51
54
51
50
51
51
51
51
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
TiMB
detected
49
41
51
51
51
51
54
51
50
51
51
51
51
9
IB
6
8
17
21
3
23
9
8
0
14
1
1
5
5
2
3
17
17
15
5
15
0
Times
detected
above
min
9
22
9
22
42
50
9
37
40
14
5
8
49
8
13
5
7
17
21
2
23
8
7
0
14
1
0
4
3
1
2
17
16
14
2
'10
0
Average
72
120
13
80
2,900
2.300
73
6,300
10,000
1,000
16
17
84 , 000
500
8,000
6,000
1,000
2,000
2.600
100
20,000
3,000
3,800
200
27
-------
o
pj
ft
(0
OJ
oo
o
TABLE 13-2 (continued)
UJ
I
o
Samples
Toxic pollutant analyzed
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadniu*
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Phthalate*
Bis(2-ethylhexyl> phthalate
Dt-n-butyl phthalate
Phenols
Pentachlorophenol
Phenol
Arimatics
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Halogenated aliphatic:
Carbon tetrachloride
Chlorodibromome thane
Chloroform
Dichlorobroraomethane
1, 1-Dichloroe thane
1 , 2-Dichloroothane
1 , 1-Dichloroe thy lene
1, 2-rroua-dichloroethylene
1 , 2-Dichloropropane
Methylene chloride
Te trach loroe thy lene
1,1, 2-Trichloroe thane
Trichloroethylene
11
31
31
31
31
31
31
31
31
11
4
31
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Number of
Times
detected
11
31
31
31
31
31
31
31
31
31
4
31
6
5
4
4
5
6
0
6
4
2
0
2
0
0
0
0
0
0
7
5
7
0
5
Sludge
Tines
detected
above
min Average
5
18
20
29
31
4
29
26
21
7
0
29
4
4
4
3
4
6
0
6
3
0
0
2
0
0
0
0
0
0
7
4
4
0
2
1,700
20
170
7, 100
7,800
1,300
1 1 , 000
29,000
12,000
23
'200
270,000
570
3,600
350
400
410
18,000
59,000
370
'10
920
170,000
2,100
870
45
Median
25
20
100
700
1,000
JO
3,000
2,300
100
'10
'200
100,000
410
70
130
240
30
240
1,300
200
<10
920
2,600
no
14
<10
Saofiles
Maximum analyzed
13.000
100
600
90,000
80,000
36,500
eo.ooo
220,000
200,000
100
<200
2,000,000
1,900
18,000
1,100
1,100
1,900
99.000
0
350,000
1,100
<10
0
1,000
0
0
0
0
0
0
900 , 000
8.200
1,200
0
130
20
21
21
21
21
22
20
21
20
21
19
20
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
Number of
Tim**
detected
20
21
21
21
21
22
20
21
20
21
19
20
3
4
1
0
11
3
1
9
0
3
10
15
13
0
0
9
0
0
17
2
11
2
4
Times
detected
above
• in
2
1
7
8
11
2
4
10
2
1
0
13
0
0
0
0
9
2
0
3
0
2
4
12
B
0
0
3
0
0
16
1
6
1
0
Average
12
a
31
43
150
20
130
290
41
'10
11
1,200
<10
<10
<10
90
163
<10
310
13
22
130
26
13
430
25
36
14
'10
Median
'10
<10
20
20
60
20
100
0
20
'10
<10
600
<10
'10
<10
16
61
<10
*10
14
<10
41
15
<10
67
25
18
14
<10
Max lulu
25
20
200
200
700
93
400
6.00O
200
30
20
8,000
<10
<10
<10
0
570
420
<10
2,700
0
15
110
570
86
0
0
40
0
0
2,200
40
110
18
<10
Pesticides and metabolites
Isophorone
-------
0
0)
ri-
tt>
TABLE 13-3.
CONCENTRATIONS OF CLASSICAL POLLUTANTS FOUND
IN PAINT PLANT WASTEWATER AND INTAKE [1]
(mg/L except as noted)
CTi
(VJ
Ul
CO
° Pollutant
BODs
COD
TOC
TSS
Total
phenols3
Oil and
grease
pH"
1— 1
I— I
.
(— '
10
1
BODs
COD
TOC
TSS
Total
phenols*
Oil and
grease
pHb
Untreated wastewater
Samples
analyzed
54
54
49
51
54
50
53
Samples
analyzed
31
32
31
31
32
30
29
Number of
Times
detected
54
54
49
51
54
SO
53
Number of
Times
detected
31
32
31
31
32
30
29
Times
detected
above
min
54
54
49
51
47
50
53
Sludge
Times
detected
above
min
31
32
31
31
25
30
29
Average
9,900
56,000
10,000
20,000
290
1,200
Average
26 , 000
190,000
37,000
100,000
630
8,600
Median
4,900
40,000
8,500
13,000
140
980
7
Median
12,000
140,000
30,000
70,000
200
2,900
7
Maximum
66,000
350,000
34,000
150,000
1,900
3,400
12
Maximum
150,000
950,000
110,000
470,000
6,000
130,000
12
Samples
analyzed
48
47
44
48
49
43
46
Samples
analyzed
21
22
20
20
22
18
20
Number of
Times
detected
48
47
44
48
49
43
46
Number of
Times
detected
21
22
20
20
22
18
20
Treated wastewater
Times
detected
above
min
46
47
44
48
43
42
46
Intake
Times
detected
above
min
1
13
18
17
5
4
20
Average
5,300
21,000
4,000
2,000
230
230
water
Average
3
10
8
3
15
1
Median
3,500
11,000
2,800
240
90
24
7
Median
2
6
8
3
16
1
7
Maximum
32,000
260,000
25,000
22,000
1,900
1,700
11
Maximum
6
40
20
11
40
5
9
Values in U9/L.
Values in pH units.
-------
O
ft)
ft
tt>
NJ
(jJ
CO
O
TABLE 13-4.
U)
i
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN INK PLANT WASTEWATER AND INTAKE [2]
Samples
Toxic pollutant analyzed
Metals and inorganics
Antinony
Arsenic
Beryllium
Cadmium
Chroniun
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
phthalates
Bis(2-ethylh«xyl) phthalate
Di-n-butyl phthalate
Phenols
Pentachlorophenol
Phenol
Aronatics
Benzene
Etnylbencene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Halogenated aliphatics
Carbon tetrachloride
Ch lorodibromomethane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroethane
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
1 , 2-Dichloropropane
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1, 2-Trichloroethane
Trichloroethylene
9
9
9
9
9
9
10
9
7
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
Un
Number of
Times
detected
9
9
9
9
9
9
10
9
7
9
9
9
9
6
5
2
5
6
3
8
3
1
1
4
O
2
2
3
1
1
4
5
2
1
4
Times
detected
above
min
3
0
0
3
9
9
8
9
3
0
0
0
6
2
2
1
2
5
3
7
2
1
1
2
0
2
1
1
0
1
4
5
2
0
4
Average
310
25
8
34
38,000
14,000
330
170,000
170
44
8
<10
4,400
15,000
170
660
120
370
4,200
1,400
13
96
43
37
21
89
15
<10
22
1,100
1,300
560
<10
1,800
Median
25
25
<10
20
20,000
800
110
50,000
11
50
<10
<10
1,000
<10
<10
660
<10
130
5,500
330
14
96
43
14
21
89
<10
<10
22
820
170
560
<10
1,200
Samples
Maximum analyzed
2,200
25
<10
90
200 , 000
100,000
2,000
900,000
1,100
50
<10
<10
20,000
87,000
770
1,300
540
1,600
6,700
6,000
17
96
43
110
0
33
170
25
<10
22
2,900
3,100
1,000
<10
5,000
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
I
1
1
1
1
1
1
1
1
1
1
Number of
Times
detected
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
1
1
1
1
0
0
0
0
0
0
0
0
0
1
0
0
0
0
Times
detected
above
min
1
0
1
1
1
1
1
1
0
0
1
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
Average Median Maxmun
<25 <25 <25
<10 <10 <10
20 20 20
<50 '50 <50
<60 <60 <60
30 30 30
<200 <200 <200
<50 <50 <50
<10 <10 <10
<10 <10 *10
1,000 1,000 1,000
<10 <10 <10
<10 <10 <10
0
0
96 96 96
2.400 2,400 2,400
1,100 1,100 1,100
<10 <10 <10
0
0
0
0
0
0
0
0
0
29 29 29
0
0
0
0
Pesticides and metabolites
Isophorone
44,000 44,000
46 46
(continued)
-------
o
DJ
rt
ro
rO
CO
00
o
TABLE 13-4 (continued)
I
M
U)
Samples
Toxic pollutant analyzed
Metals and Inorganics
Antimony
Arsenic
Beryllium
Cadniun
ChroMiun
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thalliu»
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenoli
Pentachlorophenol
Phenol
Axomatics
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Naphthalene
Halogenated aliphatlcs
Carbon tetrachloride
Chlorodibromone thane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1, 2-Dichloroethane
1, 1-Dichloroethylene
1 , 2-rrona-dichloroethylene
1 , 2-Dichloropropane
Methylene chloride
Tetrachloroethylene
1,1, 1-Tnchloroethane
1,1, 2-Tr ichloroethane
Tr ichloroe thy lene
S
s
6
6
6
6
7
6
4
6
6
5
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Number of
Tines
detected
5
5
«
6
6
6
7
6
4
6
6
S
6
2
2
0
0
4
0
4
0
0
2
6
2
0
I
0
0
0
6
0
1
0
1
Tines
detected
above
nin
1
0
0
1
5
S
0
4
1
0
0
0
i
i
0
0
0
3
0
0
0
0
1
4
2
0
0
0
0
0
6
0
0
0
0
Average
32
25
a
12
370
110
20
3,5OO
1
28
S
<10
350
87
<10
SB
<10
42
99
55
<10
150
<10
<10
Median
<10
25
-------
o
D)
rt
0>
TABLE 13-5. CONCENTRATIONS OF CLASSICAL POLLUTANTS FOUND
IN INK PLANT WASTEWATER AND INTAKE [2]
(mg/L except as noted)
^ Untreated wastewater
CO
CO
O Pollutant
BOD,
COD
TOC
TSS
Total
phenols3
Oil and
grease
PHb
l-l
l— I
t_j
to
1
l~*
BODg
COD
TOC
TSS
Total
phenols8
Oil and
grease
pHb
Samples
analyzed
10
9
9
10
10
10
9
Samples
analyzed
7
6
6
6
7
7
7
Number of
Times
detected
10
9
9
10
10
10
9
Number of
Times
detected
7
6
6
6
7
7
7
Times
detected
above
min
10
9
9
10
10
9
9
Intake
Times
detected
above
min
0
5
6
6
3
3
7
Average
14,000
42,000
10,000
990
240
620
water
Average
2
12
8
3
16
2
Median
1,500
3,000
520
740
98
110
9
Median
2
11
8
2
20
1
7
Treated
Number of
Times
detectrd
Samples Times above
Maximum analyzed detected mm
73,000 111
270,000 111
66,000 111
2,200 111
700 111
2,400 111
13 1 1 1
Maximum
2
25
13
6
20
5
8
Average Median Maximum
2,600 2,600 2,600
4,800 4,800 4,800
940 940 940
110 110 110
30 30 30
260 260 260
13 13
Values in yg/L.
Values in pH units.
-------
2,4-dimethylphenol, 2,4-dinitrotoluene, 2,6-dinitrotoluene,
fluoranthene, bis(2-chloroisopropyl) ether, trichlorofluoromethane,
N-nitrosodiphenylamine, butyl benzyl phthalate, dimethyl phthalate,
chrysene, acenaphthylene, fluorene, phenanthrene, pyrene, and
dieldrin. Also not included in Table 13-4 or 13-5 are ten toxic
pollutants found in one or more of the tap water samples at less
than the detectable limit. They are acenapthene, 1,2,4-trichloro-
benzene, trichlorofluoromethane, butyl benzyl phthalate, diethyl
and q-BHC.
II.13.3 PLANT SPECIFIC DESCRIPTION
Production characterization and statistics concerning wastewater
generation and treatment for each of the 22 paint plants and 6 ink
plants are presented in Table 13-6.
Table 13-7 through 13-10 present toxic pollutant and classical
pollutant data for four of the 22 paint plants representing the
"water-wash and/or caustic-wash" subcategory of the paint indus-
try. Tables 13-11 through 13-14 present similar data for four
of the six plants representative of the ink industry. Unless
otherwise noted, all values are generated from screening data and
averaged from two or more batches based upon batch sampling.
Whenever a "less-than" quantity was encountered, its numerical
value was used to determine the given average. Unless all of the
values used in the determination were "less-than" quantities, the
"F" symbol was dropped in the final average.
Date: 6/23/80 11.13-15
-------
o
D)
rt
(D
NJ
U)
CO
o
TABLE 13-6. PAINT AND INK PLANT CHARACTERIZATION [1, 2]
Perce
it of
production
plant Water Solvent
code thinned
1 75
2 100
3 90
4 100
6 100
8 75
9 75
11 15
12 10
13 65
14 65
15 25
16 50
17 85
IS 65
20 65
24 100
25 40
26 65
27 85
1» 65
Ink plant*
7 30
10 25
19 Q
21 35
22 0
23 20
*wt - water-thi
caustic.
V - physical
thinned
25
0
0
0
25
2
8
90
3
3
7
50
15
35
35
0
60
35
15
35
70
75C
100
65
100
80
nned ope
Percent of
Organic
5
40
5
15
5
35
25
20
45
15
10
10
10
15
s
5
85
5
60
35
5
15
65
65
ration, St
95
60
9S
85
95
65
75
80
55
85
90
90
90
85
95
95
15
95
40
65
95
85
35
95
Batch 5.OOO
Batch
Batch
Batch
Batch
Batch
Batch
Batch
Batch
Batch
Contlnuoua
Butch
Continuoua
Batch
Batch
Batch
Batch
Batch
Batch
Batch
- Solvent-thinned opera*
4,000
5,500
5, 700
4.0OO
4, SOO
900
6.OOO
70O
300
750
1,500
l.OOO
800
6,000
200
25. OOO
11,000
300
ion, CR •
st.c) , HP
Vtt
Ht
Ht
Ht , CR
Ht
ft
Ht
Ht
CR
Ht
Ht
Mt, St
Wt
Ht
Ht
Wt
Ht
Ht, CF
Ht
Wt
Ht
WR
CR»
CRa
HR, CR,.
C
CRi.
CR», SC
CR,
t_Austic r
Pfri Mt
Litpr flow to
Had/ trp«t*.f>n
0 1SC 100
0.35 75
0 27 45
0. JC 70
0.15C 65
0 1C 85
c
0. 16 99
.17 100
. 3 10O
. 3 1OO
.15 100
.06 100
.04 1OO
0.13 100
0.15 100
0.25C 100
0.0 Jc 100
0.7 100
0.23C 100
0-31° 1OO
0-07
0.13C 100
\t\se. CR> - prlwa
inse of ink tubs,
r>7
0
0
SO
0
o
0
0
0
0
0
0
0
0
50
0
75
2S
0
0
0
10
0
ry water ri
SC " cond*
so"
200
150
j
50
50d
200
d
60C
150
75
100
so"
5oJ
50"
so"
SO*
125
60C
60C
80
50°
rise frop ca
naate froM
Ho
No
Mo
Yea
Ho
4»
»..*
Yaa*
Y*a
No
Ho
Ho
No
Mo
Ho
No
Taa
!••
Ho
Ho
Yaa
Ho
T«»
Y««
Ho
Ya»
Yes
PC
PC
PC
PC
PC
PC
GS
H»»ut
PC
PC
GS
PC
PC
PC
PC
PC
PC
PC
PC
PC
GS
GS.Sk,
Haut
GS
ustic washer. CRa
steaai tub cleaner.
SodluBt blBulfat.*,
•nlonlc and
cat ionic polyMT
AlvaM, pot»,>«|u4l
hydro* Id p
etary rV^uafloc
409, poLyv*ar
Altamlnuf* sulfate.
SodTvai alu.minat.1
Halco 7722
MUM ferric.
polywer cauat Ic
poLywr
Jhqua Aactonlat
Nalco 7742A
Phoaphorlc acid
Halco 3174
Nalco 634
Mobil floe
Maain 9OOO
Coaan C-Floc 18
MUM, liaw, aoda
••h, f*crlc
Caustic, far rout)
•ulfata, DuBola
Floe 551
Draw Aawrfloc
Parrlc floe,
aulfurlc acid.
caustic
Sulfuric acid.
liM
Mater floe.
cat ionic polyME
MCI, Coaan
C-Ploc
• secondary water
C - spent
CEati«ated froai 30H survey
-------
TABLE 13-7. WASTEWATER CHARACTERIZATION, PLANT 1 (PAINT)3 [1]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic wash
Wastewater treatment description: Neutralization, settling and
clarification, chemical treatment (alum, polymer)
Untreated wastewater flowrate, gpd: 1,000-6,000
Pollutant
Metals, ug/1
Sliver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
1 , 1-Dichloroethane
1,1, 2-Trichloroethane
Chloroform
1, 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
1 , 2-Dichloropropane
Ethylbenzene
Methylene chloride
Di chlorobromomethane
Chlorodlbromomethane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Classical and others
pH, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, vg/L
TS, mg/L
TDS, mg/L
TSS, mg/L
TVS , mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
13
220,000
NA
400
<10
<20
2,200
1,200
400
46,000
59
800
30
2,000
5,000
<25
500
4,500
<10
1,700
300
ND
25
ND
ND
ND
160
ND
ND
<10
1,300
4,800
ND
ND
ND
ND
ND
ND
ND
ND
ND
18
2,700
250
7.0
3,000
51,000
10,000
1,200
<107
55
16,000
5,100
11,000
11,000
5,300C
150
22
260
Treated
effluent
<10
5,000
NA
330
<10
<20
320
130
77
3,300
27
193
60
<50
<200
«25
<50
<200
<10
600
ND
ND
ND
<10
ND
ND
ND
<10
ND
ND
390
110
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
720
17
6.4
2,800
13,000
3,200
150
<80
80
5,600
3,100
2,600
4,300
290
<50
3
300
Sludge
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Intakeb
30
600
NA
100
<10
<20
<50
100
200
2,000
o.e
'50
<50
200
400
<10
200
200
<10
1,000
ND
<10
ND
ND
ND
ND
45
ND
ND
ND
ND
690
ND
ND
ND
ND
ND
ND
ND
ND
ND
10
ND
10
6
<2.4
<5
<1
<1
<20
12
59
56
3
30
2
<50
3
<150
aAll data from 3-batch sampling except as noted.
Data from 1-batch sampling.
Value from 2-batch sampling.
Date: 6/23/80
11.13-17
-------
TABLE 13-8. WASTEWATER CHARACTERIZATION, PLANT 2 (PAINT)3 [1]
Category: Paint and Ink Fornulation
Subcategory: Water and/or caustic wash
Wastewater treatment description: Settling and clarification,
chemical treatment (alum)
Untreated wastewater flowrate, gpd: 1,000-6,000
Pollutant
Metals, ug/L
Silver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
1, 1,1-Trichloroethane
1 , 1-Dichloroethane
1,1, 2-Tr ichloroethane
Chloroform
1 , 1-Dichloroethylene
1 , 2-Tra-:t-dichloroethy lene
1 , 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dichlorobromomethane
Chlorodibromome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Classical and others
pH, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
TS, mg/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
<10
140,000
NA
26,000
«10
103
1,000
1,300
400
80,000
<5
320
150
320
350
15
300
10,500
<10
59,500
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
85
ND
ND
ND
ND
110
ND
96
ND
160
ND
ND
210
7.3
2,500
27,000
7,300
1,600
<65
107
17,000
7,900
8,900
9,500
6,700
290
67
280
Treated
effluent
<7
1,900
NA
<37
<7
<15
40
40
110
1,400
3.5
630
37
37
ISO
<10C
700
<140
<10
8,900
ND
ND
17
ND
<10
ND
22
ND
ND
ND
4,600
ND
ND
ND
ND
ND
35
ND
ND
ND
ND
45
ND
190
7.3
2,900
7,600
1,500
11
<20
70
8,600
8,500
50
3,700
13
240
45
300
Sludge
-------
TABLE 13-9. WASTEWATER CHARACTERIZATION, PLANT 4 (PAINT)3 [1]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic wash
Wastevater treatment description: Gravity separation, chemical
treatment (alum, lime)
Untreated wastewater flovrate, gpd: 1,000-6,000
Pollutant
Metals, ug/L
Silver
Aluminum
Arsenic
Bariuir
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L*1
Benzene
Carbon tetrachloride
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
1, 1-Dichloroethane
1,1, 2-Trichloroethane
Chloroform
1, 1-Dichloroethylene
1 , 2-?roi«-dichloroethylene
1, 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dlchlorobromome thane
Ch lorod ibromome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Classical and others
pH, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
TS, rog/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
<10
37,000
NA
4,300
<10
47
67
57
500
12,000
9
97
57
<50
370
<25
460
330
<10
170,000
24
ND
ND
50
ND
ND
ND
ND
ND
ND
460
4,200
ND
ND
ND
54
ND
ND
36
ND
57
270
580
ND
7.7
3,300
150,000
13,000
630
150
1,100
66,000
52,000
14,000
17,000
11,000
1,300
35
230
Treated
•ff luent
-------
TABLE 13-10. WASTEWATER CHARACTERIZATION, PLANT 9 (PAINT)3 [1]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic wath
Wastewater treatment description: Neutralixation, chemical
treatment (polymer)
Untreated wastewater flowrate, gpd: 500-1,000
Pollutant
Metals, ug/L
Silver
Aluminum
Arsenic
Barium
Beryl 1 lum
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Ti tanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachlonde
1, 2-Dichloroe thane
1,1, 1-Trichloroe thane
1, 1-Dichloroethane
1,1, 2-Trichloroe thane
Chloroform
1, 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
1 , 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dichlorobromome thane
Chi orodibromome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Tnchloroethylene
Classical and others
pH , pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
TS, mg/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
<10
200,000
NA
4,700
<10
<20
380
53
700
110,000
14,000
5,000
150
<50
300
<25
730
7,700
<10
830
9,900
10
ND
ND
ND
ND
92
ND
ND
ND
240
310
ND
ND
ND
ND
ND
ND
ND
15
100
4,900
1,700
18
7.4
6,700
84,000,.
20,000
1,800
160
170
30,000
10,000
20,000
22,000
14,000
640
25
180
Treated
effluent
<10
1,000
NA
67
<10
<20
<50
<50
200
3,000
600
130
53
<50
«200
28
300
<200
<10
<600
2,400
ND
ND
10
ND
ND
ND
<10
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
16
<10
<10
210
180
<10
7.3
2,400
8,300
2,300
50
110
190
2,200
1,900
310
1,200
250
<50
7
250
Sludge
<10
150,000
NA
18,000
<10
<20
330
57
600
260,000
115,000
9,300
150
53
470
NA
700
15,000
NA
1,200
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
7.2C
14,800
210,000
49,000
3,900
<167
477
12,000
13,000
17,000
11,000
9,400
1,300
34
220
Intake
<10
<500
NA
70
<10
<20
<50
«50
<60
'2,000
0.5
<50
<50
<50
<200
<10
<50
<200
<10
<600
13
ND
ND
ND
ND
<10
220
ND
ND
ND
ND
530
71
113
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
7.9
<2.4
<5
8
<1
<20
24
380
380
3
24
1
<50
6
<150
*A11 data from 3-batch sampling except as noted.
Data from 1-batch sampling.
cData from 2-batch sampling.
Date: 6/23/80
11.13-20
-------
TABLE 13-11. WASTEWATER CHARACTERIZATION, PLANT 10 (INK)a [2]
Category: Paint and Ink Formulation
Subcateqory: Hater and/or caustic rinse
Wastewater treatment description: Gravity separation
Untreated wastewater flowrate, gpd: 101-250
Pollutant
Metals, ug/L
Sliver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
, 1,2-Dichloroethane
1,1, 1-Tnchloroe thane
1 , 1-Dichloroethane
1,1, 2-Trichloroethane
Chloroform
1 , 1-Dichloroethylene
1 , 2-7)-an8-dichloroethylene
1 , 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dichlorobromome thane
Chlorodlbromome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Classical and others
pH, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
TS, mg/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
<10
1,000
NA
500
<10
<20
<50
8,700
430
2,300
10
53
490
<50
21,000
<25
2,200
2,300
<10
<600
300
NO
ND
ND
TO
<10
110
25
ND
ND
ND
1,600
ND
ND
ND
ND
ND
1,300
41
ND
72
ND
10
ND
8.5°
400
1,100
230
76
93
72
2,200
1,900
270
400
120
<50
23
570
Treated
effluent
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Sludge
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Intake
<10
<500
NA
70
<10
<20
<50
70
BO
<2,000
5.9
-------
TABLE 13-12. WASTEWATER CHARACTERIZATION, PLANT 21 (INK)a [2]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic rinse
Hastewater treatment description: None
Untreated wastewater flowrate, Tpd: 251-500
Pollutant
Metals, vg/L
Silver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
1, 2-Dichloroethane
1,1, 1-Tr ichloroethane
1 , 1-Dichloroethane
1,1, 2-Tr ichloroethane
Chloroform
1 , 1-Dichloroethy lene
1, 2-Trana-dichloroethylene
1, 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dichlorobromome thane
Chlorodibromomethane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroe thy lene
Toluene
Trichloroe thy lene
Classical and others
pH, pH units
BOD , mg/L
COD, mg/L
TOC , mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
IS, mg/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
wastewater
<10
30,000
NA
20,000
<10
80
<50
60,000
100,000
10,000
1,100
80
600,000
<50
200,000
50
1,000
3,000
<10
10,000
33
ND
ND
120
10
ND
ND
<10
ND
ND
ND
26
ND
ND
ND
ND
ND
ND
ND
87,000
770
170
580
19
9.9
73,000
270,000
66,000
1,500
540
510
51,000
51,000
275
78,000
220
<50
2
1,100
Treated
effluent
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Sludge
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Intake
<10
<500
NA
<50
<10
<20
<50
100
60
<2,000
<0.5
60
300
<50
<200
<10
<50
<200
<10
<600
47
ND
ND
ND
ND
ND
170
ND
ND
ND
ND
ND
23
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
6.3
<2.4
6.4
5.5
1
<20
<20
200
190
4
92
4
<50
3
<150
aAll data from 1-batch sampling.
Date: 6/23/80
11.13-22
-------
TABLE 13-13. WASTEWATER CHARACTERIZATION, PLANT 22 (INK)a [2]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic rinse
Hastevater treatment description: Gravity separation,
and clarification, neutralisation
Untreated wastewater flowrate, gpd: 1,000+
settling
Pollutant
Metals, ug/L
Silver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
1 , 2-Dichloroe thane
1,1, 1-Tr ichloroethane
1 , 1-Dichloroe thane
1, 1, 2-Tr ichloroethane
Chloroform
1 , 1-Dichloroe thy lene
1, 2-JTane-dichloroethylene
1, 2-Dichloropropane
Ethylbenzene
Me thy lene chloride
Dichlorobromome thane
Chi or od ibromome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Oi-n-butyl phthalate
Tetrachloroe thy lene
Toluene
Trichloroe thy lene
Classical and others
pB, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease. ng/L
Cyanide, ug/L
Total phenol, ug/L
TS, mg/L
TDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, atg/L
Sodium, mg/L
Untreated
wastewater
<10
20,000
NA
20,000
<10
90
900
10,000
10,000
30,000
NA
400
700
<50
90,000
<25
-------
TABLE 13-14. WASTEWATER CHARACTERIZATION, PLANT 23 (INK) [2]
Category: Paint and Ink Formulation
Subcategory: Water and/or caustic rinse
Wastewater treatment description: Gravity separation,
and clarification
Untreated wastewater flowrate, gpd: 1-100
•ettling
Pollutant
Metals, ug/L
Silver
Aluminum
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Molybdenum
Nickel
Lead
Antimony
Tin
Titanium
Thallium
Zinc
Toxic organics, ug/L
Benzene
Carbon tetrachloride
1 , 2-Dichloroe thane
1,1, 1-Trichloroethane
1 , 1-Dichloroe thane
1,1, 2-Trichloroethane
Chloroform
1 , 1-Dichloroethylene
1, 2-Trans-dichloroethylene
1 , 2-Dichloropropane
Ethylbenzene
Methylene chloride
Dichlorobromome thane
Chlorodlbroraome thane
Isophorone
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Classical and others
pH, pH units
BOD, mg/L
COD, mg/L
TOC, mg/L
Oil and grease, mg/L
Cyanide, ug/L
Total phenol, ug/L
TS , mg/L
IDS, mg/L
TSS, mg/L
TVS, mg/L
VSS, mg/L
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Untreated
vaitevater
<5
1,000
NA
500
<5
<10
<30
200
100
<900
NA
00
100
<30
4,000
<25
200
<80
<10
1,000
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
14
ND
ND
<10
<10
<10
ND
88
ND
12.9
48
190
46
<1
26
47
1,100
980
120
46
NA
<25
3
3,700
Treated
effluent
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Sludge
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Intake
<1
<50
NA
9
<1
<2
<5
<5
<6
<200
NA
<5
<5
<5
<20
NA
30
<20
NA
<60
ND
ND
ND
ND
ND
ND
41
ND
ND
ND
ND
15
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
<10
ND
7.2
<2.4
24
13
<1
<20
9
190
180
6
60
5
29
7
<15
aAll data from 1-batch sampling.
Date: 6/23/80
11.13-24
-------
II.13.4 POLLUTANT REMOVABILITY
Paint and ink plants treat wastewater in several ways. Generally
the plants can reduce or reuse the wastewater, or release it with
or without treatment. Because a majority of the plants release
the wastewater into municipal sewage systems, treatment is often
a function of the municipal restrictions on the plant.
II.13.4.1 Reduction or Reuse of Wastewater
There are two widely used general strategies for reducing the
amount of wastewater that paint and ink plants discharge to the
environment. The first is to reduce the amount of wastewater
generated; the second is to reuse as much wastewater as possible
within plant processes. The amount of wastewater generated is
influenced by the water pressure used for tank and equipment
cleaning, the degree of cleaning required, and the use of dry
cleaning techniques.
Several methods in use by some plants reduce the water usage.
Cleaning a tank with a squeegee prior to a water rinse reduces
the quantity of water needed to clean the tank. High pressure
hoses can also clean a tank in less time using less water.
Wastewater volume can also be reduced by eliminating or sealing
floor drains, assuring that water will not be used to clean the
floors. The use of these methods can significantly reduce the
wastewater volume of a paint or ink plant.
Reuse of wash or rinse water is common in the paint and ink indus-
try. Wash water can be transferred directly to a second tub or
can be reused as makeup water. The paint industry often uses wash
water for makeup in a batch of similar color paint. Ink plants
reuse the rinse water from a caustic rinse as makeup for a caustic
wash. These techniques can reduce raw material costs as well as
treatment costs. Generally, reuse of wastewater is more prevalent
in small plants than in larger ones.
II.13.4.2 Treatment Systems
Less than 26 percent of all paint plants and 15 percent of all ink
plants practice any types of wastewater treatment. The majority
of the plants that release wastewater discharge it to municipal
sewage systems. Of the plants that discharge their wastewater to
a municipal sewer, less than 40 percent of the paint plants and
33 percent of the ink plants pretreated the wastewater prior to
discharge.
The most common methods used by paint and ink plants for treating
or pretreating wastewater prior to disposal are gravity separa-
tion, settling, and neutralization. The paint industry also uses
physical/chemical treatment. Few plants from either industry use
biological treatment, and those that do usually have a combined
Date: 6/23/80 11.13-25
-------
treatment plant for wastes from other plant processes. No paint
or ink plants use advanced wastewater treatment methods such as
activated carbon or ultrafiltration.
Gravity Separation or Settling
Gravity separation or settling of paint and ink wastewater removes
many of the suspended solids but leaves a supernatant layer that
is high in solids and other pollutants. This treatment usually
requires large areas to achieve a reasonable removal of solids.
Neutralization
Neutralization is used to adjust the pH of the wastewater stream
to levels necessary for other treatment steps. The pH adjustment
can be made with the addition of either alkalies or acids depend-
ing on what pH is required. This technique can often significantly
reduce the dissolved metals by precipitation.
Physical/Chemical Treatment
Physical/chemical (P/C) treatment systems take advantage of the
natural tendency of paint wastewater to settle. Most plants
operate the treatment on a batch basis, collecting the wastewater
in a holding tank. If necessary, the pH is adjusted to an
optimal level, a coagulant (lime, alum, ferric chloride, or iron
salts) and/or a coagulant aid is added and mixed, and the batch
is allowed to settle (1 to 48 hours). The supernatant is dis-
charged and the sludge is treated as a solid waste. P/C removes
some metals and some organic priority pollutants, and achieves
a reduction in conventional pollutants.
Biological Treatment
Biological treatment has been used a» a secondary treatment
(usually following P/C) at several paint plants. Most of the
plants pretreat the raw wastewater and then combine it with other
plant wastewater. Data from this treatment indicate that bio-
logical treatment in an aerated lagoon can reduce conventional,
metal, and organic pollutant concentrations to low levels. Use
of this technique can be practical for paint plants in rural areas
that wish to further treat P/C effluent for both conventional and
toxic pollutants.
Biological treatment at ink plants is probably not feasible due to
the low flow (less than 1,000 gal/d) found in most ink plants.
Potential Wastewater Treatment Systems
Other treatment systems which have been suggested for use in the
paint and ink industry, but for which no data were available,
Date: 6/23/80 II.13-26
-------
include ultrafiltration, carbon adsorption, reverse osmosis, steam
stripping, dissolved air flotation, and sand filtration.
The following tables present data on several treatment processes.
Table 13-15 shows the average effluent characteristics and
removal efficiencies for batch physical/chemical treatment at
several paint plants. Table 13-16 presents data from one paint
plant that uses an aerated lagoon as a secondary treatment.
Table 13-17 presents data from an ink plant that practices gravity
separation, settling and clarification, and neutralization and
shows average effluent concentrations and removal efficiencies.
11.13.5 REFERENCES
1. Technical Study Report BATEA-NSPS-PRETREATMENT, Effluent
Limitations Guidelines for the Paint Manufacturing Industry
(draft contractor's report). Contract 68-01-3502,
U.S. Environmental Protection Agency, Washington, D.C.,
January 1979.
2. Technical Study Report BATEA-NSPS-PRETREATMENT, Effluent
Limitations Guidelines for the Ink Manufacturing Industry
(draft contractor's report). Contract 68-01-3502,
U.S. Environmental Protection Agency, Washington, D.C.,
January 1979.
3. NRDC Consent Decree Industry Summary - Paint and Ink Formulation.
4. Environmental Protection Agency Effluent Guidelines and
Standards for Paint Formulating. 40CFR446; 40FR31723,
July 28, 1975.
5. Environmental Protection Agency Effluent Guidelines and
Standards for Ink Formulating. 40CFR447; 40FR31723,
July 28, 1975.
Date: 6/23/80 11.13-27
-------
TABLE 13-15. EFFLUENT CHARACTERISTICS AND REMOVALS FROM
PAINT PLANTS WITH BATCH PHYSICAL/CHEMICAL
TREATMENT SYSTEMS [1]
Parameter
Classical pollutants, mg/L
BOD
COD
TOC
Oil and grease
Cyanide
Total solids
TDS
TSS
TVS
Metals, yg/L
Silver
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Antimony
Thallium
Zinc
Toxic organics, vg/L
Benzene
Carbon tetrachloride
1, 2-Dichloroethane
1, 1, 1-Trichloroe thane
1, 1, 2-Trichloroe thane
Chloroform
1 , 1-Dichloroethylene
1, 2-Dichloropropane
Ethylbenzene
Methylene chloride
Naphthalene
Nitrobenzene
Pentachlorophenol
Phenol
Bis { 2-ethylhexy 1) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Average
concentration
5,600
20,000
3,600
110
54
6,100
4,700
1,300
2,500
<10
<10
30
1,500
2,300
400
4,200
1,300
30
12
7,900
740
65
40
95
540
390
19
210
6,200
5,500
440
35
48
49
35
180
190
1,900
80
Percent
Average
35
68
65
90
23
68
35
82
77
14
19
31
43
56
68
19
54
11
6
68
54
75
61
39
62
50
33
52
65
54
47
89
59
28
60
88
70
54
51
removal
Median
21
74
75
97
0
80
17
98
88
0
0
0
32
70
93
0
68
0
0
85
65
100
84
30
100
57
0
58
79
67
66
100
96
0
86
99
100
70
62
aAverage of concentrations when detected.
Date: 6/23/80 11.13-28
-------
TABLE 13-16.
BIOLOGICAL TREATMENT BY AERATED
LAGOON AT ONE PAINT PLANT [1]
Parameter
Untreated P/C
wastewater effluent Lagoon Tap water
Classical pollutants
pHc
BOD
COD
TOC
Total phenol
TSS
Metals, yg/L
Silver
Arsenic
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Lead
Antimony
Selenium
Thallium
Zinc
7.4
>25,000
70,000
7,500
1.2
46,000
440
7
130
1,500
260
1,010
450
12,000
<1,000
<200
<200
60,000
7.0
23,400
260,000
25,000
1.1
400
<100
2
58
100
120
140
<5
98
170
400
100
4,200
8.3
17
675
200
0.003
42
<20
<1
<2
9
7
0.1
<5
<20
30
<200
<20
<60
7.6
<1
10
4
<0.002
<5
2.8
2
<2
7
16
0.1
<5
<20
<2
20
<2
<60
Toxic organics, yg/L
Benzene
1,1, 1-Tr ichloroethy lene
Chloroform
Ethylbenzene
Methylene chloride
Dichlorobromome thane
Chlorodibromome thane
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroe thy lene
Toluene
280
120
ND
730
6,300
ND
ND
<10
<10
ND
<10
110
290
200
560
23
ND
31,000
ND
ND
<10
<10
ND
<10
25
200
<10
22
ND
ND
1,000
ND
ND
ND
ND
<10
ND
ND
ND
ND
<10
37
ND
740
<10
<10
ND
ND
<10
ND
ND
ND
Sampling was by EPA regional Surveillance and Analysis personnel
without technical contractor or Effluent Guidelines representation.
"Values in mg/L except as noted.
"Values in pH units.
Date: 6/23/80
11.13-29
-------
TABLE 13-17.
TREATED WASTEWATER CONCENTRATIONS AND
PERCENT REMOVALS FROM INK PLANT 22 [2]
Average
Parameter concentration
Classical pollutants, rng/L
PH9
Oil and grease
BOD
COD
TOC
Total solids
TDS
TSS
TVS
Metals, pg/L
Cadmium
Chromium
Copper
Lead
Zinc
Toxic organics, pg/L
Benzene
Ethylbenzene
Methylene chloride
Chlorodibromome thane
Isophorone
Naphthalene
Pentachlorophenol
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Tetrachloroethylene
Toluene
V,
12. 5D
260
2,600
4,800
940
5,600
5,500
110
200
20
<50
<60
<200
1,000
96
2,400
29
ND
46
<10
ND
<10
10
ND
1,100
Average
percent
removal
89
87
0
76
75
73
93
96
78
>99
>99
>99
Vv
56
64
36
>99
Q
>41
>99
c
>99
69
NOTE: Toxic pollutants not measured in either stream
are not indicated.
aValue in pH units.
bThe plant's neutralization system malunctioned during
sampling.
Negligible removal.
Negative removal.
Date: 6/23/80
11.13-30
-------
11.14 PETROLEUM REFINING
II.14.1 INDUSTRY DESCRIPTION
II.14.1.1 General Description
The petroleum refining industry in the United States, as defined
by Standard Industrial Classification (SIC) Code 2911 of the U.S.
Department of Commerce, produces a wide variety of intermediates
and finished products. Table 14-1 summarizes information per-
taining to the petroleum refining industry in terms of the number
of subcategories, number of dischargers, pollutants and toxics
found in significant quantities, number of toxic pollutants
detected in raw wastewater and treated effluent, and candidate
treatment and control technologies. Production of crude oil or
natural gas from wells, natural gasoline production, other
activities associated with such production (those covered under
SIC Code 1311 for example), distribution activities (such as
gasoline stations), and petroleum product transportation are not
within the scope of SIC Code 2911, and they are therefore
excluded from this study of the petroleum refining industry.
Some other activities that are outside the scope of SIC Code 2911
are included because they are inherent to such integrated refin-
ery operations as steam generation, hydrogen production, and soap
manufacture for the production of greases, or they are part of
refinery pollution control such as treatment of ballast water
resulting from product transportation.
A petroleum refinery is a complex combination of interdependent
operations engaged in the separation of crude molecular constit-
uents, molecular cracking, molecular rebuilding and solvent
finishing to produce the products listed under SIC Code 2911.
The refining operations may be divided among general categories,
where each category defines a group of refinery operations. The
categories are storage and transportation, crude processes,
coking processes, cracking and thermal processes, hydrocarbon
processing, petrochemical operations, lube manufacturing proc-
esses, treating and finishing, asphalt production, and auxiliary
activities [2].
II.14.1.2 Subcategory Description
No subcategorization has yet been developed for BAT standards or
toxic pollutant wastewater characteristics [4].
Date: 6/23/80 II.14-1
-------
TABLE 14-1. INDUSTRY SUMMARY [1-4]
Industry: Petroleum Refining
Total Number of Subcategories: 1 (5 for BPT)
Number of Subcategories Studied: 1 (5 for BPT)
Number of Dischargers in Industry:
1973 [2] 1976 [3] 1976 [4]
• Direct: 230 182
• Indirect: 26 48J~
• Zero: 55
• Total: 247 256 285
Pollutants and Toxics Found in Significant Quantities:
• For direct discharge: • For indirect discharge:
BODs Cyanide Ammonia
COD Pyrenes Sulfides
TOC Phthalate Oil and grease
TSS esters Phenols
Oil and Chromium
grease Zinc
Ammonia nitrogen Cyanide
Phenolic compounds Pyrenes
Sulfides Phthalate esters
Chromium
Zinc
Number of Toxic Pollutants Found in:
• Raw wastewater: 40
• Treated effluent: 32
Candidate Treatment and Control Technologies:
• Recycle/reuse
• Powdered activated carbon
• Metals removal (precipitation)
Note: Blanks indicate data not available.
aSix of these refineries indicate intent to connect to
POTW in the near future. Some of these refineries dis-
charge only a portion of their wastewater to the POTW.
Six of these refineries reported no wastewater
generation.
Date: 6/23/80 II.14-2
-------
Subcategories were previously developed for BPT using linear
regression analysis on both refinery throughputs and process
capacities. These subcategories are listed in Table 14-2 [2].
Wastewater characterization data for the total industry and for
these subcategories are presented in the following section. The
size and process factors developed are listed in Reference 2.
TABLE 14-2.
SUBCATEGORIZATION OF THE PETROLEUM REFINING INDUSTRY
FOR BPT REFLECTING SIGNIFICANT DIFFERENCES IN WASTE-
WATER CHARACTERISTICS [2]
Subcategory
Basic refinery operations included
Cracking
Petrochemical
Topping Topping and catalytic reforming whether or not the
facility includes any other process in addition to
topping and catalytic process.
This subcategory is not applicable to facilities
which include thermal processes (coking, visbreaking,
etc.) or catalytic cracking.
Topping and cracking, whether or not the facility
includes any processes in addition to topping and
cracking, unless specified in one of the subcate-
gories listed below.
Topping, cracking, and petrochemical operations,
whether or not the facility includes any process in
addition to topping, cracking, and petrochemical
operations, except lube oil manufacturing
operations.
Lube Topping, cracking, and lube oil manufacturing proc-
esses, whether or not the facility includes any proc-
ess in addition to topping, cracking, and lube oil
manufacturing processes, except petrochemical
operations.
Integrated Topping, cracking, lube oil manufacturing processes,
and petrochemical operations, whether or not the
facility includes any processes in addition to
topping, cracking, lube oil manufacturing processes,
and petrochemical operations.
The term "petrochemical operations" shall mean the production of
second generation petrochemicals (i.e., alcohols, ketones, cumene,
styrene, etc.) or first generation petrochemical and isomerization
products (i.e., BTX, olefins, cyclohexane, etc.) when 15% or more of
refinery production is as first generation petrochemicals and iso-
merization products.
Date: 6/23/80
II.14-3
-------
II.14.2 WASTEWATER CHARACTERIZATION
II.14.2.1 Industry Description
Toxic Pollutants
Table 14-3 presents the number of values, ranges and concentra-
tions (mass loadings were not available) of toxic pollutants
found during a screening study at 17 petroleum refineries.
Intake water, raw wastewater, and final effluent samples were
taken for three consecutive 24-hr periods [4,5]. Raw wastewater
has been defined in the petroleum refining industry as the
effluent from the API separator, which is considered an integral
part of refinery process operations for product/raw material
recovery prior to final wastewater treatment [2]. The medians
were developed from individual plant data. No assumptions were
made as to sample locations for combining results. If sample
"names" were not the same, the results were not combined to find
medians.
Conventional Pollutants
Table 14-4 presents the number of values, ranges, and median
concentrations of conventional pollutants found during the screen-
ing study.
Wastewater Flows
It is apparent that significant reductions in the volume of
wastewater discharges have occured in this industry. At a number
of refineries, less wastewater than that which formed the basis
of BPT effluent limitations is being discharged. Not all plants
are well operated from the standpoint of wastewater generation.
However, a wastewater management policy can be instituted in
many cases as a first step to reduce wastewater discharge. There
is a potential for even further reduction of wastewater discharge
through recycle techniques (i.e., reuse of treated effluent as
cooling tower makeup).
The average wastewater flow is 28.3 gal of water per barrel of
feedstock throughput [4].
II.14.2.2 Subcategory Wastewater Characterization
Toxic Pollutants
No data are available to characterize wastewater by subcategories
in the petroleum refining industry for toxic pollutants [4].
Date: 6/23/80 II.14-4
-------
o
ft)
rt
TABLE 14-3.
u>
oo
o
I
cn
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND DURING A SCREENING
STUDY, IN PETROLEUM REFINING WASTEWATER [4,5]
(ug/L)
Toxic pollutants
Hetals and inorganics
Antimony0
Arsenic .
Asbestos
Beryllium1
Cadmium0
Chromium0
Copper
Cyanide
Lead*
Hercurv
Nickel*
Selenium
Silver^
Thallium0
Zinc
Pthalates
8is(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-chlorophenol
2 ,4-Dichlorophenol
2 , 4-D^nl t rophenol
2,4-Dimethylphenol
2-Nitrophenol
4-Nltrophenol
Pentachlorophenol
Phenol
4 , 6-Dinitro-o-cresol
Aromatics
Benzene
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
Number
of .
value«b
17
18
4
85
as
85
86
52
88
70
88
23
85
34
90
6
5
2
3
1
1
3
9
1
4
1
14
1
3
16
1
1
10
14
Intake
Range
3-35
<1-<20
<1-<200
1-3,000
1-300
10-60
<1-700
<1-790
2-<20
<1-<2SO
<1-2.800
ND-1.100
HD-30
ND-20
ND-<10
1ID-10
ND-14
ND-<10
API separator effluent
Median
<25
C20
ND
<2
<20
<24
10
20
<60
100
1,400
2.900
ND
250
60
ND
>100
>100
>100
Number
°f b
values
7
7
35
35
38
35
20
38
20
35
10
30
11
38
1
2
1
1
4
2
5
2
4"
1
1
1
4
OAF effluent
Range
l-<25
<4-<20
<1-<20
<1-<200
<5-2,000
3-400
10-3,000
<15-<600
<0. 1-1.1
1-<500
5-<20
<1-<250
<1-<15
30-3,000
>100-18,000
ND- 1,400
ND-34,000
ND-2,000
< 10-76, 000
Median
<25
20
<2
<2
270
9
45
<60
100
ND
ND
>100
<100
-------
O
ED
rt
CD
cr>
U)
X.
00
o
I
CTi
TABLE 14-3 (continued)
Toxic pollutants
Polycrylic aromatic hydrocarbons
Acenaphthene
hcenaphthylene
Anthracene
Benzo(a)pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlo mated b.'phenyls and related compounds
oclo 1016
oclo 1221
oclo 1^32
oclo 1242
oclo 1248
* oclo 1254
A oclo 1260
Halogenated aliphatics
Carbon tetrachloride
Chloroform
Dichlorobromonte thane
1,2-Dichloroe thane
1 , 2-Trans-dichloroethylene
Hethylene chloride
i,l 2,2-Tetrachloroethane
Tetrachloroethylene
1,1, l-Trichloroe thane
Tnchloroethylene
Pesticides and metabolites
Bldrin
a-BHC
p-BHC
5-BHC
y-BHC
Chlordane
4,4'-DDE
4,4'-DDD
or-Endosulfan
B-Endosulfan
Endosulfan sulfate
Heptachlor
Hep'.achlor epoxide
tsophorone
Number
o£ b
values
7
5
2
2
8
8
4
11
11
6
7
7
8
8
4
4
4
4
6°
1
2
3.
10"
2
4
1
2
2
1
3
2
1
1
1
1
1
1
1
2
2
2
Intake
Ranqe
ND-29
HD-0 ^
ND-33
MD-49
ND-29
ND-1
ND-2
HD-160
ND-140
ND-0.2
HD->50
ND-70
HD-11
ND-130
ND-<10
ND-50
<10-20
API separator effluent
Hedian
ND
HD
ND
17
ND
ND
ND
ND
ND
<0.1
ND
HD
HD
ND
ND
ND
ND
<5
<8
ND
ND
ND
<85
<5
<10
<50
<15
ND
HD
ND
ND
ND
2.8
ND
ND
ND
ND
ND
ND
ND
HD
Number
of .
values
5
4
1
1
5
5
2
9
8
3
5
4
g
6
2
2
2
1
9
1
2
3.
7=
2
3
1
2
1
2
1
1
1
1
2
1
Range
HD-520
KD-660
0.1-40
ND-40
ND-270
HD-3,200
5-1,100
ND-16
ND-40
ND-<10
ND-C10
ND-<10
ND-100
ND-16
ND-20
ND-1, 600
ND->50
CS-12
100 3
ND
ND 1
HD 1
<8
1
<5 1
<8
1
7
1
ND 1
13
1
<5 1
<2.5
3,600 1
DAF effluent
Range
150-390
ND-0.3
110-495
106-3,700
50-1,800
7 9-<10
3 5-<10
0 2-<10
ND-<10
ND-560
Median
270
530
1,800
ND
ND
300
700
600
5
<10
<10
<10
<5
<10
<10
<10
<5
13
30
ND
HD
<10
<5
<5
<5
0.1
<5
<5
2,500
-------
rt-
(D
N)
co
CO
o
TABLE 14-3 (continued)
Second API
separator effluent
Toxic pollutants
Hetals and inorganics
Antimony
Arsenic .
Asbestos
Beryllium0
Chromium0
Copper0
Cyanide
Lead0
Mercury
Nickel
Selenium
Silver
Thallium0
Zinc
Pthalate*
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
of b
values
2
2
10
10
13
10
5
13
11
10
6
10
5
13
1
1
1
Range
Third API
separator effluent
Number
of b
values
1
1
S
8
5
3
5
7
5
4
5
4
B
1
1
1
Range Median
<1
3
m
Fhenols
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dinitrophenol
2,4-niMthylphenol
2-Nitrophenol
4-Mitrophenol
Pentachlorophenol
Phenol
4,6-Dinitro-o-cresol
Parachloroawta cresol
Aroautics
Benzene
1,2-Dichlorobenzene
1,4-Dichlorobencene
Ethylbenzene
Toluene
m
>130
>100
MOO
850
16,000
-------
D
0)
rt
(D
TABLE 14-3 (continued)
to
OJ
CD
O
H
I
CO
second API Third API
separator effluent separator effluent
Toxic pollutants
Polycrylic aroMatic hydrocarbons
Acenaph thene
Acenaphthylene
Anthracene
Benzo(a)pyrene
Chrysene
Fluoran thene
Fluorene
Naphthalene
Phenanthrene
Pvrene
"olvchlonnated biphenyls and related compounds
Aroclo 1016
Aroclo 122.
Aroclo 1232
Aroclo 1242
Aroclo 1248
Aroclo 1254
Aroclo 1260
Number
of b
values Range
2
1
2 2-30
2 ND-9
2 ND-300
2 280-350
2 ND-90
1
1
1
2 ND-0 . 5
Number
of .
Hedian values Range
<1 , 500 1
NO
16 1
5 1
150 1
315 1
45 1
7
0.2 1
0.5 1
0.3 1
Hedian
HD
50
NT
ND
HD
ND
ND
NO
ND
Fourth API
separator effluent
Number
of
values Range
1
1
1
1
1
1
1
1
Median
50
40
20
80
ND
230
ND
ND
ND
Halogenated aliphatics
Carbon tetrachloride
Chloroform
D ichlorobroBOM thane
1,2-Dichloroethane
1,2-Trans-dichloroethylene
Nethylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
1,1.1-Trichloroethane
Trichloroethylene
Pesticides and netabolites
Aldrin
a-BHC
p-BHC
6-BHC
Y-BHC
Chlordane
4,4'-DDE
4,4'-ODD
o-Endosulfan
p-Endosulfan
Endosulfan sulfate
Heptachlor
Heptachlor epoxide
Isophorone
-------
o
0)
rt
ro
CTi
to
00
o
TABLE 14-3 (continued)
I
vo
Toxic pollutants
Hetals and inorganics
Antimony0
Arsenic ,
Asbestos
Beryllium
Cadmium0
Chromium0
Copper0
Cyanide
Lead
Mercurvr
Nickel
Selenium0
Silver
Thallium
Zinc
Pthalaces
Bis(2-ethylhe*yl) phthalate
Di-n-butyl phthalate
Oiethyl phthalate
Dunethyl phthalate
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2 ,4-Dinitrophenol
2 4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
4 , 6-Dinitro-o-cresol
Aroma tics
Benzene
i , 2-Dichlorobenzene
1 , 4-Dich]orobenzene
Ethylbenzene
Toluene
Fifth API
Number
of
values
1
1
5
8
8
5
3
5
7
5
4
5
4
8
1
1
1
1
1
1
separator effluent
Range Median
9
12,000
Chemical plant
Number
of .
values Range
1
1
5 <2-<3
5 <1-<20
5 500-800
5 <4-13
3 <30-<60
5 <15-<60
5 <0.1-<0.
5 <15-<50
1
5 <5-<25
1
5 4,100-6,5
1
1
1
1
J
1
effluent
Median
<25
<20
<2
<20
680
7
<60
<60
5 02
<50
<20
<25
'15
00 4,800
<100
40
10
90
20
>100
-------
o
Oi
ft
TABLE 14-3 (continued)
OJ
00
O
I
(-•
o
Toxic pollutants
Polycrylic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
8enzo(a)pyrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Polychlorinated biphenyls and related compounds
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Fifth API
Hurf>er
of .
values
1
1
I
1
1
1
1
1
1
separator effluent
Range Median
ND
ND
ND
ND
ND
ND
ND
HD
KD
Biopond influent
Number
of b
values Range Median
1 ND
ND
ND
ND
ND
ND
1 HD
1 HD
1 0.1
Chemical plant effluent
Number
of .
values Range Median
1 HD
1 ND
1 <0.1
1 ND
1 27
1 1
1 1
1 J.3
1 HD
1 0.1
Halooenated aliphatics
Carbon tetrachloride
Chlorofora
Dichlorobronwate thane
1,2-Dichloroethane
\,2-Trans-dichloroethylene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
1,1,1-Trichloroethane
Trichloroethylene
Pesticides and Mtabolites
ildrm
o-BHC
P-BHC
6-BHC
y-BHC
Chlordane
4,4'-DDE
4,4'-BBD
cr-Endosulfan
^-Endosulfan
Endosulfan sulfate
Heptachlor
Heptachlor enoxide
Isophorone
<100
-------
D
0)
rt
(D
NJ
u>
oo
o
TABLE 14-3 (continued)
Toxic pollutants
Metals and inorganics
Antimony
Arsenic .
Asbestos
Beryllium17
Cadmiumc
Chromium
Copperc
Cyanide
Lead
Mercury
Nicker
Selenium
Silver
Thallium
Zinc
Pthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
2-Chlorophenol
2 , 4-Dichlorophenol
2,4-Dinitrophenol
2 , 4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
4 , 6-Dinltro-o-cresol
Parachlorometa cresol
Aromatics
Benzene
1 , 2-Dichlorobenzene
1 , 4-Dichloroben2ene
Ethylbenzene
Toluene
Cooling tower blowdown
Number
values Range Median
1 <25
1 41
5 <2-<3 <2
5 <1-<20 <20
5 44-79 57
5 280-510 400
3 520-830 830
5 <15-<60 <60
S 0.4-0.7 0.5
5 64-130 88
5 <5-<2SO <25
J
-------
ft"
n>
CTi
NJ
U>
00
o
TABLE 14-3 (continued)
i
(-•
to
Cooling tower blovdovn Treated effluent
Number Number
of . of .
Tome pollutants values Range Median values Range Median
Polycrylic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)pyrene 10
Chrysene 7
Fluoranthene MD
Fluorene
Naphthalene 1 HD
Phenanthrene 21 ND
Pyrene 10
Folychlorinated biphenyls and related compounds
Aroclor 1016
Aroclor 1221 1 0.1
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Halogenated aliphatics
Carbon tetrachloride 1 ND
Chloroform 1 ND
Dichlorobromome thane
1,2-Dichloroethane 1 ND
1 , 2-Trans-dichloroethylene
Methylene chloride 1 70 0
1,1,2, 2-Tetrachloroe thane
Tetrachloroethylene
1.1.1-Trichloroetliane 1 ND
Trichloroethylene
Pesticides and metabolite.
Aldrin
0-8HC
B-BHC 0.7
o-BHC
1-BHC
Chlordane 1 ND
4.4>-DDE
4,4'-DDD
o-Endosulfan
B-Endosulfan
Endosulfan sulfate
Heptachlor
Heptachlor epoxide
Isophorone
Fin
Number
of b
values
7
5
2
2
9
9
5
11
12
7
7
7
a
9
4
4
4
4
8
1
2
3
8*
2
4
1
2
2
2
2
2
al effluent
Range
HD-6
1 3-3
ND-1 4
ND-<0.1
ND-0.1
ND-1
ND-7
ND-<10
ND-<10
ND-<10
WD-<10
ND-<10
KD-66
ND-<10
HD-<10
ND->100
ND-<10
ND-<10
ND-<5
Median
ND
ND
HD
2.2
ND
ND
ND
HD
ND
<0.1
^10
<10
<5
ND
-------
o
rt
(D
to
to
oo
o
M
H
•
H-
I
U)
TABLE 14-4. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND DURING A
SCREENING STUDY IN PETROLEUM REFINING WASTEWATER [4]
Intake
Number
of
Pollutant
BODs,a mg/L
COD , mg/L
TOC , mg/L
TSS , mg/L
Ammonia, mg/L
Cr+6, mg/L
S-2, mg/L
Oil and grease, mg/L
pH
Cyanides, mg/L
Phenols, mg/L
BOD 5°, mg/L
BOD 5 , mg/L
Flow, MGD
BOD5a, mg/L
COD , mg/L
TOC, mg/L
TSS , mg/L
Ammonia, mg/L
Cr + 6, mg/L
S-2, mg/L
Oil and grease, mg/L
pH
Cyanides, mg/L
Phenols, mg/L
BOD 5°, mg/L
BOD 5 , mg/L
Flow, MGD
values Range
40
49
48
51
49
48
50
27
44
51
51
29
12
18
4
6
6
5
6
6
6
3
6
6
5
3
6
3
<1 -
1 -
1 -
<1 -
<1 -
<0.02 -
<0.1 -
2 -
6.3 -
<0.005 -
<0.0001 -
<1 -
<1 -
1.5 -
Second
separator
32 -
170 -
46 -
36 -
7.8 -
<0.02 -
0.8 -
84 -
6.3 -
0.01 -
1 -
31 -
34 -
5.0 -
42
350
110
290
68
0.25
1.6
31
9.0
<0.10
0.21
52
35
35
API
effluent
85
690
230
200
15
0.05
15
250
8.4
0.21
22
42
>84
7.2
Median
<3
16
10
9
<1
<0.02
0.3
8
7.7
<0.02
<0.005
<3
4
4
>42
260
57
64
8.7
<0.02
3.6
140
8.2
0.05
2.1
38
>42
5.4
API separator effluent
Number
of
values Range Median
25
28
25
30
28
27
27
17
28
32
32
16
16
10
2
3
3
3
3
3
3
3
3
3
3
3
3
20 -
91 -
25 -
10 -
1 -
<0.02 -
0.3 -
24 -
5.7 -
<0.005 -
<0.001 -
<15 -
39 -
3 -
Third
separator
15 -
160 -
45 -
38 -
3.0 -
1.8 -
23 -
7.3 -
0
0.27 -
22 -
0.42 -
320
860
240
490
52
7
35
150
11
1.5
62
280
260
18
API
effluent
20
660
230
110
8.4
15
250
8.2
1.3
>84
0.46
79
330
88
68
12
0.02
4.1
51
8.6
0.05
2.8
90
82
4.1
DAF effluent
Number
of
values Range Median
21
21
21
21
21
21
18
12
17
20
21
19
7
4
36 -
150 -
39 -
7 -
5.3 -
<0.02 -
0.4 -
10 -
6.9 -
0.01 -
0.7 -
25 -
34 -
1.8 -
280
1,200
360
380
40
0.75
30
590
10.4
3.0
110
<360
250
5.4
120
440
110
37
12
<0.02
1.5
18
8.2
0.04
11
<120
80
1.8
Fourth API
separator effluent
18
180
52
62
6.2
0.02
5.3
25
7.4
0.01
0.69
58
0.44
2
3
3
3
3
3
3
3
3
3
3
3
70 -
270 -
58 -
26 -
3 -
<0.02 -
5.1 -
34 -
7.6 -
0.05 -
1.5 -
55 -
>80
430
97
94
8.4
0.05
9.1
150
7.8
0.06
9.5
100
>75
310
66
36
7.3
<0.02
6.8
65
7.7
0.06
2.0
60
Date: 6/5/79
(continued)
-------
o
0)
rt
0)
(Ti
U)
CO
o
.fc.
I
TABLE 14-4 (continued)
Fifth API separator effluent
Biopond influent
Number Number
of of
Pollutant values Range Median values Range
BOD 5 , mg/L
COD , mg/L
TOC, mg/L
TSS, mg/L
Ammonia, mg/L
Cr+6, mg/L
S~2 , mg/L
Oil and grease, mg/L
PH
Cyanides, mg/L
Phenols, mg/L
BOD5b, mg/L
BOD 5 , mg/L
Flow, MGD
BOD5a, mg/L
COD , mg/L
TOC , mg/L
TSS, mg/L
Ammonia, mg/L
Cr+6, mg/L
S-2, mg/L
Oil and grease, mg/L
pH
Cyanides, mg/L
Phenols, mg/L
BOD5b, mg/L
BOD 5 , mg/L
Flow, MGD
Note: Blanks indicate
a
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
3
4
4
3
1
data
10 - 12
83 - 92
22 - 31
16 - 48
<1 - 2.0
0.09 - 0.14
<0.1 - 12
7-25
7.1 - 8.1
0.214 - 0.294 0
10 - 18
Cooling tower blowdown
25 - 130
210 - 350
62 - 95
64 - 80
3.9 - 19
0.05 - 0.41
<0.1 - 1.0 <
6.8 - 7.1
0.02 - 0.83
0.037 - 0.056 0
36 - >160
not available.
n
11
75
23
26
1.0
0.13
1.0
9
8.1
0.02
.246
10
47
300
78
76
10
0.09
0.05
7.3
0.68
.048
42
0.17
1
3
3
3
3
3
3
3
3
3
3
1
3
3
3
3
3
3
3
3
3
4
3
3
480
50
16
20
0.08
3.5
9
7.4
0.22
83
Treated
28
120
38
18
4.5
0.2
8
7.6
0.05
<0.001
0.074
- 610
- 120
- 24
- 24
- 0.10
- 49
- 20
- 7.9
- 0.34
- 120
effluent
- 40
- 130
- 44
- 28
- 8.4
- <0.5
- 15
- 7.8
- 0.17
- 0.016
- 0.153
Median
>84
570
100
18
22
0.08
14
11
7.7
0.26
110
>84
34
130
41
20
5.6
<0.02
<0.5
11
7.7
0.10
<0.001
0.085
Chemical plant effluent
Number
of
values Range
3
3
3
3
3
3
3
3
3
1
2
3
43
48
47
47
48
45
49
27
48
53
49
38
38
240 - 810
69
78
<1. 0
0.7
6.6
<0.02
0.062
74
0.8
Final
fl
28
7
2
<1
0.01
<0. 1
3
6.9
<0.005
<0.001
<1
0.017
- 240
- 40
- 2.0
- 0.9
- 68
- <0.10
- 0.073
- 140
- 0.95
effluent
- 210
- 820
- 290
- 110
- 53
- 0.11
- 2.1
- 53
- 8.8
- 0.80
- 0.080
- 92
- 17.6
Median
340
93
36
1.1
<0.02
0.9
6.7
<0.05
0.068
34
110
0.9
<10
120
36
21
5.0
<0.02
0.5
13
7.7
<0.03
0.013
7
2.27
Seed from refinery final effluent.
=No seed.
-------
Conventional Pollutants
Table 14-5 presents ranges and median concentrations in waste-
water of conventional pollutants for the petroleum refining
industry subcategories. BOD5, COD, TOC, oil and grease, ammonia
as nitrogen, phenolic compounds, sulfide, chromium, and TSS have
been selected as significant pollutant parameters [2,3].
Table 14-6 presents the number of plants, ranges, and median
concentrations in wastewater for conventional pollutants for
indirect discharges from the topping and cracking subcategories
of petroleum refining. The available data were not sufficient
for the other subcategories. These data tend to confirm that
there are no significant differences in raw wastewater character-
istics (flow, and conventional and classical pollutants) for
indirect dischargers and for the petroleum refining industry as
a whole, and further analysis confirmed this [3].
Table 14-7 presents ranges and median loadings in raw wastewater
of conventional pollutants for the petroleum refining industry
subcategories [2],
Wastewater Flows
Table 14-8' presents the median flows for the petroleum refining
industry subcategories [2,4].
II.14.3 PLANT SPECIFIC DESCRIPTIONS
Screening studies were undertaken to do the following (a) analyze
for the presence of the 129 toxic pollutants in the plants'
intake water sources, (b) analyze the plants' raw wastewaters to
determine the net production of toxic pollutants as a result of
refinery process operations, and (c) analyze the plants' final
effluents for the presence of toxic pollutants and to determine
an indication of the removal efficiencies of BPT-type wastewater
treatment systems for these pollutants.
The screening studies were conducted by the Robert S. Kerr
Environmental Research Laboratory (RSKERL) and Burns and Roe
(B&R). The details of how the plants were selected in both
studies are available in Reference 4. The combined studies
sampled 17 refineries, at which intake water, raw wastewater, and
final effluent samples were collected for three consecutive 24-hr
periods. Preserved samples were analyzed by the following
laboratories:
(1) (EPA) Robert S. Kerr Environmental Research Laboratory
(RSKERL), Ada, Oklahoma — metals, cyanides, phenolics,
mercury
Date: 6/23/80 11.14-15
-------
TABLE 14-5.
RAW WASTEWATER CHARACTERIZATION BY
SUBCATEGORY IN PETROLEUM REFINING [2,3]
(mg/L)
Topping
subcategory
Characteristics
BOD 5
COD
TOC
TSS
Nitrogen, ammonia as
Phenolic compounds
Sulf ides
Oil and grease
Total chromium
Range
10
50
10
10
0.05
0
0
10
0
- 50
- 150
- 50
- 40
- 20
- 200
- 5
- 50
- 3
Median
23.3
107
20
2.72
0.80
0.240
25
0
Cracking
subcategory
Range
30
150
50
10
0.5
0
0
15
0
Lube
subcategory
BOD 5
COD
TOC
TSS
Nitrogen, ammonia as
Phenolic compounds
Sulfides
Oil and grease
Total chromium
100
400
100
80
1
0.1
0
40
0
- 700
- 700
- 400
- 300
- 120
- 25
. 40
- 400
- 2
100
300
50
20
1
0.5
0
20
0
- 600
- 400
- 500
- 100
- 200
- 100
- 400
- 700
- 6
Median
138
383
66.
28.
6.
1.
52.
0.
3
6
04
24
8
109
Petrochemical
subcategory
Range
50
300
100
50
4
0.5
0
20
0
- 800
- 600
- 250
- 200
- 300
- 50
- 200
- 250
- 5
Median
144
418
135
42
10
176
44
0
.1
.0
.9
.471
Integrated
subcategory
- 800
- 600
- 500
- 200
- 250
- 50
- 60
- 500
- 2
114
261
51.
14.
2.
1.
44.
0.
5
5
25
24
1
272
TABLE 14-6.
RAW WASTEWATER CHARACTERIZATION BY SUBCATEGORY IN
PETROLEUM REFINING FOR INDIRECT DISCHARGERS [3]
Topping
subcategory
Characteristics
Flow, MGD
BOD 5, mg/L
COD, mg/L
Ammonia, mg/L
Phenol ics, mg/L
Sulfides, mg/L
Oil and grease, mg/L
Total chromium, mg/L
Number
of
plants
6
1
6
5
6
6
6
6
Range
0.006
205
71
0.617
<0.05
<0.01
0.8
<0.005
- 0.258
- 323
- 905
- 127
- 63.4
- 75.3
- 195
- 8
Median
0.127
-*
275
34.0
<1.96
<0.05
32
<0.62
Number
of
plants
11
5
7
9
11
10
10
9
Cracking
subcategory
0.80
38
179
3.2
0.19
0
2
0.3
Range
- 4.42
- 756
- 5,970
- 1,130
- 213
- 51.6
- 160
- 330
Median
1.34
75
463
21.4
10.5
0.9
40
0.844
'insufficient data.
Date: 6/23/80
11.14-16
-------
rt
ro
K)
u>
00
o
I
M
-J
TABLE 14-7
RAW WASTEWATER LOADINGS IN NET KILOGRAMS/1,000 m3 OF FEEDSTOCK
THROUGHOUT BY SUBCATEGORY IN PETROLEUM REFINING [2]
Characteristics
Flow0
BOD 5
COD
TOC
TSS
Sulfides
Oil and grease
Phenols
Ammonia
Chromium
Flow0
BOD5
COD
TOC
TSS
Ammonia
Phenols
Sulfides
Oil and grease
Chromium
Topping
subcategory
Range
8.00
1.29
3.43
1.09
0.74
0.002
1.03
0.001
0.077
0.0002
68.6
62.9
166
31.5
17.2
6.5
4.58
0.00001
23.7
0.002
- 558
- 217
- 486
- 65.8
- 286
- 1.52
- 88.7
- 1.06
- 19.5
- 0.29
Lube
subcategory
- 772
- 758
- 2.290
- 306
- 312
- 96.2
- 52.9
- 20.0
- 601
- 1.23
Median
66.
3.
37.
8.
11.
0.
8.
0.
1.
0.
117
217
543
109
71.
24.
8.
0.
120
0.
6
43
2
01
7
054
29
034
20
007
5
1
29
014
046
Cracking
subcategory
Petrochemical
subcategory
Range Median
3.29
14.3
27.7
5.43
0.94
0.01
2.86
0.19
2.35
0.0008
40.0
63.5
72.9
28.6
15.2
0.61
0.52
20.9
0.12
- 2,750
- 466
- 2,520
- 320
" 36° d
- 39.5°
- 365
- 80.1
- 174
- 4.15
Integrated
subcategory
- 1.370
- 615
- 1,490
- 678
- 226
- 22.6
- 7.87°
- 269
-1.92
93.
72.
217
41.
18.
0.
31.
4.
28.
0.
235
197
329
139
59.
3.
2.
74.
0.
0
9
5
2 d
94°
2
00
3
25
1
78d
00°
9
49
Range
26.6
40.9
200
48.6
6.29
0.009
12.0
2.55
5.43
0.014
- 443
- 715
- 1,090
- 458
- 372
- 91.5
- 235
- 23.7
- 206
- 3.86
Median
109
172
463
149
48.6
0.86
52.9
7.72
34.3
0.234
After refinery API separator.
^Probability of occurrence less than or equal to 10% or 90% respectively.
°1,000 m3/l,000 m3 of feedstock throughput.
dSulfur.
-------
TABLE 14-8. SUBCATEGORY WASTEWATER FLOWS [2,4]
Median flow,
gal/bbl feedstock
throughput
1974 Guidelines
Subcategory
1974
1977
BPT flow basis,
gal/bbl feedstock
throughput
BAT flow basis,
gal/bbl feedstock
throughput
Topping
Cracking
Petrochemical
Lube
Integrated
23.3
32.5
155
41
480
7.8
17.3
24.9
40.1
36.0
20
25
30
45
48
10.5
14
19
30.5
36.5
(2) EPA Region V Laboratory, Chicago, Illinois -- metals,
mercury
(3) Midwest Research Institute (MRI), Kansas City, Missouri —
volatile and semivolatile organics
(4) Ryckman, Edgerley, Tomlinson, and Associates, Inc. (RETA),
St. Louis, Missouri — volatile and semivolatile organics,
pesticides, cyanides, phenolics, mercury, metals, asbestos,
traditional parameters
(5) Gulf South Research Institute, Baton Rouge, Louisiana —
volatile and semivolatile organics
(6) NUS Corporation, Pittsburgh, Pennsylvania — volatile and
semivolatile organics, pesticides
The conventional parameters for which refinery wastewater samples
were analyzed include BOD5, COD, TOC, TSS, oil and grease,
ammonia, sulfides, hexavalent chromium, and pH. Each of the
three consecutive 24-hr composites collected at each sampling
location in a given refinery was tested for eight of these
parameters. Grab samples collected at the end of each sample day
were used for the oil and grease analyses. Three seeding alter-
natives were used in performing the BODs analyses. Method 1 used
a seed from a domestic sewage treatment plant; Method 2 used
refinery final effluent as a seed; and no seed at all was used in
Method 3.
Analyses for semivolatiles, acid extractables, and base-neutrals
were completed.
Pesticides were looked for in samples from 11 of the refineries,
but without GC/MS verification.
Date: 6/23/80
11.14-18
-------
Samples were collected in each 24-hr period for cyanides,
phenolics, and mercury, and reported as Day 1, 2, or 3 results.
RSKERL and RETA analyzed for cyanides, mercury, and phenolics,
and "mercury (laboratory 2)" results are from EPA's Region V
Laboratory. Samples from each 24-hr period and a 72-hr composite
were analyzed for toxic pollutant metals. These analyses were
performed by RSKERL, RETA, and EPA's Region V Laboratory.
Asbestos was looked for in samples from four refineries (I, L, M,
and P). It is thought that asbestos contributions within a
refinery may be affected by rainfall; two of the four refineries
tested had dry weather, and two had significant rainfall.
Tables 14-9 through 14-25 present the analytical results on a
refinery-by-refinery basis.
II.14. 4 POLLUTANT REMOVABILITY
II.14.4.1 Toxic Pollutants
Based on the limited data received, it appears that BPT technol-
ogy (including biological treatment plus effluent polishing)
provides effective removal of toxic pollutants identified as
being present in petroleum refining raw wastewaters. It has been
shown that after the application of BPT-type technology, effluent
metals concentrations occur at the range typical of what would
occur after the application of precipitation techniques. In all
cases for which complete data are available, organic toxic pollu-
tants present in the raw wastes, sometimes at levels in the low
mg/L range, have been shown to be removed to levels in the low
yg/L range (generally less than 10 pg/L). No data on removabil-
ity of toxic pollutants other than that shown in Table 14-3 in
ranges and median concentrations for intake, raw wastewater, and
final effluent are available for toxic pollutants [4,5].
II.14.4.2 Conventional Pollutants
End-of-pipe control technology in the petroleum refining industry
relies heavily upon the use of biological treatment methods.
These are supplemented by appropriate pretreatment to insure that
proper conditions, especially sufficient oil removal and pH
adjustment, are present in the feed to the biological system.
When used, initial treatment most often consists of neutraliza-
tion for control of pH and equalization basins to minimize shock
loads on the biological systems. The incorporation of solids
removal ahead of biological treatment is not as important as it
is in treating municipal wastewaters.
The selection of plants was not based on a cross section of the
entire industry, but rather was biased in favor of those segments
of the industry that had the more efficient wastewater treatment
Date: 6/23/80 11.14-19
-------
TABLE 14-9.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY A [4,5]
Intaka
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
pH
Ammonia
Metals and inorganics, U9/L
Antunony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Day
1
<2
<2
4
1
5
<10
<0.1
7.9
<1.0
<2
<20
<24
<20
<10
<60
0.1
<50
<^5
Day
2
<1
<1
4
2
4
<10
<0.1
9.0
11
<2
<20
<24
<20
<10
<60
0.1
<50
<25
Day
3
2
4
e
2
<1
<11
O.J
8.6
1.0
<2
<20
<24
<20
<60
0.1
<50
<25
a a ^
Comp . Comp . 1
20
24
130
36
490
<520
9.0
8.6
13
<25
<20 <1 ^t
<24 <5 <24
90
50
<60 <15 149
0.1 <0.5 0.2
<50 <15 <50
<10
<25 <5 <25
<25
Separator effluent
Day
2
20
18
91
25
390
140
6.9
8.5
11
<20
<24
30
23
60
109
0.2
<50
<25
Day
3 Comp .
25
30
99
36
260
150
8.5
9.0
11
<20 <20
1,220 30
50
39 23
40
224 114
0
<50 100
-
13
>100
>100
>100
12
37
5
<5
20
>100
>50
ND
ND
ND
ND
ND
ND
ND
ND
<5
ND
>100
<10
0.433 0.427 0.432
Note: Blanks indicate data not available.
a24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional" parameters and a composite of the
three was analyzed for the toxic pollutants.
bTotal phenols, pg/L; pH, pH units.
°Not detected in sample.
Date: 6/23/80
11.14-20
-------
TABLE 14-10.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY B [4,5]
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD-i
BOD- 3
COD
TOC
TSE
Total phenols
Sulfide
Oil and grease
pH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Thallium
Zinc
Phenols, yg/L
2 , 4-Dimethylphenol
4-Nitrophenol
Phenol
p-Chloro-^-cresol
Aromatics, ug/L
Benzene
Polychlorlnated biphenyls and
related compounds, ug/~
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Halogenated aliphatica, ug/L
Chloroform
Methylene chloride
Pesticides and metabolites,
Ug/L
B-BHC
y-BHC
4,4' -ODD
Endosulfan sulfate
Heptachlor
Flow, MOD
Intake
Day Day Day
123 Comp.a Conp.*
<3 <3 2
<3 <3 <3
999
13 25 18
9 13 a
<10 <5 <5
0.2 0.2 0.4
19 7 6
8.2 8.1 8.3
<1.0 <1.0 <1.0
<25
<20
<2 <2 7 <2 <1
30 30 50 60 <5
<20 <20 <20
30 20 40 30 <5
<20 <20 <20
60 60 50 , 70 <15
<0.5
6 6 20 20 <15
<20
<1 <1 <"> *"} £**
^J- *i. ^* <£ <3
<60 <60 100 100 15
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
22
ND
ND
ND
ND
ND
3 91 3.86 4.12
DAT effluent
Day Day Day
123 Comp.
130 170 270
140 110 220
420 440 SOO
100 110 110
38 50 38
32,000 34,000 22,000
0.6 1.0 1.2
33 IB 11
9.2 8.6 9.5
8.4 7.3 6.7
<2 <2 3 <2
SO 50 60 60
<20 100 <20
<6 9 10 10
40 50 40
<20 <20 <20 <20
<0.5
<5
-------
TABLE 14-11.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY C [4,5]
Intake
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols (laboratory 3)
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics, Mg/X*
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium *6
Copper
Cyanides (laboratory 3)
Lead
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Seleniwn
Silver
Thallium
Zinc
Day
1
2
1
12
<1
4
<0.5
8
7.6
<1.0
<20
1
<1
1.4
1.0
<2
4
<1
Day
2
<3
1
8
<1
6
<0.5
10
7.8
<1.0
<20
1
<1
1.6
6.0
<2
13
3
Day Day Day
3 Composite 4 1
<2
2
5
<1
4
0.3
4
7.4
<1.0
<20
1
<1
1.3
1.0
<2
4
<1
150
110
380
88
22
12,000
<0.5
ISO
8.6
52
1
4
<1
<1
2 770
50
2
<20 1,100
1
1.3 1.1
<0.1 <1.0
1
5 11
<1
<2 <1 <1
20 <1 630
Separator effluent
Day
2
160
120
370
75
36
3,200
3.8
100
9.1
50
820
<20
120
1.2
6.0
8
<1
670
Day Day
3 Composite 4
79
85
220
49
26
l,500d
<0.3
28
a. 7
13
-------
TABLE 14-11 (continued)
Treated effluent
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols (laboratory 3)
Sulflde
Oil and grease
pH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides (laboratory 3*
Lead
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates, ug/L
Bis(2-ethylhexyl) phthalate
Phenols, ug/L
Phenol
Aromatlcs, ug/L
Benzene
Ethylbenzene
Polycyclic aromatic hydrocarbons, ug/L
Anthracene/phenanthrene
Naphthalene
Halogenated aliphatics, ug/L
Chloroforir
1 ,2-Dichloroethane
Methylene chloride
Flow, MGD
Day
1
28
130
44
20
<1
<0.5
8
7.8
8.4
13
940
<20
100
0.8
2.0
9
10
<1
930
0.0915
Day
2
34
120
39
18
14d
<0.5
15
7.7
5.6
9
470
<20
190
1.0
5.0
6
<6
<1
440
0.0848
Day
3
40
120
41
28
0.2
11
7.6
4.5
15
1,100
<20
260
1.0
7.5
44
8
<1
930
0.1526
Composite
1
6
<1
16
490
230
17
1.2
18
15
<1
780
900
ND
ND
ND
ND
ND
ND
ND
7
Final
Day Day Day
412
37 40
130 130
42 37
20 22
2 6
0.5 0.5
7 11
8.0 8.1
7.8 17
<20 <20
30 45d
26 58
1.1 1.4
<0.2 1.0 1.0
7 7
13 10
<1 3 7
519 590 620
0.1787 0.1411
effluent
Day
3
45
100
36
16
2
0.4
11
7.0
3.9
<20
60
26
1.3
6.0
7
19
<1
590
0.2357
Composite
3
5
<1
<1
3
10
50
1.3
0.3
15
19
<1
<2
700
ND
ND
ND
ND
ND
ND
ND
20
Day
4
70
0 S
<1
545
310
Mote: Blanks indicate data not available.
24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional" parameters and a
composite of the three was analyzed for the toxic pollutants.
Total phenols, ug/L; pH, pH units,
Not detected in sample.
d
Average value.
Date: 6/23/80
11.14-23
-------
TABLE 14-12.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY D [4,5]
Pollutant
Conventional pollutants , mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfiae
pH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Aromatics, yg/L
Benzene
Ethylbenzene
Toluene
Day
1
20
20
10
24
<0.1
<1.0
<20
<200
<240
<20
<40
<20
<600
0.1
<500
<250
<250
Day
2
1
4
4
5
32
<0.1
2.2
<20
<:200
<240
<20
<40
<20
<600
0.1
*500
<250
<250
Intake
DAT effluent
Day
3 Comp . Comp .
3
6
4
8
16
23
<0.1
2.0
<20
<200
<240
<20
<40
<20
<600
0.1
<500
<250
<250
<25
<200 <1
<240 <14
<40 <5
<600 <1S
0.2 <0.5
<500 <15
<10
<250 <5
<15
<250 33
NDC
ND
ND
Day
1
160
<220
1,000
300
62
3,700
15
8. 9
36
<200
1,020
<20
<40
50
<600
0.2
*500
<250
410
Day
2
140
500
150
36
5.10U
18
8. 5
29
<20
681
<20
15
60
<60
0.1
<50
<25
242
Day
3
142
<360
390
lOO
32
8,000
15
8.6
40
<20
479
<20
6
40
<60
0.2
<50
<25
181
Comp.
<20
719
7
<60
<0.5
<50
<25
262
>100
>100
>100
Day
Comp. 1
50
40
620
290
64
1.7
7.7
36
<25
<10
<1 <20
730 1,230
<20
30
<15 <60
<0.1 0.2
<15 <50
<10
<5 <25
<25
280 515
Final effluent
Day
2
110
62
670
220
60
1.1
7. 7
42
<20
1,160
<20
30
<60
0.2
<50
<25
480
Day
3
150
90
490
150
60
0.8
7.6
39
<20
875
30
<20
<60
0.2
<50
<25
338
Comp.
<20
1,080
<60
0.2
<50
<2'>
430
ND
ND
ND
Comp.
<25
<10
l.uini
<5
<15
U.5
:15
<10
•s
^25
400
Polycyclic aromatic
hydrocarbons, ug/L
Anthracene/phenanthrene
Benzo(a)pyrene
Chrysene
Fluoranthene
Naphthalene
Pyrene
Polychlorirvated biphenyls
and related compounds, ug/L
Aroclor 1221
Aroclor 1242
Flow, MGD
ND
ND
ND
2
ND
140
ND
0.1
3
190
11
ND
1.]
ND
3
1.4
ND
ND
7
<5
ND
0.9'-
Note: Blanks indicate data not available.
a24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional" parameters and a composite ot
the three was analyzed for the toxic pollutants.
Total phenol, ug/L; pH. pH units.
Not detected ]^ sample
Date: 6/23/80
11.14-24
-------
TABLE 14-13.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY E [4,5]
Pollutant
Conventional pollutants, mg/L
BOD-l
BOD-2
BOD- 3
COD
TOC
TS5
Total phenols
Sulfide
PH
Ammonia
Metals and inorganics, ljg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium *6
Topper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Day
1
3
4
43
15
14
<11
<0.1
7.7
1.0
<2
<20
25
<0.02
5
30
<60
<0.1
<50
<25
141
Day
2
2
3
59
15
19
15
<0.1
7.6
7.8
<2
<20
58
<0.02
8
<30
<60
<0.1
<50
<25
102
Intake
Day
3 composite
2
3
39
15
28
<10
<0,1
7.5
7.8
<2 <2
<20 <20
35 42
<0.02
15 10
<30
<60 <60
<0.1 <0.5
<50 <50
<25 <25
130 127
Day
Composite 1
54
56
160
48
17
6,800
1.8
7.3
13
<25
<10
<3 <2
2 <20
35 104
<0.02
8 <4
<30
23 <60
<0.1 <0.1
51 <50
<\Q
<5 <25
<15
110 61
Day
2
52
41
160
42
13
9,900
1.5
7.1
12
<2
<20
86
<0.02
<4
<30
<60
<0,1
<50
<25
47
DAF effluent
Day
3 Composite
45
44
150
39
16
11,000
1.5
7.2
15
<2 <2
<20 <20
89 89
<0.02
<4 <4
<30
<60 <60
<0.1 <0.5
<50 <50
<25 <25
54 74
Composite
<25
<10
<3
<1
76
<5
<15
<0.1
28
<1Q
<5
-15
5C
Phthalates, ug/L
Di-n-butyl pnthalate
Phenols
Phenol
2,4-Dimethylphenol
Arorratici, ug/L
Berzene
1,2-Dichlorobenzene
1,4-Dichlorobenzene
Ethylbenzene
Toluene
r'olycyclic aromatic hydrocarbons, vg/L
Acenaphthene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Pvrene
colychlorinated biphenyls and
related compounds, ug/L
Aroclor 1242
Halogenated aliphat_ 3, ug/L
Methylene chloride
Tetrachloroethylene
Tnchloroethylene
ND
ND
ND
<0.5
<0.5
ND
ND
1.8
ND
ND
<0.2
ND
ND
>100
>100
>100
ND
>100
>100
150
50
0.3
ND
110
106
5
50
50
20
Date: 6/23/80
11.14-25
-------
TABLE 14-13 (continued)
Final effluent
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
PH
Ammonia
Metals and inorganics, ..pg/L
Antimony
Arsenic
Beryllium
Cadnu jn-.
Chromluir
Chroruum **
Copper
Cyanides
Lead
Mercury
Nickel
Seler.ium
Sliver
Thallium
Zinc
Day
1
ie
le
47
10
9
13
0.3
7.6
35
<2
<20
42
<0.02
<4
<30
<60
0.1
<50
<25
49
Day
2
2
<1
75
7
20
11
0.5
7.5
11
«2
<20
52
<0.02
<4
<30
<60
<0.1
<50
<25
77
Day
3
<1
<1
55
13
13
<10
0.6
7.5
13
<2
<20
44
<0.02
<4
<30
<60
0.1
<50
<25
59
Composite Composite
<25
<10
<2 <3
<20 <1
42 36
<4 <5
<60 <15
<0.5 0.1
<50 <19
12
<25 <5
<15
44 30
Phthalates, ug/L
Di -n-butyl phthalate
Phenols
Phenol
2,4-Dzmethylphenol
Aromatics, ug/L
Benzene
1,2-Dichlorobenzene
1,4-Dichlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons,
Acenaphthene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Pyrene
Polychiorinated biphenyls and
related compounds, ug/L
Aroclor 1242
Halogenated aliphatics,
Methylene chloride
Te trachloroethylene
Trlcnloroethylene
ug/L
ND
ND
ND
<0.5
<0.1
ND
ND
ND
<0.5
10
ND
ND
ND
ND
ND
ND
<0.5
Note: Blanks indicate data not available.
24-hr composite samples on 3 consecutive days were collected. Each was analyzed
for the "traditional" parameters and a composite of the three was analyzed for the
toxic pollutants.
Total phenols, yq/L; pH, pH units.
cNot detected in sample.
Date: 6/23/80
-------
TABLE 14-14.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY F [4,5]
Intake
Pollutant
b
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
pH
Ammonia
Metals and inorganics, yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium *6
Copper
Total cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Polycyclic aromatic hydrocarbons, yg/L
Anthracene/phenanthrene
Chrysene/benz (a)anthracene
Benzo(a)pyrene/perylene
Fluoranthene
Pyrene
Polychlorinated biphenyls and related
compounds, yg/L
Aroclor 1221
Halogenated aliphatics, ug/L
Carbon tetrachloride
Methylene chloride
1 , 1 , 1-Tnchloroethane
Pesticides and metabolites, yg/L
6-BHC
Chlordane
Day
1
40
50
340
96
68
210
1.6
8.2
1.7
<20
<200
<240
<20
50
<30
<600
<0.2
<500
<250
<250
Day
2
40
52
350
110
68
210
0.9
8.1
68
<20
<200
<240
<20
190
<30
<600
<0.7
<500
<250
<250
Day
3
42
35
340
97
40
210
0.7
8.0
63
<2
<20
72
<20
184
<30
<60
<0.9
57
<250
127
Composite
<2
<20
58
151
<60
<0.5
62
<250
133
164
49
33
29
140
ND
>50
<10
>50
ND
2.8
Day
Composite 1
25
42
210
62
64
37
7.3
3.9
<25
27
<3 <2
<1 <20
60 50
50
210 278
520
<15 <60
0.6 0.4
58 64
12
<5 <250
<15
120 229
Day
2
130
>160
300
78
76
1
1.0
8.1
10
<2
<20
60
90
350
830
<60
0.5
101
<250
342
Cooling tower
Day
3
47
36
350
95
80
57
<0.1
6.8
19
<2
<20
79
410
510
830
<60
0.7
134
<25
452
Composite
<2
<20
57
405
<60
<0.5
88
<25
342
1.8
6.5
10c
ND
10
0.1
ND
70
ND
0.7
ND
Composite
<2S
41
<3
-------
TABLE 14-14 (continued)
Final effluent
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COO
TOC
TSS
Total phenols
Sulfide
PH
Ammonia
Metals and inorganics, yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium + a
Copper
Total cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Day
1
18
18
260
110
110
22
8.6
3.9
<2
<20
73
<0.02
199
60
<60
0.3
68
<25
125
Day
2
36
36
270
75
96
24
2.0
8.5
2.8
<2
<20
31
<0.02
86
70
<60
0.3
74
<25
151
Day
3 Composite
20
18
260
82
100
26
<0.1
8.6
3.9
<2 <2
<20 <20
29 45
0.03
84 125
80
<60 <60
0.3 0.5
71 64
<25 <25
112 132
Composite
31
<3
<1
7
125
<15
0.4
58
<10
<5
<15
100
Polycyclic aromatic hydrocarbons, yg/L
Anthracene/phenanthrene^
Chrysene/benz(a)anthracene
Benzo(a)pyrene/perylene
Fluoranthene
Pyrene
Polychlorinated biphenyls and related
compoundsF yg/L
Aroclor 1221
Halogenated aliphatics, yg/L
Carbon tetrachloride
Methylene chloride
1,1,1-Trichloroethane
Pesticides and metabolites, yg/L
6-BHC
Chlordane
ND
0.8
1.3
ND
10
ND
ND
ND
ND
ND
Flow, MGD
0.017
Note: Blanks indicate data not available.
Composite sample.
Total phenols, yg/L; pH, pH units.
Not detected in sample.
Average flow during 24-hr sampling period.
Date: 6/23/80
11.14-28
-------
TABLE 14-15.
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics ug/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium
Chromium +6
Copper
Cyanides
Lead
Lead0
Mercury ( laboratory 1 )
Vcrcuxy (laboratory 3)
NicXel
Selenium
Silver
Thalliua
Zinc
Zinc
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY G [4,5]
Day
1
<3
<3
20
12
<1
10
<0. 1
23
7.6
<1.0
«:2
<20
<24
<0.02
<4
<10
78
1.3
0.5
<50
<1
<25
52
-------
TABLE 14-15 (continued)
Pollutant
Conventional pollutants, mg/L
BOD- 1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
pH
Ammonia
Metals and inorganics, i*g/L
Antimony
Arsenic
Berrylium
Cadmium
Chromium
Chromium
Chromium +6
Copper
Cyanides
Lead
Lead
Mercury (laboratory 1)
Mercury (laiDOratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
c
Zinc
Day
1
240
270
250
860
200
64
22,000
18
190
9.9
14
<2
<20
526
710
<20
<4
1,900
159
270
1.1
<0.2
<50
5
<25
<1
93
44
Day
2
280
2SO
900
360
152
26,000
28
250
10.2
12
<2
<20
414
680
<20
<4
2,000
115
320
1.1
0.5
<50
13
<25
<1
94
87
DAF effluent
Day a Day
3 Composite composite -4
220
260
1,200
290
176
22,000
30
220
10.4
10
1
<4
<2 <2 <1
<20 24 <1
73 425
930 800
<20
<4 8 3
3,000 130
<60 144
360 260
1.0 0.3 0.4
1
<50 104 1
7 9
<25 <25 <1
<1 <2 <1
64 139
92 53
Day
1
15
12
200
60
36
47
2.0
24
8.3
15
<2
<20
89
<20
<4
90
107
0.85
57
32
<25
6
51
Day
2
10
<10
220
64
76
20
1.8
9
8.0
15
<2
<20
86
<20
<4
70
90
<0.2
63
9
<25
12
46
. Final effluent
Day
3 Composite
6
<14
210
56
64
32
2.1
10
8.0
12
<2 <2
<20 <20
73 <24
<20
<4 <4
300
<60 <60
0.5
<50 <50
7
<25 <25
5
64 30
Day
Composite 4
<1
5
<2
<1
1
7
170
2
<1
3
<1
<2 <1
36
Phthalates, ug/L
Bis (2-ethyihexyl) phthalate
Phenols, yg/L
Phenol
Aromatics, ug/L
Benzene
Toluene
Polycyclic aromatic hydrocarbons, ug/L
Anthracene/phenanthrene
Chrysene/benz(a)anthracene
Fluoranthene/pyrene
Naphthalene
jlychlorinated biphenyls and
related compounds, ug/L
Ar_,clor 1016
Aroclcr 1232
Aroclor 1242
Halogenated aliphati.es, yg/L
Methylene chloride
Pesticides and me-abolites, ug/L
a-Endosulfan
2,000
76,000
ND
700
7.9
3.5
0.5
ND
ND
2.60 2.27 2.04
Note: Blanks indicate data not available.
&24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional" parameters and a composite of the
three was analyzed for the toxic pollutants.
btotal phenols, yg/L; pH, pH units.
cGrab samples collected during second visit.
Not detected in sample.
Date: 6/23/80
11.14-30
-------
rt
0>
ro
oo
o
U)
TABLE 14-16,
Phthalates, yg/L
Bis(2-ethylhexyl> phthalate
Phenols, ug/L
2,4-Dichlorophenol
2,4-Dimethylphenol
Phenol
Flow, MGD
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY H [4,5]
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Day
1
<2
<2
12
9
14
11
0.3
31
8.2
-------
TABLE 14-16 (continued)
Pollutant
Conventional pollutants, ng/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
pH
Ammonia
Metals and inorganics, wg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Day
1
<6
<6
40
20
e
<10
0.2
3
7.4
6.2
<1
<2
20
<20
10
20
80
<5
<1
<60
Day
2
<6
<6
36
18
10
10
0.2
8.4
5.0
<1
<2
10
<20
10
10
30
<5
<1
60
Final effluent
Day
3 Composite
3
3
48
21
8
12
0.1
7.8
5.0
<1 <1
20 <2
10 10
<20
9 7
20
<20 30
<5 <5
<1 <1
<60 <60
Composite
<25
<20
<3
<1
<5
<5
<15
<0.5
<15
20
<5
<15
25
Phthalates, ug/L
Bis(2-ethylhexyl) phthalates
Phenols, ug/L
2,4-Dichlorophenol
2,4-Dimethylphenol
Phenol
Flow, MOD
10
ND
ND
1.2
Note: Blanks indicate data not available.
324-hr composite samples on 3 consecutive days ware collected. Each was
analyzed for the "traditional" parameters and a composite of the three
was analyzed for the toxic pollutants.
bTotal phenols, pg/L; pH, pH units.
CNot detected in sample.
Date: 6/23/80
11.14-32
-------
rt
(D
CD
O
I
U)
TABLE 14-17.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY I [4,5]
Intake
Pollutant
Conventional pollutants, mg/L
BOD-la
BOD-2b
BOD-3C
COO
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics, yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Total cyanide
Lead
Mercury (laboratory 1), pg/L
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates, ug/L
Bis(2-ethylhexyl) phthalate
Di-n-butylphthalate
Phenols, ug/L
Phenol
Day
1
<3
4
5
0.5
2
7.8
<2
<20
<24
<4
<5
<60
1.3
0.7
<50
<25
<1
69
Day
2
<3
5
4
4
8.6
<2
<20
<24
6
<5
<60
1.1
0.5
«:50
<25
<1
52
Day
3 Composite
<3
2
4
0.4
5
7.6
<2
<20
<24
20
<5
79
1.4
0.7
<50
<25
<1
836
<4
<2
<20
<24
16
78
<50
2
<25
<1
25
950
30
c
ND
Day
Composite 1
88
77
260
89
38
5,800
0.5
30
5.7
3.4
<1 <2
<1 <20
1 98
10 157
10
2 <60
1.2
<0.2
<1 7
<4
<1 <25
<1
110
Separator effluent
Day
2
76
32
260
80
46
4,400
25
9.1
4.5
<2
<20
91
167
15
<60
2.8
0.8
<2
<4
<25
<1
100
Day
3 Composite
55
66
260
75
32
5,100
0.6
42
8.9
5.0
<2
<20
102
146
<5
90
1.1
0.8
<2
7
<25
<1
100
5
<2
<20
98
157
168
5
4
<25
<2
100
300
ND
390
Composite
<1
<1
3
6
2
<50
<1
1,120
Polycyclic aromatic hydrocarbons, ug/L
Naphthalene
Flow, MOD
290
3.53 3.53
3.53
2.99
3.26
3.29
(continued)
-------
TABLE 14-17 (continued)
Pollutant
Conventional pollutants, mg/L
BOD-13
BOD-2b
BOD-3C
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
pH
Arrcnonia
Metals and inorganics, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Total cyanide
Lead
Mercury (laboratory 1), pg/L
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates, pg/L
Bis(2-ethylhexyl) phthalate
Di-n-butylphthalate
Phenols, pq/L
Phenol
Day
1
<12
<12
88
34
6
18
0.7
5
7.1
<1.0
<2
<20
<24
85
<5
<60
4.2
<0.2
<50
25
<25
<1
69
Day
2
<12
<12
76
29
8
14
3
7.2
<1.0
<2
<20
<24
22
<5
<60
1.2
<0.2
23
<25
<1
69
Final
Day
3
<12
72
29
10
12
0.4
9
7.5
1.7
<5
1.0
effluent
Composite
<1
<4
<2
<20
<24
71
211
<50
16
<25
<2
2,000
600
10
Composite
<1
<1
1
3
2
<1
<1
60
Polycyclic aromatic hydrocarbons.
Naphthalene
Flow, MGD
pg/L
2.76 2.27 2.44
Note:
a
Blanks indicate data not available.
24-hr composite samples on 3 consecutive days were collected. Each was analyzed
for the "traditional" parameters and a composite of the three was analyzed for the
toxic pollutants.
Total phenols, pg/L; pH, pH units.
Compound was not detected.
Date: 6/23/80
11.14-34
-------
TABLE 14-18.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY J [4,5]
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
TOtal phenols
Sulfide
Oil and grease
pH
Ammonia
Metals and inorganics, yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium
Chromium +a
Copper
Cyanides
Lead
Lead
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
Zincc
Day
1
<5
16
14
10
17
<0.1
16
7.5
2.0
<2
<20
<24
<20
5
10
<60
0.7
0.2d
<50
<25
<1
72
Day
2
2
40
19
3
24
<0.1
11
7.8
<1.0
<2
<20
<24
20
10
10
<60
0.9
0.2
<50
<25
<1
54
Intake
Day a
3 Composite Composite
3
20
10
1
2
0.3
11
7.3
<1.0
<1
3
<2 <2 <1
<20 <20 <1
<24 <24
<1
<20
<4 <4 1
<10
<60 <60 2
1.9 0.5
2.0
<50 <50 1
3
<25 <25 <1
<1 <2
62 72
54
Separator 1 effluent
Day
1
51
39
210
60
54
1,000
0.7
74
8.9
2.0
<2
<20
36
20
<4
10
<60
0.1
3.0
<50
7
<25
<1
150
120
Day
2
76
78
160
39
82
1,000
1.8
120
8.2
1.0
<2
<20
620
100
<20
1,370
10
958
1.2
<0.1
771
16
<25
<1
499
250
Day
3 Composite
50
160
55
22
200
l.S
36
7.9
1.7
<2 <2
<20 <20
50 52
16
30
33 25
10
<60 <60
1.2 0.5
1
<50 <50
<4
<25 <25
<1
432 257
420
Composite
<1
3
<1
<1
76
2
4
<1
5
<1
<2
320
Phthalates, yg/L
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols, yg/L
2,4-Dimethylphenol
Pentachlorophenol
Phenol
Polycyclic aromatic hydrocarbons,
Acenaphthene
Anthracene/phenanthrene
Chrysene/benz(a)anthracene
Fluoranthene/pyrene
Fluorene
Naohthalene
Polychlorinated biphenyls and
related conpounds, yg/L
Aroclor 1016
Aroclor 1232
Aroclor 1242
Flow, MGD
yg/L
110e
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
180
ND
ND
ND
ND
420
30
ND
ND
ND
ND
ND
(continued)
Date: 6/23/80
11.14-35
-------
TABLE 14-18 (continued)
Separator 2 effluent
Pollutant
b
Conventional pollutants, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Airanonia
Metals and inorganics , yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium
Chromium **
Copper
Cyanides
Lead
Lead0
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zincc
Zinc
Phthalates, vg/L
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols, vg/L
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
Polycyclic aromatic hydrocarbons* pg/L
Acenaphthene
Anthracene/phenanthrene
Chrysene/benz (a) anthracene
Fluoranthene/pyrene
Fluorene
Naphthalene
Polychlonnated biphenyls and
related compounds/ yg/L
Aroclor 1016
Aroclor 1232
Aroclor 1242
Day
1
85
>84
310
57
64
1,000
5.5
84
8.2
8.4
<2
<20
440
450
<20
<4
10
190
190
2.8
0.1
<50
16
<25
3
316
290
Day
2
>84
>84
690
200
196
2,000
11
140
8.2
14
<2
<20
1,050
1,100
40
231
10
2,080
2,000
1.6
5
69
12
<25
<1
1,400
2,100
Day
3
>84
660
230
106
2,500
15
250
8.2
8.4
<2
<20
411
390
20
<4
10
876
380
0.3
<1
<50
14
<2S
<1
790
680
Composite Composite
<1
5
<2 <1
<20 <1
584
780
55 7
810
870
0.6
61 <1
8
<25 <1
3
658
740
300
ND
NO
ND
ND
160
NDd
90d
30
ND
ND
350
0.5
0.5
0.5
Day
1
15
58
160
52
62
690
1.8
25
7.4
3.0
<2
<20
547
830
20
14
10
123
0.2
<0.1
118
17
<25
<2
194
150
Separator 3 effluent
Day
2
20
22
180
45
38
1,300
5.3
23
7.3
6.2
<2
<20
1,010
1,200
20
16
10
<60
0.6
1.0
<50
13
<25
<1
245
210
Day
3
32
220
63
34
270
1.5
54
7.3
4.5
<2
<20
350
660
40
16
10
<60
0.9
0.6
<50
31
<25
<1
280
280
Composite
<2
<20
626
25
71
1.0
63
<25
215
50
ND
ND
ND
ND
ND
ND
ND
50
ND
ND
ND
HD
ND
ND
Composite
<1
3
<1
<1
570
2
2
<1
6
1
<2
260
Flow, MOD
0.464 0.122 0.572
(continued)
Date: 6/23/80
11.14-36
-------
TABLE 14-18 (continued)
Separator
Pollutant
Conventional pollutant!, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
pH
Amrnoni-
Metals and inorganics, vg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromiumc
Chromium **
Copper
Cyanides
Lead
Lead
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
2incC
Phthalates, ug/L
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols, ug/L
2 , 4 -Dimethylphenol
Pentachlorophenol
Phenol
Polycyclic aromatic hydrocarbons, ug/L
Acenaphthene
Anthracene/phenanthrene
Chrysene/benz (a) anthracene
Fluoranthene/pyrene
Fluorene
Naphthalene
Polychlorinated biphenyls and
related compounds, ug/L
Aroclor 1016
Aroclor 1232
Aroclor 1242
Day
1
>80
100
310
66
36
9,500
6.8
65
7.7
3
<2
<20
835
1,500
<20
38
60
80
0.2
0.2
<50
25
<25
<1
411
340
Day
2
70
55
270
58
26
2,000
9.1
34
7.3
7.3
<2
<20
1,210
1,300
<20
21
50
<60
1-3
6.0d
<50
24
<25
<1
261
290
Day
3
60
430
97
94
1,500
5.1
150
7.6
8.4
<2
<20
1,860
1,700
SO
77
60
<60
1.6
2.0
<50
4
<25
<1
579
620
4 effluent
Composite
<2
<20
1,300
42
69
0.4
50
<25
304
600
NO
ND
650
850
1,600
50
230
40
20
80
NO
ND
ND
ND
Separator
Day
Composite 1
10
10
83
23
26
294
<0.1
7
8.1
2.0
1
3
<1 <2
<1 <20
1,580
1,900 2,200
140
10 51
20
164
12
0.3
<0.1
<1 189
11 7
2 31
<2 <1
464
S60 600
Day
2
12
10
75
22
16
214
1.0
9
8.1
1.0
<2
<20
2,790
4,900
130
47
20
<60
1.1
0.2
<50
29
<25
4
609
740
Day
3
IB
92
31
48
246
12
25
7.1
<1.0
<2
<20
1,500
1,800
90
51
20
<60
1.6
2.0
<50
19
<25
6
417
520
5 effluent
Composite
<2
<20
2,010
45
101
0.5
79
<25
491
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Composite
<1
9
<1
7
3,600
182
2
i
23
<1
<2
760
Flow, MGD
(continued)
Date: 6/23/80
11.14-37
-------
TABLE 14-18 (continued)
Biopond influent
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium0
Chromium *6
Copper
Cyanides
Lead
Lead0
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel
Selenium
Silver
Thallium
Zinc
Zincc
Phthalates, ug/L
Bis(2-ethylhexyl) phthalate
Di ethyl phthalate
Dimethyl phthalate
Phenols, ug/L
2,4-Dimethylphenol
Pentachlorophenol
Phenol
Polycyclic aromatic hydrocarbons, ug/L
Acenaphthene
Anthracene/phenanthrene
Chrysene/benz (a) anthracene
Fluoran tnene/pyrene
Fluorene
Naphthalene
Polychlorinated biphenyls and
related compounds, ug/L
Aroclor 1016
Aroclor 1232
Aroclor 1242
Flow, MGD
Day
1
96
£10
50
24
120,000
14
11
7.4
22
<2
<20
<24
9
80
41
220
72
2.0
<50
20
<25
<1
148
Day
2
<84
570
100
16
110,000
49
9
7.7
24
<2
<20
<25
5
100
7
340
<60
6
<50
10
<25
<1
54
Day
3
>84
480
120
18
83,000
3.5
20
7.5
20
<2
<20
<24
6
80
<4
260
<60
3.0
<50
18
<25
<1
65
Composite
<2
<20
29
17
<60
<50
<25
55
210
ND
ND
750
ND
<12,000
ND
ND
ND
ND
ND
ND
ND
ND
0.1
Day
Composite 1
6
87
34
20
8
0.2
20
7.0
6.8
-------
TABLE 14-19.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY K [4,5]
Day Day
Pollutant 1 2
Conventional pollutants, mg/L
BOD-1 4 4
BOD- 2
BOD- 3 4 4
COD 27 23
TOC 11
TSS 12 14
Total phenols <10
Sulfide 0.4 0.4
Oil and grease 9 6
pH 8.1
Ammonia <1.0 <1.0
Metals and inorganics, pg/L
Antimony
Arsenic
Beryllium <1 <1
Cadmium <2 <2
Chromium 20 10
Chromium *° <20 <20
Copper 10 10
Total cyanide <20
Lead 70 40
Mercury
Nickel <5 <5
Selenium
Silver <1 <1
Thallium
Zinc 200 70
Phenols, vg/L
2-Chlorophenol
2 , 4-Dinitrophenol
2 , 4-Dimethylphenol
4-Ni trophenol
Phenol
Aromatics, pg/L
Benzene
Ethylbenzene
Toluene
Polychlorinated biphenyls and
related compounds, pg/L
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Halogenated aliphatics, pg/L
Chloroform
1 , 2-Dichloroethane
1 , 2-trans-Uichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Intake
Day
3 Composite
<6
<6
24
10
10
0.3
14
7.4
1.0
<1 <1
3 <2
10 20
<20
10 10
60 40
<0.5
<5 <5
<1 <1
60 70
ND°
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
NO
ND
ND
ND
DAF effluent
Day Day Day
Composite" 123 Composite
<120 220 <120
<120 210 <120
80 200 <120
530 1,000 540
180 350 180
260 380 210
700
0.8 1.6 0.6
590 100 98
7.8 7.3
6.7 6.7 6.2
<25
<20
<3 <1 <1 <1 <1
<1 <2 <2 <2 <2
5 1,000 2,000 1,000 1,000
<20 40 20
6 200 400 200 300
<20
<15 50 200 60 100
<0.5
<15 9 20 <5 20
<20
<5 <1 <1 <1 <1
<15
45 1,000 3,000 1,000 2,000
315
11,000
1,150
5,800
105
20
ND
<10
<10
<10
<10
<10
<10
<10
<10
ND
ND
ND
1,100
ND
ND
Composite
<25
<20
<3
3
1,600
280
70
28
<20
<5
<15
1,400
Pesticides and metabolites, yg/L
Heptachlor epoxide
(continued)
Date: 6/23/80
11.14-39
-------
TABLE 14-19 (continued)
Pollutant
Conventional pollutants, mg/L
BOD-1
SOD-2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +s
Copper
Total cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Day
1
8
7
96
21
0.5
31
7.7
2.2
<1
<2
100
<20
60
<20
<5
<1
100
Day
2
<6
6
130
39
16
29
0.3
15
3.4
<1
<2
60
<20
10
<20
<20
<5
<1
70
Final effluent
Day
3 Composite
11
10
140
42
32
0.3
12
7.3
3.9
<1 <1
<2 <2
100 100
<20
20 30
<20 <20
<0.5
<5 <5
<1 <1
100 1,000
Composite
<25
<20
<3
1
73
18
<15
<15
<20
<5
'<15
120
Phenols, yg/L
2-Chlorophenol
2,4-Dinitrophenol
2,4-Dimethylphenol
4-Nitrophenol
Phenol
Aromatics, ug/L
Benzene
Ethylbenzene
Toluene
Polychlorinated biphenyls and
related compounds, yg/L
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor j.242
Aroclor 1248
Aroclor 1254
Aroclor 1260
ND
ND
ND
ND
ND
ND
ND
Halogenated aliphatics,
Chloroform <10
1,2-Dichloroethane <10
1,2-frrans-Dichloroethylene <10
Methylene chloride ND
1,1,2,2-Tetrachloroethane <10
Tetrachloroethylene <10
Pesticides and metabolites, yg/L
Heptachlor epoxida ND
Note: Blanks indicate data not available.
24-hr composite samples on 3 consecutive days were collected. Each was
analyzed for the "traditional" parameters and a composite of the three
was analyzed for the toxic pollutants.
Phenolics, ug/L; pH, pH units.
Compound was not detected.
Date: 6/23/80
11.14-40
-------
TABLE 14-20.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY L [4,5]
Day
Pollutant 1
Conventional pollutants, mg/L
BOD-1 2
BOD- 2 3
BOD- 3 2
COD 56
TOC 13
TSS 290
Total phenols <1
Sulfide 0.1
PH 7-2
Ammonia <1.0
Metals and inorganics, ug/L
Antimony
Arsenic
Asbestos, millions fibers/L
Beryllium <20
Cadmium <200
Chromium <240
Chromium +6 250
Copper <40
Cyanides <100
Lead <600
Mercury (laboratory 1) <0.5
Mercury (laboratory 2) <0.1
Nickel <500
Selenium
Silver <250
Thallium
Zinc 810
Phenols, ug/L
2 ,4-Dimethylphenol
Phenol
Aromatics, ug/L
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic compounds, ug/L
Acenaphthene
Acenaphthylene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Pyrene
Polychlorinated biphenyls and
related compounds , ug/L
Aroclor 1242
Halogenated aliphatics, wg/L
Chloroform
Methylene chloride
Intake
Day Day
2 3
<2
<5 <3
<3 <5
20 24
10 6
220 120
<1 <1
1.0 1.0
7.5 7.1
<1.0 <1.0
<20 <2
<200 <20
<240 <24
<20 50
<40 22
<50 <50
700 64
<0.5 <0.5
0.2 0.2
<500 <50
<250 <25
<250 125
Separator 1 effluent
Compo- Compo-
site site
<25
<20
<20 <3
<200 <1
<240 30
<40 20
<600 40
0.2
<500 21
<20
<250 <5
<15
<250 120
NDC
ND
ND
29
0.2
1
ND
0.2
1.0
1.0
0.3
0.2
ND
40
Day
1
100
130
120
390
110
140
51,400
0.9
7.9
6.2
<20
<200
1,000
<20
170
190
<600
<0.5
1.4
<500
<250
490
Day
2
100
98
350
110
110
50,900
1.5
8.3
10
<20
<200
<240
<20
<40
360
<600
<0.5
1.4
<500
<250
290
Day
3
180
170
150
530
140
120
61,800
1.2
8.6
20
<20
<200
<240
70
100
600
<600
<0.5
0.8
<500
<250
290
Compo-
site
3.4
<20
<200
<240
100
<600
1.5
<500
<250
360
>100
>100
>100
>100
>100
ND
ND
230
20
ND
270
500
ND
5.2
10
>100
Compo-
site
<25
<20
<3
290
180
45
70
<20
<5
<15
370
Flow, MGD
3.88 3.86 4.28
(continued)
Date: 6/23/80
11.14-41
-------
TABLE 14-20 (continued)
Separator 2
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD-2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
pH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Asbestos, millions fibers/L
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury (laboratory 1)
Mercury (laboratory 2)
Nickel
Selenium
Silver
Thallium
Zinc
Phenols
2 , 4-Dimethylphenol
Phenol
Aromatics, ^g/L
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic compounds, yg/L
Acenaphthene
Acenaphthylene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Pyrene
Day
1
32
38
34
200
49
0.8
8.0
7.8
<2
<20
773
50
43
160
<60
<0.5
0.6
<50
<25
382
Day
2
31
42
210
56
36
21,600
1.7
6.3
15
<2
<20
831
<20
54
210
<60
<0.5
0.4
<50
<25
304
Day
3
40
42
40
170
46
48
2,100
0.9
8.4
9.0
<2
<20
928
<20
31
80
<60
<0.5
0.4
<50
<25
314
effluent
Compo - Compo -
site site
<25
<20
<2 <3
<20 <1
802 870
42 50
<60 13
0.5
<50 16
<20
<25 <5
45
325 290
>100
>100
>100
>100
>100
3,000
ND
ND
2
9
300
280
7.0
Day
1
3
3
75
19
34
8
0.4
7.2
<2
<20
205
<20
24
<100
<60
<0.5
0.3
<50
<25
174
Final
Day
2
<4
44
15
15
0.3
6.9
3.4
<2
<20
119
110
19
800
<60
<0.5
0.3
<50
<25
157
effluent
Day Compo-
3 site
11
8
71
14
21
21
0.9
7.2
3.0
<2
<20
165
10
31
80
<60
<0.5
0.3
<50
<25
161
<2
<20
144
24
<60
0.3
<50
<25
174
ND
ND
ND
6.0
ND
1
0.3
<0.1
ND
0.1
<0.1
Compo-
site
<25
<20
<3
<1
190
39
<15
<15
<20
<5
<15
140
Polychlorinated biphenyls and
related compounds, yg/L
Aroclor 1242
Halogenated aliphatics, yg/L
ND
ND
Chloroform
Methylene chloride
Flow, MGD
<10 ND
50 60
7.15 5.37 4.98 11.03 9.23 9.26
Note: Blanks indicate data not available.
a24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional"
parameters and a composite of the three was analyzed for the toxic pollutants.
Total phenols, yg/L; pH, pH units.
CNot detected in sample.
Date: 6/23/80
11.14-42
-------
TABLE 14-21.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY M [4,5]
Conventional pollutants,
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
Oil and grease
PH
Ammonia
Day
•,/L"
<6
<6
10
6
<1
<10
0.2
4
8.0
<1.0
Day
<6
9
10
<1
<10
0.2
8
9.0
<1.0
Intake
Day compo-
<6
<6
a
4
<1
<10
0.3
11
8.1
<1. 0
DAT effluent
Compo- Day
-1
25
34
260
72
18
4,700
0.6
16
6.9
13
Day
50
52
40
220
62
9
4,200
0.5
18
8.4
9.5
Day Oonpo-
36
40
14
220
66
7
4,300
0.4
18
6.2
12
Corapo- Day
-12
<12
92
18
8
<10
0.4
13
7.7
1.0
Final effluent
Day
<6
<6
86
16
e
*10
0 4
1^
7.9
<1.0
Day Hompo- Compc-
<-fc
<6
73
.4
11
<10
0.3
14
7.8
I .0
Metals and inorganics, ug/L
Antimony
Arsenic
y urn
Chromium
Chromium +6
Copper
Cyanides
Lead
Nickel
Selenium
Thallium
Zinc
Phenols, yg/L
2 , 4-Dinitropheno_
2,4-Dimethylphenol
4-Nltrophenol
Phenol
p-chloro^m-creso '.
Aromatics, ug/1
Benzene
Toluene
Polychlorinated biphenyls and
related compounds, yg/L
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Halogenated aliph^tics, ug/L
Carbon tetrachlonde
Chloroform
Methylene chloride
Flow, MOD
<25
<20
30 10 20 20 <5
<20 <20 <20
300 IOC 100 200 180
<20 <20 <20
200 <20 40 60 25
10 5 <5 <5 <15
<20
200 90 100 100 75
ND
Nn
ND
<10
ND
14
<10
ND
ND
ND
ND
ND
ND
ND
ND
44
91
<25
<20
2 2 2 2 <3
200 100 90 100 73
750 <20 <20
10 10 9 10 6
10 20 30
<20 <20 <20 <20 <15
<5 <5 «5 <5 <15
<20
200 100 90 100 140
2,660
18,300
1,400
33,500
ND
12d
<10
<10
<1 0
<10
<10
<10
<10
<10
iOj
55^
180d
<25
<20
2 2 <1 <1 <3
3 <2 <2 <2 <1
90 100 90 100 24
20 <20 <20
10 10 20 10 S
20 <20 <20
•2^ 50 <20 30 <15
<5 <5 10 20 <15
<20
<15
90 100 100 200 90
ND
ND
ND
<10
10
Ha
<10
<10
<10
<10
<10
<10
<10
<10
<10J,
-------
TABLE 14-22.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY N [4,5]
Pollutant
Conventional pollutants, mg/L
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
pH
Ammonia
Metals and inorganics, ug/I.
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols, ug/L
2,4-Dimethyl phenol
Aromatics, ug/L
Benzene
Ethylbenzene
Toluene
p-Chloro-m-cresol
Phenol
Polycyclic aromatic hydrocarbons, ug/L
Acenaphthene
Acenaphthylene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Naphthalene
Pyrene
Polychlorinated biphenyls and
related compounds, ug/L
Aroclor 1016
Aroclor 1221
Aroclor 1232
Halogenated aliphatics, ug/L
Chloroform
Methylene chloride
Intake
Compo- Compo -
Day 1 Day 2 Day 3 site site
<5 <2
<1
40 16 28
12 8 12
18 22 26
<10 <11 <10
0.3 "0.8 1.1
8.4 7.7 7.3
<1.0 <1.0 <1.0
<25
<20
<2 <2 <20 <2 <3
<20 <20 <200 <20 <1
<24 <24 3,000 <24 7
<20 70 90
<4 <4 <40 <4 <5
<60 <30 <60
<60 <60 <600 <60 <15
<0.2 <0.1 100
Separator effluent
Day 1 Day 2 Day 3
83 100 120
360 440 40
88 120 100
68 112 76
6,200 6,570 4,700
2.9 8.1 9.2
8.1 8.1 7.9
12 15 13
<20 <20 <2
<200 <200 <20
1,000 2,000 980
<20 <20 '20
<40 <40 7
<60 40 <60
<600 <600 <60
0.4 0.6 0.4
<500 <500 <50
<250 <250 <25
480 760 5"3
Compo -
site
<2
<20
1,280
14
<60
<0.5
<50
<25
603
71
>100
>100
>100
ND
>100
522
87
140
5.5
8
302
16
1.9
0.1
0.5
15
MOO
Compo-
site
<25
<20
<3
<1
1,400
61
18
0.5
16
<20
<5
<15
570
Pesticides and metabolites, ug/L
Heptachlor epoxide
How, MGD
ND
24.69 26.84 25.91
15.25 15.25 18.25
(continued)
Date: 6/23/80
11.14-44
-------
TABLE 14-22 (continued)
Pollutant
Conventional pollutarx-s, mg/L
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulfide
pH
Ammonia
Metals and inorganics, yg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium +6
Copper
Cyanides
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols, yg/L
2,4-Dimethyl phenol
Phenol
Aromatics, yg/L
Benzene
Ethylbenzene
p-Chloro-m-cresol
Toluene
Polycyclic aromatic hydrocarbons, yg/L
Acenaphthene
Ac enaphthyl ene
Anthracene/phenanthrene
Chrysene
Fluoranthene
Naphthalene
Pyrene
Polychlorinated biphenyls and
related compounds, yg/L
Aroclor 1016
Aroclor 1221
Aroclor 1232
Halogenated aliphatics, yg/L
Chloroform
Methylene chloride
Pesticicdes and metabolites, yg/L
Heptachlor epoxide
Flow, MGD
Chemical plant effluent
Compo- Compo-
Day 1 Day 2 Day 3 site site
34
74 140
340 810 240
93 240 69
28 36 40
<260,000 73 74
0.7 0.9 0.9
6.8 6.6 6.7
1.1 <1.0 2.0
<25
<20
<2 <2 <2 <2 <3
<20 <20 <20 <20 <1
805 679 499 701 650
<20 <20 <20
<4 8 7 <4 13
<60 <30 <60
<60 <60 <60 <60 <15
<0.1 <0.4 <0.2 <0.5 <0.2
<50 <50 <50 <50 <15
<20
<25 <25 <25 <25 <5
<15
6,520 4,110 4,260 5,210 4,800
>100
40
90
20
10
>100
ND
1
<0.1
ND
27
1
1.3
ND
0.1
10
>100
4.6
0.8 0.95 0.9
Final effluent
Day 1 Day 2 Day 3
10 8 10
140 120 140
33 33 36
50 40 44
<15 <11
0.6 0.9 0.9
8.6 7.4 7.4
6.2 6.7 3.0
<2 <2 <2
<20 <20 <20
<24 159 131
<20 <20 <20
<4 <4 <4
<60 <30 <60
<60 <60 <60
0.4 0.2 0.1
<50 <50 <50
<25 <25 <25
<25 118 61
14.75 15.9 17.6
Compo-
site
<2
<20
137
<4
<60
<0.5
<50
<25
104
ND
ND
6
ND
ND
35
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
>100
ND
Compo-
site
<25
<20
<3
<1
120
11
<15
<0.1
<15
<20
<5
<15
35
Note: Blanks indicate data not available.
a
24-hr composite samples on 3 consecutive days were collected. Each was analyzed for the "traditional"
parameters and a composite of the three was analyzed for the toxic pollutants.
Total phenols, ug/L; pH, pH units.
Not detected in sample.
Date: 6/23/80
11.14-45
-------
TABLE 14-23.
SCREENING STUDY WASTEWATER CHARACTERISTICS
BY PLANT, REFINERY 0 [4,5]
n»y
Pollutant 1
Conventional pol'utants, mg/L
BOD-1 <2
BOD- 2
BOD- 3
COD 11
TOC 10
TSS 10
Total phenols <10
Sulftae 0.5
PH 7.1
Ammonia <1.0
Metals and inorcanics, ug/L
Antimony
Arsenic
Beryllium <1
Cadmium <2
Chromium <5
Chromium +6 «20
Copper <6
Cyanides <20
Lead <20
Mercury
Selenium
Silver <1
Thallium
Zinc <60
Fnthalates, yg/i.
Di-n-butyl pht.halate
Dimethyl phthulate
Phenols, yg/L
2 , 4-Dimethylp.ienol
Phenol
Aronatici, ug/L
Benzene
Toluene
Polycyclic aroibatic
hydrocarbons, vg/L
Acenaphthene
Acenaphthylene
Anthracene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics, ug/L
Chloroform
Methylene chloride
Pesticides and metabolites,
ug/L
3-BHC
Isophorone
Flow, MOD
Intake
Day Day Oompo- Compo- Day
2 3 lite lite 1
<5 <3 120
-------
TABLE 14-24.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY P [4,5]
Pollutant
Conventional pollutants, mg/L
BOD-1
BOD- 2
BOD- 3
COD
TOC
TSS
Total phenols
Sulflde
pH
Ammonia
Metals and inorganics, ug/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Chromium *6
Copper
Total cyanide
Lead
Mercury
Nickel
Selenium
Sliver
Thallium
Zinc
Phenols, ug/L
2 , 4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
4 , 6-Dinitro-o-cresol
Aromatics, ug/L
Benzene
Ethylbenzene
'oluene
Polycyclic aromatic hydrocarbons, tjg/L
Acenaphthene
Acenaphthylene
Anthracene
Naphthalene
Phenanthrene
Halogenated aliphatics, ug/L
Carbon tetrachloride
Chloroform
1 , 2-fa-cms-Dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites, ug/L
Aldrir.
B-BHC
6-BHC
8-Endosulfan
Heptachlor
Isophorone
Day Day Day
123
<2 <5 <2
<5 <2
4 6 <4
377
<1 <1 <1
<10 <5 <5
<0.1 <0.1 <0.1
7.0 6.8 6.3
<1.0 <1.0 <1.0
-------
TABLE 14-24 (continued)
Pollutant
Conventional pollutants, mg/Lb
30D-1
30D-2
30D-3
:OD
TOC
TES
Total phenols
Sulfide
PH
Ammonia
Metals and inorganics, wg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
ChroTuuir *a
Copper
Total cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols, ug/L
2 , 4-Dinitrophenol
2-Nitrophenol
4-rtitrophenol
4,6-Dinitro-o-cresol
Aromatics, ug/L
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons, ug/L
Acenaphthene
Acenaphthylene
Anthracene
Naphthalene
Phenanthrene
Halogenated aliphatics, ug/L
Carbon tetrachloride
Chloroform
1 , 2-trane-Dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroethane
Tetrachloroethylene
Trichloroethylene
Pesticides and metabolites, ug/L
Aldrin
B-BHC
6-BHC
B-Endosulfan
Heptachlor
Isophorone
Final
Day Day Day
123
<5 <5 <3
<5 <3
64 49 41
16 24 31
11 2 7
12 11 10
0.3 0.6 <0.1
7.7 7.5
1.4 2.0 2.0
<1 <1 <1
<2 <2 <2
<5 <5 <5
<20 <20 <20
<6 <6 <6
<30 <30 <30
<20 <20 <20
<5 <5 <5
<1 <1 <1
<60 <60 <60
effluent
Composite
<1
<2
<5
<6
<20
<0.5
<5
<1
<60
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
<10
<10
ND
41
<10
ND
<10
ND
ND
ND
ND
ND
ND
370
<20
<3
<1
40
<5
<15
<15
<20
<5
<15
43
24-hr composite samples on 3 consecutive days were collected. Each was analyzed
for the "traditional" parameters and a composite of the three was analyzed
for the toxic pollutants.
bTotal phenols, ug/L; pH, pH units; flow, MOD - million gallons per day.
Not detected in sample.
Date: 6/23/80
11.14-48
-------
TABLE 14-25.
SCREENING STUDY WASTEWATER CHARACTERIZATION
BY PLANT, REFINERY Q [4]
Pollutant
Conventional pollutants, ng/L
BOD-1
BOD- 3
COD
TOC
TSS
Total phenols
Sulf id*
Oil and grease
PH
Ammonia
Antimony
Arsenic
Beryllium (laboratory -
Beryllium (laboratory 3
Cadmium (laboratory 1)
Cadmium (laboratory 3)
Chromium (laboratory 1}
Chromium (laboratory 3)
Chromium **
Copper (laboratory 1)
Copper 'laboratory 3)
Total cyanide
Lead (laboratory 1)
Lead
Mercury (laboratory 1)
Mercury (laboratory 3)
Nickel (laboratory 1)
Nickel (laboratory 3)
Selenium
Silver (laboratory 1)
Silver (laboratory 3)
Zinc (laboratory 1)
Zinc (laboratory 3)
Thallium
Phthalates, ug/L
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dietnyl phthalate
Dimethyl phthalate
Phenoli, ug/L
Phenol
Aromatics, ug/L
Benzene
Halogenated aliphatics, uq/I
Toluene
Chloroform
Dichlorobromome thane
Flow, MGD
Day
1
<2
4
6
3
<1
0.4
7.1
<1.0
<2
<20
<24
<20
37
<10
<60
2.1
<50
<6
<25
70
'1
Day
2
<2
4
11
2
4
0 . 3
9
7.4
<1.0
<2
<20
<24
<20
37
20
«60
1.2
1.0
<50
6
<25
62
1:1
>le.
Xnuka
Day
3 Co
<3
24
9
<1
10
0.3
13
7.5
"1.0
<2
<20
<24
<20
20
<10
<60
3.4
6.0
<50
10
<25
329
<1
qpoaita*
7
<2
<1
<20
<1
<24
1
53
120
167
2
<50
<1
6
<25
<1
2.820
35
<2
1,100
20
20
10
<1
ND
NO
ND
Day Day
4 I
80
50
370
91
28
108
62
9.2
45
35 480
<2
<20
<24
<20
7
240 60
<20 <10
<60
0.2
<0.1 6.0
<50
9
<25
274
<1 330
'1
Day
2
40
70
330
84
10
116
9.3
48
460
<2
<20
<24
<20
<4
140
<10
<60
0.3
<0.2
<50
7
<25
444
470
<1
Day
3
66
64
260
65
12
118
38
9.8
3S
460
<2
<:20
<24
*20
6
60
30
<60
0.3
<0.2
<50
6
<25
Sll
640
"1
Conpoilta
440
<2
<1
<20
<1
•<24
1
15
210
101
10
<50
<1
10
<25
<1
1,460
470
<2
320
ND
NDC
60
894
107
6
24
Day Day
4 1
28
260
59
38
16
0 7
45
8.8
53
350 790
<2
<20
<1
<24
<20
11
380
<20 <10
<60
0.3
<0.2 6.1
<50
11
<25
245
262 380
-------
facilities. Table 14-26 indicates the types of treatment tech-
nology and performance characteristics which were observed during
the survey [2]. In most of the plants analyzed, some type of
biological treatment was utilized to remove dissolved organic
material. Table 14-27 summarizes the expected effluents from
wastewater treatment processes throughout the petroleum refining
industry. Typical efficiencies for these processes are shown in
Table 14-28.
During the survey program, wastewater treatment plant performance
history was obtained when possible. These historical data were
analyzed statistically and the individual plant's performance
evaluated in comparison to the original design basis. After this
evaluation, a group of plants was selected as being exemplary,
and data from these plants were presented in Table 14-26. The
treatment data in Table 14-28 represent the annual daily average
performance (50% probability of occurrence). There were enough
plants involving only one subcategory to make the interpretation
meaningful [2].
11.14,5 REFERENCES
1. NRDC Consent Decree Industry Summary - Petroleum Refining.
2. Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Petroleum Refining
Point Source Category. EPA-440/l-74-014-a, U.S. Environ-
mental Protection Agency, Washington, D.C., April 1974.
195 pp.
3. Interim Final Supplement for Pretreatment to the Development
Document for the Petroleum Refining Industry Existing Point
Source Category. EPA-440/1-76/083A, U.S. Environmental
Protection Agency, Washington, D.C., March 1977. 115 pp.
4. Draft Development Document Including the Data Base for the
Review of Effluent Limitations Guidelines (BATEA), New
Source Performance Standards, and Pretreatment Standards
for the Petroleum Refining Point Source Category. U.S.
Environmental Protection Agency, Washington, D.C.,
March 1978.
5. Development Document for Proposed Effluent Limitations
Guidelines, New Source Performance Standards, and Pretreat-
ment Standards for the Petroleum Refining Point Source
Category. EPA 440/1-79/014-b, U. S. Environmental Protec-
tion Agency, Washington, D. C., December 1979.
Date: 6/23/80 11.14-50
-------
a
fll
rt
fl>
••
\
ro
CO
V.
^N
00
o
H
H
•
4^
1
U1
M
TABLE 14-26. OBSERVED REFINERY TREATMENT SYSTEM AND EFFLUENT LOADINGS
Subcategory
Topping
Cracking
Cracking
Cracking
Cracking
Cracking
Petrochemical
Petrochemical
Petrochemical
Lube
Lube
Integrated
Treatment type
Oxidation pond
Aerated lagoon, polishing
pond
Aerated lagoon, filtration
Equalization, dissolved air
flotation, activated sludge
Oxidation pond
Dissolved air flotation,
aerated lagoon, polishing
pond
Dissolved air flotation,
activated sludge
Dissolved air flotation.
activated sludge
Dissolved air flotation,
aerated lagoon, polishing
pond
Equalization, trickling
filter, activated sludge
Equalization, activated sludge
Dissolved air flotation.
BOD5
8
8.0
5.9
10
3.7
13
2.7
2.6
7.4
14
17.5
(2.8)
(4.4)
(2.1)
(3.6)
(1.3)
(4.6)
(0.95)
(0.91)
(2.6)
(5.0)
(6.2)
39
68
96
71
39
67
54
57
136
320
kg/1
COD
—
(13.8)
(24)
(34)
(25.0)
(13.8)
(23.5)
—
(19)
(20)
(48)
(113)
[2]
Observed average effluent loadings, net i
,000 m3 of feedstock (lb/1,000 bbl of feedstock)
25
34
8.
4.
13.
8.
7
12
38
36
TSS
—
—
(8.7)
(12)
5 (3.0)
2 (1.5)
6 (4.8)
5 (3.0)
(2.5)
(4.3)
(13.5)
(12.7)
Oil and
grease
2.0 (0.7)
2.3 (0.8)
9 (3.2)
4.0 (1.4)
—
2.8 (1.0)
6.5 (2.3)
—
—
4 (1.4)
7.2 (2.55)
22 (7.7)
Phenolic
NHs-N compounds
0.14 (0.05)
0.003 (0.001)
0.4 (0.145)
0.37 (0.13)
4.8 (1.7) 0.05 (0.018)
0.14 (0.05) 0.006 (0.002)
4.5 (1.6) 0.06 (0.023)
—
2 (0.7)
1.2 (0.44) 0.17 (0.06)
~
2.3 (0.8) 0.017 (0.006)
Sulfide
0.03 (0.009)
—
0.2 (0.07)
0 (0)
0.03 (0.010)
0.014 (0.005)
0.05 (0.018)
—
—
—
—
0.20 (0.07)
activated sludge, polishing
pond
-------
o
ft
• •
CTl
\
U)
\
CD
O
I
U1
NJ
TABLE 14-27. EXPECTED EFFLUENTS FROM PETROLEUM TREATMENT PROCESSES [2]
Process
API separator
Clarifier
Dissolved air
flotation
Granular media
filter
Oxidation pond
Aerated lagoon
Activated sludge
Trickling filter
Cooling tower
Activated carbon
Granular media filter
Activated carbon
Process a
influent
Raw waste
1
1
1
1
2,3,4
2,3,4
1
2,3,4
2,3,4
5-9
5-9 and 11
Effluent concentration.
BOD 5
250 -
45 -
45 -
40 -
10 -
10 -
5 -
25 -
25 -
5 -
3 -
350
200
200
170
60
50
50
50
50
100
10
COD TOC
260
130
130
100
50
50
30
80
47
30
30
- 700
- 450
- 450
- 400
- 300
- 200
- 200 20 - 80
- 350
- 350 70 - 150
- 200
25 - 61
- 100 1-17
SS
50
25
25
5
20
10
5
20
4.5
10
3
1
- 200
- 60
- 60
- 25
- 100
- 80
- 50
- 70
- 100
- 20
- 20
- 15
Oil
20
5
5
6
1.6
5
1
10
20
2
3
0.8
- 100
- 35
- 20
- 20
- 50
- 20
- 15
- 80
- 75
- 20
- 17
- 2.5
mg/L
Phenol
6 -
10 -
10 -
3 -
0.01 -
0.1 -
0.01 -
0.5 -
0.1 -
<1
0.35 -
0 -
100
40
40
35
12
25
2.0
10
2.0
10
0.1
Ammonia
15
3
4
1
25
1
10
1
- 150
- 50
- 25
- 100
- 100
- 30
- 140
- 100
Sulfide
0-20
0 - 0.2
0 - 0.2
0.5 - 2
0 - 0.2
Number(s) indicates which process(es) from the process column preceeds the process discussed.
-------
rt
(D
CTl
Ul
CO
O
H
I
Ol
CO
TABLE 14-28. TYPICAL REMOVAL EFFICIENCIES FOR OIL REFINERY TREATMENT PROCESSES [2]
Process
API separator
Clarif ier
Dissolved air
flotation
Filter
Oxidation pond
Aerated lagoon
Activated sludge
Trickling filter
Cooling tower
Activated carbon
Filter
granular media
Activated carbon
Process
influent
Raw waste
1
1
1
1
2,3,4
2,3,4
1
2,3,4
2,3,4
5-9
5-9 and 11
Removal efficiency, %
BOD 5
5 -
30 -
20 -
40 -
40 -
75 -
80 -
60 -
50 -
70 -
91 -
40
60
70
70
95
95
99
85
90
95
98
COD
5
20
10
20
30
60
50
30
40
70
86
- 30
- 50
- 60
- 55
- 65
- 85
- 95
- 70
- 90
- 90
- 94
TOC SS
10 -
50 -
50 -
75 -
60 20 -
40 -
40 - 90 60 -
60 -
10 - 70 50 -
50 - 80 60 -
50 - 65 75 -
50 - 80 60 -
50
80
85
95
70
65
85
85
85
90
95
90
Oil
60
60
70
65
50
70
80
50
60
75
65
70
- 99
- 95
- 85
- 90
- 90
- 90
- 99
- 80
- 75
- 95
- 95
- 95
Phenol
0
0
10
5
60
90
95
70
75
90
5
90
- 50
- 50
- 75
- 20
- 99
- 99
- 99+
- 98
- 99+
- 100
- 20
- 99
Ammonia
0
10
33
15
60
7
33
- 15
- 45
- 99
- 90
- 95
- 33
- 87
Sulfide
70 - 100
95 - 100
97 - 100
70 - 100
Note: Blanks indicate data not available.
Number(s) indicates which process(es) from the process column preceeds the process discussed.
-------
11.16 PULP, PAPER, AND PAPERBOARD MILLS
II.16.1 INDUSTRY DESCRIPTION [1]
II.16.1.1 General Description
The pulp, paper, and paperboard industry includes 730 operating
mills, making this one of the largest industries in the United
States. (Six hundred forty four of these mills responded to 308
surveys used for data in Reference 1.) Included in this industry
are mills that produce (1) only pulp, (2) both pulp and paper
products, and (3) only paper products from pulp manufactured
elsewhere. Included in this industry are mills that use second-
ary fibers (usually waste paper) to produce paper and paperboard
products.
Production operations range from large integrated kraft pulp,
paper, and paperboard mills producing 1,814 Mg/d (2,000 ton/d) of
product to nonintegrated single-machine mills producing less than
0.9 Mg/d (1 ton/d) of product. Total annual production for the
industry is 239,516 Mg (264,075 ton).
The pulp, paper, and paperboard industry manufactures a variety
of products. The various papers differ basically in durability,
weight, thickness, flexibility, brightness, opacity, smoothness,
printability, strength, and color. These characteristics are a
function of raw material selection, pulp methods, and papermaking
techniques. End products of the industry include stationery,
tissue, printing newspapers, boxes, builder papers, and numerous
other grades of industrial and consumer papers.
There are three general classifications of mills: integrated
mills; secondary fiber mills; and nonintegrated mills. At in-
tegrated mills, pulp is produced from wood and nonwood raw mate-
rials and used to manufacture paper and board products on site.
At secondary fiber mills no pulp is produced on site with most
of the furnish (i.e., the raw materials placed in a beater for
making paper pulp) derived from waste paper. At nonintegrated
mills, the furnish consists of purchased wood pulp (or other
fibers). No pulp is made on site, but some waste paper can be
used providing the mill does not have a full deink process.
At mills that produce pulp on site, the raw materials must be
prepared for the pulping process. The preparation of wood for
pulping may require log washing, bark removal, and chipping.
Depending on the form in which raw materials arrive at the mill,
all of these steps, or none of them, may be used.
Pulping processes at integrated mills range from simple ground-
wood operations, using only mechanical defibration of full logs
and limited bleaching operations, to complex dissolving pulp
Date: 6/23/80 II.16-1
-------
mills employing extensive chemical pulping operations and
attendant recovery systems coupled with multistage bleaching
operations. Pulping operations include groundwood and modified
groundwood operations, sulfite (acid) processes, unbleached and
bleached kraft or soda processes (alkaline), and modified high-
yield processes utilizing mild chemical treatments coupled with
mechanical defibration.
After pulping, the unbleached pulp is brown or deeply colored.
The 'pulp is then bleached to remove the color bodies and produce
a light colored or white product. Bleaching is usually accom-
plished in a series of steps, using chlorination and alkaline
extraction, and various chemicals, such as chlorine dioxide, and
hypochlorite.
In recent years, secondary fiber sources such as waste paper of
various classifications have gained increasing acceptance as a
raw material fiber source. Such secondary fiber can frequently
be used without processing. For some applications, however, the
reclaimed waste papers must be deinked prior to use.
Table 16-1 presents industry summary data for the pulp and paper
point source category in terms of the total number of subcate-
gories, the number of subcategories studied by EGD (Effluent
Guidelines Division), and the number and type of dischargers.
TABLE 16-1. INDUSTRY SUMMARY [1,2]
Industry: Pulp and Paper
Total Number of Subcategories: 24a
Number of Subcategories Studied: 24
Number of Dischargers Responding to Survey: 644
• Direct Dischargers: 359
• Indirect Dischargers: 230
• Zero Dischargers: 55
aExcludes three mill groupings, which are not
considered to be subcategories.
II.16.1.2 Subcategory Descriptions
As part of the BATEA review program, an updated and more complete
data base was developed; this result led to the review and re-
vision of the previous subcategorization. The previous and
revised subcategorization is shown in Table 16-2, as reported
in Reference 1.
Date: 6/23/80 II.16-2
-------
TABLE 16-2.
PREVIOUS AND REVISED INDUSTRY
SUBCATEGORIZATION [1]
Previous subcategories
Revised subcategories3
Phase I
Unbleached kraft
NSSC - ammonia
NSSC - sodium
Unbleached kraft-NSSC
Paperboard from wastepaper
Phase II
Dissolving kraft
Market kraft
BCT-kraft
Fine kraft
Papergrade sulfite
- blow pit wash (plus allowances)
Papergrade sulfite-drum wash
- drum wash (plus allowances)
Dissolving sulfite (allowances by
grade)
Groundwood chemi-mechanical
Groundwood thermo-mechanical
Groundwood-CMN
Groundwood-fine
Soda
Deink
Nonintegrated-fine
Nonintegrated-tissue
- from waste paper
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline-fine
Alkaline-unbleached
Semi-chemical
Alkaline unbleached and semi-chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Groundwood-fine
Deink-fine and tissue
Deink-newsprint
Wastepaper-tissue
Wastepaper-board
Wastepaper-molded products
Wastepaper-construction products
Nonintegrated-fine
Nonintegrated-tissue
Nonintegrated-lightweight
Nonintegrated-filter and nonwoven
Nonintegrated-paperboard
Excludes three groupings of miscellaneous mills: integrated miscel-
laneous (including alkaline miscellaneous, groundwood chemi-mechanical,
and nonwood pulping), secondary fiber-miscellaneous, and nonintegrated-
miscellaneous.
The BPT effluent limitations for the previous subcategorizations
(as they appear in Table 16-2) are shown in Table 16-3. BPT
limitations for the revised subcategorizations are not currently
available.
As a part of the review of previous subcategories, raw waste
loads were assessed taking into account the size and age of the
mills, the treatability of the wastes produced, and the effect
of unique geographical factors. Witn the revised subcategoriza-
tion, 512 of the 644 mills responding to the data request fit
Date: 6/23/80
II.16-3
-------
TABLE 16-3.
BPT EFFLUENT LIMITATIONS FOR THE
PREVIOUS SUBCATEGORIES [1]
BOD 5, kg/Mg
Subcategory
Unbleached kraft
Sodium based NSSC
Ammonia based NSSC
Unbleached kraft-NSSC
Paperboard FWP
Dissolving kraft
Market kraft
BCT kraft
Fine kraft
Papergrade sulfite-
blow pit wash
Papergrade sulfite-
drum wash
Papergrade sulfite-
market pulp
Dissolving sulfite
Groundwood chemi-mechanical
Groundwood thermo-mechanical
Groundwood CMN
Groundwood fine
Soda
Deink
Nonintegrated-f ine
Nonintegrated-t issue
Nonintegrated-tissue FWP
Daily
max
5.6
8.0
8.0
8.0
3.0
24
15
14
11
32
27
40
41
14
11
7.4
6.8
14
18
8.2
11
14
30-Day
ave
2.8
4.4
4.0
4.0
1.5
12.25
8
7.1
5.5
17
14
21
22
7
5.6
3.9
3.6
7.1
9.4
4.2
6.2
7.1
Annual
daily
ave
6.9
4.5
4.0
3.1
9.3
7.8
12
4
3.1
2.2
2.0
4.0
5.3
2.4
3.5
4.0
Daily
max
12
11
10
12
5
37
30
24
22
44
44
40
71
20
16
13
12
24
24
11
10
17
TSS , kg/Mg
30 -Day
ave
6.0
5.5
5.0
6.2
2.5
20
16
13
12
24
24
2.6
38
11
8.4
6.8
6.3
13
13
5.9
5.0
9.2
Annual
daily
ave
11
20
7.1
6.6
13
13
21
5.8
4.6
3.8
3.4
7.2
7.1
3.2
2.8
5
pH, units
Range
6 to 9
6 to 9
6 to 9
6 to 9
6 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
5 to 9
Note:Blanks indicate no data available.
into the subcategories shown below, which are grouped as inte-
trated mills, secondary fiber mills, and nonintegrated mills.
II.16.1.2.1 Integrated Mills
In integrated mill operations, pulp is produced and processed
into pulp, pulp bales, paper, or paperboard at the same site.
Alkaline-Dissolving. At alkaline-dissolving mills,a highly
bleached wood pulp is produced in a full-cook process using a
sodium hydroxide and sodium sulfide cooking liquor and a precook
operation called "prehydrolysis". The principal product is a
highly purified dissolving pulp.
Alkaline-Market. At alkaline-market mills, a bleached
papergrade market wood pulp is produced in a full-cook process
using a highly alkaline sodium hydroxide cooking liquor. Sodium
sulfide is also usually present in the cooking liquor in varying
amounts.
Alkaline-BCT. At alkaline-BCT mills, bleached alkaline pulp
is produced and manufactured into paperboard, coarse, and tissue
(BCT) grades of paper. Bleached alkaline pulp is produced in a
process similar to that presented above for the alkaline-market
subcategory.
Date: 6/23/80
II. 16-4
-------
Alkaline-Fine. At alkaline-fine mills, bleached alkaline
pulp is produced and manufactured into fine papers, including
business, writing, and printing papers. The pulping process is
the same as that discussed in the previous two subcategories.
Alkaline-Unbleached. At alkaline-unbleached mills, an un-
bleached wood pulp is produced in a full-cook process using a
highly alkaline sodium hydroxide cooking liquor. Sodium sulfide
is also usually present in the cooking liquor in varying amounts.
The. products are coarse papers and paperboard, and may include
market pulp, unbleached kraft specialties, towers, and corrugat-
ing medium and tube stock.
Semi-Chemical. At semi-chemical mills, a high-yield wood
pulp is produced and manufactured into corrugating medium, in-
sulating board, partition board, chip board, tube stock, and
specialty boards. A variety of cooking liquors is used to cook
the wood chips under pressure; the cooked chips are usually re-
fined before being converted into board or similar products.
Alkaline-Unbleached and Semi-Chemical. At mills in this
subcategory, high-yield semi-chemical pulp (as defined in the
semi-chemical subcategory) and unbleached kraft pulp (as defined
in the alkaline-unbleached subcategory) are produced. Cooking
liquors from both processes are recovered in the same recovery
furnace. Major products include linerboard, corrugating medium,
and market pulp.
Alkaline-Newsprint. At alkaline-newsprint mills, bleached
alkaline pulp (as defined in the alkaline-market subcategory)
and groundwood pulp (as defined in the groundwood-CMN and thermo-
mechanical pulp subcategories) are produced. Newsprint is the
principal product.
Sulfite-Pissolving. At sulfite-dissolving mills, a highly
bleached and purified wood pulp is produced in a full-cook
process using strong solutions of calcium, magnesium, ammonia
or sodium bisulfite, and sulfur dioxide. The pulps produced
are viscose, nitration, cellophane or acetate grades; they are
used principally for the manufacture of rayon and other products
that require the virtual absence of lignin and high alpha-
cellulose content.
Sulfite-Papergrade. At sulfite-papergrade mills, sulfite
pulp and paper or papergrade market pulp are produced. The
sulfite wood pulp is produced by a full-cook process using strong
solutions of calcium, magnesium, ammonia or sodium bisulfite, and
sulfur dioxide. Purchased groundwood, secondary fibers or virgin
pulp are commonly used in addition to sulfite pulp to produce
tissue paper, fine paper, newsprint, market pulp, chip board,
glassine, wax paper, and sulfite specialties.
Date: 6/23/80 II.16-5
-------
Thermo-Mechanical Pulp (TMP). At thermo-mechanical pulp
mills, wood pulp is produced in a process using rapid steaming
followed by refining. A cooking liquor, such as sodium sulfite,
is added. The principal products are fine paper, newsprint, and
tissue papers.
Groundwood-CMN. At groundwood-CMN mills, groundwood pulp is1
produced using stone grinders or refiners; no separate steaming
vessel is used before the defibration. Purchased fibers are used
in addition to groundwood pulp to produce coarse papers, molded
fiber products, and newsprint (CMN).
Grounawood-Fine. At groundwood-fine mills, groundwood pulp
is produced using stone grinders or refiners; no separate steam-
ing vessel is used before the defibration. Purchased fibers are
used in addition to groundwood pulp to produce fine papers, in-
cluding business, writing, and printing papers.
II.16.1.2.2 Secondary Fiber Mills
No pulp is produced at secondary fiber mills; most of the new
material furnish is waste paper. Some secondary fiber mills
include deinking to produce a pulp, paper or paperboard product.
Deink-Fine and Tissue. At deink-fine and tissue mills, a
deink pulp is produced from waste paper. The principal products
made from the deinked pulp including printing, writing, business,
and tissue papers; they may also include products such as wall-
paper, converting stock, and wadding.
Deink-Newsprint. Deink-newsprint mills produce newsprint
from deink pulp derived mostly from over-issue and waste news.
Wastepaper-Tissue. In wastepaper-tissue mills, paper stock
furnish is derived from waste paper without deinking. The
principal products are facial and toilet paper, paper towels,
glassine, paper diapers and wadding.
Wastepaper-Board. Wastepaper-board mills use a furnish
derived from waste paper without deinking. A wide range of
products are made, including setup and folding boxboards, corru-
gating medium, tube stock, chip board, gypsum liner, and liner-
board. Other board products include fiber and partition board;
building board; shoe board; bogus, blotting, cover, auto, filter,
gasket, tag, liner, and electrical board; fiber pipe; food
board; and wrapper and speciality boards.
Wastepaper-Molded Products. At wastepaper-molded products
mills, most of the furnish is obtained from waste paper without
deinking. The principal products are molded items, such as fruit
and vegetable packs and similar throwaway containers and display
items.
Date: 6/23/80 II.16-6
-------
Wastepaper-Construction Products. Mills in the wastepaper-
construction products subcategory primarily produce saturated and
coated building paper and boards. Waste paper is the furnish; no
deinking is employed. The principal products include roofing
felt, shingles, and rolled and prepared roofing. Asphalt may be
used for saturating, and various mineral coatings may be used.
Some asbestos and nonwood fibers (fiberglass) may also be used.
At many mills, some groundwood, defibrated pulp or wood flour
may be processed and used to produce the final product.
II.16.1.2.3 Nonintegrated Mills
Nonintegrated mills purchase wood pulp or other fiber source (s)
to produce paper or paperboard products.
Nonintegrated-Fine. Nonintegrated-fine mills produce fine
papers from wood pulp or secondary fibers prepared at another
site. No deinking is employed at the papermill site. The
principal products are printing, writing, business, and technical
papers; bleached bristols; and rag papers.
Nonintegrated-Tissue. Nonintegrated-tissue mills produce
sanitary or industrial tissue papers from wood pulp or secondary
fiber prepared at another site. No deink pulp is prepared at the
papermill site. The principal products are facial and toilet
paper, paper towels, glassine, paper diapers, wadding, and
wrapping.
Nonintegrated-Lightweight. Nonintegrated lightweight mills
produce lightweight or thin papers from wood pulp or secondary
fiber prepared at another site, as well as from nonwood fibers
and additives. The principal products are uncoated thin papers,
such as carbonizing, cigarette papers, and some special grades
of tissue, such as capacitor, pattern, and interleaf.
Nonintegrated-Filter and Nonwoven. Nonintegrated-filter and
nonwoven mills produce filter papers and nonwoven items using a
furnish of purchased wood pulp, waste paper, and nonwood fibers.
The principal products are filter and blotting paper, nonwoven
packaging and specialties, insulation, technical papers, and
gaskets.
Nonintegrated-Paperboard. Nonintegrated-paperboard mills
produce various types of paperboard from purchased wood pulps or
secondary fibers. Products include linerboard; folding boxboard;
milk cartons; and food, chip, stereotype, pressboard, electrical,
and other specialty board grades.
In addition to the above, there are three miscellaneous groupings
which are not considered subcategories because they do not fit
into any one subcategory definition. These groups include
integrated-miscellaneous (including alkaline miscellaneous,
Date: 6/23/80 11.16-7
-------
groundwood chemi-mechanical, and nonwood pulping), secondary
fiber-miscellaneous, and nonintegrated-miscellaneous; and they
are described below.
Integrated-Miscellaneous. This mill grouping includes three
types of miscellaneous mills: 1) mills employing more than one
pulping process (exceptions are the alkaline-newsprints and the
alkaline-unbleached and semi-chemical subcategories); 2) miscel-
laneous processes not described above (i.e., nonwood pulping,
chemi-mechanical, miscellaneous acid and alkaline pulping mills);
and 3) mills producing a wide variety of products not covered
above.
Secondary Fiber-Miscellaneous. This mill grouping manu-
factures products or product mixes not included in the wastepaper-
tissue, wastepaper-board, wastepaper-molded products and waste-
paper construction products subcategories. Their furnish is more
than 50 percent waste paper without deinking. Products may in-
clude market pulp from waste paper and polycoated waste, filters,
gaskets, mats, absorbent papers, groundwood specialties, and
other grade mixtures. A mill producing less than 50 percent
construction paper or any other combination of products, other
than secondary fiber subcategory products, would be classified
in this grouping.
Nonintegrated-Miscellaneous. This grouping includes any
nonintegrated mill not included in the above subcategories. In-
cluded are mills making mostly asbestos and synthetic products;
paper and paperboard products that are too diverse to be classi-
fied; or products with unique process or product specifications,
commonly called specialty items.
Total production by subcategory is given in Table 16-4, as report-
ed in Reference 1.
II.16.1.3 Wastewater Flow Characterization
Total wastewater flow for the mills sampled is 2,662.7 m3/Mg
(640 kgal/ton) of product formed. Wastewater flows for each sub-
category are included in Table 16-7, which is shown in Section
II.16.2.1. Points of effluent discharge for a typical paper mill
are shown in Figure 16-1.
II.16.2 WASTEWATER CHARACTERIZATION [1]
II.16.2.1 Conventional Pollutants
Raw waste load data were collected to establish effluent limitation
guidelines and the cost of achieving such guidelines. To meet
these objectives, two representative conceptual mills were estab-
lished: the model mill and the pure mill, as described below.
Date: 6/23/80 II.16-8
-------
o
(U
rt
ro
to
OJ
CO
o
TABLE 16-4. REPORTED PULP AND PAPER PRODUCTION BY SUBCATEGORY [1]
01
I
VD
Subcategory
Integrated mills
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline- fine
Alkaline-unbleached
Semi -chemical
Alkaline-unbleached and
semi -chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Groundwood-fine
Secondary fiber mills
Deink-fine
Deink-newsprint
Wastepaper- tissue
Wastepaper-board
Wastepaper-molded products
Wastepaper-construction products
Nonintegrated mills
Nonintegrated-fine
Nonintegrated-tissue
Nonintegrated-lightweight
Nonintegrated-filter and
nonwoven
Nonintegrated-paperboard
Subtotal
Miscellaneous groups
Total
No. of
mills
3
9
8
18
29
19
10
3
6
18
2
6
8
17
3
22
147
15
58
39
26
18
16
12
512
134
646
Average
mill production
Mg/d
1,020
750
790
640
790
410
1,190
1,210
490
320
260
250
420
150
320
30
130
44
74
190
110
52
18
33
(t/d)
(1,130)
(830)
(970)
(700)
(870)
(460)
(1,320)
(1,340)
(540)
(360)
(280)
(280)
(460)
(170)
(360)
(33)
(150)
(49)
(82)
(210)
(130)
(57)
(19)
(36)
Average
production
per machine
Mg/d
430
470
250
55
400
240
340
300
490
83
100
74
120
52
240
12a
130a
5
54
73
58
19
39
20
(t/d)
(480)
(520)
(280)
(61)
(440)
(270)
(370)
(330)
(540)
(91)
(110)
(82)
(140)
(57)
(270)
(13),
(140)a
(5)
(60)
(81)
(64)
(21)
(43)
(22)
Total
annual production
Mkg
1,110
2,440
2,280
4,140
8,230
1,640
4,300
1,310
1,070
2,100
180
540
1,210
930
350
240
7,060
240
1,550
2,100
1,190
320
100
160
226,000
13,300
240,000
(1,000 t)
(1,220)
(2,690)
(2,510)
(4,570)
(9,070)
(1,810)
(4,740)
(1,440)
(1,180)
(2,310)
(200)
(590)
(1,340)
(1,030)
(390)
(260)
(7,780)
(260)
(1,710)
(2,310)
(1,320)
(350)
(110)
(180)
(249,000)
(14,700)
(264,000)
Estimated.
Note: Blanks indicate not applicable.
-------
RAW MATERIALS
FUNDAMENTAL PROCESS
QAKOUS
WASTES
LIQUID
SOLID
PULP U0«
ACID SULFITE LIQUOR
ALKALINE SULFATE LIQUOR
IKRAFT1
NBUTRAL SULPITE
• HITC WATER OR
REUSE WATER
WHITE WATER OR
FRESH WATER
ILEACMIN* AND OTHER
CHEMICALS
WATEK OR WHITE
WATER REUSE
FILLERS
DTE
SIZE
ALUM
STARCH
WATER OR
WHITE WATER REUSE
COATIN* CHEMICALS
•^EVAPORATION LOSS
^••LOW-SYSTEM
EMISSION
SMELT TANK
EMISSION
LIME XILM EMISSION
RECOVERY FURNACE
EMISSION
EVAPORATION
EMISSION
EVAPORATION
AND RtCOVIRY
L0» PLUME
SLOWDOWN
SARKEM SEARIN*
COOLIN* WATER
SARK REFUSE
WOOD PARTICLE*
AND SLIVERS
SAWDUST
SULFITE SPENT
LIOUOR
•LOW PIT COLLECTED
• PILLS
COHDENSATE
DRE« WASHIN*
MUD WASHINS
ACID PLANT
WASTE
RESIDUE*
WEAK LIOUOR
WASH WATERS
WASTE WATERS
•LEACH WASTES
CLEAN - UP
WHITE WATER
CLEAN • UP
KNOTS
FIBER
FIIER
FIBER
DIRT
FIIER
FILLERS
• POKE
• ROKE
COATINtS
FINISHED PAPER
FROOUCTI
Figure 16-1
General flow sheet - pupling and papermaking [1]
Date: 6/23/80
11.16-10
-------
A model mill was developed for each subcategory in order to pre-
sent a typical operation of mills within the subcategory. The
model mill was selected to serve as the basis for subsequent
cost and energy evaluation. The raw waste load presented for the
model mill in some subcategories is the average raw waste load of
mills within the subcategory. In other cases, the model mill raw
waste load may reflect an operation or set of operations that
typify the subcategory but may not be the arithmetic average of
the subcategory. Raw waste loads of conventional pollutants for
model mills in each subcategory are presented in Table 16-5.
TABLE 16-5. SUMMARY OF MODEL MILL RAW WASTE LOADS [1]
Model mill
size
Subcategory
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline-fine
Alkaline-unbleached
Semi-chemical
Alkaline-unbleached and
semi-chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Gr oundwood- fine
Deink-fine and tissue
Deink-newsprint
Wastepaper-tissue
Vfastepaper-board
WaBtepaper-molded
products
Wastepaper-construction
products
Noninte grated- fine
Monintegrated- tissue
Nonintegrated-lightweight
Nonintegrated- filter
Nonintegrated-paperboard
Mg/d
910
540
725
725
910
385
1,360
1,270
540
410
320
540
450
160
360
41
140
45
91
190
160
54
18
36
(t/d)
(1,000)
(600)
(800)
(800)
(1,000)
(425)
(1,500)
(1,400)
(600)
(450)
(350)
(600)
(500)
(ISO)
(400)
(45)
(160)
(50)
(100)
(220)
(180)
(60)
(20)
(40)
Raw waste load
Flow
nu/Mg
200
180
150
110
47
32
56
94
260
150
60
88
68
81
68
39
15
47
9.2
48
73
270
170
100
(kgal/t)
(48)
(43)
(36)
(26)
(11)
(7.8)
(13)
(22)
(62)
(37)
(14)
(21)
(16)
(20)
(16)
(9.4)
(3.7)
(ID
(2.2)
(12)
(18)
(64)
(41)
25
BOD5
kg/Mg
54
42
46
30
14
18
19
21
150
49
18
19
18
49
16
8.8
6.5
5.7
5.6
8.5
13
15
5
10
(Ib/t)
(110)
(83)
(91)
(61)
(28)
(37)
(37)
(42)
(310)
(97)
(37)
(37)
(35)
(97)
(32)
(18)
(13)
(11)
(12)
(17)
(26)
(31)
(10)
(20)
TSS
kg/Mg
77
32
42
66
16
22
24
57
90
33
39
48
54
140
120
27
7.7
11
8.2
30
39
46
25
42
(lb/t)
(150)
(64)
(85)
(130
(33)
(43)
(47)
(110)
(180)
(66)
(77)
(97)
(110)
(290)
(250)
(54)
(15)
(21)
(16)
(60)
(78)
(91)
(50)
84
The pure mill concept was used to establish a basis for the
development of effluent guidelines and standards which can be
applied to each mill in this industry. Because most mills are
combinations of complex processes and products, it is necessary
to isolate distinct operations that can be found in the industry.
Raw waste loads attributable to each distinct process can then
be prorated to match the combination of processes that may be
found at a particular mill. Pure mill raw waste loads are pre-
sented for each subcategory in Table 16-6. For some subcategor-
ies that are particularly well defined and discrete, the pure
mill and model mill raw waste loads may be the same.
Table 16-7 presents the average raw waste loads for all mills
sampled in each of the subcategories.
Date: 6/23/80
II.16-11
-------
TABLE 16-6. SUMMARY OF "PURE MILL" RAW WASTELOADS [1]
Raw waste load
Flow
Subcategory
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline-fine
Alkaline-unbleached
• Linerboard
• Bag
Semi-chemical
• 80%
• 100%
Alkaline-unbleached and semi-chem
Alkaline-news
Sulfite-dissolving
Sul f i te-papergrade
• 67%
• 100%
Thermo-mechanical pulp
Groundwood-CMN
• 74%
• 100%
Gr oundwood- fine
• 59%
• 100%
Deink-fine
• Pure tissue
• Pure fine
Deink-newsprint
Wastepaper tissue
• 100% Industrial
Wastepaper-board
• Board
• Linerboard
• Corrugated
• Chip and filler
• Folding box
• Set-up box
• Gypsum
Wastepaper-molded products
Wastepaper-construction products
• 100% waste paper
• 50% WP/50% TMP
Nonintegr ated- fine
Nonintegrated-tissue
Nonintegrated-lightweight
• Lightweight-electrical
Nonintegrated-filter and nonwoven
Nonintegrated
• Board
• Electrical board
mJ/Mg
220
160
150
110
47
70
32
46
56
94
270
150
200
60
88
130
68
110
81
110
68
57
15
28
4.2
10
16
20
12
52
15
12
48
73
270
410
170
100
250
(kgal/t)
(53)
(40)
(36)
(26)
(11)
(17)
(7.8)
(12)
(13)
(22)
(64)
(37)
(49)
(14)
(21)
(32)
(16)
(27)
(20)
(26)
(16)
(14)
(3.7)
(6.7)
(1.0)
(2.4)
(3.9)
(4.9)
(2.8)
(13)
(3.5)
(3.0)
(12)
(18)
(64)
(98)
(41)
(25)
(59)
BOD2
kg/Mg
65
38
46
29
14
19
18
19
19
21
170
49
68
18
19
23
18
19
49
50
16
13
11
8.9
5.3
3.5
6.1
7.3
S.8
6.5
7.6
14
8.5
13
15
12
5
10
"
db/t)
(130)
(75)
(91)
(57)
(28)
(38)
(37)
(39)
(37)
(42)
(340)
(97)
(140)
(36)
(37)
(46)
(35)
(37)
(97)
(100)
(32)
(26)
(21)
(18)
(11)
(6.9)
(12)
(15)
(12)
(13)
(15)
(28)
(17)
(20)
(31)
(23)
(10)
(20)
(--)
TSS
kg/Mg
97
48
42
53
16
21
22
38
24
57
100
33
35
39
44
78
54
55
140
220
120
40
9.9
11
4
4.5
7.1
5.7
16
11
19
10
30
39
46
38
25
42
"
(lb/t)
(190)
(97)
(85)
(110)
(32)
(41)
(43)
(77)
(47)
(110)
(200)
(66)
(69)
(77)
(97)
(160)
(110)
(110)
(290)
(430)
(250)
(81)
(20)
(22)
(7.9)
(8.9)
(14)
(11)
(32)
(23)
(39)
(20)
(60)
(78)
(91)
(75)
(50)
(84)
( — )
Excludes self-contained mills.
Date: 6/23/80
11.16-12
-------
TABLE 16-7.
SUMMARY OF AVERAGE RAW WASTE LOADS
FOR MILLS SAMPLED [1]
Raw waste load
Flow
Subcateqory
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline-fine
Alkaline-unbleached
Semi -chemical
Alkaline-unbleached and
semi-chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Gr oundwood- fine
Deink-fine and tissue
Deink-newsprint
Wastepaper tissue
Wastepaper-board
Wastepaper-molded products
Wastepaper-construction products
Nonintegrated- fine
Nonintegrated-tissue
Nonintegrated-lightweight
Nonintegrated- f i 1 ter
Nonintegrated-paperboard
ma/Mg
200
130
150
110
70
32
56
94
260
140
60
110
68
93
68
140
15
68
9.2
48
85
270
170
100
(kgal/t)
(48)
(32)
(36)
(26)
(17)
(7.8)
(13)
(22)
(62)
(34)
(14)
(27)
(16)
(22)
(16)
(32)
(3.7)
(16)
(2.2)
(12)
(20)
(64)
(41)
(25)
BOD2
kq/Mg
61
33
46
30
19
18
19
21
150
58
18
19
18
52
16
36
(6.5)
7.2
5.8
8.5
10
15
9.8
10
(Ib/t)
(130)
(65)
(91)
(61)
(38)
(37)
(37)
(42)
(310)
(120)
(36)
(39)
(35)
(100)
(32)
(72)
(13)
(14)
(12)
(17)
(20)
(31)
(20)
(20)
kq/Mq
77
29
42
66
28
22
24
57
90
46
39
67
54
160
120
94
7.7
14
8.2
30
28
46
39
42
TSS
( Ib/t )
(150)
(58)
(85)
(130)
(57)
(43)
(47)
(110)
(181)
(91)
(77)
(130)
(110)
(320)
(250)
(190)
(15)
(27)
(16)
(60)
(56)
(91)
(78)
(84)
aMills with liquor recovery.
II.16.2.2 Toxic and Nonconventional Pollutants
Approximately 200 organic compounds have been identified in pulp,
paper, and paperboard wastewaters. Those not specified by the
NRDC Consent Decree are herein considered nonconventional pollut-
ants. A summary of verification data for toxic and nonconven-
tional pollutants for each subcategory is presented in Tables 16-8
through 16-30. The available data do not include the subcategories
alkaline-dissolving and sulfite-dissolving, but do include three
miscellaneous groupings not considered subcategories: chemi-
mechanical pulp, nonwood pulping, and nonintegrated miscellaneous.
II.16.3 PLANT SPECIFIC DESCRIPTIONS
Limited plant specific data are presently available from Refer-
ence 1. Table 16-31 presents waste load flow, BOD5, and TSS for
selected mills within each subcategory and the subdivisions of
the subcategories.
These selected mills were chosen by the approximate mid-range
value of the pollutant wasteloads for the sampled plants. No
data on treated wastewater for specific plants are currently
available.
II.16.4 POLLUTANT REMOVABILITY [1]
The pulp, paper and paperboard industry employs many types of
wastewater treatment systems to reduce the levels of pollutants
Date: 6/23/80
11.16-13
-------
o
(V
r+
0>
TABLE 16-8.
00
O
ALKALINE-MARKET SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Subcategory : Alkaline-market
Raw water
Average
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed,
Pollutant detected detected Mg/L
Toxic pollutants
Metals
Chromium 202
Copper 2 0 22
Lead 2 0 <1
Mercury 2 0 <1
Nickel 203
Zinc 2 o 15
Phthalates
Bis(2-ethylhexyl)
phthalate 2 0 43
Di-n-butyl phthalate
Diethyl phthalate
Phenols
2 ,4-Dichlorophenol
Phenol
2,4, 6-Trichlorophenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride 1 1 <1
Nonconventional pollutants
Abietic acid
Dehydroabietic acid 1 1 12
Isoplmaric acid
Pimaric acid
Oleic acid
Linoleic acid
Linolenic acid
1-Chlorodehydroabietic acid
Dichlorodihydroabietic acid
3,4, 5-Trichloroguaiacol
Tetrachlorocjuaiacol
"Negative removal.
b
Aeration influent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
5
5
2
4
5
5
1
1
3
5
3
5
S
3
3
5
5
1
4
3
3
6
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
1
1
4
2
1
1
5
5
3
1
3
1
1
3
3
1
1
5
2
3
3
0
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
yg/L
12
31
9
<1
31
150
11
3
<1
4
15
11
<1
14
1
1,200
<1
180
220
58
78
300
700
35
50
29
9
11
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
6
5
4
5
6
2
6
2
2
4
3
3
6
3
3
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
2
1
0
4
0
4
4
2
3
3
0
3
3
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
26
14
10
<1
14
70
32
8
4
1
5
<1
12
<1
580
430
200
210
150
47
42
19
Percent
removal
a
55
a
~b
55
55
a
a
b
93
55
b
99
b
a
a
a
a
49
93
16
34
NOTE: Blanks indicate no data available.
-------
D
fD
rt
n>
cr>
LJ
00
O
TABLE 16-9.
I
M
cn
ALKALINE-BCT SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Subcategory. Alkallitc-BCT
Raw water
Average
concentra-
No. of No. of tlon of
samples samples pollutant
in which in which in all
pollutant pollutant sanples
was was not analyzed.
Pollutant detected detected iig/L
Toxic pollutants
Metals
Chromium 301
Copper 2 U 21
Lead 304
Mercury 3 0 *" 1
Nickel 303
Zinc 3 0 58
Phthalates
Bis{2-ethylhexyl)
phthalate 122
Di-n-butyl phthalate
Phenols
2,4-Dichlorophenol
Pentachlorophenol
Phenol i 2 <1
2,4,6-Trichlorophenol
Benzene 1 2 <1
Ethylbenzene
Toluene
Polycyclic aromatic
Hydrocarbons
Anthracene
Halogenatcd aliphatics
Chloroform
Methylene chloride 121
Tetrachloroethylene
Trichloroethylene
Nonconventional pollutants
Abiotic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Olelc acid
Linoleic acid
1-Chlorodehydroabietic acid
Dichlorodihydroabietic acid
3 , 4 , 5-Trichloroguaiacol
Tetrachloroguaiacol
Aeration influent
Ho. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
8
5
4
3
9
a
6
1
9
7
3
3
7
8
7
7
7
6
5
2
1
6
No. of
aaaples
in which
pollutant
was not
detected
0
0
0
0
0
I)
1
4
5
6
0
t
3
e
0
2
6
6
2
1
2
2
2
3
4
7
8
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
ug/L
85
46
17
•1
36
140
3
2
I
6
55
8
1
<1
1,550
2
<1
<1
1,040
740
96
110
1,080
510
52
2
<1
5
Final effluent
No. of
saiples
in which
pollutant
was
detected
9
9
9
9
9
9
6
1
2
3
4
1
1
1
8
5
7
9
7
6
3
1
1
No. Of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
3
8
7
6
5
e
8
8
1
4
2
0
2
3
6
8
8
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
55
17
18
-------
TABLE 16-10.
rt
n>
00
o
a*
i
M
cr>
ALKALINE-UNBLEACHED SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Subcategory: Alkaline-unbleached
Raw water
Average
concentra-
te, of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant sanples
was was not analyzed.
Pollutant detected detected wq/L
Toxic pollutants
Metals
Chromium 30 7
Copper 30 4
Lead 3 0 21
Mercury 3 0 <1
Nickel 307
Zinc 3 0 14
Phthalates
Bis (2-ethylhexyl)
phthalate 1 2 <1
Butyl benzyl phthalate
Di-n-butyl phthalate
Phenols
Phenol 2 1 <1
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride 12 3
Tetrachloroethylene
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic aci d
Linolenic acid
Dichlorodehydroabietic
acid
Xylenes
Negative removal.
b .
Aeration influent
No. of
samples
in which
pollutant
was
detected
a
9
9
9
9
9
5
2
4
9
1
3
7
3
7
2
9
9
9
9
9
9
3
1
6
No. of
samples
in which
pollutant
was not
detected
1
0
0
0
0
0
4
7
5
0
8
6
2
6
2
7
0
0
0
0
0
0
6
8
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
Mq/L
14
19
14
<1
6
110
18
8
2
85
<1
<1
4
<1
34
<1
2,030
740
330
320
1,070
450
170
<1
14
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
1
3
3
2
5
6
6
3
4
6
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
5
0
0
4
1
0
0
3
2
O
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
MS/I.
12
9
16
<1
5
81
<1
b
1
x
3b
<1
4
120
52
15
17
110
Percent
removal
14
53
£
~b
16
30
94
50
96
b
88
94
93
95
95
90
Negligible removal.
NOTE: Blanks indicate no data available.
-------
0
OJ
rt
to
CO
oo
o
TABLE 16-11.
I
M
^O
ALKALINE-FINE SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [I]
Subcategory : Alkaline-fine
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
Pollutant detected detected ug/L
Toxic pollutants
Metals
Chromium 302
Copper 306
Lead 303
Mercury 3 0 <1
Nickel 302
Zinc 3 0 19
Phthalates
Bis (2-ethylhexyl)
phthalate 214
Di-n-butyl phthalate
Diethyl phthalate
Phenols
2,4-Dichlorophenol 122
Pentachlorophenol
Phenol
2 , 4 ,6-Tr ichlorophenol
Honocyclic aromatics
Toluene
Haloganated aliphatics
Chloroform
Dichlorobromome thane
Hethylene chloride 122
Te trach loroe thy 1 ene
1,1, 1-Trichloroethane
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
9,10-Epoxystearic acid 1 2 37
Dichlorodehydroabietic
acid
3,4,5-Trichloroguaiacol 12 4
Tetrachloroguaiacol 12 8
Xylenes
Aeration influent
No. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
7
2
1
2
3
6
9
8
6
2
3
1
1
4
6
£
6
3
3
2
4
j
2
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
2
7
8
7
6
3
0
1
3
7
6
8
8
5
3
3
3
6
6
•j
5
2
7
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
26
22
6
<1
16
150
28
<1
<1
<1
3
7
11
23
780
4
<1
<1
a
190
18O
48
40
180
94
4
2
6
1
Final effluent
No. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
6
1
1
1
2
7
9
2
1
4
2
1
1
3
No. of
sanples
in which
pollutant
was not
detected
0
0
0
0
0
0
3
8
8
2
7
2
0
7
8
5
7
8
8
6
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/i.
7
8
6
<1
8
71
16
<1
<1
2
<1
3
52
<1
1
3
18
10
<1
2
Percent
removal
74
*J*
-
50
52
43a
-
33
86
73
93
a
99
99
90
89
50
67
Negligible removal.
NOTE: Blanks indicate no data available.
-------
D
PJ
rt
0>
CTl
NJ
00
CD
O
TABLE 16-12.
i
M
00
SEMI-CHEMICAL SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Subcatoyory : Sriru-
Raw water
Average
No. of No. of tiori of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
Pollutant detected detected pg/L
Toxic pollutants
Metals
Chromium 20 2
Copper 20 4
Cyanide 30 9
Lead 10 4
Mercury 1 1
-------
D
0)
rr
(D
to
u>
co
TABLE 16-13.
I
M
VD
ALKALINE UNBLEACHED AND SEMI-CHEMICAL SUBCATEGORY -
SUMMARY OF VERIFICATION DATA FOR TOXIC AND NONCON-
VENTIONAL POLLUTANT CONCENTRATION [1]
Subcategory : Alkaline unbleached and semi-chemical
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
NicXel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Diethylphthalate
Phenols
Pentachlorophenol
Phenol
Honocyclic aromatics
Benzene
Toluene
Polychlorinated biphenyls
and related compounds
Aroclor 1232
Aroclor 1254
Halogenated aliphatics
Chloroform
Methylene chloride
1,1, 1-Trichloroethane
Trichloroethylene
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
Xylenes
No. of
samples
in which
pollutant
was
detected
2
2
6
2
2
2
2
1
2
1
1
1
1
Raw water
Average
concentra-
No. of tion of
samples pollutant
in which in all
pollutant samples
was not analyzed.
detected pg/L
0 2
0 8
0 10
0 2
0 <1
0 2
0 6
1 <1
0 2
1 <1
1 3
1 24
1 9
Aeration influent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
6
5
4
2
1
6
3
3
3
2
3
3
2
6
6
6
6
6
6
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
2
4
5
0
3
3
3
4
3
3
4
0
0
0
0
0
0
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
29
38
16
24
<1
10
40
10
5
7
1
56
2
1
<1
1
58
3
<1
1,400
610
550
150
620
440
1 in
J. -3U
11
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
6
5
4
1
6
6
6
6
6
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
2
5
0
0
0
0
0
3
A
Average
concentra-
tion of
pollutant
in all
sanples
analyzed,
Mg/L
19
15
10
13
<1
5
25
10
2
13
710
230
190
95
410
59
Percent
removal
35
61
38
46
a
50
38
a
b
78
50
61
66
38
34
86
57
Negligible removal.
Negative removal.
NOTE: Blanks indicate no data available.
-------
o
OJ
ri-
ft
NJ
U>
CO
O
TABLE 16-14.
SULFITE PAPERGRADE SUBCATEGORY - SUMMARY OF VERIFICATION DATA
FOR TOXIC AND NONCONVENTIONAL POLLUTANT CONCENTRATION [1]
I
NJ
O
Raw water Aeration influent
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
2-Chlorophenol
2,4-Dichlorophenol
Pentachlorophenol
Phenol
2,4, 6-Tnchlorophenol
Monocyclic aromatics
Benzene
Toluene
Halogenated aliphatics
Chloroform
Dlchlorobromome thane
1 , 1-Dichloroe thane
Methylene chloride
1 , 1 , 1-Trichloroethane
Trichloroethylene
Norjconven1 .onal pollutants
Abietic acid
Dehydroabietic acid
Isopiinaric acid
Pimaric acid
Oleic acid
Linoleic acid
Linolenic acid
1- hlorodehydroabietic
cid
Di hlorodehydroabietic
cid
3, , 5-Trichloroguaiacol
Xylenes
Average
concentra-
Ho. of No. of tion of No. of
samples samples pollutant samples
in which in which in all in which
pollutant pollutant samples pollutant
was was not analyzed, was
detected detected pq/L detected
4067
4 0 15 7
40 57
4 0 <1 9
4037
4 0 26 9
2 2 66 7
1
1
3
1 3 <1 3
1328
3
3
3
8
3
3
7
3 6 414 2
3
6
9
6
2
9
6
2
6
1
3
No. of
samples
in which
pollutant
was not
detected
2
2
2
0
2
0
2
8
8
6
6
1
6
3
3
1
6
6
2
" 1
6
3
0
3
7
0
3
7
-j
3
8
6
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
pg/L
13
81
13
16
91
38
<1
<1
<1
4
53
4
1
0.2
3,200
9
4
460
3
5
140
560
62
8
170
57
12
49
82
<1
<
'1
No. of
samples
in which
pollutant
was
detected
9
9
9
12
9
12
11
1
3
3
1
8
5
5
7
12
1
12
3
2
6
9
7
1
7
4
3
1
2
Final effluent
No. of
samples
in which
pollutant
was not
detected
3
3
3
0
3
0
1
11
9
9
11
4
7
7
5
0
11
0
9
10
6
3
5
11
5
8
9
11
10
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
7
29
10
6
120
21
1
9
27
<1
41
39
12
14
430
'1
270
2
<1
51
250
13
4
47
26
2
20
<1
"-1
Percent
removal
46
64
23
a
63b
45
b
_k
b
75
15
_b
77
6
86
89
42
33
80
64
55
79
50
72
54
75
a
~b
' Noqliq iblc removal
NeqAtivo rprooval.
NOTI : Blanks indicate no data avai 1-ibLi1.
-------
TABLE 16-15.
B>
rt
0>
to
oo
o
cr>
to
CHEMICAL-MECHANICAL PULP SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
Pollutant detected detected pg/L
Toxic pollutants
Metals
Chromium 1 0 2
Copper 102
Cyanide 3 0 10
Lead 102
Mercury 3 0 <1
Nickel 102
Zinc 1 0 14
Phthalates
Bis(2-ethylhexyl)
phthalate
Phenols
Phenol
Monocyclic aromatics
Ethylbenzene
Toluene
Polychlorinated biphenyls
and related compounds
ftroclor 1254
Halogenated aliphatics
Methylene chloride 104
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
1 -Chlorodehy droabi e t ic
acid
Xylenes
a
Negative removal.
b .
Subcateyory
Chemi -nun-nan i i.al pulp
Aeration influent
No. of
samples
in which
pollutant
was
detected
3
3
3
3
1
3
3
2
3
1
2
1
2
3
3
3
3
3
3
3
2
No. Of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
0
2
1
2
1
0
0
0
0
0
0
0
1
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
3
40
13
2
<1
3
400
7
31
<1
3
<1
5
2,700
1,400
1,020
750
1,300
300
54
57
Final effluent
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
1
1
2
3
3
3
3
3
1
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
2
2
1
0
0
0
0
0
2
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
4
16
9
3
<1
6
110
1
<1
6
140
100
67
42
66
1
Percent
removal
a
60
30
3,
3
73
67
b
3
95
93
93
94
95
98
-------
o
P)
("T
CD
• •
^^
\
KJ
00
o
I
to
N>
TABLE 16-16.
GROUNDWOOD-CMN SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Subcategory: Groundwood-CMN
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Phenols
Phenol
Monocyclic aromatics
Benzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Oleic acid
Linoleic acid
Xylenes
No. of
samples
in which
pollutant
was
detected
1
1
1
1
1
1
1
1
1
1
Raw water
No. at
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
0
0
Oxidation influent
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
M9/L
2
16
10
2
1
2
10
6
8
31
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
3
3
3
3
1
2
3
2
3
1
2
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
0
0
0
2
1
0
1
o
2
1
Average
concent ra-
tion of
pollutant
in all
samples
analyzed.
M9/L
6
15
9
13
<1
8
480
8
16
9
290
<1
220
430
14
74
16
4
Final effluent
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
3
3
1
3
1
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
0
2
0
2
0
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
4
5
9
2
<1
7
1,600
9
11
31
89
70
b
89
Negligible removal.
Negative removal.
NOTE: Blanks indicate no data available.
-------
TABLE 16-17.
D
PJ
c-r
00
00
o
I
N)
CO
GROUNDWOOD-FINE SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION fl]
Subcatcqory : Groundwood-f me
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Phenols
Pentachlorophenol
Phenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride
Tetrachloroethylene
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
Linolenic acid
Raw water
No. of No. of
samples samples
in which in which
pollutant pollutant
was was not
detected detected
2 0
2 0
2 0
2 0
2 0
2 0
1 1
1 1
1 1
1 1
: i
Aeration influent
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
2
5
2
<1
5
22
2
2
3
2
17
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
4
3
3
6
1
6
6
1
1
6
6
5
2
5
3
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
2
3
3
0
5
0
0
1
5
0
0
1
4
1
3
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
5
28
9
<1
5
74
3
<1
3
28
<1
13
99
<1
<1
180
150
29
50
170
170
130
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
5
3
2
4
3
9
1
2
6
4
1
2
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
1
3
4
2
3
0
5
4
0
2
5
4
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
3
14
8
5
45
4
<1
2
^
15
2
5
26
2
3
13
39
Percent
removal
40
50
11
a
a
39
b
a
67
93
92
85
b
98
84
93
94
92
77
Negligible removal.
Negative removal.
NOTE: Blanks indicate no data available.
-------
TABLE 16-18.
Pi
r+
n>
CO
\
CD
o
cr*
i
NONWOOD PULPING SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Subcategory : Nonwood pulping
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Monocyclic aromatics
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride
1 ,1 ,1-Tnchloroe thane
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
1-Chlorodehydroabietlc
acid
Di chlorodehydroabie t l c
acid
Xylenes
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
detected detected ug/L
3 0 3
309
3 0 10
307
3 0 <1
303
3 0 66
3 0 15
2 1 <1
126
Aeration influent
No. of
sanples
in which
pollutant
was
detected
6
6
3
6
6
6
6
4
2
5
4
3
1
1
3
2
3
3
4
1
1
4
3
1
1
3
No. of
sanples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
2
4
1
2
3
5
5
3
4
3
3
2
5
5
2
3
5
5
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
gg/L
5
39
9
17
5
75
8
<1
2
12
5
3
<1
420
<1
33
82
250
16
10
220
270
6
<1
4
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
3
6
6
6
6
5
2
1
4
1
3
3
1
2
3
2
1
2
1
1
1
No. of
sanples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
4
5
2
5
3
3
5
4
3
4
5
4
5
5
5
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
gg/L
5
15
9
11
3
33
45
-------
TABLE 16-19.
0
SD
ri-
U)
oo
o
cr>
DEINK NEWSPRINT SUBCATEGORY - SUMMARY OF VERIFICATION
DATA FOR TOXIC AND NONCONVENTIONAL POLLUTANT
CONCENTRATION [1]
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Phthalates
Bis (2-ethylhexyl)
phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Phenol
Monocyclic aromatics
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
Subcategory :
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
detected detected Ug/L
103
1 0 54
1 0 10
1 0 <1
103
1 0 10
1 0 14
1 0 <1
103
Deink newspri
nt
Discharge, POTW
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
3
1
1
1
2
3
3
1
3
3
3
3
3
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
2
2
2
1
0
0
2
0
0
0
0
0
0
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
wg/L
29
76
160
1
15
340
13
5
<1
1
1
2
14
<1
<1
3,500
3,700
510
260
1,400
750
NOTE: Blanks indicate no data available.
-------
TABLE 16-20.
DEINK-FINE AND TISSUE SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
ph thai ate
Di-n-butyl ph thai ate
Diethyl phthalate
Phenols
2 , 4-Dichlorophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
2 -Ch loropheno 1
Honocyclic aroma tics
Benzene
Chlorobenzene
Ethylberzene
Toluenf
Polycyclic aromatic
hydrocarbons
Naphthalene
Polychlorinated biphenyls
and related compounds
Aroclor 1242
Aroclor 1260
Halogenated aliphatics
Chloroform
1 , 2-Dichloroethane
Methylene chloride
Tetrachloroethylene
i , 1 , 1-Trichloroethane
Trichloroethylene
Nonconventional pollutants
Abie tic acid
Dehydroabietic acid
Isopimaric acid
Pimanc acid
Oleic acid
Linoleic acid
Linolenic acid
1-Chlorodehydroabietic
acid
Dichlorodehydroabietic
acid
3,4, S-Trichloroguaiacol
Tetrachloroguaiacol
Xylenes
Negative removal.
b
Subcategory :
Raw water Aer
Average
concantra-
s amp las samples pollutant samples
in which in which In all in which
pollutant pollutant camples pollutant
was was not analyzed, was
30 59
30 49
9 0 10 9
30 39
3 0 <1 9
30 69
3 0 17 9
6
1 2 <1 4
1
4
6
5
5
1
3
3
3
9
4
1
1
1019
2
3
3
3
6
9
8
8
8
9
6
2
5
2
2
3
3
ation influel
•amples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
3
5
8
5
3
4
4
8
6
6
6
0
5
8
8
0
7
6
6
6
3
0
1
1
1
0
3
7
4
7
7
6
6
It
Average
concentra-
pollutant
in all
samples
analyzed ,
ug/L
"*'
22
34
68
61
<1
8
150
7
5
1
2
18
38
18
'1
2
14
11
25
42
1
<1
1,800
<1
4
32
7
170
640
2,200
300
69
550
150
40
130
2
5
3
4
samples
in which
pollutant
was
9
9
9
9
9
9
9
7
4
2
2
6
1
4
5
1
9
3
3
6
8
3
7
2
3
3
'
samples
in which
pollutant
detected
0
0
0
0
0
0
0
2
5
7
7
3
8
5
4
8
0
6
6
3
1
6
2
7
6
6
it
Average
concentra-
pollutant
in all
samples
6 72
10 71
89 -a
13 79fa
<1
3 63
41 72
2 71
4 SO
•=1
<1 50
15 If
8 79
16 11
2
'1 96
66 96
<1 7e
2 9?
56 51
210 99
5 98
290 43
r 96
^ b
2
NOTE. Blanks indicate no data available.
Date: 6/23/80
11.16-26
-------
(U
rt
CO
u>
\
00
o
TABLE 16-21. WASTEPAPER-TISSUE SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Subcategory : Wastepaper-tissue
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
Pollutant detected detected pg/L
Toxic pollutants
Metals
Chromium 30 10
Copper 30 4
Cyanide 90 9
Lead 30 4
Mercury 3 0 <1
Nickel 3 0 11
Zinc 30 4
Phthalates
Bis (2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Phenol
Honocyclic aromatics
Benzene
Ethy Ibenzene
Toluene
polycyclic aromatic
hydrocarbons
Naphthalene
Polychlorinated biphenyls
and related compounds
Arcolor 1254
Halogenated aliphatics
Chloroform
Methylene chloride 12 2
Tetrachloroethylene
Nonconventional pollutants
Abietic acid
Dehydroabietlc acid
Isopimaric acid
Pimaric acid
Oleic acid
Xylenes
Aeration influent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
6
5
1
2
6
1
5
3
1
I
3
2
4
6
3
1
6
5
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
o
0
1
5
4
0
8
1
0
5
5
3
1
2
0
3
5
0
1
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
l/g/L
- " ~
20
55
9
44
<1
21
490
10
3
13
41
<1
2
26
<1
2
87
74
54
370
16
3
180
28
Final effluent
No. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
9
4
4
3
2
2
1
2
1
2
7
6
1
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
5
5
3
7
7
8
7
8
7
2
3
8
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
Mg/L
10
34
9
26
<1
9
68
2
2
13
1
6
<1
<1
6
24
97
140
1
Percent
removal
50
38a
36
a
57
86
80
95
50
77
50
99
92
55
74
25
96
N^gligib!r removal.
NOTE: Blank? Lndicate no data available.
-------
0
01
rt
TABLE 16-22.
to
00
O
oo
WASTEPAPER-BOARD SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Raw water
No. of No. of
samples samples
in which in which
pollutant pollutant
Pollutant detected detected
•"ox LC pollutants
Metals
( hroouum 4
Copper 4 ?
Cyanide 18 0
Lead 4 2
Mercury 6 0
Nickel 4 2
Zinc 6 n
Bis(2-ethylhexyl)
phthalate 3 3
Butyl benzyl phthalate 3 0
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Pentachlorophenol 1 5
Phenol 2 4
2,4, 6-Tnchlorophenol 1 5
Monocyclic aroma tics
Benzene
Toluene
Polychlorinated biphenyls
and related compounds
Aroclor 1248
Aroclor 1254 1 5
Halogenated aliphatics
Brorooform
Chloroform l 5
Dibromochloromethane 2 4
DichlorobroBKjme thane 1 5
Methylene chloride 1 5
Tetrachloroethylene
1,1, 1-TriChloroethane
Trichloroethylene 1 5
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid 1
Linoleic acid
Linolenic acid
Xylenes
aNeqligible removal.
Negative removal.
COxidation influent.
Subcategory : Wastepaper-board
Aeration influent
Average Average
concent r a- concentra-
pollutant samples samples * pollutant
in all in which in which in all
samples pol lutant pol ] utant samples
ug/L detected detected yg/L
j 2 1 ' - •}
3 2 1 HO
10 3 0 74
3 7 2 150
<1 3 0 <1
4 2 1 37
22 3 0 1,400
3 3 0 23
100 3 0 30
2 1 32
3 0 79
930 1,050
<1 3 0 460
4 3 0 360
1 8 <1
30 4
2 1 *1
< 1 2 1 *!
1 2 40
1 ^ c
17 9 0 19
1
612 <1
<1 5 4 1
24 3
21 2
445 1
3 0 410
3 0 470
30 84
3 0 41
130 290
5 4 42C
c
3 6 23
1 2 fl
Final "fflu^nt
Avt?raq*>
conc»ntra-
samplcs samples pol lutant
in which in which in atl
pollutant (>ol lutant samp Ins
detected detected ug/L
12 6 31
12 f. 37
18 0 14
12 6 11
18 0 '1
12 6 1'
18 0 340
13 5 73
3 15 11
3 15 7
6 12 69
3 15 200
5 13 72
5 13 72
1 17 <1
99 ?
3 15 <1
4 14 <1
1 17 3
3 15 2
3 15 "•!
6 12 9
18 <1
3 15 <1
6 12 16
15 3 62
1 17 <1
54 27
10 8 65
1 17 <1
removal
8)
6"
HI
81
a
54
76
_b
86
84
13
81
84
a
50
a
a
93
89
a
"b
67
50
96
86
99
34
77
96
NOTE Blanks indicate no data available.
-------
o
TABLE 16-23.
NJ
00
o
WASTEPAPER MOLDED PRODUCTS SUBCATEGORY - SUMMARY
OF VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Pollutant
Toxic pollutants
Metal
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis (2-ethylhexyl)
phthalate
Phenols
Pentachlorophenol
Phenol
Monocyclic aromatics
Benzene
Toluene
Halogenated aliphatics
Methylene chloride
Nonconventional pollutants
Abietic acid
Dehydroabletic acid
Isopimaric acid
Pimaric acid
Oleic acid
Llnoleic acid
9,10-Epoxystearic acid
No. of
samples
in which
pollutant
was
detected
2
2
6
2
2
2
2
2
1
1
1
1
1
1
Raw water
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
1
1
1
1
1
1
s
ubcategory :
Wastepaper molded products
Aeration influent
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
Mg/L
2
27
10
4
3
6
12
5
2
2
2
<1
<1
37
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
3
1
3
2
3
3
3
3
3
3
1
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
2
0
1
0
0
0
0
0
0
2
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
M9/L
9
16
9
22
fl
23
390
2
2
8
<1
210
450
48
57
490
210
10
Final effluent
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
1
1
1
1
1
3
3
3
1
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
2
2
2
2
2
0
0
0
2
Average
concentra-
tion of
pollutant
in all
samples
analyzed. Percent
Mg/L removal
3 67
4 7")
9
12 45
a
3 87
52 88
<1 50
2
<1 87
<1 a
57 87
94 -b
360 27
120 41
9 10
Negligible removal.
b
Negative removal.
NOTE: Blanks indicate no data available.
-------
TABLE 16-24.
WASTEPAPER CONSTRUCTION PRODUCTS SUBCATEGORY -
SUMMARY OF VERIFICATION DATA FOR TOXIC AND
NONCONVENTIONAL POLLUTANT CONCENTRATION [1]
Subcategory: Waatepaper construction products
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Butyl benz; 1 phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Pentacnlorophenol
Phenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Polychlonnated biphenyls
and related compounds
Aroclor 1248
Aroclor 1254
Haiogenated aliphatics
Chloroform
Dlchlorobromomethane
Methylene chloride
Dlbromochloromethane
Tetrachloroethylene
1,1, 1-Trichloroe thane
Tnchloroethylene
Trichlorof luoromethane
Bromoform
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
jleic acid
Linoleic acid
Xylenes
No. of
samples
in which
pollutant
was
detected
5
5
13
6
4
5
5
2
1
1
1
1
1
1
1
2
1
2
1
1
1
1
1
1
1
1
1
1
Raw water
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
3
4
4
4
4
4
4
4
3
4
3
4
4
4
4
4
4
4
4
4
4
Discharge, POTW
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
ygA
24
40
21
38
<1
29
240
20
2
<1
<1
6
17
<1
14
10
6
<1
2
6
<1
14
94
42
14
110
50
3
No. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
9
8
3
7
6
4
8 '
2
2
7
2
2
2
1
3
1
1
6
5
1
8
8
8
8
9
8
8
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
1
6
2
3
4
1
7
7
2
7
7
7
8
6
8
8
3
4
8
1
1
1
1
0
1
1
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
yg/L
81
140
350
260
<1
40
1,000
30
3
16
29
35
100
<1
1
81
1
<1
3
2
<1
<1
<1
6
7
'1
4,200
900
960
470
1,300
850
16
NOTE: Blanks indicate no data available.
Date: 6/23/80
11.16-30
-------
TABLE 16-25.
sr
0>
to
CO
CD
O
I
U)
NONINTEGRATED FINE SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Subcagegory: Nonintegrated fine
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Phthalates
Bis (2-ethylhexyl)
phthalate
Phenols
Phenol
Monocyclic aromatics
Benzene
Toluene
Halogenated aliphatics
Chloroform
1 , 2-Dichloroethane
Methylene chloride
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Linoleic acid
No. of
samples
in which
pollutant
was
detected
3
3
3
2
3
3
1
1
1
1
1
Raw water
Average
concentra-
No. of tion of
samples pollutant
in which in all
pollutant samples
was not analyzed.
detected pg/L
0 <1
0 9
0 6
0 <1
0 4
0 26
2 1
2 <1
2 <1
2 <1
2 3
Aeration influent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
3
4
3
1
1
4
6
4
3
2
1
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
3
2
3
5
5
2
0
2
3
4
5
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
3
13
3
<1
5
55
3
6
6
<1
<1
210
440
40
12
19
33
Final effluent
No. of
samples
in which
pollutant
was
detected
9
9
9
9
9
9
7
3
2
3
6
3
4
7
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
2
6
7
6
3
6
5
2
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
yg/L
1
18
6
4
51
290
13
-------
TABLE 16-26.
rt
(D
CT>
CO
00
O
cr>
U)
to
NONINTEGRATED-TISSUE SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Subcategory : Noninteqrated-tissue
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Lead
Mercury
Nickel
Zinc
Phthalates
Bis{2-ethylhexyl)
phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Phenol
Monocyclic aromati.cs
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Tetrachloroethylene
Trichloroethylene
Nonconventional pollutants
Abietic
Dehydroabietic acid
Isopimanc acid
Pimanc acid
Oleic acid
Xylenes
Raw water
Average
concentra-
No. of No. of tion of
samples samples pollutant
in which in which in all
pollutant pollutant samples
was was not analyzed.
detected detected M9/L
1 1 <1
11 4
1 1 <1
2 0 <1
1 1
-------
D
d>
rt-
CD
cr«
CO
\
00
o
TABLE 16-27.
cr>
i
to
CO
NONINTEGRATED-MISCELLANEOUS SUBCATEGORY - SUMMARY
OF VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Subcateqory : Nonintoqrated-nii scellaneous
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Phenols
Pentachlorophenol
Phenol
2 , 4 ,6-Trichlorophenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
polychlorinated biphenyls
and related compounds
Aroclor 1254
Halogenated aliphatics
Chloroform
1 ,1 , 1-Tnchloroethane
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Linoleic acid
Xylenes
Mo. of
samples
in which
pollutant
was
detected
3
3
1
3
3
3
3
3
2
1
1
1
1
1
Raw water
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
1
2
2
2
2
2
c Ian fj cat ion influont
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
2
6
9
14
<1
3
16
6
58
<1
<1
4
J
19
No. of
samples
in which
pollutant
was
detected
9
9
3
9
9
8
9
9
2
6
3
2
1
1
3
6
3
8
3
2
1
4
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
1
0
0
7
3
6
7
8
6
6
3
6
1
6
T
8
6
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
13
46
9
14
<1
20
540
26
24
5
6
<1
<1
1
3
7
59
120
28
11
9
3
Final effluent
No. of
samples
in which
pollutant
was
detected
8
111
3
9
9
9
9
8
1
5
3
1
2
5
1
3
6
6
1
3
No. of
samples
in which
pollutant
was not
detected
1
1
0
0
0
0
0
1
8
4
6
8
7
4
6
6
3
3
8
6
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
ug/L
2
8
9
5
<1
5
140
6
8
2
6
<:!
4
2
<1
1
4
93
2
49
Percent
removal
85
83
a
64
a
75
75
62
67
60
a
a
~
- b
b
a
67
43
23
93
b
Negligible removal.
b
Negative removal.
NOTE: Blanks indicate no data available.
-------
o
B>
rt
TABLE 16-28.
CO
oo
o
U>
NONINTEGRATED-LIGHTWEIGHT SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATION [1]
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis (2-ethylhexyl)
phthalate
Di-n-butyl phthalate
Phenols
Phenol
Monocyclic aromatics
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
Methylene chloride
Nonconventional pollutants
Xylenes
No. of
samples
in which
pollutant
was
detected
1
1
3
1
1
1
1
1
1
1
Raw water
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
0
0
Subcategory :
Noninfegrated-lightweight
Aeration influent
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
Mg/L
2
23
10
4
<1
2
5
4
7
2
2
No. of
samples
in which
pollutant
was
detected
2
2
3
2
3
2
3
3
1
2
2
2
3
1
1
No. of
samples
in which
pollutant
was not
detected
1
1
0
1
0
1
0
0
2
2
1
1
0
2
5
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
2
19
9
6
<1
1
16
5
<1
2
2
2
27
<1
Final effluent
No. of
samples
in which
pollutant
was
detected
2
2
3
2
3
2
2
3
1
2
2
2
3
2
No. of
samples
in which
pollutant
was not
detected
1
1
0
1
0
1
1
0
2
1
1
1
0
1
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
2
4
9
<1
<1
<1
4
7
2
2
<1
<1
3
<1
Percent
removal
a
79
a
83
a
a
75
_b
_b
_a
50
50
89
a
Negligible removal.
Negative removal.
NOTE: Blanks indicate no data available.
-------
o
ft
^J
• •
en
CD
O
CT>
I
U>
cn
TABLE 16-29.
NONINTEGRATED-FILTER AND NONWOVEN SUBCATEGORY -
SUMMARY OF VERIFICATION DATA FOR TOXIC AND
NONCONVENTIONAL POLLUTANT CONCENTRATION [1]
Subcategory: Nonintegrated-f liter and nonwoven
Pollutant
Toxic pollutants
Metals
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Zinc
Phthalates
Bis(2-ethylhexyl)
phthalate
Phenols
Phenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Polychlorinated biphenyls
and related compounds
Aroclor 1254
Nonconventional pollutants
Dehydroabietic acid
Linoleic acid
No. of
samples
in which
pollutant
was
detected
1
1
3
1
2
1
2
1
1
1
1
Raw water
No. of
samples
in which
pollutant
was not
detected
1
1
0
1
0
1
0
1
1
1
1
Average
concentra-
tion of
pollutant
in all
samples
analyzed,
yg/L
-------
TABLE 16-30.
CD
O
i
CO
NONINTEGRATED-PAPERBOARD SUBCATEGORY - SUMMARY OF
VERIFICATION DATA FOR TOXIC AND NONCONVENTIONAL
POLLUTANT CONCENTRATIONS [1]
No. of
samples
in which
pollutant
was
Toxic pollutants
Metals
Chromium 2
Copper 2
Cyanide 6
Lead 2
Mercury 2
Nickel 2
Zinc 2
Phthalates
Bis(2-ethylhexyl)
phthalate 1
Di-n-butyl phthalate
Diethyl phthalate
Phenols
Phenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Methylene chloride 1
Tetrachloroethylene
Nonconventional pollutants
Abietic acid
Dehydroabietic acid
Isopimaric acid
Pimaric acid
Oleic acid
Xyienes
Raw water
Average
concentra-
No. of tion of
samples pollutant
in which in all
pollutant samples
was not analyzed.
0 2
0 4
0 9
0 2
0 <1
0 3
0 15
] 42
1 3
Subcategory :
Nonintegrated-paperboard
Aeration influent
No. of
samples
in which
pollutant
was
detected
3
3
3
3
3
3
3
3
3
1
3
1
3
3
1
3
1
3
3
3
3
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
0
0
2
0
2
0
0
2
0
2
0
0
0
0
0
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
pg/L
26
27
9
2
<1
18
1,300
7
180
c
4
6
<1
3C
3°
b
<1
3
7
160
8
25c
260
8C
Final effluent
No. of
samples
in which
pollutant
was
detected
6
6
6
6
6
6
6
3
2
3
1
2
4
4
3
No. of
samples
in which
pollutant
was not
detected
0
0
0
0
0
0
0
3
4
3
5
4
2
2
3
Average
concentra-
tion of
pollutant
in all
samples
analyzed.
M9/L
6
4
26
9
<1
5
72
2
29
1
<1
<1
<1
64
2
Percent
removal
77
85
a
b
72
94
71
a
83
b
67
67
58
Negative removal.
Negligible removal.
Oxidation influent.
Note: Blanks indicotn no data available.
-------
TABLE 16-31. RAW WASTE LOADS FOR SELECTED MILLS [1]
Subcategory/subdl visions
Alkaline-dissolving
Alkaline-market
Softwood mills
Hardwood mills
Mixed mills
Alkaline-BCT
Alkaline-fine
High clay mills
Low clay mills
High softwood
Mills making some groundwood
High clay-high softwood
High clay-high hardwood
Low clay-high hardwood
Alkaline-unbleached
Linerboard
Packaging items
Bag
Semi-chemical
Mills with liguor recovery
Mills with no liquor recovery
One third wastepaper
Mills not representative of
subcategory
Alkaline-unbleached and
semi-chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Groundwood- fine
Deink-fine and tissue
Mills utilizing mainly deink
furnish
Fine mills utilizing mixed
furnish
Tissue mills utilizing mixed
furnish
Wastepaper- tissue
Industrial tissue mills
Sanitary tissue mills
Wastepaper-board
Wastepaper-molded products
Wastepaper-construction products
Predominantly wastepaper
furnish
Furnish includes TMP
Furnish includes other
groundwood
Other furnish
Nonintegrated- fine
Nonintegrated- tissue
Nonintegrated- 1 ightweight
Electrical paper
Miscellaneous tissue and
carbonizing
Printing and thin paper
Carbonize, thin, cigarette
Nonintegrated-filter and
nonwoven
Nonltegrated-paperboard
Mill
number
032003
030018
030005
030028
030004
030027
030046
030051
030045
030020
030034
030060
010002
010048
010032
060004
020005
020001
020010
015003
054003
046403
040017
070001
054006
052004
140021
140007
140010
085006
090010
150006
120014
120012
120005
140065
080046
090020
105071
090015
150020
105013
105050
105073
Production,
Mg/d
490
340
1,500
870
690
680
560
870
380
640
460
850
360
750
450
170
270
560
1,620
940
420
370
140
45
440
140
320
69
42
150
40
19
210
150
54
300
810
24
58
180
18
11
14
Raw
Flow,
m3/Mg
240
180
73
150
190
72
130
94
150
120
120
160
44
220
47
49
47
19
60
50
94
360
120
79
110
66
78
54
120
140
77
46
14
7.4
4.2
8.9
61
80
260
150
200
135
170
110
waste
Bod5,
kg/Mg
54
39
18
36
58
22
31
33
65
26
39
13
33
18
28
56
24
18
19
12
280
97
18
19
29
10
55
56
38
19
10
33
13
5.5
3.9
14
13
12
2.9
8.2
20
4.9
13
load
TSS,
kg/Mg
82
48
20
24
42
33
80
41
130
78
100
25
23
17
55
52
8.1
49
29
56
15
37
39
56
79
3.5
160
130
100
59
19
10
5.1
1.5
6.5
32
44
19
150
16
57
20
42
NOTE- Blanks indicate no data available.
Date: 6/23/80
11.16-37
-------
contained in mill effluents. Biological treatment systems are
currently employed extensively by pulp, paper, and paperboard
mills to reduce BOD5 and TSS loads. A summary of treatment
systems currently employed in the pulp, paper and paperboard
industry is shown in Table 16-32. As noted, aerated stabili-
zation is the most common treatment process employed at mills
discharging directly to a receiving water. Primary treatment
only is employed at a relatively large number of plants in the
nonintegrated and secondary fiber subcategories. Primary treat-
ment can often achieve substantial BOD5 reductions, if BOD5 is
predominantly contained in suspended solids.
The mills with treatment systems exhibiting the greatest percent
BOD5 and TSS removals are shown in Table 16-33 for each subcate-
gory. BOD5 removals for these mills range from 70% to 99% with
effluent concentrations between 9 and 235 mg/L. Activated sludge
is employed at 9 of the 18 mills.
II.16.4.1 Primary and Preliminary Treatment
Often primary treatment is necessary to remove suspended organic
and inorganic materials that may damage or clog downstream treat-
ment equipment. This can be accomplished by sedimentation,
flotation or filtration. Sedimentation can involve mechanical
clarifiers, flotation units, or sedimentation lagoons. Mechani-
cal clarification is the most common technology for removing
suspended solids.
II.16.4.1.1 Dissolved Air Flotation
Dissolved air flotation (DAF) units also have been applied to
effluents from paper mills and have, in some cases, effectively
removed suspended solids. DAF units are somewhat limited because
of their inability to handle high pollutant concentrations and
shock loads.
II.16.4.1.2 Primary Clarification
Because of the biodegradable nature of a portion of the settle-
able solids present in pulp, paper and paperboard wastewaters,
clarification results in some BOD5 reduction. Typical BOD5
removals through primary clarification in integrated pulp and
paper mills varies between 10% and 30%. The exact BOD5 removal
depends on the relative amount of soluble BOD5 present in the raw
wastewater. Primary clarification can result in significantly
higher BOD5 reductions at nonintegrated mills than at integrated
mills. Responses to the data request program indicate that
roughly 50% of the raw wastewater BOD5 is commonly removed at
nonintegrated mills through primary clarification.
Date: 6/23/80 11.16-38
-------
ft
fD
K>
OJ
\
00
o
TABLE 16-32. SUMMARY OF METHOD OF DISCHARGE AND INPLACE TECHNOLOGY [1]
cr>
oo
Treatment scheme - Direct discharge
Subcategory
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline-fine
Alkal ine-unbleached
Semi -chemical
Alkaline-unbleached and
Semi-chemical
Alkaline-newsprint
Sulf ite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Groundwood-fine
Deink-fine and tissue
Deink-newsprint
Wastepaper-tissue
Wastepaper -board
Wastepaper -molded products
Was tepaper-cons true t ion
products
Nonintegrated-f ine
Nonintegrated-tissue
Nonintegrated-lightweight
Nonintegrated-filter and
nonwoven
Nonintegrated-paperboard
Subtotal
Miscellaneous mills
Total
No.
of
mills
3
9
8
18
29
19
10
3
6
18
2
6
8
17
3
22
147
15
58
39
26
18
16
12
512
132
644
Method of discharge No
Direct
3
9
8
14
28
17
9
3
6
17
2
5
7
10
11
45
2
4
18
14
14
6
5
257
102
359
Indirect
4
1
2
1
1
1
1
5
3
3
84
11
36
19
12
4
10
7
205
25
230
Self external
contained treatment
2
2
2
1
2 1
8 2
18 3
2
18 1
2 3
1
50 18
5 4
55 22
Primary
only
2
1
3
6
1
1
1
4
8
1
1
6
10
6
3
3
57
23
80
Aerated
lagoon
2
4
3
2
9
1
7
1
3
2
2
21
1
3
2
1
1
2
67
22
89
Lagoon w/
polishing
pond
1
4
2
5
6
1
2
1
21
10
31
Activated
sludge
1
1
5
4
3
1
1
1
1
1
1
3
7
1
4
2
1
40
19
59
Trickling
filter Other
1
1
5
1 7
4
1
1
1
5
3
2
2
9
3
1
1 6
1
2 53
2 21^
4 74
Miscellaneous mills not included in subcategorization.
Note: Data for 1976 calendar year.
-------
ri-
ft
en
CO
00
o
TABLE 16-33.
MILLS REPORTING BEST PERCENT REMOVAL OF
BOD5 AND TSS BY SUBCATEGORY [1]
Final effluent average day
Production
Subcategory
Alkaline-dissolving
Alkaline-market
Alkaline-BCT
Alkaline- fine
Alkaline-unbleached
Semi-chemical
Alkaline-unbleached and
semi-chemical
Alkaline-newsprint
Sulfite-dissolving
Sulfite-papergrade
Thermo-mechanical pulp
Groundwood-CMN
Groundwood- fine
Deink-fine and tissue
Wastepaper- tissue
Wastepaper-board
Nonintegrated- fine
Nonintegra ted- tis sue
Nonintegrated-lightweight
Nonintegrated-filter and
nonwoven
Mg/d
1,040
660
280
690
970
440
1,540
1,420
350
450
140
890
710
770
150
290
370
180
58
39
(tons/d)
(1,150)
(722)
(310)
(760)
(1,070)
(490)
(1,700)
(1,560)
(390)
(490)
(160)
(980)
(790)
(840)
(160)
(320)
(411)
(190)
(64)
(43)
Flow
MJ/Mg
240
170
190
70
48
34
52
98
170
93
81
120
58
90
88
5.8
110
68
220
290
(kgal/t)
(57)
(41)
(45)
(17)
(12)
(8.1)
(12)
(24)
(42)
(22)
(20)
(28)
(14)
(22)
(21)
(1.4)
(26)
(16)
(54)
(69)
kg/Mg
7.5
2.7
2.1
0.6
0.7
1.3
2.0
2.3
41
5.1
5.6
6.4
0.5
3.5
1.3
0.1
1.8
2.1
8.1
2.1
BOD 5
(Ib/ton)
(15)
(5.4)
(4.2)
(1.2)
(1.5)
(2.5)
(4.1)
(4.6)
(82)
(10)
(11)
(13)
(1-0)
(6.9)
(2-6)
(0.1)
(3.5)
(4.2)
(16)
(4.1)
(mg/L)
34
16
11
9
16
38
40
23
240
60
68
54
9
38
15
11
16
31
36
7
kg/Mg
15
3.1
3.9
1.9
1.7
1.5
3.5
2.4
11
7.5
29
4.5
2.0
6.3
0.4
0.3
2.7
0.6
2.4
3.1
TSS
(Ib/ton)
(29)
(6.1)
(7.7)
(3-9)
(3.3)
(2.9)
(6.9)
(4-7)
(22)
(15)
(59)
(9)
(3.9)
(12)
(0.8)
(0.5)
(5.4)
(1-D
(4.7)
(6.2)
(mg/L)
61
18
21
30
34
43
67
24
64
80
360
38
34
69
5
41
25
9
10
11
Treatment
type3
ASB
ASB w/Hold.
ASB
Act. SI.
ASB
Act. Si.
Act. Si.
ASB
ASB
Act. SI.
Act. Si.
Act. SI.
Act. Si.
Act. SI.
Act. SI.
ASB
ASB w/Hold.
No Sec. Trtmt
Trick. Filter
ASB
Percent
reduction
BOD 5
86
94
94
97
94
95
87
91
71
87
71
70
95
95
93
99
88
86
86
87
TSS
82
88
91
94
99
97
86
95
92
92
29
90
96
97
99
98
94
99
98
92
aASB: aerated stabilization basin; Hold.: holding pond; Act. SI.: activated sludge; Sec. Trtmt: secondary treatment;
Trick. Filter: trickling filter.
NOTE: Data represents 1976 calendar year.
-------
II.16.4.2 Biological Treatment
Currently, the most common types of biological treatment used in
the pulp, paper and paperboard industry include oxidation basins,
aerated stabilization basins, and the activated sludge process or
its modifications. Other biological systems include oxygen acti-
vated sludge, the Zurn/Attisholz process, rotating biological con-
tactors, and anaerobic contact filters.
-II.16.4.2.1 Oxidation Basins
Oxidation basins were the first type of biological treatment
systems used in the pulp, paper and paperboard industry. Typical
design BODs loads range from 56 to 67 kilograms per hectare
(kg/ha) of surface area/day (50 to 60 Ib/acre/day). Retention
times can vary from 20 to over 60 days. Literature presenting
data on the removal of toxic and nonconventional pollutants
through application of oxidation basin technology is limited.
II.16.4.2.2 Aerated Stabilization Basins
The aerated stabilization basin (ASB) evolved from the necessity
of increasing performance of existing oxidation basins due to
increasing effluent flows and/or more stringent water quality
standards. The removal efficiency of an ASB treating unbleached
kraft waste was evaluated over a 1-month period in late 1976.
Although the raw wastewater exhibited an LC-50 of 1% and 2% by
volume, all but one of the 26 treated effluent samples either
were nontoxic or exhibited greater than 50% fish survival after
96 hours of exposure. The one failure was attributed to a black
liquor spill at the mill. Average reductions of 87% BODs, 90%
toxicity and 96% total resin acids were achieved.
Pilot-scale ASB treatment of bleached kraft wastewater was
evaluated over a 5-month period. Two basins, one with a 5-day
and one with a 3-day hydraulic detention time, were studied with
and without surge equalization. The raw wastewater BOD5 varied
from 108 mg/L to 509 mg/L and was consistently toxic. The median
survival times (MST) of fish ranged from 7 to 1,440 minutes.
Mean BOD5 removals with surge equalization were 85% for the 5-day
basin and 77% for the 3-day basin. Mean effluent BOD5 levels
with surge equalization were 40 mg/L for the 5-day basin and
59 mg/L for the 3-day basin. Mean reported effluent BODs values
for the 5-day and 3-day basins without equalization were 51 mg/L
and 67 mg/L, respectively.
II.16.4.2.3 Activated Sludge Processes
The activated sludge process is a high-rate biological wastewater
treatment system. The ability of activated sludge basins to de-
toxify bleached kraft mill effluents was analyzed over a 5-month
Date: 6/23/80 11.16-41
-------
period. Two pilot-scale activated sludge systems (8-hour and
24-hour detention times) were operated with and without surge
equalization. Raw wastewater BOD5 varied from 108 to 509 mg/L.
Mean BODs removals for the 8-hour and 24-hour activated sludge
lagoon with a 12-hour surge equalization basin achieved an
average of 76% and 72% BOD5 removal, respectively. Effluent BOD5
concentration for the 24-hour system ranged from 5 mg/L to 263
mg/L with a mean of 64 mg/L. The 8-hour activated sludge system
removed an average of 72% of the BODs. Final effluent BODs con-
centrations ranged from 14 to 270 mg/L, with a mean of 64 mg/L.
The pure oxygen activated sludge process uses oxygen, rather than
air, to stimulate biological activity. Field test data by Union
Carbide Corp. confirms that the oxygen activated sludge process
is capable of achieving final effluent BOD5 concentrations on the
order of 20 to 30 mg/L with pulp, paper, and paperboard mill
wastes. Effluent TSS after clarification was generally in the
range of 40 to 60 mg/L. A summary of pilot-scale information is
presented in Table 16-34.
TABLE 16-34. OXYGEN ACTIVATED SLUDGE TREATABILITY
PILOT SCALE [1]
Production process
Alkaline-unbleached
Alkaline-unbleached
Alkaline-unbleached
Retention,
hrs
1.3 -
1.8 -
2.0 -
2.
3.
2.
2
0
9
BODs, :
Influent
280
210
265
- 460
- 210
- 300
mg/L TSS , mg/L
Effluent
20
16
25
- 41
- 22
- 30
Influent
57 -
120 -
95 -
86
120
120
Effluent
46
36
60
- 61
- 36
- 70
Sulfite/newsprint effluent was treated using an oxygen activated
sludge pilot-plant facility over an 11-month period. BOD5 re-
ductions during this time were over 90%. Final BOD5 and TSS con-
centrations ranged from 23 to 42 mg/L and 61 to 111 mg/L,
respectively.
Zurn/Attisholz System. Seven full-scale Zurn/Attisholz (Z/A)
systems are currently in use at pulp and paper mills in the United
States. These installations treat wastewaters from the following
types of manufacturing:
Deink-fine and tissue (5 mills)
Sulfite-papergrade (1 mill)
Integrated-miscellaneous (1 mill)
Most of these mills reportedly maintain final effluent BOD5 and
TSS concentrations in the range of 20 to 25 mg/L each. One mill
reportedly achieves BOD5 and TSS levels in the range of 5 to 10
mg/L each. Another mill also attained a 96% BOD5 and 99% TSS
reduction using the Z/A process.
Date: 6/23/80 11.16-42
-------
A pilot study comparing a two-stage to a single-stage activated
sludge system has recently been performed. The two-stage system
achieved a higher toxicity reduction in treating bleached kraft
wastewater than did a single-stage system.
Rotating Biological Contactor (RBC). This system involves
a series of discs on a shaft supported above a basin containing
wastewater. Pilot-scale evaluations of the RBC system treating
bleached kraft wastewater with an average influent BODs content
of 235 mg/L have resulted in substantial BODs reductions.
II.16.4.3 Chemically Assisted Clarification
Recent experience with full-scale alum-assisted clarification of
biologically treated kraft mill effluent suggests that with
proper pH adjustment, final effluent qualities of 15 mg/L each
of BOD5 and TSS can be achieved. The desired alum dosage to
attain these levels would be between 100 and 150 mg/L. A
significantly lower alum dosage could provide insufficient floe
formation, while a higher dosage would result in proportionately
high levels of chemical solids and sludge quantities that must
be removed and disposed.
As part of an EPA-sponsored study, biologically treated effluent
from an alkaline kraft mill was evaluated with alum precipitation
on a laboratory scale. Existing full-scale treatment consisted
of a primary clarifier, aerated stabilization basin and polishing
pond. Twenty-four hour composite samples of the polishing pond
effluent were taken on three separate days. The samples were
adjusted to pH 4.6 with alum and four drops of polymer per liter
of sample were added. The results are summarized in Table 16-35.
TABLE 16-35. LABORATORY EVALUATION OF ALUM PRECIPITATION ON
ALKALINE KRAFT MILL POLISHING POND EFFLUENT [1]
Concentration range, mg/L
Polishing pond Alum-treated
effluent effluent
Total
Total
resin
and fatty acids
chlorinated
derivatives
Chloroform
BOD5
2.8
0.43
0.025
43.
- 3.
- 0.
- 0.
- 51
8
45
032
•
ND
ND
0.018
0.
- 0.
- 0.
- 14
04
022
•
ND - Not detected.
In a recent EPA-sponsored laboratory study, alum, ferric chloride
and lime in combination with five polymers were evaluated in
further treatment of biological effluent from four pulp and paper
mills. Of the three chemical coagulants, alum provided the most
consistent flocculation at minimum dosages; lime was the least
Date: 6/23/80 11.16-43
-------
effective of the three. The optimum alum dose was determined for
four of the effluents and ranged between 40 and 180 mg/L at a
constant dosage of 2 mg/L polymer.
II.16.4.4 Filtration
Filtration is an available technology for application in treating
pulp, paper, and paperboard wastewaters. If properly designed
and operated, filtration can yield significant solids removal.
Table 16-36 shows the results of a study evaluating the efficien-
cy of sand filtration on four pulp and paper mill effluents.
TABLE 16-36. SAND FILTRATION RESULTS [1]
Mill
NO.
1
2
3
5
Initial
TSS, mg/L
110
5.5
70
60
TSS removal, percent
w/chemical w/o chemical
addition addition
64 14
36
71 68
23
1.16.4.5 Activated Carbon Adsorption
Researchers have indicated that pulp and paper mill wastewater
suitable for reuse can be obtained using granular carbon without
a biological oxidation step, particularly if the raw waste ex-
hibits a BOD5 of 200 to 300 mg/L. Color due to refractory
organic compounds contained in pulping effluents can also be
reduced by such treatment. Table 16-37 presents the pilot-plant
results obtained by the authors.
Extensive pilot-plant tests for treating unbleached kraft mill
wastewater with granular and fine activated carbon (AC) (the fine
activated carbon system is subject to a patent application) have
been run. The 113 L/min (30 gpm) pilot plant utilized four
different treatment processes, as follows:
1. Clarification followed by downflow granular carbon activated
columns;
2. Lime treatment and clarification followed by granular acti-
vated carbon columns;
3. Biological oxidation and clarification followed by granular
activated carbon columns; and
4. Lime treatment and clarification followed by fine activated
carbon effluent treatment (subject of a patent application).
Table 16-38 presents the results of the pilot-plant investigation,
Date: 6/23/80 11.16-44
-------
Date: 6/23/80
TABLE 16-37. RESULTS OF 'GRANULAR ACTIVATED CARBON COLUMN PILOT-PLANT
TREATING UNBLEACHED DRAFT MILL WASTE [1]
AC columns preceded by lime
precipitation
and biological oxidation
M
I \
l_i
CT>
1
U1
Property3
BOD 3, mg/L
COD , mg/L
SS , mg/L
Turbidity, JTU
Color, Pt-Co units
Odor
pH, pH units
TSS, mg/L
Influent
48
-
-
-
—
365
-
Effluent
23
-
-
-
-
13
-
Removal,
percent
52
-
-
-
—
96
-
Influent
100
-
-
-
-
185
-
AC columns
Run 1
Effluent
32
-
-
-
—
23
-
preceded by lime precipitation3
Removal ,
percent
69
-
-
-
—
88
-
Influent
82
320
120
35
28
—
12
1,280
Run 2
Effluent
12
200
74
35
0
-
10
1,200
Removal ,
percent
85
35
36
0
100
—
12
6
Columns loaded at 3.6-4.0 gpm/fta.
Note: Dashes indicate no data available.
-------
o
to
Jf
K>
U>
00
o
TABLE 16-38.
RESULTS OF ACTIVATED CARBON PILOT PLANTS
TREATING UNBLEACHED KRAFT MILL EFFLUENT [1]
Description of
carbon process
AC columns preceded by
biological oxidation and AC columns preceded by
clarification primary clarification
Influ- Efflu- Removal, Influ- Efflu- Removal, Influ-EffTu- Removal, Influ- Efflu- Removal,
ent ent percent ent ent percent ent ent percent ent ent percent
AC columns preceded by
primary clarification
AC columns preceded by
lime treatment and
clarification
FACET system
Influ- Efflu- Removal,
ent ent percent
O>
Hydraulic
load, gpm/ft2 2.13
Carbon
Contact time,
min.
Parameters
BOD, mg/L
TOC, mg/L
Color, units
Fresh carbon
dosage
kg/m3
(Ib carbon/
1,000 gal)
Granular
140
150
740
57
210
1.0
(8)
1.42
Granular
0.71
Granular
61
71
220 83
920 180
2.5
(20)
62 310 120
80 1,160 200
3.5
(28)
61
83
1.42
Granular
108
180
250
100
76
0.3
(2.5)
26
44
70
NA
Intermediate
160
160
100
73
0.5
(3.9)
36
aFine activated carbon effluent treatment.
filtered.
Note: Blanks indicate no data available.
-------
11.16.5 REFERENCES
1. Preliminary Data Base for Review of BATEA Effluent Limita-
tions Guidelines, NSPS, and Pretreatment Standards for the
Pulp, Paper, and Paperboard Point Source Category. Prepared
for USEPA by E. C. Jordan, Co., Inc., Portland, Maine 04112,
Contract No. 68-01-4624, June 1979.
2. NRDC Consent Decree Industry Summary - Pulp, Paper, and
.Paperboard Industry.
3. Environmental Protection Agency Effluent Guidelines and
Standards for Pulp, Paper and Paperboard (40 CFR 430;
FR 18742, May 12, 1974; Amended as shown in Volume 40 Code
of Federal Regulations, Revised as of July 1, 1976; 41 FR
27732, July 6, 1976; 42 FR 1398; January 6, 1977).
Date: 6/23/80 11.16-47
-------
11.17 RUBBER PROCE S SING
II.17.1 INDUSTRY DESCRIPTION [1]
II.17.1.1 General Description
The Rubber Processing Industry in the United States is covered by
seven SIC codes. They are:
SIC 2822: Synthetic Rubber Manufacturing (Vulcanizable
Elastomers)
SIC 3011: Tire and Inner Tube Manufacturing
SIC 3021: Rubber Footwear
SIC 3031: Reclaimed Rubber
SIC 3041: Rubber Hose and Belting
SIC 3069: Fabricated Rubber Products, Not Elsewhere
Classified
SIC 3293: Rubber Gaskets, Packing and Sealing Devices
This industry includes a wide variety of production activities
ranging from polymerization reactions closely aligned with the
chemical processing industry to the extrusion of automotive win-
dow sealing strips. There are approximately 1,650 plants in this
industry divided into the 11 subcategories described below.
Plant production ranges from 1.6 x 103 Mg/yr (3.6 x 106 Ib/yr)
to 3.7 x 105 Mg/yr (8.2 x 108 Ib/yr).
Table 17-1 presents a summary of the Rubber Processing Industry
regarding the number of subcategories and the number and types
of discharges. Table 17-2 presents a subcategory profile of BPT
regulations (daily maximum and 30-day averages).
Date: 6/23/80 II.17-1
-------
TABLE 17-1. INDUSTRY SUMMARY [1, 2]
Industry: Rubber Processing
Total Number of Subcategories: 11
Number of Subcategories Studied: 3a
Number of Dischargers in Industry:
Direct: 1,054
Indirect: 504
Zero: 100
Wet digestion, although not a
Paragraph 8 exclusion, was not
studied due to the lack of plant
specific data. Emulsion and
solution crumb rubber, although can-
didates for exclusion, were studied,
because of data availability.
TABLE 17-2. BPT LIMITATIONS FOR SUBCATEGORIES OF
RUBBER PROCESSING INDUSTRY [3]
(kg/Mg)
pH limitation, all Subcategories: 6 to 9
Tire and inner Emulsion
tube plants crumb rubber
Daily 30-Day Daily 30-Day
Pollutant max av max av
COD 12.0 8.0
BOD5 0.60 0.40
TSS 0.096 0.064 0.98 0.65
Oil and grease 0.0024 0.016 0.24 0.16
Zinc
Solution . .
crumb rubber Latex rubber Small GHEF* Medium CHEF3
Daily 30-Day Daily 30-Day Daily 30-Day Daily 30-Day
max av max av max av max av
5.91 3.94 10.27 6.85
0.60 0.40 0.51 0.34
0.98 0.65 0.82 0.55 1.28 0.64 0.80 0.40
0.24 0.16 0.21 0.14 0.70 0.25 0.42 0.15
Large
COD
BOD5
TSS 0.50
Oil and grease 0.26
Zinc
Pan , dry
digestion,
. Wet digestion mechanical
GMEF reclaimed reclaimed LDEHC Latex foam
14.7 6.11
3.72 2.2 2.4 1.4
0.25 1.04 0.52 0.384 0.192 6.96 2.9 2.26 0.94
0.093 0.40 0.144 0.40 0.144 2.0 0.73
0.058 0.024
Oil and grease limitations for nonprocess wastewater from plants placed in operation before 1959:
daily max, 10 mg/L; 30-day av, 5 mg/L.
General molded, extruded, and fabricated rubber.
Latex-dipped, latex-extruded, and latex-molded goods.
Note: Blanks indicate data not available
Date: 6/23/80 11.17-2
-------
II.17.1.2 Subcategory Descriptions
The Rubber Processing Industry is divided into 11 subcategories
based on raw waste loads as a function of production levels,
presence of the same or similar toxic pollutants resulting from
similar manufacturing operations, the nature of the wastewater
discharges, frequency and volume of discharges, and whether the
discharge is composed of contact or noncontact wastewaster.
Other primary considerations are treatment facilities and plant
size, age, and location. The 11 subcategories are listed below.
A brief description of each subcategory follows.
Subcategory 1: Tire and Inner Tube Manufacturing
Subcategory 2: Emulsion Crumb Rubber Production
Subcategory 3: Solution Crumb Rubber Production
Subcategory 4: Latex Rubber Production
Subcategory 5: Small-Sized General Molding, Extruding,
and Fabricating Rubber Plants
Subcategory 6: Medium-Sized General Molding, Extruding,
and Fabricating Rubber Plants
Subcategory 7: Large-Sized General Molding, Extruding,
and Fabricating Rubber Plants
Subcategory 8: Wet Digestion Reclaimed Rubber
Subcategory 9: Pan, Dry Digestion, and Mechanical Re-
claimed Rubber
Subcategory 10: Latex-Dipped, Latex-Extruded, and Latex-
Molded Goods
Subcategory 11: Latex Foam.
Subcategory 1 - Tire and Inner Tube^jjanufacturing
The production of tires and inner tubes involves three general
steps: mixing and preliminary forming of the raw materials,
formation of individual parts of the product, and constructing
and curing the final product. Seventy-three plants use these
general steps to produce tires in the United States.
The initial step in tire construction is the preparation or com-
pounding of the raw materials. The basic raw materials for the
tire industry include synthetic and natural rubber, reinforcing
agents, fillers, extenders, antitack agents, curing and accelera-
tor agents, antioxidants, and pigments. The fillers, extender,
and reinforcing agents, pigments, and antioxidant agents are
added and mixed into the raw rubber stock. This stock is non-
reactive and can be stored for later use. When curing and
accelerator agents are added the mixer becomes reactive, which
means it has a short shelf life and must be used immediately.
After compounding, the stock is sheeted out in a roller mill and
extruded into sheets or pelletized. This new rubber stock is
tacky and must be coated with an antitack solution, usually a
Date: 6/23/80 II.17-3
-------
soapstone solution or clay slurry, to prevent the sheets or
pellets from sticking together during storage.
The rubber stock, once compounded and mixed, must be molded or
transformed into the form of one of the final parts of the tire.
This consists of several parallel process by which the sheeted
rubber and other raw materials, such as cord and fabric, are made
into the following basic tire components: tire beads, tire
treads, tire cords, and the tire belts (fabric). Tire beads are
coated wires inserted in the pneumatic tire at the point where
the tire meets the steel wheel rim (on which it is mounted);
they insure a seal between the rim and the tire. The tire treads
are the part of the tire that meets the road surface; their de-
sign and composition depend on the use of the tire. Tire cords
are woven synthetic fabrics (rayon, nylon, polyester) impregnated
with rubber; they are the body of the tire and supply it with
most of its strength. Tire belts stabilize the tires and prevent
the lateral scrubbing or wiping action that causes tread wear.
The processes used to produce the individual tire components
usually involve similar steps. First the raw stock is heated
and subjected to a final mixing stage before going to a roller
mill. The material is then peeled off rollers and continuously
extruded into the final component shape. Tire beads are directly
extruded onto the reinforcing wire used for the seal, and tire
belt is produced by calendering rubber sheet onto the belt
fabric.
The various components of the tire are fitted together in a mold
to build green, or uncured, tires which are then cured in an
automatic press. Curing times range from less than one hour for
passenger car tires to 24 hours for large, off-the-road tires.
After curing, the excess rubber on the tire is ground off (de-
flashed) to produce the final product.
This subcategory is often subdivided into two groups of plants:
(1) those starting operations prior to 1959, and (2) those start-
ing operations after 1959. (Thirty-nine plants were in operation
prior to 1959.) The subdivision must be recognized in applying
limitations on plant effluents of oil and grease because its BPT
limitations are different for the two groups of plants. For
plants placed in operation after 1959, the 30-day average oil and
grease limitation is 0.016 kg/Mg of product. For plants placed
in operation prior to 1959, the limitation is the same
(0.016 kg/Mg) but only for process wastewater. Process waste-
water for these pre-1959 plants comes from soapstone solution
applications, steam cleaning operations, air pollution control
equipment, unroofed process oil unloading areas, mold cleaning
operations, latex applications, and air compressor receivers.
Water used only for tread cooling and discharges from other areas
of such plants is classified as non-process wastewater, in which
Date: 6/23/80 II.17-4
-------
oil and grease levels are limited to 5 mg/L as a 30-day average
and 10 mg/L as a maximum for a single day.
Subcategory 2 - Emulsion Crumb Rubber Production
Emulsion polymerization, the traditional process for synthetic
rubber production, is the bulk polymerization of droplets of
monomers suspended in water. Emulsion polymerization is operated
with sufficient emulsifier to maintain a stable emulsion and is
usually initiated by agents that produce free radicals. This
process is used because of the high conversion and the high
molecular weights that are possible. Other advantages include
a high rate of heat transfer through the aqueous phase, easy
removal of unreacted monomers, and high fluidity at high concen-
trations of product polymer. Over 90% of styrene butadiene
rubber (SBR) is produced by this method. Approximately 17 plants
use the emulsion crumb rubber process.
Raw materials for this process include styrene, butadiene,
catalyst, activator, modifier, and soap solution.
Polymerization proceeds stepwise through a train of reactors.
This reactor system contributes significantly to the high degree
of flexibility of the overall plant in producing different grades
of rubber.- The reactor train is capable of producing either
"cold" (277 K to 280 K, 103 kPa to 206 kPa) or "hot" (323 K,
380 kPa to 517 kPa) rubber. The cold SBR polymers, produced at
the lower temperature and stopped at 60% conversion, have im-
proved properties when compared to hot SBR's. The hot process
is the older of the two. For cold polymerization, the monomer-
additive emulsion is cooled prior to entering the reactors.
Each reactor has its own set of cooling coils and is agitated by
a mixer. The residence time in each reactor is approximately one
hour. Any reactor in the train can be bypassed. The overall
polymerization reaction is ordinarily carried to no greater than
60% conversion of monomer to rubber since the rate of reaction
falls off beyond this point and product quality begins to
deteriorate. The product rubber is formed in the milky white
emulsion phase of the reaction mixture called latex. Short stop
solution is added to the latex exiting the reactors to quench the
polymerization at the desired conversion. The quenched latex is
held in blowdown tanks prior to the stripping operation.
The stripping operation removes the excess butadiene by vacuum
stripping, then removes the excess styrene and water in a perfor-
ated plate stripping column. The water and styrene from the
styrene stripper are separated by decanting and the water is
discharged to the treatment facility. The recovered monomers are
recycled to the monomer feed stage. The latex is now stabilized
and is precipitated by an electrolyte and a dilute acid. This
coagulation imparts different physical characteristics to the
Date: 6/23/80 II.17-5
-------
rubber depending on the type of coagulants used. Carbon black
and oil can be added during this coagulation/precipitation step
to improve the properties of the rubber. This coagulated crumb
is separated from the liquor, resuspended and washed with water,
then dewatered, dried, and pressed into bales for shipment. The
underflow from the washing is sent to the wastewater treatment
facility.
Subcategory 3 - Solution Crumb Rubber Production
Solution polymerization is bulk polymerization in which excess
monomer serves as the solvent. Solution polymerization, used at
approximately 13 plants, is a newer, less conventional process
than emulsion polymerization for the commercial production of
crumb rubber. Polymerization generally proceeds by ionic
mechanisms. This sytem permits the use of stereospecific
catalysts of the Ziegler-Natta or alkyl lithium types which
make it possible to polymerize monomers into a cis structure
characteristic which is very similar to that of natural
rubber. This cis structure yields a rubbery product as opposed
to a trans structure which produces a rigid product 'that is
similar to plastics.
The production of synthetic rubbers by solution polymerization
processes is a stepwise operation very similar in many aspects
to production by emulsion polymerization. There are distinct
differences in the two technologies, however. For solution
polymerization the monomers must be extremely pure and the
solvent should be completely anhydrous. In contrast to emulsion
polymerization, where the monomer conversion is taken to approx-
imately 60%, solution polymerization systems are polymerized to
conversion levels typically in excess of 90%. The polymerization
reaction is also more rapid, usually complete in 1 to 2 hours.
Fresh monomers often have inhibitors added to them while in
storage to prevent premature polymerization. These inhibitors
and any water that is present in the raw materials must be
removed by caustic scrubbers and fractionating drying columns
to provide the solution process with the high purity and
anhydrous materials needed. The purified solvent and monomers
are then blended into what is termed the "mixed feed," which may
be further dried in a desiccant column.
The dried mixed feed is now ready for the polymerization step,
and catalysts can be added to the solution (solvent plus
monomers) just prior to the polymerization stage or in the lead
polymerization reactor.
The blend of solution and catalysts is polymerized in a series of
reactors. The reaction is highly exothermic and heat is removed
continuously by either an ammonia refrigerant or by chilled brine
Date: 6/23/80 II.17-6
-------
or glycol solutions. The reactors are similar in both design and
operation to those used in emulsion polymerization. The mixture
leaves the reactor train as a rubber cement, i.e., polymeric
rubber solids dissolved in solvent. A short stop solution is
added to the cement after the desired conversion is reached.
The rubber cement is then sent to storage tanks where antioxi-
dants and extenders are mixed in. The rubber cement is pumped
from the storage tank to the coagulator where the rubber is
precipitated with hot water under violent agitation. The solvent
and unreacted monomer are steam stripped overhead, then they are
condensed, decanted, and recycled to the feed stage. The bottom
water layer is discharged to the wastewaster treatment facility.
The stripped crumb slurry is further washed with water, then
dewatered, dried, and baled as final product. Part of the water
from this final washing is recycled to the coagulation stage,
and the remainder is discharged for treatment.
Subcategory 4 - Latex Rubber Production
The emulsion polymerization process is used by 17 production
facilities to produce latex rubber products as well as solid
crumb rubber. Latex production follows the same processing steps
as emulsion crumb rubber production up to the finishing process.
Between 5% and 10% of emulsion polymerized SBR and nearly 30% of
nitrile rubber production (NBR) are sold as latex. Latex rubber
is used to manufacture dipped goods, paper coatings, paints,
carpet backing, and many other commodities.
Monomer conversion efficiencies for latex production range from
60% for low temperature polymerization to 98% for high tempera-
ture conversion.
The monomers are piped from the tank farm to the caustic soda
scrubbers where the inhibitors are removed. Soap solution,
catalysts, and modifiers are added to produce a feed emulsion
which is fed to the reactor train. Fewer reactors are normally
used than the number required for a crumb product line. When
polymerization is complete, the latex is sent to a holding tank
where stabilizers are added.
A vacuum stripper removes any unwanted butadiene, and the steam
stripper following it removes the excess styrene. Neither the
styrene nor butadiene is recycled. Solids are removed from the
latex by filters, and the latex may be concentrated to a higher
solids level.
Date: 6/23/80 II.17-7
-------
Subcategories 5, 6, 7 - Small -, Medium-, and Large-Sized
General Molding, Extruding, and Fabricating Plants
These three closely related subcategories are divided based on
the volume of wastewater emanating from each. These subcate-
gories include a variety of processes such as compression
molding, transfer molding, injection molding, extrusion, and
calendering. An estimated 1,385 plants participate in these
subcategories.
A common step for all of the above processes is the compounding
and mixing of the elastomers and compounding ingredients. The
mixing operation is required to obtain a thorough and uniform
dispersion of the rubber and other ingredients. Wastewater
sources from the mixing operation generally derive from leakage
of oil and grease from the mixers.
Compression molding is one of the oldest and most commonly used
manufacturing processes in the rubber fabrication industry.
General steps for the processes include warming the raw
materials, preforming the warm stock into the approximate shape,
cooling and treating with antitack solution, molding by heat and
pressure, and finally deflashing (removing excess rubber).
Major products from this process include automotive parts,
medical supplies, and rubber heels and soles.
Transfer molding involves the forced shifting of the uncured
rubber stock from one part of the mold to another. The prepared
rubber stock is placed in a transfer cavity where a ram forces
the material into a heated mold. The applied force combined with
the heat from the mold softens the rubber and allows it to flow
freely into the entire mold. The molded item is cured, then
removed and deflashed. Final products include V-belts, tool
handles, and bushings with metal inserts.
Injection molding is a sophisticated, continuous, and essen-
tially automatic process that uses molds mounted on a revolving
turret. The turret moves the molds through a cyclic process
that includes rubber injection, curing, release agent treatment
and removal. Deflashing occurs after the product has been
removed. A wide range of products are made by this process,
including automative parts, diaphragms, hot-water bottles, and
wheelbarrow tires.
Extrusion forces unvulcanized rubber through a die to give long
lengths of rubber of a definite cross section. There are two
general subdivisions of this technique; one extrudes simple
products, and the other builds products by extruding the rubber
onto metal or fabric reinforcement. Products from these techni-
ques include tire tread, cable coating, and rubber hose.
Date: 6/23/80 II.17-8
-------
Calendering involves passing unformed or extruded rubber through
a set or sets of rolls to form sheets or rolls of rubber
product. The thickness of the material is controlled by the
space between the rolls. The calendar may also produce
patterns, double the product thickness by combining sheets, or
add a sheet of rubber to a textile material. The temperature
of the calender rolls is controlled by water and steam.
Products produced by this process include hospital sheeting and
sheet stock for other product fabrication.
Subcategory 8 - Wet Digestion Reclaimed Rubber
This subcategory represents a process that is used to recover
rubber from fiber-bearing scrap. Scrap rubber, water, reclaiming
and defibering agents, and plasticizers are placed in a steam-
jacketed, agitator-equipped autoclave. Reclaiming agents used
to speed up depolymerization include petroleum and coal tar-base
oils and resins as well as various chemical softeners such as
phenol alkyl sulfides and disulfides, thiols, and amino acids.
Defibering agents chemically do the work of the hammer mill by
hydrolyzing the fiber; they include caustic soda, zinc chloride,
and calcium chloride.
A scrap rubber batch is cooked for up to 24 hours and then dis-
charged into a blowdown tank where water is added to facilitate
subsequent washing operations. Digester liquor is removed by
a series of screen washings. The washed rubber is dewatered by
a press and then dried in an oven. Two major sources of waste-
waster are the digester liquor and the washwater from the screen
washings.
Two rubber reclaiming plants use the wet digestion method for
reclamation of rubber.
Subcategory 9 - Pan, Dry Digestion, and Mechanical
Reclaimed Rubber
This subcategory combines processes that involve scrap size
reduction before continuing the reclaiming process. The pan
digestion process involves scrap rubber size reduction on steel
rolls, followed by the addition of reclaiming oils in an open
mixer. The mixture is discharged into open pans which are
stacked on cars and rolled into a single-cell pressure vessel
where live steam is used to heat the mixture. Depolymerization
occurs in 2 to 18 hours. The pans are then discharged and the
cakes of rubber are sent on for further processing. The steam
condensate is highly contaminated and is not recycled.
The mechanical rubber reclaiming process, unlike pan digestion,
is continuous and involves fiber-free scrap being fed into a
horizontal cylinder containing a screw that works the scrap
Date: 6/23/80 II.17-9
-------
against the heated chamber wall. Reclaiming agents and
catalysts are used for depolymerization. As the depolymerized
rubber is extruded through an adjustable orifice it is quenched.
The quench vaporizes and is captured by air pollution control
equipment. The captured liquid cannot be reused and is dis-
charged for treatment.
Nine plants use these techniques to reclaim rubber.
Subcategory 10 - Latex-Dipped, Latex-Extruded, and
Latex-Molded Goods
These three processes involve the use of latex in its liquid
form to manufacture products. Latex dipping consists of
immersing an impervious male mold or article into the latex
compound, withdrawing it, cleaning it, and allowing the
adhering film to air dry. The straight dip process is replaced
by a coagulant dip process when heavier films are desired.
Fabric or other items may be dipped in latex to produce gloves
and other articles. When it has the required coating the mold
is leached in pure water to improve physical and electrical
properties. After air drying the items are talc-dusted or
treated with chlorine to reduce tackiness. Water is often used
in several processes, for makeup, cooling, and stripping.
Products from dipping include gloves, footwear, transparent
goods, and unsupported mechanical goods.
Latex molding employs casts made of unglazed porcelain or plaster
of paris. The molds are dusted with talc to prevent sticking,
then the latex compound is poured into the mold and allowed to
develop the required thickness. The mold is emptied of excess
rubber and then oven dried. The mold is removed and the product
is again dried in an oven. Casting is used to manufacture dolls,
prosthetics, printing matrices, and relief maps.
No description of latex extrusion is available.
Subcategory 11 - Latex Foam
No latex foam facilities are known to be in operation at this
time.
II.17.2 WASTEWATER CHARACTERIZATION
The raw wastewater emanating from rubber manufacturing plants
contains toxic pollutants that are present due to impurities in
the monomers, solvents, or the actual raw materials, or are
associated with wastewater treatment steps. Both inorganic and
organic pollutants are found in the raw wastewater, and conven-
tional pollutants may be present in significant loadings.
Date: 6/23/80 11.17-10
-------
Table 17-3 presents an industry-wide profile of the concentration
of toxic pollutants found at facilities in each subcategory (no
data are available for Subcategories 9 through 11). Table 17-4
gives a subcategory profile of the pollutant loadings (no data
are available for Subcategories 8, 10, and 11). These tables
were prepared from available 308 questionnaire data and sampling
data.
In-plant management practices may often control the volume and
quality of the treatment system influent. Volume reduction can
be attained by process wastewater segregation from noncontact
water, by recycling or reuse of noncontact water, and by the
modification of plant processes. Control of spills, leakage,
washdown, and storm runoff can also reduce the treatment system
load. Modifications may include the use of vacuum pumps instead
of steam ejectors, recycling caustic soda solution rather than
discharging it to the treatment system, and incorporation of a
more efficient solvent recovery system.
II.17.2.1 Tire and Inner Tube Manufacturing
The tire and inner tube manufacturing industry has several poten-
tial areas for wastewater production, but water recycle is used
extensively. The major area for water use is in processes re-
quiring noncontact cooling. The general practice of the industry
is to recirculate the majority of this water with a minimal
blowdown to maintain acceptable concentrations of dissolved
solids. Another water use area is contact water used in cooling
tire components and in air pollution control devices. This water
is also recirculated. Steam condensate and hot and cold water
are used in the molding and curing areas. The majority of the
water is recycled back to the boiler or hot water tank for use
in the next recycle. Soapstone areas and plant and equipment
cleanup are the final water use areas. Most facilities try to
recycle soapstone solution because of its high solids content.
Plant and equipment cleanup water is generally sent to the
treatment system. Table 17-5 presents a summary of the potential
wastewater sources and the general waste characterization for
this subcategory.
Grease and oils and suspended solids make up the major pollutants
within this industry. Organic pollutants, pH, and temperature
may also require treatment. The organics are present due
generally to poor housekeeping procedures.
II.17.2.2 Emulsion Crumb Rubber Production
In-process controls for the reduction of wastewater flows and
loads for emulsion crumb rubber plants include recycling of
finishing line wastewaters and steam stripping of heavy monomer
decanter wastewater. Recycling of finishing line wastewater
Date: 6/23/80 11.17-11
-------
G
(U
rt
(D
CTl
NJ
CO
00
o
TABLE 17-3.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
RUBBER PROCESSING INDUSTRY BY CATEGORY [1]
(mg/L)
Toxic pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Tire and inner tube manufacturing
Treatment influent Treatment effluent
Number Number
re- re-
ported Av Med Max ported Av Med Max
1 0.07 0.07
2 25 50
1 10 10 1 0.35 0.35
5 250 150 770
Fhthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Nitrogen compounds
Acrylonitrile
N-nitrosodiphenylamine
Phenols
2-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroethane
Chloroform
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-7*rans-dichloroethylene
Methylene chloride
1,1,2,2-Tetrachloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
>100
>100
16
20
40
<7
16
20
40
<7
(continued)
-------
D
fl)
rt
(D
to
U)
\
CO
o
I
M
U)
TABLE 17-3 (continued).
Emulsion crumb rubber manufacturing
Toxic pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Nitrogen compounds
Acrylonitrile
N-nitrosodiphenylamine
Phenols
2 -Ni trophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Balogenated aliphatics
Carbon tetrachloride
Chloroethane
Chloroform
1, 1-Dichloroethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-rrans-dichloroethylene
Methylene chloride
1,1,2, 2-Tetrachloroe thane
1,1, 1-Trichloroe thane
1,1, 2-Trichloroethane
Trichloroethylene
Number
re-
ported
3
2
1
1
3
2
1
1
3
2
1
1
3
2
1
4
1
3
1
1
3
1
Treatment
Av
270
210
200
390
2.5
380
20
290
310
1
<23,000
9.4
170
70
0.1
150
4.6
45
<2
93
30
1.5
influent
Med Max
90 720
250
200
390
2.5
590
20
290
260 530
14
<23,000
9.4
60 440
10
0.1
230 350
4.6
100 270
<2
93
20 70
1.5
Number
re-
ported
2
1
3
1
1
3
2
1
1
3
1
1
4
1
2
1
3
1
Treatment effluent
Av
33
220
2.4
400
<24
190
9
< 23, 000
4.9
25
-------
rt
(D
TABLE 17-3 (continued).
NO
U)
00
o
I
I-1
*>•
Toxic pollutants
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Number
re-
ported
3
4
3
1
2
1
2
3
1
Treatment
Av
30
350
70
390
1.6
160
8,100
260
9
Solution crumb rubber manufacturing
influent
Med
1
310
9
140
Treatment effluent
Max
90
720
200
390
2
160
15,900
530
9
Number
re-
ported
2
3
2
2
1
3
1
Av
1.2
160
9.4
1.5
195,000
190
6
Med Max
1.3
67 405
14
2
195,000
120 430
6
Nitrogen compounds
Acrylonitrile
N-nitrosodiphenylamine
Phenols
2-Nitrophenol
Pentachlorophenol
Phenol 3
2,4,6-Trichlorophenol
Aromatics
Benzene 3
Ethylbenzene 2
Toluene 3
Halogenated aliphatics
Carbon tetrachloride 1
Chloroethane 1
Chloroform 2
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-Trans-dichloroethylene
Methylene chloride 2
1,1,2,2-Tetrachloroethane 1
1,1,1-Trichloroethane
1,1,2-Trichloroethane 1
Trichloroethylene 1
Pesticides and metabolites
Isophorone
200
1,140
5
3
350
4,930
12
170
50
3
440
3,360
11
10
350
4,930
22
15
).l
18
10
110
1,410
2,260
1.1
260
11
10
10
37
10
<2
420
1,410
2,260
1.3
520
(continued)
-------
o
0>
ft
(D
TABLE 17-3 (continued)
to
u>
oo
o
M
M
-J
I
Treatment influent
Latex rubber manufacturing
Treatment effluent
Toxic pollutants
Number
re-
ported
Av
Hed
Max
Number
re-
ported
Av
Med
Max
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Nitrogen compounds
Acrylonitrile
N-nitrosodiphenylamine
Phenols
2-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroethane
Chloroform
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-Trans-dichloroethylene
Methylene chloride
1,1,2,2-Tetrachloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
100
100
1,480
2,350
1,480
2,350
31
31
1,500
31
31
1,500
<5
<5
<5
<5
(continued)
-------
o
0>
n-
CD
TABLE 17-3 (continued).
cr>
to
U)
oo
o
-o
I
Treatment influent
General molding, extruding, and fabricating
— a Treatment effluent
Toxic pollutants
Number
re-
ported
Av
Med
Max
Number
re-
ported
Av
Ned
Max
Metals and inorganics
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Nitrogen compounds
Acrylonitrile
N-nitrosodiphenylamine
Phenols
2-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroe thane
Chloroform
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-rrans-dichloroethylene
Methylene chloride
1,1,2,2-Tetrachloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
20
17
35
20
17
53
970
16
36
970
16
36
11,800
11,800
25
25
11
10
110
4
4
7,100
1
1,600
100
110
4
4
7,100
1
1,600
(continued)
-------
o
0)
r+ TABLE 17-3 (continued).
CD
Wet digestion reclaimed rubber
Ch Treatment influent Treatment effluent
x^ NumberNumber
M re- re-
^ Toxic pollutants ported Ay Med Max ported Av Hed Max
oo Metals and inorganics
o Cadmium 1 10 10
Chromium
Copper
Lead 1 50 50
Mercury
Nickel
Selenium
Zinc 2 250 350
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Nitrogen compounds
rj Acrylonitrile
N-nitrosodiphenylamine
L__t
^j Phenols
I 2-Nitrophenol
(_• Pentachlorophenol
^j Phenol
2,4,6-Trichlorophenol
Aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Carbon tetrachloride
Chloroethane
Chloroform
1,1-Dichloroe thane
1,2-Dichloroethane
1,1-Dichloroethylene
1,2-rrans-dichloroethylene
Methylene chloride
1,1,2,2-Tetrachloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Isophorone
Note: Blanks indicate data not available or not applicable (in the case of medians where less than 3 samples were
analyzed).
-------
o
OJ
rt
(D
TABLE 17-4.
INDUSTRY PROFILE OF TOXIC AND
CONVENTIONAL POLLUTANT LOADINGS [I]
NJ
OJ
oo
o
H
H
I
M
00
Tire and inner tube
Effluent
Effluent
Toxic pollutant
Number
re-
ported Av
Hed
Number
re-
Hax ported
Av
Hed
Max
Metals, kg/Mg
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Organics, kg/Mg
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Acrylonitrile
N-nitrosodiphenylamine
2-Nitrophenol
Pentachlorophenol
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1,1-Dichloroethane
1,1-Trans-dichloroethylene
1,2-Dichloroethane
Hethylene chloride
1,1,2,2-Tetrachloroethane
Te trachloroe thylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Others, kg/Mg
Dichlorobromome thane
Chloromethane
Conventionals
BODS, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
1 0.001
1 0.001
0.0034
0.0038
0.001
0.001
0.006
0.000005
0.0007
0.000005
0.0007
44
9.6
7.8
39
3.2
7.5
92
25
9.4
36
27
40
110
12
7.9
26
1.9
7.5
782
110
10.3
(continued)
-------
o
DJ
rt
n>
TABLE 17-4 (continued).
(Ti
UJ
oo
o
-J
I
Emulsion crumb rubber
Toxic pollutant
Metals, kg/Mg
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Organics , kg/Mg
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Acrylonitrile
N-nitrosodiphenylamine
2-Nitrophenol
Pentachlorophenol
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1 ,1-Dichloroe thane
1 , 1 -Trans-dichloroethylene
1 , 2-Dichloroe thane
Methylene chloride
1,1,2 , 2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Trichloroethylene
Others, kg/«g
Dichlorobromome thane
Chlorome thane
Conventional
BOD5, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
Effluent
Number
re-
ported Av Med
2
3
1
1
3
1
2
3
2
1
3
2
1
1
4
1
3
1
3
1
1
1
6
5
5
2
1
0.0003
4.3 0.00095
0.0033
0.006
0.056 0.0095
<1.1
0.006
2.4 0.0069
0.00015
<1.1
1.0 0.0058
0.007
<0.05
<0. 00039
0.015 0.003
0.00001
0.14 0.0003
0.00002
1.3 0.0002
0 . 00002
0.00012
<1.6
976 992
2,544 1,441
460 106
108.4
7.5
Effluent
Number
re-
Max ported
0.0006
13.1
0.0033
0.006
0.17
<1.1
0.007
<7.3
0.00018
<1.1
3.0
0.013
<0.05
<0. 00039
0.05
0.00001
0.40
0.00002
<3.8
0.00002
0.00012
1.6
2,378
7,696
1,875
210
1
2
4
1
1
3
2
1
1
3
1
1
1
3
1
2
1
3
1
1
1
7
7
7
6
3
Av
0.00013
5.8
0.06
1.26
0.005
2.3
0.00013
<1, 207.1
1.3
0.33
0.00013
<0.005
<0. 00039
0.0018
<0. 000002
0.044
<0. 000002
1.9
0.000013
0.000005
7.0
305
2,084
461
48
7.5
Med Max
0.00013
11.7
0.007 0.25
0.007 1.26
0.005
0.0056 <7.0
0.00018
<1,200
1.3
0.0005 0.98
0.00013
<0.005
<0. 00039
0.00013 0.005
<0. 000002
0.089
<0. 000002
0.0.0000068 <5.7
0.000013
0.000005
7.0
310 639
2,378 5,864
92 2,130
43.6 125
7.5 8.9
(continued)
-------
o
QJ
ft
(D
CO
o
I
to
o
TABLE 17-4 (continued).
Solution crumb rubber
Effluent
Toxic pollutant
Metals, kg/Mg
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Organics, kg/Mg
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Acrylonitrile
N-nitrosodiphenylamine
2-Nitrophenol
Pentachlorophenol
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1 , 1-Dichloroe thane
1 ,1-Trans-dichloroethylene
1 ,2-Dichloroe thane
Hethylene chloride
1 , 1 , 2 , 2-Tetrachloroe thane
Tetrachloroe thy lene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Tr ichloroe thy lene
Number
re-
ported
3
4
3
1
2
2
3
1
3
3
2
3
1
2
2
1
1
1
Av
0.01
8.2
0.09
0.006
2.2
0.07
1.3
0.0001
3.6
67
0.002
0.001
0.0003
0.06
0.001
0.004
<0. 00008
<0. 00008
Number
re-
Med Max ported
0.0007 0.04
0.009 <17
0.0003 <0.28
0.006
4.5
0.14
0.007 <5.4
0.0001
0.006 7.1
0.0007 135
0.004
0.0001 0.004
0.0003
0.12
0.0002
0.004
<0. 00008
<0. 00008
2
3
2
3
2
1
2
1
3
2
2
4
2
2
1
1
Effluent
Av Med
0.04
0.6 0 . 0004
0.17
0.07
1.9
0.003
0.00008
0.38 0.0005
0.003
0.003
0.004 0.001
0.3
0.004
0.007
<0. 00001
Max
0.09
<1.3
<0.34
0.136
1.9
0.006
0.00008
<0.76
<0.007
0.003
0.007
0.63
0.007
0.007
<0. 00001
Others, kg/Mg
Dichlorobromomethane
Chloromethane
Conventionals
BOD5, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
0.04
532
068
619
251
9.5
1,080
1,851
480
92
0.04
12,405
2,361
1,124
120
9.5
0.01
171
407
253
21
6.7
70
400
108
11
7.3
0.02
934
1,120
1,014
80
8.2
(continued)
-------
D
QJ
rt
(D
TABLE 17-4 (continued).
K3
U)
CO
o
I
to
Effluent
Latex rubber production
Effluent
Toxic pollutant
Number
re-
ported
Av
Med
Max
Number
re-
ported
Av
Hed
Max
Metals, kg/Mg
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Organics, kg/Mg
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dimethyl phthalate
Acrylonitrile
N-nitrosodiphenylamine
2-Nitrophenol
Pentachlorophenol
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1,1-Dichloroethane
1,1-Trans-dichloroethylene
1,2-Dichloroethane
Methylene chloride
1,1,2,2-Tet schloroethane
Te'-rachloroethylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Others, kg/Mg
Dichlorobromomethane
Chloromethane
Conventionals
BOD5, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
0.0004
0.0001
0.0001
0.006
0.0004
0.0001 1
0.0001 1
0.006 1
0.00004
0.00004
0.00002
0.00002
0.00004
0.00004
0.00002
0.00002
59
105
121
2.5
8.4
13
129
18
2.8
8.5
223
140
5,116
3.6
8.7
(continued)
-------
o
0>
ft
to
oo
o
TABLE 17-4 (continued).
i
to
to
General molding, extruding, and fabricating rubber
Effluent
Number
re-
Toxic pollutant ported Av Hed
Metals, kg/Kg
Cadmium
Chromium
Copper
Lead 1 0.0003
Mercury
Nickel
Selenium
Zinc
Organics, kg/Kg
Bis(2-ethylhexyl) phthalate 1 0.0002
Di-n-butyl phthalate
Dinethyl phthalate
acrylonitrile
N-nitrosodiphenylanine 1 0.0007
2-Nitrophenol
Pentachlorophenol 1 0.00003
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1 , 1-Dichloroe thane
1 , 1-Trans-dichloroethylene
1 ,2-Dichloroe thane
Hethylene chloride
1,1,2 , 2-Tetrachloroe thane
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Trichloroe thane
Trichloroethylene
Others, kg/Hg
Dichlorobromome thane
Chlorome thane
Conventionals
BODS, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
Number
re-
Max ported
1
1
0.0002 1
1
0.0007
0.00003
1
1
1
1
1
1
1
1
1
1
Effluent
Av Hed
0.0001
0.14
0.002
0.005
0.17
0.001
0.0003
0.2
0.4
0.0006
0.0006
1.0
0.0002
0.23
Max
0.0001
0.14
0.002
0.005
0.17
0.001
0.0003
0.2
0.4
0.0006
0.0006
1.0
0.0002
0.23
(continued)
-------
0
ED
ft
n>
to
CO
o
H
-J
I
NJ
OJ
TABLE 17-4 (continued).
Pan, dry digestion, and •echanical reclained
Effluent Effluent
Toxic pollutant
Nwfcer
re-
ported
Av
(fed
•Max
Niafcer
re-
ported
Av
Hed
Max
Metals, kg/Mg
Cadniun
Chroniun
Copper
Lead
Mercury
Nickel
Seleniun
Zinc
Organics, kg/Mg
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Dinethyl phthalate
Acrylonitrile
N-nitrosodiphenylamine
2-Nitrophenol
Pentachlorophenol
Phenol
Benzene
Ethylbenzene
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1,1-Dichloroethane
1,1-Trans-dichloroethylent
1,2-Dichloroethane
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Others, kg/Mg
DichlorobroMXM thane
Chlorone thane
Conventionals
BOD5, kg/d
COD, kg/d
TSS, kg/d
Oil and grease, kg/d
pH, pH units
2
1
2
2
1
390
570
3.2
13.9
7.2
775
5.2
24.4
2
2
3
3
2
49
520
13
2.6
7.3
96
690
17 22
0.07 7.7
7.5
Note: Blanks indicate data not available or not applicable (in the case of medians where less than 3 sanples were analyzed).
-------
TABLE 17-5.
Plant area
SUMMARY OF POTENTIAL PROCESS-ASSOCIATED WASTEWATER
SOURCES FROM THE TIRE AND INNER TUBE INDUSTRY [1]
Source
Nature and origin of wastewater contaminants
Oil storage
Compounding
Bead, tread, tube
formation
Cord and belt
formation
Green tire painting
Holding and curing
Tire finishing
Runoff
Washdown, spills, leaks,
discharges from wet air
pollution equipment
Washdown, spills, leaks
Washdown, spills, leaks
Washdown, spills, air
pollution equipment
Washdown, leaks
Washdown, spills, air
pollution equipment
Oil.
Solids from soapstpne dip tanks. Oil from seals in
roller mills. Oil from solids from Banbury seals.
Solids from air pollution equipment discharge.
Oil and solvent-based cements from the cementing
operation. Oil from seals in roller mills.
Organics and solids from dipping operation. Oil
from seals, in roller mills, calenders, etc.
Organics and solids from spray painting operation.
Soluble organics and solids from air pollution
equipment discharge.
Oil from hydraulic system. Oil from presses.
Solids and soluble organics from painting operation.
Solids from air pollution equipment discharge.
occurs at nearly all emulsion crumb plants with the percent
recycle depending primarily upon the desired final properties
of the crumb. Approximately 75% recycle is an achievable rate,
with recycle for white masterbatch crumb below this level and
that for black masterbatch crumb exceeding it.
Organic toxic pollutants found at emulsion crumb rubber plants
come from the raw materials, impurities in the raw materials,
and additives to noncontact cooling water. BOD, COD and TSS
levels may also reach high loadings.
Table 17-6 lists potential wastewater sources and general waste-
water contaminants for the emulsion crumb rubber industry.
TABLE 17-6.
Processing unit
SUMMARY OF WASTEWATER SOURCES FROM EMULSION
CRUMB RUBBER PRODUCTION FACILITIES [1]
Source Nature of wastewater contaminants
Caustic soda scrubber
Monomer recovery
Coagulation
Crumb dewatering
Monomer strippers
Tanks and reactors
All plant areas
Spent caustic solution
Decant water layer
Coagulation liquor overflow
Crumb rinse water overflow
Stripper cleanout rinse
water
Cleanout rinse water
Area washdowns
High pH, alkalinity, and color. Extremely low
average flow rate.
Dissolved and separable organics. Source of high
BOB and COD discharges.
Acidity, dissolved organics, suspended and high
dissolved solids, and color. High wastewater
flow rates relative to other sources.
Dissolved organics, and suspended and dissolved
solids. Source of highest wastewater volume
from emulsion crumb rubber production.
Dissolved organics, and suspended and dissolved
solids. High quantities of uncoagulated latex.
Dissolved organics, and suspended and dissolved
solids. High quantities of uncoagulated latex.
Dissolved and separable organics, and suspended
and dissolved solids.
Date: 6/23/80
II.17-24
-------
II.17.2.3 Solution Crumb Rubber Production
Solution crumb rubber production plants have lower raw wastewater
loads than emulsion crumb plants due to the thorough steam
stripping of product cement to remove solvent and permit effec-
tive coagulation. Recycling in this industry is comparable to
that in the emulsion crumb industry with about 75% of the waste-
water being recirculated.
Toxic pollutants found in the wastewater streams are normally
related to solvents and solvent impurities, product additives,
and cooling water treatment chemicals. Table 17-7 presents a
listing of the potential wastewater sources and the associated
contaminants for this industry.
TABLE 17-7.
SUMMARY OF WASTEWATER SOURCES FROM
SOLUTION CRUMB RUBBER PRODUCTION [1]
Processing unit
Source
Nature of wastewater contaminants
Caustic soda scrubber
Monomer and solvent drying
columns
Solvent purification
Monomer recovery
Crumb dewatering
All plant areas
Spent caustic solution
Water removed from mono-
mers and solvent
Fractionator bottoms
Decant water layer
Crumb rinse water overflow
Area washdowns
High pH, alkalinity, and color.
Extremely low average flow rate.
Dissolved and separable organics.
Very low flow.
Dissolved and separable organics.
Dissolved and separable organics.
Dissolved organics, and suspended
and dissolved solids. Source of
highest volume wastewater flow.
Dissolved and separable organics, and
suspended and dissolved solids.
II.17.2.4 Latex Rubber Production
No in-process contact water is currently used by the latex rubber
industry. No raw material recycling is practiced because of
poor control of monomer feeds and the buildup of impurities in
the water.
Organic toxic pollutants and chromium are present in the raw
wastewater and normally consist of raw materials, impurities, and
metals used as cooling water corrosion inhibitors.
Table 17-8 presents potential wastewater sources and general con-
taminants for this industry.
II.17.2.5 General Molding, Extruding, and Fabricating Rubber
Plants
Toxic pollutants resulting from production processes within this
industry are generally the result of leaks, spills, and poor
Date: 6/23/80
11.17-25
-------
housekeeping procedures. Pollutants include organics associated
with the raw materials and lead from the rubber curing process.
TABLE 17-8.
SUMMARY OF WASTEWATER SOURCES FROM
LATEX RUBBER PRODUCTION [1]
Processing unit
Source
Nature of wastewater contaminants
Caustic soda scrubber
Excess monomer stripping
Latex evaporators
Tanks, reactors, and
strippers
Spent caustic solution
Decant water layer
Water removed during
latex concentration
Cleanout rinse water
Tank cars and tank trucks Cleanout rinse water
All plant areas
Area washdowns
High pH, alkalinity, and color. Extremely
low average flow rate.
Dissolved and separable organics.
Dissolved organics, suspended and dissolved
solids. Relatively high wastewater flow
rates.
Dissolved organics, suspended and dissolved
solids. High quantities of uncoagulated
latex.
Dissolved organics, suspended and dissolved
solids. High quantities of uncoagulated
latex.
Dissolved and separable organics, and
suspended and dissolved solids.
II.17.2.6 Rubber Reclamation
Wastewater effuents from this industry contain high levels of
toxic organic and inorganic pollutants. These pollutants
generally result from impurities in the tires and tubes used in
the reclamation process. The wastewater from the pan process
is of low volume (0.46 m3/Mg [56 gal/1,000 lb]), but is highly
contaminated, requiring treatment before discharge. The
mechanical reclaiming process uses water only to quench the
reclaimed rubber, but it uses a much higher quantity
(1.1 m3/Mg). Steam generated from the quenching process is
captured in a scrubber and sent to the treatment system. Wet
digestion uses 5.1 m3 of water per Mg (604 gal/1,000 lb) of
product in processing, of which 3.4 m3/Mg (407 gal/1,000 lb) of
product is used in air pollution control.
II.17.2.7.
Latex-Dipped, Latex-Extruded, and Latex-Molded
Goods
Wastewater sources in this industry are the leaching process,
makeup water, cooling water, and stripping water. Toxic
pollutants are present only in insignificant levels in the
wastewater discharges.
II.17.2.8 Latex Foam
No information is available on the wastewater characteristics of
this industry.
Date: 6/23/80
11.17-26
-------
II.17.3 PLANT SPECIFIC DESCRIPTION
Only two subcategories of the rubber industry have not been
recommended as Paragraph 8 exclusions of the NRDC consent decree:
Wet Digestion Reclaimed Rubber, and Pan, Mechanical, and Dry
Digestion Reclaimed Rubber. Of these two, plant specific data
are available only for the latter. Of the nine remaining sub-
categories, plant specific information is available only for
Emulsion Crumb Rubber and Solution Crumb Rubber, and it is
presented below. Two plants in each subcategory are described.
They were chosen as representative of their industries based on
available data.
II.17.3.1 Emulsion Crumb Rubber Production
Plant 000012 produces 3.9 x 104 Mg/yr (8.7 x 107 Ib/yr) of
emulsion crumb rubber, primarily neoprene. The contact waste-
water flow rate is approximately 8.45 m3/d (5.90 x 10s gpd) and
includes all air pollution control equipment, sanitary waste,
maintenance and equipment cleanup, and direct contact waste-
water. The treatment process consists of activated sludge,
secondary clarification, sludge thickening, and aerobic sludge
digestion. Noncontact wastewater, with a flow rate of approxi-
mately 1.31 x 105 m3/d (3.46 x 107 gpd), is used on a
once-through basis and is returned directly to the river source.
Contact wastewater is also returned to the surface stream after
treatment.
Plant 000033 produces three types of emulsion crumb rubber in
varying quantities. Styrene butadiene rubber (SBR) is the bulk
of production, at nearly 3.7 x 10s Mg/yr (8.2 x 10s Ib/yr), with
nitrile butadiene rubber (NBR) and polybutadiene rubber (PER)
making up the remainder of production (4.5 x 104 Mg/yr
[1.0 x 10s Ib/yr] and 4.5 x 103 Mg/yr [1 x 107 Ib/yr], respec-
tively). Wastewater consists of direct contact process water,
NEC, noncontact blowdown, and noncontact ancillary water. The
total flow of contact water is approximately 1.27 x 104 m3/d
(3.365 x 106 gpd), and of noncontact water, it is 340.4 m3/d
(90 x 104 gpd). Treatment of the wastewater consists of coagu-
lation, sedimentation, and biological treatment with extended
aeration. Treated wastewater is discharged to a surface stream.
Tables 17-9 and 17-10 present plant specific toxic pollutant data
for the selected plants. Table 17-11 gives plant specific con-
ventional pollutant data, including BPT regulations set for each
specific plant. Both plants are within BPT regulations for the
sampling data. Plant 000012 is not within the standards for the
308 data available.
Date: 6/23/80 11.17-27
-------
ft
fD
NJ
00
o
I
to
oo
TABLE 17-9. PLANT SPECIFIC VERIFICATION DATA FOR EMULSION
CRUMB RUBBER PRODUCTION PLANT 000012a [1]
Flow rate, m3/d: contact, 8.45; noncontact, 1.31 x 10s
Location in process line
Pollutant
Cadmium
Mercury
Nickel
Bis(2-ethylexyl) phthalate
Dimethyl phthalate
N-nitrosodiphenylamine
Phenol
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1 , 1-Dichloroethylene
Hethylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
Stripper decant
Av
<1
1.5
60
290
<14
1.5
16
<30
370
41
108
51
4.8
<0.1
1.6
Hed
<1
0.7
90
250
<14
<1.0
18
<30
310
46
120
71
3.0
<0.1
<0.1
Max
<1
3.4
90
550
<16
2.5
26
<30
780
49
130
81
8.7
<0.1
4.6
Spray
Av
<1
2.0
690
490
<14
1.0
29
<30
<0.5
0.1
14
<1.7
1.0
<0.1
0.3
wash water
Hed
<1
1.1
720
260
<14
<1.0
32
<30
<0.5
0.1
11
<1.7
0.1
<0.1
0.2
Max
<1
3.8
740
1,000
<16
1.0
36
<30
<0.5
0.2
22
<1.7
2.8
<0.1
0.6
Treatment influent
Av
<2
2.5
610
260
<14
5.2
40
<30
250
4.7
27
<1.7
<0.1
1.4
1.1
Hed
<1
3.4
560
260
<14
4.0
40
<30
290
4.0
25
<1.7
<0.1
0.9
0.9
Hax
4
3.6
720
270
<16
10.4
60
<30
370
7.9
33
<1.7
<0.1
3.2
2.2
Treatment effluent
Av
<1
1.6
400
230
<14
2.0
19
<30
<0.5
0.2
4.1
<1.7
1.0
<0.1
0.3
Hed
<1
0.7
400
110
<14
1.8
19
<30
<0.5
<0.1
2.2
<1.7
<0.1
<0.1
0.2
Hax
<1
3.4
430
520
<16
3.1
20
<30
<0.5
0.3
8.5
<1.7
2.8
<0.1
0.6
Raw intake water
<1.0
1.5
<10
262
<16
<1.0
<2
<30
<0.5
0.3
8.5
<1.7
<0.1
<0.1
0.2
Based on three 24-hour sample composite analyses.
Based on second 24-hour sample composite analyses.
-------
D
D>
rt
(D
M
CO
oo
o
I
to
VD
TABLE 17-10.
PLANT SPECIFIC VERIFICATION DATA FOR EMULSION
CRUMB RUBBER PRODUCTION PLANT 000033 [1]
Flow rate, m3/d:
SBR - contact, 1.02 s 10*; noncontact, 1.9 x
NBR - contact, 1.25 x 103; noncontact, 75.7
PBR - contact, 1.25 x 103, noncontact, 75.7
Total - contact, 1.27 x 104; noncontact, 340.4
102
Location in process line
SBR stripper
Pollutant
Cadmium
Chromium
Copper
Mercury
Selenium
Bis(2-ethylhexyl) phthalate
Acrylonitrile
2-Nitrophenol
Phenol
Ethylbenzene
Toluene
Chloroform
Oichlorobromome thane
Methylene chloride
Av
fl
6
70
0.8
<4
350
26,000
<4
41
38
<0.1
1.4
0.3
110
Med
-------
O
PJ
rt
(D
(Ti
to
U)
00
o
TABLE 17-11.
I
U)
o
PLANT SPECIFIC CONVENTIONAL POLLUTANT VERIFICATION DATA
FOR SELECTED EMULSION CRUMB RUBBER PRODUCTION PLANTS [1]
Parameter
BOD5
COD
TSS
Oil and grease
PH
Cyanide
Ammonia
BODS
COD
TSS
Oil and grease
pH
Cyanide
Ammonia
Waste load,3
Influent
308 data Sampling data 308
1,400 (3,090) 1,200 (2,639) 45
2,300 (5,000) 2,100 (4,574) 900
400 (870) 10 (17.6) 250
<8 (<17.6)
7
Waste load,3
380 (840) 2,700 (5,947) 99
5,700 (12,600) 8,730 (19,240) 2,620
1,760 (3,886) 2,130 (4,688) 330
240 (525) 35
5.5 7.0
70 (155) 0.4 (0.9) 0.59
35 (76)
plant 000012
Effluent
data
(100)
(2,000)
(560)
8.2
Sampling data
4.8 (10.6)
130 (281)
35 (77.4)
8 (17.6)
BPT regulation
44 (96.7)
880 (1,933)
71 (157)
18 (38.7)
6 to 9
plant 000033
(219)
(5,777)
(731)
(78)
(1.3)
143 (315)
2,700 (5,947)
250 (542)
140 (314)
0.16 (0.35)
463 (1,019)
9,250 (20,376)
750 (1,656)
185 (408)
6 to 9
Values in kg/d (Ib/d) except for pH values; they are given in pH units.
Note: Blanks indicate data not available.
-------
II.17.3.2 Solution Crumb Rubber Production
Plant 000005 produces approximately 3.2 x 104 Mg/yr (7.0 x 107
Ib/yr) of isobutene-isopropene rubber. Wastewater generally con-
sists of direct processes and MEC water. Contact wastewater flow
rate is approximately 1,040 m3/d (2.75 x 103 gpd), and noncontact
water flows at about 327 m3/d (8.64 x 104 gpd). Treatment con-
sists of coagulation, flocculation and dissolved air flotation,
and the treated effluent becomes part of the noncontact cooling
stream of the on-site refinery.
Plant 000027 produces polyisoprene crumb rubber (4.5 x 104 Mg/yr
[1 x 108 Ib/yr]), polybutadiene crumb rubber (4.5 x 104 mg/yr
[1.0 x 10* Ib/yr]), and ethylene-propylene-diene-terpolymer
rubber (EPDM; 4.5 x 104 Mg/yr [1.0 x 10* Ib/yr]). Wastewater
consists of contact process water, MEC, cooling tower blowdown,
boiler blowdown, and air pollution control. Wastewater is
produced at about 12,100 m3/day (3.2 x 106 gpd). Treatment
consists of API separators, sedimentation, stabilization, and
lagooning, followed by discharge to a surface stream.
Tables 12-12 and 17-13 show plant specific toxic pollutant data
for the above plants. Conventional pollutant data and BPT
regulations are presented in Table 17-14.
II.17.3.3 Dry Digestion Reclaimed Rubber
An analytical data summary for plant 000134 is given in Table
17-15. Production, wastewater flow, and treatment data are
currently not available for a plant within this subcategory.
II.17.4 POLLUTANT REMOVABILITY
In this industry, numerous organic compounds, BOD, and COD are
typically found in the plant wastewater effluent. Industry-wide
flow and production data show that these pollutants can be
reduced by biological treatment. In emulsion crumb and latex
plants, uncoagulated latex contributes to high suspended solids.
Suspended solids are produced by rubber crumb fines and include
both organic and inorganic materials. Removal of such solids is
possible using a combination of coagulation/flocculation and
dissolved air flotation.
Solvents, extender oils, and insoluble monomers are used through-
out the rubber industry. In addition, miscellaneous oils are
used to lubricate machinery. Laboratory analysis indicates the
presence of oil and grease in the raw wastewater of these
plants. Oil and grease entering the wastewater streams is re-
moved by chemical coagulation, dissolved air flotation and, to
some extent, biological oxidation.
Date: 6/23/80 11.17-31
-------
o? TABLE 17-12. PLANT SPECIFIC VERIFICATION DATA FOR SOLUTION
£ CRUMB PRODUCTION PLANT 000005 [1]
(Mg/L)
CT, Flow rate, n3/d: contact, 1,040; noncontact, 327
\
NJ
U)
\
oo
o
H
I
U>
ro
Pollutant
Cadmium
Chromium
Copper
Zinc
Bis(2-ethylhexyl) phthalate
Phenol
Benzene
Ethylbenzene
Toluene
Carbon tetrachloride
Chloroform
Methyl chloride
Methylene chloride
1,1, 2-Trichloroe thane
Tr ichlo roe thy lene
Screen -
Av
-------
o
0)
rt
(D
(Ti
to
U)
CO
o
TABLE 17-13.
PLANT SPECIFIC VERIFICATION DATA FOR SOLUTION
CRUMB RUBBER PRODUCTION PLANT 000027 [1]
Total flow rate: 12,100 m3/d
Pollutant
Cadmium
Chromium
Copper
Mercury
Bis(2-ethylhexyl) phthalate
Phenol
Benzene
Ethylbenzene
Toluene
Chloroform
1,1,2, 2-Tetrachloroethene
SN/CB process
Av
U)
TABLE 17-14.
PLANT SPECIFIC CONVENTIONAL PLANT VERIFICATION DATA
FOR SELECTED SOLUTION CRUMB RUBBER PRODUCTION PLANTS [1]
Waste load9
Plant 000005
Parameter
BOD5
COD
TSS
Oil and grease
PH
Cyanide
Phenol
Influent
93.7
250
18.8
104.1
<0.02
0.006
<206.4)
(550.4)
(41.3)
(229.4)
(<0.05)
(0.0128)
Treated
effluent
66.6
135.4
11.4
13.5
<0.02
0.006
(146.8)
(298.2)
(25.2)
(29.8)
(<0.05)
(0.013)
BPT
regulation
51.4 (113.3)
504.3 (1110.7)
83.6 (184.2)
20.6 (45.3)
6 to 9
Influent
1,226 (2,701)
2.680 (5.903)
1.276 (2.811)
45 (100)
1.03 (2.26)
Plant 000027
Treated.
effluent
<90
450
11
<90
<0.2
0.16
(<200)
(1,000)
(25)
(<200)
(
-------
TABLE 17-15.
PLANT SPECIFIC VERIFICATION DATA FOR PAN, DRY
RUBBER DIGESTION, AND MECHANICAL RECLAIMING
[1]
(M9/L)
PLANT 000134
Treatment
influent
Pollutant
Cadmium
Chromium
Copper
Lead
Mercury
Zinc
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
2 ,4-Dimethylphenol
Phenol
Benzene ,
Chlorobenzene
Ethylbenzene
Toluene
Acenaphthylene
Anthracene ,
Phenanthrene
Fluorene
Naphthalene
Pyrene
Chloroform
Methylene chloride
Av Med
1
6
31
70
100
16,000 19,
58,000 61,
26,000 37,
60
8,600 2,
2,700 1,
33
1,400
2,000
102,000 61,
7,000 5,
1.9
-------
Wastewater sampling indicates that toxic pollutants found in the
raw wastewater can be removed. Biological oxidation (activated
sludge) adequately treats all of the organic toxic pollutants
identified in rubber industry wastewater streams. Significant
removal of metals was also observed across biological treatment.
The metals are probably absorbed by the sludge mass and removed
with the settled sludge. Treatment technologies currently in
use are described in the following subcategory descriptions.
II.17.4.1 Emulsion Crumb Rubber Plants
There are a total of 17 plants in the United States producing
emulsion-polymerized crumb rubber. Five of these plants dis-
charge to POTW's; 10 discharge to surface streams; 1 plant
discharges to an evaporation pond; and 1 plant employs land
application with hauling of settled solids. Of the five plants
discharging POTW's, four pretreat using coagulation and primary
treatment, and one employs equalization with pH adjustment. All
10 of the plants discharging to surface streams employ biological
waste treatment ranging from conventional activated sludge to
nonaerated wastewater stabilization lagoons.
Organic pollutants are generally found to be reduced to insignif-
icant levels (<10 M9/L) by biological treatment. Most metals are
also found' to be reduced across biological treatment; they are
generally very low levels in the treated effluent. However,
significant metal concentrations may be found in some treated
effluent.
At emulsion crumb rubber facilities, a well-operated biological
treatment facility permits compliance with BPT limitations and
reduces ogranic toxic pollutants to acceptable levels. Toxic
metals that may not be reduced include chromium, cadmium, copper,
selenium, and mercury. The need for advanced technologies such
as ion exchange and chemical precipitation will depend on
allowable limits adopted by US EPA. Tables 17-16 and 17-17 show
pollutant removal efficiencies at two emulsion crumb plants.
II.17.4.2 Solution Crumb Rubber Plants
There are 13 solution crumb rubber plants in the United States.
Twelve of these plants discharge treated wastewater to surface
streams; the other plant discharges its treated wastewater into
a neighboring oil refinery's noncontact cooling water system.
Ten of the plants discharging to surface streams employ some
form of biological treatment for waste load reduction. Two of
the plants discharging to surface streams use in-process
controls, oil removal, and primary treatment prior to discharge.
In-process control employed at one plant consists of steam
stripping of wastewaters, while in-process control at the second
Date: 6/23/80 11.17-35
-------
plant was not disclosed. The plant discharging to the oil
refinery noncontact cooling water system used coagulation, floc-
culation, and dissolved air flotation prior to discharge.
The results of the verification program showed that all organic
toxic pollutants were reduced across biological treatment.
Chloromethane, used as a solvent at plant 000005, was present at
significant levels in treated effluent.
TABLE 17-16.
TOXIC POLLUTANT REMOVAL EFFICIENCY AT
EMULSION CRUMB RUBBER PLANT 000012 [1]
Treatment technology: Activated sludge
Discharge point: Surface stream
Pollutant
Cadmium.
Mercury
Nickel
Bis(2-ethylhexyl)
phthalate
Dimethyl phthalate
N-nitrosodiphenylamine
Phenol6
Nitrobenzene
Toluene
Carbon tetrachloride
Chloroform
1 , 1-Dichloroethylene
Methylene chloride
Tetrachloroethene
1,1,1, -Tr ichloroethane
Concentration
3
Influent Effluent
1
2.5
610
260
<14
5.2
41
<30
250
4.7
27
<1.7
<0 . 1
1.4
1.0
1.6
400
220
<14
1.6
19
<30
<0 . 1
0.1
4.1
<1.7
0.9
<0 . 1
3.3
Percent
removal
100
36
34
i5
69
-
100
98
85
u.
~f
100
-f
aValues presented are averages of the values observed
for the three 24-hr composite samples.
Intake measured at 1.5 pg/L, making plant's
contribution minimal.
GAnalytical methodology for phthalates is question-
able. Therefore, significance of values reported
is unknown.
Negligible removal.
eScreening data indicate reduction to below signifi-
cant level across treatment.
Negative removal.
Date: 6/23/80
11.17-36
-------
TABLE 17-17. TOXIC POLLUTANT REMOVAL EFFICIENCY AT
EMULSION CRUMB RUBBER PLANT 000033 [1]
Treatment technology: Primary flocculation/separation,
aerated lagoons
Discharge point: Surface stream
Pollutant
Cadmium
Chromium
Copper
Mercury
Selenium
Bis(2-ethylhexyl)
phthalatee
Acrylonitrile
2-Nitrophenol
Phenol9
Ethylbenzene
Toluene
Chloroform
Dichlorobromomethane
Methylene chloride
Concentration
Influent
40
250
1,400
3.2
<20
a
, u g/L
Effluent
40
220
410
4.9
20
Percent
removal
c
12
71
_d
-c
65-140 (100) 59-130 (94) ^6
32,000
9
60
<0.1
<0.1
8.2
0.3
66
23,000
3
19
<0.1
<0.1
1.8
0.1
110
>28
67
68
_c
_c
78
67
_d
Values presented are averages of the values observed for
the three 24-hr composite samples.
Found at potentially significant levels in treatment
effluent although generally higher than during screening.
°Negligible removal.
Treatment effluent concentration exceeds that of
treatment influent.
Analytical methodology for phthalates is questionable.
Therefore, significance of values reported is unknown.
Screening data where purge and trap procedures were used
indicated a reduction of 400 pg/L to <50 pg/L across
treatment.
gScreening data indicate reduction to below significant
level across treatment.
Suspected contaminant from glassware cleaning procedures
or analytical method.
Date: 6/23/80 11.17-37
-------
Tables 17-18 and 17-19 show pollutant removal efficiencies at two
selected solution crumb rubber plants.
II.17.4.3 Latex Rubber Plants
There are 17 latex rubber production facilities in the United
States. Of these, nine plants discharge to POTW's; seven dis-
charge to surface streams; and one employs land application with
contractor disposal of solids. All seven plants discharging to
surface streams employ biological treatment before discharge.
Pretreatment for the POTW dischargers consists of coagulation,
flocculation, and primary treatment for seven of the nine
dischargers, equalization for one discharger, and biological
treatment for the other plant.
In latex rubber production, BPT regulations require that toxic
pollutants be removed across an activated sludge treatment which
will permit compliance with the regulations when applied to raw
wastewater. The application of steam stripping to heavy monomer
decanter water, although not practiced, could significantly
reduce waste loads to plants employing cold polymerization; how-
ever, steam stripping is not a viable option in plants employing
hot polymerization with high monomer conversion efficiency.
II.17.4.4 Tire and Inner Tube Manufacturing
There are a total of 73 tire and inner tube manufacturing
facilities in the United States, of which 39 were placed in
operation prior to 1959. Twenty-three of the pre-1959 plants
do not treat their wastewaters, and six of these plants discharge
to POTW's. A total of 17 plants placed in operation since 1959
provide no treatment to their wastewaters, and 10 of these plants
discharge into POTW's.
The toxic pollutants present in raw wastewaters from tire and
inner tube manufacturing operations are volatile organic pollu-
tants that are used as degreasing agents in tire production.
These toxic pollutants (methylene chloride, toluene, trichloro-
ethylene) were found to be reduced to insignificant levels across
sedimentation ponds.
The application of oil separation, filtration, or sedimentation
followed by oil separation could permit compliance of tire
plant treated effluents with BPT regulations.
II.17.4.5 Rubber Reclamation Plants
There are nine rubber reclaiming plants in the United States.
two of these use wet digestion, and all nine use pan, mechanical,
and dry digestion. Eight of the plants discharge to POTW's.
The other plant employs cartridge filtration and activated carbon
Date: 6/23/80 11.17-38
-------
TABLE 17-18. TOXIC POLLUTANT REMOVAL EFFICIENCY AT
SOLUTION CRUMB RUBBER PLANT 000005 [1]
Treatment technology: Primary flocculation/clarifi-
cation (DAF)
Discharge point: Treated effluent is discharged to a
nearby oil refinery's cooling water system
Pollutant
Cadmium
Copper
Chromium
Zinc
Bis(2-ethylhexyl)
phthalate0
Phenol
Benzene
Ethylbenzene
Toluene
Carbon tetrachloride
Chloroform
Methyl chloride
Methylene chloride
1,1, 2-Trichloroethane
Trichloroethylene
Concentration,
3
Influent Effluent
<1
9
75
14,000 13,
180
7
<22
<46
<26
35
2.2
4,900 2,
<1 . 0
<0 . 1
<0.1
<1
14
410
000
24
5
noe
<39
<26
14
1.3
200f
<1 . 0
<0 . 1
<0 . 1
Percent
removal
b
_c
_c
7
87
29
_b
_b
-b
60
41
55
b
b
b
Values presented are averages of the values
observed for the three 24-hr composite samples.
Negligible removal.
°Treatment effluent concentration exceeds that of
treatment influent.
Analytical methodology for phthalates is question-
able. Therefore, significance of values reported
is unknown.
eAverage of 320 M9/L, <11 M9/L and <11 M9/L.
Found at significant levels in treatment effluent.
Date: 6/23/80 11.17-39
-------
TABLE 17-19. TOXIC POLLUTANT REMOVAL EFFICIENCY AT
SOLUTION CRUMB RUBBER PLANT 000027 [1]
Treatment technology: Sedimentation, waste stabilization
lagoons
Discharge point: Surface stream
Concentration,3 ug/L
Pollutant
Cadmium
Chromium
Copper
Mercuryc
Bis(2-ethylhexyl)
phthalate
Phenol f
Benzene
Ethylbenzene
Toluene
Chloroform
1,1,2, 2-Tetrachloroethane
Influent
<1
440
7
1.1
120
180
3,200
<0.1
<0.1
3.0
<0.1
Effluent
1
20
5
2.0
110
11
<0.1
<0.1
<0.1
0.9
<0.1
Percent
removal
_b
95
29
-d
8
94
100
_b
-b
70
_b
aValues presented are averages of the values observed for
the three 24-hr composite samples.
Negligible removal.
clntake measured at 4 pg/L, making plant's contribu-
tion zero.
Effluent concentration greater than influent
concentration.
Analytical methodology for phthalates is questionable.
Therefore, significance of values reported is unknown.
Screening data indicate reduction to below significant
level across treatment.
for oil removal, followed by activated sludge. Table 17-20 shows
the pollutant removal efficiency at a dry digestion reclaiming
plant.
Date: 6/23/80 11.17-40
-------
TABLE 17-20. TOXIC POLLUTANT REMOVAL EFFICIENCY AT DRY
DIGESTION RECLAIMING PLANT 000134 [1]
Treatment technology: Cartridge filtration, activated carbon (oil removal),
activated sludge, sedimentation
Discharge point: Noncontact cooling water system, blowdown of this system to
surface stream
Concentration, (jg/L
Pollutant
Cadmium
Chromium
Copper
Lead
Mercury
Zinc ,
Bis(2-ethylhexyl) nhthalate
2 , 4-Dimethylphenol
Phenol9
Benzene
Ethylbenzene
Toluene
Acenaphthylene
Flourene
Naphthalene '
Phenanthrene
Pyrene
Chloroform
Treatment
influent3
1
6
28
7Q
C
100
16,000
58,000
26,000
60
8,600
2,700
<33
2,000
100,000
1,300
6,800
1.9
Treatment,
effluent3'0
3
21
12
670
2.3
2,500
4,200
25,000
4,900
<0.1
<0.1
-------
No treatment method descriptions are currently available for
this industry. Wastewater treatment technology consistent with
equalization and sedimentation may permit compliance with BPT
regulations.
II.17.5 REFERENCES
1. Review of Best Available Technology for the Rubber Processing
Point Source Category (draft contractor's report). Contract
68-01-4673, U.S. Environmental Protection Agency, Washington,
D.C., July 1978.
2. NRDC Consent Decree Industry Summary - Rubber Processing.
3. Environmental Protection Agency Effluent Guidelines and
Standards for Rubber Processing. 40 CFR 428; 39 FR 6660,
February 21, 1974 (amended by 39 FR 26423, July 19, 1974;
40 FR 2334, January 10, 1975; 40 FR 18172, April 25, 1975
[effective May 27, 1975]; and 43 FR 6230, February 14, 1978).
Date: 6/23/80 11.17-42
-------
11.18 SOAP AND DETERGENT MANUFACTURING
II.18.1 INDUSTRY DESCRIPTION
II.18.1.1 General Description [1, 2]
The uses of soaps, detergents and their derivatives in many of
the nation's industries and households make the soap and deter-
gent manufacturing industry one of the most lucrative commercial
successes in America. The industry consists of approximately 640
plants which produce a total of 28,000 Mg (62 million pounds) of
soap and related products per day [2], A vast portion of these
products or their components will invariably be deposited in the
nation's waterways and wastewater treatment facilities from
various production plant operations or after actual household
use.
Four large companies dominate the industry by owning nearly 5% of
all the plants, selling 50% of all soap products, and accounting
for 54% of total industry employment. Of these institutions,
three are multinational corporations having individual annual
sales over one billion dollars from the sale of household prod-
ucts and health and beauty aids [3]. These large corporations
are able to own and economically operate innovative production
processes and large, efficient wastewater treatment facilities
and other pollution control equipment.
The medium to small plant operations that make up the remainder
of the industry (approximately 95%), are limited to large popula-
tion centers and state of the art technology. These plants must,
in most cases, use publicly owned treatment facilities and operate
with less capital for advanced process technologies and pollution
abatement equipment.
The industry is covered under Standard Industrial Classification
(SIC) Code 2841 which includes provisions for the manufacture of
soap, synthetic organic detergents, and organic alkaline deter-
gents, or any combination of these. SIC code 2841 also includes
the manufacture of crude and refined glycerine from vegetable and
animal fats and oils. The EPA Effluent Guidelines Division has
devised a subcatergorization of this industry based upon the
specific types of manufacturing processes undertaken at a given
establishment. Table 18-1 gives information regarding the total
number of these subcategories, the number of subcategories studied
for this report, and the projected discharge status of 637 soap
and detergent manufacturing plants in the United States.
Date: 6/23/80 11.18-1
-------
TABLE 18-1. INDUSTRY SUMMARY [1, 2]
Industry: Soap and detergent manufacture
Total Number of Subcategories:
Number of Subcategories Sutdied: 13
Number of Dischargers in Industry:
Direct: 10
Indirect: 535
Zero: Unknown
Projected industry statistics by SIC 2841 unit operation Subcate-
gories are included in Table 18-2, which lists all Subcategories.
This profile audit shows that there are an estimated 1,523 proc-
ess installations which produce 28,000 Mg (62 million pounds) of
soap, detergent, and glycerine per day. Liquid detergent and dry
blended detergent manufacturing account for 47% of this production.
As shown in Table 18-2, over 75% (124,000 m3/d) of the normalized
approximate total wastewater flow (143,000 m3/d) is estimated to
come from the 40 glycerine recovery (concentration and distilla-
tion) installations.
II.18.1.2 Subcategory Descriptions [1]
The method for subcategorizing the soap and detergent manufactur-
ing industry mentioned above was established to identify potential
wastewater sources and controls, provide a permit granting author-
ity with a way to analyze a specific plant regardless of its
complexity, and permit monitoring for compliance without undue
complication or expense [1]. The categorization consists of 2
major categories and 19 Subcategories. The major categories
follow the natural division of soap manufacturing (production of
alkaline metal salts and fatty acids derived from natural fats
and oils) and detergent manufacturing (production of sulfated and
sulfonated cleaning agents from manufactured raw materials,
primarily petroleum derivatives). The Subcategories are based on
discrete manufacturing units employed by the industry for conver-
sion of raw materials to intermediate products and conversion of
intermediate products to finished/marketed products. A manufactur-
ing unit may contain a single process (e.g., continuous neutraliza-
tion for production of neat soap by fatty acid neutralization) or
£ number of processes (e.g., crutching, drying, milling, plodding,
stamping, and packaging for production of bar soaps from neat
soap).
In general, establishments in SIC 2841 employ between one and
nine subcategory technologies. Table 18-3 presents the predomi-
nant subcategory combinations employed in such establishments.
Date: 6/23/80 II.18-2
-------
a
OJ
rt
0)
\ TABLE 18-2. PROCESS INDUSTRY STATISTICS BY SIC 2841
o UNIT OPERATION SUBCATEGORIES [2]
H
H
CO
I
OJ
Subcat-
egory
1
2
3
4
5
6
7
8
9a
10a
Ua
123
13a
14a
15
16
17
18
19
Projected
number of
Subcategory title installations
Soap Manufacture by Batch Kettle
Fatty Acid Manufacture by Fat Splitting
Soap Manufacture by Fatty Acid Neutralization
Glycerine Concentration „, . _.
_, . „. . .,, . . Glycerine Recovery
Glycerine Distillation * 2
Soap Flakes and Powders
Bar Soaps
Liquid Soaps
Oleum Sulfonation and Sulfation
Air-S03Sulfation and Sulfonation
SOs Solvent and Vacuum Sulfonation
Sulfamic Acid Sulfation
Chlorosulfonic Acid Sulfation
Neutralization of Sulfuric Acid Esters and Sulfonic Acids
Spray Dried Detergent Manufacture
Liquid Detergent Manufacture
Detergent Manufacture by Dry Blending
Drum Dried Detergents
Detergent Bars and Cakes
Totals
151
22
177
40
141
69
223
54
341
289
5
11
1,523
Approx. total
production,
103 kg/day
590
1,940
2,220
415
200
1,100
1,600
6,540
9,680
3,390
36
293
28,000
Normalized
approx. total
wastewater
flow, m3/day
85.9
4,200
86.7
124,000
1.59
26.6
21.1
8,860
1,080
24.1
122
4,320
143,000
Intermediate process; statistics are included in other subcategory totals.
-------
o
0)
rt
(D
TABLE
-------
As can be seen, 346 out of the total of 638 establishments, or
54% of the total, utilize the 13 subcategory combinations listed.
The remaining 292 establishments (46%) utilize another 70 differ-
ent subcategory combinations.
The subcategories are described below.
Subcategory 1 - Soap Manufacture by Batch Kettle
Most of the soap made by this process finds its way into toilet
bar form for household usage. This use demands freedom from
offensive odors and from displeasing colors. In order to meet
this requirement, the starting fats and oils must be refined.
There is a direct relationship between quality of the fats and
quality of the finished soap.
Fat Refining and Bleaching. There are several ways in which
fats are refined. One of the most frequently used methods employs
activated clay as the extraction agent. Activated clay, having a
large ratio of surface area to weight, is agitated with warm oil
and filtered. Bleaching occurs as color bodies, dirt, etc., are
removed, usually through a plate and frame press. The clay is
disposed of as solid waste. A small amount of clay remains in
the refined fat.
Other ways in which fats are refined include caustic extraction,
steam stripping, and use of proprietary aqueous chemicals.
Soap Boiling. Although a very old process, kettle boiling
still makes a very satisfactory product, and in several well
integrated manufacturing plants this process has a very low
discharge of wastewater effluents. In this process vegetable and
animal fats and oils are alternately heated in the presence of
alkaline materials and inorganic salts to yield two fractions:
(1) a crude, unfinished soap called neat soap; and (2) crude,
dilute glycerine.
Salt Usage. In order to maintain suitable solubility for
proper processing, salt is added to the soap-making process to
maintain the required electrolytic balance. Most of the salt
charged into the process is ultimately returned to it from the
glycerine concentration step, which will be discussed later.
Practically every kettle boiling soap manufacturer concentrates
the glycerine stream, although only a few go on to the distilla-
tion of glycerine.
Subcategory 2 - Fatty Acid Manufacture by Fat Splitting
By means of fat splitting very low grade fats and oils are upgraded
to high value products by splitting the glycerides into their two
components, fatty acids and glycerine. Fat splitting is a hydro-
lytic reaction which proceeds as follows:
Date: 6/23/80 II.18-5
-------
Fat + Water -» Fatty Acid + Glycerine
Vegetable and animal fats and oils are heated to 260°C under
pressure, in the presence of various catalysts, to yield two
fractions: (1) a crude mixture of fatty acids in water, and
(2) crude, dilute glycerine. The glycerine byproduct can be
produced at a variety of concentrations depending upon how com-
plete a fat hydrolysis is desired. More concentrated glycerine
can be provided at some expense to fatty acid yields. Catalysts
employed include zinc, tin, or an aromatic sulfonic acid. The
crude mixture of fatty acids is then distilled to recover those
applicable to soap manufacturing. Sometimes this fraction is
subjected to flash hydrogenation, using nickel as a catalyst, to
reduce the amount of unsaturated fatty acids present. As in
Subcategory 1, the raw fats and oil are sometimes refined prior
to any other processing.
Subcategory 3 - Soap from Fatty Acid Neutralization
Soap making by fatty acid neutralization exceeds the kettle boil
process in speed and minimization of wastewater effluent. Widely
used by the large soap producers, it is also very popular with
the smaller manufacturer.
This route from the acids is faster, simpler (no by product
dilute glycerine stream to handle), and "cleaner" than the kettle
boil process. Distilled, partially hydrogenated acids are usually
used.
The reaction that takes place is substantially:
Caustic + Fatty Acid -» Soap
The resulting neat soap, containing about 30% moisture, is fur-
ther processed into bars or liquid formulations in the same
manner as the product from kettle boiling.
Subcategory 4 - Glycerine Concentration
The kettle boiling soap process generates an aqueous stream
referred to as sweet water lyes. This stream will contain 8% to
10% glycerine, a heavy salt concentration, and some fatty mate-
rials. It is processed by first adding a mineral acid (HC1) to
reduce the alkalinity. This is followed by the addition of alum,
which precipitates insoluble aluminum soaps. The precipitate
carries other impurities down with it. If the stream were not
treated with alum, there would be severe foaming in the evapora-
tors , and the contaminant would be carried forward into the
glycerine. The cleaned up glycerine solution is sent to the
evaporators, which are heated under reduced pressure. As the
glycerine is concentrated, the salt comes out of solution and is
removed from the evaporation kettle, filtered, and returned to
Date: 6/23/80 11.18-6
-------
the soap-making process. In many plants this separating function
is performed continuously by a centrifuge, with the filtrate
being returned to the evaporator.
The glycerine is usually concentrated to 80% by weight and then
either run to a still to be made into finished glycerine, or
stored and sold to glycerine refiners.
The sweet water glycerine from fat splitting is flashed to atmos-
pheric pressure, thereby releasing a considerable amount of water
very quickly. This can provide a glycerine stream of 20% glycer-
ine or more going to the evaporators. Since there is no salt
used in fat splitting there will be none in the sweet water.
Subcategory 5 - Glycerine Distillation
In this process, the concentrated glycerine (80%) is run into a
still which, under reduced pressure, yields a finished product of
98+% purity. At room temperature, the still bottoms (also called
glycerine foots) are a glassy, dark brown, amorphous solid rather
rich in salt. Water is mixed with the still bottoms before they
are run into the wastewater stream.
Some glycerine refining is done by passing the dilute stream over
ion exchange resin beds, both cationic and anionic, and then
evaporating it to 98+% glycerine content as a bottoms product.
There are frequently three sets, in series, of both cation and
anion exchange resins used in this process. Each step is
designed to reduce the input load by 90%. Some of the fat split-
ting plants are equipped with this type of unit.
Subcategory 6 - Soap Flakes and Powders
Neat soap (65% to 70% hot soap solution) may or may not be blended
with other products before flaking or powdering. Neat soap is
sometimes filtered to remove gel particles and run into a crutcher
for mixing with builders.
After thorough mixing, the finished formulation is run into a
flaker. This unit normally consists of a two-roll "mill." The
small upper roll is steam heated while the larger, lower one is
chilled. The soap solidifies on the lower roll and is slit into
ribbons as it sheets off the mill.
The ribbons are fed into a continuous oven heated by hot air.
The emerging flakes contain 1% moisture. All of the evaporated
moisture goes to the atmosphere, creating no wastewater effluent.
In spray drying, crutched, heated soap solution is sprayed into a
spray tower, or flash dried by heating the soap solution under
pressure and releasing the steam in the spray dryer under reduced
pressure. In either case the final soap particle has a high
Date: 6/23/80 II.18-7
-------
ratio of surface area to unit of weight, which makes it readily
soluble in water.
Subcategory 7 - Bar Soaps
In some bar soap processes additives are mixed with the neat soap
in a crutcher before any drying takes place. Another approach is
to begin the drying process with the hot neat soap going to an
"atmospheric" flash dryer followed by a vacuum drying operation
in which the vacuum is drawn by a barometric condenser. Soap is
then double extruded into short ribbons or curls and sent to
plodders for further blending or physical processing. At this
point the soap will normally have 8% to 14% moisture depending
upon the previous course of processing.
Next, a milling operation affords the opportunity to blend in
additives and to modify the physical properties of the soap. The
mill consists of two polished rolls rotating at different speeds
to maximize the shearing forces. After milling, the soap is cut
into ribbons and sent to the plodder.
The plodder extrudes and cuts the soap into small chips, after
which further mixing melts all of the individual pieces together
into a homogeneous mass.
Plodding completed, the soap is extruded continuously in a cylin-
drical form, cut to size, molded into the desired form, and
wrapped for shipment. Most of the scrap in this operation is
returned to the plodder.
The amount of water used in bar soap manufacture varies greatly.
In many cases the entire bar soap processing operation is done
without generating a single wastewater stream. The equipment is
all cleaned dry, without any washups. In other cases, due to
housekeeping requirements associated with the particular bar soap
process, there are one or more wastewater streams for air scrubbers
Subcategory 8 - Liquid Soaps
In the liquid soap process neat soap (often the potassium soap of
fatty acids) is blended in a mixing tank with other ingredients
such as alcohols or glycols to produce a finished product, or
with pine oil and kerosene for a product with greater solvency
and versatility. The final blended product may be, and often is,
filtered to achieve a sparkling clarity before being drummed.
In making liquid soap, water is used to wash out the filter press
and other equipment. Wastewater effluent is minimal.
Date: 6/23/80 II.18-8
-------
Subcategory 9 - Oleum Sulfonation and Sulfation (Batch and
Continuous
One of the most important active ingredients of detergents is
alcohol sulfate or alkyl benzene sulfonate, particularly in
products made by the oleum route.
In most cases the sulfonation/sulfation process is carried out
continuously in a reactor where the oleum (a solution of sulfur
trioxide in sulfuric acid) is brought into intimate contact with
the hydrocarbon or alcohol. Reaction is rapid. The stream is
then mixed with water and sent to a settler.
Prior to the addition of water the stream is a homogeneous liquid.
With the addition of water, two phases develop and separate. The
dilute sulfuric acid is drawn off and usually returned to an
oleum manufacturer for reprocessing up to the original strength.
The sulfonated/sulfated material is sent on to be neutralized
with caustic.
Subcategory 10 - Air-S03 Sulfation and Sulfonation (Batch
and Continuous)
This process for surfactant manufacture has numerous unique
advantages and is used extensively. In the oleum sulfation of
alcohols, formation of water stops the reaction short of comple-
tion because it reaches a state of equilibrium, resulting in low
yields. With S03 sulfation, no water is generated, hydrolysis
cannot occur, and the reaction proceeds in one direction only.
S03 sulfonation/sulfation is also quite amenable to batch proces-
sing, which can produce products having a minimum of sodium
sulfate (all of the excess S03, or sulfuric acid in the case of
oleum sulfonation, will be converted into sodium sulfate in the
neutralization step with caustic). Another advantage of the S03
process is its ability to successively sulfate and sulfonate an
alcohol and a hydrocarbon respectively.
Subcategory 11 - S03 Solvent and Vacuum Sulfonation
Undiluted S03 and organic reactant are fed into the vacuum reactor
through a mixing nozzle in this process. Recycle is accomplished
by running the flashed product through a heat exchanger back into
the reactor. The main advantage of the system is that under
vacuum the S03 concentration and operating temperature are kept
low, thereby assuring high product quality. Offsetting this is
the high operating cost of maintaining the vacuum.
Subcategory 12 - Sulfamic Acid Sulfation
Sulfamic acid, a mild sulfating agent, is used only in very
specialized quality areas because of the high reagent price. The
system is of particular value in the sulfation of ethoxylates.
Date: 6/23/80 II.18-9
-------
The small specialty manufacturer may use this route for making
high quality alcohol sulfates, equivalent to those from the
chlorosulfonic acid route, substituting high reagent cost for the
high capital costs of the chlorosulfonic route.
Subcategory 13 - Chlorosulfonic Acid Sulfation
For products requiring high quality sulfates, chlorosulfonic acid
is an excellent agent. It is a mild sulfating agent, yields no
water of sulfation, and generates practically no side reactions.
It is a corrosive agent and generates HCl as a by product.
An excess of about 5% chlorosulfonic acid is often used. Upon
neutralization it will yield an inorganic salt which is undesir-
able in some applications because it can result in salt precipi-
tation in liquid formulations, etc.
Subcategory 14 - Neutralization of Sulfuric Acid Esters
and Sulfonic Acids
This step is essential in the manufacture of detergent active
ingredients; it converts the acidic hydrophylic portion of the
molecule to a neutral salt.
Alcohol sulfates are somewhat more difficult to neutralize than
the alkylbenzene sulfonic acids due to the sensitivity to hydrol-
ysis of the alcohol derivative. For this reason, neutralization
is usually carried out as a pH above 7 and as rapidly as possible.
Subcategory 15 - Spray Dried Detergents
In this segment of processing, the neutralized sulfonates and/or
sulfates are brought to the crutcher where they are blended with
requisite builders and additives. From here the slurry is pumped
to the top of a spray tower where nozzles around the top spray
out detergent slurry of approximately 70% concentration.
Wastewater streams are rather numerous. They include many wash-
outs of equipment, from the crutchers to the spray tower itself.
One wastewater flow with high loadings comes from the air scrubber
which cleans and cools the hot gases exiting from the spray
tower. This is only one of the several units in series utilized
to minimize the particulate matter being sent into the atmosphere.
After the powder comes from the spray tower it is further blended
and then packaged. Solid wastes from this area are usually
recycled.
Subcategory 16 - Liquid Detergents
For liquid detergents the sulfonated and sulfated products for
the processes described in subcategories 9 through 14 are pumped
Date: 6/23/80 11.18-10
-------
into mixing tanks where they are blended with numerous ingredi-
ents, ranging from perfumes to dyes. From here, the fully for-
mulated liquid detergent is run down to the filling line.
Subcategory 17 - Dry Detergent Blending
In this process fully dried "active" (surfactant) materials are
blended with additives, including builders, in dry mixers. In
the more sophisticated plants mixing time is utilized to the
maximum by metering components into weighing bins prior to load-
ing into mixers. When properly mixed, the homogeneous dry product
is packed for shipment.
Subcategory 18 - Drum Dried Detergents
Drum drying of detergents is an old process. Much of the equip-
ment still in use is well over 30 years old. The process yields
a fairly friable product which can become quite dusty with any
extensive handling.
A thin layer of the filler cake on the drum is removed contin-
uously by a knife blade onto conveyors. The powder is substan-
tially anhydrous. The vapors coming off are often collected and
removed through a vapor head between the drums.
This operation should be essentially free of generated wastewater
discharge except that from an occasional washdown.
Subcategory 19 - Detergent Bars and Cakes
In answer to the need for a "bar soap" which performs satisfactor-
ily in hard water, the detergent industry manufactures and markets
detergent bars. They constitute about 20% of the toilet bar
market.
There are two types of "detergent" bars: those made of 100%
synthetic surfactant and those blended from synthetic surfactant
and soap. Most products are the latter type.
Blending methods and types of equipment are essentially the same
as those used for conventional soap.
II.18.2 Wastewater Characterization [1]
There are essentially three types of in-plant pollutants in the
wastewater effluent streams:
Impurities removed from raw materials
By products or degradation products made in the process
Very dilute product (in aqueous solution) resulting from
leaks, spills, and equipment cleanout.
Date: 6/23/80 11.18-11
-------
D
P
rt
fD
ro
to
oo
o
TABLE 18-4.
MAJOR WASTEWATER POLLUTANTS FROM PROCESSES IN SUBCATEGORIES
OF THE SOAP AND DETERGENT MANUFACTURING INDUSTRY [1]
Subcategory
Major
wastewater pollutants
Source(s) of
pollutants in process
H
H
00
4 and 5
Soap manufacture by batch kettle
Fatty acid manufacture by fat
splitting
Soap from fatty acid neutralization
Glycerine concentration and dis-
tillation (glycerine recovery)
Soap flakes and powders'
Bar soaps
Fats and oils; unrecov-
ered NaCl, Na2S04,
and NaOH; spilled and
lost soaps and by
products (glycerine)
Fatty acids, unreacted
fats and glycerine;
sodium salts and NaOH;
zinc and alkaline
earth metals, nickel
Fats and oils; unrecov-
ered NaCl, Na2S04,
and NaOH; spilled and
lost soaps and by-
products (glycerine)
Glycerine, glycerine
polymers, NaCl, and
Na2S04
Pure soap, small amounts
of free fatty material,
NaCl from spills and
leaks
Pure soap, small amounts
of free fatty material,
NaCl from spills and
leaks
Fat refining and bleaching,
fat heating, neutraliza-
tion of batch, fat handl-
ing.
Fat heating, catalytic
splitting, flash hydroge-
nation, neutralization
Fat heating, catalytic
splitting, flash hydroge-
nation, neutralization
Lye treatment, glycerine
distillation
Flaking, crutching and dry-
ing, spray drying, pack-
aging
Soap milling, crutching and
drying, packaging
(continued)
-------
CPi
TABLE 18-4 (continued)
CD
O
Subcategory
Major
wastewater pollutants
Source(s) of
pollutants in process
H
CO
I
u>
10
11
12
Liquid soaps
Oleum Sulfonation and Sulfation3
a
Air-S03 sulfation and sulfonation
S03 solvent and vacuum sulfona-
tion
Sulfamic acid sulfation3
13
a
Chlorosulfonic acid sulfation
Solvents (alcohols or
glycols), builders,
dyes, perfumes, and
potassium salts
Oily raw materials, sul-
furic acid, and sur-
factant sulfonic acid
Oily raw materials, sul-
furic acid, and sur-
factant sulfonic acid
Oily raw materials, sul-
furic acid, surfactant
sulfonic acid, and sul-
fate
Unsulfated ethoxy alco-
hols, sulfamic acid,
ammonium ether sul-
fates, fatty alcohols,
alcohol ethoxylates,
alkyl phenol ethoxy-
lates, ammonium, sodium,
and triethanol amine
salts, hydrochloric and
sulfuric acid, ammonium
and sodium ions.
No information available
Receiving and storage,
blending, packaging
Receiving and storage,
oleum fume scrubber, cool-
ing water, reactor leaks
and spills, reactor and
mixer washouts
Receiving and storage, va-
porizer condensate, dryer
and reactor washouts
Receiving and storage, va-
porizer condensate,
scrubber and degasser
Receiving and storage, reac-
tor washouts
(continued)
-------
TABLE 18-4 (continued)
ft
(D
U)
oo
o
Subcategory
Major
wastewater pollutants
Source(s) of
pollutants in process
14
15
Neutralization of sulfuric acid
esters and sulfonic acids
Spray dried detergents0
16
Liquid detergents
00
I
Products of subcategories
9, 10, and 11; neutral-
ized products; the
various cations
Receiving and storage, neu-
tralization
LAS, amide, nonionic and Receiving and storage.
alcohol surfactants,-
sodium phosphate, car-
bonate and silicate
builders; carboxmethyl
cellulose, brighteners,
perborate, dyes, fillers,
and perfume
Organic surface active
agents from cleanup and
washdown; citrate
builders and solvents
(ethanol); potassium
phosphate; silicates,-
sodium xylene sulfon-
ates, urea, various
additives
transfer, fume scrubbers,
crutching, spray drying,
blending and packaging
Storage and transfer areas,
blending washes, pack-
aging leaks and spills
17
Dry detergent blending
LAS, amide, nonionic and
alcohol surfactants;
sodium phosphate, car-
bonate and silicate
builders; carboxmethyl
cellulose, brighteners,
perborate, dyes,
fillers, and perfume
Dry blending and packaging
washouts
(continued)
-------
D
fa
rt
(0
NJ
u>
oo
o
TABLE 18-4 (continued)
Subcategory
Major
wastewater pollutants
Source(s) of
pollutants in process
18 Drum dried detergents0
19 Detergent bars and cakes*
Raw material and sur-
factants
Pure soap, small amounts
of free fatty material,
NaCl from spills and
leaks, and synthetic
surfactants
Drum drying and packaging
washouts
Soap milling, crutching, and
drying, packaging
CO
Subcategory process typically requires scrubber use.
-------
Major types of wastewater pollutants from the subcategories of
the soap and detergent manufacturing industry can be found in
Table 18-4. This table shows that resultant wastewaters depend
upon process operating parameters and the kind of soap or deter-
gent material produced.
Of these pollutants, several are of particular environmental
concern. Synthetic surface active agents not only create BOD5
and COD, but they cause water to foam and, in high concentrations,
they can be toxic to fish and other organisms. Nutrients, partic-
ularly phosphate produced in part by liquid detergent manufacture,
are of concern because of their contribution to euthrophication
of lakes. Soap production leads to wastewaters with high alkalin-
ity, high salt, and high oxygen demand. Spills of raw materials
contribute to oil and grease levels. Most of the suspended
solids come from organics (i.e., calcium soaps), and many are of
the volatile rather than nonvolatile type. Since strong acids
and strong alkalies are used in most of these subcategories, pH
can be very high or very low in wastewaters [1].
II.18.3 PLANT SPECIFIC DESCRIPTION [2]
In 1977, a survey of the industry was undertaken for the U.S.
Environmental Protection Agency. Four hundred and nine forms
were sent to U.S. establishments, and 170 responses applicable to
SIC 2841 were obtained. The survey asked for information on
parameters such as production levels, process subcategories at a
given facility, and the fate and characteristics of the wastewater
generated in each subcategory. This survey included a sampling
and analysis review to establish the presence or absence of toxic
compounds in wastewaters discharged from the various subcategories.
The results of the review, however, were suspect for all subcate-
gories except subcategory 15. This was due to possible deviations
from EPA's analytical protocol involving excessive lag times
between sample collection and extraction.
As a result, an additional sampling and analysis review was per-
formed in 1979. Wastewaters from subcategories 6, 8, and 17 were
not examined in 1979 because they comprise only 0.03% of the indus-
try's total discharges and because of the difficulty associated
with scheduling sampling and analysis surveys coincident with the
low intermittent discharge flow rates of these three subcategories
Also, since the only wastewater from subcategory 18 evolves from
pump seal water and the washdown of off-specification product,
wastewater samples were not collected from subcategory 18.
In addition, no sampling data from this effort are available
for Subcategories 9 through 14. Based on similarities in raw
materials used in each subcategory, process technologies
employed for each subcategory, and resultant subcategory final
products it was generally felt that if toxic substances were
found in the wastewaters from the omitted subcategories, they
Date: 6/23/80 11.18-16
-------
D
0
rt
CO
o
TABLE 18-5. TOXIC POLLUTANTS DETECTED IN THE 1979 SAMPLING REVIEW
OF THE SOAP AND DETERGENT INDUSTRY [2]
Total wastewater, m3/1,000 kg of product: Subcategory I, 1.9;
Subcategory 2, 7.59; Subcategory-3, 0.0075; Subcategories 4
and 5, 180; Subcategory 7, 7.34; Subcategory 15, 4.76; Sub-
category 16, 1.02; Subcategory 19, 21.6
oo
Subcategory
concentration, pg/L
Toxic pollutant
Metals and inorganics:
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Phthalates:
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols :
2-Chlorophenol
Pentachlorophenol
Phenol
2,4, 6-Tr ichlorophenol
p-Chloro-m-cresol
1 2 34 and 5
13 99
3,400 65 67 38
10 9.5 0.1
15
76
29 67 39
1,600 2,500 67 15
13 0.5
96
150
4,400 7.1 34
7 15
20
22
6.7 19
13 36
2.3
1.8 69
18
26
15
30
7.3
2.9
16
1.0
1.0
1.0
4.9
31
13
11
94
5.9
91
20
3.9
28
19
17
16
57
20
(continued)
-------
D
&)
rt
0>
H
oo
I
M
CO
TABLE 18-5 (continued)
Total wastewater, m3/l,000 kg or product: Subcategory 1, 1.9; Subcategory 2, 7.59;
Subcategory 3, 0.0075,- Subcategories 4 and 5, 180; Subcategory 7, 7.34; Subcategory 15,
4.76; Subcategory 16, 1.02; Subcategory 19, 21.6
Subcategory
concentration, pg/L
Toxic pollutant 1
Aromatics:
Benzene
Chlorobenzene
Polycyclic aromatic hydrocarbons.-
Phenanthrene/trichloroethylene
Halogenated aliphatics:
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
Trichlorome thane
Methylene chloride 59
Chloroethylene
2 34 and 57 15 16 19
0.7 0.1
22 0.6
1.8 0.4 27
18 11 25
3.3
4.8 1.1
19 1.1
12
Trichloroethylene
Tetrachloroethylene 15
Pesticides and metabolites:
r-BHC 2.2
See phenanthrene.
-------
would be comparable to those detected in the wastewaters from
subcategories actually involved in the sampling and analysis
review.
Raw wastewater data resulting from the sampling and analysis
review are presented in Table 18-5. Establishments surveyed in
1979 utilized, among others, Subcategories 7, 8, and 16. At the'
establishment employing subcategory 7 there were six production
lines. Only one line had a continuous wastewater discharge and
that amounted to less than 0.5 gal/hr of a salt water solution.
In general, all six production lines were cleaned without the use
of water; however, there was the possibility of periodic small
volumes of washdown water being discharged to the POTW. At the
establishment employing subcategory 8, any subcategory wastewaters
generated were recycled to extinction and, thus, were never
discharged from the establishment. The wastewater was not ana-
lyzed because of the nondischarge situation. The establishment
employing subcategory 16 had a very small intermittent discharge
of wastewater resulting mainly from equipment washdowns. However,
noncommingled samples of ths wastewater could not be collected.
It should be further noted that this establishment was installing
a complete recycle/reuse system for all of the wastewater gener-
ated in subcategory 16.
The data from Table 18-5 were used to calculate the volumes of
toxic pollutants in the raw wastewaters discharged from all of
the subcategories in SIC 2841 for all 638 establishments in the
industry. Values are presented in Table 18-6. The missing data
for subcategory 3 were calculated by averaging unit wastewater
data from subcategories 2 and 7. Unit wastewater data from
subcategories 1, 3, and 7 were then averaged to develop the
values for subcategories 6 and 8. Similarly, data for subcate-
gories 17 and 18 were obtained from subcategories 15, 16, and 19.
The toxic pollutant data are further summarized, by subcategory,
in Table 18-7 where the pollutants are categorized into inorganic
and organic fractions. Of the total mass of 100 kg/day (230 lb/
day) of toxic pollutants present in the industry's raw wastewaters,
72% are inorganic and 28% are organic in nature.
To project typical establishment raw wastewater characteristics,
the subcategory production rates obtained by the 1977 survey were
combined with the toxic pollutant information given in Table 18-6
and the predominant subcategory combinations shown in Table 18-3.
The projections for small establishments are shown in Table 18-8
and for large establishments in Table 18-9. Table 18-10 presents
the volumes of toxic pollutants in the direct discharges from six
establishments having NPDES permits. These discharges approximate
11.5% of the total industry's wastewater volume, yet contain only
2.8% of the total industry's inorganic toxic pollutant discharges
and 1.6% of the total industry's organic toxic pollutant discharges
Date: 6/23/80 11.18-19
-------
o
pi
(D
TABLE 18-6.
CONCENTRATIONS OF TOXIC POLLUTANTS IN TOTAL
INDUSTRY RAW WASTEWATERS [2]
to
OJ
00
H
H
M
00
o
(g,
/d)
Subcategory
Toxic pollutant
Ketals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols
2-Chlorophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
g-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene
1 2 3 4 and 5
167
195 7,400
3,800 961 2.27 2,840
11.3 140 2.27
1,090
84.8
425 2.27 2,940
6
37.
9.
19.
0.
7
6 165
98 54
5 108
454
2.72 14.5
1,850 36,800 2.27 1,100
186 109 35.8
108
2,210 1,270
4,950 105 59.9 2,570
9.53 5.44 9.98
26.
0.
5.
18.
57.
844
0.
3 144
454
0
1
2 455
454
8
299
79.8
156
1.36
20.4
209
1.36
39
145
6,710
1.81
15
687
595
1.100
72.1
2,150
1,620
465
38.6
1,880
230
91.6
674
16
9.53
9.53
9.53
48.5
300
126
107
929
58.1
900
194
4.54
271
17
0.907
0.907
0.907
124
553
1,590
24.5
480
6.8
386
22.7
80.3
356
39.5
15.9
130
1
5
16
0
5
4
0
9
3
0
0
1
18
.36
.9
.8
.454
.0
.08
.454
.07
.63
.454
.454
.36
19
130
97.5
358
127
3.63
Polycyclic aromatic hydrocarbons
Acenaphthene
Phenanthrene/trichloroethylene
Halogenated aliphatics
1,1,-Dichloroethylene
1,2-Trans-dichloroethylene
Trichloromethane
Hethylene chloride
Chloroethylene
Trichloroethylene
Tetrachloroethylene
Pesticides and metabolites
Y-BHC
27.2
15.4
30.4
1,310
66.2
16.3
0.907
11.3
2.72
5.9
89.4
2.22
824
151
107
184
72.1
142
622
81.2
53.1
48.5
293
12.7
1.36
6.8
0.907
0.454
0.454
3.18
167
20.9
6.8
6.8
75.7
Blanks indicate no dat?
-------
TABLE 18-7.
INORGANIC AND ORGANIC TOXIC POLLUTANTS
IN TOTAL INDUSTRY RAW WASTEWATERS [2]
Inorganic
pollutants
Subcategory
1
2
3
4 and 5
6
7
8
15
16
17
18
19
Totals
kg/ day
5.74
38.5
0.172
15.4
0.095
0.485
0.767
6.23
2.50
3.17
0.032
0.69
73.8
Percent of
total
7.78
52.22
0.24
20.84
0.13
0.66
1.04
8.45
3.38
4.29
0.05
0.94
100.02
Organic
pollutants
kg/ day
5.14
2.54
1.66
3.96
0.939
0.00
7.47
4.39
0.794
1.90
0.018
0.272
28.9
Percent of
total
17.80
8.79
5.05
13.72
3.25
0.00
25.87
15.18
2.75
6.58
0.07
0.94
00.00
All
pollutants
kg/ day
10.9
41.1
1.63
19.3
1.03
0.486
8.24
10.6
3.29
5.07
0.050
0.962
103
Percent of
total
10.60
40.00
1.59
18.84
1.01
0.47
8.02
10.34
3.20
4.94
0.05
0.94
100.00
TABLE 18-8.
CONCENTRATIONS OF TOXIC POLLUTANTS IN SMALL
FACILITY PREDOMINANT SUBCATEGORY COMBINATION
RAW WASTEWATERS [2]
(mg/day)
Toxic pollutant
Metals and inorganics
antuony
Arsenic
Cacsuw
Chroaum
Copper
Cyanide
Lead
Hercury
Nickel
Silver
Thalliw
Zinc
Phthalates
>li<2-eU>yU«rl) phtnalate
Di-ri-butyl phthalate
Phenols
2-Chloropbenol
Pentactilorophenol
Phenol
2.4, 6-Trichlorophenol
J>-Chloro-B-cr«iol
aroautics
Chlorobenzene
Polycyclic aroMtic hydrocarbons
Phenanthrene/trichloroe thy lane
Halogenatcd aliphatic!
1,1-Dlchloroethylene
1 ,2-Trant-dlcMorosUiylnx
Trichlorcew thane
Hethylene chloride
Chloroethylene
Trichloroethylene
Tetrachloroethylenc
Pesticides and Mtabolites
i-anc
SxAcategorv conbination
la
4.50
4.50
4.50
13.6
ei.7
36.3
27 1
254
1B.1
245
54.4
9.1
72.6
27 2
49 9
Ib
213
948
2,720
40 a
821
13.6
662
40 «
136
90 7
608
68 1
27.2
222
245
5.070
141
90.7
81.7
504
22.7
2a
4. JO
4 50
4.50
227
1,030
2,760
680
1,080
34.9
54.4
54 4
136
182
681
68 1
27.2
222
24S
1,090
141
90 7
13.2
504
22.7
3a
4.50
9 10
4.50
227
1,030
2,760
72 6
1,080
29 2
54. 4
90 7
147
68.1
685
68 1
27.2
222
245
1,090
141
90 7
13.2
504
22.7
3b
4 50
13 6
4. SO
13 6
86.2
40 6
27 2
254
22 7
245
S4 4
4 S
4 5
77.1
268
27 2
54 4
4*
4 SO
13 6
4.50
13 6
10,300
31 S
40 8
227
27 2
254
22 ^
5.210
54 4
4 5
295
77 1
13,600
27.2
54 4
45 4
4b
4 50
72 6
4 50
121
10,300
2,800
72 6
1,080
77 1
907
90 7
145
31 8
123
2,210
68 1
27 2
222
245
1,100
141
90 7
154
504
4 50
22 7
Blanki indicate no data available
"see phenanthrenc
Date: 6/23/80
11.18-21
-------
D
0)
rt
(0
cr>
to
oo
o
H
CD
I
to
TABLE 18-9.
CONCENTRATIONS OF TOXIC POLLUTANTS IN LARGE FACILITY
PREDOMINANT SUBCATEGORY COMBINATION RAW WASTEWATERS [2]
(mg/day)
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
silver
Thallium
Zinc
Phthalates
Bis(2-ethyhexyl) phthalate
Di-n-butyl phthalate
Phenols
2-Chlorophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
g-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene
Polycyclic aromatic hydrocarbons
Phenanthrene/trichloroethylene
Halogenated aliphatics
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
Trichloromethane
Methylene chloride
Chloroethylene
Trichloroethylene
Tetrachloroethylene
Pesticides and metabolites
y-BHC
Subcategory combination
la
86.2
86.2
86.2
436
2,700
1,130
957
8,360
521
811
1,740
341
2,436
1,830
957
1,660
Ib
13.6
13.6
13.6
159
6,190
2,230
.313
6,130
86.2
4,950
290
1,029
59.0
4,559
508
1,670
1,830
7,710
1,040
680
621
3,750
163
2a
99.8
99.8
99.8
203
9,800
21,600
1,270
14,500
608
13,000
2,030
1,029
403
7,000
508
1,670
19,400
8,940
1,040
680
2,280
3,750
163
2b
86.2
86.2
86.2
166
16,700
27,100
2,650
59,000
521
46,200
1,740
10,916
344
46,600
5,420
11,300
2,190
957
3,840
1,660
1,700
3a
99.8
3,980
99.8
203
9,850
21,500
1,320
1,450
608
13,400
2,030
3,061
29,900
8,390
508
1,276
1,670
531
8,940
1,040
680
2,280
3,750
163
3b
86.2
12,800
86.2
435
5,100
5,730
1,050
8,970
666
8,000
1,740
3,675
4,260
43,200
201,000
182
957
4,100
653
Blanks indicate no data available.
aSee phenanthrene.
-------
rt
(D
CTl
M
U>
CD
O
H
CO
I
TABLE 18-9 (continued)
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Phthalates
Bis(2-ethyhexyl) phthalate
Di-n-butyl phthalate
Phenols
2-Chlorophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
j>-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene
Polycyclic aromatic hydrocarbons
Phenanthrene/trichloroethylene
Halogenated aliphatics
1 , 1-Dichloroethylene
1,2-Trans-dichloroethylene
Trichloromethane
Methylene chloride
Chloroethylene
Trichloroethylene
Tetrachloroethylene
Pesticides and metabolites
y-BHC
12
83
5
1
1
8
8
1
3
6
43
303
5
4a
86.2
,800
86.2
435
,600
235
,730
,760
,050
,970
666
,200
,740
,645
,480
,212
,280
182
531
957
,650
989
4b
99.8
10,400
99.8
2,030
12,500
17,800
1,330
15,200
7,810
13,100
2,030
2,373
4,990
16,060
238,000
508.2
72.6
1,690
2,040
8,940
1,040
681
5,380
3,750
762
163
Subcategory
5a 6
4,
147,
147,
49,
1,
54,
59,
4,
104,
1,
11,
2,
194,
5,
15,
19,
24,
3,
3,
1,
8 6.. 2
340
86.2
000
000
277
100
760
500
300
230
000
740
500
220
344.8
000
420
177
800
900
000
540
030
336
700
4,
148,
154,
69,
1,
54,
65,
4,
109,
2,
12,
2,
199,
5,
17,
21,
32,
1,
4,
3,
3,
1,
combination
a
99.8
350
99.8
000
000
277
500
760
700
500
320
000
030
600
220
403.8
000
920
177
500
700
000
040
220
650
750
336
860
7a
8,
153,
99,
3,
69,
65,
65,
4,
984,
4,
19,
84,
100,
5,
17,
22,
32,
1,
4,
2,
3,
1,
99.8
240
99.8
000
000
500
500
300
500
320
000
300
700
800
000
920
540
500
800
000
040
220
280
750
860
9a
99.8
9,750
99.8
137,000
176,000
15,000
85,400
1,760
63,600
15,000
5,380
999,000
2,030
9,006
2,950
87,100
206,000
508.2
558
2,080
3,430
50,200
3,440
147
4,880
12,500
445
163
9b
99.8
9,800
99.8
153,000
112,000
14,700
111,000
65,300
65,600
5,380
999,000
2,030
19,922
73.1
87,100
148,000
5,920
558
180
22,800
50,200
3,440
5,000
3,580
12,500
109
1,860
See phenanthrene.
-------
o
01
rt-
to
OJ
oo
o
TABLE 18-10.
POLLUTANTS FOUND IN THE DIRECT DISCHARGES FOR SIX
ESTABLISHMENTS HAVING NPDES PERMITS [2]
Wastewater flow, m3/day: Establishment I, 3,290; Establishment II, 2,650;
Establishment III, 5,220; Establishment IV, 87.1; Establishment V, 2,600;
Establishment VI, 2,610; total, 16,500
Establishment
1 |
!_! Pollutant
1— i Conventional pollutants
CO BOD5
1 TSS
t^ Oil and grease
Toxic pollutants
Chromium
Copper
Cyanide
Lead
Nickel
Zinc
Di-n-butyl phthalate
Pentachlorophenol
Phenol
Benzene
Phenanthrene/trichloroethylene
1 , 1-Dichloroethylene
I
II
III
Concentration ,
6.13
6.13
2.65
0.156
0.088
0.023
0.061
0.023
0.001
0.054
0.0002
0.001
0.028
6.13
6.13
2.63
0.158
0.065
0.001
0.023
0.065
0.355
0.002
0.020
0.055
0.0002
0.001
0.028
12
12
5
0
0
0
0
0
0
0
0
0
0
.3
.3
.30
.311
.113
.046
.122
.045
.002
.108
.0004
.001
.055
0
0
0
0
0
0
0
0
0
0
0
0
0
number
IV
kg/day
.045
.091
.045
.002
.001
.0002
.001
.0002
.000
.001
.0000
.000
.0002
V
2.63
0.091
0.045
0.047
0.017
0.007
0.018
0.007
0.00002
0.016
0.0000
0.000
0.008
VI
6.13
6.13
2.63
0.156
0.057
0.023
0.061
0.023
0.001
0.054
0.0002
0.001
0.028
Total
discharge,
kg/day
33.3
31.5
13.2
0.830
0.310
0.001
0.122
0.328
0.453
0.006
0.020
0.289
0.001
0.001
0.147
Average
concentration,
ng/L
2,000
1,900
800
50
19
0.
7.
20
28
0.
1.
18
0.
0.
8.
1
4
3
2
1
2
9
Blanks indicate no data available.
-------
II.18.4 POLLUTANT REMOVABILITY
Pollutants released in the process waters from the soap and
detergent industry are generally of a nontoxic nature and can be
pretreated, removed, or ultimately disposed of under normal
controlled conditions. Treatment techniques currently in'use to
recover or remove wastewater pollutants at these facilities are
standard, well-established processes.
The industry's wastewater pollutants can be greatly reduced by
lower process water usage and/or the recycling of process water.
In addition, significant recovery of marketable soap products,
fats, glycerine, organic surface active agents, etc., can be
realized by lower water use, particularly through process redesign
or replacement. For example, by changing operating techniques
associated with barometric condensers or by replacing such conden-
sers with surface condesers, water use in most processes can be
lowered and the amount of organics released to the sewer can be
reduced. These organics can be recovered to be purified for a
possible profit. In the manufacture of liquid detergents, instal-
lation of additional water recycle piping and tankage and the use
of air (rather than water) to blow out filling lines can substan-
tially reduce water use and minimize loss of the finished product.
Table 18-11 presents treatment methods for the removal or elimina-
tion of pollutants found in wastewaters from soap and detergent
manufacture. Important features and details of the various
treatment methods and abatement systems can be readily found in
the literature. As seen in this table, organics (especially
those of a toxic nature) can be treated primarily by bioconver-
sion processes and activated carbon adsorption systems. The
remainder of the major pollutants can be treated by filtration,
sedimentation or clarifying processes, and other treatment
techniques. As an example, coagulation and sedimentation of the
wastewaters can help remove insoluble precipitate residuals
chracteristic of soap manufacturing processes. The relative
efficiency of removal of pollutants for these various processes
is given in Table 18-12, which shows that for most pollutant
treatment processes, removability efficiency can be as high as
90-95%. The efficiency achieved is governed by operating param-
eters of the various processes and by the types and amounts of
pollutants in the wastewater.
Date: 6/23/80 11.18-25
-------
TABLE 18-11
TREATMENT METHODS USED IN
ELIMINATION OF POLLUTANTS [1]
Pollutants
Treatments
Free and emulsified
oils and greases
Suspended solids
1. Gravity separation
2. Coagulation and sedimentation
3. Carbon adsorption
4. Mixed media filtration
5. Flotation
1. Plain sedimentation
2. Coagulation-sedimentation
3. Mixed media filtration
Dispersed organics
Dissolved solids
( inorganic )
Unacceptable acidity
or alkalinity
Sludge obtained from
or produced in
process
1.
2.
1.
2.
3.
4.
1.
1.
2.
3.
4.
5.
6.
7.
Bioconversion
Carbon adsorption
Reverse osmosis
Ion exchange
Sedimentation
Evaporation
Neutralization
Digestion
Incineration
Lagooning
Thickening
Centrifuging
Wet oxidation
Vacuum filtration
TABLE 18-12.
RELATIVE EFFICIENCY OF SEVERAL METHODS
USED IN REMOVING POLLUTANTS [1]
Pollutant and methoa
Removal"efficiency
Oil and grease
API type separation
Carbon adsorption
Flotation
Mixed media filtration
Coagulation-sedimentation
with iron, alum or solid
phase (bentonite etc )
Suspended solids
Mixed media filtration
Coagulation-sedimentation
Chemical oxygen demand
Bioconversions (with final
clarifier)
Carbon adsorption
Residual suspended solids
Sand or mixed media filtration
Dissolved solids
Ion exchange or reverse osmosis
Up to 90% of free oils and greases;
variable on emulsified oil
Up to 95% of both free and emulsi-
fied oils
Without the addition of solid phase,
alum or iron, 70-80% of both free
and emulsified oil; with the
addition of chemicals, 90%
Up to 95% of free oils, efficiency
in removing emulsified oils
unknown
Up to 95% of free oil; up to 90%
of emulsified oil
60-95% or more
Up to 90%
50-95%
Up to 99%
Date: 6/23/80
11.18-26
-------
II.18.5 REFERENCES
1. Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Soap and Detergent
Manufacturing Point Source Category. EPA-440/l-74-018a,
U.S. Environmental Protection Agency, Washington, D.C.,
April 1974.
2. Project Recommendations for the Soap and Detergent Manufac-
turing Industry (SIC 2841) BAT/Toxics Study. U.S. Environ-
mental Protection Agency, Washington, D.C., November 1979.
3. Economic Analysis of Effluent Guidelines for the Soap and
Detergent Industry. EPA-230/2-73-026 (PB 256 313), U.S.
Environmental Protection Agency, Washington, D.C., July 1976,
Date: 6/23/80 11.18-27
-------
11.19 STEAM ELECTRIC POWER GENERATING
II.19.1 INDUSTRY DESCRIPTION
II.19.1.1 General Description [1-4]
The steam electric power generation industry is defined as those
establishments primarily engaged in the steam generation of
electrical energy for sale. It is more commonly termed the
steam electric utility industry and includes both fossil-fueled
and nuclear plants. It does not include steam electric power
plants in industrial, commercial, or other facilities. The
industry falls under two Standard Industrial Classification
(SIC) Codes, SIC 4911 and SIC 4931.
Of the 1,068 steam electric power generating plants in operation
in 1977, 22% were built after 1971. These plants (57% of which
are 500 MW or larger in size) represent about 40% of existing
capacity. Plants built before 1960 represent 41% of the total
number of existing plants and account for 18% of total capacity.
In the operation of a power plant, combustion of fossil fuels—
coal, oil, or gas—supplies heat to produce steam that is used
to generate mechanical energy in a turbine. This energy is
subsequently converted by a generator to electricity. Nuclear
fuels, presently uranium, are used in a similar cycle except
that the heat is supplied by atomic fusion.
Wastewaters at steam electric power plants arise from a number
of sources and operations, most of which are process related.
Continuous discharges result from such sources as cooling water
systems, ash handling systems, pollution control (S02) systems,
and boiler blowdown. Regular intermittent wastewaters are
produced from such processes as regeneration of water from
treatment systems. Wastewaters from maintenance cleaning are
usually generated on an irregular, infrequent basis. Drainage
from coal and ash piles depends primarily on the amount of
rainfall rather than plant operating parameters. Finally, there
are a number of miscellaneous activities that can generate
wastewater streams. The discharge frequency for these varies
from plant to plant. Some or all of the various types of waste-
water streams occur at almost all of the plant sites in the
industry. However, most plants do not have distinct and separate
discharge points for each source of wastewater; rather, they
combine certain streams prior to final discharge.
Date: 6/23/80 II.19-1
-------
Table 19-1 presents industry summary data for the Steam Electric
Power Generating (utility) point source category in terms of the
number of subcategories and number of dischargers.
TABLE 19-1. INDUSTRY SUMMARY [1-5]
Industry: Steam Electric Power Generating
Total Number of Subcategories: 8 (6 have subdivisions,
totaling 25)
Number of Subcategories Studied: 8
Number of Dischargers in Industry:
• Direct: 1,050
• Indirect: 100
• Zero: 10
al,068 as of spring 1977.
Current BPT regulations for the Steam Electronic Power Industry
are presented in Table 19-2. "Small units" are defined by the
EPA as generating units of less than 25-MW capacity. "Old units"
are defined as generating units of 500-MW or greater rated net
generating capacity which were first placed into service on or
before January 1, 1970, as well as any generating unit of less
than 500-MW capacity first placed in service on or before Janu-
tary 1, 1974. The term "10-year, 24-hour rainfall event" refers
to a rainfall event with a probable recurrence interval of
once in 10 years as defined by the National Weather Service.
II.19.1.2 Subcategory Descriptions [1, 3, 4]
Subcategories for the steam electric utility point source cate-
gory, as shown in Table 19-3, consist of different sources of
wastewater streams within a plant. This approach is a departure
from the usual method of subcategorizing an industry according
to different types of plants, products, or production processes.
The breakdown in Table 19-3 into divisions and subdivisions is
based on similarities in wastewater characteristics throughout
the industry. Descriptions of the eight broad subcategories are
given in this section.
Condenser Cooling System
The condenser cooling system condenses spent steam (from expan-
sion in the turbine generator to produce electricity) so it may
be recycled to the boiler or discharged. Once-through or recir-
culating systems may be used.
Date: 6/23/80 II.19-2
-------
o
0)
ct
-------
TABLE 19-3. STEAM ELECTRIC POWER GENERATING SUBCATEGORIES [1]
1. Condenser Cooling System
Once-through
Recirculating (primarily cooling tower blowdown)
2. Water Treatment
Clarification
Softening
Ion exchange
Evaporation
Filtration
Other treatment
3. Boiler or Steam Generator Blowdown
4. Maintenance Cleaning
Boiler or steam generator tubes
Boiler fireside
Air preheater
Miscellaneous small equipment
Stack
Cooling tower basin
5. Ash Handling
Oil-fired plants
Fly ash
Bottom ash
Coal-fired plants
Fly ash
Bottom ash
6. Drainage
Coal pile
Contaminated floor and yard drains
Ash pile
7. Air Pollution (S02) Control Devices
8. Miscellaneous Waste Streams
Sanitary wastes
Plant laboratory and sampling systems
Intake screen backwash
Closed cooling water systems
Low level radiation wastes
Construction activity
Date: 6/23/80 II.19-4
-------
A once-through system withdraws water from a water source, such
as an ocean, a river, or a groundwater source, and then dis-
charges the water after passage through the condenser system.
Approximately 67% of the steam electric power plants use this
method. Chlorine or hypochlorite is usually added to minimize
the biofouling of heat transfer surfaces.
Recirculating systems recycle cooling water to the condenser
cooling system and may include one or more of the following:
evaporative cooling towers (wet); dry cooling towers (closed);
hybrid cooling towers (wet and dry combination); cooling lakes
and ponds; and spray lakes and ponds. Approximately 33% of the
steam electric power plants use this method. A bleed stream
(blowdown) generally must be provided, especially for evapora-
tive cooling towers, to control dissolved solids buildup.
Chemicals are added to recirculating water for corrosion, scal-
ing, or biofouling control.
Water Treatment
Boiler feedwater is treated for the removal of suspended and
dissolved solids to prevent scale formation. The basic treat-
ment processes used are clarification, filtration, lime/lime
soda softening, ion exchange, reverse osmosis, and evaporation
(excluding reverse osmosis). The principal chemical additives
used in water treatment are phosphate, caustic soda, lime, and
alum. These treatment methods are associated with wastewater
discharges.
Boiler or Steam Generator Blowdown
As a result of evaporation, total dissolved solids build up in
the boiler water. To maintain such solids within allowable
limits for boiler operation, a controlled amount of boiler water
(blowdown) is intermittently bled off. Approximately 69% of
steam electric power plants practice boiler blowdown. Power
plant boilers are of either the once-through or the drum-type
design. Once-through designs are used almost exclusively in high
pressure supercritical boilers and have no wastewater streams
associated with their operation. Drum-type boilers operate at
subcritical conditions where the steam they generate is in
equilibrium with boiler water. Boiler blowdown is usually of
high quality; it may even be of higher quality than the intake
water.
Maintenance Cleaning
As a result of combusion processes in the boiler, residues ac-
cumulate on the boiler sections and on the air preheater. To
maintain efficient heat transfer rates, these accumulated resi-
dues are removed periodically.
Date: 6/23/80 II.19-5
-------
The insides of boiler or steam generator tubes are often cleaned
with a water wash to which a variety of chemicals may be added
depending on the type of deposit, type of metal, type of boiler,
prior experience, etc. The waste stream usually contains heavy
metals.
Boiler firesides are commonly washed by spraying high pressure
water against hot boiler tubes. Waste streams contain dissolved
and suspended solids. Acid wastes are common in boilers using
high sulfur fuel.
Air preheaters are periodically water washed to remove deposits.
Waste streams are high in suspended and dissolved solids, such
as sulfates, hardness, and heavy metals. Use of high sulfur
fuels will add sulfur oxides to deposits, causing acidic efflu-
ents.
The buildup of solids on and/or in miscellaneous small equipment
(condensate copiers, hydrogen coolers, air compressor coolers,
etc.) and cooling tower basins, and soot buildup in stacks re-
quire periodic washings that produce waste streams.
Ash Handling
Ash is produced as a result of fossil fuel combustion in the
boiler. The ash may be carried in the flue gas (fly ash) and
removed by a collection device, then transported (sometimes by
water) to a disposal site. Bottom ash, which collects in the
boiler bottom, must also be removed and disposed, sometimes by
use of water.
Oil-fired boilers generate less ash than coal-fired ones; how-
ever, the ash is high in vanadium, sodium, and sulfur. Ash
produced from coal firing varies in composition depending on the
coal grade.
Wastewater streams may result from water transport of fly ash,
water removal of bottom ash, and water transport of bottom ash.
Drainage
For coal-fired units, a coal supply of approximately 90 days is
usually maintained near the site. The piles are usually not
enclosed, so the coal comes into contact with moisture and air
which can oxidize metal sulfides to sulfuric acid. Precipitation
then results in acidic coal pile runoff with minerals and metals
in the stream.
Floor and yard drains within a power plant may become contami-
nated with dust, fly ash, coal dust or oil, detergent, etc., and
may be a source of wastewater.
Date: 6/23/80 II.19-6
-------
Fly ash or bottom ash stored in an unenclosed pile will produce
contaminated runoff caused by precipitation.
Air Pollution (S02) Control Devices
Depending upon the fossil fuel sulfur content, an S02 scrubber
may be required to remove sulfur emissions in the flue gases.
Such operations result in liquid waste streams.
Miscellaneous Waste Streams
Besides the major waste streams previously discussed, there are
miscellaneous waste streams in a steam electric power plant such
as sanitary wastes, plant laboratory and sampling systems, back-
washes of the intake screen, closed cooling water systems, low
level radiation wastes (nuclear only), and runoff from construc-
tion activity.
Table 19-4 indicates the occurrence of each subcategory of the
steam electric utility industry according to the four major fuel
types.
II.19.2 WASTEWATER CHARACTERIZATION
Wastewater produced by a steam electric power plant can result
from a number of operations at the site. Some wastewaters are
discharged more or less continuously as long as the plant is
operating. Others are produced intermittently, but on a fairly
regular basis such as daily or weekly, and are still associated
with the production of electrical energy. Other intermittent
wastewaters, produced at less frequent intervals, are generally
associated with either the shutdown or startup of a boiler or
generating unit. Additional wastewaters exist that are essen-
tially unrelated to production but depend on meteorological or
other factors. Figure 19-1 presents a typical flow diagram for
fossil-fueled steam electric power plants. Wastewater flowrates
for the steam electric power generating industry are shown in
Table 19-5. The following sections present data available on
these waste streams.
II.19.2.1 Condenser Cooling System Wastewater
Wastewater generated from once-through condenser cooling systems
will vary widely depending on the quality of the source. Bio-
cides such as chlorine and hypochlorite are usually added to
systems of this type to minimize biological growth within the
condenser.
Wastewater from a recalculating condenser system (primarily cool-
ing tower blowdown) will depend on the amount of dissolved solids
allowable in the system and on the various chemical additives
Date: 6/23/80 II.19-7
-------
TABLE 19-4. OCCURRENCE OF SUBCATEGORIES BY FUEL TYPE [1]
1.
2.
Process of operation
Condenser Cooling System
Once-through
Recirculating
Water Treatment
Clarification
Softening
Ion exchange
Evaporation
Filtration
Other treatment
Nuclear
X
X
X
X
X
X
X
X
Coal
X
X
X
X
X
X
X
X
Oil
X
X
X
X
X
X
X
X
Gas
X
X
X
X
X
X
X
X
3. Boiler or Steam Generator
Blowdown
4. Maintenance Cleaning
Boiler or generator tubes
Boiler fireside
' Air preheater
Miscellaneous small
equipment
Stack
Cooling tower basin
5. Ash Handling
Bottom ash
Fly ash
6. Drainage
Coal pile
Floor and yard drains
7. Air Pollution (S02) Control
Devices
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
8. Miscellaneous Streams
Sanitary wastes
Plant laboratory and
sampling systems
Intake screen backwash
Closed cooling water
systems
Low level radiation wastes
Construction activity
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Bottom ash may be formed for heavier oils.
Date: 6/23/80
II.19-8
-------
D
P»
rt
CD
to
OJ
oo
o
vo
I
vo
RAW
HATER
t
(
_ UASTt- •—
w WATER
CHEMICALS
|
WATER
UASTt- A
__, ^ .
CHEMICALS
1 *
BOILER TUBE
SIDE A AIR'
PPlrUAUR
WASHINGS
BOILER FfEDUATCR
FUEL-*
COMB'N AIR •«
ASH
1
1
HAIfR FOR '" "'^"'Iti
PERIODIC CLEANING *
•
•\V\XX\XAXXXJk_ mruirci r
* ^ r.v .CM • %\^Vn^n^rn. IHiMICALS
COLLECTION
<•.,,.. T SCRUBBING"
i__ _, DEVICE
i i
L rLUE flURBINE | J'" ^","7771 A
• GASES ^ LGPlfPATOR ^ ^WASTEWATEH J»
STEAM ^~^ — J • rurMtrAi *i
GENERATING ^i LHimiAli
tout* /* ^s .T. . PMCE THROUGH
/ \ • " " " COOLING JATER
\ /» . »
\ J \ 1 * *
S^^^^^/ , . \ COOLING TOWER /
•• ' - \ 1
DISCHARGE TO m \ 1
WATER BOOT W 1 /r»»WrCHEMICALS
CONDENSATC WATER \ &
* MAKEUP HATER v' 'f
IT 1 «
1. .-.-, 1
SANITARY WASTES
LABORATORY 1 SAMPLING
WASTES. INTAKE SCREEN
BACKWASH, CLOSED COOLING
WATER SYSTEMS. CONSTRUC-
TION ACTIVITY
IEGENQ:
LIQUID FLOW
GAS t STEAM FLOM
OPTIONAL FLON
• UASTEWATER
Figure 19-1. Fossil-fueled steam-electric power plant - typical flow diagram.
-------
o
Q>
ft
0>
to
U)
00
o
I
I-1
o
TABLE 19-5. WASTEWATER FLOWRATES [1, 4]
Waste stream
1 Condenser cooling water
Once-through
Recirculating
2 Water treatment
Clarification
Coal
Gas
OU
Softening
Coal
Gas
Oil
Ion exchange
Coal
Gas
Oil
Evaporation
Coal
Gas
Oil
Filtration
Coal
Gas
Oil
Reverse osmosis
Coal
Gas
3. Boiler blovdovn
Coal
Gas
Oil
4. Maintenance (chemical) cleaning
Boiler tubes
Boiler fireside
Coal
Gas
Oil
Number
of
plants
-
S
88
26
14
37
40
15
104
86
42
104
83
57
155
58
58
3
11
231
189
148
7
42
40
81
Flowrate, i»3/d (qpd)
53
0.026
0 038
0.076
0.11
0.057
0.28
0.055
0.026
0.061
0.0076
0.030
0.057
0.0061
0.15
0.11
0.011
1.76
0 . 00042
0.015
0.010
570
0.010
0.0011
0.052
1.100
- 2,300
- 4,500
- 380
- 190
- 3.400
- 840
- 400
- 620
- 500
- 3,600
- 810
- 60,000
- 1,100
- 360
- 950
- 120
- 360
- 2,500
- 2,600
- 14,000
- 19,000
- 77
- 10
- 130
Range
-
(14.000
(7
(10
(20
(29
(15
(75
(14
(7
(16
(2
(8
(15
(1.6
(40
(20
(3
(470
(0.11
(4
(2.7
(150,000
(2.7
(0.3
(14
Median
- 280,000)
- 60,000)
- 1,200,000)
- 100,000)
- 50,000)
- 900,000)
- 220,000)
- 100,000)
- 160,000)
- 130,000)
- 960,000)
- 220,000)
- 15,000,000)
- 300,000)
- 94,000)
- 250,000)
- 32,000)
- 95,000)
- 650,000)
- 700,000)
- 3,800,000)
- 4,900,000)
- 20,000)
- 2,700)
- 36,000)
240
102
210
75
99
117
60
35
42
73
110
52
1,200
97
30
95
40
69
130
73
250
870
10
1.9
13
-
(63,000)
(27,000)
(58,000)
(20,000)
(26.000)
(31,000)
(16,000)
(9,300)
(11,000)
(19,000)
(29,000)
(13,000)
(320,000)
(25,000)
(7,800)
(25,000)
(11,000)
(18,000)
(33,000)
(19,000)
(66,000)
(230,000)
(2,700)
(510)
(3,400)
Freguency Remarks
-
Slowdown depends on waf.pr
guality and varies ft on
2 to 20 concentrations
_
52-365 cycles/yr Extremely variable depending
300-365 cycles/yr Extremely variable depending
_
.
25-365 cycles/yr
Once/7-100 mo
2-8 yr
(continued)
-------
G
0>
rt
rO
U)
00
o
TABLE 19-5 (continued).
Waste stream
4 Maintenance (chemical) cleaning
(continued)
Coal (total)
Gas (total)
Oil (total)
Co 1, 25-MW capacity
Co 1, 100-MW capacity
Co 1, 500-MW capacity
Ga , 25-MW capacity
Ga , 100-MW capacity
Ga , 500-MW capacity
Oil, 25-MW capacity
Oil, 25-MW capacity
Oil, 100-MW capacity
Oil, 500-MW capacity
Oil, 500-MW capacity
Miscellaneous small equipment
Stack
Number
of
plants
148
56
110
3
16
54
8
12
23
13
7
8
52
43
-
-
Flowrate, m3/d (gpd)
Range
0.010 -
0.0010 -
0.0053 -
0.021 -
0 021 -
0.010 -
0.016 -
0.0010 -
0 0020 -
0.026 -
0 0051 -
0.45 -
0.017 -
0.11 -
590
37
2,000
0 21
10
180
0.25
4.5
26
37
1.6
39
140
2,000
-
-
(2.7
(0.27
(1.4
(5.5
(5.5
(2.7
(4.1
(0 27
(0.56
(6.8
(1.4
(120
(4.6
(20
- 160,000)
- 9,900)
- 530,000)
- 55)
- 2,700)
- 47,000)
- 66)
- 1,200)
- 6,800)
- 9,900)
- 410)
- 10,000)
- 38,000)
- 530,000)
Median Frequency Remarks
41
3.7
40
0 091
2.9
17
0.095
0.91
4.2
7.7
0.29
7 0
11
88
4-12 yr
(11,000)
(980)
(11,000)
(25)
(760)
(4,600)
(25.2)
(240)
(1,100)
(2,000)
(77)
(1,900)
(3,000)
(23,000)
.
Cleaned infrequently
Cooling tower basin
5. Ash handling
Coal 24 1,800 - 78,000
Coal and gas 5 1,900 - 98,000
Coal and oil 4 19 - 2,700
Coal, oil, and gas 2 20,000 - 53,000
6. Drainage
Coal pile 4 3.1-360
Floor and yard drains 3 5.5-14
Ash pile
7. Air pollution control devices
Five gas scrubber blowdown
Coal (total) 13 27 - 57,000
Scrubber solids pond overflow
Coal (total) 7 0.95 - 8,700
Coal, 25-MH capacity 1
Coal, 100-MW capacity 1
Coal, 500-MW capacity 1
Coal, 500-MW capacity 4 27 - 6,200
8 Miscellaneous waste streans
Sanitary wastes
Plant laboratory and sampling
Intake screen backwash
Closed cooling systems
Low level radiation wastes
Construction activity
(480,000 - 21,000,000) 18,000 (4,700,000)
(500,000 - 26,000,000) 33,000 (8.700,000)
(4,900 - 720,000) 2,600 (690,000)
(5,200,000 - 14,000,000) 36,000 (9,600,000)
(810 - 96,000)
(1,400 - 3,600)
IS (3,900)
5.5 (1,400)
(7,000 - 15,000,000) 6,500 (1,700,000)
(250 - 2,300,000) 3,200 (840,000)
8,700 (2,300,000)
0.95 (250)
77 (20,300)
(7,000 - 1,700,000) 3,200 (850,000)
(5)
Cleaned infrequently
Flow dependent upon frequency,
duration, and intensity of
rainfall
Flow dependent upon frequency and
duration of cleaning and storm-
water runoff
Estimated flow 25-35 gal/capita
day
Nominal, variable flow
Guideline requires collection and
removal of debris; flow data
not significant
Variable, depending on treatment
technology, leakage, etc.
Flow dependent on rainfall
-------
used to control corrosion, sealing, and biological growth. The
fill material in natural draft cooling towers is normally
asbestos cement. Erosion of this fill material can result in
the discharge of asbestos from cooling water blowdown. Table
19-6 lists the toxic pollutants observed in condenser cooling
system wastewater.
II.19.2.2 Water Treatment Wastewater
Removal of dissolved and suspended salts from boiler feedwater
to prevent or reduce scaling may be accomplished by clarifica-
tion, softening, ion exchange, evaporation, filtration, or other
treatment.
Clarification agglomerates suspended solids and removes them
from water by settling. Chemicals such as aluminum sulfate,
ferrous sulfate, ferric sulfate, sodium aluminate, polyelectro-
lytes, and others are used as additives. Wastewater streams
from clarifiers usually contain 3,000 mg/L to 15,000 mg/L total
solids (of which 75% to 80% are suspended solids and the re-
mainder dissolved solids), 30 mg/L to 100 mg/L BOD, 500 mg/L to
10,000 mg/L COD, and pH of 5 to 9.
Softening removes hardness using chemical precipitation.
The two major chemicals used are calcium hydroxide and
sodium carbonate.
Ion exchange removes mineral salts in one step using an organic
resin which periodically must be regenerated. The pH of the
wastewater will vary depending on the type of system and resins
used. The neutralized wastewater is high in total dissolved
solids.
Evaporator wastewater, with a pH range of 6 to 9, contains con-
centrated salts from the feedwater.
Filtration is used after several other water treatment operations
and requires periodic backflushing.
Reverse osmosis is a process used by some plants to remove dis-
solved salts. Concentrated salt solution (brine) is discouraged
as a waste.
Table 9-7 presents pollutant concentrations observed in water
treatment wastewater streams.
II.19.2.3. Boiler or Steam Generator Blowdown Wastewater
Boiler blowdown is generally of fairly high quality because the
boiler feedwater must be maintained at high quality [2]. Boiler
blowdown having a high pH may contain a high dissolved solids
Date: 6/23/80 11.19-12
-------
a
(U
n-
a>
a\
\
10
m
o
vo
I
M
u>
TABLE 19-6.
CONDENSER COOLING SYSTEM - INTAKE AND RAW
WASTEWATER POLLUTANT CONCENTRATIONS [1]
Once through cooling water system
Intake
Discharge
NuBber lhaiber .
of Concentration of Concentration
Pollutant
Metals
Antiinny
Arsenic
Asbestos
Berylliust
CadBiua
Chroaiiuji
Copper
Cyanide
Lead
Mercury
Nickel
Seleniun
Silver
ThalliuH
Zinc
Phenol (total)
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Di-n-octyl phthalate
Phenols
2 , 4-Dichlorophenol
2,4-Dinitrophenol
Pentachlorophenol
Phenol
2,4, 6-Tr ichlorophenol
Aromatics
Benzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
1, 2 ,4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
2-Chloronaphthalene
Halogenated aliphatics
Bromoform
Chlofodibrocnome thane
1 , 2-Dichloroe thane
1, 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
plants Range Median plants Range
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
3
4
1
1
1
1
1
1
1
<5 - 7 <5
<5
<5 - <10 ling water srsten 'c
Discharge
Number
of Concentration
plants Range
3
3
14
4
8
8
8
6
7
3
8
3
6
3
6
5
5
3
1
1
3
3
3
2
1
6
2
BOL - 7
4-35
BDL - 160.000,000
BDL - <10
BDL - 200
2 - 555
34 - 3,800
BDL - <20
BDL - 800
4 - 200
0.7 - 80
BDL - 8
26 - 780
<10 - 36
<10 - 48
8-20
<10 - 26
<10 - 26
<10 - 26
13 - 150
65 - 9,400
13 - 26
Median
5
7
BOL
3.4
3
52
56
<20
<20
BDL
18
BDL
3
BDL
248
22
10
8
35.
45
20
20
20
82
59
< 1,600
18
Note: Blanks indicate no data available.
*Hetals concentrations are screening data; verification results not available. Organics derived from verification data.
Cooling tower blovdown
-------
ti-
ro
LO
00
o
H
H
VO
I
TABLE 19-7. UTILITY BOILERS - RAW WASTEWATER POLLUTION CONCENTRATIONS [3, 4]
Softening3 discharge
Parameter
Toxic pollutants, pg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Clarification Number
discharge of
Mean plants
3
3
3
Range Median
90 - 110
60 - 150
5-14
100
120
5
Ion
Number
of
plants
5
5
3
exchange
Range
discharge
Median Mean
20 - 200 70
20 - 1,300 20
<5 - 5 5
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates, pg/L
Bis(2-ethylhexyl) phthalate
Phenols, pg/L
2-Chlorophenol
2,4-Dichlorophenol
Phenol
Aromatics, pg/L
Benzene
1,3-Dichlorobenzene
Ethylbenzene
Toluene
Halogenated aliphatics, pg/L
Chloroform
Methylene chloride
Nontoxic pollutants, pg/L
Aluminum
Barium
Calcium
Iron
Magnesium
Manganese
Phosphorus
Potassium
Sodium
Tin
70 - 250
90 - 320
90
120
30 - 200
20 - 210
30
50
350,000
440 - 10,000
9,000
20 - 9,500
1,000
3,100
-------
o
fu
rt
ro
OJ
CD
o
TABLE 19-7 (continued)
H
VO
I
I-1
Ol
Softening3 discharge
Ion exchange discharge
Clarification Number Number
Parameter
Conventional parameters6
Ammonia
BODS
Bromide
Chloride
COD K
Flowh
Fluoride
Oil and grease
PH9
Phenols
Silica
Sulfate
TDS
TOC
TSS
Parameter
Toxic pollutants, pg/L
Antimony
Arsenic -
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates, pg/L
Bi s ( 2 -ethylhexyl ) phthal ate
Phenols, \ig/L
2-Chlorophenol
2 , 4-Dichlorophenol
Phenol
discharge of
of
Mean plants Range Median plants Range Median
3 1.8-48 10 3
3
3 37 - 560 200 3
320 3 7,500 - 17,000 16,000 4
3 1.0 1.0 5
3 190 - 23,000 1,000 3
25,000 3 40 - 9,400 1,800 4
Evaporation0 discharge Filtration
Number Number
of of
plants Range Median Mean plants Range
1
1
1
1
1
2 200 - 80 50 1
2 20 - 2,600 1,300 1
2 6-28 17 1
1
1
2 30 1
1
1
1
2 110 - 440 280 1
1
1
1
1.0 - 6.0 1.0
0.03 - 1.5 1.0
2.0 - 14 9.8
4,300 - 23,000 8,200
1.0 - 13 1.0
0.16 - 4,000 170
1.0 - 31 23
Mean
46
1,700
2,100
, Other treatment-revecse
discharge osmosis discharge
Number
of
Median plants Range
(<5,000) <5,000 1
(<13,000) 14,000 1
(0) 0 1
(<5,000) <5,000 1
(<5,000) <5,000 1
(<5,000) 21,000 1
(<5,000) 40,000 1
(<20,000) 30,000 1
(<5,000) 20,000 1
(0.390) 390 1
(<5,000) 28,000 1
(20,000) 12,000 1
(<5,000) <5,000 1
(<5,000) <5,000 1
(<5,000) 41,000 1
(1) <1 1
1
(<1) 243
(253) 13 1
Median
(<5,000)<5,000
(<5,000)<5,000
(0) 0
(<5,000)<5,000
(<5,000)<5,000
(<5,000)<5,000
(10,000)30,000
(20,000)30,000
(<5,000)<5,000
(530) 550
(<5,000)<5,000
(13,000)58,000
(9,000)<5,000
(<5,000)<5,000
(13,000)14,000
(1) <1
(<1) 27
(50) 1
-------
rt
(D
to
U)
00
o
TABLE 19-7 (continued).
H
H
VO
M
(TV
Evaporation0 discharge
Number
of
Parameter plants Range Median Mean
Aromatics , \> g/L
Benzene
1 , 3-Dichlorobenzene
Ethylbenzene
Toluene
Halogenated aliphatics, pg/L
Chloroform
Methylene chloride
Nontoxic pollutants, M9/L
Aluminum
Barium
Calcium
Iron 2 220 - 380 300
Magnesium
Manganese
Phosphorus
Potassium
Sodium
Tin
Conventional parameters
Ammonia
BOD5 2 5.1-15 10
Bromide
Chloride 190
COD . 2 21 - 76 48
Flow11 41,000
Fluoride
Oil and grease 2 1.0-1.9 1.5
pH9
Phenols
Silica
Sulfate 79
TDS 2 2,200 - 2,500 2,400
TOC
TSS 2 15-93 54
, Other treatment-reverse
Filtration discharge osmosis discharge
Number Number
of of
plants Range Median plants Range Median
1 (3) 2
1 (
-------
concentration depending on boiler pressure. Slowdown from boil-
ers treated with phosphate will contain hydroxide alkalinity
while those treated with hydrazine will contain ammonia and,
depending on boiler pressure, sulfite. Table 19-8 presents raw
waste concentrations for boiler blowdown wastewater streams.
TABLE 19-8. BOILER OR STEAM GENERATOR BLOWDOWN - RAW
WASTEWATER POLLUTION CONCENTRATIONS [4]
Boiler blowdown discharge
Number
of
Parameter plants Range Median
Toxic pollutants, ng/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium 4 20
Copper 4 20 - .190 40
Cyanide 2 5-14 10
Lead
Mercury
Nickel 4 30
Selenium
Silver
Thallium
Zinc 4 10-50 20
Conventional parameters, mg/L
BOD5
COD
Iron
Oil and grease
pn
TDS
TSS
2
2
4
2
4
2
4
11
2.0
0.03
1.0
9.0
120
2.7
- 12
- 157
- 1.4
- 15
- 12
- 1,410
- 31
11
80
0.06
7.9
10
760
7.6
lote:Blanks indicate no data available.
dValues in fibers/liter.
bValues in pH units.
Date: 6/23/80 11.19-17
-------
II.19.2.4 Maintenance Cleaning Wastewater
Boiler tubes must be cleaned occasionally to remove accumulations
of scale. Cleaning mixtures used for this purpose include alka-
line chelating rinses, proprietary chelating rinses, organic
solvents, acid cleaning mixtures, and alkaline mixtures with
oxidizing agents for copper removal. Wastes from these cleaning
operations will contain iron, copper, zinc, nickel, chromium,
hardness, and phosphates. In addition to these constituents,
wastes from alkaline cleaning mixtures will contain ammonium
ions, oxidizing agents, and high alkalinity; wastes from acid
cleaning mixtures will contain fluorides, high acidity, and
organic compounds; wastes from alkaline chelating rinses will
contain high alkalinity and organic compounds; and wastes from
most proprietary processes will be alkaline and will contain
organic and ammonium compounds. Pollutants observed in selected
boiler tube wastewater streams are presented in Table 19-9.
Table 19-10 presents pollutant concentrations observed for boiler
fireside and air preheater wastewater streams. No data were
available to describe wastewater streams generated by stack,
cooling tower basin, and small equipment cleaning.
II.19.2.5 Ash Handling Wastewater
Ash handling is the conveyance of accumulated waste products to
a disposal system. Table 19-11 presents pollutant concentrations
observed in ash handling wastewater during a verification study
of ash pond overflows.
II.19.2.6 Drainage Wastewaters
Rainfall can become a wastewater stream after running through
coal piles, floor and yard drains, or ash piles. Table 19-12
presents data on coal pile runoff and floor and yard drains.
Data on ash pile wastewater streams are not available.
II.19.2.7 Air Pollution (SO2) Control Wastewater
Wastewater characteristics of streams from air pollution control
devices will depend on the type of process used. Existing flue
gas desulfurization (FGD) processes may be divided into two
categories: nonregenerable (throwaway) and regenerable. Non-
regenerable FGD processes include lime, limestone, lime/limestone
combinations, and double alkaline systems. Magnesium oxide and
Wellman-Lord are the regenerable processes. Tables 19-13 and
19-14 present pollutant concentrations for selected nonregener-
able FGD wastewater streams. There are no wastewater or sludge
streams associated with the Wellman-Lord process. No data are
available to describe magnesium oxide wastewater streams.
Date: 6/23/80 11.19-18
-------
o
(a
rt
CD
CTi
OJ
CO
o
TABLE 19-9.
H
H
I
I-1
VD
MAINTENANCE CLEANING-BOILER OR GENERATOR TUBE WASH
SOLUTIONS-RAW WASTEWATER POLLUTANT CONCENTRATIONS [1]
Ammonia ted citric acid discharge
Number
of
Parameter operations Range Median
Toxic pollutants, pg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper 4 8,000 - 220,000 20,000
Cyanide
Lead
Mercury
Nickel 1 130,000
Selenium
Silver
Thallium
Zinc 1 390,000
Nontoxic pollutants, M9/L
Aluminum
Barium
Calcium
Iron 3 8,300,000 - 11,000,000 9,800,000
Manganese
Magnesium
Phosphorus 1 200,000
Potassium
Sodium
Tin .
Conventional parameters, mg/L
PH
TDS
TSS
BOD5
COD
TOC
Oil and grease
Phenols
NH3-N
Org-N
N02+N03-N
Silica 1 40
Bromide
Chloride
Fluoride
Sulfate
Ammoniated EDTA discharge
Number
of
operations Range
3 10,000 - 27,000
7 170 - 12,000,000
3 12,000 - 140,000
3 79,000 - 140,000
1
2 21,000 - 45,000
7 2,300,000 - 8,300,000 6
2 50,000 - 73,000
2 11,000 - 21,000
1
1
7 8.8-10
2 60,000 - 74,000
1
1
1
1
Median
12,000
120,000
120,000
31,000
33,000
,900,000
61,000
16,000
260,000
370,000
9.2
67,000
24
41
5,200
94
(continued)
-------
o
pj
n-
(D
ro
U)
c»
o
TABLE 19-9 (continued)
VD
I
NJ
O
Ammoniacal sodium bromate discharge
Number
of a
Parameter operations Range
Toxic pollutants, pg/L
Antimony
Arsenic
Asbestosc
Beryllium
Cadmium
Chromium
Coppe r
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Nontoxic pollutants, pg/L
Aluminum
Barium
Calcium
Iron
Manganese
Magnesium
Phosphorus
Potassium
Sodium
Tin
Conventional parameters, mq/L
PH
TDS
TSS
BOD 5
COD
TOC
Oil and grease
Phenols
NH3-N
Org-N
NO2+N03-N
Silica
Bromide
Chloride
Fluoride
Sulfate
3
2
3
4
6
3
3
5
3
2
5
2
2
3
5
3
3
2
2
3
2
2
3
3
2
2
2
2
2
2
2
1
2
<5
<1
ND
100,000
<10
<.02
ND
<2
<10
0.050
- 310,000
10
- <20
- <50
- 790,000
- 100
- 15,000
- 260,000
- 24,000
- 20
- 1,000
200
100
ND
ND
10
ND
10,000
70,000
3,700
<1
10
340
8
24
700
<10
0.04
7.2
<5
1.5
-3,000
- 4,900
- 40
- 2,900
- 30,000
- 220,000
- 59,000
,000
- 11
- 1.400
- 77
- 120
<5
- 2,000
- 40
- 0.51
- 14
- 52
- 6.1
Hydrochloric acid without
copper complexer discharge
.Number
of
Median operations Range
48
<10
<1
<5
<10
<.02
520
<2
20
500
<200
<100
400
1,700
30
670
20 , 000
150,000
15,000
10
1,000
71
72
<5
1,000
25
0.27
11
28
60
3.8
6
4
6
6
7
5
4
7
4
4
7
4
4
6
7
6
4
6
4
4
4
6
6
6
6
6
6
6
6
4
5
4
8
<
<1
<5
690
<10
770
<2
20
940
6,500
<100
16,000
1,100,000
6,900
5,700
1,200
1,400
31,000
<1,000
0.5
8
1,200
90
<5
0.020
80
0.06
<0.01
19
<1
- 60
:10
- 100
- 8,800
- 47,000
- 5,200
<2
- 300,000
- <4
- 70
- 370,000
- 8,200
- 400
- 74,000
- 4,200,000
- 29,000
- 8,800
- 50,000
- 2,300
- 74,000
- 7,300
- 3.3
- 120
- 9,900
- 4,600
- 23
- 0.070
- 330
- 870
- 0.07
- 240
- 10
Median
1
13
160
20
6
59
2,800
21
7
40
1
45
1
1
0
33
<10
21
,300
,000
860
<2
,000
<2
30
,000
,800
200
,000
,000
,000
,600
,000
,700
,000
,900
0.7
34
,500
230
16
.043
190
108
<0.01
66
<1
(continued)
-------
D
D>
rt
to
oo
oo
o
vo
I
Parameter
TABLE 19-9 (continued)
Hydrochloric acid with
copper complexer discharge
Number
of
operations Range Median
Hydroxyacetic/formic
acid discharge
Number
of
operations
Range
Median
Toxic pollutants, pg/L
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium 1
Copper 6
Cyanide
Lead
Mercury
Nickel 5
Selenium
Silver
Thallium
Zinc 4
Nontoxic pollutants, pg/L
Aluminum
Barium
Calcium 2
Iron 6
Manganese 1
Magnesium
Phosphorus 2
Potassium
Sodium 1
Tin b
Conventional parameters, mg/L
17,000
20,000 - 960,000 370,000 1
3,000 - 500,000 270,000 1
10,000 - 840,000 410,000 1
67,000 - 980,000 520,000
1,900,000 - 6,500,000 3,900,000
8,200
100,000 - 300,000
200,000
9,200
2,000
5,00
8,000
2,900,00 - 8,800,00 4,600,000
TDS
TSS
BOD5
COD"
TOC
Oil and grease
Phenols
NH3~N
Org-N
NO2+N03-N
Silica
Bromide
Chloride
Fluoride
Sulfate
2,400
30 - 280
160
Note: Blanks indicate no data available
aNumber of independent boiler chemical cleaning operations.
Except as noted.
GValues in Fibers/liter.
values in pHunits.
-------
ft
(D
TABLE 19-10. MAINTENANCE CLEANING - BOILER FIRESIDE AND AIR PREHEATER [1]
00
o
H
I
tsj
NJ
Parameter
Toxic pollutants, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium (total)
Chromium 6
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Boiler
Concentration
Maximum Mean
15,000 1,
<1,000
250,000 6,
900,000 70,
40,000 4,
fireside wash
Mean loading,
kg/cleaning
(Ib/cleaning)
500 6.8 (15)
20 0.09 (0.2)
000 27 (60)
000 317 (700)
000 18 (40)
Air preheater.
Air preheater wash water and fireside wash
Number of Concentration concentration
operations Range Median Intake Discharge
6
6 20
3 1,000 - 1,500 1,300 10 200
7 200
03 600
3 18,000 - 25,000 21,000 BDL 100
3 1,100 - 1,400 1,200 BDL 900
Nontoxic pollutants, pg/L
Aluminum 21,000
Calcium
Iron 14,000,000 2
Magnesium
Manganese 40,000
Sodium
Conventional parameters, mg/L
pHC
TDS
TSS
COD
Chloride
Sulfate
Oil and grease
Total hardness, as CaC03
50,000
25,000
10,000
BDL
2,000
,500,000
3,500
5,000
250
1,000
BDL
9 (20)
11,000 (25,000)
16 (35)
23,000 (50,000)
1,100 (2,500)
4,500 (10,000)
BDL
3
3
3
3
3
3
3
3
3
3
3
29,000
260,000
360,000
3.2
606
29
50
17
1,900
0.25
1,400
- 38,000
- 330,000
- 380,000
- 3.5
- 750
- 83
- 70
- 27
- 2,700
- 8.5
- 1,600
34,000
330,000
370,000
3.5
730
34
60
19
2,300
0.25
1,500
Note: Blanks indicate data not available.
Data from one plant.
Verification data.
Values in pH units.
-------
o
0)
ft
(D
CTi
NJ
U)
00
o
TABLE 19-11. ASH HANDLING - INTAKE, INFLUENT, AND EFFLUENT POLLUTANT CONCENTRATIONS [1]
H
V£>
I
U>
.
Influent
Number
of
Pollutant plants Range Median
Metals,pg/L
Antimony
Arsenic
Asbestos0
Beryllium 6 2-30 6
Cadmium 6 8 - 100 45
Chromium 6 60 - 900 200
Copper 6 50 - 200 100
Cyanide
Lead 6 50 - 1,000 200
Mercury
Nickel 6 20 - 500 95
Selenium
Silver 3 2-20 8
Thallium
Zinc 6 100 - 900 500
Phthalates, pg/L
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate 1 65
Diethyl phthalate
Di-n-octyl phthalate
Phenols , pg/L
2,4-Dichlorophenol
2 , 4-Dinitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Aromatics, pg/L
1 , 2-Dichlorobenzene
1,3-Dichlorobenzene 1 35
1 , 4-Dichlorobenzene
1 , 2 ,4-Trichlorobenzene
Polycyclic aromatic hydrocarbons, pg/L
Acenaphthylene 1 16
2-Chloronaphthalene
Halogenated aliphatics, pg/L
1 , 2-Dichloroe thane
Methylene chloride 1 5,400
Bottom
Ash"'"
Effluent
Number
of
plants
3
3
5
5
8
8
8
8
6
8
3
4
3
8
6
1
3
1
1
1
5
2
2
2
1
1
6
Range
5 -
BDL -
BDL -
BDL -
BDL -
13 -
BDL -
BDL -
BDL -
2.5 -
3 -
0.5 -
BDL -
BDL -
21 -
31 -
6 -
64 -
64 -
64 -
300 -
7
74
2.5
10
1,000
80
22
30
1.5
490
42
6
9
300
309
46
40
65
65
65
9,400
Median
6
9
<1.0
2
9
26
<20
13
<0.5
14
8
3.3
BDL
<60
22
10
36
83
50
51
14
65
65
65
52
27
>1,800
Number
of
plants
3
2
2
4
6
7
2
4
1
8
3
4
1
6
2
1
4
1
1
3
3
5
2
3
3
3
1
1
1
Intake
Range Median
3-7 4
BDL - 3
BDL - <1
BDL - 40 2
BDL - 2,000 9
<6 - 700 16
4-5 5
9-20 13
<0.5
BDL - 1,000 9
BDL - 2 2
BDL - 1.6 1.2
BDL
15 - 70 57
<10 - 21 16
<10
<10 - 33 <10
<10
<10
<25
<25
6-36 12
<25 28 27
-------
rt
(D
TABLE 19-11 (continued).
N)
U>
\
00
o
H
I
to
Influent
Pollutant
Metalsc
Antimony
Arsenic
Asbestos
Berylliun.
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Number
of
plants
2
2
2
2
2
2
2
2
Range
30 -
80 -
400 -
400 -
400 -
10 -
8.000 -
400
200
2,000
2,000
2,000
100
Median
215
140
1,200
1,200
4,000
1,200
55
10,000 9,000
Number
of
plants
1
2
2
2
2
2
2
Fly Asha
Effluent
Range
9-49
12 - 19
23 - 70
32 - 75
<60 - 1,200
Median
90
29
16
47
<0.5
54
630
Number
of
plants
1
2
2
1
2
2
Intake
Range Median
<2
12 - 2,000 1,000
13 - 90 52
15
<5 - 1,000 520
<60
Phthalates,
Bis(2-«thylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Di-n-octyl phthalate
Phenols, ug/L
2,4-Dichlorophenol
2,4-Oinitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Aromatics, ug/L
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2,4-Trichlorobenzene
Polycyclic aromatic hydrocarbons,
Acenaphthylene
2-Chloronaphthalene
Halogenated aliphatics, ug/L
1,2-Dichloroethane
Hethylene chloride
46
17 - 25
7-48
21
28
35
41
41
41
<10 - 42
26
38
>140 - >9,400 >4,800
Note: Blanks indicate no data available.
'verification data.
Coal-fueled plants only.
cvalues in fibers/liter.
-------
o
(U
ct
(D
CO
o
I
N>
cn
TABLE 19-12. DRAINAGE - RAW WASTEWATER POLLUTION CONCENTRATIONS [2]
Coal pile drainage dischar
Number
of
Parameter plants Range
Toxic pollutants, Mg/L
Antijnony
Arsenic
Asbestos0
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Nontoxic pollutants, mg/L
Aluminum
Barium
Calcium
Iron
Manganese
Magnesium
Phosphorus
Potassium
Sodium
Tin
Conventional parameters
pHd
TDS
TSS
BOD5
COD
Bromide
Chloride
Fluoride
Sulfate
Ammonia
Nitrate
Alkalinity, as CaCO
Acidity, as CaCO3
Total hardness
Oil and grease
Phenols
Flow
6
4
7
2
9
2
3
9
7
7
4
5
4
8
5
5
8
5
4
(D
(D
(1) ND -
(1) 1,600 -
(D
(1) 6 -
S30 -
60 -
89,000 -
160,000 -
2.1 -
250 -
22 -
0 -
85 -
3.6 -
130 -
0 -
0.3 -
0 -
8.7 -
130 -
17,000
3,400
23.000
1,200
93,000,000
170,000
1,300,000
7.8
44,000
3,300
10
1,100
480
22,000
1.8
2.3
82
27,000
1,900
Floor and yard drains
qe
Number
of
Median plants
(4)
(10)
1,800 (200)
1,700 (10)
(900)
1,600 (1,000)
900
1,300,000
3
5,800
610
1.5
1,100
13
3,046
0.35
1.8
10.2
10.3
620
Discharge
Number
of
Range Median plants
1
1
3
3
3
3
3
3
1
3
3
3
1
1
3
20
10
Low - Neutral
75 - 180 180
0-5 5
2-4 4
2-4 4
8-10 10
1.3
0.01 - 0.07 0.07
0.5 - 2 0.5
14 - 35 35
5
0.001
5.5 - 14 5.5
1
1
3
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Intake
Range Median
20
55
4-10 4
40
30
1,000
4,000 - 5,000 4,000
70 - 180 180
0-5 0
2-4 4
2-4 4
8-10 10
0.5 - 1.3 0.5
0.01 - 0.07 0.07
0.5 - 2.1 0.5
14 - 35 35
7-29 29
1-4 4
1
"verification data in parentheses.
bExcept as noted.
GValues in fibers/liter.
"Values in pH units.
'Values in »3/d.
Note: Blanks indicate no data available.
-------
II.19.2.8 Miscellaneous Waste Streams
The amount of sanitary wastewater depends on the number of people
at the plant, which depends on the size, age, and type of plant.
Such water is very similar to municipal wastewater except that
it does not normally contain laundry or kitchen wastes. Table
19-15 presents estimated pollutant concentrations for sanitary
wastewater streams on a per capita basis.
Wastewater from laboratories varies depending on the use of the
facilities and type of power plant.
Characteristics of wastewater from backwash of the intake screen
depend on the debris in the source water.
Closed cooling water systems have blowdown with a 1 mg/L to 2 mg/L
settleable solids content.
Low level radioactive wastewaters contain boron. The concentra-
tion and flow discharged depends on the type of water system at
the reactor.
Construction activity will generate wastewaters whose types and
amounts depend on the size and nature of the activity. Table
19-16 presents pollutant concentrations associated with construc-
tion activity at a number of selected sites.
II.19.3 PLANT SPECIFIC DESCRIPTION [1, 4]
Tables 19-17 through 19-26 present pollutant data for selected
steam electric power plants. As data for all subcategories were
not available for all plants, individual plants were chosen to
represent as many subcategories as possible. Verification data
were used unless otherwise noted. Analyses of verification
samples were performed by Richardson, Radian, GSR1, and Chicago.
Detection limits for these contractors are listed below:
Richardson Limit,
Acid extractables 25
Base-neutral compounds 10
Phenols 5
Richardson and Chicago Limit,
Zinc 60
Antimony 25
Arsenic 25
Selenium 25
Cyanide 20
Lead 20
Thallium 10
Copper 6
Date: 6/23/80 11.19-26
-------
TABLE 19-13.
AIR POLLUTION CONTROL DEVICES - NONREGENERABLE FLUE
GAS DESULFURIZATION (FGD) PROCESSES - RAW WASTEWATER
POLLUTANT CONCENTRATIONS [1]
Hist eliminator wash water
(wet limestone) discharge
concentration
Flowrate. L/min/m2
Parameter
Toxic pollutants, pg/L
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Nontoxic pollutants, pg/L
Aluminum
Barium
Boron
Calcium
Cobalt
Iron
Manganese
Magnesium
Molybdenum
Potassium
Sodium
Tin
Vanadium
40.7
2
10
42
<50
20
<10
33
<0.2
<50
12
<10
70
<200
<100
220,000
5,800
160
6,500
2,200
8,100
20.35
2
<10
13
<50
20
<10
11
<0.2
<50
24
<10
20
<200
<100
440,000
70
140
8,300
3,000
8,800
10.18
10
<10
31
<50
30
<10
16
<0.2
<50
<10
140
<200
<100
430,000
5,500
370
18,000
2,600
11,000
Bleed stream (wet
line/limestone)
discharge
concentration
range
90
<4
<2
4
10
<2
10
0.4
50
<1
10
10
30
8,000
520,000
1,000
200
90
3,000
910
5,900
14,000
3,100
1
- 2,300
- 300
- 140
- 110
- 500
- 200
- 400
- 70
- 1,500
- 2,200
- 600
- 350
- 300
- 46,000
- 3,000,000
- 700
- 8,100
- 2,500
- 2,700,000
- 6,300
- 32,000
- 2,400,000
- 3,500
- 670
Sludges - lime/limestone and
double-alkali systemb discharge
Concentration
range
4
2
4
15
2
10
0.4
0.6
10
30
180,000
4,000
5,900
10,000
- 1,800
- 180
- 110
- 500
- 560
- 520
- 70
- 2,700
- 590
- 2,000
- 2,600,000
- 2,800,000
- 100,000
- 28,000,000
Loading
range, mg/kg
0.6
0.05
0.08
10
8
0.23
0.001
2
45
105,000
0
- 52
- 6
- 4
- 250
- 76
- 21
- 5
- 17
- 430
- 270,000
- 48,000
Conventional parameters, mg/Lc
pH
TDS
COD
Alkalinity, as CaCC3
Acidity, as CaC03
Conductance
Turbidity
Silica
Fluoride
Chloride
Sulfate
Sulfite
Ammonia
Phosphate
3.1
1,000
580
64
1,300
-------
o
0)
ft
to
CO
oo
o
H
H
vo
I
NJ
00
TABLE 19-14.
POLLUTION CONTROL DEVICES - NONREGENERABLE FGD PROCESSES
INFLUENT AND TREATED EFFLUENT MEDIAN CONCENTRATIONS [1]'
- SETTLING POND
Parameter
Toxic pollutants, (jg/L
Arsenic
Lead
Mercury
Selenium
Nontoxic pollutants, Mg/L
Boron
Calcium
Magnesium
Sodium
Conventional parameters.
mg/LC
pHd
TDS
TSS
COD
Alkalinity, as CaC03
Conductivity
Chloride
Sulfate
Sulfite
Pond
Input
liquor
24
10
0.5
2
16,000
2,000,000
210,000
68
8.2
7,110
16°
2°b
81b
10.0
3,604
1,400
32
A
Supernate
5
16
0.0002
2
5,500
880,000
20,000
8.0
2,800
9
37
49
3.2
630
1,100
0.8°
Pond
Input
liquor
l,400,000b
390,000°
38,000
7.1b
6,100°
h
5.4°
2,400.
1,700*,
120°
B
Supernate
5
20
1
21
60,000
1,700,000
900
34,000
9.6
2,200
8
43
190
8.3
1,500
900
70
Input
liquor
2,600
240
60
8.1
9,000
8.2
Pond C
Supernate
6
26
0.2
3,
300
470,000
1,700
? 11
1,600
9
19
b 10°
2.4
4,200, 500
1,600
80
b 2°°b
° 0.85°
Pond
Input
liquor
240
260
0.1
90,000°
1,300,000
260,000
8.2
5,900
5.2
1,800
2,300
D
Supernate
70
10
0.2
43,000
910,000
96,000
8.4
3,400
98
19
97
3.9
980
1,000
Analyses of input liquors to four disposal ponds and subsequent supernates at one plant. All four disposal
ponds were filled with effluents representing a cross section of lime or limestone scrubber effluent conditions.
Median derived from less than three plants.
c
Values in mg/L except as noted.
values in pH units.
Values in umhos/cm.
-------
TABLE 19-15. MISCELLANEOUS WASTE STREAMS - SANITARY WASTES
- RAW WASTEWATER POLLUTANT CONCENTRATIONS [3]
Location
Office-administrative
(per capita)
Plant (per capita)
Flow, ma/d
(gpd)
0.095
(25)
0.13
(35)
db)
30
(0.071)
40
(0.09)
TSS, g
70
(0.15)
85
(0.19)
TABLE 19-16.
MISCELLANEOUS WASTE STREAMS - CONSTRUCTION ACTIVITY
- RAW WASTEWATER POLLUTANT CONCENTRATIONS [1]
Location
Number
of Median
days pH
Median
turbulence ,
JTU
Median
TSS,
mg/L
Bellefonte Construction
Drainage ditch, foot of Barge Dock Road
West drainage ditch culvert at project entrance road
East drainage ditch culvert at project entrance road
Settling pond effluent, Town Creek 2.9
Settling pond effluent. Town Creek 3.0
Drainage ditch, foot of Bellefonte Road
Intake cofferdam pump discharge
Permanent pond influent, east ditch9
Permanent pond influent, west ditch
Permanent pond influent, southwest ditch
Construction pond influent, permanent pond effluent8
Construction pond influent, berm ditch
Construction pond effluent
Hartsville Construction
Corley Branch 0.03
Mouth of unnamed tributary at CRM 283.52
Mouth of unnamed tributary at CRM 284.8
Mouth of unnamed tributary at Dixon Creek 0.46
Mouth of unnamed tributary at Dixon Creek 1.06
Monitoring
11 7.5
12
30 7.6
36
38 7.8
46
33 7.8
40
39
5 7.1
11 7.40
13
12
3 7.6
6
12
12
6
12
8
12
Monitoring
13 7.6
13 7.6
9 7.5
4 8.0
4 7.8
5
25
25
80
37
10
11
130
1,100
150
16
29
270
60
9.8
14
31
16
23
36
25
75
30
6
15
120
1,700
170
20
32
400
62
15
16
38
13
26
apH data not available.
Date: 6/23/80
11.19-29
-------
TABLE 19-17.
WASTEWATER CHARACTERIZATION, PLANT 0630 [1]
(jjg/L)
Fuel: Oil and gas
Capacity: 169 MW
Pollutant
Cooling
tower
intake
Cooling
tower
effluent'
Reverse
osmosis
intake
Reverse
osmosis
effluent0
Metals
Antimony < 5
Arsenic <5
Beryllium <5
Cadmium 10
Chromium 37
Copper 25
Cyanide 130
Lead <5
Mercury 0,
Nickel 8
Selenium <5
Silver 9
Thallium <5
Zinc 41
Phenol (total) 20
Phenols
2-Chlorophenol <1
2,4-Dichlorophenol <1
Phenol 30
Aromatics
Toluene <1
Halogenated aliphatics
Chloroform <1
Methylene chloride 15
41
6
13
<5
25
75
150
360
17
0,
100
23
32
<5
67
40
15
<1
21
91
<5
<5
<5
<5
<5
10
20
<5
0
<5
13
9
<5
13
10
255
<1
3
3
53
<5
<5
<5
<5
<5
30
30
<5
0.55
<5
58
<5
<5
14
20
27
240
13
150
5.2
1.4
Note: All unlisted organics were found in concentrations of
less than 1 pg/L.
aScreening data: Values for organics are blank adjusted
(composite sample concentration minus blank concentration).
Metals concentrations are from grab samples.
Date: 6/23/80
11.19-30
-------
rt
(D
to
u>
00
o
TABLE 19-18. WASTEWATER CHARACTERIZATION, PLANT 1226 [1]
Water source. Wells
Fuel: Bituminous coal, oil, and gas
Capacity: 1,229 MW
Pollutant
Metals
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Phenols
2,4-Dinitrophenol
Phenol
Halogenated aliphatics
Bromoform
Chlorodibromome thane
Hethylene chloride
1,1, 1-Trichloroe thane
7
4
BDL
1.8
5
47
BDL
3
BDL
6
BDL
0.7
BDL
26
150
59
Cooling tower blowdown
Chicago
Radian Richardson GSR1 (total)
(7)
(3)
(2.1)
(7) 28 20 (7)
(12) 6 (10) 50 (10)
BDL
(10)
BDL
(1-5)
(1-3)
(9) 50 BDL (70)
22b
10
8 (12)
(BDL)
(BDL)
>1,800
7
9
BDL
2
6
14
BDL
4
BDL
5.
8
0
BDL
7
Ash pond overflow - bottom ash
Chicago
Radian Richardson GSRl (total)
(7)
(3)
(2)
(7) 10 (7)
(12) 18 (10) 10 (10)
BDL
(10) 9 (12)
BDL
.5 (1.5) (27)
(BDL)
.5 (1.3)
(9) BDL (70)
21C
50 (<10)
17 (12)
300
27
Chicago
influent
(total)
9
8
300
100
200
100
8
700
Intake values given in parentheses.
Mixture of butyl benzyl and bis(2-ethylhexyl) phthalate.
Combined with di-n-octyl phthalate.
Note: Blanks indicate no data available.
Note: All unlisted organics were found in concentrations of less than 1 \tgll..
-------
TABLE 19-19. WASTEWATER CHARACTERIZATION, PLANT 1720 [1]
Fuel: Oil and gas
Capacity: 1,269 MW
Pollutant
Metals
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols (total)
Once-
through
fresh3
7
18
<5
<5
24
16
20
8
0.42
29
20
<5
<5
42
30
Fresh
intake
water8
<5
13
<5
<5
<5
<5
<20
<5
0.39
<5
20
<5
<5
<5
50
Cooling
discharge
<5
25
<5
<5
17
20
20
14
0.42
26
18
<5
<5
36
50
Filtration
plant
effluent3
<5
14
<5
5
21
40
30
20
0.39
28
12
<5
<5
41
%20
Water
treatment
wastes
7
<5
<5
<5
24
506
<20
5
0.42
9
25
37
5
<5
40
Phthalates
Bis(2-ethylhexyl) phthalate 15
Phenols
Phenol 30
Aromatics
50
<1
<1
<1
<1
<1
<1
Benzene
1 , 3-Dichlorobenzene
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
1 , 2-Trans-dichloroethylene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
Trichloroethylene
Trichlorofluorome thane
<1
<1
20
26
<1
<1
630
<1
2
2
40
3 1
<1 <1
<1 2
<1 22
7 14
<1 <1
1 24
<1 3
1 2
<1 2
<1 <1
2
1
3
46
23
<1
<1
<1
2
<1
-------
o
ft
(D
TABLE 19-20.
WASTEWATER CHARACTERIZATION, PLANT 1741 [1]
(pg/L)
to
OJ
co
o
Water source: River
Fuel: Bituminous coal and oil
Capacity: 99 MW
vo
U)
U>
Ash pond overflow9
Pollutant
Metals
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Fhthalates
Bis(Z-ethylhexyl) phthalate
Bi-n-butyl phthalate
Phenols
2 , 4-Dichlorophenol
Pentachlorophenol
Aromatics
1 , 2-Dichlorobenzenec
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene°
Halogenated aliphatics
Chloroform
1 , 2-Trans-dichloroethylene
Methylene chloride
Fly ash
Chicago
Chicago influent
Richardson GSR1 (total) (total)
30
90 (BDL) 200
12 (5) 6 (4,000) 400
15 9 (90) 400
120 (9) BDL (20) 4,000
BDL
100 (79) 50 (2,000) 400
10
1,400 1,000 (BDL) 10,000
25
40 (<10) 13
41 (<10)
41 (<10)
41 (<10)
>9,400
Bottom ash
Chicago
Chicago influent
Richardson GSR1 (total) (total)
BDL 2
10 (BDL) 10
9 (5) BDL (4,000) 60
35 10 (90) 50
BDL
14 (9) BDL (20) 50
15 (79) BDL (2,000) 20
70 (BDL) 100
309
26 (<10) 46
83 (<25)
51 (<25)
65 (<10)
65 (<10)
65 (<10)
Coal pile runoff
Chicago
Richardson GSR1 (total)
4
10
200
10
30
900
1,000
12b
32
20
20
20
17.
53d
>3,900
Intake values given in parentheses.
Combined with di-n-octyl phthalate.
Richardson did not distinguish between 1,2-, 1,3-, and 1,4-dichlorobenzene compounds.
Combination of both cis and trans forms.
Note: Blanks indicate no data available.
Note: All unlisted organics were found in concentrations of less than 1
-------
TABLE 19-21. WASTEWATER CHARACTERIZATION, PLANT 3306 [1]
Fireside wash
Concentration,
Average loading,
kg/cleaning
Parameter Maximum
Toxic pollutants
Chromium^ ( total )
Chromium 6
Copper
Nickel
Zinc
Nontoxic pollutants
Aluminum
Iron 14,
Manganese
Conventional parameters
TDS
TSS
Sulfate
Oil and grease
15,000
<1,000
250,000
900,000
40,000
21,000
000,000
40,000
50,000
25,000
10,000
Average
1,500
20
6,000
70
4,000
2,000
2,500,000
3,500
5,000
250
1,000
Virtually
(Ib/cleaning)
6.8
0.09
27
320
18
9
11,000
16
23,000
1,135
4,500
absent
(15)
(0.2)
(60)
(700)
(40)
(20)
(25,000)
(35)
(50,000)
(2,500)
(10,000)
Except conventionals, which are given in mg/L
TABLE 19-22. WASTEWATER CHARACTERIZATION, PLANT 3404 [1]
Water source: Wells
Fuel Bituminous coal and oil
apacity: 475.6 MW
Pollutant
Metals
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenol (total)
Fhtnaiates
Bis(2-ethylhexyl) phthalate
Pnenols
Pnenol
Aroroatics
Benzene
1 , 4-Dichlorobenzene
Toluene
Halogenated aliphatics
Bromoforir.
Chlorodibromome thane
Chloroform
Di chl orobromome thane
1 , 1-Dichloroethylene
Methylene chloride
Trlchlorofluoromethane
aScreening data: Values for 01
Fresh
intake
water3
<5
<5
<5
<10
<5
<5
<20
<5
0.23
<5
5
<5
<5
12
10
<1
<1
2
<1
<1
<1
1
47
17
<1
<1
<1
rganics are
Saline
intake
water
11
<5
<5
15
16
25
<20
5
0.34
21
55
40
<5
<5
36
11
<1
1
<1
3
<1
<1
3
<1
1
20
<1
blank i
Cooling
tower
blowdown
14
8
<5
40
23
13
<20
<5
0.58
29
87
64
9
<5
<10
62
<1
<1
1
3
4
3
1
<1
2
<1
1
adjusted (co
Treatment
plant
effluent
8
9
<5
10
22
30
<20
8
0.47
80
55
35
5
10
20
18
1
<1
<1
5
26
1
1
<1
1
3
<1
mposite samp
Ash
pond
effluent
12
14
<5
13
20
29
<20
5
0.32
33
42
19
<5
8
20
9
1
1
<1
3
<1
<1
<1
<1
1
4
<1
le
Slag tank
overflow
13
8
<5
25
16
23
<20
<5
0.47
21
48
41
6
5
70
16
1
1
<1
4
<1
<1
3
<1
1
1
<1
concentration minus blank concentration). Metals concentrations are from
grab samples.
Note:
Note:
Blanks indicate no data available.
All unlisted organics were found in concentrations of less than 1
Date: 6/23/80
11.19-34
-------
TABLE 19-23.
WASTEWATER CHARACTERIZATION,
PLANT 3410 [1]
Parameter
Toxic pollutants, Mg/L
Chromium
Nickel
Zinc
Nontoxic pollutants, (jg/1
Calcium
Iron
Magnesium
Sodium
Conventional parameters,
IDS
TSS
COD
P"
Oil and grease
Total hardness,
as CaCO3
Conductance
Chloride
Sulfate
Air preheater
Range
1,000 - 1,500
18,000 - 25,000
1,100 - 1,500
29,000 - 38,000
340,000 - 520,000
260,000 - 330,000
360,000 - 380,000
mg/L*
610 - 750
29 - 83
50 - 70
3.2 - 3.5
0.25 - 8.5
1,400 - 1,600
2,700 - 3,200
17 - 27
1,900 - 2,700
Median
1,300
21, 000
1,200
34,000
460,000
330,000
370,000
730
34
60
3.3
0.25
1,500
2,700
19
2,500
Except as noted.
Values in pH units.
°Values in umhos/cm.
TABLE 19-24. WASTEWATER CHARACTERIZATION, PLANT 4222 [1]
Water source: River
Fuel: Bituminous coal
Capacity: 1,500 MW
Pollutant
Metals
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenol (total)
Phthalates
Bis(2-ethylhexyl) phthalate
Halogenated aliphatics
Methylene chloride
Trlchlorofluoromethane
River
water.
intake8
<5
<5
<5
<5
<5
16
<20
<5
0.26
6
<5
<5
<5
14
<100
1
<1
<1
Det.
basin
effluent*
29
160
20
<5
11
6
<20
<5
0.21
8
32
<5
<5
10
260
<1
5
2
SIK
sluice
wastes
48
120
100
10
196
300
<20
240
0.62
250
<5
<5
29
400
<100
Storm
water
effluent
<5
<5
<5
<5
<5
6
<20
<5
0.29
21
5
<5
<5
10
<100
POTW
water
intake
<5
12
<5
<5
<5
6
<20
<5
0.36
8
5
<5
<5
23
<100
Screening data: Values for organics are blank adjusted (composite sample
concentrations minus blank concentration). Metals concentrations are from
grab samples.
Note:
Note:
Blanks indicate no data available.
All unlisted organics were found in concentrations of less than 1 pg/L.
Date: 6/23/80
II.19-35
-------
rt
fD
TABLE 19-25. WASTEWATER CHARACTERIZATION, PLANT 6387 [4]
to
OJ
oo
o
V£>
I
00
Lime softner
blowdown
Parameter
Conventional and Nonconventional
pollutants, mg/L
BOD5
COD
TDS
TSS
TS
Oil and grease
Phosphate
Surfactants
Flow3
Toxic pollutants, pg/L
Chromium ( total )
Chromium 6
Copper
Cyanide
Nickel
Zinc
Nontoxic pollutants, (Jg/L
Iron
Sample 1
1.8
200
1,000
9,400
10,000
1.0
17
110
4
150
14
90
320
10,000
Sample 2
10
560
23,000
44
23.000
1.0
7.6
100
7
120
5
90
90
440
Evaporator
blowdown
15
76
2,200
93
2,300
1.0
6.2
41
20
5
20
6
110
110
380
Ash transport
blowdown
1.2
290
1,900
1,700
3,500
1.0
0.02
45
120
9
200
112
80
80
6,200
Combined
discharge to
POTW
8.4
49
240
1,700
<1.0
0.024
520
20
6
20
6
70
70
640
Note: Blanks indicate data not available.
Values in m3/d.
-------
TABLE 19-26. WASTEWATER CHARACTERIZATION, PLANT 8392 [4]
Demineralizer
regeneration
concentration ,
Parameter Mg/L
Toxic pollutants
Chromium. (total)
Chromium 6
Copper
Cyanide
Nickel
Zinc
Nontoxic pollutants
Iron
Conventional parameters
IDS
TSS
TS
BOD5
COD
Oil and grease
Bromide
Phosphate
Surfactants
Flow
20
5
20
5
30
20
70
170
1.0
170
1.0
2.0
1.0
1.0
0.05
0.011
Boiler blowdown
Concen-
tration,
Mg/L
20
9
60
14
30
20
80
120
6.9
125.0
11
2.0
1.0
20
1.7C
Loading,
g/MWh
0.0001k
0.0003.
-
0.0001
0.0004
0.61
0.036
0.65
0.06
0.1
Combined discharge
to POTW
Concen-
tration ,
MCJ/L3
8,100
8,000
40
5
<30
2,600
710
16
<1.0
16
20
12
1.2
240C
Loading,
g/MWh
6.1
6.0
0.03
<0.005
<0.03
2.0
0.54
12
<1.0
12
15
8.9
0.91
0.76d
aExcept conventional parameters, which are given in mg/L (unless otherwise noted).
Negligible.
cValues in m3/d.
'Value in m3/MWh.
Note: Blanks indicate no data available.
Richardson and Chicago Limit,
Chromium 5
Nickel 5
Cadmium 2
Beryllium 1
Silver 1
Mercury 0.5
GSR1
All tested
pollutants
Limit, |jg/L
10
Detection limits for Radian were not available. Richardson
analyzed the indicated metals only. Arsenic, thallium, antimony,
selenium, and mercury were not analyzed in Chicago metal samples.
Date: 6/23/80
11.19-37
-------
II.19.4 POLLUTANT REMOVABILITY [1, 3, 4]
Wastewater effluents discharged to publicy owned treatment facili-
ties are sometimes treated by end-of-process physical or chemical
systems to remove pollutants potentially hazardous to the POTW or
which may be treated inadequately in the POTW. Such treatment
methods are numerous, but they generally fall into one of three
broad categories in accordance with their process objectives.
These include pH control, removal of dissolved materials, and
separation of phases.
Table 19-27 lists potential treatment methods and Table 19-28
provides a similar list of solid/liquid separation processes.
Available technologies and efficiencies removal for major pollu-
tants are listed in Table 19-29. Most of the processes listed
in these tables are in use for treatment of steam electric or
other industrial or municipal wastewaters.
Three specific plants were cited in Reference 1 in terms of
pollutant removability. Specifics for these three plants are
presented in Tables 19-30 through 19-35.
II.19.5 REFERENCES
1. Draft Technical Report for Revision of Steam Electric Effluent
Limitations Guidelines. U.S. Environmental Protection Agency,
Washington, B.C., September 1978. 607 pp.
2. Development Document for Proposed Effluent Limitations Guide-
lines and New Source Performance Standards for the Steam
Electric Power Generating Point Source Category. EPA-440/1-
73/029, U.S. Environmental Protection Agency, Washington,
D.C., March 1974. 677 pp.
3. Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Steam Electric Power
Generating Point Source Category. EPA-440/l-74/029-a, U.S.
Environmental Protection Agency, Washington, D.C., October
1974. 842 pp.
4. Supplement for Pretreatment to the Development Document for
the Steam Electric Power Generating Point Source Category.
EPA-440/1-77/084, U.S. Environmental Protection Agency,
Washington, D.C., April 1977. 244 pp.
5. NRDC Consent Decree Industry Summary - Steam Electric Power
Generating Industry.
6. Environmental Protection Agency Effluent Guidelines and Stand-
ards for Steam Electric Power Generating. 40 CFF 423; 39 FR
36186, October 8, 1974, effective November 7, 19'/4; 40 FR 7095,
February 19, 1975; 40 FR 23987, June 4, 1975; 42 FR 15690,
March 23, 1977; 43 FR 43025, September 22, 1978; 43 FR 44848,
September 29, 1978.
Date: 6/23/80 11.19-38
-------
o
rt
• •
en
\
IxJ
U)
\
00
o
TABLE 19-27. END-OF-PIPE TREATMENT TECHNOLOGIES [4]
VD
I
UJ
VD
Method
Neutralization
Chemical reduction
Precipitation
Ion exchange
Liquid/ liquid
extraction
Objectives
pH adjustment.
usually to within the
range of 6 to 9
Reduction of hexa-
valent chromium to
trivalent chromium
Removal of ions by
forming insoluble
salts
Removal of ions by
sorption on surface
of a solid matrix
Removal of soluble
organic: or chemi-
cally charged pol-
lutants
Chemicals or Process
equipment used requirements
Acid or base as
required, usually
sulfuric acid or lime
Sulfur dioxide, pH range of
sodium bilsufite, 2 to 3
sodium metabisulfite.
ferrous salts
Lime, hydrogen sul- Optimum pH
fide, organic pre- depends on the
cipitants, soda ash ions to be
removed
Synthetic cation and May require pH
anion exchange adjustment
resins
Immiscible solvents May require pH
that may contain adjustment
chelating agents
Efficiency
of removal
99.7% (removal
to <1 mg/L)
Copper - 96.6%
(removal to <1
mg/L) nickel -
91.7% chromium -
98.8% (removal to
0.006 mg/L) zinc
99.7% (removal to
0.5-2.5 mg/L)
phosphate - 93.6%
iron (removal to
0.3 mg/L)
Cyanide - 99%
chromium - 98%
(removal to
0.01 mg/L)
copper - 95%
(removal to
0.03 mg/L)
iron - 100%
cadmium - 92%
nickel - 100%
zinc - 75%
(removal to 20
mg/L)
phosphate - 90%
sulfate - 97%
aluminum - 98%
Phenol - 99%
chromium - 99%
nickel - 99%
zinc - 99%
fluoride - 68%
iron - 99%
molybdenum - 90%
Demonstration status
Practiced extensively by
industry
Practiced extensively by
industry
Practiced extensively by
industry
-
Used primarily in water treat-
ment operation for production
of boiler feedwater
Process is not highly developed
for industrial use (except
phenol extraction)
(continued)
-------
D
PI
rh
(D
(Ti
to
U)
CO
o
TABLE 27 (continued)
Method
Disinfection
Adsorption
Chemical oxidation
Distillation
Objectives
Destruction of
microorganisms
Removal of sorbable
contaminants
Destruction of
cyanides
Separation of dis-
solved matter by
Chemicals or
equipment used
Chlorine , hypo-
chlorite salts.
phenol, phenol
derivatives, ozone.
salts of heavy
metals, chlorine
dioxide
Activated carbon.
synthetic sorbents
Chlorine, hypochlo-
rite salts, ozone.
hydrogen peroxide
Multistage flash
distillation.
Process
requirements
May require pH
adjustment
May require pH
adjustment
pH =• 9.5-10
(first step).
pH = 8 (second
step)
May require pH
adjustment
Efficiency
of removal
Depends on the
nature of pol-
lutants and com-
position of waste
99.6%
100%
Demonstration status
Disinfection by chlorine is
practiced extensively by
industry
Practiced extensively by
industry
Practiced extensively by
industry
Practiced only to a moderate
extent by industry, primarily
I
*>.
o
Reverse osmosis
Electrodialysis
evaporation of the
water
Separation of dis-
solved matter by
filtration through
a semipermeable
membrane
Removal of
dissolved
polar compounds
multiple-effect
long- tube verti-
cal evaporation,
submerged tube
evaporation,
vapor compression
the submerged tube type unit
Freezing
Separation of so-
lute from liquid
by crystallizing the
solvent
Tubular
hollow fiber
modules, spiral-
wound flat sheet
membrane
Solute is exchanged
between two liquids
through a selective
semipermeable mem-
brane in response to
differences in chemi-
cal potential between
two liquids
Direct refriger-
ation, indirect
refrigeration
TDS - 93%
TDS - 62-96%
Very limited use in
industrial wastewater treatment
Not practiced by in-Sn^try
>99.5%
Unproven method in waste
treatment application
-------
o
0)
ft
(D
TABLE 19-28. SOLID/LIQUID SEPARATION SYSTEMS [4]
w
\
CO
o
Unit operation
Skimming
Clarification
Flotation
Process objectives
Removal of floating
solids or liquid wastes
from the water
Removal of suspended
solids by settling
Separation of suspended
solids by flotation
followed by skimming
Methods or
units used
Settling ponds,
clarifiers
Froth flotation,
dispersed air
flotation,
dissolved air
Retention
time
1-15 min
45 min
20-30 min
Chemicals used
None
Coagulants,
coagulant aids,
pH adjustment
Aluminum and
ferric salts,
activated silica
organic polymers
Efficiency
of removal
70-90%
To 15 mg/L
90-99%
Demonstration status
Practiced extensively by
industry
Practiced extensively by
industry
Practiced extensively by
industry
flotation,
gravity flotation,
vacuum flotation
VO
I
Microstraining
Filtration
Screening
Thickening
Removal of suspended solids
by passing the wastewater
through a microscreen
Removal of suspended
solids by filtration
through a bed of sand
and gravel
Removal of large solid
matter by passing through
screens
Concentration of sludge
by removing water
Multimedia bed,
mixed media bed
Coarse screens,
bar screens.
Gravity thickening,
air flotation
thickening
N/A
N/A
N/A
N/A
None
None
None
None
70-80%
(23 Mm)
50-60%
(3 M
-------
ft
(D
NJ
CO
o
TABLE 19-28 (continued).
H
NJ
Unit operation
Pressure
filtration
Heat drying
Ultrafiltration
Sandbed drying
Vacuum
filtration
Process objectives
Separation of solid from
liquid by passing through
a semipenneable membrane
under pressure
Reduce the water content
of sludge
Separation of macro-
molecules of suspended
matter from the waste by
filtration through a semi-
permeable membrane under
pressure
Removal of moisture from
sludge by evaporation and
drainage through sand
Solid liquid separation
by vacuum
Methods or
units. used
Plate and frame
pressure filter
Flash drying, spray
drying, rotary
kill. Ji/^n
multiple hearth
drying
Covered beds.
uncovered beds
Rotary vacuum
filter
Retention
lime Chemicals used
1-3 hr None
N/A None
N/A None
Filtration None
1-2 days
1-5 minutes None
Efficiency
of removal
To 50-75%
moisture
content
To 8%
moisture
Tot-H solid
removal ot
95% and
above
As filter
15-20%
Produces 30%
solid in
Demonstration status
Practiced by industry for
sludge dewatering
Rotary kilns are used by
industry to small extent
Used by industry primarily
tc treat oily waste
Practiced extensively by
industry
Practiced extensively
by industry
Centrifugation
Emulsion
breaking
Liquid/solid separation
by centrifugal force
Separation between
emulsified oil and water
Disc centrifuge,
basket centrifuge,
conveyor type
centrifuge
N/A None
2-8 hr Aluminum salts,
iron salts, pH
adjustment (1-4)
in filter
cake
Moisture is
reduced to
65-70%
>99%
Practiced by industry for
sludge dewatering
Practiced extensively by
industry
-------
TABLE 19-29. CHEMICAL WASTES CONTROL AND TREATMENT TECHNOLOGY [3]
Pollutant/parameter
pH
Dissolved solids
Suspended solids
BOD/ COD, Sanitary wastes
COD, Hater -reatment, chemica)
cleaning
Phosphate, Slowdown, chemical
cleaning, floor and yard drains.
plant laboratory and sampling
Iron, Water treatment, chemica..
cleaning, coal ash handling,
coal pile drainage
Copper, Once-through condenser
cooling
Copper, Slowdown , chemical
cleaning
Mercury, Coal ash handling
and coal pile drainage
Vanadium, Chemical cleaning
Centre 1 and/or
treatment
tect-.nolooy
Neutralization with
chemicals
1. Concentration and
evaporation
2. Reverse osmosis
3. Distillation
1. Sedimentation
2 Chtm.cal coagulation and
precipitation
3. Filtration
Biological treatment
1 . Chemical oxidation
2. At ration
3. Biological treatnent
1. '..heliacal coagulation and
and precipitation
2. Deep well disposal
1 Oxidation, chemical
coagulation and
precipitation
2 Deep well disposal
1 Replace condenser tubes
with stainless steel or
titanium
1. Chemical coagulation
and precipitation
2 Ion exchange
3. Deep well disposal
1 Reduction and precipitation
2. Ion exchange
3. Adsorption
1. H2S treatment and
precipitation
2. Ion exchange
Effluent
reduction
achievable
Neutral pK
Complete removal
50-95%
60-90%
90-95%
95-99%
95% (removal to 2-10 ug/L)
Neutral pH and >95% removal
85-95%
85-95%
85-95%
Ultimate disposal
Removal to 0.1 mg/L
Ultimate disposal
Elimination of discharge
Removal to 0.1 mg/L
Removal to 0.1 mg/L
Ultimate disposal
Removal to 0.3 mg/L
Removal to 0.1 mg/L
Removal to 50 Mg/L
Removal of low concentrations
difficult to achieve
Industry usage
Common
Not generally in use -
desalinization technology
Not in use - desalinization
technology
Not in use - desalinization
technology
Extensive
Moderate
Not generally practiced-water
treatnent technology
Limited usage
Limited usage
Not practiced
Not practiced
Not generally practiced-water
treatment technology
Not practiced
Limited usage
Not practiced
Done in several plants where
tubes have erroded or corroded'
not done for environmental
reasons
Limited usage
Not practiced
Not practiced
Limited usage
Not practiced
Not practiced
Not practiced
Not practiced
(continued)
Date: 6/2 V80
11.19-43
-------
TABLE 19-29 (continued).
Follutant/paraae te.-
Vanadiun, Oil ash handling
Chlorine, Once-through
condenser cooling
Chlorine, Recirculating
Aluminum/zinc, Water treatment,
chemical cleaning, coal ash
handling, coal pile drainage
Oil, Chemical cleaning, ash
handling, flopr and yard drains
Phenols, Ash handling, coal
pile drainage, floor and yard
drains
Sulfate/sulfite, Water treat-
ment, chemical cleaning, ash
handling, coal pile drainage,
S02 removal
Ammonia, Water treatment,
blowdown, chemical cleaning,
closed cooling water systems
Oxidizing agents, Chemical
cleaning
Fluoride, Chemical cleaning
Boron, Low level radwastea
Control and/or
treatment
technology
Effluent
reduction
achievable
Industry mage
1. Convert te dry collection Ultimate disposal
2. Total recycle with blowdown Complete recycle of liquid
and precipitation
Control of residual C12
with automatic
instrumentation
Control to 0.2 mg/L
2. Utilize mechanical cleaning Eliminates C12 discharge
Control of residual C12
with autonatic
instrumentation
Reduction of C12 with
sodium bisulfite
1. Chemical precipitation
2. Ion exchange
3. Deep well disposal
1
Control to 0.2 mg/L
Below detectable limits
Removal to 1.0 mg/L
Removal to 0.1 mg/L
Ultimate disposal
Oil-water separator Removal to IS mg/L
(sedimentation with slumming)
2. Air flotation
1. Biological treatment
2. Ozone treatment
3. Activated carbon
Ion exchange (sulfate)
Oxidation and ion exchange
(sulfite)
Removal to 10 mg/L
Removal to 1 mg/L
Removal to <0.01 mg/L
Removal to <0.01
75-95%
1 Stripping 50-90%
2. Biological nitrification Removal to 2 mg/L
3. Ion exchange 80-95%
Neutralization with reducing Neutral pH and >95% removal
agent and precipitation where
necessary
Chemical precipitation
Ion exchange
Removal to 1 mg/l
Keawval to 1 mg/L
Practiced in several plants
Not generally practiced
Limited usage in the industry-
Technology from sewage treatment
practiced in some plants-all
systems are not capable of
being converted to mechanical
cleaning
Limited usage in the industry
Being installed in a new
nuclear facility; however
excess NaHS03 is discharged
Limited usage
Not practiced
Common usage
Limited usage
Not practiced
Not practiced
Not practiced
Not practiced
Not practiced; several installa-
tions in sewage treatment
Not practiced for these waste
streams
Not practiced
Limited usage
Limited usage
Not generally practiced-radlo-
aetive material would concen-
trate on ion exchange resin
requiring inclusion in solid
radwaste disposal system
Date: 6/23/80
11.19-44
-------
o
01
rt
(D
NJ
U)
00
o
TABLE 19-30.
H
vo
I
*>.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 1226 [1]
Cooling tower
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Ethers
4-Chlorophenol
Phthalates
Bis(2-ethylhexyl) phthalated
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenol
Aromatics
Benzene
1 , 3-Dichlorobenzene
Ethylbenzene
Toluene
1,2, 4-Trichlorobenzenee
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene
Benz ( a ) anthracene
Benzo(b)f luoranthene9
Benzo( k) f luoranthene9
2-Chloronaphthalene
Chrysene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Concentration,
pg/L
Inlet
7
4
<0.5
1.8
5
47
5
3
0.2
6.0
<2
0.7
<1
27
<1
3.2
5.0
<1
6.1
1.7
3.8
<1
4.6
1.1
0
oa
50r
C
14r
C
>92
63
o"
c
>84
_c
>9
_c
63
63
osmosis
Ash pond effluent
Concentration,
pg/L Percent
Inlet Outlet removal
7 BDL 100b
9 <1 >89
<0.5 <0.5 -C
2.0 1.3 35
6 <2 >67
14 10 29
<1 8 Oa
4 <3 >25
<0.2 <0.2 -c
5.5 5.0 9
8 2 75
0.5 <0.2 >60
<1 <1 -c
7 <2 >57
9.9
2 3 5.5 Oa
2.0 NA -c
1.9
s-i
<1 <1 -c
<1 1.6 Oa
^
2.7
1.4
25
0.2 0.7 0 <0.2 0.3 Oa
6.0 2.9 52 5.5 6.0 Oa
<2 <2 - 8 8 0
0.7 0.9 Oa 0.5 0.4 20
<1 <1 -C <1 <1 -c
26 2 92 7 2 57
-------
o
CU
ft
0)
co
u>
CO
o
TABLE 19-30 (continued).
Chemical precipitation
Reverse
Cooling tower blowdown
Concentration ,
ug/L Percent
Toxic pollutant
Inlet Outlet
removal
osmosis
Lime
Ash pond effluent
Concentration,
ug/L
Inlet Outlet
Percent
removal
Cooling tower blowdown
Concentration,
ug/L
Inlet Outlet
Percent
removal
Ash pond effluent
Concentration,
pg/L
Inlet Outlet
Percent
removal
Halogenated aliphatics
Bromoform
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Tetrachloroethylene
1,1,1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldrin
°-BHCh
Y-BHC
4,4'-DDT
Endosulfan sulfate1
Endrin aldehyde
Heptachlor epoxide
150 ND
59 ND
4.6
<2
ND
ND
1.3
100
100
10
I
*»
en
Chemical precipitation
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Ethers
4-Chlorophenol
Phthalates
Bis(2-ethylhexyl) phthalated
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenol
7
4
<0.5
1.8
5
47
3
0.2
6.0
<2
0.7
<1
26
Lime
9
3
<0.5
1.6
3
4
<3
0.2
6.0
<2
0.4
0
0
0
c
43
c
92
7
9
<0.5
2.0
6
14
4
<0.2
5.5
8
0.5
<1
7
9
3
<0.5
3.2
4
7
<3
0.6
9.0
7
0.4
6
Activated carbon
Oa
67
_c
oa
33
50
>25
oa
oa
12
20
_c
14
<1
3.2 <1 69 <1 <1
5.0 6.8 Oa
<1 ND 100 <1
6.1 ND 100 2.3 1.5
1.7 NA -C 2.0 NA
35
(continued)
-------
D
£»
rt
CD
cr>
to
u>
CO
o
vo
I
TABLE 19-30 (continued).
Chemical precipitation
Toxic pollutant
Cooling tower
Concentration ,
ug/L
Inlet Outlet
Line -i
blowdown
Percent
reitoval
> Fe'
Ash pond effluent
Concentration ,
pg/L
Inlet Outlet
Percent
removal
Cooling tower
Concentration ,
M9/L
Inlet Outlet
Lime
blowdown
Percent
removal
Ash pond effluent
Concentration ,
pg/L
Inlet Outlet
Percent
removal
Aromatics
Benzene
1,3-Dichlorobenzene
Ethylbenzene
Toluene
1,2,4-Trichlorobenzenee
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene ,
Benz < a)anthracene
Benzo(b)fluoranthene^
Benzo(k)fluoranthene^
2-Chloronaphthalene
Chrysene
Fluoranthene
Fluorene
lndeno(1,2,3-cd)pyrene
Naphthalene f
Phenanthrene
Pyrene
Halogenated aliphatics
Bromoform
Chlorodibromonethane
Chloroform
1,2-Dichloroethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Tetrachloroethylene
1,1,1-Trichloroethane
Trichloroethylene
Pesticides and metabolites
Aldri
Y-BHCT
4,4'-DDT .
Endosulfan sulfate
Endrin aldehyde1
Heptachlor epoxide
3.8
4.6
<2
2.3
3.2
2.9
2.9
2.1
3.2
<1
5.9
5.9
<1
69
Oa
Oa
69
86
ioo
Negative removal.
Effluent concentration below detectable limits.
clndeterminate.
Combination of phenanthrene and anthracene
^Combination of benzo(b)fluoranthene and benzo(k)flui
hCombination of 6-BHC and >-BHC.
Combination of bis(2-ethylhexyl) phthalate, benz(a)anthracene, and chrysene. Combination of endosulfan sulfate and endrin aldehyde.
Combination of 1,2,4-trichlorobenzene and hexachlorobutadiene.
-------
TABLE 19-31. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 1226 [1]
Cooling
tower
Concentration
Pollutant
TOC, mg/L
pH
Methoxyclor, pg/L
Vanadium, pg/L
Inlet
<20
6.8
1.1
27
Outlet
<20
58
Reverse
blowdown
Percent
removal
_a
Ob
osmosis
Ash pond effluent
Concentration
Inlet Outlet
<20 <20
9.1
78 14
Percent
removal
_a
82
Chemical precipitation
Lime
TOC , mg/L
PH
Methoxyclor, pg/L
Vanadium, pg/L
<20
11.5
27
<20
6
a
78
<20 <20
11.5
78 78
_a
0
Chemical precipitation
TOC , mg/L
pH
Methoxyclor, pg/L
Vanadium, pg/L
<20
1.1
27
<20
12
Lime
_a
56
+ Fe+*
<20 <20
78 82
_a
Ob
Indeterminate.
^Negative removal.
Date: 6/23/80
11.19-48
-------
o
0)
ft
ft)
CTi
U)
00
o
H
H
vo
I
•t^
VD
TABLE 19-32.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 5409 [1]
Chemical precipitation
Reverse
Cooling tower blowdown
Concentration,
ug/L __._
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate0
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenoa
Aromatics
Inlet
<1
<1
3.4
0.8
37
620
5
70
0.5
4.0
<2
14
8
61
3.4
10
2.7
11
4.1
Outlet
<1
<1
<0.5
<0.5
<2
51
24
<3
<0.2
3.6
<2
1.1
4
<2
2
ND
<1
4.7
NA
Percent
removal
_a
&
>85
>37
>94
92b
ob
>96
>60
10a
92
50
>97
41
100
>63
56
_a
osmosis
Lime
Ash pond effluent
Concentration ,
ug/L
Inlet
5
74
<0.5
<0.5
<2
26
13
<3
<0.2
2.5
42
1
9
11
a
12
<1
6.7
4.1
Outlet
2.5
<1
<0.5
<0.5
<2
9
10
6.5
<0.2
1.5
6.1
1
1
2
<1
NA
Percent
removal
50
>99
_a
a
_a
65
23b
ob
_a
40
85
0
89
92
_a
_a
Cooling tower blowdown
Concentration,
ug/L
Inlet
<1
<1
3.4
0.8
37
620
70
0.5
4
<2
14
8
61
Outlet
4
2.5
0.8
<0.5
8.8
70
<3
<0.2
2.3
2.3
7.8
<1
<2
Percent
removal
o*
0D
76
>38
76
89
>96
>60
43b
0°
44
>88
>97
Ash pond effluent
Concentration,
pg/L
Inlet
5
74
<0.5
<0.5
<2
26
<3
<0.2
2.5
42
1
9
11
Outlet
4
<1
<0.5
<0.5
<2
12
<3
<0.2
2.2
52
1.1
8
<2
Percent
removal
20
>99
a
a
a
54
a
_a
12b
°b
0D
11
>82
Benzene
Ethylbenzene
Toluene
1,2,4-Trichlorobenzene
d
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene
Benz(a)anthracene0
Benzo(b)fluoranthene6
Benzo(k)fluoranthene*
2-Chloronaphthalene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
1.5
1.7
<1
6.2
3.4
2.8
2.8
<1
3.4
5.5
6.2
3.5
<1
>33
1.0
1.0
>0
1.7
3.3
2
ND
ND
1.4
2
7.4
<1
41
100
100
<1
<1
^continued)
-------
D
(U
rt
(D
CO
00
o
TABLE 19-32 (continued).
H
VO
I
Ul
o
' Chemical precipitation
Reverse
Cooling tower blowdown
Concentration ,
Toxic pollutant
Inlet
Outlet
Percent
removal
osmosis
Ash pond effluent
Concentration',
pg/L
Inlet Outlet
Percent
removal
Lime
Cooling tower blowdown
Concentration,
pg/L
Inlet Outlet
Percent
removal
Ash pond effluent
Concentration,
ug/L
Inlet Outlet
Percent
removal
Halogenated aliphatics
Chlorodibromomethane
Chloroform d
Hexachlorobutadiene
Hexachlorocyclopentadiene
Trichloroethylene
Pesticides and metabolites
Aldrin
P-BHC;
6-BHC9
Y-BHC9
4,4'-DDD
4,4'-DDT
p-Endosulfan
Endrin ,
Heptachlor
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalatec
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenol
2.4 <1
ND
>58
100
<1
1.1
1.1
Chemical precipitation
Lime + Fe z
<1.0
3.4
0.8
37
620
70
0.5
4.0
<2.0
14
8.0
61
<1.0
<0.5
0.5
<2.0
48
<3
<0.2
3.6
<2.0
1.0
1.0
<2
_a
_a
>85
37
>95
92
>96
>60
10
-a
93
>88
>97
5.0
74
<0.5
<0.5
<2.0
26
<3.0
<0.2
2.5
42
1.0
9.0
11
3.5
<0.5
<0.5
<2.0
18
<3.0
<0.2
2.0
32
1.1
7.0
<2.0
Activated carbon
30
>99
_a
_a
_a
31
.a
_a
20
24
0"
22
>82
(continued)
-------
rt
(D
NJ
OJ
00
O
TABLE 19-32 (continued).
VD
I
Ul
Chemical precipitation
Lime + Fe z
Cooling tower blowdown
Concentration ,
Toxic pollutant
Aromatics
Benzene
1 , 4-Dichlorobenzene
Inlet
1.5
Outlet
<1
1.8
Percent
removal
>33
Activated carbon
Ash pond effluent
Concentration ,
pg/L
Inlet Outlet
1.0 <1
Percent
removal
>0
Cooling tower blowdown
Concentration ,
jjg/L Percent
Inlet Outlet removal
Ash pond effluent
Concentration,
ug/L
Inlet Outlet
Percent
removal
Ethylbenzene
Toluene ,
1,2,4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(b)fluoranthene6
Benzo(k)fluoranthene6
2-Chloronaphthalene
Chrysene
Fluoranthene
Fluorene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Chlorodibromomethane
Chloroform .
Hexachlorobutadiene
Hexachlorocyclopentadiene
Trichloroethylene
Pesticides and metabolites
Aldrin
P-BHC*
6-BHC9
Y-BHC9
4,4'-ODD
4,4'-DDT
B-Endosulfan
Endrin ,
Heptachlor
<1
2.
<1
<1
ND
<1
ND
>58
100
-------
TABLE 19-33. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 54.09 [1]
Cooling
tower
Concentration
Pollutant
TOC , mg/L
pH
Vanadium, |jg/L
Inlet
21
6.8
11
Outlet
<20
16
Reverse osmosis
blowdown Ash pond effluent
Percent Concentration
removal Inlet Outlet
>5 <20 <20
. 6.7
0D 31 21
Percent
removal
_a
32
Chemical precipitation
TOC , mg/L
PH
Vanadium, M9/L
21
11
<20
6
Lime
>5 <20 <20
45 31 19
_a
39
Chemical precipitation
TOC , mg/L
PH
Vanadium, [ig/L
21
11
NA
46
Lime + Fe 2
<20 NA
Ob 31 19
39
Indeterminate.
""Negative removal.
Date: 6/23/80
11.19-52
-------
D
P<
rt
to
U)
oo
o
TABLE 19-34.
H
VO
I
Ul
u:
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 5604 [1]
Reverse
Cooling tower blowdown
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalatec
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenol
Aromatics
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene
Benz(a)anthracenec .
Benzo (b ) f luoranthene ^
Benzo ( k ) f luoranthene
Chrysene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Phenanthrene
Pyrene
Halogenated aliphatics
Chloroform
Pesticides and metabolites
B-BHCe
Heptachlor"
Concentration ,
pg/L
Inlet
5
7
<0.5
<0.5
2
180
3
<3
<0.2
6
<2
3
<1
780
1.3
2.9
<1
2.4
<1
24
<1
<1
83
SO
oa
-
99
>23
100
oa
15
b
>23,
oa
0"
>23
>63
>0
b
19
osmosis
Chemical precipitation
Lime
Ash jMMid effluent Cooling tower blowdown Ash pond effluent
Concentration ,
Mg/L
Inlet Outlet
6 3
<1 <1
2.5 5
1 <
4 <
80
22
<3 <
<0.2 <
9.5 <
3 <
5.5 2
<1 2
300 53
1.0 2.1
1.6 <1
4.9 <1
<1
NA
2.0 1.4
2.1
3.5 2.8
<1
86. <1 1
0 <0.5 <0.5 -? 2.5 0.5
>0 7S 2 <2 >0 42
89 180 48 73 80 23
82 .
67 <3 <3 -? <3 3
0 <0.2 <0.2 - <0.2 0.2
>89 6 12 Oa 9.5 0.5
>67 <2 <2 33
64 3 4 Oa 5.5 5
0 <1 <1 - <1 1
82 780 140 82 300 31
oa
>38
>80
30
20
0«
oa
100
Percent
removal
14
Oa
<80
<50
50
71
Oa
Oa
<95
0
9
Oa
90
(continued)
-------
CJ
CD
rt
ro
N)
CO
o
TABLE 19-34 (continued).
H
Ul
*>.
Cooling tower
Concentration,
ug/L
Toxic pollutant Inlet Outlet
Hetals and inorganics
Antimony 5 5
Arsenic 7 <1
Beryllium <0.5 <0.5
Cadmium <0.5 <0.5
Chromium 2 <2
Copper 180 26
Cyanide
Lead <3 <3
Mercury <0 2 <0.2
Nickel 6 3
Selenium <2 <2
Silver 3 10
Thallium <1 <1
Zinc 780 36
Phthalates
Bis(2-ethylhexyl) phthalate0
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Phenols
Phenol
Aromatics
Benzene
1 , 4-Dichlorobenzene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenapthene
Acenaphthylene
Anthracene
Benz(a)anthracenec ,
Benzo (b)f luoranthene ,
Benzo ( k) f luoranthene
Chrysene
Fluoranthene
Fluorene
Indeno(l,2 ,3-cd)pyrene
Phenanthrene
Pyrene
Halogenated aliphatics
Chloroform
Pesticides and metabolites
f)-BHCe
Heptachlor
Negative removal
Indeterminate
Chemical precipitation
Lime + Fe*2 Activated carbon
blovdown Ash pond effluent Cooling tower blowdown Ash pond effluent
Concentration, Concentration, Concentration,
Percent ug/L Percent ug/L Percent ug/L Percent
removal Inlet Outlet removal Inlet Outlet removal Inlet Outlet removal
0 6 30 0*
>86 <1 <1
-r 2.5 0.5 80
- 1 <0.5 >SO
>0 4 2 50
86 80 23 80
h b
-? <3 <3 -?
<0.2 <0.2
50. 9.5 95
-b 3 3 0
°b *•* <5 9b
95 300 25 92
1.3 1.2 7.7 1.0 <1 >0
1.9 2.4
2.9 4.2 0° 1.6 <1 >38
7.5 4.9 <1 >80
<1 <1
2.4 NA NA
<1 <1 - 2.0 <1 >50
24 3.3 >86 3.5 5.3 Oa
<1
<1
<^
1.3 1.2 7.7 1.0 <1 >0
7.8 3.7 52
7.8 3.7 52
1.3 1.2 7.7 1.0 <1 >0
2.7 1 1 59 69
<1
-------
TABLE 19-35. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN
RAW AND TREATED WASTEWATER, PLANT 5604 [1]
Cooling
Reverse osmosis
tower blowdown Ash pond effluent
Concentration Percent Concentration
Pollutant
TOC , mg/L
TSS, mg/L
PH
Vanadium, |jg/L
TOC , mg/L
TSS, mg/L
pH
Vanadium, pg/L
TOC , mg/L
TSS, mg/L
PH
Vanadium, \ig/L
Inlet
14
6.9
24
14
42
24
14
42
Outlet removal Inlet Outlet
7.6
5.6
22 8 27 5
Chemical precipitation
Lime
7.6
15
77 Oa 27 17
Chemical precipitation
Lime + Fe 2
7.6
15
Percent
removal
81
37
aNegative removal.
Date: 6/23/80
11.19-55
-------
11.20 TEXTILE MILLS
II.20.1 INDUSTRY DESCRIPTION [1]
II.20.1.1 General Description
The United States textile industries are covered by 2 of the 20
major groups of manufacturing industries in the Standard Indus-
trial Classification (SIC). They are Textile Mill Products,
Major Group 22, and Apparel and Other Textile Mill Products,
Major Group 23. The Textile Mill Products group includes 30
separate industries that manufacture approximately 90 classes of
products. The Apparel and Other Textile Products group includes
33 separate industries that manufacture some 70 classes of
products.
Major Group 22 facilities are principally engaged in receiving
and preparing fibers; transforming these materials into yarn,
thread, or webbing; converting the yarn and web into fabric or
related products; and finishing these materials at various stages
of the production. Many produce a final consumer product such as
thread, yarn, bolt fabric, hosiery, towels, sheets, carpet, etc.,
while the rest produce a transitional product for use by other
establishments in Major Groups 22 and 23.
The facilities in Major Group 23, Apparel and Other Textile Mill
Products, are principally engaged in receiving woven or knitted
fabric for cutting, sewing, and packaging. Some of the products
manufactured are dry cleaned and some undergo auxiliary process-
ing to prepare them for the consumer. In general, all processing
is dry and little or no discharge results.
The exact number of wet processing mills and the total number of
mills in the textile industry are difficult to establish because
of the relatively large numbers involved, the dynamic state of
the industry, and differing classification criteria. The number
of wet processing mills is estimated to be approximately 2,000,
and the total mills between 5,000 and 7,500. Nearly 80% of the
facilities are located in the Mid-Atlantic and Southern regions.
The remaining 20% are distributed about equally between the New
England region and the North Central and Western regions. Some
industries, particularly yarn manufacturing, weaving, and carpet
manufacturing, are heavily concentrated in a few southeastern
states.
Date: 6/23/80 II.20-1
-------
Facilities in the textile industry are engaged in various proc-
essing operations required to transform fiber — the industry's
basic raw material — into yarn, fabric, or other finished tex-
tile products. Approximately 70% of the facilities are believed
to perform manufacturing operations that require no process water
and an additional 10% are believed to use only small quantities
of process water. In contrast, the remaining 20% of the facili-
ties that scour wool fibers, clean and condition other natural
and man-made fibers, and dye or finish various textile products
generally require large quantities of process water.
Depending on the primary fiber type (wool, cotton, or man-made),
a variety of production processes, some completely dry in terms
of water requirements and some resulting in wastewater discharge,
are used to manufacture the various products of this industry. In
general, most of the dry- or low water use-processing operations
(spinning, tufting, knitting, weaving, slashing, adhesive proc-
essing, and functional finishing) precede the wet processing
operations in the manufacturing sequence.
Most high water use textile manufacturing processes occur during
the conventional finishing of fiber and fabric products. The most
significant are desizing, scouring, mercerizing, bleaching, dye-
ing, and printing. In the case of wool products, the distinct
nature of this fiber often makes additional wet processing neces-
sary prior to conventional finishing. Additional specific proc-
esses for wool include raw wool scouring, carbonizing, and
fulling.
It is not uncommon for two or more wet process operations to
occur sequentially in a single batch unit or on a continuous
range. For example, it is not unusual for desizing, scouring,
and mercerizing operations to be placed in tandem with the
continuous bleaching range to enable cotton to be finished more
efficiently. It should be understood that a variety of wet
finishing situations of this type may occur, depending upon fac-
tors such as processes employed, type and quality of materials
and product, and original mill and equipment design.
Table 20-1 presents industry summary data for the Textile Mills
point source category in terms of the number of subcategories,
number of dischargers, pollutants and toxics found in significant
quantities, total number of toxic pollutants detected, and
candidate treatment and control technologies [1], [2].
II.20.1.2 Subcategory Descriptions
Based on similarities in raw materials, final products, manufac-
turing processes, and waste characteristics, the following sub-
categories of the textile industry were established:
Date: 6/23/80 II.20-2
-------
1. Wool Scouring
2. Wool Finishing
3. Low Water Use Processing
4. Woven Fabric Finishing
a. Simple Processing
b. Complex Processing
c. Complex Processing Plus Desizing
5. Knit Fabric Finishing
a. Simple Processing
b. Complex Processing
c. Hosiery Products
6. Carpet Finishing
7. Stock and Yarn Finishing
8. Nonwoven Manufacturing
9. Felted Fabric Processing
TABLE 20-1. INDUSTRY SUMMARY [1], [2]
Industry: Textile Mills
Total Number of Subcategories: 13
Number of Subcategories Studied: 9
Number of Dischargers in Industry: 1,165
• Direct: 239
• Indirect: 926
• Zero: 0
Pollutants and Toxics Found in Significant Quantities
• 11 Heavy metals
• Cyanide
• Total phenol
Number of Toxic Pollutants Detected in:
• Raw wastewater: 58
• Treated effluent: 46
Candidate Treatment and Control Technologies:
• Chemical coagulation
• Multimedia filtration
• Coagulation plus filtration
Date: 6/23/80 II.20-3
-------
Subcategory 1 - Wool Scouring
This subcategory covers facilities that scour natural impurities
from raw wool and other animal hair fibers as the majority of
their processing. Wool scouring is conveniently separated from
other segments of the textile industry because wool and other
animal hair fibers require extensive preliminary cleaning.
Wool scouring, the first treatment performed on wool, is employed
to remove the impurities peculiar to wool fibers. These impuri-
ties are present in great quantities and variety in raw wool and
include natural wool grease and sweat, and acquired impurities
such as dirt, feces, and vegetable matter. Disinfectants and
insecticides applied in sheep dips for therapeutic purposes may
also be present. Practically all of the natural and acquired
impurities in wool are removed in the scouring process.
Two methods of wool scouring, solvent and detergent scouring, are
practiced. In the United States, the latter is used almost
exclusively. In the detergent process the wool is raked through
a series of 1,500- to 3,000-gallon scouring bowls known as a
"scouring train." Unless the first bowl is used as a steeping or
desuinting bowl, the first two bowls contain varying concentra-
tions of either soap and alkali, or nonionic detergents of the
ethylene oxide condensate class. The soap-alkali scouring baths
are generally characterized by a temperature of 32°C to 40°C
(115°F to 130°F) and a pH of 9.5 to 10.5; neutral detergent baths
normally have a pH of 6.5 to 7.5 and a temperature of 43°C to
57°C (135°F to 160°F). The last two bowls of the scouring train
are for rinsing, and a counterflow arrangement is almost always
employed using the relatively clean waters from these bowls in
preceding bowls.
Scouring emulsifies the dirt and grease and produces a brown,
gritty, turbid waste that is often covered with a greasy scum. It
has been estimated that for every pound of fibers obtained, 1.5 Ib
of waste impurities are produced. Since the wool grease present
in the scour liquor is not readily biodegradable and is of commer-
cial value, grease recovery is usually practiced. In the most
typical recovery process, the scour liquor is first piped to a
separation tank where settling of grit and dirt occurs. The
supernatant from the tank is then centrifuged (one or more stages)
into high density, medium density, and low density streams. The
high density stream consists mainly of dirt and grit, and is
discharged as waste. The medium density stream is recycled to
the wool scouring train. The low density stream contains concen-
trated grease that is normally refined further to produce lanolin.
Acid-cracking, utilizing sulfuric acid and heat, is an alternative
method of grease recovery, but it is not widely practiced at this
time.
Date: 6/23/80 II.20-4
-------
Subcategory 2 - Wool Finishing
This subcategory covers facilities that finish fabric, a majority
of which is wool, other animal hair fiber, or blends containing
primarily wool or other animal hair fibers, by employing any of
the following processing operations on at least 5% of their total
production: carbonizing, fulling, bleaching, scouring (not
including raw wool scouring), dyeing, and application of func-
tional finish chemicals. Mills that primarily finish stock or
yarn of wool, other animal hair fibers, or blends containing pri-
marily wool or other animal hair fibers and that perform carbon-
izing are included in this subcategory, and wool stock or yarn
mills that do not perform carbonizing and scouring are covered
under Subcategory 7, Stock and Yarn Finishing. Wool finishing is
differentiated from other finishing categories because of the
manufacturing processes (principally carbonizing and fulling) and
dyes and other chemicals associated with wool operations. As a
result, wool finishing operations generate high volume wastes
with pH fluctuations and oil and grease.
Processes comprising a typical wool finishing operation include
carbonizing, fulling, fabric scouring, and dyeing. Carbonizing
removes burrs and other vegetable matter from loose wool or woven
wool goods. These cellulosic impurities may be degraded to
hydrocellulose, without damaging the wool, when acted upon by
acids. It is important to remove these impurities from the wool
to prevent unequal absorption of dyes.
The first operation in carbonization is acid impregnation. Typi-
cally this consists of soaking the wool in a 4% to 7% solution of
sulfuric acid for a period of 2 to 3 hr. The excess acid is
squeezed out and the wool is baked to oxidize the cellulosic con-
taminants to gases and a solid carbon residue. The charred mate-
rial, primarily hydrocellulose, is crushed between pressure
rollers so that it may be shaken out by mechanical agitation.
Some solid waste is generated, but, with the exception of an
occasional dump of contaminated acid bath, no liquid waste
results. However, after the residue has been shaken out, the
acid must be removed. This is achieved by preliminary rinsing to
remove most of the acid followed by neutralization with sodium
carbonate solution. A final rinse is then used to remove the
alkalinity. As a result, the overall water requirements for the
carbonization of wool are substantial.
Fulling gives woven woolen cloth a thick, compact, and substan-
tial feel, finish, and appearance. To accomplish it, the cloth
is mechanically worked in fulling machines in the presence of
heat, moisture, and sometimes pressure. This allows the fibers
to felt together, which causes shrinkage, increases the weight,
and obscures the woven threads of the cloth.
Date: 6/23/80 II.20-5
-------
There are two common methods of fulling, alkali and acid. In
alkali fulling, soap or detergent is used to provide the needed
lubrication and moisture for proper felting action. The soap or
detergent is usually mixed with sodium carbonate and a sequester-
ing agent in a concentrated solution. In acid fulling, which may
be used to prevent bleeding of color, an aqueous solution of sul-
furic acid, hydrogen peroxide, and small amounts of metallic
catalysts (chromium, copper, and cobalt) is used.
Fabric scouring is employed to remove natural and acquired
impurities from the fabric. Either light or heavy scouring of
wool goods may be performed during wool finishing to remove the
acquired impurities.
Dyeing is the most complex of all the wet process operations. It
is performed essentially for aesthetic reasons in that it does
not contribute to the basic structural integrity, wearability, or
durability of the final product. In short, the function of dye-
ing is to anchor dyestuff molecules to textile fibers by a variety
of processes.
Subcategory 3 - Low Water Use Processing
Low water use processing operations include establishments pri-
marily engaged in manufacturing greige goods, laminating or coat-
ing fabrics, texturizing yarn, tufting and backing carpet,
producing tire cord fabric, and similar activities in which either
cleanup is the primary water use or process water requirements are
small, or both.
While there are a large number of facilities of these types, the
process-related wastewater generated and discharged from each is,
for the most part, comparatively small.
Subcategory 4 - Woven Fabric Finishing
This subcategory covers facilities that primarily finish fabric,
a majority of which is woven, by employing any of the following
processing operations on at least 5% of their production: desiz-
ing, scouring, bleaching, mercerizing, dyeing, printing, and
application of functional finish chemicals. Integrated mills that
finish a majority of woven fabric along with greige manufacturing
or other finishing operations such as yarn dyeing are included in
this subcategory, and total finishing production should be applied
to the applicable Woven Fabric Finishing effluent limitations to
calculate discharge allowances. Denim finishing mills are also
included in this category. Woven fabric composed primarily of
wool is covered under Subcategory 2 - Wool Finishing.
A wide variety of processes are used in finishing woven fabric,
and in terms of cumulative flow this subcategory is the largest.
Date: 6/23/80 II.20-6
-------
Desizing is a major contributor to the BOD load in woven fabric
finishing. This results in a major difference in waste character-
istics between woven and knit fabric finishing, and is responsible
for differences in the waste characteristics within the Woven
Fabric Finishing subcategory as well. In addition, the number of
processes performed at a particular mill may vary from merely
scouring or bleaching to all of those previously listed. The
following subdivisions describe the process differences.
Simple Processing. This Woven Fabric Finishing subdivision
covers facilities that perform fiber preparation, desizing,
scouring, functional finishing, and/or one of the following proc-
esses applied to more than 5% of total production: bleaching,
dyeing, or printing. This subdivision includes all Woven Fabric
Finishing mills that do not qualify under either the Complex Proc-
essing or Complex Processing Plus Desizing subdivisions.
Complex Processing. This Woven Fabric Finishing subdivision
covers facilities that perform fiber preparation, desizing of less
than 50% of their total production, scouring, mercerizing, func-
tional finishing, and more than one of the following, each applied
to more than 5% of total production: bleaching, dyeing, and
printing.
Complex Processing Plus Desizing. This Woven Fabric Finish-
ing subdivision covers facilities that perform fiber preparation,
desizing of greater than 50% of their total production, scouring,
mercerizing, functional finishing, and more than one of the
following, each applied to more than 5% of total production:
bleaching, dyeing, and printing.
Subcategory 5 - Knit Fabric Finishing
This subcategory covers facilities that primarily finish fabric
made of cotton and/or synthetic fibers, a majority of which is
knit, by employing any of the following processing operations on
at least 5% of their production: scouring, bleaching, dyeing,
printing, and application of lubricants, antistatic agents, and
functional finish chemicals. Integrated mills that finish a
majority of knit fabric along with greige manufacturing or other
finishing operations such as yarn dyeing are included in this
subcategory. Total finishing production should be applied to
the applicable Knit Fabric Finishing effuent limitations to cal-
culate discharge allowances.
Basic knit fabric finishing operations are similar to those in
the Woven Fabric Finishing subcategory and may include scouring,
bleaching, dyeing, printing, and application of lubricants, anti-
static agents, and functional finish chemicals. Knitting is
performed in conjunction with finishing at most of these facili-
ties. Desizing is not required in knit fabric finishing and
Date: 6/23/80 II.20-7
-------
mercerizing is uncommon in practice. The generally lower waste
loads of the subcategory can be attributed to the absence of these
processes.
As with woven fabric finishing, the number of processes performed
at a mill may vary considerably. In addition, hosiery manufac-
ture is distinct in terms of manufacturing and raw wastewater
characteristics. Consequently, internal subdivision is required
for this subcategory.
Simple Processing. This Knit Fabric Finishing subdivision
covers facilities that perform fiber preparation, scouring,
functional finishing, and/or one of the following processes
applied to more than 5% of total production: bleaching, dyeing,
or printing. This subdivision includes all Knit Fabric Finishing
mills that do not qualify under either the Complex Processing or
Hosiery Products subdivisions.
Complex Processing. This Knit Fabric Finishing subdivision
covers facilities that perform fiber preparation, scouring, func-
tional finishing, and/or more than one of the following processes
each applied to more than 5% of total production: bleaching,
dyeing, or printing.
Hosiery Products. This Knit Fabric Finishing subdivision
covers facilities that are engaged primarily in dyeing or finish-
ing hosiery of any type. Compared to other Knit Fabric Finishing
facilities, Hosiery Finishing mills are generally much smaller
(in terms of wet production), more frequently employ batch
processing, and more often consist of only one major wet process-
ing operation. All of these factors contribute to their lower
water use and much smaller average wastewater discharge.
Subcategory 6 - Carpet Finishing
This subcategory covers facilities that primarily finish textile-
based floor covering products, of which carpet is the primary
element, by employing any of the following processing operations
on at least 5% of their production: scouring, bleaching, dyeing,
printing, and application of functional finish chemicals.
Integrated mills that finish a majority of carpet along with
tufting or backing operations or other finishing operations such
as yarn dyeing are included in this subcategory, and total finish-
ing production should be applied to the applicable Carpet Finish-
ing effluent limitations to calculate discharge allowances. Mills
that only perform carpet tufting and/or backing are covered under
Subcategory 3 - Low Water Use Processing. Carpet Finishing is a
distinct segment of the textile industry because of the lower
degree of processing required and the typically weaker wastes
that result.
Date: 6/23/80 II.20-8
-------
Subcategory 7 - Stock and Yarn Finishing
This subcategory covers facilities that primarily finish stock,
yarn, or thread of cotton and/or synthetic fibers by employing
any of the following processing operation on at least 5% of their
production: scouring, bleaching, mercerizing, dyeing, or appli-
cation of functional finish chemicals. Facilities finishing '
stock, yarn, or thread principally of wool also are covered if
they do not perform carbonizing as needed for coverage under
Subcategory 2 - Wool Finishing. Denim finishing is included
under Subcategory 4 - Woven Fabric Finishing.
Typical stock and yarn finishing may include scouring, bleaching,
mercerizing, dyeing, or functional finishing. As a result of
process differences, the water usage and pollutant loadings of
this subcategory are lower than those found in most other
subcategories.
Subcategory 8 - Nonwoven Manufacturing
This subcategory covers facilities that primarily manufacture
nonwoven textile products of wool, cotton, or synthetics, singly
or as blends, by mechanical, thermal, and/or adhesive bonding
procedures. Nonwoven products produced by fulling and felting
processes are covered in Subcategory 9 - Felted Fabric
Processing.
The Nonwoven Manufacturing subcategory includes a variety of
products and processing methods. The processing is dry (mechan-
ical and thermal bonding) or low water use (adhesive bonding)
with the major influence on process-related waste characteristics
resulting from the cleanup of bonding mix tanks and application
equipment. Typical processing operations include carding, web
formation, wetting, bonding (padding or dipping with latex acrylic
or polyvinyl acetate resins) and application of functional finish
chemicals. Pigments for coloring the goods are usually added to
the bonding materials.
Subcategory 9 - Felted Fabric Processing
This subcategory covers facilities that primarily manufacture
nonwoven products by employing fulling and felting operations as
a means of achieving fiber bonding. Wool, rayon, and blends of
wool, rayon, and polyester are typically used to process felts.
Felting is accomplished by subjecting the web or mat to moisture,
chemicals (detergents), and mechanical action. Wastewater is
generated during rinsing steps that are required to prevent
rancidity and spoilage of the fibers.
Date: 6/23/80
II.20-9
-------
II.20.2 WASTEWATER CHARACTERIZATON [1]
Wastewater characteristics for the textile industry, in general,
reflect the products and the methods employed to manufacture
them. Because there is such a diversity in products, in process-
ing, in raw materials, and in process control, there is a wide
range in the characteristics. The variation extends vertically
within each subcategory, as well as horizontally among the sub-
categories. Nonprocess-related variables such as raw water
quality and discharge of nonprocess-related wastes (sanitary,
boiler blowdown, cooling water, etc.) contribute to this lack of
uniformity.
II.20.2.1 Subcategory 1 - Wool Scouring
Wool scouring waste contains significant quantities of natural
oils, fats, suint, and adventitious dirt that, even after in-
process grease recovery steps, cause the characteristics to be
distinctly different from those of the other subcategories.
These materials are collectively responsible for high concentra-
tions and quantities of BOD5, COD, TSS, and oil and grease.
Since the natural fat is technically a wax, it is not readily
biodegradable and must be removed by physical or chemical treat-
ment. Wastewater from the wool scouring process is usually
brown, thickly turbid, and noticeably greasy. It is strongly
alkaline and very putrescible.
II.20.2.2 Subcategory 2 - Wool Finishing
Wool finishing wastes are typically high volume, low concentra-
tion wastes (for the conventional pollutant parameters) that, in
terms of mass loadings, contribute large quantities of conven-
tional pollutants per unit of production. The nonconventional
pollutants (sulfide and color) and the toxic pollutants that have
been historically monitored (phenol and chromium) are both high
in concentration and quantity. These conditions can be attributed
to the numerous steps required in processing and finishing wool
yarn and wool fabric and to the wide variety of chemicals used.
II.20.2.3 Subcategory 3 - Low Water Use Processing
Low water use processing refers, almost exclusively, to facili-
ties that perform weaving or adhesive-related processing.
Regardless of mill size, process-related wastewaters from both
types of mills are typically very low in volume. The only mills
with large flows are those engaged in water-jet weaving and mills
discharging large volumes of cooling or other nonprocess water.
Where process-related wastewater is a large portion of the total
discharge, the wastewater characteristics are determined primarily
by the slashing process (conventional weaving), the weaving proc-
ess (water-jet weaving mills), or the dipping, padding, or
saturating process (adhesive-related mills).
Date: 6/23/80 11.20-10
-------
II.20.2.4 Subcategory 4 - Woven Fabric Finishing
The wastewater generated from the finishing of woven fabric is
represented by a rather broad range in concentration and mass
quantity for the conventional pollutant parameters. The internal
subdivisions of this subcategory (Simple Processing, Complex
Processing, Complex Processing Plus Desizing) group the estimated
336 mills into 3 reasonably distinct segments.
The differences between the three subdivisions are a function of
the complexity of the wet processing. Mills classified in the
Complex Processing subdivision perform simple processing plus
one or more additional major wet processing steps. Mills
classified in the Complex Processing Plus Desizing subdivision
perform complex processing plus desizing on the majority of their
production. The typical water use and waste mass loading values
are progressively greater for each subsequent subdivision and
generally reflect an increase in the same basic pollutant
parameters.
II.20.2.5 Subcategory 5 - Knit Fabric Finishing
The wastewater generated from the finishing of knit fabric are,
like those from the finishing of woven fabric, represented by a
rather broad range in concentration and mass quantity for the
conventional pollutant parameters. The typical waste is not
generally as great in terms of concentration as woven fabric
finishing waste, and the variability from mill to mill is also
somewhat less.
II.20.2.6 Subcategory 6 - Carpet Finishing
The wastewater volume from carpet mills is typically quite large,
although water use (gal/lb of product) is low relative to other
subcategories. This is due to the specialized nature of carpet
manufacturing and the heavy weight of carpet relative to other
textile products. The wet processing employed by a carpet mill
can include various combinations of the following operations:
scouring, bleaching, dyeing, printing, functional finishing, and
backing. Wastes from dyeing and printing are the major contrib-
utors to the high flows at these mills, but these processes do
not lead to extreme levels of conventional and nonconventional
pollutants. Scouring and bleaching are performed very little at
carpet finishing mills. Functional finishing and carpet backing
make small contributions to the total flow; the latter often
results in a latex waste that should be segregated from the rest
of the waste discharge for separate treatment.
Date: 6/23/80 11.20-11
-------
II.20.2.7 Subcategory 7 - Stock and Yarn Finishing
The volume of wastewater discharged by Stock and Yarn Finishing
facilities is comparable to that from mills in other finishing
subcategories. The wastes generated are generally not as strong
as those found in the other subcategories, and depend substan-
tially on whether natural fibers, blends, or synthetic fibers
alone are processed.
II.20.2.8 Subcategory 8 - Nonwoven Manufacturing
The nature of nonwoven manufacturing is such that a typical
facility has relatively small hydraulic and pollutant loadings.
The wastewater may contain latex and numerous other contaminants.
At a few facilities, special manufacturing operations or activi-
ties common to other subcategories might be performed with
resultant higher water use.
II.20.2.9 Subcategory 9 - Felted Fabric Processing
Felted fabric processing typically results in high volume
wastes of a generally dilute nature. The wet processing opera-
tions may include felting, dyeing, and functional finishing. The
rinses that follow felting (fulling) and dyeing, if employed,
result in considerable water use and contribute most of the
pollutants. Functional finishing may also make minor contribu-
tions to the waste load.
Table 20-2 presents the toxic pollutants found in detectable
concentrations for plant water supply, raw wastewater, and
secondary effluents. Tables 20-3 and 20-4 present the conven-
tional and classical pollutant raw wastewater concentrations
and pollutant loadings, respectively, by Subcategory. Values
in parentheses indicate the median of field sampling results.
The remaining values are generated from historical data and
from three or more plants.
II.20.3 PLANT SPECIFIC DESCRIPTION [3]
Tables 20-5 through 20-9 present toxic pollutant and classical
pollutant data for five textile mills.
Date: 6/23/80 11.20-12
-------
D
DJ
rt
CD
TABLE 20-2.
CO
o
M
O
I
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN TEXTILL MILL
WASTEWATER [1]
Concentrations observed, gq/L
Water supply
Number
of
Toxic pollutant plants
Metals and inorganics
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Nitrogen compounds
Acrylonitrile
1 , 2-Diphenylhydrazine
N-nitrosodiphenylamine
N-nitroso-di-n-propylamine
Phenols
2 -Chlorophenol
2 , 4-Dichlorophenol
2 , 4-Dimethylphenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Cresols
-Chloro- -cresol
6
4
a
4
5
5
6
4
6
4
6
6
6
4
12
6
1
3
5
Median
<5
<5
_
<5
< 10
<5
10
11
<5
0.2
<5
<5
<5
3
60
8.2
2.1
10
Raw wastewater
Number
of
Maximum plants
48
<5
_
<5
< 10
<5
47
22
45
0.8
47
23
17
3
4,540
39
1.6
5.5
36
23
14
-
5
22
37
40
10
26
10
32
10
26
5
45
27
2
7
10
4
1
1
3
1
2
11
25
4
1
Median
7
10
-
<5
<5
14
40
8.0
35
0.6
54
35
32
3
190
26
42
16
6.0
12
15
26
52
55
20
Maximum
170
200
-
40
46
880
2,400
39
750
4
300
740
130
9
7,900
860
73
67
86
14
1,600
22
72
78
41
940
4,900
27
170
Secondary effluent
Number
of
plants
16
8
-
5
15
27
28
5
16
7
18
4
15
4
30
23
1
4
1
1
2
1
1
1
1
2
7
1
1
Median
4.5
39
-
<5
6
20
32
12
46
0.4
70
47
25
3
200
18
1.5
10
12
14
Maximum
680
160
-
<5
13
1,800
290
980
120
0.7
150
97
140
18
38,000
231
3.6
9.4
1.0
400
19
5.9
8.0
4. 1
<10
15
50
19
32
aDashes indicate pollutant not analyzed for.
(continued)
-------
rt
(D
TABLE 20-2 (continued)
oo
o
H
H
•
NJ
O
I
Concentrations observed, pq/L
Toxic pollutant
Water supply
Number
of
plants Median Maximum
Raw wastewater
Number
of
plants Median Maximum
Secondary effluent
Number
of
plants Median Maximum
Monocyclic aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 6-Dinitrotoluene
Ethylbenzene
Hexachlorobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatics
Acenaphthene
Anthracene
Benzo ( b ) f luoranthene
Benzo ( k ) f luoranthene
Fluorene
Naphthalene
Pyrene
Polychlorinated biphenyls
and related compounds
2 -Chloronaphthalene
Halogenated aliphatics
Chloroform
Dichlorobromome thane
1 , 1-Dichloroe thane
1 , 2-Dichloroe thane
1 , 1-Dichloroe thylene
1 , 2-Dichloropropane
1 , 3-Dichloropropane
Methyl chloride
Methylene chloride
Tetrachloroe thylene
1,1, 1-Trichloroethane
Trichloroe thylene
Trichlorofluorome thane
Vinyl chloride
Pesticides and metabolites
4,4' -DDT
Dieldrin
TCDD
2 <4 <5 10
5
7
2
1
20
2
4 0.8 2.4 25
8
3
3 0.2 0.4 1
1
1
2 0.2 0.4 1
19
1
1
6 39 1,360 11
2 <5 <5 1
1
1
1
1
1 0.8
1
2 <5 <5 3
7
1 <5 4
10
3
1
_a
<5
25
2.0
110
54
1.3
26
410
8.7
44
48
47
<5
7.8
47
90
—
200
300
290
215
54
2,840
2
620
2,700
12
0.1
<10
<10
15
110
0.9
<10
640
6.6
14
<5
<5
100
<5
110
2,100
17
840
2,140
11
~
4
1
4
2
8
16
4
1
1
5
4
6
3
2
1
4
1
1
<5 64
3.5
10 20
0.8 1.5
63 3,000
14 1,400
610 1,580
0.5
4.4
22 255
0.2 0.3
8.5 58
<5 <5
11 17
<5
4.9 87
0.5
0.2
Dashes indicate pollutant not analyzed for.
-------
TABLE 20-3. RAW WASTEWATER POLLUTANT CONCENTRATIONS BY SUBCATEGORY [1]
rt
n>
OJ
CO
o
H
O
I
Subcategory 1
Number
of
Characteristic plants
Flow , gpd
BOD s, mg/L
COD, mg/L
TSS, mg/L
Sulfide, |jg/L
Oil and grease, mg/L
Phenol, Mg/L
Chromium, pg/L
Color, APHA units
Flow , gpd
BOD 5, mg/L
COD, mg/L
TSS, mg/L
Sulfide, Mg/L
Oil and grease, mg/L
Phenol, pg/L
Chromium, Mg/L
Color, APHA units
Flow, gpd
BOD5, mg/L
COD, mg/L
TSS, mg/L
Sulfide, Mg/L
Oil and grease, mg/L
Phenol, Mg/L
Chromium, Mg/L
Color, APHA units
11
9
4
8
7
48
32
28
26
6
11
10
16
9
71
35
29
32
3
9
9
13
9
Range
1 x 104-7.5 x 105
310-6,680
1,140-17,800
120-13,200
80-5,000
Subcategory 4a
1.5 x 104-5.5 x 106
19-2,050
200-5,020
16-2,440
25-580
6-1,440
10-600
1-530
20-10,000
Subcategory 5a
2.9 x 103-2.8 x 106
60-1,860
340-19,400
21-2,160
20-7,100
14-455
1-1,680
13-600
170-1,460
Median
7.0 x 104
2,270
7,030
3,310
(500)3
580
(120)
(2,200)
1.7 X 10s
270
900
62
72
69
49
38
800
5.6 X 10s
210
870
53
55
83
110
78
400
Number
of
plants
15
10
7
10
1
2
39
23
12
18
3
6
6
7
35
19
11
19
4
6
5
8
7
Subcategory 2
Range
5.0 x 104-4.2 x 106
66-750
280-2,000
17-245
50-155
Subcategory 4b
1.1 x 104-7.6 x 106
83-2,160
240-5,140
40-870
100-120
34-160
10-600
19-1,180
Subcategory 5b
3.0 x 104-3.5 x 106
120-920
545-3,150
18-740
50-1,470
6-110
72-230
10-180
37-940
Median
5.0 x 10s
170
590
62
(3,500)
(70)
(102)
(500)
(1,500)
4.0 X 10s
350
1,060
110
100
46
54
110
(1,400)
6.4 x 10s
270
790
60
155
52
100
80
750
Number
of
plants
13
13
8
12
1
51
36
29
28
5
5
11
57
39
27
29
4
13
10
17
8
Subcategory 3
Range
6.1 x 103-2.8 x 10s
37-2,550
115-2,960
10-530
Subcategory 4c
9 x 103-5.5 x 106
125-2,600
370-2,780
1-.1260
5-100
14-1,220
14-12,500
Subcategory 5c
1.1 x 103-4.1 x 105
38-790
450-4,980
9-180
10-8,000
15-275
26-580
10-1,200
40-1,060
Median
6.1 x 104
290
690
185
(80)
91
(4)
(10)
1.7 x 10s
420
1,240
150
(1,700)
68
150
100
(1,900)
6.0 x 104
320
1,370
82
560
99
62
80
450
Parentheses indicate value is median of field sampling results.
(continued)
-------
D
P>
ft
(D
to
00
o
TABLE 20-3 (continued)
N)
o
i
Number
of
Characteristic plants
Flow , gpd
BODS, mg/L
COD, mg/L
TSS, mg/L
Sulfide, pg/L
Oil and grease, mg/L
Phenol , pg/L
Chromium, pg/L
Color, APHA units
Flow, gpd
BOD5, mg/L
COD, mg/L
TSS, mg/L
Oil and grease, mg/L
Phenol , pg/L
Chromium, pg/L
Color, APHA units
37
10
14
12
4
5
7
7
4
11
4
3
4
3
Subcategory 6
Range
2.0 x 104-1.8 x 106
190-565
280-2,120
37-210
10-450
3-93
1-1,140
4-300
65-1,900
Subcategory 9
1.4 x 104-5 x 10s
64-630
205-3,940
59-180
10-370
Median
4.2 x 10s
440
1,190
67
175
18
130
30
490
1.0 X 10s
180
2,360
78
(60)
(40)
50
(90)
Number
of
plants
116
62
46
59
9
18
12
25
11
Subcategory 7
Range
1.2 x 104-2.6 x 106
43-1,630
140-4,760
2-4,200
1-4,440
1-180
3-620
4-1,600
57-3,000
Subcateqory 8
Number
of
Median plants Range Median
2.5 x 10s 11
185 4
680 4
38 4
200
21 3
170 3
100 2
570
2.9 X 103-4.0 X 10s 1.5 X 10s
55-380 200
230-2,090 550
68-285 120
(1,200)
8-160 28
70-1,100 575
60-500 275
(200)
Parentheses indicate value is median of field sampling results.
-------
TABLE 20-4.
RAW WASTEWATER POLLUTANT LOADINGS BY
SUBCATEGORY [1]
Characteristic
BOD5, kg/Mg
COD, kg/Mg
TSS, kg/Mg
Sulfide, g/Mg
Oil and grease, kg/Kg
Phenol , g/Mg
Chromium, g/Mg
BODC, kg/Mg
COD, kg/Mg
TSS, kg/Mg
Sulfide, g/Mg
Oil and greaie, kg/Mg
Phenol, g/Mg
Chromium, g/Mg
BOD5, kg/Mg
COD, kg/Mg
TSS, kg/Mg
Sulfide, g/Mg
Oil and grease, kg/Mg
Phenol, g/Mg
Chromium, g/Mg
BOD5, kg/Mg
COD, kg/Mg
TSS, kg/Mg
Sulfide, g/Mg
Oil and grease, kg/Mg
Phenol , g/Mg
Chromium, g/Mg
BOD5, kg/Mg
COD, kg/Mg
TSS, kg/Mg
Sulfide, g/Mg
Oil and grease, kg/Mg
Phenol, g/Mg
Chromium, g/Mg
Number
of
plants
9
4
8
7
32
28
26
6
11
10
16
35
29
32
3
9
9
13
10
14
12
4
5
7
7
4
3
4
1
1
1
3
Subcategory
Range
3.8-210
20-750
1.9-240
1.3-62
Subcategory
3.8-215
12-440
0.8-220
0.6-130
0.6-150
1.6-51
0.1-44
Subcattaorv
4.4-85
18-380
2.9-42
3.1-770
0.5-46
0.1-400
0.6-85
Subcategory
14-41
22-135
1.6-9.3
0.8-22
0.2-9.4
0.1-59
0.2-12
Subcategory
3.3-16
10-99
0.2-15
15
0.4-16
1
Median
42
130
43
10
4a
23
92
8
7.6
9.1
8.2
4.3
Sa
28
81
6.3
13
4
8.7
7.8
6
26
82
4.7
9.4
1.1
11
3.4
9
70
186
2.2
0.5
3.4
0.2
0.5
Number
of
plants
10
7
10
1
2
2
23
12
18
3
6
4
7
19
11
19
4
6
5
8
«2
46
59
9
18
12
25
Subcategory
Range
22-140
97-445
9.5-97
11-75
66-160
Subcategory
3.6-96
10-388
2-62
7.8-20
2.2-14
0.9-2S
2.4-49
Subcateaorv
8.0-140
49-500
1.3-110
6.3-110
0.4-16
3.4-37
1.4-35
Subcateaory
0.8-110
2.5-380
0.1-480
0.6-170
0.1-22
0.5-83
0.8-360
2
Median
60
200
17
7.8
43
110
4b
33
110
9.6
12.5
3.8
7,7
2.6
Sb
22
115
6.9
14
3.5
12
4.7
7
21
63
4.6
28
1.6
15.0
12.0
Number
of
plants
13
8
12
1
1
1
2
36
29
28
2
5
6
11
39
27
29
4
13
10
17
4
4
4
1
3
3
2
Subcategory
Range
0.2-22
2.7-26
0.3-4
1.5-3.4
Subcategory
5.9-190
48-900
0.2-84
15.7-290
0.4-15
0.9-150
0.6-1,520
Subcategory
1.6-140
26-630
0.3-24
2.0-400
1.4-28
1.8-150
0.4-270
Subcateqorv
15-310
64-380
16-120
2.4-130
16-500
11.7-139
3
Median
2.3
14.5
1.6
3.8
2.3
2.4
4c
45
120
15
155
4.1
13
21
Sc
26
89
6.7
100
6.6
4.2
6.4
8
6.7
38
64
117
11.2
247
75.4
Date: 6/23/80
11.20-17
-------
TABLE 20-5. WASTEWATER CHARACTERIZATION, PLANT 100 [3]
Category: Textile Mills
Wastewater treatment description: Neutralization, aeration,
clarification, carbon/sand filtration, chlorine contact
Influent flowrate, gpd: 960,000 av (650,000 to 1,400,000 range
during sampling)
Pollutant concentration, pg/L
Pollutant
Intake
water
Raw
wastewater
Clarifier
effluent
Filter
effluent
Toxic pollutants
Acrylonitrile
Benzene
Benzidine 0.4
1,2,4-Trichlorobenzene
Hexachlorobenzene 1.3
Bis(chloromethyl) ether
2,4,6-Trichlorophenol
p-Chloro-m-cresol
Chloroform
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
1,2-Dichloropropane
2,4-Dimethylphenol
Ethylbenzene 2.8
Methylene chloride 7.4
Naphthalene 0.3
N-nitrosodi-n-propylamine
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate 1.8
Diethyl phthalate 0.9
Dimethyl phthalate
Anthracene 0.4
Fluorene 0.06
Tetrachloroethylene 0.6
Toluene 2.1
Trichloroethylene
Antimony (total) <10
Arsenic (total) <1 ,
Asbestos (fibrous) NA
Beryllium (total) <0.04
Cadmium (total) 2.9
Chromium (total) <4
270
59
16
29
_a
_a
_a
20
56
190
5.9
8.7
18
1.6
425
24
18
1.0
310
2.8
10
160
19
NA
<0.04
<2
34
<100
40
<5
5
<5
3
<0.3
9
<5
18
<5
100
<0.8
13
160
4
NA
<0.04
<2
76
<100
11
<5
3
<5
3
<0.3
2.8
<5
12
<5
75
3.8
<0.5
160
4
NA
<0.04
<2
34
(continued)
Date: 6/23/80
11.20-18
-------
TABLE 20-5 (continued)
Pollutant
Pollutant concentration, pg/L
Intake
water
Raw
wastewater
Clarifier
effluent
Filter
effluent
Toxic pollutants (continued)
Copper (total)
Cyanide (total)
Lead (total)
Mercury (total)
Nickel (total)
Selenium (total)
Silver (total)
Thallium (total)
Zinc (total)
TCDD
Criteria pollutants
BOD, mg/L
COD, mg/L
TSS, mg/L
Oil and grease, mg/L
Total phenols, mg/L
Sulfide, mg/L
Color (ADMI @ pH 7.6)
pH, pH units
Other pollutants
Color (ADMI @ original pH)
63
<2
<22
<0.5
<36
1
<5
<50
420
NA
49
<2
<22
<0.5
<36
<1
<5
<50
490
NA
120
<2
<22
<36
<5
250
NA
51
<2
<22
45
13
240
NA
Pollutant concentration,
units as specified
NA
15
NA
0.002
<0.003
<5
7.3
<5
NA
230
25
NA
0.81
0.044
130
6.9
130
NA
130
130
NA
0.02
0.006
110
7.6
120
NA
130
74
NA
0.018
0.009
110
7.6
110
Note: Blanks indicate that concentrations were below detection limit.
aTotal of 56 pg/L.
Not analyzed.
Date: 6/23/80
11.20-19
-------
TABLE 20-6. WASTEWATER CHARACTERIZATION, PLANT 200 [3]
Category: Textile Mills
Wastewater treatment description: Lime and ferric chloride reactors,
polyelectrolyte addition, primary clarification, aeration, secondary
clarification, chlorination, multimedia pressure filter
Influent flowrate, gpd: 440,000 av (90,000 to 840,000 range during sampling)
Pollutant concentration, |jg/L
Pollutant
Intake
water
Raw
wastewater
Primary
clarifier
effluent
Secondary
clarifier Filter
effluent effluent
Toxic pollutants
Acrylonitrile
Benzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
2,4,6-Trichlorophenol
p-Chloro-m-cresol
Chloroform
1,2-Dichlorobenzene
Ethylbenzene
Fluoranthene
Methyl chloride
Naphthalene
N-nitrosodi-n-propylamine
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Anthracene
Fluorene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony (total)
Arsenic (total)
Asbestos (fibrous)
Beryllium (total)
Cadmium (total)
Chromium (total)
Copper (total)
Cyanide (total)
Lead (total)
0.4
360
6.0
0.2
9.0
0.8
9.3
26
0.5
0.2
7.0
0.8
8.0
5.0
0.4
0.3
1.9
3.2
<10
-------
TABLE 20-6 (continued)
Pollutant concentration, pg/L
Pollutant
Primary
Intake Raw clarifier
water wastewater effluent
Secondary
clarifier Filter
effluent effluent
Toxic pollutants (continued)
Mercury (total)
Nickel (total)
Selenium (total)
Silver (total)
Thallium (total)
Zinc (total)
TCDD
<36
<5
<50
45
NA
230
22
<50
1,040
NA
180
10
460
NA
150
<5
51
NA
220
10
150
NA
Pollutant concentration, units as specified
Criteria pollutants
BOD, mg/L
COD, mg/L
TSS, mg/L
Oil and grease, mg/L
Total phenols, mg/L
Sulfide, mg/L
Color (ADMI @ pH 7.6)
pH, pH units
Other pollutants
Color (ADMI @ original pH)
NA
15 4
5
NA
<0.002
0.059
5
7.4
NA
,530
885
NA
0.19
0.45
30
5.5
31
NA
,000
40
NA
0.030
0.098
35
5.3
90
NA
110
10
NA
<0.002
0.02
30
8.2
15
NA
96
7
NA
0.002
<0.003
13
8.0
13
Note:
a.
Blanks indicate that concentrations were below detection limit.
'Not analyzed.
Date: 6/23/80
11.20-21
-------
TABLE 20-7. WASTEWATER CHARACTERIZATION, PLANT 400 [3]
Category: Textile Mills
Wastewater treatment description: Holding basin, aeration basins,
clarification, sand filtration, chlorine contact
Influent flowrate, gpd: 260,000av (230,000 to 320,000 range during
sampling)
Pollutant concentration,
Pollutant
Toxic pollutants
Acrolein
Acrylonitrile
Benzene
1,2, 4-Trichlorobenzene
2 , 4 , 6-Trichlorophenol
p-Chloro-m-cresol
Chloroform
1 , 2-Dichlorobenzene
Ethylbenzene
Methylene chloride
Naphthalene
N-nitrosodi-n-propylamine
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) phthalate
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony (total)
Arsenic (total)
Asbestos (fibrous)
Beryllium (total)
Cadmium (total)
Chromium (total)
Copper (total)
Cyanide (total)
Lead (total)
Mercury (total)
Nickel (total)
Selenium (total)
Silver (total)
Thallium (total)
Intake
water
22
4.8
<10
<1
NA3
<0.04
<2
<4
11
<5
<22
<0.2
<36
<1
<5
<50
Holding
pond
effluent
200
90
2.1
30
0.9
110
8.7
3.7
4.8
190
1
NA
<0.04
5.3
<4
17
<5
99
<0.2
69
3
19
<50
Secondary
clarifier
effluent
<100
<1
<2
<5
<5
<5
<0.5
<0.3
<1
<5
<5
<5
<0.8
<0.5
39
84
NA
<0.04
<2
<4
8
<5
40
20
16
<50
pg/L
Filter
effluent
120
<100
<1
<2
<5
<5
77
<0.5
<0.3
<1
<5
<5
<5
<0.8
<0.5
59
81
NA
<0.04
<2
<4
6
<5
71
54
12
Not analyzed.
(continued)
Date: 6/23/80
11.20-22
-------
TABLE 20-7 (continued)
Pollutant concentration,
units as specified
Pollutant
Intake
water
Holding
pond
effluent
Secondary
clarifier
effluent
Filter
effluent
Toxic pollutants (continued)
Zinc (total) 33 340 58 71
TCDD NA3 NA NA NA
Criteria pollutants
BOD, mg/L NA NA NA NA
COD, mg/L 6.3 1,740 190 130
TSS, mg/L 12 200 50 35
Oil and grease, mg/L NA NA NA NA
Total phenols, mg/L 0.011 0.034 0.007 0.006
Sulfide, mg/L <0.003 0.050 0.012 <0.003
Color (ADMI @ pH 7.6) 8 160 79 73
pH 8.0 7.2 7.6 7.6
Other pollutants
Color (ADMI @ original pH) 50 160 83 74
Note: Blanks indicate that concentrations were below detection limit
Not analyzed.
Date: 6/23/80
11.20-23
-------
TABLE 20-8. WASTEWATER CHARACTERIZATION, PLANT 500 [3]
Category: Textile Mills
Wastewater treatment description: Holding basin, aerated lagoon,
clarifier, dissolved air flotation, chlorine contact, polishing
pond
Influent flowrate, gpd: 276,000 (252,000 to 288,000 range during
sampling)
Pollutant concentration,
Pollutant
Intake
water
Raw
wastewater
Secondary
clarifier
effluent
DAF
effluent
Toxic pollutants
Acrylonitrile <100 <100
Benzene 0.3 0.3 <1 <100
1,2,4-Trichlorobenzene <2 <2
1,1,1-Trichloroethane 2.8
1,1,2,2-Tetrachloroethane 21
2,4,6-Trichlorophenol <5 <5
p-Chloro-m-cresol <5 <5
Chloroform 21
1,2-Dichlorobenzene <0.5 <0.5
l^-iFmns-dichloroethylene 4.5
2,4-Dimethylphenol 20
Ethylbenzene 1.1 <0.3 <0.3
Methylene chloride 11 82
Naphthalene 210 <1 <1
N-nitrosodi-n-propylamine <5 <5
Pentachlorophenol 2.1 <5 <5
Phenol <5 <5
Bis(2-ethylhexyl) phthalate <0.5
Butyl benzyl phthalate 1.6 160
Di-n-butyl phthalate 0.6 3.0
Diethyl phthalate 150
Acenaphthylene 4,400
Anthracene 0.05
Tetrachloroethylene 1.8 890 320 220
Toluene 7.3 2.9 2.0 1.2
Trichloroethylene 0.6 3.1 24 2.8
Antimony (total) 24 515 450 375
Arsenic (total) 2 4
Beryllium (total) <0.04 <0.04 <0.04 <0.04
Asbestos (fibrous) NAa NA NA NA
Cadmium (total) 2 <2 <2 <2
Chromium (total) 6 4 6 <4
Copper (total) 46 44 14 <4
Not analyzed
(continued)
Date: 6/23/80
11.20-24
-------
TABLE 20-8 (continued)
Pollutant concentration, pg/L
Pollutant
Intake
water
Raw
wastewater
Secondary
clarifier
effluent
DAF
effluent
Toxic pollutants (continued)
Cyanide (total)
Lead (total)
Mercury (total)
Nickel (total)
Selenium (total)
Silver (total)
Thallium (total)
Zinc (total)
TCDD
Criteria pollutants
BOD, mg/L
COD, mg/L
TSS, mg/L
Oil and grease, mg/L
Total phenols, mg/L
Sulfide, mg/L
Color (ADMI @ pH 7.6)
pH, pH units
Other pollutants
Color (ADMI @ original pH)
<2
53
130
<2
14
<50
19
NA
12
62
130
<2
11
<50
75
NA
<2
46
150
16
54
NA
<2
25
110
15
45
NA
Pollutant concentration,
units as specified
NA
8.0
6
NA
0.006
<0.003
280
7.6
280
NA
,380
100
NA
0.048
<0.003
120
7.9
140
NA
480
26
NA
0.021
<0.003
82
7.7
81
NA
150
8
NA
0.10
<0.003
49
7.3
48
Blanks indicates that concentrations were below detection limit.
Not analyzed.
Note:
a
Date: 6/23/80
11.20-25
-------
TABLE 20-9. WASTEWATER CHARACTERIZATION, PLANT 700 [3]
Category: Textile Mills
Wastewater treatment description: Aerated equalization, ferric
chloride addition, flocculation, clarification
Influent flowrate, gpd: 467,000 av (400,000 to 525,000 range
during sampling)
Pollutant concentration, pg/L
Pollutant
Toxic pollutants
Acrylonitrile
Benzene
Chlorobenzene
1,2, 4-Trichlorobenzene
1,1,2, 2-Tetrachloroe thane
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
Chloroform
2-Chlorophenol
2 , 4-Dimethylphenol
Ethylbenzene
Methylene chloride
Naphthalene
4-Nitrophenol
N-nitrosodi-n-propylamine
Pentachlorophenol
Phenol
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Anthracene
Phenanthrene
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony (total)
Arsenic (total)
Asbestos (fibrous)
Beryllium (total)
Cadmium (total)
Chromium (total)
Copper (total)
Cyanide (total)
Lead (total)
Mercury (total)
Nickel (total)
Intake Aeration
water effluent
0.2
0.3
6.3
2.6
1.7
0.1
0.2
0.7
0.4
36
a
NA3
<0.04
<3
8
48
<5
55
<1
150
0.2
0.4
0.1
8.5
1.0
10
2.3
0.3
4.0
5.5
240
33
5.1
1.4
0.2
1.6
0.3
200
3
NA
<0.04
4
23
40
<5
63
<1
150
Clarifier
effluent
<100
<1
17
7.4
<5
<5
0.3
38
20
<5
49
24
2
15
67
NA
<0.04
7
19
8.3
<5
71
140
Filter
effluent
<100
<1
19
11
<5
55
0.3
38
69
<0.8
1.6
23
60
NA
<0.04
6
14
7.7
<5
63
150
(continued)
Date: 6/23/80
11.20-26
-------
TABLE 20-9 (continued)
Pollutant concentration,
Pollutant
Intake
water
Aeration
effluent
Clarifier
effluent
Filter
effluent
Toxic pollutants (continued)
Selenium (total)
Silver (total)
Thallium (total)
Zinc (total)
TCDD
Criteria pollutants
BOD, mg/L
COD, mg/L
TSS, mg/L
Oil and grease, mg/L
Total phenols, mg/L
Sulfide, mg/L
Color (ADMI @ pH 7.6)
pH, pH units
Other pollutants
Color (ADMI @ original pH)
2
43
<50
270
NA
3
51
<50
140
NA
45
640
NA
49
45
NA
Pollutant concentration,
units as specified
NAa
21
8
NA
0.013
<0.003
10
8.2
14
NA
740
58
NA
0.069
0.420
110
7.45
140
NA
530
50
NA
0.084
0.086
92
7.0
94
NA
420
18
NA
0.096
<0.003
68
6.4
67
Note: Blanks indicate that concentrations were below detection limit.
Not analyzed.
Date: 6/23/80
11.20-27
-------
II.20.4 POLLUTANT REMOVABILITY [1]
This section addresses current treatment technologies and pollu-
tant removability associated with the Textile Industry.
II.20.4.1 Industry Application of Wastewater Treatment
The following is a summary of methods and removal efficiencies
for systems for which data were obtained.
(1) Aerated lagoons (see Table 20-10)
Used by: Direct dischargers - 33
Indirect dischargers - 12
(2) Activated sludge (see Table 20-11)
Used by: Direct dischargers - 94
Indirect dischargers - 11
(3) Stabilization lagoons (see Table 20-12)
Used by: Direct dischargers - 44
Indirect dischargers - 17
(4) Polishing ponds
Subcategory 7, one plant sampled (see Table 20-13)
Subcategory 9, one plant sampled (see Table 20-14)
(5) Coagulation, chemical or polymer (see Table 20-15)
Used by: Direct dischargers - 16
Indirect dischargers - 15
Zero dischargers - 3
Date: 6/23/80 11.20-28
-------
TABLE 20-10. EFFECTIVENESS OF AERATED LAGOONS [1]
Subcat-
egory
4c
4a
4c
5a
7
7
Dis-
charge
Direct
Indirect
Indirect
Indirect
Direct
Direct
hp/
Mgal
45
400
780
150
25
1,000
Detention
time , hr
60
24
86
18
75
0.5
BOD,
mg/L
Inf Eff
370
69
1,740
390
110
250
94
69
160
190 1
14
250
COD,
Inf
835
640
-
,760
560
mg/L
Eff
810
580
-
1,220
430
TSS,
Inf
_
54
560
21
—
mg/L
Eff
89
68
600
12
110
Mgal = Million gallons.
TABLE 20-11. EFFECTIVENESS OF ACTIVATED SLUDGE [1]
Subcat-
egory
1
4c
4a
4c
4c
4c
4c
4a
4b
5b
5a
5a
5b
5b
6
7
7
7
Dis-
charge
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Direct
Indirect
Indirect
hp/
Mgal
160
120
60
41
58
250
80
60
90
60
74
40
75
160
44
80
500
80
Detention,
time , hr
99
110
24
75
130
97
78
120
80
48
82
420
110
76
130
33
44
50
BOD,
Inf
1,560
475
130
270
400
330
640
180
250
270
190
200
180
1,100
210
150
1,630
125
mg/L
Eff
125
19
22
24
8
23
105
9
5
45
19
13
5
11
29
6
230
5
COD,
Inf
16,200
-
472
840
-
2,970
1,240
470
-
690
340
745
-
-
610
500
4,760
""
mg/L
Eff
2,600
-
310
340
250
590
660
160
-
350
160
230
120
260
230
126
1,840
160
TSS,
Inf
3,970
-
34
-
80
-
170
26
220
28
97
49
18
280
93
36
140
46
mg/L
Eff
1,230
91
38
27
8
44
180
18
48
55
63
62
18
45
50
27
195
21
aMgal = Million gallons.
Calculated based on average flow and basin volume available for the year
1976.
Date: 6/23/80 11.20-29
-------
TABLE 20-12. EFFECTIVENESS OF STABILIZATION
LAGOONS [1]
Effluent
concentration,
mg/L
Subcategory
4c
4c
4b
5b
5b
5a
5c
7
7
8
8
Discharge
Direct
Direct
Indirect
Indirect
Indirect
Indirect
Indirect
Indirect
Indirect
Direct
Indirect
BOD
53
35
480
325
145
140
210
230
110
17
79
COD
175
115
2,190
810
—
860
550
630
790
—
~
TSS
14
35
18
40
—
—
—
59
945
29
180
a
Influent data were not presented.
TABLE 20-13. EFFECTIVENESS OF A POLISHING POND,
SUBCATEGORY 7 [1]
Conventional and nonconventional
pollutant treatability
Pollutant Influent Effluent
COD, mg/L 78 140
TSS, mg/L 37 28
Phenols, M9/L 36 51
Sulfide, pg/L 2 ND
Color, ADMI 210 220
Priority pollutant treatabilty
Influent, Effluent,
Priority pollutant pg/L pg/L
Trichlorofluoromethane 48 ND
Bis(2-ethylhexyl) phthalate 40 11
Lead 36 ND
Zinc 865 120
aNot detected.
Date: 6/23/80 11.20-30
-------
TABLE 20-14. EFFECTIVENESS OF A POLISHING POND,
SUBCATEGORY 9 [1]
Conventional and nonconventional
pollutant treatability
Parameter Influent Effluent
COD , mg/L
TSS, mg/L
Phenols, (jg/L
Sulfide, pg/L
Color, ADMI
550
91
52a
NDa
280
260
22
28
ND
300
Priority pollutant treatability
Influent, Effluent,
Priority pollutant pg/L pg/L
Naphthalene 56 NDa
Bis(2-ethylhexyl) phthalate 18 ND
Chromium 35 ND
Copper ND 18
Selenium 32 18
Zinc 45 100
aNot detected.
Date: 6/23/80 11.20-31
-------
TABLE 20-15. EFFECTIVENESS OF COAGULATION [1]
Subcat-
egory
2
4b
4ba
4c
4c
4ca
4C3
5a
5a
5a
7
7
8
Coagulants
Alum,
polymer
Alum
_
_
Polymer
Ferric
chloride,
lime
-
-
Polymer
Polymer
Alum,
polymer
Chlorinated
copperas.
lime
_
Treatment
step
BOD,
Inf
mg/L
Eff
COD,
Inf
mg/L
Eff
TSS,
Inf
mg/L
Eff
Direct dischargers
Secondary
clarifier
Secondary
clarifier
Flotation
unit
Secondary
clarifier
Secondary
clarifier
Coag/floc
raw waste
-
Coag/floc
secondary
Secondary
clarifier
Injection
prefiltra-
tion
Secondary
clarifier
Secondary
clarifier
Flotation
postbio-
logical
150
83
-
200
-
-
760
330
-
280
330
60
~
11
14
51
51
7
4
12
24
24
5
20
15
6
900
310
-
845
850
1,400
1,600
1,265
-
930
1,570
330
—
-
150
480
660
160
99
250
210
270
200
480
130
~
175
43
-
82
-
170
420
-
-
41
26
31
•~
64
35
190
140
54
30
99
40
65
7
23
11
14
Indirect dischargers
2
4aa
4ca
4ab
4aa
4a
Lime
Lime,
alum
Ferric
chloride
Aluminum
chloride
Alum
Alum
Coag/floc
raw waste
Flotation
Coag/clarify
print waste
Flotation
print waste
Coag/clarify
print waste
Recycle
Flotation
-
-
-
-
320
-
250
420
340
130
1,330
-
-
-
1,980
560
400
695
885
260
-
—
-
-
460
560
30
120
210
72
plant
300
10
-
1,550
-
5
Fabric printing is a signficant portion of production.
''Latex and PVC coating operations.
Date: 6/23/80
11.20-32
-------
II.20.4.2 Other Methods and Industry Applications
Other full-scale treatment methods that have been cited in the
literature, but for which no data were presented, include:
screening, neutralization, equalization, biological processes,
and biological beds.
II.20.5 REFERENCES
1. Technical Study Report BATEA-NSPS-PSES-PSNS - Textile Mills
Point Source Category (draft contractor's report). Contracts
68-01-3289 and 68-01-3884, U.S. Environmental Protection
Agency, Washington, D.C., November 1978.
2. NRDC Consent Decree Industry Summary - Textile Mills.
3. MRC internal sampling data on file at Effluent Guidelines
Division of EPA, 1978.
Date: 6/23/80 11.20-33
-------
11.21 TIMBER PRODUCTS PROCESSING
II.21.1 INDUSTRY DESCRIPTION [1]
II.21.1.1 General Description
The Timber Products Processing Industry encompasses manufacturers
and processors who use forest materials to produce their goods
and merchandise. The Environmental Protection Agency recognizes
15 distinct subcategories of manufacturers and/or processors
engaged in utilization of timber. This section addresses three
major subsections of the entire industry, (encompassing five
subcategories): wood preserving, both steaming and Boulton
processes; insulation board manufacturing; and both SIS and S2S
hardboard manufacturing.
Table 21-1 presents industry summary data for the Timber Products
Processing point source category in terms of the number of sub-
categories and number of dischargers [1, 2].
II.21.1.2 Subcategory Descriptions
This section presents general descriptions and process descrip-
tions for the following five subcategories of the Timber Products
Processing point source category: wood preserving (steaming and
Boulton processes), insulation board manufacturing, and hardboard
manufacturing (SIS and S2S). The remaining ten subcategories
have been classified as Paragraph 8 exclusions and will not be
discussed in this report.
Wood Preserving
According to information from the American Wood Preserver's
Association there are approximately 300 companies, with a total
employment of about 11,000, engaged in wood preserving in the
United States. Fifty percent of the industry capacity is control-
led by 10 companies. Over three-quarters of the plants are
concentrated in two distinct regions. One area extends from east
Texas to Maryland and corresponds roughly to the natural range of
the Southern pines, the major species utilized. The second,
smaller area is located along the Pacific Coast, where Douglas
fir and western red cedar are the predominant species.
The three most prevalent types of preservatives used in wood
preserving are creosote, pentachlorophenol (PCP), and various
Date: 6/23/80 II.21-1
-------
TABLE 21-1. INDUSTRY SUMMARY [I, 2]
Industry: Timber Products Processing
Total Number of Subcategories: 15
Number of Subcategories Studied: 5
Number of Dischargers in Industry:
• Direct: 15
• Indirect: 49
• Zero: 363
formulations of water-soluble inorganic chemicals, the most com-
mon of which are the salts of copper, chromium, and arsenic.
Fire retardants are formulations of salts, the principal ones
being borates, phosphates, and ammonium compounds. Eighty per-
cent of the plants in the United States use at least two of the
three types of preservatives. Many plants treat with one or two
preservatives plus a fire retardant.
The wood preserving process consists of two basic steps:
(1) preconditioning the wood to reduce its natural moisture
content and to increase the permeability, and (2) impregnating
the wood with the desired preservatives.
The preconditioning step may be performed by one of several
methods including (1) seasoning or drying wood in large, open
yards; (2) kiln drying; (3) steaming the wood at elevated pres-
sure in a retort followed by application of a vacuum; (4) heating
the stock in a preservative bath under reduced pressure in a
retort (Boulton process); or (5) vapor drying, heating of the
unseasoned wood in a solvent to prepare it for preservative
treatment. All of these preconditioning methods have as their
objective the reduction of moisture content of the unseasoned
stock to a point where the requisite amount of preservative can
be retained in the wood.
Conventional steam conditioning (open steaming) is a process in
which unseasoned or partially seasoned stock is subjected to
direct steam impingement at an elevated pressure in a retort. The
maximum permissible temperature is set by industry standards at
118°C and the duration of the steaming cycle is limited by these
standards to no more than 20 hours. Steam condensate that forms
in the retort exits through traps and is conducted to oil-water
separators for removal of free oils. Removal of emulsified oils
requires further treatment.
Date: 6/23/80 II.21-2
-------
In closed steaming, a widely used variation of conventional steam
conditioning, the steam needed for conditioning is generated in-
situ by covering the coils in the retort with water from a reser-
voir and heating the water by passing process steam through the
coils. The water is returned to the reservoir after oil separa-
tion and reused during the next steaming cycle. There is a
slight increase in volume of water in the storage tank after each
cycle due to water exuded from the wood. A small blowdown from
the storage tank is necessary to account for this excess water
and also to control the level of wood sugars in the water.
Modified closed steaming is a variation of the steam conditioning
process in which steam condensate is allowed to accumulate in the
retort during the steaming operation until it covers the heating
coils. At that point, direct steaming is discontinued and the
remaining steam required for the cycle is generated within the
retort by utilizing the heating coils. Upon completing the steam-
ing cycle, the water in the cylinder is discarded after recovery
of oils.
Preconditioning is accomplished in the Boulton process by heating
the stock in a preservative bath under reduced pressure in the
retort. The preservative serves as a heat transfer medium. After
the cylinder temperature has been raised to operating temperature,
a vacuum is drawn, and water removed in vapor form from the wood
passes through a condenser to an oil-water separator where low-
boiling fractions of the preservative are removed. The Boulton
cycle may have a duraction of 48 hours or longer for large poles
and piling, a fact that accounts for the lower production per
retort day as compared to plants that steam condition.
The vapor-drying process consists of exposing wood in a closed
vessel to vapors from any one of many organic chemicals that
are immiscible with water and have a narrow boiling range.
Table 21-2 presents a summary of information pertaining to the
wood preserving category.
Insulation Board Manufacturing
Insulation board is a form of fiberboard, which in turn is a
broad generic term applied to sheet materials constructed from
ligno-cellulosic fibers. Insulation board is a "noncompressed"
fiberboard, which is differentiated from "compressed" fiber-
boards, such as hardboard, on the basis of density. Densities
of insulation board range from about 0.15 to 0.50 g/cm3
(9.5 to 31 lb/ft3).
There are 18 insulation board plants in the United States with
a combined annual production capacity of over 330 million square
meters (3,600 million square feet) on a 13-mm (0.5-in.) basis.
Sixteen of the plants use wood as a raw material for some or all
Date: 6/23/80 II.21-3
-------
TABLE 21-2. WOOD PRESERVING SUBCATEGORY SUMMARY [1, 2]
Number of Dischargers :
Boulton Steaming Inorganic salt Nonpressure
• Direct: 0 10 1 0
• Indirect: 11 23 5 0
• Zero: 24 57 56 23
Pollutants and Toxics Found in Significant Quantities:
Pentachlorophenol Arsenic
Phenol BOD
2,4-Dimethylphenol TSS
2,4-Dichlorophenol COD
Copper Oil and grease
Chromium Phenols (standard methods)
Number of Toxic Pollutants Found in:
• Raw wastewater: 39
• Treated effluent: 39
Candidate Treatment and Control Technologies:
Primary oil water separation
Secondary oil water separation
Biological treatment
Reuse and recycle
Evaporation
aThose plants responding to questionnaires for industry study.
of their production. One plant uses bagasse exclusively, and
one plant uses waste paper exclusively for raw material. Four
plants use mineral wool, a nonwood-based product, as a raw mate-
rial for part of their insulation board production. Production
of mineral wood board is classified under SIC 3296 and is not
within the scope of this section. Five plants produce hardboard
products as well as insulation board at the same facility.
Insulation board can be formed from a variety of raw materials
including wood from softwood and hardwood species, mineral fiber,
waste paper, bagasse, and other fibrous materials. In this
section, only those processes employing wood as raw materials are
considered. Plants utilizing wood may receive it as roundwood,
fractionated wood, and/or whole tree chips. Fractionated wood
can be in the form of chips, sawdust, or planer shavings.
Date: 6/23/80 II.21-4
-------
At the time of this compilation only limited data were available
on this subcategory. Available data are contained in the tables
in Section II.21.2. Table 21-3 summarizes information pertaining
to the insulation board manufacturing subcategory.
TABLE 21-3. INSULATION BOARD MANUFACTURING
SUBCATEGORY SUMMARY [1, 2]
Number of Dischargers:
• Direct: 8
• Indirect: 6
• Zero: 2
Pollutants and Toxics Found in Significant Quantities:
Copper
Chromium
Arsenic
BOD
TSS
Number of Toxic Pollutants Found in:
• Raw wastewater: 17
• Treated effluent: 13
Candidate Treatment and Control Technologies:
Biological treatment
Reuse and recycle
Evaporation
Those plants responding to questionnaires for indus-
try study.
Includes three self-contained dischargers-spray
irrigation.
Hardboard Manufacturing
Hardboard is a form of fiberboard, which is a broad generic term
applied to sheet materials constructed from ligno-cellulosic
fibers. Hardboard is a "compressed" fiberboard, with a density
over 0.50 g/cm3 (31 lb/ft3). The thickness of hardboard products
ranges between 2 and 13 mm (nominal 1/12 to 7/16 in.).
Production of hardboard by the wet process method is accomplished
by thermo-mechanical fiberization of the wood furnish. One plant
produces wet-dry hardboard using primarily mechanical refining.
Date: 6/23/80 II.21-5
-------
Dilution of the wood fiber with fresh or process water then allows
forming of a wet mat of a desired thickness on a forming machine.
This wet mat is then pressed either wet or after drying. Chemical
additives help the overall strength and uniformity of the product.
The uses of manufactured products are many and varied, requiring
different processes and control measures. The quality and type
of board are important in the end use of the product.
Hardboard which is pressed wet immediately following forming of
the wet-lap is called wet-wet or smooth-one-side (SIS) hardboard;
that which is pressed after the wet-lap has been dried is called
wet-dry or smooth-two-side (S2S) hardboard.
There are 16 wet process hardboard plants in the United States,
representing an annual production in excess of 1.5 million metric
tons per year. Seven of the plants produce only SIS hardboard.
Nine plants produce S2S hardboard. Of these nine, five plants
also produce insulation board, while three plants also produce
SIS hardboard.
Table 21-4 presents a summary of pertinent information pertaining
to the hardboard manufacturing subcategory.
TABLE 21-4. HARDBOARD MANUFACTURING SUBCATEGORY SUMMARY [1, 2]
Number of Dischargers:
• Direct: 12
• Indirect: 2
• Zero: 2
Pollutants and Toxics Found in Significant Quantities:
Copper
Chromium
Arsenic
BOD
TSS
Number of Toxic Pollutants Found in:
• Raw wastewater: 23
• Treated effluent: 17
Candidate Treatment and Control Technologies:
Biological treatment
Reuse and recycle
Evaporation
Those plants responding to questionnaires for indus-
try study.
Date: 6/23/80 II.21-6
-------
II.21.2 WASTEWATER CHARACTERIZATION [1]
II.21.2.1 Wood Preserving
The quantity of wastewater generated by a wood preserving plant
is a function of the method of conditioning used, the moisture
content of the wood being treated, and the amount of rainwater
draining toward the treating cylinder. Most wood preserving
plants treat stock having a wide range of moisture contents.
Although most plants will predominantly use one of the major
conditioning methods, many plants will use a combination of
several conditioning methods, and the actual quantity of waste-
water generated by a specific plant may vary considerably. The
average wastewater volume from 14 Boulton plants is reported to
be 21,210 L/d (5,600 gal/d) or 139 L/m3 (1.03 gal/ft3). The
average wastewater volume for eight closed loop steaming plants
is 5,200 L/d (1,370 gal/d) or 60.0 L/m3 (0.45 gal/ft3). The
average wastewater volume for 10 plants which treat significant
amounts of dry stock is 13,300 L/d (3,510 gal/d) or 121 L/m3
(0.91 gal/ft3). Additionally the average wastewater volume for
13 open steaming plants is 24,700 L/d (8,810 gal/d) or 324 L/m3
(2.43 gal/ft3).
Table 21-5 presents concentrations of toxic pollutants found in
the raw wastewater (for both steaming and Boulton processes) and
treated effluent (for steaming and Boulton processes combined).
Table 21-6 similarly presents toxic pollutant loadings in kg/m3
of product derived from the concentrations given in Table 21-5
for the wood preserving subcategory. Conventional pollutant
concentrations are shown in Table 21-7 and corresponding
pollutant loads in Table 21-8.
II.21.2.2 Insulation Board Manufacturing
Insulation board plants responding to the data collection portfo-
lio reported fresh water usage rates ranging from 95 to 5,700
liters per day for process water (0.025 to 1.5 MGD). One insula-
tion board plant, Plant 543, which also produces hardboard in
approximately equal amounts, uses over 15 million liters per day
(4 MGD) of fresh water for process water.
Water becomes contaminated during the production of insulation
board primarily through contact with the wood during fiber prep-
aparation and forming operations, and the vast majority of pol-
lutants are fine wood fibers and soluble wood sugars and
extractives.
More specifically potential sources of wastewater in an insula-
tion board plant include:
Date: 6/23/80 II.21-7
-------
TABLE 21-5.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
STEAMING AND BOULTON SUBCATEGORY WASTEWATER
(pg/D
[1]
Raw wastewater
Treated effluent
Steaming process Boulton process steaming and Boulton
Number
of
Toxic pollutant plants Rajige
Number
of
Median plants Range
Number
of
Median plants Range
process
Median
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Phenols
2-chloropnenol
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
2, 4,6-Trichlorophenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene/phcnanthrene
Benzo (a) anthracene
Benzo (a)pyrene
Benzo (b) f luoranthene
Benzo (ghi) perylene
Benzo (k)f luoranthene
Chrysene
Dibenzo (ah] anthracene
Fluoranthene
Fl uorene
Indeno ( 1 , 2 , 3-cd ) pyrene
Naphthalene
Pyrene
Halogenated aliphatics
Methyl chloride
Methylene chloride
8
12
8
8
11
12
8
8
8
8
a
8
8
5
5
5
12
5
5
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
4
BDL -
BDL -
BDL -
BDL -
BDL -
8 -
1 -
BDL -
3 -
BDL -
BDL -
BDL -
119 -
BDL -
BDL -
BDL -
BDL -
1,400
BDL -
3 -
37 -
27 -
1,060
BDL -
195 -
BDL -
BDL -
BDL -
BDL -
BDL -
BDL -
BDL -
633 -
820 -
BDL -
464 -
360 -
BDL -
BDL -
47
14,200
19
10
13,900
3,910
91
3.7
210
S3
6
10
78,200
437
42
6,600
306,000
- 87,000
533
2,800
2,100
3,200
- 55,000
1,210
39,000
7,700
2,700
1,680
315
3,900
4,700
430
35,000
48,000
5,500
45,000
22,000
702
20
1.5
24
BDL
1
23
165
12.5
M).l
24
1
BDL
1
360
126
15
1,300
23,600
16,000
252
1,050
380
500
1,700
933
6,720
157
7
BDL
BDL
17
98
a
1,600
2,310
BDL
3,470
1,100
77
_c
3
1
1
2
1
1
1
1
1
3
3
3
3
3
3
3
1
3
3
3
3
3
3
1
1
BDL - 1,460 433
BDL
BDL
BDL - 27,000 10
71
BDL
BDL
BDL
BDL
BDL - 2,830 -"
BDL - 2,060 -*
BDL - 1,510 920
BDL BDL
BDL BDL
BDL BDL
BDL BDL
BDL - 18 -*
BDL BDL
BDL - 262
BDL - 824
BDL BDL
BDL - 3,140 -C
BDL - 194 -°
2,600
9
7
11
7
7
11
11
7
7
7
7
7
7
8
7
5
5
17
5
5
5
5
5
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
5
5
BDL
BDL
BDL
BDL
1
18
BDL
BDL
2
BDL
BDL
BDL
47
BDL
BDL
BDL
32
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
_
-
-
_
-
-
-
-
-
-
_
.
14
6,980
13
7
6,600
4,000
37
2
150
39
4
7
41,000
305
4
140
134,000
16,000
5
33
20
140
18,000
190
37,000
3.400
290
2,500
63
210
19,000
BDL
BDL
BDL
BDL
BDL
BDL
13
BDL
_
-
.
„
-
_
—
17,000
16,000
110
36,000
9,400
1,900
23
1
29
BDL
MJ.S
22.5
92
4
MJ.05
14.5
1
BDL
BDL
252
9
BDL
BDL
5,300
15
BDL
10
BDL
23
90
4
59
BDL
BDL
BDL
BDL
BDL
BDL
BDL
106
36
BDL
33
77
140
BDL
Includes plants treating with organic preservatives only plus those treating with both organic and inorganic preservatives;
steaming and/or Boulton process or both.
See also conventional pollutants.
°Detected in one sample only.
Date: 6/23/80
II.21-8
-------
D
0>
rt
(D
NJ
U)
00
o
TABLE 21-6.
H
•
K)
I-1
I
VD
TOXIC POLLUTANT LOADINGS FOUND IN STEAMING AND BOULTON
SUBCATEGORY WASTEWATER [1]
[lb/ft3 (kg/m3)]
Raw wastewater
Steaming process
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
Number
of
plants
8
12
8
8
11
12
8
8
8
8
8
8
8
5
3
3
15
3
3
Range
<0.01
(<0.16
<0.01
(<0.16
<0.01
(<0.16
<0.01
(<0.16
<0.01
(<0.16
0.06
(1.0
0.01
(0.16
<0.01
(<0.16
0.02
(0.32
<0.01
(<0.16
<0.01
(<0.16
<0.01
(<0.16
0.66
(10.6
<0.1
(<1.6
BDL
(BDL
2.3
(37.0
<0.1
(<1.6
311
(5,010
BDL
(BDL
- 0.82
- 13.2)
- 246
- 3,960)
- 0.01
- 0.16)
- 0.03
- 0.48)
- 116
- 1,870)
- 9.59
- 154)
- 1.6
- 25.8)
- 0.03
- 0.48)
- 5.97
- 96.1)
- 0.35
- 5.6)
- 0.03
- 0.48)
- 0.13
- 2.09)
- 652
- 10,500)
- 6.4
- 103)
- 0.7
- 11.3)
- 107
- 1,720)
- 1,970
- 31,700)
- 425
- 6,840)
- 10.4
- 167)
Treated
Boulton process Steaming and
Number Number
of of
Median plants Range Median plants
0.01
(0.16)
0.2
(3.2)
<0.01
(<0.16)
<0.01
(<0.16)
0.4
(6.4)
1.5
(24.2)
0.07
(1.1)
<0.01
(<0.16)
0.13
(2.09)
0.03
(0.48)
<0.01
(<0.16)
0.01
(0.16)
3.38
(54.4)
1.4 3
(22.5)
0.3 1
(4.8)
24.3 1
(391)
214 3
(3,440)
321 1
(5,170)
4.4 1
(70.8)
11
11
7
7
11
11
7
7
7
7
7
7
7
<0.1 - 17.1 10.8 7
(<1.6 - 275) (174)
BDL 5
BDL 5
-------
o
0*
TABLE 21-6 (continued)
to
OJ
oo
o
ro
M
I
M
O
Raw wastewater
Toxic pollutant
Monocyclic aromatics
Benzene
Ethy Ibenzene
Toluene
Polycyclic aromatic
hydrocarbons
Acenaphthene
Acenapthalene
Anthracene/phenanthrene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f luoranthene
Benzo (ghi) perylene
Benzo (Jt) f luoranthene
Chrysene
Dibenzo ( ah ) anthracene
Fluoranthene
Fluorene
Indeno (1,2, 3-cd) pyrene
Naphthalene
Pyrene
Halogenated aliphatics
Methyl chloride
Methylene chloride
Steaming
process
Number
of
plants Range
3
3
3
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
1
3
10.3 -
(165 -
7.4 -
(119 -
9.7 -
(156 -
8.3 -
(134 -
0.1 -
(1.6 -
13.5 -
(217 -
<0.1 -
(<1.6 -
BDL -
(BDL -
BDL -
(BDL -
0.1 -
(<1.6 -
BDL -
(BDL -
<0.1 -
(<1.6 -
<0.1 -
(<1.6 -
4.9 -
(78.9 -
6.4 -
(103.0 -
<0.1 -
(<1.6 -
4.1 -
66.0 -
2.8 -
(45.1 -
1 -
(16.1 -
<0.1 -
(<1.6 -
31.5
506)
15.1
243)
49.5
797)
75.9
1,220)
23.2
374)
200
3,220)
27.3
440)
23.5
378)
29.3
472)
5.5
88.6)
29.3
472)
24.9
401)
1.6
25.8)
112
1,800)
61.1
984)
20.3
327)
540
8,690
84.4
1,360)
12.2
196)
0.1
1.6)
Median
18.3
(294)
7.7
(124)
11.8
(190)
33.0
(531)
9.2
(148)
94.7
(1,530)
3.0
(48.3)
0.1
(1.6)
0.2
(3.2)
<0.1
(<1.6)
0.2
(3.2)
3.1
(49.9)
<0.1
(1.6)
20.3
(327)
29.1
(469)
0.1
(1.6)
17.2
(277)
16.1
(259)
1.5
(24.2)
-
Boulton
process
Number
of
plants Range Median
1
1
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
1
<0.1 -
(<1.6 -
<0.1 -
(<1.6 -
<0.1 -
1.6 -
<0.1 -
(<1.6 -
<0.
(<1.
<0.
(<1.
<0.
<
<0.01
«0.2>
<0.01
(<0.2)
<0.01
(<0.2)
<0.08
(1.3)
0.06
(1.0)
<0.01
(<0.2)
<0.1
(1.6)
0.05
(0.8)
2.7
(43.5)
<0.1
(<2)
dlncludes plants treating with organic preservatives only plus those treating with both organic and inorganic preservatives. Steaming
and/or Boulton process or both.
-------
o
(U
rt
(D
NJ
00
O
to
I-1
I
TABLE 21-7. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND IN
STEAMING AND BOULTON SUBCATEGORY WASTEWATER [1]
(mg/L)
Raw wastewater
Steaming process
Pollutant
Phenols
PCP
Oil and grease
COD
TSS
Number
of
plants Range
15 0.640 - 501
15 BDL - 306
15 11 - 1,900
15 1,360 - 15,700
Number
of
Median plants
53.6
23.6
627
6,730
3
3
3
3
1
Treated effluent
Boulton process Steaming and
Number
of
Range Median plants
BDL - 1,270 184 17
BDL - 27 0.01 14
12.3 - 1,360 39.4 17
520 - 7,320 3,700 17
81
Boulton process
Range
0.048
0.032
9.3
100
- 680
- 134
- 1,220
- 10,600
Median
18
5
52
2,290
.9
.8
.3
-------
D
0)
rt
(D
CTi
OJ
00
o
N)
I-1
I
M
NJ
TABLE 21-8.
LOADINGS OF CONVENTIONAL POLLUTANTS FOUND IN
STEAMING AND BOULTON SUBCATEGORY WASTEWATER [1]
[lb/1,000 ft3 (kg/1,000 m3)]
Raw wastewater
Steaming process
Pollutant
Phenols
PCP
Oil and grease
COD
TSS
Number
of
plants Range
15 0.011
(0.1771
15 <0.0001
(<0.0016
15 0.0627
(1.01
15 (10.2
(164
- 11.4
- 184)
- 1.97
- 31.7)
-30.4
- 489)
- 283)
- 4,560)
Median
1.06
(17.1)
0.214
(3.44)
7.72
(124)
47.7
(768)
Boulton process
Number
of
plants Range
3
3
3
3
1
<0.0001
(<0.0016
•C0.0001
(<0.0016
0.0718
(1.16
3.44
(55.4
- 14.9
- 240)
- 0.179
- 2.88)
- 38.6
- 621)
- 208
- 3,350)
Treated effluent
Steaming and
Number
of
Median plants
1.
(24.
0.
(0.
0.
(7.
21.
(348)
0.
(8.
53 17
6)
0001 14
0016)
461 17
42)
6 17
537
65)
Boulton process
Range
0.0003
(0.0048
0.0004
(0.0064
0.0626
(1.01
0.821
(13.2
-6.92
- Ill)
-2.44
- 39.3)
- 13.5
- 217)
- 162
- 2,610)
Median
0.385
(6.20)
0.0336
(0.541)
0.706
(11.4)
23.8
(383)
-------
Chip wash water
Process Whitewater generated during fiber preparation
(refining and washing)
Process Whitewater generated during forming
Wastewater generated during miscellaneous operations
(dryer washing, finishing, housekeeping, etc.)
Reference 1 considers an average unit flow for Plant 97, which is
8.3 L/kg (2,000 gal/ton) to be representative of an insulation
board, mechanical refining plant which produces a full line of
insulation board products and which practices internal recycling
to the extent practicable.
Table 21-9 presents concentrations of toxic pollutants found in
insulation board manufacturing raw wastewater. Table 21-10
similarly presents toxic pollutant metals loading for this
subcategory.
II.21.2.3 Hardboard Manufacturing
Production of hardboard by wet process requires significant
amounts of water. Plants responding to the data collection
portfolio reported fresh water usage rates for process water
ranging from approximately 190 thousand to 19 million liters
per day (0.05 to 5 MGD). One plant, 543, which produces both
hardboard and insulation board in approximately equal amounts,
reported fresh water use of over 15 million liters per day
(4 MGD).
Water becomes contaminated during the production of hardboard
primarily through contact with the wood raw material during the
fiber preparation, forming, and—in the case of SIS hardboard—
pressing operations. The vast majority of pollutants consist
of fine wood fibers, soluble wood sugars, and extractives.
Additives not retained in the board also add to the pollutant
load.
The water used to process and transport the wood from the fiber
preparation stage through mat formation is referred to as process
Whitewater. Process Whitewater produced by the dewatering of
stock at any stage of the process is usually recycled to be used
as stock dilution water. However, due to the buildup of sus-
pended solids and dissolved organic material which can cause
undesirable effects in the board, there may be a need to bleed
off a quantity of excess process Whitewater.
More specifically, potential wastewater sources in the production
of wet process hardboard include:
Date: 6/23/80 11.21-13
-------
TABLE 21-9.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
INSULATION BOARD SUBCATEGORY RAW WASTEWATER [1]
(yg/L)
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Halogenated aliphatics
M 1 ^ f -m-TTL
Number
of
plants
4
4
4
4
4
4
4
4
4
4
4
4
4
•5
Range
0.67
1.6
0.5
0.5
1.3
200
1.3
1
8.8
3.3
0.5
0.5
250
1™> T*\T
- 3
- 3.3
- 0.83
- 1.0
- 11
- 450
- 21
- 7.5
- 240
- 5.0
- 0.6
- 0.83
- 720
•in
Median
1.46
2.5
0.5
0.565
4.9
310
3.3
5.8
58.5
4.5
0.5
0.7
534
•OT-iT
Phenols
Phenol
Monocyclic aromatics
Benzene
Toluene
3
3
BDL-40
BDL-70
BDL-60
BDL
40
40
One sample of raw wastewater contained 20 yg/L of
chloroform. Plant intake water contained 10 yg/L of
chloroform.
Plant 97 intake water contained 50 yg/L and 30 yg/L of
benzene and toluene, respectively.
Date: 6/23/80
11.21-14
-------
D
0)
rt
fD
to
LO
\
00
° TABLE 21-10. LOADINGS OF TOXIC POLLUTANT METALS FOUND IN
I
M
cn
INSULATION BOARD SUBCATEGORY RAW WASTEWATER [1]
[lb/106 ton (kg/106 Mg)]
Toxic pollutant
Range
Median
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
4.2 -
25 -
8.3 -
5.6 -
11 -
82 -
11 -
41 -
180 -
14 -
4.2 -
5.6 -
5,900 -
49
120
20
20
840
7,200
340
1,600
1,700
27
20
33
12,000
(2.1 -
(13 -
(4.2 -
(2.8 -
(5.5 -
(41 -
(6 -
(21 -
(90 -
(7 -
(2.1 -
(2.8 -
(3,000 -
25)
60)
10)
10)
470)
3,600)
170)
80)
850)
14)
10)
17)
6,000)
157
44
12.
13.
175
4,150
81.
62
1,040
70
10.
10.
9,200
5
5
5
4
6
-------
Chip wash water
Process Whitewater generated during fiber preparation
(refining and washing)
Process Whitewater generated during forming
Hot press squeezeout water
Wastewater generated during miscellaneous operations
(dryer washing, finishing, housekeeping, etc.)
A unit flow of 12 L/kg (2,800 gal/ton) is considered to be
representative in Reference 1 of an SIS hardboard plant which
produces a full line of hardboard products and which practices
internal recycling to the extent practicable. A unit flow of
24.6 L/kg (5,900 gal/ton) is considered to be representative in
Reference 1 of an S2S hardboard manufacturing plant which pro-
duces a full line of hardboard products and practices internal
recycling to the extent possible.
Available data analyses list primarily metals and inorganics as
toxic pollutants; no base/neutrals data are presented. Table
21-11 presents concentrations and pollutant loadings for toxic
pollutants found in hardboard manufacturing raw wastewater.
Table 21-12 similarly presents concentrations and loadings for
conventional pollutants.
II.21.3 PLANT SPECIFIC DESCRIPTIONS
Due to the nature of available plant specific data, only subcate-
gory wastewater characteristics could be derived, and plant
specific wastewater characterization information is not presented.
II.21.4 POLLUTANT REMOVABILITY
The following sections address the current level of in-place treat-
ment technology and the raw and treated effluent loads and percent
reduction for several pollutants and several plants. Information
is organized with respect to the aforementioned subcategories
[wood preserving including steaming and Boulton processes, insula-
tion board manufacturing, and hardboard manufacturing (SIS and
S2S)1 .
II.21.4.1 Wood Preserving
Tables 21-13 through 21-17 present the current level of in-place
treatment technology for Boulton-no dischargers, Boulton-indirect
dischargers, steaming-no dischargers, steaming-direct dischargers,
and steaming-indirect dischargers, respectively.
Tables 21-18 through 21-20 present average raw and treated waste
loads and percent removal for COD, phenols, oil and grease, and
pentachlorophenol for plants with less than BPT technology in
place, current pretreatment technology in place, and current BPT
technology in place.
Date: 6/23/80 11.21-16
-------
TABLE 21-11.
CONCENTRATIONS AND LOADINGS OF TOXIC
POLLUTNATS FOUND IN HARDBOARD MANUFAC-
TURING SUBCATEGORY RAW WASTEWATER ]1]
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phenols
Phenol
Monocyclic aromatics
Benzene
Ethylbenzene
Toluene
Halogenated aliphatics
Chloroform
1,1, 1-Trichloroethane
Number
of
plants
6
6
6
6
6
6
6
6
6
6
6
6
6
2
3
2
3
2
2
2
3
Concentration, pg/L
Range
0.5 -
1 -
0.5 -
0.5 -
1 -
33 -
2 -
0.05 -
3.3 -
0.8 -
0.5 -
0.5 -
190 -
BDL -
BDL -
BDL -
BDL -
BDL -
15 -
BDL -
BDL -
8
1.3
0.67
5
420
530
55
18
270
3.8
7
1.5
2,300
680b
300
b
80
9°b
2°b
70
20b
90
Median
2.65
1.2
0.5
0.5
52.5
355
4
1.35
7.5
2.15
0.585
0.585
665
c
BDL
BDL
BDLC
c
BDL
Loading, Ib/ton (kg/Mg)
Range
17 - 200 (9 - 100)
23 - 51 (12 - 26)
1-25 (0.5 - 13)
13 - 120 (7 - 60)
34 - 11,000 (17 - 5,500)
880 - 27,000 (440 - 14,000)
40 - 1,500 (20 - 750)
2.5 - 620 (1.2 - 310)
110 - 4,700 (55 - 2,400)
35 - 110 (18 - 55)
10 - 350 (5 - 180)
10 - 26 (5-13)
5,000 - 48,000 (2,500 - 24,000)
Median
99
31
14.5
35.5
475
7,150
102
28
190
46.5
17
21
15,500
(52)
(15.5)
(7.5)
(18)
(240)
(3,600)
(51)
(14.5)
(100)
(23.5)
(9)
(11)
(8,000)
fl
Pesticides and metabolites
Aldrin
BBC's
Chlordane
Heptachlor
<0.001
0.015
<0.001
<0.001
*S1S and S2S combined for metals - no observed difference.
bSIS type hardboard; no loading data.
CS2S type hardboard; no loading data.
dS!S and S2S processes combined; number of plants was not specified.
TABLE 21-12.
CONCENTRATIONS AND LOADINGS OF CONVENTIONAL
POLLUTANTS FOUND IN HARDBOARD MANUFACTURING
SUBCATEGORY RAW WASTEWATER3 [1]
Untreated wastewater concentration,
ng/L
Untreated wastewater loading,
Ib/ton (kg/Mg)
Pollutant
Range
Median
Range
Median
BODB
Total phenols
BDL - 8.9 0.335
3.77 - 232 (1.89 - 116) 74.7 (37.4)
0.006 - 0.086 (0.003 - 0.043) 0.019 (0.009)
Date: 6/23/80
11.21-17
-------
TABLE 21-13. CURRENT LEVEL OF IN-PLACE TECHNOLOGY,
BOULTON, NO DISCHARGERS3 Ul
~~~~~Number
of
plants Percent
Primary oil separation
Oil separation by DAF
Evaporation ponds
Spray or soil irrigation
Cooling tower evaporation
Thermal evaporation
Effluent recycle to boilers
or condensers
No discharge
20
1
15
1
4
1
4
2
83
4
63
4
17
4
17
8
Plants may use more than one technology.
TABLE 21-14. CURRENT LEVEL OF IN-PLACE TECHNOLOGY,
BOULTON, INDIRECT DISCHARGERS3 [1]
Number
of
plants Percent
Primary oil separation 11 100
Chemical flocculation and/
or oil absorbent media 4 36
Biological treatment 2 18
aPlants may use more than one technology.
Date: 6/23/80 11.21-18
-------
TABLE 21-15.
CURRENT LEVEL OF IN-PLACE TECHNOLOGY,
STEAMING, NO DISCHARGERS3 [1]
Gravity oil-water separation
Chemical flocculation or oil
absorptive media
Sand filtration
Oxidation lagoon
Aerated lagoon
Spray irrigation
Holding basin
Thermal evaporation
Solar evaporation pond
Spray assisted solar
evaporation
Effluent recycle to boiler
or condenser
Number
of
plants
44
5
8
3
10
9
22
2
20
17
10
Percent
77
8.
14
5
17
16
39
3.
35
30
17
8
5
Some plants use more than one technology.
TABLE 21-16.
CURRENT LEVEL OF IN-PLACE TECHNOLOGY,
STEAMING, DIRECT DISCHARGERS3 [1]
Gravity oil-water separation
Chemical flocculation or oil
absorptive media
Sand filtration
Oxidation lagoon
Aerated lagoon
Spray irrigation
Holding basin
Solar evaporation pond
Spray assisted solar
evaporation
Effluent recycle to boiler
or condenser
Number
of
plants
10
3
2
2
2
1
2
5
2
2
Percent
100
30
20
20
20
10
20
50
20
20
Some plants use more than one technology.
Date: 6/23/80
11.21-19
-------
TABLE 21-17.
CURRENT LEVEL OF IN-PLACE TECHNOLOGY,
STEAMING, INDIRECT DISCHARGERS51 [1]
Number
of
plants Percent
Gravity oil-water separation
Chemical flocculation or oil
absorptive media
Sand filtration
Oxidation lagoon
Aerated lagoon
Holding basin
Spray assisted solar
evaporation
Effluent recycle to boiler
or condenser
23
7
3
1
2
17
2
2
100
30
13
4
9
74
9
9
Some plants use more than one technology.
TABLE 12-18.
WOOD PRESERVING CONVENTIONAL POLLUTANT
DATA AVERAGES FOR PLANTS WITH LESS
THAN EQUIVALENT OF BPT TECHNOLOGY
IN-PLACE [1]
Pollutant
COD
Phenols
Oil and grease
Pentachlorophenol
Number
of
plants
3
3
3
3
Waste load,
lb/1,000 ft3
Raw Treated
92.8 31.2
1.77 1.01
8.71 1.75
0.498 0.151
Percent
removal
66.4
42.9
79.9
69.7
TABLE 21-19.
WOOD PRESERVING CONVENTIONAL POLLUTANT
DATA AVERAGES FOR PLANTS WITH CURRENT
PRETREATMENT TECHNOLOGY IN-PLACE [1]
Pollutant
COD
Phenols
Oil and grease
Pentachlorophenol
Number
of
plants
10
10
10
7
Waste load,
lb/1,000 ft3
Raw Treated
80.7 41.5
3.11 2.03
7.82 0.908
<0.294 0.0716
Percent
removal
48.6
34.7
88.4
<75.6
Date: 6/23/80
11.21-20
-------
TABLE 21-20.
WOOD PRESERVING CONVENTIONAL POLLUTANT
DATA AVERAGES FOR PLANTS WITH LESS
THAN THE EQUIVALENT OF BPT TECHNOLOGY
IN-PLACE [1]
Pollutant
COD
Phenols
Oil and grease
Pentachlorophenol
Number
of
plants
6
6
6
5
Waste load,
lb/1
Raw
31.3
2.41
4.32
<0.268
,000 ft3
Treated
6.00
0.0061
<0.821
0.0135
Percent
removal
80.8
99.7
>81.0
<95.0
Table 21-21 presents average raw and treated waste loads and
percent removals of methylene chloride, trichloromethylene,
benzene, ethylbenzene, and toluene for plants with current BPT
technology in place. Tables 21-22 and 21-23 present similar
data for base/neutral toxic pollutants for current pretreatment
technology and current BPT technology in place.
Tables 21-24 and 21-25 present similar data for wood preserving
phenols for plants with current pretreatment technology in place
and current BPT technology in place.
Additionally, Tables 21-26 through 21-30 present average metals
raw and treated waste loads and removals in a similar manner for
the wood preserving subcategory.
II.21.4.2 Insulation Board Manufacturing
Table 21-31 summarizes the current level of in-place treatment
technology for six plants. Tables 21-32 through 21-37 present
treated effluent characteristics and various average raw and
treated waste characteristics and removals for the insulation
board manufacturing subcategory.
II.21.4.3 Hardboard Manufacturing
Table 21-38 summarizes the current level of in-place treatment
technology for 13 hardboard manufacturing plants. Tables
21-39 through 21-45 present treated effluent characteristics
and various raw and treated waste characteristics and removals
for the hardboard manufacturing subcategory.
Date: 6/23/80
11.21-21
-------
TABLE 21-21.
WOOD PRESERVING VOLATILE ORGANIC ANALYSIS
DATA FOR PLANTS WITH CURRENT BPT TECHNOL-
OGY IN-PLACE [1]
Pollutant
Methylene chloride
Trichloromethylene
Benzene
Ethylbenzene
Toluene
Number
of
plants
3
3
3
3
3
Waste
lb/1,
Raw
0.0049
<0.0001
>0.0200
0.101
0.0237
load,
000 ft3
Treated
0.0043
<0.0002
<0.0003
<0.0001
<0.0009
Percent
removal
12.2
>98.5
>99.9
96.2
TABLE 21-22.
WOOD PRESERVING BASE NEUTRALS DATA
AVERAGES FOR PLANTS WITH CURRENT
TREATMENT TECHNOLOGY IN-PLACE [1]
Pollutant
Fluoranthene
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Pyrene
Benzo (a)pyrene
Indeno (1,2, 3-cd ) pyrene
Benzo (ghi ) perylene
Phenanthrene/anthracene
Benz (a) anthracene
Dibenz (ah) anthracene
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Chrysene
Bis(2-ethylhexyl) phthalate
Number
of
plants
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Waste load,
lb/106 ft3
Raw
<5.7
<0.1
<0.1
<3.8
<0.1
<0.1
<0.1
32.4
<0.6
<0.1
<13.7
<15.8
<11.7
<11.6
<0.3
<6.2
Treated
<0.3
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.8
<0.1
<0.1
<7.2
<0.8
<1.0
<0.3
<0.1
-------
TABLE 21-23.
WOOD PRESERVING BASE NEUTRALS DATA
AVERAGES FOR PLANTS WITH CURRENT
BPT TECHNOLOGY IN-PLACE [1]
Pollutant
Fluoranthene
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Pyrene
Benzo (a) pyrene
Indeno ( 1 , 2 , 3-cd ) pyrene
Benzo (ghi) perylene
Phenanthrene/anthracene
Benz (a) anthracene
Dibenz (ah) anthracene
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Chrysene
Bis(2-ethylhexyl) phthalate
Number
of
plants
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
Waste load,
lb/10« ft3
Raw
53.0
<9.1
12.7
39.5
<10.5
<7.3
<1.5
121
<12.9
<0.5
>186
43.6
4.9
34.4
<11.2
<0.2
Treated
8.8
<1.4
<1.5
3.2
<1.8
•<1.0
<0.4
<7.1
<2.4
<0.1
<0.4
2.2
<0.2
<1.5
<1.5
<0.1
Percent
removal
85.4
85.7
>89.7
93.0
83.9
89.6
78.9
>94.0
86.0
83.3
>99.8
95.3
>97.0
>95.9
83.1
66.7
Negligible removal.
TABLE 21-24.
WOOD PRESERVING PHENOLS DATA AVERAGES
FOR PLANTS WITH CURRENT PRETREATMENT
TECHNOLOGY IN-PLACE [1]
Pollutant
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
2,4, 6-Trichlorophenol
Pentachlorophenol
Number
of
plants
2
2
2
2
7
Haste load,
lb/103 ft3
Raw Treated
6.6 0.2
<0.1 <0.1
<0.1 <0.1
<0.1 <0.1
419 69.7
Percent
removal
97.1
_a
_a
_a
83.4
Negligible removal.
TABLE 21-25.
WOOD PRESERVING PHENOLS DATA AVERAGES
FOR PLANTS WITH CURRENT BPT TECHNOL-
OGY IN-PLACE [1]
Pollutant
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
2,4, 6-Trichlorophenol
Pentachlorophenol
Number
of
plants
3
3
3
3
5
Haste
lb/10
Raw
352
<0.4
44.5
<5.0
73.6
load,
3 ft3
Treated
<0.2
<0.1
<1.0
<0.1
13.5
Percent
removal
>99.9
75.0
>97.8
98.0
97.6
Date: 6/23/80
11.21-23
-------
TABLE 21-26.
WOOD PRESERVING METALS DATA, ORGANIC
PRESERVATIONS ONLY, AVERAGES FOR
PLANTS WITH CURRENT PRETREATMENT
TECHNOLOGY IN-PLACE [1]
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Number
of
plants
2
2
2
2
2
2
2
2
2
2
2
2
2
Waste load,
lb/106 ft3
Raw
<0.01
0.03
<0.01
<0.01
0.01
1.37
0,08
<0.01
0.05
0.01
<0.01
0.01
3.38
Treated
0.02
0.05
<0.01
<0.01
0.09
0.97
0.02
<0.01
0.01
0.05
<0.01
0.02
9.99
Percent
removal
_a
_a
_b
_a
29.2
75.0,
_a
_a
_b
_a
Negative removal.
Negligible removal.
TABLE 21-27.
WOOD PRESERVING METALS DATA, ORGANIC
PRESERVATIONS ONLY, AVERAGES FOR
PLANTS WITH CURRENT BPT TECHNOLOGY
IN-PLACE [1]
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Number
of
plants
4
4
4
4
4
4
4
4
4
4
4
4
4
Waste load,
lb/10« ft3
Raw Treated
0.22 <0.08
61.6 34
<0.01 <0.01
<0.01 <0.02
0.12 0.1
0.48 0.35
0.43 <0.21
<0.01 <0.01
0.10 0.1
0.02 0.02
<0.01 <0.01
<0.01 <0.01
1.63 0.96
Percent
removal
>63.6
44.8
_a
_b
16.7
27.1
>51.2
_a
_a
_a
a
_a
41.1
Negative removal.
Negligible removal.
Date: 6/23/80
11.21-24
-------
TABLE 21-28.
WOOD PRESERVING METALS DATA, ORGANIC
AND INORGANIC PRESERVATIVES. AVERAGES
FOR PLANTS WITH LESS THAN CURRENT BPT
TECHNOLOGY IN-PLACE [1]
Pollutant
Arsenic
Chromium
Copper
Waste load,
lb/106 ft3
Raw Treated
0.43 0.44
0.53 0.56
1.67 1.71
Percent
removal
_a
a
a
Negative removal.
TABLE 21-29.
WOOD PRESERVING METALS DATA, ORGANIC
AND INORGANIC PRESERVATIVES, AVERAGES
FOR PLANTS WITH CURRENT PRETREATMENT
TECHNOLOGY IN-PLACE [1]
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Waste
lb/10
Raw
<0.05
<0.30
<0.01
<0.02
<7.28
3.9
0.03
<0.01
0.62
0.19
0.02
<0.01
60.1
load,
6 ft3
Treated
<0.03
<0.60
<0.01
<0. 03
<6.34
2.64
0.05
<0.01
0.67
0.14
<0.01
<0.01
56.1
Percent
removal
40
12
32
26
>50
6
.0
3i
.9
.3
.3
. o.
-
.7
Negative removal.
''Negligible removal.
Date: 6/23/80
11.21-25
-------
TABLE 21-30.
WOOD PRESERVING METALS DATA,
ORGANIC AND INORGANIC PRE-
SERVATIVES, AVERAGES FOR
PLANTS WITH CURRENT BPT
TECHNOLOGY IN-PLACE [1]
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Waste
lb/10
Raw
<0.01
2.53
<0.01
0.02
0.45
1.5
0.31
0.03
1.94
<0.01
<0.01
<0.01
2.33
load,
6 ft3
Treated
<0.01
2.5
<0.01
0.1
0.95
1.8
0.3
0.01
0.34
<0.01
<0.01
<0.01
3.06
Percent
remova 1
_a
a
~b
~b
~b
66.7
82.5,
_a
a
a
"t,
Negligible removal.
Negative removal.
TABLE 21-31.
IN-PLACE TREATMENT TECHNOLOGY
AT SIX INSULATION BOARD MANU-
FACTURING PLANTS [1]
Plant
number
Product/process
Treatment system
125 Structural/decorative
insulation board,
thermomechanical
373 Insulation board/
hardboard, thermo-
mechanical
531 Mechanical process
insulation board
555 Structural/decorative
insulation board,
mechanical process
931 Structural/decorative
insulation board,
mechanical process
1071 Insulation board/S2S
hardboard, thermo-
mechanical
Clarifier, aerated lagoon
Oxygen-activated sludge system,
clarifier
Aerated lagoon, evaporation pond,
self-contained discharger
(irrigation)
Clarifier, activated sludge
Floe clarifier, aerated lagoon,
discharge to POTW
Settling ponds, aerated lagoon,
oxidation pond
Date: 6/23/80
11.21-26
-------
TABLE 21-32. INSULATION BOARD THERMOMECHANICAL REFINING
TREATED EFFLUENT CHARACTERISTICS (ANNUAL
AVERAGE) [1]
Plant
number
125a
373b
1071
Production
Mg/d
139
145
605
359
tons/d
153
160
665C
395C
1,000
1.
1.
51.
21.
Flow
L/Mg
68
75
3
9
1,000
0.
0.
12.
5.
gal/ton
45
419
3
26
BOD
kg/Mg
2.
1.
4.
2.
03
94
06
15
Ib/ton
4.06
3.87
8.12
4.31
TSS
kg/Mg
1.71
1.13
12.3
0.94
Ib/ton
3.42
2.26
24.5
1.88
First line of data lists 1976 average annual daily data; second line lists 1977
average annual data, except as noted.
Data are taken before paper wastewater is added.
Includes both insulation board and hardboard production.
TABLE 21-33. INSULATION BOARD MECHANICAL REFINING
ANNUAL AVERAGE RAW AND TREATED WASTE
CHARACTERISTICS [1]
Plant
number
931a
555C
531
BOD,
Raw waste
4.33 (8.67)
20.8 (41.6)
20.9 (41.8)
1.27 (2.54)
kg/Mg ( Ib/ton )
Treated
effluent
1.05 (2.10)
0.28 (0.56)
0.28 (0.56)
0.07 (0.14)
Percent
reduction
76
99
99
94
TSS,
Raw waste
0.71 (1.42)
45.2 (90.5)
31.4 (62.9)
0.46 (0.923)
kg/Mg (Ib/ton)
Treated
effluent
1.15 (2.30)
2.64 (5.29)
1.46 (2.91)
0.16 (0.32)
Percent
reduction
_b
94
95
65
Raw waste loads were calculated from 1977 verification sampling data.
Negative removal.
°First line of data lists 1976 average annual daily data, second line lists 1977 average annual
daily data.
Date: 6/23/80 11.21-27
-------
TABLE 21-34.
INSULATION BOARD THERMOMECHANICAL REFINING
ANNUAL AVERAGE RAW AND TREATED WASTE
CHARACTERISTICS [1]
Plant
number
1253
373
1071
Raw
17.0
23.5
29.8
43.2
BOD,
waste
(34.
(47.
(59.
(86.
o!b
5)
3)
kg/Mg (Ib/ton)
Treated
effluent
2.03
1.94
4.06
2.15
(4.06)
(3.87)
(8.12)
(4.31)
Percent
reduction
88
92
86
95
TSS,
Raw waste
42.8
38.6
28.6
(85.7)b
(77.3)b
(57.1)
—
kg/Mg (Ib/ton)
Treated
effluent
1.71 (3
1.13 (2
12.3 (24
0.94 (1
.42)
.26)
.5)
.88)
Percent
reduction
96
97
57
__
aFirst line of data lists 1976 average annual daily data, second line lists 1977 average annual
daily data.
Data obtained during 1977 and 1978 verification sampling programs.
TABLE 21-35.
RAW AND TREATED EFFLUENT LOADS AND PERCENT
REDUCTION FOR TOTAL PHENOLS, INSULATION
BOARDa [1]
Plant
number
555
231
931
125
Raw waste load
kg/Mg
0.00095
0.007
0.0024
0.009
0.00040
0.0022
0.0055
Ib/ton
0.0019
0.014
0.0048
0.018
0.00079
0.0045
0.011
Treated waste load
kg/Mg
0.00010
0.00012
—
0.00008
0.00014
0.00065
Ib/ton
0.00021
0.00025
—
6.00015
0.00029
0.0013
Percent
reduction
89
98
—
81
94
88
Total phenols concentration data obtained during 1977 and
1978 verification sampling programs. Average annual daily
waste flow and production data for 1976 and 1977 supplied
by plants in response to data collection portfolio were used
to calculate waste loads.
Date: 6/23/80
11.21-28
-------
ft
(D
TABLE 21-36.
U)
oo
o
NJ
M
I
RAW AND TREATED EFFLUENT LOADINGS AND PERCENT
REDUCTIONS FOR INSULATION BOARD METALS [1]
Plant 931
Waste load, kg/108 Mg
(lb/10« ton) Percent
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Raw
2.1
(4.2)
13
(25)
4.2
(8.3)
2.8
(5.6)
6
(11)
1,900
(3,700)
6
(11)
2.1
(4.2)
800
(1,600)
14
(27)
2.1
(4.2)
2.8
(5.6)
3,000
(5,000)
Treated reduction
18
(35)
6 56
(11)
2.1 49
(4.2)
3.5
(6.9)
22
(44)
900 51
(1,900)
6 -b
(11)
0.4 80
(0.8)
600 31
(1,100)
7 52
(13)
2.1 -b
(4.2)
8
(15)
1,400 44
(2,800)
Plant 231
Waste load, kg/108 Mg
(lb/10« ton) Percent
Raw
25
(49)
27
(54)
7
14
8
(16)
60
(120)
2,300
(4,600)
170
(34)
41
(82)
850
(1,700)
35
(70)
4.9
(9.8)
4.1
(8.2)
4,200
(8,400)
Treated reduction
21 14
(42)
13 52
(26)
12
(24)
13
(26)
20
(40)
20 13
(40)
21
(41)
13
(26)
9 5
(18)
25 30
(49)
17
(33)
4.1 -b
(8.2)
4,700 -a
(9,500)
Plant 125
Waste load, kg/108 Mg
(Ib/lO" ton)
Raw
(27)
60
(120)
10
(20)
10
(20)
470
(940)
41
(82)
27
(53)
21
(41)
250
(490)
70
(140)
10
(20)
17
(33)
5,000
(10,000)
Treated
2.8
(5.6)
6
(12)
1
(1.0)
1
(1.0)
6
(11)
180
(350)
3.8
(7.5)
1.9
(3.8)
13
(26)
4.4
(8.7)
1.3
(2.5)
1.3
(2.5)
170
(330)
Percent
reduction
79
9O
90
90
98
a
85
91
94
93
88
92
96
Waste load,
(lb/10*
Raw
22
(44)
17
(34)
5.5
(11)
5.5
(11)
120
(220)
360
(7,200)
55
(11)
80
(160)
90
(180)
35
(7)
5
(11)
6.5
(13)
6,000
(12,000)
Plant 555
kg/108 Mg
ton)
Treated
48
(95)
20
(40)
6
(11)
6
(11)
90
(170)
1,200
(23,000)
18
(16)
0.7
(1.3)
37
(74)
32
(63)
7
(13)
8
(16)
800
(1,600)
Percent
reduction
a
a
a
a
26
68
85
99
58
10
a
a
86
Negative removal.
-------
TABLE 21-37.
INSULATION BOARD TOXIC POLLUTANT
DATA, ORGANICS [1]
Average concentration, vig/L
Pollutant
Chloroform
Benzene
Toluene
Phenol
Plant 231
20
70
40
BDL
Raw wastewater
Plant 555
BDLb
40°
40C
40
Plant 125
BDL
BDL
BDL
BDL
Treated
Plant 555
BDL
BDL
BDL
BDL
effluent
Plant 125a
BDL
BDL
BDL
BDL
One treated effluent sample contained 40 ug/L of trichlorofluoro-
methane.
One sample of raw wastewater contained 20 pg/L of chloroform. Plant
intake water contained 10 pg/L of chloroform.
Plant intake water contained 50 yg/L and 30 pg/L of benzene and
toluene, respectively.
TABLE 21-38.
IN-PLACE TREATMENT TECHNOLOGY AT 13
HARDBOARD MANUFACTURING PLANTS [1]
Plant
number
24
28
42
64
248
262
373
428
444
606
824
888
1071
Product
SIS, S2S
SIS
SIS, S2S
SIS
S2S
SIS
S2S
SIS, S2S
SIS
SIS
SIS
SIS
S2S
Treatment system
Activated sludge, aerated lagoon
Lime neutralization, discharge to POTW
Activated sludge, humus ponds, aerated
lagoons, settling pond
Settling ponds
Kinecs air pond, Infilco aero accelerators,
aerated lagoons, facultative lagoon
Settling pond, aerated lagoon
Not specified
Settling pond, aerated lagoon
Settling ponds, aerated lagoon
Settling ponds, activated sludge, aerated
lagoon
Aerated lagoons, settling ponds
Settling ponds, activated sludge, aerated
lagoon; no discharge
Clairfier, aerated lagoon, oxidation ponds
Date: 5/23/80
11.21-30
-------
TABLE 21-39. SIS HARDBOARD TREATED EFFLUENT CHARACTERISTICS
(ANNUAL AVERAGE) [1]
Plant
number
444
606
824
888C
42
24
64d
262
Production
Mg/d
88.7
194
194
117
115
91.9
343
1,450
111
111
67,0
64.1
tons/d
97.5
213
213
129
127
101
377
1,590
122
122
73.8
70.7
1,000
46.
7.
9.
8.
15.
—
4.
9.
4.
0.
21.
17.
Flow
L/Mg
6
38
35
84
2
16
40
24
62
4
2
1,000 gal/ton
11
1
2
2
3
-
1
2
1
0
5
4
.2b
.78
.24
.12
.65
-
.00
.26
.02
.15
.14
.12
BOD
kg/Mg
9.00
5. OS
9.35
6.85
3.06
—
0.13
0.97
18.5
5.10
5.85
5.35
Ib/ton
18. Ob
10.1
18.7
13.7
6.13
—
0.26
1.93
36.9
10.2
11.7
10.7
kg/
17.
4.
8.
10.
10.
—
0.
1.
1.
0.
13.
12.
TSS
Mg
1
05
50
1
2
12
14
59
59
8
2
Ib/ton
34. lb
8.10
17.0
20.2
20.4
—
0.24
2.27
3.18
1.17
27.6
24.5
aFirst line of data lists 1976 average annual daily data; second line lists 1977 average
annual data, except as noted.
Hardboard and paper waste streams are comingled.
CA11 of the treated effluent is recycled.
dSecond line lists data from October 1976 through February 1977.
TABLE 21-40. S2S HARDBOARD ANNUAL AVERAGE RAW AND
TREATED WASTE CHARACTERISTICS [1]
Plant
nuober
248'
1071
373
428
*First
Production
Mg/d
210
218
359
605
611
line of
(tons/d)
(231)
(240)
(395b)
(665b)
(343)
data lists
BOD,
Flow
1,000 t/Mg
18.3
21.6
21.9
51.3
25.8
1976 average
(1,000 gal/ton)
(4.39)
(5.17)
(5.26)
(12.3)
(6.18)
annual daily data.
Raw waste
66.5 (133)
62.0 (124)
43.2 (86.3)
29.8 (59.5)
116 (232)
second line
kg/Mg (Ib/ton)
TSS,
Treated Percent
effluent reduction
4.44 (8.88)
2.54 (5.07)
2.15 (4.31)
4.06 (8.12)
20.8 (41.5)
lists 1977 average
93
96
95
86
82
annual
Raw waste
.
11.
28.
20.
daily
.
7 (23.4)
6 (57.1)
0 (40.0)
data.
Kg/Mq (Ib/ton)
Treated
effluent
_
5.05 (10.1)
0.4 (1.88)
12.3 (24.5)
43.8 (87.6)
Percent
reduction
57
57
-
h
Negative reaoval.
Date: 6/23/80 11.21-31
-------
o
Q)
ti-
ro
en
NJ
OJ
CO
0 Plant
number Raw
444b 32.7
606 29.3
25.4
824 35.6
E 33.8
M 262 37.4
iL 42.0
42 1.89
24 21.9
TABLE 21-41.
BOD,
SIS HARDBOARD ANNUAL AVERAGE RAW AND
TREATED WASTE CHARACTERISTICS3 [I]
kg/Mg (Ib/ton)
Treated
waste
(65
(58
(50
(71
(67
(74
(84
(3
(43
.4)
.6)
.7)
.2)
.7)
.8)
.0)
.77)d
-8)e
effluent
9.00
5.05
9.35
6.85
3.06
5.85
5.35
0.13
0.97
(18.0)
(10.1)
(18.7)
(13.7)
(6.13)
(11.7)
(10.7)
(0.26)
(1.93)
Percent
TSS, kg/Mg (Ib/ton)
Treated
reduction
72
83
63
81
91
84
87
93
96
6.
12.
12.
22.
13.
12.
6.
0.
5.
Raw waste
90 (13.8)
4 (24.8)
8 (25.7)
5 (44.9)
0 (25.9)
6 (25.2)
45 (12.9)
56 (1.15)d
85 (11.7)6
effluent
17.
4.
8.
10.
10.
13.
12.
0.
1.
1 (34.
05 (8.
50 (17
1 (20.
2 (20.
8 (27.
2 (24.
12 (0.
14 (2.
1)
10)
.0)
2)
4)
6)
5)
24)
27)
Percent
reduction
c
67
34
55
21
c
c
79
81
aFirst line of data lists 1976 average annual daily data, second line lists 1977 average annual
daily data.
Hardboard and paper waste streams are comingled.
Q
Negative removal.
Raw waste loads shown are for combined weak and strong wastewater streams.
6 Raw waste load taken after primary clarification, pH adjustment, and nutrient addition.
-------
TABLE 21-42. RAW AND TREATED EFFLUENT LOADS AND PERCENT
REDUCTION FOR TOTAL PHENOLS, HARDBOARDa [1]
Plant
number
262b
42
24
824b
28
22
428b'd
Raw waste load
kg/Mg
0.005
0.0010
0.01
0.003
0.055
0.031
—
0.0015
0.10
Ib/ton
0.01
0.021
0.02
0.006
0.11
0.062
—
0.003
0.21
Treated waste loada
kg/Mg
0.00030
0.00020
0.00015
—
0.00046
0.065
0.003
0.0028
0.0005
0.00095
Ib/ton
0.00059
0.00040
0.0003
—
0.00092
0.13
0.006
0.0055
0.001
0.0019
Percent
reduction
94
98
98
—
99
—
c
99
Total phenols concentration data obtained during 1977 and
1978 verification sampling programs. Average annual daily
waste flow and production data supplied by plants in
response to data collection portfolio were used to calculate
waste loads.
First line lists 1976 data, second line lists 1977 data.
C
Negative removal.
1976 historical data supplied by plant in response to data
collection portfolio.
Date: 6/23/80
11.21-33
-------
o
ft)
rt
CD
CTi
CD
o
TABLE 21-43,
RAW AND TREATED EFFLUENT LOADINGS AND PERCENT
REDUCTIONS FOR HARDBOARD METALS [1]
H
•
tv)
M
I
U)
Plant 824
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Waste load,
(lb/106
Raw
200
(400)
12
(23)
6
(12)
290
(570)
290
(580)
3,900
(7,800)
60
(120)
18
(35)
2,400
(4,700)
18
(35)
6
(12)
13
(26)
9,000
(17,000)
kg/106 Mg
ton) Percent
Treated reduction
8.5 96
(17)
20
(40)
4.5 25
(9)
4.5 98
(9)
6 98
(11)
1,400 64
(2,800)
20 67
(40)
18 -b
(35)
200 92
(4,700)
6 33
(12)
0.5 92
(1)
7 46
(14)
2,500 72
(4,900)
Waste load,
(lb/106
Raw
80
(150)
26
(51)
13
(25)
60
(120)
190
(370)
14,000
(27,000)
120
(240)
1.3
(2.5)
1,800
(3,500)
20
(40)
180
(350)
13
(25)
4,800
(9,600)
Plant 248
kg/106 Mg
ton) Percent
Treated reduction
9 89
(18)
24 8
(48)
9 31
(18)
37 38
(74)
43 77
(85)
9,000 36
(17,000)
37 69
(74)
37
(74)
330 82
(660)
19 8
(37)
85 53
(170)
13 -b
(25)
800 83
(1,600)
Plant 42
Waste load,
(lb/106
Raw
80
(150)
16
(32)
8
(16)
7
(13)
100
(190)
440
(880)
800
(1,500)
27
(05.3)
800
(1,500)
50
(100)
7
(13)
13
(26)
3,000
(5,000)
kg/106 Mg
ton)
Treated
10
(20)
17
(14)
2.8
(5.6)
8
(16)
24
(47)
17
(33)
33
(65)
1.1
(2.2)
24
(47)
20
(39)
33
(66)
23
(45)
260
(520)
Percent
reduction
87
56
65
a
76
96
96
59
97
60
53
82
91
(continued)
-------
TABLE 21-43 (continued)
rt
(D
00
o
I
U)
Ui
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Plant 824
Waste load, kg/108 Mg
(lb/10e ton) Percent
Raw Treated reduction
24
(48)
14
(27)
15
(10)
15
(10)
90
(170)
1,100
(2,100)
20
(40)
11
(21)
60
(120)
24
(48)
5
(10)
5
(10)
24,000
(48,000)
Plant 248
Waste load, kg/108 Mg
(lb/106 ton) Percent
Raw
9
(17)
17
(34)
9
(17)
9
(17)
17
(34)
9,000
(17,000)
35
(69)
310
(62)
60
(110)
60
(110)
9
(17)
9
(17)
14,000
(27,000)
Treated reduction
9 -b
(17)
17 -b
(34)
9 -b
(17)
9 -b
(17)
35
(69)
4 , 000 56
(7,900)
26 26
(52)
70 77
(140)
35 42
(69)
47 15
(93)
9 -b
(17)
9 -b
(17)
6,000 53
(13,000)
Plant 42
Waste load,
(lb/108
Raw
100
(200)
15
(31)
7
(13)
7
(13)
6,000
(11,000)
3,300
(6,500)
42
(83)
22
(43)
120
(230)
23
(45)
9
(17)
9
(17)
7,000
(14,000)
kg/108 Mg
ton)
Treated
11
(23)
0.4
(0.9)
4.8
(9.6)
4.8
(9.6)
820
(160)
4.8
(96)
36
(71)
0.4
(0.7)
60
(110)
19
(38)
60
(110)
8
(16)
1,900
(3,800)
Percent
reduction
89
97
31
31
86
99
14
98
50
17
a
11
73
Negative removal.
Negligible removal.
-------
TABLE 21-44.
SIS HARDBOARD SUBCATEGORY TOXIC
POLLUTANT DATA, ORGANICS [1]
Average concentration, yg/L
Pollutant
Raw wastewater Treated effluent
Plant 262a Plant 824 Plant 262 Plant 824
Chloroform
Benzene
Ethylbenzene
Toluene
Phenol
BDL
BDL
20
15
BDL
20
80
BDL
70
680
BDL
10
BDL
BDL
BDL
BDL
80
BDL
70
20
*Plant 262 intake water contained 10 yg/L toluene and
97 yg/L phenol.
TABLE 21-45.
S2S HARDBOARD SUBCATEGORY TOXIC
POLLUTANT DATA, ORGANICS [1]
Average concentration, wg/L
Raw wastewater
Treated effluent
Pollutant
Plant 248 Plant 428 Plant 663 Plant 248 Plant 428 Plant 663
Chloroform
1,1, 2-Trichloroe thane
Benzene
Toluene
Phenol
BDL
BDL,
BDL
BDL
BDL
20
BDL
90a
60a
300
BDL
90
BDL
10
BDL
BDL
BDL
BDL.
ioob
BDL
BDL
BDL
40
30
BDL
BDL
BDL
BDL
BDL
BDL
Plant intake water was measured at 120 yg/L benzene and 80 ug/L toluene.
Plant reported a minor solvent spill in final settling pond prior to sampling.
Date: 6/23/80
11.21-36
-------
II.21.5 REFERENCES
1. Revised Technical Review of the Best Available Technology,
Best Demonstrated Technology, and Pretreatment Technology for
the Timber Products Processing Point Source Category (draft
contractors report). Contract 68-01-4827, U.S. Environmental
Protection Agency, Washington, D.C., October 1978.
2. NRDC Consent Decree Industry Summary - Timber Products
Processing.
Date: 6/23/80 11.21-37
-------
11.22 PUBLICLY OWNED TREATMENT WORKS (POTW'S)
II.22.1 INDUSTRY DESCRIPTION [1]
II.22.1.1 General Description
Publicly owned treatment works (POTW's), although not a true
industry, are discussed in this manual to support the evaluation
of industrial treatment facilities and practices. POTW's often
treat a variety of wastes including treated and untreated
industrial wastewater. Discharge at these facilities is normally
directly to a stream or lake. This section presents the results of
a pilot study of two selected POTW's, These two POTW's are the
initial effort to study 40 POTW's to determine the fate of toxic
pollutants entering POTW's, sponsored by the U.S. Environmental
Protection Agency, Effluent Guidelines Division. At this time,
only the two plants discussed here have been sampled and ana-
lyzed. Descriptions of these facilities are included in the
plant-specific description section of this report.
II.22.1.2 Subcategory Description
No subcategories are currently defined for POTW's.
II.22.2 WASTEWATER CHARACTERIZATION
POTW's do not generate wastewater to be treated. Instead, the
wastewater that is treated in the POTW originates from several
sources. The pollutant loading from these sources varies
considerably depending on the percentage of industrial and
municipal flow rates and loadings. Because of this variability
each POTW will have influent characteristics unique to that
facility. This section presents raw influent wastewater
characterization data on two individual POTW's.
POTW A accepts a large proportion of its influent total flow from
industrial sources, yielding a higher incidence of toxic pollu-
tants than POTW B. In all, 52 organic toxic pollutants and nine
toxic metals were found in the influent to this facility. Eight-
een organic toxic pollutants were measured above the minimum
detection limit and seven toxic metals were found in higher
concentrations than in POTW B. POTW A generally had higher
concentrations than POTW B of both toxic and conventional (BOD,
COD, TSS, etc) pollutants. Only a small percentage of industrial
Date: 6/23/80 11.22-1
-------
wastewater ±s mixed with the predominantly municipal influent at
POTW B. Thirty-three toxic organic pollutants were detected and
only five of these were detected above the minimum quantifiable
limit. Nine metallic toxic pollutants were found. Only zinc had
a higher concentration in POTW B than in POTW A.
Tables 22-1 through 22-4 presents an initial screening study of
raw wastewater characterization data for these two facilities.
TABLE 22-1.
CONCENTRATONS OF CONVENTIONAL POLLUTANTS
FOUND IN THE RAW WASTEWATER ENTERING
POTW A [1]
Samples
Pollutant analyzed
BOD5
COD
TOC
TSS
Total phenols
Oil and grease
27
26
27
27
83
78
Number of
Times
detected
above min
27
26
27
27
82
78
Concentration, mg/L
Average
220
430
210
180
< 0.130
49
Median
180
440
240
130
0.050
40
Minimum Maximum
80
180
39
77
<0.006
18
450
630
340
560
5.20
340
II.22.3 PLANT-SPECIFIC DESCRIPTIONS
Plant A has a design capacity of 4.5 x 105 m3/d (120 MGD) with
approximately 70% of its organic loading and 30% of its flow
contributed by industry. Plant B has a design capacity of
5.7 x 104 m3/d (15 MGD) with approximately 2% industrial flow.
The following paragraphs describe these facilities in greater
detail.
Plant A
The design capacity of Plant A is 1.1 x 106 m3/d (300 MGD)
primary flow and 4.5 x 10s m3/d (120 MGD) secondary flow.
Under normal dry weather conditions, the flow through this
system varies between 85% and 90% of its secondary capacity.
During the first week of sampling at the plant, the flow aver-
aged only 3.4 x 10s m3/d (91.0 MGD).
The original primary treatment facility was constructed in 1924,
and most of the sewers are as old or older than the primary
system. It is estimated that the collection system is
separate sewers and 40% combined sewers.
Date: 6/23/80
II.22-2
-------
TABLE 22-2.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
THE RAW WASTEWATER ENTERING POTW A [1]
Toxic Pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Number of
Samples Times
analyzed detected
23
23
23
23
23
23
84
23
23
23
23
23
23
23
Detected
above mm.
0
0
0
21
23
23
57
16
15
22
0
18
0
23
Concentration ua/L
Average Median Minimum Maximum
1-50
1-50
1-2
450
190
120 - 130
55 - 61
0.0 - 0.3
<98
1-50
<8
1-50
260
<50
<50
<2
9
370
150
24
41
0.3
66
<50
9
<50
260
<50
<50
<2
<2
63
35
10
20
0.2
<10
<50
<2
<50
23
<50
<50
<2
40
1400
860
1300
220
0.
350
<50
18
<50
500
.8
Ethers
Bis(2-chloroethoxy)methane
0-1
Phthalates
Bis ( 2-ethylhexyl ) phthalate
Butyl benzyl phthalate
Dl-n-butyl phthalate
Diethyl phthalate
Di-n-octyl phthalate
Dimethyl phthalate
Phenols
Pentachlorophenol
Phenol
2,4, 6-Trichlorophenol
p-Chloro-m-cresol
Aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1*, 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
chrysene
Fluoranthene
Flourene
Indeno(l, 2, 3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Balogenated aliphatics
Bromoform
Carbon tetrachloride
Chlorodlbromomethane
Chloroform
Dlchlorobromome thane
1 , 1-Dichloroethane
1,2-Dlchloroethane
1 , 1-Dichloroethylene
1 , 2-frans-dichloroethylene
Hexachlorobutadiene
Methyl ene chloride
Tetrachloroethylene
1,1, 1-Trichloroe thane
1,1, 2-Tnchloroethane
Trichloroethylene
Trichloro fluorome thane
28
28
28
28
28
28
28
28
28
28
82
82
28
28
28
82
28
82
28
28
28
28
28
28
28
28
28
28
28
82
82
82
82
82
82
82
82
82
28
82
82
87
82
82
82
26
11
19
17
1
11
7
27
1
1
81
9
15
6
14
75
1
81
1
2
1
21
5
8
8
2
23
21
10
1
6
1
79
1
19
1
60
69
1
82
81
71
3
81
2
14
1
14
0
0
0
0
9
0
0
45
0
0
0
0
28
0
56
0
0
0
0
0
0
0
0
1
0
1
0
1
0
67
0
0
0
5
18
0
20
58
45
1
49
0
25
1
1
1
0
1
1
13
0
0
-
-
-
-
-
29
4
8
6
1
3
2
19
1
1
290
0
1
1
1
21
0
35
0
0
0
1
0
1
1
0
1
1
3
0
0
0
43
0
1
0
1
4
0
8
47
15
-
_
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
—
_
_
-
_
_
.
-
-
_
-
-
.
1
5
2
S
27
1
38
1
1
1
7
1
2
2
1
8
7
6
1
1
1
44
1
2
1
7
11
1
16
50
18
<3
28
0
-
—
32
1
5
ND
ND
ND
ND
<10
ND
ND
37
ND
<10
ND
<5
<10
ND
13
ND
ND
ND
<10
ND
ND
ND
ND
<10
<10
ND
ND
ND
ND
21
ND
ND
ND
< 10
< 10
ND
< 10
16
10
ND
11
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
250
12
44
< J.Q
-------
TABLE 22-3.
CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND
IN THE RAW WASTEWATER ENTERING POTW B [1]
Number of
Pollutant
BODs
COD
TOC
TSS
Total phenols
Oil and grease
Saa(lefi
analyzed
7
7
7
7
42
40
Times
detected
above ain.
7
7
7
7
40
40
Concentration, mq/L
Average
95
180
70
97
<0.020
24
Median
96
180
69
87
0.012
26
Minimum
73
150
61
55
<0.001
5
Maxi
130
230
82
230
• o.
48
jouin
160
TABLE 22-4.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN THE
RAW WASTEWATER ENTERING POTW B [1]
Toxic Pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Phenols
Pentachlorophenol
Phenol
Aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 6-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Anthracene
Fluoranthene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Chlorodibromomethane
Chloroform
Dichlorobromomethane
1 , 1-Dichloroethane
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
1 , 2-Dichloropropane
Methylene chloride
Tetrachloroethylene
1,1, 2-Tnchloroethane
Pesticides and metabolites
Isophorone
Samples
analyzed
7
7
7
7
7
7
41
7
7
7
7
7
7
7
6
6
6
6
6
6
6
6
42
42
6
6
6
6
42
42
6
6
6
6
6
42
42
42
42
42
42
42
42
42
42
6
Number o:
Times
detected
6
6
S
5
1
4
1
4
31
2
5
1
1
1
18
32
3
3
4
3
3
3
40
4
2
2
16
1
39
41
14
1
f
Detectet
above mil
0
0
0
6
7
7
34
2
5
7
0
2
0
7
3
0
0
0
0
0
0
0
4
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
5
0
0
0
i
i. Ave
1
1
1
77
16
0.0
1
1
1
e
i
i
i
i
i
0
i
7
0
1
0
0
0
1
1
1
1
1
1
1
0
1
0
0
0
1
0
6
1
1
0
Concentration, pq/L
rage
- 50
- 50
- 2
<4
71
54
- 78
- 30
- 0.3
30
- 50
- 2
- 50
280
- 14
- 10
- 8
- 8
- 5
- 6
- 1
- 6
- 14
- 1
- 8
- 1
- 1
- 1
- 4
- 8
- 5
- 5
- 6
- 5
- 5
- 1
- 9
- 1
- 1
- 1
- 3
- 1
- 14
- 9
- 3
- 1
Median
<50
<50
<2
4
67
55
66
<20
0.2
31
<50
<2
<50
300
1
<10
<10
<10
<5
<10
ND
<10
<10
ND
<10
ND
ND
ND
ND
<10
<5
<5
<10
<5
<5
ND
<10
ND
ND
ND
ND
ND
<10
<10
ND
ND
Minimum
<50
<50
<2
<2
12
39
<10
<20
<0.2
11
<50
<2
<50
110
<10
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Maximum
<50
<50
<2
9
130
72
240
79
0.4
48
<50
6
<50
440
19
<10
<10
<10
<10
<10
<10
<10
260
<10
<10
<10
<10
<10
<10
37
<10
<10
<10
<10
<10
<10
<10
<10
<10
13
<10
<10
180
<10
<10
<10
Date: 6/23/80
II.22-4
-------
Sludge handling at this POTW involves primary sludge thickening
by gravity thickeners, secondary sludge thickening by dissolved
air flotation (DAF), vacuum filtration, and incineration. During
the sampling period at Plant A, the primary sludge flow averaged
1.2 x 10s m3/d (325,000 gal/d) and the secondary (waste activated)
sludge flow averaged 5.7 x 103 m3/d (1.5 MGD).
Industrial contributions to the flow are primarily from several
major industries: pharmaceutical manufacture, petrochemicals,
plating operations, and automotive foundries. Also contributing
to Plant A's sewage collection system are some coking operations
and some food processing plants.
The treatment unit operations at this conventional activated
sludge POTW begin with gravity flow from the drainage area to the
bar screens and grit chambers, from which lift pumps elevate the
wastewater for gravity flow through the rest of the plant. After
the lift pumps, the wastewater passes through pre-aeration,
primary settling, and clarification, and then proceeds into the
aeration chambers. After aeration, clarification, and chlorina-
tion, the wastewater is discharged to a local stream.
Tables 22-5 and 22-6 present conventional and toxic pollutant
data for the influent and final effluent streams of this facility.
Data are also presented for the effluent prior to chlorination,
and for the primary and secondary sludges.
TABLE 22-5.
CONCENTRATIONS OF CONVENTIONAL POLLUTANTS, FOUND
IN PUBLICLY OWNED TREATMENT WORKS (POTW),
PLANT A [1]
Pollutant
BOD 5
COD
TOC
TSS
Total phenols
Oil and grease
Concentration,
mg/L
Effluent Final
Influent pre-Cl, Effluent
200 22
420 69
260 55
140 10
0.18
53
13
68
65
20
0.013
4-6
Concentration, mg/L
Percent
removal
94
34
75
86
92
89 - 92
Primary
sludge
20,000
58,000
24,000
47,000
0.670
9,100
Secondary
sludge
6,000
6,700
2,700
6,300
<0.037
<480
Combined
sludge
6,700
18,000
8,200
1,800
-
-
1 average results.
Prechlorination
Plant B
The design capacity of Plant B is 5.7 x 104 m3/d (15 MGD), but
under normal operations between 3.0 x 104 m3/d and 3.7 x 104 m3/d
(8 and 10 MGD) receive secondary treatment. During the sam-
pling period of this pilot study the influent flow to the facility
Date: 6/23/80
II.22-5
-------
0>
rf
to
w
CO
o
TABLE 22-6.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND IN
PUBLICLY OWNED TREATMENT WORKS (POTW),
PLANT A [1]
Concentration range
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Ethers
Bis ( 2-chloroethoxy ) methane
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Acrylonitrile
3,3' -Dichlorobenzidine
Phenols
2-Chlorophenol
2 , 4-Dimethylphenol
P ent achl or opheno 1
Phenol
2,4,6-Trichlorophenol
p-Chloro-m-cresol
Influent
0-50
0-50
0-2
12
440
190
18
56
0.3
98
0-50
8
0-50
252
0-1
32 -36
1-4
2-9
0-6
0-4
ND
ND
ND
ND
ND
0-3
13 - 19
ND
ND
Effluent,
pre-C!2
<50
<50
<2
<4
42
13
-
<20
<0.4
50
<50
<2
<50
42
ND
<19
ND
<3
ND
ND
ND
ND
ND
ND
<3
<7
<10
ND
ND
, pg/L
Final
effluent
0-50
0-50
0-2
4-5
46
27
3-11
0-20
0.4
40
0-50
0-2
0-50
90
ND
11 - 16
0-4
0-6
0-3
0-1
0-1
ND
0-1
0-1
0-1
0-1
18 - 23
ND
ND
Percent Concentration, pg/L
removal Primary
range sludge
150
1,300
37
60 - 65 1,200
90 15,000
86 77,000
15 - 83 630
58 - 100 47,000
24 <3.1
59 13,000
10
74 - 100 25
2
64 150,000
ND
50 - 69 2,200
1
ND
ND
ND
ND
ND
ND
ND
ND
93
0-5 94
ND
ND
Secondary
sludge
<22
63
10
340
18,000
9,000
<75
1,600
<2.6
3,300
23
180
<1
13,000
ND
42
ND
ND
ND
ND
ND
3
ND
ND
ND
110
68
ND
ND
Combined
SJ.uage
66
180
<12
600
18,000
24,000
-
11,000
<2.7
3,200
<12
82
<1
48,000
ND
1,200
ND
ND
ND
ND
ND
ND
ND
ND
15
33
ND
(continued)
-------
o
pj
TABLE 22-6 (continued)
to
to
oo
o
S3
-vl
Concentration range, pg/L Percent
Toxic pollutant
Aromatics
Benzene
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 3 -Di Chlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
Hexachlorobenzene
Nitrobenzene
Toluene
1,2, 4-Trichlorobenzene
Polycyclic aromatic hydrocarbons
Acenaphthene
Acenaphthy 1 ene
Anthracene
Fluor an thene
Indeno (1,2, 3-cd )pyrene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Carbon tetrachloride
Chlorodibromomethane
Chloroform
Dichlorobromome thane
1 , 1-Dichloroethane
1 , 2-Dichloroethane
1 , 1-Dichloroethylene
1 , 2-Trans-di chloroethylene
1 , 2-Dichloropropane
Hexachlorobutadiene
Methylene chloride
Tetrachloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
Note: Blanks indicate sufficient
a, -,4.
Effluent,
Influent pre-Cl^
5-13
0-2
0-4
0-4
0-4
30 - 36
ND
ND
18 - 23
ND
0-1
ND
0-7
0-3
ND
1-8
0-7
0-3
1-2
ND
49 - 50
ND
0-2
ND
1-8
0-8
ND
ND
6-14
53 - 57
17 - 20
24 - 29
ND
data are not
<1
ND
ND
ND
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<28
ND
ND
ND
<5
ND
ND
ND
<10
<10
<10
<9
ND
available
Final removal
effluent range
0-5
ND
0-1
0-1
0-3
0-7 77-99
ND
ND
0-9 51-100
ND
ND
ND
0-4
0-4
0-1
0-4
0-4 1,600
0-6
ND 100
ND
15 - 21 57 - 70
0-2
ND
ND
0-7
0-2
ND
ND
1-10 0-91
1-9 83-98
0-7 59 - 100
0-9 65 - 100
0-1
Concentration, \tq/L
Primary
sludge
170
ND
ND
ND
ND
280
ND
ND
280
ND
170
ND
1,600
ND
ND
200
4
760
11
17
ND
57
11
ND
9
23
ND
ND
220
290
24
280
ND
Secondary
sludge
10
ND
ND
ND
ND
<4
ND
ND
2
ND
ND
ND
4
ND
8
4
840
ND
6
29
ND
56
ND
ND
ND
ND
ND
ND
250
7
ND
<1
ND
Combined
sludge
-
-
ND
ND
ND
-
ND
ND
-
ND
75
ND
840
ND
ND
<23
350
-
-
-
-
-
-
—
—
-
ND
-
-
—
-
Priority pollutant not detected in any sample are not listed.
-------
averaged 3.0 x 104 m3/d (8.09 MGD). This 18-year old treatment
facility (updated and expanded most recently in 1973) is designed
for a discharge with an effluent quality of not more than 10 mg/L
biochemical oxygen demand (BOD) and 12 mg/L of suspended solids.
The average BOD and total suspended solids discharges during the
week of sampling were 25 mg/L and 19 mg/L, respectively.
The treatment unit operations utilized at this conventional
activated sludge facility are as follows. Wastewater flows from
the sewer system to a diversion chamber from which it is pumped
to a height which allows gravity flow to the rest of the plant.
The wastewater then passes through parallel detritus tanks (grit
chambers), communitors, preaeration chambers and into the primary
settling tank. After primary settling, wastewater flows to the
aeration tanks, secondary settling, and chlorination, and, then
is discharged.
The primary sludge flow at this POTW is pumped to holding tanks
where it is combined with the thickened (via DAF) waste-activated
sludge. From this point, the combined sludge passes to the sludge
conditioning facilities where it is heated and pressurized prior
to vacuum filtration. The decant from the sludge conditioning
system and the filtrate is either returned to the sludge condi-
tioning building, or bled to the head of the aeration tanks.
The filter cake is incinerated and the resulting ash is slurried
to a diked lagoon on the plant property.
During the sampling period, the primary sludge flow averaged 110
m3/d (29,400 gal/d).
The sewer system for Plant B consists primarily of combined
sewers. Four main trunk lines cover the far sections of the
7.61 x 106 m2 (29.4 mi2) drainage area. The sewer lines are mostly
concrete construction and average 20 years in age, with some lines
over 50 years old. The age of the sewer lines accounts for the
estimate that as much as 40% to 50% of the total flow to the POTW
can be attributed to infiltration in the subsystems and intercep-
tors, according to the facilities plan, completed under the
authority of Section 201 of the Clean Water Act (PL 95-217). The
industrial contribution to the wastewater flow to Plant B can be
considered minimal. The areawide waste treatment management plan
under Section 208 of the Clean Water Act lists the zoning breakdown
of the drainage area as 96.6% residential, 1.0% retail business and
offices, and 2.4% industrial. The industries associated with this
drainage area are grain elevators, oil and fuel terminals, machine
tool and metalworking companies, box and insulation companies, and
one major chemical facility with its own National Pollutant Dis-
charge Elimination System (NPDES) discharge permit. With such a
small industrial flow, Plant B is considered to give a general
approximation of a typical residential treatment facility.
Date: 6/23/80 11.22-8
-------
Tables 22-7 and 22-8 present conventional and toxic pollutant
data for the influent, final effluent, prechlorination effluent,
and sludge streams for this facility.
TABLE 22-7. CONCENTRATIONS OF CONVENTIONAL POLLUTANTS FOUND
IN PUBLICLY OWNED TREATMENT WORKS (POTW),
PLANT Ba [1]
Concentration, mg/LConcentration, mg/L
Tap Effluent Final Percent Secondary Combined DAF
Pollutant water Influent pre-cl effluent removal sludge sludge blanket
BODS
COD
TOC
TSS
Total phenols
Oil and grease
<10
<1
22
3
0.006
7
95
180
70
97
0.020
24
20 25
52 57
29 33
12 19
<0.004
<8
74
69
53
80
84
67
8,500
32
12
22
0.008
<250 3
,000
,000
,000
0.460 2.800
,500 11,000
aWeek 1 average
Prechlorination
II.22.4 POLLUTANT REMOVABILITY
Wastewater treatment at POTW's can significantly reduce the con-
centration of pollutant parameters in the influent to the facility.
In the sampling at Plant A, BOD was reduced from an average influ-
ent concentration of 200 mg/L to 13 mg/L (94% removal) and the TSS
level was reduced from 140 mg/L to 20 mg/L (86% removal). Chromi-
um and copper were reduced to less than 50 pg/L (90% and 86% remov-
al, respectively). Cadmium, nickel, and zinc were removed to a
lesser extent (59% to 65% removal). Nine organic toxic pollutants
were detected in the influent at an average concentration over
10 pg/L. Eight of the nine were reduced by a minimum of 50%. Only
phenol at the levels measured was not effectively removed.
Plant B achieves typical removals of BOD and TSS (74% and 80%
removal, respectively). Toxic metals, already in low concentra-
tions, were often reduced below their detection limit. Cadmium,
copper, and zinc levels were reduced to between 69% and 81%.
Lead and nickel were removed less effectively. Organic toxic
pollutants at Plant B occurred at low levels and removal
efficiencies are not meaningful.
Removal percentages for these facilities are given in Tables 22-4
through 22-7 in the plant-specific description section.
Date: 6/23/80 II.22-9
-------
TABLE 22-8.
CONCENTRATIONS OF TOXIC POLLUTANTS FOUND
IN PUBLICLY OWNED TREATMENT WORKS (POTW),
PLANT B [1]
Concentration. ua/L Concentration, pg/L
Toxic pollutant
Metals and inorganics
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Phthalates
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Nitrogen compounds
Acrylonitrile
3,3' -Dichlorobenzidine
Phenols
2 -Ni tropheno 1
4-Nitrophenol
Pentachlorophenol
Phenol
Aromatics
Benzene
1,2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 6-Dinitrotoluene
Ethylbenzene
Toluene
Polycyclic aromatic hydrocarbons
Acenaphthylene
Anthracene
Chrysene
Fluor an thene
Naphthalene
Phenanthrene
Pyrene
Halogenated aliphatics
Bromoform
Chlorodibromomethane
Chloroform
Dichlorobromomethane
1 , 2 -Dichloroe thane
1 , 1-Dichloroethylene
1, 1-rrans-dichloroethylene
Methylene chloride
1,1, 1-Trichloroethane
Tri chl or oethyl ene
Pesticides and metabolites
Isophorone
Note: Blanks indicate sufficient
Tap
water
<50
<50
<2.0
<2.0
<5
6
<10
<20
<0.2
<10
<50
<2
<50
7
< 1Q
< 3.0
<10
< ]_o
ND
ND
ND
ND
ND
ND
ND
<10
ND
<10
ND
ND
ND
ND
<10
ND
ND
ND
ND
ND
ND
ND
<10
20
75
ND
ND
ND
ND
30
ND
ND
ND
data
Effluent Final Percent Secondary
Influent
0-50
0-50
<2.0
4-5
71
54
77 - 78
16 - 30
<0.3
30
0-50
1-3
0-50
280
9-14
0-10
0-8
0-8
0-5
0-7
ND
ND
ND
ND
0-2
0-7
7-14
0-8
0-2
0-2
0-2
0-4
1-8
ND
0-5
ND
0-5
0-7
0-5
0-5
ND
0-1
0-10
0-1
0-1
0-4
ND
6-14
0-2
<0 - 3
0-2
pre-Cl
<50
<50
<2.0
<2
26
11
<23
<0.2
21
<50
<7
<50
83
<11
<3
<6
<3
<1
<1
ND
ND
<8
<34
<4
<9
<1
<1
<3
ND
ND
<0.5
<5
<1
ND
ND
ND
ND
ND
ND
<2
<10
<2
<2
<2
<0.5
<9
<1
<0.5
ND
are not available;
effluent removal sludge
<50
<50
<2.0 890.0
<2 55 - 100
22 69
10 81
<140 340
<20
<0.2 5 - 100
20 33
<50
<2 0-84
<50
52 81
<9
<5
<6
<3
<3
<1
ND ND ND
<1
<4
<14
<1
<9
<4 44-84 <5
<4
<5
ND
ND
<1 5
<7 25
<3
ND
<1
ND
<4
ND
ND
ND ND ND
<3 ND
<10 0-91 ND
<3 35
<2 ND
<3 ND
ND ND ND
<10 180
<0.5 ND
0.5 ND
ND
priority pollutants not
Combined
sludge
39
150
<12.0
310
8,100
11,000
1,700
7,400
5.1
3,100
<28
<79
<2
<27,000
1,500
ND
ND
ND
ND
ND
41
ND
ND
ND
ND
4
33
ND
ND
ND
ND
2
340
ND
91
8
ND
91
91
45
ND
9
ND
74
ND
ND
ND
250
ND
ND
ND
DAF
blanket
890.0
2,900
<50
ND
10
10
230
ND
ND
ND
35
ND
ND
ND
250
ND
ND
detected in any sample are not listed.
aWeek 1 average.
Prechlorination.
Date: 6/23/80
11.22-10
-------
11. 22. 5 REFERENCES
1. Fate of Priority Pllutants in Publicly Owned Treatment
Works - Pilot Study. EPA-440/1-79-300, U.S. Environmental
Protection Agency, Washington, D.C., October 1979.
Date: 6/23/80 11.22-11
•ftU.S. GOVERNMENT PRINTING OFFICE: 1 98 0-3 25 ' 1 C *i /6 3 9 0
------- |